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CHAPTER

7 Chemical Equilibrium

Chemical Equilibrium Application of KC or KP

Consider a reversible reaction, ™ More is the value of K P or K C more is the extent of

aA + bB   r reaction.
 cC + dD
f

r b
™ Stability of reactant increases when value of K decreases.
At Equilibrium State ™ Stability of Product increases when value of K increase.
Rate of forward reaction (rf) = rate of backward reaction (rb)
Characteristics of Equilibrium Constant
So, at equilibrium,
Predicting the direction of reaction: Reaction Quotient (Q) is
[C]c [D]d K f
KC = = In terms of active mass expressed in the same way as for equilibrium constant, except that
[A]a [B]b K b
the concentrations may not necessarily be at equilibrium.
[PC ]c [PD ]d In general for the reversible reaction:
KP = In terms of partial pressure
[PA ]a [PB ]b aA + bB  cC + dD
c d
[X C ] [X D ] [C]c [D]d
KX = In terms of mole fraction Q=
[X A ]a [X B ]b [A]a [B]b
KP = KC(RT)Dng = KXPDng [PC ]c [PD ]d
Q= (in terms of pressure)
While determining Dng take only gaseous species. [PA ]a [PB ]b
The active mass of solid & pure liquid is a constant quantity
If Q = Keq then system is in equilibrium
(unity) because it is an intensive property.
If Q > Keq then system proceed in backward direction to attain
Graphs equilibrium.
If Q < Keq then system proceed in forward direction to attain
Concentration

Concentration

Product
Product
equilibrium.
Reactants
Reactants Degree of dissociation (a)
Time Time No. of moles of reactant dissociated
α=
No. of mole of reactant present initially
+ve catalyst –ve catalyst
rf Le-chatelier’s Principle
Concentration
Equilibrium
State r1 = rb

If a system at equilibrium is subjected to a change of any one of

Rate

the factors such as concentration, pressure or temperature then

rb Product
the equilibrium is shifted in such a way as to nullify the effect
Time Time
of change.
Unit of Equilibrium constant Le-Chatelier’s principle is applicable for both chemical and
   KC = (mol L–1)Dng; KP = (atm)Dng physical equilibrium.
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Chemical Equilibrium
Dng = 0 Dng > 0 Dng < 0
Effect due to change in
AB A2B 2AB
Concentration (i) ↑ [A] Forward direction Forward direction Forward direction

(ii) ↓ [A] Backward direction Backward direction Backward direction

Pressure (i) ↑ in pressure Unchanged Backward direction Forward direction

(ii) ↓ in pressure Unchanged Forward direction Backward direction

Temperature (i) ↑ in Endothermic Forward direction Forward direction Forward direction

(ii) ↑ in Exothermic Backward direction Backward direction Backward direction

Dissociation (i) ↑ in pressure Unchanged Dissociation Dissociation
Decreases Increases
(ii) ↑ in volume Unchanged Dissociation Dissociation
Increases Decreases
Mixing of inert gas (i) at constant P Unchanged Dissociation Dissociation
Increases Decreases
(ii) at constant V Unchanged Unchanged Unchanged

Relationship between Equilibrium Constant K, Reaction Quotient Q and Gibbs Energy G

DG = DG° + RT ln Q …(i) where, DG° = Standard free energy difference between the products and reactant, T = Absolute temperature
in kelvin, R = Universal gas constant.
At equilibrium, when DG = 0 and Q = Kc, then equation (i) becomes
0 = DG° + RT ln Kc or DG° = –RT ln Kc or ln Kc = (–DG°/RT)
Case I: If DG° < 0, then (–DG°/RT) is positive, i.e., e(–DG°/RT) > 1 hence Kc > 1, which implies a spontaneous reaction, i.e., the reaction
proceeds in the forward reaction.
Case II: If DG° > 0, then (–DG°/RT) is negative, i.e., e(–DG°/RT) < 1, hence Kc < 1, which implies a non-spontaneous reaction or the
reaction proceeds in the forward direction to a very small extent i.e., only a very small quantity of product is formed.

Ionic Equilibrium
ACID BASE

Strong Weak Strong Weak

HClO4 HClO3 H2CO3 Group-1 hydroxide All other bases

HI HClO2 HNO2 except-LiOH like
HBr HClO H2SO3 NaOH NH4OH
KOH
H2SO4 H3PO4 HCN Zn(OH)2
RbOH
HCl H3PO2 H3BO3 Group-2 hydroxide Al(OH)3
HNO3 H3PO2 HF except Be(OH)2 Fe(OH)3
H 2S Almost all and Mg(OH)2 Cu(OH)2
organic acid **Ca(OH)2 etc.
Like: acetic acid Sr(OH)2
oxalic acid
Ba(OH)2

Acid Base Theories (Arrhenius Concept)

Acid Base
Which produce H+ ion in aqueous solution. e.g. HCl, H2SO4, Which produce OH– ion in aqueous solution. e.g. NaOH,
HClO4, H3PO4, CH3COOH but H3BO3 is not an Arrhenius acid. Mg(OH)2, Ba(OH)2
Major Limitation: Defined only in water solvent.

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Bronsted – Lowry Concept

Acid: Which gives H+ in any solvent. ™ To find conjugate base of any Acid → Remove one H+
Base: Which accepts H+ in any solvent ™ To find conjugate acid of any Base → add one H+
™ Water is Amphiprotic solvent (can accept as well as lose H+)
HCl + NH3  Cl– + NH4+
Acid Base Conjugate Conjugate H2O  H+ + OH–
Base Acid
H2O + H+  H3O+
Major Limitation: Does not explain acidic behaviour of aprotic
acids e.g. SO2, CO2, AlCl3, SiCl4

Lewis Theory
Acid Base
Types of Lewis Acid Types of Lewis Base
Lewis acid is an electron pair acceptor. Lewis base is an electron pair donor.
1. Having Incomplete octet: 1. Neutral molecule having lone pair
.. .. ..
BF3, BCl3, B(OH)3, AlCl3 etc. N
.. H..3, R–NH2,..R2–NH,
H–O .. –H, R – O
.. – R etc.
2. Having vacant d-orbitals: 2. Anions:
SF4, SF6, SnCl2, SnCl4 etc. O2–, SO42–, CO32–, Cl–, Br–, I–, CH3COO– etc.
™ All the Lewis bases are Bronsted bases but all the Lewis
3. Having multiple bonds between atoms of different EN:
CO, SO2, SO3 etc. acids are not Bronsted acids.
™ All Arrhenius acids are Bronsted acid but it is not so
4. Cations for bases.
Ag+, Li+, Al+3, Mg2+
False cations (which cannot act as Lewis acid):]
NH4+, H3O+, PH4+ etc.

OstwalD’s Dilution Law

OSTWALD’S DILUTION LAW FOR PURE WATER
(Only for weak electrolytes) 1. [H+]
= [OH–]
a ∝ dilution dilution ↑ ⇒ a ↑ 2. pH = pOH
Explanation of water pK w
H2O  H+ + OH– 3. (pH)pure water =
2
Kw = Ionic product of water  pH of an acidic solution is always less than pH of pure
pKw = pH + pOH water.
Kw = dissociation constant of water  pH of a basic solution is always greater than pH of pure
Kw water.
K = [H O] [[H 2 O] = 55.5]
2

Hydrolysis of Salts
Salt Hydrolysis Resulting Hydrolysis constant Degree of pH
solution (Kh) hydrolysis (h)
Weak acid and Anionic Alkaline kw / ka 11
Kh pH==
pH [pK
[pKw w++pK
pKa a++log
logC]C]
Strong base pH > 7 h=
C 22
Strong acid and Cationic Acidic kw / kb 1
Kh pH = [pK w – pK b – log C]
Weak base pH < 7 h=
C 2

Weak acid and Anionic and Neutral, kw / (ka . kb) 1

h = Kh
Weak base Cationic both pH = 7 pH
= [pK w + pK a – pK b ]
2
(If Ka = Kb)

P
W Equilibrium 19
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Buffer Solutions Ksp = [Ag+] [Cl–]

The solutions which resist change in pH on dilution or with the Ksp depends only on temperature.
addition of small amounts of acid or alkali are called buffer Expressions of Ksp : AxBy  xAy+ + yBx–
solutions.
General form Ksp = [Ay+]x [Bx–]y
Buffers are classified into two categories:
™ Simple buffers: These are the solutions of salts of weak acid
In terms of ‘S’: Ksp = (xS)x (yS)y = xx⋅yy⋅S(x+y)
and weak base. For example, CH3COONH4 (ammonium Ionic Product [Qsp]
acetate).
™ Mixed buffers: These are the mixtures of two solutions.
AxBy  xAy+ + yBx– ; Qsp[Ay+]x [Bx–]y
These are further of two types: In Qsp the concentration taken are at any time but in Ksp the
 Acidic buffers: These are the solutions of mixtures of concentration are at equilibrium time/saturation time.
weak acid and salt of this weak acid with strong base. For Application
example, CH3COOH + CH3COONa. They have pH value
1. If Qsp < Ksp [unsaturated]
lesser than 7.
 Basic buffers: These are the solutions of mixtures of
2. If Qsp = Ksp [saturated]
weak base and salt of this weak base with strong acid. 3. If Qsp > Ksp [super saturated/ppt. will form]
For example, NH4OH + NH4Cl. They have the pH value
Effect of Common Ion
more than 7.
Presence of common ion decreases the solubility but has no effect
™ pH of an acidic buffer: on Ksp as it depends only on temperature.
[Salt] [Conjugate base]
pH = pKa + log = pKa + log Effect of Odd Ion
[Acid] [Acid]
Presence of odd ion increases the solubility but has no effect
™ pH of a basic buffer: on Ksp.
[Salt]
pOH = pKb + log = pKb + log [Conjugate acid] Acid-base Titration
[Base] [Base]
Type of pH range
No. of moles of acid or base added Suitable indicators
titration of titration
per litre of buffer
Buffer capacity =
Change in pH SA/SB 3-11 All indicators (MeOH, HPh etc.)
The range of pH over which the buffer solutions remain effective
is called buffer range. Methyl orange (MeOH) and methyl
SA/WB 3-7
Buffer Buffer range in pH red
Acidic pKa ± 1
Basic (pKw – pKb) ± 1 WA/SB 7-11 Phenolphthalein (HPh)

Solubility (s) & Solubility Product (Ksp) WA/WB 6.5-7.5 Phenol red
Solubility
Key Tips
The maximum amount of solute that can be dissolved in a particular
amount of solvent at a given temperature is called solubility(s). It No. of moles of acid/base added per litre
™ Buffer capacity =
is generally expressed in molarity. change in pH of buffer solution
AgCl(s)  AgCl(aq) → Ag+ + Cl– ™ Maximum buffer action when [salt] = [acid]
dissolution dissociation
™ pH of Amphiprotic species: (NaHPO4, NaHCO3) which can
Solubility Product (Ksp) pKa1 + pKa 2
donate as well as accept H+; pH =
AgCl  Ag+ + Cl– 2

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