Partition

If you have two immiscible liquids like ether and water, and
shake them up in a separating funnel, they obviously form two
layers. The ether is less dense than water, and so forms the top
layer.

Now suppose you shake up a mixture of ether and water

containing a substance which is soluble in both of them. Let's
suppose that the substance, X, is more soluble in ether than it
is in water.

Particles of X will cross the boundary between the two liquid

layers, and you will soon get a dynamic equilibrium set up. For
every particle which moves into the top layer, one will move
back down into the bottom one.

You could write an equation for this:

. . . and like any other equilibrium, you can find an equilibrium
constant:

This equilibrium constant is called the partition coefficient,

and is often given the symbol Kpc.

Like other equilibrium constants, partition coefficients are

constant at a constant temperature, but they have some other
restrictions as well. They only work properly for fairly dilute
solutions, and the solute must be in the same chemical form in
both solvents. It mustn't react, or ionise or associate (join
together in dimers, for example).

Partition coefficient calculations

A note on units

Notice that the partition coefficient is a simple ratio of two

concentrations. It doesn't matter what concentration units you
use - as long as you use the same ones top and bottom.

You could use mol dm-3, but more often you use g cm-3 - grams
per cubic centimetre.

Technically, the square brackets can only be used for

concentration in mol dm-3, but the Application Support Booklet
and CIE's mark schemes both use it for other units as well.

I'm not prepared to do that, and so shall use the term

"concentration of X" rather than [X] where non-standard
concentration units are used.
Calculating a partition coefficient

When a solution of 1.00 g of X in 100 cm3 of water was shaken

with 10 cm3 of ether, 0.80 g of X was transferred to the ether
layer. Calculate the partition coefficient of X between ether
and water.

If you are asked to calculate a partition coefficient between

two solvents, the concentration of the first solvent mentioned
goes on top of the Kpc expression. So in this case:

You have enough information to calculate both concentrations

in g cm-3.

concentration of X in ether = 0.80/10 g cm-3

If 0.80 g were transferred to the ether, 1.00 - 0.80 g = 0.20 g

were left in the water.

concentration of X in water = 0.20/100 g cm-3

So:

Obviously, you could work out the concentrations in ether and

in water as actual numbers before you put them into the
expression. Do it however you feel most comfortable.

Partition coefficients like this don't have units - the units

cancel out because they are the same top and bottom.
Calculations involving partition coefficients

The CIE syllabus says specifically that you should be able to

calculate a partition coefficient (in other words, what we have
just done). It says nothing whatsoever about using them to
calculate other things. These extra calculations are discussed
in the Application Support Booklet and have been asked twice
in exams up to June 2013 (both in 2009).

The Coursebook doesn't include them (quite properly!) because

the syllabus doesn't mention them, and this book has been
endorsed by CIE examiners as a "complete and precise
coverage" of the syllabus. So does that mean that CIE won't
ask any more questions in the future? Don't count on it!

A basic example

We will use the same case as before - the same solvents, the
same X and the same partition coefficient we have just
calculated.

This time we will work out how much would have been
extracted into the ether layer if we had shaken the original
solution of 1.00 g of X in 100 cm3 of water with just 5 cm3 of
ether.

We are trying to work out the mass of X extracted. Let's call

that m.

Now work out an expression for the concentration of the

solution of X in ether.

concentration of X in ether = m/5 g cm-3

What about the water? There will be (1.00 - m) g of X left in the
water. So:

concentration of X in water = (1.00 - m)/100 g cm-3

Now you can put all this into the partition coefficient
expression. Remember that we have already calculated the
partition coefficient of X between ether and water as 40.

You are then just faced with a simple, but slightly tedious, bit
of algebra:

Making it more tedious!

In the original calculation to find the partition coefficient, you

were told that if you shook the original solution of 1.00 g of X in
100 cm3 of water with 10 cm3 of ether, you extracted 0.80 g of
X.

Shaking it with 5 cm3 of ether, we have just worked out that

you would extract 0.67 g of X.
That would leave 0.33 g of X behind in the 100 cm3 of water.
Suppose you had carefully kept this solution, and then shook it
with a second fresh 5 cm3 of ether.

How much of X would you extract in total by using the ether as

two separate lots of 5 cm3 instead of the 10 cm3 in one go?

Let's call the mass of X extracted by the second lot of ether n -

so that we don't get confused.

Work out an expression for the concentration of the solution of

X in ether.

concentration of X in ether = n/5 g cm-3

What about the water? There will be (0.33 - n) g of X left in the

water after the second extraction. So:

concentration of X in water = (0.33 - n)/100 g cm-3

Now you can put all this into the partition coefficient
expression for X between ether and water as before.

That means that if you were to combine the two 5 cm3 lots of
ether, you would have extracted a total of 0.67 + 0.22 g of X.
That is 0.89 g.
You were originally told that if you had only done this once,
using the ether as a single lot of 10 cm3, you would only have
extracted 0.80 g.

You get a more efficient extraction by splitting your solvent up

into smaller volumes as above.

You use this sort of technique during the preparation of some

organic compounds. You extract what you are trying to make
from some messy solution in water so that it ends up in an
organic solvent. You then remove the solvent by careful
distillation.