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Abrasion and Erosion 1

Abrasion and Erosion


Klaus Schneemann, Hüls AG, Marl, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . . . 1 5.1. Sliding Wear, Elastic Rolling Wear,


2. Types of Wear and Wear Mechanisms 1 and Oscillation Wear . . . . . . ..... 18
3. Behavior of Materials . . . . . . . . . . . 8 5.2. Abrasion Wear . . . . . . . . . . ..... 19
3.1. Metals . . . . . . . . . . . . . . . . . . . . . 9 5.3. Damage by Particle Erosion . ..... 20
3.2. Plastics and Elastomers . . . . . . . . . 13
5.4. Solid Particles-Free Erosion . ..... 22
3.3. Ceramics . . . . . . . . . . . . . . . . . . . 15
4. Surface Treatment and Coatings . . . 15 5.5. Damage Caused
5. Practical Examples of Abrasion and by Erosion – Corrosion . . . . . ..... 23
Erosion Damage . . . . . . . . . . . . . . 17 6. References . . . . . . . . . . . . . ..... 25

1. Introduction Wear, friction, and lubrication are described


under the term tribology as the science of the
Practical experience with industrial equipment, study, industrial application, and modification
machinery, and plant has shown that components of the phenomena and processes occurring be-
have only limited service lives. Damage and ul- tween surfaces which are acting against each
timate failure of the component can occur as a other and moving relative to one another; this
result of changes in the material that originate at includes boundary surface interactions between
the surface, even if the components are designed solids, and between solids and their gaseous or
such that long-term action of the forces alone liquid surroundings. Since at least two compo-
causes neither fracture nor undue deformation. nents of a system are involved in wear, it is not
If the reactions responsible for the damage a pure material characteristic, but only a sys-
are of electrochemical or predominantly chemi- tem characteristic. Wear itself is generally un-
cal nature, the term corrosion is normally used, derstood as progressive loss of material from the
whereas mechanical damage to the surface of surface of a solid body caused by mechanical
the component is defined as wear. Attempts to action, i.e., contact and relative motion with a
avoid a loss of material due to wear, or at least solid, liquid, or gaseous phase.
to reduce the loss, concentrate on making the af-
fected surface more resistant to wear. This can
be achieved by mechanical, thermal, or thermo- 2. Types of Wear and Wear
chemical treatment of the surface or by applying Mechanisms
or depositing metallic coatings. Under some cir-
cumstances the wear conditions can be changed The treatment of wear must take the diversity
by design measures so that the danger for the of tribological processes into account, and this
affected component surface is eliminated or re- requires precise analysis of the loads and of the
duced to a tolerable level. appearance of the damage. It is usual to sub-
With few exceptions (e.g., running-in of bear- divide the large number of wear processes into
ings), wear in engineering means an undesired types of wear and wear mechanisms, in which
change that causes very high costs every year; different mechanisms have to be allocated to one
in a highly developed, industrialized country this and the same type of wear.
can amount to ca. 1 – 2 % of the gross national The kinematic conditions and the types of
product [1]. materials involved in the wear determine the
Plant construction typical of the chemical in- types of wear, such as sliding wear, elastic
dustry plays an insignificant role, and wear is rolling wear, impact wear, and shock wear.
correctly known as “the problem child of me- Oscillating wear stress, or oscillation wear,
chanical engineering” [2]. is caused by oscillating sliding and by oscillat-

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.b01 09
2 Abrasion and Erosion
Table 1. Classifaction of types of wear (based on DIN 50 320)
Abrasion and Erosion 3

ing sliding parts when rolling or even on im- More often the material is removed by cut-
pact. Wear mechanisms characterize the ener- ting; so-called microchips are obtained. In duc-
getic and material interactions between the in- tile materials these two processes are predom-
dividual elements of a wear system. DIN 50 320 inant, but in relatively brittle materials micro-
differentiates between adhesion, abrasion, sur- particles break away and microgouging occurs.
face destruction, and tribochemical reaction as Depending on the number of components in-
the principle mechanisms (Table 1) [3]. volved, a distinction is made between two-body
and three-body abrasion wear. Sliding, shock,
Adhesion. If the micro-roughnesses on the and rolling are possible types of wear, see Ta-
“clean” surfaces of two solid bodies are in con- ble 2 [5].
tact with each other, high surface pressures Oscillating mechanical loads in the surface of
are generated locally; relative movements cause a solid can lead to surface destruction by mate-
cold welding which can lead to separation of ma- rial fatigue. This appears as formation and prop-
terial. Material transfer, scales, and shear dim- agation of cracks, and may lead to separation of
ples are typical wear patterns. material particles.
Tribological stress in the system can lead
Abrasion. When two bodies of different to tribochemical reactions in addition to purely
hardnesses slide against each other, abrasion physical processes. As a result layers can appear
causes the softer surface of the base body to on or between the touching surfaces. In general
be scratched by the harder counter body. This these wear mechanisms do not act in pure form
harder body can be a micro-roughness of the in practice; they usually occur in combinations.
counter body or a wear particle that has already According to [4] the relative proportions of
been removed. The penetration of the harder microplowing and microcutting can be deter-
counter body and the relative movement pro- mined from the profile of a wear groove (Fig. 2).
duce wear grooves or furrows in the softer body, The so-called f ab value is defined by
for which reason it is also called furrow wear
Av − (A1 +A2 )
(Fig. 1). If the softer material is plastically de- fab =
Av
formed and is displaced to the furrow edges, the
process is called microplowing. Material is not so that for the two extreme cases, pure mi-
removed in a single event but by the simulta- croplowing and pure microcutting, f ab becomes
neous action of many abrasive particles or by 0 and 1, respectively.
repeated furrowing by one particle [4].

Figure 2. Profile of a wear groove

The linear wear intensity W l/s is defined as


∆h
Wl/s =
s
where ∆h represents the reduction of thickness
of the worn component and s is the wear path.
Using the f ab value allows the wear intensity to
Figure 1. Mechanisms of material damage in furrow wear
A) Microplowing; B) Microcutting; C) Microfatigue; D) be expressed as
Microgouging p
Wl/s =ϕfab ·
Hdef
4
Table 2. Comparison of the characteristics of abrasive sliding, abrasive impact, and three-body abrasive wear

Abrasion and Erosion


Abrasion and Erosion 5

where p is the surface pressure, H def is the tion of the ratio HVdef /f ab in accordance with
hardness of the wearing material in the strain- the above equation. For different materials with
hardened state, and ϕ is the form factor. The the same hardness, the wear resistance increases
f ab value is a function of the effective surface with increasing strain-hardening capability; see
deformation caused by the abrading particles, Figure 4 [4].
the ductility of the worn material, and the ma- This assumes that in the test method the wear
terial’s strain-hardening behavior [6]. The value takes place at the so-called upper shelf of the
decreases with increasing ductility, increasing wear characteristic. In the treatment of wear
strain-hardening capability, and decreasing sur- problems, Wahl was the first to draw atten-
face deformation. tion to the connection between abrasive particle
hardness and wear [7]. He found that at a certain
value of the particle hardness the wear increases
sharply, and at higher values remains virtually
constant; see Figure 5.
Note, however, that the pure furrowing de-
scribed here occurs in tests with bonded parti-
cles, a condition which occurs relatively rarely
in practical situations. More typical is the case
where unbonded, loose particles are carried over
the surface of the component, and additional
rolling motion is also possible.
With increasing particle mobility, the wear
caused by loose particles represents the transi-
tion from abrasive sliding wear to erosion (abra-
sive – erosive attack).

Erosion. Erosion phenomena are caused by


flow, in which the flowing fluid itself is erosive
or the fluid carries particles that are unable to
follow the filaments of flow at surface irregu-
larities. In this case a shock component is often
superimposed on the plowing mechanism; this
causes local deformation and destruction.
If the fluid is a gas, tribochemical reactions
with the solid are only possible at fairly high
temperatures where the ablation mechanism can
act through the processes of sublimation, vapor-
ization, or fusion.
Figure 3. Dependence of the abrasive wear resistance of Pure liquid erosion occurs relatively rarely
metallic materials on the hardness of the material (A) and because even at high flow velocities the forces
on the ratio of the particle hardness to the factor f ab (B), acting are hardly sufficient to cause removal of
measured by the abrasive paper method, (SiC, 80 grain, material; exceptions to this are additional corro-
p = 3.54 MPa)
sive elements and the involvement of cavitation.
According to the above equation, a high wear
resistance means a small f ab value and a high Cavitation. Since the term cavitation is used
material hardness in the strain-hardened state. to describe the processes occurring in the liquid
According to this model, hardness alone often and also the resulting damage to the material sur-
fails to provide a reliable assessment of the ex- face, the latter is often called cavitational erosion
pected wear resistance. to avoid confusion. These processes are caused
Figure 3 A shows the wear resistance 1/W l/s by the formation and subsequent collapse of va-
as a function of hardness for various metals, por or gas bubbles in liquids. When the pressure
and Figure 3 B shows the resistance as a func- falls, dissolved gases evolve from small gaseous
6 Abrasion and Erosion

Figure 4. Schematic representation of the abrasive wear resistance in the upper shelf and the wear mechanisms plotted versus
the material hardness

uated by the interposed liquid layer [8]. Damage


is therefore only caused by bubbles which col-
lapse directly at or close to the surface.

Figure 5. Lower and upper shelf wear characteristic (abra-


sive paper method, 80 grain, p = 0.37 MPa)

nuclei, or evaporation takes place if the pressure


falls locally below the vapor pressure. In regions
of higher pressure in the liquid the bubbles im-
plode. If this implosion takes place directly at the
Figure 6. Dependence of drop impingement wear (wear
surface of the component, the cyclic, locally con- depth per centimeter impinging liquid column) on the im-
fined compressive stresses finally lead to micro- pact velocity for various materials
scopic fatigue phenomena. This resembles the a) Glass; b) Aluminum; c) Polyurethane; d) Sintered alu-
behavior of materials under vibratory stress. If mina
the vapor bubbles formed do not implode di- If the pressure differences are caused solely
rectly at the surface the shock intensity is atten- by flow, the resulting process is called flow cav-
Abrasion and Erosion 7

itation. However, vibrations of sufficiently high During hydraulic transport the particles fol-
frequency can initiate vibrational cavitation. low the streamlines of the fluid better than in
The material damage described can take pneumatic transport due to the smaller differ-
place by purely mechanical means, but in prac- ence in densities. Sliding jet wear is always
tice it is often considerably intensified by super- present in horizontal pipeline transport due to
imposed corrosion stress. the influence of gravity.
Comparable damage can occur through the Where changes in direction of flow occur,
repeated impact of drops or liquid jets at high (e.g., at pipe bends) the particles, due to their
velocity. After the deformability has become ex- higher density, are pressed to an increasing ex-
hausted in tough materials, initial cracks appear; tent against the surface, where they have an ero-
these develop into breaks and progress to deep sive action (Fig. 7) [10].
fissuring. This wear, known as drop impinge- The wear increases distinctly with increasing
ment, depends on the impact velocity (Fig. 6) velocity and can be described by the empirically
and the angle of impact [9]. determined expression
In chemical technology and process engi-
neering, the most important instances of erosion W (α) =C v n(α)
are those where the fluid contains solid parti-
cles. If the fluid is a liquid this type of wear where α is the angle of impact, C is a constant
is called hydroabrasive wear or scouring wear; that depends on the material and the abrasive, v is
with gaseous fluids it is called jet wear. In both the velocity, and n is a velocity exponent which
types of wear, plowing is active as the essen- depends on the material, the abrasive, and the
tial mechanism, and with steeper angles of im- angle. This equation is also valid for jet wear, in
pact there is an additional component causing which material is removed by impacting and/or
destruction of the material. Tribochemical reac- plowing particles in a carrier gas. Because of the
tions also occur. large number of forms which occur in practice
During hydraulic transport of solids in it is necessary to distinguish between the sliding
pipelines, the flow path lines near the surface jet, in which the particle slides over the surface
travel essentially parallel to the surface. The ero- of the workpiece, and the impact jet, in which the
sive effect of the particles is generally slight pro- particle strikes perpendicularly; all intermediate
vided that the flow remains undisturbed. Flow forms of jet (0◦ ≤ α ≤ 90◦ ) are called inclined
separation at irregularities causes turbulence, jets.
which can force the particles against the wall
and produce erosion. Typical irregularities in
pipelines are the protruding roots of welds. Fur-
thermore, in turbulent flow more collisions be-
tween particles occur, leading to impacts with
the enclosing walls.

Figure 8. Energy balance for the impact, without breakage,


of a hard particle on a ductile metal surface

The basic process in jet wear is the impact of


a particle against the surface at some arbitrary
Figure 7. Path of motion of hydraulically transported parti- angle. About 90 % of the kinetic energy of the
cles of various densities and diameters (calculated for water particle is converted into plastic deformation and
at 18 ◦ C and a flow rate of 2 m/s) heat (Fig. 8) [11]. The main energy conversion
takes place in the softer body [12].
8 Abrasion and Erosion

Estimates give values of a few thousand Soft, ductile materials exhibit higher wear un-
megapascals [13] for the pressures occurring on der furrowing conditions. At α = 0◦ , the vertical
impact and of microseconds [14] for the impact component of the force theoretically approaches
times (Fig. 9). The fatigue mechanism is domi- zero, so after a maximum the wear should also
nant where the impact is predominantly perpen- approach zero, but this situation does not actu-
dicular, while at shallow incident jet angles the ally occur in practice (Fig. 10) [15].
particle has a plowing action on the surface un-
der the influence of a normal force component Erosion – Corrosion. Under certain corro-
[15]. These result in different requirements for sive conditions many metals form covering lay-
the material involved: ers. If these are sufficiently dense they act as
protective films against corrosive removal of
1) Very hard materials are best for withstanding material. An example of this is the protective
plowing processes layer of iron oxide formed in unalloyed or low-
2) Impact processes cause little damage if the alloy boiler tubes. Erosion – corrosion is under-
energy can be absorbed elastically or plasti- stood as the combined action of mechanical sur-
cally. face removal and corrosion. With some soft and
loose layers the shear forces obtained with pure
flowing liquids at medium flow velocities are
sufficient to damage the protective layer with-
out the involvement of abrasive solid particles.
Where drop impingement or cavitation are in-
volved the mechanical removal of material is
understandable. On the other hand, diffusion-
controlled corrosion inhibition may be nullified
in flowing fluids as a result of saturation of the
boundary layer [16]. The resulting purely chem-
ical removal of material therefore no longer cor-
responds to the usual term of erosion – corrosion
and is now called flow-induced corrosion [17].

Figure 9. Variation of the calculated impact force of a sphere


(diameter 1 mm, velocity 100 m/s) with time for: 3. Behavior of Materials
a) C60H; b) St 37; c) Rubber
The many outward forms assumed by wear
mechanisms make it necessary to design the
component to be resistant to wear, at least on
the surface under attack. This can be accom-
plished by selecting a suitable base material or
by modifying the surface by mechanical, ther-
mal, or thermochemical treatment or by apply-
ing protective coverings of other materials [18].
Adequate wear resistance of a component is nor-
mally only one of several criteria in the require-
ment profile. Adequate strength, toughness, cor-
rosion resistance, and other properties, such as
ease of repair, are requirements which must also
be met. Economic criteria also have to be con-
Figure 10. Influence of the jet angle on the wear rate
a) Rubber; b) St 37; c) C60H
sidered. In general, theoretical considerations
and laboratory tests do not lead to a quick so-
Since hard materials normally have low duc- lution, and in most cases the final suitability is
tility, wear is low at small angles, but fragments proved under operational conditions. Wear prob-
are removed easily with perpendicular impact. lems can often be overcome by changes in de-
Abrasion and Erosion 9

sign or in the process technology. Metals, plas- the loading of the material is confined to the sur-
tics, ceramics, and protective coatings or layers face region, and in abrasive wear a penetration
are compared below purely from the aspect of process occurs that is similar to the hardness
material technology. tests. Unlike hardness tests, an additional tan-
gential force component also has to be taken into
account in the case of wear, which initiates ef-
3.1. Metals fects such as increase in temperature (possibly
associated with phase changes), reaction layer
There is still no comprehensive correlation avail- formation, and strain hardening by plastic de-
able between wear and hardness of materials. formation, and can therefore lead to permanent
Depending on the wear mechanism, other prop- changes in the tribological system.
erties, such as the state of the material’s mi-
crostructure, also play a significant role. Because
of the simplicity of the hardness test it is, how-
ever, useful to know which wear processes de-
pend essentially on hardness alone. In any case,

Figure 12. Dependence of wear intensity on the hardness


of the abrasive particles for particle furrowing for various
materials

It is usual to subdivide furrow wear into:


1) counterbody furrowing, in which the miner-
alogical grains are fixed on the surface of the
counterbody (e.g., a grinding wheel), and
2) particle furrowing, in which the wear is
caused by freely moving particles.
In trials both types show a similar dependence
Figure 11. Dependence of wear intensity on the hardness of of the wear rate on the hardness of the attacking
the abrasive particles for counterbody furrowing for various particle (lower shelf/upper shelf characteristic);
materials (abrasive paper method, p = 0.1 MPa, v = 0.25 m/s)
a) Rubber; b) Polystyrene; c) Cast basalt; d) Steel St 37; see Figs. 11 [19] and 12 [20].
e) C60H; f) Hard metal G4; g) Hard metal H2 For steels an increase in wear resistance is
observed with increasing hardness, whereby in-
10 Abrasion and Erosion

Figure 13. Wear resistance of cast iron towards particle furrowing (wear pot method, quartz sand)
a) Martensitic cast iron alloyed with Cr and Ni; b) Unalloyed and low-alloy pearlitic cast iron; c) Steels with 0.15 – 0.5 % C
and gray cast iron with lamellar or spheroidal graphite

Figure 14. Linear relationship between wear resistance and hardness in the upper shelf region (abrasive paper method, corun-
dum, 180 grain, p = 0.94 MPa)

creasing the hardness by alloying elements has hibit a linear relationship between resistance and
a greater effect than increasing the hardness by material hardness (Fig. 14) [22].
heat treatment.
With cast iron the wear resistance also tends Jet Wear. Materials in chemical plants are
to increase with increasing hardness. The maxi- usually transported through pipelines and con-
mum resistance values increase in the following verted in enclosing containers. Compressors and
order: gray cast iron with lamellar or spheroidal fans are used as the conveying units when
graphite, pearlitic cast iron, and martensitic cast gaseous materials are transported, while pumps
iron (Fig. 13) [21]. are normally used for liquids. The resulting wear
In the upper shelf region and in the presence phenomena are therefore associated with the
of normal abrasive particles, all pure metals ex- type of flow involved, and the various types of
wear are covered by the term erosion.
Abrasion and Erosion 11

Even at very high velocities pure gases are (Table 3) which relates predominantly to steel
only capable of damaging the enclosing solid and cast iron.
body when the temperature is high enough
to lead to thermally induced reactions. Prob- Wear with Liquids. The forces that
lems with gas conveying are therefore only to particle-free liquids exert on metal surface are so
be expected when entrained solid particles are low at the usual flow velocities of a few meters
present. In jet wear the material is elastically or per second that they do not cause any removal of
elastically/plastically deformed by impact of the material. According to Heil, no erosion effects
particles against the surface. could be detected with plain carbon steel, even
Apart from particle velocity the most impor- at 60 m/s, in a test method similar to that with
tant factor in jet wear is the jet angle: brittle met- the rotating disc [26]. Damage caused by liquid
als exhibit increasing wear with increasing an- flow alone is therefore relatively rare in practice.
gle of impact, with a maximum at 90◦ ; whereas The situation is different if, for example, a liquid
with tough metals, wear increases up to an an- under high pressure emerges with high velocity
gle of 15◦ – 40◦ , after which the loss decreases into a space of lower pressure; it may have an
at steeper angles. The ductility and strain hard- erosive action on the metal at the exit point.
ening at the surface are thought to be responsible This applies to an even greater extent if the fluid
for this behavior (Fig. 15) [23]. forms dense protective layers with the metal.
If these layers are removed mechanically, they
must be reformed, otherwise erosion will act in
combination with corrosion, which is known as
erosion – corrosion. This situation occurs very
frequently in practice as many metals can only
be used, for example, with water because a thin,
usually oxidic layer protects the metal against
corrosive attack. Table 4 gives guide values for
maximum permissible flow velocities for pure
water and, for comparison, for the more aggres-
sive seawater [27].
Since technical pure liquids usually contain
very fine solid particles, it is often difficult in
practice to differentiate between pure fluid ero-
sion and so-called hydro-abrasive wear. As with
jet wear, the number, hardness, and velocity of
entrained particles determine the extent to which
the protective covering layer is removed and the
extent of the pure metal wear. If mechanical
Figure 15. Impact jet and sliding jet components in jet wear
stressing due to entrained particles is predom-
a) Experimental curve for cast iron (2.8 % C, 21 % Cr); inant then hardness and strength are of decisive
b) Experimental curve for St 37; c) Impact jet component importance for metals, as shown in Figure 16 for
for cast iron; d) Impact jet component for St 37; e) Sliding copper alloys [28].
jet component for cast iron; f) Sliding jet component for St
37
Cavitation and Drop Impingement. Ac-
The relationship between wear resistance and cording to Grein all materials succumb to the
material hardness known from abrasion is valid exceptionally high mechanical stress occurring
only at small jet angles because of the compa- during cavitation if the intensity is sufficiently
rable wear mechanisms. According to Bitter high [29]. In soft materials such as aluminum,
[24], abrasion is dominant with the sliding jet cavitation erosion appears in the form of plas-
and surface destruction with the impacting jet. tic indentations caused by single implosions.
For the first-named conditions Wahl [25] With higher strength metals the damage starts
gives an appraisal of working characteristics by roughening of the surface after a certain in-
cubation time; as the destruction progresses the
12 Abrasion and Erosion
Table 3. Performance properties of wear resistant materials

Material Tensile strength, MPa Fracture strain, % Wear resistance

Low-alloy austenitic manganese steel 600 15 very low


Austenitic manganese hard steel 550 50 medium
Unalloyed steels 420 20 extremely low
High-strength low-alloy steels 600 18 extremely low
Pearlitic steels 500 – 600 12 extremely low
Martensitic steels 500 – 600 15 – 20 medium
Ledeburitic steels 600 2 high
Heat-treated 66 (gray cast iron) 250 < 0.5 very low
Heat-treated 666 (nodular iron) 500 3 low
Pearlitic white cast iron 250 < 0.5 high
Martensitic white cast iron 350 < 0.5 very high
High-chromium white cast iron 500 < 0.5 very high
Co – Cr – W – C alloy 500 < 0.5 very high
Hard metal 500 < 0.5 extremely high

interconnected holes eventually form a spongy soft, or very brittle, grain boundaries reduce the
structure. resistance.
Table 4. Maximum permissible flow rates for pure water and sea-
water
Material Flow rate, m/s

Pure water Seawater

Aluminum 1.2 – 1.5 1.0


Copper 1.8 1.0
Copper + As 2.1 1.0
Copper + Fe 4.0 1.5
CuZn28Sn 2.0 – 2.4 1.5 – 2.0
Al bronze ca. 3.0 ca. 2.0
CuNi10Fe 5.0 2.4
CuNi30Fe 6.0 4.5
Steel 3–6 2–5
Nickel alloys 30 15 – 25
Plastics 6–8 6–8

The following factors increase the resistance


to cavition erosion:
1) High corrosion resistance
Figure 16. Maximum tolerable flow rates (water) as a func- 2) Homogeneity
tion of material hardness for various copper alloys 3) Ductility
4) Compressive residual stress
In general, the strength and the fatigue 5) High strain-hardening capability
strength are the most important material param- 6) Smooth surface
eters for resistance to cavitation; hardness is 7) Fine-grained structure
therefore often used as a measure. With simi- 8) Fine-grained hard inclusions
lar microstructures, the metal with the higher 9) High content of hard components
hardness has the more favorable behavior, and 10) Layer structure
where different metals have the same hardness, 11) Wrought structure
the resistance improves with increasing tough-
ness. As cavitation attack takes place locally, the while the following reduce the resistance:
behavior is determined by the structural consti-
tution to a greater extent with this type of erosion 1) Low corrosion resistance
than with others. A homogeneous, fine-grained 2) Heterogeneity
microstructure is required; soft inclusions and 3) Brittleness
4) Tensile residual stress
Abrasion and Erosion 13

5) Low strain-hardening capability


6) Rough surface
7) Coarse-grained structure
8) Coarse-grained hard inclusions
9) High content of soft components
10) Dendritic structure
11) Cast structure
The data provided by Piltz [30] and Rein-
gans [31] can be used as guides for the selection
of materials.
As with other types of erosion, the superpo-
sition of a corrosion process also has to be taken
into account where damage by cavitation occurs.
Removal of material by corrosion after destruc-
tion of protective covering layers often repre-
sents the more intensive attack, and the corrosion
resistance of the material is then the dominant
property.
A comparable stress occurs with drop im-
pingement, characterized by repeated, short-
time liquid impacts. The comments made above
about cavitation also apply here to the material
behavior.

Figure 18. Wear relative to St 37 as a function of impact


angle for various materials (abrasive: quartz sand, particle
size 0.2 – 1.5 mm, HV = 1250)

Since residual stresses counteract the external


loading of the material they can increase resis-
tance to destruction perceptibly. In this sense,
strain hardening has a similar effect to carbur-
ization and nitriding [32].

3.2. Plastics and Elastomers

Figure 17. Relationship between wear and the reciprocal The relationship between wear and surface hard-
product of tensile strength S and fracture strain ε for poly- ness obtained for metals would predict a com-
mers paratively poor behavior for polymers. However,
1) Poly(methyl methacrylate); 2) Low-density polyethy- their special structural features give rise to prop-
lene; 3) Polystyrene; 4) Polyoxymethylene; 5) Polyamide
66; 6) Polypropylene; 7) Epoxy resin; 8) Polytetraflu- erties that can play a special role in wear.
oroethylene; 9) PMMA – acrylonitrile copolymer; 10) The viscoelastic deformation behavior is
Polyester; 11) Polychlorotrifluoroethylene; 12) Polycar- characterized by time-, temperature- and
bonate; 13) Polyamide 11; 14) ABS; 15) Poly(phenylene velocity-dependent deformation processes. Rel-
oxide); 16) Polysulfone; 17) Poly(vinyl chloride); 18)
Poly(vinylidene chloride) atively low levels of hardness and strength,
high plasticity, low thermal conductivity, and
14 Abrasion and Erosion
Table 5. Jet wear of polymers and metals

Material Hardness Abrasive * Relative wear W /W St37

Steel T 80 H 590 HV II 0.109


Polyurethane 18 Shore D II 0.143
Poly(vinyl chloride) 5 Shore D II 0.143
Polyurethane 34 Shore D II 0.403
Poly(vinyl chloride) 10 Shore D II 0.42
Rubber 17 Shore D II 0.57
Poly(vinyl chloride) 14 Shore D II 0.96
Steel St 37 122 HV I 1.0
Low-pressure polyethylene 60 Shore D I 1.06
Steel St 34 124 HV I 1.07
Poly(vinyl chloride) 17 Shore D II 1.12
Polyamide 6, Grilon R 50 62 Shore D I 1.33
Polyamide 6, Grilon R 70 64 Shore D I 1.33
Copper 99 HV I 1.36
High-pressure polyethylene 42 Shore D II 1.4
Low-pressure polyethylene 58 Shore D II 1.4
Polyamide 11, Rilsan Besvo 71 Shore D I 1.81
Low-pressure polyethylene 58 Shore D I 2.0
Low-pressure polyethylene 60 Shore D II 2.0
Polyamide 6, Ultramid 70 Shore D I 2.21
Aluminum 39 HV II 2.68
Brass 150 HV I 2.76
Aluminum 29 HV II 3.23
Polyamide 11 69 Shore D I 3.31
Poly(vinyl chloride) 52 Shore D II 4.2
Poly(vinyl chloride) 78 Shore D II 6.3
Resitex 89 Shore D II 8.2
Poly(vinyl chloride) 76 Shore D II 8.5
Glass 6 – 7 Mohs II 9.7
Lead 4 HV II 10.5
Plexiglas 85 Shore D II 10.75
Pertinax 92 Shore D II 18.5
Epoxy resin with glass fiber 86 Shore D II 19.5
Epoxy resin with hardener and quartz powder 84 Shore D II 31

* Abrasive I: sand, HV = 5000 MPa, particle size ≤ 0.9 mm; Abrasive II: sand, HV = 7200 – 8100 MPa, particle size 0.3 – 0.5 mm

high thermal expansion are effects of the weak Due to their material properties, polymers
secondary bonding forces between the macro- have proved successful where streams of small
molecules and their coiled structures. particles cause impact stress in addition to slid-
In particular, the low tendency to adhesion ing wear, i.e., with abrasive impact wear and
gives polymers their good slip characteristics with erosive attack. Although polymers gener-
with steels as the sliding partners – in the ab- ally have poor resistance to abrasive sliding at-
sence of additional abrasive particles – because tack, their ductility, especially of elastomers,
of the low frictional forces involved, and the leads to a behavior superior to that of met-
slip system is characterized by additional emer- als when the impacting component is dominant
gency running properties. Polyamide and PTFE (Fig. 18) [36]. Their behavior therefore differs
occupy the prime positions here as they possess significantly depending on the angle of impact.
good cohesive linkage properties compared with The material becomes heated due to internal fric-
other unreinforced polymers [33], [34]. tion, which can lead to complete failure at high
If abrasive sliding stress is present, the de- jet intensities.
pendence on hardness known for metals can- The preferred elastomers include the
not really be depicted in the same way. It polyurethanes and synthetic rubbers because
has been demonstrated that polymers exhibit a of their outstanding resistance to wear. In
good relationship between wear resistance and polyurethanes, greater resistance is found in the
crack propagation energy, or even between wear hardness range 70 – 95 Shore A, whereas normal
and the product of tensile strength and fracture grades of rubber reach their optimum between
strain; see Figure 17 [35]. 50 and 70 Shore A [37]. It is not possible to
Abrasion and Erosion 15

separate the influencing factors systematically hardness and melting point, but they are much
with respect to tribological behavior because of more brittle than the oxides and are only used
the large number of additives, types of rubber, in isolated instances as wearing bodies. Silicon
and applications (see Table 5) [38], [39]. carbide is characterized by its low thermal ex-
If, for rubber and C 60 H steel, the amount of pansion and high thermal conductivity and has
wear relative to St 37 steel is plotted versus the proved to be more resistant to thermal shock
impact angle and the hardness of the jet material than oxides. Zirconia is tougher than alumina; its
then, according to [40], it is possible to show the modulus of elasticity is only about half as large
very different wear behavior of these two mate- and is comparable with that of steel. Zirconia is
rials (Fig. 19). therefore very suitable for compound structures
with steel. At present the applications of ceramic
sintered materials in chemical plant construction
3.3. Ceramics are slide rings, pump parts, and slide bearings.
Ceramic materials have gained increasing im-
portance over the last few decades; in addition
to corrosion resistance and suitability for high
4. Surface Treatment and Coatings
temperatures the resistance to wear is the im-
The fact that wear starts at the surface of the
portant property of these materials. The above-
workpiece suggests that only the tribologically
mentioned properties of the sintered body can be
stressed surface should be strengthened instead
varied over a wide range by adjusting the pow-
of making the entire component out of wear-
dered raw material.
resistant material. It should be borne in mind
The nonmetallic, mechanically resistant ma-
that the base material has to fulfill other, for ex-
terials which are constituents of the ceramic ma-
ample, load-bearing functions as well as surface
terials can be subdivided into oxidic and nonoxi-
stressing, i.e., the surface which has been made
dic materials [41]. High melting points and hard-
wear-resistant must not interfere unduly with the
nesses are the outstanding properties, as shown
component.
in Table 6. :
If the material involved can be hardened then
Table 6. Hard materials various methods can be used to harden the sur-
Material mp, ◦ C , g/cm3 Vickers hard-
face to a certain depth by structural transforma-
ness HV0.2 tion, making it resistant to wear. These include
induction, flame hardening, HF impulse, elec-
Oxides
Al2 O3 2050 3.9 2300 tron, and laser jet methods. In case hardening,
ZrO2 2700 5.7 1100 a steel which originally cannot be hardened is
TiO2 1860 4.2 1000 made hardenable by inward diffusion of carbon,
Carbides
TiC 3150 4.9 3200 sometimes also with nitrogen; hardening is then
TaC 3780 14.5 1790 carried out by rapid quenching. The hardness
WC 2600 15.7 2080
SiC 2180 3.2 3000 achieved is governed essentially by the contents
B4 C 2450 2.5 3500 of dissolved C and N; the usual depths of appli-
Nitrides
TiN 2950 5.2 2450
cation are 0.5 to 2 mm.
TaN 3090 13.8 3230 Nitride layers are produced after treatment
Si3 N4 1900 3.2 1400 in a salt bath or in a gas atmosphere by inward
diffusion, usually below 600 ◦ C. Unlike trans-
BN (cubic) 3000 * 3.48 8000
Borides
TiB2 2900 4.4 3480 formation hardening, which is effected by lattice
ZrB2 2990 6.0 2200
Carbon
distortion as a result of embedded carbon atoms,
Diamond 3750 3.5 8000 – 10 000 nitriding and boriding provide the surface with
an exceptional increase in hardness by the for-
* Sublimes.
mation of an intermetallic bonding layer. These
bonding layers also increase the general corro-
Alumina is the most important oxidic sion resistance, but they are so thin that they can
abrasion-resistant material. Metal carbides are break by mechanical point loading.
in some ways superior to oxides with respect to
16 Abrasion and Erosion

Figure 19. Dependence of jet wear on the jet angle and the hardness of the impinging mineral

Hardfacing, on the other hand, is a thick tance is required. Where flat or rotationally sym-
layer process. By means of various welding tech- metrical surfaces have to be coated over large
niques, wear resistant alloys in rod, wire, or areas, automatic or fully-mechanized welding is
powder form build strong metallurgical bonds much cheaper than manual welding [42].
in the fused state with the surface, which is also Sheet metal plating by roll-bonded or explo-
fused. Mixing should be kept as low as possible. sion plating is not always as effective as weld
There is an exceptionally large variety of addi- plating with respect to adhesion. As the plating
tives available on the market and, among other material must be very plastically deformable to
things, the requirement for mechanical worka- achieve an intimate bond with the supporting
bility must be taken into account. Most filler material, highly wear resistant and high-strength
metals are alloyed on an Fe-base, but Ni or Co materials are unsuitable for the purpose. Never-
can also be the main constituents where high- theless, this method is widely used in chemical
temperature and/or additional corrosion resis- technology because to a large extent corrosion
Abrasion and Erosion 17

stresses are superimposed on the wear processes. Typical materials and applications for vac-
The selection of highly corrosion resistant alloys uum plasma spraying are:
applied to mechanically heavily stressed base
bodies provides satisfactory solutions to the ma- 1) M – Cr – Al – Y alloys for protection against
jority of problems in the construction of vessels corrosion by hot gases
and pipes [43]. 2) Carbides (WC, Co – Cr3 C2 , NiCr – TiC –
Thermal spraying can cause even greater NbC) for protection against abrasive wear and
adhesion problems than those of the above- erosion
mentioned coating methods. Unlike hardfacing, 3) Oxides and refractory metals for the forma-
after the coating additive has been fused in a tion of thick protective coatings [44]
flame, arc, or plasma it is projected against the The use of chemical vapor deposition (CVD)
cold or only slightly heated base. Adhesion to and physical vapor deposition (PVD) for form-
the surface and the density of the layer itself can ing coatings of carbides, borides, nitrides, and
differ greatly depending on the intensity of the oxides has increased. The CVD method has been
spraying and the possibility of reaction with the furthest developed for the deposition of TiC,
surrounding medium on the way to the base ma- TiN, CrC, WC, and Al2 O3 [45–48].
terial. From a micrograph it can be seen that, Surface treatment and coating of metals
depending on the process used, the layers have are discussed in more detail in → Corrosion,
a particular structure caused by agglomeration Chap. 5. and in → Metals, Surface Treatment.
of many fine globules of molten material, which
become deformed on impact and leave a visible
porosity in the composite material.
The most important groups of materials for 5. Practical Examples of Abrasion
wire flame spraying and arc spraying are and Erosion Damage
1) Low- and high-alloy steels Chemical industry with its manifold process
2) Bronzes, nonferrous metals such as nickel, steps involves conveying products from vessels
copper, zinc, Monel metal, brass, aluminum or tanks through pipelines to other vessels where
Powder flame spraying is a versatile method new products are produced by chemical reac-
of thermal coating and also handles tions, and then to still further apparatuses where
the solutions or mixture of products are sepa-
1) Special steel alloys with embedded mechani-
rated from one another. The process steps also
cally resistant materials
include mechanical processing such as com-
2) Ceramics with fairly high melting points
minution, kneading, and granulating. Produc-
3) So-called self-flowing Cr – Ni – B – Si alloys
tion of large quantities requires a continuous
which, after the actual spraying process –
material flow. This can be achieved most easily
without any adhesion layer – are submitted in
with fluid phases which are transported in con-
a second operation to subsequent treatment at
veying units. Erosion and abrasion are therefore
about 1100 ◦ C (liquid-phase sintering); this
the predominant types of wear in the main chem-
produces virtually pore-free layers with good
ical plant components, while sliding wear, elas-
adhesion characteristics.
tic rolling wear, and oscillation wear are found
Substantially higher temperatures are more in drives and machinery.
reached in the plasma process, so protective Transport velocities remain within defined
layers can be produced from high-melting ox- limits and material flows are relatively constant,
ides, carbides, and borides. The higher thermal so characteristic wear data which have been
energy and higher velocity produce improved determined under realistic conditions are quite
homogeneity and adhesive strength. readily transferable. Wear, as a form of damage,
The quality of this method is improved by the does not play a dominant part in chemical plants.
use of an inert atmosphere under reduced pres- Nevertheless, it does occur and the following ex-
sure. Individual alloying elements are not burnt amples give an impression of the diversity.
off, oxide and nitride formation is suppressed,
and adhesion and layer structure is improved.
18 Abrasion and Erosion

5.1. Sliding Wear, Elastic Rolling Wear, and for increasing the pressure of the transported
and Oscillation Wear medium. Its roller bearings are highly stressed
parts with a limited life. This can be shortened
The pulsation in gases which have been com- considerably if axial shocks are transmitted from
pressed in reciprocating compressors must be the flowing liquid as a result of large numbers of
adequately damped before the gases are trans- stops and starts, i.e., predominantly discontinu-
ferred to heat exchangers for cooling. This ous operation. This is often indicated by running
damping was not sufficient in the case of oxygen tracks displaced towards the edges (Fig. 22).
compression described here, so that the baffles
were continuously striking against the support-
ing spacer tubes; they deformed them increas-
ingly and caused sliding wear to the tubes seated
tightly against them (Fig. 20).

Figure 22. Surface destruction of a ball-bearing inner race


as a result of intermittent axial overloading

Predominantly transient stressing (radial im-


Figure 20. Sliding wear on copper tubes of a heat exchanger
pacts) occurred at the piston of an oxygen com-
for oxygen pressor where the surface of a stuffing box cham-
ber ring showed tribochemical reaction zones
Instances of damage caused by sliding oc- as a result of heating in contact with oxygen
cur quite frequently in piston machines. In the (Fig. 23). Because of the danger of spontaneous
rotary compressor shown (Roots type) for am- ignition of metals in the presence of compressed
monia compression the damage occurred after oxygen any processes involving friction in such
approximately 60 000 h operation (Fig. 21). machines must be treated with great caution.

Figure 21. Sliding wear damage on the rotary piston of a


Roots compressor for ammonia Figure 23. Tribochemical reaction and surface destruction
on the brass piston of an oxygen compressor
The centrifugal pump is the most important
hydraulic machine for setting a fluid in motion
Abrasion and Erosion 19

5.2. Abrasion Wear

Where abrasive impact wear occurs in hammer


mills, such as those used for comminution of raw
coal in power stations, continuous replacement
of plain plates of unalloyed steel is preferred to
the application of sustantially more expensive
materials with only moderately improved ser-
vice lives.
Three-body abrasive wear occurs relatively
frequently in machines used for process engi-
neering as the materials processed often contain
additives with abrasive properties. This is par-
ticularly true for the large number of barrel ex- Figure 25. Impact ribs (18 % Cr steel) of a wet comminution
truders used for kneading and milling processes. mill eroded by water containing carbon black
It is found, for example, in the draining of un- The screw housings which enclose the screw
vulcanized rubber, in which the moisture con- shafts are exposed to high stresses, similar to
tent is reduced from 60 to 10 % under a pres- those in the screw combs of the extruders. The
sure of 6 – 8 MPa. Screw elements made of 13 % product, which is processed under high pres-
Cr steel withstood these conditions for several sures, stresses the surface to an exceptional ex-
years without any signs of wear. However, when tent, especially in the so-called kneading zones
the unvulcanized rubber contains carbon black of worm extruders. If glass fibers or glass balls
the service life of screws made of X 40 Cr 13 are added to the product (in this case, polypropy-
is only about one year, even after hard-facing lene), even wear-protecting layers (60 % Ni,
with Hastelloy C (16 % Cr, 16 % Mo, remainder 18 % Co, 13 % Cr, 2 % Mo, 1 % C) applied by
Ni), Figure 24. This carbon black can be pro- centrifugal casting have only limited service life
cessed, for example, in a wet comminution mill: (Fig. 26). A suitable method of coating with ap-
1.5 t/h carbon black is ground with 30 t/h water at propriate protective material should be selected
3000 rpm between a stator and a rotor adjusted to to suit the type of stressing.
a gap of approximately 0.4 mm. Both parts have
impact ribs with special profiling and various
flow diverters. In this case the most economi-
cal solution was again to design the elements as
wearing parts made of 18 % Cr steel and replace
them after 7000 – 10 000 h operation (Fig. 25).

Figure 26. Abrasive wear caused by glass-fiber-containing


polypropylene on the high-alloy protective coating (60 %
Ni, 18 % Co, 2 % Mo, 1 % C) of a screw housing

Permanent magnet pumps with no seals are


being used increasingly for the sake of imission
Figure 24. Three-body abrasive wear, caused by carbon protection. The medium to be transported, in this
black, on a draining screw, hard-faced with Hastelloy C, case liquefied petroleum gas, flows through a
used for unvulcanized rubber gap of less than 1 mm around the non-contact
internal rotor, which is fitted with permanent
20 Abrasion and Erosion

magnets. Magnetite particles (Fe3 O4 ) originat-


ing from the pipeline adhere to the outer surface
of the internal rotor and cause permanent slid-
ing abrasion at the isolation shell and the rotor,
(Fig. 27); finally, this causes the entire pump sys-
tem to leak.

Figure 28. Hydroabrasive wear caused by a liquid contain-


ing carbon black in an unalloyed steel pipe as a result of
turbulences behind a weld

High mechanical stressing occurs when dis-


persions of plastics are atomized at high pres-
sure. Under some circumstances the acceleration
Figure 27. Abrasive wear on the inner rotor of a canned in a cone leading to the jet hole (a few tenths of
pump caused by adhering magnetite particles a millimeter in diameter) and passage through
the hole can change the geometry of a jet in a
very short time by erosion. This can affect hard
5.3. Damage by Particle Erosion metals and oxide ceramics as well as steel. Due
to the forces of acceleration produced in cen-
Abrasive wear is found predominantly in con- trifugal pumps, they are particularly liable to
veying equipment, but in pipelines and appara- hydroabrasive wear. Corrosion-resistant pumps
tus erosive wear is more typical, and is caused by made of cast CrNi (1.4408) had to be replaced af-
tribological stressing during the flow of fluids, ter only 6 months’ operating time; this was due to
usually with the involvement of solid particles. the erosion damage shown in Figure 29 because
Unlike the welded joints in apparatus, the butt the sharp-edged CuBi catalyst suspended in the
welds in pipelines can normally only be made aqueous solution had almost eroded through the
from the outside. Depending on geometrical fac- pump cover.
tors (e.g., edge misalignment, difference in wall
thickness) and the welding method, weld seam
roots are often produced which have a very con-
siderable sag. This can cause a great reduction
in the flow cross section and also, depending
on the flow conditions, marked turbulences be-
hind the roots. Figure 28 shows a section of a
pipe made of St 35.8 (unalloyed steel) in which
the carbon black content in a liquid mixture of
organic compounds caused a breach in the wall
after 15 months’ operating time as a result of hy-
droabrasion. The wall retained its original thick-
ness only a few centimeters behind the point of
turbulence, which illustrates the effect of the an- Figure 29. Pump cover (18-8 CrNi cast) eroded by sharp-
edged catalyst particles in the liquid
gle of incidence of the particle on the surface.
Even a ducted-wheel pump made of G-X3
CrNiMoCu 24 6 (Noridur 9.4460) hardly lasted
any longer, but the tempered and quenched cast
Abrasion and Erosion 21

alloy G-X170 CrMo 25 2 (Niroloy NL 262) had role here – and the protective layer and the tube
a service life of several years. elbow are worn away in a very restricted area,
When solid particles are carried in a gas as if with a milling cutter (Fig. 31).
stream and not in a guided liquid stream, any
changes in flow direction are very important as,
due to the large difference in density, the solid
particles are pressed with high force on to the
tube surface which guides the flow. The veloci-
ties of the transported gas may be very high and
then, as a result of intensive sliding jet wear at
localized points, lead to short term, but usually
accelerated, loss of wall thickness and to rupture
of the tube bends.
An example of this is provided by bends from
tube furnaces for the production, for example, of
ethylene. Because of the high operating temper-
atures of over 900 ◦ C, the required creep strength Figure 31. Tube elbow of a waste heat boiler whose pro-
and oxidation resistance are usually obtained by tective coating has been worn away in a restricted area by
using high-alloy materials (e.g., 30 % Cr, 30 % inclined jet wear, which ultimately penetrated the tube
Ni) and considerably increasing the wall thick-
ness at the bends. Figure 30 shows localized
penetration of this type. The wear stressing oc-
curs during repeated decoking with superheated
steam.

Figure 32. Plasma-coated protective shell of a steam super-


heater tube, damaged by impact jet wear at ca. 1000 ◦ C

Superimposition of flow and transient stress-


ing by particles in the gas flow, which is charac-
Figure 30. Bend in a tube furnace for ethylene production, teristic of impact wear and inclined jet wear, is
worn by sliding jet wear (material: CrNi 30/30 alloy) not found to any great extent in chemical plants
A comparable situation occurs in waste heat but does occur in power stations. It affects the
boilers that utilize the high temperature of syn- first contact heating surfaces where the ash par-
thesis gas (CO, H2 ) produced in an oil gasifica- ticles, at temperatures up to 1000 ◦ C rising at
tion plant for generating steam. Condensing and ca. 10 m/s with the flue gas, lead to impact jet
solidifying particles of slag often form a dense wear. These tubes, which are under high steam
and tightly adhering coating in the gas-carrying pressure, are therefore usually protected with
tubes, with the result that over a long period the heat-resistant wear-protecting half shells. In the
system provides its own protection against jet case described, comparative tests have shown
wear on the heat-resistant, low-alloy steels used. that high-alloy austenitic alloys (with 25 % Cr,
When there are changes in the mode of opera- 20 % Ni, and Si) last longer than high-chromium
tion, this protective action often fails locally – ferritic steels that have been plasma coated with
the gas velocity apparently plays an important an oxide layer (Fig. 32). It is assumed that metal-
22 Abrasion and Erosion

lurgical changes and chemical reactions caused if the heating is carried out with incompletely
by the high temperature combine with the purely dried steam at 2 MPa (Fig. 34).
mechanical stressing to form the complex out-
ward appearance.
However, if the wear-induced break occurs
in steam tubes, the expanding steam escaping at
high velocity causes erosion on adjacent tubes.
Although in this case there are again solid par-
ticles entrained in the flue gas, microscopic ob-
servation of the affected surface shows that, un-
like the situation with particle jet wear, there is
an ripple structure, typical of steam jet action
(Fig. 33).

Figure 34. Steam-heated high-pressure pipe showing liquid


erosion damage due to condensate carried with the steam

Rotary compressors include liquid ring


pumps, in which a rotor eccentric to the hous-
ing opens and closes chambers of different sizes
with the aid of a liquid ring; they are used as
compressors and vacuum pumps. Under some
circumstances cavitation of spontaneously va-
porizing liquid can lead to damage to the ro-
tor at the narrowest gap between the rotor and
the housing, as in the example shown in Fig-
Figure 33. Scanning electron micrograph of the surface of
a steam tube (material: 12 % Cr steel) damaged by a steam
ure 35, where the rotor is made of nodular cast
jet iron GGG 42. The different resistance to cavita-
tional stressing can be seen clearly on the sur-
face, where the harder iron phosphide eutectic is
largely retained, while the iron matrix has been
5.4. Solid Particles-Free Erosion worn away (Fig. 36). There is also the possibil-
ity that a certain corrosive component has con-
Heat transfer systems are one of the basic re- tributed to the damage, so this may be a case of
quirements of thermal process technology. De- cavitation corrosion.
pending on the purpose of the heat exchange, the
terms evaporator, liquefier or condenser, super-
heater, boiler, and many others, are also used.
If the flows of material taking part in the heat
transfer are separated from one another by walls,
the process is called indirect heat exchange. In
general, the flow conditions and prevailing ther-
mal conditions are sufficiently defined and main-
tained, so only in critical cases does mechanical
damage occur by erosion alone.
Liquid erosion damage is to be expected if
heating steam contains a proportion of conden-
sate – again dependent on the angle of incidence.
When compared with austenitic steels, steam-
Figure 35. Cavitation damage on a cast iron pump rotor
heated, high-pressure pipes made of low-alloy
ferritic steel prove to be insufficiently resistant
Abrasion and Erosion 23

impingement of droplets at a water content of ap-


proximately 8 % at room temperature (Fig. 38).

Figure 36. Micrograph of the rotor shown in Figure 35; al-


though the iron matrix has been removed by cavitation, the
more resistant iron phosphide eutectic remained unaffected
Figure 38. Impingement attack on a steam turbine blade (X
20 Cr 13)

A type of drop impingement can also lead to


purely mechanical damage and deformation on
such parts where a liquid-filled gap, in this case
between parts of a canned motor pump made of
steel 1.4408, is submitted to transient stressing
in the axial direction with simultaneous oscillat-
ing radial movement without contact between
the metal surfaces (Fig. 39).

Figure 37. Cavitation erosion in a steel (St. 35.8) heat ex-


changer tube due to excessive heating

Comparable conditions also caused the dam-


age shown in the following examples. Damage
occurred only in the region of the gas inlet of
a shell-and-tube heat exchanger in which the
tubes carry water in closed circuit for cooling.
This was because local vaporization of the water
followed immediately by collapse of the vapor
bubbles led to deep holes, while immediately Figure 39. Surface destruction of the case (18-8 CrNi steel)
after the gas inlet point the existing protective of a canned motor pump
layer remained completely undamaged on the The reason for this unusual type of stress-
unalloyed steel. The weakening visible in the ing was incorrect assembly in which the jointed
micrograph resembles that of pitting corrosion, parts had not been correctly secured.
and clearly the already broken protective layer
remains electrochemically active so that a corro-
sive removal mechanism is superimposed. The 5.5. Damage Caused by
hammering effect of the micro jet becomes ob- Erosion – Corrosion
vious from Figure 37. In steam turbines even a
chromium steel X 20 Cr 13 with otherwise good The chemical resistance of many metals to elec-
resistance properties is permanently damaged by trolytes is achieved because the reaction prod-
ucts adhere to the surface, hindering ionic trans-
24 Abrasion and Erosion

port that controls the electrochemical dissolu- umn made of 15 Mo 3 (DN 300). The high veloc-
tion process. Guide values can therefore be pro- ity together with the slightly corrosive medium
vided, for example, for the maximum velocity is entirely responsible for the loss in wall thick-
of drinking water up to which certain copper al- ness (Fig. 41).
loys, steels, and titanium retain their protective
coatings, and only when the measured values
are exceeded is removal of the protective layer
to be expected. In many cases unalloyed steel
and cooling water operating under defined flow
conditions represent the most economical solu-
tion for heat exchangers in the chemical indus-
try. Even then, the alternating actions of erosion
and corrosion can cause significant damage due
to the design and the associated changes in flow
direction, although with smooth flow it is pos-
sible to maintain a protective covering layer for
many years.
Cases of this type of damage can be clearly Figure 41. Erosion – corrosion due to turbulence of the liq-
demonstrated in heat exchangers from a CO con- uid caused by the reduction in diameter of a pipe (nominal
version process in which the gas preheats the re- diameter 300 mm, 15 Mo 5)
circulating water (nominal pressure 6.4 MPa) to
Occasionally the free fall of a corrosive liquid
a maximum of 220 ◦ C: excessive water veloci-
is also sufficient to remove protective layers and
ties through perforated impact plates, at changes
promote the corrosion process, as can be seen
in direction, and at tube openings through baffles
in a melting apparatus for dodecanedioic acid
prevented the formation of a complete protective
(Fig. 42).
layer; this led to progressive wear through liquid
erosion accelerated by electrolytic dissolution of
the metal (Fig. 40). It was possible to eliminate
this type of erosion on the internal surfaces of
vessels completely and permanently when they
were spray-coated with stainless Cr – Ni steel.

Figure 42. Erosion – corrosion caused by dripping molten


acid (material: 18-8 CrNi steel)

Crystalline acid with a moisture content of


10 – 20 % is fed through a filling hopper and
melted by heating tubes made of 18-8 CrNi steel,
Figure 40. Due to the high flow velocity of the cooling wa- and the vapor produced is driven off. This dam-
ter, the protective layer was removed from heat exchanger age, a combination of erosion and corrosion,
tubes (St. 35.8) and sheets (St. 37), leading to intensive ero- occurred at the region of highest temperature.
sion – corrosion
The complex stress profile of the extruder screw
Loss of material by preferential erosion – may also be demonstrated with the example of
corrosion caused by the flow conditions can be a kneader for unvulcanized rubber, in which, as
seen at a product outlet connection of a wash col- a result of a localized escape of fumaric acid
Abrasion and Erosion 25

and very small quantities of water, serious dam- 4. K. H. Zum Gahr: “Grundlagen des
age occurred within one day due to superim- Verschleißes,” in: Metallische und
posed erosion and corrosion of a kneading ele- nichtmetallische Werkstoffe und ihre
ment made of quenched and tempered ionitrided Verarbeitungsverfahren im Vergleich, part III,
chromium steel X 35 CrMo 17 (Fig. 43). VDI-Ber. 600.3 (1987) 29 – 56.
5. H. Uetz, K. Sommer:
“Abrasiv-Gleitverschleiß,” in: H. Uetz (ed.):
Abrasion und Erosion, Carl Hanser Verlag,
München – Wien 1986, pp. 108 – 157.
6. K. H. Zum Gahr: “Einfluß des Makroaufbaus
von Stahl/Polymer-Faserverbundwerkstoffen
auf den Abrasivverschleiß,” Z. Werkstofftech.
16 (1985) 297 – 305.
7. H. Wahl: “Verschleißprobleme im
Braunkohlenbergbau,” Braunkohle Wärme
Energie 3 (1951) 75 – 87.
8. R. Schulmeister: “Zur Untersuchung der
Werkstoffzerstörung durch Kavitation und
Korrosion mit Ultraschall-Koppelschwingern,”
Figure 43. Superposition of erosion and corrosion in a Metalloberfläche 21 (1967) no. 1, 17 – 25.
kneading element of a rubber extruder (material: X 35 CrMo 9. H. Rieger: Kavitation und Tropfenschlag,
17, ionitrided) Werkstofftechnische Verlagsgesellschaft,
Karlsruhe 1977.
10. H. Brauer, E. Kriegel: “Probleme des
Conclusion. In chemical plants the prob- Verschleißes von Rohrleitungen beim
lems of wear play a significantly smaller role pneumatischen und hydraulischen
than those of errosion. Damage in the component Feststofftransport,” Maschinenmarkt 71
equipment and pipelines is met relatively rarely, (1965) no. 68, 140 – 151.
although abrasion and erosion can occasionally 11. J. M. Hutchings: “Some Comments on the
be very detrimental to the potential availabil- Theoretical Treatment of Erosive Particle
ity of the plant components at risk. However, Impacts,” Proc. 5th Int. Conf. on Erosion by
it is a different question with machines and con- Solid and Liquid Impact, Cambridge 1979.
veying units, in which exceptionally high wear 12. G. Gommel: Stoßuntersuchungen
stresses can sometimes result from the influence Stahlkugel/Stahlplatte im Zusammenhang mit
of high flow velocities and high accelerations at Strahlmittelzertrümmerung und
housing walls, and especially at sliding seal el- Strahlverschleiß, Dissertation, TH Stuttgart
1966.
ements. The manufacturing industries make use
13. J. S. Rinehard, J. Pearson: Behavior of Metals
of the most modern materials technology to con-
Under Impulsive Load, American Society of
trol these problems. Nevertheless, design mea- Metals, Cleveland 1954.
sures also have to be chosen so that components 14. K. Wellinger, H. Uetz: “Strahlverschleiß,”
which are exposed to particular stresses and have Tech. Rundsch., 8 (1958) 1 – 8.
limited service lives are designed as easily re- 15. J. Föhl: “Strahl- und Spülverschleiß,” in: K. H.
placeable wearing parts. Zum Gahr (ed.): Reibung und Verschleiß,
Deutsche Gesellschaft für Metallkunde,
Oberursel 1983, pp. 157 – 176.
6. References 16. H.-G. Heitmann, W. Kastner:
“Erosionskorrosion in
1. BMFT-Report: Damit Rost und Verschleiß Wasser-Dampf-Kreisläufen – Ursachen und
nicht Milliarden fressen, BMFT, Bonn 1984. Gegenmaßnahmen, VGB Kraftwerkstech. 62
2. B. Genath: “Der Verschleiß ist das Sorgenkind (1982) 211 –219.
im Maschinenbau,” VDI-Nachr. 52 (1971) 17. H. Tischner: “Korrosionserscheinungen in
no. 47, 1, 6, 7. strömenden Medien am Beispiel von
3. DIN 50 320:Dec. 1979. Chemiepumpen,” Chem. Ing. Tech. 62 (1989)
no. 3, 220 – 228.
26 Abrasion and Erosion

18. C. Razim, C. Düll, W. Räuchle: “Über die der Basis von Modellrechnungen sowie
Beeinflussung der Bauteil-Grundeigenschaften experimentellen Ergebnissen,” Fortschr. Ber.
durch Verschleißschutzschichten,” VDI-Ber. VDI Z. Reihe 5 96 (1985).
333 (1979) 11 – 22. 35. J. K. Lancaster: “Abrasive Wear of Polymers,”
19. K. Wellinger, H. Uetz: “Gleitverschleiß, Wear 14 (1969) 223 – 239.
Spülverschleiß, Strahlverschleiß unter der 36. K. Wellinger, H. Uetz, G. Gommel:
Wirkung von körnigen Stoffen,” “Verschleiß durch Wirkung von körnigen
VDI-Forschungsh. 449, ed. B(1955) no. 21. mineralischen Stoffen,” Materialprüfung 9
20. M. Y. Gürleyik: (1967) no. 5, 153 – 160.
Gleitverschleißuntersuchungen an Metallen 37. H.-D. Ruprecht: “Elastomere-Polyurethane,”
und nichtmetallischen Hartstoffen unter in: H. Uetz (ed.): Abrasion und Erosion, Carl
Wirkung körniger Gegenstoffe, Dissertation, Hanser Verlag, München – Wien 1986,
TH Stuttgart 1967. pp. 438 – 450.
21. F. Henke: “Niedrig- und hochlegierter 38. H. P. Lachmann: “Elastomere-Gummi,” in H.
verschleiß-fester Vergütungsstahlguß,” Uetz (ed.): Abrasion und Erosion, Carl Hanser
Gießerei-Prax. 1975, no. 23/24, 377 – 407. Verlag, München – Wien 1986, pp. 451 – 465.
22. M. M. Krushchov, M. A. Babichev: 39. H. Brauer, E. Kriegel: “Untersuchungen über
“Experimental Fundaments of Abrasive Wear den Verschleiß von Kunststoffen und
Theory,” Russ. Eng. J. (Engl. Transl.) (1964) Metallen,” Chem. Ing. Techn. 35 (1963)
no. 6, pp. 43 – 48. 697 – 707.
23. H. Uetz, K. J. Groß: “Strahlverschleiß,” in: H.
40. K. Wellinger, H. Uetz: “Verschleiß durch
Uetz (ed.): Abrasion und Erosion, Carl Hanser
körnige mineralische Stoffe,” Aufbereit. Tech.
Verlag, München – Wien 1986, pp. 236 – 278.
4 (1963) 193 – 204, 319 – 335.
24. J. G. A. Bitter: “A Study of Erosion
41. E. Dörre: “Nichtmetallische Hartstoffe,” in H.
Phenomena,” Part I: Wear 6 (1963) 5 – 21; Part
Uetz (ed.): Abrasion und Erosion, Carl Hanser
II: Wear 6 (1963) 69 – 190.
25. W. Wahl: “Unterschiedliche Verlag, München – Wien 1986, pp. 451 – 465.
Werkstoffbewährung bei abrasiv 42. W. Wahl, I. Kretschmer, J. Wabnegger:
beanspruchten Bauteilen,” VDI-Ber. 600.3 “Auftragschweißen,” in H. Uetz (ed.):
(1987) 245 – 286. Abrasion und Erosion, Carl Hanser Verlag,
26. K. Heil: Erosionskorrosion an unlegierten München – Wien 1986, pp. 374 –394.
Eisenwerkstoffen in schnellströmenden 43. H. Gräfen: “Beschichtungen in der
Wässern, Dissertation, TH Darmstadt 1979. Chemietechnik,” in: Beschichtungen für
27. D. Kuron: “Korrosion durch Kühlwasser und Hochleistungs-Bauteile, VDI-Ber. 624
Schutzmaßnahmen,” in W. J. Bartz (ed.): Die (1986) 273 – 296.
Praxis des Korrosionsschutzes, Expert Verlag, 44. H.-M. Höhle: “Thermische Spritzverfahren,”
Grafenau 1981. in: Beschichtungen für
28. H. Sick: “Die Erosionsbeständigkeit von Hochleistungs-Bauteile, VDI-Ber. 624 (1986)
Kupferwerkstoffen gegenüber strömendem 71 – 83.
Wasser,” Werkst. Korros. 23 (1972) no. 1, 45. F. Wendl: “Aktuelle Trends bei der
12 – 18. Oberflächenbehandlung von Werkzeugen in
29. H. Grein: “Kavitation – eine Übersicht,” Sulzer der Kunststoffverarbeitung,” Thyssen Edelstahl
Forschungsh. 1974, 87 – 112. Tech. Ber. 15 (1989) no. 2, 110 – 125.
30. H. H. Piltz: Werkstoffzerstörung durch 46. H.-A. Mathesius: “Herstellen von
Kavitation, VDI-Verlag, Düsseldorf 1966. verschleißfesten Schichten mit Hilfe von
31. W. J. Rheingans: “Cavitation in Hydraulic CVD-Verfahren,” in: Beschichtungen für
Turbines,” Symp. on Erosion and Cavitation, Hochleistungs-Bauteile, VDI-Ber. 624 (1986)
ASTM Spec. Tech. Publ. 307 (1962) 17 – 31. 37 – 48.
32. K. H. Habig: Verschleiß und Härte von 47. H. Weiß: “Elektrochemische Beschichtung
Werkstoffen, Carl Hanser Verlag, München – und Sonderverfahren der Oberflächentechnik,”
Wien 1980, p. 215. Thyssen Edelstahl Tech. Ber. 15 (1989) no. 2,
33. H. Uetz, J. Wiedemeyer: Tribologie der 85 – 114.
Polymere, Carl Hanser Verlag, München – 48. H. Simon, M. Thoma: Angewandte
Wien 1985. Oberflächentechnik für metallische Werkstoffe,
34. J. Wiedemeyer: “Deutung des tribologischen
Carl Hanser Verlag, München – Wien 1985.
Verhaltens ungeschmierter Thermoplaste auf
Abrasives 1

Abrasives
Jean-Claude Menard, Federation of European Producers of Abrasives, 75041 Paris, France
Newman W. Thibault, Norton Co., Worcester, Massachusetts 01606, United States

1. Introduction . . . . . . . . . . . . . . . 1 5. Physical and Chemical Properties . 11


2. Natural Abrasives . . . . . . . . . . . . 1 5.1. Hardness . . . . . . . . . . . . . . . . . . 11
2.1. Quartz . . . . . . . . . . . . . . . . . . . 1 5.2. Grain Strength or Fracture Tough-
2.2. Garnet . . . . . . . . . . . . . . . . . . . 2 ness . . . . . . . . . . . . . . . . . . . . . 11
2.3. Corundum and Emery . . . . . . . . 2 5.3. Resistance to Attrition or Plastic
2.4. Diamond . . . . . . . . . . . . . . . . . . 2 Flow . . . . . . . . . . . . . . . . . . . . . 12
3. Manufactured Abrasives . . . . . . . 3 6. Loose-Grain Applications . . . . . . 12
3.1. Fused Aluminum Oxides . . . . . . . 3 7. Bonded Abrasive Products . . . . . . 13
3.1.1. Raw Materials . . . . . . . . . . . . . . . 3 7.1. Vitrified Bonds . . . . . . . . . . . . . . 13
3.1.2. Furnace Designs . . . . . . . . . . . . . 3 7.2. Organic Bonds . . . . . . . . . . . . . . 14
3.1.3. Fused Alumina Types . . . . . . . . . . 3
7.3. Metal Bonds . . . . . . . . . . . . . . . 15
3.2. Fused Zirconia – Aluminas . . . . . . 5
8. Coated Abrasive Products . . . . . . 15
3.3. Sintered Aluminas . . . . . . . . . . . 5
3.4. Silicon Carbide . . . . . . . . . . . . . 6 8.1. Components . . . . . . . . . . . . . . . 15
3.5. Boron Carbide . . . . . . . . . . . . . . 6 8.2. Production . . . . . . . . . . . . . . . . 16
3.6. Diamond . . . . . . . . . . . . . . . . . . 7 8.3. Applications . . . . . . . . . . . . . . . 16
3.7. Cubic Boron Nitride . . . . . . . . . . 7 9. International Quality Specifications 16
4. Manufacture and Testing of Sized 10. Safety . . . . . . . . . . . . . . . . . . . . 16
Grains . . . . . . . . . . . . . . . . . . . 8 11. References . . . . . . . . . . . . . . . . . 18

1. Introduction available on almost any aspect of the applica-


tion of their products. Most of them, as well as
An abrasive has been defined as “any of a wide some universities and miscellaneous organiza-
variety of natural or manufactured substances tions, also have Internet sites.
used to grind, wear down, rub away, smooth,
scour, clean or polish, often combined with a
binder to make grinding wheels or affixed with 2. Natural Abrasives
glue to the surface of paper or cloth” [1].
Although this broad definition could include 2.1. Quartz
such products as plastic pads, metal wool,
pumice, and various tools employing large sin- Quartz [14808-60-7] is found worldwide. Ma-
gle diamonds, as in bits for oil-well drilling, this jor applications include the abrasive for common
article is limited to granular abrasives as hard flint sandpaper used industrially for the finish-
as, or harder than, quartz (crystalline silicon di- ing of nonmetallic substances, such as leather
oxide) with grit sizes from about 5 mm average and felt, and also for miscellaneous household
diameter down to 1 µm or smaller. The abra- applications. Other uses are in sandblasting, in
sives can be used in their loose, bonded (grinding lapping of soft materials, as the cutting medium
wheel), or coated (sandpaper) forms. in wire sawing of soft stone, such as marble, and
Abrasives have applications that are so ex- in scouring compounds. The use of this abrasive
tensive and varied that only the major ones are has declined greatly because inhalation of free
mentioned in this article. For further informa- silica dust may lead to silicosis. Quartz has been
tion see [2–12]. In addition major manufactur- replaced to a considerable extent by manufac-
ers of abrasives, bonded and coated products, tured abrasives, such as fused aluminum oxide
and related trade organizations have their own and silicon carbide, as well as by garnet, glass,
brochures, reprints of published articles, etc., and slags.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 001
2 Abrasives

2.2. Garnet amounts of other minerals, particularly mag-


netite [1309-38-2] and hematite [1317-60-8].
Mineralogically, the term garnet refers to a group High-quality emery has been produced on the
of minerals with similar crystal structure but Greek island of Naxos for at least 2000 years
varying considerably in chemical composition. and also is mined in Turkey. Major uses include
Most abrasive garnet is almandite [1302-62-1], polishing metals with the coated products and
an iron aluminum silicate, Fe3 Al2 (SiO4 )3 . incorporation of the abrasive in nonslip floors,
Almost all of the garnet used for high- pavements, and stair treads.
performance coated abrasives is mined in the The term “emery” has also been applied to
Adirondack area of New York State. The ore is a rock mined near Peekskill in New York State.
crushed and beneficiated and the resulting gar- Also known as spinel emery, it contains little or
net is separated into various grit sizes and heat no corundum. However, because of its content
treated. This particular garnet is unique, as the of spinel [1302-67-6], a mineral with hardness
mineral fractures to produce grains having sharp, between quartz and corundum, this “emery” has
continuous edges that are optimum for use as a utility in less demanding applications. Very lit-
coated abrasive. Also its hardness is at the upper tle, however, is used for coated abrasives.
end of the range for garnets. The coated product Estimated world emery production in 1990
is used for finish sanding of wood in furniture was 20 000 t/a and has decreased sharply since
and woodworking plants. 1983.
Other U.S. operations in New York, Idaho,
and Maine, and those elsewhere in the world,
produce garnet of inferior quality for coated 2.4. Diamond
applications, but which is used extensively for
sandblasting, metal lapping, and the fine grind- Diamonds [7782-40-3] apparently were found
ing of glass. first in India and Borneo over 2000 years ago,
Estimated 1996 world production in 103 t/a but the discovery of them in South Africa in 1866
are [49]: began an era of great expansion that is still con-
tinuing (→ Carbon).
United States 68.2 Diamonds may be classified as gem quality,
India 15
Australia 40
high-grade industrial, and bort, the borderlines
China 15 between grades overlapping and varying with
Others 16.8 demand. Bort contains inclusions, microcracks,
Total 155
and other flaws, giving rise to translucency or
opacity, off-color, etc. The material therefore
Approximately 30 % of U.S. production was is used almost exclusively in grain and powder
used for water-filtration applications. forms. Most natural diamonds are single crys-
tals, but carbonado [12414-51-6], a type found
in Brazil, and ballas, found in Brazil and Africa,
2.3. Corundum and Emery are polycrystalline in structure. They are espe-
cially tough because of the absence of well-
Corundum [1302-74-5] is a naturally occurring developed cleavage planes, and are particularly
aluminum oxide mineral of high purity. Esti- useful for heavy-duty applications, such as tru-
mated production in 1990 in 103 t/a was [50]: ing and dressing grinding wheels.
South America 0.25 World production of natural industrial dia-
Europe + CIS 10 monds in 1996 in 106 carats, including bort,
Africa 20
Asia (India) 2 which accounts for over 85 %, was:
World total 32.25 Congo (Kinshasa) 15
Russia 9.2
The major use of corundum is for the loose- Botswana 5
grain grinding and polishing of optical compo- Republic of South Africa 6
Australia 23.1
nents. All others 3.3
Emery [12415-34-8] consists predomi- Total 61.6
nantly of corundum but also contains varying
Abrasives 3

Australia is the worlds largest producer since The alumina from the indirect Bayer process
the startup of the Argyle alluvial operation in contains about 99 % Al2 O3 . The type commonly
Western Australia in January 1983. used for fused alumina production contains ap-
Major uses of diamonds are discussed in Sec- proximately 0.4 – 0.5 % Na2 O, the remainder
tion 3.6. being small amounts of SiO2 , Fe2 O3 , and water.

3. Manufactured Abrasives 3.1.2. Furnace Designs


3.1. Fused Aluminum Oxides Two general types of furnace are employed, one
resulting in a batch process and the other in a
Differences in the composition of natural corun- continuous one.
dum and emery gave rise to variability in grind- The first, generally known as the Higgins fur-
ing wheel manufacture and in end-use perfor- nace, consists of an open-ended, slightly tapered
mance. Therefore attempts were made to pro- cylinder of sheet steel, smaller diameter up, rest-
duce more consistent synthetic corundum abra- ing on a hearth protected by a carbon coating
sives. [14]. Fusion of the bauxite is accomplished using
Although some early work was carried out an electric arc. Water continuously flows down
in Europe, the first commercially successful the outside of the shell, keeping it from melt-
product resulted from the experiments of C. B. ing during the process. After fusion is complete,
Jacobs, C. M. Hall, and A. C. Higgins in the the product is cooled for several days, resulting
United States at the end of the 19th century in a coarsely crystalline material. This is sorted
and the beginning of the 20th [13]. This tech- and rough crushed to yield crude abrasive about
nology was the foundation for a variety of 50 mm in size.
fused aluminum oxide [1344-28-1] abrasives Continuous furnaces are patterned after the
(→ Aluminum Oxide). batch type except that they are generally much
larger and arranged for tilting and tapping the
molten products into suitable containers [15],
3.1.1. Raw Materials [16]. For economic reasons most fused aluminas
being produced in similar large-capacity casting
Bauxite [1318-16-7] is used directly for the pro- furnaces where fusion may continue uninter-
duction of some fused alumina types, and in- ruptedly for many days or even months.
directly, through the Bayer process, for other
varieties. Largely for economic reasons, baux-
ites used for the production of fused aluminum
3.1.3. Fused Alumina Types
oxide abrasives are of relatively high Al2 O3 con-
tent. Materials from various sources are usually The fused alumina produced in largest tonnage
blended, a typical specification being: is known as regular aluminum oxide. The raw
Al2 O3 ∗ = 82 % minimum materials are calcined bauxite, carbon usually
SiO2 = 8 % maximum in the form of coke, and iron borings, a typ-
Fe2 O3 = 8 % maximum ical mass ratio being 80 : 15 : 5. Because the
TiO2 = 4 % maximum relative ease of reduction of the bauxite feed
to metal in the fusion process with carbon is
∗ determined by subtracting total SiO2 , Fe2 O3 > SiO2 > TiO2 > Al2 O3 , an abrasive of
Fe2 O3 , and TiO2 from 100 %. considerably higher Al2 O3 content than that of
Abrasive-grade bauxite consumption in the the furnace feed can be attained. During fusion
United States and Canada was quoted as two immiscible liquids exist. The upper one be-
197 × 103 t in 1994 and 133 × 103 t in 1995, comes the abrasive on crystallization, and the
both on a dry basis. This is less than 2 % of lower one becomes a byproduct, ferrosilicon.
the total consumption of bauxite, 90 % of which Regular aluminum oxide is brown and has a
was used for the production of aluminum. chemical composition of approximately 95 %
4 Abrasives

Al2 O3 , 1.5 % SiO2 , less than 0.5 % Fe2 O3 , high purity, only fusion and crystallization take
and 3 % TiO2 . Because of very slow cooling place. The resulting abrasive has about the same
in the Higgins furnace, the crystals of alumina chemical composition as the alumina. However,
are coarse, averaging 10 – 15 mm in diameter. If a small amount of the soda is volatilized, giving
the fused material is cast, the upper liquid must rise to pores in the resulting product. Sometimes
be poured into very large molds holding at least small amounts of chromium oxide [1308-38-9]
5 t of product to insure similar slow cooling and are added to the furnace feed, producing a pink
coarse crystallization. or ruby-colored abrasive. Similarly, a small ad-
A second brown type is semifriable fused alu- dition of vanadium oxide [1314-34-7] results in
mina. It is purer than regular, containing approx- an emerald green color. Although claims have
imately 97 % Al2 O3 , 0.5 % SiO2 , less than 0.5 % been made for the value of such additions, con-
Fe2 O3 , and 2 % TiO2 . Both batch and continu- trolled grinding tests have failed to detect pos-
ous processes are used to produce this variety. itively any advantages. The major use for the
Because the regular and semifriable types are white abrasive is in vitrified-bonded wheels for
close in composition, the present trend is to- toolroom grinding or precision grinding of heat-
ward a single brown fused alumina of intermedi- sensitive steels.
ate composition, produced in casting furnaces. Monocrystalline aluminum oxide is a very
The relative friabilities are adjusted by crush- high purity abrasive, produced directly from
ing and processing methods to give different bauxite in a single-stage fusion [17]. The pre-
grain shapes, the more equidimensional being ferred method employs a furnace feed consist-
the regular and the sharper, less blocky being ing of bauxite, pyrite (FeS2 ) [1309-36-0] or sul-
the semifriable. fur [7704-34-9], carbon, and iron borings. When
In general, the major use of fused alumina subjected to fusion in the Higgins batch furnace,
abrasives is for processing high-tensile-strength two immiscible liquids are formed as with reg-
ferrous metals, such as carbon steels. The reg- ular aluminum oxide. However, in the present
ular kind is employed in loose-grain form in case very slow cooling of the upper liquid results
blasting, lapping, and barrel finishing, in bonded in essentially pure, individual crystals of Al2 O3
form mostly in nonprecision operations, such in a matrix of sulfides. After the pig has cooled
as cutting off and rough grinding in organic- and been crushed, the matrix is removed chemi-
bonded products. Semifriable alumina is more cally and mechanically. This treatment releases
commonly used in vitrified-bonded products for alumina crystals in the range of sizes required
precision grinding operations, and on coated by the industry.
belts and discs. Little or no crushing is needed, so in this re-
A third type, similar in composition and fu- spect this abrasive is entirely different from all
sion method to the above, is known as microcrys- the other types of fused aluminas in use today.
talline. In order to produce an abrasive with very Chemical analysis approximates 99.2 % Al2 O3 ,
small alumina crystals, rapid cooling of the melt 0.6 % TiO2 , 0.2 % impurities. This abrasive also
is required. This is effected by pouring it into may be produced in a casting furnace provided
small molds or onto pans to produce slabs. The that the fusion is poured into a large receptable
resulting abrasive has higher intrinsic strength capable of holding many tons of product to per-
than the others. It formerly was used extensively mit slow cooling of the melt. The size distri-
in heat-treated form for very heavy duty grinding bution of the resulting abrasive crystals can be
wheel applications, such as the conditioning of varied by changes in manufacturing parameters.
steel slabs and billets using resin-bonded prod- Surprisingly the monocrystalline type also may
ucts. For the most part this abrasive has been su- be produced from a mixture of Bayer process
perseded by fused zirconia – alumina of the ZS alumina, elemental sulfur, and carbon [18]. In
type (Section 3.2), or by sintered alumina of the this process only one liquid is present in the fur-
76 Alundum type (Section 3.3). nace during fusion, but otherwise the sequence
White fused alumina is produced by direct of operations is similar, and the resulting prod-
fusion of Bayer process alumina [14]. Either uct is the same as that produced directly from
the batch or the continuous casting process may bauxite. This premium-priced abrasive is found
be employed. Because the raw material is of to be more cost efficient than others, such as the
Abrasives 5

semifriable type, in many precision operations [19]. The alumina may be derived from baux-
using vitrified-bonded wheels. ite or from the Bayer process, and the zirconia
Production. World production capacity for from the mineral zircon (a zirconium silicate)
fused aluminum oxide is listed in Table 1. [14940-68-2], baddeleyite (a naturally occurring
mineral high in ZrO2 ) [12036-23-6], or fused
Table 1. World production capacity (103 t/a) for fused aluminum
zirconium oxide. Zirconia and alumina are fused
oxide in 1996 and 1997 (estimated) [49] by electric-arc casting furnaces to give primary
1996 1997
crystals of alumina with diameters no greater
than about 300 µm but typically less than 30 µm
USA and Canada 220 220 in a matrix of a eutectic of alumina and zirconia.
Australia 75 50
Austria 60 60 The resulting abrasive is dense and very tough.
Brazil 100 100 The grains dull slowly during heavy-duty grind-
China 450 500
France 45 45
ing operations, as with resin-bonded wheels
Germany 150 150 on floorstand machines in foundries. They also
India 20 20 have a longer life on high-speed, high-pressure
Japan 55 55
Others 125 100 grinders used for conditioning billets and slabs,
World total (rounded) 1300 1300 particularly those made of alloy steels or of stain-
less steel, where better surface finish is required
than produced by the sintered alumina of the 76
Trade Names: Alundum, Aloxite, etc. Alundum type (Chap. 3.3.).
Trade Names: ZF-ZS Alundum, BX, BZ,
etc.
3.2. Fused Zirconia – Aluminas Zirconia Content 40 wt %. The raw materi-
als and fusion methods are similar to those dis-
The most outstanding commercial development cussed above; however, in this case the melt must
in the area of alumina-containing abrasives in be solidified very rapidly in order to produce ex-
the last two decades was the invention of fused tremely small crystals [20]. In addition to a rela-
zirconia – alumina products. For the applica- tively slow dulling rate, these grains tend to frac-
tions in which they are most useful, they re- ture to a greater extent than the 25 % analogue
sult in substantially greater efficiencies (lower and do so in such a manner as to provide new
total grinding costs) than the fused aluminas pre- cutting edges rather than being shed from the
viously employed. United States and Canadian grinding wheel or coated abrasive product. Ma-
production for 1980 was 17.2 × 103 t, amount- jor applications include resin-bonded portable
ing to 11 % of all fused aluminas, including the wheels, cones and plugs, cloth-backed resin-
zirconia – aluminas. No production data were bonded belts, and fiber-backed discs for grinding
available for 1981 or 1983; however, 1982 pro- castings of steel, gray and ductile iron, and stain-
duction was quoted as 7.3 × 103 t or 6 % on the less steel alloys. In some cases mixtures of this
same basis as the 11 % for 1980. This reduction abrasive with the less expensive fused alumi-
was caused by the severe depression in those seg- nas or with silicon carbide are used for specific
ments of the metal-working industry in which purposes; for example, the latter blend can effi-
zirconia – alumina abrasives are most applica- ciently clean and grind castings having burned-
ble. on sand.
These abrasives also are produced in Japan, Trade Names: NZ Alundum, etc.
France, Austria, Federal Republic of Germany,
and possibly other countries. However, produc-
tion data are not available for them. 3.3. Sintered Aluminas
Zirconia Content 25 wt %. Although the ba-
sic patent specified an abrasive alloy consisting From Bauxite. Calcined bauxites are ground
essentially of zirconium oxide [1314-23-4] and to a fine powder, mixed with an organic binder,
aluminum oxide, with the content of the for- such as grease, extruded through an orifice, cut,
mer between 10 and 60 wt %, the resulting com- and fired statically or in a rotary furnace to tem-
mercial product typically contains about 25 % peratures between 1400 and 1600 ◦ C [21]. This
6 Abrasives

results in limited recrystallization of the alu- today in furnaces similar to the one he patented
mina, increased density, and great strength of the in 1893 [24]. Silica sand plus carbon in the form
particles, which have the desired grain size with- of coke, or low-ash coal in the approximate mass
out being crushed. The major use of this abrasive ratio of 60 : 40 is heated in a troughlike electric
is the conditioning of stainless steel billets and resistance furnace to produce SiC according to
slabs using hot-pressed resin-bonded wheels. the equation:
Trade Names: 76 Alundum, SO 200, etc.
From Alumina Gels. A colloidal dispersion SiO2 + 3 C −→ SiC + 2 CO
of alumina monohydrate [12252-67-4] and of
modifying oxides, such as zirconia and/or mag- Several grades of this abrasive are produced.
nesia [1309-48-4], is formed, and the resulting The most common black or gray type is used
gel dried to produce chunks. These are crushed in bonded and coated form for grinding low-
and air fired (sintered) to above 1250 ◦ C, re- tensile, nonferrous metals such as aluminum,
sulting in considerable shrinkage and forma- brass, copper; some cast irons; and nonmetallics,
tion of a dense, sharp, and extremely tough such as glass, stone, concrete, ceramics, and re-
abrasive [22], [23]. These expensive abrasives fractories. A higher purity green variety is em-
are now widely used in industry as they sig- ployed for those operations, such as rough grind-
nificantly outperform fused alumina grains for ing of cemented carbide tools with vitrified-
high-precision grinding and creep-feed grind- bonded wheels, in which this abrasive’s more
ing. They are mostly used in vitrified wheels, friable characteristic and the light green color are
but specific operations requiring organic-bonded helpful. A type lower in purity than that used for
wheels, such as flute grinding, surfacing, and bonded and coated products has utility in loose-
calibrating with disk grinders, also use sol – gel grain applications, such as wiresawing and lap-
aluminas. Coated abrasives are also produced ping.
with these grains for foundry snagging with belts World production capacity for silicon carbide
and fiber disks and for other work on stainless abrasives is listed in Table 2.
steel and high-resistance alloys. As new types of
sol – gel aluminas are developed and production Table 2. World production capacity (103 t/a) for silicon carbide abra-
volume grows, they are progressively replacing sives in 1996 and 1997 (estimated) [49]
fused aluminas in many operations. 1996 1997
Trade Names: Cubitron, SG, TG, etc. Often
referred to with the generic name “ceramic abra- USA and Canada 90 90
Argentina 5 5
sives”. Brazil 43 43
China 450 450
France 16 16
Germany 36 36
3.4. Silicon Carbide India 5 5
Japan 90 90
Mexico 60 60
The discovery of silicon carbide [409-21-2] Norway 80 80
by Edward G. Acheson in 1891 was indeed Venezuela 40 40
epoch-making because it was the first synthetic Others 185 185
World total (rounded) 1100 1100
abrasive invented and commercialized, and sig-
naled the gradual decline in the use of natural
abrasives (→ Silicon Carbide). In an attempt to Trade Names: Carborundum, Crystolon, etc.
make diamonds by an electric-arc heating pro-
cess, Acheson produced a very few hard crys-
tals. Knowing that they were not diamond but 3.5. Boron Carbide
thinking that they were a combination of carbon
and corundum, he called them “carborundum,” Abrasive boron carbide, B4 C [12069-32-8], is
a term that remained even after the crystals were produced in electric resistance furnaces from
determined to be silicon carbide. Carborundum a charge of high-purity boron oxide glass and
became the name of the company he organized to high-purity coke according to the equation [25]:
exploit the discovery. Abrasive SiC is produced
Abrasives 7

2 B2 O3 + 7 C −→ B4 C + 6 CO World production of synthetic diamond is


listed in Table 3.
As explained in Section 5.3, this abrasive is In general, diamonds, both natural and manu-
unsuited for use in bonded or coated products. factured, are used for lapping carbides and other
However, for loose-grain applications, such as hard materials, and for grinding, drilling, and
the lapping of cemented carbides and other hard sawing cemented carbides and a wide variety
materials, it is used alone or mixed with silicon of nonmetallics, such as plastics, glass, stone,
carbide. concrete, ceramics, refractories, and such elec-
Trade Names: Norbide, etc. tronic materials as silicon and quartz. Silicon
carbide also can be used for these same ma-
terials. However, bonded diamond products, in
3.6. Diamond spite of their higher cost, often are more effi-
cient, resulting in lower total costs per unit of
Commercial availability of manufactured dia- work performed. This is particularly true in ce-
mond [7782-40-3] is the most important abra- mented carbide grinding, where diamond, now
sive development in the 20th century (→ Car- nearly always one of the manufactured types,
bon). Not only did it eliminate occasional short- is used almost exclusively except for offhand
ages of natural diamond grain, but also it made roughing with vitrified-bonded green silicon car-
possible a great variety of diamonds with vastly bide wheels. Because of the affinity between di-
different characteristics, thereby increasing dia- amond (carbon) and iron, diamonds are not eco-
mond efficiency and consequent use. nomical for grinding ferrous metals except those
Commercial manufacture of diamond re- containing relatively large amounts of hard con-
quires high pressure (5.0 – 6.5 GPa) and high stituents, such as certain vanadium steels.
temperature (> 1400 ◦ C) [26]. Depending upon The cost of synthetic diamond has greatly
manufacturing parameters, a wide range of prop- decreased since the mid-1980s, and this has al-
erties may be obtained, from very friable com- lowed it to be used in nonprecision applications
posite structures of small diamond crystals to such as cutting masonry materials, stones and
stronger single crystals containing various de- bricks with steel disks on hand-held grinders.
fects and inclusions, to very strong, almost flaw- The disks have laser-welded, metal-bonded dia-
less crystals, equidimensional in shape, with mond segments, and their low cost and long life
well-developed crystal faces. One leading pro- have allowed them to replace most conventional
ducer offers no fewer than seven different basic silicon carbide cutting-off disks.
types. Over the years the major manufacturers
have gradually been able to produce economi-
cally high-quality single diamonds of larger and 3.7. Cubic Boron Nitride
larger size, now up to 20 – 25 mesh (approx-
imately 700 – 850 µm in diameter). No doubt The second, and eventually possibly the most
they will continue to extend availability further important development in the abrasive area this
in the coarse direction. century, was the invention [28] of cubic boron ni-
The two major producers further improved tride (CBN) [10043-11-5], first introduced com-
the efficiency of diamonds for use in resin- mercially in 1969 (→ Boron Carbide, Boron Ni-
bonded products by introducing metal-clad va- tride, and Metal Borides).
rieties in 1966 [27]. These coatings are believed This abrasive may be made in any of the high-
to improve wheel efficiency by controlling abra- pressure, high-temperature apparatuses used for
sive breakdown, and by acting as a heat sink be- diamond production. By using different raw ma-
tween the abrasive and the bond, retarding dete- terials and manufacturing conditions, a variety
rioration of the latter from heat generated during of products having a range of friabilities may be
grinding. The most commonly employed coat- produced. Color ranges from almost colorless
ings are nickel-based (30, 55, or 60 wt %) or through shades of yellow, red, and black. As with
copper (50 wt %). Although used mostly with diamonds, the producers supply CBN in sized
manufactured diamonds, the 55 % nickel coat- grains and flours. Metal cladding of this abrasive
ing is also available on natural diamonds. also has improved its efficiency in resin-bonded
8 Abrasives
Table 3. Estimated world production of synthetic diamond (103 carat)

1992 1993 1994 1995 1996

Belarus 30 000 30 000 25 000 25 000 25 000


China 15 000 15 000 15 000 15 000 15 000
Czech Republic 10 000 ∗ 5 000 5 000 5 000 5 000
France 3 500 3 500 3 500 3 000 3 000
Greece 750 1 000 1 000 1 000 750
Ireland 60 000 65 000 65 000 60 000 60 000
Japan 30 000 32 000 32 000 32 000 32 000
Poland 320 98 271 256 250
Romania 3 000 5 000 5 000 5 000 5 000
Russia 80 000 80 000 80 000 80 000 80 000
Slovakia 5 000 5 000 5 000 5 000
South Africa 60 000 60 000 60 000 60 000 60 000
Sweden 25 000 25 000 25 000 25 000 25 000
Ukraine 10 000 10 000 8 000 8 000 8 000
USA 90 000 103 000 104 000 115 000 114 000
Total 418 000 440 000 434 000 440 000 439 000

∗ Czechoslovakia

products [29]. A 60 % nickel-based coating is Production of CBN by region is summarized


used commonly. in Table 4.
Initial successful applications of CBN were Table 4. Production of CBN by region (106 carat) [51]
for high-performance grinding of difficult to
grind ferrous metals where use of fused alumina 1992 1993 1998
abrasives results in high rates of wheel wear per Pacific Rim 12.5 13.2 18.8
unit of material removed from the workpiece and United States 10.9 13.1 37.7
in rapid dulling of the abrasive grains. Therefore Europe 9.9 10.9 19.5
Total 33.3 37.2 76.1
machine productivity is low and grinding costs
high, as is the liability of metallurgical damage
to the work. Because of its hardness (inferior Trade Names: Borazon, Amber Boron Ni-
only to diamond), strength, low coefficient of tride, etc.
friction during operation, and thermal and chem-
ical stability to well over 1000 ◦ C, CBN wheels,
although expensive, increase productivity. This 4. Manufacture and Testing of Sized
is because of much lower wheel wear, improved Grains
workpiece integrity, and fewer rejections and re-
works. Now, with the development of computer- As mentioned in Chapter 3, some abrasive types
controlled, high-production systems especially are produced directly to size for use in bonded or
designed for use with this abrasive, its applica- on coated products. Other abrasives, such as the
tion is being extended to more common, less dif- fused aluminum oxides, must be crushed, sized,
ficult to grind ferrous metals. This has resulted and otherwise treated before use.
in increased productivity for such operations as Crushing is accomplished by a variety of
camshaft grinding in the automobile industry. means, depending on the shape and other char-
In 1981 one producer introduced a CBN fam- acteristics of the desired product. Jaw crushers,
ily (trade names: Borazon 550, 560, 570) with hammer mills, roll mills (in which precrushed
sized grain that is polycrystalline and extremely crude is passed through sets of alloy steel rolls),
tough. In certain applications resinoid- and and ball or rod mills commonly are employed. If
vitrified-bonded wheels containing this abrasive exceptionally equidimensional particles are de-
have shown lower wheel wear than similar prod- sired, the grain may be mulled by the use of
ucts containing the usual monocrystalline CBN. heavy steel rollers working the grain in a revolv-
However, the expense of the abrasive has been ing pan.
a problem in establishing lower overall grinding To produce specific grit sizes, screening is
costs in many cases. used for the coarser ones (macrogrits; >50 µm
Abrasives 9
Table 5. Standards for sizing of abrasive grains

Type of abrasive Screen sizes (macrogrits) Subsieve sizes (microgrits)

All except diamond and CBN for :


Grinding wheel and ANSI B74.12−1992 [30] ANSI B74.10−1977 (R1992)
general industrial usage FEPA 42/93 FEPA 42/93
ISO 8486, part 1 (1996) ISO 8486, part 2 (1996)
Coated Applications ANSI B74.18−1996 ANSI B74.18−1996
FEPA 43/93 FEPA 43/93
ISO 6344, parts 1 and 2 (1998) ISO 6344, part 3 (1998)
Diamond, CBN, all uses ANSI B74.16−1995 ANSI B74.20−1997
FEPA 61/97 FEPA 60/77 (under revision)

F90 154
in diameter). Finer sizes (micogrits) are sepa- F100 129
rated by various elutriation methods. Centrifug- F120 109
ing often is employed for the finest grains. F150 82
F180 69
For checking the sizing of abrasive grits, the F200 58
standards shown in Table 5 are used. Microgrits
F230 55.7 ± 3
Conventional (i.e., non-diamond and non- F240 47.5 ± 2
CBN) abrasive grits are sized according to stan- F280 39.9 ± 1.5
dards that assign each size a number and de- F320 32.8 ± 1.5
F360 26.7 ± 1.5
fine the mean size and the proportion and di- F400 21.4 ± 1
mensions of coarser and finer sizes that can be F500 17.1 ± 1
F600 13.7 ± 1
present. The standards usually differ for bonded F800 11 ± 1
and coated abrasives, as the optimum perfor- F1000 9.1 ± 0.8
mance of the products requires different grain F1200 7.6 ± 0.5

shapes and a different size distribution for each


grit number. For example, FEPA (Federation of The grit numbers and the mean particle sizes
European Producers of Abrasive Products) has in micrometers in the P series (aluminum oxide
issued two standards: FEPA 42/93, which de- and silicon carbide grains for coated abrasives
fines the F series for bonded abrasives, and FEPA are as follows:
43/93, which defines the P series for coated abra- Macrogrits
sives. Similarly, ISO has issued ISO 8486 for P12 1815
P16 1324
bonded and ISO 6344 for coated abrasives. The P20 1000
grit numbers and the mean particle sizes in mi- P24 764
crometers in the F series (aluminum oxide and P30 642
P36 538
silicon carbide grains for grinding wheels and P40 425
other bonded abrasives are as follows: P50 336
P60 269
Macrogrits P80 201
F4 4890 P100 162
F5 4125 P120 125
F6 3460 P150 100
F7 2900 P180 82
F8 2460 P220 68
F10 2085 Microgrits
F12 1765 P240 58.5 ± 2
F14 1470 P280 52.2 ± 2
F16 1230 P320 46.2 ± 1.5
F20 1040 P360 40.5 ± 1.5
F22 885 P400 35 ± 1.5
F24 745 P500 30.2 ± 1.5
F30 625 P600 25.8 ± 1
F36 525 P800 21.8 ± 1
F40 438 P1000 18.3 ± 1
F46 370 P1200 15.3 ± 1
F54 310 P1500 12.6 ± 1
F60 260 P2000 10.3 ± 0.8
F70 218 P2500 8.4 ± 0.5
F80 185
10 Abrasives

Figure 1. Example of size gradations of the FEPA standard F series for bonded abrasive grits

The approximate relationship between the Figure 1 shows the relationship between grit
FEPA and other national diamond and CBN grit size designations, sieve numbers, aperture size
size designations is summarized in Table 6. of sieves, and micrometer dimensions of par-
ticles for both screen-size and subscreen-size
Table 6. Approximate relationship between the FEPA and other na-
tional diamond and CBN grit size designations grains according to FEPA standards [31].
In practice various manufacturers use other
FEPA grit designation ∗ ASTM 11 BS 1987
(approx. mean size, µm) equipment for checking abrasive sizing, such as
the Coulter counter.
Narrow-range grades
1181 16/18 14/16
The major suppliers of subsieve diamond and
1001 18/20 16/18 cubic boron nitride products offer their own se-
851 20/25 18/22 ries, many items of which are extremely well
711 25/30 22/25
601 30/35 25/30 classified into the very narrow ranges demanded
501 35/40 30/36 by the trade. One supplier, for example, offers
426
356
40/45
45/50
36/444
44/52
17 sizes from 40 – 80 µm down to 0 – 0.5 µm.
301 50/60 52/60 After sizing, grits are washed, processed fur-
251 60/70 60/72 ther, and tested using the methods in Table 7.
213 70/80 72/85
181 80/100 85/100 Instrumental techniques such as atomic ab-
151 100/120 100/120 sorption, emission spectroscopy, and X-ray flu-
126 120/140 120/150
107 140/170 150/170
orescence are used in practice for chemical anal-
91 170/200 170/200 yses. Eventually new standards based on such
76 200/230 200/240 methods will be forthcoming.
64 230/270 240/300
54 270/325 300/350 Strength of abrasive grains containing glass
46 325/400 350/400 as a minor impurity, as in regular fused alumina,
Wide-range grades
1182 16/20 14/18 can be increased significantly by heat treatment
852 20/30 18/25 in air to 1250 – 1350 ◦ C. The glass migrates to
602 30/40 25/36 the surface, sealing microcracks, and thus re-
502 35/45 30/44
427 40/50 36/52 pairing damage caused by the crushing opera-
252 60/80 60/85 tion. Alternatively, the grain may be coated with
∗ The grit designation is prefixed with a “D” to denote diamond a glass frit that matures at 800 – 1000 ◦ C. Such
and a “B” to denote CBN. treatments increase abrasive efficiency in heavy-
Abrasives 11
Table 7. Test methods for abrasive grain properties

Application Test method Comments

Presence of magnetic particles ANSI B74.19−1990 (R1995)


Measure of coating weight for diamond FEPA 62/93
and CBN grains
Relative strength of saw diamond grits FEPA 63/93
Degree of capillarity ANSI B74.5−1964 (revised 1995) capillarity is increased by heating to 500 – 600 ◦ C
ISO 9137 (1990) used for conventional abrasives
FEPA 44/93, part 3 used for conventional abrasives
Grain shape ANSI B74.4−1992 (R1997) equidimensional shapes pack to a higher bulk
density than flat or slivery ones
ANSI B74.17−1973 (revised 1993) this method is used for testing diamond and CBN
Bulk density ISO 9136, parts 1 and 2 (1989) used for conventional abrasives
FEPA 46/93, part 2
Grain strength (friability) ANSI B74.8−1987 ball mill test (see Section 5.2 for interpretation of
strength data)
FEPA 46/93 used for fused aluminum oxides
Chemical analysis (classical wet methods)
ISO 9285 (1995) used for fused aluminum oxides
ANSI B74.14−1992 used for fused aluminum oxides
ISO 9286 (1995) used for silicon carbides
FEPA 45/93 used for silicon carbides
ANSI B74.15−1992 used for silicon carbides
Sampling and splitting ISO 9138 (1993) used for conventional abrasives
FEPA 44/93, part 1 used for conventional abrasives
Test-sieving machines ISO 9284 (1992) used for conventional abrasives

duty applications, such as in the conditioning of number. Values of K100 for common abrasives
steel slabs and billets with resinoid wheels. compared with the Mohs’ hardness scale gener-
Sometimes grits are treated with a liquid sili- ally used by mineralogists are:
cone resin before being incorporated into resin-
Knoop, K100 Mohs’
bonded products. Silicon carbide grain may be
subjected to froth flotation to remove free car- Quartz (silica) 820 7
Spinel (magnesium aluminate) 1270
bon and/or treated with a sodium hydroxide so- Garnet (almandite from Adirondacks, U.S.) 1360 8
lution to remove free silicon. In order to insure Fused zirconia-alumina (NZ Alundum type) 1600
vitrified-bonded products free from iron spot- Fused alumina (white type) 2050 9
Silicon carbide 2480
ting, fused alumina grains, especially the white Boron carbide 2800
variety, may be acid-treated to remove ferro- Cubic boron nitride 4700
Diamond 7000 – 8000 10
silicon or tramp steel not eliminated by magnetic
separation.

5. Physical and Chemical Properties 5.2. Grain Strength or Fracture


Toughness
5.1. Hardness
The hardness level required of an abrasive obvi- Strengths resulting from three different proper-
ously depends upon the specific use. However, ties are important and usually act together during
the vast majority of industrial applications ne- an abrasive operation. First is the grain shape, the
cessitates abrasives at least as hard as quartz. blocky or equidimensional one being referred
A common means for determining hardness to as a strong shape, that with many flakes and
is by use of the Knoop indenter, a gem-quality slivers as a weak shape. Second, grains contain-
diamond carefully lapped to the shape of an ing microcracks and other flaws produced by
elongated pyramid. This device indents the ma- crushing tend to be weaker than those produced
terial to be tested under controlled-load condi- directly to size without subsequent comminu-
tions [32]. The applied gram load must be spec- tion, assuming that the grains are otherwise of
ified, e.g., K100 , because it can cause consider- about the same overall shape. Third, is the in-
able variation in the resulting Knoop hardness trinsic strength of the body of the abrasive itself.
12 Abrasives

Although this is difficult to measure in finished on the abrasive grains and so the loss of much or
grain form because of the effect of shape and all of their stock-removal capabilities [34–36].
crushing, relative intrinsic strengths may be es- For loose-grain lapping operations, hardness
timated. If the difference between abrasives is and strength are the most important abrasive
large, this is done by means of data derived from properties. However, stock removal with fixed
ball milling (method of ANSI B 74.8−1977) or abrasives is a complicated process involving the
by crushing or blasting tests, provided that the interaction of hardness, strength, and chemical
difference in grain shape has at least been mini- properties of both the abrasive and the work-
mized and crushing histories are similar. piece. In addition the conditions of operation
The fracture strength or toughness of ce- also must be considered.
ramics is determined by studying the cracking
produced by indenting polished sections with
a Vickers indenter. The load is such that frac- 6. Loose-Grain Applications
tures are produced at the corners of the indenta-
tions. The fracture toughness (K c ) may be calcu- Blasting. In this operation, screen-size abra-
lated by measuring the average crack length and sives, such as quartz sand, garnet, fused alumina,
the diagonals of the indentations when Young’s and silicon carbide, impact the work material by
modulus and the microhardness are known [33]. means of compressed air, centrifugal force, or
This method of measuring intrinsic strength or pressurized water. Blasting is used to descale
toughness of abrasives is destined to replace the or otherwise clean and deburr metal parts, clean
other procedures because it is a direct one. buildings, and carve letters and designs on stone.
Wire Sawing. Endless, multistrand, twisted
wire under tension is used to carry a slurry of
5.3. Resistance to Attrition or Plastic water and abrasive for sawing blocks or slabs
Flow of stone such as limestone, marble, and gran-
ite. Quartz sand may be used to cut the softest
When abrasive boron carbide was first produced stones, but fused alumina or silicon carbide is
in the early 1930s, its hardness was greater than required for the harder granites and sandstones.
that of any known material except diamond. Its This method is used both in the quarrying pro-
effectiveness as an abrasive in loosegrain lap- cess itself and to shape and slice blocks removed
ping operations, such as on cemented carbides, from the quarry.
correlated well with relative hardnesses, being Barrel Finishing. Metal parts requiring
greatly superior to silicon carbide and fused alu- cleaning, deburring, and/or refining of surface
minas, but inferior to diamond. For that rea- finish are tumbled in a slowly rotating barrel with
son boron carbide was excepted to have exten- water, acid or alkaline cleaning compounds, and
sive applications in bonded products, replacing suitable abrasives. Depending upon the work
those older, softer abrasives. However, extensive material and finishing requirements, the abra-
grinding tests proved boron carbide to be com- sives may be natural ones, such as emery or
pletely unsuitable in any such operation because crushed granite, or, more commonly, manufac-
the wheels quickly became dull. The major rea- tured abrasives, such as fused aluminas. The lat-
sons appear to be oxidation of the boron carbide, ter may be used as such, or they may be bonded
and the reaction or diffusion between the abra- with vitrified or organic materials into specific
sive and the material being ground. A similar ex- shapes, such as triangles, stars, or pins. A more
planation appears to apply to the relatively poor efficient finishing method, involves vibrating
performance of diamond when grinding com- the materials in bowls or tubs.
mon ferrous metals. Temperatures at the inter- Lapping. Loose abrasives in a vehicle of wa-
face may approach the melting point of steel. ter, soluble oil, kerosine, greases, etc., can be
Under these conditions both the abrasive and used to fine grind flat, cylindrical, or other sur-
piece being worked are greatly softened, with faces. Laps of cast iron and other metals are used,
reaction or diffusion between the two greatly ac- and the abrasive grains may become embedded
celerated. The result is attritious wear or plastic to some degree in these during the operation. The
flow, leading to the development of polished flats choice of abrasive depends upon the nature of
Abrasives 13

the workpiece. Harder abrasives, such as boron clay, fluxes, or frits, molding the mix to a prede-
carbide and diamond, are most suitable for lap- termined mass : volume ratio, drying it, altering
ping cemented carbides, whereas quartz, garnet, the shape in the green state by shaving, if neces-
and emery may be used on relatively soft materi- sary, and finally maturing the bond by firing in a
als. Gear lapping is accomplished by feeding an kiln, usually at 850 – 1250 ◦ C or above. After it
abrasive slurry between the parts as they revolve. cools, a wheel may be sided and faced, and the
Buffing. Abrasives, such as fused aluminas hole reamed or bushed.
and silicon carbide of subsieve size, are bonded Products are characterized by volume per-
with greases or waxes into cakes or sticks. These centages of abrasive, bond, and pores (Fig. 2).
are applied dry to the face of rotating resilient Softer grades contain higher pore volumes, and
wheels made of such materials as felt and other lower structure numbers have higher grain vol-
cloth types. The bond melts during the buffing umes. The final product is inspected by measur-
operation so the abrasive is not fixed. A small ing mass : volume, modulus of elasticity, and
amount of material is removed from the work, resistance to penetration by a rotating chisel or
usually a metal; but, more importantly, a lus- by a blast of a known volume of sand or other
trous, satin, or mirror-like finish is produced. abrasive under known pressure. The pores of the
wheel may be filled with sulfur or waxes to im-
prove grinding action by retarding loading of the
7. Bonded Abrasive Products wheel face with swarf during operation. A com-
posite wheel can be made with a stronger center
These are rigid or only slightly flexible bod- portion (finer grit abrasive, harder grade) to in-
ies, such as grinding wheels, which normally crease the overall strength of the body. Also the
have more than a single layer of abrasive grains portion adjacent to the hole can be treated with
bonded with glass (vitrified bonds), organic ma- a liquid epoxy resin for the same purpose.
terials, or metals. The products are manufac-
tured in a wide variety of shapes and sizes,
including wheels (mounted and unmounted),
segments, bricks, sticks, etc. For details see
ANSI B74.2−1974, Specifications for Shapes
and Sizes of Grinding Wheels. . . . The spec-
ifications for diamond and CBN wheels are
given in ANSI B74.3−1974 (revised 1980),
and for marking of abrasive products in ANSI
B 74.13−1977. Considering possible variations
in types of abrasives, grit sizes, bond types,
structure of the bodies (variations in volume per-
centages of abrasive, bond, and pores), and size
and shape of the bodies themselves, it is un-
derstandable that major manufacturers produce
several hundred thousand varieties of grinding
wheels alone.

Figure 2. Relationship of hardness to structure in bonded


7.1. Vitrified Bonds abrasives
Bv) Bond volume; Gv) Grain volume; Pv) Pore volume
Abrasives bonded with glass include silicon car-
bide, diamond, cubic boron nitride, and all of the Because of the high cost of diamond and cu-
fused alumina types. bic boron nitride (CBN), only a small portion of
With fused alumina and silicon carbide, a the body contains these abrasives, the remain-
typical manufacturing method involves coating der being the core or “preform”. A “green” pre-
the abrasive grain with premixed temporary and pressed ceramic body is first formed, placed in
permanent bonding ingredients such as feldspar,
14 Abrasives

a mold, and the abrasive-bond mix packed be- bonded products, such as thin wheels for cutting-
tween preform and mold assembly. Bonds com- off operations and portable wheels for offhand
monly employed are of the borosilicate type grinding, are reinforced by molding sheets of
from frits or raw materials of the same general woven fiberglass onto the sides, within the body,
composition. After pressing and stripping from or both.
the mold, the product is fired to 900 – 1000 ◦ C. Resin-bonded alumina and silicon carbide
Because diamond oxidizes at such temperatures, products are used for precision-grinding, roll-
firing is usually in nitrogen; CBN may be fired grinding, centerless-grinding, and, most com-
in air. monly, for rough-grinding operations where di-
Content of diamond and CBN in bonded mensional tolerances and finish are less critical,
products is based on volume percentages, 100 as in offhand grinding of rough castings and the
concentration being 25 vol % and others be- conditioning of steel billets and slabs.
ing proportional. For diamond-containing items, Most diamond and CBN products are hot
concentrations are almost always in the range pressed, and preforms are employed, as with the
of 25 – 100, whereas for CBN the range is vitrified-bonded analogs. Uses are mentioned in
50 – 200. Average porosities are lower and the Sections 3.6 and 3.7.
items more durable than those containing fused
aluminas and silicon carbide. Rubber. Natural or synthetic rubbers or com-
For the most part, vitrified bonds are used binations are milled between rolls to break down
for precision operations, such as surface, inter- the fibers, after which the abrasive grain, fillers,
nal, and cylindrical grinding, where close di- and sulfur for vulcanization are added. After be-
mensional tolerances are required. ing mixed, the batch is calendered to the re-
quired thickness, cut to shape, and heated to
150 – 175 ◦ C to vulcanize the rubber. Depend-
7.2. Organic Bonds ing on the amount of sulfur, type of rubber, and
variety and amount of fillers, the product may
Phenol – Formaldehyde Polymers. Most range from soft and resilient to hard.
organic bonds are of this type. They have grad- Because of strength and resiliency, rubber
ually replaced vitrified types in rough grinding cutoff wheels, particularly thin ones, give ac-
applications because the wheels are stronger curate cuts with good surface finish and little
and more shock resistant and so can be operated burring in wet-grinding operations. Another ap-
safely at higher speeds with resulting greater ef- plication is the grinding of ball bearing races and
ficiency. Diamond and all of the manufactured centerless feed wheels.
abrasives described in Chapter 3 are available in
this bond type. Shellac. Shellac is a natural polymer pre-
For abrasives other than diamond and CBN, pared by heating and filtering the secretion of
a common cold-pressed manufacturing method the lac insect, a parasite found on tress in India
involves wetting the abrasive with furfural and surrounding countries. A common wheel-
[98-01-1] or liquid phenolic resin followed making process involves coating the abrasive
by coating it with a premixed blend of pow- with shellac and hot pressing the mixture in
dered phenol – formaldehyde resin and fillers steel molds. The mix also may be calendered
or grinding aids, such as pyrite (FeS2 ), cryo- into thin sheets, from which wheels are cut and
lite [15096-52-3], or potassium tetrafluorobo- cured at 150 – 175 ◦ C. Another method involves
rate [14075-53-7]. Molding is similar to that moistening the abrasive with a shellac solvent,
for vitrified products. Curing is carried out in adding powdered shellac, mixing, cold pressing,
an oven at 140 – 200 ◦ C, or dielectrically. Very and postcuring. Shellac wheels exhibit a con-
low porosity products may be produced by hot siderable degree of thermoplasticity, giving rise
pressing at 160 – 175 ◦ C followed by oven cur- to a soft grinding action with a distinct polish-
ing, as with the cold-pressed products. ing characteristic. They are used in some wet,
When a softer grade action is desired, the light grinding operations, particularly for finish-
phenolic resins may be modified with epoxies, ing steel rolls.
rubbers, or other thermoplastics. Some resin-
Abrasives 15

Polyimide Polymers. For limited, special- in 1982, has permitted a much higher bonding
ized applications, such as the grinding of flutes strength, virtually eliminating loss of segments
on carbide drills, and edge-grinding of carbide because of weakening of the joint from the heat
inserts on certain types of machines, diamonds generated during the cutting operations.
in a polyimide bond have proved to be advanta- Electroplated products normally have a rigid
geous [37]. This particular polymer has consid- core, a nickel bond, and a single layer of ei-
erably higher resistance to thermal degradation ther diamond or CBN. Examples are: diamond-
than the phenol – formaldehydes. coated mounted points and discs used by
dentists, relatively inexpensive diamond-coated
wheels for offhand sharpening of carbide tools,
7.3. Metal Bonds and wheels of complicated shapes coated with
diamond or CBN used for form grinding of
The abrasive most often bonded with metal is workpieces, where great precision can be at-
manufactured diamond, but the use of cubic tained because of little or no tool wear.
boron nitride (CBN) in metal bonds is expected
to increase very significantly.
Three types of metal-bonded products are 8. Coated Abrasive Products
made:
1) Those in which the abrasive zone is bonded In coated abrasives a single layer of abrasive
directly to the core by a heating process; grains is bonded with an adhesive to flexible or
2) Those in which segments or rims are produced semirigid backings.
and then attached to the core or steel blade af-
terward;
3) Those bonded by electroplating. 8.1. Components
For the first type, a core or preform is placed
in a mold, and the abrasive-metal mix added Abrasives include quartz, known in the trade
and then pressed. After being stripped from the as flint; garnet; emery, usually the Turkish va-
mold, the body usually is sintered to maximum riety; fused aluminas of the regular, semifri-
density, or it may be sintered to controlled poros- able, white, and pink types; sintered aluminas
ity followed by infiltration with a liquid metal, made from gels; fused zirconia – alumina of the
such as a silver solder. Alternatively, the prod- NZ Alundum variety; silicon carbide, black and
uct may be hot pressed in a graphite mold. Bond green types; and diamond and CBN, for very
compositions vary greatly. Commonly used ones limited applications.
include bronzes, various cobalt and nickel al-
loys, steels, and cemented carbides. Maturing Backings include Paper of different
temperatures vary from 500 ◦ C for bronzes to weights: A for fine hand sanding with sheets, C
1200 ◦ C for cemented carbides. Firing is in neu- for medium hand operations or machine finish-
tral or reducing atmospheres. In general softer ing, E for heavy machine grinding.
bonds are used with hard, dense work materials, Cloth: woven cotton or polyester, stitch-
whereas harder ones are used to grind relatively bonded polyester. They must be specially treated
soft but abrasive materials. For example, bronze before being coated with abrasives on cloth-
bonds commonly are used on dense alumina, ce- finishing lines to give them the appropriate me-
mented carbides, and quartz crystals, whereas chanical characteristics. Different weights are
carbide bonds often are used to groove concrete used, depending on the operation: J for flexi-
highways and cut sandstones. ble products, X or Y for coarse grits or use on
In the case of rims and segments, similar powerful machines.
bonds, manufacturing methods, and firing tem- Combinations of paper plus cloth: used when
peratures are employed. In the production of dia- limited backing stretching and high resistance to
mond blades for use in the construction industry, tearing are necessary: wide belts for high power
segments have been attached to the steel center machines, drum sanders.
by brazing. However, laser welding, introduced
16 Abrasives

Vulcanized fiber made of several layers of the minimum amount needed to satisfy end-use
cotton-based paper gelatinized with zinc chlo- conditions is employed.
ride and vulcanized together. Different thick-
nesses are used, from 0.4 to 0.75 mm, depending
upon the required stiffness and strength. Main 8.3. Applications
use is fiber disks for portable machines for rough
grinding and semi-finishing. The jumbo rolls are cut and converted into many
Polyester films for microfinishing and polish- different shapes: narrow rolls, sheets, disks, end-
ing of mechanical, electronic and optic compo- less belts 10 to 3000 mm wide and 250 to
nents with very fine P series grits and micron or 7000 mm long, flap wheels and flap disks, spi-
sub-micron sizes Abrasive grains are aluminium rally wound cones and pencils. These shapes
oxide, silicon carbide, diamond and special ma- are used by hand or on sanding machines in
terials such as alumina flour and chromium, iron, practically all industries for roughing, finish-
and cerium oxides. ing, and polishing of wood, sheet and struc-
tural metal, mechanical parts, weldings, lac-
Adhesives used are high-quality hide glue; quers, glass, plastic, rubber, plaster, semicon-
phenol – or urea – formaldehyde resins; and ductors, etc.
polyurethane or epoxy-based varnishes. These
adhesives may contain mineral fillers to modify
the physical properties of the bond, or to aid the 9. International Quality
operations in other ways (see Section 7.2).
Specifications

8.2. Production Because of the mature nature of the abrasive in-


dustry and the use of various specifications, truly
A strip of backing material up to 1.5 m or more international standards have been slow in devel-
in width is passed into a making machine where oping.
a thin film of bond, known as the maker coat, is However, the International Organization for
applied. Sized abrasive is fed onto it by grav- Standardization (ISO) has been active in es-
ity, or an electrostatic field is used to orient tablishing specifications relating to bonded and
the longer dimension of the grain perpendicu- coated products, and, to a lesser extent, to the
lar to the backing. The coating may be closed, abrasive grain itself. This organization has is-
in which the abrasive entirely covers the adhe- sued ISO standards, some 21 of which relate to
sive, or open, in which 50 – 75 % of the surface those items [38]. Eleven of them cover designa-
is covered. The item is dried at about 60 ◦ C after tions and dimensions of various coated products,
which another layer of adhesive, known as the nine of bonded items, including diamond and
sizing coat, is applied to secure more firmly the CBN, and one relates to grit sizes of diamond
abrasive grains. This second coat may be of the and CBN.
same composition as the first, or it may be dif- National standards exist in the United States
ferent, e.g., resin used over glue. Then the bond (ANSI) [30], Japan, Japanese Industrial Stan-
is dried further and cured at about 150 ◦ C. The dards (JIS) [42], and Europe (FEPA) [31].
coated abrasive is then coiled into a large roll
known as a jumbo.
For most uses a further operation is required 10. Safety
to improve product flexibility. This involves
breaking the bond in a controlled manner. In Bonded abrasive products are not indestructible.
single flexing, cracks are developed at right an- Strengths vary with such factors as the type of
gles to the length of the strip. In double flexing, bond, the grit size of the abrasive, and the struc-
there are two series of cracks at about 45◦ to ture and grade of the product required to effi-
the length. Triple flexing is a combination of ciently perform a particular grinding operation.
the other two types. Because of disturbance to Therefore, the user must take special precautions
the abrasive bond layer by such operations, only to see that these products are properly handled,
Abrasives 17

mounted correctly on the machine, and not oper- tions and wheel dimensions. Drawings of suit-
ated at excessive speed. The latter is the most fre- able equipment are included. Similarly, “Ven-
quent cause of wheel breakage, leading to dam- tilation and Safe Practices of Abrasive Blast-
age of equipment and possible personal injury. ing Operations,” ANSI Z9.4−1979, 12 p., in-
Most wheels are marked for maximum operat- cludes sections on dust risks, equipment, and op-
ing speeds or instructions are packaged with the erational procedures. It contains information on
items. minimum air volumes for blast cleaning rooms
“Safety Requirements for the Use, Care occupied by blasters.
and Protection of Abrasive Wheels,” ANSI Most abrasive products are inert, producing
B 7.1−1988, 106 p., is particularly useful be- dusts classified as inert or nuisance types when
cause it includes sections on definitions of the the work material also is inert. When the dust
various types of grinding operations, and on is not inert, not only must the amount to which
wheel shapes with their limitations, and han- the operator is exposed be known, but also its
dling and storage of abrasive products. General composition. Most of the dust generated from
conditions of machines, safety guards, flanges, dry grinding and coated-abrasive operations is
proper methods for mounting, general operat- from the work material, with lesser amounts
ing rules, and, most importantly, standard and derived from the abrasive products themselves.
special maximum operating speeds are covered Some abrasive products incorporate active fillers
also. or grinding aids containing sulfur or fluorine
“Safety Requirements for the Construction, compounds. Use of coated abrasives containing
Care and Use of Grinding Machines,” ANSI quartz (free silica) as the abrasive may require
B11.9−1975, 71 p., is likewise helpful because special controls. Only when both the amount and
it contains sections on design of machines, the composition of the airborne dust are known
guards and flanges; on operating risks, and on can a determination be made as to whether the
the responsibilities of manufacturer, employer, requirements of the particular jurisdiction (city,
and employee in connection with the care and country, etc.) are being met, and the health of the
use of equipment. operator safeguarded.
An EC standard concerning the safety of For further details see “Fundamentals of In-
grinding machines is in preparation (EN 13218). dustrial Hygiene” [43], which relates specifi-
Japanese Industrial Standards (JIS), cally to requirements in the United States but
R6240−1972 and R6241−1972 [42], as well which should be of interest worldwide. Par-
as the European Safety Code, FEPA standard ticularly valuable are the appendices and their
12/87, are similar to ANSI B7.1 but vary in de- revisions [44–47]. For requirements in Europe
tails. Requirements in Germany (VBG 49) are (MAK), see [48].
more stringent than in most other countries be- With respect to disposal of wastes from abra-
cause high-speed wheels must carry a certificate sive products, the major concern is related to the
with certifying that they have been tested by the chemical composition of the swarf because of
manufacturer in accordance with the specifics its finely divided nature and consequently large
of ZH 1/670. Independent tests also are carried surface area, which accelerates solubility and
out to assure compliance with ZH 1/670. chemical reactions. Because most of the grind-
EC standards concerning the safety of ing debris originates from the work material,
bonded, coated, and diamond/CBN abrasives are primary interest resides in its composition, solu-
in preparation [52]. bility, and toxicity, with secondary emphasis on
Another potential risk involves the effect of those properties of the bonded or coated abra-
breathing dusts generated during abrasive opera- sive used in the operation. Knowledge of such
tions, such as grinding and polishing or blasting, factors is required to determine the method of
particularly when done in a dry operation. disposal that will not have an adverse impact on
“Ventilation Control of Grinding, Polishing the environment.
and Buffing Operations,” ANSI Z 43.1−1966, Disposal of organic-bonded wheels and
21 p., is of particular interest because it covers coated abrasives is also becoming a problem as
exhaust hoods and enclosures, with minimum they release phenol when leached by rain water
exhaust volumes specified for various opera- in open landfills.
18 Abrasives

11. References 15. Norton Co., US 2 426 643, 1947 (R.


R. Ridgway).
1. P. B. Gove (ed.): Webster’s Third New 16. Norton Co., US 2 579 885, 1951 (J. A. Upper).
International Dictionary, Merriam-Webster, 17. Norton Co., US 2 003 867, 1935 (R.
Inc., Springfield, Mass. 1981. R. Ridgway).
2. T. J. Drozda, C. Wick (eds.): Tool and 18. Norton Co., US 3 216 794, 1965 (S.
Manufacturing Engineers Handbook, 4th ed., J. Roschuk).
vol. 1, Machining, Chapter 11, Grinding, 130 19. Norton Co., US 3 181 939, 1965 (D.
pages, Society of Manufacturing Engineers, W. Marshall, S. J. Roschuk, N. W. Thibault).
Dearborn, Mich.1983, see especially pages 20. Norton Co., US 3 891 408, 1975 (R. A. Rowse,
11 – 1 to 11 – 15, 11 – 49 to 11 – 130. G. R. Watson).
3. Coated Abrasives – Modern Tool of Industry, 21. Norton Co., US 3 079 243, 1963 (H. F. G.
1st ed., Coated Abrasives Manufacturers’ Ueltz).
Institute, Cleveland, Ohio 1982, esp. 22. 3 M Co., US 4 314 827, 1982 (M.
p. 80 – 426. A. Leitheiser, H. G. Sowman).
4. R. Williams (ed.): Machining Hard Materials, 23. Kennecott Corp., GB 2 099 012 A, 1982 (R.
1st ed., Society of Manufacturing Engineers, J. Seider, A. P. Gerk).
Dearborn, Mich. 1982, p. 131 – 243. 24. Carborundum Co., US 492 767, 1893 (E. G.
5. R. L. McKee: Machining with Abrasives, Van Acheson).
Nostrand Reinhold Co., New York 1982, esp. 25. Norton Co., US 1 897 214, 1933 (R.
1 – 36, 123 – 304. R. Ridgway).
6. P. Daniel (ed.): Advances in Ultrahard 26. General Electric Co., US 2 941 241 to 248
Materials Applications Technology, vol. 1, inclusive, and 250 to 252 incl., 1960 (various
DeBeers Industrial Diamond Division, Ascot, G. E. Co. personnel). US 2 947 608 to 611
England 1982, esp. 16 – 71, 92 – 103. incl., 1960 (H. T. Hall, 608; H. M. Strong, 609;
7. Ultrahard Materials in Industry, Grinding Hall, Strong, 610; F. P. Bundy, 611).
Metals with Abrasive Boron Nitride, DeBeers 27. Industrial Distributors (1946) Ltd., US
Industrial Diamond Division, Ascot, England 3 902 873, 1975 (F. H. Hughes). ASEA, US
1982, p. 1 – 63. 3 904 391, 1975, US 3 957 461, 1976 (O.
8. W. Burkart, K. Schmotz: Grinding and Lindstrom, E. Lundblad).
28. General Electric Co., US 2 947 617, 1960 (R.
Polishing Theory and Practice, 1st ed.
H. Wentorf, Jr.).
(English), Portcullis Press, Redhill, England
29. General Electric Co., US 3 645 706, 1972 (H.
1981, esp. 47 – 239.
P. Bovenkerk, W. A. Berecki).
9. F. T. Farago: Abrasive Methods Engineering,
30. ANSI, standards available from American
Industrial Press, Inc., New York 1980, vol. 1,
National Standards Institute, Inc., 1430
366 p., vol. 2, 508 p.
Broadway, New York, NY.
10. F. Hughes: Diamond Grinding of Metals, 2nd
31. FEPA, Fédération Européenne des Fabricants
ed., Industrial Diamond Information Bureau,
de Produits Abrasifs, Standards,20, Avenue
Ascot, England 1978, esp. 39 – 290.
Reille, F-75014, Paris, France; Internet:
11. K. B. Lewis, W. F. Schleicher: The Grinding
http://www.fepa-abrasives.org.
Wheel, 3rd ed., Grinding Wheel Institute,
32. N. W. Thibault, H. L. Nyquist, Trans. Am. Soc.
Cleveland, Ohio 1976, esp. 36 – 463.
Met. 38 (1947) 271 – 330.
12. P. Daniel (ed.): Industrial Diamond Review, 33. A. G. Evans, E. A. Charles, J. Am. Ceram. Soc.
DeBeers Industrial Diamond Division, Ascot, 59 (1976) 371 – 372.
England. (Includes articles on the application 34. T. N. Loladze, G. V. Bokuchava, G.
of diamond and CBN as well as a section E. Davidova in J. H. Westbrook, H. Conrad
devoted to abstracts relating to various aspects (eds.): The Science of Hardness Testing and Its
of diamond, cubic boron nitride and other hard Research Applications, Am. Soc. for Metals,
materials), published1940 – present. Metals Park, Ohio 1973, p. 251 – 257.
13. V. L. Eardley-Wilmot: “Artificial Abrasives 35. T. N. Loladze, G. V. Bokuchava, G.
and Manufactured Abrasive Products and E. Davidova in J. H. Westbrook, H. Conrad
Their Uses,” Abrasives, Canada Dept. Mines, (eds.): The Science of Hardness Testing and Its
no. 699, part 4, Ottawa 1929. Research Applications, Am. Soc. for Metals,
14. Ind. Miner. (London) 149 (Feb. 1980) 55 – 57. Metals Park, Ohio 1973, p. 495 – 502.
Abrasives 19

36. L. Coes, Jr.: Abrasives, Springer Verlag, New 45. OSHA Safety & Health Standards (29 CFR
York-Wien 1971, p. 154 – 163. 1910), OSHA 2206, U.S. Department of Labor
37. E. I. du Pont, US 3 179 631, 1965 (A. Occupational Safety & Health Administration,
L. Endrey). Washington, D.C., July 1997, esp. Subpart G,
38. “Tools”, ISO Standards Handbook 6, 1st ed., Section 1910.94: Ventilation.
ISO Central Secretariat, Case postale 56, 46. RTECS, US Department of Health and Human
CH-1211 Geneva 20, Switzerland 1980, Services, Cincinnati, 1997.
p. 81 – 86, 121 – 133, 164 – 185, 289 – 292, 47. OSHA hazard communication standard (29
330 – 334, 400 – 405, 417, 465, 519 – 521, CFR 1910–1200) and material safety data
589 – 591, 663, 683 – 703. sheets available from chemical manufacturers.
39. Industry and Trade Summary: Abrasives, U.S. 48. Deutsche Forschungsgemeinschaft (ed.):
Dept. Commerce, International Trade Maximum Concentrations at the Workplace
Commission, Washington, D.C.1995, 30 and Biological Tolerance Values for Working
pages. Materials 1995 (MAK), VCH
40. P. Harben, Ind. Miner. (London) 134 (Nov. Verlagsgesellschaft, Weinheim 1995.
1978) 62. 49. US Geological Survey, Mineral Commodity
41. T. Dickson, Ind. Miner. (London) 159 (Dec.
Summaries, Jan. 1988.
1980) 70.
50. Mineral Facts and Problems, US Bureau of
42. JIS Standards, available from ANSI, American
Mines Bulletin, 675 (1985)
National Standards Institute, Inc., 1430
51. F. J. Kuzler: Hard and Superhard
Broadway, New York, NY.
43. B. A. Plog (ed.): Fundamentals of Industrial Materials–World Markets, Applications, and
Hygiene, 4th ed., National Safety Council, Opportunities: 1993 –1998 Analysis , World
Itasca, Ill., 1995, esp. pp. 175 – 182, 456 – 459, Information Technologies, Northport, NY
538 – 539, 574 – 576. 1993.
44. American Conference of Governmental 52. EN 12413: Safety of Bonded Abrasives
Industrial Hygienists. (ACGIH) (ed.): (1998); EN 13236: Safety of Diamond/CBN
Threshold Limit Values for Chemical Abrasives (in preparation); Safety of Coated
Substances 1998 – 99, (TLV), Cincinnati, Ohio Abrasives (in preparation).
1998, esp. pp. 15 – 86.

ABS → Polystyrene and Styrene Copolymers


Acaricides 1

Acaricides
Franz Müller (formerly Novartis Crop Protection AG, Basel), Allschwil, Switzerland (Chaps. 2, 3, 4)
Hans Peter Streibert, Novartis Crop Protection AG, Basel, Switzerland (Chap. 1; Chaps. 2 and 3 in part)
Saleem Farooq, Novartis Crop Protection AG, Basel, Switzerland (Chap. 1; Chaps. 2 and 3 in part)

1. Phytophagous Mites and Their Con- 3.6. Halogenated Benzhydrol Derivatives . 14


trol . . . . . . . . . . . . . . . . . . . . . . . 1 3.7. Organometallic Compounds . . . . . . 15
1.1. Possible Reasons for the Mite Problem 1 3.8. Other Compounds . . . . . . . . . . . . . 15
1.2. Mite Species of Economic Importance 1 4. Toxicology . . . . . . . . . . . . . . . . . . 20
1.3. Possibilities for Mite Control . . . . . . 3 4.1. Organophosphates and
1.4. Mite Resistance . . . . . . . . . . . . . . . 3 (Oxime)Carbamates . . . . . . . . . . . 20
2. Older Acaricides . . . . . . . . . . . . . . 3 4.2. Pyrethroids . . . . . . . . . . . . . . . . . 30
3. Insecticides with Acaricidal Activity . 4 4.3. Formamidines . . . . . . . . . . . . . . . 31
3.1. Organophosphates 4.4. Nitrophenyl Esters . . . . . . . . . . . . . 32
and (Oxime)Carbamates . . . . . . . . 4 4.5. Sulfonic Acid Ester . . . . . . . . . . . . 32
3.2. Pyrethroids . . . . . . . . . . . . . . . . . 11 4.6. Halogenated Benzhydrol Derivatives . 33
3.3. Formamidines . . . . . . . . . . . . . . . 13 4.7. Organometallic Compounds . . . . . . 33
3.4. Nitrophenyl Esters . . . . . . . . . . . . . 13 4.8. Other Compounds . . . . . . . . . . . . . 34
3.5. Sulfonic Acid Esters . . . . . . . . . . . . 14 5. References . . . . . . . . . . . . . . . . . . 38

1. Phytophagous Mites and Their this increase of mites are manifold and not yet
Control completely understood. Intensified agricultural
production methods, such as monocultures, ex-
Mites belong to the phylum Arthropoda, the tensive use of fertilizers, improved irrigation
class Arachnida, and the order Acarina. They systems, and cultural practices such as pruning
have developed an astonishing variety of feeding have improved the vigor and nutritional value
habits. Some mites are predators, while others of the plants. However, these conditions also are
feed on detritus in soil or water. The economi- beneficial to the development of phytophagous
cally important species are parasitic on either an- mites and may result in higher rates of repro-
imals (e.g., ticks, scab mites) or plants (e.g., spi- duction. Furthermore, the indiscriminate use of
der mites, eriophyid mites). Phytophagous mites pesticides in the past may have reduced or even
are found in all parts of the world on practi- eliminated the populations of natural enemies
cally all crop plants and may cause consider- of the mites (predatory mites and beneficial in-
able damage. Approximately 8 – 10 % (annually sects) thereby encouraging the development of
ca. $ 400×106 ) of the total insecticide-acaricide certain phytophagous mite species. In addition,
market is spent on the control of phytophagous some insecticides (e.g., DDT, Carbaryl) used for
mites. the control of insect pests, may promote the re-
production of phytophagous mites [6–8].

1.1. Possible Reasons for the Mite


Problem 1.2. Mite Species of Economic
Importance
In recent decades, attacks by mites on food crops
and fibers have increased so drastically that in The economically important species of the phy-
many situations mite control has become an im- tophagous mites are as follows:
portant feature of crop protection. Reasons for

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 017
2 Acaricides

Tetranychidae – Spider mites der mites is their enormous reproductive poten-


Tetranychus urticae (Koch), Two-spotted tial: a female of the European red mite (Panony-
mite, widespread on fruit and on grapes, veg- chus ulmi) produces 14 – 30 eggs during its life-
etables, cotton, hops, roses, ornamentals, and time, the female two-spotted mite as many as
greenhouse cultures. 70 – 120. The tiny, pale green eggs are usually
Tetranychus cinnabarinus (Boisduval), carmine deposited on the underside of the leaves within
mite, widely spread in the warmer climatic re- the webbing [9–11].
gions on cotton, fruit cultures, ornamentals, and The eggs hatch after 3 – 4 days in the case
in greenhouses. of Tetranychus species, whereas in the Euro-
Tetranychus kanzawai (Kishida), tea red spider pean red mites the first instar larva appears af-
mite, found on tea in Asia. ter 6 – 20 days. All the spider mites go through
Tetranychus mcdanieli (McGregor), McDaniel five stages in their life cycle: egg, six-legged
mite, found on fruit on the west coast of the larva, eight-legged protonymph, deutonymph,
United States, as are other, different Tetranychus and adult. These stages are separated by rest-
species. ing stages followed by molts. The time for the
Panonychus ulmi (Koch), European red mite, whole development depends strongly upon the
widespread on fruit (apples, peaches, pears, temperature, humidity, and the host plant. Un-
prunes, plums) and on grapes. der favorable conditions, the postembryonal de-
Panonychus citri (McGregor), citrus red mite, velopment in Tetranychidae is completed within
found in citrus cultures worldwide. 8 – 14 days.
Tenuipalpidae – False spider mites Orchard mites usually develop six to eight
Various Brevipalpus species, flat mites, found generations per season, depending on the areas
on citrus and different subtropical fruits, tea, where they occur. In greenhouses and in warm
greenhouse cultures. climates, the two-spotted mite may develop up
Tarsonemidae – Soft-bodied mites to 30 generations per vegetation period, whereas
Hemitaronemus latus (Banks), citrus silver for Panonychus species only 6 – 20 generations
mite, found on cotton, citrus, attacks a wide can be expected.
range of agricultural crops and ornamental and The climatic conditions during the summer
indigenous plants in tropical and subtropical re- months have a strong influence on the popula-
gions. tion build-up during the following spring. Most
Eriophyidae – Gall mites spider mites overwinter as bright orange adult
Phyllocoptruta oleivora (Ashmead), citrus females within bark crevices or in plant debris
rust mite, found on citrus. on the ground. The European red mite is an ex-
Aceria sheldoni (Ewing), citrus bud mite, found ception, overwintering as a winter egg on twigs.
on citrus. Many weed species are excellent host plants
Life cycles and behavioral and morphologic from which the spider mites may move on to
characteristics of mites vary greatly. The de- crop plants, either by crawling or by balloon-
scription of life history given here concentrates ing (transport by wind). All mites live on the
on the agriculturally important Tetranychidae sap of the plant, piercing the leaf tissue with the
family. two sharp lances attached to the mouth and thus
The spider mites are 0.3 – 0.5 mm long, puncturing the cells in the leaf epidermis. The
eggshaped, eight-legged animals covered with leaves then become speckled, later turn brown,
hairlike appendages. These hairs (setae) are im- and, if the attack is severe, may drop. As a conse-
mobile and are sense organs. Spider mites live quence, photosynthesis and respiration are im-
in dense colonies, mainly on the underside of paired and this may affect the number of flower
the leaves. In such colonies, usually all the de- buds in the following season. A mass attack of
velopment stages are present: eggs, larvae, and phytophagous mites on deciduous fruit may re-
nymphs, as well as adults of both sexes. sult in yield losses of up to 40 % [12].
Many spider mite species produce protective The gall mites (Eriophyidae) are very tiny
webbing composed of almost invisible strands rodshaped mites with threadlike appendages.
of silk; these webs produce a favorable micro- Gall mites are very host specific and have
climate on the leaf surface. Characteristic of spi- high reproductive potential. They destroy buds,
Acaricides 3

leaves, and fruit, and they also transmit viruses. become problematic. Because of the large num-
They may cause serious economic damage, es- ber of generations per season, selection may oc-
pecially in citrus fruits. cur very rapidly in a mite population. Resistance
After a heavy attack of citrus rust mites is induced by repeated application of the same
(Phyllocoptruta oleivora), the fruit turns reddish or closely related chemicals. To compensate for
brown and shrinks because of the loss of wa- this effect, higher dosages are needed, but this is
ter. The citrus bud mite (Aceria sheldoni) causes not a long-term solution to the resistance prob-
malformation of citrus fruits. lem. New compounds with new modes of ac-
tion must continue to be developed to replace
the older ones, that have decreased in effective-
1.3. Possibilities for Mite Control ness.
New control concepts, such as integrated pest
Chemical treatment can be aimed either at over- management, have made it possible to reduce
wintering eggs (e.g., those of Panonychus ulmi) the number of acaricide treatments in many sit-
or at the mobile stages of the mites. Winter eggs uations, and this has slowed development of re-
often are treated with mineral oils. For the effec- sistance in mite populations.
tive control of mites during the vegetative period,
a number of chemicals are available. However,
compounds that are effective against all develop- 2. Older Acaricides
ment stages and have a long-term residual effect
are preferred. Products introduced at the beginning of the pes-
The compounds used should be well toler- ticide era still find limited use as acaricides in
ated by the plants, and the effects on environ- various parts of the world.
ment and beneficial insects should be minimal. Nitrophenols , in combination with mineral
The population of these natural enemies, which oil, were used to fight mites in orchards by elim-
could control mite populations effectively, has inating their overwintering eggs. However, the
been reduced severely or eliminated in most or- phytotoxicity of these compounds has been a
chards, vineyards, and citrus groves as a result drawback [16, p. 527]. For a review of nitrophe-
of the use of broadspectrum pesticides aimed at nols with acaricidal activity see [17, p. 2] and
targets other than mites. [18, p. 537].
Biological control of phytophagous mites by Sulfur [7704-34-9], used mainly as a protec-
releasing their natural enemies, such as preda- tive fungicide to control powdery mildews, is
tory bugs or coccinellids, has been successful effective against the mobile stages of various
in greenhouses or in plastic tunnels. However, mite species. It is used in combination with other
only limited success has been achieved under fungicides and insecticides mainly in vineyards
field conditions [13–15]. [17, p. 2].
Integrated pest management, which makes Azobenzene [103-33-3] has been used as a fu-
use of a variety of possible techniques, includ- migant in greenhouses against insects and mites,
ing chemicals, to keep the pest population be- especially against eggs [17, p. 2].
low the economic threshold, is far more promis- Binaparcryl [485-31-4] has been used as a
ing than simple biological control. In integrated nonsystemic acaricide, mainly against all stages
pest management systems, chemicals are used of spider mites and powdery mildew of apples,
only when the population density reaches a cer- citrus fruits, cotton, etc. [19, p. 73].
tain level (economic threshold) and if possible, Chlorfenson [80-33-1] has been used as a
selective acaricides are chosen so as not to harm nonsystemic acaricide with long residual ovici-
beneficial insects and predatory mites. dal activity. It is effective against mites of citrus
and other fruits [19, p. 150].
Tetrasul [2227-13-6] has been used as a non-
1.4. Mite Resistance systemic acaricide, particularly suitable for the
control of various phytophagous mites which hi-
In many areas, mites have developed resistance bernate in winter egg form. It has been used on
to certain chemicals: their control therefore has vegetables and fruits [19, p. 790].
4 Acaricides

Chlorpropylate [5836-10-2] has been used as Chlorfenvinphos [470-90-6], 2-chloro-1-


a nonsystemic contact acaricide on cotton, fruits, (2,4-dichlorophenyl)vinyl diethyl phosphate,
and ornamentals [19, p. 169]. C12 H14 Cl3 O4 P, M r 359.6, mp − 23 to − 29 ◦ C,
Aldoxycarb [1646-88-4] is a systemic in- bp 167 – 170 ◦ C, is a colorless liquid which is
secticide and nematicide, and is a potent sparingly soluble in water, and miscible with
cholinesterase inhibitor. It has been used on to- most organic solvents [20, p. 211].
bacco and as a cotton seed dressing [19, p. 9].
Chlorobenzilate [510-15-6] is a nonsystemic
acaricide with little insecticidal activity. It has
been used against phytophagous mites on fruits
and vegetables [19, p. 162].

3. Insecticides with
Acaricidal Activity
3.1. Organophosphates and Chlorfenvinphos is produced by reaction of
(Oxime)Carbamates 2,4-dichloroacetophenone with triethyl phos-
phite [22].
Organophosphates and carbamates, used as Chlorfenvinphos (announced in 1952) is used
broad-spectrum insecticides but also exhibiting for soil application to control root flies, root
acaricidal action, were able to contain the mite worms, and insects in vegetables and fruit flies
problem for some time. However, development in maize.
of mite resistance toward these compounds has Trade Names. Birlane (Cyanamid); Apachlor
made them less and less effective as acaricides. (Rhône-Poulenc).

Aldicarb [116-06-3], 2-methyl-2-(methyl- Chlorpyrifos-methyl [5598-13-0], O,O-


thio)propanal O-methylcarbamoyloxime, dimethyl O-3,5,6-trichloro-2-pyridyl phos-
C7 H14 N2 O2 S, M r 190.3, mp 98 – 100 ◦ C, forms phorothioate, C7 H7 C13 NO3 PS, M r 322.5, mp
colorless crystals which are practically insoluble 45.5 – 46.5 ◦ C, consists of colorless crystals
in heptane and mineral oils, moderately soluble which are sparingly soluble in water but sol-
in water, and soluble in most organic solvents uble in acetone, benzene, chloroform, hexane,
[20, p. 26]. and methanol [20, p. 237].

Aldicarb is produced by reaction of isobutene Chlorpyrifos-methyl is produced by reaction


with nitrosyl chloride followed by reaction of the of 3,5,6-trichloro-2-pyridinol with dimethyl-
product with sodium methyl sulfide; the result- thiophosphoryl chloride [23].
ing oxime is then converted into the carbamate Chlorpyrifos-methyl is used to con-
with methyl isocyanate [21]. trol aquatic larvae, flies, household pests,
Aldicarb (announced in 1965) is a mosquitoes, pests in stored grain, and various
cholinesterase inhibitor which is metabolically foliar crop pests.
activated to sulfoxide. It is applied to soil to con- Trade Name. Reldan (DowElanco); Pyriban
trol chewing and sucking insects, spider mites, (Aimco).
and nematodes in glasshouse and outdoor orna-
mentals, vegetables, sugar beet, peanuts, fruits, Diazinon [333-41-5], O,O-diethyl O-2-
etc. isoproyl-6-methylpyrimidine-4-yl phosphoro-
Trade Names. Temik (Rhône-Poulenc); thioate, C12 H21 N2 O3 PS, M r 304.3, bp
Sanacarb (Sanachem).
Acaricides 5

83 – 84 ◦ C (26.6 mPa), is a clear colorless liquid


which is sparingly soluble in water but com-
pletely miscible with common organic solvents
[20, p. 354].
Dimethoate is produced by reaction of the
sodium salt of O,O-dimethyldithiophosphoric
acid with N-methylchloroacetamide [26].
Dimethoate (announced in 1948) is effective
against houseflies and Diptera of medical impor-
tance.
Trade Names. Cygon, Roxion (Wilbur-Ellis);
Diazinon is produced by condensation of Perfekthion (BASF); Champ (Searle India);
isobutyramidine with acetoacetate to yield the Danadim (Cheminova); Robgor (Ramcides).
intermediate 2-isopropyl-4-methylpyrimidine,
which is transformed into the final product by Disulfoton [298-04-4], O,O-diethyl
treatment with diethylthiophosphoric acid [24]. S-(2-ethylthio)ethyl phosphorodithioate,
Diazinon (announced in 1953) is a nonsys- C8 H19 O2 PS3 , M r 274.4, mp < −25, bp 128 ◦ C,
temic insecticide/acaricide with contact, stom- is a colorless oil which is sparingly soluble in
ach, and respiratory action. It is used to control water but readily miscible with common organic
sucking and chewing insects and mites on a va- solvents [20, p. 438].
riety of crops.
Trade Names. Basudin (Novartis); Dianon (Nip-
pon Kayaku); Knox-out (Elf Atochem).

Dicrotophos [141-66-2], dimethyl (E)-2-


dimethylcarbamoyl-1-methylvinyl phosphate,
C8 H16 NO5 P, M r 237.2, bp 460 ◦ C, is a yellow-
Disulfoton is produced by reaction of the
ish liquid which is completely miscible with wa-
sodium salt of diethyldithiophosphoric acid with
ter and common organic solvents [20, p. 382].
ethylmercaptoethyl chloride [27].
Disulfoton (announced in 1952) is used to
control aphids, thrips, mealybugs, other sucking
insects, and spider mites in potatoes, vegetables,
cereals and other crops.
Trade Names. Disyston (Bayer); Solvirex,
Fremin AL (Novartis).
Dicrotophos is produced by reaction of
trimethyl phosphite with 2-chloro-N,N-di- EPN [2104-64-5], O-ethyl O-4-nitrophenyl
methyl-3-oxobutyramide [25]. phenylphosphonothioate, C14 H14 NO4 PS, M r
Dicrotophos (announced in 1965) is used to 323.3, mp 34.5 ◦ C, consists of yellow crystals
control sucking, chewing, and boring insects and which are practically insoluble in water but sol-
mites in cotton, coffee, rice, sugar cane, and to- uble in common organic solvents [20, p. 464].
bacco.
Trade Names. Bidrin (Cyanamid); Dicron (Hui
Kwang).

Dimethoate [60-51-5], O,O-dimethyl S-(N-


methylcarbamoyl)methyl phosphorodithioate,
C5 H12 NO3 PS2 , M r 229.2, mp 51 – 52 ◦ C, con-
sists of colorless crystals which are moder-
ately soluble in water, soluble in alcohols, ben- EPN is produced by reaction of benzene with
zene, chloroform, dichloromethane, ketones, phosphorus trichloride in the presence of alu-
and toluene [20, p. 550]. minum chloride and treatment of the resulting
6 Acaricides

product with phosphenyl chloride to give the by reaction of an excess of dichlorobutane with
thiophosphonic acid, which is converted to ethyl phenol in the presence of potassium hydroxide
phenyl thiophosphonate chloride by treatment [30].
with ethanol, followed by condensation of the Fenothiocarb (announced in 1985) is a non-
product with the sodium salt of p-nitrophenol systemic acaricide used to control eggs and
[28]. young stages of Panonychus citri, Panonychus
EPN (announced in 1948) is used against a ulmi, and other Panonychus spp.
broad range of Lepidoptera larvae, especially Trade Name. Panocan (Kumiai).
ballworms and Alabama argillacea in cotton,
Chilo spp. in rice, and other leaf-eating larvae Formothion [2540-82-1], O,O-dimethyl S-
in fruit and vegetables. [formyl(methyl)carbomylmethyl] phosphoro-
Trade Name. EPN (Nisson). dithioate, C6 H12 NO4 PS2 , M r 257.3, mp
25 – 26 ◦ C, is a pale yellow viscous liquid or
Ethion [563-12-2], O,O,O ,O -tetraethyl crystalline mass which is moderately soluble

S,S -methylene bis(phosphorodithioate), in water but completely miscible with common
C9 H22 O4 P2 S4 , M r 384.5, bp 164 – 165 ◦ C organic solvents [20, p. 625].
(40 Pa), is a colorless to amber liquid which is
practically insoluble in water but miscible with
most common organic solvents [20, p. 480].

Formothion is produced by reaction of the


sodium salt of O,O-dimethyldithiophosphoric
acid with N-methyl N-formyl carbamoylmethyl
chloride [31].
Ethion is produced by reaction of Formothion (announced in 1960) is used
diethyldithiophosphoric acid with formalde- against a wide range of sucking and mining in-
hyde in the presence of sulfuric acid [29]. sects, such as Aphididae, bugs, Cicadellidae,
Ethion (announced in 1957) is used to con- Cocidae, as well as against some chewing in-
trol spider mites, aphids, scale insects, thrips, sects and spider mites on a variety of field crops,
and lepidopterous larvae in fruits, vegetables, fruit trees, citrus and other tropical fruit, cotton,
and turf. ornamentals, rice, tobacco, and vegetables.
Trade Names. Ethiol, Rhodocide (Rhône- Trade Name. Anthio (Novartis).
Poulenc); Tafethion (Rallis); Dhanumix
(Dhanuka). Mecarbam [2595-54-2], O,O-diethyl S-(N-
ethoxycarbonyl-N-methylcarbamoylmethyl)
Fenothiocarb [62850-32-2], S-4-phenoxy- phosphorodithioate, C10 H20 NO5 PS2 , M r 329.4,
butyl dimethylthiocarbamate, C13 H19 NO2 S, bp 144 ◦ C (2.7 Pa), is a pale yellow to brown oil
M r 253.4, mp 40 – 41 ◦ C, consists of colorless which is sparingly soluble in water, soluble in
crystals which are sparingly soluble in water aliphatic hydrocarbons, and miscible with alco-
but readily soluble in cyclohexanone, acetoni- hols, esters, and ketones [20, p. 774].
trile, acetone, xylene, methanol, and hexane [20,
p. 517].

Mecarbam is produced by reaction of


Fenothiocarb is produced by reaction of the sodium salt of O,O-diethyldithiophos-
the sodium salt of N,N-dimethylcarbamothioate phoric acid with N-ethoxycarbonyl-N-
with phenoxybutylchloride, which is obtained methylcarbamoylmethyl chloride [32].
Acaricides 7

Mecarbam (announced in 1961) possesses Methidathion [950-37-8], O,O-di-


slight systemic properties, contact and stomach methyl S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-
action, and long residual activity. It is used to thiadiazol-yl methyl phosphorodithioate,
control aphids, suckers, whitefly, scale insects, C6 H11 N2 O4 PS3 , M r 302.3, mp 39 – 40 ◦ C, con-
mealybugs and red spider mites on a variety of sists of colorless crystals which are sparingly
crops; and leaf hoppers, plant hoppers, and min- soluble in water, moderately soluble in hexane
ers on rice. and n-octanol, and soluble in ethanol, acetone,
Trade Name. Murfatox (Efthymiadis). and toluene [20, p. 811].

Methacrifos [62610-77-9], (E)-O-2-


methoxycarbonylprop-1-enyl O,O-dimethyl
phosphorothioate, C7 H13 O5 PS, M r 240.2, bp
90 ◦ C (1.3 Pa), is a colorless liquid which is
sparingly soluble in water and miscible with
many organic solvents [20, p. 806]. Methidathion is produced by reaction
of 2-methoxy-1,3,4-thiadiazol-5(4H)-one with
dimethyldithiophosphoric acid via the N-
chloromethyl derivative or in a one-step reaction
in the presence of formaldehyde [35].
Methidathion (announced in 1965) is a non-
Methacrifos is produced by reaction of 2- systemic insecticide and acaricide with contact
hydroxymethylenepropionic acid methyl ester and stomach action that is used against a wide
with dimethylthiophosphoryl chloride [33]. range of sucking and chewing insects and spider
Methacrifos (announced in 1977) is an in- mites in many crops.
secticide and acaricide with respiratory, contact, Trade Names. Supracide (Novartis); Suprathion
and stomach action. It is used for control of (Makhteshim-Agan).
arthropod pests in stored products by incorpo-
ration or by surface treatment. Methiocarb [2032-65-7], (3,5-dimethyl-
Trade Name. Damfin (Novartis). 4-methylthio)phenyl methylcarbamate,
C11 H25 NO2 S, M r 225.3, mp 119 ◦ C, consists
Methamidophos [10265-92-6], O,S-di- of colorless crystals which are sparingly soluble
methylphosporamidothioate, C2 H8 NO2 PS, M r in water, moderately soluble in hexane, and sol-
141.1, mp 44.9 ◦ C, consists of colorless crystals uble in dichloromethane and isopropanol [20,
which are highly soluble in water, isopropanol, p. 813].
and dichloromethane, and moderately soluble
in hexane and toluene [20, p. 808].

Methamidophos is prepared by isomerization


of O,O-dimethylthiophosphamidate [34]. Methiocarb is produced by reaction of 4-
Methamidophos (announced in 1970) is a methyl-3,5-dimethylphenol with chloroacetoac-
systemic insecticide and acaricide with contact etate [36].
and stomach action. It is used for control of Methiocarb (announced in 1962) is used for
chewing and sucking insects and spider mites control of slugs and snails in a wide range of
on ornamentals, vegetables, and fruits. agricultural applications: broad-range control of
Trade Names. Monitor (Bayer, Tomen, Valent); Lipidoptera, Coleoptera, Piptera, Thysanoptera,
Tamaron (Bayer); Metaphos (Eftymiadis); Pat- and Homoptera in vegetables, fruits, oilseed
role (Pruductos OSA). rape, and ornamentals.
8 Acaricides

Trade Names. Draza, Mesurol (Bayer). Monocrotophos [2157-98-4], dimethyl (E)-


1-methyl-2-(methylcarbamoyl)vinyl phosphate,
Methomyl [16752-77-5], S-methyl-N- C7 H14 NO5 P, M r 223.2, mp 54 – 55 ◦ C, consists
(methylcarbamoyloxy) thioacetimidate, of colorless, hygroscopic crystals which are sol-
C5 H10 N2 O2 S, M r 162.2, mp 78 – 79 ◦ C, con- uble in water, methanol, acetone, and n-octanol
sists of colorless crystals which are fairly soluble [20, p. 849].
in water and highly soluble in methanol, ethanol,
acetone, isopropanol [20, p. 815].

Monocrotophos is produced by reaction of


trimethylphosphite with chloroacetoacetic acid
Methomyl is produced by chlorination of methylamide in the presence of a base [39].
acetaldoxime and conversion of the resulting Monocrotophos (announced in 1959) is used
α-chlorooxime with sodium methylmercaptide for control of a wide range of pests on cotton,
[37]. rice, maize, vegetables, and ornamentals.
Methomyl (announced in 1968) controls a Trade Names. Azodrin (Cyanamid); Nuvacron
wide range of insects and spider mites in fruits, (Novartis); Apadrin (Rhône-Poulenc); Balwan
vines, olives, hops, vegetables, and ornamentals. (Rallis); Monodhan (Dhanuka).
Trade Names. Lannate (Du Pont); Methavin
(Rhône-Poulenc); Methosan (Sanachem); Omethoate [1113-02-6], O,O-dimethyl S-
Nudrin (Cyanamid). methylcarbamoylmethyl phosphorothioate,
C5 H12 NO4 PS, M r 213.2, mp − 28 ◦ C (de-
Mevinphos [26718-65-0], 2-methoxycarbonyl- comp.), bp ca. 135 ◦ C, is a colorless liquid which
1-methylvinyl dimethyl phosphate, C7 H13 O6 P, is readily soluble in water, alcohols, acetone, and
M r 224.1, bp 21 ◦ C (E isomer), 6.9 ◦ C (Z iso- many hydrocarbons, slightly soluble in diethyl
mer), is a colorless liquid which is completely ether, and almost insoluble in petroleum ether
miscible with water and many organic solvents [20, p. 896].
[20, p. 844].

Omethoate is produced by reaction of O,O-


dimethylphosphorylmercaptoacetic acid with
methyl isocyanate [40].
Omethoate (announced in 1959) is used for
control of spider mites, aphids, beetles, caterpil-
lars, scale insects, thrips, and other pests on fruit,
hops, cereal, rice, ornamentals, and other crops.
Trade Name. Folimat (Bayer).
Mevinphos is produced by reaction of
trimethyl phosphite with chloroacetoacetate Oxamyl [23135-22-0], N,N-dimethyl-2-
[38]. methylcarbamoylimino-2-(methylthio)acetam-
Mevinphos (announced in 1953) is used for ide, C7 H13 N3 O3 S, M r 219.3, mp 100 – 102 ◦ C,
control of chewing and sucking insects and spiter consists of colorless crystals which are readily
mites on a wide range of crops. soluble in water, methanol, ethanol, acetone,
Trade Names. Phosdrin (Cyanamid, Amvac); and fairly soluble in toluene [20, p. 909].
Duraphos (Amvac); Mevindrin (Hui Kwang).
Acaricides 9

Phorate is produced by reaction of O,O-


diethyldithiophosphoric acid with ethanethiol
and formaldehyde [43].
Phorate (announced in 1948) is a sys-
Oxamyl is produced by chlorination of temic insecticide and acaricide used for con-
the oxime of methylglycolate, reaction with trol of Agromyzidae, Aleyrodidae, Aphididae,
methanethiol and alkali, and conversion to the Chrysomelidae, Noctuidae, Pyralidae, Tetrany-
carbamate with methyl isocyanate [41]. chidae, and certain nematodes in a variety of
Oxamyl (announced in 1968) is used for con- crops.
trol of chewing and sucking insects, spider mites, Trade Names. Thimet (Cyanamid); Ramcides
and nematodes in ornamentals, vegetables, pota- (Kunurai); Umet (United Phosphorus).
toes, and other crops. Phosalone [2310-17-0], O,O-diethyl S-(6-
Trade Name. Vydate (DU Pont). chloro-2,3-dihydro-2-oxobenzoxazol-3-yl)me-
thyl phosphorodithioate, C12 H15 ClNO4 PS2 , M r
Phenthoate [2597-03-7], O,O-dimethyl 367.8, mp 42 – 48 ◦ C, consists of colorless crys-
S-(α-carboethoxy)phenylmethyl phosphoro- tals which are sparingly soluble in water, fairly
dithioate, C12 H17 O4 PS2 , M r 320.4, mp soluble in hexane, and readily soluble in many
186 – 187 ◦ C, consists of colorless crystals organic solvents [20, p. 961].
which are slightly soluble in water but readily
soluble in many organic solvents [20, p. 952].

Phosalone is produced by treating


O,O-diethyldithiophosphoric acid with N-
Phenthoate is produced by reaction of the chloromethyl-5-chlorobenzoxazolone [44].
sodium salt of O,O-dimethyldithiophosphonic Phosalone (announced in 1963) is used as a
acid with phenylbromoethyl acetate [42]. nonsystemic acaricide and insecticide, primarly
Phenthoate (announced in 1955) is used for in pome and stone fruit trees against Coleoptera,
control of aphids, scale insects, jassids, lace- Homoptera, Lepidoptera and Thysanoptera.
bugs, etc., in cereals, maize, rice, coffee, sun- Trade Name. Zolone (Rhône-Poulenc).
flowers, sugar cane, and other crops.
Trade Names. Elsan (Nissan); Cidial (Isagro); Phosmet [732-11-6], O,O-dimethyl S-
Aimsan (Aimco). (N-phthalimidomethyl) phosphorodithioate,
C11 H12 NO4 PS2 , M r 317.3, mp 72 – 72.7 ◦ C,
Phorate [298-02-2], O,O-diethyl S- consists of colorless crystals which are sparingly
(2-ethylthio)methyl phosphorodithioate, soluble in water but readily soluble in acetone,
C7 H17 O2 PS3 , M r 260.4, mp < − 15 ◦ C, bp toluene, xylene, and methanol [20, p. 963].
118 – 120 ◦ C (0.1 kPa), is a colorless liquid
which is sparingly soluble in water but mis-
cible with alcohols, ketones, ethers, and esters
[20, p. 959].

Phosmet is produced by reaction


of N-chloromethylphthalimide with di-
methyldithiophosphoric acid [45].
Phosmet (announced in 1961) is used for
control of lepidopterous larvae, aphids, suckers,
10 Acaricides

fruit flies, and spider mites on pome fruit, stone followed by reaction with dimethylphosphoryl
fruit, citrus fruit, ornamentals, and vines. chloride [47].
Trade Names. Prolate (Gowan); Fosdan (Gen- Pirimiphos-methyl (announced in 1966) is
eral Quimica); Inovat (Productos OSA). used for control of a wide range of insects
and mites in warehouses, stored grain, and an-
Phosphamidon [13171-21-6], O,O-di- imal houses, as well as industrial and domestic
methyl O-(2-chloro-2-diethylcarbamoyl-1- premises.
methyl)vinyl phosphate, C10 H19 ClNO5 P, M r Trade Names. Actellic (Zeneca); Actellifog
299.7, bp 162 ◦ C (2 kPa), is a pale yellow liquid (Hortochem).
which is miscible with water and many organic
solvents with the exception of aliphatic hydro- Profenofos [41198-08-7], O-4-bromo-2-
carbons [20, p. 965]. chlorophenyl O-ethyl S-propyl phosphoro-
thioate, C11 H15 BrClO3 PS, M r 373.6, bp 100 ◦ C
(1.8 Pa), is a pale yellow liquid which is spar-
ingly soluble in water but readily miscible with
most organic solvents [20, p. 1006].

Profenofos is produced by reaction of


O-(4-bromo-2-chlorophenyl) O,O-diethyl thio-
phosphate with propylbromide and triethyl-
enediamine in acetonitrole [48].
Phosphamidon is produced by reaction of Profenofos (announced in 1975) is used for
trimethylphosphite with α,α-dichloroacetic acid control of insects, particularly Lepidoptera, and
diethylamide [46]. mites on cotton, maize, sugar beet, soya beans,
Phosphamidon (announced in 1956) is used potatoes, vegetables, tobacco, and other crops.
for control of sucking, chewing, and boring in- Trade Names.Curacron (Novartis); Sanofos
sects, and spider mites on a wide range of crops. (Sanonda).
Trade Names. Dimecron (Novartis); Rilan (Ral-
lis); Kinadon (United Phosphorus). Quinalphos [13593-03-8], O,O-diethyl O-qui-
noxalin-2-yl phosphorothioate, C12 H15 N2 O3 PS,
Pirimiphos-methyl [29232-93-7], O,O-di- M r 298.3, mp 31 – 32 ◦ C, consists of colorless
methyl O-2-diethylamino-6-methylpyrimidin- crystals which are sparingly soluble in water but
4-yl phosphorothioate, C11 H20 N3 O3 PS, M r readily soluble in many organic solvents [20,
305.3, bp 15 – 18 ◦ C, is a straw-colored liquid p. 1077].
which is sparingly soluble in water but miscible
with most organic solvents [20, p. 988].

Quinalphos is produced by cyclization of o-


phenylenediamine with chloroacetic acid, ox-
Pirimiphos-methyl is produced by conden- idation of the resulting 2-hydroxyquinoxaline
sation of diethylguanidine with ethyl acetate, and reaction with diethylthiophosphoryl chlo-
ride [49].
Acaricides 11

Quinalphos (announced in 1969) is used to is a pale yellow oil which is sparingly solu-
control many insect pests such as Lepidoptera, ble in water and readily soluble in acetone,
Coleoptera and Diptera on fruit trees, cotton, dichloromethane, methanol, isopropanol, ethyl
vegetables, peanuts, and many other crops. acetate [20, p. 1226].
Trade Names. Ekalux (Novartis); Hubelux
(Sanonda); Starlux (Shaw Wallace).

Sulfotepp [3689-24-5], O,O,O ,O -


tetraethyl dithiopyrophosphate, C8 H20 O5 P2 S2 ,
M r 322.3, bp 136 – 139 ◦ C (266 Pa), is a pale
yellow liquid which is sparingly soluble in wa- Triazophos is produced by reaction of
ter but miscible with most organic solvents [20, 1-phenyl-3-hydroxy-1H-1,2,4-triazole, sus-
p. 1131]. pended in acetone, with diethoxythiophosphoryl
chloride in the presence of triethylamine [52].
Triazophos (announced in 1970) is used for
control of aphids, thrips, midges, beetles, lepi-
dopterous larvae, and other soil insects, spider
mites and other species of mites in ornamentals,
fruit trees, vines, bananas, and many other crops.
Sulfotepp is produced by reaction of Trade Names. Hostthion, Trilka, Spark
diethylthionophosphoric acid chloride with wa- (AgrEvo); Try (Sanonda).
ter in the presence of pyridine and potassium
carbonate [50]. Vamidothion [2275-23-2],O,O-dimethyl
Sulfotepp (announced in 1944) is used for fu- S-2-(1-methylcarbamoylethylthio)ethyl phos-
migation control of aphids, thrips, spider mites, phorodithioate, C8 H18 NO4 PS2 , M r 287.3, mp
and whiteflies on glasshouse crops, and sciarid 43 ◦ C, consists of colorless crystals which are
flies and phorid flies on mushrooms. readily soluble in water, benzene, toluene, ace-
Trade Name. (Bayer). tonitrile, dichloromethane, cyclohexanone, and
chloroform and sparingly soluble in cyclo-
Thiometon [640-15-3], O,O-dimethyl hexane, petroleum ether [20, p. 1263].
S-(2-ethylthio)ethyl phosphorodithioate,
C6 H15 O2 PS2 , M r 246.3, bp 110 ◦ C (13 Pa),
is a colorless liquid which is sparingly soluble
in water but readily soluble in common organic
solvents [20, p. 1199].
Vamidothion is produced by reaction
of O,O-dimethylphosphoric acid chloride
with the sodium salt of N-methylcarb-
amylethylmercaptoethanethiol [53].
Thiometon is produced by reaction of the Vamidothion (announced in 1962) is a sys-
sodium salt of O,O-dimethyldithiophosphoric temic insecticide and acaricide that provides per-
acid with ethylmercaptochloroethanol [51]. sistent control of Eriosoma lanigerum and other
Thiometon (announced in 1952) is used piercing and sucking Homoptera in cotton, hops,
for control of sucking insects, bryobia mites, pome and stone fruit, and rice.
tetranychid mites, and fruit-tree red spider mites Trade Name. Kilval (Rhône-Poulenc).
on a wide range of crops.
Trade Name. Mavrik (Novartis).
3.2. Pyrethroids
Triazophos [24017-47-8], O,O-diethyl O-1-
phenyl-1H-1,2,4-triazol-3-yl phosphorothioate, Some pyrethroids, with their toxicity to insects,
C12 H16 N3 O3 PS, M r 313.3, mp − 2 to − 5 ◦ C, show acaricidal activity initially, but later the
12 Acaricides

mite population often increases [54]. It is im-


probable that pyrethroids will be able to provide
long-term solutions to mite problems.

Acrinathrin [101007-06-1], (S)-α-cyano-


3-phenoxybenzyl-(Z)-(1R,3S)-2,2-dimethyl-
3-[2-(2,2,2-trifluoro-1-trifluoromethylethoxy-
carbonyl)vinyl]cyclopropanecarboxylate,
C26 H21 F6 NO5 , M r 541.4, mp 81.5 ◦ C, consists
of colorless crystals which are sparingly soluble
in water, and moderately to highly soluble in
most organic solvents [20, p. 16].

Trade Name. Talstar (FMC).

Fenpropathrin [64257-84-7], (R,S)-α-


cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcy-
clopropanecarboxylate, C22 H23 NO3 , M r 349.4,
mp 45 – 50 ◦ C, is a yellow-brown solid which is
Acrimathrin is produced by esterification sparingly soluble in water and soluble in xylene,
of 2,2-dimethyl-3-[3-oxo-3-{2,2,2-trifluoro-1- cyclohexanone, and methanol [20, p. 524].
(trifluoromethyl)ethoxy}-1-propenyl]cyclopro-
panecarboxylic acid with cyano(3-phen-
oxyphenyl)methanol [55].
Acrimathrin (announced in 1983) acts on the
central nervous system and is a contact and stom-
ach acaricide/insecticide. It is effective against
a wide range of phytophagous mites on vegeta- Fenpropathrin is produced by reaction of α-
bles, fruits, hops, ornamentals, vines, tobacco, cyano-3-phenoxybenzyl alcohol with 2,2,3,3-
and other crops. tertamethylcyclopropanecarboxylic acid chlo-
Trade Name. Rufast (AgrEvo). ride [57].
Fenpropathrin (announced in 1981) is used
Bifenthrin [82657-04-3], 2-methylbiphe- to control many species of mites and insects on
nyl-3-methyl-(Z)-(1RS,3RS)-3-(2-chloro-3,3,3- fruits, vegetables, field crops, ornamentals, and
trifluoroprop-1-enyl)-2,2-dimethylcyclopro- cotton.
panecarboxylate, C23 H22 ClF3 O2 , M r 422.9, Trade Names. Danitol (Valent/Sumitomo);
mp 51 – 56 ◦ C, is a viscous liquid, crystalline Rody (Sumitomo/Cyanamid).
or waxy product which is sparingly soluble in
water, slightly soluble in heptane, methanol, sol- Fenvalerate [51630-58-1], (R,S)-α-cyano-
uble in acetone, chloroform, diethyl ether, and 3-phenoxybenzyl-(R,S)-2-(4-chlorophenyl)-3-
toluene [20, p. 118]. methylbutyrate, C25 H22 ClNO3 , M r 419.9, mp
Bifenthrin is produced by reaction of 3- 39.5 – 53.7 ◦ C, is a viscous yellow or brown
(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-di- liquid product, sometimes partly crystalline at
methylcyclopropanecarboxylic acid with 3- room temperature, which is practically insolu-
(bromomethylene-2-methyl)biphenyl in the ble in water, moderately soluble in hexane and
presence of potassium hydroxide [56]. methanol, and soluble in xylene [20, p. 539].
Bifenthrin (announced in 1984) is effective
against a broad range of foliar pests. It also con-
trols some species of Acarina on cereals, citrus,
cotton, fruits, grapes, and ornamentals.
Acaricides 13

formamidine, C19 H23 N3 , M r 293.4, mp


86 – 87 ◦ C, colorless needles, has low solubility
in water (ca. 1 mg/L at 20 ◦ C) but is soluble in
acetone and toluene [16, p. 15].

Fenvalerate is produced by reaction of α-


cyano-3-phenoxybenzyl alcohol with 2-(4-chlo-
rophenyl)-3-methylbutyric acid chloride [58].
Fenvalerate (announced in 1974) is used
to control a wide range of pests, including Amitraz is produced by the reaction of 2,4-
those resistant to organochlorine, organophos- xylidine, ethylorthoformate, and methylamine
phorous, and carbamate insecticides, in fruits, [60].
vines, olives, hops, nuts, vegetables, cotton, and Amitraz is active against a wide range of
oilseed rape. mites and against all stages of phytophagous
Trade Names. Sumicidin (Sumitomo); Sanvaler- mites [61].
ate (Sanachem); Shasicidin (Sanonda). Trade Names. Taktic, Mitac (AgrEvo, NOR-
AM); ByeBye (Agriphar); Edrizer (Siapa);
Halfenprox [111872-58-3], 2-(4-bromodi-
Sender (Sanonda).
fluoromethoxyphenyl)-2-methylpropyl-3-phen-
oxybenzyl ether, C24 H23 BrF2 O3 , M r 477.3,
bp 291 ◦ C, is a colorless clear liquid which is Formetanate [22259-30-9], 3-(di-
sparingly soluble in water [20, p. 654]. methylaminomethyleneamino)phenyl N-
methylcarbamate, C11 H15 N3 O2 , M r 221.3, mp
102 ◦ C, yellow crystals, negligible vapor pres-
sure, has a solubility in water of < 1 g/L at
20 ◦ C and is soluble in acetone, chloroform, and
methanol [17, p. 5], [16, p. 284].
Formetanate is produced by the reac-
Halfenprox is produced by reaction of 3- tion of 3-dimethylaminomethyleneaminophenol
phenoxybenzyl-2-(4-hydroxyphenyl)-2-methyl with methyl isocyanate [62].
propyl ether and the potassium salt of tert-bu-
tanol with difluorodibromomethane in 1,3-di-
methyl-2-imidazolidinone [59].
Halfenprox (announced in 1987) is a broad-
spectrum acaricide with contact activity, it con-
trols all stages of red spider mites, fruit tree red Formetanate is active against the mobile
mites, two-spotted spider mites, and rust mites stages of fruit tree spider mites and is recom-
on citrus fruit, vines, tea, ornamentals, and other mended also for use in greenhouses.
crops. Trade Names. Dicarzol (AgrEvo); Carzol
Trade Names. Anniverse, Sirbon (Mitsui (NOR-AM).
Toatsu).

3.4. Nitrophenyl Esters


3.3. Formamidines
These compounds are effective as fungicides
Products derived from the formamidines are against powdery mildews and as acaricides. The
used both as acaricides and as effective and se- compounds are nonsystemic and are less phyto-
lective insecticides. This class of compounds toxic than the corresponding phenols.
acts mainly as an ovicide on mites.

Amitraz [33089-61-1], N 1 -methyl-N 2 -


1
(2,4-xylyl)-N -[N-(2,4-xylyl)-formimidoyl]
14 Acaricides

Dinobuton [973-21-7], 2-sec-butyl- slightly soluble in water, has low solubility in


4,6-dinitrophenyl isopropyl carbonate, acetone and alcohols, but is more soluble in aro-
C14 H18 N2 O7 , M r 326.3, mp 60 – 62 ◦ C, yel- matic hydrocarbons, chloroform, and dioxane
low crystals, negligible vapor pressure at room [16, p. 505], [17, p. 4], [18, p. 543].
temperature, is insoluble in water but soluble
in most organic solvents [16, p. 207], [17, p. 3],
[18, p. 540].

Tetradifon is produced by the Friedel – Crafts


reaction of 2,4,5-trichlorobenzenesulfonyl chlo-
ride and chlorobenzene [67].
Dinobuton is produced by esterification Tetradifon is recommended for use on tree
of 2-sec-butyl-4,6-dinitrophenol with isopropyl fruit, citrus, grapes, vegetables, ornamental
chloroformate [63]. plants, and nursery stock.
Dinobuton is used against red spider mites in Trade Names. Tedion V-18 (Uniroyal); Du-
greenhouses and in the field. racide (Endura); Tedone (Siapa).
Trade Names. Acrex (Keno Gard AB, Murphy,
Wacker); Dessin (Union Carbide).
3.6. Halogenated Benzhydrol
Dinocap [39300-45-3], 2-(1-methylheptyl)- Derivatives
4,6-dinitrophenyl crotonate, C18 H24 N2 O6 , M r These selective contact acaricides show activity
364.4, bp 138 – 140 ◦ C at 6.7 × 10−5 kPa, dark toward a large variety of phytophagous mites.
brown liquid, very low vapor pressure at 20 ◦ C, They are active against all postembryonal stages
is insoluble in water but soluble in most organic and eggs and are further characterized by their
solvents [19, p. 305]. nonsystemic and good residual activity. Despite
their resemblance to DDT they show no insecti-
cidal activity.

Bromopropylate [18181-80-1], isopro-


pyl-4,4 -dibromobenzilate C17 H16 Br2 O3 , M r
428.1, mp 76 – 78 ◦ C, colorless crystals, va-
Dinocap is produced by nitration of o-(1- por pressure 6.8 × 10−9 kPa at 20 ◦ C, is almost
methylheptyl)phenol followed by esterification insoluble in water (< 10 mg/L at 20 ◦ C) but sol-
with crotonic acid [64]. The industrial product uble in most organic solvents [16, p. 54], [17,
is a mixture of isomers [65] and is analyzed by p. 5].
the Kjeldahl method [66].
Trade Name. Acrex (Efthymiadis).

3.5. Sulfonic Acid Esters

Compounds in this class show mainly contact


activity and have long residual effects without Bromopropylate is produced by esterification
any adverse phytotoxic effects. of 4,4 -dibromobenzilic acid with 2-propanol
[68].
Tetradifon [116-29-0], 4-chlorophenyl- Bromopropylate is used against mites on cit-
2,4,5-trichlorophenyl sulfone C12 H6 Cl4 O2 S, rus, grapes, cotton, vegetables, soybeans, apple
M r 356.0, mp 146.5 – 147.5 ◦ C, colorless crys- and stone fruit, and ornamentals.
tals, vapor pressure 3.2 × 10−11 kPa at 20 ◦ C, is Trade Name. Neoron (Novartis).
Acaricides 15

Dicofol [115-32-2], 2,2,2-trichloro-1,1- 1,2,4-triazole or by the reaction of 1,2,4-triazole


bis(4-chlorophenyl)ethanol C14 H9 Cl5 O, M r with bis-tricyclohexyltin oxide [71].
370.5, mp 78.5 – 79.5 ◦ C, colorless crystals, very Azocyclotin shows activity against a broad
low vapor pressure at 20 ◦ C, is practically in- spectrum of spider mites [71].
soluble in water but soluble in most organic Trade Name. Peropal (Bayer)
solvents [16, p. 183], [17, p. 4], [18, p. 534].
Cyhexatin [13121-70-5], tricyclohexyltin
hydroxide, (C6 H12 )3 SnOH, C18 H34 OSn, M r
385.2, mp 195 – 198 ◦ C, colorless crystals, va-
por pressure negligible at 25 ◦ C, is practically
insoluble in water (< 1 mg/L at 25 ◦ C), soluble
in acetone, chloroform, and methanol, but other-
Dicofol is produced by chlorination of chlor- wise has low solubility in most organic solvents
fenethol [69] or by partial hydrolysis of 1,1,1,2- [17, p. 6], [18, p. 142].
tetrachloro-2,2-bis(4-chlorophenyl)ethane with Cyhexatin is produced by the Grignard reac-
80 – 90 % formic acid in the presence of a sul- tion of cyclohexylmagnesium chloride with tin
fonic acid at 120 – 125 ◦ C [70]. tetrachloride followed by hydrolysis with aque-
Dicofol has been used successfully against ous sodium hydroxide [72].
spider mites on citrus, cotton, deciduous fruit, Cyhexatin is an effective acaricide against a
and other crops. wide range of mites, mainly in deciduous fruit. It
Trade Names. Kelthane (Rohm & Haas); acts is by contact against the mobile stages [57].
Acarin, Mitigan (Makhteshim-Agan); Cecudi- Trade Names. Acarotine (Siapra); Pennstyl (Elf
fol (Ceguisa). Atochem); Aramol (Diachem).

Fenbutatin oxide [13356-08-6], bis[tris(2-


3.7. Organometallic Compounds methyl-2-phenylpropyl)tin] oxide, C60 H78 OSn2 ,
M r 1053, mp 138 – 139 ◦ C, colorless crystalline
Chemicals of this class, all tin compounds, have
powder, is insoluble in water, but soluble in
opened a new era in mite control and are among
acetone, dichloromethane, and benzene [16,
the most important acaricides in use. They are
p. 259].
characterized by their nonsystemic and excellent
residual effectiveness. They control the mobile
stages of a large variety of mites and show little
phytotoxicity.

Azocyclotin [41083-11-8], 1-tricyclohexyl-


tin-1H-1,2,4-triazole, C20 H35 N3 Sn, M 436.2, Fenbutatin oxide is produced by the treat-
mp 218.8 ◦ C, colorless crystals, vapor pressure ment of tris(2-methyl-2-phenylpropyl)tin chlo-
< 5×10−6 kPa at 25 ◦ C, is practically insoluble ride with sodium hydroxide [74].
in water, and slightly soluble in cyclohexane, Fenbutatin oxide gives effective control of
dichloromethane, toluene, and 2-propanol [19, mites on citrus, fruit, vines, and ornamental
p. 44]. plants.
Trade Names. Osaden, Torque (Cyanamid);
Vendex (Cyanamid, DuPont).

3.8. Other Compounds


Abamectin [7151-41-2], a mixture contain-
ing at least 80 % avermectin B1a (C48 H72 O14 ,
Azocyclotin is produced by the reaction of M r 873.1) and not more than 20 % avermectin
tricyclohexyltin chloride with the sodium salt of B1b (C47 H70 O14 , M r 860.1), mp 150 – 155 ◦ C,
16 Acaricides

consists of colorless to pale yellow crystals Buprofezin is prepared by cyclocondensation


which are sparingly soluble in water, fairly solu- of N-phenyl-N  -tert-butylthiourea with N-
ble in chloroform, ethanol, methanol, n-butanol, methylenechloride N-carbonylchloride-2-pro-
and cyclohexane, and soluble in toluene, ace- pylamine [77].
tone, and isopropanol [20, p. 3]. Buprofezin (announced in 1981) is probably
Abamectin is obtained from fermentation of a chitin synthesis and prostaglandin inhibitor. It
Streptomyces overmitilis [75]. inhibits moulting of nymphs and larvae and also
Abamectin (announced in 1981) acts by stim- suppresses oviposition by adults. It is effective
ulating the release of γ-aminobutyric acid, an in- against Cicadellidae and Homoptera in rice, Ci-
hibitory neurotransmitter. It is an insecticide and cadellidae in potatoes, and Aleyrodidae in citrus,
acaricide with contact and stomach action that cotton, and vegetables.
is used to control motile stages of mites, leaf Trade Name. Applaud (Nihon Nohyaku).
miners, suckers, and other pests, on vegetables,
fruits, and other crops. Chinomethionate [2439-01-2], quinome-
Trade Names. Dynamec (Merck); Abacide thionate, 6-methyl-[1,3]dithiolo[4,5-b]quin-
(Mauget). oxalin-2-one, C10 H6 N2 OS2 , M r 234.3, mp
171 – 172 ◦ C, yellow crystals, vapor pressure
Benzoximate [29104-30-1], 3-chloro-α- 2.7 × 10−8 kPa at 20 ◦ C, is practically insolu-
ethoxyimino-2,6-dimethoxybenzyl benzoate, ble in water but soluble in dimethylformamide,
C18 H18 ClNO5 , M r 363.8, mp 73 ◦ C, colorless cyclohexanone, and petroleum oils [16, p. 463],
crystalline solid, is practically insoluble in wa- [17, p. 6], [18, p. 561].
ter but soluble in benzene, hexane, xylene, and
dimethylformamide [16, p. 35].

Chinomethionate is produced by the reaction


of carbonyl chloride with 6-methyl-2,3-quin-
oxalinedithiol in aqueous alkaline solution [79].
Chinomethionate is a nonsystemic acaricide
useful against mites on fruits, vegetables, and
Benzoximate is produced by reaction of ornamental plants [80].
ethyl-3-chloro-2,6-dimethoxyhydroximate with Trade Name. Morestan (Bayer)
benzoyl chloride in the presence of a base [76].
Benzoximate is a nonsystemic acaricide for Clofentezine [74115-24-5], 3,6-bis-(2-chlo-
use against mites on apples and citrus fruits. rophenyl)-1,2,4,5-tetrazine, C14 H8 Cl2 N4 , M r
Trade Names. Acarmate (Sipcam); Artaban 303.1, mp 182.3 ◦ C, forms magenta crystals
(Procida); Citrazon (Nippon Soda). which are sparingly soluble in water, moderately
soluble in hexane, ethanol, and fairly soluble in
Buprofezin [69327-76-0], 2-tert-butyl- dichloromethane, and acetone [20, p. 254].
imino-3-isopropyl-5-phenyl-1,3,5-thiazinan-
4-one, C16 H23 N3 OS, M r 305.4, mp
104.5 – 105.5 ◦ C, consists of colorless crystals
which are sparingly soluble in water but soluble
in most organic solvents [20, p. 157].

Clofentezine is obtained by treatment of 2-


chlorobenzoylchloride with hydrazine [81].
Clofentezine (announced in 1981) is a spe-
cific acaricide with contact action and prolonged
residual activity. It inhibits embryo develop-
ment. It is used to control eggs and young motile
Acaricides 17

stages of Panonychus ulmi and Tetranychus spp. Dienochlor is produced by the catalytic
on pome fruit, stone fruit, nuts, vines, and hops. reduction of hexachlorocyclopentadiene [82],
Trade Name. Apollo (AgrEvo). [83].
Dienochlor is used mainly for control of mites
Cymizaol [61676-87-7], N-2,3-dihydro- on ornamentals and may act as an inhibitor of
3-methyl-1,3-thiazol-2-ylidene-2,4-xylidine, oviposition.
C12 H14 N2 S, M r 218.3, mp 44 ◦ C, forms col- Trade Name. Pentac (Novartis).
orless crystals which are sparingly soluble
in water but soluble in benzene, methanol, Endosulfan [115-29-7], 6,7,8,9,10,10-
dichloromethane, and hexane [20, p. 197]. hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-
methano-2,4,3-benzodioxathiepine 3-oxide,
C9 H6 Cl6 O3 S, M r 406.9, mp > 80 ◦ C, consists
of colorless crystals which are sparingly solu-
ble in water but readily soluble in ethyl acetate,
dichloromethane, toluene, ethanol, and hexane
[20, p. 459].
Cymizaol is produced by cyclocondensation
of N-2,4-dimethylphenyl-N  -methylthiourea
with chloroacetaldehyde [78].
Cymizaol (announced in 1977) is used in dips
or as a spray to control all Acarina species,
including strains resistant to organochlorines,
organophosphates, and carbamates. Endosulfan is produced by reaction of
Trade Name. Tifatol (Novartis). 1,2,3,4,7,7-hexachloro-5,6-dihydroxymethyl-
bicylo[2,2,1]-hept-5-ene, obtained by con-
Dienochlor [2227-17-0], perchlorobi(2,4-
densation of cis-1,4-dihydroxybut-2-ene with
cyclopentadienyl), C10 Cl10 , M r 474.6, mp
hexachlorocyclopentadiene, with thionyl chlo-
122 – 123 ◦ C, tan crystalline solid, vapor pres-
ride [84].
sure 10−6 kPa at 25 ◦ C, is insoluble in water,
Endosulfan (announced in 1956) acts as an
slightly soluble in ethanol, acetone, and aliphatic
antagonist of the GABA receptor chloride chan-
hydrocarbons, and moderately soluble in aro-
nel complex, and is used to control sucking,
matic hydrocarbons [16, p. 186], [18, p. 529].
chewing, and boring insects and mites on a broad
range of crops.
Trade Names. Fan (FMC); Thiodan (AgrEvo);
Thionex (Makhteshim-Agan).
18 Acaricides

Fenazaquin [120928-09-8], 4-tert- Fenpyroximate (announced in 1990) inhibits


butylphenylmethyl quinazolin-4-yl ether, mitochondrial electron transport at complex I;
C20 H22 N2 O, M r 306.4, mp 77.5 – 80 ◦ C, con- it possesses quick knockdown activity against
sists of colorless crystals which are practically larvae, nymphs and adults. It is used to control
insoluble in water but soluble in many organic important phytophagous mites such as Tetrany-
solvents [20, p. 506]. chidae, Tarsonemidae, and other pests on citrus,
apples, pears, grapes, tea, cherries, and melons.
Trade Names. Danitorante, Danitron (Nihon
Noyaku).

Flucycloxuron [94050-52-9], 1-[α-(4-


chloro-α-cyclopropylbenzylideneamino-
Fenazaquin is produced by reaction of 4- oxo)-p-tolyl]-3-(2,6-difluorobenzoyl)urea,
hydroxyquinazoline with phosphite and chlo- C25 H20 ClF2 N3 O3 , M r 483.9, mp 143.6 ◦ C, con-
rine, and treating the resulting haloquinazoline sists of off-white to yellow crystals which are
with 4-tert-butylphenylethanol [85]. insoluble in water, sparingly soluble in cy-
Fenazaquin (announced in 1992) affects the clohexane, xylene, ethanol, and soluble in N-
metabolism by inhibiting the mitochondrial methylpyrrolidone [20, p. 562].
electron transport chain by binding with com-
plex I at coenzyme Q. It is a contact acari-
cide with good knockdown activity on motile
forms, as well as true ovicidal activity, prevent-
ing eclosion of mite eggs. It is used against Eu-
tetranychus, Panonychus and Tetranychus spp.,
and Brevipalpus phoenics in almonds, apples,
citrus, cotton, grapes, and ornamentals.
Trade Name. Magister (DowElanco).
Flucycloxuron is produced by reaction of 4-
chlorocyclopropylphenone with hydroxylamine
Fenpyroximate [111812-58-9], tert-butyl to yield the corresponding oxime, which is
(E)-α-(1,3-dimethyl-5-phenoxypyrazol-4-yl- treated with 4-nitrobenzylbromide, followed by
methyleneaminooxy)-p-toluate, C24 H27 N3 O4 , reduction to give the corresponding amine,
M r 421.5, mp 101.1 – 102.4 ◦ C, is a colorless which is further treated with 2,6-difluorobenzoyl
crystalline powder which is practically insolu- isocyanate [87].
ble in water, moderately soluble in methanol, Flucycloxuron (announced in 1988) is a
and highly soluble in acetone, dichloromethane, chitin synthesis inhibitor that is only active
chloroform, and THF [20, p. 530]. against egg and larval stages (does not affect
adult mites and insects). It is used on a variety
of crops.
Trade Name. Andalin (Uniroyal).

Flufenoxuron [101463-69-8], 1-[-4-


(2-chloro-α,α,α-trifluoro-p-tolyloxy)-2-
fluorophenyl]-3-(2,6-difluorobenzoyl)urea,
C21 H11 ClF6 N2 O3 , M r 488.8, mp 169 – 172 ◦ C,
is a colorless crystalline solid which is prac-
Fenpyroximate is produced by reaction of tically insoluble in water and moderately sol-
tert-butyl 4-(bromomethyl)benzoate with 1,3- uble in acetone, xylene, dichloromethane [20,
dimethyl-5-phenoxypyrazole-4-carboxalde- p. 568].
hyde oxime in the presence of potassium hy-
droxide in dimethylsulfoxide [86].
Acaricides 19

3-(2,6-difluorobenzoyl)urea, C17 H8 Cl2 F8 N2 O3 ,


M r 511.2, mp 164.7 – 167.7 ◦ C, forms color-
less crystals which are practically insoluble in
water, moderately soluble in ethanol, toluene,
n-octanol, and n-hexane, and readily soluble in
acetone [20, p. 753].
Flufenoxuron is produced by reaction
of 2-fluoro-4-hydroxyaniline in potassium
hydroxide-containing dimethyl sulfoxide with
3,4-dichlorotrifluoromethyltoluene to give the
corresponding phenoxyaniline, which is treated
with 2,6-difluorophenyl isocyanate [88].
Flufenoxuron is a chitin synthesis inhibitor
and insect and acarid growth regulator with con-
tact and stomach action. It is used for control of
immature stages of many phytophagous mites Lufenuron is produced by condensation
and insect pests on pome fruits, vines, citrus of 2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropro-
fruits, tea, cotton, maize, vegetables, ornamen- pyloxy)aniline with 2,4-difluorobenzyl iso-
tals, etc. cyanate in anhydrous toluene [90].
Trade Name. Cascade (Cyanamid). Lufenuron inhibits chitin synthesis and acts
mostly by ingestion; larvae are unable to molt
Hexythiazox [78587-05-0], (4RS,5RS)- and also cease feeding. It is used for control
5-(4-chlorophenyl)-N-cyclohexyl-4-methyl- of Lepidoptera and Coleoptera larvae on cotton,
2-oxo-1,3-thiazolidine-3-carboxamide, maize, and vegetables and citrus whiteflies and
C17 H21 ClN2 O2 S, M r 352.9, mp 108.0 – 108.5 ◦ C, rust on citrus fruit.
consists of colorless crystals which are sparingly Trade Name. Match (Novartis).
soluble in water, fairly soluble in hexane, ace-
tonitrile, and soluble in chloroform, methanol, Propargite [2312-35-8], 2-(4-tert-
and acetone [20, p. 679]. butylphenoxy)cyclohexyl 12-propynyl sulfite,
C29 H26 O4 S, M r 350.5; the technical product is
a dark, viscous oil, d 25
4 1.085 – 1.115, practically
insoluble in water but soluble in most organic
solvents [16, p. 447], [17, p. 4], [18, p. 560].

Hexythiazox is produced by treat-


ment of trans-4-methyl-5-(4-chlorophenyl)-2-
thiazolidinone with phenylisocyanate [89]. Proargite is produced by the reaction of
Hexythiazox (announced in 1982) possesses 4-tert-butylphenol with 1,2-epoxycyclohexane,
ovicidal, larvicidal, and nymiphicidal activity. It followed by treatment with thionyl chloride to
is used against eggs and larvae of many phy- give the chlorosulfinate, then with 2-propynol
tophagous mites on fruit, vines, vegetables, and (propargyl alcohol) in the presence of a base
cotton. [91].
Trade Names. Cesar (AgrEvo); Zeldox Propargite is used mainly for the control of
(Zeneca); Ordoval (BASF); Matacar (Sipcam); mites on fruit and other crops.
Hexygon (Gowen). Trade Names. Omite (Uniroyal); Redador (Pro-
Lufenuron [103055-07-8], (RS)-1-[2,5-di- ductos OSA).
chloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]
20 Acaricides

Pyridaben [96489-71-3], 2-tert-butyl-5- Tebufenpyrad (announced in 1988) is a mi-


(4-tert-butylbenzylthio)-4-chloropyridazin-3- tochondrial respiration inhibitor that acts in the
(2H)-one, C19 H25 ClN2 OS, M r 364.9, mp electron transport chain at site I. It is a nonsys-
111 – 112 ◦ C, consists of colorless crystals temic acaricide that acts by contact and inges-
which are practically insoluble in water, moder- tion. It is used for control of all stages of Tetrany-
ately soluble in ethanol, hexane, and n-octanol, chus, Panonychus, Origonychus, and Eotetrany-
and readily soluble in acetone, benzene, xylene, chus spp. on top fruit, vines, citrus, vegetables,
and cyclohexane [20, p. 1061]. hops, ornamentals, melons, and cotton.
Trade Names. Comanché, Masai, Oscar
(Cyanamid); Pyranica (Mitsubishi).

4. Toxicology
Pyridaben is produced by reaction of The following summary gives an overview of the
mucochloric acid with 4-tert-butylmercapto- toxicological profile of various acaricides. The
toluene, followed by cyclocondensation of the data were assembled by searching the literature
resulting malealdehydic acid derivative with N- and databanks available to the public. Because
tert-butylhydrazine [92]. most of these compounds are proprietary prod-
Pyridaben (announced in 1988) is active ucts, many of the toxicological data are not pub-
against all developing stages, especially against lished. Information in well-documented mono-
the larval and nymph stages, and is used for con- graphs, (e.g., WHO/FAO), in which the original
trol of Acari, Aleyrodidae, Aphididae, Cicadel- data from the companies are available, were pre-
lidae and Thysanoptera on field crops. ferred to other published data, (e.g., handbooks),
Trade Name. Sanmite (Nissan). because the studies submitted to WHO/FAO
were performed according to internationally ac-
Tebufenpyrad [119168-77-3], cepted test protocols and good laboratory prac-
N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1- tices. The values presented should be viewed as
methylpyrazole-5-carboxamide, C18 H24 ClN3 O, a broad estimate of human toxicity as limited by
M r 333.8, mp 61 – 61 ◦ C, consists of colorless strain, number of animal tested, study design,
crystals which are sparingly soluble in water and applicability of the biological model.
but soluble in acetone, methanol, chloroform,
acetonitrile, hexane, and benzene [20, p. 1148].
4.1. Organophosphates and
(Oxime)Carbamates

Toxic Action. Cumulative inhibition of


cholinesterase causes toxic effects at doses not
effective acutely. Delayed neurotoxicity leading
to demyelination is observed with compounds
that inhibit neurotoxic esterase. Carbamates act
similarly, but reactivation of esterase occurs
Tebufenpyrad is produced by treatment of 4-
more rapidly [94, p. 531, p. 539].
chloro-1-methyl-3-ethyl-pyrazole-5-carboxylic
acid with thionyl chloride under reflux, followed
by reaction of the resulting acid chloride with
4-tert-butylbenzylamine [93].
Acaricides 21

Aldicarb [116-06-3] NOEL/NOAEL:


Reproduction.
LD50 (rat, oral) 0.62 – 1.23 mg/kg [95]
Rat (two-generation feed): 0.05 mg kg−1 d−1 [97,
LD50 (mouse, oral) 0.58 – 1.5 mg/kg [95]
(parental and p. 15]
LD50 (guinea pig, 1.0 mg/kg [95]
developmental)
oral)
Teratogenicity.
LD50 (rabbit, oral) 1.3 mg/kg [95]
LD50 (chicken) 9.0 mg/kg [95] Rat (gavage): 1.0 mg kg−1 d−1 [97,
LD50 (rat, dermal) 3.2 to > 10 mg/kg [95] (maternal) p. 15]
LD50 (rabbit, dermal) 5.0 to > 10 mg/kg [95] 7.0 mg kg−1 d−1 [97,
Rabbit: nonirritating to eyes and skin [95] (developmental) p. 15]
Guinea pig: not a skin sensitizer [95] Rabbit (gavage): < 25 mg kg−1 d−1 [97,
Nonmutagenic [95] (maternal) p. 15]
NOEL/NOAEL: 100 mg kg−1 d−1 [97,
Reproduction. (developmental) p. 15]
Rat (feed): 0.3 mg kg−1 d−1 [96, Chronic.
p. 33] Rat (2-year feed): 0.15 mg kg−1 d−1 [97,
Teratogenicity. p. 15]
−1 −1 −1 −1
Rat (gavage): 0.125 mg kg d [96, Mouse (2-year feed): 3.7 mg kg d [97,
(maternal) p. 33] p. 15]
−1
0.25 mg kg−1 d−1 [96, Dog (one-year feed): 2.8 mg kg d−1 [97,
(developmental) p. 33] p. 15]
Chronic. ADI: 0.0005 mg kg−1 d−1 [97, p. 15]
Rat (93-day feed): 0.1 mg kg−1 d−1 [96,
p. 33]
Mouse (103-week 0.9 mg kg−1 d−1 [96,
feed): p. 33] Chlorpyrifos-methyl [5598-13-0]
Dog (one-year feed): 0.05 mg kg−1 d−1 [96,
p. 33] LD50 (rat, oral) 2680 – 3069 mg/kg [98,
Human. p. 115]
(single oral dose): 0.025 mg kg−1 d−1 [96, LD50 (mouse, oral) 1122 – 2440 mg/kg [98,
(cholinesterase) p. 33] p. 115]
ADI: 0.003 mg kg−1 d−1 [96, p. 33] LD50 (rabbit, oral) ca. 2000 mg/kg [98,
p. 115]
LD50 (chick, oral) > 7950 mg/kg [98,
p. 115]
Chlorfenvinphos [470-90-6] LD50 (rat, dermal) > 2000 mg/kg [97,
p. 15]
LD50 (mouse, dermal) > 2856 mg/kg [98,
LD50 (rat, oral) 9.6 – 39 mg/kg [97,
p. 115]
p. 15]
LC50 (rat, 4-h inhalation) 0.76 mg/L air [98,
LD50 (mouse, oral) 117 – 200 mg/kg [97,
p. 115]
p. 15]
Rabbit: nonirritating to skin and eyes [98,
LD50 (rabbit, oral) 300 – 1000 mg/kg [97,
p. 115]
p. 15]
Guinea pig: not a skin sensitizer [98,
LD50 (dog, oral) > 12000 mg/kg [97,
p. 115]
p. 15]
Nonmutagenic [98,
LD50 (guinea pig, oral) 125 – 250 mg/kg [97,
p. 115]
p. 15]
NOEL/NOAEL:
LD50 (rat, dermal) 30 – 108 mg/kg [97,
Reproduction.
p. 15]
LD50 (rabbit, dermal) 412 – 4700 mg/kg [97, Rat (3-generation feed): 3 mg kg−1 d−1 [98,
p. 15] p. 115]
Rabbit: slightly irritating to skin [97, Teratogenicity.
p. 15] Rat (gavage): 250 mg kg−1 d−1 [98,
Rabbit: nonirritating to eyes [97, p. 115]
−1 −1
p. 15] Rabbit (gavage): 1.0 mg kg d [96,
Nonmutagenic [97, p. 111]
p. 15] Chronic.
Rat (2-year feed): 1.0 mg kg−1 d−1 [96,
p. 111]
Mouse (78-week feed): 3.9 mg kg−1 d−1 [98,
p. 115]
Dog (2-year feed): 1.0 mg kg−1 d−1 [98,
p. 115]
Human.
(4-week capsule): 0.1 mg kg−1 d−1 [98,
p. 115]
−1 −1
ADI: 0.01 mg kg d [96, p. 111]
22 Acaricides

Diazinon [333-41-51] Dimethoate [60-51-5]


LD50 (rat, oral) 300 – 1012 mg/kg [99, LD50 (rat, oral) 600 – 700 mg/kg [100,
p. 57] p. 1015]
LD50 (mouse, oral) 187 mg/kg [99, LD50 (mouse, oral) 60 mg/kg [100,
p. 57] p. 1015]
LD50 (rat, dermal) > 2150 mg/kg [99, LD50 (rabbit, oral) 500 mg/kg [100,
p. 57] p. 1015]
LD50 (rabbit, dermal) > 20 mg/kg [99, LD50 (cat, oral) 100 mg/kg [100,
p. 57] p. 1015]
LC50 (rat, 4-h inhalation) 2.3 mg/L air [99, LD50 (guinea pig, oral) 550 mg/kg [100,
p. 57] p. 1015]
Rabbit: nonirritating to eyes and skin [99, LD50 (horse, oral) > 50 mg/kg [101]
p. 57] LD50 (sheep, oral) 80 mg/kg [101]
Guinea pig: not a skin sensitizer [99, LD50 (cattle, oral) 70 mg/kg [101]
p. 57] LD50 (hen, oral) 50 mg/kg [101]
Nonmutagenic [99, LD50 (pheasant) 15 – 20 mg/kg [101]
p. 57] LD50 (rat, dermal) 100 – 443 mg/kg [100,
NOEL/NOAEL: p. 1015]
Reproduction. LD50 (rabbit, dermal) 1500 mg/kg [100,
Rat (2-generation feed): 0.5 mg kg−1 d−1 [99, p. 1015]
(parental and p. 57] LC50 (rat, 4-h inhalation) > 0.2 mg/L air [100,
developmental) p. 1015]
Teratogenicity. Rabbit: nonirritating to skin and eyes [100,
Rat (gavage): 20 mg kg−1 d−1 [99, p. 1015]
(maternal and p. 57] Guinea pig: not a skin sensitizer [102,
developmental) p. 79]
Nonmutagenic [102,
Rabbit (gavage): 25 mg kg−1 d−1 [99,
p. 79]
(maternal) p. 57]
NOEL/NOAEL:
100 mg kg−1 d−1 [99, Teratogenicity.
(developmental) p. 57]
Rabbit (gavage): 10 mg kg−1 d−1 [102,
Chronic.
−1 −1 p. 79]
Rat (99-week feed): 0.07 mg kg d [99, Chronic.
p. 57]
Rat (2-year feed): 0.05 mg kg−1 d−1 [102,
Dog (one-year feed): 0.02 mg kg−1 d−1 [99, p. 79]
p. 57] −1 −1
ADI: 0.01 mg kg d [102, p. 79]
Human.
(34 – 36-day capsule): 0.025 mg kg−1 d−1 [99,
p. 57]
ADI: 0.002 mg kg−1 d−1 [99, p. 57]
Disulfoton [298-04-4]
LD50 (rat, oral) 1.9 – 9.6 mg/kg [103]
LD50 (mouse, oral) 7.0 – 28 mg/kg [103]
LD50 (dog, oral) ca. 5 mg/kg [103]
Dicrotophos [141-66-2] LD50 (rat, dermal) 15.9 – 22.6 mg/kg [103]
LD50 (mouse, dermal) 35 mg/kg [103]
LD50 (rat, oral) 17 – 22 mg/kg [20, LC50 (rat, 4-h inhalation) 0.015 mg/L air [103]
p. 382] Guinea pig: not a skin sensitizer [103]
LD50 (mouse, oral) 15 mg/kg [20, Nonmutagenic [103]
p. 382] NOEL/NOAEL:
LD50 (rat, dermal) 110 – 180 mg/kg [20, Reproduction.
p. 382] Rat (2-generation feed): 0.15 mg kg−1 d−1 [103]
LD50 (rabbit, dermal) 224 mg/kg [20, (parental)
p. 382] 0.05 mg kg−1 d−1 [103]
LC50 (rat, 4-h inhalation) 0.09 mg/L air [20, (developmental)
p. 382] Teratogenicity.
Rabbit: slightly irritating to skin and eyes [20, Rat (gavage): 0.3 mg kg−1 d−1 [103]
p. 382] (maternal)
NOEL/NOAEL: 0.1 mg kg−1 d−1 [103]
Reproduction. (developmental)
−1 −1
Rat (3-generation feed): 0.02 mg kg d [20, Rabbit (gavage): 0.3 mg kg−1 d−1 [103]
p. 382] (maternal)
Chronic. 1.5 mg kg−1 d−1 [103]
Rat (2-year feed): 0.05 mg kg−1 d−1 [20, (developmental)
p. 382] Chronic.
Dog (2-year feed): 0.04 mg kg−1 d−1 [20, Rat (2-year feed): 0.06 mg kg−1 d−1 [103]
p. 382] Mouse (99-week feed): 0.55 mg kg−1 d−1 [103]
Dog (2-year feed): 0.03 mg kg−1 d−1 [103]
Human.
0.01 mg kg−1 d−1 [103]
ADI: 0.0003 mg kg−1 d−1 [103]
Acaricides 23

EPN [2104-64-5] Formothion [2540-82-1]


LD50 (rat, oral) 24 – 36 mg/kg [20, LD50 (rat, oral) 365 – 500 mg/kg [20,
p. 464] p. 625]
LD50 (mouse, oral) 60 – 95 mg/kg [20, LD50 (mouse, oral) 190 – 195 mg/kg [20,
p. 464] p. 625]
LD50 (rat, dermal) 538 – 2850 mg/kg [20, LD50 (rabbit, oral) 570 mg/kg [20,
p. 464] p. 625]
NOEL/NOAEL: LD50 (cat, oral) 210 mg/kg [20,
Chronic. p. 625]
−1 −1 LD50 (rat, dermal) > 1000 mg/kg [20,
Rat (2-year feed): 0.15 mg kg d [20,
p. 464] p. 625]
−1 −1 LC50 (rat, 4-h inhalation) 3.2 mg/L air [20,
Mouse (78-week feed): 0.7 – 3.6 mg kg d [20,
p. 464] p. 625]
Rabbit: slightly irritating [20,
to skin p. 625]
NOEL/NOAEL:
Chronic.
Ethion [563-12-2] Rat (2-year feed): 4.0 mg kg−1 d−1 [20,
p. 625]
LD50 (rat, oral) 47 mg/kg [20, Dog (2-year feed): 2.0 mg kg −1
d −1
[20,
p. 480] p. 625]
LD50 (mouse, oral) 40 – 45 mg/kg [20,
ADI: 0.02 mg kg−1 d−1 [20, p. 625]
p. 480]
LD50 (guinea pig, oral) 40 – 48 mg/kg [20,
p. 480]
LD50 (rabbit, dermal) 1084 mg/kg [20,
p. 480] Mecarbam [2591-54-2]
LC50 (rat, 4-h inhalation) 0.45 mg/L air [20,
p. 480] LD50 (rat, oral) 36 – 53 mg/kg [20,
NOEL/NOAEL: p. 774]
Teratogenicity. LD50 (mouse, oral) 106 mg/kg [20,
Rat (gavage): 0.06 mg kg−1 d−1 [104, p. 774]
(maternal) p. 65] LD50 (rat, dermal) > 1220 mg/kg [20,
0.2 mg kg−1 d−1 [104, p. 774]
(developmental) p. 65] LC50 (rat, 6-h inhalation) 0.7 mg/L air [20,
Chronic. p. 774]
Rat (2-year feed): 0.3 mg kg−1 d−1 [20, NOEL/NOAEL:
p. 480] Chronic.
Dog (2-year feed): 0.05 mg kg−1 d−1 [20, Rat (2-year feed): 0.21 mg kg−1 d−1 [105,
p. 480] p. 89]
−1 −1
Human. Dog (one-year feed): 0.35 mg kg d [105,
0.15 mg kg−1 d−1 [104, p. 89]
−1 −1
p. 65] ADI: 0.002 mg kg d [105, p. 89]
ADI: 0.002 mg kg−1 d−1 [20, p. 480]

Methacrifos [62610-77-9]
Fenothiocarb [62850-32-2]
LD50 (rat, oral) 678 mg/kg [106,
LD50 (rat, oral) 1150 – 1200 mg/kg [20, p. 276]
p. 517] LD50 (mouse, oral) 58 – 66 mg/kg [106,
LD50 (mouse, oral) 4875 – 7000 mg/kg [20, p. 276]
p. 517] LD50 (dog, oral) 573 mg/kg [106,
LD50 (mouse, dermal) > 8000 mg/kg [20, p. 276]
p. 517] LD50 (chicken, oral) 101 mg/kg [106,
LD50 (rat, dermal) 2075 – 2425 mg/kg [20, p. 276]
p. 517] LD50 (rat, dermal) > 3100 mg/kg [106,
LC50 (rat, 4-h inhalation) > 0.79 mg/L air [20, p. 276]
p. 517] LD50 (rabbit, dermal) 2732 mg/kg [106,
NOEL/NOAEL: p. 276]
Chronic. LC50 (rat, 6-h inhalation) 2.5 mg/L air [106,
Rat (2-year feed): 1.86 – 1.94 mg kg−1 d−1 [20, p. 276]
p. 517] Rabbit: mildly irritating to skin [106,
Dog (one-year feed): 1.5 – 3.0 mg kg−1 d−1 [20, p. 276]
p. 517] Rabbit: nonirritating to eyes [106,
p. 276]
ADI: 0.0075 mg kg−1 d−1 [20, p. 517]
Guinea pig: not a skin sensitizer [106,
p. 276]
Nonmutagenic [106,
p. 276]
24 Acaricides

NOEL/NOAEL:
Methidathion [950-37-8]
Reproduction.
LD50 (rat, oral) 26 – 43.8 mg/kg [104,
Rat (2-generation feed): 0.5 mg kg−1 d−1 [104,
p. 233]
(parental and p. 101]
LD50 (rat, oral) 26 mg/kg [104,
developmental)
p. 233]
Chronic.
LD50 (mouse, oral) 17 mg/kg [104,
Rat (2-year feed): 0.5 mg kg−1 d−1 [104, p. 233]
p. 101] LD50 (hamster, oral) 30 mg/kg [104,
Mouse (21-22-month 15 mg kg−1 d−1 [104, p. 233]
feed): p. 101] LD50 (guinea pig, oral) 25 mg/kg [104,
Dog (26-week feed): 2.5 mg kg−1 d−1 [104, p. 233]
p. 101] LD50 (rabbit, oral) 80 mg/kg [104,
Human. p. 233]
−1 −1
0.06 mg kg d [104, LD50 (dog, oral) 200 mg/kg [104,
p. 101] p. 233]
−1 −1
ADI: 0.006 mg kg d [104, p. 101] LD50 (chicken, oral) 80 mg/kg [104,
p. 233]
LD50 (rat, dermal) 1546 – 1663 mg/kg [104,
p. 233]
Rabbit: irritating to eyes [104,
Methamidophos [10265-92-6] p. 233]
Rabbit: very slightly irritating to skin [104,
LD50 (rat, oral) ∼ 20 mg/kg [104, p. 233]
p. 105] Guinea pig: not a skin sensitizer [104,
LD50 (rabbit, oral) 10 – 30 mg/kg [20, p. 105]
p. 808] Nonmutagenic [104,
LD50 (dog, oral) 10 – 30 mg/kg [20, p. 233]
p. 808] NOEL/NOAEL:
LD50 (cat, oral) 10 – 30 mg/kg [20, Reproduction.
p. 808] Rat (2-generation feed): 0.43 mg kg−1 d−1 [104,
LD50 (guinea pig, oral) 30 – 50 mg/kg [20, (parental and p. 233]
p. 808] developmental)
LD50 (rat, dermal) 130 mg/kg [20, Teratogenicity.
p. 808]
Rat (gavage): 1.0 mg kg−1 d−1 [104,
LC50 (rat, 4-h inhalation) 0.2 mg/L air [20,
(maternal) p. 233]
p. 808]
Rabbit: nonirritating to skin [20, 2.5 mg kg−1 d−1 [104,
p. 808] (developmental) p. 233]
Rabbit: slightly irritating to eyes [20, Rabbit (gavage): 6 mg kg−1 d−1 [104,
p. 808] (maternal) p. 233]
Guinea pig: not a skin sensitizer [104, 12 mg kg−1 d−1 [104,
p. 105] (developmental) p. 233]
Nonmutagenic [104, Chronic.
p. 195] Rat (2-year feed): 0.16 mg kg−1 d−1 [104,
NOEL/NOAEL: p. 233]
−1 −1
Chronic. Mouse (23-month feed): 1.4 mg kg d [104,
Rat (2-year feed): 0.1 mg kg−1 d−1 [104, p. 233]
−1
p. 105] Dog (one-year feed): 0.1 mg kg d−1 [104,
Mouse (2-year feed): 0.7 mg kg−1 d−1 [20, p. 233]
p. 808] Human.
Dog (one-year feed): 2.5 mg kg−1 d−1 [104, 0.11 mg kg−1 d−1 [104,
p. 105] p. 233]
Neurotoxicity. ADI: 0.001 mg kg−1 d−1 [104, p. 233]
Hen: 0.3 mg kg−1 d−1 [104,
p. 105]
Human.
(21-day): 0.04 mg kg−1 d−1 [104,
p. 105]
−1 −1
ADI: 0.004 mg kg d [104, p. 105]
Acaricides 25

Methiocarb [2032-65-7] NOEL/NOAEL:


Reproduction.
LD50 (rat, oral) 13 – 135 mg/kg [100,
Rat (feed): 2.5 mg kg−1 d−1 [105,
p. 95]
(parental and p. 97]
LD50 (mouse, oral) 52 – 58 mg/kg [20,
developmental)
p. 813]
Teratogenicity.
LD50 (guinea pig, oral) 14 – 100 mg/kg [100,
p. 95] Rat (feed): 8.5 mg kg−1 d−1 [105,
LD50 (dog, oral) 10 – 25 mg/kg [100, (maternal) p. 97]
p. 95] 34 mg kg−1 d−1 [105,
LD50 (rat, dermal) > 300 – > 5000 mg/kg [100, (developmental) p. 97]
p. 95] Rabbit (gavage): 6 mg kg−1 d−1 [105,
LD50 (rabbit, dermal) > 2000 mg/kg [100, (maternal) p. 97]
p. 95] 16 mg kg−1 d−1 [105,
LC50 (rat, 4-h inhalation) 0.32 mg/L air [100, (developmental) p. 97]
p. 95] Chronic.
Rabbit: nonirritating to skin and eyes [20, Rat (2-year feed): 2.5 mg kg−1 d−1 [105,
p. 813] p. 97]
Nonmutagenic [100, −1 −1
Mouse (2-year feed): 8.7 mg kg d [105,
p. 1161] p. 97]
−1
NOEL/NOAEL: Dog (2-year feed): 3.1 mg kg d−1 [105,
Chronic. p. 97]
Rat (2-year feed): 1.3 mg kg−1 d−1 [107, Human.
p. 31] Cholinesterase (in vitro): I50 = 265 µmol/L [108,
−1 −1
Dog (2-year feed): 0.13 mg kg d [107, p. 157]
p. 31] ADI: 0.01 mg kg−1 d−1 [105, p. 97]
ADI: 0.001 mg kg−1 d−1 [107, p. 31]

Mevinphos [26718-65-03]
Methomyl [16752-77-5]
LD50 (rat, oral) 3.7 – 7 mg/kg [100,
LD50 (rat, oral) 17 – 45 mg/kg [105, p. 1006]
p. 97] LD50 (mouse, oral) 4.3 – 12.9 mg/kg [100,
LD50 (rabbit, oral) 30 mg/kg [105, p. 1006]
p. 97] LD50 (rat, dermal) 4.2 – 4.7 mg/kg [100,
LD50 (chicken, oral) 28 mg/kg [105, p. 1006]
p. 97] LD50 (mouse, dermal) 40 – 50.2 mg/kg [100,
LD50 (dog, oral) 20 mg/kg [105, p. 1006]
p. 97] LD50 (rabbit, dermal) 16 – 33 mg/kg [20,
LD50 (chicken, oral) 28 mg/kg [105, p. 844]
p. 97] LC50 (rat, one-h 0.125 mg/L air [20,
LD50 (rat, dermal) > 1000 mg/kg [105, inhalation) p. 844]
p. 97] Rabbit: mildly irritating to eyes and skin [20,
LC50 (rat, 4-h inhalation) 0.30 mg/L air [105, p. 844]
p. 97] NOEL/NOAEL:
Rabbit: irritating to eyes [20, Chronic.
p. 815] Rat (2-year feed): 0.02 mg kg−1 d−1 [108,
Guinea pig: not a skin sensitizer [20, p. 385]
p. 815] −1 −1
Dog (2-year capsule): 0.025 mg kg d [108,
Nonmutagenic [105, p. 385]
p. 97] Human.
0.014 mg kg−1 d−1 [108,
p. 385]
ADI: 0.01 mg kg−1 d−1 [108, p. 385]
26 Acaricides

Monocrotophos [6923-22-4] NOEL/NOAEL:


Chronic.
LD50 (rat, oral) 14 – 23 mg/kg [108,
Mouse (2-year feed): 2.1 – 3.1 mg kg−1 d−1 [110,
p. 423]
p. 117]
LD50 (mouse, oral) 15 mg/kg [108, −1 −1
Dog (one-year gavage): 0.025 mg kg d [110,
p. 423]
p. 117]
LD50 (rat, dermal) 112 – 126 mg/kg [20,
p. 849] Rat (3-month feed): 0.05 mg kg−1 d−1 [110,
LD50 (rabbit, dermal) 130 – 250 mg/kg [20, p. 117]
p. 849] ADI: 0.0003 mg kg−1 d−1 [110, p. 117]
LC50 (rat, 4-h inhalation) 0.08 mg/L air [20,
p. 849] Oxamyl [23135-22-0]
Rabbit: nonirritating to skin and eyes [20, LD50 (rat, oral) 2.5 – 16 mg/kg [111]
p. 849] LD50 (mouse, oral) 2.3 – 3.3 mg/kg [111]
Mutagenicity: ambiguous [99, LD50 (guinea pig, oral) 7.1 mg/kg [111]
p. 333] LD50 (rat, dermal) > 1200 mg/kg [111]
NOEL/NOAEL: LD50 (rabbit, dermal) 130 mg/g [106,
Reproduction. p. 310]
Rat (3-generation feed): 0.05 mg kg−1 d−1 [99, LC50 (rat, 1-h inhalation) 0.12 – 0.17 mg/L air [111]
(parental and p. 333] Rabbit: mildly irritating to skin and eyes [111]
developmental) Guinea pig: not a skin sensitizer [111]
Teratogenicity. Nonmutagenic [106,
Rat (gavage): 0.3 mg kg−1 d−1 [99, p. 310]
(maternal) p. 333] NOEL/NOAEL:
2.0 mg kg−1 d−1 [99, Teratogenicity.
(developmental) p. 333] Rabbit (gavage): 1 mg kg−1 d−1 [112,
Rabbit (gavage): 1.0 mg kg−1 d−1 [99, (maternal) p. 59]
(maternal) p. 333] 2 mg kg−1 d−1 [112,
3.0 mg kg−1 d−1 [99, (developmental) p. 59]
(developmental) p. 333] Rat (feed): ca. 4 mg kg−1 d−1 [106,
Chronic. (maternal) p. 310]
−1 −1
Rat (2-year feed): 0.005 mg kg d [109, 20 mg kg−1 d−1 [106,
p. 78] (developmental) p. 310]
−1 −1
Mouse (2-year feed): < 0.15 mg kg d [109, Reproduction.
p. 78] Rat (3-generation feed): 2.5 mg kg−1 d−1 [106,
Dog (2-year feed): 0.0125 mg kg−1 d−1 [108, (parental) p. 310]
p. 423] 2.5 mg kg−1 d−1 [106,
Human. (developmental) p. 310]
(oral, 30-day): 0.006 mg kg−1 d−1 [99, Chronic.
p. 333] Rat (2-year feed): 2.5 mg kg−1 d−1 [112,
−1 −1
ADI: 0.0006 mg kg d [99, p. 333] p. 59]
−1 −1
Mouse (2-year feed): 3.6 mg kg d [112,
p. 59]
−1
Dog (2-year feed): 2.5 mg kg d−1 [112,
Omethoate [1113-02-6] p. 59]
ADI: 0.03 mg kg−1 d−1 [112, p. 59]
LD50 (rat, oral) 28 – 68 mg/kg [97,
p. 151] Phenthoate [2597-03-7]
LD50 (mouse, oral) 27 – 36 mg/kg [97, LD50 (rat, oral) 245 – 440 mg/kg [106,
p. 151] p. 404]
LD50 (rabbit, oral) 50 mg/kg [97, LD50 (mouse, oral) 360 – 840 mg/kg [106,
p. 151] p. 404]
LD50 (cat, oral) 50 mg/kg [97, LD50 (dog, oral) > 500 mg/kg [106,
p. 151] p. 404]
LD50 (guinea pig, oral) 100 mg/g [97, LD50 (guinea pig, oral) 377 mg/kg [106,
p. 151] p. 404]
LD50 (hen, oral) 125 mg/kg [97, LD50 (rabbit, oral) ca. 210 mg/g [106,
p. 151] p. 404]
LD50 (rat, dermal) 200 mg/kg [97, LD50 (chicken, oral) ca. 255 mg/kg [106,
p. 151] p. 404]
LC50 (rat, 4-h inhalation) ca. 0.3 mg/L air [20, LD50 (rat, dermal) 2100 mg/kg [106,
p. 896] p. 404]
Rabbit: nonirritating to eyes and skin [110, LD50 (rabbit, dermal) 1830 mg/kg [106,
p. 117] p. 404]
LC50 (rat, 4-h inhalation) > 0.8 mg/L air [20,
p. 952]
Rabbit: nonirritating to eyes and skin [106,
p. 404]
Nonmutagenic [106,
p. 404]
Acaricides 27
NOEL/NOAEL: LD50 (rabbit, dermal) 1530 mg/kg [99,
Reproduction. p. 347]
−1 −1 LC50 (rat, 4-h inhalation) 64 mg/L air [108,
Rat (3-generation feed): 5 mg kg d [106,
(parental and p. 404] p. 493]
developmental) Nonmutagenic [99,
Teratogenicity. p. 347]
−1 −1 NOEL/NOAEL:
Rabbit (gavage): 10 mg kg d [106,
(maternal and p. 404] Reproduction.
developmental) Rat (2-generation feed): 2.5 mg kg−1 d−1 [99,
Chronic. (parental and p. 347]
Rat (20-month feed): 0.5 mg kg−1 d−1 [106, developmental)
p. 404] Teratogenicity.
Mouse (18-month feed): 4.5 mg kg−1 d−1 [112, Rat (gavage): 10 mg kg−1 d−1 [99,
p. 64] (maternal and p. 347]
Dog (2-year feed): 0.29 mg kg−1 d−1 [106, developmental)
p. 404] Rabbit (gavage): 10 mg kg−1 d−1 [99,
ADI: 0.003 mg kg−1 d−1 [112, p. 64] (maternal and p. 347]
developmental)
Chronic.
Phorate [298-02-2] Rat (2-year feed): 0.2 mg kg−1 d−1 [99,
p. 347]
LD50 (rat, oral) 1.9 – 10 mg/kg [113, Mouse (2-year feed): 23 – 31 mg kg−1 d−1 [99,
p. 101] p. 347]
LD50 (mouse, oral) 3 – 11 mg/kg [113,
Dog (107-week feed): 5 mg kg−1 d−1 [99,
p. 101]
p. 347]
LD50 (rat, dermal) 3.9 – 9.3 mg/kg [113,
p. 101] ADI: 0.001 mg kg−1 d−1 [99, p. 347]
LD50 (rabbit, dermal) 5.2 mg/kg [113,
p. 101]
LC50 (rat, 4-h inhalation) 0.06 mg/L air (male) [113, Phosmet [732-11-6]
p. 101] LD50 (rat, oral) 100 – 300 mg/kg [113,
0.011 mg/L air (female) [113, p. 119]
p. 101] LD50 (mouse, oral) 20 – 50 mg/kg [113,
Nonmutagenic [113, p. 119]
p. 101] LD50 (guinea pig, oral) 200 mg/kg [113,
NOEL/NOAEL: p. 119]
Reproduction. LD50 (rabbit, dermal) > 5000 mg/kg [113,
Rat (2-generation feed): 0.17 mg kg−1 d−1 [113, p. 119]
(parental and p. 101] LC50 (rat, 4-h inhalation) 0.15 mg/L air [113,
developmental) p. 119]
Mouse (3-generation 0.23 mg kg−1 d−1 [113, Rabbit: nonirritating to skin [113,
feed): p. 101] p. 119]
Teratogenicity. Rabbit: mildly irritating to eyes [113,
Rat (gavage): 0.3 mg kg−1 d−1 [113, p. 119]
(maternal and p. 101] Mutagenicity: ambiguous [113,
developmental) p. 119]
NOEL/NOAEL:
Rabbit (gavage): 0.15 mg kg−1 d−1 [113,
Reproduction.
(maternal) p. 101]
Rat (2-generation feed): 1.3 mg kg−1 d−1 [113,
1.2 mg kg−1 d−1 [113,
(parental) p. 119]
(developmental) p. 101]
Chronic. 5.0 mg kg−1 d−1 [113,
(developmental) p. 119]
Rat (2-year feed): 0.05 mg kg−1 d−1 [113,
Teratogenicity.
p. 101]
Rat (gavage): 5 mg kg−1 d−1 [113,
Mouse (18-month feed): 0.45 mg kg−1 d−1 [113,
(maternal) p. 119]
p. 101]
15 mg kg−1 d−1 [113,
Dog (one-year capsule): 0.05 mg kg−1 d−1 [113,
(developmental) p. 119]
p. 101]
Rabbit (gavage): 5 mg kg−1 d−1 [113,
ADI: 0.0005 mg kg−1 d−1 [113, p. 101]
(maternal) p. 119]
2 mg kg−1 d−1 [113,
(developmental) p. 119]
Chronic.
Phosalone [2310-17-0] Rat (2-year feed): 1.8 mg kg−1 d−1 [113,
LD50 (rat, oral) 110 – 130 mg/kg [99, p. 119]
p. 347] −1 −1
Mouse (2-year feed): 4.0 mg kg d [113,
LD50 (mouse, oral) 93 – 205 mg/kg [99, p. 119]
−1
p. 347] Dog (2-year feed): 1.0 mg kg d−1 [113,
LD50 (guinea pig, oral) 82 – 150 mg/kg [99, p. 119]
p. 347] ADI: 0.01 mg kg−1 d−1 [113, p. 119]
LD50 (rat, dermal) 700 to mg/kg [99,
> 2560 p. 347]
28 Acaricides

Phosphamidon [13171-21-6] Teratogenicity.


Rat (gavage): 15 mg kg−1 d−1 [96,
LD50 (rat, oral) 24 mg/kg [100,
(maternal and p. 325]
p. 1031]
developmental)
LD50 (mouse, oral) 6.5 – 220 mg/kg [100,
Rabbit (gavage): <1 mg kg−1 d−1 [96,
p. 1031]
(maternal) p. 325]
LD50 (rat, dermal) 107 – 143 mg/kg [100,
p. 1031] 16 mg kg−1 d−1 [96,
LC50 (rat, 4-h inhalation) 0.18 mg/L air [20, (developmental) p. 325]
p. 963] Chronic.
Rabbit: slightly irritating to skin [20, Rat (2-year feed): 0.5 mg kg−1 d−1 [96,
p. 963] p. 325]
Rabbit: moderately irritating to eyes [20, Mouse (80-week feed): 0.5 mg kg−1 d−1 [96,
p. 963] p. 325]
Nonmutagenic [105, Dog (2-year capsule): 2 mg kg−1 d−1 [96,
p. 169] p. 325]
NOEL/NOAEL: Human.
Reproduction. Oral (28-56-day): 0.25 mg kg−1 d−1 [96,
−1 −1 p. 325]
Rat (2-generation feed): ca. 0.3 mg kg d [105,
−1 −1
(parental and p. 169] ADI: 0.03 mg kg d [96, p. 325]
developmental)
Teratogenicity.
Rat (gavage): 0.5 mg kg−1 d−1 [105,
(maternal) p. 169] Profenofos [41198-08-7]
2 mg kg−1 d−1 [105,
(developmental) p. 169] LD50 (rat, oral) 358 – 502 mg/kg [104,
Rabbit (gavage): 3 mg kg−1 d−1 [105, p. 123]
(maternal) p. 169] LD50 (mouse, oral) 298 mg/kg [104,
10 mg kg−1 d−1 [105, p. 123]
(developmental) p. 169] LD50 (Chinese hamster, 153 mg/kg [104,
Chronic. oral) p. 123]
−1 −1
Rat (2-year feed): 0.05 mg kg d [105, LD50 (rabbit, oral) 700 mg/kg [104,
p. 169] p. 123]
−1 −1
Dog (one-year capsule): 0.1 mg kg d [105, LD50 (dog, oral) > 500 mg/kg [104,
p. 169] p. 123]
ADI: 0.0005 mg kg−1 d−1 [105, p. 169] LD50 (rat, dermal) 3300 mg/kg [104,
p. 123]
LD50 (rabbit, dermal) 475 – 2540 mg/kg [104,
p. 123]
Pirimiphos-methyl [29232-93-7] LC50 (rat, 4-h inhalation) 3 – 3.6 mg/L air [104,
LD50 (rat, oral) 1667 – 1861 mg/kg [96, p. 123]
p. 325] Rabbit: moderately irritating to eyes [104,
LD50 (mouse, oral) 1180 mg/kg [96, p. 123]
p. 325] Rabbit: irritating to skin [104,
LD50 (rabbit, oral) 1150 – 2300 mg/kg [96, p. 123]
p. 325] Nonmutagenic [104,
LD50 (guinea pig, oral) 1000 – 2000 mg/kg [96, p. 123]
p. 325] NOEL/NOAEL:
LD50 (cat, oral) 575 – 1150 mg/kg [96, Reproduction.
p. 325] Rat (3-generation feed): 1.0 mg kg−1 d−1 [104,
LD50 (dog, oral) > 1500 mg/kg [96, (parental and p. 123]
p. 325] developmental)
LD50 (hen, oral) 30 – 60 mg/kg [96, Teratogenicity.
p. 325] Rat (gavage): 30 mg kg−1 d−1 [104,
LD50 (quail, oral) ca. 140 mg/kg [96, (maternal) p. 123]
p. 325] 18 mg kg−1 d−1 [104,
LD50 (rat, dermal) > 4592 mg/kg [20, (developmental) p. 123]
p. 988] Rabbit (gavage): 30 mg kg−1 d−1 [104,
LC50 (rat, 4-h inhalation) > 5.04 mg/L air [20, (maternal) p. 123]
p. 988] 175 mg kg−1 d−1 [104,
Rabbit: slightly irritating to eyes and skin [20, (developmental) p. 123]
p. 980] Chronic.
Guinea pig: not a skin sensitizer [20, Rat (2-year feed): 5.7 mg kg−1 d−1 [104,
p. 988] p. 123]
Nonmutagenic [96, −1 −1
Mouse (85-96-week feed): 5.8 mg kg d [104,
p. 325]
p. 123]
NOEL/NOAEL: −1
Reproduction. Dog (6-month feed): 2.9 mg kg d−1 [104,
−1 −1 p. 123]
Rat (3-generation feed): 5 mg kg d [96,
(parental and p. 325] ADI: 0.01 mg kg−1 d−1 [104, p. 123]
developmental)
Acaricides 29

Quinalphos [13593-03-8] Triazophos [24017-47-8]


LD50 (rat, oral) 51 – 56 mg/kg [114]
LD50 (mouse, oral) 55 – 59 mg/kg [114] LD50 (rat, oral) 57 – 59 mg/kg [116,
LD50 (rat, dermal) 850 – 940 mg/kg [114] p. 395]
LC50 (rat, 4-h inhalation) 0.71 mg/L air [114] LD50 (mouse, oral) 29 – 31 mg/kg [116,
Rabbit: nonirritating to eyes and skin [114] p. 395]
Guinea pig: not a skin sensitizer [114] LD50 (rat, dermal) 2000 mg/kg [116,
Nonmutagenic [114] p. 395]
NOEL/NOAEL: LC50 (rat, 4-h inhalation) 0.53 mg/L air [116,
Reproduction. p. 395]
Rat (3-generation feed): 70.5 mg kg−1 d−1 [114] Rabbit: nonirritating to skin and eyes [116,
(parental and p. 395]
developmental) Guinea pig: not a skin sensitizer [116,
Teratogenicity. p. 395]
Nonmutagenic [105,
Rat (gavage): 5.0 mg kg−1 d−1 [114]
p. 187]
(maternal)
NOEL/NOAEL:
12.0 mg kg−1 d−1 [114] Reproduction.
(developmental)
Rat (2-generation feed): 2–3 mg kg−1 d−1 [98,
Rabbit (gavage): 4 mg kg−1 d−1 [114] (parental and p. 303]
(maternal and developmental)
developmental) Teratogenicity.
Chronic.
Rat (feed): 22 mg kg−1 d−1 [105,
Rat (2-year feed): 0.2 – 0.26 mg kg−1 d−1 [114] (maternal and p. 187]
Mouse (18-month feed): 0.7 mg kg−1 d−1 [114] developmental)
Dog (2-year feed): 0.012 – 0.014mg kg−1 d−1 [114] Rabbit (gavage): 4 mg kg−1 d−1 [105,
(maternal and p. 187]
developmental)
Sulfotep [3689-24-5] Chronic.
Rat (2-year feed): 0.17 mg kg−1 d−1 [98,
LD50 (rat, oral) ca. 10 mg/kg [20, p. 303]
p. 1131] −1 −1
Mice (2-year feed): 4.5 mg kg d [98,
LD50 (rat, dermal) 262 mg/kg [20,
p. 303]
p. 1131] −1
LC50 (rat, 4-h inhalation) 0.05 mg/L air [20, Dog (one-year feed): 0.12 mg kg d−1 [98,
p. 1131] p. 303]
Rabbit: nonirritating to skin and eyes [20, Human.
p. 1131] (3-week oral): 0.0125 mg kg−1 d−1 [98,
NOEL/NOAEL: p. 303]
−1 −1
Chronic. ADI: 0.001 mg kg d [99, p. 391]
Rat (2-year feed): 0.5 mg kg−1 d−1 [20,
p. 1131]
Mouse (2-year feed): 7 mg kg−1 d−1 [20,
p. 1131] Vamidothion [2275-23-2]
ADI: 0.001 mg kg−1 d−1 [20, p. 1131]
LD50 (rat, oral) 64 – 105 mg/kg [115,
p. 453]
LD50 (mouse, oral) 64 mg/kg [115,
Thiometon [640-15-3] p. 453]
LD50 (rat, oral) 100 – 125 mg/kg [115, LD50 (guinea pig, oral) 85 mg/kg [115,
p. 397] p. 453]
LD50 (mouse, oral) 62 – 66 mg/kg [115, LD50 (rabbit, oral) 160 mg/kg [115,
p. 397] p. 453]
LD50 (guinea pig, oral) 261 mg/kg [115, LD50 (dog, oral) 110 mg/kg [115,
p. 397] p. 453]
LD50 (rabbit, oral) 95 mg/kg [115, LD50 (mouse, dermal) 1460 mg/kg [115,
p. 397] p. 453]
LD50 (rat, dermal) 1429 – 1997 mg/kg [115, LD50 (rabbit, dermal) 1160 mg/kg [115,
p. 397] p. 453]
LC50 (rat, 4-h inhalation) > 1.93 mg/L air [20, LC50 (rat, 4-h inhalation) 1.73 mg/L air [20,
p. 1199] p. 1263]
NOEL/NOAEL: NOEL/NOAEL:
Reproduction. Reproduction.
−1 −1
Rat (2-generation feed): >1 mg kg d [116, Rat (2-generation gavage):0.5 mg kg−1 d−1 [117,
(parental and p. 503] (parental and p. 75]
developmental) developmental)
Chronic. Subchronic.
Rat (2-year feed): 0.12 mg kg−1 d−1 [116, Rat (3-month feed): 0.054 mg kg−1 d−1 [117,
p. 503] p. 75]
Dog (2-year feed): 0.15 mg kg−1 d−1 [116, Mouse (3-month feed): 0.137 mg kg −1
d −1
[117,
p. 503] p. 75]
−1 −1
ADI: 0.003 mg kg d [116, p. 503]
30 Acaricides

Chronic. Rabbit (gavage): 2.7 mg kg−1 d−1 [96,


Dog (one-year gavage): 0.5 mg kg−1 d−1 [117, (maternal) p. 79]
p. 75] >8 mg kg−1 d−1 [96,
Human. (developmental) p. 79]
−1 −1
(5-day oral): 0.08 mg kg d [117, Chronic.
p. 75] Rat (2-year feed): 4 mg kg−1 d−1 [96,
ADI: 0.008 mg kg−1 d−1 [117, p. 75] (males) p. 79]
7.5 mg kg−1 d−1 [96,
(females) p. 79]
Mouse (20-month feed): 7.6 mg kg−1 d−1 [96,
(males) p. 79]
4.2. Pyrethroids 37 mg kg−1 d−1 [96,
(females) p. 79]
Toxic action. General nerve activation with Dog (one-year capsule): 1.5 mg kg−1 d−1 [96,
convulsion, paralysis, and respiratory failure; cis (females) p. 79]
−1 −1
ADI: 0.02 mg kg d [96, p. 79]
isomers are metabolized poorly and have higher
toxicity [94, p. 586].
Fenpropathrin [64257-84-7]
Acrinathrin [101007-06-1] LD50 (rat, oral) 49 – 164 mg/kg [99,
p. 233]
LD50 (rat, oral) > 5000 mg/kg [20, LD50 (mouse, oral) 58 – 154 mg/kg [99,
p. 16] p. 233]
LD50 (mouse, oral) > 5000 mg/kg [20, LD50 (rabbit, oral) 510 – 675 mg/kg [99,
p. 16] p. 233]
LD50 (rat, dermal) > 2000 mg/kg [20, LD50 (dog, oral) > 1000 mg/kg [99,
p. 16] p. 233]
LC50 (rat, 4-h inhalation) 1.6 mg/L air [20, LD50 (rat, dermal) 870 – 1600 mg/kg [99,
p. 16] p. 233]
Rabbit: nonirritating to skin and eyes [20, LD50 (mouse, dermal) 740 – 920 mg/kg [99,
p. 16] p. 233]
Guinea pig: not a skin sensitizer [20, LD50 (rabbit, dermal) 510 – 675 mg/kg [99,
p. 16] p. 233]
Nonmutagenic [20, LC50 (rat, 2-h inhalation) > 96 mg/L air [99,
p. 16] p. 233]
NOEL/NOAEL: LC50 (mouse, ?-h 43 – 100 mg/L air [99,
Subchronic. inhalation) p. 233]
−1 −1
Rat (90-day feed): 2.4 – 3.1 mg kg d [20, Rabbit: slightly irritating to eyes [99,
p. 16] p. 233]
Chronic. Rabbit: nonrritating to skin [99,
Dog (one-year feed): 3.0 mg kg−1 d−1 [20, p. 233]
p. 16] Guinea pig: not a skin sensitizer [99,
ADI: 0.02 mg kg−1 d−1 [20, p. 16] p. 233]
Nonmutagenic [99,
p. 233]
Bifenthrin [82657-04-3] NOEL/NOAEL:
LD50 (rat, oral) 56 mg/kg [96, Reproduction.
p. 79] Rat (3-generation feed): 3 mg kg−1 d−1 [99,
LD50 (mouse, oral) 43 mg/kg [96, (parental and p. 233]
p. 79] developmental)
LD50 (rabbit, dermal) > 2000 mg/kg [96, Teratogenicity.
p. 79] Rat (gavage): 3 mg kg−1 d−1 [99,
Rabbit: nonirritating to skin [96, (maternal) p. 233]
p. 79] 10 mg kg−1 d−1 [99,
Rabbit: slightly irritating to eyes [96, (developmental) p. 233]
p. 79] Rabbit (gavage): 4 mg kg−1 d−1 [99,
Guinea pig: not a skin sensitizer [96, (maternal) p. 233]
p. 79] 36 mg kg−1 d−1 [99,
Nonmutagenic [96, (developmental) p. 233]
p. 79] Chronic.
NOEL/NOAEL: Rat (2-year feed): 7 mg kg−1 d−1 [99,
Reproduction. p. 233]
−1 −1
Rat (2-generation feed): 3 mg kg d [96, −1 −1
Mouse (2-year feed): 56 mg kg d [99,
(parental) p. 79] p. 233]
5 mg kg−1 d−1 [96, Dog (one-year feed): 3 mg kg−1 d−1 [99,
(developmental) p. 79] p. 233]
Teratogenicity. ADI: 0.03 mg kg−1 d−1 [99, p. 233]
Rat (gavage): 1 mg kg−1 d−1 [96,
(maternal) p. 79]
>2 mg kg−1 d−1 [96,
(developmental) p. 79]
Acaricides 31

Fenvalerate [51630-58-1] 4.3. Formamidines


LD50 (rat, oral) 451 mg/kg (DMSO) [118]
> 3200 mg/kg [118] Amitraz [33089-61-1]
(PEG/Water)
LD50 (mouse, oral) 100 – 300 mg/kg (DMSO) [118] LD50 (rat, oral) 600 mg/kg [106,
1002 mg/kg [118] p. 1]
(PEG/Water) LD50 (mouse, oral) > 1600 mg/kg [106,
LD50 (chinese hamster, 83 – 98 mg/kg (DMSO) [118] p. 1]
oral) LD50 (guinea pig, oral) 400 – 800 mg/kg [106,
LD50 (hen, oral) > 1500 mg/kg [118] p. 1]
LD50 (rat, dermal) 5000 mg/kg [118] LD50 (rabbit, oral) > 100 mg/kg [106,
LD50 (rabbit, dermal) 1000 – 3200 mg/kg [118] p. 1]
LC50 (rat, 3-h inhalation) > 101 mg/L air [118] LD50 (dog, oral) 100 mg/kg [106,
LC50 (mouse, 3-h 101 mg/L air [118] p. 1]
inhalation) LD50 (babboon, oral) 100 – 250 mg/kg [106,
Rabbit: nonirritating to skin and eyes [118] p. 1]
Guinea pig: not a skin sensitizer [118] LD50 (rat, dermal) > 600 mg/kg [106,
Nonmutagenic [119, p. 1]
p. 299] LD50 (rabbit, dermal) > 200 mg/kg [106,
NOEL/NOAEL: p. 1]
Reproduction. LC50 (rat, 6-h inhalation) 65 mg/L air [106,
Rat (3-generation feed): 2.5 mg kg−1 d−1 [118] p. 1]
(parental) Rabbit: nonirritating to skin and eyes [106,
2.5 mg kg−1 d−1 [118] p. 1]
(developmental) Guinea pig: not a skin sensitizer [106,
Teratogenicity. p. 1]
Nonmutagenic [106,
Mouse (gavage): 15 mg kg−1 d−1 [118]
p. 1]
(maternal)
NOEL/NOAEL:
50 mg kg−1 d−1 [118] Reproduction.
(developmental)
Rat (3-generation feed): 1 mg kg−1 d−1 [106,
Rabbit (gavage): 25 mg kg−1 d−1 [118] p. 1]
(maternal) Teratogenicity.
50 mg kg−1 d−1 [118] Rat (gavage): 1 mg kg−1 d−1 [106,
(developmental) p. 1]
Chronic. Chronic.
Rat (2-year feed): 12.5 mg kg−1 d−1 [120] Rat (two-year feed): 3 mg kg−1 d−1 [123,
Mouse (78-week feed): 11.9 mg kg−1 d−1 [121] p. 14]
Dog (90-day feed): 12.5 mg kg−1 d−1 [119, Mouse (80-week feed): 2.5 mg kg −1
d −1
[123,
p. 299] p. 14]
ADI: 0.02 mg kg−1 d−1 [122, p. 28] Dog (2-year feed): 0.25 mg kg −1
d−1 [123,
p. 14]
ADI: 0.003 mg kg−1 d−1 [106, p. 1]

Halfenprox [111872-58-3]
LD50 (rat, oral) 132 – 159 mg/kg [20, Formetanate [22259-30-9]
p. 654]
LD50 (mouse, oral) 121 – 149 mg/kg [20, LD50 (rat, oral) 15 – 26 mg/kg [100,
p. 654] p. 1159]
LD50 (rat, dermal) 2000 mg/kg [20, LD50 (mouse, oral) 13 – 25 mg/kg [100,
p. 654] p. 1159]
LC50 (rat, 4-h inhalation) 0.36 – 1.38 mg/L air [20, LD50 (dog, oral) 19 mg/kg [100,
p. 654] p. 1159]
NOEL/NOAEL: LD50 (rabbit, dermal) > 10200 mg/kg [100,
Chronic. p. 1159]
Rat (2-year feed): 1.4 mg kg−1 d−1 [20, LD50 (rat, dermal) > 5600 mg/kg [100,
p. 654] p. 1159]
−1 −1
ADI: 0.014 mg kg d [20, p. 654] LC50 (rat, 4-h inhalation) 0.28 – 2.9 mg/L air [100,
p. 1159]
Rabbit: irritating to eyes [20,
p. 623]
Guinea pig: skin sensitizer [20,
p. 623]
Nonmutagenic [100,
p. 1159]
32 Acaricides

NOEL/NOAEL: NOEL/NOAEL:
Teratogenicity. Reproduction.
Not teratogenic [100, Rat (feed): 6.4 mg kg−1 d−1 [128,
p. 1159] p. 75]
Reproduction. Teratogenicity.
Rat (2-generation feed): 2.5 g kg−1 d−1 [106, Mouse (gavage): 10 mg kg−1 d−1 [128,
(parental and p. 1] (developmental) p. 75]
developmental) 40 mg kg−1 d−1 [128,
Chronic. (maternal) p. 75]
−1 −1
Rat (2-year feed): 0.52 mg kg d [20, Rat (gavage): 100 mg kg−1 d−1 [128,
p. 623] (maternal and p. 75]
−1 −1
Mouse (2-year feed): 8.2 mg kg d [20, developmental)
p. 623] Syrian hamster (gavage): 25 mg kg−1 d−1 [128,
Dog (one-year feed): 0.37 mg kg−1 d−1 [20, (maternal) p. 75]
p. 623] 12.5 mg kg−1 d−1 [128,
ADI: 0.037 mg kg−1 d−1 [20, p. 623] (developmental) p. 75]
Rabbit (gavage): 0.5 mg kg−1 d−1 [128,
(developmental) p. 75]
Chronic.
Rat (30-month feed): 6.4 mg kg−1 d−1 [128,
(males) p. 75]
4.4. Nitrophenyl Esters 8.1 mg kg−1 d−1 [128,
(females) p. 75]
Toxic Action. Uncoupling of oxidative Dog (one-year feed): 0.4 mg kg−1 d−1 [128,
p. 75]
phosphorylation; cataract formation [94, Eye cateracts in duck and 9 mg kg−1 d−1 [128,
p. 556]. rabbit: NOAEL (rabbit, p. 75]
gavage)
ADI: 0.001 mg kg−1 d−1 [128, p. 75]
Dinobuton [973-21-7]
LD50 (rat, oral) 140 mg/kg [124]
LD50 (mouse, oral) 2540 mg/kg [125]
LD50 (rat, dermal) > 5000 mg/kg [126]
NOEL/NOAEL: 4.5. Sulfonic Acid Ester
Chronic.
−1 −1
Rat (2-year feed): 3–6 mg kg d [127]
Dog (one-year feed): 4.5 mg kg−1 d−1 [127] Tetradifon [116-29-0]
LD50 (rat, oral) > 14700 mg/kg [20,
p. 1177]
LD50 (rabbit, dermal) > 10000 mg/kg [20,
Dinocap [39300-45-31] p. 1177]
LC50 (rat, 4-h inhalation) > 3 mg/L air [20,
LD50 (male rat, oral) 1581 – 2321 mg/kg [128, p. 1177]
p. 75] Rabbit: nonirritating to skin [20,
LD50 (female rat, oral) 510 – 1493 mg/kg [128, p. 1177]
p. 75] Rabbit: slightly irritating to eyes [20,
LD50 (mouse, oral) 150 – 180 mg/kg [128, p. 1177]
p. 75] Nonmutagenic [20,
LD50 (rabbit, oral) 2000 – 3000 mg/kg [128, p. 1177]
p. 75] Not teratogenic in rat and rabbit [20,
LD50 (dog, oral) 100 mg/kg [128, p. 1177]
p. 75] NOEL/NOAEL:
LD50 (rabbit, dermal) > 4700 [128, Reproduction.
p. 75] Rat (2-generation feed): ca. 10 mg kg−1 d−1 [20,
LC50 (rat, 4-h inhalation) 0.36 mg/L air [20, p. 1177]
p. 426] Chronic.
Rabbit: moderately to markedly irritating, to skin and eyes [20, Rat (2-year feed): 15 mg kg−1 d−1 [20,
p. 426] (males) p. 1177]
Nonmutagenic [20,
p. 426]
Acaricides 33
NOEL/NOAEL:
4.6. Halogenated Benzhydrol Reproduction.
Derivatives Rat (2-generation feed): 0.25 mg kg−1 d−1 [107,
(parental) p. 137]
2.1 mg kg−1 d−1 [107,
Bromopropylate [18181-80-1] (developmental) p. 137]
Teratogenicity.
LD50 (rat, oral) > 5000 mg/kg [99, Rat (gavage): 0.25 mg kg−1 d−1 [107,
p. 39] (maternal) p. 137]
LD50 (mouse, oral) 8000 mg/kg [99, 25 mg kg−1 d−1 [107,
p. 39] (developmental) p. 137]
LD50 (rabbit, oral) > 6000 mg/kg [99,
Rabbit (gavage): 0.4 mg kg−1 d−1 [107,
p. 39]
(maternal) p. 137]
LD50 (rat, dermal) > 4000 mg/kg [99,
4 mg kg−1 d−1 [107,
p. 39]
(developmental) p. 137]
LD50 (rabbit, dermal) > 2020 mg/kg [99,
Chronic.
p. 39]
LC50 (rat, 4-h inhalation) > 4458 mg/L air [99, Rat (2-year feed): 0.22 mg kg−1 d−1 [107,
p. 39] p. 137]
−1 −1
Rabbit: nonirritating to eyes and skin [99, Mouse (78-week feed): > 40 mg kg d [107,
p. 39] p. 137]
Guinea pig: not a skin sensitizer [99, Dog (one-year feed): 0.82 mg kg−1 d−1 [107,
p. 39] p. 137]
Nonmutagenic [99, ADI: 0.002 mg kg−1 d−1 [107, p. 137]
p. 39]
NOEL/NOAEL:
Reproduction.
Rat (2-generation feed): 9 mg kg−1 d−1 [99, 4.7. Organometallic Compounds
(parental and p. 39]
developmental)
Teratogenicity. Toxic Action. Interference with lymphocyte
Rat (gavage): 50 mg kg−1 d−1 [99,
(maternal) p. 39]
function; induction of heme oxygenase; de-
700 mg kg−1 d−1 [99, creased liver hemoprotein level [94, p. 353].
(developmental) p. 39]
Rabbit (gavage): 20 mg kg−1 d−1 [99,
(maternal) p. 39] Azocyclotin [41083-11-8]
120 mg kg−1 d−1 [99, LD50 (rat, oral) > 150 mg/kg [116,
(developmental) p. 39] p. 50]
Chronic. LD50 (rat, oral) 209 – 363 mg/kg [20,
Rat (2-year feed): 3.7 mg kg−1 d−1 [99, p. 69]
p. 39] LD50 (guinea pig, oral) 261 mg/kg [20,
Mouse (2-year feed): 16 mg kg−1 d−1 [99, p. 69]
p. 39] LD50 (mouse, oral) 870 – 980 mg/kg [20,
Dog (one-year feed): 2.7 mg kg−1 d−1 [99, p. 69]
p. 39] LD50 (rat, dermal) > 5000 mg/kg [116,
p. 50]
ADI: 0.03 mg kg−1 d−1 [99, p. 39]
LC50 (rat, 4-h inhalation) ∼ 0.02 mg/L air [116,
p. 50]
Rabbit: irritating to skin and eyes [116,
Dicofol [115-32-3] p. 50]
LD50 (rat, oral) 587 – 595 mg/kg [107, Guinea pig: not a skin sensitizer [116,
p. 137] p. 50]
LD50 (mouse, oral) 669 – 675 mg/kg [107, NOEL/NOAEL:
p. 137] Reproduction.
LD50 (rabbit, oral) 1820 mg/kg [107, Rat (2-generation feed): 1.0 mg kg−1 d−1 [129,
p. 137] p. 22]
LD50 (dog, oral) > 4000 mg/kg [107, Teratogenicity.
p. 137] Rabbit (gavage): 0.1 mg kg−1 d−1 [129,
LD50 (rat, dermal) > 5000 mg/kg [107, (maternal) p. 22]
p. 137] 1.0 mg kg−1 d−1 [129,
LD50 (rabbit, dermal) > 2500 mg/kg [107, (developmental) p. 22]
p. 137] Chronic.
LC50 (rat, 4-h inhalation) > 5 mg/L air [107, Rat (2-year feed): 0.25 mg kg−1 d−1 [129,
p. 137] p. 22]
Rabbit: nonirritating to eyes [107, −1 −1
Mouse (2-year feed): 2.14 mg kg d [129,
p. 137]
p. 22]
Rabbit: irritating to skin [107,
p. 137] Dog (2-year feed): 0.25 mg kg−1 d−1 [129,
Guinea pig: not a skin sensitizer [134] p. 22]
Nonmutagenic [107, ADI: 0.007 mg kg−1 d−1 [129, p. 22]
p. 137]
34 Acaricides

Cyhexatin [13121-70-5] Chronic.


Rat (2-year feed): 2.5 mg kg−1 d−1 [96,
LD50 (rat, oral) 540 mg/kg [20,
p. 193]
p. 302] −1 −1
Dog (2-year gavage): 15 mg kg d [96,
LD50 (rabbit, oral) 500 – 1000 mg/kg [20,
p. 193]
p. 302]
LD50 (guinea pig, oral) 780 mg/kg [20, ADI: 0.03 mg kg−1 d−1 [96, p. 193]
p. 302]
LD50 (rabbit, dermal) > 2000 mg/kg [20,
p. 302]
Rabbit: irritating to eyes [20,
p. 302]
Rabbit: nonirritating to skin [20, 4.8. Other Compounds
p. 302]
NOEL/NOAEL: Abamectin [71751-41-2]
Reproduction.
Rat (2-generation feed): 0.1 mg kg−1 d−1 [113, LD50 (rat, oral) 8.7 – 12.8 mg/kg [96,
(parental) p. 65] p. 3]
0.7 mg kg−1 d−1 [113, LD50 (mouse, oral) 13.6 – 23.8 mg/kg [96,
(developmental) p. 65] p. 3]
Teratogenicity. LD50 (dog, oral) ca. 8 mg/kg [96,
Rabbit (gavage): 0.75 mg kg−1 d−1 [113, p. 3]
(maternal) p. 65] LD50 (monkey, oral) > 24 mg/kg [96,
Chronic. p. 3]
−1 −1
Mouse (2-year feed): 3 mg kg d [113, LD50 (rat, dermal) > 330 mg/kg [96,
p. 65] p. 3]
−1 −1
Dog (one-year feed): 0.75 mg kg d [98, LD50 (rabbit, dermal) > 1600 mg/kg [96,
p. 129] p. 3]
−1 −1 Rabbit: nonirritating to skin [96,
ADI: 0.007 mg kg d [113, p. 65]
p. 3]
Rabbit: very slightly irritating to eyes [96,
p. 3]
Guinea pig: not a skin sensitizer [96,
Fenbutatin oxide [13356-08-6] p. 3]
Nonmutagenic [96,
LD50 (rat, oral) 4400 mg/kg [96, p. 3]
p. 193] NOEL/NOAEL:
LD50 (mouse, oral) 1450 mg/kg [96, Reproduction.
p. 193] Rat (2-generation gavage): 0.05 mg kg−1 d−1 [96,
LD50 (dog, oral) > 1500 mg/kg [96, (parental) p. 3]
p. 193]
0.12 mg kg−1 d−1 [96,
LD50 (rabbit, oral) 1500 – 3000 mg/kg [96,
(developmental) p. 3]
p. 193]
Teratogenicity.
LD50 (rat, dermal) > 1000 mg/kg [96,
p. 193] Mice (gavage): 0.05 mg kg−1 d−1 [96,
LD50 (rabbit, dermal) > 2000 mg/kg [96, (maternal) p. 3]
p. 193] 0.2 mg kg−1 d−1 [96,
LC50 (rat, 4-h inhalation) 0.072 mg/L air [96, (developmental) p. 3]
p. 193] Rat (gavage): 1.6 mg kg−1 d−1 [96,
Rabbit: irritating to skin [96, (maternal) p. 3]
p. 193] < 1.6 mg kg−1 d−1 [96,
Rabbit: severely irritating to eyes [96, (developmental) p. 3]
p. 193] Rabbit (gavage): 1.0 mg kg−1 d−1 [96,
Nonmutagenic [96, (maternal and p. 3]
p. 193] developmental)
NOEL/NOAEL: Chronic.
Reproduction. Rat (> 2-year feed): 2.5 mg kg−1 d−1 [96,
−1 −1
Rat (2-generation feed): 6.0 mg kg d [96, p. 3]
(parental and p. 193] Mouse (94-week feed): 4 mg kg−1 d−1 [96,
developmental) p. 3]
Teratogenicity. Dog (52-week feed): < 0.25 mg kg−1 d−1 [96,
Rabbit (gavage): 15 mg kg−1 d−1 [96, p. 3]
(maternal) p. 193] ADI: 0.0001 mg kg−1 d−1 [96, p. 3]
30 mg kg−1 d−1 [96,
(developmental) p. 193]
Rabbit (gavage): 1 mg kg−1 d−1 [96,
(maternal and p. 193]
developmental)
Acaricides 35

Benzoximate [29104-30-1] Cymizaol [61676-87-7]


LD50 (rat, oral) 5000 – 15000mg/kg [20, LD50 (rat, oral) 758 mg/kg [20,
p. 113] p. 197]
LD50 (mouse, oral) 12000 – 14500 mg/kg [20, LD50 (rat, dermal) > 3100 mg/kg [20,
p. 113] p. 197]
LD50 (rat, dermal) > 15000 mg/kg [20, LC50 (rat, 4-h inhalation) 2.8 mg/L air [20,
p. 113] p. 197]
LD50 (mouse, dermal) > 15000 mg/kg [20, Rabbit: slightly irritating to skin and eyes [20,
p. 113] p. 197]
NOEL/NOAEL: NOEL/NOAEL:
Chronic. Chronic.
−1 −1
Rat (2-year feed): 20 mg kg d [20, Rat (2-year feed): 0.5 mg kg−1 d−1 [20,
p. 113] p. 197]
Mouse (2-year feed): 14 mg kg−1 d−1 [20,
p. 197]

Buprofezin [69327-76-0]
LD50 (rat, oral) 1635 – 2355 mg/kg [98, Chinomethionate [2439-01-2]
p. 75]
LD50 (mouse, oral) > 1000 mg/kg [98, LD50 (rat, oral) 1800 – 4800 mg/kg [131]
p. 75] LD50 (guinea pig, oral) 1500 mg/kg [20,
LD50 (hamster, oral) > 10000 mg/kg [98, p. 198]
p. 75] LD50 (rat, dermal) > 5000 mg/kg [20,
LD50 (rabbit, oral) > 5000 mg/kg [98, p. 198]
p. 75] LC50 (rat, 4-h inhalation) 3.0 mg/L air [20,
LD50 (rat, dermal) > 5000 mg/kg [98, p. 198]
p. 75] Rabbit: slightly irritating to skin and eyes [20,
LC50 (rat, 4-h inhalation) > 4.6 mg/L air [98, p. 198]
p. 75] Nonmutagenic [102,
Rabbit: mildly irritating to skin [98, p. 27]
p. 75] NOEL/NOAEL:
Rabbit: nonirritating to eyes [98, Reproduction.
p. 75] Rat (one-generation feed): ca. 1 mg kg−1 d−1 [102,
Nonmutagenic [98, (parental and p. 27]
p. 75] developmental)
NOEL/NOAEL: Teratogenicity.
Reproduction. Rat (gavage): 25 mg kg−1 d−1 [102,
Rat (one-generation feed): 6.4 mg kg−1 d−1 [98, (maternal and p. 27]
(parental and p. 75] developmental)
developmental) Rabbit (gavage): 30 mg kg−1 d−1 [102,
Teratogenicity. (maternal and p. 27]
−1 −1
Rat (gavage): 50 mg kg d [98, developmental)
(maternal) p. 75] Chronic.
166 mg kg−1 d−1 [98, Rat (2-year feed): 0.6 mg kg−1 d−1 [102,
(developmental) p. 75] p. 27]
Rabbit (gavage): 50 mg kg−1 d−1 [98, Mouse (21-month feed): 16 – 21 mg kg −1
d −1
[102,
(maternal and p. 75] p. 27]
developmental) Dog (one-year feed): 0.6 mg kg−1 d−1 [102,
Chronic. p. 27]
−1 −1
Rat (2-year feed): 0.9 mg kg d [98, ADI: 0.006 mg kg−1 d−1 [102, p. 27]
p. 75]
−1 −1
Mouse (2-year feed): 1.82 mg kg d [98,
p. 75]
Dog (2-year capsule): 2 mg kg−1 d−1 [98,
p. 75]
ADI: 0.01 mg kg−1 d−1 [98, p. 75]
36 Acaricides

Clofentezine [74115-24-5] Endusolfan [115-29-7]


LD50 (rat, oral) > 3200 mg/kg [115, LD50 (rat, oral) 70 – 110 mg/kg [20,
p. 17] p. 459]
LD50 (mouse, oral) > 3200 mg/kg [115, LD50 (dog, oral) 77 mg/kg [20,
p. 17] p. 459]
LD50 (hamster, oral) > 3200 mg/kg [115, LD50 (hamster, oral) 118 mg/kg [132]
p. 17] LD50 (rat, dermal) 500 mg/kg (female) [20,
LD50 (dog, oral) > 2000 mg/kg [115, p. 459]
p. 17] > 4000 mg/kg (male) [20,
LD50 (guinea pig, oral) > 1500 mg/kg [115, p. 459]
p. 17] LD50 (rabbit, dermal) 359 mg/kg [20,
LD50 (rat, dermal) > 1332 mg/kg [115, p. 459]
p. 17] LD50 (guinea pig, 1000 mg/kg [132]
LC50 (rat, 6-h inhalation) > 9.08 mg/L air [115, dermal)
p. 17] LC50 (rat, 4-h inhalation) 0.0345 – 0.913
mg/L air (male) [107,
Rabbit: mildly irritating to skin and eyes [115, p. 95]
p. 17] Guinea pig: not a skin sensitizer [107,
Guinea pig: not a skin sensitizer [115, p. 95]
p. 17] Nonmutagenic [107,
Nonmutagenic [115, p. 95]
p. 17] NOEL/NOAEL:
NOEL/NOAEL: Reproduction.
Reproduction. Rat (2-generation feed): 1.0 mg kg−1 d−1 [107,
Rat (2-generation feed): ca. 2.7 mg kg−1 d−1 [115, (parental) p. 95]
(parental and p. 17] 6.0 mg kg−1 d−1 [107,
developmental) (developmental) p. 95]
Teratogenicity. Teratogenicity.
Rat (gavage): 320 mg kg−1 d−1 [115, Rat (gavage): 0.66 mg kg−1 d−1 [107,
(maternal) p. 17] (maternal) p. 95]
1280 mg kg−1 d−1 [115, 2.0 mg kg−1 d−1 [107,
(developmental) p. 17] (developmental) p. 95]
Rabbit (gavage): 250 mg kg−1 d−1 [115, Rabbit (gavage): 0.7 mg kg−1 d−1 [107,
(maternal) p. 17] (maternal) p. 95]
1000 mg kg−1 d−1 [115, 1.8 mg kg−1 d−1 [107,
(developmental) p. 17] (developmental) p. 95]
Chronic. Chronic.
Rat (118-week feed): 2 mg kg−1 d−1 [115, Rat (2-year feed): 0.6 – 0.7 mg kg−1 d−1 [107,
p. 17] p. 95]
−1 −1 −1 −1
Mouse (105-week feed): 5 mg kg d [115, Mouse (2-year feed): ∼ 0.9 mg kg d [107,
p. 17] p. 95]
−1 −1
Dog (52-week feed): 1.2 mg kg d [115, Dog (one-year feed): ∼ 0.6 mg kg−1 d−1 [107,
p. 17] p. 95]
ADI: 0.02 mg kg−1 d−1 [115, p. 17] ADI: 0.006 mg kg−1 d−1 [107, p. 95]

Dienochlor [2227-17-0] Fenazaquin [120928-09-8]


LD50 (rat, oral) > 5000 mg/kg [20, LD50 (rat, oral) 134 – 138 mg/kg [20,
p. 385] p. 506]
LD50 (rat, dermal) > 2000 mg/kg [20, LD50 (mouse, oral) 1480 – 2449 mg/kg [20,
p. 385] p. 506]
LD50 (rabbit, dermal) > 3160 mg/kg [20, LD50 (rabbit, dermal) > 5000 mg/kg [20,
p. 385] p. 506]
LD50 (rat, 4-h inhalation) 0.08 mg/L air [20, LC50 (rat, 4-h inhalation) 1.9 mg/L air [20,
p. 385] p. 506]
Rabbit: mildly irritating to eyes and skin [20, Rabbit: slightly irritating to eyes [20,
p. 385] p. 506]
Guinea pig: not a skin sensitizer [20, Rabbit: nonirritating to skin [20,
p. 385] p. 506]
Guinea pig: not a skin sensitizer [20,
p. 506]
Nonmutagenic [20,
p. 506]
Not teratogenic or carcinogenic [20,
p. 506]
ADI: 0.005 mg kg−1 d−1 [20, p. 506]
Acaricides 37

Fenpyroximate [111812-58-9] Flufenoxuron [101463-69-8]


LD50 (rat, oral) 245 – 480 mg/kg [133] LD50 (rat, oral) > 3000 mg/kg [20,
LD50 (mouse, oral) 440 – 520 mg/kg [133] p. 568]
LD50 (rat, dermal) > 4000 mg/kg (female) [134] LD50 (rat, dermal) > 2000 mg/kg [20,
LC50 (rat, 4-h inhalation) 0.0002 – 0.0003 mg/L air [133] p. 568]
Rabbit: nonirritating to skin [134] LD50 (mouse, dermal) > 2000 mg/kg [20,
Rabbit: slightly irritating to eyes [134] p. 568]
Nonmutagenic [133] LC50 (rat, 4-h inhalation) 5 mg/L air [20,
NOEL/NOAEL: p. 568]
Reproduction. Rabbit: nonirritating to skin and eyes [20,
Rat (2-generation feed): 2.0 mg kg−1 d−1 [133] p. 568]
(parental and NOEL/NOAEL:
developmental) Subchronic.
Teratogenicity. Rat (90-day feed): ca. 3.3 mg kg−1 d−1 [20,
Rat (gavage): 25 mg kg−1 d−1 [133] p. 568]
−1 −1
(maternal and Mouse (90-day feed): ca. 7.1 mg kg d [20,
developmental) p. 568]
Rabbit (gavage): 2.5 mg kg−1 d−1 [133] Dog (one-year feed): ca. 2.5 mg kg−1 d−1 [20,
(maternal) p. 568]
>5 mg kg−1 d−1 [133]
(developmental)
Subchronic.
Rat (13-week feed): 1.3 mg kg−1 d−1 [133] Hezythiazox [78587-05-0]
Dog (13-week feed): 2 mg kg−1 d−1 [133]
Chronic. LD50 (rat, oral) > 5000 mg/kg [98,
Rat (2-year feed): 1.0 mg kg−1 d−1 [133] p. 265]
Mouse (18-month feed): 9.5 mg kg−1 d−1 [133] LD50 (mouse, oral) > 5000 mg/kg [98,
Dog (one-year feed): 5.0 mg kg−1 d−1 [133] p. 265]
ADI: 0.01 mg kg−1 d−1 [133] LD50 (dog, oral) > 5000 mg/kg [98,
p. 265]
LD50 (rat, dermal) > 50000 mg/kg [98,
p. 265]
LC50 (rat, 4-h inhalation) > 2.0 mg/L air [98,
Flucycloxuron [94050-52-9] p. 265]
Rabbit: nonirritating to skin [98,
LD50 (rat, oral) > 5000 mg/kg [20, p. 265]
p. 562] Rabbit: slightly irritating to eyes [98,
LD50 (rat, dermal) > 2000 mg/kg [20, p. 265]
p. 562] Guinea pig: not a skin sensitizer [98,
LC50 (rat, 4-h inhalation) 3.3 mg/L air [20, p. 265]
p. 562] Nonmutagenic [98,
Rabbit: nonirritating to skin [20, p. 265]
p. 562] NOEL/NOAEL:
Rabbit: mildly irritating to eyes [20, Reproduction.
p. 562]
Rat (2-generation feed): 4.22 – 5.34 mg kg−1 d−1 [98,
Nonmutagenic [20,
(parental and p. 265]
p. 562]
developmental)
Nonteratogenic [20,
Teratogenicity.
p. 562]
Rat (gavage): 240 mg kg−1 d−1 [98,
Noncarcinogenic [20,
(maternal and p. 265]
p. 562]
developmental)
NOEL/NOAEL:
Reproduction. Rabbit (gavage): 360 mg kg−1 d−1 [98,
(maternal and p. 265]
Rat (2-generation feed): ca. 10 mg kg−1 d−1 [20,
developmental)
p. 562]
Chronic.
Chronic.
Rat (2-year feed): 3.2 – 4.02 mg kg−1 d−1 [98,
Rat (2-year feed): ca. 6 mg kg−1 d−1 [20,
p. 265]
p. 562]
Mouse (2-year feed): < 6.7 mg kg−1 d−1 [98,
p. 265]
Dog (one-year feed): 2.87 – 3.17 mg kg−1 d−1 [98,
p. 265]
ADI: 0.03 mg kg−1 d−1 [98, p. 265]
38 Acaricides

Lufenuron [103055-0-8] NOEL/NOAEL:


Chronic.
LD50 (rat, oral) > 2000 mg/kg [20,
Rat (2-year feed): 1.4 mg kg−1 d−1 [20,
p. 753]
p. 1061]
LD50 (rat, dermal) > 2000 mg/kg [20, −1 −1
p. 753] Mouse (78-week feed): 0.81 mg kg d [20,
LC50 (rat, 4-h inhalation) > 2.35 mg/L air [20, p. 1061]
p. 753]
Rabbit: nonirritating to skin and eyes [20,
p. 753]
Guinea pig: not a skin sensitizer [20, Tebufenpyrad [119168-77-3]
p. 753]
Nonmutagenic [20, LD50 (rat, oral) 595 – 997 mg/kg [20,
p. 753] p. 1148]
NOEL/NOAEL: LD50 (mouse, oral) 210 – 224 mg/kg [20,
Chronic. p. 1148]
−1 −1
Rat (2-year feed): 2.0 mg kg d [20, LD50 (rat, dermal) > 2000 mg/kg [20,
p. 753] p. 1148]
LC50 (rat, 4-h inhalation) 2.66 – 3.1 mg/L air [20,
p. 1148]
Rabbit: nonirritating to skin [20,
Propargite [2312-35-8] p. 1148]
Rabbit: slightly irritating to eyes
LD50 (rat, oral) ∼ 2800 mg/kg [130, Guinea pig: not a skin sensitizer (guinea pig) [20,
p. 403] p. 1148]
LD50 (rabbit, oral) 311 mg/kg [130, Nonmutagenic [20,
p. 403] p. 1148]
LD50 (rabbit, dermal) 4000 mg/kg [130,
p. 403]
LC50 (rat, 4-h inhalation) 0.89 mg/L air [130,
p. 403]
Rabbit: severely irritating to skin and eyes [130,
p. 403] 5. References
Guinea pig: not a skin sensitizer (guinea pig) [130,
p. 403]
NOEL/NOAEL: General References
Reproduction. 1. R. Bovey, M. Bagglioni, A. Bolay, E. Bovay,
Rat (3-generation feed): 15 mg kg−1 d−1 [130, R. Corbaz, G. Mathys, A. Meylan, R.
(parental and p. 403]
developmental)
Murbach, F. Pelet, A. Savary, G. Trivelli: La
Teratogenicity. Défense des Plantes Cultivées, 7th ed., Payot,
Rat (gavage): 100 mg kg−1 d−1 [130, Lausanne 1979.
(maternal and p. 403]
developmental)
2. R. Gasser, Mitt. Schweiz. Entomol. Ges. 24
Chronic. (1957) 217.
Rat (2-year feed): 15 mg kg−1 d−1 [130, 3. T. H. Hughes: Mites or the Acari, University
p. 403] of London, The Athlone Press, London 1959.
−1 −1
Dog (one-year feed): 22 mg kg d [130,
p. 403] 4. J. E. Laing, Acarologia 11 (1969) 32.
ADI: 0.15 mg kg−1 d−1 [130, p. 403] 5. A. E. Pritchard, E. W. Baker: A Revision of the
Spider Mite, Family Tetranychidae, Pacific
Coast Entomological Society, San Francisco
Pyridaben [96489-71-3] 1955.

LD50 (rat, oral) 820 – 1350 mg/kg [20, Specific References


p. 1061]
LD50 (mouse, oral) 383 – 424 mg/kg [20, 6. F. Chaboussou, Z. Angew. Zool. 53 (1966) 257.
p. 1061] 7. F. Löcher, Z. Angew. Zool. 45 (1958) 201.
LD50 (rat, dermal) > 2000 mg/kg [20, 8. V. Dittrich, P. Streibert, P. A. Bathe, Environ.
p. 1061]
LD50 (rabbit, dermal) > 2000 mg/kg [20, Entomol. 3 (1974) 534.
p. 1061] 9. A. McMurtry, C. B. Huffaker, M. Van de Vrie,
LC50 (rat, 4-h inhalation) 0.62 – 0.66 mg/L air [20, Hilgardia 40 (1970) 331.
p. 1061]
Rabbit: nonirritating to skin and eyes [20, 10. M. Van de Vrie, J. A. McMurtry, C.
p. 1061] B. Huffaker, Hilgardia 41 (1972) 343.
Guinea pig: not a skin sensitizer (guinea pig) [20, 11. H. Grob, Mitt. Schweiz. Entomol. Ges. 24
p. 1061]
Nonmutagenic [20, (1951) 163.
p. 1061] 12. W. Kolbe, Erwerbsobstbau 10 (1968) 41.
Acaricides 39

13. D. A. Chant, Can. Entomol. 93 (1961) 437. 45. Stauffer, US 2 767 194, 1956 (L. W. Fancher).
14. C. B. Huffaker, M. Van de Vrie, J. 46. Novartis, BE 552 284, 1955 (E. Beriger, R.
A. McMurtry, Annu. Rev. Entomol. 14 (1969) Sallmann).
125. 47. Zeneca, GB 1 019 227, 1966 (G. V. McHattie).
15. U. Gerson, M. Van de Vrie, Proc. 4th Int. 48. Novartis, DE 2 249 462, 1973 (E. Beriger, J.
Congr. Acarology 1974, 629 – 635. Drabek).
16. C. R. Worthing: The Pesticide Manual, 6th 49. Novartis, NL 6 611 511, 1967.
ed., The British Crop Protection Council, 50. Bayer, DE 848 812, 1950 (G. Schrader, R.
Croydon, U.K., 1979. Mühlmann).
17. Ullmann, 4th ed., 7, 1. 51. Novartis, CH 319 579, 1953 (K. Lutz, O.
18. R. Wegler: Chemie der Pflanzenschutz- und Jucker).
Schädlingsbekämpfungsmittel, vol. 1, Springer, 52. AgrEvo, S. Afr. 68 08 471, 1968 (O. Scherer,
Berlin-Heidelberg-New York 1970. H. Mildenberger).
19. C. D. S. Tomlin: The Pesticide Manual, 10th 53. Rhône-Poulenc, BE 575 106, 1961 (J.
ed., British Crop Protection Council, Croydon Metivier).
1994. 54. H. Riedl, S. S. Hoying, J. Econ. Entomol. 73
20. C. D. S. Tomlin: The Pesticide Manual, 11th (1980) 117.
ed., British Crop Protection Council, 1997. 55. Roussel-UCLF, FR 2 486 073, 1982 (J. Martel,
21. Union Carbide, FR 1 377 474, 1965 (L. K. J. Tessier, A. Teche).
Payne, M. H. J. Weiden). 56. FMC, GB 2 085 005, 1982 (J. F. Engel).
22. Shell, US 3 116 201, 1960 (R. R. Whestone, D. 57. Sumitomo, DE 2 231 312, 1973 (T. Matsuo et
Harman). al.).
23. Dow, FR 1 360 901, 1964 (R. H. Rigterink). 58. Sumitomo, DE 2 335 347, 1974.
24. Novartis, DE 910 652, (H. Gysin, A. Margot). 59. Mitsui Zoatsu, DE 3 708 231, 1987 (S.
25. Shell, US 2 956 073, 1960 (R. R. Whestone, D. Numaka et al.).
Harman). 60. I. R. Harrison et al., Pestic. Sci. 3 (1972) 679;
26. Cyanamid, US 2 494 283, 1948 (J. T. Cassady, 4 (1973) 901.
E. I. Hoegberg). 61. I. R. Harrison, A. Kozlik, J. F. McCarthy, B. H.
27. Bayer, DE 917 668, 1952 (W. Lorenz). Palmer, D. M. Weighton, Meded. Fac.
28. Du Pont, US 2 503 390, 1952 (A. G. Jenkins). Landbouwwet Rijksuniv. Gent. 37 (1972) 765.
29. Food Machenery and Chem. Corp., 62. AgrEvo, DE 1 169 194, 1962 (H. Peissker, A.
US 2 873 228, 1959 (J. L. Willard, J. F. Jäger, W. Steinhausen, G. Boroschewski).
Henahan). 63. Murphy Chem., GB 1 019 451, 1961 (M.
30. H. Ogawa, Jpn. Pest. Info 1985, 11. Pianka, D. J. Polton).
31. Novartis, DE 1 148 806, 1960 (K. Lutz, M. 64. Rohm & Haas Co., US 2 526 660, 1946, (W. F.
Schuler). Hester, W. E. Craig).
32. M. Pinda, Chem. and Ind. 1961, 324. 65. R. D. Clifford, D. A. M. Watkins, D.
33. Novartis, DE 2 119 488, 1971 (E. Beriger). Woodcock, Chem. Ind. (London) 1965, 1654.
34. Bayer, NL 6 508 556, 1966. 66. U.S. Dept. Agriculture, Agricultural Research
35. K. Rüfenach (Novartis), Helv. Chim. Acta Division, Method 580-0.
(1968) 518. 67. N. V. Philips’ Gloeilampenfabrieken, DE
36. Bayer, US 912 895, 1962 (E. Schegk, G.
1 023 761, 1958 (J. Meltzer, H. O. Huisman).
Schrader, K. Wedemeyer).
68. Agripat, CH 471 065, 1965 (K. Gubler).
37. Du Pont, US 3 576 834, 1971 (J. B. Buchanan).
69. S. Reuter, K. R. S. Ascher, Experientia 12
38. Shell, US 2 685 552, 1952 (a. R. Stiles).
(1956) 316.
39. Novartis, US 2 908 605, 1959 (E. Beriger, R.
70. Rohm & Haas Co., US 2 812 280, 1954 (H.
Sallmann).
F. Wilson, E. Y. Shropshire, W. E. Craig).
40. Bayer, DE 1 251 304, 1962 (G. Oertl, A.
71. I. Hamman, K. H. Büchel, K. Bungarz, L.
Dörken).
Born, Pflanzenschutz Nachr. 31 (1978) 60.
41. Du Pont, US 3 530 220, 1968 (J. B. Buchanan).
72. E. Krause, R. Pohland, Ber. Dtsch. Chem. Ges.
42. Bayer, DE 1 011 416, 1955 (G. Schrader).
57 (1924) 532.
43. Cyanamid, US 2 586 655, 1948 (E. O. Hook,
73. W. E. Allison, A. E. Doty, J. L. Hardy, E. E.
Ph. H. Moss).
Kenaga, W. K. Whitney, J. Econ. Entomol. 61
44. Rhône-Poulenc, FR 1 482 025, 1966 (J.
(1968) 1254.
Metivier).
40 Acaricides

74. H. Zimmer, I. A. Hornberg, M. Jayawant, J. 105. Pesticide Residues in Food-1986, FAO Plant
Org. Chem. 31 (1966) 3857. Prod. Prot. Paper 78/2 (1987).
75. J. Putter et al., Exoerientia, 37 (1981) 963. 106. Pesticide Residues in Food-1980, FAO Plant
76. K. K. Siccama, R. Heynderickx, M. Asada En, Prod. Prot. Paper 26 Sup. (1981).
H. F. A. de Lange, Meded. Fac. Landbouwwet. 107. Pesticide Residues in Food-1987, FAO Plant
Rijksuniv. Gent. 42 (1977) 1479. Prod. Prot. Paper 84 (1987).
77. Nihon Noyaku, DE 2 824 126, 1978 (K. Ikeda, 108. 1972 Evaluations of some Pesticide Residues
H. Kanno, M. Yasui, T. Harada). in Food, WHO Pesticide Residues Series, No.
78. Novartis, DE 2 619 724, 1976 (D. Duerr, W. D. 2 (1973).
Traber). 109. 1975 Evaluations of some Pesticide Residues
79. Bayer, DE 1 088 965, 1958 (K. Sasse, R. in Food, WHO Pesticide Residues Series, No.
Wegler, G. Unterstenhöfer). 5 (1976).
80. K. Sasse, R. Wegler, G. Unterstenhöfer, F. 110. Pesticide Residues in Food-1985, FAO Plant
Grewe, Angew. Chem. 72 (1960) 973. Prod. Prot. Paper 72/2 (1986).
111. G. L. Kennedy, Fundam. Appl. Toxicol. 6
81. Fisons, EP 5 912, 1979 (J. H. Persens).
(1986) 423.
82. Hooker Chemical Corp., US 2 908 723, 1959
112. Pesticide Residues in Food-1984, FAO Plant
(J. T. Rucker).
Prod. Prot. Paper 62 (1985).
83. Hooker Chemical Corp., US 2 934 470, 1960 113. WHO/PCS/95.2 (1995).
(J. T. Rucker). 114. Regulatory Affairs Department, SDS Biotech
84. AgrEvo, DE 1 015 797, 1954. K. K., J. Pesticide Sci. 16 (1991) 337.
85. Lilly Eli, EP 380 264, 1950 (W. I. Glaisby). 115. 1973 Evaluations of some Pesticide Residues
86. Nihon Noyaku, EP 234 945, 1987 (H. R. M. F. in Food, WHO Pesticide Residues Series, No.
Hamaguchi et al.). 3 (1973).
87. Duphar, EP 117 320, 1984 (M. S. Brouwer, 116. Industrieverband Agrar e.V. Frankfurt (M.):
A. C. Grosscourt). “Physikalisch-chemische und toxikologische
88. Shell, US 161 019, 1985 (M. Anderson). Daten”,Wirkstoffe in Pflanzenschutz- und
89. Nippon, DE 3 037 105, 1981 (I. Iwakaki, M. Schädlingsbekämpfungsmitteln, 2nd ed.,
Kaeriyama, N. Matsui). Frankfurt (Main) 1990, p. 50.
90. Novartis, EP 179 022, 1986 .(J. Drabek, M. 117. Pesticide Residues in Food-1988, FAO Plant
Boeger). Prod. Prot. Paper 93/2 (1989).
91. U.S. Rubber Co., US 3 272 854, 1963 (R. 118. “Fenvalerate”, WHO Environmental Health
A. Covey, A. E. Smith, W. L. Hubbard). Criteria 95 (1990).
92. Nissan, JP 62 67 076, 1987 (H. Suzuki, M. 119. Pesticide Residues in Food-1979, FAO Plant
Kawashima, Z. Ogura). Prod. Prot. Paper 20 Sup. (1980).
93. Mitsubishi, EP 289 879, 1988 (I. Okada, S. 120. C. M. Parker, D. R. Patterson, G. A. van Gelder,
Okui, Y. Takahashi, T. Fukuchi). F. B. Gordon, M. G. Valerio, W. C. Hall, J.
94. C. D. Klassen, M. O. Amdur, J. Doull (eds.): Toxicol. Environm. Health 13 (1984) 83.
Casarret and Doull’s Toxicology, 3rd ed., 121. Y. Okuno, S. Ito, T. Seki, T. Hiromori, M.
Macmillan Publ. Co., New York 1986 p. 556. Murakami, T. Kadota, J. Miyamoto, J. Toxicol.
95. R. L. Baron, T. L. Merriam, revs. Environm. Sci. 11 (1986) 53.
Contaim. Toxicol. 105 (1988) 1. 122. Pesticide Residues in Food-1986, FAO Plant
96. WHO/PCS/93.34 (1993). Prod. Prot. Paper 77 (1986).
97. WHO/PCS/95.2 (1995). 123. Pesticide Residues in Food-1990, FAO Plant
98. WHO/PCS/92.52 (1992). Prod. Prot. Paper 102 (1990).
99. WHO/PCS/94.4 (1994). 124. T. B. Gaines, Toxicol. Appl. Pharmacol. 14
100. W. J. Hayes, E. R. Laws (eds.): Handbook of (1969) 515.
125. NIOSH Registry: Tracor Jitco. U.S.
Pesticide Toxicology, Academic Press, New
Government Printing Office, Washington, DC,
York 1991.
1982.
101. “Dimethoate”, WHO Environmental Health
126. R. T. Meister (ed.): Farm Chemical Handbook,
Criteria 90 (1989).
Meister Publishing Co., Willoughby, Ohio,
102. Pesticide Residues in Food-1987, FAO Plant
1980 – 1982.
Prod. Prot. Paper 86/2 (1988). 127. H. Martin, C. R. Worthing (eds.): Pesticide
103. WHO/PCS/92.52 (1992) 151. Manual, 5th ed., British Crop Protection
104. WHO/PCS/91.47 (1991). Council, Croydon1977.
Acaricides 41

128. Pesticide Residues in Food-1991, FAO Plant 4 (1975).


Prod. Prot. Paper 111 (1991). 132. “Endosulfan”, WHO Environmental Health
129. Pesticide Residues in Food-1989, FAO Plant Criteria 40 (1984).
Prod. Prot. Paper 100/2 (1990). 133. Pesticide Residues in Food-1995, FAO Plant
130. Pesticide Residues in Food-1977, FAO Plant Prod. Prot. Paper 133 (1996) 86.
Prod. Prot. Paper 10 Sup. (1978). 134. T. Tsuda, J. Tamura, H. Ueda, I. Ichimoto, J.
131. 1974 Evaluations of some Pesticide Residues Pesticide Sci. 17 (1992) 261.
in Food, WHO Pesticides Residues Series No.

Accumulators → Batteries
Acenaphthene → Hydrocarbons
Acetaldehyde 1

Acetaldehyde
Marc Eckert, Wacker Chemie AG, Werk Burghausen, Germany
Gerald Fleischmann, Wacker Chemie AG, Werk Burghausen, Germany (Chap. 1, 2, 3, 4, 5, 6, 7 and 8)
Reinhard Jira, Wacker Chemie AG, Werk Burghausen, Germany (Chap. 1, 2, 3, 4, 5, 6, 7 and 8)
Hermann M. Bolt, Institut für Arbeitsphysiologie an der Universität Dortmund, Dortmund, Germany
(Chap. 9)
Klaus Golka, Institut für Arbeitsphysiologie an der Universität Dortmund, Dortmund, Germany (Chap. 9)

1. Introduction . . . . . . . . . . . . . . . 1 4.3.3. Isomerization of Ethylene Oxide . . . 10


2. Physical Properties . . . . . . . . . . . 2 4.4. Production from C1 Sources . . . . . 11
3. Chemical Properties and Uses . . . . 3 4.5. Production from Hydrocarbons . . 11
3.1. Addition Reactions . . . . . . . . . . . 3 5. Quality and Analysis . . . . . . . . . . 11
3.2. Derivatives of Aldol Addition . . . . 3 6. Storage and Transportation . . . . . 11
3.3. Reaction with Nitrogen Compounds 3 6.1. Storage . . . . . . . . . . . . . . . . . . . 11
3.4. Oxidation . . . . . . . . . . . . . . . . . 4 6.2. Transportation . . . . . . . . . . . . . . 12
3.5. Reduction . . . . . . . . . . . . . . . . . 4 6.3. Other Regulations . . . . . . . . . . . 12
3.6. Miscellaneous Reactions . . . . . . . 4
7. Economic Aspects . . . . . . . . . . . . 12
3.7. Consumption . . . . . . . . . . . . . . . 4
8. Polymers of Acetaldehyde . . . . . . 13
4. Production . . . . . . . . . . . . . . . . 4
4.1. Production from Ethanol . . . . . . . 5 8.1. Paraldehyde . . . . . . . . . . . . . . . 13
4.2. Production from Acetylene . . . . . . 6 8.2. Metaldehyde . . . . . . . . . . . . . . . 13
4.3. Production from Ethylene . . . . . . 7 8.3. Polyacetaldehyde . . . . . . . . . . . . 14
4.3.1. Direct Oxidation of Ethylene . . . . . 7 9. Toxicology and Occupational Health 14
4.3.2. Acetaldehyde as Byproduct . . . . . . 10 10. References . . . . . . . . . . . . . . . . . 15

1. Introduction acetic acid between 1914 and 1918 in Germany


(Wacker-Chemie and Hoechst) and in Canada
Acetaldehyde (ethanal), CH3 CHO [75-07-0], (Shawinigan).
was observed in 1774 by Scheele during re- Acetaldehyde is an intermediate in the
action of black manganese dioxide and sulfuric metabolism of plant and animal organisms, in
acid with alcohol. Its constitution was explained which it can be detected in small amounts.
in 1835 by Liebig who prepared pure acetalde- Larger amounts of acetaldehyde interfere with
hyde by oxidation of ethanol with chromic acid biological processes. As an intermediate in al-
and designated this product “aldehyde,” a con- coholic fermentation processes it is present in
traction of the term “alcohol dehydrogenatus.” small amounts in all alcoholic beverages, such
Acetaldehyde is a mobile, low-boiling, as beer, wine, and spirits. Acetaldehyde also has
highly flammable liquid with a pungent odor. been detected in plant juices and essential oils,
Because of its high chemical reactivity, acet- roasted coffee, and tobacco smoke.
aldehyde is an important intermediate in Commercial production processes include
the production of acetic acid, acetic anhy- dehydrogenation or oxidation of ethanol, addi-
dride, ethyl acetate, peracetic acid, butanol, 2- tion of water to acetylene, partial oxidation of
ethylhexanol, pentaerythritol, chlorinated acet- hydrocarbons, and direct oxidation of ethylene.
aldehydes (chloral), glyoxal, alkyl amines, pyri- In the 1970s, the world capacity of this last pro-
dines, and other chemicals. The first commercial cess, the Wacker-Hoechst direct oxidation, in-
application was the production of acetone via creased to over 2×106 t/a. However, the impor-

c 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 031.pub2
2 Acetaldehyde
Heat capacity of liquid
tance of acetaldehyde as an organic intermediate
cp (l) at 0 ◦ C 2.18 J g−1 K−1
is now steadily decreasing, because new pro- at 20 ◦ C 1.38 J g−1 K−1
cesses for some acetaldehyde derivatives have For further values between −80 ◦ C (cp = 1.24 J g−1 K−1 )
been developed, such as the oxo process for and +120 ◦ C (cp = 1.50 J g−1 K−1 ), see [17].
Heat capacity of vapor
butanol and 2-ethylhexanol and the Monsanto
cp (g) at 25 ◦ C, 101.3 1.24 J g−1 K−1
process for acetic acid. In the future, new pro- kPa
cesses for acetic anhydride (Halcon, Eastman, For dependence on temperature (nonlinear) between 0 ◦ C (cp
Hoechst), for vinyl acetate (Halcon), and for = 1.17 J g−1 K−1 ) and 1000 ◦ C (cp = 2.64 J g−1 K−1 ), see
[17].
alkyl amines (from ethanol) will diminish the
use of acetaldehyde as a starting material. cp /cv (= κ) at 30 ◦ C, 1.145 [18]
101.3 kPa
Thermal conductivity
of liquid at 20 ◦ C 0.174 J m−1 s−1 K−1 ;
for more values, see
2. Physical Properties [19]
of vapor at 25 ◦ C 1.09×10−2 J m−1 s−1 K−1
Acetaldehyde, C2 H4 O, M r 44.054, is a color- for further values,
see [20].
less liquid with a pungent, suffocating odor that Cubic expansion 0.00169
is slightly fruity when diluted. coefficient per K (0 –

20 C)
Heat of combustion of 1168.79 (1166.4 [12]) kJ/mol
bp at 101.3 kPa 20.16 ◦ C liquid at constant p
mp –123.5 ◦ C Heat of solution in water 17 906 J/mol
Critical temperature t crit 181.5 ◦ C (infinite dilution)
other values 187.8 ◦ C [12], 195.7 ◦ C [13] Latent heat of fusion 3246.3 J/mol
Critical pressure pcrit 6.44 MPa Latent heat of 25.73 kJ/mol
other values 5.54 MPa [12], 7.19 MPa [13] vaporization at 20.2 ◦ C
Relative density d4 = 0.8045−0.001325·t (t in ◦ C)
t
other values 27.2 [21], 30.41, 27.71 [12], 26.11 [22]
[3] kJ/mol
Refractive index ntD = 1.34240−0.0005635·t (t in For dependence on temperature (nonlinear) between -80 ◦ C

C) [14] (32.46 kJ/mol) and 182 ◦ C (0 kJ/mol), see [17].
Molar volume of the gas Heat of formation ∆H from the elements at 25 ◦ C for gaseous
at 101.3 kPa and 23.40 L/mol acetaldehyde
20.16 ◦ C −166.47 (−166.4 [21]) kJ/mol

at 25.0 C 23.84 L/mol For dependence of heat of formation for gaseous and liquid
For dependence on T (293.32 – 800 K) and p (0.1 – 30 acetaldehyde, and enthalpy of vaporization on temperature up to
MPa), see [15]. 800 K and 30 MPa, see [15].
Specific volume of the Gibbs free energy of formation ∆G from elements
vapor at 25 ◦ C for gaseous −133.81 kJ/mol
at 20.16 ◦ C 0.531 m3 /kg acetaldehyde
at 25.0 ◦ C 0.541 m3 /kg other values 133.72 [12], 132.9 [21] kJ/mol
Vapor density (air = 1) 1.52 Entropy for gaseous acetaldehyde

Vapor pressure at 25 C 265.9 J mol−1 K−1
t, ◦ C −20 −0.27 5.17 14.76 50 100 Entropy for liquid acetaldehyde
p, kPa 16.4 43.3 67.6 82.0 279.4 1014.0 at 20.16 ◦ C 172.9 J mol−1 K−1
Entropy of vaporization
For further values between −60 and +180 ◦ C, see [14]
at 20.16 ◦ C 91.57 J mol−1 K−1
Viscosity of liquid η First ionization potential 10.5 eV
at 9.5 ◦ C 0.253 mPa · s Dissociation constant at 0.7×10−14 mol/L
at 20 ◦ C 0.21 mPa · s 0 ◦C (H3 CCHO− H2 CCHO + H+ )
Viscosity of vapor η For the second virial coefficient of the equation of state for gaseous
at 25 ◦ C 86×10−4 mPa · s acetaldehyde at 31 ◦ C, 66 ◦ C, and 85 ◦ C, see [23].


For further values between 35.0 and 77.8 C and between 0.13 Acetaldehyde is completely miscible with
and 0.40 kPa, see [16].
Surface tension γ at 21.2×10−2 mN cm−1
water and most organic solvents. It forms no
20 ◦ C azeotrope with water, methanol, ethanol, ace-
Dipole moment (gas 2.69 ± 2 % D [12] tone, acetic acid, or benzene. Binary azeotropes
phase)
are formed with butane (bp −7 ◦ C, 84 wt % of
Dielectric constant butane) and diethyl ether (bp 18.9 ◦ C, 23.5 wt %
of liquid at 10 ◦ C 21.8
of vapor at 20.16 ◦ C, 1.0216
of ether).
101.3 kPa
Acetaldehyde 3

Other Physical Data. Compressibility and forms crystalline acetaldehyde ammonia. Acet-
viscosity at higher pressure are given in [24], va- aldehyde and hydrocyanic acid react to give lac-
por pressure of aqueous acetaldehyde solutions tonitrile (α-hydroxypropionitrile), a possible in-
in [25]. For solubility of carbon dioxide, acety- termediate in acrylonitrile production [30].
lene, and nitrogen in acetaldehyde, see [11]; for Acetaldehyde reacts with acetic anhydride to
freezing points of aqueous acetaldehyde solu- give ethylidene diacetate, an intermediate in the
tions, see [11]; for vapor – liquid equilibria of vinyl acetate process of Celanese Corp. [31] (→
binary systems of acetaldehyde with water, eth- Vinyl Esters).
anol, acetic acid, and ethylene oxide, see [26,
pp. 392, 561, 565, and 570], with vinyl acetate,
see [27]. 3.2. Derivatives of Aldol Addition
Two molecules of acetaldehyde combine in
Safety Data. Flash point (Abel – Pensky; the presence of alkaline catalysts or dilute
DIN 51 755; ASTM 56 – 70) −20 ◦ C (−40 ◦ C acids at room temperature or with mod-
according to the safety regulations of the Berufs- erate heating to form acetaldol [107-89-1],
genossenschaft der Chemischen Industrie, Fed- CH3 CH(OH)CH2 CHO. At increased temper-
eral Republic of Germany). Ignition tempera- atures, water is cleaved easily from this ac-
ture (DIN 51 794; ASTM D 2155 – 66) 140 ◦ C; etaldol, forming crotonaldehyde (→ Aldehydes,
for ignition retardation when injected into a hot Aliphatic and Araliphatic). Further condensa-
air stream, see [28]. Explosive limits in air: 4 – tion under more stringent conditions to form
57 vol %; for influence of pressure on explosive aldehyde resins (e.g., synthetic shellac) now has
limits, see [29]. no industrial importance.
Urea and acetaldehyde condense in the
presence of H2 SO4 to form crotonylidenedi-
3. Chemical Properties and Uses urea (6-methyl-4-ureidohexahydropyrimidin-2-
one [1129-42-6]), which is used as a long-term
Acetaldehyde is a highly reactive compound nitrogen fertilizer (→ Fertilizers).
showing all of the typical aldehyde reactions as Acetaldehyde is also an intermediate in the
well as those of an alkyl group in which hydro- butadiene synthesis starting from acetylene and
gen atoms are activated by the carbonyl group in proceeding via acetaldol and its hydrogenation
the α position. When heated above 420 ◦ C acet- product, 1,3-butanediol [32]. This process was
aldehyde decomposes into methane and carbon introduced around 1918 and is still carried out
monoxide. on a commercial scale in some Eastern European
countries.
Acrolein is obtained by aldol condensation
3.1. Addition Reactions of acetaldehyde and formaldehyde and subse-
quent water elimination, analogous to the for-
With water, acetaldehyde forms an unstable mation of crotonaldehyde. This method is also
hydrate; isolable solid hydrates are known without commercial importance today, whereas
only with chlorinated acetaldehydes. Alcohols the production of pentaerythritol from acetalde-
add to acetaldehyde giving hemiacetals, which hyde and a fourfold amount of formaldehyde in
form acetals (→ Aldehydes, Aliphatic and Ar- the presence of Ca(OH)2 or NaOH is very im-
aliphatic) with additional alcohol in the presence portant industrially (→ Alcohols, Polyhydric).
of acids by removal of water. Diols give cyclic
acetals; for example, 2-methyl-1,3-dioxolane is
obtained from ethylene glycol and acetalde- 3.3. Reaction with Nitrogen Compounds
hyde, and 2-methyl-1,3-dioxane from 1,3-pro- With primary amines, Schiff bases,
panediol. CH3 CH=NR, are formed. Nitrogen compounds
Aqueous sodium bisulfite solution and acet- such as hydroxylamine, hydrazine, phenylhy-
aldehyde give a crystalline adduct from which drazine, and semicarbazide react with acetal-
acetaldehyde can be liberated. Dry ammonia dehyde to give easily crystallizable compounds
4 Acetaldehyde

that are used for the analytical determination 3.5. Reduction


and characterization of aldehydes (semicar-
bazone, mp 162 – 163 ◦ C; p-nitrophenylhy- Acetaldehyde is hydrogenated readily to etha-
drazone, mp 128.5 ◦ C; 2,4-dinitrophenylhydra- nol. Prior to 1939, that is, before petrochemically
zone, mp 168 ◦ C; oxime, mp 47 ◦ C). Many other produced ethylene became available in Europe,
aldehydes and ketones can be characterized in this reaction was used industrially to produce
the same way because their analogous deriva- ethanol from acetaldehyde and, therefore, from
tives generally have sharp melting points. acetylene.
The synthesis of pyridine and pyridine Mono-, di-, and triethylamine [75-04-7],
derivatives is of increasing importance. 5-Ethyl- [109-89-7], [121-44-8] can be produced from
2-methylpyridine is obtained in the presence of acetaldehyde, ammonia, and hydrogen in the
fluoride ions by the reaction of aqueous am- presence of a hydrogenation catalyst [33] (→
monia with acetaldehyde (or with paraldehyde, Amines, Aliphatic).
which slowly releases the monomer). In the
added presence of formaldehyde or acrolein,
mixtures of pyridine and alkylpyridines form (→ 3.6. Miscellaneous Reactions
Pyridine and Pyridine Derivatives).
The Tishchenko reaction of acetaldehyde gives
the commercially important solvent ethyl acetate
3.4. Oxidation (→ Acetic Acid); it is catalyzed by aluminum al-
coholate.
The major part of the acetaldehyde produced As a “radical trapping agent,” acetaldehyde
commercially is used for manufacturing acetic is used to control chain length in the polymer-
acid by oxidation with oxygen or air (→ Acetic ization of vinyl compounds.
Acid). Acetaldehyde monoperacetate is formed Oligomers of acetaldehyde are treated in
as an intermediate and decomposes into per- Chapter 8.
acetic acid and acetaldehyde at elevated temper-
atures and in the presence of catalytic amounts
of iron or cobalt salts. In the presence of Mn2+ 3.7. Consumption
salts, acetic acid is obtained from acetaldehyde
monoperacetate, and in the presence of Co2+ The consumption of acetaldehyde has changed
and Cu2+ salts, acetic anhydride can be formed. during the last few years. Since 1993 in the USA,
Oxidation with nitric acid gives glyoxal acetaldehyde is no longer used for the produc-
(→Glyoxal and → Glyoxylic Acid). Halo- tion of acetic acid, butanol, or 2-ethylhexanol,
genated acetaldehydes are prepared by halo- which are now produced by other routes (Table
genation. 1). The consumption of acetaldehyde for some
other chemicals like peracetic acid or pyridine
bases is increasing.

4. Production
Raw materials that have been used for the pro-
duction of acetaldehyde are:

Mono-, di-, and trichloroacetaldehydes (→ 1) Ethanol from fermentation of carbohydrates


Chloroacetaldehydes) and tribromoacetalde- or from hydration of ethylene
hyde (bromal) are useful for producing insec- 2) Acetylene
ticides (e.g., DDT, DDD), pharmaceuticals, and 3) Ethylene
dyes. 4) Lower hydrocarbons
5) Carbon monoxide and hydrogen
6) Methanol
Acetaldehyde 5
Table 1. Consumption of acetaldehyde (103 t) in 2003 [56]

Product USA Mexico W. Europe Japan Total


Acetic acid/acetic anhydride 11 89 47 147
Acetate esters 35 8 54 224 321
Pentaerythritol 26 43 11 80
Pyridine and pyridine bases 73 10 * 83
Peracetic acid 23 * 23
1,3-Butylene glycol 14 * 14
Others 5 3 10 80 98
Total 176 22 206 362 766
* Included in others (glyoxal/glyoxalic acid, crotonaldehyde, lactic acid, n-butanol, 2-ethylhexanol).

The economy of the commercial processes 4.1. Production from Ethanol


depends essentially upon prices and the avail-
ability of raw materials. In highly industrialized For the production of acetaldehyde, ethanol can
countries maintaining high prices for ethanol by either be dehydrogenated or oxidized in the pres-
fiscal measures or where petrochemical ethanol ence of oxygen. Between 1918 and 1939, dehy-
was not available, as in Germany or Japan before drogenation took precedence over oxidation be-
1939, acetylene was the favored starting mate- cause of the simultaneous production of hydro-
rial for acetaldehyde. The acetylene process is gen. Later, however, the catalytic vapor-phase
still operated in some Eastern European coun- oxidation of ethanol became the preferred pro-
tries and also by companies where cheap acety- cess, probably because of the long catalyst life
lene is available. Petrochemically produced eth- and the possibility of recovering energy.
anol, however, was the favored raw material in
the other countries, whereas ethanol made by Dehydrogenation of Ethanol. In the first
fermentation was and still is used on a small work on ethanol dehydrogenation, published in
scale in countries with less chemical industry. 1886, ethanol was passed through glass tubes at
In Western countries, including Japan, all 260 ◦ C.
these processes have now been almost com- CH3 CH2 OH (l) →CH3 CHO (l) +H2 (g)
pletely replaced by the direct oxidation process ∆H = +82.5 kJ/mol
developed in the late 1950s by Wacker-Chemie
and Hoechst. This is because ethylene is avail- Improved yields are obtained in the presence
able at a lower price than acetylene. of catalysts such as platinum, copper, or oxides
Even the two-stage processes using ethanol of zinc, nickel, or cobalt. In later patents, zinc
from ethylene as starting material are no longer and chromium catalysts [34], oxides of rare earth
competitive because of the decreasing impor- metals [35], and mixtures of copper and chromi-
tance of acetaldehyde as an organic intermediate um oxides [36] have been reported. The lowest
(see Chap. 7). amounts of decomposition products are obtained
Generally, all processes based on acetylene, using copper catalysts. Frequent regeneration of
ethylene, and ethanol are more selective than the the catalysts is required, however.
oxidation of saturated hydrocarbons. This is be- Process Description. Ethanol vapor is
cause, in the latter case, other oxidation products passed at 260 – 290 ◦ C over a catalyst consist-
are formed in addition to acetaldehyde. Because ing of copper sponge or copper activated with
of the great expense of separating the product chromium oxide in a tubular reactor [37]. A con-
mixture, such processes are economical only in version of 25 – 50 % per run is obtained. By
large units and when all main and secondary washing with alcohol and water, acetaldehyde
products obtained in the process are utilized. and ethanol are separated from the exhaust gas,
which is mainly hydrogen. Pure acetaldehyde
is obtained by distillation; the ethanol is sepa-
rated from water and higher-boiling products by
6 Acetaldehyde

distillation and flows back to the reactor. The fi- The waste gas consists mainly of nitrogen,
nal acetaldehyde yield is ca. 90 %. Byproducts hydrogen, methane, carbon monoxide and car-
include butyric acid, crotonaldehyde, and ethyl bon dioxide; it is burned as lean gas with
acetate. low calorific value in steam generators. Small
amounts of acetic acid are obtained as a byprod-
Oxidation of Ethanol. Oxidation of ethanol uct.
is the oldest and the best laboratory method for
preparing acetaldehyde. In the commercial pro-
cess, ethanol is oxidized catalytically with oxy- 4.2. Production from Acetylene
gen (or air) in the vapor phase.
The most important catalysts for the industrial
CH3 CH2 OH (g) +1/2O2 (g) →CH3 CHO (l) +H2 O (l)
water addition (hydration) are mercury com-
∆H = −242.0kJ/mol
pounds:
Copper, silver, and their oxides or alloys are
the most frequently used catalysts [38].
For an example of a simultaneous oxidation
– dehydrogenation process, see [39].

Veba-Chemie Process (Fig. 1). Ethanol is This method only succeeds industrially when
mixed with air and passed over a silver catalyst the polymerization and condensation products
at 500 – 650 ◦ C (c). The temperature depends of acetaldehyde formed in the acid medium
on the ratio of alcohol to air and the flow rate are eliminated. To achieve this, the Consor-
of the gas through the catalyst. Alcohol conver- tium für elektrochemische Industrie in 1912 pro-
sion varies between 50 and 70 % and the yield posed a process using excess acetylene at an
is between 97 and 99 % depending on the reac- elevated temperature and removing the acetal-
tion conditions. Acetaldehyde and unconverted dehyde product immediately from the reaction
alcohol are removed from the waste gas by wash- liquid. At the same time, the heat of reaction
ing with cold alcohol (e) and separated by frac- is removed by distilling an appropriate amount
tional distillation (h); after concentration the al- of water. Secondary reactions, such as the oxi-
cohol returns to the reactor. Heat formed in the dation of acetaldehyde to form acetic acid and
reaction is utilized for steam production using carbon dioxide, result in reduction of Hg2+ to
a waste-heat recovery system immediately after metallic mercury. In Western countries, acetal-
the reaction zone. dehyde production from acetylene has now been
discontinued.

Wet Oxidation Process (Hoechst). The wet


oxidation process avoided direct handling of
the toxic mercury compounds. It was oper-
ated, among others, by Wacker-Chemie until the
changeover to ethylene as the starting material
in 1962.
In this method, iron(III) sulfate is added to
reoxidize the mercury metal to the mercury(II)
salt, thus ensuring sufficient concentrations of
active catalyst. The acetylene reacts at 90 –
95 ◦ C with the aqueous catalyst solution; bet-
ween 30 and 50 % of the injected acetylene re-
Figure 1. Acetaldehyde production by the Veba-Chemie
process acts in one run. The gas emerging from the reac-
a) Air compressor; b) Heat recovery system; c) Reactor; tor is cooled; mainly water and traces of mercury
d) Cooler; e) Waste-gas scrubber; f) Washing-alcohol and are separated and returned to the reactor. Acet-
return pump; g) Cooler; h) Acetaldehyde rectification aldehyde and water are condensed in additional
coolers and the acetaldehyde finally is washed
Acetaldehyde 7

out with water from the cycle gas which has been 4.3. Production from Ethylene
cooled to 25 – 30 ◦ C. An 8 – 10 % aqueous acet-
aldehyde solution is obtained. Nitrogen is intro- Ethylene is now the most important starting ma-
duced with the feed gas while carbon dioxide is terial for the production of acetaldehyde. Most
formed as a byproduct; to avoid excessive accu- of the present capacity works by the direct oxi-
mulation, these gases are removed by withdraw- dation of ethylene (Wacker process).
ing a small stream of the cycle gas. Iron(II) sul-
fate is formed in the reaction and is oxidized in
a separate reactor with 30 % nitric acid at 95 ◦ C. 4.3.1. Direct Oxidation of Ethylene
Pure acetaldehyde is obtained by fractional dis-
tillation of the aqueous solution at about 200 This process was developed between 1957 and
kPa. For further details of this process, see [40]. 1959 by Wacker-Chemie and Hoechst [42]. For-
mally, the reaction proceeds as follows:
Chisso Process [41]. The Chisso process
C2 H4 +1/2O2 →CH3 CHO∆H = −244 kJ/mol
also uses sulfuric acid/mercury sulfate solution
as a catalyst. The acetylene reacts completely An aqueous solution of PdCl2 and CuCl2 is
with the catalyst solution at 68 – 78 ◦ C and a used as catalyst. Acetaldehyde formation had
gauge pressure of 140 kPa. A combination of already been observed in the reaction between
pressure and vacuum process stages at low tem- ethylene and aqueous palladium chloride. This
perature and without excess acetylene is used; reaction is almost quantitative:
pure acetaldehyde can be isolated and distilled
by utilizing the heat of the reaction. As in the C2 H4 +PdCl2 +H2 O→CH3 CHO+Pd+2HCl
Hoechst process, the catalyst can be regenerated
In the Wacker-Hoechst process, metallic pal-
with nitric acid. Production of acetaldehyde by
ladium is reoxidized by CuCl2 , which is then
this method was discontinued at Chisso Corp.
regenerated with oxygen:
more than a decade ago.
Pd+2CuCl2 →PdCl2 +2CuCl
Production via Vinyl Ether. Reppe at
BASF developed the process using vinyl ether 2CuCl+1/2O2 +2HCl→2CuCl2 +H2 O
[40]; it was operated in a pilot plant between
1939 and 1945. The use of toxic mercury com- Therefore only a very small amount of PdCl2
pounds is avoided altogether. Methanol is added is required for the conversion of ethylene. The
to acetylene at 150 – 160 ◦ C and 1600 kPa in reaction of ethylene with palladium chloride is
the presence of potassium hydroxide to form the rate-determining step.
methyl vinyl ether [107-25-5]. The methyl vinyl One- and two-stage versions of the process
ether is then hydrolyzed with dilute acid: are on stream. In the one-stage method, an eth-
ylene – oxygen mixture reacts with the catalyst
solution. During the reaction a stationary state
is established in which “reaction” (formation of
acetaldehyde and reduction of CuCl2 ) and “ox-
Production via Ethylidene Diacetate. Ad- idation” (reoxidation of CuCl) proceed at the
dition of acetic acid to acetylene in the pres- same rate. This stationary state is determined
ence of mercury(II) salts yields ethylidene di- by the degree of oxidation of the catalyst, as ex-
acetate [542-10-9], CH3 CH(OCOCH3 )2 , which pressed by the ratio cCu2+ / (cCu2+ +cCu+ ). In the
decomposes into acetaldehyde and acetic anhy- two-stage process the reaction is carried out with
dride at 130 – 145 ◦ C in the presence of acid cat- ethylene and then with oxygen in two separate
alysts (e.g., ZnCl2 ). This process was developed reactors. The catalyst solution is alternately re-
by the Societe Chimique des Usines du Rhône duced and oxidized. At the same time the degree
on an industrial scale in 1914 but is now without of oxidation of the catalyst changes alternately.
importance. Air is used instead of pure oxygen for the cata-
lyst oxidation.
8 Acetaldehyde

Reaction Mechanism. The first step of the re-


action is the complexation of ethylene to give a
palladium ethylene complex
The rate of reaction is diminished by the acid
[PdCl4 ]2− +H2 C = CH2 [(C2 H4 ) PdCl3 ]− +Cl− formed in the reduction of palladium chloride.
This can be prevented by buffering the acid with
Kinetic studies of this reaction show that
basic copper salts (copper oxychloride, copper
chloride ions have a inhibiting effect which is
acetate). Reformation of the basic copper salts
explained by the following substitution of a fur-
takes place during catalyst oxidation.
ther chloride ligand by a water molecule:
One-Stage Process (Fig. 2). Ethylene and
[(C2 H4 ) PdCl3 ]− +H2 O [(C2 H4 ) PdCl2 (H2 O)] +Cl− oxygen are charged into the lower part of the re-
action tower (a); the catalyst is circulated via the
Dissociation of hydrogen ions explains the separating vessel (b) by the airlift principle and
inhibiting effect of acids: thoroughly mixed with the gas. Reaction con-
ditions are about 130 ◦ C and 400 kPa. An acet-
[(C2 H4 ) PdCl2 (H2 O)] [(C2 H4 ) PdCl2 (OH)]− +H+
aldehyde – water vapor mixture, together with
It is assumed that the hydroxyl complex has unconverted gas, is withdrawn from the separat-
the trans geometry. Evidence for the trans – cis ing vessel; from this mixture the reaction prod-
isomerisation of this complex was revealed by a ucts are separated by cooling (c) and washing
detailed kinetic study of the reaction. π-Bonded with water (d); unconverted gas is returned to
ethylene ligands in the trans position weaken the the reactor. A small portion is discharged from
metal – chlorine bonds, so that the chloro ligand the cycle gas as exhaust gas to prevent accumu-
can be easily substituted by a water molecule lation of inert gases in the cycle gas; these inert
from which a hydrogen ion dissociates. gases are either introduced as contamination of
the feed gas (nitrogen, inert hydrocarbons) or
trans−[(C2 H4 ) PdCl2 (OH)]− +H2 O
 − formed as byproducts (carbon dioxide). A par-
(C2 H4 ) PdCl(OH)2 +H+ +Cl− tial stream of catalyst is heated to 160 ◦ C (m) to
The OH− ligand in the trans position is re- decompose byproducts that have accumulated in
placed by a Cl− ion, leading to a cis complex: the catalyst.
 −
Crude acetaldehyde obtained during washing
(C2 H4 ) PdCl(OH)2 +H+ +Cl−  of the reaction products is distilled in two stages.
cis−[(C2 H4 ) PdCl2 (OH)]− +H2 O The first stage (g) is an extractive distillation
with water in which lights ends having lower
The next reaction step is the formation of a
boiling points than acetaldehyde (chlorometh-
σ-bonded hydroxyethylpalladium species. This
ane, chloroethane, and carbon dioxide) are sep-
reaction has been regarded as a cis ligand inser-
arated at the top, while water and higher-boiling
tion reaction in which the OH− ligand attacks
byproducts, such as acetic acid, crotonaldehyde,
the π-bonded olefin:
or chlorinated acetaldehydes, are withdrawn to-
cis−[(C2 H4 ) PdCl2 (OH)]− [HOCH2 CH2 PdCl2 ]− gether with acetaldehyde at the bottom. In the
second column (i) acetaldehyde is purified by
Hydride transfer to give an α-hydroxy- fractional distillation.
ethylpalladium complex is followed by reduc- Two-Stage Process (Fig. 3). Tubular reactors
tive elimination, which is the rate-determining (a), (d) are used for both “reaction” and “oxi-
step: dation”. The gases react almost completely in
the presence of the catalyst. Reaction of ethyl-
[HOCH2 CH2 PdCl2 ]− [CH3 CH (OH) PdCl2 ]−
ene takes place at 105 – 110 ◦ C and 900 – 1000
kPa. Catalyst solution containing acetaldehyde
[CH3 CH (OH) PdCl2 ]− →CH3 CHO+Pd+H+ +2Cl− is then expanded in a flash tower (b) by reduc-
For a detailed description, see [43]. The rate ing the pressure to atmospheric level. An acetal-
of reaction can be given by the following equa- dehyde – water vapor mixture distills overhead
tion [44]: while catalyst is sent via the pump (c) to the ox-
idation reactor (d), in which it reacts with oxy-
Acetaldehyde 9

Figure 2. One-stage process


a) Reactor; b) Separating vessel; c) Cooler; d) Scrubber; e) Crude aldehyde tank; f) Cycle-gas compressor; g) Light-ends
distillation; h) Condensers; i) Purification column; l) Product cooler; m) Regeneration

Figure 3. Two-stage process


a) Reactor; b) Flash tower; c) Catalyst pump; d) Oxidation reactor; e) Exhaust-air separator; f) Crude-aldehyde column;
g) Process-water tank; h) Crude-aldehyde container; i) Exhaust-air scrubber; k) Exhaust-gas scrubber; l) Light-ends distil-
lation; m) Condensers; n) Heater; o) Purification column; p) Cooler; q) Pumps; r) Regeneration

gen at about 1000 kPa. As oxidation and reaction exhaust air (nitrogen from the “oxidation”) in (i)
are carried out separately, no high-purity start- and exhaust gas (inert gas from the “reaction”)
ing gas is required. Generally, air is used instead in (k) free of acetaldehyde. Scrubber water then
of oxygen. Oxygen conversion is almost com- flows to the crude aldehyde column (f).
plete; the exhaust air from (e) can be used as A two-stage distillation of the crude acet-
inert gas for plant use. The oxidized catalyst so- aldehyde follows. In the first stage (l), low-
lution separated from exhaust air in the separator boiling substances, such as chloromethane,
(e) is reused for the reaction with ethylene in (a). chloroethane and carbon dioxide, are separated.
Acetaldehyde – water vapor mixture from In the second stage (o), water and higher-boiling
the flash tower (b) is preconcentrated in col- byproducts, such as chlorinated acetaldehydes
umn (f) to 60 – 90 % acetaldehyde by utilizing and acetic acid, are removed from acetaldehyde,
the heat of reaction. Process water discharged at and the latter is obtained in pure form over-
the bottom of (f) is returned to the flash tower head. Chlorinated acetaldehydes become con-
to maintain a constant catalyst concentration. A centrated within the column as medium-boiling
portion of the process water is used for scrubbing substances and are discharged laterally. From
10 Acetaldehyde

this mixture, monochloroacetaldehyde can be Construction Materials. During process


obtained as the hemihydrate. Residual byprod- development, serious problems have been
ucts can be returned to the catalyst for oxidative caused by the extremely corrosive aqueous
decomposition. This oxidative self-purification CuCl2 – PdCl2 solution. These problems have
is supported by thermal treatment of a partial been solved in the two-stage process either by
stream of catalyst at about 160 – 165 ◦ C (regen- constructing parts in contact with the catalyst
eration, r). solution entirely from titanium or by lining those
When gas mixtures obtained in naphtha parts with the metal. In the one-stage process,
cracking processes are used as raw material, con- the reactor is lined with acid-proof ceramic ma-
ventional towers are used as reactors instead of terial, the tubing is made of titanium, and certain
coiled pipes; So far, these processes have not other parts are of tantalum.
been developed industrially. Such mixtures con-
tain 30 – 40 % ethylene in addition to inert hy- Waste Air. The waste air from the oxidation
drocarbons and hydrogen [45]. process contains small amounts of unconverted
Comparison of the Two Methods. In both ethylene, some acetaldehyde, and side products
one- and two-stage processes the acetaldehyde from the reaction such as ethane, chlorometh-
yield is about 95 % and the production costs are ane, chloroethane, and methane. In Germany the
virtually the same. The advantage of using di- waste air must be purified of these side products
lute gases in the two-stage method is balanced to meet the criteria of TA-Luft [47]. The by-
by higher investment costs. Both methods yield products are oxidized over a chromium oxide
chlorinated hydrocarbons, chlorinated acetalde- catalyst. The hydrogen chloride generated is re-
hydes, and acetic acid as byproducts. Generally, moved by washing, so that the waste air contains
the choice of method is governed by the raw mainly carbon dioxide.
material and energy situations as well as by the
availability of oxygen at a reasonable price. Wastewater. Side products of the oxidation
process that enter the wastewater are acetic
Balance of Reaction and Side Products. acid, crotonaldehyde and chlorinated aldehy-
The yield in both type of process is nearly the des. Some of the chlorinated aldehydes are
same. The balance of the two stage process is as highly toxic and show high antimicrobial activ-
follows: ity. Therefore they must be treated before enter-
100 parts of ethylene gives: ing the wastewater plant to render them biolog-
ically degradable. Cleavage of organic chlorine
95 parts acetaldehyde by alkaline hydrolysis is a possible method. If
1.9 parts chlorinated aldehydes the chlorinated compounds can not be destroyed
1.1 parts unconverted ethylene the wastewater has to be incinerated.
0.8 parts carbon dioxide
0.7 parts acetic acid
0.1 parts chloromethane 4.3.2. Acetaldehyde as Byproduct
0.1 parts ethyl chloride
0.3 parts ethane, methane, crotonaldehyde Acetaldehyde is also formed in the production
and other minor side products of vinyl acetate from ethylene or acetylene (→
Vinyl Esters). It is separated by distillation and
The chlorinated aldehydes consist of chloro-
is normally converted to acetic acid for reuse. In
acetaldehyde, dichloroacetaldehyde, trichloro-
one version of the method starting from ethyl-
acetaldehyde, and 2-chloro-2-butenal.
ene, vinyl acetate and acetaldehyde are obtained
in a molar ratio of 1 : 1. This makes the process
Process Variant. An interesting variant of
nearly self-sufficient in acetic acid.
the process, although so far of no technical im-
portance, uses glycol as the reaction medium.
The cyclic acetal of acetaldehyde, namely the 4.3.3. Isomerization of Ethylene Oxide
easily hydrolyzable 2-methyl-1,3-dioloxane, is
obtained. An advantage of this method is the Research was carried out on this process [48] be-
high rate of reaction [46]. fore adopting the direct oxidation of ethylene.
Acetaldehyde 11

Catalysts were Al2 O3 , SiO2 , and acid salts of [54]. If the importance of acetaldehyde as an or-
mineral acids, such as sulfuric acid, phosphoric ganic intermediate were to decrease in the future
acid, or molybdic acid. Yields of 90 – 95 % have as outlined in Chapter 8, this method might be
been reported, but the process has not gained in- of some interest for the economical production
dustrial importance. of small quantities of acetaldehyde.

4.4. Production from C1 Sources 4.5. Production from Hydrocarbons

Since the increases in oil price in 1973/74 and Acetaldehyde is a byproduct of the production
1977, C1 material has gained interest as a feed- of acrolein, acrylic acid, and propene oxide from
stock for organic chemicals and as a substitute propene. It is also formed in the oxidation of sat-
for petrochemicals. However, for acetaldehyde urated hydrocarbons (e.g., propane or butane) in
production, C1 material seems to be of minor im- the gas phase as operated by Celanese in the
portance because most of the classical acetalde- United States [55] (→ Acetic Acid).
hyde derivatives can be made from C1 sources.

Production Directly from Synthesis Gas. 5. Quality and Analysis


Acetaldehyde is formed with low selectivity and
a yield of ca. 30 % from synthesis gas, together High demands on acetaldehyde purity generally
with acetic acid, ethanol, and saturated hydro- are made; a typical specification is:
carbons, mainly methane. Catalysts are cobalt
Color practically colorless
and rhodium compounds activated by iodine Acetaldehyde more than 99.5 wt %
compounds or magnesium chloride and sup- Acid (as acetic acid) less than 0.1 wt %
ported on a silicate carrier [49]. There is so far Water less than 0.02 wt %
no industrial use of this process. Chlorine less than 30 mg/kg
Dry residue less than 10 mg/kg

Production via Methanol, Methyl Ac- The acid content is determined directly by
etate, or Acetic Anhydride. Hydroformylation titration, water content using the Karl Fischer
of methanol with CO/H2 has been well known reagent or empirically from the cloud point of
since the discovery of the oxo process [50]. It a carbon disulfide – acetaldehyde mixture, and
takes place in the presence of hydroformyla- chlorine content (mostly in the form of organic
tion catalysts, such as cobalt, nickel, and iron chlorine compounds) by combustion in a hydro-
salts (e.g., CoBr2 , CoI2 ) or the corresponding gen stream and determination of the hydrochlo-
metal carbonyls, at increased temperature (180 ric acid in the condensate.
– 200 ◦ C) and high pressure (30 – 40 MPa). An
acetaldehyde selectivity of 80 % or more has
been claimed using an iron – cobalt carbonyl 6. Storage and Transportation
or alternatively a cobalt – nickel catalyst in the
presence of tertiary amines, phosphines, or ni- 6.1. Storage
triles as the catalyst [51, 52].
Similarly, high selectivity has been claimed For storage of acetaldehyde, the national regu-
for the hydrocarbonylation of methyl acetate lations must be observed. In Germany the or-
with palladium or rhodium catalysts in the pres- dinance on operational safety (Betriebssicher-
ence of tertiary phosphines and iodine com- heitsverordnung) applies, under which acetalde-
pounds as well as cobalt – ruthenium catalysts hyde is classified as highly inflammable liquid
in the presence of methyl and sodium iodides (F+). In the USA, loading and storage of acetal-
[53]. dehyde are governed by the EPA.
Some patents describe the formation of acet- In Japan the Fire Defense Law and the sup-
aldehyde by reduction of acetic anhydride with plement “Cabinet Order for Control of Danger-
hydrogen over palladium or platinum on a car- ous Articles” applies. According to these regu-
rier at low pressures and moderate temperatures lations, outer storage tanks must not be made of
12 Acetaldehyde

copper, magnesium, silver, mercury, or alloys of population is specified, for which the concen-
these metals. They must be equipped with cool- tration of the material in the air is limited. The
ing facilities in order to keep the temperature maximum level of acetaldehyde allowed at the
below 15 ◦ C, and also with an inert-gas sealing boundary of the factory or place where acetal-
system. dehyde is handled is 0.5 ppm.
For safety data, see Chapter 2. Environmental problems are dealt with by
the respective national laws (see above). If acet-
aldehyde is highly diluted with water it can eas-
6.2. Transportation ily be degraded biologically. In higher concen-
trations it kills bacterial flora.
International Regulations. Acetaldehyde
is classified as a flammable liquid. Transporta-
tion is governed by: 7. Economic Aspects
IMDG Code (sea transport): class 3, UN 1089,
packing group I Today the most important production process
RID (rail): class 3, UN 1089, packing group I worldwide is the direct oxidation of ethylene. In
ADR (road): class 3, UN 1089, packing group Western Europe there is also some capacity for
I the production of acetaldehyde by oxidation of
ADNR (inland waterways), class 3, UN 1089, ethanol (7 %) and hydration of acetylene (17 %).
packing group I In South America the entire capacity for produc-
IATA-DGR (air transportation): class 3, UN tion of acetaldehyde is based on the oxidation of
1089, packing group I, PAC forbidden, CAC ethanol.
packing instruction 304, 30 L max. However, the demand for acetaldehyde
worldwide has continued to decrease primar-
ily as a result of less consumption for acetic
National Regulations. Germany: GGVSE acid manufacture, as the industry continues to
(road and rail); GGVSee (sea). USA: Regula- move toward the more efficient methanol car-
tions of the U.S. Department of Transportation: bonylation process. All manufacture of acetic
CFR 49. acid from acetaldehyde in North America has
Types and sizes of packaging and containers been discontinued, and in Europe significant ca-
are recommended by the regulations mentioned pacity for this transformation has been perma-
above. nently shut down. Acetaldehyde use for acetic
acid manufacture in Asia continues but is under
pressure and will decline because of the estab-
6.3. Other Regulations lishment of methanol carbonylation technology.
Since 1995, some 360 000 t of acetaldehyde ca-
In Germany, any accidental release of acetalde- pacity has been shut down in Western Europe,
hyde into the air, water, or soil must be reported and Mexico has eliminated its acetaldehyde ca-
to the appropriate authorities according to the pacity. New acetaldehyde capacity has been in-
ordinance on operational safety (Betriebssicher- stalled in China, but this is the only area where
heitsverordnung) or the regulations on units for new capacity has been added. Further carbon-
storing, filling, and moving materials danger- ylation capacity will be added between 2006 and
ous to water supplies (Hazardous Incident Or- 2008, but afterward the demand for acetaldehyde
dinance, Störfallverordnung, 2005). for acetic acid will eventually be phased out. Ca-
In the United States, a similar regulation ap- pacity in China is expected to be around 860 000
plies according to the Comprehensive Environ- t by 2008 and is expected to remain at those lev-
mental Response, Compensation, and Liability els for at least five more years.
Act of 1980. Incidents must be reported to the Table 2 gives production data for acetalde-
National Response Center for Water Pollution. hyde.
In Japan, acetaldehyde is specified as an Of- Important producers and their production ca-
fensive Odor Material by the Offensive Odor pacities (103 t) are listed in the following [56]:
Control Law. Under this law a district of dense
Acetaldehyde 13
Table 2. Production of acetaldehyde (103 t) [56]

Year USA W. Europe Mexico Japan China Total


1990 283 603 190 384 1460
1995 111 668 271 395 400 1845
2000 155 370 113 401 400 1439
2003 142 212 57 362 500 1273

Celanese Chemicals Europe GmbH, Germany 120


Eastman Chemical Company, USA 225
Production. Paraldehyde is produced from
ECROS, SA, Spain 90 acetaldehyde in the presence of acid catalysts,
Japan Aldehyde Company Ltd., Japan 69 such as sulfuric acid, phosphoric acid, hy-
Jilin Chemical Industrial Company, China 180 drochloric acid, or acid cation exchangers. In the
Kyowa Yuka Company Ltd., Japan 61
Showa Denko K.K., Japan 300
homogeneous reaction, acetaldehyde is added,
Sinopec Yangzi Petrochemical Co., China 78 (400 planned) with stirring and cooling, to paraldehyde con-
Wacker Chemie AG, Germany 65 taining a small amount of sulfuric acid. After
the addition is completed, stirring is continued
for some time to establish the equilibrium; the
sulfuric acid is exactly neutralized with a sodium
8. Polymers of Acetaldehyde salt, such as sodium acetate, sodium carbonate,
or sodium bicarbonate; the reaction mixture is
8.1. Paraldehyde separated into acetaldehyde, water, and paralde-
hyde by fractional distillation [57].
Paraldehyde, 2,4,6-trimethyl-1,3,5-trioxane For continuous production, liquid acetalde-
[123-63-7], C6 H12 O3 , M r 132.161, is a cyclic hyde at 15 – 20 ◦ C or acetaldehyde vapor at 40
trimer of acetaldehyde: – 50 ◦ C is passed over an acid cation exchanger
[58]. Conversion is greater than 90 %. Acetal-
dehyde and paraldehyde are separated by dis-
tillation. For depolymerization, acetaldehyde is
slowly distilled off in the presence of acid cat-
alysts. Paraldehyde also can be decomposed in
the gas phase. Catalysts are HCl, HBr, H3 PO4 ,
Properties. Paraldehyde is colorless and has or cation exchangers. The reaction is first or-
an ethereal, penetrating odor. der. Other catalysts described in the literature
are Al2 O3 , SiO2 , ZnSO4 , and MgSO4 [59].
bp 124.35 ◦ C
mp 12.54 ◦ C Uses. Paraldehyde is used in chemical syn-
Critical temperature t crit 290 ◦ C thesis as a source of acetaldehyde whereby resin
Solubility in 100 g water at 12 g
13 ◦ C formation and other secondary reactions are

at 75 C 5.8 g largely eliminated. Such synthetic reactions are,
In the solid state, four different crystal forms exist; transition for instance, used for the production of pyridines
points: 230.3 K, 147.5 K, 142.7 K.
Paraldehyde is miscible with most organic solvents. and chlorination of chloral. Between 1939 and
Density d204 0.9923 1945 paraldehyde was used as a motor fuel.
Refractive index n20 D 1.4049

Viscosity at 20 C 1.31 mPa · s
Heat of combustion at constant 3405 kJ/mol
pressure 8.2. Metaldehyde
Heat capacity cp at 25 ◦ C 1.947 J g−1 K−1
Entropy (l) at 25 ◦ C 2.190 J g−1 K−1 Metaldehyde [9002-91-9], C8 H16 O4 , M r
Free energy (l) at 25 ◦ C 276.4 J/g 176.214, is the cyclic tetramer of acetaldehyde:
Heat of vaporization 41.4 kJ/mol
Latent heat of melting 104.75 J/g
Heat of formation from −113.0 kJ/mol
acetaldehyde(calculated from
combustion enthalpies)
The equilibrium 3 acetaldehyde  paraldehyde is 94.3 % on the
paraldehyde side at 150 ◦ C.
14 Acetaldehyde

Properties. Metaldehyde forms tetragonal HNO3 , CF3 COOH, AlCl3 in ether, and partic-
prisms, mp (closed capillary) 246.2 ◦ C, subli- ularly BF3 in liquid ethylene [61]. Al2 O3 and
mation temperature (decomp.) 115 ◦ C, heat of SiO2 also seem to be good initiators [62].
combustion at constant volume 3370 kJ/mol. The polymer has a rubber-like consistency
Metaldehyde is insoluble in water, acetone, and is soluble in common organic solvents. It
acetic acid, and carbon disulfide. depolymerizes at room temperature, liberating
Depolymerization of metaldehyde to acetal- acetaldehyde. It evaporates completely within a
dehyde begins at 80 ◦ C, and is complete above few days or weeks. Acidic compounds accel-
200 ◦ C. Depolymerization takes place faster and erate depolymerization, and amines (e.g., pyri-
at lower temperatures in the presence of acid dine) stabilize polyacetaldehyde to a certain ex-
catalysts, such as dilute H2 SO4 or H3 PO4 . Met- tent. A complete stabilization (as, for instance, in
aldehyde does not show the typical acetaldehyde the case of polyformaldehyde) has not yet been
reactions. It is stabilized by ammonium carbon- achieved, so the polymer is still of no practical
ate or other weakly basic compounds which neu- importance.
tralize acidic potential catalysts. Copolymers with propionaldehyde, butyr-
aldehyde, and allylacetaldehyde also have been
Production. Metaldehyde is obtained in ad- produced [63]. Crystalline, isotactic polymers
dition to large amounts of paraldehyde during have been obtained at low temperatures (for ex-
polymerization of acetaldehyde in the presence ample, −75 ◦ C) by using anionic initiators [64].
of HBr and alkaline earth metal bromides, such Suitable initiators are alkali metal alkoxides, al-
as CaBr2 , at temperatures below 0 ◦ C. However, kali metals, or metal alkyls in hydrocarbon sol-
yields are scarcely higher than 8 %. Yields of vents. The products are insoluble in common or-
14 – 20 % have been reported when working in ganic solvents but have an acetal structure like
the presence of 7 – 15 % of an aliphatic or cyclic the amorphous polymers’ [65]. Polymerization
ether at 0 – 20 ◦ C [60]. Insoluble metaldehyde is of acetaldehyde to poly(vinyl alcohol), which in
filtered out. Acetaldehyde is then distilled from contrast to polyacetaldehyde has a pure carbon
the filtrate following depolymerization of the backbone, has not yet been achieved [66].
paraldehyde and is returned to the polymeriza-
tion. Recycling of the large amounts of acetal-
dehyde results in losses that increase the process 9. Toxicology and Occupational
costs. Health
Uses. Metaldehyde in pellet form is marketed Acetaldehyde. At higher concentrations (up
as a dry fuel (Meta). Mixed with a bait, metalde- to 1000 ppm), acetaldehyde irritates the mucous
hyde is used as a molluscicide. membranes. The perception limit of acetalde-
hyde in air is in the range between 0.07 and 0.25
ppm [67, 68]. At such concentrations the fruity
8.3. Polyacetaldehyde odor of acetaldehyde is apparent. Conjunctival
irritations have been observed after a 15-min ex-
Polyacetaldehyde [9002-91-9] is a high-mo- posure to concentrations of 25 and 50 ppm [69],
lecular-mass polymer with an acetal structure but transient conjunctivitis and irritation of the
(polyoxymethylene structure): respiratory tract have been reported after expo-
sure to 200 ppm acetaldehyde for 15 min [69,
70]. The penetrating odor, the low perception
limit, and the irritation that acetaldehyde causes,
By using cationic initiators, mainly an amor- give an effective warning so that no serious cases
phous polymer is obtained. Temperatures be- of acute intoxication with pure acetaldehyde
low −40 ◦ C are preferred in this case. Above have been reported. Acute acetaldehyde intoxi-
−30 ◦ C, mainly paraldehyde and metaldehyde cation can also be observed following combined
are produced. The initiator activity also depends ingestion of disulfiram (Antabuse) and ethanol
on the solvent used. Suitable initiators include [73]. In animal experiments at high concentra-
H3 PO4 in ether and pentane, as well as HCl, tions (3000 – 20 000 ppm), pulmonary edema
Acetaldehyde 15

and a narcotic effect become evident. The clin- nism of action is assumed to be analogous to that
ical course is similar to alcohol intoxication. of formaldehyde, acetaldehyde is regarded as a
Death occurs by breath paralysis or — with re- suspected carcinogen [80].
tardation — by pulmonary edema. When taken up by the organism, acetalde-
For rats, the LC50 (30 min inhalation) is hyde is metabolized rapidly in the liver to acetic
20 500 ppm [71]. No studies on subchronic or acid. Only a small proportion is exhaled un-
chronic toxicity of acetaldehyde in humans are changed. After intravenous injection, the halflife
available. Investigations of sister chromatid ex- in the blood is approximately 90 s [81].
change in cell cultures [72] and in human lym-
phocytes [74] and studies of single- and double- Paraldehyde acts as a sedative with few side
strand breaks in human lymphocytes incubated effects. Ingested paraldehyde partly is metabo-
with acetaldehyde [75] have revealed mutagenic lized to carbon dioxide and water and partly is
effects of acetaldehyde. Long-term exposures of exhaled unchanged. It generates an unpleasant
Syrian golden hamsters to concentrations in the odor in the expired air and therefore is not much
range 1650 – 2500 ppm have resulted in inflam- used.
matory hyperplastic and metaplastic alterations
of the upper respiratory tract with an increase Metaldehyde decomposes slowly to acetal-
in carcinomas of the nasal mucosa and the lar- dehyde in the presence of acids, so ingestion may
ynx [76]. Male and female Wistar rats were ex- cause irritation of the gastric mucosa with vom-
posed to aldehyde concentrations of 0 ppm, 750 iting. As characteristic signs of a metaldehyde
ppm, 1500 ppm for 6 h daily, 5 d per week for 52 intoxication, especially in children, heavy con-
weeks. In the highest dose group, the initial alde- vulsions (sometimes lasting several days) have
hyde concentration of 3000 ppm was reduced to been reported, with lethal outcomes, after in-
1000 ppm in the course of the study due to toxic gestion of several grams of metaldehyde [82].
effects. The dose-dependent effects found were For these reasons, those molluscicides and solid
increased mortality in all dose groups and de- fuels which contain metaldehyde must be kept
layed growth in the middle- and highest-dose away from children.
group. Adenocarcinomas were observed at all
three investigated concentrations. An increased
rate of squamous epithelial carcinomas was only 10. References
seen at 1500 ppm or more. Histological signs of
irritation were observed in the larynx region in General References
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16 Acetaldehyde

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(1960) 32. Schädlingsbekämpfungsmittel, Abriß einer
Consortium für elektrochemische Industrie, Toxikologie und Therapie von Vergiftungen,
DE 1 106 075, 1958 (J. Smidt, J. Sedlmeier). Hundt-Verlag, Hattingen 1972.
Acetic Acid 1

Acetic Acid
Hosea Cheung, Celanese Ltd., Chemicals Division, Technical Center, Corpus Christi, Texas 78469,
United States
Robin S. Tanke, Celanese Ltd., Chemicals Division, Technical Center, Corpus Christi, Texas 78469, United
States
G. Paul Torrence, Celanese Ltd., Chemicals Division, Technical Center, Corpus Christi, Texas 78469, United
States

1. Introduction . . . . . . . . . . . . . . 1 10.1.1. Aluminum Acetate . . . . . . . . . . . 19


2. Physical Properties . . . . . . . . . . 1 10.1.2. Ammonium Acetate . . . . . . . . . . 19
3. Chemical Properties . . . . . . . . . 3 10.1.3. Alkali Metal Salts . . . . . . . . . . . 21
4. Production . . . . . . . . . . . . . . . . 3 10.2. Esters . . . . . . . . . . . . . . . . . . . 21
4.1. Carbonylation of Methanol . . . . . 4 10.2.1. Methyl Acetate . . . . . . . . . . . . . 22
4.2. Direct Oxidation 10.2.2. Ethyl Acetate . . . . . . . . . . . . . . 22
of Saturated Hydrocarbons . . . . 10 10.2.3. Butyl Acetate . . . . . . . . . . . . . . 22
4.3. Acetaldehyde Process . . . . . . . . 13 10.2.4. 2-Ethylhexyl Acetate . . . . . . . . . . 23
4.4. Other Processes . . . . . . . . . . . . 15
10.2.5. Other Esters . . . . . . . . . . . . . . . 23
4.5. Concentration and Purification . . 17
10.3. Acetyl Chloride . . . . . . . . . . . . 23
4.6. Construction Materials . . . . . . . 17
10.4. Amides . . . . . . . . . . . . . . . . . . 23
5. Wastewater and Off-Gas Problems 17
10.4.1. Acetamide . . . . . . . . . . . . . . . . 23
6. Quality Specifications . . . . . . . . 18
7. Analysis . . . . . . . . . . . . . . . . . 18 10.4.2. N,N-Dimethylacetamide . . . . . . . . 24
8. Storage, Transportation, 10.5. Phenylacetic Acid . . . . . . . . . . . 24
and Customs Regulations . . . . . . 18 11. Economic Aspects . . . . . . . . . . . 24
9. Uses . . . . . . . . . . . . . . . . . . . . 19 12. Toxicology
10. Derivatives . . . . . . . . . . . . . . . 19 and Occupational Health ...... 25
10.1. Salts . . . . . . . . . . . . . . . . . . . . 19 13. References . . . . . . . . . . ...... 26

1. Introduction 2. Physical Properties


Acetic acid [64-19-7], CH3 COOH, M r 60.05, is Acetic acid is a clear, colorless, corrosive liquid
found in dilute solutions in many plant and ani- that has a pungent odor and is a dangerous vesi-
mal systems. Vinegar, an aqueous solution con- cant. It has a pK a of 4.77 [2]. It melts at 16.75 ◦ C
taining about 4 – 12 % acetic acid, is produced [3] and boils at 117.9 ◦ C [4] under 101.3 kPa [5].
by the fermentation of wine and has been known It has a pungent vinegarlike odor. The detectable
for more than 5000 years. odor is as low as 1 ppm. The acid is combustible
The major producers of acetic acid, account- with a low flash point of 43 ◦ C. The explosion
ing for ca. 70 % of total worldwide produc- limits of acetic acid vary from the upper explo-
tion, are the United States, Western Europe, and sion limit (UEL) of 16 % at 92 ◦ C to the lower
Japan. World capacity exceeds 7 × 106 t/a [1]. explosion limit (LEL) of 4 % at 59 ◦ C. The liq-
The largest end uses are in the manufacture of uid is usually available as glacial acetic acid with
vinyl acetate [108-05-4] and acetic anhydride less than 1 wt % water and over 98 % purity. Be-
[108-24-7]. Vinyl acetate is used in the produc- sides water, the acid contains traces of impurities
tion of latex emulsion resins for applications such as acetaldehyde, oxidized substances, iron,
in paints, adhesives, paper coatings, and tex- and chlorides.
tile treatment. Acetic anhydride is used in the Occasionally, the acid may be colored due to
manufacture of cellulose acetate textile fibers, the presence of ethyl acetoacetate [141-97-9].
cigarette filter tow, and cellulose plastics.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 045
2 Acetic Acid
Table 3. Dependence of the density of pure acetic acid on tempera-
The acetate is easily mistaken for formic acid ture
because it reduces mercuric chloride. Traces of
mercury may cause extensive corrosion by re- t, ◦ C , g/cm3 t, ◦ C , g/cm3

action with aluminum. Aluminum is a common 20 1.0491 130 0.9235


material for containers to ship the acid [6]. 26 1.0420 139 0.9119
34 1.0324 140 0.9092
Glacial acetic acid is very hydroscopic. The 52 1.0134 145 0.9030
presence of 0.1 wt % water lowers the freezing 60 1.0060 156 0.8889
63 1.0007 180 0.8555
point significantly [7]. Measuring the freezing 75 0.9875 220 0.7941
point is a convenient way to evaluate acetic acid 85 0.9761 260 0.7136
purity. This is shown in Table 1 [8]. 97 0.9611 300 0.5950
100 0.9599 320 0.4615
Table 1. Freezing points for various acetic acid – water mixtures 107 0.9506 321 0.3506
117 0.9391
wt % fp, wt % fp,
CH3 COOH CH3 COOH
◦ ◦
C C
Due to the difficulty in eliminating traces of
100 16.75 96.8 11.48
99.6 15.84 96.4 10.83
water from acetic acid, the value for the boil-
99.2 15.12 96.0 10.17 ing point varies from 391 to 392 K [10]. Care-
98.8 14.49 93.5 7.1 ful studies prove that pure acetic acid boils at
98.4 13.86 80.6 − 7.4
98.0 13.25 50.6 −19.8 391.10 K under 101.325 kPa [16]. The critical
97.6 12.66 18.1 − 6.3 temperature and critical pressure are 594.45 K
97.2 12.09
and 5785.7 kPa [3].
Precise data on vapor pressure of acetic acid
Acetic acid forms azeotropes with many
are available from a regression equation (Eq. 1)
common solvents, such as benzene, pyridine,
[10], which covers the range from the normal
and dioxane. Acetic acid is miscible with wa-
boiling point to the critical point.
ter, ethanol, acetone, benzene, ether, and carbon
tetrachloride. However, it is not soluble in CS2 P = Pc exp(A + B/T r + C lnT r + DT 6r ) (1)
[2].
The physical properties of acetic acid are where P is vapor pressure in kPa; T r is reduced
well documented, and their accuracy is impor- temperature T /T c , T is temperature in K; T c is
tant for commercial production. For instance, 594.45 K, Pc is 5785.7 kPa, A is 10.08590, B is
design and operation of distillation processes re- − 10.37932; C is − 3.87306, and D is 0.29342.
quires precise data. High-precision values pro-
vide a valuable asset to the chemical industry
Table 4. Vapor pressure of pure acetic acid
[9], [10].
The density of mixtures of acetic acid and wa- t, ◦
C p, mbar t, ◦
C p, mbar
ter [11–13] is listed in Table 2. The density ex-
0 4.7 150.0 2 461.1
hibits a maximum between 67 wt % and 87 wt %, 10 8.5 160 3 160
corresponding to the monohydrate (77 wt % 20 15.7 170 4 041
30 26.5 180 5 091
acetic acid). The density of pure acetic acid as a 40 45.3 190 6 333
function of temperature is listed in Table 3 [14], 50 74.9 200 7 813
[15]. 60 117.7 210 9 612
70 182.8 220 11 733
Table 2. Densities of aqueous acetic acid solutions at 15 ◦ C 80 269.4 230 14 249
90 390.4 240 17 057
100 555.3 250 20 210
wt % , wt % ,
110 776.7 260 23 854
CH3 COOH g/cm3 CH3 COOH g/cm3
118.2 1013 270 28 077
130.0 1386.5 280 32 801
1 1.007 60 1.0685
140.0 1841.1
5 1.0067 70 1.0733
10 1.0142 80 1.0748
15 1.0214 90 1.0713
20 1.0284 95 1.0660 The vapor pressure of pure acetic acid is given
30 1.0412 97 1.0625
40 1.0523 99 1.0580 in Table 4 [17]. The density of the vapor cor-
50 1.0615 100 1.0550 responds to approximately twice the molecular
Acetic Acid 3

mass because of vapor-phase hydrogen bond- Specific heat capacity


Gaseous acid, cp 1.110 J g−1 K−1 at 25 ◦ C [33]
ing [8]. Hydrogen-bonded dimers and tetramers Liquid acid, cp 2.043 J g−1 K−1 at 19.4 ◦ C
have both been proposed. Reports indicate that Crystalline acid, cp 1.470 J g−1 K−1 at 1.5 ◦ C
in the gas phase, the acid exists mainly in an equi- 0.783 J g−1 K−1 at −175.8 ◦ C
Heat of fusion 195.5 J/g [29]
librium between monomer and dimer (Eq. 2) ac- Heat of combustion −874.2 kJ/mol at 20 ◦ C [30]
cording to vapor density data [18], [19] molec- Cryoscopic constant −269.56 ◦ C [30]
ular modeling, IR analysis [20], and gas-phase Ebullioscopic constant 270.62 ◦ C [30]
Melting point 6.76 ◦ C [31]
electron diffraction [21]. Triple-point temperature 16.93 ◦ C [19]
Boiling point 118.0 ◦ C at 101.3 kPa [32]
Density 1265.85 kg/m3 (solid at mp)
Viscosity 11.83 mPa · s at 20 ◦ C [26]
10.97 mPa · s at 25 ◦ C [27]
8.18 mPa · s at 40 ◦ C [26]
0.067 mPa · s at critical point [28]
(2) Dielectric constant 6.194 at 20 ◦ C [30]
Dipole moment 5.804 × 10−30 C · m [34]
Electrolyte conductivity 112.0 pS/m [33]
In the gas phase, monomic and dimeric acetic Refractive index n20
D 1.372 [33]
acid undergo extensive hydrolysis [22], [23]. Enthalpy of formation
∆H 0 (l, 25 ◦ C) −484.50 kJ/mol [35]
In the liquid state, acetic acid equilibrates be-
∆H 0 (g, 25 ◦ C) −432.25 kJ/mol
tween monomer and dihydrated dimer or cyclic Normal entropy
dimer (Eqs. 2 and 3) [24]. As the concentration S ◦ (l, 25 ◦ C) 159.8 J mol−1 K−1 [35]
of acetic acid increases, the equilibrium shifts S ◦ (g, 25 ◦ C) 282.5 J mol−1 K−1
Flash point 43 ◦ C (closed cup) [36]
to the right, favoring dimeric acetic acid. As the 57 ◦ C (open cup)
temperature is increased, the system shifts to the Autoignition point 465 ◦ C [36]
Flammability 4.0 to 16.0 vol % in air [36]
left, favoring the monomer. In addition, the acid Critical data
may also form open-chain trimers and higher pc 5.786 MPa [3]
oligomers. However, at about 95 wt %, the acid Tc 321.45 ◦ C [3]

exists mainly as a cyclic dimer and is no longer


associated with water.
3. Chemical Properties
Many useful materials are made from acetic
acid; several are discussed in Chapter 9. Acetate
esters are formed by reaction of olefins or al-
cohols with acetic acid [37]. Acetamide is pre-
(3) pared by the thermal decomposition of ammo-
nium acetate. Acetic acid can be converted to
Up to 32 wt %, mixing acetic acid with water acetyl chloride with phosphorous trichloride or
leads to evolution of heat. At higher acid con- thionyl chloride.
centrations heat is absorbed [25]. The measured Acetic acid is a raw material for a number
values of the heat of mixing are consistent with of commercial processes. It can be converted to
the calculated values based on the dimers and vinyl acetate with ethylene and oxygen (→ Vinyl
tetramers described above. The aqueous mix- Esters). Acetic acid is used in the manufacture
ture of acetic acid forms a eutectic mixture at of acetic anhydride (→ Acetic Anhydride) via
− 26 ◦ C. This eutectic mixture prevented earlier ketene and in the production of chloroacetic acid
attempts to concentrate the acid by freezing. A (→ Chloroacetic Acids) using chlorine.
way to obtain pure acid is to add urea or potas-
sium acetate to the acid. Then, glacial acetic acid
can be distilled.
Other physical properties of acetic acid are
4. Production
listed below.
Vinegar is still made by fermentation (→ Vi-
negar). However, the most important synthetic
4 Acetic Acid

routes to acetic acid are methanol carbonyla- meet acetic acid supply shortages in the United
tion and liquid-phase oxidation of butane, naph- States.
tha, or acetaldehyde. Methanol carbonylation Monsanto developed a low-pressure acetic
has been the method of choice for the past 25 acid process in the late 1960s with a rhodium
years [38–40] and will likely remain the pre- iodide promoted catalyst system that demon-
ferred route for large-scale production. strated significantly higher activity and selec-
Several new technologies for producing tivity than the cobalt-based process. Methanol
acetic acid are being studied. Showa Denko may can be carbonylated even at atmospheric pres-
produce acetic acid by the gas-phase reaction sure with yields of 99 % and 90 % with re-
of ethylene with oxygen over a supported pal- spect to methanol and carbon monoxide, respec-
ladium catalyst that contains a heteropolyacid tively [49]. This process was proven commer-
or salt [41]. Numerous patents and publications cially in 1970 at Texas City, Texas. The initial
discuss the production of acetic acid directly plant capacity of 135 000 t/a has been expanded
from ethane and oxygen. Production of acetic to 270 000 t/a since 1975 [1]. Operating condi-
acid and acetate salts by microorganisms has tions in the reactor are much milder (3 MPa and
also received considerable attention. 180 ◦ C) than in the BASF process [50]. Soon af-
ter the Monsanto process was commercialized,
the BASF process became uncompetitive, so the
4.1. Carbonylation of Methanol Monsanto process is the preferred technology
for grass-roots acetic acid units. Since the start-
The manufacture of acetic acid from methanol up of the Texas City plant by Monsanto, more
[67-56-1] and carbon monoxide [630-08-0] at than ten companies have licensed and operated
high temperature and high pressure was de- this technology worldwide.
scribed by BASF as early as 1913 [42]. In 1978 at the Clear Lake Texas Plant,
Celanese Chemical Company (now Celanese,
CH3 OH + CO −→ CH3 COOH ∆H = − 138.6 kJ Ltd.) was the first licensee to demonstrate com-
mercially the rhodium-catalyzed Monsanto pro-
In 1941 Reppe at BASF demonstrated the ef- cess. Initial capacity was 27 000 t/a [51]. In
ficiency of group VIII metal carbonyls as cata- the early 1980s, Celanese developed a pro-
lysts for carbonylation reactions, including hy- prietary low-reaction-water rhodium-catalyzed
droformylation [43], [44]. This led to the de- methanol carbonylation process by modifica-
velopment of a high-pressure, high-temperature tion of the original Monsanto high-reaction-
process (700 bar, 250 ◦ C) with a cobalt iodide water chemistry. Modifications to the catalyst
catalyst. The thrust of this work was to de- system by the addition of inorganic iodide salts
velop an acetic acid process not dependent on improved catalyst stability and activity signif-
petroleum-based feedstocks. The current advan- icantly [52]. This technology improvement en-
tage of the methanol carbonylation route to abled the Clear Lake unit to expand by more than
acetic acid is the favorable raw material and en- three times the original capacity to 900 000 t/a
ergy costs. The synthesis gas raw material re- with minor capital cost [53].
quired for this process can be obtained from a In 1986, BP Chemicals purchased from Mon-
variety of sources, which range from natural gas santo the high-reaction-water, low-pressure,
to coal. The cobalt-based carbonylation process rhodium-catalyzed methanol carbonylation
was commercialized in 1960 by BASF in Lud- technology and licensing rights. The acquisi-
wigshafen, Federal Republic of Germany [43], tion of the technology did not include the im-
[45–47]. The initial capacity of 3600 t/a was ex- provements developed by Celanese Chemical
panded to 45 000 t/a by 1981 [48]. In 1966 Bor- Company.
den Chemical Co. started up a 45 000 t/a acetic Monsanto in the early 1960s also discov-
acid unit in Geismar, Louisiana, United States, ered that iridium, like rhodium, is an effec-
based on the BASF technology [43], [45]. The tive methanol carbonylation catalyst. This cat-
unit was expanded to 64 000 t/a by 1981 before alyst system has since been developed commer-
it was shut down in 1982 [1], [48]. This unit was cially by BP in the early 1990s and is known as
brought on stream again in 1988 for one year to the Cativa process [54]. This process was uti-
Acetic Acid 5

lized to convert the original rhodium-catalyzed Once formed, this acyl intermediate cannot un-
methanol carbonylation plant in Texas City to dergo simple reductive elimination of acetyl io-
an iridium-based process. Several advantages dide because iodide is not coordinated to cobalt.
claimed by BP for the Cativa process over the Acetyl iodide is formed from the reaction of hy-
conventional rhodium-catalyzed high reaction drogen iodide with the acyl complex to regener-
water carbonylation process include superior ate the cobalt carbonyl anion. Rapid hydrolysis
catalyst stability, operation at lower reaction wa- of the acetyl iodide forms acetic acid and hydro-
ter, and less liquid byproducts [55]. gen iodide. All of the individual steps involved
in the otherwise similar mechanism can be as-
Chemistry and Reaction Conditions. The sumed to occur at a lower rate for cobalt than for
chemistry of the cobalt- (BASF), rhodium- rhodium and iridium. This explains the higher
(Monsanto and Celanese), and iridium- temperature needed for the BASF process. In
catalyzed (BP) processes is similar in requiring addition, higher carbon monoxide partial pres-
promotion by iodide, but the different kinetics sures are required to stabilize the [Co(CO)4 ]−
indicate different rate-determining steps. In all complex at the higher reactor temperatures.
three processes, two important catalytic cycles Byproducts in the BASF process are CH4 ,
are common, one that involves the metal car- CH3 CHO, C2 H5 OH, CO2 , C2 H5 COOH, alkyl
bonyl catalyst and one that involves the iodide acetates, and 2-ethyl-1-butanol [58–60]. About
promoter [56], [57]. 3.5 % of the methanol reactant leaves the system
The cobalt-catalyzed BASF process uses as CH4 , 4.5 % as liquid byproducts, and 2 % is
cobalt(II) iodide [15238-00-3] for in situ gen- lost as off-gas. Some 10 % of the CO feed is
eration of [Co2 (CO)8 ] and hydrogen iodide converted to CO2 by the water gas shift reaction
[10034-85-2]. Compared to other methanol car- (Eq. 4b).
bonylation processes, severe conditions are re-
CO + H2 O −→ CO2 + H2 (4b)
quired to give commercially acceptable reaction
rates. The rate of reaction depends strongly on The Monsanto process with rhodium carbonyl
both the partial pressure of carbon monoxide and catalyst [38255-39-9] and iodide promoter op-
the methanol concentration. Acetic acid yields erates under milder conditions than the BASF
are 90 % based on methanol and 70 % based on cobalt-catalyzed process. Methanol and carbon
carbon monoxide. A proposed mechanism for monoxide selectivities of greater than 99 % and
the iodide-promoted reaction is summarized in 90 %, respectively, are obtained [49]. The sys-
Figure 1 [43], [56], [57]. tem is not as sensitive to hydrogen as the BASF
The generation of the active nucleophile, process, and therefore reduction products such
[Co(CO)4 ]− , can be considered a water-gas as methane and propionic acid are comparatively
shift reaction [Eq. (4a); cf. Eq. (4b)] in which insignificant.
[Co2 (CO)8 ] is the catalyst and the hydrogen The chemistry of the rhodium-catalyzed
formed is dissociated via the hydridocarbonyl methanol carbonylation reaction has been stud-
complex. ied in detail [57]. Kinetic studies show the re-
action to be zero-order in carbon monoxide and
[Co2 (CO)8 ] + H2 O + CO −→ 2 [Co(H)(CO)4 ] + CO2 (4a) methanol, and first-order in rhodium and iodide
promoter. The carbonylation rate is strongly af-
Subsequently, the methyl iodide formed from fected by the reaction media, but the overall ki-
hydrogen iodide and methanol undergoes nu- netics are unaffected by the solvent, which sug-
cleophilic attack by the [Co(CO)4 ]− anion. Io- gests that it does not participate in the transi-
dide facilitates this reaction because it is a bet- tion state of the rate-determining step [61–64].
ter leaving group than OH− . The CH3 I re- Methanol carbonylation in polar solvents gen-
acts with a coordinatively saturated d10 com- erally provides a rate enhancement, especially
plex, which is the preferred electron configu- with the addition of protic solvents. An acetic
ration of cobalt(I). Therefore, the methyl mi- acid/water solvent medium is preferred [65].
gration to form the acyl cobalt carbonyl com- Many different rhodium compounds act as
plex, [CH3 C(O)Co(CO)3 ], is less favored than effective catalyst precursors for methanol car-
the same process for the rhodium(III) species. bonylation at common reaction temperatures of
6 Acetic Acid

Figure 1. Reaction cycle proposed for the cobalt-catalyzed methanol carbonylation reaction (BASF process)

150 – 200 ◦ C. The iodide promoter is normally gration gives the pentacoordinate acyl interme-
methyl iodide, but other forms of iodide, such as diate. The acyl intermediate eliminates acetyl io-
hydrogen iodide or iodine, can be used without dide and regenerates [Rh(CO)2 I2 ]− . The acetyl
marked differences in reaction rates. iodide reacts with water to regenerate hydrogen
Spectroscopic investigations have shown that iodide and produce acetic acid. Hydrogen iodide
rhodium(III) halides can be reduced in aque- reacts with methanol to form methyl iodide. In
ous or alcoholic media to [Rh(CO)2 X2 ]− [50]. this way both the original rhodium complex and
The reaction rate is independent of the rhodium methyl iodide promoter are regenerated.
precursor charged to the reaction provided ad- In the 1980s Celanese made innovative im-
equate iodide, generally methyl iodide, and provements to the rhodium catalyst system of
carbon monoxide are available. Under these the Monsanto process with the implementa-
conditions, [Rh(CO)2 I2 ]− is the predominant tion of the proprietary acetic acid optimization
rhodium species in the reaction solution. These (AO) technology which incorporates catalyst
observations strongly suggest the generation of co-promoters. Advantages of AO technology
[Rh(CO)2 I2 ]− as the active catalyst species [50]. are enhanced carbonylation rates and increased
The catalytic cycle shown in Figure 2 is carbon monoxide and methanol efficiencies at
based on kinetic and spectroscopic studies [66– lower reaction-water concentrations [52]. These
78]. The complex anion [Rh(CO)2 I2 ]− reacts modifications represent the most significant de-
in the rate-determining step with methyl io- velopment in rhodium-catalyzed methanol car-
dide by oxidative addition to form the transient bonylation since the development of the Mon-
methylrhodium(III) intermediate. Methyl mi- santo process. The AO technology enabled the
Acetic Acid 7

Figure 2. Reaction cycle proposed for the rhodium-catalyzed methanol carbonylation reaction (Monsanto process) and with
inorganic iodide co-promotion (Celanese process)

Celanese Clear Lake Plant to more than triple The primary byproducts and major ineffi-
unit capacity from 27 000 t/a since start-up in ciency with respect to carbon monoxide in the
1978 to 90 000 t/a acetic acid in 1998 with very rhodium-catalyzed process are carbon dioxide
low capital investment [51], [53]. and hydrogen via the water gas shift reaction
The increased carbonylation rates at low re- (Eq. 4). The water gas shift reaction is also
action water concentrations are achieved by catalyzed by [Rh(CO)2 I2 ]− [50], [79–81]. The
catalyst promotion with iodide and acetate overall two-step reaction is summarized in the
anions [38], [70–72]. This unique enhance- following:
ment in catalyst activity is due presumably to
[Rh(CO)2 I2 ]− + 2 HI −→ [Rh(CO)I4 ]− + H2 + CO
the generation of a strongly nucleophilic five- [Rh(CO)I4 ]− + 2 CO + H2 O −→ [Rh(CO)2 I2 ]− + CO2 + 2 HI
coordinate dianionic catalyst species, namely,
[Rh(CO)2 I2 (L)]2− (L = I− or OAc− ), which is CO + H2 O −→ CO2 + H2
more active than [Rh(CO)2 I2 ]− toward oxida-
tive addition of methyl iodide. This additional The proposed kinetic pathway for the water
reaction pathway is summarized in Figure 2. gas shift reaction is shown in Figure 2, which
emphasizes the interrelation between methanol
8 Acetic Acid

carbonylation and water gas shift reaction as vation is consistent with the greater stability of
catalyzed by [Rh(CO)2 I2 ]− . The addition of the methyliridium(III) complex associated with
inorganic iodide co-promoters in the Celanese the hydrogenation of the iridium – carbon bond
process reduces significantly the proportion of [83].
[Rh(CO)2 I2 ]− that catalyzes the water gas shift Other transition-metal complexes have been
reaction. As a result, the conversion of carbon investigated as promising catalysts for methanol
monoxide and methanol to acetic acid is im- carbonylation, in particular, nickel complexes by
proved over the conventional Monsanto process, Halcon and Rhône-Poulenc [57], [89], [90].
and the rate of methanol carbonylation is in-
creased [38]. BASF Process [91] (Fig. 4).
Compared to the cobalt-based process, Carbon monoxide, methanol (containing up
byproducts derived from methanol such as CH4, to 60 % dimethyl ether), catalyst recycle, cat-
CH3 CHO, and C2 H5 COOH are formed in very alyst makeup, and methyl iodide recycle (from
small amounts, even in the presence of sig- the wash column) are sent to the high-pressure
nificant amounts of hydrogen in the carbon reactor (b; stainless steel lined with Hastelloy).
monoxide feed gas [82]. This low methanol in- Part of the relatively low heat of reaction is used
efficiency is associated with occurrence of the to preheat the feed and the rest is ultimately dis-
rate-determining step prior to formation of a sipated through the reaction vent. The reaction
organometallic compound, the short lifetime of product is cooled and sent to the high-pressure
the methylrhodium complex, and the rapid re- separator (d). The off-gas goes to the wash col-
ductive elimination of the acylrhodium com- umn (o) and the liquid is expanded to a pressure
plex to form acetyl iodide, which is rapidly hy- of 0.5 – 1.0 MPa in the intermediate-pressure
drolyzed to acetic acid and hydrogen iodide. separator (e). The gas released is also sent to the
Similar to the rhodium-based carbonyla- wash column; the liquid from the intermediate-
tion processes, the reaction chemistry of the pressure separator is sent to the expansion cham-
BP iridium-catalyzed methanol carbonylation is ber (f). The gas from the chamber goes to the
well characterized [50], [56], [57], [78], [85– scrubber (p). The gas from the scrubber and the
88]. The iridium-catalyzed reaction proceeds wash column is discarded as off-gas. Both scrub-
through a series of similar reaction pathways to ber and wash column use the methanol feed to re-
the rhodium-catalyzed system but involves a dif- cover methyl iodide and other iodine-containing
ferent rate-determining step. The proposed rate- volatile compounds; this methanolic solution is
determining step is methyl migration to form returned to the reactor. The off-gas composition
the iridium acyl complex. This pathway involves in vol % is 65 – 75 CO, 15 – 20 CO2 , 3 – 5 CH4 ,
the elimination of iodide and the subsequent ad- and the balance CH3 OH.
dition of carbon monoxide. The direct depen- The raw acid from the expansion chamber
dence of the reaction rate on carbon monox- contains 45 wt % acetic acid, 35 wt % water,
ide concentration and the inhibiting effect of and 20 wt % esters, mainly methyl acetate. The
low concentations of iodide are consistent with acid is purified in five distillation towers. The
the rate-determining step [55], [83]. The pro- first column (h) degasses the crude product; the
posed catalytic scheme for the reaction is given off-gas is sent to the scrubber column. The cat-
in Figure 3 [55]. Model studies at 25 ◦ C demon- alyst is then separated as a concentrated acetic
strate that the oxidative addition of methyl iodide acid solution by stripping the volatile compo-
to iridium is about 120 – 150 times faster than nents in the catalyst separation column (i). The
for rhodium [55], [83]. However, methyl migra- acid is then dried by azeotropic distillation in the
tion on iridium is 105 to 106 times slower than drying column (k). The overhead of the drying
for rhodium [83]. The main byproducts of the column contains acetic and formic acids, water,
iridium-catalyzed process are also carbon diox- and byproducts that form an azeotrope with wa-
ide and hydrogen via the water gas shift reac- ter. This overhead is a two-phase system that is
tion (Eq. 4b). The mechanism of this reaction is separated in the chamber (g). Part of the organic
similar to the rhodium-catalyzed process [57]. phase, composed mainly of esters, is returned to
The production of CH4 derived from methanol is column (k), where it functions as an azeotrop-
higher for iridium than for rhodium. This obser- ing agent. The remainder of the organic phase
Acetic Acid 9

Figure 3. Reaction cycle proposed for the iridium-catalyzed methanol carbonylation reaction (Cativa process)

Figure 4. Production of acetic acid (BASF process)


a) Preheater; b) Reactor; c) Cooler; d) High-pressure separator; e) Intermediate pressure separator; f) Expansion chamber;
g) Separation chamber; h) Degasser column; i) Catalyst separation column; k) Drying column; l) Pure acid column; m) Residue
column; n) Auxiliary column; o) Wash column; p) Scrubbing column
10 Acetic Acid

is sent to the auxiliary column (n) where heavy of the original Monsanto process, the overall
ends are separated at the bottom of the column, general process is presumably the same, pos-
and light esters from the overhead are recycled to sibly with some modifications [54], [93], [94].
the reactor. The aqueous phase and the catalyst
solution are returned to the reactor. The base of
the drying column is sent to a finishing column 4.2. Direct Oxidation of Saturated
(l), in which pure acetic acid is taken overhead. Hydrocarbons
The bottom stream of the finishing tower is sent
to the residue column (m). The overhead of this Liquid-phase oxidation (LPO) of aliphatic hy-
residue column is sent back to the dehydration drocarbons was once practiced worldwide [95].
column. The bottom of the residue column con- Due to competition from carbonylation technol-
tains about 50 wt % propionic acid, which can ogy, plants have reduced production by LPO sig-
be recovered. nificantly. The process changes depending on
the availability of raw materials. Raw materials
Monsanto Process [38], [83], [92] (Fig. 5). include n-butane and light naphtha [96]. In the
Carbon monoxide and methanol are intro- United States and Canada, Celanese employs bu-
duced continuously into a back-mixed liquid- tane, while BP in the United Kingdom uses light
phase reactor (a) at ca. 150 – 200 ◦ C and naphtha to produce acetic acid [97]. Capacities
30 – 60 bar [38], [83], [92]. The noncondensable of related production are shown in Table 5 [99].
byproducts (CO2 , H2 , and CH4 ) are vented from
the reactor to control the carbon monoxide par- Table 5. Butane liquid-phase oxidation processes

tial pressure in the reactor. The off-gas from the Company Location Acetic acid capacity,
reactor and the purification sections of the pro- t/a
cess are combined and sent to a vent recovery Celanese Pampa, Texas 250 000 [43]
system in which the light ends, including organic Edmonton, Alberta, 75 000 [99]
iodides such as methyl iodide, are scrubbed from Canada
BP Hull, England 210 000
the vent before the noncondensable gases are AKZO Zout Chemie Europoort, The 110 000 [100]
flared. The light ends from the vent recovery Netherlands
system are recycled to the reactor. The reactor
solution is forwarded to the flasher (b) where the
catalyst is separated as a residue stream from Reaction Mechanism. Oxidation of hydro-
the crude acetic acid product and recycled to carbons follows similar kinetics, both in the gas
the reactor. The crude acetic acid, which con- and liquid phases, especially in slightly polar
tains methyl iodide, methyl acetate, and water, solvents [98]. However, the mechanism of the
is taken overhead in (b) and sent to the light- reaction is very complicated. The reaction can
ends column (c). The light components (methyl be considered roughly as a radical chain reac-
iodide, methyl acetate, and water) are recycled tion [99]. For example, the oxidation of butane
to the reactor as a two-phase overhead stream, proceeds through initiation, oxidation, propaga-
while wet acetic acid is removed as a side stream tion, and decomposition steps [96]. The initia-
from (c) and sent to the dehydration column (d). tion and propagation probably involve radicals
An aqueous acetic acid overhead stream from (c) abstracting hydrogen from a secondary carbon
is recycled to the reactor and a dry acetic acid atom of butane. Subsequent reaction with oxy-
product residue stream is forwarded to a heavy gen yields hydroperoxides. These intermediates
ends column (e). As a residue stream in (e), pro- decomposes to produce acetic acid. Catalysts,
pionic acid, which is the major liquid byprod- agitation, and high temperature accelerate the
uct of the process is removed with other higher decomposition.
boiling carboxylic acids. Product acetic acid is Catalysts are not essential for LPO [100].
removed in (e) as a sidestream, and the overhead However, metal catalysts may influence the dis-
stream is recycled to the purification section of tribution of products, induction period, and op-
the process. erating temperature [101], [102].
Since the Cativa process as demonstrated in In a simple mechanism, the first step of oxida-
the Sterling Plant at Texas City, Texas is a retrofit tion is the abstraction of a secondary hydrogen
Acetic Acid 11

Figure 5. Production of acetic acid (Monsanto process)


a) Reactor; b) Flasher; c) Light-ends column; d) Dehydration column; e) Heavy-ends column

atom (Eq. 5) to give alkyl radicals. The oxygen


in the solvent rapidly converts these radicals to
sec-butylperoxy radicals [103] (Eq. 6). In other
interpretations, oxygen is believed to directly re-
act with one or two alkane molecules to form
radicals (Eqs. 7 and 8) [104], [105], [106]. Ini-
tiation, especially with catalysts, affects the in-
duction period significantly [107].

RH + In• −→ R• + HIN (5)

R• + O2 −→ ROO• (6)

RH + O2 −→ R• + HOO• (7) (15)

In general, peroxy radicals do not abstract


2 RH + O2 −→ 2 R• + HOOH (8)
hydrogen efficiently from other molecules, so
the reaction medium contains an abundance of
ROO• + RH −→ ROOH + R• (9)
these radicals. Each radical abstracts hydrogen
from an alkane to form a hydroperoxide and an
ROOH −→ RO• + HO• (10)
alkyl radical (Eq. 9). Alkyl radicals propagate
ROO• + ROO• −→ ROOOOR (11)
the chain (Eq. 6).
The hydroperoxide decomposes to give an
ROO• + Mn+ −→ ROO− + H+ + M(n+1)+
alkoxy radical by thermolysis. The radical un-
dergoes a bimolecular reaction to terminate the
−→ ROOH (12)
formation of radicals (Eq. 11). In the steady
state, the termination of radicals is balanced by
ROOH + Mn+ −→ RO• + OH− + M(n+1)+ (13)
their production. This mechanism is too simple
to explain the reaction in detail. In real systems,
ROOOOR −→ RO• + O2 + RO• (14)
thermolysis may not be the only course of de-
composition [108].
12 Acetic Acid

Alternatively, hydroperoxides may come Besides acetaldehyde, 2-butanone or methyl


from the complexation of metal catalysts with ethyl ketone is another major byproduct. The
peroxy radicals (Eq. 12). Hydroperoxide radi- ketone is the result of the termination of sec-
cals generate new radicals (Eqs. 10, 13). There- butylperoxy radical by the Russel mechanism
fore, the catalyst is important in maintaining a (Eq. 15).
constant flux of radicals. However, in certain Other impurities include propionic acid and
cases, catalysts may actually inhibit the decom- butyric acid. sec-Butoxy radicals undergo β-
position [109]. scission to yield propionaldehyde. Oxidation of
Manganese and cobalt are common catalysts the aldehyde gives propionic acid. Butyric acid
for LPO. These metals accelerate the decompo- is derived from n-butyl radicals.
sition of hydroperoxide. There is evidence that Higher paraffins are oxidized by similar
manganese may enhance the oxidation of ketone mechanisms to that of butane. However, the
intermediates through a mechanism involving products include shorter chain methyl ketones
enols [110]. and difunctional intermediates. These are the
The peroxy radicals terminate by forming results of intramolecular hydrogen abstraction.
tetroxides (Eq. 11), which decompose to yield European countries usually produce acetic acid
alkoxy radicals and oxygen (Eq. 14). from naphtha since naphtha is cheap and avail-
If the tetroxide has an α-hydrogen atom, the able. However, the naphtha-based processes
decomposition may follow a Russel mechanism yield large amounts of impurities that increase
[111]. The products are oxygen, a ketone, and the cost of purification.
an alcohol (Eq. 15). However, the mechanism is
controversial. Recent reports both support [112] Industrial Operation [6, 114–116] (Fig. 6).
and challenge the mechanism [113]. Air or oxygen-enriched air can be used as the
Besides hydrogen abstraction, alkoxy radi- oxidant. Multivalent metal ions, such as Mn,
cals can participate in β-scission (Eq. 16). Prod- Co, Ni, and Cr, are used as catalysts. Some
ucts vary depending on the structure of the radi- processes, however, are noncatalytic. Reaction
cals. Primary, secondary, and tertiary alkoxy rad- conditions are 150 – 200 ◦ C for a range of reac-
icals yield alcohols, aldehydes, and ketones, re- tion pressures that include 5.6 MPa. The reaction
spectively. pressure for naphtha oxidation is lower. The re-
The mechanism of butane oxidation is com- action solvent consists of acetic acid, varying
plex. However, with detailed understanding of amounts of intermediates, water, and dissolved
product distribution and rates, a mathematical hydrocarbons. Control of the water concentra-
model was developed [103]. tion below some maximum level appears to be
About 25 % of the carbon of consumed bu- critical.
tane appears as ethanol in the initial step as the The reaction section (a – d) of a liquid-phase
first isolable non-peroxidic intermediate. The re- oxidation unit consists of a sparged tubular re-
action probably involves decomposition of sec- actor or column (a) and one or more phase sep-
butoxy radicals to form acetaldehyde and an aration vessels (b – d) for separating the gas and
ethyl radical (Eqs. 16, 17). Another source of two liquid phases from the reactor. The hydro-
acetaldehyde is the oxidation of ethanol. Ac- carbon vapor exiting the reactor (a) can be re-
etaldehyde then reacts rapidly to produce acetic covered for recycling. Normally the reactor va-
acid. Therefore, acetaldehyde is a major inter- por is expanded through a turbine (b) to recover
mediate in butane LPO. duty to compress air for use in the reactor. The
consequent reduction in temperature condenses
the hydrocarbon. The top organic layer from the
phase separator (d) is rich in hydrocarbons and
(16) is recycled to the reactor. The bottom, aqueous
layer, is distilled to recover the hydrocarbon for
CH3 CH•2 + O2 −→ CH3 CH2 OO• recycle.
2 CH3 CH2 OO• −→ 2 CH3 CH2 O• + O2
The residual, hydrocarbon-free product con-
sists of volatile, neutral oxygenated deriva-
CH3 CH2 O• + RH −→ CH3 CH2 OH + R• (17) tives (aldehydes, ketones, esters, and alcohols),
Acetic Acid 13

water, volatile monocarboxylic acids (formic, Propagation:


acetic, propionic, and butyric from butane),
and nonvolatile materials (difunctional acids, γ-
butyrolactone, condensation products, catalyst
residues, etc).
The volatile neutral substances can be recov- (20)
ered as mixtures or individually. They are used
for derivatives, sold, or recycled to the reactor.
Most of these components generate acetic acid
on further oxidation.
The separation of water and formic acid from
acetic acid involves several distillations (f). Wa-
ter removal is the most difficult and costly step
of the purification process. It is accomplished by
azeotropic distillation with entrainment agents, (21)
such as ethers, or by extractive methods.
Formic acid is separated from the resulting Peracetic acid reacts with acetaldehyde
anhydrous acetic acid usually by fractionation to generate acetaldehyde monoperacetate
with an azeotroping agent. The remaining higher [7416-48-0]. The acetaldehyde monoperacetate
boiling acids are separated from acetic acid as a decomposes efficiently to acetic acid by a hy-
residue stream by fractionation. dride shift in a Baeyer – Villiger reaction. The
In some cases, hydrocarbons such as heptane methyl migration leads to the byproduct methyl
and isooctane can be added to the reactor to im- formate [118]:
prove separation. These chemicals form a high-
boiling azeotrope with formic acid.
In the case of naphtha oxidation, diacids such
as succinic acids are isolated for sale [117]. The
nonvolatile residue can be burned to recover en-
ergy.

4.3. Acetaldehyde Process

Oxidation of acetaldehyde represents a major


process for making acetic acid [6], [8] (Eq. 18).

CH3 CHO + 1/2 O2 −→ CH3 COOH (18)


The alkyl migration becomes more pro-
Although oxidation reactions are rather com-
nounced with higher aldehydes, particularly
plex, a simplified view is presented here. The ox-
aldehydes having a branch at the α-position.
idation of acetaldehyde to acetic acid proceeds
Chain termination occurs primarily through
through a free-radical chain which produces per-
bimolecular reactions of acetylperoxy radicals
acetic acid as an intermediate.
via an intermediate tetroxide (Eq. 22). [119].
Iniation:

(19) (22)
14 Acetic Acid

Figure 6. Oxidation of n-butane in the liquid phase (Chemische Werke Hüls process)
a) Reactor; b) Air cooler; c) Collector; d) Separation vessel; e) Pressure column; f) Distillation column

At low oxygen concentrations another free-


radical decomposition reaction becomes impor-
tant (Eq. 26).

(23)

(26)

The rate of decarbonylation increases with in-


(24) creasing temperature. Decarbonylation becomes
significant when insufficient oxygen is present
to scavenge the acetyl radicals.
Catalysts can play several important roles in
aldehyde oxidations [120]. Catalysts decompose
peroxides and so minimize the explosion hazard
(Eq. 27). In addition, manganese also reduces
acetylperoxy radicals [121] directly to peroxy
(25) anions [122]:

Equations (23) – (25) are the source of most


of the carbon dioxide, methanol, formaldehyde,
and formic acid byproducts. Uncatalyzed oxida-
tion is efficient so long as the conversion of acet- (27)
aldehyde is low and there is a significant concen-
tration of aldehyde in the solvent. This keeps the
steady state concentration of acetylperoxy rad-
icals low and favors the Baeyer – Villiger reac-
tion over the reactions (23) – (25). Special pre-
(28)
cautions must be taken in the uncatalyzed reac-
tion to prevent the concentration of acetaldehyde Reaction with Mn2+ assists in suppressing
monoperacetate from reaching explosive levels the concentration of acetylperoxy radicals. The
[6]. Mn3+ formed can generate the acyl radical for
Acetic Acid 15

the propagation step (Eq. 28), but does not con- cal in the liquid phase. Other catalysts, for exam-
tribute to inefficiency-generating reactions. ple phosphomolybdic acids [128], also catalyze
Manganese also greatly increases the rate of acetaldehyde oxidation.
reaction of peracetic acid and acetaldehyde to Additional byproducts from acetaldehyde
produce acetic acid [123]. The reaction in the oxidation include ethylidene diacetate, crotonic
presence of manganese is first-order with respect acid, and succinic acid.
to peracid, aldehyde, and manganese. In addi-
tion, the decomposition replenishes the supply Industrial Operation. A typical acetalde-
of radicals. This is important since the oxidation hyde oxidation unit is depicted in Fig-
requires a constant flux of radicals. Manganese ure 7. The reactor (a) is sparged with air or
ions increase both the rate and efficiency of ox- oxygen-enriched air. Temperatures are typically
idation. 60 – 80 ◦ C with pressures of 0.3 – 1.0 MPa. The
Copper can interact synergistically with a reaction mixture is circulated rapidly through an
manganese catalyst [124]. Manganese has some external heat exchanger to remove the heat of re-
negative aspects associated with the fact that it action. The vent gas is cooled and then scrubbed
greatly increases the reaction rate [125]. The with recirculated crude product (which goes to
increased reaction rate leads to oxygen starva- the reactor) and finally with water (which goes
tion and an increasing steady state concentra- to the aldehyde recovery column). The reactor
tion of radicals. Both contribute to byproduct product is fed to the aldehyde recovery column
formation by decarbonylation and decarboxyla- (b), from which the aldehyde is recycled, and
tion. However, Cu2+ can oxidize acetyl radicals then to a low-boilers column (c) in which methyl
very rapidly (Eq. 29) [126]. acetate is removed. The next column is the acetic
acid finishing column (d), where water is re-
moved overhead by azeotropic distillation and
finished product comes off as a vapor sidestream.
Yields are generally in excess of 90 % and purity
(29) is greater than 99 %.
The acetylium ion can react as shown in
Equation (30).
4.4. Other Processes
Acetic Acid from Ethylene. Efforts to con-
vert ethylene directly to acetic acid without go-
ing through an acetaldehyde isolation step have
been of interest. Although the price of ethylene
generally makes this process unattractive, some
developments are noteworthy. Effective oxida-
tion of ethylene to acetic acid has been demon-
strated with metal oxides such as vanadium pen-
toxide. Seone et al. [129] demonstrated that the
(30) presence of palladium enhances etylene oxida-
tion to acetic acid as temperatures as low as
Peroxide or Mn3+ can reoxidize the Cu+ .
230 ◦ C. Showa Denko combined palladium with
Copper diverts a fraction of the reaction through
heteropolyacids and patented a catalyst for pro-
a nonradical pathway and consequently provides
ducing acetic acid from ethylene and oxygen.
a termination step that does not result in ineffi-
The catalyst contains palladium, an heteropoly-
ciency.
acid, such as silicotungstic acid, and potassium
Another effective catalyst is cobalt. At low
tellurite or potassium selenite. The process is
concentration, this catalyst shortens the induc-
operated at 150 ◦ C and 0.7 MPa. Although wa-
tion period [126]. The cobalt catalyst is regener-
ter is not consumed in the reaction, the presence
ated by decomposing peracetic acid. In kinetic
of water enhances the selectivity to acetic acid
studies [127], CH3 CO3 was the main free radi-
and is recommended.
16 Acetic Acid

Figure 7. Oxidation of acetaldehyde to acetic acid


a) Reactor; b) Acetaldehyde column; c) Methyl acetate column; d) Finishing column; e) Column for recovering entrainer;
f) Off-gas scrubber column

Acetic Acid from Ethane. Several groups enhances selectivity to acetic acid from the oxi-
have investigated catalysts for the conversion of dation of ethane and/or ethylene. Again, water is
ethane to acetic acid (Eq. 31). used to enhance selectivity to acetic acid. Stan-
dard Oil [139] claims good selectivity to acetic
C2 H6 + 3/2 O2 −→ CH3 CO2 H + H2 O (31) acid with a vanadyl pyrophosphate catalyst con-
Union Carbide [130] developed the Ethoxene taining a transition metal. Hoechst [140] claims a
process for the production of ethylene from catalyst containing molybdenum and palladium
ethane and oxygen. The earliest catalysts con- as effective for the production of acetic acid from
sisted of molybdenum, vanadium, and niobium ethane. An acetic acid selectivity of 84 % was at-
oxides and were very selective for ethylene tained at 250 ◦ C and 7 bar with a 14-s residence
at temperatures below 300 ◦ C. Unfortunately, time.
ethane conversions were low (about 10 %) due Although ethane is an inexpensive raw mate-
to inhibition by the product. Further develop- rial and high selectivities to acetic acid have been
ment [131] focused on the coproduction of ethy- achieved, it is unlikely that ethane oxidation will
lene and acetic acid with a catalyst comprised compete with methanol carbonylation in the near
of molybdenum, vanadium, niobium, calcium, future. The oxygen concentration must be lim-
and antimony. The addition of water enhances ited for safety reasons and therefore ethane con-
acetic acid formation. A later patent [132] dis- version is limited per pass in the reactor. Al-
closes that the addition of water and an ethylene though staged addition of oxygen is possible,
hydration catalyst improves selectivity to acetic product inhibition remains a problem and limits
acid. ethane conversion. Since the addition of water is
Rhône-Poulenc [133], [134] has patented a needed to improve selectivity to acetic acid, wa-
process to make acetic acid from ethane with a ter must be removed from the acetic acid, usually
vanadium oxide or vanadyl pyrophosphate sup- by extractive distillation.
ported on titanium dioxide. Tessier et al. [135]
found that acetic acid production was favored Acetic Acid from Microorganisms Since
over ethylene and carbon oxides at temperatures about 10 000 b.c., aqueous solutions of acetic
below 300 ◦ C. Roy et al. [136] demonstrated that acid have been prepared from spoiled wine
the addition of molybdenum enhanced acetic [141], [142]. Ethanol and sugar were the pri-
acid selectivity. Desorption of acetic acid from mary feedstocks for microorganism production
the catalyst surface was speculated to be the rate- of acetic acid, although biomass has been pro-
determining step of the reaction. posed [143]. The concentration of acetic acid
BP Chemicals [137], [138] claims that the ad- in solution is limited by the ability of bacteria
dition of rhenium to mixed metal oxide catalysts to thrive in low-pH solutions. Consequently,
Acetic Acid 17

researchers have focused on improving acetic mary amines are generally not suitable extrac-
acid productivity and lowering the pH of the tion additives due to their water solubility. Sec-
bacterial culture. Mutant strains of Clostrid- ondary amines have high extraction coefficients
ium thermoaceticum [144] have been developed [147] but can form amides during the acid re-
to produce acetic acid in solutions below pH covery process. Tertiary amines such as triocty-
5. Improvement of acetic acid productivity of lamine [148] have extraction coefficients which
an Acetobacter aceti strain was achieved by are strongly dependent on amine concentration
amplification of the aldehyde dehydrogenase and the cosolvent used. Eyal and Canari [149]
gene with a multicopy vector [145]. Bacterial discuss how anion exchange, ion-pair forma-
production is gaining interest since it is a en- tion, hydrogen-bond formation, and solvation
vironmentally friendly process. Nevertheless, all play important roles in amine-based extrac-
cost-effective acetic acid concentration and pu- tion of acetic acid. In addition to amines, dibutyl
rification remain a challenge. phosphonate [150] and trioctyl phosphine oxide
[151] have high extraction coefficients relative
to alcohols, ethers, or esters.
4.5. Concentration and Purification The selection of a water-removal method de-
pends on economics. Extraction is generally pre-
In most commercial processes acetic acid is pu- ferred at low concentrations of acetic acid.
rified from an aqueous acetic acid solution by
straight distillation methods that are economi-
cally viable provided the acetic acid is in high 4.6. Construction Materials [152], [153]
concentrations when initially isolated from the
reaction system of the process. Other acetic acid Little is known about construction materials for
purification techniques can be used, in partic- equipment in acetic acid processes. The infor-
ular, for dilute acetic acid such as byproduct mation on materials is usually considered a trade
streams of important industrial processes, e.g., secret. Liquid streams containing acetic acid cor-
cellulose acetate production (→ Cellulose Es- rode metals. The corrosion increases with in-
ters). Azeotropic distillation, solvent extraction, creasing concentrations of acetic acid, halides,
and extractive distillation can recover acetic acid and formic acid. High temperatures (> 200 ◦ C)
from these aqueous streams. Direct distillation also increase the corrosion rate. AISI 316 stain-
requires a significant number of plates and a high less steel [12597-68-1] is used for processes
reflux ratio in the columns. In extractive distil- without reducing agents and halides. In the pres-
lation, the vapor streams of acetic acid and wa- ence of reducing agents, AISI 321 stainless steel
ter are scrubbed with a high-boiling solvent that is necessary. Hastelloy B or C or other mate-
preferentially dissolves one of the components. rials are required if halides are present. Alu-
Azeotropic Distillation. In azeotropic distil- minum [7429-90-5] and AISI 304 stainless steel
lation, a compound that decreases the boiling are used in storage tanks, pumps, and piping at
point of water is used. If the azeotropic agent is room temperature and high acid concentrations.
immiscible with water, it can be separated eas- AISI 316 stainless steel contains 16 – 18 wt %
ily from water and recycled. Esters, ethers, ben- Cr, 10 – 14 wt % Ni and 2 – 3 wt % Mo. AISI 321
zene, and chlorinated hydrocarbons have been stainless steel has 17 – 19 wt % Cr, 9 – 12 wt %
proposed as azeotropic agents [146]. Ni and > 0.4 wt % Ti. AISI 304 stainless steel is
Solvent Extraction. Acetic acid is removed comprised of 18 – 20 wt % Cr and 8 – 10.5 wt %
from aqueous solutions (0.5 – 5 wt % acetic acid) Ni.
by solvent extraction. The aqueous solution is
contacted with an organic solvent, often con-
taining an organic base, and then acetic acid
is stripped from the base in a distillation pro- 5. Wastewater and Off-Gas
cess and separated from the cosolvent, usually Problems [154]
an alkane, by phase separation. Consequently,
it is important for the organic solvent to have a Waste streams from acetic acid process usu-
high affinity for acetic acid relative to water. Pri- ally contain residual acetic and formic acids.
18 Acetic Acid
Table 6. Sales specifications for glacial acetic acid [76]
These acids must be recycled, diluted, or treated
chemically and then degraded biologically. Eu- Sales specifications Limits
ropean countries require neutralization or bio-
Acetic acid, wt % min. 99.85
logical degradation of these waste streams [6], Distillation range (including 118.1), ◦ C max. 1.0
[8]. Freezing point, ◦ C min. 16.35
Acetic acid is corrosive and can damage hu- Color, Pt – Co units max. 10
Water content, wt % max. 0.15
man skin and internal organs. Acetic acid should Reducing substances, as formic acid, max. 0.05
be handled with care to avoid breathing vapors. wt %
Aldehydes, as acetaldehyde, wt % max. 0.05
If a spill occurs, neutralize soil and wash with Iron, ppm max. 1
soda ash or lime. The Clean Water Act (USA) Heavy metals, as Pb, ppm max. 0.05
and Superfund (USA) dictate that a reportable Chlorides, ppm max. 1
Sulfates, ppm max. 1
quality (RQ) of 2270 kg (5000 lb) [155]. Sulfurous acid, ppm max. 1
In Germany [156], no more than 3 kg/h may Permanganate time min. 2h
be emitted in vent gases, with a maximum of
150 mg/m3 . The vent gas is scrubbed or chilled
to eliminate the acids.
Under the same German regulations, the 7. Analysis
maximum emissions for methyl acetate, ethyl
acetate, butyl acetate, and phenyl acetate are Gas chromatography is the usual technique for
300 mg/m3 . The off-gas is limited to 6 kg/h [8]. determining the acetic acid content of a volatile
The recommended methods of removal of the mixture. Packed columns can be used, but cap-
acetic acid are thermal condensation, washing illary columns are preferred. Carbowax 20M,
with nonvolatile organic solvent, physical ab- terephthalic acid terminated [41479-14-5], is the
sorption or burning. preferred substrate.
In the United States, the United States Clean
Air Act governs the amount of emissions. Each
state also sets individual emission limits. The 8. Storage, Transportation, and
limits range from 0.25 mg/m3 to 0.37 mg/m3
(North Dakota), to 0.4 mg/m3 (Virginia) to Customs Regulations [8], [152], [159]
0.5 mg/m3 (Connecticut and South Dakota) to
0.595 mg/m3 (North Carolina) [154]. DOT regulations regard glacial acetic acid
(99.7 %) as a hazard. The acid belongs to
UN/DOT Hazard Class 8 and Shipping Group
II [160]. Acetic acid should be stored in a cool,
6. Quality Specifications dry place away from contact with oxidizing ma-
terials. Containers should be kept closed and la-
There is essentially one commercial grade of beled as “Corrosive”. Precautionary labels such
acetic acid sold in the United States. Elsewhere, as “Flammable” are recommended. Even when
three or more grades are available differing as emptied, the containers may still retain acid
to specifications for heavy metals, chloride, sul- residue. Wash the container with water. The
fate, arenic, and iron [157]. Also, depending emptied container should still have a warning
on specific end uses, additional product criteria label.
must be considered. For example, in the man- The acid can be stored and transported in
ufacture of vinyl acetate, halides are important containers lined with stainless steel, glass, or
since they are a catalyst poison in vinyl acetate polyethylene. Another material for containers is
processes. One of the most critical specifications aluminum. Aluminum forms a protective coat-
for all end uses of acetic acid is “permanganate ing of aluminum oxide or aluminum acetate
time.” The test for “permanganate time” is a when exposed to acetic acid. The coating pre-
semi-quantitative wet method for the measure- vents further corrosion. Caution is warranted to
ment of oxidizable impurities. One manufac- prevent water and mercury contamination. Wa-
turer’s sales specification is given Table 6 [76]. ter and small amounts of mercury accelerate the
Acetic Acid 19

corrosion. Maintaining a high acid concentra- 10. Derivatives


tion and not using a mercury thermometer help
to prevent catastrophic corrosion. This section contains information about acetic
The limits for shipping concentrated acetic acid derivatives that are not discussed in de-
acid in passenger aircraft or railcar is 1 L, and tail elsewhere in this encyclopedia (→ Acetic
30 L in cargo aircraft. Acetic acid has a low melt- Anhydride, → Cellulose Esters, → Chloroacetic
ing point of 16 ◦ C. Transporting the acid in cold Acids, → Esters, Organic, → Vinyl Esters).
weather requires the vessels to be heated. Stor-
age containers, tank trucks, and pipes for con-
centrated acid should be equipped with heated 10.1. Salts
coils. Storage vents also need to be heat traced
to prevent the acid from crystallizing. 10.1.1. Aluminum Acetate

German Legal Requirement for Food- Three aluminum acetates are known, two
stuffs. Commercial vinegar exceeding 11 wt % basic and one neutral: Al(OH)2 CO2 CH3
acetic acid may be sold in closed containers. [24261-30-1], Al(OH)(CO2 CH3 )2 [142-03-0],
The material of the containers should be resis- and Al(CO2 CH3 )3 [139-12-8].
tant to acetic acid. The container must be clearly Properties. Al(CO2 CH3 )3, M r 204.1, is a
marked with a label warning as “Handle with white, water-soluble powder that decomposes at
Care.”, “Do Not Swallow Undiluted.” Solutions about 130 ◦ C to give acetic anhydride along with
containing more than 25 wt % acetic acid are not basic aluminum acetates [161].
available to the public. Commercial dealers are Production. Neutral aluminum acetate is
allowed to handle the acid. made from aluminum metal and glacial acetic
acid that contains 0.1 – 1 % acetic anhydride,
German Customs Requirements (Vinegar which scavenges any water present [162]. The
Law) [5]. The Vinegar Law, Paragraph 1, dic- anhydrous triacetate cannot be made from aque-
tates that the transfer of synthetic vinegar in re- ous solutions. The basic acetates can be prepared
tail markets is taxable. The tax is known as the from Al(OH)3 and aqueous acetic acid solutions
Vinegar Tax. Both imported and local products [163].
are subjected to the tax. With changing of vine- Uses. Aluminum acetate is used as a dye mor-
gar price, the tax is adjusted. dant in the dyeing of fabrics.
Tax exempt status is granted for acetic acid
used in commercial purposes. Another case for
tax exempt status also deals with commercial 10.1.2. Ammonium Acetate
uses where the acid is consumable by humans.
Properties. Ammonium acetate [631-61-8].
CH3 CO2 NH4 , M r 77.08, mp 114 ◦ C, forms col-
9. Uses orless, hygroscopic needles. The solubilities of
this salt in 100 g of water or methyl alcohol are,
Acetic acid has a broad spectrum of applica- respectively, 148 g (4 ◦ C) and 7.9 g (15 ◦ C).
tions. An outline of these is given in Figure 8 Production. Ammonium acetate is manufac-
[1], [48]. Greater than 65 % of the acetic acid tured by neutralizing acetic acid with ammo-
produced worldwide goes into polymers derived nium carbonate or by passing ammonia gas into
from vinyl acetate (→ Vinyl Esters), or cellulose glacial acetic acid [114]. Acidic ammonium ac-
(→ Cellulose Esters). Most of the poly(vinyl ac- etate, CH3 CO2 NH4 · CH3 CO2 H [25007-86-7],
etate) is used in paints and coatings or for mak- is manufactured by dissolving the neutral salt in
ing poly(vinyl alcohol) and plastics. Cellulose acetic acid.
acetate is used to produce acetate fibers. Acetic Uses. Ammonium acetate is used in the man-
acid and acetate esters are used extensively as ufacture of acetamide and as a diuretic and di-
solvents. aphoretic in medical applications. The wool in-
dustry also uses this salt as a dye mordant.
20 Acetic Acid

Figure 8. Uses of acetic acid


Acetic Acid 21

10.1.3. Alkali Metal Salts Esterification involves an equilibrium be-


tween reactants and product (Eq. 33). Adding
Properties. All of the alkali metals (Li, Na, excess reactants or removal of water drive the
K, Rb, Cs) form acetates. The aqueous solu- equilibrium to favor the formation of ester.
bilities of these salts increase with increasing Azeotroping agents eliminate water and force
atomic mass of the alkali metal [164]. The potas- the reaction to completion. Common agents are
sium salt [127-08-2]. M r 98.14, mp 292◦ C, and cyclohexane, benzene, and toluene.
sodium salt [127-09-3], M r 82.04, mp 324◦ C,
are the most common. The former crystallizes [CH3 COOR] [H2 O]
Keq = (33)
from water as white columns. The latter can be [CH3 COOH] [ROH]
purified by crystallization from acetic acid. Sev-
Esterification with acetic anhydride offers an
eral acetic acid solvates of the alkali metal salts
alternative route for making acetates. Due to its
are known [163].
high reactivity, acetic anhydride readily forms
Production. Potassium and sodium acetates
esters with alcohols. The reaction is irreversible.
normally are manufactured from glacial acetic
The esterification goes to completion without
acid and the corresponding hydroxides. The salts
eliminating products or water.
also can be prepared from acetic acid on treat-
Additions of acetic acid to olefins present an
ment with the metal, the metal carbonate, or the
alternative way to make acetates, especially for
metal hydride [163].
branched esters. Synthesis of these hindered es-
Uses. Potassium acetate is used to purify
ters by esterification is not efficient. The equi-
penicillin. It is also used as a diuretic and as a
librium does not favor the desirable products.
catalyst to make polyurethane. The sodium salt
Rhône-Poulenc uses this method to prepare iso-
is used frequently in water as a mild alkali.
propyl acetate from acetic acid and propylene
[172]. Catalysts can be strong protic or Lewis
acids, like sulfuric acid or BF3 · OEt2 [173].
10.2. Esters (→ Esters, Organic) [166–169]
Ethyl acetate can also be produced directly from
Properties. Physical properties of acetate es- acetaldehyde.
ters are listed in Table 7 [168]. Adding hydrogen and carbon monoxide to
acetic acid or acetic anhydride can produce ac-
Production. The reaction of an alcohol and etates. Alternatively, hydrogenation of acetic
an organic acid produces an ester in the presence acid yields ethanol and ethyl acetate. Many stud-
of an acid catalyst [166]. The reaction, esterifi- ies relate to supported heterogeneous catalysts
cation, is the most common process for manu- with molybdenum and group VIII metals (Pd,
facturing acetate esters (Eq. 32). Rh, or Ru). Additionally, homogeneous cataly-
sis with ruthenium can result in high selectivity
ROH + CH3 COOH  CH3 COOR + H2 O (32) [172].
Commercial processes also include the re-
Other industrial processes include the reac-
action of aldehdyes to make esters. The Tis-
tion of acetic anhydride with alcohols and the
chenko reaction uses alkoxide catalysts. Typi-
Tishchenko reaction. Other methods for synthe-
cal catalysts are aluminum alkoxide, boric acid
sizing acetate esters are the addition of acetic
and magnesium or calcium aluminum alkoxides
acid to olefins, carbonylation of acetic acid or
[173].
anhydride, and reductive methods involving car-
boxylic acids or anhydride.
Uses. Applications of acetates depend on
Commercial processes for esterification are
their physical properties such as boiling point
usually continuous and are performed in the liq-
and evaporation rate. Therefore, uses of acetates
uid phase. The reaction requires strong acids
cover many products such as coatings, solvents
such as sulfuric acid or organic sulfonic acids.
for plastics, lacquers, resins, and gums.
Another type of catalyst is ion-exchange resins.
In contrast, gas-phase technology is available
with sulfonated polymer [170] or supported
phosphoric acid as catalyst [171].
22 Acetic Acid
Table 7. Physical properties of acetate esters

Ester CAS no. Mr n20


D d20
20 bp, ◦ C fp, ◦ C Flash pt., ◦ C

Methyl acetate [141-78-6] 74.1 1.36 0.93 57.0 −98.1 −10


Ethyl acetate [108-05-4] 88.1 1.37 0.902 77.1 −83.6 − 4
Propyl acetate [109-60-4] 102.13 1.38 0.887 101.6 −92.5 13
Isopropyl acetate [108-21-4] 102.13 1.38 0.872 90.1 −73.4 2
Butyl acetate [123-86-4] 116.16 1.39 0.882 126.0 −73.5 22
Isobutyl acetate [110-19-0] 116.16 1.39 0.871 117.2 −98.6 18
sec-Butyl acetate [105-46-4] 116.16 1.39 0.876 112.0 31
tert-Butyl acetate [540-88-5] 116.16 1.39 0.867 97.0
n-Pentyl acetate [628-63-7] 130.18 1.40 0.876 149.2 −70.8
2-Ethylhexyl acetate [103-09-3] 172.26 1.42 0.873 199.3 −93.0 71

10.2.1. Methyl Acetate vantage of the alcohol – ester – water azeotrope.


After decanting and purification, the final yield
Properties. Methyl acetate is colorless and of the ester can reach as high as 95 %.
has a pleasant odor. Methyl acetate forms Another means of making ethyl acetate is
azeotropes with water (3.5 wt % H2 O, bp theTischenko reaction. Two moles of acetalde-
56.5 ◦ C) and methanol (19 wt % MeOH, bp hyde can undergo bimolecular reaction to yield
54.0 ◦ C). Other properties are listed in Table 7. ethyl acetate with a metal alkoxide catalyst at
Production. Most commercially available low temperature (Eq. 34). A popular catalyst is
methyl acetate is a byproduct in the manufacture aluminum alkoxide.
of acetic acid. Another method is the esterifica-
tion of methanol and acetic acid with sulfuric
acid as catalyst. The product ester is removed as
the methanol/methyl acetate azeotrope.
Uses. Methyl acetate has the lowest boiling (34)
point (55.8 – 58.2 o C) of all organic acetates. It
Uses. Ethyl acetate is a common solvent for
evaporates about five times faster than butyl ac-
coatings, adhesives, ink, cosmetics, and film
etate [166]. Therefore, methyl acetate finds uses
base. Specialty chemicals and pharmaceutical
where rapid evaporation is necessary. It is em-
industries use ethyl acetate as a solvent for syn-
ployed as a process solvent for preparing cellu-
thesis. Coffee is occasionally decaffeinated with
lose nitrates. Transesterification to make esters
ethyl acetate in an extraction process.
uses methyl acetate as a reagent. In addition, the
production of acetic anhydride requires the ac-
etate. 10.2.3. Butyl Acetate

Properties. All four of the esters, n-


10.2.2. Ethyl Acetate
butyl [123-86-4], sec-butyl [105-46-4], isobutyl
Properties. Ethyl acetate has a pleasant odor. [110-19-0], and tert-butyl acetate [540-88-5],
It forms azeotropes with water (8.2 wt % H2 O, are colorless liquids with pleasant odors.
bp 70.4 ◦ C), ethanol (30.8 wt % EtOH, bp Azeotropic data for the butyl acetates are given
71.8 ◦ C), and methanol (44 wt % MeOH, bp in Tables 8 and 9 [5]. Other properties are listed
60.2 ◦ C). With water and ethanol, the ester forms in Table 7.
a ternary azeotrope (7.8 wt % H2 O, 9.0 wt % Table 8. Binary azeotropes with the butyl acetates
EtOH, bp 70.3 ◦ C). Other properties are listed ◦
Component A Component B bp, C wt % B
in Table 7.
Production. Ethyl acetate is made from n-Butyl acetate Water 90.2 26.7
sec-Butyl acetate Water 86.6 19.4
ethanol [64-17-5] and acetic acid in batch or con- Isobutyl acetate Water 87.4 –
tinuous processes. A major step in the continu- n-Butyl acetate n-Butanol 117.2 47
ous process is the removal of the ester. The dis- sec-Butyl acetate sec-Butanol 99.6 86.3

tillation process separates the ester by taking ad-


Acetic Acid 23
Table 9. Ternary azeotropes with the butyl acetates

Component A Component B Component C bp, C wt % B wt % C

n-Butyl acetate Water n-Butanol 89.4 37.3 37.3


sec-Butyl acetate Water 2-Butanol 86.0 23.0 45.0
Isobutyl acetate Water Isobutyl alcohol 86.8 30.4 23.1

Production. Esterification of butanol and Production. The normal industrial method


acetic acid produces butyl acetate. The catalyst is involves reaction of acetic anhydride [108-24-7]
sulfuric acid. The removal of water by azeotropic with anhydrous hydrogen chloride [7647-01-0]
separation forces the reaction to completion. The [179], [180]. On the laboratory scale, it can
acid catalyst is neutralized and the ester purified be produced from acetic acid and reagents
by distillation [8]. such as thionyl chloride [7719-09-7], phospho-
Uses. Butyl acetate is used primarily in coat- rus trichloride [7719-12-2], or phosphorus pen-
ings. It is a good solvent with low volatility. The tachloride [10026-13-8] [181].
lacquer and enamel industries employ butyl ac- Acetyl chloride is normally consumed at the
etate as a solvent for making acylic polymers, site of generation since transportation and stor-
vinyl resins, and nitrocellulose. Other industries age are difficult. Glass, enamel, porcelain, clay,
utilizing the acetate as solvent include printing, and polytetrafluoroethylene are suitable materi-
photographic, adhesives, extraction and pharma- als for handling acetyl chloride.
ceutical. Uses. Acetyl chloride is an efficient acety-
lating agent for alcohols and amines to produce
esters and amides. It is important in the synthesis
10.2.4. 2-Ethylhexyl Acetate of dyes and pharmaceuticals. Acetyl chloride is
used in the Friedel – Craft acylation of benzene
2-Ethylhexyl acetate is prepared by esterifica- to yield acetophenone.
tion of 2-ethyl-1-hexanol with acetic acid with
the aid of an acid catalyst. Distillation with a
low-boiling azeotropic solvent removes water 10.4. Amides
from the reaction. The ester is used in lacquers,
in silk-screen inks, and in paints as a coalescing 10.4.1. Acetamide
agent. Properties are listed in Table 7.
Properties. Acetamide [60-35-5],
CH3 CONH2 , M r 59.07, mp 81.5 ◦ C, bp 222◦ C,
10.2.5. Other Esters d 20 1.161, forms deliquescent hexagonal crys-
tals that are odorless when pure. Acetamide is
Properties of some other esters are given in Ta- soluble in water and low molecular mass alco-
ble 7. Most esters are colorless liquids with a hols.
mild fruity smell. The esters are used as solvents Production. Acetamide can be produced by
for making cellulose and elastomers [178]. several methods. Ammonia reacts vigorously
with acetyl halides or acetic anhydride to pro-
duce acetamide. Alkyl acetates also react with
10.3. Acetyl Chloride ammonia to yield acetamide. Dehydration of
ammonium acetate is the standard procedure for
Properties. Acetyl chloride [75-36-5] M r preparation of acetamide. Finally, acetonitrile is
78.5, n20 20 ◦ hydrolyzed to yield acetamide in the presence of
D 1.3871, d 4 1.1051, bp 51.8 C, mp

− 112.86 C is a colorless, corrosive liquid. an acid or base catalyst. Metal catalysts [183],
Acetyl chloride reacts with moist air to produce [184] and biocatalysts [185] are claimed to cat-
hydrogen chloride and acetic acid. alyze the hydrolysis of acetonitrile. This method
of acetamide production is popular because ace-
tonitrile is a byproduct of acrylonitrile produc-
tion.
24 Acetic Acid

Uses. Acetamide is used as a solvent and as per annum, while world acetic acid capacity
a plasticizer. will grow by an average of 4 % per annum. In
1996 total world acetic acid capacity was ca.
7.1 × 106 t/a and total world production was ca.
10.4.2. N,N-Dimethylacetamide 5.5 × 106 t/a.
In 1996, North America was the region with
Properties. N,N-Dimethylacetamide, the greatest acetic acid production at ca. 36 % of
[127-19-5], CH3 CON(CH3 )2 , M r 87.1, mp the world total. Western Europe was second with
− 20 ◦ C, bp 165.5 ◦ C, d 20 0.943, is a color- ca. 24 % followed by Japan at 15 % and Eastern
less liquid which is soluble in a wide variety of Asia with 14 %. By 2006 the share of acetic acid
solvents. production in North America, West Europe, and
Production. N,N-Dimethylacetamide is pre- Japan is expected to drop to ca. 32 %, 17 %, and
pared by reaction of dimethylamine with acetic 11 %, respectively, while East Asian production
acid, acetic anhydride, or acetate esters. Heat- will increase to 18 %. Consumption and produc-
ing dimethylamine acetate with [186], [187] tion of acetic acid in Asia are forecast to grow
or without [188] a catalyst affords N,N- strongly from 1998 to 2006.
dimethylacetamide. Reaction of dimethylamine The largest end uses of acetic acid are for the
with acetate esters requires a catalyst; sodium manufacture of vinyl acetate, acetic anhydride,
methoxide is typically used. acetate esters, monochloroacetic acid, and as a
Uses. N,N-dimethylacetamide is an excellent solvent in the production of dimethyl terephtha-
solvent and often acts as a catalyst in halogena- late and terephthalic acid. Figure 8 provides a
tion, cyclization, and alkylation reactions. N,N- detailed summary of acetic acid end uses. Vinyl
Dimethylacetamide is used in the spinning of acetate is by far the most significant end use for
polyacrylonitrile and as a solvent in the process- acetic acid. About 43 % of world production of
ing of other polymers. N,N-dimethylacetamide acetic acid in 1996 was used in the manufacture
lithium chelate complexes intercalate cationic of vinyl acetate. About 12 – 15 % of world acetic
sites in layered silicates [189]. acid production is used for each of the remaining
major end uses of acetic acid.
There is little doubt that the technology of the
10.5. Phenylacetic Acid future is methanol carbonylation. In 1972, low-
pressure methanol carbonylation in the United
Properties. Phenylacetic acid [103-82-2], States accounted for only 10 % of the total acetic
C6 H5 CH2 CO2 H, M r 136.14, bp 265.5 ◦ C, mp acid capacity, whereas in 1982 the share had in-
78 ◦ C, d 79.8 1.0809, forms white leaflets on vac- creased to 40 %. By 1993, 46 % of the acetic
uum distillation. It dissolves in hot water but is acid was produced by methanol carbonylation.
only slightly soluble in cold water. Over 90 % of all new acetic acid is manufac-
Production. Hydrolysis of benzyl nitrile or tured by low-pressure methanol carbonylation
carbonylation [190] of benzyl halides or alco- technology.
hols produces phenylacetic acid [191]. BP Chemicals purchased the technology and
Uses. Penylacetic acid is a starting material license rights to the Monsanto methanol car-
in the synthesis of synthetic perfumes and cos- bonylation process in 1986 and has continued to
metics [192]. It is used in the synthesis of peni- license in joint ventures this high-reaction-water
cillin G to stimulate benzylpenicillinase in E. process. Technology improvements have been
Coli. Penicillin G, after extraction from the cul- made in the rhodium-catalyzed carbonylation
ture, is converted to 6-aminopenicillanic acid process since this process was first implemented
and phenylacetic acid. commercially [52]. Celanese in the early 1980s
departed from the Monsanto high-water technol-
ogy to develop a proprietary low-reaction-water
11. Economic Aspects [1] process. BP also has developed a low-reaction-
water technology based on iridium called Cativa
World acetic acid production between 1998 and
2006 is forecast to grow by an average of 3 – 4 %
Acetic Acid 25

that has several advantages over the rhodium- skin more severely than other mineral acids be-
catalyzed high-reaction-water process [55] orig- cause it is miscible with lipids.
inally developed by Monsanto. These develop- Acetic acid irritates the eyes, nose, and throat
ments, as well as others, will most likely ensure above 10 ppm. Repeated exposure to 26 ppm for
that in the future the low-pressure methanol car- ten days causes adverse effects. Over 100 ppm,
bonylation processes will remain the most eco- the acid may even damage organs as described
nomical routes to manufacture acetic acid. above.
Acetic acid from low-pressure methanol car- Concentrated acid can damage skin severely.
bonylation is gradually replacing the more ex- Avoid exposure to glacial acetic acid or inhaling
pensive acetic acid produced by the oxidation vapor. In case of contact, wash the exposed area
of acetaldehyde, butane, and naphtha and by with plenty of water. Therefore, handling of the
high-pressure methanol carbonylation. The ox- acid requires caution.
idation routes to acetic acid in most cases are Oral ingestion of the acid causes pain in the
not competitive with low-pressure methanol car- digestive tract and in the mouth. It may lead to
bonylation. Acetaldehyde oxidation units are vomiting, and respiratory and circulatory dis-
only economically viable provided an acetic tress. If the person is conscious, wash the mouth
acid producer has a captive source of acet- with water and consult physicians.
aldehyde. Similarly, n-butane or naphtha oxi- Acetic acid has a low flash point of 39 ◦ C
dation processes are not competitive with low- [196]. It is readily combustible with an autoigni-
pressure methanol carbonylation unless byprod- tion point of 516 ◦ C. Fortunately, the acid lowers
uct credits are considered. As a result, many its flammability significantly when mixed with
high-cost acetic acid units have ceased opera- water. Beyond 56 %, the flash point is no longer
tion, such as the acetaldehyde oxidation pro- a danger [197].
cesses of Celanese in Clear Lake and Bay City Organic acetates do not cause severe dam-
Texas, and a similar process of Eastman Chem- age unless high exposure occurs. The TLVs vary
ical in Kingsport, Texas. Additionally, the bu- from 5 to 400 ppm [198]. The LD50 for small
tane oxidation plant operated by Union Carbide mammals range from 0.4 to 16 g/kg. The toxic-
at Brownsville, Texas, and the high-pressure ity of the esters decreases as the molecular mass
methanol carbonylation plant of Borden in Geis- increases from C1 to C4 . The LD50 of isoamyl
mar, Louisiana, have ceased operation. acetate (7.42 g/kg) is twice that of methyl acetate
(3.7 g/kg). However, ingestion or absorbtion of
methyl acetate poses a hazard since the ester is
12. Toxicology and Occupational converted to methanol.
Acetates irritate the mucous membrane
Health slightly. When ingested or absorbed, esters are
readily hydrolyzed to the corresponding alco-
Acetic acid has a pK a of 4.5. The acid is not as
hols and carboxylic acids. Some volatile esters
strong as mineral acids or formic acid. However,
act as asphyxiants and narcotics.
its corrosiveness justifies caution in handling.
Ethyl acetate has an LD50 of 4.97 g/kg in the
Table 10 lists exposure limits for acetic acid
rabbit. The toxicity of acetates is usually in the
and derivatives [194].
range of 100 – 250 ppm. Ethyl acetate has the
When humans ingest acetates, the esters are
highest PEL of 500 ppm. Humans can tolerate
hydrolyzed readily to the corresponding alco-
up to 400 ppm before nose and throat irritation.
hols and carboxylic acids. A study using ra-
n-Butyl acetate differs from its isomers.
dioactive labeling shows that the liver and brain
When tested with rats, n-butyl acetate has an
cholesterol incorporate acetic acid [195]. No cu-
oral LD50 of 14 mg/kg. For humans, irritation in
mulative toxicity has been reported.
the throat starts at an exposure of 200 ppm [194].
Dilute acid with 5 % acetic acid such as vine-
Severe eye and nose irritation occurs at 300 ppm.
gar can cause irritation to human mucous mem-
sec-Butyl acetate poses less hazard than its nor-
branes. Vinegar contains 3 – 6 % acid. Persons
mal isomer, with less odor and less irritation.
of older than two years can take as much as
The lethal dose for sec-butyl acetate in rabbits
2.1 g daily. However, the dilute acid damages
is 4.8 mg/kg.
26 Acetic Acid
Table 10. Exposure limits to acetic acid and its derivatives [93], [94]

Substance TLV MAK

TWA STEL
3
ppm mg/m ppm mg/m3 mL/m3 mg/m3

Acetic acid 10 25 15 37 10 25
n-Butyl acetate 150 713 200 950 200 950
sec-Butyl acetate 200 950 200 950
Dimethylacetamide (skin) 10 36 10 35
Ethyl acetate 400 1400 400 1400
Methyl acetate 200 606 250 757 200 610

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Pergamon Press, New York 1966.
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Acetic Anhydride and Mixed Fatty Acid Anhydrides 1

Acetic Anhydride and Mixed Fatty Acid Anhydrides


Heimo Held, Wacker-Chemie GmbH, Werk-Burghausen, Burghausen, Federal Republic of Germany
(Sections 1.1 – 1.3.2, 1.4 – 1.7, and Chaps.2 and 3)
Alfred Rengstl, Wacker-Chemie GmbH, Werk-Burghausen, Burghausen, Federal Republic of Germany
(Section 1.3.3)
Dieter Mayer, Pharma Forschung Toxikologie, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of
Germany (Chap. 4)

1. Acetic Anhydride . . . . . . . . . . . 1 1.3.2. Oxidation of Acetaldehyde . . . . . 8


1.1. Physical Properties . . . . . . . . . . 1 1.3.3. Carbonylation of Methyl Acetate . . 9
1.2. Chemical Properties . . . . . . . . . 2 1.4. Analysis . . . . . . . . . . . . . . . . . 11
1.2.1. Acetylation . . . . . . . . . . . . . . . 2 1.5. Quality Specifications . . . . . . . . 11
1.2.2. Dehydration . . . . . . . . . . . . . . . 5 1.6. Storage and Transportation . . . . 12
1.2.3. Reactions of the α-Protons . . . . . 5 1.7. Uses . . . . . . . . . . . . . . . . . . . 12
1.2.4. Reactions of a Single Carbonyl 2. Mixed Fatty Acid Anhydrides . . 12
Group . . . . . . . . . . . . . . . . . . . 5 2.1. Physical Properties . . . . . . . . . . 12
1.2.5. Production of Silver Ketenide . . . . 5 2.2. Chemical Properties . . . . . . . . . 13
1.3. Production . . . . . . . . . . . . . . . 6 2.3. Production . . . . . . . . . . . . . . . 13
1.3.1. Ketene Process . . . . . . . . . . . . . 6 2.4. Uses . . . . . . . . . . . . . . . . . . . 13
1.3.1.1. Production of Ketene . . . . . . . . . 6 3. Economic Aspects . . . . . . . . . . 13
1.3.1.2. Reaction of Ketene with Acetic Acid 7 4. Toxicology and Occupational
1.3.1.3. Pure Anhydride Distillation . . . . . 8 Health . . . . . . . . . . . . . . . . . . 13
1.3.1.4. Environmental Problems . . . . . . . 8 5. References . . . . . . . . . . . . . . . 14

−195
1. Acetic Anhydride Density d 20
20 1.0838; d 20 1.3290; d −79
20 1.277;
d 15 50
4 (1.0870) up to d 4 (1.0443), see [1]
Refractive index n20
D 1.39038
Acetic anhydride [108-24-7], (CH3 CO)2 O, was n16
322nm 1.4174
16
first prepared by C. Gerhardt in 1852 by the n667.8nm 1.3897, see [2]
1
H NMR absorption see [3]
reaction of benzoyl chloride with molten potas- UV absorption
sium acetate. Today it is one of the most impor- maximum 217 nm
tant organic intermediates and is used widely in Specific heat capacity
(23 – 122 ◦ C) 1.817 J/g
both research and industry. Heat of vaporization
at 18.5 ◦ C 496.5 J/g
at 137 ◦ C 276.7 J/g
Heat of combustion at constant volume
1.1. Physical Properties at 25 ◦ C 1804.5 kJ/mol
Thermal conductivity
at 25 ◦ C 2.215 mJ cm−1 s−1 K−1 [4]
Acetic anhydride, C4 H6 O3 , M r 102.09, mp Electric conductivity
−73.1 ◦ C, bp 139.5 ◦ C (at 101.3 kPa), is a col- at 20 ◦ C 2.3×10−8 Ω−1 cm−1 [5]
Dielectric constant
orless liquid with a pungent odor and is strongly at 20 ◦ C 20.5
lachrymatory. The most important physical data Viscosity

are given below. at 15 C 0.971 Pa s
at 30 ◦ C 0.783 Pa s
(for temperature dependence, see [2], [6])
Critical pressure 4680 kPa Cubic expansion coefficient
Critical temperature 296 ◦ C
at 18 ◦ C 1.13×10−9 K−1
Vapor pressure
Adiabatic compressibility
constant 4.86×108 cm2 /N
t, ◦ C 20 40 60 80 100 120
p, kPa 0.4 1.7 5.2 13.3 28.7 53.3 Molecular refraction 22.38 cm3

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 065
2 Acetic Anhydride and Mixed Fatty Acid Anhydrides
Surface tension
special reactions of acetic anhydride are sum-
marized in [9].
t, ◦ C 15 20 40 60 100 139.5
σ, mN/m 33.4 32.7 30.0 28.1 23.3 18.6

Acetic anhydride is miscible with polar sol-


vents and dissolves in cold alcohol with slow
decomposition. The solubility of acetic anhy-
dride in water at 20 ◦ C is 2.6 wt %, with slow
decomposition; the solubility of water in acetic
anhydride at 15 ◦ C is 10.7 wt %, with gradual
decomposition. An overview of the solubilities
of several anhydrous organic and inorganic com-
pounds is given in [7].
Data on the kinetics of hydrolysis in water or
aqueous mixtures of acids, bases, or organic sol-
vents, with or without additives and at different
temperatures, are given in [8]. Rate constants for
the solvolysis in alcohols or alcoholic mixtures
of organic solvents, with or without additives,
are also given.
Melting points of acetic acid – acetic anhy-
dride mixtures are as follows: Figure 1. Equilibrium curve: acetic acid – acetic anhydride

% acetic 100 80 60 40 20 10 1.2.1. Acetylation


acid
mp,◦ C 16.7 5.4 −5.8 −19.8 −44.8 −68.1
O-Acetylation. Acetic anhydride is particu-
larly suitable for the esterification of alcohols,
The vapor-liquid equilibrium curve for mix- a reaction that is difficult or impossible with
tures of acetic acid and acetic anhydride is shown acetic acid. Acetic acid is set free in the course
in Figure 1; this is of great importance in in- of the reaction. Bases and strong acids as well
dustry. Further vapor – liquid equilibria, for ex- as salts, such as sodium acetate, are suitable
ample, with water, benzene, diketene, propi- as catalysts. Examples of the reaction with hy-
onic acid, pyrimidine, and water + acetic acid are droxyl groups are the formation of acetyl cel-
given in [8]. lulose, acetylsalicylic acid (Aspirin), and glyc-
Safety data: erol triacetate (→ Cellulose Esters, → Salicylic
Flash point 52.5 – 53 ◦ C (closed cup, ASTM Acid, → Glycerol).
56−70, DIN 51755) Carboxylic Acid reactions are described
Ignition temperature 315 ◦ C
Explosive limits in air in Chap. 2 (→ Carboxylic Acids, Aliphatic;
(20 ◦ C, 101.3 kPa) → Carboxylic Acids, Aromatic).
Hydrogen peroxide reacts with acetic anhy-
dride to give peracetic acid [79-21-0] or diacetyl
peroxide [110-22-5], depending on the molar ra-
1.2. Chemical Properties
tio of the reactants:
Acetic anhydride undergoes a large variety of
(CH3 CO)2 O + 2 H2 O2  2 CH3 CO3 H
chemical reactions and is by far the most re-
searched aliphatic carboxylic acid anhydride. In (CH3 CO)2 O + H2 O2  CH3 COOH + CH3 CO3 H
about half of the several thousand relevant publi- (CH3 CO)2 O + CH3 CO3 H  CH3 CO-OO-COCH3
cations and patents over the last 25 years, acetic
+ CH3 COOH
anhydride was used for the acetylation of OH or
NH groups (at least for the primary step). Many
Acetic Anhydride and Mixed Fatty Acid Anhydrides 3

N-Acetylation. Acetylation of compounds of the latter group is the acetylation of 2,3-


containing NH groups yields acetamides follow- dimethylbutadiene tricarbonyl iron in the pres-
ing the general equation: ence of aluminum chloride [15] to give the
following complex:
RR NH + (CH3 CO)2 O → RR N-COCH3 + CH3 COOH

where R, R = H or alkyl.
Amines. Aliphatic amines usually react
without heating. Aniline gives acetanilide
(→ Aniline), the acetyl group of which pre-
vents oxidation during subsequent nitration.
The reaction of ketones with acetic anhy-
N-Acetylation generally occurs faster than the
dride using boron trifluoride as a catalyst gives
acetylation of OH groups. Therefore partial
β-diketones [16]. Triacetylmethane [815-68-9]
acetylation of compounds with several func-
can be synthesized directly from isopropenyl
tional groups is possible. Examples of such
acetate, acetic anhydride, and aluminum chlo-
reactions are the production of N-acetylamino
ride catalyst [17]. In the same way, unsaturated
acids, such as N-acetylmethionine-S-oxide (1)
methyl ketones can be produced by acetylation
[10] and of N-acetylanthranilic acids (2) [11].
of olefins with acetic anhydride in the presence
of zinc chloride as catalyst [18]:

Amides and Carbamides. Aliphatic and aro-


matic carboxylic acid amides as well as car-
bamides with a free NH group can be acety-
lated with acetic anhydride. Strong acids, such
as sulfuric acid, are most often used as catalysts. Acetylation of Mineral Acids. The reac-
The breadth of application of this reaction can tion of nitric acid with acetic anhydride gives
be seen from the following products: N,N,N ,N - acetyl nitrate [591-09-3], which is used often
tetraacetylethylenediamine [10543-57-4] [12], as a nitrating agent in organic chemistry. For
(CH3 CO)2 NCH2 CH2 N(COCH3 )2 example, it is used in the production of 2-nitro-
and 2,4,6,8-tetraacetylazabicyclo [3.3.1] cyclohexanone [4883-67-4], a precursor of ε-
nonane-3,7-dione [13]: caprolactam [19]. Acetyl nitrate can be synthe-
sized also from dinitrogen pentoxide and acetic
anhydride.
Other strong acids that form mixed anhy-
drides include sulfuric acid [20], sulfonic acids
[21], and hydrochloric acid. The reaction of
acetic anhydride with phosphorous acid leads to
1-hydroxyethane-1,1-diphosphonic acid [22]:
C-Acetylation. Compounds with reac-
tive CH bonds can be acetylated with
acetic anhydride, with the aid of a cata-
lyst if necessary. Examples are the produc-
tion of ethyl α-cyanoacetoacetate [634-55-9],
CH3 COCH(CN)COOC2 H5 , (catalyst: K2 CO3 )
[14] and the Friedel-Crafts reaction of acetic Acetylation of Oxides. Acetic anhydride re-
anhydride with aromatic hydrocarbons, for acts with antimony trioxide to give antimony tri-
example, with benzene to form acetophe- acetate, Sb(OCOCH3 )3 [5692-86-4] [23]. The
none (→ Ketones), as well as with unsatu- corresponding reaction with chromium trioxide
rated hydrocarbons. An interesting example
4 Acetic Anhydride and Mixed Fatty Acid Anhydrides

leads to chromyl acetate solutions [24], which 1,4-Diacetoxy-2-butene [18621-75-5] can be


often are used to oxidize olefins and hydrocar- obtained from butadiene in a similar manner
bons and which may occasionally explode [25]. [36].

Acetylation of Salts. Various salts react Production of Mixed Diacyl Peroxides. Di-
with carboxylic acid anhydrides in the same acyl peroxides can be made by the reaction of
way as the corresponding free acids [26]: oxygen with mixtures of aliphatic aldehydes and
acetic anhydride in the presence of sodium ac-
Li-C ≡ CR + (CH3 CO)2 O etate [37]:
→ CH3 CO-C ≡ CR + CH3 COOLi

With barium peroxide, diacetyl peroxide


[110-22-5] is obtained [27]:
Reaction with N-Oxides. Reactions with
BaO2 + (CH3 CO)2 O −→ (CH3 CO)2 O2 + BaO N-oxides lead to a variety of products, depend-
ing on the type of N-oxide. From pyridine-
A general method of producing vinyl ketones is
N-oxide, 2-acetyloxypyridine is obtained [38].
the reaction of vinyl magnesium bromides and
However, 4-picoline-N-oxide yields a mixture
acetic anhydride [28]:
of 4-acetyloxymethylenepyridine and 3-acetyl-
oxy-4-methyl- pyridine [39]. In the Polonovski
reaction of N-oxides, formaldehyde and unsat-
urated aldehydes are formed as well as the acid
amides [40], as in the following example:
Production of Acetoxy Silanes. Acetic an-
hydride reacts with silanes according to the
equation:

where X = H, Cl [29]; OR [30]; NR2 [31].


Reaction with S-Oxides. The reduction of
Addition to Heterocyclic Compounds with sulfoxides to sulfides with acetic anhydride is
Ring Cleavage. These reactions differ only for- known as the Pummerer reaction [41]:
mally from those described above. Examples
are the production of ethylene glycol diacetate CH3 SOR + (CH3 CO)2 O
[111-55-7] from ethylene oxide in the presence → CH3 COOCH2 SR + CH3 COOH
of strongly acidic [32] or basic [33] catalysts and
the production of oxymethylene diacetates from An interesting use of this reaction is the
trioxane [34]. oxidation of primary and secondary alcohols,
even when sterically hindered, by mixtures of
Oxidative Addition to Carbon-Carbon dimethylsulfoxide (or tetramethylene sulfoxide)
Double Bonds. Oxidative addition leads to the and acetic anhydride, to give the corresponding
corresponding diacetates, as for example in the carbonyl compounds [42]:
addition of ethylene, which leads to ethylene
glycol diacetate [35]:
Acetic Anhydride and Mixed Fatty Acid Anhydrides 5

Production of Acylals and Vinyl Acetates.


Aldehydes react with acetic anhydride in the
presence of acid catalysts to form acylals:

RCHO + (CH3 CO)2 O −→ RCH(OCOCH3 )2

If R has an α-hydrogen atom available, the cor- Alkyl cyanides can be made by dehydrating
responding vinyl acetate forms by elimination aldoximes with acetic anhydride [49].
of acetic acid. The temperature required for the RCH=NOH + (CH3 CO)2 O −→ RCN + 2 CH3 COOH
reaction can be lowered by adding catalysts [43–
45]. Acetic anhydride serves as a dehydrating agent
in a large number of cyclization reactions.

1.2.3. Reactions of the α-Protons


The Perkin reaction is used for the production of
A similar process is particularly suitable α, β-unsaturated acids from aromatic aldehydes,
for the synthesis of 2,2-dichlorovinyl acetate such as benzaldehyde, in the presence of potas-
[36597-97-4]. Here, in the absence of an α- sium acetate or sodium acetate. This reaction
proton, cleavage of the acetic acid moiety is fa- is also suitable for synthesizing cinnamalacetic
cilitated by the presence of zinc [46]: acid [50]:

Other examples of this type of reaction are the


Boron Trifluoride. Acetic anhydride and oxidative carboxymethylation with acetic anhy-
substituted acetic anhydrides can be converted dride and oxidizing agents [51] and the conver-
into acetyl ketones via a boron trifluoride com- sion of long-chain alkenes to the corresponding
plex that decomposes in warm water [16], [47]. carboxylic acid derivatives [52].

1.2.4. Reactions of a Single Carbonyl Group


1.2.2. Dehydration
In some cases, it is possible to make just one
Acetic anhydride is used as a dehydrating agent, of the carbonyl groups of acetic anhydride par-
for example, in the explosives industry. The ticipate in a reaction. Examples are the reaction
most important example of dehydration is in the with hydrogen cyanide, in the presence of a base,
production of hexogen (1,3,5-trinitrohexahydro- to form (3) [53] and in the presence of Grignard
1,3,5-triazine) [121-82-4] [16]: reagent (RMgBr) to form (4) [54]:

1.2.5. Production of Silver Ketenide


In the production of the nitroester of 1,2,4,5-
tetrahydroxy-3,6-dinitrocyclohexane [48], the Silver acetate and acetic anhydride react at room
water-binding property of the anhydride is used temperature in pyridine to form a pyridine com-
again: plex of silver ketenide. When an excess of an-
hydride is used, silver ketenide is obtained after
6 Acetic Anhydride and Mixed Fatty Acid Anhydrides

fractional distillation of pyridine and acetic acid 1.3.1. Ketene Process


[55], [56]:
The ketene process for the production of acetic
anhydride proceeds in two steps: the thermal
cleavage of acetic acid to form ketene and the
reaction of ketene with acetic acid:

CH3 COOH → CH2 =C=O + H2 O


∆H = 147 kJ/mol
1.3. Production
CH2 =C=O + CH3 COOH → (CH3 CO)2 O
History. The oldest process for making ∆H = − 63 kJ/mol
acetic anhydride is based on the conversion of
sodium acetate with an excess of an inorganic
chloride, such as thionyl chloride, sulfuryl chlo-
ride, or phosphoryl chloride. In this process,
half of the sodium acetate is converted to acetyl 1.3.1.1. Production of Ketene
chloride, which then reacts with the remaining
sodium acetate to form acetic anhydride: Thermal Cleavage of Acetic Acid. Hot
acetic acid vapor is broken into ketene and water
CH3 COONa + X-Cl −→ CH3 COCl + XONa at 700 – 750 ◦ C in the presence of traces of phos-
phoric acid catalyst. The pressure in the reactor
CH3 COONa + CH3 COCl −→ (CH3 CO)2 O + NaCl is generally reduced so that the ketene can be
isolated before it reacts with acetic acid or with
where X = SOCl, SO2 Cl, POCl2 . water. The cleavage takes place in a multicoil
A further development, the conversion of reactor with coils made of highly heat-resistant
acetic acid with phosgene in the presence of alu- steel alloys. The alloy Sicromal, containing
minum chloride, has the advantage that it allows 25 % Cr, 20 % Ni, and 2 % Si, is particularly
continuous operation: suitable. Triethyl phosphate is employed as the
catalyst [57].
2 CH3 COOH + COCl2 −→ (CH3 CO)2 O + 2 HCl + CO2 Figure 2 shows how the vacuum process op-
erates. Acetic acid is fed continuously into the
Two other methods also were used in the past: evaporator (a). The acetic acid vapor leaving the
the cleavage of ethylidene diacetate to form acet- evaporator passes over the catalyst evaporator
aldehyde and acetic anhydride in the presence (b), which is supplied continuously with cata-
of acid catalysts, such as zinc chloride, and the lyst, and thence into the ketene oven (c). The
reaction of vinyl acetate with acetic acid on pal- acetic acid is heated (d) and then cleaved (e).
ladium(II) contacts to form acetaldehyde and As soon as the cracked gases have left the oven,
acetic anhydride [16]. Not one of these processes ammonia is added to prevent the ketene from
is now of any industrial importance. reacting with the water or with the remaining
Today, acetic anhydride is made mostly by ei- acetic acid. For the same reason, and also to re-
ther the ketene process or the oxidation of acet- move condensable gases, the hot gas is cooled in
aldehyde. Production by another process, the combined water and brine condensers (f), (g). A
carbonylation of methyl acetate (Halcon pro- 40 – 48 % aqueous solution of acetic acid con-
cess), was begun in 1983. In Western Europe, denses at about 0 ◦ C and is separated (h) from the
77 % of acetic anhydride is made by the ketene cleavage gas (0 – 10 ◦ C). About 4 – 8 % of this
process and 23 % by the oxidation of acetalde- acetic acid results from the reaction of the con-
hyde. Since production by the Halcon process densed acetic anhydride with water. This process
began at the Tennessee-Eastman plant, 25 % of has been developed by the Consortium für Elek-
acetic anhydride in the United States has been trochemische Industrie, the research institute of
made by this process and 75 % by the ketene Wacker-Chemie.
process.
Acetic Anhydride and Mixed Fatty Acid Anhydrides 7

(a) and (b), which are filled with Raschig rings


[62]. The circulation is maintained by centrifu-
gal pumps and the heat of reaction removed by
coolers (f). Most of the ketene is absorbed in
scrubber (a), the rest in scrubber (b). The liquid
mixture leaving scrubber (a) contains 85 – 90 %
raw anhydride and is collected in (g), cooled and
used in scrubber (c) to wash the off-gas from (b).
The off-gas from (c) is finally washed with brine-
Figure 2. Cleavage of acetic acid by the vacuum process
cooled, dilute acetic acid in scrubber (d) in order
a) Acetic acid evaporator; b) Catalyst evaporator; c) Ketene to remove acid.
oven; d) Convection zone; e) Cleavage zone; f) Water cooler;
g) Brine cooler; h) Separator; i) Receiver

The construction of the ketene oven de-


pends strongly on the power required. In small
ovens (ca. 50 t/month), separate preheating and
cleaving ovens are preferred. The acetic acid is
cleaved in a spiral tube which is usually electri-
cally heated. Ovens of medium size (up to ca.
700 t/month), however, are often constructed as
single-chamber ovens, generally heated with gas
or oil. For capacities of 700 t/month, product loss
is to be expected. This is because of the unsatis-
factory pressure conditions in the cleavage zone. Figure 3. Scrubber process
Ovens with much greater capacities work satis- a), b), c), d) Scrubbers; e) Centrifugal pumps; f) Coolers;
factorily with three- and four-chamber systems g) Collecting vessel; h) Vacuum pump; i) Ring – balance
manometer
and partial gas flows [58]. It is also possible to
operate several ovens with acetic acid supplied
from a central evaporator. Wacker Process (Liquid-ring pump pro-
cess) (see Fig. 4). The ketene emerging from
Thermal Cleavage of Acetone. This varia- the separator (Fig. 2) is pumped through a Nash
tion of the ketene process (cleavage of acetone Hytor liquid-ring pump (a) at about 13 – 20 kPa.
into ketene and methane [59]) has no economic It reacts in the pump, at about 45 – 55◦ C, with
significance for the manufacture of acetic anhy- acetic acid. At the same time, the liquid-ring
dride today. pump provides the vacuum required for the
acetic acid cleavage. Reaction and compression
heat are removed by passing the raw anhydride
1.3.1.2. Reaction of Ketene with Acetic Acid through a cooler (c). This serves simultaneously
as separator for the off-gas from the cleavage
Two processes are available for the reaction of reactor. The off-gas is burnt in the ketene oven
ketene with acetic acid. The classical scrub- after passing the measuring point (d) or is led
ber process is being replaced gradually by the to a flare system. The raw anhydride (90 %) is
Wacker process with liquid-ring pumping [60]. collected continuously. Part of the anhydride is
A further process [61], in which the reaction oc- returned to the reaction pump, where it is used as
curs at higher temperatures, has not yet gained the reaction medium. Advantages of this process
industrial importance. stem from the impressive simplicity of the appa-
ratus and operation, which lead to high reliability
Scrubber Process (see Fig. 3). The ketene and the possibility of producing raw anhydride
emerging from the separator (Fig. 2) is absorbed of higher purity [60].
by glacial acetic acid circulating in scrubbers
8 Acetic Anhydride and Mixed Fatty Acid Anhydrides

acid is required, taking account of the reconcen-


trated dilute acetic acid. The yield is over 96 %
at about 75 % cleavage.

1.3.1.4. Environmental Problems

No significant environmental problems arise


Figure 4. Wacker process (Liquid – ring pump process) with the processes described above. The off-gas
a) Liquid – ring pump; b) Pump; c) Cooler; d) Measuring occurring in the production of ketene consists
point
of ca. 45 % carbon monoxide, 15 – 20 % carbon
dioxide, ca. 15 % ethylene, ca. 10 % methane,
ca. 7 % propylene, and less than 1 % acetic acid
1.3.1.3. Pure Anhydride Distillation and ethane. The remainder is air. The off-gas
can be burnt in the ketene oven saving energy
The raw anhydride can be distilled either con- (ca. 10 %), or led to a flare system. There are no
tinuously or discontinuously. In discontinuous wastewater problems.
distillation, three fractions are obtained:
Forerun (1 %) is about 40 % acetic acid; the
rest consists of volatile liquids, particularly 1.3.2. Oxidation of Acetaldehyde
methyl acetate and acetone.
Middle run (about 10 %). Depending on the Acetic anhydride can be obtained directly by
quality of the column, it contains 30 – 60 % liquid-phase oxidaton of acetaldehyde. The per-
acetic anhydride; the rest is acetic acid. acetic acid formed from oxygen and acetalde-
Pure Anhydride. Using discontinuous distil- hyde reacts under suitable conditions with a sec-
lation at normal pressures, the purity of the ond molecule of acetaldehyde to form acetic an-
anhydride cannot exceed 99 % (the remainder hydride and water [64]:
is acetic acid) because, at the still temperature
required, a certain amount of decomposition
occurs. These difficulties can be overcome by
operating under reduced pressure. Rapid removal of the reaction water and the
use of suitable catalysts are essential in this pro-
For continuous distillation, two or three cess. Mixtures of acetic acid and acetic anhy-
columns are used, depending on the required dride are always obtained; their ratio can be var-
number of fractions (forerun and middle run are ied within wide limits by changing the reaction
separated). The middle run portion is returned conditions. Generally, the highest possible an-
to the reactor as reagent acid. The residue of the hydride yield is sought.
distillation contains small amounts of tarry prod- Because of the rapid hydrolysis of acetic an-
ucts and is worked up continuously in a Sambay hydride above 60 ◦ C, the process is operated
evaporator. preferably between 40 ◦ C and 60 ◦ C [65]. Suit-
A newer continuous and energy-saving vac- able catalysts are combinations of metal salts
uum process works with two evaporators and [66]. Particularly important are mixtures of man-
only one column [63]. ganese acetate and copper acetate [67], of cobalt
The Wacker process, described above (see acetate and nickel acetate, and of cobalt and cop-
Fig. 4), is also particularly suitable as a workup per salts of higher fatty acids [68]. Manganese
process. Waste acids, such as those from cel- acetate should hinder the formation of explosive
lulose acetylation, can be processed after con- amounts of peracetic acid during the oxidation
centration without difficulty. No auxiliary ma- of acetaldehyde. For increasing the rate of oxi-
terials are necessary, only energy in the form dation, the use of pure oxygen at a pressure of
of gas, oil, or electric current. The process has several hundred kilopascals instead of air has
been adopted by many firms. For the production been proposed [69].
of 100 kg acetic anhydride, about 122 kg acetic
Acetic Anhydride and Mixed Fatty Acid Anhydrides 9

The strongly exothermic reaction requires ef- aldehyde is introduced at the top of this column.
ficient cooling. For this purpose, the addition of The condensates from both the cooler (b) and
low-boiling solvents has been found to be of as- the column (c) are distilled to obtain the prod-
sistance. Methyl and ethyl acetates are favored uct. Acetaldehyde is recovered from the branch
because they form azeotropic mixtures with wa- stream (d) of the non-condensable gas. The other
ter (but not with acetic acid or acetic anhydride) part of the gas flow is supplemented with air and
and hence allow a rapid, continuous separation returned to the reactor.
of the water formed in the reaction. The ratio
of acetic anhydride to acetic acid in the product
depends on the ratio of ethyl acetate to acetalde-
hyde in the initial mixture (Table 1).
Table 1. Formation of acetic anhydride by oxidation of acetaldehyde

Ethyl acetate: Acetaldehyde Acetic anhydride


acetaldehyde in conversion, % yield based on
starting mixture acetaldehyde, %

20 : 80 80 13.5
30 : 70 80 57
60 : 40 80 64 Figure 5. Acetaldehyde oxidation
70 : 30 80 68.5 a) Reactor; b) Condenser; c) Column; d) Branch
stream (acetaldehyde recovery from non-condensable gas);
In practice, a 1 : 2 mixture of acetaldehyde e) Pump
and ethyl acetate is oxidized with the addition of Both towers and vessels are suitable as reac-
0.05 to 0.1 % cobalt acetate and copper acetate tors if the heat of reaction can be dissipated. The
at 40 ◦ C; the ratio of Co:Cu is 1:2. The ratio of process of Distillers Co. [69] is shown in Fig-
acetic anhydride to acetic acid obtained is 56:44, ure 6 as an example. The off-gas contains com-
whereas on oxidizing in the absence of ethyl ac- bustible low-boiling products, such as acetalde-
etate this ratio is only 20:80 [16]. The optimiza- hyde, and solvents, such as methyl acetate and
tion of other reaction conditions can also lead to ethyl acetate. These can be flared off.
an increase in the acetic anhydride-acetic acid
ratio. For example, at 55 ◦ C and atmospheric
pressure, a ratio of 80:20 was achieved [70]. At
a higher temperature (62 – 90 ◦ C, 200 – 300 kPa,
acetaldehyde concentration in the final mixture
of up to 40 %) a ratio of 75:25 was obtained at
high aldehyde conversion [71].
Other suitable low-boiling solvents are
Figure 6. Reactor for the acetaldehyde oxidation (Distillers
methylene chloride, diisopropyl ether, cyclohex- Co.)
anone, or ethylidene diacetate. Nonvolatile es- a) Reactor tubing; b) Cooling bath; c) Separator; d) Circu-
ters also can be used as diluents, provided they lation pump
do not have to be removed from the reaction
zone. These include alkyl benzoates and alkyl
phthalates [72].
The acetaldehyde oxidation is illustrated in 1.3.3. Carbonylation of Methyl Acetate
Figure 5 by the process of Usines de Melle [73].
The gas mixture containing oxygen and acet- The thermal decomposition of acetic acid to
aldehyde is pumped into the reactor (a). The ox- form ketene requires a large amount of energy,
idation takes place in the liquid phase and in a disadvantage of the conventional process for
the presence of catalysts. The reactor effluent is the production of acetic anhydride. Moreover,
sent through a water-cooled condenser (b) con- processes based on synthesis gas have been de-
structed as a separator; non-condensable gases veloped that allow the manufacture of products
are sent to the packed column (c). Fresh acet- from coal that were hitherto produced from oil.
An important example is the acetic acid produc-
10 Acetic Anhydride and Mixed Fatty Acid Anhydrides

tion process developed by Monsanto (→ Acetic The methyl acetate is dried with acetic an-
Acid). hydride [77] and is sent to a reactor (b) lined
In 1973 Halcon patented the carbonylation of with Hastelloy. Carbon monoxide is compressed
methyl acetate in the presence of a rhodium cata- (a) to the reaction pressure and then added.
lyst to form acetic anhydride [74]. However, the The reaction proceeds continuously at 175 ◦ C
first plant (Eastman-Kodak Co., in Kingsport, in the presence of a catalyst consisting of
Tenn., USA) using this process was not put into RhCl3 · 3 H2 O, CH3 I, and LiI. The considerable
operation before 1983. Because no exact de- amount of heat generated by the reaction is re-
scription of the process has so far been available, moved by heat exchange and is used both for
the following details are based upon information preheating methyl acetate and for the production
from the patent literature. of low-pressure steam. The unreacted carbon
Methyl acetate is carbonylated to acetic an- monoxide leaves the top of the reactor, is freed
hydride in the liquid phase at a temperature of of condensable gases (methyl iodide, methylac-
160 – 190 ◦ C and at a carbon monoxide partial etate, acetic anhydride, acetic acid, and ethyli-
pressure of 2 – 5 MPa: dene diacetate) by cooling (f), and is then recir-
culated. However, part of the circulating gas is
separated from the main stream to avoid buildup
of inert gases, which may be present in the car-
The starting material, methyl acetate, can be bon monoxide. The side stream is washed (g)
produced by esterification of acetic acid with with a countercurrent of pure acetic anhydride;
methanol. However, the methyl acetate obtained in this way, the loss of methyl iodide in the off-
as a byproduct of the acetic acid synthesis from gas can be kept below 0.1 % [78]. This acetic
methanol and carbon monoxide is used prefer- anhydride is combined with the top condensate
ably. from the reactor (b), supplemented with fresh
Catalysts. Rhodium [74] and nickel com- catalyst as required, and recirculated. The liquid
pounds [75], activated by CH3 I, HI, LiI, I2 , or reaction product leaving the reactor is expanded
other iodides, are particularly appropriate as cat- and subjected to flash distillation (c) [78]. To
alysts. Rhodium catalysts have about a tenfold prevent catalyst decomposition, this distillation
higher activity than nickel catalysts. The selec- is performed in a carbon monoxide-hydrogen at-
tivity is higher than 95 % for both catalysts. Their mosphere at about 500 kPa [79]. At the bottom
activities and lifetimes are increased by mix- of the evaporator (c) a stream of liquid contain-
ing the carbon monoxide used for the synthesis ing the catalyst is separated and recirculated into
with 2 – 7 % hydrogen. Chromium compounds the carbonylation reactor. The vapor leaving the
have been used to shorten the induction phase of top of the evaporator is condensed and passed
the reaction [74]. Kinetic investigations on the over adsorbers (d) to remove traces of rhodium
rhodium system have shown that the reaction is and iodine compounds.
zero order with respect to the methyl acetate and The raw anhydride is purified by distillation
carbon monoxide concentrations [76]. As possi- in three consecutive and continuously operating
ble byproducts, only acetic acid and ethylidene columns (e). In the first column, methyl iodide
diacetate are mentioned. and methyl acetate are distilled overhead and
The process also can start from dimethyl ether recirculated to the carbonylation reactor. In the
[74]. In this case, dimethyl ether is first car- second column, acetic acid is distilled overhead.
bonylated to methyl acetate, which is then con- The bottom product is distilled in a third column
verted to acetic anhydride by using more carbon to acetic anhydride of 99 % purity. The bottom
monoxide in the same reactor: product of the third column contains ethylidene
diacetate and unidentified high-boiling compo-
nents. To further reduce the iodide content of the
pure anhydride, a solution of potassium acetate
in acetic anhydride is added to the top of the
Process Description. The carbonylation column [80].
method is illustrated by the Halcon process, Other processes. Other processes and cata-
shown schematically in Figure 7. lysts for the carbonylation of methyl acetate have
Acetic Anhydride and Mixed Fatty Acid Anhydrides 11

Figure 7. Halcon process for the production of acetic anhydride


a) Compressor; b) Carbonylation reactor; c) Evaporator; d) Adsorber; e) Distillation column; f) Condenser; g) Scrubber

been patented by various companies: Hoechst water, which is determined by the Karl Fischer
[81] (rhodium catalyst), Air Products and Chem- method.
icals Co.[82] (rhodium catalyst), Mitsubishi Gas In the aniline method [85], the total acid con-
and Chemical Co. [83] (nickel catalyst), and tent is first determined. After addition of aniline
Rhône-Poulenc [84] (nickel catalyst). Several to a second sample, the aniline number is es-
patents also describe the carbonylation of esters tablished with alkali and the acetic anhydride
of higher alcohols and carboxylic acids. This re- content determined from the difference.
action results in the formation of the correspond- A rapid determination of the anhydride con-
ing mixed anhydrides [74], [83]. tent can be obtained from the refractive index.
Environmental problems do not arise. The If the temperature remains constant to within
off-gas from the acetic anhydride production ± 0.05 ◦ C, the precision obtainable is ± 0.2 %.
contains large quantities of carbon monoxide, Gas chromatography also is recommended for
some inert gases (nitrogen, rare gases, and car- purity determination. Analytical methods are
bon dioxide), and traces of hydrogen, methane, discussed in detail in [86].
methyl iodide, and methyl acetate. It can be
burned. There are no problems with waste water.
1.5. Quality Specifications
Acetic anhydride is marketed with more than
1.4. Analysis 95 % purity; the normal product is over 98 %
pure, but it is marketed also as over 99 % pure.
A very reliable method for determining the con- The color number (APHA) should be below 10
tent of acetic anhydride consists of mixing sto- (DIN 53409). The nonvolatile part should not
ichiometric quantities of the sample and water, exceed 0.003 %. The product also should con-
then heating carefully to reflux temperature. Af- tain as few substances as possible that reduce
ter completion of the reaction, two drops of con- permanganate. According to American Chem-
centrated sulfuric acid are added, and the mix- ical Society specifications, for example, a 2 g
ture is boiled for 20 min to insure that the last sample should not decolorize 0.4 ml of a 0.1 N
traces of the anhydride have reacted. The an- potassium permanganate solution within 5 min.
hydride content is calculated from the unused In particular applications, the impurities that
12 Acetic Anhydride and Mixed Fatty Acid Anhydrides

can be oxidized by potassium chromate are also 3) Explosives, particularly hexogen production
of interest. They may not consume more than (see Section 1.2.2.).
200 ppm of oxygen. The contents of phosphate, 4) The production of certain types of brake flu-
sulfate, chloride, aluminum, and iron may not ids.
exceed 1 ppm each. Heavy metals should be ab- 5) The production of auxiliaries for drilling flu-
sent. ids.
6) The detergent industry, for the produc-
tion of cold – bleaching activators such as
1.6. Storage and Transportation tetraacetylethylenediamine [12].
7) The dyeing industry, where acetic anhydride
For storage and transportation of pure acetic an- is used chiefly in mixtures with nitric acid as
hydride, tanks made of aluminum, stainless steel a nitrating agent. Here, the solvent and de-
(18 % Cr, 8 % Ni, and 2 % Mo), or polyethylene hydrating properties of acetic anhydride are
normally are used, although glass or enamel con- used.
tainers also may be employed. Iron is highly re- 8) In the preparation of organic intermediates,
sistant to acetic anhydride, provided moisture is such as chloroacetylchloride, diacetyl perox-
excluded. Therefore it is possible to use iron in ide, higher carboxylic anhydrides, acetates,
the production and workup in certain instances, and the boron trifluoride complex.
for example, in pumps and tanks. 9) In the production of pharmaceuticals, such as
Because there are no international arrange- acetylsalicylic acid, p-acetylaminophenol,
ments for the storage of dangerous goods, acetanilide, acetophenacetin, theophyllin,
the specifications of individual countries must acetylcholine chloride, sulfonamides, a
be observed. Also, acetic anhydride (EG-no. number of hormones and vitamins, and the x-
607−008−00−9) is subject to various industrial ray contrast agent 2,4,6-triiodo-3,5-diacetyl-
working regulations, for example, Appendix I, amidobenzoic acid.
no. 1.1 of the EEC Guidelines. 10) In the food industry, mainly in the acetylation
of animal and plant fats, in order to obtain the
Transportation. IMDG-Code, class 8, UN- desired solubilities; in the production of ace-
no. 1715; United Kingdom: Blue Book: Corro- tostearins, the edible packing materials; and
sive, IMDG-Code E 8018; United States: DOT to clarify plant oils.
Safety Act, Title 46 and Title 49; Cor. M; Eu- 11) Flavors and fragrances (production of esters
rope: RID, ADR, and ADNR: class 8, no. 21 e and cumarin).
(from 1985: class 8, no. 32 e), RN 801, 2801, and 12) Herbicides such as metolachlor (Dual) and
6801, respectively. International air transporta- alachlor (Lasso).
tion: IATA-DGR, class 8, UN-no. 1715, RAR
art. no. 9, Cor. M.
2. Mixed Fatty Acid Anhydrides
1.7. Uses 2.1. Physical Properties
Acetic anhydride is used chiefly as an acetylat- Important mixed anhydrides, that is, anhydrides
ing and dehydrating agent; it is used on a large with two different fatty acid radicals, are com-
scale for the acetylation of cellulose. Other areas piled in Table 2. The lower anhydrides can be
of application for acetic anhydride are: distilled partly undecomposed at reduced pres-
1) The production of poly(methylacrylimide) sure. At high temperature they disproportion-
hard foam, where acetic anhydride is used ate fairly rapidly into the symmetrical anhy-
for binding the ammonia that is liberated on drides. Only acetoformic anhydride distills (at
conversion of two amide groups to an imide 127 – 130 ◦ C) at normal pressure, although with
group. partial decomposition to acetic acid and car-
2) Acetylated plastic auxiliaries, such as glyc- bon monoxide. The first four mixed anhydrides
erol triacetate, acetyl tributyl citrate, and have odors very similar to pure acetic anhydride;
acetyl ricinolate. acetic isovaleric anhydride has a fruitlike odor.
Acetic Anhydride and Mixed Fatty Acid Anhydrides 13
Table 2. Mixed fatty acid anhydrides

Anhydride Formula bp or mp,◦ C Preferred


production
method
(Section 2.3)

Acetoformic anhydride HCOOCOCH3 bp 32 (at 2.7 kPa) 3


Acetic propionic anhydride CH3 COOCOC2 H5 bp 25 – 27 (at 0.15 kPa) 3
(decomposes at 30 ◦ C)
Acetic butyric anhydride CH3 COOCO(CH2 )2 CH3 – 3
Acetic isobutyric anhydride CH3 COOCOCH(CH3 )2 – 3
Acetic valeric anhydride CH3 COOCO(CH2 )3 CH3 (decomposes above 130 ◦ C) 3
Acetic isovaleric anhydride CH3 COOCOCH2 CH(CH3 )2 – 3
Acetic 2,2-dimethylpropanoic anhydride CH3 COOCOC(CH3 )3 – 3
Acetic hexanoic anhydride CH3 COOCO(CH2 )4 CH3 – 3
Acetic octanoic anhydride CH3 COOCO(CH2 )6 CH3 – 3
Acetic hexadecanoic anhydride CH3 COOCO(CH2 )14 CH3 mp 62.5 (decomposes on 2,3
crystallization from polar
solvents)
Acetic octadecanoic anhydride CH3 COOCO(CH2 )16 CH3 – 3
Butyric tetradecanoic anhydride CH3 (CH2 )2 COOCO(CH2 )12 CH3 mp 52.7 2
Hexanoic dodecanoic anhydride CH3 (CH2 )4 COOCO(CH2 )10 CH3 mp 42.4 2
Octanoic decanoic anhydride CH3 (CH2 )6 COOCO(CH2 )8 CH3 mp 16 2

2.2. Chemical Properties 3) Reacting ketene with a carboxylic acid [92–


94].
Acetoformic anhydride [2258-42-6] acts as a The latter two processes are more useful
formylation agent in acylation reactions. In the than the first. According to the patent litera-
other mixed acetic – fatty acid anhydrides, the ture, mixed anhydrides also can be produced by
higher acyl group is more reactive; for exam- carbonylating the corresponding esters (Section
ple, in the reaction with benzene in the presence 1.3.3).
of aluminum chloride, compound (5) is formed
preferably.
2.4. Uses
Acetoformic anhydride often is used as a formy-
lating agent. Acetic propionic [13080-96-1] and
acetic butyric [7165-13-1] anhydrides are used
where R = alkyl. in the production of acylated cellulose.
Branching of the higher acyl group at its
α position leads to a decrease in the yield of
the acylbenzene (5) in favor of acetophenone 3. Economic Aspects
(6) [87]. From acetic chloroacetic anhydride,
mainly ω-chloroacetophenone is formed [87]. Production data are given in Table 3. Annual
Changes in reaction conditions have little influ- capacity data for acetic anhydride are as fol-
ence on the ratio of reaction products. lows: Western Europe (1978) 357 000 t, (1980)
362 000 t, (1996) 500 000 t; United States (1980)
905 000 t, (1982) 929 000 t, (1996) 1 000 000 t,
2.3. Production (2001) 1 160 000 t. No data for the mixed anhy-
drides are available.
Three processes are generally employed for pro-
ducing mixed anhydrides:
4. Toxicology and Occupational
1) The reaction of acetic anhydride with a Health
higher organic acid [88].
2) Heating an acyl chloride with a fatty acid salt, In acute oral studies in rats, an LD50 value of
usually a sodium or potassium salt [89–91]. 1780 mg/kg was determined for acetic anhy-
14 Acetic Anhydride and Mixed Fatty Acid Anhydrides
Table 3. Production of acetic anhydride (in kt) [95], [96], [97], [98]

1961 1971 1974 1979 1980 1981 1982 1989 1990 1996 2001

United States 571 686 741 567 481 778 830 1000 1160
Germany∗) 32 47 74 91 85 77 76 108 112
Japan 33 96 115 114 150 145 144 205 1160

∗) 1961 - 1989 Fed. Rep. of Germany

dride. The dermal LD50 in rabbits is 4000 mg/kg 5. References


[99]. Inhalation of 2000 ppm for 4 h causes death
in rats [100]. The lowest published lethal con- 1. D. T. Lewis, J. Chem. Soc. 1940, 33.
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1000 ppm [101]. 268.
3. L. H. Meyer, A. Saika, H. S. Gutowsky, J. Am.
In rabbits, skin contact for 24 h causes only
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[104]. In rabbits, 250 µg causes severe irrita- 7. G. Jaudes, E. Rüsberg, H. Schmidt, Z. Anorg.
tion. Human occupational exposure can cause Chem. 255 (1948) 238.
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(1964) 1787.
drolyzing and reaches the iris in concentrations
11. S. S. Parmar, R. C. Arora, J. Med. Chem. 13
high enough to cause iritis. (1970) 135.
Inhalationcan lead to asthmoid bronchitis 12. BASF DE-OS 2 118 281, 1971; NL 7 204 899,
with lung edema [108]. Human exposure to con- 1972 (C. Palm, G. Matthias).
centrations of 800 ppm cannot be tolerated for 13. Henkel u. Cie., DE-OS 2 112 557, 1971.
longer than 3 min because of the burning sensa- 14. J. Hori, H. Midorikawa, Sci. Pap. Inst. Phys.
tion in the nose and throat. Humans are believed Chem. Res. (Tokyo) 56 (1962) 216.
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Chemie, 4th ed., vol. VII/2a, Thieme Verlag,
the water content of the tissues.
Stuttgart 1983, p. 457.
Systemic effects after repeated exposure are
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Acetic Anhydride and Mixed Fatty Acid Anhydrides 15

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16 Acetic Anhydride and Mixed Fatty Acid Anhydrides

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Acetoacetic Acid → Oxocarboxylic Acids


Acetone 1

Acetone
Stylianos Sifniades, Allied Signal Inc., Morristown, New Jersey 07962, United States

Alan B. Levy, Allied Signal Inc., Morristown, New Jersey 07962, United States

1. Introduction . . . . . . . . . . . . . . . . 1 8. Uses . . . . . . . . . . . . . . . . . . . . . 10
2. Physical Properties . . . . . . . . . . . 1 8.1. Methyl Methacrylate . . . . . . . . . . 10
3. Chemical Properties . . . . . . . . . . . 2 8.2. Bisphenol A . . . . . . . . . . . . . . . . 11
4. Production . . . . . . . . . . . . . . . . . 3 8.3. Aldol Chemicals . . . . . . . . . . . . . 11
4.1. Cumene Oxidation (Hock Process) . 3 8.4. Solvent Uses . . . . . . . . . . . . . . . . 11
4.2. Dehydrogenation of 2-Propanol . . . 6 9. Economic Aspects . . . . . . . . . . . . 12
4.3. Propene Oxidation . . . . . . . . . . . . 7
10. Toxicology and Occupational Health 13
4.4. Oxidation of 2-Propanol . . . . . . . . 8
11. Derivatives . . . . . . . . . . . . . . . . . 13
4.5. Oxidation of p-Diisopropyl Benzene 8
4.6. Fermentation of Biomass . . . . . . . 8 11.1. Acetone Cyanohydrin . . . . . . . . . . 13
5. Environmental Protection . . . . . . . 8 11.2. Diacetone Alcohol . . . . . . . . . . . . 15
6. Quality Specifications and Analysis . 9 11.3. Miscellaneous Derivatives . . . . . . . 16
7. Storage and Transportation . . . . . . 10 12. References . . . . . . . . . . . . . . . . . 16

1. Introduction 2. Physical Properties


Acetone, 2-propanone, dimethyl ketone, Acetone has the following physical proper-
CH3 COCH3 , [67-64-1], is the first and most ties: M r 58.081; bp at 101.3 kPa, 56.2 ◦ C;
important member of the homologous series of mp − 94.7 ◦ C; relative density, d 04 0.81378,
aliphatic ketones. It is a colorless, mobile liquid d 15 20
4 0.79705, d 4 0.7908; relative vapor den-
widely used as a solvent for various polymers. sity (air = 1) 2.0025; refractive index n20 D
Its largest application, however, is as an inter- 1.35868; critical temperature 235.0 ◦ C, crit-
mediate in the synthesis of methyl methacrylate, ical pressure 4.6 MPa (46 bar), critical den-
bisphenol A, diacetone alcohol, and other prod- sity 0.278 g/cm3 ; cubic expansion coeffi-
ucts. cient (18 ◦ C) 1.43 × 10−3 K−1 ; compressibil-
Acetone was first manufactured by the dry ity coefficient (18 ◦ C) 1.286 × 10−6 kPa−1
distillation of calcium acetate [62-54-4]. Cal- (1.286×10−4 bar−1 ).
cium acetate was originally a product of wood Viscosity in mPa · s: 1.53 (− 80 ◦ C), 0.71
distillation, and later was obtained by fermenta- (− 40 ◦ C), 0.40 (0 ◦ C), 0.32 (20 ◦ C), 0.27
tion of ethanol. Carbohydrate fermentation di- (40 ◦ C). Surface tension in mN · m−1 : 38.1
rectly to acetone and butyl and ethyl alcohols (− 91.09 ◦ C), 23.9 (15 ◦ C), 23.3 (20 ◦ C), 23.0
displaced these processes in the 1920s. The car- (24.8 ◦ C), 22.0 (30 ◦ C), 21.6 (42 ◦ C).
bohydrate route, in turn, was replaced in the Thermal properties: Specific heat capacity,
1950s and 1960s by the 2-propanol dehydro- cp (20 ◦ C) 2.135 kJ kg−1 K−1 ; heat of fusion
genation process and by the oxidation of cumene (− 95 ◦ C) 98.47 kJ kg−1 ; heat of vaporization
to phenol [108-95-2] plus acetone. Together with (30 ◦ C) 545.2 kJ kg−1 , (0 ◦ C) 588.2 kJ kg−1 ;
direct propene oxidation, these methods account molar entropy 0.2001 kJ mol−1 K−1 ; heat of
for over 95 % of the acetone produced world- combustion 1804 kJ mol−1 ; heat of formation
wide. (20 ◦ C) 235.3 kJ/mol; thermal conductivity of
the liquid 1.976 W m−1 K−1 .
Vapor Pressure in kPa: 24 (20 ◦ C), 37.3
(30 ◦ C), 56.0 (40 ◦ C), 82.8 (50 ◦ C), 114.8

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 079
2 Acetone

(60 ◦ C), 214.8 (80 ◦ C), 372.8 (100 ◦ C), 929.6 3. Chemical Properties
(140 ◦ C).
Electrical properties: Electric conductivity Pure acetone is essentially inert to air oxidation
(20 ◦ C) 5.5 × 10−8 Ω −1 cm−1 ; dipole moment and to diffuse sunlight under ambient conditions.
(20 ◦ C) 2.69 Debye; dielectric constant of Its chemical stability diminishes significantly in
the liquid 21.58 (0 ◦ C), 22.64 (10 ◦ C), 20.70 the presence of water. Acetone may react vio-
(25 ◦ C), 19.38 (40 ◦ C); dielectric constant of the lently and sometimes explosively, especially in
vapor 1.0235 (24.8 ◦ C), 1.0277 (29.8 ◦ C). a confined vessel [5]. For example it is partic-
At ambient temperature acetone is a clear, ularly sensitive to oxidizing agents, such as ni-
colorless liquid with a characteristic odor. It is trosyl chloride [6] [2696-92-6], chromium tri-
miscible in all proportions with water and po- oxide [7] [1333-82-0], and hydrogen peroxide
lar organic solvents, such as the lower molecu- [8] [7722-84-1], or organic peroxides [9]. Mix-
lar mass alcohols, carboxylic acids, and ethers. tures of acetone with chloroform [67-66-3] may
It is miscible in limited proportions with non- react violently in the presence of alkali [10]. Re-
polar solvents, such as hydrocarbons. Some action even may be initiated by surface alkali on
azeotropic mixtures are shown in Tables 1 and 2 new glassware [11]. Acetone has a flash point
[3], [4]. of −17 ◦ C (closed cup). Flammability limits in
air are: lower 2.13 vol %, upper 13 vol %; au-
Table 1. Acetone binary azeotropes ∗ toignition temperature 465 ◦ C. The flammabil-
ity of acetone can be reduced by mixing it with
Second component Acetone, wt % bp (101.3 kPa), less flammable and/or less volatile solvents [12].

C
Fires have been started during recovery of ace-
Carbon tetrachloride 88.5 56.08 tone from air by adsorption on activated carbon
2-Butylchloride 80 55.75
Hexane 53.5 49.7 when air flow was too low to effectively remove
Methyl acetate 49 55.65 the heat generated by surface oxidation [13].
Diethylamine 38 51.55 Acetone undergoes typical carbonyl reac-
Carbon disulfide 33 39.25
tert-Butylchloride 25 49.2 tions with particular ease. Acid- or base-
Isoprene 20 30.5 catalyzed self-condensation produces the dimers
n-Propylchloride 15 45.8
Methanol 14 55.59 diacetone alcohol and mesityl oxide and the cy-
clic trimer isophorone.
∗ Source and further examples [3]. Under strongly basic conditions hydrogen
cyanide adds to acetone to form 2-cyano-
Table 2. Acetone ternary azeotropes ∗ 2-propanol (acetone cyanohydrin), an impor-
Components (A is acetone) Composition, bp (101.3 kPa),
tant intermediate in the manufacture of methyl
wt % ◦
C methacrylate and other methacrylate esters (Sec-
tion 8.1).
B water 0.81 38.04
C carbon disulfide 75.21 In liquid ammonia solution acetone con-
B water 0.4 32.5 denses with acetylene [74-86-2] in the presence
C isoprene 92.0
B chloroform 46.7 57.5
of catalytic amounts of alkali metals to form 2-
C methanol 23.4 methyl-3-butyn-2-ol [115-19-5], an intermedi-
B chloroform 70.2 55.0 ate in the synthesis of isoprene [14] [563-46-2].
C ethanol 6.8
B methanol 16 51.1 Catalytic hydrogenation of acetone yields 2-
C cyclohexane 40.5 propanol [67-63-0]. Pyrolysis produces methane
B methyl acetate 5.6 49.7
C hexane 43.3
[74-82-8] and ketene [463-51-4], a powerful
acetylating agent. A more economical source of
∗ Source and further examples [4]. ketene, however, is the pyrolysis of acetic acid,
which produces ketene and water.
Acetone dissolves many synthetic Reductive ammonolysis of acetone yields
resins, e.g., nitrocellulose, acetylcellulose, isopropylamine [75-31-0]. Condensation with
poly(acrylate esters), and alkyd resins. It also 2 mol phenol in the presence of an acidic catalyst
dissolves most natural resins, fats, and oils. yields bisphenol A (Section 8.2), an important
Acetone 3

monomer used in the manufacture of polycar- Fermentation of cornstarch and molasses to


bonate resins. acetone and 1-butanol was important in the past.
Perchlorination yields hexachloroacetone It is believed to be practiced today to a limited
[116-16-5], which is cleaved into chloro- extent in several countries.
form [67-66-3] and sodium trichloroacetate
[650-51-1] upon treatment with sodium hydrox-
ide. 4.1. Cumene Oxidation (Hock Process)
(Fig. 1)

Propene [115-07-1] is added to benzene


4. Production [71-43-2] to form cumene [98-82-8], which is
then oxidized by air to cumene hydroperoxide
Approximately 83 % of the acetone produced (1), and cleaved in the presence of an acid cat-
worldwide is manufactured from cumene as a alyst. Phenol [108-95-2] and acetone produced
coproduct with phenol. In the United States and in the process are recovered by distillation.
Western Europe dehydrogenation of 2-propanol
is also important, whereas in Japan catalytic ox-
idation of propene is used as a second process.
Cumene, 2-propanol, and propene together as
starting materials account for over 95 % of the
acetone produced worldwide. Because propene
is used in the manufacture of both cumene and
2-propanol, propene is the ultimate raw material
for the production of acetone. The alkylation of benzene by propene pro-
Small amounts of acetone are made by oxida- ceeds under typical Friedel – Crafts conditions.
tion of p-diisopropyl benzene and of p-cymene. In 1996, a number of processes using zeolite cat-
Coproducts from these reactions are hydro- alysts came on-stream. The cumene produced is
quinone and p-cresol, respectively. Acetone is purified by chemical means and refined by dis-
also produced by propene oxidation and as a tillation to 99.9 % minimum purity. Oxidation-
byproduct of acetic acid manufacture. grade cumene must meet strict quality standards.

Figure 1. Cumene phenol – acetone process (Allied)


a) Oxidizers; b) Flash column; c) Carbon adsorber; d) Alkaline extraction and wash; e) Cumene hydroperoxide decomposer;
f) Dicumyl peroxide decomposer; g) Ion exchange; h) Crude acetone column; i) Acetone-refining column; j) Cumene column;
k) α-Methylstyrene column; l) Phenol column; m) Phenol residue topping column
AMS = α-methylstyrene
4 Acetone
Table 3. Specifications for oxidation-grade cumene (zeolite process) [15]

Property ASTM test Specification

Appearance Clear, colorless liquid


Color, Pt – Co scale D1209-79 15 max.
d 15.5
15.5 D891-59 0.864 – 0.867
Acid wash color, W scale D848-62 2 max.
Sulfur compounds D853-47 Free from H2 S and SO2
Copper corrosion D849-47 No iridescence, gray or black
Distillation range D950-56 1.0 ◦ C max.
Cumene content 99.93 % min.
Phenolics content 5 ppm max.
Cumene hydroperoxide content 200 ppm max.
Sulfur content 0.1 ppm max.

The newer zeolite-based processes have led to For these reasons, most plants operate between
slightly tighter specifications (Table 3) [15]. 25 and 40 wt % in the last oxidation reactor.
A minor but significant byproduct of the oxi-
Cumene Oxidation. The oxidation of dation is dicumyl peroxide [80-43-3]. This arises
cumene is a free-radical chain reaction [16]. during the termination of the chain reaction.
The chain initiator is cumene hydroperoxide, Dicumyl peroxide also contributes to chain ini-
the main product of the reaction. The rate of tiation [17], but to a much lesser degree than
oxygen consumption can be approximated by cumene hydroperoxide. Other minor byproducts
the following expression: are formaldehyde and formic acid, which are
 produced along with acetophenone by methyl
−dcO2 2ki cROOH group degradation.
= kp · cRH
dt kt The oxygen needed for cumene oxidation is
supplied by air. Use of pure oxygen has been sug-
cRH and cROOH are the concentrations of gested [18] but is disfavored by both economic
cumene and cumene hydroperoxide, respec- and safety considerations [19]. At low initiation
tively; k i , k p , and k t are the rate constants for rates, the rate of the reaction is essentially inde-
chain initiation, propagation, and termination. pendent of the oxygen concentration at a partial
The expression shows that the rate of oxi- pressure of oxygen over 33 kPa (0.33 bar) [20].
dation is zero in the absence of cumene hydro- A detailed study of the rate of oxygen uptake
peroxide. This is not exactly true, because the in a bubble column as a function of temperature
expression is only an approximation; but the and partial oxygen pressure has been made [21].
oxidation of cumene does require long induc- The study served as a basis for a mathematical
tion periods when starting with pure cumene. model of the oxidation [22], [23].
Consequently, the industrial oxidation always is Two cumene oxidation processes are used
carried out in a series of continuous reactors; in the United States, which with minor vari-
the concentration of cumene hydroperoxide is ations are practiced also in the rest of the
at least 8 wt % in the first reactor. Because the world [19], [22]. One process was developed by
sum of cRH and cROOH remains roughly con- Hercules and licensed by Kellogg (previously
stant during the reaction, the rate of reaction BP/Hercules) and GE/Lummus [24]. The other
cannot increase indefinitely as cROOH increases. process was developed by Allied and licensed
The maximum rate is achieved at approximately by Allied/UOP [25–28].
35 wt % cumene hydroperoxide. In both processes several reactors are em-
Besides cumene hydroperoxide, both di- ployed in series. Fresh and recycled cumene are
methylphenylmethanol and acetophenone are fed to the first reactor, which may operate at
also formed as byproducts during this oxida- 8 – 12 wt % cumene hydroperoxide. The con-
tion. These arise from a secondary chain reac- centration increases by 4 – 8 wt % in each suc-
tion that proceeds in parallel with the main chain. cessive reactor; the last reactor may operate at
Byproduct formation is accelerated as the con- 25 – 40 wt % cumene hydroperoxide. Fresh air
centration of cumene hydroperoxide increases.
Acetone 5

is pumped in parallel to each reactor and vented The cleavage proceeds through an ionic
at the top after removal of organic vapors. mechanism and releases approximately 252 kJ/
In the Hercules process, the oxidation of mol of cumene hydroperoxide decomposed [30].
cumene is carried out at approximately 620 kPa The reaction rate accelerates rapidly with in-
(6 bar)/90 – 120 ◦ C, in the presence of a sodium creasing temperature. Consequently, decompo-
carbonate buffer [29]. Under these conditions sition of cumene hydroperoxide commonly is
the residence time in the oxidizer train is carried out in a continuously stirred reactor in
4 – 8 h and the hydroperoxide molar selectivity which the steady-state concentration of cumene
90 – 94 %. The spent air is first passed through hydroperoxide is maintained at a low level. The
water cooled and refrigerated condensers in se- heat released by the reaction can be used to esti-
ries to remove organic vapors, and is finally mate the concentration of hydroperoxide present
vented. The condensate is returned to the oxi- in the reactor at any time [33].
dizers after treatment [29]. The molar selectivity of the cleavage to phe-
In the Allied/UOP process (Fig. 1) the oxida- nol and acetone is higher than 99.5 % at tempera-
tion is carried out at atmospheric pressure. No tures below 70 ◦ C, but it decreases at higher tem-
buffer or promoter is added, but great care is peratures as increasing amounts of dimethylphe-
taken to wash all streams recycled to the oxi- nylmethanol and acetophenone (in addition to
dizer with alkali and water [27]. Temperature those present in the cumene oxidate) are formed
is maintained at 80 – 100 ◦ C. Residence time in (Table 4) [28].
the oxidizer train is 10 – 20 h and hydroperox-
Table 4. Formation of byproducts during cumene hydroperoxide
ide molar selectivity is 92 – 96 %. Spent air is decomposition ∗
vented after organic vapors are removed by con-
Temp. ◦ C Molar ratio (byproducts/phenol)×100
densation followed by activated carbon adsorp-
tion. The recovered materials are washed with DMPM equivalents∗∗ Acetophenone
aqueous sodium hydroxide and water, then re- 70 0.36 0.06
turned to the oxidizers. 90 0.61 0.06
The oxidation of cumene generates approx- 110 1.24 0.15
122 2.19 0.25
imately 116 kJ of heat per mole of cumene ox- 146 5.04 0.69
idized [30]. Part of this heat is carried to the
∗ Pure cumene hydroperoxide added to
condensers by organic vapors (this part is larger phenol – acetone – cumene solution containing initially 0.5 wt %
in the Allied/UOP process because of the lower water and 100 ppm sulfuric acid; data from [28].
operating pressure). The rest is removed by heat ∗∗ Sum of dimethylphenylmethanol, α-methylstyrene, and their
condensation products.
exchangers.
In both processes cumene hydroperoxide is
Acetone produced during the cleavag