SOLIDS, LIQUIDS,

10
CHAPTER
AND PHASE TRANSITIONS

10.1 Bulk Properties of Gases, Liquids, and Solids:

Molecular Interpretation
10.2 Intermolecular Forces: Origins in Molecular
Structure
10.3 Intermolecular Forces in Liquids
10.4 Phase Equilibrium
10.5 Phase Transitions
10.6 Phase Diagrams

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I2(s)

I2(g)

I2(s)

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10.1 BULK PROPERTIES OF GASES, LIQUIDS,
AND SOLIDS: MOLECULAR INTERPRETATION
 Molar Volume
Solids, liquids: 10–100 cm3 /mol, 3–5 Å between molecules
(cf. bond lengths; 0.5–2.5 Å)
Gases: 24000 cm3 /mol, ~30Å between molecules

Fig. 10.1 Intermolecular

forces create structure in
liquids and solids.
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 Compressibility
1  dV 
 Isothermal compressibility, κT = −  
V  dP T
~ Fractional volume decrease against the pressure increase
Solids, liquids: nearly incompressible, (nearly) in contact,
strong intermolecular forces
Gases: highly compressible, space between molecules

 Thermal Expansion
 Thermal Expansion Coefficient, α
~ Fractional volume increase against the temperature increase
1  ∂V 
α=  
V  ∂T  P

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 Ideal gas
1  ∂V  1  ∂ ( nRT / P )  1 nR dT nR 1
α
=  =   =  = =
V  ∂T  P V  ∂T  P V P dT nRT T

At 0oC, → 0.366% volume increase

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 Fluidity and Rigidity
- Fluidity of gases and liquids vs. rigidity of solids
- shear viscosity: the resistance of a material to macroscopic flow
most liquids 16 orders of magnitude smaller than those of solids

 Diffusion
- Molecules of one type migrate into regions initially occupied only
by the other type.

- diffusion constant: measuring the rate of diffusive mixing

- In liquids, quickly changing the neighbors and finding new

interactions due to low shear viscosity
In solids, a durable arrangement of neighbors

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Fig. 10.2 Computer simulated picture of the motion of atoms in a

tiny melting crystal, the atoms at the center(in the solid) moves erratically
about the particular sites. The atoms at the surface (in the liquid) move
much greater distance.

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◈ Surface tension, γ
→ Resistance of the surface of a liquid to an increase in its
area in unit of N·m–1 or J·m–2
→ Surface tension is the net inward pull of surface molecules.
→ Liquids with strong intermolecular interaction have high
surface tension.

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Fig. 10.3 (a) Spherical shape of a water droplet after it hits the surface
of a pool and bounced up. (b) A water drop and a mercury drop at the
dropper tip. The mercury drop is a perfect sphere whereas the water
drop sags slightly due to difference in the surface tension.
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TABLE. Interionic and Intermolecular Interactions

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10.2 INTERMOLECULAR FORCES: ORIGINS IN
MOLECULAR STRUCTURE
 Ion-Ion Forces
 Strong, Long-range, Not directional
1
U∝ Coulombic potential
R

 Dipole-Dipole Forces

 Depends on orientations of two dipolar molecules.

1
 Potential energy between two dipoles ∝
R3
~ shorter range than Coulomb potential

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 Weaker than thermal energy:
~ Can not hold a rigid molecular assembly
 Strong enough to influence b.p., m.p., and molecular orientations

Fig 10.5 The dipole-dipole forces between two HCl molecules depend
on their orientations.
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 Ion-Dipole Forces
1
 Potential energy between ion and dipole ∝ 2
R
 Dissolution of salts in water (polar solvent)

Fig 10.6 Na+ and Cl− ions are surrounded by water dipoles.
Orientation of water molecules are reversed.

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 Charge-Induced Dipole Forces
1
 Potential energy between ion and induced dipole ∝
R4
 Weak and short range
 Electrical polarizability
~ Relative tendency of a charge distribution to be distorted
from its normal shape by an external electric field
~ Measure by the magnitude of the induced dipole moment

Fig. 10.7 Distortion of electron distribution of Ar as an ion is approached.

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 Induced Dipole-Induced Dipole Forces
1
 Potential energy between two induced dipoles ∝
R6
 Weak (~1 kJ/mol) and short range,
 Attraction between Ar atoms: London dispersion force
Fluctuation of electron distribution in one molecule
→ Temporary dipole
Second temporary dipole in the other → ···

Fig. 10.8 A fluctuation of the electron distribution on one atom induces

a corresponding
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- A large molecule is likely to have a
stronger London interactions than
a smaller one.

C5H12; mobile liquid

C15H32; viscous liquid
C18H38; waxy solid

- Halogens: gases (F2, and Cl2); liquid (Br2); solid (I2)

- Rod-shaped (pentane; Tb = 36 oC) vs.
spherical (2,2-dimethylpropane; Tb = 10 oC)

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◈ INTERACTIONS
Q1Q2
▶ Ion – Ion (Coulomb): EP =
4πε 0 r
▶ Ion – Dipole: E ∝ − z µ
P
r2
µµ
▶ Dipole – Dipole: E P ∝ − 1 3 2
r
▷Rotating polar gas molecules*:
µ1µ2
EP ∝ −
r6
µ12α 2
▶ Dipole – Induced dipole*: E P ∝ − 6
r
▶ London (dispersion)*: α1α 2
(Induced dipole – EP ∝ − 6
r Potential Energies
Induced dipole) between ions,
C ions and dipoles,
* Van der Waals interactions EP ∝ − 6 stationary dipoles, and
r rotating dipoles.
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Ar + Ar : dispersion only

HCl + HCl : dipole-dipole

and dispersion

Cl + Cl : covalent interaction

K+ + Cl- : ion-ion interaction

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 Shape of Molecules and Electrostatic Forces
 Electrostatic potential energy map
~ Shows the shape and size of the molecule, the sign and
magnitude of the electrostatic potential at the “surface” of
the molecule.

Fig. 10.10 Electrostatic potential Fig. 10.11 Electrostatic potential

energy map of acetone. energy map of acetaldehyde.

→ The dipole moment and charge separation are shown in both figures.
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10.3 INTERMOLECULAR FORCES IN LIQUIDS

 Hydrogen bonding, ~ 20 kJmol-1
H bonded to O, N, F (electronegative, lone-pair) interacts with
a lone electron pair of another nearby O, N, or F
O—H·······:O linear but asymmetric
Strong electrostatic interaction; stronger than most intermolecular
interactions Ex. H2O, HF, NH3

Fig. 10.13 A single hydrogen bond between water molecules forms

a dimer and the electrostatic potential energy map for H2O.
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Fig. 10.12 The boiling points of hydrides of some main group

elements and
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The structure of ice

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 Special Properties of Water
Maximum density at 3.98°C, high Tb , high heat capacity

Density of ice is smaller than water!

Ice remains
General atI the surface. Warm water under the ice.
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- Hydrogen fluoride, (HF)n - Acetic acid dimer (vapor)

- upright - DNA
trees double
strand

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Example

Identify the kinds of intermolecular forces that might arise between

molecules of each of the following substances:

(a) NH2OH; (b) CBr4; (c) H2SeO4; (d) SO2

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10.4 PHASE EQUILIBRIUM

 Phase ~ a sample of matter uniform throughout in both
chemical and physical states
 Phase Equilibrium
dynamic process; no net flow of matter between phases
rate of evaporation = rate of condensation
independent of the direction (with enough material)

Fig.Chemistry
General 10.16 Approach
I to equilibrium in evaporation and condensation.
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Fig. 10.17 Vapor pressure vs. temperature. The temperature at which the vapor
pressure becomes 1 atm defines the normal boiling point of liquid and the
normal sublimation point of a solid.

Pvapor(water) = 0.03126 atm (at 25°C)

= 1 atm (at 100oC) ← normal boiling point
Pvapor(CO2) = 1 atm (at –78.5oC) ← normal sublimation point
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10.5 PHASE TRANSITIONS

~ Transformation of a thermodynamic system from one
phase or state of matter to another

P = 4.52 atm
V = 5.50 L (Ideal gas: PV = nRT)
= 4.74 L (van der Waals Eq.)
P > 4.52 atm
liquefying (l), freezing (s)

 Liquefying:
intermolecular attractions
> kinetic energy (3/2 RT)

Fig. 10.18. Compression of 1 mol SO2 at 30oC.

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 Phase transitions between three states
Condensation →

Gas ←
Evaporation
 Liquid Boiling point, Tb
Freezing
Liquid 
← → Solid Melting (Freezing) point, Tf
Melting

Deposition
Gas 
← → Solid Sublimation point, Ts
Sublimation

 Superheating
~ Raising the temperature of a liquid
above its f.p. without it becoming a gas

 Supercooling (undercooling)
~ Lowering the temperature of a liquid or
a gas below its f.p. without it becoming
a solid
Fig. 10.19 Six phase transitions.
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10.6 PHASE DIAGRAMS

 Phase Diagram
A plot of P vs. T showing the stable state of a substance
Phase boundaries, Triple point, Critical point
 Triple point
Three phases coexist in equilibrium
T = 0.01oC, P = 0.006 atm for water
 Critical point
Terminal point of liquid-gas boundary
Supercritical fluid ~ no phase boundary (no meniscus)
~ critical opalescence
Tc = 374.2 oC, Pc = 218 atm for water

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 Critical point
Tc = 374.2oC
Pc = 218 atm

 Triple point
Tt = 0.01oC
Pt = 0.006 atm

Fig. 10.21 Phase diagram for water.

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above Tc

• Supercritical fluid – formally a gas, but is dense

as a liquid phase and can act as a solvent for
liquids and solids.

supercritical CO2: solvents for green chemical

reactions; no use of harmful solvents and
rapid extraction due to high mobility
i.e.) removing caffeine from coffee beans

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Fig. 10.23 Phase diagrams of Ar, CO2, and water.

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high
pressure

liquid layer

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General Chemistry I
 10 Problem Sets

For Chapter 10,

8, 16, 22, 26, 32, 36, 42, 50, 56, 62

General Chemistry I