PRINCIPLES OF CHEMISTRY II

CHEM 1212

CHAPTER 11

DR. AUGUSTINE OFORI AGYEMAN

Assistant professor of chemistry
Department of natural sciences
Clayton state university
 CHAPTER 11

LIQUIDS AND SOLIDS

KINETIC MOLECULAR THEORY

- Three physical states

Solids
Liquids
Gases

- Distinguished by five physical properties of matter

 KINETIC MOLECULAR THEORY

The physical state of matter depends on

- the strengths of the intermolecular attractions

- The average kinetic energy of the molecules

Intermolecular forces: forces between particles

Intramolecular forces: forces within particles (chemical bonds)

 KINETIC MOLECULAR THEORY

- Atoms and molecules possess kinetic energy since they have

mass and are in motion

- Molecules have no tendency of sticking together when the

average kinetic energy is greater than the attractive
energy between the molecules
 KINETIC MOLECULAR THEORY
- Matter is composed of tiny particles (atoms, molecules,
or ions) that have definite and characteristic sizes that do
not change

- The particles are in constant random motion and therefore

possess kinetic energy (velocity)

- The particles interact with one another through attraction

and repulsion and therefore possess potential energy

Electrostatic Interaction
- Unlike charges attract and like charges repel
 KINETIC MOLECULAR THEORY

- The average kinetic energy of molecules is proportional to

the absolute temperature

- Some molecules have less energy than the average whereas

others have more than the average
(Maxwell-Boltzmann Distribution)

- The particles in a system transfer energy to each other through

elastic collisions
(kinetic energy remains constant)
 KINETIC MOLECULAR THEORY

Elastic Collision
Two objects collide, bounce off, and continue moving
(two tennis balls or molecules)

Inelastic Collision
Two objects collide and stick together with no resulting movement
(two balls of putty or mashed potatoes)
 PHYSICAL STATE
Five physical properties of matter

- Volume

- Shape

- Density

- Compressibility
(change in volume due to pressure change)

- Thermal expansion
(change in volume due to temperature change)
 PHYSICAL STATE

Five physical properties of matter are used to distinguish between

the three physical states: solids, liquids, and gases

Property Solid Liquid Gas

volume definite volume definite volume indefinite volume

shape definite shape indefinite shape indefinite shape
density high high (< solid) low
compressibility small small (> solid) large
thermal expansion small small (> solid) moderate
 PHYSICAL STATE

Solid
Attractive energy > > kinetic energy of molecules

Liquid
Attractive energy ≈ kinetic energy of molecules

Gas
Attractive energy < < kinetic energy of molecules
 PHYSICAL STATE: SOLIDS

- Potential energy (cohesive forces) domineer over

kinetic energy (disruptive forces)

- Particles are drawn close together in a regular pattern by

the strong cohesive forces present

- Particles occupy and vibrate about fixed positions

(vibrations are due to the disruptive forces present)
 PHYSICAL STATE: SOLIDS

Properties

- Definite volume due to strong cohesive forces

- Definite shape due to strong cohesive forces resulting in

fixed particle positions

- High density due to closely packed particles

- Increased pressure has little effect (small compressibility)

- Increased temperature has little effect (small thermal expansion)

 PHYSICAL STATE: LIQUIDS

- Potential energy (cohesive forces) and kinetic energy

(disruptive forces) have similar magnitudes

- Particles are randomly packed but relatively near one another

- Particles freely slide over each other (due to disruptive forces)

- Cohesive forces are fairly strong and particles do not separate

 PHYSICAL STATE: LIQUIDS
Properties

- Definite volume due to fairly strong cohesive forces

- Indefinite shape since cohesive forces are not strong enough to

prevent particles from sliding over each other
(takes the shape of its container)

- High density but less than solid (particles are not widely separated)

- Increased pressure has little effect (small compressibility)

- Increased temperature has little effect (small thermal expansion)

 PHYSICAL STATE: GASES

- Complete dominance of kinetic energy (disruptive forces) over

potential energy (cohesive forces)

- Particles move randomly and independently of one another

- Particles move in straight lines until they collide with

one another or with the walls of the container
 PHYSICAL STATE: GASES
Properties

- Indefinite volume
(cohesive forces are overcome by kinetic energy)

- Indefinite shape since disruptive forces dominate completely

(takes the shape of its container and completely fills the container)

- Low density (particles are widely separated)

- Increased pressure decreases gas volume (large compressibility)

- Increased temperature increases particle velocity

(moderate thermal expansion)
 PHASE CHANGES
- A process in which a substance is transformed from one
physical state to another physical state

- Most substances can exist in all three states depending on

the temperature and pressure

- Chemical composition remains constant

- Usually accomplished by heating or cooling a substance

(a substance absorbs or releases heat)

Endothermic Change: heat energy is absorbed

Exothermic Change: heat energy is released

 PHASE CHANGES

Six terms used in describing change of state

Melting
- Change from solid state to liquid state
- Heat energy is absorbed

Freezing
- Change from liquid state to solid state
- Heat energy is released
 PHASE CHANGES

Six terms used in describing change of state

Evaporation
- Change from liquid state to gaseous state
- Heat energy is absorbed

Condensation
- Change from gaseous state to liquid state
- Heat energy is released
 PHASE CHANGES

Six terms used in describing change of state

Sublimation
- Change from solid state to gaseous state
- Heat energy is absorbed

Deposition
- Change from gaseous state to solid state
-Heat energy is released
 PHASE CHANGES
gas

Condensation Evaporation
Heat released Heat absorbed

Deposition Sublimation
Heat released liquid Heat absorbed

Freezing Melting
Heat released Heat absorbed

solid
 EVAPORATION OF LIQUIDS
- Evaporation occurs when molecules escape from the liquid phase
to the gas phase

- Evaporation is a surface phenomenon (it is easier for surface

molecules to escape since they are not completely surrounded by
other molecules and are subject to fewer attractive forces

- Rate of evaporation increases with increased surface area

- Rate of evaporation increases with increasing temperature

- Evaporation causes decrease in the amount of liquid and

lowering of liquid temperature
 VAPOR PRESSURE

- Molecules that escape to the gas phase are collectively

known as vapor

- Vapor pressure is pressure exerted by a vapor above a liquid

when the liquid and vapor are in equilibrium with each other

- Rate of evaporation is equal to rate of condensation

at equilibrium

- Vapor pressure depends on the nature and temperature

of the liquid
 VAPOR PRESSURE

- Liquids with strong attractive forces between molecules have

lower vapor pressures than liquids with weak attractive forces

- Substances with weak attractive forces between molecules that

readily evaporate at room temperature are said to be volatile
 VAPOR PRESSURE

- Vapor pressure increases with increase in temperature

- Rate of evaporation and equilibrium vapor pressure increase

with increasing temperature

State of Dynamic Equilibrium

- Two opposing changes occur at equal rates

- There is no net apparent change

 VAPOR PRESSURE
Evaporation

Rate
Condensation

Time

- Rate of evaporation is constant at constant temperature

- Rate of condensation increases and becomes equal to

rate of evaporation

- State of dynamic equilibrium reaches

 BOILING

- Vapor pressure increases with increase in temperature until it

becomes equal to the external pressure above the liquid
(atmospheric pressure for open containers)

- Vapor bubbles begin to form, rise to the surface, and escape

- This process is known as boiling

 BOILING

Boiling Point
- The temperature at which the vapor pressure of a liquid
becomes equal to the external pressure exerted on the liquid

- Kinetic energy overcomes the intermolecular forces

Normal Boiling Point

- The temperature at which a liquid boils under a pressure
of 1 atm (760 mmHg)
 LIQUID-VAPOR EQUILIBRIUM
Enthanlpy of Vaporization (ΔHvap)
- The enthalpy change that accompanies the conversion of 1 mol
of a substance from the liquid state to the gaseous state at
constant temperature

Evaporation results in
- lower average kinetic energy
- lower temperature
(unless heat is added)

- Implies vaporization is an endothermic process

- The stronger the intermolecular attractions the greater the ΔHvap

 LIQUID-VAPOR EQUILIBRIUM

Vaporization

H2O(l) → H2O(g) ΔHvap = +44.0 kJ/mol

Condensation (opposite of vaporization)

H2O(g) → H2O(l) ΔHcon = -44.0 kJ/mol

 LIQUID-VAPOR EQUILIBRIUM

Calculate the energy necessary to boil 120.0 g of water at its

normal boiling point
(B. P. = 100.0 oC, ΔHvap = +44.0 kJ/mol)

Molar mass H2O = 18.02 g/mol

1mol H 2 O
mol H 2 O  120.0 g H 2 O x  6.659 mol H 2 O
18.04 g H 2 O

44.0 kJ
ΔH vap  6.659 mol H 2 O x  293.0 kJ
mol
 LIQUID-VAPOR EQUILIBRIUM

What is the enthalpy change when 150.0 g of hydrogen chloride

condenses at its boiling point
(B. P. = -83.7 oC, ΔHvap = +15.1 kJ/mol)

ΔHcon = -15.1 kJ/mol

Molar mass HCl = 36.46 g/mol

1 mol HCl
mol HCl  150.0 g HCl x  4.114 mol HCl
36.46 g HCl

- 15.1 kJ
ΔH con  4.114 mol HCl x  - 62.12 kJ
mol
 CRITICAL TEMPERATURE

- The maximum temperature at which a substance can exist

in the liquid state

- Substance remains in the ‘gaseous state’ above

the critical temperature
(irrespective of the applied pressure)

- Depends on the strength of intermolecular forces

- Substances with strong intermolecular forces have high

critical temperatures
 CRITICAL PRESSURE
- The minimum pressure needed to liquefy the substance at the
critical temperature

SUPERCRITICAL FLUID
- The single phase that exists above
the critical temperature and pressure
 LIQUID-SOLID EQUILIBRIUM
Melting Point
- The temperature at which the solid and liquid phases are in
equilibrium

- Particles have enough kinetic energy to overcome the

intermolecular forces that are keeping the particles
in fixed position

Enthalpy of Fusion (ΔHfus)

- The enthalpy change that accompanies the conversion of 1 mol
of a substance from the solid state to the liquid state at
constant temperature (Endothermic process)
 LIQUID-SOLID EQUILIBRIUM

Melting

H2O(s) → H2O(l) ΔHfus = +6.01 kJ/mol

Freezing/Solidification (opposite of melting)

H2O(l) → H2O(s) ΔHfreez = -6.01 kJ

For any substance, ΔHvap > ΔHfus

 HEATING CURVE FOR H2O

C
Temperature, oC

100
D

A
0
B

Heat added
 HEATING CURVE

- Heat capacity of a substance determines the rate of

temperature change

- At the melting point, temperature remains constant as long as

both solid and liquid phases are present (A to B)

- Heat added at the melting point is used to overcome the

attractive forces between solid molecules
(well-stirred ice and water at 0oC)
 HEATING CURVE

- Temperature rises after all solid has been converted to liquid

(B to C)
(determined by the heat capacity of the liquid)

- At the normal boiling point, the temperature stays constant again

(C to D)

- Added heat is used to overcome the intermolecular attractions

 HEATING CURVE

- Temperature increases again after sample is completely vaporized

(determined by the heat capacity of the vapor)

- Lengths of constant temperature portions are proportional to the

enthalpies of fusion and vaporization
 SOLID-GAS EQUILIBRIUM

Sublimation
- The direct conversion of a substance from the solid state to the
gaseous state

Deposition
- Conversion of a gas directly to the liquid state

Examples
I2(s) ↔ I2(g)

CO2 (dry ice) sublimes at normal pressure

 SOLID-GAS EQUILIBRIUM

Enthanlpy of Sublimation (ΔHsub)

- The enthalpy change for conversion of one mole of a solid

to the gaseous state

(Process is endothermic)
 Increasing energy

Deposition

Sublimation
Gas

Condensation

Solid
Vaporization

Freezing
Liquid
ENTHALPY DIAGRAM

Fusion or
Melting
 PHASE DIAGRAM
Pressure

C
Solid Liquid

1 atm

T Gas

Temperature
 PHASE DIAGRAM

- The physical state of a substance reflects the strength of

intermoleculer attractions

- Temperature and pressure determine which phase is stable

- A phase diagram is a graph of pressure versus temperature

- Shows the region of stability for each of the physical states

- Three line segments show the pressure and temperature at which

any two phases exist in equilibrium
 PHASE DIAGRAM

- Shows three regions separated by the line segments

- Only one phase is present in each region

Vapor Pressure Curve

- The line separating the liquid from the gas
 PHASE DIAGRAM
Triple Point

- Unique combination of pressure and temperature at which all

three phases exist in equilibrium (point T)

- Occurs where the three equilibrium lines meet (point T)

- A liquid boils and freezes at the same temperature and pressure

The triple point of CO2 is at -56.4 oC and 5.11 atm
The triple point of H2O is at 0.0098 oC and 4.58 torr
 PHASE DIAGRAM

- The liquid gas equilibrium line ends at the critical point (C)

- Only one fluid phase exists above the critical pressure

This fluid phase is considered to be

- a liquid below the critical temperature

- a gas above the critical temperature

 PHASE DIAGRAM

Using the phase diagram of a given substance

- A horizontal line at constant pressure meets

the solid-liquid line at the freezing point

the liquid-vapor line at the boiling point

- The substance sublimes if the constant pressure line is lower

than the triple-point pressure
 PHASE DIAGRAM
Effect of pressure

- The solid-liquid equilibrium line is nearly vertical

(Unlike the liquid-gas and the solid-gas equilibrium lines)

- Melting point changes very slightly with change in pressure

(Unlike boiling point and sublimation temperature)

- Large difference between densities of gas and liquid phases

(~ 1000 x)

- Effect of pressure on the liquid-gas equilibrium

is much greater than solid-liquid equilibrium
 PHASE DIAGRAM
Effect of pressure

- Generally, increase in pressure results in decrease in volume

- For two phases in equilibrium, decrease in volume is a result

of the formation of a denser phase

For example
- Solid CO2 is denser than liquid CO2
- An increase in pressure of solid and liquid CO2 at equilibrium
reduces the volume by forming the solid from the liquid CO2
- Melting point increases with increase in pressure
 PHASE DIAGRAM
Effect of pressure

By contrast

- Solid H2O is less dense than liquid H2O

- Reason why ice floats on water
- An increase in pressure results in increase in volume
- An increase in pressure causes some of the solid to melt
- Melting point decreases with increase in pressure

You cannot use salt to melt ice and snow when the temperature
is below -21oC
 INTERMOLECULAR FORCES
- Attractive forces between molecules

Intramolecular Forces
- Attractive forces within molecules (covalent and ionic bonding)

- Intermolecular forces are weaker than intramolecular forces

Three main types of intermolecular forces

- Dipole-dipole interactions
- London dispersion forces
- Hydrogen bonds

Electrostatic attraction
Attraction between charges of opposite sign
 INTERMOLECULAR FORCES
Dipole-dipole Interactions
- Occurs between polar molecules

- A polar molecule has a negative end and a positive end (a dipole)

(partial positive and partial negative charges are due to
unequal sharing of electron pairs)

- The positive end of one molecule attracts the negative end of

another molecule

- The greater the polarity of the molecule (greater dipole moment),

the greater the strength of dipole-dipole interactions,
and consequently, the higher the boiling point of the liquid
(ClF-chlorine monofluoride)
 INTERMOLECULAR FORCES
London Dispersion Forces
- A weak temporary intermolecular force that occurs between
an atom or molecule (polar or nonpolar) and another atom or
molecule (polar or nonpolar)

- Result from uneven distribution of electrons in molecules

(induced polarity)

- Happens several times per second throughout a liquid

- The larger the molecules (molar masses),

the higher the strength of London forces,
and the higher the boiling point of the liquid
 INTERMOLECULAR FORCES

Polarizability

- The ease with which the electron cloud of a molecule is

distorted by a nearby charge

- Increases with size of electron cloud

- Greater number of electrons in a molecule implies

more polarizable

- Induced dipole increases with increase in polarizability

and magnitude of electrostatic attraction increases
 INTERMOLECULAR FORCES

Polarizability

In general
dispersion forces dominate over dipole-dipole interactions
when the strengths of the two types of forces predict
different trends in boiling points

- Dipole-dipole and dipole-induced forces are collectively called

van der Waals forces
 INTERMOLECULAR FORCES
Hydrogen Bonding

- Dipole-dipole interactions in hydrogen-containing molecules

- Occurs between a hydrogen atom (which is covalently

bonded to a highly electronegative element of small
atomic size) and a lone pair of electrons on another small,
highly electronegative atom
- Small highly electronegative atoms: F, O, N
(HF, H2O, NH3)

- Highly polar (due to high electronegativity and small size)

resulting in extra bond strength
 INTERMOLECULAR FORCES
Hydrogen Bonding

- Small size of hydrogen allows stronger attraction to

lone pair of electrons on the electronegative atom,
also resulting in extra bond strength

- Up to 30 kJ/mol compared to less than 4 kJ/mol of other

intermolecular forces

- Weaker than covalent bonds (140 – 600 kJ/mol)

- Longer than covalent bonds

H-bond in H2O ~177 pm
Covalent bond is H2O ~99 pm
 PROPERTIES OF LIQUIDS

Surface Tension In Liquids

- The energy necessary to increase the surface area of a liquid

Units: J/m2

- The stronger the intermolecular forces the higher the

surface tension

- A small drop of any liquid assumes a spherical shape due to

surface tension
 PROPERTIES OF LIQUIDS
Consider a liquid in a beaker

- Molecules in the interior are attracted by surrounding molecules

equally in all directions

- Molecules at the surface are attracted towards the interior so

has a net force towards the interior (no molecules above)

- Liquids adopt a spherical shape (smallest surface area) due to

the unbalanced force

- Energy is required to increase the surface area known as the

SURFACE TENSION
 PROPERTIES OF LIQUIDS
Capillary Action

- Cause water to rise in a small-diameter glass tube (capillary tube)

- A result of intermolecular attractions

- Two kinds of intermolecular attractions involved

Cohesive forces
- Attractions between molecules of the same substance

Adhesive forces
- Attractions between molecules of different substances
 PROPERTIES OF LIQUIDS

Capillary Action

- Water rises in a capillary tube because the adhesive forces between

the water and the glass (polar SiO2) are quite strong

- Liquid mercury is depressed in capillary tube because

cohesive forces are stronger than adhesive forces
 PROPERTIES OF LIQUIDS

Capillary Action

- The upward or downward curvature of a liquid surface

is known as the meniscus

- The direction of curvature depends on the relative strengths

of the cohesive and the adhesive forces

Examples
- Ability of plants to draw water out of the ground
- Ability of paper towels and cloth to absorb water
 PROPERTIES OF LIQUIDS

Viscosity

- Resistance of a fluid to flow and is related to intermolecular

attractions

- The stronger the attractions the more viscous the fluid

- Viscosity also depends on the structure, shape, and size of molecules

Example
- The surface tension of water is greater than that of glycerol
- Glycerol is more viscous than water due to long and polar
glycerol molecules
 PROPERTIES OF SOLIDS

Two categories of solids

Crystalline Solid
- Units making up the substance are arranged in a
regular and repeating pattern

Amorphous Solid
- No crystalline order and consists of large molecules
(plastics, glass)

- Liquid states of amorphous solids are quite viscous

 PROPERTIES OF SOLIDS
Limited to Crystalline Solids

Molecular Solids
- Consist of atoms or small molecules held together by
van der Waals forces or hydrogen bonds or both

- Physical properties depend on intermolecular attractions

- Usually soft substances and exist in the liquid or gaseous state

at room temperature

- Melting points mostly below 300 oC

(CO2, H2O, I2)

 PROPERTIES OF SOLIDS

Limited to Crystalline Solids

Covalent Network Solids

- All atoms are held in place by covalent bonds

- Have very high melting points and are hard

materials

- Diamond, cubic BN, SiC, quartz, SiO2

 PROPERTIES OF SOLIDS
Limited to Crystalline Solids

Allotropes
- Two or more molecular or crystalline forms of an element in
the same physical state but exhibit different physical and
chemical properties

Allotropes of Carbon
- Diamond is the hardest substance known (each carbon atom
covalently bonded to four other carbon atoms; sp3 hybridization)

- Graphite consists of layers of covalently bonded carbon atoms

(layers are held together by van der Waals forces)
 PROPERTIES OF SOLIDS
Limited to Crystalline Solids

Ionic Solids
- Made up of oppositely charged ions held together by strong
electrostatic attractions

- Hard, brittle, and have high melting points

- Good conductors of electricity in the liquid state but do not

conduct electric current in the solid state

Examples
Binary compounds consisting of metals and nonmetals
NaCl, CaO
 PROPERTIES OF SOLIDS
Limited to Crystalline Solids

Metallic Solids
- Crystalline solids formed by metal atoms through metallic
bonding

- Exhibit high thermal conductivity, good electrical conductivity,

and metallic luster

- Malleable

- Valence electrons in metals are easily removed and form a sea

of electrons which are mobile
 STRUCTURES OF CRYSTALLINE SOLIDS
X-ray
- Short wavelength electromagnetic wave (radiation)

Constructive interference
- Occurs when waves are in phase (maximum and minimum
amplitudes occur at the same place

Destructive Interference
Occurs when waves are out of phase (waves cancel each other and
no radiation is observed)
 STRUCTURES OF CRYSTALLINE SOLIDS

Bragg Equation
- Used to interpret the diffraction of a narrow beam of x-rays by
crystals

- Useful only when the spacing between the layers and the
wavelength of the radiation are the same order of magnitude

nλ = 2dsinθ
λ = wavelength of x-rays used
d = distance between layers of atoms in the crystal
θ = angle between the diffracted x-rays and the layers of atoms
n = order (positive integers)
 STRUCTURES OF CRYSTALLINE SOLIDS

What is the wavelength of X-rays in which the first-order

diffraction occurs at 13.4 degrees from layers of atoms spaced
315 pm apart?

nλ = 2dsinθ

n=1

2dsinθ (2)(315 pm)(sin13. 4 o )

λ   146 pm
n 1
 STRUCTURES OF CRYSTALLINE SOLIDS
- The geometric pattern within crystals are defined using X-ray
diffraction data

Lattice Points
- Set of points in the regular geometric pattern of crystals with
the same distances and angles from one another

Crystal Lattice
- Refers to the geometric arrangement of the lattice points

Crystal Structure
- Refers to the crystal lattice and the arrangement of physical
particles with respect to the lattice points
 STRUCTURES OF CRYSTALLINE SOLIDS

Unit Cell

- A small and regular geometric figure that defines the

repeating pattern of the lattice points

- Lattices can be grouped into seven systems

- Systems are defined by the relative lengths of the edges of

the unit cell (a, b, and c) and the angles between the edges (α,
β, and γ)

- We will consider only cubic systems

STRUCTURES OF CRYSTALLINE SOLIDS

Cubic Systems

- All three edges are equal, that is a = b = c

- All angles are 90 degrees, that is α = β = γ = 90o

Example
- Sodium chloride (NaCl) crystals are perfect cubes

- Octahedral and rectangular shapes are also observed in

substances whose unit cells belong to the cubic system
 STRUCTURES OF CRYSTALLINE SOLIDS

Cubic Systems

- Three kinds of cubic unit cells depending on the locations of

the lattice points within the cells

- Assume that an atom is centered at each of the eight corners

of a cube
STRUCTURES OF CRYSTALLINE SOLIDS
Cubic Systems

Simple (primitive) Cubic Cell

- Only eight atoms are present
STRUCTURES OF CRYSTALLINE SOLIDS
Cubic Systems

Body-Centered Cubic Cell (BCC)

- An additional atom is at the center of the cube
STRUCTURES OF CRYSTALLINE SOLIDS

Cubic Systems

Face-Centered Cubic Cell (FCC)

- Six additional atoms are present, each at the center
of the six faces of the cube
STRUCTURES OF CRYSTALLINE SOLIDS

Intrinsic Property
- A property of a substance itself and depends on chemical
composition
(elemental composition and density)

Extrinsic (Bulk) Property

- Can be found from crystal structure and dimensions of unit
cell
(empirical formula and density)

- Experimentally determined densities of most metal samples

differ slightly from those calculated from the unit cell
 STRUCTURES OF CRYSTALLINE SOLIDS

- Intrinsic properties are consistent with the bulk properties of

the substance (due to repetitions of unit cell)

To Determine the Number of Atoms or Ions in A Unit Cell

- Atoms at the corners are shared by eight unit cells
- Implies 8 corner atoms = (8 x 1/8) = 1 atom

- Atoms centered on the faces are shared by two unit cells

- Implies 6 face-centered atoms = (6 x ½) = 3 atoms
 STRUCTURES OF CRYSTALLINE SOLIDS
Nichel crystallizes in a face-centered cubic array of atoms in
which the edge of the unit cell is 351 pm. Calculate the
density of the metal

8 corner atoms = (8 x 1/8) = 1 atom

6 face-centered atoms = (6 x ½) = 3 atoms
Number of atoms = 4
58.69 g 1 mol  22
Mass Ni  4 atoms Ni x x 23
 3.898 x 10 g Ni
1 mol 6.022 x 10 atoms
3
 1 cm 
Volume   351 pm x 10   4.32 x 10  23 cm 3
 10 pm 

mass 3.898 x 10 22 g

Density    23 3
 9.02 g/cm 3
volume 4.32 x 10 cm
 STRUCTURES OF CRYSTALLINE SOLIDS
Nichel crystallizes in a face-centered cubic array of atoms in
which the edge of the unit cell is 351 pm. What is the radius of
an atom of nickel?

Atoms are assumed to be spherical and in contact

Length of diagonal of one face = 4 times radius
Using Pythagoras theorem

Length of diagonal  a2  a2  a 2

4xra 2
a 2 (351 pm)( 2 )
r   124 pm
4 4
 STRUCTURES OF CRYSTALLINE SOLIDS
Close-Packing Structures
- Minimum empty space
- Atoms are viewed as spheres that are in contact with each other

- Each sphere is in contact with 12 other spheres

- 6 in the same layer and 3 in each of the layers above and below

Coordination Number
- The number of nearest neighbors

- Coordination number in close-packing arrays = 12

- Largest possible and results in smallest volume of free space
- 74% of total volume is occupied
 STRUCTURES OF CRYSTALLINE SOLIDS

Hexagonal Close Packing (hcp)

- Known as ABA stacking
- Atoms in the third layer are directly above atoms in the first
layer

Cubic Close Packing (ccp)

- Known as ABC packing
- Atoms in the third layer do not sit directly on atoms in the
first layer
- Same as the face centered cubic
 STRUCTURES OF CRYSTALLINE SOLIDS

Ionic Structures

- Two kinds of particles: cations and anions

- Unit cell is described in terms of the arrangement of only the

cations or only the anions

- Oppositely charged ions occupy specific locations within the

cell

- The type of crystal lattice depends on the relative charges and

sizes of the oppositely charged ions
 STRUCTURES OF CRYSTALLINE SOLIDS

Ionic Structures

- The ratio of the number of cations to the number of anions in

a unit cell must be consistent with the formula of the
compound

Sodium chloride crystal

- Face-centered cubic array of Cl- ions
Na+ at the center of each of the 12 edges and one at the center
of the cell