Nguyn Hu THPT Chuyn Hng Yn

T VN Mt trong nhng ni dung c bn , quan trng ca phn in ho hc l pin in, sc in ng ca pin v th in cc chun ca kim loi . Nhng kin thc gip ta gii thch nhiu vn trong thc tin nh s n mn kim loi, kh nng phn ng ca kim loi khc nhau vi dung dch axit, dung dch mui... Mt khc , n cn gip ta bit cch thit lp cc cp pin c kh nng hot ng tt, xc nh c sc in ng ca pin. Trong nhng nm qua, thi hc sinh gii Quc gia thng hay cp ti phn pin in di nhiu gc khc nhau. Tuy nhin, trong sch gio khoa ph thng , do iu kin gii hn v thi gian nn nhng kin thc trn ch c cp n mt cch s lc. Qua thc tin ging dy i tuyn hc sinh gii Quc gia nhiu nm ti nghin cu, chn la v h thng nhng kin thc l thuyt c bn, trng tm, nhng bi tp in hnh son ra mt chuyn ging dy v pin in gip cho hc sinh hiu su v vn dng c tt nhng kin thc trn vo vic gii cc bi tp. Ni dung gm: PHN A: K hiu cho h in ho theo cng c ca IUPAC (1968)
I. II. III.

T bo in ho in cc T bo Galvani

PHN B: Gii thiu mt s bi tp p dng

Nguyn Hu THPT Chuyn Hng Yn

NI DUNG
PHN A: K HIU CHO H IN HO THEO CNG C CA IUPAC (1968) I. T BO IN HO ( in ho) : L mt h gm 2 in cc l hai vt dn in loi mt (vt dn in electron: dy dn) nhng vo mt hay hai dung dch in li hoc cht in li nng chy( vt dn loi 2: dn in nh ion). Mt in cc cng vi cht in li ca n mt ngn in cc (cng c th hai in cc tham gia vo cng mt ngn) VD1: T bo Vonta in cc Zn , Cu nhng vo dung dch H2SO4 VD2: T bo aniel in cc Zn nhng vo dung dch ZnSO4 in cc Cu nhng vo dung dch CuSO4 Zn ZnSO4 CuSO4 Cu
Phn loi t bo in ho: 2 loi

- T bo Galvani (hay Galvani): Nhng t bo in ho sinh ra dng in nh phn ng oxi ho - kh t pht xy ra trong ( ho nng bin thnh in nng). Khi phn ng ho hc trong t bo c G < 0 v E > 0.
-

T bo in phn: L nhng t bo in ho trong xy ra qu trnh oxi ho- kh cng bc

di tc ng ca ngun in ngoi .(Khi t bo in ho tiu th cng in bin thnh ho nng trong sn phm in phn.). Khi phn n trong t bo in ho c G > 0 v E < 0. (T bo: H n gin nht) II. IN CC: 1. KN: Mi t bo in ho c hai in cc . Mi in cc nhng vo dung dch in li to thnh mt ngn in cc Ti mi in cc c c mt cp oxi
2

Nguyn Hu THPT Chuyn Hng Yn ho - kh . Khi t bo in ho hot ng c dng in chy t in cc ny sang in cc kia . trn b mt in cc xy ra s oxi ho hoc s kh ( na phn ng oxi ho hoc na phn ng kh) Catot: L in cc ti lun xy ra na phn ng Kh Ox + ne kh:
c c

(c: catot) (a: anot)

Anot: L in cc ti lun xy ra na phn ng oxi ho: Kh a - ne Ox a hoc Kh Ox + ne a a

Oxc + Kh a Ox a + Kh c Catot (+) cn Anot (-) Catot (-) cn Anot (+)

( C hai loi t bo Galvani v in phn u nh vy) -Trong t bo Galvani: -Trong t bo in phn: Ngc nhau

Phng trnh Nernst cho th in cc:

Trong trng hp chung in cc c xt khng phi l in cc c iu kin tiu chun . Chng hn vi s pin: Pt , H2 (1 atm) H+ (C = 1,0 M) Mn+ (C 0) M Ta c :
E pin = E pin - R T ln nF
0
+

CH . CM
2 CM . PH2 n+

(1)

H2

CH

= 1,0 ; P H
E

= 1 atm ; i vi cht rn nguyn cht, hot

= E0 +
Mn+/ M

aM CM 1,0
E pin =
Mn+/ M

RT nF

ln C
Mn+

(1a)

Khi xt 250C thay gi tr bit ca R, F vo (1a) v thc hin cc bin i thch hp ta c:

E
M /M
n+

= E0
Mn+/ M

0,059 n

lg C
M
n+

(1b)

2. Phn loi in cc
1- n cht tip xc vi ion ca n trong dung dch

+ in cc kim loi: Mt thanh kim loi nhng vo trong dung dch mui ca n. c vit: M(r)Mn+ (aq) .
3

Nguyn Hu THPT Chuyn Hng Yn Phn ng in cc Mn+ (aq) + ne

(2)

M (r)

Th in cc c xc nh bng biu thc Nernst:

E = E0 - 0,059 lg [Kh] n [Ox]

[Kh] ph thuc vo s nguyn t nm trn b mt khng i nn:

E = E0 + 0,059 lg [Mn+] n (3)

+ in cc kh: Gm mt thanh kim loi tr (hay graphit) ng vai tr vt dn in ng thi l vt mang cc phn t kh , c nhng trong dung dch cha ion tng ng v c bo ho bng kh tng ng (in cc tip xc ng thi vi kh v dung dch cha ion ca n) c vit: VD: in cc hiro c vit : (Pt) H2 H+ ; in cc kh clo: (Pt) Cl2 Cl- ... 1/2 H2 (k) + H2O Phn ng in cc hiro l: H3O+ + e Th ca in cc c xc nh theo phng trnh:
E = E0 - 0,059 lg
H2
+

Pt (r) X2 (k) Xn+ (aq) Pt (r) X2 (k) Xn- (aq)

(4)

[H3O ] H V E03O +/ H2

= 0 v thng thng P = 1 atm nn (3) c dng:

E = 0,059 lg [ H3O+] = - 0,059 pH (5)

2 - ( in cc oxi ho - kh): Kim loi tr in ho(hoc graphit) nhng

vo dung dch cha ng thi dng oxi ho v dng kh ca cp oxi ho kh Mm+/ Mn (in cc trong kim loi v kh khng tham gia trc tip vo phn ng in cc), c vit: PtMn+, Mm+ Phn ng xy ra in cc c dng tng qut: Ox + ne
4

Kh

Nguyn Hu THPT Chuyn Hng Yn Th ca in cc c xc nh theo phng trnh: Hay:

E = E0 - RT ln K nF E = E0 - 0,059 lg [Kh] n [Ox] (6) (7)

VD: Pt Fe2+ , Fe3+ l in cc oxi ho - kh v lc ny ch xy ra : Fe3+ + e Fe2+ Sn phm ca s kh (Fe2+) v sn phm ca s oxi ho (Fe 3+) khng thot ra trn in cc m vn trong dung dch
3 - Kim loi tip xc vi mt mui t tan ca n trong dung dch ca mt

mui khc c cng anion, c vit: Phn ng in cc: Th in cc: MX(r) + ne

M(r) MX(r) Xn- (aq) M(r) + Xn-(aq)

(8)

E = E0 + 0,059 lg [Mn+] n

VD: + in cc bc - bc clorua: Ag AgCl , KCl + in cc calomen : Hg Hg2Cl2 , KCl Phn ng in cc calomen: Hg2Cl2 + 2e 2Hg + 2ClV Mn+ tn ti trong dung dch cha anion c th to thnh vi n mui t tan nn Mn+ c xc nh bi tch s tan ca mui kh tan v nng ca anion tng ng:
[ Hg22+] = T Hg Cl
2 2

[ Cl- ]2

Nn :

E = E0 + 0,059 lg Hg2Cl2 n [ Cl- ]2

(9)

Khi [ Cl-] = 1 mol/lit :

E = E0 + 0,059 lg T Hg2Cl2 n = 0,792 + 0,03 lg 1,3. 10-18 5 (10)

Nguyn Hu THPT Chuyn Hng Yn

= 0,2556 (V)

Mt s dng in cc thng gp: in cc - KL/ ion KL - C kh K hiu M(r)Mn+ (aq) . Cp Ox / kh Mn+/M Na phn ng Mn+ (aq) + ne Xn+(aq) + ne 1/2 X2 (k) + ne MX(r) + ne (aq) Ox + ne M (r) 1/2 X2 (k) Xn-(aq) M(r) + X nKh

Pt (r) X2 (k) Xn+ Xn+ / X2 (aq) X2 / XnnPt (r) X2 (k) X (aq) - KL/ Mui t MXn/ M, Xntan M(r) MX(r) XnOx/ Kh (aq) - Ox / Kh Pt (r)Ox (aq) , Kh (aq)

3. in cc hiro tiu chun, in cc tiu chun, th in cc tiu chun a. in cc hiro tiu chun
Cu to: in cc gm mt bn platin ph mui (bt mn) platin trn b

mt , hp ph kh H2 P = 1atm 298K nhng vo dung dch c nng H + 1M. S ca in cc hiro tiu chun c vit: Pt H2 (1 atm) H+ ( C = 1.0M) Quy c: Ti 250C
+ E0 2 H / H 2

= 0,00 V

b. in cc tiu chun: Trong in cc tiu chun nng cht tan l 1 mol/ lit , cht kh (nu c mt) c p sut ring phn bng 1 atm ti 250C. c. Th in cc tiu chun( E0) : Th in cc o c iu kin tiu chun. Khi mt pin c to ra t hai in cc tiu chun th sut in ng ca pin ch cn: E pin = E0 pin E0 pin c xc nh bng thc nghim nh sau: Lp mt pin gm in cc hiro tiu chun bn tri vi in cc tiu chun ca in cc cn xt bn phi
6

Nguyn Hu THPT Chuyn Hng Yn Chng hn , ta cn kho st in cc M Mn+ pin c lp nh sau: Pt H2 (1 atm) H+ Mn+ (C = 1,0M) M
+ Theo quy c: E0 2 H / H 2 = 0,00V + n+ E pin = E phi - E tri = E0 M / M - E0 2 H / H 2

E0

E0 M n + / M l th in cc tiu chun tng i theo thang hiro ca in cc M Mn+ Mt khc E pin > 0 , do : - Nu in cc hiro l in cc m( ng vai tr anot: lun xy ra qu trnh oxi ho) th in cc cn o l in cc dng v phn ng trong pin qui c
+ n+ E0 M / M > E0 2 H / H 2

- Ngc li: Phn ng trong pin ngc vi chiu qui c

+ n+ hay E0 M / M < E0 2 H / H 2

( Trong thc t , lm in cc so snh ngi ta thng dng in cc calomen HgHg2Cl2 KCl bo ho c th bng 0,2415V so vi in cc tiu chun hiro do in cc calomen c th rt n nh, lp li cao, d s dng v bo qun). III. T BO GALVANI (pin Galvani hay Pin in ho )
1. Cu to ca mt pin Galvani: Zn - Cu ( pin anien -

Jacobi)
Hnh v:

e Zn Cu mui + Cu

dd ZnSO4 1M

Zn2+

Cu2+ dd CuSO4 1M

Cu to pin anien - Jacbi Kt qu: Kim in k lch trong mch c dng in

2. Gii thch hot ng ca pin:

7

Nguyn Hu THPT Chuyn Hng Yn

Xt in cc Zn Zn2+:

Zn (vi cc nguyn t Zn b mt)

Zn2+ + 2e

Kt qu: +Cc ion Zn2+ tch t tong dung dch dung dch tch in dng + Cc eletron tch t thanh Zn thanh Zn tch in m Tng t nh mt t in: - Mt bn l Zn - Mt bn l Zn2+ Hiu s in th gia hai bn ca lp in kp Th kh ca cp Ox - kh Zn / Zn Mi in cc c mt th xc nh (tu theo bn cht ca kim loi v Cion trong dung dch) khi ni c in th khc nhau bng dy dn qu trnh cn bng in th gia hai in cc lm xut hin dng in trong mch. in cc Cu c th cao hn electron chuyn t Zn Cu.
2+

Kt qu :

a. cc Zn: Cn bng Zn chuyn i b. cc Cu: Cn bng Cu2+ + 2e n b mt thanh Cu nhn e Phn ng trong pin: Zn + Cu2+ Zn2+ + Cu
Vic b tr tch bit 2 cp Ox/kh cho php li dng s truyn electron gia

Zn2+ + 2e (qt Ox Zn)

chuyn phi b li s e

Cu ( qt kh Cu2+) chuyn tri, cc ion Cu2+

cht kh v cht oxi ho sinh ra dng in . Vy : Mun bin ho nng in nng ta phi thc hin s oxi ho mt ni v s kh mt ni v cho electron chuyn t cht kh sang cht oxi ho qua mt dy dn. l nguyn tc hot ng ca mi pin. Pin : l dng c cho php s dng s trao i electron trong cc phn ng oxi ho - kh sn sinh ra dng in (ho nng bin thnh in nng) . Khi pin hot ng :

Nguyn Hu THPT Chuyn Hng Yn + Cc cation chuyn ri t tri phi, cng chiu vi chiu chuyn ng ca cc electron trong dy dn + Chiu dng in mch ngoi ngc chiu vi chiu chuyn ng ca cc electron.
Cu mui : Bng ng thu tinh bn trong cha thch c tm dung dch bo

ho ca cht in li thch hp ( KCl hoc KNO 3). Hai u ca cu mui u c lp xp SO4- c th i qua, thng l bng thu tinh. C tc dng ng kn mch cho pin hot ng.
Thanh kim loi : Va ng vai tr dng kh va ng vai tr vt dn

2. Phn loi pin: Ngi ta thng phn chia hai loi pin da vo c s to ra ngun in : * Mch ho hc hay pin ho hc: Khi pin lm vic c phn ng ho hc xy ra VD: in li hay.... VD: 3. S pin: a. C s vit s pin: Ta xt mch in ho anien - Jacbi: Zn + Cu2+ na hay bn phn ng: Zn Cu2+ + 2e (-) Hoc : (-) Zn2+ + 2e Cu Zn2+ + Cu thu c dng in t phn ng trn ta phi b tr thch hp v tr cc (-) Cu Cu2+ ( C = 0,1M ) Cu2+ ( C = 1M ) Cu (+) ... (-) Zn Zn2+ ( C ) Cu2+ ( C ) Cu (+) *Mch nng hay pin nng : Da vo s chnh lch ca nng cht

Trong tng hp mch anien - Jacbi , s nh sau: Zn ZnSO4 ( C )CuSO4 ( C )Cu (+) Zn Zn
2+

( C ) Cu

2+

(C)

S mch in Cu (+) ho hay S pin

Vy : C s vit s pin l g? Ta bit rng pin l dng c trong nng lng ca phn ng ho hc bin thnh nng lng dng in. Vy phn ng
9

Nguyn Hu THPT Chuyn Hng Yn ho hc dng lm c s ca pin phi l phn ng t xy ra iu kin c xt. Ngha l phn ng ny c G < 0 Theo biu thc lin h gia G v Epin :
G = - n F E pin Epin > 0

T ta c qui c sau y: Sc in ng ca pin s dng ( Epin hoc E0pin > 0) nu khi pin lm vic trong s pin cc cation chuyn ri t tri phi, trong dy dn cc electron cng chuyn ri theo chiu . Vy c E pin > 0 cn c : in cc bn tri : E0 pin = E0phi - E0tri =

cc m ( anot) E0(+) - E0(-) = E0catot - E0anot

in cc bn phi : Cc dng ( catot) Vy: khi xc nh pin:

in cc c th kh chun (tiu chun) ln hn c lm cc dng (catot)

lun bn phi
in cc c th kh chun (tiu chun) nh hn c lm cc m (anot)

lun bn tri b. K hiu ca t bo in ho: Anot ( tri ) - B mt phn chia gia hai pha , k hiu : - B mt tip gip gia 2 dd in li , k hiu : hoc + K hiu : khi gia hai dd ni vi nhau qua mt cu mui loi tr th khuych tn. + K hiu : khi gia hai dd khng c cu ni xut hin th khuych Vi ngn ami ng 2 dd tip xc nhau,tc khuych tn khng u gi Zn2+
Cu2+

Catot ( phi )

tn do s trao i khng tng ng cc ion.

10

Nguyn Hu THPT Chuyn Hng Yn Chnh lch in tch + chnh lch in th th khuych tn (ng gp mt phn vo sc in ng) trnh iu ta ni hai dung dch bng cu ni cha ddKCl . Qu trnh khuych tn ch yu l K+ , Cl- t dd KCl vo 2 dd hai bn. v khuych tn ca Cl- v khuych tn ca K+ Th khuych tn b loi tr. CuSO4 v ZnSO4 c tnh cht l ho khc nhau ngn cch nhau cu ni. - Nu in cc hoc dd gm nhiu cht th gia cc cht c du phy. Ch : * vit y t bo in ho cn phi: - Vit na phn ng catot, na phn ng anot ri cng li c phn ng tng cng - Xc nh catot (qu trnh kh) , xc nh anot (qu trnh oxi ho) - Vit k hiu ca t bo in ho * Trong trng hp cc cp oxi ho - kh m c dng oxi ho v dng kh u l cc ion trong dung dch ( VD: Fe3+/Fe2+ , Sn4+ / Sn2+ , MnO4-...) hay mt trong cc dng th kh hoc th lng (VD: H+/H2 , Cl2/ Cl-, Hg22+/Hg...) ngi ta phi dng mt kim loi tr lm vt dn in (Pt) , trong mt s trng hp ngi ta dng graphit). K hiu pin dng vt dn tr: (-) Pt Fe2+ , Fe3+ Sn4+ , Sn2+ Pt (+) (-) Pt H2 H+ Cl- Cl2 Pt (+) hoc (-) (Pt) H2 H+ Cl- Cl2 (Pt) (+) (-) Pt , H2 H+ Cl- Cl2 , Pt (+)

11

Nguyn Hu THPT Chuyn Hng Yn

PHN B: GII THIU MT S BI TP P DNG

Bi tp1: C cc in cc: Cu/Cu2+; Mg/Mg2+, (Pt)Cl2/Cla) Hy vit s pin dng xc nh th tiu chun ca mi in cc

theo qui c. Vit PTP xy ra trn mi in cc v trong pin.

b) Cho EoMg
2+

/Mg

= -2,363V, EoCl 2 /Cl = 1,36V; Eo Cu

2+

/ Cu

= 0,34V.

Hy xc nh li s pin ng theo qui c Eo > 0. Bi lm: a .Theo ng qui c th s pin in c vit: (Pt) H2 (P H (1) Ant (-) : Catt (+) : qt oxi ho : qt kh :
+
2

= 1atm)| H+ (C H

= 1M) H2

Cu2+ (C Cu

2+

= 1)|Cu

2H+ + 2e Cu

Cu2+ + 2e H2 + Cu2+ 2H+ + Cu

Phn ng trong pin:

(Pt) H2 ( PH 2 = 1atm)H+ (CH =1M) Mg2+ (C=1M)Mg Ant (-) : Catt (+): qt oxi ho: qt kh: H2 Mg2+ + 2e
+

(2)

2H+ + 2e Mg 2H+ + Mg (3)

Phn ng trong pin: H2 + Mg2+

(Pt) H2 ( PH 2 = 1at)H+ (CH =1M) Cl- (C=1M)Cl2 (Pt) (-) Ant: (+) Catt: qt OXH: qt kh : H2 2H+ + 2e 2Cl2H+ + 2ClCl2 + 2e

Phn ng trong pin: Cl2 + H2 c) Da vo th ca EoOXH/Kh

o EoOXH/Kh > E2H+/H2 = 0 th s pin khng thay i v phn ng trong pin

trng vi chiu qui c. Da vo theo : th pin (1) v (3) l khng thay i.

0 EMg2+/Mg < 0 pin (2) c vit li:

MgMg2+ (C Mg =1M) H+ (CH =1M) H2 (Pt)

2+

Phn ng cc v trong pin (-) Ant: Mg Mg2+ + 2e

12

Nguyn Hu THPT Chuyn Hng Yn (+) Catt: 2H+ + 2e Phn ng trong pin: H2 Mg + 2H+ Mg2+ + H2
M

Bi tp 2: Cho dy hot ng ho hc v cc th tng ng. Mn+ + ne E0 n+/M M K -2,92 Sn -0,14 Na -2,71 Pb -0,13 Mg -2,37 H 0,00 Al -1,66 Cu 0,34 Zn -0,76 Ag 0,80 Fe -0,44 Pt 1,20 Ni -0,23 Au 1,50

E0 n+/M M Hy gii thch :

a) Fe, Mg, Al tan c trong HCl b) Cu, Ag khng tan trong HCl c) Fe kh c Cu2+ d) Ag khng kh c ion Cu2+

Bi lm: Eo n+/M < Eo +/H2 H+ l cht oxi ho mnh, M l cht kh mnh do M 2H phn ng: M + nH+ Mn+ + (n/2) H2
Mg E02+/Fe ; Eo 2+/Mg ; Eo 3+/Al < Eo +/H2 = 0 Fe Al 2H

Do Fe, Mg, Al tan c trong HCl. b, c, d gii thch tng t da vo th ca cc cp tng ng. Bi tp 3: Cho Feo /Fe2+ E3+ Eo +/Ag Ag trong pin. Bi tp 4: ChoAgo/Ag E+ = 0,799V; Ni2+/Ni Eo = -0,23V
1. Vit s pin dng xc nh Eo. Ch r cc dng, cc m. 2. Cho bit sc in ng ca pin, phn ng xy ra trong pin theo qui c v

= 0,771 V;

E Cu2+/Cu

= 0,337V;

Eo +/H2 2H

= 0,00V ;

= 0,80V

Hy thit lp pin c th c to thnh; vit s pin v cc phn ng xy ra

theo thc t.
3. Nu ghp 2 in cc tiu chun Ag v Ni th sc in ng ca pin Epin=?

Phn ng trong pin nh th no? Bi tp 5: ChoCu2+/Cu Eo = 0,34V; Ago+/Ag E

13

= 0,80V; Feo /Fe E3+

= - 0,44V.

Nguyn Hu THPT Chuyn Hng Yn

1. Vit s pin xc nh cc th kh chun v vit phng trnh phn ng

xy ra khi pin hot ng.

2. Hy vit cc s pin khi ghp in cc Fe vi in cc Cu, in cc Cu

vi in cc Ag. Vit phng trnh phn ng v tnh E0pin. Bi lm: 1. S pin xc nh cc th kh chun. Eo 2+/Cu = 0,34V > Eo +/H2 = 0,00V 2H Cu E Ag+/Ag S pin: H2 (Pt)H+ (C = 1M)Cu2+ (C = 1M)Cu cc m (ant): qt OXH cc dng (catt): qt kh Phn ng trong pin: H2 + Cu2+ (1/2)H2 + Ag+ E Fe2+/Fe
o o

= 0,80V+/H2 Eo 2H >

= 0,00V

H2

2H+ + 2e Cu

Cu2+ + 2e Cu + 2H+

H2 (Pt)H+ (C = 1M)Ag+ (C = 1M)Ag Ag + H+ = 0,00V = -0,44V < Eo 2H+/H2

S pin: FeFe2+ (C = 1M)H+ (C = 1M)H2 (Pt) Fe + 2H+ Fe2+ + H2 a. S pin khi ghp in cc Fe vi in cc Cu Eo Cu
2+

/ Cu

= 0,34 > E0 Fe

2+

/ Fe

= -0,44V

Cu/Cu2+ : cc dng (catt) Fe/Fe2+ : cc m (ant) S pin FeFe2+ (C = 1M)Cu2+ (C = 1M)Cu Phn ng trong pin: Eopin = Eof Eot = Eo Cu
2+

Fe + Cu2+
/ Cu

Fe2+ + Cu
/ Fe

- E0 Fe

2+

Eopin = 0,34 (- 0,44) = 0,78 (V) b. Ghp cc Cu vi cc Ag

14

Nguyn Hu THPT Chuyn Hng Yn E0 Ag

+

/ Ag

> Eo Cu

2+

/ Cu

Ag/Ag+ : cc dng (catt) Cu2+/Cu: cc m (ant) S pin: (-) CuCu2+ (C = 1,0)Ag+ (C = 1,0)Ag (+) Phn ng trong pin: Eopin = E0 Ag Fe3+/Fe2+ [Fe(CN)6]3-/[Fe(CN)6]4NO3-, H+/ NO, H2O NO3-, H2O/ NO2Al3+/Al Da vo s liu trn hy:
1. Lp cc pin; Epin (ghi kt qu theo th t gim dn) 2. Vit phng trnh phn ng xy ra trn mi in cc v phn ng xy ra
+

Cu + 2Ag+
2+

2Ag + Cu2+

/ Ag

- Eo Cu

/ Cu

= 0,8 0,34 = 0,46 (V) 0,77V (1) 0,36V (2) 0,96V (3) 0,1V (4) -1,66V (5)

Bi tp 6: Tr s Eo ca mt s in cc 25oC

trong pin (vit s pin) khi ghp:

a) T in cc 2 5 b) T in cc 3 5 c) T in cc 3 4

Bi lm: 1. Theo bi ra ta c bng s liu. S th t 1 2 3 4 5 6 7 8 9 in cc + 3 1 2 4 3 1 3 1 2

15

in cc 5 5 5 5 4 4 2 2 4

Eopin (V) 2,62 2,43 2,02 1,76 0,86 0,67 0,60 0,41 0,26

Nguyn Hu THPT Chuyn Hng Yn 10 2. a. in cc 2 5. E0 Fe(CN )

6 3

3 = -1,66V

0,19

/ Fe ( CN ) 6 4

= 0,36 > E0 Al

3+

/ Al

Pt[Fe(CN)6]3-;[Fe(CN)6]4- : cc dng (catt) Al/Al3+ S pin: AlAl3+ (C = 1M)[Fe(CN)6]3-/ [Fe(CN)6]4-Pt cc m (ant): qt OXH cc dng (catt): qt kh phn ng trong pin: Al + 3[Fe(CN)6]3b. in cc 3 5 E3 > E5 S pin: AlAl3+ (C = 1M)NO3-, H+NO (Pt) cc m (ant): qt OXH cc dng (catt): qt kh Phn ng trong pin: Al + NO3- + 4H+ c. in cc 3 4. S pin: (-) PtNO3-, NO2-NO3-, H+NO (Pt) (+) cc m (ant): qt OXH cc dng (catt): qt kh Phn ng trong pin: 3NO2- + 2OHsau: a. Fe2+ + Ag+ Fe3+ + Ag Ag2CrO4 + 2Fe2+
16

: cc m (ant)

Al

Al3+ + 3e [Fe(CN)6]4-

[Fe(CN)6]3- + e

Al3+ + 3[Fe(CN)6]4-

Al

Al3+ + 3e NO + 2H2O

NO3- + 4H+ + 3e

Al3+ NO + 2H2O

E3 > E4

NO2- + 2OH-

NO3- + H2O + 2e NO + H2O

NO3- + 4H+ + 3e

NO3- + NO + H2O

Bi tp 7: Thit lp s pin sao cho khi pin hot ng xy ra cc phn ng

b. 2Fe3+ + 2Ag + CrO42-

Nguyn Hu THPT Chuyn Hng Yn c. HSO4- + CH3COOBi lm: a. b. PtFe2+, Fe3+ Ag+Ag AgAg2Cr2O4; CrO42- Fe3+, Fe2+Pt (1/2)H2 e H+ CH3COOH H+ + SO42(1/2)H2 CH3COO- + H+ Cc dng (catt): Qu trnh kh: HSO4H+ + e pin c thnh lp: (Pt) H2CH3COO-; CH3COOH HSO4-, SO42-H2 (Pt) Bi tp 8: Thit lp cc s pin da vo cc phng trnh phn ng sau. 1. Zn + Cu2+ 2. Ag+ + Cl3. Zn + Cl2 4. Ce4+ + Fe2+ 6. Ag + Fe3+ 7. Cd + CuSO4 8. 2Ag+ + H2 9. Ag+ + I10. H2 + Cl2 12. Pb + 2HCl Bi lm: Thit lp s pin da vo phng trnh phn ng 1. Zn + Cu2+ Cu + Zn2+ Zn Zn2+ + 2e Cu Cu2+ + 2e cc m (ant): qt OXH cc dng (catt): qt kh S pin: ZnZn2+ (C1)Cu2+ (C2)Cu
17

CH3COOH + SO42-

c. Cc m (anot): Qu trnh OXH:

Cu + Zn2+ AgCl ZnCl2 Ce3+ + Fe3+ Mn2+ + Cl2 + H2O CdSO4 + Cu 2Ag + 2H+ AgI 2HCl ZnSO4 + 2Hg PbCl2 + H2 Ag+ + Fe2+

5. MnO4- + H+ + Cl-

11. Zn + Hg2SO4 (r)

Nguyn Hu THPT Chuyn Hng Yn 2. Ag + ClAgCl Ag + ClAg+ + e AgCl + e Ag

cc m (ant): qt OXH cc dng (catt): qt kh S pin

Ag,AgClCl-(C1)Ag+ (C2)Ag 3. Zn + Cl2 ZnCl2 Zn Zn2+ + 2e 2ClCl2 + 2e cc m (ant): qt OXH cc dng (catt): qt kh S pin: ZnZn2+ (C1)Cl- (C2)Cl2 (Pt) 4. Ce4+ + Fe2+ Ce3+ + Fe3+ Fe2+ Fe3+ + e Ce3+ Ce4+ + e cc m (ant): qt OXH cc dng (catt): qt kh S pin PtFe2+, Fe3+Ce4+, Ce3+Pt 5. MnO4- + H+ + Clcc m (ant): qt OXH cc dng (catt): qt kh S pin: (-) Cl2 (Pt)Cl-MnO4-, H+, Mn2+Pt (+) 6. Ag + Fe2+ Ag+ + Fe2+ Ag Ag+ + e Fe2+ Fe3+ + e cc m (ant): qt OXH cc dng (catt): qt kh S pin: (-) AgAg+ (C1)Fe3+, Fe2+Pt (+) 7. Cd + CuSO4 CdSO4 + Cu (-) CdCdSO4CuSO4Cu (+) 8. 2Ag+ + H2 2Ag + 2H+
18

Mn2+ + Cl2 + H2O 2ClCl2 + 2e Mn2+ + 4H2O MnO4- + 8H+ + 5e

tng t s pin:

S pin:

Nguyn Hu THPT Chuyn Hng Yn (-) H2H+ (C1)Ag+Ag (+) 9. Ag+ + IAgI (-) Ag, AgII-Ag+Ag (+) 10. H2 + Cl2 2HCl (-) 11. Zn + Hg2SO4 Zn cc m (ant): cc dng (catt): S pin: (-) ZnZn2+SO42-Hg2SO4, Hg (+) 12. Pb + 2HCl PbCl2(r) + H2 Pb + 2Cl2H+ + 2e PbCl2(r) + 2e H2 cc m (ant): cc dng (catt): S pin: (-) Pb, PbCl2Cl- H+H2 (Pt) (+) Bi tp 9: a) Hy to ra pin trong c xy ra phn ng sau: Pb(r) + CuBr2 (dd 0,01M) PbBr2 (r) + Cu (r) b) Vit s pin v phn ng xy ra mi in cc cho E0 Pb
2+

S pin (tng t cu 2)

S pin: (Pt) H2H+Cl-Cl2 (Pt) (+) ZnSO4 + 2Hg Zn2+ + 2e 2Hg + SO42Hg2SO4 + 2e

/ Pb

= -0,126V; E0 Cu

2+

/ Cu

= 0,34V

c) 25oC Epin = 0,442V th T PbBr = ?

2

Bi 10 : AgCl l hp cht halogen khng tan v mu trng. kho st tan da vo bt in ho, ngi ta thit lp 1 pin in ho gm 2 phn c ni bi cu mui. + bn tri l mt thanh Zn c nhng vo dd Zn(NO3)2 0,2M + bn phi l mt thanh Ag c nhng vo dd AgNO3 0,1M Vmi dd = 1 lt a) Vit phng trnh phn ng xy ra khi pin phng in v tnh Epin
19

Nguyn Hu THPT Chuyn Hng Yn b) Gi s pin phng in hon ton v lng Zn d. Tnh in lng phng trong TN. c) Trong 1 TN khc ngi ta cho KCl rn vo bn phi pin ban u cho n khi [K+] = 0,3M. Xy ra s kt ta Ag v thay i s. Sau khi thm E = 1,04V. + Tnh [Ag+] = ? + [Cl-] = ? v TAgCl = ? bit E0 Zn
2+

/ Zn

= -0,76V

E0 Ag

/ Ag

= 0,8V

20

Nguyn Hu THPT Chuyn Hng Yn

KT LUN
Trn y ch l mt s vn nh ca ni dung kin thc phn in ho hc, nhm mc ch gip hc sinh tho g nhng kh khn, lng tng khi gii cc bi tp v pin in Trong vic bi dng hc sinh gii nhng nm qua vic p dng chuyn ny thc s gip cc em hc sinh gii quyt tt nhng bi tp v pin in ; n gip cc em h thng ho kin thc mt cch nhanh v y nht t vn dng vo cc dng bi tp c th mt cch d dng. Ni dung kin thc n luyn cho i tuyn hc sinh gii quc gia phn in ho hc cn rt nhiu vn , ti xin c tip tc cp nhng chuyn tip theo. Hng Yn - 2008

Ti liu tham kho:

1. Mt s vn chn lc tp 2 2. Ho hc phn tch - Nguyn Tinh Dung 3. C s l thuyt ho hc - Nguyn Hnh 4. C s l thuyt cc qu trnh ho hc - V ng 5. Nguyn nh Chi 6. Ti liu dng bi dng hc sinh gii - 2002. B GD v o to - Tr 20 7. C s LT ho hc (phn BT) - L Mu Quyn 8. Ti liu nng cao v m rng kin thc ho hc - Tr 49 21

Nguyn Hu THPT Chuyn Hng Yn

22

Nguyn Hu THPT Chuyn Hng Yn II. S ph thuc ca th vo nng PT Nernst Cc yu t nh hng n cn bng OXH kh 1. S ph thuc th theo nng Xt: aOx + ne E=E
o OXH/kh

bkh

RT [Ox] a ln + nF [ Kh]b

ti 25oC; R = 8,314 E=E

o OXH/kh

0,059 [Ox] a lg + n [ Kh]b

VD 1: Tnh th ca in cc Pt nhng trong dd Fe3+ 0,01M, Fe2+ 0,1M bit E0

Fe 3 + / Fe 2 +

= 0,77V Fe3+ + e Fe2+

0,059 [Ox] a + n lg [ Kh]b

Bi lm: PT Nernst E =E
o 0 Fe 3 + / Fe 2 +

= 0,77 +

0,059 0,01 lg = 0,712 (V) 1 0,1

VD 2: Thit lp th in cc theo PT Nernst i vi cc phn ng sau v tnh. 1.

4

MnO4- + 8H+ +5e

Mn2+ + 4H2O
2+

C MnO = 0,2M; pH = 1; C Mn = 0,1M E = E0 2. E0 Fe(CN ) 3. 4.

6
MnO4

/ Mn

2+

0,059 [ MnO4 ][ H + ]8 + 5 lg [ Mn 2+ ]
4 Fe(CN) 6

Fe(CN) 3 + e 6
4

/ Fe ( CN ) 6 4

= -0,2;

C Fe(CN ) = 0,25M; C Fe(CN ) = 0,1M

4 6 3 6

Fe(OH)3 + e cho pH = 10 O2 + 2H+ + 4e

Fe(OH)2 + OH2H2O

E0 Fe (OH ) Eo = 1,23V

/ Fe ( OH ) 2

= -0,52

bit PO 2 = 0,5at; pH = 1
23

Nguyn Hu THPT Chuyn Hng Yn 2. Hng s cn bng ca phn ng OXH kh OX1 + ne Kh2 Kh1 OX2 + ne Eo OXH Eo OXH
1

/ kh1

= Eo1

Go1

/ Kh2

= Eo2 G02

Go = Go1 + G02 = -nF Eo1 + nF Eo2 = -nFEo Eo = Eo1 - Eo2 Ta li c: Go = -RTlnK -RTlnK = -nFEo lgk = 2,303 RT E lgk = n n
1 nF
o

Ti 25oC

E o k = 10 0,059

VD 1: Xt kcb = ? ca cc phn ng sau: a. Mg + 2H+ Cho E0 Mg

2+

Mg2+ + H2 = -2,363V Cu2+ + 2Ag = 0,8V; Eo Cu

2+

/ mg

b. 2Ag+ + Cu bit E0 Ag
+

/ Ag

/ Cu

= 0,34V

c. Phn ng OXH Cl- bng MnO4bit E0 MnO

4

/ Mn 2 +

= 1,51V; E0 Cl

/ 2 Cl

= 1,36V
3+

d. Phn ng kh H2S bi Fe3+. E0 Fe H2S cho pk1 = 7,02; pk2 = 12,9

/ Fe 2 +

= 0,77V; E0 S / S = -0,48
2

3. nh gi chiu hng v mc phn ng OXH kh VD 2: Fe3+ + Ag

3+

Fe2+ + Ag+
+

k=? = 0,799V

bit E0 Fe

/ Fe 2 +

= 0,771V; E0 Ag

/ Ag

VD 3: Tnh hng s K ca phn ng kh H2S bng Fe3+ bit E0 Fe H2S Bi tp Bi1: Cho cc in cc.
24
3+

/ Fe 2 +

= 0,771V; E0 S / S = -0,48
2

pk1 = 7,02; pka 2 = 12,9

Nguyn Hu THPT Chuyn Hng Yn a. CdCd2+ (C Cd = 0,1M)

2+

Eo = -0,403V

b. (Pt) Cl2(p = 1atm)Cl- (C Cl = 0,01M) c. Ag, AgBrBr- (C = 0,005M) d. PtSn2+ (C1 = 0,02M), Sn4+ (C2 = 0,04M) e. Hg, Hg2SO4SO42- (C = 0,015) 1. Vit phn ng in cc v tnh cc th in cc

Eo = 1,36V Eo = 0,071V Eo = 0,15V Eo = 0,62V

2. Nu ghp tng i in cc a c; a d; b c to thnh pin th hy vit s pin v tnh Epin Bi 2: Cho bit th O K tiu chun E0 Cu E0 Cu
2+

/ Cu

= 0,16V = 0,52V

E0 Fe

3+

/ Fe 2 +

= 0,77V = -0,44V

/ Cu

E0 Fe

2+

/ Fe

Hy cho bit hin tng g xy ra trong TH sau.

1. Cho bt Fe vo dd Fe2(SO4)3 0,05M 2. Cho bt Cu vo dd CuSO4 1M

Bi 3: Xt s sau: ZnZn2+ (0,18M)Ag+ (0,3M)Ag a. Xc nh th in cc ca mi in cc trn. Vit phn ng xy ra trn mi in cc v tnh Epin = ? b. kcb = ? bit E0 Zn Bi 4: 1. Cho E0 O
2
2+

/ Zn

= -0,76V; E0 Ag

/ Ag

= 0,8V

/ H 2O

= 1,23V; pkW = 14 = ? 25oC

+

E0 O

/ OH

2. Xt kh nng ho tan ca Ag trong H2O c O2 khng kh bit E0 Ag Bi 5: Thit lp s pin gia Cr2O72- vi Fe2+ vi pH = 0 Cho E0 Cr O
2 7 2

/ Ag

= 0,8V

/ Cr 3 +

= 1,33V

C Fe = 0,1M
3+

C Cr O
2 3+

= 0,1M

E0 Fe

3+

/ Fe 2 +

= 0,77V

C Fe = 0,01M
2+

C Cr = 0,2M

thnh phn mi dd khi pin phng in hon ton

, 77 Bi 6 Cho O2 0,68V H2O2 1V H2O

1. a) Vit phng trnh phn ng

25

Nguyn Hu THPT Chuyn Hng Yn b) So snh bn tng i ca 3 dng c) E0 O

2

/ H 2O

. H2O2/H2O; O2/H2O; O2/H2O2

2. Thit lp s ph thuc ca th in cc vo pH ca cc cp

3. Cho E0 MnO

/ Mn 2 +

= 1,51V. Vit phng trnh phn ng v thit lp s pin

gia MnO4- v H2O2. 1 lt dd cha 0,15 mol KMnO 4; 0,085 mol H2O2 v 0,8 mol H2SO4. Tnh CM cc cht sau phn ng. Bi 7: a) Hy to ra pin trong c xy ra phn ng sau: Pb(r) + CuBr2 (dd 0,01M) PbBr2 (r) + Cu (r) b) Vit s pin v phn ng xy ra mi in cc cho E0 Pb
2+

/ Pb

= -0,126V; E0 Cu

2+

/ Cu

= 0,34V

c) 25oC Epin = 0,442V th T PbBr = ?

2

Bi 8: AgCl l hp cht halogen khng tan v mu trng. kho st tan da vo bt in ho, ngi ta thit lp 1 pin in ho gm 2 phn c ni bi cu mui. + bn tri l mt thanh Zn c nhng vo dd Zn(NO3)2 0,2M + bn phi l mt thanh Ag c nhng vo dd AgNO3 0,1M Vmi dd = 1 lt a) Vit phng trnh phn ng xy ra khi pin phng in v tnh Epin b) Gi s pin phng in hon ton v lng Zn d. Tnh in lng phng trong TN. c) Trong 1 TN khc ngi ta cho KCl rn vo bn phi pin ban u cho n khi [K+] = 0,3M. Xy ra s kt ta Ag v thay i s. Sau khi thm E = 1,04V. + Tnh [Ag+] = ? + [Cl-] = ? v TAgCl = ? bit E0 Zn
2+

/ Zn

= -0,76V

E0 Ag

/ Ag

= 0,8V

Bi 9: nh gi kh nng phn ng gia Cu2+ vi dd KI d bit E0 Cu

2+

/ Cu

= 0,34V; E0 Cu

/ Cu

= 0,52V
26

Nguyn Hu THPT Chuyn Hng Yn E0 I

3

/ 3I

= 0,55V; CuI

Cu+ + I-

Ks = 10-12

Bi 10: Phn ng gia AgNO3 vi KCl trong dd to AgCl v gii phng nng lng. Ta c th to ra 1 t bo in ho sinh cng nh phn ng .
1. Vit CT t bo quang in v vit phn ng trn ant, catt. 2. Go298k ca phn ng kt ta AgCl v Eo298 ca t bo in ho

cho TAgCl = 1,6.10-10 25oC Bi 11: a. Kcb ca phn ng: Fe3+ + Sn2+ cho E0 Fe E0 Fe
3+

Fe2+ + Sn4+
2+

/ Fe 2 +

= 0,77V =?

E0 Fe

/ Fe

= -0,44V

E0 Sn

4+

/ Sn 2 +

= 0,15V

3+

/ Fe

b. cho E0 Fe bit

3+

/ Fe 2 +

= 0,77V tnh E0 Fe(OH ) Fe3+ + 3OHFe2+ + 2OH-

/ Fe ( OH ) 2

=?

Fe(OH)3 Fe(OH)2
2

Ks1 = 10-37,5 Ks2 = 10-15,6

c. E0 S / S = -0,48V bit H2S Eo S / H S = ?

2

pk1 = 7; pk2 = 12,9

d. E0 Ag e. E0 Fe

/ Ag

= 0,8V = 0,77V

E0 Ag CrO
2

/ Ag

=?
2+

pk sAg CrO = 12
2 4

3+

/ Fe 2 +

E0 FeF / Fe = ?
3

Fe3+ + 3F-

FeF3

= 1012

27

Nguyn Hu THPT Chuyn Hng Yn Ngy 21 Thng 7 nm 2007 KIM TRA CHUYN IN HO HC (Thi gian : 150 pht)
Cu I: Da vo th in cc chun ca cp oxi ho - kh . Hy d on chiu phn ng xy ra trong cc h sau y 1. KMnO4 + FeSO4 + H2SO4 2. KMnO4 + FeCl3 + H2SO4 3. K2Cr2O7 + FeBr3 + H2SO4 4. K2Cr2O7 + KI + H2SO4 Cc th tiu chun cn xt: E0 4-, H+/Mn2+ = 1,51V E0 2O72-, H+/Cr3+ = 1,33V Cr MnO
0 EFe3+/Fe2+

= 0,77V = 1,36V

E0Br2/ 2Br E0 I2/ 2I -

= 1,07V = 0,54V

E0 2/ 2ClCl

Cu II : 1. Khi ghp thnh pin th cp AgBr/Ag ng vai tr anot, cp Fe3+/ Fe2+ ng vai tr catot. Hy vit s pin, phng trnh phn ng ca pin khi pin hot ng. M t chiu dch chuyn ca cc in tch trong pin 2. Cho E0 pin = 0,698V E0 = 0,771V E0Ag+/ Ag = 0,799V
AgBr = ? Tnh T

3. Tnh E pin nu C - = 0,1M ; Br

CFe 3+

= 0,001M ;

C Fe 2+

= 0,1M

4. Tnh nng ca mi ion trong dung dch khi pin phng in hon ton. Tnh th ca mi in cc ti thi im . Cu III: 1. Cho pH = 14 v s sau: ClO30,35V

ClO2-

0,58V

ClO-

0,93V

Cl -

a. Vit phng trnh ion ca cc na phn ng. b. So snh bn ca cc dng oxi ho - kh.
0 c. Tnh EClO3-, / Cl-

pH = 0

2. Thit lp s pin khi xy ra phn ng di y: Cu2+ + 4NH3 Cu(NH3)4 2+ Cu IV: Thit lp khu vc pH c th oxi ho c trn 80% Br- v di 5% Cl- t hn hp KBr 0,1M v KCl 1 M bi dung dch K2Cr2O7. E0 2O72-, H+/Cr3+ = 1,33V E0 Br2/ 2Br = 1,07V Cr
0 ECl2/ 2Cl-

= 1,36V

Cu V : 1.Tnh cn bng trong dung dch cha hn hp K2Cr2O7 0,1M , KBr 1M v Cr3+ 0,05M ti pH=0 Cho E0 2O72-, H+/Cr3+ = 1,33 V ; E0Br2/ 2Br - = 1,07V. Cr 2. Cho phn ng sau: 28

Nguyn Hu THPT Chuyn Hng Yn

NaBH4 + C0 KMnO4 = 0,16 M NaH2BO3 + MnO2 = 0,03M = 0,59V ;
NaBH4

; MnO40 C-

Xc nh s pin v thnh phn cn bng bit :

0 EMnO4-/ MnO2

E0H2BO3-/ BH4-

= 0,05V.

Cu VI: in phn dung dch cha Cu2+ 0,01M , Ni2+ 1M , Ag+ 0,001M , H+ 0,1M v ClO4- ; dng in cc Pt. 1. C 4- = ? trong dung dch. ClO
Ag 2. Cho E0 +/ Ag dy R dn

= 0,8V ;

E0 2+/ Cu = 0,34V ; Cu

E0Ni2+/ Ni = - 0,23V

= 0,5 ; Cng dng in I = 2 ;O2/ 0H2O E

= 1,23V. Qu th ca O2O2 /Pt

=0,5V Tnh th t vo qu trnh in phn bt u xy ra? Nu in phn ht Ag+ th Cu2+ b in phn cha ?. 3. Trong iu kin in phn c th in phn c Ni2+ khng?.

29