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Statistical Entropy
Description of entropy from microscopic point of view. The
arrangements of molecules over the available energy levels
S = k lnW
Statistical Entropy
Example: Suppose a tiny system of four molecules A, B, C, and D that
can occupy three equally spaced levels of energies 0, and 2 and say
total energy is 4. The 19 arrangements are possible, so W = 19.
Statistical Entropy
At T = 0, all molecules are in lowest possible energy level. So W = 1.
Therefore, S = 0. Boltzmanns formula agrees with Third Law.
When T > 0, the molecules can occupy energy levels above the lowest
one, and many different arrangements of the molecules will correspond
to the same total energy. That is, when T > 0, W > 1, So S > 0.
Boltzmanns formula is consistent with the entropy of a substance
increasing with temperature.
Residual Entropy
Boltzmanns formula provides an explanation for the entropy of some
substances is greater than zero at T = 0. This contribution is called the
Residual entropy of a solid.
Example: We can estimate the value of residual entropy of CO molecules
at T =0 using Boltzmanns formula. Each CO molecule can lie in either of
two orientation. Then the total no. of ways of arranging N molecules is
(222)N times = 2N
Then, S = k ln 2N or S = N k ln 2. Sm = NAV k ln 2 = R ln2 = 5.8 JK-1mol-1
Or
TS 0
Gibbs Energy
Define the Gibbs (free) energy G as
G S
Extensive state function with units of energy. As just seen, at
constant T and p, G = T(S)tot and so for spontaneous
process at constant T and p, G < 0.
For infinitesimal change at given T and p, and no work other
than that of expansion/compression, dG 0
For a closed system at given T and p, with only pdV work,
G < 0 for a spontaneous process, and G is therefore
minimum at equilibrium for such a system
dG = SdT + Vdp
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Chemical Potential
In a homogeneous solution of say k components, one may
write any extensive property E as E = njj where j called
a partial molar property represents the contribution per mole
that species j makes to the property E in that solution at the
given T and p.
The partial molar Gibbs energy is of special significance, is
denoted by j, and called the chemical potential of the
species j in the given solution at the given T and p
For a pure substance, the chemical potential is just the
molar Gibbs energy, = G/n.
Phase Diagram
Map showing ranges of T
and p over which various
phases are stable.
Phase BoundariesMelting, Vaporization and
Boiling Curves
Triple Point, Critical Point
Phase Rule F = C P + 2