2nd Law of thermodynamics

- first explicit statement was given by Rudolf Julius Emmanuel Clausius(1822-1888)

1. Statements of the Second Law

General Statement of the second law:
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 increase in entropy

Clausius’ statement of the second law:

- It is not possible to construct a device operating in a cycle whose sole effect is to transfer heat from a body of
lower temperature to a body of higher temperature
- extracting heat from a hot reservoir and using it all to do work would constitute a perfect heat engine which is
forbidden by by the second law

Kelvin- Plank’s statement of the second law:

- it is not possible to construct a device operating in a cycle that will convert heat completely to work
- Spontaneous flow of heat from a cold body to a hot body would constitute a perfect refrigerator

2. Perpetual motion machines

A. Perpetual motion machines of the first kind
 A device that violates the first law of thermodynamics
B. Perpetual motion machines of the second kind
 A device that violates the 2nd law of thermodynamics

The Carnot Cycle

In the early 19th century, steam engines came to play an increasingly important role in industry and
transportation. However, a systematic set of theories of the conversion of thermal energy to motive power by
steam engines had not yet been developed. Nicolas Léonard Sadi Carnot (1796-1832), a French military
engineer, published Reflections on the Motive Power of Fire in 1824. The book proposed a generalized theory
of heat engines, as well as an idealized model of a thermodynamic system for a heat engine that is now known
as the Carnot cycle. Carnot developed the foundation of the second law of thermodynamics, and is often
described as the "Father of thermodynamics."

The Carnot cycle consists of the following four processes:

I. A reversible isothermal gas expansion process. In this process, the ideal gas in the system absorbs qin
amount heat from a heat source at a high temperature Thigh , expands and does work on surroundings.
 II. A reversible adiabatic gas expansion process. In this process, the system is thermally insulated. The
gas continues to expand and do work on surroundings, which causes the system to cool to a lower
temperature, Tlow .
III. A reversible isothermal gas compression process. In this process, surroundings do work to the gas at
Tlow , and causes a loss of heat, qout .
IV. A reversible adiabatic gas compression process. In this process, the system is thermally insulated.
Surroundings continue to do work to the gas, which causes the temperature to rise back to Thigh.

Figure 11 : An
ideal gas-piston model of the Carnot cycle.

P-V Diagram

The P-V diagram of the Carnot cycle is shown in Figure 1 . In isothermal processes I and III, ∆U=0 because
∆T=0. In adiabatic processes II and IV, q=0. Work, heat, ∆U, and ∆H of each process in the Carnot cycle are
summarized in Table 1 .
 Figure 1 : A P-V
diagram of the Carnot Cycle.

Table 1 : Work, heat, ∆U, and ∆H in the P-V diagram of the Carnot Cycle.
Process w q ΔU ΔH

−nRnCv(Thigh−Tlow)l
I nRThighln(V2/V1) 0 0
n(V2/V1)

nCv(Tlow−Thi nCp(Tlow−Th
II nCv(Tlow−Thigh) 0
gh) igh)

III −nRTlowln(V4/V3) nRTlowln(V4V3) 0 0

nCv(Thigh−Tl nCp(Thigh−Tl
IV nCv(Thigh−Tlow) 0
ow) ow)
 Table 1 : Work, heat, ∆U, and ∆H in the P-V diagram of the Carnot Cycle.
Process w q ΔU ΔH

Full −nRThighln(V2/V1) nRThighln(V2/V1)+nRTlo

0 0
Cycle −nRTlowln(V4/V3) wln(V4/V3)

T-S Diagram

The T-S diagram of the Carnot cycle is shown in Figure 2 . In isothermal processes I and III, ∆T=0. In adiabatic
processes II and IV, ∆S=0 because dq=0. ∆T and ∆S of each process in the Carnot cycle are shown in Table 2 .

Figure 2 : A T-S diagram

of the Carnot Cycle.

Table 11 : Work, heat, and ∆U in the T-S diagram of the Carnot Cycle.
Process ΔT ΔS

I 0 −nRln(V2V1)

II Tlow−Thigh 0

III 0 −nRln(V4V3)
 Table 11 : Work, heat, and ∆U in the T-S diagram of the Carnot Cycle.
Process ΔT ΔS

IV Thigh−Tlow 0

Full Cycle 0 0

Efficiency

The Carnot cycle is the most efficient engine possible based on the assumption of the absence of incidental
wasteful processes such as friction, and the assumption of no conduction of heat between different parts of the
engine at different temperatures.

1. Carnot heat engine

The efficiency of the carnot engine is defined as the ratio of the energy output to the energy input.

Wout QH  Q L Q
   1 L
QH QH QH

Where QH = heat rejected to a low temperature sink at TL

QL = heat absorbed from a high temperature reservoir at TH

Thermal efficiency of a Carnot heat engine or any reversible heat engine is given by

TL
  1
TH

2. Carnot refrigerator or heat pump

 A hypothetical engine that operates on the reversible reverse Carnot cycle
QL QL
 The coefficient of performance of any refrigerator or heat pump COPref  
(reversible or irreversible) is given by: Wnet ,in QH  QL
QL QH
COPhp  
Wnet ,in QH  QL
1 TL
COPref  
TH / TL  1 TH  TL
1 TH
COPhp  
1  TL / TH TH  TL
Where Q