Ch.

4: Entropy

1. Entropy

Entropy is a measure of disorder in a system. If a system undergoes a reversible

process, and takes in an amount of heat đQ at a temperature T, we define the change

in its entropy by the relation

dQ
dS  
T

The differential dS is exact.

The entropy change of a system taken from an initial state to a final state along

a reversible path is

f
dQ
S  S f  Si   
i
T

The value of S for the system is the same for all paths connecting the same initial

and final states; therefore, we conclude that S = 0 for any reversible cycle. The

meaningful quantity in describing a process is the change in entropy S, not S.

2. A Quasi-Static Reversible Process for an Ideal Gas

Suppose that an ideal gas undergoes a quasi-static reversible process from an initial

state having temperature Ti and volume Vi to a final state described by Tf and Vf.

1
 P

f
Tf

i
Ti

dQ  CV dT  PdV ;

dQ dT dV dT dV
dS   CV P  CV  nR ,
T T T T V

Tf Vf
dT dV
S f  Si  
Ti
CV
T
 nR 
Vi
V
.

If CV is constant, then we can write

Tf Vf
S  CV ln  nR ln 
Ti Vi

The above equation can be written as

S  CV ln T  nR ln V  S 0 ,

2
where S0 is a certain reference entropy. The third law of thermodynamics states that

the entropy of every system in thermodynamic equilibrium can always be taken

equal to zero at 0 K.

3. T-S Diagrams

The quantity of heat transferred in a reversible process from an initial state to a final

state is given by

Q   T dS = the area under a curve on a T-S diagram.

i

For a reversible isothermal process, T is a constant and the process is represented by

a horizontal line. For a reversible adiabatic process, dS  0 if T  0 (S is a

constant), and the process is represented by a vertical line.

Example: Draw the T-S diagram for the Carnot cycle.

A B
T1

T2 C
D

S2 S1 S

3
 If two equilibrium states are infinitesimally near each other, then

dQ dS
dQ  T dS or T 
dT dT

At constant volume,

 dQ   S 
CV    T   .
 dT V  T V

At constant pressure,

 dQ   S 
CP    T   .
 dT  P  T  P

4. Entropy Changes in Irreversible Processes

All natural processes are irreversible. The change in entropy of the universe is

S (universe)  S (system)  S (surroundings).

The entropy of the universe always increases for an irreversible process and remains

constant for a reversible process.

When a system undergoes an irreversible process between an initial equilibrium

state and a final equilibrium state, the entropy change of the system is

4
 f
dQ
S   ,
i
T

where the integration is performed over a reversible path connecting the same two

states.

Example: Adiabatic free expansion of an ideal gas.

The irreversible process is replaced by a reversible isothermal expansion from a

volume Vi to a volume Vf. Since Ti  T f ,

Vf
S (gas )  n R ln 
Vi

Vf
Since S (surroundings) = 0, S (universe)  n R ln  0.
Vi

Example: Entropy change of an object whose temperature is changed from Ti to Tf.

We can imagine that Ti is changed to Tf by a series of heat reservoirs differing

infinitesimally in temperature, the first reservoir being at Ti and the last being at Tf.

Such a series of very small changes in temperature would approximate a reversible

process. If the mass of the object is m and its specific heat is c, then

Tf
dQ dT Tf
S (object)    mc   m c ln 
T Ti
T Ti

Example: Transfer of heat Q through a system from a hot reservoir at T1 to a cold

reservoir at T2.

5
 S (system) 0 ,
Hot reservoir at T1

Q Q
S (hot reservoir)   ,
T1

System
Q
S (cold reservoir)   ,
T2
Q

Cold reservoir at T2
Q Q
S (universe)    0.
T2 T1

From the previous examples, we see that S (universe)  0 for any irreversible

process. The principle of increase of entropy states that, for any process,

S (universe)  0.

Example: Maximum efficiency of a heat engine.

Hot reservoir at T1

Q W Q
S (universe)    0, Q
T2 T1

H.E. W
System
 T 
W  Q 1  2  ,
 T1 
QW

Cold reservoir at T2

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  T  W T
Wmax  Q 1  2    max  max  1  2 
 T1  Q T1

Problems

5.

373
S (water)  (2 kg) (4186 J / kg.K) ln  2613 J / K.
273

Q  (2) (4186) (373  273)  8.37  105 J.

8.37  105 J
S (reservoir)     2244 J / K.
373 K

S (universe)  (2613  2244) J / K  369 J / K.

8.

Heat lost by copper = heat gained by water.

(50 g) (0.09 cal / g.K ) (373 K  Te )  (150 g) (1 cal / g.K ) (Te  293 K)  Te  295.3 K.

295.3 295.3
S (universe)  (50 g) (0.09 cal / g.K ) ln  (150 g) (1 cal / g.K ) ln  0.12 cal / K.
373 293

9.

 1000 1000 
S (universe)     cal / K  1.33 cal / K.
 300 500 

S (rod)  0.

11.

Q  I 2 R t  (2.2 A) 2 (20 ) (60 s)  5808 J.

7
 S (resistor)  0.

5808 J
S (running water)   19.8 J / K.
293 K

S (universe)  19.8 J / K.

12.

VC
 3.
VA

T2 T
 C  0.2  1   2  0.8 .
T1 T1

 1
 VB  T2
  
 VC  T1

0.33
 VB  VB
   0.8   0.51 .
 VC  VC

VB VB VC
   0.51  3  1.53 .
V A VC V A

VB
S (gas)  n R ln  (100 mol) (8.31 J / mol.K) ln 1.53  353 J / K.
VA

13.

Q  I 2 R t  (2 A) 2 (10 ) (2 s)  80 J.

Q  m c T

80 J  (5 g ) (1 J / g.K) (T f  293 K)  T f  309 K.

Tf 309
S (resistor)  m c ln  (5 g) (1 J / g.K) ln  0.266 J / K.
Ti 293