INTERMOLECULAR FORCES

Introduction:
The physical properties of
Melting point
Boiling point,
vapor pressure,
Evaporation,
viscosity,
surface tension, and
solubility are related to the strength of
attractive
forces between molecules.
 Intermolecular forces
These attractive forces are called Intermolecular
Forces. The amount of "stick togetherness" is
important in the interpretation of the various
properties listed above.

There are four types of intermolecular forces.

Most of the intermolecular forces are identical to
bonding between atoms in a single molecule.
Intermolecular forces just extend the thinking to
forces between molecules and follows the
patterns already set by the bonding within
molecules.
 1. IONIC FORCES
The forces holding ions together in
ionic solids are electrostatic forces.
Opposite charges attract each other.
These are the strongest intermolecular
forces. Ionic forces hold many ions in a
crystal lattice structure.
IONIC FORCES
 Ion - Ion Interactions
Two oppositely-charged particles flying about in a
vacuum will be attracted toward each other, and the
force becomes stronger and stronger as they
approach until eventually they will stick together and
a considerable amount of energy will be required to
separate them.
They form an ion-pair, a new particle which has a
positively-charged area and a negatively-charged
area.
There are fairly strong interactions between these
ion pairs and free ions, so that these the clusters
tend to grow, and they will eventually fall out of the
gas phase as a liquid or solid (depending on the
temperature).
A small representative bit of a sodium
chloride lattice
exploded version of a sodium chloride
lattice
NaCl(s)
 Ionic Bonding
Ionic bonding is best treated using a simple
electrostatic model . The electrostatic model is simply
an application of the charge principles that opposite
charges attract and similar charges repel.
An ionic compound results from the interaction of a
positive and negative ion, such as sodium and chloride
in common salt.The IONIC BOND results as a balance
between the force of attraction between opposite plus
and minus charges of the ions and the force of
repulsion between similar negative charges in the
electron clouds.
In crystalline compounds this net balance of forces is
called the LATTICE ENERGY. Lattice energy is the
energy released in the formation of an ionic compound.
 Ionic Bonding
DEFINITION: The formation of an IONIC BOND is the
result of the transfer of one or more electrons from a
metal onto a non-metal.Metals, with only a few electrons
in the outer energy level, tend to lose electrons most
readily. The energy required to remove an electron from
a neutral atom is called the IONIZATION POTENTIAL.

Energy + Metal Atom ---> Metal (+) ion + e-

Non-metals, which lack only one or two electrons in the

outer energy level have little tendency to lose electrons -
the ionization potential would be very high.
 Ionic Bonding

Instead non-metals have a tendency to gain

electrons. The ELECTRON AFFINITY is the energy
given off by an atom when it gains electrons.

Non-metal Atom + e- --- Non-metal (-) ion + energy

The energy required to produce positive ions

(ionization potential) is roughly balanced by the
energy given off to produce negative ions (electron
affinity). The energy released by the net force of
attraction by the ions provides the overall stabilizing
energy of the compound.
 METALLIC STRUCTURES
What is a metallic bond?
Metals tend to have high melting points
and boiling points suggesting strong
bonds between the atoms.
Even a metal like sodium (melting point
97.8C) melts at a considerably higher
temperature than the element (neon)
which precedes it in the Periodic Table.
 Metallic bonding in sodium

Na(23) ---1s22s22p63s1.
When sodium atoms come together, the electron
in the 3s atomic orbital of one sodium atom
shares space with the corresponding electron on
a neighbouring atom to form a molecular orbital -
in much the same sort of way that a covalent
bond is formed.
 Metallic bonding in sodium
The difference, however, is that each sodium
atom is being touched by eight other sodium
atoms - and the sharing occurs between the
central atom and the 3s orbitals on all of the
eight other atoms. And each of these eight is
in turn being touched by eight sodium atoms,
which in turn are touched by eight atoms -
and so on and so on, until you have taken in
all the atoms in that lump of sodium.
 Metallic bonding in sodium
All of the 3s orbitals on
all of the atoms overlap to
give a vast number of
molecular orbitals which
extend over the whole
piece of metal. There
have to be huge numbers
of molecular orbitals, of
course, because any
orbital can only hold two
electrons.
The electrons can move freely within these
molecular orbitals, and so each electron
becomes detached from its parent atom. The
electrons are said to be delocalised. The
metal is held together by the strong forces of
attraction between the positive nuclei and
the delocalised electrons.
 Metallic bonding in sodium
This is sometimes
described as "an array
of positive ions in a sea
of electrons".

If you are going to use

this view, beware! Is a
metal made up of atoms
or ions? It is made of
atoms.
 Metallic bonding in Sodium
Each positive centre in the
diagram represents all the
rest of the atom apart from
the outer electron, but that
electron hasn't been lost - it
may no longer have an
attachment to a particular
atom, but it's still there in
the structure. Sodium metal
is therefore written as Na -
not Na+ or potassium metal
is written as K but not K+.
 Alkali Metals

Eight touching neighbour Co-ordination No. is eight

Metallic bonding in magnesium
If you work through the same argument with magnesium,
you end up with stronger bonds and so a higher melting
point.

Magnesium has the outer electronic structure 3s 2. Both of

these electrons become delocalised, so the "sea" has
twice the electron density as it does in sodium. The
remaining "ions" also have twice the charge (if you are
going to use this particular view of the metal bond) and so
there will be more attraction between "ions" and "sea".

More realistically, each magnesium atom has one more

proton in the nucleus than a sodium atom has, and so not
only will there be a greater number of delocalised
electrons, but there will also be a greater attraction for
them.
Metallic bonding in magnesium

Magnesium atoms have

a slightly smaller radius
than sodium atoms, and
so the delocalised
electrons are closer to
the nuclei. Each
magnesium atom also
has twelve near
neighbours rather than
sodium's eight. Both of
these factors increase
the strength of the bond
still further.
 Metallic bonding in transition
elements

Transition metals tend to have

particularly high melting points and
boiling points.
The reason is that they can involve the
3d electrons in the delocalisation as
well as the 4s.
The more electrons you can involve,
the stronger the attractions tend to be.
 d-block elements
Remember that the 4s orbital
has a lower energy than the
3d orbitals and so fills first.
Once the 3d orbitals have
filled up, the next electrons
go into the 4p orbitals as
you would expect.
d-block elements are
elements in which the last
electron to be added to the
atom is in a d orbital. The
first series of these contains
the elements from scandium
to zinc, which you probably
called transition elements or
transition metals.
The terms "transition
element" and "d-block
element" don't quite have
the same meaning, but it
doesn't matter in the present
context.
 d-block elements
d electrons are almost always described
as, for example, d5 or d8 - and not written
as separate orbitals.
Remember that there are five d orbitals,
and that the electrons will inhabit them
singly as far as possible. Up to 5
electrons will occupy orbitals on their
own. After that they will have to pair up.

d5 means:

d8 means :
 d-block elements
Notice in what follows that all the 3-
level orbitals are written together, even
though the 3d electrons are added to
the atom after the 4s.
Sc: 1s22s22p63s23p63d14s2
Ti:1s22s22p63s23p63d24s2
V :1s22s22p63s23p63d34s2
Cr:1s22s22p63s23p63d54s1
Whoops! Chromium breaks the sequence. In chromium, the electrons in the
3d and 4s orbitals rearrange so that there is one electron in each orbital. It
would be convenient if the sequence was tidy - but it's not!
 d-block elements
Mn: 1s22s22p63s23p63d54s2 (back to being tidy again)
Fe : 1s22s22p63s23p63d64s2
Co: 1s22s22p63s23p63d74s2
Ni : 1s22s22p63s23p63d84s2
Cu: 1s22s22p63s23p63d104s1 (another awkward one!)
Zn: 1s22s22p63s23p63d104s2 (And at zinc the process of
filling the d orbitals is complete.)

A transition element is defined as one which

has partially filled d orbitals either in the
element or any of its compounds. Zinc (at the
right-hand end of the d-block) always has a
completely full 3d level (3d10) and so doesn't
count as a transition element.
 The metallic bond in molten
metals
In a molten metal, the metallic bond is
still present, although the ordered
structure has been broken down.
The metallic bond isn't fully broken
until the metal boils. That means that
boiling point is actually a better guide
to the strength of the metallic bond
than melting point is.
On melting, the bond is loosened, not
broken.
The physical properties of metals
Melting points and boiling points
Metals tend to have high melting and boiling points
because of the strength of the metallic bond. The
strength of the bond varies from metal to metal and
depends on the number of electrons which each atom
delocalises into the sea of electrons, and on the
packing.
Group 1 metals like sodium and potassium have
relatively low melting and boiling points mainly because
each atom only has one electron to contribute to the
bond.
They have relatively large atoms (meaning that the
nuclei are some distance from the delocalised
electrons) which also weakens the bond.
A metal that melts in hot water
The physical properties of metals

Electrical conductivity
Metals conduct electricity. The delocalised
electrons are free to move throughout the
structure in 3-dimensions. They can cross
grain boundaries. Even though the pattern
may be disrupted at the boundary, as long as
atoms are touching each other, the metallic
bond is still present.
Liquid metals also conduct electricity,
showing that although the metal atoms may
be free to move, the delocalisation remains
in force until the metal boils.
Electrical conductivity of metals
Electric current is the flow of electrons in a wire. In metals, the outer
electrons of the atoms belong to a cloud of delocalised electrons.
They are no longer firmly held by a specific atom, but instead they
can move freely through the lattice of positive metal ions. Normally
they move randomly. However, when the wire is connected to a cell,
they are pushed away from the negative terminal and drawn to the
positive one. The cloud of electrons drifts through the wire. The drift
velocity of the cloud is about 3 mm s-1. The electrons within the cloud
are still moving randomly (at much higher speeds) - rather like a
swarm of bees leaving a hive.

Animation showing electrons

moving randomly and then
the movement of electrons
through a wire
 Thermal conductivity
Metals are good conductors of heat.
Heat energy is picked up by the
electrons as additional kinetic energy
(it makes them move faster).
The energy is transferred throughout
the rest of the metal by the moving
electrons.
 Ionic vibrations
The positive metal ions in a metal structure are packed
closely together in a symmetrical geometric
arrangement. They dont move from their position in
the lattice but they are constantly vibrating. If a metal is
heated, the positive metal ions vibrate more vigorously.
These ions collide with neighbouring ions and make
them vibrate more vigorously too. In this way, the
energy is passed, or conducted, through the metal.

A cool lattice. If we
heat the left hand end,
then the energy will
be carried along by
conduction.
 Free electrons
However, metals are particularly good conductors of
heat. In general, they are better than ionic compounds
which also have strong bonds. So we need another
mechanism to explain their especially good
conductivity. It is their free electrons.
Free electronsThe ions in the lattice are vibrating . The
ions at the hot end of a piece of metal vibrate more.

Let's look at just a few electrons.

The electrons at the hot end will speed up they gain
kinetic energy from the vigorously vibrating ions.
Some of them will move down to the cooler end and
collide with ions that are vibrating less vigorously than
those at the hot end.
In these collisions, the electrons will lose kinetic energy
and make the ions vibrate more vigorously.
In effect, the electrons have carried the vibrational
energy from the hot end to the cold end. And, because
they are free to move through the lattice, they are able to
do this more quickly than the bonds between the ions in
the lattice
Thermal conductivity of metals
Metals are good conductors of heat. There are two
reasons for this:

the close packing of the metal ions in the lattice

the delocalised electrons can carry kinetic energy
through the lattice

How a metal conducts by the

movement of free electrons.
 Strength and workability
Malleability and ductility
Metals are described as malleable (can be beaten into sheets) and
ductile (can be pulled out into wires).
This is because of the ability of the atoms to roll over each other
into new positions without breaking the metallic bond.
If a small stress is put onto the metal, the layers of atoms will start
to roll over each other.
If the stress is released again, they will fall back to their original
positions. Under these circumstances, the metal is said to be
elastic.
 Strength and workability

If a larger stress is put on, the atoms

roll over each other into a new position,
and the metal is permanently changed.
 The hardness of metals
This rolling of layers of atoms over each
other is hindered by grain boundaries
because the rows of atoms don't line up
properly. It follows that the more grain
boundaries there are (the smaller the
individual crystal grains), the harder the
metal becomes.
Offsetting this, because the grain boundaries
are areas where the atoms aren't in such
good contact with each other, metals tend to
fracture at grain boundaries. Increasing the
number of grain boundaries not only makes
the metal harder, but also makes it more
brittle.
Controlling the size of the crystal grains
If you have a pure piece of metal, you can control the
size of the grains by heat treatment or by working the
metal.
Heating a metal tends to shake the atoms into a more
regular arrangement - decreasing the number of grain
boundaries, and so making the metal softer. Banging the
metal around when it is cold tends to produce lots of
small grains. Cold working therefore makes a metal
harder. To restore its workability, you would need to
reheat it.
You can also break up the regular arrangement of the
atoms by inserting atoms of a slightly different size into
the structure. Alloys such as brass (a mixture of copper
and zinc) are harder than the original metals because the
irregularity in the structure helps to stop rows of atoms
from slipping over each other.
 Metallic Bonding

A. Outermost electrons wander freely through metal. Metal consists of

cations held together by negatively-charged electron "glue.

B. Free electrons can move rapidly in response to electric fields,

hence metals are a good conductor of electricity.

C. Free electrons can transmit kinetic energy rapidly, hence metals are
good conductors of heat.

D. The layers of atoms in metal are hard to pull apart because of the
electrons holding them together, hence metals are tough. But
individual atoms are not held to any other specific atoms, hence
atoms slip easily past one another. Thus metals are ductile. Metallic
Bonding is the basis of our industrial civilization.
 2. DIPOLE FORCES
Polar covalent molecules are sometimes
described as "dipoles", meaning that the
molecule has two "poles". One end
(pole) of the molecule has a partial
positive charge while the other end has a
partial negative charge. The molecules
will orientate themselves so that the
opposite charges attract principle
operates effectively.
FORCES BETWEEN MOLECULES
There are in fact three basic types of
interaction between molecules which
are, in order of increasing strength:
van der Waals interactions or
dispersion forces,
dipole-dipole interactions,
hydrogen bonds,
and these secondary bonding
interactions, like the primary bonding
interactions, involve the electrons
(atomic glue!).
 DIPOLE FORCES
In the example on the
right,hydrochloric acid
is a polar molecule
with the partial positive
charge on the
hydrogen and the
partial negative charge
on the chlorine.
A network of partial +
and - charges attract
molecules to each
other.
 Polar Covalent Compounds
Introduction to Covalent Bonding:
Bonding between non-metals consists of two
electrons shared between two atoms. In
covalent bonding, the two electrons shared
by the atoms are attracted to the nucleus of
both atoms. Neither atom completely loses
or gains electrons as in ionic bonding.
There are two types of covalent bonding:
1. Non-polar bonding with an equal sharing
of electrons.
2. Polar bonding with an unequal sharing of
electrons. The number of shared electrons
depends on the number of electrons needed
to complete the octet.
 Polar Covalent Compounds
POLAR BONDING results when two different
non-metals unequally share electrons between
them. One well known exception to the identical
atom rule is the combination of carbon and
hydrogen in all organic compounds.
The non-metal closer to fluorine in the Periodic
Table has a greater tendency to keep its own
electron and also draw away the other atom's
electron. It is NOT completely successful.
As a result only partial charges are established.
One atom becomes partially positive since it
has lost control of its electron some of the time.
The other atom becomes partially negative
since it gains electron some of the time.
 WATER
Water, the most universal compound on
all of the earth, has the property of being a
polar molecule.
As a result of this property, the physical
and chemical properties of the compound
are fairly unique.Hydrogen Oxide or water
forms a polar covalent molecule.
The graphic on the right shows that
oxygen has 6 electrons in the outer shell.
Hydrogen has one electron in its outer
energy shell.
Since 8 electrons are needed for an octet,
they share the electrons.However, oxygen
gets an unequal share of the two electrons
from both hydrogen atoms.
Again, the electrons are still shared (not
transferred as in ionic bonding), the
sharing is unequal.
The electrons spends more of the time
closer to oxygen. As a result, the oxygen
acquires a "partial" negative charge.
At the same time, since hydrogen loses
the electron most - but not all of the time,
it acquires a "partial" charge. The partial
charge is denoted with a small Greek
symbol for delta.
If the difference in electronegativity is not so
great, however, there will be some degree of
sharing of the electrons between the two
atoms. The result is the same whether two
ions come together or two atoms come
together:
Polar Molecule
Polar molecules can interact with
ions:
Ion - Dipole Interactions
 or with other polar
molecules:
Dipole - Dipole Interactions
 HYDROGEN BONDING
To recognize the possibility of hydrogen
bonding, examine the Lewis structure of the
molecule.
The electronegative atom must have one or
more unshared electron pairs as in the case of
oxygen and nitrogen, and has a negative partial
charge.
The hydrogen, which has a partial positive
charge tries to find another atom of oxygen or
nitrogen with excess electrons to share and is
attracted to the partial negative charge. This
forms the basis for the hydrogen bond.
 3. HYDROGEN BONDING
The hydrogen bond is really a special
case of dipole forces. A hydrogen bond is
the attractive force between the hydrogen
attached to an electronegative atom of
one molecule and an electronegative
atom of a different molecule. Usually the
electronegative atom is oxygen, nitrogen,
or fluorine.
In other words - The hydrogen on one
molecule attached to O or N that is
attracted to an O or N of a different
molecule.
 HYDROGEN BONDING
In the graphhic on the right,
the hydrogen is partially
positive and attracted to the
partially negative charge on
the oxygen or nitrogen.
Because oxygen has two
lone pairs, two different
hydrogen bonds can be
made to each oxygen.
This is a very specific bond
as indicated. Some
combinations which are not
hydrogen bonds include:
hydrogen to another
hydrogen or hydrogen to a
carbon.
 HYDROGEN BONDING
Hydrogen bonding is usually stronger
than normal dipole forces between
molecules. Of course hydrogen
bonding is not nearly as strong as
normal covalent bonds within a
molecule - it is only about 1/10 as
strong.
This is still strong enough to have
many important ramifications on the
properties of water.
PHYSICAL PROPERTIES OF WATER
RELATED WITH IMF
For most substances, solids are
more dense than liquids. This is not
true for water. Water is less dense
as a solid
ice floats on liquid water! Strong
hydrogen bonds formed at freezing
lock water molecules away from
each other.
When ice melts, the structure
collapses and molecules move
closer together. This property plays
an important role in lake and ocean
ecosystems.
Floating ice often insulates and
protects animals and plants living in
the water below.
Hydrogen Bonds in ice and liquid
water
In liquid water each molecule is hydrogen bonded
to approximately 3.4 other water molecules. In ice
each each molecule is hydrogen bonded to 4
other molecules.
Compare the two structures below. Notice the
empty spaces within the ice structure
Hydrogen Bonds in liquid water
Hydrogen bonds are
much weaker than
covalent bonds.
However, when a large
number of hydrogen
bonds act in unison
they will make a
strong contributory
effect. This is the case
in water.
 Hydogen Bonds in liquid water
Liquid water has a partially ordered
structure in which hydrogen bonds are
constantly being formed and breaking up.
 Evaporation of Liquid Water
This animation shows
how water molecules
are able to break the
forces of attraction i.e.
the hydrogen bonds to
each other and escape
as the gas molecule.
This is what is
happening inside the
gas bubble as it is
rising to the surface to
break and release the
water gas molecules.
 Hydrogen Bonding
and the Boiling Point of Water
Boiling Point Definition:
In a liquid the molecules are packed
closely together with many random
movements possible as molecules
slip past each other.
As a liquid is heated, the temperature
is increased. As the temperature
increases, the kinetic energy
increases which causes increasing
molecular motion (vibrations and
molecules slipping pas each other).
Eventually the molecular motion
becomes so intense that the forces
of attraction between the molecules
is disrupted to to the extent the
molecules break free of the liquid
and become a gas.
At the temperature of the boiling
point, the liquid turns into a gas. The
molecules are not in contact each
other in the gaseous state.
Evaporation
 Polarity and Boiling Point:
The polarity of the molecules determines the
forces of attraction between the molecules in
the liquid state.
Polar molecules are attracted by the opposite
charge effect (the positive end of one
molecule is attracted to the negative end of
another molecule.
Molecules have different degrees of polarity
as determined by the functional group
present.

The greater the forces of attraction the higher the boiling point or the
greater the polarity the higher the boiling point.
 The evidence for hydrogen bonding
Many elements form compounds with
hydrogen - referred to as "hydrides".
If you plot the boiling points of the hydrides
of the Group 4 elements, you find that the
boiling points increase as you go down the
group.

The increase in boiling point happens because the molecules are

getting larger with more electrons, and so van der Waals dispersion
forces become greater.
The evidence for hydrogen bonding
If you repeat this exercise with the
hydrides of elements in Groups 5, 6 and
7, something odd happens.
The evidence for hydrogen bonding
Although for the most part the
trend is exactly the same as in
group 4 (for exactly the same
reasons), the boiling point of
the hydride of the first element
in each group is abnormally
high.
In the cases of NH3, H2O and HF
there must be some additional
intermolecular forces of
attraction, requiring
significantly more heat energy
to break.
These relatively powerful
intermolecular forces are
described as hydrogen bonds.
 The origin of hydrogen bonding
The molecules which have this extra bonding
are:

Notice that in each of these molecules:

The hydrogen is attached directly to one of the most
electronegative elements, causing the hydrogen to acquire a
significant amount of positive charge.
Each of the elements to which the hydrogen is attached is not
only significantly negative, but also has at least one "active" lone
pair.
Lone pairs at the 2-level have the electrons contained in a
relatively small volume of space which therefore has a high density
of negative charge. Lone pairs at higher levels are more diffuse and
not so attractive to positive things.
 Hydrogen Bonding in Water
Consider two water molecules
coming close together.
The + hydrogen is so strongly
attracted to the lone pair that it
is almost as if you were
beginning to form a co-ordinate
(dative covalent) bond. It
doesn't go that far, but the
attraction is significantly
stronger than an ordinary
dipole-dipole interaction.
Hydrogen bonds have about a
tenth of the strength of an
average covalent bond, and are
being constantly broken and
reformed in liquid water.
 Water as a "perfect" example of
hydrogen bonding
Notice that each water molecule can potentially form
four hydrogen bonds with surrounding water
molecules. There are exactly the right numbers of +
hydrogens and lone pairs so that every one of them
can be involved in hydrogen bonding.
This is why the boiling point of water is higher than
that of ammonia or hydrogen fluoride. In the case of
ammonia, the amount of hydrogen bonding is limited
by the fact that each nitrogen only has one lone pair.
In a group of ammonia molecules, there aren't
enough lone pairs to go around to satisfy all the
hydrogens.
In hydrogen fluoride, the problem is a shortage of
hydrogens. In water, there are exactly the right
number of each. Water could be considered as the
"perfect" hydrogen bonded system.
Harmony molecule Distilled water Tap water
Ice sphere
 The hydrogen halides
The hydrogen halides are colourless gases at room
temperature, producing steamy fumes in moist air.
Hydrogen fluoride has an abnormally high boiling point
for the size of the molecule (293 K or 20C), and could
condense to a liquid on a cool day.
 Hydrogen fluoride
Hydrogen fluoride's boiling point is
higher than you might expect
because it forms hydrogen bond
Fluorine is the most
electronegative of all the elements
and the bond between it and
hydrogen is very polar. The
hydrogen atom carries quite a lot
of positive charge ( +); the fluorine
is fairly negatively charged ( -).
In addition, each fluorine atom has
3 very active lone pairs of
electrons. Fluorine's outer
electrons are at the 2-level, and the
lone pairs represent small highly
charged regions of space.
Hydrogen bonds form between the
+ hydrogen on one HF molecule
and a lone pair on the fluorine of
another one.
 The other hydrogen halides

The other hydrogen halides don't form

hydrogen bonds.
The other halogens aren't as electronegative
as fluorine, and so the bonds in HX are less
polar. As well as that, their lone pairs are at
higher energy levels.
That makes the lone pairs bigger, and so
they don't carry such an intensely
concentrated negative charge for the
hydrogens to be attracted to.
More complex examples of hydrogen bonding
When an ionic substance dissolves
in water, water molecules cluster
around the separated ions. This
process is called hydration.Water
frequently attaches to positive ions
by co-ordinate (dative covalent)
bonds. It bonds to negative ions
using hydrogen bonds.
The diagram shows the
potential hydrogen bonds
formed to a chloride ion,
Cl-. Although the lone
pairs in the chloride ion
are at the 3-level and
wouldn't normally be
active enough to form
hydrogen bonds, in this
case they are made more
attractive by the full
negative charge on the
chlorine.
 Hydrogen Bonding
However complicated the negative
ion, there will always be lone pairs
that the hydrogen atoms from the
water molecules can hydrogen
bond to.
Any molecule which
has a hydrogen atom
attached directly to an
oxygen or a nitrogen is
capable of hydrogen
bonding. Such
molecules will always
have higher boiling
points than similarly
sized molecules which
don't have an -O-H or
an -N-H group. The
hydrogen bonding
makes the molecules
"stickier", and more
heat is necessary to
separate them.
 Hydrogen bonding in alcohols
An alcohol is an organic
molecule containing an -O-H
group.

Ethanol, CH3CH2-O-H, and

methoxymethane, CH3-O-CH3,
both have the same molecular
formula, C2H6O.
Have same no. of electrons
Similar length to the molecule
Both have Dispersion forces
and dipole dipole attractions
B.Pt. - Ethanol = 78.50C
Methoxy methane = (-)24.80C

WHY?
 Hydrogen bonding in alcohols

Ethanol has a hydrogen atom attached

directly to an oxygen - and that oxygen
still has exactly the same two lone pairs
as in a water molecule. Hydrogen
bonding can occur between ethanol
molecules, although not as effectively
as in water. The hydrogen bonding is
limited by the fact that there is only one
hydrogen in each ethanol molecule ,
however , with sufficient + charge
 Hydrogen bonding in alcohols
In methoxymethane, the lone pairs on the oxygen are still there,
but the hydrogens aren't sufficiently + for hydrogen bonds to
form. Except in some rather unusual cases, the hydrogen atom
has to be attached directly to the very electronegative element
for hydrogen bonding to occur.
The boiling points of ethanol and methoxymethane show the
dramatic effect that the hydrogen bonding has on the
stickiness of the ethanol molecules:
ethanol (with hydrogen bonding) 78.5C
 Hydrogen bonding in alcohols

methoxymethane (without hydrogen

bonding) -24.8C

The hydrogen bonding in the ethanol has

lifted its boiling point about 100C.
 Arrange following compounds in terms
of increasing B.Pt.

1) Butan-1-ol
2) 2-methyl propane -1-ol
3) Pentane
?
It is important to realise that hydrogen bonding exists
in addition to van der Waals attractions. For example,
all the above molecules contain the same number of
electrons, and the first two are much the same length.
The higher boiling point of the butan-1-ol is due to the
additional hydrogen bonding.

Comparing the two alcohols (containing -OH groups),

both boiling points are high because of the additional
hydrogen bonding due to the hydrogen attached
directly to the oxygen - but they aren't the same.

The boiling point of the 2-methylpropan-1-ol isn't as

high as the butan-1-ol because the branching in the
molecule makes the van der Waals attractions less
effective than in the longer butan-1-ol.
 Hydrogen bonding in organic
molecules containing nitrogen
Hydrogen bonding also occurs in organic
molecules containing N-H groups - in the
same sort of way that it occurs in ammonia.
Examples range from simple molecules like
CH3NH2 (methylamine) to large molecules like
proteins and DNA.
The two strands of the famous alpha-helix in
DNA are held together by hydrogen bonds
involving N-H groups.
 Polarity and Boiling Point:
In the case of water, hydrogen bonding,
which is a special case of polar dipole
forces exerts a very strong effect to
keep the molecules in a liquid state until
a fairly high temperature is reached.
This is shown in the graphic on the left
for a similar set of molecules in Group
VI of the periodic table. If water behaved
as a normal polar molecule it would
have boiled at about - 100 C (shown in
red). The other molecules are slightly
polar and show the increase in boiling
point with molecular weight which is
normal.
Instead, water boils at +100 C, which is
very abnormal. The major reason for
this abnormal behavior is the strong
attractions afforded by the hydrogen
bonds. It takes a lot more kinetic energy
in an increased temperature to break the
hydrogen bonds to free the water
molecules as the gas.

More normal behavior is seen in dimethyl ether (CH3)2O which has no

hydrogen bonds possible
 Surface tension of water
Water molecules at the surface
(next to the air) hold closely
together, forming an invisible film.
We call this waters surface
tension.
Waters surface tension can hold
weight that would normally sink.
You can carefully float a sewing
needle or paper clip on top of
water in a glass.
Surface tension allows many
aquatic insects, like water spiders
and pod skaters, to walk across
rivers and streams.
Next to mercury water has the
highest surface tension of all
commonly occurring liquids
Surface tension is essential for
the transfer of energy from wind
to water to create waves. Waves
are necessary for rapid oxygen
diffusion in lakes and seas
Surface tension of water
The water strider is an insect of characteristic
length 1cm and weight 10 dynes that resides on
the surface of ponds, rivers, lakes and the open
ocean. Its weight is supported by the surface
tension force generated by curvature of the free
surface. Its body and legs are covered by
thousands of hairs that render its legs
effectively non-wetting (Andersen 1982).
The water strider propels itself by driving its
central pair of legs in a sculling motion. In order
for it to move, it must transfer momentum to the
underlying fluid. It was previously assumed that
this transfer occurs exclusively through
capillary waves excited by the leg stroke (Denny
1993). Our experiments reveal that, conversely,
the strider transfers momentum to the fluid
principally through dipolar vortices shed by its
driving legs. The strider thus generates thrust by
rowing, using its legs as oars, and the meniscii
beneath its driving legs as blades.
Cohesion and Adhesion
Temperature Effects on Water Density
This figure illustrates a model of
the molecular structure of ice
(left). Notice how individual
water molecules are all present
at the maximum distance from
adjacent molecules due to
hydrogen bonding.
Hence, water exhibits its
minimum density when it is in
the form of ice. The
transformation of ice to water is
accompanied by the breaking of
some of the hydrogen bonds,
leading to a dramatic increase
in density.
The graph at right illustrates the
anomalous temperature:density
interrelationship for water. Note
that the lowest density is at 0
but the maximum density is at
3.97. Because of this
relationship, ice floats.
Six dancers
The abnormal behaviour of water:
At 4 C, water has its highest
density. It actually contracts as
the temperature rises from 0 C
to 4C.
This means that in regions with
severe winters, lakes cool at the
surface, and when the surface
water reaches 4 C, that water,
being more dense, sinks. A
temperature gradient is set up,
and when the water freezes, it
does so at the surface.
Eventually, the ice, which floats
on water, acts as an
insulator,protecting the water
below it from further cooling.
This results in lakes freezing
from the top down, and not from
the bottom up. This means that
fishes can survive below the ice
even if the air temperature is far
below 0 C for prolonged periods.
ice floats on water
 HYDROGEN BONDING
Comparison of Bond
Lengths:
The graphic on the right
shows a cluster of water
molecules in the liquid state.
Water is a polar molecule,
with the oxygen (red) being
the negative area and the
hydrogen (white) being the
more positive area. Opposite
charges attract.
The bond lengths give some
indication of the bond
strength. A normal covalent
bond is 0.96 Angstroms,
while the hydrogen bond
length is is 1.97 A.
Electrostatic Potential as an Indication of Polarity
The molecular electrostatic
potential is the potential energy of a
proton at a particular location near
a molecule.
Negative electrostatic potential
corresponds to a attraction of the
proton by the concentrated electron
density in the molecules (from lone
pairs, pi-bonds, etc.) (colored in
shades of red).
Positive electrostatic potential
corresponds to repulsion of the
proton by the atomic nuclei in
regions where low electron density
exists and the nuclear charge is
incompletely shielded(colored in
shades of blue).
The polarity of the water molecule
with the attraction of the positive
and negative partial charges is the
basis for the hydrogen bonding.
Molecular Electrostatic Potential

Introduction:
Electrostatic potential correlates with
dipole moment, electronegativity, and
partial charges. It provides a visual
method to understand the relative
polarity of a molecule.
Molecular Electrostatic Potential
Electronegativity:Linus Pauling first defined
electronegativity as: "The power of an atom
in a molecule to attract electrons to itself."
A numerical scale based upon a physical
measurements allows a comparison between
atoms.A rough approximation for
comparison of atoms is to say, the the closer
an atom is to Fluorine in the periodic table,
the greater the electronegativity compared to
an atom further away.
The greater the electronegativity difference
between atoms in a bond, the more polar the
bond.
Molecular Electrostatic Potential
Partial Charges:
Electronegativity of atoms in molecules indicates
where partial charges are likely to be found - the most
electronegative atoms are most negative, the others
are less negative or more positive.
Quantum mechanical calculations generate values for
partial charges for the atoms in a molecule. These are
related to electron densities around various atoms
resulting from bonding and lone pairs of electrons.
The calculated partial charges represented as spheres
(yellow is negative, red is positive) show how the
molecule would interact with an approaching proton.
The greater the difference in partial charges, the more
polar the molecule.
partial charges
 Electrostatic Potential:
The graphic on the right shows both
partial charge and contours of
electrostatic potential.
The molecular electrostatic potential
is the potential energy of a proton at
a particular location near a
molecule.
Negative electrostatic potential
corresponds to a attraction of the
proton by the concentrated electron
density in the molecules (from lone
pairs, pi-bonds, etc.) (colored in
shades of red).
Positive electrostatic potential
corresponds to repulsion of the
proton by the atomic nuclei in
regions where low electron density
exists and the nuclear charge is
incompletely shielded(colored in
shades of blue).
 partial charges
The calculated partial charges represented as spheres
(yellow is negative, red is positive) show how the
molecule would interact with approaching protons or
positive charges.
When a unit of positive charge (proton) approaches a
positive region of the molecule, the repulsive interaction
results in an increasing positive potential energy (colored
in shades of blue).
As a proton approaches a negative region an attractive
interaction results in negative potential energy (colored in
shades of red).
The electron density isosurface is a surface on which the
molecule's electron density has a particular value and
that encloses a specified fraction of the molecule's
electron probability density.
The electrostatic potential at different points on the
electron density isosurface is shown by coloring the
isosurface with contours.
 partial charges

The more red / blue differences, the more polar the

molecule. If the surface is largely white or lighter color
shades, the molecule is mostly non-polar.
 Hydrogen Bonding
A. Water molecules are asymmetrical. The positively-charged
portions of one are attracted to the negatively-charged parts of
another. It takes a lot of energy to pull them apart. Hence:
Water melts and boils at unusually high temperatures for such a
light molecule.
Water has a high heat capacity.
It takes a lot of energy to melt ice and vaporize water.
Thus water is the principal heat reservoir on the Earth.

B. The asymmetrical charge distribution on a water molecule

makes it very effective in dissolving ionically-bonded materials.
However, it is not an effective solvent of covalently bonded
materials (oil and water don't mix). Hence:
Water is very effective at weathering rocks and minerals. It is the
closest thing to a universal solvent.
Water is very effective at transporting ions and dissolved
nutrients in the human body.
Water is not an effective solvent of organic molecules. Thus we
do not dissolve in our own cell fluids. Nifty feature.

C. When water freezes, it assumes a very open structure and

actually expands. Most materials shrink when they freeze and
sink in their liquid phases. Implications:
If ice sank like most frozen solids, it would accumulate at the
bottoms of frozen lakes and seas. Most of the world's water would
be ice.
Expansion of ice in rocks is a powerful weathering agent.
 4. INDUCED DIPOLE FORCES
Forces between essentially non-
polar molecules are the weakest
of all intermolecular forces.
"Temporary dipoles" are formed
by the shifting of electron clouds
within molecules. These
temporary dipoles attract or repel
the electron clouds of nearby
non-polar molecules.
The temporary dipoles may exist
for only a fraction of a second but
a force of attraction also exist for
that fraction of time. The strength
of induced dipole forces depends
on how easily electron clouds can
be distorted. Large atoms or
molecules with many electrons
far removed from the nucleus are
more easily distorted.
Nonpolar Covalent Compounds
Introduction to Covalent Bonding:
Bonding between non-metals consists of two
electrons shared between two atoms. In covalent
bonding, the two electrons shared by the atoms
are attracted to the nucleus of both atoms.
Neither atom completely loses or gains electrons
as in ionic bonding.
There are two types of covalent bonding:
1. Non-polar bonding with an equal sharing of
electrons.
2. Polar bonding with an unequal sharing of
electrons. The number of shared electrons
depends on the number of electrons needed to
complete the octet
Nonpolar Covalent Compounds

NON-POLAR BONDING results when two

identical non-metals equally share
electrons between them.
One well known exception to the identical
atom rule is the combination of carbon
and hydrogen in all organic compounds.
Nonpolar Covalent Compounds
IODINE:
Iodine forms a
diatomic non-polar
covalent molecule.
The graphic on the
right shows that iodine
has 7 electrons in the
outer shell. Since 8
electrons are needed
for an octet, two iodine
atoms EQUALLY share
2 electrons.
Nonpolar Covalent Compounds
OXYGEN:
Molecules of oxygen, present in
about 20% concentration in air
are also a covalent molecules .
See the graphic on the left the
Lewis symbols.
There are 6 electrons in the
outer shell, therefore, 2
electrons are needed to
complete the octet. The two
oxygen atoms share a total of
four electrons in two separate
bonds, called double bonds.
The two oxygen atoms equally
share the four electrons.
Non-polar Molecule
Fluctuating Dipole in a Non-polar Molecule

These instantaneous dipoles may be induced and

stabilized as an ion or a polar molecule approaches the
non-polar molecule.
Ion - Induced Dipole Interaction
Dipole - Induced Dipole Interaction
 Dispersion Forces
Interactions between ions, dipoles, and induced dipoles
account for many properties of molecules - deviations
from ideal gas behavior in the vapor state, and the
condensation of gases to the liquid or solid states.

In general, stronger interactions allow the solid and

liquid states to persist to higher temperatures.

However, non-polar molecules show similar behavior,

indicating that there are some types of intermolecular
interactions that cannot be attributed to simple electrical
attractions. These interactions are generally called
dispersion forces.
 Dispersion Forces
Electrical forces operate when the molecules are
several molecular diameters apart, and become
stronger as the molecules or ions approach each
other.
Dispersion forces are very weak until the molecules
or ions are almost touching each other, as in the
liquid state.
These forces appear to increase with the number of
"contact points" with other molecules, so that long
non-polar molecules such as n-octane (C8H18) may
have stronger intermolecular interactions than very
polar molecules such as water (H2O), and the boiling
point of n-octane is actually higher than that of
water.
GIANT COVALENT STRUCTURES
Giant covalent substances like

diamond,
graphite and
silicon dioxide (silicon(IV) oxide),

and relates those structures to the

physical properties of the substances.
 The structure of diamond
The giant covalent
structure of diamond
Carbon has an
electronic
arrangement of
1s2,2s22p2. In
diamond, each carbon
shares electrons with
four other carbon
atoms - forming four
single bonds.
 The structure of diamond
The diamond
crystal bond
structure gives the
gem its hardness
and differentiates it
from graphite.
 The structure of diamond
In the diagram some
carbon atoms only seem
to be forming two bonds
(or even one bond), but
that's not really the case.
We are only showing a
small bit of the whole
structure.
This is a giant covalent
structure - it continues on
and on in three
dimensions. It is not a
molecule, because the
number of atoms joined up
in a real diamond is
completely variable -
depending on the size of
the crystal.
Diamond
The physical properties of diamond

Diamond
has a very high melting point (almost 4000C). Very
strong carbon-carbon covalent bonds have to be broken
throughout the structure before melting occurs.
is very hard. This is again due to the need to break very
strong covalent bonds operating in 3-dimensions.
doesn't conduct electricity. All the electrons are held
tightly between the atoms, and aren't free to move.
is insoluble in water and organic solvents. There are no
possible attractions which could occur between solvent
molecules and carbon atoms which could outweigh the
attractions between the covalently bound carbon atoms.
 The structure of graphite
The giant covalent
structure of graphite
Graphite has a layer
structure which is
quite difficult to draw
convincingly in three
dimensions.
The diagram on the
right shows the
arrangement of the
atoms in each layer,
and the way the layers
are spaced.
 The structure of graphite
Notice that you can't really
draw the side view of the
layers to the same scale as
the atoms in the layer
without one or other part of
the diagram being either
very spread out or very
squashed.
In that case, it is important
to give some idea of the
distances involved. The
distance between the layers
is about 2.5 times the
distance between the atoms
within each layer.
The layers, of course,
extend over huge numbers
of atoms - not just the few
shown above.
You might argue that
carbon has to form 4
bonds because of its 4
unpaired electrons,
whereas in this diagram it
only seems to be forming
3 bonds to the
neighbouring carbons.
This diagram is
something of a
simplification, and shows
the arrangement of atoms
rather than the bonding.
 The bonding in graphite
Each carbon atom uses three of its electrons to
form simple bonds to its three close neighbours.
That leaves a fourth electron in the bonding
level.
These "spare" electrons in each carbon atom
become delocalised over the whole of the sheet
of atoms in one layer.
They are no longer associated directly with any
particular atom or pair of atoms, but are free to
wander throughout the whole sheet.
 The bonding in graphite
The bonding in graphite is like a vastly
extended version of the bonding in
benzene.
Each carbon atom undergoes sp2
hybridisation, and then the
unhybridised p orbitals on each carbon
atom overlap sideways to give a
massive pi system above and below the
plane of the sheet of atoms.
Allotropes of Carbon
 Graphite to diamond animation
This animation shows how graphite becomes diamond under extreme heat and pressure
An orbital model for the benzene
(C6H6) structure
Building the orbital model
Benzene is built from hydrogen atoms (1s1)
and carbon atoms (1s22s22px12py1).
Each carbon atom has to join to three other
atoms (one hydrogen and two carbons) and
doesn't have enough unpaired electrons to
form the required number of bonds, so it
needs to promote one of the 2s2 pair into the
empty 2pz orbital.
This is exactly the same as happens
whenever carbon forms bonds - whatever else
it ends up joined to.
 Benzene structure

Because each carbon is only joining to three

other atoms, when the carbon atoms
hybridise their outer orbitals before forming
bonds, they only need to hybridise three of
the orbitals rather than all four. They use the
2s electron and two of the 2p electrons, but
leave the other 2p electron unchanged.
 Benzene structure
Each carbon atom
The new orbitals formed now looks like the
are called sp2 hybrids,
because they are made diagram below.
by an s orbital and two This is all exactly
p orbitals reorganising the same as
themselves. happens in
The three sp2 hybrid ethene.
orbitals arrange
themselves as far apart
as possible - which is at
120 to each other in a
plane. The remaining p
orbital is at right angles
to them.
 Benzene structure
The difference in benzene
is that each carbon atom
is joined to two other
similar carbon atoms
instead of just one.
Each carbon atom uses
the sp2 hybrids to form
sigma bonds with two
other carbons and one
hydrogen atom.
The diagram on the right
shows the sigma bonds
formed, but for the
moment leaves the p
orbitals alone.
Remember: A sigma bond is formed by the end-to-end overlap between atomic
orbitals.
 Benzene structure
In common with the great majority
of descriptions of the bonding in
benzene, we are only going to
show one of these delocalised
molecular orbitals for simplicity.

In the diagram, the sigma bonds

have been shown as simple lines
to make the diagram less
confusing.
The two rings above and below
the plane of the molecule
represent one molecular orbital.
The two delocalised electrons can
be found anywhere within those
rings. The other four delocalised
electrons live in two similar (but
not identical) molecular orbitals.
Resonance in Benzene
 Warning!
Be very careful how you phrase this in
exams. You must never talk about the p
orbitals on the carbons overlapping
sideways to produce a delocalised pi
bond.
This upsets examiners because a pi
bond can only hold 2 electrons -
whereas in benzene there are 6
delocalised electrons.
Talk instead about a "pi system" - or just
about the delocalised electrons
Relating the orbital model to the
properties of benzene
The shape of benzene
This is easily explained. Benzene is a regular
hexagon because all the bonds are identical. The
delocalisation of the electrons means that there
aren't alternating double and single bonds.
The energetic stability of benzene
This is accounted for by the delocalisation. As a
general principle, the more you can spread electrons
around - in other words, the more they are
delocalised - the more stable the molecule becomes.
The extra stability of benzene is often referred to as
"delocalisation energy".
Relating the orbital model to the
properties of benzene
The reluctance of benzene to undergo addition
reactions
With the delocalised electrons in place, benzene is
about 150 kJ mol-1 more stable than it would
otherwise be. If you added other atoms to a benzene
ring you would have to use some of the delocalised
electrons to join the new atoms to the ring. That
would disrupt the delocalisation and the system
would become less stable.
Since about 150 kJ per mole of benzene would have
to be supplied to break up the delocalisation, this
isn't going to be an easy thing to do.
Relating the orbital model to the
properties of benzene
The symbol for benzene

Although you will still come across the

Kekul structure for benzene, for most
purposes we use the structure on the
right.
The hexagon shows the ring of six
carbon atoms, each of which has one
hydrogen attached. (You have to know
that - counting bonds to find out how
many hydrogens to add doesn't work in
this particular case.)
The circle represents the delocalised
electrons. It is essential that you include
the circle. If you miss it out, you are
drawing cyclohexane and not benzene.
 Solubility and
Intermolecular Forces
Like dissolves like
Polar solutes dissolve in polar solvents
Nonpolar solutes dissolve in nonpolar
solvents
Molecules with similar intermolecular
forces will mix freely
Ionic Solute with
Polar Solvent
Ionic Solute with
Nonpolar Solvent
Nonpolar Solute with
Nonpolar Solvent
Nonpolar Solute
with Polar Solvent
 Comparison of the Properties of Substances with Ionic,
Covalent, Metallic or Intermolecular Bonds
Ionic Covalent Metallic Intermolecular
Bond Strong Very strong Variable strength, Weak
strength generallymoderat
e

Hardness Moderate to high Insulators in Low to moderate; Crystal soft and

solids and liquid ductile, malleable somewhat
states plastic

Electrical Conducts by ion Low Good conductors; Insulators in

conductivity transport, but only conducts by both solid and
when liquid or electron transport liquid states
dissociated
Melting Moderate to high Very high Generally high Low
point
Solubility Soluble in polar Very low Insoluble except Soluble in
solvents solubility in acids or alkalis organic
by chemical solvents
reaction
Examples Most minerals Diamond, oxygen, Cu, Ag, Au, other Organic
hydrogen, organic metals compounds
molecules
 Boiling Point of Various Material (C)
Noble gas Helium He -269
neon Ne -246
argon Ar -186
Nonpolar covalent hydrogen H2 -253
oxygen O2 -183
methane CH4 -164
chlorine Cl2 -34
polar covalent ammonia NH3 -33
hydrogen 19.5
fluoride HF
water 100
H2O
ionic potassium KCl 771
chloride
sodium NaCl 1413
chloride
magnesium MgO 2826
oxide
metallic copper Cu 2567
iron Fe 2750
tungsten W 5660
 REFERENCES
VIRTUAL CHEMBOOK
http://www.elmhurst.edu/%7Echm/vchembook/index.html

Gary L. Bertrand
Department of Chemistry
University of Missouri-Rolla

chemguideHelping you to understand Chemistry

Jim Clark 2005
http://www.chemguide.co.uk/

Minerals
http://www.uwgb.edu/dutchs/EarthSC202Notes/minerals.htm