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 be exothermic.

A reaction in which heat energy is absorbed is said to be endothermic.

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, O 2,
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 be energetically 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!

Two common enthalpy change measurements

Enthalpy changes involving solutions

The experiments

There are a whole range of different enthalpy changes that can be

measured by reacting solutions (or a solution plus a solid) in a simple
expanded polystyrene cup. A common example would be the
measurement of the enthalpy change of neutralisation of, say,
hydrochloric acid and sodium hydroxide solution.

The polystyrene cup serves to insulate the reaction mixture, and slows
heat losses from the side and bottom. Heat is still lost from the
surface of the liquid mixture, of course, and that can be reduced by
using a polystyrene lid with a hole for a thermometer.

You can allow for heat losses during the reaction by plotting a cooling
curve.

All of this is described in some detail at the beginning of Chapter 5 of

my chemistry calculations book, and I can't repeat it on Chemguide.

There are other sources of error in these experiments - in particular in

the accuracy of the thermometer used. Since the temperature rise
probably won't be very great, you would need to use the most accurate
thermometer possible in order to keep the percentage error low.

The calculations

The heat evolved or absorbed during a reaction is given by the

expression:

Heat evolved or absorbed = mass x specific heat x

temperature change

That can be written in symbols as

Heat evolved or absorbed = m s ΔT

You will find that the specific heat is sometimes given the symbol "s"
and sometimes the symbol "c".

The specific heat of a substance is the amount of heat needed to

increase the temperature of 1 gram of it by 1 K (which is the same as
1°C).

So for water (the value you are most likely to come across), the
specific heat is 4.18 J g-1 K-1.

That means that it takes 4.18 joules to increase the temperature of 1

gram of water by 1 K (or 1°C).

In experiments of this sort, you will quite commonly have measured

out a volume of solution rather than a mass, and it is very common to
assume that the density of the solution is exactly the same as water (1
g cm-3). That means that 25 cm3 of solution would have a mass of 25 g.

That is an approximation, though, and it does introduce some error.

The assumption is also made that the specific heat of a solution is the
same as the specific heat of water. That's another approximation, and
it also introduces errors into the answer.

What is generally true is that these errors are relatively small

compared with errors caused by heat losses, and so on.

Anyway . . .

To do the calculation, you would normally just work out the amount of
heat evolved or absorbed in your particular reaction, and then scale it
up to give an enthalpy change per mole.

You will find examples of this in Chapter 5 of my chemistry

calculations book.

Enthalpy changes of combustion

As normally measured in a lab at this level, these are far less accurate
than the simple solution reactions above. It is impossible to eliminate
heat losses, or to be sure that you have complete combustion.

You will find these experiments discussed in my chemistry

calculations book, but you will also find that a Google search will
throw up endless versions with practical details, and possibly sample
calculations.

The examples in my book include a fairly simple way of getting around

the heat loss problem.

I'm afraid that is as far as I am prepared to go on this topic without

risking sales of my book, or breaching my contract with my publishers.
Sorry!

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.

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.

Standard enthalpy changes of combustion, ΔH°c are relatively easy to

measure. For benzene, carbon and hydrogen, these are:

ΔH°c (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 ΔH 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 at both 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:

ΔH - 3267 = 6(-394) + 3(-286)

Rearranging and solving:

ΔH = 3267 + 6(-394) + 3(-286)

ΔH = +45 kJ mol-1

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.

ΔH°f (kJ mol-

1
)

C2H4(g) +52.2

HCl(g) -92.3

C2H5Cl(g
-109
)
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.

And now the calculation. Just write down all the enthalpy changes
which make up the two routes, and equate them.

+52.2 - 92.3 + ΔH = -109

Rearranging and solving:

ΔH = -52.2 + 92.3 - 109

ΔH = -68.9 kJ mol-1

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.

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 is

essential. 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 as mean
(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.

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
+1077
monoxide

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.

ΔH + 2(805) + 436 = 1077 + 2(464)

ΔH = 1077 + 2(464) - 2(805) - 436

ΔH = -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

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 ΔHvap or ΔHv.

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
+805
dioxide

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:

ΔH + 2(805) + 2(41) + 4(464) = 4(413) + 2(498)

ΔH = 4(413) + 2(498) - 2(805) - 2(41) - 4(464)

ΔH = -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.
LATTICE ENTHALPY (LATTICE ENERGY)

This page introduces lattice enthalpies (lattice energies) and Born-

Haber 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.

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.

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.

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 as you go down Group 1. The
next bar chart shows the lattice enthalpies of the Group 1 chlorides.

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 Born-Haber
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 lattice energies.

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, ΔH°a.

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.

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

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.

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 lattice enthalpy. 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 Born-Haber 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.

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:

ΔHf = +148 + 738 + 122 - 349 - 753

ΔHf = -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 +14

Mg 8

+73
1st IE of Mg
8

atomisation enthalpy of +12

Cl 2

electron affinity of Cl -349

lattice enthalpy -753

calculated ΔHf -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
 +145
2nd IE of Mg
1

atomisation enthalpy of Cl
+244
(x 2)

electron affinity of Cl (x 2) -698

lattice enthalpy -2526

calculated ΔHf -643

You can see that much more energy is released when you make MgCl 2
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 1- and 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

+145
2nd IE of Mg
1

+773
3rd IE of Mg
3

atomisation enthalpy of Cl
+366
(x 3)

electron affinity of Cl (x 3) -1047

lattice enthalpy -5440

+394
calculated ΔHf
9

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.

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.

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 Mg 2+) 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 . . .

ΔHsol = +2258 - 1650 + 2(-364)

ΔHsol = -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.