Nov.

, 1949 POLAROGRAPHIC KINETICSTUDIES

UREA-FORMALDEHYDE 3731

[CONTRIBUTION
FROM THE CHEMISTRY
DEPARTMENT,
UNIVERSITY
OF DELAWARE
]

Polarographic Urea-Formaldehyde Kinetic Studies

BY GEORGEA. CROWE,J R . , ~ AND CECILC. LYNCH

I n a previous paper2 we have shown polaro- and formaldehyde to form monomethylolurea are
graphically the reaction between formaldehyde given in Table I . The equilibrium constant ap-
and urea to be reversible a t 25 in 0.05 N lithium pears to be constant within experimental error
hydroxide. It seemed desirable to study the ef- (*5% of the value determined) for changes of
fects of change in temperature and PH on this re- temperature and PH over the ranges tested.
action. Such a study is presented here.
TABLE I
Smythe3measured the urea-formaldehyde reac-
tion rate in neutral solution between 30 and 60 RATES FOR THE REACTIONNH2CONH2 HCHO F! +
and found that the reaction was bimolecular. PU2CONHCHgOH, AND AVERAGE POLAROGRAPHIC
(Crowe and Lynch2showed that the reaction was CURRENT OF FORMALDEHYDE AT VARIOUS PH

reversible in 0.05 N lithium hydroxide a t 25, and VALUESAND FOR VARIOUSTEMPERATURES

found that the reverse reaction was monomolecu- K Av. pol.
From current of
lar.) J a h ~ d a , ~Bieber
J and T r i i m ~ l e rand
~ , ~Ves- .From equi- 0.00354 M
reac- lib- formalde-
ely and BrdickaJ observed that the electroreduc- Temp., tion rium hyde,
OC. pH kf (sec.-) kr (sec-1) rates data mma.
tion of formaldehyde a t the dropping mercury
25 12.7 2.97 X 10-2 1.45 X 10-3 20 26 12.0
electrode was very low a t 25 in neutral solution. 25 11.2 3.56 X 10-3 6.04 X 10-5 59 35 4.8
As the pH or temperature was increased, the rate 25 10.1 6.10 X 10-4 1.75 X 10-5 35 55 1.20
of reduction was greatly increased. It was postu- 25 8.7 2.14 X 10-4 1 . 3 8 X 10-5 16 60 0.34
lated6s7nsthat formaldehyde was normally hy- 15 12.7 1.71 X 10-2 18 5.97
20 12.7 2.67 x 10-2 14 8.75
drated, and that the amount of electroreduction 25 12.7 3.36 x 10-2 30 12.0
of formaldehyde was a measure of its dehydration 25 1 2 . 7 2.97 x 10-3 1 . 4 5 x 10-8 20 26 12.0
rate; maximum dehydration was found to occur 30 1 2 . 7 9.80 x 10-2 21 17.8
above 80, or a t PH 13.14 a t 25.4p8 38 1 2 . 7 0.129 20 24.9
40 1 2 . 7 0.158 21 26.2
The kinetic study described in this paper indi-
cates that both dehydration of formaldehyde The average polarographic reduction current
and the assumption of the formation of an anion for formaldehyde with varying temperature and
of urea are necessary to account for the increase PH is also given in Table I. As can be seen from
of urea-formaldehyde reaction rate with increase the table, for a given decrease in polarographic
of PH. Increase of temperature probably affects current, lowering the pH from 12.7 slows down the
the rate of dehydration of formaldehyde without urea-formaldehyde reaction rate more than low-
markedly changing the rate of formation of this ering the temperature. The amount of electrore-
anion form of urea. duction of formaldehyde to methanol occurring a t
Experimental the dropping mercury electrode was about 0.2%
of the formaldehyde in solution per hour, and oc-
The apparatus, chemicals and general technique curred only when -1.65 volts or more was ap-
were as described previously.2 The supporting plied to the electrodes. Therefore the amount of
electrolytes consisted of 0.05 N lithium hydroxide reduction of formaldehyde was negligible in com-
(PH 12.7), 0.1 M sodium carbonate (pH 11.2), parison to the amount involved in reaction with
0.1 M sodium bicarbonate (pH 8.7) and a buffer urea.
mixture of 0.05 M boric acid, 0.05 M lithium chlo- The change of the polarographic wave height
ride and 0.045 J!l lithium hydroxide (PH 10.1). of formaldehyde with temperature is shown for
All reagents were C. P.Baker Analyzed except the PH 8.7 and pH 12.7 in Fig. 1. The log of formal-
lithium hydroxide which was hferck and Com- dehyde wave height is plotted vs. the reciprocal of
pany lithium hydrate. The solutions were made the absolute temperature, as in an equation de-
up to twice the concentrations given above, and rived from the Arrhenius equation
diluted with an equal volume of urea, formalde-
hyde or monomethylolurea solution to be tested.
Reaction rates for the reversible reaction of urea
(1) Present address: Hercules Powder Company, Hercules Ex- where i l and iz are the formaldehyde wave heights
periment Station, Wilmington, Delaware. for absolute temperatures T I and T,, and A E a a is
(2) Crowe and Lynch, THISJOURNAL, 70, 3795 (1948). the apparent energy of activation for the reduction
(3) Smythe, J . Phys. Colloid Chem., 61, 369 (1947).
(4) Jahoda, Coll. Czcchoslov. Chem. Commun.,7 , 415 (l(135). of formaldehyde a t the dropping mercury elec-
(5) Kolthoff and Lingane, Polarography, Interscieiice Pub- trode. The lower, steeper slopes are limited by
lishers, Inc., New York, N. Y., 1941, p. 353. the rate of dehydration of formaldehyde; the up-
(6) Bieher and Trumpler, Helv. Chim. Acta, 80, 706 (1947). per, less steep slope is dependent only on the
(7) Wawzonek, Anal. Chem., 21, 61 (1949).
(8) Vesely and Brdicka, Coll. Czcchoslozk Chcm. Commun.,12, 313
change of viscosity of the solution and the change
(1947). of mercury mass and drop time with temperature.
3733 GEORGEA. CROWE,JR., AND CECILC. LYNCH Vol. 71

The sum of the effects of change of viscosity, mer-
cury mass and drop time would give an apparent
activation energy of about 4000 cal. per mole, as
compared to the upper slope of 3560 cal. per mole.
This indicates that only free formaldehyde is
present above 55' a t pH 12.7, and above 81' a t
pH 8.7. This latter value is in agreement with
the value of 80' found by Y a h ~ d a . ~
2.0
1.6
mole. Calculated by the Arrhenius equation from
Table I, the effective energy of activation (A&)
a t PH 12.7 was 15,900 cal./rnole, which is in agree-
ment with Smythe within the limits of experi-
mental error.
Equations were developed to relate the urea-
formaldehyde reaction rate and the polarographic
wave height of formaldehyde for changes of pH
and temperature.
From the Arrhenius equation a n d equation (l),
a relationship was found between urea-formalde-
hyde forward reaction rates (kl and k2) a t two
temperatures and polarographic wave heights of
formaldehyde (il and &) a t the same two tempera-
tures, and a t a constant pH.

where AEa was 15,900 cal./mole and AEaa was

x 1.2 10,000 cal./mole for pH 12.7 over the range of 15
9
EI
to 40'. Using these values, kr was calculated
.e
*.a
v
from formaldehyde wave height, and a t pH 12.7.
.C -kf (pH 12.7)--
1, o c . Calcd. Found
3 0.8
15 0.015 0.017
20 ,028 .027
25 .045 .034
30 .085 ,098
38 .14 .I3
0.4 40 .16 .I6
For changes of pH a t a given temperature, the
urea-formaldehyde forward reaction rate was
calculated from the polarographic wave height of
0 formaldehyde by the equation
kf = i B / A ( A - i) (3)
(I/T) x 103.
where kr was the forward reaction rate, i the form-
Fig. 1.-Formaldehyde dehydration with temperature.
aldehyde wave height, and A and B constants.
Equation (3) was deduced from analogy to the
The extent of dehydration of formaldehyde was second-order equation kt = x/a(a - x ) and consid-
estimated as the ratio of the actual formaldehyde eration of the relative amount of formaldehyde
wave height to the total dehydrated wave height available for either electroreduction or reaction
from Fig. 1. At 25' the formaldehyde was found with urea. From the values in Table I, a t 25'
t o be about 4170 dehydrated a t PH 12.7, and about withA = 15and B = 0.12
1.2% dehydrated a t pH 8.7.
The forward urea-formaldehyde reaction rates ...
flH Calcd. Found
were calculated with corrected formaldehyde val- 12.7 0.032 0.030
ues, and the same reaction rates were obtained as 11.2 .0038 .0036
before, within experimental error. Since the ex- 10.1 .00070 .00061
tent of the reaction was small in evaluation of ini- 8.7 .om19 .00021
tial slopes, the values of the reaction rate constants
obtained and the equilibrium constant should not Reverse reaction rates k, can be calculated from
differ significantly from the values given previ- the forward reaction rate kr and the equilibrium
0us1y.~ The results showed this to be true. It constant K , where K = kr/k,.
appeared impossible to calculate the observed ef- The mechanism and reaction rate of the urea-
fect of change in reaction rate with pH from the formaldehyde reaction to form monomethylolurea
data included here, since not only does the con- appears t o involve the dehydration of formalde-
centration of formaldehyde in the reaction vary hyde (the hydrated form, H2C(OH)z, does not
with pH, but also the concentration of the anion of react) and also the formation of an anion of urea.

-
urea appears to vary with pH. This anion is assumed to be a resonance structure
For the change of urea-formaldehyde reaction 0 0-
rate with temperature in neutral solution, Smythea
found the energy of activation to be 14,700 calm/ Ngd-NH- NHr-dNH
Nov., 1949 OF QUINOLINE
SPECTRA DERIVATIVES
With changing PH, both urea and formaldehyde
activation equilibria are shifted ; whereas with
changing temperature, the main change appears t o
be in the rate of dehydration of the formaldehyde.
Thus for a given decrease of formaldehyde reduc-
tion current, the urea-formaldehyde reaction rate
is affected more by changing the PH than chang-
ing the temperature, indicating that the amount of
the anion of urea is affected by PH change more
than by temperature change.
Summary
The effects of varying pH and temperature on
the reversible reaction HCHO +
NH2 CONHz $
[CONTRIBUTION FROM THE DEPARTMENTO F RESEARCH I N CHEMICAL PHYSICS AND
P U R E CHEMISTRY O F MELLONINSTITUTE]
Ultraviolet and Infrared Spectra of Quinoline Derivatives : 2- and 4-Thiols
BY R. B. HANNAN, AND ALICE G. RENFREW
JR., J. H. LIEBLICH
This investigation was undertaken in an
attempt to determine the type of linkage between
the sulfur atom and the quinoline nucleus in the
substituted 2- and 4-quinolinethiols. Two struc-
tures are possible for these compounds: a thiol
structure (A) and a thione structure (B).
S quinolinethiol
I1
A B
(These may be in tautomeric equilibrium.)
Ewing and Steck have attacked the same prob-
lem in the hydroxyquinolines by the use of ultra-
violet spectra, and i t was hoped that their method
would be successful with the sulfur analogs.
The infrared spectra of these sulfur compounds
have also been studied. Unfortunately neither
approach has provided an answer to the problem.
Since the data may be of some utility, the results
will be described briefly.
Ultraviolet and infrared absorption spectra of
the following compounds are presented.
SH
I I1 I11
2-Xaphtha- 7-Methyl-2-quino- 7-Methyl-4-
lenethiol linethiol quinolinethiol
( 1 ) Ewing aud Sterk, THISJ O U R N A L , 68, 2181 (1946); Steck,
Ewing and Nachod, Abstracts, Washington hleeting, A. C. S., Sept.
1948. page 12L.
3733
NHzCONHCHzOH have been studieq, using the
polarograph to measure formaldehyde concen-
tration. Equations are presented to relate the
urea-formaldehyde reaction rate to the polaro-
graphic current of formaldehyde for changes of PH
or temperature.
The urea-formaldehyde reaction rate appears to
be dependent both upon the rate of dehydration of
formaldehyde and rate of anion formation of urea.
A method is given for estimating the fraction of
dehydrated formaldehyde a t various temperatures
and PH ,values, based on polarographic wave
heights of formaldehyde.
XEWARK,
DELAWARE MARCH18, 1949
RECEIVED
THE DEPARTMENT
O F RESEARCH
IN
IV V
7-Chloro-4-rnethyl-2- 7-Chloro-4-methyl-2-n-
butylthioquinoline
VI
7-Chloro-4-n-butylthio-
2-methylquinoline
Few data for comparison are available in the
literature. Morton and Stubbs2 have reported
the ultraviolet absorption spectra of 4-methyl-2-
quinolinethiol and its ethers in neutral alcoholic
solution only. Clinton and Suter3 give spectro-
photometric measurements for two 4-dialkyl-
aminoalkyl sulfides of 7-chloroquinoline, The
curve for 7-chloro-4-quinolylmercaptoacetic acid
is given by S ~ r r e y . ~
Experimental
The preparation and properties of the quino-
linethiols (11, I11 and IV) have been reported by
RenfrewS6 The preparation of the t w o thio-
ethers is described below.
V) .-This
7-Chloro-4-methyl-2-n-butylthioquinoline6(
sulfide was synthesized by the procedure described by
(2) Morton and Stubbs, J . Chcm. Soc., 1321 (1939).
(3) Clinton and Suter, THIS JOURNAL, 70, 491 (1948).
(4) Surrey, ibid., 70, 2190 (1948).
( 5 ) Renfrew, ibid., 68, 1433 (1946).
(6) Mrq. Pauline C. Piatt of the Department of Research in Pure
Chemistry carried out much of the synthetic work.