INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, VOL.

v, 769-776 (1973)

Reactions in the Gas and Liquid Phases:

Comparison of Kinetic and Thermodynamic
Data
C. R. PATRICK
Chemistv Dekartment, University o j Birmingham, Birminghnm 15, England

Abstract
An analysis is made of relationships to be expected between the enthalpies and entropies
of reactions carried out in the gas and liquid phases, assuming ideal thermodynamic be-
havior of the components. The results of the analysis are compared with experimental
results reported in the literature. Some discrepancies are noted. These may be the conse-
quence of experimental error or may be due to substantial deviations from thermodynamic
ideality. If the latter is commonplace, there will be difficulties in making useful predic-
tions and correlations of thermodynamic and kinetic parameters in the liquid phase.

1. Introduction
Considerable progress has been made in the estimation of the enthalpy and
entropy changes accompanying reactions in the gas phase, and the results have
been used constructively in the estimation of rate parameters for gas reactions [ 11.
I t would be of great value if similar calculations could be made for reactions in
liquids. There are two methods of approach to the solution of the problem of
predicting or correlating the thermodynamic or kinetic parameters for reactions
in liquids. The first is to formulate directly rules for the estimation of the en-
thalpies and entropies of liquid substances. The second is to formulate rules for
the correlation of the enthalpies and entropies of liquids and gases so that by the
use of established correlations of the parameters for the gases, those for the corre-
sponding liquids may be estimated. As a contribution to the second of these
methods of approach to the problem, we will examine the relationships between
kinetic or thermodynamic data for a reaction carried out in the gas and liquid
phases. Although such comparisons have been discussed [2,3,4], certain features
have not been fully appreciated.

2. Formal Relationships between Thermodynamic Parameters for

Reactions in Gases and Liquids
We shall compare first the thermodynamic parameters for the equilibria
between substances whose behavior is thermodynamically ideal in the two phases.
769
@ 1973 by John Wiley & Sons, Inc.
7 70 PATRICK

The heats or enthalpies of reaction in the gas and liquid states,

(1) AHRO,, = Z AH,O (products, g ) - Z AHfO (reactants, g)

and
AHRO,~= Z AHfO (products, 1) - Z AH,O (reactants, I )
with respect to the gases in their reference states ( p = 1 atm) and the liquids in
their reference states (P = 1 atm), are related to the heats of vaporisation AH,O
of the liquid substances to give the respective vapors at p = 1 atm, thus:

(3) A H R o , ,- A H R " , =
~ Z AH,O (products) - Z AH,O (reactants)
Similarly, the entropies of reaction in the two phases are related by

(4) A S R o , , - ASRo,l = Z AS,O (products) - 2 ASVo(reactants)

where the entropies of vaporization, AS,", relate to those changes in state specified
for AH,O.
Heats of the vaporization of simpler substances (containing up to about 15
carbon atoms) are about 5 to 10 kcal molk'. In equilibria which involve no

ZAH,O (products) -
changes in the numbers of molecules or reactants and products, it is likely that
ZAH,O (reactants), so that the differences between the heats
of reaction in the two phases will be small. In associative equilibria such as
those of the type A +B = C, the disparities between ZAH,O (products) and
ZAH,O (reactants) are likely to be greater, so that A H R " , , - AHRO,~
will be signi-
ficant and negative. The consequences of eq. (4)have not previously been ex-
amined in detail.

3. Relationships between the Entropies of Reaction in Gas and

Liquid Phases
Trouton's rule states that the entropies of vaporization of many liquids at
their boiling points are nearly equal, and are equal to about 21 cal K-I molt'.
The rule may be extended to apply to show that the entropies of vaporization of
many liquids at other temperatures, if defined so as to represent the vaporiza-
tion to vapors at pressures of 1 atmosphere, are also approximately equal and share
the same approximate value. Specimen calculations suggest that the extended
form of Trouton's rule applies at temperatures from about 0.55T, to at least
0.85T, (when T,K is the critical temperature of the substance), and there are
indications that it extends more closely to the critical region. As the critical
region is approached, the contribution of the nonideality of the gas phase contri-
butes an increasing proportion to the entropy of vaporization of the substance to
the chosen reference state of 1 atmosphere pressure for the vapor. The rule may
be used, therefore, to correlate the differences between the entropies of reaction
in the gas and liquid phase in the sense we are discussing, but it cannot be used to
 GAS AND LIQUID PHASES 771

predict correlations between enthalpies of reaction in the two phases very close to
the critical temperature.
Although there may be uncertainties about the standard entropies of vaporiza-
tion of dissolved substances at about their critical temperatures, the situation is
better defined for the vaporization of substances from solutions at temperatures
at which the dissolved substances are above their critical temperatures and are
real gases. The dissolution of a gas in a liquid with which it shows no strong
specific interaction (that is, to form an essentially ideal solution), is not ac-
companied by a change in enthalpy that is comparable with the enthalpy of
vaporization of a real liquid at temperatures remote from the critical temperature.
The dissolution is, however, accompanied by a significant change in entropy,
and this, when it is extrapolated to the limit at which the substance is regarded
as the hypothetical liquefied gas, gives for the entropy of vaporization of the hypo-
thetical liquid gas to gas at a pressure of 1 atmosphere a value of about 22 cal
K-I mol-I, similar to that which follows from Trouton's rule. This result may be
deduced from much earlier work [5] but was only recently stated explicitly IS].
Its physical significance may easily be appreciated [7]. The entropy change is
that accompanying the restriction of the freedom of motion enjoyed by molecules
in the reference state in the gas to the small volume in which they are confined in
the liquid. I n the terms of some models for liquids, the latter volume is spoken
of as the free volume. The change in entropy is likely to be similar for all mole-
cules since, in the terms of the physical models referred to, the change in volume
must be of a similar magnitude, at least for simpler molecules.
Inasmuch as the entropies of vaporization from liquid mixtures, in the terms
just defined, are approximately equal, we may write, to a good approximation,

where Z V B is the difference between the numbers of molecules of products and

rear tants in the stoichiometric representation of the equilibrium; and ASTrouton,
equal to about 21 cal K-I mol-', is the nearly universal standard entropy of vapori-
zation. For equilibria involving no change in the numbers of molecules, Z v B = 0,
so that (ASRO,, - ASRO,~)1/ 0, and for associative equilibria of the type specified
above, in which Z V B = - 1 , (ASRO,, - ASRO,~)'v -21 cal K-' mol-l.

4. Comparison w i t h Experimental Results

The predictions relating to equilibria involving no change in molecularity are
+
verified by the results reported for equilibria of the type XZ Yz = 2XY between
halogens and interhalogen compounds. For such equilibria, the enthalpies of
the reactions in the gas phase differ from those in the liquid phase by 1 kcal
mol-I or less, and the corresponding entropies of reaction differ by 2 kral K-' mol-I
or less [4,8].
Associative equilibria are less well illustrated. Results in accordance with our
772 PATRICK

prediction are provided by the heats of dimerization of carboxylic acids [9].

The entropies of these dimerizations in the gas phase [ - (34 to 36) cal K-' mol-'1
are numerically greater than those in solution [ - (10 to 14) cal K-I mol-'1, and
the enthalpies of dimerisation in the gas phase [ - (14 to 16) kcal mol-'1 are also
greater than those in liquids [ - (8 to 10) kcal mol-'1. The differences between
the entropies of dimerization in the two phases are about -(20 to 22) cal K-'
mol-I. These are as we would expect, and do not, as asserted by Allen and
Caldin [9], imply any special interaction between the reactants and the solvents
(benzene or chlorobenzene).
The enthalpy and entropy of dimerization of nitrogen dioxide (to give Nz04)
in the gas phase are, respectively [lo], - 13.7 kcal mol-' and -41.6 cal K-' mol-'.
The dimerization was studied in a variety of solvents by Cundall [ 1 11. The heats
of dimerization calculated from Cundall's results by Moelwyn-Hughes [3] are
about - 20 kcal mol-'. The corresponding entropies, not previously reported,
are about -40 cal K-' mol-'. The reaction has also been studied as the dis-
sociation of liquid dinitrogen tetroxide (121. The enthalpy of dimerization in this
system is - 19.5 kcal mol-', and the entropy of dimerization is about -40 cal K-'
mol-'. The quantities for the liquid phase differ from those in the gas phase in the
unexpected sense. The behavior of the enthalpies of reaction could be accounted
for if, as has been suggested 1121 for the case of liquid dinitrogen tetroxide, the
effective heat of vaporization were small compared with the heat of vaporization
of the dimer. This hypothesis could be reconciled with the likely situation that
the hypothetical pure liquid nitrogen dioxide, at the temperatures of observation
(close to room temperature), relate to a substance that is close to its critical region,
for which the effective heat of vaporization cannot be predicted with confidence.
The behavior of the entropies of dimerization is more diffcult to understand.
In the work so far reported, the assumption has been made that the extinction
coefficients for the monomer are the same in the two phases. The detailed spectra
of the substance in the two phases differ appreciably [ 131. This suggests the need
to reassess the assumption regarding the extinction coefficients and may also have
other implications regarding the state of the substance in the liquid phase. If the
assumption regarding the extinction coefficients were shown to be incorrect, the
consequent changes in the estimates of the values of the entropies of reaction could
be large and probably more significant than those of the enthalpies of reaction in
liquid solutions.
Further support for the predictions is available indirectly. Studies of the
dissociation of hexaphenylethane in various solvents show that the entropies of
association of triphenylmethyl radicals in liquids are about - 18 cal K-' mol-' [ 141.
The entropy of the reaction in the gas phase, estimated using empirical methods
(for example, of ref. l ) , is about -40 cal K-' mol-'. These values differ as
expected. It is inappropriate, on the basis of our predictions, to compare, as is
sometimes done, the dissociation energy of hexaphenylethane measured in solution
 GAS AND LIQUID PHASES 773

with the dissociation energies of other carbon-carbon bonds measured in the gas
phase.
The enthalpy and entropy of dimerization of 1,l-diphenylethylene in solution
are -12 kcal mol-' and -29 cal K-' mol-', respectively [15]. The heat of
dimerization in the gas phase is - 25 kcal mol-', and the estimated entropy of the
reaction in the gas phase is about -45 cal K-' mol-I, consistent with our predic-
tions
Empirical calculations suggest that the entropies of association of polyatomic
species in the gas phase lie about -(35 to 45) cal K-' mol-', but become larger
with the increasing molecular weight and complexity of the species. The entropies
of association of such reactions in solution should therefore lie approximately in
the range of - (15 to 25) cal K-' mol-I or be larger. Some recent results reported
[IS] for equilibria for the association of some trialkylamines with some phenols
(to form ion pairs) in liquid solutions give for the entropies of association values
of about -30 cal K-' mol-'. These conform with our expectations.
Although our analysis has related to thermodynamically ideal systems, it
offers a useful basis for considering the behavior of nonideal systems. The
analysis could be extended to nonideal systems by the introduction into our equa-
tions of additional enthalpy and entropy terms, these being, respectively, the
excess enthalpies and entropies of mixing of the real or hypothetical liquid sub-
stances to form the liquid mixtures.

5. Relationship to Kinetic Parameters

Rate coefficients and, therefore, the equilibrium constants to which they may
be related are conventionally expressed in terms of concentrations (usually M ) .
If the equilibrium constants for the gas and liquid phase reactions, set in concen-
tration terms, are written as K c , gand K c , l , respectively, then we have

where V , is the volume of 1 mol of the liquid solution and RT is the volume of
gas (assumed ideal) which contains 1 mol. For reactions involving no change in
the numbers of molecules, the ratio of the equilibrium constants is unity. In the
range of temperature 0-IOO'C, R T is approximately 25 to 30 1. mol-', and for
reactions in commonly used simple liquids, V , is about 0.1 1. mol-'. Thus, for
associative equilibria ( Z Y B = - 1)

The temperature coefficients, written as R T 2 (8 In K c / T ) , of the equilibrium

constants just used, are not equal to the standard heats of reaction defined earlier
in the paper [17]. The differences are R T Z V B and R T 2 a, ZVB, for the cases of
reactions in the gas and liquid phases, respectively, where as is the coefficient of
7 74 PATRICK

expansion of the liquid solution. The latter correction is frequently misquoted.

For simple liquids in the temperature range 0-100°C, cy, is typically about K-I,
so that the numerical value of the differences between A H R ' . ~and R T 2 (a In
K.,,/aT) for associative reactions ( Z V B = - 1) are less than 0.3 kcal mol-' and
are frequently negligible compared with experimental uncertainties. They are
also much smaller than the corresponding difference, about 0.6 to 0.8 kcal mol-I,
between AHR',, and R T 2 (a In K,,,/aT) for reactions in gases, in the temperature
range specified.
Since the equilibrium constant for an association equilibrium constant in a
gas differs from that in the liquid phase, the rate coe'fficients for either or both of
the related associative or dissociative reactions in the two phases must differ.
Transition state treatments relate the difference between the energies of activa-
tion for a reaction in the two phases to the respective enthalpies of activation and
therefore to the difference between the enthalpies of vaporization of the transi-
tion complex and the reactants from which it is formed. Some authors (21 have
assumed that this difference is zero or argued apriori that it is small, about (1-n)RT
for an n-molecular reaction [25]. Others [ 141 have accepted experimental evi-
dence to demonstrate that the difference is negligible both for unimolecular
reactions and for associative reactions.
I n a unimolecular reaction, the transition state may be regarded as a relaxed,
but possibly otherwise modified, form of the reactant. The enthalpy of vaporiza-
tion of the transition complex is likely, therefore, to be close to (but possibly a
little greater than) that of the reactant. The entropies of vaporization of the
transition state and reactant are also likely to be nearly equal (as in the general
case for Z V B = 0). This implies the near equality of rate coefficients and Ar-
henius factors for unimolecular reactions in the two phases, and this is supported
by experimental evidence that is frequently cited (2,4] and also by recent evidence
relating to the isomerization of cyclobutenes [ 181.
The situation for bimolecular reactions is less clear. A commonly quoted
instance of a bimolecular reaction for such comparisons is the dimerization of
cyclopentadiene. Both the enthalpies and entropies of such an association reac-
tion should differ in the two phases. From measurements of the equilibria be-
tween solutions of each of the substances and their respective vapors (261, the
heats of vaporization of cyclopentadiene and its dimer from liquid paraffin are,
respectively, about 6.2 and 7.9 kcal mol-I. The first of these quantities is a little
smaller than the value (6.8 kcal mol-') reported for the heat of vaporization of the
pure liquid [27]. The discrepancy implies some deviations from thermodynamic
ideality in the solutions, but may be due in part to imprecision in the measure-
ments on the solutions. We infer from these data that the enthalpy of dimeriza-
tion in liquid parafin should differ from that in the gas by about 4.5 kcal mol-I.
The energies of activation for the dimerization of cyclopentadiene in the gas
phase [ 191, in liquid cyclopentadiene [ZO], in carbon tetrachloride [ZO], and in
liquid parafin [21] are, respectively, 16.7, 16.2, 17.1, and 17.3 kcal mol-I. The
 GAS AND LIQUID PHASES 775

corresponding preexponential factors are 1.4 X lo6, 6.4 X lo5, 5.0 X lo6, and
1.3 X lo7 1. mol-' s-l. Both the energies of activation and the preexponential
factors are more nearly equal than would be expected from our arguments.
The energy of activation reported for the decomposition of the dimer in liquid
paraffin [20,2 11 is 34.5 kcal mol-', and the corresponding preexponential factor
is 5 X 1012s-1. The derived enthalpy of dimerization in liquid paraffin is close
to - 17 kcal mol-I, and the corresponding entropy of dimerization is -33 cal
K-' mol-'.
Wassermann and his coworkers [19,20,21] report widely quoted data for the
dissociation of the dimer endodicyclopentadiene in the gas phase, but these were
not determined experimentally. From direct experimental investigation of the
decomposition in the gas phase, the energy of activation has been reported as
33.7 kcal rnol-l, and the preexponential factor, as 1013s-l [23]. Subsequent in-
vestigators [24] have reported that the data, when fitted by the least-mean squares
procedure, give the energy of activation as 31.4 kcal mol-', and the preexponential
factor, as 9 X 10" s-l. A more recent investigation [24] has given the energy
of activation as 33.97 kcal mol-l, and the preexponential factor, as 1 X 1013SKI.
Using the more recent values and combining them with the kinetic data for the
dimerization reaction in the gas phase, we find that the enthalpy and entropy of
dimerization in the gas phase are - 17 kcal mol-' and - 36 cal K-' mol- . Direct
studies of the equilibrium in the gas phase [22] give very similar values, namely,
- 16 kcal mol-' for the heat of dimerization and -36.4 cal K-' mol-l for the
entropy of dimerization. These thermodynamic parameters for the dimerization
of cyclopentadiene in the gas phase seem well established. The enthalpy of
dimerization in the gas phase is, unexpectedly, almost equal to that in liquid
paraffin. We have predicted a difference between the enthalpies of reaction in
the two phases. The difference between the entropy of dimerization in the gas
phase (- 36 cal K-' mol-') and that in liquid paraffin (about - 25 cal K-' mol-I)
also is smaller than we would expect, by about 10 cal K-' mol-I. We suggest that
the kinetic parameters for the reactions in solution are thermodynamically in-
consistent and that it should not be inferred from them, as has often been the case,
that they imply the approximate equality of the respective Arrhenius parameters
for a bimolecular reaction in the two phases.
A major intention of this communication is to draw attention to the urgent need
to obtain more, and more reliable, comparative kinetic results for bimolecular
reactions in the gas and liquid phases with which to test our hypothesis that the
Arrhenius parameters for these should be different. Unless such a basis of com-
parison is established, there can be little progress toward the prediction or correla-
tion of kinetic data even for simple reactions in liquids. The substantiation of our
analysis for systems that are thermodynamically ideal will be important even if
it should prove necessary to make corrections for substantial deviations from
ideality.
7 76 PATRICK

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Received November 29, 1972

Revised March 12, 1973