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On the derivation of the Gibbs–Helmholtz equation

Article  in  ChemTexts · April 2016

DOI: 10.1007/s40828-016-0023-7

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ChemTexts (2016) 2:5
DOI 10.1007/s40828-016-0023-7

LECTURE TEXT

On the derivation of the Gibbs–Helmholtz equation

Balázs Roósz1 • Csaba Visy1 • István Nagypál1

Received: 1 February 2016 / Accepted: 19 February 2016

Ó Springer International Publishing Switzerland 2016

Abstract Based on a real event in the classroom during This fundamental equation is very important, since it is
the physical chemistry course for undergraduate students, a the starting point to the van’t Hoff equation, expressing the
new derivation is presented for the proof of the Gibbs– temperature dependence of the equilibrium constant that
Helmholtz equation. Tried in subsequent years, it received interprets quantitatively the shift of chemical equilibrium
positive reflection from chemistry BSc students proving upon temperature change, predicted in the Le Chatelier–
that this straightforward derivation, which leads from the Brown principle.
definition of G to the final expression in five steps, is more In a widely used physical chemistry lecture book [1] the
easily comprehensible. At the same time it helps the starting point to the G–H equation is the definition of
instructor to shed light—based on their temperature Gibbs’ free energy, and the relation between its tempera-
dependence—on the relationship between thermodynamic ture coefficient and entropy:
state functions.  
oG
G ¼ H  TS; S ¼ : ð2Þ
oT p
Keywords Physical chemistry  Thermodynamics 
Undergraduate students  More comprehensible derivation As a next step, these two equations are combined to
result
 
oG GH
Introduction ¼ ð3Þ
oT p T
There are several paths in the different textbooks [1–5] for and a transformation gives
the derivation of the Gibbs–Helmholtz (G-H) equation:  
  oG G H
oG=T H  ¼ : ð4Þ
¼ 2 ð1Þ oT p T T
oT p T
Then it is suggested to recognize the validity of the
The Gibbs–Helmholtz equation expresses the tempera- equation
ture dependence of the ratio of G/T at constant pressure,    
which is a composite function of T as G itself also depends oG G o G
 ¼T : ð5Þ
on the temperature. oT p T oT T p

However, this conclusion is not self-evident for the

average chemistry student, as its approval needs not only
the derivation of a composite function:
     
& Csaba Visy o G 1 oG o 1
[email protected] ¼ þG ð6Þ
oT T p T oT p oT T p
1
Department of Physical Chemistry and Materials Science, but also a comparison with the rearranged form of Eq. 4:
University of Szeged, Rerrich sq. 1, Szeged 6720, Hungary

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5 Page 2 of 3 ChemTexts (2016) 2:5

  "  #
o G 1 oG G H Thus, Eqs. 8–13 represent a direct, straightforward path
¼  ¼ 2 ð7Þ to obtain G-H equation from the definition of G in five
oT T p T oT p T T
steps. We are aware that in one of the referred textbooks
As it can be seen, the train of thought is not totally [4] the derivation through Eqs. (8–10) and (13) is pre-
straightforward, which hampers the logic of the derivation. sented. However, McQuarrie and Simon have to refer also
According to classroom experiences, the derivation rises to previous equations to prove validity of Eq. 13, where
difficulties in the sense that it is not so easy to realize that they come to the conclusion in four further steps. Thus, the
the left side of Eq. 5 is the product of T with the derivative derivation consists altogether of eight elements. We
of G/T. emphasize that our derivation in five steps includes the
Some years ago during the Physical Chemistry course, concrete proof that the sum of the first and third term in
one of the then students (B.R.) of us (C.V. and I.N.) sug- Eq. (10) is zero.
gested the following derivation: let us take the definition of It is illuminating to point out that—assuming that H and
G S were temperature independent quantities—we could
derive the Gibbs–Helmholtz equation in one step from
G ¼ H  TS ð8Þ
Eq. 10. But the assumption is evidently wrong. The coin-
and divide both sides by T cidence, however, reveals that the first derivatives of H and
S with respect to temperature are related, and this relation
G H
¼ S ð9Þ results in the elimination of the first and third terms in
T T
Eq. 10.
If we derive this equation with respect to T at constant Finally we may mention in the basic course the so-called
pressure, compensation effect [6]. It expresses that the change of
 H      G is, in general, much less sensitive to the change of the
o T S 1 oH H oS
¼  2 ð10Þ different parameters than that of the change of H and
oT p T oT p T oT p S. This is clearly reflected in the above mentioned elimi-
we receive Eq. 10 consisting of three terms. Comparing it nation when the changing parameter is the temperature.
with Eq. 1, it can be realized that the first and the third Further details of the compensation effect, however, are
terms are missing, they assumingly have cancelled each treated in the master courses.
other. Seemingly, it might be also the result if H and S were Although we do not have at hand exact statistical data
independent of the temperature. Since it is evidently not the concerning the usage of physical chemistry lecture
case recognized also by himself, this striking coincidence books, the presented straightforward derivation in this
prompted us to find an easily comprehensible proof, and to simple, tutorial form, leading from the definition equa-
show the students through a simple reasoning, why the sum tion of G to the final form of the G-H equation in five
of these two terms in Eq. 10 gives zero. steps, is not found in the generally used textbooks [1–5].
For the first term we have Our experiences in the classroom are unambiguous
  that—when presented to our students during the subse-
1 oH Cp
¼ ð11Þ quent semesters—majority of them reflected that it was
T oT p T
easier to comprehend than the derivation given in their
In order to receive the third term, we consider that for textbook [1]. Beyond the didactic advantage, the pre-
the infinitesimal change in entropy at constant pressure we sented derivation and its arguments shed light on the fact
have that the temperature dependence of H and S are related,
and that this relation is the basis of the compensation
dqrev Cp dT
dS ¼ ¼ ð12Þ effect.
T T
Equation 12 implies that
 
oS Cp
¼ ð13Þ
oT p T
References
so that we obtained the same expression for the first and
1. Atkins PW (2005) Physical chemistry, 6th edn. vol 1. Oxford
third element in Eq. 10. Since the first and third term at the Press, London, pp 45–46
right side in Eq. 10 are identical but with opposite sign, 2. Alberty RA, Silbey RJ (1913) Physical chemistry, 1st edn. vol 1.
they are cancelled. Quod erat demonstrandum. Wiley, New York (and its later editions), pp 117–118

123
ChemTexts (2016) 2:5 Page 3 of 3 5

3. Noggle JH (1989) Physical chemistry, 2nd edn. vol 1. Scott, 5. Tester JW, Modell M (1997) Thermodynamics and its applica-
Foresman and Company, Glenview, pp 145 tions, 3rd edn. Prentice Hall, New Jersey, pp 153, 341
4. McQuarrie DA, Simon JD (1997) Physical chemistry: a molecular 6. Benson SW (1976) Thermochemical kinetics, 2nd edn. Wiley,
approach, vol 1. University Science Books, Sousalito, pp 854–855 New York, pp 21–23
and 902–903

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