Chap. 3: The 2nd Law of Thermodynamics 3.1: The 2nd Law of Thermodynamics 3.2: Heat Engines 3.

3: Entropy 3.4: Calculation of Entropy Changes 3.5: Entropy, Reversibility, and Irreversibility 3.6: The Thermodynamic Temperature Scale 3.7: What is Entropy?

3.1: The 2nd Law of Thermodynamics

Sadi Carnots work in 1824:
How the heat engines work
The efficiency of a heat engine

Clausiuss and Thomsons work in 1850: Kelvin-Planck Statement of 2nd Law:

It is impossible for a system to undergo a cyclic process whose sole effects are the flow of heat into the system from a heat reservoir and the performance of an equivalent amount of work by the system on the surroundings.

 Clausius Statement:

It is impossible for a system to undergo a cyclic process whose sole effects are the flow of heat into the system from a cold reservoir and the flow of an equal amount of heat out of the system into a hot reservoir.

3.2: Heat Engines

Heat Engine

qH

qC

 Heat Engine
Hot Reservoir H qH

Efficiency of Heat Engine

e work output per cycle energy input per cycle -w qH w qH

Heat Engine

For a cycle of operation:

w

U thus,

0 q w qH w qH w qH qH qH qC qC

qC qC 1 qH 0

qC
Cold Reservoir C

Because qC e 1

0 and qH

 Carnots Principle:

No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures H and C. The maximum amount of work from a given supply of heat is obtained with a reversible engine. e(real engine) e(reversible engine) eirrev erev

 Carnot Cycle: See Fig-3.4 on p. 83

P 1

12: Isothermal Expansion

23: Adiabatic Expansion

34: Isothermal Compression
2 41: Adiabatic Compression

All processes are reversible!

4
3

12: Reversible Isothermal Expansion

T1 dU 1 T2
2 H

and dU 1
2

2 2

0 ( U 1 0 dq1

2 2

0) dw1
2

dq1

dw1

nRT Reversible process : dw1 2 PdV ( PV nRT P ) V dq1 2 nR nRT dq1 2 dw1 2 PdV dV and dS1 2 dV V T V Note that : T 2 H for process 1 w1 q1
V2 2 V1

nR V
2

dV ln

nR V2 V1 nR

lnV V

V2
1

nR

V2 ln V1 V2 V1 0

w1 q1

nR w1

and S1 ln V2 V1

nR ln ln

U 1

nR

V2 V1

23: Reversible Adiabatic Compression

dq2
3

dU 2

dq2

dw2

dw2

nRT Note that : dU 2 3 CV dT , dw2 3 PdV and P V nRT Thus we can establish the equation : CV dT PdV dV V nRT dT dV CV dT dV CV nR (Note : T2 H , T3 C) V T V V3 dV C P CV V3 dV nR V3 dV C dT C dT CV nR V2 V V2 V H T H T CV V2 V CV ln T
C H
C H

CP V3 1 lnV V 2 CV V2 V3
1 1 CV3 1 H V2

ln
1

C H

V3 1 ln V2
1

V2 ln V3
1 CV3

TV

const.

H V2

From TV

1 H

V2

C 3

, we get : T

V2 V
H 1 1

1 C 1

V3 V

Because dw2 dw2 nR V nR

PdV V2 V
1 V3 V2 1

nRT dV and T V dV nR
H

V2 V

1 V2 V V
1

dV
1 V3

nR nR

V2

dV V V2 V3 0
1

w2

H V2

V dV nR

nR

H V2

V
1

1V

1 q2 T

Thus, q2

0, w2

1 nR
H

V2 V3 V2 V3

, and S 2
1

U 2

q2

w2

34: Reversible Isothermal Compression

w3 S 3
4

V4 nR C ln , q3 V3
4

w3 q3

V4 nR C ln V3 w3
4

V4 nR ln , U 3 V3

41: Reversible Adiabatic Compression

q4
1

0, w4 q4 T

nR
1

1 0, U 4

V4 V1 q4
1

S 4

w4

nR
1

V4 V1

 Summary:
q1 q2 q3 q4 S1 S 2 S 3 S 4
2

nR 0

V2 ln V1

w1 w2 w3 w4
1 1

nR nR

V2 ln V1 1 V2 V3
1

V4 nR C ln V3 0
2

V4 nR C ln V3 nR
C

V2 nR ln V1 0 nR ln 0 V4 V3
H V1

1
1 1

V4 V1
1

CV4

H V2

CV3

V2 V1

V3 V4

V2 V1

V3 V4

V2 V3

V1 V4

 qtot:

qtot qtot qtot qtot

q1 nR nR nR

q2
H

q3

q4

V2 ln V1 V2 ln V1
C

V4 0 nR C ln V3 V3 nR C ln V4 V2 ln V1

wtot wtot

wtot:
w1
2

w2
H

w3

w4 nR
H

nR

V2 ln V1 nR
C

1 1 V2 V1 V4 V1

1
1

V2 V3

V4 nR C ln V3 wtot wtot wtot nR

1 ln

nR 1 nR 1

V2 V3
C

1 C C

V4 V1

nR nR

V2 ln V1 V2 ln V1

 Stot:

S tot S tot S tot S tot S tot

S1

S 2

S 3

S 4 0

V2 nR ln V1 V2 nR ln V1 V2 nR ln V1 0

V4 0 nR ln V3 V3 nR ln V4 V2 nR ln V1

 Utot:
U tot U tot U 1 0
2

U 2
H

U 3
1

U 4 0 nR

nR

V2 V3 V2 V3
C

1 V4 V1

1
1

V4 V1

U tot U tot U tot

nR 1 nR 1 0

1 C C

 Efficiency, erev:
erev wtot qH nR erev nR erev 1
C H H

wtot q1
H 2

V2 ln V1

H H

V2 ln V1

qC e 1 qH

erev

C H

3.3: Entropy
Sadi Carnot noticed the importance of q/T in

his work. But he cannot give a clear physical picture of that term! Clausiuss contribution on Entropy Entropy the spirit of the 2nd Law of Thermodynamics 1. See Fig-3.5 on p. 85 dqrev 2. The definition of Entropy: dS S T 3. Molar entropy: S m n 4. The chain of reasoning that led to entropy

3.4: Calculation of Entropy Changes

1. Cyclic Process: S 0 (S is a state function) 2. Reversible Adiabatic Process: S 0

dqrev 0 ds = dqrev/T = 0 S 0 3. Reversible Phase Change at Const. T and P:

H S T 2 dq 1 2 qP H rev S dqrev 1 T T 1 T T Example 3.1 on p. 88: Find S for the melting of 5.0 g ice (heat of fusion = 79.7 cal/g) at 0 C and 1 atm. Find S for the reverse process.

4. Reversible isothermal process:

2 1

dqrev T

1 T

2 1

dqrev

qrev T

qrev T

5. Const-P heating with no phase change

dq P dS S

dH dqrev T
2 1

C P T dT dq P CP T dT T T 2 C T dT P 1 T

dS

 Example 3.2: See p. 88

The specific heat capacity of water, CP, is nearly constant at 1.00 cal/g C in the temperature range 25 C to 75 C at 1 atm. (a)Find S when 100 g of water is reversibly heat from 25 C to 50 C at 1 atm. (b) Without doing the calculation, state whether S for heating 100 g of water from 50 C to 75 C at 1 atm will be greater than, equal to, or less than S for the 25 C to 50 C heating.

(a) 25 C to 50 C heating:
S S
2 1

dq rev T

2 1

C P dT T

T2 C P ln T1 8.06 cal/K 33.7J/K

323 .15K 100 cal/K ln 298 .15K

(b) 50 C to 75 C heating:
S S
3 2

dq rev T

3 2

C P dT T

T3 C P ln T2 7.46 cal/K 31.2J/K

348 .15K 100 cal/K ln 323 .15K

6. Reversible change of state of a perfect gas

dU dqrev dS rev S S

dqrev CV dT dqrev T

dwrev PdV

dqrev CV dT

dU

dwrev

nRT dV V

dT dV CV nR T V 2 T2 V2 dT dV dS CV nR 1 T1 V1 T V T2 C T dT V2 V nR ln T1 T V1

7. Irreversible change of state of a perfect gas

Construct the virtual reversible processes!

 Example 3.3:

Let n moles of a perfect gas undergo an adiabatic free expansion into a vacuum (the Joule experiment). (a) Express S in terms of the initial and final temperature and volumes. (b) Calculate Sm if V2 = 2V1.
S S If V2
T2 T1 V2 V1

CV T dT T dV nR V

V2 V1

dV nR V

(Note that dT

0)

V2 nR ln V1
V2 V1

2V1 , S m

dV R V

2V1 R ln V1

R ln 2

8. General change of sate from (P1, T1) to (P2,

T2): See 4.5 Create a series of virtual processes: (P1,T1) (P2,T1) (P2,T2) Step 1: Isothermal process Step2: Isobaric process 9. Irreversible phase change: Create a series of virtual processes 10. Mixing of different inert perfect gas at constant P and T: See Fig-3.8
S Sa Sb V na R ln Va V nb R ln Vb

3.5: Entropy, Reversibility, and Irreversibility 1. Suniv = Ssys + Ssurr Reversible Process: Suniv 0 Irreversible Process: Suniv > 0
2. Entropy and Equilibrium

Thermodynamic equilibrium in an isolated system is reached when the systems entropy is maximized.

Example: Comparing the total entropy changes for a small

amount of energy, for example, 9J, to be transferred (1) from a large, hot reservoir at 900 K to a large, cold reservoir at 300 K; (2) from the 300 K reservoir to the 900K reservoir; (3) between two 600 K reservoirs. 1) Hot reservoir: Qh = - 9J, Sh = Qh/Th = - 9J/900K = - 0.01 J/K Cold reservoir: Qc = +9J, Sc = Qc/Tc = +9J/300K = +0.03 J/K Universal entropy change: Suniv = Sh + Sc = +0.02 J/K > 0 2) Hot reservoir: Qh = +9J, Sh = Qh/Th = +9J/900K = +0.01 J/K Cold reservoir: Qc = - 9J, Sc = Qc/Tc = - 9J/300K = - 0.03 J/K Universal entropy change: Suniv = Sh + Sc = - 0.02 J/K < 0 3) 1st reservoir: Q1 = - 9J, S1 = Q1/T = - 9J/600K = - 0.015 J/K 2nd reservoir: Q2 = +9J, S2 = Q2/T = +9J/600K = +0.015 J/K Universal entropy change: Suniv = S1 + S2 = 0 J/K

3.6: The Thermodynamic Temperature Scale The triple point of water 273.16 K at 4.58 torr The perfect gas temperature scale and the thermodynamic temperature scale are numerically identical.

3.7: What is Entropy

Carnot & Clausius:

The ratio of heat delivered to the cold reservoir and the temperature at which it is delivered.

Qrev T

Entropy, S, is a measure of the unavailability

of a system to do work! Spontaneous processes tend to move from ordered states to random states. + NaCl(s) + H2O Na (aq) + Cl (aq) Entropy: a measure of the disorder of a system (This is a bad description of entropy)

Entropy: Towards the Most Probable State

most random states

most ordered state

most ordered state

1 16

4 16

6 16

4 16

1 16

Randomly throwing 4 balls in 2 boxes

300

(n) = 210 =1024

252 250

Lucky pennies!
1 0 1000000000 0100000000 0010000000 0001000000 0000100000 0000010000 0000001000 0000000100 0000000010 0000000001

210

210

# of microstates, (n)

200

150

120

120

100

10

50

45

45

10 1

10 1

0
0 1 2 3 4 5 6 7 8 9 10

 The equilibrium thermodynamics state of an isolated system is the most probable state. The increase in S in an isolated system proceeds toward equilibrium is directly related to the systems going from a state of lower probability to higher probability. See the analysis on p. 98 100. Boltzmann Constant:

kB = R/NA = = 1.3806

10-23 J/K

Statistics &Thermodynamics
Statistics
Macrostates (observable) The # of microstates: (n) Total # of microstates: (n) The most probable state (n)

Chemistry / Physics
Thermodynamic states Multiplicity / Degeneracy Complexity Equilibrium Entropy, S

Boltzmann described the entropy on molecular level. Each thermodynamic state has a specific number of microstates, , associated with it.

S = kBln