Industrial Physical Chemistry

Youn Jeong Jang

Department of Chemical Engineering

Chapter 5. Simple Mixtures

1)Partial molar quantities
2)Thermodynamics for the simple mixture
: Raoult’s law & Henry’s law
3) Colligative properties
- Boiling point Elevation
5. Mixtures - outline

Simple mixtures

: Henry’s law/Raoult’s law

: Colligative properties
- Boiling point elevation - Osmotic pressure
- Solubility - Freezing point depression
5-1 Partial molar quantities

5-1-1 Partial molar volume

Simple mixtures
** difference with molar volume, 𝑽𝒎 ?

Considering a solution containing 𝒏𝑨 moles of A, 𝒏𝑩 moles of B

𝝏𝑽
Partial molar volume of A 𝑽𝑨 =
𝝏𝒏𝑨 𝒑, 𝑻, 𝒏
′

The change on volume per mole of A added to a large volume of mixture.

5-1 Partial molar quantities

5-1-1 Partial molar volume

V (𝒏𝑨 , 𝒏𝑩) at constant pressure and temperature

𝝏𝑽 𝝏𝑽
𝒅𝑽 = 𝒅𝒏𝑨 + 𝒅𝒏𝑩
𝝏𝒏𝑨 𝒑, 𝑻, 𝒏𝑩 𝝏𝒏𝑩 𝒑, 𝑻, 𝒏𝑨

Once 𝑉𝐴 , 𝑉𝐵 are known, then total volume V is at given temperature, composition

𝑽 = 𝑽𝑨 𝒏 𝑨 + 𝑽𝑩 𝒏 𝑩
5-1 Partial molar quantities

5-1-1 Partial molar volume

Example
- at 25℃, volume of 1 kg water and ethanol mixture can be measured.
𝑽 = 𝟏𝟎𝟎𝟐. 𝟗𝟑 + 𝟓𝟒. 𝟔𝟔𝟔𝟒𝒙 − 𝟎. 𝟑𝟔𝟑𝟗𝟒𝒙𝟐 + 𝟎. 𝟎𝟐𝟖𝟐𝟓𝟔𝒙𝟑
where V=total volume [cm3], x=mole of Ethanol,𝒏𝑬[mol] in mixture
-Calculate partial molar volume for Ethanol
5-1 Partial molar quantities

5-1-2 Partial molar Gibbs energy

𝝏𝑮
𝝁𝑨 = 𝒑, 𝑻, 𝒏′
𝝏𝒏𝑨

𝑮 = 𝝁𝑨 𝒏 𝑨 + 𝝁𝑩 𝒏 𝑩

𝒅𝑮 = 𝑽𝒅𝒑 − 𝑺𝒅𝑻 + 𝝁𝑨 𝒅𝒏𝑨 + 𝝁𝑩 𝒅𝒏𝑩 + … .

= 𝑽𝒅𝒑 − 𝑺𝒅𝑻 + ෍ 𝝁𝒊 𝒅𝒏𝒊

At constant T, P

𝒅𝑮 = ෍ 𝝁𝒊 𝒅𝒏𝒊 = 𝒅𝒘𝒂𝒅𝒅,𝒎𝒂𝒙
5-1 Partial molar quantities

5-1-3 Partial molar internal energy

𝒅𝑼 = −𝒑𝒅𝑽 − 𝑽𝒅𝒑 + 𝑺𝒅𝑻 + 𝑻𝒅𝑺 + 𝒅𝑮

= −𝒑𝒅𝑽 − 𝑽𝒅𝒑 + 𝑺𝒅𝑻 + 𝑻𝒅𝑺 + 𝑽𝒅𝒑 − 𝑺𝒅𝑻 + ෍ 𝝁𝒊 𝒅𝒏𝒊

= −𝒑𝒅𝑽 + 𝑻𝒅𝑺 + ෍ 𝝁𝒊 𝒅𝒏𝒊

At constant V, S

𝒅𝑼 = ෍ 𝝁𝒊 𝒅𝒏𝒊
5-1 Partial molar quantities

5-1-4 Gibbs-Duhem equation

𝑮 = 𝝁𝑨 𝒏 𝑨 + 𝝁𝑩 𝒏 𝑩 + …

At constant T, P 𝒅𝑮 = ෍ 𝝁𝒊 𝒅𝒏𝒊

𝒏𝑨 𝒅𝝁𝑨 + 𝒏𝑩 𝒅𝝁𝑩 + ⋯ = 𝟎 ෍ 𝒏𝒊 𝒅𝝁𝒊 = 𝟎

Gibbs-Duhem equation
5-1 Partial molar quantities

5-1-4 Gibbs-Duhem equation

Example
- The composition of solution is given ; 𝒏𝑨 = 𝟐𝒏𝑩
- When chemical potential for A is changed as much as ∆𝝁𝑨 = +𝟏 𝑱 /𝒎𝒐𝒍
- Calculate chemical potential change for B?
 Industrial Physical Chemistry
Youn Jeong Jang
Department of Chemical Engineering

Chapter 5. Simple Mixtures

1)Partial molar quantities
2)Thermodynamics for the simple mixture
: Raoult’s law & Henry’s law
3) Colligative properties
- Boiling point Elevation
5-2 Thermodynamics for the sample mixture

5-2-1 Gibbs energy for perfect gas mixture

𝜇𝐴,𝑖 = 𝜇𝐴0 + 𝑅𝑇𝑙𝑛 𝑝 𝜇𝐵,𝑖 = 𝜇𝐵0 + 𝑅𝑇𝑙𝑛 𝑝

𝑝
𝜇= 𝜇0 + 𝑅𝑇𝑙𝑛 0 = 𝜇0 + 𝑅𝑇𝑙𝑛 𝑝
𝑝
5-2 Thermodynamics for the sample mixture

5-2-1 Gibbs energy for perfect gas mixture

𝜇𝐴,𝑖 = 𝜇𝐴0 + 𝑅𝑇𝑙𝑛 𝑝 𝜇𝐵,𝑖 = 𝜇𝐵0 + 𝑅𝑇𝑙𝑛 𝑝

𝐺𝐴,𝑖 = 𝑛𝐴 𝜇𝐴,𝑖 = 𝑛𝐴 (𝜇𝐴0 + 𝑅𝑇𝑙𝑛 𝑝) 𝐺𝐵,𝑖 = 𝑛𝐵 𝜇𝐵,𝑖 = 𝑛𝐵 (𝜇𝐵0 + 𝑅𝑇𝑙𝑛 𝑝)

𝑮𝒊 = 𝑛𝐴 𝜇𝐴,𝑖 + 𝑛𝐵 𝜇𝐵,𝑖
= 𝒏𝑨 𝝁𝟎𝑨 + 𝑹𝑻𝒍𝒏 𝒑 + 𝒏𝑩 (𝝁𝟎𝑩 + 𝑹𝑻𝒍𝒏 𝒑)

𝑮𝒇 = 𝑛𝐴 𝜇𝐴,𝑓 + 𝑛𝐵 𝜇𝐵,𝑓
= 𝒏𝑨 𝝁𝟎𝑨 + 𝑹𝑻𝒍𝒏 𝒑𝑨 + 𝒏𝑩 (𝝁𝟎𝑩 + 𝑹𝑻𝒍𝒏 𝒑𝑩 )
𝑝𝐴 +𝑝𝐵 = 𝑝

𝑝
𝜇 = 𝜇0 + 𝑅𝑇𝑙𝑛 0 = 𝜇0 + 𝑅𝑇𝑙𝑛 𝑝
𝑝
5-2 Thermodynamics for the sample mixture

5-2-1 Gibbs energy for perfect gas mixture

∆𝑚𝑖𝑥 𝐺 = 𝐺𝑓 − 𝐺𝑖
𝒑𝑨 𝒑𝑩
= 𝒏𝑨 𝑹𝑻𝒍𝒏 + 𝒏𝑩 𝑹𝑻𝒍𝒏
𝒑 𝒑

= 𝒏𝑨 𝑹𝑻𝒍𝒏 𝒙𝑨 + 𝒏𝑩 𝑹𝑻𝒍𝒏 𝒙𝑩

∆𝒎𝒊𝒙 𝑮 <0
5-2 Thermodynamics for the sample mixture

5-2-1 Gibbs energy for perfect gas mixture - Entropy

𝜕∆𝒎𝒊𝒙 𝑮
∆𝑚𝑖𝑥 𝑆 = − 𝑝
𝜕𝑇

= −𝒏𝑨 𝑹𝒍𝒏 𝒙𝑨 + 𝒏𝑩 𝑹𝒍𝒏 𝒙𝑩

= −𝒏𝑹(𝒙𝑨 𝒍𝒏 𝒙𝑨 + 𝒙𝑩 𝒍𝒏 𝒙𝑩 )

∆𝒎𝒊𝒙 𝑺 >0
5-2 Thermodynamics for the sample mixture

5-2-1 Gibbs energy for perfect gas mixture - Enthalpy

∆𝑚𝑖𝑥 𝐻 = ∆𝑚𝑖𝑥 𝐺 + 𝑇∆𝑚𝑖𝑥 𝑆

= −𝒏𝑹(𝒙𝑨 𝒍𝒏 𝒙𝑨 + 𝒙𝑩 𝒍𝒏 𝒙𝑩 ) −𝒏𝑹𝑻(𝒙𝑨 𝒍𝒏 𝒙𝑨 + 𝒙𝑩 𝒍𝒏 𝒙𝑩 )

∆𝒎𝒊𝒙 𝑯=0
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture

Ideal solution
- Defined by complete uniformity of cohesive force
- Mixing between similar components
- Obeys Raoult’s law

Solution chemical potential depends on

composition and chemical potential of vapor

𝝁𝑨 𝒍 = 𝝁𝑨 𝒈 at equilibrium
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture

Chemical potential for pure liquid

∗
𝒑 𝑨
𝝁∗𝑨 𝒍 = 𝝁𝒐𝑨 𝒈 + 𝑹𝑻 𝒍𝒏 𝒐
𝒑𝑨

= 𝝁𝒐𝑨 𝒈 + 𝑹𝑻 𝒍𝒏 𝒑∗𝑨
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture

Chemical potential for ideal liquid mixture

𝝁𝑨 𝒍 = 𝝁𝒐𝑨 𝒈 + 𝑹𝑻 𝒍𝒏 𝒑𝑨

𝝁𝑨 𝒍 = 𝝁∗𝑨 𝒍 − 𝑹𝑻 𝒍𝒏 𝒑∗𝑨 + 𝑹𝑻 𝒍𝒏 𝒑𝑨

𝒑𝑨
𝝁𝑨 𝒍 = 𝝁∗𝑨 𝒍 + 𝑹𝑻 𝒍𝒏
𝒑∗𝑨
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture - Raoult’s law

Raoult’s law
𝒑𝑨 = 𝒙𝑨 × 𝒑∗𝑨

𝝁𝑨 𝒍 = 𝝁∗𝑨 𝒍 + 𝑹𝑻 𝒍𝒏 𝒙𝑨

For real solution, it holds for very dilute solution (𝒙𝑨 → 𝟏) or mixture
between similar molecules (ex) Benzene and Toluene
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture – Raoult’s law

𝒑𝑨 = 𝒙𝑨 × 𝒑∗𝑨

For real solution, it holds for very dilute solution (𝒙𝑨 → 𝟏) or mixture
between similar molecules (ex) Benzene and Toluene
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture - Henry’s law

Henry’s law

𝒑𝑩 = 𝒙𝑩 × 𝑲𝑩 for 𝒙𝑩 → 𝟏

or
𝒑𝑩 = 𝒃𝑩 × 𝑲𝑩

where 𝑥𝐵 - mole fraction, 𝑏𝐵 -molar

concentration, and 𝐾𝐵 - empirical constant
(pressure dimension)

The law is related with solubility of gases in liquids

: Solubility depends on attractive energy between solute and solvent
molecules
5-2 Thermodynamics for the sample mixture

5-2-2 Gibbs energy for ideal liquid mixture

 Industrial Physical Chemistry
Youn Jeong Jang
Department of Chemical Engineering

Chapter 5. Simple Mixtures

1)Partial molar quantities
2)Thermodynamics for the simple mixture
: Raoult’s law & Henry’s law
3) Colligative properties
- Boiling point Elevation
5-3 Colligative Properties

5-3-1 Colligative Properties

- number of particles dependent only - their identities independent

5-3 Colligative Properties

5-3-2 Boiling point elevation

Assumption
- no vapor from solute
- solute does not dissolve in solvent

𝝁∗𝑨 𝒈 = 𝝁𝑨 𝒍 = 𝝁∗𝑨 𝒍 + 𝑹𝑻 𝒍𝒏 𝒙𝑨

𝒙𝑨 + 𝒙𝑩 = 𝟏 in liquid

∗ ∗ ∆𝒗𝒂𝒑 𝑮
𝝁𝑨 𝒈 −𝝁𝑨 𝒍
𝒍𝒏 𝒙𝑨 = =
𝑹𝑻 𝑹𝑻
5-3 Colligative Properties

5-3-2 Boiling point elevation

𝝁∗𝑨 𝒈 = 𝝁𝑨 𝒍 = 𝝁∗𝑨 𝒍 + 𝑹𝑻 𝒍𝒏 𝒙𝑨

𝒅𝒍𝒏 𝒙𝑨 𝟏 𝒅(∆𝒗𝒂𝒑 𝑮/𝑻) ∆𝒗𝒂𝒑 𝑯

= =− 𝑹𝑻𝟐
𝒅𝑻 𝑹 𝒅𝑻

∆𝒗𝒂𝒑 𝑯
𝒅𝒍𝒏 𝒙𝑨 =− 𝒅𝑻
𝑹𝑻𝟐

∆𝒗𝒂𝒑 𝑯 𝟏 𝟏
𝒍𝒏 𝒙𝑨 = 𝒍𝒏 𝟏 − 𝒙𝑩 = ( − ∗)
𝑹 𝑻 𝑻
5-3 Colligative Properties

5-3-2 Boiling point elevation

∆𝒗𝒂𝒑 𝑯 𝟏 𝟏
𝒍𝒏 𝒙𝑨 = 𝒍𝒏 𝟏 − 𝒙𝑩 = ( − ∗)
𝑹 𝑻 𝑻

When 𝒙𝑩 ≪ 𝟏

∆𝒗𝒂𝒑 𝑯 𝟏 𝟏
−𝒙𝑩 = ( − ∗)
𝑹 𝑻 𝑻
5-3 Colligative Properties

5-3-2 Boiling point elevation

𝑹𝑻∗𝟐
∆𝑻𝒃 = 𝑲 𝒙𝑩 𝑲=
∆𝒗𝒂𝒑 𝑯

∆𝑻𝒃 = 𝑲𝒃 𝒃
5-3 Colligative Properties

5-3-3 Freezing point depression

𝝁∗𝑨 𝒔 = 𝝁∗𝑨 𝒍 + 𝑹𝑻 𝒍𝒏 𝒙𝑨

𝑹𝑻 ∗𝟐
∆𝑻𝒇 = 𝑲′ 𝒙𝑩 𝑲′ =
∆𝒇𝒖𝒔 𝑯

∆𝑻𝒇 = 𝑲𝒇 𝒃
5-3 Colligative Properties

5-3-4 Solubility

𝝁∗𝑩 𝒔 = 𝝁∗𝑩 𝒍 + 𝑹𝑻 𝒍𝒏 𝒙𝑩

∆𝒇𝒖𝒔 𝑯 𝟏 𝟏
𝒍𝒏 𝒙𝑩 = ( − )
𝑹 𝑻𝒇𝒖𝒔 𝑻
5-3 Colligative Properties

5-3-5 Osmotic pressure

𝝁∗𝑨 𝒑 = 𝝁𝑨 𝒙𝑨 , 𝒑 + 𝚷

𝝁𝑨 𝒙𝑨 , 𝒑 + 𝚷 = 𝝁∗𝑨 𝒑 + 𝚷 + 𝑹𝑻 𝒍𝒏 𝒙𝑨

𝒑+𝚷
𝝁∗𝑨 𝒑 + 𝚷 = 𝝁∗𝑨 𝒑 + න 𝑽𝒎 𝒅𝒑
𝒑

𝒑+𝚷
−𝑹𝑻 𝒍𝒏 𝒙𝑨 = න 𝑽𝒎 𝒅𝒑
𝒑
5-3 Colligative Properties

5-3-5 Osmotic pressure

𝒑+𝚷
−𝑹𝑻 𝒍𝒏 𝒙𝑨 = න 𝑽𝒎 𝒅𝒑
𝒑

𝑹𝑻𝒙𝑩 = 𝚷𝑽𝒎

𝚷 = [𝑩]𝑹𝑻
𝑽𝒂𝒏′ 𝒕 𝑯𝒐𝒇𝒇 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏