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CHAPTER : REDOX REACTIONS

Red means reduction ox means oxidation . The reactions in which oxidation and reduction occur simultaneously are called redox reactions. OXIDATION AND REDUCTION CLASSICAL CONCEPT: Oxidation: A process which involves addition of oxygen or removal of hydrogen is called oxidation . e.g C + O2 CO2 KI + H2O2 I2 + 2KOH Oxidising agent : A substance which brings about oxidation is called oxidising agent. e.g O2 , Cl2 etc. Reduction: A process which brings about addition of hydrogen or removal of oxygen is called reduction . e.g N2+ H2 2NH3 ZnO + C Zn + CO Reducing agent : is a substance which brings about reduction. e.g H2 , C ELECTRONIC CONCEPT : Oxidation : It is a process in which an atom or ion loses one or more electrons . Na Na+ + e Reduction : It is a process in which an atom or ion gains one or more electrons Cl + e- ClOxidising agent : A substance which oxidizes others and itself get reduced is called oxidising agent e.g Cl2 , O2 Reducing agent : A substance which reduce others and itself get oxidized is called reducing agent e.g Na , Fe etc. Redox reactions : Reactions in which both oxidation and reduction occur simultaneously are known as redox reactions e.g 2Mg + O2 2MgO Mg Mg +2 + 2 e- ( Oxidation) [O] + 2e- O2- ( Reduction ) 2Na + Cl2 2NaCl Na Na+ + 1e- (Oxidation) Cl+ 1e- Cl- (Reduction) Redox Reactions Copyright www.chemistrymantra.com Page 1

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CLASSIFICATION OF REDOX REACTIONS Redox reactions are classified into two types : Direct redox reactions and Indirect redox reactions DIRECT REDOX REACTIONS : A redox reaction in which both oxidation and reduction takes place in the same beaker is called direct redox reactions . e.g. When a zinc rod is dipped in CuSO4 solution ,the following observations are made:

1.Zn rod start dissolving and loses its weight gradually . 2. The blue colour of the solution slowly fades away . 3.The reddish brown precipitates of Cu settles down at the bottom of the beaker . 4. The reaction is exothermic . 5.The solution remains electrically neutral. Oxidation : Zn(s) Zn +2 (aq)+ 2eReduction : Cu+2 (aq)+ 2e- Cu(s) Overall Zn (s)+ Cu +2 (aq) Zn +2(aq) + Cu(s)

INDIRECT REDOX REACTIONS: The redox reaction in which oxidation and reduction takes place in two separate containers are called indirect redox reaction. Electrochemical cell :A device which is used to convert chemical energy produced in a redox reaction into electrical energy is called electrochemical cell. Take two beakers and fill them separately with solutions of ZnSO4 and CuSO4 . Place a Zn rod in ZnSO4 and Cu rod in CuSO4 solution. ZnSO4 solution is connected to CuSO4 through a salt bridge.

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Observation : 1. The voltmeter shows deflection indicating electrons are flowing in the circuit . 2. The Zn rod loses weight and Cu rod gains weight . 3. The weight of Zn dissolved and weight of Cu deposited are in the ratio of their equivalent weights . 4. The concentration of ZnSO4 solution increases in Zn half cell and concentration of CuSO4 decreases. 5. The solution remains electrically neutral . 6. The cell stops working after some time . Reactions : At anode : Zn(s) Zn +2 (aq)+ 2eAt cathode: Cu+2 (aq)+ 2e- Cu(s) Overall Zn (s)+ Cu +2 (aq) Zn +2(aq) + Cu(s)

SALT BRIGE A salt bridge is actually consist of a u- shaped tube filled with a semi-solid paste obtained by adding gelatin or agar agar to the solution of strong electrolyte (such as K2SO4 , KCl , KNO3 etc.) .The essential requirements are : 1. The electrolyte should be inert i.e the ions of the electrolyte should not react chemically with the species of two half cells . 2. The mobility of cations and anions of electrolyte should almost be same. Redox Reactions Copyright www.chemistrymantra.com Page 3

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Functions of salt bridge : 1. It completes the inner circuit by flow of ions from one solution to another. 2. It helps in maintaining the solution electrically neutral. If the salt bridge is not employed the flow of electric current will not occur . The moment two electrodes are connected by a wire , the flow of electrons from Zn to Cu rod starts . As a result of this a net positive charge is developed near the Zn rod due to accumulation of Zn+2 ions . On the other hand Cu +2 ions accept the electrons released by Zn rod . This leads to excess of SO42- ions in the solutions .Because of this further flow of electrons will stop. But when we apply salt bridge then towards Zn+2 ions , SO42- will move and towards SO42- ions there is a migration of positive charged ions . Hence two solutions become electrically neutral. Symbolic Representation Of Galvanic Cell: 1. Anode is written on left hand side .Solid phase first and then metal ion. 2. Cathode is written on right hand side . Metal ion first then solid phase . 3. Between anode and cathode ,salt bridge is present [represented in form of ] 4. Concentration is written along with ions in brackets. Zn / Zn +2 (1M)Cu +2(1M) / Cu Cu / Cu +2 (1M) Ag+ (1M) / Ag

Difference between Direct redox reaction and Indirect redox reaction: Direct Redox Reaction Indirect Redox Reaction

1.The reaction takes place through internal 1. The reaction takes place through external circuit. 2.Heat is liberated in this reaction 3.Electrical energy is not produced 4.Reaction proceeds towards completion circuit 2. Heat is not liberated in this reaction 3. Electrical energy is produced 4. Reaction is not completed

5.The cations accept the electrons in the 5. The cations accepts the electrons at the solution and metal formed settles down at the surface of cathode and metal formed get bottom deposited at the cathode

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www.chemistrymantra.com ELECTRODE POTENTIAL :

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The tendency of an electrode to loose or to gain electrons under standard condition is called Electrode Potential. Oxidation Potential: The tendency of an electrode to lose electrons is called oxidation potential . O.P 1/ Concentrations of ions at electrode Reduction Potential: The tendency of an electrode to gain electrons is called reduction potential. R.P concentrations of ions Electrode potential depends upon : (i) (ii) (iii) Concentration of ions in the solutions Nature of the reactants Temperature

Standard Electrode Potential : The electrode potential which is measured under standard conditions like 298 K temperature and 1 Molar concentration is called Standard Electrode Potential

STANDARD HYDROGEN ELECTRODE :[SHE] As electrode potential of single electrode cannot be determined therefore electrode potential can be measured by using some reference electrodes . i.e SHE . SHE consist of platinum wire fitted in a glass tube and has platinum foil attached to it. The coil is coated with finally divided platinum which act as Platinum Electrode . It is dipped in acid solution containing H+ ions in 1M concentration . Pure Hydrogen gas is bubbled into the solution .

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www.chemistrymantra.com If SHE act as anode : H2 (g) 2H+ + 2eIf SHE act as cathode : 2H+ + 2e- H2(g) Electrode potential of SHE is zero

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Importance : It helps in the determination of electrode potential values of other electrodes .

ELECTROMOTIVE FORCE: EMF The difference between the electrode potential of two half cells is known as EMF Eocell = Eo(right) Eo (left) If EMF of the cell is positive then the reaction is spontaneous . If the EMF of the cell is negative then the reaction is non spontaneous . Measurement Of Standard Electrode Potential : Measurement of standard electrode potential of Zinc electrode : Insert Zn rod in 1M ZnSO4 solution. Connect it with SHE as shown in the figure .The flow of electrons is from Zn electrode to hydrogen electrode . In this case Zn rod act as anode and SHE act as cathode .The voltmeter shows reading 0.76 volt.

Eocell = Eo(right) Eo (left) = Eo(cathode) Eo (anode) 0.76 = 0.00 - Eo (Zn/Zn+2) Eo (Zn/Zn+2) = - 0.76 Volt ELCTROCHEMICAL SERIES: The arrangement of elements in order of increasing reduction potential value is called electrochemical series . Redox Reactions Copyright www.chemistrymantra.com Page 2

www.chemistrymantra.com Electrode Li K Na Mg Zn Fe Cd Sn Pb H2 Cu Ag F Electrode Reaction Li+(aq) + e - Li (s) K+(aq) + e - K(s) Na+(aq) + e - Na(s) Mg2+(aq) +2 e - Mg (s) Zn2+(aq) +2 e - Zn (s) Fe2+(aq) +2 e - Fe (s) Cd 2+(aq) +2 e - Cd (s) Sn2+(aq) +2 e - Sn (s) Pb2+(aq) +2 e - Pb (s) 2H+(aq) +2 e - H2 (s) Cu 2+(aq) +2 e - Cu (s) Ag+(aq) + e - Ag (s) F2(g) +2 e - 2F-(aq)

www.cbseanswers.com Standard Reduction Potentials -3.05 -2.93 -2.71 -2.36 -0.76 -0.44 -0.40 -0.14 -0.13 0.00 +0.34 +0.80 +2.87

Application of electrochemical series: 1. To compare the relative oxidizing and reducing power: Greater the reduction potential , more easily is the substance get reduced and stronger is oxidizing agent .Here F2 is stronger reducing agent while Li+ is stronger oxidizing agent 2. To compare the relative reactivities of metals. Lower the reduction potential of a metal , more easily it can lose electrons and hence greater is the reactivity. 3. To calculate the EMF of any electrochemical cell. Eocell = Eo(right) Eo (left) = Eo(cathode) Eo (anode) 4. To predict whether a metal reacts with acid to liberate hydrogen gas : A metal which has high tendency to loose electrons with respect of hydrogen can liberate hydrogen gas i.e the metal should have a negative reduction potential. 5. To predict the spontaneity of a reaction : If EMF of redox reaction comes out to be positive the reaction is spontaneous.

Redox Reactions

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www.chemistrymantra.com NUMERICALS:

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1. Calculate the standard EMF of a cell which involves the following cell reaction Zn + 2 Ag+ Zn +2+ 2 Ag Given Eo Zn+2 / Zn = - 0.76V , Eo Ag+/ Ag = 0.80 V Solution : Eocell = Eo(cathode) Eo (anode) = 0.80 (-0.76) = 1.56 V 2. Find out whether Zn and Ag reacts with 1M H2SO4 to give H2 gas or not . Given Eo Zn+2 / Zn = - 0.76V , Eo Ag+/ Ag = 0.80 V Solution (i) Zn + 2 H+ Zn +2+ H2 Eocell = Eo(cathode) Eo (anode) = 0-(-0.76) = + 0.76 volts As EMF of cell comes out to be positive so reaction is spontaneous (ii) 2 Ag + 2 H+ 2Ag ++ H2 Eocell = Eo(cathode) Eo (anode) = 0 0.80 = -0.80 volt As EMF of cell comes out to be negative so reaction is nonspontaneous 3. Reason out whether 1M AgNO3 solution can be stored in Cu vessel or 1M CuSO4 solution can be stored in Ag vessel . Given EoCu+2 / Cu = 0.34V , EoAg+/ Ag = 0.79 V Solution: Cu + 2 Ag+ Cu +2+ 2 Ag Eocell = Eo(cathode) Eo (anode) = 0.79 0.34 = 0.46 V As EMF of cell comes out to be positive so reaction is spontaneous so we cannot store AgNO3 in Cu vessel. Cu +2 + 2 Ag Cu + 2 Ag+ Eocell = Eo(cathode) Eo (anode) = 0.34 0.80 = -0.46 V As EMF of cell comes out to be negative so reaction is nonspontaneous so CuSO4 can be stored in Ag vessel .

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www.chemistrymantra.com OXIDATION NUMBER:

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It is the charge assigned to an atom of a molecule or of an ion according to some arbitrary rules. Rules for determination of Oxidation Number 1. The oxidation number of an element in the free state is zero. E.g oxidation no. of He is zero , Hydrogen =0. 2. The oxidation number of an ion is same as the charge on ion K + = +1 , Ca+2 = +2 Al +3 = +3. 3. In binary compounds of metals and non metals , the oxidation number of metal is always while nonmetal , the oxidation number is negative e.g NaCl oxidation number of Na = +1 and Cl = -1 . 4. In all the compounds of hydrogen , the oxidation number of hydrogen is +1 except in hydrides of active metals such as LiH , NaH , KH etc. the oxidation number of Hydrogen is -1. 5. In compounds containing oxygen , the oxidation number of oxygen is -2 except in peroxides such as Na2O2 and in OF2 where oxidation number of oxygen is -1 and +2 respectively. 6. Oxidation number of alkali metals is always +1 7. Oxidation number of alkaline earth metals is always +2. 8. Oxidation number of halogens is always -1. 9. In interhalogen compounds of Cl , Br , the more electronegative of two halogens get the oxidation number of -1 . 10. For neutral molecule like NH3 the oxidation number is zero .And for complex ions like SO4 2- oxidation number is -2 . Various examples to find out the oxidation number: 1. Find the oxidation number of S in (i) H2SO4 (ii) H2SO3 (iii) SO42- (i) SO3 2(i) H2SO4 +1 x -2 H2 S O4 2(1) + x + 4(-2) = 0 x-6=0 x=6 (iii) SO4 2x + 4 (-2) = -2 x- 8 = -2 Redox Reactions (iv) SO3 2x + 3 (-2) = -2 x- 6 = -2 Copyright www.chemistrymantra.com Page 1 (ii) H2SO3 +1 x -2

H2 S O3 2(1) + x + 3(-2) = 0 x4=0 x=4

www.chemistrymantra.com x=+6 x = +4

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2 . Find the oxidation number of Fe in K4[Fe(CN)6] +1 x -1 K4[Fe(CN)6] Ans = +3 DIFFERENCE BETWEEN VALENCY AND OXIATION NUMBER S.NO 1. VALENCY OXIDATION NUMBER ,x+46=0 ,x=+2

3. Calculate the oxidation number of N in nitrous acid (HNO2)

Valency of an atom is combining O.N is charge assigned to an atom o a capacity of atom with other element molecule according to some rules. It may have sign +ve or ve

2. 3.

It is only number without any sign.

Except noble gases , valency of no O.N of any element can be zero other element is zero.

4. 5. 6.

Valency is always a whole number Element has fixed valency

It can be fractional It is usually different

Some elements may show variable One element may have variable oxidation valency but it has normally not more number. than two values

REDOX REACTIONS : The reactions in which both oxidation and reduction occurs simultaneously are called redox reactions
Increase in O.N

+1-1 0

+1-1

HBr + Cl2 2HCl + Br2

Decrease in O.N

Increase in oxidation number is oxidation . Decrease in oxidation number is reduction . Types Of Redox Reactions 1. Combination reactions : The reactions in which two or more than two atoms or molecules combine to form a new molecule is called combination reaction. 0 0 +2 -2

2Mg + O2 2MgO Redox Reactions Copyright www.chemistrymantra.com Page 2

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2. Decomposition reactions :The reactions in which molecule breake down to simple components are called decomposition reactions . +1 -2 0 0

2H2O 2H2 + O2 3. Displacement reactions :The reactions in which an atom or ion is displaced by an atom or or ion of another element are called displacement reactions . Displacement reactions are of two types (i) Metal displacement reactions : 0 +2+6 -2 2+6-2 0

Zn + CuSO4 ZnSO4 + Cu (ii) Non metal displacement reactions : Na + H2O 2NaOH + H2 Zn + HCl ZnCl2 + H2 Among all halogens F2 is strongest oxidising agent . It can displace chlorine, bromine and iodine from their salt solutions .It can even displaces H2 from H2O(l) 2F2 + 2H2O 4HF + O2 4. Disproportionation reactions : The reactions in which same element can reduced as well as oxidized such reactions are called disproportionation reactions . -1 -2 0

2H2O2 2H2O + O2 BALANCING OF REDOX REACTIONS: BALANCING THE EQUATION BY OXIDATION NUMBER METHOD: 1. Write down the skeletal equation. 2. Write down the oxidation number of each element . 3. Calculate the increase or decrease in oxidation number per atom. 4. Balance the increase or decrease in oxidation number by multiplying increase or decrease in O.N per atom by the number of atom undergoing that change. 5. Multiplying the reactants by suitable integers so as to equalize the total increase or decrease in oxidation number 6. Balance all atoms other than H and O 7. In acidic medium : Balance O- atom by adding H2 O to side deficient in oxygen. And balance H- atom by adding H+ to the side deficient in hydrogen in acidic medium 8. In Basic medium : Balance O- atom by adding OH- to side deficient in O- atom. Redox Reactions Copyright www.chemistrymantra.com Page 3

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Balance H- atom by adding one molecule of H2O for each H- atom on the side deficient in H atom and equal number of OH- ions in opposite direction . Problems Based On Balancing Of Redox Reactions: (a) Balance the given reaction in acidic medium MnO4 - + Fe+2 Mn+2 + Fe+3 .
+7

1.MnO4 - + Fe+2 Mn+2 + Fe+3

Decrease in O.N by 5 +7

2.MnO4 - +Fe+2 Mn+2 +Fe+3

Increase in O.N by 1

3.Balance increase or decrease Increase 1 x 5 = 5 , Decrease 5 x 1 = 5 4.Multiply MnO4- by 1 and Fe+2 by 5 we get MnO4 - + 5Fe+2 Mn+2 + Fe+3 5.Balance all atoms other than H and O MnO4 - + 5Fe+2 Mn+2 + 5Fe+3 6.Balance O-atom by adding H2O to side deficient in oxygen. MnO4 - + 5Fe+2 Mn+2 + 5Fe+3+ 4H2O 7.Balance H-atom by adding H+ to the side deficient in hydrogen MnO4 - + Fe+2+ 8 H+ Mn+2 + 5Fe+3+ 4 H2O The above reaction is balanced now. (b) Balance the given reaction in acidic medium 1. Cr2O7 2- + Fe+2 Cr+3 + Fe+3
+6 2. -2

Cr2O7 2- + Fe+2 Cr+3 + Fe+3

Dec. in O.N by 3 per atom

(6 per two atom)

3. Cr2O7 + Fe Cr+3 + Fe+3

Inc . in O.N by 1 per atom

2-

+2

4. Balance inc. or dec. Increase 1x 6 = 6 , Decrease = 6 x 1 = 6 5. Cr2O7 2- + 6Fe+2 Cr+3 + Fe+3 6. Cr2O7 2- + Fe+2 2Cr+3 + Fe+3 7. Cr2O7 2- + Fe+2 Cr+3 + Fe+3+ 7H2O 8. Cr2O7 2- + Fe+2+ 14 H + Cr+3 + Fe+3 +7 H2O Hence Balanced . Redox Reactions Copyright www.chemistrymantra.com Page 4

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(c) Balance the given reaction in Basic medium. 1. Cr2O4 2- + SO3 2- [Cr(OH4]- + SO4 22. +6
2+4 2+3 +6

Cr2O4 + SO3
1.

[Cr(OH4] + SO4 2-

Dec. in O.N by 3 per atom

Cr2O4 2- + SO3 2- [Cr(OH4]- + SO4 2-

Inc. in O.N by 6 per atom

4. Inc 2 x 3 = 6 , Dec 3 x 2 = 6 5. 2Cr2O4 2- + 3SO3 2- [Cr(OH4]- + SO4 26. 2Cr2O4 2- + 3SO3 2- 2[Cr(OH4]- + 3SO4 27. 2Cr2O4 2- + 3SO3 2- + 3OH- 2[Cr(OH4]- + 3SO4 28. 2Cr2O4 2- + 3SO3 2- + 3OH-+ 5 H2O 2[Cr(OH4]- + 3SO4 2-+ 5 OHBALANCED

BALANCING THE EQUATION BY ION ELECTRON METHOD: 1. Write down O.N of all the elements. 2. Find out the species which are oxidized and reduced 3. Split the reactions into two half i.e oxidation half and reduction half. 4. Balance all the atoms other than hydrogen and oxygen. 5. The O.N of elements are balanced by adding electrons to whatever side necessary. 6. The charge is balanced by adding H+ ions if reaction occurs in acidic medium or by OHions if reaction occurs in basic medium. 7. H and O are balanced by adding water molecules to the side deficient . 8. The two half equations then multiplied with suitable integer so that the total no. of electrons gained in on half equation is equal to number of electrons lost in the other half equation . The two half equations are then added up.

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www.chemistrymantra.com Problems Based On Balancing Of Redox Reactions: (a) Balance the equation by ion electron method Cr2O7 2- + Fe+2 + H+ Cr+3 + Fe+3 + H2O Solution :

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1. Find out the elements whose O.N undergo a change Oxidation Fe+2 Fe+3 , Reduction Cr2O7 2- Cr+3 2. Balance the Oxidation half equation : (i) (ii) (iii) Fe+2 Fe+3 Add electrons to side which is deficient of electrons Balance the charge : Both sides has +2 charge Cr2O7 2- Cr+3 Balance all atoms other than H and O : Cr2O7 2- 2Cr+3 Add e- to side deficient of electrons : Cr2O7 2- + 6 e- 2Cr+3 Balance the charge : Cr2O7 2- + 6 e- + 14 H+ 2Cr+3 Balance H and O by adding H2O : Cr2O7 2- + 6 e- + 14 H+ 2Cr+3 + 7 H2O Fe+2 Fe+3 + 1e-

3. Balance the Reduction half equation: (i) (ii) (iii) (iv) (v)

4. Add oxidation half and reduction half [Fe+2 Fe+3 + 1e-]x 6 Cr2O7 2- + 6 e- + 14 H+ 2Cr+3 + 7 H2O Cr2O7 2- ++ 6 Fe+2 + 14 H+ 2Cr+3 + 6 Fe +3 + 7 H2O (b) Balance the equation MnO4 - + H2C2O4 Mn+2 + CO2 in acidic medium by half reaction method . Solution : 1. Oxidation half : H2C2O4 CO2 , Reduction Half : MnO4 - Mn+2 2. Balance the oxidation half : (i) (ii) (iii) (iv) H2C2O4 CO2 H2C2O4 2CO2+ 2 eBalance charge by adding H+ ions: H2C2O4 2CO2+ 2H+ +2 eH and O are already balanced. MnO4 - Mn+2 MnO4 - + 5 e- Mn+2 MnO4 - + 8 H++ 5 e- Mn+2 Copyright www.chemistrymantra.com Page 6

3. Balance the reduction half : (i) (ii) (iii)

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www.chemistrymantra.com (iv) MnO4 - + 8 H++ 5 e- Mn+2 + 4 H2O

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4. Add oxidation half and reduction half: [H2C2O4 2CO2+ 2H+ +2 e-]x5 MnO4 - + 8 H++ 5 e- Mn+2 + 4 H2O 2MnO4 - + 6 H++ 5 H2C2O4 2Mn+2 +10 CO2+ 8 H2O (c) Balance the equation Zn + NO3 - Zn+2 + NH4+ in basic medium Solution: 1. Oxidation half: Zn Zn+2 , Reduction half : NO3 - NH4+ 2. Balance oxidation half: (i) (ii) Zn Zn+2 Zn Zn+2 + 2 eNO3 - NH4+ NO3 - + 8 e- NH4+ NO3 - + 8 e- NH4+ + 10 OHNO3 - ++7H2O + 8 e- NH4+ + 10 OH-

3. Balance reduction half: (i) (ii) (iii) (iv)

4. Add oxidation half and reduction half : [Zn Zn+2 + 2 e-] x 4 NO3 - +7H2O + 8 e- NH4+ + 10 OH4 Zn +NO3 - +7H2O 4Zn+2 + NH4+ + 10 OH-

Redox Reactions

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