CHNG III

TNG TC ION ION

TRONG DUNG DCH IN LY

CHNG III
III.1. Cn bng nhit ng trong dung dch
in ly. Hot v h s hot
III.2. Thuyt tnh in Debye Hckel

1. Cn bng nhit ng trong dung dch

in ly. Hot v h s hot
Tng tc ion-dipol : gii thch s to thnh v tnh bn vng
ca dung dch in ly.
Tuy nhin cha m t nh lng tnh cht ca dung
dch in ly.

Sai st nh lng , Kpl

V SAO ?

Ch c th p dng cn bng phn ly vo

dung dch long ca cht in ly yu.
Tng tc ion-ion

Khi nim HOT

M t hnh thc

Ton b tng tc
trong dung dch in ly

m t mt cch
hnh thc

S dng hot
thay cho nng .

Biu thc nhit ng vit cho dung dch l

tng nhng thay nng bng hot
th s ph hp vi kt qu thc nghim.

[ H ][ A ]
K
[ HA ]

a H a A
a HA

Hot v h s hot
aC = C.C
am = m.m
aX = X.X
Cch biu
din nng

n v

mol
molan

mol/l

phn mol

mol/kg dung
mi

C, m, X,
(hay fC, fm, fX)

Nng
C, M
m
X, N

h s hot
(mol, molan v
phn mol)

K hiu
Hot H s hot
aC
f,
am
m
aX, aN

X, N
5

Ha th
Ha th ca ht i, i - cng a mt mol ht i t chn khng vo dung
dch cho m khng lm thay i nhit , p sut v s ht cc cu
t j ( i) trong h

G
i
N i

N j i ,T , P

G nng lng t do Gibbs;

Ni - s ht loi i; Nj - s ht loi khc, trong c c dung mi.

U
i
N i

S ,V , N j i N i

S , P , N j i N i

T , P , N j i N i

T ,V , N j i

Dung dch l tng :

lt io (T ) RT ln X i
i

thuc io (T ) RT ln ai

Dung dch thc :

ithuc io (T ) RT ln ai io (T ) RT ln Ci RT ln i

thuc
i

RT ln i g
lt
i

gi* c trng cho tng tc gia ht i vi cc tiu

phn khc trong dung dch cng a mt mol cu
t i t dung dch l tng sang dung dch thc.

BA = +

B+

BA = ++ +

o
BA
o o

Dung dch l tng :

lt
BA

o
BA

Dung dch thc :

RT ln C BA

RT ln C
lt

lt o RT ln C

thuc
o
BA
BA
RT ln aBA

thuc
o RT ln a

thuc

RT ln a
o

RT ln aBA RT ln a RT ln a

aBA a .a
TN khng th xc nh
hot ca tng loi ion

hot trung bnh

8

Hot trung bnh (a) v

h s hot trung bnh (f hay )

a a a
a

1 /

a (a .a )

1 /

m (m .m )

( . )1 /

Dung dch v cng long :

(aC C)C0

(am m)m0

(aX X)X0

C = m = X = 1
9

So snh tnh
khng l
tng gia dd
khng in ly
v dd in ly

Log m
J. Koryta, Principles of Electrochemistry, John Wiley & Sons
Ltd. (1993).
10

Xc nh h s hot c th bng nhiu phng php :

p sut thm thu, h bng im, tng ph
im, p sut hi bo ho, sc in ng
C, mol/l 0,00010 0,0100 0,0500 0,100
f

(1)
(2)
(3)

0,965
0,965
0,965

0,900
0,899
0,899

0,813
0,809
0,815

0,763
0,762
0,764

0,500

1,00

2,00

0,638
0,644

0,596
0,597

0,563
0,569

H s hot ion trung bnh ca dung dch KCl nhit

25oC xc nh bng php o p sut thm thu (1), h bng
im (2) v sc in ng (3).
11

H s hot - nng . Pt LewisRandallBrnsted

H s hot ion trung bnh ca dung dch MgCl2 theo nng
C

0,100

0,200

0,400

0,800

1,00

2,00

5,00

0,516

0,468

0,442

0,445

0,479

0,668

1,550

Lewis v Randall :

Lgf

HCl

KNO3

NaCl

H s hot trung bnh

ca dung dch long ph
thuc vo nng ca tt
c cc ion trong dung dch
v in tch ca chng.

KCl

Lc ion I

12

Lc ion I

1
I mi Z i2
2 i

hay

1
I Ci Z i2
2 i

Pt thc nghim Lewis Randall:

lg f h I
H s hot trung bnh ( , f ) ca cht in ly l
mt hm tng hp ca lc ion I ca dung dch.
H s hot ca mt cht trong dung dch ph thuc vo nng ca tt c
cc ion trong dung dch v in tch ca chng ch khng ph thuc vo bn
cht v nng ca chnh cht .

Pt TN Brnsted
nc, 20oC, 1-1, long: A 0,5 lt3/2 mol1/2:

lg f 0,5 C
13

Lgf
CaCl2

Pt TN Lewis Randall
ch ng cho vng
nng thp:
m 0,02
K2SO4
ZnSO4

14

p dng khi nim hot vo thuyt in ly Arrhenius

B+A_ +Bz+ + Az

Hng s phn ly tht - K:

K hng s phn ly biu kin

nc, 25oC, 1-1:

B A 10

+ = = 1

0,5 I

; BA 1

lg lg A I 0,5 I

K'

B A

K .10

I
15

 phn ly:

. . .C .C 1
K'

C (1 )
(1 )

Dung dch in ly yu, tng i long:

K << C

16

K =

K =

K =

C
S ph thuc in ly vo nng ca cc cht in ly
yu c hng s in ly biu kin khc nhau
17

2. Thuyt tnh in Debye Hckel

.2.1 S phn b ion trong dung dch in ly. M
hnh bu kh quyn ion
2.2 Th ca bu kh quyn ion. Nng lng
tng tc
2.3 Thuyt Debye- Hckel v h s hot
2.4 Phn tch u, nhc im ca thuyt DebyeHckel v s pht trin tip theo
2.5 p dng thuyt Debye Hckel cho cht
in ly yu

18

III.2.1 S phn b ion trong dung dch in ly.

M hnh bu kh quyn ion
-

Dd l tng: Cc ion khng tng

tc. (Arrhenius)
1806, T. Grotthuss: l thuyt u tin
v in phn

Dd thc (Debye v Hckel - 1923 ):

Tng tc tnh in Xung
quanh mi ion s tp trung nhiu
ion tch in tri du vi n.

+
+

Dd l tng
-

+
+

+
-

Dd thc
Atkins, Physical Chemistry. 6th ed. Figure 10.2

19

Tnh cht ca thuyt Debye v Hckel

(i) cht in ly phn ly hon ton ( = 1; trong dung
dch khng tn ti phn t khng phn ly);
(ii) dung dch: mi trng ng nht vi hng s in
mi khng i;
(iii) tng tc gia cc ion ch tun theo nh lut tnh
in Coulomb.
(iv) Ion phn b theo m hnh kh quyn ion, c tnh
i xng cu

20

 Mi ion c khuynh hng phn

b gn cc ion tri du vi n
Ion trung tm
S phn b ca cc ion quanh
ion trung tm tun theo nh lut
phn b Maxwell - Boltzmann:
ph thuc vo nng lng
tng tc gia ion trung tm vi
cc ion khc.
M hnh kh quyn ion theo
thuyt Debye - Hckel

Do chuyn ng nhit: cc ion

lun i ch cho nhau kh
quyn ion mang tnh thng k.

Nng lng tng tc tnh in ca mi ion vi cc ion

khc trong dung dch chnh l nng lng tng tc ca
ion vi kh quyn ion bao quanh n.
21

2.2 Th ca bu kh quyn ion. Nng lng tng

tc
Bu kh quyn ion c tnh i xng cu: pt Poisson -

d 2 2 d

2
o dr
r dr

= niZieo

: th; : mt in tch

ni : nng cc b ca ion loi i

ni lin h vi nng th tch nio bng phn b Boltzmann:

W
ni nio exp( )
kT

W = Zieo

ni nio exp(

W: nng lng tng tc tnh in

kT: nng lng chuyn ng nhit
Z i eo
kT

Z i eo
nio Z i eo . exp

kT 22

 Z i eo
nio Z i eo . exp

kT

2
x
x
x
e
1 x
e 1 x ....
2!
x << 1
nng lng tng tc tnh in rt nh so
vi nng lng chuyn ng nhit.

Z i eo
1
kT

nio Z i2 eo2
Z i eo
[nio Z i eo .1
)
] (nio Z i eo ) (
kT
kT

Dung dch trung ha v in

(nioZieo) = 0

eo2
2
(ni o Z i )
kT

23

1 eo2
2

n
z

io i i
o kT i

t:

eo2
2

(
n
Z

io i )
o kT

d 2 d
2
2
dr
r dr
2

iu kin bin:

Nghim chung

r 0

Z i eo
A1
4 o
ion l cc in tch im

A1

A2

A2 0
e r
A1
r
24

Z i eo e r

4 o r

a = [ - i]r 0

th ca bu kh
quyn ion

th gy bi bu kh quyn ion
ti v tr ca ion trung tm

i : th ca in trng do ion trung tm

Z i eo
i
4 o r

1/ : bn knh bu kh
quyn ion

Z i eo
a
4 o

e r 1

r 0

Z i eo
a
4 o
25

Z i eo
a
4 o

Z i eo
i
4 o r

tng tc gia ion trung tm vi bu kh quyn ion = tng

tc tnh in gia hai ion c in tch tri du, Zieo v Zieo,
nm cch nhau mt khong 1/.

q1q2
U
4 o d

Nng lng tng tc tnh cho 1 ion

Z i2 eo2
U
8 o
+
-

+
+

1/
Z ie o

Z ie o

1/

-Zieo

Z ie o
26

2.3 Thuyt Debye- Hckel v h s hot

S khc bit ca dung dch thc so vi dung dch l tng l
do nng lng tng tc ca ion vi bu kh quyn ion

thuc
i

RT ln i g
lt
i

Z i2 eo2
RT ln i N A U N A
8 o

eo2
2

(
n
Z

io i )
o kT
Z i2 eo2
ln i
8 ( o kT ) 3 / 2
1
I Ci Z i2
2 i

k = R/NA

2 2
Z
2
i eo
(nio Z i ) 8 ( kT) 3 / 2
o

2.103 N A I

C+ = C = C

I=C
11

27

lg i Z h I
2
i

(1,6022.1019 ) 3 (2.6,022.1023.103 )1/ 2

1
1,825.106
1/ 2
3 / 2
h
.

(
l
/
mol
)
.
K
2,3026.8.3,1416.(0,88542.1011.1,3807.1023 ) 3 / 2 (T ) 3 / 2
(T ) 3 / 2

H s hot ca mi ion ph thuc vo in tch ca ion ,

nhit , hng s in mi ca dung mi v lc ion.
Khng kim chng bng thc nghim c h s hot trung bnh

1 /

( . )

lg

( lg lg )

2
2

Z

lg Z Z h I
lg h I .
(xem trong ti liu)

nh lut gii hn Debye-Hckel

28

lg Z Z h I
ph hp vi nh lut TN ca Lewis-Randall

H s hot ca cc dung dch c cng lc ion phi bng nhau

1,825.106
lg
C 0,507 C
3/ 2
(80,1.293)
Nc, cht in ly 1-1, 20oC:
/l GH Debye-Hckel

Pt TN Brnsted

lg f 0,5 C

Nc, cht in ly 1-1, 20oC, dd long :

29

2.4 Phn tch u, nhc im ca thuyt DebyeHckel v s pht trin tip theo

M t ng n s ph thuc ca h s hot (dd long) vo I v T

Tnh cc i lng nhit ng mol ring phn ca dung dch nh:

entropy mol, nhit dung mol, nn mol, n nhit mol, ...

Tin on Hpha long dung dch in ly (khi pha long tng tc gia
cc ion gim). Theo thuyt Debye- Hckel: nng nh, Hpha long
dung dch phi t l thun vi C1/2 thc nghim xc nhn.

nh lut gii hn Debye-Hckel khng cha cc

thng s thc nghim

30

Gii hn
Gi tr h s hot thc nghim v tnh theo nh lut gii hn DebyeHckel cho dung dch NaCl

0,0001

0,001

0,005

0,010

0,050

0,100

TN

0,975

0,9649

0,9275

0,9024

0,8205

0,7813

LT

0,971

0,9634

0,9200

0,8890

0,7652

0,6896

Ch ph hp vi thc nghim khi nng dung dch 0,01 m

Zi cng ln sai lch gia thc nghim v l thuyt cng tng

Ti sao ?
31

Nguyn nhn
B qua kch thc ion so vi khong cch gia cc ion.

Zieo << kT
Khng tnh n s thay i dung mi trong qu trnh ha tan
Xem ion l nhng in tch im
Ch xt tng tc tnh in, b qua cc loi tng tc khc

ch ng cho dung dch long

gn ng bc hai Debye v Hckel: kch thc ca ion

32

lim[ - i]ra

Z i eo
e a
A1
4 o (1 a)

lg

Z Z h. I
1 a

Z Z h. I
1 aB I

B = /I1/2)

Dd nc NaCl 0,1 m, 25oC a = 4,8

Guntenberg

1-1, nc 25oC

a 3,04 , a.B 1

lg

Z Z h. I
1 I

33

So snh gi tr h s hot thc nghim v tnh theo php gn ng bc hai

Debye Hckel cho dd nc ca NaCl 25oC vi a = 4,8 .

0,001

0,005

0,010

0,050

0,100

logTN

0,0155

0,0327

0,0445

0,0859

0,072

logLT

0,0154

0,0325

0,0441

0,0844

0,077

gn ng bc ba Debye Hckel:

C - hng s thc nghim

lg
m=12

Z Z h. I
1 aB I

CI
34