1

Physical Chemistry II
Prof. Dr. Ishak Ahmad
PPSKTM, FST, UKM
G150 (Chemistry Building)
gading@ukm.edu.my
Course content (Ishak Ahmad)
Part I:
2
nd
and 3
rd
Laws of thermodynamic
Spontaneous change
Dispersal of energy
Entropy
2
nd
law of thermodynamic
Entropy changes accompanying specific processes
Carnot cycle
Third law of thermodynamic
Nernst heat theorem
Gibbs free energy
Relation between H, S and G
Standard reaction Gibbs energies
Helmholtz and Gibbs energies
Maximum work
Properties of internal energy
Properties of Gibbs energy

2
3
Part II
Physical transformations of pure substances
The stabilities of phases
Phase boundaries
Supercritical fluids
Three typical phase diagram
Thermodynamic criterion of equilibrium
The dependence of stability on the condition
The location of phase boundaries
Solid-liquid boundary
Liquid-vapour boundary
Clausius-Clapeyron equation
Ehrenfest Calssification of phase transitions

4
SECOND LAWS OF
THERMODYNAMICS
Many processes are reversible and yet tend
to proceed in a direction in which they are
said to be spontaneous.
What makes a reaction spontaneous? What
drives the reaction in one direction and not
the other?

2.1 Spontaneous Processes
Spontaneous change: Occurs by itself,
without continuous outside assistance under
specific condition (temperature, pressure,
and concentration).
Non spontaneous: Occurs with continuous
outside assistance. As soon as supply
energy cut off, the process stop.


5
Some spontaneous changes occur very
rapidly i.e. biochemical reactions.
Touch something very hot, spontaneous
jerk hand quickly.

Others occur slowly and many years such
as erosion of mountain.
Spontaneous process cannot occur in
both direction under the same conditions.

6
Dispersal of Energy
Spontaneous changes are accompanied
by dispersal of energy into a more
disordered form.

Bouncing ball:
Ball does not return to original height, as
energy is redistributed to molecules in the
floor and ball as heat - inelastic energy
losses.
Ball eventually comes to rest, losing all
energy (dispersed) into thermal motion of
atoms in the floor
the reverse process will never occur!
7
Heated floor and ball:
Molecules and atoms in the floor (and
ball) undergo thermal (random) motion
In order for the ball to spontaneously
bounce, it would require a
spontaneous localization of motion,
to create an upwards motion of all of
the atoms - a virtually impossible
process**
8
Normally, spontaneous processes occur so
as to decrease the energy of the system,
e.g. spring in a clock unwind.
Examples of spontaneous chemical
reactions that are exothermic (most cases):

2 Al(s) + 3 Br
2
(l) 2 AlBr
3
(s) H
o
= -511 kJ/mol

2 H
2
(g) + O
2
(g) 2 H
2
O(g) H
o
= -241.82 kJ/mol

P
4
(s) + 5 O
2
(g) P
4
O
10
(s) H
o
= -2984 kJ/mol




9
However endothermic reaction can also
spontaneous e.g. ice melts spontaneous
above 0
o
C.

E.g.:
1. Decomposition of mercury(II) oxide:
2HgO(s) 2Hg(l) + O
2
(g)
AH= +ve

2. Dissolution of ammonium nitrate in
water
NH
4
NO
3
(s) NH
4
+
(aq) + NO
3
-
(aq)
AH= +ve


10
Conclusion:
Exothermic favors the spontaneity of
reaction but does not guarantee it.
Just as it possible for an endothermic
reaction to be spontaneous.
It is also possible for an exothermic
reaction to be nonspontaneous.
We cannot confirm a chemical reaction
will occur spontaneously solely on the
basis of energy changes (AH) in the
system.

Another thermodynamic quantity must be
take into consideration which turns out to
be entropy.
11
2.2 ENTROPY
A measure of the randomness or
disorder of a system.
Symbol S.
The greater the disorder of the system,
the greater its entropy.
Conversely, the more ordered a system,
the smaller its entropy.
Particles in the solid state are more
ordered than those in the liquid state,
which in turn are more ordered than
those in gaseous state.
S
solid
< S
liquid
<< S
gas


12
Figure shows several processes that
lead to an increase in entropy.
In each case more ordered stated
to less ordered.
Factors that increase the entropy
of the system
13
Melting and vaporization
Melting and vaporization processes
have S > 0.
S
solid
< S
liquid
<< S
gas

Molecules in the liquid state have
more space than in the solid state.
Less ordered.
H
2
o
The solution process usually leads to
an increase in entropy.
Consequently, the solution is more
disordered than the pure solute and
pure solvent.
Two factors to entropy increase:
solution process
dissociation into the compound into
ions.
NaCl(s) Na+(aq) + Cl-(aq)


Solution process
14
Heating also increases the entropy of
the system.
The higher the temperature the greater
the molecular motion.
Increase in randomness at molecular
level lead to an increase in entropy.

Increase temperature
15
Polymorphism and Molar mass
For different substances in the same
phase, the molecular complexity and
molar mass determine which ones
have higher entropy.
Case 1:
Diamond and graphite. Diamond has
a smaller entropy because its
structure is more ordered.
Case 2:
Neon and Helium. Neon has greater
entropy because its molar mass is
greater.
16
The Second Law of
Thermodynamics
The connection between entropy and the
spontaneity of reaction Second
Law of Thermodynamics.
Definition:
The entropy of an isolated system
increases in the course of a spontaneous
process, AS
tot
> 0 or AS
univ
> 0

Universe system and surroundings.
AS
univ
= S
sys
+ S
surr

Spontaneous process:
AS
univ
= S
sys
+ S
surr
> 0
Equilibrium process:
AS
univ
= S
sys
+ S
surr
= 0

2
nd
law and entropy
First Law
Uses internal
energy, U, to
identify permissible
changes
Second Law
Uses entropy, S, to
identify the
spontaneous changes
among the permissible
changes
17
The law used to identify spontaneous
change, and can be quantified in terms of a
state function* known as entropy
*Value depends only on the current state of the system
and is independent of how the state has been prepared
18
The change in a disorderly manner
depends on the quantity of energy
transferred as heat.
The thermodynamic definition of
entropy is based on the expression:



For a measurable change between two
state i and f this expression integrates
to

}
= A
f
i
T
dq
s
19
Entropy change: Reversible
Isothermal Expansion of
Perfect Gas
AU = 0 so q = -w (AU = q + w)

AV = V
f
- V
i
so w < 0

OR
q = nRT ln V
2

V
1


Hence,
AS = nR ln V
2

V
1
or
S = - nR ln P
2
P
1


|
|
.
|

\
|
=
=
}
1
2
2
1
ln
V
V
nRT w
V
dV
nRT w
V
V
Work expansion = -ve
20
The Variation of Entropy
with Temperature
From the measurable change
between two state i and f;

}
= A
f
i
T
dq
s
S(T
f
) = S(T
i
) +
}
f
i
T
dq
or
From the definition of constant-pressure
heat capacity;
q
p
= C
p
AT
Consequently, at constant pressure;
}
+ =
f
i
p
i f
T
dT C
) T ( S ) T ( S
21
When C
p
is independent of temperature,
we obtain:

}
+ =
f
i
p i f
T
dT
C ) T ( S ) T ( S
Finally;
|
|
.
|

\
|
+ =
i
f
p i f
T
T
ln C ) T ( S ) T ( S
The same expression applies at constant
volume, but with C
p
replaced by C
v
.
22
Variation of Entropy with
Temperature for Expansion of
Perfect Gas
By combining the entropy at different
temperature:

|
|
.
|

\
|
= A
i
f
p
T
T
ln nC ) sys ( S
and the entropy of the isothermal
expansion of perfect gas:


1
2
V
V
ln nR S = A
Hence we get (factor T and V are
included):

1
2
1
2
V
V
ln nR
T
T
ln C ) sys ( S
p
+
|
|
.
|

\
|
= A
Quiz
Write the equation for each types of
work:
a. Free expansion
b. Expansion against constant pressure
c. Isothermal reversible expansion


23
Answer

24
Entropy at phase transition
25
Melting of a solid and vaporization of a
liquid correspond to accept thermal energy
Energy flow into a system, at a constant
temperature
These inflows of thermal energy
correspond to the heats of fusion and
vaporization.
The entropy increase associated with
melting, for example, is just H
fusion
/T
m
.
Heat capacity, C of a phase expresses
the quantity of heat required to change the
temperature by a small amount T.

At 1 atm : standard entropy of a substance
At 298K, and are expressed in units of J K
1
mol
1


Entropy at a Phase Transition
Consider the phase transitions of water, at transition
temperatures T
trs
.
For ice water, T
trs
= 273 K, ice in equilibrium with liquid
water at 1 atm.
The external pressure is constant for a glass of ice
water, and in order to match attractive forces between
ice molecules, energy must come from kinetic energy
of the water molecules or the surroundings.
At T
trs
, any transfer of heat between the system and
surroundings is reversible since the two phases in the
system are in equilibrium (the forces pushing the ice
towards melting are equal to those pushing the water
towards freezing) - so a phase transition is
reversible.
It does not matter how the ice melts (what path it
takes) since entropy is a state function. What does
matter for this particular expression is that the system
be isothermal. If it was not isothermal, one would
have a problem examining the process in steps as
we shall see.
26
27
Entropy of Phase
Transition Temperature
Because at constant pressure,
q = A
trans
H

The change in molar entropy of the
system is;





trs
trs
trs
T
H
S
A
= A
Troutons Rule
Troutons Rule: This empirical observation
(see Table 4.2) states that most liquids have
approximately the same standard entropy of
vaporization,
vap
S
o
85 J K
-1
mol
-1
: So,

vap
H
o
= T
b
85 J K
-1
mol
-1

(See Table 3.1 Atkins 9
th
ed)

Exceptions:
In water, molecules are more organised in
the liquid phase (due to hydrogen bonding),
so a greater change of disorder occurs upon
vapourization
In methane, the entropy of the gas is slightly
low (73.2 J K
-1
mol
-1
at 298 K) and in light
molecules very few rotational states are
accessible at room temperature -
associated disorder is low
28
Examples
Calculate S when argon at 25
o
C and 1.00 atm
in a container of volume 500 cm
3
expands to
1000 cm
3
and is simultaneously heated to
100
o
C. C
p,m
(Ar) = 20.786 J K
-1
mol
-1


29
Methodology:
Since S is a state function, we can choose a convenient
path from initial to final state: (1) isothermal expansion
to final volume, then (2) reversible heating at constant
volume to final temperature
Amount of Ar present is n = pV/RT = 0.0204 mol
C
p,m
(Ar) = 20.786 J K
-1
mol
-1

(1) Expansion from 500 cm
3
to 1000 cm
3
at constant T:
S = nR ln 2.00 = +0.118 J K
-1

(2) Reversible heating from 25
o
C to 100
o
C at constant
V:
S =(0.0204 mol)(12.47JK
-1
)ln(373 K/298 K)
= +0.057 J K
-1
Overall entropy change:
S = +0.118 J K
-1
+ 0.057 J K
-1
= +0.173 J K
-1

Entropy Change of Melting Ice
Consider the entropy changes for putting
an ice cube in a glass of warm water and
letting it melt (adiabatic container).



Start at Ti
(1) Calculate S to cool the water to 0
o
C by
reversibly removing heat, q
1
, from the system
(2) At T
fus
, calculate the amount of heat, q
2
, to be
added to the system to melt the ice cube
(3) Calculate the difference between the two
amounts of heat and add back remaining heat so
that the total heat lost or gained is zero
(adiabatic system) - determine the entropy change
in this process
At each step, the infinitesimal entropy change for
the system, dS, is just dq divided by the T. For the
cooling and heating of water, integrate over the
temperature range, since the temperature is not
constant.
30
Entropy Change of Melting Ice, 2
Step 1: Entropy decrease for the
system as the water is cooled



Step 2: Melt the ice at T
fus
= 0
o
C (q
fus
=
q
2
)



Step 3: Balance the heat by (in this
example) adding an amount of heat
31
i
fus
p
Tf
T
p
T
T
T
T
C
T
dT
C
T
dq
S
fus
i
fus
i
ln
1
= = = A
} }
T
H
T
q
S
sur
sur
surr
A
= = A
|
|
.
|

\
|
= A
fus
f
surr
T
T
Cp S ln
Is the process spontaneous? (We know
intuitively that it is - sticking an ice cube
into warm water melts the ice cube!!).

How do we prove this?
Show that the total entropy change (the
system plus the surroundings) is positive.
The entropy change of the system we
know is:
S
1
+ S
2
+ S
3
32
Adiabatic Changes

33
Carnot Cycle
The Carnot cycle, named after Sadi Carnot, has
four reversible stages
1. Reversible isothermal expansion from A to B at
T
h
, S = q
h
/T
h
, q
h
is heat supplied from a hot source,
and is positive
2. Reversible adiabatic expansion from B to C, no
heat leaves system (S = 0), temperature falls from
T
h
to T
c
, where T
c
is the temperature of the cold sink
3. Reversible isothermal compression from C to D,
S = q
c
/T
c
, qc is heat released into a cold sink, and is
negative
4. Reversible adiabatic compression from D to A,
no heat enters the system (S = 0), temperature rises
from T
c
to T
h
34
1
st
law analysis of Carnot cycle
Step 1 : Isothermal expansion, U
1
= q + w

Step 2 : Adiabatic expansion, U
2
= w
2

Step 3 : Isothermal compression, U
3
= q
2
+ w
3

Step 4 : Adiabatic compression, U
4
= w
4
35
Total entropy change in Carnot cycle:



This S zero since

36
}
+ =
c
c
h
h
T
q
T
q
dS
c
h
c
h
T
T
q
q
=
S = 0 for Carnot Cycle
for reversible isothermal expansion of a
perfect gas:



And for reversible adiabatic processes


Multiplying the expressions

and simplifying:


Finally we get:

37
|
|
.
|

\
|
=
A
B
h h
V
V
nRT q ln
|
|
.
|

\
|
=
C
D
c c
V
V
nRT q ln
c
c D
c
h A
T V T V =
c
h B
c
c C
T V T V =




c
i i
c
f f
T V T V =
R
C
c
m V ,
=
c
c
c
h B D
c
c
c
h C A
T T V V T T V V =
C
D
B
A
V
V
V
V
=
|
|
.
|

\
|
=
B
A
c c
V
V
nRT q ln
Thermodynamic in Carnot Engine
Step 1 : Isothermal expansion,


Step 2 : Adiabatic expansion, U
2
= w
2





Step 3 : Isothermal compression, U
3
= q
2
+ w
3


Step 4 : Adiabatic compression, U
4
= w
4

38
|
|
.
|

\
|
=
1
2
V
V
nRT w ln
c
i i
c
f f
T V T V =
R
C
c
m V ,
=
|
|
.
|

\
|
=
3
4
V
V
nRT w ln
If we combine the net work of
the engine:

39
|
|
.
|

\
|
=
1
2
c - h
V
V
) T nR(T w ln
Efficiency
The same calculation just completed for
gases applies to all types of materials and
systems. We define the efficiency, c, of a
heat engine:



The greater the work output from
a given supply of heat, the
greater the efficiency of the
engine
Work performed by the engine is
the difference between heat supplied from
the heat source and returned to the cold sink:



Since q
c
< 0,
40
h
q
w
= =
absorbed heat
performed work
c
h
c
h
c h
q
q
q
q q
+ =
+
= 1 c
h
c
T
T
= 1 c
Carnot cycles and Engines
2
nd
Law: all reversible engines have the
same efficiency regardless of
construction - Two engines A and B,
assume A more efficient than B, coupled
together using the same reservoirs.
41
A: takes heat q
h
, releases heat q
c
,
B: takes heat q
c
releases q
h

Since A more efficient than B, not
all work A produces is needed for
this process, and difference can
be used to do work
42
Net result: cold reservoir stays the
same, hot reservoir loses energy,
and work has been produced.

Problem: heat (disordered thermal motion)
has been converted directly into work
(ordered molecular motion) without the need
for a cold sink - assumption that reversible
engines A and B can have different
efficiencies is false!

Relationship between heat transfers and
temperatures must be independent of
working materials