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Reversible reaction (forward and backward reaction)

Equilibrium constant (K
c
and K
p
)
Factors affecting equilibrium- Le Chateliers principle
Recap on AS level- Chemical
equilibrium
Strong and weak acids and bases
Acids which dissociate almost completely in
solution.
Lower pH (1-2)
Eg: Mineral acids- HCl, HNO
3
, H
2
SO
4

HCl (g) + H
2
O (l) H
3
O
+
(aq) + Cl
-
(aq)

Strong
acids
Acids which are only partially dissociated in
solution.
pH is much higher compared to strong acid (pH 3-
5)
Eg: Organic acids- HCN, hydrogen sulfide and
carbonic acid
CH
3
COOH (l) + H
2
O (l) CH
3
COO
-
(aq) + H
3
O
+
(aq)

Weak acids
Strong
bases
Bases which dissociate almost completely in solution.
High pH- (12-14)
Eg: Group 1 metal hydroxides
NaOH (s) + aq Na+ (aq) + OH- (aq)

Weak bases
Bases which are only partially dissociated in solution.
pH is much lower compared to strong acid (10-11)
Eg: Ammonia, amines and some hydroxides of
transition metals
NH
3
(g) + H
2
O (l) NH
4
+
(aq) + OH
-
(aq)

Extension to Bronsted-Lowry definition is the presence of conjugate
acid and base. Note that WEAK ACID would produce a conjugate
base, and WEAK base would produce a conjugate acid. Look at
following example:
CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+

Given CH
3
COOH = acid, hence conjugate base =
Likewise, H
2
O = base, hence conjugate acid =
The important equilibrium in water
Water can acts as an acid (donating proton, H+) or a
base (by accepting proton, H+). In pure water, the
following equilibrium exists.

Ionic product of water, K
w

H
2
O(l) + H
2
O(l) H
3
o
+
(aq) +
-
OH (aq)
The equilibrium can be simplified by writing H
3
O
+
as
simple hydrogen ions, H
+
H
2
O(l) H
+
(aq) +
-
OH (aq)
Ionic product of water, K
w

The equilibrium expression for this reaction is:
The extent of ionisation of water is very low.
-Concentration of H
+
and

OH ions in water is very low
- K
c
is extremely small
- Concentration of water can be regarded as constant
The equilibrium expression then becomes:
Ionic
product
of water
Its value at 298K is 1.00 x10
-14
mol
2
dm
-6
The pH of pure water-
why does pure water has a pH of 7?
In pure water at room temperature the K
w
value tells us that:


For each water molecule that ionises, one H
+
ion and one

OH ion
are produced. Concentration of H
+
ion equals to the of hydroxide
ion
We can rewrite the equilibrium expression


Taking the square root of each side gives the concentration of H
+
in
pure water


Converting that into pH
pH = -log
10
[H
+
]
pH = 7
K
w
= [H
+
][OH
-
]= 1.00 x 10
-14
K
w
= [H
+
]
2
= 1.00 x 10
-14
[H
+
] = K
w
= 1.00 x 10
-14
= 1.00 x 10
-7
mol dm
-3
(pH of pure water
at room
temperature)
The variation of the pH of pure
water with temperature
H
2
O(l) H
+
(aq) +
-
OH (aq) H = +57kJ mol
-1

The forward reaction absorbs heat.
According to Le Chatelier's Principle, if you make a change
to the conditions of a reaction in dynamic equilibrium, the
position of equilibrium moves to counter the change you
have made.
When temperature is increased, the equilibrium
position will shift to favour the forward reaction.
More H
+
and OH
-
ion produced. This increased the
value of K
w
(C) K
w
(mol
2
dm
-6
) pH
0 0.114 x 10
-14
7.47
10 0.293 x 10
-14
7.27
20 0.681 x 10
-14
7.08
25 1.008 x 10
-14
7.00
30 1.471 x 10
-14
6.92
40 2.916 x 10
-14
6.77
50 5.476 x 10
-14
6.63
100 51.3 x 10
-14
6.14
If the pH falls as
temperature increases,
does this mean that
water becomes more
acidic at higher
temperatures?
NO!

A solution is acidic if there is an excess of hydrogen ions over
hydroxide ions. In the case of pure water, there are always the same
number of hydrogen ions and hydroxide ions. That means that the
water remains neutral - even if its pH changes.
pH is a measure of the
concentration of hydrogen ions in
a solution
Lower pH indicates higher
concentration of H
+
ions




pH calculation
Calculate the pH of the following solutions:
a) [H
+
] = 3.00 x 10
-4
mol dm
-3
b) [H
+
] = 1.00 x 10
-2
mol dm
-3
c) [H
+
] = 4.00 x10
-8
mol dm
-3
Calculating pH values from [H
+
]
Note in c) although the pH is alkaline, they still have
small concentration of H
+
because H
2
O H
+
+
-
OH is an
equilibrium
pH = -log
10
[H
+
]
[H
+
] =10
-pH
Calculating [H
+
] from pH
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
Strong acids completely ionised in solution.
It follows from this, that the concentration of
hydrogen ions in solution is approximately the same
as the concentration of the acid. (Assuming that the
concentration of H
+
arising from ionisation of water
molecules is very small)
Examples:
pH of 0.1 mol dm
-3
HCl is log (1x10
-1
mol dm
-3
) = pH 1
pH of 0.01 mol dm
-3
HCl is log (1x10
-2
mol dm
-3
) = pH 2
pH of 0.001 mol dm
-3
HCl is log (1x10
-3
mol dm
-3
) = pH 3




The pH of strong acids
Diluting the acid by 10 times
-Reduces the value of the H
+
ion concentration by one-tenth
-Increases the pH by a value of one
Strong bases eg NaOH ionises completely in solution
The concentration of hydroxide ion in a solution of NaOH
will be same with the concentration of the NaOH

To calculate the pH of strong base solution, we need to
know:
The concentration of OH ions in solution
The equilibrium expression for the ionisation of water
The value of K
w
for water




Calculating the pH of strong bases
K
w
= [H
+
][OH
-
]

[H
+
] = K
w
/ [OH
-
]
pK
w
= pH + pOH

14 = pH + pOH
CHECK-UP
Find the pH of the following strong acids and strong bases:
a) 1.00 mol dm
-3
HNO
3
b) 0.500 mol dm
-3
HNO
3
c) An aqueous solution containing 3.00 g HCl per dm
3
d) 0.00100 mol dm
-3
KOH (K
w
= 1.00 x 10
-14
mol
2
dm
-6
)
e) An aqueous solution containig 0.200 g of NaOH per dm
3

(K
w
= 1.00 x 10
-14
mol
2
dm
-6
)
Strength of weak acid or base depends on their dissociation
constant. For acid, it is assigned K
a
(acid dissociation
constant), while dissociation constant of base is K
b
.
These however apply only for weak acids and bases. Strong
acid/base do not have K
a
or K
b
as their dissociation proceed to
completion.



STRENGTH OF ACID AND BASES
Even if water
is present in
the equation,
it is not
included in the
K
a
or K
b
expression
CH
3
COOH (aq) + H
2
O (l) CH
3
COO
-
(aq) + H
3
O
+
(aq)

The equation can be simplify
CH
3
COOH (aq) CH
3
COO
-
(aq) + H
+
(aq)





HA H
+
+ A

Therefore, the higher the K
a
, the stronger is the acid.
Likewise for K
b
and strength of base.

-A high K
a
value (eg 40 mol dm
-3
) indicates that the position
of equilibrium lies to the right. The acid is almost completely
ionised
- A low value for K
a
(eg 1.0x 10
-4
mol dm
-3
) indicates that the
position of equilibrium lies to the left.
The balanced equation for the partial ionisation of
weak acid, HA is:
Since K
a
values for many acids are very low, the weak acids
and bases strength are also expressed in terms of pK
a
or pK
b
.


Hence, the lower the pK
a
(less positive), the stronger is the
acid.
Monoprotic acid = one K
a
value
Polyproptic acid = several K
a
value depending on the basicity
of the acid
In most occasion, K
a
for first step disscociation is higher than
the second, and second is higher than third etc.

Example = H
3
PO
4
3 K
a
values
In order to obtain the average K
a
value for complete
dissociation, K
a
= K
a1
x K
a2
x K
a3

pK
a
= - log K
a

HA H
+
+ A

Calculating K
a
and pH for weak acid
K
a
for a weak acid is related to:
the concentration of the acid, [HA]
the pH of the solution, pH = -log
10
[H
+
]
Each molecules of HA ionises to form one H
+
ion and one
A
-
ion. (This assumes that we ignore the H
+
ions arising
from the ionisation of water)
[H
+
] = [A
-
]
Therefore,
Calculating K
a
and pH for weak acid
2 assumptions made for the calculation of K
a
and pH of
weak acids:
1. Concentration of H
+
produced by the ionisation of
water molecules in the solution is ignored. Because
of ionic product of water (1.00 x10
-4
mol
2
dm
-6
) is
negligible compared with the value of most weak
acids

2. Ionisation of weak acid is so small. Undissociated
HA molecules present at equilibrium is
approximately same as that of original acid.

CHECK-UP
Calculate the value of K
a
and pK
a
for the following
acids:
i) 0.0200 mol dm
-3
2-aminobenzoic acid, which has a
pH of 4.30
ii) 0.0500 mol dm
-3
propanoic acid, which has a pH of
3.10
iii) 0.100 mol dm
-3
2-nitrophenol, which has a pH of 4.10
CHECK-UP
a) Given the K
a
value of 0.0200 mol dm
-3

aqueous benzoic acid is 6.3x10
-5
mol dm
-3
,
work out the pH of the solution.
b) 0.0100 mol dm
-3
hydrated aluminium ions has
a K
a
value of 1.0 x10
-5
mol dm
-3
. Find the pH of
the solution.
The purpose of titration is usually either to determine the
concentration of a solution or to produce salts. In both
cases, titration proceeds to a point where the [H
+
] = [OH
-
].

That point is known as the equivalence point consist of
salt and water ONLY
ACID-BASE TITRATION
Introducing indicators
In order to help us determine the completion of a titration,
indicator is often included in the sample.
Acid-base indicator is a dye or mixture of dyes which
functions by exhibiting colour change at certain pH.

The point where indicator show colour change in a titration is
known as end point of titration.





When pH is low, equilibrium shift___________, solution has
colour . When pH is high, concentration of _______ is
high, solution has colour .
Considered indicator as
weak acids. The acid (HIn)
and conjugate base (In
-
)
have different colours
Un-ionised indicator
Colour A
Conjugate base
Colour B
HIn H
+
+ In


Litmus indicator
Litmus is a weak acid. It has a seriously complicated molecule,
so we will simplify to HLit.
The equilibirum established when this acid dissolves in water is
as follow:

Un-ionised litmus
Red colour
Conjugate base
Blue colour
Adding hydroxide ion: Adding hydrogen ion:
Litmus indicator
If the concentration of HLit and Lit- are equal:
The colour will be mixture of the two. For litmus, it so
happens that the 50/50 colour does occur at close to pH 7.
[Not necessary all neutral solution or solution having equal
concentrations of H
+
and

OH ions occur at pH 7]
Methyl orange indicator
The equilibrium established between the 2 forms of
methyl orange is as follow:

Un-ionised methyl orange
Red colour
Conjugate base
Yellow colour
In the methyl orange case, the half-way stage where the
mixture of red and yellow produces an orange colour
([H-Meor] and [Meor
-
] are equal) happens at pH 3.7 -
nowhere near neutral.
Phenolphthalein indicator
The equilibrium established for phenolphthalein is shown
below:
The half-way stage happens at pH 9.3. Since a mixture of
pink and colourless is simply a paler pink, this is difficult
to detect with any accuracy!
The pH range of indicators
Because indicator just like any other weak acid, we can
write an expression for K
a
for it. We will call it K
ind

At the halfway stage (equivalence point), the
concentrations of acid [Hind] and its conjugate base [Ind]
are equal
pH = pK
ind
That means that the end point for the indicator depends
entirely on what its pK
ind
value is.
Indicators don't change colour sharply at one particular pH
(given by their pK
ind
). Instead, they change over a narrow
range of pH.

Normally is between 1 and 2 pH unit from the end-point
(pKind)
indicator pK
ind
pH range
litmus 6.5 5 - 8
methyl orange 3.7 3.1 - 4.4
phenolphthalein 9.3 8.3 - 10.0
Name of dye Colour at
lower pH
pH range End-
point
Colour at
higher pH
Methyl violet Yellow 0.0-1.6 0.8 Blue
Methyl yellow Red 2.9-4.0 3.5 Yellow
Methyl orange Red 3.2-4.4 3.7 Yellow
Bromophenol blue Yellow 2.8-4.6 4.0 Blue
Bromocresol
green
Yellow 3.8-5.4 4.7 Blue
Methyl red Red 4.2-6.3 5.1 Yellow
Bromothymol
blue
Yellow 6.0-7.6 7.0 Blue
Phenolphthalein Colourless 8.2-10.0 9.3 Pink/violet
Alizarin yellow Yellow 10.1-13.0 12.5 Orange/red
CHOOSING INDICATORS FOR TITRATIONS
1) STRONG ACID STRONG BASE TITRATION

Initial pH is low
indicates strong
acid.
Amount of acid to
be neutralised =
0.05 L (0.1M)
Since HCl reacts
with NaOH at 1:1
ratio, hence the
amount of NaOH
required to
neutralise HCl =
0.05 L as well.
A sharp increase in the graph line between pH 3.5-10.5. a tiny
addition of H
+
ions result in a rapid change in pH

At this point, [H
+
] = [OH
-
], @ Equivalence point. Since the salt
produced, NaCl is neutral, the pH at the midpoint of the steep
slope (equivalence point) = 7.

Because the sharp pH change occurs over such a wide range,
the indicators suitable to determine the end point of such
titration is phenolphthalein, bromothymol blue and methyl
red as the colour change takes place close to the equivalence
point (within the pH jump).
Interpretation of the graph:
Strong acid-strong base titration
Equivalence point
2) STRONG ACID WEAK BASE TITRATION

Initial pH is low, and the
final pH is not that high
compared to the previous
graph as weak base has
relatively low pH than
strong base.

Suitable indicators:
(i) Methyl red (pH
range = 4.2-6.3)
(ii) Bromo. Blue
(iii) Bromocresol green



A sharp increase in the graph line
between pH 3.5 7.5
The midpoint of the steep slope is at
about pH 5
Despite of the difference in the strength of acid/ base, the
amount of base required to neutralise the acid is depends on
the stoichiometry of the reaction, i.e.
M
1
V
1
= M
2
V
2
The pH of the equivalence point in this case is not 7. Although
at equivalence point acid and base has totally neutralised each
other producing salt and water, the pH 7.

This is due to the cationic hydrolysis of the salt produced.
Reaction between strong acid and weak base often produce
salt that are acidic. Example: HCl + NH
3

The salt produced = NH
4
Cl

NH
4
+
+ H
2
O NH
3
+ H
3
O
+

Cl
-
+ H
2
O HCl + OH
-

3) WEAK ACID STRONG BASE TITRATION
Initial pH is quite high as it is
a weak acid, pH usually 2
4.
The final pH is high due to
the presence of strong
base.
Before the equivalence
point, the increase in the
pH is slow due to
neutralisation between
acid and base. This region
is called the buffering
region.
Suitable
indicator =
phenolphthalein

The pH at the equivalence point is greater than 7.
It is due to anionic hydrolysis of basic salt produced
from the neutralisation. Eg: NaOH +CH3COOH produce
CH
3
COONa

CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-


Na
+
+ H
2
O NaOH + H
+

4) WEAK ACID WEAK BASE TITRATION

Initial pH = relatively high, and
final pH = relatively low
Shape:
(i) Similar like weak acid
strong base, the initial pH
increased slightly drastic before
slowing down.
(ii) No sharp rise in pH at the
equivalence point. Hence no
suitable indicator.

Compare the difference
between weak acid-weak base
titration curve with that of
strong acid-strong base as
shown.


The pH of the equivalence point depends on the K
a

and K
b
of the cation and anion of the salt produce
respectively.
If K
a
of cation > K
b
of anion, hence the hydrolysis
will produce acidic solution, vice versa
Example: CH
3
COONH
4





Since K
a
of CH
3
COO
-
is almost the same as K
b
of NH
+
,
hence the hydrolysis of the salt produce neutral
solution.
CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-

NH
4
+
+ H
2
O NH
3
+ H
3
O
+
pH of equivalence point will be different from case to
case
CHECK-UP
Draw sketch graphs to show the pH changes in the flask when the following
acids or alkalis are titrated. Indicate the pH and the volume of acid or alkali
added on your graphs and indicate suitable indicators for the titration
a 20 cm
3
of 0.2 mol dm
-3
sodium hydroxide is placed in the flask and titrated
with 0.2 mol dm
-3
sulfuric acid. [4]
b 20 cm
3
of 0.1 mol dm
-3
hydrochloric acid is placed in the flask and titrated with
0.1 mol dm
-3
sodium hydroxide. [4]
c 25 cm
3
of 0.1 mol dm
-3
ethanoic acid is placed in the flask and titrated with
0.1 mol dm
-3
sodium hydroxide. [4]
d 15 cm
3
of 0.1 mol dm
-3
ammonia is placed in the flask and titrated with
0.1 mol dm
-3
ethanoic acid.
A buffer must contain
a relatively large quantity of acid to react with any OH
ions that might be added to it
A relatively large quantity of base to react with any H+ ions
that might be added to it
The acid and base components of the buffer solution must
not neutralise each other.

BUFFER SOLUTION
Buffer solution is a solution that is able to resist change
in pH when a little acid or base is added to it.
ACID BUFFER SOLUTION
-Mixture of weak acid with
its conjugate base
HA + H
2
O A
-
+ H
3
O
+
BASIC BUFFER SOLUTION
-Mixture of weak base with its
conjugate acid
B + H
2
O HB
+
+ OH
-
Example of Acidic Buffer solution (pH slightly < 7)
CH
3
COOH / CH
3
COONa buffer solution
CH
3
COOH CH
3
COONa
Additional H
+

CH
3
COO
-
+ HCl CH
3
COOH + Cl
-

Additional OH
-

OH
-
+ CH
3
COOH CH
3
COO
-
+ H
2
O
CH3COOH (aq) CH3COO
-
(aq) + H
+
(aq)
CH3COONa (s) Na
+
(aq) + CH3COO
-
(aq)
Example of basic buffer solution (pH slightly > 7)
Aqueous NH
3
and NH
4
Cl
NH
3
(aq) + H
2
O (l) NH
4
+
(aq) + OH
-
(aq)
NH
4
Cl (aq) NH
4
+
(aq) + Cl
-
(aq)
NH
3
NH
4
Cl
Additional H
+

NH
3
+ HCl NH
4
Cl
Additional OH
-

OH
-
+ NH4
+
NH3 + H
2
O
pH of a buffer solution can be predicted using an equation
known as Henderson-Hasselbalch equation.

Derivation of the equation is based on the assumption
that
1) extent of dissociation of weak acid is very small that it
is negligible
2) dissociation of conjugate salt is complete.
pH and pOH of BUFFER SOLUTION
CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+
Have the following reaction:


In the dissociation of NH
3,
the K
b
for the equation can be expressed as:
K
a
= [CH
3
COO
-
] [H
3
O
+
]
[CH
3
COOH]
The above equation can be rearranged into:
[H
3
O
+
] = K
a
[CH
3
COOH]
[CH
3
COO
-
]
-log to the above equation yields:
-log [H
3
O
+
] = -log K
a
- log [CH
3
COOH]
[CH
3
COO
-
]

pH = pK
a
log [Acid]
[Salt]
The concentration of acid and salt is their initial concentration.
Similarly,
pOH = pK
b
log [Base]
[Salt]

CHECK-UP
Calculate the pH of the following buffer solutions:
i) 0.0500 mol dm
-3
methanoic acid and 0.100 mol dm
-3

sodium methanoate. (K
a
of methanoic acid = 1.60 x 10
-4

mol dm
-3
)
ii) 0.0100 mol dm
-3
benzoic acid and 0.0400 mol dm
-3
sodium
benzoate. (K
a
of benzoic acid = 6.3 x 10
-5
mol dm
-3
)

Importance of buffer solutions
Application of buffer solution:
-In industrial processes
1) Pharmaceutical industries buffer is added to maintain pH
of drugs or medicine and to maintain stability of drug in
different aqueous solution.
2) Dyeing industries Color strength of dyes is closely
related to narrow pH range which is maintained by using
different buffer systems

-In laboratory used to make sure that pH meter record the
correct pH
Importance of Buffer Solution to
Human Body
In human body, the pH of blood is kept between 7.35 and
7.45 by a number of different buffers in the blood:
hydrogencarbonate ions, HCO
3
-
haemoglobin and plasma proteins
Dihydrogenphosphate (H
2
PO
4
-
) and hydrogenphosphate
(HPO
4
-
) ions
Role of HCO3
-
in controlling pH of blood
The cells in our body produce carbon dioxide as a product of
aerobic respiration (the oxidation of glucose to produce
energy).
Carbon dioxide combines with water in the blood to form a
solution containing H
+
ions
CO
2
(aq) + H
2
O (aq) HCO
3
-
(aq) + H
+
(aq)
If [H
+
] increases:
The position of equilibrium lies to
the left
H
+
and HCO
3
-
combines to form
CO
2
and H
2
O
This reduces [H
+
] in the blood and
helps keep pH constant
If [H
+
] decreases:
The position of equilibrium lies to
the right
CO
2
and H
2
O combines to form H
+

and HCO
3
-
This increases [H
+
] in the blood
and helps keep pH constant
Applies to sparingly soluble salt.
Addition of excess sparingly soluble salt in water would
produce an equilibrium between the dissolved salts(ions from
the salts) and undissolved salt. The solution is said to be
saturated as it can no longer accept more ions.


SOLUBILITY PRODUCT, K
sp

Example: Solid silver chloride
added into water, some of the
salt dissolved, and some remain
as solid (in contact with the
saturated solution). Indication
that equilibrium is achieved.
AgCl (s) Ag
+
(aq) + Cl- (aq)

Solubility product, K
sp
of a sparingly soluble salt is the
product of concentration of ions in the saturated solution
of the salt, raised to the power equal to the stoichiometry
coefficient of the respective ions at constant temperature.
The equilibrium expression for the silver chloride:


Since for any solid, the concentration of the solid phase
remains constant, we can rewrite the equilibrium expression
as:
Example:
Fe
2
S
3
(s) 2Fe
3+
(aq) + 3S
2-
(aq)
Unit of K
sp
depends
on the number of
each type of ion
present in solution
Solubility product calculation and
solubility
Important!! Write down the equilibrium equation
Then calculate the concentration of each ion in
solution separately
According to the
equation, when 1 mol of
Fe
2
S
3
is dissolved in
water, 2 mol of Fe
3+
and
3 mol of S
2-
ions is found
in the water
K
sp
depends on molar solubility of a substance, which is the
number of moles that dissolve per liter of solution
Molar solubility of Fe
2
S
3
is 5.7 x 10
-3
mol dm
-3
.This means there will be
2 x 5.7 x 10
-3
mol of Fe
3+
ions and 3 x 5.7 x 10
-3
mol of S
2-
ions dissolved
in 1 dm
3
of water
K
sp
= [2 x 5.7 x 10
-3
]
2
[3 x 5.7 x 10
-3
]
3

Calculate the solubility product of the following solutions:
i) A saturated aqueous solution of cadmium sulfide, CdS
(solubility = 1.46 x 10
-11
mol dm
-3
)
ii) A saturated aqueous solution of calcium fluoride, CaF
2
,
containing 0.0168 g dm
-3
CaF
2

iii) Calculate the solubility in mol dm
-3
of zinc sulfide, ZnS.
(K
sp
= 1.6 x 10
-23
mol
2
dm
-6
)
iv) Calculate the solubility of silver carbonate, Ag
2
CO
3
(K
sp
=
6.3x 10
-12
mol
2
dm
-6
)

CHECK-UP
Besides giving an indication on the solubility of a salt, K
SP
IS
ALSO USED TO PREDICT THE OCCURRENCE OF
PRECIPITATION when two soluble salts are mixed together.
For example,
AB (aq) + HD (aq) --------> AD (s) + HB (aq)
We must consider the equilibrium for the insoluble salt
formed when dissolving in water:
AD (s) A
+
(aq) + D
-
(aq)
If the amount of A
+
and D
-
introduced into the system exceeds
the saturation level, precipitation will takes place as a mean to
reduce the concentration. The saturation level is indicated by
the K
sp
.
Hence, if
[A
+
] [D
-
] > K
sp
: Precipitation will takes place

[A
+
] [D
-
] K
sp
: Precipitation does not take place

Example:
Both barium chloride and sodium carbonate are soluble salts,
but the product formed from mixing the two salt solutions,
barium carbonate is relatively insoluble.
BaCl
2
(aq) + Na
2
CO
3
(aq) BaCO
3
(s) + 2NaCl (aq)
BaCO
3
(s) Ba
2+
(aq) + CO
3
2-
(aq)

The saturation level, K
sp
= [Ba
2+
][CO
3
2-
] = 5.5 x 10
-10
mol
2
dm
-6

IF [Ba
2+
][CO
3
2-
] > 5.5 x 10
-10
mol
2
dm
-6
, precipitate will form

IF [Ba
2+
][CO
3
2-
] < 5.5 x 10
-10
mol
2
dm
-6
, no precipitate will form
CHECK-UP
Will a precipitate form if we mix equal volumes of
solutions of 1.00 x 10
-4
mol dm
-3
Na
2
CO
3
and 5.00 x 10
-5

mol dm
-3
BaCl
2
? Note K
sp
of barium carbonate= 5.5 x 10
-10

mol
2
dm
-6

Equal volumes of each solution are combined, so each
solution has diluted the other by 2.
[Ba
2+]
= 5.00x10
-5
/ 2 = 2.50 x 10
-5
mol dm
-3
[CO
3
2-
] = 1.00 x 10
-4
/ 2= 5.00 x 10
-5
mol dm
-3


[Ba
2+
][CO
3
2-
] =

Calcium sulfate is a sparingly soluble salt which can be made by
mixing solutions containing calcium and sulfate ions. A 0.00100
mol dm
-3
solution of aqueous calcium chloride, CaCl
2
, is mixed
with an equal volume of 0.00100 mol dm
-3
solution of aqueous
sodium sulfate, Na
2
SO
4
.
i. Calculate the concentration of calcium and sulfate ions
when these solutions of calcium chloride and sodium sulfate
are mixed.
ii. Will a precipitate of calcium sulfate form? (K
sp
of calcium
sulfate = 2.0 x 10-5 mol
2
dm
-6
)
Reactions of the halide ions- Testing
for halide ions
Aqueous halide
ions
Cl
-
, Br
-
and I
-
( from KI, KBr, KCl)
Dissolve in dilute
nitric acid
Silver nitrate
solution
AgNO
3
(aq)
Coloured
precipitate
Silver halide
NO
3
-
+
+
Overall equation: X
-
(aq) + AgNO
3
(aq) AgX (s) + NO3
-
(aq)
Ionic equation: X
-
(aq) + Ag
+
(aq) AgX (s)
White Cream
Pale yellow
Colour of silver
halide precipitate
Confirming the precipitate using ammonia solution
(Dilute NH
3
solution & Concentrated NH
3
solution)
Testing for halide ions
Precipitate Effect on precipitate of
adding DILUTE ammonia
solution
Effect on precipitate of
adding CONCENTRATED
ammonia solution
AgCl Precipitate dissolve-
obtain colourless solution
Precipitate dissolve-
obtain colourless solution
AgBr Precipitate remain
insoluble
Precipitate dissolve-
obtain colurless solution
AgI Precipitate remain
insoluble
Precipitate remain
insoluble
Confirming the precipitate using ammonia
solution (Dilute NH
3
solution & Concentrated NH
3

solution)
A precipitate is form when the
concentration of ions in solution
exceed the solubility product,
K
sp
value
Note that solubility product,
decreases from AgCl> AgBr> AgI.
So AgI will likely form precipitate.
What is the ammonia doing?
Confirming the precipitate using ammonia
solution (Dilute NH
3
solution & Concentrated NH
3

solution)
Le Chateliers Principle Increasing concentration of NH
3
will shift
equilibrium to right. So lesser Ag
+
ion. Precipitate dissolves in solution
Common ion effect
The common ion effect is the reduction in the solubility of
a dissolved salt achieved by adding a solution of a
compound which has an ion in common with the dissolved
salt. This often results in precipitation.
In a saturated solution of silver chloride in water, the following
equilibrium:
AgCl (s) Ag
+
(aq) + Cl
-
(aq)

If a solution of sodium chloride is added:
the chloride ion is common to both sodium chloride and silver
chloride
the added chloride ions shift the position of the equilibrium to
the left
silver chloride is precipitated. Thus, solubility of silver chloride
decreases.
Considering the ionic product of the saturated solution of
silver chloride:
K
sp
= [Ag
+
][Cl
-
] = 1.0 x 10
-10

On addition of a little sodium chloride, the [Cl
-
] increases and
the ionic product:

[Ag
+
][Cl
-
] > K
sp
Hence, in order to maintain the value at 1.0x 10
-10
, the
concentration of Ag
+
must decrease. This is possible only if
some of the Ag
+
in solution combine with Cl
-
to form AgCl
The solubility of AgCl is also decreased if we add silver
nitrate (which provides the common ion, Ag+) to
saturated silver chloride solution
The solubility of lead(II) chloride in water

Lead(II) chloride is sparingly soluble in water, and this equilibrium
is set up between the solid and its ions in solution:

K
sp
= [Pb
2+
][Cl
-
]
2
= 1.7 x 10
-5
mol
3
dm
-9


In order to find solubility, let the solubility be = s
K
sp
= s x (2s)
2
= 4s
3
= 1.7 x 10
-5

s = 1.62 x 10
-2
mol dm
-3

HIGHLIGHT: SOLUBILITY PRODUCT MAY BE
CONSTANT BUT SOLUBILITY ITSELF IS NOT
CONSTANT!!!
K
sp
= [Pb
2+
][Cl
-
]
2
= 1.7 x 10
-5
mol
3
dm
-9


Now, [Cl-] = 0.10 mol dm
-3
, and let [Pb
2+
] = s
K
sp
= s (0.10)
2
= 1.7 x 10
-5
mol
3
dm
-9

s = 1.7 x 10
-3
mol dm
-3
If you tried to dissolve some lead(II) chloride in some 0.100
mol dm
-3
sodium chloride solution what happens to the
solubility?

Solubility in water Solubility in 0.10 mol dm
-3

sodium chloride solution
1.62 x 10
-2
mol dm
-3
1.7 x 10
-3
mol dm
-3
Reduction in solubility due to common ion effect
(presence of Cl
-
ion which is common with the
dissolved salt PbCl2)
CHECK-UP
A saturated solution of nickel(II) hydroxide, Ni(OH)
2
, contains 1.00
x 10
4
g of Ni(OH)
2
dissolved in 1 dm
3
of water.
a Write an equilibrium expression for the solubility product
of nickel(II) hydroxide. [1]
b Use the A
r
values (Ni = 58.7, H=1, O= 16) to calculate the
value of the solubility product of nickel(II) hydroxide,
stating the units. [5]
c Nickel(II) sulfide has a solubility of 4.0 x 10
5
mol dm
3
in
water. Nickel(II) fluoride has a solubility of 2.65 x 10

1
mol dm
3
in water. What will you observe when 20 cm
3
of
an aqueous solution of 0.01 mol dm
3
nickel(II) fluoride is
added to an equal volume of a saturated solution of
nickel(II) sulfide? Explain your answer. [3]
3 Barium chromate, BaCrO
4
, is a sparingly soluble salt. K
sp
=
1.17 x 10
10
mol
2
dm
6
.
a What does the term solubility product mean?
[2]
b Calculate the solubility of barium chromate in pure
water. [3]
c What does the term common ion effect mean?
[2]
d Calculate the solubility of barium chromate in an
aqueous solution of 0.01 mol dm
3
barium nitrate.
[2]
e Explain the difference in your answers to parts b
and d. [2]

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