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Cu I
E 2o = E1o + 0,059 lg
Cu +
Ks
+
12
[Cu2+] = [I-] = 1M Cu = = 10 M
I
Eo2 = 0,15 + 0,059lg1012 = 0,86 > Eo(I2/I-)
Vy c phn ng: Cu2+ + 3I- CuI + I2.
nh lng I2 theo phn ng: I2 + Na2S2O3 Na2S4O6 + 2NaI
2)
Cu2+ + 2e Cu
Eo1 = 0,34V
Cu2+ + e Cu+
Eo2 = 0,15V
][ ]
[ ]
[ ] [ ]
2)
Cu+ + e Cu
Eo3 = 0,34.2 0,15 = 0,53V
CuI + e Cu + IEo4 = Eo3 + 0,059lg10-12 = -0,17V
Vy c phn ng: 2Cu + 2HI 2CuI + H2
3)
Cu+ + e Cu
Eo1 = 0,53V
2+
+
Cu + e Cu
Eo2 = 0,15V
2Cu+ Cu + Cu2+
Eo = 0,53 0,15 = 0,38V
Vy Cu2SO4 l mui tan trong nc, khng bn trong dung dch:
Cu2SO4 Cu + CuSO4
OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng A):
loi tr cc ion NO3- trong nc (cc ion NO3- c mt trong nc xut pht t phn bn)
c th kh n thnh NO2- bng cch cho i qua li c cha bt Cd.
1) Vit na phn ng ca hai cp NO3-/HNO2 v HNO2/NO trong mi trng axit. Chng
minh rng HNO2 b phn hy trong mi trng pH = 0 n 6.
2) pH = 7, nng NO3- l 10-2M. Vit phn ng gia Cd v NO3-. Hi NO3- c b kh hon
ton 25oC trong iu kin ny khng? Tnh nng NO3- cn li trong nc khi cn
bng.
3) Tnh th kh (th oxy ha - kh) chun ca cp NO3-/NO2- pH = 14 v 25oC
Cho bit cc s liu sau 25oC: Eo(NO3-/HNO2) = 0,94V; Eo(HNO2/NO) = 0,98V;
Eo(Cd2+/Cd) = -0,40V; Ka(HNO2) = 5.10-4; Ks(Cd(OH)2) = 1,2.10-14.
BI GII:
1)
NO3- + 3H+ + 2e HNO2 + H2O;
Eo = 0,94V
HNO2 + H+ + e NO + H2O;
Eo = 0,98V
pH = 0 th Eo(HNO2/NO) > Eo(NO3-/HNO2) nn HNO2 b phn hy theo phn ng:
3HNO2 NO3- + 2NO + H+ + H2O
pH = 6 th:
Eo(NO3-/HNO2) = 0,94 + 0,059/2(lg10-6) =
Eo(HNO2/NO) = 0,98 + 0,059lg10-6 = 0,626V
Eo(HNO2/NO) vn ln hn Eo(NO3-/HNO2) nn HNO2 vn khng bn
Cd + NO3- + H2O Cd2++ NO2- + 2OHGi thit phn ng l hon ton th [Cd2+] = [NO3-]b = 10-2M
pH = 7 th [Cd2+] = Ks/[OH-]2 = 1,2M. Nng Cd2+ sau phn ng nh hn nhiu so vi
1,2M nn khng c kt ta Cd(OH)2.
tnh [NO3-] khi cn bng cn tnh hng s cn bng K ca phn ng trn:
K
Cd + NO3- + H2O + 3H+
Cd2+ + NO2- + 2OH- + 3H+
K1
K1
K2
Cd2+ + HNO2 + 2H2O
Cd2+ + H+ + NO2- + 2H2O
K = K1.K2.K3.
2(0,94 + 0,40)
lg K 1 =
= 45,42 K 1 = 2,65.10 45
0,059
2OH10-7
Nh vy ta c:
10 2.10 2.(10 7 ) 2
1,325.1014 =
= NO3 = 7,55.10 33 M
o
2( E NO
+
0,40)
o
3 / NO2
3)
lg K 1 =
E NO
= 0,017V
3 / NO2
0,059
OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng A):
C th ho tan hon ton 100mg bc kim loi trong 100ml dung dch amoniac nng
0,1M khi tip xc vi khng kh c khng?
Cho bit nguyn t khi ca Ag = 107,88; hng s in li baz ca amoniac l Kb =
1,74.10-5; cc hng s bn ca phc [Ag(NH3)i]+ tng ng l: lg1 = 3,32(i = 1) v lg2 = 6,23(i =
2).
Cc th kh (th oxy ha - kh) chun 25oC: Eo(Ag+/Ag) = 0,799V; Eo(O2/OH-) =
0,401V. p sut ring phn ca oxy trong khng kh l 0,2095atm. Phn ng c thc hin
25oC.
BI GII:
NAg = 0,100 : 107,88 = 9,27.10-4mol
S mol cc i ca NH3 cn to phc l: 9,27.10-4 . 2 = 1,854.10-3M ngha l nh hn
nhiu so vi s mol NH3 c trong dung dch (10-2M). Vy NH3 rt d ho tan lng Ag nu xy
ra phn ng.
Chng ta s kim tra kh nng ho tan theo quan im in ha v nhit ng:
Ag+ + e Ag
E1 = Eo1 + 0,059lg[Ag+]
PO2
0,059
E 2 = E 2o +
lg
4
4
OH
O2 + 4e + H2O 4OHKhi cn bng E1 = E2. Trong dung dch NH3 = 0,1M (lng NH3 phn ng khng ng
k) ta c: [OH-] = (Kb.C)1/2 = 1,32.10-3M
E2 = 0,5607V.
V E2 = E1 nn t tnh ton ta c th suy ra c [Ag+] = 9,12.10-5M
Nng tng cng ca Ag+ trong dung dch:
[Ag+]o = [Ag+] + [Ag(NH3)+] + [Ag(NH3)2+]
= [Ag+](1 + 1[NH3] + 12[NH3]2) = 15,5M
Gi tr ny ln hn nhiu so vi lng Ag dng cho phn ng. V vy cc iu kin in
ha v nhit ng thun li cho vic ho tan 0,100g Ag
OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng B):
1) Trn hai th tch bng nhau ca hai dung dch SnCl2 0,100M v FeCl3 0,100M. Xc nh
nng cc ion thic v st khi cn bng 25oC. Tnh th ca cc cp oxy ha - kh khi
cn bng.
2) Nhng mt si Ag vo dung dch Fe2(SO4)3 2,5.10-2M. Xc nh nng ca Fe3+; Fe2+ v
Ag+ khi cn bng 25oC. Tnh th ca cc cp oxy ha - kh khi cn bng.
Cho bit Eo(Sn4+/Sn2+) = 0,15V; Eo(Fe3+/Fe2+) = 0,77V; Eo(Ag+/Ag) = 0,80V
BI GII:
1) Sn2+
+
2Fe3+
Sn4+
+
2Fe2+
Ncb: 0,05- x
0,05 2x
x
2x
21
lgK = 2(0,77 015)/0,059 = 21 K = 10 .
[ Fe ] = 6.10
3+
] [
6.10 3
= 0,80 + 0,059 lg 4,38.10 2 = 0,72V
2
4,38.10
K THI CHN HC SINH GII QUC GIA VIT NAM 2002 (BNG A)
1. Bit th oxi ha-kh tiu chun :
Ecb = 0,77 + 0,059 lg
Cho : axit c H2S pK1 = 7,00, pK2 = 12,90; HSO4- c pK = 2,00; Tch s tan
ca PbS = 10-26 ; PbSO4 = 10-7,8 ; PbI2 = 10-7,6.
Eo Fe3+/Fe2+ = 0,77 V ; Eo S/H2S = 0,14V ; Eo I2/2I- = 0,54V ; Ecal bo ho = 0,244V
BI GII:
1. a) Eo Fe3+/Fe2+ = +0,77 V
>
Eo Fe2+/Fe = -0,44 V nn:
Tnh oxi ho: Fe3+ mnh hn Fe2+
Tnh kh:
Fe mnh hn Fe2+
Do phn ng t pht xy ra gia 2 cp l: 2 Fe3+ + Fe 3 Fe2+
Nh vy Fe tan trong dung dch Fe(SO 4)3 to thnh mui FeSO4, lm nht mu vng ( hoc
nu) ca ion Fe3+ v cui cng lm mt mu (hoc to mu xanh nht) dung dch.
b) Eo Cu+/Cu = + 0,52 V > Eo Cu2+/Cu+ = + 0,16 V nn:
Tnh oxi ho: Cu+ mnh hn Cu2+
Tnh kh:
Cu+ mnh hn Cu
S2- + 2H+ H2S (C H2S = 0,010 < S H2S nn H2S cha bo ho, khng thot ra
khi dung dch)
Phn ng:
+ 2 H+
K=1021
0,1
0,01
0,08
0,02
0,02
3+
2+
2 Fe + 2I 2 Fe
+
I2
K=107,8
0,08
0,06
0,02
0,02
0,08
0,030
3+
Thnh phn trong dung dch: Fe 0,020 ; Fe2+ 0,080 ;I2 0,030M ;H+ 0,02M
E Fe3+/Fe2+ = 0,77 + 0,059 lg 0,02/0,08 = 0,743V (cc dng)
Ecal = 0,244V ( cc m)
Epin = E+ E = 0,743 0,244 = 0,499V
+
S pin:
3+
2+
Hg | Hg2Cl2 | KCl bh || Fe , Fe | Pt
Phn ng:
2 Hg + 2 Cl- = Hg2Cl2 + 2 e
+ 2x Fe3+ + e
= Fe2+
2 Hg + 2 Fe3+ + 2 Cl- = Hg2Cl2
K THI CHN HC SINH GII QUC GIA VIT NAM 2002 (BNG A)
Cho dng in 0,5A i qua dung dch mui ca mt axit hu c trong 2 gi. Kt qu sau
qu trnh in phn l trn catot to ra 3,865 gam mt kim loi v trn anot c kh etan v kh
cacbonic thot ra.
1. Cho bit mui ca kim loi no b in phn? Bit rng 5,18 gam ca kim loi y c
1,59 gam Cu t dung dch ng sunfat.
2. Cho bit mui ca axit hu c no b in phn?
3. Vit cc phng trnh phn ng xy ra trn cc in cc.
BI GII:
Khi lng mol ca kim loi: A = n. . V kim loi ny y ng ra khi dung dch nn
ng lng ca Cu:
A1 = 103,6 x 1 = 103,6
A2 = 103,6 x 2 = 207,2
A3 = 103,6 x 3 = 310,8
V khng c nguyn t vi A > 240 v bng 104 c tnh kim loi v c mc oxi ho l +1.
Do kim loi phi tm ch c th l Pb (A = 207,6).
CH3COO
= CH3 + CO2
2 CH3
= C2H6
Tng qut: 2 CH3COO 2e = C2H6 + CO2.
K THI CHN HC SINH GII QUC GIA VIT NAM 2004 (BNG A)
Dung dch A gm AgNO3 0,050 M v Pb(NO3)2 0,100 M.
1. Tnh pH ca dung dch A.
2. Thm 10,00 ml KI 0,250 M v HNO3 0,200 M vo 10,00 ml dung dch A. Sau phn ng ngi ta
nhng mt in cc Ag vo dung dch B va thu c v ghp thnh pin (c cu mui tip xc hai
dung dch) vi mt in cc c Ag nhng vo dung dch X gm AgNO 3 0,010 M v KSCN 0,040
M.
a) Vit s pin .
b) Tnh sc in ng Epin ti 250C .
c) Vit phng trnh phn ng xy ra khi pin hot ng.
d) Tnh hng s cn bng ca phn ng .
Cho bit : Ag+ + H2O
AgOH + H+ (1) ; K1= 10 11,70
Pb2+ + H2O
PbOH+ + H+ (2) ; K2= 10 7,80
Ch s tch s tan pKs : AgI l 16,0 ; PbI2 l 7,86 ; AgSCN l 12,0 .
RT
0
ln = 0,0592 lg
EAg
;
=
0
,799
V
+
F
/Ag
2. Epin s thay i ra sao nu: a) thm mt lng nh NaOH vo dung dch B ; b) thm mt lng
nh Fe(NO3)3 vo dung dch X?
BI GII:
1. Ag+ + H2O AgOH + H+ ; K1 = 10-11,7
(1)
2+
+
+
-7,8
Pb + H2O PbOH + H
; K2 = 10
(2)
Do K2 >> K1 nn cn bng 2 quyt nh pH ca dung dch
Pb2+ + H2O PbOH + H+ ; K2 = 10-7,8 (2)
0,10
0,10 x
[]
x
= 10 7 ,8
x = 10-4,4 = [H+]
; pH = 4,40
0,1 x
2.a) Dung dch B: Thm KI : CAg+ = 0,025 M; CPb2+ = 0,050
CI- = 0,125M ; CH+ = 0,10M
Ag+
+
I
AgI
0,025
0,125
0,10
2+
Pb
+
2I
PbI2
0,05
0,10
Trong dung dch c ng thi hai kt ta AgI v PbI2
AgI Ag+ + I
;
Ks1 = 1.10-16 (3)
PbI2 Pb2+ + 2 I
;
Ks2 = 1.10-7,86 (4)
Ks1 << Ks2, vy trong dung dch cn bng (4) l ch yu. S to phc
2+
hidroxo ca Pb l khng ng k v c H+ d:
2
-7,86
-3
(2x) x = 10
x = 1,51.10 M
2x = [I ] = 2,302 . 10-3M
s1
16
3
] [
= 3,31.10 14 M .
Dung dch X:
E 1 = 0,001V
Ag+ +
SCN AgSCN ;
1012,0
0,010
0,040
0,030
0,010
Ag
b)
AgI
PbI2
AgSCN
SCN 0,03 M
Ag
K=
KsAgSCN
KsAgI
12
= 10
16
= 104
10
2IO4 /I2(r) = 1,31V; 2IO3 /I2(r) = 1,19V; 2HIO/I2(r) = 1,45V ; I2(r)/2I = 0,54V
(r): ch cht trng thi rn.
1. Vit phng trnh na phn ng oxi ha - kh ca cc cp cho.
RT
F
25oC, ln
BI GII:
1.
2 IO4 + 16 H+ + 14 e
2 IO3
+ 12 H+ + 10 e
2 H+ + 2 e
2 HIO +
I2 (r)
+ 2e
+ 6 H2O
I2(r) + 2 H2O ; Eo
2I
K5 = K1. K2 1
-10Eo2/0,0592
I2(r) + 6 H2O ; K2 = 10
2 HIO + 2 H+ + 2 e
10Eo2/0,0592
; K3 1 = 10
-2Eo3/0,0592
8E 6/0,0592
K6 = 10
= K2. K3 1
o EIO
= Eo6 =
3 /HIO
V IO
E3-/HIO
3.
+ 10 H+ + 8 e
2 IO3
= 0,54 V = Eo4
Eo5 = EoIO4-/IO3-
I2(r) + 2 H2O
; Eo
+ 12 H+ + 10 e
2 IO3
= 1,45 V = Eo3
2 IO3 + 12 H+ + 10 e ; K2 1 = 10
2 IO4 + 4 H+ + 4 e
= 1,19 V = Eo2
I2 (r)
= 1,31 V = Eo1
I2(r) + 6 H2O ; Eo
2 IO4 + 16 H+ + 14 e
2.
I2(r) + 8 H2O ; Eo
10 E2O 2 E3O
8
o
< EHIO/I
2
= 1,125 (V)
nn HIO s t oxi ho - kh
4
2 HIO + 2 H+ + 2 e
2 HIO + 4 H2O
10 HIO
I2(r) + 2 H2O
2 IO3
+ 10 H+ + 8 e
4 I2(r) + 2 IO3
+ 2 H+ + 4 H2O
2+
o
o
I2/2I- (Eo4 nh nht) nn u tin s xy ra phn ng:
4 /Mn = 1,51V >> E
4. a)EMnO
2
MnO4 + 8 H+ + 5 e
Mn2+ + 4 H2O
2I
CO
2 MnO4
0,24
+ 10 I + 16 H+
0,4
I2(r) + 2 e
2 Mn2+ + 5 I2(r) + 8 H2O ; K = 10 163
C 0,04 2 0,04 10
0,04 2
C
0,16
0
1
0,08
+ 8 H+ + 5 e
MnO4
I2(r)
+ 6 H2O
CO
C
C
Mn2+ + 4 H2O
2 IO3
2 MnO4 + I2(r) + 4 H+
0,16
0,2
0,08 2
0,08
0
0,12
1
0,04 5
0, 2
+ 12 H+ + 10 e
Thnh phn hn hp sau phn ng: IO3 = 0,16 M; Mn2+=0,24 M; I2(H2O)=5.10 4M; )
I2(r) = 0,12M; pH = 0.
[ ][ ]
2
2
0,0592
lg IO3 H + = 1,18V
3
10
E so vi in cc calomen bo ho: 1,18 0,244 = 0,936V
5.
2IO3- + 12H+ + 10e I2(r) + 6H2O : K2 = 1010.1,19/0,0592
I2(r)
I2(H2O)
S = 5.10-4M
+
E7o/0,0592
2IO3 + 12H + 10e I2(H2O) + 6 H2O; K7 =10
=1010.1,19/0,0592.S
Suy ra E7o = 1,17V
K THI CHN HC SINH GII QUC GIA VIT NAM 2005 (BNG A)
Mt bnh in phn cha dung dch NaOH (pH=14) v mt bnh in phn khc cha
dung dch H2SO4 (pH = 0) 298K. Khi tng hiu in th t t hai cc mi bnh ngii ta thy
c kh ging nhau thot ra c hai bnh ti cng in th.
1. Gii thch hin tng trn. Vit cc phng trnh phn ng xy ra mi bnh (khng xt s to
thnh H2O2 v H2S2O8).
2. Tnh hiu in th ti thiu phi t vo hai cc mi bnh cho qa trnh in phn xy ra.
3. Ngi ta mun gim pH ca dung dch NaOH xung cn 11. C th dng NH4Cl c khng?
Nu c, hy gii thch v tnh khi lng NH4Cl phi dng gim pH ca 1 lt dung dch
NaOH t 14 xung cn 11.
4. Khi pH ca dung dch NaOH bng 11, th hiu in th ti thiu phi t vo hai cc ca bnh
in phn cho qa trnh in phn xy ra l bao nhiu?
Cho bit: H
E2oO, 1/2 O2 / 2OH = 0,4V; Eo2H+, 1/2 O2 / H2O=1,23 V; pKb(NH3) = 4,75.
o
E = EIO
/I
2 (r)
BI GII:
1.
Trong th nghim ny, nc b in phn cng mt in th.
a) Dung dch NaOH:
anot:
2 OH
H2O + 1/2 O2 + 2 e
catot:
2 H2O + 2 e
H2 + 2 OH
H2O
H2 + 1/2 O2
H2O
2 H+ + 2 e
1/2 O2 + 2 H+ + 2 e
H2
H2O
H2 + 1/2 O2
2 lg (1014)2 = 0,83 V
Ecatt = 0 + 0,0592
U min = E ant E catt = 0,4 + 0,83 = 1,23 V
b) Dung dch H2SO4:
Eant = 1,23 V
Ecatt = 0 V
Umin = E ant E catt = 1,23 V
(khi tnh Umin khng xt n qu th).
NH3 + H2O
pOH ca dung dch NaOH thm NH4Cl gim pH ca dung dch NaOH t 14
xung 11 c tnh theo cng
thc:
+
[NH4 ]
pOH = pKb + lg[NH3]
3 = 4,75 + lg [NH4+]
[NH3]
Khi pH ca dung dch NaOH gim t 14 xung 11 th [OH ] ca dung dch gim i: 1
3
10 = 0,999 mol. y chnh l s mol NH3 hnh thnh. Vy [NH3] = 0,999 mol/L v:
[NH4+] = 0,0178 0,999 0,0178 (mol/L)
S mol NH4Cl phi thm vo 1 lt dung dch:
n= n
NH4+
+ n
NH3
Khi lng NH4Cl phi thm vo 1 lt dung dch: 1,0168 53,5 = 54,4 (gam)
4. Khi pH = 11, dung dch NaOH:
Eanot = 0,4 V + 0,0592 lg
1
11 2 3 2
2
Ecatt = 0 + 0,0592lg (10 (10
) )
2 = 0,4 + 3 0,0592 + 0,0592 11 1,23 V
U min = E anot E catot
II.
OLYMPIC HA HC QUC T:
K THI OLYMPIC HA HC QUC T LN TH 30:
Vng kim loi thng c pht hin trong cc loi aluminosilicat v b phn tn
nhuyn trong cc khong cht khc. Vng c th c tch bng cch cho nghin vn tc dng
vi dung dch natri xianua sc khng kh. Trong qa trnh ny vng km loi c chuyn chm
thnh [Au(CN)2]- tan c trong nc (phn ng (1)).
Sau khi t n cn bng, phn dung dch (pha dung dch) c bm ra v vng kim loi
c thu hi bng cch cho phc vng tc dng vi km, km c chuyn thnh [Zn(CN)4]2(phn ng 2).
1) Vit v cn bng cc phng trnh ion ca phn ng (1) v (2).
Vng trong t nhin thng dng hp kim vi bc v bc cng b oxy ho bi dung dch
natri xianua sc khng kh.
2) 500L dung dch cha [Au(CN)2]- 0,0100M v [Ag(CN)2]- 0,0030M c cho bay hi n
ch cn mt phn ba th tch ban u v c x l bng km (40g). Gi thit rng s sai
lch so vi iu kin tiu chun l khng quan trng v cng gi thit l cc phn ng oxy
ha kh xy ra hon ton. Hy tnh cc nng ca [Au(CN)2]- v [Ag(CN)2]- sau khi phn
ng kt thc.
Cho bit:
[Zn(CN)4]2- + 2e- Zn + 4CNEo = -1,26V
[Au(CN)2]- + e- Au + 2CNEo = -0,60V
[Ag(CN)2]- + e- Ag + 2CNEo = -0,31V
3) [Au(CN)2]- l mt phc rt bn trong mt s iu kin nht nh. Nng ca natri xianua
l bao nhiu gi c 99% theo s mol ca vng trong dung dch dng phc xianua?
Bit Kb([Au(CN)2]-) = 4.1028.
4) c mt s c gng pht trin cc qa trnh tch chit vng khc thay th cch trn.
Ti sao?. Hy chn phng n ng:
a) Dung dch natri xianua n mn cc dng c khai thc m.
b) Natri xianua thot vo nc ngm trong t v to ra hydroxianua rt c vi nhiu
ng vt.
c) Vng thu c t phng php ny khng tinh khit.
BI GII:
1) Phn ng (1): 4Au + 8CN- + O2 + 2H2O 4[Au(CN)2]- + 4OHPhn ng (2): Zn + 2[Au(CN)2]- [Zn(CN)4]2- + 2Au
2) EoAg/Zn = -0,31 (-1,26) = 0,95V
EoAu/Zn = -0,60 (-1,26) = 0,66V
EoAg/Zn > EoAu/Zn. V vy phc Ag(I) s b kh trc.
nAg(I) = 1,5mol
nAu(I) = 5,0mol
nZn = 0,61mol
1mol Zn s phn ng vi 2 mol Ag(I) hoc Au(I).
Nn 0,61 mol Zn s tiu th 1,2mol [Ag(CN)2][Ag(CN)2]- cn li = 1,5 1,2 = 0,3mol
[Au(CN)2]- khng b kh.
Nng [Au(CN)2]- khi phn ng kt thc = 0,010.3 = 0,030M
Nng [Ag(CN)2]- khi phn ng kt thc = 0,3.3/500 = 0,002M
3)
Au+ + 2CN- [Au(CN)2]Kb = 4.1028.
[ Au(CN ) ]
Kb =
[ Au ][CN ]
[ Au(CN ) ] = 99
[ Au ] + [ Au (CN ) ] 100
][
BI GII:
1. Cu trc ng thng:
N
Au
2.
3.
4.
5.
4KAu(CN)2 + 4KOH
4Au + 8KCN- + O2 + 2H2O
mKCN = (20/197).(8/4).65,12 = 13,024g
Cch 1: E = Eo (0,059/n)lgQ
Lc t cn bng: Q = K, E = 0; K = [AuCl4-]/[Au3+][Cl-]4
Eo = (0,059/n)lgK K = 1025,42 = 2,6.1025.
Cch 2: Go1 + Go2 = Go3
(-nFEo1) + (-nFEo2) = -RTlnK
E = (RT/nF)lnK = (0,059/n)lgK K = 1025,42 = 2,6.1025.
6.
a)
III.
BI TP CHUN B CHO OLYMPIC HA HC QUC T:
OLYMPIC HA HC QUC T LN TH 32:
K thut in ha hc thng c dng xc nh tnh tan ca cc mui kh tan. Do sc
in ng l hm bc nht theo logarit ca nng cho nn c th xc nh c cc nng d
rt nh.
Bi tp ny s dng mt pin in ha gm hai phn, c ni bng cu mui. Phn bn tri
ca s pin l mt thanh Zn(r) nhng trong dung dch Zn(NO3)2(aq) 0,200M; cn phn bn phi
l mt thanh Ag(r) nhng trong dung dch AgNO3(aq) 0,100M. Mi dung dch c th tch 1,00L ti
25oC.
a) V gin pin v vit phng trnh phn ng tng ng ca pin.
b) Hy tnh sc in ng ca pin v vit phng trinh phn ng khi pin phng in.
Gi s pin phng in hon ton v lng Zn c d
c) Hy tnh in lng phng thch trong qa trnh phng in.
Trong mt th nghim khc, KCl(r) c thm vo dung dch AgNO3 pha bn phi ca
pin ban u. Xy ra s kt ta AgCl(r) v lm thay i sc in ng. Sau khi thm xong, sc in
ng bng 1,04V v [K+] = 0,300M.
d) Hy tnh [Ag+] ti cn bng.
e) Hy tnh [Cl-] ti cn bng v tch s tan ca AgCl.
Th in cc chun ti 25oC nh sau:
Zn2+(aq) + 2e Zn(r)
Eo = -0,76V
Ag+(aq) + e Ag(r)
Eo = +0,80V
BI GII:
a) Gin pin: Zn(r) Zn2+(aq) Ag+(aq)Ag(r).
Gin pin ny tho quy c ca IUPAC vi qa trnh oxy ha (cho electron) pha bn
tri:
Tri, oxy ha: Zn(r) Zn2+(aq) + 2e
Phi, kh: Ag+(aq) + e Ag(r) (nhn cho 2)
Phn ng ca pin Zn(r) + Ag+ Zn2+(aq) + 2Ag(r).
b) Eopin = Eo(phi) Eo(tri) = 1,56V
Phng trnh Nernst tng ng vi pin nu trn (Cng c th trnh by theo na pin v cc
bn phn ng):
Hot a ca mt cht tan tnh gn ng t nng ca cht y (chia cho nng tiu
chun) v hot ca mt cht rn bng 1
2
0,05916 a Zn 2 + .(a Ag + )
0,05916
0,200
o
E pin = E pin +
lg
= 1,56
lg
= 1,52V
2
n
2
a Zn .(a Ag + )
(0,100) 2
Tr s dng ca Epin cho thy rng phn ng pin vit nh trn l phn ng c th t xy ra
trong qa trnh phng in.
Phn ng c th t xy ra: Zn(r) + Ag+ Zn2+(aq) + 2Ag(r).
c) Khi phng in hon ton, Epin = 0 v phn ng trong pin t cn bng
0 = 1,56 0,05916/2.lgK K = 5,5.1052; ngha l cn bng ca phn ng pin dch chuyn
hn v bn phi, nn thc t khng cn ion Ag+ trong dung dch
Lng Ag+ v electron vn chuyn:
n(Ag+) = [Ag+].V = 0,100mol v n(e-) = n(Ag+) = 0,100mol
Hng s Faraday F l s in lng ng vi 1 mol electron
Q = n(e-).F = 9648,5C
d) Gi x l nng Ag+ cui ([Ag+])
in cc bn tri khng i, ngha l nng [Zn2+] duy tr ti 0,200M
0,05916 0,200
1,04 = 1,56
lg
x = Ag + = 7,3.10 10 M
2
2
e) [Cl ] = nng thm - nng gim do AgCl kt ta = 0,300 (0,100 - 7,3.10-10)
= 0,200M
Ks(AgCl) = 7,3.10-10.0,200 = 1,5.10-10M2.
OLYMPIC HA HC QUC T LN TH 31:
Ga tr Eo cho cc bn phn ng ca Fe v Ce nh sau:
Fe3+ + e- Fe2+
Eo = 0,77V
4+
3+
Ce + e Ce
Eo = 1,61V
Th ti im tng ng ca s chun Fe2+ v Ce4+ l 1,19V. Hai cht ch th mi c
th s dng xc nh im tng ng:
Di Bolane(dip): InOx + 2e
Inred
Eodip = 0,76V
Tm
khng mu
p-nitro-di-bolane(pn): InOx +
2e
Inred
Eopn = 1,01V
Tm
khng mu
C hai cht ch th u i mu khi [InOx]/[Inred] = 10. Vy cht ch th no l thch hp cho
s chun Fe2+- Ce4+?
BI GII:
0,059 [ oxh]
o
lg
Vi di-bolane: E dd = E dip +
[ red ]
2
0,059 [ oxh]
o
lg
= 0,79V
Khi [InOx]/[Inred] = 10 th: E dd = E dip +
[ red ]
2
Ti 0,79V, tnh [Fe3+]/[Fe2+]
0,059 Fe 3+
o
E dd = E Fe +
lg
1
Fe 2+
[
[
]
]
[ Fe ] [ Fe ] = 2,2
0,79 = 0,77 + 0,059 lg
[ Fe ] [ Fe ]
3+
3+
2+
2+
o
Khi [InOx]/[Inred] = 10 th: E dd = E pn +
0,059 [ oxh]
lg
= 1,04V
[ red ]
1
[
[
[ Fe
1,04 = 0,77 + 0,059 lg
[ Fe
3+
]
]
] [ Fe ] = 3,80.10
] [ Fe ]
2+
3+
2+
[ H ] = {P
+
2
H2
.e
( 2 FE opin / RT )
{P
2
H2
.e
( 2 FE opin / RT )
} 1 / 6 cho
[ ]
]
e) pH = 5: Thay [H+] = 10-5M vo biu thc (*) trn ta tnh c [Mn(mn)2+] = 4,7.10-10M
pH = 8: Thay [H+] = 10-8M vo biu thc (*) trn ta tnh c [Mn(mn)2+] = 4,7.10-16M
f) t kim
OLYMPIC HA HC QUC T LN TH 33:
a) Mt dung dch cha ion Sn2+ c chun in ha bng dung dch Fe3+. Th kh tiu chun
ca cp Sn4+/2+ v Fe3+/2+ c cho di y:
Sn4+ + 2e = Sn2+
Eo = 0,154V
3+
2+
Fe + e = Fe
Eo = 0,771V
i) Vit phng trnh phn ng tng qut v tinh nng lng t do ca phn ng.
ii) Xc nh hng s cn bng ca phn ng.
b) Nu 20ml dung dch Sn2+ 0,10M c chun bng dung dch Fe3+ 0,20M. Tnh sc in
ng ca pin trong cc iu kin sau:
i) Khi thm 5mL Fe3+.
ii) Ti im tng ng.
iii) Khi thm 30mL dung dch Fe3+
in cc calomel (EoS.C.E = 0,242V) c s dng lm in cc chun.
c) Mt trong s nhng phng php phn tch quan trng nh lng ion Cu2+ l php
chun iot. Trong phn ng ny Cu2+ s b oxy ha v Cu+ bng I- v I2 t do sinh ra s phn
ng vi dung dch chun Na2S2O3. Phn ng chun Cu2+ xy ra theo phng trnh:
2Cu2+ + 4I- 2CuI(r) + I2(aq)
Th chun ca cc qa trnh oxy ha - kh s l:
Cu2+ + e = Cu+
Eo = 0,153V
I2 + 2e = 2IEo = 0,535V
Da vo th chun th phn ng trn khng th xy ra c. Tuy nhin phn ng ny vn
xy ra mt cch nh lng. Chng ta hy tm hiu l do thng qua cc d kin sau:
i) trong dung dch nc th CuI c tch s tan b vi Ksp = 1,1.10-12. Tnh th kh chun
biu kin ca qa trnh CuI(r) = Cu+ + I-.
ii) S dng kt qa cu i), tnh th kh chun biu kin ca phn ng v hy da vo cho
bit chiu phn ng.
iii) Tnh hng s cn bng ca phn ng t cc d kin cho cu ii).
BI GII:
a) i) Phn ng xy ra theo phng trnh:
Sn2+ + 2Fe3+ = 2Fe2+ + Sn4+
Eo = 0,617V
G = -nFE = -119kJ
ii) 0,0592/n(lgK) K = 6,92.1020.
b) Trc im tng ng, E ca phn ng c tnh bi phng trnh:
0,0592 Sn 2+
o
E pin = ox E So.C .E + kh E Sn
lg
4+
/ Sn 2 +
2
Sn 4+
i) Khi thm 5,00mL Fe3+ th lng Sn2+ chuyn sang Sn4+ s l 5,00/20,00.
Nh vy:
Sn 2+ 15,0 / 20,0
=
=3
5,0 / 20,0
Sn 4+
Thay vo biu thc tnh E ta thu c kt qa E = -0,102V
ii) Ti im tng ng ta tnh E theo cng thc:
o
o
2 ESn
+ E Fe
4+
3+
/ Sn 2 +
/ Fe 2 +
E=
= 0,118V
3
iii) Khi thm 30,00mL Fe3+ vo th trong dung dch cn d 10mL Fe3+:
Fe 2+
20,0
=
=2
3+
10,0
Fe
Thay vo biu thc tnh E ta c: E = 0,511V
c) i) G = -RTlnKsp = 68,72kJ
[
[
[
[
[
[
]
]
]
]
]
]
nap
phong
2Ni(OH)2(r) + Cd(OH)2(r)
][ ]
[
]
0,059 AsO43 H +
E1 = E +
lg
2
AsO33
o
1
o
Khi pH = 1 th E1 = E1 0,059 +
[
[
0,059 Ce 4 +
lg
2
Ce3 +
Eeq = E1 = E2
E2 = E2o +
]
]
= E1o +
[ ]
]
]
[
[
2
0,059
0,059 AsO43
lg H + +
lg
2
2
AsO33
[
[
]
]
0,059 AsO43
lg
2
AsO33
3
4
3
3
3+
3
3
3
4
4+
3+
3
3
3
4
4+
3+
eq
RT
ln a ( Ag + ) = 0,331V a( Ag + ) = 1,22.108 M
F
Vi i lng ny th [Ag+] = a(Ag+)
TAgI = 1,48.10-16.
c) E3 = Ecalomen E(AgI (bo ho), PbI2 (bo ho)/Ag)
E(AgI (bo ho), PbI2 (bo ho)/Ag) = 0,012V
Tng t nh phn b, kt qa thu c y l [Ag+] = 4,89.10-14M
Phn nng ion iodua sinh ra t AgI cng bng nh vy.
S dng tch s ho tan i vi AgI tnh c phn b ta c:
[I-] = 3,02.10-3M
Phn nng in iodua sinh ra t AgI l khng ng k so vi ga tr ny. Nh vy nng
ion ch s l 0,5[I-].
T(PbI2) = 0,5[I-]3 = 1,38.10-8M3.
OLYMPIC HA HC C 1999 (Vng 3):
Cho cc th chun sau y:
AgBr(r) + e Ag + BrEo1 = 0,0713V
+
Ag + e Ag
Eo2 = 0,7996V
a) Trn c s hy tnh TAgBr 25oC.
b) T hy tnh Go i vi qa trnh: AgCl(r) Ag+(aq) + Cl-(aq). Bit SAgCl(25oC) = 1,274.105
M.
BI GII:
a) Eo1 c lin quan n mt bn t bo, trong trn mt lp kt ta bc bromua nng
ion bromua l 1,00M. Nh c Eo2 ngi ta c th theo phng trnh Nernst tnh c nng
ion bc trong t bo v t nh c [Br-] = 1,00M c th tnh c tch s ho tan.
RT
E1o = E2o +
ln C1 4,81.10 13 M TAgBr = 4,81.10 13 M 2
F
b) T ho tan ta c: [Ag+] = [Cl-] = 1,274.10-5M v nh vy l tch s ho tan T =
(1,274.10-5)2. T cng l hng s cn bng KC i vi phn ng: AgCl(r) Ag+(aq) + Cl-(aq)
KC ngoi ra cng l hng s cn bng nhit ng lc hc. iu ny c ngha l:
Go = -RTlnT = 55,8kJ/mol.
o
E(AgI (bo ha)/Ag//Ag) = E +