EQUILIBRI

A
Outline:
1. Conjugate acid – base pairs (New to A
Level)
2. Ionic product of water
3. pH calculations (for strong acids and
bases)
4. The concept of weak acids and pH
calculations
5. Indicators (AS Level)
6. Buffer solutions
7. Equilibrium and solubility
1. Conjugate acid – base
pairs
 Acid – base concepts
 Arrhenius concept – H+ and OH- ions in solution
 Lewis concept - electron transfer
 Bronsted-Lowry concept – H+ (proton) transfer
 Identify conjugate acid – base pairs
 A conjugate acid is an acid formed when a
base accepts a proton; and
 A conjugate base is a base formed after an
acid has lost a proton.
 A conjugate pair is formed when a reactant is
linked to a product by the transfer of a proton
Question.
 Identify the conjugate acid – base pairs in the
following equations:
(a) HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

(b) NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

(c) HClO4 + CH3COOHCH3COOH2+ + ClO4-

(d) HCl + HI H2Cl+ + I-

(e) HCOOH + HClO2 ClO2- + HCOOH2+

2. Ionic Product of
Water, Kw.
 Water is a very weak electrolyte. It
dissociates partially to establish an
equilibrium as shown:

H2O(l) H+(aq) + OH-(aq)

Or
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

 Applying equilibrium
  law
[ H (aq )][OH (aq )] to the system we
K 
get;
c
[ H O(l )]
2
Cont…
 The [H2O(l)] is constant and combining it
with the constant Kc we get:

Kw = [H+][OH-]

 This new equilibrium constant, Kw, is called

ionic product of water.
Cont…
 Ionic product of water, Kw, is the product
of the concentrations of the ions of
water, i.e. H+ and OH-

 The value of Kw at 298K is 1.00 x 10-14

mol2dm-6
 pH of water
 pH is defined as the negative logarithm
to the base 10 of the hydrogen ion
concentration.
i.e. pH = -log10[H+]
 For water, Kw = [H+][OH-]
 But, for pure water, [H+] = [OH-]
 Thus, Kw = [H+]2
[H+] = √Kw = √1.00 x 10-14 = 1.00 x
10-7
 Thus, pH = -log(1.00 x 10-7)
 pKw
 The ionic product of water expression is:
Kw = [H+][OH-]
 Introducing –log10 to this equation we get;
-log Kw = -log[H+] – log[OH-]

 But, -log[H+] = pH; – logKw = pKw, and -log[OH-] = pOH

 Thus, pKw = pH + pOH

 Since Kw = 1.00 x 10-14,

 Hence, 14 = pH + pOH
3. pH calculations.
 pH is defined as the negative logarithm to the
base 10 of the hydrogen ion concentration.
i.e. pH = -log10[H+]
Questions.
1. Calculate the pH of the following
solutions:
(a) [H+] = 3.00 x 10-4 moldm-3
(b) [H+] = 1.00 x 10-2 moldm-3
(c) [H+] = 4.00 x 10-8 moldm-3
(d) [H+] = 5.40 x 10-12 moldm-3
(e) [H+] = 7.80 x 10-10 moldm-3
Cont…
2. Calculate the concentration of hydrogen
ions in solutions having the following
pH values.
(a) pH 2.90
(b) pH 3.70
(c) pH 11.2
(d) pH 5.40
(e) pH 12.9
Calculating pH of strong
bases
Steps:
 Determine [H+] from the expression of ionic
product of water
 Determine the pH

 Remember,
K w [ H  ][OH  ]

 and, Kw
[H  ] 
[OH  ]
 Question.
 Find the pH of the following strong acids and
bases.
(a) 1.00mol.dm-3 HNO3
(b) 0.500 moldm-3 HNO3
(c) an aqueous solution containing 3.00g HCl
per dm3
(d) 0.00100 moldm-3 KOH
(e) an aqueous solution containing 0.200g of
NaOH per dm3
(Use Kw = 1.00 x 10-14 mol2 dm-6)
4. Weak acids and Bases
 Weak acid is an acid that dissociates only
partially in solutions.
Example: all organic acids
 A weak base is one that dissociates only partially

in solutions.
Example: NH4OH, all organic bases
 Weak acids and bases establish equilibrium when
dissolved in water.
e.g.
CH3COOH CH3COO- + H+

NH4OH NH4+ + OH-

Acid dissociation constants,
Ka.
 Weak acids, e.g. ethanoic acid, CH3COOH, when
dissolved in water establish an equilibrium.
CH3COOH(aq) CH3COO-(aq) + H+(aq)
 Equilibrium expression for this reaction is:

Ka 
CH COO H 
3
 

CH 3COOH 
 Ka is called acid dissociation constant.
 The value of Ka indicates the extent of
dissociation of an acid.
 The higher the Ka value, the stronger the acid and
vice versa
Comparing the strength of
acids
 We can use Ka values to compare the
strength of acids.
 The higher the Ka value, the stronger the
acid.
 But as Ka values for many acids are very
small, we also use pKa values to compare
the strength of acids.
 pKa = -log10Ka
 The smaller the pKa value (less positive), the
stronger the acid.
Calculating Ka values for weak acids.

 For a general weak acid HA;

 The equilibrium expression K
is:a 
H A  H 
   2

HA HA
 Thus we can calculate the value of Ka if we
know:
 (i) The concentration of the acid
 (ii) The concentration of H+/A- and or pH
 Assumptions:
 We ignore the [H+] ions produced by the
ionisation of water
 [HA] at equilibrium is equal to that of the original
acid.
Questions.
1. (a) Calculate the value of Ka for the
following acids.
(i) 0.02 mol.dm-3 2-aminobenzoic acid
which has a pH of 4.30
(ii) 0.05mol.dm-3 propanoic acid with a
pH of 3.10
(iii) 0.10mol.dm-3 2-nitrophenol with a
pH of 4.10
(b) Calculate pKa values for each of the
acids in part (a)
Cont…
2. Propanoic acid is a weak acid. A 0.05 mol.dm -3 solution
of propanoic acid has a pH of 3.1. Calculate the value
of Ka for propanoic acid. Show all your working.
3. Use relevant data from Table 21.2, pg. 308,
Chemistry course book, 2nd edition, by Lawrie
Ryan, to work out the pH values of the following
solutions.
(a) 0.02 moldm-3 aqueous benzoic acid
(b) 0.01 moldm-3 hydrated aluminium ions
(c) 0.10 moldm-3 aqueous methanoic acid

4. ESQ pg. 460, qn. 1

5. ESQ, pg. 461, qn. 6
 5. Buffer Solutions.
 A buffer solution is a solution in which the
pH does not change significantly on addition
of small amounts of acids or bases.

 A buffer solution resists change in its pH

when small amounts of acids or bases are
added.

 A buffer solution is made by mixing either a

weak acid and its salt, or a weak base and
its salt. Example:
Types of buffer solutions.

Depending on the substances mixed,

there are two types of buffer solutions:
(i) Acidic buffer: prepared by
mixing a weak acid and its salt.
E.g. CH3COOH & CH3COONa
(ii) Basic buffer: prepared by
mixing a weak base and its salt.
E.g. NH4OH (NH3 aq.) & NH4Cl
Cont…
 Buffer capacity:- the ability of the
buffer solution to resist change in its pH

 Buffer range:- the pH range within

which a buffer solution can resist change
in its pH
Mechanism of buffer
action
(i) Acidic buffer (e.g. ethanoic acid - sodium
ethanoate buffer)
 The equilibrium existing in solution is:
CH3COOH CH3COO- + H+
CH3COONa CH3COO- + Na+
 The buffer solution contains relatively large
amounts of CH3COOH and CH3COO-. i.e. there are
reserve supplies of the acid and its conjugate
base.
 What happens when an acid or base is
added to this buffer solution?
Cont…
(a) When an acid is added
HCl H+ + Cl-
 The addition of H+ ions shifts the position of

equilibrium to the left by combining with CH 3COO-

from CH3COOH.
CH3COO- + H+ CH3COOH
 The large reserve supply of CH3COO- ensures that
the [CH3COO-] in solution does not change
significantly.
 Thus H+ ions added from the acid are all removed
and the pH does not change significantly.
Cont…
(b) When a base is added
NaOH Na+ + OH-
 The added OH- ions combine with H+ to form

water, the position of equilibrium shifts to the

right and CH3COOH ionise to form more H+ ions.
H+ + OH- H2 O
 The large reserve supply of CH3COOH and
CH3COO- ensures that their concentrations in
solution do not change significantly.
 Thus OH- ions added from the base are all
removed and the pH does not change
significantly.
Cont…
(ii) Basic buffer (e.g. aqueous ammonia –
ammonium chloride buffer)
 The equilibrium existing in solution is:

NH4OH NH4+ + OH-

NH4Cl NH4+ + Cl-
 The buffer solution contains relatively large
amounts of NH4OH and NH4+ . i.e. there are reserve
supplies of the weak base and its conjugate acid.
 What happens when an acid or base is added
to this buffer solution?
Cont…
(a) When an acid is added
HCl H+ + Cl-
 The added H+ ions from the acid combine with OH-
to form water, the position of equilibrium shifts to
the right and NH4OH ionise to form more OH- ions.
H+ + OH- H2O
 The large reserve supply of NH4OH and NH4+
ensures that their concentrations in solution do
not change significantly.
 Thus H+ ions added from the acid are all removed
and the pH does not change significantly.
Cont…
(b) When a base is added
NaOH Na+ + OH-
 The addition of OH- ions shifts the position of

equilibrium to the left by combining with NH 4+ from

NH4OH.
NH4+ + OH- NH4OH.
 The large reserve supply of NH4+ and NH4OH
ensures that their concentrations in solution do not
change significantly.
 Thus OH- ions added from the base are all removed
and the pH does not change significantly.
Note:
 The effectiveness of a buffer solution
depends on the relative amounts of acid
and its conjugate base or the amount of a
weak base and its conjugate acid.
 A buffer solution is more effective if
 [Acid]/[salt] = 1
 [Base]/[Salt] = 1
 The buffering capacity of a solution works
best when the pH value is close or
equal to the pKa value.
 CO2 as a buffer
 In unpolluted areas, the rainwater has a
pH of around 5.7.

 CO2 + H2O H2CO3

 H2CO3 H+ + HCO-

 This does not work in highly polluted

areas. Why?
Question.
 A mixture of 0.500 mol.dm-3 aqueous
ammonia and 0.500 mol.dm-3
ammonium chloride acts as a buffer
solution.
(a) explain how this buffer solution
minimises changes in pH on addition
of:
(i) dilute hydrochloric acid
(ii) dilute sodium hydroxide
(b) Explain why dilute aqueous
ammonia alone will not act as a
Calculating pH of a Buffer solution

 Consider an acid buffer

CH3COOH/CH3COONa.
 Dissociation equations are:
CH3COOH CH3COO- + H+
CH3COONa CH3COO- + Na+
 
 From the K [CH COO
equilibrium of][ H
the ] weak acid;
a 
3
[CH 3COOH ]

 [CH 3COOH ]
[ H ] K a .
and [CH 3COO ]
Cont…
 But [CH3COOH] = [Acid] and [CH3COO-]
= [Salt]
 [ Acid
Thus theequation can ]be written as:
[ H ] K a .
[ Salt ]

 Then, -log10[H+] gives us the pH.

 If we introduce –log10 in the above
equation H we get:
Ka  [ Salt ] 
P P  log  
 [ Acid ] 
 Questions.
1. Qn. 9, pg. 450
2. Qn. 10, pg. 450
3. Find the pH of:
(a) a 0.1mol/dm3 ethanoic acid
(b) a mixture of 0.1 moles of ethanoic
acid with 0.5 moles of sodium
ethanoate dissolved in
water to make one litre of
solution. (Ka for ethanoic acid is 1.8 x 10 -
5
)
Question 4
5. A solution composed of 0.2 mol/dm 3
ethanoic acid and 0.02 mol/dm3 sodium
ethanoate gives a pH of 3.75 at 25ºC.
Find the acid dissociation constant, Ka,
of ethanoic acid.
6. Calculate the concentrations of
ethanoic acid and sodium ethanoate
needed to prepare ethanoic acid/sodium
ethanoate buffer solution whose pH is
4.50. (Use Ka value obtained in qn. 5
above)
7. Calculate the change in pH when 1
drop (0.01cm3) of 1.00 mol/dm3 NaOH
is added to 1dm3 of buffer solution
containing 0.1 mol/dm3 ethanoic acid and
0.1 mol/dm3 sodium ethanoate. (Ka for
ethanoic acid = 1.8 x 10-5 ).
8. (a) Explain how an aqueous solution
containing ethanoic acid and sodium
ethanoate resists changes in pH when
contaminated with small amounts of acid or
alkali.
(b) it can be shown that for solutions
described

in part (a) 
[ sodium ethanoate ]
p H  p Ka  log  
 [ethanoic acid ] 

(i) state the significance of the value of

the pH when [sodium ethanoate] =
[ethanoic acid]
(ii) Calculate the mass of sodium
ethanoate which must be dissolved in
1 dm3 of ethanoic acid of
concentration 0.10 moldm-3 to produce a
solution with a pH value of 5.5 at
298K. Assume there is no volume
change on dissolving the salt.
9. ESQ, pg. 460, qn. 2
10. ESQ, pg. 461, qn. 4
Blood as a buffer system
 The pH of the human blood is kept
between 7.35 and 7.45 by a number of
different buffers in the blood.
 hydrogencarbonate ions HCO3-
 haemoglobin and plasma proteins
 dihydrogenphosphate (H2PO4-) and
hydrogenphosphate (HPO42-) ions
Cont…
 The body cells produce CO2 as a product
of respiration.
 CO2 combines with water to form weak
carbonic acid which dissociates partially
to form a solution containing H+ and
HCO3- ions.
 CO2 + H2O H2CO3 H+ + HCO3-
 Too much H+ ions in the body will lower
the blood pH and cause ‘’acidosis’’ which
will affect some body functions
Cont…
 The equilibrium existing in the blood
which helps to control its pH is:
CO2 + H2O H+ + HCO3-
 If the [H+] increases in the blood:
 The position of the above equilibrium shifts
to the left
 H+ ions combine with HCO3- ions to form CO2
 This reduces [H+] in the blood and pH
remains constant
Cont…
 If the [H+] decreases:
 The position of equilibrium shifts to the
right
 CO2 and H2O combine to form H+ and HCO3-
ions until equilibrium is restored
 This increases [H+] in the blood and the pH
is kept constant.

Question.
Qn. 11, pg.452
6. Solubility and solubility
product
Outline.
 Definitions of Solubility and Solubility

product
 Solubility product expressions (Ksp
expressions)
 Calculations of:

 Solubility product (Ksp)

 Solubility.
 Common ion effect
6.1. Solubility.
 Solubility is defined as the number of
grams or number of moles of a
compound needed to saturate 100g or
1kg of water at a given temperature.
 A saturated solution is one in which no
more solute dissolves in it.
 NaCl is regarded as a soluble salt: a
saturated solution contains 36g per 100g of
water.
 PbCl2 is regarded as insoluble salt: a
saturated solution contains 0.99g per 100g
6.2. Solubility product
 An equilibrium is established when an
undissolved (sparingly soluble) ionic
compound is in contact with a saturated
solution of its ions.
Example:
AgCl(s) Ag+(aq) + Cl-(aq)
 Equilibrium expression for this equation is:

 The concentration of a solid phase remains

constant and can be combined with the value
of Kc.
Cont…
 The equilibrium expression then
becomes:
Ksp = [Ag+(aq)] [Cl-(aq)]
 The new constant, Ksp is called
solubility product and its defined as
the product of the concentrations of
each ion in a saturated solution of a
sparingly soluble salt at 298K, raised to
the power of their relative
concentrations.
Cont…
 Generally Ksp expression for a salt CxAy is
given by: Ksp = [Cy+ (aq)]a [Cx-(aq)]b
 Where:
 a is the number of Cy+ cations in one
formula unit of the compound and
 b is the number of Ax- anions in one formula
unit of the compound
6.3. Ksp (equilibrium)
expressions
 Consider the compound Fe2S3(s)
 The equilibrium existing between the salt and
its ions is:
Fe2S3(s) 2Fe3+(aq) + 3S2-(aq)
and the Ksp (equilibrium) expression is:

Ksp = [Fe3+(aq)]2 [S2-(aq)]3

Note:
 The idea of solubility product only applies to

ionic compounds that are slightly(sparingly)

soluble.
Questions.
(a) Write equilibrium expressions for the
solubility products of the following:
(i) Fe(OH)2
(ii) Fe2S3
(iii) Al(OH)3
(b) State the units of solubility products for
each of the compounds in part (a).
6.4. Solubility product
calculations.
(a) Calculating solubility product, Ksp, from
solubility.
Example.
 A saturated solution of magnesium fluoride, MgF ,
2
has a solubility of 1.22 x 10-3 mol.dm-3. Calculate
the solubility product of magnesium fluoride.
Step 1: Write the equilibrium equation.
Step 2: Calculate the concentration of each ion in
solution.
Step 3: Write down the Ksp/equilibrium expression
Step 4: Substitute the values
Step 5: Add correct units
Questions.
1. Calculate the solubility product of the
following solutions:
(i) a saturated solution of cadmium
sulfide, CdS, with a solubility of
1.46 x 10-11 mol.dm-3.
(ii) a saturated solution of calcium
fluoride, CaF2, with a solubility of
0.0168 gdm-3 CaF2.
(b) Calculating solubility from solubility
product.
Example:
 Calculate the solubility of copper (II) sulfide in

mol.dm-3. (Ksp for CuS = 6.3 x 10-36 mol2dm-6)

Step 1: Write down the equilibrium equation
Step 2: Write the equilibrium expression in
terms of solubility S in mol.dm-3.
Step 3: Substitute the value of Ksp
Step 4: Calculate the solubility in mol.dm -3.
Questions.
1. Calculate the solubility in mol.dm-3 of
zinc sulfide, ZnS. (Ksp = 1.6 x 10-23 mol2
dm-6)
2. Calculate the solubility of silver
carbonate, Ag2CO3. (Ksp = 6.3 x 10-12
mol3dm-9)
3. A saturated solution of magnesium
fluoride, MgF2, has a solubility of 1.22 x
10-3 mol.dm-3. Calculate the solubility
product of magnesium fluoride.
4. Calculate the solubility of copper (II)
5. Which one of these is the correct
numerical value for the solubility
product for bismuth sulfide, Bi2S3?
Solubility of Bi2S3 = 3.6 x 10-8 mol.dm-3
A. 6.53 x 10-36
B. 1.30 x 10-39
C. 7.77 x 10-15
D. 4.35 x 10-36
6.5. Predicting precipitation of a
salt.

 We can use the solubility product, Ksp,

to predict whether precipitation will
occur or not when two solutions are
mixed.
 If Ksp value = product of the ions; no ppt
forms, we have saturated solution.
 If Ksp value > product of the ions, the salt
dissolves to reach equilibrium
 If Ksp value < product of the ions, the salt
will not dissolve, ppt forms
Example.
 Will a precipitate form when we mix a solution
of barium chloride, BaCl2, with a very dilute
solution of sodium carbonate?
Solution.
 Both BaCl and Na CO are soluble salts, but
2 2 3
BaCO3 is sparingly soluble. We have to consider
the equilibrium for the insoluble salt dissolved
in water.
 BaCO (s) Ba2+(aq) + CO32-(aq)
3
 The solubility product is given by:
 Ksp = [Ba2+] [CO32-] = 5.5 x 10-10 mol2 dm-5
 Cont…
 If [Ba2+] [CO32-] is greater than 5.5 x 10-10
mol2dm-6, a precipitate will form.

 If [Ba2+] [CO32-] is less than 5.5 x 10-10

mol2dm-6 no precipitate will form
Questions.
1. Will a precipitate form if we mix equal volumes of
solutions of 1.00 x 10-4 mol.dm-3 Na2CO3 and 5.00
x 10-5 mol.dm-3 BaCl2? Ksp for BaCO3 is 5.5 x 10-10
mol2dm-6.
2. A solution is prepared by mixing 50cm3 of 0.005
mol.dm-3 of CaCl2 solution and 80cm3 of 0.006
mol.dm-3 of ZnF2 solution at 25ºC.
(i) Calculate the concentration of calcium and
fluoride ions in the solution.
(ii) Given that the solubility product, Ksp, for
CaF2 is 3.95 x 10-11 mol3dm-9, state with
reasons whether precipitation will occur or not.
Cont…
3. Calcium sulfate is a sparingly soluble salt that
can be made by mixing solutions containing
calcium and sulfate ions. A 0.00100 moldm-3
solution of calcium chloride, CaCl2, is mixed with
an equal volume of 0.00100 moldm-3 solution of
aqueous sodium sulfate, Na2SO4.
(a) Calculate the concentration of calcium
and sulfate ions when equal volumes of these
solutions of CaCl2 and Na2SO4 are mixed.
(b) Will a precipitate of calcium sulfate form?
(Ksp for CaSO4 = 2.0 x 10-5 mol2dm-6)
4. A saturated solution of copper (I) sulfide, Cu2S, contains
1.91 x 10-12g of Cu2S dissolved in 1 dm3 of water.
(Ar values: Cu = 63.5, S = 32.1)
(a) Write an equilibrium expression for the
solubility product of copper (I) sulfide. [1]
(b) Calculate the value of the solubility product
of copper (I) sulfide, stating the units. [5]
(c) Copper (II) chromate has a solubility of
1.9 x 10-3 mol.dm-3. Copper (II) sulfate has a
solubility of 1.4 x 10-1 mol.dm-3. What will you
observe when 10cm3 of an aqueous solution of 0.01
mol.dm-3 copper sulfate is added to an equal volume
of a saturated solution of copper (II) chromate?
Explain your answer. [3]
5. Calcium sulfate is a sparingly soluble salt that can
be made by mixing solutions containing calcium
and sulfate ions. A 0.00100 mol.dm-3 solution of
aqueous calcium chloride, CaCl2, is mixed with an
equal volume of 0.00100mol.dm-3 solution of
aqueous sodium sulfate, Na2SO4.
(i) Calculate the concentration of calcium
and sulfate ions when equal volumes of
these solutions of calcium chloride
and sodium sulfate are mixed.
(ii) Will a precipitate of calcium sulfate form?
(Ksp of calcium sulfate = 2.0 x 10-5 mol2dm-6)
6.6. Common ion effect
 Common ion effect is the reduction in
the solubility of a dissolved salt due to
the addition of a solution of a compound
containing an ion common with the
dissolved salt.
 Common ion effect often results in
precipitation of the salt.
 Note:
 In calculations involving common ions, the
concentration of the common ion is taken
as that of the strong electrolyte.
Questions.
1. Calculate the solubility of barium sulfate in;
(a) water and
(b) 0.1mol.dm-3 H2SO4, given that its solubility
product,Ksp, is 1.0 x 10-10 mol2 dm-6
at 298K.
2. The solubility product of lead (II) chloride has a
value of 1.6 x 10-5 mol3dm-9 at 298K. Calculate
the solubility of PbCl2 in;
(a) water
(b) 0.1 mol.dm-3 lead (II) nitrate
(c) 0.1 mol.dm-3 sodium chloride
3. ESQ, qn.3, pg. 460
Cont…
5. The solubility of lead (II) sulfate at 25ºC
is 0.40gdm-3.
(i) what is its solubility product?
(ii) calculate the solubility in g.dm-3
in a 0.01 moldm-3 sodium sulfate
solution.
 7. Partition Coefficients
M5-L4-68

If we put two immiscible solvents, say 1 and 2 in a beaker,

they form two layers.

What happens if we add a solute that is soluble in both

layers?
 Distribution of Solute between solvents
M5-L4-69

Video: 5_4_1_DistributionOf SoluteBetweenSolvents.wmv

 7.1. The distribution law

 If a solid or liquid, X, is added to a mixture

of two immiscible liquids , in both of which
it is soluble, it will distribute itself
between the two liquids according to the
distribution or partition law.
 The law states that, “ the ratio of the
concentration of a solute between
two immiscible solvents is a constant
provided that
concentrat iontemperature
of X in solventis A
constant and the solute is in the K
same concentrat ion of state
molecular X in in solvent
both B
Cont…
 K is an equilibrium constant, known as
partition coefficient, Kpc.

 It is a constant for a given substance, and

varies with temperature.

 Partition coefficient, Kpc, is defined as the

ratio of the concentrations of a solute between
two immiscible solvents in contact with each
other when equilibrium has been established.
Conditions for Kpc to remain constant.
(Limitations of partition law).

 Solute should be in the same molecular

state in both solvents, i.e. it should not
dissociate or associate in either of the
solvents.
 Temperature should be constant
 The solvents must be immiscible
 There should not be any reaction
between the solute and the solvents.
 7.2.What affects the value of Kpc?

 The value of Kpc depends on the relative

solubilities of the solute in the two solvents
used in the partitioning.
 Solubility depends on the strength of

intermolecular forces between the solute and the

solvent.
 This in turn depends on the nature/polarity of the

molecules of solute and solvent.

Example:
Kpc of NH3 between CHCl3 and H2O is less than 1
but the Kpc of I2 between C6H12 and H2O is greater
than 1.
Questions.

 1. A solid X is added to a mixture of

benzene and water. After shaking well
and allowing to stand, 10cm3 of the
benzene layer was found to contain
0.13g of x and 100cm3 of water layer
contained 0.22g of X. Calculate the
value of partition coefficient.
 Density of benzene = 0.8765g/cm3,

density of water = 1.0g/cm3

Solution.

 Concentration of x in benzene (Cb) = 0.13/10 =

0.013gcm-3
 Concentration of x in water (Cw) = 0.22/100 =
0.0022gcm -3
 According to the distribution law, partition
coefficient
(Cb /(Cw) = (0.013/0.0022) = 5.9

 This value of distribution coefficient implies that

the solid x dissolves more in benzene than in
water (as shown in the concentrations)
2. An aqueous solution of a monobasic
organic acid A was allowed to reach an
equilibrium distribution in a separating
funnel containing 50cm3 of diethyl ether.
The ether layer required 22.5cm3 of
1moldm-3 NaOH solution and 25cm3 of
the aqueous layer required 9cm3 of
0.1moldm-3 NaOH solution. Calculate the
partition coefficient of A between ether
and water.
3.100cm3 of a 0.100 mol dm-3 solution of ammonia
in water at 20ºC was shaken with 50cm3 of an
organic solvent and left in a separating funnel
for equilibrium to be established.
A 20cm3 portion of the aqueous layer was run
off and titrated against 0.200 moldm-3 dilute
HCl. The end-point was found to be 9.40cm 3 of
acid. What is the partition coefficient of
ammonia between these two solvents at 20ºC?
Comment on the solubility of ammonia in the
two solvents.
Note: Ammonia reacts with HCl as follows:
NH3(aq) + HCl(aq) NH4Cl(aq)
4. X is a weak tribasic acid of RMM
210g which is soluble in benzene and in
water with the same molecular state.
After 2.8g of X had been shaken with
100cm3 of benzene and 50cm3 of water,
it was found that 25cm3 of the aqueous
layer needed 14.5cm3 of 1moldm-3 NaOH
for neutralisation. Calculate the partition
coefficient of X between benzene and
water.
Cont…
5. When 100cm3 of an aqueous solution
containing 2.0g of the organic dye X
was shaken with 20cm3 of hexane, it
was found that 1.6g of the dye had
been extracted into the hexane.
(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 0.1g.
Cont…
6. A solution of iodine in trichloroethane (TCE)
was shaken with water. The iodine content of
the two layers was determined by titration
with aqueous sodium thiosulfate. A 25cm 3
portion of the aqueous layer required 9.5cm 3
of 0.02 mol dm-3 thiosulfate to reach the end
point, whereas 5cm3 of the TCE layer required
17.5cm3 of 0.2 moldm-3 thiosulfate. Calculate
the Kpc for iodine between TCE and water.
equation for the rxn is:
I2 + 2S2O32- 2I- + S4O62-
 7.3. Solvent extraction
 This is one of the methods which can be
used to separate mixtures, and it’s one of
the applications of distribution law.
 It is used to extract/remove a solute from
a solution using another solvent which is
immiscible with the first solvent.
 Principle of solvent extraction.
 If the extracting solvent is used in small
portions, i.e. many extractions are
conducted, it will result into more solute
being extracted than if the whole extracting
solvent is used once.
 Multiple Extraction
M5-L5-82
Why is Multiple Extraction More Efficient?
M5-L5-83

Case 1: Using all the ether in one lot of 100 ml

Distribution
Law:

Thus, 66% of substance is extracted.

Why is Multiple Extraction More Efficient
M5-L5-84

Case 2: Using the ether in two portions of 50ml.

= 50%

The substance left in water layer is ½ A = 50%

= 25%

Thus, a total of 75% of substance is extracted by using two 50ml

portions
Question.

1. (a) Suppose 8g of solute is dissolved in 60cm3

of water and 60cm3 of ether is available for
extracting the solute. The partition
coefficient between ether and water is 3.
How much solute will remain in water after
the extraction?
(b) Calculate the mass of solute in water after
double extraction using 30cm3 of ether in
each.
(c) What mass of solute will remain if the
solute above is extracted by using three
portions of 20cm3 of ether?
2. A solution of butanedioic acid (BDA) in ether
contains 0.034mol of BDA in 29 cm3 of
ether. This solution is shaken with 50cm3 of
water. The amount of BDA extracted into the
water layer after shaking was 0.032 mol.
(a) Calculate the concentration of BDA in
the aqueous layer after shaking
(b) Calculate the concentration of BDA in
the ether layer after shaking
(c) Determine the value of the partition
coefficient, Kpc.
Cont…
3. 8g of an unknown substance G, was
shaken with 100cm3 of water. What
percentage of G would be extracted after
(a) a single extraction using
100cm3 of benzene
(b) five successive extractions
using 20cm3 of benzene in
each round?
Given that partition coefficient of G
between benzene and water is 4.
Cont…
4. The Mogul oil company is disturbed by the
presence of impurities A in its four star
petrol. One dm3 of petrol contains 5 g of A. In
the efforts to reduce the concentration of A in
the petrol, Mogul has discovered the secret of
extracting A from the petrol by using
solvent S. The partition coefficient of A
between petrol and S is 0.01.
(a) Define the term partition coefficient
(b) What are the conditions necessary
for the partition coefficient of a solute
between the two given solvents to
remain constant?
(c)State the principle of solvent extraction
(d)Calculate the total mass of A removed
from one dm3 of petrol using one
portion of 100cm3 of solvent S. In the
other case use two 50cm3 portions of
solvent S.
(e)What can you conclude from the results
of extractions obtained in part (d)
above?