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

To calculate Smix , we need to find a reversible path between the two states.
constant T A+B
piston permeable to A only piston permeable to B only

back to initial state

Sdemix = Smix

function of state

For demixing process

U = 0

qrev = w rev = pAdVA + pB dVB

work of compression of each gas

Sdemix =

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

Put in terms of mole fractions Ideal gas

XA = VA V XB = VB V

XA =

nA n

XB =

nB n

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Sdemix = nR [XA ln X A +XB ln XB ] Smix = nR [X A ln XA +XB ln XB ] Smix > 0

Since XA , XB < 1

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) Spontaneous, increased randomness Reversible, no change in disorder Impossible, order cannot happen in isolation

S > 0 S = 0 S < 0

There is an inexorable drive for the universe to go to a maximally disordered state. Examples of S calculations In all cases, we must find a reversible path to calculate (a) Mixing of ideal gases at constant T and p

qrev
T

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

Smix = nR [X A ln XA +XB ln XB ]

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(b) Heating (or cooling) at constant V A ( T1 , V) = A ( T2 , V )

S =

qrev
T

T2
1

CV dT T

if CV is

T -independent

T CV ln 2 T1

[Note S > 0 if T2 >T1 ] (c) Reversible phase change at constant T and p

e.g. H2O (l, 100C, 1 bar) = H2O (g, 100C, 1 bar)

q p = Hvap
vap qp H vap Svap (100C ) = = Tb Tb

(Tb = boiling Temp at 1 bar)

(d)

Irreversible phase change at constant T and p

e.g. H2O (l, -10C, 1 bar) = H2O (s, -10C, 1 bar) This is spontaneous and irreversible. We need to find a reversible path between the two states to calculate S. H2O (l, -10C, 1 bar)
irreversible

H2O (s, -10C, 1 bar)

qrev = C p ( A )dT
H2O (l, 0C, 1 bar)
reversible

qrev = C p ( s ) dT

rev p

H2O (s, 0C, 1 bar)

= Hfus

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Lecture #10

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S = Sheating + Sfus + Scooling =

Tfus
1

C p ( A ) dT Hfus T C p ( s ) dT + + Tfus T Tfus T

1

Hfus

S =

Hfus

Tfus

T1

C p ( A ) C p ( s ) T

dT

S =

+ C p ( A ) C p ( s ) ln

Tfus T1

if Cp values are T-independent