The Four Intermolecular Forces and How They

Affect Boiling Points

by JA MES
in AL CO H OL S , F UN C TI O NA L GR O UP S , GE NE RA L C HE MI S TRY , OR G AN IC CH E MIS TRY 1

Its amazing how much chemistry comes down to simple

attraction between opposite charges and repulsion
between like charges.
This is the driving force behind chemical bonding, of
course. But its also responsible for the
forces between molecules. This means that properties
like melting and boiling points are a measure of how
strong the attractive forces are between individual
atoms or molecules.
There are four types of these interactions and they are
all different manifestations of opposite charges
attract.
It all flows from this general principle: as bonds become
more polarized, the charges on the atoms become
greater, which leads to greater intermolecular
attractions, which leads to higher boiling points.
Ionic bonds > H bonding > Van der Waals dipole-dipole
interactions > Van der Waals dispersion forces.
Lets look at them individually, from strongest to
weakest.
1. Ionic forces are interactions between charged atoms
or molecules. Positively charged ions, such as Na(+) ,
Li(+), and Ca(2+), are termed cations. Negatively

charged ions, such as Cl(), Br(), HO() are called

anions (I always got this straight through remembering
that the N in Anion stood for Negative) The
attractive forces between oppositely charged ions is
described by Coulombs Law, in which the force
increases with charge and as decreases as the distance
between these ions is increased. The highly polarized
(charged) nature of ionic molecules is reflected in their
high melting points (NaCl has a melting point of 801 C)
as well as in their high water solubility (for the alkali
metal salts, anyway; metals that form multiple
charges like to leave residues on your bathtub)

2. Hydrogen bonding occurs in molecules

containing the highly electronegative elements F, O,
or N directly bound to hydrogen. Since H has an
electronegativity of 2.2 (compare to 0.9 for Na and 0.8
for K) these bonds are not as polarized as purely ionic
bonds and possess some covalent character. However,
the bond to hydrogen will still be polarized and possess
a dipole.

The dipole of one molecule can align with the dipole from another molecule, leading to an attractive
interaction that we callhydrogen bonding. Owing to rapid molecular motion in solution, these bonds
are transient (short-lived) but have significant bond strengths ranging from (9 kJ/mol (2 kcal/mol) (for
NH) to about 30 kJ/mol (7 kcal) and higher for HF. As you might expect, the strength of the bond
increases as the electronegativity of the group bound to hydrogen is increased.
So in a sense, HO, and NH are sticky molecules containing these functional groups will tend to
have higher boiling points than you would expect based on their molecular weight.

3. Van Der Waals Dipole-dipole interactions.

Other groups beside hydrogen can be involved in polar
covalent bonding with strongly electronegative atoms.
For instance, each of these molecules contains a dipole:

These dipoles can interact with each other in an

attractive fashion, which will also increase the boiling
point. However since the electronegativity difference
between carbon (electronegativity = 2.5) and the
electronegative atom (such as oxygen or nitrogen) is not
as large as it is for hydrogen (electronegativity = 2.2),
the polar interaction is not as strong. So on average

these forces tend to be weaker than in hydrogen

bonding.
4. Van der waals Dispersion forces (London forces)
The weakest intermolecular forces of all are
called dispersion forces or London forces. These
represent the attraction between instantaneous
dipoles in a molecule. Think about an atom like argon.
Its an inert gas, right? But if you cool it to 186 C, you
can actually condense it into liquid argon. The fact that it
forms a liquid it means that something is holding it
together. That something is dispersion forces. Think
about the electrons in the valence shell. On average,
theyre evenly dispersed. But at any given instant, there
might be a mismatch between how many electrons are
on one side and how many are on the other, which can
lead to an instantaneous difference in charge.

Its a little like basketball. On average, every player is

covered one-on-one, for an even distribution of players.
But at any given moment, you might have a double-team
situation where the distribution of players is lumpy (it

also means that somebody is open). In the valence

shell, this lumpiness creates dipoles, and its these
dipoles which are responsible for intermolecular
attraction.
The polarizability is the term we use to describe how
readily atoms can form these instantaneous
dipoles. Polarizability increases with atomic
size. Thats why the boiling point of argon (186 C) is
so much higher than the boiling point of helium (272
C). By the same analogy, the boiling point of iodine, (I-I,
184 C) is much higher than the boiling point of fluorine
(F-F, 188C).
For hydrocarbons and other non-polar molecules which
lack strong dipoles, these dispersion forces are really
the only attractive forces between molecules. Since the
dipoles are weak and transient, they depend on contact
between molecules which means that the forces
increase with surface area. A small molecule like
methane has very weak intermolecular forces, and has a
low boiling point. However, as molecular weight
increases, boiling point also goes up. Thats because
the surface over which these forces can operate has
increased. Therefore, dispersion forces increase with
increasing molecular weight. Individually, each
interaction isnt worth much, but if collectively, these
forces can be extremely significant. How can a gecko
lizard walk on walls? Look at its feet.

[Determining trends for hydrocarbons can get a little bit

tricky depending on the exact structure symmetry also

plays a role in boiling points and melting points. I talked

about this in detail previously.]
Bottom line:
1. The intermolecular forces increase with increasing
polarization of bonds.
2. Strength of forces (and therefore impact on boiling
points) is ionic > hydrogen bonding > dipole dipole >
dispersion
3. Boiling point increases with molecular weight, and
with surface area.

What are intermolecular attractions?

Intermolecular versus intramolecular bonds
Intermolecular attractions are attractions between one molecule
and a neighbouring molecule. The forces of attraction which hold
an individual molecule together (for example, the covalent bonds)
are known as intramolecular attractions. These two words are so
confusingly similar that it is safer to abandon one of them and
never use it. The term "intramolecular" won't be used again on this
site.
All molecules experience intermolecular attractions, although in
some cases those attractions are very weak. Even in a gas like
hydrogen, H2, if you slow the molecules down by cooling the gas,
the attractions are large enough for the molecules to stick together
eventually to form a liquid and then a solid.
In hydrogen's case the attractions are so weak that the molecules
have to be cooled to 21 K (-252C) before the attractions are
enough to condense the hydrogen as a liquid. Helium's
intermolecular attractions are even weaker - the molecules won't
stick together to form a liquid until the temperature drops to 4 K (269C).

van der Waals forces: dispersion forces

Dispersion forces (one of the two types of van der Waals force we
are dealing with on this page) are also known as "London forces"
(named after Fritz London who first suggested how they might
arise).
The origin of van der Waals dispersion forces
Temporary fluctuating dipoles
Attractions are electrical in nature. In a symmetrical molecule like
hydrogen, however, there doesn't seem to be any electrical
distortion to produce positive or negative parts. But that's only true

on average.

The lozenge-shaped diagram represents a small symmetrical

molecule - H2, perhaps, or Br2. The even shading shows that on
average there is no electrical distortion.
But the electrons are mobile, and at any one instant they might find
themselves towards one end of the molecule, making that end -.
The other end will be temporarily short of electrons and so
becomes +.
Note: (read as "delta") means "slightly" - so + means
"slightly positive".

An instant later the electrons may well have moved up to the other
end, reversing the polarity of the molecule.

This constant "sloshing around" of the electrons in the molecule

causes rapidly fluctuating dipoles even in the most symmetrical
molecule. It even happens in monatomic molecules - molecules of
noble gases, like helium, which consist of a single atom.
If both the helium electrons happen to be on one side of the atom
at the same time, the nucleus is no longer properly covered by
electrons for that instant.

How temporary dipoles give rise to intermolecular attractions

I'm going to use the same lozenge-shaped diagram now to
represent any molecule which could, in fact, be a much more
complicated shape. Shape does matter (see below), but keeping
the shape simple makes it a lot easier to both draw the diagrams
and understand what is going on.
Imagine a molecule which has a temporary polarity being
approached by one which happens to be entirely non-polar just at
that moment. (A pretty unlikely event, but it makes the diagrams
much easier to draw! In reality, one of the molecules is likely to
have a greater polarity than the other at that time - and so will be
the dominant one.)

As the right hand molecule approaches, its electrons will tend to be

attracted by the slightly positive end of the left hand one.
This sets up an induced dipole in the approaching molecule,
which is orientated in such a way that the + end of one is attracted
to the - end of the other.

An instant later the electrons in the left hand molecule may well
have moved up the other end. In doing so, they will repel the
electrons in the right hand one.

The polarity of both molecules reverses, but you still have +

attracting -. As long as the molecules stay close to each other the
polarities will continue to fluctuate in synchronisation so that the

attraction is always maintained.

There is no reason why this has to be restricted to two molecules.

As long as the molecules are close together this synchronised
movement of the electrons can occur over huge numbers of
molecules.

This diagram shows how a whole lattice of molecules could be held

together in a solid using van der Waals dispersion forces. An
instant later, of course, you would have to draw a quite different
arrangement of the distribution of the electrons as they shifted
around - but always in synchronisation.

The strength of dispersion forces

Dispersion forces between molecules are much weaker than the
covalent bonds within molecules. It isn't possible to give any exact
value, because the size of the attraction varies considerably with
the size of the molecule and its shape.
How molecular size affects the strength of the dispersion
forces
The boiling points of the noble gases are
helium

-269C

neon

-246C

argon

-186C

krypton

-152C

xenon

-108C

radon

-62C

All of these elements have monatomic molecules.

The reason that the boiling points increase as you go down the
group is that the number of electrons increases, and so also does
the radius of the atom. The more electrons you have, and the more
distance over which they can move, the bigger the possible
temporary dipoles and therefore the bigger the dispersion forces.

Because of the greater temporary dipoles, xenon molecules are

"stickier" than neon molecules. Neon molecules will break away
from each other at much lower temperatures than xenon molecules
- hence neon has the lower boiling point.
This is the reason that (all other things being equal) bigger
molecules have higher boiling points than small ones. Bigger
molecules have more electrons and more distance over which
temporary dipoles can develop - and so the bigger molecules are
"stickier".

How molecular shape affects the strength of the dispersion

forces
The shapes of the molecules also matter. Long thin molecules can
develop bigger temporary dipoles due to electron movement than
short fat ones containing the same numbers of electrons.
Long thin molecules can also lie closer together - these attractions
are at their most effective if the molecules are really close.
For example, the hydrocarbon molecules butane and 2methylpropane both have a molecular formula C4H10, but the atoms
are arranged differently. In butane the carbon atoms are arranged
in a single chain, but 2-methylpropane is a shorter chain with a
branch.

Butane has a higher boiling point because the dispersion forces are
greater. The molecules are longer (and so set up bigger temporary
dipoles) and can lie closer together than the shorter, fatter 2methylpropane molecules.

van der Waals forces: dipole-dipole interactions

Warning! There's a bit of a problem here with modern
syllabuses. The majority of the syllabuses talk as if dipoledipole interactions were quite distinct from van der Waals
forces. Such a syllabus will talk about van der Waals forces
(meaning dispersion forces) and, separately, dipole-dipole
interactions.
All intermolecular attractions are known collectively as van
der Waals forces. The various different types were first
explained by different people at different times. Dispersion
forces, for example, were described by London in 1930;
dipole-dipole interactions by Keesom in 1912.
This oddity in the syllabuses doesn't matter in the least as far
as understanding is concerned - but you obviously must
know what your particular examiners mean by the terms they
use in the questions. Check your syllabus.
If you are working to a UK-based syllabus for 16 - 18 year
olds, but don't have a copy of it, follow this link to find out
how to get one.

A molecule like HCl has a permanent dipole because chlorine is

more electronegative than hydrogen. These permanent, in-built
dipoles will cause the molecules to attract each other rather more
than they otherwise would if they had to rely only on dispersion

forces.
Note: If you aren't happy about electronegativity and polar
molecules, follow this link before you go on.

It's important to realise that all molecules experience dispersion

forces. Dipole-dipole interactions are not an alternative to
dispersion forces - they occur in addition to them. Molecules which
have permanent dipoles will therefore have boiling points rather
higher than molecules which only have temporary fluctuating
dipoles.
Surprisingly dipole-dipole attractions are fairly minor compared with
dispersion forces, and their effect can only really be seen if you
compare two molecules with the same number of electrons and the
same size. For example, the boiling points of ethane, CH 3CH3, and
fluoromethane, CH3F, are

Why choose these two molecules to compare? Both have identical

numbers of electrons, and if you made models you would find that
the sizes were similar - as you can see in the diagrams. That
means that the dispersion forces in both molecules should be much
the same.
The higher boiling point of fluoromethane is due to the large
permanent dipole on the molecule because of the high
electronegativity of fluorine. However, even given the large
permanent polarity of the molecule, the boiling point has only been
increased by some 10.

Here is another example showing the dominance of the dispersion

forces. Trichloromethane, CHCl3, is a highly polar molecule
because of the electronegativity of the three chlorines. There will be
quite strong dipole-dipole attractions between
one molecule and its neighbours.

On the other hand,

tetrachloromethane, CCl4, is
non-polar. The outside of
uniformly - in all directions.
only on dispersion forces.

the molecule is
CCl4 has to rely

So which has the highest boiling point? CCl4 does, because it is a

bigger molecule with more electrons. The increase in the
dispersion forces more than compensates for the loss of dipoledipole interactions.
The boiling points are:
CHCl3

61.2C

CCl4

76.8C

Trends in the forces

While the intramolecular forces keep the atoms in a moleucle
together and are the basis for the chemical properties, the
intermolecular forces are those that keep the molecules
themselves together and are virtually responsible for all the
physical properties of a material. The intermolecular forces
increase in strength according to the following:

London dispersion < dipole-dipole < H-bonding < ion-ion

Now, as these things increase in strength it becomes harder to remove the
molecules from each other. Therefore, one would expect the melting and boiling
points to be higher for those substances which have strong intermolecular forces.
We know that it takes energy to go from a solid to a liquid to a gas. This energy is
directly related to the strength of attraction between molecules in the condensed
phases. Since energy is directly proportional to the temperature, the above trends
ought to hold true.
In addition, there are energies associated with making these phase transitions:

Each of these processes are endothermic, and scale with the magnitude of the
intermolecular forces. Thus, as these intermolecular forces increase, so do the
energies requires to melt, vaporize, or sublime (go from solid to a gas) a species.

Intermolecular forces dipole-dipole, London forces, hydrogen bonding versus

Covalent bonds
Dr. Walt Volland, all rights reserved 1998-2011 revised Nov 3, 2011

Attractions between molecules are classified as

Dipole-dipole interactions , example: ammonia, NH 3

London forces also known as van der Waals forces,

example: methane, CH4

Hydrogen bonding example: water, H2O .

Relative magnitudes of forces

The relative size of these interactions is important so the
relative effects are understood.
The relative typical strengths for the different interactions
are listed here in descending strength.
Covalent
bonds >
Hydrogen
Dipole-dipole
London
bonding >
interactions >
forces
400 kcal >
12-16 kcal >

2-0.5 kcal >

less than 1
kcal

From this we can see that normal covalent bonds are

almost 40 times the strength of hydrogen bonds.

Covalent bonds are almost 200 times the strength of

dipole-dipole forces, and more than 400 times the size of
London forces.

Dipole-dipole interactions
Dipole-dipole interactions exist between molecules that are
permanently polar. This requires the presence of polar
bonds and a asymmetric molecule. These molecules have
a permanent separation of positive and negative charge. In
the illustration the H end of HCl is permanently slightly
positive charge. The Cl end of HCl has a permanent slight
negative charge. the "H" in one molecule is attracted to the
"Cl" in a neighbor. The intermolecular force is weak
compared to a covalent bond. But this dipole-dipole
interaction is one of the stronger intermolecular attractions.

London forces
London forces exist in
nonpolar molecules.
These forces result from
temporary charge
imbalances. The
temporary charges exist
because the electrons in
a molecule or ion move
randomly in the structure.
The nucleus of one atom
attracts electrons form
the neighboring atom. At
the same time, the
electrons in one particle

repel the electrons in the

neighbor and create a
short lived charge
imbalance.

These temporary charges in one molecule or atom attract

opposite charges in nearby molecules or atoms. A local
slight positive charge (lower case Greek delta) in one
molecule will be attracted to a temporary instantaneous
slight - negative charge in a neighboring molecule.

London forces in hydrocarbons and organic

molecules
The temporary separations of charge produce London
force attractions are what associate one nonpolar organic
molecule with its neighbors. The possibilities for these
interactions go up with increasing molecular size and
surface area. A larger surface increases the chances for
the "induced" charge separations to interact. If the
molecules are linear they have more surface area than if
they are folded into a sphere. The linear molecules have
higher melting and boiling points because of the increased
attractions.

Hydrogen bonding
Hydrogen bonding is a unique type of intermolecular
molecular attraction. There are tworequirements.
First, there must be a covalent bond between a H atom and
either F, O, or N. (These are the three most electronegative
elements.)
Second, the H atom in the polar bond -O-H, -N-H, F-H
inteact with a lone pair of electrons on a nearby atom of F,
O, or N in another molecule or for BIG molecules in
another part of the molecule.

The normal boiling point for water is 100oC. The graph

below shows how high this boiling point is compared to the
predicted ( green circles) boiling points.
The observed boiling point of 100oC is almost four times
greater than the expected value at about -80 oC or -100oC .
The predicted boiling point (green circles) from the trend of
boiling points for H2Te, H2Se, H2S and H2O is very low. If
the trend continued the predicted boiling point would be
below -62 oC. The "anomalous" boiling point for water is the
result of hydrogen bonding between water molecules.

When can hydrogen bonding exist?

Possible combinations where hydrogen bond can exist.
The first entry shows the covalent bond to the O or N atom.
These atoms form two and three covalent bonds. The
single covalent bond between O,N,F is shown and the
dashed line shows the hydrogen bond. NOTICE the H
atom is attracted to a lone pair on the nearby N, O, F atom.
A covalent bond between -O-H ---- :OA covalent bond between -N-H----- :OA covalent bond between F-H ------ :OA covalent bond between -O-H ---- :NA covalent bond between -N-H---- :NA covalent bond between F-H ----- :NA covalent bond between -O-H ----- :FA covalent bond between -N-H ---- :FA covalent bond between F-H ------ :F-

Hydrogen bonding in an ice crystal model

Summary on hydrogen bonding
Hydrogen bonding is responsible for the expansion of
water when it freezes. The water molecules in the solid
have tetrahedral spatial arrangement for the two lone pairs
and two single bonds radiating out from the oxygen. The
lone pairs on the "O" atoms are attracted to nearby water
molecules through hydrogen bonds. A cage like structure
results. The cage has an hexagon shaped opening.

Click for more on hydrogen bonding in water

Exercise: Which of the following molecules display
hydrogen bonding?
Methane, CH4

methyl ether, CH3OCH3

Hydrogen peroxide, H2O2

methyl alcohol, CH3OH

Answer: The hydrogen peroxide and methyl alcohol have

hydrogen bonding between molecules.

The methane lacks highly electronegative atoms bonded to

the hydrogen atoms. The methyl ether has an oxygen but
the carbons are bonded to the "O" . The hydrogen atoms
are not bonded to very electronegative "O" atom.

Dr. Walt Volland, all rights reserved 1998--2011

revised November 3, 2011

Intermolecular Forces

Key Concepts
Three types of force can operate between covalent molecules:

Dispersion Forces
also known as London Forces (named after Fritz London who first described these forces
theoretically 1930) or as Weak Intermolecular Forces or as van der Waal's Forces1(namd
after the person who contributed to our understanding of non-ideal gas behaviour).

Dipole-dipole interactions

Hydrogen bonds

Relative strength of Intermolecular Forces:

Intermolecular forces (dispersion forces, dipole-dipole interactions and hydrogen bonds)

are much weaker than intramolecular forces (covalent bonds, ionic bonds or metallic
bonds)

dispersion forces are the weakest intermolecular force (one hundredth-one thousandth
the strength of a covalent bond), hydrogen bonds are the strongest intermolecular force
(about one-tenth the strength of a covalent bond).

dispersion forces < dipole-dipole interactions < hydrogen bonds

Dispersion Forces (London Forces, Weak Intermolecular Forces, van der Waal's Forces)

are very weak forces of attraction between molecules resulting from:

a. momentary dipoles occurring due to uneven electron distributions in neighbouring

molecules as they approach one another
b. the weak residual attraction of the nuclei in one molecule for the electrons in a
neighbouring molecule.

The more electrons that are present in the molecule, the stronger the dispersion forces
will be.

Dispersion forces are the only type of intermolecular force operating between nonpolar molecules, for example, dispersion forces operate between hydrogen (H2)
molecules, chlorine (Cl2) molecules, carbon dioxide (CO2) molecules, dinitrogen tetroxide
(N2O4) molecules and methane (CH4) molecules.

Dipole-dipole Interactions

are stronger intermolecular forces than Dispersion forces

occur between molecules that have permanent net dipoles (polar molecules), for
example, dipole-dipole interactions occur between SCl2 molecules, PCl3 molecules and
CH3Cl molecules.
If the permanent net dipole within the polar molecules results from a covalent bond
between a hydrogen atom and either fluorine, oxygen or nitrogen, the resulting

intermolecular force is referred to as a hydrogen bond (see below).

The partial positive charge on one molecule is electrostatically attracted to the partial
negative charge on a neighbouring molecule.

Hydrogen bonds

occur between molecules that have a permanent net dipole resulting from hydrogen
being covalently bonded to either fluorine, oxygen or nitrogen. For example, hydrogen
bonds operate between water (H2O) molecules, ammonia (NH3) molecules, hydrogen
fluoride (HF) molecules, hydrogen peroxide (H2O2) molecules, alkanols (alcohols) such
as methanol (CH3OH) molecules, and between alkanoic (caboxylic) acids such as
ethanoic (acetic) acid (CH3COOH) and between organic amines such as methanamine
(methyl amine, CH3NH2).

are a stronger intermolecular force than either Dispersion forces or dipole-dipole

interactions since the hydrogen nucleus is extremely small and positively charged and
fluorine, oxygen and nitrogen being very electronegative so that the electron on the
hydrogen atom is strongly attracted to the fluorine, oxygen or nitrogen atom, leaving a
highly localised positive charge on the hydrogen atom and highly negative localised
charge on the fluorine, oxygen or nitrogen atom. This means the electrostatic attraction
between these molecules will be greater than for the polar molecules that do not have
hydrogen covalently bonded to either fluorine, oxygen or nitrogen.

Effect of Intermolecular forces on melting and boiling points of molecular covalent

substances:
Since melting or boiling result from a progressive weakening of the attractive forces between
the covalent molecules, the stronger the intermolecular force is, the more energy is required to
melt the solid or boil the liquid.
If only dispersion forces are present, then the more
electrons the molecule has (and consequently the
more mass it has) the stronger the dispersion forces
will be, so the higher the melting and boiling points will
be.
Consider the hydrides of Group IV, all of which are nonpolar molecules, so only dispersion forces act between
the molecules.
CH4 (molecular mass ~ 16), SiH4 (molecular mass ~
32), GeH4 (molecular mass ~ 77) and SnH4(molecular
mass ~ 123) can all be considered non-polar covalent
molecules.
As the mass of the molecules increases, so does the
strength of the dispersion force acting between the
molecules, so more energy is required to weaken the
attraction between the molecules resulting in higher
boiling points.

Boiling Points of Group IV Hydrides

If a covalent molecule has a permanent net dipole then

the force of attraction between these molecules will be
stronger than if only dispersion forces were present
between the molecules. As a consequence, this
substance will have a higher melting or boiling point
than similar molecules that are non-polar in nature.
Consider the boiling points of the hydrides of Group VII
elements.
All of the molecules HF (molecular mass ~ 20), HCl
(molecular mass ~ 37), HBr (molecular mass ~ 81) and
HI (molecular mass ~ 128) are polar, the hydrogen
atom having a partial positive charge (H+) and the
halogen atom having a partial negative charge (F-, Cl-,
Br-, I-).
As a consequence, the stronger dipole-interactions
acting between the hydride molecules of Group VII
elements results in higher boiling points than for the
hydrides of Group IV elements as seen above.
With the exception of HF, as the molecular
massincreases, the boiling point of the hydrides
increase.
HF is an exception because of the stronger force of
attraction between HF molecules resulting from
hydrogen bonds acting bewteen the HF molecules.
Weaker dipole-dipole interactions act between the
molecules of HCl, HBr and HI. So HF has a higher
boiling point than the other molecules in this series.

Boiling Points of Group VII hydrides

Effect of Intermolecular Forces on Solubility

In general like dissolves like:

non-polar solutes dissolve in non-polar solvents

Paraffin wax (C30H62) is a non-polar solute that will dissolve in non-polar solvents like oil,
hexane (C6H14) or carbon tetrachloride (CCl4).
Paraffin wax will NOT dissolve in polar solvents such as water (H2O) or ethanol (ethyl
alcohol, C2H5OH).

polar solutes such as glucose (C6H12O6) will dissolve in polar solvents such as water
(H2O) or ethanol (ethyl alcohol, C2H5OH) as the partially positively charged atom of the
solute molecule is attracted to the partially negatively charged atom of the solvent
molecule, and the partially negatively charged atom of the solute molecule is attracted
to the partially positively charged atom of the solvent molecule.
Glucose will NOT dissolve in non-polar solvents such as oil, hexane (C6H14) or carbon
tetrachloride (CCl4).

Ionic solutes such as sodium chloride (NaCl) will generally dissolve in polar solvents but
not in non-polar solvents, since the positive ion is attracted the partially negatively
charged atom in the polar solvent molecule, and the negative ion of the solute is
attracted to the partially positively charged atom on the solvent molecule.

Hydrogen bond

Sign In
Register

If you like us, please share us on social media, tell your friends, tell
your professor or consider building or adopting a Wikitext for your
course.

BioWiki

GeoWiki

StatWiki

PhysWiki

MathWiki

SolarWiki
Periodic Table of the Elements

Reference Tables

Physical Constants

Units & Conversions

ChemWiki

Lab Techniques

Textbook Maps
Organic Chemistry Textbook Maps
Map: Bruice 6ed "Organic Chemistry"
1. Electronic Structure and Bonding (Acids and Bases)
1.11 The Bonds in Water

ChemWiki: The Dynamic Chemistry E-textbook > Textbook Maps > Organic Chemistry Textbook Maps > Map: Bruice 6ed
"Organic Chemistry" > 1. Electronic Structure and Bonding (Acids and Bases) > 1.11 The Bonds in Water

1.11 The Bonds in Water

1 Water the molecule
In water, each hydrogen nucleus is covalently bound to the central oxygen atom by a pair of electrons that are
shared between them. In H 2O, only two of the six outer-shell electrons of oxygen are used for this purpose,
leaving four electrons which are organized into two non-bonding pairs. The four electron pairs surrounding the
oxygen tend to arrange themselves as far from each other as possible in order to minimize repulsions between
these clouds of negative charge. This would ordinarily result in a tetrahedral geometry in which the angle
between electron pairs (and therefore the H-O-H bond angle) is 109.5. However, because the two non-bonding
pairs remain closer to the oxygen atom, these exert a stronger repulsion against the two covalent bonding pairs,
effectively pushing the two hydrogen atoms closer together. The result is a distorted tetrahedral arrangement in
which the HOH angle is 104.5.

Water's large dipole

hydrogen bonding

moment

leads

to

The H2O molecule is electrically neutral, but the positive and negative charges are not distributed uniformly. This
is illustrated by the gradation in color in the schematic diagram here. The electronic (negative) charge is
concentrated at the oxygen end of the molecule, owing partly to the nonbonding electrons (solid blue circles), and
to oxygen's high nuclear charge which exerts stronger attractions on the electrons. This charge displacement
constitutes an electric dipole, represented by the arrow at the bottom; you can think of this dipole as the electrical
"image" of a water molecule.

Opposite charges attract, so it is not surprising that the negative end of one water molecule will tend to orient
itself so as to be close to the positive end of another molecule that happens to be nearby. The strength of
this dipole-dipole attraction is less than that of a normal chemical bond, and so it is completely overwhelmed by
ordinary thermal motions in the gas phase.

Hydrogen bonding in water

But when the H2O molecules are crowded together in the liquid, these attractive forces exert a very noticeable
effect, which we call (somewhat misleadingly) hydrogen bonding. And at temperatures low enough to turn off the
disruptive effects of thermal motions, water freezes into ice in which the hydrogen bonds form a rigid and stable
network.

Notice that the hydrogen bond (shown by the dashed green line) is somewhat longer than the covalent OH
bond. It is also much weaker, about 23 kJ mol1 compared to the OH covalent bond strength of 492 kJ mol1.

2 Forty-one anomalies of water" some

of them rather esoteric.
Water has long been known to exhibit many physical properties that distinguish it from other small molecules of
comparable mass. Although chemists refer to these as the "anomalous" properties of water, they are by no
means mysterious; all are entirely predictable consequences of the way the size and nuclear charge of the
oxygen atom conspire to distort the electronic charge clouds of the atoms of other elements when these are
chemically bonded to the oxygen.

Boiling point
The most apparent peculiarity of water is its very high boiling point for such a light molecule. Liquid methane
CH4 (molecular weight 16) boils at 161C. As you can see from this diagram, extrapolation of the boiling points
of the various Group 16 hydrogen compounds to H2O suggests that this substance should be a gas under normal
conditions.

Surface tension
Compared to most other liquids, water also has a high surface tension.
Have you ever watched an insect walk across the surface of a pond? The water strider takes advantage of the
fact that the water surface acts like an elastic film that resists deformation when a small weight is placed on it. (If
you are careful, you can also "float" a small paper clip or steel staple on the surface of water in a cup.) This is all
due to the surface tension of the water. A molecule within the bulk of a liquid experiences attractions to
neighboring molecules in all directions, but since these average out to zero, there is no net force on the molecule.
For a molecule that finds itself at the surface, the situation is quite different; it experiences forces only sideways
and downward, and this is what creates the stretched-membrane effect.

The distinction between molecules located at the surface and those deep inside is especially prominent in H 2O,
owing to the strong hydrogen-bonding forces. The difference between the forces experienced by a molecule at
the surface and one in the bulk liquid gives rise to the liquid's surface tension.

This drawing highlights two H2O molecules, one at the surface, and the other in the bulk of the liquid. The surface
molecule is attracted to its neighbors below and to either side, but there are no attractions pointing in the 180
solid angle angle above the surface. As a consequence, a molecule at the surface will tend to be drawn into the
bulk of the liquid. But since there must always be some surface, the overall effect is to minimize the surface area
of a liquid.
The geometric shape that has the smallest ratio of surface area to volume is the sphere, so very small quantities
of liquids tend to form spherical drops. As the drops get bigger, their weight deforms them into the typical tear
shape.

Ice floats on water

The most energetically favorable configuration of H 2O molecules is one in which each molecule is hydrogenbonded to four neighboring molecules. Owing to the thermal motions described above, this ideal is never
achieved in the liquid, but when water freezes to ice, the molecules settle into exactly this kind of an arrangement
in the ice crystal. This arrangement requires that the molecules be somewhat farther apart then would otherwise
be the case; as a consequence, ice, in which hydrogen bonding is at its maximum, has a more open structure,
and thus a lower density than water.

Here are three-dimensional views of a typical local structure of water (left) and ice (right.) Notice the greater
openness of the ice structure which is necessary to ensure the strongest degree of hydrogen bonding in a
uniform, extended crystal lattice. The more crowded and jumbled arrangement in liquid water can be sustained
only by the greater amount of thermal energy available above the freezing point.
When ice melts, the more vigorous thermal motion disrupts much of the hydrogen-bonded structure, allowing the
molecules to pack more closely. Water is thus one of the very few substances whose solid form has a lower
density than the liquid at the freezing point. Localized clusters of hydrogen bonds still remain, however; these are
continually breaking and reforming as the thermal motions jiggle and shove the individual molecules. As the
temperature of the water is raised above freezing, the extent and lifetimes of these clusters diminish, so the
density of the water increases.

At higher temperatures, another effect, common to all substances, begins to dominate: as the temperature
increases, so does the amplitude of thermal motions. This more vigorous jostling causes the average distance
between the molecules to increase, reducing the density of the liquid; this is ordinary thermal expansion.
Because the two competing effects (hydrogen bonding at low temperatures and thermal expansion at higher
temperatures) both lead to a decrease in density, it follows that there must be some temperature at which the
density of water passes through a maximum. This temperature is 4 C; this is the temperature of the water you
will find at the bottom of an ice-covered lake in which this most dense of all water has displaced the colder water
and pushed it nearer to the surface.

3 Structure of liquid water

The nature of liquid water and how the H2O molecules within it are organized and interact are questions that have
attracted the interest of chemists for many years. There is probably no liquid that has received more intensive
study, and there is now a huge literature on this subject.
The following facts are well established:

H2O molecules attract each other through the special type of dipole-dipole interaction known as

hydrogen bonding
a hydrogen-bonded cluster in which four H 2Os are located at the corners of an imaginary tetrahedron is

an especially favorable (low-potential energy) configuration, but...

the molecules undergo rapid thermal motions on a time scale of picoseconds (1012 second), so the
lifetime of any specific clustered configuration will be fleetingly brief.
A variety of techniques including infrared absorption, neutron scattering, and nuclear magnetic resonance have
been used to probe the microscopic structure of water. The information garnered from these experiments and
from theoretical calculations has led to the development of around twenty "models" that attempt to explain the
structure and behavior of water. More recently, computer simulations of various kinds have been employed to
explore how well these models are able to predict the observed physical properties of water.
This work has led to a gradual refinement of our views about the structure of liquid water, but it has not produced
any definitive answer. There are several reasons for this, but the principal one is that the very concept of
"structure" (and of water "clusters") depends on both the time frame and volume under consideration. Thus
questions of the following kinds are still open:

How do you distinguish the members of a "cluster" from adjacent molecules that are not in that cluster?
Since individual hydrogen bonds are continually breaking and re-forming on a picosecond time scale, do

water clusters have any meaningful existence over longer periods of time? In other words, clusters are transient,
whereas "structure" implies a molecular arrangement that is more enduring. Can we then legitimately use the
term "clusters" in describing the structure of water?
The possible locations of neighboring molecules around a given H2O are limited by energetic and
geometric considerations, thus giving rise to a certain amount of "structure" within any small volume element. It is
not clear, however, to what extent these structures interact as the size of the volume element is enlarged. And as
mentioned above, to what extent are these structures maintained for periods longer than a few picoseconds?
In the 1950's it was assumed that liquid water consists of a mixture of hydrogen-bonded clusters (H 2O)n in
which n can have a variety of values, but little evidence for the existence of such aggregates was ever found. The
present view, supported by computer-modeling and spectroscopy, is that on a very short time scale, water is
more like a "gel" consisting of a single, huge hydrogen-bonded cluster. On a 10 12-109 sec time scale, rotations
and other thermal motions cause individual hydrogen bonds to break and re-form in new configurations, inducing
ever-changing local discontinuities whose extent and influence depends on the temperature and pressure.

Current views of water structure

The present thinking, influenced greatly by molecular modeling simulations beginning in the 1980s, is that on a
very short time scale (less than a picosecond), water is more like a "gel" consisting of a single, huge hydrogenbonded cluster. On a 10-12-10-9 sec time scale, rotations and other thermal motions cause individual hydrogen

bonds to break and re-form in new configurations, inducing ever-changing local discontinuities whose extent and
influence depends on the temperature and pressure.

Recent work from Richard SayKally's labratory

shows that the hydrogen bonds in liquid water break
and re-form so rapidly (often in distorted
configurations) that the liquid can be regarded as a
continuous network of hydrogen-bonded molecules.

This computer-generated nanoscale view of

liquid water is from the lab of Gene
Stanley of Boston University. The oxygen
atoms are red, the hydrogen atoms white

4 Ice
Ice, like all solids, has a well-defined structure; each water molecule is surrounded by four neighboring H 2Os. two
of these are hydrogen-bonded to the oxygen atom on the central H 2O molecule, and each of the two hydrogen
atoms is similarly bonded to another neighboring H2O.

Ice forms crystals having a hexagonal lattice structure, which in their full development would tend to form
hexagonal prisms very similar to those sometimes seen in quartz. This does occasionally happen, and anyone
who has done much winter mountaineering has likely seen needle-shaped prisms of ice crystals floating in the
air. Under most conditions, however, the snowflake crystals we see are flattened into the beautiful fractal-like
hexagonal structures that are commonly observed.

Snowflakes
The H2O molecules that make up the top and bottom plane faces of the prism are packed very closely and linked
(through hydrogen bonding) to the molecules inside. In contrast to this, the molecules that make up the sides of
the prism, and especially those at the hexagonal corners, are much more exposed, so that atmospheric H 2O
molecules that come into contact with most places on the crystal surface attach very loosely and migrate along it
until they are able to form hydrogen-bonded attachments to these corners, thus becoming part of the solid and
extending the structure along these six directions. This process perpetuates itself as the new extensions
themselves acquire a hexagonal structure.
Why is ice slippery?
At temperatures as low as 200 K, the surface of ice is highly disordered and water-like. As the temperature
approaches the freezing point, this region of disorder extends farther down from the surface and acts as a
lubricant.
The illustration is taken from from an article in the April 7, 2008 issue of C&EN honoring the physical chemist
Gabor Somorjai who pioneered modern methods of studying surfaces.

5 "Pure" water
To a chemist, the term "pure" has meaning only in the context of a particular application or process. The distilled
or de-ionized water we use in the laboratory contains dissolved atmospheric gases and occasionally some silica,
but their small amounts and relative inertness make these impurities insignificant for most purposes. When water
of the highest obtainable purity is required for certain types of exacting measurements, it is commonly filtered,
de-ionized, and triple-vacuum distilled. But even this "chemically pure" water is a mixture of isotopic species:
there are two stable isotopes of both hydrogen (H 1 and H2, the latter often denoted by D) and oxygen (O 16 and O18)
which give rise to combinations such as H 2O18, HDO16, etc., all of which are readily identifiable in the infrared
spectra of water vapor. And to top this off, the two hydrogen atoms in water contain protons whose magnetic
moments can be parallel or antiparallel, giving rise to ortho- and para-water, respectively. The two forms are
normally present in a o/p ratio of 3:1.
The amount of the rare isotopes of oxygen and hydrogen in water varies enough from place to place that it is
now possible to determine the age and source of a particular water sample with some precision. These
differences are reflected in the H and O isotopic profiles of organisms. Thus the isotopic analysis of human
hair can be a useful tool for crime investigations and anthropology research.

6 More about hydrogen bonding

Hydrogen bonds form when the electron cloud of a hydrogen atom that is attached to one of the more
electronegative atoms is distorted by that atom, leaving a partial positive charge on the hydrogen. Owing to the
very small size of the hydrogen atom, the density of this partial charge is large enough to allow it to interact with
the lone-pair electrons on a nearby electronegative atom. Although hydrogen bonding is commonly described as
a form of dipole-dipole attraction, it is now clear that it involves a certain measure of electron-sharing (between
the external non-bonding electrons and the hydrogen) as well, so these bonds possess some covalent
character.

Hydrogen bonds are longer than ordinary covalent bonds, and they are also weaker. The experimental evidence
for hydrogen bonding usually comes from X-ray diffraction studies on solids that reveal shorter-than-normal
distances between hydrogen and other atoms.

Hydrogen bonding in small molecules

The following examples show something of the wide scope of hydrogen bonding in molecules.
Ammonia (mp 78, bp 33C) is hydrogen-bonded in the
liquid and solid states.

Hydrogen bonding is responsible for ammonia's remarkably

high solubility in water.

Many organic (carboxylic) acids form hydrogen-bonded

dimers in the solid state.

Here the hydrogen bond acceptor is the electron cloud of a

benzene ring. This type of interaction is important in
maintaining the shape of proteins.

Hydrogen fluoride (mp 92, bp 33C) is another common substance that is

strongly hydrogen-bonded in its condensed phases.
The bifluoride ion (for which no proper Lewis structure can
be written) can be regarded as a complex ion held together
by the strongest hydrogen bond known: about 155 kJ mol1.

"As slow as molasses in the winter!" Multiple hydroxyl

groups provide lots of opportunities for hydrogen bonding
and lead to the high viscosities of substances such
as glycerine and sugar syrups.

Hydrogen bonding in biopolymers

Hydrogen bonding plays an essential role in natural polymers of biological origin in two ways:

Hydrogen bonding between adjacent polymer chains (intermolecular bonding);

Hydrogen bonding between different parts of the same chain (intramolecular bonding;
Hydrogen bonding of water molecules to OH groups on the polymer chain ("bound water") that helps
maintain the shape of the polymer.
The examples that follow are representative of several types of biopolymers.

Cellulose
Cellulose is a linear polymer of glucose (see above), containing 300 to over 10,000 units, depending on the
source. As the principal structural component of plants (along with lignin in trees), cellulose is the most abundant
organic substance on the earth. The role of hydrogen bonding is to cross-link individual molecules to build up
sheets as shown here. These sheets than stack up in a staggered array held together by van der Waals forces.
Further hydrogen-bonding of adjacent stacks bundles them together into a stronger and more rigid
structure.

Proteins
These polymers made from amino acids RCH(NH 2)COOH depend on intramolecular hydrogen bonding to
maintain their shape (secondary and tertiary structure) which is essential for their important function as biological
catalysts (enzymes). Hydrogen-bonded water molecules embedded in the protein are also important for their
structural integrity.
The principal hydrogen bonding in proteins is between the -NH groups of the "amino" parts with the -C=O
groups of the "acid" parts. These interactions give rise to the two major types of the secondary structure which
refers to the arrangement of the amino acid polymer chain:

alpha-helix
[images]

beta-sheet
Although carbon is not usually considered particularly electronegative, CH----X hydrogen bonds are also now
known to be significant in proteins.

DNA (Deoxyribonucleic acid)

Who you are is totally dependent on hydrogen bonds! DNA, as you probably know, is the most famous of the
biopolymers owing to its central role in defining the structure and function of all living organisms.

Each strand of DNA is built from a sequence of four different nucleotide monomers consisting of a deoxyribose
sugar, phosphate groups, and a nitrogenous base conventionally identified by the letters A,T, C and G. DNA itself
consists of two of these polynucleotide chains that are coiled around a common axis in a configuration something
like the protein alpha helix depicted above. The sugar-and-phosphate backbones are on the outside so that the
nucleotide bases are on the inside and facing each other. The two strands are held together by hydrogen bonds
that link a nitrogen atom of a nucleotide in one chain with a nitrogen or oxygen on the nucleotide that is across
from it on the other chain.

Efficient hydrogen bonding within this configuration can only occur between the pairs A-T and C-G, so these two
complementary pairs constitute the "alphabet" that encodes the genetic information that gets transcribed
whenever new protein molecules are built.
Water molecules, hydrogen-bonded to the outer parts of the DNA helix, help stabilize it.

Contributors

Stephen Lower, Professor Emeritus (Simon Frasier U.) Chem1 Virtual Textbook
Search

Save as PDF
Email page

The Core
Analytical Chemistry
Biological Chemistry
Inorganic Chemistry
Organic Chemistry
Physical Chemistry
Theoretical Chemistry

Wikitexts
Diablo Valley College
Hope College
Howard University
Purdue University
Sacramento City College
United Arab Emirates U
UC Davis
UC Irvine

Textbook Maps
General Chemistry
Analytical Chemistry
Organic Chemistry
Physical Chemistry
Theoretical Chemistry

An NSF funded Project

Powered by MindTouch

Unless otherwise noted, content in the UC Davis ChemWiki is

licensed under a Creative Commons Attribution-Noncommercial-Share Alike 3.0 United States
License. Permissions beyond the scope of this license may be available at [email protected]. Questions
and concerns can be directed toward Prof. Delmar Larsen ([email protected]), Founder and Director. Terms
of Use