1

Chng IV
CHUYN NG CA ION
TRONG DUNG DCH IN LY.
TNH DN IN CA
DUNG DCH IN LY
1
2
IV.1. dn in ca dung dch in ly
IV.2. Phng php xc nh dn in, s ti v
linh ion
IV.3. nh hng ca cc yu t ti dn in
v s ti ca dung dch in ly
CHNG IV
2
3
1. dn in ca dung dch in ly
1.1. S chuyn ng ca tiu phn
trong dung dch.
1.2. dn in ring
1.3. dn in mol, ng lng
1.4. Vn tc chuyn ng ion, Linh
ion. dn in mol, ng lng
ion.
1.5. S ti ca ion
3
.1Chuyn ng ca ion
4 qu trnh chuyn ng c bn trong dung dch in ly:
i lu: chuyn ng cht hoc nng lng do ni lc
Truyn nhit: gradient nhit gia h thng v mi trng
Khuch tn: gradient nng
in di: chuyn in tch, cht do gradient in trng

4
J
i
= C
i
v
i
J
i
: dng lu cht, mol cm
-2
s
-1

C
i
: nng , mol cm
-3

v
i
: tc ca ht i i qua n v din tch, cm s
-1

5
dn in
Faraday phn loi:
- Dn in loi mt : in t
(kim loi, R nh, dn gim khi T tng)
- Dn in loi hai: ion
(dd in ly, nng chy, in ly rn, keo, cht lng ion, kh ion ha, )
Dung dch in ly:
C cation v anion u tham gia vo qu trnh dn in.
Nng
R nh, dn in tng khi T tng
* Polymer dn in: in t v ion
* Cht bn dn: in t v l trng
R ln hn KL cn nng lng kch thch, dn in tng khi T
tng)

5
Tnh cht dn ca vt liu khi- bn dn
6
Bn dn pha tp n- type
Bn dn pha tp p- type
Di dn (CB)
Di cm (FB)
Di ha tr (VB)
CB
VB
CB
VB
CB
VB
Bn dn Vt liu dn Cch in
Eg < 5eV FB
Eg > 5eV FB
E
dn in ca dung dch in ly
dn in (G): nghch o vi in tr (R):
7
G S (siemens)
R O
k S m
-1
k: dn in ring
l: khong cch gia 2 bng in cc, m
Cho hai bng in cc c thit din
A t song song, dn o c l:
1
G
R
=
1 A
G
R l
k = =
8
1.2. dn in ring
dn in ring l dn ca khi dung dch nm gia hai
in cc song song c thit din 1 cm
2
v cch nhau 1 cm.
theo h SI : dn in ring l dn ca khi dung dch nm gia
hai in cc song song c din tch 1 m
2
v t cch nhau 1 m.
8
1
. .
l l
G
A R A
k = =
[k] = ohm
1
.cm
1
= S.cm
1
(hay [k] = S.m
1
)
1 S = 1 ohm
1

9 9
1
2
. 0
R
R
R R I
M X CD
= =
C
D
R
X
R
M

R
2
R
1

Cu Wheatstone
Phng php xc nh dn in ring
dng dng xoay chiu
c tn s cao
o in tr
n nh nhit
1 1
.
l K
R A R
k = = =
K: hng s bnh hay hng s in cc
in cc
l
a
b
V d
- in cc o dn c thit din 6,00 cm
2
t
cch nhau 1.5 cm. Tnh hng s bnh (hng s
in cc).
- dn ca dung mi nc l 5,0 x10
-6
S. Tnh
dn in ring ca nc.
- dn ca dung dch KCl 10
-4
M l 6,42 x10
-5

S.
Tnh dn in ring ca KCl.
10
11 11
1.3. dn in mol, ng lng
dn in mol: dn in ca khi dung dch nm gia
hai in cc cch nhau 1 cm v c thit din sao cho khi dung
dch cha 1 mol cht in ly.
1
2 1
:
1000.
: /
:
M
M
s cm
C mol L
C
s cm mol
k
k

A =

dn in ng lng ( hay
N
): dn in ca
khi dung dch nm gia hai in cc cch nhau 1 cm v
c thit din sao cho khi dung dch cha 1 ng
lng gam cht in ly.
2 1
: lg/
1000
: lg
N d L
N
s cm d
k

A =

1.3. dn in mol, ng lng

Dung dch in ly mnh l tng: A khng ph
thuc nng
Dung dch tht: A ph thuc vo nng do:
Tng tc ion ion = 1
Dung dch in ly yu: A ph thuc vo nng do:
- Phn ly khng hon ton ca dd in ly.
12
13 13
1.4. Linh ion, linh mol, ng lng
dn in
nng
vn tc chuyn ng
in tch
14 14
. .
1
R
.
E
X
l
E E E
I A
l
l
A
k
k
A
=
A A A
= = =
X
l
+

+

Lc in trng, F
t
: lc coulomb
t i o
E
F Z e
l
A
=
Lc ma st, F
ms
:
F
ms
= 6tqr
i
v
i

F
ms
= F
t

6
i o i i
E
Z e rv
l
tq
A
=
Ion c/ u:
Ion chuyn ng khi c in trng in di
15 15
. .
6
i o
i i
i
Z e E
v u X
r l tq
A
= =
Vn tc chuyn ng c hng (v
i
) ca ion di tc dng ca lc in
trng X :
X= 1 V/cm
u
i
: Linh ion (vn tc tuyt i ca ion)
6
o
i o
i i
i
Z e
v u
r tq
= =
[v
i
] = cm/s; [u] = cm
2
.V
1
.s
1

Ion H
+
Na
+
K
+
Zn
2+
OH

Cl

Br

SO
4
2

u.10
4
36,2 5,19 7,62 5,47 20,6 7,91 8,09 8,29
Linh (cm
2
.V
1
.s
1
) ca mt s ion trong nc 25
o
C.

16 16
dn in mol ion: tch ca linh ion vi s Faraday

M
= u
i
.z.F
N
= u
i
F
2
6
N
i o A
i
Z e N
r

tq
=
I = I
+
+ I

I
+
= e
o
Z
+
n
+
v
+
A
I

=

e
o
Z

A

I =

I
+
+ I

= e
o
Z
+
n
+
v
+
A

+

e
o
Z

A

o o
. . .
E E
I e Z n Au e Z n Au
l l
+ + +
A A
= +
e
o
Z
+
n
+
= e
o
Z

1000
.
o o
F N
N
N e Z n
N
N e Z n
A
A
A
A
= =
+ +
Nu cht in ly phn ly
hon ton (o = 1) :
6
i o
i
i
Z e
u
r tq
=
.
i i
E
v u
l
A
=
AE
+

+

l
v
+
v

A
17 17
Nu cht in ly phn ly mt phn (o < 1) :
1000
. .
o o
F N
e Z n e Z n
o
= =
+ +
( . . ). .
1000 1000
N N E
I u F u F A
l
o o
+
A
= +
Thay u
i
.F bng
i
:
( ) . .
1000
N E
I A
l
o

+
A
= +
( )
1000
N o
k
+
+
=
. .
E
I A
l
k
A
=
Mt khc:
( )
1000
N o
k
+
+
=
1000
N
k
A =
.
1000
N
k
A
=
A = o(
+
+

)
18 18
Dd v cng long o = 1 v k hiu dn in v cng long l A
o

A
o
=
0
+
+
0

A
0
(A

) : dn in ng lng gii hn
Kohlrausch, 1875, thc nghim :
nh lut v s tnh dn in c lp ca cc ion: dn
in ng lng ca dung dch v cng long bng tng linh
ng lng ( dn in ng lng cation v anion)
1000
.
C o
N
o
k
A = A =
Linh ng lng ( dn in gii hn) ca mt s ion (S.cm
2
lg
-1
)
Ion H
+
Na
+
K
+
Zn
2+
OH

Cl

Br

SO
4
2

i
o
349,8 50,1 73,5 53,5 197,6 76,3 78,3 80,0
A = o(
+
+

0
i
: dn in ng lng gii hn ca ion (linh ng lng ti hn)
ng dng ca nh lut chuyn ng c lp ca ion
Xc nh dn in mol ti hn ca cht in ly yu.


19
K
C
=

o
o
2
1

C
= o.
o

1 1 1
2

=
o o
K
C ( )
HA A
-
+ H
+

V d: dn in mol ca dung dch acid HA
(0,004 M) l 359 S cm
2
mol
-1
. dn in mol ti
hn ca HA l 385 S cm
2
mol
-1
. Tnh in ly v
hng s phn ly Ka.
20
dn in ring c tnh cng:
Th d, dn in ring ca hn hp dung dch cha KCl
v NaOH s l tng dn in ring ca dung dch KCl v
NaOH.
dn in ng lng khng c tnh cng (tr dd v
cng long):
Khng c khi nim dn in ng lng ca mt
hn hp, ch c dn in ng lng ca mt cht in
ly.
Ch
21
1.5. S ti ca ion
V
i
khc nhau phn ng gp ca tng ion vo dn in
S ti (t
i
) : t l ng gp ca loi ion i vo dn in chung
Q
q
I
I
t
i i
i
= =
E t
i
= 1
1
. .
1000
i o i i i i i
E E
I e z n Au N A
l l

A A
= =

=
i i
i i
i
N
N
t

Nu dung dch ch c hai loi ion:

t
+
+ t

= 1

+
+
+
=
+


t

+
+
=

t
22
2. Phng php xc nh dn in, s
ti v linh ion
2.1. ng dng dn in
2.2. Phng php xc nh s ti
a) Phng php Hittorf
b) Phng php ranh gii chuyn ng
c) Xc nh s ti nh mch nng c ti
2.3. Phng php xc nh linh ion

22
23
Chun dn
k
.

m
S

Ion H
+
Na
+
K
+
Ag
+
NH
4
+
Cl

NO
3

AcO

OH

i
o
349,8 50,1 73,5 61,9 73,5 76,3 71,5 40.9 197,6

i
o
: 25
o
C, nc
24
V
t

k, mS
V, ml
AgNO
3
+ KCl AgCl+ + KNO
3
Ag
+
+ NO
3

+ K
+
+ Cl

AgCl+ + K
+
+ NO
3

NO
3

Cl

Ag
+
K
+
Phn tch
phn ng
gp ca cc
loi ion vo
k trong qu
trnh chun

25
a) Phng php Hittorf
b) Phng php ranh gii chuyn ng
c) Xc nh s ti nh mch nng c ti
2.2. Phng php xc nh s ti
T tham kho ti liu !
2.3. Phng php xc nh linh ion
26
V d: in phn dung dch CuSO
4
0,20 M tnh s ti. Th
tch catolit l 36,4 ml. Lng Cu
++
sau khi in phn cn li
trong catolit l 0,44 g. Lng bc gii phng trong coulomb
k bc l 0,285 g. Tnh s ti ca cc ion trong dung dch
sulfat ng.
Phng php Hittorf
Phng php Hittorf xc nh s ti da trn mi lin
quan gia s thay i nng trong vng dung dch
nm st vi in cc v in lng i qua dung
dch trong qu trnh in phn
27
Phng php ranh gii chuyn ng
A
C
MX
MX
t
t = 0
D
B
+
q
N h S
q
N V
q
q
t
. . .
= =
+
=
+
V d. Trong mt th nghim xc nh s ti ca KCl, ng
th nghim c ng knh trong l 4,146 mm cha KCl
0,021 mol/l. Cng dng in l 18,2 mA. Mng phn
cch di chuyn c 318 mm sau thi gian 1000 giy. Tnh
s ti ca ion K
+
, vn tc chuyn ng tuyt i ca K
+
v
linh ng lng ca K
+
.

q l in lng, h l khong cch m
mng AB dch chuyn, S l thit din
ngang ca ng th:
28
3. nh hng ca cc yu t ti dn
in v s ti ca dung dch in ly
3.1. dn in vi bn cht ca cht in ly
3.2. dn in vi bn cht dung mi
3.3. nh hng ca nng n dn in v
s ti
3.4. nh hng ca nhit
3.5. S ph thuc ca dn in cht in ly
mnh vo nng
3.6. S ph thuc ca s ti vo nng
28
29
3.1. dn in vi bn cht ca cht in ly
dn in ng lng 25
o
C trong nc ([A
o
] = S.cm
2
lg
1
)
H
2
SO
4

HCl
HNO
3

429,8
426,2
412,2
KOH
NH
4
OH
NaOH
271,1
271,0
247,0
KCl
KNO
3

NaCl
149,9
145,0
126,4
Acid > Baz > Mui
30
Linh ng lng ion trong nc v bn knh ca cc ion 25
o
C
([
i
o
] = S.cm
2
lg
1
)
Ha tr ion nh nhau th linh ng lng tng khi bn knh ion
tng (tr trng hp I

v Br

).
Khi bn knh ion gn hoc bng nhau th linh ng lng ca
cation ln hn ca anion.
Ion H
+
v ion OH

c linh ng lng bt thng, ln hn ca

cc ion khc t 3 - 8 ln.
Ion
r ()

i
o

H
+

0,00
350
Li
+

0,68
38,7
Na
+

0,98
50,1
Ag
+

1,13
61,9
K
+

1,33
73,5
Cs
+

1,65
76,8
NH
4
+

-
73,0
Ion
r ()

i
o

Ni
+

0,74
54,0
Fe
2+

0,80
53,5
Cu
2+

0,80
54,0
Zn
2+

0,83
53,5
Cd
2+

0,99
54,0
Pb
2+

1,26
70,0
Ba
2+

1,38
63,7
Fe
3+

0,67
68,0
Al
3+

0,57
63,0
Ion
r ()

i
o

F

1,23
55,4
Cl

1,81
76,3
Br

1,96
78,3
I

2,20
76,8
NO
3

-
71,4
OH

-
198
H
2
PO
4

-
36,0
HPO
4
2

-
57,0
SO
4
2

-
80.0
31
Linh bt thng ca H
+
v OH

32
IV.3.4. nh hng ca nhit
o |
t t o o
o
t t t t = + [ ( ) ( ) ] 1
2
H
+
NH
4
+
Na
+
OH

Cl

IO
4

(Scm
2
lg
1
)
o
349,8
0,0142
73,5
0,0187
50,1
0,0208
198,3
0,0196
76,35
0,0194
54,5
0,0144
H s nhit ca dn in ca mt s ion
33
S ti nhit
t
i
> 0,5
t
i
< 0,5
t
i
= 0,5
Nng tng
T,
o
C
Na
+

Ag
+

H
+

Li
+

K
+

0
0,387
0,461
0,844
0,321
0,498
18
0,396
0,471
0,833
25
0,404
0,481
0,822
0.336
0.490
30
0,442
-
0,784
45
0,404
0,347
0,487
100
0,406
0,352
0,479
34
IV.3.2. dn in vi bn cht dung mi
nh lut Walden-Pisajevski:
const v
const
o
o
=
=
q
q
.


const N
r
e Z
e N
r
e Z
F v
A
i
o i
i o A
i
o i
io i
= = = =
t
q
tq

6
. .
6
2
o o
i
o i
io
r
e Z
v
tq 6
=
35
IV.3.3. nh hng ca nng n dn in
dn in ring
dn in ng lng
lun gim khi nng tng
k u tin tng khi nng tng, t cc
i, sau gim.
V tr cc i ph thuc vo bn cht v
nng ca cht in ly.
KCl

C
= o.
o

36
C A
o C
=
A - hng s thc nghim h s Kohlrausch.

o

nh lut thc nghim Kohlrausch
C

C

0
V SAO ?
37
IV.3.5. dn in cht in ly mnh vo nng
Thuyt Debye-Onsager gii p
Hiu ng in di
Hiu ng bt i xng
Gii thch phng trnh kinh nghim ca Kohlrausch
V sao dn in ca cht in ly mnh gim khi nng tng ?
38
Thuyt Debye-Onsager
in di
Bt i xng
C b Z
d
d i
= A
2 / 1
3 2
10 . 2
6
|
|
.
|

\
|
=
kT
N N e
b
o
A A o
d
cc tq
( )
2 / 1
o
3
o
3
10 2
24
2 2 ) . (
|
|
.
|

\
|
=
+
kT
N
kT
e Z Z
b
A
o
bdx
c c c tc
C b
b
o
i
bdx
= A

=
o
(b
d
+ b
bx

o
)
C

39
Hiu ng Wien: tng t ngt v tin ti
o
khi dng xung
t mt in trng rt ln (X = 20-40 MV/m) vo dung
dch

Hiu ng Debye-Falkenhaghen: dn in ng lng
tng khi tng tn s dng xoay chiu