Chemistry 86

Chemistry for Engineers

Solids and Modern Materials

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 boiling point
forces are much weaker melting point
than intramolecular forces. DHvap
DHfus
DHsub 2
Summary diagram for analyzing the intermolecular forces in a sample.

INTERACTING PARTICLES
(atoms, molecules, ions)
ions present ions not present

ions only polar molecules only nonpolar

IONIC BONDING DIPOLE-DIPOLE molecules only
(Section 9.2) FORCES DISPERSION
FORCES only
H bonded to
ion + polar molecule
N, O, or F
ION-DIPOLE FORCES polar + nonpolar
molecules
HYDROGEN DIPOLE-
BONDING INDUCED DIPOLE
FORCES

DISPERSION FORCES ALSO PRESENT

SAMPLE PROBLEM 12.3 Predicting the Type and Relative Strength of
Intermolecular Forces
PROBLEM: For each pair of substances, identify the dominant
intermolecular forces in each substance, and select the
substance with the higher boiling point.
(a) MgCl2 or PCl3
(b) CH3NH2 or CH3F

(c) CH3OH or CH3CH2OH

CH3
(d) Hexane (CH3CH2CH2CH2CH2CH3)
CH3CCH2CH3
or 2,2-dimethylbutane
CH3
PLAN: Use the formula, structure and Table 2.2 (button).

•Bonding forces are stronger than nonbonding(intermolecular) forces.

•Hydrogen bonding is a strong type of dipole-dipole force.
•Dispersion forces are decisive when the difference is molar mass or
molecular shape.
 SAMPLE PROBLEM 12.3 Predicting the Type and Relative Strength of
Intermolecular Forces
continued

SOLUTION:
(a) Mg2+ and Cl- are held together by ionic bonds while PCl3 is covalently
bonded and the molecules are held together by dipole-dipole interactions. Ionic
bonds are stronger than dipole interactions and so MgCl 2 has the higher boiling
point.
(b) CH3NH2 and CH3F are both covalent compounds and have bonds which are
polar. The dipole in CH3NH2 can H bond while that in CH3F cannot. Therefore
CH3NH2 has the stronger interactions and the higher boiling point.
(c) Both CH3OH and CH3CH2OH can H bond but CH3CH2OH has more CH for
more dispersion force interaction. Therefore CH3CH2OH has the higher boiling
point.
(d) Hexane and 2,2-dimethylbutane are both nonpolar with only dispersion
forces to hold the molecules together. Hexane has the larger surface area,
thereby the greater dispersion forces and the higher boiling point.
Unit Cells and Basic Structures

The striking beauty of crystalline solids

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.

lattice
point At lattice points:
• Atoms
• Molecules
• Ions
Unit Cell Unit cells in 3 dimensions
10
Seven Basic Unit Cells

11
Three Types of Cubic Unit Cells

12
 A Corner Atom, a Edge-Centered Atom and a Face-
Centered Atom

Shared by 4 Shared by 2
Shared by 8
unit cells unit cells
unit cells

13
Figure 12.24 (1 of 3) The three cubic unit cells.

Simple Cubic

1/8 atom at
8 corners

Atoms/unit cell = 1/8 * 8 = 1

coordination number = 6
Figure 12.24 (2 of 3) The three cubic unit cells.

Body-centered
Cubic

1/8 atom at
8 corners

1 atom at
center

Atoms/unit cell = (1/8*8) + 1 = 2

coordination number = 8
Figure 12.24 (3 of 3) The three cubic unit cells.

Face-centered
Cubic

1/8 atom at
8 corners

1/2 atom at
6 faces

Atoms/unit cell = (1/8*8)+(1/2*6) = 4

coordination number = 12
Figure 12.26 Packing of spheres.

simple cubic
(52% packing efficiency)

body-centered cubic
(68% packing efficiency)
 Figure 12.26 (continued) layer a

hexagonal layer b
closest cubic closest
layer a layer c
packing packing

closest packing of first

and second layers

abab… (74%)
abcabc… (74%)

hexagonal expanded face-centered

unit cell side views unit cell
Relation Between Edge Length and Atomic Radius

19
When silver crystallizes, it forms face-centered cubic cells. The
unit cell edge length is 409 pm. Calculate the density of silver.

m
d= V = a3 = (409 pm)3 = 6.83 x 10-23 cm3
V
4 atoms/unit cell in a face-centered cubic cell

107.9 g 1 mole Ag
m = 4 Ag atoms x x = 7.17 x 10 -22 g
mole Ag 6.022 x 1023 atoms

m 7.17 x 10-22 g 3
d= = = 10.5 g/cm
V 6.83 x 10-23 cm3

20
Problem 1

The edge length of the titanium unit cell

is 3.28 A. Using a body centered cubic
structure, what is the atomic radius and
density of Ti?

Answer: r=142pm
D=4.5 g/cm3
Problem 2

The atomic radius of Pb is 174 pm.

Using a cubic closest packing structure,
what is the length of the unit cell and the
density of Pb in g/cm3?

Answer: a=492 pm
D=11.6 g/cm3
X-ray Crystallography

An Arrangement for Obtaining the X-ray Diffraction Pattern of a Crystal

23
 Reflection of X-rays from Two Layers of Atoms

Extra distance = BC + CD = 2d sinq = nl (Bragg Equation)

24
Problem 3

X-rays with wavelength of 125pm was

used to study a crystal which produced
a reflection at an angle of 17.4°.
Assuming first order diffraction, what is the
distance between planes of atoms?

Answer: d=209 pm
Problem 4

The second order diffraction for a

certain crystal was 18.4 degrees using
x-rays with a wavelength of 1.42. What is
the interplanar spacing of atoms in this
crytals?

Answer: d=450pm
Types of Crystalline Solids

27
Types of Crystalline Solids
Table 12.5 Characteristics of the Major Types of Crystalline Solids
Interparticle Physical
Particles Forces Behavior Examples (mp,0C)

Atomic Atoms Dispersion Soft, very low mp, poor Group 8A(18)
thermal & electrical [Ne-249 to Rn-71]
conductors
Molecular Molecules Dispersion, Fairly soft, low to moderate Nonpolar - O2[-219],
dipole-dipole, mp, poor thermal & C4H10[-138], Cl2
H bonds electrical conductors [-101], C6H14[-95]
Polar - SO2[-73],
CHCl3[-64], HNO3[-
42], H2O[0.0]
Ionic Positive & Ion-ion Hard & brittle, high mp, NaCl [801]
negative ions attraction good thermal & electrical CaF2 [1423]
conductors when molten MgO [2852]
Metallic Atoms Metallic bond Soft to hard, low to very Na [97.8]
high mp, excellent thermal Zn [420]
and electrical conductors,
Fe [1535]
malleable and ductile
Network Atoms Covalent bond Very hard, very high mp,
usually poor thermal and
electrical conductors
 The sodium chloride structure.

expanded view space-filling

 Crystal structures of metals.

cubic closest packing hexagonal closest packing

Which of the following is an ionic solid?

a. CaCl2
b. Ni
c. C6H6O2 ANSWER: A
d. He
e. SiC

Which of the following elements is ductile?

a. NaF ANSWER: D
b. Ar
c. BN
d. Cu
e. Diamond
Which of the following can conduct electricity in the molten state?

a. SiC
b. NaBr ANSWER: B
c. Xe
d. H2O
e. CO2
Amorphous Solids

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 Non-crystalline
quartz (SiO2) quartz glass 32
Crystalline and amorphous silicon dioxide
Ceramics

Classification of ceramic materials on the basis of application

Ceramics are compounds of metallic and non-metallic

elements, for which the interatomic bonding is predominantly
ionic.
Glasses are noncrystalline silicates containing other oxides,
notably CaO, Na2O, K2O, and Al2O3, which influence the glass
properties.
Cements

The characteristic feature of these materials is that when

mixed with water, they form a paste that subsequently sets and
hardens.

Hydraulic cement is a type of cement that hardens by chemical

reactions with water.

Reaction for Hydraulic Cement (e.g. Portland cement)

Graphene is a single atomic layer of graphite, composed of
hexagonally sp2 bonded carbon atoms.

Graphene is the strongest known material (~130 GPa), the

best thermal conductor (~5000 W/m∙K), and has the lowest
electrical resistivity (10−8 Ω∙m).

The band of molecular orbitals in lithium metal

Semiconductors and Band Theory

The band of molecular orbitals in lithium metal

Electrical conductivity in a conductor, semiconductor, and insulator.

conductor insulator

semiconductor
References

1. Callister, W.D. Jr. and Rethwisch, D.G. Fundamentals of Materials Science

and Engineering: An Integrated Approach, 5th Edition. John Wiley & Sons, Inc.
2. Chang, R. (2010). Chemistry, 10th Edition. McGraw Hill.
3. Silberberg, M. (2013). Principles of Chemistry, 3rd Edition. McGraw Hill.