2/23/2010

Chemistry 8ed, Whitten etal, TB/C 2007

Solids and liquids are condensed states.

states.

their atoms, ions, or molecules are much closer
to one another than in gases.

are highly incompressible.

The intermolecular forces of attractions in

liquids and solids are strong.
strong.

Chemistry 8ed, Whitten

etal, TB/C 2007

 Schematic representation of the three  If we compare the strengths of

common states of matter. interactions among particles and the
degree of ordering of particles, we see
that

Gases< Liquids < Solids

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

Ion-ion interaction
– forces between individual particles • the force of attraction between two
(atoms, molecules, and ions) of a oppositely charged ions
substance • is governed by Coulomb’s law

• Ion-ion interaction
• Dipole-dipole
• H-bonding
• London forces or Dispersion forces

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007 6

1
 2/23/2010

Ion-ion interaction Ion-ion interaction

Coulomb’s law determines:
• the melting and boiling points of ionic compounds  table of melting points
• the solubility of ionic compounds.
Melting Points of Some Ionic Compounds
• Ionic substances containing multiply charged ions, (eg
Al3+ , Mg2+ , O2- , S2- ) usually have higher melting/boiling Compound Mp (o C) Compound Mp (o C) Compound Mp (o C)
points than singly charged ions NaF 993 CaF2 1423 MgO 2800
NaCl 801 Na2 S 1180 CaO 2580
• For a series of ions of similar charge, the closer approach
NaBr 747 K2 S 840 BaO 1923
of smaller ions results in stronger interionic attractions
and consequently higher melting/boiling properties

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 7 etal, TB/C 2007

Dipole-dipole interactions Hydrogen-bonding

• the force of attraction between two • also a force of attraction between two polar
polar molecules molecules BUT ONLY APPEARS IN
MOLECULES HAVING A HYDROGEN ATOM
Example: BrF (a polar molecule) ATTACHED TO N, O, F (the three
electronegative atoms).

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 9 etal, TB/C 2007 10

Dispersion forces Dispersion forces

Consider He as an isolated atom.
- also called London forces and are very weak  In a group of He atoms, the temporary dipole in one
forces atom induces other atomic dipoles.
- this is the only attractive force in nonpolar
molecules
- occurs only in extremely short distances,
i.e. 1/d7

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 11 etal, TB/C 2007 12

2
 2/23/2010

Dispersion forces Dispersion forces

 Similar effects occur in a group of I2  Induced dipole- induced dipole interaction
molecules.
Interaction strictly between nonpolar
molecules

 Dipole-induced dipole (originally, this is not

considered as London forces)

Interaction between a dipole (polar) molecule
and a nonpolar molecule

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 13 etal, TB/C 2007

Dispersion forces
 are most important when POLARIZABILITY is
high:  in general, the trend for IMFA strength is:

high # of electrons (SQUISHY MOLECULE) ion-ion> {ion-dipole}

appearance of π delocalized bonds (that actually
> H-bonding
makes the molecule FLAT due to sp2 and sp3 > dipole-dipole
hybrid) > London dispersion

overall molecule is LARGE {dipole - induced dipole > induced dipole -

molecule covers a larger area induced dipole}

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

Properties at the Solid State

• A molecule may have MORE THAN ONE
TYPE OF IMFA when it interacts with similar
molecules.
• When comparing properties, it is best to
look at the OVERALL NET EFFECT OF THE
EXISTING IMFA for the molecule as it acts in
the ENTIRE SUBSTANCE (not just between
two molecules).
AMORPHOUS & CRYSTALLINE
• Amorphous solids do not have a well ordered molecular
structure.
– Examples include waxes, glasses, asphalt.
• Crystalline solids have well defined structures that consist
of extended array of repeating units called unit cells.
cells
– Crystalline solids display X-ray diffraction patterns
which reflect the molecular structure.

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 18
etal, TB/C 2007

3
 2/23/2010

Properties at the Solid State Properties at the Solid State

AMORPHOUS & CRYSTALLINE UNIT CELLS
 are the smallest repeating unit of a crystal

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

Properties at the Solid State Properties at the Solid State

There are seven basic crystal systems.  There are four types of unit cell.
- primitive - face centered
- body centered - side centered

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

Properties at the Solid State Molecular Solids

• According to Bond between Particles
• have molecules in each of the positions of the unit
Molecular Solids Network Covalent cell
• have low melting points, are volatile, and are
electrical insulators.
– Examples: water, sugar, carbon dioxide, benzene

Ionic solids Metallic Solids

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

4
 2/23/2010

Network Covalent Solids Ionic Solids

• have atoms that are covalently bonded to one • have ions that occupy the positions in the unit cell
another – Examples: CsCl, NaCl, ZnS
– Examples: Diamond, graphite, SiO2 (sand), SiC

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

Metallic Solids Properties at the Solid State

• may be thought of as positively charged nuclei Melting Point
surrounded by a sea of electrons. • the temperature at which the solid form
• the positive ions occupy the crystal lattice positions. of a substance is at equilibrium with its
liquid state
– Examples: Na, Li, Au, Ag
• normal melting point is the
temperature at which the solid melts at
exactly 1.00 atm of pressure

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007

Properties at the Solid State

Sublimation Viscosity
• process where the solid
transforms directly to the  the resistance to flow
vapor phase without
compare how water
passing through the pours out of a glass
liquid phase compared to molasses,
• solid CO2 or “dry” ice syrup or honey
does this well

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 etal, TB/C 2007 30

5
 2/23/2010

Capillary Action
Surface Tension

 is a measure of the  is the ability of a

unequal attractions liquid to rise (or fall)
that occur at the in a glass tube or
surface of a liquid other container
 the molecules at the  affects meniscus of
surface are attracted liquids
unevenly
Chemistry 8ed, Whitten Chemistry 8ed, Whitten
etal, TB/C 2007 31 etal, TB/C 2007 32

 Water exhibits a capillary rise.

 Cohesive forces are the forces that hold
 Mercury exhibits a capillary fall.
liquids together.
 Adhesive forces are the forces between a
liquid and another surface.

Capillary rise implies that the:
▪ Adhesive forces > cohesive forces

Capillary fall implies that the:
▪ Cohesive forces > adhesive forces

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 33 etal, TB/C 2007 34

Evaporation Boiling Point

 the process in which molecules escape from
the surface of a liquid and become a gas; is
temperature dependent.
 is the temperature at which the liquid’s vapor
pressure is equal to the applied pressure
 normal boiling point is the boiling point
when the pressure is exactly 1 atm
 Distillation is a method we use to separate
mixtures of liquids based on their
differences in boiling points.

Chemistry 8ed, Whitten Chemistry 8ed, Whitten

etal, TB/C 2007 35 etal, TB/C 2007 36

6
 2/23/2010

Vapor Pressure Vapor Pressure as a function of temperature.

 is the pressure exerted by a liquid’s vapor
on its surface at equilibrium.

 Vapor Pressure (torr) and boiling point for three

liquids at different temperatures.

0oC 20oC 30oC normal boiling point

diethyl ether 185 442 647 36oC
ethanol 12 44 74 78oC
water 5 18 32 100oC
Chemistry 8ed, Whitten Chemistry 8ed, Whitten
etal, TB/C 2007 37 etal, TB/C 2007 38

Comparing boiling point of

Comparing substances at substances at condensed state
condensed state
IMFA strength leads to

Higher melting point

Higher boiling point

Lower vapor pressure

Lower evaporation rate

Stronger surface tension

Higher viscosity

Chemistry 8ed, Whitten Chemistry 8ed, Whitten 40

etal, TB/C 2007 etal, TB/C 2007

“You can't just follow your heart.

heart. Your
heart can be deceived. You have to lead
your heart.
heart. ”

- from the movie, fireproof -

questions?