1

Solubility


alt
Solubility II
 Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

7 Equilibria
This topic illustrates that many chemical reactions are reversible and involve an equilibrium process.
The consideration of the many factors that can affect an equilibrium is an important aspect of physical
chemistry.

alt
Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

Learning outcomes
Candidates should be able to:

7.1 Ionic
7.2 Chemical equilibria:
equilibria a) show
a) explain, in terms of rates
understanding of the
of, and use,forward and reverse reactions,
the Brønsted-Lowry theory of what
acids is
reversible reactions; meant by a reversible reaction and dynamic equilibrium
and bases, including the use of the acid-I base-I, acid-II base-II concept
dynamic equilibrium b) state Lequalitatively
Chatelier’s the
principle and apply it to deduce qualitatively
b) explain differences in behaviour between strong and
(from appropriate information) the effects of changes
weak acids and bases and the pH values of their aqueous in temperature,
solutions in
concentration
terms or pressure
of the extent on a system at equilibrium
of dissociation
c) explain
c) state whether changes
the terms pH, Kin ,temperature, concentration or pressure or the
a pKa and Kw and use them in calculations
presence of a catalyst affect the value of the equilibrium constant for a
d) calculate [H+(aq)] and pH values for strong and weak acids and
reaction
strong bases
d) deduce expressions for equilibrium constants in terms of concentrations,
e) explain the choice of suitable indicators for acid-base titrations,
Kc , and partial pressures, Kp (treatment of the relationship between Kp
given appropriate data
and Kc is not required)
f) describe the changes in pH during acid-base titrations and explain
e) calculate the values of equilibrium constants in terms of concentrations
these changes in terms of the strengths of the acids and bases
or partial pressures from appropriate data
g) (i) explain how buffer solutions control pH
f) calculate the quantities present at equilibrium, given appropriate data
(ii)
(suchdescribe and explain
calculations the uses
will not require theofsolving
buffer of
solutions,
quadraticincluding
equations)the
–
role of HCO3 in controlling pH in blood
g) describe and explain the conditions used in the Haber process and the
h) calculate the pH as
Contact process, of examples
buffer solutions, given appropriate
of the importance data
of an understanding of
i) show
chemicalunderstanding
equilibrium inof,
theand use, the
chemical concept of solubility product,
industry
Ksp
j) calculate Ksp from concentrations and vice versa
k) show understanding of the common ion effect

7.3 Partition coefficients a) state what is meant by partition coefficient; calculate and use a
partition coefficient for a system in which the solute is in the same
molecular state in the two solvents

Back to contents page www.cie.org.uk/alevel 25

 increases with temperature. It also shows why two different liquids
do not have the same boiling point. As a‘Dynamic’
liquidisisa key heated, itsunderstanding
vapour of what is

Saturated vapo
A B word in our
pressure1 atmincreases. When the temperature happeningof the liquid isequilibria.
in liquid–vapour raisedIt to implies continuous
activity and helps explain many everyday phenomena relating to
the point at which the vapour pressuretheequals behaviour the external
of liquids, including pressure,
the variation of boiling point
3 occur throughout thewith

Saturated vapour pressure

1
vaporization can atmospheric pressure.
liquid. Thus, bubbles of
Figure 17.3 shows how the saturated vapour pressure of a liquid
vapour form in the liquid and rise to the surface.
increases Since Itvaporization
with temperature. also shows why two different liquids
do not have the same boiling point. As a liquid is heated, its vapour
no longer occurs only at the surface, itpressure can proceed
increases. When very rapidly.ofThis
the temperature the liquid is raised to
the point at which the vapour pressure equals the external pressure,
T
7. 1 Iodine, water and hexane
Temperature A T B situation we call ‘boiling’; the temperature at which it occurs is the
vaporization can occur throughout the liquid. Thus, bubbles of
‘boiling point’. If the container is not sealed, vapour formthen theand
in the liquid liquid will
rise to the boilSince vaporization
surface.
Whenvapour
■ Figure 17.3 Saturated a small quantity
pressure of iodine iswhen
curves shaken its with
vapour a mixture
pressure T is equal T to that
no longer occurs only at the surface, it can proceed very rapidly. This
of
situation the
we atmosphere.
call ‘boiling’; the temperature at which it occurs is the
Temperature A B
for two liquids A and of B,
water
whereand hexane, some iodine willLiquid
A (e.g. ethanol, dissolve A17.3isinSaturated
bothvapour
more volatile thancurves B. We can see on the graph that, at
‘boiling point’. If the container is not sealed, then the liquid will boil

alt
22 ■ Figure pressure
Quantitative equilibria when its vapour pressure is equal to that of the atmosphere.
liquids.than
b.p. 78 °C) is more volatile The Bwater and hexane doany
(e.g. water, not temperature,
mixfor and areA and
two liquids said
liquid toAA (e.g. ethanol,
B, where
(ethanol, for instance)
Liquid A is more has a
volatile higher
than B. Wevapourcan see on the graph that, at
b.p. 78 °C) is more volatile than B (e.g. water, any temperature, liquid A (ethanol, for instance) has a higher vapour
b.p. 100 °C) be a pair of immiscible liquids. pressureb.p. 100
Figure 22.4 Iodine partitioned between

than °C) liquid B (say, water). Consequently,

water and hexane
pressure than liquidliquid A boils
B (say, water). at a liquid A boils at a
Consequently,
lower temperature than liquid B (Figure 17.3). So,lower at 1 atmosphere, ethanol boils at 78 °C, while
temperature than liquid B (Figure 17.3). So, at 1 atmosphere, ethanol boils at 78 °C, while
water boils at 100 °C.
water boils at 100 °C. Looking more closely at these curves it is possible to see why water, for instance, boils at a
lower temperature at a higher altitude. In Denver, Colorado – the mile-high city – water boils
Looking more closely at these curves it is possible at 95 °C, whileto see why
it would boilwater,
at 69 °C onforthe instance,
summit of Everest. boilsAs weat a
rise above sea level,
lower temperature at a higher altitude. In Denver, Colorado – the mile-high city – water boils
atmospheric pressure is reduced. As water is heated at altitude, its vapour pressure reaches
equality with this reduced atmospheric pressure at a lower temperature. And so the water boils
at 95 °C, while it would boil at 69 °C on the summit of Everest. As we rise above sea level,
at this lower temperature.
586 17 Equilibrium atmospheric pressure is reduced. As water is heated at altitude, its vapour pressure reaches
Partitioning When some iodine crystals are shaken with a mixture of hexane and water until no
further change takes place, and the two layers allowed to separate (see Figure 22.4),
When a small quantity of iodine is shaken with a mixture of water and hexane (Figure 17.4),
equality with this reduced atmospheric pressure at aiodine lower temperature.
in both liquids.And soandthe water do notboils
we find that the ratio of the concentrations of iodine in each layer is a constant.
■ Figure 17.4 Iodine This is true if we use only a small amount of iodine, or a much larger amount. This
some will dissolve The water
constant is the equilibrium constant for the change: hexane mix and are said to
‘Dynamic’ is a key word in our
If theunderstanding of what
into two is
dissolved in a mixture
at this lower temperature.
A B of hexane (upper
be a pair of immiscible
I2(aq) liquids.
I2(hexane) mixture is allowed to separate layers and left
until equilibrium is established (Figure 17.5), the iodine concentration in each layer can be
[I2 (hexane)]

happening in liquid–vapour equilibria. It implies continuous

K=

7. 2 iodine, water and hexane layer) and water [I2 (aq)]

determined by titration with sodium thiosulfate (see Chapter 9).
1 atm Partitioning
K is the partition coefficient of iodine between hexane and water. An alternative
(lower layer)
activity and helps explain many everyday phenomena relating to
phrase is distribution coefficient. Like all equilibrium constants, the value of a
partition coefficient changes with temperature.
I2 (aq) ! I2 (hexane)
If the mixture
When aissmallallowed to separate intoistwo layers anda of
It is important always to write an equation alongside a value of a partition

quantity of iodine shaken

the behaviourwith mixture of water
Experiments using different masses ofthe
liquids, including and hexane
iodine,variation
(Figureof17.4),
coefficient. Following the usual equilibrium constant expression:

water and hexane boiling

show point
that at a fixed temperature
■ Figure 17.4 Iodine [products]

left until equilibrium is established, we find thatatmospheric

the
Theratio
Saturated vapour pressure

K=

some iodine will dissolve in both liquids.

with water the ratioandpressure.
of the hexane do not
concentrations
[reactants]
mix inand
of the iodine the twoarelayers
said to
is constant:
dissolved in a mixture
we need to know which solution is the ‘product’ and which is the ‘reactant’. There is

of the concentrations
be a pair of immiscibleof iodineliquids.
in eachIf layer is a 17.3
the mixture is allowed toKseparate into two layerspressure
and leftof a liquid
no universally accepted convention, but usually the organic solution is the ‘product’
concentration of iodine in water
of hexane (upper
Figure shows how the saturated
on the right-hand side.
D= vapour
concentration of iodine in hexane
The equilibrium is a dynamic one: iodine molecules are constantly crossing the

constant.
equilibrium is established (Figure
until increases 17.5),with the iodine
temperature. concentration It also in each
shows why layer
two can be liquids
different
interface between the two solvents. Equilibrium is established when the rates of these
two processes are equal:
layer) and water The constant KD is called the partition coefficient or distribution coefficient for
rate of leaving aqueous layer = k1[I2(aq)]

determined by titration with sodium do thiosulfate

not have the(seesame Chaptertheboiling 9). point. As a liquid
solvents atis heated, its vapour
Figure 22.5 At equilibrium, the rates at
rate of leaving hexane = k2[I2(hexane)]
which I2 leaves each layer are equal.
solute distributed between two a given temperature. The partition or
(lower layer) (k1 and k2 are rate constants).

distribution law states that at a fixed temperature a solute distributes itself between
At equilibrium,

pressure
I
increases. hexane
When two immiscible solvents so that the ratio of the concentrations of solute to
the temperature
k1[I2(aq)] = k2[I2(hexane)]2 of the liquid is raised in each layer
I2 (aq) ! I2 (hexane)
[X(in S)] solvent S

the point at which the vapour pressure equals the external pressure,
[ I2 (hexane)] k1
is constant.
[ I2 (aq)]
=
k2
=K

Paper chromatography and other chromatographic techniques (see Chapter

Notice that partition coefficients do not usually have units.

Experiments using different massesvaporization canwater occur throughout theof partitioning.

liquid. Thus, bubbles ofseparation
I water

of iodine, water and21) hexane show that at a fixed temperature

The technique of solvent extraction2 depends on partition. This is used when
[X(aq)]
depend on the principle It is also the basis for the
an organic compound is extracted from an aqueous solution by an organic solvent,
technique of solvent extraction (see Chapter 20). We also need to know particular
vapour form in the liquid and rise to the surface. Since vaporization
which is immiscible with water. Examples would be if the aqueous solution contained

the ratio of the concentrations of the iodine in the twopartition layerscoefficients

is constant:
a perfume component or a pharmaceutical extracted from a plant, or contained the
when developing pesticides and insecticides. Pesticides and
■no longer occurs
molecules only at theneed surface, it can
in the proceed
fatty tissues ofvery rapidly.
that theyThis
22_05 Cam/Chem AS&A2
Figure
Barking Dog Art
17.5 Iodine insecticides to be soluble the animals are

T concentration
T ofequilibrium
iodine
between the two layers – a
situation we in
call water‘boiling’;
designed to kill, but much less soluble in water so that the chemicals are not simply
washed the
away by temperature
rain. at which it occurs
377
is the
Temperature A KD = B dynamic is set up

concentration of iodine
‘boiling in hexane
point’.
181333_22_A_Chem_BP_367-380.indd 377
If the container is not sealed, then the liquid will boil 14/10/14 1:52 PM

■ Figure 17.37. 3Saturated

iodine, vapour
water pressure curves
and hexane when its vapour pressure is equal to that of the atmosphere.
for two liquids A and B, where The constant KD is called the
A (e.g. ethanol, Liquid partition
A is more coefficient volatileorthan distribution
B. We can coefficient
see on the for graph that, at
The equilibrium is a
the dynamic
solute
b.p. 78 °C) is more volatile than B (e.g. water, one: iodine
distributed molecules
between two are
solvents at a given temperature. The partition or vapour
any temperature, liquid A (ethanol, for instance) has a higher
I2 b.p. 100 °C)
constantly
hexane
crossing the interface
distribution law between
states that theat two
a fixed temperature a solute
pressure than liquid B (say, water). Consequently, liquid A boils at a distributes itself between
solvents. Equilibrium two immiscible
is established solvents
when so
thethat
Brates theofratio ofSo, theatconcentrations
1 atmosphere,ofethanol solute in each layer
829055_17_IB_Chemistry_585-605.indd 586 18/05/15 10:5

lower temperature than liquid (Figure 17.3). boils at 78 °C, while

these two processes is constant.
are equal:
water boils at 100 °C.

Paper more
Looking chromatography
closely and other
at these curveschromatographic
it is possible to see techniques
why water, (seefor Chapter
instance, boils at a
I2 rate of water
leaving aqueous layeron= rate of leaving hexane

21) depend the principle of partitioning. It is

lower temperature at a higher altitude. In Denver, Colorado – the mile-high city – water boils also the basis for the separation
technique
at 95 °C, whileofitsolvent
would extraction
boil at 69 °C (seeonChapter
the summit 20). We also need
of Everest. Astowe know rise particular
above sea level,
partition coefficients when developing pesticides
atmospheric pressure is reduced. As water is heated at altitude, its vapour pressure and insecticides. Pesticides and reaches
■ Figure 17.5 Iodine molecules insecticides need to be soluble in the fatty tissues
equality with this reduced atmospheric pressure at a lower temperature. And so the water boils of the animals that they are
between the two layers – a designed
at this to kill, but much less soluble in water so that the chemicals are not simply
lower temperature.
dynamic equilibrium is set up washed away by rain.
Partitioning
■ Figure 17.4 Iodine
7. 4 iodine,When
watera and
smallhexane
quantity of iodine is shaken with a mixture of water and hexane (Figure 17.4),
some iodine will dissolve in both liquids. The water and hexane do not mix and are said to
dissolved inThis
a mixture
is true if we
be use only
a pair of a small amount
immiscible of iodine,
liquids. or a
If the mixture is allowed to separate into two layers and left
of hexane (upper
much larger amount. This constant is the equilibrium
until equilibrium is established (Figure 17.5), the iodine concentration in each layer can be
layer) and water
constant for the change:
by titration with sodium thiosulfate (see Chapter 9).
determined
(lower layer)
I2 (aq) ! I2 (hexane)
55_17_IB_Chemistry_585-605.indd 586 18/05/15 10:50 am

Experiments [Iusing different masses of iodine, water and hexane show that at a fixed temperature
2] hexane
Kpartition =
the ratio of the
[I2]concentrations
aqueous of the iodine in the two layers is constant:
concentration of iodine in water
KD =
concentration of iodine in hexane

The constant KD is called the partition coefficient or distribution coefficient for

the solute distributed between two solvents at a given temperature. The partition or
I2 hexane distribution law states that at a fixed temperature a solute distributes itself between
two immiscible solvents so that the ratio of the concentrations of solute in each layer
Bilal Hameed is constant. Solubility
Bilal Hameed Marginalizer
Paper chromatography and other chromatographic techniques (see Chapter
I2
water 21) depend on the principle of partitioning. It is also the basis for the separation
technique of solvent extraction (see Chapter 20). We also need to know particular
 4 2
22 Quantitativ

7. 5 iodine, water and

Figure 22.4 hexane
Iodine partitioned between
water and hexane
Kpc is the partition coefficient of iodine between hexane
and water.

alt
Like all equilibrium constants, the value of a partition
coefficient changes with temperature.

[I2] hexane
Kpartition =
[I2] aqueous

When some iodine crystals are shaken with a mixture of hexane and wate
further change takes place, and the two layers allowed to separate (see F
7. 6 iodine, water and hexane we find that the ratio of the concentrations of iodine in each layer is a co
This is true if we use only a small amount of iodine, or a much larger am
The equation is always written alongside the valueconstant
of a is the equilibrium constant for the change:
partition coefficient.
I2(aq) I2(hexane)
[I2 (hexane)]
There is no universally accepted convention, but usually
K=
[I2 (aq)]
the organic solution is the ‘product’ on the right-hand
K is the partition coefficient of iodine between hexane and water. An a
side.
phrase is distribution coefficient. Like all equilibrium constants, the val
partition coefficient changes with temperature.
It is important always to write an equation alongside a value of a partit
Partition coefficients do not have units.
 coefficient. Following the usual equilibrium constant expression:
[products]
K=
[reactants]
we need to know which solution is the ‘product’ and which is the ‘reacta
22 Quantitative equilibria
no universally accepted convention, but usually the organic solution is th
on the right-hand side.
Figure 22.4 Iodine partitioned between The equilibrium is a dynamic one: iodine molecules are constantly cros
7. 7 Partition coefficient
water and hexane
interface between the two solvents. Equilibrium is established when the r
two processes are equal:
Partition: The distribution of a dissolved substance rate of leaving aqueous layer = k1[I2(aq)]
Figure 22.5 At equilibrium, the rates at
between two solvents rate of leaving hexane = k2[I2(hexane)]
which which dolayer
I2 leaves each notaremix
equal.(they are
(k1 and k2 are rate constants).
immiscible).
At equilibrium,

[X(in S)] solvent S k1[I2(aq)] = k2[I2(hexane)]

[ I2 (hexane)] k1
= =K
[ I2 (aq)] k2
When some iodine crystals are shaken with a mixture of hexane and water until no
further change takes place, and the two layers allowedNotice that
to separate (see partition
Figure 22.4), coefficients do not usually have units.
we find that the ratio of the concentrations of iodine in each layer is a constant.
water The technique of solvent extraction depends on partition. This is use
This is true if we use only a small amount of iodine, or a much larger amount. This
constant is the equilibrium constant for the change: an organic compound is extracted from an aqueous solution by an organi
[X(aq)]
I2(aq) I2(hexane) which is immiscible with water. Examples would be if the aqueous solutio
[I2 (hexane)]
K= a perfume component or a pharmaceutical extracted from a plant, or con
[I2 (aq)]
K is the partition coefficient of iodine between hexane and water. An alternative
22_05 Cam/Chem AS&A2
phrase is distribution coefficient. Like all equilibrium constants, the value of a
partition coefficient changes with temperature.
Barking Dog Art It is important always to write an equation alongside a value of a partition

7. 8 Partition coefficient [products] coefficient. Following the usual equilibrium constant expression:

K=
[reactants]

Shaking a solid with two immisciblewe need to know whichsolvent produces

solution is the ‘product’ an
and which is the ‘reactant’. There is
no universally accepted convention, but usually the organic solution is the ‘product’

equilibrium system to which the equilibrium

on the right-hand side.
The equilibrium
181333_22_A_Chem_BP_367-380.indd
law applies
377 is a dynamic one: iodine molecules are constantly crossing the
at equilibrium. The ratio ofinterfacethe
two concentrations in the two
between the two solvents. Equilibrium is established when the rates of these
processes are equal:
rate of leaving aqueous layer = k [I (aq)]
layers is constant, at a givenratetemperature:
Figure 22.5 At equilibrium, the rates at
of leaving hexane = k [I (hexane)]
which I2 leaves each layer are equal. 2 2
1 2

(k1 and k2 are rate constants).

At equilibrium,

[X(in S)] solvent S k1[I2(aq)] = k2[I2(hexane)]

[ I2 (hexane)] [X]
k1
= K organic solvent S
Kpartition =
=
[ I (aq)]
2 k2

water
[X] aqueous
Notice that partition coefficients do not usually have units.
The technique of solvent extraction depends on partition. This is used when
an organic compound is extracted from an aqueous solution by an organic solvent,
[X(aq)]
which is immiscible with water. Examples would be if the aqueous solution contained
a perfume component or a pharmaceutical extracted from a plant, or contained the

22_05 Cam/Chem AS&A2

Barking Dog Art

377

181333_22_A_Chem_BP_367-380.indd 377 14/10/14 1:52 PM

Solubility Marginalizer Bilal

Bilal Hameed
Hameed
 3 5

7. 9 Partition coefficient
Partition coefficient is the ratio of concentration of a
solute in two immiscible layers at a particular temperature

alt
at equilibrium.

The partition obeys the equilibrium law only so long as

the dissolved chemical has the same molecular structure
on both solvents.

7. 10 Skill check
A solution of 5.00 g of an organic compound X in 50 cm3
of water was shaken with 100 cm3 of ether. After
separation, the aqueous solution was found to contain
0.80 g of X. Determine the partition coefficient of x
between ether and water.

7. 11 Skill check
When 100 cm3 of an aqueous solution containing 2.0 g of
organic dye X was shaken with 20 cm3 of hexane, it was
found that 1.6 g of the dye had been extracted into the
hexane.

(a) Calculate the partition coefficient of X between hexane

and water.

7. 12 Skill check
(b) Calculate the minimum volume of hexane needed to
reduce the amount of X in the aqueous layer to less than
0.1 g.

Bilal Hameed
Bilal Hameed Marginalizer Solubility
 6 4

7. 13 Skill check
When 40.0 cm3 of hexane was shaken with 10.0 cm3 of a
solution containing 0.25 g of Q in 10.0 cm3 of methanol, it

alt
was found that 0.060 g of Q was extracted into the
hexane.

Calculate the partition coefficient, Kpartition, of Q between

hexane and methanol.

7. 14 Solvent extraction
The technique of solvent extraction depends on partition.
This is used when an organic compound is extracted
from an aqueous solution by an organic solvent, which is
immiscible with water.

If we know the value of the partition coefficient for the

compound, we can calculate how much would be
extracted into the organic layer. Octan-1-ol is often used
as the organic solvent.
PHYSICAL CHEMISTRY

7. 15 Skillproduct
check formed during a synthetic reaction carried out in a laboratory. If we know
the value of the partition coefficient for the compound, we can calculate how much
The partitionwould
coefficient for the
be extracted into distribution of cyclohexanone
the organic layer.
between water and octanol
Industrially, is 24.
octan-1-ol Calculate
is often used asthe
the mass
organicof
solvent.
cyclohexanone that would be extracted if 20 cm of octanol 3
Worked example
was shaken with 100 cm3 of an aqueous solution containing
The partition coefficient for the distribution of cyclohexanone between water and
2.5g of cyclohexanone.
octanol is 24.
O O
(aq) (in octanol) K = 24

cyclohexanone
Calculate the mass of cyclohexanone that would be extracted if 20 cm3 of octanol was
shaken with 100 cm3 of an aqueous solution containing 2.5 g of cyclohexanone.

Answer
Let [X] be the concentration of cyclohexanone expressed in g cm –3; let the mass of
cyclohexanone extracted be x g; the mass remaining in the aqueous layer will therefore be
(2.5 − x) g
7. 16 Successive K=
extractions
[X(octanol)]
[X(aq)]
Solvents are [X(octanol)]
often expensive
= [X(aq)] × Kand flammable, and can
also be polluting to xthe  2.5 − x 
=  environment.
=  × 24

20  100 
5x = (2.5 − x) × 24
It is sensible, therefore, to use the minimum amount of
5x = 60 − 24x
solvent that is needed x = 2.07achieve
to g the intended goal.
This process has extracted about 83% of the 2.5 g of cyclohexanone that was in the water.
If we wanted to extract more cyclohexanone, we could repeat the process. But this
would require another 20 cm3 of octanol. However, if we were to split the original 20 cm3 of
octanol into two 10 cm3 portions, and use these for successive extractions, our yield of
extracted material would increase. The following calculations will make this clear.
1 Let the mass of cyclohexanone extracted by the first 10 cm3 portion of octanol be y g. The
mass remaining in the water will therefore be (2.5 – y) g
y  2.5 − y 
= × 24
10  100 
10y = (2.5 − y) × 24
10y = 60 − 24y
y = 1.765 g
This first extraction results in 2.5 − 1.765 = 0.735 g of cyclohexanone remaining in the
aqueous layer.
Solubility Marginalizer 2 We can now calculate how much of this remaining cyclohexanone can be extracted
Bilal Hameed
Bilal Hameed
by
using the second 10 cm3 portion of octanol.
Let the mass of cyclohexanone extracted by the second 10 cm3 portion of octanol be
z g. The mass remaining in the water will be (0.735 – z) g.
z  0.735 − z 
 5 7

7. 17 Successive extractions
In an earlier skill check a solution of 5.00 g of an organic
compound X in 50 cm3 of water was shaken with 100

alt
cm3 of ether. After separation, the aqueous solution was
found to contain 0.80 g of X.

The use of 20 cm3 of hexane allowed 1.6 g of the dye X

to be extracted from its aqueous solution, i.e. (1.6/2.0) x
100 = 80%.

A Level Science Applications Support Booklet: Chemistry

Example 1:
7. 18 Successive extractions
Question: We can extract more (89%) than this if we use two
When 100 cm3 of an aqueous solution containing 2.0 g of the organic dye X was shaken with 20 cm3 of
separate 10 cm3 portions of hexane, rather than one 20
hexane, it was found that 1.6 g of the dye had been extracted into the hexane.
cm3 portion.
(i) Calculate the partition

coefficient of X between hexane and water.

(ii) Calculate the minimum volume of hexane needed to reduce the amount of X in the aqueous layer
to less than 0.1 g.

Answer:
(i) If 1.6 g of X had been extracted by the hexane, 0.4 g must have been left in the aqueous layer.
The two concentrations are therefore:
In the hexane layer: 1.6/20 = 0.08 g cm–3. In the water layer: 0.4/100 = 0.004 g cm–3
Kpc = [X(hexane)]/[X(aq)] = 0.08/0.004 = 20
(ii) If the mass left in the aqueous layer is to be less than 0.1 g, then the mass extracted must be at
least 1.9 g. The corresponding concentrations are as follows:
in the hexane layer: 1.9/v g cm–3 in the water layer: 0.1/100 = 0.001 g cm–3
7. 19 1st
(where v = volume extraction
of hexane needed)
Kpc = [X(hexane)]/[X(aq)]
20 Let=us assume that x grams of X have been extracted by
(1.9/v)/0.001
v the=first 10 cm 3. The equilibrium 3concentrations will
1.9/(20 × 0.001) = 95 cm
therefore be:

Successive extractions
in the hexane layer: x/10 g cm—3

Solvents are often expensive and flammable, and can also be polluting to the environment. It is
sensible, therefore,intothe
use the layer:
water minimum(2.0 amount
– x)/100ofg solvent
cm—3 that is needed to achieve the intended
goal. Thus in the example above, the use of 20 cm3 of hexane allowed 1.6 g of the dye X to be
extracted from its aqueous solution, i.e. (1.6/2.0) × 100 = 80%.
We can extract more than this if we use two separate 10 cm3 portions of hexane, rather than one 20
cm3 portion. The following calculation will make this clear.
Example 2:
1st extraction: Let us assume that x grams of X have been extracted by the first 10 cm3. The
7. 20 1st
equilibrium concentrations extraction
will therefore be:
in the hexane layer: x/10 g cm–3 in the water layer: (2.0 – x)/100 g cm–3
x / 10
K sp = 20
(2.0 x ) / 100
x/10 = (40 – 20x)/100
100x = 10(40 – 20x)
100x = 400 – 200x
x = 1.33 g
Thus the amount extracted = 1.33 g, so the amount remaining in the aqueous layer = 0.67 g
Thus the amount extracted = 1.33 g, so the amount
2nd extraction: We now
remaining in the
separate 10 cm3 oflayer
theaqueous hexane= 0.67 g
solution of X from the aqueous layer, and add
another 10 cm3 of hexane and shake again. Let us assume that the second 10 cm3 will extract y
grams of X, the equilibrium concentrations will be:
in the hexane layer: y/10 g cm–3 in the water layer: (0.67 – x)/100 g cm–3
y / 10
K sp = 20
(0.67 y ) / 100
By a calculation similar to the one shown above, we find that
y = 0.44 g
The total amount of X extracted by two successive 10 cm3 portions of hexane is therefore
Bilal
1.33 + 0.44 Hameed
= 1.77 This represents 89% of the original 2.0 g amount of X in the 100 cm3Marginalizer
Bilalg.Hameed of water. Solubility
 pc
20 = (1.9/v)/0.001
v = 1.9/(20 × 0.001) = 95 cm3

Successive extractions
8
Solvents are often expensive and flammable, and can also6be polluting to the environment. It is
sensible, therefore, to use the minimum amount of solvent that is needed to achieve the intended
goal. Thus in the example above, the use of 20 cm3 of hexane allowed 1.6 g of the dye X to be
extracted from its aqueous solution, i.e. (1.6/2.0) × 100 = 80%.
7. 21
We can extract more than2nd
this ifextraction
we use two separate 10 cm3 portions of hexane, rather than one 20
cm3 portion. The following calculation will make this clear.
We now separate the 10 cm of hexane solution of X
3
Example 2: from the aqueous layer, and add another 10 cm3 of

alt
1st extraction: Lethexane
us assumeandthat x grams
shake of X Let
again. haveusbeen extracted
assume thatbythe first 10 cm3. The
thesecond
equilibrium concentrations will therefore be:
10 cm
in the hexane layer: x/10will
3
g cmextract
–3 yingrams of layer:
the water X, the(2.0
equilibrium
– x)/100 g cm–3
concentrations will K
be:
x / 10 = 20
sp
(2.0 x ) / 100
in the hexane x/10
layer:= y/10 g cm—3

(40 – 20x)/100
100x = 10(40 – 20x)
in the water layer:
100x (0.67
= 400 –– y)/100
200x g cm
—3

x = 1.33 g
Thus the amount extracted = 1.33 g, so the amount remaining in the aqueous layer = 0.67 g

2nd extraction: We now separate the 10 cm3 of hexane solution of X from the aqueous layer, and add
another 10 cm3 of hexane and shake again. Let us assume that the second 10 cm3 will extract y
7. 22 2nd
grams of X, the equilibrium extraction
concentrations will be:
in the hexane layer: y/10 g cm–3 in the water layer: (0.67 – x)/100 g cm–3

 K sp
y / 10
= 20
(0.67 y ) / 100
By a calculation similar to the one shown above, we find that
With the above calculation, y = we0.44find
g that y = 0.44g

The total amount of X extracted by two successive 10 cm3 portions of hexane is therefore
1.33 + 0.44 = 1.77 g. This represents 89% of the original 2.0 g amount of X in the 100 cm3 of water.
The total amount of X extracted by two successive 10
cm3 portions of hexane is therefore 1.33 + 0.44 = 1.77 g.

This is 89% of the original 2.0 g amount of X in the 100

88
cm3 of water.
© University of Cambridge International Examinations 2010

PHYSICAL CHEMISTRY

7. 23 Skill check
product formed during a synthetic reaction carried out in a laboratory. If we know
the value of the partition coefficient for the compound, we can calculate how much
When 20 would
cm3 ofbeoctanol
extracted is shaken
into withlayer.
the organic 100 cm3 of an
aqueous solution containing
Industrially, octan-1-ol2.5g of used
is often cyclohexanone,
as the organic solvent.
2.07g of cyclohexanone is extracted. What mass of
Worked
cyclohexanone example
would be extracted if instead we use two
separate 10 cm portions
The 3
partition offor
coefficient octanol. The Kofpartition
the distribution is 24. between water and
cyclohexanone
octanol is 24.
O O
(aq) (in octanol) K = 24

Calculate the mass of cyclohexanone that would be extracted if 20 cm3 of octanol was
shaken with 100 cm3 of an aqueous solution containing 2.5 g of cyclohexanone.

Answer
Let [X] be the concentration of cyclohexanone expressed in g cm –3; let the mass of
cyclohexanone extracted be x g; the mass remaining in the aqueous layer will therefore be
7. 24 Skill
(2.5 check
− x) g
[X(octanol)]
K=
The partition coefficient of X between ethoxyethane and
[X(aq)]
water is 40.0. A solution
[X(octanol)] contains
= [X(aq)] ×K 4.00 g of X dissolved in
0.500 dm3 of water.  2.5 − x  the mass of X that can be
x Calculate
=
=  × 24
20  100 
extracted from this5xaqueous solution by shaking it with

= (2.5 − x) × 24
5x = 60 − 24x
(a) 0.050 dm3 of ethoxyethane.

x = 2.07 g
This process has extracted about 83% of the 2.5 g of cyclohexanone that was in the water.
(b) two successive
If we wantedportions
to extractofmore
0.025 dm3 of we could repeat the process. But this
cyclohexanone,
ethoxyethane.
would require another 20 cm 3
of octanol. However, if we were to split the original 20 cm3 of
octanol into two 10 cm3 portions, and use these for successive extractions, our yield of
extracted material would increase. The following calculations will make this clear.
1 Let the mass of cyclohexanone extracted by the first 10 cm3 portion of octanol be y g. The
mass remaining in the water will therefore be (2.5 – y) g
y  2.5 − y 
= × 24
10  100 
10y = (2.5 − y) × 24
10y = 60 − 24y
y = 1.765 g
Solubility Marginalizer Bilal
Bilal
This first extraction results in 2.5 − 1.765 = 0.735 g of cyclohexanone remaining
Hameed
inHameed
the
aqueous layer.
2 We can now calculate how much of this remaining cyclohexanone can be extracted by
using the second 10 cm3 portion of octanol.
3