Liquids, Solids, and Phase

Changes
LECTURE 9
Part 1
• Physical States and Phase Diagrams
• Intermolecular Forces
• Some Properties of Liquids
• Solids: Types, Structure and Properties
PHASE
A phase is a homogeneous
part of the system in contact
with other parts of the system
but separated from them by a
well-defined boundary.

2 Phases
solid phase: ice
liquid phase: water
PHASE
Characteristic Properties of Gases, Liquids, and Solids
State of Motion of
Matter Volume/Shape Density Compressibility Molecules
Gas Assumes the Low Very Very free motion
shape and compressible
volume of its
container
Liquid Has a definite High Only slightly Slide past one
volume but compressible another freely
assumes the
shape of its
container
Solid Has a definite High Virtually Vibrate about
volume and incompressible fixed positions
shape
FORCES OF ATTRACTION
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.

Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
INTRAMOLECULAR FORCES OF ATTRACTION
IONIC COVALENT METALLIC

The force of attraction between two oppositely charged ions is

governed by Coulomb’s Law.

q+q-
Fa ∝
d2
q+ and q- are the ion charges
d is the distance between the ions
INTRAMOLECULAR FORCES OF ATTRACTION
IONIC COVALENT METALLIC

Coulomb’s Law determines:

1. The melting and boiling points of ionic compounds.
2. The solubility of ionic compounds.

Example:
Arrange the following ionic compounds in the expected
order of increasing melting and boiling points.
NaF, CaO, CaF2
INTRAMOLECULAR FORCES OF ATTRACTION
IONIC COVALENT METALLIC

Ionic substances containing multiply charged ions, (eg Al3+ , Mg2+ ,

O2- , S2- ) usually have higher melting/boiling points than singly
charged ions

For a series of ions of similar charge, the closer approach of smaller

ions results in stronger interionic attractions and consequently
higher melting/boiling properties
q+q-
Fa ∝ NaF, CaO, CaF2
d2
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
“measures” of intermolecular force
• boiling point
• melting point
• DHvap
• DHfus
• DHsub
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Dipole-Dipole Forces
• attractive forces between polar molecules
• occurs only for molecular compounds (covalently bonded
molecules) without charges

Orientation of Polar Molecules in a Solid

INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Hydrogen Bond
• The hydrogen bond is a special dipole-dipole interaction
between the hydrogen atom in a polar N-H, O-H, or F-H bond
and an electronegative O, N, or F atom.
A H… B or A H… A
A & B are N, O, or F
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Why is the hydrogen bond considered a “special” dipole-dipole
interaction?
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Hydrogen Bond
• H-bonding in water

around a molecule in the solid in the liquid

INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Which of the following can form hydrogen bonds with water?
1. CH3OCH3
2. CH4
3. F2
4. HCOOH
5. Na+
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Ion-Dipole Forces
• attractive forces between an ion and a polar molecule

Ion-Dipole Interaction
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Ion-Dipole Forces
• attractive forces between an ion and a polar molecule

Interaction of water and cations

INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
London Forces or Dispersion Forces
attractive forces that arise as a result of temporary dipoles
induced in atoms or molecules
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
London Forces or Dispersion Forces
attractive forces that arise as a result of temporary dipoles
induced in atoms or molecules

• instantaneous dipole- instantaneous dipole

interaction strictly between nonpolar molecules
• ion-induced dipole
interaction between an ion and a nonpolar molecule
• dipole-induced dipole
interaction between a dipole (polar) molecule and a nonpolar molecule
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
London Forces or Dispersion Forces
• attractive forces that arise as a result of temporary dipoles
induced in atoms or molecules

ion-induced dipole-induced
dipole interaction dipole interaction
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Dispersion Forces
• Polarizability is the ease with which the electron distribution in
the atom or molecule can be distorted.
• Polarizability increases with: Melting Points of Similar
greater number of electrons Nonpolar Compounds
more diffuse electron cloud Melting Point
Compound (oC)
CH4 -182.5
CF4 -150.0
CCl4 -23.0
CBr4 90.0
CI4 171.0
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
What type(s) of intermolecular forces exist between the
following pairs?
(a) HBr and H2S

(b) Cl2 and CBr4

(c) I2 and nitrate

(d) NH3 and CH3COCH3

(e) SO42- and NO

INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
In general, the trend for IMFA strength is:

ion-ion
ion-dipole
H-bonding
dipole-dipole
dipole-induced dipole
induced dipole-induced dipole
INTERMOLECULAR FORCES OF ATTRACTION (IMFA)
Which liquid in the following pairs has the higher boiling
point?
a. H2O and H2S
b. CH3CH2CH2OH and HOCH2CH2OH
c. CH3CH2CH3 and CH3CH2F
d. CH3CH2CH2CH3 and CH3CH3
THE CONDENSED PHASES: SOLIDS AND LIQUIDS
Condensed phase – phases in which particles react strongly
LIQUID STATE: PROPERTIES

Surface tension is a measure

of the unequal attractions
that occur at the surface of a
liquid; The molecules at the
surface are attracted
unevenly.
LIQUID STATE: PROPERTIES
Cohesive forces are the forces
that hold liquids together.
Adhesive forces are the forces
between a liquid and another
surface.

capillary capillary
rise fall
LIQUID STATE: PROPERTIES
Capillary action is the ability
of a liquid to rise (or fall) in a
glass tube or other container
LIQUID STATE: PROPERTIES
Viscosity is a measure of a Viscosity of Some Common
fluid’s resistance to flow. Liquids at 20 oC
Viscosity
Compound (N s/m2)
Acetone (C3H6O) 3.16 x 10-4
Benzene 6.25 x 10-4
Blood 4.00 x 10-3
Ethanol (C2H6O) 1.20 x 10-3
Glycerol (C3H8O3) 1.49
Water 1.01 x 10-3
LIQUID STATE: PROPERTIES
Vapor Pressure is the pressure exerted by a liquid’s vapor on its
surface at equilibrium
LIQUID STATE: PROPERTIES
Boiling point is the temperature at which the liquid’s vapor pressure
is equal to the applied pressure.
The normal boiling point is the boiling point when the pressure is
exactly 1 atm.
Distillation is a method we use to separate mixtures of liquids based
on their differences in boiling points.
LIQUID STATE: PROPERTIES
Higher IMFA strength leads to:

R higher boiling point

R lower vapor pressure (also means lower evaporation rate)
R stronger surface tension
R higher viscosity (more viscous liquid)
LIQUID STATE: PROPERTIES
All of the following substances are liquid at room temperature:

n-butane tert-butane n-butanol acetic acid acetone

Identify the liquid/s;

1) with highest polarity
2) with highest boiling point
3) that is most volatile
4) that can hydrogen bond
5) most viscous
PHASE CHANGES

SOLID

LIQUID GAS
HEAT TRANSFERS AND PHASE DIAGRAMS

Heat Transfers involving liquids

Xl,T1 Xl,T2 Xg,T2

q = mc∆T = nCp∆T
used when temperature changes

q = ∆Hphase transition • moles substance

only used at the temperature where phase change occurs
ISOTHERMAL heat transfer
HEAT TRANSFERS AND PHASE DIAGRAMS
EXAMPLE
How many joules of energy must be absorbed by 5.00 x 102 g of H2O(l)
at 50.0oC to convert it to steam at 120oC? The molar heat of
vaporization of water is 40.7 kJ/mol and the molar heat capacities of
liquid water and steam are 75.3 J/mol oC and 36.4 J/mol oC, respectively.
HEAT TRANSFERS AND PHASE DIAGRAMS
SOLUTION
1 2 3
H2O(l), 50 ºC➝ H2O(l), 100 ºC ➝ H2O(g), 100 ºC ➝ H2O(g), 120 ºC

q1 = nCp∆T = 27.78 mol (75.3 Jmol-1oC-1)(100-50)ºC = 104.59 kJ

q2 = ∆Hvap • molesH2O = 40.7 kJ mol-1 • 27.78 mol = 1130.65 kJ
q3 = nCp∆T = 27.78 mol (36.4 Jmol-1oC-1)(120-100)ºC = 20.22 kJ
qtotal = q1 + q2 + q3 = 1.26x103 kJ
LIQUID-VAPOR INTERFACE

Because the vapor (gas phase) is directly affected by pressure and

temperature changes, boiling process may occur at different
pressures
Normal boiling point occurs at 100oC at 1 atm. Is it the same if the
external pressure is decreased e.g. at higher altitudes?
LIQUID-VAPOR INTERFACE
The Clausius-Clapeyron Equation

determine vapor pressure of a liquid at a new T

determine what T we must heat something to get a specified vapor
pressure
way to determine ΔHvap if we know pressure at 2 Ts

You can only use this equation to calculate vapor pressure-

temperature at the equilibrium condition!
LIQUID-VAPOR INTERFACE
The normal atmospheric pressure is 630 torr when the gAang is flying
through Appa. At what temperature will the water boil if firebenders
attack Katara’s waterbent shield during their flight?

J3
630 torr40.7 x 10 1 1
ln = mol ( − )
760 torr 8.314 J 373 K T1
K mol
SOLID-LIQUID INTERFACE
The normal melting point is the temperature at which the solid melts
(liquid and solid in equilibrium) at exactly 1.00 atm of pressure.

The melting point increases as the strength of the intermolecular

attractions increase.
SOLID-LIQUID INTERFACE
At the solid-liquid interface, the external pressure directly affects the
volume of the condensed phase, hence the temperature at which it
melts/crystallizes.

The Clapeyron Equation: only used in solid to liquid interfaces

ΔHfus T1 −T2
P1 = P2 + ( )
ΔVfus T2
PHASE CHANGES

SOLID

LIQUID GAS
PHASE DIAGRAM
summarizes the conditions at which a substance exists as a solid,
liquid, or gas.
INTERPRETING PHASE DIAGRAM
Melting/freezing points
INTERPRETING PHASE DIAGRAM
Boiling points
INTERPRETING PHASE DIAGRAM
Sublimation points
INTERPRETING PHASE DIAGRAM

Critical Point

CRITICAL TEMPERATURE – above this

temperature, the gas cannot be liquefied
(gas and liquid phases not seen)

CRITICAL PRESSURE – the pressure

needed to liquefy the gas AT ITS critical
temperature

- Above the critical points, the substance

behaves as a SUPERCRITICAL FLUID
INTERPRETING PHASE DIAGRAM
Identify the following by providing the necessary parts (points or lines)
from the given phase diagram:

1. freezing points
2. sublimation points
3. boiling points
4. normal boiling point
1 atm 5. normal freezing point
6. three phases exist
7. substance changes from vapor
to liquid
8. substance melts
SOLIDS
Dependence of properties on structure:

rigidity/hardness – crystal form/lattice

melting point – strength of

atomic/molecular interactions

conductivity – electron distribution

along entire solid
TYPES OF SOLIDS ACCORDING TO STRUCTURE
Amorphous solids do not have a well-ordered molecular structure.
e. g. amorphous solids include waxes, glasses, asphalt.
Crystalline solids have well-defined structures that consist of extended
array of repeating units called unit cells.
CRYSTAL
Unit cells are the smallest repeating unit of a crystal.
TYPES OF SOLIDS ACCORDING TO BOND BETWEEN
PARTICLES
Molecular Solids Network Covalent

Ionic solids Metallic Solids

MOLECULAR SOLIDS
Molecular Solids have molecules in each of the positions of the unit cell.
• Molecules are held only by IMFAs
• Molecular solids have low melting points, are volatile, and are
electrical insulators.

Examples of molecular solids include:

• ice, sugar, dry ice (carbon dioxide), naphthalene
NETWORK COVALENT SOLIDS
Network Covalent Solids have atoms that are covalently bonded to one
another
Some examples of covalent solids are:
diamond, graphite, SiO2 (sand), SiC
IONIC SOLIDS
Ionic Solids have ions that occupy the positions in the unit cell.
Examples of ionic solids include:
CsCl, NaCl, ZnS
METALLIC SOLIDS
Metallic Solids - positively charged nuclei surrounded by a sea of
electrons.
Examples of metallic solids include:
• Na, Li, Au, Ag
THE SOLID STATE
The normal melting point is the temperature at which the solid melts
(liquid and solid in equilibrium) at exactly 1.00 atm of pressure.

The melting point increases as the strength of attraction increases.

Which requires more energy?

NaCl(s). ⇋ NaCl(l)

H2O(s) ⇋ H2O(l)
THE SOLID STATE

Variations in Melting Points for Molecular Solids

What are the intermolecular forces in each solid?

Compound Melting Point (oC)

ice 0.0
ammonia -77.7
benzene, C6H6 5.5
naphthalene, C10H8 80.6
benzoic acid, C6H5COOH 122.4
THE SOLID STATE

Variations in Melting Points for Ionic Solids

Compound Melting Point (oC)

LiF 842
LiCl 614
LiBr 547
LiI 450
BAND THEORY OF SOLIDS
Extension of MO theory to solids

Sodium’s 3s orbitals can interact to produce overlapping orbitals

BAND THEORY OF SOLIDS
The 3s orbitals can also overlap with unfilled 3p orbitals
BAND THEORY OF SOLIDS