Lecture 6

Entropy

Reversible change of a perfect/ideal gas:

=
=
=

If CV is constant in this range,

+
+

ln

ln

Irreversible change of a perfect/ideal gas:

Entropy
Heating at constant pressure:
=
If Cp is constant in this range,

=
=

ln

Q. Find S when 100g of water is heated reversibly from 25C to 50C

at 1 atm. Specific heat capacity of water in this temperature range
1.00 cal g-1 C -1

Entropy

Irreversible phase change:

Say, 1 mole of supercooled water at -10C and 1 atm pressure
changes its phase to form 1 mole of ice at -10C and 1 atm pressure.
Irreversible
Ice at -10C and 1 atm

Liquid water at -10C and 1 atm

q1

Reversible

Liquid water at 0C and 1 atm

q2
273 '
ln
263 '

q3
Ice at 0C and 1 atm

4567
263 '
=
= ,123
+ , 8 ln
+
273 '
273 '
&
273 ' 79.7 "#$ % 18 %
&
&
+
= 1.01 "#$ % ' 18 % ln
263 '
273 '
263 '
&
&
+ 0. 50"#$ % ' 18 % ln
273 '

Entropy

69

7:73

76

7:73

76

Reversible process
69

=
=
69

69

=0
=0

7:73
7:73

76
7:73

Entropy
Irreversible process

When the system does work,

+

Clausius inequality

Entropy
If the system is isolated from its surroundings,

=0

2nd Law of Thermodynamics

In an isolated system, entropy can not decrease when a spontaneous
change occurs.
The universe is an isolated system !!
Clausius statement for the 1st and 2nd Laws:
The energy of the universe is constant. The entropy strives to
reach a maximum.

3rd Law of Thermodynamics

Statistical view of Entropy
= < ln =

Boltzmann formula for entropy,

< = >?$@AB#

D "? D@# @ =

EF

= 1.381 10&

H' &

= = IBJKL ?M BN"L?D@#@KD ?M # DOD@KB

- system can exist in only some specific energy states
- more the number of such possible states, more is the entropy
At 0 K, all molecular motion ceases, in a perfect crystal :
localization of matter: zero randomness: entropy zero!!
So, at 0 K; = = 1, so

= < ln 1 = 0

3rd Law of Thermodynamics

Nernst heat theorem
Entropy change in a physical or chemical process approaches zero, as
the temperature approaches zero, provided all the substances are
perfectly ordered.
0 as

0'

The entropies of all perfect crystalline substances is

zero at T = 0 K
3rd Law of Thermodynamics

Entropy changes in chemical reactions

S(T) : standard entropy at T K
Standard reaction entropy = rS
=

WX6837

2832937

Pure and separated reactants

in their standard state of
aggregation (all considered
positive for reactants and
products alike)

Fe2O3 (s) + 3H2 (g) 2Fe(s) + 3H2O (l)

= 2 Y ZK, D + 3 Y 4 [, $ Y ZK [G , D 3 Y(4 , %)
= R 2 3.28 + 3 8.4131 10.51 3(15.7041) = 214.7H' & B?$ &
Entropy of gases entropy of other phases
Standard reaction entropies are likely to be positive if there is a net
formation of gases in the reaction

Entropy and spontaneity

= 4

Heating at constant pressure,

4
At constant enthalpy,

4 =0;

b,

c,

Heating at fixed volume,

At constant internal energy,

=0;

Spontaneity
at constant V

e=

4 at constant p

Helmhotz energy

Gibbs energy

f=4

So, at constant T

e=

f= 4

At equilibrium, no change occurs.

Criterion for
spontaneous
change

=0

and

=0

Helmhotz free energy

Now,

and

e
e=
V2j

V2j

= maximum amount of (negative) work got out of the system

or maximum energy transferable to work

For a measurable change,

e =

V2j

Helmhotz free energy

e =

V2j

Helmhotz free energy is the maximum, reversible work done

More negative e, more is the work done

Q.

1.0 mol of glucose is oxidized to CO2 and H2O at 25C.

= 2808 <H B?$ & , = 259.13 H' & B?$ & .
How much of this energy change can be extracted as
a). Heat at constant p
b). Work?
Assume all gases involved as ideal gas.