Академический Документы
Профессиональный Документы
Культура Документы
OPERATIONS TRAINING
SUBJECT
PAGE
CHEMICAL BONDING
Ionic bond.
Covalent bond.
Inter-molecular forces.
Vandar Valls forces.
Hydrogen bonding.
Metallic bonding.
PERIODIC TABLE
The general properties of the first 26 D-block
Period.
Catalyst.
The chemistry of selected transition metals.
CHEMICAL EQUILIBRIUM
The equilibrium constants Kc and Kp.
Altering the state of equilibrium.
Calculate Kc and Kp from concentrations and
partial pressures.
REACTION KINETICS
Chemical kinetics.
Example of first order reaction.
Fast rates of reaction.
Slow rates of reaction.
The rate determining step in reaction
mechanism.
ADVANCED SCIENCE
1________________
8
8
12
16
17
18
19
21
27
29
31
31
31
34
40
43
43
50
50
50
51
____C&G PART 3 _
OPERATIONS TRAINING
SECTION
18.4.6.
18.4.7.
18.4.8.
18.5.
18.5.1.
18.5.2.
18.5.3.
18.5.4.
18.5.5.
18.5.6.
18.5.7.
18.5.8.
18.5.9
18.6.
18.6.1.
18.7.
18.7.1.
18.7.2.
18.7.3.
18.7.4.
18.7.5.
18.8.
18.8.1.
18.9.2.
18.8.3.
SUBJECT
PAGE
56
59
60
63
63
67
67
68
69
69
71
72
73
76
76
83
83
83
84
84
93
98
98
98
99
SECTION 2: MATHEMATICS
ADVANCED SCIENCE
2________________
____C&G PART 3 _
OPERATIONS TRAINING
SECTION 2: MATHEMATICS
SECTION
18.9.
18.9.1.
18.9.2.
18.9.3.
18.10.
18.10.1.
18.10.2.
18.11.
18.11.1.
18.11.2.
18.11.3.
18.11.4.
18.11.5.
18.12.
18.12.1.
18.12.2.
18.12.3.
18.12.4.
18.12.5.
18.12.6.
18.13.
18.13.1
18.13.2
18.13.3.
18.13.4.
18.14.
18.14.1.
18.14.2.
18.14.3.
18.15.
18.15.1.
18.15.2.
18.15.3.
18.15.4.
18.15.5.
18.15.6.
SUBJECT
PAGE
LOGARITHMS
Definition of logarithms.
The laws of logarithms.
Solution of index or exponential equations.
LINEAR EQUATIONS.
Linear simultaneous equations with three
unknowns.
The linear law.
QUADRATIC EQUATIONS
Multiplying binomials on sight.
Factorization.
The difference of to squares.
Solution by factors.
Solution by formula.
EXPONENTIAL FUNCTION
The distinguishing property of v = ex.
The exponential function.
Growth and decay laws.
Rates of change.
Natural logarithms.
Solution of equations involving ex.
DIFFERENTIATION.
Rate of change.
Functional notation.
Negative n values.
Zero and unity n values.
INTEGRATION.
The primitive.
Integration.
Direct rule.
TRIGONOMETRY
Introduction
Sine values.
Cosine values.
The tangent function.
The tangent curve.
Combined rules.
118
118
120
123
126
126
ADVANCED SCIENCE
3________________
129
135
135
136
139
140
142
144
144
146
149
150
152
153
157
157
162
167
169
173
173
173
175
180
180
182
184
186
187
192
____C&G PART 3 _
OPERATIONS TRAINING
SUBJECT
PAGE
201
201
204
205
206
207
207
207
207
210
212
ADVANCED SCIENCE
4________________
213
214
215
216
217
218
218
219
220
220
221
222
223
223
224
____C&G PART 3 _
SECTION
18.19.
18.19.1.
18.19.2.
18.19.3.
18.19.4.
18.19.5.
18.19.6.
18.19.7.
18.19.8.
18.19.9.
18.19.10.
18.20.
18.20.1.
18.20.2.
18.20.3.
18.20.4.
18.20.5.
18.20.6.
18.20.7.
18.21.
18.21.1.
18.21.2.
18.21.3.
18.21.4.
OPERATIONS TRAINING
SUBJECT
PAGE
ELECTROMAGNETIC INDUCTION
Magnetic fields produced by an electric
current.
Force on a conductor.
Magnitude of force on a conductor in magnetic
field is directly proportional to three factors.
The motor principle.
The conductor moving through a magnetic
field.
Lenzs law.
The generator principle.
Inductance.
Mutual inductance.
The energy stored in inductive circuits.
SINGLE PHASE SERIES CIRCUITS.
Pure resistance in the AC circuit.
Pure inductance in the AC circuit.
Pure capacitance in the AC circuit.
Series RLC circuit.
Power in AC circuit.
Series resonance.
Calculation of resonant frequency.
SINGLE PHASE TRANSFORMERS
The two coil transformer.
Phaser diagrams for the ideal transformer.
The transformer on load.
The practical transformer.
225
225
ADVANCED SCIENCE
5________________
226
227
227
229
231
231
232
235
238
240
240
240
241
243
247
252
252
256
256
258
259
264
____C&G PART 3 _
OPERATIONS TRAINING
SUBJECT
PAGE
INTRODUCTION
ANALOGUE CONTROL
Types of controller.
APPLICATION OF A CLOSED LOOP
CONTROL SYSTEM
Ratio control.
Cascade system.
Feed forward control system.
DIGITAL CONTROL SYSTEM
The nature of analogue and digital control
systems.
Digital to analogue and analogue to digital
convertors.
NUMBERS and CODES FOR DIGITAL
SYSTEMS.
Decimal number system.
Binary number system.
Hexadecimal.
The octal number system.
DIGITAL SYSTEM COMPONENTS
Logic gates.
The Flip-Flop - FF.
Logic circuits from NAND or NOR gates.
The arithmetic function.
Binary counter.
Decoders.
Encoder.
Multiplexer (data selector).
Demultiplexer (data distributers).
265
266
266
274
ADVANCED SCIENCE
6________________
274
275
276
277
277
277
279
279
280
287
288
289
289
291
293
294
297
297
298
299
300
____C&G PART 3 _
SECTION
18.27.
18.27.1.
18.27.2.
18.27.3.
18.27.4.
18.28.
18.28.1.
18.28.2.
18.28.3.
18.28.4.
18.28.5.
18.29.
18.29.1.
18.29.2.
18.29.3.
18.29.4.
18.29.5.
18.30.
18.30.1.
18.30.2.
18.31.
18.31.1.
18.31.2.
18.31.3.
18.31.4.
OPERATIONS TRAINING
SUBJECT
PAGE
THE MICROPROCESSOR
Internal architecture of a microprocessor.
Arithmetic/logic unit, ALU.
Accumulator and registers.
Programme control, PC.
THE MICROPROCESSOR SYSTEM or THE
MICROCOMPUTER.
Components of microprocessor system or
microcomputer.
The organization of microprocessor.
Memory.
Input/output devices.
Inter-connection buses.
DEVELOPMENT OF COMPUTER
CONTROL
Digital supervisory control.
Direct digital control.
Distribution computer control.
Programmable logic control. PLC.
Main parts of PLC system.
THE INSTRUCTION SET and
ADDRESSING MODES OF
MICROPROCESSOR
Instruction classification.
The addressing modes.
MACHINE CODE PROGRAMMES.
Assembly language.
Implementing an instruction.
The flo chart example.
Translate flow chart to assembler code.
301
301
302
303
304
305
ADVANCED SCIENCE
7________________
305
306
307
310
311
314
314
315
316
318
319
321
321
322
324
324
325
326
329
____C&G PART 3 _
OPERATIONS TRAINING
Ionic Bond:
ADVANCED SCIENCE
8________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 1.1
The sodium chloride crystal. (Top) A photograph showing the cubic shape of sodium
chloride crystals. (Right) A model of a portion of the crystal detailing the regular
arrangement of sodium ions and chloride ions. Each sodium ion is surrounded by six
chloride ion and each chloride ion by six sodium ions.
Li+(1s2) + e
Once formed, the Li+ and F ions attract one another because of
their opposite charges. It is this attraction between the ions that
constitutes the ionic bond.
When a reaction between lithium and fluorine actually takes place
in real life, huge numbers of atoms are involved and equally huge
numbers of ions are formed.
ADVANCED SCIENCE
9________________
____C&G PART 3 _
OPERATIONS TRAINING
These ions pack them selves together to form the ionic solid, LiF. It
is important to remember that an ionic solid such as this does not contain
discrete molecules, but instead contains ions packed so that the attractive
forces between ions of opposite charge are maximized. While repulsive
forces between ions of the same charge are minimized.
Lewis Electron Dot symbols:
The preceding equation for the electron transfer between Na and Cl
can be simplified by writing Lewis electron dot symbols for the atoms
and monatomic ions (ions formed from a single atom).
In these symbols, the electrons in the valence shell of the atom or
ion are represented by dots placed a round the letter symbol of the
element. Table (1.1) lists the Lewis symbol and corresponding valence
shell electron configurations for the atoms of the second and third
periods.
Note that the dots are placed one to each side of the letter symbol
until all four sides, are occupied.
Table 1.1
Lewis Electron-Dot Symbols and Valence-Shell Electron Configurations for Atoms of
the Second and Third Period
Second period
Third period
Then the dots are written to a side until all valence electrons are
accounted for. (The exact placement of the single dots is immaterial. For
example, the single dot in the Lewis symbol for chlorine can be written
on any one of the four sides.)
The equations representing the transfer of an electron from the
sodium atom to the chlorine atom is written.
..
..
_
+
Na . + . Cl :
Na + | : Cl : |
..
..
ADVANCED SCIENCE
10________________
____C&G PART 3 _
OPERATIONS TRAINING
Example 1.2:
What is the formula of an ionic compound formed between Mg and P?
Solution:
Magnesium is in-group IIA and therefore will lose two electrons to
achieve a noble gas configuration. The ion formed is Mg2+.
Phosphorus is found in group VA and must acquire three electrons
to attain a noble gas structure. This produces that ion P 3. To make the
compound neutral, the total positive or negative charges must be a
multiple of both the 2+ and 3. The smallest number that is divisible by
both 2 & 3 is 6, so
(2+) x 3 = 6+
(3-) x 2 = 6net
0
The formula has to be Mg3P2.
1. 2. The Covalent Bond:
ADVANCED SCIENCE
11________________
____C&G PART 3 _
OPERATIONS TRAINING
..
H : Cl :
..
ADVANCED SCIENCE
12________________
____C&G PART 3 _
OPERATIONS TRAINING
A: B
H ++
: NH
H. .
: N : H
..
H
Multiple Bonds:
So far, the molecules we have described have had only single
bonds, that is, covalent bonds in which a single pair of electrons is shared
by two atoms. But it is possible for two atoms to share two electron pairs
to give a double bond or three pairs to give a triple bond. As examples,
consider ethylene, C2H4, and acetylene, C2H2. Their Lewis formulas are
H
or
C=C
C::C
Ethylene
H:C:::C:H
or
HC CH
Acetylene
ADVANCED SCIENCE
13________________
____C&G PART 3 _
OPERATIONS TRAINING
:
S
and
C
O
2-
2-
2-
14________________
ADVANCED SCIENCE
____C&G PART 3 _
OPERATIONS TRAINING
H . (g) + H . (g)
H
H
|
|
HC. + .CH
|
|
H (g)
H (g)
15________________
____C&G PART 3 _
OPERATIONS TRAINING
As the order increases, the bond length decreases, and the strength
of the bond increases and so does the vibrational frequency and bond
energy.
Data that illustrate this are shown in Table (1.2)
Table 1.2
Bond
CC
C=C
CC
CO
C=
O
CN
C
N
Bon
d
order
Average
Bond length
(A)
Average
Bond energy
kJ/mol
Average
vib.
frequency
1
2
3
1
2
1.54
1.37
1.20
1.43
1.23
370
699
960
350
750
3.0 x 1013
4.9 x 1013
6.6 x 1013
3.2 x 1013
5.2 x 1013
1
3
1.47
1.16
300
730
3.7 x 1013
6.8 x 1013
1. 3. Intermolecular forces:
The attractive forces between molecules are much weaker than the
chemical bonding forces that exist between atoms in a molecule. We can
classify intermolecular forces into two types.
a. Vander waals forces.
b. Hydrogen bonding.
Table (1.3) lists the types of intermolecular forces and compares
their energies with those of chemical bonds.
Table 1.3
ADVANCED SCIENCE
16________________
____C&G PART 3 _
Type of force
OPERATIONS TRAINING
Approximate energy
kJ/mol
Intermolecular
Vander waals
Hydrogen bonding
0.1 - 10
10 - 40
Chemical bonding
Ionic
Covalent
100 1000
100 1000
ADVANCED SCIENCE
17________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 1.2
Hydrogen bonding in water, (a) the electrons in the O-H bond of H 2O molecules are
attracted to the oxygen atoms, leaving the positively charged protons partially
exposed. A proton on one molecule will be attracted to a lone pair on an oxygen atom
in another water molecule. (b) Hydrogen bonding between water molecules is
represented by a series of dots.
ADVANCED SCIENCE
18________________
____C&G PART 3 _
OPERATIONS TRAINING
19________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 1.3
Delocalized bonding in sodium metal. The metal consists of positive sodium ions in a
sea of valence electrons. Valence (bonding) electrons are free to move throughout
the metal crystal (colored area)
20________________
____C&G PART 3 _
OPERATIONS TRAINING
Period
Fig. 2.1
Classification of the transition elements.
ADVANCED SCIENCE
21________________
____C&G PART 3 _
OPERATIONS TRAINING
The f-block transition elements are the two rows of elements at the
bottom of the periodic table. The elements in the first row are called the
lanthanides or rare earths; the elements in the second row are called
actinides.
All of the actinides are radioactive and from neptunium (element
93) onwards are synthetic. They have been produced in nuclear reactors
or by using particle accelerators.
The transition elements have a number of characteristics that set
them apart from the maingroup elements.
1. All of the transition elements are metals and, except for the
IIB elements, have high melting point, high boiling points,
and are hard solids. Thus in the fourth period elements from
scandium to copper, the lowest melting metal is copper
(1083C) and the highest melting point is vanadium
(1890C). In the main group metals, only beryllium melts
above 1000C, and the rest melt at appreciably lower
temperatures.
2. With the exception of the IIIB and IIB elements, each
transition element has several oxidation states. Chromium,
for example, exists in all oxidation states from 0 to +6. Of
the maingroup metals, only the heavier ones display several
oxidation states. Because of their multiplicity of oxidation
states, the transition elements are often involved in oxidation
reduction reactions.
3. Transition-metal compounds are often colored, and many are
Para-magnetic. Most of the compounds of the main group
metals are colorless and diamagnetic.
Melting points, Boiling points, and Hardness, are shown in Table
(2.1). All of these properties depend on the strengths of metal bonding,
which in turn depend roughly on the number of unpaired electrons in the
metal atoms.
Table 2.1
Properties of the fourth-period transition elements
ADVANCED SCIENCE
22________________
____C&G PART 3 _
OPERATIONS TRAINING
Note:
Common oxidation states are in bold face, asterisks denote the
stables states. Additional oxidation states, particularly zero and negative
values, may be observed in complexes with CO and with organic
compounds.
Colored Ions:
ADVANCED SCIENCE
23________________
____C&G PART 3 _
OPERATIONS TRAINING
Complex Ions:
Many metal ions, especially those of the transition elements, form
coordinate bonds with molecules or anions having lone pairs of electrons.
For example, the silver ion, Ag+, can react with NH3 to form the
Ag(NH3)2+ ion. The lone pair of electrons of the N atom of NH 3 form a
coordinate covalent bond to the silver ion:
Ag+ + 2(: NH3)
(H3N : Ag : NH3)+
The formation constant, or stability constant, K, of a complex ion
is the equilibrium constant for the formation of the complex ion from the
aqueous metal ion and the ligands (NH3 molecules). Thus the formation
constant of Ag(NH3)2+ is.
ADVANCED SCIENCE
24________________
____C&G PART 3 _
OPERATIONS TRAINING
Ag[NH3]2+
K =
[Ag+] [NH3]2
The large value of K means that the complex ion is quite stable.
Table (2.4) lists values for the formation constants of some complex ions.
Table 2.4
Formation constants of complex ions at 25C
Para magnetic:
Among the first complexes studied were those of chromium (III).
There are a great number of these, including the violet complex hexaaqua chromium chloride, [Cr(H2O)6]Cl3, and the yellow complex hexaamine chromium chloride [Cr(NH3)6]Cl3.
Almost all chromium complexes have the coordination number 6,
and thus are octahedral complexes. All are paramagnetic, displaying
magnetism equivalent to that of three unpaired electrons.
The orbital diagram for the metal atom in the complex, [Cr(NH3)6]Cl3:
Ar
3d
4s
4p
4d
ADVANCED SCIENCE
25________________
____C&G PART 3 _
OPERATIONS TRAINING
Ar
3d
4s
4p
4d
Co(CN)63-:
Ar
4s
ADVANCED SCIENCE
4p
26________________
4d
____C&G PART 3 _
OPERATIONS TRAINING
Coordination
number
2
4
6
Geometry
Linear
Tetrahedral
Square
planer
Octahedral
Hybrid
orbital
sp
sp3
dsp2
d2sp3 or sp3d2
2. 2. Catalyst:
1. Fe with K2O and Al2O3.
In Haber process for ammonia
N 2 3H 2 2NH 3
2. Pt Rh mixture.
In Ostwald process for nitric acid (NO reacts with O2 and H2O to give
HNO3)
4NH 3 5O 2 4NO 6H 2 O
3. Pt, V2O5.
Contact process for sulfuric acid (SO3 reacts with H2O to give H2SO4).
2SO 2 O 2 2SO 3
ADVANCED SCIENCE
27________________
____C&G PART 3 _
OPERATIONS TRAINING
C H
2
H2
6. Ni.
Catalytic methanation (preparation of substitute natural gas).
CO 3H 2 CH 4 H 2O
7. Fe CO mixtures.
Fischer Tropsch process (preparation of synthetic gasoline).
8CO 17H 2 C8H18 8H 2O
9. Al2O3.
Industrial synthesis of carbon disulfide.
CH 4 2S2 CS3
2H 2S
ADVANCED SCIENCE
28________________
____C&G PART 3 _
OPERATIONS TRAINING
Natural gas
C S H 2 O g CO g H 2 g
Coal
In the presence of ZnO and Cr 2O3, carbon monoxide and hydrogen
give methanol, CH3OH. Methanol is the starting material for
formaldehyde, CH2O, which is used to make plastics, carbon monoxide
and hydrogen also react in catalytic methanation to give methane for
substitute natural gas, the catalyst is nickel.
Study of the catalysts and reaction conditions for the various
reactions of CO and H2 has become an active research area. These
reactions make it possible to convert a variety of organic materials,
including coal and organic wastes, to gaseous and liquid fuels and all of
the industrial chemicals presently obtained from petroleum.
2. 3. The chemistry of selected transition metals:
Iron and titanium are the most abundant of the transition elements.
In fact, iron is the fourth most abundant element in the earths crust, after
oxygen, silicon, and aluminum. The transition elements occur in most
cases as oxide or sulfide ores. Table (2.6) lists some of these ores. The
least reactive elements, such as gold, silver, copper, and platinum, are
found as uncombined metals.
Table 2.6
Some ores of the transition metals
ADVANCED SCIENCE
29________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
30________________
____C&G PART 3 _
OPERATIONS TRAINING
aA bB cC dD
[C]c [D]d
[A]a [B]b
ADVANCED SCIENCE
31________________
____C&G PART 3 _
OPERATIONS TRAINING
N2
3H 2
g 2NH 3 g
Solution:
a. The expression for the equilibrium constant is:
Kc =
[CH4] [H2O]
[CO] [H2]3
[NH3]
[N2] [H2]
ADVANCED SCIENCE
32________________
____C&G PART 3 _
OPERATIONS TRAINING
Exercise:
Write the equilibrium-constant expression, Kc, for the equation
2NO 2
7H 2
g 2NH 3 g 4H 2 O g
2 g
7 H2
2
NH
3 g
2H O
2
pressure
gauge
Fig. 3.1
The concentration of a gas at a given temperature is proportional to the pressure.
33________________
____C&G PART 3 _
OPERATIONS TRAINING
PCH4 PH2O
PCO PH2 3
Kp =
298
800
1000
1200
Kc
4.9 x 1027
1.38 x 105
2.54 x 102
3.92
ADVANCED SCIENCE
34________________
____C&G PART 3 _
OPERATIONS TRAINING
35________________
____C&G PART 3 _
OPERATIONS TRAINING
2 g
2 g
exothermic
2HI
H 9.6 kJ
g
endothermic
2NO g H 180 kJ
acid
alkali
add acid
chromate
(yellow)
dichromate
(orange)
add alkali
equilibrium state (A)
ADVANCED SCIENCE
36________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 3.2
Equilibrium is soon formed. A further increase in the concentration
of H ions leads to a new equilibrium state (B), which has a more intense
orange colour. There has been an increase in the concentration of
dichromate ions due to a chemical reaction, which reduced the
concentration of H+ ions.
+
aq
2H
aq
Chromate
yellow
Cr O 2 2 7
acid
H O
aq
alkali
acid
(ex H2SO4)
dichromate
orange
4 gas molecules
2NH 3 g
37________________
____C&G PART 3 _
N 2 g O2 g
OPERATIONS TRAINING
2NO g
2 gas molecules
2 gas molecules
nitrogen monoxide
An increase of pressure reduces the gas volume but does not affect
the position of equilibrium, according to Le Chatelier, because a
movement towards products or reactants will not reduce the effect of the
increased pressure since there are equal numbers of N2, O2 and NO
molecules.
Haber process for the manufacture of ammonia:
Nitrogen reacts with hydrogen and forms ammonia. The reaction is
reversible.
N 2 g 3H 2 g
nitrogen
hydrogen
2NH 3 g
H 91 kJ
ammonia
ADVANCED SCIENCE
38________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
39________________
____C&G PART 3 _
OPERATIONS TRAINING
It was stated earlier that for reactions involving gases, Kp and Kc are not
necessarily equal. For the general equation
aA bB cC dD
PCc PDd
Kp =
PAa PB b
and
Kc =
[C]c [D]d
[A]a [B]b
Concentration, you recall, has the units moles per liter, or n/V.
Assuming ideal gas behaviour, we can use the ideal gas law,
PV = n R T
To obtain the concentration of a gas, x, in a mixture as,
[x] =
nx
Px
=
V
RT
[C]c [D]d
(R T)(c + d) (a + b)
[A]a [B]b
or
Kp = Kc (R T)(n)
where n is the change in the number of moles of gas when going from
reactants to products.
n = number of moles of products number of moles of reactants
ADVANCED SCIENCE
40________________
____C&G PART 3 _
OPERATIONS TRAINING
2SO 2 g O 2 g
2SO 3
Kp = Kc (R T)(n)
Solving equation for Kc , we obtain
Kc = Kp (R T)(-n)
n = (2 3) = - 1
T = (25 + 273) = 298 K
R = 0.0821 liter.atm/mol.K
Kc = (3 x 1024 atm-1) [(0.0821 liter.atom.mol-1.K-1) (298K)]- (-1)
Therefore, Kc = 7 x 1025 mol/liter
Exercise:
Phosphorus pentachloride dissociates on heating:
PCl 5 g
PCl 3 g
Cl 2
-2
ADVANCED SCIENCE
41________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
42________________
____C&G PART 3 _
OPERATIONS TRAINING
These are the factors, which after a lengthy period of research on a pilot
plant, are known to affect the speed or rate at which products are formed.
However, the final choice of conditions, such as the operational
temperature or concentration, is always based on those, which produce an
economic yield and not on those, which provide the greatest rate of
reaction.
4. 1. Chemical kinetics:
Is the study of how reaction rates change over varying conditions
and what molecular events occur during the overall reaction.
a. Rate of reaction:
Defined as the rate of decrease of concentration of one of the
reactants or the rate of increase in concentration of one of the products.
Rate units are expressed in term of mol/(l.sec).
The study of the rate, or speed, of reaction has important
applications. In the manufacture of ammonia from nitrogen and
hydrogen, we may wish to know what conditions will help the reaction to
proceed in a commercially feasible length of time.
Further reason for studying reaction rates is to understand how
chemical reaction occurs. By notting how the rate of reaction is affected
by changing condition.
Example:
The following example will illustrate the meaning and concept of
reaction rate.
When zinc granules are adds to 1M hydrochloric acid solution,
bubbles of hydrogen gas quickly form. After starting a stopclock, the
hydrogen gas evolved is collected and its volume measured in a gas
syringe at different times. The results are plotted on a Volume Time
graph.
ADVANCED SCIENCE
43________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 4.1
The shape of the graph indicates that the rate of formation of
hydrogen is greatest at the start of the reaction and slowly decreases with
time.
Eventually, when all the zinc has reacted, no more hydrogen is
formed and its volume remains constant. At this point, the rate of
formation of hydrogen is zero.
For gas reactions, pressures are used as a measure of concentration.
The higher the pressure of a gas, the greater is the number of (gas
particles/unit volume) and hence the greater the concentration.
Progress of the zinc-hydrochloric acid reaction would also have
been followed by plotting the concentration of HCl against time.
Note that this graph looks different to the hydrogen graph. Here,
the acid is being consumed and its concentration decreases with time.
Fig. 4.2
ADVANCED SCIENCE
44________________
____C&G PART 3 _
OPERATIONS TRAINING
change in HCl
concentration
mol/l
=
time change
sec
>
R2 >
R3
2 mol
1 mol
45________________
____C&G PART 3 _
OPERATIONS TRAINING
2NO2F (g)
ADVANCED SCIENCE
46________________
____C&G PART 3 _
OPERATIONS TRAINING
dD + eE
c = catalyst
2NO2F (g)
Once we know the rate law for a reaction and have found the value
of the rate constant, we can calculate the rate of reaction for any value of
reactant concentrations.
Knowledge of the rate law is also useful in understanding how the
reaction occurs at the molecular level.
c. Molecularity:
ADVANCED SCIENCE
47________________
____C&G PART 3 _
OPERATIONS TRAINING
NO + CO2
(previous example).
NO3 + NO
ADVANCED SCIENCE
48________________
____C&G PART 3 _
OPERATIONS TRAINING
NO3 + NO
(elementary reaction)
NO3 + CO
NO3 + NO
(elementary reaction)
+
NO3 + CO
NO2 + CO
NO + CO2
ADVANCED SCIENCE
49________________
____C&G PART 3 _
OPERATIONS TRAINING
H+
2O2 (g)
methane
oxygen
ignite
CO2 (g) +
2H2O (g)
Ca (HCO3)2
50________________
____C&G PART 3 _
OPERATIONS TRAINING
2H2
2H2O
N2
N2O2
H2
N2O + H2O
N2O +
H2
N2 + H2O
N2O2
The sum of these steps in the sequence does give us the overall
balanced equation.
Reaction mechanism, such as the one just described, are usually
arrived at by bringing together both theory and experiment. For instance,
suppose we wish to study the following hypothetical reaction in hopes of
discovering the mechanism.
2A + B
ADVANCED SCIENCE
C + D
51________________
____C&G PART 3 _
OPERATIONS TRAINING
C + D
A2
C + D
ADVANCED SCIENCE
52________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
2A
53________________
____C&G PART 3 _
OPERATIONS TRAINING
A2
A2
2A
A2 + B
C + D
A2
fast
C + D
slow
= rate r = k r [A2]
or simply
k f [A]2 = k r [A2]
Solving this equation for [A2], we have
k f [A]2
kr
We can now substitute this into equation and combine all the
constants to give still another constant, let us say k. This gives the rate
expression
[A2] =
ADVANCED SCIENCE
54________________
____C&G PART 3 _
OPERATIONS TRAINING
NO2 + Cl
NO2 + Cl2
What would be the observed experimental rate law if the first step
were slow and the second were fast?
Solution:
If the first reaction is the slow step, it is also the rate-determining
step. The rate law for the overall reaction should be the same as the rate
law for the rate-determining step.
Since only one molecule of NO2Cl is involved, the rate law for the
first reaction as well as for the overall reaction would be
rate = k [NO2Cl]
4. 6. The experimental determination of reaction rate:
Rate of reaction is usually measured by following the change in
concentration per second, of a reactant or product. i.e. we must determine
the concentration of reactants during the course of reaction.
Measurement can be achieved in different ways:
ADVANCED SCIENCE
55________________
____C&G PART 3 _
OPERATIONS TRAINING
1. One way to do this for a slow reactions is to take samples from the
reaction vessel at various times and analyze them.
Example:
The rate of reaction of ethylacetate with water in acidic solution.
O
|
|
|| |
C C - O C C + H2O
|
|
| |
H+
O
|
|
||
C C OH + HO C CH3
| |
or
O
||
CH3CH2OCCH3
Ethylacetate
+ H2 O
water
H+
O
||
CH3CH2OH + HOCCH3
Ethanol
Acetic acid
ADVANCED SCIENCE
56________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 4.3
An experiment to follow the change of pressure during the decomposition of N2O at
45C. Pressure values can be related to the concentration of N2O5 in the flask.
Example:
The decomposition of dinitrogen pentoxide in the gas phase:
2N2O5 (s)
Table. 4.1
ADVANCED SCIENCE
Time
sec
N2O5
Mol/l
0
600
1.65 x 10-2
1.24 x 10-2
Rate
Mol/l.se
c
6.8 x 10-6
5.2 x 10-6
3.7 x 10-6
3.0 x 10-6
57________________
2.3 x 10-6
1.7 x 10-6
____C&G PART 3 _
OPERATIONS TRAINING
0.93 x 10-2
0.71 x 10-2
0.53 x 10-2
0.39 x 10-2
0.29 x 10-2
1200
1800
2400
3000
3600
[N2O5]
t
0.31 x 10-2
=
600
The rate of reaction during each time interval has been calculated
in this way and given in the above Table (4.1).
Note that the rate slows as the reaction proceeds.
ADVANCED SCIENCE
58________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
59________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
energetic collisions
total number of
= 3 x 1020 = 1
3 x 1033
1013
60________________
____C&G PART 3 _
OPERATIONS TRAINING
collisions
We can see that only one in (1013) collisions results in chemical
change.
The collision theory is useful in that it offers an explanation for
why there is a change in rate of reaction when there is a change in
reaction conditions.
Collision theory explanation of effect on reaction rate:
We can now use that collision theory to explain how the reaction rate
is affected by:
a. Particle size of solids:
Fig. 4.4
The smaller the particle size, the greater the surface area and,
consequently, the greater the number of solid surface atoms
likely to collide within molecules in the surrounding liquid or gas.
Increased collision frequency leads to an increased rate of reaction.
ADVANCED SCIENCE
61________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 4.5
b. Concentration of solution:
By increasing a concentration of a solution a greater number of
more solute particles are present in unit volume. The reduction in
distance leads to an increased collision frequency and a consequent
increased in reaction rate.
c. Pressure in gases:
An increase of pressure pushes gas particles closer together and
increases the collision frequency. Thus, reaction rate increases with
increase of pressure.
18. 5. CATALYSIS
5. 1. Catalyst-definition:
ADVANCED SCIENCE
62________________
____C&G PART 3 _
OPERATIONS TRAINING
Type of catalysis:
There are two types of catalysis homogenous and heterogeneous.
ADVANCED SCIENCE
63________________
____C&G PART 3 _
OPERATIONS TRAINING
1. Homogeneous catalysis:
This term is applied to reaction in which the catalyst is in the same
phase as the reactants. It usually takes place in the liquid phase, as a
gaseous catalysis is very rare.
Example:
In the commercial preparation of sulfuric acid, its anhydride sulfur
trioxide is obtained by oxidizing sulfur dioxide, SO2.
Sulfuric acid is then obtained from SO 3 is normally very slow. In
an early industrial process, this reaction was carried out in the presence of
nitric oxide. NO, because it is then much faster
2SO2 (g) + O2 (g)
NO
2SO3 (g)
Nitric acid, NO, does not appear in the overall equation, nor does it
in any way affect the final composition of the reaction mixture. Thus, it
act as a catalyst.
A possible mechanism for the nitrite oxide catalyst is
2NO + O2
2NO2
NO2 + SO2
SO3 + NO
The last step occurs twice each time the first step occurs once.
Thus, two molecules of nitric oxide are used up in the first step and are
regenerated in the second step.
This catalytic reaction in a homogeneous phase is called
homogeneous catalysis.
2. Heterogeneous catalysis:
ADVANCED SCIENCE
64________________
____C&G PART 3 _
OPERATIONS TRAINING
H
\
/
C=C
/
\
+
H
H2
Pt
H H
|
|
HCCH
|
|
H H
ethane
ADVANCED SCIENCE
65________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 5.1
The mechanism of the catalytic hydrogenation of C2H4. (a) C2H4 and H2 molecules
diffuse to the catalyst. (b) The molecules form bonds (dotted lines on the catalyst
surface. The H2 molecule dissociates to atoms. (c) These H atoms migrate to the C 2H4
molecule, where they react to form C2H6. (d) C2H6 diffuses away from the catalyst.
ADVANCED SCIENCE
66________________
____C&G PART 3 _
OPERATIONS TRAINING
Thermal
decomposition
Al2O3
Cu
ADVANCED SCIENCE
67________________
____C&G PART 3 _
OPERATIONS TRAINING
However, the idea that a small amount of the catalyst can cause a
large amount of reaction does not mean that the catalyst concentration is
unimportant.
In fact, when the reaction does not entail a chain mechanism, the
rate of the reaction is usually proportional to the concentration of the
catalyst, while such a simple relationship may not often exist in solidcatalyzed reactions (heterogeneous reactions), in homogenous catalysis
there is frequently a direct concentration.
For example, the hydrolysis of esters in an acid solution will
depend on the concentration of hydrogen ion acting as a catalyst.
5. 4. Activity of different d-block element catalyst:
1. Metals or metal conductors such as (Fe, Pt, Ag, Ni, etc . . ):
Metals Chemisorb oxygen and hydrogen and therefore are usually
effective catalysts for oxidation- reduction and hydrogenationdehydrogenation reactions, thus platinum is a successful catalyst for the
oxidation of SO2, and Ni is used effectively for hydrogenation of
hydrocarbons.
The Pt catalyst is more active at about 400C, but because of its
susceptibility to poisons and sensitivity to high temperature, the Pt
catalyst has largely been replaced by V2O5.
The Haber process, the industrial process for producing ammonia,
uses an iron catalyst, high temperatures (550 - 600C) and high pressures
(100 - 200 atm).
N2 (g) + 3H2 (g)
2NH3 (g)
ADVANCED SCIENCE
68________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
69________________
____C&G PART 3 _
OPERATIONS TRAINING
The forces attracting the fluid molecules to the solid surface are
relatively weak. The binding forces are equivalent to van der waals
forces. The energy of activation for physical adsorption is small (usually)
no more than 1 kCal/g.mole).
The amount of physical adsorption decreases rapidly as the
temperature increases. This is an evidence that physical adsorption is not
responsible for catalysis, physical adsorption studies are valuable in
determining the physical properties of solid catalysts. Thus the question
of surface area and pore-size distribution in porous catalysts can be
answered from physical-adsorption measurements.
2. Chemical adsorption (chemisorption):
This type of adsorption involves forces much stronger than in
physical adsorption. The binding forces are similar to chemical
compound formation, i.e., the adsorbed molecules are held to the surface
by valence forces of the same type as those occurring between atoms in
molecules.
Because of high heat of chemical adsorption, the energy passed by
chemisorbed molecules can be substantially different from that of the
molecules alone.
Hence the energy of activation for reactions involving chemisorbed
molecules can be considerably less than that for reactions involving gasphase molecules. It is on this bases that chemisorptions offers an
explanation for the catalytic effect of solid surfaces.
Two kinds of chemisorption are encountered:
1. Activated:
It means that the rate varies with temperature.
2. Non-activated:
This type is less frequent. In this case chemisorption occurs very
rapidly, i.e., activation energy near zero.
It is often found that for a given gas and solid the initial
chemisorptions is non-activated, while later stages of the process are slow
and temperature dependent (activated chemisorption).
ADVANCED SCIENCE
70________________
____C&G PART 3 _
OPERATIONS TRAINING
k1 (N2)
H23
NH32
k-1
NH32
H23
N2 + 2S
2NS
N2 chemisorption
Step 2:
3H2 + 6S
6HS
H2 chemisorptions
2NH3 + 8S
surface reaction
ADVANCED SCIENCE
71________________
____C&G PART 3 _
N2 + 2S
2NS + 3H2
OPERATIONS TRAINING
2NS
2NH3 + 2S
(1)
A + x1
Ax1
Chemisorption:
B + x2
Bx2
(3)
Ax1 + Bx2
Cx1
(4)
C + x1
(5)
(6)
Surface reaction:
Desorption of product:
Poisoning:
Thermal deactivation:
Cx1
P + x1,2
x1,2
x1,2
(2)
(7)
ADVANCED SCIENCE
72________________
____C&G PART 3 _
OPERATIONS TRAINING
Ax1
C + x1
73________________
____C&G PART 3 _
OPERATIONS TRAINING
Chemical change
Iron
nitrogen/hydrogen mixture
ammonia NH3
sulphur (VI)
oxide
(sulphur dioxide)
Platinum + 10% rhodium
ammonia/air
(sulphur trioxide-for
sulphuric acid
production)
nitrogen oxide, NO
(nitrogen monoxide-for
nitric acid production)
ADVANCED SCIENCE
74________________
____C&G PART 3 _
OPERATIONS TRAINING
e.g.
Solid catalyst
Chemical change
Nickel at 140C
hydrogenation of alkenes
e.g.
e.g.
C2H6 (g)
ethane
catalytic cracking of alkanes
kerosene vapor
alkenes, cycloalkanes
Nickel catalyst at
900C
naphtha
from crude oil
distillation
alkanes
a mixture of CO and H2
ADVANCED SCIENCE
75________________
____C&G PART 3 _
OPERATIONS TRAINING
6.1. Explain the function of buffer solution and give the composition
of
typical buffer solution.
What we wish to examine in this section is how and why reactions
between electrolytes take place in solution.
Lets begin by considering the reaction that takes place when a
solution containing 1 mole of sodium chloride is added to a solution of 1
mole of silver nitrate. When these two solutions are combined, 1 mole of
the white solid, silver chloride is formed and the solution that remains
contains 1 mole of sodium nitrate, the chemical equation that represents
the change that has occurred during this reaction is.
NaCl (aq) + AgNO3 (aq)
ADVANCED SCIENCE
76________________
____C&G PART 3 _
OPERATIONS TRAINING
HC2H3O2
OH- + HC2H3O2
H2O + C2H3O2-
NH4+
OH- + NH4+
H2O + NH3
[H+] [C2H3O2-]
[HC2H3O2]
[HC2H3O2]
[C2H3O2-]
6.1
know ka for the weak
dissociate in aqueous
the solution from this
and by the number of
ADVANCED SCIENCE
77________________
____C&G PART 3 _
OPERATIONS TRAINING
1.0
1.0
= 1.8 x 10-5
The pH of this solution is 4.74
Notice that when the concentrations of the acid and anion are the
same in a buffer, the H+ concentration in that solution is equal to the Ka of
the weak acid, and the pH = pka. Thus, if a buffer were prepared by
mixing 0.1 mol of forming acid (ka = 1.8 x 10-4 from table 6.1) and 0.1
ADVANCED SCIENCE
78________________
____C&G PART 3 _
OPERATIONS TRAINING
pH = 3.74
HC2H3O2
[H+] =
[C2H3O2-] =
[HC2H3O2] =
Initial
Final
1.8 x 10-5 M
1.00 M
1.00 M
x
1.0 0.2 = 0.8 M
1.0 + 0.2 = 1.2 M
1.20
0.80
= 2.7 x 10-5 M
The pH of the buffer after the 0.2 mol of H+ is added is 4.57, a
change of only 0.17 pH units from its initial pH of 4.74.
Suppose now that we were to add 0.2 mol of H+ to 1 liter of a
solution of HCl whose pH = 4.74 (that is, a 1.8 x 10 -5 M HCl solution).
Since Cl- has virtually no tendency to react with H+, the final H+
ADVANCED SCIENCE
79________________
____C&G PART 3 _
OPERATIONS TRAINING
H2O + C2H3O2-
The numbers of moles per liter before the addition are the same as
above, but the number of moles per liter after 0.20 mol of OH - is added
would be
Concentration after addition of 0.2 mol of OH-.
[H+] =
[C2H3O2-] =
[HC2H3O2] =
x
1.0 + 0.2 = 1.2
M
1.0 - 0.2 = 0.8 M
ADVANCED SCIENCE
80________________
____C&G PART 3 _
OPERATIONS TRAINING
0.12 mol
= 0.24 M
0.50 lit
[NH4+]
0.09 mol
= 0.18 M
0.50 lit
a. The OH- concentration for this alkaline buffer is found by using the
kb for NH3:
NH4+ + OH-
NH3 + H2O
[NH4+] [OH-]
kb =
[NH3]
Rearranging and solving for [OH-] we have.
[OH-] = kb
[NH3]
[NH4+]
0.24
0.18
= 2.4 x 10-5 M
pOH = 4.62
pH = 9.38
b. The neutralization reaction for H+ in this buffer is:
ADVANCED SCIENCE
81________________
____C&G PART 3 _
OPERATIONS TRAINING
H+ + NH3
NH4+
[OH-] =
[NH3] =
[NH4+] =
Initial
Final
2.4 x 10-5 M
0.24 M
0.18 M
x
0.24 0.04 = 0.2 M
0.18 + 0.04 = 0.22 M
0.20
0.22
= 1.6 x 10-5 M
pOH = 4.8
The pH is therefore 9.20, a decrease of 0.18 pH units.
Buffers find many important applications. Living systems employ
buffers to maintain nearly constant pH so that biochemical reactions can
follow their correct paths.
For example, blood contains, among other things, H 2CO3/HCO3buffer system that helps maintain the pH at 7.4.
In the laboratory may inorganic & organic chemical reactions are
performed in buffered solutions to minimize any adverse affects caused
by acids or bases that may be consumed or produced during reaction.
18. 7. CORROSION
ADVANCED SCIENCE
82________________
____C&G PART 3 _
OPERATIONS TRAINING
7. 1. Definitions:
Destruction of metal by other than mechanical means is defined as
corrosion failure and is the result of a destructive attack by chemical or
electrochemical reaction with its environment or (corrosion is the passage
of the metal into the chemically combined state).
Corrosion is a natural phenomenon which proceeds according to
well understood laws. Plastics and other non metallic substances are not
included in the above definition.
The mechanism of attack for these materials differs from that of
metallic materials.
7. 2. The corrosion reaction:
The most common example is the rusting of iron.
2Fe + 2H2O + O2
2Fe(OH)2
2Fe
4OH-
ADVANCED SCIENCE
83________________
____C&G PART 3 _
OPERATIONS TRAINING
& (2), and canceling the electrons from each side, yields the
chemical reaction equation.
7. 3. The requirements for corrosion:
1. A metal capable of under going an oxidation reaction.
2. An environment containing a corrodent capable of oxidizing the
metal to a chemically combined state. For steel suitable corrodents
are:
a. Dissolved oxygen.
b. Hydrogen ions (e.g. mineral acid HCl).
3. An environment that is electrolytically conducting. This is because
corrosion proceeds by an electrochemical mechanism. If any one of
these requirements in eliminated than there will be no corrosion.
7. 4. Forms of corrosion:
Corrosion
Uniform
Localized
General
Non-mechanical
Galvanic
Crevice
Deposit
Pitting
Intergranular
Biological corrosion
Mechanical
Stress corrosion cracking
Corrosion fatigue
Erosion
Cavitation
Fretting
General corrosion:
ADVANCED SCIENCE
84________________
____C&G PART 3 _
OPERATIONS TRAINING
85________________
____C&G PART 3 _
OPERATIONS TRAINING
The relative areas between the anode and cathode are important.
Since corrosion is caused by the flow of current from the anode to the
cathode, an unfavorable area ratio is a small anode and large cathode.
For example, steel rivets in a copper plate will corrode much more
quickly than copper rivets in a steel plate. If it is necessary to use
dissimilar metals, an attempt should be made to use two metals as close
as possible to each other in the galvanic series.
The further apart the metals are in the series the greater the
accelerated attack on the more active (anode) metal. Galvanic corrosion
can be prevented by insulating dissimilar metals from each other.
Galvanic series of metals from each other:
86________________
____C&G PART 3 _
OPERATIONS TRAINING
Cr(OH)3 + 3H-
(acid)
Characteristics:
1. Associated with passivatable metals (particularly stainless steel).
2. Takes time to initiate.
3. Is difficult to stop once started.
4. May occur in crevices formed between:
a. Two similar or dissimilar metals.
b. A metal and non-metal.
c. At a badly made weld.
Typical examples:
1. An austenitic stainless steel shaft in packed gland exposed to saline
water.
2. Many threaded joints.
3. One tube side of many tube/tube plate assemblies in heat
exchangers.
ADVANCED SCIENCE
87________________
____C&G PART 3 _
OPERATIONS TRAINING
Sensitive to:
1. Environment composition (especially oxygen and chloride
content).
2. Environment conductivity.
3. Crevice dimensions.
Deposit corrosion:
Analogous to crevice corrosion with many of its characteristics.
The lateral variation in solution composition and potential form between
deposit covered and deposit-free areas. Metal loss occurs under deposit.
Again, it is a problem that particularly affects passive metals.
Typical example:
Austenitic stainless steel in stagnant or low flow areas where environment
contains entrained solids.
Pitting corrosion:
This type occurs on normally passive metals, and corrosion
develops in localized areas, resulting in cavities or pits. These cavities or
pits can range from deep penetration of relatively small diameters to
larger diameter shallow cavities.
The depth of pitting can be expressed by the term pitting factor,
which is the ratio of deepest metal penetration to average metal
penetration. (see Fig. 7.1)
Fig. 7.1
Pitting corrosion
ADVANCED SCIENCE
88________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
89________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig. 7.2
Biological corrosion:
Corrosion of metal can be caused by the metabolic activity of
microorganisms either directly or indirectly. There are two types of
microorganisms associated with this type of corrosion-aerobic and
anaerobic.
Aerobic microorganisms grow in an atmosphere containing
oxygen, while anaerobic species grow in an environment devoid of
atmospheric oxygen.
The activity of these microorganisms can cause corrosion by:
1. Producing a corrosive environment.
2. Altering the resistance of the surface film.
3. Having an effect on the rate of anodic or cathodic reaction.
4. Creating electrolytic concentration cells on the metal surface.
5. Altering the environment composition.
ADVANCED SCIENCE
90________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
91________________
____C&G PART 3 _
OPERATIONS TRAINING
Corrosion fatigue:
When a metal is subjected to cyclic or repeated stress conditions,
the protective oxide films present rupture at a rate greater than new films
can be formed.
This condition results in the formation of anodic areas at the point
of the film rupture. This, in turn causes the formation of pits, which serve
as a stress concentration point for the origin of the cracks, leading to
ultimate failure.
This phenomenon results in the reduction of the ability of the metal
to resist cyclic or repeated stresses. Corrosion of the metal surface lowers
the fatigue resistance, and stressing of the surfaces will tend to accelerate
corrosion.
Typical example:
Structural steel in seawater (e.g. Oil production platforms).
Erosion corrosion:
Occurs when high velocity fluid flow disrupts passive films or
prevents their formation. Damage to passive film may be due to the
erosive effect of the fluid and/or entrained solid or gases.
Fluid is then corrosive towards the un-protected metal. Turbulent
flow in pipe work may initiate erosion corrosion. Flow disturbance
produced at bends and tees, in pumps and valves, or by orifice plates and
badly made welds, can cause problems.
Typical example:
1. Damage at elbows in gas production tubing.
2. Damage to copper pipework at high velocities (> 2 m/sec) on
seawater systems.
3. Damage to copper-based heat exchanger tubes at inlet end.
4. Vessel wall damage near badly directed inlet tube.
ADVANCED SCIENCE
92________________
____C&G PART 3 _
OPERATIONS TRAINING
Cavitation corrosion:
This is more correctly termed cavitation erosion. It is caused by the
formation of bubbles and their collapse on the metal surface, causing
mechanical erosion of the surface, which in turn destroys the protective
oxide film.
This results in more rapid corrosion attack as a result of the
destruction of the protective film. This phenomenon is experienced
around propellers, rudders, struts, the water-cooled side of diesel engines,
and the rotors of pumps.
Since the bubbles are formed when a vacuum condition exists, and
they collapse when pressure exists, a redesign of the operation or the use
of more resistant alloy can correct this condition.
Fretting corrosion:
Fretting corrosion is defined as damage occurring at the interface
of two surfaces in contact, one or both of which are metals, subject to
slight relative slip.
Fretting corrosion is responsible for the failure of both heads,
contacts of electrical relay, connecting rods, and various parts of vibrating
machinery. This type of corrosion can be prevented and/or greatly
reduced by the following methods.
1. Use of lubricants.
2. Use of a soft metal with a hard metal.
3. Use of gasketing materials like (Teflon).
4. Design of contacting surfaces to avoid slip.
7. 5. Corrosion control:
By design:
Good design can permit the effective use of cheaper materials. Bad
design may render good materials selection wholly ineffective.
ADVANCED SCIENCE
93________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
94________________
____C&G PART 3 _
OPERATIONS TRAINING
5. Cathodic protection.
e.g. Zinc rich paints.
Cathodic protection:
Cathodic protection can be achieved by the use of either an
impressed electric current or a sacrificial anode.
Although it cannot be used above the water line (out the area of the
electrolyte), it can be effectively used to eliminate corrosion fatigue,
Intergranular corrosion, and stress corrosion cracking, dezincification of
brass, or pitting of steels in seawater or steel in soil.
Fig. 7.3
Cathodic protection
ADVANCED SCIENCE
95________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
96________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
97________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
98________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.1
Percentage CO2 available for removal
Fig: 8.2
Percentage NH3 available for removal
ADVANCED SCIENCE
99________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.3
Percentage H2S available for removal
Fig: 8.4
Forced draft aerator
b. Clarification:
Suspended matter in raw water-supplies is removed by various
methods to provide a water suitable for domestic purposes and most
industries requirement. Removal is generally accomplished by
coagulation; flocculation and sedimentation, often referred to us
conventional clarification.
Coagulation is the process to promote aggregation of small
particles into large particles. Flocculation is the process of bringing
together the coagulated particles to form a large agglomeration or
flocculation.
ADVANCED SCIENCE
100________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.5
Up flow sludge blanket clarifier
Fig: 8.6
Solid-contact clarifier
c. Filtration:
ADVANCED SCIENCE
101________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.6
Vertical-type pressure sand filter
ADVANCED SCIENCE
102________________
____C&G PART 3 _
OPERATIONS TRAINING
Ca (HCO3)2
Fig: 8.7
Sludge-contactor softener
ADVANCED SCIENCE
103________________
____C&G PART 3 _
OPERATIONS TRAINING
CaCO3 + H2O
2CaCO3 + 2H2O
Mg (OH)2 +2CaCO3 + 2H2O
Mg (OH)2 + CaSO4
MgCl2 + Ca (OH)2
Mg (OH)2 + CaCl2
SO4
Mg
Na2SO4
+ 2NaOH
Cl2
ADVANCED SCIENCE
Mg(OH)2 +
2NaCl
104________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.8
Calcium reduction
vs.
Carbonate alkalinity.
Fig: 8.9
Magnesium reduction
vs.
Causticity
105________________
____C&G PART 3 _
OPERATIONS TRAINING
involved in this treatment method. The use of lime and soda ash permits
hardness reduction down to 0.5 grain per gallon, or about 8 ppm as
calcium carbonate.
Magnesium is reduced to 2 to 5 ppm because of the greater
insolubility of magnesium hydroxide at the elevated temperature.
Fig: 8.10
Down flow design of hot-process softener.
Silica reduction:
Hot process softening also permits a very good silica reduction.
Silica reduction is accomplished by sorption of silica on the magnesium
hydroxide precipitate. If there is insufficient magnesium present in the
raw water to reduce silica to the desired value, magnesium compounds
such as MgO, MgSO4, MgCO3, . . . etc, may be used.
Silica reduction by cold or warm processes is not nearly as good as
with hot process.
ADVANCED SCIENCE
106________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.11
Approximate magnesium oxide
Requirements for silica removal
In a hot process softener
e. Ion exchange:
All natural water contains in varying concentrations, dissolved salts
that dissociate in water to form charged particles called ions. The
negatively charged ions are called anions; the positively charged ions are
called cations.
Calcium, magnesium and sodium cation, along with bicarbonate,
sulfate and chloride anions are present in most raw water supplies.
Ion exchangers are materials that exchange one ion for another,
hold it temporarily and release it to a regenerante solution. A proper
regenerant can replace undesirable ions. For example the commonly used
ADVANCED SCIENCE
107________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.12
Sodium zeolite softener
108________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.13
Strong base anion resins.
Fig: 8.14
Schematic of hydrate strong-acid
Cation exchanger
The strong cation and the strong base anion resins can convert
neutral salts into their corresponding acids and base respectively.
This ability called salt splitting, results in different treated water
quality than that obtained by treatment with WC or WB resins. SC resins
derive their exchange activity from sulphonic acid functional groups
ADVANCED SCIENCE
109________________
____C&G PART 3 _
OPERATIONS TRAINING
(HSO3-) when operated on the hydrogen cycle they will remove nearly
all-raw water cations according to these reactions.
Ca
2HCO3
Mg SO4
+ 2ZSO3H
2Na 2Cl
2ZSO3
Ca
2HCO3
Mg + H2SO4
2Na
2HCl
2ZCOO
Ca
Mg + H2CO3
2Na
ADVANCED SCIENCE
110________________
____C&G PART 3 _
OPERATIONS TRAINING
R N CH3
|
CH3
An ethanol group replaces one of the methyl groups in type II resin.
CH3
+
|
R N CH2CH2OH
|
CH3
The principal difference between the two resins operationally, is
that type I has a greater chemical stability and type II has a slightly
greater regeneration efficiency, and capacity.
In the hydroxide from SB resin will remove all commonly
encountered inorganic acid according to these reactions:
H2SO4
2HCl
2H2SiO3
2H2CO3
+ 2ZOH
SO4
2Z 2Cl
2HSiO3
2HCO3
+ 2H2O
Like the cation resin reactions, the anion exchange reactions are
also reversible, regeneration with a strong alkali, such as caustic soda,
will return the resins to the hydroxide form.
Weak anion resins derive their functionality from primary (R NH 2),
Secondary (R NHR) and tertiary (R N R2) amine groups
WB resin absorb such free mineral acids such hydrochloric acid,
sulphuric acid and nitric acid, the reaction may represent as:
H2SO4
2HCl
2HNO3
+ 2ZOH
SO4
2Z 2Cl
NO3
+ 2H2O
ADVANCED SCIENCE
111________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.15
Calcium sulfate-fouled resin
Fig: 8.16
Iron-fouled resin
ADVANCED SCIENCE
112________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.17
Organic-fouled resin
Demineralization:
Demineralization, as applied to water treatment, is the removal of
essentially all inorganic salts by ion exchange. In this process, hydrogen
cation exchange converts dissolved salts to their corresponding acids, and
basic anion exchange removes these acids.
The only other commercial process, which produces water of
comparable purity, is distillation. Because demineralization of most fresh
water supplies is substantially less expensive than distillation, it is widely
used.
Principles of demineralization:
The demineralizer system consists of one or more ion exchange
resin columns, which is includes a strong cation unit and a strong anion
unit.
The cation resin exchanges hydrogen for raw water cation as
shown by these reactions:
Ca
Mg
2Na
SO4
2Cl
2HCO3
2NO3
+ 2HZ
2Z
Ca
Mg
2Na
H2SO4
+ 2HCl
2H2CO3
2HNO3
The anion resin exchanges hydroxyl anions for the highly ionized
anions as shown by these reactions:
H2SO4
2HCl
+ 2ZOH
2HNO3
ADVANCED SCIENCE
SO4
2Z 2Cl
2NO3
113________________
+ H2O
____C&G PART 3 _
OPERATIONS TRAINING
+ ZOH
HCO3
Z HSiO3
+ H2O
Ca
Mg
2Na
+ 2HCl
2ZSO3H
Ca
Mg
2Na 2Cl
+ 2NaOH
Na2SO4
2NaCl
2ZOH + 2NaNO
3
2NaHCO3
2NaHSiO3
ADVANCED SCIENCE
114________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.18
Mixed bed ion exchange unit, showing internal distribution
Equipment:
The demineralization system will vary according to the
requirements of the application. Fig. 8.19 shows nine basic demineralizer
systems and lists areas of application, typical treated water quality and the
relative advantages/disadvantages of each.
The cation and anion exchange columns for demineralization are
similar for hydrogen zeolite softening. The only difference is the use of
anion resin in the anion exchange column.
The piping, valves and fittings are made of lined or acid resistant
material, when required the decarbonator or vacuum degasifier is
identical in design to the unit used in split-stream softening.
ADVANCED SCIENCE
115________________
____C&G PART 3 _
OPERATIONS TRAINING
ADVANCED SCIENCE
116________________
____C&G PART 3 _
OPERATIONS TRAINING
Fig: 8.19
Dematerialize systems.
ADVANCED SCIENCE
117________________
____C&G PART 3 _