87

Chuong 4: DNG HOC MT S QUA TRINH

DIN CUC THUONG GP
I. Dng hoc qua trinh thoat hydro:
Ion H
+
tn tai trong dung dch nc di dang ion hydroxoni b hydrat hoa H
3
O
+

(H
+
.H
2
O). Cac ion nay tac dung vi in t cua in cc tao thanh phn t hydro thoat ra
ngoai. Qua trnh in cc bao gm nhiu giai oan:
Trong mi trng axit:
O H H Me e O H Me
hp 2 3
) ( ) ( + +
+
(a)
2
2 ) ( ) ( H Me H Me H Me
hp hp
+ + (b)
Hay vic tao thanh phn t H
2
co th xay ra theo c ch in hoa:
O H H Me e O H H Me
hp 2 2 3
) ( + + + +
+
(c)
Trong mi trng kim:
Do nng H
3
O
+
rt nho nn:

+ + OH H Me e O H Me
hp
) ( ) (
2
(a)
sau o:
2
2 ) ( ) ( H Me H Me H Me
hp hp
+ + (b)
Hay:

+ + + + OH H Me e O H H Me
hp 2 2
) ( (c)
Do vy, qua trnh thoat hydro trn in cc co th b km ham bi trong mt cac
qua trnh sau:
+ Chm khuych tan ion H
3
O
+
n in cc.
+ Chm nhn in t (chm phong in) (giai oan c, c)
+ Chm tai kt hp thanh phn t H
2
theo c ch hoa hoc (giai oan b, b)
+ Chm tai kt hp thanh phn t H
2
theo c ch in hoa hoc (giai oan c, c)
1.1. Chm khuych tan ion H
3
O

dn din cuc.
Ta xet mt axit rt loang a ui ht kh, th s vn chuyn ion H
3
O
+
n in cc
rt nho n mc ma qua trnh in cc b khng ch bi qua trnh khuych tan.
Ta co dong khuych tan:

) (
*
,
+ + +

=
H H H
H c
C C FD
i (4.1)
Trong o:
+
H
D : h s khuych tan cua ion H
+
(khoang 10
-4
cm
2
/s).
+ +
H H
C C ,
*
: nng cua ion H
+
trong dung dch va sat b mt in cc (mol/cm
3
).
: chiu day cua lp khuych tan (khoang 0.001 0.003 cm)
Dong in gii gii han:

*
,
+ +
=
H H gh
C FD
i
H c
(4.2)
T o ta xac nh c qua th thoat hydro trn in cc bng:
88
) 1 ln(
,
,
gh
H c
H c
cb H
i
i
F
RT
= = (4.3)
Gia tr cua 0 < =
cb H
v ) (
cb
<
1.2. Chm phong din:
Trong dung dch axit:
O H H e O H
hp 2 3
) ( + +
+

Ap dung phng trnh Butler-Volmer ta co:
) (
) 1 (
, 0
,
H H
nf nf
H
H c
e e i i

=
+
(4.4)
- Khi qua th hydro be, ta co:
+
=
H
H c
H
Fi
RTi
, 0
,
(4.5)
Vy khi qua th hydro be th qua th hydro la ham s bc 1 cua mt dong.
- Khi qua th hydro ln, ta co:
H c H
i
F
RT
const
,
ln
2
= (4.6)
Trong o tha nhn h s chuyn in tch 5 . 0 =
+
H
, va
+
=
H
i
F
RT
const
, 0
ln
2

Trong dung dch kim:

+ + OH H e O H
hp
) (
2

ta co:

=
OH
H c H
C
F
RT
i
F
RT
const ln ln
) 1 (
,

(4.7)
trong o:
+

=
H
i
F
RT
const
, 0
ln
) 1 (

1.3. Chm tai kt hop cac nguyn tu hydro theo phuong phap hoa ho c:
Giai oan chm nht la thai hydro hp phu theo phan ng:

) ( 2
'
2
khi
K
hp
H H (b)
Theo ng hoa hoc th tc phan ng (b) bng:

2
'
Hi
Hi
C K
dt
dC
=
Mc khac tc tao thanh nguyn t hydro ty l thun vi mt dong in:
i
K dt
dC
Hi
"
1
= (
"
1
K
: h s ty l)
Nu bo qua phan ng thun nghch tc la qua trnh phn li phn t H
2
thanh
nguyn t th qua trnh tin hanh n nh, s nguyn t tao thanh catt phai bng s tai
kt hp. T o suy ra:

" '
'
"
1
2
K K
i
C C K i
K
Hi Hi
= = (4.8)
89
in th in cc cn bng cua hydro:

0
0
ln ln ln ln
H
H
H
H
cb
C
F
RT
C
F
RT
K
F
RT
KC
C
F
RT
+ = =
+
+
(4.9)
Do o khi dong in i qua:

0
ln ln ln
Hi
H
i
C
F
RT
C
F
RT
K
F
RT
+ =
+
(4.10)
Thay gia tr C
Hi
vao (4.10):
i
F
RT
K K
F
RT
C
F
RT
K
F
RT
H
i
ln
2
" ' ln
2
ln ln + + =
+

[ ] i
F
RT
C K K
F
RT
H
cb i H
ln
2
) ( " ' ln
2
2 0
= =
+
(4.11)
Vy: i b a
H
ln ' + =
(4.12)
Trong o:
[ ]
F
RT
b
C K K
F
RT
a
H
2
'
) ( " ' ln
2
2 0
=
=
+
(4.12)
Hay: i b a
H
log + =
Vi:
F
RT
b
2
303 . 2
=
T (4.12) ta thy rng a phu thuc vao ban cht cua kim loai thng qua hng s
tc cua phan ng tai kt hp K:

RT A
e q K
/
. '

= th gia tr nay vao (4.12) ta co:
) ln 2 (
2
0
+
=
H
C
RT
A
B
F
RT
a (4.13)
trong o:
q: h s ty l
A: nng lng kch ng cua phan ng tai kt hp
) " ln( q K B =
T (4.13) ta nhn thy a cang m khi nng lng kch ng cang ln va qua th
hydro cang tr nn m hn. Noi cach khac, kim loai cang xuc tac phan ng tai kt hp
kem (A ln) th qua th hydro trn no cang ln.
Bongphe a chng minh rng, hoat tnh xuc tac cua kim loai thay i song song
vi qua th hydro.
Chiu tng hoat tnh xuc tac

Pt, Pd, W, Ni, Fe, Ag, Cu, Zn, Sn, Pb

Chiu tng qua th
90
Ngha la kim loai co qua th ln th xuc tac phan ng tai kt hp kem hn kim loai
co qua th nho.
Tuy nhin thuyt tai kt hp b nhiu ngi phan i v:
Theo l thuyt tai kt hp, kim loai nao hp phu hydro nhiu se co qua th
nho, nhng kim loai Ta (tantal) hp phu hydro nhiu hn kim loai nhom st lai
co qua th rt ln.
Nhng s liu thc nghim cho thy
H
phu thuc vao pH dung dch, cac ion
la, khuy ch tan cua lp in tch kep, s co mt cua cac cht hoat ng b
mt. Th l thuyt tai kt hp khng giai thch c.
Qua th khi kim loai phong in, khi thoat oxy, trong cac phan ng oxy hoa
kh u tun theo phng trnh Tafel. Nh vy co th noi rng nguyn nhn
gy qua th cua cac qua trnh trn tng tu nhau, nhng trong phn ln cac
qua trnh trn khng thy hin tng tai kt hp.
Qua th thoat hydro con xut hin mt dong thp, tai o khng co hydro
thoat ra.
Ly thuyt tai kt hp tm thy
F
RT
b
2
303 . 2
= trong khoi o thc nghim cho
thy vi phn ln cac kim loai th
F
RT
b
303 . 2
2 = , ngha la 4 ln ln hn.
1.4. Chm tai kt hop cac nguyn tu hydro theo phuong phap din hoc:
Hydro b hp phu co th b loai khoi b mt in cc theo c ch:

2
H e H H
hp
+ +
+

Nu giai oan nay chm th trn in cc se tch tu hydro b hp phu va khi o
qua th se bng:

hp
cb
i
hp H
=
trong o:

hp
i
H hp i
hp
KC
C
F
RT +
+ = ln
) ( 0


hp
cb
H hp hp
cb
KC
C
F
RT +
+ = ln
) ( 0

vi:

i
hp
: in th in cc hydro tai mt dong in i

hp
cb
: in th in cc hydro tai cn bng.

hp
cb
hp
i
C C , : nng hydro hp phu tai mt dong in i va tai cn bng.
Do o:
hp
i
hp
cb
H
C
C
F
RT
ln = (4.14)
Tc phan ng in cc theo phan ng trn:
91

+
=
H
hp
i H c
C kC i
,

Khi co cn bng th tc phan ng thun bng tc phan ng nghch:

0
i C kC i i
H
hp
cb
= = =
+


Th cac gia tr
hp
cb
hp
i
C C , vao (4.14) ta co:

H c
H c
H
i
F
RT
i
F
RT
i
i
F
RT
, 0
0
,
ln ln ln = = (4.15)
t:
0
lni
F
RT
a =
ta c:
H c H
i a
,
log 059 . 0 = 25
o
C
Ta nhn thy rng h ng s b y bng 1/2 cua thuyt chm phong in va
gp i thuyt chm kt hp. Do o cn c vao hng s b ta co th xac nh c c
ch cua phan ng thoat hydro.
II. Su khu oxy trn catt va co ch cuano:
Trong mi trng axit, s kh tun theo phan ng tng quat sau:
O H e H O
2 2
2 4 4 + +
+

Trong mi trng trung tnh va kim:

+ + OH e O H O 4 4 2
2 2

Phan ng kh oxy catt bao gm nhiu giai oan:
- Giai oan khuych tan oxy t th tch dung dch n b mt in cc.
Dong in gii han cua s kh:

*
2
2 2
4
O
O
gh
O
C
FD i =
vi: s cm D
O
/ 10
2 5
2

= tai 25
o
C
3 7 *
/ 10 . 2
2
cm mol C
O

= tng ng vi srj bao hoa khng kh trong dung dch.

cm
3
10 . 5

=
th:
2
/ 15 . 0
2
cm mA i
gh
O
=
Trong dung dch tnh th gia tr
gh
O
i
2
giam i 10 ln, con trong dung dch khuy trn
manh lit th gia tr
gh
O
i
2
tng ln 5 ln do giam. Trong cac h thng tr nh b tng, t,
le d nhin dong in gii han cua oxy cang be. Trong dung dch trung tnh, trn b mt
kim loai co phu mt lp g, s khuych tan oxy cang b can tr manh nn rt kho anh gia
gia tr
gh
O
i
2
.
Trong mi trng trung tnh va kim ta xac nh c qua th cua oxy:
( )
( )
( )
( )
bm OH
OH
O
bm
O
O
C
C
F
RT
C
C
F
RT

+ =
*
*
ln
4
ln
4
2
2
2
(4.16)
92
Khi
gh
O O
i i
2 2
th s hang th nht tin ti (-) con s hang th hai tin ti mt gia tr
nht nh va nho hn s han th nht nn:

( )
( )
*
2
2
2
ln
4
O
bm
O
O
C
C
F
RT
=
trong o:
*
2 2
, ) (
O bm O
C C : la nng oxy trn b mt va trong dung dch tng ng.
Tng tu nh trng hp phn cc nng , ta co:

=
gh
O
O
O
i
i
F
RT
2
2
2
1 ln
4
(4.17)
Trong o:
*
2
2
2
2
1
O
O
gh
O
O
C
C
i
i
=

Trong trng hp ng thi xay ra phan kh hydro va phan ng kh oxy, th
ng cong phn cc catt xay ra phc tap hn:

2
O H
i i i + = (4.18)
trong o:

=
RT
F
i
RT
F
i
i
RT
F
i i
H
O H
H
gh
H
H
H
H H

) 1 ( exp
) 1 ( exp 1
) 1 ( exp
0
0
0
2
(4.19)
s hang th nht ng vi phan ng:

2
2 2 H e H +
+

s hang th hai ng vi phan ng:

+ + OH H e O H 2 2 2
2 2

=
RT
F
n
i
i
RT
F
n
i i
O
e
gh
O
O
O
e
O O
2
2
2
2
2 2
) 1 ( exp 1
) 1 ( exp
0
0

(4.20)

0
2
O
i : la dong in troa i cua oxy trn kim loai in cc, thng co gia tr rt nho
ngay ca tn in cc khng co lp phu oxyt va khoang t 10
-10
10
-13
A/cm
2
.
Do o ta co th vit lai phng trnh (4.18):
93

=
RT
F
i
RT
F
i
i
RT
F
i i
H
O H
H
gh
H
H
H
H

) 1 ( exp
) 1 ( exp 1
) 1 ( exp
0
0
0
2

RT
F
n
i
i
RT
F
n
i
O
e
gh
O
O
O
e
O
2
2
2
2
2
) 1 ( exp 1
) 1 ( exp
0
0

(4.21)
Phng trnh (4.21) co th c n gian hn nu oxy phong in la chu yu. Khi
o s hang th nht v phai cua phng trnh co th bo qua, con s thoat hydro t nc
theo phan ng

+ + OH H e O H 2 2 2
2 2
ch ang k khi qua th hydro ln.
Nh vy nu qua th hydro nho th dong catt ch tng ng vi s kh oxy theo
phng trnh (4.20). Dong in se tng theo ham s mu khi chuyn dch in th v pha
m hn, sau o dng cong phn cc se xut hin oan nm ngang tng ng vi dong
gii han cua s kh oxy. Khi qua th hydro ln, phn t nc bt u phong in va dong
catt tng theo ham s mu.
i(mA/cm
2
)

-1.0 -

-0.8 -

-0.6 -

-0.4 - 2 1

-0.2 -


-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -(V)
Hinh 4.1. ng cong phn cc catt kh oxy ng thi vi hydro trn in cc Ni
Dung dch NaOH + NaCl 0.5M
1. Dung dch a ui oxy
2. Dung dch cha ui oxy
Hnh 4.1. cho thy n tn in th -0.8 V s kh oxy vn chu yu. Tht vy, khi
ui ht oxy bng kh tr (N
2
chng han) th dong in qua dung dch nho hn (ng 1)
rt nhiu so vi khi cha ui oxy (ng 2).
Con khi in th m hn -0,8 V ch con nc phong in theo phan ng trn.
94
Phng trnh (4.20) cha noi ht s phc tap cua qua trnh kh oxy. Khi nghin
cu s kh oxy trn in cc catt thuy ngn ta nhn thy:
I(A)

-10 -

- 8 -

- 6 -

- 4 -

- 2 -


0 -0.5 -1.0 -1.5 -2.0 -(V)
Hinh 4.2. ng cong phn cc catt kh oxy trn in cc giot
thuy ngn trong dung dch KCl
ng cong phn cc co hai song, trong o in th m nht co s kh ng
thi nc thanh hydro va kh hp cht trung gian H
2
O
2
. V qua trnh phong in cua oxy
gm hai giai oan ni tip:
Trong mi trng trung tnh va kim:

+
+ + +
OH e O H
OH O H e O H O
2 2
2 2
2 2
2 2 2 2

Trong mi trng axit:
O H e H O H
O H e H O
2 2 2
2 2 2
2 2 2
2 2
+ +
+ +
+
+

ng cong ch co hai song khi cn phai co qua th ln kh H
2
O
2
. Khi y s
kh oxy thanh H
2
O
2
a b khng ch bi khuych tan oxy va dong kh oxy at ti gii
han. Ch co in th u m H
2
O
2
mi tip tuc b kh tip va dong kh H
2
O
2
cung at ti
gii han. C n lu y rng, s tao thanh H
2
O
2
cung nh s kh no thanh H
2
O hoc thanh
OH
-
cung g m nhiu giai oan.
V du: s tao thanh H
2
O
2
trong mi trng axit:

2 2 2
2 2
2 2
2
O H H HO
HO e HO
HO e H O
+
+
+ +
+

+

Tuy nhin, trn in cc Pt nhn cho thy khng co cht trung gian H
2
O
2
.
V vy, trong mi trng axit xay ra phan ng sau:
95

O H e H OH
O OH HO
HO e H O
2
2 2
2 2
2
1
2
+ +
+
+ +
+
+

Con trong mi trng kim th:

+
+
+ +
+
OH e OH
O OH HO
OH HO O H O
O e O
2 2
2 2 2
2 2
2
1

III. Su kt tua din cua kim loai:
Qua trnh in kt tua kim loai t dung dch nc la c s cua phng phap thuy
luyn kim va ma in.
1/ Diu kin xut hin pha moi:
Khi cac phan ng in cc xay ra thng co s hnh thanh pha mi. V du, kh
ion H
+
se tao thanh cac bot kh, khi kh cac ion kim loai se xut hin tinh th kim loai.
S tao thanh pha mi thng bt u t s tao mm tinh th (rn) hoc giot (long).
S xut hin pha mi thng gp tr ngai va tn nng lng. V vy, mun kt
tinh mui t dung dch hoc ngng tu giot cht long t pha hi th nng mui va ap
sut hi phai at ti mt qua bao hoa nht nh.
2/ Qua th kt tua kim loai o din cuc:
Qua trnh in kt tua kim loai t dung dch nc la c s cua phng phap thuy
luyn kim va ma in. No th ng c tin hanh trong cac dung dch mui n hoc
phc va noi chung bao gm cac giai oan sau:
[ ] [ ]
+ +

Z
lkep x
Z
dd x
O H Me O H Me ) ( ) (
2 2
(a)
[ ] O xH Me O H Me
Z Z
lkep x 2 2
) ( +
+ +
(b)

nguyentu
Z
Me ze Me +
+
(c)

the t mam nguyentu
Me Me
. .
(d)

tinhthe luoi the t mam
Me Me
. . .
(e)
Nhng giai oan sau y co th khng ch qua trnh kt tua kim loai:
Giai oan (d) hoc (e) b chm tr: chm kt tinh.
Giai oan (c) b chm tr: chm phong in.
2.1. Ly thuyt chm kt tinh:
Volmer gia thit rng, trong qua trnh in kt tinh kim loai th qua th ong vai
tro nh qua bao hoa khi kt tinh tinh th t dung dch, hay gradient nhit trong
trng hp nong chay.
96
Qua trnh kt tua kim loai co th b khng ch bi tc tao thanh mm tinh th
hai hoc ba chiu.
a/ Tc tao thanh mm tinh th ba chiu khng ch ng hoc qua trnh kt
tua in.
Mm tinh th ba chiu la mt vi th mi xut hin trong pha cu. Mm nay phai co
kch thc u ln th mi tn tai cn bng vi pha cu.
ng hoc qua trnh kt tua in kim loai se b khng ch bi tc tao mm tinh
th ba chiu khi kim loai kt tua trn b mt in cc la hoc trn in cc cung loai
nhng b thu ng hay ng c. Trong trng h p nay qua th cua kim loai ong vai tro
nh qua bao hoa:

S
C
C
RT ZF ln = (4.22)
trong o: C, C
S
: nng qua boa hoa va bao hoa.
Tc tao thanh mm tinh th ba chiu co th biu din bng phng trnh:

RT A
Ke i
/
3

= (4.23)
trong o:

= =
2
2 2
2 3
3
ln
16
3
1
. 6
3
1
S
i i
C
C
T R
V
S A

(4.24)
A
3
: cng tao mm tinh th (cng se giam khi tng qua bao hoa
S
C
C
)
S: din tch b mt phn t.
V: th tch phn t.
S 6: ng vi 6 mt cua mt tinh th lp phng.
Xac sut W tao mm tinh th mi quan h vi cng theo phng trnh sau:

=
RT
A
B W
3
exp (4.25)
B: hng s; khi A
3
giam th xac sut tao mm tng ln.
Thay (4.24) va (4.22) vao (4.23) ta co:
i b a log
1
2
=

(4.26)
Trong o:
K
V
F Z
a ln
32
2 3
2 2

=

2 3
2 2
32
303 . 2
V
F Z
b

=
S tao thanh mm tinh th kim loai ba chiu co y ngha rt ln vi ng hoc cua
qua trnh chuyn pha. No thng xay ra trong trng hp kt tua kim loai trn b mt
97
in cc hay la tinh th mi sinh ra khng th ln ln c na, nn mun tao thanh pha
mi phai tao thanh mm tinh th ba chiu mi.


cb








'
i


i


t
Hinh 4.3. Bin thin in th in cc theo thi gian t khi kt tua kim
loai trn in cc la.
cb i i
, ,
'
ien the ng vi mt dong i, i, va cn
bng.
Ban u v phai nap in tch cho lp kep va in cc la nn cn phai dch chuyn
in th in cc v pha m ti mt qua th ban u la + u tao thanh mm tinh
th u tin. Nhng khi a co mt lp tinh th mi trn in cc th qua th giam xung
con v b mt in cc khng phai la la na. Nu ngt dong in th in th in cc
tr v in th cn bng
cb
.
b/ Tc tao thanh mm tinh th hai chiu khng ch ng hoc qua trnh kt
tua in.
Khi a co mm tinh th th cac tinh th ln ln theo tng lp. o la s tao mm
tinh th hai chiu. Tht vy, tinh the ln ln do tip nhn cac phn t mi. Cac phn t
mi nay c giu lai trn b mt tinh th bi cac lc hut. Cac lc hut nay ch co tac dung
trong mt khoang cach rt nho va thng ch co tac dung vi cac phn t k cn.



I III




II
Hinh 4.4. S hnh thanh tinh th hai chiu.
98
Trn s trn th nng lng cn thit se nho nht khi phn t cu truc c in
vao v tr III, v tr II oi hoi nng lng ln hn, con v tr I cn nhiu nng lng nht.
V tr I tng ng vi thi im bt u phat trin tinh th, con khi trn b mt a co tp
hp nhng phn t cu tao th co kha nng in nhiu ln vao v tr III la v tr co li nht
v mt nng lng. Kiu tao mm trn trn goi la tao mm tinh th hai chiu.
Nu goi A
2
la cng cn thit tao mm tinh th hai chiu bn vng, ta co:

RT A
e K i
/
1
2

= (4.27)
i: tc tao mm tinh th hai chiu.
K
1
: hng s
S
C
C
RT
S
A
ln
2
2

= (4.28)
: sc cng bin.
S: b mt phn t.
qua bao hoa can thit tao mm tinh th lin quan n qua th theo cng
thc:
S
C
C
ZF
RT
ln =
Do o:

ZF
S
e K i
2
1

=
Hay:
i b a
i b a
ln
1
ln
1
=

=

(4.29)
Trong o:

1
2
ln K
S
ZFRT
a

=

S
ZFRT
b
2

=
Nh a trnh bay trn khng phai ion phong in trn in cc bt k ch nao
ma ch nhng ni co li v mt nng lng nht. Sau o nguyn t con phai dch
chuyn trn b mt in cc va tm ch thch hp chuyn vao mang li tinh th. Do
o, chung cn phai thng tr lc cua mi trng bao quanh trung tm phat trin.
thng tr lc o cn phai co mt qua th nht nh. Khi y gia qua th va mt
dong co mi quan h bc 1 theo nh lut Ohm:
Ki = (4.30)
Volmer chia kim loai thanh hai nhom:
Nhom kim loai phn cc nho: Hg, Cu, Zn, Cd, Ag, Bi. Phn cc kt tinh la
chu yu.
99
Nhom kim loai co phn cc ln gm cac kim loai nhom st. Nhom nay phn
cc gy ra bi chm phong in.
Con kim loai Pb chim v tr trung gian.
Thuy ngn ch co phn cc nng .
2.2. Ly thuyt chm phong din:
Hin nay ngi ta a chng minh rng co th dung l thuyt chm phong in cho
qua trnh kt tua in va ion hoa kim loai. xa in th cn bng, tc phan ng
nghch co th bo qua va ta co phng trnh Tafel:
i b a log + = (4.31)
trong o:
ZF
RT
b
) 1 (
303 . 2

=

0
ln
) 1 (
303 . 2 i
ZF
RT
a

=
i
0
: mt dong trao i cua phan ng: Me Ze Me
Z
+
+

Qua th tng gia tr m khi giam i
0
, v vy nho m st co i
0
nho nht nn qua th
cung ln nht v gia tr tuyt i va qua trnh phong in cua cac ion nhom st b khng
ch bi qua trnh chm phong in.
3/ Ly thuyt v su pho ng din dng thoi cua cac cation kim loai:
Trong dung dch bao gi cung co nhiu ion hoc cac phn t hoa tan. V du, trong
dung dch nc thng co cac ion H
+
, ion kim loai va oxy hoa tan. Do o khi in phn
nhiu cht phan ng co th phong in. Nghin cu qui lut phong in ng thi cua cac
ion co y ngha ky thut quan trong, no giup chung ta iu ch c cac kim loai co
tinh khit cao, ch tao cac hp kim bng phng phap in hoa, ...
Co hai thuyt c ban v s phong in ng thi cua ion.
3.1. Phong in ng thi cua ion trong h thng l tng khng lin kt:
i




i
1




i
2



cb1

cb2

x
-
Hinh 4.5. S phong in ng thi cua cac ion 1 va 2
100
y tc phong in cua tng ion ring bit khng thay i, ngha la khng co
tac ng tng h giua cac ion.
iu kin cac ion phong in ng thi la in th in cc cua chung phai
bng nhau: = + +
1 1
1
0
1
ln a
F n
RT
2 2
2
0
2
ln + + a
F n
RT
(4.32)
T phng trnh trn ta nhn thy, khi in th in cc tiu chun
0
2
0
1
, cua cac
ion cach xa nhau ta co th xch gn in th in cc cua chung lai gn nhau bng hai
cach:
Thay i hoat cua dung dch
Thay i qua th
Hnh 4.5. cho thy tai cung in th
x
, tc phong in cua cac ion 1 va 2 la i
1

va i
2
, vi i
1
i
2
.
Tc phong in tng cng:

+ = =
2 1
i i i i
i k

Trong thc t nhiu khi ch cn mt ion phong in, con s phong in cua ion
khac se co hai hoc v giam hiu sut dong in hoc v giam tinh khit cua san phm.
Nu k hiu A la hiu sut dong in cho ion cn phong th:

k
i
i
i
i
i
i
i
A = =

i
i
: tc cua ion cn phong
i
k
: tc phong in tng cng cua cac ion
Thng thng A<1.
V du trong dung dch nc, ngoai ion kim loai con co ion H
+
. Nu in th
x
m
hn in th cn bng cua cua ion H
+
trong dung dch, th H
+
se ng thi phong in vi
ion kim loai:
k
Me
Me
i
i
A = ;
k
H
H
i
i
A = ; hay
H Me
Me
Me
i i
i
A
+
=
Tuy nhin co nhng khi ta cn phai phong in ng thi cac cation. Trong trng
hp o ta c gng lam cho in th cac ion phong in xch lai gn nhau.
Cng thc (4.32) cho thy khi thay i hoat cua ion phong in (1) ln 10 ln
th in th th in th ch dch chuyn ln 0.029V so vi ion (2), con khi thay i hoat
ln 1000 ln th in th ch tng ln khoang 0.087V. Do vy, khi in th in cc
tiu chun cua cac ion khac xa nhau nhiu th vic thay i hoat khng co hiu qua.
Tht vy, khng th nng cao v han nng cua ion co in th in cc tiu chun m
hn v hoa tan cua ion co han. Con giam nng cua ion co in th in cc tiu
chun dng hn se lam cho tc phng in i cua no tr nn qua nho va tr thanh
khng co gia tr.
V du: in phn ch tao hp kim Ag-Pb.
Ta bit: V V
Pb Ag
13 . 0 ; 798 . 0
0 0
= + =
101
Vy [AgNO
3
] phai bng bao nhiu V
Ag
13 . 0 =
Theo phng trnh Nernst ta rut ra c [ ]
3 19 16
/ 10 10 cm mol M Ag
+
=
Nu ly chiu day lp khuych tan s cm D cm
Ag
/ 10 ; 1 . 0
2 5
= = ta co:
Ag e Ag +
+


2 18
19 5
/ 10
1 . 0
10 . 10 . 96500 . 1
cm A
C nFD
i
Ag Ag
Ag
gh

= =

Nh vy trn in cc hu nh ch co Pb thoat ra. Vy cho Ag phong in
ng thi vi Pb, th phng phap co hiu qua nht la tao phc cho cac ion co in th
in cc tiu chun dng hn, do o dch chuyn in th in cc cua no v pha m
hn ( y tao phc cho Ag).
V du trong dung dch cyanua, in th thoat Ag m hn Zn trong khi o mui
n th in th thoat Ag dng hn Zn khoang 1.5V.
Mt khac ta cung co th thay i qua th cua ion cung co th lam cho in th
phong in cua chung xch lai gan nhau hoc xa nhau thm. Khi chuyn t dung dch
mui n sang mui phc th qua th cung tng.
3.2. Phong in ng thi cua ion trong h thng k hp:
Trong thc t cac ion phong in ng thi lun lun tac ng ln nhau nn tc
phong in ng thi cua chung phu thuc vao cu tao lp in tch kep, vao trang
thai cua ion trong dung dch va vao cu tao cua lp nn. Trong trng hp nay ta s dung
cng thc sau:
= + + +

hk
i i
a
a
F n
RT
a
F n
RT
1
1 1
1
1
1
0
1
ln ln

hk
i i
a
a
F n
RT
a
F n
RT
2
2 2
2
2
2
0
2
ln ln

+ + +

(4.33)
trong o:
i
: h s c trng cho kha nng xm nhp vao lp kep cua ion i.
hk hk
2 1
, : qua th khi phong in ng thi cua cac ion 1, 2 trong h thng kt hp.
S hang th 3 trong ca v trai va v phai cua phng trnh trn biu th s dch
chuyn in th khi co cac ion i tham gia lp kep.
3.2.1. Anh hng cua lp in kep va trang thai cua ion trong dung dch:
Nng ion trong lp kep c tnh theo cng thc Boltzmann:
[ ] [ ]
RT nF
dd
n
lk
n
e Me Me
/
1
.
+ +
=
Khi co cac ion khac cung phong in th nng cua mt loai ion se nho hn
bnh thng v b ion kia y ra khoi lp kep. Do o khi phong in ng thi hai ion th
thng mt ion hoc ca hai ion b giam tc .
3.2.2. Anh hng cua ban cht lp nn:
Lp nn lam ha in th phong in cua ion. Tac dung kh phn cc cua nn
do chung tao thanh hp kim vi ion phong in.
V du: Na
+
phong in trn in cc thuy ngn in th V 7 . 1 = thay v -2.7V.
102
Lp nn lam tng in th phong in cua ion.
Khi nghin cu s kt tua Ag ta thy tc kt tua cua no khca nhau cac ni
trn b mt in cc. Nguiyn nhn cua hin tng o la do b mt in cc
khng ng nht. Tai ni b mt hoat ng th tc phan ng xay ra nhanh, tai
ni b mt b ng c, thu ng, b bao phu mt lp cht haot ng b mt, ... th
tc phan ng xay ra chm, thm ch b ngng hn.
IV. Su hoa tan ant cua kim loai:
Phan ng hao tan cua kim loai co th theo phng trnh chung sau:
Ze Me Me
Z
+ =
+

Trong dung dch cac cation kim loai co th tn tai cac dang khac nhau: dang
hydrat hoa:
+ Z
x
O H Me ) (
2
, dang thuy phn:
x
Z
O H MeOH ) .( ) (
2
) 1 ( +
, dang phc:
[ ] [ ] ,... ) ( , ) (
2
4
2
4 3
+
CN Cd NH Cu
S hoa tan cua kim loai bao gm nhiu giai oan:
*
happhu luoi
Me Me (giai oan pha mang li)
* [ ] Ze Me Me
bm
Z
happhu
+
+
(giai oan chuyn in tch)
* [ ]
+ +

Z
bm
Z
Me Me (giai oan khuych tan ion t b mt vao dung dch)
Khac vi nguyn t kim loai trong mang li tinh th kim loai, cac nguyn t hp
phu kim loai co linh ng ln hn nhiu.
Qua th hoa tan kim loai c xac nh theo cng thc sau:

happhu
cb
happhu
Me
ZF
RT

ln = (4.34)
happhu
cb
happhu
, : phu b mt cua cac nguyn t hp phu trang thai cn bng va
tc phan ng nao o.
Nu 0 > >
Me happhu
cb
happhu

Ngoai ra qua th kim loai co th do s chm tr cua qua trnh chuyn in tch gy
ra, luc o ta co th xac nh tc hoa tan kim loai nh sau:

=
Me
Me
bm
Me
Me
cb
happhu
happhu
Me
a
Me
RT
ZF
C
C
ZF
RT
i i

) 1 (
exp exp
0
0
(4.35)
trong o:
0
,
Me
bm
Me
C C : nng cua ion kim loai tai b mt in cc va nm su trong dung dch.
Nu s vn chuyn ion kim loai vao dung dch ch do khuych tan khng ch, khi
o ta co:

0
Me
bm
Me
Me
a
Me
C C
ZFD i
Z

=
+
(4.36)
Trong qua trnh hoa tan ant th
0
Me
bm
Me
C C . Nh vy, v nguyn tc
a
Me
i co th rt
ln, tr trng hp trn b mt kim loai co xut hin mt mang che phu can tr s hoa
103
tan. V du, khi lp sat b mt in cc b bao hoa cac cation kim loai hoa tan ri dn ti
kt tinh mui kim loai o, luc o ta co tc cua qua trnh kt tua:

0
) (
+
+
=
Z
Z
Me
Me
c
gh Me
C
ZFD i (4.37)
T (4.36) va (4.37) ta co:
c
gh Me
a
Me
Me
bm
Me
i
i
C
C
Z
Z
) (
0
1 =
+
+
thay vao phng trnh (4.35) trong trng hp 1 =
cb
happhu
happhu

ta co:

=
Me
c
gh Me
Me
Me Me
Me
a
Me
RT
ZF
i
i
RT
ZF
ZF
RT
i i

) 1 (
exp 1
) 1 (
exp exp
) (
0
0
(4.38)
V. Su hoa tan ant cua cac hop kim:
Trong cac hp kim a pha th cac pha c lp vi nhau v phng din in hoa
hoc. Cac pha ch hoa tan ant khi in th ant at ti in th ion hoa. in th ion hoa
phu thuc vao tnh cht hoa l cua tng pha. Tt nhin cac pha co in th m nht se hoa
tan trc. Ch sau khi chung hoa tan hoan toan hoc in th ant at ti in th ion hoa
cua cac pha dng hn th nhng pha nay mi b hoa tan.
Nu pha co in th ion hoa m hn hoa tan d dang va ham lng cua no trong
hp kim tng i ln th in th in cc ant thng khng at ti in th hoa tan
pha dng hn. Khi y cac pha ng se ri xung di dang mun.
Con nhng hp kim dang mt pha la nhng hp cht hoa hoc hay dung dch rn
cua cac kim loai khac nhau se hoat ng nh mt kim loai duy nht khi ta phn cc ant.
VI. Su thu dng hoa cua kim loai:
Mt s kim loai hay hp kim nhng iu kin c bit cua mi trng (co cht
oxy hoa), hay phn cc ant th chung t nhin mt kha nng hoa tan va tr nn tr, ta
noi rng kim loai hay hp kim o a b thu ng. Cac kim loai Cr, Ni, Fe va hp kim cua
chung d b thu ng.
Trn ng cong phn cc co 3 khu vc:
Tai khu vc in th thp, kim loai hoa tan bnh thng, goi la khu vc hoat
ng
Tai in th E
t.
, mt dong in t ngt giam xung ti gia tr rt nho va
kim loai a tr nn thu ng. Ta goi in th E
t.
la in th khi u thu ng.
Mt dong in ng vi E
t.
goi la mt dong ti han i
t.h
.
in th dng hn E
t.
, in cc b thu ng hoan toan, mt dong in
i
t.
rt nho, goi la khu vc thu ng.
Trn b mt kim loai b thu ng co phu mt lp oxyt bao v kim loai khoi b hoa
tan: ye yH O Me O yH xMe
y x
2 2
2
+ + +
+

104
Tip tuc dch chuyn in th in cc v pha dng hn, co th lai lam cho mt
dong in tng ln, ta goi hin tng nay la s qua thu ng. in th ma tai o ttc
qua trnh tng ln goi la in th qua thu ng E
q.t.
, luc nay kim loai b hoa tan thanh
cac ion kim loai co hoa tr cao hn ng thi co s thoat oxy. i khi in th cha at
ti gia tr in th qua thu ng nhng mt dong in vn tng ln do co s pha huy
cuc b mang thu ng hoc a at ti in th thoat oxy theo phan ng:
e O H O OH 4 2 4
2 2
+ +

Cac anion Cl
-
, Br
-
, I
-
, ... thng gy ra pha huy mang thu ng.
E(v)

Thoat oxy: e O H O OH 4 2 4
2 2
+ +

Khu vc qua thu ng
E
q.t.



Pha huy cuc b Khu vc thu ng
ye yH O Me O yH xMe
y x
2 2
2
+ + +
+



E
t.


Khu vc hoat ng
Ze Me Me
Z
+
+


logi
t.
logi
t.h
logi
Hinh 4.6. ng cong phn cc ant khi kim loai b thu ng
VIII. Dng hoc phan u ng thoat oxy:
Phan ng thoat oxy la mt phan ng ant phc tap, bao gm nhiu giai oan ni
tip nhau:
Trong mi trng axit:
e H O O H
O O
O O H OH
e H OH O H
hp
hp hp
hp
4 4 2
2
) 2 ( 2
) ( 4
2 2
2
2
2
+ +


+
+ +
+
+

Trong mi trng kim:
105
e O H O OH
O O
O O H OH
e OH OH
hp
hp hp
hp
4 2 4
2
) 2 ( 2
) ( 4
2 2
2
2
+ +


+
+

Hin nay co nhiu y kin khac nhau v c ch cua phan ng thoat oxy v:
- Phan ng thoat oxy co nhiu phan ng phu.
- Kho o chnh xac in th thun nghch tiu chun cua in cc oxy.
- Trang thai b mt in cc thay i theo thi gian, chon ant n nh trong
iu kin thoat oxy rt kho khn. Tht vy, mun cho oxy thaot ra t dung
dch axit co a
H+
= 1 th in th in cc phai dng hn +1.23V
( V
O H O
23 . 1
0
/
2 2
+ = ). Nhng phn ln cac kim loai u b hoa tan trc khi at
ti in th o. V vy, mun nghin cu qua trnh thoat oxy trong mi trng
axit phai dung kim loai nhom Pt, Au va mt s kim loai qu khac.
Trong dung dch kim, in th thoat oxy m hn ( V
OH O
41 . 0
0
/
2
+ =

khi OH
-
= 1)
nn co th dung kim loai nhom Fe, Cd va mt s kim loai khac lam ant. Oxy thoat ra t
nhiu b oxy hoa.
Qua th oxy tng ln t t theo thi gian (nhom Fe, Pt) hoc nhay vot (Pb, Cu), do
o ta phai ly gia tr n nh cua no.
Trong khoang mt dong trung bnh, qua th oxy trong dung dch kim tng
theo day: Co, Fe, Cu, Ni, Pb, Au, Pt.
Khi trong dung dch co cac cation la th qua th oxy cung tng ln.
Qua th oxy phu thuc vao ban cht cua lp oxyt tao thanh trn b mt in cc.