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physical processes : Solid -liquid, liquid - gas and solid - gas equilibria, Henry’s law, general characteristics of equilibrium involving physical processes. Equilibria involving chemical processes : Law of chemical equilibrium, equilibrium constants (K p and Kc ) and their significance, significance of ΔG and ΔGº in chemical equilibria, factors affecting equilibrium concentration, pressure, temperature, effect of catalyst; Le Chatelier’s principle. Ionic equilibrium : Weak and strong electrolytes, ionization of electrolytes, various concepts of acids and bases (Arrhenius, Bronsted - Lowry and Lewis) and their ionization, acid - base equilibria (including multistage ionization) and ionization constants, ionization of water, pH scale, common ion effect, hydrolysis of salts and pH of their solutions, solubility of sparingly soluble salts
and solubility products, buffer solutions.
CHEMICAL EQUILIBRIA
It is established in chemical reaction
Ex. N2 + 3H2 2NH3(g) N2(g) + O2(g) 2NO(g)
The state of equilibrium is a state in which the measurable properties of the system do not undergo any noticeable change under a particular set of conditions.
LAW OF MASS ACTION
According to Guldberg and Waage, “The rate of a chemical reaction is directly proportional to the product of active masses of the reactants”.
Active mass of reactant = [mole L–1]
Since, active mass = Concentration of reactant × Activity coefficient.
= Molarity × γ
For dilute solution; γ = 1
EQUILIBRIUM CONSTANT (K) IN TERMS OF CONCENTRATION AND PRESSURE (KC & KP)
CHAPTER INCLUDES
Chemical Equilibria
Law of Mass Action
Equilibrium Constant (K)
Relationship
between K p and Kc
Le–Chatelier's Principle
Ionic Equilibrium
Acids–Bases
pH scale
Buffer Solutions
Salt Hydrolysis
KC =
Molar concentration of product or multiplication of molar concentrations of products with stoichiometric quantity as a power
Molar concentration of reactant or multiplication of molar concentrations of reactants with stoichiometric quantity as a power
Solubility Product
KP =
Partial pressure of gaseous product or multiplication of partial pressures of gaseous products with stoichiometric quantity as a power
Partial pressure of gaseous reactant or multiplication of partial pressures
Note : For liquids and solids, the partial pressure is taken to be unity.
RELATIONSHIP BETWEEN KP AND KC
K = K (RT)Δng
where
Δ n g = np – nr
= no of moles of gaseous product – no. of moles of gaseous reactant.
if Δng = 0; Kp = Kc ;
Example :
N2(g) + O2(g)
2NO(g).
if Δng > 0; Kp > Kc ;
Example :
PCl5(g)
PCl3(g) + Cl2(g)
if Δng < 0; Kp < Kc ;
Unit of Kp and Kc
Unit of Kp = (atm)Δng
Example :
N2 (g) + 3H2 (g) 2NH3(g)
Unit of Kc = (mol L−1)Δng
If Δng = 0,
no unit of Kp and Kc
Relation between degree of dissociation ( α ) and Vapour density
For equilibrium reaction
PCl5 (g) PCl3 (g) + Cl2 (g)
N2O4(g) 2NO2(g)
For (i) & (ii) n = 2
D = vapour density of the gas before dissociation = molecular weight/2 d = vapour density of equilibrium mixture
n = total no. of moles obtained after dissociation from 1 mole of dissociating molecule.
Relation between Equilibrium Constant (K) and Standard free energy Change (ΔG°)
LE-CHATELIER’S PRINCIPLE
It states that, if a system in equilibrium is disturbed by any external agency such as pressure, temperature, concentration etc. then equilibrium will get shifted to counter balance the effect of that disturbance.
Factors affecting Equilibrium
Concentration
Addition of any reactant or removal of products leads to forward reaction or vice-versa.
Temperature
In an endothermic reaction (ΔH= + ve) increase in temperature favours the forward reaction, while decrease in temperature favours backward reaction.
For exothermic reaction (ΔH= − ve) increase in temperature favours backward reaction, while decrease in temperature favours forward reaction.
Pressure
Effect of pressure is mainly applicable to gaseous reactions, since liquids & solids are incompressible in nature.
If Δng = 0
Δng > 0
pressure has no effect on equilibrium constant.
then on increasing pressure, equilibrium will get shifted in the backward direction.
Δng < 0 then on increasing pressure, equilibrium will shift towards forward direction.
Catalyst
A catalyst has no effect on state of equilibrium but it enables the state of equilibrium to reach very quickly.
Inert gas
The introduction of inert gas to any equilibrium is visualized under the condition of constant volume and constant pressure.
at constant volume
If Δng = 0
Δng > 0
Δng < 0
no effect on equilibrium on addition of inert gas
at constant pressure
If Δng = 0 no effect on equilibrium
Equilibrium will get shifted in that direction where no. of moles are more.
if Δng > 0⎪⎫ In forward direction
⎬
Δng < 0⎪ In backward direction
Example :
Δng > 0
PCl5 (g) PCl3 (g) + Cl2 (g)
Example:
Δng < 0
2SO2(g) +O2 (g) 2SO3 (g)
IONIC EQUILIBRIUM
Dissociation of weak acids or weak bases and Ostwald dilution law
When weak acid or weak base is dissolved in aqueous medium equilibrium exists between dissociated ions and undissociated molecules.
CH3COOH CH3COO– + H+
Initially C 0 0
At equilibrium C (1-α) Cα Cα where α the degree of dissociation
∴ Ka
= Cα ⋅ Cα = Cα2
C(a − α)
or
[If α << 1]
and
Similarly for weak base
or
ACIDS AND BASES
Arrhenius Concept :
An acid is a substance which furnishes H+ ions in aqueous solution HCI H+ + CI– strong acid
CH3COOH CH3COO– + H+ weak acid
A base is a substance which furnishes OH– ions in aqueous solution NaOH Na+ + OH– strong base
NH4OH NH + + OH– weak base
The strength of an acid depends upon its tendency to furnish H+ or OH– ions in solution.
Bronsted – Lowry Concept :
An acid is a proton donor while base is a proton acceptor. NH3 + H2O NH + (aq) + OH– (aq)
base1 acid2 acid1 base2
A pair of acids and bases which differ by a proton is known as conjugate pair of acid and base.
Stronger is the acid, weaker is its conjugate base and vice versa.
The strength of acids (or bases) also depends upon the tendency of base (or acid) which accept proton.
Lewis Concept :
An acid is an electron pair acceptor.
(c) A base is an electron pair donor.
EXPRESSING HYDRONIUM ION CONCENTRATION–pH SCALE
pH is
A scale for measuring acidity of a solution.
Mathematically pH = –log [H+]
= –log [H3O+]
Similarly pOH is defined as
A scale for measuring basicity of a solution pOH = – log [OH–]
BUFFER SOLUTIONS
A Solution whose pH remains constant either on keeping for a longer period or by the addition of small quantity of some external electrolyte (i.e. an acid or a base) is known as Buffer solution.
Types of Buffer Solutions
Acidic buffer : A mixture of weak acid and its salt with a strong base form acidic buffer. e.g.
CH3COOH + CH3COONa HCOOH + HCOONa C6H5COOH +C6H5COONa
Basic buffer : It is a mixture of
Ex. (1) NH4OH + NH4Cl
Cu(OH)2 + CuCl2
Mg(OH)2 + MgSO4
∴ pH= 14 – pOH
⎛
= 14 – ⎜pKb + log
⎝
[Salt] ⎞
⎟
[base] ⎠
⎛
pH = pKw – ⎜pKb + log
[Salt] ⎞
⎟
[base] ⎠
SALT HYDROLYSIS
Consider the salt BA, which on hydrolysis will give acid and base inside the aqueous solution.
BA + H2O BOH + HA
Salt made up of strong acid, strong base will not hydrolyse it will simply ionise. And pH of aqueous solution will be neutral. The pH of aqueous solution is independent with dilution i.e., pH = 7. e.g., NaCl, Na2SO4.
Salt made up strong acid and weak base will hydrolyse. e.g., NH4Cl.
pH =
1
2 [pKw – pKb – logC]
Salt made up of weak acid and strong base. e.g., CH3COONa.
1
pH = 2 [pKw + pKb + logC]
Salt made up of weak acid and weak base. The pH of these salt solution depends on Ka and Kb but independent with concentration. e.g., CH3COONH4.
1
pH = 2 [pKw – pKb + pKa]
SOLU
When a sparingly soluble salt is dissolved in water they form saturated solution but concentration of salt is very low. Therefore in saturated solution of such electrolytes, solid electrolyte is in equilibrium with the ions as represented below:
AgCl
KH
Note : KH = Ch2, h =
C , where h = degree of hydrolysis.
BILITY PRODUCT
Ag+ + Cl–
Applying Law of chemical
[Ag+ ] [Cl− ]
K =
[AgCl]
K[AgCl] = [Ag+] [Cl–]
K sp = [Ag+ ] [Cl− ]
where Ksp is a constant known as solubility product. It remains constant at constant temperature for a given salt and defined as the product of ionic concentration of a sparingly soluble electrolyte in a saturated solution.
if Ksp = I.P. (Ionic product) then solution is said to be saturated if Ksp > I.P. then solution is said to be unsaturated
if Ksp < I.P. then solution is said to be supersaturated (Condition for precipitation)
Relation between Solubility and Solubility Product
For binary electrolyte; Ksp = s2 (AgCl, AgBr) for ternary electrolyte;
Ksp = 4s3 (CaF2, BaCl2) for Quarternary Electrolyte;
Ksp = 27s4
❑ ❑ ❑
PHYSICS-15-10- 11th (PQRS) SOLUTION
XI (PQRS) PHYSICS REVIEW TEST-5 Select the correct alternative. (Only one is correct) [15 × 3 = 45] There is NEGATIVE marking. 1 mark will be deducted for each wrong answer. Q.31 Two trains, which are moving along different tracks in opposite directions towards each other, are put on the same track due to a mistake. Their drivers, on noticing the mistake, start slowing down the trains when the trains are 300 m apart. Graphs given below show their velocities as function of time as the trains slow down. The separation between the trains when both have stopped, is: (A) 120 m (B) 280 m (C) 60 m (D*) 20 m 1 [Sol: x1 = 2 1 × 10 × 40 = 200 m; x2 = – 2 × 8 × 20 = –80 m xreletive = x1 + x2 = 280 separation = 300 – 280 = 20 m (D) ] Q.32 One end of a thin uniform rod of length L and mass M is riveted to the centre of a uniform circular disc of radius r and mass 2 M so that the rod is normal to the disc. The centre of mass of the combination from the centre of the disc is at dist
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