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UNIT 8

REDOX REACTIONS

Where there is oxidation, there is always reduction --Chemistry is essentially a study of redox systems. Oxidation reaction and reduction reaction Oxidation reaction Reduction reaction 1. Addition of oxygen Removal of oxygen C + O2 --- CO2 Fe3O4 + 2C --- 3Fe + CO2 2 Removal of hydrogen .Addition of oxygen. 3 Removal of electron/s Addition of electron/s. n ! 2e- -- n+2 Cl + e- -- Cl4. Addition of anion/s i.e Reaction "ith nonmetal/ Removal of anion/s or electro-ve element electro!ve element # Removal of electro+ve element Addition of ectro+ve element .$ Oxidation no. increases Oxidation no. decreases Redox reaction Reactions in "hich %oth oxidation and red&ction reactions ta'e (lace sim&ltaneo&sly. e.g. Or Reactions "hich involve change in oxidation n&m%er of the interacting s(ecies.

Oxidizing agent/oxidant i.e. acce ter o! e"ectron#--Reactant that oxidi)e the other reactant and itself that get red&ce in given reaction is 'no"n as oxidi)ing agent or oxidant. Reducing agent/reductant i.e. donar o! t$e e"ectron#----Reactant that red&ce the other reactant and itself that get oxidi)ed in given reaction is 'no"n as red&cing agent or red&ctant. Oxidation nu%&er''' Oxidation n&m%er denotes the oxidation state of an element in a com(o&nd ascertained according to a set of r&les form&lated on the %asis that electron in a covalent %ond %elongs entirely to more electronegative element.

Di!!erence &et(een oxidation no. and )a"enc*''' Oxidation no. *alency 1. +t is d&e to the (artial shifting of electrons +t is d&e to the com(lete loss of electrons +. Related to the covalent %ond formation. Related to the ionic %ond Formation ,. +t may %e different in different com(o&nds for same +t remain same in all com(o&nd for an element. element ,exce(t transition elements.e.g. Fe e.t.c.+t may %e in fraction +t al"ays in "hole n&m%er Ru"e# to deter%ine t$e oxidation nu%&er''' .. +n elements/ in the free or the &ncom%ined state/ each atom %ears an oxidation n&m%er of )ero. 0vidently each atom in 12/O2/ Cl2/ O3/ 24/ 34/ 5a/ 6g/ Al has the oxidation n&m%er )ero. 2. For ions com(osed of only one atom/ the oxidation n&m%er is e7&al to the chargeon the ion. 8h&s 5a+ ion has an oxidation n&m%er of +./ 6g2+ ion/ +2/ Fe3+ ion/ +3/ Cl! ion/ !./ O2! ion/ !29 and so on. +n their com(o&nds all al'ali metals have oxidation n&m%er of +./ and all al'aline earth metals have an oxidation n&m%er of +2. Al&mini&m is regarded to have an oxidation n&m%er of +3 in all its com(o&nds. 3. 8he oxidation n&m%er of oxygen in most com(o&nds is !2. 1o"ever/ "e come acrosst"o 'inds of exce(tions here. One arises in the case of (eroxides and s&(eroxides/ the com(o&nds of oxygen in "hich oxygen atoms are directly lin'ed to each other. :hile in (eroxides ,e.g./ 12O2/ 5a2O2-/ each oxygen atom is assigned an oxidation n&m%er of !./ in s&(eroxides ,e.g./ ;O2/ R%O2- each oxygen atom is assigned an oxidation n&m%er of !,<-. 8he second exce(tion a((ears rarely/ i.e. "hen oxygen is %onded to fl&orine. +n s&ch com(o&nds e.g./ oxygen difl&oride ,OF2- and dioxygen difl&oride ,O2F2-/ the oxygen is assigned an oxidation n&m%er of +2 and +./ res(ectively. 8he n&m%er assigned to oxygen "ill de(end &(on the %onding state of oxygen %&t this n&m%er "o&ld no" %e a (ositive fig&re only. 4. 8he oxidation n&m%er of hydrogen is +./ exce(t "hen it is %onded to metals in %inary com(o&nds ,that is com(o&nds containing t"o elements-. For exam(le/ in =i1/ 5a1/ and Ca12/ its oxidation n&m%er is !.. #. +n all its com(o&nds/ fl&orine has an oxidation n&m%er of !.. Other halogens ,Cl/ >r/ and +- also have an oxidation n&m%er of !./ "hen they occ&r as halide ions in their com(o&nds. Chlorine/ %romine and iodine "hen com%ined "ith oxygen/ for exam(le in oxoacids and oxoanions/ have (ositive oxidation n&m%ers. $. 8he alge%raic s&m of the oxidation n&m%er of all the atoms in a com(o&nd m&st %e )ero. +n (olyatomic ion/ the alge%raic s&m of all the oxidation n&m%ers of atoms of the ion m&st e7&al the charge on the ion. 8h&s/ the s&m of oxidation n&m%er of three oxygen atoms and one car%on atom in the car%onate ion/ ,CO3-2! m&st e7&al !2. Trend o! ox. No./ox.#tate in t$e eriodi ta&"e +n a (eriod it increases ,.to ?- from left to right. +n a gro&( ,as "e go do"n in the gro&(- it remains same. 8he oxidation n&m%er state of a metal in a com(o&nd is sometimes (resented according to the notation given %y @erman chemist/ Alfred 3toc'. +t is (o(&larly 'no"n as Stoc. notation. According to this/ the oxidation n&m%er is ex(ressed %y (&tting a Roman n&meral re(resenting the oxidation n&m%er in (arenthesis after the sym%ol of the metal in the molec&lar form&la. 8h&s a&ro&s chloride and a&ric chloride are "ritten as A&,+-Cl and A&,+++-Cl3. T* e# o! redox reaction# '''' .. Co%&ination reaction#AReaction in "hich t"o reactants com%ine together to form a single (rod&ct is 'no"n as com%ination reaction. A + > B-- C e.g. C,s- + O2 ,g----- CO2,g36g,s- + 52,g------- 6g352,s+. Deco% o#ition reaction/ Cecom(osition reactions are the o((osite of com%ination reactions. A decom(osition reaction leads to the %rea'do"n of a com(o&nd into t"o or more com(onents. 0xam(les 212O ,l-------- 212 ,g- + O2,g25a1 ,s------- 25a ,s- + 12,g2;ClO3 ,s----------- 2;Cl ,s- + 3O2,g-

5oteA All decom(osition reactions are not redox reactions. For exam(le/ decom(osition of calci&m car%onate is not a redox reaction. CaCO3 ,s--------- CaO,s- + CO2,g,. Di# "ace%ent reaction# +n a dis(lacement reaction/ an ion ,or an atom- in a com(o&nd is re(laced %y an ion ,or an atom- of another element. i.e. D+E FD +E Cis(lacement reactions have t"o categoriesA ..metal dis(lacement and 2. non-metal dis(lacement. 0a1 2eta" di# "ace%ent: A metal in a com(o&nd can %e dis(laced %y another metal in the &ncom%ined state. A((licationsA +n metall&rgical (rocesses in "hich (&re metals are o%tained from their com(o&nds in ores. exam(les ---

3ig. Redox reaction %et"een )inc and a7&eo&s sol&tion of co((er nitrate occ&rring in a %ea'er.

C&3O4,a7- + n ,s- F C&,s- + n3O4 ,a7*2O# ,s- + #Ca ,s- -----2* ,s- + #CaO ,s8iCl4 ,l- + 26g ,s- ------8i ,s- + 2 6gCl2 ,sCr2O3 ,s- + 2 Al ,s- -------Al2O3 ,s- + 2Cr,s+n each case/ the red&cing metal is a %etter red&cing agent than the one that is %eing red&ced "hich evidently sho"s more ca(a%ility to lose electrons as com(ared to the one that is red&ced. 0&1 Non'%eta" di# "ace%ent: 8he non-metal dis(lacement redox reactions incl&de hydrogen dis(lacement and a rarely occ&rring reaction involving oxygen dis(lacement. All al'ali metals and some al'aline earth metals ,Ca/ 3r/ and >a- "hich are very good red&ctants/ "ill dis(lace hydrogen from cold "ater. 25a,s- + 212O,l- F 25aO1,a7- + 12,gCa,s- + 212O,l- F Ca,O1-2 ,a7- + 12,g=ess active metals s&ch as magnesi&m and iron react "ith hot "ater and steam to (rod&ce dihydrogen gasA 6g,s- + 212O,l- ----- 6g,O1-2,s- + 12,g2Fe,s- + 312O,l--------- Fe2O3,s- + 312,g6any metals/ s&ch as Cadmi&m and tin dis(lace the hydrogen from acids areA n,s- + 21Cl,a7- F nCl2 ,a7- + 12 ,g-----------------------,. 6g ,s- + 21Cl ,a7- F 6gCl2 ,a7- + 12 ,gFe,s- + 21Cl,a7- F FeCl2,a7- + 12,g-----------------------,2 Reactions ,.G2- are &sed to (re(are dihydrogen gas in the la%. 1ere/ the reactivity of metals is reflected in the rate of hydrogen gas evol&tion/ "hich is the slo"est for the least active metal Fe/ and the fastest for the most reactive metal/ 6g. *ery less active metals/ "hich may occ&r in the native state s&ch as silver ,Ag-/ and gold ,A&- do not react even "ith hydrochloric acid. Reactivity of )inc , n-/ co((er,C&- and silver ,Ag- is in the order nH C&HAg. =i'e metals/ activity series also exists for the halogens. 8he (o"er of these elements as oxidising agents decreases as "e move do"n from fl&orine to iodine in gro&( .? of the (eriodic ta%le. 8his im(lies that fl&orine is so reactive that it can re(lace chloride/ %romide and iodide ions in sol&tion. +n fact/ fl&orine is so reactive that it attac's "ater and dis(laces the oxygen of "ater A 212O ,l- + 2F2 ,g- F 41F,a7- + O2,g-

5oteA +t is for this reason that the dis(lacement reactions of chlorine/ %romine and iodine &sing fl&orine are not generally carried o&t in a7&eo&s sol&tion. On the other hand/ chlorine can dis(lace %romide and iodide ions in an a7&eo&s sol&tion as sho"n %elo"A Cl2 ,g- + 2;>r ,a7- F 2 ;Cl ,a7- + >r2 ,lCl2 ,g- + 2;+ ,a7- F 2 ;Cl ,a7- + +2 ,sAs >r2 and +2 are colo&red and dissolve in CCl4/ can easily %e identified from the colo&r of the sol&tion. 8he a%ove reactions can %e "ritten in ionic form asA 1ence the a%ove reactions are the %asis of identifying >r! and +! in the la% and the test (o(&larly 'no"n as 45a*er Te#t6. >romine li'e"ise can dis(lace iodide ion in sol&tionA >r2 ,l- + 2+ ! ,a7- F 2>r! ,a7- + +2 ,sFl&orine is the strongest oxidi)ing agent9 there is no "ay to convert F! ions to F2 %y chemical means. 8he only "ay to achieve F2 from F! is to oxidise electrolytically. -. Di# ro ortionation reaction# Cis(ro(ortionation reactions are a s(ecial ty(e of redox reactions. +n a dis(ro(ortionation reaction an element in one oxidation state is sim&ltaneo&sly oxidised and red&ced. One of the reacting s&%stances in a dis(ro(ortionation reaction al"ays contains an element that can exist in at least three oxidation states. 212O2 ,a7- F 212O,l- + O2,g1ere the oxygen of (eroxide/ "hich is (resent in !. state/ is converted to )ero oxidation state in O2 and decreases to !2 oxidation state in 12O. 2hos(horo&s/ s&l(h&r and chlorine &ndergo dis(ro(ortionation in the al'aline medi&m as sho"n %elo" A 24,s- + 3O1!,a7-+ 312O,l- F 213,g- + 3122O2! 34,s- + .2 O1! ,a7- F 432! ,a7- + 232O32!,a7- + $12O,lCl2 ,g- + 2 O1! ,a7- F ClO! ,a7- + Cl! ,a7- + 12O ,l8he last reaction descri%es the formation of ho&sehold %leaching agents. 8he hy(ochlorite ion ,ClO!- formed in the reaction oxidises the colo&r-%earing stains of the s&%stances to colo&rless com(o&nds. 3ame trend follo"ed %y %romine and iodine .Fl&orine sho"s deviation from this %ehavio&r "hen it reacts "ith al'ali. 2 F2,g- + 2O1!,a7- F 2 F!,a7- + OF2,g- + 12O,l>eca&se F is the most electronegative element/ it cannot exhi%it any (ositive oxidation state. 8his means that among halogens/ fl&orine does not sho" a dis(ro(ortionation tendency.

7a"ancing o! Redox Reaction#8


Redox Reaction# a# t$e 7a#i# !or Titration# +n acid-%ase systems "e come across "ith a titration method for finding o&t the strength of one sol&tion against the other &sing a (1 sensitive indicator. 3imilarly/ in redox systems/ the titration method can %e ado(ted to determine the strength of a red&ctant/oxidant &sing a redox sensitive indicator. 8he &sage of indicators in redox titration is ill&strated %elo"A ,i- +n one sit&ation/ the reagent itself is intensely colo&red ,'no"n as self indicator-/ e.g./ (ermanganate ion/ 6nO4 ! . 1ere 6nO4! acts as the self indicator. 8he visi%le end (oint in this case is achieved after the last of the red&ctant ,Fe2+ or C2O42!- is oxidised and the first lasting tinge of (in' colo&r a((ears at 6nO4! concentration as lo" as .I!$ mol dm!3,.I!$ mol =!.-. ,ii- +f there is no dramatic a&to-colo&r change ,as "ith 6nO4! titration-/ there are indicators "hich are oxidised immediately after the last %it of the reactant is cons&med/ (rod&cing a dramatic colo&r change. 8he %est exam(le is afforded %y Cr2O?2!/ "hich is not a self-indicator/ %&t oxidises the indicator s&%stance di(henylamine J&st after the e7&ivalence (oint to (rod&ce an intense %l&e colo&r/ th&s signalling the end (oint. ,iii- 8here is yet another method "hich is interesting and 7&ite common. +ts &se is restricted to those reagents "hich are a%le to oxidise +! ions/ say/ for exam(le/ C&,++-A 2C&2+,a7- + 4+!,a7- F C&2+2,s- + +2,a78his method relies on the facts that iodine itself gives an intense %l&e colo&r "ith starch and has a very s(ecific reaction "ith thios&l(hate ions ,32O32!-/ "hich too is a redox reactionA +2,a7- + 2 32O32!,a7-F2+!,a7- + 34O$2!,a7+2/ tho&gh insol&%le in "ater/ remains in sol&tion containing ;+ as ;+3.

On addition of starch after the li%eration of iodine from the reaction of C&2+ ions on iodide ions/ an intense %l&e colo&r a((ears. 8his colo&r disa((ears as soon as the iodine is cons&med %y the thios&l(hate ions. 8h&s/ the end-(oint can easily %e trac'ed. REDOX REACTIONS AND E5ECTRODE 9ROCESSES :e o%served if )inc rod is di((ed in co((er s&l(hate sol&tion. 8he redox reaction ta'es (lace and d&ring the reaction/ )inc is oxidised to )inc ions and co((er ions are red&ced to metallic co((er d&e to direct transfer of electrons from )inc to co((er ion. C&ring this reaction heat is also evolved. 5o" "e modify the ex(eriment in s&ch a manner that for the same redox reaction transfer of electrons ta'es (lace indirectly. :e can do that %y ma'ing a se(aration %et"een n metal and co((er s&l(hate sol&tion. As in fig.

9re aration o! #a"t &ridge'''' :e connect sol&tions in t"o %ea'ers %y a salt %ridge ,a K-t&%e containing a sol&tion of (otassi&m chloride or ammoni&m nitrate &s&ally solidified %y %oiling "ith agar agar and later cooling to a Jelly li'e s&%stance-. Signi!icance o! #a"t &ridge-----8his (rovides an electric contact %et"een the t"o sol&tions "itho&t allo"ing them to mix "ith each other. :e 'no" that the flo" of c&rrent is (ossi%le only if there is a (otential difference %et"een the co((er and )inc rods 'no"n as e"ectrode# here. 8he (otential associated "ith each electrode is 'no"n as e"ectrode otentia". +f the concentration of each s(ecies ta'ing (art in the electrode reaction is &nity ,if any gas a((ears in the electrode reaction/ it is confined to . atmos(heric (ress&re- and f&rther the reaction is carried o&t at 2L4;/ then the (otential of each electrode is said to %e the Standard E"ectrode 9otentia". >y convention/ the standard electrode (otential ,0IM of hydrogen electrode is I.II volts-. 8he e"ectrode otentia" )a"ue for each electrode (rocess is a meas&re of the relative tendency of the active s(ecies in the (rocess to remain in the oxidised/red&ced form. A negative 0I means that the redox co&(le is a stronger red&cing agent than the 1+/12 co&(le. A (ositive 0I means that the redox co&(le is a "ea'er red&cing agent than the 1+/12 co&(le. 8he standard electrode (otentials are very im(ortant and "e can get a lot of other &sef&l information from them.

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