05 - 01 - The Second Law of Thermodynamics

1
2010 Imam Siswanto Kimia Fisika I

universitas airlangga
excellence with morality
KIMIA FISIKA I
Second Law of Thermodynamics
2
AH = -1000 kkal
3
AH = +700 kkal
4
???
AH = -300 kkal
5
AH = -3000000 kkal
6
The first law of thermodynamics does not define the ease or extent of
convertibility of one form of energy into another.

Formulation by Kelvin :

No process is possible in which the sole result is the absorption of
heat from a reservoir and its complete conversion into work
7
Entropy
The second law of thermodynamics can also be expressed in term of
the entropy :

The entropy of an isolated system increases in the course of a spontaneous
change :
0
tot
S A >
8
Entropy
The thermodynamic definition of entropy is based on the
expression :

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

rev
dq
dS
T
=
f
rev
i
dq
S
T
A =
}
9
Entropy Change in Isolated Systems
Isolated system :
a system and heat reservoir adiabatically insulated from their
surrounding.

Suppose that the substance in the cylinder undergoes an
isothermal and reversible expansion from volume V
1
and V
2
.
The substance will absorb from the reservoir a quantity of heat q
r
,
and the reservoir will lose a quantity of heat q
r
.
r
s
q
S
T
A =
r
r
q
S
T
A =
1
0
s r
S S S A = A + A =
10
If we compress the substance now isothermally and reversibly from
V
2
to V
1

Further the total change in entropy for the complete cycle, AS, is

'
r
s
q
S
T
A = '
r
r
q
S
T
A =
2
' ' 0
s r
S S S A = A + A =
1 2
0 S S S A = A + A =
11
If the process is irreversible
1
0
r
q q
S
T T
A = >
2
' ' 0
s r
S S S A = A + A =
0
r
q q
S
T T
A = >
12
The Second Law of Thermodynamics
If instead of finite changes we consider infinitesimal ones, it can be
summarized that for any process occurring in an isolated system the entropy
change dSi is given by
0
i
dS >
All process in nature tend to occur only with an increase in entropy
and that the direction of change is always such as to lead to the
entropy increase
13
Entropy Change for Systems Only
When we ignore the surroundings, the entropy of the system can be zero,
positive, or negative.

The differential change in entropy :

Or

Form the first law : dq = dE + dW, where dW consist in pdV as well as other types
of works, dw, then
0
i r
dS dS dS = + >
/
r
dS dq T =
0 TdS dq >
14

Then we get

When only P V work is involved dw = 0, we get

However, for reversible process p = P, dw = dw
m
, we obtain :

And when dw
m
= 0,
' dq dE pdV dw = + =
' 0 TdS dE pdV dw >
0 TdS dE pdV >
' 0
m
TdS dE PdV dw =
0 TdS dE PdV =
15
Variable T and V

See page 305
Dependence of Entropy on Variable of a System
V T
S S
dS dT dV
T V
c c
| | | |
= +
| |
c c
\ . \ .
T T
E S
T P
V V
c c
| | | |
=
| |
c c
\ . \ .
v
V
C P
dS dT dV
T T
c
| |
= +
|
c
\ .
16
Variable T and P

See page 306
P T
S S
dS dP dP
T P
c c
| | | |
= +
| |
c c
\ . \ .
1
T T
S H
V
P T P
( c c
| | | |
=
| | (
c c
\ . \ .

p
P
C
V
dS dT dP
T T
c
| |
=
|
c
\ .
17
Also on rearrangements we have

and

T V
E P
T P
V T
c c
| | | |
=
| |
c c
\ . \ .
T P
H V
V T
P T
c c
| | | |
=
| |
c c
\ . \ .
18
Entropy Change in Ideal Gases
In the case of T and V, we have

Or if we deal with n moles of gas, it is more convenient to write C
v
as nC
v
.
And for ideal gas, PV = nRT , finally
v
V
C P
dS dT dV
T T
c
| |
= +
|
c
\ .
2 2
1 1
ln ln
T V
S nCv nR
T V
A = +
19
In the case of T and P, we have

Or if we deal with n moles of gas, it is more convenient to write C
v
as nC
v
.
And for ideal gas, PV = nRT , finally
p
P
C
V
dS dT dP
T T
c
| |
=
|
c
\ .
2 2
1 1
ln ln
p
T P
S nC nR
T P
A =
20
Example

1. Calculate the entropy change involved in the isothermal reversible
expansion of 5 moles of an ideal gas from a volume of 10 liters to a
volume of 100 liters at 300
0
K.

2. For a certain ideal gas C
p
= 5/2 R cal mole-1 degree-1. Calculate the
change in entropy suffered by 3 moles of the gas on being heated from
300 to 600
0
K at
(a) Constant pressure
(b) Constant volume
21
Entropy of Mixing for Ideal Gases
Suppose : n
1
, P
1
0
+ n
2
, P
2
0
P
1
and P
2

For any constant temperature the change in entropy accompanying a change
in pressure is given by:

1
1 1
0
1
ln
P
S n R
P
A =
0
1
1
1
ln
P
n R
P
=
0
2
2 2
2
ln
P
S n R
P
A =
22
Entropy of Mixing for Ideal Gases
And the total entropy of mixing is

But according to Daltons law : P
1
= N
1
P
t
and P
2
= N
2
P
t

And for special instance where P
1
0
= P
2
0
= P
t
,

1 2 m
S S S A = A + A
0 0
1 2
1 2
1 2
ln ln
P P
n R n R
P P
= +
0 0
1 2
1 2
1 2
ln ln
m
t t
P P
S n R n R
N P N P
A = +
1 1 2 2
( ln ln )
m
S n R N n R N A = +
23
Entropy Change in Physical Transformations
The transition enumerated take place reversibly at constant temperature T
and pressure P and are accompanied by an absorption or evolution of DH cal
of heat for a given quantity of substance.
Therefore, for all such processes

Of necessity this equation is valid only when reversible conditions obtain
during the transformation, i.e., when equilibrium exists between the two
forms.
r
q H
S
T T
A
A = =
24
Example

Find the entropy change for the transition :
H
2
O(l, 1 atm) = H
2
O(g, 1 atm) AH
373.2 K
= 9717 cal mole
-1

AS = AH/T = 9717/373.2 eu = 26.04 eu
25
Example

Find the entropy change for the transition :
H
2
O(l, 1 atm) = H
2
O(g, 0.1 atm)

AS = AS
vaporization
+ AS
expansion
1
2
ln
H P
R
T P
A
= +
9717 1
4.58log 30.62
373.2 0.1
eu = + =
26
Entropy Change in Chemical Reactions
The entropy change accompanying a chemical reaction is defined as the
difference between the sum of the entropies of all the products and the sum
of the entropies of all reactants.

aA + bB + . . . = cC + dD + . . .

The entropy change is given by

AS = (cSc + dSD + . . . ) (aSA + bSB + . . . )

Or in another form :
2
1
2 1
T
p
T
dT
S S C
T
A A = A
}
2
1
ln
p
T
C
T
= A

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2010 Imam Siswanto Kimia Fisika I

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