Oxidation and reduction Oxidation and reduction are opposite processes that occur together. A reaction where both reduction and oxidation are taking place is called a redox reaction. Oxidation and reduction may be defined in four ways — see Table 13.2, p. 64, 62 Oxidation number An oxidation number indicates the oxidation state of an element in its free state or in a compound, Sometimes the oxidation number appeats in the ame of the compound where it refers to the element after whose name it is written, e.g. copperitt) oxide ~ oxidation number of copper is 2. An oxidation number can be assigned to each element in its free state or within a compound. RULES FOR ASSIGNING OXIDATION NUMBERS I The oxidation number of all atoms of an element in its free state is zero, eg. cu= , N atoms in Nz =0 2 The oxidation number of elements that exist as simple ions in fonic : ‘compounds is the same as the charge on the ion, eg. in AlCl: Al* = 43, CI7 3 The oxidation number of elements in radicals or in covalent compounds ‘may vary; often they appear in the name of the ion or compound, eg manganate(vi) ion, MnO, — oxidation number of manganese =-+7 nitrogenitv) oxide, NO, ~ oxidation number of nitrogen = +4 See Table 13.1 4 The sum of all oxidation numbers of elements in a compound is zero, eg. AlOs: oxidation number of Al) + 3(oxidation number of ©) =0 243) + 3-2) =0 +6 + -6 =0 sum of all oxidation numbers of elements in a radical is equal to the charge on the ion,eg. 80,2: (oxidation number of S) + 4(oxidation number of 0) = —2 (oxidation number of S) + 4-2) -2 (oxidation numiber of S) + -8 =2 oxidation number of S$ =~248 +6 ' The SO,?- ion may, therefore, be called the sulphate(vi) ion Element Oxidation | Notes number Hydrogen +1 Except in hydrides of metals, e.g. —1 in NaH and CaH Chlorine -1 Except when present in radicals, e.g. +1. Bromine in CIO; +3 in ClO,~; +5 in CIO,-, Bro,~ lodine and 103 ‘Oxegen -2 Except in peroxides, e.g, —1 in H;0> and NayO2 Sulphur 2 Except when present in radicals or covalent compounds, e.g. +4 in $0.7 and $02; +6 in HSO,", SO,2- and SOa Nitrogen -3 Except when present in radicals or covalent compounds, e.g. 3 in NH,* and NH3; +2 in NO; +3 in NOz; +4 in NOp; +5 in NOs Carbon e.8. —4 in CH; +2 in CO; +4 in HCO3-, C03? and CO Transition metals when | Vary Oxidation number of metal appears in present in radicals, name of ion, e.g. Cr20;7- is the Tabb sed tutes fo Ihe g(Nn0y Crs 01 7 dichromate(w) ion — oxidation number of assigning oxidation numbers chromium is +6 (see sample question to elements whose oxidation Bloed numbers vary ‘Sample question What is the oxidation number of chromium in the Cr:0,2> ion? 2(oxidation number of Cr) + 7(oxidation number of 0) = —2 (oxidation number of Cr) + 7-2) -2 2(oxidation number of Cr) + -14 =-2 2 (oxidation number of Cr) = -2 +14 +12 ‘Oxidation number of Cr a2 =16 i 63—_ Ee ‘uonionpss pue UoRepRO Jo Sojdulex® pue SUORILYOA Z"ET a1qeL ‘aseas0ep 0} swore 19 eu Jo saquunu uonepxo aly pasneo y) ~ quae Bulonpes oun SI IY ‘@see10U! 0} Uo} Punoduios | punodwoo e una eum | —punodwos | —_punoduoo wewiare quar Buia e uu =1 249 40 saquunu UonepRO a4p pesned 1! — ueBE BUISIPHKO AUN SI Fg 700 U0) poseaioap | W226 | Ue 0 28 quawoyo weusre S24 SUIONe [9 alp Jo JeqUITU UoRePHO eu1 — peonped Uddq sey Ig | 9S U | ay-sHul | UeJO Ares | Ue 40 areIS wows ue} quawere ue} — eey yu} — 904 su Ul Ope tower | Js2quinu ] Jo sequin | queweje ue | quowoye ue xo ‘524 UO! _} a4 Jo seqUITU UoREPKE 24) ~ PEsIPIKE U99q se) vir ici nepne oui ~ esipxo seq S24 D1 | “Uenepxo | uonepxo | yo saquinu | yo sequnu | ew 28) ott © "t+ :siequinu uonepro | uleseeep | ureseaiou | — uonepxo | —uonepxo | sequunu (21+ (Deo —— "10+ (beyDIZ esosneg | ue sosneg | ui eseoisea | uj asearouy | uonepixo Zig 2up 01 su0MOa/9 eneB 1! — quoBe Bujonpas aun s} og d J 24} WON) SuoNOg|e PenoUted }! ~ UBBe SUISIPIX ou | 71 Suo| _I9 wo) & suoRdd|9 paUjes sey 2! ~ peonpas useq seu 19 ~ (8)_109@ —— 09 + )19€ sean -1I9 — e+ :uons9j9 9uo Sure WORE 1g Yoe® ‘Ei9ay Sumo} Uo! 4.84 AU Uo} 0 suot9e}9 3801 Set 1) ~ PASIPHO UB9q Sey ed (9),224¢ —— _09 — (s)04g s1e090 a ‘emer vortanpeal ‘sso 69 —— 6-9. s aie ‘1 uoReDKO ~ 914 10) :Suonn9jo dain S@s0} wore ag yoed ‘E1994 Sumo} suonsi | —suonoeja | suonoaja | suonsare )F1o8sz —— (B)*10€ + (Saaz, soap | sanowoy Jo ule j0.ss01 | suonoaig 719 @un 0} uaBoupfy ene® y - ude Buronpes tn si STH SH ln Woy UsBoIDKy penowies 1! - uEBE BuISIPIKO aun SI 219 10H WHO} 0) uafosOKY pouleR seu i — paanpes usaq sey 219 10} 0} UaBOUPK 1 pas SN GSES AL BOF Seu BowtPno used se SH] sammy | uatony| —ussounty| —_usupAy ()s + @oHZ —— @20+ @lstH sonia | senowioy joule 40.8801 | uoBoupsy (nd eu) Woy YeBAKo Penowiad 3! — quOBe Bujonpes ap S| ey 7H a4) 0) UOBAK0 BABB 2! ~ qUEBe BuIsIpEXo OWN Si OND Ng wuos 0} UBBAK ySo] sey 2] ~ Peonpes used sey OND, 7H Woy sey. — seu 4 ae ate ete ool ig peeiPecp ces oer vaBihKO UeBhix0 eho 9860, 07H + (8)n9 —— (7H + (s)ono sen0wOy —sen jo sso so wep ueBKKo quoBe quoze so suuor ut | sf aidwexa | Buonpey | Busipxo | uononpey | uonepo | uontuyegOxidation and reduction Recognising redox reactions Write a balanced equation for the reaction. 2 Assign an oxidation number to each different element in its free state or combined within a compound. Write these numbers below the elements in the equation. Radicals which remain unchanged during a reaction may be ignored. 3 Determine the element whose oxidation number has increased ~ this has been oxidised by the other reactant. The other reactant is, therefore, the oxidising agent. 4 Determine the element whose oxidation number has decreased — this has, been reduced by the other reactant. The other reactant is, therefore, the reducing agent. 5 If the oxidation number of alll elements remains unchanged the reaction is not a redox reaction, Example Zn(s) + HaSO.(aq) ——> ZnSO,(aq) + Hoe) Oxidation numbers: 9 +, +2 ° « The SO,?> ion remains unchanged, therefore it may be disregarded. « The oxidation number of zine has increased from 0 to +2, therefore zinc has been oxidised by the sulphuric acid. Sulphuric acid is the oxidising agent. * The oxidation number of the hydrogen in the sulphuric acid has decreased from +1 to 0, therefore the sulphuric acid has been reduced by the zinc. Zinc is the reducing agent. Oxidising and reducing agents TESTING FOR OXIDISING AND REDUCING AGENTS When a substance acts as an oxidising agent, the substance itself is, reduced. When a substance acts as a reducing agent, the substance itself is, oxidised. Oxidising Reducing agent 222-=c1_ agent AS + 2B} ¢+D Reduced Oxidised byB by A # To test for an oxidising agent, mix the substance being tested with a known reducing agent that gives a visible change when it acts as a reducing agent, i.e. when it is oxidised. ‘To test for a reducing agent, mix the substance beirig tested with a known oxidising agent that gives a visible change when it acts as an oxidising agent, ie. when it is reduced. 65Table 13.3 Some common oxidising agents Table 13.4 Some common reducing agents Oxidising agent Visible change when it acts as oxidising agent Explanation of vi change Acidified (H2S04) potassium manganate(w), KMn0/H* Purple to colourless, Purple MnO,” ion forms colourless Mn2* ion Acidified (H2SO.) potassium dichromate(w), KoCr207/H* Orange to green Orange Cr20;?- ion forms green Cr>* ion lronii) salts, Fe®* Yellow to pale green Yellow Fe®* ion forms pale green Fe?* ion Dilute or concentrated nitric acid, HNO Brown gas evolved NO2 produced — a brown gas Concentrated sulphuric acid (usually hot), HaSO4 A pungent gas evohed S02 produced pungent gas Sodium chlorateti) (bleach), Nacio Depends on other reagent — tums many yes colourless Many dyes, when oxidised, lose their colour Others: oxygen, Oz; chlorine, Cl; manganese(w) oxide, MnOz Reducing agent Visible change when it acts as reducing agent Explanation of visible change Potassium iodide, KI Colourless to brown In(s) produced — dissolves in Kl(aq) to form brown iodine solution Hydrogen sulphide, HaS Yellow precipitate formed ‘S(s) produced ~ yellow and insoluble Iron) salts, Fe™* Pale green to yellow Pale green Fe?* ion forms yellow Fe®* ion Concentrated hydrochloric acid, HCL Yellow-green gas evolved lz produced ~ a yellow-green gas Others: hydrogen, He; carbon, C; carbon monoxide, CO; reactive metalsTable 13.5 Summary of ‘commen tests for oxidising and reducing agents Oxidation and reduction Tests for oxidising agents ‘Tests for reducing agents Test Colour change if | Test Colour change if oxidising agent reducing agent present present ‘Add Kita) Colourless to ‘Add KMInO«(aq) | Purple to brown acidified with colourless, H2S0,(aq) Bubble HS(g) | Yellow precipitate | Add K2Cr207(aq) | Orange to green through produced acidified with substance HoS0.(aq) Add aqueous Pale green to Add aqueous Yellow to pale iron(u) salt yellow iron(u) satt green SUBSTANCES THAT CAN BEHAVE AS BOTH OXIDISING AND REDUCING AGENTS Sulphur dioxide (SO2) In the presence of water, sulphur dioxide is usually a reducing agent; if reacted with a stronger reducing agent, it acts as an oxidising agent. © With chlorine it acts as a reducing agent: SOz(g) + 2H,01)) + Cliigh —— Hy Oxidation 44-2. +1,-2, 0 numbers: SO,(aq) + 2HCllaq) 6-20 Hh-t Teihetion The oxidation number of the chlorine atoms in the chlorine has decreased from 0 to —1, therefore the chlorine has been reduced by the sulphur dioxide. * With hydrogen sulphide, a stronger reducing agent, it acts as an oxidising agent 2H2S(g) + SO2(g) ——> 35\s) + 2H,0(l) Oxidation numbers: 41,-2 +4,-2 0 41-2 ‘ridation The oxidation number of the sulphur in the hydrogen sulphide has increased from —2 to 0, therefore the hydrogen sulphide has been oxidised by the sulphur dioxide. Acidified hydrogen peroxide (H202/H*) This is usually an oxidising agent; if reacted with a stronger oxidising agent, it acts as a reducing agent: * With potassium iodide solution it acts as an oxidising agent, oxidising the iodide ions to iodine, * With acidified potassium manganate(vu), a stronger oxidising agent, it acts as a reducing agent, reducing the purple MnO,~ ion to the colourless Mn?* ion,Electrochemistry and electrolysis Introduction some DEFINITIONS * Electric current; a flow of charged particles — electrons or ions (see below) * Conductor: a substance that allows electricity to pass through, e.g. all metals, graphite (carbon). ‘ * Insulator (non-conductor): a substance that does not allow electricity to pass through, e.g. non-metals, plastics, * Electrolyte: a molten substance or solution that allows electricity to pass through causing it to decompose, e.g. molten salts, aqueous solutions of acids, alkalis and salts. * Non-electrolyte: a molten substance or solution that does not allow electricity to pass through, e.g. organic solvents, aqueous solutions of organic substances such as glucose, molten covalent substances such as wax. METALLIC AND ELECTROLYTIC CONDUCTION * Metallic conduction involves the flow of free electrons through a metal; these electrons are present in the electron pool. The metal remains chemically unchanged. * Electrolytic conduction involves the movement of free ions through a molten substance or a solution. The substance is chemically decomposed during electrolytic conduction. STRONG AND WEAK ELECTROLYTES * Strong electrolytes are substances that are fully ionised, i.e. they contai large number of ions, e.g. strong acids, strong alkalis, solutions of salts, molten salts. * Weak electrolytes are substances that are partially ionised, ic. they contain few ions, e.g. weak acids, weak alkalis, pure water. A note about pure water Pure water is an extremely weak electrolyte. Approximately one molecule in every 560.000000 molecules is ionised: H,O(l) == H*(aq) + OH7 (aq) Electrolysis etectrotysis is the chemical change occurring when an electric current is passed through an electrolyteFig. 14.1. The theory of electrolysis Electrochemistry and electrolysis Electrolysis involves the use of electrodes connected to a battery. The electrodes carry the current Into or out of the electrolyte. Electrodes are usually made of inert (unreactive) substances e.g. graphite (carbon), platinum: * The anode is the positive electrode, connected to the positive terminal Of the battery. * The cathode is the negative electrode, connected to the negative terminal of the battery. During electrolysis: 1 Anions (—) are attracted to the anode (+) where they lose electrons to form neutral atoms, i.e. they are discharged: A™ —ne> —— A Oxidation therefore occurs at the anode. 2 Electrons, lost at the anode, are ‘sucked along’ to the positive terminal of the battery and pushed out of the negative terminal to the cathode. 3 Cations (+) are attracted to the cathode (—-) where they gain the { electrons from the anode to form neutral atoms, i.e. they are discharged. ch 4nem — Reduction therefore occurs at the cathode. —— — ee ao watery : a a ~~ eae eee eae Somer . Je “Serer mower“ © cathode 9 Electrolyte, CA (| or aq)Electrolysis of — motten electrolytes contain only two kinds of ion. Both are discharged during molten electrolysis. electrolytes Example Electrolysis of molten lead{(i!) bromide using inert electrodes lons present: Pb?*(I), Br- (I) At anode: Br~ ions are attracted to the anode, and discharged, i.e. they lose electrons to form bromine atoms: Br-() -e~ ——> Br Pairs of bromine atoms immediately join to form bromine molecules: Br+Br —— Brg) Overall reaction: 2Br~ (I) —2e- —— Brig) At the temperature required to melt lead) bromide, brown bromine vapour is released. At cathode: Pb?* ions are attracted to the cathode and discharged, electrons to form lead atoms: Pb?*(I) +2e> — Poi!) Molten lead drips off the cathode. e. they gain Electrolysis An aqueous solution usually contains at least two different cations and two different anions owing to the presence of H* and OH™ ions from the water. of AQUEOUS ory one type of ion of each charge Is usually discharged at each electrode. solutions Three factors determine which ions are discharged 1 Position of the ion in the electrochemical series. (See Table 14.1.) Cations] TAnlone ‘The lower an ion is in the electrochemical series, the more likely it is to be « SO, discharged from solution, oe 2 Relative concentration of the ions. lat r met | Br The greater the concentration of an ion, the more likely it is to be a [re discharged. This applies particularly to solutions containing halide ions (Cl- me | on Br-, I"), e.g. electrolysis of concentrated hydrochloric acid and sodium Fett chloride solution (see Table 14.2) he 3 Nature of the electrode. cu An electrode which is not inert can take part in a reaction. If an active re electrode is used, then the reaction occurring is the one that requires least energy, e.g. electrolysis of copper sulphate solution using a copper Table 14.1 The anode (see Table 14.2); electrolysis of sodium chloride solution using a electrochemical series, mercury cathode (see p. 115).Electrochemistry and electrolysis (panunucs) ‘suonnjos snosnbe awos jo sissonoag z'pt eigen ft a (be)_19 pue (be), en Buneo| ‘panouias aie (be) HO ue (be), H :pexequeduoD ‘alu! sawooaq uoRniog 4 Souinjon z 29 awinjon 'Sesef Jo oUInjon © Panjona se8 ueBouphy BVH — _07 + (be) Hz FEN ueu Sol198 jeolwoyoonc9j@ Ul J8Mo| ‘paBieyosID .} :epoyteD Panjona se UoSAxo (80 + (Wo%Hz —— ay ~ (be)_Hor -1o ew, S01198 [eolWua4oonoa}9 UI J8Mo| ‘peBIeUIsIP _HO :epouy © woes 4o winuneld ~ wou PN :18N Woy (be)_HO “(be),.H :0°H wos (be)I9eN eanyp 12, (be)_Ho pue (be) ,H Buine9| 24 auunjon 7:29 euunjon T 18988 Jo ouinjon © Panjona seB uaBosphy GH —— _9¢ + (be), Hz sopompeg « panjona se euNOIYD 4190 —— _a¢ - (be)_10z s voqueo Jo winuneid repouyleg 21g Aq yoene ysise H HOH wos ‘alow sew099q ploy ‘S908 [eoILUeyoo:R08/8 Ul 1aM0) ‘peHIeYOSIp _HO :epouy » penouios axe (be)_{9 pue (be), ©} uoqied :epouy (be), H 10° wo ‘einiIp 210w sewoosg pioy | _HO eUR UoNeNUEdLIOD JoUBIY ‘poBLeYosIp _19 :epouy ‘you (be)IOH peyenueou0D (peonposd ‘ae 2} Sauinjon Z pue 2 ‘aunjon T ‘a s@|oW y Asana 40) 24 S@UuNjOA Z :0 aUINjON T !S96eB Jo ouinjon « anions se8 ueBoupsH BH —— _2¢ + (be) Hz opomeg « PON|OKa SeB UaBAKO (be)_z%08 pue (be) 4 c ra 2 Bungay paroiuos ale (be). r10 B70+ WorHe _9% ~ (b2)_HOy rosy (eliH rosea ue (be), H :peyenueou0s _2fos vey, uogieo (be) Ho “(be), 4 :02H wo 4 wnune|d ~ yeu (be)"os?H einua exsjonjo9ja ut soBueyD sionpoid pue suonova: eponoe(y soponoarg quasaid suo!/afjonse13Chemistry: a concise revision course for CXC Joxfo1my S198 apoureo ‘paysodap saddog (Inq —— _22 + (be),n9 4H usw soues Jeojwiayoonseyo u samo} ‘paBseuosip ,~n9 :epoueg « souutn S168 epouy saddoo 10 uoqueo ‘wnuneid / (02) 4290 — -82— 9) 9POUPD | (oe) _z¥OS “be),2NO *OSNO Wold apouneo 01 apoue wos, Ho Jo eBreyosip uewn MBs0U9 S591 (omnoe) (02)-HO ‘(be).4 :07H woud pauajsuen si seddoo :eBueyo oN | saiinbos ‘,_ng 0} paveAuos epansare Woy (s)ng :epouy «| _saddao :opouy (be}*osno sonfojun 5183 apouned ‘paysodap sweddoo UNOIG>IUld (9179 —— _2z + (be),.09 4H ue saves Panowias (be), 2nd Jeo1wayoono9[@ Ul J8Mo| ‘paByeyosip ,2N9 :@poyeD © :onjq s0yed sauo99q vonnios panjono Se UoBAXO. be) _.m Sal CHE a SU ae HOU) (02)...70S “(be).2N9 :*OSND wo -zFos vetn uuocues (be)_Ho ‘(be),H :0°H wouy Solias eoluayoonde}9 Ul Jomo] ‘paBleyosIp _HO :epouy © 40 wnuneld ~ weuy (be)"osng (be)_Ho pue (be),eN Sunes) 244 awinjon T 219 BUINION T 189888 Jo OUINIOA « panjona seB ueZouphy BH — 02 + (be) He 4eN ueWn sous JeolWayoonRde Ul JOM ‘paBLeYOSIP ,H !epOURED © payors se eunolua, 419 ———.__ez— 19% tuogiee 40 winuneyd sapoujed 9 Aa yoene 181891 be) .2N ‘1oBN Woy panowias aie (be)_19 pue (be), H © voqued :ep0uy 2) H :O7H wold E sewiogeq uonnios | _HO etn UoReAUBOUOD J8UBIY ‘PpeBIeUDSIP 19 :epouy & woul EN peyesueDu0D ‘eukjoqoa19 ut soBueUD ‘syonpoid pue suonoees eponsera ‘seponse(3 qwuasaud suot/arkion9013Electrochemistry and electrolysis Uses of 1. INDUSTRIAL EXTRACTION OF REACTIVE METALS electrolysis (see also p. 94) Example Extraction of sodium in the Down’s cell Molten NaCl and Cad), (CaCl, lowers melting point of NaCi) Clg from anede 1 t ‘Stee! hood ~ prevents —f Su | UGE > Moiten Na out ae ar == o%6 | Molten Na from cathode stee um —| gee “0 = cathode — eet | aio Na” ions are discharged: Natt) +e > Nag) Electrolyte - molten meee anode gain Canoe Fig. 14.2 The Down's cell 20h) 26 —> Chin + 2 PURIFICATION OF METALS Example Purification of copper {ile Anode — tan pare neh ie kya Cathode — stip pure metal Sree: Gunes eae irraae te Sacer Sora Co ns deca Cu(s) - 2e° —» Cu?*(aq) CuP*(aa) + 26> Cuts) Soe pu ccper ete te Bly shin comaning foes he ara eula reeias Fig 143 Puntcaton of pee copper ‘anode