Two objects hot and cold

cold hot thermal

equilibrium

Found : thermal equilibrium
process occurs spontaneus
heat flows from hot to cold object
T
2
(Hot)

T
1
(Cold)

w
q
2


q
1


q
1


q
2


w
w
q
2


q
1


Possible



Possible



Forbidden
possible : absorb q
2
from T
2
,doing work w and release q
1
to
T
1

forbidden : return from T
1
to T
2
( cyclic process), then

Scientists proposed a Carnot Heat Engine.

T
2
(Hot)
T
2
(Cold)
q
1
(release)
q
2
(Absorb)
Forbidden w
Possible
Contain
working
fluid
Basic idea : PV = nRT plot P against V at constant T
gives

T (Isothermal)
V
P P
V
T2
T1
P P
V V
A
B
C
D
A
B
C
D
Heat engine Heat pump
For complete one cycle:
A to B : isothermal reversible expansion
B to C : adiabatic reversible expansion
C to D : isothermal reversible compression
D to A : adiabatic reversible compression
Efficiency, c :
2
1 2
2
) net ( total
q
) q q (
q
w

= = c
2
1 2
2
1 2
2
T
) T T (
| q |
| q | | q |
| q |
| w |
=

= = c
Heat Pump :
Coefficient of performance, |




If the working fluid is an ideal gas, then ideal gas
law is obeyed.

) T T (
T
| q | | q |
| q |
| w |
| q |
1 2
1
1 2
1 1

= = |
Qualitative :
a measure of disorder ; entropy increases if the
level of disorder increase.

In a Carnot cycle , two things happen:
- heat change into work and
- transfer of heat from hot reservoir into cold
reservoir spontaneously and at same time
disorder occurs in the cold reservoir. Heat
released by the system (-dq) is absorbed by the
cold reservoir(+dq).



9
2
1 2
2
1 2
T
| T | | T |
q
| q | | q |
=

= c
2
2
1
1
T
| q |
T
| q |
=
0
T
| q |
T
| q |
2
2
1
1
= +
T
q
rev
Then proposed

Is a State function
Quantitative:

Or:

2
1
2
1
T
T
1
| q |
| q |
1 =
For a reversible process:
t tan cons
T
| q |
T
| q |
2
2
1
1
= =
Or:

10
Clausius define entropy, S as:




where heat absorbed by the system is reversible at
T.


T
dq
dS
rev
=
T
dq
S S S dS
rev
1 2
} }
= = A =
11
irreversible



* A * B
reversible
} } }
+ =
T
dq
T
dq
T
dq
rev irrev
) S (S
T
dq
T
dq
B A
irrev
+ =
} }
a) Entropy for irreversible process

12
Clausius:
0
T
dq
irrev
s
}
0 ) S S (
T
dq
T
dq
B A
irrev
s
(

+ =
} }
}
>
T
dq
) S S (
irrev
A B
13
dq
irreversible
= 0
Then : S
B
S
A
> 0 or S
B
> S
A

entropy increases for spontaneous or irreversible
process .

14
0
T
dq
rev
=
}
Because dq
reversible
= 0
S
B
= S
A
( called isentrop )
0 dq
rev
=
Therefore :
process occurs at constant T is assume reversible,
Example: Phase changes
Solid liquid



liquid gas
15
int po melting
melting
melting
T
H
S
A
= A
boiling
on vaporizati
on vaporizati
T
H
S
A
= A
Troutons rule S
vapourisation
21 eu mol
-1

H
vap
( in cal mol
-1
) 21 T
boiling point


16
S = S ( T, V ) and first law
Divided by T



For ideal gas:



Constant T: Constant V:




dV
T
P
dT
T
C
dS
V
|
.
|

\
|
+
|
.
|

\
|
=
1
2
1
2
V
V
V
ln nR
T
T
ln C S + = A
1
2
V
V
ln nR S = A
1
2
V
T
T
ln C S = A
17
From equation:



So:
Integrate
dV
T
P
dT
T
C
dS
V
|
.
|

\
|
+
|
.
|

\
|
=
T
C
T
S
V
V
=
|
.
|

\
|
c
c
Important!
Similarly:
T
C
T
S
P
P
=
|
.
|

\
|
c
c
Important!
aA + bB cC + dD

S = [cS
C
+ dS
D
] [ aS
A
+ bS
B
]



assume C
P
constant

| |

=
|
.
|

\
|
c
A c
) R ( P ) R ( (Pr) P (Pr)
P
C n C n
T
1
T
S
T
C
T
S
P
P
A
=
|
.
|

\
|
c
A c