Chapter 10

Spontaneity, Entropy, and Free Energy

Concept for second law of

thermodynamic

Isothermal expansion device

One-Step Expansion (No Work)

Mass M1 is removed from the pan, the gas

will expand, moving the piston to the right

end of the cylinder.
P11/4P1, V14V1,
No work is done. W0=0
Free expansion

One-Step Expansion
M1 is replaced by M1/4.

P1
Pex
4
W1 Pex V
P1
3
W1 ( )(4V1 V1 ) P1V1
4
4

Two-Step Expansion
Work for s tep 1 P11/2P1, V12V1
P1
P1V1
'
W ( 2V1 V1 )
2
2
Work for s tep 2 1/2P11/4P1, 2V14V1
P1
P1V1
''
W ( 4V1 2V1 )
4
2
W2 P1V1

PV diagram two-step expansion

The PV diagram six-step expansion

Infinite-Step Expansion
n

Wn Pi Vi

(dV: V0 )

i 1

Pex is changed by infinitesimally small increments.

Wrev Pex dV
V1

Wrev nRT

V2

V1

Wrev

W2

V2

W1

V1

(dW PdV dW PdV )

V2

dV
V

(P

nRT
)
V

V2
4V1
nRT(lnV2 lnV1 ) nRTln( ) nRTln(
)
V1
V1

Wrev nRTln4 1.4nRT 1.4P1V1

q rev Wrev nRTln(

V2
)
V1

x2

x1

x2
1
dx ln
x
x1

Reversible expansion

Reversible Process
Reversible process: the system is always

infinitesimally close to equilibrium, and an

infinitesimal change in conditions can
reverse the process to restore both system
and surroundings to their initial states.

A heat engine operating between two

temperatures

Heat Engines
A heat engine converts some of the random

molecular energy of heat flow into

macroscopic mechanical energy.
qH: the working substance from a hot body
-w: the performance of work by the working
substance on the surroundings
-qC: the emission of heat by the working
substance to a cold body

The Second Law of Thermodynamics

Kelvin-Planck statement for heat engine

It is impossible to extract an amount of heat

qH from a hot reservoir and use it all to do

work W. Some amount of heat qC must be
exhausted to a cold reservoir.
This is sometimes called the "first form" of
the second law, and is referred to as the
Kelvin-Planck statement of the second law.

A system that violates the second law

Heat Efficiency
For a heat engine q w 0, - w 0 and - q c 0
so w 0 and q c 0
work
-w w
heat efficiency e

energy input q H q H
For a cycle of operation, U 0
0 q w q H qc w -w q H qc
e

q H qc
qH

qc
1
qH

qc 0 , q H 0 e 1

The Second Law of Thermodynamics

Clausius statement for refrigerator

It is not possible for heat to flow from a

colder body to a warmer body without

any work having been done to accomplish
this flow. Energy will not flow
spontaneously from a low temperature
object to a higher temperature object.
The statements about refrigerators apply to
air conditioners and heat pumps which
embody the same principles.

Carnots Principle
No heat engine can be more efficient than a

reversible heat engine when both engines work

between the same pair of temperature H and C.
Isothermal Process: the temperature of the
system and the surroundings remain constant at
all times. (q=-w)
Adiabatic: a process in which no energy as heat
flows into or out of the system. (U=w)

Carnot cycle
Carnot cycle is a four stage reversible

sequence consisting of
1. isothermal expansion at high temperature T2
2. adiabatic expansion
3. isothermal compression at low temperature T1
4. adiabatic compression
5. back to stage 1 and continue.

Carnot Efficiency

nRT
P
and dU CV (T)dT
V
dU dq dw dq PdV
nRT
CV (T)dT dq
dV
V
dT dq
dV
CV (T)

nR
T
T
V
dT
dq
dV
CV (T) T T nR V

T2
T3
T4
T1
dT
dT
dT
dT
dT
CV (T) T T1 CV (T ) T T2 CV (T ) T T3 CV (T ) T T4 CV (T ) T

TC
TH
dT
dT
dT
T2 CV (T ) T TH CV (T ) T TC CV (T ) T
T1
TH
dT
dT
C
(
T
)

C
(
T
)
V
V
T4
TC
T
T
dT
CV (T ) T 0
T3

T2 dq
T3 dq
T4 dq
T1 dq
dq

0
T T1 T T2 T T3 T T4 T

0
T2 dq
T4 dq
dq
qH qC

0
T T1 T T3 T TH TC

erev

qH qC TH TC

qH
TH

Carnot Efficiency

Adiabatic Process
U w ( q 0 )
Cv
nRT
R
nCv dT PdV nCv dT
dV
dT dV
V
T
V
T2 1
V2 1
T2
V2
V1
Cv dT R
Cv ln( ) R ln( ) R ln( )
T1 T
V1 V
T1
V1
V2
T2 Cv
V1 R
T2 Cv
V1 (C p Cv )
( ) ( ) ( ) ( )
(C p - C v R)
T1
V2
T1
V2
T2
V1
( )( )
T1
V2

Cp
Cv

1)

V1 1 C p
( ) (
)
V2
Cv

 1
1
1
2

T2 V

T1 V

for ideal gas

1
PV
PV
T
PV
V

1 1
2 2 2 2 2 1 1 PV

PV
1 1
2 2
T1
T2
T1 PV
V2
1 1

For isothermal process PV

1 1 PV
2 2

For adiabatic process PV

PV
1 1
2 2

U=0 for an isothermal process, q=-w

V2

V2

V1

V1

W P dV nRT
V2
q nRT ln
V1

V2
1
dV nRT ln
V
V1

No heat transfer (q=0) for adiabatic

process, U=w

PV K
K
W P dV
dV
V1
V1 V
1
1
K (V2 V1 )
W
1
V2

V2

Adiabatic Process
Process in which no heat transfer takes place

3
U nR (T2 T1 ) W
2

Application of Carnot Cycle

P (atm)

V (L)

10

1.5

20

25.5

12.75

Calculate Q, U, W
First law:

U = QH QL + W
W = QL - Q H

Spontaneous Process and Entropy

Spontaneous Process: A

process occurs without

outside intervention.
Entropy: In qualitative
terms, entropy can be
viewed as a measure of
randomness or disorder
of the atoms or
molecules in a
substance.

Definition of Entropy
S=kBln
kB: Boltzmanns constant
: the number of microstates
corresponding to a given state

For one particle

S1=kBln1
S2=kBln2
S=S2-S1= kBln2-kBln1=kBln(2/1)
S= kBln(21/1)=kBln2

 M104

4 2 24=16
M104

For five particles

2
25
1
For one mole of particles
2
6.021023
2
1
S k B ln(2

6.021023

) (6.02 10 )( k B ln 2)
23

N 0 k B ln 2 R ln 2
M104

Definition of entropy in term of probability

2 V2

1 V1
For 1 mole of gas
For n mole of gas

SV1 V2

V2
R ln( )
V1

SV1 V2

V2
nR ln( )
V1

Entropy for Isothermal Process

q w U 0 q w
V2
V2
S nR ln (
) and q rev nRT ln (
)
V1
V1
q rev
S
T
V2

V2

V1

V1

W P dV nRT
V2
q nRT ln
V1

V2
1
dV nRT ln
V
V1

Quantity of Entropy for Reversible

Process
dqrev dU dWrev nCv dT PdV Cv dT nRT

dV
V

dqrev
dT
dV
dS
nCv
nR
T
T
V
T2
V2 dV
dT
S n Cv (T )
nR
T1
V1 V
T
T2
dT
V2
S n Cv (T )
nR ln
T1
T
V1
If the temperature change is not large, it may be a good
approximation to take C v constant.
T2
V2
S nCv ln nR ln
T1
V1

Entropy and Physical Changes

Temperature Dependence
qrev
S
T
T
T dq
dqrev
rev
dS
ST T T dS T
T
T
For P constant
T dq p
T dT
T2
dq p nC p dT ST T T
nC p T
nC p ln
T
T
T1
2

For V constant
T2

dqv nCv dT ST T T
1

dq p
T dT
T2
nCv T
nCv ln
T
T
T1
2

Entropy and Physical Changes

Change of State
qrev
S
T

Change of state from solid to liquid

qrev=Hfusion
T=melting point in K
Change of state from liquid to gas
qrev=Hvaporization
T=boiling point in K

The Second Law of Thermodynamics

The Third Statement
In any spontaneous process, there

is always an increase in the

entropy of the universe.
dq/T is the differential of a state
function S that has the property
Suniv 0 for any process

Entropy and Second Law of

Thermodynamics
Suniv= Ssys+Ssurr

S surr

Gibbs Free Energy

At constant T and P
G
H
G H T S

S
T
T
H
G
Q S surr

S surr S sys Suniv
T
T
G 0 spontaneous
Suniv>0, so G<0
G 0 equilibrium
G 0 non-spontaneous

Free Energy and Chemical Reactions

S

0
reaction

0
products

G H T S
0

0
reactants

Third Law of Thermodynamics

The entropy of a perfect crystal at 0 K is zero.

lim S 0
T 0

It is impossible to reach a temperature of

absolute zero
It is impossible to have a (Carnot) efficiency
equal to 100% (this would imply Tc = 0).

(a) T=0 K, S=0

(b) T>0 K, S>0

The Dependence of Free Energy on

Pressure
G G 0 RT ln( P )
N 2 3H 2 2 NH 3
0
0
0
G 2[GNH

RT
ln(
P
)]

[
G

RT
ln(
P
)]

3[
G
NH 3
N2
N2
H 2 RT ln( PH 2 )]
3
0
0
0
(2GNH

3
G
N2
H 2 ) RT [2 ln( PNH 3 ) RT ln( PN 2 ) 3ln( PH 2 )]
3
0
2
3
G Greaction
RT [ln( PNH
)

ln(
P
)

ln(
P
N2
H 2 )]
3
0
G Greaction
RT ln[

2
PNH
3
3
H2

( PN2 )( P )

0
G Greaction
RT ln(Q) (Q=

]
2
PNH
3
3
H2

( PN2 )( P )

Free Energy and Equilibrium

At equilibrium
G G products Greactants 0 G

0
reaction

0
reaction

RT ln( K )

RT ln(Q )

The Temperature Dependence of K

G 0 RT ln( K ) H 0 T S 0
H 0 S 0
H 0 1 S 0
ln( K )

( )
RT
R
R T
R
H 0 S 0
ln( K 2 )

RT2
R
H 0 S 0
ln( K1 )

RT1
R
K2
H 0 1 1
ln( )
[ ]
K1
R T2 T1

Free Energy and Work

For a process at constant T and P
dqrev dqirrev
dS rev

dqirrev TdS rev

T
T
dqirrev dU dw TdS dU TdS dw U TS w
G H-TS U PV TS G TS w PV TS w PV
dG dw PdV VdP dw PdV
dw dwP V dwother PdV dwother
dG PdV dwother PdV dG dwother
G wmax