These statements introduce entropy and entropy changes, and will

only be examined at the end of a two year course.

Before you go on, you should find and read the statements in your copy
of the syllabus.

Statement 5.3(a)

This statement explains what entropy is. At this level, in the past, we
have usually just described it as a measure of the amount of disorder
in a system. A very regular, highly ordered system (diamond, for
example) will have very low entropy. A very disordered system (a
mixture of gases at a high temperature, for example) will have high
entropy.

The CIE statement expands on this a bit, but luckily not too much!
Let's look at this with a couple of thought experiments . . .

Suppose you held a stack of ten coins between your finger and thumb.
That's a fairly ordered state for them to be in. And then you dropped
them on the floor. Every time you did this, you would get a different
random pattern of coins on the floor - arranged just by chance. That is
now a disordered system.

Now, it is just imaginable that when you dropped them, by chance they
would fall into a neat stack of coins like the one you started with, but
the probability of that happening, compared to all the other ways that
the coins might fall, is so very, very tiny that you would be totally
amazed if it happened.

Technically, entropy applies to disorder in energy terms - not just to

disordered arrangements in space. But we often just quickly look at
how disordered a system is in space in order to make a judgement
about its entropy. A system which is more disordered in space will
tend to have more disorder in the way the energy is arranged as well.

Suppose you managed to arrange some gaseous molecules in a

container so that they were all exactly evenly spaced and so that they
all had exactly the same energy - a fairly ordered state. And then you
let them go and do what molecules do - move around, and bump into
each other and the walls of the container.

Each collision between two molecules will cause them to change

direction, and it will probably speed up one of them, and slow down
the other. After a very short time, their arrangement in space will be
chaotic, and so will the way energy is shared between them. The
faster moving particles have more energy; the slower ones less. The
entropy has increased in terms of the more random distribution of the
energy.

The syllabus says "explain that . . . a system becomes more stable

when its energy is spread out in a more disordered state".

That is really all you need to know. If you look in textbooks or on the
web, you will find explanations of increasing difficulty - some very
scary indeed! Don't waste time on these at this level.

Statement 5.3(b)

This is about the entropy changes which occur during certain physical
or chemical changes.

Statement 5.3(b)(i)

This covers entropy changes during a change of state, including solid

to liquid, liquid to gas and solid to aqueous solution.

Entropy is given the symbol S, and standard entropy (measured at 298

K and a pressure of 1 bar) is given the symbol S°. You might find the
pressure quoted as 1 atmosphere rather than 1 bar in less recent
sources. Don't worry about it - they are nearly the same. 1 bar is 100
kPa; 1 atmosphere is 101.325 kPa. Use whatever units the examiners
give you.

Here are some standard entropies for a few solids, all with the units J
K-1mol-1:

carbon (as 2.4

 diamond)

41.
calcium
4

68.
calcium fluoride
9

calcium 92.
carbonate 9

These all have low entropies because they are highly ordered solids,
but notice that the entropy usually increases as the solid gets more
complicated.

What happens during change of state? The following figures are for the
standard entropy of water in different states.

ice (approximate
48
value)

69.
liquid water
9

steam 189

The entropy increases as the molecules become more disordered as

you go from solid to liquid to gas.

Notice that there isn't very big jump in entropy when ice turns to
water. That's because the hydrogen bonding between the liquid
molecules imposes a fair amount of order on them even in the liquid.

. . . and for benzene:

liquid 17
benzene 3
 benzene 26
vapour 9

Notice that the benzene values are bigger than those of water-steam.
This is because benzene is a more complicated molecule. There are
more ways of arranging the energy of the molecule in a disordered way
over bigger molecules than smaller ones.

What happens when an ionic solid dissolves in water?

The ionic solid is highly ordered, and so has a relatively low entropy.
Pure liquid water also has a certain amount of order as explained
above. But when the solid dissolves in water, the whole system
becomes highly disordered as the crystal breaks up and the ions find
their way between the water molecules. Entropy increases.

Statement 5.3(b)(ii)

This covers the change in entropy during a temperature change.

Obviously if increasing the temperature involves a change of state in

the material, then you have increased the entropy . . . and we have
already looked at that.

Suppose there isn't a change of state.

Think back to having some gas particles in a container with a high

degree of disorder both in their spacial arrangement, and in their
energies - they are moving at all sorts of different speeds, changing all
the time.

If you add more energy by heating the gas, the number of different
possibilities for arranging the energy over the molecules increases.
And so increasing the temperature increases the entropy of the
system.

Statement 5.3(b)(iii)
This covers changes in entropy in reactions involving at least some
gas molecules.

Gases have higher entropies than solids or liquids because of their

disordered movement. That means that during a reaction in which
there is a change in the number of molecules of gas present, entropy
will change.

Reactions involving an increase in the number of gas molecules

For example, the effect of heat on calcium carbonate, or the reaction

between a carbonate and an acid:

In both cases, there are no gases on the left-hand side of the equation,
but carbon dioxide appears on the right. Entropy will increase during
such a reaction, because of the increased disorder.

Reactions involving a decrease in the number of gas molecules

For example, the production of ammonia:

In this case, there is a decrease in entropy during the forward reaction

because there are fewer gas molecules than you had to start with.
That means that there fewer ways of arranging the energy of the
system over those molecules, and so entropy decreases.

This statement asks you to be able to predict the sign of the entropy
change during a particular process.

Before you go on, you should find and read the statement in your copy
of the syllabus.

In statement 5.3(b) we looked at the entropy changes which occurred

during various processes - physical and chemical.
This statement 5.3(c) just asks you to be able to predict whether
entropy will increase or decrease during straightforward processes
chosen by the examiners. You obviously can't do that if you aren't
familiar with statement 5.3(b).

Some examples:

This is just a crystalline solid going into solution. The solid is highly
ordered; the solution is disordered. There is an increase in entropy.

The water is changing from the highly disordered gas into a more
ordered liquid. The entropy will fall.

There are three moles of gas on the left-hand side of the equation, but
only one on the right. The starting materials are more disordered than
the products, and so there is a decrease in entropy.

Notice that if the water had been formed as steam, you couldn't easily
predict whether there was an increase or a decrease in entropy,
because there would be three moles of gas on each side.

The presence of the five moles of liquid water on the left-hand side
means that there will be far more disorder before the change than
there is in the products. The copper(II) sulphate crystals formed will
be very ordered. Entropy will decrease.

This statement is about calculating entropy changes for a reaction

given values of standard entropies for everything taking part.
Before you go on, you should find and read the statement in your copy
of the syllabus.

Standard entropies, S°

Entropy is given the symbol S, and standard entropy (measured at 298

K and a pressure of 1 bar) is given the symbol S°. You might find the
pressure quoted as 1 atmosphere rather than 1 bar in less recent
sources. Don't worry about it - they are nearly the same. 1 bar is 100
kPa; 1 atmosphere is 101.325 kPa. Use whatever units the examiners
give you.

The units of entropy are J K-1mol-1. The thing you must be most careful
about is the fact that entropy is measured in joules, not kilojoules,
unlike most of the other energy terms you will have come across.

In an exam, you will be given values for all the standard entropies you
need.

Entropy changes, ΔS°

Working out entropy changes for a reaction is very easy.

You add up the entropies for everything you end up with, and take
away the entropies of everything you started with.

Change in entropy = what you end up with - what you

started with

Or if you like things mathematical:

ΔS° = ΣS°(products) - ΣS°(reactants)

Where Σ (sigma) simply means "the sum of".

In statement 5.3(c) we looked at the following reaction and worked out
that there would be a decrease in entropy. Let's now do the
calculation.

CH4(g) O2(g) CO2(g) H2O(l)

S° (J K-1mol-
1 186 205 214 69.9
)

You started with 1 mole of methane and 2 moles of oxygen.

Total starting entropy = 186 + 2(205) = 596 J K-1mol-1

You ended up with 1 mole of carbon dioxide and two moles of liquid
water.

Total entropy at the end = 214 + 2(69.9) = 353.8 J K-1mol-1

Entropy change = what you end up with - what you started with.

Entropy change = 353.8 - 596 = -242.2 J K-1mol-1

Notice that it is a negative value. The entropy has decreased - as we

predicted it would in the earlier statement. That's because there is a
decrease in the total number of gas molecules present.

And that is all there is to it! You will, of course, need to practise doing
this until you are completely confident, but you will need to find your
own examples. There are lots in my calculations book if you have a
copy. If you look at those, you can ignore any reference to the word
"system" - CIE doesn't need this.

These statements introduce the idea of Gibbs free energy change, and
show how it can be calculated.
Before you go on, you should find and read the statements in your copy
of the syllabus. You won't be able to understand this topic unless you
are already familiar with entropy changes from previous statements.

Standard Gibbs free energy change, ΔG°

Defining ΔG°

For the purposes of these statements, I am just going to show how

standard Gibbs free energy change is calculated. The importance of it
will be dealt with in statements 5.4(c) and(d).

ΔG° = ΔH° - TΔS°

That's all you need to know. Learn it!

Calculating ΔG°

If you know (or can work out) the enthalpy change for the reaction,
and you know (or can work out) the entropy change, and you know the
temperature (in kelvin), then it would seem to be really easy to work
out ΔG°.

There is an easy mistake to be made though! You have to remember

that the entropy change is calculated in energy units of joules, but ΔG°
and ΔH° are both measured in kJ.

You must remember to change the entropy change value into kJ before
you start, otherwise you will get the calculation completely wrong.

That might matter more than you think. In the final two statements in
this section, you will find that the sign (positive or negative) of ΔG°
matters. If you get that wrong in the calculation by not converting the
entropy change value into kJ, it could mean that you couldn't complete
the rest of a question properly.

In statement 5.3(d), we calculated the entropy change for the reaction

ΔS° worked out as -242.2 J K-1mol-1.

Before you do anything else, convert this to kJ by dividing by 1000.

ΔS° = -0.2422 kJ K-1mol-1.

This reaction is actually the combustion of methane, and so we can

just take a value of this from a Data Book. But you should, of course,
know how to calculate this from enthalpy changes of formation.

ΔH° = -890.4 kJ mol-1.

So if you had to calculate the Gibbs free energy change at, say, 298 K,
you can just slot the numbers in:

ΔG° = ΔH° - TΔS°

ΔG° = -890.4 - 298(-0.2442) = -817.6 kJ mol-1

It is easy as long as you remember to convert the entropy change

value into kJ.

You will, of course, have to find some questions to practise on.

These statements are about using ΔG° to decide whether or not a

change will be spontaneous, and how changing the temperature might
affect the spontaneity.

Before you go on, you should find and read the statements in your copy
of the syllabus.

Spontaneous changes

In everyday life, something is spontaneous if it happens of its own

accord, without any input from outside. The same thing is true in
chemistry, but there is one major difference which defies everyday
common sense.
If you drop marble chips (calcium carbonate) into dilute hydrochloric
acid, there is an immediate fizzing. You don't need to do anything else
- the reaction happens entirely of its own accord. It is a spontaneous
change.

But in chemistry, a spontaneous change doesn't have to be rapid; in

fact, it can be very, very, very slow indeed - even infinitely slow!

For example, carbon burns in oxygen to make carbon dioxide, but a

piece of carbon will stay totally unchanged however long you keep it
unless you first heat it. The energetics are right for a reaction to
happen, but there is a huge activation energy.

Chemistry counts the reaction between carbon and oxygen as

spontaneous! Personally, I think that is daft, and I prefer the word
"feasible", which is often used in this topic. However, CIE uses the
technical term "spontaneous", and so that is what we will use too.

Spontaneous changes and ΔG°

Whether or not a reaction (or other physical change) is spontaneous

depends on the sign of ΔG°. If ΔG° is positive, then the reaction isn't
spontaneous under standard conditions - it can't happen.

For a reaction to be spontaneous under standard conditions, ΔG° has

to be negative.

Remember that although it may be feasible (a better word than

spontaneous!), the reaction may not actually happen in any sensible
time scale if there is a high activation energy barrier.

ΔG changes with temperature

You have met the equation:

ΔG = ΔH - TΔS
Using this equation is easily illustrated using the decomposition of
calcium carbonate:

The value of ΔS for this reaction is +160.4 J K-1 mol-1.

Remember that if you are using this in ΔG calculations, you first have
to convert into kJ.

ΔS = +0.1604 kJ K-1 mol-1.

Suppose you had some calcium carbonate in the lab at 293 K. You can
calculate a value of ΔG as:

ΔG = +178 - 293(+0.1604) = +131 kJ mol-1

The value is positive and so the reaction isn't spontaneous (feasible).

It cannot happen at this temperature.

But suppose you heated it to 1000°C (1273 K). Recalculating gives:

ΔG = +178 - 1273(+0.1604) = -26.2 kJ mol-1

This value is negative, and so the reaction is spontaneous at this

temperature. And you know, of course, that if you heat calcium
carbonate strongly enough, it decomposes to give calcium oxide and
carbon dioxide.

So how strongly do you have to heat it? You can work out an
approximate temperature by finding out at what point ΔG becomes
negative (i.e. less than 0).

For a reaction to be spontaneous, the value of ΔG has to be less than

0. In mathematical terms, it is spontaneous if:

ΔG < 0

Because ΔG = ΔH - TΔS, that means that for a spontaneous reaction:

 ΔH - TΔS < 0

If you know values for ΔH and ΔS, then you can work out a value for T
which makes this expression less than 0.

In the case we are looking at

ΔH = +178 kJ mol-1, and

ΔS = +0.1604 kJ K-1 mol-1

Putting those values into the expression ΔH - TΔS < 0 gives

178 - T x 0.1604 < 0

You can treat the "less than" sign just like an equals sign, and so
rearranging this gives:

178 < T x 0.1604

178 / 0.1604 < T

1110 < T

That's a strange way of looking at it, of course ("1110 is less than T.").
But that is just the same as saying that T has to be greater than 1110
K.

Working out the effect of temperature without doing calculations

Look again at the equation:

ΔG = ΔH - TΔS

Remember that for a reaction to be spontaneous, ΔG has to be

negative.

ΔH could be negative (an exothermic reaction) or positive (an

endothermic reaction). Similarly ΔS could be either positive or
negative.
There are four possible combinations of the signs of ΔH and ΔS. I want
to look at those in turn.

Where ΔH is negative and ΔS is positive

In the equation ΔG = ΔH - TΔS:

ΔH is negative. TΔS is positive, and so -TΔS is negative.

Both terms are negative irrespective of the temperature, and so ΔG is

also bound to be negative. The reaction will be spontaneous at all
temperatures.

Where ΔH is positive and ΔS is negative

In the equation ΔG = ΔH - TΔS:

ΔH is positive. TΔS is negative, and so -TΔS is positive.

Both terms are positive irrespective of the temperature, and so ΔG is

also bound to be positive. The reaction will not be spontaneous at any
temperature.

Where ΔH is positive and ΔS is positive

In the equation ΔG = ΔH - TΔS:

ΔH is positive. TΔS is positive, and so -TΔS is negative.

Now increasing the temperature will change things. At higher

temperatures, -TΔS will become more and more negative, and will
eventually outweigh the effect of ΔH.

The reaction won't be spontaneous at low temperatures, but if you

heat it, there will be a temperature at which it becomes spontaneous,
because ΔG becomes negative.
The decomposition of calcium carbonate is a case like this, and we
have done three calculations around it.

Where ΔH is negative and ΔS is negative

In the equation ΔG = ΔH - TΔS:

ΔH is negative. TΔS is negative, and so -TΔS is positive.

Again there will be a temperature effect. As temperature increases, -

TΔS will become more and more positive, and will eventually outweigh
the effect of ΔH.

At low temperatures, ΔG will be negative because of the effect of the

negative ΔH, but as you increase the temperature, the effect of the
positive -TΔS will eventually outweigh that. The value of ΔG will then
become positive, and the reaction will no longer be spontaneous.

In summary

I really wouldn't suggest you tried to learn this - it is too confusing.

Make sure that you understand it, so that when a question comes up
you can work it out at the time.

If you want to practise on a real case, look at Q7(c) in the specimen

paper for the 2016 syllabus. That is the only question available at the
time of writing, and there won't be anything else available until after
the June 2016 exams.

But it isn't too difficult to make up questions for yourself which would
help you through the whole topic. Choose a simple reaction where you
can find entropy values for everything involved. Use a data book if you
have one, or find the equivalent information online, and avoid anything
which involves solutions.

Use enthalpies of formation to work out the enthalpy change for the
reaction. (If you use combustion reactions, for example, then you can
just look up the enthalpy of combustion to save you the bother!)
Then work out the entropy change during the reaction. Decide what
the effect of temperature will be on the feasibility of the reaction, and
then work out values of ΔG at some widely different temperatures to
see if you are right. (When you are doing those calculations, don't
forget to correct the entropy change value from joules to kJ!)