SOLIDS AND

PHASE CHANGES
(General Chemistry I; Lecture 12)

NELSON M. PANAJON
Department of Chemistry
CENTRAL LUZON STATE UNIVERSITY

Chemistry: The central science (12E) by Brown etal.

Copyright 2011 by Prentice Hall. All Rights Reserved
 https://initiate.alphacoders.com/download/wallpaper/84298/images4/jpg/0471305485

SOME CHARACTERISTIC PROPERTIES OF THE STATES OF MATTER

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 CLASSIFICATION OF SOLIDS

▪ DUE TO INTERMOLECULAR FORCES

▪ DUE TO CRYSTAL STRUCTURE

PAGE 3 SOLIDS AND PHASE CHANGES I NMPanajon

 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES

▪ Metallic solids
▪ Ionic solids
▪ Network-covalent solids
▪ Molecular solids
▪ Polymers
▪ Nanomaterials

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 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES
▪ Metallic solids -
- held together by a delocalized “sea” of collectively
shared valence electrons

Alloy
- combinations of two or more elements, majority of
which are metals, with changed properties of the
mixture to suit different purposes

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 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES

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 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES
Types of Alloy

Substitutional Alloy
- a second element
takes the place of a
metal atom

Interstitial Alloy
- a second element fills a space in the lattice of metal atoms.

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 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES
▪ Ionic solids -
- held together by the mutual attraction between
cations and anions

▪ Network-covalent solids
- held together by an extended network of covalent
bonds.

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 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES
▪ Molecular solids
- held together by the intermolecular forces

▪ Nanomaterials
- solids in which the dimensions of individual crystals
have been reduced to the order of 1–100 nanometers.

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 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES
▪ Polymers
- contain long chains of covalently-bonded atoms,
where adjacent chains are held to one another
largely by weaker intermolecular forces
- molecules of high molecular mass made by
sequentially bonding repeating units called
monomers

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NMPanajon
 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES
▪ Polymers

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PAGE 12 SOLIDS AND PHASE CHANGES I NMPanajon
 CLASSIFICATION OF SOLIDS
DUE TO INTERMOLECULAR FORCES

Chemistry: The central science (12E) by Brown etal.

Copyright 2011 by Prentice Hall. All Rights Reserved

PAGE 13 SOLIDS AND PHASE CHANGES I NMPanajon

 General Chemistry (10E) by Petrucci etal.
Copyright 2011 by Prentice Hall.
All Rights Reserved

PAGE 14 SOLIDS AND PHASE CHANGES I NMPanajon

 CLASSIFICATION OF SOLIDS
DUE TO CRYSTAL STRUCTURE

- structures of many solids have patterns that repeat over

and over in three dimensions and can thus be classified
as either crystalline solids or amorphous solids

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 CLASSIFICATION OF SOLIDS
DUE TO CRYSTAL STRUCTURE

▪ Crystalline solids
- follow highly ordered arrangement of
its atoms; have flat surfaces, or
faces, that make definite angles
with one another
- examples are sodium chloride,
quartz and diamond

Chemistry: The central science (12E) by Brown etal.

Copyright 2011 by Prentice Hall. All Rights Reserved

PAGE 16 SOLIDS AND PHASE CHANGES I NMPanajon

 CLASSIFICATION OF SOLIDS
DUE TO CRYSTAL STRUCTURE

▪ Amorphous solids
- at the atomic level the structures
of amorphous solids are
similar to the structures of
liquids but the molecules,
atoms, and/or ions lack the
freedom of motion they have
in liquids
Chemistry: The central science (12E) by Brown etal.
Copyright 2011 by Prentice Hall. All Rights Reserved

PAGE 17 SOLIDS AND PHASE CHANGES I NMPanajon

 CLASSIFICATION OF SOLIDS
DUE TO CRYSTAL STRUCTURE

▪ Amorphous solids
- lack the order found in crystalline
solids
- examples are rubber, glass, and
obsidian (volcanic glass)

Chemistry: The central science (12E) by Brown etal.

Copyright 2011 by Prentice Hall. All Rights Reserved

PAGE 18 SOLIDS AND PHASE CHANGES I NMPanajon

 CLASSIFICATION OF SOLIDS
DUE TO CRYSTAL STRUCTURE

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 CLASSIFICATION OF SOLIDS
DUE TO CRYSTAL STRUCTURE

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 The structure
of a crystalline solid
is defined by
(a) the size and shape of the
repeating unit and
(b) the locations of atoms within that
repeating unit

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 UNIT CELL AND THE CRYSTAL LATTICE

Unit cell
- the smallest, unique arrangement of atoms that
serves as the repeating unit and embodies the
structure of the solid

Crystal lattice
- a three-dimensional, geometrical pattern of points
designating the actual positions of the components
in the substance; in effect, an abstract scaffolding
for the crystal structure
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 UNIT CELL AND THE CRYSTAL LATTICE

Representing the unit cell in the crystal lattice.

Chemistry: The central science (12E) by Brown etal.

Copyright 2011 by Prentice Hall. All Rights Reserved

PAGE 23 SOLIDS AND PHASE CHANGES I NMPanajon

 UNIT CELL AND THE CRYSTAL LATTICE

Representative crystal lattices.

Chemistry: The central science (12E) by Brown etal.
Copyright 2011 by Prentice Hall. All Rights Reserved

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 THE SEVEN PRIMITIVE CRYSTAL LATTICES

Chemistry: The central science (12E) by Brown etal.

Copyright 2011 by Prentice Hall. All Rights Reserved

PAGE 25 SOLIDS AND PHASE CHANGES I NMPanajon

 General Chemistry (10E) by Petrucci etal.

PAGE 26
Copyright 2011 by Prentice Hall. All Rights Reserved

(eg. Po)
THE CUBIC LATTICE

(eg. Fe)
(eg. Cu)
SOLIDS AND PHASE CHANGES I NMPanajon
 General Chemistry (10E) by Petrucci etal.

PAGE 27
Copyright 2011 by Prentice Hall. All Rights Reserved
THE CUBIC LATTICE

SOLIDS AND PHASE CHANGES I NMPanajon

THE CUBIC LATTICE:
The Number of Atoms in a Cell

Cubic Cell Lattice Number of atoms inside the cell

Simple
Cubic 1
Body-centered
Cubic 2
Face-centered
Cubic 4

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THE CUBIC LATTICE:
Packing Efficiency

PACKING EFFICIENCY
- results from the incomplete packing of the
spherical atoms inside the cell which
leaves some voids or holes
- related to density and is given by the
equation:
Volume of atoms inside the cell
PACKING EFFICIENCY = x 100
Volume of the unit cell
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THE CUBIC LATTICE:
Packing Efficiency
For simple cubic cell:
Volume of atoms inside the cell
%PE = Volume of the unit cell
x 100
1 x (4/3)πr3
= 3
x 100
s
1 x (4/3)πr3
= (2r)3 x 100

= 52%

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THE CUBIC LATTICE:
Packing Efficiency
For a face-centered cubic cell:
Volume of atoms inside the cell
%PE = Volume of the unit cell
x 100
4 x (4/3)πr3
= 3
x 100
s
4 x (4/3)πr3
= [r(8)1/2]3 x 100

= 74%

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THE CUBIC LATTICE:
Packing Efficiency
For a body-centered cubic cell:

%Packing Efficiency = ???

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THE CUBIC LATTICE:
Packing Efficiency
For a body-centered cubic cell:
Volume of atoms inside the cell
%PE = Volume of the unit cell
x 100
2 x (4/3)πr3
= 3
x 100
s
2 x (4/3)πr3
= [4r/(3)1/2]3 x 100

= 68%

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THE CUBIC LATTICE:
Atomic radius (r), cell length (a) and
Packing Efficiency

Percent Packing
Atomic Radius (r)
Efficiency

Simple
Cubic r = a/2 52%
Face-centered
Cubic r = a / (81/2) 74%
Body-centered
Cubic r = a (31/2) / 4 68%

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 DENSITY OF A UNIT CELL (ρ)

total atomic mass nMW

ρ =
volume
=
VNA
where
ρ - density of the cell
n - number of atoms per unit cell
MW - molecular/atomic weight
V - volume of the cell
NA - Avogadro’s number (6.02 x1023 atoms/mole)

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 COORDINATION NUMBER

- refers to the number of other atoms attached to the

concerned atom in a unit cell
- related to the number of ions in the unit cell by the
equation:

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 COORDINATION NUMBER

Cubic Cell Lattice Coordination Number

Simple
Cubic 6
Body-centered
Cubic 8
Face-centered
Cubic 12

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 STRUCTURE AND
BONDING IN METALS
CLOSEST PACKING
- the model of packing a unit cell with hard
spherical atoms maximizing the use of
most available space possible
- can be hexagonal closest packed (hcp)
structure or tetragonal closest packed
(tcp) structure

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 STRUCTURE AND
BONDING IN METALS

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 STRUCTURE AND
BONDING IN METALS

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 STRUCTURE AND
BONDING IN METALS

hexagonal
closest
packed (hcp)
structure in
abab packing

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 STRUCTURE AND
BONDING IN METALS

cubic closest
packed (ccp)
structure in
abc packing

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 EXERCISE
Classify each of the following substances
according to the type of solid it forms.
a. Gold
b. Carbon dioxide
c. Lithium fluoride
d. Krypton

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 EXERCISE
Silver crystallizes in a cubic closest packed
structure. The radius of a silver atom is 144 pm.
Calculate the density of solid silver.

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 EXERCISE
Gold (Au) crystallizes in a cubic close-packed
structure and has a density of 19.3 g/cm3. Calculate
the atomic radius of gold in picometers.

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 EXERCISE
Shown on the right is
a zinc oxide unit cell.
What is the formula of
the compound?

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 EXERCISE
The unit cell of a binary
compound of copper and oxygen is
shown here. Given this image and
the ionic radii rCu+ = 0.74 Angstrom
and rO2- = 1.26 Angstrom;
(a) determine the empirical
formula of this compound.

PAGE 47 SOLIDS AND PHASE CHANGES I NMPanajon

 EXERCISE
The unit cell of a binary
compound of copper and oxygen is
shown here. Given this image and
the ionic radii rCu+ = 0.74 Angstrom
and rO2- = 1.26 Angstrom;
(b) determine the coordination
numbers of copper and
oxygen.

PAGE 48 SOLIDS AND PHASE CHANGES I NMPanajon

 EXERCISE
The unit cell of a binary
compound of copper and oxygen is
shown here. Given this image and
the ionic radii rCu+ = 0.74 Angstrom
and rO2- = 1.26 Angstrom;
(c) estimate the length of the
edge of the cubic unit cell.

PAGE 49 SOLIDS AND PHASE CHANGES I NMPanajon

 EXERCISE
The unit cell of a binary
compound of copper and oxygen is
shown here. Given this image and
the ionic radii rCu+ = 0.74 Angstrom
and rO2- = 1.26 Angstrom;
(d) estimate the density of the
compound.

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 THE PHASE DIAGRAM

A graphical representation
of the conditions of temperature
and pressure at which solids,
liquids, and gases (vapors) exist,
either as single phases, or
states, of matter or as two or
more phases in equilibrium with
one another.

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 THE PHASE DIAGRAM

Generic Phase Diagram for a pure substance.

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 THE PHASE DIAGRAM

Phase diagram for iodine.

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 THE PHASE DIAGRAM

Phase diagram for carbon dioxide.

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 THE PHASE DIAGRAM

Phase diagram for water.

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 INTERPRETING THE PHASE DIAGRAM

Use the given phase

diagram for methane (CH4) to
answer the following questions.

(a) What are the approximate

temperature and pressure of
the critical point??

PAGE 56 SOLIDS AND PHASE CHANGES I NMPanajon

 INTERPRETING THE PHASE DIAGRAM

Use the given phase

diagram for methane (CH4) to
answer the following questions.

(b) What are the approximate

temperature and pressure of
the triple point

PAGE 57 SOLIDS AND PHASE CHANGES I NMPanajon

 INTERPRETING THE PHASE DIAGRAM

Use the given phase

diagram for methane (CH4) to
answer the following questions.

(c) Is methane a solid, liquid, or

gas at 1 atm and 0 °C?

PAGE 58 SOLIDS AND PHASE CHANGES I NMPanajon

 INTERPRETING THE PHASE DIAGRAM

Use the given phase

diagram for methane (CH4) to
answer the following questions.

(d) If solid methane at 1 atm is

heated while the pressure is
held constant, will it melt or
sublime?

PAGE 59 SOLIDS AND PHASE CHANGES I NMPanajon

 INTERPRETING THE PHASE DIAGRAM

Use the given phase

diagram for methane (CH4) to
answer the following questions.

(e) If methane at 1 atm and 0 °C

is compressed until a phase
change occurs, in which
state is the methane when
the compression is
complete?
PAGE 60 SOLIDS AND PHASE CHANGES I NMPanajon
REFERENCES
Brown, Lemay, Bursten, Murphy & Woodward
© 2012. Chemistry: The Central
Science (12th edition)
Petrucci, Herring, Madura & Bisonnette © 2011.
General Chemistry: Principles and
Modern Applications (10th edition).