Physical Chemistry 1, Lecture Notes Unit 5

56
UNIT 5. Gibbs Energy and Equilibrium: General Thermodynamic Relations

This Unit is equivalent to sections 3.5, 3.6, 3.9 and 5.1b Atkins 8
th
edition


This unit is largely theoretical, presenting a more formal method of introducing the major thermodynamic quantities U
(the internal energy), H (the enthalpy), S (the entropy), A (the Helmholtz energy), and especially G, the Gibbs energy, as
well as the relations, both integral and differential, between these quantities. For a chemist, the Gibbs energy G is the
function that will prove most useful in considering chemical equilibrium in open systems. Thus, Unit 5 serves mainly to
define the basic thermodynamic functions, and to state the formal relations needed when we discuss their application in
Unit 6 (chemical equilibrium) and Unit 7 (phase equilibrium).

5.1 Helmholtz and Gibbs energies

Just as we defined a new quantity H, enthalpy, as H = U + pV in eq. 2.8, and then went on to show the practical
application of this new quantity, we will now define two new thermodynamic functions: the Helmholtz energy A, and the
Gibbs energy G.

A = U TS 5.1
G = H TS 5.2

The Helmholtz and the Gibbs energies are the thermodynamic functions that determine the equilibrium position in
systems with physical or chemical changes. The Helmholtz energy A(V,T) is most conveniently applied in systems at
constant volume. For that reason, it is the more commonly discussed property in physics. The Gibbs energy G(p,T) is the
most convenient property in systems at constant pressure, and it is the quantity most useful in systems of interest in
chemistry. Note that both A and G will have the units of energy and work, i.e. J or kJ. We will now use the differential
forms of eqs. 5.1 and 5.2 to see the relation between A, G, and the equilibrium state.

dA = dU TdS SdT 5.3a
dG = dH TdS SdT 5.3b

Substitute eqs. 2.6, dU = dq pdV and 2.9b, dH = dq + Vdp

dA = dq pdV TdS SdT
dG = dq + Vdp TdS SdT
Physical Chemistry 1, Lecture Notes Unit 5
57

We find that for a reversible process, with dq = dq
rev
= TdS:

dA = pdV SdT 5.4a
dG = +Vdp SdT 5.4b

For an irreversible process, dq
irrev
< TdS (eq. 4.7) and therefore dq
irrev
TdS <0 :

dA < pdVSdT 5.5a
dG < +Vdp SdT 5.5b

These differential forms of the definition equations for A and G tell us the following: for a small reversible change (p,V,T
change, phase change, chemical change), the variables that determine a small change in A (dA) are V and T, the variables
connected with the change in G (dG) are p and T. From eq. 5.4, for the case of a reversible and isothermal process (dT =
0) carried out at constant volume (dV = 0) we find:

(dA)
V,T, reversible process
= 0 5.6

For G, the function most useful in chemistry, for a reversible isothermal and constant pressure process (dp = 0, dT = 0),
we find:

(dG)
p,T, reversible process
= 0 5.7

In other words, for isothermal systems at constant pressure, eq. 5.7 tells us that we will be at equilibrium if for small
changes dG = 0. For instance, we will have a phase equilibrium when in transferring substance from one phase to another,
the Gibbs energy is constant (dG = 0), in other words, the Gibbs energy of the substance is the same in each phase when
the phases are in equilibrium.

The Gibbs energy function is also useful in determining the direction of spontaneous change in irreversible processes.
From eq. 5.5b:
(dG)
irreversible process
< +Vdp SdT 5.8

and therefore, for any spontaneous isothermal process at constant pressure:

(dG)
irreversible process
< 0 5.9
Physical Chemistry 1, Lecture Notes Unit 5
58

We could have applied the same reasoning to the Helmholtz energy A for constant volume processes. eq. 5.9 tells us that
if we find that the Gibbs energy change in a certain process is zero, then we are at equilibrium. If the Gibbs energy change
is negative, we have a spontaneous (irreversible) process. If we find the Gibbs energy change to be positive for a given
process, then the spontaneous process will occur in the opposite direction, for which, analogous to Hess law, the Gibbs
energy change will be negative. Particularly important in this section are eqs. 5.5 and 5.7. Eq. 5.7 defines the equilibrium
position and ultimately will serve as the connection between the equilibrium constant and the Gibbs energy, while eq. 5.5
allows us to determine entropy and volume changes for chemical reactions from the temperature and pressure derivatives
of the Gibbs energy. However, first we will return to more practical matters in the next section.

5.2 The standard Gibbs energy

For a discrete change in an isothermal process (SdT = 0), the definition equation for G, eq. 5.2 or 5.3, can be written as:

AG = AH TAS 5.10

This is of course how the Gibbs energy was introduced in your first year textbook. We now recognize that the term TAS is
really a simplification of A(TS) for the isothermal case. Indeed, we will almost universally apply Gibbs energy
calculations only to isothermal processes. We can apply eq. 5.10 to phase changes or chemical reactions. When the
process is at equilibrium we apply eq. 5.7:

(AG)
p,T.,reversible process
= 0 5.7

Equation 5.10 can be applied to any isothermal system. Under standard conditions, 298K, gases at 1 atm partial pressure
each for both products and reactants, pure condensed substances as their normally occurring liquids or solids, solutes in a
(possibly hypothetical) 1M solution, etc. we write:

AG
o
= AH
o
TAS
o
5.11

If the process is a formation reaction (remember its definition, section 3.2) under standard conditions we can write:

AG
f
o
= AH
f
o
TAS
o
5.12

where AS
o
is the difference in standard (absolute) entropies of (products reactants) in the formation reaction. Eq. 5.8
defines the standard Gibbs energy of formation of compounds. Values for AG
f
o
are collected in the thermodynamic tables
Physical Chemistry 1, Lecture Notes Unit 5
59
such as in the appendix or Atkins Tables 2.5 and 2.6. The standard Gibbs energy of elements in their naturally occurring
state at 1 atm, 25
o
C is zero. Standard Gibbs energies of formation of elements are zero, of compounds they can be
positive or negative, just as the standard enthalpies (and different from the absolute entropies, which are always positive).

Example 5.1. Calculate the standard Gibbs energy of formation of methanol, CH
3
OH, using only the standard enthalpies
and absolute entropies as listed in the Appendix. Compare your answer to the value of 166 kJ/mol in the Appendix.

Answer. This question is not as straightforward as you might think. The reason is that we cannot just use eq. 5.12 with the
standard enthalpy and the absolute entropy of liquid methanol. Doing that, and with T = 298 K, would yield 276 kJ/mol,
obviously not the answer in the data tables (the value in the table is AG
f
o
= 166.3 kJ/mol). The reason is that the
entropies of the elements on the left hand side of the formation reaction are not zero. Therefore, we first have to calculate
the AS for the formation reaction: C(s) + 2H
2
+ O
2
CH
3
OH(l), AS = 126.8 (5.7 + 2x130.7 + x205.1) = 242.9
J/(K.mol). Now we can calculate AG
f
o
with eq. 5.12, remembering that the standard enthalpies of the elements on the left
hand side are all zero: AG
f
o
= 238.7 298x(0.2429) = 166 kJ/mol, exactly the value in Atkins Table 2.6, as it should
be since we use this table for the AH
f
o
and S
o
values. Notice that the AS of the formation reaction is negative, as expected
(why?), but that the large gain in enthalpy overcomes this unfavourable entropy, making the formation reaction under
standard conditions spontaneous, at least in principle. In reality of course it would be very difficult to combine carbon,
hydrogen and oxygen to make methanol directly.


Again, we can use the A
f
G
o
values in the thermodynamic tables to calculate standard Gibbs energy changes of chemical
reactions:

AG
rxn
o
= EAG
f
o
(products) EAG
f
o
(reactants) 5.13


Example 5.2. Calculate the standard Gibbs energy change for the watergas reaction:
C(s) + H
2
O(g) CO(g) + H
2
, using the AG
f
o
values of the Appendix.

Answer. We can simply apply eq. 5.13 to this reaction, recognizing that the standard Gibbs energies of the elements are
zero. Note that we specified H
2
O(g), so at 298 this would be a hypothetical reaction. AG
o
= 137.2 (228.6) = +91.4 kJ.
This positive value indicates that the watergas reaction as written is not spontaneous at 298 K and 1 atm H
2
O, 1 atm CO
and 1 atm H
2
all in contact with graphite. Instead, the opposite (equally hypothetical) reaction would occur spontaneously
under these conditions.
Physical Chemistry 1, Lecture Notes Unit 5
60
5.3 The temperature dependence of the Gibbs energy.

The differential form for the Gibbs energy, eq. 5.5b, can be used to derive relations for its temperature and pressure
dependence.

dG = Vdp SdT 5.5b

S
T
G
p
= |
.
|

\
|
c
c
5.14
V
p
G
T
+ =
|
|
.
|

\
|
c
c
5.15
The temperature derivative in eq. 5.14 is particularly important in chemistry. We will have to do some manipulation to see
why. Instead of differentiating G at constant pressure, lets have a look at what we get when we differentiate G/T with
respect to temperature:


p
2
p
T
G
T
1
T
G
T
G
T
|
.
|

\
|
c
c
+ = |
.
|

\
|
c
c


The c/cT means the differentiation with respect to temperature, or the variation of G/T with temperature at constant
pressure Now we substitute eq. 5.14 in the right hand side:
) TS G (
T
1
T
S
T
G
T
G
T
2 2
p
+ = = |
.
|

\
|
c
c


And since G + TS equals H, we have found the Gibbs-Helmholtz equation:


2
p
T
H
T
G
T
= |
.
|

\
|
c
c
5.16

Equation 5.16 is an important equation that we will see back in various forms. It allows us to calculate the variation of the
Gibbs energy change for a given reaction as a function of temperature with as only input the enthalpy of reaction. We can
Physical Chemistry 1, Lecture Notes Unit 5
61
see this by recognizing that all the manipulations and differentiations involved in deriving eq. 5.16 can also be performed
with AG
rxn
, AH
rxn
and AS
rxn
, to arive at:


2
rxn
p
rxn
T
H
T
G
T
A
= |
.
|

\
| A
c
c
5.17

We can integrate both the left and right hand side of eq. 5.17 with respect to T to obtain the integrated form of the Gibbs
Helmholtz equation:


|
|
.
|

\
|
A + =
A

A
1 2 1
1
2
2
T
1
T
1
H
T
G
T
G
5.18

With the integration of 5.17 to obtain 5.18 we have assumed that AH is independent of temperature in the range T
1
to T
2
.

In interpreting eqs. 5.17 or 5.18, it is important to realize that the AG values are for an isothermal process, e.g. the AG
rxn
at
temperatures T
1
and T
2
.

The integrated form of 5.17 can also be written as:

. const
T
H
T
G
+
A
+ =
A


Comparing this equation to eq. 5.10: AG = AH TAS, we see that the integration constant equals AS in eq. 5.10. For this
reason, often eq. 5.10 is also called the Gibbs-Helmholtz equation, and indeed it can be used in the same way as eq. 5.18
to calculate AG
rxn
at non-standard temperature, with the assumption that both AH and AS are independent of temperature.
We now can see that eq. 5.16 is always the correct starting point, not involving any assumption, and for the case that H =
f(T), we can always perform the correct integration as long as the functional form of this temperature dependence is
known (see Unit 3 section 3.2.3).
Physical Chemistry 1, Lecture Notes Unit 5
62

Example 5.3. Using the thermodynamic tables (Appendix), calculate the standard Gibbs energy change for the reaction:
N
2
O
4
(g) 2NO
2
(g), a) at 298K, and b) at 500K.

Answer. a) At 298K: AG
o
(T = 298) = 2x(+51.3) (+97.9) = +4.8 kJ.
b) Also from the Appendix table, AH
o
= 2x(+33.3) (+9.2) = +57.4 kJ. Applying eq. 5.18, with T
1
= 298, and T
2
= 500,
we have: AG
2
/500 4,800/298 = 57,400(1/500 1/298), which gives AG
2
(T = 500) = 30.8 kJ.

The reaction in example 5.3 is a particularly interesting case. The dissociation of N
2
O
4
is endothermic (AH
rxn
is positive),
not surprising since we are breaking chemical bonds. The calculation of AG
o
at 298 K shows that at this temperature the
entropy gain in the dissociation reaction (a favourable effect) is insufficient to overcome the unfavourable enthalpy
change. However, as T increases, the TAS term of course increases, and tends to shift AG to more negative values, with
as a result that at 500K the dissociation reaction has become spontaneous (AG is now negative). We say that this reaction
is entropy driven. Note in particular that in fact eqs. 5.16 and 5.18 show the thermodynamic basis for the principle of van
t Hoff-Le Chatelier, which you used in your first year course to make qualitative predictions based on knowing whether a
reaction was endo- or exothermic. Now we can make those predictions based on formal thermodynamics, and we can
make them quantitatively.


5.4 The chemical potential

The Gibbs energy of a substance has the units kJ/mol, in other words, it is an extensive property of the substance. When
we have a mixture of components, the Gibbs energy of the mixture can still be considered as the sum of the individual
molar Gibbs energies, just like the total volume of a mixture is the sum of the individual volume contributions by the
components in the mixture.

G
mixture
=

i
i , m
i
G n
i , m G is the molar Gibbs energy of component i in the mixture, i.e. it is the contribution (on a per mol basis) that
component i makes to the total Gibbs energy of the mixture. We call the molar Gibbs energy the chemical potential, for
which we use the symbol . Thus we write, for the total Gibbs energy of a mixture:

G
mixture
=

i
i i
n 5.19
Physical Chemistry 1, Lecture Notes Unit 5
63
For a pure single substance, the chemical potential is simply the Gibbs energy per mole, symbol
o
:

n
G
o
= 5.20
In a mixture, and in particular in liquid mixtures, the chemical potential of component i will be dependent on its
interactions with the other components, therefore in the general case the chemical potential will be a function of
composition and/or concentration. As a result, the chemical potential of each component must be expressed as a
differential of the total mixture Gibbs energy:


T , p , n
i
i
j
n
G
|
|
.
|

\
|
c
c
= 5.21

In general, in a mixture
i
=
i
o
. Expressed in words, eq. 5.21 states that the chemical potential of component i in a
mixture equals the change in total mixture Gibbs energy when 1 mol of i is added to the mixture at constant p, T, and
constant composition. As we will see in later units, we will expand the equilibrium condition in the case of mixtures by
stating that not only dG
mixture
, but also d
i
for each component must be zero. For instance, in the case of phase equilibrium
of mixtures, each component i must have the same chemical potential
i
(= molar Gibbs energy of i) in the phases at
equilibrium.


5.5. Summary of the formal thermodynamic relations

In Units 2-5 we have introduced all functions (heat, work, energy, enthalpy, entropy, Helmholtz energy, Gibbs energy)
used in chemical thermodynamics. The remaining units of this course will show how we use these functions in a variety of
chemical applications. Below, we will summarize the relevant definition equations in integral and differential form,
together with the relationships between these quantities.
Physical Chemistry 1, Lecture Notes Unit 5
64


Summary of integral and differential
relationships
Integral form Differential form
w = }p
ext
dV dw = p
ext
dV
U = q + w dU = TdS pdV
H = U + pV dH = TdS + Vdp
A = U TS dA = pdV SdT
G = H TS dG = Vdp SdT

2
p
2
V
p T V T
T
H
T
G
T T
U
T
A
T
S
T
G
V
p
G
S
dT
A
p
V
A
= |
.
|

\
|
c
c
= |
.
|

\
|
c
c
= |
.
|

\
|
c
c
+ =
|
|
.
|

\
|
c
c
= |
.
|

\
| c
= |
.
|

\
|
c
c



And, in the more common form, the equations important for chemical reactions:

AG = AH TAS (condition: isothermal system)

Equilibrium condition:
dG = 0, thus dH = TdS (condition: equilibrium = reversible process)

and in integral form:
AG = 0 thus AH = TAS
(note that the equilibrium condition is AG = 0, not AG
o
= 0!)

AG
rxn
o
= AH
rxn
o
TAS
rxn
o
(condition: isothermal system)


Physical Chemistry 1, Lecture Notes Unit 5
65
Finally the differential (eq. 5.22) and integral (eq. 5.23) form of the Gibbs-Helmholtz equation

2
o
rxn
p
o
rxn
T
H
T
G
T
A
=
|
|
.
|

\
| A
c
c
5.22.

|
|
.
|

\
|
A + =
A

A
1 2
o
rxn
1
1
o
rxn
2
2
o
rxn
T
1
T
1
H
T
) T ( G
T
) T ( G
5.23



Theory and concept questions

T5.1. Explain the difference between AG and AG
o
.

T5.2. Relate the difference between spontaneous (irreversible) and reversible processes in terms of the Gibbs energy.

T5.3. Express in words what is meant by (dG)
p,T
.

T5.4. What is the condition for the equation AG = AH TAS? What is the proper equation to use if this condition is not
met?

T5.5. In Unit 4 we stressed that the absolute entropy of an element at standard conditions is not zero but must be
positive. Since AG = AH TAS, why is AG
f
o
of elements at standard condition zero?


Problems

5.1. 3.5 mol of an ideal gas are compressed isothermally at 400 K from p = 1 atm to p = 10 atm. Calculate AU, AH,
AS and AG.
Answer. First the easy 50%! Ideal gas, isothermal, so AU = AH = 0. For AS we use eq. 4.15: AS = 3.5x8.314ln(1/10) = 67 J/K, then
for AG we can use eq. 5.10, since it is an isothermal process, and we find AG = +67x400 = 26.8 kJ. Note that for this compression AS
is negative, and since it is an isothermal ideal gas process with AH = 0, AG = TAS. As a final note, we will not normally calculate
AG for processes that involve a change in temperature, since we cannot evaluate the SdT integration in eq. 5.5. Note also that AG = w
= q!
Physical Chemistry 1, Lecture Notes Unit 5
66

5.2. 1.2 mol of an ideal gas is expanded isothermally at 350 K from V = 1 L to V = 20 L. Calculate AS and AG.
Answer. AS = 29.9 J/K; AG = 10.5 kJ.

5.3. Using the data for AH
f
0
and S
o
in the Appendix, calculate the standard Gibbs energy of formation of benzene(l) at
298K. Compare your answer to the number given in Table 2.5.
Answer. We first have to calculate AS for the formation reaction of benzene(l): 6C(s) + 3H
2
C
6
H
6
(l). AS
f
o
= 173.3 3x130.7
6x5.74 = 253.2 J/K. AG
f
o
= AH
f

o
TAS
f

o
= +49.0 298x(0.2532) = +124.5 kJ. Very close to the number in Table 2.5, i.e. +124.3
kJ.

5.4. Using the data for AH
f
0
and S
o
only, calculate the standard Gibbs energy of formation of CuSO
4
(s) at 298K.
Compare your answer to the number given in the data tables.
Answer. 662.2 kJ; Table 2.6 gives 661.8 kJ.

5.5. Using any appropriate data from the thermodynamic tables, calculate the standard Gibbs energy change of the
reaction: CO
3
2
(aq) + H
2
O(l) HCO
3

(aq) + OH

(aq) at 298K. Is the reaction spontaneous under standard conditions?

Answer. We simply look up the AG
f
o
values: AG
rxn
o
= 586.8 157.2 (527.8) (237.1) = +20.9 kJ. Under standard conditions the
reaction is not spontaneous to the right, the reverse reaction is. Note however that standard conditions would be when we mix
carbonate ions, bicarbonate ions, and OH

ions, each at 1M, in water!

5.6. Using any appropriate data from the thermodynamic tables, calculate the standard Gibbs energy change of the
reaction: NH
4
+
(aq) + OH

(aq) NH
3
(aq) + H
2
O(l) at 298K. Is this reaction spontaneous under standard conditions?
What are standard conditions in this case?
Answer: AG
rxn
o
= 27.1 kJ. The standard reaction (i.e. 1M ammonium ion, 1 M hydoxide and 1 M NH
3
mixed together in water) is
spontaneous to the right.


Additional problems and exercises in Atkins 9
th
edition.
Exercises 3.9a,b, 3.11a,b, 3.12a,b, 3.16a,b, 3.19a,b (chemical potential = Gibbs energy!), 3.20a,b (this is for the read
only section, but a useful exercise!
Numerical problems 3.16, 3.17