1

n mn v bo v kim loi. NXB i hc quc gia H Ni 2006.

T kho: n mn v bo v kim loi, dn in, Linh ion, S vn ti, Dung dch cht
in ly, o dn in.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc
ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc

Chng 2 S n in ca dung dch cht in li ..................................................2
2.1 M u ..........................................................................................................2
2.2 dn in ring v dn in ng lng ..............................................2
2.2.1 dn in ring.......................................................................................2
2.2.2 dn in ng lng...........................................................................3
2.3 Quan h gia dn in ring v tc chuyn ng ca ion......................4
2.4 Linh ion ....................................................................................................5
2.5 S ph thuc ca dn in vo nng dung dch cht in li ..................7
2.6 S vn ti.....................................................................................................10
2.7 Phng php o dn din v ng dng....................................................13
2.7.1 Phng php o dn in ....................................................................13
2.7.2 ng dng ca phng php o dn in..............................................14



Chng 2. S n in ca dung dch cht in li
Trnh Xun Sn
2
Chng 2
S n in ca dung dch cht in li
2.1 M u
Dung dch cht in li cn gi l cht dn in loi hai, s dn in ca n nh s ti
in ca cc ion. Kim loi v oxit kim loi dn in bng electron c gi l cht dn in
loi 1 v c in tr khong 10
6
10
3
.cm.
Nghin cu v dn in ca dung dch cht in li c lin quan cht ch vi hin
tng n mn in ho v cho php gii thch s khc bit v tc n mn trong mi trng
nc bin v nc sng, ao, h.

nh gi kh nng dn in ca dung dch cht in li ngi ta s dng hai i lng:
dn in ring v dn in ng lng ca dung dch cht in li.
2.2 dn in ring v dn in ng lng
2.2.1 dn in ring
dn in ring ca dung dch cht in li cho l dn in ca n c t gia
hai in cc song song c din tch 1 cm
2
v cch nhau 1 cm.
dn in ring l i lng nghch o ca in tr sut.
=

1
(2.1)
tm n v o ta xt in tr ca mt ng dung dch cht in li tng t mt dy
dn kim loi c chiu di l (cm) v tit din S (cm
2
), in tr sut ca dy kim loi l .
Vy in tr R ca dy dn c tnh:
R = .

S
(2.2)
Suy ra: =

1
=
1
R
.

S
(
1
.cm
1
) (2.3)
Khc vi cht dn in kim loi, dn in ring ca cht dn in loi 2 tng khi tng
nhit .

t
=
18
[1 + k(t 18
o
C)] (2.4)
trong :
t
dn in ring nhit t bt k, t
o
C > 18
o
C;

18
dn in ring nhit 18
o
C.
Gi tr h s k thay i tu thuc vo bn cht dung dch, i vi dung dch axit mnh k
= 0,0164, i vi dung dch baz mnh k = 0,0190, i vi dung dch mui k = 0,022.
3
2.2.2 dn in ng lng
dn in ng lng ca dung dch cht in li kho st l dn in ca mt
dung dch cha ng mt ng lng gam cht in li c t gia hai in cc platin
song song vi nhau v cch nhau 1 cm.
Gia dn in ng lng v dn in ring c quan h vi nhau theo phng
trnh:
=
1000.
C
(2.5)
trong C l nng ng lng gam/lit.
T suy ra n v o ca bng
1
.cm
2
.lg
1
.
Nu t V =
1
C
gi l pha long th cng thc (2.5) c dng:
= 1000.V. (2.6)
T phng trnh (2.5) cho thy khi dung dch rt long (C 0) th gi tr t n gi
tr ti hn

.
i vi dung dch cht in li yu, s ph thuc ca dn in ng lng vo
nng cht in li thc cht l ph thuc vo s bin i in li (hnh 2.1).
Vy:
C
= .

(2.7)
Suy ra: =

C
(2.8)
trong :
C
dn in ng lng ca dung dch c nng C.

Hnh 2.1
S ph thuc ca dn in ng lng vo pha long V

4
2.3 Quan h gia dn in ring v tc chuyn ng ca ion
Trong trng hp n gin ta hy xt mt ng dung dch cht in li 1-1 (v d KCl,
KNO
3
...). MA phn li thnh cc ion M
+
v A

.


Gi U
o
- tc chuyn ng tuyt i ca cation M
+

v V
o
- tc chuyn ng tuyt i ca anion A

.


Nu t ng dung dch vo in trng E (V/cm) th:
Tc chuyn ng ca cation:
U = U
o
.E (cm/giy) (2.9)
Tc chuyn ng ca anion:
V = V
o
.E (cm/giy) (2.10)
Khi E = 1 (V/cm) th U = U
o
v V = V
o


=


2
cm
cm / V.s
s.(v / cm)

Di tc dng ca in trng, trong mt n v thi gian 1 giy s cation
+
v anion

i qua tit din S = 1 cm
2
bng:

+
= C
/

+
N
A
.U
o
.E (2.11)


= C
/


N
A
.V
o
.E (2.12)
trong : C
/
=
C
1000
gi l nng ion trong mt n v th tch 1 cm
3
.
U
o
v V
o
l tc tuyt i ca cation v anion v chnh l di do cation di chuyn
trong 1 n v thi gian 1 giy vi E = 1 (V/cm).


Hnh 2.2
S di chuyn ca cc ion di tc dng ca in trng
Phng trnh (2.11) v (2.12) c th vit:

+
= C
+
N
A
.U
o
.E.10
3
(2.13)


= C

N
A
.V
o
.E.10
3
(2.14)
trong : - phn li;

+
,

- s cation v anion;
5
N
A
- l s Avogaro.
Nu gi Q l in lng do cation v anion ti th:
Q =
+
Z
+
. e +

Z

. e (2.15)
trong : Z
+
, Z

l s oxi ho ca cation v anion;
e l in tch c bn, e = 1,602.10
19
C.
i vi cht in li

1-1, Z
1
= Z

= 1
hoc Q = C N
A
e.10
3
.E (
+
Z
+
U
o
+

Z

V
o
) (2.16)
Dung dch cht in li lun trung ho in nn
+
Z
+
=

Z

= Z
Vy phng trnh (2.16) c dng:
Q = i = 10
3
C F Z (U
o
+ V
o
)E (2.17)
y lng in Q do ion ti trong mt n v thi gian i qua 1 cm
2
chnh l cng
dng in i i qua ng dung dch (hnh 2.2).
Tng t i vi dy dn kim loi c in tr R c dng in i i qua dy dn v in th
E, i vi ng dung dch cht in li (hnh 2.2), theo nh lut m ta c:
i = .E (2.18)
So snh (2.17) v (2.18) rt ra:
= 10
3
C F Z (U
o
+ V
o
) (2.19)
Mt khc, ta c:
=

dlg/ l
1000.
C
= F (U
o
+ V
o
) (2.20)
Cc phng trnh (2.19) v (2.20) th hin mi quan h gia dn in ring v dn
in ng lng vi tc chuyn ng tuyt i ca cation v anion.
2.4 Linh ion
Tch s ca hng s Faraday v tc tuyt i ca cation U
o
c gi l linh cation:
U = F . U
o
(2.21)
v linh anion: V = F . V
o
(2.22)
Kt hp (2.22) v (2.20) ta c:
= (U + V) (2.23)
i vi dung dch long C 0, 1 khi dn in ng lng c gi l
dn in ng lng nng v cng long

v phng trnh (2.23) c dng:

= U

+ V

(2.23a)
trong U

v V

l linh cation v anion nng v cng long (cn gi l linh
ti hn) hoc:

=
+

(2.24)
6
+

l dn in ng lng ca cation v anion nng v cng long (C

0).
Da vo cng thc (2.24) khi bit dn in ng lng ca ion ti nng v cng
long tnh c dn in ng lng phn t nng v cng long.
V d: Tnh

ca axit axetic cho bit:

Cht in li HCl CH
3
COONa NaCl

(
1
.cm
2
.lg
1
)
426,00 91,00 126,50
Theo cng thc (2.24) ta c th vit:

(CH
3
COOH) =

(H
+
) +

(CH
3
COO
)

=

(HCl) +

(CH
3
COONa)

(NaCl)
= 426,00 + 91,00 126,50 = 390,6
Gi tr linh ti hn ca ion
+
3
H O v OH

rt ln so vi cc cation v anion khc. Trong
mi trng nc cc ion ny chuyn ng theo c ch c bit - c ch truyn cho proton
gia chng v phn t HOH bn cnh.



Bng 2.1 Gi tr linh ti hn ca mt s cation v anion
Cation
+
3
H O Na
+
K
+

+
4
NH Ca
2+
Zn
2+
Gi tr linh
V

(25
o
C)
349,8 50,1 73,5 73,5 59,5 52,8
Anion OH

F

4
ClO

3
HCO
2
4
SO
Gi tr linh
V

(25
o
C)
197,6 55,4 67,3 64,6 80
i vi ion OH






Mt khc trong cng
mt
iu kin gi tr linh ti hn ca ion ph thuc vo nng ,
nhit v dung mi (xem bng 2.2).
H O H
H
+
+ O H
H
O
H
H +
+
H O H
H
+ O
H
H O H
H
+
O
H
O
H
7
Bng 2.2 Gi tr linh ti hn ca ion ph thuc vo mt s iu kin
Dung mi 25
o
C Nhit
Nng H
+

25
o
C
H
2
O C
2
H
5
OH 0
o
C 50
o
C 0,01N 0,1N
Gi tr linh
U

(H
+
)
349,8 62 240 465 338,9 325,5
Trong dung mi nc
2.5 S ph thuc ca dn in vo nng dung dch cht in li
dn in ca
dung
dch cht in li ph thuc vo ton b ion c mt trong dung dch,
ngha l ph thuc vo nng dung dch v in li .
i vi cht in li
yu
1-1 vi nng C v in li :
AB A

+ B
+

Vy tng s ion trong mt n v th tch 1 cm
3
bng:

+
+

=

A
2. .C.N
1000
= const .C (2.25)
Tng s ion trong mt n v th tch t l vi tch s .C.
i vi dung dch cht in li yu, trong dung dch m c in li rt nh. V vy,
nng ion t l vi tch s ca .C v trong dung dch khng c khi nim kh quyn ion. Khi
dung dch rt long, khong cch gia cc ion rt ln cho nn cc ion chuyn ng mt cch
c lp, dn in ng lng ca cc ion t gi tr ti hn
+

.
dn in ring v dn in ng lng ca dung dch cht in li yu c tnh
theo cc phng trnh sau:
=
.C
1000
(
+

) (2.26)
v = (
+

) (2.27)
Kt hp vi (2.24) ta c:
=

(2.28)
Vy dn in ring ca cht in li yu ph thuc vo nng (xem hnh 2.3) song
s bin i ca n rt nh khi tng nng cht in li.
8

Hnh 2.3
S ph thuc ca dn in ring vo nng C
i vi cht in li mnh c lin kt ion, v d hp cht mui, mng tinh th ca n cu
to t cc ion v khi ho tan trong nc hoc trong cc dung mi c hng s in mi ln th
xung quanh ion lun hnh thnh cc lp v hirat (hoc xonvat) ngn cn s ti kt hp to
thnh cc phn t. Trong nhng mi trng cht in li b phn li hon ton hoc gn hon
ton ngay c khi nng cao v nng ion bng nng dung dch. Vy dn in ng
lng ca hp cht bng tng s dn in ng lng ca cc ion:
=
+
+

(2.29)
Vy dn in ng lng ca cc cht in li mnh trong dung dch nc ph thuc
vo nng c xc nh ch yu bng cc lc tng tc gia cc ion, ngha l vo khong
cch gia cc ion v bn cht ca mi trng.
S c mt ca nhng tng tc ny gy ra s km hm nht nh i vi s chuyn ng
ca cation v anion, ngha l lm gim linh ca chng khi tng nng .
Gi

l dn in ng lng ti hn ca dung dch cht in li mnh trong dung
dch rt long khng tnh n tng tc gia cc phn t trong dung dch. Ti nng xc
nh, dn in ng lng (2.29) lun lun nh hn

v bng:
=


I

II
(2.30)
trong :

I
l hiu ng km hm in di do s tng tc tnh in ca lp v ion ngc du vi
ion trung tm b dch chuyn di tc dng ca in trng ngoi. Theo Onsage hiu ng km
hm
I
t l vi cn bc hai nng C .

II
l hiu ng km hm phc hi cn li gi l hiu ng bt i xng. S tn ti ca
hiu ng ny l do s tng tc ca mt phn lp v kh quyn ion c in tch tri du cha
b ph v hon ton vi ion trung tm b dch chuyn di tc dng ca in trng ngoi.
Hiu ng
II
cng t l vi C v nht.
Phng trnh (2.30) c th vit:
=

a C (2.31)
Phng trnh (2.31) ch p dng cho dung dch cht in li mnh c nng khng vt
qu 10
2
lg/l.
9
H s a ph thuc vo bn cht dung mi, ngha l vo hng s in mi cng nh
nht ca n, vo nhit . C th xc nh n bng thc nghim hoc tnh trn c s l thuyt
dung dch.
Cng cn phi nhn mnh rng, i vi dung dch cht in li mnh rt long C 0 th

v trong dung dch khng cn tn ti kh quyn ion v c th vit:

=
+

(2.32)
Phng trnh (2.32) tng t phng trnh (2.24) p dng cho dung dch cht in li yu
v cng c gi l nh lut chuyn ng c lp ca ion.
T s gia dn in ng lng ca cht in li mnh ti nng cho trc so
vi dn in ng lng ti hn

gi l h s dn f

. i lng ny c trng cho

s tng tc gia cc ion.
f

=
+
+

+
+
(2.33)
H s dn ph thuc vo ho tr ca cc ion (xem bng 2.3).
Bng 2.3 Gi tr h s dn f

ph thuc vo ho tr ion
Loi dung dch cht in li vi nng 0,1N 1-1 1-2 1-3
Gi tr f

0,8 0,75 0,4
Khi dung dch rt long, lc tng tc tnh in rt nh, tc dng km hm rt nh v c
th b qua s khc bit ca f

ph thuc vo ho tr ion.
dn in ring ca cht in li mnh ph thuc vo s ion trong 1 cm
3
dung dch v
tc tuyt i ca chng. Khi tng nng th s ion trong 1 cm
3
dung dch tng ln song
tc tuyt i gim. S tng quan gia cc yu t dn n s xut hin dn in
ring cc i (xem hnh 2.3).
Vic so snh nh hng ca nng n dn in ng lng ca cc cht in li
mnh v yu c th hin trn cc ng cong biu din s ph thuc ca vo nng C
(hnh 2.4) v vo C (hnh 2.5).



10

Hnh 2.4
S ph thuc ca dn ng lng vo nng C
Hnh 2.5
S ph thuc ca dn in in ng lng vo C lg/l
Cht in li mnh c dn in ng lng rt ln ngay c i vi dung dch m dc.
Khi tng pha long dn in ng lng tng.
Trong min dung dch long s ph thuc ca vo C i vi cht in li mnh c
quan h tuyn tnh v tun theo phng trnh (2.31) (xem hnh 2.5).
i vi dung dch cht in li yu, ngay c khi nng rt long gi tr dn in
ng lng cng rt nh v ch khi nng rt nh C 0 th n tng t ngt t n gi
tr ti hn

. Trn hnh 2.5 cng cho thy s ph thuc v C i vi cht in li yu l

tuyn tnh ti vng nng rt nh.
Da vo ng cong trn hnh (2.5) cho php ngoi suy v tnh c

i vi cht in
li mnh (i vi dung dch KCl, LiCl).
2.6 S vn ti
Khi dng in mt chiu i qua dung dch cht in li, trn catot xy ra phn ng phng
in ca cc cation v trn anot cc anion nhng in t hoc c s ho tan kim loi. Hin
tng gi l s in phn.
Theo nh lut Faraday, lng cht c thot ra hoc b mt i trn cc in cc trong
qu trnh in phn t l vi lng in i qua bnh in phn cng nh t l vi ng lng
ho hc ca cc cht.
c c mt ng lng gam cht thot ra hoc mt i trn cc in cc cn phi c
mt Faraday (96493 C) - 1 F in lng i qua bnh in phn.
Biu thc nh lng ca nh lut Faraday:
=
g
a
=
I.t
96493
(2.34)
trong :
11
- S ng lng cht bin i trn in cc,
g - Lng cht thot ra hoc mt i trn in cc (gam),
a - ng lng cht tnh theo gam v a = A/Z, trong A l khi lng phn
t (hoc nguyn t tnh theo gam), Z l s electron tham gia phn ng (hoc s oxi
ho - ho tr ca ion);
I - Cng dng in (Ampe) i qua bnh in phn;
t - Thi gian (giy) in phn.
Vy t (2.34) ta c:
g =
A
Z
.
I.t
96493
=
A
Z
.
I.t
F
(2.35)
Khi in phn, cc ion chuyn in tch, lng in i qua cc in cc lun lun bng
nhau, nhng mi loi ion chuyn in khng ging nhau v tc chuyn ng ca chng
khc nhau.
Phn in do cation hoc anion ti i trong qu trnh in phn gi l s ti t.
S ti cation l:
t
+
=
+
o
o o
U
U V
=
+
+

+
=
+
U
U V
(2.36)
t
+
l s vn ti cation bng t s tc tuyt i ca cation so vi tng tc tuyt i
ca hai loi ion (hoc biu din qua linh ion).
Tng t t

l s ti anion chnh bng t s tc tuyt i ca anion so vi tng tc
tuyt i ca c hai loi ion (hoc biu din qua linh ion).
t

=
o o
o
V U
U
+
=
V U
U
+
=
+

+

(2.37)
Vy t
+
+ t

= 1

(2.38)
Da vo s bin i nng ti cc khu vc catot v anot c th xc nh c s ti.
Xt qu trnh in phn vi cc in cc tr (platin). Gi thit chia bnh in phn thnh
ba khu vc - khu catot, khu gia v khu anot (xem hnh 2.6).

Hnh 2.6
S cc khu vc ca bnh in phn ng vi s bin i nng khi t s tc chuyn ng tuyt
12
i U
o
/V
o
= 2/3
1. Trng thi trc in phn;
2. Trng thi sau in phn
Trc khi in phn nng hai khu catot v anot bng nhau (mi du +, th hin phn
ng lng gam, v d 0,01 lg).
Gi thit tc tuyt i cation U
o
v anion V
o
l
o
o
U
V
=
2
3
, ngha l khi xy ra in phn
c 0,01 2 ng lng gam cation c chuyn n catot, ngc li c 0,01 3 ng
lng gam anion c chuyn n anot (xem hnh 2.4, trng thi 2). Nhng ion khng cp i
tham gia phng in v tng s ng lng cation v anion phng in trn catot v anot
u bng:
0,03 + 0,02 = 0,05 lg = n
Gi n
a
v n
c
l gin nng ng lng ca cht in li ti khu anot v khu catot
sau in phn, ta c:

a
c
n
n
=
o
o
U
V
=
0,01.2
0,01.3
=
2
3
(2.39)
Mt khc:
n = n
a
+ n
c
(2.40)
T (2.39) v (2.40) ta c:
t
+
=
+
o
o o
U
U V
=

a
n
n

v t

=
+
o
o o
U
U V
=

c
n
n
(2.41)
T (2.41)
rt
ra:
S ti cation t
+
bng t s gim nng ti anot (n
a
) so vi gim lng cht ca
ton b (n) qu trnh in phn, mt cch tng t s ti anion t

chnh bng t s gim
nng ti khu catot (n
c
) so vi gim lng cht ca ton b qu trnh in phn (n).
Trong mt s trng hp s ti cation t
+
bng t s gim nng ti khu catot (n
c
) v
s ti anion t

bng t s gim nng ti khu anot (n
a
) so vi gim lng cht ca
ton b qu trnh in phn (n). V d tnh s ti t
+
v t

i vi qu trnh in phn dung
dch NaOH v H
2
SO
4
.
S hiu bit v s ti c ngha nht nh i vi l thuyt dung dch cht in li, cho
php tnh c gi tr dn in ca ion theo cng thc:

+

.t
+
(2.42)

- dn in ng lng ca phn t nng v cng long.

13
2.7 Phng php o dn din v ng dng
2.7.1 Phng php o dn in
S dng cu o bng dng xoay chiu xc nh dn in ca dung dch cht in li
(xem hnh 2.7).

Hnh 2.7
S mch o dn in ca dung dch cht in li
Cc in tr R
1
v R
2
c chn trc c
1
2
R
R
= 1. iu chnh R
M
sao cho khng c
dng in i qua CD. Khi ng h G ch s khng (hoc dng ng nghe c gi tr nh
nht). Khi cu cn bng ta c:
I
1
R
M
= I
2
R
1

v I
1
R
x
= I
2
R
2

Vy
M
x
R
R
=
1
2
R
R
= 1 R
M
= R
x

R
x
- l in tr ca bnh o in ho gm hai in cc platin ph kim loi platin c din
tch hnh hc 1cm
2
v cch nhau 1 cm, trong cha dung dch cht in li cn xc nh in
tr.
Cc in tr R
1
v R
2
c chn trc.
in tr mu R
M
(bin i).
R
x
- in tr bnh o dn.
Theo cng thc (2.3) dn in ring ca dung dch in li c tnh:
=
x
1
R
=

S
=
x
K
R
(2.43)
K =

S
[cm
1
] gi l hng s bnh.
R
x
c xc nh bng thc nghim, bit hng s K l tnh c .
14
xc nh hng s K phi s dng dung dch chun KCl 0,02N c gi tr bit, =
0,002765
1
.cm
1
25
o
C. Bng thc nghim o in tr R
KCl
ca dung dch 0,02N KCl v
suy ra hng s K:


K = 0,002765.R
KCl

Theo phng trnh (2.43), bit hng s K c th o c in tr R
x
ca dung dch cht
in li bt k v suy ra dn in ring .
2.7.2 ng dng ca phng php o dn in
Phng php o dn in c rt nhiu ng dng trong nghin cu v thc t, di y
xin nu hai trng hp.
a) Xc nh tan mui t tan
i vi dung dch mui t tan, tan S (tnh theo s ng lng gam c trong mt lt
dung dch) chnh bng nng C (lg/ hoc mol/l) ca mui t tan trong dung dch. tan
rt nh v xem dung dch l v cng long khi dn in ng lng ca dung dch
c tnh bng:


=
1000.
S
S =

1000.
(2.44)
o gi tr ,

- dn in ng lng nng v cng long cho trc (

= U

+
V

), t suy ra S.
b) Chun bng phng php o dn in (chun dn in k)
Nguyn tc ca vic chun dn in l l o dn in ring theo di s thay th ion
c linh ion ln (H
+
) bng ion c linh b hn (OH

) hoc ngc li. T xc nh im

tng ng cho qu trnh chun .
V d: Chun dung dch axit mnh HCl bng baz mnh NaOH (xem hnh 2.8).
Phn ng xy ra trong qu trnh chun :
HCl + NaOH = H
2
O + NaCl (2.45)
H
+
+ OH

= HOH (2.46)
Ti im A - ng vi nng ban u ca ion H
+
c gi tr ln nht. Theo s tng dn
s ml dung dch NaOH cho vo dung dch axit ban u xy ra phn ng (2.45), (2.46), nng
ion H
+
gim do dn in gim, c gi tr cc tiu khi [H
+
] = [OH

].
15

Hnh 2.8
ng cong chun dn in k
AOB - chun axit HCl bng dung dch NaOH;
AOB - chun axit yu bng baz mnh; V - im tng ng
Cho d [OH

] th dn in tng theo ng OB. im O c xc nh bng cch
ngoi suy 2 on thng AO v BO, v gi l im tng ng ca php chun . ng
thng OB lun lun c dc nh hn OA l v linh ion H
+
ln hn linh OH

.
ng AOB biu din s bin i ca dn in ring ph thuc vo s ml dung
dch NaOH trong qu trnh chun axit yu bng baz mnh.
Axit yu phn li thnh H
+
vi rt nh, vy nng H
+
rt nh v dn in rt
nh (im A). Khi thm dung dch NaOH vo dung dch axit yu, dung dch axit yu b
long ra v th nng [H
+
] v nng [Na
+
] tng ln v dn n s tng dn gi tr dn
in theo on thng AO.
Tng dn nng OH

, khi OH

d v dn in ca dung dch tng theo OB.
dc on thng OB ln hn OA v linh OH

ln. im ngoi suy O ct nhau ca 2
on thng AO v OB chnh l im tng ng ca qu trnh chun .