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Standard Reaction Entropies

rS = iSim (products) iSim (reactants)


For 2 H2(g) + O2(g) 2 H2O(l) at 298 K
rS= 2 Sm(H2O(l)) ( 2 Sm(H2(g)) + Sm(O2(g)) )

= 327 J/K. ( Why negative?)


However, the reaction is explosively spontaneous.

Need to consider the total entropy change ie., of the system


and the surroundings. For this reaction, rH298 = 572 kJ, so
that
(S)surr = 572x103 / 298 = 1.92x103 J/K
and (S)tot = 1.59x103 J/K
indicating that the reaction is spontaneous.
Note: This reaction is also spontaneous in an isolated
container (Explain).

Statistical Entropy
Description of entropy from microscopic point of view. The
arrangements of molecules over the available energy levels

determines the value of the statistical entropy.


Boltzmann Eqn.:

S = k lnW

k = Boltzmanns constant = 1.38110-23 JK-1

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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.

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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.

When container expands, the levels occupied by the molecules get


closer together, and the number of ways of arranging the molecules for
a given total energy increases. So W increases and S increases.
Boltzmanns formula is consistent with the entropy of a gas increasing as
the volume it occupies is increased.
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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

Sm(0) = 5.8 JK-1mol-1

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Spontaneity and Equilibrium


The criterion for the spontaneity of a process in an
isolated system is
dS > 0
Isolated system spontaneously moves to states of
ever greater entropy.

The equilibrium state of an isolated system is


therefore characterized by maximum entropy for
the given internal energy U and volume V.
What about systems other than isolated?
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Spontaneity and Equilibrium


In the chemistry laboratory, one is most commonly
concerned with systems at constant T and p. At constant
pressure, q = = qsurr so that
(S)tot = S ()/T 0
(> for irreversible and = for reversible process).

Or

TS 0

If T is constant, this may be written as


(H TS) 0
(< for irreversible and = for reversible process)
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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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Spontaneity and Equilibrium

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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.

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Equilibrium and Spontaneity Criteria


In terms of intensive properties, the criteria of equilibrium
are:
Thermal equilibrium: Uniformity of temperature T
Heat transfer occurs spontaneously in the direction of
decreasing temperature
Mechanical equilibrium: Uniformity of pressure
Displacement of wall occurs spontaneously in the direction
of decreasing pressure
Material equilibrium (transfer of substance j): Uniformity of
the chemical potential of j
Net transfer of substance j occurs in the direction of
decreasing chemical potential j
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Thermodynamics of Phase Equilibrium


At given T and p, the stable phase of a pure substance is
that of minimum molar Gibbs energy Gm.
At 1 atm, ice is the stable phase of water below 0C, while
above 0C but below 100C, liquid water is the stable
phase, and above 100C, steam is the stable phase.
At this pressure, ice and liquid water have the same value
of Gm at 0C, and coexist in equilibrium, while at 100C,
liquid water and steam have the same Gm, and coexist in
equilibrium.
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Variation of G with p and T


dG = dU + d(pV) d(TS)
and with dU = TdS pdV one has
dG = SdT + Vdp
It follows that
(Gm/p)T = Vm
and
(Gm/T)p = Sm

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Variation of G with p at constant T


(Gm/p)T = Vm
Vapour stable at low
pressures, liquid at
intermediate pressures,
and solid at high
pressures.
Transition
when
molar
Gibbs
energies are equal

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Variation of G with T at constant p


(Gm/T)p = Sm
Solid stable at low
temperatures, liquid at
intermediate temperatures
and vapour at high
temperatures. Transition
when molar Gibbs energies
are equal

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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

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Enthalpy and Entropy changes


Heat transfer accompanying a phase change at constant p is
H. States must be completely specified.
Energy supplied as heat at constant pressure for the fusion
of 1 mol of substance under standard condition i.e. pure solid
substance at 1 bar changing to pure liquid at 1 bar, is the
standard enthalpy of fusion fus
Similarly , vap, the standard enthalpy of vaporization
sub = fus + vap (Hess Law).
If the word standard is removed, then it refers to the value at
the pressure (and T) at which there is equilibrium.
Since the transformations are at equilibrium, and hence
reversible, transS = trans/T where T refers to the equilibrium
temperature at the given p.
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