Intermolecular

Forces (IMFs)
Liquids, and
Solids
CHM2046:
Chapter
11
O H
H
C
O
H
C
C
H
H
H
H
H
C O
H
C C
H
H
H
H
H
Elucidate macroscopic properties of
solids & liquids by investigating the
microscopic level;
-forces between molecules,
ions, & atoms!
OBJECTIVE
Chem I: electronegativity; Lewis structures; VSEPR;
polar bonds; polar molecules and dipole moment.
enthalpy; ionic cmpds.
INTERMOLECULAR FORCES
-short range attractive forces
operating between the
particles in a liquid or solid

NOT covalent nor ionic bonding:
INTRAMOLECULAR FORCES


4
IMF & Phase Changes

(inc KE > IMF)
(reduced KE < IMF)
Which direction is exothermic; endothermic?
INTERMOLECULAR FORCES
- INFLUENCE STRUCTURES
IMPORTANT!!
- AFFECT MPs & BPs
- INFLUENCE SOLUBILITIES
-GASES FORM LIQUIDS

[are weaker than ionic & covalent:
known as intramolecular forces]
6
Why are MOLECULES attracted to each other?
Intermolecular forces are due to attractive forces
between opposite charges on polar molecules


(example,
o+
H
2
O
o-

o+
H
2
O
o-
)

Smaller charges, Q weaker attraction
Greater distance, d weaker attraction

These IMFs are weak relative to
ionic/covalent bonding
-due to partial charges & greater distances
d
Q Q
E
A C

7
Which is/are polar or nonpolar?
B) CH
3
Cl
C) NH
3
D) BF
3
E) CH
2
Cl
2
A) CS
2
8
What are the 3 types of IMFs that exist
between neutral molecules?
9
DISPERSION FORCES in Noble Gases
electrons on one side of He
An instantaneous dipole on any He atom induces
instantaneous dipoles on adjacent atoms, which
then attract each other
o- o+
o- o+ o+
o-
10
Noble Gases (atoms) are
polar or nonpolar?
LDF become stronger as
the atom (molecule)
becomes larger
Boiling Points of the Noble Gases
Molar Mass
Noble Gas g/mol Boiling Point (K)
He 4.00 4.2
Ne 20.18 27
Ar 39.95 87

Kr 83.80 120

Xe 131.30 165
A. Polarizability of the electrons (ease with
which e- can be moved to form a dipole)
11
Boiling Points of n-Alkanes
bp = 9.5
o
C (lower; gas)

12
B. Effect of Molecular Shape on Magnitude
of Dispersion Force
Which has the lower bp? Which is a gas at room temp?
13
2. Dipole-Dipole Forces
dipole force
The permanent dipole leads to the attractive forces
between the acetone molecules.
Polar molecules have a permanent dipole
This is due to bond polarity and shape of molecule
(NB: induced dipole is always present in these molecules)





14
Effect of Dipole-Dipole Attraction on Boiling and
Melting Points
formaldehyde
30. 0 g/mol
C
H
H
H
C
H
H
H
C
O
H H
30. 1 g/mol
ethane
Which substance has the higher bp and mp?
15
Intermolecular Forces and Solubility
POLAR solutes will dissolve in POLAR solvents



Like dissolves like
(miscible with each other)
Solubility depends on the attractive forces between
solute and solvent molecules.
CH
3
CH
2
OH dissolves in CH
3
OH and HOH
hydrophilic groups = ?
16

Polar substances dissolve in polar substances
(miscible with each other)

Dichloromethane
(methylene chloride)
Ethanol
(ethyl alcohol)
Solubility depends on the attractive forces between .
CH
2
O will dissolve in which of the above?
17
Nonpolar substances dissolve in nonpolar
substances (miscible with each other)
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
n-hexane
C H
C H
C
H
CH
CH
C
CH
3
toluene
C
Cl
Cl
Cl
Cl
Like dissolves like
hydrophobic groups are:
C-H, C-C
C
2
H
6
dissolves in which?
Recap: True or False?
18
a) For molecules with similar molecular
weights, the dispersion forces become stronger
as molecules become more polarizable
b) For noble gases, the dispersion forces
decrease, while boiling points increase as you
go down the column
c) Generally, dispersion forces between linear
molecules are greater than dispersion between
molecules with nearly spherical shapes
19
Immiscible Liquids
(polar & nonpolar groups do not mix
under standard conditions)

Suggest others!
20

3. Hydrogen-Bonding

HF
HF
HF
(Key examples: HF, H
2
O, H
3
N)
When H bonds to F, the atoms acquire relatively large
partial charges, giving rise to strong dipole-dipole
attractions between HF molecules.
HF, H
2
O, H
3
N: high bps due to ?
22
Which substance in a) and b) is a liquid at RT
(the other is a gas)?
a) CH
3
OH CH
3
CHF
2

b) CH
3
-O-CH
2
CH
3
CH
3
CH
2
CH
2
NH
2

23
4. Ion-Dipole Attraction
When an ionic compound is dissolved in water, the
ions are attracted to the dipole of polar H
2
O molecules

24
Summary of IMFs (Fig. 11.14)
25
What types of intermolecular forces are in the following?
Which compd has weakest IMFs, strongest IMFs; lowest
bp, highest bp; most likely a liquid @ 25
o
C?
a) CH
4

b) CH
3
Cl
c) CH
3
CH
2
CH
2
OH
d) SO
2

e) CO
2

Liquids: Properties & Structure
IMFs in liquids result in capillary
action, viscosity, and surface
tension
Capillary action: ability of a liquid to flow
against gravity up a narrow tube.
27
IMFs in Liquids
Surface tension
Generally,increases with increasing IMFs.

Viscosity is a measure of a fluids resistance to flow;
Generally,increases with increasing IMFs.
H
2
O forms H-bonds, a stronger IMF

compare H
2
O (polar) & CH
2
O (polar)

Liquids
The two key properties we need to describe are
EVAPORATION (vaporization) and its opposite
CONDENSATION

Break IM bonds
Make IM bonds
Add energy
Remove energy
LIQUID
VAPOR
Condensation
Evaporation
Supplement starts here
29
Distributions of Thermal Energies for H
2
O @ 2 Temps.
At a higher T, a larger number of molecules has high enough
energy to break IMFs & move from liquid to vapor phase.
High E molecules carry away heat E.
We cool down while sweating or during/after swimming.
at higher T, is the rate of evaporation slower or faster?
Liquids: heat of vaporization

LIQUID + heat VAPOR (endothermic)
H
2
O(liq) + 40.7 kJ H
2
O(g)

Compd. H
vap
(kJ/mol) Type of IMF
H
2
O 40.7 (100
o
C) ?
SO
2
26.8 (-47
o
C) ?
Xe 12.6 (-107
o
C) ?
The enthalpy of vaporization, H
vap
, is the heat
required (constant P; @ the T
b
) to vaporize 1 mole
of the liquid.
C
2
Cl
3
F
3
has a normal boiling point of 47.6
o
C. Calculate
the heat required to convert 35.0 g of C
2
Cl
3
F
3
from a
liquid at 10.00
o
C, to a gas at 105.00
o
C?
AH
vap
C
2
Cl
3
F
3
= 27.49 kJ/mol
Specific heat of C
2
Cl
3
F
3
(liq) = 0.91 J/g.K
Specific heat of C
2
Cl
3
F
3
(gas) = 0.67 J/g.K
Solve for Total heat = q1 + q2 + q3 = 7.7 kJ
changes:
C
2
Cl
3
F
3
(liq) will be heated from 10.00 to 47.6
o
C : q1
C
2
Cl
3
F
3
(liq) will be vaporized at 47.6
o
C : q2
C
2
Cl
3
F
3
(gas) will be heated from 47.6 to 105.00
o
C: q2



Question: Do question 11.43
33
Consider the following molecules: a) methane, CH
4

b) chloromethane, CClH
3
c) propyl alcohol,
CH
3
CH
2
CH
2
OH
Which requires less energy to cause evaporation?

At a fixed temperature, which evaporates fastest?

In the vapor phase, which requires the removal of the
most energy in order to cause condensation to form
the liquid?

liquids that evaporate easily are ... (weak IMF)
(gasoline, fingernail polish remover; alcohol)

liquids that do not evaporate easily are ..
(cumulative strong LDF: motor oil, cooking oil)
Liquids
EQUILIBRIUM VAPOR
PRESSURE: the pressure exerted
by a vapor over a liquid in a closed
container when the rate of
evaporation = the rate of
condensation (dynamic equilibrium).
When molecules of a liquid are in the vapor state (gas),
they exert a VAPOR PRESSURE.
Vapor Pressure vs T CURVES
Vapor Pressure T Curves
1. The curves show T and P where LIQUID
and VAPOR are in EQUILIBRIUM
2. As the T inc (x), the VP increases exponentially (y)
3. When VP = external P, the liquid boils

BPs of liquids change with altitude (AP)
" " C 78 atm 0.32 ft) (29,035 Everest Mt
O) H (bp C 100 atm 1.0 ft) (20 Boston
o
o
2
4. If external P = 760 mmHg (760 torr, 1 atm),
the T of boiling is the NORMAL BOILING
POINT

Vapor pressure
Opposite of above:
5. Liquid: Strong IMF
high BP high H
vap

low VP
Try to do question 11.52 in BLBMW
T, VP, H
vap
, & Clausius-Clapeyron Equation
Clausius-Clapeyron eqn used
to calculate H
vap
.
The nat. logarithm of the VP
is H
vaporization
and to 1/T.

C
RT
H
- P ln
vap
+
|
|
.
|

\
|
A
=
R
H -
slope -
vap
A
=
C
T
1
R
H
- P l n
vap
+
(

=
Plot of ln VP vs 1/T
The Clausius-Clapeyron equation can
be expressed in the following manner:
(

=
|
|
.
|

\
|
1 2
vap
1
2
T
1
T
1
R
H
-
P
P
l n
This is the 2-point form of the equation!!
40
Determine the normal boiling point of a substance whose vapor
pressure is 325.9 torr at 135C and has an AH
vap
of 32.1 kJ/mol.
|
|
.
|

\
|

=
|
|
.
|

\
|
K 408
1 1
K . / 314 . 8
/ 10 1 . 32
9 . 325
760
ln
2
3
T mol J
mol J
mmHg
mmHg
Given: T
1
= 135
o
C (408 K); P
1
= 325.9 torr; AH
vap
= 32.1 kJ/mol
Calculating temperature
(

=
|
|
.
|

\
|
1 2
vap
1
2
T
1
T
1
R
H
-
P
P
ln use,
P
2
= 760 torr (gives normal bp)
Find: T
2
when P
2
= 760 torr. Substituting the values.
41
Note that T
2
> T
1
, since P
2
> P
1
(see Q8 in Supp; 7 & 9)
T
2
= 448 K (175
o
C)
Vapor pressure temperature curves do not
continue exp. upward indefinitely!
As T and P increase, the CRITICAL T and P are
eventually obtained
Critical T and P
The substance that exist under these conditions:
SUPERCRITICAL FLUID



SC fluid: gas under very high P;
- its density similar to the liquid;
- its viscosity similar to gas.


Metallic and Ionic Solids
Properties & Structure


Fundamental Classification
Fundamental Classification
solids
46
Crystal Lattice
The arrangement of the particles in a crystalline
solid is called the crystal lattice

X-Ray crystallography allows us to determine the
arrangement of the particles in a crystalline
solid & distances between them.

The smallest unit that shows the pattern of
arrangement for all the particles is called the
........

47
Unit Cells
3-dimensional
-repeated over and over to give the macroscopic
crystal structure (3-D) of the solid
-each particle in a unit cell occupies a lattice point
Crystalline lattice can be represented by a small
collection of molecules, atoms, or ions:

Cubic Unit Cells (atomic solids: metals)

Po: Simple
cubic (SC)
Na: Body-
centered
cubic (BCC)
Al: Face-
centered
cubic (FCC)
Cubic Unit Cells
( ) = = -
3
edge of length cube a of Volume
a
b
c
all 90 angles between corners of the unit cell
Generally: assume unit cell is made of spherical particles
of each particle on a face is within the cube
of each particle at a corner is within the cube
all the edges have equal length = l
An atom at the center, belongs entirely to that cube
of each particle on an edge is within the cube
50
Cubic Unit Cells
of each particle at
a corner is within
each cube
of each particle on
a face is within each
cube
of each particle
on an edge is within
each cube
51
Cubic Unit Cells: Simple Cubic
8 particles, one at each corner of a cube


i.e, each particle is a part of 8 cells

Net no. of particles in each unit cell = 1
8 corners 1/8
-length of edge of unit cell = twice the
radius
l = 2r
coordination number of 6
2r
cell unit in the lies particle each of th
8
1
52
Cubic Unit Cells: Body-Centered Cubic
9 particles, one at each corner of a
cube + one in center
1/8 th of each corner particle lies
within the unit cell
Net no. of particles in each unit
cell = 2
8 corners 1/8 + 1 center
edge of unit cell, l = (4r/\ 3)
(pg. 10 of supplement)
coordination number of 8
3
4r
53
Cubic Unit Cells: Face-Centered Cubic
14 particles, one at each corner (8) +
one in center of each face (6) of a
cube
1/8th of each corner particle + of
face particle lies in the unit cell

Net no. of particles in each unit cell
8 corners 1/8 + 6 faces = 4

length of edge of unit cell
l = 2r\2
2 2r
coordination number = ?


Cubic Unit Cells of Metals


Unit Cell Type l Net Number Atoms PE CN
(8) SC
(9) BCC
(14) FCC
2r
2 2r
(4r/\ 3)
l l l
fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 10
23
atoms
Q. Calculate the density of Al if it crystallizes in a fcc
unit cell and has a radius of 143 pm
fcc unit cell, & r = 143 pm
density, g/cm
3

summary:
Solution:
Plan:



Relation-
ships:
Given:
Find:
1 pm = 10
-12
m, 1 m = 10
2
cm,
l r V
mass
fcc
m/V
d
# Al atoms mass 1 Al atom
l = 2r2, V = l
3

l = 2r2 V = l
3

Calculate the density of Al if it crystallizes in a fcc and
has a radius of 143 pm
the accepted density of Al at 20C is 2.71 g/cm
3

ANS:
Solution:
Concept
Plan:


Relation-
ships:
Given:
Find:
l r V
mass
fcc
m/V
d

density, g/cm
3
mass = 1.792 10
-22
g
r = 1.43 10
-8
cm; l? V?
l = 2r2, V = l
3

57
Cesium Chloride Structures
Structures of many ionic solids are built by taking a SC or FCC
lattice of X
n-
, & placing M
n+
in the holes (SC, O
h
, T
d
) in the lattice.
coordination number = 8
of each Cl

(181 pm) inside the
unit cell (net = 1 Cl
-
)
one Cs
+
(167 pm) inside the unit
cell, occcupies
cubic hole = central space in
simple cubic arrangement of Cl

ions.

Cs:Cl = 1: (8 ), therefore the
formula (empirical) is CsCl
58
Rock Salt Structures: NaCl
coordination number = 6
Cl

ions (181 pm) in a face-centered

cubic arrangement (green)
of each corner Cl

inside the unit cell
of each face Cl

inside the unit cell
Cl
-
: ( 8) + ( 6) = 4

each Na
+
(97 pm) in holes between Cl


Na
+
in octahedral holes
1 Na
+
in center of unit cell
of each edge Na
+
inside the unit cell

Na
+
: = ( 12) + 1 = 4
NET = 4:4 = 1:1 (smallest ratio)
therefore the formula is NaCl
complete unit cell
59
Phase Diagrams
critical point :

triple point:
describe the different phases and phase changes that occur at
various T & P (3 regions, 3 lines, 2 points) section 11.8
3 regions represent phases:
3 lines represent state changes
-the liquid/vapor line is the ---------------- curve
both phases exist simultaneously @ liquid/vapor line
The 2 points

61
62
Band Theory
When 2 atomic orbitals (AO) combine, they produce
both a bonding and an antibonding molecular
orbital

When many atomic orbitals combine they
produce a band of bonding molecular orbitals
and a band of antibonding molecular orbitals

the band of bonding molecular orbitals is called
the ---------

the band of antibonding molecular orbitals is called
the ----------
63
Molecular Orbitals of Polylithium
Li: [He] 2s
1
64
Types of Band Gaps and Conductivity
as the temperature rises, some of the electrons may acquire enough
energy to jump to the conduction band.
The difference in energy between the valence band and conduction
band is called the BAND GAP!
The larger the band gap, the fewer electrons there are with enough
energy to make the jump
@ absolute zero, all the electrons will occupy the valence band