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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008 Lecture #10 page 1

Entropy and Disorder

• Mixing of ideal gases at constant T and p

nA A (g, VA, T) + nB A (g, VB, T) = n (A + B) (g, V, T)

nA nB spontaneous n =
nA +
nB
VA VB mixing V
= V

A +
VB

To calculate ΔSmix , we need to find a reversible path between

the two states.

constant T A B
A+B

piston piston back to initial state

permeable permeable
to A only to B only

ΔSdemix = −ΔSmix function of state

For demixing process

⇒ ΔU = 0 ⇒ qrev = −w rev = pAdVA + pB dVB
work of compression of each gas

dqrev VA p dV VB p dV V V
∴ ΔSdemix = ∫ = ∫ A A + ∫ B B = nAR ln A + nB R ln B
T V T V T V V

nA nB
Put in terms of mole fractions XA = XB =
n n

VA VB
Ideal gas ⇒ XA = XB =
V V
5.60 Spring 2008 Lecture #10 page 2

∴ ΔSdemix = nR [XA ln X A +XB ln XB ]

⇒ ΔSmix = −nR [X A ln XA +XB ln XB ]

Since XA , XB < 1 ⇒ ΔSmix > 0 mixing is always spontaneous

The mixed state is more “disordered” or “random” than the

demixed state.
Smixed > Sdemixed

This is a general result ⇒

Entropy is a measure of the disorder of a system

∴ For an isolated system (or the universe)

ΔS > 0 Spontaneous, increased randomness

ΔS = 0 Reversible, no change in disorder
ΔS < 0 Impossible, order cannot “happen” in isolation

There is an inexorable drive for the universe to go to a

maximally disordered state.

Examples of ΔS calculations
đqrev
In all cases, we must find a reversible path to calculate ∫ T

(a) Mixing of ideal gases at constant T and p

nA A (g, VA, T) + nB A (g, VB, T) = n (A + B) (g, V = VA + VB, T)

ΔSmix = −nR [X A ln XA +XB ln XB ]

5.60 Spring 2008 Lecture #10 page 3

(b) Heating (or cooling) at constant V

A ( T1 , V) = A ( T2 , V )

đqrev T2 CV dT if CV is
T
ΔS = ∫ T
= ∫T
1 T =
T -independent
CV ln 2
T1
[Note ΔS > 0 if T2 >T1 ]

(c) Reversible phase change at constant T and p

e.g. H
2O (l, 100°C, 1 bar) = H2O (g, 100°C, 1 bar)

q p = ΔHvap

q pvap ΔH vap
ΔSvap (100°C ) = = (Tb = boiling Temp at 1 bar)
Tb Tb

(d) Irreversible phase change at constant T and p

e.g. H
2O (l, -10°C, 1 bar) = H2O (s, -10°C, 1 bar)

This is spontaneous and irreversible.

∴ We need to find a reversible path between the two states

to calculate ΔS.

irreversible
H2O (l, -10°C, 1 bar) = H2O (s, -10°C, 1 bar)

đqrev = C p ( A )dT đqrev = C p ( s ) dT

reversible
H2O (l, 0°C, 1 bar) = H2O (s, 0°C, 1 bar)
q rev
p = −ΔHfus
5.60 Spring 2008 Lecture #10 page 4

ΔS = ΔSheating + ΔSfus + ΔScooling

Tfus C p ( A ) dT −ΔHfus T C p ( s ) dT
∫T +∫
1
= +
1 T Tfus Tfus T

−ΔHfus Tfus dT
∴ ΔS = +∫ ⎣⎡C p ( A ) − C p ( s ) ⎦⎤ T
T T1

−ΔHfus Tfus
ΔS = + ⎡⎣C p ( A ) − C p ( s ) ⎤⎦ ln if Cp values are T-independent
T T1