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D. Tài Liệu Hóa- Vương Bá Huy- THPT Chuyên Bắc Ninh
D. Tài Liệu Hóa- Vương Bá Huy- THPT Chuyên Bắc Ninh
PIN IN HA
Phn I: TNG QUAN
I. TM QUAN TRNG, VAI TR CA PHN NG TRONG PIN IN:
Trong chng trnh ho hc ph thng c cp ti phn ng oxi ha - kh, trong
loi phn ng ny c th chia lm hai loi:
Loi th nht l phn ng trong c s trao i electron trn b mt ca cc cht tip,
y l loi phn ng oxi ha kh ph bin.
Loi th hai l phn ng trao i electron trn b mt ca hai in cc, loi ny c
gp trong in phn v trong pin in.
Phn ng oxi ha kh xy ra trong pin in chng trnh hc sinh cc trng ph
thng gp khng nhiu. Nhng trong chng trnh chuyn ha v c bit trong cc bi thi
hc sinh gii cp Quc gia v Quc t c cp ng k.
II. TNH HNH THC T NI DUNG KIN THC V PIN IN TRONG
CC TI LIU HIN HNH:
Trong cc ti liu hin hnh th ch yu l cc ti liu cho hc sinh n luyn thi i
hc v cao ng, cc ti liu ny qu nhiu m khng c s thng nht mt l thuyt chun
mc m nng v bi tp tnh ton gy cho hc sinh li hc th ng, khng c tnh sng
to v km t duy v ho hc. Bn cnh nhng ti liu ny thy cc ti liu dnh cho hc
sinh gii, hc sinh chuyn cn t v c bit ti liu dnh cho thi HSG Quc gia, Quc t
thc s l qu t.
V ni dung kin thc cc loi phn ng trong cc ti liu hin hnh ch yu cp
nhiu v phn ng trao i ion to ra cht kt ta, phn ng axit - baz v phn ng oxi
ho kh do s trao i electron trn b mt ca cc cht. Cn phn ng oxi ha kh xy ra
trong pin in trong sch gio khoa vit rt s ng v c bit mi lin h v nh hng
ca cc loi phn ng ha hc trong pin in sch gio khoa ph thng l khng c. Mt
2
khc trong cc ti liu sch dng cho sinh vin cng ch vit theo mt h thng c bn,
cha c h thng su rng v a dng cc loi pin in. iu c bit l cha xy dng
mi lin kt cc loi phn ng trong pin in.
Chnh v nhng kh khn trn y, ti xy dng ti: Phn loi, xy dng
cu trc cc bi tp v pin in ha phc v cho vic bi dng hc sinh gii Quc gia
III. MC TIU CA TI:
Mc tiu ca ti ny l xy dng cu trc cc bi tp v pin in, qua phn
loi, nh gi tc dng ca cc bi tp phn ng oxi ha - kh trong pin in v cc phn
ng lin quan phc v cho vic bi dng hc sinh gii Quc gia.
IV. PHNG PHP THC HIN:
- Nghin cu l thuyt v cc qu trnh oxi ha, qu trnh kh cc in cc, s vn
dng l thuyt phn ng oxi ha kh trong ging dy ho hc trng ph thng v cc
trng chuyn. Xt cc mi quan h gia cc loi phn ng khc nhau c lin quan n
phn ng oxi ha kh.
- iu tra thu thp cc ti liu c lin quan n phn ng oxi ha kh qua h
thng sch gio khoa, sch bi tp ph thng, cc thi tuyn sinh vo cc trng i hc
v cao ng, cc thi hc sinh gii cc tnh, thi hc sinh gii Quc gia vng mt v
vng hai, ti liu Olympic Vit Nam Quc t, ti liu chun b cho thi Olympic Quc t
v mt s ti liu khc.
- Phn tch c chn lc cc bi tp trong sch gio khoa, cc thi hc sinh gii v
mt s bi xut thm phn loi nh gi cc bi tp v phn ng trong pin in.
- T nh ra cc cu trc cc bi tp v phn ng xy ra trong pin in.
V. VAI TR CA BI TP TRONG VIC BI DNG HC SINH GII
QUC GIA:
t ra c cc yu cu cho hc sinh trong qu trnh ging dy th vic la chn,
xy dng cc bi tp l mt vic lm ht sc quan trng v cn thit i vi mi gio vin.
Thng qua bi tp, gio vin s nh gi c kh nng nhn thc, kh nng vn dng
kin thc ca hc sinh. Bi tp l phng tin c bn nht dy hc sinh tp vn dng
kin thc vo thc hnh. Qu trnh vn dng kin thc thng qua cc bi tp c rt nhiu
3
hnh thc phong ph v a dng. Thng qua vic gii cc bi tp m kin thc c cng
c khc su, chnh xc ho, m rng v nng cao. Cho nn bi tp va l ni dung, va l
phng php, va l phng tin thc y vic dy tt v hc tt.
c bit, bi tp ho hc l phng tin c bn dy hc sinh vn dng cc kin
thc ho hc vo thc t i sng, sn xut v tp nghin cu khoa hc. Bi tp ho hc
c tc dng gio dc tr dc v c dc rt ln. l:
- Rn luyn cho hc sinh kh nng vn dng c cc kin thc hc.
- o su v m rng kin thc mt cch phong ph, hp dn.
- n tp, cng c v h thng ho kin thc mt cch d hiu nht.
- Rn luyn c k nng cn thit v ho hc, nh k nng cn bng phng trnh, k
nng tnh ton, k nng t duy c th ring ca mn ho hc,.v.v...
- Pht trin nng lc nhn thc, tr thng minh cho hc sinh.
- Gio dc t tng, o c, tc phong nh rn luyn tnh kin nhn, trung thc, sng
to, chnh xc, khoa hc. Nng cao lng yu thch hc tp b mn. Qua , pht trin mt
cch ton din nhn cch cho hc sinh.
2. in cc loi II:
L mt h in ha gm mt kim loi b bao ph mt hp cht kh tan (mui hoc
hiroxit hoc oxit) nhng vo mt dung dch cha anion ca hp cht kh tan :
M, MA A(C) .
V d 1: in cc Ag, AgCl KCl(C). Cho Ks = 10-10, EoAg+/Ag = 0,799V. Tnh EoAgCl/Ag v
EAgCl/Ag khi C = 2M.
Phn tch: y l mt h in ha c qu trnh xy ra ca phn ng oxi ha kh
v cn bng ca hp cht t tan. Hc sinh c th vn dng a dng vi cc hp cht t tan
khc.
Hng dn:
* Tnh EoAgCl/Ag:
+ Tnh theo t hp cn bng:
Ag+ + e Ag
K1 = 100,799/0,0592
Ks = 10-10
Ka
(*)
Vi PH2=1 atm; [H+] = (Ka.[HA])1/2 (Ka.CHA)1/2 (khi gi thit HA l axit yu hay rt yu)
thay vo (*), ta c:
E2HA/H2 = (0,0592/2)lgKa + (0,0592/2)lgCHA => Khi bit CHA, o c E2HA/H2 l
tnh c Ka.
b) in cc kh clo:
V d 5: Vit in cc, na phn ng v biu thc lin quan ti th kh ca in cc kh
clo.
Hng dn:
in cc Pt, Cl2( x atm) Cl- (C)
Na phn ng: Cl2 + 2e 2Cl=> ECl2/2Cl- = EoCl2/2Cl- + (0,0592/2)lgPCl2/(CCl-)2
Khi x = 1 ; => ECl2/2Cl- = EoCl2/2Cl- - 0,0592lgCClc) in cc kh oxi:
V d 6: Vit in cc, na phn ng v biu thc lin quan ti th kh ca in cc kh
oxi.
Phn tch: Phn ny gip cho hc sinh hiu qu trnh kh ca oxi trong cc mi
trng khc nhau v kh nng oxi ha ca oxi ph thuc vo pH ca mi trng. Qua biu
thc thy c nu pH cng nh th kh nng oxi ha ca oxi cng mnh.
Hng dn:
+ Vi in cc:
9
(**)
EoZnO22-/Zn=-1,22V;
EoHgO/Hg=0,12V
3. Pin Zn - PbO2 c nhng trong dung dch H2SO4 38%. EoPbO2/Pb = 1,455V
10
sinh suy lun dng oxi ha v dng kh to ra khi pin lm vic s tham gia phn ng
ion CO32- khng i.
+ Na phn ng anot: H2 + CO32- CO2 + H2O + 2e
Na phn ng catot: 1/2 O2 + 2e + CO2 CO32=> Phng trnh phn ng khi pin hot ng:
H2 + 1/2 O2 H2O
=> S pin:
(-) C-Ni, H2 Na2CO3(n/c) O2, C-Ni-Ni (+)
2)
H+ + RCOO- RCOOH
2)
3)
4)
5).
6)
AgCl + 2CN- [Ag(CN)2]- + ClPhn tch: y l mt loi pin in m phng trnh phn ng ca pin in li
khng phi l phn ng oxi ha kh (phn ng axit baz, phn ng to hp cht t tan,
phn ng chuyn t cht t tan sang cht t tan hn, phn ng to phc, phn ng chuyn
t phc km bn sang phc bn, phn ng chuyn t hp cht t tan sang dng phc,...).
vit c s ca loi pin in ny, hc sinh phi xc nh:
- Hai in cc u c cng dng ox/kh, ch c iu s tn ti ca mi dng oxi ha hoc
dng kh (thng dng oxi ha) l khc nhau.
- Gi tr th ca dng ox/kh no ln hn.
Hng dn: T cc cp ox/kh v nhn thy gi tr th ca cc cp,... c cc s
pin in v cc na phn ng trn in cc l:
1) S pin in c phn ng: H+ + RCOO- RCOOH
(-) Pt, H2(P) RCOO-(C1) H+(C2) H2,(P) Pt (+)
Na phn ng anot: H2 + 2RCOO- 2RCOOH + 2e
Na phn ng catot: 2H+ + 2e H2
2) S pin in c phn ng: 2Ag+ + SO42- Ag2SO4
(-) Ag, Ag2SO4 K2SO4(C1) Ag+(C2) Ag (+)
16
B. BI TP VN DNG:
I. Vit s pin, cc qu trnh, phng trnh phn ng khi
pin hot ng, tnh sut in ng ca pin:
V d 11: Thm 0,40 mol KI vo 1 lt dung dch KMnO4 0,24 M pH = 0
a) Tnh thnh phn ca hn hp sau phn ng.
b) Tnh th ca in cc platin nhng trong hn hp thu c so vi in cc
calomen bo
Cho pH = 0 v 25oC th in cc tiu chun E o ca mt s cp oxi
ho - kh c cho nh sau: 2IO4/ I2 (r) = 1,31V; 2IO3/ I2 (r) = 1,19V;
17
0,24
0,4
C 0,08
C
+ 10 I + 16 H+
0,4
0,16
0,08
0, 2
= 10 176
CO
0,16
0,16
0,2
0,08
0,08
0,12
0,16
0, 24
18
AgOH + H+
(1) ;
K1= 10 11,70
Pb2+ + H2O
PbOH+ + H+
Ch s tch s tan pKs: AgI l 16,0 ; PbI2 l 7,86 ; AgSCN l 12,0; E0Ag+/Ag = 0,799V.
Phn tch: y l bi ton h in ha gm hai in cc u l in cc kim loi
c bao ph bi hp cht t tan, cc qu trnh xy ra mi in cc c nh hng ca
hp cht t tan, nn th kh ca mi cp s thay i. hiu v lm c dng bi ny,
hc sinh phi nm trc cn bng ca hp cht t tan, phn nng cao ca bi ton l cho h
in ha c nhiu hp cht t tan, nn hc sinh phi xt n cn bng chnh. Khi hc sinh
tnh th kh ca cp ox/kh, thng hc sinh kh hiu gi tr ca dng oxi ha v dng kh
trong biu thc tnh theo phng trnh Nec (hoc hiu l gi tr ban u ca dng oxi ha,
dng kh) l bao nhiu ? iu ny gio vin nhn mnh cho hc sinh thy c gi tr
dng oxi ha, dng kh trong biu thc tnh, chnh l gi tr tn ti trng thi cn bng
ca cn bng chnh.
Hng dn:
1a) Dung dch B: Thm KI : CAg+ = 0,025 M; CPb2+ = 0,050
CI- = 0,125M ; CH+ = 0,10M
19
Ag+
AgI
I-
0,025
0,125
0,10
Pb2+
PbI2
2 I-
0,05
0,10
Ag+ + I-
PbI2
Pb2+ + 2I-
Ks1 << Ks2, vy trong dung dch cn bng (4) l ch yu. S to phc
hiroxo ca Pb2+ l khng ng k v c H+ d:
Pb2+ + H2O
PbOH + H+ ;
PbOH 10
Pb 10
7 , 8
10 6,8 PbOH Pb 2
PbI2
Pb2+ +
x
(2x)2x = 10-7,86
x = 1,51 . 10-3M
.10
Ag KI 31,02
.10
16
s1
K2 = 10-7,8
2I-
Ks2 = 1.10-7,86
2x
2x = [I-] = 2,302 . 10-3M
3,31.10 14 M .
Ag
E 1 0,001V
Dung dch X
20
Ag+ + SCN-
AgSCN
0,01
0,04
(0,03-x)
KS-1 = 1012,0
(0,01-x)
x(0,03-x) = 10-12
=> Ag x
10 12
3,33.10 11
2
3x10
Ag
b)
AgSCN
SCN - 0,03M
Ag
I-
AgI
+
Ag
I-
AgI
d)
K s ( AgSCN )
K s ( AgI)
+
+
SNC SNC -
10 12
10 4
16
10
V d 13:
1. Thit lp s pin v vit na phn ng khi pin hot ng xy ra phn ng:
CH3COO- + HSO4- CH3COOH + SO4221
2. Tnh Gpin
3. Tnh nng mol cc ion trong dung dch khi Ipin = 0.
4. Ghp pin xung i:
(-) Pt H2 CH3COO- (0,080M) HSO4- (0,050M) H2 Pt (+)
vi pin: (-) Ag,AgCl HCl (1,50M) KCl(bo ho) Hg2Cl2, Hg (+)
Cho EoAgCl/Ag = 0,222V; EHg2Cl2/Hg = 0,244V; KaCH3COOH = 10-4,76 ; KaHSO4- = 10-2,00
Vit cc bn phn ng ng xy ra mi in cc v cc phng trnh phn ng ?
Hng dn:
1. y l mt dng pin in m phn ng xy ra khi pin hot ng khng phi l
phn ng oxi ha kh (phn ng axit baz). xy dng c s pin in hc sinh
phi xc c dng oxi ha v dng kh mi in cc v th kh no ln hn xc
nh in cc catot (cc dng).
Do ion H+ t HSO4- nhiu hn ion H+ t CH3COO- nn c s pin l:
(-) Pt H2 (1 atm) CH3COO- (0,08M) HSO4- (0,05M) H2 (1 atm) Pt (+)
Na phn ng antot:
H2 + 2CH3COO- 2CH3COOH + 2e
Na phn ng catot:
2HSO4- + 2e H2 + SO42=> Phn ng xy ra khi pin hot ng:
CH3COO- + HSO4- CH3COOH + SO422. Tnh Gpin
Hng dn: tnh c Gpin ca loi pin in m phn ng xy ra ca pin khng
phi phn ng oxi ha kh (phn ng axit baz hoc phn ng to hp cht t tan hoc
phn ng to phc), hc sinh tnh theo th kh ca qu trnh kh mi in cc, sau
tnh ra sut in ca pin v tnh nng lng Gipx: Gpin = - nFEpin
+ Tnh E(-):
Theo cn bng:
CH3COO- + H2O CH3COOH + OHCo
1
22
Kb = Ka-1.Kw = 10-9,24
[]
(1-x)
=> K = ....= x2/(1-x) = 10-9,24 (vi 0 < x < 1) => x = [OH-] = 10-4,62
=> [H+] = 10-14/10-4,62 = 10-9,38
=> E(-) = 0 + (0,0592/2)lg[H+]2/PH2 = 0,0592lg10-9,38 = - 0,56(V)
+ Tnh E(+):
Theo cn bng:
HSO4Co
[]
(1-y)
H+ + SO42y
K = 10-2
=> K = .... = y2/(1-y) = 10-2 (vi 0 < y < 1) => y = [H+] = 0,095
=> E(+) = 0,0592lg[H+] = 0,0592lg0,095 = - 0,061(V)
Vy Epin = E(+) - E(-) = - 0,061 - (-0,56) = 0,499(V)
=> G = - nFEpin = - 2.96500.0,499 = - 96307(J) = - 96,307kJ
3. Tnh nng mol cc ion trong dung dch khi Ipin = 0.
Hng dn : Khi Ipin = 0, tc l pin ngng hot ng, lc ny hc sinh hiu rng
E(+) = E(-), nn Epin = 0 => G = 0, c ngha phn ng phn ng xy ra trong pin t ti
trng thi cn bng. V vy tnh nng ca cc ion cn bng .
Khi I = 0 c ngha l pin ngng phng in, tc l phn ng trong pin t n trng thi
cn bng:
CH3COO- + HSO4- CH3COOH +
Co
0,08
0,05
[]
(0,03+x)
(0,05-x)
0,08
[]
(0,08-x)
K = 10-9,24
=> K = ... = x2/(0,08-x) = 10-9,24 (vi 0 < x < 0,08) => x = 6,78.10-6
=> E(-) = 0,0592lg[H+] = 0,0592lg(10-14/6,78.10-6) = -0,52(V)
- in cc catot:
HSO4- H+ + SO42Co
0,05
[]
(0,05-x)
K = 10-2
=> K = ... = x2/(0,05-x) = 10-2 (vi 0 < x < 0,05) => x = 0,018
=> E(+) = 0,0592lg[H+] = 0,0592lg0,018 = - 0,103(V)
=> Epin(1) = E(+) - E(-) = -0,103 -(-0,52) = 0,417 (V)
+ Xt pin 2: (-) Ag, AgCl HCl (1,50M) KCl(bo ho) Hg2Cl2, Hg (+)
- Bn phn ng anot:
Ag + Cl- AgCl + e
=> EAgCl/Ag = EoAgCl/Ag + 0,0592lg(1/CCl-) = 0,222 + 0,0592lg(1/1,5) = 0,212(V)
=> Epin(2) = E(+) - E(-) = 0,244 - 0,212 = 0,032(V)
V Epin(1) = 0,417 > Epin(2) = 0,032(V), nn pin (1) c vai tr cung cp in cho pin (2) (pin
c np in). Do vy s pin c ni nh sau v cc bn phn ng xy ra:
Pin:
H2 + 2CH3COO-2CH3COOH +2e
I
/p:
2+
/Zn
0,0592
2+
lg[Zn ]
2
1. V axit HA l axit yu nn: Eo(2HA/H2) < Eo(2H+/H2) = 0V < Ecal (bo ho) = 0,244V, v vy
c s pin in l
(-) Pt, H2(1 atm) HA (C) KCl (bo ho) Hg2Cl2, Hg (+)
2. Ta lp dng c theo pin in trn, dng vn k o c sut in ng ca pin v
da biu thc:
E(-) = Eo2H+/H2 + (0,0592/2)lg[H+]2/PH2
= 0,0592lg[H+] = - 0,0592pH
=> Epin = E(+) - E(-) = 0,244 - (-0,0592pH); y o c Epin th s tnh c pH.
V d: Tnh pH ca dung dch HA khi Epin = 0,303V).
Ta c Epin = E(+) - E(-) = 0,244 - (-0,0592pH) = 0,303
=> pH = 1
3. Khi xc nh hng s cn bng ca mt axit yu HA (c nng mol/l l C). Ta
lp dng c s pin nh phn 1, o c sut in ng ca pin. T E pin, tnh c pH,
t pH tm c: [H+] = [A-] = 10-pH v [HA] = C 10-pH; => Ka = ([H+].[A-])/[HA]. V d:
Tnh Ka(HA) khi C = 10-2; Epin = 0,444V. Cho Ecal (bo ho) = 0,244V.
+ Tng t phn (2), ta c:
Epin = E(+) - E(-) = 0,244 - (-0,0592pH) = 0,444
=> pH = 3,38. Hay [H+] = 10-3,38 (M)
Xt cn bng:
HA
H+ + A-
K=?
Co 10-2
[ ] (10-2-10-3,38)
10-3,38 10-3,38
K1 = 104.1,23/0,0592
Kw = 10-14
O2 + 4e + 2H2O 4OH-
K2 = 104E/0,0592
=> K2 = K1.Kw4
Eo = (1,23 14.0,0592) = 0,40V
M Eo(O2, H2O/OH-) = Eo + (0,0592/4)lg(1/[OH-)4
27
Theo phn ng trn thy K rt nh, mt khc nng NaCl li long, nn qu trnh
chuyn sang AgCl l rt t. V vy sut in ng ca pin coi khng i.
c) Khi thm NH3 0,2M vo in cc anot, c phn ng:
AgI + 2NH3 Ag(NH3)2+ + I-
Theo phn ng trn thy K ln, nn qu trnh chuyn sang phc bn gn nh hon ton,
do ion Ag+ gim i, E(-) gim. V vy sut in ng ca pin tng.
e) Khi thm dung dch HNO3 0,2M vo in cc anot, c phn ng I - b oxi ha bi HNO3
lm nng ion I-, dn n nng ion Ag+ tng (trong mi trng axit ion Ag + khng
tham gia qu trnh to phc hiroxo), nn E (-) tng. V vy sut in ng ca pin gim,
n lc no c th i chiu dng in.
V d 17: Cho s pin:
(-) Ag AgNO31,000.10-1M; NH3 1M Ag2SO4(bo ho) Ag (+)
1. Tnh hng s to phc Ag(NH3)2+ bit EoAg+/Ag = 0,800V; KsAg2SO4 = 1,100.10-5;
Epin = 0,390V
30
Ks = 1,10.10-5
0,1
1
(0,8+2x)
=?
0
(0,1-x)
nn khi cho mui NaCN vo lm nng ion Ag + gim do E(-) gim. V vy sut in
ng ca pin tng.
b) Thm HCl vo in cc anot.
Khi thm HCl vo in c anot c phn ng:
Ag(NH3)2+ + 2H+ Ag+ + NH4+
Do phn ng trn lm nng ion Ag + tng, nn E(-) tng ln. V vy sut in ng ca
pin gim v n lc no pin ngng hot ng v i chiu dng in trong pin.
c) Thm CH3COONa 0,01M vo in cc anot.
Khi thm CH3COONa vo in cc anot c phn ng:
Ag(NH3)2+ + CH3COO- CH3COOAg + 2NH3
K = 10-7,24.(10-2,7)-1 = 10-4,54
(nh)
Theo phn ng trn thy K nh, mt khc nng CH3COONa li long v vy lng
phc mt i rt t. V vy sut in ng ca pin coi khng i.
d) Thm mui BaCl2 bo ho vo in cc catot.
Khi thm BaCl2 vo in cc catot c phn ng:
Ba2+ + 2Cl- + Ag2SO4 BaSO4 + 2AgCl
Theo cn bng trn cho thy nng ion Ag + in cc catot gim, nn lm E (+) gim =>
lm sut in in ca pin gim v n lc no c th pin i chiu dng in.
e) Thm mui NaCN bo ho vo in cc catot.
32
Hng dn gii:
1.
Pb(NO3)2
0,010
----Ba(NO3)2
0,020
----H2SO4
0,130
----HSO4 +
0,130
0,110
HSO4
0,110
Pb2+
2NO3
0,010
Ba2+
2NO3
0,020
H+
HSO4
0,130
2+
Ba
0,020
----Pb2+
0,010
0,130
BaSO4 +
PbSO4 +
33
H+ ;
0,130
0,150
H+ ;
0,150
107,93
105,66
C
[ ]
0,100
----0,160
HSO4
H+
+
SO42 ;
10-2
0,100
x
x
(0,100 - x)
(0,160 + x)
x
-2
x (0,160 + x)/(0,100 - x) = 10
x = [SO42] = 5,69.10-3 (M)
[ H+] = (0,160 + x) = 0,1657 (M)
pH = 0,78
2+
2
-9,93
-3
[Ba ] = K(BaSO
) /[SO4 ] = 10
/5,69.10 = 2,0.10-8 (M)
S
2
-7,66
[Pb2+] = K((PbSO
) /[SO4 ] = 10
/5,69.10-3 = 3,84.10-6 (M)
S
4
2. a) Cc Hiro: 2 H+
CH3COOH
C
0,01
[ ]
0,01 - x
2
x /(0,01 - x) = 10-4,76
E2H
/H2
+ 2e
H+
H2
+ CH3COO
; K a = 10-4,76
x
x
+
x = [H ] = 4,08.10-4 M
pH = 3,39
Cc Pb/PbSO4:
PbSO4 +
Pb
2e
SO42
o
o
/Pb = EPb2+/Pb+ (0,0592/2) lg KS(PbSO )
M EPbSO
4
Pb
0,005
-----
CH3COO + H2O
0,010
0,010 - x
2
x /( 0,010 - x) = 10-9,24
H2 (Pt)
(CH3COO)2Ba +
2 CH3COOH + Ba(OH)2
0,010
-----
C
[ ]
CH3COOH
0,005
CH3COOH + OHx
2H2O
K b = 10-9,24
x = 10
-5,62
34
pH = 8,38
(+)
E2H
/H2
(anot)
(catot)
H+
lg*1 = -2,17
H+
lg*2 = -7,80
H+
lg*3 = -8,96
E0
=
Fe3+ /Fe2+
0
0,771 V; ES/H
= 0,141 V; E 0
2S
=
Pb2+ /Pb
RT
ln = 0,0592lg
F
pKS(PbS) = 26,6; pKS(ZnS) = 21,6; pKS(FeS) = 17,2. (pKS = - lgKS, vi KS l tch s tan).
pK a1(H2S) = 7,02; pK a2(H 2S) = 12,90; pK
Hng dn gii:
1.
Fe3+ + H2O FeOH2+ +
a(NH +
4)
H+
35
*1 = 10-2,17
(1)
2/ Pb + H2S
PbS + 2H
K2 = 106,68
0,10
0,05
0,25
2+
+
3/ Zn + H2S ZnS + 2H
K3 = 101,68
4/ Fe2+ + H2S FeS + 2H+
K4 = 10-2,72
K3 v K4 nh, do cn phi kim tra iu kin kt ta ca ZnS v FeS:
'
'
V mi trng axit C Zn2+ = C Zn 2+ = 0,010 M; CFe2+ = C Fe2+ = CFe3+ = 0,050 M.
i vi H2S, do Ka2 << Ka1 = 10-7,02 nh kh nng phn li ca H2S trong mi
'
trng axit khng ng k, do chp nhn [H +] = CH+ = 0,25 M tnh CS2- theo cn
bng:
H2S S2- + 2H+
Ka1.Ka2 = 10-19,92
CS' 2-
= Ka1.Ka2
0,1
[H 2S]
-19,92
(0,25) 2 = 10-19,72.
[H ]2 = 10
'
'
'
'
Ta c: C Zn2+ . CS2- < KS(ZnS) ZnS khng xut hin; CFe2+ . CS2- < KS(FeS) FeS khng
tch ra.
Nh vy trong hn hp B, ngoi S, ch c PbS kt ta.
0,0592 K S(PbS)
0,0592
lg
lg [Pb2+] = - 0,126 +
= - 0,33 V
2
[S2- ]
2
0,0592 [H + ]2
lg
, trong [H+] c tnh nh sau:
2
p H2
CH3COONH4 NH 4 + CH3COO1
1
+
NH 4
NH3 + H
Ka = 10-9,24 (5)
CH3COO- + H2 O CH3COOH + OH- Kb = 10-9,24 (6)
Do Ka = Kb v C NH +4 CCH3COO- pH = 7,00 [H+] = 10-7
(c th tnh [H+] theo iu kin proton hoc t hp 2 cn bng (5) v (6))
36
Vy: E 2H+ /H =
2
0,0592 [H + ]2
0,0592 10-14
lg
=
lg
= -0,415 V < EPbS/Pb = - 0,33 V
2
p H2
2
1,03
Trn catot:
Trn anot :
H2 + 2CH3COO- 2CH3COOH + 2e
Phn ng trong pin: PbS + H2 + 2H+ + 2CH3COO- Pb + H2S +
2CH3COOH
V d 21:(Chn QT 2006).
Dung dch A c to thnh bi CoCl2 0,0100 M, NH3 0,3600 M v H2O2
3,00.103 M.
1. Tnh pH v nng ion Co2+ trong dung dch A.
2. Vit s pin v tnh sc in ng E ca pin c hnh thnh khi
ghp (qua cu mui) in cc Pt nhng trong dung dch A vi in
cc Ag nhng trong dung dch K 2CrO4 8,0.103 M c cha kt ta
Ag2CrO4.
Cho: pKa: NH4+ 9,24; HCrO4 6,50; pKs (ch s tch s tan)
Ag2CrO4: 11,89.
EO: Co3+/Co2+ 1,84V; H2O2/2OH 0,94V; Ag+/Ag 0,799V.
Log hng s to phc: Co 3+ + 6NH3
Co(NH 3)63+ ;
lg1
= 35,16
Co 2+ + 6NH3
RT
4,39 F
Co(NH 3)62+ ;
ln = 0,0592 lg
Hng dn gii:
1.
CoCl2
0,0100
-----
Co2+
0,0100
37
2Cl
lg2 =
Co(NH3)62+
2 = 104,39
0,0100
2 (0,94 E
o2 )
2 Co(NH3)62+ + H2O2
(1)
o
E1
0,0592
Co(NH3)62+
2
o
E2 = E1 +10,0592 lg
K2 = K1 11 2
;
11
0,0592
K1 = 10
;o E2 2
K2 = 10
2 (0,94
K = 100,0592
= 0,0184
K = 10
)
= 10 31
0,0592
2 Co(NH3)62+ + H2O2
2 Co(NH3)63+ + 2OH ;
(1)
0,0100
0,0030
0,0040
----0,0060
0,0060
Thnh phn gii hn ca h:
Co(NH3)62+
0,0040 M
Co(NH3)63+
0,0060 M
NH3
0,3000 M
K = 1031
OH
0,0060 M
H2O
NH4+
OH
(2)
C
[ ]
0,3000 M
0,3000
(0,3000 - x)
x (0,0060 +
x)
0,3000 - x
x
= 104,76
38
6.10-3
(6.10-3 + x)
x = 7,682.104 <<
[OH] = 6,768.103
pH = 11,83
0,3000
10-4,39
Pt
3 6
3,788.10-
0,0320 (V)
Tnh E ca in cc Ag: Th ca in cc Ag do cp
Ag2CrO4/2Ag quyt nh (hoc Ag+/Ag).
Ag2CrO4 + 2e
2Ag
+
CrO42
o
Ag
EAg = E2CrO4/2Ag
o
Tnh E4 :
+
lg
CrO42
0,0592
2
Ag2CrO4
2
2Ag+
Ag+ + 2e
CrO422Eo3 ; Ks = 10-11,89
0,0592
Ag
2Eo
K 32 = 10
0,0592
(E3 = 0,799 V)
Ag2CrO4 + 2e
K4 = K32. Ks
2Ag
0,0592
E4 = E3 2+
CrO42 ; K4 = 10
lg Ks = 0,447 (V)
CrO42
+
-3
8.10
8.10-3 - x
x
H2O
HCrO4
x
-3
8.10 - x
Ag2CrO4
= 10-7,5
OH ;
Kb = 10-7,5
x
x = 1,6.10-5 << 8.10-3
2Ag+
C
39
CrO42
8.10 -3
Ks = 10-11,89
[]
2x
8.10-3 + x
(2x)2 (8.10-3 + x) = 10-11,89
x = 6,3.10-6 << 8.10-3
[CrO42] = 8.10-3 M
1
EAg = 0,447
+
lg
2
0,0592 CrO4
o
2
/Ag= E
(C th tnh theoAgEAg
+
= 0,5090 (V)
+ 0,0592 lg [Ag+])
Ag l catot, Pt l anot.
S pin:
(a)
Pt Co(NH3)62+ , Co(NH3)63+ , NH3
Ag2CrO4 , CrO42
Ag
(c)
Epin = Ec Ea = 0,5090 0,0302 = 0,479 (V)
V d 22: (Chn QT 2007) Dung dch A gm FeSO4 0,020 M; Fe2(SO4)3 v H2SO4.
a) Ly chnh xc 25,00 ml dung dch A, kh Fe3+ thnh Fe2+; chun Fe2+ trong hn hp
( iu kin thch hp) ht 11,78 ml K2Cr2O7 0,0180 M. Hy vit phng trnh ion ca
phn ng chun . Tnh nng M ca Fe2(SO4)3 trong dung dch A.
b) Tnh nng M ca H2SO4 trong dung dch A, bit dung dch ny c pH = 1,07.
c) Ghp cc Pt nhng trong dung dch A (qua cu mui) vi cc Ag nhng trong dung
dch AgNO3 0,0190 M c thm K2CrO4 cho n nng 0,0100 M (coi th tch c gi
nguyn).
Hy cho bit anot, catot v vit phng trnh phn ng xy ra khi pin hot ng. Tnh
sc in ng ca pin.
Cho pKa: HSO4- 1,99; Fe3+( Fe3+ + H2O FeOH2+ + H+) 2,17;
Fe2+( Fe2+ + H2O FeOH+ + H+) 5,69.
Ch s tch s tan pKs ca Ag2CrO4 11,89.
Eo : Fe3+/ Fe2+ 0,771 V; Ag+/Ag 0,799 V; (RT/F)ln = 0,0592 lg.
Hng dn gii:
2
C1 = 0,01544 M
hay
CFe2(SO4)3 = 0,01544 M.
b) Trong dd A c: Fe2+ 0,020 M; Fe3+ 2C1; H+ (C, M); HSO 4 (C, M); cc cn bng:
H3O+ + OH-
2 H2O
Fe2+ + 2 H2O
Kw = 10-14
FeOH+ + H3O+
Ka1 = 10-5,96
(1)
(2)
Fe3+ + 2 H2O
FeOH2+ + H3O+
Ka2 = 10-2,17
(3)
HSO 4 + H2O
SO 24
Ka = 10-1,99
(4).
+ H3O+
(a)
(b).
Fe
/ Fe
+ 0,0592 lg([Fe3+]/[Fe2+])
Fe3+ + 2 H2O
C
[
FeOH2+ + H3O+
10-2,17
0,03089
]
0,03089 x
10-1,07
CrO 24
0,019
0,010
5. 10-4
Ag2CrO4
Ag2CrO4
2 Ag+
CrO 24
5.10-4
C
[ ]
2x
41
5.10-4 + x
Ks = 10-11,89
C:
o
EAg = E Ag
/ Ag
CrO 24 Ag2CrO4 + 2e
catot 2x Fe3+
2 Ag
+ CrO 24 + 2Fe3+
Fe2+
Ag2CrO4 + 2 Fe2+
H+
H+
3 OH
1= 10-3,8
2 = 10-5,92
KS = 10-29,8
K = 10-14
(E0x)
42
5 OH
K1 = 10
K2 = 10-14
Kw-1 =1014
E0
= -0,13 V < E0
K3 =10
= 0,96 V
NO3- + 4 H+ + 3 e NO + 2 H2O
Ti anot:
CrO2- + 4 OH4
CrO42- + 2 H2O + 3e
HOH
NO3- + CrO2-
H+ + OHCrO42- + NO
2. Phn ng to phc:
Zn2+ + 4 CN [[Zn(CN)4]2-]
Theo bi, rt d CN- nn s to phc xy ra hon ton, tnh nng ion Zn2+ cn bng
to phc theo nng ion phc, phi t v lin quan vi hng s to phc. T biu thc:
E (o c) = 1,6883 = ECal EZn = 0,247 EZn
EZn = 0,247 1,6883 = 1,4413 V
EZn = 0,7628 + (0,0592/2)lg [Zn2+] = 1,4413 (V)
=> tnh c = 1018,92
CCr3
*
+1
1 + hCho: E 0 = 0,80V; E 0
= -0,15V; E 0Au
Ag Ag
AgI/Ag,I
+
3+
/Ag
Phn ng cc m:
Ag(r) + I(aq)
AgI(r) + e
K 11
Phn ng cc dng:
Ag+(aq) + e
Ag(r)
K2
AgI(r)
K S-1
(1)
KS = 1,0.1016.
Ag+ + IS
KS = 10-16
KS =1,0.10-8 M
2. Theo qui c: qu trnh oxi ha Fe2+ xy ra trn anot, qu trnh kh Au3+ xy ra trn catot,
do in cc Pt nhng trong dung dch Fe3+, Fe2+ l anot, in cc Pt nhng trong dung dch
Au3+, Au+ l catot:
(-)
Phn ng cc m:
2x
Phn ng cc dng:
Phn ng trong pin:
(+)
Fe2+(aq)
Fe3+(aq) + e
K 11
Au3+(aq) + 2e
Au+(aq)
K2
Au+(aq) + 2Fe3+(aq)
Au3+(aq) + 2Fe2+(aq)
(2)
Fe3+ + 3e
Fe
E0(1) = -0,037 V,
G0(1) = -3FE0(1)
Fe2+ + 2e
Fe
E0(2) = -0,440 V,
G0(2) = - 2F E0(1)
Fe3+ + e
Fe2+ E0(3) =
0
0
-G 0 (3)
= G (1) - G (2) = 3E0(1)- 2E0(2) = 0,77V
F
F
Fe2+ Fe3+ + e
Bn phn ng cc dng:
45
mc lc
Tr
in. .............
II. Tnh hnh thc t ni dung kin thc v pin in trong cc ti liu hin
hnh.
III-
Mc
tiu
thc
hin. ................................................................
VI- Vai tr ca bi tp trong vic bi dng HSG Quc
ti. ....................................................................
IVPhng
php
ca
gia. ........
4
5
5
5
5
5
5
5
7
8
10
10
14
14
15
15
17
17
25
1. V d minh ha:
25
26
33
47