How does hydrogen bonding affect The peculiar properties of water

boiling point? 1 Enthalpy change of vaporisation and

Some compounds may have higher boiling points than boiling point
expected. This can be due to hydrogen bonding. Figure
Water has a much higher enthalpy change of vaporisation
4.43 shows a graph of the boiling points of the hydrogen
and boiling point than expected.
halides, HF, HCl, HBr and HI, plotted against the position
This is due to its extensive hydrogen bonding. Figure
of the halogen in the Periodic Table.
4.44 shows the enthalpy changes of vaporisation of water
and other Group 16 hydrides.
+50
The rise in enthalpy change of vaporisation from H 2S
u0 to H 2Te is due to the increasing number of electrons in
--c:
·o
0..
0 the Group 16 atoms as we go down the group. This leads
tojncreased van der Waals' forces as the molecules get
:§ -50 bigger. If water only had van der Waals' forces between
·o
a:, its molecules, we would expect its enthalpy change to be
-100 about 17kJmo1- 1. But the enthalpy change of vaporisation
of water is much higher. This is because water is
extensively hydrogen bonded. The boiling point of water
HF HCI HBr HI
is also much higher than predicted by the trend in boiling
Figure 4.43 The boiling points of the hydrogen halides. points for the other Group 16 hydrides. This also indicates
that much more energy is required to break the bonds
The rise in boiling point from HCl to HI is due to the between water molecules compared with other hydrides of
increasing number of electrons in the halogen atoms as we Group 16 elements.
go down the group. This leads to increased van der Waals'
forces as the molecules get bigger. If hydrogen fluoride
only had van der Waals' forces between its molecules,
50
I
we would expect its boiling point to be about -90 °C. - 40
-0 L
However, the boiling point of hydrogen fluoride is 20 °C, 0
a, E
which is much higher. This is because of the stronger ~32
intermolecular forces of hydrogen bonding between the ii
l'O - -
§ 30
HF molecules.
~-;
.;; :s
l'O · -

C: 0..
w £;? 20
QUESTION

13 The table lists the boiling points of some Group 15 10--r--r--,-.-.--,,-.-.--,----,--r---.---.--,,--,

hydrides. 0 20 40 60 80 100 120 140
Number of elec;trons
Hydride I Boiling point / °C
Figure 4.44 Enthalpy changes of vaporisation for Group 16
ammonia, NH 3 -33 hydrides plotted against number of electrons present.
phosphine, PH 3 -88
arsine, AsH 3 -55 2 Surface tension and viscosity
L stibine, SbH 3 - 17 Water has a high surface tension and high viscosity.
Hydrogen bonding reduces the ability of water
a Explain the trend in the boiling points from molecules to slide over each other, so the viscosity of
phosphine to stibine.
water is high. The hydrogen bonds in water also exert a
b Explain why the boiling point of ammonia does not significant downward force at the surface of the liquid.
follow this trend.
This causes the surface tension of water to be higher than
for most liquids.
 onding and physical
B erties
3 Ice is less dense than water . .
. I' uids. 1111s ,s
proP 0din. between atoms, ions or molecules
Most solids are denser than their ' \ acked in the
Th e cype ofthe
bo ?al roperties of a substance.
physic P
because the molecules are more dos 1Yp . there is a . f)uences
fwater In ice, 10
solid state. But this is not true O • k of water te at room temperature and
ded networ
three-dimensional hydrogen- b on . h'ch each physical sta
molecules. This produces a ngi · 'd Iattice 1n w 1£hydrogen
t trahedron o pressure
oxygen atom is surrounded bYa e the relatively
, ,
atoms. This more open arrang ·
ement due to
' ul s to be . mpounds
ter mo1ec e 1on1c CO olids at room temperature and
long hydrogen bonds, allows th e wa . 6) So unds ares
· ·d (Figure 4·4 ·
. th e 1iqm Ionic compo .
slightly further apart than m 1bis is because.
. ·d water.
the density of ice is less than that ofl 1qm P ressure. . (' · b d )
electrostatic forces ionic on s holding
• there a~e-strondg egative ions togethe r
os1t1ve an n . (
t he P ly arranged in a lattice see Chapters)
· are regu Iar •
• the ions . 1 charged ions close to each other.
with the opposite y
e high melting points, h igh boiling
• mpoun d s h aV
Ionic co . h thalpy changes of vaporisation. It
oints and hig en l
P f to overcome the strong e ectrostatic
takes a lot o energy
attractive forces.

Metals
mercury are solids. Most metals have
Metal s, apar t from ' . .
high melting points, high boiling pomts _and high enthalpy
changes of vaporisation. This is because 1t takes a lot of
energy to overcome the strong attractive forces between
the positive ions and the 'sea' of delocalised electrons.
Figure 4.45 Ice floats on water.
Covalent compounds
Covalently bonded substances with a simple molecular
structure, for example water and ammonia, are usually
liquids or gases. This is because the forces between the
molecules are weak. It does not take much energy to
overcome these intermolecular forces, so these substances
have low melting points, low boiling points and low
enthalpy changes of vaporisation compa red with ionic
compounds. Some substances that have covalently bonded
molecules may be solids at room temperature for example
iodine and poly(eth ene). These are usually molecu
' 1es
where the van de w 1 , c H ver:
r aa s 1orces are considerable. owe '
the melting po· t Ofth · ]
ms ese substances are still fairly ow
compared with ·0 ·
• ruc compoun ds or most metals.

Solubility
Ionic compounds
Figure 4.46 A model of ice. Oxygen atoms are red, hydrogen Most ionic com ust
atoms are white, hydrogen bonds are lilac. This hydrogen- water pou nd s are soluble in water. This is beca
1
mo ecules are p O1 he
bonded arrangement makes ice less dense than water. ions on th ar and they are attracted to t
e surface of th . . . s
are called ion-di e iomc solid. These attraction
pole attractions (see page 265). These
 Chapter 5: States of matter

high electron density in certain parts of the molecule (see Graphene

electrophilic addition on page 209). Graphene is a single isolated layer of graphite (Figure 5.18).
A second type of fullerene is a class of molecules described The hexagonally arranged sheet of carbon atoms is not
as nanotubes. Nanotubes are fullerenes of hexagonally completely rigid and it can be distorted.
arranged carbon atoms like a single layer of graphite
bent into the form of a cylinder (Figure 5.17}. The first
nanotubes to be made were one layer of carbon atoms in
thickness. More recently nanotubes have behave been made . . .·
with thicker walls with several tubes inside one another.
Although the diameter of a nanotube is very small, it . . .

can be made relatively long. The length of the nanotube

- . "'-- . · . .
cylinder can be a million times greater than its diameter. . - . . .""' ~-...
•
Figure 5.18 a Part of a graphene sheet. b 'Waves' in a sheet
of graphene.

Graphene has some of the properties of graphite, but they

are more exaggerated. For example:
Graphene is the most chemically reactive form of carbon.
Single sheets of graphene burn at very low temperatures
and are much more reactive than graphite.
Graphene is extremely strong for its mass.
For a given amount of material, graphene conducts
electricity and heat much better than graphite.
Figure 5.17 Part of the structure of a nanotube. The ends of
It has been said that 'a one square metre hammock made
the cylinder are often closed .
of graphene could support a 4 kg cat but would weigh
only as much as the cat's whisker'. Potential applications
Nanotubes have characteristic properties:
of graphene include use in tiny electrical circuits and for
They have high electrical conductivity along the long axis tiny transistors, touchscreens, solar cells and other energy
oftITT! cylm-d-er. This is because, like graphite, some of the
storage devices.
electrons are delocalised and are able to move along the
cylinder when a voltage is applied.
They have a very high tensile strength when a force is QUESTION
applied along the long axis of the cylinder. They can be up to
~ e s stronger than steel of the same thickness. 13 Suggest, using ideas of structure and bonding, why:
· They have very high melting points (typically about 3S00'C). a buckminsterfullerene, C60' is converted from a
This is because there is strong covalent bonding thrpughout solid to a gas at a relatively low temperature
the structure. b graphene is a good conductor of electricity
Fullerenes have a large range of potential uses. c nanotubes condu ct electricity better along the
Reactive groups can be attached to their surfaces and long axis of the tube than across the tube
metal complexes (see page 371) can also be formed. d buckminsterfullerene, C60' is relatively soft.
Small molecules or atoms can be trapped in the cage
ofbuckminsterfullerenes. Possible medical uses
include delivering drugs to specific places in the body. Conserving materials
Nanotubes are used in tiny electrical circuits as 'wires'
and as electrodes in paper-thin batteries. They can be Why conserve materials?
incorporated into clothing and sports equipment for added There is only a limited supply of metal ores in the Earth.
strength. They have also been used in the treatment of If we use them all up, they cannot be replaced. The things
certain types of cancer. we make from metals and other materials from the
 Standard enthalpy changes The equation that describes the reaction must be given.
For example, the equation:
Standard conditions
To make any comparison of en h H (g) + ½O2 (g)
2
HzO(l) t:.H'; = -286 kJ mo1-1
comparison we t t alpy changes a fair
' mus use the sa me c d' .
called standard conditions: on itions. These are shows us the enthalpy change when one mole of water is
formed from hydrogen and oxygen. In this case 286 kJ of
a pressure of 10s Pa (lQSp .
_ atmospheric P~ ure) a is 1OO kPa, approximately n~ mal energy are released.
However, if we write the equation as
a temperature of 298 K (25 "C) (add 273 t h .
temperature to c - o t e Celsius
onvert a temperature into kelvin) 2Hz{g) + Oz(g) 2H 2O(1) t:.H'; = -572 kJ mo1-1
each substance involved in the react1·on i· . ·t
ph . I s ID I s normal
ys1ca state (solid, liquid or gas)at1os Pa and 298 K. two moles of water are formed from hydrogen and oxygen.
In this case 572 kJ of energy are released.
The symbol e- indicates that the entha)py h f, -:z::i
a t· . c ange re ers to
reac
Th ion. earned out under stand ard con d'1tions.
. Standard enthalpy change of
e information in the equation:
fjmation, ll.Wf
CH4(g) + 20/g) COi(g) + 2Hz0(1)
tlH&= -890.3kJmo1- 1
C The standard enthalpy change of formation is the
enthalpy change when one mole of a compound is
shows us that whe n one mo Ie O f methane gas reacts with formed from its elements under standard conditions. The
reactants and products must be in their standard states.
two moles of oxygen gas to form one mole of carbon
d10x,de gas and two moles of water in the liquid state the

I
standard enthalpy change is _ 890 _3 kJ mol- i. The symbol for standard enthalpy change of formation is
t:..H1. Enthalpy changes of formation can be exothermic
A variety of enthalpy changes or endothermic. We write the formula of the compound
We can describe enthalpy changes according to the type in square brackets after t:.H1 to help us when we do
of chemical reaction taking place. For example: calculations involving enthalpy changes. Examples are:

ell1hallll£,alaAge-ef formaJio.fl 2Fe(s) + l½O 2 (g) Fe2 O/s)

~thalpY..fllilnge of combustion
enthalpy ~ng_e of neu~ation t:.H1 [Fe 2O/s)] = -824.2 kJ mol- 1
enthalpy change of solution
C(graphite) + 2S(s) CSz(l)
enthalpy change of atomisatLon
enthalpy change of hydration. t:..H1[CSz(l)] = +98 .7kJmol- 1
In more general cases we can use the term: Note that the state symbol for carbon is shown as
enthalpy change of reaction. 'graphite'. This is because there are several forms of
carbon but the most stable is graphite and we choose the
Standard enthalpy change of most stable form when writing equations where enthalpy
changes are shown.
reaction, ll.H~ By definition, the standard enthalpy change of
formation of any element in its standard state is zero.
The standard enthalpy change of reaction is the enthalpy
change when the amounts of reactants shown in Standard enthalpy change of
the equation react to give products under standard combustion, t:.H-eC
conditions. The reactants and products must be in their
standard states.
The standard enthalpy change of com bustion is the
enthalpy change when one mole of a substance is burnt in
Tue symbol for standard enthalpy change of reaction is excess oxygen under sta ndard conditions. The reactants
t!.H ';. Enthalpy changes ofreaction can be exothermic and prod ucts must be in their standa rd states.

or endothermic.