REDOX REACTIONS A chemical reaction is a process that leads to the transformation of one set of chemical substances toanother substance. Classically, chemical reactions encompass changes that strictly involve the motion of electron in the forming and breaking of chemical bonds. The concept of electron transfer can easily explain in the redox reactions in the case of ionic substances. However, for covalent compounds we use a new term oxidation number to explain oxidation and reduction or redox reactions. Redox reactions are the chemical reactions which involve both oxidation as well as reduction simultaneously. In fact, oxidation and reduction go hand in hand. OXIDATION AND REDUCTION Classical Concept : (A) Oxidation a Oxidation is a chemical reaction in which oxygen is added ®) w@ 2) 2HNO, +O, —92HNO,; 2CH,CHO+0,—> 2CH,COOH Hydrogen is removed i.e. hydrogen becomes less Zn+2HC|—>ZnCl, +H, ; Cu+4HNO, —>Cu(NO,)}+ 2NO, +2H.0 Electronegative clement is added 2FeCl, +Cl, —>2FeCl,; 2Sb+3Cly=—>2SbC1, Electropositive elementis removed 2Nal+H,0, ——+2NaQH +l: Reduction @ Gi) i, (iv) ) ‘Addition of Hydrogen. H,+Cl,—> 2HCl, ——-N,+ 3H, —+ 2NH, Loss of Oxygen. Fe,0, +2Al —> 2Fe+Al,0, Cr,0, + 2Al —+ 2Cr + ALO, Addition of electropositive element. 2HgCl, + SnCl, —> Hg,Cl,+SnCl, CuCl, + Cu —+ Cu, Cl, Losss of electronegative element. 2FeCl, + H, —+> 2FeCl, + 2HCI PbS +H, —> Po + HS ‘Valency of electropositive element decreases. CuSO, +Fe—>FeSO, +Cu (Cu") (cu’) FeCl, +H,S—>FeCl, +2HCI+S. (Fe) er) } ‘Modern Concept : Oxidation The reaction in which an element oran atom or an ion or molecule loses electron(s) is called oxidation. Illustrative examples in various cases are given below. “ww o Neutral atom : When a neutral atom loses electron(s), it gets converted to a positive ion. Na —+ Nat +e Al —+ AI +3" Cation : When a cation loses electron(s), there is an increase in its positive charge. Sn? —+ Sn't + 2e Hg"? —+ Hg? +e Anion : When an anion loses electron(s) equal to its negative charge, it gets converted toa neutral atom. 20? 4 0, + 4e 2N? —+ N, + 6¢ ‘Complex Anion : When a complex anion loses electron(s), its negative charge decreases. [Fe(CN),]* —+ [Fe(CN),}? + ¢ Molecule : When a molecule loses electron(s), it breaks up into it constituents, HO, —+ 21" +0, + 2€ Note : Jn oxidation reactions ~ Positive charge increases and negative charge decreases. (B) Reduction ‘The reaction in which an clement o an atom or an ion (positive or Negative ora molecule accepts clectron(s), is called reduction. Illustrative examples in various ¢ases are given below, oO wi ®) ‘Neutral Atom :When a neutral clemént or atom aécepts clectron(s), it get converted into an anion, N + 3¢ —y NP See —» S* ‘Cation 2 When a tation accepts electron(s) equal to its charge, it gets converted into a neutral ‘atin. Mg"? + 2e- —-» Mg” AI? +3e —> AP Similarly, when a cation accepts electron(s) than, its positive charge decreases. For example Cu? +e —+ Cut Fe? +e —+ Fe? Anion : When an anion accepts electron(s), its negative charge increases. MnO, +e —» MnO,? [Fe(CN),J* + © —+ [Fe(CN),]* Molecule : When a molecule accepts electron(s), it is a reduction reaction. 0, +4e —+ 207 1+2e —> 24 Note : Jn reduction reactions~ Positive charge decreases and negative charge increases, BASIC TERMS (1) Molecular equations : When the reactants and products involved in a chemical change are written in molecular forms in the chemical equation, itis termed as molecular equation.@ 8) @) 6) Example : MnO, +4HCI—> MnCl, +2H,0+Cl, Inabove example the reactants and products have been written in molecular forms, thus the equation is termed as molecular equation. Tonic equations : When the reactants and products involved ina chemical change are ionic compounds, these will be present in the form of ions in the solution. The chemical change is written in ionic forms in chemical equation, itis termed as ionic equation. Example, MnO, +4H" +4Cl > Mn™ +2Cl +2H,0+C1, Inabove example the reactants and products have been written in ionic forms, thus the equation is termed as ionic equation. Spectator Ions : Species that are present in the solution but not take part in the reaction and are also omitted while writing the net ionic reaction are called spectator ions or bystander ions. ‘Zn + 2H’ + 2Cl- > Zn"? + 2Ch +H, In this reaction ions are omitted and are called as spectator ions and appear on the reactant as well as product side. Oxidising agent : The substance (atom, ion or molecule) that gaingeléctrgiis and is thereby reduced toa low valency state is called an oxidising agent. Reducing agent : The substance that loses eleétfon¥and isthere#y oxidised to a higher valency state is called a reducing agent. TYPES OF (REDOX! REACTIONS a) 2 @) Direct and Indirect redox reaction Direct redox reaction : When both oxidation and reduction reactions occurs in same vessel Indirect Redox reaction : When oxidation and reduction reactions occur in different vessels. Inter molecular redox reactions ‘Two substances react one of them is oxidant and other is reductant, Zn (s) + CuSO, (aq) ZnSO, (aq) + Cus) ‘Oxidation Zn(s)— Zn"? (aq) + 2e— Reduction Cur? (aq) + 2° —> Cu(s) Intra-molecular redox reactions (One clement of a compound is oxidised and other element of the same compound is reduced. eg. (NH,),Cr,0, —> N, + Cr,0,+ 44,0 ‘Oxidation 2N>-—> (N°), + 6e~ Reduction (Cr'*), +6 —> (Cr),@ ‘One and the same substance may act simultaneously as an oxidising agent and as a reducing agent with the result that a part of it gets oxidised to a higher state and rest of itis reduced to lower state of oxidation. Such a reaction, in which a substance undergoes simultancous oxidation and reduction is called disproportionation and the substance is said to disproportionate. Following are the some examples of disproportionation, incense Y 3% decrease HO, +110, = 110 +0, © 3% ! 2) 4kCIo, + 3KCfo, +e 2 9 ee ig qa decrease decrease oO + 3 oO -l 8) 4P + 3NaOH + 3H.0 + 3NaH_PO+ PH, (4) 3Cl, + 6NaOH —> S$ NaCl Systio,- 3HO ut L__., 4p intone inerahe ‘Comproportionation reaction Seieatte Nitrogen in this compound has ~3 ind so itis nota definite value, so its not a disproportion reaction. Its an reaction which isa case of redox reaction in which element from tw9 state gets converted into a single oxidation state. OXIDISERS .AND REDUCERS Oxidizers o @ ) @) ‘Substances that have the ability o oxidize other substances are said to be oxidative oroxidizing and are knownas oxidizing agents, oxidants, or oxidizers. Put another way, the oxidant (oxidizing agent) removes electrons from another substance; ic. it oxidizes other substances, and is thus itself reduced. And, because it “accepts” electrons, itis also called an electron acceptor. (Oxidants are usually chemical elements or substances with elements in high oxidation states. Important oxidising agents Molecules made up of electronegative elements. Example: O,, 0, and X, (halogens). ‘Compounds containing an element which is in the highest oxidation state. Example: KMnO,,K,Cn,0,, Na,Cr,0,, CrO, H.SO,, HNO,, NaNO, FeCl, ,HgCl;,.KCIO,,SO,,CO,,H,0,¢tc. Oxides of elements, MgO,CuO,Cr0,,CO,,P,0,,, ete. Fluorine is the strongest oxidising agent.Reducers @ (ai) ) ™ ‘Substances that have the ability to reduce other substances are said to be reductive or reducing and are known as reducing agents reductants, or reducers. The reductant (reducing agent) transfers electrons to another substance; i.c., it reduces others, and is thus itself oxidized. And, because it “donates” electrons, also called an electron donor. Electron donors can also form charge transfer complexeswith electron acceptors. Important reducing agents (i) All metals e.g. Na, Zn, Fe, Al, etc. (ii) A few non-metals e.g. C, H,,S ete. (iii) Hydracids : HCI, HBr, HI, HS ete. (iv) A few compounds containing an element in the lower oxidation state (ous). Example : FeCl, FeSO,, SnCl,, Hg,Cl;, Cu,0 ete. (v) Metallic hydrides e.g. NaH, LiH ete. (vi) Organic compounds like HCOOH and (COOH), and their salts, aldehydes, alkanes etc. (vii) Lithium is the strongest reducing agent in solution. (viii) Cesium is the strongest reducing agent in absence of water. Substances which act as oxidising as well as reducing agents, Examples : H,0,,SO,,H,SO,,HNO,,NaNO,,Na,SQ,,0} ete? Tips for the identification of oxidising and reducing agents fan element is in its highest possible oxidation state in a compound, the compound can function as an oxidising agent Example»KMnO,, K,Cg0,, HNO,, H.SO,, HCIO, ete. fan element isin its lowest possible oxidation state in a compound, the compound can function only as a reducing agent. Example : H,S, H,C,O,, FeSO,, Na,$,0,, SnCl, etc. If.an clement is in its intermediate oxidation state in a compound, the compound can function both asan oxidising agent as well as reducing agent. Example; H,O,, H,SO,, HNO,, SO, ete, Ifa highly clectronegative clement isin its highest oxidation state ina compound, that compound can function asa powerful oxidising agent. Example : KCIO,, KCIO,, KBrO,, KIO, etc. Ifan electronegative element isin its lowest possible oxidation state in a compound or in free state, itcan function as a powerful reducing agent. Example : 1", Br’, N° ete.