CHAPTER 10: FORCES BETWEEN IONS AND MOLECULES

Problems:10.1-10.4, 10.9-10.31, 10.33-10.36, 10.91-10.94, 10.99-10.100, 10.104-10.105

10.1 INTERACTIONS BETWEEN IONS IN SALTS

Ion-ion Interactions and Lattice Energy
electron affinity: energy associated with 1 mole of gaseous atoms to gain 1 mole of electrons
X(g) + e

X(g)

A quantitative measure of an atoms ability to accept an electron

The higher the electron affinity
more likely an atom can gain an electron
Note: Electron affinity is NOT the same as electronegativity (in Chapter 8).
The following shows the energy changes associated with forming NaCl from solid Na and Cl2
gas:

So why do ionic compounds form if the process requires energy (ionization energy, etc.)?
Ionic bonds form when cations and anions bond to form the 3D network (crystal lattice) of ions.
Many bonds forming a lot of energy is released.
The energy released is far greater than the ionization energy required.
lattice energy: energy released when an ionic compound forms from gaseous ions
quantitative measure of the strength of the ionic bonds in the compound
Note: Since lattice energy is released, it is negative.
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Ex. 1: Based on the types of bonds formed, compare sodium chlorides lattice energy of
-787 kJ/mol with magnesium oxides lattice energy of -3916 kJ/mol. Which releases
more energy when the lattice (ionic compound) forms? Is this expected?

Ex. 2: As bond strength increases, lattice energy _______.

increases

Thus, lattice energy and bond strength are ______ related.

directly

decreases
inversely

10.2 INTERACTIONS INVOLVING POLAR MOLECULES

10.3 DISPERSIONS FORCES
INTERMOLECULAR FORCES (IMFs)
phase (=physical state): solid, liquid, or gas
condensed states: solid and liquid phases
In solids and liquids, molecules are attracted to one another.
These attractions are called intermolecular forces.
To undergo a change in physical state (e.g. solid liquid or
intermolecular forces must be overcome.

liquid gas), these

Ion-Dipole Forces
Attraction between an ion and the oppositely charged end of a polar molecule
e.g. between Na+ and the negative end (O atom) of a H2O molecule or between Cl and the
positive end (H atoms) of a H2O molecule

Note that when an ionic compound like NaCl dissolves in water, the formation of ion-dipole
forces between the Na+ (or Cl) ions with water molecules results in the ionic bonds breaking.
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London Forces or Dispersion Forces (also called Induced-dipole Forces)

named after a German-American physicist named Fritz London (1900-1954)
In nonpolar molecules (shown as green) the
electrons may shift and concentrate on one end
temporary dipole (red = + end; blue = end)
The temporary dipole in one molecule causes the
electrons to shift in an adjacent molecule
another temporary dipole.
Their temporary dipoles cause them to be
attracted to one another.
Attraction lasts only until the electrons shift
again, and the temporary dipoles go away.
Nonpolar molecules experience only LDFs.
Polar molecules also experience LDFs, but they
also experience other IMFs that are often stronger.
The bigger the molecule the more electrons it
has and the further the electrons are from nucleus

the greater its polarizability (ability to distort electron clouds to get a temporary dipole)
the stronger its London forces.
Note: Molar mass is generally used as a measure of the size and polarizability of a molecule.
The higher the molar mass of an atom/molecule, the stronger its London forces.

Dipole-Dipole Forces: Attraction

between polar molecules
generally stronger than
London dispersion forces
because attraction is due to
permanent dipoles that do
not go away like induced
dipoles

Hydrogen Bonding:
Especially strong type of dipole-dipole force
Exist between molecules that contain the
following bonds: HF, HO, HN
because these are small atoms with large
electronegativity differences
very strong dipole in the molecule
Strongest type of intermolecular force
Responsible for ice being less dense than
liquid water, the relatively high melting and
boiling points for water, and the bending and
twisting in proteins and DNA.
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Hydrogen bonds are responsible for the bending and twisting in proteins, DNA, and other
important biological molecules.

Image from http://blog.targethealth.com/?p=6846

Note:

Hydrogen bonds are the strongest type of intermolecular forces between

different molecules, BUT ionic and covalent bonds (holding ions or atoms together
in compounds) are stronger than hydrogen bonds!

The term van der Waals forces is also used to refer to intermolecular forces (London/dispersion
forces, dipole-dipole forces, or hydrogen bonds) but not ion-dipole forces.

How to determine type of intermolecular forces involved:

Is the molecule polar

or nonpolar?

nonpolar
London Forces

CHEM 161 Chapter 10

polar

Any H-F, H-O, or H-N

bonds in the molecule?

yes

hydrogen bonds
and London Forces

no
dipole-dipole forces
and London Forces

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Ex. 1: Label all of the intermolecular forces between molecules in the following:
London/dispersion forces (LDF), dipole-dipole forces (D-D), hydrogen bonding (H bond).

______________

i. Br2(l)

______________

iii. H2S(l)

______________

ii. NH3(l)

______________

iv. CCl4(l)

Ex. 2: For each of the following,

i. Identify the bond between atoms as ionic, polar covalent, or nonpolar covalent.
ii. Identify the intermolecular forces as London dispersion forces, dipole-dipole
forces, and/or hydrogen bonding.
Water (H2O)

B
A

A: __________________________

B: __________________________

HCN (H=white, C=charcoal, N=blue)

A: __________________________
CHEM 161 Chapter 10

B: __________________________
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Ex. 3:

Indicate the bond(s) or intermolecular forces described for each below:

A. ionic bond
B. polar covalent bond
C. nonpolar covalent bond

_________ i.

D. London forces
E. dipole-dipole forces
F. hydrogen bonding

G. ion-dipole forces

What holds two I2 molecules together in a sample of I2(s)?

_________ ii. What holds atoms together in HF?

_________ iii. What holds atoms together in a nitrogen molecule?

_________ iv. What holds two ammonia molecules together in liquid ammonia?

_________ v. What holds two methane molecules together in liquid methane?

_________ vi. What holds two CH2O molecules together in a sample of CH2O(l)?

_________ vii. The bonds broken when water boils.

_________ viii. The bonds broken when NaCl(s) melts.

_________ ix. The bonds formed when KBr dissolves in water.

Ex. 4 Circle the molecule in each pair that experiences the stronger intermolecular forces
and explain why.
a. N2

or

NO

Why?

CHEM 161 Chapter 10

b. H2S
Why?

or

H2O

c. Cl2

or

F2

Why?

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VAPOR PRESSURE AND PHASE CHANGES

vaporization: liquid gas
From a molecular viewpoint, a molecule escaping from the liquid to gaseous state
vapor: The gas above a liquid when the liquid and gaseous states are both present
In the examples below, there is more vapor is (b) than in (a).

vapor pressure: the pressure exerted by the gas molecules above a liquid
In the examples above, the sample in (b) has higher vapor pressure than the sample in (a).
vaporization: liquid + heat vapor
condensation: vapor liquid + heat
Liquid-Gas Equilibrium:

vaporization

vapor
liquid + heat

condensati on

When the molecules in the liquid have enough energy, they escape to the gas phase.
In a closed system, when enough vapor exists above the liquid, some gaseous
molecules condense back to the liquid.
Ultimately, the rate of vaporization = the rate of condensation.
The system has reached a state of dynamic equilibrium in which the forward
process occurs at the same rate as the reverse process.
In an open system, when molecules in the liquid have enough energy to escape to the gas
phase, the molecules continue to escape in a process called evaporation.
The vaporized molecules continue to escape few gas molecules condense to liquid
Ultimately, all of the liquid is converted into a gas.
Since vaporization requires energy, the liquid molecules take energy from the
surroundings, so the temperature of the surroundings decreases.
why evaporation is a cooling process that can reduce body temperature
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Vapor Pressure (v.p.): pressure exerted by gas molecules above a liquid

for a molecule to go from liquid to gas, it has to break the intermolecular forces with or
attraction to the other liquid molecules around it
weaker the intermolecular forces are easier to break
more gas molecules higher vapor pressure
stronger the intermolecular forces are harder to break
fewer molecules go from liquid to gas lower vapor pressure
Boiling Point: temperature where vapor pressure of liquid is equal to external pressure
(usually atmospheric pressure)
For a liquid to boil, its vapor pressure must equal atmospheric pressure.
Since intermolecular forces influence vapor pressure, they also influence boiling point.
Weaker intermolecular forces more gas molecules higher vapor pressure
Less energy is needed to get vapor P = atmospheric P lower boiling point
Stronger intermolecular forces fewer gas molecules lower vapor pressure
More energy is needed to get vapor pressure = atmospheric pressure
higher boiling point
normal boiling point is the boiling point at a pressure of 1 atm
e.g. Water boils at 100C at 1 atm but at ~95C in Denver where Patm =~0.85 atm.
Ex. 1: If hexane (C6H14) molecules are nonpolar, fill in the blanks for the following statements
about water and hexane:
a. Hexanes intermolecular forces are ________________________.
b. Waters intermolecular forces are ________________________.
c. Water's intermolecular forces are _________ than hexane's.

stronger

weaker

d. Water has a __________ vapor pressure compared with hexane.

higher

lower

e. Water has a ____________ boiling point than hexane.

higher

lower

Ex. 2: Circle the compound in each pair below with the higher boiling point:
a.

CO

or

O2

b.

HF

or

HCl

c.

CCl4

or

CF4

Ex. 3: NH3 molecules experience hydrogen bonds while NCl3 molecules experience dipoledipole forces. Explain how the boiling point for NCl3 (71C) can be higher than the
boiling point for NH3 (-33.3C).

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AN INTRODUCTION TO STRUCTURES AND TYPES OF SOLIDS

Solids can be crystalline or amorphous.

CRYSTALLINE SOLIDS: Have an ordered arrangement extending over a long range

different types of crystalline solids: molecular solids, covalent network solids, ionic and
metallic solids.

Molecular Solids: molecules often arranged in recurring patterns

exist as molecules held together by intermolecular forces

Ionic Solids: lattice of metal and nonmetal ions (eg. NaCl, MgO, etc.)
Have high melting points because of 3-D network of ions held together by ionic bonds
Some are slightly soluble in water (See Solublity Rules!)
Conduct electricity when melted or dissolved in solution

Atomic Solids (or Covalent Network Solids)

consist of one type of atom typically held together by covalent bonds
e.g. diamond exists as covalently bonded carbon atoms
covalent network solids never dissolve in any solvent

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Molecular Solids: consist of molecules held together by intermolecular forces

The Structure and Properties of Ice
Ice is an example of a molecular solid.
The hydrogen bonds between water molecules
are responsible for many unusual properties of
ice and water.
The density of ice (d=0.917 g/cm3) is lower than the
density of liquid water (d=1.00 g/cm3). This is an
exception! For all other substances, the solid is
more dense than its liquid.
When ice melts, the water molecules fill in the
holes, so liquid water is more dense than ice.
Because of hydrogen bonding, water molecules
in the ice are in a tetrahedral arrangement
"holes" or empty space.
Note the hexagonal holes in the molecular-level
image for ice at the right.
Snowflakes have hexagonal symmetry because of the hexagonal holes in the
molecular-level arrangement of water molecules in ice!

IONIC CRYSTALS: lattice of metal & nonmetal ions

e.g. NaCl, MgO, CaBr2
3D network of ions held together by electrostatic attraction = ionic bonds
high melting points, hard and brittle
conduct electricity only when melted or dissolved in solution

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CARBON AND SILICON: NETWORK ATOMIC SOLIDS

SOME COVALENT NETWORK SOLIDS
Graphite (a) and diamond (b) are two forms of carbon that are network covalent solids.

Network Covalent Solids: covalently bonded atoms forming a large network of indefinite size.
(a) Graphite is made up of layers of covalently bonded sp2 hybridized carbon atoms, and
the layers are held together by bonds that are delocalized over the entire solid.

(b) Diamond consists of covalently bonded carbon atoms that form such a network of sp3
hybridized carbon atoms in 3D tetrahedral structure.
Diamond is so hard because so many covalent bonds must be broken to break up the
diamond crystal.
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Ex. 1: Indicate the types of bonds or intermolecular forces that must be broken to melt the
following substances, and indicate which solid would have the higher melting point.
a.

ice

or

diamond (a form of carbon)

b.

ice

or

sodium chloride

Ex. 2: If sodium chlorides melting point is 801C while diamonds melting point is about
3550C, compare the relative strength of the ionic bonds in sodium chloride with the
covalent bonds in diamond.

Ex. 3: If graphite is the lead used in pencils, compare the strength of the bonds between
layers in graphite with the bonds holding carbon atoms together in a diamond.

AMORPHOUS: solids lacking 3D arrangement of atoms

may be similar to liquids in appearance since they lack the ordered
structure of crystalline solids
Silica (SiO2) makes up sand and quartz
glass: optically transparent solid of
inorganic materials cooled to a
rigid but non-crystalline
arrangement of Si-O bonded
atoms called quartz glass

SiO2
CHEM 161 Chapter 10

Glass
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