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September 10, 2001

Reading: Chapter Three


Homework: 3.1,3.2,3.4,3.5,3,6

Entropy and the Criterion for Equilibrium:


For any given system, it either remains as it is if it is initially at equilibrium or
undergoes a spontaneous irreversible process moving toward equilibrium if it is
initially at nonequilibrium. The attainment of the equilibrium coincides with the
entropy reaching the maximum. Hence entropy can be used as a criterion for
determining the equilibrium state.
Taking

dS =

P
1
dU + dV .
T
T

If U and V are fixed, then dU = 0 and dV = 0. Consequently, dS =0, which implies


that S = S(U,V) is at extremum. Since entropy increases as the system
spontaneously moves toward equilibrium, S must be at maximum rather than
minimum. So, Equilibrium occurs in a system of constant internal energy and
constant volume when entropy of the system is maximized.
Taking

dU = TdS PdV .

If S and V are fixed, then dS = 0 and dV = 0. Consequently, dU =0, which implies


that U = U(S,V) is at extremum. Since internal energy decreases as the system
spontaneously moves toward equilibrium, U must be at minimum rather than
maximum. So, Equilibrium occurs in a system of constant entropy and constant
volume when internal energy is minimized.
Example 1: Maximization of S for fixed U and V for equilibrium.

Adiabatic
enclosure

T1
Idea gas

T2

diaphragm

Assuming T2 > T1. Opening diaphragm, heat flows from T2 to T1 until equilibrium
when T2 decreases to T2 and T1 increases to T1.
For the U in the total system remains fix (i.e., energy gain in the left half = energy
lost in the right half):

CV (T1' T1 ) = CV (T2 T2' )

T2' = T1 + T2 T1'

So,

In general, for the time being we take T1 and T2 unequal to each other.
T1'

T2'

T1'

T2'

q
q
dT
dT
S = 1 + 2 =CV
+ CV
T T T
T
T
T
T
T
1

S = CV ln

TT
T (T1 + T2 T1 ' )
= CV ln
T1T2
T1T2
' '
1 2

'
1

For the entropy, S, to be maximized, so the function ln


hence

T1' (T1 + T2 T1 ' )


, and
T1T2

T1' (T1 + T2 T1 ' )


d (S )
is to be maximized. Therefore,
= 0 translates into
T1T2
dT1'

d T1' (T1 + T2 T1 ' )

=0
T1T2
dT1'

i.e.,

T1 + T2 2T1 ' = 0
T1 ' =

And
Thus, at T1 ' = T2 ' =

T1 + T2
2

T2 ' = T1 + T2 T1 ' =

T1 + T2
2

T1 + T2
, the S is at the extremum. Furtheremore,
2
d 2 T1' (T1 + T2 T1 ' ) 2
< 0.

=
T1T2
d (T1' ) 2
T1T2

So, the S is at the maximum. Therefore, we show that at fixed U and V,


maximization of entropy provides the criterion of equilibrium ( T1 ' = T2 ' ).
Example 2: (problem 3.3) One mole of a monatomic ideal gas undergoes a
reversible expansion at constant pressure during which the entropy of the gas
increases by 14.41 J/K and the gas adsorbs 6236 joules of heat. Calculate the
initial and final temperatures of the gas.

Solution: Since we have two unknowns, we need to set up two equations. The first
one related entropy change to the two unknown temperatures and the send one
relates the heat to the two unknown temperatures.

For constant pressure process:


q p
dT
= Cp
dS =
T
T
T2
T
dT
S = C p
= C p ln 2
T
T1
T1
q p = C p (T2 T1 )

(1):

14.41 = 2.5 8.3144 ln


0.693255 = ln

(2):

(3)+(4):

(1)
(2)

T2
T1

T2
T1

T2 = 2T1
6236 = 2.5 8.3144 (T2 T1 )
T2 = T1 + 300

(3)
(4)

T1 = 300 K, T2 = 600 K.

Example 3: (problem 3.3) One mole of a monatomic ideal gas undergoes a


reversible isothermal expansion during which it doubles its volume, performs
1729 joules of work and increases its entropy by 5.763 J/K. Calculate the
temperature at which the expansion was conducted.

Solutions: Since we only have one unknown, we need one single equation (of
state) that relates the unknown to the two given quantities.
For an isothermal process, dU = 0, q = w
q w
=
dS =
T
T
q w
T = constant:
S = =
T T
w
1729
T=
So,
=
= 300 K.
S 5.763
We can actually solve the problem without the need of information of actual
volume change (doubling).
V2
V2
V
RT
w = PdV =
dV = RT ln 2 = RT ln 2
Alternatively,
V
V1
V1
V1
So,

T=

w
1729
=
= 300 K
R ln 2 8.3144 0.693

We solve the problem without the need of information of entropy. This is because
for an isothermal process, volume change defines entropy change
S = R ln(V2 / V1 ) and we need to know only one of them.

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