Chapter 1

Thermodynamics of Solution

At any temperature T

Pure substance G(A) = Ga

Pure substance G(B) = Gb

When Above is mixed in Xa and Xb amount such that Xa+Xb = 1

G = H TS

If amount remain separated

Then DelG = XaGa + XbGb (Proportional Amount)

However, we form random solution and there is change in change in Entropy

Entropy of mixing = - R(XaLnX+XbLnXb)

Suppose there is no enthalpy change ( i,e DelH = 0 )

Mixing amount G =0 (-RT( XalnXa + XblnXb) )taking T = 298K , 25deg C

Therefore, entropy of mixing = +ve

And Gibbs energy change due to mixing is -ve

Del G = Proportional amount (G) + Mixing Amount(G)

= ( xaGa + XbGb ) + ( RT (XaLnXa + XbLnXb)

Suppose there is Excess Gibbs energy

Experimentally exces Gibbs Energy was found to be =AXaXb

Value of excess gibbs energy is associated with H change

Suppose enthalpy change is H = ZXaXb

Hence

G change = H ( Proportional amount (G) + Mixing Amount(G))

= H (( xaGa + XbGb ) + ( RT (XaLnXa + XbLnXb))

Ideal Solution Mixing - Plot ((((x*-4) +(1-x)*30))+ 8.314*8(x*ln x+(1-x)*ln(1-x))),x*-4+(1-x)*30

Regular solution : (( xaGa + XbGb ) + ( RT (XaLnXa + XbLnXb)) + ZXaXb

Hence for positive value of Z the curve can split as shown below. ( T = 8K)
Hence, for two component system , one phase will split into two phases at Lower temperature.

At higher temperature, this miscibility gap closes ( T = 40K )

This implies there exit a temperature at which this miscibility gap disappear
G change = F(x)

There is no miscibility if d2(F(x)/dx2 has same sign throughout composition . It is point where G
acquire maxima

Critical T , where d2(F(x)/dx2 = 0 is called temperature where miscibility gap disappear

 Chapter 2

From the above discussion, it is obvious that a solid phase will split into two distinct composition
phase at lower temperature, provided heat of mixing is positive.

Above and below Critical temperature, the component exist as single phase or more.

L1(s) --- L2(s)+L3(s)

Note here , there is no liquid to solid transformation, it just same phase split into same phase with
distinct composition.

Note : In gaseous Phase , every thing can be mixed in any proportion

In Liquid Phase , solute and solvent solubility decrease, and there is temperature below
which they may not be soluble.

In solid Phase, solubility is limited.

Gibbs Phase Rule

Chemical potential is driving force and when this driving force is equal then component exists in
different phase at same temp
 Chapter 3

Activities, Gibbs free energy and Multicomponent system Algebra

We know that G ( T,P,n1,n2,n3..)

delG = (dG/dT)*DT + (dG/dP)*DP+(dG/dn1)*Dn1+ .

At constant temperature and Pressure

delG = (dG/dn)*Dn

The term dG/dn1 is defined as chemical potential of component 1 - 1

Hence DG = 1dn1 + 2dn2 ndn

This mean at constant Temperature and Pressure

G = u1n1 + u2n2 utnt

Now Differentiating G

dG = (u1dn1 + u2dn2 + u3dn3 ..utdnt) + (n1du1 + n2du2 + n3du3 ..)

Part A + Part B

At constant P,T

dG = part A

Part B = 0
nidui = 0 ( This is know as Gibbs Duheum Equation)

Let N = n1+n2+nt
X1 =n1/N
Xi = 1

Gibbs Duheum Equation = uiXi = 0

And G = uini , Chemical potential is nothing but molar gibbs energy

Gibbs Duheum Equation for Binary System

X1dU1 + X2dU2 = 0

X1+X2 = 1

dx1+dx2 = 0

dX1 = - dX2
x1dU1/(dx1) + x2dU2/(dx2) = 0

x1dU1/dx1 = x2dU2/dx2

Regular solution : (( xaGa + XbGb ) + ( RT (XaLnXa + XbLnXb)) + ZXaXb , Xa+Xb=1

Comparing it with aXa+bXb

We get

a = Ga+ RTlnXa + Z(Xb)^2 , = Ga+ RTlnXa + Z(1-Xa)^2

b = Gb + RTlnXb + Z(Xa)^2 , = Gb + RTlnXb + Z(1-Xb)^2
Similarly

a = Ga + RTlnXa - xa*( d(excessG )/dx )

b = Gb + RTlnXb +(1-x) *( d(excessG )/dx )
Chemical dependence of partial Pressure

dG = - Sdt + VdP+dni

Now, (dG/dT)T,x0 = V and (dG/dn)P,T =

Now ,

dG = nd

dG/dP = N d/dP

V /N = d/dP

= o + RT ln( P /Po) PV = nRT

Clausis Clepyron Relationship

Phase transformation of a pure substance

Atmospheric pressure is 5.2 bar.

At critical point, there is no distinction between liquid and gas phase.

Prediction of phase which is more stable under particular (P,T)

Blue line in Graphite , Red is diamond.

There exist a pressure above which diamond is more stable.
dG/dP = V
 Clausis clepyron

If two phase co exists ..over (P,T)

Then Ga = Gb
From it follows ..
-S(a)dt+V(a)dp+dn = S(b)dt+V(b)dp+dn
Na = Nb
dP/dT = (Sb -Sa)/(Vb-Va)

This relationship is called clausis clepyron equation

For Phase transformation: ds = dq/T = Latent heat of fusion ( L)
dP/dT = L/T(dV)
dv = nRT/P
dP/dT = LP/RT^2
dP/P = L/(RT^2) dT