Liquids and Solids

Gas: particles are far apart and are in rapid, random motion,
exerting small forces on each other
low density and high compressibility
Solid: greater density, rigid, and exert large attractive forces
H2O(s)  H2O(l) Hofus = 6.02 kJ/mol
H2O(l)  H2O(g) Hovap = 40.7 kJ/mol

Liquid (25oC, 1065 atm) 1.046

Gas (400oC, 242 atm) 0.157

The liquid and solid states show many similarities and are strikingly
different from the gaseous state.

16.1 Intermolecular Forces

Recall that atoms can form stable units called molecules by sharing
electrons. This is called intramolecular (within the molecule)
bonding.

The properties of the condensed states of matter (liquids and solids)

and the forces that cause the aggregation of the components of a
substance to form a liquid or a solid.

These forces may involve covalent or ionic bonding, or they may

involve weaker interactions usually called intermolecular forces
( because they occur between molecules).
The changes of state are caused by changes in the forces among the
molecules rather than those within the molecules.
H2O(l)  H2O(g) Hovap = 40.7 kJ/mol
H2O(g)  2 H + O HoO-H = 934 kJ/mol

1
Dipole-dipole Forces:
Molecules with polar bonds often behave in an electric field as if they
had a center of positive charge and a center of negative charge; that is,
they exhibit a dipole moment.

Molecules with dipole moments can attract each other electrostatically

by lining up so that the positive and negative ends are close to each
other.
This is called a dipole-dipole attraction.
In a condensed state such as a liquid, the
dipoles find the best compromise between
attraction and repulsion.
Dipole-dipole forces are only about 1%
strong as covalent or ionic bonds, and
they rapidly become weaker as the distance
between the dipoles increases

Hydrogen bonding: strong dipole-dipole force

hydrogen is bound to a highly electronegative atom (N, O, F)
the great polarity of the bond and the close approach of the dipoles

The boiling points for

the covalent hydrides

Large electronegativity values of the lightest element (N, O, F)

Small size of the first element of each group (N, O, F)
The nonpolar CX4: bp. CH4 < SiH4 < GeH4 < SnH4

2
London Dispersion Forces
This instantaneous dipole can then induce a similar dipole in a
neighboring atom.
The relatively weak forces that exist among noble gas atoms and
nonpolar molecules are called London dispersion forces

The dipole-dipole and London dispersion forces are called

van der Waals forces.
A momentary nonsymmetrical electron distribution
 A temporary dipolar arrangement, instantaneous dipole
 induce a similar dipole in a neighboring atom

Freezing point
 The mass
 The number of electrons
 Chance of the occurrence
of momentary dipole
 Higher polarizability
The importance of the Landon dispersion forces greatly increases
as atomic size increases.

3
16.2 The Liquid State

A molecule in the interior is attracted to

the molecules surrounding it.
A molecule at the surface is attracted by
molecules below it and on each side of it.

The resistance of a liquid to an increase in its surface area is called the

surface tension of the liquid.

Capillary action: the spontaneous rising of a polar liquid in a narrow

tube
Cohesive forces: intermolecular forces among the molecules
Adhesive forces: the forces between the liquid and their container

Nonpolar mercury: convex meniscus

Hg: Adhesive < Cohesive

Poar water: a concave meniscus.

H2O: Adhesive > Cohesive

4
Another property of liquids that is strongly dependent on
intermolecular forces is viscosity, a measure of a liquid’s resistance
to flow.
Liquids with large intermolecular forces tend to be highly viscous

Glycerol: highly viscous, hydrogen bonds

Gasoline, n = 3 ~ 8, nonviscous
CH3 (CH2)n CH3
Grease, n = 20 ~ 25, very viscous
Gas: intermolecular forces are negligible
Liquid: strong intermolecular forces and molecular motions
Solid: the molecular motions are minimal

This magnetorheological (MR) fluid

10

5
16.3 An Introduction of Structures and Types of Solids
Crystalline solids: a highly
regular arrangement of their
components
The regular arrangement of the
components of a crystalline solid
at the microscopic level produces
the beautiful, characteristic shapes
of crystals.

Amorphous solids: considerable

disorder in their structures

6
 Rhodochrosite fluorite

amethyst pyrite

The positions of the components in a crystalline solid are usually

represented by a lattice, a three-dimensional array of points
designation the centers of the components (atoms, ions, or
molecules) that shows the repetitious pattern of the components.
The smallest repeating unit of the lattice is called the unit cell.

Simple cubic
f v  0.52 CN=6

Body-centered cubic
f v  0.68 CN=8

Face-centered cubic
f v  0.74 CN=12

7
 X-ray Analysis of Solid
Bragg equation: constructive interference
The difference in distance traveled after reflection is an integral
number of wavelengths.

xy  yz  n
xy  yz  2d sin   n

15

X-ray diffraction: constructive interference, destructive interference

in phase out of phase

16

8
Types of Crystalline Solids:
Atomic solid Ionic solid Molecular solid
Graphite, NaCl sugar
Diamond H 2O

17

16.4 Structure and Bonding in Metals

hexagonal closest packed（hcp）structure

Octahedral hole

tetrahedral hole

cubic closest packed（ccp）structure

18

9
 19

Hexagonal closest packed (hcp) structure

Each sphere has 12 equivalent nearest

neighbors. (CN=12)
6 in the same layer, 3 in the layer above,
and 3 in the layer below 20

10
Cubic closest packed (ccp) structure (face-centered cubic)

1 1
(8  )  (6  )  4
8 2

Each sphere has 12 equivalent

nearest neighbors. (CN=12)
4 in the same layer, 4 in the layer above,
and 4 in the layer below 21

1 1
(8  )  (6  )  4
8 2

Corner: 1/8
Edge: 1/4
Face center : 1/2
Body center: 1 22

11
Example 16.1
Silver crystallizes in a cubic closest packed structure. The radius of
silver atom is 1.44 Å. Calculate the density of solid silver.

d 2  d 2  ( 4r ) 2  2d 2  16r 2
d 2  8r 2
e  d  r 8  1.44( 8 )  4.07
mass
density 
volume
4 atom 107.9 g 1 mol
 8
 
(4.07  10 cm) 1 mol 6.022 10 23 atoms
3

7.167  10  22 g
  10.6 g / cm3
6.74  10  23 cm3
23

fv = volume occupied by sphere in the unit cell

/ volume of the unit cell

for closest packed structure (ccp and hcp)

4  43 r 3 4  43 r 3
fv    0.74
e3 (r 8 ) 3

for simple cubic packing structure

1
(8  )  1
8

1  43 r 3 1  43 r 3
fv    0.524
e3 ( 2r ) 3 24

12
Body-Centered Cubic Packing

e 2  e 2  f 2  2e 2
b 2  (4r ) 2  f 2  e 2  3e 2
4r 1
e (8  )  1  2
3 8
2  43 r 3 2  43 r 3 3
fv     0.68
e 3 4r 3 8
( )
3 25

Bonding in Metals: malleability, ductility and the efficient and

uniform conduction of heat and electricity in all directions.
The bonding in most metals is both
strong and nondirectional.

The electron sea model

A regular array of metal cations in a
sea of valence electrons.
The mobile electrons conduct heat
and electricity, and the cations are
easily moved around as the metal is
hammered into a sheet (malleable) or
pulled into a wire (ductile).

(a) Alkali metal

(b) Alkaline earth metal
26

13
 The band model
The molecular orbital (MO)
The electrons travel around
the metal crystal in MOs
formed from the valence
atomic orbitals of the metal
atoms.

When many metal atoms interact, the large

number of resulting MOs become closely
spaced, forming a virtual continuum of levels,
called bands 27

Band
Partially
filled
Highly
mobile
electron
Conduction
bands
The electrons in the 1s, 2s and 2p orbitals are close
to the nuclei and thus are localized on each Mg.

A crystal with n Mg atoms has available n(3s) and n(3p) valence

orbitals which overlap and mix to form the MOs. Electrons in
these energy levels can travel throughout the crystal.
28

14
Metal Alloys: a mixture of elements and has metallic properties.
A substitutional allay: host atoms are replaced
by other metal atoms of similar size.

A interstitial allay: some of the interstices (holes)

in the closest packed metal structure are
occupied by small atoms.
The presence of the interstitial atoms changes
the properties of the host metal.
Mild steel: < 0.2% Ductile and malleable
Medium steel: 0.2 – 0.6 % Cr Ni Mn

 harder
200 18 5 7
High carbon steel: 0.6-1.5% 300 18 8~10

A alloy steel: viewed as being mixed interstitial and substitutional

29

16.5 Carbon and Silicon: Network Atomic Solids

Network solids: solids contain strong
directional covalent bonds
Brittle, poor heat and electricity conductor

Allotropes (different forms) : C, diamond,

graphite and fullerenes (C60, C70, …)
graphene (2010 Nobel Prize in Physics).

30

15
 Diamond
Tetrahedral
Covalent bond
sp3 hybridized AO
The localized electron model by the overlap of sp3 hybridized atomic
orbitals.
insulator

conductor

diamond metal 31

Graphite is slippery (lubricant), black and a conductor.

Layers of carbon atoms arranged infused six-membered rings.
The localized electron model predicts sp2 hybridization.
One 2p orbital is perpendicular to the plane.   MO
a). the stability of the graphite layers
b). delocalized electrons  electrical conductivity

The corresponding resistivity of the graphene sheet would be 10−6 Ω⋅cm.

This is less than the resistivity of silver, the lowest known at room
temperature 32

16
1,2,3-superconductor: Y1Ba2Cu3O6+x
Zero electrical resistance
Diamagnetism (Meissner effect)

1986

77 N2

33

Perovskite Structure

34

17
 Ceramics are made from clays that are hardened by firing at
high temperatures.
Nonmetallic materials are strong, brittle and resistant to heat and
attack by the chemicals.
A glass is a homogeneous, noncrystalline ‘ frozen solution’
A ceramic is heterogeneous: minute crystals of silicates that are
suspended in a glassy cement
The mineral feldspar: K2O·Al2O3·6SiO2 and Na2O·Al2O3·6SiO2
An aluminosilicate in which aluminum as well as silicon atoms
are part of the oxygen-bridged polyanion.
Kaolinite : tiny thin platelets Al2Si2O5(OH)4
 H2O, slide over one another, its plasticity
 dry, platelets interlock again
 fired, the silicates and cations form a glass that binds
the tiny crystals of kaolinite 35

CO2: sp hybrid orbital Silicate anions: O:Si greater 2:1

and a  bond

Silica, SiO2
A network of SiO4
tetrahedra

Metal cations polyatomic Si-O anions

36

18
 Crystalline, quartz Amorphous, glass

37

Semiconductors
A few electrons can cross the gap at 25℃, making silicon a
semiconducting element, or semiconductor.
The small conductivity of silicon can be enhanced at normal
temperatures if the silicon crystal is doped with certain other elements.

38

19
 Semiconductors: Si, Ge,
Doped As Doped Ga
n-type p-type

Semiconductor: the conductivity increases with increasing temperature.

39
Metal: the conductivity decreases with increasing temperature.

This produces an n-type semiconductor, a substance whose

conductivity is increased by doping it with atoms having more valence
electrons than the atoms in the host .
n-type: negative electron p-type: positive hole

Doped As
n-type

Doped B
p-type

When semiconductors are doped with atoms having fewer valence

electrons than the atoms of the host crystal, they are called p-type
semiconductors. 40

20
 p-n junction
Contact potential
Junction potential
A small number of
electrons migrate from
the n-type into the p-type.

Reverse bias:
no current flows
Forward bias:
current readily flows.

A p-n junction is a rectifier,

a device that produces direct
current from an alternating
current. 41

16.6 Molecular Solids

Discrete molecular units at each lattice position.
Ice, dry ice, S8, P4, C60, C70, and others.
Strong covalent bonding within the molecules but relatively weak
forces between the molecules.

Zero dipole
London dispersion forces 42

21
Sulfur crystals (yellow) contain S8 molecules.
White phosphorous contains P4 molecules. It is
so reactive with the oxygen in air that it must be
stored under water.

Polar molecules,
intermolecular force
are greater

43

16.7 Ionic Solids

Ionic solids are stable, high-melting
substances held together by the
strong electrostatic forces that exist
between oppositely charged ions.

Binary ionic solid: MmXn, NaCl

Anions are packed in one of closest
packing arrangements, while the
smaller cations fit into holes among
the closest packed anions.

The holes size:

Trigonal < tetrahedral < octahedral
44

22
Octahedral holes
d  2e  2 (2 R)  2( R  r )
r  ( 2  1) R  0.414 R

(2 R) 2  (2 R) 2  d 2  8R 2 d  8R  2 2 R  2( R  r )
d  2( R  r ) r  ( 2  1) R  0.414 R 45

Tetrahedral holes

f  2R
e  2R
b  6R

f 2  e 2  e 2  (2 R) 2
e  2R
b 2  f 2  e 2  (2 R) 2  ( 2R) 2
b  6R  2(r  R )
6
r(  1) R  0.225 R
2 46

23
 Cubic holes

(2 R  2r ) 2  b 2  e 2  f 2  3e 2  3(2 R) 2  12 R 2
2( R  r )  12 R  2 3R
r  ( 3  1) R  0.732 R
47

Guideline for Filling Octahedral and Tetrahedral Holes

In the closest packed arrangement, the X- ions are touching.
However, if M+ ions are forced into holes in the structure that are
smaller than the M+ ions, the X- ions are forced apart, decreasing the
X-…X- repulsions. On the other hand, M+ and X- will direct contact
maximizing the M+…X- interactions.

Size of M+ Type of Hole Filled

0.225 < r+/R- < 0.414 Tetrahedral
0.414 < r+/R- < 0.732 Octahedral
0.732 < r+/R- Cubic

The ions behave as hard spheres and that only ionic forces occur.
 These guideline are not always obeyed. 48

24
16.8 Structures of Actual Ionic Solids

1 1
The face-centered cubic unit: (8  )  (6  )  4
8 2
There are twice as many tetrahedral holes as there
are packed spheres in the closest packing.
The number of octahedral holes in the ccp structure
is the same as the number of packed spheres.
1
(12  )  1  4 rNa = 0.66 RCl, Na in Oh hole
4
Halides of Li, Na, K, Rb; CsF
CsCl, CsBr, CsI: Cs in cubic hole of X simple cubic
49

NaCl: Na in Oh hole CsCl: Cs in cubic hole

1 1 1
(8  )  (6  )  4
8 2 8 ( )  1
8
1
(12  )  1  4
4

Fluorite structure
Ca2+: ccp
F-: tetrahedral holes
CaF2, SrF2, BaCl2,
1 1
PbF2, CdF2
(8  )  (6  )  4
8 2 50

25
 Zinc blende
S2-: ccp
Zn2+: tetrahedral hole

Wurtzite
S2-: hcp
Zn2+: Td hole

51

16.9 Lattice Defects

All real crystals have imperfections.

Schottky defects Frenkel defects

Missing particles Migrate to nonstandard positions

52

26
 16.10 Vapor Pressure and Changes of State
Called vaporizations, or evaporation, this process is endothermic,
because energy is required to overcome the relatively strong
intermolecular forces in the liquid.
Standard heat of vaporization, Standard enthalpy of vaporization, Hvap
The energy required to vaporize 1 mole of liquid at a pressure of 1 atm.
Equilibrium Pvapor Rate of evaporation = Rate of condensation

53

Barometer measures the vapor of a liquid.

Liquids with high vapor pressures are said to be volatile. 54

27
The size of the intermolecular forces  the vapor pressure
The intermolecular forces are large have relatively low pressures.
H2O: the strong hydrogen bonding  low vapor pressure
Large molar masses  large dispersion forces, low vapor pressure

Vapor pressure increases significantly with temperature.

T 0 10 20 25 30 40 60 70 90
P 4.579 9.209 17.535 23.756 31.824 55.324 149.4 233.7 525.8
55

G 0  H 0  TS 0   RT ln K
H 0  1  S 0
ln K    
R T  R
H vap  1 
ln( Pvap )    C
R T 

H vap
The slope = 
R

56

28
 H vap 1
T1
ln( Pvap ) ( )C G 0   RT ln K  H 0  TS 0
R T1
H 0 1 S 0
H vap 1 ln K   ( )
R T R
T2
ln( Pvap ) ( )C
R T2
H vap 1 H vap 1
T1
ln( Pvap ) ( )  C  ln( Pvap
T2
) ( )
R T1 R T2
H vap 1 1
T1
ln( Pvap )  ln( Pvap
T2
) (  )
R T2 T1
T1
Pvap H vap 1 1
ln( T2
) (  )
Pvap R T2 T1
Sublimation: goes directly from solid to the
gaseous state without passing through the
liquid state. I2, dry ice; CO2 57

Changes of State

boiling point,
enthalpy of vaporization

Melting point, heat of fusion; enthalpy of fusion

58

29
 m.p. Hfus
Case I
O2 -218 0.45
Case II
HCl -114 1.99
CHCl3 -64 9.20
HI -51 2.87
CCl4 -23 2.51
H2O 0 6.01
NaCl 801 30.2
NaF 992 29.3

The vapor pressure of ice increases more rapidly for a given rise in
temperature than does the vapor pressure of water.
Melting point: liquid and solid have identical vapor pressures 59

Case I:
Pvap of solid > Pvap of liquid
Temperature > Melting point
Only the liquid state can exist.

Case II:
Case II: Case III:
Pvap of solid
P of solid < Pvap of liquid Pvap of solid = Pvap of liquid
Pvap of liquid
< vap
Temperature < Melting point Temperature = Melting point
Temperature
Only the solid state can exist.
< Melting point
60

30
Normal melting point: the temperature at which the solid and liquid
states have the same vapor pressure under conditions where the total
pressure is 1 atm.

Normal boiling point: the temperature

at which the vapor pressure of liquid is
exactly 1 atm.

Pvap of liquid is less than 1 atm

No bubbles of vapor
The pressure on the surface of the
liquid is greater than the pressure in
any spaces in the liquid.

61

Supercooled: water can be cooled below 00C at 1 atm and still

remain in the liquid state.

The degree of
organization needed
to form ice at 00C.

Superheated: raised to temperature above its boiling point.

bumping 62

31
 16.11 Phase Diagrams Which state exits at a given T and P.
Pure substance, in a close system

63

The critical point is

fluid
374℃ and 218 atm

P1 = 1 atm, Tm = 0 oC, Tb = 100 oC;

P2 = 2.0 torr, sublimation at –10 oC;
P3 = 4.588 torr, triple point T3 = 0.0098 oC, ice, water, and vapor coexist;
P4 = 225 atm, critical point, Tc and Pc, Tc: the vapor cannot be liquefied
above this temp, Pc: the pressure required to liquefied at Tc 64

32
Closed system
A negative slope:
Melting point of water decreases as the pressure increases.

The freezing point < O0C

when
Ice P > 1 quasiliquid
skating: atm

Insulated for water pipes

Antifreeze in water-cooled
engine
Aquatic life
Tb = 100.3 0C, P = 770 torr
Tb = 70 0C, P = 240 torr

65

66

33
 A positive slope, solid CO2 is more dense than liquid CO2.

Tc = 31 oC
Pc = 72.8 atm

T3 = -56.6 oC
at P = 5.1 atm

Tm = -78 oC
at P =1 atm
67

16.12 Nanotechnology
1-100 nm in size
high surface area of nanoparticles: useful for catalyzing
tiny size allows them to penetrate into very small spaces:
ex. Au nanoshells penetrate the tangle of capillaries supplying
blood to a cancerous tumor. Heated with infrared radiation,
and kills the surrounding cancer cells.

Carbon Nanotubes
Carbon nanotubes contain
networks of carbon atoms in
interconnected six-membered
rings (like “chicken wire”)
organized into slender tubes.

68

34
 69

Medical Applications of Nanotechnology

A biomedical species smaller than about 50 nm can easily enter most
cells (10,000-20,000 nm in diameter), and those smaller than 20 nm
can exit blood vessels.
Nanoscale biomedical devices can easily interact with biomolecules
inside and outside cells.
"quantum dots": CdSe, ZnS, an organic polymer that can be
attached to molecules.
tracked by fluorescence
MRI (magnetic resonance imaging)
Nanocapsule: contains molecules lethal to tumors
linked to a molecule that has a specific affinity for the
receptors on the surfaces of cancer cells
Nanotoxicology
particulate matter (PM): PM2.5 = 2.5 m = 2,500 nm 70

35