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New Phase or
One or more
mixture of
Phases in an
new phases
alloy
G = H - TS
H = E + PV
Internal Energy: (Kinetic energy) + (Potential Energy)
volume
Change Change in
of the internal
H = E + PV system energy
PV E
At constant volume : W = P dV = 0
dE = q – W =q , Increase or decrease in E => Heat absorbed or released
At constant pressure: dH = q , Increase in enthalpy => Heat absorbed
Decrease in enthalpy => Heat released
For condensed phases: PV <<<< E => H ~ E
Entropy: Measure of randomness of the system
volume.
Binary Solutions
• In single component systems all phases
have the same compositions
Mixing
• After step 1 the free energy of the system is
given by; G1 = XAGA+XBGB Jmol-1
∆Η mix is the heat absorbed or evolved during step 2, i.e it is the heat of
solution , and ignoring volume changes during the process, it represents
only the difference in internal energy (E) before and after mixing.
Ideal Solutions
∆Η mix = 0 =0
In statistical thermodynamics,
S = k ln ω
(2)
S
S th
S config
• In case of thermal entropy, ω is the number of
ways in which the thermal energy of the solid
can be divided among the atoms or
The total numbers of ways in which vibrations
can be set up in the solid
• In solutions, additional randomness exist due to
the different ways in which the atoms can be
arranged leading to the configurational entropy
• If there is no volume change or heat exchange
during mixing then the only contribution to ∆
Smix is the change in configurational entropy
• If there is no volume change or heat
change during mixing then the only
contribution to ∆Smix is the change in
configurational entropy
• Before mixing , A & B atoms are held
separately in the system and there is only
one distinguishable way in which the
atoms can be arranged
S1= k ln 1 = 0
∆Smix = S2
• Assuming that A & B mix to form a
substitutional solid solution
• All configurations of A & B atoms are equally
probable
• The number of distinguishable ways of
arranging the atoms on atom sites is
ω = (NA+ NB) ! / NA ! NB ! (3)
(
Ln N ! = N ln N - N 1
)
Na k = R (
2
∆Smix = - R (X A ln X A + X B ln X B)
GA G2
G
A
Chemical Potential
• In alloys it is of interest to know how the free
energy of a given phase will change when atoms
are added or removed
• If a small quantity of A, dnA mol, is added to a
large amount of a phase at constant T & P , the
size of the system will be increase by dnA
• Therefore, the total free energy of the system will
also increase by a small amount dG’
• If dnA is a small enough dG’ will be proportional to
the amount of A added
dG’ = µ A dnA ( T, P , nB constant )
• The proportionality constant is called the
partial molar free energy of A or alternatively
the chemical potential of A in the phase.
∀ µ A depends on the composition of the , and
therefore dnA must be so small that the
composition is not significantly altered
µ A = (δG’ / δnA) T,P,n(B)
∆ Hmix - T ∆ Smix
• For exothermic solutions ∆Η mix < 0 and
mixing results in a free energy decrease at
all temperatures
• For ∆Η mix > 0 , the situation is more
complecated,
At high temperature: T∆Smix > ∆Η mix
For all compositions and free energy curve
has a positive curvature at all points.
At low temperature: T∆Smix < ∆Η mix
Free energy develops a negative curvature
in the middle
>
Pringles
• Differentiating; ∆Smix = - R (X A ln X A + X B ln X B)
• As X A or X B 0 the T∆Smix curve becomes
vertical whereas the slope of ∆Hmix curve tends to
a finitevalue Ω, this means that, except at absolute
zero, ∆Gmix always decreases on addition of a
small amount of solute
• The actual free energy of the alloy depends on the
values chosen for G A & G A and is given by;
G = XAGA+XBGB +Ω X A X B + RT(X A ln X A + X B ln X B)
Using, X A X B = X A X 2B + X 2A X B
G = XAGA+XBGB + Ω X A X B + RT(X A ln X A + X B ln X B)
G= µ A XA + µ B XB
2
ln (a A / X A ) = Ω (1 - X A )2/ RT
ln (a B / X B ) = Ω (1 - X B )2/ RT
Assuming A & B have the same crystal
structure, the relationship between a
and X can be represented as shown in
fig.
For an ideal solution a A = X A
If ∆Hmix< 0 , activity of the components
in the solution will be less in an ideal
solution (line 2)
If ∆Hmix> 0, vice versa
• The ratio (a A / X A ) is usually referred
to as , γ Α the activity coefficient of A,
that is
γ Α = (a A / X A )
• For the dilute solution of B in A
• Letting in above equation X B 0
γ Α = (a A / X A ) ~ 1 (Raoult’s law)
γ Β = (a B / X B) ~ constant (Henry’s law)
• The activity of a component is just
another means of describing the
state of the component in a
solution