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Other gas laws - Boyle's Law and Charles' Law

This page takes a simple look at Boyle's Law and Charles' Law, and is
suitable for 16 - 18 year old chemistry students doing a course the equivalent
of UK A level. The aim is simply to show how these laws relate to Kinetic
Theory (in a non-mathematical way), and to the ideal gas equation.
Before you waste time on this, be sure that you actually need to know about it.
Certainly in the UK exam system, it is pretty rare for chemistry students to be
expected to know either of these laws these days. They have been almost
completely replaced by the ideal gas equation.

Boyle's Law
Statement
For a fixed mass of gas at constant temperature, the volume is
inversely proportional to the pressure.
That means that, for example, if you double the pressure, you will halve the
volume. If you increase the pressure 10 times, the volume will decrease 10
times.
You can express this mathematically as
pV = constant

Is this consistent with pV = nRT ?


You have a fixed mass of gas, so n (the number of moles) is constant.

R is always constant - it is called the gas constant.


Boyle's Law demands that temperature is constant as well.
That means that everything on the right-hand side of pV = nRT is constant,
and so pV is constant - which is what we have just said is a result of Boyle's
Law.

Simple Kinetic Theory explanation


I'm not going to try to prove the relationship between pressure and volume
mathematically - I'm just showing that it is reasonable.
This is easiest to see if you think about the effect of decreasing the volume of
a fixed mass of gas at constant temperature.
Pressure is caused by gas molecules hitting the walls of the container.
With a smaller volume, the gas molecules will hit the walls more frequently,
and so the pressure increases.
You might argue that this isn't actually what Boyle's Law says - it wants you to
increase the pressure first and see what effect that has on the volume. But, in
fact, it amounts to the same thing.
If you want to increase the pressure of a fixed mass of gas without changing
the temperature, the only way you can do it is to squeeze it into a smaller
volume. That causes the molecules to hit the walls more often, and so the
pressure increases.

Charles' Law
Statement

For a fixed mass of gas at constant pressure, the volume is


directly proportional to the kelvin temperature.
That means, for example, that if you double the kelvin temperature from, say
to 300 K to 600 K, at constant pressure, the volume of a fixed mass of the gas
will double as well.
You can express this mathematically as
V = constant x T

Is this consistent with pV = nRT ?


You have a fixed mass of gas, so n (the number of moles) is constant.
R is the gas constant.
Charles' Law demands that pressure is constant as well.
If you rearrange the pV = nRT equation by dividing both sides by p, you will
get
V = nR/p x T
But everything in the nR/p part of this is constant.
That means that V = constant x T, which is Charles' Law.

Simple Kinetic Theory explanation


Again, I'm not trying to prove the relationship between pressure and volume
mathematically - just that it is reasonable.

Suppose you have a fixed mass of gas in a container with a moveable barrier something like a gas syringe, for example. The barrier can move without any
sort of resistance.

The barrier will settle so that the pressure inside and outside is identical.
Now suppose you heat the gas, but not the air outside.
The gas molecules will now be moving faster, and so will hit the barrier more
frequently, and harder. Meanwhile, the air molecules on the outside are hitting
it exactly as before.
Obviously, the barrier will be forced to the right, and the volume of the gas will
increase. That will go on until the pressure inside and outside is the same. In
other words, the pressure of the gas will be back to the same as the air again.
So we have fulfilled what Charles' Law says. We have a fixed mass of gas
(nothing has been added, and nothing has escaped). The pressure is the
same before and after (in each case, the same as the external air pressure).
And the volume increases when you increase the temperature of the gas.
What we haven't shown, of course, is that there is a "directly proportional"
relationship. It can be done, but it needs some maths.

REAL GASES

This page looks at how and why real gases differ from ideal gases,
and takes a brief look at the van der Waals equation. If you have
come straight to this page via a search engine, it might be a good
idea to read the page about ideal gases first.

Real gases v ideal gases


Real gases and the molar volume
I want to use this to illustrate the slight differences between the
numerical properties of real and ideal gases at normal
temperatures and pressures.
If you have read the page about ideal gases, you will remember
that we used the ideal gas equation to work out a value for the
molar volume of an ideal gas at stp (standard temperature and
pressure).
If you know the density of a gas at a particular temperature and
pressure, it is very easy to work out its molar volume.
For example, at 273 K and 1 atmosphere pressure, the density of
helium is 0.1785 g dm-3.
That means that 0.1785 g of helium occupies 1 dm 3 at stp. It is a
fairly simple sum to work out what 1 mole of helium, He, would
occupy.
1 mole of He weighs 4 g, and would occupy 4 / 0.1785 dm 3 = 22.4
dm3.
That's the same (at least to 3 significant figures) as the ideal gas
value, suggesting that helium behaves as an ideal gas under these

conditions.
Note: If your maths isn't very good, and you can't understand why I divided
4 by 0.1785 to get the answer, think of it like this:
Replace the awkward value of 0.1785 by something simple, like 2. If 2 g of
He occupied 1 dm3, what would 4 g occupy? It is obviously twice as much, 2
dm3 - but how did you get at that mathematically? You found out how many
times 2 would go into 4 - in other words, you divided 4 by 2. Do exactly the
same with the more complicated number.

If you do this for a random sample of other gases, you get these
values (to 3 significant figures) for the molar volume at stp (273 K
and 1 atmosphere pressure).
density (g dm-3)

molar volume at stp

He

0.1785

22.4

N2

1.2506

22.4

O2

1.4290

22.4

CH4

0.717

22.3

CO2

1.977

22.3

C2H4

1.260

22.2

NH3

0.769

22.1

SO2

2.926

21.9

So although for simple calculation purposes we use the value 22.4


dm3 for all gases, you can see that it isn't exactly true. Even at
ordinary temperatures and pressures, real gases can deviate
slightly from the ideal value. The effect is much greater under more
extreme conditions, as we will see next.

Compression factors
For an ideal gas, pV = nRT. If pV and nRT are the same, and you
divide one by the other, then the answer will, of course, be 1. For
real gases, pV doesn't equal nRT, and so the value will be
something different.
The term pV / nRT is called the compression factor. The graphs
below show how this varies for nitrogen as you change the
temperature and the pressure.

Note: These diagrams were generated using data produced from Patrick

Barrie's program, and converted into graphs using Excel. The figures are
derived from the van der Waals equation - not because it is the best source,
but because it is the only one you are likely to come across at this level, and
I shall mention it below. If you wanted to play around with some of the other
equations, you would find that the results produce similarly shaped curves,
but the absolute sizes of the deviations would vary.

If nitrogen was an ideal gas under all conditions of temperature and


pressure, every one of these curves would be a horizontal straight
line showing a compression factor of 1. That's obviously not true!

Things to notice

At low pressures of about 1 bar (100 kPa - just a bit less


than 1 atmosphere), the compression factor is close to 1.
Nitrogen approximates to ideal behaviour at ordinary
pressures.

The non-ideal behaviour gets worse at lower temperatures.


For temperatures of 300 or 400 K, the compression factor is
close to 1 over quite a large pressure range. The nitrogen
becomes more ideal over a greater pressure range as the
temperature rises.

The non-ideal behaviour gets worse at higher pressures.

There must be at least two different effects causing these


deviations. There must be at least one effect causing the
pV / nRT ratio to be too low, especially at low temperatures.
And there must be at least one effect causing it to get too
high as pressure increases. We will explore those effects in
a while.

Other gases

Is the same behaviour shown by other gases? The next diagram


shows how the compression factors vary with pressure for a variety
of gases at a fixed temperature.

If you were to redo the set of original nitrogen graphs (at varying
temperatures) for any of these other gases, you would find that
each of them will produce a set of curves similar to the nitrogen
ones. What varies is the temperature at which the different graph
shapes occur.
For example, if you look at the carbon dioxide graph at 273 K, it
looks similar to the nitrogen one at 100 K from the first set of
curves, although it doesn't increase so steeply at higher pressures.
It is easy to say that gases become less ideal at low temperatures,
but what counts as a low temperature varies from gas to gas. The
closer you get to to the temperature at which the gas would turn
into a liquid (or, in the case of carbon dioxide, a solid), the more
non-ideal the gas becomes.

What causes non-ideal behaviour?


In the compression factor expression, pV / nRT, everything on the
bottom of the expression is either known or can be measured
accurately. But that's not true of pressure and volume.
In the assumptions we make about ideal gases, there are two
statements which say things which can't be true of a real gas, and
these have an effect on both pressure and volume.

The volume problem


The kinetic theory assumes that, for an ideal gas, the volume taken
up by the molecules themselves is entirely negligible compared
with the volume of the container.
For a real gas, that assumption isn't true. The molecules
themselves do take up a proportion of the space in the container.
The space in the container available for things to move around in is
less than the measured volume of the container.

This problem gets worse the more the gas is compressed. If the
pressure is low, the volume taken up by the actual
molecules isinsignificant compared with the total volume of the

container.
But as the gas gets more compressed, the proportion of the total
volume that the molecules themselves take up gets higher and
higher. You could imagine compressing it so much that the
molecules were actually all touching each other. At that point the
volume available for them to move around in is zero!
Suppose at some high pressure, you measure the volume of the
container as, say, 1000 cm3, but suppose the molecules
themselves occupy as much as 100 cm3 of it.
The ideal gas equation was worked out by doing calculations based
on Kinetic Theory assumptions. The V in pV is assumed to be the
volume which the molecules are free to move around in - but in this
case, it would only be 900 cm3, not 1000 cm3.
If you worked out the compression factor, pV / nRT, by putting the
total volume of the container into the formula, the answer is bound
to be higher than it ought to be. It doesn't allow for the volume
taken up by the molecules themselves.
Let's just repeat one of the earlier diagrams so that you can see
this effect in operation.

For an ideal gas, the compression factor would be 1 over the whole
pressure range. For a real gas like nitrogen, notice how the
compression factor tends to increase with pressure.
The value of the compression factor is too high at high pressures
for a real gas. The reason for that is that the measured volume that
you put into the expression is too high because you aren't allowing
for the volume taken up by the molecules. That error gets relatively
worse the more compressed the gas becomes.

The pressure problem


Another key assumption of the Kinetic Theory for ideal gases is that
there are no intermolecular forces between the molecules. That is
wrong for every real gas.
If there weren't any intermolecular forces then it would be
impossible to condense the gas as a liquid. Even helium, with the
weakest of all intermolecular forces, can be turned to a liquid if the

temperature is low enough.


So what effect do intermolecular forces have?
For a gas molecule in the middle of the gas, there is no net effect. It
will be attracted to some extent to all the other molecules around it,
but, on average, those attractions will cancel each other out.
Attractions from behind a molecule, tending to slow it down, will be
cancelled out by attractions from in front of it, tending to speed it
up.

Despite all the intermolecular forces it is experiencing, the molecule


picked out in green will just continue to move in the same direction
at the same speed.
That's different if the molecule is just about to hit the wall of the
container.

Now there aren't any gas molecules in front of it, and the net pull is
backwards into the body of the gas. The molecule will slow down
just before it hits the wall.
If it slows down, it will hit the wall less hard, and so exert less
pressure.
The overall effect of this is to make the measured pressure less
than it would be if the gas was ideal. That means that if you put the
measured pressure into the expression pV / nRT, the value of the
compression factor will be less than it would be if the gas was ideal.
This is why, under some conditions, graphs of compression factors
drop below the ideal value of 1.
Look yet again at the nitrogen curves:

This effect is most important at low temperatures. Why is that?


At lower temperatures, the molecules are moving more slowly on
average. Any pull they feel back into the gas will have relatively
more effect on a slow moving particle than a faster one.
At higher temperatures, where the molecules are moving a lot
faster, any small pull back into the body of the gas is hardly going to
be noticeable. At high temperatures, the effect of intermolecular
forces is indeed negligible.
And there is one final effect concerning intermolecular forces which
is slightly more hidden away.
As pressure increases, the molecules are forced more closely
together. If they are closer, the intermolecular forces will become
more important. So, as pressure increases, you would expect more
lowering of the compression factor relative to the ideal case. The
molecules which slow down the one just about to hit the wall will be

closer to it, and so more effective.


Is that what happens? Yes, up to a point.
Look again at the nitrogen curve at 100 K. As the pressure
increases, at first the value of the compression factor falls.
But it soon starts to rise again. Why? Because at this point, the
effect of the size of the molecules starts to become more important
- and as the pressure is increased even more, this other effect
becomes dominant.

Which is the most ideal gas?


You are looking for a gas with the smallest possible molecules, and
the lowest possible intermolecular forces. That is helium.
A helium molecule consists of a single small atom, and the van der
Waals dispersion forces are as low as it is possible for them to be.
Note: If you aren't happy about the factors which affect the size of van der
Waals dispersion forces, follow this link. Use the BACK button to come back
to this page afterwards.

Like helium, a hydrogen molecule also has two electrons,


and so the intermolecular forces are going to be small - but
not as small as helium. In the hydrogen molecule, you have
two atoms that you can distribute the charges over.
As molecules get larger, then dispersion forces will
increase, and you may get other intermolecular forces such
as dipole-dipole attractions as well. Gases made of
molecules such as these will be much less ideal.

The van der Waals Equation


The van der Waals equation was the first attempt to try to
produce an equation which related p, V, n and T for real
gases. It looks like this:

If you think this looks complicated, you should see some of


the more modern attempts! Incidentally, you may come
across the equation in a simpler form for 1 mole of a gas
rather than for n moles. Under those circumstances, every
single n in the equation disappears.
Look at the left-hand side in two stages. First the pressure
term.
Remember from above, that the measured pressure is less
than the ideal pressure for a real gas. van der Waals has
added a term to compensate for that.
In the volume term, van der Waals has subtracted the value
nb to allow for the space taken up by the molecules
themselves.
a and b are constants for any particular gas, but they vary
from gas to gas to allow for the different intermolecular
forces, and molecular sizes. That means that, unfortunately,
you no longer have a single equation that you can use for
any gas.
Fortunately, however, the ideal gas equation works well
enough for most gases at ordinary pressures, as long as

the temperature is reasonably high.

DEAL GASES AND THE IDEAL GAS LAW

This page looks at the assumptions which are made in the


Kinetic Theory about ideal gases, and takes an introductory
look at the Ideal Gas Law: pV = nRT. This is intended only
as an introduction suitable for chemistry students at about
UK A level standard (for 16 - 18 year olds), and so there is
no attempt to derive the ideal gas law using physics-style
calculations.

Kinetic Theory assumptions about ideal gases


There is no such thing as an ideal gas, of course, but many
gases behave approximately as if they were ideal at
ordinary working temperatures and pressures. Real gases
are dealt with in more detail on another page.
The assumptions are:
Gases are made up of molecules which are in
constant random motion in straight lines.
The molecules behave as rigid spheres.
Pressure is due to collisions between the molecules

and the walls of the container.


All collisions, both between the molecules
themselves, and between the molecules and the walls
of the container, are perfectly elastic. (That means
that there is no loss of kinetic energy during the
collision.)
The temperature of the gas is proportional to the
average kinetic energy of the molecules.
And then two absolutely key assumptions, because these
are the two most important ways in which real gases differ
from ideal gases:
There are no (or entirely negligible) intermolecular
forces between the gas molecules.
The volume occupied by the molecules themselves is
entirely negligible relative to the volume of the
container.

The Ideal Gas Equation


The ideal gas equation is:
pV = nRT
On the whole, this is an easy equation to remember and
use. The problems lie almost entirely in the units. I am
assuming below that you are working in strict SI units (as
you will be if you are doing a UK-based exam, for example).

Exploring the various terms


Pressure, p
Pressure is measured in pascals, Pa - sometimes
expressed as newtons per square metre, N m-2. These
mean exactly the same thing.
Be careful if you are given pressures in kPa (kilopascals).
For example, 150 kPa is 150,000 Pa. You must make that
conversion before you use the ideal gas equation.
Should you want to convert from other pressure
measurements:
1 atmosphere = 101,325 Pa
1 bar = 100 kPa = 100,000 Pa

Volume, V
This is the most likely place for you to go wrong when you
use this equation. That's because the SI unit of volume is
the cubic metre, m3 - not cm3 or dm3.
1 m3 = 1000 dm3 = 1,000,000 cm3
So if you are inserting values of volume into the equation,
you first have to convert them into cubic metres.
You would have to divide a volume in dm3 by 1000, or in

cm3 by a million.
Similarly, if you are working out a volume using the
equation, remember to covert the answer in cubic metres
into dm3 or cm3if you need to - this time by multiplying by a
1000 or a million.
If you get this wrong, you are going to end up with a silly
answer, out by a factor of a thousand or a million. So it is
usually fairly obvious if you have done something wrong,
and you can check back again.

Number of moles, n
This is easy, of course - it is just a number. You already
know that you work it out by dividing the mass in grams by
the mass of one mole in grams.
You will most often use the ideal gas equation by first
making the substitution to give:

I don't recommend that you remember the ideal gas


equation in this form, but you must be confident that you
can convert it into this form.

The gas constant, R


A value for R will be given you if you need it, or you can
look it up in a data source. The SI value for R is 8.31441 J

K-1 mol-1.
Note: You may come across other values for this with
different units. A commonly used one in the past was 82.053
cm3 atm K-1 mol-1. The units tell you that the volume would be
in cubic centimetres and the pressure in atmospheres.
Unfortunately the units in the SI version aren't so obviously
helpful.

The temperature, T
The temperature has to be in kelvin. Don't forget to add 273 if you
are given a temperature in degrees Celsius.

Using the ideal gas equation


Calculations using the ideal gas equation are included in my
calculations book (see the link at the very bottom of the page), and
I can't repeat them here. There are, however, a couple of
calculations that I haven't done in the book which give a reasonable
idea of how the ideal gas equation works.
The molar volume at stp
If you have done simple calculations from equations, you have
probably used the molar volume of a gas.
1 mole of any gas occupies 22.4 dm3 at stp (standard temperature
and pressure, taken as 0C and 1 atmosphere pressure). You may
also have used a value of 24.0 dm3 at room temperature and
pressure (taken as about 20C and 1 atmosphere).
These figures are actually only true for an ideal gas, and we'll have
a look at where they come from.

We can use the ideal gas equation to calculate the volume of 1


mole of an ideal gas at 0C and 1 atmosphere pressure.
First, we have to get the units right.
0C is 273 K. T = 273 K
1 atmosphere = 101325 Pa. p = 101325 Pa
We know that n = 1, because we are trying to calculate the volume
of 1 mole of gas.
And, finally, R = 8.31441 J K-1 mol-1.
Slotting all of this into the ideal gas equation and then rearranging it
gives:

And finally, because we are interested in the volume in cubic


decimetres, you have to remember to multiply this by 1000 to
convert from cubic metres into cubic decimetres.
The molar volume of an ideal gas is therefore 22.4 dm 3 at stp.
And, of course, you could redo this calculation to find the volume of
1 mole of an ideal gas at room temperature and pressure - or any
other temperature and pressure.

Finding the relative formula mass of a gas from its density


This is about as tricky as it gets using the ideal gas equation.
The density of ethane is 1.264 g dm-3 at 20C and 1 atmosphere.

Calculate the relative formula mass of ethane.


The density value means that 1 dm3 of ethane weighs 1.264 g.
Again, before we do anything else, get the awkward units sorted
out.
A pressure of 1 atmosphere is 101325 Pa.
The volume of 1 dm3 has to be converted to cubic metres, by
dividing by 1000. We have a volume of 0.001 m 3.
The temperature is 293 K.
Now put all the numbers into the form of the ideal gas equation
which lets you work with masses, and rearrange it to work out the
mass of 1 mole.

The mass of 1 mole of anything is simply the relative formula mass


in grams.
So the relative formula mass of ethane is 30.4, to 3 sig figs.

Now, if you add up the relative formula mass of ethane, C 2H6using


accurate values of relative atomic masses, you get an answer of
30.07 to 4 significant figures. Which is different from our answer so what's wrong?

There are two possibilities.

The density value I have used may not be correct. I did the
sum again using a slightly different value quoted at a
different temperature from another source. This time I got an
answer of 30.3. So the density values may not be entirely
accurate, but they are both giving much the same sort of
answer.

Ethane isn't an ideal gas. Well, of course it isn't an ideal gas


- there's no such thing! However, assuming that the density
values are close to correct, the error is within 1% of what you
would expect. So although ethane isn't exactly behaving like
an ideal gas, it isn't far off.

If you need to know about real gases, now is a good time to read
about them.
AN INTRODUCTION TO CHEMICAL ENERGETICS

This page deals with the basic ideas about energy changes
during chemical reactions, including simple energy diagrams
and the terms exothermic and endothermic.

Energy changes during chemical reactions


Obviously, lots of chemical reactions give out energy as heat.
Getting heat by burning a fuel is a simple example, but you
will probably have come across lots of others in the lab.
Other reactions need a continuous supply of heat to make
them work. Splitting calcium carbonate into calcium oxide and

carbon dioxide is a simple example of this.


Any chemical reaction will involve breaking some bonds and
making new ones. Energy is needed to break bonds, and is
given out when the new bonds are formed. It is very unlikely
that these two processes will involve exactly the same amount
of energy - and so some energy will either be absorbed or
released during a reaction. You will find this discussed in
more detail in the page about bond enthalpies.

Simple energy diagrams


A reaction in which heat energy is given off is said to
beexothermic.
A reaction in which heat energy is absorbed is said to
beendothermic.
You can show this on simple energy diagrams.
For an exothermic change:

Notice that in an exothermic change, the products have a


lower energy than the reactants. The energy that the system

loses is given out as heat. The surroundings warm up.

For an endothermic change:

This time the products have a higher energy than the


reactants. The system absorbs this extra energy as heat from
the surroundings.

Expressing exothermic and endothermic changes in numbers


Here is an exothermic reaction, showing the amount of heat
evolved:

This shows that 394 kJ of heat energy are evolved when


equation quantities of carbon and oxygen combine to give
carbon dioxide. The mol-1 (per mole) refers to the whole
equation in mole quantities.
How do you know that heat is evolved? That is shown by the
negative sign.

You always think of the energy change during a reaction from


the point of view of the reactants. The reactants (carbon and
oxygen) have lost energy during the reaction. When you burn
carbon in oxygen, that is the energy which is causing the
surroundings to get hotter.
And here is an endothermic change:

In this case, 178 kJ of heat are absorbed when 1 mole of


calcium carbonate reacts to give 1 mole of calcium oxide and
1 mole of carbon dioxide.
You can tell that energy is being absorbed because of the plus
sign. A simple energy diagram for the reaction looks like this:

The products have a higher energy than the reactants. Energy


has been gained by the system - hence the plus sign.
Whenever you write values for any energy change, you must
always write a plus or a minus sign in front of it. If you have an
endothermic change, and write, say, 178 kJ mol-1 instead of
+178 kJ mol-1, you risk losing a mark in an exam.

Energetic stability
You are likely to come across statements that say that
something is energetically more stable than something else.
For example, in the next page in this section you will find that I
have said that oxygen, O2, is more energetically stable than
ozone, O3. What does this mean?
If you plot the positions of oxygen and ozone on an energy
diagram, it looks like this:

The lower down the energy diagram something is, the more
energetically stable it is. If ozone converted into ordinary
oxygen, heat energy would be released, and the oxygen would
be in a more energetically stable form than it was before.
So why doesn't ozone immediately convert into the more
energetically stable oxygen?
Similarly, if you mix petrol (gasoline) and air at ordinary
temperatures (when you are filling up a car, for example), why
doesn't it immediately convert into carbon dioxide and water?
It would be much more energetically stable if it turned into
carbon dioxide and water - you can tell that, because lots of
heat is given out when petrol burns in air. But there is no

reaction when you mix the two.


For any reaction to happen, bonds have to be broken, and new
ones made. Breaking bonds takes energy. There is a minimum
amount of energy needed before a reaction can start
-activation energy. If the molecules don't, for example, hit each
other with enough energy, then nothing happens. We say that
the mixture is kinetically stable, even though it may
beenergetically unstable with respect to its possible products.
So a petrol and air mixture at ordinary temperatures doesn't
react, even though a lot of energy would be released if the
reaction took place. Petrol and air are energetically unstable
with respect to carbon dioxide and water - they are much
higher up the energy diagram. But a petrol and air mixture is
kinetically stable at ordinary temperatures, because the
activation energy barrier is too high.
If you expose the mixture to a flame or a spark, then you get a
major fire or explosion. The initial flame supplies activation
energy. The heat given out by the molecules that react first is
more than enough to supply the activation energy for the next
molecules to react - and so on.
The moral of all this is that you should be very careful using
the word "stable" in chemistry!
Note: You will find a bit more about activation energy on the
introductory page about rates of reaction.

VARIOUS ENTHALPY CHANGE


DEFINITIONS

This page explains what an enthalpy change is, and then gives a
definition and brief comment for three of the various kinds of
enthalpy change that you will come across. You will find some more
definitions on other pages in this section.
It is essential that you learn the definitions. You aren't going to be
able to do any calculations successfully if you don't know exactly
what all the terms mean.

Enthalpy changes
Enthalpy change is the name given to the amount of heat evolved
or absorbed in a reaction carried out at constant pressure. It is
given the symbol H, read as "delta H".
Note: The term "enthalpy change" only applies to reactions
done at constant pressure. That is actually how most lab
reactions are done - in tubes or flasks (or whatever) open to the
atmosphere, so that the pressure is constant at atmospheric
pressure.
The phrase "at constant pressure" is an essential part of the
definition but, apart from that, you are unlikely to need to worry
about it if you are doing a UK-based exam at the equivalent of A
level.

Standard enthalpy changes


Standard enthalpy changes refer to reactions done understandard
conditions, and with everything present in theirstandard states.
Standard states are sometimes referred to as "reference states".
Standard conditions

Standard conditions are:

298 K (25C)

a pressure of 1 bar (100 kPa).

where solutions are involved, a concentration of 1 mol dm -3


Warning! Standard pressure was originally defined as 1
atmosphere (101.325 kPa), and you will still find that in older
books (including my calculations book). At the time of writing
(August 2010) there was at least one UK-based syllabus that
was still talking in terms of "1 atmosphere". It is essential to
check your syllabus to find out exactly what you need to learn.

Standard states
For a standard enthalpy change everything has to be present in its
standard state. That is the physical and chemical state that you
would expect to find it in under standard conditions.
That means that the standard state for water, for example, is liquid
water, H2O(l) - not steam or water vapour or ice.
Oxygen's standard state is the gas, O2(g) - not liquid oxygen or
oxygen atoms.
For elements which have allotropes (two different forms of the
element in the same physical state), the standard state is the most
energetically stable of the allotropes.
For example, carbon exists in the solid state as both diamond and
graphite. Graphite is energetically slightly more stable than
diamond, and so graphite is taken as the standard state of carbon.
Similarly, under standard conditions, oxygen can exist as O 2(simply
called oxygen) or as O3 (called ozone - but it is just an allotrope of

oxygen). The O2 form is far more energetically stable than O3, so


the standard state for oxygen is the common O2(g).

The symbol for standard enthalpy changes


The symbol for a standard enthalpy change is H, read as "delta
H standard" or, perhaps more commonly, as "delta H nought".
Note: Technically, the "o" in the symbol should have a
horizontal line through it, extending out at each side. This is
such a bother to produce convincingly without the risk of
different computers producing unreliable results, that I shall use
the common practice of simplifying it to "o".

Standard enthalpy change of reaction, Hr


Remember that an enthalpy change is the heat evolved or
absorbed when a reaction takes place at constant pressure.
The standard enthalpy change of a reaction is the enthalpy
change which occurs when equation quantities of materials
react under standard conditions, and with everything in its
standard state.
That needs exploring a bit.
Here is a simple reaction between hydrogen and oxygen to make
water:

First, notice that the symbol for a standard enthalpy change


of reaction is Hr. For enthalpy changes of reaction, the "r"

(for reaction) is often missed off - it is just assumed.

The "kJ mol-1" (kilojoules per mole) doesn't refer to any


particular substance in the equation. Instead it refers to the
quantities of all the substances given in the equation. In this
case, 572 kJ of heat is evolved when 2 moles of hydrogen
gas react with 1 mole of oxygen gas to form 2 moles of liquid
water.

Notice that everything is in its standard state. In particular,


the water has to be formed as a liquid.

And there is a hidden problem! The figure quoted is for the


reaction under standard conditions, but hydrogen and
oxygen don't react under standard conditions.
Whenever a standard enthalpy change is quoted, standard
conditions are assumed. If the reaction has to be done under
different conditions, a different enthalpy change would be
recorded. That has to be calculated back to what it would be
under standard conditions. Fortunately, you don't have to
know how to do that at this level.

Some important types of enthalpy change


Standard enthalpy change of formation, Hf
The standard enthalpy change of formation of a compound
is the enthalpy change which occurs when one mole of the
compound is formed from its elements under standard
conditions, and with everything in its standard state.
Note: When you are trying to learn these definitions, you can
make life easier for yourself by picking out the key bit, and
adding the other bits on afterwards. The key bit about this
definition is that you are forming 1 mole of a compound from its

elements. All the stuff about enthalpy change and standard


conditions and standard states is common to most of these
definitions.

The equation showing the standard enthalpy change of formation


for water is:

When you are writing one of these equations for enthalpy change
of formation, you must end up with 1 mole of the compound. If that
needs you to write fractions on the left-hand side of the equation,
that is OK. (In fact, it is not just OK, it isessential, because
otherwise you will end up with more than 1 mole of compound, or
else the equation won't balance!)
The equation shows that 286 kJ of heat energy is given out when 1
mole of liquid water is formed from its elements under standard
conditions.

Standard enthalpy changes of formation can be written for any


compound, even if you can't make it directly from the elements. For
example, the standard enthalpy change of formation for liquid
benzene is +49 kJ mol-1. The equation is:

If carbon won't react with hydrogen to make benzene, what is the


point of this, and how does anybody know what the enthalpy
change is?
What the figure of +49 shows is the relative positions of benzene

and its elements on an energy diagram:

How do we know this if the reaction doesn't happen? It is actually


very simple to calculate it from other values which wecan measure
- for example, from enthalpy changes of combustion (coming up
next). We will come back to this again when we look at calculations
on another page.
Knowing the enthalpy changes of formation of compounds enables
you to calculate the enthalpy changes in a whole host of reactions
and, again, we will explore that in a bit more detail on another page.

And one final comment about enthalpy changes of formation:


The standard enthalpy change of formation of an element in its
standard state is zero. That's an important fact. The reason is
obvious . . .
For example, if you "make" one mole of hydrogen gas starting from
one mole of hydrogen gas you aren't changing it in any way, so you
wouldn't expect any enthalpy change. That is equally true of any
other element. The enthalpy change of formation of any element
has to be zero because of the way enthalpy change of formation is
defined.

Note: Some sources say that the enthalpy change of formation


of elements is taken as zero by convention. That is simply
nonsense! The standard enthalpy change of formation of
elements is zero because of the way the enthalpy change is
defined.
If this confuses you, ignore it!

Standard enthalpy change of combustion, Hc


The standard enthalpy change of combustion of a
compound is the enthalpy change which occurs when one
mole of the compound is burned completely in oxygen
under standard conditions, and with everything in its
standard state.
The enthalpy change of combustion will always have a negative
value, of course, because burning always releases heat.
Two examples:

Notice:

Enthalpy of combustion equations will often contain


fractions, because you must start with only 1 mole of
whatever you are burning.

If you are talking about standard enthalpy changes of


combustion, everything must be in its standard state. One
important result of this is that any water you write amongst
the products must be there as liquid water.

Similarly, if you are burning something like ethanol, which is


a liquid under standard conditions, you must show it as a
liquid in any equation you use.

Notice also that the equation and amount of heat evolved in


the hydrogen case is exactly the same as you have already
come across further up the page. At that time, it was
illustrating the enthalpy of formation of water. That can
happen in some simple cases. Talking about the enthalpy
change of formation of water is exactly the same as talking
about the enthalpy change of combustion of hydrogen.

HESS'S LAW AND ENTHALPY CHANGE CALCULATIONS

This page explains Hess's Law, and uses it to do some simple


enthalpy change calculations involving enthalpy changes of
reaction, formation and combustion.

Hess's Law
Stating Hess's Law
Hess's Law is the most important law in this part of chemistry.
Most calculations follow from it. It says . . .
The enthalpy change accompanying a chemical change is
independent of the route by which the chemical change
occurs.

Explaining Hess's Law


Hess's Law is saying that if you convert reactants A into
products B, the overall enthalpy change will be exactly the
same whether you do it in one step or two steps or however
many steps.
If you look at the change on an enthalpy diagram, that is
actually fairly obvious.

This shows the enthalpy changes for an exothermic reaction


using two different ways of getting from reactants A to
products B. In one case, you do a direct conversion; in the
other, you use a two-step process involving some
intermediates.
In either case, the overall enthalpy change must be the same,
because it is governed by the relative positions of the
reactants and products on the enthalpy diagram.
If you go via the intermediates, you do have to put in some
extra heat energy to start with, but you get it back again in the
second stage of the reaction sequence.
However many stages the reaction is done in, ultimately the
overall enthalpy change will be the same, because the
positions of the reactants and products on an enthalpy

diagram will always be the same.


Note: It is possibly confusing that I am switching between the
terms enthalpy and energy. Enthalpy change is simply a particular
measure of energy change. You will remember that the enthalpy
change is the heat evolved or absorbed during a reaction
happening at constant pressure.
I have labelled the vertical scale on this particular diagram as
enthalpy rather than energy, because we are specifically thinking
about enthalpy changes. I could have just kept to the more general
term "energy", but I prefer to be accurate.

You can do calculations by setting them out as enthalpy diagrams


as above, but there is a much simpler way of doing it which needs
virtually no thought.
You could set out the above diagram as:

Hess's Law says that the overall enthalpy change in these two
routes will be the same. That means that if you already know two of
the values of enthalpy change for the three separate reactions
shown on this diagram (the three black arrows), you can easily
calculate the third - as you will see below.
The big advantage of doing it this way is that you don't have to
worry about the relative positions of everything on an enthalpy

diagram. It is completely irrelevant whether a particular enthalpy


change is positive or negative.
Warnings!
Although most calculations you will come across will fit into a
triangular diagram like the above, you may also come across other
slightly more complex cases needing more steps. That doesn't
make it any harder!
You need to take care in choosing your two routes. The pattern
will not always look like the one above. You will see that in the
examples below.

Enthalpy change calculations using Hess's Law cycles


I can only give a brief introduction here, because this is covered in
careful, step-by-step detail in my chemistry calculations book.

Working out an enthalpy change of formation from enthalpy


changes of combustion
If you have read an earlier page in this section, you may remember
that I mentioned that the standard enthalpy change of formation of
benzene was impossible to measure directly. That is because
carbon and hydrogen won't react to make benzene.
Important: If you don't know (without thinking about it too much)
exactly what is meant by standard enthalpy change of formation or
combustion, you must get this sorted out now. Re-read the page
about enthalpy change definitions before you go any further and learn them!

Standard enthalpy changes of combustion, Hc are relatively easy


to measure. For benzene, carbon and hydrogen, these are:
Hc (kJ mol-1)
C6H6(l)

-3267

C(s)

-394

H2(g)

-286

First you have to design your cycle.

Write down the enthalpy change you want to find as a simple


horizontal equation, and write H over the top of the arrow.
(In diagrams of this sort, we often miss off the standard
symbol just to avoid clutter.)

Then fit the other information you have onto the same
diagram to make a Hess's Law cycle, writing the known
enthalpy changes over the arrows for each of the other
changes.

Finally, find two routes around the diagram, always going


with the flow of the various arrows. You must never have one
of your route arrows going in the opposite direction to one of
the equation arrows underneath it.

In this case, what we are trying to find is the standard enthalpy


change of formation of benzene, so that equation goes horizontally.

You will notice that I haven't bothered to include the oxygen that the
various things are burning in. The amount of oxygen isn't critical
because you just use an excess anyway, and including it really
confuses the diagram.
Why have I drawn a box around the carbon dioxide and water at the
bottom of the cycle? I tend to do this if I can't get all the arrows to
point to exactly the right things. In this case, there is no obvious
way of getting the arrow from the benzene to point atboth the
carbon dioxide and the water. Drawing the box isn't essential - I just
find that it helps me to see what is going on more easily.
Notice that you may have to multiply the figures you are using. For
example, standard enthalpy changes of combustion start with 1
mole of the substance you are burning. In this case, the equations
need you to burn 6 moles of carbon, and 3 moles of hydrogen
molecules. Forgetting to do this is probably the most common
mistake you are likely to make.
How were the two routes chosen? Remember that you have to go
with the flow of the arrows. Choose your starting point as the corner
that only has arrows leaving from it. Choose your end point as the
corner which only has arrows arriving.
Now do the calculation:
Hess's Law says that the enthalpy changes on the two routes are

the same. That means that:


H - 3267 = 6(-394) + 3(-286)
Rearranging and solving:
H = 3267 + 6(-394) + 3(-286)
H = +45 kJ mol-1
Note: If you have a good memory, you might remember that I gave
a figure of +49 kJ mol-1 for the standard enthalpy change of
formation of benzene on an earlier page in this section. So why is
this answer different?
The main problem here is that I have taken values of the enthalpies
of combustion of hydrogen and carbon to 3 significant figures
(commonly done in calculations at this level). That introduces small
errors if you are just taking each figure once. However, here you
are multiplying the error in the carbon value by 6, and the error in
the hydrogen value by 3. If you are interested, you could rework the
calculation using a value of -393.5 for the carbon and -285.8 for the
hydrogen. That gives an answer of +48.6.
So why didn't I use more accurate values in the first place?
Because I wanted to illustrate this problem! Answers you get to
questions like this are often a bit out. The reason usually lies either
in rounding errors (as in this case), or the fact that the data may
have come from a different source or sources. Trying to get
consistent data can be a bit of a nightmare.

Working out an enthalpy change of reaction from enthalpy


changes of formation
This is the commonest use of simple Hess's Law cycles that you
are likely to come across.
In this case, we are going to calculate the enthalpy change for the

reaction between ethene and hydrogen chloride gases to make


chloroethane gas from the standard enthalpy of formation values in
the table. If you have never come across this reaction before, it
makes no difference.
Hf (kJ mol-1)
C2H4(g)

+52.2

HCl(g)

-92.3

C2H5Cl(g)

-109
Note: I'm not too happy about the value for chloroethane! The data
sources I normally use give a wide range of values. The one I have
chosen is an average value from the NIST Chemistry WebBook.
This uncertainty doesn't affect how you do the calculation in any
way, but the answer may not be exactly right - don't quote it as if
it was right.

In the cycle below, this reaction has been written horizontally, and
the enthalpy of formation values added to complete the cycle.

Again, notice the box drawn around the elements at the bottom,
because it isn't possible to connect all the individual elements to

the compounds they are forming in any tidy way. Be careful to


count up all the atoms you need to use, and make sure they are
written as they occur in the elements in their standard state. You
mustn't, for example, write the hydrogens as 5H(g), because the
standard state for hydrogen is H2.
Note: In truth, if I am doing this type of enthalpy sum myself (with
nobody watching!), I tend to just write the word "elements" in the
bottom box to save the bother of working out exactly how many of
everything I need. I would be wary of doing that in an exam,
though.

And now the calculation. Just write down all the enthalpy changes
which make up the two routes, and equate them.
+52.2 - 92.3 + H = -109
Rearranging and solving:
H = -52.2 + 92.3 - 109
H = -68.9 kJ mol-1
Note: I am afraid that this is as much as I feel I can give you on
this topic without risking sales of my book, or ending up in breach
of contract with my publishers. Unfortunately, it isn't enough for you
to be confident of being able to do these calculations every time.
Apart from anything else, you need lots of practice.
I have talked this through more gently in the book, with lots of
examples. If you chose to work through chapter 5 in the book, you
would be confident that you could do any chemical energetics
calculation that you were given.
Obviously I'm biased, but I strongly recommend that you either buy
the book, or get hold of a copy from your school or college or local
library. Don't just take my word for it - read the reviews on

the Amazon website .

BOND ENTHALPY (BOND ENERGY)


This page introduces bond enthalpies (bond energies) and looks at
some simple calculations involving them.
One of the most confusing things about this is the way the words
are used. These days, the term "bond enthalpy" is normally used,
but you will also find it described as "bond energy" - sometimes in
the same article. An even older term is "bond strength". So you can
take all these terms as being interchangeable.
As you will see below, though, "bond enthalpy" is used in several
different ways, and you might need to be careful about this.
Note: Bond enthalpies quoted from different sources often vary
by a few kilojoules, even if they are referring to exactly the same
thing. Don't worry if you come across slightly different values. As
you will see later on this page, calculations involving bond
enthalpies hardly ever give accurate answers anyway.
You may even find differences in values between different pages
of Chemguide, or differences between Chemguide and my
calculations book. If so, I apologise, but I tend to use a lot of
different data sources which have varied over the years.

Explaining the terms


Bond dissociation enthalpy and mean bond enthalpy

Simple diatomic molecules


A diatomic molecule is one that only contains two atoms. They
could be the same (for example, Cl2) or different (for example, HCl).
The bond dissociation enthalpy is the energy needed to break
one mole of the bond to give separated atoms - everything being in
the gas state.
Important! The point about everything being in the gas state
isessential. You cannot use bond enthalpies to do calculations
directly from substances starting in the liquid or solid state.
As an example of bond dissociation enthalpy, to break up 1 mole of
gaseous hydrogen chloride molecules into separate gaseous
hydrogen and chlorine atoms takes 432 kJ. The bond dissociation
enthalpy for the H-Cl bond is +432 kJ mol-1.

More complicated molecules


What happens if the molecule has several bonds, rather than just
1?
Consider methane, CH4. It contains four identical C-H bonds, and it
seems reasonable that they should all have the same bond
enthalpy.
However, if you took methane to pieces one hydrogen at a time, it
needs a different amount of energy to break each of the four C-H
bonds. Every time you break a hydrogen off the carbon, the
environment of those left behind changes. And the strength of a
bond is affected by what else is around it.
In cases like this, the bond enthalpy quoted is an average value.
In the methane case, you can work out how much energy is
needed to break a mole of methane gas into gaseous carbon and

hydrogen atoms. That comes to +1662 kJ and involves breaking 4


moles of C-H bonds. The average bond energy is therefore
+1662/4 kJ, which is +415.5 kJ per mole of bonds.
That means that many bond enthalpies are actually quoted
asmean (or average) bond enthalpies, although it might not
actually say so. Mean bond enthalpies are sometimes referred to
as "bond enthalpy terms".
In fact, tables of bond enthalpies give average values in another
sense as well, particularly in organic chemistry. The bond enthalpy
of, say, the C-H bond varies depending on what is around it in the
molecule. So data tables use average values which will work well
enough in most cases.
That means that if you use the C-H value in some calculation, you
can't be sure that it exactly fits the molecule you are working with.
So don't expect calculations using mean bond enthalpies to give
very reliable answers.
You may well have to know the difference between a bond
dissociation enthalpy and a mean bond enthalpy, and you should
be aware that the word mean (or average) is used in two slightly
different senses. But for calculation purposes, it isn't something you
need to worry about. Just use the values you are given.
Important: The rest of this page assumes that you have already
read the page about Hess's Law and enthalpy change
calculations. If you have come straight to the current page from a
search engine, you won't make sense of the way the calculations
are set out unless you first read the Hess's Law page.

Finding enthalpy changes of reaction from bond


enthalpies
I can only give a brief introduction here, because this is covered in
careful, step-by-step detail in my chemistry calculations book.

Cases where everything present is gaseous


Remember that you can only use bond enthalpies directly if
everything you are working with is in the gas state.
Using the same method as for other enthalpy sums
We are going to estimate the enthalpy change of reaction for the
reaction between carbon monoxide and steam. This is a part of the
manufacturing process for hydrogen.

The bond enthalpies are:


bond enthalpy (kJ mol-1)
C-O in carbon monoxide

+1077

C-O in carbon dioxide

+805

O-H

+464

H-H

+436

So let's do the sum. Here is the cycle - make sure that you
understand exactly why it is the way it is.

And now equate the two routes, and solve the equation to find the
enthalpy change of reaction.
H + 2(805) + 436 = 1077 + 2(464)
H = 1077 + 2(464) - 2(805) - 436
H = -41 kJ mol-1

Using a short-cut method for simple cases


You could do any bond enthalpy sum by the method above - taking
the molecules completely to pieces and then remaking the bonds. If
you are happy doing it that way, just go on doing it that way.
However, if you are prepared to give it some thought, you can save
a bit of time - although only in very simple cases where the
changes in a molecule are very small.
For example, chlorine reacts with ethane to give chloroethane and
hydrogen chloride gases.

(All of these are gases. I have left the state symbols out this time to

avoid cluttering the diagram.)


It is always a good idea to draw full structural formulae when you
are doing bond enthalpy calculations. It makes it much easier to
count up how many of each type of bond you have to break and
make.
If you look at the equation carefully, you can see what I mean by a
"simple case". Hardly anything has changed in this reaction. You
could work out how much energy is needed to break every bond,
and how much is given out in making the new ones, but quite a lot
of the time, you are just remaking the same bond.
All that has actually changed is that you have broken a C-H bond
and a Cl-Cl bond, and made a new C-Cl bond and a new H-Cl
bond. So you can just work those out.
bond enthalpy (kJ mol-1)
C-H

+413

Cl-Cl

+243

C-Cl

+346

H-Cl

+432

Work out the energy needed to break C-H and Cl-Cl:


+413 + 243 = +656 kJ mol-1
Work out the energy released when you make C-Cl and H-Cl:
-346 - 432 = -778 kJ mol-1
So the net change is +656 - 778 = -122 kJ mol-1

Note: Even if you choose not to use this method, it might be a


good idea to be aware of it. It is possible to imagine an examiner
setting a question which assumes that you will use this method,
and therefore doesn't give a particular bond enthalpy value that
you would need if you did it by the longer method. For example, in
the case above, you don't actually need to know the C-C bond
enthalpy.

Cases where you have a liquid present


I have to keep on saying this! Remember that you can only use
bond enthalpies directly if everything you are working with is in the
gas state.
If you have one or more liquids present, you need an extra energy
term to work out the enthalpy change when you convert from liquid
to gas, or vice versa. That term is the enthalpy change of
vaporisation, and is given the symbol Hvap or Hv.
This is the enthalpy change when 1 mole of the liquid converts to
gas at its boiling point with a pressure of 1 bar (100 kPa).
(Older sources might quote 1 atmosphere rather than 1 bar.)
For water, the enthalpy change of vaporisation is +41 kJ mol -1. That
means that it take 41 kJ to change 1 mole of water into steam. If 1
mole of steam condenses into water, the enthalpy change would be
-41 kJ. Changing from liquid to gas needs heat; changing gas back
to liquid releases exactly the same amount of heat.
To see how this fits into bond enthalpy calculations, we will
estimate the enthalpy change of combustion of methane - in other
words, the enthalpy change for this reaction:

Notice that the product is liquid water. You cannot apply bond
enthalpies to this. You must first convert it into steam. To do this
you have to supply 41 kJ mol-1.
The bond enthalpies you need are:
bond enthalpy (kJ mol-1)
C-H

+413

O=O

+498

C=O in carbon dioxide

+805

O-H

+464

The cycle looks like this:

This obviously looks more confusing than the cycles we've looked
at before, but apart from the extra enthalpy change of vaporisation
stage, it isn't really any more difficult. Before you go on, make sure

that you can see why every single number and arrow on this
diagram is there.
In particular, make sure that you can see why the first 4 appears in
the expression "4(+464)". That is an easy thing to get wrong. (In
fact, when I first drew this diagram, I carelessly wrote 2 instead of 4
at that point!)
That's the hard bit done - now the calculation:
H + 2(805) + 2(41) + 4(464) = 4(413) + 2(498)
H = 4(413) + 2(498) - 2(805) - 2(41) - 4(464)
H = -900 kJ mol-1
The measured enthalpy change of combustion is -890 kJ mol -1, and
so this answer agrees to within about 1%. As bond enthalpy
calculations go, that's a pretty good estimate.
Note: Because this is all covered in more detail in mycalculations
book, I am afraid that this is as far as I am prepared to go with
this topic. The book will give you a lot more examples, including
some variations such as calculating bond enthalpies from
enthalpies of formation, and vice versa.

LATTICE ENTHALPY (LATTICE ENERGY)


This page introduces lattice enthalpies (lattice energies) and BornHaber cycles.
Lattice enthalpy and lattice energy are commonly used as if they
mean exactly the same thing - you will often find both terms used
within the same textbook article or web site, including on university

sites.
In fact, there is a difference between them which relates to the
conditions under which they are calculated. However, the difference
is small, and negligible compared with the differing values for lattice
enthalpy that you will find from different data sources.
Unless you go on to do chemistry at degree level, the difference
between the two terms isn't likely to worry you.
Note: While I have been writing this section, the different values for the
same piece of data from different data sources has driven me crazy,
because there is no easy way of knowing which is the most recent or
most accurate data.
In the Born-Haber cycles below, I have used numbers which give a
consistent answer, but please don't assume that they are necessarily the
most accurate ones. If you are doing a course for 16 - 18 year olds,
none of this really matters - you just use the numbers you are given.
If you use my chemistry calculations book, you will find a slightly
different set of numbers. These came from the Chemistry Data Book
edited by Stark and Wallace, published by John Murray. Values from this
now fairly old book often differ slightly from more recent sources.
Don't worry about this. It doesn't affect the principles in any way. Just
don't assume that any bit of data you are given (even by me) is
necessarily "right"!

What is lattice enthalpy?


Two different ways of defining lattice enthalpy
There are two different ways of defining lattice enthalpy which
directly contradict each other, and you will find both in common
use. In fact, there is a simple way of sorting this out, but many

sources don't use it.


I will explain how you can do this in a moment, but first let's look at
how the problem arises.
Lattice enthalpy is a measure of the strength of the forces between
the ions in an ionic solid. The greater the lattice enthalpy, the
stronger the forces.
Those forces are only completely broken when the ions are present
as gaseous ions, scattered so far apart that there is negligible
attraction between them. You can show this on a simple enthalpy
diagram.

For sodium chloride, the solid is more stable than the gaseous ions
by 787 kJ mol-1, and that is a measure of the strength of the
attractions between the ions in the solid. Remember that energy (in
this case heat energy) is given out when bonds are made, and is
needed to break bonds.
So lattice enthalpy could be described in either of two ways.

You could describe it as the enthalpy change when 1 mole of


sodium chloride (or whatever) was formed from its scattered
gaseous ions. In other words, you are looking at a downward
arrow on the diagram.

In the sodium chloride case, that would be -787 kJ mol -1.

Or, you could describe it as the enthalpy change when 1


mole of sodium chloride (or whatever) is broken up to form
its scattered gaseous ions. In other words, you are looking at
an upward arrow on the diagram.
In the sodium chloride case, that would be +787 kJ mol -1.

Both refer to the same enthalpy diagram, but one looks at it from
the point of view of making the lattice, and the other from the point
of view of breaking it up.
Unfortunately, both of these are often described as "lattice
enthalpy".

This is an absurdly confusing situation which is easily resolved. I


suggest that you never use the term "lattice enthalpy" without
qualifying it.

You should talk about "lattice dissociation enthalpy" if you


want to talk about the amount of energy needed to split up a
lattice into its scattered gaseous ions.
For NaCl, the lattice dissociation enthalpy is +787 kJ mol -1.

You should talk about "lattice formation enthalpy" if you want


to talk about the amount of energy released when a lattice is
formed from its scattered gaseous ions.
For NaCl, the lattice formation enthalpy is -787 kJ mol -1.

That immediately removes any possibility of confusion.


So . . .

The lattice dissociation enthalpy is the enthalpy change


needed to convert 1 mole of solid crystal into its scattered
gaseous ions. Lattice dissociation enthalpies are always
positive.

The lattice formation enthalpy is the enthalpy change when


1 mole of solid crystal is formed from its scattered gaseous
ions. Lattice formation enthalpies are always negative.
Note: Find out which of these versions your syllabus is likely to want
you to know (even if they just call it "lattice enthalpy") and concentrate
on that one, but be aware of the confusion!
Incidentally, if you are ever uncertain about which version is being used,
you can tell from the sign of the enthalpy change being discussed. If the
sign is positive, for example, it must refer to breaking bonds, and
therefore to a lattice dissociation enthalpy.

Factors affecting lattice enthalpy


The two main factors affecting lattice enthalpy are the charges on
the ions and the ionic radii (which affects the distance between the
ions).
The charges on the ions
Sodium chloride and magnesium oxide have exactly the same
arrangements of ions in the crystal lattice, but the lattice enthalpies
are very different.

Note: In this diagram, and similar diagrams below, I am not interested


in whether the lattice enthalpy is defined as a positive or a negative
number - I am just interested in their relative sizes. Strictly speaking,
because I haven't added a sign to the vertical axis, the values are for
lattice dissociation enthalpies. If you prefer lattice formation enthalpies,
just mentally put a negative sign in front of each number.

You can see that the lattice enthalpy of magnesium oxide is much
greater than that of sodium chloride. That's because in magnesium
oxide, 2+ ions are attracting 2- ions; in sodium chloride, the
attraction is only between 1+ and 1- ions.

The radius of the ions


The lattice enthalpy of magnesium oxide is also increased relative
to sodium chloride because magnesium ions are smaller than
sodium ions, and oxide ions are smaller than chloride ions.

That means that the ions are closer together in the lattice, and that
increases the strength of the attractions.
You can also see this effect of ion size on lattice enthalpy as you go
down a Group in the Periodic Table.
For example, as you go down Group 7 of the Periodic Table from
fluorine to iodine, you would expect the lattice enthalpies of their
sodium salts to fall as the negative ions get bigger - and that is the
case:

Attractions are governed by the distances between the centres of


the oppositely charged ions, and that distance is obviously greater
as the negative ion gets bigger.
And you can see exactly the same effect if as you go down Group
1. The next bar chart shows the lattice enthalpies of the Group 1
chlorides.

Note: To save anyone the bother of getting in touch with me to point it


out, it's not strictly fair to include caesium chloride in this list. Caesium
chloride has a different packing arrangement of ions in its crystal, and
that has a small effect on the lattice enthalpy. The effect is small enough
that it doesn't actually affect the trend.

Calculating lattice enthalpy


It is impossible to measure the enthalpy change starting from a
solid crystal and converting it into its scattered gaseous ions. It is
even more difficult to imagine how you could do the reverse - start
with scattered gaseous ions and measure the enthalpy change
when these convert to a solid crystal.
Instead, lattice enthalpies always have to be calculated, and there
are two entirely different ways in which this can be done.
You can can use a Hess's Law cycle (in this case called a BornHaber cycle) involving enthalpy changes which can be measured.
Lattice enthalpies calculated in this way are described as
experimental values.
Or you can do physics-style calculations working out how much
energy would be released, for example, when ions considered as

point charges come together to make a lattice. These are described


as theoretical values. In fact, in this case, what you are actually
calculating are properly described as latticeenergies.
Note: If you aren't confident about Hess's Law cycles, it isessential that
you follow this link before you go on.

Experimental values - Born-Haber cycles


Standard atomisation enthalpies
Before we start talking about Born-Haber cycles, there is an extra
term which we need to define. That is atomisation enthalpy, Ha.
The standard atomisation enthalpy is the enthalpy change
when 1 mole of gaseous atoms is formed from the element
in its standard state. Enthalpy change of atomisation is
always positive.
You are always going to have to supply energy to break an element
into its separate gaseous atoms.
All of the following equations represent changes involving
atomisation enthalpy:

Notice particularly that the "mol-1" is per mole of atoms formed NOT per mole of element that you start with. You will quite
commonly have to write fractions into the left-hand side of the

equation. Getting this wrong is a common mistake.

Born-Haber cycles
I am going to start by drawing a Born-Haber cycle for sodium
chloride, and then talk it through carefully afterwards. You will see
that I have arbitrarily decided to draw this for lattice formation
enthalpy. If you wanted to draw it for lattice dissociation enthalpy,
the red arrow would be reversed - pointing upwards.

Focus to start with on the higher of the two thicker horizontal lines.
We are starting here with the elements sodium and chlorine in their
standard states. Notice that we only need half a mole of chlorine
gas in order to end up with 1 mole of NaCl.
The arrow pointing down from this to the lower thick line represents
the enthalpy change of formation of sodium chloride.
The Born-Haber cycle now imagines this formation of sodium
chloride as happening in a whole set of small changes, most of
which we know the enthalpy changes for - except, of course, for the
lattice enthalpy that we want to calculate.

The +107 is the atomisation enthalpy of sodium. We have to


produce gaseous atoms so that we can use the next stage in
the cycle.

The +496 is the first ionisation energy of sodium. Remember


that first ionisation energies go from gaseous atoms to
gaseous singly charged positive ions.

The +122 is the atomisation enthalpy of chlorine. Again, we


have to produce gaseous atoms so that we can use the next
stage in the cycle.

The -349 is the first electron affinity of chlorine. Remember


that first electron affinities go from gaseous atoms to
gaseous singly charged negative ions.

And finally, we have the positive and negative gaseous ions


that we can convert into the solid sodium chloride using the
lattice formation enthalpy.
Note: If you have forgotten about ionisation energies orelectron
affinities follow these links before you go on.

Now we can use Hess's Law and find two different routes around
the diagram which we can equate.
As I have drawn it, the two routes are obvious. The diagram is set
up to provide two different routes between the thick lines.
So, here is the cycle again, with the calculation directly underneath
it . . .

-411 = +107 + 496 + 122 - 349 + LE


LE = -411 - 107 - 496 - 122 + 349
LE = -787 kJ mol-1

Note: Notice that in the calculation, we aren't making any assumptions


about the sign of the lattice enthalpy (despite the fact that it is obviously
negative because the arrow is pointing downwards). In the first line of
the calculation, I have just written "+ LE", and have left it to the
calculation to work out that it is a negative answer.

How would this be different if you had drawn a lattice dissociation


enthalpy in your diagram? (Perhaps because that is what your
syllabus wants.)
Your diagram would now look like this:

The only difference in the diagram is the direction the lattice


enthalpy arrow is pointing. It does, of course, mean that you have

to find two new routes. You can't use the original one, because that
would go against the flow of the lattice enthalpy arrow.
This time both routes would start from the elements in their
standard states, and finish at the gaseous ions.
-411 + LE = +107 + 496 + 122 - 349
LE = +107 + 496 + 122 - 349 + 411
LE = +787 kJ mol-1
Once again, the cycle sorts out the sign of the lattice enthalpy for
you.
Note: You will find more examples of calculations involving Born-Haber
cycles in my chemistry calculations book. This includes rather more
complicated cycles involving, for example, oxides.
If you compare the figures in the book with the figures for NaCl above,
you will find slight differences - the main culprit being the electron affinity
of chlorine, although there are other small differences as well. Don't
worry about this - the values in the book come from an older data
source. In an exam, you will just use the values you are given, so it isn't
a problem.

Theoretical values for lattice energy


Let's assume that a compound is fully ionic. Let's also assume that
the ions are point charges - in other words that the charge is
concentrated at the centre of the ion. By doing physics-style
calculations, it is possible to calculate a theoretical value for what
you would expect the lattice energy to be.
And no - I am not being careless about this! Calculations of this
sort end up with values of lattice energy, and not latticeenthalpy. If

you know how to do it, you can then fairly easily convert between
the two.
There are several different equations, of various degrees of
complication, for calculating lattice energy in this way. You won't be
expected to be able to do these calculations at this level, but you
might be expected to comment on the results of them.
There are two possibilities:

There is reasonable agreement between the experimental


value (calculated from a Born-Haber cycle) and the
theoretical value.
Sodium chloride is a case like this - the theoretical and
experimental values agree to within a few percent. That
means that for sodium chloride, the assumptions about the
solid being ionic are fairly good.

The experimental and theoretical values don't agree.


A commonly quoted example of this is silver chloride, AgCl.
Depending on where you get your data from, the theoretical
value for lattice enthalpy for AgCl is anywhere from about 50
to 150 kJ mol-1 less than the value that comes from a BornHaber cycle.
In other words, treating the AgCl as 100% ionic
underestimates its lattice enthalpy by quite a lot.
The explanation is that silver chloride actually has a
significant amount of covalent bonding between the silver
and the chlorine, because there isn't enough
electronegativity difference between the two to allow for
complete transfer of an electron from the silver to the
chlorine.

Comparing experimental (Born-Haber cycle) and theoretical values


for lattice enthalpy is a good way of judging how purely ionic a
crystal is.
Note: If you have forgotten about electronegativity it might pay you to
revise it now by following this link.

Why is magnesium chloride MgCl2?


This section may well go beyond what your syllabus
requires. Before you spend time on it, check your syllabus
(and past exam papers as well if possible) to make sure.
The question arises as to why, from an energetics point of
view, magnesium chloride is MgCl2 rather than MgCl or
MgCl3 (or any other formula you might like to choose).
It turns out that MgCl2 is the formula of the compound which
has the most negative enthalpy change of formation - in
other words, it is the most stable one relative to the
elements magnesium and chlorine.
Let's look at this in terms of Born-Haber cycles.
In the cycles this time, we are interested in working out what
the enthalpy change of formation would be for the imaginary
compounds MgCl and MgCl3.
That means that we will have to use theoretical values of
their lattice enthalpies. We can't use experimental ones,
because these compounds obviously don't exist!
I'm taking theoretical values for lattice enthalpies for these

compounds that I found on the web. I can't confirm these,


but all the other values used by that source were accurate.
The exact values don't matter too much anyway, because
the results are so dramatically clear-cut.
We will start with the compound MgCl, because that cycle is
just like the NaCl one we have already looked at.

The Born-Haber cycle for MgCl

Find two routes around this without going against the flow of

any arrows. That's easy:


Hf = +148 + 738 + 122 - 349 - 753
Hf = -94 kJ mol-1
So the compound MgCl is definitely energetically more
stable than its elements.
I have drawn this cycle very roughly to scale, but that is
going to become more and more difficult as we look at the
other two possible formulae. So I am going to rewrite it as a
table.
You can see from the diagram that the enthalpy change of
formation can be found just by adding up all the other
numbers in the cycle, and we can do this just as well in a
table.
kJ
atomisation enthalpy of Mg

+148

1st IE of Mg

+738

atomisation enthalpy of Cl

+122

electron affinity of Cl

-349

lattice enthalpy

-753

calculated Hf

-94

The Born-Haber cycle for MgCl2


The equation for the enthalpy change of formation this time
is

So how does that change the numbers in the Born-Haber


cycle?
You need to add in the second ionisation energy of
magnesium, because you are making a 2+ ion.
You need to multiply the atomisation enthalpy of
chlorine by 2, because you need 2 moles of gaseous
chlorine atoms.
You need to multiply the electron affinity of chlorine by
2, because you are making 2 moles of chloride ions.
You obviously need a different value for lattice
enthalpy.
kJ
atomisation enthalpy of Mg

+148

1st IE of Mg

+738

2nd IE of Mg

+1451

atomisation enthalpy of Cl (x 2)

+244

electron affinity of Cl (x 2)

-698

lattice enthalpy

-2526

calculated Hf

-643

You can see that much more energy is released when you
make MgCl2 than when you make MgCl. Why is that?
You need to put in more energy to ionise the magnesium to
give a 2+ ion, but a lot more energy is released as lattice
enthalpy. That is because there are stronger ionic
attractions between 1- ions and 2+ ions than between the 1and 1+ ions in MgCl.
So what about MgCl3? The lattice energy here would be
even greater.

The Born-Haber cycle for MgCl3


The equation for the enthalpy change of formation this time
is

So how does that change the numbers in the Born-Haber


cycle this time?
You need to add in the third ionisation energy of
magnesium, because you are making a 3+ ion.
You need to multiply the atomisation enthalpy of
chlorine by 3, because you need 3 moles of gaseous
chlorine atoms.
You need to multiply the electron affinity of chlorine by

3, because you are making 3 moles of chloride ions.


You again need a different value for lattice enthalpy.
kJ
atomisation enthalpy of Mg

+148

1st IE of Mg

+738

2nd IE of Mg

+1451

3rd IE of Mg

+7733

atomisation enthalpy of Cl (x 3)

+366

electron affinity of Cl (x 3)

-1047

lattice enthalpy

-5440

calculated Hf

+3949

This time, the compound is hugely energetically unstable,


both with respect to its elements, and also to other
compounds that could be formed. You would need to supply
nearly 4000 kJ to get 1 mole of MgCl3 to form!
Look carefully at the reason for this. The lattice enthalpy is
the highest for all these possible compounds, but it isn't
high enough to make up for the very large third ionisation
energy of magnesium.
Why is the third ionisation energy so big? The first two
electrons to be removed from magnesium come from the 3s

level. The third one comes from the 2p. That is closer to the
nucleus, and lacks a layer of screening as well - and so
much more energy is needed to remove it.
The 3s electrons are screened from the nucleus by the 1
level and 2 level electrons. The 2p electrons are only
screened by the 1 level (plus a bit of help from the 2s
electrons).

Conclusion
Magnesium chloride is MgCl2 because this is the
combination of magnesium and chlorine which produces
the most energetically stable compound - the one with the
most negative enthalpy change of formation.
ENTHALPIES OF SOLUTION AND HYDRATION
This page looks at the relationship between enthalpies of
solution, hydration enthalpies and lattice enthalpies.
Note: You really ought to have read the pages about Hess's Law
cycles and lattice enthalpies before you continue with this page.

Enthalpy change of solution


Defining enthalpy change of solution
The enthalpy change of solution is the enthalpy change
when 1 mole of an ionic substance dissolves in water to
give a solution of infinite dilution.

Enthalpies of solution may be either positive or negative - in other


words, some ionic substances dissolved endothermically (for
example, NaCl); others dissolve exothermically (for example
NaOH).
An infinitely dilute solution is one where there is a sufficiently large
excess of water that adding any more doesn't cause any further
heat to be absorbed or evolved.
So, when 1 mole of sodium chloride crystals are dissolved in an
excess of water, the enthalpy change of solution is found to be +3.9
kJ mol-1. The change is slightly endothermic, and so the
temperature of the solution will be slightly lower than that of the
original water.

Thinking about dissolving as an energy cycle


Why is heat sometimes evolved and sometimes absorbed when a
substance dissolves in water? To answer that it is useful to think
about the various enthalpy changes that are involved in the
process.
You can think of an imaginary process where the crystal lattice is
first broken up into its separate gaseous ions, and then those ions
have water molecules wrapped around them. That is how they exist
in the final solution.
The heat energy needed to break up 1 mole of the crystal lattice is
the lattice dissociation enthalpy.
The heat energy released when new bonds are made between the
ions and water molecules is known as the hydration enthalpy of
the ion.
The hydration enthalpy is the enthalpy change when 1

mole of gaseous ions dissolve in sufficient water to give an


infinitely dilute solution. Hydration enthalpies are always
negative.

Factors affecting the size of hydration enthalpy


Hydration enthalpy is a measure of the energy released when
attractions are set up between positive or negative ions and water
molecules.
With positive ions, there may only be loose attractions between the
slightly negative oxygen atoms in the water molecules and the
positive ions, or there may be formal dative covalent (co-ordinate
covalent) bonds.
With negative ions, hydrogen bonds are formed between lone pairs
of electrons on the negative ions and the slightly positive hydrogens
in water molecules.
Note: You will find the attractions between water molecules and
positive ions discussed on the page about dative covalent bonding.
You will find the attractions between negative ions and water
molecules discussed on the page about hydrogen bonding.

The size of the hydration enthalpy is governed by the amount of


attraction between the ions and the water molecules.

The attractions are stronger the smaller the ion. For


example, hydration enthalpies fall as you go down a group in
the Periodic Table. The small lithium ion has by far the
highest hydration enthalpy in Group1, and the small fluoride
ion has by far the highest hydration enthalpy in Group 7. In
both groups, hydration enthalpy falls as the ions get bigger.

The attractions are stronger the more highly charged the ion.

For example, the hydration enthalpies of Group 2 ions (like


Mg2+) are much higher than those of Group 1 ions (like Na +).

Estimating enthalpies of solution from lattice enthalpies and


hydration enthalpies
The hydration enthalpies for calcium and chloride ions are given by
the equations:

The following cycle is for calcium chloride, and includes a lattice


dissociation enthalpy of +2258 kJ mol-1.
We have to use double the hydration enthalpy of the chloride ion
because we are hydrating 2 moles of chloride ions. Make sure you
understand exactly how the cycle works.

So . . .
Hsol = +2258 - 1650 + 2(-364)

Hsol = -120 kJ mol-1


Whether an enthalpy of solution turns out to be negative or positive
depends on the relative sizes of the lattice enthalpy and the
hydration enthalpies. In this particular case, the negative hydration
enthalpies more than made up for the positive lattice dissociation
enthalpy.
Important: This diagram is basically just to show you how to do
these calculations, but I have no confidence whatsoever in the
accuracy of the data I have used. The measured value for the
enthalpy of solution for anhydrous calcium chloride (the value which
we are trying to calculate here) is about -80 kJ mol-1. That bears little
relationship to the value calculated here!
I have no idea what the source of this discrepancy is. One or more of
the figures I am using is obviously inaccurate. Trying to find reliable
values for energy terms like lattice enthalpies or hydration enthalpies
has been a total nightmare throughout the whole of this energetics
section. Virtually every textbook I have available (and I have quite a
few!) gives different values. Virtually every textbook that you can
access via Google Books has different values. Virtually every
website that you look at seems to have its own combination of values
which may or may not agree with any of the books.
Despite the fact that I am now totally fed up with this whole topic, it
shouldn't affect you as a student or a teacher working towards an
exam the equivalent of UK A level. You have to work with whatever
values your examiners give you. What is important is that you
understand what you are doing. As long as the answer you come up
with is consistent with the data you are given, that is actually all that
matters to you.

ENTHALPY CHANGE OF
NEUTRALISATION

This page looks briefly at enthalpy changes of neutralisation. In


common with my experience with most of the other pages in this
section, searches for reliable data throw up various values for the
same reaction. Don't worry too much about this. It doesn't actually
affect the arguments.

Enthalpy change of neutralisation


Defining standard enthalpy change of neutralisation
The standard enthalpy change of neutralisation is the
enthalpy change when solutions of an acid and an alkali
react together under standard conditions to produce 1 mole
of water.

Notice that enthalpy change of neutralisation is always


measured per mole of water formed.
Enthalpy changes of neutralisation are always negative - heat is
given out when an acid and and alkali react. For reactions involving
strong acids and alkalis, the values are always very closely similar,
with values between -57 and -58 kJ mol-1.
That varies slightly depending on the acid-alkali combination (and
also on what source you look it up in!).

Why do strong acids reacting with strong alkalis give closely


similar values?
We make the assumption that strong acids and strong alkalis are
fully ionised in solution, and that the ions behave independently of
each other. For example, dilute hydrochloric acid contains hydrogen
ions and chloride ions in solution. Sodium hydroxide solution

consists of sodium ions and hydroxide ions in solution.


The equation for any strong acid being neutralised by a strong
alkali is essentially just a reaction between hydrogen ions and
hydroxide ions to make water. The other ions present (sodium and
chloride, for example) are just spectator ions, taking no part in the
reaction.
The full equation for the reaction between hydrochloric acid and
sodium hydroxide solution is:

. . . but what is actually happening is:

If the reaction is the same in each case of a strong acid and a


strong alkali, it isn't surprising that the enthalpy change is similar.
Note: Actually, of course, the enthalpy changes should be the same,
not similar, if the assumptions we are making are exactly true! The
small differences between strong acid-strong base combinations are
almost invariably glossed over at this level. In fact, I can't remember
ever seeing this discussed in any source - textbook or web. It isn't
uncommon to find a list of enthalpy changes of neutralisation showing
some variability in the strong acid-strong alkali cases, and then a few
lines later on, this is ignored completely with a statement that in these
cases, the enthalpy changes of neutralisation are the same,
because . . .
I have decide not to waste time trying to sort out the exact reasons for
the problem, because I suspect it will take ages and ages, and it is
never going to get asked at this level anyway.

Why do weak acids or weak alkalis give different values?

In a weak acid, such as ethanoic acid, at ordinary concentrations,


something like 99% of the acid isn't actually ionised. That means
that the enthalpy change of neutralisation will include other
enthalpy terms involved in ionising the acid as well as the reaction
between the hydrogen ions and hydroxide ions.
And in a weak alkali like ammonia solution, the ammonia is also
present mainly as ammonia molecules in solution. Again, there will
be other enthalpy changes involved apart from the simple formation
of water from hydrogen ions and hydroxide ions.
For reactions involving ethanoic acid or ammonia, the measured
enthalpy change of neutralisation is a few kilojoules less exothermic
than with strong acids and bases.
For example, one source which gives the enthalpy change of
neutralisation of sodium hydroxide solution with HCl as -57.9 kJ
mol-1, gives a value of -56.1 kJ mol-1 for sodium hydroxide solution
being neutralised by ethanoic acid.
For very weak acids, like hydrogen cyanide solution, the enthalpy
change of neutralisation may be much less. A different source
gives the value for hydrogen cyanide solution being neutralised by
potassium hydroxide solution as -11.7 kJ mol-1, for example.