SECOND LAW OF THERMODYNAMICS

• The second law of thermodynamics states that any spontaneously occurring

process will always lead to an escalation in the entropy (S) of the universe.

• Spontaneous process – process that occurs in a system left to itself; once started,
no action from outside the system is necessary to make the process continue.

• Ex: the spontaneous flow of heat is always unidirectional from the higher to the
lower temperature; rusting of iron; neutralization; melting of ice
• Entropy (S) – related to the degree of disorderliness

• Ex: mixing of gases

A+B
S(mixture) > S initial

Ex: melting of the ice

ENTROPY
The entropy of a system depends only on the initial and final states of
the system.

∆ 𝑺= 𝑺 𝟐 − 𝑺 𝟏 (1)
𝒅 𝒒𝒓
𝒅𝑺= (2)
𝑻
T=constant

𝒒𝒓
∆ 𝑺= (3)
𝑻
T = absolute temperature
ENTROPY
entropy unit (eu) – calorie per degree
 I. Entropy Change in Isolated Systems
A. Isothermal process
𝒒𝒓
∆ 𝑺𝒔 = (4)
𝑻
𝒒𝒓
∆ 𝑺𝒓 = (5)
𝑻
* 1 to 2 – substance undergoes isothermal and reversible expansion from V1 to V2

∆ 𝑆1=∆ 𝑆 𝑠 + ∆ 𝑆𝑟 (6)
𝑞𝑟 𝑞 𝑟
∆ 𝑆1 = +
𝑇 𝑇

∆ 𝑆1 = 0
I. Entropy Change in Isolated Systems (cont’d)
* 1 to 2 – substance undergoes isothermal and reversible compression from V2 to V21
𝑞𝑟
∆ 𝑆 ′ 𝑠=
𝑇
(7)
𝑞𝑟
∆ 𝑆 ′𝑟 = (8)
𝑇
∆ 𝑆2=∆ 𝑆 ′ 𝑠 +∆ 𝑆′ 𝑟 (9)
𝑞𝑟 𝑞𝑟
∆ 𝑆1 = + (10)
𝑇 𝑇
∆ 𝑆1 = 0
∆ 𝑆=∆ 𝑆 1+ ∆ 𝑆 2 Total change in the entropy of a
complete cycle (11)
∆ 𝑆 =0
 I. Entropy Change in Isolated Systems (cont’d)
* 1 to 2 – substance undergoes isothermal and irreversible expansion from V1 to V2
𝑞𝑟 𝑞
∆ 𝑆1 =
𝑇
+
𝑇
(12)
But, and

𝑞𝑟 𝑞
∆ 𝑆1 = + >0
𝑇 𝑇
(13)
𝑞𝑟 𝑞
∆ 𝑆= + >0
𝑇 𝑇 (14)
* 2 to 1 – substance undergoes isothermal and reversible compression from V2 to V1
𝑞 𝑟 𝑞𝑟
∆ 𝑆2 = + =0
𝑇 𝑇
(15)
∆ 𝑺 >𝟎
I. Entropy Change in Isolated Systems (cont’d)
B. Non-Isothermal process

𝑻𝟐
𝒅 𝒒𝒓
∆ 𝑺=∫
𝑻𝟏
𝑻
I. Entropy Change in Isolated Systems (cont’d)
1. For any reversible process or cycle ∆ 𝑆 =0
2. For any irreversible process or cycle ∆ 𝑆 >0
The Second Law of Thermodynamics
𝑑𝑆𝑖 ¿ 0
All processes 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.
 II. Entropy Change in Systems Only
𝑑𝑆𝑖 = 𝑑𝑆+ 𝑑 𝑆 𝑟 ¿ 0 𝑑𝑞 (16)
𝑑𝑆𝑟 =−
𝑑𝑞 𝑇
𝑑𝑆 − ¿0
𝑇

𝑇𝑑𝑆 − 𝑑𝑞 ¿ 0
𝑑𝑞=𝑑𝐸+𝑝𝑑𝑉 +𝑑𝑤 ′
𝑇𝑑𝑆 − 𝑑𝐸 − 𝑝𝑑𝑉 − 𝑑𝑤 ′ ¿ 0
𝑇𝑑𝑆 − 𝑑𝐸 − 𝑝𝑑𝑉 >0 When only
II. Entropy Change in Systems Only (cont’d)

However, for reversible processes

′
𝑇𝑑𝑆 − 𝑑𝐸 − 𝑃𝑑𝑉 − 𝑑 𝑤 𝑚 =0

And

𝑻𝒅𝑺 − 𝒅𝑬 − 𝑷𝒅𝑽 =𝟎
 II. Entropy Change in Systems Only (cont’d)
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 300K.
Solution:

𝑑𝐸 =0
𝑃𝑑𝑉
𝑑𝑆 =
𝑇
𝑛𝑅𝑑𝑉
𝑑𝑆=
𝑉
On making the substitution . Consequently, we get on integration

∆ 𝑆 =𝑆 2 − 𝑆1
𝑉2
∆ 𝑆 =𝑛𝑅𝑙𝑛
𝑉1
100
∆ 𝑆 =5 ( 1.987 ) ( 2.303 ) 𝑙𝑜𝑔 ∆ 𝑆=22.88 𝑐𝑎𝑙 𝑑𝑒𝑔𝑟𝑒𝑒 − 𝑜𝑟 𝑒𝑢
10
II. Entropy Change in Systems Only (cont’d)
Dependence of Entropy on Variables of a System
Variables T and V. If the entropy of a substance is a function of T and V, then,

𝑑𝑆=
𝜕𝑆
𝜕𝑇 ( )𝑉
𝑑𝑇 +
𝜕𝑆
𝜕𝑉 ( )𝑇
𝑑𝑉

Again, the first law gives for reversible conditions

𝑑𝐸 =𝑑𝑞 𝑟 − 𝑑𝑤 𝑚

𝑪𝒗
𝒅𝑺=
𝑻
𝒅𝑻 + ( 𝝏 𝑷
𝝏𝑻 ) 𝑽
𝒅𝑽
II. Entropy Change in Systems Only (cont’d)
Dependence of Entropy on Variables of a System
Variables T and P

𝑪𝒑
𝒅𝑺=
𝑻
𝒅𝑻 + ( 𝝏 𝑽
𝝏𝑻 ) 𝑷
𝒅𝑷
 III. Entropy Change in Ideal Gases
𝑇 2
𝑑𝑄 From 1st Law:
∆ 𝑆 =∫
𝑇 1
𝑇
𝑇
𝑑𝐸 + 𝑑𝑊
2

∆ 𝑆 =∫
𝑇 1
𝑇
𝑇 𝑇
𝑑𝐸 𝑑𝑊
2 2

∆ 𝑆 =∫ +∫
𝑇 1
𝑇 𝑇
𝑇 1

𝑇 𝑇
2
𝑛 𝐶 𝑣 𝑑𝑇 𝑃 𝑑𝑉
2

∆ 𝑆 =∫ +∫
𝑇 1
𝑇 𝑇
𝑇 1

𝑻𝟐 𝑽𝟐
∆ 𝑺=𝒏 𝑪 𝒗 𝒍𝒏 + 𝒏𝑹𝒍𝒏
𝑻𝟏 𝑽𝟏
 III. Entropy Change in Ideal Gases (cont’d)
𝑇 But:
𝑑𝑄
2

𝑆 =∫
𝑇 1
𝑇
𝑇
𝑑𝐻 − 𝑉𝑑𝑃
2

=∫
𝑇 1
𝑇
𝑇 𝑃
𝑑𝐻 𝑉 𝑑𝑃
2 2

=∫ −∫
𝑇 1
𝑇 𝑃
𝑇 1

𝑃2
2
𝑛 𝐶 𝑝 𝑑𝑇 𝑛𝑅𝑇 𝑑 𝑃
∫ 𝑇
−∫
𝑃𝑇
1 𝑃 1

𝑻𝟐 𝑷𝟐
𝒏 𝑪 𝒑 𝒍𝒏 − 𝒏𝑹𝒍𝒏
𝑻𝟏 𝑷𝟏
IV. Entropy of Mixing for Ideal Gases
𝑃1
∆ 𝑆1 =− 𝑛1 𝑅𝑙𝑛 0
𝑃1
𝑃0
1
∆ 𝑆1 =𝑛 1 𝑅𝑙𝑛
𝑃1
Similarly, we have for the second gas 0
𝑃2
∆ 𝑆2 = 𝑛2 𝑅𝑙𝑛
𝑃2
And hence the entropy of mixing is
∆ 𝑆𝑛 =∆ 𝑆1 + ∆ 𝑆2
0 0
𝑃1 𝑃2
∆ 𝑆𝑚 =𝑛1 𝑅𝑙𝑛 +𝑛2 𝑅𝑙𝑛
𝑃1 𝑃2
IV. Entropy of Mixing for Ideal Gases
But according to Dalton’s law of partial pressures, and where and are the mol fractions of the two gases and
is the total pressure of the mixture. Introducing these identities into the previous equation we get

0 0
𝑃1 𝑃2
∆ 𝑆𝑚 =𝑛1 𝑅𝑙𝑛 +𝑛2 𝑅𝑙𝑛
𝑁1 𝑃𝑡 𝑁 2 𝑃𝑡
In the special instance of , the previous equation reduces to
∆ 𝑆𝑚 =−(𝑛 ¿ ¿ 1 𝑅𝑙𝑛 𝑁 1 +𝑛 2 𝑅𝑙𝑛 𝑁 2) ¿
IV. Entropy Change in Physical Transformations
∆ 𝑆 =𝑆 2 − 𝑆1

𝑞𝑟 ∆ 𝐻
∆ 𝑆= =
𝑇 𝑇
IV. Entropy Change in Physical Transformations
(cont’d)
Example: Consider the problem of finding entropy difference for the transition

𝐻 2 𝑂 ( 𝑙 ,1 𝑎𝑡𝑚 ) = 𝐻 2 𝑂 (𝑔 , 1 𝑎𝑡𝑚) ∆ 𝐻 373.2 𝐾 = 9717 𝑐𝑎𝑙 𝑚𝑜𝑙𝑒−1

Since at 373.2K and 1 atm pressure, the normal boiling point of water, is in equilibrium with then

∆ 𝐻
∆ 𝑆 =𝑆 𝑔 − 𝑆 𝑙=
𝑇
9717
∆ 𝑆 =
373.2
−1
∆ 𝑆 =26.04 𝑒𝑢 𝑚𝑜𝑙𝑒
 IV. Entropy Change in Physical Transformations
(cont’d)
Entropy changes may be calculated for irreversible transitions, but the change in entropy will no longer be given
by the previous equation. Consider first the process
𝐻 2 𝑂 ( 𝑙 ,1 𝑎𝑡𝑚 ) = 𝐻 2 𝑂 (𝑔 , 1 𝑎𝑡𝑚)
At 373.3K. Since the change in entropy does not depend on the manner of accomplishing the change, we may
first vaporize the water isothermally and reversibly to steam at 1 atm pressure and then expand the steam
reversibly and isothermally from 1 to 0.1 atm. The total change in entropy will then be
∆ 𝑆 =∆ 𝑆 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 + ∆ 𝑆 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛
∆ 𝐻 𝑃 1
𝑆= + R ln
𝑇 𝑃 2
9717 1
𝑆= + 4.58 log
373.2 0.1
− 1
𝑆 =30.62 𝑒𝑢 𝑚𝑜𝑙𝑒
IV. Entropy Change in Chemical Reactions
𝛼 𝐴 + 𝑏𝐵 + … =𝑐𝐶 + 𝑑𝐷 + …
Δ 𝑆 = ( 𝑐 𝑆 𝑐 + 𝑑 𝑆𝑑 + … ) − (𝛼 𝑆 𝐴 +𝑏 𝑆 𝐵 +…)

∆ 𝑆2 𝑇2
∆ 𝐶𝑝
∫ 𝑑 ( ∆ 𝑆 )=∫
𝑇
𝑑𝑇
∆ 𝑆1 𝑇1

𝑻 𝟐
∆ 𝑪𝒑
∆ 𝑆2 − ∆ 𝑆1 = ∫ 𝒅𝑻
𝑻 𝟏
𝑻
𝑻
𝒅𝑻
𝟐

∆ 𝑆2 − ∆ 𝑆1 = ∆ 𝑪 𝒑 ∫ 𝑻
𝑻 𝟏

𝑻 𝟐
∆ 𝑆2 − ∆ 𝑆1 = ∆ 𝑪 𝒑 𝒍𝒏
𝑻 𝟏
END
III. Entropy Change in Ideal Gases
For an ideal gas, PV = nRT, and differentiation yields

( 𝝏 𝑷
𝝏 𝑻 )𝑽
=
𝒏𝑹
𝑽
𝐶
𝑇 𝜕𝑇 𝑉 ( )
Hence for ideal gases, the equation,𝑑𝑆= 𝑣 𝑑𝑇 + 𝜕 𝑃 𝑑𝑉 , becomes
𝑛 𝐶 𝑉 𝑑𝑇 𝑛𝑅𝑑𝑉
𝑑𝑆= +
𝑇 𝑉

And on integration between the indicated limits we get for

𝑇2 𝑉
𝑛 𝐶 𝑣 𝑑𝑇 𝑛 𝑅 𝑑𝑉
2

∆ 𝑆 =∫ +∫
𝑇1
𝑇 𝑉
𝑉
1

𝑇 2
𝑛 𝐶 𝑣 𝑑𝑇 𝑉1
∆ 𝑆 =∫ +𝑛𝑅 𝑙𝑛
𝑇 1
𝑇 𝑉2
III. Entropy Change in Ideal Gases (cont’d)
When is constant over the temperature interval in question, the previous equation reduces to

𝑻𝟐 𝑽𝟐
∆ 𝑺=𝒏 𝑪 𝒗 𝒍𝒏 + 𝒏𝑹𝒍𝒏
𝑻𝟏 𝑽𝟏
In case of T and P as the independent variables, we may substitute for in the equation
𝐶𝑝
𝑑𝑆 =
𝑇
𝑑𝑇 + ( 𝜕 𝑉
𝜕 𝑇 ) 𝑃
𝑑𝑃
Where is now the heat capacity per mole of gas. Again, from differentiation of we obtain

( 𝝏 𝑽
𝝏𝑻 ) 𝑷
=
𝑛𝑅
𝑃
𝐶𝑝
Subsituting into equation,𝑑𝑆=
𝑇
𝑑𝑇 +
𝜕𝑉
𝜕𝑇 ( ) 𝑑𝑃
𝑃
, FOR n moles of an ideal gas becomes

𝑇 2
𝑛 𝐶𝑝 𝑛𝑅
𝑑𝑆 =∫ 𝑑𝑇 − 𝑑𝑃
𝑇 1
𝑇 𝑃
III. Entropy Change in Ideal Gases (cont’d)
And hence on integration between the indicated limits

𝑇 𝑃2
2
𝑛 𝐶 𝑝 𝑑𝑇 𝑛𝑅𝑑𝑃
∆ 𝑆 =∫ −∫
𝑇1
𝑇 𝑃
𝑃 1
𝑇2
𝑛 𝐶 𝑝 𝑑𝑇 𝑃2
∆ 𝑆 =∫ − 𝑛𝑅𝑙𝑛
𝑇 1
𝑇 𝑃1

If is may be considered constant, then the previous equation yields

𝑻𝟐 𝑷𝟐
∆ 𝑺=𝒏 𝑪 𝒑 𝒍𝒏 − 𝒏𝑹𝒍𝒏
𝑻𝟏 𝑷𝟏