Proc. Natl. Acad. Sci.

USA
Vol. 93, pp. 7452-7453, July 1996
Chemistry

Persistent confusion of total entropy and chemical system

entropy in chemical thermodynamics
(van't Hoff equation/model dependent thermodynamics)
GREGORIO WEBER
University of Illinois School of Chemical Sciences, 600 South Mathews Avenue, Urbana, IL 61801
Contributed by Gregorio Weber, February 29, 1996

ABSTRACT The change in free energy with temperature (dG) dH dSj

at constant pressure of a chemical reaction is determined by T d -Si. [5]
the sum (dS) of changes in entropy of the system of reagents, dT dT dT
dS;, and the additional entropy change of the surroundings, Eq. 4 refers the changes in free energy to the entropy of system
dSH, that results from the enthalpy change, dH. A faulty and surroundings, as demanded by the second law of thermo-
identification of the total entropy change on reaction with dS; dynamics, whereas Eq. 5 expresses the free energy change in
has been responsible for the attribution of general validity to terms of properties intrinsic to the system. If we neglect this
the expressions (dAG/dT)p = -AS; and d(AG/1)/d(1/T) = difference and simply write Eq. 5 in the form
AH, which are found in most textbooks and in innumerable
papers. dG dH dS
[5']
The free energy associated to each reagent entering in chem- dT) dT dTS
ical reaction under constant temperature and pressure is given we risk concluding from Eqs. 4 and 5' that
by the familiar Gibbs function
G = H - TSi.
(dG/dT)p= -Si [6]
[1]
and inadvertently also that SH + Si = Si. Yet the simple mistake
Eq. 1 is a statement of the heat content of the reagent, part of embodied in Eq. 6 has been exhibited by textbooks and is
which is actual and determined by its intrinsic entropy Si, and current in the literature for the last 70 and perhaps more years.
partly potential, determined by H, the energy locked in the That dSi does not represent the total entropy change is brought
bonds that partake in the chemical reaction. In an isothermal out by the many cases in which the standard change in Si in the
reaction reaction is negative. These instances do not contradict the
dG = dH - TdSi, [2] second law because of the larger entropy increase of the
surroundings that follows the decrease in H. In fact, an
the actual change in the composition of the system does not immediate corollary of the second law is that: If the entropy
provide a measure of the enthalpy change dH, which can only of any part of a system decreases in the course of an isothermal
be appraised by the corresponding change in heat content of process, there must be a concomitant and larger increase in
the surroundings of magnitude dQH = -dH. Similarly, TdSj another part of the same system.
provides for an additional change in the heat content of the The erroneous identification of the entropy change of the
surroundings of magnitude dQi. Calorimetric measurements chemical system dSi with the total entropy change dSH + dSj
do not separate these two interdependent but distinct heat leads immediately to a fixed relation of the changes in enthalpy
changes and only their sum dQ = - (dQH + dQj) is measurable. and entropy with temperature: If dG/dT = -Si, it follows from
Neglecting the very small contribution to the external work, Eq. 5' that
pdV, which is the case in practically all reactions in solution, the
change in free energy of a reagent in an isothermal reaction dH/dT = T(dSj/dT) [7]
may be expressed as a change in entropy dS of its surroundings,
the sum of changes dSH and dSj is valid for each reagent in a chemical reaction, and then for
all reactions
dG = - T(dSH + dSi) = - TdS. [3] dAH/dT = T(dASj/dT), [8]
As such, Eq. 3 satisfies Planck's criterion (1, *) that the
decrease in free energy in a spontaneous process is determined where AH and ASi are the standard changes in enthalpy and
by the change in entropy of all the bodies in which the heat intrinsic entropy in the reaction, respectively.
content changes in the reaction, a condition essentially re- It also follows that
quired by the second law (2). It follows from Eq. 3 that the free 1 dAH dASj
energy change of the reagent with temperature at constant -
[8']
pressure equals T d(l1/T) d(l1/T)
(dG/dT)p = - S. [4] *Planck establishes the distinction between the entropy of the envi-
ronment, 40, and that of the reagents, 4, states the application of the
From Eq. 1, we have second law to reactions as d(4 + 40) - 0, and consistently uses 4) in
the same way as I use Si. He notes that dU = dH - pdVoften exceeds
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The publication costs of this article were defrayed in part by page charge
Tdo, thus justifying Berthelot's rule. Unfortunately, he did not
explicitly state that in these cases one can have do 0, which should
-

payment. This article must therefore be hereby marked "advertisement" in have precluded the systematic erroneous identification of S = (A + (A.
accordance with 18 U.S.C. §1734 solely to indicate this fact. with Si = (A.
7452
 Chemistry: Weber
Starting with the Gibbs relation AG =
Al TASi and dividing
by T,
AG/T= AH/T-AS,
and
d(AG/T) 1 dAH dASi
=
AH + -___
d(l/T) Td(1/T) d(1/T)
but, according to Eq. 8', because the second and third term
cancel each other
d(AG/T) = AH
d(1/T)
The last is the celebrated van't Hoff equation that has been
used for so long in the determination of enthalpy changes in
chemical reactions that all papers and most textbooks consider
it unnecessary to enter into a detailed discussion of its deri-
vation. Actual examples of the mistaken derivation of Eq. 11
encountered in classical textbooks of chemical thermodynam-
ics are given elsewhere (3). No textbook that I have consulted
writes explicitly Eq. 10, which could have prompted somebody
to ask what happens when AH = 0 and ASi > 0. Instead they
omit all differences in notation necessary to distinguish Si from
S of Eq. 3, and then from Eqs. 4 and 5' derive Eq. 8' and with
this in hand declare the universal worth of the van t'Hoff
relation of Eq. 11. The most important consequence of the
dismissal of the relations in Eqs. 8 and 8' is that in a chemical
reaction, there are no fixed relations between the standard
changes in enthalpy and entropy deducible from the laws of
thermodynamics. Consequently, calculation of the effects of
pressure and temperature on the chemical equilibria require
suitable thermodynamic models that describe the relations of
H and S expected for each reagent. While success of these ad
hoc models will not confer on the results the certainty wrongly
attributed in the past to the standard changes in enthalpy and
entropy determined by the van't Hoff equation, they provide
us with an opportunity to establish meaningful relations between
macroscopic thermodynamics and microscopic chemistry.
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Proc. Natl. Acad. Sci. USA 93 (1996) 7453
It may be asked why the van't Hoff equation has proven
useful in spite of its spurious derivation. It is simply that most
chemical reactions, as already recognized by Berthelot (4) in
[9] 1897, are driven by the change in enthalpy. Any error owing to
the neglect of the much smaller entropy contribution would
pass unnoticed because we have no other means of indepen-
dently evaluating either AHl or ASi. The consideration of the
association of protein subunits, which are typical entropy
[10] driven reactions (5, 6), led me to observe the extremely
different results obtained from Eqs. 10 and 11 when specific
relations of H and S of the reagents were assumed (7, 8) to
permit modeling the reaction. Eventually, I was able to trace
the origin of Eq. 11 to the erroneous Eqs. 8 and 8', and the
[1] original confusion between Si and S = SH + Si. This long-
standing mistake has clearly arisen from inability to distinguish
between the variational conditions that define the chemical
equilibrium, originally stated by Gibbs (9), and the application
of the laws of thermodynamics to actual processes like those
that result from finite changes in temperature or pressure. It
provides a striking example of Truesdell's dictum (10): In
thermodynamics, " Confusion of the nature of the equilibrium
of a large class of bodies with the effect of processes undergone
by members of a small class of bodies is nearly universal."
I thank Drs. H. G. Drickamer, D. M. Jameson, G. U. Nienhaus, and
G. D. Reinhart for their comments and suggestions. This work was
supported by U.S. Public Health Service Grant GM11223.
1. Planck, M. (1922) Treatise on Thermodynamics (Dover, New
York), pp. 103-119.
2. Serrin, J. (1977) Arch. Rational Mech. Anal. 70, 355-371.
3. Weber, G. (1995) J. Phys. Chem. 99, 13051.
4. Berthelot, M. (1897) Thermochimie (Gauthier-Villars, Paris),
Vol. 1, p. 13.
5. Lauffer, M. (1975) Entropy Driven Reactions in Biology (Springer,
New York).
6. Silva, J. L. & Weber, G. (1993) Annu. Rev. Phys. Chem. 44,
89-113.
7. Weber, G. (1993) J. Phys. Chem. 97, 7105-7115.
8. Weber, G. (1993) J. Phys. Chem. 99, 1052-1059.
9. Gibbs, J. W. (1993) Scientific Papers I: Thermodynamics (Ox Bow,
Woodbridge, CT), pp. 56-62.
10. Truesdell C. (1984) Rational Thermodynamics (Springer, New
York), 2nd Ed., p. 31.