Thermodynamics of Materials-

MTEN 204/604
Department of Materials Science and Engineering
University of Ghana
Lecturer: Dr. Emmanuel Nyankson
Email: loyankemon@yahoo.com, enyankson@ug.edu.gh
Behavior of Solutions: Raoult’s and Henry’s Law
A dynamic equilibrium is
established where the rate of
evaporation (re)of liquid A is
equal to the rate of condensation
(rc) of vapor A.
𝑟𝑐(𝐴) = 𝑘𝑝𝐴𝑜
And
𝑟𝑒(𝐴) = 𝑘𝑝𝐴𝑜
Similar expressions can be
Filled with Liquid A evaporates until
Empty Vessel the pressure in the vessel written for liquid B
pure Liquid A
at T is reaches the saturated 𝑟𝑐(𝐵) = 𝑘 𝐼 𝑝𝐵𝑜
vapor pressure of liquid
A (𝑃𝐴𝑜 )
𝑟𝑒(𝐵) = 𝑘 𝐼 𝑝𝐵𝑜
 Behavior of Solutions: Raoult’s and Henry’s Law
➢ A can only evaporate from sites occupied by A
➢ The rate of evaporation of A is decreased by a
factor XB.

𝑟𝑒(𝐴) 𝑋𝐴 = 𝑘𝑝𝐴
Similarly for liquid B containing a small amount of A
𝑟𝑒(𝐵) 𝑋𝐵 = 𝑘𝑝𝐵
It can be deduced that
Addition of
small amount Both Liquids A and B 𝑝𝐴 = 𝑋𝐴 𝑝𝐴𝑜
of Liquid B to evaporates RAOULT’S LAW
liquid A
𝑝𝐵 = 𝑋𝐵 𝑝𝐵𝑜
 Behavior of Solutions: Raoult’s and Henry’s Law
𝑝𝐴 = 𝑋𝐴 𝑝𝐴𝑜
𝑝𝐵 = 𝑋𝐵 𝑝𝐵𝑜
The Raoult’s law states that the vapor pressure exerted by a component i in a
solution is equal to the product of the mole fraction of i in the solution and the
saturated vapor pressure of pure liquid I at the temperature of the solution.

➢Derivation of the Raoult’s law is based on the assumption that the intrinsic
rates of evaporation of A and B are independent of the composition of the
solution.
➢This implies that that magnitude of the A-A, A-B, and B-B bond energies in
the solution are identical.
Behavior of Solutions: Raoult’s and Henry’s Law

𝑷𝑶
𝑩 The components of
a solution which
obeys the Raoult’s
𝑷𝑶
𝑨
Law are said to
Vapor Pressure

exhibits Raoultian
behavior

A XB B
 Behavior of Solutions: Raoult’s and Henry’s Law
Consider the case where A-B is more negative (Stronger) than A-A and A-B.
Also consider a solution of A in B which is dilute that every A atom on the
surface is surrounded by only B atoms.
➢For such cases, the rate of evaporation of A is decreased.
𝐼
𝑟𝑒(𝐴) 𝑋𝐴 = 𝑘𝑝𝐴
It can be deduced that

𝐼
𝑟𝑒(𝐴)
𝑝𝐴 = 𝑋𝐴 𝑝𝐴𝑂
𝑟𝑒(𝐴)
 Behavior of Solutions: Raoult’s and Henry’s Law

𝑝𝐴 = 𝑘𝐴 𝑋𝐴
a similar consideration for a dilute solutions of B in A gives

𝑝𝐵 = 𝑘𝐵 𝑋𝐵
These expressions are obeyed over an initial range of concentration.
𝑝𝐴 = 𝑘𝐴 𝑋𝐴
HENRY’S LAW
𝑝𝐵 = 𝑘𝐵 𝑋𝐵
In the range of composition in which Henry’s law is obeyed, the solutes are said
to exhibits Henrian behavior
The Thermodynamic Activity of a Component
Solution
 The Thermodynamic Activity of a Component
Solution
The thermodynamic activity of a component I is given as
𝑓𝑖
𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑖 = 𝑎𝑖 =
𝑓𝑖𝑜
In a condensed solution, 𝑓𝑖 is the fugacity of the component i in the solution at T
and 𝑓𝑖𝑜 is the fugacity of pure I (the standard state) at T.
➢If the vapor in equilibrium with the condensed solution is ideal, then 𝑓𝑖 = 𝑝𝑖
𝑝𝑖
Then 𝑎𝑖 =
𝑝𝑖𝑜
➢If the component exhibits Raoultian behavior, 𝑎𝑖 = 𝑋𝑖
➢If the component exhibits Henrian behavior, 𝑎𝑖 = 𝑘𝑖 𝑋𝑖
 Partial Molar Properties
Solution properties can be calculated from partial properties

• The total thermodynamics properties of a homogenous phase are functions of

T, P and the number of moles of the individual species which comprise the
phase:
𝑛𝑀 = 𝑀(𝑇, 𝑃, 𝑛1 , 𝑛2 … … . . 𝑛𝑖 … . . )

𝜕(𝑛𝑀) 𝜕(𝑛𝑀) 𝜕(𝑛𝑀)

𝑑 𝑛𝑀 = 𝑑𝑃 + 𝑑𝑇 + σ𝑖 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗
 Partial Molar Properties
Since the first two variables are evaluated at constant n
𝜕(𝑀) 𝜕(𝑀)
𝑑 𝑛𝑀 = 𝑛 𝑑𝑃 + 𝑛 𝑑𝑇 + σ𝑖 𝑀𝑖 𝑑𝑛𝑖 Summability Relations
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥

With 𝑛𝑖 = 𝑥𝑖 𝑛, 𝑀 = ෍ 𝑥𝑖 𝑀𝑖
𝑑𝑛𝑖 = 𝑥𝑖 𝑑𝑛𝑖 + 𝑛𝑖 𝑑𝑥𝑖 𝑖

And
𝑑 𝑛𝑀 = 𝑛𝑑𝑀 + 𝑀𝑑𝑛 𝑛𝑀 = ෍ 𝑛𝑖 𝑀𝑖
𝑖
It can be deduced from the above equations that:
𝜕𝑀 𝜕𝑀
𝑑𝑀 = 𝑑𝑃 + 𝑑𝑇 + σ𝑖 𝑀𝑖 𝑑𝑥𝑖 and 𝑀 = σ𝑖 𝑥𝑖 𝑀𝑖
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
 The Gibbs-Duhem Equation
Generally the Gibbs Duhem Equation is stated as;

෍ 𝑛𝑖 𝑑𝑄ത𝑖 = 0, 𝑜𝑟 ෍ 𝑋𝑖 𝑑𝑄ത𝑖 = 0, 𝑤ℎ𝑒𝑟𝑒 𝑄 𝑖𝑠 𝑎𝑛 𝑒𝑥𝑡𝑒𝑛𝑠𝑖𝑣𝑒 𝑚𝑜𝑙𝑎𝑟 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦

𝑖 𝑖

The Gibbs-Duhem equation for the partial molar Gibbs free energy of a binary
solution is
𝑋1 𝑑∆𝐺1ҧ + 𝑋2 𝑑∆𝐺ҧ2 = 0
 The Gibbs Free Energy of Formation of a Solution
For a binary solution at a fixed T and P, The molar Gibbs Free energy can be expressed
as
𝐺 𝐼 = 𝑛𝐴 𝐺𝐴ҧ + 𝑛𝐵 𝐺ҧ𝐵
Where 𝐺𝐴ҧ 𝑎𝑛𝑑 𝐺ҧ𝐵 are the partial molar Gibbs free energies of A and B, respectively.
This can be written as
𝐺 = 𝑋𝐴 𝐺𝐴ҧ + 𝑋𝐵 𝐺ҧ𝐵
It can further be deduced that
𝑑𝐺 𝑑𝐺
ҧ
𝐺𝐴 = 𝐺 + 𝑋𝐵 ҧ
𝑎𝑛𝑑 𝐺𝐵 = 𝐺 + 𝑋𝐴
𝑑𝑋𝐴 𝑑𝑋𝐵
These expressions relates the dependence on composition of the partial molar Gibbs
free energies of the components of a binary solution and the molar Gibbs free energy
of the solution.
 The Gibbs Free Energy of Formation of a Solution

Compute the partial molar enthalpies of the two components in a binary solution
with an enthalpy of mixing (molar enthalpy of the solution) given by

∆𝐻𝑚𝑖𝑥 = ∆𝐻 = 𝑎𝑋1 𝑋2
The change in G Due to the Formation of a Solution
A pure component i occurring in a condensed state at T, exerts an equilibrium
vapor pressure 𝑝𝑖𝑜 , and when occurring in a condensed solution at T, it exerts a
lower equilibrium pressure 𝑝𝑖 , consider the ff isothermal three-step process:
a. The evaporation of 1 mole of pure condensed i to vapor i at the pressure 𝑝𝑖𝑜
b. A decrease in the pressure of 1 mole of vapor I from 𝑝𝑖𝑜 to 𝑝𝑖
c. The condensation of 1 mole of vapor I from the pressure 𝑝𝑖 to the condensed
solution.
The processes in steps a and c are conducted in equilibrium so the change in
Gibbs energy is zero.
𝑝𝑖
∆𝐺(𝑏) = 𝑅𝑇𝑙𝑛 𝑜
𝑝𝑖
The change in G Due to the Formation of a Solution

The molar Gibbs free energy of the solution of i is

∆𝐺(𝑏) = 𝐺𝑖 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 𝐺𝑖 𝑃𝑢𝑟𝑒 = 𝐺ҧ𝑖 − 𝐺𝑖𝑜 = ∆𝐺ҧ𝑖𝑀 = 𝑅𝑇𝑙𝑛𝑎𝑖
∆𝐺ҧ𝑖𝑀 is the partial molar Gibbs free energy of 1 mole of i in solution. If 𝑛𝐴
moles of A and 𝑛𝐵 moles of B are mixed to form a solution at constant T and P,
The Gibbs free energy before mixing = 𝑛𝐴 𝐺𝐴𝑂 + 𝑛𝐵 𝐺𝐵𝑂
The Gibbs free energy after mixing =𝑛𝐴 𝐺𝐴ҧ + 𝑛𝐵 𝐺ҧ𝐵
The change in the Gibbs free energy caused by the mixing process, ∆𝐺 𝐼𝑀 ,
referred to as the integral Gibbs free energy of mixing is the difference between
these quantities, that is
∆𝐺 𝐼𝑀 = 𝑛𝐴 𝐺𝐴ҧ − 𝐺𝐴𝑂 + 𝑛𝐵 (𝐺ҧ𝐵 − 𝐺𝐵𝑂 )
The change in G Due to the Formation of a Solution

∆𝐺 𝐼𝑀 = 𝑛𝐴 𝐺𝐴ҧ − 𝐺𝐴𝑂 + 𝑛𝐵 (𝐺ҧ𝐵 − 𝐺𝐵𝑂 )

It can be deduced that,

∆𝐺 𝐼𝑀 = 𝑛𝐴 ∆𝐺𝐴ҧ 𝑀 + 𝑛𝐵 ∆𝐺ҧ𝐵𝑀 OR ∆𝐺 𝐼𝑀 = 𝑅𝑇(𝑛𝐴 𝑙𝑛𝑎𝐴 + 𝑛𝐵 𝑙𝑛𝑎𝐵 )

For 1 mole of a solution

∆𝐺 𝑀 = 𝑋𝐴 ∆𝐺𝐴ҧ 𝑀 + 𝑋𝐵 ∆𝐺ҧ𝐵𝑀 OR ∆𝐺 𝑀 = 𝑅𝑇(𝑋𝐴 𝑙𝑛𝑎𝐴 + 𝑋𝐵 𝑙𝑛𝑎𝐵 )

The variation of ∆𝐺 𝑀 with composition is shown in the lecture material

 Graphical Determination of Partial Molar Properties
In terms of solution properties;
. 𝑑𝐺 𝑑𝐺
𝐺𝐴ҧ = 𝐺 + 𝑋𝐵 𝑎𝑛𝑑 𝐺ҧ𝐵 = 𝐺 + 𝑋𝐴
𝑑𝑋𝐴 𝑑𝑋𝐵
Can be written as
𝑀 𝑀
XA=XB 𝑑∆𝐺 𝑑∆𝐺
∆𝐺𝐴ҧ 𝑀 = ∆𝐺 𝑀 + 𝑋𝐵 𝑎𝑛𝑑 ∆𝐺ҧ𝐵𝑀 = ∆𝐺 𝑀 + 𝑋𝐴
o p 𝑑𝑋𝐴 𝑑𝑋𝐵

Consider the composition XA (point P on the figure). At XA

ΔGM ∆𝐺 𝑀 = 𝑝𝑞 𝑎𝑛𝑑 𝑋𝐵 = 𝑟𝑞
∆𝐺ҧ𝐵𝑀 𝑑∆𝐺 𝑀
= 𝑡ℎ𝑒 𝑠𝑙𝑜𝑝𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑎𝑛𝑔𝑒𝑛𝑡 𝑡𝑜 𝑡ℎ𝑒 ∆𝐺 𝑀 𝑐𝑢𝑟𝑣𝑒 𝑎𝑡 𝑋𝐴
𝑑𝑋𝐴
∆𝐺𝐴ҧ 𝑀
𝑑∆𝐺 𝑀 𝑟𝑠
=
r 𝑑𝑋𝐴 𝑟𝑞
q It can be deduced that
s ∆𝐺𝐴ҧ 𝑀 = 𝑜𝑠 = 𝑡ℎ𝑒 𝑡𝑎𝑛𝑔𝑒𝑛𝑡𝑖𝑎𝑙 𝑖𝑛𝑡𝑒𝑟𝑐𝑐𝑒𝑝𝑡 𝑎𝑡 𝑋𝐴 = 1
Similarly at composition XA
XB B ∆𝐺ҧ𝐵𝑀 = 𝑡ℎ𝑒 𝑡𝑎𝑛𝑔𝑒𝑛𝑡𝑖𝑎𝑙 𝑖𝑛𝑡𝑒𝑟𝑐𝑐𝑒𝑝𝑡 𝑎𝑡 𝑋𝐵 = 1
A
The change in G Due to the Formation of a Solution

Given the integral heats of mixing (∆𝐻 𝐽Τ𝑚𝑜𝑙) of Zn with its mole fraction, in a
Zn-Cd alloy, calculate the partial molar heat of mixing of Zn and Cd containing
0.6 atom fraction of Zn at 700 ℃.
𝑿𝒁𝒏 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

∆𝐻𝑀 753 1326 1728 1958 2054 2000 1774 1377 787
 Evaluation of the PMPs of One Component from
Measured Values of PMPs of the Other
➢ The partial molar property of one component can be determined from the partial
molar property of another component.

The Gibbs-Duhem equation for the partial molar Gibbs free energy of a binary solution
is
𝑋1 𝑑∆𝐺1ҧ + 𝑋2 𝑑∆𝐺ҧ2 = 0
Rearrange to solve 𝑑∆𝐺1ҧ
𝑋2
𝑑∆𝐺1 = − 𝑑∆𝐺ҧ2
ҧ
𝑋1
𝑋2
𝑋2
∆𝐺1ҧ = − න 𝑑∆𝐺ҧ2
𝑋2 =0 𝑋1
 Evaluation of the PMPs of One Component from
Measured Values of PMPs of the Other
𝑋2
𝑋2
∆𝐺1ҧ = − න 𝑑∆𝐺ҧ2
𝑋2 =0 𝑋1
We can write
𝑑∆𝐺ҧ2
𝑑∆𝐺ҧ2 = 𝑑𝑋2
𝑑𝑋2
The integral form of the Gibbs-Duhem Equation above can be written as

𝑋2
𝑋2 𝑑∆𝐺ҧ2
∆𝐺1ҧ = − න 𝑑𝑋2
𝑋2 =0 𝑋1 𝑑𝑋2
 Properties of Raoultian Ideal Solutions
The components of a Raoultian ideal solution obey the relation:

𝑎𝑖 = 𝑋𝑖 , ℎ𝑒𝑛𝑐𝑒 𝑓𝑜𝑟 𝑎 𝑏𝑖𝑛𝑎𝑟𝑦 𝐴 − 𝐵 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

∆𝐺 𝑀 = 𝑅𝑇(𝑋𝐴 𝑙𝑛𝑎𝐴 + 𝑋𝐵 𝑙𝑛𝑎𝐵 ) can be written as

∆𝐺𝑀,𝑖𝑑 = 𝑅𝑇 𝑋𝐴 𝑙𝑛𝑋𝐴 + 𝑋𝐵 𝑙𝑛𝑋𝐵

With
∆𝐺𝐴ҧ 𝑀,𝑖𝑑 = 𝑅𝑇𝑙𝑛𝑋𝐴 𝑎𝑛𝑑 ഥ𝐺𝐵𝑀,𝑖𝑑 = 𝑅𝑇𝑙𝑛𝑋𝐵
 Properties of Raoultian Ideal Solutions
From 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + σ 𝜇𝑖 𝑑𝑛𝑖
For specie i occurring in solution

𝜕𝐺ഥ𝑖
= 𝑉ത𝑖
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝
And for Pure i,

𝜕𝐺𝑖𝑜
= 𝑉𝑖𝑜
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝
Change in Volume Accompanying the Formation of
an Ideal Solution
𝜕𝐺ഥ𝑖 𝜕𝐺𝑖𝑜
= 𝑉ത𝑖 and = 𝑉𝑖𝑜
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝

Subtracting the above equations

𝜕 𝐺ҧ𝑖 − 𝐺𝑖𝑜
= 𝑉ത𝑖 − 𝑉𝑖𝑜
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝

𝜕∆𝐺ҧ𝑖𝑀
= ∆𝑉ത𝑖𝑀
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝
Change in Volume Accompanying the Formation of
an Ideal Solution

𝜕∆𝐺ҧ𝑖𝑀
= ∆𝑉ത𝑖𝑀
𝜕𝑃 𝑇,𝐶𝑜𝑚𝑝
In an ideal solution ∆𝐺ҧ𝑖𝑀,𝑖𝑑 = 𝑅𝑇 ln 𝑋𝑖 , 𝑋𝑖 𝑖𝑠 𝑛𝑜𝑡 𝑎 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑃
Hence:
∆𝑉ത𝑖𝑀,𝑖𝑑 = 0
The change in volume due to mixing ∆𝑉 𝐼𝑀 is the difference between the
volumes of the components in the solution and the volume of the pure
components.
Change in Volume Accompanying the Formation of
an Ideal Solution
The change in volume due to mixing ∆𝑉 𝐼𝑀 is the difference between the
volumes of the components in the solution and the volume of the pure
components.
That is for a binary A-B solution containing nA moles of A and nB moles of B
∆𝑉 𝐼𝑀 = 𝑛𝐴 𝑉ത𝐴 + 𝑛𝐵 𝑉ത𝐵 − 𝑛𝐴 𝑉𝐴𝑂 + 𝑛𝐵 𝑉𝐵𝑂
= 𝑛𝐴 𝑉ത𝐴 − 𝑉𝐴𝑂 + 𝑛𝐵 𝑉ത𝐵 − 𝑉𝐵𝑂
= 𝑛𝐴 ∆𝑉ത𝐴𝑀 + 𝑛𝐵 ∆𝑉ത𝐵𝑀
For an ideal gas, ∆𝑉ത𝑖𝑀,𝑖𝑑 = 0, and thus it is seen that the change in volume
accompanying an ideal gas solution is zero, that is

∆𝑉𝑀,𝑖𝑑 = 0
 Heat of Formation of an Ideal Solution
The heat of formation of a solution (or the heat of mixing of the components) is
the difference between the enthalpies of the components in the solution and the
enthalpies of the pure components before mixing.
Thus for nA moles of A and nB moles of B;
∆𝐻 𝐼𝑀 = 𝑛𝐴 𝐻 ഥ𝐴 + 𝑛𝐵 𝐻𝐵 − 𝑛𝐴 𝐻𝐴𝑂 + 𝑛𝐵 𝐻𝐵𝑂
= 𝑛𝐴 𝐻 ഥ𝐴 − 𝐻𝐴𝑂 + 𝑛𝐵 𝐻 ഥ𝐵 − 𝐻𝐵𝑂
= 𝑛𝐴 ∆𝐻 ഥ𝐴𝑀 + 𝑛𝐵 ∆𝐻ഥ𝐵𝑀
For an ideal gas, ∆𝐻 ഥ𝑖𝑀,𝑖𝑑 = 0, and thus it is seen that the heat of formation of an
ideal gas solution is zero, that is
Starting from first principle show that
∆𝐻𝑀,𝑖𝑑 = 0
∆𝐻𝑀,𝑖𝑑 = 0
 Entropy of Formation of an Ideal Solution
From 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + σ 𝜇𝑖 𝑑𝑛𝑖 , at constant T and composition;
𝜕𝐺
= −𝑆
𝜕𝑇 𝑃,𝐶𝑜𝑚𝑝
For the formation of a solution
𝜕∆𝐺 𝑀
= −∆𝑆 𝑀
𝜕𝑇 ∆𝑆𝑀,𝑖𝑑 is independent
𝑃,𝐶𝑜𝑚𝑝
of temperature
For an ideal solution
∆𝐺𝑀,𝑖𝑑 = 𝑅𝑇 𝑋𝐴 𝑙𝑛𝑋𝐴 + 𝑋𝐵 𝑙𝑛𝑋𝐵
Hence;
𝜕∆𝐺 𝑀,𝑖𝑑
∆𝑆𝑀,𝑖𝑑 = − = −𝑅 𝑋𝐴 𝑙𝑛𝑋𝐴 + 𝑋𝐵 𝑙𝑛𝑋𝐵
𝜕𝑇 𝑃,𝐶𝑜𝑚𝑝
 Entropy of Formation of an Ideal Solution
The variation of ∆𝑆𝑀,𝑖𝑑 with composition is shown in the lecture notes provided.
∆𝑆 𝑀 = 𝑋𝐴 ∆𝑆𝐴ҧ 𝑀 + 𝑋𝐵 ∆𝑆𝐵ҧ 𝑀
In an ideal solution
∆𝑆𝐴ҧ 𝑀,𝑖𝑑 = −𝑅𝑙𝑛𝑋𝐴 𝑎𝑛𝑑 ∆𝑆𝐵ҧ 𝑀,𝑖𝑑 = −𝑅𝑙𝑛𝑋𝐵
For any solution
∆𝐺 𝑀 = ∆𝐻 𝑀 − 𝑇∆𝑆 𝑀
For an ideal solution, ∆𝐻𝑀,𝑖𝑑 = 0, hence

∆𝐺𝑀,𝑖𝑑 = −𝑇∆𝑆𝑀,𝑖𝑑
 Nonideal Solution
A nonideal solution is one in which the activities of the components are not
equal to their mole fractions.
The ratio of the activity of the component to its mole fraction is the activity
coefficient.
For component i,
𝑎𝑖
𝛾𝑖 =
𝑋𝑖

𝛾𝑖 = 1 → 𝑖𝑑𝑒𝑎𝑙 𝑅𝑎𝑜𝑢𝑙𝑡𝑖𝑎𝑛 𝑏𝑒ℎ𝑎𝑣𝑖𝑜𝑟

𝛾𝑖 > 1 → 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑑𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑅𝑎𝑜𝑢𝑙𝑡𝑖𝑎𝑛 𝑏𝑒ℎ𝑎𝑣𝑖𝑜𝑟
𝛾𝑖 < 1 → 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑑𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑅𝑎𝑜𝑢𝑙𝑡𝑠 𝑏𝑒ℎ𝑎𝑣𝑖𝑜𝑟
 Nonideal Solution
𝑎𝑖
with 𝛾𝑖 = ,
𝑋𝑖
∆𝐺ҧ𝑖𝑀 = 𝑅𝑇𝑙𝑛𝑎𝑖 = 𝑅𝑇 𝑙𝑛𝛾𝑖 + 𝑙𝑛𝑋𝑖

𝛾𝑖 < 1

𝜸𝒊 > 𝟏
 Nonideal Solution-Application of Gibbs Duhem
Relation to the Determination of Activity
σ𝑖 𝑋𝑖 𝑑𝑄𝑖 for binary solution, 𝑋𝐴 𝑑∆𝐺𝐴ҧ 𝑀 + 𝑋𝐵 𝑑∆𝐺ҧ𝐵𝑀 = 0

∆𝐺ҧ𝑖𝑀 = 𝑅𝑇𝑙𝑛𝑎𝑖 , then 𝑋𝐴 𝑑𝑙𝑛𝑎𝐴 + 𝑋𝐵 𝑑𝑙𝑛𝑎𝐵 = 0

It can be deduced that

𝑙𝑜𝑔𝑎𝐵 𝑎𝑡 𝑋𝐴 =𝑋𝐴
𝑙𝑜𝑔𝑎𝐴 𝑎𝑡 𝑋𝐴 = − න 𝑋𝐵 Τ𝑋𝐴 𝑑𝑙𝑜𝑔𝑎𝐵
𝑙𝑜𝑔𝑎𝐵 𝑎𝑡 𝑋𝐴 =1
 Nonideal Solution-Application of Gibbs Duhem
Relation to the Determination of Activity
1. At 𝑋𝐵 → 1, 𝑎𝐵 → 1, 𝑙𝑜𝑔𝑎𝐵 →
0, 𝑎𝑛𝑑 𝑋𝐵 Τ𝑋𝐴 → ∞. Thus the curve exhibits a
tail to infinity as 𝑋𝐵 → 1
2. At 𝑋𝐵 → 0, 𝑎𝐵 → 0, 𝑎𝑛𝑑 𝑙𝑜𝑔𝑎𝐵 → −∞, .
Thus the curve exhibits a tail to minus infinity
as 𝑋𝐵 → 0
 Nonideal Solution-Application of Gibbs Duhem
Relation to the Determination of Activity
The tail to minus infinity can be eliminated by considering activity
coefficients instead of the activity

𝑋𝐴 + 𝑋𝐵 = 1, 𝑇ℎ𝑢𝑠 𝑑𝑋𝐴 + 𝑑𝑋𝐵 = 0

𝑑𝑋𝐴 𝑑𝑋𝐵
Therefore 𝑋𝐴 + 𝑋𝐵 = 0 𝑂𝑅 𝑋𝐴 𝑑𝑙𝑜𝑔𝑋𝐴 + 𝑋𝐵 𝑑𝑙𝑜𝑔𝑋𝐵 = 0
𝑋𝐴 𝑋𝐵

Subtracting the above equation from 𝑋𝐴 𝑑𝑙𝑜𝑔𝑎𝐴 + 𝑋𝐵 𝑑𝑙𝑜𝑔𝑎𝐵 = 0, gives

𝑋𝐴 𝑑𝑙𝑜𝑔𝛾𝐴 + 𝑋𝐵 𝑑𝑙𝑜𝑔𝛾𝐵 = 0
 Nonideal Solution-Application of Gibbs Duhem
Relation to the Determination of Activity
it can be deduced that

𝑙𝑜𝑔𝛾𝐵 𝑎𝑡 𝑋𝐴 =𝑋𝐴
𝑙𝑜𝑔𝛾𝐴 𝑎𝑡 𝑋𝐴 = − න 𝑋𝐵 Τ𝑋𝐴 𝑑𝑙𝑜𝑔𝛾𝐵
𝑙𝑜𝑔𝛾𝐵 𝑎𝑡 𝑋𝐴 =1
 Nonideal Solution-Application of Gibbs Duhem
Relation to the Determination of Activity
Calculate the activity of Bismuth in a Bi-Zn alloy containing 75 atom % Zn at 600 C from the following data:

𝑿𝒁𝒏 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

𝛾𝑍𝑛 2.591 2.303 2.098 1.898 1.721 1.551 1.384 1.219 1.089
 The α-Function
the α-function is defined as
𝑙𝑛𝛾𝑖
𝛼𝑖 = 2
1 − 𝑋𝑖
The α-function is always finite.

For the components of a binary A-B solution

𝑙𝑛𝛾𝐴 𝑙𝑛𝛾𝐵
𝛼𝐴 = 2 𝑎𝑛𝑑 𝛼𝐵 = 2
𝑋𝐵 𝑋𝐴
 The α-Function
it can be deduced that:
𝑑𝑙𝑛𝛾𝐵 = 2𝛼𝐵 𝑋𝐴 𝑑𝑋𝐴 + 𝑋𝐴2 𝑑𝛼𝐵 𝑎𝑛𝑑
𝑋𝐵
𝑑𝑙𝑜𝑔𝛾𝐴 = − 𝑑𝑙𝑜𝑔𝛾𝐵
𝑋𝐴
𝑑𝑙𝑛𝛾𝐴 = −2𝛼𝐵 𝑋𝐵 𝑑𝑋𝐴 − 𝑋𝐴 𝑋𝐵 𝑑𝛼𝐵

It can also be deduced that

𝑋𝐴 =𝑋𝐴
𝑙𝑛𝛾𝐴 = −𝑋𝐵 𝑋𝐴 𝛼𝐵 − න 𝛼𝐵 𝑑𝑋𝐴
𝑋𝐴 =1
 The α-Function
Calculate the activity of Tin in an Al-Sn alloy containing a 4 atom % Sn at 723 C
from the following data.

𝑿Al 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

𝛾Al 1.041 1.106 1.199 1.292 1.415 1.557 1.722 1.933 2.148
Direct Calculation of the integral Molar Gibbs Free
Energy of Mixing
𝑑𝐺
From 𝐺𝐴ҧ = 𝐺 + 𝑋𝐵 , for solutions
𝑑𝑋𝐴
𝑑∆𝐺 𝑀
∆𝐺𝐴ҧ 𝑀 = ∆𝐺 𝑀 + 𝑋𝐵
𝑑𝑋𝐴
Rearranging and dividing by 𝑋𝐵2 ,
∆𝐺 𝑀 ∆𝐺𝐴ҧ 𝑀
𝑑 = 2 𝑑𝑋𝐴
𝑋𝐵 𝑋𝐵
Integrating
𝑋𝐴
∆ 𝐺ҧ𝐴𝑀
∆𝐺 𝑀 = 𝑋𝐵 න 2 𝑑𝑋𝐴
0 𝑋𝐵
Direct Calculation of the integral Molar Gibbs Free
Energy of Mixing
𝑋𝐴
∆𝐺𝐴ҧ 𝑀
∆𝐺 𝑀 = 𝑋𝐵 න 2 𝑑𝑋𝐴
0 𝑋𝐵
With ∆𝐺𝐴ҧ 𝑀 = 𝑅𝑇𝑙𝑛𝑎𝐴

𝑋𝐴
𝑙𝑛𝑎𝐴
∆𝐺 𝑀 = 𝑅𝑇𝑋𝐵 න 2 𝑑𝑋𝐴
0 𝑋𝐵
Direct Calculation of the integral Molar Gibbs Free
Energy of Mixing
As an example, the measure activity of Ni in Fe and Cu in Fe can be used to
obtain;

𝑋𝑁𝑖
𝑙𝑛𝑎𝑁𝑖
∆𝐺 𝑀 (𝑖𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝐹𝑒 − 𝑁𝑖) = 𝑅𝑇𝑋𝐹𝑒 න 2 𝑑𝑋𝑁𝑖
0 𝑋𝐹𝑒

𝑋𝐶𝑢
𝑙𝑛𝑎𝐶𝑢
∆𝐺 𝑀 (𝑖𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝐶𝑢 − 𝐹𝑒) = 𝑅𝑇𝑋𝐹𝑒 න 2 𝑑𝑋𝐶𝑢
0 𝑋𝐹𝑒
Direct Calculation of the integral Molar Gibbs Free
Energy of Mixing
Similarly,

𝑋𝐴
∆𝐻ഥ𝐴𝑀
∆𝐻 𝑀 = 𝑋𝐵 න 2 𝑑𝑋𝐴
0 𝑋𝐵
And

𝑋𝐴
∆𝑆𝐴ҧ 𝑀
∆𝑆 𝑀 = 𝑋𝐵 න 2 𝑑𝑋𝐴
0 𝑋𝐵
 Regular Solutions
The Two classes of solutions discussed so far are:
ഥ𝑖𝑀 = 0, ∆𝑉ത𝑖𝑀 = 0 𝑎𝑛𝑑
1. Ideal or Raoultian solutions in which 𝑎𝑖 = 𝑋𝑖 , ∆𝐻
∆𝑆𝑖ҧ 𝑀 = −𝑅𝑙𝑛𝑋𝑖

ഥ𝑖𝑀 ≠ 0
2. Nonideal solutions in which 𝑎𝑖 ≠ 𝑋𝑖 𝑎𝑛𝑑 ∆𝐻

For regular solutions

𝑅𝑇𝑙𝑛𝛾𝐵 = 𝛼 𝐼 𝑋𝐴2 𝑎𝑛𝑑 𝑅𝑇𝑙𝑛𝛾𝐴 = 𝛼 𝐼 𝑋𝐵2
 Regular Solutions
𝑋𝐴 =𝑋𝐴
From: 𝑙𝑛𝛾𝐴 = −𝑋𝐵 𝑋𝐴 𝛼𝐵 − ‫= 𝑋׬‬1 𝛼𝐵 𝑑𝑋𝐴
𝐴
It can be deduced that,
𝑙𝑛𝛾𝐴 = −𝑋𝐵 𝑋𝐴 𝛼𝐵 − 𝛼𝐵 𝑋𝐴 − 1
= −𝑋𝐵 𝑋𝐴 𝛼𝐵 + 𝛼𝐵 𝑋𝐵
= 𝛼𝐵 𝑋𝐵2
Since 𝑙𝑛𝛾𝐴 = 𝛼𝐴 𝑋𝐵2
It implies that 𝛼𝐵 = 𝛼𝐴 = 𝛼 𝑙𝑛𝛾𝑖
𝛼𝑖 = 2
1 − 𝑋𝑖

𝛼𝐼
From 𝑅𝑇𝑙𝑛𝛾𝐴 = 𝛼 𝐼 𝑋𝐵2 , 𝛼 =
𝑅𝑇
 Regular Solutions
Hildebrand defined a regular solution as one in which
ഥ𝑖𝑀 ≠ 0
1. ∆𝐻
2. ∆𝑆𝑖ҧ 𝑀 = ∆𝑆𝑖ҧ 𝑀,𝑖𝑑 = −𝑅𝑙𝑛𝑋𝑖

The properties of a regular solution are best examined by means of the concept
of excess functions.
The excess value of an extensive thermodynamic solution property is simply the
difference between its actual value and the value that it would have if the
solution were ideal.
 Regular Solutions
Example: as applied to the Gibbs free energy of solution;

𝐺 = 𝐺 𝑖𝑑 + 𝐺 𝑋𝑆
Where
𝐺 𝑋𝑆 = 𝑡ℎ𝑒 𝐸𝑥𝑐𝑒𝑠𝑠 𝑚𝑜𝑙𝑎𝑟 𝐺𝑖𝑏𝑏𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝐺 𝑖𝑑 = 𝑡ℎ𝑒 𝑚𝑜𝑙𝑎𝑟 𝐺𝑖𝑏𝑏𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑤ℎ𝑖𝑐ℎ 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑤𝑜𝑢𝑙𝑑 ℎ𝑎𝑣𝑒 𝑖𝑓 𝑖𝑡
𝑤𝑒𝑟𝑒 𝑖𝑑𝑒𝑎𝑙
𝐺 = 𝑡ℎ𝑒 𝑚𝑜𝑙𝑎𝑟 𝐺𝑖𝑏𝑏𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Subtracting the Gibbs free energy of the unmixed components 𝑋𝐴 𝐺𝐴𝑜 + 𝑋𝐵 𝐺𝐵𝑜
from both sides the above expression yields
∆𝐺 𝑀 = ∆𝐺𝑀,𝑖𝑑 + 𝐺 𝑋𝑆
 Regular Solutions
For any solution;
∆𝐺 𝑀 = 𝑅𝑇 𝑋𝐴 𝑙𝑛𝑎𝐴 + 𝑋𝐵 𝑙𝑛𝑎𝐵
∆𝐺 = ∆𝐻 𝑀 − 𝑇∆𝑆 𝑀 But
And for an ideal solution: 𝑎𝑖 = 𝑋𝑖 𝛾𝑖

∆𝐺𝑀,𝑖𝑑 = −𝑇∆𝑆𝑀,𝑖𝑑 ∆𝐺𝑀,𝑖𝑑 = 𝑅𝑇 𝑋𝐴 𝑙𝑛𝑋𝐴 + 𝑋𝐵 𝑙𝑛𝑋𝐵

It can be deduced that, for a regular solution; 𝐺 𝑋𝑆 = ∆𝐺 𝑀 − ∆𝐺𝑀,𝑖𝑑
𝐺 𝑋𝑆 = ∆𝐻 𝑀
With 𝑙𝑛𝛾𝐴 = 𝛼𝑋𝐵2 and 𝑙𝑛𝛾𝐵 = 𝛼𝑋𝐴2 , it can be deduced that
𝐺 𝑋𝑆 = 𝑅𝑇𝛼𝑋𝐴 𝑋𝐵
𝛼𝐼
With 𝛼 = ,
𝑅𝑇
𝐺 𝑋𝑆 = 𝛼 𝐼 𝑋𝐴 𝑋𝐵
 Regular Solutions
It is thus seen that, the excess Gibbs free energy of a regular solution is
independent of temperature.
This can also be shown as follows:
𝑑𝐺 𝑋𝑆 = 𝑉 𝑋𝑆 𝑑𝑃 − 𝑆 𝑋𝑆 𝑑𝑇 + ෍ 𝜇 𝑋𝑆 𝑑𝑛
𝜕𝐺 𝑋𝑆
= −𝑆 𝑋𝑆
𝜕𝑇 𝑃,𝐶𝑜𝑚𝑝
As 𝑆 𝑋𝑆 for a regular solution is zero, then 𝐺 𝑋𝑆 and hence ∆𝐻 𝑀 are independent
of temperature.
 Regular Solutions
The molar excess Gibbs free energy can be obtained from a knowledge of the
dependence, on composition , of the activity coefficient of one component by

𝑋𝐴
𝑙𝑛𝛾𝐴
𝐺 𝑋𝑆 = 𝑅𝑇𝑋𝐵 න 2 𝑑𝑋𝐴
0 𝑋𝐵
Thus for a Raoultian solution, as 𝛾𝐴 = 1, 𝐺 𝑋𝑆 = 0, and for a regular solution
as
𝑙𝑛 𝛾𝐴 Τ𝑋𝐵2 = 𝛼, 𝐺 𝑋𝑆 = 𝑅𝑇𝛼𝑋𝐴 𝑋𝐵