CHM012

Chemistry  for  
Engineers
Topic 6:
Liquids and Solids

Tel.   | Page
 States  of  Matter
❖ The fundamental difference between states of matter
is the strength of the intermolecular forces of
attraction.

❖ Stronger forces bring molecules closer together.

❖ Liquids and solids are the condensed states of matter

because they are formed by forces that may involve:
✔ Covalent  bonding  
✔ Ionic  bonding  
✔ Intermolecular  forces

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 Intermolecular  Forces
They  are  forces  that  occur  between  molecules.

The  attractions  between  molecules  are  not  nearly  as  strong   as  the  
intramolecular   attractions  (bonds)   that  hold  compounds   together.

Many  physical  properties   reflect  intermolecular   forces,  like  boiling  

points,   melting   points,   viscosity,   surface  tension,   and  capillary  
action.
Types  of  Intermolecular  Forces,  IMFs
(Weakest  to  strongest   forces)

❖ dispersion   forces  (or  London   dispersion   forces)

❖ dipole–dipole   forces
❖ hydrogen   bonding   (a  special  dipole–dipole   force)
❖ ion–dipole   forces

Note:  The  first  two  types  are  also  referred   to  collectively  as  van  der  Waals  forces.
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 London  Dispersion  Forces
✔ They exist among noble gas atoms and nonpolar
molecules.
❖ Instantaneous dipole that occurs accidentally in a given
atom induces a similar dipole in a neighboring atom which
instigates weak and short-­‐lived interatomic attraction.
❖ The tendency of an electron cloud to distort is called its
polarizability.
Factors  that  Affect  Dispersion  Force  in  a  Molecule

1. number   of  electrons   in  an  atom  (more   electrons,   more  

dispersion   force)  – large  atoms  easily  polarizable.
2. size  of   atom  or  molecule/molecular   weight
3. shape  of  molecules  with  similar  masses  (more   compact,  
less  dispersion   force)

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 Dipole–Dipole  Forces
Exhibited  by  molecules   with  polar  bonds   that  behave  in  an  electric  field
• Attract  each  other  electrostatically  
• Also  called  dipole–dipole  attraction

Dipoles   find  the  best  compromise   between  attraction  and  repulsion.

Characteristics:  
✔ Only  1%  as  strong   as  covalent  or  ionic  bonds  
✔ Forces  grow  weaker  as  distance  between  dipoles   increase

a. The  electrostatic  interaction   of  two  polar   molecules

b. The  interaction   of  many  dipoles   in  a  condensed   state

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 Dipole–Dipole  Forces

Note:  For  molecules  of  approximately   equal  mass  and  size,  the  more  polar   the  molecule,   the  higher   its  boiling   point.

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 Hydrogen  Bonding
❖ Strong   dipole–dipole   forces  can  be  noticed   when  H  is  
bound   to  lone   pairs  on  highly   electronegative   atoms  
like  N,  O,  and F.

❖ Strength   of  interactions   can  be  characterized  by:

• Polarity  of  the  bond
• Close  approach   of  the  dipoles
• Small  size  of  the  hydrogen   atom  

❖ Such  bonding   affects  the  physical  properties   of  

elements
• Important  in  organic  molecules  

Note:  Blue  dotted  lines represent   intermolecular   forces  

between  the  water  molecules

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 The  Boiling  Points  of  the  Covalent  Hydrides  of  the  
Elements  in  Groups  4A,  5A,  6A,  and  7A
Which   Have  a  Greater  Effect:
Dipole–Dipole   Interactions   or  Dispersion  
Forces?

✔ If  two  molecules  are  of  comparable  

size  and  shape,  dipole–dipole  
interactions  will  likely  be  the  
dominating   force.

✔ If  one  molecule   is  much  larger  than  

another,   dispersion   forces  will  likely  
determine   its  physical  properties.

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 Ion–Dipole  Interactions
❖ Ion–dipole   interactions   are  found   in  solutions   of  ions.
❖ The  strength   of  these  forces  is  what  makes  it  possible   for  ionic  substances  to  dissolve  in  polar  solvents.

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 Intermolecular  Forces  – Summary

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 Example
1.  Based  on  the  following   Lewis  structures,   which  molecule  has  a  higher   boiling   point?   Why?

2.  Which  gas  would   behave  more   ideally  at  the  same  pressure   and  temperature?   Why?

CO N2

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 Characteristics  of  Liquid
Liquids exhibit low compressibility, lack of rigidity,
and high density
Surface tension is the resistance of a liquid to an
increase in its surface area – Liquids with large
intermolecular forces tend to have high surface
tensions
Capillary action is a spontaneous rising of a liquid
in a narrow tube -­‐ involves adhesive and cohesive
forces
✔ Adhesive  forces  attract  the  liquid   to  the  wall  
of  the  tube.
✔ Cohesive  forces  attract  the  liquid   to  itself.

❖ Water  has  stronger   adhesive  forces  with  glass;  

mercury  has  stronger   cohesive  forces  with  itself.

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 Characteristics  of  Liquid
Viscosity refers  to  the  measure  of  a  liquid’s   resistance  to  flow.  

Liquids   with  large  intermolecular   forces  or  molecular  complexity  tend  to  be  
highly   viscous

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 Phase  Change
Conversion from one state of matter to another is
called a phase change.

Energy is either added or released in a phase change.

Phase changes:
✔ melting/freezing -­‐ the heat of fusion (ΔHfus) is the
energy required to change a solid at its melting
point to a liquid.

✔ vaporizing/condensing -­‐ the heat of vaporization

(ΔHvap) is the energy required to change a liquid
at its boiling point to a gas.

✔ subliming/depositing -­‐ the heat of sublimation

(ΔHsub) is the energy required to change a solid
directly to a gas.

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 Heating  Curves
❖ A  plot  of  temperature   vs.  heat  added  is  called  a  heating  
curve.

❖ Within  a  phase,  the  amount   of  heat  needed   to  raise  the  

temperature   of  a  substance  is  the  product   of  specific  heat,  
sample  mass,  and  temperature   change.

Heat  =  m  x  Cp x  ΔT

❖ The  temperature   of  the  substance  does  not  rise  during   a  

phase  change  because  the  added  energy  is  used  to  
overcome   the  attractive  forces  between  molecules.

❖ During   the  phase  change,  the  product   of  mass  and  the  

heat  of  fusion   or  vaporization   is  heat.

Heat  =  m  x  ΔHvap

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 Vapor  Pressure
At any temperature, some liquid molecules have
enough energy to escape the surface and
become a gas.

As the temperature rises, the fraction of

molecules that have enough energy to break
free increases.

As more molecules escape the liquid, the

pressure they exert increases.

The liquid and vapor reach a state of dynamic

equilibrium: liquid molecules evaporate, and
vapor molecules condense at the same rate.

The vapor pressure present at equilibrium is also

called equilibrium vapor pressure

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 Estimation  of  Vapor  Pressure  Using  a  Simple  Barometer
Vapor pressure can be
determined principally by the
size of intermolecular forces in
the liquid.
Liquids with large intermolecular
forces have relatively low vapor
pressures -­‐ molecules need a
higher energy to escape the
vapor phase.
Substances with large molar
masses have low vapor
pressures -­‐ attributed to larger
dispersion forces.

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 Boiling  Point
✔ The boiling point of a liquid is the temperature at
which its vapor pressure equals atmospheric pressure.

✔ The normal boiling point is the temperature at which

its vapor pressure is 760 torr or 1 atm.

✔ Normal melting point: Temperature at which solid

and liquid states have identical vapor pressure, and
total pressure = 1 atm

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 Clausius–Clapeyron  Equation
❖ The natural log of the vapor pressure of a liquid is
inversely proportional to its temperature. This relationship
is quantified in the Clausius–Clapeyron equation.

❖ When the values of ΔHvap and P vap at constant temperature

are known, it is easy to calculate the value of Pvap at
another temperature.

Note: R  =  8.3145  J/mol  K

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 Example
The  vapor   pressure  of  water  at  25°C  is  23.8  torr,   and  the  heat  of  vaporization   of  water  at  25°C  is  43.9  kJ/mol.  Calculate  
the  vapor  pressure  of   water  at  50°C.

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 Phase  Diagrams
❖ A  convenient   way  of  representing  
the  phases  of   a  substance  as  a  
function   of   its  temperature  and  
pressure

❖ Triple  point:  The  temperature  at  

which  all  three  phases  exist  
simultaneously

❖ Critical  point:  The  critical  pressure  

and  critical  temperature,   together,  
define   this  point

✔ Critical  pressure:  Pressure  required   to  produce   liquefaction   at  critical  temperature.

✔ Critical  temperature:  The  temperature   above  which  a  liquid   cannot  be  liquefied,   irrespective  of  pressure  
applied  

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 Phase  Diagram  of  Water
❖ At  point  X  on  the  phase  diagram,   water  is  a  solid
❖ As  the  external  pressure  is  increased  while  the  
temperature   remains  constant,  the  solid/liquid   line  is   Liquid

crossed  and  the  ice  melts  

❖ The  solid/liquid   boundary   line  is  a  negative  slope
✔ Melting   point   of  ice  decreases  with  increased   Solid
external  pressure
❖ At  the  melting   point,   liquid   and  solid  are  in  dynamic  
X
equilibrium  
✔ When  pressure   is  applied,   the  volume  is  reduced Gas
✔ A  given  mass  of  ice  has  more   volume  at  0°C  than  
the  same  mass  of  water  in  liquid   state  
✔ Freezing   point   of  water  is  less  than  0°C  when  
pressure   is  greater  than  1  atm

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 Phase  Diagram  of  Carbon  dioxide
❖ The  liquid   state  does  not  exist  at  a  pressure   of  1  atm

❖ The  solid/liquid   line  has  a  positive  slope,   since  the  density  of  
solid  carbon   dioxide  is  greater  than  that  of  liquid   carbon  
dioxide
Interpretations:  
• Solid/liquid   line  is  a  positive   slope  
• Triple  point   occurs  at  5.1  atm  and  −56.6°C
• Critical  point  can  be  noticed  at  72.8  atm  and  31°C
• Sublimation   occurs  at  −78°C

Applications:
• Dry  ice  -­‐ A  convenient   refrigerant   because  it  does   not  
undergo   the  liquid   phase  under   normal   atmospheric  
conditions  
• Liquid   form  is  used  in  fire  extinguishers   at  25°C  under  
high   pressure  
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 Concept  Check
As  intermolecular   forces  increase,  what  happens  to  each  of  the  following?

a. Boiling   point  
b. Freezing   point
c. Viscosity
d. Vapor  pressure
e. Surface  tension  
f. Heat  of  vaporization
g. Enthalpy  of  fusion  

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 Classification  of  Solids
❖ Amorphous  solids  have  disordered   structures.  Example  -­‐ Glass
❖ Crystalline  solids  have  a  highly   regular  arrangement   of  components.   Positions   of  components   are  represented   by  
lattice(s).  A  three-­‐dimensional   system  of  points   that  designates  the  position   of  the  components   of  a  substance.

Unit  Cell

• The  basis  of  a  repeating  pattern  is  the  unit  cell.

• The  structure   of  a  crystalline  solid   is  defined   by:
✔ the  size  and  shape  of  the  unit   cell.
✔ the  locations  of  atoms  within  the  unit   cell.

Lattice  Points

• Positions   that  define   the  overall  structure  of  the  crystalline  compound   are  called  lattice  points.
• Each  lattice  point   has  an  identical  environment.
• Lattice  vectors connect  the  points   and  define  the  unit  cell.

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 2-­D  Lattices

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 3-­D  Lattices

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 Primitive  vs.  Centered  Lattices
Primitive  lattices have  atoms  only in  the  lattice  points.

Centered  lattices have  atoms  in  another   regular  location,  

most  commonly   the  body-­‐center  or  the  face-­‐center.

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 Cubic  Structures
Not  every  part  of   an  atom  on   a  lattice  point  
is  completely   within  that  unit   cell.    One  can  
determine   how  many  atoms  are  within   each  
unit  cell.
Eight  cubes  meet  at  a  corner,   therefore   only  
1/8  of   that  corner  atom  is  within  any  one  
unit  cell  meeting   there.
Two  cubes  meet  at  a  face,  therefore   only  1/2  
of  that  face  atom  is  within  any  one  unit  cell  
meeting   there.
A  body-­‐centered   atom  is  entirely  
within  the  unit  cell.

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 X-­Ray  Analysis  of  Solids
❖ X-­‐ray  diffraction  is  used  to  determine  the   Bragg  Equation
structure  of  crystalline  solids.
Where:   n - is  an  integer  
❖ Diffraction   occurs  due  to:   λ -­‐ is  the  wavelength  of  the  X-­‐rays  
✔ Constructive  interference   when  parallel  beam   d -­‐ is  the  distance  between  atoms  
waves  are  in  phase   θ -­‐ is  the  angle  of  incidence  and  reflection  
✔ Destructive  interference   when  waves  are  out  
of  phase

❖ Distance  traveled  by  waves  depends   on  the  

distance  between  the  atoms.

❖ A  diffractometer   is  used  to  carry  out  X-­‐ray  analysis  

of  crystals

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 Example
X-­‐rays  of  wavelength   1.54  Å  were  used  to  analyze  an  aluminum   crystal.  A  reflection  was  produced   at  θ =  19.3  degrees.  
Assuming   n  = 1,  calculate  the  distance  d  between  the  planes  of  atoms  producing   this  reflection

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 Types  of  Crystalline  Solid
❖ Ionic  solids  possess   ions  at  the  points   of  the  lattice  
that  describe  their  structures  

❖ Molecular  solids  have  discrete  covalently  bonded  

molecules  at  each  lattice  point(s)

❖ An  atomic  solid  has  atoms  at  the  lattice  points  that  

describe  its  structure
✔ Metallic  solids
✔ Network  solids
✔ Group   8A  (18)  solids

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 Structures  of  Metals
Closest  packing  is  an  arrangement   that  assumes  that  metal  atoms  are  hard,  uniform   spheres.
• These  spheres   are  packed  in  layers.  
• Each  successive  layer  is  formed   when  spheres  occupy  a  dimple  formed   by  the  spheres  of   the  previous   layer.  

Forms   of  closest  packing:

aba  packing  
abc  packing

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 aba  Packing
❖ The  2nd layer  is  like  the  1st,  but  it  is  displaced,   so  that  each  sphere   in  the  2nd layer  occupies  a  dimple   in  the  1st layer
❖ The  spheres   in  the  3rd layer  occupy  dimples   in  the  2nd layer.  Spheres  in  the  3rd layer  lie  directly  over  those  in  the  1st
layer
❖ The  resultant   structures  are  called  hexagonal  closest  packed  (hcp)  structures
• The  spheres   in  every  layer  occupy  the  same  vertical  position
• When  the  spheres  are  aba  closest  packed,  the  unit  cell  is  a  hexagonal  prism

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 Hexagonal  Closest  Packing,  hcp

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 abc  Packing
❖ The  spheres   in  the  3rd layer  occupy  dimples   in  the  2nd layer  
❖ Spheres   in  the  3rd layer  do  not  rest  above  spheres   in  the  1st layer
❖ The  4th layer  is  like  the  1st
❖ The  resultant   structure  is  termed  a  cubic  closest  packed  (ccp)  structure
• The  spheres   in  every  fourth   layer  occupy  the  same  vertical  position  
• In  abc  packing,   the  unit   cell  is  face-­‐centered  cubic

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 Cubic  Closest  Packing,  ccp

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 Common  Characteristics  of  the  hcp  and  the  
ccp  Structures  
✔ Each  sphere  in  both  structures   possesses  12  equivalent   nearest  neighbors  

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 Example
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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 Concept  Check
1. Determine   the  number   of   metal  atoms  in  a  unit  cell  if  the  packing  is:
a. Simple   cubic
b. Cubic  closest

1. A  metal  crystallizes  in  a  face-­‐centered  cubic  structure.  Determine   the  relationship   between  the  radius  of  the  metal  
atom  and  the  length   of  an  edge  of  the  unit  cell.  

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 Bonding  Models  of  Metal
A  successful  bonding   model  for   metals  must  consider:
✔ Malleability
✔ Ductility
✔ Efficient  uniform   conduction   of  heat  and  electricity

Bonding   models  for   metals  include:  

✔ Electron  sea  model
✔ Band  model  (Molecular   Orbital  model)

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 Electron  Sea  Model
❖A  regular  array  of  metal  cations  are  considered   to  be  in  a  sea  of   mobile  valence  electrons
❖Mobile   electrons  conduct  heat  and  electricity  
❖Ions  can  freely  move  around   when  the  metal  is  hammered   or  drawn  into   a  wire  
❖The  electrical  and  thermal  conductivity,   ductility,   and  malleability  of  metals  is  explained   by  this  model.

a. Representation  of  an  

alkali  metal  (Group  1A)  
with  one  valence  
electron

a. Representation  of  an  

alkaline  earth  metal  
(Group  2A)  with  two  
valence  electrons

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 Molecular  Orbital  Model
❖ As the number of atoms in a
chain increases, the energy gap
between the bonding orbitals
and between the antibonding
orbitals disappears, resulting in a
continuous band of energy.

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 Molecular  Orbital  Model
Most  metals  have  d and  p
orbitals  to  consider.

Their  MO  diagrams  lead  to  

more  bands   that  better  explain  
conductivity   and  other  
properties   of  metals.

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 Metal  Alloys
An  alloy is  a  substance  that  contains  a  mix  of  elements  and  possesses  metallic  properties

Classification  of  alloys:

1. Substitutional  alloy  -­‐ where  some  of  the  host  metal  atoms  are  replaced  by  other   metal  atoms  of   similar  size.  (Ex.  
Brass)  
2. Interstitial   alloy  -­‐ where  some  of  the  holes  in  the  closest  packed  metal  structure  are  occupied  by  small  atoms.  (Ex.  
Steel)
3. Heterogeneous  alloys  -­‐ components   not  dispersed   uniformly.

Topic  6:  Liquids  and  Solids | Page 45

 Network  Solids
Network  solids  are  those  atomic  solids   that  contain  directional  covalent  bonds   which  form   solids  that  can  be  viewed  as  
“giant  molecules”  

Properties:
✔ Brittle  nature
✔ Ineffective  conductors   of  heat  and  electricity  

Important  elements:
• Carbon  – ex.  Diamond   and  graphite  
• Silicon  

Topic  6:  Liquids  and  Solids | Page 46

 Diamond
Hardest  naturally  occurring   substance  
Each  C  atom  is  surrounded   by  a  
tetrahedral  arrangement   of  other  C  
atoms

Structure   as  per  the  localized  electron  

model:
✔ Stable  structure  is  obtained   via  
covalent  bonds
✔ Formed   by  the  overlap   of  sp3
hybridized   C  atomic  orbitals  

Structure   as  per  the  molecular  orbital  

theory:  
✔ Large  gaps  between  filled  and  
empty  levels
✔ Electron  transfer  is  not   easy  

Topic  6:  Liquids  and  Solids | Page 47

 Graphite
Slippery,   black,  and  a  conductor   of  heat  and  
electricity  
Structure   is  based  on  layers  of  C  atoms  arranged   in  
fused   six-­‐membered  rings.

Structure   as  per  the  localized  electron  model:  

• Shows  trigonal   planar  arrangement  
• 120-­‐degree  bond   angles  
• sp2 hybridization   -­‐ three  sp2  orbitals   on  each  C  
atom  fuse  to  form   σ  bonds   with  three  other  C  
atoms.  One  2p orbital  remains  unhybridized,  
perpendicular   to  the  plane.

Structure   as  per  the  molecular  orbital  theory:

• All  orbitals  combine   to  form   π  MOs  -­‐ assist  in  
the  stability  of   graphite.  Delocalized  electrons  
account  for  good   electrical  conductivity.

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 Semiconductors
They  have  a  gap  between  the  occupied   MOs  
(valence  band)  and  the  unoccupied   ones  
(conduction   band).

Electrons  must  enter  the  conduction   band  for  

electron  transfer.

Group   IVA  elements  have  gaps  between  the  bands  

of  0.08  to  3.05  eV  (7  to  300  kJ/mol).

Note:  Band  gaps  over  3.5  eV  lead  to  the  material  
being   an  insulator.

Topic  6:  Liquids  and  Solids | Page 49

 Semiconductors
Among   elements,   only  Group   IVA,  all  of   which  have  4  valence  electrons,   are  semiconductors.
Inorganic  semiconductors   (like  GaAs)  tend  to  have  an  average  of  4  valence  electrons  (3  for  Ga,  5  for   As).

Topic  6:  Liquids  and  Solids | Page 50

 Semiconductors  -­ Doping
Doping – is  changing   the  conductivity   of  
semiconductors   by  adding   an  element  with  more   or  
fewer  electrons

n-­‐type  semiconductor:  A  substance  whose  conductivity  

is  increased  by  doping   with  atoms  that  have  more  
valence  electrons  than  those  in  the  host  crystal.
✔ n-­‐type  have  more  electrons,   so  the  negative  charge  
travels  in  the  conductance  band.
p-­‐type  semiconductors:  A  substance  whose  
conductivity   is  increased  by  doping   with  atoms  having  
fewer  valence  electrons  than  the  atoms  of  the  host  
crystal.
✔ p-­‐type  have  fewer  electrons,   so  the  “hole”  travels  in  
the  valence  band.

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 Molecular  Solids
Possess  strong   covalent  bonding   within  molecules  but  weak  forces  between  molecules.
Forces  among  the  molecules  depend   on  the  nature  of  the  molecules.
✔ CO2,  I2,  P4,  and  S8 -­‐ No  dipole   moment;  possess  London   dispersion   forces.
✔ Molecules  that  possess  dipole   moments   have  greater  intermolecular   forces,  especially  when  hydrogen   bonding  
is  viable.

Solid   CO2 (Dry   Ice)   Solid   H2O  (Ice)

Topic  6:  Liquids  and  Solids | Page 52
 Ionic  Solids
In  ionic  solids,   the  lattice  comprises   alternately  charged  
ions.  Held  together   by  strong   electrostatic  forces  between  
oppositely   charged  ions.

Structure   is  based  on  closest  packing  of  spheres   so  that:

✔ Electrostatic  attraction  between  oppositely   charged  
ions  is  maximized.
✔ Repulsion   among   ions  with  like  charges  is  minimized.

Ionic  solids   have  very  high   melting  and  boiling   points  and  
are  quintessential   crystals.

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 Ionic  Solids
Most  favorable  structures   have  cation–
anion  distances  as  close  as  possible,   but  
the  anion–anion   and  cation–cation  
distances  are  maximized.

Three  common   structures  for  1:1  salts:

1. CsCl  structure
2. NaCl  (rock  salt)  structure
3. Zinc  blende   (ZnS)   structure

Topic  6:  Liquids  and  Solids | Page 54

 Effect  of  Ion  Size  on  Structure
The  size  of  the  cation  compared   to  the  anion  
(radius   ratio)  is  the  major  factor  in  which  
structure  is  seen  for   ionic  compounds.

Topic  6:  Liquids  and  Solids | Page 55

 Example
Determine   the  net  number   of  Na+ and  Cl− ions  in  the  sodium   chloride   unit  cell.

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 Types  and  Properties  of  Solids
Type  of  Solid: Atomic Molecular Ionic
Network Metallic Group  8A
Structural  Unit: Atom Atom Atom Molecule Ion
Type  of  Bonding: Directional Nondirectional  covalent London Polar  molecules: Ionic
covalent bonds  involving  electrons dispersion dipole–dipole
bonds that  are  delocalized forces interactions
throughout  the  crystal
Nonpolar  molecules:
London  dispersion  forces
Typical   Hard Wide  range  of  hardness Soft Hard
Properties:
High  melting Wide  range  of  melting Very  low Low  melting  point High  melting
point points melting  point point
Examples: Insulator Conductor Insulator Insulator
Diamond Silver Argon(s) Ice  (solid  H2O) Sodium  chloride
Iron Dry  ice  (solid  CO2) Calcium  fluoride
Brass
Topic  6:  Liquids  and  Solids | Page 57
 Example
Using  the  table  on  the  types  and  properties   of  solids,   classify  each  of   the  following   substances  according  to  the  type  of  
solid  it  forms
a. Gold
b. Carbon  dioxide
c. Lithium  fluoride  
d. Krypton  

Topic  6:  Liquids  and  Solids | Page 58