Formula sheet of
Ionic equilibrium
1. Introduction of Electrolytes
a. Definition and Classification of electrolytes
(A) Weak acid: all organic acids
Inorganic Acid:
(B) Weak base:
NH4OH,
(c) Salt of weak acid and weak base:
CH3COONH4, HCOONH4
(d) Salt of strong acid and weak base:
NH4Cl, NH4NO3, etc.
(e) Salt: Strong base + weak acid
2. Classification of acids and bases
a. All theories of acids and bases
Acid-base concept:
Arrhenius acid: Those molecules or ions which are soluble in polar solvent and further dissociated to give
H+ ion concentration.
Example:
Arrehenius Base:
Those molecules or ions which are soluble in polar solvent and further dissociate to give OH- ion
concentration.
Example:
Bronsted Lowry Acid-Base Concept
Acid: Those molecules or ions which donates H+ ion concentration to other molecule or ion in aqueous
medium.
Base: Those molecules or ions which accepts H+ ion concentration from acid.
This concept is based on acid-base conjugation.
Lewis acids and bases are described by the Lewis theory of acid-base reactions as electron-pair acceptors and
electron pair donors respectively. Therefore, a Lewis base can donate a pair of electrons to a Lewis acid to
form a product containing a coordinate covalent bond. This product is also referred to as a Lewis adduct. An
illustration detailing the reaction between a Lewis acid and base leading to the formation of a coordinate
covalent bond between them is given below.
Lewis acids and bases are named after the American chemist Gilbert Newton Lewis, who also made invaluable
contributions in the fields of thermodynamics and photochemistry.
3. Ionisation of water
a. Ionic product of water
About H2O:
In water auto-provocation or auto-protolysis occur between H2O molecules. Due to this the following
equilibrium is established.
4. pH scale
a. Introduction of pH and pOH in aqueous solution
pH- It is defined as the strength of acid and. It is negative logarithmic value of H+(Hydrogen ion) concentration
for dilute solution.
pOH: It is defined strength of base and it is negative logarithm value of OH- (hydroxyl ion) concentration for
dilution.
5. Calculation of pH
a. Aqueous solution of strong acid or strong base and its combination
Case l : For acid solution
Case II: For neutral solution
Case III : For basic solution
b. pH calculation in case of dilution and mixing of aqueous solution
pH on dilution
For H+
pH on mixing
In general
c. Ostwald dilution law for weak acid and weak base
OSTWALD'S DILUTION LAW
According to Arrhenius theory of electrolytic dissociation, the molecules of an electrolyte in solution are constantly splitting into ions and the ions are
constantly reuniting to form unionized molecules. Therefore, a dynamic equilibrium exists between ions and unionized molecules of the electrolyte in
solution. It was pointed out by Ostwald that like chemical equilibrium, law of mass action can be applied to such systems also.
Consider a binary electrolyte AB which dissociates into A+ and B- ions and the equilibrium state is represented by the equation:
So, dissociation constant may be given as:
For very weak electrolytes,
Concentration of any ion
d. Common ion effect
Case-3 Weak electrolyte + Weak electrolyte
e. Polyprotic acid and base
6. Salt hydrolysis
a. Introduction and salt of weak acid and strong base
SALT HYDROLYSIS
It is defined as a reaction in which the cation or anion or both of a salt react with water produce acidity
or alkalinity.
As the nature of the cation or the anion of the salt determines whether its solution will be acidic or basic. It is
proper to divide the salts into four categories.
(i) Salt of a strong acid and a weak base. Examples: FeCl3, CuCl2, AICI3, NH4Cl, CuSO4, etc.
(ii) Salt of a strong base and a weak acid. Examples: CH3COONa, NaCN, NaHCO3, Na2CO3, etc.
(iii) Salt of a weak acid and a weak base. Examples: CH3COONH4, (NH4)2CO3, NH4HCO3, etc.
(iv) Salt of a strong acid and a strong base. Examples: NaCl, K2SO4, NaNO3, NaBr, etc.
Salt of a weak acid and a strong base
b. Salt of strong acid and weak base
Salt of a strong acid and a weak base
The solution of such a salt is acidic in nature. The cation of the salt which has come from weak base is
reactive. It reacts with water to form a weak base and H+ ions
c. Salt of weak acid and weak base
Salt of a weak acid and a weak base
Maximum hydrolysis occurs in the case of such a salt as both the cation and anion are reactive and react with
water to produce H+ and OH- ions. The solution is generally neutral but it can be either slightly acidic or slightly
alkaline if both the reactions take place with slightly different rates. Consider, for example, the salt
CH3COONH4. It gives CH3COO- and NH 4+ions in solution.
d. Amphiprotic salt
Let us consider hydrolysis of amphiprotic anion only, i.e., when counter cation is not hydrolysed. Example of
some salts of this category are NaHCO3, NaHS, Na2HPO4, NaH2PO4.
7. Buffer solution
a. Introduction of buffer solution and acidic buffer
A solution whose pH is not altered to any great extent by the addition of small quantities of either an acid (H+
ions) or a base (OH-ions) is called the buffer solution. It can also be defined as a solution of reserve acidity or
alkalinity which resists change of pH upon the addition of small amount of acid or alkali.
General Characteristics of a Buffer Solution
(i) It has a definite pH, i.e., it has reserve acidity or alkalinity.
(ii) Its pH does not change on standing for long.
(iii) Its pH does not change on dilution.
(iv) Its pH is slightly changed by the addition of small quantity of an acid or a base.
This is known as Henderson's equation
b. Basic buffer
Basic buffer:
It consists it is of a weak base and its salt with strong acid. Ionisation of a weak base, BOH, can be
represented by the equation,
Knowing pOH, pH can be calculate by the application of the formula
pH + pOH = 14
c. Buffer action and buffer capacity
BUFFER CAPACITY
It is defined as (amount) moles of strong acid or strong base is added to 1 liter of Buffer solution to change its
pH by unity Let there be a buffer solution of volume 1 L with 'b' mole of salt and 'a' mol of acid. The pH of the
buffer would be given by
Maximum Buffer Capacity
It can be proved that the maximum buffer capacity is achieved when the salt and acid or base concentration is
equal. Differentiating buffer capacity with respect to 'b', the amount of salt present in and equating it to zero,
gives
It is difficult to give an exact limit upto which a buffer can be used. It is generally accepted that solution has
useful buffer capacity provided that the value of [Salt] / [Acid] lie within the range of 0.1. Therefore, the pH
range of a buffer solution is generally specified as
8. Indicators
a. Acidic and basic indicators and its function
For a distinct colour, usually it is assumed that one form of indicator must be at least ten times the other form:
9. Acid-base titrations
a. Titration curves
10. Solubility product
a. Introduction and Calculation of Ksp
At constant temperature;
In general,
b. Effect of adding common ion
11. Precipitation
a. Simple precipitation and condition of precipitation
Selective precipitation:
b. Application in qualitative analysis
12. Complex Equilibrium
a. Formation of complex ion and formation constant
The Formation Constant
The replacement of water molecules from [Cu(H2O)6]2+ by ammonia occurs in sequential steps. Omitting the
water molecules bound to Cu2+ for simplicity, we can write the equilibrium reactions as follows:
The sum of the stepwise reactions is the overall equation for the formation of the complex ion: The hydrated
Cu2+ ion contains six H2O ligands, but the complex ion that is produced contains only four NH3 ligands, not six.
The equilibrium constant for the formation of the complex ion from the hydrated ion is called the formation
constant (Kf). The equilibrium constant expression for Kf has the same general form as any other equilibrium
constant expression. In this case, the expression is as follows:
The Effect of the Formation of Complex Ions on Solubility
The magnitude of the equilibrium constant indicates that almost all Ag+ ions in solution will be immediately
complexed by thiosulfate to form [Ag(S2O3)2]3−. We can see the effect of thiosulfate on the solubility of AgBr by
writing the appropriate reactions and adding them together:
13. Miscellaneous Problems
a. Solubility Vs Buffer and Solubility Vs Hydrolysis
Solubility v/s Buffer
for monoprotic
For diprotic:
Solubility V/s salt hydrolysis