Professional Documents
Culture Documents
Note 2 (增修版) - Chapter 2
Note 2 (增修版) - Chapter 2
The internal energy can be described as a function of any two of the variables;
The heat absorbed by the system can be obtained from the first law, i.e. dQ dU dW ;
H U PV (2.5)
A thermally insulated ideal gas was allowed to expand freely into an insulated chamber, which was
initially vacuous. The final temperature was found to be the same as the initial temperature, i.e.
T1=T2.
T1 T2
Vacuum
Before After
CV UT V dU
dT or dU CV dT (2.9)
C P HT P T
(U PV )
P
U
T P
( PV )
T P
dU
dT
T
( Nk B T )
P
dU
dT
( Nk B T )
T (2.11)
CV Nk B (2.12)
dU dW pdV , dU CV dT
CV dT PdV 0 (2.14)
Using PV NkBT
dT dNk
( PV )
B
PdVNkBVdP (2.15)
2
(2.14) CV ( PdVNkBVdP ) PdV 0 ,
CVP 0,
C
or
dP
P
dV
V
dP
P
dV
V
0 ( CVP )
C
(2.17)
dP
P
dV
V , dP
P
dVV
ln P ln V constant (2.19)
PV constant (2.20)
Using PV NkBT
PV ( )V Nk BTV 1 constant
NkBT
V
Adiabatic
P
Isotherm
V
Fig. 2.2 An adiabatic line has a steeper slope than an isotherm.
Carnot Cycle
In a cyclic transformation, the final state is the same as the initial state, and therefore U 0 . A
reversible cyclic process can be represented by a closed loop in the PV diagram;
The working substance is arbitrary, but we illustrate it for an ideal gas in Fig. 2.3, where T2 > T1.
The system absorbs heat Q2 along the isotherm T2 and reject heat Q1 along T1. By the first law, the
net work output is
3
W Q Q2 Q1 (2.23)
In one cycle of operation, the efficiency of the Carnot engine is defined as
QW Q QQ 1 QQ
2
2
2
1 1
2
(2.24)
which is 100% if there is no waste heat, i.e. Q1=0. But, as we shall see, the second law of
thermodynamics states that this is impossible.
Q2, T2
Q1, T1
V
Fig. 2.3 Carnot cycle on the PV diagram of an ideal gas.
T2
Q2
T1
Q1
Fig. 2.4 Schematic representation of a Carnot engine.
4
Second Law of Thermodynamics
It is stated by Clausius:
There does not exist a thermodynamic transformation whose sole effect is to deliver heat from a
reservoir of low temperature to a reservoir of higher temperature.
There does not exist a thermodynamic transformation whose sole effect is to extract heat from a
reservoir and convert it entirely into work.
Absolute Temperature
The second law implies that a Carnot engine cannot be 100% efficient, for otherwise all the heat
absorbed from the upper reservoir would be converted into work in one cycle of operation.
We can show that no engines working between two given temperatures can be more efficient than a
Carnot engine. Since only two reservoirs are present, a Carnot engine means a reversible engine.
Consider a Carnot engine C and engine X working between the reservoirs T2 and T1, with T2 > T1,
as shown in Fig. 2.5. The total work output is
Now arrange to have Q2 Q2 , i.e. no net heat was extracted from the reservoir T2.
'
An amount of
heat Q1 Q1 was extracted from the reservoir T1 and converted entirely into work with no other
'
effect. This would violate the second law, unless Q1 Q1' . Dividing both sides of this inequality
by Q2 , and using the fact Q2 Q2 , we have
'
Q1'
Q1
Q2 Q2' (2.26)
Q'
1 Q12 1 Q1' C X
Q
Therefore 2
or (2.27)
5
Q’2 Q2
T2
X W W C
T1
Q’1 Q1
Fig. 2.5 Driving a Carnot refrigerator C with an arbitrary engine X.
As a corollary, all Carnot engines have the same efficient, since X may be a Carnot engine. This
shows that the Carnot engine is universal, in that it depends only on the temperatures involved, and
not the working substance.
We define the absolute temperature θ of a heat reservoir such that the ratio of the absolute
temperatures of two reservoirs is given by [form (2.24)]
1
Q12 1
Q
2 (2.28)
where is the efficiency of a Carnot engine operating between the two reservoirs. Since Q1 0
according to the second law, the absolute temperature is bounded from the below:
0 (2.29)
The absolute zero θ=0 is a limiting value which we can never reach, according to the second law.
0
dQ
P T (2.30)
where the equality holds if P is reversible. To prove the assertion, divide the cycle P into K
segments labeled i = 1, … , K. Let the ith segment be in contact with a reservoir of temperature Ti,
from which it absorbs an amount of heat Qi. The total work output of P is, by the first law and
∆U=0,
K
W Qi (2.31)
i 1
6
Note that not all the Qi can be positive, for otherwise heat would have been converted to work with
no other effect, in contradiction to the second law.
Qo1 Qo2
Reservoir To
C2
C1
T1 T2 T3
Q1 Q2
T4
Closed cycle P
Image a reservoir at a temperature To > Ti (all i), with Carnot engines Ci operating between To and
each temperatue Ti, as illustrated in Fig. 2.6.
As (2.28), we have
Qi( o )
To
Qi Ti (2.32)
In one cycle of operation of the joint operations {P+C1+ … + CK}
▲ The reservoir Ti experience no net change, for it receives Qi, and delivers same to the system.
K K
Qtot Qi( o ) To QTii (2.33)
i 1 i 1
(2.31): W Qi
i 1
An amount of heat Qtotal would be entirely converted to work with no other effect, and thus violate
the second law, unless Qtot 0 , or
7
K
i 1
Qi
Ti
0 (according to (2.33)) (2.35)
0
dQ
P T (2.36)
0.
dQ
If P is reversible, the sign for Qi are then reversed, and we conclude that P T
Combining
this with (2.36). We have
0
dQ
P T (if P is reversible) (2.37)
dQ
For a reversible open path P, the integral P T
depends only on the endpoints.
0
dQ dQ dQ dQ dQ
T P T P' T P T P' T
dQ dQ P
Thus, P T P' T (2.38)
-P’
Entropy
dS dQ
T (2.39)
defines a state function S called the entropy. The entropy difference between any two states B and
A is given by
B dQ
S ( B ) S ( A) (along any reversible path) (2.40)
A T
What if we integrate along an irreversible path? Let P be an arbitrary path from A to B. Let R
8
be a reversible path with the same endpoint. The combined process P-R is a closed cycle, and
P (arbitrary path)
A B
-R (reversible path)
0 ,
dQ
therefore by Clausius’s theorem PR T
or
dQ dQ
P T R T (2.41)
Since the right side is the definition of the entropy difference between final state B and the initial
state A, we have
B dQ
S ( B) S ( A) (2.42)
A T
where the equality holds if the process is reversible. For an isolated system, which does not
exchanges heat with the external world, we have dQ 0 , and therefore
S 0 (2.43)
That is, the entropy of an isolated system never decreases and it remain constant during a reversible
transformation.
to the integral only if the path from A to B is reversible. Otherwise, it is generally larger than
the integral.
9
Entropy of Ideal Gas
In Fig. 2.7, we approach point A along two alternative paths, with V kept fixed along path 1. T
kept fixed along path 2 (isothermal). Along path 1, we have (from (2.40))
T dQ
S (V , T ) S (V , To ) ( dW PdV 0 along path 1, dQ dU )
T T
o
T
S (V , T ) S (V , To ) CV dT
S (V , To ) CV ln TTo (2.44)
To T
S (V , T1 ) S (V , To ) CV ln T1o
T
(2.44)
Therefore, we conclude
S (V , To ) Co Nk B lnV (2.47)
From (2.44)
S (V , T ) Co Nk B lnV CV ln T (2.48)
S (V ,T ) Co Nk B ln(VT 3 / 2 ) (2.49)
P
Path 2 (isothermal)
A
T1
Path 1
To
V
Fig. 2.7 Calculating the entropy at point A.
10