Chapter 09

General Chemistry I (2022) Lecture by B. H.
Hong
Chapter 09. PHYSICAL EQUILIBRIA
PHASES AND PHASE TRANSITIONS

9.1 Vapor Pressure
9.2 Volatility and Intermolecular Forces
9.3 The Variation of Vapor Pressure with Temperature
9.4 Boiling
9.5 Freezing and Melting
9.6 Phase Diagrams
9.7 Critical Properties
SOLUBILITY
9.8 The Limits of Solubility
9.9 The Like-Dissolves-Like Rule
9.10 Pressure and Gas Solubility: Henry’s Law
9.11 Temperature and Solubility
9.12 The Enthalpy of Solution
9.13 The Gibbs Free Energy of Solution
General Chemistry I (2022) Lecture by B. H. Hong
COLLIGATIVE PROPERTIES
9.14 Molality
9.15 Vapor-Pressure Lowering
9.16 Boiling-Point Elevation and Freezing-Point Depression
9.17 Osmosis
BINARY LIQUID MIXTURES

9.18 The Vapor Pressure of a Binary Liquid Mixture
9.19 Distillation
9.20 Azeotropes
IMPACT ON BIOLOGY AND MATERIALS

9.21 Colloids
9.22 Bio-based Materials and Biomimetic Materials
Key Ideas Dynamic equilibrium;

the molar Gibbs free energies are the same.
Solutes change the thermodynamic properties.
Goal Transformation between states

⇒ Chemical and biochemical transformations
⇒ Solutions in the body and in oil production, ···
9.1 Vapor Pressure

Nearly all we encounter in our daily life are mixtures
or solutions; air, oceans, blood plasma, ···
Phase changes in pure substances & effects
of solutes & colloids
Phase equilibrium; ΔG = 0
Dynamic equilibrium; no net flow of matter between phases
Independent of the direction (with enough material)
Rate of evaporation = rate of condensation
Vapor pressure increases with T;
Solid also exerts a vapor pressure; sublimation

9.2 Volatility and Intermolecular Forces
High (low) vapor pressure

low (high) intermolecular forces between liquid molecules
Dimethyl ether (CH3–O–CH3; gas)

vs. ethanol (CH3–CH2–OH; liquid, hydrogen bonding)
Rate of evaporation =
rate of condensation
Pressure dependence of the Gibbs free energy of an ideal gas
At constant T, P1 P2 (ideal gas)
By choosing P1 = 1 bar as the reference (standard) state
(P in bar, dimensionless)
The Gibbs free energy of a liquid is almost independent

of pressure:
P1 = 1
For the phase equilibrium (not a standard state!)

between H2O(l) and H2O(g) with a vapor pressure P at T,
Fig 9.3
1 atm
H2O
Note that the Clausius-Clapeyron equation is a special case

of the van't Hoff equation for the temperature dependence
of the equilibrium constants:
Ex 8.1 At , the vapor pressure of CCl4 is

405 torr and = 33.05 kJ/mol.
Vapor pressure at ?

9.4 Boiling
Evaporation vs. boiling

Boiling point vs. normal boiling point Tb
Freezing point vs. normal freezing point Tf

(= normal melting point)
Supercooling https://www.youtube.com/watch?v=fSPzMva9_CE
(magic heat pack; supercooled Na2CO3 solution), ···
Tf of most substances increases with P;

Vm,solid < Vm,liquid, Le Châtelier's principle
Solid inner core of the earth

Tf of water decreases with P; Vm,solid > Vm,liquid ;
open structure of ice due to hydrogen bonding
9.6 Phase Diagrams
Gibbs phase rule: f=c–p+2
f; degrees of freedom, c; # of components, p; # of phases
# of independent mole fractions = c – 1 (x1 + ··· + xc = 1)
# of intrinsic variables = 2 (P and V) + p(c – 1)
# of phase equilibria = p – 1
# of phase equilibrium conditions for all components = c(p – 1)
⇒ Degrees of freedom = 2 + p(c – 1) – c(p – 1) = c – p + 2

9.6 Phase Diagrams
One-component phase diagram
H 2O
Phase boundaries; coexistence curves, dynamic equilibrium
Fig 9.11
Negative slope of the solid (ice I)-liquid coexistence curve
At least ten kinds of ice Fig 9.9
9.6 Phase Diagrams
H2O
CO2
9.6 Phase Diagrams
S
9.6 Phase Diagrams

9.6 Phase Diagrams

Triple point;
ice, water, and vapor coexist at 273.16 K and 0.006 atm.
(f = 1 – 3 + 2 = 0)
Quadruple points never exist for a one-component system.
CO2
Positive slope of the solid-liquid

coexistence curve
S
Two solid (S8) phases; rhombic
and monoclinic
Fig 9.8
Critical point (Tc, Pc) at the end of the liquid-vapor

coexistence curve
Meniscus disappears at the critical point.
Supercritical fluid (T > Tc & P > Pc);

formally a gas but as dense as a liquid phase
Supercritical CO2;
extracting solvent for caffeine, drugs, perfumes,
sesame oil, ···
Supercritical hydrocarbons;
extracting solvent for coals from ash, ···
Figs 9.13, 14

SOLUBILITY
Dissolving in water Fig 9.15
Saturation; dynamic equilibrium Fig 9.17
Classification (at ): Soluble; > 10 g/L
Slightly soluble; 0.1–10 g/L
Insoluble; < 0.1 g/L
Molar solubility
SOLUBILITY
Saturation; dynamic equilibrium

SOLUBILITY
"Like dissolves like" rule:

Polar liquids are good solvents for ionic or polar solutes,
and nonpolar liquids are good solvents for nonpolar solutes.
Fig 8.19
SOLUBILITY

SOLUBILITY

Surfactants (surface active agents);
amphiphilic with a hydrophilic head and a hydrophobic tail
Soaps; sodium salts of long-chain carboxylic acids
Detergent;
cleaning agent, usually a mixture containing surfactants
SOLUBILITY
9.10 Pressure and Gas Solubility: Henry's Law
At a constant temperature,
the solubility of a gas is proportional to its partial pressure P.
CO2 in beverages, O2 in blood, volatile pollutants,

pH of the rain, ···
SOLUBILITY
Dissolving rate vs. solubility
Temperature dependence of solubility
From Le Châtelier's principle

(better treatment should be done using the van't Hoff
equation, see ),
SOLUBILITY
For most gases near room temperature, .

⇒ It is likely that . ⇒ s decreases with T.
For most solids, .
⇒ It is likely that .
⇒ s increases with T.
For solids with ions hydrated

extensively in water, .
⇒ It is likely that .
⇒ s decreases with T.
Fig 9.22;
Na2SO4 · 10H2O (already hydrated)
vs. Na2SO4 (to be hydrated)
SOLUBILITY

SOLUBILITY
Enthalpy of solution
Limiting enthalpy of solution;

negligible solute-solute interactions in solution
Lattice enthalpy
High charge and small ionic radius

contribute to high ΔHL.
SOLUBILITY
Enthalpy of hydration
Exothermic (ΔHhyd < 0) for ionic compounds

and molecules forming hydrogen bonds with water
High charge and small ionic radius contribute

to high (large negative) ΔHhyd.
Nitrate (NO3–); big singly charged anion low ΔHL
Hydrogen bonds with water molecules

large negative ΔHhyd highly soluble
SOLUBILITY
Carbonate (CO32–); same size as nitrate but doubly charged

higher ΔHL much harder to break ions out of solids
Hydrogen carbonate (bicarbonate; HCO3–);

singly charged lower ΔHL more soluble than carbonate
Hard water; Ca2+, Mg2+
Temporary hardness vs. permanent hardness;

hydrogen carbonates vs. sulfates and/or chlorides
SOLUBILITY
Typically, ΔS > 0 when a solid dissolves. Fig 9.24
⇒ If ΔHsol < 0, then ΔG < 0; most substances

with negative ΔHsol are soluble.
Sometimes, ΔS < 0 when the solvent molecules

form cagelike structures around the solute.
⇒ If ΔHsol > 0, then ΔG > 0; insoluble

⇒ ΔG can be positive if ΔHsol is slightly negative;
heptane is insoluble in water although ΔHsol < 0.
When ΔHsol > 0, ΔG can be negative only if TΔS is large enough.

SOLUBILITY

SOLUBILITY
However, ΔG varies as the (dissolving) reaction proceeds.

⇒ Equilibrium (saturation)
Even when ,
the reaction proceeds
to the equilibrium ( ).
Temperature dependence of
solubility
SOLUBILITY
If and do not vary much with temperature,
van't Hoff equation

9.14 Molality
Colligative properties;
solvent properties which are affected by the number
of solute particles
Vapor-pressure lowering, boiling-point elevation,

freezing-point depression, osmosis
Mole fraction
9.14 Molality
Molarity & molality
Percent composition
9.14 Molality
Molarity
Molality
39
9.14 Molality
Parts per million, parts per billion, & parts per trillion
9.15 Vapor Pressure Lowering
Raoult's law for ideal solutions
Ideal solution; solute-solute

interactions are the same
as solute-solvent interactions
(ΔHsol = 0)
As xsolvent 1, nonideal solutions Ideal solutions; limiting law
Nonelectrolyte solution; < 0.1 M

Electrolyte solution; < 0.01 M
Stronger and longer range interactions between ions

9.15 Vapor Pressure Lowering

9.16 Boiling Point Elevation and

Freezing Point Depression
Boiling point elevation; for a vapor pressure of 1 atm,

Tb has to be increased to compensate for the vapor
pressure lowering.
Entropy (disorder) increase caused by the solute molecules

Lowering of Gm,solution(solvent)
Elevation of Tb to satisfy the equilibrium condition;
Gm,solution(solvent) = Gm,vapor(solvent)

For a dilute solution (< 10–3 M); i(NaCl) = 2; Na+ + Cl–

i(CaCl2) = 3; Ca2+ + 2 Cl–
HCl in benzene; i = 1, HCl in water; i = 2
Weak acid HA dissociating 5%, i = 0.95 + (0.05 2) = 1.05


Freezing point depression
Entropy (disorder) increase caused by the solute molecules

Lowering of Gm,solution(solvent)
Depression of Tf (Gm,solution(solvent) = Gm,solid(solvent))

9.17 Osmosis
Osmosis; flow of solvents through a semipermeable membrane

into a more concentrated solution
Large solutes, hydrated ions may not pass through

(depending on the membrane).
"Life depends on osmosis."
Cell walls Fig 9.32
Dehydration; salted meat
Entropy increase caused by the solute molecules
Lowering of Gm,solution (solvent)

Flow of solvent molecules (open system); osmosis
9.17 Osmosis
van't Hoff equation;

Jacobus van't Hoff (1887)
Osmometry; (very large) molar mass determination

Reverse osmosis;
reverse process of osmosis, squeezing water out of solution
Strong membrane, water purification, desalination

9.17 Osmosis
Vapor pressure of a mixture of volatile components

Separation by distillation

Composition of the vapor (yi) in equilibrium Fig 9.36
with the liquid mixture
The vapor is enriched in the more volatile component.


9.19 Distillation
9.19 Distillation
Fractional distillation
9.19 Distillation
9.19 Distillation
Mixture boils over a range of temperatures
(with different vapor compositions).
Distillation column; T decreases with height in the column

Fig 9.39
Petroleum refining tower
9.19 Distillation
9.20 Azeotropes
9.20 Azeotropes
Azeotropes
9.20 Azeotropes
THE IMPACT ON BIOLOGY AND MATERIALS
9.21 Colloids
9.21 Colloids
Suspension of particles to small to be seen

but large enough to scatter light
Tab 9.9 Classification of colloids (8 kinds)

9.21 Colloids
9.21 Colloids
Hydrophobic colloids; milk, mayonnaise
Hydrophilic colloids; gels, puddings, gelatin
Faraday's colloidal gold (1857)

Bio-based materials from natural

materials in living things
Hyaluronic acid (hyaluronan);

many –OH groups for hydrogen
bonding with water
Fig 9.46
Biological lubricants, healing of wounds and joint injuries
Biomimetic materials;
modeled after naturally occurring materials
Gels, flexible polymers ( Fig 19.9 ),

artificial spider silk ( Fig 19.23 ), ··· (Chapter 19)



Box 9.1 Drug delivery systems

Transdermal patches
Implants
Controlled-release drug delivery systems;
phospholipids, nanotechnology, smart gels, ···

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General Chemistry I (2022) Lecture by B. H.

Chapter 09. PHYSICAL EQUILIBRIA

PHASES AND PHASE TRANSITIONS

Chapter 09. PHYSICAL EQUILIBRIA

BINARY LIQUID MIXTURES

IMPACT ON BIOLOGY AND MATERIALS

Chapter 09. PHYSICAL EQUILIBRIA

Key Ideas Dynamic equilibrium;

Goal Transformation between states

9.1 Vapor Pressure

Dynamic equilibrium; no net flow of matter between phases

Independent of the direction (with enough material)

Rate of evaporation = rate of condensation

Vapor pressure increases with T;

Solid also exerts a vapor pressure; sublimation

9.2 Volatility and Intermolecular Forces

High (low) vapor pressure

Dimethyl ether (CH3–O–CH3; gas)

9.3 The Variation of Vapor Pressure with Temperature

Pressure dependence of the Gibbs free energy of an ideal gas

At constant T, P1 P2 (ideal gas)

By choosing P1 = 1 bar as the reference (standard) state

The Gibbs free energy of a liquid is almost independent

9.3 The Variation of Vapor Pressure with Temperature

For the phase equilibrium (not a standard state!)

9.3 The Variation of Vapor Pressure with Temperature

9.3 The Variation of Vapor Pressure with Temperature

Note that the Clausius-Clapeyron equation is a special case

Ex 8.1 At , the vapor pressure of CCl4 is

9.3 The Variation of Vapor Pressure with Temperature

9.4 Freezing and Melting

Evaporation vs. boiling

9.5 Freezing and Melting

Freezing point vs. normal freezing point Tf

Tf of most substances increases with P;

Solid inner core of the earth

9.6 Phase Diagrams

Gibbs phase rule: f=c–p+2

f; degrees of freedom, c; # of components, p; # of phases

# of independent mole fractions = c – 1 (x1 + ··· + xc = 1)

# of intrinsic variables = 2 (P and V) + p(c – 1)

⇒ Degrees of freedom = 2 + p(c – 1) – c(p – 1) = c – p + 2

9.6 Phase Diagrams

One-component phase diagram

9.6 Phase Diagrams

9.6 Phase Diagrams

9.6 Phase Diagrams

9.6 Phase Diagrams

Quadruple points never exist for a one-component system.

Positive slope of the solid-liquid

9.7 Critical Properties

Critical point (Tc, Pc) at the end of the liquid-vapor

Meniscus disappears at the critical point.

Supercritical fluid (T > Tc & P > Pc);

9.7 Critical Properties

9.8 The Limits of Solubility

Dissolving in water Fig 9.15