Equilibrium

Equilibrium and its dynamic nature

• Equilibrium is the state at which the concentration of reactants and
products do not change with time
• N2(g) + 3H2(g) 2NH3(g)
• what are the factors which can affect the --- The amount of reactants
left------
• Experimental conditions
• Concentration, pressure,temperature, nature of reaction
• Which are three type of extent in the above reaction
• The chemical reaction which proceed nearly to completion , only
negligible quantity of reactant is left
• Small amount of product is left, most of the reactants kept unchanged
• Concentration of reactants and products are comparable
• So state of chemical equilibrium – classified into three –depending on
the extent of reaction
• How can you control the extent of reaction ?????
State of equilibrium
• What is meant by state of equilibrium ?????
• Macroscopic level: nothing is happening
• Molecular level: continuous change
• N2(g) + 3H2(g) 2NH3(g)--- the important aspect of equilibrium
system is reversibility
• Rate of backward reaction= rate of forward reaction
• Microscopic level- the system is in motion –Dynamic in nature – but
no apparent change
Physical and chemical equilibrium

•One example for each

equilibrium????
Equilibrium

• Physical equilibrium: equilibrium set up in physical process is called

physical equilibrium
• Eg: evaporation of water to steam
• Chemical equilibrium: the equilibrium set up in chemical processes
• Decomposition of calcium carbonate
Equilibrium in physical processes
Equilibrium in Physical Process - Solid liquid Equilibrium – YouTube
No change in the mass of ice or water-as long as the temperature
remains constant
Number of molecules going from ice to water=water to ice
Rate of melting=rate of freezing
The temperature at which the solid and liquid phases are at equilibrium
at atmospheric pressure is called the normal freezing point or melting
point of that substance
• At equilibrium
• Both the processes of melting and freezing occur simultaneously
• Both the processes occur at the same rate so that the amount of
substance on both the sides become constant
Liquid-vapour(or gas) equilibrium
• Liquid Gas Equilibrium – YouTube
• At initial stage: mercuric level in the two limbs of the manometer will
be the same
• As evaporation continues, the pressure goes on increasing, the level in
the right hand limb starts rising
• After some time, pressure becomes constant – no more water is
evaporating even though some liquid water is still present
• Explain the molecular processes
• Rate of evaporation=Rate of condensation
• The pressure exerted by the vapours in the equilibrium with the liquid at a
particular temperature is called equilibrium vapour pressure or vapour
pressure of the liquid
• With the increase in temperature , the vapour pressure increases and is
independent of the amount of water present
• Equilibrium cannot be attained in an open vessel.
• For a liquid at atmospheric pressure , the temperature at which the liquid
and vapours are at equilibrium, is called boiling point of the liquid
• Boiling point depends upon the atmospheric pressure
• At high altitudes boiling point decreases
Solid- gas (or vapour) equilibrium
• Solid –gas equilibrium exists in systems where solid sublimes to
vapour
• Iodine Crystal Sublimation – YouTube
• Rate of sublimation of solid I2 to form vapour= rate of condensation of
I2 vapour to solid
Equilibrium- dissolution of solids in liquids
and gases in liquids
• Solids in liquids
• Dissolution of sugar in water(273 K)
• How will you prepare (i) unsaturated solution (ii) saturated solution
• At saturation, rate of dissolution of sugar will be equal to the rate of
crystallization of sugar
•
• Gases in liquids
• CO2 dissolved in soda water
• A state of equilibrium exists between the molecules in the
gaseous state and the molecules dissolved in the liquid
• The stability of gas in liquid depends on the pressure
• The dependence of the solubility of a gas and its pressure
above the solvent is given by Henry’s law
• Henry’s law : the mass of a gas dissolved in a given mass of a solvent
at a particular temperature is proportional to the pressure of the gas
above the solvent
• mαp
• m=kp
• Can you explain fizzing out of a soda bottle in terms of Henry’s law?
• Solubility of a gas in a liquid decreases with increase in temperature
Expression which acquire constant value at
equilibrium
Process Expression which acquire constant value at
equilibrium

Liquid vapour Pressure of the vapour above the liquid becomes

H2O(l) H2O(g) constant at a particular temperature (pH2O is
constant)

Solid liquid Two phases can coexist only at a definite temperature

H2O(s) H2O(l) (melting point or freezing point)at
1atm(1.013bar)pressure.(melting point at constant
pressure)
Solute(s) solute(solution) Concentration of solute in solution is constant a given
Sugar(s) sugar(in solution) temperature
Concentration of sugar(in solution)at constant
temperature
Gas(g) gas(aq) (gas(aq)/gas(g)) is constant at a given temperature
CO2(g) CO2(aq) Ratio of concentration of CO2(aq) and CO2(g)at
constant temperature
General characteristics of physical equilibria
• The measurable properties of the system become constant at equilibrium
• Equilibrium can be established only in case of closed system
• At equilibrium both the opposing processes occur at the same rate , ie
equilibrium is dynamic
• When equilibria is attained, there exists an expression of concentrations
of the substances involved in equilibrium which becomes constant at a
given temperature
• The magnitude of the constant value of the concentration related
expression (equilibrium constant)gives an indication of the extent to
which the reaction proceeds before acquiring the equilibrium
Equilibria involving chemical systems
• Reversible reactions are the reactions in which the products formed
can also react with one another under suitable conditions to give back
the reactants
• H2(g) + I2(g) 2HI(g)
• N2(g) +O2(g) 2NO(g)
• PCl5(g) PCl3(g) +Cl2(g)
• The chemical reactions in which the products formed do not combine
to give back the reactants are known as irreversible reactions
• 2KClO3-2KCl +3O2
• In the case of irreversible reaction, chemical equilibria can be attained
even though some starting material is left
• Reversible reactions go to completion and no starting material are left
 Chemical equilibria
• Decomposition of calcium carbonate :heating at 1073 K  CaO and CO2
Chemical equilibria
• Combination hydrogen and iodine: when hydrogen gas and iodine
vapours are heated in a closed vessel at a constant temperature ,
717K , the two reacts to form hydrogen iodide
• State in which the measurable properties of the system (pressure,
density, colour or concentration ) do not undergo any further
noticeable change under given set of conditions is said to a state of
equilibrium
Attainment of equilibrium
• A+B C+D
• At the start of the experiment, the reactants A and B are present in the
definite concentrations
• As the rection proceeds, effective collision - products
• A+B - C+D, forward reaction
• With the passage of time, the concentration of the reactants decreases
while those of the products increases
• Since it is a closed system, products will react together - reactants
C+D-- A+B, backward reaction
• An equilibrium state will reach when rate of forward reaction will be
equal to rate of backward reaction
• Same state equilibrium will reach, if we start with C and D, when no A
and B are present initially
• Equilibrium can be attained from either direction.
Characteristics of chemical equilibria
• chemical equilibrium is dynamic in nature: explain the dynamic
nature of chemical equilibria by taking the example of formation and
decomposition of HI
• Demonstration of dynamic nature of chemical equilibrium: synthesis
of ammonia by Haber’s process
• 2. the properties of the system become constant at
equilibrium and remain unchanged thereafter
• Eg: in the decomposition of CaCO3, pressure becomes
constant
• 3. equilibrium can be attained only when the system is closed
• 4. the equilibrium can be approached from either direction
• Equilibrium between nitrogen tetraoxide(colourless at 273K) and
nitrogen dioxide, a reddish brown gas at 373 K
• N2O4(g) 2NO2(g)
• At very low temperature, 273K, N2O4 is stable and exists as pure
colourless gas
• At 298K, two gases exist as equilibrium mixture having pale brown
colour
• At 373K, it decomposes completely to NO2 – dark brown in colour
• The Effect of Temperature on Equilibrium - N2O4 to 2NO2 - YouTube
• 5. a catalyst does not alter the equilibrium point: in a reversible
reaction, a catalyst increases the rate of forward as well as the
backward reaction to the equal extent
• Equilibrium may attained earlier in the presence of a catalyst
Law of mass action
• Norwegian chemists , Cato Maximillian Guldberg and Peter Waage
(1864)
• A quantitative relationship between the rate of reactions and
concentration of the reacting substances- laws of mass action
• Statement: the rate of a chemical reaction is
directly proportion to the product of the molar
concentrations of the reactants at a constant
temperature at any given time
• The molar concentration ie., number of moles per litre is also called
active mass
• Eg x g of NaOH is dissolved in V litre of solution
• Concentration of NaoH= x g in V litre
• Molar mass of NaOH =40gmol^-1
• Molar concentration or moles per litre of NaOH= (x/40*v)moles/litre
• This is active mass of given NaOH
• The molar concentration of A is expressed as (A)
• Consider the reaction A+B products
• According to laws of mass action, rate of reaction rα(A)(B)=k(A)(B),
where (A) and (B) are molar concentrations of the reactants A
and B , k is the rate constant or velocity constant, a constant of
proportionality for forward reaction
• If the concentration of A and B are in unity
• rα(A)(B)=k(A)(B)= k*1*1=k
• Rate of constant of a reaction is defined as the rate of the
reaction when the concentration of each of the reactant is unity
• General reaction
• 2A+3B -- products
according to law of mass action, the rate at which A reacts α(A) (A) or
(A)^2
• The rate at which B reacts α(B)(B)(B) OR (B)3
• Rate of reaction between A and B α(A)^2(B)^3
• Rate of reaction=k (A)^2(B)^3
• For general reaction, aA +bB+cC- products
• Rate of reaction, r=k(A)^a(B)^b(C)^c
• Restatement of laws of mass action: the rate of a chemical
reaction at any particular temperature is proportional to the
product of the molar concentrations of reactants with each
concentration term raised to the power equal to the number of
molecules of the respective reactants taking part in the reaction
• The number of molecules of a reactant taking part in a reaction
is also called its stoichiometric coefficient .a,b,c are
stoichiometric coefficient of A,B, C
Law of chemical equilibrium and equilibrium
constant
• The law of mass action may be applied to a reversible reaction to
derive a mathematical expression for equilibrium constant known as
law of chemical equilibrium
• Consider simple reversible reaction
• A+B C +D, in which an equilibrium exists between the
reactants(A and B ) and the products (C and D). The forward reaction
is
• A+ B - C+D
• According to law of mass action,
• Rate of forward reaction α(A)(B) =kf(A) (B), where kf is the rate of
constant for the forward reaction and (A) and (B) are molar
concentrations of A and B
• Backward reaction C+ D - A+B
• Rate of backward reaction α(C) (D)= kb (C) (D), kb is the rate
constant for backward reaction and (C ) and (D) are molar
concentration of products
• At equilibrium the rates of two opposing reactions becomes equal
• Rate of forward reaction=rate of backward reaction
• Kf(A) (B)= kb(C ) (D)
• Kf/kb= (C ) (D) / (A) (B)
• K= (C ) (D) / (A) (B)
• Combined constant K is called equilibrium constant and has a
constant value for a reaction at a given temperature
• The above equation is known as law of chemical equilibrium
• Concentration ratio or concentration quotient (Q)=(C ) (D)/ (A) (B)
• Q=K , if reaction is at equilibrium
• For a general reaction, aA +bB cC+dD
• The equilibrium constant=K= ((C)^c (D)^d)/(A)^a(B)^b
• Where a,b ,c d have the same values as those in balanced equation
• Equilibrium constant=the ratio between the product of molar
concentrations of the products to that of molar contration of the
reactants with each concentration term raised to a power equal to its
stoichiometric coefficient in the balanced chemical equation at a
constant temperature.
• H2(g) +I2(g) 2HI(g)

• Kc=(HI(g)) 2eq/(H2(g)eq*(I2(g))eq
Equilibrium constants in Gaseous systems
• aA +bB cC +dD
• The equilibrium constantKp=(pC)^c *(pD)^d/(pA)^a(pB)^b
• Where pA, pB,pC,pD are partial pressures of A,B,C,D
• Kp and Kc are not always equal
Relation between Kp and Kc
• Consider aA+bB cC +dD
• Kc =(C)^c(D)^d/(A)^a (B)^b------1
• In terms of partial pressure
• The equilibrium constantKp=(pC)^c *(pD)^d/(pA)^a(pB)^b
• pV=nRT
• P=n/v *RT where n/v=concentration C(n is the amount of gas in mole )
• P=CRT or (gas)RT
• At constant temperature pαC
• P=CRT
• pA=(A)RT, where(A)is molar concentration of A
• pB=(B)RT, pC=(C )RT , pD=(D)
• Kp=((C) RT) *((D)RT) )/ ((A) RT *((B)RT)
c d a b

• =( C )c (D)d (RT)c+d / (A)a(B)b (RT)a+b

=( C )c (D)d (RT)c+d –a+b/ (A)a(B)b

Kc(RT)^(c+d)-(a+b)= Kc(RT)^Δng
Where Δng is the number of moles of gaseous products –number of moles of
gaseous reactants in the balanced chemical reaction
FACTORS affecting the state of equilibrium
–Le Chatelier’s Principle
• Le –Chatelier and Braun (1884)-French Chemists
• Certain generalizations to explain the effect of changes in concentration,
temperature or pressure on the state of system in equilibrium
• Statement: if a system in equilibrium is subjected to change in any of the
factors that determine the equilibrium conditions of a system then the
equilibrium will shift in the direction so as to reduce or counteract the
effect of the change
• The Principle is helpful in predicting qualitatively the effect of change of
change in concentration , pressure or temperature on a system in
equilibrium
Effect of change of concentration
• When the equilibrium is disturbed by the addition or removal of any
reactant and product, then the equilibrium shifts in the direction to
counteract the effect of change in concentration of reactants or
products
• When a substance, a reactant or product is added to an equilibrium
mixture, then the stress is relieved by the net reaction in the direction
that consumes the added substance
• When a substance(reactant or product) is removed from an
equilibrium mixture, the stress ids relieved by the net reaction in the
direction that replenishes the removed substance
H2(g) + I2(g) 2HI(g)
• According Le-Chatlier, the equilibrium will shift in the direction in
which the concentration of H2 is decreased
• A new equilibrium will set up in which concentration of H2 should be
less than it was after the addition of H2 but more what was in the
original mixture
• Equilibrium will shift to forward reaction
• If you consider reaction quotient Qc
• Qc=(HI)2/(H2)(I2)
• At equilibrium Qc=K
• If H2 is added at equilibrium, H2 increases and Qc becomes less than
K, reaction moves in forward until Qc=K
• In general
• If concentration of one or all the reactant species is increased, the
equilibrium shifts in the forward direction and more of the products
formed
• If the concentration of one or all the product species is increased, the
equilibrium shifts in the backward direction forming more reactants
• Removal of a product from the reaction mixture often has great
importance in the industry--- how????
• If the system is gaseous, the concentrations are taken as partial
pressure
• Application:
• 1. Carriage of oxygen by haemoglobin in blood : Hb carries O2 to
tissues
• Hb(s) + O2(g) HbO2(s)
• Lungs – blood in equilibrium with oxygen, but in tissues pO2 is low
• According to Le-Chatlier, HbO2 give up oxygen
• When blood returns to lungs , pO2 is more in lungs , equilibrium
favours the formation of HbO2
• 2. removal of CO2 from the tissue by blood
• CO2 (g)+ H2O(l) H2CO3 H+(aq) + HCO3-(aq)
• Explain
• 3. sweet substances causes tooth decay
• Ca5(PO4)3OH(s) 5Ca2+(aq) + 3PO43-(aq) +OH-(aq)
When sugar substances are taken, sugar is absorbed on teeth and gets
fermented to give H+ ions
H+ will disturb the equilibrium by combining with OH- to form water
and with PO43- to form HPO4^2-
Equilibrium shift towards right, hydroxy apatite dissolves, demineralization occurs,
tooth decay
• 2. effect of change of temperature: if the temperature of a system at
equilibrium is increased , the equilibrium will shift in the direction in
which the added heat is absorbed
• Equilibrium will shift towards endothermic reaction
• Decrease in temperature will shift the equilibrium to exothermic
reaction
• In general, the temperature dependence of the equilibrium constant
depends on the sign of ΔH for the reaction
• The equilibrium constant for an exothermic reaction (ΔH negative)
decreases as temperature increases
• The equilibrium constant for an endothermic reaction (ΔH
positive)increases as temperature increases
• N2(g) +3H2(g) 2NH3(g),ΔH=-92.38kJ

• Explain increase /decrease of temperature in the above reaction

• Effect of change of pressure:
• Increase of pressure on a system at equilibrium will shift the
equilibrium in the direction in which pressure is reduced
• As the pressure increases what will happen to volume ????
• Total number of moles /litre???????
• N2(g) +3H2(g) 2NH3(g)
CO(g) +3H2(g) CH4(g) +H2O(g)
• 4. effect of volume change: increase in pressure –decrease in volume
• Effect of change of volume will be exactly reverse to that of pressure
• Decrease the volume of a mixture of gases at equilibrium shifts the
equilibrium in the direction of lesser number of gaseous molecules
• Increase in the volume shifts the equilibrium in the direction of large
number of gaseous molecules
• 5. effect of catalyst:
• Catalyst has no effect on equilibrium
• It helps to achieve equilibrium quikly
• Catalyst has no effect on the equilibrium composition of a reaction
mixture catalyst does not shift the equilibrium in any direction
• Example 2SO2(g) +O2(g) 2SO3(g), Kc =1.7*10^26
• This reaction is very slow , but in presence Pt or vanadium pentoxide
V2O5, the rate of reaction-- increasing
• 6. effect of addition of inert gas
• Addition of an inert gas at constant volume: when inert gas is added
at constant volume, then the total pressure will increase
• But concentration of reactants and products will not change
• So no effect on the equilibrium
• Addition of inert gas at constant pressure: volume will increase,
number of moles per unit volume will decrease
• Equilibrium will shift in a direction in which there is increase in moles
of gases
• 2SO2(g) + O2(g) 2SO3(g)
• The addition of inert gas at constant pressure will shift the equilibrium
to the backward reaction
• 2NH3 (g) N2(g) +3H2(g)
• Here the equilibrium will shift to forward reaction
• H2(g) +I2(g) 2HI (g)
• No effect
Application of Le –Chatlier’s principle of
physical equilibrium
• A. Dissolution of ammonium chloride in water
• NH4Cl(s) +H2O NH4^+(aq) +Cl^-(aq),ΔH=+ve
• It is endothermic in nature
• If the temperature increased, then the equilibrium shifts in the
direction to counteract the effect of increased temperature
• Solubility will increase with increase in temperature in the case of
endothermic reaction
• B. dissolution of sodium hydroxide in water
• NaOH (s) + H2O Na+ (aq) + OH-(aq), ΔH=-ve
• The solubility will decrease with rise in temperature in the case of exothermic
reaction

• C. solubility of gas in a liquid:

• At equilibrium between gas and its solution in equilibrium
• When pressure is increased, volume of the system decreases
• Consequently the system proceeds in the direction in which the pressure of
the gas decreases and some of the gas dissolves in the liquid
• Increase in pressure increase the solubility of gas in the liquid
• But decrease in pressure decrease the solubility of gas
• Eg:Opening of soda bottle
• Consider the reaction
• 2SO2(g) + O2(g) 2SO3(g) + 189.4kJ
• Indicate the direction in which the equilibrium will shift when
• 1. temperature is increased
• 2. volume is increased
• 3. a catalyst is added
• 4. pressure is decreased
• 5. concentration of SO2 is increased
• 6. helium gas is added at constant volume so that the total pressure is increased
• Helium gas is added at constant pressure
Ionic equilibrium in solutions
• Ionic equilibrium:
• Michael Faraday classified the substances into two types : electrolytes
and non electrolytes
• The substances which conducts electricity in their molten state or in
the aqueous solution are called electrolytes , eg: acids , bases and
salts
• The substances which do not conduct electricity in their molten state
or in the aqueous solution are called non electrolytes. Eg sugar , urea
• When an electrolyte dissolves in water it splits up into ions
• Solid NaCl – an aggregate of cations and anions held together by
strong electrostatic force of attraction
• When it dissolves in water, the high dielectric constant of water cuts
down the force of attraction between the ions
• Dissolution of NaCl - YouTube
• The force of attraction between oppositely charged ions are inversely
proportional to the dielectric constant of the medium
• Greater the dielectric constant , greater the dissolving power of
solvent
• Here NaCl is almost completely ionised
• All substances do not ionise to same extent
• The degree of ionisation depends upon the polarity and the strength
of the bond and the extent of solvation of the ions formed
• Depending on the extend of ionization, the electrolytes are divided
into two classes: strong and weak
• 1. strong electrolytes: the substances which ionize completely into
ions in aqueous solution. Eg: HCl , H2SO4 , HNO3, NaOH, KOH,NaCl.,
KNO3
• Equation for ionization of strong electrolytes are written with single
headed arrow
• HCl + H2O --- H3O+ + Cl-
• Weak electrolytes: the substances which ionize to a small extent in
aqueous solution are called weak electrolytes
• eg: CH3COOH , NH4OH
• Here, molecules are in equilibrium with its ions
• CH3COOH + H2O H3O+ + CH3COO-
• In the case of weak electrolytes , a partial ionization takes place, so a
dynamic equilibrium is established between the ionized and unionized
molecules ----- ionic equilibrium
• Equilibrium which is established between the unionized molecules
and the ions in the solution of weak electrolytes ----- ionic equilibrium
Acid –base concept
• What is an acid and base ?????
Acid –base concept
• 1. Arrhenius concepts of acids and bases (1887):
• An acid is a substance which dissociates in water to give hydrogen ions
, H+(aq) and base is a substance which dissociates in water to give
hydroxyl ions, OH-(aq)
• Ionisation of an acid HX in water.
• HX(aq)--- H+(aq) + X-(aq)
• Or HX(aq) +H2O(l) --- H3O+ (aq) + X-(aq)
• Ionisation of base MOH
• MOH(aq)--- M+(aq) + OH-(aq)
• According to the concept: acids give H+ ions in water while
bases give OH- ions in water
• The strength of an acid or base depends on its capacity of
ionization to H+ and OH- ions
• 2. Bronsted – Lowry concept:
• An acid is a substance which can donate proton (H+)(proton donor)
while a base is a substance which can accept proton(H+) (proton
acceptor)
• HCl (aq) + NH3(aq) NH4+(aq) + Cl-(aq)
• Here HCl loses a proton is an acid
• NH3 accepts a proton and is a base
• Main advantage of this concept: it is not restricted to neutral
molecule
• Acids and bases can be either neutral molecules or ions
• Identify acids and bases in the following examples
• HCl(aq) + H2O(l) H3O+(aq) +Cl-(aq)

• NH4+(aq) + H2O (l) H3O+(aq) +NH3(aq)

• H2O(l) + CO3 ^2-(aq) HCO3-(aq) + OH-(aq)
• Acid base reactions are regarded as proton transfer reactions
• Substances which are capable of donating as well as accepting the
proton – amphoteric substances
• Eg H2O , HCO3-,HSO4-
•All Arrhenius acids are also Bronsted
acids but Arrhenius bases are not
Bronsted base –justify with an example
• Conjugate Acid-Base pairs

• HCl(aq) + NH3(aq) NH4+(aq) +Cl-(aq)

• The base formed from an acid – conjugate base of an acid
• Acid formed from a base – conjugate acid of the base
• The pairs of acids and bases which are formed from each other by
gain or loss of a proton are called conjugate acid base pairs
• Acid=conjugate base +H+
• Base + H+ = conjugate acid
• Each conjugate acid has an extra proton and conjugate base has one
proton less
• Each acid base reaction involves two pairs of conjugate acids and
bases, labelled as 1 and2
• acid 1 base1 acid2 base2
• Eg, HNO3 + H2O H3O + + NO3-
• H2SO4 +H2O H3O+ + HSO4-
Relative strength of conjugated acids and
bases
• According Bronsted –Lowry concept, a strong acid means a good
proton donor and a strong base means a good proton acceptor

• HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

• HCl is a strong acid , strong tendency to donate protons
• But Cl-ion has very little tendency to accept protons – weak base
• Equilibrium towards right hand side
• Conjugate base of a strong acid is a weak base
• CH3COOH (aq) +H2O (l) CH3COO-(aq) +H3O+(aq)

• Equilibrium towards left

• Strong base has a weak conjugated acid
• Weak base has a strong conjugated acid
Advantages of Bronsted –Lowry concept
over Arrhenius concept
• Bronsted – lowry concept can explain the basic character of
substances like Na2CO3, NH3 (which do not contain OH- group, hence
were not bases (Arrhenius))on the basis of that they accept proton
• Bronsted concept is not limited to molecules, but also covers even
ionic species to act as acids or bases
• Bronsted concept can explain the acid base reactions in the non
aqueous medium also
Limitations of Bronsted Lowry concept
• It cannot explain the reactions between acidic oxides like
CO2,SO2,SO3 etc and basic oxide like CaO, BaO, MgO which can takes
place even in the absence of the solvent
• CaO + SO3 --- CaSO4
• Substances like BF3 , AlCl3 etc are known to behave as acid but they
do not have protons to donate
Lewis concept of Acids and Bases
• GN Lewis (1923)
• An acid is a substance(molecule or ion) which can accept a pair of
electrons while a base is a substance(molecule or ion) which can
donate a pair of electrons
• A + B -- A-B

• Acids- electron pair acceptors

• Bases – electron pair donors
•Any substance which has an unshared
pair of electrons can act as a Lewis base
•Any substance which has an empty
orbital that can accommodate a pair of
electron act as Lewis acid
Lewis bases
• Neutral species having at least one lone pair of electrons
• Eg, Ammonia, amines alcohols are Lewis bases – they contain pair of
electrons
• Negatively charged species or anions: chloride, cyanide, hydroxide
ions
• Eg, CN-., Cl-, OH-
Lewis acids
• Molecules in which the central atom has incomplete octet
• Eg BF3, AlCl3,central atom has only six electrons around it
• Simple cations can act as Lewis acids
• All cations are expected to act as Lewis acids
• Na+, K+, Ca2+ have a very little tendency to accept electrons
• H+ and Ag+ ions have a greater electron accepting tendency
• Molecules in which central atom has empty d orbitals
• Due to the presence of empty d orbital, central atom can expand their
outer octet by accepting electrons from other substances (Lewis bases)
• Eg: SiF4, PF5,SnCl4- act as Lewis acids
• Molecules in which atoms of dissimilar electronegativities are joined
by multiple bonds
• Co2 and SO2 act as Lewis acids
• O=C=O +OH- --- HCO3- or
• All Bronsted bases are also Lewis bases but
all Bronsted acids are not Lewis acids .
Justify
Acid base reaction according to Lewis theory
• H+ and NH3
• Combination between BF3 and F- ion
• Reaction between BF3 and NH3
Limitations of Lewis concepts
• Lewis concept is too general and includes all the coordination
compounds and coordination reactions. This however may not always
be true
• It does not explain the behaviour of well known protonic acids like HCl
., H2SO4 which do not form coordinate bonds with bases . These are
not considered as acids by Lewis concept
• It does not explain the relative strength of acids and bases
• Acid base reactions are usually fast but the formation of coordination
compounds is slow. Hence it is not fit in the acid base reaction
concept
• The catalytic activity of many acids is due to H+(aq) ion . Since a Lewis
acid need not contain hydrogen, therefore many Lewis acids will not
possess catalytic property
Exit card
• What are conjugate base of each of the following
• HS-, H3O+, H2PO4-, HSO4-, CH3COOH,
• Give conjugate acids of the following
• OH-, HCO3-, , , HS-
• Which of the following behave both as Bronsted acids as well as
Bronsted bases
• H2O, HCO3-,H2SO4,H3PO4,HS-
• HS- : S2-
• H3O+ : H20
• H2PO4- :HPO4^2-
• HSO4-, :SO4^2-
• CH3COOH, : CH3COO-
• TO WRITE CONJUGATE ACID, ADD H+
• TO WRITE CONJUGATE BASE, SUBTRACT H+
• H2O, HCO3- AND HS- Behave both as acids and bases – amphoteric
substances
Ionisation constant of water and ionic product
of water
• H2O(l) + H2O(l) H3O+ (aq) +OH-(aq)
• Water as a weak electrolyte undergoes self dissociation
• Dissociation constant for the ionization of water
• K= (H3O+) (OH-)/ (H2O) 2

• Since the degree of dissociation of water is very small., the concentration of

undissociated water is taken as a constant
• K* (H2O)2 = (H3O+) (OH-)
• K* constant= (H3O+) (OH-)
• Kw= (H3O+) (OH-)

• Kw is a constant at a particular temperature and known as ionic product of water

• It varies with change in temperature
• At 298K, Kw= 1.008*10^-14 mol^2L^-2
• Kw= (H3O+) (OH-)= 1.008*10^-14 mol^2L^-2
• Kw =1*10^-14 at 298K
• In pure water, (H3O+) =(OH-)
• Kw= (H3O+) (OH-)= 1.008*10^-14 mol^2L^-2
• (H3O+)^2= 1.008*10^-14 mol^2L^-2
• (H3O+) =1.008*10^-14 mol^2L^-2 = 1.0* 10^-7 molL^-1
• In pure water, (H3O+) =(OH-)=1.0*10^-7 molL-1 at 298K
• The density of pure water is 1000g/L and its molar mass is 18g/mol-1
• Molarity of pure water = (H2O)= 1000g/L/ 18g/mol-1 =55.55M
• Ratio of dissociated water to undissociated water is
• 1.0*10^-7 molL-1 / 55.55M=1.8* 10^-9
• Equilibrium mainly towards undissociated water
Effect of temperature on Kw
• The value of Kw increases with rise in temperature
• H2O(l) + H2O(l) H3O+ (aq) +OH-(aq)
• Apply Le chatlier, increase in temperature - shift the equilibrium to
right
Hydrogen and hydroxyl ion concentration in
aq solution of acids and bases
• Ionic product controls the relative concentrations the H+ and OH-
because their product is a constant
• In pure water, the concentration of H3O+ and OH- ions are equal
• When an acid or base is added to the neutral solution, then
concentration of H3O+ and OH- ions change and do not remain equal
• But Kw remains constant at a particular temperature irrespective of
pure water, or base or acid addition
• Change in H3O+ and OH- ion concentration on the addition of an
acid :
• If we add HCl, the concentration of H3O+ ions becomes large ,
equilibrium shift to formation of undissociated water, so that Kw
remains constant
• (OH-) = Kw/(H3O+)
• The concentration of H3O+ ions will be more than the concentration
of OH- ions in the acidic solution
• Change in H3O+ and OH- ion concentration on the addition of base:
• If few drops of base is added to pure water, the concentration of OH-
ions increases, but the concentration of H+ ion decreases
• (H3O+)=Kw/(OH-)
• In basic solution , the concentration of H3O+ ions will be less than
OH- ions concentration
• in acidic (H3O+)>(OH-)
• In basic (H3O+)<(OH-)
• Neutral solution (H3O+)=(OH-)
Expression of hydrogen ion concentration –
pH scale
• In pure water, (H3O+)=(OH-)=1*10-7molL-1 at 298K
• Concentration of H+ ion gives an idea about the nature of solution
• Sorensen, 1909- suggested a new term pH scale
• pH is defined as the negative logarithm of the H3O+ ion concentration
in moles per litre
• pH=-log(H3O+) or log1/(H3O+)
• For neutral solution at 298K, (H3O+)=(OH-)=1*10-7molL-1
• =-log(H3O+)= -log(1*10-7molL-1)=7
• Rough measurement of pH of given solutions---explain
• Indicators: chemical substances which undergo pH dependant colour
changes as they are weak acids possessing different colours in their
acid and conjugate base forms
• Hin(aq) + H2O (l) H3O+(aq) + In-(aq)
Indicator conjugate base colourB
Acid
Colour A
• Like pH , pOH is defined as =-log(OH-)
• But (H3O+)(OH-) = Kw
• Log (H3O+)(OH-) =log Kw
• Log (H3O+)+ log (OH-) =log Kw
• -pH-pOH= -p Kw

• pH+ pOH=pKw
• At 25degree celcius, pKw=14
• pH +pOH = 14
• pH between 0-2-----strongly acidic
• 2-4---- moderately acidic
• 4-7 weakly acidic
• 7-10 weakly basic
• 10-12 moderately basic
• 12-14 strongly basic
Problems
Acid –base equilibria and ionization of acids
and bases
• The extent of dissociation is different for different acids and bases (in
aq medium)
• The strength of an acid is measured experimentally by determining its
dissociation or ionization constant
• Strong acids dissociates completely- molar concentration of H+ will be
same as that of acid
• Eg, HBr(aq), HI(aq), HNO3(aq), H2SO4(aq)
• Similarly , strong bases-------
• Dissociation equilibrium of a weak acid HA
• HA(aq) + H2O(l) H3O+(aq) + A-(aq)
• Applying law of chemical equilibrium
• K= (H3O+) (A-)/(HA)(H2O)
• Since water is present in large quantity , its concentration practically-
constant, so concentration of water may combined with K to gave
another constant Kα=K*(H2O)
• Kα= (H3O+) (A-)/(HA), where Kα is called dissociation or ionization
constant of an acid
• Larger the value of Kα, higher is the concentration of (H3O+),
stronger the acid
• The ionization constant can be used to calculate the degree of
dissociation or ionization and the concentration of H+ ions
• Degree of dissociation or ionization may be defined as
• The fraction of total number of molecules of an electrolyte(acid
or base) which ionizes into ions
• Degree of dissociation α = number of molecules of electrolytes
which ionize/ total number of molecules of the electrolyte
• If c is the number of moles of acid in one litre of the solution and α is
the degree of dissociation , then concentration of each species
at equilibrium
• HA(aq) + H2O(l) H3O+(aq) + A-(aq)
• Initial c 0 0
• Equi c(1- α) cα cα
• (HA)=c(1- α),(H3O+)=c α, (A-)=c α
• Kα= (H3O+) (A-)/(HA)= c α* c α/c(1- α)= c α^2/1- α
• For weak acid α is very small, so 1- α=1
• K α=c α^2 or α= K α/c
• (H3O+)= c α=c K α/c =K αc
• We may also write
• pK α=-logK α
• Stroger acid will have higher K α, but smaller pK α
• Weaker acid –small K α , but higher pK α
• Knowing the value of ionisation constant, K α of an acid and its
initial concentration , we can calculate the equilibrium
constants, degree of ionization and pH
• (H3O+)= c α=c K α/c =K αc
• pH=-log(H3O+)
• Dissociation or ionization constant of base
• B(OH)(aq) B+(aq) +OH-(aq)
• Ionisation constant of base Kb=(B+)(OH-)/((BOH)
• Concentration of water remains constant , if c is the number of moles
of the base in one litre of the solution and α is the degree of
ionization
• (B+)=c α,(OH-)=c α, (BOH)=c(1- α)
• Kb= c α^2/1- α, for weak bases αis very small, then1- α=1
• Kb=c α^2
• Α= Kb/c
• (OH-)= c* Kb/c =Kb*c

From this (H3O+) and pH can be calculated

H3O+= Kw/(OH-)
pH=-log(H3O+)
• Like pK α, we can define pKb=-logKb
• Strong base- higher Kb, smaller pKb
• Larger the value of pKb, weaker the base
Calculation of pH and pOH of weak
electrolytes
• Step1: write primary reaction for equilibrium:
• If more than one reaction, write balanced equation for all
• Find out the equation with higher K α or Kb---- identify it as primary
reaction
• Eg HF+ H2O H3O+ +F-, K α=3.2*10^-4
• H2O + H2O H3O+ + OH- K w= 1.0* 10^-14
• Which equation????
• Step 2: write in tabular form the following values
• Initial concentration c
• Change in concentration as proceeding to equilibrium in terms of
degree of ionisation α
• Equilibrium concentrations
• Step3: Substitute all equilibrium concentrations into equilibrium
constant equation for the reaction and solve for α
• Step4: calculate the concentration of the species present
• Step 5: calculate pH as pH= -log(H3O+)
Relation between K α and Kb
HA (aq) +H2O H3O+(aq) +A-(aq)
Write the equation for K α(HA)=
=(H3O+) (A-)/ (HA)-------(1)
HERE A- IS --------
Weak acid
A- + H2O HA +OH-
Kb=
=(HA)(OH-)/ (A-)------(2)
• MULTIPLY 1 and 2
• K α (HA)* Kb(A-) =(H3O+) (A-)/ (HA ) * (HA)(OH-)/ (A-)
• =Kw

• In general,
• K α of acid * Kb of conjugate base =Kw =???
• =10^-14mol^2L^-2 at 298K
• Taking negative logarithm on both side
• -log K α-logKb = -log Kw
• pKa+ pKb= pKw
• pKw=-log10^-14=14
• pKa acid + pKb con= pKw=14
Poly protic acids and bases
• Bronsted acids which can donate more than one proton – polyprotic
acid or polybasic acid
• Eg H2SO4- dibasic acid, H3PO4 is a tribasic acid
• Ionisation reaction for a dibasic acid
• H2X(aq) H+ (aq) + HX-(aq)
• HX-(aq) H+ (aq) + X2-(aq)
• Ionisation constants K α1=(H+)(HX-)/(H2X)-first ionization
constant
• K α2=(H+)(X2-)/(HX-)---- second ionization constant
• Acidic strength of polyprotic acid decreases as protons lost
• Polyacidic base is a species which can accept more than one proton
• Eg CO3^2-, PO4^3- etc
Common ion effect in the ionization of acids
and bases
• CH3COOH(aq) CH3COO- (aq) + H+(aq)
• Determine K α
• What will happen if H+ ions are added at equilibrium
• If an anions is added????
• This is called ion effect
Factors affecting the acid strength
• In general strength of an acid HA depends on
• Strength and polarity of H-A bond
• When strength of H-A bond decreases, then the energy required to
break the bond decreases
• Electronegativity differences between atoms (H and A) increases,
there is significant charge separation and cleavage of bond becomes
easier and thereby increasing the acid strength
• Acid strength of the hydroacids of the elements of second period
increases as:
• CH4< NH3< H2O <HF
• Electronegativity of these elements increases in the order
• C<N<O<F
• With the increase in electronegativity , the element has more and more
tendency to withdraw strongly the electron pair from H . Ionic character
generally increases
• The release of hydrogen ion becomes more easy and acidic character
increases
• The relative strength of hydroacids of a group increases as we go
down the group
• HF< HCl< HBr<HI
Buffer solution
• The solution which resists changes in the hydrogen ion concentration
on the addition of small amount of acid or base
• Buffer solutions are of two types
• Acidic buffer: acidic buffer solution contains equimolar quantities of a
weak acid and its salt with strong base
• Eg: Acetic acid and sodium acetate ( 4.74)
• Basic buffer: basic buffer solution contains equimolar quantities of a
weak base and its salt with a strong acid
• Eg: ammonium hydroxide and ammonium chloride (pH=9.25)
• Buffer action: the ability of the buffer solution to resist the changes in
pH value on the addition of small amount of an acid or a base, is
called buffer action
Solubility product
• Lattice enthalpy and solvation enthalpy
• Lattice enthalpy- amount of energy required to break one mole of
solid salt into its ions
• Solvation enthalpy: amount of energy released when one mole of a
solid salt get dissolved in a solvent
• Salt will be soluble in a solvent: when solvation enthalpy> lattice
enthalpy
Solubility product constant
• AgCl(s) Ag+(aq) +Cl-(aq)
• Apply law of equilibrium and write K=
• Concentration of pure solid substance remains constant
• K* (AgCl)=(Ag+) (Cl-)
• K* constant= Ksp(solubility product constant) =(Ag+) (Cl-)
• Solubility product of a salt at a given temperature is
• Equal to the product of the concentrations of its ions in the saturated
solution, with each concentration term raised to power equal to the
number of ions produced on dissociation of one mole of the substane
• Equilibrium: Equilibrium in physical and chemical processes, dynamic
nature of equilibrium, law of mass action, equilibrium constant,
factors affecting equilibrium - Le Chatelier's principle, ionic
equilibrium- ionization of acids and bases, strong and weak
electrolytes, degree of ionization, ionization of poly basic acids, acid
strength, concept of pH, buffer solution, solubility product, common
ion effect (with illustrative examples).