Page | 1

MT NG DNG CA GIN LATIMER V

NH HNG CA MI TRNG N TH OXI HA KH




Page | 2


MT NG DNG CA GIN LATIMER V
NH HNG CA MI TRNG N TH OXI HA KH
Nguyn Thnh Tr
Th X Ty Ninh- Tnh Ty Ninh
1. Gii thiu gin Latimer.
Nu mt nguyn t c th tn ti nhiu trng thi oxi ha, th ta c th tra cu cc th in
cc ri sp xp chng theo th t gim dn, km theo nhng mi tn t trng thi ny sang trng
thi khc ni ln s chuyn ha t dng ny sang dng khc. Cch sp xp ny c ngh
bi Wendell Latimer (1893 1955).
Gii thiu mt s gin :

0,56 2,26 0,95 1,51 1,18 2 3 2 0
4 4 2
MnO MnO MnO Mn Mn Mn
+ + + + + +





1,19 1,21 1,64
4 3 2
ClO ClO HClO HClO
+ + +





0,374 0,295 0,681 0,421 1,358
4 3 2 2
ClO ClO ClO ClO Cl Cl
+ + + + +



7 5 1
1,70 1,14 1,45 0,54
5 6 3 3
H I O I O HO I I I
+ + +
+ + + +



2. ng dng ca gin Latimer: Tnh th kh chun ca cc cp oxi ha kh khng
gn nhau.
2.1 Tnh gin tip:
C s ca cch tnh ny l da vo mi quan h gia G A

v E

ca qu trnh: G A

chung ca
n qu trnh lin tip nhau bng tng G A

ca n qu trnh. S tng qut:
-0,481 +1,071
+1,70
+1,23
+1,51
ClO
2

+1,15
+1,27
Cl
-

+1,47
Cl
2

+1,36
+1,63
+1,20
ClO
2
-


+0,89


Page | 3


1.52 V
( / ) ( / ) ( / )
1 2 3
1 ( / ) 1 ( / )
2 ( / ) 2 ( / )
3 ( / ) 3 ( / )
1 2 3 ( / ) ( / ) ( / ) ( / )
1 2 3 ( / )
( )
( )
A B B C C D
E E E
n e n e n e
A B A B
B C B C
C D C D
A D A B B C C D
A D
A B C D
A n e B G n FE
B n e C G n FE
C n e D G n FE
A n n n e D G G G G
n n n FE
+ + +

+ A =
+ A =
+ A =
+ + + A =A + A + A
= + +

1 ( / ) 2 ( / ) 3 ( / ) 1 2 3 ( / )
( ) ( )
A B B C C D A D
F n E n E n E F n n n E + + = + +


Rt ra cng thc kinh nghim:
1 ( / ) 2 ( / ) 3 ( / )
( / )
1 2 3
A B B C C D
A D
n E n E n E
E
n n n
+ +
=
+ +

(1)

2.2 Tnh trc tip:
Sp xp cc dng khc nhau ca nguyn t (c th l hp cht hoc l ion cha nguyn t )
theo th t s oxi ha gim dn.
Cc mi tn cho bit qu trnh oxi ha, km theo gi tr E

tng ng vi mi qu trnh.
Vn dng cng thc:
i i
nE n E A = A

(2)
Trong :
An, E

: l s thay i s oxi ha v th kh chun khi chuyn t trng thi ny sang trng thi
khc.
An
i
,
i
E

: l s thay i s oxi ha v th kh chun ca tng trng thi trung gian.

*Ch quan trng: Vic nhn phng trnh ca bn phn ng vi mt hng s bt k khng
lm thay i gi tr ca th.
Bi 1: Cho
2 2
3 2 2
/ ( )
/ ( )
1.60 , 1.52
HBrO Br H O
BrO Br H O
E V E V

= =

. Tnh
3
/ BrO HBrO
E

.
Gii:
Cch 1:
Ta vit cc bn phn ng kh:
2 2
3 2 2
2( ) 2 / ( )
3 2( ) 2 / ( )
2 2 2 2 1.60
2 12 10 6 1.52
l HBrO Br H O
l BrO Br H O
HBrO H e Br H O E V
BrO H e Br H O E V
+
+
+ + + =
+ + + =

Bin i:
3 2 2
2 2
3
3 2( ) 2 / ( )
2( ) 2 / ( )
3 2 /
2 12 10 6 1.52
2 2 2 2 1.60
2 10 8 2 4 ?
l BrO Br H O
l HBrO Br H O
BrO HBrO
BrO H e Br H O E V
Br H O HBrO H e E V
BrO H e HBrO H O E V

+
+
+
+ + + =

+ + + =

+ + + =

Theo cng thc (1) trn, ta c:
3
/
1.52 10 2.( 1.60)
1.50
8
BrO HBrO
E V

+
= =

.
Cch 2:
Sp xp cc dng tn ti ca Br theo trnh t oxi ha gim dn, km theo E

tng ng.
5 1 0
1.60
2
3
x V
Br O H Br O Br
+ +

Page | 4



Theo cng thc (2): 5 0 1.52 5 1 1 0 1.60
5 1.52 4 1.60
1.50
x
x
x V
= +
= +
=

Bi 2: nng 1M v 25
0
C, th in cc chun ca mt s cp oxi ha kh c cho nh
sau:
2
4 2
3 2 2
/ ( )
2 /
2 / ( ) ( )/ 2
1.31 1.45
1.19 0.54
HIO I r
IO I
IO I r I r I
E V E V
E V E V

= =
= =



a. Vit phng trnh bn phn ng oxi kh ca cc cp oxi ha kh cho.
b. Tnh
4 3
/
.
IO IO
E

c. Tnh
3
/
.
IO HIO
E

(Trch thi Olympic 30/4 nm 2011, Trng THPT Chuyn Nguyn Bnh Khim, S Gio
dc v o to tnh Qung Nam)
Gii:
a. Vit phng trnh bn phn ng oxi kh ca cc cp oxi ha kh cho.
4 2
3 2
2
2
4 2 2
2 /
3 2 2
2 /
2 2 /
2
( )/ 2
2 16 14 ( ) 8 1.31
2 12 10 ( ) 6 1.19
2 2 2 ( ) 2 1.45
( ) 2 2 0.54
IO I
IO I
HIO I
I r I
IO H e I r H O E V
IO H e I r H O E V
HIO H e I r H O E V
I r e I E V

+
+
+

+ + + =
+ + + =
+ + + =
+ =

b. Tnh
4 3
/
.
IO IO
E

Cch 1:
4 2
3 2
4 3
4 2 2
2 /
2 2 3
/
4 3 2
/
2 16 14 ( ) 8 1.31
( ) 6 2 12 10 1.19
2 4 4 2 2 ?
IO I
IO I
IO IO
IO H e I r H O E V
I r H O IO H e E V
IO H e IO H O E V

+
+
+
+ + + =

+ + + =

+ + + =

Theo cng thc (1):
4 3
/
1.31 14 10 ( 1.19)
1.61
4
IO IO
E V

+
= =

.
Cch 2:
7 5 0
1.19
2
4 3
x V
I O I O I
+ +




p dng cng thc (2): 7 1.31 1.19 5 2 1.61 x x V = + =

c. Tnh
3
/
.
IO HIO
E

Cch 1:
3 2
2
3
3 2 2
2 /
2 2 /
3 2
/
2 12 10 ( ) 6 1.19
( ) 2 2 2 2 1.45
2 10 8 2 3 ?
IO I
HIO I
IO HIO
IO H e I r H O E V
I r H O HIO H e E V
IO H e HIO H O E V

+
+
+
+ + + =

+ + + =

+ + + =

1.31 V


Page | 5

x
1.19 V
Theo cng thc (1):
3
/
1.19 10 2 ( 1.45)
1.125
8
IO HIO
E V

+
= =

.
Cch 2:




Theo cng thc (2): 1.19 5 4 1.45 1 1.125 x x V = + =
Bi 3: Cho gin Latimer:
5 6 1 0 3
1.12 1.57 2.05 2.89 3 2
4 4 2 2 3
V V V V
PO PO H PO P P H
+ + +



Tnh
2 2 3
/ H PO PH
E

trong mi trng kim.

(Trch thi Olympic 30/4 nm 2011, Trng THPT Chuyn Nguyn Bnh Khim,
S Gio dc v o to tnh Vnh Long)
Gii:
Gi x l gi tr ca
2 2 3
/ H PO PH
E

cn tm. Theo cng thc (2), ta c:

4 2.05 3 ( 2.89) 2.68 . x x V = + =
3. nh hng ca mi trng n th oxi ha kh.
Trong iu kin thc t, ngoi phn ng trao i electron, cht oxi ha v cht kh thng
tham gia nhng phn ng ph vi cc cht (hoc ion) c mt trong dung dch nh phn ng acid
base, phn ng kt ta, phn ng to phc.
Nhc li: iu kin tiu chun c quy c nh sau:
Nhit 25
o
C, p sut 1atm.
Kh quyn: Khng kh (oxygen chim 21% th tch).
Dung mi: Nc.
Nng cht: 1M.
pH: Acid (pH=0), Base (pH=14), Trung tnh (pH=7).
Khi , nng cht oxi ha v cht kh thay i so vi iu kin tiu chun tc l nh hng
n th oxi ha kh. Ta gi, th oxi ha kh mi ny l th oxi ha kh tiu chun iu
kin (gi tt l th iu kin).
3.1 nh hng ca pH:
Bi 1: Cho 3- 2-
4 3
3- + 2- o
4 3 2 AsO / AsO
AsO + 2H + 2e AsO + H O E = 0.57V. Tnh th oxi ha
kh tiu chun iu kin ca cp
3- 2-
4 3
AsO / AsO trong mi trng NaHCO
3
c pH=8.0
Gii:
Ti iu kin chun: pH=0 tc [H
+
]=1M.
3 2
4 3
3 2
4 3 2 /
2 2 0.57 .
AsO AsO
AsO H e AsO H O E V
+
+ + + =

| |
3 2 3 2
4 3 4 3
2
3
4
2 / /
3
0.059
lg
2
AsO AsO AsO AsO
AsO H
E E
AsO

+

(

= +
(

Trong mi trng NaHCO
3
c pH=8.0 tc [H
+
]=10
-8
M.
5 1 0
1.45
2
3
x V
I O H I O I
+ +

Page | 6

| |
| |
3 2 3 2
4 3 4 3
3 2
4 3
3 2
/
4 3
2
3
4
2 / /
3
3
2
4
2 /
3
'
0.059
lg
2
0.059 0.059
lg lg
2 2
AsO AsO
AsO AsO AsO AsO
AsO AsO
E
AsO H
E E
AsO
AsO
E H
AsO



+

(

= +
(

(

= + +
(

| |
( )
3 2 3 2
4 3 4 3
2
/ /
8
0.059
' lg
2
0.57 0.059lg 10
0.098 .
AsO AsO AsO AsO
E E H
V

+

= +
= +
=


Nh vy, th tiu chun iu kin (ti pH=8) gim so vi th tiu chun (pH=0) tnh oxi ha
ca
3
4
AsO

gim v tnh kh ca
3
3
AsO

tng.
3.2 nh hng ca cht t tan:
Nu trong dung dch c ion to kt ta vi cht oxi ha hoc cht kh th nng ca cht to
kt ta s gim. Nu cht to kt ta dng oxi ha th nng cht ny gim xung, ko theo s
gim tnh oxi ha ca c h thng.
Bi 2: Tnh
o
E ' ca bn phn ng sau:
( ) ( ) r r
AgCl e Ag Cl

+ + ti pCl=1.50.
Cho
+
o
AgCl
Ag / Ag
E = 0.799V, pT = 9.75.
Gii:
Ch thch:
1.50
1.50 [ ] 10 pCl Cl M

= =
Phng trnh Nernst cho Ag
+
/Ag:
/
/
0.059lg
Ag Ag
Ag Ag
E E Ag
+
+
+
( = +

Khi c Cl
-
trong dung dch:
| |
AgCl
T Ag Cl
+
( =


| |
| |
/ ,
/
/
/
'
0.059lg
1
0.059lg 0.059lg
AgCl Ag Cl
AgCl
Ag Ag
Ag Ag
Ag Ag AgCl
E
T
E E
Cl
E T
Cl
+

+

+

= +
= + +

| |
0
/ , / ,
' 0.059lg
0.799 0.059 9.75 0.059 1.5 0.31
AgCl
AgCl Ag Cl AgCl Ag Cl
T
E E
Cl
V


= +
= + =


Nh vy, s c mt ion Cl
-
trong dung dch lm th oxi ha thay i, hay ni cch khc s to
thnh kt ta AgCl lm gim ng k tnh oxi ha ca Ag
+
trong dung dch. C th ng dng
trng hp ny trong vic lm chm li phn ng oxi ha kh:
3 3 2 2
2 Ag HNO AgNO NO H O + + + .
3.3 nh hng ca cht to phc:
Trong nhiu trng hp phn ng oxi ha kh xy ra trong dung dch c cha cc cht to phc vi cc
dng oxi ha v dng kh. Chng hn, nu c mt ligand to phc vi cht oxi ha th nng dng oxi
ha gim, ko theo E gim, lm gim tnh oxi ha ca c h thng. Ngc li, nu ligand to phc vi dng
kh, E tng, tnh oxi ha tng v tnh kh ca dng kh gim.


Page | 7

0.337V
Bi 3: Tnh
2+ +
o
Cu /Cu
E ' trong dung dch c d NH
3
to phc Cu(NH
3
)
4
2+
c pK
1-4
=12 v
Cu(NH
3
)
2
2+
c pK
1-2
=10.9. Bit
+ 2+
o o
Cu / Cu Cu /Cu
E = 0.521V, E = 0.337V.
Gii:
tnh c
2
/
'
Cu Cu
E
+ +

, ta phi bit gi tr
2
/ Cu Cu
E
+ +

. Xy dng gin Latimer:

0.521 2 0 x V
Cu Cu Cu
+ +



Ta c: 2 0.337 0.521 0.153 x x V = + = .
Vy
2
/
0.153 .
Cu Cu
E V
+ +
=

2
0.153 Cu e Cu E V
+ +
+ =

.
p dng phng trnh Nernst:
| |
| |
2 2
2
/ /
0.059lg
Cu Cu Cu Cu
Cu
E E
Cu
+ + + +
+
+
= +

Khi c NH
3
th c hai ion Cu
2+
v Cu
+
u to phc vi ligand ny.
( )
( )
| |
| |
2
2 3
4 2 12
3 3 1 4 4 4 2
3
4 10
Cu NH
Cu NH Cu NH K
Cu NH
+
+
+

+
(

+ = =
( )
( )
| |
| |
3
2 10.9
3 3 1 2 2 2
3
2 10
Cu NH
Cu NH Cu NH K
Cu NH
+
+
+

+
(

+ = =
| |
| |
| |
| |
| |
| |
2 2
2
2
2
/
2
/ /
2
2
3 4 1 2 3
4 /
3 2 1 4 3
2
2
3 4 3 1 2
4 /
1 4
3 2 3
'
0.059lg
( )
0.059lg
( )
( )
0.059lg 0.059lg
( )
Cu Cu
Cu Cu Cu Cu
Cu Cu
Cu Cu
E
Cu
E E
Cu
Cu NH K NH
E
Cu NH K NH
Cu NH NH
K
E
K
Cu NH NH
+ + + +
+ +
+ +
+ +
+
+
+

= +
(

= +
(

(

= + +
(

2 2
1 2
/ /
1 4
10.9
12
' 0.059lg
10
0.153 0.059lg 0.218 .
10
Cu Cu Cu Cu
K
E E
K
V
+ + + +

= +
= + =


Nhn xt: C th nh tnh trc kt qu ca bi ton ny nh sau: So snh gi tr hng s phn li
ca 2 phc ng: Cu(NH
3
)
4
2+
c K
1-4
=10
-12
< Cu(NH
3
)
2
2+
c K
1-2
=10
-10.9
ngha l khi c 2 u to
phc, th Cu(NH
3
)
2
2+
c xu hng phn li ngc tr li thnh Cu
+
v Cu
+
tc dng tip tc vi
NH
3
d to phc. Nh vy, nng Cu
+
gim nhanh hn Cu
2+
, tc l dng oxi ha tng ln
(nhng tng khng nhiu). Vy th iu kin tng ln so vi iu kin chun. R rng:
2 2
/ /
' 0.218 0.153
Cu Cu Cu Cu
E E
+ + + +
= > =

.
Bi 4: Cho hng s bn cc phc
4-
6
Co(CN)
lg = 19.09,
2-
CoY
lg = 16.31. Th oxi ha kh ca cc
cp
- 2- 3- 4-
6 6
o o
CoY /CoY Co(CN) /Co(CN)
E = 0.674V, E = -0.81V . Tnh:
a. Tnh
3-
6
Co(CN)
.
b. Tnh
-
CoY
.
Bit:
2+
2+ o
Co / Co
Co + 2e Co E = -0.277V


Page | 8

3+ 2+
3+ 2+ o
Co /Co
Co +e Co E = 1.84V
Gii:
a. Tnh
3
6
( ) Co CN
|

.


p dng phng trnh Nernst:
| |
| |
3 2 3 2
3
/ / 2
0.059lg
Co Co Co Co
Co
E E
Co
+ + + +
+
+
= +

Khi c CN
-
th Co
3+
v Co
2+
u to phc vi ligand ny.
| || |
| || |
3
6 3 3
6 3 6
3
4
6 2 4
6 4 6
3
( )
6 ( )
( )
6 ( )
Co CN
Co CN Co CN
Co CN
Co CN
Co CN Co CN
Co CN
|
|

+
+

+
+
(

+ =
(

+ =

| |
| |
| |
| |
| |
3 2 3 2
3 2
3 2
3 4
( ) / ( )
6 6
3
/ / 2
6
3
6 4
6 /
4
6 3
6
3
6 4
/
4
3
6
'
0.059lg
( ) . .
0.059lg
( ) . .
( ) .
0.059lg 0.059lg
( ) .
Co CN Co CN
Co Co Co Co
Co Co
Co Co
E
Co
E E
Co
Co CN CN
E
Co CN CN
Co CN CN
E
Co CN CN
|
|
|
|
+ + + +
+ +
+ +

+
+

= +
(

= +
(

(

= + +
(

| |
6

3 4 3 2
6 6
3 4 3 2
6 6
3 4 3 2
( ) / ( ) /
6 6
4
( ) / ( ) /
3
( ) / ( ) /
4
3
'
0.81 1.84
19.09 64
0.059 0.059
3 4
' 0.059lg
'
lg
0.059
10 10 10 10 .
Co CN Co CN Co Co
Co CN Co CN Co Co
Co CN Co CN Co Co
E E
E E
E E
|
|
|
|
| |
+ +
+ +
+ +

= +

=
= = =




b. Tnh
CoY
|

.
3 2
3 2
/
1.84
Co Co
Co e Co E V
+ +
+ +
+ =

p dng phng trnh Nernst:
| |
| |
3 2 3 2
3
/ / 2
0.059lg
Co Co Co Co
Co
E E
Co
+ + + +
+
+
= +

Khi c Y
4-
th Co
3+
v Co
2+
u to phc vi ligand ny.
| |
| || |
| |
| || |
3 4
1
3 4
2
2 4 2
2
2 4
CoY
Co Y CoY
Co Y
Co
Co Y CoY
Co Y
|
|

+
+

+
+
+ =
+ =

2
2
/
2 0.277
Co Co
Co e Co E V
+
+
+ =

Page | 9

| |
| |
| | | |
| | | |
| |
| |
3 2 3 2
3 2
3 2
2
/
3
/ / 2
4
2
/ 2 4
1
2
/ 2
1
'
0.059lg
. .
0.059lg
. .
0.059lg 0.059lg
CoY CoY
Co Co Co Co
Co Co
Co Co
E
Co
E E
Co
CoY Y
E
CoY Y
CoY
E
CoY
|
|
|
|
+ + + +
+ +
+ +

+
+

= +
= +
= + +

2 3 2
2 3 2
2 3 2
/ /
2
/ /
1
/ / 2
1
'
1.84 0.674
16.31 36
0.059 0.059
1 2
' 0.059lg
'
lg
0.059
10 10 10 10 .
CoY CoY Co Co
CoY CoY Co Co
CoY CoY Co Co
E E
E E
E E
|
|
|
|
| |
+ +
+ +
+ +

= +

=
= = =





BI TP T GII
Bi 1: Cho 0.80 Ag e Ag E V
+
+ =

a. Tnh th oxi ha kh tiu chun iu kin ca cp Ag
+
/Ag trong dung dch c d NH
3

to phc Ag(NH
3
)
2
+
. Bit pK
1-2
ca Ag(NH
3
)
2
+
=7.20. C th kt lun g v tnh kh ca Ag
trong dung dch ny?
b. Bit
2
( ) 0.42 Ag CN e Ag CN E V

+ + =

. Hy d on bn ca phc Ag(CN)
2
-
so
vi phc Ag(NH
3
)
2
+
, t tnh hng s bn tng cng ca phc Ag(CN)
2
-
.
p s:
a. 0.38V.
b.
20.7
10 | = .
Bi 2: Tnh hng s bn tng hp ca phc Au(CN)
2-
theo phn ng:
2 2
2 ( ) ? Au CN Au CN |
+
+ =
Bit
/
1.68
Au Au
E V
+
=

,
2
( ) /
0.58
Au CN Au
E V

.
p s:
38.3
2
10 | = .
Bi 3: Tnh ' E

ca bn phn ng sau:
2
( )
2 2 2 2
r
Cu I e CuI
+
+ + ti pI=1.0.
Cho
2
/
0.159 , 11.96
CuI
Cu Cu
E V pT
+ +
= =

.
p s:0.807.