ct of pH on Hydrolysis
of Chlsroacetic Acid
L. F. BERHENKE AND E. C. BRITTON
The Doto Chemical Company, Midland, Mich.
A continuous titration method at constant pH has been
used to measure the rate of hydrolysis of chloroacetic acid
in 3 N aqueous solution at reflux temperature, 104' C.
With this method the rate studies have been carried
out at various pH values from 1 to 13. At pH 1 the titrating
solution was silver nitrate, and at all others it was sodium
hydroxide. The data thus obtained indicate: A t constant
pH the measured reaction is first order; the rate is nearly
constant a t 1.55*0.15% per minute in the pH range 3 to
10; the rate for the free acid (pH 1) is 0.024% per minute,
increasing rapidly to 1.75 at pH 3; the rate falls slowly to
1.40% per minute at pH 6 and increases again to 2.00 at
pH 11.5; above pH 11.5 the rate increases exponentially to
5.8% per minute at pH 13. Users of chloroacetic acid who
need to neutralize the acid should always add the alkali
to the acid, not the acid to the alkali. Furthermore, good
stirring is essential.
ANY studies have been made on the hydrolysis of chloro-
acetic acid and its sodium salt, starting with Buchanan
(1, 6 ) in 1871 and continuing through the extensive series of
studies of Dawson ( 9 , 4 , 6 )and co-workers in 1943.
Almost from the first there has been a suggestion that the pH
of the reaction medium htEs an effect on the rate of halogen elimi-
nation. Buchanan (8) showed that the reaction was much faster
Kith excess alkali in the reaction system. Kastle and Keiser
(8) and Laseen and Eichloff (9) showed the effect of the reactant
concentrations as well as the amount and concentration of excess
alkali on the rate of halogen removal. Dawson and Pycock also
indicate the effect of pH in their work.on hydrolysis of mixtures
of chloroacetic acid and its sodium salt. They found a maiiimum
velocity of chlorine removal in solutions containing approxi-
mately 0.7 M sodium chloroacetate and 0.3 M chloroacetic acid.
The later work of Dawson, Pycock, and Smith indicates also that
the hydroxyl ion plays an important role in the halogen removal,
especially if its concentration is sufficiently high.
With these numerous references in the literature to the effect
of pH on the rate of halogen removal, it is surprising that no
systematic study has been made of the relation of pH t o hydroly-
siE rate. Likewise, no case hag been found where an attempt
wae made t o neutralize the acid formed during the reaction.
Csually, the effect of this acidification has been minimized by
determining the rate from only the fist portion of the hydrolysis.
Because of the importance of chloroacetic acid, and especially
its sodium salt, in chemical synthesis, the present work was un-
dertaken t o obtain more explicit data on the rate of hydrolysis
as affected by changes in the acidity or alkalinity of the system.
Furthermore, it was desirable to have this data a t approximately
the concentrations which would be used commercially.
APPARATUS AND PROCEDURE
Since it was desired to carry out the velocity studies at con-
stant pH, continual neutralization of the hydrochloric acid
formed in the reaction was required. If this neutralization is
done with sufficient care, the reaction can be followed by noting
the volume of sodium hydroxide solution added a t various times.
544
Temperature control was achieved simply by operating under
reflux. The concentration of the reacting solutions selected w'as
such that their boiling points were about 104" C.; hence t h e
temperature of the refluxing solution did not change more than
0.5' C. during a run. The error thus introduced is not large.
I n the runs made with the free acid, it proved impractical t o
maintain the pH by the addition of alkali, and so the procedure
was modified and the chlorides precipitated continuously by the
addition of silver nitrate solution.
The reactions were carried out in a one-liter, multinecked,
round-bottom flask fitted with a stirrer, reflux condenser, ther-
mometer, reagent inlet from the solenoid valve, and two elec-
trodes for the cell system. Heat was supplied by an electrical
heater.
The actual control of pH during the reactions wtis automatic.
The antimony-saturated calomel cell system used for pH meas-.
urement was connected to a Leeds & Sorthrup recording and
controlling potentiometer. This, in turn, opened or closed a
small glass solenoid valve to add sodium hydroxide as requirtd
to maintain the set pH value. In the unbuffered range (pH 6 or
above) this system gave control xithin * 0.2 pH unit; in the
buffered range the control as even closer. For the run a t pH
1 (free acid) the antimony electrode was replaced with a silver
electrode and silver nitrate added automatically t o precipitate
the chloride formed in the reaction.
The behavior of the antimony electrode was checked on a
number of runs a t various pH values by withdrawing a sample
from the reaction flask at the end of a run, cooling it rapidly t o
room temperahre, and immediately measuring the pH with a
glass electrode. The p1-I values agreed within 0.2 unit.
For the runs a t pH 3 and above, 95 grams of commercial
chloroacetic acid (freezing point 61" C.) were dissolved in 200
ml. of water and placed in the reaction flask. This WLIS warmed
to 50-55' C., and then 50y0 sodium hydroxide was added to
neutralize the acid. . Thetheat of neutralization was sufficient t o
heat the reaction mixture to reflux. A slight excess of sodium
hydroxide was usually added, since the normal hydrolysis rap-
idly brought the solution back to the desired pH. Khen this
point was reached, the controller was turned on, timing of the
run was started, and the volumes of sodium hydroxide required
to maintain the p H were recorded. For the runs at pH 3, 4,
and 5, only sufficient sodium hydroxide was added to give the
deeired pH. For the run on the free acid (pH l),the neutraliza-
tion with sodium hydroxide was omitted, the reaction heated
directly to reflux, and the controller turned on. Timing was
started after the chlorides, formed during t'he heating period,
had been precipitated.
CALCULATIONS
The method of Guggenheim (Y), which eliminates the use of
the uncertain infinity reading, was used t o calculate the specific
velocity coefficients for a first-order reaction. Readings wcre
therefore made at 5-minute intervals over a period of 2 hours.
The constant int,erval between pairs of readings was usually 1
hour. I n a fev cases, noted in Table I, an infinity reading was
made, and this value was taken L\S the second reading of the pair.
May, 1946 INDUSTRIAL AND ENGINEERING CHEMISTRY 545

These differences over a one-hour period are recorded in Table I. of the reaction mixture with the.standard alkali and by changes in
These data were then plotted on semilogarithmic paper, and the total ionic concentrations. These are valid criticisms of the
best straight line was drawn through the points, giving all equal method, but the errbrs thus introduced are probably not large.
weight. I n a few cases there was,a marked deviation toward the EXPERIMENTAL.Those runs made in the buffered range
end of the run, and these points were therefore not considered in (pH 3 to 6) were subject t o somewhat larger experimental error
drawing the best straight line. than the others. This was due t o the fact that the volume of
The first-order specific velocity constants were then calculated sodium hydroxide which had to be added to cause response in
from the slope of the line by reading off the half time and using the controller was several times larger than that required outside
the relation, the buffcred range. Thus, while in the buffered range the actual
pH control was better, the experimental error was larger. The
k = ( l / t ) In l00/50 = 0.693/t value of pH 1 for the hydrolysis of the free acid is an apprordma-
where t = half time
tion. Actual measurement at 25" C., using a glass electrode,
Because of t h e gave a value of 1.3 a t the beginning of the run and 0.6 a t the end.
slowness of the re- CALCULATION. Dawson and co-workers showed that the re-
action at pH 1, the moval of chlorine from chloroacetic acid is not a monomolecular
data were handled reaction, and although it is influenced by a number of factors, it
somewhat differ- frequently behaves like one of the first order. Therefore, for
ently. Infinity ti- the sake of uniformity, all the specific velocity coefficients re-
trations were cal- ported here were calculated on the assumption that the reaction
tulated from solu- measured was first order. I n defense of this choice, it might be
tion concentrations, pointed out that, for most of the runs semilogarithmic plots of
and the logarithms concentration against time gave straight lines, as would be ex-
of the concentra- pected for first-order reactions.
tions in terms of
milliliters of silver DISCUSSION O F RESULT6
nitrate were plotted
against time. This The results here presented are generally in conformity with
was done because the data already in the literature. The increased speed of hy-
the reaction waa drolysis at high pH values is again shown. The observation of
followed for such Dawson afid Pycock of a maximum rate of chlorine removal from
a short time t h a t a mipture of 70 mole % sodium chloroacetate and 30 mole %
plotting on semi- chloroacetic acid is confirmed by the maximum a t pH 3 in Figure
PH logarithmic paper 1. The amount'of sodium hydroxide required t o neutralize the
Figure 1. Effect of pH on Hydroly- was not sufficiently chloroacetic acid to pH 3 indicates that about two thirds of the
sis Rate of Chloroacetic Acid at accurate. The acid was neutralized a t this pH.
104' C. and 3 N Concentration The effect of the pH of the reaction medium on the rate of
velocity coefficient
was then calculated '
halogen removal as shown here may also account for some of the
from the slope of the line as above, and the*half time was rather anomalous results reported in the literature. Drushel
and Simpson did not find a constant first-order k for the hydroly-
calculated.
Table I presents the data for the various runs. Concentration sis of sodium chloroacetate. This is no doubt due to the fact
that, as hydrolysis proceeds, the solution becomes more acid.
is given in terms of differences in the pairs of readings for the
various times. Values in the laat column for specific reaction Senter (IO) gave the relative rates of hydrolysis of acetic acid,
constant k (the fraction hydrolyeed per minute) are plotted as a the sodium salt, and the sodium salt with one equivalent sodium
hydroxide as 1:3.6:36. These ratios are not confirmed in this
function of pH in Figure 1.
work, and the difference may be in the different concentrations
POSSIBLE ERRORS used. He found little change in k with concentration for the free
acid, but a considerable increase when the concentration of the
THEMETHOD. The method used here may be open t o criti- sodium salt was increased. The relative rates found here are:
cism, since Drushel and Simpson (6) found some discrepancy in '
the silver and alkali titrations of reaction mixtures such as those 1 7 13
used here. Furthermore, some error is introduced by the dilution
fRelative
H rate 0.00024
1
0.0146
62
0.058
247

TABLE
I. EFFECTOF pH ON HYDROLYSIS
RATEOF CHLOROACETIC
ACID AT 104' c. AND 3 N CONCENTRATION
pH 0 min. 5 min. 10 min. 15 min.
Concentration
20 min. 25 min. 30 min. 35 min. 40 min. 45 min. 50 min. 55 min. 60 min.
. Half
Time 100 k
13 79.2
190
60.2
161
45.2
136
33.2
114
23.2
95
l9,2
80
11.2
65
...
51
4.2
40
1.9
31
1.2
23
.. .. 11.8 5.8
12.5 18 14 19.1 3.65a
11.5 52.5 48.5 44.0 39.8 36.3 33.0 29.5 26.7 24.5 22.0 19.8 18.0 16.2 35.0 1.98
10 65.0 60.0 ' 55.0 51.0 46.5 42.8 39.0 36.0 33.0 30.5 28.5 25.5 23.5 41.5 1.67
8 110.5 103.3 96.8 89.8 83.8 77.8 71.4 66.0 61.0 66.1 51.8 48.0 44.7 45 5 1.52
185.0 175.0 164.5 154.0 144.0 133.0 125.0 116.5 108.5 101.0 94.0 87.5 82.0 50.0 1.3ga
7 81.8 70.0 65.5 60.5 56.0 51.5 47.8 44.0 41.0 38.2 35.0 31.4 45.0 1.54
111.0 l04:5 98.3 91.3 85.8 79.8 74.2 68.0 64.0 60.5 50.2 51.7 48.0 49.5 1.40
106.0 100.0 93.0 86.5 81.0 76.0 70.3 65.3 60.0 56.0 52.0 49.2 44.5 49.0 1.41
6 98.0 91.5 86.0 80.5 75.0 70.3 65.0 61.0 56.0 52.5 49.2 46.3 50.0 1.39
171.5 161.5 151.5 141.5 131.5 122.5 114.0 105.5 98.5 91.5 86.0 78.5 73:5 48.5 1.43'"
5 89.0 82.0 76.0 73.0 69.0 62.7 58.0 55.0 53.0 50.0 46.0 41.0 40.5 49.5 1.40
4 69.8 64.5 60.5 57.0 53.0 48.5 44.5 41.0 37.5 35.0 31.5 29.0 26.0 43.0 1.61
3 47.5 43.5 39.5 36.5 33.0 30.5 27.8 25.5 23.2 21.0 19.5 18.0 16.5 39.0 1.77
60.0 54.8 49.8 45.7 42.0 38.5 35.7 32.9 30.7 28.8 26.6 25.0 23.5 41.0 1.69
0 min. 30 min. 40 min. 90 min. 150 min. 180 min. 210 min. 240 min. 270 min. 300 min. 330min. 360min. 390min.

(')
279
484
...
480
276
...
273
472
.. .
466
267
.. .
...
459
263.5
... . ..
452
260
...
...
445
257
... ii8
3010 0.0235
2890 0.024a
a Infinity reading used a6 second reading of pair.
546 INDUSTRIAL AND ENGINEERING CHEMISTRY
These data also indicatc why certain practices in the handling
of chloroacetic acid have been beneficial. For example, in many
preparations in the literature, the use of sodium carbonate has
been specified for the neutralization of chloroacetic acid. This
has served t o prevent excessively. high- alkalinit,ies during- thr
neutralizat,ion j n d thus reduced the amount of hydrolysis.
The same result' can be achieved by careful neutralization with
sodium hydroxide with good stirring and cooling. It further
indicates the inadvisability of adding the acid to the jlkali in
neutralization.
As already mentioned, plots of log conccntrution against time
indicated that most of the runs were of the first order. The es-
ception was the run a t pH 12.5; this plot sh0n-s a deviation from
a straight line, in the dircction of a more rapid reaction. Thi:
Cyclization
-
of Pseudoionone
by Acidic Reagents
E. EARL ROYALS
Georgia School of Technology, Atlanta, G u .
A study has been made of the cyclization of pseudoionone
by various acidic reagents to yield mixtures of a- and j3-
ionones. Particular attention has been given to the iu-
fluence of the cyclizing agent on the composition of the
resulting ionone mixture. The mechanism of the reaction
is discussed, and suitable preparative procedures for CY- and
6-ionone are recommended.
SECDOIOKO?;E (I) under the influence of acidic reagents is
converted into a mixture of a-iononc (11)and Pionone (111),
the artificial violet odor of commerce (3, 10, 11). Because of the
great technical irnportancc of the ionones, a number of methods
have been developed for the cyclization of pseudoionone. These
are dcsrribed mainly in the patent literature (4, 6, 7 ) .
CI-I,
v successively 17-ithm ~ t e r 5yc
p, I
--CEI=< II-t.=O
1
I1 I11
Although the relative proportions of CL- and 8-iononcs obtained
on cyclization of pseudoionone are dependent on the cyclizing
:tgc:nt used, little attention has been given to this phase of the
problem beyond the general statements that concentrated sul-
furic acid gives mainly 3-ionone (Q), n-hereas phosphoric, formic
(Q), acetic, and benzoic acids (8) produce mainly the alpha isomer.
Hibbert and Cannon develdped laboratory procedures for the
preparation of an ionone said to be essentially the alpha isomcr
(4). Ito studied in some detail the cyclization of pscudoiononc
by sulfuric and phosphoric acids, and showed that the proportion
of isomeric ionones obtained is dependent on the concentration
of the cyclizing acid ( 5 ) . The present invest'igation was under-
taken to ex%end existing knowledge as to the effect of the cycliz-
ing agent on the relative proportions of a-and p-ionones obtaincd
VoI 38, No. 5
deviation started lvhen about 65% had reacted and may have
been due to a slight increase in pH.
LITERATURE CITED
(1) Buchanan, Ber., 4 , 340 (18i1).
(2j [hid., 4 1 sG3 (1871).
(3) D a w o n and Pycock, J . Chtnz. Soc., 1934, i 7 8 ,
(4) I b i d , , 1936, 153,
( 5 ) D ~ \Pycock, ~ ~ alld~ Smith,
~ , hid., 1943, 517.
(0) Drushel and Simpsoii, J . A m . C'hem. Soc., 39, 2456 (L017).
( 7 ) Guggenheim, Phil. .Vag.. [ i ]2 , 538 (1920).
( 8 ) Kastle and Keiser, A m . C'hem. J . , 15, 471 (1393).
!9) Lassen and Eirhloff, 342, (1905!.
(10) senter, J . them. yoc.,91, 460 (190:).
. .
pREsErTzD on the program of the Division of Physical and Inorganic Chem-
istry of t h e 1945 I\ieeting-in-Print, AMERICAY CHF,XICAI,SOCIETY.
'
on cyclizing pseudoionone, to throw light on the meciianism of
the cyclization reaction, and t o dcvelop practical method. for tho
production of CY- and 3-iononcs.
CYCLIZATION PROCEDURES
Citral was obi ained from Fritzsche Brothers, Inc., and \\-as uwd
v-ithout further purification. The acetone and vnrious ncidin
reagents were of C.P. gradc. Phosphoric acid of strength grcatvr
than 85yGwas preparcd by adding the cnlciilatcd qi:antity o f
phosphorus pentoxide t o the ordiiiary sirupy wid, Psoudoionoiic..
n-as prepared according t o the following procerliire ( 1 1 ) : A niis-
ture of 200 grams (1.31 moles) of citral, 200 grams (3.44 moles) of
acetone, and 200 cc. of a saturated solution of barium liydrosidn
~ m vigorously
s stirred for 3-4 days at room temperature (about
28" C , ) . The organic materid was taken up in ether and waslied
, tartaric acid solation, and again \\-it11
n-zter. The ethcr solution \vas dried over sodium sulfate, thc
ether n-\.asremoved by distillation, and the residue w a ~distilled
under reduced pressure. The fraction boiling arouiid 150-165 C'.
(15 nini.) was collected. This material wai fvcc:d of citral a i d
condensation products of acetone by steam distilling until about,
one liter of distillate 11-a~collected. The residue was c!ricd over
nnhj-drous sodium sulfatc and fractionated unticr reduced pres-
sure through an 8-inch column packed n-ith glacis hcli
terrially heated. The portion boiling at 144-149' C. (10-11 inin.)
and showing ti2: of 1.5230-1.5280 (succesbive fractions) K:IS
taken for use as pseudoionone. The literature reports f o r preudo-
ionone prepared by this method (ff), 143-143" C. (12 nirn.) and
1.5275, respectively.
The cyclizations of pseudoionone (Table 1) were carried out,
in the following general manner: The cyclizing agent as placed
in a 200-cc. three-necked flask fitted n-ith a mechanical stirrer, a
dropping funnel, and a thermometer reaching into the reaction
mixture. The flask wi,s cooled in an ice bath, and the cyclizing
agent was vigorously stirred xhile 20 grams of pseudoionone were
added dropvise during 15-30 minutes; the rate of addition was
adjusted so that the temperature of the reaction mixture did n o t
csceed 10-15" C. Khen the pseudoionone had all been added,
the cooling bath was removcd, and stirring was continued for a
period considered sufficient t o permit complete reaction. T h e
reaction mixture was poured into 500 cc. of ice watcr and cs-