Thermodynamics of chemical process 39

2. THERMODYNAMICS OF
CHEMICAL PROCESSES

Thermodynamics (Greek: therm =heat; dynamys =power) studies the
effects of changes in temperature, pressure and volume on physical systems at the
macroscopic scale by analysing the collective motion of their particles by using
statistical methods.
Chemical thermodynamics has as main objectives:
- the thermal effects of chemical transformation;
- the quantity of work, accompanying thermodynamic process which can
include a chemical reaction;
- the laws describing the processes in which the energy pass from one
state to another;
- the possibility, the direction and the limits of natural and industrial
process;
- the organization or disorganization state of thermodynamic systems;
- the chemical system and thermal equilibrium after physical chemical
transformations;
- establish the determining conditions for equilibrium.




40 GENERAL CHEMISTRY

2.1. Thermodynamic systems

Thermodynamic system: a part of the universe separated by a real or
imaginary boundary from the rest of the universe. The surroundings comprises the
region outside the system, where we make our measurements.

Figure 13. Schematic representation of a thermodynamic system

Phase part of a system having the same properties in all its points and
separated from the rest of the system by a separation surface.
Thermodynamic systems are classified as follows:
- fromphysical point of view
homogenous formed from only one phase. It has the
same properties in all its points (gas, solution, mixture of
gases)
heterogenous formed from 2 phases or many (ex.
Physical equilibrium H
2
O
L
H
2
O
V
the properties
vary in at least 2 points)

- from point of view of interaction with the environment
isolated system, there is no energy or mass exchange with
the environment;
System
Surrounding
Boundary
Thermodynamics of chemical process 41

no isolated or open system it changes energy and mass
with the environment;
closed system it does not exchange mass but it can
exchange energy (when the system allows energy to
escape as heat system is called diathermic);
adiabatic system there is no change of heat with the
environment.

The properties of a system could be:
- intensive they do not depend on quantity of substance: pressure,
temperature;
- extensive they depend on quantity of substance: internal energy (U),
enthalpy (H), Gibbs free energy (G), Helmholtz free energy (A or F).
In order to describe a thermodynamic process state equations are used:
f(P,V,T) =0 for a monocomponent system and
f(P,V,T,x
i
) =0 for multicomponent system.
where P is the pressure, T is the temperature, V is the volume and x
i
is the
molar ratio of the i
th
component -
n
n
x
i
i
= ; n
i
is the number of moles of i
th

component and n is the total number of moles.
Thermodynamic process the energetic evolution of a thermodynamic
system proceeding from an initial state to a final state. This evolution is determined
by the variation of one or more state parameters.
The thermodynamic processes are classified as follows:
- reversible the process passes spontaneously from the initial
state to the final state and from the final state to the initial state
through the same sequence of intermediate states;
- irreversible the process in which the system can not come
back from the final state to the initial state through the same
sequence of intermediate states.
42 GENERAL CHEMISTRY


2.2. The Thermodynamics laws

2.2.1 Zeroth law of thermodynamics

If two systems are in thermal equilibrium with a third system, then they
must be in thermal equilibrium with each other.
This principle introduces the temperature parameter, T. When two
different systems are in thermal contact, the big body called also thermostat
preserves unchanged its properties while the small body, called also thermometer
varies its properties.

Figure 14. Schematic representation of zeroth law of thermodynamic

For the temperature there are several notations and units:
- t C (Celsius degrees)
- T K (Kelvin degrees) (T =t + 273,16)
- F =9/5 C +32 (Fahrenheit degrees) (anglosaxon system)

2.2.2. First law of thermodynamics

Energy is neither created nor destroyed; it changes from one form to
another.


Thermostat
thermometer
Thermodynamics of chemical process 43

Consequences
- It is impossible to create a perpetual motion machine of I type (machine
which produces energy from nothing) Helmholtz 1847;
- If a quantity of energy disappears from a system, a new form of energy,
in an equivalent quantity appears in its place;
- The internal energy of an isolated system is constant Equivalence
Law of J oule
cal J const
Q
W
Q
W
/ 18 , 4
2
2
1
1
= = = [1]
where:
W The Work is done when an object is moved against an opposing force;
Q The Heat: the system gives or receives heat.
The first law of thermodynamic postulate that U the change in internal
energy of the system is given by:
W Q U + = [2]
Or in other words:
The change in internal energy of a closed system is equal to the energy that
passes through its boundary as heat or/and work.
All these dimensions are expressed in J (J oule) or cal (calorie):
1J =4,186 cal
The internal energy is a state function. It is depending on the initial and
final state and not on the way, while the heat and the work are functions which
depend on the followed way. So we can write for the change in internal energy we
can write:

1 2
U U U = [3]
1 2
2
1
U U dU U = =

[4]

= 0 dU for a reversible cycle [5]

44 GENERAL CHEMISTRY

Sign convention:
(+) any quantity which increases the energy of the system (the heat
absorbed by the system, the work done on the system);
(-) any energy lost by the system.
Examples:
Heat:
(+) received by the system (evaporation, endothermic reaction)
(-) lost by the system (solidification, exothermic reaction)
Work:
(+) performed by the surrounding on the system (compression)
(-) performed by the system (expansion)

In these conditions the internal energy is given by:
W Q U + = - for a finite process
And:
W Q dU + = - for an elemental process [6]
Q , W are infinite small quantities.
Exemplification for expansion work:
pdV Sdl
S
F
Fdl W = = =
pdV W = [7]
That means that the system receives work when its volume is reduced.
In these equations F is the force, l is the distance, S and V are the surface and the
volume respectively.

Examples Reversible processes (perfect gas)
a) isotherm process (constant temperature)
1 2
U U U = [8]
Thermodynamics of chemical process 45

= =

2
1
) (
T
T
v
dT C U T f U [9]
(where C
v
is the molar heat capacity at constant volum)
0 ,
1 2
= = U U U [10]
W Q = [11]
1
2
2
1
2
1
ln
V
V
nRT dV
V
nRT
pdV W = = =

[12]

nRT pV = [13]
V
nRT
p = [14]
constant temperature
2 2 1 1
V p V p = [15]
2
1
1
2
p
p
V
V
= [16]

2
1
ln
p
p
nRT W = [17]
b) isochoric process (constant volum)
0 0 = = W dV [18]
Q U = [19]
c) adiabatic process 0 = Q
W U =
) (
1 2
T T C W
V
=

=

2
1
T
T
V
dT C U [20]
This means that the temperature will increase when the system is
compressed and the temperature will decrease when the system will undergoes an
expansion.


46 GENERAL CHEMISTRY

d) isobar process (constant pressure)
A new state function is introduced in order to characterize the isobar
process:
H Enthalpy, calorific function of Gibbs
PV U H + [21]
H H H dH = =

2
1
1 2
[22]
0 =

dH for a reversible cycle [23]

Because the enthalpy is a state function its elemental change is an exact
differential.
VdP PdV dU dH + + = [23]
If the system is in mechanical equilibrium with its surroundings at a given
pressure P and undergoes only expansion work, we can write: PdV dW =
VdP PdV PdV Q dH + + = [25]
VdP Q dH + =
, 0 = dP (constant pressure)
( )
p
Q H = [26]
Q
p
=H [27]

The thermal effects of all process which take place at constant pressure
(chemical reactions, phase transitions, solubilization) represent the change in
enthalpy for that system.

2.2.2.1. Applications of the first law to the material constants
Heat capacity represents the amount of heat necessary to increase the
temperature of the system by 1C.
Specific heat capacity (specific heat) of a substance represents the heat
capacity divided by the mass, usually in grams or, in other words, it represents the
Thermodynamics of chemical process 47

heat quantity necessary to increase the temperature of one gram of substance by
1C:
T m
Q
c

= [28]

Molar heat capacity heat quantity necessary to increase the temperature
of one mole of substance by 1C:
M
m
n
T n
Q
C =

= [29]
C
v
- the molar heat capacity at constant volume
- the change of the molar internal energy of the substance with the
temperature, at constant volume;
C
p
the molar heat capacity at constant pressure
- the change of the molar enthalpy of the substance with the
temperature, at constant pressure.
C
V
and C
p
are state functions
For certain temperature range C
p
=a +bT +cT
2
+.
Between C
P
and C
V
there is the following relation:
C
p
C
v
=R [30]
Equation [30] is called Mayer equation. In this equation R represents the
universal (ideal) gas constant taking the following values depending on units used:
R=1.987 cal / mol K
R =8.31 J / mol K
R =0.082 L atm / mol K

2.2.2.2 Thermochemistry
In thermodynamics and physical chemistry, themochemistry is the study
of the heat evolved or absorbed in chemical reactions. Thermochemistry,
generally, is concerned with the heat exchange accompanying transformations,
such as mixing, phase transitions, chemical reactions, etc, which include
48 GENERAL CHEMISTRY

calculations of quantities such as the heat capacity, heat of absorption, heat of
formation, etc.
Considering the following chemical equation:
H A A A A A A A
r
i i i i
+ + + + + + + + .... ... ... ...
' ' '
2
'
2
'
1
'
1 3 3 2 2 1 1

where H
r
is (+) for endothermic reactions and () for exothermic
reactions
At a given temperature and pressure:

=
react
i i
prod
i i P T
r
H H H
' '
,
[31]
where v
i
is the number of moles for i
th
reactant; H
i
is the molar enthalpy of i
th

reactant; v
i
is the number of moles for i
th
product; H
i
is the molar enthalpy of i
th

product.
Example:
3 2 2
2NH 3H N +
2 2 3
3 2
, N H NH P T
r
H H H H =

a) Heat of formation
The enthalpy change for a reaction at a given temperature and pressure can
be derived from heat of formations of the reactants and products in the following
way:

=
react
i
f
i
prod
i
f
i P T
r
H H H
' '
,
[32]
The values for standard enthalpy
0
298
H
f
(standard conditions, 1 atm and
298 K (reference state)) are collected in thermodynamic tables.
The standard enthalpy of formation
0
H
f
of a substance is the standard
reaction enthalpy for the formation of the compound from its elements in their
reference states.
Example:
) ( 2 ) ( ) ( ) ( 3 2
3 2 3
g s g s
CO Fe CO O Fe + +
Thermodynamics of chemical process 49

mol kcal H
s O Fe
f
/ 2 . 196
0
) ( , 298
3 2
=
mol kcal H
g CO
f
/ 4 . 26
0
) ( , 298
=
mol kcal H
g CO
f
/ 968 . 93
0
) ( , 298
2
=
0
0
, 298
=
Fe
f
H (generally
0
298
H
f
is equal with zero for elements)
( ) ( ) ( ) kcal H
r
504 . 6 4 . 26 3 2 . 196 968 . 93 3
0
298
= =

b) Heat of combustion
The heat of combustion is the energy released as heat when one mol of a
compound undergoes complete combustion to upper stable oxides.
mol kcal H
c
/ 79 . 212 O 2H CO 2O CH
0
298 (l) 2 (g) 2 2(g) 4(g)
= + +

=
'
' '
,
i
i
c
i
i
i
c
i P T
r
H H H [33]
Other heat type:
- heat of solubilization
- heat of decomposition
- heat of neutralization
- heat from bond energy

2.2.2.3 The laws of thermochemistry

a) Hesss law (1840)
The heat exchange accompanying a transformation is the same,
independently whether the process occurs in one or several steps.
The standard enthalpy of an overall reaction is the sum of the standard
enthalpies of the individual reactions into which a reaction may be divided.
The thermal effects of one reaction depend only on the nature and the state
of the reactants and products and not on the way in which takes place the reaction.



50 GENERAL CHEMISTRY

Example:


cal H CO O CO
cal H CO O C
cal H CO O C
g g g
g g s
g g s
67640 2 / 1
26390 2 / 1
94030
3 ) ( 2 ) ( 2 ) (
2 ) ( ) ( 2 ) (
1 ) ( 2 ) ( 2 ) (
= +
= +
= +

3 2 1
H H H + =

b) Kirchhoff s law
The variation with temperature of the thermal effects of a chemical
reaction is equal to the stoichiometric molar heat capacity of the system (constant
pressure).

+ =
2
1
1 2
, ,
T
T
P
r
P T
r
P T
r
dT C H H [34]
Equation [34] represent the integral form of Kirchhoff equation
Usually:
...
2
2
+ + + =
+ + =
cT bT a C
cT bT a C
r r r
P
r
P

Generally:
T
1
=298K and P =1 atm. (standard heat of formation)
( )

+ + + + =
2
2
298
0
298
0
...
T
r r r r
T
r
dT cT bT a H H [35]
H C
p
> 0 increases when the temperature increases
H C
p
< 0 decreases when the temperature increases
H C
p
= 0 is constant
C
CO
CO
2
H
2

H
3

O
2

O
2

O
2

H
1

Thermodynamics of chemical process 51

If phase transitions take place in the temperature range considered, the
enthalpies of transition should be taken into account.

+ + =
2
2
1
1 1 2
0 0
T
T
P
r tr
T
T
P
r
T
r
T
r
tr
tr
dT C H dT C H H [36]
where represents the mole numbers of the substance undergoing the phase
transition. The transition enthalpy will be positive when a product is phase
transformed and will be negative when a reactant undergoes a phase transition.
1
P
C and
2
P
C are the change in heat capacity calculated with the values of heat
capacity function of the phase.

Example:
Calculate the thermal effect for the reaction:
Al
2
O
3
+3CO 2Al +3CO
2

at 1000 K and 1 atm.
It is known: cal H
r
177080 298
0
= , melting temperature of aluminium is
930 K, mol cal H
Al
melt
/ 2500
0
= and the values of heat capacities at constant
pressure, given in the following table:
Substance C
p
, cal/molK
Al
2
O
3 22 +810
-3
T
CO 6.6 +1,210
-3
T
CO
2 10.3 +2.810
-3
T
Al
(s)
4.8 +3.2 10
-3

Al
(l)
7

Solution:
3 2 2
) ( 2
3 3 2
O Al CO CO s Al
P P P P P
r
C C C C C + =
T T T
T T C
P
r
3 3 3
3 3
10 2 . 3 3 . 1 ) 10 8 22 ( ) 10 2 . 1 6 . 6 ( 3
) 10 8 . 2 6 . 10 ( 3 ) 10 2 . 3 8 . 4 ( 2
1


+ = + +
+ + + =

52 GENERAL CHEMISTRY

3 2 2
) ( 2
3 3 2
O Al CO CO l Al
P P P P P
r
C C C C C + =
T
T T T Cp
r
3
3 3 3
2
10 2 . 3 1 . 3
) 10 8 22 ( ) 10 2 . 1 6 . 6 ( 3 ) 10 8 . 2 6 . 10 ( 3 7 2

=
= + + + + =

+ = +
+ + + + =

) 298 930 ( 3 . 1 177080 ) 10 2 . 3 1 . 3 (

2500 2 ) 10 2 . 3 3 . 1 ( 177080
3
1000
930
3
930
298
0
1000
dT T
dT T H
r

+ +

+

2
930 1000
10 2 . 3 ) 930 1000 ( 1 . 3 2500 2
2
298 930
10 2 . 3
2 2
3
2 2
3

cal H
r
182501
0
1000
=

c) Lavoisier and Laplaces law (1782)
The heat exchange accompanying a transformation is equal in absolute
value and opposite in sign to the heat exchange accompanying the reverse
transformation.

Example:
1 (l) 2 (g) 2 (g) 2 (g) 4
O H CO 2O CH H
r
+ +
2 (g) 2 (g) 4
(l)
2 (g) 2
2O CH O 2H CO H
r
+ +
mol kcal H
mol kcal H
r
r
/ 7 . 212
/ 7 . 212
2
1
=
=


Consequence
When one mole of a chemical compound is decomposed into chemical
elements quantity of heat is absorbed or evolved a quantity of heat equal to the heat
evolved or absorbed when one mole is formed from the constituent elements.
H H
d f
= [37]
where H
f
represents heat of formation and H
d
heat of decomposition.

Thermodynamics of chemical process 53

2.2.3 The second law of thermodynamics

Similarly to the I
st
law, the II
nd
law of thermodynamics is the result of
generalization of the huge human experience. It cannot be demonstrated. At the
earth scale it was not infirmed by any particular case.
Clausius formulation (1850)
Heat cannot spontaneously flow from a colder to a hotter material.
Kelvin formulation
No process is possible in which the sole result is the absorption of heat
from a reservoir and its complete conversion into work. Such a kind of machine
will be a perpetual Motion Machine of II
nd
type.
A heat engine is a mechanical device that provides useful work based on
the difference in temperature of two bodies. In other words, a heat engine is a
mechanical device that continuously transforms heat into an useful work. Therefore
in order to function such an engine necessarily has to be endowed with two heat
reservoirs: a hot source (T
1
) and a cold source (sink) (T
2
) (figure 15)


Figure 15. Schematic representation of the functioning of heat engine

During the functioning of this engine some heat Q
1
is absorbed from the
hot source, a part is transformed into work and the rest Q
2
is transferred to the sink.
Sign convention
(+) for heat received by the system
(-) for heat lost by the system
2 1 2 1
) ( Q Q Q Q W + = = [38]

Hot body
T
1

Engine
Q
1

W
Q
2

Cold body
T
2

54 GENERAL CHEMISTRY

The efficiency is given by:
1
2 1
1
Q
Q Q
Q
L +
= = [39]
Sadi Carnot (1824) established the ideal efficiency of heat engines for an
engine which work through cycles formed from two isotherm transformations
(constant temperature) and two adiabatic transformations (Q =ct). Such a cycle is
called Carnot cycle (figure 16).

1
2 1
T
T T
= [40]


Figure 16. Carnot Cycle

Homework: demonstrate the eq. [40] knowing the heat for the isotherm
transformations:
1
2
1 1
ln
V
V
RT Q = and
1
2
2 2
ln
V
V
RT Q =

Consequence
The maximum efficiency of a heat engine does not depend on the nature of
substance which follows the transformations. It is determined only by the
temperature of the two sources.
For an irreversible cycle the efficiency will be lower than the ideal
efficiency.

+
process reversible for
process le irreversib for

1
2 1
1
2 1
T
T T
Q
Q Q
[41]
V
A
B
C
D
T
1

T
2

Q
1

Q
2

P
Thermodynamics of chemical process 55


2.2.3.1. State functions introduced by the II
nd
Law of Thermodynamics
a) The Entropy
1
2 1
1
2 1
T
T T
Q
Q Q

+
[42]
1
2
1
2
1 1
T
T
Q
Q
+ [43]
1
1
2
2
T
Q
T
Q
[44]
0
2
2
1
1
+
T
Q
T
Q
[45]
The ratio
T
Q
between the heat exchanged in an isotherm and reversible
process and the temperature corresponding to this exchange is called reduced heat.
For any elemental cycle it can be written in the following way:
0
2
2
1
1
+
T
Q
T
Q
[46]
By summing all the reduced heats one obtaines:
0 =

T
Q
rev

0 <

T
Q
irrev

[47]
The ratio
T
Q
rev

is equal with to dS where the S function, introduced by

Clausius in 1894 is called entropy. The entropy is referred to a reversible cycle:

= 0 dS [48]
The entropy is a state function, so its elemental variation is an exact
differential:

= =
2
1
1 2
S
S
S S S dS [49]
The entropy is an extensive function. The units are cal/molK or J /molK.

56 GENERAL CHEMISTRY

For an irreversible process
dS
T
Q
irev
<

[50]
dS
T
Q

[51]
Eq. [51] represents the most general mathematical formulation of the
second law of thermodynamics.
TdS Q [52]
) ( law I pdV dU Q
st
+ = [53]
pdV dU TdS + [54]
Eq [54] represents the correlation expression between I
st
law and II
nd
law of
thermpdynamics.
If U and V are constant
( ) 0
,

V U
dS the entropy change of an isolated system is positive for
spontaneous processes or nule at equilibrium state.
In nature, at constant U and V, take place spontaneously only the
phenomena in which an increase of entropy, ( ) 0
,
>
V U
dS exists. So the II
nd
law of
thermodynamics can be formulate in terms of entropy as follows:
In one isolated system the entropy of the system can not decrease, it is
constant ( ) 0
,
=
V U
dS if in the system only reversible processes take place, and it
increases (dS>0) in any irreversible process. This is why the II
nd
law of
thermodynamics is called also the entropy law.

Entropy for a chemical reaction
For a general chemical reaction like:
.......... ..... .... .......
' ' '
2
'
2
'
1
'
1 2 2 1 1
+ + + + + + +
i i i i
A A A A A A
the variation of the entropy is:

=
react
i i
prod
i i
r
S S S
' '
[55]
Thermodynamics of chemical process 57

where v
i
is the number of moles for i
th
reactant; S
i
is the molar entropy of i
th

reactant; v
i
is the number of moles for i
th
product; S
i
is the molar entropy of i
th

product.
When some phase transitions take place:
T
Q
dS

= ; at constant pressure Q
P
=H so for elemental processes
dH Q = .
T
dH
dS = [56]
For a finite process:
tr
tr
tr
T
H
S S S

= =
1 2
[57]
Ex.
v
vap
vap
T
H
S

=
For a chemical reaction:


+

+ =
2
2
1
1
1 2
T
T
P
tr
tr
i
T
T
P
T
r
T
r
tr
tr
dT
T
C
T
H
dT
T
C
S S [58]
Example:
Calculate the entropy for the reaction:
3CO 2Al 3C O Al
3 2
+ +
At 1000 K and 1 atm. It is known grd cal S
r
/ 88 , 138
0
298
= , the melting
temperature for aluminium 930K, mol cal H
Al
melt
/ 2500 = and the heat capacities
listed in the table below:
Substance C
p
, cal/mol K
Al(s) 4.8 +3.2 10
-2
T
Al(l) 7
CO(g) 6.6 +1,2 10
-3
T
Al
2
O
3
(s) 22 +9 10
-3
T
C(s) 2.7 +2.6 10
-3
T
58 GENERAL CHEMISTRY


Solution:

+

+ + =
1000
930
930
298
298 1000
2 1
2
T
dT
C
T
H
T
dT
C S S
p
r
m
m
p
r r r

) 3 ( 3 2
) ( ( 3 2 ) ( ) ( 1
)
s C s O Al g CO s Al
p p p p p
r
C C C C C + + =
T C
p
r 3
1
10 8 . 6 7 . 0

=
) 3 ( 3 2
) ( ) ( 3 2 ) ( ) ( 2 s C s O Al g CO l Al
p p p p p
r
C C C C C + + =
T C
p
r 3
10 2 . 13 7 . 3
2

=



+

+

+ =
1000
930
3 930
298
3
1000
10 2 . 13 7 . 3
930
2500 2 10 8 . 6 7 . 0
88 . 138 dT
T
T
dT
T
T
S
r

grd cal S
r
/ 51 . 138
1000
=

b) Thermodynamic potentials Helmholtz Free Energy (A or F), Gibbs
Free Energy (G)
According to the correlation between I
st
and II
nd
laws:
L dU TdS [59]
L TdS dU [60]
( ) L
T
TS - U d [61]
= reversible process
< irreversible process
It is defined:
A TS U or F [62]
(A from German word Arbeit =work)
The IUPAC (International Union of Pure and Applied Chemistry)
recommends the letter A as well as the denomination of Helmholtz energy. In
practice it is simply called the free energy.
A (F) the Helmholtz free energy introduced by Helmholtz
Thermodynamics of chemical process 59

( ) V T A A , = - state function

= 0 dA [63]

= =
2
1
1 2
A A A dA [64]
( ) L dA
T
[65]

The Helmholtz free energy is a thermodynamic potential which measures
the useful work obtainable from a closed thermodynamic system at a constant
temperature.
Similarly:
pdV dU TdS + [66]
PV U H + = [67]
VdP PdV dU dH + + = [68]
VdP PdV dH dU = [69]
PdV VdP PdV dH TdS + [70]
VdP dH TdS [71]
VdP TdS dH [72]
( ) VdP TS H d
T
[73]
By definition:
TS H G [74]
G Gibbs free energy
( ) P T G G , = state function [75]

= 0 dG [76]
G G G dG = =
1 2
2
1
[77]
( ) VdP dG
T
[78]
if the pressure is constant then
( ) 0
,

P T
dG [79]
60 GENERAL CHEMISTRY

In a system, at constant temperature and pressure can take place
spontaneously only the processes in which the Gibbs free energy is
decreasing( ) 0
,
<
P T
dG . At equilibrium the Gibbs free energy of the system is
minimum and it is maintained constant ( ) 0
,
=
P T
G
dT
T
G
dP
P
G
dG
T

= [80]
TS H G =
SdT TdS dH dG =
VdP TdS dH =
VdP SdT dG + = [81]
Comparing equation [80] with equation [81] one gets:
V
P
G
T
=

[82]
and S
T
G
P
=

[83]
for a finite process:
S
T
G
=

[84]
TS H G =
P
T
G
T H G

+ = [85]
P
r
r r
T
G
T H G

+ = [86]
Equation [86] is called Gibbs Helmholtz equation and establishes the
connection between the chemical affinity, G
r
and the reaction heat H
r
.


Thermodynamics of chemical process 61


2.2.4. Third Law of thermodynamics

The Nernst heat Theorem
The entropy change accompanying any physical or chemical
transformation approaches zero as the temperature approaches zero: S0 as T0
provided all the substances involved are perfectly ordered.

Planck affirmation:
At 0 K not only S is zero but also the molar entropy (S) of any crystalline
pure element is zero.
0
0
= S [87]
S
0
=0 [88]
Equation [88] represents the mathematical expression of the III
rd
law of
thermodynamic.
Summarized Third Law of thermodynamics is: The entropy of all perfect
crystalline substances is zero at T =0 K.

2.2.5. Chemical Potential

In open systems formed from many substances, (so the composition is
varying due to the changes with the surroundings), the expressions of the
thermodynamics functions established in the frame of I
st
and II
nd
Laws should be
completed with composition variables:
.....) ,......, , , , (
2 1 i
n n n S V U U = [89]
.....) ,......, , , , (
2 1 i
n n n S P H H = [90]
.....) ,......, , , , (
2 1 i
n n n S V F F = [91]
.....) ,......, , , , (
2 1 i
n n n P T G G = [92]
The elementary variation for the Gibbs free energy will be:
62 GENERAL CHEMISTRY

...
) ( 3 1 3 2
, ,
2
,.., , . ,
2
1
,..., , , ,
1
+

+ + =

i
n P T
i
n n n P T n n n P T
dn
n
G
dn
n
G
dn
n
G
VdP SdT dG
i j j i i

[93]
The partial molar function:
( )
i
n P T
i
i
i j j
n
G
G =

, ,
[94]
is called chemical potential (Gibbs)

+ + =
i
i i
dn VdP SdT dG [95]

2.3. Chemical equilibrium

The experience showed that the chemical reactions occur in forward
direction as well as in opposite direction.
Example:
H
2
+I
2
2 HI
In a chemical process, chemical equilibrium is the state in which the
chemical activities or concentrations of the reactants and products have no net
charge over time. Usually, this state results when the forward chemical process
proceeds at the same rate as their reverse reaction. The reactions rates of the
forward and reverse reactions are generally not zero but, being equal, there are no
net charges in any of the reactant or product concentrations.

2.3.1. Thermodynamical condition of chemical equilibrium.
Reaction isotherm

Let take a chemical reaction in general form:
... ...
2 2 1 1
+ + + +
i i
A v A v A v ... ...
' '
2
'
2
'
1
'
1
'
+ + + + i i A v A v A v
Thermodynamics of chemical process 63

The chemical potentials (free partial molar Gibbs energy) are:
, ,
2 1
, ...,
i
for reactants ,
' '
2
'
1
..., , , ly respective
i
for products.
The expression:
( ) 0
' '
,
= =

react
i i
prod
i i P T
r
v v G [96]
is the thermodynamical condition of the chemical equilibrium.
For p =1 atm

=
react
i i
prod
i i
T
r
v v G
' ' 0
[97]
representing the standard Gibbs energy of the reaction.
The expression:
a T
r
K RT G ln
0
= [98]
links thermodynamic data with chemical important equilibrium constant K.
K
a
is the equilibrium constant, calculated with activities:

=
react
v
i
prod
v
i
a
i
i
a
a
K
'
'
[99]
where : a
i
is the activity of i
th
component at equilibrium. It is a kind of
effective mole fraction:
*
i
i
i
p
p
a = ; [100]
where p
i
is the vapor pressure of i
th
component (at equilibrium) when it is a
component of solution and
*
i
p vapor pressure of pure i
th
component at
equilibrium;
- notation for product operator.
For gases instead of activities fugacities f are used which have pressure
dimensions: 1 lim
0
=

p
f
p
.
For an ideal gas mixture p f = :
64 GENERAL CHEMISTRY

=
react
v
i
prod
v
i
p
i
i
p
p
K
'
'
[101]
For very diluted solutions activities can be replaced by corresponding
concentrations:
x a
K K or
m a
K K or
c a
K K

=
react
v
i
prod
v
i
x
i
i
x
x
K
'
'

=
react
v
i
prod
v
i
m
i
i
m
m
K
'
'

=
react
v
i
prod
v
i
a
i
i
c
c
K
'
'
[102]
where: x
i
molar ratio at equilibrium
t
i
i
n
n
x = [103]
m
i
molal concentration (moles of substance in 1 kg of solvent) at
equilibrium
c
i
molar concentration (mols of substance in 1L of solution) at
equilibrium
In this case the free Gibbs energies of reaction will be:
( ) ( ) ( )
c T
r
m T
r
T
r
G G G
0 0 0
[104]
where
x T
r
K RT G ln
0
=

m m T
r
K RT G ln ) (
0
=
c c T
r
K RT G ln ) (
0
=

2.3.2 Expression of equilibrium constants for reactions among
gases

i
i
v
i
v v
v
i
v v
p
p p p
p p p
K
...
...
2 1
' '
2
'
1
2 1
' '
2
'
1

= [105]

Thermodynamics of chemical process 65

a)
i i
Px p = ,
where:
i
p is partial pressure of i
th
component at equilibrium
P is the total pressure
x
i
is molar ratio of i
th
component at equilibrium
v
x
v
v
v
i
v v v
v
i
v v v
p
P K
P
P
x x x x
x x x x
K
i
i
i
i
i
i

=
'
3 2 1
' '
3
'
2
'
1
... ...
... ...
3 2 1
' '
3
'
2
'
1
[106]

=
i i
v v v
'
[107]
b) RT n V p
i i
= [108]
RT c RT
V
n
p
i
i
i
= = [109]
( )
( )
( )

= RT K
RT
RT
c c c c
c c c c
K
c
i
i
p
i
i
i
i
'
3 2 1
' '
3
'
2
'
1
... ...
... ...
3 2 1
' '
3
'
2
'
1
[110]
R =0.082 Latm / molK
c)

= ) (RT K P K
c x
[111]

=
RT
P
K K
X
c
[112]
If there is no change of mole numbers in a reaction, 0 = v ,
c x p
K K K = = [113]
These equilibrium constants are dimensionless.

Example
For the reaction COCl
2
CO +Cl
2
, at equilibrium, at 550C and 1 atm
77% of COCl
2
is dissociated. Calculate K
x
, K
p
and K
c
.

Solution:
COCl
2
CO +Cl
2

Initial: 1 0 0 moles
Equilibrium: 1 moles Total 1 + + =1 + moles
66 GENERAL CHEMISTRY

1
100
77
= moles of COCl
2
dissociated.

+
=
1
CO
x

+
=
1
2
Cl
x

=
1
1
2
COCl
x
( )( )

+
=
+

+
=
1 1
1
1
1 1
2
x
K
( )
( )( )
456 . 1
77 . 0 1 77 . 0 1
77 . 0
2
=
+
=
x
K

= P K K
x p
1 1 1 1 = + =
456 . 1 1 456 . 1 = =
p
K
( )

= RT K K
p c

0215 . 0
823 082 . 0
1
456 . 1 =

=
c
K

2.3.3 Estimation of the equilibrium constant from
thermodynamic data

It is known that
a T
r
K RT G ln
0
=
But
0 0 0
T
r
T
r
T
r
S T H G = [114]
dT
T
C
S S
T
p
r
r
T
r

+ =
298
0
298
0
[115]

+ =
T
p
r r
T
r
dT c H H
298
0
298
0
[116]
So
RT
G
K
T
r
a
0
ln

= [117]
Thermodynamics of chemical process 67

or
R
S
RT
H
K
T
r
T
r
a
0 0
ln

+

= [118]
or

=

T
p
r
T
p
r T
r r
a
dT
T
c
dT c
T R R
S
RT
H
K
298 298
0 0
298
1 1
ln [119]
The equation [119] solves the most important problem of chemical
equilibrium: the integral calculus of equilibrium constant from thermodynamical
data - reaction heat, molar heat capacities, and entropies.

2.3.4. The shift of chemical equilibrium; Le Chatelier Brawn
principle

If a dynamic equilibrium is disturbed by changing the conditions, the
position of equilibrium shifts in order to counteract the change.
A system at equilibrium, when subjected to a disturbance, responds in a
way that tends to minimize its the effect.

2.3.4.1 Temperature influence on the equilibrium constant. Equation
Vant Hoff
T
G
R
K
r
a
0
1
ln

= [120]
Differentiation of
a
K ln with respect to temperature gives:
dT
T
G
d
R dT
K d
r
a

=
0
1 ln
[121]
From the Gibbs Helmholtz equation we have:
2
0
0
RT
H
dT
T
G
d
r
r

[122]
So:
68 GENERAL CHEMISTRY

2
ln
RT
H
dT
K d
r
a

= [123]
The equation [123] is called vant Hoff equation
From the equation [123] one can see the following:
- for endothermic reactions
a
r
K H > 0
0
increases with the
increasing temperature. So the increase the temperature will have as
effect the shift of the reaction to the right side;
- for exothermic reaction
a
r
K H < 0
0
decreases with the increasing
temperature. Thus the increase of the temperature will result in the
shift of the reaction to the left side

2.3.4.2. Pressure influence on the equilibrium constant
It is known
RT
G
K
r
p
0
ln

=
Since
0
G
r
is not depending on pressure K
p
is not depending on pressure.
However the pressure has influence on the equilibrium composition:

v
p x
P K K

=

x
K v > 0 decreases with the increases of pressure
Example: CO
2
CO +
2
1
O
2

2
1
= v

x
K v < 0 increases when the pressure increases
Example: N
2
+3H
2
2NH
3
2 = v

x
K v = 0 does not depend on pressure
Example: O H CO
2
+ CO
2
+H
2
0 = v
Example
For the reaction
(g) 3 (g)
SO CO +
2(g) 2
SO CO + the values for standard
enthalpy and free Gibbs energy are: kcal H
r
14 . 44
0
298
= and
Thermodynamics of chemical process 69

kcal G
r
72 . 44
0
298
= . Calculate
0
400
G
r
and K
p
at 400 K, supposing that
0 =
p
C cal/K for the temperature range 298 - 400K, and an ideal gases behavior.

Solution:
2
0
ln
RT
H
dT
K d
r
p

=


=
2
1
2
1
2
0
ln
T
T
r
K
K
p
T
dT
R
H
K d
P
P

=
2 1
0
1 1
ln
1
2
T T R
H
K
K
r
P
P

0
298 1
298 G K T
r
=
0
400 2
400 G K T
r
=
p T
r
K RT G ln
0
=
2
0
400
1
0
298
2 1
ln ln
RT
G
K
RT
G
K
r
P
r
P

2 1
0
1
0
298
2
0
400
1 1
T T R
H
RT
G
RT
G
r r r

=
2 1 1
0
298
2
0
400
1 1
T T
H
T
G
T G
r
r

+ =
400
1
298
1
14 . 44
298
72 . 44
400
0
400
G
r

kcal G
r
45
0
400
=
2
0
400
ln
RT
G
K
r
p

=
51 . 56
400 987 . 1
45000
ln
400
=

=
p
K
24
10 5 . 3 =
p
K .
70 GENERAL CHEMISTRY