23-Entropy and Gibbs free energy

Define the term entropy, S?

Entropy(S): The number of possible arrangements of the particles and their energy in a given system.

 At this level, in the past, we have usually just described entropy as a measure of the amount of disorder in a
system. A very regular, highly ordered system (diamond, for example) will have a very low entropy. A very
disordered system (a mixture of gases at a high temperature, for example) will have a high entropy.
 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 "number of possible arrangements of the particles and their energy in a given system" has increased.
And so the entropy has increased because of the more random distribution of the energy.
 System becomes more stable when its energy is spread out in a more disordered state.

Predict and explain the sign of the entropy changes that occur?

A) During a change in state, e.g. melting, boiling and dissolving (and their reverse)?

These all have low entropies because they are highly

ordered solids, but notice that the entropy usually
increases as the solid gets more complicated

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.

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.
 B) During a temperature change?
 If you add more energy by heating the gas, they are moving at all sorts of different speeds, changing all the
time, the number of different possibilities for arranging the energy over the molecules increases. And so
increasing the temperature increases the entropy of the system.

C) During a reaction in which there is a change in the number of gaseous 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.

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.

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.

Calculate the entropy change for a reaction?

State and use the Gibbs equation ΔG⦵ = ΔH⦵ – TΔS ⦵ 2and perform calculations using the equation ΔG⦵ =
ΔH⦵ – TΔS?

 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.

State whether a reaction or process will be feasible by using the sign of ΔG?

 In chemistry, a feasible 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.
  Whether or not a reaction (or other physical change) is feasible depends on the sign of ΔG°. If ΔG° is positive,
then the reaction isn't feasible under standard conditions - it can't happen.
 For a reaction to be feasible under standard conditions, ΔG° has to be negative.
 Remember that although it may be feasible, the reaction may not actually happen in any sensible time scale
if there is a high activation energy barrier.

Where ΔH is positive and ΔS is negative:

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 feasible at any temperature.

Where ΔH is positive and ΔS is positive:

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 feasible at low temperatures, but if you heat it, there will be a temperature at which
it becomes feasible, because ΔG becomes negative.

Where ΔH is negative and ΔS is negative:

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 feasible.