Physical Properties

Intermolecular Forces
An intermolecular attractive force is any force that causes otherwise independent
atom, molecules or ions to cluster together. Intermolecular forces are responsible
for phase changes such as condensation and solidification, and these forces
must be overcome during changes such as melting and vaporization.
Dipole Moments
The dipole moment (µ) is a measure of a molecules molecular dipole. The SI unit
for dipole moment is the coulomb meter (C m), but a much smaller unit the debye
(D) is commonly used for molecules. It is defined as the magnitude of the charge Q
at either end of the molecular times the distance of separation.
µ = Q x r 1 D = 3.33 x10-30 C m

Dipole Electro- Dipole Electro- Dipole Electro-

Moment negativity Moment negativity Moment negativity
(D) Difference (D) Difference (D) Difference
between between between
atoms atoms atoms
HF 1.82 1.8 H2O 1.85 1.2 NH3 1.47 0.8
HCl 1.08 1.0 H2S 0.97 0.4 PH3 0.58 0.0
HBr 0.28 0.8 AsH3 0.20 0.1
HI 0.44 0.4 SbH3 0.12 0.2
Sec. 5 - Physical Properties Forsey 1
The dipole moment increases with increasing electronegativity difference
between the bonded atoms. This is expected, since bond polarities also
increase with increasing electronegativity differences.

net dipole = 1.85 net dipole = 1.47

Sec. 5 - Physical Properties Forsey 2

 Ion-Ion Forces
Ionic bonds are very strong and a large amount of thermal energy is required to
break electrostatic lattice forces that act between the positive and negative ions.
Ionic compounds are solids at room temperature and have very high melting
points. The boiling points of ionic compounds are usually so high that most
compounds decompose before they boil.

Sec. 5 - Physical Properties Forsey 3

 Ion-Dipole Forces δ− δ− δ+ δ+
δ+ δ+ δ−
δ−
Important in aqueous solutions The magnitude of the
δ+ + δ−
interaction energy (E) depends on the charge of the ion δ+ δ−
δ− δ+
(z) and the inverse square of the distance (r). E = zµ/r 2 δ− δ+

Dipole-Dipole Forces
Many molecules have permanent dipoles that give rise to intermolecular forces.
Although the molecules are in constant motion and their orientations keep changing, the
polar molecules will, on average, be oriented so that oppositely charged ends are closer to
each other than ends with like charges
Because of the combination of attraction
and repulsion coupled with random
thermal motion dipole-dipole forces are
short range in nature, effective only for
molecules that are relatively close to each
other.
The strength of the dipole-dipole
interaction increases with the polarity of
the participating molecules.
i.e. Br2 which is nonpolar boils at 59oC
whereas ICl which is isoelectronic (they
have the same number of electrons) and
is polar boils at 97oC - 38 degrees higher.
Sec. 5 - Physical Properties Forsey 4
van der Waals or London Dispersion Forces
A polar molecule exerts a distorting effect on the electron clouds of nearby molecules; in this
way, it adds additional polarity to the existing polarity of each neighbor. This increase in
polarity enhances the mutual attraction. Even nonpolar species such as Cl2 or He can acquire
a temporary polarity when it is in the vicinity of a polar atom or molecule. An atom that is
temporarily polarized by another species is said to have an induced dipole. Nonpolar atoms
and molecules can induce temporary dipoles in each other. The motion of electrons in an atom
or molecule gives rise to fluctuating charge distributions and these, in turn, polarize
neighboring atoms and molecules. These induced dipoles are temporary and are effective only
at short distances but result in net attractive forces called a London dispersion force. The
strength of the London force depends on the magnitude of the induced dipole and this, in turn,
depends on how easily the electron cloud is polarized. Generally larger atoms and molecules
are more easily polarized than small atoms and molecules and will have higher melting and
boiling points. (when other effects are absent) I2 is more easily polarized than F2 because the
outer electrons in I2 are farther away from the nuclei and their clouds are more subject to
distortion than the electron clouds in F2
δ + δ - +

n o n p o la r m o le c u le in d u c e d d ip o le io n

δ + δ - δ + δ - δ + δ -
δ + δ -

in d u c e d d ip o le in d u c e d d ip o le p o la r m o le c u le

Sec. 5 - Physical Properties Forsey 5

 Generally substances consisting of large atoms and molecules will have higher
melting and boiling points than substances consisting of small atoms and
molecules.
This is just a rule of thumb since there are other factors that will effect melting
and boiling points such as hydrogen bonding
Substance Molar Mass (g) Melting Point (oC) Boiling Point (oC)
He 4.0 -272 -269
Ne 20.2 -249 -246
Ar 39.9 -189 -186
Kr 83.8 -157 -152
Xe 131.3 -112 -107
F2 38.0 -220 -108
Cl2 71.0 -101 -35
Br2 159.8 -7 59
I2 253.8 114 184
CF4 88.0 -150 -129
CCl4 153.8 -23 77
CBr4 331.6 90 190

Sec. 5 - Physical Properties Forsey 6

Hydrogen Bond (Dipole-Dipole)

When a hydrogen atom is bonded to a small, highly electronegative atom such as

oxygen, nitrogen, or fluorine, hydrogen is at the positive end of a very polar bond.
This hydrogen atom will be attracted to the negative ends of nearby polar molecules
the dipole-dipole interactions will be especially strong when the negative ends are
also nitrogen, oxygen or fluorine atoms.
Hydrogen bonding is a very strong intermolecular attractive force. 13 to 40 KJ/mol of
energy is required to disrupt hydrogen bonds, compared to 1 to 25 kJ/mol for other
types of dipole interactions.

Hydrogen
bonding
O
H
H H
O
O
H H
H
O O
H H H
H
Sec. 5 - Physical Properties Forsey 7
Boiling points usually increase going down a group because van der Waals
forces increase with increasing molecular size. Exceptions are H2O, HF, and
NH3, whose boiling points are unusually high because of hydrogen bonding.

The boiling point of water is about 160o higher than H2S because it is a less
polar compound and hydrogen bonding does not play a significant role

Sec. 5 - Physical Properties Forsey 8

An example of organic molecules that do and do not exhibit hydrogen
bonding are ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). Even
though both molecules have the same molecular weight ethanol boils at
78.5o C and dimethyl ether which cannot form hydrogen bonds boils at
-23.6o C.

Sec. 5 - Physical Properties Forsey 9

Surface tension
In a liquid molecule stick together (adhere). Therefore a molecule in the bulk
liquid has a lower potential than the one in the free gas and it takes energy to dig
out a molecule from the bulk and deposit into the gas.
Molecules at the surface of the liquid have an energy intermediate to the bulk and
free gaseous molecules. Therefore the potential energy decreases as you move
into the bulk liquid.
The attractive force that tends to draw molecules into the bulk solution is called
tension → surface tension.
Liquids minimize surface area and form spheres because the maximum number of
molecules will be in the bulk. → sphere provides the smallest surface to volume
ratio.
H
H
H H H
H O
O
H H O H
Air H
H O H
H
O O O H
H H O
H H H
H O H O
O H
O O
H H
H H O H
O H
Water H H

Glass

Sec. 5 - Physical Properties Forsey 10

Why do we get capillary action
Cohesive forces → intermolecular attraction between like molecules.
Adhesion → intermolecular attraction between unlike molecule

Adhesive forces between glass and water > cohesive

forces in the water. H2O creeps up inner walls and
additional H2O is pulled up as surface tension acts to
reduce the surface area of the film. It will rise until the
adhesive force between the H2O and glass equals the
gravitational force. The polar water molecule is
attracted to the silica oxide surface of the glass due to
intermolecular forces such as hydrogen bonding and
van der Waals forces.

Cohesive forces within liquid > than adhesive

forces between liquid and glass. In a nonpolar
solution such as carbon tetrachloride (CCl4) the
van der Waals attractive forces between
molecules is greater than the attractive forces
to the polar glass.
Magnitude of capillary effect is increased
with increasing surface tension and decreases with capillary width.
The intermolecular force also provides understanding to why specific compounds
dissolve into different solutions; or why solutions are miscible with each other.
Sec. 5 - Physical Properties Forsey 11
Solubilities
Dissolution of a solid in a liquid requires the orderly crystal structure of the solid to be
destroyed and form a more disorderly arrangement of the molecules (or ions) in solution.
The energy required to overcome lattice energies and intermolecular or inter ionic attractions
(that hold the solid together) comes from the formation of new attractive forces between
solute and solvent.
Ionic compounds have large lattice and interionic attractions. Only water and a few very polar
solvents are capable of dissolving ionic compounds.
These solvents dissolve ionic compounds by hydrating or solvating the ions.
They are able to do this because they can create large dipole-ion attractive forces large
enough to overcome the attractive forces of the Crystal.

Sec. 5 - Physical Properties Forsey 12

 A solution is a homogeneous mixture of two or more substances.

Solvent → greater concentration

Solute → smaller concentration

Generally like dissolves like → structurally similar compounds such as

ethanol and water are soluble in each other and will form a homogenous
mixture. Whereas structurally dissimilar compounds such as benzene and
water do not form homogeneous mixtures.

→ ethanol (CH3CH2OH) is miscible in water (H2O)

→ naphthalene dissolves in benzene

Protic solvent → Has a proton attached to an electronegative atom such as a N

or O that is usually rapidly exchangeable with D2O and that can hydrogen
bond to an electron pair donor. Solvents such as water, alcohols and
carboxylic acids

Aprotic solvent → solvents that do not have a proton attached to an

electronegative atom does not exchange with D2O such as diethyl ether,
chloroform, hexane, acetone, acetonitrile and benzene.

Sec. 5 - Physical Properties Forsey 13

Sec. 5 - Physical Properties Forsey 14
 Conceptualization of Molecular Forces
and Interactions
van der Waals only van der Waals + polar H H
H H
H
H C CH
δ+

CHC H C
H H H C δ+ C H
H HC H
C
H H C δ- O H
H H
H HC HC H H
δ- O
H H H C H
HH C H
H HCH H C H H C H
H δ C
+
C H C H C O
H C C H
H Oδ - H H C H
H H H

dipole : dipole dipole : induced dipole

van der Waals + polar + H-bonding ion : dipole

H-bonding O H δ+
δ+
H δ+ H
δ- H H _ δ+
O O H δ- δ+
H O H Cl H
δ- O +
H
H N CH H δ+ O
δ+
O van der Waals H H 3
δ-
CH3 O H
O
H δ-
H
dipole : induced dipole O
H δ-
δ+

Sec. 5 - Physical Properties Forsey 15

Summary of Attractive Electric Forces

Sec. 5 - Physical Properties Forsey 16

 Boiling Points
Boiling point → Temperature at which a compounds vapor pressure is equal to the external
pressure, usually 1 atm.
The vapor pressure is inversely related to the energy that causes the molecules to attract one
another. If the intermolecular attractive forces are weak little energy must be supplied in order
for vaporization to occur.
Vapour pressure α 1/cohesive forces
Alkanes
• The motion of electrons within a molecule are mutually correlated to produce a net
attraction at all times between molecules. (this has to be, otherwise the liquid would fly
apart).
• Attractive force varies 1/r6 → significant for only close molecules
• If to close and repulsion of electron charge clouds occur
• van der Waals interactions depends approximate on the area of contact between two
molecules. Therefore the greater the area the greater the attractive force.
B.P. Density increasing surface area or contact area
Methane -161.7 ---- creates stronger dispersion forces also
pentane 36.1 0.5572 getting heavier.
octane 125.7 0.7026

increasing contact area with increasing length of chain

Sec. 5 - Physical Properties Forsey 17
 Branched chained hydrocarbons

Branched chained hydrocarbons are more compact; therefore generally have a

higher density but low boiling point because of weaker interactions between
molecules.
B.P. °C M.P. °C

Pentane 36.1 -129.8

c5H12

Isobutane -11.7 -159.4

c5H12
neopentane even
with an extra carbon neopentane
9.4 -16.8 ?
has a lower B.P.
than pentane c6H14

packs steric
better interaction
causes weaker
interactions

Sec. 5 - Physical Properties Forsey 18

Branched chained hydrocarbons and melting points

A factor in melting points is that symmetrical molecules tend to

pack better in the crystalline lattice and have higher melting
points

Makes it harder to predict trends in melting points.

Sec. 5 - Physical Properties Forsey 19

 Factors that effect Boiling Point
1) Molecular Weight
2) Intermolecular forces: Dispersion, Dipole-Dipole, Hydrogen bonding (dipole-dipole)
3) Steric interaction

M.W B.P Hydrogen Hydrogen Soluble

bonding bonding in
with water Water
72 36°
70 30°
O
72

OH 74

88 99°
OH
O 74 35°
O
72 74°
H
O
74
O
O
74
OH

Between 4 to 6 carbons a ketone, aldehyde, ester or a carboxylic

acid become insoluble.
Sec. 5 - Physical Properties Forsey 20
 How about amines
Hydrogen
Hydrogen Bond
M.W. B.P Bonding with
with itself
water

NH 2 59

H
59
N

N 59

H H
Like an ether – CH3CH2OCH2, MW = 60, B.P. = 10.8°

R N What has a higher boiling point 1-propylamine or 1-propanol, why?

R
R

Sec. 5 - Physical Properties Forsey 21

Saponification of Triglycerides – Soaps and Detergents

O
CH2OC(CH2)16CH3 CH2OH
O CHOH + 3 CH3( CH2)16CO2 Na+
CHOC(CH2) 16CH3 + 3 NaOH CH2OH stearic acid
O
lye glycerol
CH2OC(CH2)16CH3 soap
could also use (glycerine)
glyceryl tristearate
(trisearin) wood ash (K2CO3)

CO2-
water and Na+ ions CO2-
CO2- CO2-
CO2- CO2- CO2- CO2-
-
O2C

CO2-

dirt, grease or oil -

O2C
micelle

CO2-
CO2-

Sec. 5 - Physical Properties Forsey 22

The problem with soaps is that they precipitate with hard water that
contain Ca2+, Mg2+, Fe3+ etc. which leaves a residue (bathtub ring)
Synthetic detergents or surfactants are long chained sulfonate salts
that do not precipitate with metal ions in hard water. These are anionic
surfactants like the fatty acids that form soap.

CH3(CH2) 11OSO3- Na+

CH3(CH2) 11 SO3- Na+

sodium dodecyl sulfate

(sodium lauryl sulfate)
sodium p-dodecylbenzenesulfonate

O
CH3
+ RCOCH2CH2O (CH2CH2O)2 CH2CH2OH
CH2 N C12H25Cl-
a neutral surfactant
CH3
benzalkonium chloride
a cationic surfactant

Sec. 5 - Physical Properties Forsey 23

 http://simscience.org/membranes/advanced/page4.html

http://simscience.org/membranes/advanced/page4.html

Good site for general knowledge of

surfactants
http://www.chemsoc.org/chembytes/eSec. 5 - Physical Properties Forsey 24
zine/2003/hargreaves_jul03.htm
 The Fluid Mosaic Model of the Cell Membrane
The most widely accepted model of the cell membrane is the "Fluid Mosaic
Model". By this concept the cell membrane consists of a continuous, fluid, double
layer of phospholipids. Proteins either are embedded in the bilayer or associated
with either the cytoplasmic or extracellular face. Carbohydrates are linked to the
proteins (glycoproteins) or lipids (glycolipids) only on the extracellular side. The
phospholipid profiles of the cytoplasmic and extracellular layers differ.
Cholesterol, in varying amounts depending on the cell type, lies within the
membrane serving to stabilize it.

http://www.erin.utoronto.ca/~w3bio315/cell%20membrane.htm

Sec. 5 - Physical Properties Forsey 25

 Bone Growth

Promotes calcium
self assembles into
crystallization along it
long tubular
axis much like natures
aggregates
collagen template

Sec. 5 - Physical Properties Forsey 26