Unit IV

Solubility equilibria
Solubility:
The solubility of a substance is the amount of that substance that will dissolve in a
given amount of solvent. Solubility may be considered to be equilibrium; the
equilibrium is between solid and ions in solution. Any ionic solid is 100% ionized in
aqueous solution; once it actually dissolves.
NaCl(s)

H 2 O

NaCl(aq)

Na+(aq)

+ Cl(aq)

The solubility of a substance fundamentally depends on the physical and chemical

properties of the solute and solvent as well as on temperature, pressure and the pH of the
solution. The extent of the solubility of a substance in a specific solvent is measured as
the saturation concentration, where adding more solute does not increase the
concentration of the solution and begin to precipitate the excess amount of solute.
Solubility product
Solubility product (Ksp), is the mathematical product of its dissolved ion
concentrations raised to the power of their stoichiometric coefficients. This statement is
called the solubility product principle.
MyXz (s)

yMZ+ (aq) + zXY-(aq)

K sp M z

Example:

X
y

y z

Ca3(PO4)2 3Ca2+ + 2PO43

Ksp = [Ca2+]3 [PO43]2

The dissolving of a precipitate is an equilibrium process. For example the dissolving of

barium sulphate is represented as
BaSO4 Ba2+ + SO42
The dissolving of BaSO4 to form Ba2+ and SO42 ion occurs at the same rate as the
recombination of the Ba2+ and SO42 ion and thus we have equilibrium. A special form of
the equilibrium constant is useful here. Because the amount of undissolved BaSO 4 does
not affect the equilibrium system and it doesnt make sense to refer to the concentration
of an undissolved chemical, the equilibrium expression is modified and only the product
of the concentration of the two ions appears. This constant is referred to as the solubility
product constant Ksp.
Ksp = [Ba2+] [SO42]

---------- (1)

Example 2: For a solution of AgCl in water, the equilibrium is:

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Ag+(aq) + Cl (aq)

AgCl(s)

The solubility product constant (Ksp) = [Ag+] [Cl]

Solubility and solubility product:
Let us consider the reaction
BaSO4 Ba2+ + SO42
The BaSO4 that dissolves result in the formation of one Ba2+ ions and one SO42 ions.
(a)The solubility of BaSO4, which can be expressed as the number of moles of
BaSO4 that dissolve per litre, is equal to the concentration of the Ba 2+ ion and
also the concentration of the SO42 ion in these saturated solutions.
(b)The Ba2+ concentration and the SO42 concentration are equal since for each
BaSO4 unit that dissolves one Ba2+ and one SO42 ion form.
The above two points can be summarised as follows
Solubility = s = [Ba2+] = [SO42]
From equation (1) we know that
Ksp = [Ba2+] [SO42]
Ksp = s s = s2
Thus, given the solubility of solid ionic compound, the Ksp can be calculated.
Problem 1: Calculate the Ksp value of BaSO4 which has a solubility of 3.9105 mol/L at
25C.
Solution:

BaSO4(s) Ba2+(aq)+ SO42-(aq)

Ksp = [Ba2+] [SO42]
Ksp = s s = s2
= 3.9105 3.9105
= 1.52109

Problem 2: What is the solubility of AgCl if the Ksp is 1.6 x 10-10

Solution:
AgCl(s) Ag+(aq) + Cl-(aq)
Ksp = [Ag+][Cl-]
If s is the solubility of AgCl, then:
[Ag+] = s and [Cl-] = s
Ksp = s s = s2 = 1.6 x 10-10
s=

1.6 x 10 -10

s = 1.3 x 10-5 mol/L.

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Problem 3: What is the solubility of CuS if the Ksp is 1.27 1045.

Solution:
Cu2+

CuS

+ S2

Ksp = [Cu2+] [S2]

= [s] [s]
= s2
s =

K sp
-45

= 1.27 x 10
= 3.56 1023 M
Problem 4: What is the solubility of Ca(OH)2 if the Ksp is 7.9 x 10-6
Solution:
Ca(OH)2 (s)

Ca2+ (aq) + 2OH-(aq)

K sp Ca 2

OH
1

K sp 1 s 2 s
1

K sp (1s ) (2 s ) (2 s )
K sp (1 2 2) ( s s s )

But , K sp 7.9 10 6
K sp 4s 3

7.9 10 6
s3
4

7.9 10 6 4 s 3
1.97 10 6 s 3
s 3 1.97 10 6 1.25 10 2 M

Problem 5: What is the solubility of Mg(OH)2 if the Ksp is 1.6 x 10-10

Solution:
Mg(OH)2(s) Mg2+(aq) + 2 OH-(aq)
Ksp = [Mg2+][OH-]2 = 8.9 x 10-12
If the solubility of Mg(OH)2 is s mol/L
[Mg2+] = s mol/L and [OH-] = 2s mol/L,
Ksp = (s)(2s)2 = 4s3 = 8.9 x 10-12
s = 1.3 x 10-4 mol/L.

PRECIPITATION TITRATIONS
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A special type of titrimetric procedures involves the formation of precipitates

during the course of a titration. The titrant reacts with the analyte forming an insoluble
material and the titration continues till the very last amount of analyte is consumed. The
first drop of titrant in excess will react with an indicator resulting in a color change and
announcing the termination of the titration.
Argentometric Titrations
The most widely applicable precipitation titrations involve the use of silver nitrate
with chlorides, bromides, iodides, and thiocyanate. Since silver is always there,
precipitation titrations are referred to as Argentometric titrations. This implies that this
type of titration is relatively limited.
Conditions for precipitation titration:
Any precipitation reaction could in theory be adopted to a volumetric technique,
provided that
(1) The precipitation reaction reaches equilibrium very rapidly after each addition
of titrant.
(2) No interfering situations like co-precipitation, occlusion or adsorption of
foreign ions occur.
(3) An indicator capable of locating the stochiometric equivalence point
accurately is available.

Determination of chloride by Volhards method:

Volhards method is used in the estimation of chloride ions with standard solution
of AgNO3. It is an example of titration in which indicator forms a coloured complex ion
with the titrant (i.e) Silver nitrate.
In this method, excess of AgNO3, solution is added in order to precipitate out the
anions to be estimated. Then excess (unreacted) Ag + ions are determined by back titration
with standard potassium or ammonium thiocyanate solution.
The end point is detected by adding indicator like ferric ammonium sulphate or
ferric alum which forms a soluble red complex with excess of titrant (i.e) NH 4SCN or
KSCN.
Determination of Cl ion involves:
(a) Preparation of standard ammonium thiocyanate:
By weighing appropriate quantity of ammonium thiocyanate, its 250ml of
0.1M solution is prepared in distilled water.
(b) Determination of unknown chloride ions:
Given chloride solution is diluted to 250ml using distilled water. From this
25ml solution is pipette out into a titration flask, to which 25ml of 0.1M
AgNO3 is added. After shaking the solution, 2ml of nitrobenzene and 5ml of
50% HNO3 and ferric alum is added as an indicator. It is then titrated with
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standard NH4SCN till reddish brown colour is obtained to supernatant

solution.
Suppose the reading is X ml. Then, (25X) ml will be the amount of
NH4SCN required to precipitate Cl ions. Using following chemical reactions
amount of Cl ions in given solution can be calculated.
Cl + AgNO3

AgCl

Ag+ + SCN

AgSCN

Fe3+ + SCN

+ NO3 + AgNO3

Fe(SCN)2+

Adsorption indicators:
Commonly used indicators for titration of chloride against silver nitrate are
Fluorescein, Dichlorofluorescein and Eosin.
(a) Fluorescein: It is a suitable indicator for very dilute solution of chloride
with silver nitrate in neutral or faintly acidic solution. At the end point
there is a sudden change of white precipitate in greenish yellow medium to
distinctly red.
(b) Dichlorofluorescein: It is a suitable indicator for every dilute solution of
chloride (say drinking water) and works even in the presence of acetic acid
and weakly acid solution. The end point is from yellowish green to red.
(c) Eosin: It is used for the titration of bromide and iodide with silver
nitrate(from burette) in the presence of acetic acid. The end point is the
change from pink to reddish violet.
Adsorption indicator Technique:
Titration of chloride by silver ion:
In fajans method of titrating Cl with Ag+, the adsorption indicator fluorescein is
used. During the titration and up to the equivalence point the precipitate of AgCl adsorbs
Cl ions present in excess in solution. The fluorescein ion being negative is repelled by
the negatively charged precipitate surface. The solution at this stage has the yellow-green
colour imparted by fluorescein. At the equivalence point, all the adsorbed Cl ions are
removed by Ag+. On the addition of the first excess of Ag +, AgCl surface adsorbs Ag+ ions
and the surface becomes positively charged.
The fluorescein ions now strongly get adsorbed on this positive surface. The silver
fluorescein formed has a deep red colour and the formation of this colour signals the end
point. A little excess of Ag+ is required to form the silver fluorescein and to indicate the
endpoint.

Gravimetric methods of analysis:

Gravimetric procedures always involve the separation of the analyte constituent
from the sample so that it can be isolated and weighed. This separation can be a physical
separation, such as through solubility or volatilization or it can be a chemical separation
(i.e) by chemical reaction, so as to form a precipitate that can be weighed.
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Steps in a Gravimetric Analysis

After appropriate dissolution of the sample the following steps should be followed for
successful gravimetric procedure:
1. Preparation of the Solution: This may involve several steps including adjustment of the
pH of the solution in order for the precipitate to occur quantitatively and get a precipitate of
desired properties, removing interferences, adjusting the volume of the sample to suit the
amount of precipitating agent to be added.
2. Precipitation: This requires addition of a precipitating agent solution to the sample
solution. Upon addition of the first drops of the precipitating agent, super saturation occurs,
then nucleation starts to occur where every few molecules of precipitate aggregate together
forming a nucleus. At this point, addition of extra precipitating agent will either form new
nuclei or will build up on existing nuclei to give a precipitate.
3. Digestion of the Precipitate: The precipitate is left hot (below boiling) for 30 min to 1
hour in order for the particles to be digested. Digestion involves dissolution of small particles
and reprecipitation on larger ones resulting in particle growth and better precipitate
characteristics. This process is called Ostwald ripening. An important advantage of digestion
is observed for colloidal precipitates where large amounts of adsorbed ions cover the huge
area of the precipitate.
4. Washing and Filtering the Precipitate: It is crucial to wash the precipitate very well in
order to remove all adsorbed species which will add to weight of precipitate. One should be
careful not to use too much water since part of the precipitate may be lost. Also, in case of
colloidal precipitates we should not use water as a washing solution since peptization would
occur. In such situations dilute nitric acid, ammonium nitrate, or dilute acetic acid may be
used. Usually, it is a good practice to check for the presence of precipitating agent in the
filtrate of the final washing solution. The presence of precipitating agent means that extra
washing is required. Filtration should be done in appropriate sized Gooch or ignition filter
paper.
5. Drying and Ignition: The purpose of drying (heating at about 120-150 oC in an oven) or
ignition in a muffle furnace at temperatures ranging from 600-1200 oC is to get a material
with exactly known chemical structure so that the amount of analyte can be accurately
determined.
6. Precipitation from Homogeneous Solution: In order to make Q (concentration of
reactants before precipitation) minimum we can, in some situations, generate the
precipitating agent in the precipitation medium rather than adding it. For example, in
order to precipitate iron as the hydroxide, we dissolve urea in the sample. Heating of the
solution generates hydroxide ions from the hydrolysis of urea. Hydroxide ions are
generated at all points in solution and thus there are no sites of concentration. We can also
adjust the rate of urea hydrolysis and thus control the hydroxide generation rate. This type
of procedure can be very advantageous in case of colloidal precipitates.

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Factors which affect solubility of precipitate:

Temperature: heat is absorbed as most solids dissolve. Therefore the solubility of
precipitates increases with increasing temperature. Solubility products for most sparingly
soluble compounds increase at higher temperatures.
Solvent composition: The nature of solvent influences the solubility of most inorganic
substances. It is markedly less in mixtures of water and organic solvents than in pure
water.
Common ion effect and Diverse ion effect: The solubility of a slightly soluble salt is
decreased by the presence of an ion which is in common with one of the ions of the
slightly soluble salt. For example, in the precipitation of AgCl from a solution of AgNO 3
using KCl as the precipitant, the addition of an excess of KCl will serve due to common
ion effect to reduce the molar solubility of AgCl. However the solubility of AgCl becomes
significantly large in solutions containing a high chloride concentration, such as 1.0M or
above owing to the formation of AgCl 2. and AgCl32 species. The benefit of the common
ion effect in suppressing the solubility of a precipitate is lost in the need to wash the
precipitate throroughly to remove the common ion.
Diverse ion effect: Many slightly soluble salts show an increased solubility in the
presence of increased concentration of certain salts having no ion in common with those
of the slightly soluble salt. Thus, AgCl is more soluble in KNO 3 solution than in water.
This effect is called the diverse ion or neutral salt effect.

Purity of Precipitates:
Purity of a precipitate is a vital aspect for successful gravimetric determination.
The precipitate may be contaminated with one or more other substances because those
other substances are themselves insufficiently soluble in the mother liquid. A precipitated
phase can become contaminated with substances from its mother liquid even when the
equilibrium solubilities of those other substances are not exceeded. The surface of a
precipitate has positive and negative centres and these may attract negative and positive
ions form the mother liquid. Such attracted ions would get adsorbed on the surface and
thus contaminate the precipitate.

General rules of precipitation:

(a) Precipitation should be carried out in dilute solution to minimize the error due to
co-precipitation.
(b) The reagents should be mixed slowly with constant stirring. This will keep the
degree of super saturation low, promoting the growth of large crystals.
(c) A slight excess of the reagent is generally required to ensure complete
precipitation.
(d) Precipitation is effected in hot solutions, provided the product is thermally stable.
At higher temperatures the solubility is increased with a consequent reduction in
the degree of super saturation.

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(e) The completion of precipitation should be ascertained by adding a few drops of

the precipitant through the side of the beaker and observing for absence of fresh
precipitate formation in the supernatant liquid.
(f) Crystalline precipitates should be digested preferably overnight, except in those
cases, where post precipitation may occur. Digestion on the stream bath is
desirable. Digestion has no effect upon amorphous or gelatinous precipitate.
(g) The precipitate should be washed with the appropriate dilute solution of an
electrolyte
(h) If appreciable co-precipitation is a possibility, the precipitate should be dissolved
in a suitable solvent and reprecipitated.

Types, care and use of crucibles:

Different types of crucibles are used for collecting and weighing the precipitates.
They are mainly of two types.
(1) Crucibles made of silica or porcelain are used when the precipitates are ignited to
constant weights.
(2) Sintered crucibles are used for precipitates which are weighed after drying in airoven.
Crucibles are expensive. They should be handled properly for obtaining reliable
gravimetric data. They should never be touched but must always be handled with
a pair of tongs. They should not be placed on the table but only on a clean tile.
Porcelain crucibles: These are usually of 3 to 4 cm in diameter. These should be
carefully hated with a small flame in order to avoid fracture before being heated to
a high temperature. These are suited for heating the precipitates to very high
temperatures. Porcelain crucibles are suitable for use up to a temperature of
1000 1200 C.
Silica crucibles: These are more expensive than porcelain crucibles. However,
these may be safely exposed to sudden changes of temperature without any risk of
fracture. These must not be used for alkalis or hydrofluoric acid, because these
chemicals attack silica. Certain precipitates tend to adhere strongly to these
crucibles and hence these crucibles should be carefully cleaned immediately after
use.
Platinum Crucible: Platinum crucibles are marketed in various shapes and sizes.
The choice for an experiment is decided by the quantity of precipitate handled.
These are very expensive and hence their use is very much restricted to cases
where they are indispensable. These crucibles can be more readily and more
uniformly heated to redness than porcelain crucibles.
The Gooch crucible: A Gooch crucible is made of porcelain with the bottom
perforated with a number of small holes. It is usually fitted into a glass adaptor
(Gooch funnel) by means of narrow rubber ring, the adapter passing through the
rubber stopper of a filter flask. The bottom of the crucible is covered with
asbestos. This covering is done by shaking the asbestos fibre bits with water and
pouring the mixture into the crucible. The water drains leaving the asbestos as a
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thin cover at the bottom. A Gooch crucible is used usually for drying precipitates
only up to 250C because above this temperature, the asbestos in it loses its
weight.
Gravimetric factor:
A gravimetric factor converts grams of a compound into grams of a single
element.
Example: To find the gravimetric factor of SO42 in BaSO4
BaSO4
Gravimetric factor =

Ba2+ + SO42

mass of SO 24 Molecular Mass of BaSO 4

96
=
Molecular Mass of BaSO 4

Von Weimann Ratio:

Von weiman discovered that the particle size of precipitates is inversely proportional
to the relative supersaturation of the sol. During the precipitation process.
Relative supersaturation =

Q-S
S

Q = Instantaneous concentration of each of the constituents in the mixture.

S = Solubility.
Paneth-Fajans Hahn Law:
This law gives an idea about the nature of adsorption. According to this law, a
precipitate preferentially adsorbs that ion which forms the least soluble compound with a
lattice ion. For example, calcium oxalate preferentially adsorbs magnesium ions than sodium
ions because magnesium oxalate is less soluble than sodium oxalate. Ion adsorption is
selective; it depends on the nature of electrical attraction, concentration of ions in solution,
size of ion, in addition to the solubility as indicated by the paneth-Fajans-Hahn law.

The degree of contamination in gravimetric process

The types of contamination we come across in gravimetry is
(a)Co-precipitation (b) Post-precipitation
(a)Co-precipitation: Soluble impurities which are getting precipitated along with the
formation of the precipitate. There are two other forms of co-precipitation (i) Inclusion
(ii) Occlusion.
(i)Inclusion is the process of impurities being randomly distributed in the form of
individual ions or molecules throught the crystal. Occlusion is a non-homogeneous
distribution of impurities present within the imperfect crystal lattice of the precipitate.
(ii)Occlusion occurs, when whole droplets of solutions containing impurities are trapped
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by a rapidly growing crystal. Contaminants are located within the crystal and therefore
washing will not remove these impurities form the precipitate.
(b)
Post-precipitation: After the formation of the precipitate, the impurities will
get soluble. This is another type of precipitate contamination.
Example: When calcium is determined as its oxalate and if the solution contains
magnesium ions, magnesium oxalate will be precipitated slowly on calcium oxalate. This
post precipitation is greater when the precipitate is kept in contact with the mother liquid
longer. It occurs with sparingly soluble substances which form supersaturated solutions.
These substances usually have an ion in common with the primary precipitate.
Ca2+

CaC2O4

(NH4)2C2O4

If Mg2+ is present as an impurity in Ca2+, then we can have a post precipitation of

MgC2O4 over CaC2O4. The post precipitation can be avoided by keeping a high pH.
Differentiate post-precipitation and co-precipitation:
S.No

Post-precipitation

Co-precipitation

Increases with time and When we allow the main precipitate

increases with higher with another, liquor, then they will
temperature
go into solution

Magnitude
of
error/ Contamination will be less
contamination in post
precipitation is greater

Post precipitation can be avoided

(a) By adding some masking agents
(b)By maintaining a high pH.
Examples of co-precipitation are
When estimating barium
Ba2+ + SO42
Contaminated with CrO42

BaSO4
BaCrO4

The contaminants will go and get occluded inside the crystal lattice of BaSO4.
These are the ways the co-precipitation can cause erroneous results. In order to
minimise this co-precipitation we digest the precipitate. Digesting the precipitate in
suitable solvent and reprecipitation gives good yield on co-precipitation.

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