5) OXIDATION AND REDUCTION f a Majority of reactions are occurring by the transfer of electrons from one species to another. Therefore, oxidation is called de-electronation while Reduction is called electronation, Since the loss or gain of electrons are relative terms, the gain oy loss of electrons takes’ place simultaneously in a chemical reaction are known as redox reactions. For example the reaction between Zn and CuSO, solution shown as: Zn +CuSO,——> ZnSO, +Cu 2n+¥Cu?* —5 Zn +Cu Since Zn atom loses two electrons i.e. oxidised to Zn while Cu” gains the same number of electrons lost by Zn atom gets reduced to Cu atom. Thus redox reaction consists of two reactions - The reaction showing oxidation is called oxidation half reaction while that representing reduction. is called reduction half reaction. “2n—— > Zn* +2e" (Oxidation half reaction) Cu* +2e"——_ Cy (Reduction half reaction) It may be noted that the number of electrons lost or gain reactions is equal and the reaction mixture of redox reaction The oxidation, according to electronic concept can be defined as loss of electrons by an atom or group of atoms takes place. Due more electrons the atoms or ion changes into a more electro) +ve charge) or less electronegative (decrease in loses electron is said to be oxidised, e.g, (i) neutral atoms lose electrons in two opposite half a reaction in which to the loss of one or positive (increase in -ve charge). The substance which K— >K* +1e" Al—> Al** + 3¢- (ii) Positively charged ions loose electrons and chan charged ions. ge into higher’ positively é Fe® —__, Fo 4 16- (iii) Negatively ion loose electron to give neutral atom or molecules 2 Ty De" (iv), Negative ions loose electrons which results in decrease in negative chargeMnO,* ——+ MnO,” +167 [Reduction according to electronic concept is defined as a reaction which involves gain of electron by an atom or group of atoms, Due to gain of one or more electrons, the atoms or the ions changes into less electro-positive (or more electronegative) state. The substance which gains clectrons is said to be reduced. e.g. (i) Neutral atoms or molecules which gains electrons and changes to negative ions. S+2e ——+s* O, +4e° ——> 20" (ii) Positive ions gains one or more electrons to change into either less positively charged ions or neutral atoms. Fe* +1e° ——» Fe” Fe* +2e" >Fe Sn?" +2e° —>Sn (iii). Negative ion gains electrons resulting in increase in negative charge MnO, +e” ——> MnO, »_loxidising agent (oxidant) and Reducing agent (Reductant) : Oxidising agent {atom, ion or molecule) is that substance which oxidises some other substance and is itself reduced to a lower valency state by gaining-one or miore electrons. While reducing agent (atom, io or molecule) is that substance which reduces some other substance and is itself oxidised to a higher valency state by losing one or more electrons. Let us consider the following reversible redox reaction : Zn+Cu® ——» Zn +Cu |. Reducing oxidising reducing oxidising agent agent agent agent L-#lectrode potential : The potential difference between a metal and a solution. containing its own ions in equilibrium is called electrode potential of that metal or electrode. Metal 7,80,sdlution (Formation of double electric layer gives rise to potential difference between the metal and solution containing its own ions). Depending on the tendency of a metal to lose or gain electrons, the clectrode potential may be of two types namely oxidation Potential and reduction potential. Oxidation potential of a metal indicates its electronConcepts of Chemis! am a whi duction p' pr ts the lee Stenth oe city loosing tendency epee ie fhe ‘ode potential is a Bere ot of elect f electric current per second throu aining 14.4521 gm. mercury at ; i aed directly. First of all, we assign an arbitrary i r “nthe potenti electrode potential to a reference or standard electrode ane pete ie pl ‘ial of the given electrode is measured with respect 2 ase Ho haere Standard electrode potential (Bcc) It can be See a loctrode : r ‘ode. In simple words, with respect to a normal hydrogen electro , potential ofa metal-metal ion electrode is defined as the potential difference between a normal hydrogen electrode and the metal-metal jon elect eee. immersing the metal in its salt solution of 1M concentration at 25°C or = 298 K. It is designated as E’y.4° ‘Types of electrode potential : 1) Oxidation electrode potential (Eq)? It is the potential of the electrode at which ‘oxidation takes place and hence is a measure of the tendency of the electrode’.in a half cell to: get oxidised or to lose electrons. For example, standard oxidation potential of Zn,,/Zn*,,, electrode which is equal to +0.76V, is for the oxidation reaction taking-place at the electrode. ES, or Eo '0.76V znfen?* of the metal. The unit to flow one coulomb o} mercury, 106.3 om long cont single electrode can not be mea t O°C. The potential of a 2g 2 ER, #2 2) Reduction electrode potential (E,,,).,...% It is the potential of the electrode at.which reduction takes place and hence is a measure of the tendency of the electrode:in a half cell to get ‘reduced or to gain electrons. For example, standard reduction potential of Cu,,/Cu”,,, electrode. is 0.34 V is for the reduction reaction taking place vat the electrode.<." ot 3 N = Cup, #2e7%4 = Cus, Ba oF Boag, =0-34V i Redox Potential : Relative strength of oxidising agents or reducing agents can ee brain by comparing their tendencies to accept or furnish electrons. This endency is measured by i redox in te aaleaahnisn tehagtendeneiiis gee'up'an Clecuatvand ieeieteie the solution. While the ions already in olntion will ‘he a eee ae electrons to get discharge as the metal, Bee ee ce eae eres M, Mr i, > +1e This is a reversible reacti me _ Th revers ction representing the oxid 7 ‘onan E xidation o i iti fone at aie reaction and the reduction of positive ions to nets Se ard Redox sea eatential developed at equilibrium is known as rodent ae 2C-Redox stability in water : The ion or molecule present regomipotential: ayed by Redox reactions. The stability of tone ae ey be stable a ‘J ms depend. yf 0 Pe tieaitres if s on nature o! ye us consides ¥arious reactions with water," SS0Wved Oxygen in solution. pia): ith water : Water can act as oxi and liberate hydrogen gas. 's oxidising agent, it will accept electronUrtauner ewes 220 +2e7 > Aggy + 20H gq) “= -(0.059 V) pH. Water may also act as reducing agents when it is oxidised to O,. On(q) + 4H aq) + 47 4.2. H, Oy [B= 1.23 V - (0.059 V) pH. tt is considered that when metal reacts with aqueous acids, it is actually’ the oxidation of the metal by water or by H’ ions. j + 1 Ms) + 220 > Maa) + Fata + OFF tan Mig) + Haq) 9 M* ag) + 3 Hyg) Some metal ions may also get reduced by water with the evolution of oxygen. 3 4 Cola + 2H,0u, ‘ >4 Collin + Orig) +4 cay A reducing agent that can reduce water to Hj tapidly or’an oxidising agent that can oxidise water to O, rapidly cannot survive.in aqueous solution, therefore, "The stability field of water is the range of values of potential and pH for which water is thermodynamically stable towards both oxidation /and reduction.” The stability field of natural water lies between H, production line and O, production line, The area is also confined between the DpH = 4 & pH =9, it is the range of common pH of water found in lakes and streams. Presentation of potential data : The relative thermodynamic stabilities of the series of the species in which one element exists with various oxidation states can be shown diagrammatically. There are various _ ways;such as Frost, Latimer and Pourbaix diagrams to represent potential data. ‘0-5 Frost Diagram : Consider a Redox reaction X(N)+Ne7——>X(O) E° where N = oxidation number, X is the element. A graph plotted of NE against the oxidation number N is known as Frost diagram. Frost diagram can’ also be regarded as a plot of standard reaction Gibb's energy against oxidation. number. The maxima observed in the diagram corresponds to most stable oxidation number. The slope of line joining any two points in a frost diagram is equal to the standard potential of the couple formed by the two species the points represents.Concepts of Chemistry — —— Consider a species which is in two oxidation states y and N’. X(N')+n'e’ —>X(0) Most stable oxidation state t AG? = =n! f | (1) NE X(N")4 1" —>X(0) i | AG"=-n" f EP (2) Substracting equation (2) from (1) we get, oxid.Num —> X(N')-X(-N")+n'e" -n"e= ——>X (0) - X(O) -- (3) o. X(N')+(n'-n") ee X(N"), Similarly 4AG° = AG® - 4G‘ =-(n'FE°-n"FE%) NEP Lemiaee 1 pO "Bo 2 Therefore, .B° = "=_—" 2 n'=n |. ‘This is nothing but‘a slope;of a line’ ’ Interpretation of Frost diagram : ogation aimber 1) If the point lies above the line connecting to adjacent species then it will be unstable with respect to disproportionation. 2) Two species will tend to comproportionation in to an i intermediate species that lies below the straight line joining the terminal spe cies, NE* Unstable with Fospect to lsproportionation NE NE Oxidation number ‘Oxidation number. Manganese exhibit various oxidation states i.e, +1 to +7. The Frost. diagram for Mn species in acidic solution shows a minima for Mn® hence Mn” is more stable as compare to other species, This has been shown in the following diagram.oxidation & Reduction 1 75 HM 904 “4 oe Latimer Diagram : Oxidation number, N 7) The species are arranged according to the oxidation states. The most highly oxidised form is written to the left and the least oxidised form is written to the right. 9) The standard oxidation potential in'volts is'written over the alrow present between the elements in different oxidation states: For example, chlorine shows oxidation state -1 to +7. i f ClO, changes to CIO, in this oxidation state of chlorine changes from +7 to +5. rr 10% aq) + 2g) + 2° 10 t0q) + Ha B= +1.20V This reaction in Latimer diagram can be represented as clo; —7°-> clo; Re Similarly the reaction Pe ClO; +2 High + 26° — HClO 2 (oa + OF ag) E°=1.18V can be represented as - clo; 28> HCIO, (Other steps involved in the redox reactions are as follows : HCIO, +2H* +2e° —>HCl0 + H,0 E°=1.65V ie. HCIO, 1% HCIO 2QHCIO+2H* +e —>Cl, +2H,O E?= 1.67V ie. HCIO—>Cl, ; Cl, +e +H’ —>Cl + HCl E)= 1.36V he. Ch 12 Scr, The latimer diagram-for chlorine in acidic solution at a glance is4186 CL -1 __ 4167 _ 5 Cl 0 conbepts.of Chemist oe . i 65_5 HI - +hr8 ClO: thy Clog 882-9105 __s8 5 HCIOn if +5 +3 +7 i aie i activit ¥ os Sa anaes used to study the general Te Bee ity P i 2 s s i Pr risted eelty. In this, & graph of potential ae read ee ‘Consider the Pourbaix diagram for Iron. The re Sein 24 i Feet +e —> Fe ‘) ; hea i i H, Hence/in the diagram give: jons and independent of pl see ee ioe does not involve H* ‘nt contents a couple whi horizontal line but if the environme to following mechanism. Fe** + 3H,O——> Fe (OF a sea Fe(OH); +3H' +e Fe’ + 3H,0 ‘These reaction depends on pH of the solution ‘The line has been drawn for Fe concentration of 10 mol L. The regions of poten ial and pH that lie above this line correspond to conditions in. which the oxidised species [Fe (OH),].is stable, the regions talow it corresponds to conditions under which the reduced species: (Fe) is stable ee oe that a stronger oxidising agent is required to oxidise and precipitate Fe” jons-in acidic media than in basic media. ‘The vertical line at pH =:9 divides the region: the products are stable in the reaction. Be ae Fe% +2 H,Qy ——> Fe (OH )aja) +2 Haad ‘This reaction is not a redox reaction and the vertical line is drawn at a pH.that corresponds to Fe” equilibrium concentration of 10 mol L;', Another line separates the regions in which Fe (OH), and Fe (OH), are stable. é Fe(OH) 3,5) + Hag) + ——> Fe(OH) (.) + H2Q, bs Whe pong of this reduction depends on the pH. Finally we have drawn on the agram & two sloping lines that act as boundaries for the stability field of water. rinciples involved in the extraction of the elements : pea eee ome act ; In the extraction of metals oxidation-reductions are . For example, Magnessium can be extracted from MgO using coke. roi MgQ,xy + Cx) A> Mg, + CO, Jn this reaction carbon acts as reduci in ies cts a lucing agent and itself is oxidi: i gO i peau ae as an oxidising agent. 96% pure silicon is obi Mee , ' purity coke above the temperature 1500°C. oe eee Step I* Step II" .s in'which either the reactants or SiQyy +26, SEs Si, 20 | 2S8iG, + SiO, —> 3 Si, sacle a) + Sil i Iron is extracted by Nibs hot coi bl ie ie duced firs siny in a blast furnace. Fe*| oxide i: . ide is ret first s to i.Uxtumieer ee oon a er reduced to Fé 8 aa CO is oxidised: to.CO,. The FeO formed ih to Fe. FeQ,, +CO,, am ee 5) FCO) The extraction of a metal by reduction of aqueous solutions of its ions by using» H, or scrap iron as the reducing agent is known as hydrometallurgical extraction. *For example, Cu ions which are reached from low grade ores are reduced by hydrogen. The reaction’can be'represented as Cue) + Hq —> Cus) + 2 Fog) Elements extracted by oxidation : Halogens are extracted by oxidation process. The reaction is non-spontaneous at ordinary conditions.- (4 G°\= 422 Kg mol). But the extraction can be carried out under the influence’ of current (2:2 V). Hence by the electrolysis of aqueous solutions of halides we get halogens. 2.Claqy + 2 H,Q) ——> 2. Faq) + Haig) + Clayay F, is prepared by ‘the electrolysis’ of an‘unhydrous mixture of KF and HF. The more oxidisable halogens, Br, and I, aré obtained by’ chemical oxidation of the aqueous halide with chlorine. Sulphur in the elemental form is produced by the oxidation of HS, the process is known as Claus process in:which"H,S is oxidised to'SO,. In the second stage this $0, is allowed to react ini the presence of Al,O, with HS. 2H,S +30; >2S0, +2H,O 2H,S + So, —siecaat cialis!» 3S. 2H,0 among the metals only Gold can be cxtincted by oxidation methods: The Gold dissolved in appropriate solvent formed complex with CN’. This complex is ‘then reduced by Zinc. 2[Au (CM), Kraay, * 274s > 2 Aus +1Zn (CN)a Fey Solved Examples 1) Construct a Frost diagram for Oxygen from the Latimer diagram. 0, 22 Fo, 8 > H,0 +1.23 Sol.: The oxidation numbers of 0 to 0, -1 and -2 in the three species. For the change of oxidation number from 0 to -1 (O, to H,O,) E? = 0.70 V and N = -1, so NE? = -0.70V. Because the oxidation number of 0 in H,O is -2, N = -2, and E? for the formation of H,O is +1.23 V, NEY = -2.46 Vv, The Frost diagram for 0 in acidic solution (full line) and basic solution broken line. Oxidation number, NConcepts of Chemistry . ix diagram drawn pelow for manganese. Identify th. ne eee corresponding hydrous oxides are 2 th eatient in which the solid MnO, or its important. oy Manganese dioxide is thermodynamically favoured only ij > +0.6 V Under mildly reducing conditions, the stable species is Mn” a Thus Mno, is important in well aerated waters wher: E approaches the, value for the 0,/H,0 couple. pH 3) Assessing the importa: (V1) ions are unstable with respect to disproportanatio nce of disproportionation show that Manganate n into Mn (VII) and Mn (11) in acidic aqueous solution. Ans. : The overall reaction must involve reduction of one Mn (VI) to Mn (II) balanced by four Mn (VI) oxidising to Mn (VII). The equation is therefore a a wu 5 HMn Ojai) + 3 Hag ——> 4 MNOj (aq) + Meg) + 4 HO, ‘This reaction can be expressed as the difference of the reduction half reactions HMnOj aq) +7 Hag) + 4° —> Mri, + 4,0) B= + 1.63 4 MnO 5 (aq) + 4 Hag) + 4° ——>4 HMO} (o E°=+0.90V The difference of the standard potentials is +0.73 V, so the disproportionation is es$entially complete (K = 10° at 298 K, because V = 4). A practical consequence of the disprportionation is that high concentrations of MnO?" ions cannot be obtained in acidic solution but inust be prepared in a basic solution. 4) Extracting E° for nonadjascent oxidation states use the Latimer diagram to calculate the value of E° for reduction of HCIO to CI in aqueous acidic solution. Ans. : The oxidation number of.chlorine changes from +1 to 0 in one step (V' = 1) and from 0 to -1 (V" = 1) in the subsequent step. we can write ie 3 1 ACl0 9a) + Hag, + & — 95 Chatgy + Hay, E°=+1.63V 1 - 2 5 Ca) + © ——> Cag, Y= S1.36V We see that V'= 1 and V" = 1 soV = 2. It follows that the standard potential of the HCIO/CI couple is 2 2 =+L50Voxidation & Reduction 25 3) 9) 10) 1) 12) 13) 14) 15) 16) 17) 18) 19) 20) 21) 22) QUESTIONS Define the following terms : ( a) Oxidation b) Reduction c) Oxidant d) Reductant What is electrode potential? What are its types. Define the term : Standard electrode potential and give its types. Standard potential data suggest that gaseous oxygen rather than gaseous chlorine should be the anode product in electrolysis of aqueous NaCl. In fact only traces of oxygen are produced. Suggest an explaination. Use the latimer diagram for chlorine to determine the potential for reduction of CIO, to Cl,. Write a balanced equation for this half reaction. : Draw a Frost diagram for mercury in acid solution given the following latimer diagram : Hg? 2915 Fig?+ 0798 _, Fig Comment on the tendency of any of the species to act as an oxidising agent, a reducing agent, or to undergo disproportionation. Calculate E° for the reduction of ClO,’ to HGIO in aqueous acidic solution. Construct a Frost diagram from the Latimer diagram for.Tl : 71st 128g 7p 2084 ay #1.23 f The standard potentials for the couples Fe*/Fe and Fe**/Fe® are -0.41 V and +0.77 V respectively can Fe? disproportionate under standard conditions. How you will explain redox stability in water? What is Frost diagram ? How will you interprete it? Describe the latimer diagram with. suitable example. How you will explain the relation between redox activity and Bronsted acidity with the help of Pourbaix diagram. Describe the principle involved in the extraction of elements by reduction. Explain the thermodynamic aspect of extraction of elements by reduction. How the elements be extracted by oxidation? Explain with suitable example. Identify oxidising agents and reducing agents from the following () KMnO, (i) K,Cr,0, (iii) MnO, (iv) H,C,0, , (v) FeSO, (vi) FeSO,,(NH,),S0,.6H,O (vii) Na,S,0, (viii) I, (b) SnCl, (x) Cerric ammonium sulphate. "Oxidation and reduction is a simultaneous process". Justify with suitable example. Give the names of elements which can be extracted by oxidation process. Give the names of elements which can be extracted by reduction process. Which of the following elements are extracted by reduction. Give the reactions involved (a) Si (b) Mg (c) Fe (d) F,. Which of the following elements are extracted by oxidation. Give the reactions involved (a) Cu (b) Au_ (c) halogen. e@ e 6