The Second Law of

Thermodynamics
Dr. Setyanto Tri Wahyudi

1
Review: The 1st Law of Thermodynamics
∆𝑈 = 𝑄 − 𝑊
𝑄 = ∆𝑈 + 𝑊
› Statement of Conservation of Energy
› Enable to calculate the energy changes of chemical reaction

› Drawback: Does not enable us to predict wheter a reaction can

occur or cannot occur.
› Nothing directional about it

2
An example Limitation of First Law
› According to 1st Law: ∆𝑈 = 𝑄 − 𝑊.

𝑊<0 𝑊<0 𝑊>0

𝑄<0 𝑄>0

∆𝑈 = 0 ∆𝑈 = 0
𝑄<0
1st Law. √ √

COLD PLATE Practice. √ 𝑋

3
Fact in nature: Arrow Time

4
The 2nd Law : What help us ?
› The 2nd Law of Thermodynamics will help us do:
– Determine what is possible, and what is not possible
– Dictates limits on the behavior of the process/systems
– Provide of thermodynamics hierarchy of isotherm
– Provide a basis of thermodynamics scales of temperature
– Define a very useful property : Entrophy
– Help us derive a number of relation between thermodynamic
property.

5
The 2nd Law : History and Statement
› Nicolas Léonard Sadi Carnot (1796-1832). A French Engineer
› Carnot wanted to answer two questions about the operation
of heat engines:
– Is the work available from a heat source potentially unbounded?
– Can heat engines in principle be improved by replacing the steam
with some other working fluid or gas?
› Carnot interesting on Improving of the efficiency of the Engine
› Carnot Theorem:
“A reversible Engine will be the most efficient engine”
6
The 2nd Law : History and Statement
› Rudolf Julius Emanuel Clausius (1822-1888) was a German
physicist, and he developed the Clausius statement, which
says:

"Heat generally cannot flow spontaneously from a

material at a lower temperature to a material at a
higher temperature."

7
The 2nd Law : History and Statement
› William Thompson, also known as Lord Kelvin:
› “ It is impossible by cyclic process to take heat from a
reservoir and to convert it into work without
simulatenously transferring heat from a hot to a cold
reservoir”

8
The 2nd Law : History and Statement
› Max Karl Ernst Ludwig Planck:
› States:
› It ist impossible to construct an engine which, working in
a complete cycle, will produce no effect other than
raising of weight and the cooling of a heat reservoir”

9
The 2nd Law : History and Statement
› Kelvin-Placnk Principle:
› States:
› “No Process is possible whose sole result is the absorption of
heat from a reservoir and the conversion of this heat into
work”
Qabs > 0
Engine Wout > 0

10
The 2nd Law : History and Statement
› Constantin Carathéodory, a Greek mathematician
› States:
› "In the neighborhood of any initial state, there are states
which cannot be approached arbitrarily close through
adiabatic changes of state."

11
The Heat Engine

12
The Heat Engine
› Heat engine :
1. a Cyclic device
- Initial state, 2-3 step, stop state, initial state
2. Work is an output. That’s mean, work done by the engine should be
positive, (𝑊 > 0). This is the Net Work by the engine.
3. Heat supply to the engine, to produce amount of work

Qnet > 0
𝑄𝑛𝑒𝑡 = 𝑊𝑛𝑒𝑡
Engine Wnet > 0

13
Efficiency of The Heat Engine
› The Thermal Efficiency of The Heat Engine. The Term Thermal
sometimes replace by Energy.

Qnet split into 2 term: supply and rejected

Qsup >0 𝑄𝑠𝑢𝑝 − 𝑄𝑟𝑒𝑗 = 𝑊𝑛𝑒𝑡

𝑊𝑛𝑒𝑡 𝑄𝑟𝑒𝑗
Engine Wnet > 0 The Efficiency: 𝜂 = =1−
𝑄𝑠𝑢𝑝 𝑄𝑠𝑢𝑝
Qrej <0
14
Thermal Energy Reservoir
› The idea of thermal Energy Reservoir is an idealized
thermodynamics system which reduce derivations.
› Thermal Energy Reservoir:
– A system that finite amount of heat transfer from or to reservoir the
reservoir does not lead any changes in temperature.
– Each Reservoir will characterized by its temperature.
oC
0Tres o
1000
Tres C
Treservoir
Tres

100 o
Tres C

15
1T Heat Engine
› 1T Heat Engine indicating that heat engine with only 1
thermal energy reservoir.
Treservoir
Tres

𝑄𝑖𝑛𝑝 > 0 𝑊𝑛𝑒𝑡 𝑄𝑖𝑛𝑝

𝜂= = =1
Engine 𝑊𝑛𝑒𝑡 > 0 𝑄𝑠𝑢𝑝 𝑄𝑖𝑛𝑝

Possible or Not Possible ?

16
2T Heat Engine – 2 Absorb
𝑇1 ≠ 𝑇2
T
Tres
𝑊𝑛𝑒𝑡 = 𝑄1 + 𝑄2
1
𝑄𝑠𝑢𝑝 = 𝑄1 + 𝑄2
𝑎𝑏𝑠𝑜𝑟𝑏 𝑄1 > 0
E 𝑊𝑛𝑒𝑡 > 0
𝑎𝑏𝑠𝑜𝑟𝑏 𝑄2 > 0 𝑊𝑛𝑒𝑡 𝑄𝑖𝑛𝑝
𝜂= = =1
Tres 𝑄𝑠𝑢𝑝 𝑄𝑖𝑛𝑝
T2
Possible or Not Possible ?
17
2T Heat Engine – 1 Absorb
𝑇1 ≠ 𝑇2
T
Tres
𝑊𝑛𝑒𝑡 = 𝑄1 − 𝑄2
1

𝑎𝑏𝑠𝑜𝑟𝑏 𝑄1 > 0 𝑄1 > 𝑄1

E 𝑊𝑛𝑒𝑡 > 0 𝑄𝑠𝑢𝑝 = 𝑄1

𝑟𝑒𝑗𝑒𝑐𝑡𝑒𝑑 𝑄2 < 0 𝑊𝑛𝑒𝑡
𝜂= <1
Tres
T2 𝑄𝑠𝑢𝑝
Possible or Not Possible ?
18
2T Heat Engine – another Engine
𝑇1 ≠ 𝑇2
T
Tres
1 T
Tres
1

𝑄1 > 0 𝑄1′ < 0

′
E 𝑊𝑛𝑒𝑡 > 0 E’ 𝑊𝑛𝑒𝑡 >0
𝑄2 < 0 𝑄2′ = 𝑄2
Tres Tres
T2 T2

19
2T Heat Engine – another Engine
𝑇1 ≠ 𝑇2
T
Tres
1

𝑄1 > 0 𝑄1′ < 0

E 𝑊𝑛𝑒𝑡 > 0 E’ 𝑊′𝑛𝑒𝑡 > 0
𝑄2 < 0 𝑄2 = 𝑄2′
Tres
T2
𝑄2 < 𝑄1 𝑄2′ < 𝑄1 𝑄1′ < 𝑄2′ < 𝑄1
20
2T Heat Engine – re-scheme Engine

T
Tres
1

′
𝑎𝑏𝑠𝑜𝑟𝑏 𝑄1 − 𝑄
1T Heat Engine
1

E & E’ 𝑊𝑛𝑒𝑡 + 𝑊′𝑛𝑒𝑡 > 0

21
2T Heat Engine Will Work Only in One Way
𝑇1 ≠ 𝑇2
T
Tres
1 T
Tres
1

𝑄1 𝑄1′
′
E 𝑊𝑛𝑒𝑡 > 0 E 𝑊𝑛𝑒𝑡 >0
𝑄2 𝑄2′
Tres
T2 √
Tres
T2 Ꭓ

22
2T Heat Engine: Direct Contact Reservoir
𝑇1 ≠ 𝑇2
T
Tres
1

𝐵 Possibility of Heat Flow

𝐴
𝑄𝐴 𝑄𝐵

Tres
T2

23
2T Heat Engine: Direct Contact Reservoir
𝑇1 ≠ 𝑇2
T
Tres
1 T
Tres
1
𝑄1 𝑄1 + 𝑄𝐴
𝑄𝐴 E E+A 𝑊𝑛𝑒𝑡 > 0
𝑊𝑛𝑒𝑡 > 0
𝑄2 𝑄2+𝑄𝐴
Tres Tres
T2 T2
2 T Heat Engine
24
2T Heat Engine: Direct Contact Reservoir
𝑇1 ≠ 𝑇2
T
Tres
1
𝑄1
𝑄𝐵 E
𝑊𝑛𝑒𝑡 > 0 1T Heat Engine
𝑄2
Tres
T2

25
Temperature Level &
Performance Parameter

26
Resume: 2T Heat Engine
𝑇1 ≠ 𝑇2 Can we say T1 Higher than T2 ?
T
Tres
1 T
Tres
1
𝑄1 𝑄1
E 𝑊𝑛𝑒𝑡 > 0 𝑄𝐴
E
𝑊𝑛𝑒𝑡 > 0
𝑄2 𝑄2
√ √
Tres
T2 Tres
T2

27
Higher and Lower Temperature
› Logic in Math:
› If A > B, and B > C, then A > C

› Given 3 Temperature: T1, T2 and T3.

› 𝑇1 ≠ 𝑇2 , 𝑇2 ≠ 𝑇3 , 𝑇1 ≠ 𝑇3

28
Build Engine From T1, T2, and T3

T
Tres
1 T
Tres
2
𝑄1,12 𝑄1,23
E12 E23
𝑄2,12 𝑊12 > 0 𝑄2,23 𝑊23 > 0
Tres Tres
T2 T3

29
Build Engine From T1, T2, and T3

T
Tres
1 T
Tres
1
𝑄1,13 𝑄1,13
E13 E13
𝑄2,13 𝑊13 > 0 𝑄2,13 𝑊31 > 0
Tres Tres
T3 T3
𝐴 𝐵
Which way will it work ?
30
Higher and Lower Temperature
T
Tres
1 T
Tres
2 T
Tres
3

𝑄4 𝑄1 𝑄2 𝑄2 𝑄3 𝑄3

E12 E23
𝑊12 > 0 𝑊23 > 0

E13
𝑊31 > 0
31
Higher and Lower Temperature

𝑄3 < 𝑄2 < 𝑄1

𝑄2 < 𝑄1
𝑄4 < 𝑄3
𝑄4 < 𝑄1
32
Simplified Engine

1T Heat Engine
Engine
𝑊 = 𝑊12 + 𝑊23 + 𝑊31 𝑄𝑠𝑢𝑝 = 𝑄1 − 𝑄4
33
Build Engine From T1, T2, and T3

T
Tres
1 T
Tres
1
𝑄1,13 𝑄1,13
E13 E13
𝑄2,13 𝑊13 > 0 𝑄2,13 𝑊13 > 0
Tres Tres
T3 T3
𝐴 𝐵 Ꭓ
Which way will it work ?
34
Higher and Lower Temperature

𝑇1 > 𝑇2 𝑇2 > 𝑇3 𝑇1 > 𝑇3

35
Hierarchy of Temperature

𝑄𝑎𝑏𝑠 𝑄𝑟𝑒𝑗
E13

36
Performance Parameter

37
Resume: 2T Heat Engine
𝑇1 > 𝑇2
T
Tres
1 T
Tres
1
𝑄1 𝑄1
E 𝑊𝑛𝑒𝑡 > 0 𝑄𝐴
E
𝑊𝑛𝑒𝑡 > 0
𝑄2 𝑄2
√ √
Tres
T2 Tres
T2

38
Refrigerator
𝑇1 > 𝑇2 T
Tres
1

T
Tres
1 𝑄1
𝑄1 E 𝑊𝑛𝑒𝑡 > 0
E 𝑊𝑛𝑒𝑡 > 0 𝑄2
𝑄2 √
Tres
T2
X
Tres
T2
𝑊𝑛𝑒𝑡 > 0

39
Performance Parameter: Heat Engine
𝑇1 > 𝑇2
Performance Parameter:
T
Tres
1 Efficiency
𝑄𝑠𝑢𝑝
𝑊𝑛𝑒𝑡
E 𝑊(𝑤𝑎𝑛𝑡) > 0 𝜂= <1
𝑄𝑠𝑢𝑝
𝑄𝑟𝑒𝑗
Tres
T2

40
Performance Parameter: Refrigerator
𝑇1 > 𝑇2
Performance Parameter:
T1
Tres
Coefficienf of Performance
𝑄1 = 𝑄2 + 𝑊 (COP)
𝑄2
E 𝑊(𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑) > 0 𝐶𝑂𝑃 =
𝑊𝑠𝑢𝑝
𝑄2(𝑛𝑒𝑒𝑑 𝑡𝑜 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟)
Tres
T2 COP is a finite number

41