Thermodynamic parameters in a binary system

Previously, we considered one element only.

Now we consider interaction between two elements.

This is not straightforward since elements can interact differently and

thermodynamic parameters may change accordingly.

Let us consider a binary system with elements A and B

For our analysis, we consider XA mol of A and XB mol of B, so that

X A + XB =1

That means we consider total one mole of the system. That further means we
consider total number of atoms equal to the Avogadro number, No (= 6.023x1023),
where Xi= Ni/No. Ni is the number of atoms of element i.

Unlike single component system, where we determine the change in free energy
with temperature, in the binary case we shall find the change in free energy with the
change in composition at different constant temperature at a time.

Let us consider the free energy for one mole of

element A is GA and one mole of B is GB.

So before mixing when kept separately, XA mole of A

and XB mole of B will have the free energy of XAGA and
XBGB, respectively.

Total free energy before mixing G0 = X AG A + X B GB


After mixing there will be change in free energy.

Total free energy after mixing G = G0 + ∆Gmix

∆Gmix is the free energy change of the alloy because of mixing

∆Gmix = G − G0 = H − TS − (H 0 − TS 0 ) = (H − H 0 ) − T (S − S 0 )

∆Gmix = ∆H mix − T∆S mix

So, once we determine the change in free energy because of mixing, we can
determine the total free energy after mixing.

Let us first determine, the enthalpy change because of mixing ( ∆H mix ) and the
change in entropy because of mixing ( ∆S mix )

Note that system always tries to decrease enthalpy and increase entropy for
stability.
 The change in enthalpy because of mixing, DHmix

We take the following assumptions:

 The molar volume does not change because of mixing.

 Bond energies between the pure elements do not change with the change in composition
 We neglect the role of other energies.

After mixing, the system can have three different types of bonding, A-A, B-B and A-B

Enthalpy of mixing can be expressed as ∆H mix = N 0 ZX A X B ∆ε

N 0 is the Avogrado number, Z is the coordination number

1

The change in internal energy ∆ε = ε AB − (ε AA + ε BB )
2
ε AB is the bond energy between A and B
ε AA is the bond energy between A and A
ε BB is the bond energy between B and B

It can be written as ∆H mix = ξX A X B where ξ = N 0 Z∆ε

 There can be three situations:

Situation 1: Enthalpy of mixing is zero ∆H mix = ξX A X B = 0

1
That means ε AB = (ε AA + ε BB )
2

There will be no preference to choose neighbouring atoms. Atoms can sit
randomly at any lattice points .
Situation 2: Enthalpy of mixing is less than zero

∆H mix = ξX A X B < 0

1
That means ε AB < (ε AA + ε BB )
2

Because of transformation internal energy will decrease. That means

transformation is exothermic. Atoms will try to maximize A-B bonds.

Situation 3: Enthalpy of mixing is greater than zero

∆H mix = ξX A X B > 0

1
That means ε AB > (ε AA + ε BB )
2

Because of transformation internal energy will increase. That means

transformation is to be endothermic. Atoms will try to maximize A-A and B-B
bonds.
 Slope/maximum/minimum of the enthalpy of mixing curve

(
∆H mix = ξX A X B = ξ X B − X B2 )

d (∆H mix )
= ξ (1 − 2 X B )
dX B

d (∆H mix ) This implies XB= 0.5. That means maximum or

At maximum/minimum =0
dX B minimum will be at XB= 0.5

d (∆H mix ) lim That means the slope at the beginning has a
Further, at =ξ
dX B XB → 0 finite value of ξ
 The change in entropy because of mixing, DSmix

Since we are considering transformation at a particular temperature, the change

in entropy because of the change in temperature can be neglected.

We need to consider only the configurational entropy change. Configurational

entropy change comes from the possibilities of different ways of arrangement of
atoms

Following statistical thermodynamics the configurational entropy can be

expressed as

S = k ln w
(k is the Boltzmann constant and w is the measure of randomness)

∆S mix = S − S 0 = k ln w − k ln 1 = k ln w
since atoms at their pure state before mixing can be arranged in only one way

If we consider the random solid solution, then

(n A + n B )!
w= nA and nB are the number of atoms of A and B
n A !n B !
Following Stirling’s approximation

ln N!= N ln N − N
So ∆Smix can be written as

∆S mix = k ln w = k {[(n A + nB ) ln(n A + nB ) − (n A + nB )] − [n A ln n A − n A ] − [nB ln nB − nB ]}

 nA nA 
= −k n A ln + nB ln 
 n A + n B n A + n B

Number of atoms can be related to the mole fraction, X and the Avogadro number,
No following

nA = X A N0 nB = X B N 0
XA + XB =1 n A + nB = N 0

∆S mix = −kN 0 [ X A ln X A + X B ln X B ]
= − R[X A ln X A + X B ln X B ]

where, R is the gas constant

 Slope/maximum of the entropy of mixing curve
6

Entropy of mixing, ∆Smix

4

0
0.0 0.2 0.4 0.6 0.8 1.0
Composition, XB

d (∆S mix )  1 1  XB
= − R − ln(1 − X B ) − (1 − X B ) + ln X B + X B  = − R ln
dX B  (1 − X B ) XB  1− X B

d (∆S mix )
=0 at maximum, this corresponds to XB = 0.5
dX B

Further, the slope at XB →0 is infinite. That means the entropy change is very high
in a dilute solution

As mentioned earlier the total free energy after mixing can be written as

G = G0 + ∆Gmix
where

G0 = X A G A + X B G B

∆Gmix = ∆H mix − T∆S mix

∆H mix = ξX A X B

∆S mix = − R[ X A ln X A + X B ln X B ]

So ∆Gmix can be written as

∆Gmix = ξX A X B + RT [X A ln X A + X B ln X B ]

Following, total free energy of the system after mixing can be written as

G = X A G A + X B G B + ξX A X B + RT [X A ln X A + X B ln X B ]