Chapter II:

PROPERTIES OF MIXTURE
I. THERMODYNAMIC DESCRIPTION OF MIXTURE
1. Solution
a. Concepts
v Solution: a homogeneous system (phase) consists of 2 or more
substance of which compositions varies in a limited range.
v Solvent: the major substance
v Solute: the minor substance
v The method to express the composition of a solution:
Ø Percent concentration:
Ø Molar concentration (morlarity):
Ø Molal concentration (molality):
Ø Mole fraction:
I. THERMODYNAMIC DESCRIPTION OF MIXTURE
1. Solution
b. Classification of solutions
v Ideal solution:
Ø For a given solution of A and B substance:
Interaction: FA-A = FB-B = FA-B
Enthalpy of mixture formation: ∆Hmix = 0

Volume effect of mixture formation: ∆Vmix = 0

v Real solution:
Ø For a given solution of A and B substance:
Interaction: FA-A ≠ FB-B ≠ FA-B
Enthalpy of mixture formation: ∆Hmix ≠ 0
Volume effect of mixture formation: ∆Vmix ≠ 0
I. THERMODYNAMIC DESCRIPTION OF MIXTURE
1. Solution
b. Classification of solutions
v Ideal-dilute solution:
Ø For a given solution of A and B substance: nA >> nB
Interaction: FA-A is the majority
Enthalpy of mixture formation: ∆Hmix ≈ 0

Volume effect of mixture formation: ∆Vmix ≈ 0

Ideal-dilute solution ≈ ideal solution

I. THERMODYNAMIC DESCRIPTION OF MIXTURE
2. Colligative properties
v Application extent: Ideal-dilute solution of which solute is is not
volatile, not electrolyzed
v Colligative properties: these properties of solution depend only on the
number of solute particles present, not their identity
I. THERMODYNAMIC DESCRIPTION OF MIXTURE
2. Colligative properties
a. Lowering of vapor pressure
Vapor pressure of solution: P = P!" − x#P!"

Lowering of vapor pressure compared to solvent:

DP = P10 - P10 .x 1 = P10 (1 - x 1 ) = P10 x 2

I. THERMODYNAMIC DESCRIPTION OF MIXTURE
2. Colligative properties
b. Elevation of boiling point, the depression of freezing point

Elevation of boiling point Depression of freezing point

∆Tb= Tb* – Tb1 = Kb.Cm ∆Tf= Tf1 – Tf* = Kf.Cm
Cm molality Cm molality
Kb empirical boiling-point constant Kf empirical freezing-point constant
of the solvent of the solvent
#
#
𝑅𝑇$! 𝑀! 𝑅𝑇(! 𝑀!
𝐾$ = (K.kg/mol) 𝐾( = (K.kg/mol)
1000𝜆%&' 1000𝜆)%*
I. THERMODYNAMIC DESCRIPTION OF MIXTURE
2. Colligative properties
c. Osmosis
vSemipermeable membrane: a membrane
permeable to the solvent but not to the solute
vThe osmotic pressure of a solution: the
pressure that must be applied to the solution
Solution Solvent
to stop the influx of solvent.
vMeasurement of osmotic pressure

h
Solution

Solvent

vEquation n
p= RT = CRT
V
vIsotonic, hypotonic, haemolysis:
II. DISSOLUTION OF A GAS IN A LIQUID
Gas:
- Not react with solvent
- Not be separated in solution
- Form an ideal-dilute solution
1. Effect of pressure on the dissolution of a gas
vHenry’s equation: xi=KH.Pi
KH: an empirical constant
II. DISSOLUTION OF A GAS IN A LIQUID
2. Effect of temperature on the dissolution of a gas.
Shreder’s equation
𝑑𝑙𝑛𝑥! 𝜆#!$
Shreder’s equation =
𝑑𝑇 " 𝑅𝑇 %
Gas i Solution i

Condensation Solvation

Liquid i i in solution
Dilute liquid i

λdis =λcon + λdil + λsol

For the ideal-dilute solution: λdil = 0 λsol = 0

λdis ≈ λcon
III. MISCIBLE LIQUIDS. SOLUTION – VAPOR EQUILIBRIA
1. Ideal binary mixtures
a. Raoult’s law

In an ideal solution of which substances are volatile, partial vapor

pressure of each substance is proportional to its mole fraction
Pi = Poi.xi

For a binary mixture of A and B

(solution of A and B): P P
PA = PoA.xA = (1 – xB)PoA (1)
PB = PoB.xB (2) P0B
(3)
Vapor pressure of the solution:
P0A

P = PA + PB = (PoB-PoA)xB +PoA (3)

(2) (1)

Ideal binary mixture obeys

Raoult’s law 0 1
xB
III. MISCIBLE LIQUIDS. SOLUTION – VAPOR EQUILIBRIA
1. Ideal binary mixtures
b. Composition of vapor phase – Konovalov’s rule 1

yB xB
= a.
yA xA
Consequences:
1. Composition of a substance in vapor phase is proportional to its
composition in solution (When composition of a substance in
solution increases, its composition in vapor phase also increases).
2. Composition of a substance with lower boiling point in vapor
phase is higher than that in solution.
III. MISCIBLE LIQUIDS. SOLUTION – VAPOR EQUILIBRIA
2. Real binary mixtures
a. Vapor pressure
P P P P

P0B
P0B

P0A P0A

0 1 0 1
xB xB

Positive deviation Negative deviation

III. MISCIBLE LIQUIDS. SOLUTION – VAPOR EQUILIBRIA
2. Real binary mixtures
b. Composition of vapor phase – Konovalov’s rule 2
For a solution of A and B:
At extreme point in P – x diagram: xB = yB; xA = yA
P P
Liquid Liquid
L⇌V L⇌V

L⇌V L⇌V

Vapor Vapor

0 xB Low-boiling 1 0 xB High-boiling 1
azeotrope azeotrope
yB x
= a. B 𝛂 = 1 at extreme point
yA xA
III. MISCIBLE LIQUIDS. SOLUTION – VAPOR EQUILIBRIA
3. Component separation using distillation
v Distillation: the process of separating the substances from a liquid
mixture by using selective evaporation and condensation.
III. MISCIBLE LIQUIDS. SOLUTION – VAPOR EQUILIBRIA
3. Component separation using distillation

(yB)1 (yB)2
n n
it o it o
ra

Co
Co
o ra
ap nd

nd
o
v ap en

en
E v sa
E

sa
tio

tio
n

n
(xB)1 (xB)2 (xB)3

vDistillation of ideal solution and real solution (not azeotrope).

vDistillation of azeotrope.
IV. IMMISCIBLE LIQUIDS. PHASE DIAGRAM
1. Phase separation
v Phenol is added to a sample of water at a temperature T.
(1) As the amount of phenol is smaill: phenol dissolves completely,
and the binary system remains a single phase.
(2) As more phenol is added: the sample now consists of 2 phases in
equilibrium with each other.
(3) When more phenol is added: water dissolves in phenol slightly, and
the system reverts to a single phase.
v In the case of 2 phases

Water phase
Phenol/water

Phenol phase
Water/phenol
 IV. IMMISCIBLE LIQUIDS. PHASE DIAGRAM
2. Liquid – liquid phase diagram
T T T T
TK
Q
T3 Q2
B1 B2 P1 P P2
T2 T2

H1 H2
T1
A1 A2 H
T1

0 1 0 x1 x x2 1
(H2O) xphenol (Phenol) (H2O) xphenol (Phenol)

v At T = const, composition changes v At composition = const, T changes:

E.g1. At T1, phenol is added to water. E.g2. System with composition x,
A1: phenol phase appears temperature T1
H→P→Q
A2: water phase dissappears T1 → T2 → T3
H1 → P1 → Q
H2 → P2→ Q2
 IV. IMMISCIBLE LIQUIDS. PHASE DIAGRAM
2. Liquid – liquid phase diagram

T T T T T
T

0 1 0 1 0 1
xphenol (Phenol)
(H2O) (H2O) xtriethylamine (Triethyl- (H2O) xnicotine (Nicotine)
amine)

Phase diagram of Phase diagram of Phase diagram of

water – phenol water – triethylamine nicotine – water
system system system
IV. IMMISCIBLE LIQUIDS. PHASE DIAGRAM
3. Critical solution temperature T T

v The upper critical solution temperature TK

(Tuc)
(Tuc): the highest temperature at which
phase separation occurs.
Above Tuc, the two substances are fully
miscible.
E.g. Mixture of phenol and water. 0 1
xphenol
T T
v The lower critical solution
temperature (Tlc): below Tlc,
substances mix in all proportions
Above Tlc, substances form two phases.
E.g. Mixture of triethylamine and TK
water. (Tlc)
0 1
xtriethylamine
IV. IMMISCIBLE LIQUIDS. PHASE DIAGRAM
3. Critical solution temperature

T T

E.g. Mixture of nicotine TK

and water. (Tuc)

TK
(Tlc)

0 1
xnicotine
V. LIQUID - SOLID DIAGRAMS
1. The crystallization from solution
For two almost immiscible solids and their completely miscible liquids.
E.g.: NaCl – H2O, KCl – LiCl, medicine – C2H5OH
T
b
a, b: melting point
LAB of A, B, respectively
a
aeb: liquid line

SB ⇌ L ass’b: solid line

SA ⇌ L
e e: eutecti
s s
’

0 E 1
(100% A) xB (100%B)
V. LIQUID - SOLID DIAGRAMS
2. Eutectics

v A mixture at eutectic composition: the mixture with the lowest

melting point.
• Application: Prepare the mixtures for healing
VI. EXTRACTION. NERNST DISTRIBUTION LAW
1. Extraction
v Extraction from a solid mixture: separate the
substance from a solid mixture by using a
solvent.

v Extraction from a solution: separate the

substance from a solution by using a solvent.
VI. EXTRACTION. NERNST DISTRIBUTION LAW
2. Nernst distribution law
A system of A, B solvent and Y solute:
- Y can dissolve in A
- Y can dissolve in B
- A and B are immiscible
v Nernst distribution law:
CY / A
=K (T, P = const)
CY / B

K: distribution constant
VI. EXTRACTION. NERNST DISTRIBUTION LAW
2. Nernst distribution law
v Application of Nernst distribution law:
A solution of volume Vo contains a mol of the solute Y.
Extraction with solvent of volume Vc
xn: mol of solute A after n times of extraction
𝐶5/$6789:;
𝐾= >1
𝐶5/$67<;!6:
a − x1
Ø After 1st extraction: 𝐶&/𝒔𝒐𝒍𝒗𝒆𝒏𝒕 V V3
= K = x2 x1 = a.
C&/𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 1 V3 + KV4
V3
n
æ V0 ö
Ø After nth extraction: xn = a.çç ÷÷
è V0 + K .Vc ø