J. Phys. Chem.

1996, 100, 9193-9195 9193

vant Hoffs Equation for Endoreversible Chemical Reactions

F. Angulo-Brown* and L. A. Arias-Hernandez

Departamento de Fsica, Escuela Superior de Fsica y Matematicas, Instituto Politecnico Nacional,
Edificio # 9, UP Zacatenco, 07738, Mexico, DF, Mexico
ReceiVed: October 9, 1995; In Final Form: February 25, 1996X

We propose that the so-called vant Hoffs equation for the enthalpy changes in a chemical reaction may be
modified in the context of endoreversible thermodynamics. This modification takes into account the role
played by the heat supplied by the thermal bath for maintaining constant the temperature of the chemical
system. We analyze the reaction of hydrogen iodide synthesis by means of the modified vant Hoffs equation.

1. Introduction
In the last two decades an endoreversible thermodynamics
(ET) has been developed.1-5 This discipline started from the
study of Carnot-like models for thermal engines operating in
finite time. These models consist of a class of irreversible heat
engines where their whole entropy production is ascribed only
to the coupling between the working substance and its sur-
roundings and it is permitted that the working fluid undergoes
only reversible transformations. By means of this approach it
has been possible to obtain successful models and optimizations
of real heat engines.6-9 The ET scope has been extended
beyond the ordinary heat engines, such as occurred with the
early thermodynamics in the past century.10-15 In particular,
Ondrechen et al.,16,17 De Vos,18,19 and Gordon et al.20,21 extended
Figure 1. Pressure-volume diagram of an infinitesimal Carnot cycle.
the endoreversibility concept toward chemical engines, i.e.,
engines that convert differences in chemical potential into work. efficiency C of the cycle is
These engines are the analogues of heat engines driving heat
transfer for producing work from temperature differences. In dA T - dT dT
C ) )1- ) (1)
ref 10 another ET extension was introduced. In that paper the |Q| T T
superconducting transition was analyzed by means of the so-
called method of Carnot cycles (MCC)11 in a finite-time In a second step, dA is evaluated in terms of the variables of
thermodynamics context, obtaining a generalized Rutgers the thermodynamic space considered for the working substance,
relation for the finite discontinuity of the specific heat at the and so a relationship among the variables defining dA, the heat
superconducting critical temperature. In the present paper involved in the process, and the temperature is obtained.
following a method of endoreversible Carnot cycles (MECC) Naturally, all the relations obtained with this method can also
applied to the vant Hoff equilibrium box, we obtain a be derived by using thermodynamic potentials.
generalized vant Hoffs equation for gas reactions. The new As is well-known, the reversible Carnot efficiency, given by
equation is used for analyzing experimental data of heat of
reaction for the formation of hydrogen iodide. T2
C ) 1 - (2)
T1
2. Method of Endoreversible Carnot Cycles
with T2 and T1 the absolute temperatures of the cold and hot
By means of the second law of thermodynamics in its original reservoirs, respectively, is an upper bound for the efficiency of
form, Becker22 and other authors23,24 have obtained several real heat engines. This maximum efficiency limit is only
important thermodynamic equilibrium relations, for example, reachable in the completely reversible regime with no delivered
the Clausius-Clapeyron equation, the Rutgers relation, the law power and with vanishing entropy production. Thus, eq 1 has
of mass action, and the Stefan-Boltzmann law. This is the same restraints as eq 2. Within the finite-time thermody-
accomplished by applying the so-called method of Carnot cycles namics context it has been possible to build endoreversible heat
(MCC). This method takes into account the constraints of engine models which produce power output and entropy. For
reversibility and equilibrium of the classical thermodynamics example, for the endoreversible Curzon and Ahlborn (CA)
through the properties of the Carnot cycle. Briefly, the method engine,25 where the working fluid exchanges heat with its
consists in letting the system of interest undergo a virtual reservoirs by means of the so-called Newtons law of heat
infinitesimal Carnot cycle between two very close isotherm conduction, there exists a maximum power regime with ef-
branches at temperatures T and T - dT, as shown in Figure 1. ficiency given by
If the area of the cycle is denoted as dA and the absorbed heat
in the isothermic branch at temperature T is Q, then the Carnot

x
T2
CA ) 1 - (3)
X Abstract published in AdVance ACS Abstracts, April 15, 1996. T1

S0022-3654(95)03017-6 CCC: $12.00 1996 American Chemical Society

9194 J. Phys. Chem., Vol. 100, No. 21, 1996 Angulo-Brown and Arias-Hernandez

of this device and the MCC, obtained the so-called vant Hoffs
equation, given by

d ln KC Q
) 2 (9)
dT RT
where Q is the molar heat of reaction, R is the gas constant,
and KC is the constant of mass action, for example, given by

CACB
KC(T) ) (10)
CAB

for the reaction

A + B ) AB (11)
Figure 2. Temperature-entropy diagram of an endoreversible Carnot being CA,B,AB the molar concentrations in the equilibrium box
cycle: (a) with thermal resistances r1 and r2 at both couplings; (b) with (moles per unit volume). In Beckers derivation of eq 9 by
thermal resistance r2 at the cold coupling and thermal equilibrium at means of the reaction A + B f AB in a box at temperature T
the hot coupling; (c) with thermal resistance r1 at the hot coupling and and the inverse reaction AB f A + B in a box at temperature
thermal equilibrium at the cold coupling.
T - dT, the following equation is obtained22
which is between zero and C. If the CA engine works in a
regime maximizing the function E, given by h
dA h
Q h -Q
A
) ) (12)
dT T T
E ) P - T2 (4)
where Ah is the total gain in work, Q
h is the heat supplied by the
where P is the power output of the cycle, the total entropy heat bath used to keep T constant, and Q is the molar heat of
production (system plus surroundings) per cycle, and T2 is the reaction. From eq 12 and using the expression for A h , given
temperature of the cold reservoir, then ref 26 shows that the by22

[ ]
cycles efficiency will be
CA0CB0
E 1/2(C + CA) (5) h ) RT ln
A - ln KC - 1 (13)
0
CAB
This optimization criterion leads to a configuration of the
CA cycle such that for maximum E, it produces around 80% 0
with CA,B,AB the molar concentrations of substances A, B, and
of the maximum power and only about 30% of the entropy AB in the auxiliary containers of the vant Hoffs box, Becker
produced in the maximum power regime. De Vos27 showed immediately obtains eq 9. If we follow step by step Beckers
that eq 3 holds for the three cycle configurations depicted in procedure but using eq 8 instead eq 1, we obtain
Figure 2. Thus, we can use the case b in such a figure for
applying results as eqs 3 and 5 to the infinitesimal Carnot cycle h
dA RQ
h R(A
h - Q)
of Figure 1. For the endoreversible maximum power regime ) - (14)
dT T T
we have,
h and substituting it
Using eq 13 to obtain the derivative of A
CA )
dA
Q
)1-
x T - dT dT
T

2T
(6) into eq 14, we obtain

h
Q Q + (1 - R)Q
h
d ln KC Q
and for the maximum E regime we obtain ) 2 + (1 - R) 2 ) (15)
dT 2

( xT -T dT) dT/ T
RT RT RT
dA 1 T - dT
E ) 1- +1- (7) which is a generalized vant Hoffs equation for endoreversible
Q 2 T 4
3 conditions. For the full reversible case R ) 1 w (1 - R) ) 0
In both cases we cut off a Taylor expansion at first order. In and eq 9 is recovered.
an arbitrary finite-time regime we have
4. Application to the Hydrogen Iodide Case
dA dT
FT )R (8) We shall now apply eq 15 to the case of formation of
Q T hydrogen iodide. The experimental data we shall use for the
with 0 e R e 1, where for example, R ) 1/2 for the maximum heat of reaction are due to Bodestein28 and Taylor and Crist.28
power operation, R ) 3/4 for the maximum-E case, and R ) 1 The studied reaction is
for the maximum efficiency regime. The coefficient R will have H2 + I2 ) 2HI (16)
implications for every result obtainable from the MCC. Thus,
R in eq 8 is not a fitting parameter but a consequence of a If we assume that the true equilibrium heat of reaction (for
second-law analysis. Equation 8 is the basis of a method of this chemical transformation) is that obtained by means of
endoreversible Carnot cycles (MECC). equilibrium statistical mechanics,29 applied over a mixture of
ideal gases, which is given [for the temperature interval 666.6-
3. Endoreversible vant Hoff Isotherm
781.25 K] by
The vant Hoff equilibrium box is a device for performing a
gas chemical reaction in a reversible way. Becker,22 by means Q ) HreV ) -13.3 kJ/mol (17)
Endoreversible Chemical Reactions
we can estimate the deviations of the H experimental data
respect to this value (H is the enthalpy). For example, Taylor
and Crist (TC)28 reported for the chemical equation (16) a heat
of reaction
HTC ) -12.6 ( 0.076 kJ/mol (18)
[for the temperature interval 666.8-763.8 K]. As it can be seen
the experimental error is very small (in the order of 0.077 kJ/
mol). These authors showed in their paper Bodensteins
experimental points, in KC Vs 1/T, for the same reaction. A
least-squares fitting of these data leads to
HB ) -15.7 kJ/mol (19)
[for the temperature interval 666.66-781.25 K]. Both experi-
mental values of the heat of reaction were obtained by
integration of equation (9), given by
H endoreversibly, and all irreversibility sources are located at the
ln KC ) - +b (20)
RT
where H/R is the slope of this straight line in the plane ln KC
- 1/T and b is a constant. If we assume that experimental H
values mentioned here correspond to endoreversible values,
given by eq 15
Hexp ) Her ) Q + (1 - R) Q
h ) Hrev + (1 - R) Q
h Thermoeconomics; Taylor and Francis: New York, 1990.
(21)
then we can make comparisons between the theoretical equi-
librium value Hrev, and the experimental ones given by
Bodenstein and Taylor-Crist. For the TC case we have
HTC ) -12.6 kJ/mol ) -13.3 kJ/mol + (1 - R) Q
h (22)
and therefore
(1 - R) Q
h ) 0.7 kJ/mol (23)
which is a quantity considerably larger than the experimental
error in eq 18. Thus, since (1 - R) g 0, the heat supplied by
the heat bath Qh must be a positive quantity, just as expected
for a endothermic formation reaction. In the case of Boden-
steins experiment, we have
HB ) -15.7 kJ/mol ) -13.3 kJ/mol + (1 - R) Q
h (24)
and
(1 - R) Q
h ) -2.4 kJ/mol (25)
which implies (1 - R) e 0, since Q h (the heat supplied by the
bath) is necessarily positive. Unfortunately, Bodensteins
experimental errors are not available to us, since his original
paper was published on 1897.28 Thus, in this case, the
experimental HB is not consistent with the Carnot theorem.
Therefore, Bodensteins data violate the second law of ther-
modynamics and it is necessary to provide a possible explanation
for this fact. As we said, Bodensteins data were taken from
the TC paper,28 and these authors assert that due to the plot of
ln KC against 1/T of Bodensteins experimental data shows
considerable deviation from a straight line and a proper
estimation of the slope can not be made without some means
of weighting the high and low temperature values.... Appar-
ently, Taylor and Crist made such weighting for fitting Boden-
steins data to a straight line with a well-defined slope. We
J. Phys. Chem., Vol. 100, No. 21, 1996 9195
believe that this operation was the cause of an overestimation
of HB beyond the values permitted by a second law analysis.
5. Conclusions
Endoreversible thermodynamics has shown that it may be
useful to treat problems beyond thermal engines. In this paper
we propose that by means of ET ideas it is possible to modify
the expression of the so-called vant Hoffs isotherm for the
case where finite exchanges of heat between the system and its
reservoirs are considered. These exchanges unavoidably gener-
ate entropy and this fact must be expressed in a modification
of equilibrium relations. For the reaction studied here, we
propose that experimental deviations from theoretical equilib-
rium values of H are influenced for irreversible heat flows.
In fact, the endoreversible contributions (1 - R) Q h are
considerably larger than experimental errors in Hexp. Thus,
our treatment gives some insights over the analysis of experi-
mental heat reactions. Our approach permits reactions to occur
links between system and surroundings.
Acknowledgment. This work was partially supported by
COFAA-IPN (FAB) and CONACYT (L.A.A.H.).
References and Notes
(1) Sieniutycz, S., Salamon, P., Eds. Finite Time Thermodynamics and
(2) De Vos, A. EndoreVersible Thermodynamics of Solar Energy
ConVersion; Oxford University Press: Oxford, U.K., 1992.
(3) Callen, H. B. Thermodynamics and an Introduction to Thermosta-
tistics; Wiley: New York, 1985.
(4) Andresen, B.; Salamon, P.; Berry, R. S. Phys. Today 1984, 37, 62.
(5) Bejan, A. AdVanced Engineering Thermodynamics; Wiley: New
York, 1988.
(6) Mozurkewich, M.; Berry, R. S. Proc. Natl. Acad. Sci. U.S.A. 1981,
78, 1986.
(7) Mozurkewich, M.; Berry, R. S. J. Appl. Phys. 1982, 53, 34.
(8) Hoffmann, K. H.; Watowich, S. J.; Berry, R. S. J. Appl. Phys. 1985,
58, 2125.
(9) Angulo-Brown, F.; Fernandez-Betanzos, J.; Daz-Pico, C. A. Eur.
J. Phys. 1994, 15, 38.
(10) Angulo-Brown, F.; Yepez, E.; Zamorano-Ulloa, R. Phys. Lett. A
1993, 183, 431.
(11) Torres, J. L. Il NuoVo Cimento 1991, 13D, 177.
(12) Watowich, S. J.; Hoffmann, K. H.; Berry, R. S. J. Appl. Phys. 1985,
58, 2893.
(13) Watowich, S. J.; Hoffmann, K. H.; Berry, R. S. Il NuoVo Cimento
1989, 104B, 131.
(14) Brown, G. R.; Snow, S.; Andresen, B.; Salamon, P. Phys. ReV. A
1986, 34, 4370.
(15) Gordon, J. M.; Zarmi, Z. Am. J. Phys. 1989, 57, 995.
(16) Ondrechen, M.; Berry, R. S.; Andresen, B. J. Chem. Phys. 1980,
72, 5118.
(17) Ondrechen, M.; Berry, R. S.; Andresen, B. J. Chem. Phys. 1980,
73, 5838.
(18) De Vos, A. J. Phys. Chem. 1991, 95, 4534.
(19) De Vos, A. Solar Cells 1991, 31, 181.
(20) Gordon, J. M.; Orlov, V. N. J. Appl. Phys. 1993, 74, 5303.
(21) Gordon, J. M. J. Appl. Phys. 1993, 73, 8.
(22) Becker, R. Theory of Heat; Springer: Berlin, 1967; Chapter 17.
(23) Pippard, A. B. Elements of Classical Thermodynamics; Cambridge
University Press: Cambridge, U.K., 1981.
(24) Sears, F. W. An Introduction to Thermodynamics, the Kinetic Theory
of Gases, and Statistical Mechanics; Addison-Wesley: New York, 1966.
(25) Curzon, F. L.; Ahlborn, B. Am. J. Phys. 1975, 43, 22.
(26) Angulo-Brown, F. J. Appl. Phys. 1991, 69, 7465. Arias-Hernandez,
L. A.; Angulo-Brown, F. ReV. Mex. Fs. 1994, 40, 866.
(27) De Vos, A. Am. J. Phys. 1985, 53, 570.
(28) Taylor, A. H., Jr.; Crist, R. H. J. Am. Chem. Soc. 1941, 63, 1377.
(29) McQuarrie, D. A. Statistical Thermodynamics; Harper and Row:
New York, 1973; Chapter 9.
JP953017Q