THE SECOND LAW OF

THERMODYNAMICS
Statements of the Second Law
1. KELVIN-PLANCK STATEMENT: No apparatus can operate in such a
way that its only effect (in system and surroundings) is to convert
heat absorbed by a system completely into work done by the
system.
• It is impossible by a cyclic process to convert the heat absorbed by a system
completely into work done by the system.

2. CLAUSIUS STATEMENT: No process is possible which consists solely

in the transfer of heat from one temperature level to a higher one.
Heat Engines
• Heat engines are devices or machines that produce work from heat in
a cyclic process.
• Heat (QH) is absorbed into the system at a high temperature (TH).
• Heat (QC) is rejected to the surroundings at a lower temperature (TC).
| 𝑊 |=|𝑄 𝐻|−|𝑄 𝐶|

Efficiency, 

 ≡ |𝑊 | |𝑄 𝐻|−|𝑄 𝐶|
𝜂 =
|𝑄 𝐻| |𝑄 𝐻|

  |𝑄 𝐶|
𝜂=1−
|𝑄 𝐻|
Carnot Engine
• Carnot Engine
• Step 1. A system at an initial temperature of a cold reservoir at TC undergoes a reversible
adiabatic process that causes its temperature to rise to that of a hot reservoir at TH.
• Step 2. The system maintains contact with the hot reservoir at TH, and undergoes a reversible
isothermal process during which QH is absorbed from the hot reservoir.
• Step 3. The system undergoes a reversible adiabatic process in the opposite direction of step
1 that brings the temperature back to that of the cold reservoir at TC.
• Step 4. The system maintains contact with the reservoir at TC, and undergoes a reversible
isothermal process in the opposite direction of step 2 that returns it to its initial state with
rejection of heat QC to the cold reservoir.
• CARNOT’S THEOREM. For two given heat reservoirs no engine can
have a thermal efficiency higher than that of a Carnot engine.

• Carnot engine is the most efficient engine permitted by the Second law of
Thermodynamics.

  =1− |𝑄 𝐶| 𝑇𝐶
𝜂 =1−
|𝑄 𝐻| 𝑇𝐻
ENTROPY
• There exists a property called entropy (S), which is an intrinsic
property of a system, functionally related to the measurable
coordinates which characterize the system.

dQrev
• For a reversible process: t
dS 
T

t dQrev
• For a system undergoing a finite reversible process: S  
T
• Mathematical statement of the Second law:
Stotal  S sys  S surr  0
• Entropy changes of an ideal gas:
T dT P
S   C P  R ln
T0 T P0

• Entropy changes of liquids and solids:

T dT
S   C P
T0 T
Entropy Balance for Open System
 
 d  mS  dS t 
 S m   cv
  SG  0
  fs dt dt For steady-state:

    Q 
d  mS  cv Q  S m     SG  0
  
 S m   

 SG  0   fs i T , j
  fs dt i T , j
For steady-state, with one entrance
and one exit, with mass flow rate same
T,j – temperature in the surroundings for both:
Q
S    SG  0
i T , j
Example 1
In a steady-state flow process, 1 mol/s of air at 600 K and 1 atm is
continuously mixed with 2 mol/s of air at 450 K and 1 atm. The product
stream is at 400 K and 1 atm. Determine the rate of heat transfer and
the rate of entropy generation for the process. Assume that air is ideal
gas with CP = 3.5R, that the surroundings are at 300 K, and that kinetic-
and potential-energy changes are negligible.
Calculation of Ideal Work
• For a completely reversible process, the entropy generation (SG) is
zero.

W ideal 


1 2

   
   H  2 u  zg m  T  S m 
 fs   fs

• For single-stream, negligible PE and KE:

      
  H m   T  S m 
W ideal
  fs   fs

Wideal  H  T S
Example 2
What is the maximum work that can be obtained in a steady-state flow
process from 1 mol of N2 at 800 K and 50 bar?

The temperature and pressure of the surroundings are 300 K and 1.033
bar, respectively.
Lost Work
• LOST WORK: work that is wasted as the result of irreversibilities in a
process.
Wlost  WS  Wideal Wlost  T S  Q

   
Q

  Q 
SG  S 
W lost  T  S m    T S G T
  fs T 
 
Example 3
A steady-flow adiabatic expander accepts an ideal gas at 550 K and 4
bar, and discharges at 403 K and 1.2 bar. Determine W, Wideal, Wlost, and
SG. Take CP = 2.5R and T = 300 K.