Chem120B
Problem Set 3
Due: February 11, 2011
Simon’s
Physical Chemistry
textbook.
For problem 1737 explain in terms of energy and entropy why
f
J
/f
0
has a local maximum.
For problems I1 and I2 a handful of values of
x
is sufficient (say, 0.005, 0.01, 0.05, and 0.1).
2. In thermodynamics temperature is defined by the derivative
1
T
=
p
∂S
∂E
P
N,V
(i) A system at temperature
T
absorbs a small amount of energy
Δ
E
. By how much does its entropy
change? To answer this question, write a Taylor series for
Δ
S
ordered in powers of
Δ
E
. Since the
energy change
Δ
E
is small, you may neglect terms of order
Δ
E
2
and higher (i.e., include only the
term proportional to
Δ
E
).
(ii) Now consider two systems initially at temperatures
T
1
and
T
2
. What is the total change in entropy
Δ
S
= Δ
S
1
+ Δ
S
2
when a small amount of energy
Δ
E
is transferred from system #1 to system #2?
(iii) Our physical intuition says that heat flows from hot systems to cold systems. In other words,
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 Spring '09
 JAMESAMES
 Physical chemistry, Thermodynamics, pH, Energy, partition function

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