CHEMICAL EQUILIBRIUM Reversible and Irreversible Reactions Irreversible Reactions: The reactions in which products formed do not react

with one another to give original reactants under any conditions, are called irreversible reactions. Eg. 2Na + 2H2O 2NaOH + H2 C + O2 CO2 Reversible Reactions: These are the reactions in which the products formed react with one another under some conditions to give back original reactants. When steam is passed over red hot iron, H2 gas is evolved. 3Fe + 4H2O Fe3O4 + 4H2 And when H2 gas is passed over heated steam Fe3O4 is evolved. Fe3O4 + 4H2 3Fe + 4H2O (g) If such reaction is carried out in a closed vessel both forward and backward reaction will occur and the reaction is represented by putting two arrows pointing in opposite directions. 3Fe + 4H2O Fe3O4 + 4H2

Equilibrium can be achieved only in reversible reaction. N2 (g) + 3H2 (g) 2SO2 (g) + O2 (g) PCl5 (g) 2NH3 (g) 2SO3 (g)

PCl3 (g) + Cl2 (g)

Equilibrium in Physical Processes (a) Solid Liquid

Solid and liquid co-exist in equilibrium at a temp. known as m.p. At eqbm, rate of melting = rate of freezing. (b) Liquid Gas equilibrium

Evaporation of water in a closed vessel results into the equilibrium state. (c) Dissolution of Solid in Liquid A solution in which no more solute can be dissolved is called a saturated solution and saturated solutions represent equilibrium state. Dissolution Undissolved solute dissolved solute Crystallization At equilibrium, Rate of dissolution = Rate of crystallization Solubility: It is the amount of solute required to prepare a saturated solution in a give quality of solvent is known as solubility of the solute at a given temperature. Solubility of a solid in any liquid depends upon temperature and pressure has no significant effect on the solubilitys of solid in liquids. (d) Dissolution of gas in liquid: Dissolution by gas in liquid is affected by the pressure and is governed by Henrys Law.

Equilibrium state is that state of the system when the conc. of reactants and products become constant. Equilibrium state is that state of the system when the two op[posing reactions are proceeding at same rate. Equilibrium state is that state of the system when the measurable properties (vapour pressure, colour, density, etc.) of the system donot show any noticeable change under the given set of conditions. Vapour Pressure: It is the pressure exerted by the vapours in equilibrium with its liquid at a given temp. The vapour pressure of the liquid depends on the nature of the liquid and temp. but independent of the amount of liquid and surface area. Henrys Law: The mass of the gas dissolved in the given amount of liquid is directly proportional to the pressure of the gas in equilibrium with liquid at a given temp. m p

More the pressure of the gas above liquid move the dissolution. Solubility of gas in liquid increases with the increase in pressure but decreases with the increase in temp. Henrys law is not applicable when (i) (ii) (iii) Pressure is too high Temp is too low The gas chemically reacts with the solvent.

Chemical Equilibrium The equilibrium involving chemical processes is chemical equilibrium. Eg. H2
(colourless)

+ I2 (violet colour)

2HI

(colourless)

Characteristics of Equilibrium 1. Equilibrium is dynamic in nature: The constantly in the observable properties of the system at equilibrium does not mean that the reaction has been stopped altogether, but it simply means that both forward and backward reactions are taking place at same rate so that no net reaction is taking place. That shows the reaction does not stop even after attaining equilibrium. Following example will prove: Suppose the reaction of H2 and I2 to produce HI is in equilibrium H2 + I2 2HI

If small amount of radioactive iodine is added to the reaction mixture, we will find after sometime that HI also becomes radioactive. That show dynamic nature of equilibrium saturated sugar solution. 2. The equilibrium can be attained only in a closed vessel i.e. when the products are not allowed to escape the reaction vessel so that they are available for the backward reaction. 3. At equilibrium, the measurable properties of the system (such as vapour pressure, colour, density etc.) donot show any noticeable change under the given set of conditions.

4. The equilibrium is not affected by the use of catalysts. Catalyst increases the rate of forward reaction as well as backward reaction by some amount so it only helps in attaining the equilibrium earlier. 5. The equilibrium can be attained from either side, i.e. we. May start with the reactants or products but the position of equilibrium at a given temp will be same. Eg. N2O4 and NO2 exist in equilibrium at 298 k as pole brown gas. Pure N2O4 exist at 273 k as colourless gas. Pure NO2 exists at 373 k as reddish brown gas. Take equilibrium mixture of N2O4 and NO2 in two sealed bulbs. Bulb A is placed in ice bath and bulb in boiling water both. So now Bulb A has pure N2O4 and Bulb B has pure NO2. Now place both the bulbs in a water bath at 298 k. In Bulb A, the colour will start appearing due to decomposition of N2O4. N2O4 2NO2

In Bulb B, reddish brown colour will start fading due to formation of N2O4, 2NO2 N2O4

When both bulbs attain the temp. 298 k, both the bulbs have some colour that shows equilibrium is attained. Law of Mass Action: The rate at which a substance reacts depends on its active mass i.e. molar concentration (Conc. of moles/lt.)

The rate of reaction at a given temp. is directly proportional to the product of the conc. of reactants with each concentration term raised to power equal to the no. of moles of that species taking part in the reaction. Suppose A Product r |A| or CA Square brackets represent conc. in moles/lt.

A + B Product r |A||B|

2A + B Product Or A + A + B Product r |A||A||B| or r |A|2|B|

aA + bB Product r |A|a|B|b k Rate constant, specific velocity constant, its value depend on the nature of reactants and temp. Ratio constant is the rate of reaction when the concentration of reactant is taken as unity. Law of Chemical Equilibrium (with the help of law of mass action) Suppose a hypothetical reaction at equilibrium aA + bB lL + mM

According to Law of Mass Action: Rate of Forward Reaction r |A|a|B|b kf Rate constant for forward reaction

rf = kf|A|a|B|b Rate of Backward Reaction r |L|l|M|m

rb = kb|L|l|M|m At equilibrium

kb Rate constant for backward reaction

rf = rb kf|A|a|B|b = kb|L|l|M|m

kf and kb are constant so their ratio is also constant and is replaced by a new constant equilibrium constant kc

Definition of Equilibrium constant At a given temp., the equilibrium constant is the ratio of the product of the equilibrium concentration of products to that of reactants with each conc. term raised to power equal to the no. of moles of that species taking part in the reaction.

In case of gaseous components, the concentration is expressed in terms of partial pressure and equilibrium constant is expressed as kp. aA + bB lL + mM

Relation between kp and kc Ideal gas equation: PV = nRT

If V = lts P = CRT

{(l+m)-(a+b)} {(l+m)-(a+b)} = Change in no. of moles of gaseous compound = kc x RT

kp = kc (RT) kp = kc Characteristics of Equilibrium Constant 1. The value of k is independent of the initial conc. of reactants. 2. The value of k is also independent of the use of catalyst. 3. The value of k is affected temp. i.e. the value of k changes with the change in temp. 4. The value of k for forward reaction is just inverse of the value of k for backward reaction.

Suppose of equilibrium constant for the reaction

What will be the equilibrium constant for the reaction?

5. The value of k gives the extent to which the reaction will occur. Higher the value of k means the reaction has tendency to proceed in forward direction.

Homogenous and Heterogeneous Equilibrium Homogenous Equilibrium: It is equilibrium established when all the reactants and products are in one phase i.e. homogenous mixture.

Heterogeneous Equilibrium: When the reactants and products are not in one phase or they are different phases.

(i)

10

Conc. of solid remains constant so it is taken as unity. (ii)

Conc. of water liquid remains constant so it is taken as unity. (iii) NH3 (aq.) + H2O(l) NH4+(aq) + OH-(aq.)

Conc. of solvent also remains constant so taken as unity Le-Chateliers Principle: Whenever an equilibrium system is subjected to some stress (change in conc., temp., pressure, etc.) the equilibrium will shift in that direction so to undo the effect of stress imposed. Effect of Change in Concentration Suppose a hypothetical reaction in equilibrium

If conc. of A is increased, the equilibrium will shift in that, direction in which conc. of A is decreased, conc. of A decreases only if move of products are
11

formed. It means increase in conc. of A will shift the equilibrium in forward direction. Similarly increase in conc. of B will shift the equilibrium in forward direction or forward reaction will be forwarded. It means increase in conc. of any one or more of reactants will shift the equilibrium in forward direction. If conc. of C or D is increased, the equilibrium will shift in that direction so that conc. of C or D may decrease i.e. backward reaction will be favoured. Increase in conc. of any one or more of reactant will shift the equilibrium in forward direction and increase in conc. of any one or more of products will shift the equilibrium in backward direction. 2. Effect of Temperature: In a reversible reaction, if forward reaction is exothermic, backward will be endothermic. When temp. is increased is an equilibrium process i.e. heat is added, equilibrium will shift in that direction. So that added heat may be absorbed Heat is absorbed in endothermic process. It means increase of in temp will shift the equilibrium in the direction of endothermic process. Similarly when temp is decrease, equilibrium will shift in the direction of exothermic process. N2(g) + 3H2(g) Hg = -ive In this reaction, when temp. is increased, the equilibrium will shift is backward direction. 3. Effect of pressure: Pressure affects the equilibrium only when the reactants and products involve gaseous component and the reaction proceeds with change in no. of moles of gaseous component. Eg. N2(g) + I2(g) 2HI(g) 2NH3(g)

Hg = 0 So pressure will have no effect on such an equilibrium

12

PCl5(g)

PCl3(g) + Cl2(g) Pressure will affect this equilibrium

When pressure is increased, volume is decreased and no. of moles/unit volume is increased. The equilibrium will shift in that direction in which no. of moles per unit volume decreases or no. of moles decreases. It means increase in pressure will shift the equilibrium in that direction which proceed with decrease in no. of moles of gaseous component and decrease in pressure will shift the equilibrium in that direction which proceed with increase in no. of moles of gaseous component. PCl5(g) PCl3(g) + Cl2(g)

Increase in pressure will shift the equilibrium in backward direction. 4. Effect of volume: Increase in volume will shift the equilibrium in the direction which proceed with increase in no. moles of gaseous components. 5. Catalyst: Catalyst does not affect the equilibrium state. It only helps in attaining the equilibrium earlier. 6. Addition of inert gas: a. Addition of inert gas at constant volume: When the inert gas is added to the equilibrium mixture at constant volume, pressure will increase, but the partial pressure of each gas in the mixture remains the same. So addition of inert gas at constant volume will have no effect on equilibrium. b. Addition of inert gas at constant pressure: When the inert gas is added to the equilibrium mixture at constant pressure, the volume will increase and then the partial pressure of each gas in the mixture decrease. Now th equilibrium will shift in that direction in which no. of molesof gaseous component are increasing i..e where volume is increasing.

13

Ionic equilibria: Strong Electrolyte: - Strong electrolytes are those which are completely dissociated in aqueous medium. Eg. HCl, H2SO4, NaCl, NaOH, etc. HCl NaCl So no equilibrium is established. Weak Electrolyte: Weak Electrolytes are those which are weakly dissociated in aqueous medium. Eg. HF, CH3COOH, NH4OH, etc. CH3COOH H+ + CH3COOH+ + ClNa+ + Cl-

It means there exist equilibrium between undissociated molecule and its ions in solution. This equilibrium is ionic equilibrium. Zonic Equilibrium: It is the equilibrium established between undissociated molecule and its ions in solution. Case I: Ionic equilibrium involving soluble weak electrolyte. Eg. HF, CH3COOH, NH4OH etc

Suppose C mol/lt is the initial conc. of HA be the degree of dissociation So amount of HA dissociated C

14

Degree of dissociation ( ): It is the fraction of total no. of molecules that dissociated

Initial Conc. Amount Dissociated Eqbm Conc

C mol/lt C C-C

C C

C C

As the electrolyte is weak, may be taken as unity.

will be very small as compared to one and so 1 -

15

Degree of dissociation of weak electrolyte is inversely proportional to the square root of the initial conc. of electrolyte. It means degree of dissociation increases with the decrease in concentration on degree of dissociation increases with the increase in dilution. This generalization is known as Ostwadls Dilution Law. At infinite dilution, when C 0, the degree of dissociation becomes equal to one. i.e. at infinite dilution, every weak electrolyte are completely dissociated. In homeopathic medicines, Ostwalds dilution law is used. Case II. Ionic equilibrium involving sparingly soluble weak electrolyte

Eg. AgCl, Ag2CrO4, CaF2, etc. AgCl is a sparingly soluble salt, when small amount of AgCl is put into water, immediately a saturated solution results. Even in this saturated solution, conc. of AgCl is very less in solution. So whatever amount of AgCl dissolves in water is completely dissociated and so can ionic equilibrium is established between solid undissociated electrolyte and its ions in solution.

| | |

| replaced by a new constant

16

Conc. of solid AgCl is constant no matter how much of it is in contact with water. Solubility Product | |

It is the product of the conc. of ions in a saturated solution with each conc. term raised to appropriate power at a given temperature. How to determine solubility product? Solubility product can be determined, if we know the solubility of sparingly soluble salt. Solubility of BaSO4 = 1.1 x 10-5

17

Solubility of SrF2 in mol/lt:

( Applications of Solubility Product:

)(

1. In determining the solubility of sparingly soluble salt Ksp (AgBr) = 3.3 x 10-13

Ksp (PbCl2) = 1.0 x 10-6

18

2. In predicting the precipitation reaction With the help of solubility product, we can predict whether a ppt will four or not when two solutions are mixed. We will determine ionic product of the electrolyte which is to be precipitated and compare with its solubility product. I.P. < Ksp (Unsaturated) No Precipitation
19

I.P. = Ksp (Saturated) I.P. > Ksp (Super Saturated) Precipitation will occur 3. In precipitation of soluble salt We can precipitate our even soluble salt by applying the principle that precipitation will occur when I.P. is greater than solubility product. Eg. Sodium Chloride is purified by passing HCl gas through the saturated solution of crude NaCl. Saturated solution of impure NaCl, I.P. = Ksp

HCl gas is passed. HCl gas will provide Cl- ion in solution. This will increase the I.P. of NaCl than by its solubility product and pure Sodium Chloride is thrown out as precipitate. 4. In qualitative inorganic analysis Common in effect: It is the suppression of degree of dissociation of weak electrolyte in the presence of strong electrolyte having one ion common. Eg. NH4OH is a weak electrolyte and is weakly dissociated into NH+4 and OHion and so an ionic equilibrium is established.

Say small amount of NH4Cl is added (strong electrolyte) it will provide NH+4. So due to common ion, degree of dissociation.
20

of NH4OH will be decreased as we are increasing the conc. of NH+4 ion, the equilibrium dissociation of NH4OH will shift in backward direction i.e. weak electrolyte will become weaker. In this case by increasing the conc. of NH+4 ion, we have decreased the conc. of OH- ion.

Acid Base Equilibrium Arrhenius Concept of Acids and Bases: This concept of acids and bases is based on Arrhenius theory of ionization. Acid: is a hydrogen containing substance which on dissociation in aqueous medium furnished Hydrogen ion. Eg. HCl, HNO3, CH3COOH, H2SO4, etc.

Base: Any hydroxyl group containing substance which on dissociation in aqueous medium furnishes hydroxide ion base. Eg. NaOH, KOH, Ba(OH)2, etc.

Acid Base reaction, according to this theory is the combination of H+ ion from acid with OH- ion from base to form water.
21

Basicity of an acid is the no. of hydrogen ion furnished by its one molecule in aqueous solution. Eg. HCl is a monobasic acid H2SO4 is a dibasic acid Basicity = 1 Basicity = 2

Acidity of a base is the no. of hydroxyl ion furnished by its one molecule in aqueous solution. Eg. NaOH Ba(OH)2 Acidity = 1 Acidity = 2 Monoacidic Base Diacidic Base

Limitation of this theory: 1. Nature of H+ ion: H+ ion is nothing but a proton and it has very high charge density and so cannot exist independent. It is strongly attracted by the molecule to form H3O+ ion, So H+ ion does not exist in water but it exists as hydronium ion (Recent researchers have shown that H+ ion exist in water as HgO4+ ion) 2. Limited Scope: This theory applicable only in aqueous medium. 3. Acids and Bases without H3O+ and OH- ion: There are many substances which are acting as acids but do not contain hydrogen e.g. CO2, SO2, AlCl3, BF3, etc. There are many substances which are acting as based but contain any hydroxyl group. Eg. NH3, Na2CO3, NaHCO3, etc. Lowry Bronsted theory of Acids and Bases. Bronsted Theory: Acid: Any substances which can donate a proton is acid, Acid is proton donor.
22

Base: Any substance which can accept a proton is base. Base is proton acceptor. According to this theory acid-base reaction involves the transference of a proton from acid to base. This theory is also known as proton transfer theory. Eg. NH3 (g) + HCl (g) NH+4 + Cl-(g) (base) (acid)

According to this theory Acid-base reaction is complimentary reaction i.e. give and take i.e. An acid is acid only if some other substances is present which can accept a proton and the base is base only if some other substance is present which can donate a proton. Eg. HCl is acid in water as a water can accept a proton but HCl is not an acid in benzene because benzene does not accept a proton.

According to this theory even ions can act as acid as well as bases. We find from the above examples that some substances are acting as acids as well as bases. Such substances which are acting as acids as well as bases are known as amphoteric substances.

23

Conjugate Acid-Base Pair: Acids after donating a proton becomes its conjugate base in the backward reaction and the base after accepting a proton becomes its conjugate acid in the backward reaction. Such pair of substances which are formed from one another by the loss or gain of proton are known as conjugate acid-base pairs. Conjugate acid + Conjugate Base

Name the conjugate base of the following conjugate acids

Strong Acid The acid which has higher tendency to donate a proton is strong acid. The acid which has lesser tendency to donate a proton is weak acid. Similarly strong base is a substance which has higher tendency to accept a proton.

24

In this case, equilibrium of the reaction lies very much towards the left. It means acetic acid is a weak acid and its conjugate base acetate ion is a strong base.

Equilibrium of this reaction lies towards the right. It means HCl is a stronger acid and its conjugate base chloride ion is a weak base. We conclude that conjugate base of a strong acid is a weak base and conjugate base of a weak acid is strong base and so on. All Arrhenius acids are also Bronsted acids but all Arrhenius bases are not Bronsted bases. Justify Arrhenius Acid: Any Hydrogen containing substance which on dissociation in aqueous medium furnishes H+ ion is acid. Bronsted Acid: Any hydrogen which can donate a proton is acid. According to both the theories, acid should be a hydrogen containing substance and should furnish H+ ion or proton. Eg. HCl is acid according to both the theories as it can furnish H+ ion in aqueous medium as well as it can donate a proton. Arrhenius Base: Any substance which on dissociation in aqueous medium furnishers OH- ion is base. Bronsted Base: Any substance which can accept a proton. It is not necessary that a substance which can furnish OH- ion may also be able to accept a proton. Eg. NaOH can furnish OH- ion in aqueous medium so it is Arrhenius base but it cannot accept a proton as such so it is not a Bronsted base. So all Arrhenius bases are not Bronsted bases.

25

Limitation of Bronsted Theory There are some substances which are acting as acid but donot donate proton. Eg. CO2, SO2, AlCl3, BF3, etc. Lewis Concept of acids and Bases Lewis Acid: Any substances which can accept a lone pair of electron is lewis acid. Lewis acid is electron acceptor. Lewis Base: Any substances which can donate a lone pair of electron is lewis base. Lewis base is electron donor. According to this theory acid-base reaction is the transference of a pair of electron from base to acid to form a native or coordinate bond between the two. e.g. NH3 + BF3 H3N BF3 Types of Lewis acid: CH2 (a) All cations are Lewis acid. E.g. H+, Ag+, Cu2+ etc. (b) Neutral molecule in which central atom has incomplete octet of electron and can accept a pair of electron. E.g. Alcl3, BF3, SO3 etc. (c ) Neutral molecule in which central atom has completed octet of electron but has empty d-orbitals to accept a pair of electron. e.g. SiCl4, SnCl4 etc. (d) Neutral molecule in which there is a multiple bond between two atoms having different value of electronegativity. e.g. CO2, So2 etc. Types of Lewis bases:
26

(a) All anions are Lewis bases. E.g. OH-, Cl-, CN-, CH3Coo- etc. (b) Neutral molecules in which central atom has one or more lone pair of electron to donate e.g. NH3, H2O, CH3-CH2-OH, R-O-R etc. NH3 + H+ NH4+ Limitations of Lewis concept: 1. This theory is too general and includes the formation of all kinds of co-ordination compounds. 2. This theory does not account for the strength of acids and bases. 3. Formation of co-ordination compound is a slow process but acid-box reaction is very fast, so it does not account for this fact. 4. It can not explain the acidic nature of well known protonic acids which do not form co-ordinate bonds e.g. HCl, HNO3 etc. HCL do not accept a pair of electron as such. So it is all Bronsted bases are also Lewis bases but not all a Lewis acid Bronsted acids are not Lewis acids. JustifyBronsted box: Any substance which can accept a proton is Bronsted base. Lewis box: Any substance which can donate a pair of electron is Lewis box. Both the theories amount to same i.e. a substance which can donate a pair of electron can also accept a proton. e.g. NH3 can donate a pair of electron so it is Lewis box. NH3 + BF3 H3N BF3 NH3 can accept a proton so it Bronsted box.

Bronsted acid: Any substance which can donate a proton is Bronsted acid Lewis acid: Any substance which can accept a pair of electron is Lewis acid.

27

It is not necessary that a substance which can accept a pair of electron, can also donate a proton. E.g. BF3 can accept a pair of electron so it is Lewis acid but it has no hydrogen to donate as proton an dit is not a Bronsted acid. HCL can donate a proton so it is Bronsted acid but it can not accept a pair of electron as such so it is not a Lewis acid.

These two substances are acids & base acc. To all 3 theories Strength of Acids and bases (Airhenius Theory) Strength of acids: The properties of acid in solution is due to presence of H+ ion or H3O+ ion. Higher the cone of H3O+ ion in solution, stranger will be the acid. Conc. Of H3O+ ion in solution will depend on the degree of inisation of acid hich in turn depend on the nature of acid. Strong acid: is one which is completely dissociated in aqueous solution to furnish longer cone. Of H3O+ . e.g. HCL, H2SO4, HNO3 etc. Weak acid is one which is weakly dissociated in aqueous solution to furnish smaller cone of H3O+. e.g. HF, CH3COOH etc.

28

The acid having higher degree dissociation will be stronger acid. We can compare the strength of weak acids in term of dissociation constant of acid higher the Ka value stronger will be acid.

Strength of bases: The properties of bases in solution are due to the presence of OH- ion. Higher the cone. Of OH- ion in solution, stronger will be the base. Strong bases: are those which are completely dissociated in aqueous solutions to give layer cone. Of OH- ion e.g. NaoH, KoH etc. NaoH Na+ + OHWeak bases: are those which are weakly dissociated in aqueous solution to give smaller cone. Of OH- ion e.g. NH4OH, Cu(OH)2 etc.

29

Dissociation

Higher the cone of OH-, higher will be the value of

and stronger the box it is.

Self ionization of water: (Ionisation product of water) KW water is a very very weak electrolyte and is very weakly dissociated to give equal no. of OH- ion. and

Cone of remains constant and so ionic product of water. The value of The value of

is replaced by a new constant

at 298 K was found to be 1 x 10-14 increases with the increase in temperature:

30

As dissociation of water will increase the increase in temp, so In pure water,

also increase.

In pure water,

at 298 K. when small amount of acid is added: i.e. H3O+ ion are added. The addition of H3O+ ion to water will disturb the equilibrium dissociation of acid and will shift the equilibrium in background direction. As the value of increase in keep the value of ion concentration will decrease the cone of constant and cone of is constant, so ion as to

in solution given by:

As the cone of In acidic solution

is more than

ion so solution is acidic.

31

When small amount of box is added: i.e. ion is increased, the cone of value of constant and cone of

ions are added, again the

equilibrium dissociation of water will shift in backward direction. As the cone of ion must decrease so as to keep the is given by

As the cone of is basic. In basic solution:

ion is more than cone of

ion in solution, the solution

So solution may be acidic, basic or neutral it contains both type of ion. (neutral)

Or

32

PH scale: PH = It is the negative logarithm of PH = PH of neutral solution: or ion concentration

=7 PH of acidic solution will be less than 7. PH = 7 PH > 7 PH < 7 PH scale 0 1 2 (neutral) (basic) (Acidic) Acidic character increases 3 4 5 6 7 Neutral basic character increases 8 9 10 11 Moderately strong box 12 13 14

Strong acid

Moderately strong acid

Weak acid

Weak box

Strong box

PH =

33

Relationship between Ionisation constant of a base and Ionisation constant of its conjugate acid.

Ionization of

conjugate acid of B is represented as:

Multiplying (i) and (ii)

Like

Taking log

Or
34

So

or

Hycholysis of salts: It may be defined as the process in which water reacts with salt to form an acid and a base. It means hycholysis of salt is just the reverse of neutralization.

We can write

Since water remains practically constant during hydrolysis, Kn hydrolysis constant of salt. The fraction of total salt that is hydrolysed at equilibrium is called degree of hydrolysis. I is denoted by h. In hydrolysis, either cation or anion or both of salt interact with water to give acidic, basic or neutral solution respectively. Cation + H2O weak base + H+ Anion + + H2O weak acid + OH-

35

Cation + Anion + + H2O weak acid + weak base HCL, H2SO4, HNO3 strong acids. NaOH, KOH, Ba(OH)2 strong bases. 1. Hydrolysis of a salt of weak acid and strong base: e.g. Na2CO3, KCN, CH3COONa etc. this type of salt will produce alkaline solution on hydrolysis. Hydrolysis of a salt MX.

In solution MX and MOH undergo complete dissociation whereas acid HX being weak acid remains almost undissociation. So we can write:

remains constant. For the dissociation of weak acid HX we can write .

Multiply Ka with Kn.

36

Degree of hydrolysis

C Ch C ch C (1 - h) Initial cone of salt is c and h degree of hydrolysis.

substituting the value of Kn.

Hydronium ion conc and PH.

2. Hydrolysis of salt of strong acid and weak base: e.g. Z4(NO3)2, CUSO4, Al2(SO4)3, NH4Cl, FeCl3 etc.

37

This type of salt will produce acidic solutions on hydrolysis.

In solution MX and HX are completely dissociated and MOH will remain almost undissociated since it is weak.

For dissociation of weak base we can write .

Multiplying Kn with Kb.

Degree of hydrolysis

Suppose initial conc. Of salt is C and h degree of hydrolysis So

substituting the value of Kn

38

ion concentration and PH.

2. Hydrolysis of salt of a weak acid and a weak base e.g. Calcium carbonate, ammonium acetate, ammonium phosphate etc. Aq. Solution of such salts are almost neutral.

Applying law of mass action.

Dissociation of weak base MOH and weak acid HX may be expressed as.

39

Degree of hydrolysis:

Suppose initial conc. of

In case of salts of weak acid bases, degree of hydrolysis does not depend upon the concentration of salt. hydromium conc and PH.

Putting the value of h

40

In case Ka = Kb,

PH = 7 In case Ka> Kb, the solution will be slightly acidic and PH will be less than 7. On the other hand if Ka > Kb, the solution would be slightly basic and the PH would be greater than 7. 3. Salt of a strong acid and a strong base: e.g. Nacl, Kcl, KNo3, Na2SO4 etc. salt these type are not hydrolysed and hence their aqueous solutions are neutral. MX, MOH and HX are completely dissociated.

Acid-base Indicators: These are the substances which change color according to hydrogen ion concentration of the solution to which they are added. They are usually weak acids or weak bases. Let us consider an indicator which is a weak acid (HIn). The equilibrium between indicator and its conjugate base (In) may be written as.

At low PH, the conc. of is high so the equilibrium is pushed toward left and the equilibrium solution has color A. at high PH, the conc. Of is low so the equilibrium will be pushed to the right and the equilibrium solution has color B.

PKIn = PH
41

The PH of the solution at the end point is equal to PKIn. When PH of the solution is equal to PKIn, half of the indicator is in the acid form and half in the form of its conjugate box. The range of an indicator is the PH range over which it changed color. An indicate is most effective if it undergoes a distinct changes in color over a narrow of PH. For most of the indicators the range is within of the PKIn value. A universal indicator is a mixture of indicators which gives a gradual change from one color to the other over a wide range of PH. The approximate PH of the solution can be determined from the color obtained when a few drops of universal indicator are added to the solution. Acid-base Titrations: In acid-base titrations, generally an acid solution of known concentration is taken in a burette and in added to an alkaline solution of unknown concentration taken in a conical flask. At end point, all the alkali has been neutralized and t6he solution contains salt and water only. The end point is indicated by color change of the indicator. A graph of the PH versus the volume (v) of titrating solution is known as titration curve. With the help of titration curves we can choose proper indicator for a particular titration. It may be noted that at the equivalence point there is a sharp increase in PH except in case of titration of a weak base with a weak acid. A proper acidbase indicator is the one whose PH range falls on the vertical portion of the titration curve and such an indicator gives a sharp change at the end point. 1. Titration of strong acid against strong alkali: (curve A) NaOH(al) + HCL (al) Nacl(al) + H2O(e) In this case as the alkali is addeds to acidic solution, the PH slowly changes in the beginning. However, at the equivalence point PH changes rapidly from about 3.5 to 10. Thus any indicator having PH range between 3.5 and 10 will identify the equivalence point. So phenolphthalein, methyl orange could be used as indicator.

2. Titration of strong acid against weak alkali: (curve B) In this case the PH changes rapidly from 3.5 to 7.0 at the equivalence point. Methyl orange, Methyl red are suitable indicators for this type of titration. Phenolphthalein is unsuitable because its PH range lies outside the vertical portion of the curve.
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3. Titration of weak acid against strong box: (curve c) CH3CooH + NaOH CH3CooNa + H2O The vertical portion of this titration curve lies between PH 7 and PH 10.6. phenolphthalein is suitable indicator for this titration.

Titration of weak acid against weak base: CH3CooH + NH4OH CH3CooNH4 + H2O In this type of titration there is no sharp increase in PH at the equivalence point. No indication is suitable for this type of titration. Buffer solution: It is a solution which resists the change in H3O+ ion cone. Or PH value on addition of small amount of acid, base or on dilution. Buffer solutions have reserve acidity or reserve acidity e.g. Human blood is a natural buffer having PH value in slightly basic region I.e. PH ~ 7.3-7.4. Types of buffer solution: 1. Acidic buffer: The buffer solution having PH in acidic region. It is prepared by mixing equimolar amount of weak acid and its salt with strong box. E.g. CH3CooH + CH3CooNa PH = 4.74 2. Basic buffer: The buffer soluti9on having PH in basic region. It is prepared by mixing equimoles amount of weak base an its salt with strong acid. E.g. NH4OH + NH4cl PH = 9.26 3. Neutral buffer: Buffer solution having PH = 7. A solution of the salt of weak acid-weak base can also act as neutral buffer e.g. CH3CooNH4, PH = 7. Buffer action: It is the ability of the buffer solution to resist the change in PH value on addition of small amount of acid, base or dilution. Buffer action of acidic buffer: e.g. Acidic buffer CH3CooH + CH3CooNa . This solution will have high conc. Of undissociation acetic acid molecules, acetate ions and sodium ion due to common ion effect.
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This solution will have low conc. Of H3O+(al) When small amount of acid is added: i.e. H3O+ ions are added, H3O+ will combine with acetate ion to form undissociated molecules of acetic acid. It means added H3O+(al) are neutralized by acetate ions. So reserve basicity is due o acetate ions. When small amount of base is added: i.e. OH- ions are added OH- ions will combine with ions furnished by acetic acid molecules to form water. This will disturb the equilibrium.

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