vectorstock.com/3687784 Ths Nguyén Thanh Ti eBook Collection DAY KEM QUY NHO'N OLYMPIAD PHAT TRIEN NOI DUNG VAI NET VE DIEN HOA TRONG ON HOC SINH GIOI TRONG CAC ki THI CHON HOC SINH GIO! CAP TINH, CAP KHU VUC, CAP QUOC GIA (KEM DAP AN CHI TIET) WORD VERSION | 2020 EDITION ORDER NOW / CHUYEN GIAO QUA EMAIL TAILIEUCHUANTHAMKHAO@GMAIL.COM Tai liéu chuGin tham khdo Phat trién kénh bot Ths Nguyén Thanh Tit Don vi tai tr’ / phat hanh / chia sé hoc thuét : Nguyen Thanh Tu Group Hé trg tryc tuyén ‘book.comPHAN II: NOI DUNG ILL. CAC KHAINIEM CO BAN IL1.1. Phiin ieng oxi héa - khit Phan ting oxi héa ~ khir la ning phan img xay ra do sur trao déi electron gta ede chit phan tmg, trong dé chit khir nhurong electron va bj oxi héa thinh dang khirlign hop cén chat oxi hhoa sé thu electron va bi khirthanh dang khtt lién hop. So dd phin img: Ox; + ne = Khy Khy Ox + ne yy Kh + Ox) = Kh) +Ox \ Nhu vay phan img oxi hoa — Khir ludn gm 2.quatrink ~ Qua tinh khir (1) ka qué trinh nhén electron, img voi cép Oxh— khir = Qua trinh oxh (1.2) la qua trinh nhumg electron, img voi cap Oxh Do do trong phan img oxh — khir phai ¢6 it nhit hai cap 77 q chigu hudng va mic 6 xay ra phan tng phu thude vao nhieu yeu to, trong do yeato ih la the dién cue cia cic cp oxh — Khir. Néu sy chénh Ich thé dign cue cia h — khir eang lem thi mite d6 xxdiy ra phiin img gitta ching s¢ cang dé. IL1.2, Bign exe -Phitn logi dign ewe * Dién oye so sinh ie loai 2 : Kim loai phi mét hop chit it tan MA nhing = Mot s6 dign cue thing di trong dd chia anion ciibop cl A™.Sodé: A" | MAM Phin tng did = M+a™ Phuong trinh RT, 1 0,052, 1 0,0592 Ey = = ln = Ey + ks Say 2 ef A” SN eT "] ve ude [A] nén khi [A™] khéng d6i thi La ciing khéng di nén dign cye duge ding 4 ief'cue so sinh, dul: dign eye calomen KC! (bao hoa)| Hg:Cl, Hg Phan img dign cue: HgsCh-2e = 2Hg+2Cr Ptthé dign cue: By = Ey + ay Ex, - 0,0592.g[ Cr] Khi KCI bao hoa c6 E., = 0,244(V). Vidw2: Dign cuc bac clorua Cl’ | AgCLAgPhan imgdign cue: AgCl+le = Ag+CT. Pt dién cue: E, ~0,0592.1g(CI]; 25°C thi Ei,,,, =0,2224V 1004 7B ‘ “hehe “he Enscua Brey phu thude vao [Cl-] : Khi [CI] = constant lam dién cute so sanh, khi [CI] thay di he sit dung lim din ewe chi thi * Din cue chi thi a) Yéu edu: Dign eve phai lam vige thuén nghich véi ion nghign ctu, phan img phai me x, thudn nghich. Dién cue c6 céu tao don gidn, dé bao quan, dé sir dung, +b) Mét s6 dign cuc thuong gap: - Dign cue tro: Khéng tham gia phan img dién cue, chi la dang trung chuyéhe thughg ding, trong oxi hod- khit. Néu moi trudng oxi hoa manh thuimg ding C, Pt... 18 oxi hod vvima phai thi ding Ag, Mo, +. Biigm cue khi: Pt, Khi(A) | dd chira ion tao khi A O Vidu: dign cuc hidro : Pt, He | HY Phan img di¢n cue: 2H'+2e = Hy PL.Ch | Cl : Phin tng dign cue : Ch +20 2tr PL.Oy | OH : Phan img dién cue : O24 = 404 + Dign cuc oxi hod-khir: Pt | chat kh, cl Vidw: Pt| Fe Fe Pt |Mm, MnO¥, HY Pt | H2Q,Q itn cue Quinhidron phan img dign aA 2H'+2e = HQ Sain nF [HQ] Voi [Q]= [14:0] thi Eon2o= B’gnno + 0,0592lg[H']= E"quzo- 0,0592.pH vag ~ EXquing= 0,69: ign eve Quit ing dé xe dinh pH, lim vige thuin nghich vai H”D& C= Cjng nn kim S digncye: M™ +ne = M ong tinh dién owe : Exon = Ermine gM] a Ptdign cue: Equag: = Bign cue ming chon Ie: duge tao ra tir ede mang de biet, thé cla dién eye phy thude mot eich chon Ipc vio hoat 45 cia I ion nhat dinh va dign eye kim vige theo co ché trao di ion, khong 6 su trao ddi e & phan img dign cue. So dé dign hoa khi do thé cia dign cue mang chon loc: dlign cye so sinh I | dd (1) | Mang | dd (2) | dign cue so sinh (2) 5Hay sit dung nbat la dién cuc mang thuy tinh lam vige thudn nghich voi ion H ‘Ag, AgCl | HC10,1M | mang Thuy tinh Phuong trinh dign eye : Err = E°rr + e In(HH') y= Err + 2,303 a le(H)ys 2 : 0, + 0, RT =Brr+ DIM(H)u= Er bpH (voib=2,303. “) 2 rrkhng hing dinh ma phu thu vo thin pin mang thy ih va tinh phn dl wong IL1.3, Thé dign cure \y = Quy ude vé dau cia thé dign cue tigu chuéin: Thé dign eure tiéu chudin dic pa ft trinh khir Chitoxiha + ne = — Chit khir AS - Dé xée dinh gid tri thé tuong d6i cua mot dign eve ndo 46 6 itu kn chiiin, ngudi ta ghép ign cue do vii dign cue hidro chudn tao thanh dign theo so dé (POH,,p, = latm| }) = 1fOxh, kh Trong dé: dign cue bén trai la dign cue hidro ti ccue bén phai la dign eure nghin eu, xiy ra qui tr pin dign tao thanh theo qui tac trén, Ein G day, E' ppp la thé didn tigu chudin Bown la thé cy xi héa~ Khir nghién iru tigu chuan Bang thuc nghiém, t thé xéc dinh duge Eyin con dai luong E°y p/p), khing xéc dinh duge. Do dé, ta kh@hg thé ~ Vivi juy woe: E*>py*/4 h gia duoc Bsa 0. Tird6, E’wn = Epin Vay thé iia m6t cBp oxh ~ khnr (thé kh chudn) chinh la ste dign dong cua mét pin dig khi mg mot dién cue nghién citu (co hoat 46 ciia cde chat trong dung dich déu bing 1 va aks ap suat bing | atm) véi mot ign cue hidro ti8u chun (Gu hoat d6 ciia dang oxi héa va dang khit khéc | thi: Equa # E*saan va khi d6 gid tri 9g 1, $8 duoe xe dinh theo phuong trinh Nernst Doi voi nia phan img: Ox +ne = Kh (Ox) RT) f, RT, [Ox] Tacé: B= B's + nl =e $n + ‘cb mnt eM) Boman t ee teh f,. , 0,0592 , [Ox] 625°C B= Evan + 29592 jg far 4, 9.0592, [Ox] ee tn SEK]+ Néu f= fin = (dung dich rat lodng) thi E = E° n+ oe (os) n [Kh] A ae 0,0592, [Ox] ~ Néu fox, fin # 1 thi: E=B’ oun + 7 ‘sen VoiB an = Pann t 20522 jg fa. no fy Khi do, Baus duoc goi la thé tigu chun thu (hay thé tiéu chun diéu kign) Nhu vay, dua vao phuong trinh Nernst ta c6 thé xae dinh duge eae gia tri E, E etaybat oxh ~ Khir ndo trong nhing diéu kign eu thé, tir d6 cho phép ta cé thé dénh gid ning oxh — khit cita mt chit trong diéu kién chudin cing nhu trong diéu ki hnung cua Ie ion va ede qua trinh phy khée. 114, Hing sé cin bing <* = Hing s6 can bing K 1a dai lugng cho biét chiéu eiing nhi iy ra phan tmg déi ‘Gi hg can bang oxi héa — kintrthuan nghich. ~ Dé xa dinh hing sé can bing K ta dya vao + Caich 1: Dua vao su bién thién ning luon; chudn AG” ‘Ta co AG =~ nFAE® =- RTInK, ‘su anh RT nF Ink =2,3031gK = — AB? Igk = ——_ Ar" ehK 2A oh 2,303RT 0 625°C (298K) thi Igk = = ors"! vai AB = B — Fy + Cach 2 — nia phan ting ORF ne = Rhy K, =10= =o sets Kh = 0x) +m Ky Ox, + Kh = Kh + Ox K = Ky, Kh 10 How genase e = |y thuyét vé nhiét déng hoe, dé phan ing xay ra theo chigu thuén cng manh gi tr oF ang dm, nghia ki AE" phai dng lim. Do vay, dé phin img oxi héa— khir xy ra eding ih thi higu thé dign cue tigu chun cia hai cp oxi héa — khir phai cang lin, Thé nhung dé danh gia dinh hung hom ta can dura vao hang s6 can bang K. Gi trj K céng lan thi phan img xay ra theo chigu thudn cing manh, néu K cing nhé thi mie dé thudn nghich cia phan img cding ting ‘va kha ning phin img xay ra theo chigu nghich s@ cang lon ‘Trong truémg hop mudin dénh gia dinh Iugng mét each chat ché hon, ta can tinh thanh phin cia hé phan tig sau khi dat t6i cn bing. Tuy nhién, viée tinh todn cén bing trong cde hé oxh ~ khir kit phe tap vi ludn ¢6 ede qua tinh phu xy ra kém theo, Do dé, trong trong hop 7don gian, khi cn bang oxh — khir duoe thuc hién 6 nhiing diéu kién xe dinh (pH, chat tao phue phu, tao hop chat it tan...) thi ta e6 thé danh gia edn bing dura vao hing s6 can bing diéu kién K’ theo eae bude sau ~ Bue 1: Tinh thé oxi hoa - khir diéu kién (E) cla cae cp oxi hoa khir ~ Buée 2: Tinh hing s6 cn bing diéu kign (K’) bing cdch t6 hop cdn bing oxi hoa ~ Khir theo cach thing thudmg, ~ Bude 3: Tinh can bang theo dinh luat tac dung khoi Luong. 11.2. CAC YEU TO ANH HUONG DEN CAN BANG OXH - KHU ‘Theo phuomg trinh Nemst, thé oxi hoa — khir eda cde cp phu thude vio hy wa dang oxi hia — khit. Do vay, khi 6 mét yéu té nao do lim bién d&i hoat dé cjg cag dang thi thé oxi héa— khit sé bi thay d6i va do dé sé anh hug dén edn bing oxi hog rong khudn ikhd ca ludn vain nay, di tuong chit yéu la hoe sinh phd thong, do we ig bai tip va vidu ‘minh hoa ching t6i coi hoat dé ciia cdc chit chink fa ning 46 (hay § 85 hoat dé bing 1) Cc yéu 16 quan trong anh hung dén cén bing oxi héa. khiNag/g6m: 2.1. Anh hucing eka pH a. Anh Ineéng tre tiép QS pH s& anh huog true tép dén edn bing px It Khi trong phuong tinh mia phn mg oxi héa khir 6 mat ion H” hode OH 't ‘Vi du: Xét ban phan ung: 4H Ng Ge 2Cr* +7H,0 Tacé: B= E), ‘CoOF a 0592 = 80592 rary 4 930592, [Cr,0F] eee Eo. 1 (Hy -0,138pH cso nee" ‘coy ne tathdy thé diéu kién E phy thude vio pH, khi pH cang gidm (moi trubng cang axit) thi ting, hi d6 tinh oxi héa ciia Cr,O,”" céng manh va nguoe lai khi pH cdng ting thi E' cing fam va do dé tinh oxi héa ciia Cr,0,* cing sé cang giam. b. Anh ucong gin tiép Khi trong phuong trinh nita phan tng oxi hia ~ khir khéng o6 mat H” hoae OH tham gia, nnhung trong hé lai e6 sir tao phite hidroxo cia cde ion kim loai hoe c6 str trao di proton cia cite chat oxi hia, chat khir la axit hoe bazar yéu thi khi d6 pH s& co anh hudmg gidn tiép dén céin bang oxi héa ~ Khir‘Vi du: Xét anh hung cua pH t6i tinh oxi hoa kit ctia cap Fe"'/ Fe" (coi (i [i]) Fe" +e Fe* Et oaggs 207TV - GO pH<2: Fe’, Fe™ tao phute hidroxo khGng dang ké nén thé khdng phu thude vao pH [Fe*] [Fe] - 6 2< pH <6,6: Fe, Fe* tao phite hidroxo dang ké Fe* +H,0 = Fe(OH)" +H" “By = Fe* +H,O = Fe(OH)’ +H" *B, =10°" Vi *Bn, lon hon *Pjy nén khi pH ing, ndng d6 ion Fe** giim nhiéu hgffyina,dgFe”’ E +:0,0592 Ig: rene’ = pe ree do dé thé oxi hoa cua cp Fe /Fe™ gim nghia ki tinh oxi hoa cia Fe™ gi knit cita Fe™* s& tang lén. Dén mot pH nao dé khi Fe va Fe chuyén hoan toan t hire hidroxo, lac dé trong hé sé xuat hign mot cap 1a — khit mai. Fe(OH)* +¢ = Fe(OH)" [Fe(OH)"] E=E! +0,0592|; 2 Fe(OH)" O diy: E? = E?~0,05921g Pu. o morris giam. Nhu vay khi pH ting thi E ~ 1 tinh khir eda Fe(II) ting va tinh oxi hda eda Fe(II) - O pH> 66 méi, tai dudi dang hidroxit nén trong hé s® xuat hign cp oxi hoa — khir Fe(OH), 4 +e Fe(OH), 4+OH" EE? =-0,52V. cry E=B-0,0592Ig(0H"] vay, khi pH ting, nghia la khi ndng d OH ting thi thé cita cdp Fe(OH)s/Fe(OH), sé 214m dan, do dé tinh oxi hia eiia Fe(OH); gidm va tinh khir eta Fe(OH). tang. 11.2.2, Anh ucéng cia sy tao phite Khi trong hé c6 chira cdu tir co kh ning tao phite voi cae dang oxh, dang khir thi nding d6 cia cde dang nay s€ bi thay d4i va do do thé oxh — Khir cua ching sé bi thay adi ‘Trong thue té dang oxi hoa cé kha nang tao phire manh hon dang khit, do dé thé oxi héa ~ Khir thuong gim khi c6 mat chat tao phite.‘Vi du: Xét kha ning oxi hoa cla Fe" khi 6 mat F” du ‘Trong hé, khi co mat F’ du thi Fe’* tn tai chii yéu o dang FeP,. Le nay trong dung dich 6 cae can bing sau FeF = ore + ar pia Fe +e = Fett K,= 1078 Foe, +e = Fe + GFK = p'K, = 108 ott a JAK, = 102" 19 av = ES = E} - 0,0592.12,06 = 0,771 - 0,0592.12,06 = 0,059 V A E} =0,059V< E} =0,771V Nhu vay, tinh oxi héa ctia Fe gidm manh khi c6 mat cua F- a Oi voi hé ion kim loai — kim loai, thi su tao phite chi xaj hi co mat chat tao phuc thi nong dé M™ giam va do dé the oxi cap M™/ M cing sé iam 1.2.3. Anh hucéng cia sy tgo think hop chat ittan Ciing giéng nhu trong truang hap c6 sur trong hé c6 cau tir c6 kha nding tao hop chat it tan voi dang oxi héa hode dang gt qua ciing lam gidm ning d6 cia dang 46 va do do thé dién cuc cing sé bi thay d6i daigenthieu va mite dé ciia phin img ciing bi thay di ‘Vi du: Xet kha nding oxi hia —K Trong hé 6 cée “@P ae Bs ig e108 Ag +Cr k,= 10" e = Ag 4+cr Ky = 10K, k, 1 + 0,0592 Ig K, = 0,799 + 0,05921g(10") = 0,209V te = .e ring Ye E 0,799V. Nhu vay, khi c6 mat ion CT tinh oxi hoa eta Ag* giim xuéng, \a'/ Ag khi co mat ion CI 0 ‘ata lai tinh khir cia Ag tang lén. Tit vi du trén ta nhan thay, thé ciia ep Ag'/Ag phu thude vao tich sO tan (K,) cua hop cchit it tan AgC1, Néu xét di véi hé oxi hoa khir bat ki thi khi dang oxi héa hoc dang khir tao hop chat it tan v6i thuoc thir phy c6 tich s6 tan K, céng be thi thé oxi héa ~ khir thay déi cang nhieu va do d6 mite d6 anh hung dén chiéu husng ciia cén bang oxi hoa — khir cang lon,113: HE THONG CAU HOI, BAL TAP ‘Dé phéin loai, ching t6i tién hanh tap hop va phén tich cde bai tip dinh tinh e6 lién quan dén thé dign cue va pin dign trong cdc dé thi hoc sinh gidi mot sé tinh, dé thi hoc sinh gidi Quée gia trong mét sO nd tro lai day va mot s6 tai ligu kha. 113.1. Cac bai tip vé tinh thé dign cre. ‘Moi phan tng oxi hoa khir déu xuat phat tir hai cap oxh- khir voi gia tri thé dién eye tuong ting ciia mBi cap. Tuy nhién, khing phai cap oxh— khir nao cing e6 sin gi tri thé cue trong bang tra ciu, va eling khong phai Ie ndo cding e6 thé sir dung cde gi tri N eu\kién chuan. Vi vay, dang bai tap dau tién ching t6i dura ra la bai tap tinh thé dign c chudn va digu kign bat ki G 113.1.1. Céch tinh thé dign ee chudn S * Thé dign ewe chudn chi lién quan t6i phin ieng oxi hod - uN Bai tp 1: 6 25°C thé khir chuan cia mét sé cp oxi hoa - khtr — mg axit) durge cho nha sau fo FE" Be =~0,440V ; ES 2 jpg OTT 1 Huéng din. Dé tinh thé dign cue chuan cia 1egp. ctu: - Viet phuong tri nia phin img oxh-khit ~ Chon ef edn bing tuong ting trang t 10 d6 ma khéng cé trong bang tra Hcp cd thict kp E° ig thai cudi ctia nira phan img 43 viet ~ Thiét lgp biéu thire tinh K hoc AG theoY?. Tuy nhién, trong dang bai tap nay, can nbn manh cho hoc sinh: céch tinh gia tr! a thudng dugc tinh cho phan ig ma trong dé chi xdy ra su oxi héa— khtr, con of SS K c6 thé tinh cho ca phan img trong dé bao g6m c& qua trinh phu nhur tao phite, tao ittan ‘Voi dang bai tapthay, c0 The o6 2 cach lam: iC}ban phan img Ki= 10%". note AG? LLFE! (1). Pe Ba Fe Ka= 10°; hotle AG? =-2F ES (2) 1) + (2) ta duoc: 9 Re+3e= Fe Ky= 10°: bode AG? =-10F ES (1) + Néu tinh theo K: => Ky=KiKo=> 3 £9 =2E! + EP => EY = (0,771 - 2.0443 = -0,0363(V) + Néu theo AG? => AG} = AG? + AGS => 3B} =2E) +E! => E}=-0,0363(V) ich 2: Khong m6 ti bin phin tng ma chi m6 ti so a6:Tit so do trén taco: ny EP =m. E3+ mE? => EB} = (0,771 -2.0,44)/3 = -0,0363(V) trudng hop khi mé ta ban phan img theo so dé sé aBy dang hon va trinh nhim lan khi té hop cée cén bing \ Nhin xét: Doi voi mot G pH = 0 va & 25°C thé dién cue tiéu chun E° cia mat sO cap oxi, nny sau: 20,7 1p (F) 1,31 V , 21057 () 119 V5 2HIO/T, (r) 1 b (Wr 054 V. (0) chi chat 6 trang thai ran. 1. Viet phuong trinh niza phan tig oxi hoa - khir cia cae 2. Tinh E* cita cac cap 10.7 105" va 1057 HIO. Huéng dan Bai tp nay tuong tu nhur vi du 1. Yéu edu a viét cdc ban phan img oxi hoa - Khir ca cde e&p da cho, day ki Ki ning co ban hoe sinh can chi y ghi thm ca trang thai trinh, 1. Cée phuong trinh niza phifyjmg'oxi ho’ - Khir eda ede cip 8 cho. 2107 + 16H + I(r) +810; EB) =131V 210; + 12 ig bai tp thé dign cue. Trong phan nay, cee chat (ran, khi..) khi viet cdc phuong hr) +6720; EB + 2HOTY IW Me = by) +2H0; EL=145V “ Pl la x giong vi dy 1. Hoe sinh 06 thé lam theo 2 cach nhung don gian va nhanh nat la 19 ta so do phan ting cac trang thai oxi hoa cé ign quan dén cp oxi héa khir can tinh thé 54V ar > BRS clu tinh gid tr thé dign cuc chun ciia2 cp 10y/ 10s" va 10s/ HIO. Cach ap da biét thé tiéu chuan, ‘Vi du: dé tinh thé cita c&p 10,7 10" dua vao so dé sa PF’, FP, 210, ———» 210; ———» n=de n=l0e =10E) +4E!>E = 14.131-10.119 =161() Tuong tu dé tinh thé ia cBp 1057 HIO ta 06 sod: F 0 A 210; —"—»2H10 + Cho gidn dé qué trinh kit thé kh: qua trinh khir dign ra theo offiéy mbiisén, thé khir chuan due ghi trén cde mili tén va do & pH= 0. 40298 Rode La) cavy (cro) 2S cqvy SS cravy “68, oor BS cy 1. Tinh E? va E om 1h Cr* va Cr(VI) due khong? ; Cr va tinh a6 bién thién thé cia hé & 2. Dra vio tinh toan, cho biét Cr(IV) 06 thé 3. Vigt qué trinh xiy ra véi he oxi héa - mhigt d6 298 K, khi pH tng I dom vi pH. oe ina A kh RY tf! Cho: El, 3,¢0+7 133 V; Hang khi R ~ 8,3145 J." mol"; Hing sé Faraday F = 968%5 C Phot” Huéng din Bai toan duoe ig gidn dé Latime. Qua bai toan nay, hoe sinh sé duge hoe é Khir chun ciia mat cp oxi héa— Khir trong gin d6 latime tir cdc aid tri da cho, hé suy Tuan tinh én cia dang oxi hoa hay dang khir nio d6 cé trong Tir gith dé ta c6: 3 (0,744) =-0,408 + 2E° > E? =-0,912(V) Y 0,55 + 1,34 + BY -3.0,744 = 6.0293 > E? = 42,1 (V) 9 % Theo nhigt dng hoc, Cr(IV) c6 thé di phan thanh Cr* va Cr(VI) khi AG" ciia qua inh <0. 2Cr(IV) + 2e + 2Cr* (1) > AG? =-nBPF=-22,1F CHVI) + 2¢ + CAIV) (2) ssh 0945 (V) = AG} =-nE}F=-2.0,945.F ‘Tir (1) va (2) ta ¢6 qua trinh tw phan hity eda Cr(1V) 133Cr(IV) > 2Cr* + Cr(VI) AG! AG! = AG! AG? = - 2.(2,1 - 0,945).F <0 > Vay Cr(LV) 06 thé tur phan hiy tao thanh ce vace 3. C10 + 14H’ + 6e 2Cr* + THO - O gif tri pH ban dau va 6 gia tri pH ting | don vi, gid tri thé dién cue lan luot duce tinh theo cic bigu thir: GAGE B= 1334 RU jg {Cur }.00" oF! (Gy ‘S 2 (yore 1334 RE (CuO. Uo "| oF (cr FP b-B6 biénthién a thé: B, -, = S5!45-298 painio! —-o.ry NN 6. 96485 Cho gidn dé Latimer eva dioxi (02) trong moi truing axit. 0,695V_ 0, 2%) to, LIB, to SS trong dé Os, Hs0s va HO la ede dang oxi oa - hi a inde oi bd giim din, Cas 0,695V va 1,763V chi thé khir cia cde cp oxh ~ ahh béi cac dang tuong img: Ox/HO2, ‘H;0,/H20. a. Viet cde nira phan img cia cac\cap t b. Tinh thé khir cia c&p Ox/ ol ¢. Chimg minh ring g phin huy thanh ede chit chira oxi 6 mire oxi hod cao hom va thap hon theo phan = 0; +210 tap thong thudng, chi nhim kiém tra kién thite eo ban ciia hoe sinh fin, cach viét ban phurong trinh khit tir cp oxi héa- khir di cho, cdch t6 (tinh gia wi thé din ewe ota ep yéu edu. Tir gi tri thE dign eve tinh a itu tr din bign cia qua trinh dua vao bigu thie Ién hé git nding luong ty do a fién cuc chuan. Doi voicip OwHLO:: O2 + 2H + 2e > HO: (I) B=0695V ai v6i cap HsOvELO: HO: + 2H" + 2e + 2H0 (2) E2=1,763V b, Nita phan img ciia cp 0,/H,0: O, + 4H’ + de + 2H,0 (3) Es? Céng cae phan img (1) va (2)s8 thu duye (3). Do dé APE, = -2FE", + (2FE‘) hay E's = 26 +E%) 4 = 2x2431/4 = 123 V c. Déc6 phan img di licia HO: HO: > 1202 + H:0(4) 14ta lay (2) tri (I): (2)-(1) = 2HpO) > > + 2H,0 hay 1:02 + 1/202 + H20 a AG's= 1/2 [-2FE*) - (-2FE*)] = F(E°,-E":) = F(0,695 - 1,763) = - 1,068F <0. AG, <0, str phin huy cita Hy0> la tu dién bién ve phuong dign nhiét dong hoe. Nhdin xéte Trong gin d6 Latime, néu gia tri thé dign cy sau lim hon gid tr thé dign cu tag thi dang oxh — Khir & gitta khdng bén, bi phan hiy thinh 2 dang bén canh 6 diéu kign my Bai tip 5: Tinh céc gid tri the dién cure chuan cita cae cap sau day: \ a. Eiing BEE gy = 150V; El, =1A1V v 7 . Bosna SIV; E' Haring dis Bai tp nay hoan toan giéng vai cde vi du 1,2: cue chuén chi lign quan dén phan img oxh ~ khit. Hoe sinh ¢6 thé lam theo 2 (s Spin bing ke mo when sod Két qué tinh duoe nhur sau: =151V iyi? b. Ee =151V N/M" 6; Gian dé thé khir cl in (méi trudng axit): no, “OY > MnO, —_, Mn®* *E5IY ygg2e x +1,23V ‘thé Kh chuan MnO,/ MnO> ; MnOx/Mn** : Bai tip nay gidng voi BT 3 p sb: 2,27V va 0,95V. Cho cae gid tri thé dién cue tigu chuan sau day: 0 =0:564Vs E - oe E ona = 05645 E aot Mao: 226N; E outa O55; 0 Ps . B° = yg = HS1VS Enystay = b18V a. Viet cde ban phuong trinh khit img voi mdi cap oxh- Khir trén. b. Xae dinh cde dang bén nhigt dng ciia Mn pH =0 heing dan:Bai tap nay gidng véi cde vi du 3,4. Dé xac dinh cde dang bén nhiét d6ng, ta 06 thé tinh ning luong tu do Gip d6i véi cée qua trinh tyr phén hiiy cua cde dang kém bén (gidng vi du 3.4) hod so sinh cac gia tri E° cia cde cap oxh — khir lién tip dé tim ra cde dang c6 kha ning tur oxh hit = 0,564V < E) ‘a0 o0, Tat Bea 2.26V, do dé trong dung dich (pH=0) MnO; vira la dang oxh (B° Idn), vita la dang khir (E” nhd) nén MnO} sé tu oxh Khir theo phuong trinh: 3MnO +4H* = 2MnO; + MnO, +2H,0 yy TuOng 1H, ER, nyo, = 226V > Ep, ye = 0.95V trong dung dich 6 ey khir: MnO? +2MMn** +2H,O = 3MnO, +4H" Eben ~ O95V < Exenge = SIV nén 06 me oxh = khit 2Mn** +2H,0 = MnO, + Mn’ + 4H" Eo Mn LSIV > Bhs. “LI8V nen i trinh sau xay ra trong dung dich: 2Mn* +Mn = 3Mn™ Nhu vay, ede dang bén nhiét dng ctia Mn 6 pl * Tinh thé dién cure chudn lién qual =Mn02 va MnO; ‘Boi voi dang bai nay, vie tinh the dién chit yéu lién quan dén cdc phan img tao phite, phan img tao hop chat it tan, ne axit ~ bazar. Céch lam don gian va d8 hiéu nha déi Gi hoe sinh dé la céich t6 hopred inh va tinh theo K. Bai tp 8: Tinh the ca cac — kchir chua biét sau Cho E? 76V ,)4]2* = 108"; Tinh ES a) Cho Era Bizn(NHs)4] .? 2081 b) Ch % 0,34V 5 Kcus= 10°? ; Tinh Exysicy ? pe Tinh Eso =? inh Enq, 025°C. Bigt B®... =0,96V; EXoyy,= L7ISV. ‘NO;/NH, 'NOVINO at; = 0306V, PK NH) = 9.24, ©) Cho E° ‘co 1c 33V; Kc(OH)s= 10%; Tinh Buen,” Cho: CLOF + 1b0 = 2HCrO; — pK=1,36 HCO, = COP + HE pKs=6,50 Huéng din a) Té hop can bang oxi hoa - khit va cn bang tao phitc. 16Zn* +2e = Zn K, = 1076000592 os ‘Zn(NHs)° = Zn? +4NHs Bizn(NHs),)* =! Zn(NHh)e* +2e = Zn + 4NHs K = 10° => K=Ki. Bezn(NE)]* > Eesoaan "8023 (V) 0,0592 . Hote Eien ~ Enaiiay *—3— 'Bfzngnt)d* 0,0592 = 076 + 22 igo = 100309) AY - Nhu vay, nin chung, ki cd surtao phite eda ion kim loai trong din G thi thé dign eye chudin bao gid eding dm hon }) Té hop cain bang oxi hoa - khir va cn bing tao hgp chit wk cu +2 = Cu K,= 1900 CuS = Cu + S* Ks= 10% Ss CuS +2 = Cu + S* K= 10%" => K=KiKy => Eoscy So V). 0.0592 92 Hodc E" = E® Igl0* = -0,70192(V). cusca Eee $y dang khir li OH”. Khi Wb, tur hoc sinh sé nhan ra can phai to hop thém can bing cua H;O trong. ~ qua trinh tinh ie cla clip 03/2 OH. Cu thé nhu sau: + WH +2e = 0,+H,0 RS pe LO = H +O Ky 03+ H,0+2e = 0; +20H" K= s Bae =12412(V). 4d) Bé tinh duge gid tri thé khir chun etia e&p NO; / NH, tir ede dit kign d& cho doi hoi hoe sinh phai nhin duge sw lién quan gitta cae dang oxi héa khit ciia Nito, Déng thai lai biét két hop voi céin bing axit- bazo cla NH} va can bing phiin li cla H,O, cling nhu cde hé sé cin nhan thém yao khi t8 hop cdc edn bing. Dén day bai toan tinh thé dién cue chudn cla mot capoxi hoa khir bat ki da tro nén phic tap hon nhigu, doi hoi hoc sinh phai c6 sw nhay ben, tur duy logie ‘To hop cde ean bing sau 2.[NO; +3e+4H’ = NO+2HO K,=10"°? a) 2NO+4e+4H" = Ny +2H,O Ky = 10" 1780057 Q) No +6e+8H* = 2NH,* Ky = 190s? 3) \Y 2.| NH = NHs + HT Ki=K.= 10° (4) » a » = H+ OW Ks=Ky=10™ N 6 2NO; + 16e+ 12:0 = 2NH3+ [80H K =(Ki)Kiks "ex => EB, =-0,097V. ¢) Tuong ty nhu phan d, & phan nay ciing doi hai phai co ‘ca nhieu qua trinh, dng thvi phi van dung linh hoat cdc ditkign dé bai cho. Dé bai cho gia tri thé dign cue ella Cr(VIY) Crp clu tinh gia tri thé cia Cr(VIYCr(I) trong moi 1g trong mdi trudng axit, va yeu 8 hop cée cn bing trong d6 c6 suc mat ciia H’, OH” ‘To hop cae edn bang: Xe C107 + HO pK=1,36 (1) 2x | HCrO; 5 pK.=650 (2) 102+ 2H pK=14,36 (3) e+ GH = 2Cr + THO K = 10°! 50592 (4) 30H = CKOH)s — KsC(OH);= 10%" (5) H,0 = H+ OH Ky= 10" (6) cae can bang (3), (4), (5), (6) ta co: 2CrO,* +8H,0 + 6e = 2Cr(OH); + 10 0H" K = 10°" FE Co 2" = 0,133 (V). 9; Tinh gid tr cdc gid tri thé dign eye tigu chun sau i aE! on = 10% aE cut acm Bit Epes OTTIVS Begoyg = 10" Breen i en = 1095 ae) + Eaten PEE, c32°= LBAVSBeseunps = LOPS Besos = 10 Hung din:Bai tap nay thude dang bai tinh thé dign cu tiéu chuan c6 Lin quan dén cae phan img tao phite, {go hop chat it tan... Hoc sinh chi edn t6 hop cae can bing thich hop theo gid thiét =0,018V Bap 38: oop man = 03560 5 Ene eso 1113.1.2. Thé dign ewe & didu kign bat ky Dang bai tap nay nhim ciing ¢6 cho hoe sinh phan kién thute lién quan dén phuong trinh Nersnt, ‘Trong khudn khé cua dé tai nay, chip nhiin gin ding: néng d6 cae chat bing hoat d6 ciia ching. Do vay, trong cic phuong trinh Nersnt déu biéu dién su phy thudc thé theo nong 46. a) Tinh thé cia mét dign eye Pt nhing trong dung dich gam Cr,0: or O,S0M; H’ 1,50M. Cho Ee, opp. = 133V « ) Tinh thé ca dign cue khi nhung dién eye Cu vao dung wg’ IM; NHs 1,00M, Biet E°cy2tjcu= 0.34V: Bou NHS).2* = 10'7 ¢) Tinh thé dign cue ki nhing dién cue Pb vio mu E’pyypp=-0,126V: Kippgo,= 107% Hucing din Dé tinh the dign cuc & diéu kién khins ),1M; NaSO, 2M. Cho ir dung phuomg trinh Nernst m6 ta su i trong. Co nhiéu trumg hgp, néng 46 i khac nhau khi tao thanh hop chat it tan, tao pphu thude thé theo néng 46 chat oxi hoa, ol ciia cae chat trong phan img oxi hoa- khir thay’ phite do dé thé cia phan img cing a) Tinh theo bain phan img dygtrgtghug trinh Nernst Cr,0F + Qe 2C8* + 7k 208, lonor yay tory 00592, 2x(1,5)"* poe, = 1,363(V) & 6 (05° My) ee ccéc phin img oxi héa-khit od ion H* hode ion OH truc tiép tham gia phan img ve thude true tiép vio pH. Cops nay ign quan dén phan tmg tao phite cia dang oxh trong thé dién cue nhu trong phin FY thuyét di trinh bay. Sy tao phic vai dang oxh, dang khir sé kim thay d6i nong 46 cia ching, do dé lam thay di thé oxh-khit day xét hé ion kim loai-kim loa: M™ + ne = M Thi su tao phite chi xay ra gitta dang oxi héa, M™ voi phoi tir L: M"+pL = ML,"Do dé khi cd mat chat tao phite L thi ndng dé ion M™ gidm va thé oxh- khir giam. Dé lam duoc bai nay, gido vién néu ra nguyén tie chung cho hoe sinh: di voi mot he bat ki, bao gid’ ciing xét cdc qua trinh xay ra hoan toan, dé xét thinh phan gidi han, sau do moi xét dén cdc can bang trong hé; tir d6 tinh nong d6 cn bang céc ion trong dung dich va tinh thé dign cue. Tacd: Cu’ +4NH3 = Cu(NHs),?* ndbd 0112 ndeb 0 08 0,1 yy ‘Dé tinh thinh phan can bang ta tinh cn bing nguoc lai oS Cu(NH)."* = Cu +4NHSB Cuan) 2°= 107 c ol 08 « eb Obx x 084x OS . w= MOB—4" 19-7 5 y=487.10M Ol-x = Ecu(Nos)2/Cu= Eu cu * (0.0592/2)le{Cus =034+ = 8) = 0.0044 (V) c) Su chuyén mét trong hai dang oxi héa hode wanfNhop chit it tan voi mét sO thude thr phy lam gidm néng d6 cia céu tr d6, vi vay thé ut thay di, do dé chiéu cia phan ung thay doi, O day ta thay nong d6 Pb™ giam =tinh. cia Pb giam va tinh khit ciia Pb tang. Cac bude lam phin nay cing wong ty read Tacd: Pb” +S0," ndbd 04 & ndecb 01 ‘Dé tinh thar in biing ta tinh cn bing ngugc lai: ~ & P+ S00 Ke= 107 hut 19 1x x 19-x 10 x= 115.10" M Ol-x Eppsoypo=E'pp/pp + (0:0592/2)IPb] = 0,126 + oct tlis 107)=-0,391(V) Bai tip 11: Thiét lap sur phu thudc ca thé theo pH ciia cp Fe™/Fe™* Cho bidt Tryon, = 38:10, Tron, =48:10", Bla. =0,71V Huéng din Bai nay lign quan dén sw anh hug cia pH dén thé dign cue ciia cap oxh ~ khit. 6 day khing phai la su anh hudng truc tiép ma la anh hudng gidn tiép qua ndng dé oiia cdc dang oxh va dang 20hit. O cde khoang pH khae nhau, Fe va Fe’* 6 thé ton tai 6 dang tu do trong dung dich hoae dang hidroxit Fe(OH);, Fe(OH):. Khi d6 ndng d6 edn bing eiia ede dang nay sé bj thay di va déng thai trong phuong trinh Nernst cia cap nay sé xuat hién dai long pH. Mudn vay, trude het, hoe sinh phai tinh duge cae gid tri pH ma 6 do bat dau xudt hign két ta Fe(OH)s, Fe(OH): Coi [Fe] = [Fe] = 1M. - Nong d6 OH tai d6 xuat hién két tia Fe(OH); la: = J au 10 = 107°" (M), khi dé pH = 1,53 oe ~ Néng d6 OH tai dé xudt hién két tia Fe(OH)» Li: = [eso _ sue" 210° (kh © [Fe"] & ‘Xét bin phuong trinh: Fe* +e = Fe", tacé - Trong khodng 0 < pH <1,53 thé ctia c§p Fe" /Fe™* = phy thu Exonger= Ep a _ Trong khoing 1,53 pH £ 6,34 , Fe™ tin tai cha Q E giam xX [Fe] ro 7 c oe "e(OH)s, nén [Fe] gia, do vay Traom, ny TN eum pOH= 1,04—0,177 pH -Trong khoang 6,34 < pH va Fe déu tin tai 6 dang Fe(OH); va Fe(OH):. Do E, —Ig{Fe"')) +0,0592Ig Ss 0s oy rovines = Epoeire vay néng dé 2 ion nay du gia iam ~ 592 Is Ir if =0,771+0,0592| | j Spey ony, Trou, (OWT IF (OH), T+ 0,0! je 8 05021 [H*]= 0,292 - 0,0592pH. x aa0%10" eee Ne 2 QQ a Tinh thé cia dign cue cadimi nhing trong dung dich Cd(Cl0:): 0,2000M va NEb ° = 10 IM. Cho Ese, -O4O2V5 Baggy 7 10 b, Tinh thé eda dign cue Ag nhiing trong dung dich AgNO; 0,020M vi NayS2Os 1,04M. = 19 Cho Ei 4g= 080V s Byiso,p-= 10 c. Tinh thé cia dign eye Ni nhing trong dung dich Ni(CI0,), 0,100M va NH 2,600M, 0.233 5 By, gy ge = 10 iN 21Huong din ‘Trong bai tp nay, ta s® xae dinh thinh phén gidi han cia hé, sau do xét cde eéin béing c6 thé xay ra va tinh ndng d6 can bang cdc cdu tir trong dung dich. Ap dung phuong trinh Nernst dé tinh the dign owe. a. Xét phin img: Cd*+4NH, = Cd(NH,);* ndbd 0,200 1,800 ndeb 0 1,00 0200 ‘é xae dinh thanh phan cén bing ta xét edn béing nguoe: Cd(NH,)* = Cd + 4NH, C0200 1,00 eb 0200-x x 1,00-4x XU,00—4%)* geo _ 0,200-x Gia tri thé cia hé ng: E = Ef, ¢y* (0.08922) mes b. Tuong ty ta c6: E=-0,098V c. E=0,562V Bai tip 13: Tinh thé cia dign eye Platin nh Ae dung dich sau a. TiO™ 0,010M va Ti* 0,020M @ pI 3,00. b. MnO; 0,20M; Mn’ 0, fF HgSO, 0,10M c eae 0M ° Cho Eoin ? a= LSIV, Eon phan img khir va tinh theo phuong trinh Nersnt. Trong phin b, chit y lung dich H»SO; 0,10M. ps: a-0.273V, b129V; .0,121V Y 1 gd a, TrOn hai thé tich bing nhau cua hai dung dich SnCl 0,100M va FeCls 0,100M. Xae nong d6 cae ion thiée va sit khi cén bing 6 25°C. Tinh thé cita cde cp oxy hoa - khir khi cin bang b. Nhung mét soi Ag vao dung dich Fe,($O.); 2,5.10°M. Xée dinh ning dé cia Fe; Fe vi Ag’ khi edn bing & 25°C. Tinh thé eta cde cdp oxy ha - khir khi edn bing. Cho bigt E%Sn“*/Sn?*) = 0,15V, EFe*/Fe”*) = 0,77V; EX(Ag’/Ag) =0,80V 22Bai tap nay van thudc dang tinh thé @ diéu kién bat ki theo phuong trinh Nersnt. Hoc sinh eding phai tinh thanh phéin cn bing dua vao dinh ludt tic dung khdi long va tinh hing s6 edn bing tir ce gia tr] thé chuan, aSn* + 2Fe* > Sn? + Fe Ndeb:0,05-x 0,05 -2x x 2x Igk = 2(0,77-015)/0,059=21 = K=1074 K rit lén va ning d6 Fe" cho phan ting nhé hon nhiéu so véi Sn” > phin ung ey hhodn toan: 2x = 0,05 [Fe] = 0,05M; [Sn“*] = 0,025M; [Sn’*] = 0,025M; [Fe*]=eM Oo = BOP5.(005)" 1 1g2t = 00025 5 = [re J 58.10" 0,025.6" e Ki cin bing Es =0,77+ 00591 O1SM b Tuong ty ta e6: Ag + Fe Ag+ deb: 0,05-x x x Igk = (0.77 -0,80V/0,059 =-0,51 > K, Taco [Fe ]=4,38.10°M 0,05-x [Fe“]=6. pe Ey= wn hee”, = 0,80 +0,059Ig 438.107 =0,727 Bai ip 15: ~ Xéts <> id tri the dign cue cita cp Po™/Pb theo pH. Cho nong dé ban dau cia Pb" 1400 *& Eterm = O13Vs Tryon, = 10 POOH), + OH” = PW(OH), fa xét tai cdc khodng pH khac nhau cé céc qua trinh turong img xay ra. = pHT bit dd két tia Pb(OH): 1a pHi =6,65M Khi Pb(OH)> tan hod toan thi ( Pb(OH); } = 0,01M, lie d6 pH = 13,3 Xét cde khoang pH Khi0 < pl <6,65, E ny Eng phy thuse pH va bing -0,189V. Khi 6,65< pH < 13,3 hé tro thanh he di thé. 2310 ep eto EP fof cory 0.0592 2 Khi pH > 13,3, trong dung dich khong cdn Pb™ nita nén thé ciia dung dich la thé cita cap Pb(OH); PP. Pb(OH); + 3H’ + 2e = Pb + 3H,0 \y Bang cach t6 hop cn bing, tinh duge E®, _, =0,699V AY [Pb] = Tryon nen: Epo, =— 013+ (Ig10”” + Ig[H*})=0,245 - 0,0592pH ib PACOH PD Khi 6: Ee Boag * 2057 ¢Pb(OH); HP =0,639- ng 1113.2. Thiét lip so db pin va viét ede phin trng xy ra 6 dign ewe & 1.3.2.1. Thi lip so’ dé pin dea vio cic cfip thé dign ewe OQ Dang niy la dang bai eo ban nhit vé pin dign héa. Ba bai tap xudi: tir cde cp thé dign cour thiét lap so dé pin bing céch so sanh gia tri thé dig xiic dinh anot, catot cua pin ign, va vidt ptpur xy ra khi pin boat dng. Bai toa phite tap hon khi trong dung dich 6 xay ra ede qué tinh phu Cho E" 6 25°C eiia cde cp Fe”) Ss tuong mg bing -0,440V va 0,800V, Ding cia pin duge diing dé xic dinh cae thé dign cue da them dign cue hidro tiéu chuan, vi cho, Hay cho biét phan img xj i pin duoc lap tir hai cp dé hoat déng, Hicing di Bai tip nay la dig bai van dung ly thuyét don thudn. Bi v6i dang bai tip nay, gido vign huéng dan boc ditt theo cae burée sau: - So shih Mf tyythé dign cue chudin, xic dinh anot va catot ei pin 5 Lap’ in <= ban phuong trinh phan img xay ra @ cde dign cue va phuong trinh phan img i Pin hoat dong. 9g eg - OAMOV < E},,.,, = 0 nén cp Fe™/Fe dng vai tr anot (cue am), clp 2H'/H2 dong i tro catot (cue duong) So d6 pin: @Fe|Fe* IM | [HT IM] Hb (p= Latm) (Pr) @ Phan img: Fe = Fe +e 2H’ + 2e = Th Fe + 2H" ret m4Bing 708 V > Eby, 0 nem Cap Ag'/Ag dong vai to eatot; eBp Fe""/Fe déng vai tro anot So dé pin: © (Pt),H> (p= latm)|H"IM| | Ag" IM| Ag @ Phan img Hs = 2H +e Ag+ ec = Ag Hy + 2Ag'= 2Ag+ 20" Mogg = —OAAV Bo, = 0,44 nn Tinh oxi héa: Fe manh hon Fe va tinh khir: Fe manh hon Fe™ 25Do dé phan tng tu phat xayra gita 2 cap la: 2 Fe" + Fe > 3 Fe Nhu vy Fe tan trong dd Fe(S0,)s tao thanh mudi FeSO,, fam nat mau vng (hode d6 nau) cia ion Fe** va cudi cing lam mat mau (hode tao mau xanh nhat) dd. b) Bsjey = 052V > Ebro = 016V nen: Tinh oxi hod: Cu’ manh hon Cu” vattinh kh: Cu" manh hon Cu Do dé phan img tu phat xay ra gitta 2 cap la: Cu" + Cu’ > Cu + Cu Phan img nghich (Cu™* phan img véi Cu tao thanh ion Cu) khdng xay ra. Do dé khi bd bé yy vvao dd CuSO, khong xaiy ra phan tig, khong thay ¢6 hign tuong gi n cuc trong digu kign bat ki va “¢ sor din tir 2) Phan nay két hop 2 dang bai tap: Tinh thé cdc gia tri thé dign cue tinh duoc. Déi voi phan (a), trude hét ta phai xic din cn ® baze hode tho thirty hing sé bang cia hé (gidng nhu phuong phip chung d& néu) bing cach xét cde xh khirc6 thé xay ra di véi cde ion trong he. Xét Kin lugt cde cen bang tr lin dén bé Khi axit hod dung dich X 6 phin img: Vi Cys= 0,010 < Sy, .nén HS chia bao h fhodt ra khdi dung dich. Liic nay sé xay ra phan tmg oxi hoa khtr gidta Fe™* voi HS Phanimg = 2Fe™ +H, DS. K=10" Ol mS 0.02 ey > 2Fe +h K=10" 060.02 0,02 - 0,08 0,030 ‘TPGH cia dy Ken 0,020; Fe* 0,080; 1 0,030M. icMEO mdi trudng rit axit nén b6 qua cde qué trinh tao phite hidroxo cia Fe hé cuddung dich luc nay la thé cua cap Fe*/Fe™. [Fe] (Fe = 0,77 + 0,05921g(0,02/0,08) = 0,743V = 0,743V > Eqy = 0,244V nén khi hinh thanh pin dign, dign cue ealomen = Ege +0,0592Ig dong vai trd anot cia pin, edn dung dich X dong vai tro catot eta pin. Ejin= Bs ~E.= 0,743 0,244 =0,499V Sodé pin: © Hg|HgxCk, KCI bh| |Fe*, Fe*|Pte Phining = = 2Hg+2Clr =HgCh +2e 26@2| Fe*+e =Fe™ 2Hg+2Fe" +2Cl =HgCh) Tinh Eins cap CO. /CrO> va NOSNO @ dieu kign tiéu chun Cho: CrOHs| = HY + COy + HO k=10" 10 = W+0r Kw=10" \vy Eo =0,96 V; E° = 0,13 V; 625°C 06 asa 0,0592 N lap so dé pin va viet phuong trinh phan tmg xy ra trong pin duge ghép bai NOR H'NO ‘r07ICHOH),4,08 Huing din (g)|Pt (5). Cho gia tri thé dign cue chun & 25°C: =0,40V , RTIn1O/F =0,0592 a Tinh site dign dng chudn cia pin dign hia 6 25°C. b. Viet cde ban phuong trinh xay ra mdi dign cyre va phan img tong quat dong. Tinh hang sé cin bang cia phan img dién hia d Tinh sire dién dng cita pin 6 25'C khi [Fe™*}-0,015M, pH, pin dign héa la lim duge. Digu thi vi trong bai ton nay the té tao cho hoe sinh cé si him thi khi hoc hia a. Byg=B, - BY. = 040 (0,44)=" ws Harding din Ing nhiing kién thi rt eo ban vé cho hye sinh ning kign thie b-Taianot: 2Fe + 2Fe* + de 'Vé mat héa hoe, bai ton nay rét dom gin. Hoe sinh chi - Tai catot: 0) + 2H:O +4e 2Fe%\ + 40H” Phin img ting quit: 2Fe + bO + 2Fe* + 40H ne* Oe", = [OH]= 10°. i © K=10%%% 2 F675! = 094-2052 ts (10°) Lov dick ), 0,5M. Dign cue thir hai ki mét day Pt nhiing vao dung dich Fe”, Fe véi luong sao clio fig") = 2 [Fe], Ding mot day dan dign tro R ndi 2 dau Cu va Pt. Q ho biét déu cia 2 eue pin. Viet so dé pin va cée phan img dién cue. Tinh ste dign déng 3 ia pin. Biét ring thé tich ciia dung dich CuSO, kha Ion, hy tim ty s6 iH 7s due to ra tir2 din cue. Mot din cue gém m6t tim Cu nhing trong dung khi pin nging hhoat déng. Cho cde thé chun (E") cita cp oxi hoa khir: Cu/Cu =0,34 Fe™/ Fe = 0,771 fing din Xét cp oxi hod khir Cu"/Cu: 28Cut+2e=Cu 06:4, = 0,34+ oe e[cur] Lic déu 6, -0.M4 S22 g0,5<0331V Déi voi cap Fe Fe [Fe"] [Fe] Lite du 4, = 0,71 + 0,05921g2 = 0,788V WY Vilic dau: o2> 1. Nhu thé cuc (+) la cap Fe*/Fe™: cue (-) lacap Cu/Cu Oo 65 =0,771+0,0592lg: Fe* +e=Fe* 6 dign eye Cu cé phan img oxi hoa: Cu = Cu* + 2¢ 6 dign cue Pt ¢6 phan img khir Fe" +e=Fe™ « Phan tng tng quat trong pin s& la: Cu+ 2Fe** = Cu’* +2Fe™* Sod pin: (~) Cul Cu"*(0,5M)]] Fe™(2aM); Fe" (aM)|Pt(+) Epin = 92 — 1 = 0,788 - 0,331 = 0,457V Khi pin ngimg hoat ding thi sic dién dong E= 2-9 0,5M; do dé: y 0,771 +0,0592Ig. [fe Fi [Fe Baitip2t; Mot pin gm dién cue Pt nhi vei dign cue Ag nhang =-0,145V. Tinh E2 ‘C10= 10105 oF SE une va thidt lap so dd pin = 0,63944 V b () Ag|Agh 10° M| Clo; 10°Mclo;,01 | Pt (+) elo db pin, nia phan img va pp ki pin hoat dng trong ca truémg hop sau 1. Pin gém hai dign cue Pt nhiing trong dung dich HCI, khi clo @ hai dign exe of P hic nhau. Hoe mét dign eue bom khi H>, cdn dign cue kia bom khi clo, Hofe dién eve Ag, AgCl d- uuge nhing trong dung dich HCl véi dign eu khi clo. 2, Pin Zn Hg duge nhiing trong dung dich KOH Cy. Cho: E'7n0;2 727-1 22V; E'yigoytig-0.12V 5 Elza izn = -0,76V 3. Pin Zn PbO: duge nhiing trong dung dich HeSOx 38%. Cho E*ppo,/pb = 1 455V 294, Pin Zn O> duoe nhiing trong dung dich NECl Cy. 5, a) Viet so dé ciia de quy chi, cae ban phin img va phurong trinh phan img khi ée quy chi phong din va nap din b) Khi nap dign véi l= 19,3, t= 1,5 gid, Hoi c6 bao nhigu gam PSO, bi phan tich? 6. Co mot pin dign (goi la pin nhién ligu, ding dé cung e4p dign ning va nde tinh Khiét cho cdc chuyén gia bay trong vi tru) gm dign eye anot (C-Ni), dién eye catot 6 (C-Ni-NiO) nhiing vio NaxCOs néng chay va nap Hz vao dign cue anot, O: vio dign eye catot. Viet cae phin tng, phong trinh phan img khi pin hoat dng va so dé pin. Huéng dan, Bai tap nay nhim gitp hoe sinh c6 durge str lin hé gitta ly thuyét va cdc log pI due sir dung, Digu nay s€ tao cho hoe sinh sy himg thi khi lam bai 1, - So dd pin 1: (-) PtCls (Ps) | HCK(aq) | Ch(P:), Pt (+) (Voi Pa < Nita phan img 6 anot (-): 2Cl > Ch + 2e Nita phan img 6 catot (+): Ch + 2e > 2Cr = So dé pin 2: (-) PtH (Pa) | HCl(aq) | Cla(Pa), Pt (+) ( ) => Phan iing xay ra trong pin’ 2HCI - Sa dé pin 3: (-) Ag. AgCI| HCI | Cl(P atm Nita phan img 6 anot(-): Ag + CI + le, 2 Nia phan ing 6 catot (+): Ch + 2e => Phan img khi pin hoat 2Ag + Clr + 2AgCl 2. So dd pin dién: (Zn | KOH(C) | 40H — Zn(OH),* +2€ (+): HgO + 2e + HhO = Hg + 20H x | Zn?"(©), HaS0.(C) | PbSOs, PbO, Pe) Ee img Ganot(-): Zn + Zn’ + 20 Nita phan img 6 catot (+): PbO: + 2e + 4H" + $0," + PbSO, + 2H,0 => Phan img khi pin hoat dong: Zn + PbO; + 4H’ +S," — Zn’ + PbSO, + 2H,0 4, Sado pin dién: () Zn | Zn(NH).", NHLCI(aq)| O>, Pt) Nita phin tng 6 anot(-): Zn + 4NHy' —> [Zn(NHs),f" + 2e + 4H ‘Nita phan ing 6 catot (+); O) + 4e + 4H” > 2H,0 30=> Phan tng khi pin hoat dong: 2Zn +O; +8NHy’ + 2[Zn(NH;)4]”* + 2H;0 + 4H" 5..a) + Khi pin phong dign, co sor d6 pin dién: (-) Pb | H:SO, 38%| PbO: (+) ‘Nua phan img 6 anot (-): Pb + SO,” > PbSO,+ 20 ‘Nita phan img 6 catot (+): PbOz + 2e + SO? +4H* — PbSO, + 2H;0 => Phan img khi pin hoat d6ng Pb + PbO: + 2H:S0; — 2PbSO, + 240 + Khi pin nap din (nhu m6t binh dién phan), Nira phan img anot (+): PbSO, +2H;0 + PbO, + 4H* +2e +S02° Ay Nita phan tg 6 catot (-): PbSO; + 2e + Pb + SO, sO => Phin img khi pinnap dign: 2PbSO, + 2H;O > PbO, + Pb + +) Theo phan img khi nap dién ta e6: ™mppso, = Mnppgo, = 303(Iv/2F).2 = 303(10.1.5 “< 55() 6, So dd pin: ()CNi, Hz | NaCOyae | O2, C-Ni-Ni (4) + Nita phan ing 6 anot: Hy + CO;* + CO) 2e + Niza phan img 6 catot: 1/2 0 +2e + i => Phuong trinh phan img khi pin H; + 12.0, + 20 Diiy la dang bai ngue: tir ptpu trot ic dinh cae cp oxh— khit, xe dinh anot va catot cia pin, tirdé viet so dé pin. \) Bai tip 23: Cho ce ph haf img vi qua trinh xy ra trong pin nhu sau: 25F eae 8H = SRe* + Mn + 41b0 CH;COOH + NaOH + CH3COONa + H;0. +A 3 HA "AgCl + Br —> AgBr + Cr 8Ag(NH)T + 2CN — [ABICNDT + 2NHs 9.AgCl + 2CN > [Ag(CN)T + Cr ‘Viet nia phan img trong pin va thiét ldp so dé pin Huwiing di ic phan tng xay ra trong ra trong pin c6 thé la phan img oxi héa khir don gian, phan 1113.2.2. Thiét lip so'dé pin dea trén * phn iing ting quat img oxi héa-khir c6 swt tham gia ciia méi trudmg, phin img tao thanh hop chat it tan, tao phite hode phan img axit, bazo... Mudn kim duoe bai tap dang nay déi hoi hoe sinh phai nim duoe 31ban chat ciia phan ting oxi hoa —khir, phan ung cita hop chat it tan, phan img tao phite, Ddi voi mi phin ing cin phai xée dinh duge cde ep oxi hoa-khir hode ede dign cue lim vide dé tao thanh pin dign 1, Day la phan img oxi héa- khir don gian kim loai tac dung vei mudi = dé dang xée dinh duoc cap oxb-Khir; Mg™/Mg va Cu/Cu So dé pin dign: (-)Mg|Mg™ | | Cu" | Cu (+) ‘Nua phan img 6 anot: Mg > Mg” + 2e Nira phan img & catot: Cu” + 2e + Cu 2. Day ld phan img oxh-khir o6 sur tham gia ctia mi trong. Trong méi trumg axit MnO¢ vé Mn’, hinh thinh 2 cap oxi hoa- khir: MnO,’ | Mn?* va Fe®* | Fe”. \\ Qua trinh oxi hoa xay ra trén anot; Fe* + Fe* +e (Qua trinh khir xéy ra trén catot: MnO," + Se+ 8H" -» Mn” +4 ~ Vay ta 06 so dé pin dign (a) Pt | Fe, Fe (aq)| | MnOy, Mn?*(aq),* 3. 6 phan nay c6 sw tao thinh hop chat it tan, ching ta phi ‘Gi ion tao hop chat it tan va c6 mot dién cue kim loai bi on dithgye lam vige thuan nghich m6t hop chit it tan duroe nhiing sinh gid tri thé dién cue ciia 2 ‘vao mét dung dich chita anion ca hop chat it tan 464 dign cue due tht lap Phan img Ag’ +CT + AgCl | xdy ra kém ning dé ion Ag’, phai chon dign eve lam vige thudin nghich véi ion Ag": Ag |Ag Thé cia dign ewe Ag due ti phurong trinh Evie = Paging + 00592 hir vay dign eye nio c6 thé duong hom (tice la 6 [Ag"] lim hon) sé la catot es -G anot X@yga quatrinh oxi hoa: Ag + Cl > AgCl +e ne qua trinh Khir: Agite > Ag a So dé pin (-)Ag | AgCl, cr | | Ag’ [Ag (+) 4, Phan nay thanh bgp chat phite. Cach lim tuong ty di vei hop chet it tan. +: IN’ = Ag(CN)y xay ra kém theo sy thay dai néng dé ion Ag’, do do phi chon di vige thudn nghich véi ion Ag’: Ag | Ag’ va Ag| Ag(CN)s, CN. 9 Nita phin img 6 anot: Ag+2CN + Ag(CN)y +e Nita phan img catot: Ag" +e — Ag Vay ta 66 so dé pin: () Ag | Ag(CN), KCN(C)| | Ag” Ag (+) 5. Vi cic chat tham gia trong phan ting trén déu ld axit, bazo — phan Ung xdy ra kém theo sur thay di ning d9 ion hidro,vi vay phai chon dign cye lam vige thudn nghjch véi ion hidro 06 thé due tinh theo phuong trinh: 0,0592 [HP Biz,, =e 2H" Hy Zz % Pu 32Nhu vay thé ciia cd 2 dién cue déu phu thude vao [H'], do dé dién cue hidro nhing trong, dung dich (CH,COOH) ed [H'] lon hon sé la catot, Vay ta co so dé pin (HPD, Pa, atm|NaOH| | CH:COOH| Px, = latm, H(Pt) (+) Tat catot’ CH;COOH = CH:COO' +H 2H + 2e b 2. CHsCOOH + 2e =H; + 2 CH;COO' (1) YY Wiest atte oe W+OW =H0 Hy + 20H = 2H,0+2e (2) Té hop (1) va (2) ta duge: CH;COOH + OH = H,0 + eK 6, Tuong tu: ‘Nira phan tng @ anot’ Hy +2A° > 2H, ew Nita phan ing 6 catot: 2H" +2¢ — So dé pin dign: (Pt HAP) | AC) | | HC P+) 7. Chi y 6 phain niy: Ks aga < Kangen nén fA) ett cue co chira AgBr nhé hon & dign eye 6 chita AgCI nén co: ‘Nita phan img 6 ano oe fs AgBr +e ‘Nita phan img & te Ag+ Cr Sadi pinditn” (2) “en (C)| [KCKC) | AgCI, Ag (+) 8. Tuong tu é dau [Ag cue dé lam anot cua pin. Nii Ganot Ag + 2CN > AgCN); +e {mg G catot: Ag(NHs)s"+e— Ag + 2NHs Sodé moat C) Ag | Ag(CN):; KCN(C)| | NHC); Ag(NHs)" | Ag(+) 9. Tah Nita phin img é anot’ Ag + 2CN’ +> Ag(CN)y +e vy Nita phan img é catot: AgCl +e > Ag + Cr @ pih dign. (-) Ag | Ag(CN)s KCN(C) | | KCNC) | AgCl, Ag (+) Bai tip 24: |, Hay thiét lap so d6 pin dé khi pin nay hoat déng xay ra phan tng sau: Zn+NO;+H" Zn" +NHj+H,O (1) 33Hiy viét cdc nira phuong trinh phan tng xay ra trén cae dign cue. 2 0,12V; E®.. =-0,763 V pKa (NHy")=9.24; Ky = 10 tn 1on (RI/F)in=0,0592Ig, Hay tinh En Hung din 1 Day la phan ting oxi héa ~ khir co sirtham gia ciia méi tubng. Trong méi trubmg axit, NO; bi hit vé NH}; con Zn bi oxi héa lén Zn, Cac ban phan tg xay ra 6 cde dign ou: WY -Taicatot: |NO;+6H:O + 8¢ = NHs+ 90H Oo 9| WH +OH = 0 NH; +H = NH} NO;+ 10H” +8¢ = NH; +3120 « -Taianot: Zn = Zn + 20 So dé pin dign’ (i2n|zn**(IM)|NO, M) NFS M),H (IM) |Pt(+) 2. Dé tinh duge sie dign dong chun cia pin, ta phi L.) cae gia tri thé khir chuan cia anot Ns don gin nhat la t6 hop can bang NO; + 6H he Sissi Ki=10 OH os = 0 Ky'=10" = Ni va catot. Do dé, trude hét ta phai tinh gia tri E' K,!= 10% ms Seat 3+ IOH' +8e = NH}+3H0 = =-K,=10 Q .Ko"= 10" Tirdo tinh duoc E? =0881 ‘Nop HTH ~ E, = 0,881 - (- 0,763) = 1,644. Muéi c6 thé tw khuéch tn dung dich dc sang dung dich loding khi tgp xtc. Qua trinh tr jéch tn la qua trinh gidi phong nang Iugng. Ta ¢6 thé tao ra mot té bao dién hod (pin) sinh cng dign nbiy qua trinh khuéch tn ion Cu?* tir dung dich CuSO; IM sang dung dich CuSO, 01M. a) Viet cae nia phan img tai catot, anot va cng thie cia pin dién hoa. b) Tinh sie dign déng 25°C cia t pin dign od. Huéng Pin dign héa da cho thuéc loai pin ning d6, ion lim vige thuén nghich li [Cu] 34a) Nita phan tng oxi hod @ anot: cu Cu +2¢ ‘Nita phan img khir 6 catot Cu +2e> Cu So dé pin didn hoa: (anot) Cu | dd CuSO, 0,1M| |dd CuSO, 1,0M| Cu (catot) ) Tinh site dién dong: Egg) = Eeaiv~ Emit 00592, [Cu? 00,0592, 1,0M 24 = eas = SO Ig 203 mo > Fic, 2 801M Phan img sit AgNO; véi KCI trong dung dich tao thanh két tia Agel va, eY img do. tai anot va catot. b) Tinh AG},, cita phan img két ta AgCl va Sy, ciia té bao &. 5% ( ) a) Viét céng thire ca té bao dién hod theo quy tic IUPAC va cae x Cho Tage 25°C bing 1.6.10" Hwéng dan Nira phan img oxi hoa & anot Ag-e+@ SS Nua phan img khtr 6 catot: (.) > Ag Phan img tong quat: Ag’ + @ NC AgCl (1) Céng thisc cia pin dign hod: (anot) Ag| a dd AgNOs| Ag (catot) b) Tinh AG}, va Ex, \ i 2 i ‘Xét phan img Ag “+ Cl > — Zee 1610 6,25.10° 7, acc AGS,, =-RTInK = 14x298x In(6,25.10°) = -55884J / mol = -55,884kJ / mol 55884 +27 = 40,5792(V) = +0,58V 1.96487 oe phan img tong quat xdy ra trong nguyén t6: [4elH,),] =2NHs + Ag" + Hay tit lap nguyén 16 dién hod vi tinh hing sO khong bén eiia phire [Ag(NH,),} biét rang doi voi cde nita nguyén t6 6 25°C: Agi +e=Ag E?=0,7996V [4e(NH,),}' += Ag+ 2NHy £°=0373V 35Vé co ban, bai tap nay la m6t truong hop cita bai tap trén, Nhung co thém phan tinh toan hing sd cn bing, Phan ting @ anit Ag-e=Ag™ Phan ting 6 catot [4e(H,),} += Ag+ 2NHs Phan img ting quit: [4g(NH,),} +e= Ag" +2NH; So dé pin: Ag| AgNO,|[4g(NH, ) Tag E°_0373-0,7996 4 yy ities Ws =-722 1 Kyy=6.10 BK 055° 0059 "2 He \“ 1113.3. Cac bai tip tong hop vé pin dign c6 lign quan dén pH, cin bing nhs it tan vi cn bing tgo phite 1113.3.1. Pin dign héa lién quan dén phiin tng tgo hgp chét ittan < ‘Taco thé phan loai ra hai dang bai tap eo bain: ~ Bai toan xudi: Cac bai tap tinh tich sO tan tir cde di igu vebthé dign cue, pin dign hoa nim ving vé phan img oxi Quge trang bi su sie kién thire vé lign quan, Dé giai quyét duoc dang bai tép nay doi hoi hod-khit, phin (ing tao hop chit it tan, mit khéie hoe pin dign ~ Bai toan nguge: Cho cae phan tn it tan, dya vdo Iugng chat va tich s6 tan bai cho tinh duoc ndng dé can bing cua cde ra thé dién cue cho timg cp oxb/kh va tir do xdy dung so 46 pin, tinh sire di ciia pin. Cae bai toan nguoe nay thuémg gap nhieu Hwony ay dang bai toan xudi, tr tit kip mot loai pin véi nding d6 cde chat lay tuy y. Thong qua i thé dign cue tigu chuan cia cde c&p oxi hod - khir cho biét va dura vao thue nghi&m do i dign dOng cua pin tir do tinh ra duge tich s6 tan cla hgp chat it tan tiép xiie voi dién kim loai Don gin va dé hiéu nbat, & day hung dan HS giai bai toan bing cach viet biéu thie tinh Ep dua vao phuong trinh Nernst bigu dign gid tri thé tai mdi dién cue. +0,0592Ig{Ag*] - E? 0 ‘Ag'INg Ag" + 0,05921g Sw [cr] ing O05921BK sagen ~0,05921[CF ] 36E.= Eg, +0,0592Ig{Zn"*] Vay Epa =E.-E. ‘eiagt 0059218 K, age ~ 0592 1G[CT]- (2,27, + 0,0592gfZn""]) Zaft = 0,799 + 0,05921gK asc ~0,0592Ig (0.5) — (0,763 + 0,0592Ig(0,1)) ign cue loai II duoe edu tao ti kim loai duge bao phi bai hgp chit Kho SY ‘mudi it tan) cia kim loai d6 vi duge nhing vio dung dich chira anion eta hop chéf Kho Yag hay. Dign cue Ag, AgCl/ CI va dién cue calomen Hg, Hg,Cly/ Cl la nhing vi di a tia dig cue loai nay, Gia tr thé tgu chudin cia pin dig héa (-)Ag, AgCI|CI fe +) B= 0,0455V 6 T= 298K. 1. Viet cae nira phuong trinh xay ra 6 mdi rink tong quat khi pin hoat déng. 2. Tinh bién thién nang lung tir do chun \ n img xy ra trong pin & 298K. Tir d6 nhin xét chigu tu dign bién cia phan img Eh ing 206 799V va tich w gC la K; = 1.73.10". Tinh gia tri thé khir chuan cia cp Ag, AgCUCl waders inh bigu dign sw phu thude gita E\..,.. va ‘Aging ‘Agagcucr 0 Hee 4, Xée dinh tich 6 Ch, biét rang E = 0,798V. Huong diin Noi du kha don gian thuéc dang bai tap xudi, nham gidp HS nhé lai va van dung cdc kign’ fan da duoc nghién citu trong phan pin dign héa cé lign quan dén hop chit it tan, Ngodi MA plain 2 di hoi HS phi nim duoe bigu thi lién hé gita bién thién nding luong tu, d@Pehlin Gip cia phan img oxi hoa khir trong pin dign vi gia tr site dign dng chun cia nfra phn Ung xiy ra 6 ede dién eve: - Tai catot(xay ra qua trinh khiy); %sHgsCl +e = Hg + Cr ~ Tai anot (xiy ra qua trinh oxi hoa): Ag + Cr = AgCl +e Phan img ting quit: Ag+ %HgxCh = Hg + AgCl 2. Bién thién nding luong ty do Gip ctia phan img 6 298K AG? =n FE! = - 1. 96497C mol". 0,0455V=-4,93kI. mol <0 C6 AG®< 0 nén qua trinh xay ra trong pin tur didn bién 37Kua (cr] 3. Tacd: Ei, scuer = Engeiayt 00592Ig [AB Eyeing + 0,0592 Ig = Bing * 0,0592 le Keager (vi [Ct] = 1M) 0 Tird6 tinh duge E), 4 -ycy-= 0,799 + 0,0592lg (1,73. 10°") = 0,222V 0 pe 0 . 4. Ta cd Bly = Fi secuier ” Eseagver Nem 0 stgtecicr = E pin E Pat By (0455+ 0,222 =0,2675 V. \y Tuong tu nhu dign cue AgCl, CIY Ag lac: \ 0 Be = -0,440V. ° Ha y: 1. a. Thiét lap mét so d6 pin dé xac dinh tich s6 ‘Viet cde pipu xay ra trén mdi Cy dign cue va trong pin, b. Tinh dé tan (s) tai 25°C cia Agl tron 2. a. Lap pin dign trong dé xay ra su’ fi ton Fe™* thanh ion Fe™ va ion Au* bi khir thinh ion Au’. Viét cic phuong trint ting xdy ra trén mj dign cue va trong pin. b. Tinh sie dign dng chugin ig ph va hing sé cin bing ea phan tng xiy ra trong pin nay. Huong din Bai tip nay, La mt bai tap xudi dién hinh vai day dit nhimg dang cau hoi ea ban cita mét bai in dién héa 6 lién quan dén phan tmg tao hgp chat it tan. Mai cau hai cia dé bai ee ‘mét goi y bude lam cho hoc sinh. Hoe sinh chi can van dung nhing kkién thie co Bag ve pin dign, the dign cuc, céch to hgp can bang la cd thé Pl my bai tip. Doi voi 1 tan, cin chit y thém vé kha nigm dé tan trong dung dich bao hia. fc dinh tich sO tan Ks ca Agl, cn thiét lap so do pin c6 cae dién cue Ag lam viée nghich véi Ag’. Dign cuc Ag nhiing trong dung dich nao co [Ag'] lon hon st dong vai tro tot. Rd rang dung dich khéng c Agl két tia sé co [Ag] Ién hon. Vay so dé pin nhur sau: (-) Ag | Taq), Aelit) | Ag‘(aq) | Age) (+) Hoe: (-) Ag, Aatte) | Mag) |] As'(ag) | Aste) = Phan img 6 cue am: Ag() +1 (aq) = Agl(r) +e iG =Phaniimgé cue duong: Ag'(aq)+e == gt) Ky = Phan img xay ra trong pin: Ag’(aq) + Taq) = Agl(r) KS (1) 381 ts ios 2 K= 10 sen hanes =1,0.10 + Ks=1,0.107% b.GoiS. ih 6 tan cita Agl trong nude nguyén chat, ta co: Agll = Ag+ Tr Ks=10"* Sos Vi qua trinh tao phir hidroxo cua Ag’ khong ding ké, [14 anion cia axit manh HI, nén $= vk 2. Theo qui usc: qua trinh oxi hoa Fe™ xay ra trén anot, qua trinh khir Au™ xay ra trén catot, ay, dign cuc Pr nhiing trong dung dich Fe, Fe” la anot, dign cue Pt nhiing trong dung dich AN catot: () Pt] Fe*(aq), Fe*(aq) |] Au™(aq), Au‘taq) | Pt (+) v 0.10% M. Phin imgé cue dm: 2x |Fe"(aq) = > Fe“(ag)te Kj! Phin img cue duong: Au’ (ag)+2e = —» Au'(aq) Phan imgtrong pin: Au’*(aq) + 2Fe*(aq) > Au‘(aq) are ) 3 K= (Kj! Ks= 10° oe NR ‘Trong dé thé khir chudin cla cp Fe’’/Fe* due tinh nhur s Fe"+3e = Fe E'(I)= -0037V, (1) fa at Eee Fe¥+2e Fe E%2)=-0,440 V, = - 2F B(1) o 5 Fe"+e Fe Bay = AG wea 2) | 26%(2) =0,77V [hpeaeornvoasse — yqiset > K=(Ky yh 6 digu kign tigu chun, sire wan cia pin trén sé la atagt E'pSteae = O49V AgNOs 0,050 M va Pb(NOs)> 0,100 M. Ae iia dung dich A whee 10,00 ml_KI.0,250 M va HNO30,200 M vao 10,00 ml dung dich A. Sau phan gj ta nhiing mét dién cue Ag vio dung dich B via thu duoe va ghép thinh pin (co cau 9g gp xe hai dung dich) voi mot dign cue e6 Ag nhiing vio dung dich X gm AgNO; 0,010 ‘va KSCN 0,040 M. a) Vigt so d3 pin b) Tinh site dign déng Epix tai 25°C ©) Viet ptpu xay ra khi pin hogt dng ) Tinh hing s6 can bang cia phan ing Cho biét: Ag'+ HO = AgOH+H" (1); Ki 107” 39Po" + HO = POH +H" QQ); Ke 107 Chi sé tich 6 tan pK: Agl 18 16,0 ; Pb 147,86 ; AgSCN la 12,0 eg — ODOV Blin = 00592Ig 3. Eyins thay di ra sao néur a) thém mét luong nhd NaOH vo dung dich B b) thém mot luong nh6 Fe(NO3); vao dung dich X? \V ‘Huéng din 1. Bé xie dinh pH cia h, HS cin so sénh ci edn bing tao phir hidroxo = jehbem cn bing nio la chit yéu va quyét dinh pH cia he Ag’ + HO = AgOH + HO K)=10'7 Pb* + HO = PhOHY + HY; K,=107% Do K2>> Kj nén cn bang 2 quyét dinh pH cia dung diel Pb* + HO = PbOH + H’ ; Q) Cc 0,10 {] 0,10-x. x =107 = x=10=(H] = 4,40 ~ khir quyét dinh thé cia dung dieh thi phai xe dinh ludn vay, true hét phai dua ra duoe TPGH cia dung 2. O phin 2, dé xi dinh duge ede duge thinh phan edn bang cia dt dich, tir d6 xét cae edn bang ‘tinh toan theo can bang cha yeu. a) Déi véi Dung ‘Thém KI: 5M; Cros. = 0,050 Wy125M ; Ce = 0,10M Ne + ros Aglt 025 0,125 \ : 0,10 Ye Poe + 02 > Phd 9 . 0,05 0,10 ‘Trong dung dich c6 ding thoi hai két tia Agl 4 va Pol: Ag) = Ag+ ro; Ky =1.10% (3) Pbht = Pb* +2r Kg =1.107 (4) 40Ky < [PDOH] <<[Pb"] ‘Xét cfin bing: Pb) = Pb* +26 Kg =1107° x lx \V =1,51.10°M > 2x= [I] =2,302 . 102M \ =3,31.10"M © E ca cue Agtrong dung dich A: Ag’ + ¢ = Ag F,=E?.. , +0,0592Ig{Ag*}=0,799+0,05921g23,31 gS, As Déivoidung dich X: Ag’ + SCN” = AgSCN: Ww " 0010 0,040 ei 0,030 0, ‘TPGH cia dung dich X: AgSCN 0,010M; SCN\IRBOM. Xét can bang sau trong dung dich X: AgSCNY = Ag’ + SCN" io" SS" 10+ x) Taco: [r= Add +e = Agh + SCN” Agl + SCN” 3, Phin 3 yéu cdu HS dya vao cée yéu 16 dinh hudng dén thé dién cue, suy lun sir thay d6i cua Epin khi tic dng mot sO yeu 6, a) Khi thém luong nhé NaOH vio dd B, c6 thé xay ra 3 truing hop: 41+ Luong NaOH qiia it khéng dit dé trung hoa HNOs: Su tao phie hidroxo cua Pb” van khéng dang ké, do d6 Eyiy khOng thay d6i, ~ Lurgng NaOH dii dé trung hoa HNOs: Cé str tao phite hidroxo cua Pb** do dé [Pb*] gid, Nong 46, ISB ting lén, do dé ning d6 Ag" gm xuéng, E; gidm ; vay Eyia ting. - Luong NaOH dui du dé trung hoa hét HNOs va hoa tan Pbl; tao thanh PbO, do do [Pb*'] giam va Epis ting, Pb + 40H ~ PbOy +2H,0 +21 b) Thém it Fe vio dung dich X: Fe’ + SCN” — FeSCN?* yy Nong d6 ion SCN" gidm, do dé néng d@ ion Ag” ting, Ba ta Oo Dung dich A gom FeSO, 0,020 a) Ly chinh xe 25,00 ml dd A, trong hin hop (6 digu kign thich hop) hét 11,78 ml KsCrs0; 0,0180 M. Hay viét eS ion cia phin img chudn 46. Tinh néng d6 M cita Fe;(SO,); trong dd A. >) Tinh ndng d6 M cia H2SOs trong dd A, biét d wr 07. ) vai cue Ag nhiing trong dung 0,0100 M (coi thé tich duge git vin (ing xy ra khi pin hoat dng. Tinh ©) Ghép cue Pt nhiing trong dung dich A (q dich AgNOs 0,0190 M 6 thém KeCrO. cho dén nguyén), Hay cho biét anot, catot va viét phe sire dign dng ciia pin Cho pKy: HSO¢ 1,99: Fe (Fe + Chi sé tich s6 tan Gandy 104 11,89. E*. Fe*/ Fe Huong din ~ Bai to (chuan 46), ign quah dén nfiiéu kién thire nhu: can bing tao hop chat it tan hay su tao phite hidroxo cia kim le@isCac Rien thire nay phire hop voi nhau, doi hoi hoc sinh phai het site tinh tao, nhay bén xem oe doan phi hgp cic cn bang cé the xay ra, dé tim gid tri thé cita cae dign cue mot cach xi. nhiéu bai todin nho, cé lin quan dén cae kién thie phan dinh Iuong i bazo (céu b), phan phan ting oxi héa- khir (pin din), Trong phin c, Iai a) Déi voi phan a, hoe sinh chi can viét duoc ptpu chuan dG, rai ap dung dinh luat duong luong. Phan ting chudn d6: Cr0? +6 Pe" + 14H 4 2Cr* +6 Fe +70 Cy = Cras, + 2Craysop, 7002 +2C1 C, .-25,00 = 6. (Con Vesoe) => 25,00(0,020 + 2C,) = 6(0,0180 . 11,78) > Ci=0,01S44M hay C,, 9, = 0,01544 M 2+) Déi véi phan b, c6 nhigu can bing trong dung dich tao ra proton. Sau khi so sanh thay pH dung dich phu thue déng thii vao hai edn bing Do vay, cich nhanh nhait a ta ap dung din luat bao toan proton dé tinh. Bay ciing la cach giai tong quat co thé ap dung cho moi bai toan co cdc cn bling axit - bazo. ‘Trong dd A eb: Fe 0,020 M; Fe** 2Ci, Ht (C, M); HSO; (C, M). Xét cae cn bing tao proton trong dd: 2H,0 == H,0'+0OH" Ky= lo (1) Fe*+2H0 ==? FeOH*+ HO Ky = 108 Q) wv Fe" +2H0 == FeOH"+ HO" Ky = 1077 3) HSO;+H,O == SOP +H30° K, = 10%" « So sinh ta thy (3) va (4) la eha yéu va tuong dong nau Ap dung dinh uat bao toan proton, ta co [H:0"] = Cy," + [FeOH”] + [SO] Tir(3)c6— [FeOH™] / [Fe] =K./ [Hs0°] = [FeOH™] / Cre} = Kaa (Kaa + [H30°]) = 107” rs > [FeOH™] = 0,0736 Cre * =0,0736 . 0.9133 Tuong tu, tir(4) 06 [S07 Y[HSO ;]-KJ[H:0"] 1 [807] /Cusoz = * 10") [SOF] =0,107¢; Phuong trinh (a) tris the Tit(b) 05: Cyso, = C+ 00736 Cr+ 0,107 C (b). y™ _ 0.0736 . 0,03089) / 1,107 =0,07483M )Tinh thé oi) hai, ¢, 80 sénh, xée dinh anot va catot ciia pin, Tir dé viet phuong trinh phan tg khi pi =F fe ] Ei. ine Fe Be e"] deren [Fe™*] theo edn bing tao phite hidroxo: Ve Fe + 2H,O = FeOH"+ HO" = 102” 9 © 0.03089 [1 0,03089-x x 10M x1oe" 27 By (0.03089-%) U [Fe’*] =0,03089 - 0,002273 = 0,02862 M [Fe] = Cre? = 0,020 M (vi Kat rit be) Vay: En =0,771 +0,0592 lg (00862 / 0,020) = 0,780 V. B*Tinh Eag! ‘Xét phin ung: 2Ag + COP > AgsCr0,)K= 10" 0,019 0,010 5.10° ‘TPGH ciia hé: CrO:” 5.10°M, AgsCrOx|. Xéc dinh [CrO.7] AgCrOs) === 2Agy + COP K=10"" iG s.10* {1 2x S104 +x Ve 1 (2x 6.10% +x)= 10" 1 x=2,08.105 ( Co: [Ag’] =2x=4,96.10°M. ~ Eag= Bi sy +0,0592 Ig [Ag"] = 0.799 + 0,0592 194, 96.105) eX ViEag Eqn = Ey - Ey = 0.244 - (-0,0592pH) = 0,303 => pH=1 2. Tuong tur phan trén, ta c6: 45Epin= Eqs ~ Ep) = 0,244 - (-0,0592pH) = 0,444 => pH = 3,38. Hay [H’]=10°"M Vay: a%HA = (10°°%/0,01), 100% = 4.17%. 3. Tuong tyr nhu trén tinh duoc [H*] = 1078 Xetednbing HA > HWo+ A C10? [07.10% 1058 1038 LEAT _ jg 3393 SA = (10 PK if] ( yA => K= 338) = 194% (H 1 Thém HySOj vao dung dich gm Pb(NOs)3 0,010M va Ba(NO;)> a «46 0,130M (coi thé tich dung dich khéng di khi thém axit). Hay tinh pH vafndpa loai trong dung dich A thu due. jc3¢ ion kim 2. a) Hay bigu dign so dé pin gim dign cue hidro (p,,= Yatn\dtige nhiing trong dung dich CH;COOH 0,010M ghép (qua cau mudi) véi cign cue PUghiing Weg dung dich A. Hay chi 16 anot, catot. b)Thém 0,0050mol Ba(OH) vao 1 lit dung ign cue hidro (coi thé tich khong thay Adi), Tinh Eyiq va viét ptpu xay ra khi pin he Cho: pK, (HSO;) 2,00 ; pK. (CH Chi sé tich s6 tan pK, (BaSOs) 9.9 4) 7.66 123 V p/P fa ciing xét cdc phin img hoan toan gitta cae ion co the xity bing K ciia phin ting (Khi K > 10° coi nhu phin img xay iH clia hé xem xét va so sinh cde cfin bing co thé xay ra, tinh duge ra hodn toan). Sf gg pH vandng d oe ion trong he. “ae qhiairinh dign li trong he ~ PD(NOs)> > Pb + = 2NOS 0.010 9 oo 0,010 Ba(NO;)2 > = Ba’ + NO 0,020 _ 0,020 WSO > OH + CHOP 0,130 _ 0,130 0,130 Cac phan ting c6 the xay ra: 46HSO; + Ba + BaSOd + HO K=10% 0,130 0,020 0,130 0,110 co 0,150 HSO; + Pb + PbSO.d + H K= 10°" 0110 0,010 0,150 0,100 _ 0,160 ‘TPGH ciia hé: HSOs 0,100 M, H! 0,160M, BaSOz¥ , PbSO,) . Cn bing chinh quyét eX, cea hé WSO; > HY + Sofg- K=107 \ Cc 0,100 0,16 x © [] (@100-x) — (0,160+x) x « x(0,160+x) _ Tivos 0? + x=[807]=5.69 Nang d6 cain bang cde ion trong dung dich: [HSO.] = 0,0943 (M) SS [H'] = (0,160+x) = 0,1657(M) 8 . K, pat) = Awan = [soe] 5,69.10% [Pb™] = [sor] 2. Dé thiét lap due so dé pinaph duge gia tri thé ita 2 dién cue tir d6 xde dinh anot vi catot ctia pin, Muén vay, pha inh duoc ndng a6 céin bing céic ion trong mdi dung dich dién cue va ap dung phurongtinh Nefsnt dé tinh. a). Vor idtco: 2H’ +2¢ = Kh Xét edn bang ja CHCOOH dé xae dinh pH cia he: Seven H’ + CHCOO” Ky =10*” 001 O0l-x x x = 107 — x= [H"]=4,08.10°M — pH =3,39 = -0,0592 pH = - 0,0592 x 3,39 = - 0,2006 (V) + Voi ditn cue Pb/PbSO, PbSO, + H’ +2e = Phy + HSO; 0 —,0,0592),_ IH") [HSO,] | sours 718. Pb 40,0592,,_K, Trong dé: Etssoy = Eins + 2 Sgor] = -0291 i 0,0592 | 0.1657 + Ema 0,291 +202 pg ONO 395 (yy < E " 2 8 003 78M) ing ¢6 thé tinh theo cap Pb*/Pb: E=-0,123 + Ig[Pb*]=-0,123 + lg 3,84.10°=- 0,283 (V) Vay cuge Pb la anot; cut hidro 1a catot. () (anot) Pb | PbSO.t , BaSO, , H’, HSO,' || CH;COOH | H2,(PO) (catot) (+) yy adi b) Khi thém Ba(OH)p vao dién cue hidro s€ xay ra phin img axit — at hay ning d H* trong dung dich. Do vay, thé ciia dign cuc hidro thay di kéo t i. Xet phan img axit ~ haze os 2CH;COOH + Ba(OH); —» (CH,COO)Ba + 2@ 0,010 0,005 ee 0,005 ‘TPGH cia hé: CH;COO" 0,010M; Ba” 0,005M. quyét dinh pH eta hé la can bing cia CHyCOO™ CH:COO + HO = CHC Ky =10°* c 0010 SS x 0,010-x =-0,0592 pH OX £38 = -0,496V(anot) va Eni= -0,284V(catot) [1 0010 -x 1 — Ar 10° pH =8,38 Vay Epo =~ 0584 (-0496) = 0,212 V. Phin img diem G Hh 2H + 2e \ 2.CH,COO" + 2H" = 2CH,COOH 2CH;COO’ + Hz = 2CH:COOH + 2e \ catol PLSO.L +H’ +20 = Pol + HSOF pec ra trong pin Q PhSOWL + He +2CHCOO'+ HT = PbL + 2.CHACOOH+ HS0- I 1 i: Dung dich A gim Fe(NOs)s 0,05 M; Pb(NO;); 0,10 M; Zn(NOs), 0,01 M 1. Tinh pH cata dung dich A. 2. Sue khi H:S vao dung dich A dén bao hoa ([H:S] = 0,10 M), thu duoe hén bop B. Nhiing két tla nao tach ra tirhdn hop B? 4B3. Thiét lép so do pin bao gdm dién cue chi nhiing trong hn hop B va dién cue platin nhiing trong dung dich CH;COONH, | M duoc bao hoa béi khi hidro nguyén chat 6 ap suat 1,03 atm. Viet phan tng xay ra trén timg dién cuc va phan img trong pin khi pin lam vige Cho: Fe* + HO = FeOH™ + H’ Ig*B,=-2,17 Pb* + HO = PbOH + H’ lg*f:=-780 Zn + HO = ZnOH’ + H’ Ig*B;=-8,96 9 0 Oo 8 RT Ef ote TOTTI Vs ESans= O41 V5 Ep2yp,=O126V 5 & 25°C: 2303 In=0, Bay pK gs) = 26,6; pK syzns) = 21,6; pKsires) = 17,2. (pKs = -IgKs, voi Ks la tich s6 “oS PK aris) = 7.02; PK oa.s) = 12.90; PK ye, = 9.24, PRyc,coony =4,76 ‘A Hing din < Dung dich da cho chi gdm cée cation kim loai, HS edn so sinh egacangfang Yao phite hidroxo trong hé tim ra cn bang cha yéu quyet dinh pH cia hé. Fe" +10 = FeOH* + HO *pi=102 ( Pb +H,O = PbOHY + H+ 3 Zn +10 = ZH + HE @) 1") mO = OW + H >> Kyl tinh pH theo (1): So sinh (1) + (4): *Bi.C,.3.>> "Bo. Cyps > Fe* + HO. Coos {] 005-x x x =0,0153 M > pHa = 1,82. 6 thé tach ra, trude hét xét cde phan tng c6 thé xéy ra theo thir tur én bé, so sinh va cho biét mize d6 xy ra ctia mbi phin img. Xée Giai ra t@quoc: t cde cin bang co thé co va xét digu kién xudt hign két tia Do V> Egaus £0,141 Ven: 1/2Fe* + HoS = 2Fe* + $) + 2H* Ki= 10% Ae : 0,05 0,05 2/Pb” + HyS <= PbS] + 2H" Ko= 10%" 0,10 0,05 - 025 3/Zn"' + HyS = ZnS] + 2H K3= 10!" A/Fe" + HS = FeS| + 2H" Ky= 10°" 49K; va Ks nho, do dé can phai kiém tra digu kign ket tia cia ZnS va FeS: Vi méi trudng axit =C,,»-= 0,050 M (b6 qua qué trinh tao phi hidroxo) Déi voi HbS, do Ko << Ka) = 10” nho —, kha nding phan li cia HyS trong méi truong axit khéng dang ké, do dé chap nhin [11"] = C,.=0.25 M_, tinh C.. theo cén bing ting hep sau HS = S* + lr Ku Ko= 10°? 0. [H2S] _ j give = 10” Ky Ko oP = 10" asp = 10 ts Tad: C2. Cy pH=7,00 9 [H']=107 gn proton hoc t6 hop 2 can bing (5) va (6)) op id PT 2 20592 102-0415 V< Eman == 033 V Py, 2 LB (cé thé tinh [HY t Vay. E ‘2H"F ddign Suc chi la catot, dign eve platin la anot. So dé pin: Re (p=1,03atm) | CHsCOO" IM; NH} IM || S; PbS; HaS IM; H’ 0.25M; Fe” 0,05M; M g [Pb +) Trén anot: Hh > 2H’ +2e 2x| H+ CHsCOO > CHCOOH Th + 2CHsCOO" > 2CHsCOOH + 2c Tren catot PbS + 2H* + 2e > Pb| + HS Phan img trong pin; PbS+H,+2H' +2CH;COO' + Pb| + H»S +2CH,COOH 3 50Dé xac dinh hing s6 dign li ciia axit axetic, nguii ta thiét lap mét pin: PLH, | CH,COOH(0,01M)|H"IM|HL, Pt Voi ap suat H, la 1 atm. Site dign dng cita pin bing 0,1998V (25°C). Tinh hing sé dién li ciia axit axetic Huéng din Bai todn nay la dang bai tép nguoe: tinh K, hoe cée dai luong lién quan dén can bing a bazo tir sie dién déng cia pin ‘Trong bai nay, dién cue bén phai la dién cuc hidro tiéu chudn, Cu thé: ~ Eyin= E.-E.=0-E.=0,1998V — E.=-0,1998V B.=0,0592Ig(H*] > [H']=10°°%M. a Xét edn bing phan li « CH,COOH = H’ + CH,COO 9 0.011038 10359355 —[WCH,COO J _ . K, &1,8.10°5 Co [CH,COOH] Bai tip 3! Tinh ste dign dng ota pin Pt, Hp (Latm) | HCI 0,02 5 Bai nay thude dang bai ~ dlign dng cia pin tir gi tri pH c6 thé tinh duge INa (0,04M) | AgCl, Ag cH,coon =18:10°. cho: Eo Cho: EAgci/ Ag ap xu DAgCI+ Hy = 2Ag +2CT + 2H" \ CH;COO’ + H = CH;COOH Cc 0,04 0,02 9 » Tl 002 = 0,02 CH;COOH = CH;COO + H com 0 o 0,02-x 0,02 +x x 3 0249) bg toe 0.02—x x< 0,02 = x= 18.10% StCl 0,02M, CH,COO™ 0,02M = pin: Pt, H, (latm) pin Ph HE, Cam) 8 10° CH,COOH 0,02M secu E +0,059.1g—- = 0,322 [cr] = Baim 0059 jglHT _o,28v 2° De YY Sebi AY ~ Cho biét site dign déng cita pin: Pt (H) | dd do] KCI IM | Hg:Cb | 0 1V. Hay tinh pH cia dung dich do. Cho E.sonen = 0,282V aS C6 E, = -0,0592pH = Ecatonen ~ Epin = -0,289V 1 pH = 4,898. Bai tip 41° 298K, nguyént6: Hg, HgsCh|KCI(b.h)|CHsCO ), quinhidron|Pt 6 site dign dong E = 0,2215V biét ring 6° qui ,699V, thé cia dién cue calomen bio hhoa bing 0.2415V. Tink hing s6 phan li ci Dip 86: K = 1,92.10° A tip 42: Hay xe dinh site ‘Ua pin dign sau 6 25°C: PH, ) [ddA |] KCI bao hoa | HesCly | Hg ~ Dung dich A tao thinh khi trn 10ml dd NaOH 0,02M véi 40ml ddHCN 5.10M. Cho biét Exh =0.242V, pKucw = 9,35. Trude ht xe din E 0 E.=-0.0592pH, Tinh pH dung dich A 9 Nong d6 sau khi trdn: Cyson = 0.4.10°M; Crew = 4.10°M ‘TPGH cia hé sau khi xay ra phan img gitta NaOH va HCN gdm: HCN 3,6.10°M; CN'0,4.107M; H:0 —+h@ nay la hé dé. Cie edn bing xay ra trong hé HO = H + OW K,=10" 52HCN = HW + CN” K,=10%" CN + HO = HCN + OH K,=K,K ‘Tinh gin ding pH ctia he theo pHyem CO: [H]=K, LRCN] _ 8 3.6.10 {CN} 0,4.10 Nhur vay mai trutmg ciia dung djch la mi truémg bazo. Do vay can bing ciia CN’ la * my 910° «107 chi yéu quyét dinh pH cia hé Tinh todn can bing ciia CN’ theo dinh ludt tac dung khdi hung ta duge {01 alo pH = 8,396 E.=-0,0592pH =-0,497 — Bpa= Eztonen ~ E.= 0,242 - (-0,497) = 0,739 QO Bai tip 43. 1, Thiét lp so d6 pin va viét nia phan ing dé khipit ing xily ra phan img: CH;COO" + HSOy = CH\COOH + SO; 2. Tinh AG' jin 3. Tinh ndng d6 mol cae ion trong di Ein = 0. 4, Ghép pin xung doi: | () PtH: | CHyCQO"C@,080M) | SO, (0,050M)| Hz Pt (+) v6i pin: (-) Ag AgCl IM)| | KCI(ba0 hoa)| HCl, He (+) Cho E°4 gcyAag= 9.222V; ig 9244V. KxcH COOH = 10"; Kego,= 10” Viet cae ban phan y ra 6 méi dign cyc va cae phuong trinh phan img ? Huéng dan: Phan 1, 2 oga bai y khong c6 van dé gi khé khan. Hai van dé méi trong bai tap nay nim & eon 34a. 3, yeu edu tinh néng d6 cde ion khi Ip = 0 hay khi pin nging hoat dong, c6 ia mg ting trong pin dat dén trang thai cdn bing, G phan 4, ehép xung di 2 pin véi no 6 site dign déng lin hon sé cung cap dién cho pin con li, hay ndi céch khéc pin stte dign d6ng bé hon tro thanh binh dign phan. Qo ion H* tir HSOy nhigu hon ion H° tir CHyCOO nén c6 so dé pin la (-) Pt Hz (I atm) | CHsCOO"(0,08M) | | HO. (0,05M) He (1 atm) Pt (+) Nita phan img @antot: He + 2CHsCOO" + 2CHsCOOH + 2° Nita phan img 6 catot: 2HSO; +2e + Hy + $02 2. Tinh Bn + Tinh Ey: ‘Theo edn bang: 53CH;COO" + H,0 = CH,COOH + OH Ky=K,"K,= 10°" el (1 (x) x x => K= x'i(l-x)=10°™ (voi x= [OH] = 10%" => [HY = 10104 = 10° => BY) =0+ (0,05922)lg{H'T/Py, = 0,05921g10°** = - 0,56(V) + Tinh E's) Theo cfn bang \V Hor = H+ soe K=107 av el © f(y) yoy S => K =y"i(1-y)= 10" (void y= [H']=0,095 => Ey) = 0,05921g{H'] = 0,05921g0,095 = - 0,061(V) Vay Byin= E)- E% =~ 0,061 - (0,56) =0.499(V), => AG®=- nFE* ia = -2.96500.0,499 = -96307(J) 3. Tinh ndng d6 mol cdc ion trong dung dich khi Ipin = an bing c a Khi I=0 cé nghia la pin ngimg phong a an tng trong pin dat dén trang thai CH;COO" + HSOy = CH;COOH ui K= 107,10" = 1077 008 0.05 (0.03+x) x wy (0,05-x) =oK = eacsiaae 0°" = 1,43.10°(M) => [CH;COOH [S (5-1.43.10" = 0,049857(M), (HsO=4! [CHsCOO] = 0,03 + 1.43.10 =0,030143(M). 4. + Xét pin Ns 1» | CH\COO' (0,080M) || HSO¥ (0,050M) | Hb Pt(+) — anot CHsCOO +H:0 = CHsCOOH + OH K=10°** 0,08 [1 (0,08-x) x x => K =x71(0,08-x) = 10°! (vai 0 x= 6,78.10° E(y = 0,0592Ig(H] = 0,05921g(10"/6,78.10") = -0,52(V) - Dign cue catot HSOr = H+ SO? K=10° C008 54[] (05x) x x => K =x7((0,05-x) = 10” (v6i 0< x < 0,05) => x= 0,018 => By) = 0,0592lg(H'] = 0,05921g0018 = -0,103(V) => Epa) = Eqs) = Bey =-0,103 (0,52) = 0,417 (V) + Xet pin2: (-) Ag AgCl | HC1(1,50M)|] KCl(bao hoa) | Hg,Ch, Hg (+) Bin phin img Gano: Ag + Cl + AgCl +e = FAgciAg=F’agcVAg + 0.05921g(VUCcr) =0,222 + 0,05921g(1/1,5) = ew, => Bpuie) = Ee - Bey = 0,244 - 0,212 = 0,032(V) y Vi Epa) = 0,417 > Epo) = 0,032(V), nén pin (1) 6 vai tr cung cip di a (2) (pin duge nap dién), Do vay ede ban phin tng xy ra nhu sau © Pin: (-) PtH; | CHsCOO"(0,080M)| | HSO,"(0,050M)| Hs Hs +2CH\COO2CH;COOH #2e — 2HSOy #2e > SO. Dign phin (-) Ag AgCl| HCl (1,50M)| | KCI(bao hoa) | Hd CY 2AgCl +2e + 2Ag+ 2Cr 2Hg + 2CT + AlgsCl ~ Phin img xay ra trong pin (phéng dign): HSO,' + CH\COO" + CH,COOH + ig tu xiy ra) ~ Phan img xay ra khi nap dign 2Hg + 2AgCl + HesCh gin img khing ty xay ra) ‘X¢t kha ning phan img ciia Br”, whe, trong ede trudng hop: a) OpH=0 b) Trong dung dich hohe (Ka= 10°") ©) Opl=7 = Cho Eo ev ih i Bai tpnay lighyquan dén sur nh hutng cita pH dén thé dién eue cla clip oxi hoa — khit, tinh gia i uc theo pH. Tir dé, so sénh kha nding oxi hoa, khir cia cae dang va két ludn vé chigu =1,36V, E? 20 =1,09V ‘a,rer fén ra cia phan tng can x¢t. Ce ban phin img Khir img véi cée eli oxi héa ~ Khir Cl, #2e2 2c Br, +2e = 2Br MnO; +8H° +Se= Mn +4H,0 Eig =L51V 55‘Ta thay, gid tri thé dign cue ciia cp Cly2 CI" , Bry/2 Br” khéng phu thude vao gid tri pH, edn gid tri thé dign cue iia cp MnO;/Mn’* phu thude vio pH theo biéu thire: 0.0592 , [MnO JH" t 3 [Mn] 0 4 90592, [MnO,] , 8.0,0592 swccna 5 gy gD Coi [Mn0;]= [Mn™*]= 1M thi E, 1,51 -0,09472 pH nn ONAL PH = 0-H Exige = Eis = ESI > E? Eh ome = h09V én MnO; oxi hoa duge Br” va CI b) Néu trong dung dich CHsCOOH 1M ta xét edn bang: & CH,COOH = CH,COO” + HI = 1047 ‘noi (Lx) x x > = 10% 10° => pH=2,38 (Fy Tird6 tinh duge: E, = 151-0,0472 RG Vv Ma Be nee =136V> Expocnaee = 4285 eur = bO9V nén MnO; khong oxi hoa duge CI, con oxi hia duge Br° c) Neu pH=7 thi \) Exojae = 151 -, 00 5 OBHV < Eh age = LO9V < Bb ge =136V nen MnO; khong axi po o gi tri hing s6 bén ca phi, ti ste dign déng eta pin din hia. ~ Bai ji cho gid tr site dign dong cia pin dign boa, tinh hing sb bén cia phe & bai tp dang nay, phan img tao phic thutm, dune ghep vi cdc loi phn ing Kh. ey ‘thanh mét bai toan phite hop. ‘Vang kim loai thing duge tim iy trong cée quing dé aluminosilicat va thuimg phin tan trong mot s6 céc loai dé khic, No c6 thé duve phan tach ra bing cach xit ly da nghién voi dung dich NaCN. Trong qua trinh nay, ving kim loai din chuyén sang dang phite [Au(CN):J' tan duge trong nude (phn img 1) 56Khi dat t6i trang thai edn bing, dung dich phute durce bom ra ngoai va vang kim loai duoe thu hdi bing céch cho phi vang phan img véi Zn, dé chuyén thanh phite [Zn(CN),]* (phan img. 2). a, Viet cde phan tg 1,2. b. Vang trong tur nhién thudng co Kin bac, va bac eting bi oxh béi dung dich NaCN. Co 5001 dung dich hn hgp [Au(CN);] 0,010M va [Ag(CN)s} 0,003M duge cho bay hari dén 1/3 thé tich ban dau, va duge xir ly bang 40g Zn, Hay tinh néng 46 [Au(CN)sJ va [Ag(CN)e] sa phiin (mg xy ra hoan ton, Coi nhu khong e6 sir sai khdie no ding ké so véi khi tinh! dite Cho [zn(CN),F + 2e = Zn + 4CN cae? [AW(CN),. + @ = Au + 2CN7 EF [Ag(CN),F + € = Ag + 2CN” E' c. [Au(CN),J la mot phite bén, Tinh ndng dé dung djch & vang nim dui dang phite trong dung dich. Cho Ky = 4.1 Huéng din Bai toan nay chi doi hoi hoe sinh nhimg ki ‘vé phan tmg oxi héa khir c6 sur tham gia cuia pit 18 99% luong van va viet phuong trinh rat co ban a, Viét cate phuong trinh phan ting 1,2: - Phin img 1: 4Au + 8CN: 30 — 4[Au(CN):] + 40H [Zn(CN),* + 2Au, = Phan img 2: Zn + 2d b. Dé lam duge phiin nay, ey ‘aya vio thé khir chudin dé bai da cho dé xée dinh xem Ti phan img ndo xay rat -1,26)=0,95V = (-1.26)= 0,66V < E%(Ag/Zn) nén phire bac bi Khis trude 0,003 = 1,5mol =500.0,010=5,0mol + 5,38 = 0,61 mol ve gyn Fan eng = 2 zn = 2.0,61 = 1,22(mol) 9 én =1,5~1,22 = 0,28(mol), [Ag(CN)sJ chua bi khi EX(AgiZn) BY Aws >on TARICN), dts ‘Vay sau phin ting, [Au(CN).J = 0,01.3 = 0,03(M) [Ag(CN):] = 0,28 3/500 = 0,00168M. ©. Xétednbing Au’ + 2CN- + [Au(CN),) K,=4.10" Dé 99% lung ving edn Iai trong dung dich phite tite la [AU(CN),. 99 Tr} UCN Eig 2 MN I=LAWCN)T 199 37[Au(CN),T [Au'} {CNP Dé Thi chon Dai tuyén Quée Té - nim 2008) Khidotir — K, = co Ky=99/(CNF 0 [CN]=5.10'%M Bai tp 46: (Phin Dé xae dinh hang sé tao phic (hay hang s6 bén) cia ion phite [Zn(CN).}", nguisi ta lam nu sau: ‘Thém 99,9 ml dung dich KCN 1M vao 0,1 ml dung dich ZnCl 0,1 M48 thu duge 100ml dung dich ion phite [Zn(CN),}* (dd A). Nhiing vao A hai dién cue: dign cue kém tinh es dign cue so sinh la dién cue calomen bao hoa c6 thé khéng d6i la 0,247V (dién AS trong trudmg hap nay li eye duong), NOi hai dign cue d6 voi mot dign thé ke, d gilla ching duge gid ti 1,6883V. Hay xac dinh hang s6 tao phite cia ion a She thé oxi hod - khir tigu chudn eta c&p Zn”'/Zn bang -0,7628 V. Huéng din Bay la bai toan nguge: Xéc dinh hing s6 tao phite tir sire < pin, Muén tinh hang sé bén, ta biéu dign ndng 46 ion kim loai qua hing s6 phite, Tur sire dign ding xée dinh ndng d6 ion kim loai ra hing s6 bén. Phan img tao phite: Zn" +4. CN = [[Zn < lie va ng d6 ion tao [2Zn(CN),F ‘Hang 6 tao phate: fy, = 33 = Eca - Ezn = 0,247 -Ezn = 0,247 - 16883 =- 14413 V BSP. [Zn*] = -1,4413 (V) > [Zn] = 10, ing dich A duoc tao thnh bai CoC 1, Tinh pH va ndng d6 ion Co™ trong dung dich A 2. Viét so d6 pin va tinh sie dign déng E ciia pin duge hinh thanh khi ghép (qua céu muéi) dign cue Pt nhiing trong dung dich A vai dign cue Ag nhing trong dung dich KCrOy 8.0.10" M 6 chira két tha AgsC10, 58Cho: pK: N Hy" 924; HCrO,- 6,50; pK, (chi s6 tich sO tan) AgsCrOy: 11,89. E": Co™/Co™ 1,84V; H:0:/20H” 0,94V; Ag'/Ag. 0,799V. Log hiing s6 tao phire: Co” + 6NH; = Co(NHs)s" ; IgBi Co" + 6NH; = Co(NHs)” ; IgBo= 439 = iy ld mot bai tdp tng hop thude loai bai ton xudi,¢6 lita quan dén nhiéu phin kién Oy ug dign cue bi anh huéng bai cén bing tao phife va cfn bing tao hop chit it tan, ddi hoi phai c6 dupe kha nang phan doan, nhan xét, va KT nang tinh toan than thao méi RY thin duoe bai tap. Cy 1. Trong dd A, vira xiy ra phan tng tao phir, vita xay ra phan ting oxh Cy vil 1,05 . Dé xc dinh TPGH cia dd A phai xét hét cac phan img nay. Quitrinh dignlicia: CoCh + Co + 2Cr 0,0100 _ 0,010 (Qua trinh tao phite cia ion coban voi NH Ss Co + 6NH; = Co(N = 10° 0.0100 03600 oa 0,3000 ~ 0 (Qua trinh oxi hod Co(NHs) M0006) 19-4 , x= 7682, wack (0,300-x) + [OH]=6,768.107 > pH=118: © Tinh ndng d6 ctia Co™ trong dung dich: Két qui tinh theo (2) cho thiy [NH] = 0,3 ing: Co(NHs)s"* = Co™ 10°” C 0,040 SS [1] (@0040-x) A 0 + ae x= [Co™]=2,117.10% <<0,3000 (0, Vi vay vige coi [NHs) Ko) 00) la dung. 2. Tinh Epa “Tpogiddien cue Pt {Co ¥ caus = 0.0060 M (vi Birt lam; c6 dur NIL) 2] = 4.10 = 2,117.10 = 3,788.10 (M) ¥ E = 0,0184 + 0,0592 Ig © _ = 90320 (v) ‘cont Cant * 3,788.107 Q *Tinh E cia dign cue Ag: ¢ cla dién cuc Ag do cip Ag>CrOy/2Ag quyét dinh (ho&e Ag’/Ag). AgCrOy + 2¢ = 2Ag + CO” 0,0592, 1 Exe =Eecoune +9 Siero] Tinh E),,c0,ing bang cach t6 hop cde cfn bing: 60AgCrO = 2Agy + CO? K=10" at ax| Agi +2e = Ag Ke= (Bi = 0,799 V) AgCrOd + 2e = 2Ag + COP Ky= 100" 0,0592 Ki=Ke. Ks > Exgcouag= Ey = Es + J leks = 0447 (V) Tinh ndng d6 CrO,* thong qua hai can bang c6 lién quan: \V COF + HO = HCO; + OH K,=107 \ © 810° a [J 810°-x x x 107 — x=16.105 <8, ma AgCrOd = 2Agh + CO" & ¢ 8.10° Ss if 2x Hey = (2x)? x (8.103 + x)= 10 x =6,3.10%< (Cr0.]=8.10° M Eq= 0447+ ie ms 5090 (V) Tacd: Eq > En — Agi PL i anot. =~ —* (0008-3) 8 So dé pin: (a) Pt| Co(NHs).**, oF Hs AgCrOst ,CrOx* | Ag (©) Fyn =BQQEs — 0,0302=0,479 (V) Bai tip 48° MO bai hai dign cue: dign cue thir nhdt gdm m6t thanh déng nhing trong dung digh' Ong dé la 0,01M; dign cue thir hai gom mét thanh déng nhiing trong dung dich 1u(NH3):}* ¢6 nding d6 ki 10°M. Sire dign dong cia pin & 25°C la 38mV. mana (itoLI") cia ion Cu” trong dung dich 6 dign cue ém va tinh hing 6 bén cia phite (Cu(N).F* [i bai todn nguoc kha dom gidn: tinh hing s6 bén tir gia tri sire dign dng. Trong bai todn nay, pin dign ha la pin ning d lim vige thudn nghich véi ion Cu", ign cue [Cu(NH3),)"/Cu cc ning d6 Cu’* nhé hon nén déng vai tr la cue am cia pin Ta c6: Epa =E,-E, ‘Trong d6 Bee BY ge tgtcu™ | =0,337 + oS g0.01 =0,2778V ‘caica *9 Do dé: E. = 02778 - 0,038 = 0,2398V. 61ad ee Ig(Cu’*] =02398V 0 [Cu*]= 10°. Xét can bing: Cu(NH,),* = Cu” + 4NH, 01 10°28 19° 4.10% [Cu(NH,),F* __0,01-10°* — 9,75.10" (Cu INH, ()AB/ARICN)A"(Cu) CN’ | | Ag(Cw) “AB (+) a. Nguéi ta lam thay di ndng d6 CN’ trong nita pin bén trai, Bigu dign sy iota site dign dng cita pin nay vao n, pKys va [CN’]. biét [CN'] due lay du sao so véi néng d6 cia phite chat. b, Tinh n va pK biét rang E = 1,20V vai [CN] = IM; B= is ON 10M Huéng din: Pay la bai toan nguge 6 dang tng qua, cach lam tong ip tr8n, a. Pin dign hoa la pin ndng 46 voi dign cue ch Gi) la cuc am. dl Ta oi: E,, =0,0592le ra Tro rs ndag 45 Agé tr do trong dung dich Dé nghién citu su tao phite clia Ag’ v6i CN’ nguoi ta ghép pin dién héa sau: Ay ing ding ke pric: [har] = Ket Aat CN Kx + 0,0592.n 1g [CN] {é bai cho vao duoc hé 2 phuong trinh 2 an, gidi ra ta duoe: pKy, = so dé pin: (-) Ag | Ag(NHs)." (0,01M)| | AgsSO, (bao hoa) | Ag (+) Tinh hing s6 tao phize Ag(NHs):’ biét E°Ag'/Ag = 0,800V; Ksag,s0, = 1,100.10" lov 2, Suat dign dong cia pin thay Oi nhur thé nao néu ta thay dOi nbur sau: a) Thém mudi NaCN IM vao dign cue anot b) Thém HC! vao dign cue anot ¢) Thém CH;COOH 0,01M vao dign cue anot 4) Thém mudi BaC bao hod vao dign cue catot ¢) Thém mudi NaCN bao hoa vio dién eye catot. 62Cho BAg(CN)s"= 10" KscH,COOAg= 107"; Kspaso, = 10°™. Huong dan: Bai tip nay kha tng hop. Phin a [a bai todin nguoe: tinh hing sé bén cita phite tir gia tri site dign dng, Phan b li xét sy nh huding cia cae yéu td dén site dign dong cua pin 6 ca hai dign eve: + Tinh Ey ‘Theo can bing: AgSO, = 2Ag’ + SO." — K,=1,10.10° 23S \y => [Ag’T [$0.7] = (28).S=K, => [Ag’]=28=2(KJ/4)"" ~ => Eq) = E’Aag' Ag + 0,05921g[Ag'] ag'iAg + 0,05921g2 (K,/4)'3 = 0,8 + 0,05921g2.(1,1.10°/4)'5 = 0,708 + Tinh Ey ‘Theo ean bang, & Ag(NI)” = Ag’ +2NH; f=? 9 => B= [Ag INKS =4[AgTTAg(NHD)"] = ‘Ag(NH;)o* => [Ag ]=(Cag(niiy)'/ 84)" > By = P’agiiag* 0,05921(Ca p(n), ws =0,8 + (0,0592/3}1g0,01/4 ~ (0,059: 749 - (0,0592/3)le8 => Eqn =0,708 - 0,749 + (0,0592/3)Ig8 * 0,102 => p= 1075 a) Khi thém mudi NaCN yao Wign ete anot cé phan img: Ag(NHs)." + 2CN" = A Hy K= 107.108 = 10"*(rat lim), nén Khi cho mudi NaCN véo lam néng d6 ’eiim do d6 Ey gidm. Vi vay suat dign déng cia pin tang. b) Them ee anot Ag’ + NES phatiuing trén lim nong dé ion Ag’ ting, nén E,, ting lén. Vi vay suat dién dong ciia ri x lic néo do pin ngimg hoat dng va dai chiéu dong din trong pin Vv ‘Thém CH\COONa 0,01M véo dién eye anot. * Kh thém CHCOONa vio dign cue anot c6 phan ing: Ag(NH);" + CH;COO" H,COOAg + 2NH; K 104,107)" = 10 (nh) ‘Theo phan ting trén thay K nha, mat Khe ndng 46 CHsCOONa lai loang vi vay hong phite mat di rat it. Vi vy sudt dign dong cita pin coi khong d6i 4d) Thém mudi BaCh; bio hod vao din cue catot. Khi thém BaCl: vao dign eye catot c6 phan img, Ba” + AgSO, = BaSO, + 2Ag’ K=10*"(10% 10° (lon) 63‘Theo cn bing trén cho thiy néng d6 ion Ag’ o dién cuc catot gidm, nén lam Ej.) gidm => lim suat dign dién ciia pin gidm (va dén Iie nao d6 co thé pin di chiéu dong dign. e) Thém mui NaCN bao hoa vio dign eye catot. Khi thém mudi NaCN bao hoa vao cé phan img: AgSO, + 4CN’ = 2Ag(CN)y + SO" K=10%,(10°4)? = 10%" (rat lon) ‘Tir phan img trén thay K rat lim, nén phan img xay ra nhanh va hoan toan vi vay By.) gidm nhanh, nén Ep giém nhanb, 64