3106 W. J.

SVIRBELY
AND JAMES F. ROTH Vol. 75
Bond energy
Bond term, kcal Parent compound
I>(h-H) 88 0 Hydrazine
D(-K-S-) 33 7 Hydrazobenzene
F(- X e s - ) -82 7 p -Aminoazobenzene
F(==S-X-) -45 1 Phenylhydrazine
The determination of the stabilization energy of D( ) refers to the dissociation of the bond and
the three nitrogen groups in each of these com- F( ) to the formation of the bond. With the
pounds can be made only after a careful estimation use of these values and equation (5) the heat of
of the contributions of the bond energy terms for formation of diazoaminobenzene is calculated to be
the N-H, N-N and N=N bonds. To do this,
the tnethod of Gilbert and Anderson12was applied
12C(g) + 11H(g) + 3N(gi = Ci2HiiK3(S)
AH293 = -2810 5 kcal (9)
to the compounds The value of 2810.5 kcal. per mole obtained from
H €I these calculations compares favorably with the
D - - X - S - c 3 ) (6) value computed from the observed heat of com-
bustion and justifies the use of Cole and Gilbert’s
H bond energy terms in conjunction with the bond
energy terms of WhelandI4 in the calculation of the
stabilization energy of diazoaminobenzene. How-
ever, the values of Wheland, based in part on the
It is obvious that the energy of formation of calculation of Pauling,l5 were derived by use of a
hydrazobenzene (6) differs from that of diazo- value of 124.3 kcal. per gram atom for the heat of
aminobenzene (7) chiefly by th2 energy of one N-H sublimation of graphite rather than the value
bond, the energy of one -N-N- bond, the energy of 171.7 kcal. per gram atom used in the above cal-
=N-N- bond and the energy of one -N=N- bond. culations. Recalculation on the basis of Wheland’s
The heat of formation of hydrazobenzene from the values gives for equation (9)
gaseous atoms is given by 1”c(g) + 11H(g) -I- 3 x ( g ) = Ci2Hiix3(~)
-2239.0
AH298 = kea1 (10)
12C(g) + 12H(g) + 2X(g) = Cr~Hiz?Jz(s) Using a heat of sublimation for diazoaminobenzene,
A%s = -2804.4 kcal. (8) estimated to be the same as that for hydrazoben-
zene, of 20.0 kcal. per mole one obtains
The values of the bond energy terms taken from
the work of Cole and Gilbert,13 are listed below
12C(g) + 11H(g) + 3 s ( g ) = Ci?HiiNa(g)
____ AH2gb = -2219 0 kcal (11)
with the parent compounds from which they were (14) G W Wheland, “The Theory of Resonance,” Chap 3, J
determined. Wiley and Sons, Inc , New York, N Y , 1944
(12) G. hf. Anderson and J. B. Gilbert, THIS JOURNAL, 64, 281
(15) L Pauling, “The Nature of the Chemical Bond,” 2nd Ed Cor-
ne11 University Press, Ithaca, N Y 1940
(1942).
(13) I,. C. Cole and E. C . Gilbert, ibid.,73,5423 f l 9 3 l ) . L’ETVORLEANS,
LA

[CONTRIBUTIOsFROM THE CHEMISTRY DEPARTMENT,

UNIVERSITY O F MARYLAND]

Carbonyl Reactions. I. The Kinetics of Cyanohydrin Formation in Aqueous Solution1

BY W.J. SVIRBELY
AND JAMES F. R O T H ~
RECEIVED
NOVEMBER
26, 1952

The kinetics of the formations of the cyanohydrins of acetaldehyde, propionaldehyde and acetone have been studied in
dilute aqueous solution a t 25”. Measurements were conducted in acetate buffers under various conditions to ascertain the
influence of ionic strength, pH and buffer composition on the rate constants. The following results were obtained : (1) the
reactions of these carbonyl compounds with HCN follow a second-order equation; ( 2 ) the kinetic salt effect is quite small;
( 3 ) acetaldehyde and propionaldehyde react quantitatively with HCIC’ whereas acetone does not; (4)general catalysis was
not detected for either acetone or acetaldehyde cyanohydrin formation ; (5) in the propionaldehyde reaction a small general
catalytic effect is indicated. It is shown that in the absence of general catalysis there are a number of different mechanisms
which are equally consistent with the experimental rate equation. On the basis of the kinetics alone, with or without general
catalysis, there is no justification for preferring the Lapworth mechanism. A consistent mechanism for carbonyl addition
reactions is proposed.

Introduction slow
The generally accepted mechanism for cyanohy- A0 + CN- + A(CN)O-
fast
drin formation is based on the qualitative studies
of Lapworth. The mechanism is
A(CX)O- + H + -+ A(OH)(CN) (la)

(1) (a) Abstracted from a thesis submitted by James F. Roth t o t h e The above mechanism does not involve catalysis
Graduate School of the University of Maryland in partial fulfillment in the sense that there is either a protolytic reaction
of t h e requirements for the degree of Doctor of Philosophy; (b) pre- between a catalyst and the carbonyl molecule or
sented in part a t the New York City Meeting of the International
Congress of Chemistry, September, 1951.
formation of a n intermediate complex between
(2) National Institutes of Health Research Fellow, 1950-1961. these two entities. This feature of the mechanism
(:I)A. I.apworth, I . C h r i ~ r S. O L . ,83, 9% (1903); 85, 1206 (1904) is surprising when one considers that other carbonyl
July 5, 1953 KINETICSOF CYANOHYDRIN
FORMATION 3107

reactions such as semicarbazone, oxime and phenyl- the acetone was shaken with anhydrous potassium carbon-
hydrazone formation are generally conceded t o pro- ate and then fractionally distilled. The center portion,
boiling a t 55.8' was collected; l t * O ~was 1.3587.
ceed through a n addition compound analogous to a (c).-Eastman Kodak Co. acetaldehyde was dried over
cyanohydrin. Quantitative studies on these lat- calcium chloride and fractionally distilled in an atmo-
ter reactions4ssas well as recent studies on acetalde- sphere of nitrogen. The center portion was collected.
hyde hydrate formation6 have demonstrated a pro- Water.-Boiled, distilled water was used in the prepara-
tion of all solutions.
nounced general catalysis. Apparatus.-The reactions were carried out in a glass
The cyanohydrin reaction is readily subject t o apparatus similar to one used by Baker and Hemming.lo
catalysis. None of the studies conducted by Lap- A slight modification was employed, in that the gas bottle
worth or any of the subsequent investigators7-10 and manometer were eliminated and a gas bubbler filled
with sulfuric acid was inserted between the nitrogen source
of the kinetics of the cyanohydrin reaction provide and the three-way stopcock. The pipet delivered approxi-
data which could be used to examine clearly the mately 9 ml. of reaction mixture with a reproducibility of
possibility of general catalysis. j ~ 0 . 0 1ml.
Therefore, it was deemed advisable to make a The apparatus was immersed in a water-bath maintained
at 24.97 =k 0.02'. The thermometer was calibrated against
quantitative study of cyanohydrin formation, par- a similar one which had been certified by the National Bu-
ticularly with reference to the nature of the cataly- reau of Standards.
sis involved. Accordingly, the kinetics of propion- All watches used in the rate experiments were calibrated
aldehyde, acetaldehyde and acetone cyanohydrin against the National Bureau of Standards time signal.
formation have been studied a t 25' under various Experimental Method
conditions of ionic strength and buffer composi- In preparing a reaction mixture, the following procedure
tion. Since the initial presentation of these re- was used: ( 1 ) when initial concentrations of carbonyl were
sults,lb Yates and Heider" have reported data on desired, a definite amount of the freshly distilled carbonyl
acetaldehyde cyanohydrin formation but their in- was weighed out from a weight pipet into a volumetric
flask which contained some of the solvent medium, either
vestigation provides no information on the nature water or buffer solution. When initial concentrations were
of catalysis. not required, approximate amounts were placed in a volu-
metric flask. The flask in all cases was then filled to the
Materials and Apparatus mark with solvent and immersed in the water-bath; (2) if
Potassium Thiocyanate.-J. T. Baker C.P. potassium a higher ionic strength was required, a weighed sample of
thiocyanate was purified by a procedure in the literature.'* potassium nitrate was placed in the volumetric flask prior
Silver Nitrate.-J. T. Baker C.P. silver nitrate was dried to introduction of the solvent; (3) fifty ml. of the stock hy-
in an oven a t 120". drogen cyanide solution was pipetted into the reaction flask
Standard Solutions.-Solutions of potassium thiocyanate which was immersed in the water-bath after flushing with
and silver nitrate were prepared from the above reagents. nitrogen. When initial concentrations of hydrogen cyanide
The silver nitrate solution was standardized against the po- were required, several samples of the stock solution were
tassium thiocyanate. analyzed prior to use in each experiment; (4) after the hy-
Hydrogen Cyanide .-Liquid hydrogen cyanide was pre- drogen cyanide and carbonyl solutions had come to tem-
pared according to a method described in "Organic Synthe- perature equilibrium, 50 ml. of the carbonyl solution was
S ~ S . ' ' ~A~ solution, approximately 0.2 N in hydrogen cy- pipetted into the reaction flask which was shaken imme-
anide, was immediately prepared from the liquid hydrogen diately to ensure mixing; (5) samples of the reaction mix-
cyanide. The absence of substances capable of forming ture were removed a t suitable time intervals by the pipet
silver precipitates (other than cyanide) in the hydrogen in the apparatus. The samples were forced into the pipet
cyanide solution was shown experimentally. by means of a current of nitrogen. Each sample was then
Acetate Buffers.-The acetate buffers were prepared by delivered into a flask containing 25 ml. of 0.1 N silver nitrate
mixing the appropriate quantities of standard sodium hy- and 6 ml. of 6 N nitric acid. It has been shown by Ultee14
droxide and acetic acid solutions. The sodium hydroxide that cyanohydrins do not give a silver cyanide precipitate
solution was prepared from carbonate-free sodium hydrox- in acidified silver nitrate. Furthermore, the reaction is
ide and was standardized against a Kational Bureau of stopped in acidified silver nitrate since strong acid arrests
Standards standard sample of potassium acid phthalate. the further formation of cyanohydrin; (6) the unreacted
The acetic acid solution was standardized against the sodium cyanide formed a precipitate with silver nitrate. The mix-
hydroxide solution. The acetic acid content of the buffer ture was filtered and the residue thoroughly washeti with
was determined by titration with the standard sodium hy- several portions of water. The excess silver nitrate in the
droxide solution. filtrate was determined by titration with 0.1 N potassium
Potassium Nitrate .-Eimer and Amend potassium ni- thiocyanate using 2 ml. of saturated ferric alum solution as
trate was dried in an oven a t 120" and used as the inert elec- an indicator; (7) the reaction was allowed to reach equilib-
trolyte. rium and the equilibrium concentration of hydrogen cyanide
Carbonyl Compounds. (a).-Matheson Co., propion- was determined.
aldehyde was dried over calcium chloride and fractionally Owing to the volatility of hydrogen cyanide, experiments
distilled in an atmosphere of nitrogen. The center portion were performed to determine whether any significant losses
boiling a t 47.4' was collected; n z owas
~ 1.3632. of hydrogen cyanide from the reaction vessel occurred in the
(b).-U. S. Industrial acetone was refluxed over potas- sampling process during the course of a run. Analysis of
sium permanganate for about 10 hours, and then allowed to several samples from a typical hydrogen cyanide solution
stand over the permanganate for a day. After filtration, yielded titration values reproducible to iz0.03 ml.
The rate of reaction is extremely sensitive to changes in
(4) J. B. Conant and P. D . Bartlett, THISJOURNAL, 64, 2881 (1932). pH and even a small amount of oxidation of aldehyde alters
( 5 ) G. H. Stempel and G . S. Schaffel, ibid., 66, 1158 (1944). the pH sufficiently to affect the rate. Therefore, freshly
(6) R. P. Bell and B. de B. Darwent, T r a n s . Faraday S O C . ,46, 34' distilled aldehyde was used for each run.
(1950). The effect of the addition of hydrogen cyanide on the p H
(7) E. Moller, Doctoral Dissertation, Hamburg University, 1929. of a buffer was checked experimentally. The pH of a buffer
(8) A. Albers and K . Hamann, Biochem. Z., 266, 44 (1932). consisting of 0.0341 N acetic acid and 0.0342 N sodium ace-
(9) T. D . Stewart and B. J. Fontana, THISJOURNAL, 62, 3281 tate was measured at 25' with a Coleman PH electrometer and
(1940). found to be 4.62. This value is in agreement with the value
(10) J. W. Baker and M. L. Hemming, J . Chem. SOC., 161, 191 obtainable from interpolation tables.15 The pH of a similar
(1942). solution containing 0.1 N hydrogen cyanide was also 4.62.
(11) W. F . Yates and R . L. Heider. THISJOURNAL, 74, 4153 (1952).
(12) I. M. Kolthoff and J. J. Lingane, i b i d . , 67, 2126 (1935). (14) A. J. Ultee, Rec. trau. chim., 28, 248 (1909).
(13) "Organic Syntheses," Co!!. Vo!. I, John Wiley and Sons, IRC., (16) E. J. Cohn, F. F. Heyroth and M. F. Menkin, THISJOURNAL,
New York, N. Y . , 1943. 60, 696 (1928).
3108 W. J. SVIRBELY
AND JAMES F. ROTH VOl. 75

Discussion CHOA~.If, in a series of buffers, the concentration

The rate equations pertinent to the experimental of base (;.e., OAc-) and acid are varied a t constant
conditions explored may be derived by assuming, ionic strength and a t a fixed ratio, then constancy
for illustrative purposes only, the validity of the of the rate constant would not permit us to distin-
Lapworth mechanism. Using the Bronsted method guish between any of the mechanisms listed. How-
and realizing that the primary salt effect for a reac- ever, if the rate would vary with buffer concentra-
tion between a molecule and a n ion is small, the tion a t a fixed ratio, then general catalysis would
rate of cyanohydrin formation is exist16 and mechanism (la) could be rejected be-
cause of incompatibility with the kinetics.
dxldt = kOCAOCCN- (2)
in which A 0 designates the carbonyl compound. If Experimental Data and Results
the reaction is run in acetate buffers, then by use of All velocity data were collected in a PH range of
the equations about 4.0 to 5.0. From the dissociation constant
of hydrogen cyanide,” 4.0 X 10-lo, calculations
show that in this p H range over 99.9% of the cya-
nide exists as undissociated hydrogen cyanide.
Thus the analytically determined cyanide was
taken to represent the species HCN.
Evidence that the reactions of propionaldehyde
and acetaldehyde with hydrogen cyanide go virtu-
equation ( 2 ) becomes ally to completion was obtained as follows: (1)
when the aldehyde concentration was initially in ex-
cess of hydrogen cyanide, then a t equilibrium the
If experiments are run at constant ionic strength and addition of a sample of reaction mixture to acidified
in a buffer where the ratio COAC-ICHOAC is con- silver nitrate produced no precipitate; (2) when
stunt, then equation (6) becomes the resulting mixture was titrated with potassium
thiocyanate, the titration value corresponded ex-
dx/dt = k‘CAOCHCN (7) actly to all of the silver nitrate used.
The experimentally determined rate constant Data were obtained to show that the amount of
relative to the concentrations of the species A 0 and hydrogen cyanide (AHCN) which disappeared in a
HCN will be k’, and k’ can be evaluated by m a n s run corresponded, within experimental error, to the
of the equation for a second-order equation, amount of propionaldehyde initially present. These
namely results are given in Table I. Therefore, for our
k’j
2.303
=- b(a - X) calculations, changes in hydrogen cyanide concen-
log --___
u - a(b - X) tration were determined analytically and changes
where a and b are the initial concentration and (a - in carbonyl concentration were assumed to occur
x ) and ( b - x) are the existing concentrations a t on the mole for mole basis.
any time. In a series of runs a t a constant ionic TABLE
I
strength the value of k 1 should be proportional to PROPIONALDEHYDE
BY WEIGHTAND BY ANALYSIS
the ratio COA~-/CHOA~. An examination of equa- Equilibrium Initial
tion (6) for secondary salt effects as the ionic Initial H C N
concn., moles/l.
HCN
concn., moles/l.
AHCN,
moles/l.
propionaldehyde
concn., moledl
strength is varied indicates a negligible secondary
0.1082 0.0412 0.0670 0.0663
salt effect. The activity coefficients of non-ionic
.lo69 .0376 .0693 .0692
hydrogen cyanide and acetic acid may be set equal
.lo57 .0364 .0693 .0693
to 1 in dilute solution and the ratio of fOAc-/fCN-
.0950 .0306 .0644 .0654
will be practically constant in dilute solution.
.OS93 .0277 .0616 .0615
However, in addition to the mechanism repre-
sented by equation (la) it can be shown that other The rate constants for the propionaldehyde and
mechanisms involving cyanide ion or, alternatively, acetaldehyde reactions were evaluated by the
hydrogen cyanide may be written which lead to the graphical method usually employed for a reaction
same rate equation, namely equation (6). Among which obeys equation (5). The use of first- and
these are third-order equations led to inconsistent results.
slow A typical set of data for each of these reactions is
A0+ CK- + HzO d products (lb) shown in Table 11. Experiments were performed
fast slow in which the initial HCN/propionaldehyde ratio
A0 + H20 AO-H20 + CN- +products (IC) varied from 1.5 to 0.75. The k’ values obtained
slow in these experiments were in agreement with one
A 0 + H C N + OH- + products (Id) another, showing a true second-order reaction.
fast slow The results are given in Table 111. In the remain-
A 0 + OH- A(0H)O- + HCN -+ products t le) der of the propionaldehyde runs in buffered solu-
fast slow tions and in all of the acetaldehyde runs, the hydro-
AO+ HCN AQHCN + OH- --+ products (If) gen cyanide was initially in excess of the aldehyde
For each of these mechanisms, the value of the (16) L. P. Hammett, “Physical Organic Chemistry,” McGraw-Hi11
Book Co., Inc., New York, N: Y.,1940, pp. 215-222.
rate constant in solutions of constant ionic strength (17) R H Harmon and F l’ Worlry, Tpans F o r a d a v Sor , 20, 502
should hc proportional to the ratio of C O A/~ (192%)
July 5, 1953 KINETICS
OF CYANOHYDRIN
FORMATION 3109

in amounts varying from 0.0469 to 0.0273 mole/l. x existing concentration of A a t any time t
Tables V and VI summarize the data on the effects f =b-a
of ionic strength and buffer composition. Any- K = k'lk11
where from two to four runs were made under the integrated equation for the rate constant of the
each set of conditions. The rate constants were re- forward reaction is
producible to within 1 to 2%.
2.303 x -I.(f+ x. WK)) + +
TABLE
I1 klt = 2x. + +
f (1/K) log x - Xa
Propionaldehyde: buffer composition, 0.1010 N HOAc, constant (9)
0.0509 N NaOAc; p = 0.0509; final concn. of HCN,
( a - b ) = 0.0424 N . The rate constants of the acetone reaction were
evaluated by a graphical method based on equation
Slope of log 8s. t = 0.01244
b - x (9). A typical set of data is shown in Table IV.
k' = 0.676 liter/mole-min. Table VI summarizes the data for the acetone reac-
Aldehyde (calc.), tions.
t (min.) (a -HCN (exp),
x ) , moles/l. (b - X I , moles/l.
TABLE
V
2.78 0.0990 0.0566
5.33 .0906 .0482
STRENGTH
I N F L ~ NOFC IONIC
E IN THE PROPIONALDEHYDE
REACTION
8.17 .OB0 .0406
Buffer composition Ionic
15.23 .0706 .0282 HOAc, NaOAc, HOAc/ strength, kr,
19.80 .0653 .0229 N N OAc- p l./mole-min.
0.0341 0.0342 1.00 0.0342 1.23 & A.D.M.0.01
Acetaldehyde: buffer composition, 0.1372 N HOAc,
0.0503 N NaOAc; p = 0.0503; final concn. of HCN, .0234 .0234 1.00 ,0234 1.23 .01
( a - b ) = 0.0273 N . .0234 .0234 1.00 .0900 1.24 * .Ol
a - x ,0234 .0234 1.00 .2000 1.25 * 02
Slope of log -as. t = 0.002491 .0102 1.98 .0102 0.628 .005
b - x .0202
k' = 0.210 liter/mole-min. .0202 ,0102 1.98 .0509 .655 .OOl
3.28 0.0657 0.0384 .0319 .0101 3.15 ,0101 .390 ,002
11.12 .0619 .0346 .0319 .0101 3.15 ,0506 .405 .ooo
24.43 .0569 .0296 .0401 .0102 3.94 ,0102 .305 .OOl
40.35 .0515 -0242 .0401 .0102 3.94 ,0509 .317 .002
67.22 .0463 .0190
TABLEVI
TABLE I11 EFFECT OF BUFFERCOMPOSITION
DATAFOR THE PROPIONALDEHYDE
EXPERIMENTAL REAC- Buffer composition Ionic k?
HOAc, NAOAc, HOAc/ strength, I./mole-min.
TIONS FOR HOAc/OAc = 1, p = 0.0342 Series N N OAc- p f A.D.M.
Initial Initial Final Propionaldehyde reaction
HCN. aldehyde, HCN kl,
moles/l. moles/l. moles/l. l./mole-min. .. 0 0 0 0 0.542
0.0950 0.06% 0.0306 1.22 .. 0 0 0 0 ,487
.0911 .0519 .0392 1.23 .. 0 0 0 0 .404
.0893 .0615 .0277 1.22 A 0.1010 0.0509 1.98 0.0509 .677 0.001
.om .1189 .... 1.25 B .0202 .0102 1.98 .0509 ,655 .001
Av. k 1 1.23 f 0.01 A .E95 .0506 3.15 ,0506 ,425 .003
TABLE IV
B .0319 .0101 3.15 ,0506 .405 .OOO
A .2006 .0509 3.94 .0509 ,335 .003
Acetone: buffer composition, 0.0441 N HOAc, 0.0496 N
NaOAc; p = 0.0496. Initial H C N concn., a = 0.0758 N; B .0401 .0102 3.94 .0509 ,317 .002
equilibrium concn. of HCN, xe = 0.0366 N . Initial ace- Acetaldehyde reaction
tone concn., b = 0.1164 N ; equil. concn. of acetone =
0.0772 N . Equil. constant, K = 13.87 (mole/liter)-l. A 0.1372 0.0503 2.73 0.0503 0.212 0.002
f = ( b - a ) 0.0406 N; f ~e
mole/l.; 2x, +f +
(1/K) = 0.1859 mole/l.
+ +
( l / K ) = Q = 0.1493 B 0.0275 0.0101 2.73 0.0503 0.209 0.002

Slope of log ( x +
Q ) / ( x - x e ) us. t = 0.000628
k' = 0.00778 liter/mole-min. A
Acetone reaction
0.0441 0.0496 0.889 0.0496 0.00774 0.00008
t (min.) x L (min.) x B 0.0110 0.0124 0.889 0.0496 0.00772 0.00007
4.37 0.0748 265.4 0.0610
73.23 ,0710 346.7 .0584 Discussion of Results
172.5 .0655 434.4 ,0557 Results in Unbuffered Solutions.-The first
The reaction of acetone with hydrogen cyanide three values of k1 listed in Table VI show that in
does not go to completion and it is necessary to take unbuffered water solutions the rate is unreproduc-
into account the back reaction. For the general re- ible. This behavior is fairly characteristic of acid-
action base catalyzed reactions in water. If i t were
possible t o conduct experiments in water, free from
kl
A + B S C
any acid-base impurities, the PH would be con-
k11
trolled by the dissociation of HCN and the reaction
x (n + f) ( a - x ) would occur in a medium of constantly changing
PH. Thus the kinetics would be expected to follow
where a and b = initial concentrations of reactants a 3/2-order law, first order relative to aldehyde and
A and B, respectively. 1/2 order relative to HCN. H ~ w e v q in , each of
 31 10 W. J. SVIBBELY
AND JAMES F. ROTH VOl. 75

the runs in unbuffered solution the data ielded a fourth experiment only indicates that oxidation
Y
linear second-order plot. We may there ore infer
that the pH was sensibly constant during a run
might have occurred to the extent of 1.5%.
Magnitude of Equilibrium and Velocity Con-
and that the p H was probably controlled by some stants.-As mentioned before, our results show that
species other than HCN. Small but varying the acetaldehyde and propionaldehyde reactions
amounts of propionic acid, produced by oxidation go virtually to completion. JoneslB reports an
of the aldehyde, could have produced the observed equilibrium constant of 139.2 for the formation of
results in unbuffered solution. acetaldehyde cyanohydrin in aqueous solution a t
Influence of Ionic Strength.-The influence of 25'. Yates and Heiderll have reported a value for
ionic strength on the propionaldehyde reaction is il- the equilibrium constant of the acetaldehyde re-
lustrated in Table V. The ionic strength in- action a t 25' which is in agreement with our results
fluence is small, amounting to a maximum of 4.3% as to the degree of completion of the reaction.
for the range studied, Thus an acceptable mech- Values of the equilibrium constant for acetone
anism must not produce either an appreciable cyanohydrin formation in dilute aqueous solution
primary or secondary salt effect. at 25' have been reported by Jane@ and by
Nature of Catalyst.-Table VI illustrates the ef- Stewart and c o - w ~ r k e r s . ~ Their
~ ~ ~ values are
fect of buffer composition on the rate constants for 12.56 and 15.38, respectively. Our value, the
all three reactions. In all of the experiments de-
signed to test for general catalysis, the ratio of
mean of four experiments, is 13.97 A.D.M. 0.08.*
The results of Jones are unreliable as examination
HOXc/OAc- is the same for series (A) and (B). of his data will show. We cannot explain the dis-
The constancy of ionic strength for series (A) and crepancy between our value of 13.97 and Stewart's
(B) suppresses any salt effect. value of 15.38.
In the reactions of acetone and acetaldehyde, the Yates and Heiderl' provide data on the rate of
values of k1 are constant within the probable error acetaldehyde cyanohydrin formation in unbuffered
and it is evident that no general catalysis is de- solution over a temperature range, Extrapolation
tectable. In the propioaaldehyde reaction, a of their data to 25' yields a value of 0.69 X
comparison of the rate constants in each series (A) for k z l , wherein kz1 is equivalent to our k1 multiplied
and series (R) shows a variation of k1 in a manner by the hydrogen ion concentration. Using 1.752
which indicates general catalysis. In all cases, the X as the value of K A for acetic acid and using
rate decreases with decreasing buffer composition. the simple Debye-Hiickel limiting law to allow for
The variation in k' is not large, varying from 3.4 the influence of ionic strength on the activity co-
to 5.770, depending on the ratio involved. efficients of the ions, the hydrogen ion concentra-
Judging from the reproducibility of k1 values for tion in our solutions is calculated to be 8.1 X
a given series, the variation observed is greater With an average of 0.210 for kl, we ob-
than the experimental error. A source of error tain a value of 1.7 x 10" t o be compared with
is the oxidation of the aldehyde, and unfortunately 0.69 X The discrepancy may partly be
such oxidation would exert the same effect on the due to small amounts of oxidation of acetaldehyde
rate constant as general catalysis. Our calcula- in the work of Yates and Heider. This is a highly
tions indicate that a 2(& oxidation could account probable occurrence based on general experience
€or the k' values of 0.677 and 0.655; a 3.570 oxida- with acetaldehyde even when unusual precautions
tion for the values of 0.425 and 0.405; and a 5% are exercised to avoid oxidation.20 Such oxidation
oxidation for the values of 0,335 and 0.317. Thus, could have raised the ionic strength to a value for
different amounts of oxidation must be assumed to which the activity coefficient of hydrogen ion would
explain the variations observed as due to oxidation. be smaller than that assumed by Yates and Heider.
The reproducibility of rate constants for a given The use of a smaller activity coefficient would result
medium would require that the amount of oxida- in a higher hydrogen ion concentration for a given
tion be fairly constant. Since all of the experi- measured p H and, correspondingly, a higher value
ments for the propionaldehyde reaction listed in for the rate constant.
Table VI involve the same procedure, one would Mechanism.-Since the variations observed in
expect the same constancy to hold for all of the k 1 for the propionaldehyde reaction appear to lie
experiments, For example, a 5v0 oxidation can outside experimental error, one must conclude that
explain the last set of k 1 values; yet.a ,5:& oxidation this reaction is subject to general catalysis. There-
in the first set would cause k 1 to vary from 0.0'77 fore, the Lapworth mechanism as a general mecha-
to 0.625 rather than to 0.655. nism for cyanohydrin formation is not compatible
The best indication of the extent of oxidation with the observed kinetics.
would be experimental evidence. Since the pro- The presence of general acid catalysis is widely
pionaldehyde reaction proceeds quantitatively, one interpreted to signify that the initial step in the
would expect that in experiments with hydrogen mechanism involves a proton transfer.21*22If
cyanide in excess, the amount of hydrogen cyanide proton transfer is the initial step in the mechanism
which would disappear at the completion of the for cyanohydrin formation, then the following
reaction should correspond to the amount of 118) W. J. Jones, J . Chem. SOC.,106, 1547, 1560 (1914).
propionaldehyde initially present. If oxidation (19) C. Li and T.D. Stewart, THISJOURNAL, 69, 2596 (1937).
of the aldehyde had occurred, this would not be SO. (20) R. P. Bell and W. C. E. Higginson. Pvoc. Roy. SOC.(London),
Al97, 1 4 1 (1949).
Table I summarizes some data which can be used (21) R. P. Bell. "Acid Base Catalysis," Oxford Press, London, 1941,
to test this point. The initial propionaldehyde p. 114.
concentration was determined by weight. The (22) Ref. 16, pp. 330, 334.
July 5; 1953 OF GASEOUS
PHOTODECOMPOSITION DI-~-BUTYL
PEROXIDE 3111

mechanism should be applicable, namely slow

>C=O.. .HzO + CN- >C(CN)OH + OH-
fast
RzC = 0 + HA ----+ (RzCOH)+ + A- (loa) fast
(Ilb)

(RzCOH)’ + CN- slow

+ RzC(0H)CN
>C=O + CN- >C(CN)O- (12a)
(lob) slow
However, such a mechanism is not compatible with >C(CN)O- + HzO + >C(CN)OH + OH- (12b)
slow
the observed kinetics since the second-order rate
constant relative to carbonyl and HCN would be
>CEO + HzO + CN- + >C(CN)OH + OH- (13)
independent of the p H and this is not the case. The mechanism l l a , l l b is preferred because:
In the case of general acid catalysis, if the value (1) reaction 12b requires that a simple proton
of a in the Bronsted catalytic equation is close to transfer to an oxygen atom be rate-determining,
zero,23 general acid catalysis may be obscured whereas experience indicates that such a process is
since the solvent molecules which are present in instantaneous; (2) the usual argument against a
large excess may act as an acid. It is possible that true termolecular process.
this is the case in cyanohydrin formation as evi- The mechanism represented by ( l l a , b) is gener-
denced by the fact that a small general catalytic alized for any carbonyl addition by
effect existed in the propionaldehyde reaction and fast
none in the other two reactions. Accordingly,
there are three possible mechanisms of interest.
>C=O + HA J_ >C=O...HA (14a)
slow OH
fast >C=O - .. HA + B + >C( + A- (14b)
>C=O + HzO I_ >C=O.. .HzO (hydrogen bond)
B
(Ila) in which HA is any acid and B is the nucleophilic
(23) A. A. Frost and R. G. Pearson, “Kinetics and Mechanism,”
reagent.
John Wiley and Sons, Inc., New York, N . Y., 1953,p. 219. PARK,MD.
COLLEGE

[CONTRIBUTION FROM THE O F CHEMISTRY, UNIVERSITY OF CALIFORNIA, DAVIS1

DEPARTMENT

Photochemical Reactions in the Gas Phase Systems : Di-t-butyl Peroxide,

Peroxide-Butadiene and Acetone-Butadiene
BY DAVIDH. VOLMAN M. GRAVEN^
AND WENDELL
RECEIVED
DECEMBER
12, 1952

The absorption spectrum of gaseous di-t-butyl peroxide gave no evidence of structure. Combined with photochemical
results obtained, this gives evidence for a primary decomposition yield of unity. Methyl and t-butoxy radicals from photo-
decomposing di-t-butyl peroxide add to butadiene and initiate polymerization. The activation energy for chain propaga-
tion is about 5.8 kcal./mole for peroxide initiation and about 5.0 kcal./mole for acetone initiation. The polymerization rate
is linear with butadiene concentration for the peroxide initiation but reaches a maximum and then falls off for the acetone
initiation. This is evidence for a photoactivated state and collisional deactivation of acetone molecules. When acetone is
photolyzed in the presence of butadiene, ethane is eliminated as a product. Under these conditions butadiene acts as an
efficient free radical “trap” for methyl. This shows that ethane cannot be produced by an intramolecular process. A
combination of data for the decomposition of the peroxide and acetone in the absence and in the presence of butadiene leads
to activation energies of 11.2 f 2 and 13.5 f 2 kcal./mole for the decomposition of t-butoxy and acetyl radicals, respectively.

Few studies of the photochemistry of dialkyl results to a consideration of the activation energies
peroxides are reported in the literature. Prior to of t-butoxy and acetyl radical decomposition.
the initiation of our experiments, the only work
which had come to our attention was a brief report Experimental
on the photodecomposition products of diethyl Reactions were carried out in a 32 X 197 mm. cylindrical
peroxide12and a single experiment to determine the quartz cell, 158-ml. volume, contained in an air thermostat.
decomposition products of liquid di-t-butyl per- The whole cell was uniformly illuminated. Pressure changes
were measured by a quartz spiral gage. At the end of a
oxide.3 Results on the photodecomposition of run, the contents of the reaction vessel were separated by
gaseous di-t-butyl peroxide4 appeared while this use of a Toepler pump into a volatile fraction, non-conden-
work was in progress. The results obtained in our sable a t -120°, and a non-volatile sample, the remainder.
study largely substantiate those obtained by Analyses of both fractions were made by a consolidated
mass spectrometer.
Dorfman and Salsburg. However, we have ex- Di-t-butyl peroxide was obtained from Shell Chemical
tended the work to include the initiation of chain Co. and was further purified by bulb-to-bulb distillation
polymerization of butadiene by radicals from the under vacuum. The refractive index was found t o be 12%
photolyses of the peroxide and have applied the 1.3888. This compares well with published values of
1.388g4and 1.3890.6 Butadiene was Matheson C.P. grade.
(1) Based on a portion of a thesis presented by W. M . Graven in A Hanovia Type A burner operated on direct current was
partial satisfaction of the requirements for the degree of Doctor of used in all the experiments as the light source. A potassium
Philosophy in the University of California. triiodide solution was used as a filter to limit the radiation
(2) M . Barak and D. Style, Nature, 136,307 (1935). t o the 2537 A. region in some of the runs.
(3) E. R. Bell, F. F. Rust and W. E. Vaughan, THISJOURNAL, 79,
337 (1950). (5) J. H. Raley, F. F. Rust and W. E. Vaughan, ibid.. 70, 88
(4) L. M . Dorfman and Z. W. Salsburg, i b i d . , 73, 255 (1951). (1948).