PE 258 Thermodynamics II

Lecture 6: Solutions
Dr. Yen Adams Sokama-Neuyam
Department of Petroleum Engineering
College of Engineering
KNUST, Kumasi.
Office Address: Casely-Hayford Building Rm F25
Email: asokama@knust.edu.gh
Kinds of Solutions
§ A solution is a homogeneous mixture of chemical species
dispersed on a molecular scale. By this definition, a solution is
a single phase. A solution may be gaseous, liquid, or solid.
§ Binary solutions are composed of two constituents, ternary
solutions three, quaternary four. The constituent present in the
greatest amount is ordinarily called the solvent, while those
constituents-one or more-present in relatively small amounts
are called the solutes.
§ The distinction between solvent and solute is an arbitrary one. If
it is convenient, the constituent present in relatively small
amount may be chosen as the solvent.
Kinds of Solutions
Ideal Solutions
§ An ideal solution is defined as a solution in which the
chemical potential of each component is given for all
compositions by the formula:

𝜇𝑖 𝑇, 𝑃 = 𝜇𝑖∗ 𝑇, 𝑃 + 𝑅𝑇 ln(𝑥𝑖 )

§ Where 𝜇𝑖∗ 𝑇, 𝑃 is the chemical potential of the pure component

𝑖 when it is at the same temperature 𝑇 and pressure 𝑃 as the
solution and 𝑥𝑖 is the mole fraction of component 𝑖 in the
solution.
Raoult’s Law
§ Raoult’s law states that:

𝑃𝑖 = 𝑃𝑖∗ 𝑥𝑖

§ Where 𝑃𝑖 is the partial vapor pressure of substance 𝑖, defined as

the partial pressure of substance 𝑖 in the vapor phase that is at
equilibrium with the solution, 𝑃𝑖∗ is the equilibrium vapor
pressure of the pure substance 𝑖 at the temperature and
pressure of the solution and 𝑥𝑖 is the mole fraction of substance
𝑖 in the solution.
Raoult’s Law
§ We can show that a component of an ideal solution obeys
Raoult’s law if the solution is at equilibrium with an ideal gas
mixture.
§ From the fundamental fact of phase equilibrium, we can write:

𝑜(𝑔) 𝑃𝑖
𝜇𝑖∗ 𝑇, 𝑃 + 𝑅𝑇 ln(𝑥𝑖 ) = 𝜇𝑖 + 𝑅𝑇 ln 𝑜
𝑃

𝑜(𝑔)
§ where, 𝜇𝑖 is the chemical potential of the gas in its standard
state. Thus, the chemical potential of component 𝒊 has the
same value in the solution and in the vapor.
Raoult’s Law
§ At equilibrium, the chemical potential of pure component 𝑖 is
equal to the chemical potential of gaseous component 𝑖 at
pressure 𝑃𝑖∗ , so that:
∗
∗ ∗ ∗ 𝑜(𝑔) 𝑃𝑖
𝜇𝑖 𝑇, 𝑃 ≈ 𝜇𝑖 𝑇, 𝑃 = 𝜇𝑖 + 𝑅𝑇 ln 𝑜
𝑃
§ Combining the equations yield:

∗
𝑜(𝑔) 𝑃𝑖 𝑜(𝑔) 𝑃𝑖
𝜇𝑖 + 𝑅𝑇 ln 𝑜 + 𝑅𝑇 ln(𝑥𝑖 ) = 𝜇𝑖 + 𝑅𝑇 ln 𝑜
𝑃 𝑃
Raoult’s Law
§ Cancelling and combining terms yields:

𝑃𝑖∗ 𝑥𝑖 𝑃𝑖
𝑅𝑇 ln 𝑜
= 𝑅𝑇 ln 𝑜
𝑃 𝑃
§ And therefore

𝑃𝑖 = 𝑃𝑖∗ 𝑥𝑖

§ Which is Raoult’s law. An ideal solution is sometimes defined as a

solution in which every substance in the solution obeys Raoult’s
law for all compositions.
The Thermodynamic Variables of An Ideal Solution

§ For a component of an ideal solid solution, the standard state is

the pure solid at pressure 𝑃𝑜 . We will define all of our standard
states to correspond to a pressure 𝑷𝒐 .

§ Assuming the chemical potential of a pure liquid or solid

substance is independent of pressure, we can write:

𝜇𝑖 𝑇, 𝑃 = 𝜇𝑖𝑜 𝑇 + 𝑅𝑇 ln(𝑥𝑖 )
The Thermodynamic Variables of An Ideal Solution

§ The thermodynamic functions of a solution are usually expressed

in terms of the quantities of mixing.
§ The Gibbs energy change of mixing is giving as:

∆𝐺𝑚𝑖𝑥 = 𝐺 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 𝐺(𝑢𝑛𝑚𝑖𝑥𝑒𝑑 𝑜𝑟 𝑝𝑢𝑟𝑒)

§ Which can be expressed as:

𝐶 𝐶

∆𝐺𝑚𝑖𝑥 = ? 𝑛𝑖 𝜇𝑖 − ? 𝑛𝑖 𝜇𝑖∗
𝑖=1 𝑖=1
The Thermodynamic Variables of An Ideal Solution

§ But
𝐶

𝐺 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = ? 𝑛𝑖 [𝜇𝑖∗ + 𝑅𝑇 ln(𝑥𝑖 )]

𝑖=1
§ Which gives us:
𝐶

∆𝐺𝑚𝑖𝑥 = 𝑅𝑇 ? 𝑛𝑖 ln(𝑥𝑖 )
𝑖=1
§ For an ideal solution.
The Thermodynamic Variables of An Ideal Solution

§ Entropy change of mixing

§ Recall the Maxwell Relation:
𝜕𝐺
= −𝑆
𝜕𝑇 𝑃,𝑛

§ It can be shown that the entropy of an ideal solution is then

given by:
𝐶
𝜕𝜇𝑖∗
𝑆 = − ? 𝑛𝑖 + R ln(𝑥𝑖 )
𝜕𝑇 𝑃
𝑖=1
The Thermodynamic Variables of An Ideal Solution

§ For the unmixed components:

𝐶

𝑆 𝑢𝑛𝑚𝑖𝑥𝑒𝑑 = −𝑅 ? 𝑛𝑖 ln(𝑥𝑖 )
𝑖=1
§ Which gives us:
𝐶

∆𝑆𝑚𝑖𝑥 = −𝑅 ? 𝑛𝑖 ln(𝑥𝑖 )
𝑖=1
The Thermodynamic Variables of An Ideal Solution

§ Enthalpy change of mixing

§ The enthalpy change of mixing is given by:
∆𝐻𝑚𝑖𝑥 = ∆𝐺𝑚𝑖𝑥 + 𝑇∆𝑆𝑚𝑖𝑥

§ Which can be expressed as:

𝐶

∆𝐻𝑚𝑖𝑥 = 𝑅𝑇 ? 𝑛𝑖 ln 𝑥𝑖 − ln 𝑥𝑖 =0
𝑖=1

§ Similarly, it can be shown that ∆𝑽𝒎𝒊𝒙 = 𝟎 for ideal solution.

Colligative Properties
§ The colligative properties can be defined as the properties of
solutions which is wholly determined by the ratio of the
number of solute particles and the number of solvent
molecules in a particular solution, and are completely
independent of the nature of the chemical species present.

§ The number ratio can be calculated by using various units that

determine the concentration of solutions. The general
assumption is that in the case of an ideal solution, the
properties are independent of the nature of solute particles
present in it and are somewhat approximate for dilute real
solutions.
Colligative Properties
Colligative Properties of a Solution Include:

1. Relative lowering of vapor pressure

2. Elevation of boiling point
3. Depression of freezing point
4. Osmotic pressure
Colligative Properties
§ For a particular mass ratio of solute and solvent, all colligative
properties should be inversely proportional to solute molar
mass.

§ Relative molar masses can be determined by measuring

colligative properties for a dilute solution of a non-ionized
solute.

§ Colligative properties are mostly applicable for dilute solutions

as their behavior may often be approximated. This is because
they are ideal solutions.
Relative Lowering of Vapour Pressure
§ On dissolving the non-volatile solute in a pure solvent, the
vapour pressure of a pure solvent gets gradually decreased.
§ Let us assume that 𝑝 is the vapour pressure of the solvent and 𝑝𝑠
is the vapour pressure of the solution, then the lowering of
vapour pressure can be written as (𝑝 – 𝑝𝑠).
§ This lowering of vapour pressure relative to the vapour pressure
of the pure solvent is called the Relative lowering of Vapour
pressure. Thus,

𝑃 − 𝑃3
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝐿𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑜𝑓 𝑉𝑃 =
𝑃
Relative Lowering of Vapour Pressure
§ From Raoult’s law, the relative lowering of the vapor pressure
of a dilute solution is equal to the mole fraction of the solute
present in dilute solution.

𝑃 − 𝑃3 𝑛
=
𝑃 𝑛+𝑁

Where n is the number of moles of the solute and N is the number

of moles of the solvent.
Tutorial 6
1. Calculate the Gibbs energy change of mixing, the entropy
change of mixing, the enthalpy change of mixing, and the
volume change of mixing for a solution of 1.200 mol of
benzene and 1.300 mol of toluene at 20.00 ℃. Assume the
solution is ideal.
2. Find ΔSmix, ΔGmix, ΔHmix, and ΔVmix if 125.0 g of benzene
and 25.0 g of naphthalene are mixed at 60.0 °C.
Home Work 6
Twenty grams of a solute are added to 100g of water at 25℃. The
vapor pressure of pure water is 23.76 mmHg; the vapor pressure
of the solution is 22.41 mmHg.
a. Calculate the molar mass of the solute.
b. What mass of this solute is required in 100g of water to reduce
the vapor pressure to one-half the value for pure water?