2/23/2010

Intermolecular
Forces, Liquids
and Solids

Intermolecular Attractions
-Remember: We are talking about attractions between
molecules (intermolecular forces), or ions; not the
bonds between the atoms that make up the molecule.
-Ion attractions tend to be the strongest forces (700 to
1100kJ/mol) vs. covalent (100-400kJ/mol)

Why are Intermolecular Forces

Important
-They are directly related to properties such as
melting point,
point boiling point,
point and the energy needed to
convert a solid to a liquid or a liquid to a vapor
(enthalpy
enthalpy [latent heat] of fusion and vaporization).
vaporization
MPNaCl = 801oC

MPHe = -272.19oC MPH2O = 0oC

- They are important in determining the solubility of

gases, liquids, and solids in various solvents
- They are crucial in determining the structures of
biologically important molecules such as DNA and
proteins (primary, secondary, tertiary and quaternary
structures)

Dipole-Dipole Interactions

There are different types of

attractions between molecules/ions
IonIon-Ion; IonIon-Dipole; DipoleDipole-Dipole; London Forces,
Forces etc.
Electrostatic attractions determined by Coulombs
Law
F = kq1q2/r2

k=8.988x109Nm2/C2

Attractive forces depend upon three factors:

- The distance between the ion and the dipole. The
closer the ion and dipole, the stronger the attraction
- The charge on the ion. The higher the ion charge, the
stronger the attraction.
- The magnitude of the dipole. The greater the
magnitude of the dipole, the stronger the attraction

Effects of intermolecular forces

Affects solvation energy (enthalpy of hydration):
Dissolving substances in one another
Exothermicity depends upon 1/r
In general: Like substances dissolve like substances
(Polar in polar (ionic); nonpolar in nonpolar, etc.)
Permanent dipole-attractions: Hvap increases with
polarity and molar mass

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Nonpolar Molecular Interactions

*Dipole-Induced Dipole
*London (dispersion) Forces (induced dipoles)
-Produces momentary
momentary dipoles
dipoles that hold the
molecules together
-Caused by the temporary shifting of the
electron clouds through interactions between
molecules

Like Dissolved Like

-For an homologous series (CH4, C2H6, C3H8,

etc.) polarizability increases with molar mass
(greater electron cloud shifting)

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Hydrogen Bonding
Special case of polar intermolecular attractions
Comes from molecules containing one or more of the following:
H-N
H-O
H-F
bonds.
The EN for the bonds (H=2.2; N=3.0; O=3.5; F=4.0) creates a
strongly polar molecule that produces greater intermolecular
attractions. (between 5 and 30kJ/mol typically).

Properties of Water

Boiling Points

Due to hydrogen bonding

- Tetrahedral arrangement of hydrogens around each oxygen
- Open-caged structure (unique) in its solid form (10% less dense
than the liquid form)
- Oxygens are arranged at the corners of a puckered, six-sided
ring. (snowflakes are all six-sided)
- Water has a relatively high melting and boiling point

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Heliacal structure

Hydrogen bonding is
responsible for some of the
secondary and tertiary structure
in proteins (note the hydrogencarbonyl attraction
Pleated structure

Related Questions:
Exercise 13.1
which should have the more negative hydration energy, For Cl-?
Exercise 13.2
You mix water, CCl4, and hexane. What type of
intermolecular forces can exist between each pair of
these compounds? If you mix the three liquids, describe
what observations you might make.
Exercise 13.3
Using structural formulas, describe the hydrogen
bonding between methanol molecules. What physical
properties of methanol are likely to be affected by
hydrogen bonding?

13.1
Because F- is the smaller ion, water molecules can approach most
closely and interact more strongly. Thus, F- should have the more
negative heat of hydration.
13.2
Water is a polar solvent, while hexane and CCl4 are nonpolar.
London dispersion forces are the primary forces of attraction
between all pairs of dissimilar solvents. For mixtures of water with
the other solvents, dipole-induced dipole forces will also be
present. When mixed, the three liquids will form two separate
layers, the first being water and the second consisting of a mixture
of the two nonpolar liquids.
13.3
The polar structure (hydrogen bonding) of methanol will affect
things such as enthalpies of fusion and vaporization and solubility.
H3C
O
H

O
H3C

Standard Molar Enthalpy of Vaporization

Properties of Liquids

Hovap (in kJ/mol)

-Vaporization
-Vapor Pressure
-Boiling Points
-Critical Properties
-Surface Tension; Capillary Action; Viscosity (cohesive / adhesive)

Vaporization (endothermic) Condensation (exothermic)

Vaporization (Evaporation)
Liquid to the vapor (gas) state

Energy
Distribution at
temperatures T1
and T2 for a liquid

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Note that for

the hydrogen
halides, only
HF relies on
hydrogen
bonding. The
rest rely on
dispersion
forces
(increase with
molar mass)

Vapor Pressure

Pressure due to a
volatile liquid in a
sealed container
Increases with
increasing
temperature
Condensation and
evaporation rate are
in dynamic

equilibrium

The Relationship Between Vapor Pressure and Enthalpy

of Vaporization:
The Clausius-Clapeyron Equation

H 0 vap
ln P =
+C
RT

H 0 vap
H 0 vap

ln P2 ln P1 =
+ C
+ C
RT2
RT1

1 1
P
vap
ln 2 =

P1
R T1 T2

R = 8.314472J/molK, T in Kelvin

Boiling Point
The boiling point of a liquid is the temperature at which its
vapor pressure is equal to the prevailing external pressure.
If the external pressure is 760torr it is known as the normal
boiling point.

Critical Temperature and Pressure

As a liquid is heated in a sealed container:
Vapor Pressure Increases
The density of the liquid phase decreases
The density of the vapor phase increases
At the critical point, the vapor/liquid phases are
indistinguishable
Known as a supercritical fluid
Occurs for a substance at its critical temperature (Tc) and
Pressure (Pc)

Question:
Benzaldehyde, C6H5CHO, has a normal boiling point
of 179.0oC and a critical point at 422oC and 45.0atm.
Estimate its vapor pressure at 100.0oC.
CO2 becoming supercritical
Supercritical CO2 is used in
the natural extraction of
caffeine from coffee. The
caffeine is soluble in
supercritical CO2 and when
the pressure and temperature
are decreased the caffeine
precipitates out and the CO2
is reused.

Answer:
ln (45.0/1.0) = (Hovap/8.314)(1/452.15 1/695.15)
Hovap = 40,936.4 J/mol
ln (P2 /1.00) = (40,936.4/8.314)(1/452.15 1/373.15)
P2 = .099711 = .0997atm

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Question:
The normal boiling point of acetone, an important
laboratory and industrial solvent, is 56.2oC and its
Hvap is 25.5kJ/mol. At what temperature (in Celsius)
does acetone have a vapor pressure of 375mmHg?

Answer:

Question:
At its normal boiling point, the enthalpy of
vaporization of chloroform, CHCl3 is 247J/g.
a. How many grams of CHCl3 can be vaporized with
6.62kJ of heat?
b. What is Hvap of CHCl3 expressed in kilojoules per
mole?
c. How much heat, in kilojoules, is evolved when
19.6g of CHCl3(g) condenses?

ln(375/760) = (25,500/8.314)(1/329.35 1/T2)

T2 = 306.129K

Answer:

306.129K 273.15K

a. 6,620J / 247J/g = 26.8016 = 26.8g

b. .247kJ/g (119.378g/mol) = 29.4864 = 29.5kJ/mol
c. 19.6g(.247kJ/g) = 4.84kJ

= 32.9791 = 33.0oC

Heating/Cooling Curve for Water

Phase Diagram Regions

Fusion
Curve
Triple
Point

Vapor Pressure
Curve
Supercooling

Sublimation
Curve

Super Critical
Fusion
Region

Hosublimation= Hofusion + Hovaporization

Phase Diagram for Water

(Note negative fusion curve and triple point)

Phase Diagram for Carbon Dioxide

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Polymorphism

Question:
Assume that a skater has a mass of 80.kg and that
his skates make contact with 2.5cm2 of ice.
Calculate the pressure in atm exerted by the skates
on the ice.
b. if the melting point decreases by 1.0oC for every
125atm of pressure, what would be the melting point
of the ice under the skates?
Answer:
((80.kg)(9.8m/s2)/[(2.5cm2)(1m/100cm)2])(1atm/101,300Pa)
= 30.95 = 31atm
31atm (1.0oC/125atm) = .248
0oC - .248oC = -.248 = -.25oC

Question:
You decide to cool a can of soda pop
quickly in the freezer compartment of
a refrigerator. When you take out the
can the soda pop is still liquid; but
when you open the can, the soda pop
immediately freezes. Explain why this
happens.

Question:
Sketched here are two hypothetical phase diagrams for a
substance, but neither of these diagrams is possible. Indicate
what is wrong with each one.

Answer:
The pop has become supercooled in the
refrigerator. Once you agitate the pop by opening
it, it immediately freezes because its temperature is
below the freezing point.

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Surface Tension:
Tension The "skin" on the surface of a liquid caused by
the increase in downward force on surface molecules from by the
molecules that exist below the surface. (i.e. there is no counter
force from above).
By definition, surface tension (), is the amount of work required to
extend a liquid surface. Units are usually expressed in J/m2.
Surface tension decreases with an increase in temperature.

Lower Energy

Answer: In the first picture, the vapor pressure curve cant dip down such that
it goes from vapor to liquid and back to vapor again.
In the second picture, the sublimation curve can never be just an extension of
the vapor pressure curve. There must be a discontinuity at the triple point.
Since the slope of the lnP vs. 1/T for the vapor pressure curve is the Hovap,
the sublimation curve slope would be given by Hosub. These two slopes
cannot be exactly the same since Hosub = Hofus + Hovap

Cohesive forces:
forces Attraction between identical molecules in a liquid
(responsible for surface tension).

Higher
Energy

Characteristics of Crystalline Solids

Adhesive forces:
forces Attraction between different molecules (e.g. the
way water is attracted to the side of a glass producing a meniscus).
This also accounts for capillary action.
Read to the bottom of a concave meniscus and to the top of a convex
meniscus
Viscosity:
Viscosity A liquid's resistance to flow caused by the strength of
attraction between the molecules and often their length. Viscosity is
related to intermolecular forces and especially hydrogen bonding.
(The common unit is the poise (P). The SI unit is 1 N s m-2 = 10P)
Surface tension and viscosity decrease with an increase in
temperature
Meniscus
of mercury
and water

Cohesive vs
Adhesive

The Structure of Crystals

The seven 3dimensional unit cells

Crystal: A solid substance with a regular shape having plane

surfaces and sharp edges that intersect at fixed angles.
A unit cell is the smallest representative unit of the repeating
pattern that makes up the crystal.
Nature uses seven three-dimensional unit cells. They differ
from one another in that their sides have different relative
lengths and their edges meet at different angles.
The simplest of the seven is the cubic unit cell (the focus of
this section)
- Edges of equal length
- 90o angles

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Body (one
whole atom)

Different
positions
within the unit
cell.

Face (one-half
atom)

Simple cubic (sc)

(aka primitive
cubic)
Body centered
cubic (bcc)
Face-centered
cubic (fcc)
(aka cubic close
packed.

Edge (onefourth atom)

Corner (oneeigth atom)

Arrangements for hexagonal close-packed (hcp) and

cubic close-packed (ccp)[face-centered cubic] structures
(note tetrahedral and octahedral holes)

Cubic Structures

Face
There are twelve of
these octahedral
edge types

There are eight of

these tetrahedral
types

Corner
Face
Face

Face

Corner
Corner

Face
Face

Face

Face

Face
Face

Face
Face

Face
There is one of
these octahedral
center types

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Simple Cubic Geometry

Body-centered Cubic Geometry

Ionic
Compounds

Face-centered Cubic Geometry

Examples of Ionic Compound Crystals

(ions can often reside in the holes between other ions)
Ex. Mn+ ions occupying all the cubic holes of a simple
cubic Xn- lattice as in CsCl

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Examples of Ionic Compound Crystals

(ions can often reside in the holes between other ions)
Ex. Mn+ ions in all the octahedral holes in a faceface-centered
cubic Xn- lattice as in NaCl

There are 4 octahedral hole atoms possible 12 edges x

each and one in the center.

Examples of Ionic Compound Crystals

(ions can often reside in the holes between other ions)
Ex. Mn+ ions occupying half of the tetrahedral holes in a
face--centered cubic Xn- lattice as in ZnS
face

There are 8 possible tetrahedral holes in the fcc lattice

Remember: The number of ions of each type in the

unit cell should be consistent with the stoichiometry of
the ionic compound (i.e. the ion ratios in the empirical
formula)

Question:
Tungsten has a body-centered cubic crystal
structure. Using a metallic radius of 139pm for the W
atom, calculate the density of tungsten.

Allotropes of Carbon
Covalent (molecular) Network Solids
Diamond
sp3 hybridized
M.P. = 3500oC

Answer: The diagonal through the body is 4 radii =

4(139pm) = 556pm (designated as c)
c2 = a2 + 2a2
c2 = 3a2
a = (c2/3)1/2
a = (5562/3)1/2 = 321.007pm (cube edge length)

Nonconductive

bcc crystals have 2 atoms per unit cell

183.9g/mol (1mol/6.022x1023atoms)(2atoms) =
6.1076x10-22g
Density = 6.1076x10-22g / (3.21007x10-8cm)3 = 18.464
= 18.5g/cm3

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Graphite

Buckminsterfullerine

sp2 hybridized

Buckyball or fullerenes

Conductive

C60

Lubricant

Caged-Structure

All of these forms of carbon

are known as allotropes
(Two of more forms of an
element that differ in their
basic molecular structure)

Amorphous Solids

Carbon nanotubes
Discovered
Graphene sheet (like
chicken wire), rolled and
capped to make structure.

Structures vary in length

from a few nanometers to a
micrometer or more. Their
diameters are generally in
the range of a few
nanometers.
(This picture is a bundle of
single-walled nanotubes)

Solids, such as glass (composed

of silicon and oxygen) do not
have a regular structure or any
long range order
Sometimes glass is thought of as
a supercooled liquid.

These solids dont melt at one

specific temperature, but over a
range of temperatures

Other examples are polyethylene

and nylon.

Physical Properties of Solids

Heat energy absorbed on melting = enthalpy of fusion
= Hofusion (kJ/mol)
Heat energy evolved on freezing = enthalpy of
crystallization = - Hofusion (kJ/mol)
Some substances go directly from the solid to vapor
state (sublimation)
Enthalpy of sublimation
= Hofusion + Hovaporization

Sublimation of iodine

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Examples:

Enthalpies of fusion crystallization

1. One unit cell of the mineral perovskite is illustrated here. This

compound is composed of calcium and titanium cations and oxide
anions. Based on the unit cell, what is the formula of perovskite?
Enthalpies of fusion
correlate with melting
point temperatures.

2. If an ionic solid has a fcc lattice of anions (X) and all of the
tetrahedral holes are occupied by metal cations (M), is the formula
of the compound MX, MX2 or M2X?

Answers:
Each edge is , each corner is 1/8 and there is 1 whole
in the middle
12 O2- (1/4) = 3 O28 Ca2+ (1/8) = 1 Ca2+
1 Ti4+ (1) = 1 Ti4+
CaTiO3
FCC anions means 8 corners *(1/8) + 6 faces*(1/2)
= 4 anions
There are 8 possible tetrahedral holes = 8 cations
M2X

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