Article

pubs.acs.org/jchemeduc

A Simple Method To Calculate the Temperature Dependence of the

Gibbs Energy and Chemical Equilibrium Constants
Francisco M. Vargas*
Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas 77005, United States
*
S Supporting Information

ABSTRACT: The temperature dependence of the Gibbs

energy and important quantities such as Henrys law constants,
activity coecients, and chemical equilibrium constants is
usually calculated by using the GibbsHelmholtz equation.
Although, this is a well-known approach and traditionally
covered as part of any physical chemistry course, the required
mathematical treatment for solving the equation can be
tedious and prone to mistakes especially when polynomial
expressions for the heat capacities are used. In this article, an
alternative approach is introduced in which a simple algebraic
equation can provide quick and accurate results for the
temperature dependence of the Gibbs energy and chemical
equilibrium constants. The comparison against the conven-
tional methods and values reported in the literature validate the eectiveness of the proposed equation.
KEYWORDS: Second-Year Undergraduate, Upper-Division Undergraduate, Physical Chemistry, Problem Solving/Decision Making,
Thermodynamics

T he calculation of changes of the Gibbs energy (G) can give

information on whether a process at xed pressure and
temperature is spontaneous (G < 0), nonspontaneous (G >
G1
T1
G
0 =
T0
T0
T1 1
T2
(H 0 + T 0
T
Cp dT ) dT
(5)
0), or in equilibrium (G = 0). The mathematical denition of Assuming that the isobaric heat capacity is a polynomial function
the Gibbs energy is based on the Legendre transform applied to of the temperature:
the fundamental property relation of enthalpy:1
Cp = a + bT + cT 2 + dT 3 (6)
H
G = H S
S P (1) where a, b, c, and d are constants dened for a given substance.
The solution to the GH equation, eq 5, can be expressed as eq
This leads to the following well-known identity for the Gibbs 7:
energy:
(2) G1 G 1 1 T T
G = H TS 0 = H0 + aln 1 + 0 1
where H, S, and T are the enthalpy, entropy, and temperature, T1 T0 T1 T0 T0 T1
respectively. From eq 2, it can be deduced that G is associated
b T2 c T 3T0 T3
2 2
with changes in pressure and temperature (measurable proper- + T1 2T0 + 0 + 1 + 0
ties of a system). Eq 3 is the fundamental property relation for the 2 T1 3 2 T1
Gibbs energy of a pure substance:
d T1 4T0
3 3
T 4
d G = V dP S d T (3) + + 0
4 3 T1 (7)
For an isobaric process, the temperature dependence of Gibbs
energy is usually calculated using the GibbsHelmholtz (GH) From this equation, G can be calculated after some additional
equation: algebraic manipulation. However, this procedure is tedious and
prone to calculation mistakes.
G H
= 2 The extension of the GibbsHelmholtz equation to calculate
T T T (4) the temperature dependence of chemical equilibrium constants
By dening reference states, Go and To, the eect of temperature results in the well-known vant Ho equation (vHE):
on the Gibbs energy can be calculated by a double integration,
according to eq 5: Published: February 26, 2014
2014 American Chemical Society and
Division of Chemical Education, Inc. 396 dx.doi.org/10.1021/ed3006874 | J. Chem. Educ. 2014, 91, 396401
Journal of Chemical Education Article

Grxn Hrxn and a nite change in this property can be expressed as

=
T RT RT 2 (8) G = H (TS) (14)
Grxn,1 Grxn,0 T1 Hrxn(T ) G = H (TS
= T dT 1 1 T0S0) (15)
RT1 RT0 RT 2 (9)
where subscripts 0 and 1 stand for the initial and nal states,
0

K T1 respectively.
Hrxn(T )
ln 1 = +
K0
T RT 2
dT It is possible to manipulate the expression algebraically, by
0 (10) introducing a new term, T1S0, to get
where Grxn and Hrxn are the Gibbs energy and enthalpy of G = H (TS
1 1 T0S0 + TS
1 0 TS
1 0) (16)
reaction, respectively, and K0 and K1 are the chemical equilibrium
constants at temperatures T0 and T1, respectively. G = H (S0(T1 T0) + T1(S1 S0))
For the most accurate calculations, the enthalpy of reaction
should be considered a function of the temperature by using the = H S0T T1S (17)
polynomial expressions for the heat capacities of reactants and
products as shown in eq 6. Substituting the denitions for changes in enthalpy and entropy
Elliot and Lira2 show that the solution for eq 10 can be at constant pressure:
expressed as T1

J a b c 2 d 3
H = T 0
Cp dT = Cp (T1 T0) (constant P)
(18)
ln K1 = + ln T1 + T1 + T1 + T1 I
RT1 R 2R 6R 12R
(11a) T1 Cp T1
where
S = T 0 T
dT = Cp ln
T0
(constant P)
(19)

o
J = Hrxn,0 aT0
b 2 c 3 d 4
T0 T0 T0 where C p corresponds to the average isobaric heat capacity and
2 3 4 (11b) C p is a logarithmic average, dened according to eqs 20 and 21,
respectively.
o
Grxn,0 J a b c 2 T
I= + ln T0 + T0 + T0 T 1 Cp dT
RT0 RT0 R 2R 6R o
Cp =
d 3 T1 T0
+ T0 b c d
12R (11c) a(T1 T0) + 2 (T12 T02) + 3 (T13 T03) + 4 (T14 T04)
=
However, because of the signicant eort that is required to T1 T0
evaluate eqs 11ac, it is a common practice to neglect the (20)
temperature dependence of the enthalpy of reaction to get an T C
estimate of the equilibrium constant at temperature T1. If this is T 1 Tp dT
the case, a = b = c = d = 0 and the vHE can be Cp = o
T1
approximated as ln T0

K Hrxn 1 1
ln 1 =
a ln ( ) + b(T T ) + (T
T1
T0 1 0
c
2
2
1
d
T02) + 3 (T13 T03)
K0 R T1 T0 (12) =
ln( )
T1
T0
Although eq 12 is simple to use, it might lead to a signicant error
in the calculation of the chemical equilibrium constant K1, if the (21)
temperature dierence, T1 T0, is large. Substitution of eqs 18 and 19 into eq 17 leads to eq 22, which
The objective of this article is to present an alternative allows the direct calculation of the change of the Gibbs energy as
approach to calculate Gibbs energy and chemical equilibrium a function of the temperature. This equation is the foundation of
constants as a function of the temperature in a simple but also the work presented in this article:
accurate form. Also, this work aims to enhance the learning
T1
experience of this topic, by including concepts related to state G = (Cp S0)(T1 T0) TC
1 p ln
functions, reference conditions, Gibbs energy, and absolute T0 (22)
entropy. This novel methodology can be introduced in a physical
where T0 and T1 are the initial and nal temperatures,
chemistry or thermodynamics course in conjunction with the
respectively, and S0 is the molar absolute entropy of the pure
traditional GibbsHelmholtz and vant Ho equations.
substance at temperature T0, and C p and C p are given by eqs 20
PROPOSED METHODS
Simple Method To Calculate the Temperature Dependence
and 21, respectively. The values for C p and C p for selected species
are available online as Supporting Information. The temperature
dependence of these parameters is also presented in Figure 1.
of the Gibbs Energy From Figure 1 it is clear that C p is always greater than C p and
Starting from eq 2, an innitesimal change in the Gibbs energy that the dierence between these average values increases with
can be dened as increasing temperature and with the complexity and size of the
molecule. For simple molecules, and for liquid and solids, C p
dG = dH d(TS) (13) C p and the values are less sensitive to changes in the temperature.
397 dx.doi.org/10.1021/ed3006874 | J. Chem. Educ. 2014, 91, 396401
Journal of Chemical Education Article

Writing similar equations for components B, C, and D and also

using the fact that at equilibrium G = 0:
yP
i 1

iRT1 ln = iGi(T0,P0) (Cp ,i Si ,0)
i P0 i
T1
(T1 T0) + TC
1 p , i ln
T0 (27)
where yi is the mole fraction of species i, i is the stoichiometric
number and by convention, it is positive for products and
negative for reactants.
By algebraic manipulation, eq 27 is transformed into eqs 28
and 29a:
yP
i 1
i
RT1 ln = Grxn,0
o
i(Cp ,i Si ,0)
i P0 i
Figure 1. Comparison between the average heat capacities C p (black
line) and C p (gray line) calculated using eqs 20 and 21, respectively, as T1
functions of the nal temperature, T1, for selected species. The (T1 T0) TC
1 p , i ln
T0 (28)
polynomial expressions for Cp are taken from Elliot and Lira2 and T0 =
298 K.
1 o
ln K1 = {Grxn,0 i(Gi)P }
RT1 i (29a)

Consequently, for simple molecules in the gaseous state and for with
liquids and solids: T1
(Gi)P = (Cp , i Si ,0)(T1 T0) TC
1 p , i ln
T T0 (29b)
G = (Cp S0)(T1 T0) CpT1 ln 1
T0 (23) where (Gi)p is the change of Gibbs energy with temperature for
where Cp can be calculated as an average value within the component i at constant pressure, and K1 is the chemical
temperature interval (e.g., Cp = C p), or for small changes in equilibrium constant at temperature T1, which is dened as
temperature, it can be taken as the heat capacity at the reference
yP
i 1
i
temperature, Cp,0, which is usually readily available in the K1 =
i 0
literature. P (30)
Simple Method To Calculate the Temperature Dependence
of Chemical Equilibrium Constants In this case,
The proposed method to calculate the temperature dependence yC P1 yD P1
of the Gibbs energy can be readily extended to the analysis of a
K1 =
( )( )
P0 P0
reactive system at equilibrium. Consider a hypothetical reaction yB P1
yA P1
in gaseous phase in which the behavior of the species can be
assumed ideal:
( )( )
P0 P0 (31)

A (g) + B(g) C(g) + D(g) because P0 = 1 bar,

(24)
In this case, for each substance, the Gibbs energy can be (yC P1) (yD P1)
K1 =
calculated at any pressure and temperature (T1, P1), starting from (yA P1) (yB P1) (32)
a reference state (T0, P0).
For instance, the Gibbs energy for substance A in a mixture of If eq 32 is used, it is important to keep in mind that the partial
ideal gases is given by pressures must be expressed in the same units as P0.
The value for Gorxn,0 is calculated from the Gibbs energies of
GA (T1 , P1) = GA (T0 , P0) + (CP ,A SA,0)(T1 T0) formation for the dierent species, at the same reference
T1 y P1 conditions.
TC
1 P ,A ln + RT1 ln A
T0 P0 (25) o
Grxn,0 = iGf ,i(T0 , P0) = iGof ,i
where yA is the mole fraction of A in the gaseous mixture. Note i i (33)
that SA,0 is the absolute entropy of A at P0 and T0. In this case, the The procedure developed here, that is, eqs 29a,b, represents an
standard state for every component is taken as pure ideal gas at P0 alternative approach to the solution of existing vHE, eq 10.

= 1 bar and T0 = 298 K.
For the reactive system at equilibrium (i.e., nal state),
Grxn(T , P) = GC(T , P) + G D(T , P) GA (T , P)
G B (T , P )
APPLICATION EXAMPLES
The following examples explain the procedure to calculate the
temperature dependence of the Gibbs energy and the chemical
(26) equilibrium constants, using dierent methods.
398 dx.doi.org/10.1021/ed3006874 | J. Chem. Educ. 2014, 91, 396401
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Table 1. Thermodynamic Data for Species Involved in Ammonia Synthesis Reactiona

Cp = a + bT + cT2 + dT3, J mol1 K1
Hof / Gof / So/ C p at 400 K/ C p at 400 K/
1 1
Species kJ mol kJ mol J mol1 K1 a b c d J mol1 K1 J mol1 K1
N2 (g) 0 0 191.61 31.15 1.357 102 2.680 105 1.168 108 29.19 29.19
H2 (g) 0 0 130.68 27.14 9.274 103 1.381 105 7.645 109 29.01 29.01
NH3 (g) 46.11 16.45 192.45 27.31 2.383 102 1.707 105 1.185 108 37.21 37.13
a
Hof , Gof and So are taken from ref 3. The coecients for Cp are taken from ref 2.

Example 1: Change in Gibbs Energy with Temperature G = G1 G0 = (35.06 192.45)(400 298)

Calculate the change in Gibbs energy when 1 mol of gaseous 400
ammonia is heated at constant pressure P = 1 bar from T0 = 298 K (35.06)(400)ln = 20.18 kJ mol1
298
to T1 = 400 K. Assume that gaseous ammonia at these conditions
behaves as an ideal gas. The expression for the heat capacity of In this case, the error produced by the approximation C p = C p =
ammonia is reported in literature2 as Cp,0 is less than 0.1%. Also, eq 35 gives the same result (i.e., G =
20.18 kJ mol1) when Cp,0 is used.
Cp = 27.31 + 2.383 102T + 1.707 105T 2 Example 2: Chemical Equilibrium Constant at a Given
Temperature
1.185 108T 3 (34)
Calculate the chemical equilibrium constant for the formation of
1 1 ammonia from its elements, in a gaseous phase reaction at T =
where Cp is given in units of J mol K and T in K.
Solution via the GibbsHelmholtz Equation. The Gibbs 400 K, assuming that all the species behave as ideal gases.
energy of formation of gaseous ammonia at 298 K is 16.45 kJ The chemical reaction that takes place in this case is
mol1 and the absolute entropy, S0, at the same temperature is N2(g) + 3H 2(g) 2NH3(g) (36)
192.45 J mol1 K1.3 Thus, H = G + TS = 16,450 + (298)
(192.45) = 40,900 J mol1. This method makes use of the and relevant thermodynamic data for this reaction is given in
integrated form of the GibbsHelmholtz equation, eq 7, Table 1.
The values of C p and C p are taken from the Supporting
G = G1 G0 Information, and are calculated using eqs 20 and 21 with the
T 1 coecients for Cp from ref 2. More information on thermo-
1
= G0 1 1 T1 H0 physical properties can be found in ref 4.
T0 T1 T0 Solution via Method 1. Full Solution of vant Ho
Equation. Applying the solution to the vHE proposed by Elliot
T T b T2 and Lira,2 with eqs 11ac): a = 57.95, b = 3.341 102, c
+ aln 1 + 0 1 + T1 2T0 + 0
T0 T1 2 T1 = 4.877 105, and d = 3.496 108; Horxn,0 = 92,220 J,
Gorxn,0 = 32,900 J, J = 76,795.7 J, I = 21.32,
c T1 3T0
2 2
T 3 d T 3 4T03 T 4
+ + 0+ 1 + 0 76,795.7 57.95
3 2 T1 4 3 T1 ln K1 = + ln(400)
(8.314)(400) 8.314
(35) 3.341 102 4.877 105
+ (400) +
Substituting the known values, G0 = 16,450 J mol1, T0 = 298 K, 2(8.314) 6(8.314)
T1 = 400 K, a = 27.31, b = 2.383 102, c = 1.707 105, and d = 2 3.496 108
1.185 108 into the eq 35, G = G1 G0 = 20.20 kJ mol1. (400) + (400)3 + 21.32
12(8.314)
Solution via the New Equation. Using the new approach
proposed in this work, the Gibbs energy is directly calculated by ln K1 = 3.58 K1 = 36.04
applying eq 22.
Solution via Method 2. Approximated Solution of vant
T1 Ho Equation. In this method, the eect of temperature on the
G = (Cp S0)(T1 T0) TC
1 p ln enthalpy of reaction is neglected, and the chemical equilibrium
T0 (22) constant is obtained by solving eq 12:
The values of C p = 37.2 J mol1 K1 and C p = 37.1 J mol1 K1 are K Hrxn 1 1
taken from Table A.1 (in the Supporting Information), and S0 = ln 1 =
192.45 J mol1 K1 as in the previous method. With this K0 R T1 T0
o
1
o
information, the change of the Gibbs energy can be readily Grxn,0 Hrxn 1
obtained: G = G1 G0 = 20.20 kJ mol1. Note that the values ln K1 =
RT0 R T1 T0
obtained by the two methods are identical but the second
o o
method oers a simpler procedure. Hrxn,0 = 92,220 J Grxn,0 = 32,900 J
When the temperature dependence of the heat capacities is
unknown or the interest is on a rough estimate of the changes of 32,900 92,220 1 1
ln K1 =
Gibbs energy, it can be assumed that C p = C p = Cp,0, where Cp,0 is (8.314)(298) 8.314 400 298
the heat capacity at 298 K. For ammonia, Cp,0 = 35.06 J mol1
K1.3 ln K1 = 3.78 K1 = 44.14

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Figure 2. Comparison of dierent methods to calculate the temperature dependence of equilibrium constant K1.

Solution via Method 3. New Equation (C p Cp and Both 1

ln K1 = {+32,900 [(2)( 20,215.9)
Are Functions of T). Applying eq 29b to the three species, with (8.314)(400)
the information provided in Table 1: (GN2) = 20,003.9 J
+ 20,003.9 + (3)(13,786.2)]}
mol1, (GH2) = 13,786.2 J mol1, (GNH3) = 20,206.5 J
mol1. And substituting the values in eq 29a with Grxn,0 =
ln K1 = 3.60 K1 = 36.56
32,900 J, one can readily get
1 Solution via Method 3b. New Equation (C p = Cp= Cp,0 =
ln K1 = {+32,900 [(2)( 20,206.5) Constant). In this case, the heat capacities are assumed to be
(8.314)(400) independent of the temperature. Thus, C p = C p = Cp,0, where Cp,0
+ 20,003.9 + (3)(13,786.2)]} is obtained from evaluation of the heat capacity polynomials at T
= 298 K. These values are 29.2, 28.9, and 35.6 J mol1 K1 for N2,
H2, and NH3, respectively. Substituting these numbers in eq 29b:
ln K1 = 3.59 K1 = 36.36 (GN2) = 20,004.1 J mol1, (GH2) = 13,784.5 J mol1,
Solution via Method 3a. New Equation (C p = C p and Cp (GNH3) = 20,190.5 J mol1. And substituting the values in eq
Is a Function of T). In this case, only one average heat capacity is 29a, with Gorxn,0 = 32,900 J, one can readily get
required. C p = C p = T1
T0 (Cp dT)/(T1 T0), (GN2) = 20,003.9
1
J mol1, (GH2) = 13,786.2 J mol1, (GNH3) = 20,215.9 J ln K1 = {+32,900 [(2)( 20,190.5)
(8.314)(400)
mol1. And substituting the values in eq 29a with Gorxn,0 =
32,900 J, one can readily get + 20,004.1 + (3)(13,784.5)]}

400 dx.doi.org/10.1021/ed3006874 | J. Chem. Educ. 2014, 91, 396401

Journal of Chemical Education
ln K1 = 3.58 K1 = 36.07
From all the ve methods tested, the approximated solution of
vHE (method 2) shows the greatest deviation from the value
obtained using the full solution of vHE (method 1). The
equation proposed in this work and its variants (methods 3, 3a,
and 3b) give very similar results to the full solution of vHE
(method 1). In fact, the small dierence between methods 1 and
3 is due to round-o errors.
These two examples illustrate the application of the dierent
methods to calculate the temperature dependence of the
chemical equilibrium constants, and it is clear that although the
solution of the full vHE oers an accurate result, the eort to
solve the necessary equations is also signicant. The model that is
proposed in this work oers the same level of accuracy, but with a
simpler procedure.
VALIDATION OF THE PROPOSED EQUATION
To provide a full validation of the proposed model and a more
detailed analysis of the limitation of the other methods, four
dierent reactions in a wide range of temperatures (2731500
K) have been studied. The full solution of the vHE (method 1)
for the dierent cases is used as a reference (i.e., exact solution)
and the simplied solution of vHE (method 2), the new equation
(method 3) as well as two of its variants (methods 3a and 3b) are
also tested in this study.
The results are presented in Figure 2. In all the cases, the new
equation (method 3, represented by a continuous black line in
Figure 2), perfectly matches with the results obtained from the
full vHE (method 1, black circles) in the entire temperature
range, which is expected, because the two methods are
mathematically equivalent. The simplied solution of vHE
(method 2, gray line) works well for the ethylene hydration
reaction, but increasingly underperforms as the temperature
increases for the other three reactions. Method 2 works
particularly well when the Cp is small, which is the case for
the ethylene hydration reaction. As expected, the error increases
with increasing temperature and for larger magnitudes of Cp.
The sign of Cp denes the type of deviation in the calculation.
Positive values of Cp cause underprediction of the value of lnK1,
whereas negative values of Cp cause overprediction. In method
3a, it is assumed that the two average heat capacities are equal and
that C p is a function of the temperature. The results shown in
Figure 2 as a dashed line validate that this method gives a good
approximation, while it reduces the eort in calculating the
average heat capacity values. In method 3b, it is assumed that the
heat capacities are constants, independent of the temperature (C p
= C p = Cp,0) where Cp,0 is the heat capacity at 298 K.
Method 3b, represented in Figure 2 by a dotted line, gives a
better prediction than the simplied solution of vHE (method 2)
for cases where Cp is large, and the values of the heat capacities
do not change signicantly with the temperature. As presented in
Figure 1, this is especially the case for simple molecules, such as
H2, N2, O2, NO, CO. In fact, a combination of methods 3a and 3b
is feasible, in which C p = C p = Cp,0 can be used for simple
molecules involved in the reaction, whereas a full calculation is
done to determine C p and C p, from eqs 20 and 21, for more
complex molecules. The worst result obtained by method 3b is
for the ethylene hydration reaction because both ethylene and
ethanol double the values of their heat capacities from 273 to
1500 K.
401
Article
CONCLUSIONS AND PEDAGOGICAL
IMPLICATIONS
A new method to calculate the temperature dependence of the
Gibbs energy has been developed. The proposed model enables
an accurate and simple method for determining the changes in
Gibbs energy as a function of the temperature. Furthermore, the
procedure can be readily extended to the calculation of chemical
equilibrium constants at any temperature. In the conventional
vant Ho method, it is usually assumed that the enthalpy of
reaction is independent of the temperature to facilitate the
calculations, which can induce a signicant error in the case of
reactions occurring at high temperature and/or when the
dierence Cp is large. In the new model, the assumption of
constant enthalpy of reaction is not required, and the simplicity
of the equations is retained. Furthermore, as it was also proven in
this article, the new equation gives the same level of accuracy as
the full van Ho equation, but because the calculation procedure
is greatly simplied, it is less prone to calculation mistakes.
ASSOCIATED CONTENT
* Supporting Information
S
Heat capacity table. This material is available via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: fvargas@rice.edu.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
The author gratefully acknowledges support from Tecnologico de
Monterrey, through Catedra de Energia Solar y Termociencias
(Grant CAT-125). The support of Shyam Benny Kadali and
Sameer Punnapala in early versions of this manuscript is also
greatly appreciated. The author also thanks the anonymous
reviewers for their careful assessment, which helped to improve
this article. In particular, section 4 is largely the result of
addressing the constructive feedback of one of the referees.
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(2) Elliot, J. R.; Lira, C. T. Introductory Chemical Engineering
Thermodynamics, 2nd ed.; Prentice Hall: New York, 2009; pp 652657.
(3) Atkins, P.; de Paula, J. Physical Chemistry, 9th ed.; W.H. Freeman:
and Co.: New York, 2009; pp 918923.
(4) NIST Chemistry WebBook. http://webbook.nist.gov/chemistry/
(accessed Feb 2014).
dx.doi.org/10.1021/ed3006874 | J. Chem. Educ. 2014, 91, 396401