THE OXIDATION OF HYDRAZOBENZENE BY AMMONIUM

PERSULPHATE IN ACETONITRILE-WATER SOLUTION'

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ABSTRACT
In a given experiment, second order kinetics were displayed during the greater
part of the reaction over a considerable range of initial concentrations of re-
actants. In general, the seco~idorder behavior was maintained t o greater extent
of reaction when hydrazobenzene was in excess. The calculated second order
rate constant, k , decreased with increase in initial hydrazobenzene concentration
and increased with increase in initial concentratio11 of ammonium persulphate.
For different equin~olarconcentrations of reactants, k was virtually independent
of initial concentrations. The value of k was proportional t o the square root of
the ratio of the initial conceiltrations of persulphate and hydrazobenzene. T h e
activation energy of the over-all reaction was 16 kcal. per mole. A free radical
mechanism appears t o account reasonably well for the major experimental
observations.

INTRODUCTION
Can. J. Chem. 1956.34:1154-1162.

The oxidation of mercaptans by potassium persulphate in glacial acetic

acid -water solution has been discussed in a previous paper from this labora-
tory (3). In respect of persulphate disappearance, the reaction was found t o
change from first to second order as the mercaptan concentration was reduced
t o a sufficiently low value. The calculated first order constant decreased with
increase of persulphate concentration, but was independent of the chain length
of the aliphatic mercaptan used. A secondary salt effect was observed; sulphate
ions and sulphuric acid increased the rate, while potassium ions retarded it.
An activation energy of 26,000 cal. per mole was found for the reaction. T h e
experimental data were explained by a mechanism involving the attack on
mercaptan by sulphate ion radicals formed by thermal decomposition of
persulphate ions. Although Levitt (6) has recently suggested that the data
could be more satisfactorily interpreted if sulphur tetroxide rather than the
sulphate ion radical were considered the reactive entity, Eager and
McCallum (2) have shown by radioactive evidence that such a mechanism is
untenable.
Bartlett and Nozacki (I) have found that the addition of methanol t o a
buffered aqueous solution of persulphate largely increased the rate of per-
sulphate decomposition. The rate was found t o be three-halves order in per-
sulphate and half order in methanol. T h e results appear t o be satisfactorily
explaiiled by a free radical mechanism, in which the initial formation of sul-
phate ion radicals resulted from the direct reaction of persulphate with
methanol rather than unimolecular decomposition of persulphate. Bartlett's
mechanism has been challenged by Kolthoff et al. (5) since the addition of ally1
acetate virtually eliminates the rapid disappearance of persulphate in the
presence of methanol.
lilla?zuscript received A j r i l 25, 1956.
Contribzltion jronz the Physical Che~>zistry Laboratory, JlcGill University, Montreal, Quebec,
werithfina7zcial assista?zce from the Natio7zal Research Cou?zcil.
1154
 WHALLEY ET AL.: I-IYDRAZOBENZENE 1155

The present study was made with a view to obtaining further information
about the oxidation of organic molecules by persulphate in homogeneous
systems, particularly when the organic reactant is one that might be considered
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exceedingly susceptible of oxidation. T o this end hydrazobenzene was chosen

as the substrate.

EXPERIMENTAL AND RESULTS

The glacial acetic acid - water solvent used in the previous study with
mercaptans was unsatisfactory for present purposes, owing to the formation
of a blue-black coloration, followed by a dark precipitate, when hydrazobenzene
was added to the solution of persulphate. A mixed solvent consisting of 100 ml.
acetonitrile and 12.5 ml. water was found to be satisfactorily stable under the
experimental conditions it was desired to use; a t 25" C., the rate of disappear-
ance of ammonium persulphate (0.0015 M ) in the solvent was negligible, while
a t 45" C., a rate of only 0.3y0 per hour was measured when the initial concen-
tration was 0.006 M.
Technical grade acetonitrile (Brickman and Co., Montreal) was dried over
sodium sulphate and distilled through a Widmer column. The fraction boiling
Can. J. Chem. 1956.34:1154-1162.

between 82.0" and 82.5" C. was collected. I t was found that acetoilitrile once
distilled in this way gave rate data that were within 5y0 of values obtained
when doubly distilled solvent was used; hence for practically all the experi-
ments the acetonitrile was distilled only once.
Distilled water that had been redistilled through a quartz condenser was
used for most of the work, although regular laboratory distilled water from a
Barnstead still was found to give equally good results.
Ammonium persulphate, reagent grade, from Brickman and Co., RiIontreal,
was used as received. I t was stored in brown bottles in a vacuum desiccator
over sulphuric acid.
Hydrazobenzene was obtained from the same company and stored under
vacuum. Before use, it was recrystallized from ethanol and washed with ice-cold
soy0ethanol-water until the filtrate showed no yellow color. The pure white
crystals were immediately transferred to a vacuum desiccator and pumped dry
with a high vacuum pump. The melting point of the purified material was
invariably sharp a t 126.5" C. (uncorr.).
The rate of reaction between hydrazobenzene and persulphate was measured
by determining the rate of formation of azobenzene with a Fisher Electro-
photometer. Formation and intensification of a yellow color in the solution
was shown to be due to azobenzene by comparing the absorption spectrum of
a reaction mixture after about lOyo reaction with that for azobenzene in
acetone, using a Beckman spectrophotometer, model DU. For analytical
purposes, the electrophotometer was calibrated against solutions of azo-
benzene of known concentrations in the acetonitrile-water solvent.
Some experiments were made in which the sulphuric acid formed during
reaction was titrated with standard base. This method of following the reaction
was only approximate, owing to a difficult end point in the yellow reaction
mixture. Phenol red was the only indicator found to be a t all satisfactory.
 1156 CANADIAN JOURNAL O F CHEMISTRY. VOL. 34, 1956

Attempts to follow the disappearance of persulphate by the volumetric

method of Kolthoff et al. (4) were unsuccessful, owing to some ulldetermined
effect of hydrazobenzene; differential potentiometric titrations (7) also were
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unsuccessful.
Preliminary experiments indicated that hydrazobellzeile was rapidly oxidized
when a solution of it in acetonitrile-water was exposed to air. Hence, experi-
mental conditions were arranged to minimize the amount of oxygen in the
solvent and entrained in the solid reactants. Acetonitrile was deoxygenated b y
refluxing it for half an hour, after which it was cooled and stored under a
positive pressure of oxygen-free nitrogen. Distilled water was deoxygellated
with a stream of oxygen-free nitrogen and stored under a positive pressure of
the gas. By suitable techniques for sweeping with oxygen-free nitrogen it mas
possible to prevent contamination of the reaction mixture with oxygen while
it was being made and while samples were being talten for analysis. Checks
were made for oxygen contamination with blank experiments (no persulphate
present) under the same conditioils and a t the same time that each series of
experiments with persulphate was in progress. At no time was any correction
necessary for oxidation due to oxygen.
Can. J. Chem. 1956.34:1154-1162.

In a preliminary experiment with hydrazobenzene in excess over persulphate

(0.024 M and 0.0060 M respectively) it was found that when reaction was
complete the yield of azobenzene was within 2.5y0 of the amount that should
be formed if one mole of persulphate oxidized one mole of hydrazobenzene.
The stoichiometry of the reaction may therefore be represented

Experiments were made to determine the order of the reaction and the
effect on specific rate of varying the initial reactant concentrations. T h e data
were found to conform best to a second order rate equation, and are presented
accordingly.
In Fig. 1 are shown some typical second order plots for different initial
concentrations of hydrazobenzene a t given (0.0060 initial persulphate
concentration. T h e increase in calculated second order rate constant towards
the end of reaction was observed in most of the experiments. In general, it
appeared that, when either hydrazobenzene or ammonium persulphate concen-
tration was held constant a t 0.006 M, and the concentration of the other
increased, second order linearity tended to be preserved to larger extents of
reaction. This seemed to be particularly true when hydrazobenzene was the
reactant in excess. At persulphate concentrations below 0.006 M, secoild order
linearity appeared to exist to larger extents of reaction when hpdrazobeilzene
concentrations were correspondingly low. T h e dependence of extent of linearity
on which of the reactants was in excess was more pronounced a t higher than a t
lower temperatures.
The calculated second order rate constant was dependent upoil initial
concentration of the reactants in the manner sho\\rn in Table I and Fig. 2.
Although the results were generally reproducible within about 5Yo a t the
higher concentrations, they tended to be more variable a s the co~lcentrations
 WHALLEY E T AL.: HYDRAZOBENZENE
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TIME-HR.

- om
Can. J. Chem. 1956.34:1154-1162.

o 4 8 12
TIME-HR.

FIG.1. Typical second order plots.

Temp. 25.02f 0.02"C.
Initial concentration a m m o n i ~ ~ ~me r s u.l ~ h a.t0.00600
e. mole/liter.
Initial concentration hvdrazoben~ene:
Upper frame: C)-0.0120 mole/liter.
0-0.0240 mole/liter.
Lower frame: C)-0.00300 mole/liter.
0-0.00150 mole /liter.

TABLE I
EFFECT OF DIFFERENT IXITIAL CONCETTRATIONS O F H P D R . ~ Z O B E ~ \ ' Z E N E ~ A S D:\blhIONIUhf
PERSULPHATE ON THE CALCULATED SECOND ORDERIRATE
COXSTAXT

i\mmonium
persulphate = 0.006 RII.11. Hydrazobenzene = 0.006 M./1.
--
Hydrazo- k (I. nl.-l hr.-1) Ammoriiu111 k (1. nl.-l hr.-l)
benzene, persulphate,
NI.11. 25.02f 35.28f 45.75f M./I. 25.02A 35.28f 45.75f
O.Ol°C. O.Ol°C. 0.02"C. O.Ol°C. O.Ol°C. 0.02OC.
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 34, 1956

150
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0 10 20 30
I N I T I A L CONC. ( @ N H ) ~X I O - ~ M / L

0 10 20 30
I N I T I A L C O N C . ( N ~ & S ~ O ~l X
C3M/~

FIG.2. Dependence of second order rate constant on initial concentration of the reactants.
Upper frame: Initial concentration of ammonium persulphate, 0.00600 mole/liter.
Can. J. Chem. 1956.34:1154-1162.

Lower frame: Initial concentration of hydrazobenzene 0.00600 mole/liter.

Temperatures: top curves, 25.02"C.
middle curves, 35.28"C.
bottom curves, 45.75"C.

were reduced. However, there appears to be no doubt that the changes in k

represented by Fig. 2 are real.
When experiments were made a t 25' C. with equimolar concentrations
lower than 0.006 M, the rates were relatively independeilt of concentration of
the reactants, as indicated by the following data:

Initial concn. of
hyclrazobenzene ancl k (I. III.-~hr.-l)
a n ~ m o n i u npersulphate
~
(M./l.)

Two experiments made a t 0' C. with O.OOG0 i

W persulphate gave the fol-
lowing results:

Initial concn. of
hydrazobenzene k (1. m.-I hr.-l)
(M./l.)

These data, together with those of Table I, were used to calculate the
activation energy for the reaction a t different relative conce~ltrationsof the
 WHALLEY ET AL.:HY DRAZOBENZENE 1159

two reactants. There appeared to be no significant change of activation energy

with initial concentration of reactants, and a value of 1 6 f 0.5 ltcal. per mole
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may be assigned t o the over-all reaction.

An attempt t o determine the effect of added sulphuric acid on the reaction
rate was frustrated by the almost immediate formation of a white precipitate
in the reaction mixture. A similar precipitate, determined in one experiment
by filtration and weighing to amount to about 3% of the hydrazobenzene and
2y0 of the persulphate talten, was observed in most of the reaction mixtures as
reaction approached completion. This precipitate was insoluble in acetonitrile
and in water, and did not melt below 300" C. Its identity was not established,
since it represented such a small proportion of the reactants consumed.
Three experiments were made in which the increase in titratable acid in the
reaction mixture was followed simultaneously with photometric determinations
of the azobenzene formed. The initial concentrations of hydrazobenzene and
ammonium persulphate were 0.0060 iM and 0.0060 M,0.0090 M , and 0.012 M
respectively. As indicated earlier, the acidity determinations were rather
approximate but all three experiments showed that less titratable acid was
formed than would be expected from the amount of hydrazobenzene consumed.
Can. J. Chem. 1956.34:1154-1162.

The deficit amounted to 1 5 2 0 % .

DISCUSSION
Although the stoichiometry and the reasonably good second order ltinetie
behavior of the reaction might be interpreted in terms of a single step oxi-
dation, it seems more probable (8) that a t least two single electron transfer
steps are involved. I n view of this, the following reaction sequence is suggested:

The scheme neglects a possible reaction, viz.

inclusion of which makes mathematical treatment difficult.

If, for ease of representation, P = S208=, IT = C G H ~ N H N H C ~AH ~=,
C6H5NNC6H5, the usual steady state assumptions give the rate of formation
of azobenzene as
 1160 CANADIAN JOURNAL O F CHEMISTRY. VOL. 34. 1956

However, because of the apparent second order kinetics of the greater part
of most of the reactions, the usual second order rate equation was assumed to
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be applicable, that is:

where k is the calculated second order rate constant recorded in Table I and
Fig. 2. Hence,

[41

Equation [4]predicts, for a reaction scheme of the type postulated, that the
calculated second order rate constant, k, should be large for relatively large
concentrations of ~ersulphate,small for relatively large concentrations of
hydrazobenzene, and independent of concentration for equimolar concen-
trations of the two reactants. All of these conditions were realized experi-
mentally.
In Fig. 3 are plotted the values of k against ~ [ P ] / [ .HExtrapolation
Can. J. Chem. 1956.34:1154-1162.

] of

FIG.3. Plots of second order rate constant against d [ ~ c r s ~ ~ l ~ h a t e ] / [ ~ ~ d r a z o b e n z e n e ] .

@-Initial concentration ammonium persulphate, 0.00600 mole/liter.
A-Initial concentration hydrazobenzene, 0.00600 mole/liter.
Temperatures for lo\ver, middle, and upper curves wcre 25.02", 35.2g0, and 45.55"C.
respectlvcly.

these lines to zero gave

- values of kl, the second order rate constant for the
attack of hydrazobenzene by persulphate ion, the chain initiation step, a t the
three temperatures. The values so obtained were
 WHALLEY ET AL.: HYDRAZOBENZENE 1161

These values give a very satisfactory Arrhenius line, corresponding to an

activation energy of 17.5 kcal./mole.
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I t should be mentioned, perhaps, that conductance measurements indicated

ammonium persulphate in the acetonitrile-water solvent used to be only
weakly ionized. Hence, true persulphate ion concentrations in the reaction
mixture would be less than values used in the calculatiolls and plots. The
discrepancy would be the less, the higher the temperature. Unfortunately,
correction of the persulphate concentration was not possible since, as usual
with weakly ionized solutes, curvature of the relation between equivalent
conductance and square root of the concentration did not permit evaluation
of the conductance a t infinite dilution, hence the degree of dissociation.
T o determine whether the rate constant kl evaluated from individual
experiments would be independent of initial concentration of reactants (to
replace the concentration dependent k ) , equation [2] was integrated to yield

- In
klt -( [ P I- [>I12 - ,/Tr-?1/jPT+ k5
2
,/([IIFirn[~]--x)+
k
Can. J. Chem. 1956.34:1154-1162.

where k 5 = k 3 / 4 k T 4and kl is the rate constant for the initiation step.

Expansion of equation [6]gives

Values of k and A were calculated for different times in a given experiment

a t 25.02" C. for various initial concentrations of the reactants, and average
values of the two quantities obtained.
From a plot of k against A , a value for k5 a t 25.02" C. of 0.6 was obtained.
This value of k 5 was put into Equation [6]and the second term on the right-
hand side of this equation was plotted against time for various concentrations
of hyclrazobenzene and persulphate. From the slopes of these plots, values of
kl were obtained and these in turn were plotted against initial concentrations
of h>~cIrazobenzeneand persulphate, with the results shown in Fig. 4 . The
superiority of kl over k in respect of dependence on initial concentration (cf.
Figs. 2 and 4 ) is sufficient perhaps to indicate that the approach outlined is
sound. A more satisfactory test would have been possible if sufficient data had
been available a t the higher temperatures, but unfortunately it was not possible
to obtain a satisfactory evaluation of the necessary quantities with the data
recorded for these temperatures.
 CANADIAN JOURNAL OF CHEMISTRY. VOL. 34. 1956
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1 1 1 1 1 1 1 1 ~ 1 1 1
O 6 9 12 15
I N l A L CONC. (0NHI2 Y.Io-~ M A

1 1 1 1 1 1 1 1 1 ~ ~ J
0 6 9 12 15
lNrrlbL CONC. (NH&S& M/L

FIG. 4. Effect of different concentrations of hydrazobenzene on kl, the corrected rate

constant.
Temp. 25.02"C.
Upper frame: Initial concentration ammonium persulphate, 0.00600 mole/liter.
Lower frame: Initial concentration hydrazobenzene, 0.00600 molc/liter.
Can. J. Chem. 1956.34:1154-1162.

T h e second order kinetics displayed in individual experiments for consider-

able variation in initial coilcelltrations of reactants would indicate that a
compeilsatioil existed in the reaction to modify the behavior predicted by the
relati011 k ot ~ [ P ] / [ I. II ]t is iilhereilt in this relation that in a given experi-
ment, unless the reactants are in equimolar concentrations, the calculated
specific rate should decrease during the course oi reaction when hydrazo-
benzene is in excess and increase when persulphate is in excess. Actually, the
deviatioils from linearity were always in the direction of apparent increase in
specific rate. Much of the compensation might have been due to an increased
dissociatioil of persulphate as its collsumptioll progressecl, but it seems likely
that some other factor or factors not yet identified also contributed to the
observed behavior.
T h e interpretation of the experimental data suggests that the reaction is
initiated by the formation of sulphate ion radicals resulting from direct attack
by persulphate ions rather than by sulphate ion radicals from ~unimolecular
decomposition of persulphate.

REFERENCES
1. BARTLETT,P. D. and NOZACKI, I<. J. Am. Chem. Soc. 71: 1419. 1949.
2. EAGER,R. L. and MCCALLUDI, K. J. Can. J. Chem. 32: 692. 1954.
3. EAGER,R. L. and WIXIUER,C. A. Can. J. Research, B, 26: 527. 1948.
4. KOLTHOFF, I. M., CUSS,L. S., MAY, D. Ti., and MEDALIA,A. I. J. Polymer Sci. 1: 340.
1QdG
-,,
A-.

5. KOLTHOFF,I. M., MEEHAN,E. J., and CARR,E. M. J. Am. Chem. Soc. 75: 1439. 1953.
6. LEVITT,L. S. Can. J. Chem. 31: 915. 1953.
7. MACINNES, D. A. and DOLE,M. J . Am. Chem. Soc. 51: 119. 1929.
8. MICHAELIS, L. Chem. Revs. 16: 243. 1935.