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Deffinetion:

Saturated salution:

The solution which is incontact with the undissolved solute is


called saturated solution.

Saturated solution of CaF2.

Equation:

Saturated solution of Ag2S.

The Solubility Product Expression

Silver chloride is so insoluble in water (.0.002 g/L) that a saturated solution


contains only about 1.3 x 10-5 moles of AgCl per liter of water.

H2O
AgCl(s) Ag+(aq) + Cl-(aq)
Strict adherence to the rules for writing equilibrium constant expressions for
this reaction gives the following result.

(Water isn't included in the equilibrium constant expression because it is


neither consumed nor produced in this reaction, even though it is a vital
component of the system.)

The [Ag+] and [Cl-] terms represent the concentrations of the Ag+ and Cl-ions
in moles per liter when this solution is at equilibrium. The third term [AgCl]
is more ambiguous. It doesn't represent the concentration of AgCl
dissolved in water because we assume that AgCl dissociates into Ag+ions and
Cl- ions when it dissolves in water. It can't represent the amount of solid AgCl
in the system because the equilibrium is not affected by the amount of
excess solid added to the system. The [AgCl] term has to be translated quite
literally as the number of moles of AgCl in a liter of solid AgCl.

Since the [AgCl] term is a constant, which has no effect on the equilibrium, it
is built into the equilibrium constant for the reaction.

[Ag+][Cl-] = Kc x [AgCl]

This equation suggests that the product of the equilibrium concentrations of


the Ag+ and Cl- ions in this solution is equal to a constant. Since this constant
is proportional to the solubility of the salt, it is called thesolubility product
equilibrium constant for the reaction, or Ksp.

Ksp = [Ag+][Cl-]

The Ksp expression for a salt is the product of the concentrations of the ions,
with each concentration raised to a power equal to the coefficient of that ion
in the balanced equation for the solubility equilibrium.

Examples :

NaCl(s) Na+ + Cl-


NaCl(s) Na+ + Cl-

Ksp = [Na+][Cl-]

AgCl(s) Ag+ + Cl-

Ksp = [Ag+][Cl-]

PbCl2(s) Pb2+ + Cl-

PbCl2(s) Pb2+ + 2 Cl-

Ksp = [Pb2+][Cl-]2

DIFFERENCE b/w solubility product and Ksp:

The Relationship Between Ksp And the Solubility of a Salt

Ksp is called the solubility product because it is literally the product of the
solubilities of the ions in moles per liter. The solubility product of a salt can
therefore be calculated from its solubility, or vice versa.

Photographic films are based on the sensitivity of AgBr to light. When light
hits a crystal of AgBr, a small fraction of the Ag+ ions are reduced to silver
metal. The rest of the Ag+ ions in these crystals are reduced to silver metal
when the film is developed. AgBr crystals that do not absorb light are then
removed from the film to "fix" the image.

Example: Let's calculate the solubility of AgBr in water in grams per liter, to
see whether AgBr can be removed by simply washing the film.

We start with the balanced equation for the equilibrium.

H2O
AgBr(s) Ag+(aq) + Br-(aq)

We then write the solubility product expression for this reaction.

Ksp = [Ag+][Br-] = 5.0 x 10-13


One equation can't be solved for two unknowns the Ag+ and Br- ion
concentrations. We can generate a second equation, however, by noting that
one Ag+ ion is released for every Br- ion. Because there is no other source of
either ion in this solution, the concentrations of these ions at equilibrium
must be the same.

[Ag+] = [Br-]

Substituting this equation into the Ksp expression gives the following result.

[Ag+]2 = 5.0 x 10-13

Taking the square root of both sides of this equation gives the equilibrium
concentrations of the Ag+ and Br- ions.

[Ag+] = [Br-] = 7.1 x 10-7M

Once we know how many moles of AgBr dissolve in a liter of water, we can
calculate the solubility in grams per liter.

The solubility of AgBr in water is only 0.00013 gram per liter. It therefore
isn't practical to try to wash the unexposed AgBr off photographic film with
water.

Solubility product calculations with 1:1 salts such as AgBr are relatively easy
to perform. In order to extend such calculations to compounds with more
complex formulas we need to understand the relationship between the
solubility of a salt and the concentrations of its ions at equilibrium. We will
use the symbol Cs to describe the amount of a salt that dissolves in water.

APPLICATIONS:

If the solubility product for a compound is known then the solubility of a


compound can be calculated.

Ksp = [Ag+]2[S2-]
We then substituted the relationship between the concentrations of these
ions and the solubility of the salt into this equation.

[2 Cs]2[Cs] = 6.3 x 10-50

When they see this for the first time, students often ask: "Why did you
double the Ag+ ion concentration and then square it? Aren't you counting this
term twice?"

This question results from confusion about the symbols used in the
calculation. Remember that the symbol Cs in this equation stands for the
solubility of Ag2S in moles per liter. Since we get two Ag+ ions for each Ag2S
formula unit that dissolves in water, the Ag+ ion concentration at equilibrium
is twice the solubility of the salt, or 2 Cs. We square the Ag+ion concentration
term because the equilibrium constant expression for this reaction is
proportional to the product of the concentrations of the three products of the
reaction.

Ksp = [Ag+][Ag+][S2-]

It is just more convenient to write this equation in the condensed form.

Ksp = [Ag+]2[S2-]

Another common mistake in solubility product calculations occurs when


students are asked to write an equation that describes the relationship
between the concentrations of the Ag+ and S2- ions in a saturated Ag2S
solution. It is all too easy to look at the formula for this compound Ag2S
and then write the following equation.

[S2-] = 2 [Ag+]

This seems reasonable to some, who argue that there are twice as many
Ag+ ions as S2- ions in the compound. But the equation is wrong. Because two
Ag+ ions are produced for each S2- ion, there are twice as many silver ions as
sulfide ions in this solution. This solution is correctly described by the
following equation.

[Ag+] = 2 [S2-]
PURIFICATION OF COMMON SALT:

If HCL is passed through a saturated solution iof NaCl,the ionic product

[Na+] [Cl-] exceeds solubility product of NaCl thus pure solid NaCl is
precipitated

GROUp ANALYSIS:

For the precipitation of ionic metallic radicals use is made of the solubility
product principle.

COMMON ION EFFECT:

The dgree of ionization of an electrolyte is suppressed by the addition of a strong


electrolyte containing common ion. This effect is known as common ion effect.

In others words

The phenomena of lowering the degree of ionization of a weak electrolyte by adding


a solution of strong electrolyte having a common ion called common ion effect.

EXPLAINATION:
common-ion effect, decrease in solubility of an ionic salt, i.e., one that dissociates in
solution into its ions, caused by the presence in solution of another solute that contains one of
the same ions as the salt. The common-ion effect is an example of chemical equilibrium.

Example
silver chloride, AgCl, is a slightly soluble salt that in solution dissociates into the ions Ag+ and
Cl−, the equilibrium state being represented by the equation AgClsolidAg++Cl−. According to Le
Châtelier's principle, when a stress is placed on a system in equilibrium, the system responds
by tending to reduce that stress. In the system taken as an example, if another solute
containing one of those ions is added, e.g., sodium chloride, NaCl, which supplies Cl− ions, the
solubility equilibrium of the solution will be shifted to remove more Cl− from the solution, so
that at the new equilibrium point there will be fewer Ag+ ions in solution and more AgCl
precipitated out as a solid.

APLLICATIONS OF COMMON ION EFFECT:


PRECIPITATION OF THE
CATIONS OF GROUP II
Sulphides of basic radicals of groups II are
precipitated by passing H2S gas through the
acidified solution by HCl.
Ionization of H2S:
H2S 2H+ + S-2
Here HCl provides common ion H+ which shifts
the above equilibrium to the left as given by
Le-Chatelier's principle.
HCl H+ + Cl-
Addition of HCl suppresses the ionization of H2S
and lowers the concentration of S-2 ions, just
enough to exceeds the KSP of II group sulphides.
In this way only cations of group II are
precipitated as CuS, PbS, CdS etc. but
precipitation of the sulphides of group IV is
prevented because they have high KSPvalues as
compared to the sulphides of group II.
PRECIPITATION OF THE
CATIONS OF GROUP IV
Cations of groups IV are precipitated as
sulphides by passing H2S gas through the
solution in the presence of NH4OH.
Ionization of NH4OH:
NH4OH NH4+ + OH-
In this analysis NH4OH provides OH- ions which
combines with H+ ions of H2S to form H2O.
H2S 2H+ + S-2 : H+ +
OH- H2O
+
Removal of H ions from product side shifts the
equilibrium to right and the concentration of S-
2
increases which is enough to exceed the KSP of
the sulphides of group IV. In this way CoS, NiS
or ZnS can easily be precipitated.
PRECIPITATION OF THE
CATIONS OF GROUP IV
Cations of groups III are precipitated as
hydroxides by passing NH4OH in the presence of
NH4Cl. Here
NH4Cl provides common ion NH4+ which
suppresses the ionization of NH4OH.
NH4OH NH4+ + OH- : NH4Cl
+ -
NH4 + Cl
Common ion NH4+ shifts the equilibrium to left
side and the concentration of OH- ions decreases.
Under these circumstances, the KSP of the
hydroxides of Al, Fe and Cr is only exceeded and
they are precipitated as Al (OH)3, Fe (OH)3 and Cr
(OH)3 but the hydroxides of Zn, Ni and Co are not
precipitated as they have high values of KSP.
Complex formation:

When the metal ion is bonded to a group of surrounding molecules or ions are called
metal complexes or simply complexes. This phenomena is known as complex formation.
Some terms of complexes:
LIGANDS:

Ligands are the lewis bases attached to the metal in acomplex . an ion or the
molecule that coordinates to the metal atom or to ametal ion to form a complex is called a
ligand

CENTRAL METAL ATOM:

A metal or ion usually surrounded by anumber of ligands is called a central


central metal atom or ion .

COORDINATION SPHERE:

In forming a complex the ligands are said to be coordinated to the metal and the
ligand s bound to it constitute the coordination sphere of the complex

COORDINATION NUMBER:

The coordination number of metal atom in complex is the total number of bonds the
metal atom forms with ligands .

CHELATION:

The word chelation is derived from Greek χηλή, chelè, meaning claw; the ligands lie around the
central atom like the claws of a lobster.[2]

Chelation is the formation or presence of two or more separate coordinate bonds between
a polydentate(multiple bonded) ligand and a single central atom.[1]Usually
these ligands are organic compounds, and are called chelants, chelators, chelating agents, or
sequestering agents.

The ligand forms a chelate complex with the substrate. Chelate complexes are contrasted
withcoordination complexes composed of monodentate ligands, which form only one bond with
the central atom.