1

Chng 2. S n in ca dung dch cht in li

Trnh Xun Sn
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
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 106 103 .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 cm2 v cch nhau 1 cm.
dn in ring l i lng nghch o ca in tr sut.
=

(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 (cm2), in tr sut ca dy kim loi l .
Vy in tr R ca dy dn c tnh:
R = .
Suy ra:

(2.2)

1 A

R S

(1.cm1)

(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 18oC)]

(2.4)

trong : t dn in ring nhit t bt k, toC > 18oC;

18 dn in ring nhit 18oC.
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.

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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.

(2.5)

trong C l nng ng lng gam/lit.

T suy ra n v o ca bng 1.cm2.lg1.
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).
C = .

Vy:
Suy ra:

(2.7)

(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

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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,
KNO3...). MA phn li thnh cc ion M+ v A.
Gi Uo - tc chuyn ng tuyt i ca cation M+
v Vo - 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 = Uo.E (cm/giy)

(2.9)

Tc chuyn ng ca anion:
V = Vo.E (cm/giy)

(2.10)

cm

Khi E = 1 (V/cm) th U = Uo v V = Vo
= cm 2 / 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 cm2 bng:

trong : C/ =

+ = C/ + NA.Uo.E

(2.11)

= C/ NA.Vo.E

(2.12)

C
1000

gi l nng ion trong mt n v th tch 1 cm3.

Uo v Vo 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 + NA.Uo.E.103

(2.13)

(2.14)

= C NA.Vo.E.10
trong :

- phn li;

+, - s cation v anion;

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NA

- 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 = 1,602.1019C.
i vi cht in li 1-1, Z1 = Z = 1
hoc

Q = C NA e.103.E (+ Z+ Uo + Z Vo)

(2.16)

Dung dch cht in li lun trung ho in nn + Z+ = Z = Z

Vy phng trnh (2.16) c dng:
Q = i = 103 C F Z (Uo + Vo)E

(2.17)

y lng in Q do ion ti trong mt n v thi gian i qua 1 cm2 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:

= 103 C F Z (Uo + Vo)

(2.19)

Mt khc, ta c:
=

1000.
Cd lg/ l

= F (Uo + Vo)

(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 Uo c gi l linh cation:
U = F . Uo
v linh anion:

(2.21)
V = F . Vo

(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)

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+ v 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

( 1.cm2.lg1)

HCl

CH3COONa

NaCl

426,00

91,00

126,50

Theo cng thc (2.24) ta c th vit:

(CH3COOH) = (H+) + (CH3COO)
= (HCl) + (CH3COONa) (NaCl)
= 426,00 + 91,00 126,50 = 390,6
Gi tr linh ti hn ca ion H3+ 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.

H
O

H
O

H
+
O + H

H
O

Bng 2.1 Gi tr linh ti hn ca mt s cation v anion

Cation
Gi tr linh
V (25oC)
Anion
Gi tr linh
V (25oC)

H3+ O

Na+

K+

NH4+

Ca2+

349,8

50,1

73,5

73,5

59,5

OH

ClO4

HCO3

SO24

197,6

55,4

67,3

64,6

80

2+

Zn

52,8

i vi ion OH
H
O

H
O

H
O

H
O

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).

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Bng 2.2 Gi tr linh ti hn ca ion ph thuc vo mt s iu kin

Gi tr linh

U (H+)

Nng
25 C

H+

Dung mi 25oC

Nhit

H2 O

C2H5OH

0oC

50oC

0,01N

0,1N

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 U A + B+
Vy tng s ion trong mt n v th tch 1 cm3 bng:
+ + =

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

.C
1000

( + + )

= ( + + )

(2.26)
(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.

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 102 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
Gi tr f

1-1

1-2

1-3

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 cm3 dung dch v
tc tuyt i ca chng. Khi tng nng th s ion trong 1 cm3 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:
=
trong :

g
a

I.t
96493

(2.34)

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- 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=

I.t

Z 96493

A I.t
Z

(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+ =

Uo
U o + Vo

+
+ +

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 =

Uo

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

t+ + t = 1

Vy

(2.37)

(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

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i Uo/Vo = 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 Uo v anion Vo l

Uo
Vo

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 na v nc l gin nng ng lng ca cht in li ti khu anot v khu catot
sau in phn, ta c:
n a
n c

Uo
Vo

0,01.2

0,01.3

2
3

(2.39)

Mt khc:
n = na + nc

(2.40)

T (2.39) v (2.40) ta c:
t+ =
v

t =

Uo
U o + Vo
Uo
U o + Vo

=
=

n a
n
n c
n

(2.41)

T (2.41) rt ra:
S ti cation t+ bng t s gim nng ti anot (na) 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 (nc) 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 (nc) v
s ti anion t bng t s gim nng ti khu anot (na) 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 H2SO4.
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.

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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 R1 v R2 c chn trc c

R1
R2

= 1. iu chnh RM 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:
I1 RM = I2 R1
I1 Rx = I2 R2

RM

Vy

Rx

R1
R2

= 1 RM = Rx

Rx - l in tr ca bnh o in ho gm hai in cc platin ph kim loi platin c din

tch hnh hc 1cm2 v cch nhau 1 cm, trong cha dung dch cht in li cn xc nh in
tr.
Cc in tr R1 v R2 c chn trc.
in tr mu RM (bin i).
Rx - in tr bnh o dn.
Theo cng thc (2.3) dn in ring ca dung dch in li c tnh:
=
K=

1
Rx

K
Rx

[cm1] gi l hng s bnh.

Rx c xc nh bng thc nghim, bit hng s K l tnh c .

(2.43)

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xc nh hng s K phi s dng dung dch chun KCl 0,02N c gi tr bit, =
0,002765 1.cm1 25oC. Bng thc nghim o in tr RKCl ca dung dch 0,02N KCl v
suy ra hng s K:
K = 0,002765.RKCl
Theo phng trnh (2.43), bit hng s K c th o c in tr Rx 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/A 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 = H2O + NaCl
+

H + OH = HOH

(2.45)
(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].

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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 .