Chemistry 360

Spring 2012
Dr. Jean M. Standard
March 2, 2012
Example Calculations of Helmholtz and Gibbs Energy Changes
1 ) Reversible Isothermal Expansion or Compression
If a substance such as an ideal gas undergoes a reversible isothermal expansion, the change in Helmholtz energy
!A may be calculated. The calculation begins with the fundamental equation for A,

!
dA = " SdT " PdV . (1)
For an isothermal process,
!
dT = 0, and the second term in Eq. (1) drops out, leaving only

!
dA = " PdV . (2)
Then, for an expansion or compression from
!
V
1
to
!
V
2
, the change in Helmholtz energy may be determined by
integration,
!
"A = # P dV
V
1
V
2
$
.
(3)
The expression in Eq. (3) is identical with that for the work in a reversible isothermal expansion. Thus, the
Helmholtz energy corresponds to the maximum work available in an isothermal process.
Exampl e
Determine the change in Helmholtz energy !A when 1 mole of H
2
gas is compressed
isothermally and reversibly from 10.0 L to 1.0 L at 500 K. Assume ideal gas behavior.
Using the equation above, an expression for P from the ideal gas equation may be substituted,

!
"A = # P
V
1
V
2
$
dV = #
nRT
V
dV
V
1
V
2
$
.
(4)
For an isothermal process, the temperature T may be pulled out of the integral along with the constants n and R
and the integral evaluated to yield

!
"A = # nRT
1
V
dV
V
1
V
2
$
= # nRT ln
V
2
V
1
%
&
'
(
)
*
.
(5)
Substituting,

!
"A = # nRT ln
V
2
V
1
$
%
&
'
(
)
= 1 mol ( ) 8.314 Jmol
-1
K
-1
( )
500 K ( ) ln
1.0 L
10.0 L
$
%
&
'
(
)
"A = 9570 J .
(6)
2
2 ) Phase Transitions
One quantity of interest to be calculated for phase transitions is the change in Gibbs free energy, !G. Starting
from the definition of G, we have

!
G = H " TS .
(7)
Rewriting this equation in terms of changes in the variables,
!
"G = "H # " TS ( ) .
(8)
For a process occurring under constant temperature conditions such as a phase transition, Eq. (8) simplifies to
!
"G = "H # T"S . (9)
Eq. (9) is an important thermodynamic relation that may be used not only for phase transitions, but also for
chemical reactions and other processes if they occur at constant temperature.
Exampl e
Determine !S and !G when 1 mole of liquid water is vaporized at 100C and 1 bar
pressure.
Under the constant pressure conditions of a phase transition, the entropy change is given by

!
"S =
"H
T
. (10)
The standard molar enthalpy of vaporization,

!
"H
vap
!
, for water is reported in the literature as 44.0 kJ/mol. The
entropy of vaporization of 1 mole of water is therefore

!
"S
vap
=
n"H
vap
!
T
vap
=
1 mol ( ) 44.0#10
3
J/mol
( )
373 K
"S
vap
= 118 JK
$1
. (11)
The change in Gibbs free energy for the vaporization process may then be calculated using Eq. (9),

!
"G
vap
= "H
vap
# T
vap
"S
vap
= n"H
vap
!
# T
vap
"S
vap
= 1 mol ( ) 44.0$10
3
J/mol
( )
# 373 K ( ) 118 JK
#1
( )
"G
vap
= 0 .
(12)
Here, we see that the Gibbs free energy change for the phase transition equals 0. The Gibbs free energy
change for all phase transitions equals 0, not just for this specific example.
An alternative calculation of the Gibbs free energy change of a phase transition starts with the fundamental
equation for G,
!
dG = " SdT + VdP .
(13)
For a phase transition at constant temperature and pressure,
!
dT = dP = 0, and therefore
!
dG = 0, or
!
"G = 0.
3
3 ) Chemical Reactions
Because G is a state function, the standard molar Gibbs free energy change for a chemical reaction,

!
"G
r
!
, may
be calculated using a method similar to that for calculating standard molar enthalpies of reaction,

!
"G
r
!
= #
i
"G
f ,i
!
products
$
#
i
"G
f ,i
!
reactants
$
.
(25)
In Eq. (25), the first sum is over all the different products in the reaction and the second sum is over all the
different reactants (i labels each species in the reaction),
!
"
i
corresponds to the stoichiometric coefficient, and

!
"G
f ,i
!
is the standard molar Gibbs free energy of formation of species i.
As is the case for standard molar enthalpies of formation, the standard molar Gibbs free energy of formation of a
an element in its standard state equals zero,


!
"G
f
!
(element, standard state) = 0 . (27)
In addition, the standard molar Gibbs free energy change may be used to predict whether a reaction will occur
spontaneously. As will be shown in class, the criterion for spontaneity at constant temperature and pressure is
!
"G # 0 .
(27)
Thus, if the standard molar Gibbs free energy of reaction is less than zero, we would predict that the chemical
reaction occurs spontaneously.
Example 1
Determine the standard molar Gibbs free energy change at 298 K for the combustion
reaction

!
CH
4
g ( ) + 2 O
2
g ( ) " CO
2
g ( ) + 2 H
2
O ! ( ) . ( 26)
Using Eq. (25), the standard molar Gibbs free energy change of reaction is

!
"G
r
!
= "G
f
!
CO
2
, g ( ) + 2 "G
f
!
H
2
O," ( ) # "G
f
!
CH
4
, g ( ) # 2 "G
f
!
O
2
, g ( ) . (27)
The standard molar Gibbs free energies of formation at 298 K for each of the species may be found in the
Appendices of your textbook. For this reaction, the required values are given in the table below.
Substance

!
"G
f ,i
!
(kJ/mol)
CH
4
(g) 50.8
O
2
(g) 0
CO
2
(g) 394.35
H
2
O (l) 237.14
Substituting,


!
"G
r
!
= "G
f
!
CO
2
, g ( ) + 2 "G
f
!
H
2
O," ( ) # "G
f
!
CH
4
, g ( ) # 2 "G
f
!
O
2
, g ( )
= #394.35 ( ) + 2 #237.14 ( ) # #50.8 ( ) # 2 0 ( ) kJ/mol
"G
r
!
= #817.8 kJ/mol .
(28)
For a combustion reaction like this one, the negative value of standard molar Gibbs free energy indicates that
the reaction occurs spontaneously.
4
Example 2
Determine the standard molar Gibbs free energy change at 298 K for the acid/base
neutralization reaction

!
NaOH 1 M, aq ( ) + HCl 1 M, aq ( ) " NaCl 1 M, aq ( ) + H
2
O ! ( ) . ( 26)
The overall reaction is

!
OH

1 M, aq ( ) + H
+
1 M, aq ( ) " H
2
O ! ( ) . ( 2 6 )
Using Eq. (25), the standard molar Gibbs free energy change of reaction is

!
"G
r
!
= "G
f
!
H
2
O," ( ) # "G
f
!
OH

, aq
( )
# "G
f
!
H
+
, aq
( )
. (27)
The standard molar Gibbs free energies of formation at 298 K for each of the species may be found in the
Appendices in your textbook. For this reaction, the required values are given in the table below.
Substance

!
"G
f ,i
!
(kJ/mol)
OH

(aq) 157.28
H
+
(aq) 0
H
2
O (l) 237.14
Substituting,


!
"G
r
!
= "G
f
!
H
2
O," ( ) # "G
f
!
OH

, aq
( )
# "G
f
!
H
+
, aq
( )
= #237.14 ( ) # #157.28 ( ) # 0 ( ) kJ/mol
"G
r
!
= # 79.86 kJ/mol .
(28)
Here, we see that acid/base neutralization in solution is a spontaneous process on the basis of the negative value
for the standard molar Gibbs free energy of reaction.