The distribution of ammonia or iodine between two immiscible solvents

Distribution of iodine between two immiscible solvents

Using iodine crystals dissolved in equal volumes of two immiscible solvents, students can
create an equilibrium distribution.

Class practical or Demonstration

Students observe iodine crystals dissolving in equal volumes of two immiscible solvents,
aqueous potassium iodide and cyclohexane, and familiarize themselves with the different
colours of the two solutions. To each solution they add the other solvent and observe the
gradual extraction of the iodine from one layer to the other until an equilibrium
distribution is reached. If the quantity of iodine and the volume of each solvent are the same
in both tubes, they should be able to observe that the same equilibrium position has been
reached in both tubes. Using further volumes of the two solvents, they can demonstrate that
it is possible to achieve almost complete extraction from one solvent to the other.

Apparatus Chemicals

For a class practical, each Cyclohexane (HIGHLY FLAMMABLE, HARMFUL,

working group will need: DANGEROUS FOR THE ENVIRONMENT),
3
10 cm (Note 1)
Eye protection
Iodine crystals (HARMFUL, DANGEROUS FOR THE
Test-tubes, 2
ENVIRONMENT), a few small crystals (Note 2)
Corks to fit test-tubes, 2
Potassium iodide solution, 0.5 M, 20 cm3
Test-tube rack
Refer to Health & Safety and Technical notes section
Dropping pipettes, 2 below for additional information.
Spatula

Wear eye protection.

Cyclohexane, C6H12(l), (HIGHLY FLAMMABLE, HARMFUL, DANGEROUS FOR THE

ENVIRONMENT).

Iodine, I2(s) (HARMFUL, DANGEROUS FOR THE ENVIRONMENT).

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Procedure

a Select two small crystals of iodine of the same size (do NOT touch the crystals - iodine stains
skin and clothes), and put one into each of two test-tubes.

b Pour a 2 cm depth of cyclohexane into one test-tube and a 2 cm depth of potassium iodide
solution into the other. Cork the test-tubes and shake until the iodine dissolves. Observe the
different colours formed in the two solvents.

c Take the tube with the cyclohexane solution, and add an equal volume of potassium iodide
solution, without shaking.

d Take the tube with the potassium iodide solution, and add an equal volume of cyclohexane,
without shaking.

e Watch for colour developing in the newly added solvent in each tube.

f Cork both tubes and shake them gently, watching for changes in colour intensity in each
tube.

g Finally shake both tubes vigorously for 15 seconds, allow the two layers to settle out, then
compare the colours in each solvent between both tubes. The situation you should have
achieved is called an equilibrium.

h Use a dropping pipette to remove the bottom layer (coloured potassium iodide solution)
from one test-tube, then add the same volume of fresh potassium iodide solution to the
cyclohexane layer and shake.

i Repeat the removal of the coloured potassium iodide solution and addition of fresh
potassium iodide solution two or three times. What happens to the amount of iodine left in
the cyclohexane layer?

j At the end of the experiment, pour the residues from both tubes into the waste container
provided – do NOT pour down the sink.

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 The distribution of ammonia or iodine between two immiscible solvents

Teaching notes

The solubility of iodine in organic solvents such as cyclohexane produces a purple solution,
similar in colour to iodine vapour, in which non-polar iodine molecules have simply been
separated from each other in the original crystal structure by non-polar solvent molecules.

Iodine is only slightly soluble in water. Its solubility in aqueous potassium iodide, to form a
yellow-brown solution is due to the formation of a stable tri-iodide ion, I3−. The tri-iodide
anion dissociates back to iodine molecules and iodide ions, resulting in the equilibrium:

I2(aq) + I−(aq) ⇌ I3−(aq)

The important point for students in this experiment is that they grasp the idea that iodine
molecules can move between the two solvents, eventually producing an equilibrium which
is the same no matter which direction it is approached from, as achieved in step h above.

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 The distribution of ammonia or iodine between two immiscible solvents

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, the 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
dilute solutions, and the solute must be in the same chemical form in both solvents. It must
not react, or ionise or associate (join together in dimers, for example).

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Partition coefficient calculations

A note on units

Notice that the partition coefficient is a simple ratio of two concentrations. It does not 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.

The square brackets can only be used for concentration in mol dm-3.

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:

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:

Work out the concentrations in ether and in water as actual numbers before you put them
into the expression.

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Partition coefficients like this do not have units - the units cancel out because they are the
same top and bottom.

Calculations involving partition coefficients

A basic example

Use the same case as before - the same solvents, the same X and the same partition
coefficient which was just calculated.

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.

Work out the mass of X extracted = m.

Work out an expression for the concentration of the solution of X in ether.

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

There will be (1.00 - m) g of X left in the water.

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

Put all this into the partition coefficient expression. The calculated the partition coefficient
of X between ether and water as 40.

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In the original calculation to find the partition coefficient, 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, you would extract 0.67 g of X.

That would leave 0.33 g of X behind in the 100 cm3 of water. This solution is kept, 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?

The mass of X extracted by the second lot of ether n.

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

There will be (0.33 - n) g of X left in the water after the second extraction.

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

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.

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.
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Question

Ammonia is soluble in both water and organic solvents.

An aqueous solution of ammonia is shaken with the immiscible organic solvent trichloromethane. The mixture
is left to reach equilibrium.

Samples are taken from each layer and titrated with dilute hydrochloric acid.

A 25.0 cm3 sample from the trichloromethane layer requires 13.0 cm3 of 0.100 mol dm–3 HCl to reach the end-
point.

A 10.0 cm3 sample from the aqueous layer requires 12.5 cm3 of 0.100 mol dm–3 HCl to reach the end-point.

Calculate the partition coefficient, Kpc, of ammonia between trichloromethane and water. Show your working.

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