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S
T
dT =
U,V
S
n
U,V
n
T
dT
1a
U,V
PV
n
dT =
dT.
T
RT T2
1b
so that
2011 American Association of Physics Teachers
74
S
n
=
U,V
.
T
P 3 1
Z ,
RT th int
Tf
dS = PV
Ti
1 i 5
1 f 5
T f RT f 2
Ti RTi 2
Tf
Ti
TdS
1
P
Tf
= PV ln NA h2/2mkB3/2 c P lnTiT f ln .
2
R
Ti
6
Here, c P = cV + R is the specific heat at constant pressure c P
= 3.48R for dry air, that is, there is a contribution of 21 R to cV
for each of three translational degrees of freedom and two
rotations, but vibrations are not excited at room temperature.
To obtain a sense for the magnitude of these changes,
consider a 4 m 5 m 2.5 m room with volume V
= 50 m3 and atmospheric pressure whose temperature is
raised from Ti = 273 K to T f = 300 K. We have to expel thermal energy Q 10 MJ or 2.8 kW h, provided we make the
room completely air tight and thermally insulated as soon as
the final temperature is reached. From the equation of state
we have that n f T f = niTi so that in this heating process about
10% of the air has been expelled. The entropy change is
S 26 kJ/ K. To put this number into perspective, we
note that the magnitude of this entropy change is about the
same as that occurs by heating and transforming four liters of
water completely into vapor at 1 atm pressure, for which
about 9 MJ is required S and Q positive.
As Sommerfeld and others have discussed,4,5 although the
internal energy remains constant, the molar internal energy
u = U / n increases by
75
,
5
Q=
u f ui = cVT f Ti.
S
T
dT =
P,V
S
n
P,V
n
T
dT.
P,V
We write
n
T
=
P,V
V/ T P,n
.
V/ nT,P
V
T
10
.
P,n
V
n
=
T,P
2G
=
P n
P
=
T,n
V
.
n
11
The last equality results from the fact that, for constant T, the
GibbsDuhem equation
H. J. Kreuzer and S. H. Payne
75
V
S
d = dT + dP
n
n
12
n
T
= n .
13
P,V
=
P,V
P/ nS,V
P/ SV,n
14
P
n
=
S,V
2U
=
V n
V
S T
n V
S,n
15
S,n
V P
n V
16
,
S,n
P
S
=
V,n
so that
S
n
=
P,V
T
2U
=
V S
V
S,n
S V P
n n V
S,n
17
V
T
=
S,n
S V P
n n T
P,n
T
V
=
P,n
S 1 cP
.
n T
S,n
18b
S
T
= n s
P,V
dS = n s
cP
.
T
cP
dT,
T
19
20
U
dU =
T
cP
dT = n h
dT,
P,V
21
1 V
V T
P,n
1 S
S T
22
dT,
P,n
1 V
V T
P,n
1 H
H T
dT.
23
P,n
18a
S V S
=
n n T
dU = nh
S
n
dS = ns
P
T
dT =
V,n
V/ T P,n
dT = dT.
V/ PT,n
T
24
76
77
77