Chemistry: for

Engineering Students

Chapter 8: Molecules and Materials

8.1 INSIGHT INTO Carbon
8.2 Condensed Phases—Solids
8.3 Bonding in Solids: Metals, Insulators, and
Semiconductors
8.4 Intermolecular Forces
8.5 Condensed Phases—Liquids

Mar-16 Chapter-8 1
Chemistry: for
Engineering Students Carbon

….but the discoveries of C60 and the

For decades, chemistry textbooks
nanotubes ushered in a new form of
said that there were two forms of
carbon and also a new branch of
the element carbon: graphite and
science: Nanotechnology.
diamond….

C60

diamond C-nanotubes
graphite
What are their unique
Why is the Why is a lubricant?
mechanical, electronic
hardest material? What are the
and optical properties?
properties of Carbon
Mar-16 fibers? Chapter-8 2
Chemistry: for
Engineering Students Carbon

General form of
Phase Diagrams (Pc,Tc)

Liquid

Pressure
Phase
stability
regions Solid
What conditions are
Phase required for synthesizing
Equilibrium diamond?
curves
Gas

Triple point (Pt,Tt)

Critical point
Temperature
Mar-16 Chapter-8 3
Chemistry: for
Engineering Students Condensed Phases-Solids

Why studying solid structure?

The properties of solids

and their applications are
totally determined by
their atomic &
molecular structure and
the nature of the
chemical bond.

NaCl

Mar-16 Chapter-8 4
Chemistry: for
Engineering Students Condensed Phases-Solids
Solids can be classified into two broad types: crystalline and amorphous.

Crystalline solids→ atoms or molecules are Amorphous Solids → lack the

arranged in an orderly repeating pattern. order found in crystalline solids. At
Bonding forces are thus maximized and can be the atomic level the structures of
of various kinds: ionic, covalent, metallic, van amorphous solids are similar to the
der Waals, H-bonds or some combination of structures of liquids, but the
them. molecules, atoms, and/or ions lack
the freedom of motion they have in
liquids.

Ex:
Crystalline Ej:
quartz Amorphous
(SiO2) glass
(SiO2)

Mar-16 Chapter-8 5
Chemistry: for
Engineering Students Condensed Phases-Solids
A short primer on the structure of crystalline solids

•Orderly repeating pattern.

•The unit cell is made up of a
unique arrangement of atoms
and embodies the structure of
the solid.
•7 Crystalline systems,
14 Bravais lattice, etc.
•Lattice points: occupied by
atoms, ions ,and other chemical
Simple cubic lattice species, even macromolecules

•Chemical bonding across

Unit lattice points: metallic, ionic,
cell covalent, or intermolecular forces
Only 1 lattice position
is fully contained in the unit cell
Mar-16 Chapter-8 6
Chemistry: for
Engineering Students Condensed Phases-Solids
Simple cubic lattice
The crystalline structures of ionic and metallic solids
cc
tend to maximize the contact among
neighboring lattice positions, increasing thus the
stability of solids through attractive bonding forces.

•What is the coordination

index of each lattice position Unit
in the simple cubic lattice? cell
a

• Determine the packaging efficiency of the simple cubic lattice.

Mar-16 Chapter-8 7
Chemistry: for
Engineering Students Condensed Phases-Solids

The face-centered cubic lattice yields a highly

compact packaging and maximizes bonding Very common in
between near neighbors (high coord. Index) metals and ionic solids!

fcc
A

A
Face-centered cubic lattice
Coord. index=12 74% occ.
Close packaging
ABCABC….
Mar-16 Chapter-8 8
Chemistry: for
Engineering Students Condensed Phases-Solids
Stable crystal structure for the solid state of the elements
• Solids of most of the
elements crystallize in a
cubic lattice, but a few less
common crystal
arrangements are also
known.

• Materials engineers must

know the solid structures of
metals before
reengineering them by
exchanging some atoms for
those of other elements.
• Many elements (including
carbon) form more than one
solid phase that can differ
dramatically in their
physical properties!

Mar-16 Chapter-8 9
Chemistry: for
Engineering Students Condensed Phases-Solids
Diamond Graphite
Each C atom gives four C-C Each C atom is covalently bonded
covalent bonds in a tetrahedral to three other C atoms in the same
arrangement. layer to form interconnected
hexagonal rings.
Covalent
network 1.42 Å
solid
Graphite layers offset so that the C atoms in a given layer
sit over the middle of the hexagons of the layer below

1.54 Å

3.41 Å

Melting point : 3550 oC Melting point: 3652 oC

Mar-16 Chapter-8 10
Chemistry: for Bonding in Solids: Metals, Insulators and Semiconductors
Engineering Students

Metals exhibit physical properties that lead to their widespread use in countless
designs. They’re malleable, meaning they can be formed into useful shapes or foils.
They are ductile, meaning they can be pulled into wires. Metals are good
conductors of electricity and heat.
Crystalline structure

Cu(s)

Melting
point:
1084 oC

FCC lattice
How does the bonding in metals help
Coord.
explain these properties?
Index (Cu)=12
Mar-16 Chapter-8 11
Chemistry: for Bonding in Solids: Metals, Insulators and Semiconductors
Engineering Students

Crystalline structure Delocalized metallic bond!

Cu(s)

Melting
point:
1084 oC

+
-
FCC lattice
Coord. Electron-sea model: Lattice positions
Index (Cu)=12 corresponding to cationic atoms (+ charges) are
immersed in the electron density sea (− charge)
constituted by valence electrons. The electron
sea is uniformly distributed throughout the metal.
Mar-16 Chapter-8 12
Chemistry: for Bonding in Solids: Metals, Insulators and Semiconductors
Engineering Students

The electron-sea model of metal bonding explains qualitatively the

malleability and ductility of metals.

Mechanical stress reshapes the lattice structure, but hardly perturbs the
metallic bond. Thus changes in the positions of the atoms are partly
accommodated by a redistribution of the valence electrons.
Mar-16 Chapter-8 13
Chemistry: for Bonding in Solids: Metals, Insulators and Semiconductors
Engineering Students

ε0 Atomic orbital (2s1 valence shell of Li)

Li
Quantitative models for
ε2
metallic bonding are based
ε1 on the Band Theory.
Molecular orbitals
ε3 and orbital energies
ε2
ε1
Electronic band
ε4
ε3
ε2
ε1 Fermi level: εF
infinite chain of Li atoms (Li wire)
Occupied

Mar-16 Chapter-8 14
Chemistry: for Bonding in Solids: Metals, Insulators and Semiconductors
Engineering Students

Unpaired To have mobile conducting

conducting e− electrons, we need an unfilled
E band or portion of a band that is
close in energy to a filled band or
portion of a band.

Unoccupied
Band band
overlap
∆ε ~RT
Half-filled band Energy
Gap
∆ε >>RT

Metal Metal Insulator Semiconductor

(odd # e−) (even # e−)
Mar-16Cu Mg Chapter-8
C(diamond) Si 15
Chemistry: for
Engineering Students Intermolecular Forces

The very same existence and physical properties of the states of

matter are the macroscopic consequence
of the intermolecular forces.

Mar-16 Chapter-8 16
Chemistry: for
Engineering Students Intermolecular Forces
•Short distance Pauli repulsion
Repulsive
•ion-ion (same charge sign)

•ion-ion (opposite sign)

Classification: •Coulombic •ion-dipole
Forces
Intermolecular …
forces
between two
•dipole-dipole
molecules •van
Attractive der
Waals •dispersion
Typical values of
intermolecular interaction
energies lie in the 1-20
kJ/mol interval. •H-bonds (partially covalent forces)

Mar-16 Chapter-8 17
Chemistry: for
Engineering Students Intermolecular Forces
Molecular Polarizability
F2: non-polar molecule E (1.3 Vcm −1 )

q1=0.00 e q2=0.00 e Applying an q1=-0.016 e q2=+0.016 e

Electrostatic
Field

F F F F
d=1.41Å d=1.41Å

µ=0.00 D µind=0.15 D
µind││E
Either polar or non-polar molecules respond to
the presence of an external electric field by
creating an induced dipole moment.

µind = α E α ∝ # of e− and molecular volume

Polarizability indicates how susceptible a molecule is to
Polarizability having its charge distribution perturbed by an external field

Mar-16 Chapter-8 18
Chemistry: for
Engineering Students Intermolecular Forces
Dispersion forces

+ − + −

− +

Two non-polar Electron clouds are not Instantaneous (transient)

atoms or rigid and experience dipole induces another
molecules extremely rapid dipole in the neighbor
approach each fluctuations. The molecule, provoking thus a
other. asymmetrical electron net attractive force
cloud results in an
instantaneous dipole

Mar-16 Chapter-8 19
Chemistry: for
Engineering Students Intermolecular Forces
Dispersion forces

•Ubiquitous intermolecular forces

that are always present

•Dispersion force between two

molecules is proportional to their
molecular polarizabilities. propane
molecules
1
•Short range forces U disp ∝ −
r6
•Do not depend on the
relative orientation
Dispersion interactions
•Always attractive among hydrocarbon molecules

•As a rule of thumb, the larger molar mass, volume and

molecular surface, the stronger dispersion interactions.
Mar-16 Chapter-8 20
Chemistry: for
Engineering Students Intermolecular Forces
Dipole-dipole forces
The presence of a permanent dipole moment in polar molecules gives rise to
dipole–dipole forces. These forces originate from electrostatic attractions between
the partially positive end of one molecule and partially negative end of a
neighboring molecule.

2  1  µ12 µ 22
2

U ( µ1 , µ 2 ) = −  
ε Example
3 RT  4πε  r 6 E1

• Decrease with temperature. θ2

θ1 μ2
• Always attractive. μ1 r

•For large dipoles (µ=1-2 D), they

are stronger than dispersion CH3Cl
forces for equal molar mass M
CH3Cl

Mar-16 Chapter-8 21
Chemistry: for
Engineering Students Intermolecular Forces
Hydrogen bonding

Hydrogen bonding is a special type of intermolecular attraction between the H atom in

a polar bond (particularly H-F, H-O, and H-N) and the nonbonding electron pair on a
nearby small electronegative ion or atom usually F, O, or N (in another molecule)

2.8 Å
Water dimer
δ − δ+ H

Y H δ−
O
X O
H H

120-180o H

X,Y= O, F, N, Cl,…
(electronegative elements)

H-bonds possess geometry and identity

Mar-16 Chapter-8 22
Chemistry: for
Engineering Students
Intermolecular Forces
Hydrogen- bonding and Water

The water molecule is

perfect for H-bonding

q(O)=-0.82
μ1 μ2
O
H H
0.96Å
O: electronegative Td arrangement of q(H)=0.41
q(H)=0.41
element 8 valence e−
4 electron groups μ = 2.2 D
Lewis Angular Polar molecule
Structure geometry

Properties of individual One H2O molecule can Macroscopic

H2O molecules form up to 4 H-bonds properties of the
with neighboring waters H2O substance
Mar-16 Chapter-8 23
Chemistry: for
Engineering Students Intermolecular Forces
• Which type(s) of intermolecular forces need to be overcame to convert each
of the following from liquids to gases? (a) Ne, (b) CO, (c) CH4, (d) NH3. Rank
these substances in order of increasing boiling points.
Lewis Formula and Molar Dispersion Dipole-Dipole H-bonds?
mass
Shape forces? forces?
(g/mol)

Mar-16 Chapter-8 24
Chemistry: for
Engineering Students Intermolecular Forces
• The boiling points of acetic acid (CH3COOH), propanol (CH3CH2CH2OH)
and decanol (CH3(CH2)8CH2OH) are 391, 370 and 506 K, respectively.
Compare the relative strength of the intermolecular forces holding together
the molecules in the liquid phase to rationalize their different boiling points.

• The molecules shown below have the same molecular formula (C3H8O)
but different normal boiling points, as shown. Rationalize the difference in
boiling points.

Mar-16 Chapter-8 25
Chemistry: for
Engineering Students Condensed Phases: Liquids

Physical properties of liquids depend dramatically on intermolecular

interactions (cohesive forces among the liquid molecules)

Consequences
1-2 H-bonds
Surface per H2O
There is no general
equation of state
for liquids

Liquids exhibit new physical

properties : surface tension,
viscosity, relative permittivity, Bulk
vapor pressure, etc. Water
2-3 H-bonds
microdroplet
per H2O

Mar-16 Chapter-8 26
Chemistry: for
Engineering Students Condensed Phases: Liquids
Surface tension

• Surface tension explains why the surface

shows a membrane-like behavior.

•In the absence of external forces, liquids adopt a

spherical shape that minimizes surface tension effects L

T
• Bubbles also tend to adopt a spherical shape. Liquid const.
Pressure inside the bubble is greater than
Gas
outside r
P2 P1

P1>P2
Mar-16 Chapter-8 27
Chemistry: for
Engineering Students Condensed Phases: Liquids
Surface tension
Surface tension
• Surface tension increases with stronger (mJ m–2)
(CH3)2CO 24
intermolecular forces among molecules
CHCl3 27
in the liquid phase. CH3OH 24
C8H18 24
• Surface tension decreases with C6H6 29
temperature: the larger kinetic energy C2H5OH 24
of molecules, the lesser efficient the H2O 72
intermolecular forces are. C3H8O3 63

• Addition of some chemicals can change the surface tension of liquids.

Surfactant chemicals generally diminish the value of γ. For instance, soap
is a water surfactant.

Mar-16 Chapter-8 28
Chemistry: for
Engineering Students Condensed Phases: Liquids
• Hydrazine (H2NNH2), hydrogen peroxide (HOOH), and water (H2O) all
have exceptionally high surface tensions compared with other
substances of comparable molecular weights. (a) Draw the Lewis
structures for these three compounds.(b) What structural property do
these substances have in common, and how might that account for the
high surface tensions?

Mar-16 Chapter-8 29
Chemistry: for
Engineering Students Condensed Phases: Liquids
• The ability of a liquid to wet or not a surface is controlled by intermolecular forces
(adhesion forces). Basing on the following molecular model, explain why water
wets glass (represented here as the crystallographic form of SiO2 quartz).
Water
nanodroplet

O
H H

O O
Si
O O

SiO2(s)

Quartz layers

Mar-16 Chapter-8 30
Chemistry: for
Engineering Students Condensed Phases: Liquids

Volatility expresses the tendency of liquids to

evaporate (i.e., to undergo the liquid to vapor phase change)

Molecular kinetic energy distribution

Number of molecules
Low temperature

Threshold energy
to escape the
liquid phase
High
temperature

Kinetic energy

Volatile liquid
(e.g., acetone, ether,
water,…)
Mar-16 Chapter-8 31
Chemistry: for
Engineering Students Condensed Phases: Liquids
0
Pvap of a volatile liquid is the pressure exerted by its vapor in equilibrium
with the liquid phase within a closed vessel and at constant T.

Vapor
P0 vap pressure
Closed at equilibrium Once that the liquid-vapor
system Hg equilibrium is reached, the
manometer
rate of liquid molecules
evaporating must be equal
to that of vapor molecules
condensing into the liquid

The higher vapor pressure,

The manometer records the pressure variation the more volatile a liquid is!
ongoing from the initial situation in which all
molecules were in the liquid phase to the final
liquid-vapor equilibrium
Mar-16 Chapter-8 32
Chemistry: for
Engineering Students Condensed Phases: Liquids
0
Pvap of some pure liquids at 25 oC
0 0 0
Pvap (mm Hg) Pvap (mm Hg) Pvap (mm Hg)
water 23.8 benzene 95.2 n-hexane 151.2
carbon 114.6 bromine 215.4 carbon 361.3
tetrachloride disulfide
ethanol 59.0 benzaldehyde 1.3 diethyl-ether 537
Methanol 127.0 chloro-benzene 11.8 mercury 0.0020

• Explain the different volatility of Br2 and CS2.

Chemistry: for
Engineering Students Condensed Phases: Liquids

Pvap increases exponentially with T Normal

boiling point
ether ethanol water
( 1 atm)
Vapor pressure (mm Hg)

Tb(oC) •The lower Tb,

the higher
ether 34.6 volatility
1 atm
ethanol 78.3

water 100.0
Tb

Temperature (K)
•When Pvap matches external
(atmospheric) pressure, all
liquids boil.º

Mar-16 Chapter-8 34
Chemistry: for
Engineering Students Problems and Exercises
8.3 What property of diamond leads to the most engineering applications? Which types
of applications would benefit from this property?
8.4 Which variables must be controlled and in what manner to produce diamonds from
graphite?
8.6 Use the web to look up information on nanotubes. Distinguish between single-walled
and double-walled nanotubes.
8.8 What is the difference between an amorphous solid and a crystalline solid?
8.16 Explain why graphite is described as having a layered structure.
8.20 Manganese has a body-centered cubic unit cell and has a density of 7.88 g/cm3.
From this information, determine the length of the edge of the cubic cell.
8.2 The sea of electrons model is not generally used for quantitative predictions of
properties. What factors are left out of this model that might prevent quantitative
precision?
8.26 What is the key difference between metallic bonding (in the sea of electrons model)
and ionic bonding (as described in Chapter 7) that explains why metals conduct
electricity and ionic solids do not?
8.34-36 What type of atom is needed as a dopant in an n-type semiconductor? Why is it
called n-type? Is an n-type semiconductor actually negatively charged?
Mar-16 Chapter-8 35
Chemistry: for
Engineering Students Problems and Exercises
8.38 Suppose that a device is using a 15.0-mg sample of silicon that is doped with 1 ×
10–5% (by mass) phosphorus. How many phosphorus atoms are in the sample?
8.42 What is the relationship between polarizability and dispersion forces?
8.46 Which of the following compounds would be expected to form intermolecular
hydrogen bonds in the liquid state? (a) CH3OCH3 (dimethyl ether), (b) CH4, (c) HF,
(d) CH3CO2H (acetic acid), (e) Br2, (f ) CH3OH (methanol)
8.48 What type of intermolecular forces must be overcome in converting each of the
following from a liquid to a gas? (a) CO2, (b) NH3, (c) CHCl3, (d) CCl4.
8.50 Rank the following in order of increasing strength of intermolecular forces in the
pure substances. Which exists as a gas at 25°C and 1 atm? (a) CH3CH2CH2CH3
(butane), (b) CH3OH (methanol), (c) He.
8.54 What makes a chemical compound volatile?
8.58 Predict the order of increasing vapor pressure at a given temperature for the
following compounds: (a) FCH2CH2F, (b) HOCH2CH2OH, (c) FCH2CH2OH.
8.60 Suppose that three unknown pure substances are liquids at room temperature. You
make vapor pressure measurements and find that substance Q has a pressure of 110
torr, substance R has a pressure of 42 torr, and substance S has a pressure of 330 torr.
If you slowly increase the temperature, which substance will boil first and which will boil
last?
Mar-16 Chapter-8 36
Chemistry: for
Engineering Students Problems and Exercises
8.87 Use the vapor pressure curves illustrated here to answer the questions that follow.
(a) What is the vapor pressure of ethanol at 60°C?
(b) Considering only carbon disulfide and ethanol,
which has the stronger intermolecular forces in the
liquid state?
(c) At what temperature does heptane have a
vapor pressure of 500 mm Hg?
(d) What are the approximate normal boiling
points of each of the three substances?
(e) At a pressure of 400 mm Hg and a
temperature of 70°C, is each substance a liquid, a
gas, or a mixture of liquid and gas?

8.89 The following data show the vapor pressure of liquid propane as a function of temperature. (a)
Plot a vapor pressure curve for propane and use it to estimate the normal boiling point. (b) Use
your curve to estimate the pressure (in atm) in the propane tank supplying fuel for a gas barbecue
grill on a hot summer day when the temperature is 40 oC. (c) What implications might your answer
to (b) have for an engineer designing propane storage tanks?

Mar-16 Chapter-8 37
Chemistry: for
Engineering Students Problems and Exercises
11.5 (TCS ) Using this graph of CS2 data, determine
(a) the approximate vapor pressure of CS2 at 30
°C, (b) the temperature at which the vapor
pressure equals 300 torr, (c) the normal boiling
point of CS2.

11.89 (TCS) Acetone, (CH3)2CO, is widely used as an

industrial solvent. (a) Draw the Lewis structure for the
acetone molecule and predict the geometry around
each carbon atom. (b) Is the acetone molecule polar
or nonpolar?
(c) What kinds of intermolecular attractive forces exist between acetone molecules? (d)
1-Propanol, CH3CH2CH2OH, has a molecular weight that is very similar to that of
acetone, yet acetone boils at 56 oC and 1-propanol boils at 97.2 °C. Explain the
difference.
11.2 (TCS) a)Which kind of intermolecular
attractive force is shown in each case
here? (b) Predict which of the four
interactions is the weakest.

Mar-16 Chapter-8 38