CHAPTER AT A GLANCE F OXIDATION AND REDUCTION REACTIONS tion is defined as the addition of oxygen or elect ‘agen or electropositive element from a substance: res hydrogen is called an 7.1. CLASSICAL IDEA Of ‘according to it the term oxi : to.a substance or removal of hydrc oneganive er wg to this concept, a substance which gives oxygen OF remoN ‘Accordin oxidising agent or oxidant Forexample, (@) Addition of oxygen C +0, + CO; ‘Addition of electronegative element @) Ca + Ch — CaCh (0) Removal of hydrogen 2H,S + 0; —> 2S + 2H:0 (d) Removal of electropositive radical OKI + H,O + 03 —> b + 2OHE oy tropositive element toa substance oF removal “addition of hydrogen or elec ant from a substance. Reduction is defined a of oxygen or electronegé Following are the examp! (@) Addition of hydrogen CH, =CHo&) + 2) 5 HyC— CH) (0) Addition of electropositive element 2FigCls (ag) + SAC) —? Hg,Ch() + Sachs (a) (0) Removal of oxygen 2Hg0() 7 2H () + 02) igative element ) —» 2FeCh, (ag) + 2H1C1 (aq) ‘substance which gives hydrogen or ative elemel Jes of reduction processes= (@ Removal of electrone eC H, 2FeCls (a) * ay removes oxygen is called a ‘According to this concept: 9 reducing agent or reductant. Scanned with CamScanner7.2. REDOX REACTIONS ee Oxidation and reduction reactions always occur simultaneously be side'by, " example, the reaction a. ses HgCly (ag) + SnCly (ag) —> HpaCl(@) + SnCh (ag) In the above reaction, stannous chloride (SnCl,) is oxidised to stannic chloride (Snel,) addition of electronegative element chlorine to it. Simultaneously mercuric ‘chloride gree reduced to mercurous chloride (Hg3Cl) because of addition of electropositive element is to it. Thus, SnCl is oxidised by HgCl, while HgCl, is reduced by SnCly, Therefore, Hy yey ‘oxidant while SnCh acts as reductant during the reaction. 18h ats Such reactions in which oxidation and reduction occur simultaneously are called Fed0x reaction, 7.3. ELECTRONIC CONCEPT OF OXIDATION AND REDUCTION According to electronic concept, oxidation is defined as a process which involves lose of more electrons by anatom, ion ormolecule. Thus the process ofoxidationinvolvesdeelectonagge For example, Na —> Nat + & Fe? —> Fe* + & 2cr —> Cl, + 26° H,0, —> Q) + 2H* + 26° Reduction is defined as a process which involves gain of one or more electrons BY an atom, anion ora molecule. ‘Thus the process of reduction involves electronation. For example, + 2° —> S Fe + & —> Fe* MnOq + & —> MnOF Cl + 26° —> 2Cr N TRANSFER REACTIONS a redox reaction consists of two half involves loss of electron or electrons (oxidation). Thisiscalled ” half involves gain of one or more electrons (reduction) ands f electrons involved in both the half reactions shoul 7.4, REDOX REACTIONS IN TERMS OF ELECTRO! Since oxidation and reduction always occur simultaneously, reactions. One half of the reactior oxidation half reaction. The othe called reduction half reaction. The number o! be the same since no free electrons appear 1n the overall redox reaction. This may be illustrated with the help of following examples: 4Na (5) + O> (s) —> 2Na,0(5) 2Na(s) + Ch (g) —> 2NaCl (s) Both these reactions are redox reactions since in both of them sodium is oxidised due to chet addition of oxygen or more electronegative chlorine, At the same time, oxygen and chlorine ate feduced due to gain of electropositive element sodium. vcs onide and sodium chloride are fonic compounds maybe ‘According to chemical bonding, sodi written as (Na*),0* (8) and Na‘CI (5). j Due to the development of charges on the species produced, we can write these reactions it following manner: % a oss of 20 Scanned with CamScanneract of the above processes ean be considered ne toss of electrons fe, oxidation and the other os MO a halt ae bi vo of salt peroxide (Na,O eat be lustrated ee lectrons j,, reduction. form Na 6) Onl) + ) > Nat +(e] 4 (oxidation half reaction) 2 4 Oe (reduction half reaction) halo 4Na (8) + O2@) 5 2(Nat sion of sodium chloride can be aie ‘or Na;O;(overall redox reaction) 2N “ la (8) —> 2Nat (g) + 2° (oxidation half reaction) Ch, (@) + 26 —5 2c ; amos half reactions gives the overall redox ba : ST ai sean 2Na (9) + Ch @) —9 INa'Cr (@) or 2NaCl 6) reactions soditum, which is oxidised, spabove Ke 0 | acts as a reducing agent because it donates electron Beef the clement interacting with it and thus helps in fencing hr CHE ad oe reduced and act as oxidising agents because these accept electrons (rome soa oxidising agent is a substance which can accept one or more electrons Whil edict \t mpaabstance which can give one or more electrons, non al s COMPETITIVE ELECTRON TRANSFER REACTIONS. jp this method, itis always assumed that there isa complete transfer of electrons from a less Hecionegative atom 0 a more electronegative atom, For example ifwe place stip of metallic zincin an aqueous solution of per nitrate (Fig. 71) for about one tout it is noticed that the strip becomes coated with reddish metallic copper and the blue colour of the solution disappears. Formation of Zn" ions among the products can easily be judged when fhe blue colour of the solution due to Cu2* has disappeared. If hydrogen sulphide gas is passed through the colourless solution containing Zn? ions, appearance of white zinc sulphide, ZnS can ‘peseen on making the solution alkaline with ammonia, { ensy ot blue colour Finally Cu? is ‘nr0d ploced _is reduced deposited as Cu in copper an ‘irate solution i Cu deposited Initial stage Intermediate stage Final stage 8 Fig. 71 Redox reaction between zine and aqueous solution of copper nitrate occuring na ‘beaker. ‘etween metallic zinc and the aqueous solution of copper nitratel is Zn (s) + Cu(NOs)2 (ag) —> Zm(NO3)2 (ag) + Cu(s) + Cue (aq) —> Zn?* (ag) + Cu(s) zn and, therefore, zinc is oxidised. At the same time ced by gaining electrons from the zine, Therefore, the The reaction b or Zn(s) Here, zinc has Jost electrons to form accepting the electrons copper ion is redu | above reaction may be written as : release of 2e~ Zan (9) + CUP™ (aq) —> ZC) +H) gain of 2° ‘Similarly, if a copper rod is placed in AgNO, solution, it develops blue colour due to the formation ‘Cu ions. Scanned with CamScannerlee of oe) Cu (s) + 2Agt (ag) > Cu2* (aq) + 248 (9) Legain ofa Based upon this relative electron releasing tendencies, metals have been arranged in the, the series known as activity series or electrochemical series. In this series, the metal which, ahigher position loses electrons (acts a reducing agent) while the metal whose ions accep, (acts an oxidising agent) occupies a lower position in the series. 7.6. OXIDATION NUMBER Oxidation number denotes the oxidation state of an element in a compound, which is ass according to a set of rules formulated on the basis that electron in a covalent bond belongs me tomore electronegative element. Oxidation number of an element may be defined as the charge which an atom of the element has in its ion or appears to have when present in the combined state with other atoms, Rules for the calculation of oxidation number. These are given below : (® Inclements, in the free or the uncombined state, each atom has an oxidation number of ze. For example, oxidation number of hydrogen in Fz, oxygen in O, or O3, phosphorus in Py ang ong lecting sulphur in Sy is zero. (i) The oxidation number of an element in a simple monoatomic ion is equal to the charge present jon number of Na is +1, in A** oxidation number of Alis on the ion. For example, in Na*, oxi +3and in S* oxidation number of S is ~ 2. (iii) The oxidation number of oxygen in most of its compounds is ~ 2. However, in peroxides (€g., HO,, Na,0.), each oxygen atom is assigned an oxidation number of ~1 and in superoides (eg., KO,, RbO;), each oxygen atom is assigned an oxidation number of ~ (4). The oer exception is when oxygen is bonded to fluorine, In such compounds eg., oxygen difluoride (OF,) and dioxygen difluoride (O2F.), the oxygen is assigned an oxidation number of + 2and +1, respectively. (ia) The oxidation number of hydrogen is + 1, except when it is bonded to metals in binary compounds (that is compounds containing two elements). For example, in LiH NaHand (Cal; its oxidation number of hydrogen is ~ 1. (2) Inall its compounds, fluorine has an oxidation number of ~ 1. Other halogens (Cl, Br and 1) also have an oxidation number of ~ 1, when they occur as halide ions in their compounds. But chlorine, bromine and iodine when combined with oxygen 2 fluorine for example in oxoacids, oxoanions, et, have positive oxidation numbers. (vi) The algebraic sum of the oxidation numbers of all the atoms in a compound must be ze (vil) In polyatomic ion, the algebraic sum of all the oxidation numbers of atoms of the io equal the charge on the ion. A few examples of calculating oxidation numbers are given below : (i) To calculate oxidation number of $ in NaySO, 41 x -2 Na, 8 Scanned with CamScanner-2 e 2ee+12 or x46 ready mentioned the oxidation number is A826, the oxidation state of carbon is +4, ae nn ny ciel le oa Cor state as well a oxidation number of oxygen is 2. aa nee sid ne oxidation state of an elementin.a compound. is implies that the oxidation number i idation number has been used in definin Br idea of OX! een used in defining oxidati A Bee on : It i i tion, Oxidation : It involves an increase in the rie omiree Leen in the gis iven substance. Reduction : It involves decrease in the oxidation number of the element in the given substance. ven 7 . Oxidising Agent or Oxidant : A reagent which can increase the oxidation number of an element in a given substance. Reducing Agent or Reductant : A reagent which lowers the oxidation number of an element ina given substance. ‘* Redox Reactions : Reactions which involve change in oxidation number of the interacting’ species. 77. PARADOX OF FRACTIONAL OXIDATION NUMBER itis found that in some cases, correct oxidation numbers are not obtained by applying the common | rules. For example, | (@) Oxidation of Cr in CrOs. x+5(-2)=0 or x=+10 This is not the correct oxidation number of Cr. It is due to the reason’ that Cr has only five electrons in 3d-orbitals and one electron in 4s-orbital. vnidation number is determined by means of the chemical structure of the In such a case, icture of CrOs is | compound. For example, stru | oO. oO [>< =~ o~ Il So ° We know that in a peroxide linkage, oxidation number of OXYES is-t. 741 « 2) eerie Forcr. Forone Fert oxygen oxygenat of ‘Cr in CrOs is +6- “x= +6 ie, oxidation number 0! 3 ae oer of sulphur in Care's addy H,SO5. (b) Oxidation number of st % Scanned with CamScanner241) + x #3 x (2) + 2E1)=0 Fortwo Forsulphur For} Fortwo hydrogen atom ‘oxygen oxygen atoms ‘tom toms or X¥+2-6-2=0 or x=46 +: Oxidation number of S in H,SOs is +6, 7.8. STOCK NOTATION Its used only in case of metallic compounds. Here in oxidation state of the element ig by Roman numeral written in parenthesis immediately after name or symbol of the elem example copper forms two chlorides, CusClp and CuCl, In CuzCly, oxidation state of Cy! while it is +2 in CuCl. Ex, () Ch, or t (I) chloride; Cu (11) Cl, Copper (II) chloride. Stock notations compounds Agiven mee eno ie Cu;0 Copper (I) oxide Cu, 0 cu Copper (Il) oxide cudo FeCl, Iron (11) chloride Fe (I) Ch FeCl; Iron (IM) chloride Fe (II) Cl, Hg,Cl Mercury (1) chloride Hg» (1) Cly HgCl, Mercury (II) chloride Hg (I) Cl, MnO Manganese (II) oxide Mn (I) O MnO, ‘Manganese (IV) oxide ‘Mn (IV) Oy 7.9. TYPES OF REDOX REACTIONS 1. Combination Reactions : The chemical reactions in which two or more elements or compounds combine to form a single substance are called combination reactions. In general, combination reaction may be denoted in the manner A+B—>C For such a reaction to be redox reactions, either A and B or both A and B must be in the elemental form. All combustion reactions, which make use of elemental dioxygen, as well as other reactions involving elements other than dioxygen, are redox reactions. For example, ° ° 4-2 @ C6) +O) —*+ CO,@) 0 0 H- (ii) Hy (g) + Cl (g) —> 2HCI @) 0 0 42-3 (iii) 3Mg (5) + No (¢) > MgsNo (6) 4a ° 4g) omaee (io) CH, (g) + 20; (g) —4-> COs (g) + 220 (/) 2. Decomposition Reactions : A decomposition reaction involves the break down of a compound into two or more components at least one of which must be in the elemental state. Examples of ana this class of reactions are : 41-2 0 0 @ 2H,0 (1) —4> 2H (g) + Or (g) 41-1 0 0 2NaH (s) > 2Na (s) + Hy (g) 1ay be noted that all decomposition reactions are not redox reacti Scanned with CamScannersacement Reactions :Ina displacement react jonan atom orion in es pyar on or atom of another element. It may be denoted as : n inva compound is XYZ See kz + Y i | | ament actions areof two types:(0)metadsplacementand (#)ron-metal disp plac petal Displacement : A metal in ; @ Me ombined stale Por evant a compound is displaced by another metal in the 4246-2 ° 2. 0 A ‘CuSO, (aq) + Zn (8) —9 Cus) + y 804 (00) ao o ~ 432 0 CrOs (6) + 2AL (6) —45 ALO, (5) + 2Cr (5) (@ Non-metal Displacement : The non-metal displacement redox reactions are chiefly displacement. fovdrogen displacement and a rarely occurring reaction involving Ben For example, | 0. H2 2a 0 2Na (s) + 2H,0 (1) —> 2NaOH (aq) + Hp (8) ° a2 2a ° Cals) + 2H,0() —> Ca(OH) (a) + Ho) Less active metals such as magnesium and iron react with steam to produce dihydrogen 539° 0 HW peu 0 Mg (s) + 2H,0() 29 Mg(OH)2(6) + Fh @) 9 12 82 ° 2Fe (3) + 3H,O() —4> Fex03 6) + 3H (g) ble of displacing, ding those which do not react Many metals, inclu s. For example, hydrogen from acid ° 4 24 ° ‘Za(6) + 2HCI (ag) —> ZnCl (an) + Ha) 0 al 24 0 Mg (s) + 2HC1 (aq) —> MCh (@f) * Hog) cases as we move down from fluorine ‘alements as oxidising agents de to iodine in group 17 of periodic able: This imp replace chloride, bromide “ind iodide ions in solution. In fact, attacks water and displaces the oxygen of water + me 0 a4 0 21,0 (I) + 2F2 @ — 4H (aq) + O28) .n displace bromide and jodide fons in an aqueous solu 0 aa 4-1 0 ) —2KCl (ag) + Bra sidatni is? — 2KCI (ag) + be () dissolve in CCly, they can easily be identified from the Ties that fluorine is s0 reactive that it ca The power of fluorine is so reactive that it tion as shown below = Chlorine cai o Ch + 2K 10) ‘are coloured and ‘As Br, and Ip colour of the solution. a * ‘Above reactions form me Dasie of identifying Brand Tin the laboratory through the test ‘Layer Test’. popularly known as 14¥ humical equations by oxidation 14m that number must be The basic principle for balancing chemic during a redox reaction, total increase in oxidation in oxidation ee ee ones Scanned with CamScanner7.10. BALANCING OF REDOX REACTIONS intermediate oxidation state; and both higher and lower oxidation states of thay formed in the reaction. The clecomposition of hydrogen peroxide is a familiar «, reaction, where oxygen experiences disproportionation. For example, a4 2 ° @ 2H,0, (aq) —> 2H,0 (I) + 0; (g) Here, the oxygen of hydrogen peroxide, which is present in= 1 state is conver oxidation state in O, and decreases to - 2 oxidation state in H,O. 2 0 4 A (i) Cl (g) + 2OH™ (ag) —> CIO (aq) + CI (aq) + 1,0 (I) Here, the oxidation state of chlorine changes from 0 to ~1 and +1, Two methods are used to balance chemical equations for redox reactions. These are : (2) Oxidation number method (8) Half reaction or ion electron method (@) Oxidation Number Method : Balancing is carried out by following the following steps, Step 1 + Write theskeletal redox equation by writing the correct formula for ach rattan product. Step 2 : Assign oxidation number to alll the elements in each compound, Step 3: Identify element or elements which undergo change in oxidation number in the rectn Step 4 + Calculate the increase or decrease in the oxidation number per atom and for whole the molecule/ion in which it occurs. If these are not equal then multiply by suitable coefficients so that these become equal Balance the equation with respect to all other atoms except oxygen and hydrogen. Finally balance oxygen and hydrogen. To balance oxygen atoms, add H,0 molecules to the side deficient in oxygen. Tobalance hydrogen; add H'* ions to the side deficient init, if the reaction takes place in acidic medium. But if the reaction occurs in basic medium, add HO moleculesto the side deficient in hydrogen and at the same time add equal number of OFPionsto the other side of the equation. Example : Using Oxidation Number Method : Permanganate ion reacts with bromide ion ia basic medium to give manganese dioxide and bromate ion. The skeletal ionic equation is : MnO; (aq) + Br (ag) —> MnO, (s) + BrO3 (aq) Step 1 : Assign oxidation numbers for Mn and Br Step 5 : Step 6 Step7 : MnOj (aq) + BE (aq) —> MnO, (6) + BLO5 (a) ‘This indicates that permanganate ion is the oxidant and bromide ions the Step 2 : Calculate the increase and decrease of oxidation number. Oxidation number decreases by 3 per atom i 47 1 is ee i MnOp + Bir-—» MnO, + ‘BrOz Scanned with CamScannerScanned with CamScannerScanned with CamScanner7.3, to electrical energy. The set up d electrochemical cell, emical energy is converted into electrical energy. anes Place in two different compartments called half cells, In each Placed ina suitable electrolytic solution. When the electrodes are anelectrochemical cell isa devi ‘i chemical reaction involved take jalf cell a metallic conductoi icein which ch bya wire and the two compartments tte foflow. ‘he salt bridge jectrolyte such as KCl arid NHNOs, Antinere Fy chemical change. The electroly tic solution in and then cooling into a jelly like substance The metallic rods oF conductors, 5 ctrolyte is the one whose ions are not involved in the U-tube is solidified by y boiling with agar-agar witha provision for an ammeter and ¢ g The metal rods dipping in the half reaction occurs is called called cathode. Here, zinc ‘Witch. salt solution are call anode and the acts as anode w! led electrodes. The elec ‘trode at which oxidation one at which reduction h, lf reaction takes place is hile copper acts as cathode. The reactions involved are : Atanode : 20 > Zn2* 4.6 At cathode : _ Cu? 2a Cu Overall reaction Zn Ci erp The cell may be represented as Zn, Zn™ (ag) || Cu2+ (@q), Cu or Zn| Zn? (aq) | Cu** (ag) | Cu When the switch is in the off position, no Feaction takes place in either of the half celle and no current flows through the metallic Wire. As soon as the switch is in the on Position, we make following obsery, 1. The transfer of el from Zn to Cu?* Current flow <— Electron flow —s Switch ‘ations : lectrons takes place through the metallic ite connecting the two rods (Fig, 72), The current from solution in one beaker {0 Solution in the other beaker flows by the migration of ions through the sat bridge. Scanned with CamScannerCalculation of cell potential : The cell potential or emf of a cell can be calculated relation : setter ertgtis el aa Scanned with CamScanner