Thermodynamic Definition of Entropy

-w

= qH

qH + q L
qH

qH + qL T HT L
qH = T H

any process
reversible process

qL
TL
1+q =1 T
H
H
qL
qH
=

TL
TH
qL qH
TL + TH = 0

for a Carnot Cycle

qrev
S= T
dqrev
dS = T
Need to show that
dqrev
a. S is a state function for a general cycle: o T = 0
dq
b. for irreversible cycles: o < 0
T
dq
c. S
T
d. Entropy always increases for a spontaneous process in an isolated system
Entropy is a State Function for a General Cycle
1. let number of small cycles ->
qrev
2. the sum of T = 0 around each
small cycle

3. sum over the high temperature

isotherms then over the low temperature
isotherms = 0

dq
Clausius Inequality: Irreversible cycles: o T < 0

< max

qH + qL T HT L
qH < T H

< for irreversible process

qL
TL
1+q <1 T
H
H
qL
qH
<

TL
TH
qL qH
T L + T H < 0 or

dq
T <0

for a Carnot Cycle

for a General Cycle: divide into many Carnot Cycles (as before):
dq
o 0
< for irreversible process = for reversible process
T
S
dq
o T 0
f

Clausius inequality

dq
T

irreversible

dqrev
dq
T + f T 0
i

reversible

V
f

dqrev
dq
T i T 0
i
f

dq
T S 0

dq

> for irreversible process

= for reversible process

Entropy always increases for a spontaneous process in an isolated system

for an isolated system

dq = 0

S 0