You Ever Ask???

• Why is water usually a liquid and

not a gas?
• Why does liquid water boil at
such a high temperature for
such a small molecule?
• Why does ice float on water?
• Why do snowflakes have 6
sides?
• Why is I2 a solid whereas Cl2 is a
gas?
• Why are NaCl crystals little
cubes?
1
Chapter 11: Liquids, Solids and
Intermolecular Forces

2
 Chapter
Chapter Topics
Objectives
• Kinetic-Molecular Description of Liquids & Solids

• Intermolecular (IMF) Attractions & Phase

Changes
• Properties of Liquids
– Viscosity, Surface Tension, Capillary Action
– Evaporation, Vapor Pressure,
– Boiling Points & Distillation, Heat transfer
• Phase Changes
The following will NOT be covered in class
Types of crystals

3
 States of Matter

• List all the differences between

– Solids
– Liquids
– Gases
• Kinetic Energy?

4
 States of Matter (KE of Matter)

The fundamental difference between states of

matter is the distance between particles.

Intermolecular attractions in liquids & solids are strong:

KE of molecules << IMF 5
 States of Matter

Because in the solid and liquid states

particles are closer together, we refer to them
as condensed phases (depends on T and P).

6
The States of Matter

• The state a substance is in

at a particular temperature
and pressure depends on
two antagonistic entities:

– The kinetic energy of

the particles
– The strength of the
attractions between the
particles

7
 Examples

1. What is the difference between

intermolecular forces and intramolecular
forces?
2. List all the intermolecular forces you are
familiar with.
3. List all the intramolecular forces you are
familiar with.
4. Which forces are stronger?
8
 Intermolecular Forces

The attractions between molecules are not nearly as strong

as the intramolecular attractions that hold compounds
together.
Intermolecular forces are weaker than intramolecular forces ( to
break 2 O-H in bonds in water: 930 kJ/mol; to vaporize water:
43 kJ/mol)
Responsible for the existence of condensed states (liquids, solids)
9
 Intermolecular Forces

They are, however, strong enough to control physical

properties such as boiling and melting points, vapor
pressures, surface tension, and viscosities (reflect the
strength of the bond).

INTRAmolecular forces—the forces that holds atoms

together o form molecules
INTERmolecular forces: the forces between molecules, ions
and molecules-ions.
10
 Intermolecular Forces

These intermolecular forces as a group are

referred to as van der Waals forces (electrostatic
forces).

11
 IMF Problem
For each of the molecules below,
Determine the geometry of the molecule
Determine the polarity of the molecule
List the types of intermolecular force which act
between pairs of these molecules.
(a) CH4
(b) PF3
(c) CO2
(d) HCN,
(e) HCOOH (methanoic acid)
12
 Types of IMF
• Ion – Ion
• Van der Waals Forces
Dipole – dipole (for molecules with dipole moments)
Dipole – induced dipole
Dispersion forces (London)
Hydrogen Bond (special case of dipole-dipole (IMF)
London Dispersion Forces (induced dipole-dipole)
• Ion – induced dipole
• Ion – dipole
• Total attraction between molecules may depend on
more than one type of intermolecular force.
13
Ion – Ion Forces

08M16VD1

14
 Ion-Ion Forces

• Ion-ion forces: electrostatic forces of attraction

between __________________ of ionic
compounds. Generally very strong → 250 kJ.
(not a true intermolecular force)

• Ionic compounds: metal and nonmetal or

polyatomic anions (NH4+)

• Coulomb’s law & the attraction energy determine:

– melting & boiling points of ionic compounds
– the solubility of ionic compounds
15
 IMF: Ionic Solids
• Ion-ion interactions
– force of attraction between two oppositely charged
ions is determined by Coulomb’s law

F
 q+   q-
d2
• Energy of attraction between two ions is given by:

E = Fd =
q q + -
d
d2

=
q q 
+ -

D:\Media\Movies\08M17AN1.MOV
17
 Ion-Ion Forces
for comparison of magnitude

Na+—Cl- in salt
These are the strongest
forces.
Lead to solids with high
melting temperatures.

NaCl (lattice energy = 788

kJ/mol), mp = 800 oC

MgO (lattice energy = 3890

kJ/mol) , mp = 2800 oC
18
 Covalent Bonding Forces
for comparison of magnitude

C=C, 610 kJ/mol

C–C, 346 kJ/mol

C–H, 413 kJ/mol CN, 887 kJ/mol

19
Ion – Dipole Force

20
 Ion-Dipole Interactions
• Ion-dipole interactions are an important force in
solutions of ions.
• The strength of these forces are what make it
possible for ionic substances to dissolve in polar
solvents.

Na+(g) + 6H2O(l)→ [Na(H2O)6]+(aq) ΔHrxn = -405 kJ

21
Hydrated Ions? Coordination Number?
 Attraction Between Ions and Permanent
Dipoles

••
water
- dipole
O
H
••

H +

22
Attraction Between Ions and
Permanent Dipoles

Attraction between ions and dipole depends on ion

charge and ion-dipole distance.
Measured by ∆H for Mn+ + H2O → [M(H2O)x]n+

- H - H - H
••• O
H
•••O •••O
H H
+
Mg2+ Na+
+ +

Cs+

-1922 kJ/mol -405 kJ/mol -263 kJ/mol

23
 Dipole – Dipole Force

D:\Media\Movies\13M04AN2.MOV

24
 Dipole-Dipole Forces
Molecules that have permanent dipoles are attracted to
each other.
The positive end of one is attracted to the negative end
of the other and vice-versa.
These forces are only important when the molecules are
close to each other.
Note the difference between solid and liquid.

Liquid
liquid

Solid
25
 Effect of Dipole Moment on BP

Substance MM Dipole BP, K

moment
C3H8 44 0.1 231
propane

CH3OCH3 46 1.3 248

dimethyl ether

CH3CHO 44 2.7 294

Acetyl aldehyde

CH3CN 41 3.9 355

acetonitrile

26
 Dipole-Dipole Interactions

The more polar the molecule (higher μ), the

higher is its boiling point.
• Basic attraction : electrostatic, Coulomb’s Law
Examples: HCl, CO, SO2, NF3, etc 27
 IMF: Dipole-Dipole
• Dipole-dipole are of the order of 5 to 20
kJ/mol. (KE due to temp at 25oC about 4
kJ/mol). Cmpds that have these forces
(dipole-dipole) are frequently solids and
liquids at room temp.
• The stronger the forces, the ______ the
melting and boiling points of the
compounds.

28
Hydrogen Bond: type of dipole-dipole
force

13M07AN2

29
 Boiling Points of Simple Hydrogen-Containing
Compounds

The nonpolar
series (SnH4 to
CH4) follow the
expected trend.

The polar series

follows the trend
from H2Te
through H2S, but
water is quite an
anomaly.

EXPLAIN! 30
 Intermolecular Forces: H-bond
Which of these are capable of forming
hydrogen bonds among themselves?
a) CH3OH
b) C2H4
c) CH3NH2
d) HCN
e) NH4+
f) KF
g) CH3COOH

31
 Hydrogen Bonding

• The dipole-dipole
interactions experienced
when H is bonded to N, O,
or F (HIGH
ELECTRONEGATIVITY)
are unusually strong.
• Hydrogen nucleus is
exposed.
• We call these interactions
hydrogen bonds.

32
Hydrogen Bonding

33
H-Bonding Between Methanol and Water

- H-bond
+

-

34
Hydrogen Bonding in H22O
H-bonding is especially
strong (40 kJ/mol) in water
because
• the O—H bond is very
polar
• there are 2 lone pairs on
the O atom
Accounts for many of water’s
(and other molecules such
as DNA, proteins) unique
properties such as
anomalous high BP and
high viscosity.
35
 Hydrogen
Hydrogen Bonding
Bonding in
in H
H22O
O

Ice has open

lattice-like
structure.
Ice density is
< liquid.
And so solid
floats on water.

Snow flake:
www.snowcrystals.com
36
 Hydrogen Bonding in H22O
Ice has open lattice-like structure.
Ice density is < liquid and so solid floats on water.

One of the VERY few

substances where
solid is LESS DENSE
than the liquid.
37
 Hydrogen Bonding
Bonding

H bonds leads to
abnormally high
boiling point of water.

D:\Media\Movies\13M07AN
1.MOV

See Screen 13.7

38
 Boiling Point of Hydrides in ºC

Group VIA Group VIIA Group IVA Group VA

H2O 100 HF 20 NH3 -33 CH4 -161

H2S -65 HCl -85 PH3 -87 SiH4 -112

H2Se -45 HBr -69 AsH3 -60 GeH4 -90

H2Te -15 HI -35 SbH3 -25

39
 Hydrogen
Hydrogen Bonding
Bonding in
in Biology
Biology
H-bonding is especially strong in biological
systems — such as proteins and DNA.
D:\Media\Movies\09S03AN1.MOV
DNA — helical chains of phosphate groups and
sugar molecules. Chains are helical because
of tetrahedral geometry of P, C, and O.
Chains bind to one another by specific
hydrogen bonding between pairs of
Lewis bases.
—adenine with thymine
—guanine with cytosine 40
 Double helix
of DNA

Portion of a
DNA chain

41
Base-Pairing through H-Bonds

42
Induced Dipole –Induced Dipole
(London Dispersion Forces)

43
 London Dispersion Forces

While the electrons in the 1s orbital of helium

would repel each other (and, therefore, tend
to stay far away from each other), it does
happen that they occasionally wind up on the
same side of the atom.
44
 London Dispersion Forces

Instantaneous dipole

The helium atom becomes polar, with an excess

of electrons on the left side and a shortage on the
right side. Instantenous dipole forms (for an
instant)
45
 London Dispersion Forces

Another helium nearby, then, would have a

dipole induced in it, as the electrons on the
left side of helium atom 2 repel the electrons
in the cloud on helium atom 1.
46
 London Dispersion Forces

London dispersion forces, or dispersion

forces, are attractions between an
instantaneous dipole and an induced dipole.

47
 London Dispersion Forces

• These forces are present in all molecules,

whether they are polar or nonpolar.
• The tendency of an electron cloud to distort in
this way is called POLARIZABILITY.

48
Forces Involving Dipole -Induced Dipole

• Process of inducing a
dipole is polarization
• Degree to which
electron cloud of an
atom or molecule can
be distorted in its
polarizability.

49
 IMF: London Dispersion Forces
• Induced Dipoles: the temporary separation of positive
and negative charges in a neutral particle due to the
proximity of an ion, dipole, or another induced dipole.
On average μ = 0.

• London Dispersion Forces: attractive forces

(electrostatic in origin) that arise as a result of temporary
dipoles induced in atoms or molecules (instantaneous
dipoles). Weak: 0.1- 5 kJ/mol

• Dispersion forces allow non-polar molecules to

condense.

• Exist in all molecules!!!!! Importance depends on

the type of intermolecular forces.

50
 IMF: London Dispersion Forces

• London Forces
very weak
only attractive force in nonpolar molecules

Ar atom Cluster of Ar atoms 51

Factors Affecting London Forces

• The shape of the molecule

affects the strength of dispersion
forces: long, skinny molecules
(like n-pentane tend to have
stronger dispersion forces than
short, fat ones (like neopentane).
• This is due to the increased
surface area in n-pentane.

52
Effect of Geometry (shape) on BP of Molecules

Compound MM BP, ºC
N-butane 58 -0.45
Isobutane 58 -12.0

N-pentane 72 36.1
2-methyl butane 72 27.8
2,2 methyl propane 72 9.5

•Given the same molecular mass, GEOMETRY is important

53
 Factors Affecting London Forces

• The strength of dispersion forces tends to

increase with increased molecular weight.
• Larger atoms have larger electron clouds, which
are easier to polarize (larger polarizability.

54
 Boiling Points of Hydrocarbons
Molecule MM BP (oC)
CH4 (methane) 16 - 161.5
C2H6 (ethane) 38 - 88.6
C3H8 (propane) 44 - 42.1
C4H10 (butane) 58 - 0.5

C4H10
Note: linear
relationship C3H8
between BP and
MM (Polarizability C2H6
increases).

CH4

55
 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.

56
Dipole – Induced Dipole

57
FORCES INVOLVING INDUCED DIPOLES

How can non-polar molecules such as O2 and I2

dissolve in water?
The water dipole INDUCES a dipole
in the O2 electric cloud.

Dipole-induced
Dipole-induced
dipole
dipole 58
Forces Involving Dipole -Induced DIPOLE
Solubility increases with mass of the gas

59
 Forces Involving Dipole -induced Dipole

Consider I2
dissolving
in ethanol,
CH3CH2OH.
-
I-I I-I
The alcohol
+
- O temporarily
R H creates or - O
+ INDUCES a R H
dipole in I2. + 60
Summary of Intermolecular Forces
• Ion-dipole forces (very strong; solubility of ions in water)
• Dipole-dipole forces (larger dipole moments)
– Special dipole-dipole force: hydrogen bonds
• Induced dipoles (occur in all substances; important for
nonpolar molecules); increase with molar mass (glues);
depend on geometry. For large molecules may exceed
the force of dipole-dipole force (polymers, glues)

In general: ionic forces the strongest; then

hydrogen bonding; dipole-dipole; and lastly
dispersion for species of similar molar mass.
London Dispersion Forces exist in all molecules
and ions.
61
Summarizing Intermolecular Forces

62
Summary of dipole forces

63
Intermolecular Forces Summary

64
 Intermolecular Forces

Figure 13.13

65
 Example

What type of intermolecular forces exist between

the following pairs?
1. HBr and H2S
2. Cl2 and CBr4
3. I2 and NO3-
4. NH3 and C6H6

1. Dipole-dipole; dispersion;
2. dispersion;
3. ion-induced dipole; dispersion
4. dipole-induced dipole; dispersion
66
 Intermolecular Forces: Examples

5. Order the following compounds in order of increasing MP and BP:

a) N2, O2, H2
b) Cl2, F2, I2, Br2
c) SiH4, GeH4, SnH4, CH4

Order of MP and BP:

(a) H2< N2<O2
(b) F2<Cl2<Br2<I2
(c) CH4<SiH4<GeH4<SnH4
• Always compare like species.

6. But what about HF, HCl, HBr, HI

7. and H2O, H2S, H2Se, H2Te
8. and NH3, PH3, AsH3 and SbH3.
67
 Examples
1. List the IMF and arrange the substances
BaCl2, H2, CO, and Ne in order of
increasing boiling points.
2. In which of the following substances is
hydrogen bonding possible?
a. Methane
b. Methyl alcohol
c. Hydrazine (H2NNH2)
d. Methyl fluoride
e. Hydrogen sulfide
f. Carboxylic acid
68
 Intermolecular Forces: Examples

4. Arrange in order of increasing BP:

CO2 CH3OH CH3Br , RbF

5. Which one in each pair has the higher BP?

a) CH4 and C2H6

b) H2S and H2Te
c) NH3 and PH3
d) HCl and HF
e) I2 and ICl
69
 Example (London Forces)

6. Arrange the following molecules in order of

increasing strength of intermolecular forces.
F2
Br2
Cl2
I2
7. Explain the trend in the normal boiling points of
these liquids in terms of intermolecular forces.
CH4 normal boiling point: -161.5°C
CF4 normal boiling point: -28°C
CCl4 normal boiling point: +77°C
CBr4 normal boiling point: +190°C
70
 Intermolecular Forces: Examples

8. (11.100) Which of the following

substances has the highest
polarizability?
CH4, H2, CCl4, SF6, H2S

71
 Identify “intermolecular” forces

9. H2O 16. C6H6

10. CH2Cl2 17. Fe
11. KBr 18. CS2
12. F- + H2O 19. BCl3
13. I2 20. Na+ + NH3
14. CH3OH
15. PCl3

21. Dimethyl ether (CH3OCH3) and ethanol (C2H5OH)

have the same formula (C2H6O) but the BP of the ether is
-25ºC and of the ethanol 78ºC. Explain. 72