I.

Phn ng oxi ha kh
- P xy ra c s thay i s oxy ha ca cc nguyn t.
BI 1: NHNG KHI NIM CHUNG
Gm hai qu trnh:
Cht kh 1 oxiha 1
Cht oxiha 2 kh 2
- e
-
+ e
-
QT oxi ha
QT kh
Cht kh 1 + cht oxi ha 2 oxi ha 1 + cht kh 2
V d: Zn + CuSO
4
ZnSO
4
+ Cu
0
0
+2
+2
Zn
0
- 2 e Zn
2+
Cu
2+
+ 2e Cu
0
Zn dng kh / Zn
2+
dng oxi ha
Cu
2+
dng oxi ha/ Cu dng kh
Vy: Zn + Cu
2+
Zn
2+

+ Cu
Phn ng trn xy dng t 2 cp oxi ha-kh:
Zn
2+
/Zn v Cu
2+
/Cu
Mi cp oxi ha kh c 1 th in cc c trng

oxi ha /kh

3.Th in cc phng trnh Nernst
- Th in cc l i lng th hiu c trng cho
qu trnh in cc hay in cc, k hiu l .
0
ln
ox
kh
a RT
nF a
= + Phng trnh Nernst
n: s electron trao i trong qu trnh in cc;
a
ox
, a
kh
: hot cc cht tham gia dng oxyha ,
dng kh;
F: s Faraday (96484 culong/mol)
R: hng s kh (8,314 J/mol)
T: nhit tuyt i.

0
: Th in cc tiu chun
ph thuc:
- bn cht in cc
- nhit
- nng
a
ox
= [OX].f
ox
; a
kh
= [KH].f
kh

f
ox
, f
kh
h s hot dng oxi ha, kh.
i vi dung dch long: f
ox
= f
kh
= 1

25
0
C:
0
0, 059 [ ]
lg
[ ]
Ox
n Kh
= +
3 3
2 2
3
2
[ ]
0, 059lg
[ ]
o
Fe Fe
Fe Fe
Fe
Fe

+ +
+ +
+
+
= +
V du: Tnh cua Fe
3+
/Fe
2+
25
0
C biet [Fe
3+
] =0,5M , [Fe
2+
] =1M
= 0,77 + 0,059 lg0,5 (V)
Fe
3+
+ 1e Fe
2+

0
Fe3+/Fe2+
= + 0,77V
i vi in cc kim loi (vd: Fe
2+
+ 2e Fe)


0
0, 059
lg[ ] Ox
n
= +
2
0 2
/
0, 059
lg[ ]
2
Fe Fe
Fe
+
+
= +
i vi cht kh (vd: 2H
+
+ 2e H
2
)


0
0, 059 [ ]
lg
Ox
n p
= +
2
2
0
2 /
0, 059 [ ]
lg
2
H H
H
H
p

+
+
= +

oxi hoa 1/kh 1

LN
Oxi hoa 1 : tnh oxi hoa |
Kh 1 : tnh kh +

oxi hoa 2/kh 2

NHO
Oxi hoa 2 : tnh oxi hoa +
Kh 2 : tnh kh |
Cc yu t nh hng n
a) nh hng ca nng H
+
(pH mi trng)
Khi [H
+
] gim (pH tng) gim
Vd: Cr
2
O
7
2-
+14H
+
+6e 2Cr
3+
+ 7H
2
O (
0
= 1,33 V)


Gi s [Cr
2
O
7
2-
] = [Cr
3+
] = 1
pH = 2, = 1,054 V
pH = 3, = 0,916 V
2 14
0
2 7
3 2
[ ].[ ] 0, 059
lg
6 [ ]
Cr O H
Cr

+
+
= +
b) nh hng ca phn ng to kt ta
Vd: Cu
2+
+ e Cu
+
(
0
= 0,158 V)


Khi c mt I
-
, Cu
+
+ I
-
CuI (T
CuI
= 5,1.10
-12
)
Khi :

Gi s: [Cu
2+
].[I
-
] = 1
= 1,72 V
Tnh oxi ha ca Cu
2+
tng ln ng k
2
0
[ ]
0, 059lg
[ ]
Cu
Cu

+
+
= +
2
0
[ ].[ ]
0, 059lg
CuI
Cu I
T

+
= +
c) nh hng ca phn ng to phc
Khi cht oxi ha hay cht kh ca cp oxi ha kh lin hp
tham gia phn ng to phc th th oxi ha kh b bin i
Vd: Fe
2+
- e Fe
3+
(1)
Khi c mt F
-
: Fe
3+
+ 6F
-
[FeF
6
]
3-
| = 10
16
(2)
Cng (1) vi (2): Fe
2+
+ 6F
-
- e [FeF
6
]
3-


3 2
0
/
( 0, 77 )
Fe Fe
V
+ +
=
3
0'
6
2 6
[ ]
0, 059lg
[ ].[ ]
FeF
Fe F


+
= +
Lc ny th oxi ha tiu chun =
0
khi:
(3)
3
6
2 6
[ ]
1
[ ].[ ]
FeF
Fe F

+
=
Theo phng trnh (2):

3
2 16
[ ] 1
[ ] 10
Fe
Fe
+
+
=
3
16
6
3 6
[ ]
10
[ ].[ ]
FeF
Fe F
|

+
= = (4)

Chia (3) cho (4):

Nh vy:

3 2 3 2
3
0
2 16
/ /
[ ] 1
0, 059lg 0, 77 0, 059lg 0,17
[ ] 10
Fe Fe Fe Fe
Fe
V
Fe

+ + + +
+
+
= + = + =
Khi c d F
-
kh nng oxi ha ca Fe
3+
gim, kh nng
kh ca Fe
2+
tng.

II.PIN IEN HOA (NGUYEN TO GALVANIC)
1.Phan ng oxi hoa kh va dong ien
a.Phan ng oxi hoa kh xay ra trong dung dch
Zn + Cu
2+
Cu + Zn
2+
,
mol / kcal 82 , 51 H
o
298
= A
Hoa nang nhiet (S trao oi e trc tiep )
ZnSO
4
CuSO
4

mang xop
Zn() (+)Cu
b.Khong cho chat oxi hoa va kh tiep xuc trc tiep
Zn
0
- 2 e Zn
2+
Cu
2+
+ 2e Cu
0
Co s trao oi e qua day dan
dong ien
2.Pin ien hoa (nguyen to galvanic)
- Gom 2 ien cc noi vi nhau bang mot day dan kim loai.
- ien cc n gian : 1 thanh kim loai nhung trong dung dch chat ien li
cua no
ZnSO
4
CuSO
4

mang xop
Zn () (+) Cu
Hoat ong cua nguyen to CuZn:
Nguyen to CuZn:
() Zn | Zn
2+
|| Cu
2+
| Cu (+)
Zn + Cu
2+
Cu + Zn
2+
,
Xem pin in ha
K hieu pin ien hoa:
(-) M
I
| ddM
I
|| ddM
II
| M
II
(+)
Cap oxh/kh 1
Cap oxh/kh 2
M: Kim loai
ddM : dung dch muoi
(nhng e)
(nhan e)
VD1: Xac nh pin tao thanh t 2 cap oxi hoa /kh: Pb
2+
/Pb va Ag
+
/Ag
Cho
0
(Pb
2+
/Pb) = - 0,126V ;
0
(Ag
+
/Ag)=+0,799 V
(-) Pb | Pb
2+
|| Ag
+
|Ag (+)
Cc am: Pb -2e Pb
2+
Cc dng: Ag
+
+ e Ag
Suat ien ong cua pin E (V)
E = (+) - (-)
E
o
=
0
(+) -
0
(-)
VD1: Xac nh pin tao thanh t 2 cap oxi hoa /kh: Pb
2+
/Pb va Ag
+
/Ag
Cho
0
(Pb
2+
/Pb) = - 0,126V ;
0
(Ag
+
/Ag)=+0,799 V
(-) Pb | Pb
2+
|| Ag
+
|Ag (+)
E
0
= 0,799 (-0,126) = 0,925V
VD2: Tnh suat ien ong va cho biet cac qua trnh ien cc, phan ng oxy hoa -
kh xay ra trong pin () Mg / Mg
2+
// Zn
2+
/ Zn (+) :
a. ieu kien chuan.
b. Khi [Mg
2+
] = 0,1 mol/ lit ; [Zn
2+
] = 0,01 mol/ lit.
Cho:
V 76 , 0 ; V 37 , 2
o
Zn
o
Mg
Zn
2
Mg
2
= =
+ +
III. CC LOI IN CC
IN CC SO SNH
IN CC CH TH
1.in cc so snh
L in cc m th ca n khng i, khng ph thuc dung
dch in ly m n nhng vo.
1.1 in cc hydro Pt, H
2 (1atm)
/ HCl
(1M)

L in cc chun dng xc nh in th ca cc in
cc khc v xc nh in th chun ca cc cp oxi ha kh
khc.
2H
+
+ 2e H
2

2
2
0
0, 059
lg
2
1; 1
H
H
H
H
a
p
a p atm

+
+
= +
= = Khi

v 25
0
C th =
0
= 0,000

Cu to in cc hydro

Dng in cc hydro xc nh th in cc chun ca
cc in cc

2
/ 2 /
/
/
0, 8 0, 000
0, 8
Ag Ag H H
Ag Ag
Ag Ag
E
V

+ +
+
+
=
+ =
= +
o
1.2 in cc bc bc clorua Ag/AgCl
bo ha
, Cl
-

Gm kim loi nhng vo dung dch mui t tan ca n. Dng
lm in cc so snh trong chun in th ca cc phn
ng trung ha, kt ta.
Phn ng in cc: Ag
+
+ e Ag hay AgCl + e Ag + Cl
-
Th in cc:
0
/
/
0
/
/
0 0
/
/
0
/ /
0, 059lg[ ]
0, 059lg 0, 059lg[ ]
0, 059lg
0, 059lg[ ]
AgCl Ag
Ag Ag
AgCl Ag AgCl
Ag Ag
AgCl Ag AgCl
Ag Ag
AgCl Ag AgCl Ag
Ag
T Cl
T
Cl




+
+
+
+

= +
= +
= +
=
trong o
vay
0 0 10
/
/
0, 059lg 0,8 0, 059lg1, 6.10 0, 222
AgCl Ag AgCl
Ag Ag
T V
+

= + = + =
25
0
C, T
AgCl
= 1,6.10
-10
v
0
Ag+/Ag
= 0,8 V
Khi :

Gi tr ca th in cc bc (
AgCl/Ag
) ph thuc [Cl
-
] :
in cc Gi tr
AgCl/Ag
(V)

1,00N KCl, AgCl/Ag 0,222
0,10N KCl, AgCl/Ag 0,2810
3,00N KCl, AgCl/Ag 0,1938
0,10N HCl, AgCl/Ag 0,2810
Cu to in cc bc

1. Dung dch HCl
2. Mui AgCl
3. Dy bc kim loi
4. Dy dn in
5. L b sung dung dch
6. L xp
1.3 in cc Calomel: Hg/Hg
2
Cl
2
, Cl
-

Gm Hg nhng vo dung dch mui ca n (Hg
2
Cl
2
). C gi
tr th rt n nh nhng v Hg c nn xu hng dng in
cc bc hn.
Phn ng in cc: Hg
2
Cl
2
+ 2e 2Hg + 2Cl
-

Th in cc:
2 2 /
2 2
0
/
0, 059lg[ ]
Hg Cl Hg
Hg Cl Hg
Cl

=
2
2 2
2
2 2 18 0
2
/ 2
[ ].[ ] 2.10 ; 0, 7961
Hg Cl
Hg Hg
T Hg Cl V
+
+
= = =
25
0
C
Khi :

2
2 2 2 2
2
0 0
/
/ 2
0, 059
lg 0, 274
2
Hg Cl Hg Hg Cl
Hg Hg
T V
+
= + =
Th in cc calomen ph thuc nng Cl
-
v nhit :
Cu to in cc calomen

1. Thy tinh xp
2. Thy tinh xp
3. Hg
2
Cl
2

4. Hg
5. Dy Pt
6. Dy dn in
7. Dung dch KCl
8. L np dung dch KCl
2. in cc ch th
L in cc m th ca n thay i, ph thuc vo nng
cht kho st trong dung dch m in cc nhng vo.
2.1 in cc ch th kim loi loi 1
Gm 1 in cc lm bng kim loi M nhng vo dung dch
ion M
n+
. in th cc ch ph thuc vo nng ion M
n+

0
/
0, 059
lg[ ]
n
n
M M
M
n

+
+
= +
ng dng: nh lng cc cation kim loi: Cu
2+
, Cd
2+
,
Pb
2+
trong nc, thc phm .

2.2 in cc ch th kim loi loi 2
Gm 1 kim loi A tip xc vi 1 mui t tan ca A v 1 mui
t tan ca B (nhng mui B tan nhiu hn mui A). C 2
mui c cng chung anion
VD: Ag/Ag
2
C
2
O
4
; CaC
2
O
4
/Ca
2+

Hg/Hg
2
C
2
O
4
; CaC
2
O
4
/Ca
2+
HOC:
Gm 1 kim loi A tip xc vi 1 phc bn ca A v 1 phc ca
B (nhng phc ca B km bn hn ca A). C 2 phc c
cng chung ligan
VD: Hg/HgY
2+
; MY
2-
/M
2+
(c bit M
2+
l Ca
2+
, Mg
2+
)

2.3 in cc oxi ha kh
Gm 1 kim loi tr (vd Pt) tip xc vi dung dch cha cp
cht oxi ha kh (Fe
3+
/Fe
2+
, MnO
4
-
/Mn
2+
).
VD1: in cc Pt/Fe
3+
,Fe
2+
Fe
3+
+ e Fe
2+



VD2: in cc Pt/MnO
4
-
,H
+
,Mn
2+

3 2
3
0
2
/
[ ]
0, 059lg
[ ]
Fe Fe
Fe
Fe

+ +
+
+
= +
2 2
4 4
5
0
4
2 4
, / , /
2
[ ].[ ] 0, 059
lg
5 [ ].[ ]
MnO H Mn MnO H Mn
MnO H
Mn H O

+ + + +
+
+
= +
2.4 in cc mng chn lc
Cu to in cc mng gm mt mng mng phn cch gia
2 dung dch:
-Dung dch X l dung dch cn xc nh nng
-Dung dch Y l dung dch chun, nm bn trong mng, cha
cng ion dung dch X.
in th in cc xut hin do s trao i khng ng u
gia ion cha trong mng (dd Y) v ion cn xc nh (dd X)
2.4.1 in cc thy tinh
Cu to:
Bu thy tinh cha dd HCl. in cc so snh Ag/AgCl
nhng vo dd ny.
Do s chnh lch nng ion H
+
gia lp mng bn
trong v lp mng bn ngoi s lm xut hin mt th
in cc
o pH ca dung dch X ngi ta ghp in cc thy tinh
vi in cc so snh (in cc calomen bo ha). Khi :
Ag/AgCl/dd HCl (dd Y) // dd X, Cl
-
/Hg
2
Cl
2
/Hg
( )
/
( )
( ln )
H X
calomen Ag AgCl bdx
H Y
a
RT
E
nF a

+
+
= + +

bx
: in th bt i xng (do c s khc bit v lng
H
+
khuch tn 2 mt ca mng thy tinh).
E = L + 0,059lga
H+

E = L 0,059pH
I.Nguyn tc
o th ca in cc ch th so vi in cc so snh. p dng
phng trnh Nersnt s tnh c hot ca cht cn phn
tch.
BI 2: PHNG PHP O TH TRC TIP
Nhc im ca phng php
-Mun xc nh nng cn phi bit h s hot (khng
d).
-Th o c thng khng lp li
- kt qu c chnh xc <1% th E
o
phi chnh xc n
0,25mV
-Phi bit in th khuch tn E
j
(hiu in th gia 2 mt
tip xc ca 2 dd)
Do : E
o
= E
catod
E
anod
+ E
j
gim E
j
cn chn cc dd c linh cation v anion cng
gn nhau cng tt.
VD: (-)Hg,Hg
2
Cl
2
/KCl
bo ha
// Fe
3+
,Fe
2+
,HCl 0,1M/Pt(+)
E
calomen (KCl bh)
= 0,244 V/NHE; E
Fe3+/Fe2+
= 0,771 V/NHE;
E
j
= 0,0047 V ; E
o
= 0,527 V. Tnh [Fe
3+
]/[Fe
2+
]
II. Cc phng php xc nh nng
I I .1 Phng php so snh (Pin nng )
Dng in cc M nhng vo dung dch X (cha ion M
n+
cn
xc nh) v in cc M nhng vo dung dch Y (cha ion
M
n+
bit chnh xc nng ). Nng 2 dd cn gn nhau.
M/M
n+
(X) // M
n+
(Y) /M
[ ( )]
ln
[ ( )]
n
n
RT M Y
E
nF M X
+
+
=
I I .2 Phng php lp ng chun
Xy dng ng chun vi 5-7 nng dd chun. T th
ng chun ta xc nh nng ca dd cn o da trn gi
tr th o c
[M
n+
]
E
E
o

[M
n+
]
kq

I I .3 Phng php thm chun
Dd kho st c nng X
n+
(cha bit) vi th tch V
x
, th
o c l E
1
. Thm vo 1 th tch V
c
chnh xc c nng
X
n+
( bit), th o c l E
2
.
2 1
[ ] .
[ ]
( ).10
( ).
0, 059
n
n
dabiet c
chuabiet
R
x c x
X V
X
V V V
E E n
R
+
+

=
+

=
n: S electron trao i
I.Nguyn tc
Dng in cc ch th v in cc so snh theo di s
thay i th ca dung dch theo nng cht kho st (trong
mu) khi thm dung dch chun vo mu.
u im ca PP:
-Dng cho cc trng hp khng c ch th hoc dd c mu
- nhy cao (C < 10
-5
M)
-D t ng ha, trnh c cc sai s ch quan.
BI 3: PHNG PHP O TH GIN TIP
(CHUN TH)
chnh xc ca PP ty thuc vo:
- chnh xc khi o th tch dung dch.
- chnh xc khi xc nh im tng ng.
iu kin p dng ca PP:
-Tc phn ng ln, khng c phn ng ph.
-Phn ng xy ra theo 1 chiu xc nh.
-C in cc ch th thch hp.
C 2 phng php:
-PP in th khng dng (i = 0)
-PP in th c dng