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Nguyen tac
ac iem cua phng phap
ien cc
Can bang chuan o
Cach xac nh iem tng ng
Nguyen tac
) Thc
hien s chuan o
) Nhung vao dd chuan
o ien cc co tham gia
phan ng ien hoa vi
mot trong nhng cau t
co trong can bang chuan
o.
) Khao sat s bien thien
the can bang cua ien
cc theo lng thuoc th
them vao
) T ng cong E =
f(V), xac nh iem tng
ng
Buret, C
ien cc
so sanh
ien cc
ch th
dd phan
tch, X
E 0 n+
/M
M
0
E n+
/M
M
0
= E MA
/ M
M / M n+ hay M / An
n+
n+
n
M ne
M , M +A
MA
0,059
+
lg[ M n+ ] -Th du: /c Ag
n
+
Ag e
Ag
0,059 TMA
+
lg n
0,059
+
n
[ A ] Ecb = E 0 +
lg[ Ag ]
+
Ag / Ag
1
0,059
1
+
lg n
0,059
1
0
lg
n
[ A ] hay Ecb = E AgCl / Ag +
1
[Cl ]
- S
o ien cc
- P ien cc
Pt / Ox , Kh
-Th du: /c
Pt / Fe 3+ / Fe 2+
Ox + ne
Kh
0,059 [Ox ]
0
Ecb = EOx / Kh +
lg
n
[ Kh]
Fe 3+ + e Fe 2+
Ecb = E 0
Fe 3+ / Fe 2 +
0,059 [ Fe 3+ ]
lg
+
1
[ Fe 2+ ]
+
Natt
+
H tt
+
Nadd
Ag
H+
(a2
const)
Cau
truc
cua
ien
cc
thuy
tinh
AgCl
H+
(a1)
Glass membrane (64% SiO 2,
28% Na2O, 8% MgO) (0,06 0,10
mm)
8
a1
a1
a2
a2
Lp gel tren
mat trong
thuy tinh
0,059 a1
e1 = K1 +
lg '
1
a1
0,059 a2
lg '
e2 = K 2 +
1
a2
K1 K 2 ; a '1 a '2
0,059 a1
E = e1 e2 =
lg
1
a2
Vi a2 la hang so
E = K + 0,059 lg a1 = K 0,059 pH
9
10
+
ne
M
+
A
- P ien cc
E cb =
0
E MA
/ M
0,059
1
+
lg n
n
[A ]
Cau
truc
cua
ien
cc
so
sanh
11
S o ien cc Ag/AgCl
Do the va Chuan do dien the
12
ien cc Calomel
/c Calomel Kim loai Hg c phu muoi Hg2Cl2
nhung vao dd Cl- co nong o xac nh
- S o ien cc Hg , Hg 2Cl 2 /[Cl ]
- P ien cc
E cb =
Hg2Cl 2 +2e
2 Hg +2Cl
0
E Hg
2Cl 2 / 2 Hg
0
= E Hg
2Cl 2
1
0,059
+
lg 2
2
[Cl ]
0
,
059
lg[
Cl
]
/ 2 Hg
13
Saturated Calomel
Electrode
Calomel bao hoa (S.C.E
Satured Calomel
Electrode) vi dd KCl bao
hoa, E = 0,244 v 250C
Calomel nguyen chuan
(N.C.E Normal Calomel
Electrode) vi dd [KCl] =
1M, E = 0,284 v 25 0C
14
ien cc kh
Cau tao Kim loai tr nh Pt, Au, tiep xuc ong
Pt , H 2 / H +
- P ien cc
H 2 2e
2H +
Ecb = E 0
0,059 [ H + ]2
+
lg
2
pH 2
2H + / H2
ien cc
Hydro khong
tien dung,
c dung
lam ien cc
chuan e
nh nhng
the khac
15
16
E=
0
E AgCl
/ Ag
0,059
1
lg
+
1
[Cl ]
/c thuy tinh
E = K + 0,059 lg a1 = K 0,059 pH
ien cc so sanh
ien cc ghep
ien cc thuy tinh
17
ien cc ghep
S o
ien
cc
ghep
(ien
cc
thuy
tinh)
18
19
H + + OH
H 2O
-Ve ng cong
chuan o thc
nghiem pH = f (V).
T o nh iem
tng ng
Do the va Chuan do dien the
Buret, H+
ien cc ch
th (ien cc
thuy tinh)
ien cc so
sanh
(Ag, AgCl/Cl-)
dd phan
tch, OH-
Edo
0,059
20
ien cc thch hp
- Phan ng chuan o
Ag + + Cl
AgCl
- Phan ng ien cc
Ag e
Ag +
ien cc so
sanh
(Ag, AgCl/Cl-)
Buret,
Ag+
ien cc ch th
(/c Ag kim
loai)
dd phan tch,
Cl-
21
Buret,
Ag+
ien cc ch th
(/c Ag kim
loai)
ien cc so
sanh
(Ag, AgCl/Cl-)
dd phan tch,
Cl-
E do = E chithi E sosanh
E chithi =
=
0
E +
Ag / Ag
E0 +
Ag / Ag
+ 0,059 lg[ Ag ]
+ 0,059 lg
E chithi = E 0
Ag + / Ag
TAgCl
[Cl ]
+ 0,059 lg TAgCl
22
- Phan ng ien cc
Ag e
Ag
ien cc so sanh
(Ag, AgCl/Cl-)
TAgBr = 5,3 10 13
TAgCl = 1,8 10 10
TAgI = 8,3 10 17
Buret, Ag+
ien cc ch th
(ien cc Ag kim loai)
23
E chithi =
0
E +
Ag / Ag
E do = E chithi E sosanh
+ 0,059 lg TAgBr
E chithi = E
Ag + / Ag
+ 0,059 lg TAgCl
E = E 2 E 1
0,059 T2
T2
lg( ) 0,2 hay
10 6,8
2
T1
T1
24
- Phan ng chuan o
Ox 2 + Kh1
Kh2 + Ox1
ien cc so
sanh
(Ag, AgCl/Cl-)
- Phan ng ien cc
E do = E chithi E sosanh
Buret,
Ox2
ien cc ch
th
(ien cc Pt)
dd phan tch,
Kh1
25
E chithi =
0
EOx1 / Kh1
0,059 [Ox1 ]
lg
+
n1
[ Kh1 ]
E chithi
n1 E10 + n2 E 20
=
n1 + n2
E chithi =
0
EOx2 / Kh2
0,059 [Ox 2 ]
lg
+
n2
[ Kh2 ]
26
- Phan ng ien cc
Hg 2e
Hg
2+
[ MY ]
=
[ M ][Y ]
E do = E chithi E sosanh
E chithi =
E chithi =
E 0 2+
Hg / Hg
E 0 2+
Hg / Hg
0,059
+
lg[ Hg 2+ ]
2
0,059
[M ]
0,059
[M ]
+
lg( K
) = A+
lg(
)
2
[ MY ]
2
[ MY ]
27
( 2) HgY
HgY
Hg
2+
+Y
[ HgY ]
21,8
=
= 10
2+
4
[ Hg ][Y ]
Khi them Y vao, Y tham gia ong thi 2 can bang (1) va (2)
2
[ HgY ] [ HgY ] [ M ] MY
[ Hg ] =
=
4
[ MY ]
HgY
HgY [Y ]
2+
=
Do the va Chuan do dien the
[ HgY 2 ]
HgY
MY
[M ]
[ MY ]
28
29
30
31
440
= 24,34 ml
440 + 590
590
= 24,34 ml
Vtd = 24,40 0,10
440 + 590
E td = 233 + 83
Vtd = 24,30 + 0,10
440
= 268 mV
440 + 590
32
440
= 24,34 ml
Vtd = 24,30 + 0,10
440 + 590
590
= 24,34 ml
Vtd = 24,40 0,10
440 + 590
E td = 233 + 83
440
= 268 mV
440 + 590
33
H + OH
H 2O
-Ve ng cong
chuan o thc
nghiem pH = f (V).
T o nh iem
tng ng
ien cc so
sanh
(Ag, AgCl/Cl-)
ien cc ch th
(/c thuy tinh)
E do = E chithi E sosanh
dd phan
tch, OH-
= K 0,059 pH E sosanh
= 0,059 pH
hay pH =
Buret, H+
Edo
0,059
34
V HCl
pH
0,00
5,00
10,00
10,669
10,172
8,520
12,30
12,40
12,50
12,60
12,70
8,487 - 0,117
- 0,003
8,370
- 0,120 + 0,005
8,250
8,135 - 0,115 + 0,012
- 0,103
8,032
20,00
6,478
30,00
30,10
30,20
30,30
30,40
4,382
- 0,236 - 0,051
4,146
- 0,287
+ 0,039
3,859
- 0,248
3,611
+ 0,076
- 0,181
3,430
35,00
40,00
2,190
1,910
Vtd 2
0,003
= 12,44 mL
0,008
0,051
= 30,10 + 0.10
= 30,16 mL
0,090
35
36
CuY
[CuY ]
=
[Cu 2+ ][Y 4 ]
T = [Cu+ ]2[S2-]
Do the va Chuan do dien the
37