Solid-Liquid-Gas

Associate Professor
Dr.Somsak Woramongkolchai

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

A crystalline solid possesses rigid and long-range order. In a

crystalline solid, atoms, molecules or ions occupy specific
(predictable) positions.
An amorphous solid does not possess a well-defined
arrangement and long-range molecular order.
A unit cell is the basic repeating structural unit of a crystalline
solid.
At lattice points:

lattice
point

Unit Cell

Unit cells in 3 dimensions

Atoms

Molecules

Ions

Shared by 8
unit cells

Shared by 2
unit cells

1 atom/unit cell

2 atoms/unit cell

4 atoms/unit cell

(8 x 1/8 = 1)

(8 x 1/8 + 1 = 2)

(8 x 1/8 + 6 x 1/2 = 4)

When silver crystallizes, it forms face-centered cubic

cells. The unit cell edge length is 409 pm. Calculate
the density of silver.
d=

m
V

V = a3 = (409 pm)3 = 6.83 x 10-23 cm3

4 atoms/unit cell in a face-centered cubic cell

1 mole Ag
107.9 g
-22
x
m = 4 Ag atoms x
=
7.17
x
10
g
23
mole Ag 6.022 x 10 atoms
7.17 x 10-22 g
m
3
=
=
10.5
g/cm
d=
V
6.83 x 10-23 cm3

Extra distance = BC + CD = 2d sin = n

(Bragg Equation)

X rays of wavelength 0.154 nm are diffracted from a

crystal at an angle of 14.170. Assuming that n = 1,
what is the distance (in pm) between layers in the
crystal?
n = 2d sin

n=1
n

= 14.170 = 0.154 nm = 154 pm

1 x 154 pm
=
= 77.0 pm
d=
2 x sin14.17
2sin

Types of Crystals
Ionic Crystals
Lattice points occupied by cations and anions
Held together by electrostatic attraction
Hard, brittle, high melting point
Poor conductor of heat and electricity

CsCl

ZnS

CaF2

Intermolecular Forces
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)

Measure of intermolecular force
Generally,
intermolecular
forces are much
weaker than
intramolecular
forces.

boiling point
melting point
Hvap
Hfus
Hsub

Types of Crystals
Covalent Crystals
Lattice points occupied by atoms
Held together by covalent bonds
Hard, high melting point
Poor conductor of heat and electricity
carbon
atoms

diamond

graphite

Types of Crystals
Molecular Crystals
Lattice points occupied by molecules
Held together by intermolecular forces
Soft, low melting point
Poor conductor of heat and electricity

Types of Crystals
Metallic Crystals
Lattice points occupied by metal atoms
Held together by metallic bonds
Soft to hard, low to high melting point
Good conductors of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell emobile sea
of e-

Types of Crystals

An amorphous solid does not possess a well-defined

arrangement and long-range molecular order.
A glass is an optically transparent fusion product of inorganic
materials that has cooled to a rigid state without crystallizing

Crystalline
quartz (SiO2)

Non-crystalline
quartz glass

Intermolecular Forces
Dipole-Dipole Forces
Attractive forces between polar molecules
Orientation of Polar Molecules in a Solid

Intermolecular Forces
Ion-Dipole Forces
Attractive forces between an ion and a polar molecule
Ion-Dipole Interaction

Intermolecular Forces
Dispersion Forces
Attractive forces that arise as a result of temporary
dipoles induced in atoms or molecules

ion-induced dipole interaction

dipole-induced dipole interaction

Intermolecular Forces
Dispersion Forces Continued
Polarizability is the ease with which the electron distribution
in the atom or molecule can be distorted.
Polarizability increases with:

greater number of electrons

more diffuse electron cloud

Dispersion
forces usually
increase with
molar mass.

What type(s) of intermolecular forces exist between

each of the following molecules?

HBr
HBr is a polar molecule: dipole-dipole forces. There are
also dispersion forces between HBr molecules.

CH4
CH4 is nonpolar: dispersion forces.

SO2

SO2 is a polar molecule: dipole-dipole forces. There are

also dispersion forces between SO2 molecules.

Intermolecular Forces
Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction
between they hydrogen atom in a polar N-H, O-H, or F-H bond
and an electronegative O, N, or F atom.
A

HB

or

A & B are N, O, or F

HA

Why is the hydrogen bond considered a

special dipole-dipole interaction?

Decreasing molar mass

Decreasing boiling point

Properties of Liquids
Surface tension is the amount of energy required to stretch
or increase the surface of a liquid by a unit area.

Strong
intermolecular
forces
High
surface
tension

Properties of Liquids
Cohesion is the intermolecular attraction between like molecules
Adhesion is an attraction between unlike molecules
Adhesion

Cohesion

Properties of Liquids
Viscosity is a measure of a fluids resistance to flow.

Strong
intermolecular
forces

High
viscosity

Water is a Unique Substance

Maximum Density
40C
Density of Water

Ice is less dense than water

T2 > T1

Condensation

Evaporation

Least
Order

Greatest
Order

The equilibrium vapor pressure is the vapor pressure

measured when a dynamic equilibrium exists between
condensation and evaporation
H2O (l)

Dynamic Equilibrium
Rate of
condensation

Rate of
evaporation

H2O (g)

Before
Evaporation

At
Equilibrium

Molar heat of vaporization (Hvap) is the energy required to

vaporize 1 mole of a liquid.
Clausius-Clapeyron Equation
Hvap
ln P = +C
RT

P = (equilibrium) vapor pressure

T = temperature (K)
R = gas constant (8.314 J/Kmol)

The boiling point is the temperature at which the

(equilibrium) vapor pressure of a liquid is equal to the
external pressure.
The normal boiling point is the temperature at which a liquid
boils when the external pressure is 1 atm.

The critical temperature (Tc) is the temperature above which

the gas cannot be made to liquefy, no matter how great the
applied pressure.

The critical pressure

(Pc) is the minimum
pressure that must be
applied to bring about
liquefaction at the
critical temperature.

The melting point of a solid

or the freezing point of a
liquid is the temperature at
which the solid and liquid
phases coexist in equilibrium

Freezing

H2O (l)

Melting

H2O (s)

Molar heat of fusion (Hfus) is the energy required to melt

1 mole of a solid substance.

Molar heat of sublimation

( Hsub) is the energy required
to sublime 1 mole of a solid.

Hsub = Hfus + Hvap

( Hesss Law)

Deposition

H2O (g)
Sublimation

H2O (s)

A phase diagram summarizes the conditions at which a

substance exists as a solid, liquid, or gas.

Phase Diagram of Water

Gases

Elements that exist as gases at 250C and 1 atmosphere

Physical Characteristics of Gases

Gases assume the volume and shape of their containers.

Gases are the most compressible state of matter.

Gases will mix evenly and completely when confined to

the same container.

Gases have much lower densities than liquids and solids.

Force
Pressure = Area

Units of Pressure
1 pascal (Pa) = 1 N/m2
1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa
Barometer

10 miles

4 miles
Sea level

0.2 atm

0.5 atm
1 atm

As P (h) increases

V decreases

Boyles Law

P 1/V
P x V = constant
P1 x V1 = P2 x V2

Constant temperature
Constant amount of gas

A sample of chlorine gas occupies a volume of 946 mL

at a pressure of 726 mmHg. What is the pressure of
the gas (in mmHg) if the volume is reduced at constant
temperature to 154 mL?

P1 x V1 = P2 x V2
P1 = 726 mmHg

P2 = ?

V1 = 946 mL

V2 = 154 mL

P1 x V1
726 mmHg x 946 mL
P2 =
=
= 4460 mmHg
154 mL
V2

As T increases

V increases

Variation of gas volume with temperature

at constant pressure.

Charles &
Gay-Lussacs
Law

VT
V = constant x T
V1/T1 = V2/T2

Temperature must be
in Kelvin
T (K) = t (0C) + 273.15

A sample of carbon monoxide gas occupies 3.20 L at

125 0C. At what temperature will the gas occupy a
volume of 1.54 L if the pressure remains constant?

V1/T1 = V2/T2
V1 = 3.20 L

V2 = 1.54 L

T1 = 398.15 K

T2 = ?

V2 x T1
T2 =
=
V1

1.54 L x 398.15 K
3.20 L

= 192 K

Avogadros Law
V number of moles (n)
V = constant x n
V1/n1 = V2/n2

Constant temperature
Constant pressure

Ammonia burns in oxygen to form nitric oxide (NO)

and water vapor. How many volumes of NO are
obtained from one volume of ammonia at the same
temperature and pressure?

4NH3 + 5O2
1 mole NH3

4NO + 6H2O
1 mole NO

At constant T and P
1 volume NH3

1 volume NO

Ideal Gas Equation

1
Boyles law: V (at
constant n and T)
P
Charles law: V T(at constant n and P)
Avogadros law: V n(at constant P and T)
nT
V
P

nT
nT
V = constant x
=R
P
P

R is the gas constant

PV = nRT

The conditions 0 0C and 1 atm are called standard

temperature and pressure (STP).
Experiments show that at STP, 1 mole of an ideal
gas occupies 22.414 L.

PV = nRT
(1 atm)(22.414L)
PV
R=
=
nT
(1 mol)(273.15 K)
R = 0.082057 L atm / (mol K)

What is the volume (in liters) occupied by 49.8 g of HCl

at STP?
T = 0 0C = 273.15 K

PV = nRT
nRT
V=
P

P = 1 atm
1 mol HCl
n = 49.8 g x
= 1.37 mol
36.45 g HCl

1.37 mol x 0.0821

V=
V = 30.6 L

Latm
molK

1 atm

x 273.15 K

Argon is an inert gas used in lightbulbs to retard the

vaporization of the filament. A certain lightbulb
containing argon at 1.20 atm and 18 0C is heated to
85 0C at constant volume. What is the final pressure of
argon in the lightbulb (in atm)?

PV = nRT

n, V and R are constant

nR
= P = constant
T
V
P1
P2
=
T1
T2

P1 = 1.20 atm
T1 = 291 K

P2 = ?
T2 = 358 K

T2
= 1.20 atm x 358 K = 1.48 atm
P2 = P1 x
291 K
T1

Density (d) Calculations

PM
m
d=
=
V
RT

m is the mass of the gas in g

M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M=
P

d is the density of the gas in g/L

Gas Stoichiometry

What is the volume of CO2 produced at 370 C and 1.00

atm when 5.60 g of glucose are used up in the reaction:
C6H12O6 (s) + 6O2 (g)

6CO2 (g) + 6H2O (l)

g C6H12O6

mol C6H12O6

5.60 g C6H12O6 x

6 mol CO2
1 mol C6H12O6
x
= 0.187 mol CO2
180 g C6H12O6
1 mol C6H12O6

V=

nRT
=
P

mol CO2

V CO2

Latm
x 310.15 K
molK
1.00 atm

0.187 mol x 0.0821

= 4.76 L

Daltons Law of Partial Pressures

V and T
are
constant

P1

P2

Ptotal = P1 + P2

Consider a case in which two gases, A and B, are in a

container of volume V.

nART
PA =
V

nA is the number of moles of A

nBRT
PB =
V

nB is the number of moles of B

PT = PA + PB
PA = XA PT

nA
XA =
nA + nB
PB = XB PT
Pi = Xi PT

nB
XB =
nA + nB

A sample of natural gas contains 8.24 moles of CH4,

0.421 moles of C2H6, and 0.116 moles of C3H8. If the
total pressure of the gases is 1.37 atm, what is the
partial pressure of propane (C3H8)?

Pi = Xi PT

PT = 1.37 atm

Xpropane =

0.116
8.24 + 0.421 + 0.116

= 0.0132

Ppropane = 0.0132 x 1.37 atm = 0.0181 atm

Bottle full of oxygen

gas and water vapor

2KClO3 (s)

2KCl (s) + 3O2 (g)

PT = PO2 + PH 2O

Kinetic Molecular Theory of Gases

1. A gas is composed of molecules that are separated from
each other by distances far greater than their own
dimensions. The molecules can be considered to be points;
that is, they possess mass but have negligible volume.
2. Gas molecules are in constant motion in random directions.
Collisions among molecules are perfectly elastic.
3. Gas molecules exert neither attractive nor repulsive forces
on one another.
4. The average kinetic energy of the molecules is proportional
to the temperature of the gas in kelvins. Any two gases at
the same temperature will have the same average kinetic
energy

Kinetic theory of gases and

Compressibility of Gases
Boyles Law
P collision rate with wall
Collision rate number density
Number density 1/V
P 1/V

Charles Law
P collision rate with wall
Collision rate average kinetic energy of gas molecules
Average kinetic energy T
PT

Kinetic theory of gases and

Avogadros Law
P collision rate with wall
Collision rate number density
Number density n
Pn

Daltons Law of Partial Pressures

Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = Pi

Apparatus for studying molecular speed distribution

The distribution of speeds

of three different gases
at the same temperature

The distribution of speeds

for nitrogen gas molecules
at three different temperatures

urms =

3RT
M

Gas diffusion is the gradual mixing of molecules of one gas

with molecules of another by virtue of their kinetic properties.

NH4Cl

NH3
17 g/mol

HCl
36 g/mol

Deviations from Ideal Behavior

1 mole of ideal gas

PV = nRT
PV = 1.0
n=
RT

Repulsive Forces

Attractive Forces

Effect of intermolecular forces on the pressure exerted by a gas.