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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 conventional 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

G
G1
0 =
T1
T0

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 >
0), or in equilibrium (G = 0). The mathematical denition of
the Gibbs energy is based on the Legendre transform applied to
the fundamental property relation of enthalpy:1

G = H S
S P

Cp dT ) dT

(5)

(6)

1
T

G
T
G1
1
0 = H0 + aln 1 + 0 1

T1
T0
T0
T1
T1
T0

where H, S, and T are the enthalpy, entropy, and temperature,


respectively. From eq 2, it can be deduced that G is associated
with changes in pressure and temperature (measurable properties of a system). Eq 3 is the fundamental property relation for the
Gibbs energy of a pure substance:
(3)

For an isobaric process, the temperature dependence of Gibbs


energy is usually calculated using the GibbsHelmholtz (GH)
equation:

2
2
T2
T3
b
c T 3T0
T1 2T0 + 0 + 1
+ 0
2
T1
3
2
T1

3
3
T 4
d T1 4T0

+ 0
4
3
T1

(7)

From this equation, G can be calculated after some additional


algebraic manipulation. However, this procedure is tedious and
prone to calculation mistakes.
The extension of the GibbsHelmholtz equation to calculate
the temperature dependence of chemical equilibrium constants
results in the well-known vant Ho equation (vHE):

(4)

By dening reference states, Go and To, the eect of temperature


on the Gibbs energy can be calculated by a double integration,
according to eq 5:
2014 American Chemical Society and
Division of Chemical Education, Inc.

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
7:

(2)

H
G
= 2

T T
T

1
(H 0 +
T2

Cp = a + bT + cT 2 + dT 3

This leads to the following well-known identity for the Gibbs


energy:

d G = V dP S d T

T1

Assuming that the isobaric heat capacity is a polynomial function


of the temperature:

(1)

G = H TS

Published: February 26, 2014


396

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Article

Hrxn
Grxn

=
T RT
RT 2

Grxn,1
RT1

Grxn,0

K
ln 1 = +
K0

RT0

T1

and a nite change in this property can be expressed as


(8)

T1

Hrxn(T )
RT 2

Hrxn(T )
RT 2

dT

(9)

dT
(10)

o
Grxn,0

RT0
d 3
T0
+
12R

H =

S =

T1

Cp dT = Cp (T1 T0) (constant P)

T1

Cp

dT = Cp ln

T1
(constant P)
T0

(18)

(19)

where C p corresponds to the average isobaric heat capacity and


C p is a logarithmic average, dened according to eqs 20 and 21,
respectively.

(11b)

Cp =

T 1 Cp dT
o

T1 T0
b

(11c)

a(T1 T0) + 2 (T12 T02) + 3 (T13 T03) + 4 (T14 T04)


T1 T0
(20)
T C

Cp =

T 1 Tp dT
o

ln

(12)

T1
T0

( ) + b(T T ) + (T
ln( )

a ln

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
temperature dierence, T1 T0, is large.
The objective of this article is to present an alternative
approach to calculate Gibbs energy and chemical equilibrium
constants as a function of the temperature in a simple but also
accurate form. Also, this work aims to enhance the learning
experience of this topic, by including concepts related to state
functions, reference conditions, Gibbs energy, and absolute
entropy. This novel methodology can be introduced in a physical
chemistry or thermodynamics course in conjunction with the
traditional GibbsHelmholtz and vant Ho equations.

T1
T0

c
2

2
1

T02) + 3 (T13 T03)

T1
T0

(21)

Substitution of eqs 18 and 19 into eq 17 leads to eq 22, which


allows the direct calculation of the change of the Gibbs energy as
a function of the temperature. This equation is the foundation of
the work presented in this article:

G = (Cp S0)(T1 T0) TC


1 p ln

T1
T0

(22)

where T0 and T1 are the initial and nal temperatures,


respectively, and S0 is the molar absolute entropy of the pure
substance at temperature T0, and C p and C p are given by eqs 20
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.
From Figure 1 it is clear that C p is always greater than C p and
that the dierence between these average values increases with
increasing temperature and with the complexity and size of the
molecule. For simple molecules, and for liquid and solids, C p
C p and the values are less sensitive to changes in the temperature.

PROPOSED METHODS

Simple Method To Calculate the Temperature Dependence


of the Gibbs Energy

Starting from eq 2, an innitesimal change in the Gibbs energy


can be dened as

dG = dH d(TS)

However, because of the signicant eort that is required to


evaluate eqs 11ac, it is a common practice to neglect the
temperature dependence of the enthalpy of reaction to get an
estimate of the equilibrium constant at temperature T1. If this is
the case, a = b = c = d = 0 and the vHE can be
approximated as

(17)

Substituting the denitions for changes in enthalpy and entropy


at constant pressure:

J
a
b
c 2
ln T0 +
T0 +
T0
+
2R
6R
RT0
R

K
Hrxn 1
1
ln 1 =

R T1
T0
K0

(16)

= H S0T T1S

where

I=

(15)

G = H (S0(T1 T0) + T1(S1 S0))

(11a)

b 2 c 3 d 4
T0
T0
T0
2
3
4

G = H (TS
1 1 T0S0)

G = H (TS
1 1 T0S0 + TS
1 0 TS
1 0)

J
a
b
c 2
d 3
T1 I
T1 +
T1 +
+
ln T1 +
RT1
R
2R
6R
12R

o
J = Hrxn,0
aT0

(14)

where subscripts 0 and 1 stand for the initial and nal states,
respectively.
It is possible to manipulate the expression algebraically, by
introducing a new term, T1S0, to get

where Grxn and Hrxn are the Gibbs energy and enthalpy of
reaction, respectively, and K0 and K1 are the chemical equilibrium
constants at temperatures T0 and T1, respectively.
For the most accurate calculations, the enthalpy of reaction
should be considered a function of the temperature by using the
polynomial expressions for the heat capacities of reactants and
products as shown in eq 6.
Elliot and Lira2 show that the solution for eq 10 can be
expressed as
ln K1 =

G = H (TS)

(13)
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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

P0

iGi(T0,P0) (Cp ,i Si ,0)


i

(T1 T0) + TC
1 p , i ln

T1

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
i 1
o
RT1 ln = Grxn,0

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
functions of the nal temperature, T1, for selected species. The
polynomial expressions for Cp are taken from Elliot and Lira2 and T0 =
298 K.

1
o
{Grxn,0

RT1

(23)

i(Gi)P }

(28)

(29a)

T1
T0

(29b)

where (Gi)p is the change of Gibbs energy with temperature for


component i at constant pressure, and K1 is the chemical
equilibrium constant at temperature T1, which is dened as
yP
i
i 1
K1 =
P
i 0

Simple Method To Calculate the Temperature Dependence


of Chemical Equilibrium Constants

(30)

In this case,
yC P1

The proposed method to calculate the temperature dependence


of the Gibbs energy can be readily extended to the analysis of a
reactive system at equilibrium. Consider a hypothetical reaction
in gaseous phase in which the behavior of the species can be
assumed ideal:

K1 =

yD P1

( )( )
( )( )
P0

P0

yA P1

yB P1

P0

(31)

P0

because P0 = 1 bar,

(24)

In this case, for each substance, the Gibbs energy can be


calculated at any pressure and temperature (T1, P1), starting from
a reference state (T0, P0).
For instance, the Gibbs energy for substance A in a mixture of
ideal gases is given by

K1 =

(yC P1) (yD P1)


(yA P1) (yB P1)

(32)

If eq 32 is used, it is important to keep in mind that the partial


pressures must be expressed in the same units as P0.
The value for Gorxn,0 is calculated from the Gibbs energies of
formation for the dierent species, at the same reference
conditions.

(25)

o
Grxn,0
=

where yA is the mole fraction of A in the gaseous mixture. Note


that SA,0 is the absolute entropy of A at P0 and T0. In this case, the
standard state for every component is taken as pure ideal gas at P0
= 1 bar and T0 = 298 K.
For the reactive system at equilibrium (i.e., nal state),

iGf ,i(T0 , P0) = iGof ,i


i

(33)

The procedure developed here, that is, eqs 29a,b, represents an


alternative approach to the solution of existing vHE, eq 10.

APPLICATION EXAMPLES
The following examples explain the procedure to calculate the
temperature dependence of the Gibbs energy and the chemical
equilibrium constants, using dierent methods.

Grxn(T , P) = GC(T , P) + G D(T , P) GA (T , P)


G B (T , P )

T1

T0

(Gi)P = (Cp , i Si ,0)(T1 T0) TC


1 p , i ln

where Cp can be calculated as an average value within the


temperature interval (e.g., Cp = C p), or for small changes in
temperature, it can be taken as the heat capacity at the reference
temperature, Cp,0, which is usually readily available in the
literature.

GA (T1 , P1) = GA (T0 , P0) + (CP ,A SA,0)(T1 T0)


y P1
T1

TC
+ RT1 ln A
1 P ,A ln
T0
P0

with

Consequently, for simple molecules in the gaseous state and for


liquids and solids:

A (g) + B(g) C(g) + D(g)

(T1 T0) TC
1 p , i ln

ln K1 =

T
G = (Cp S0)(T1 T0) CpT1 ln 1
T0

i(Cp ,i Si ,0)

(26)
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Article

Table 1. Thermodynamic Data for Species Involved in Ammonia Synthesis Reactiona


Cp = a + bT + cT2 + dT3, J mol1 K1

Hof /
1

Gof /
1

So/
J mol1 K1

C p at 400 K/
J mol1 K1

C p at 400 K/
J mol1 K1

191.61
130.68
192.45

31.15
27.14
27.31

1.357 102
9.274 103
2.383 102

2.680 105
1.381 105
1.707 105

1.168 108
7.645 109
1.185 108

29.19
29.01
37.21

29.19
29.01
37.13

Species

kJ mol

kJ mol

N2 (g)
H2 (g)
NH3 (g)

0
0
46.11

0
0
16.45

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)


400
(35.06)(400)ln
= 20.18 kJ mol1
298

Calculate the change in Gibbs energy when 1 mol of gaseous


ammonia is heated at constant pressure P = 1 bar from T0 = 298 K
to T1 = 400 K. Assume that gaseous ammonia at these conditions
behaves as an ideal gas. The expression for the heat capacity of
ammonia is reported in literature2 as

In this case, the error produced by the approximation C p = C p =


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


1.185 108T 3

Example 2: Chemical Equilibrium Constant at a Given


Temperature

(34)
1

Calculate the chemical equilibrium constant for the formation of


ammonia from its elements, in a gaseous phase reaction at T =
400 K, assuming that all the species behave as ideal gases.
The chemical reaction that takes place in this case is

where Cp is given in units of J mol K and T in K.


Solution via the GibbsHelmholtz Equation. The Gibbs
energy of formation of gaseous ammonia at 298 K is 16.45 kJ
mol1 and the absolute entropy, S0, at the same temperature is
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
integrated form of the GibbsHelmholtz equation, eq 7,

N2(g) + 3H 2(g) 2NH3(g)

and relevant thermodynamic data for this reaction is given in


Table 1.
The values of C p and C p are taken from the Supporting
Information, and are calculated using eqs 20 and 21 with the
coecients for Cp from ref 2. More information on thermophysical properties can be found in ref 4.
Solution via Method 1. Full Solution of vant Ho
Equation. Applying the solution to the vHE proposed by Elliot
and Lira,2 with eqs 11ac): a = 57.95, b = 3.341 102, c
= 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,

G = G1 G0

1
1
= G0 1 1 T1 H0

T0
T0

T1
T

T
T2
b
+ aln 1 + 0 1 + T1 2T0 + 0
T1
T1
2
T0

2
2
T 3 d T 3 4T03
T 4
c T1 3T0

+ 0+ 1
+ 0
3
2
T1
4
3
T1

76,795.7
57.95
+
ln(400)
(8.314)(400)
8.314
3.341 102
4.877 105
+
(400) +
2(8.314)
6(8.314)
3.496 108
2
(400) +
(400)3 + 21.32
12(8.314)

ln K1 =

(35)

Substituting the known values, G0 = 16,450 J mol1, T0 = 298 K,


T1 = 400 K, a = 27.31, b = 2.383 102, c = 1.707 105, and d =
1.185 108 into the eq 35, G = G1 G0 = 20.20 kJ mol1.
Solution via the New Equation. Using the new approach
proposed in this work, the Gibbs energy is directly calculated by
applying eq 22.
T1

G = (Cp S0)(T1 T0) TC


1 p ln
T0

(36)

ln K1 = 3.58 K1 = 36.04

Solution via Method 2. Approximated Solution of vant


Ho Equation. In this method, the eect of temperature on the
enthalpy of reaction is neglected, and the chemical equilibrium
constant is obtained by solving eq 12:

(22)

The values of C p = 37.2 J mol1 K1 and C p = 37.1 J mol1 K1 are


taken from Table A.1 (in the Supporting Information), and S0 =
192.45 J mol1 K1 as in the previous method. With this
information, the change of the Gibbs energy can be readily
obtained: G = G1 G0 = 20.20 kJ mol1. Note that the values
obtained by the two methods are identical but the second
method oers a simpler procedure.
When the temperature dependence of the heat capacities is
unknown or the interest is on a rough estimate of the changes of
Gibbs energy, it can be assumed that C p = C p = Cp,0, where Cp,0 is
the heat capacity at 298 K. For ammonia, Cp,0 = 35.06 J mol1
K1.3

K
Hrxn 1
1
ln 1 =

R T1
T0
K0
o
o
Grxn,0
Hrxn
1
1
ln K1 =


RT0
R T1
T0
o
Hrxn,0
= 92,220 J

ln K1 =

o
Grxn,0
= 32,900 J

32,900
92,220 1
1

(8.314)(298)
8.314 400
298

ln K1 = 3.78 K1 = 44.14
399

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Article

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


Are Functions of T). Applying eq 29b to the three species, with
the information provided in Table 1: (GN2) = 20,003.9 J
mol1, (GH2) = 13,786.2 J mol1, (GNH3) = 20,206.5 J
mol1. And substituting the values in eq 29a with Grxn,0 =
32,900 J, one can readily get
ln K1 =

ln K1 =

1
{+32,900 [(2)( 20,215.9)
(8.314)(400)
+ 20,003.9 + (3)(13,786.2)]}

ln K1 = 3.60 K1 = 36.56

Solution via Method 3b. New Equation (C p = Cp= Cp,0 =


Constant). In this case, the heat capacities are assumed to be
independent of the temperature. Thus, C p = C p = Cp,0, where Cp,0
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:
(GN2) = 20,004.1 J mol1, (GH2) = 13,784.5 J mol1,
(GNH3) = 20,190.5 J mol1. And substituting the values in eq
29a, with Gorxn,0 = 32,900 J, one can readily get

1
{+32,900 [(2)( 20,206.5)
(8.314)(400)
+ 20,003.9 + (3)(13,786.2)]}

ln K1 = 3.59 K1 = 36.36

Solution via Method 3a. New Equation (C p = C p and Cp


Is a Function of T). In this case, only one average heat capacity is
required. C p = C p = T1
T0 (Cp dT)/(T1 T0), (GN2) = 20,003.9
J mol1, (GH2) = 13,786.2 J mol1, (GNH3) = 20,215.9 J
mol1. And substituting the values in eq 29a with Gorxn,0 =
32,900 J, one can readily get

ln K1 =

1
{+32,900 [(2)( 20,190.5)
(8.314)(400)
+ 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

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.

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.

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.

REFERENCES

(1) Beegle, B. L.; Modell, M.; Reid, R. C. AIChE J. 1974, 20, 1194
1200.
(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).

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