Chng IV

CHUYN NG CA ION
TRONG DUNG DCH IN LY.
TNH DN IN CA
DUNG DCH IN LY

CHNG IV
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

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

.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

Ji = Ci vi
Ji : dng lu cht, mol cm-2 s-1
Ci : nng , mol cm-3
vi : tc ca ht i i qua n v din tch, cm s-1

 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

E
Di dn (CB)

CB

CB

Di cm (FB)

VB

Eg < 5eV

Di ha tr (VB)

CB
FB

VB
Vt liu dn

Bn dn

Eg > 5eV

FB

VB
Cch in

Bn dn pha tp n- type

Bn dn pha tp p- type

 dn in ca dung dch in ly
dn in (G): nghch o vi in tr (R):
1
G
R

Cho hai bng in cc c thit din

A t song song, dn o c l:
1
A
G
R
l
: dn in ring
l: khong cch gia 2 bng in cc, m
G
R

S (siemens)

S m-1
7

1.2. dn in ring

l 1 l
G. .
A R A
dn in ring l dn ca khi dung dch nm gia hai
in cc song song c thit din 1 cm2 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 m2 v t cch nhau 1 m.

[] = ohm1.cm1 = S.cm1 (hay [] = S.m1)

1 S = 1 ohm1

Phng php xc nh dn in ring

1 l K
.
R A R

b
in cc

K: hng s bnh hay hng s in cc

a
l

RM

RX

R1

R2
D

Cu Wheatstone

I CD 0 R X RM .

R2
R1

o in tr
dng dng xoay chiu
c tn s cao
n nh nhit

V d
- in cc o dn c thit din 6,00 cm2 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

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.
M

1000.
C

: s cm 1

C : mol / L
: s cm 2 mol 1
M

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.

1000

N : d lg/ L

2
1

:
s
cm
d
lg

11

1.3. dn in mol, ng lng

Dung dch in ly mnh l tng: khng ph

thuc nng
Dung dch tht: ph thuc vo nng do:
Tng tc ion ion 1
Dung dch in ly yu: ph thuc vo nng do:
- Phn ly khng hon ton ca dd in ly.

12

1.4. Linh ion, linh mol, ng lng

nng
dn in

vn tc chuyn ng
in tch

13

Ion chuyn ng khi c in trng in di

l
+

X
E
X
l

E
E
E
+
I

. A.
1 l
R
l
.
A
E
Ft Z i eo
Lc in trng, Ft: lc coulomb
l
Lc ma st, Fms :
Fms = 6rivi
E
F
=
F
Ion c/ u:
Zi eo
6 rv
ms
t
i i
l
14

Vn tc chuyn ng c hng (vi) ca ion di tc dng ca lc in

trng X :

vi

Z i eo E
.
ui . X
6 ri l

ui: Linh ion (vn tc tuyt i ca ion)

X= 1 V/cm

Z i eo
v ui
6 ri
o
i

[vi] = cm/s;

[u] = cm2.V1.s1

Linh (cm2.V1.s1) ca mt s ion trong nc 25oC.

Ion

H+

Na+

K+

Zn2+

OH

Cl

Br

SO42

u.104

36,2

5,19

7,62

5,47

20,6

7,91

8,09

8,29
15

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

ui

Z i eo
6 ri

M = ui.z.F N = ui F

2
o

Zi e N A

6 ri

I = I+ + I

I+ = eoZ+n+v+A

v+
+

I = eoZnvA
I = I+ + I = eoZ+n+v+A + eoZnvA
E
vi ui .
l

E
E
I eo .Z n A.u
eo Z n A.u
l
l

eoZ+n+= eoZn
n Z eo N A n Z eo N A N .F

NA
NA
1000
Nu cht in ly phn ly
hon ton ( = 1) :
16

Nu cht in ly phn ly mt phn ( < 1) :

n Z eo n Z eo

.N .F
1000

N
N
E
I ( u F .
u F .
). A.
1000
1000
l

Thay ui.F bng i :

N
E
I ( )
. A.
1000
l
E
Mt khc: I . A.
l

1000
N

( ) N
1000

. N
1000

( ) N
1000

= (+ + )
17

 = (+ + )
Dd v cng long = 1 v k hiu dn in v cng long l o

o = 0+ + 0

0 () : 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)
0i : dn in ng lng gii hn ca ion (linh ng lng ti hn)

1000
C . o
N

Linh ng lng ( dn in gii hn) ca mt s ion (S.cm2lg-1)

Ion

io

Na+

K+

Zn2+

Cl

Br

SO42

349,8 50,1

73,5

53,5 197,6 76,3

78,3

80,0

H+

OH

18

ng dng ca nh lut chuyn ng c lp ca ion

Xc nh dn in mol ti hn ca cht in ly yu.
HA A- + H+

2C
K
1
C = .o

( C )
2
o K o

V d: dn in mol ca dung dch acid HA

(0,004 M) l 359 S cm2 mol-1 . dn in mol ti
hn ca HA l 385 S cm2 mol-1. Tnh in ly v
hng s phn ly Ka.
19

Ch
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.

20

1.5. S ti ca ion
phn ng gp ca tng ion vo dn in

Vi khc nhau
S ti (ti) :

t l ng gp ca loi ion i vo dn in chung

I i qi
ti
I
Q

ti = 1

i N i
ti
i N i

E
1
E
I i eo zi ni A.ui

Ni i A.
l
1000
l
Nu dung dch ch c hai loi ion:

t+ + t = 1

21

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

. mS

Chun dn

io : 25oC, nc
Ion

io

H+

Na+

349,8 50,1

K+

Ag+ NH4+ Cl NO3 AcO OH

73,5 61,9

73,5 76,3 71,5

40.9

197,6
23

Phn tch
phn ng
gp ca cc
loi ion vo

, mS

AgNO3 + KCl AgCl + KNO3

Cl
K+

trong qu

trnh chun

NO3
Ag+

Vt

V, ml

Ag+ + NO3 + K+ + Cl AgCl + K+ + NO3

24

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

T tham kho ti liu !

25

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

V d: in

phn dung dch CuSO4 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.
26

Phng php ranh gii chuyn ng

q l in lng, h l khong cch m
mng AB dch chuyn, S l thit din
ngang ca ng th:

q V .N S.h.N
t

q
q
q

MX

t=0

MX

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
27
linh ng lng ca K+ .

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

3.1. dn in vi bn cht ca cht in ly

dn in ng lng 25oC trong nc ([o] = S.cm2lg1)
H2SO4
HCl
HNO3

429,8
426,2
412,2

KOH
271,1
NH4OH 271,0
NaOH 247,0

KCl
KNO3
NaCl

149,9
145,0
126,4

Acid > Baz > Mui

29

Linh ng lng ion trong nc v bn knh ca cc ion 25oC

([io] = S.cm2lg1)
Ion
r ()

H+
0,00
350

Li+
0,68
38,7

Na+
0,98
50,1

Ag+
1,13
61,9

K+
1,33
73,5

Ion
r ()

Ni+
0,74
54,0

Fe2+
0,80
53,5

Cu2+
0,80
54,0

Zn2+
0,83
53,5

Cd2+ Pb2+
0,99 1,26
54,0 70,0

Ba2+
1,38
63,7

Fe3+
0,67
68,0

Ion
r ()

F
1,23
55,4

Cl
1,81
76,3

Br
1,96
78,3

I
2,20
76,8

NO3 OH
71,4 198

H2PO4

HPO42 SO42
57,0
80.0

io
io
io

Cs+
1,65
76,8

NH4+
73,0

Al3+
0,57
63,0

36,0
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

30
cc ion khc t 3 - 8 ln.

Linh bt thng ca H+ v OH

31

IV.3.4. nh hng ca nhit

t t [1 (t to ) (t to ) ]
2

H s nhit ca dn in ca mt s ion
H+
(Scm2lg1) 349,8

0,0142

NH4+

Na+

OH

Cl

IO4

73,5

50,1

198,3

76,35

54,5

0,0187

0,0208

0,0196

0,0194

0,0144

32

S ti nhit
ti > 0,5

ti = 0,5
ti < 0,5
Nng tng

T, oC
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

33

IV.3.2. dn in vi bn cht dung mi

nh lut Walden-Pisajevski:

o const
vo . const
2
Z
e
Z
e
oi vio F i o N A .eo oi . i o N A const
6 ri
6ri

Z i eo
v io
6 ri

34

IV.3.3. nh hng ca nng n dn in

dn in ring

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

dn in ng lng
lun gim khi nng tng

C = .o

35

nh lut thc nghim Kohlrausch

C

C o A C

A - hng s thc nghim h s Kohlrausch.

V SAO ?

36

IV.3.5. dn in cht in ly mnh vo nng

Thuyt Debye-Onsager gii p
V sao dn in ca cht in ly mnh gim khi nng tng ?

Hiu ng in di
Hiu ng bt i xng

Gii thch phng trnh kinh nghim ca Kohlrausch

37

Thuyt Debye-Onsager

d Z

in di

bd C
1/ 2

eo2 N A 2 N A .10 3

bd
6 o kT

bdx oibb C

Bt i xng

bbdx

= o (bd + bbxo)

1/ 2

( Z .Z ) 2 2 eo3 2 N A10 3

24 o kT
o kT

C
38

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

39