TRNG AI HOC CONG NGHIEP THANH PHO HO CH MINH

KHOA CONG NGHE HOA HOC

&

BAI GIANG

IN HA L THUYT

Ngi soan : ang Kim Triet

TP. HCM, 01-2005

CHNG I :

C S LY THUYET VE CAC QUA TRNH IEN CC

I. LP IEN TCH KEP:
1. M au:
Khi cho 2 pha tiep xuc nhau th gia chung se tao thanh be mat phan
chia pha. Khi tao thanh be mat phan chia pha thng co s phan bo lai ien
tch gia cac pha. Khi ay be mat phan chia pha se tao thanh lp ien tch
kep va xuat hien bc nhay ien the gia cac pha.
Cac trng hp phan bo lai ien tch :
- Chuyen ien tch qua be mat phan chia gia cac pha . V du : Khi
nhung mot thanh kim loai vao trong dung dch th nhng ion kim loai se
chuyen vao dung dch va be mat dung dch ni tiep xuc ( be mat phan
chia pha) se tch ien dng, con be mat kim loai se tch ien am.
- Hap phu khong eu nhau cac ion trai dau (hap phu chon loc). V du :
Hap phu ion Cl- tren be mat kim loai tr. Khi ay, be mat kim loai tch ien
am va se hut ien tch dng cua dung dch va lp ien tch kep hnh thanh.
- Hap phu va nh hng cac phan t lng cc.
Tren cung mot be mat phan chia gia cac pha co the xay ra hai hoac nhieu
trng hp tren. Cho nen be mat phan chia gia hai pha co the bao gom
nhieu lp, nhng ta van goi lp ien tch hnh thanh tren be mat phan chia
gia cac pha la lp ien tch kep.
a. The ben trong, the ben ngoai, the be mat:
. The ben trong (the Galvani) : La ien the ben trong cua pha so vi
mot iem xa vo cung trong chan khong khong tch ien.
Theo nh ngha tren e chuyen mot ien tch e nao o t vo cc vao
ben trong cua mot pha can phai ton mot cong la e.
Thc ra ieu o ch thc hien c trong tng tng v can phai co
mot ien tch co tnh chat ac biet. ien tch o phai het sc nho e khi no
xuat hien va bien mat khong anh hng g en phan bo ien tch trong pha
va ac biet khong c tac dung len ien tch o mot lc hoa hoc nao. Thc
ra nghiem khac ma noi th cac lc hoa hoc ay cung co tnh chat ien.
. The ben ngoai () hay con goi la the Volta : La ien the cua mot
iem tren be mat cua pha so vi mot iem xa vo cung trong chan
khong khong ien tch.
2

Nh vay e chuyen mot ien tch e t vo cung en be mat pha can

phai ton mot cong la e.
The ben ngoai xuat hien la do tha ien tch t do tren be mat.
The Volta bang khong khi be mat khong mang ien tch.
.The be mat ( ) : Xuat hien khi tren be mat co s nh hng cac
lng cc cua dung moi hoac khi co s hap thu ac biet cac ion, nguyen t
hay phan t. Gia the ben trong, the ben ngoai, the be mat co moi lien he
sau :
= +
The be mat se trung vi the ben trong, khi the ben ngoai bang khong
ngha la khi tren be mat khong co ien tch t do.
= 0 va =
b. Hieu the Galvani va hieu the Volta :
. Hieu the Galvani 1,2 : La hieu so ien the ben trong cua 2 pha.
1,2 = 1 - 2
Sc ien ong E cua mot mach bao gom nhieu pha tiep xuc vi nhau
bang hieu so the ben trong cua 2 pha cuoi giong het nhau cua mach (1 va 1).
o chnh la hieu the Galvani.
E = = 1 - 1
V du : Trong mach ben (H.1) ta co the viet :
MeIII
MeI
ien giai I ien giai II MeII
MeIII
1
2
3
4
5
6
7=1
E = 1MeIII - 7MeIII
Noi mot cach khac sc ien ong E cua mach bang tong so ai so cua
cac hieu ien the Galvani gia cac pha noi tiep nhau cua mach.
ieu o the hien ro rang hnh 1. Ta khong o c trc tiep tng
hieu so ien the ben trong rieng biet. Ngc lai tong E co the o c.
. Hieu the Volta ( 1,2 ) :
Hieu the Volta 1,2 gia pha 1 va 2 la hieu so cua cac the ben ngoai
cua 2 pha o.
1,2 = 1 - 2
Trong mach co 2 pha au va cuoi giong nhau 1 va 1 ta cung co the
viet:
1 - 1 = 1 - 1 = E
E = 1 - 1 = i,i + 1
3

He thc nay co the kiem tra bang thc nghiem v hieu the volta gia
cac pha co the o c.
. S lien he gia the Volta va ien the ien cc :
Bc nhay ien the nay sinh gia cac pha ngha la gia cac iem
trong kim loai va trong dung dch goi la ien the ien cc tuyet oi.
Hien nay ta khong o c ien the ien cc tuyet oi. Do o danh t
ien the ien cc tha nhan la e ch sc ien ong cua 1 pha gom ien cc
a cho va ien cc hyro trang thai tieu chuan ngha la khi a H 3O + = 1 va

PH 2 = 1amt. Do o tren thc te ien the ien cc Men+/ Me nao o se la sc

ien ong cua pin :
H2 Pt/H3O+( a H 3O + = 1), H2O//Men+, H2O/Me

(I)

Ta xet s lien he gia the volta va ien the ien cc, tc la xet s
lien he gia the volta va sc ien ong E cua pin tren.
Gia s kim loai 1 la Pt nhung trong dung dch L1 cha ion H3O+ vi
a H O + = 1 va PH 2 = 1amt, con 2 la kim loai nhung trong dung dch L2 cha ion
3

Men+ can bang vi Me va kim loai 2 va 2 la 2 kim loai giong nhau.

E

Hnh 2 tng ng vi pin (I) sc ien

ong cua mach (hnh 2 ) Chnh la sc ien
ong cua pin (I) hay noi cach khac i chnh la
ien the ien cc Men+/Me .

2'

Ta co the viet :
E = 2 - 2 = i,i + 1 hay viet mot cach khac

Hnh 2

:
E = 2,L 2 + L 2 ,L 1 + L 1 ,1 + 1,2
= ( 2,L 2 2) (1,L 1 - 1) + L 2 , L 1 .
L 1 ,L 2 la th khuyech tan gia L1 va L2. Thn L 1 ,L 2 nho , bo
qua.
E = (2,L 2 2) (1,L 1 - 1)

Neu lay ien cc hydro lam ien cc tieu chuan vi 2H+/H 2 = 0 th :

1,L 1 - 1

=0
4

Ta thay E =2,L 2 2 tc la ien the ien cc khong phai ch la

bc nhay ien the dung dch ien cc ma bao gom 2 hieu so ien the
trong o mot la bc nhay dung dch ien cc va phan khac la mot phan
cua hieu so ien the tiep xuc kim loai kim loai.
c. The ien hoa :
Trong nhieu trng hp khong the dung the hoa hoc ma phai dung
th ien hoa ( i ). Gia th hoa hoc va th ien hoa co he thc :
i = i + Zi F

F : So Faraday
: The ben trong (the Galvani)
Zi : Gia tr ai so cua ien tch. oi vi cac phan t khong tch
ien Zi = 0
2. S dung phng phap nhiet ong e nghien cu lp kep:
a. Thuyet Gui - Sapman:
Theo Hemtholtz th lp ien tch kep co the hnh dung nh mot tu
ien phang song song. Pha dung dch ch co mot lp ion day ac ep sat vao
ien cc con pha ien cc co mot lp ien tch trai dau.

S o cau tao
Bien thien ien the theo khoang cach
kieu Helmtholtz

Mau ien tch kep cua Helmtholtz con qua gian n. No khong giai
thch c mot so hien tng nh :
- ien dung cua lp kep phu thuoc vao nong o chat ien giai va ien
the ien cc.
- Co ton tai mot the ien ong nho hn M la trai dau vi M.

Sau Helmtholtz th Gui - Sapman a phat trien lp ien tch kep.

Theo ho th cac ion co chuyen ong nhiet t do, mat khac cac ion cung dau
se ay nhau nen cau tao cua phan lp ien tch nam pha dung dch khong
day ac nh Helmtholtz quan niem ma co cau tao khuyech tan. Vi mot ien
cc phan cc ly tng th co the noi rang gia mot iem bat ky nao o trong
lp kep va mot iem trong the tch dung dch, co ton tai mot can bang :
i lp kep = iS
q s = 16 - + 6 +

aM=10
+
+
+
+
+
+
+
+
+
+

+
-

1
l1

S o cau tao kieu Gui-Sapman

Phan bo ien the theo khoan g cach

Trong o :
i

lp kep,

i s : The ien hoa cua cac ion o trong lp kep va trong the

tch dung dch.

Biet :
i lp kep = io + RT ln Ci + Zi F
i s

= ios+ RT ln Cis + Zi F s

Trong o :
Ci, Cis : la nong o cua ion trong lp ien tch kep va trong the tch
dung dch.
ien the s tha nhan bang khong, x la khoang cach en ien cc.
Do o co the viet :
i lp kep = io + RTlnCi + Zi F = ios + RT ln Cis
Gan ung coi : Io = ios ta co the viet :
RT ln

Ci
= - ZiF
Ci S

ln

Ci
= - Zi F
S
Ci
RT

Ci
at f = F ta co : ln S = Zif

Ci
RT
Ci
Do o : S = e -Zif rut ra : Ci = Cis.e-Zif
Ci

Phng trnh tren cho biet qui luat phan bo ion trong dung dch va
trong lp ien tch kep.
Theo Gui-Sapman ien tch khuyech tan tong cong phan bo pha
dung dch di tac dung cua lc tnh ien va chuyen ong nhiet tai x = 0 la :
DRTCi S
q = -2
2

1/ 2

Sh

Zf 0
2

D : hang so ien moi

0 : ien the tai x =0
ien dung vi phan cua lp kep :
C=

qkt
M

DZ 2 F 2 Ci S
=
2RT

1/ 2

cosh

zf M
2

T cong thc tren ta thay ien dung cua lp kep phu thuoc vao nong
o chat ien giai va ien the ien cc. ieu nay thuyet Hemtholzt khong giai
thch c.
b. Ly thuyet Stern
Trong ly thuyet Gui- Sapman cac ion coi nh cac ien tch iem co
the tiep can ien cc en mot khoang cach nho bao nhieu cung c. Nhng
trong thc te th cac ion eu co kch thc xac nh nen theo Stern th cac ion
ch co the tiep can ien cc en mot mat phang tiep can cc ai nao o. Mat
phang nay la chung cho ca Cation va anion. Nh vay lp ien tch kep chia
lam 2 khu vc :
- Lp day ac nam gia mat phang ien cc va mat phang tiep can cc
ai. Ta goi la lp Helmtholtz hay la lp ben trong.
- Lp khuech tan trai rong t mat phang tiep can cc ai vao sau trong
dung dch.
Stern thay can phai phan biet hai mau lp ien tch kep.
Mau Stern khong co hap phu
ion

Mau Stern co s hap phu ac biet cac

8+
+
+
+
+
+
+
+

+
+
+
+
+
+

6+

10 - + 2 +

+
+
-

12 - + 6 +

x1

x
1

- Mau khong co hap phu ac biet

- Mau co hap phu ac biet
qM = - (q1 + q2 )
Trong o : qM : ien tch tren be mat kim loai
q1 : ien tch trong lp day ac
q2 : ien tch cua lp khuech tan

q1 = 2FCi d

+ + 1 F
RT

+ 1F
RT

-e

+- : Bien thien the nang khi chuyen mot phan t vat chat t gia
dung dch en be mat ien cc khi 1 = 0.
q2 = -2

DRT S
Ci
2

Sh

f1
2

c. Thuyet Grahame :
Gahame gia thuyet rang khi khong co hap phu ac biet cac ion th q1
= 0 do o qM = -q2.
e gia thuyet phu hp vi mo hnh cua lp kep Grahame a ra khai
niem hai mat phang tiep can cc ai. Trung tam cua cac ion b hap phu co
the en sat be mat ien cc hn va cach ien cc mot khoang bang x1. x1 la
khoang cach tiep can cc ai, mat phang qua x1 va song song vi ien cc
c goi la mat phang Helmtholtz ben trong. ien the tai mat phang ay so
vi dung dch ky hieu la I. Mat khac ion tham gia vao chuyen ong nhiet va
8

tao thanh lp khuech tan khong the tiep can en ien cc gan hn mot
khoang x = x2. Mat phang qua x2 va song song vi ien cc c goi la mat
phang Helmtholtz ngoai, ien the tai mat phang o ky hieu la o.
Mat phang ben trong va ben ngoai khac
nhau khong phai ch khoang cach ien cc.
0
Mat phang ben trong la mot lp ion nam trong
<
<

h the nang ac biet. Nhng ion o mat het

hoac mot phan vo hydro hoa. Chuyen ion o

vao trong dung dch phai ton mot nang lng
x1
x2
e thang cong hap phu ac biet cua s tac
dung cua ion vi ien cc. Mat khac chuyen ion t dung dch vao mat phang
Helmtholtz ben trong ton 1 cong- Cong kh hydro hoa. Chuyen ion vao gan
ien cc hn x1 vap phai sc ay cua ien tch ien cc. Mat phang tiep can
cc ai ngoai khong phai la mot lp ma ch la gii han co the tiep can c
cua cac ion chuyen ong nhiet.
Grame chng minh rang neu nh khong co s hap phu ac biet th qM
= - q2 va lp kep coi nh hai tu ien mac noi tiep.
1
1
1
=
+
C C1 C2

C : ien dung vi phan cua lp kep

C1 : ien dung vi phan cua lp kep day ac
C2 : ien dung vi phan cua lp kep khuech tan
3. Cac phng phap nghien cu lp kep:
a. Phng phap ien mao quan:
. Phng trnh Lpman : Phng phap ien mao quan da tren phep
o s phu thuoc sc cang be mat cua kim loai long nh Hg vao ien the va
nong o chat ien giai. ay la phng phap tin cay e nghien cu s hap phu
ien hoa tai be mat phan chia ien cc va dung dch. ieu kien e cho s o
lng trong phng phap ien mao quan c gian n la tren ien cc
khong xay ra mot phan ng ien hoa nao. Khi ay toan bo ien tch en be
mat ien cc ch dung e tao nen lp kep. Ta goi ien cc ay la ien cc
phan cc ly tng. Co nhieu kim loai co the dung lam ien cc phan cc ly
tng nhng trong dung dch nc tot nhat la dung Hg v qua th H2 tren Hg
rat ln.
9

Khi tren be mat tch tu ien

tch am hay dng th no se hut
ien tch trai dau pha dung
dch vabe mat phan chia ien cc
- dung dch co the coi nh mot tu
ien.

I'
I

Calomen

S o nguyen ly cua phng phap ien mao quan

Xet s o di ay :

I,I la 2 kim loai giong nhau

Sc ien E cua mach :
E = i ,i +1
= I - I
= (I - ) + ( - ) + ( - II) + (II - I)
Hay : E + ( - I) + ( - ) + (II - ) + (I - II) = 0
Vi phan phng trnh tren ta co :
dE+ d( - ) + d(II - ) = 0
(1)
(V neu la Hg th -I la hang so. Mat khac I - II la hang so )
Rut ra : d( - ) =-dE - d(II - )
(2)
Ap dung phng trnh Gib trong trng hp ien cc phan cc ly tng
vi chat khong mang ien th :
(3)
d = - i di
Trong o :
: Sc cang be mat
i : o d tng oi be mat cua cau t
Trong trng hp co hap phu ien hoa th phai thay i bang i . Vay :
w
d = - i , d i , i , d i , (4)

i la phan t bat ky trong pha va .

V

i ,

= i , + i e

nen t (4) co the viet lai nh sau :

d = i , d i , i , d i , i ei , d i ei , d
Lng Zie i co the coi nh la ien tch trong pha va trong o ien
t va ion Hg+ la cac cau t i mang ien trong pha va ion chat ien giai la
cau t mang ien trong pha .
10

Vay :

qi,

= i ei ,

qi,

= i ei ,

V phai am bao trung hoa ien nen :

qi, = - qi,
Do o :
d = - i , d i , i , d i , qi , (d d )

(5)

Neu nh

pha la Hg nguyen chat th d i , = 0 va khi thanh phan dung dch khong oi

th i , d i , = 0. Mat khac t phng trnh (2) ta co :
- dE= d( - )
(V khi thanh phan dung dch khong oi th d(II - ) = 0)
Do o : phng trnh (5) co the viet :
d = -qi, dE

= qi, = qM

E i , ,T ,P

Hay : -

(6)

qM la ien tch d tren be mat kim loai ien cc. Phng trnh (6) goi la
phng trnh Lpman.
. ng cong mao quan :
Thanh lap ng cong mao quan:
T phng trnh (6) ta thay rang ien tch be mat ien cc T, P kh6ng oi
co the tnh theo phng trnh Lpman :

E i , ,T ,P

qM = -

neu nh cac the hoa hoc khong oi

Phng trnh Lpman chng minh rang co the tm c ien tch tao
thanh moi pha cua be mat phan chia pha bang cach xac nh o doc cua
ng cong bieu dien s phu thuoc sc cang be mat vao ien the E (hnh
ve).
Phng trnh Lpman co the dung cho he thong co ien so sanh bat ky
ch can thanh phan cua he khong oi.
Phng trnh Lpman cho thay s khac nhau c ban gia ien cc
phan cc ly tng va ien cc khong phan cc ly tng v sc ien ong cua
he thong khong phan cc ly tng phu thuoc vao T,P va nong o cac cau t
nen khong the thay oi E khi T, P va thanh phan dung dch khong thay oi
nh thay phng trnh Lpman. V vay phng trnh Lpman ch dung cho
ien cc phan cc ly tng.

11

ng bieu dien quan he phu thuoc sc cang

be mat vao ien the ( ng cong - E) goi la
+q
dng cong mao quan.
ien tch qM = 0 tai nh Parabol. ien the
tng ng vi iem ay goi la ien the iem
Ez
khong tch ien.
0
q=0
-E
V qM > 0 vi E > EZ va qM < 0 vi E <
EZ nen cac anion b hut vao ien cc khi E >
EZ (qM > 0) con Cation b hut vao ien cc khi
-q
-q E < EZ (qM < 0 ). Cac ion b hut vao ien cc
se ay nhau, do o e tang them mot n v be
mat phan chia ien cc- dung dch oi hoi mot cong nho hn khi khong co tac
dung tnh ien gia cac ion va ien cc (qM = 0, cac ion khong b hut vao
ien cc ). Do o sc cang be mat se giam i khi tang gia tr tuyet oi cua qM
va ng cong mao quan se cc ai tai ien the iem khong tch ien.
Anh hng cua s hap phu cac ion va phan t trung hoa en dang
ng cong mao quan:
Dang cua ng cong mao quan phu thuoc rat nhieu vao s hap phu
cac ion va chat trung hoa tren be mat ien cc s phu thuoc o manh yeu
khac nhau tuy thuoc ban chat ion va phan t trung hoa.
+ oi vi anion co the chia lam 2 nhom :
- Nhng anion khong hoat ong be mat nh : F -, CO-, OH-, SO42-,
HPO42- th sc cang be mat thay oi rat t. ien the iem khong tch
ien EZ khong thay oi.
- Nhng anion hoat ong be mat nh : NO-, NO3-, CNS-, I-, Br- ha
thap sc cang tren be mat tch ien dng hoac khong tch ien.
Lng anion b hap phu thuoc vao ien tch be mat. Khi be mat tch
ien dng th hap phu ln, be mat tch ien am yeu th t hap phu.
Tang ien tch am cua be mat len (tang ien the ien cc u am) th
lc ay tnh ien ln hn lc hap phu ac biet, cac anion se b nha ra
khoi be mat ien cc. Do o ien the E u am ng cong mao
quan cua dung dch co chat hoat ong be mat va khong se trung nhau
va khi o dang cua ng cong mao quan t phu thuoc ban chat chat
ien giai ien the u am. Khi hap phu cac anion ien the EZ se
chuyen ve pha am hn.
+ oi vi Cation
,q

12

- Khac vi anion cac Cation vo c hap phu yeu (tr Tl+). con cac
Cation hu c hap phu manh len be mat Hg. V du : Cac Cation
[(CH3)4 N]+, [(C2H5)4N]+, [(C4H9)4N]+. Cac Cation hap phu tren be
mat tch ien am va tang len khi tang ien tch am be mat. Khi ien
tch be mat u dng cac cation b nha ra.

KOH

420
400
NaCl
380
360 KCNS KI
340
320
300
280
260
240
220

Na2 SO4
+

[(C4 H9)4 N]

-E

-E

ng cong mao qun trong dung dch cc ng cong mao qun

cht in gii khc nhau( Hap ph anion). trong d.d.cc cht in gii
khc nhau(Hap ph Cation)
+ Khi ta cho vao dung dch chat ien giai tr

nhng hp chat hu c trung hoa th sc cang

KNO 3
be mat cung ha thap xuong. S ha thap sc
cang be mat do hap phu cac chat hu c
thng xay ra ien the iem khong tch
ru
ien hoac be mat tch ien yeu. Khi be mat
tch ien am hoac dng manh th cac chat
hu c b nha va ng cong mao quan cua
dung dch sach va dung dch co chat hoat
-E
ong be mat trung nhau.
ng cong mao quan khi co hap phu
Muon biet anh hng cua ien tch be
cac chat hu c trung hoa
mat en s hap phu cac phan t chat hu c
D : Hang so ien moi
ta xet nang lng cua tu ien theo ly thuyet
d : khoang cach gia 2 ban tu ien
tnh ien th nang lng W cua tu la :
W=

2d 2
qM
D

Ta thay khi qM cang ln th W cang ln . Neu qM khong oi th W giam

khi tang D (Hang so ien moi) hoac giam d.
13

He thong co khuynh hng t nhien la giam nang lng cua mnh e co

nang lng cc tieu, nen lp ien tch kep co khuynh hng hut vao
nhng phan t dung moi (nc) co hang so ien moi ln va ay cac chat
hoat ong be mat (cac phan t hu c) co phan t ln (d ln). Do o he thong
tang D giam d e ha thap W xuong.
o ng cong mao quan bang ien cc thuy ngan:
e o s phu thuoc sc cang be mat vao ien the ta dung dung cu
nh hnh ve :
Bnh thuy tinh A o ay dung dch chat ien
B
k
+ giai. Nhung ong thuy tinh K co mao quan C
vao dung dch o. Bnh B noi vi ong K
bang mot ong cao su e co the thay oi
chieu cao cua bnh B. Ong K va bnh B
cha ay thuy ngan. ien the c a vao
be mat phan chia ien cc thuy ngan va
A C
dung dch nh mot he thong ien hoa bao
gom mao quan C va ien cc so sanh
S o ng cong ien mao quan Calomen.
Nh a biet, sc cang be mat phu thuoc vao ien the ap at tren be
mat phan chia ien cc Hg- dung dch. Bay gi ta thay oi ien the ien cc
va ieu chnh o cao h cua cot thuy ngan sao cho be mat phan chia gi
nguyen v tr. Trong ieu kien o sc cang be mat can bang vi lc trong
trng theo phng trnh :
2r cos = r2 Hg h.g (*)
Trong o :
r : Ban knh mao quan
: tiep xuc
: Sc cang be mat
: Ty trong cua Hg

g : gia toc trong trng

mao quan
h : chieu cao cua cot Hg
o chieu cao h cac ien the khac nhau suy ra theo phng trnh (*).
Do o ta ve c ng cong ien mao quan.
b. Phng phap o ien dung cua lp kep bang dong ien xoay
chieu:
14

Lp kep co the coi nh mot tu ien, mot ban cua no la be mat kim
loai tch ien con be mat kia la lp ion trai dau nam cach be mat ien cc
mot khoang d bang ban knh cua ion a b solrat hoa.
Trong trng hp lp kep ch co lp day ac ma khong co lp khuech
tan th 1 = 0, khi ay ta co :
C=

q dc
D
=
dc

4d

Trong o :
C : ien dung cua 1cm2 be mat
q /c :Mat o ien tch tren be mat kim loai
D : Hang so ien moi
d : Khoang cach gia cac ban cua tu ien.
Vi tu ien thng gom hai ban kim loai trong o q/c va d la hang so th
ien dung tch phan xac nh theo cong thc tren trung vi ien dung vi phan
:
C=

dq
d

Trong ien hoa ta ch o c bien thien ien the d va bien thien d

tng ng, ngha la o c ien dung vi phan.
Lu y rang ch trong trng hp ien cc phan cc ly tng th toan bo
ien lng a vao mi dung e nap lp kep. Con tren ien cc khong phai
la ien cc phan cc ly tng th mot phan ien lng a vao ien cc se b
tieu hao cho phan ng ien hoa tren be mat ien cc. Do o ien cc co the
coi nh mot tu ien b ro ien, ngha la mot tu ien mac song song vi mot
ien tr R.
R

C lk

S o tng ng cua lp kep tren be mat ien cc khong phan cc

ly tng
Co 2 phng phap o ien dung bang dong ien xoay chieu
- Phng phap cau can bang
- Phng phap so sanh
15

. Phng phap cau can bang:

e o ien dung cua lp kep ta dung cau o xoay chieu (hnh) Khi o
ta thu c ien dung cua bnh ien phan.

~
c

i1

z2

b
i

r : May phat dao ong

Zi : Cac tong tr cua cau
O : Dao ong ky
D : Cuon cam e ngan dong xoay
chieu

C
d

i3

z3

S o cau can bang e o c ien dung lp kep

S o tng ng cua bnh ien phan nh hnh ve :

Cx

Rx

Cphu

C k-a
S o tng ng cua bnh ien phan

Trong o :
CX : ien dung cua lp kep cua ien cc nghien cu
RX : ien tr cua dung dch trong dung dch ien phan
CPhu : ien dung cua ien cc phu
Ck a : ien dung gia Anot va Catot
V ien cc Catot va anot cach nhau rat xa nen Ck a rat nho va v Ck
a mac song song trong mach tren nen ta co the bo qua Ck a.
ien cc nghien cu va ien cc phu mac noi tiep nen ien dung
tong cong o c C co the xac nh bang phng trnh :
1
1
1
=
+
C dd C x C phu

Cdd =

C x .C phu
C x + C phu

16

T cong thc tren ta thay rang khi hai tu ien mac noi tiep th ch xac
nh c ien dung cua tu ien co gia tr ien dung be nhat. That vay neu
CX << Cphu th Cd = CX. Cho nen khi o ien dung thng s dung ien cc
phu co dien tch ln hn ien cc nghien cu hang tram lan. ong thi phai
cho qua bnh ien phan mot dong ien xoay chieu bien o thap (5 10 mv
)tan so cao. Trong ieu kien nh tren, dao ong ien the tren ien cc nghien
cu ln hn tren ien cc phu nhieu nen CX << Cphu. Nguyen tac lam viec
cua cau la ieu chnh tong tr sao cho co can bang ien the gia 2 iem a va
c. Khi ay :
Z1i1 = Z4i4
Z2i2 = Z3i3
Biet rang i1 = i2, i3 = i4 nen khi chia hai he thc tren cho nhau ta co :
Z1 Z 4
=
Z2 Z3

Z1Z3 = Z2Z4
Chon Z1 = Z2 ( thng la 2 ien tr, hai tu ien hoac hai cuon cam ).
Khi ay ieu kien can bang cua cau la :
Z3 = Z4
Nh a biet khi ien tr va ien dung mac noi tiep th tong tr Z se
bang:
j
j
, Z 4 = R4
Z = R j/C
(Z3 = R3
)
c3
c4
j = 1, : Tan so goc x chieu
Khi ien tr va ien dung mac song song :
Z=

1
1
jc
R

Theo ieu kien bang nhau cua 2 so phc th :

C = C va R = R
Trong o C, R la gia tr o c cua ien dung va ien tr tren
nhanh Z3 mac noi tiep.
. Phng phap so sanh:
Vi cac dung dch nghien cu am ac co o dan ien cao co the
dung phng phap so sanh.

17

Nguyen tac cua phng phap la trong khi cho mot dong ien xoay
chieu co cng o khong oi i i qua ta o ien the ri X tren bnh ien
phan va m tren ien dung mau.
Khi o ien dung can tm se bang :
1
i
m
Cm
= Cm
C = Cm
x
1
i Rx2 + 2 2
Cx

Cthc nghiem =

Cx
R .C x2 2 + 1
2
xz

RX va CX la cac thanh phan ien tr va ien dung mac noi tiep cua
bnh ien phan. Nhng thanh phan o se ng vi ien tr dung dch va ien
dung cua lp kep khi tren ien cc khong co phan ng ien hoa nao xay ra.
T phng trnh tren ta thay rang Cthc nghiem ch bang CX khi tan so
goc thap va ien tr dung dch nho, tc la khi bat ang thc sau c
nghiem ung :
RX2CX2X2 << 1
Phng phap o ien dung bang dong ien xoay chieu co the dung e
kiem tra ly thuyet lp ien tch kep.
Thanh pho Ho Ch Minh ngay 01 thang 9 nam 2005

DUYET

GIAO VIEN BIEN SOAN

ang Kim Triet

NHAN XET:
- Nen bo phan m au khong can thiet
- Thi lng hi thieu

18

II. ONG HOC QUA TRNH IEN CC :

1. ong hoc qua trnh ien cc n gian khong kem theo hap phu
Vat ly va Hoa hoc :
a. S phan cc:
Muon hieu ban chat cua khai niem S phan cc ta xet cac v du
sau :
- V du 1 : Co mot bnh cha dung dch CuCl2 hoat o aCu++ = 1. Neu ta
nhung vao dung dch o 2 ien cc bang ong, ien cc ong se can bang
vi ion ong trong dung dch va ien the ien cc can bang cua 2 ien cc
bang nhau va bang +0,34v. Noi 2 ien cc vi nguon ien ben ngoai th ien
the ien cc cua ong se dch khoi gia tr can bang. ien the cua ien cc
noi vi cc am cua nguon se co gia tr am hn + 0,34v, con ien cc noi vi
cc dng cua nguon se co gia tr dng hn + 0,34v.
<

>

+0,34v

Hien tng chung ta va xet thng gap trong qua trnh ien phan.
- V du 2 : Xet mot pin gom 2 ien cc co ien the ien cc can bang
anot la aCb va Catot cCb. Dung dch ien giai gia hai cc co ien tr R.
Noi 2 ien cc vi nhau ( gia thuyet ien tr mach ngoai bang 0), o
cng o dong ien phat sinh trong mach ta thay I nho hn gia tr cng o
tnh theo nh luat Ohm:
I

cbc cba
R

Thc te R hang so, nen I nho hn gia tr tnh theo nh luat Ohm ch
co the do t so giam (tc hieu so cCb - aCb giam).
Thc vay, neu chung ta o cac ien the ien cc ci va ai khi mach co
dong ien i qua th thay ci tr nen am hn cCb va ai dng hn aCb.
+

cCb

>

ci

ia
<

a
Cb

Trong ca hai v du tren ta thay, ien the ien cc eu dch chuyen khoi
trang thai can bang . Hien tng o goi la s phan cc ien cc, goi tat la s
phan cc va bieu dien bang cong thc :
= i - Cb
19

i, Cb : ien the ien cc khi co dong ien i i qua mach ien hoa va
khi can bang.
b. Qua trnh Catot va anot:
- Qua trnh Catot : La qua trnh kh ien hoa, trong o cac phan t phan
ng nhan ien t t ien cc.
V du : Cu2+ + 2e = Cu
- Qua trnh anot: La qua trnh oxy hoa ien hoa, trong o cac phan t
phan ng nhng ien t cho ien cc
V du: Cu = Cu2+ + 2C
- Catot la ien cc tren o xay ra qua trnh kh.
- Anot la ien cc tren o xay ra qua trnh oxy hoa.
Nh vay
trong cac nguon ien th anot la cc am con Catot la cc dng.
Trong cac bnh ien phan th anot la cc dng va Catot la cc am.
- Phan cc Catot : La s chuyen ien the Catot ve pha am khi co dong
ien Catot.
- Phan cc Anot : la s chuyen ien the anot ve pha dng hn khi co
dong ien anot.
Nh vay trong trng hp he thong ien hoa la nguon ien th phan
cc se lam cho ien the ien cc xch lai gan nhau . Do o hieu so ien the
c i -a i se nho hn so vi cCb - aCb va dan en giam cng o dong
ien.
Trong trng hp ien phan th phan cc se lam cho ien the ien
cc tach xa nhau ra, v vay ien the ap t ngoai vao phai ln hn hieu so ien
the aCb- cCb th qua trnh ien phan mi xay ra.
c. Nguyen nhan gay nen s phan cc:
Hien nay co nhieu gia thiet giai thch nguyen nhan va c che gay nen
s phan cc. Phan cc co the do :
- Cham phong ien, tc la cham qua trnh chuyen nhan ien t.
- Cham loai vo hydrat cua ion.
- Cham ket tinh cua kim loai tren be mat ien cc.
- Cham khuech tan chat phan ng en ien cc.
- Cham thai cac phan t kh ra khoi be mat ien cc.
- Cham ket hp nguyen t thanh phan t
Trong cac gia thuyet tren khong co gia thiet nao co the giai thch mot
cach thoa ang cac qui luat ve ong hoc cua cac phan ng ien cc.
20

Tuy trng hp cu the, ta ap dung thuyet nay hay thuyet khac e giai
thch cac hien tng thc nghiem.
Hien nay ngi ta quan niem rang qua trnh ien cc bao gi cung co
nhieu giai oan nh khuech tan cac chat phan ng en ien cc, phong ien,
thai san pham cua qua trnh ien cc Tuy theo giai oan nao trong cac giai
oan ke tren b cham tre th no se quyet nh toc o cua toan bo qua trnh
ien cc va se la nguyen nhan gay phan cc.
d. Phng trnh cua ng cong phan cc (khi khong co s hap
phu) :
II
I
O
Xet qua trnh ien cc gian n co hai phan t
O
hoa tan tham gia :
0 + ne D R
R
R
Phan ng tren gom cac giai oan sau :
III
IV
- Giai oan I : Vat chat 0 pha ngoai lp
khuech tan cua lp ien tch kep, con n ien t tren Cac giai oan cua phan ng
ien cc.
- Giai oan II : Vat chat 0 nam tren mat phang tiep can cc ai, con n
ien t nam tren ien cc.
- Giai oan chuyen ien tch :
0 + ne D R
- Giai oan III : la giai oan vat chat R ton tai tren be mat tiep can cc
ai.
- Giai oan IV : Vat chat R ngoai lp khuech tan cua lp ien tch kep.
r
Goi : toc o cua phan ng thuan la i
toc o cua phan ng nghch la i
Khi M = cbM th dong ien thuan bang dong ien nghch.
cb:in th in cc ng vi mt dng
r
s
i = i = io

r
i , i va can bng)

(io : Mat o dong ien trao oi)

Ngi ta a chng minh c rang :

r
i i0. e nf K
s
i = i0. e (1 ) nf K

Trong o :
: He so chuyen ien tch
n : So ien t tham gia phan ng
21

( M,

F
RT
K : qua the tren Catot
r
Neu tha nhan rang khi kh co dong ien dng (dong Catot i ) va khi
s
oxy hoa co dong ien am ( i ) ta co :
r s
i = ( i i )= i0 (e nf _ e (1 ) nf )
(*)

f=

ay la phng trnh Butler Volmer- Phng trnh c ban cua ien

hoa.
e. Tnh chat cua ng cong phan cc:
- Neu nh qua the :
<<

1
1
hoac <<
nf
(1 )nf

Th sau khi phan tch thanh liet cua ham so mu cua phng trnh (*) ta

x
1!

c quan he bac 1 sau ay gia dong ien va qua the : e x = 1 + +

x2
....
2!

i = i0 (1 + nf k 1 + (1 ) nf k )

k =
i = i0 nf k

i
nfi0

Nh vay gia qua the va mat o dong ien co quan he bac nhat.
Phng trnh K =

i
nfi0

ung vi khong vt qua 15-20mv

- Khi qua the ln :

>>

1
1
hay >>
nf
(1 )nf

Th mot so hang cua phng trnh (*) co the bo qua va khi ay hoac
qua trnh anot la chu yeu hoac qua trnh Catot la chu yeu. T phng trnh
(*) rut ra :
Qua trnh Catot :
k =

1
1
ln i
ln i0
nf
nf

Qua trnh anot :

k =

1
1
ln i
ln i0
(1 ) nf
(1 )nf

T 2 phng trnh neu at :

22

ni0
nf

oi vi qua trnh catot

2,303
b=

nf
a=

va
1

ni0
(1 )nf

oi vi qua trnh anot

2,303

b=

(1 )nf
a=

Ta co the viet lai mot cach tong quat :

= a + blg i
o chnh la phng trnh Tafel.
f. ng cong phan cc hon hp :
Ta bieu dien cac phng trnh toc o phan ng bang o th :
r s
Cac ng cong i , i la ng phan cc bo phan. Tai moi gia tr nhat
nh cua ien the ca 2 qua trnh anot va Catot eu xay ra va
r

r s
i , i eu

M
th i = i = i0. Dong ien tong bang 0.
khac 0. Khi M = Cb

i
1

i
io

io
2

cb

pha phai cua ien the can bang la qua trnh kh, pha trai la qua trnh
oxy hoa.
ng noi cac iem 1, Cb, 2 la ng cong phan cc toan phan cho biet
toc o cua qua trnh anot va Catot phu thuoc vao ien the.
ng cong phan cc toan phan la 1 trong nhng d lieu quan trong e
nghien cu ong hoc qua trnh ien cc. Ta o c ng cong nay bang
thc nghiem.
2. ong hoc qua trnh khuech tan:
23

a. ac iem cua ng cong phan cc:

Muon phong ien ien cc th cac phan t phan ng phai trai qua 4
giai oan. Giai oan II va IV la giai oan khuech tan.
Khi mat o dong ien khong ln lam,
i
toc o phan ng ien cc khong ln th
toc o khuech tan co the am bao cung cap
cac phan t phan ng en ien cc hoac
II
III
thai kp thi cac san pham phan ng khoi
I
khu vc ien cc. Nhng khi cng o
-
dong ien tang len kha ln th s khuech Cb
tan cac phan t phan ng en ien cc co
Cac khu vc cua ng cong phan cc
the khong u ln va toan bo qua trnh ien
cc se b toc o khuech tan khong che. Khi ay du co thay oi ien the th qua
trnh van khong tang len c. Ta lay qua trnh Catot lam v du. ng cong
phan cc gom 3 khu vc :
Khu vc I : Toc o qua trnh do yeu to ien hoa khong che. ng cong phan
cc trong oan I co dang ham so mu.
Khu vc II : Qua o
Khu vc III : Khong che do khuech tan
Neu trong dung dch co hai hoac nhieu phan t co the kh Catot th
ng cong phan cc co dang sau :
V du : Co hai ion MeI++ va MeII++ cung ton tai trong dung dch. ien
the can bang cua chung la ICb va IICb. Neu ta cho ien the ien cc dch
chuyen ve pha am hn th khi ien the vt qua ICb ion MeI++ se phong ien
va at ti dong gii han Igh (I). Khi ay i
ien the van tang nhng Igh (I) khong tang.
Khi ien the vt qua IICb th MeII++ bat
au phong ien va dan ti dong gii han
igh(II)
Igh (II), Igh(I) va Igh(II) goi la dong gii han.
Dong ien gii han tong quat la
igh(I)
:
I
Cb

CbII
Igh(K) = Igh (I) + Igh (II) (1)
b. Toc o khuech tan:
Khi phan ng ien cc tien
hanh th nong o cua cac phan t phan
24

ng nam trong vung cach be mat ien cc la se giam xuong, cang tang thi
gian th khoang cach b thay oi nong o cang tang len.
Neu v ly do nao o on nh th theo nh luat Fick 1, ta co :
dm
C D(Co C )
= D
=
(2)
d

Phn b nng o cht phn ng theo

khong cach n in cc thi gian in
phn (t1<t2<t3).
Trong o :
C0 : Nong o chat phan ng trong the tch dung dch.
C : Nong o chat phan ng sat be mat ien cc.
m: so mol chat phan ng khuech tan en 1 n v be mat ien cc.
Khi phan ng th mot mol chat phan ng trao oi vi ien cc mot
ien lng la ZF. Do o mat o dong ien khuech tan se la :
id = ZF

dm
D
= ZF (Co C )
d

(3)

D : He so khuech tan
id : Mat o dong ien khuech tan.
Neu toc o ien cc u ln th C = 0 va id tien ti i gh.
igh = ZF

D
Co

(4)

igh goi la dong ien gii han hay la toc o gii han.
Y ngha cua toc o gii han :
- dong ien gii han toc o khong thay oi khi ien the thay oi.
Thc vay trong cong thc tren igh ch phu thuoc vao C0 ma khong phu
thuoc vao ien the.
-Toc o gii han phu thuoc vao nong o.
-Mat o dong gii han phan biet ranh gii gia vung ket tua kim loai chat,
xt vi vung ket tua kim loai bot. No cung c ap dung trong cc pho e
phan tch.
c. Phan cc nong o :
Khi khong co dong ien chay qua th nong o cua chat phan ng khu vc
ien cc bang nong o the tch dung dch tc la C = C0 va khi ay ien the
ien cc can bang se bang :
Cb = 0 +

RT
ln Co
ZF

25

Khi dong ien iK i qua th nong o chat phan ng sat ien cc

giam xuong en C. ien the ien cc luc o :
i,k = 0 +

RT
C
ZF

(gia thiet rang phan cc hoa hoc khong ang ke)

Theo cong thc (3) ta co :
id(K) = ZF
at K = ZF

D
(Co C )

v vi mot che o lam viec nhat nh, mot dung

dch nhat nh th Z, D, la nhng hang so.

Rut ra :
id ( K )

C = C0 -

(5)

Khi C = 0 ta co :
igh(K) = KC0 do o : C0 =

igh(k )
(5)
K

The gia tr cua C0 vao phng trnh (5) ta co :

C=

i gh ( K )
K

id ( K )
K

i gh ( K ) id ( K )
K

(6)

Ta biet rang dch chuyen ien the khi co phan cc nong o :

nong o = i,K - Cb
Nen :

nong o =

(7)

RT
C
ln
ZF Co

The gia tr cua C, C0 trong cac cong thc (5)va (6) vao cong thc (7) ta co :
igh( K ) id ( K )

nong o =
=

RT
ln
ZF
RT
ln
ZF

hay nong o =

K
igh( K )
K
igh( K ) id ( K )
igh( K )

id ( K )
RT
ln(1
) (8)
ZF
igh( K )

Theo cong thc tren th nong o se tien ti - khi id(K) = igh(K). Nhng thc
te nong o khong tien ti vo cung v co ion khac tiep tuc phong ien.
d. Anh hng cua dong ien di c va chat ien giai tr en mat o
dong gii han :
Chat phan ng chuyen ong en ien cc bang hai cach :
- Do khuech tan : dong khuech tan id.
26

- Do chuyen ong cua ion en ien cc di tac dung cua ien trng :
Dong di c im
+ Trng hp Cation phong ien Catot :
Goi toc o cua Catot la iK. Khi ay dong khuech tan va di c cung chieu.
iK = id + im
im = i Kt+
t+ : la so chuyen van cua Cation
id = iK iKt+ = iK (1 t+) = iKtt - : la so chuyen van cua anion
+ Trng hp anion phong ien anot :
id = iA(1 t - ) = iAt+
iA : Toc o anot
+ Trng hp anion phong ien Catot :
V du : Cr2O7- + 14H+ + 6e = 2Cr3+ + 7H2O
Chieu chuyen ong cua ion di tac dung cua ien trng va khuech tan
ngc chieu nhau.
iK = id im = id ikt_
id = iK (t - + 1)
+ Trng hp Cation phong ien anot :
V du : Fe2+ Fe3+ + e
Tng t ta co :
id = iA (t+ + 1)
Thay gia tr cua id phng trnh (3) vao ta co :
*Trng hp Cation phong ien Catot :
ZF

D
(Co C ) = iK(1 t+ )

ZF D
iK =
(Co C )
1 t+

Khi C = 0
igh(K) =

ZF D
Co
1 t+

*Trng hp anion phong ien anot :

27

igh(A) =

ZF D
Co
1 t

*Trng hp Cation phong ien anot :

igh (A) =

ZF D
Co
t+ + 1

*Trng hp anion phong ien Catot :

igh(K) =

ZF D
Co
t + 1

Khi trong dung dch co nhng chat ien giai tr khong tham gia vao qua
trnh ien cc ma ch ong vai tro chuyen ien th dong ien cua cac ion
tham gia phan ng ien cc se nho i. V du :
igh(K) =
Trong o : =

ZF
D
Co
1 t +

x
x + x'

x, x : o dan ien rieng cua ion tham gia va khong tham gia qua trnh ien
cc.
Khi x >> x th 0
igh(K) = ZF

D
Co

d .Phng trnh khuech tan khong on nh oi vi ien cc phang:

phan tren ta a xet qua trnh khuech tan on nh ngha la trong qua trnh
o toc o khuech tan khong thay oi theo thi gian. Trong phan nay ta xet
qua trnh khuech tan khong on nh, trong o toc o cua qua trnh thay oi rat
nhieu theo thi gian.
Xet qua trnh khuech tan khong on nh v :
- Qua trnh nay thng gap trong thc te.
- Xet e biet c khi nao th xay ra khuech tan on nh, khong on
nh.
Ta xet qua trnh khuech tan khong on nh gian n nhat la vi ien cc
phang nhung trong dung dch khong b khuay tron. Gia s tren ien cc
phang thang goc vi truc x co xay ra phan ng ien
z
hoa sau :
0 + ne D R
y
e tien li ta xet ien cc phang co kch
x
thc 1 x 1cm2. V chieu day cua lp khuech tan
thng dao ong trong khoang 10-2 10-3 cm nen
28

kch thc cua ien cc ln hn kch thc cua lp khuech tan nhieu. Do o
khong can xet en qua trnh tien hanh ra ien cc va gia thuyet rang nong
o cua chat phan ng ch phu thuoc khoang cach x en ien cc ma khong
phu thuoc vao cac toa o z,y.
Trong trng hp nay ta coi be mat ien cc la vo cung ln va kch
thc cua thung ien phan theo chieu x cung coi la vo cung ln so vi lp
khuech tan va do o tai khoang cach x u ln nong o cua chat phan ng
trong dung dch se khong thay oi.
e n gian ta gia thiet rang khi phan cc th nong o cua dang oxy
hoa cua chat phan ng b thay oi con dang kh th khong.
Theo nh luat Fick th 2 ta co bien thien nong o vat chat 0 theo thi gian :
C 0 ( x, t )
2 C ( x, t )
= D0
t
2x

Trong o :
t : Thi gian t khi bat au ien phan
x : khoang cach ti ien cc
Nong o dang oxy hoa Co (x,t) phu thuoc ca vao toa o (x) va thi
gian (t) phan ng.
Giai phng trnh vi phan tren va rut gon ta co :
C o Co
C o ( x, t )
x x=0 = 1 / 2 D 1 / 2 t 1 / 2

o
bm

Cobm : Nong o chat oxy hoa be mat ien cc.

Gradien nong o cua chat b kh tren be mat ien cc (x = 0) ty le nghch
vi can so bac 2 cua thi gian t.
Hnh ve bieu dien s phan bo nong o cua vat chat 0 be mat catot tai cac
thi iem t1 < t2 < t3 < t4 sau khi at
len ien cc mot ien the khong
oi.
Qua hnh ve ta thay rang tng
t nh phng trnh tren Gradien
nong o be mat ien cc cung
giam theo thi gian t. Mat o dong
ien se bang :
i d = ZFD0 (

C o ( x, t )
)x = 0
x
29

id =

ZFDo

(C o C o )
1/ 2 1/ 2
t

1/ 2

bm

Phan bo nong o chat b kh be mat catot tai

thi iem khac nhau khi cho vao ien cc mot
ien the khong oi.

Theo phng trnh tren th mat o dong ien i giam theo can so bac 2
cua thi gian t.
Neu nh ien the a vao ien cc am hn ien the 0 nhieu th Cobm =
0 va khi ay co dong ien khuech tan gii han qua ien cc :
1/ 2

ZFD0 C o
1/ 2t 1/ 2
1

i gh(K) =
Quan he bac nhat gia id va

t 1/ 2

a c thc nghiem xac nh la ung.

Do o thay rang cang tang thi gian ien phan th i d cang giam va khong
the co che o khuech tan on nh c khi t th id 0 va nong o chat
phan ng be mat ien cc va trong dung dch bang nhau.
Quan he gia igh va

1
t

1/ 2

rat thuan tien e xac nh he so khuech tan be

mat ien cc.

Phng trnh dong khuech tan gii han tren anot cung tng t nh phng
trnh tren catot.
T hai phng trnh tren ta thay rang thi iem ong mach ngha la khi t =
0, mat o dong ien ban au, i (t = 0) = . Tren thc te th i (t = 0) khong the
ln vo cung c v khi ay phan ng ion hoa se khong che toc o cua qua
trnh.
d. Phng trnh khuech tan khong on nh oi vi ien cc hnh cau:

Ky hieu ban knh hnh cau la ro. V hnh cau oi

xng nen hng trong khong gian khong quan trong. Tai
cac iem cach eu tam ien cc th nong o va Gradien

nong o bang nhau. Do o co the xet nong o bat ky

iem nao o trong dung dch tai thi iem bat ky nh la
ham cua hai bien so : Thi gian t va o dai cua vect ban knh r (ngha la
khoang cach ti tam hnh cau )
Khi r = ro th :
0

C o (r , t )
)r = ro =
r

C0
Do t

Co
ro

Phng trnh tren gom 2 thanh phan :

30

Thanh phan th nhat tng ng vi bieu thc cua dong khuech tan en
ien cc phang, thanh phan nay ty le vi t .
Thanh phan th hai la hang so.
Khi t nho th so hang th nhat ln hn so hang th hai nhieu va s khuech
tan en be mat hnh cau giong nh en be mat phang. Khi t tang th so hang
th nhat giam v phan dong ien tng oi cua so hang th hai tang len. Neu
tiep tuc tang thi gian th dong ien khong giam ti khong ma ch ti 1 gia tr
khong oi.
`

igh =

ZFDo C o
ro

Ngha la khuech tan chuyen t trang thai khong on nh thanh trang

thai on nh (khong phu thuoc t)
Ngi ta cung chng minh c rang, s thiet lap trang thai khuech
tan on nh khong phai do dang hnh cau cua ien cc quyet nh ma do kch
thc co han cua ien cc.
Vi ien cc hnh cau ban knh 1mm khi Do co gia tr bnh thng th
thi gian can thiet e khuech tan chuyen thanh on nh la 300 giay. Do o
trong khoang 10 giay au tien sau khi ien phan, chieu day cua lp khuech
tan con nho so vi ban knh hnh cau th co the ap dung c nh luat
khuech tan en ien cc phang cho s khuech tan en ien cc hnh cau.
3. Phng trnh ong hoc tong quat cho ca hai khu vc khong che kch
ong va khong che khuech tan:
phan tren ta thay, ng cong phan cc toan phan gom3 khu vc chnh :
- Khu vc ong hoc (khong che kch ong )
- Khu vc qua o (khong che hon hp )
- Khu vc khuech tan (khong che khuech tan)
Phng trnh tong quat cho ca 3 khu vc la :
i=

i phong i gh
i gh + i phong

T phng trnh tren ta thay :

- Neu iphong >> igh th i = igh tc la toc o cua qua trnh b km ham bi
giai oan khuech tan.
- Neu igh >> iphong th i = iphong tc la toc o cua qua trnh b km ham bi
giai oan phong ien.
Cung t phng tren ta co the viet :
31

1 i gh + i phong
=
i
i gh .i phong
hay :

1
1
1
=
+
i i phong i gh

CHNG II : ONG HOC MOT SO QUA TRNH IEN CC

I. ong hoc qua trnh thoat H2 :
Theo Frumkin th qua the cua phan ng ien hoa hoc la ai lng bieu
dien s chuyen ien the ien cc gay ra bi phan cc ien hoa hoc. Ngi ta
phan biet 2 loai qua the anot A va qua the catot K.
A = Cb - iA (< 0 )
Cb : ien the ien cc H2 trang thai can bang.
iA : ien the ien cc anot a b phan cc ( v du : Phan ng ion hoa
phan t H2)
oi vi phan ng Catot (khi ay ien the dch chuyen ve pha am hn) th :
K = Cb - iK (K > 0)
Theo nh ngha tren th A se co gia tr am khi phan cc anot con K co
gia tr dng khi phan cc Catot.
Theo Tafel khi mat o dong ien u ln th gia qua the cua H2 va mat o
dong ien co phng trnh sau :
K = a + blgiK
a va b la hai he so khong phu thuoc vao mat o dong ien.
Nhan xet :
-oi vi phan ln kim loai phng trnh tren phu hp vi thc nghiem trong
khoang mat o kha rong t 10-9 10 A/m2 ( vi ien cc Hg trong dung dch
HCl)
Tuy nhien theo phng trnh Tafel th khi iK tien ti 0 th tien ti -,
trong khi o theo nh ngha khi iK tien ti 0 th
tien ti khong.
H
2
Trong thc te khi phan cc nho :

= kiK
H
2
Trong o : k la hang so
Khi phan cc nho qua the phu thuoc mat o dong ien theo quan he bacnhat.
-Hang so a phu thuoc vao ban chat ien cc , trang thai be mat cua no,
thanh phan chat ien gia va nhiet o. Hang so a co gia tr nam trong khoang
32

t 0,3- 1,7volt. Gia tr cua a ac biet cao vi mot so kim loai nh: Ch, Thuy
ngan, kem, Catmi, thiec.
-Hang so b t phu thuoc vao ban chat kim loai va thanh phan dung dch.
-Cac so lieu thc nghiem cho thay rang qua the phu thuoc vao nhiet o,
thanh phan dung dch. Trong khoang ap suat t 1-200atm qua the khong phu
thuoc vao ap suat. Levin va Dunberphoc thay rang qua the giam khi chuyen
t dung dch nc sang ru trong cac ieu kien tng ng. Qua the phu
thuoc rat nhieu vao pH dung dch. Trong khoang pH = 2-7 qua the tang t
0,055-0,058 ( 22oC) khi tang 1 n v pH.
-Cac anion hoat ong be mat nh Cl-, Br-, I- lam giam qua the Hydro khi
mat o dong ien khong ln. Khi mat o dong ien ln cac anion b ay ra
khoi be mat ien cc (ien the u am) do o anh hng cua anion bien mat.
Ngi ta cung thay rang qua the tang len khi be mat ien cc hap phu nhng
ion tch ien dng (v du cac Cation hu c).
Hien nay co nhieu gia thuyet ve qua the H2. Tieu chuan e xet gia thuyet
ung nhat la cac phng trnh rut ra t gia thuyet o phai giai thch c cac
so lieu, hien tng thc nghiem a neu tren.
II.ong hoc phan ung thoat Oxy :
Phan ng thoat oxy la mot phan ng anot phc tap, bao gom nhieu giai
oan noi tiep nhau :
Trong moi trng kiem :
Trong moi trng kim:
M + OH MOH + e
(I)
MOH + OH MO + H2O + e
2MO
2M + O2
hay : M + OH- MOH + e
2MOH MO + M + 2H2O
2 MO
2M + O2
Trong moi trng axt th giai oan (I) la :
M + H2O MOH + H+ + e
Chat trung gian co the la MO hoac MOH
Hien nay co nhieu y kien khac nhau ve c che cua phan ng thoat oxy
v:
- Phan ng thoat oxy co nhieu phan ng phu.
- Kho o chnh xac ien the thuan nghch tieu chuan cua ien cc oxy.
33

- Trang thai be mat ien cc thay oi theo thi gian, chon anot on nh
trong ieu kien thoat oxy rat kho khan. Thc vay, muon cho oxy thoat ra t
dung dch axt co aH+ = 1 th ien the ien cc phai dng hn +1,24v. Nhng
phan ln cac kim loai eu b hoa tan trc khi at ti ien the o. V vay
muon nghien cu qua trnh thoat oxy trong moi trng axt phai dung kim
loai nhom Platin, vang va mot so kim loai qu khac. Trong moi trng axt,
cac kim loai o c mot lp oxt ben vng bao ve.
Trong dung dch kiem, ien the thoat oxy am hn (+0,41v khi aOH- = 1) nen
co the dung kim loai nhom Fe, Cd va mot so kim loai khac lam anot. Oxy
thoat ra tren be mat t nhieu b oxy hoa.
- Qua the cua oxy tang len t t theo thi gian (Fe, Pt) hoac nhay vot
(Pb,Cu) do o ta phai lay gia tr on nh cua no.
- Tren ng bieu dien phu thuoc logia thng thay nhieu oan
O
2
thang co o ln khac nhau, phan anh s thay oi ot ngot ong hoc cua qua
trnh. Cac oan thang o tuan theo nh luat Tafel :
= a + b logia
O
2
Gia tr cua hang so a, b phu thuoc vao nhiet o, vat lieu ien cc va thanh
phan dung dch.
- Trong khoang mat o dong trung bnh, qua the oxy trong dung dch
dang kiem tang theo day : Co, Fe, Cu, Ni, Pb, Au, Pt.
- Khi trong dung dch co cacCation la th qua the cua oxy cung tang len.
- Qua the cua oxy con phu thuoc ban chat cua lp oxt tao thanh tren be
mat ien cc. V du khi chuyen t -PbO2 sang -PbO2 th a giam 0,4v.
III.ong hoc qua trnh kh Oxy :
Phan ng kh oxy Catot la mot phan ng thng gap trong thc te, nhat
la trong an mon kim loai.
Nghien cu bang cc pho thay qua trnh kh oxy gom 2 song :
- Song th nhat ng vi phan ng :
O2 + 2H+ + 2e H2O2
- Song th hai:
H2O2 + 2H+ +2e 2H2O

34

+10
+5
0
0,5

-0,5 -1,0 -1,5 -2,0v

ng cong cc pho cua qt kh O2 tren Hg.

Trong phan ng kh oxy Ca ot giai oan hoa hoc khong khong che qua
trnh.
Nguyen nhan gay qua the chu yeu do cham phong ien va khuyech tan.
Qua trnh phong ien cua Oxy gom 2 giai oan noi tiep :
Trong moi trng trung tnh va kiem :
O2 + 2H2O + 2e " H2O2 + 2OHH2O2 + 2e
" 2OHTrong moi trng axt :
O2 + 2H+ + 2e
" H2O2
H2O2 + 2H+ + 2e " 2H2O
ng cong phan cc co hai song khi can phai co qua the ln e kh
H2O2. Khi ay s kh oxy thanh H2O2 a b khong che bi s khuech tan oxy
va dong kh oxy at ti gii han. ien the u am H2O2 mi tiep tuc b kh
tiep va dong kh H2O2 cung at gia tr gii han.
IV . S ket tua ien kim loai:
1. ieu kien xuat hien pha mi :
Khi cac phan ng ien cc tien hanh thng kem theo s xuat hien
cac pha mi. V du : Khi kh ion Hydro th co bot kh tao thanh, khi kh cac
ion kim loai se xuat hien tinh the kim loai.
S tao thanh pha mi thng bat au t tao mam tinh the (ran ) hoac
giot au tien (long). Xuat hien mam tinh the tren be mat catot kim loai
thng gap tr ngai ln, do o oi hoi ton mot nang lng ln. Cung v vay
muon ket tinh muoi t trong dung dch, ngng tu giot chat long t pha hi th
nong o muoi va ap suat hi phai ln hn bao hoa tc la phai at mot o qua
bao hoa nhat nh. Trong trng hp ket tua ien kim loai th can phai dch
chuyen ien the ve pha am so vi can bang th ion kim loai mi b kh thanh
nguyen t kim loai va tao thanh pha mi.
Cong tao mam tinh the c xac nh theo cong thc :
A3 =

1
6
3

16 3V 2
C
R 2T 2 ln
Cs

35

Trong o :
: sc cang be mat
V : Th tch phan t
C : Nong o dung dch qua bao hoa
CS : nong o can bang cua dung dch bao hoa
C/CS : o qua bao hoa cua dung dch
T phng trnh tren ta thay cong se giam khi tang o qua bao hoa.
So 6 ng vi 6 mat cua mot tinh the lap phng.
Xac suat W tao thanh tinh the mi quan he vi cong theo phng
trnh sau :
W = Bexp (-

A3
)
RT

B : Hang so
Khi A3 giam th xac suat tao mam tinh the tang len.
2. Qua th ket tua kim loai ien cc:
Qua trnh ket tua ien kim loai thng tien hanh trong cac dung dch
muoi n hoac phc va noi chung bao gom cac giai oan sau :
[Me(H2O)x]Z+dung dch D [Me(H2O)x]Z+lp kep (a)
[Me(H2O)x]Z+lp kep D MeZ+ + XH2O
(b)
Z+
Me + Ze
D Menguyen t
(c)
Menguyen t
D Memam tinh the
(d)
Memam tinh the
D Me li tinh the
(e)
Nhng giai oan sau ay co the khong che qua trnh ket tua ien kim
loai.
- Giai oan d hoac e b cham tre : Cham ket tinh
- Giai oan c b cham tre : Cham phong ien
a. Ly thuyet cham ket tinh:
Volmer gia thiet rang, trong qua trnh ien ket tinh kim loai th qua
the ong vai tro nh o qua bao hoa khi ket tinh tinh the t dung dch.
Qua trnh ket tua ien kim loai co the b khong che bi toc o tao
thanh mam tinh the hai hoac ba chieu.
. Toc o tao thanh tinh the ba chieu khong che ong hoc
qua trnh ket tua ien :
Mam tinh the ba chieu la mot v the mi xuat hien trong pha cu.
Mam nay phai co kch thc u ln th mi ton tai can bang vi pha cu.
36

Cong can thiet e tao thanh mam tinh the ba chieu co the tnh theo
phng trnh:
A3 =

1
6
3

16 3V 2
C
R 2T 2 ln
Cs

ong hoc qua trnh ket tua ien kim loai se b khong che bi toc o tao
mam tinh the ba chieu khi kim loai ket tua tren be mat ien cc la hoac tren
ien cc cung loai nhng b thu ong hoa hay ngo oc. Trong trng hp nay
qua th cua kim loai ong vai tro nh o qua bao hoa :
ZF = RTln C/CS
Toc o tao thanh mam tinh the ba chieu co the bieu dien bang
phng trnh :
i = Ke A3 / RT
Thay A3 t phng trnh tren va RTlnC/CS = ZF vao ta co :
1/2 = a blogi
Vi a =

Z 2F 2
ln K
32 3V 2

,b=

2,3Z 2 F 2
32 3V 2

S tao thanh mam tinh the ba chieu co y ngha rat ln vi ong hoc
qua trnh chuyen pha. No thng xay ra trong trng hp ket tua kim loai
tren be mat ien cc hay la tinh the mi sinh ra khong the ln len c na
nen muon tao thanh pha mi phai tao mam tinh the ba chieu.
Hnh ve trnh bay quan
he ien the Thi gian cua qua
trnh ket tua ien kim loai tren
be mat ien cc la.

Bien thien ien the ien cc theo th

gian khi ket tua kim loai tren ien cc la.
i, i, Cb ien the ng vi mat o dong
ien i, iva can bang (i= 0)
Ban au v phai nap lp kep va ien cc la nen can phai dch chuyen
37

ien the ien cc ve pha am ti mot qua the ban au la + u e tao

thanh mam tinh the au tien.
Nhng khi a co mot lp tinh the mi tren ien cc th qua the giam
xuong con . V be mat ien cc khong phai la la na.
Neu ngat dong th ien the ien cc dan dan tr ve ien the can bang
Cb.
. Tao mam tinh the hai chieu khong che qua trnh ong hoc:
Khi a co mam tinh the roi th cac tinh the ln len se tien hanh theo
tng lp do tao thanh cac mam tinh the hai chieu.
Neu nh be mat phat trien cua
tinh the c bieu dien bang hnh ve th
nang lng co li nhat khi phan t
chiem v tr III, v tr II kem li hn va
toi nhat la v tr I v tr tng ng vi
thi gian au qua trnh phat trien tinh
the. Con khi tren be mat a co tap hp
nhng phan t cau tao th co kha nang
ien nhieu lan vao v tr th III la v tr co li nhat ve phng dien nang
lng. Kieu tao mau nh tren goi la tao mam hai chieu.
Neu goi A2 la cong can thiet e tao mam tinh the hai chieu ben vng,
ta co :
i = K1. e A2 / RT
i : toc o tao mam tinh the hai chieu
K1 : Hang so
A2 =

2 S
C
RT ln
Cs

: sc cang bien

S : Be mat phan t
o bao hoa can thiet e tao mam tinh the lien quan vi qua the theo
cong thc :
=

RT C
ln
ZF Cs

Sau khi bien oi va rut gon, ta co :

=

1
1
= a b ln i
hay
a b ln i

Vi :
38

a =

ZFRT
ln K1
2 S

,b=

ZFRT
2 S

Nhng cac ion phong ien tren ien cc khong phai bat k cho nao
tuy y ma ch ni li nhat ve mat nang lng. Sau o nguyen t con phai
dch chuyen tren be mat ien cc va tm cho thch hp e chuyen vao mang
li tinh the. Cho nen chung can phai thang tr lc cua moi trng bao quanh
trung tam phat trien.
e thang tr lc o phai co mot qua the nhat nh. Khi ay gia qua
the va mat o dong ien co quan he bac 1 :
= ki
Volmer chia kim loai thanh 2 nhom :
- Nhom kim loai co phan cc nho nh : Hg, Cu, Zn, Ag, Bi (phan cc
ket tinh la chu yeu ).
- Nhom kim loai co phan cc ln gom kim loai nhom sat.
Ch chiem v tr trung gian .Thuy ngan ch co phan cc nong o.
Kim loai nhom sat phan cc gay ra bi cham phong ien.
b. Ly thuyet cham phong ien :
xa ien the can bang toc o phan ng nghch co the bo qua va co
phng trnh Tafel :
= a + blogi
a =-2,303

RT
RT
log i mo , b = 2,303
ZF
ZF

iom : Dong ien trao oi cua phan ng:

MeZ+ + Ze D Me
Qua the tang khi giam iom v vay nhom sat co iom nho nhat nen qua
the cung ln nhat va qua trnh phong ien cua cac ion nhom sat b khong che
bi s cham phong ien.
3. Ly thuyet ve s phong ien ong thi cua cac cation kim
loai :
Trong dung dch bao gi cung co nhieu ion. Do o trong khi ien
phan khong phai bao gi cung ch co 1 ion ma nhieu ion ong thi phong
ien. Nghien cu cac qui luat ong thi phong ien cua ion co y ngha ky
thuat rat quan trong. Nh no ta co the ieu che c kim loai co o tinh khiet
cao cha rat t tap chat, co the che tao c cac loai hp kim bang phng
phap ien hoa hoc. Co hai thuyet c ban ve s phong ien ong thi cua ion.

39

- Phong ien ong thi cua ion trong he thong ly tng khong lien ket:
Khi ay toc o phong ien cua tng ion rieng biet khong thay oi khi phong
ien ong thi ngha la gia cac ion khong co tac dung tng ho.
- Phong ien ong thi trong he thong ket hp : Khi ay gia cac ion co s
tac dung tng ho do o qui luat kh ion rieng biet b pha v.
a.Phong ien ong thi cua ion trong he thong ly tng khong lien ket:
ieu kien e cac ion phong ien ong thi la ien the ien cc cua
chung phai bang nhau.
o1 +

RT
RT
o
ln a1-1 = 2 +
ln a2 - 2
n1 F
n2 F

(1)

o1, o2 : ien the ien cc tieu chuan cua ion 1 va 2

n1, n2 : hoa tr cua ion 1 va 2
1, 2 : Qua the cua ion 1 va 2.
T hnh ve ta thay tai cung ien the x, toc o phong ien cua cac ion la
i1, i2, i1 i2.
Toc o phong ien tong cong :
iK = ii = i1 + i2
Trong thc te nhieu khi ch
can 1 ion phong ien, con s phong
ien cua ion khac se co hai v lam
giam hieu suat dong ien hoac giam
o tinh khiet cua san pham.
Neu ky hieu A la hieu suat
dong ien cho ion can phong th :
A=

ii
i
= i
ii i K
S o phong ien ong thi cua
cac ion1 va 2

ii : Toc o cua ion can phong

iK : Toc o phong ien tong cong cua cac ion.
Thong thng A < 1
V du : Trong dung dch nc, ngoai ion kim loai con co ion H+. Neu ien the
Catot am hn ien the can bang cua ion H+ trong dung dch th H+ se phong
ien ong thi vi ion kim loai.

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AMe =

Me

, AH =

iH
iK

, hay AMe =

i Me
i Me + i H

Co khi ta can phai phong ien ong thi cac cation. Trong trng hp o ta
lam cho ien the cac ion phong ien xch lai gan nhau bang cach :
- Thay oi hoat o cua ion trong dung dch : Nhn cong thc (1) ta thay
tang hoat o cua ion len 10 lan dch chuyen ien the 0,029volt vi ion hoa tr
2 va khi tang 1000 lan ch chuyen 0,087v. Do o s xch gan ien the lai se
gap kho khan khi o khac nhau qua nhieu.
- Cho cac ion co ien the dng hn phong ien dong gii han.
V du : Zn, Cd co ien the can bang la 0,76v va 0,4v nh vay khi
ien phan Cd se phong ien dong gii han va ien the se at ti ien the
phong ien cua Zn (Trong trng hp nay H2 khong thoat ra v qua the cua
Hydro tren Zn va Cd ln)
i = iCd + iZn
2+
V nong o Zn ln rat nhieu so vi
i
2+
Cd nen dong di c do Cd2+ khong ang ke,
Cd2+ chuyen chu yeu do khuech tan.
4
iCd = idCd = Hang so
3
Do o thay oi ien the co the tao
2
c hp kim co thanh phan theo y muon.
1
Tuy nhien t dung phng phap nay

-0,6
-0,7
v ket tua ien thng khong at yeu cau. -0,4
Bien thien ien the ien cc khi
ket ta hp kim Zn Cd t dungdch
2N ZnSO4 va 0,2N CdZO4 20 oC .
-To thanh phc cht:
Phng php co hieu qua nhat e xch gan ien the la tao thanh phc
chat kim loai co ien the dng hn do o dch chuyen ien the cua no ve
pha am hn. S tao thanh phc chat khong nhng xch gan ien the cua cac
kim loai khac nhau lai ma con thay oi v tr cua chung.
V du : Trong dung dch muoi n gian ien the cua Ag+ dng hn
cua Zn2+ la 1,5v. Trong dung dch Xyanua th ien the thoat cua Ag am hn
cua Zn.

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Mat khac thay oi qua the cua ion cung lam cho ien the phong ien cua
ion xch lai gan nhau. Khi chuyen t dung dch cha ion n gian sang dung
dch cha ion phc qua the cung tang.
b . Phong ien ong thi trong he thong ket hp:
Trong thc te th cac ion phong ien ong thi luon tac ong lan nhau
nen toc o phong ien cua chung phu thuoc vao cau tao lp ien tch kep,
ong thi vao trang thai cua ion trong dung dch va cau tao lp nen. Cho nen
thay v cong thc (1) ta phai dung cong thc :
o1 +

a
RT
RT
kh
ln a1 +
ln 1 1 -
n1 F
n1
iai

= o2 +

a
RT
RT
kh
ln 2 2 -2
ln a2 +
n2 F
n 2 F iai

Trong o :
i : he so ac trng cho kha nang xam nhap vao lp kep cua ion i.
1kh, 2kh : qua the khi phong ien ong thi cua cac ion 1, 2 trong he
thong ket hp.
So hang th 3 trong ca ve phai va ve trai bieu th s dch chuyen ien
the khi co cac ion i tham gia lp kep.
. Anh hng cua lp ien tch kep va trang thai cua ion trong dung dch:
Nong o cua ion trong lp kep c tnh theo cong thc ;
[Men+]lk = [Men+]dd e- nF1/RT
Khi co cac ion khac cung phong ien th nong o phong ien cua mot
loai ion se nho hn bnh thng v b ion kia ay ra khoi lp kep. Do o khi
phong ien ong thi hai ion th thng mot ion hoac ca hai ion b giam toc
o.
. Anh hng cua ban chat lp nen :
-Lp nen lam ha thap ien the phong ien cua ion. Tac dung kh phan
cc cua nen do chung tao thanh hp kim vi ion phong ien.
V du : Na+ phong ien tren ien cc Hg ien the 1,7v thay v
2,7v.
- Lp nen lam tang ien the phong ien cua ion
Khi nghien cu s ket tua cua Ag ta thay, toc o ket tua cua no khac
nhau cac ni tren be mat ien cc. Nguyen nhan cua hien tng o la do
be mat ien cc khong ong nhat.

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V . Ly thuyet hoa tan ien hoa hoc kim loai :

Neu kim loai hoa tan anot va tao thanh cac ion hydrat hoa n gian
th co bieu dien no bang phng trnh :
[M] + xH2O = MeZ+aq + Ze
Neu tao thanh ion phc th :
[M] + xA- + yH2O = [MAx]aqZ-X + Ze
Kim loai hoa tan anot ien the dng hn ien the can bang co
ngha la hoa tan kem theo phan cc anot :
a = ia - Cb
Co phan cc anot la do co s cham chuyen van, cham phan huy pha
rn hay la cham chuyen ien tch ngha la ngc lai qua trnh catot tng
ng. gan trang thai can bang co mot s oi xng nao o gia qua trnh
thoat kim loai catot va hoa tan kim loai anot.
.
Tnh chat cua kim loai trong qua trnh hoa tan anot t c nghien cu, tuy
nhien co the dung ly thuyet cham phong ien cho kim loai nhom sat :
a = aa + bblogi
aa, bb la cac hang so
Trong qua trnh hoa tan, tren be mat kim loai co the tao thanh cac
mang oxt do tac dung hoa hoc cua anot vi cac chat oxy hoa hoac do oxy
hoa anot. S tao thanh lp oxt be mat lam cho kim loai b thu ong qua trnh
hoa tan b can tr hay ngng han va ien the anot tang len. Khi ay cac ion
khac se tham gia vao phan ng ien cc. V du : ion OH- se phong ien giai
phong oxy.
VI.S HOA TAN ANOT CUA CAC HP KIM :
Trong cac hp kim a pha th cac pha oc lap vi nhau ve phng
dien ien hoa hoc. Cac pha ch hoa tan anot khi ien the anot at ti ien the
ion hoa. Cac pha co ien the am nhat se hoa tan trc. ch sau khi chung hoa
tan hoan toan hoac ien the anot at ti ien the ion hoa cua cac pha dng
hn th nhng pha nay mi b hoa tan.
Neu pha co ien the am hn hoa tan de dang va ham lng cua no
trong hp kim tng oi ln th ien the ien cc anot thng khong at ti
ien the hoa tan pha dng hn. Khi ay cac pha dng se ri xuong di
dang mun.
Nhng hp kim mot pha la nhng hp chat hoa hoc hay dung dch ran
cua cac kim loai khac nhau se hoat ong nh mot kim loai duy nhat khi ta
phan cc anot. Hoat o cua kim loai am trong hp kim nho hn trang thai
43

t do va ien the hoa tan cua hp kim nam gia ien the hoa tan cua 2 cau t
c s ( tuy nhien ien the hoa tan cua hp kim nay thng gan ien the hoa
tan cua cau t am hn).
VII.IEN PHAN:
ien phan la s phan huy hoa hoc cua cac chat trang thai nong
chay hay trong dung dch khi co dong ien chay qua.
Khi tien hanh qua trnh ien phan Catot Cation nao o co ien the
dng hn se phong ien trc, con anot anion nao o co ien the am hn
se phong ien trc.

44