404 Ind. Eng. Chem. Process Des. Dev.
1981, 20, 404-407
Kinetics of Nitration of Aromatic Compounds with “Mixed Acid”: Reinterpretation of
Published Data
The nitration reaction is generally assumed to be first order In nitric add and also first order In aromatic compounds.
This assumption is based on nitration studies with sulfuric acid as the reaction medium and where very low
concentrations of reactants were employed and the acidity of the system remained practically constant. However,
in the case of nitrations performed under industrially relevant conditions, the acid strength changes significantly
and the value of the rate constant changes severalfold. The assumption of first-order behavior with respect to
aromatic compounds is also open to doubt. An attempt has been made, therefore, to reexamine the published
kinetic data with the help of the HR acidity function.
Introduction
The nitration of aromatic compounds is commonly af-
fected by a mixture of nitric and sulfuric acids, called
“mixed acid” and the subject has attracted the attention
of several investigators in the recent past (Albright and
Hanson, 1976). The intrinsic rate expression used by many
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of the investigators is given by
r =
M^hnOsCai (1)
The first-order behavior with respect to nitric acid and
aromatic substrate was observed by various investigators
in the homogeneous acid phase nitration by employing very
low concentrations of reactants. The concentration of the
aromatic compound was of the order of 6 mol Lr1 while
that of nitric acid was approximately equal to 3 X 10'2 mol
Lr1. In the nitration reaction, nitronium ion is known to
be the real electrophilic species and its concentration is
almost proportional to that of nitric acid as the acid
strength of the reaction medium practically remains con-
stant. Hence, eq 1 is valid under such conditions.
In the case of heterogeneous mixed acid nitrations,
however, the acid strength changes significantly and eq 1
may not be applicable. The use of eq 1 for the interpre-
tation of kinetic data results in widely varying values of
k2. It is for this reason that empirical correlations have
been reported in the literature to relate the rate of nitration
with the acid phase composition. For example, McKinley
and White (1944) have used eq 2 to express the rate of
nitration of toluene.
Rk(XT)(N)p
=
(2)
The value of P, the order of reaction with respect to nitric
acid, varies from 0.6 to as high as 18.
In the nitration of benzene, Biggs and White (1956) have
proposed a linear relationship between the apparent rate
constant obtained by eq 1 and a factor representing the
composition of the acid phase on the log log scale.
Sehiefferle et al. (1976) have found eq 3 as a suitable
expression to correlate the rate of nitration of benzene.
R ==
Hva36A115(/iCAr)0-6(CHNo3)4'45 (3)
Hanson and co-workers have studied the macrokinetics
of heterogeneous nitration of toluene (1971) and chloro-
benzene (1974) with mixed acid of composition 15 mol %
HN03, 30 mol % H2S04, and 55 mol % H20. However,
no consideration has been given to the change in the
acidity of the acid phase and its effect on the change in
the rate constant.
From the foregoing discussion it is seen that the com-
position of the acid phase is an important factor and a
small change in the proportion of sulfuric acid or nitric acid
in the acid mixture significantly affects the rate of nitra-
tion. It is believed that nitronium ion is the real electro-
philic species involved in nitration. Thus it would be
highly desirable to know the relationship between the
0196-4305/81/1120-0404$01.25/0
composition of the acid phase and the concentration of
nitronium ion.
The direct determination of nitronium ion concentration
is not possible for mixed acid, which is commonly used for
mononitration, as it is below the limits of spectroscopic
determination. To overcome this problem, the similarity
of behavior of triphenylcarbinol or its derivatives in sulfuric
acid with that of nitric acid could be used (Westheimer
and Kharasch, 1946; Lowen et al., 1950; Deno and Stein,
1956).
The ionization of triphenylcarbinol, or its substituted
derivative, represented by ROH, in sulfuric acid to produce
the corresponding triphenylcarbonium ion is analogous to
the ionization of nitric acid to produce nitronium ion
ROH + H+ R+ + H20
<=* (4)
HN03 + H+ N02+ + H20 (5)
The measurement of the ionization ratios Cr+/Croh by
colorimeter for indicators undergoing ionization according
to eq 4 has become the basis of an acidity function. The
acidity function is denoted by Hr and is defined as
Hr =
-pfcRoH
"
log Cr+/Croh (6)
Relationship between k2 and Hr. The validity of
expression (1) for the homogeneous acid phase nitration
suggests the interaction of the nitronium ion with the
aromatic substrate to be the slow, rate-limiting step. The
rate expression, therefore, should have been
rate = ^ 02+0 2+ (?)
From the use of eq 1 and the concept of acidity function
the following relationship can be readily derived
Thno3TathTr+
log k2 =
-Hr + log kKnNO, + log (8)
Troh
Thus if other terms are assumed to be constant, a linear
relationship should exist between log h2 and -Hr with a
slope of unity. This has been ascertained for nitration of
various substrates such as nitrobenzene, p-chloronitro-
benzene, phenyltrimethylammonium ion, etc., for homo-
geneous nitration in the medium of sulfuric acid. A similar
treatment is warranted for the nitration of aromatic com-
pounds with mixed acid under industrially relevant con-
ditions. However, no information is available for the values
of acidity function for mixtures of nitric acid and sulfuric
acid. It was, therefore, thought desirable to obtain such
data.
Experimental Section
Triphenylcarbinol was used for the determination of
values of Hr acidity function of mixtures of nitric acid and
sulfuric acid. The reagent was prepared by reaction of
phenylmagnesium bromide with methyl benzoate as re-
ported by Bachmann and Hetzner (1941).
&copy; 1981 American Chemical Society
 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981 405

Table I. Experimental and Predicted Values of-Hr for

Synthetic Mixtures of Nitric Acid and Sulfuric Acid
1

SV -Hr, caled
no.
Ch2so4 CHN03 O CtfTJ
01
by eq 7
1 3.501 4.949 6.462 6.452
2 3.501 5.360 6.687 6.688
3 3.501 5.771 6.912 6.924
4 3.50.1 6.144 7.112 7.139
5 3.501 6.592 7.362 7.396
6 3.501 7.115 7.662 7.697
7 3.501 7.787 8.022 8.084
8 3.501 4.342 6.112 6.102
9 3.874 4.342 6.485 6.487
10 4.201 4.342 6.810 6.824
11 4.551 4.342 7.150 7.184
12 4.878 4.342 7.475 7.521
13 5.275 4.342 7.860 7.929
14 5.625 4.342 8.210 8.290
15 5.998 4.342 8.575 8.675

Synthetic mixtures of nitric and sulfuric acids were

prepared and the desired quantity of triphenylcarbinol
added so as to have its concentration of the order of 10"5
mol L'1. Absorbance values of only those compositions
Figure 1. Data of McKinley and White: plot of log ,/ ^ va·
Hr.
were determined which were reasonably stable (no change
in absorbance values over a period of 3-4 h) and are listed
in Table I. For other compositions of mixed acid, the
indicator was not stable and the direct measurement could
not be made. However, the variation of acidity function
with the composition of acid mixture could be correlated
satisfactorily by the following empirical equation (Table
I).
-Hr =
1.03CH2so4 + 0.575CHNo3 0)
The same expression was assumed to be applicable for
the compositions of mixed acid used for nitration studies,
and the respective values of HR were predicted.
Discussion
Correlation of Apparent Rate Constant with HR:
In the literature there are extensive kinetic data available
for the nitration of aromatic compounds such as benzene,
toluene, etc. However, in order to avoid complications due
to the role of mass transfer, only the data pertaining to Figure 2. Data of Biggs and White: plot of log R,/XbCkso¡ vs. Hr.
those cases where the kinetic regime is known to prevail
were considered. In the case of toluene, the intrinsic rates pounds. However, a close scrutiny of the data indicates
of nitration are extremely high and it may not be possible
that the reaction under industrially relevant conditions is
to eliminate mass transfer effects, particularly when ni-
not first order with respect to aromatic species. For ex-
ample, Schiefferle and co-workers have reported the order
trating mixtures of very high acid strength are used. with respect to aromatic compounds as 0.6 for the nitration
However, for nitrating mixtures containing less than, say, of benzene with mixed acid under the conditions of a ki-
30 mol % sulfuric acid, the intrinsic rates could be low
netic regime. Further, the examination of their plot of rate
enough to permit elimination of mass transfer effects with of reaction against composition of the organic phase in-
efficient agitation. In a recent review, Strachan (1976) has
dicates that, up to 40% conversion based on benzene, the
inferred that for the data of McKinley and White, the
reaction rate might be independent of the organic phase
kinetic regime is most likely to prevail.
The plot of (-Hr) vs. log RJXrCm0z for the data of composition (Figure 3). This could be possible if the
formation of nitronium ion is the rate-limiting step, par-
McKinley and White for the nitration of toluene is shown
in Figure 1. Most of the points lie close to the straight ticularly when the conversion levels based on aromatic
line with a slope of 1.04. Similarly, the plot of -Hr against compounds are low.
Another important observation which strengthens doubt
the values of log RJXb‘CÍWos for the data of Biggs and
about the validity of first-order behavior with respect to
White for the nitration of benzene is a straight line as
aromatic compounds is the difference in relative rates of
expected and is shown in Figure 2. Thus there seems to nitration of toluene, benzene, and chlorobenzene for ho-
be good agreement between the observed and expected
nature of the plot. mogeneous nitration and for nitration under industrial
conditions. In the homogeneous nitration with sulfuric
The Intrinsic Rate Expression acid as the reaction medium where the nitration reaction
As in the case of homogeneous nitration, it has been is known to be first order with respect to aromatic com-
assumed that the reaction of nitronium ion with aromatic pounds, Coombes et al. have reported the rate of nitration
species is the rate-controlling step under the industrially of toluene to be 25 times greater than that of benzene.
relevant conditions. In such a situation, the reaction is Similarly, benzene reacts 30 times faster than chloro-
expected to be first order with respect to aromatic com- benzene (Coombes et al., 1969). Thus the reactivities of
406 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981

Future 3. Nitration of benzene: data of Schiefferle and co-workers. Figure 4. Data of McKinley and White: plot of log fi,/CHNOa va·
(-Hr + log Crjo)·
toluene, benzene, and chlorobenzene show a severalfold
difference when the attack of nitronium ion on the aro-
matic substrate is the rate-limiting step. In contrast to
these observations, in commercial nitrations the rate of
nitration of toluene has been reported to be 1.3 to 4 times
that of benzene (McKinley and White, 1944; Hanson et
al., 1971; Schielferle, 1976), while the rate of nitration of
chlorobenzene is about 0.25 times that of benzene (Hanson
et al., 1974). The ratio of rate of nitration of toluene to
that of benzene is also reported to vary from 1.3 to 2.8 as
the conversion level increases (Hanson et al., 1971).
The solubility of aromatic compounds like benzene or
toluene in mixed acid is of the order of 10"3 mol L"1. This
corresponds to values of concentration approximately 100
times more than those used in studies with homogeneous
acid phase nitration. This is quite an important difference
between the two processes and may render the interaction
of nitronium ion with aromatic species faster than for-
mation of the nitronium ion, making the latter a rate-lim-
iting step particularly for low levels of conversion. In view
of these considerations, it was thought desirable to reex-
amine the kinetic data.
A simplified scheme for the nitration of aromatic com-
pounds may be presented as Figure 5. Data of Biggs and White: plot of log RJCm0s vs. (-Hr
+ log CH2o)·
HN03 + H+ N02+ + H20 (10)
Reexamination of Data. The plot of log RJCHNOs vs.
N02+ + ArH ArN02 + H+
—
(11)
(-Hr + log CHjo) f°r the data of McKinley and White for
If the rate of formation of nitronium ion is the rate- the nitration of toluene is shown in Figure 4 and is a
limiting step, the nitronium ion formed may rapidly dis- straight line with a slope of 1.09. Points corresponding to
appear by reaction 11 and hence the reverse reaction as runs where the conversion based on toluene exceeds 90%
represented by eq 10 may be ignored. The rate expression deviate significantly from the straight line. Under such
would then be given by conditions the concentration of aromatic compound is low
and probably the interaction of nitronium ion and aromatic
rate = CH+CHN03 Yhno3 Yh+ (12)
compound assumes importance. The plot of log RJ CHno3
If the nitration is assumed to be zero order with respect vs. (-Hr + log Ch2o) for the data of Biggs and White for
to aromatic compounds and first order with respect to the nitration of benzene is shown in Figure 5 and the
nitric acid, we have agreement between the actual and expected natures of the
rate
plot is fairly good. In the studies the conversion based on
=
k°^ptCHm3 (13) benzene was not more than 60%.
The relationship between k°ejpt and Hr may be readily It may appear rather contradictory that the same kinetic
derived and we have data could be correlated satisfactorily whether formation
of nitronium ion is assumed to be the rate-controlling step
log fc°„Pt =
or its interaction with aromatic compound. However, it
YhoO YuNOa Yr+ may be due to the limited accuracy of the proposed cor-
-Hr + log CH2O + log k° + log —4;---
r ROH
(14) relation. It is also likely that the difference between the
rate of formation of nitronium ion and that of its inter-
Thus if other terms are assumed to be constant, a linear action with the aromatic compound may not be of ap-
relationship should exist between log fc°eipt and (-Hr + preciable magnitude under the industrially relevant con-
log CHi!o) with a slope of unity. ditions.
 Ind. Eng. Chem. Process Des. Dev. 1981, 20, 407-409 407

Conclusion H20 = water

It may be concluded that the concept of the HR acidity
function could be used in a satisfactory manner to correlate
the effect of change in composition of the acid phase on
the apparent rate constant in nitration reactions performed
under industrially relevant conditions. It appears that
formation of nitronium ion is the rate-limiting step in the
nitration of benzene and toluene at lower levels of con-
version.
Nomenclature
C = concentration in mol L"1
Hv = volume fraction of acid phase in the emulsion
hCfo = interfacial concentration of benzene in mol L"1
k, k2 = reaction velocity constant in L mol"1 min'1 K =
equilibrium constant
k°, kexpt = reaction velocity constant in min"1
N = mole percent nitric acid in the acid phase
P = a constant depending upon the sulfuric acid concentration
in the acid phase
pK log of equilibrium constant
—
HN03 = nitric acid
H2S04 = sulfuric acid
N02+ = nitronium ion
R+ = triphenylcarbonium ion
ROH = triphenylcarbinol
T = toluene
Literature Cited
Albright, L. F.; Hanson, C. "Industrial and Laboratory Nitrations”, Symposium
Serles, American Chemical Society, 1976.
Bachmann, W. E.; Hetzner, . P. In "Organic Syntheses”, Collect. Vol. Ill,
Wiley: New York, 1941; p 839.
Biggs, R. D.; White, R. R. AIChEJ. 1956, 2(1), 26.
Chedln, J. C. R. Acad. Sel., Ser. B1935, 200, 1397.
Coombes, R. G.; Moodle, R. B.; Schofield, K. J. Chem. Soc. B 1969, 800.
Deno, N. C.; Stein, R. J. Am. Chem. Soc. 1956, 78, 578.
Hanson, C.; Marsland, J. G.; Wilson, G. Chem. Eng. Scl. 1971, 26, 1513.
Hanson, C.; Marsland, J. G.; Naz, . A. Chem. Eng. Sci. 1974, 29, 297.
Lowen, A. M.; Murray, M. A.; Williams, G. J. Chem. Soc. 1950, 3318.
McKinley, C.; White, R. R. Trans. AIChE 1944, 40, 143.
Schiefferle, D. F.; Hanson, C.; Albright, L. F. In “Industrial and Laboratory
Nitrations", Albright, L. F.; Hanson, C., Ed.; Symposium Series, American
Chemical Society, 1976; Chapter 11.
Strachan, A. N. In “Industrial and Laboratory Nitrations”, Albright, L. F.; Han-

son, C., Ed.; Symposium Series, American Chemical Society, 1976; Chap-
r, R = rate of nitration in mol L"1 min"1 ter 13.
= rate of nitration in mol L"1 min'1 based on acid
RB phase Westhelmer, F. H.; Kharasch, M. S. J. Am. Chem. Soc. 1946, 68, 1871.
X = mole fraction of unnitrated aromatic compound in the
organic phase Department of Chemical Technology Jayant M. Kanhere
Y =
Activity University of Bombay Sampatraj B. Chandalia*
Matunga
Subscripts Bombay 400019, India
= aromatic compound
B = benzene Received for review April 10,1980
H+ = hydrogen ion Accepted December 16, 1980

UNIFAC Group Contribution Method for Silicone Compounds

The UNIFAC group contribution method is applied to solutions of silicone compounds. Reliable vapor-liquid
equilibrium data are used to estimate interaction parameters between six common groups and two groups containing
silicon. A general purpose optimization package is used to estimate the Interaction parameters.

Introduction In 7; =
In 7¡c + In 7R (1)
In the recent years a new method has been developed
for predicting thermodynamic properties of liquid mix- The combinatorial part is expressed by the equation
tures. This method, called UNIFAC, was proposed in 1975
Z
by Fredenslund et al. (1975). The significant contribution ,
.

In 7¡
1
= In -
+ -

q¡ In -

-H, - -

2Zxjlj (2)
of UNIFAC is its capability of predicting activity coeffi- i
cients for mixtures for which no experimental data are
available. h =
(r¡
-

<7¡)
"" -

Ul z- 10 (2a)
g
Liquid mixtures of silicone compounds, especially
polymers, have found numerous applications (Morton, QíXí W
1973). Surprisingly, few phase equilibrium data have been
,

^ ;
-
—

(2b)
published. Hence, the application of UNIFAC in this area X-QjXj XxjXj
is appropriate.
Theoretical Background The parameters r, and q¡ are functions of the group van
The group contribution concept put forward by Lang- der Waals volumes and surface areas, Vk and Ak, respec-
muir represents the basis of the UNIFAC method. It tively.
considers the liquid mixture to consist of functional groups =
%; =
(3)
T¡ <?; Zv{i)Qk
such as CH3, COOH or OH rather than molecules of var- k k
ious components. Hence the thermodynamic properties
of the mixture are determined by the properties of the Rk =
VV15.17; Qk =
A*/(2.5 X 10») (3a)
groups.
The assumptions involved in the derivation of the i'*w is the number of groups of type k in molecule i. The
UNIFAC model are clearly stated in a recent monograph residual part is
(Fredenslund et al., 1977). The activity coefficiets are In JiR =
(> [In * -
In *( )] (4)
divided into a combinatorial part and a residual part k

0196-4305/81/1120-0407$01.25/0 &copy; 1981 American Chemical Society