Chapter 11

States of Matter; Liquids and Solids

Phase transitions - a change in substance from one state to another

Melting - change from a solid to a liquid state

Freezing - change of a liquid to the solid state

Vaporization - change of a liquid to the vapor state

Condensation - change of a gas to the liquid state

Sublimation - change of a solid directly to the vapor state.

Deposition – change of a gas directly to the solid phase.

Heat of Fusion - the heat needed for the melting of a solid. Also known as the enthalpy of
fusion, ∆Hfus

Heat of Vaporization - the heat needed for the vaporization of a liquid. Also known as the
enthalpy if vaporization, ∆Hvap.

Vapor Pressure of a liquid - the partial pressure of the vapor over the liquid measured at
equilibrium at a given temperature.
Rates of vaporization and condensation of liquid over time

Variation of vapor pressure with temperature

Boiling point - the pressure at which the vapor pressure of a liquid equals the pressure exerted
on the liquid (atm pressure).

Freezing point - the temperature at which a pure liquid changes to a crystalline solid, or freezes.

Melting point - the temperature at which a crystalline solid changes to a liquid, or melts.

Heating curve for water

Any change of state involves the addition or removal of energy as heat to or from the substance.

Calculating the Heat required for a Phase Change

Example:

Calculate the enthalpy change upon converting 1.00 mol of ice at -25°C to steam at 125°C under
a constant pressure of 1 atm. The specific heat of ice, water, and steam are 2.03, 4.18, and
1.84 J/g*K, respectively. For H2O, ΔHfus = 6.01 kJ/mol and ΔHvap = 40.67 kJ/mol.
The heat of vaporization of ammonia is 23.4 kJ/mol. How much heat is required to vaporize
1.00kg of ammonia? How many grams of water at 0ºC could be frozen to ice at 0ºC by the
evaporation of this amount of ammonia?

Clausius- Clapeyron Equation: vapor pressure of a substance depends on temperature.

Ln P = -(A/T) +B

P = the natural log of the vapor pressure A and B are positive constants,
assuming the vapor pressure behaves like an ideal gas, shows that the constant A is proportional
to the heat of vaporization of the liquid. If you make your y = lnP and x = 1/T

Examples:

Carbon disulfide, CS2, has a normal boiling point of 46°C and a heat of vaporization of 26.8 kJ/mol.
What is the vapor pressure of carbon disulfide at 35°C in mm Hg?
Selenium tetrafluoride is a colorless liquid. It has a vapor pressure of 757 mmHg at 105°C and
522 mmHg at 95°C. What is the heat of vaporization of selenium tetrafluoride?

Phase Diagrams
Solid liquid and gaseous states of H2O exist under different temperatures and pressure
conditions.

A phase diagram is a graphical way to summarize the conditions under which the different states
of a substance are stable.

Phase diagram for water

Triple point - the point in a phase diagram representing the temperature and pressure at which
three phases of a substance coexist in equilibrium

.
Phase Diagram of CO2 Phase Diagram of CH4
Critical Temperature - the temperature above which the liquid state of a substance no longer
exists regardless of the pressure.

Critical Pressure - the vapor pressure at the critical temperature.

Example:

Properties of Liquids; Surface Tension and Viscosity

Surface tension - the energy required to increase the surface area of a liquid by a unit amount.

Capillary rise is a phenomenon related to surface tension.

Viscosity - the resistance to flow that is exhibited by all liquids and gases.

Intermolecular forces - the forces of interaction between molecules, normally weakly attractive.

Three types of intermolecular forces are known to exist between neutral molecules.

1. London Dispersion forces

A weak attractive force between molecules resulting from the small, instantaneous
dipoles that occur because of the varying positions of the electrons during their motion at the
nuclei.
2. Dipole - dipole

An attractive intermolecular force resulting from the tendency of polar molecules to align
themselves such that the positive end of one molecule is near the negative end of another.

3. Hydrogen Bonding

A weak to moderate attractive force that exists between a hydrogen atom covalently
bonded to a very electronegative atom, X, and a lone pair of electrons on another small
electronegative atom, Y.

Example:

1. List the different intermolecular forces you would expect for each of the following
compounds:

A) propanol

B) methane

C) fluoromethane

2. Arrange the following hydrocarbons in order of increasing vapor pressure: ethane, propane,
butane, hexane.

Classification of Solids
Types of solids:
1. Molecular solid - a solid that consists of atoms or molecules held together by intermolecular
forces.

2. Metallic solid - consists of a positive core of atoms held together by a surrounding sea of
electrons.
3. Ionic solid - consists of cations and anions held together by the electrical attraction of opposite
charges.

4. Covalent network solid - consists of atoms held together in large networks or chains by
covalent bonds

Lattice Energy – the energy needed to separate a crystal into isolated ions.

Physical Properties:
Structural effects on:

Melting point - an increase in intermolecular forces gives an increase in melting points.

Hardness - depends on how easily the structural units of a solid can be moved relative to one
another.

Electrical Conductivity - dependent on the availability of delocalized valence electrons.

Structures of Solids:
Crystalline solid is composed of one or more crystals; each crystal has a well defined ordered
structure in 3 dimensions.

Example: table salt

Amorphous solid has a disordered structure; it lacks the well defined arrangement of basic units
found in a crystal.

Example: window glass

Q: Classify each of the following solids according to the forces of attraction that exist between
the structural units:

a. zinc, Zn b. sodium iodide, NaI c. silicon carbide, SiC d. methane, CH4

Q: Arrange the following elements in order of increasing melting point:

Silicon, hydrogen, lithium

Q: Decide what type of solid is formed for each of the following substances and arrange these in
order of increasing melting point:

C2H5OH, CH4, CH3Cl, MgSO4