TNG TC ION ION

TRONG DUNG DCH IN LY

CHNG III
1
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
2
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.
V SAO ?
Sai st nh lng o, K
pl

Ch c th p dng cn bng phn ly vo
dung dch long ca cht in ly yu.
Tng tc ion-ion
M t hnh thc
Khi nim HOT
3
Ton b tng tc
trong dung dch in ly
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.
] [
] ][ [
HA
A H
K
+
=
HA
A H
a
a a
K
+
=
m t mt cch
hnh thc
4
Hot v h s hot
a
C
= C.
C

a
m
= m.
m

a
X
= X.
X

Cch biu
din nng
n v
K hiu
Nng Hot H s hot
mol
mol/l
C, M a
C
f,
molan
mol/kg dung
mi
m a
m

m

phn mol X, N a
X
, a
N

X
,
N

C
,
m
,
X
,
(hay f
C
, f
m
, f
X
)
h s hot
(mol, molan v
phn mol)
5
Ha th
6
P T
i j
N
i
i
N
G
, ,
=
|
|
.
|

\
|
c
c
=
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 nng lng t do Gibbs;
N
i
- s ht loi i; N
j
- s ht loi khc, trong c c dung mi.
i j i j i j i j
N V T
i
N P T
i
N P S
i
N V S
i
i
N
F
N
G
N
H
N
U
= = = =
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
, , , , , , , ,

7
Dung dch l tng :
i
o
i
lt
X RT T
i
ln ) ( + =
Dung dch thc :
i
o
i
thuc
a RT T
i
ln ) ( + =
i i
o
i i
o
i
thuc
i
RT C RT T a RT T ln ln ) ( ln ) ( + + = + =
-
= =
i i
lt
i
thuc
i
g RT ln
g
i
*
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.
8
BA = v
+
B
+
+ v

BA
= v
+

+
+ v

o o o
BA + +
+ = v v

+ + +
+ =
+ =
+ =
C RT
C RT
C RT
lt
lt
BA
o
BA
lt
BA
ln
ln
ln
o
o




+ +
+
+ =
+ =
+ =
a RT
a RT
a RT
thuc
thuc
BA
o
BA
thuc
BA
ln
ln
ln
o
o



+ +
+ = a RT a RT a RT
BA
ln ln ln v v

+
+
=
v
v
a a a
BA
.
Dung dch l tng : Dung dch thc :
TN khng th xc nh
hot ca tng loi ion
hot trung bnh
9
Hot trung bnh (a

)

v
h s hot trung bnh (f

hay

)
v v v
v v v
v v v

v
v v
/ 1
/ 1
/ 1
) . (
) . (
) . (
+
+
+
+
+
+
+
+
=
=
= =
=
m m m
a a a a
a a a
Dung dch v cng long :
(a
C
C)
C0

;
(a
m
m)
m0

;
(a
X
X)
X0

C
=

m
=
X
= 1

10
Log m
J . Koryta, Principles of Electrochemistry, John Wiley & Sons
Ltd. (1993).
So snh tnh
khng l
tng gia dd
khng in ly
v dd in ly
11
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 0,500 1,00 2,00

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

0,638
-
0,644

0,596
-
0,597

0,563
-
0,569
H s hot ion trung bnh ca dung dch KCl nhit
25
o
C xc nh bng php o p sut thm thu (1), h bng
im (2) v sc in ng (3).
H s hot - nng . Pt LewisRandallBrnsted
12
C 0,100 0,200 0,400 0,800 1,00 2,00 5,00
f

0,516 0,468 0,442 0,445 0,479 0,668 1,550

H s hot ion trung bnh ca dung dch MgCl
2
theo nng
HCl NaCl
KCl
KNO
3

C
Lgf

Lewis v Randall :
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.
Lc ion I
13
Lc ion I
2 2
2
1
2
1
i
i
i i
i
i
Z C I hay Z m I

= =
Pt thc nghim Lewis Randall:
I h f =

lg
Pt TN Brnsted
nc, 20
o
C, 1-1, long: A ~ 0,5 lt
3/2
mol
1/2
:
C f 5 , 0 lg =

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 .
14
Lgf

C
CaCl
2

K
2
SO
4

ZnSO
4

Pt TN Lewis Randall
ch ng cho vng
nng thp:
m s 0,02
15
p dng khi nim hot vo thuyt in ly Arrhenius
B
v+
A
v_
v
+
B
z+
+ v

A
z
K hng s phn ly biu kin
nc, 25
o
C, 1-1: v
+
= v

= 1 I I A 5 , 0 lg lg = = =
+

1 ; 10
5 , 0
= = =

BA
I
A B

I
A B
K
K
K 10 . ' = =

Hng s phn ly tht - K:
16
phn ly:
) 1 (
.
) 1 (
. . .
'
1
o
o
o
o v v
v v v v v v

+
+
C
C
C
K
Dung dch in ly yu, tng i long:
K << C
17
o
C
K = K = K =
S ph thuc in ly vo nng ca cc cht in ly
yu c hng s in ly biu kin khc nhau
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 Debye-
Hckel v s pht trin tip theo
2.5 p dng thuyt Debye Hckel cho cht
in ly yu
18
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.

-
-
-
-
-
+
+
+
+
+
+
-
-
-
-
-
-
+
+
+
+
+
+
-
Atkins, Physical Chemistry. 6
th
ed. Figure 10.2
Dd l tng
Dd thc
19
III.2.1 S phn b ion trong dung dch in ly.
M hnh bu kh quyn ion
20
Tnh cht ca thuyt Debye v Hckel

(i) cht in ly phn ly hon ton (o = 1; trong dung
dch khng tn ti phn t khng phn ly);
(ii) dung dch: mi trng ng nht vi hng s in
mi c 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
21
M hnh kh quyn ion theo
thuyt Debye - Hckel
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.
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.
2.2 Th ca bu kh quyn ion. Nng lng tng
tc
Bu kh quyn ion c tnh i xng cu: pt Poisson -
22
dr
d
r dr
d
o

cc

2
2
2
2
+ = =
V
: th; : mt in tch
= En
i
Z
i
e
o

n
i
: nng cc b ca ion loi i
n
i
lin h vi nng th tch n
io
bng phn b Boltzmann:
) exp(
kT
W
n n
io i
=
W: nng lng tng tc tnh in
kT: nng lng chuyn ng nhit
W = Z
i
e
o

) exp(
kT
e Z
n n
o i
io i

=

|
.
|

\
|
=
kT
e Z
e Z n
o i
o i io

exp .
23

|
.
|

\
|
=
kT
e Z
e Z n
o i
o i io

exp .
....
! 2
1
2
+ + + =
x
x e
x
x e
x
+ =1
x << 1
1 <<
kT
e Z
o i

nng lng tng tc tnh in rt nh so
vi nng lng chuyn ng nhit.
) ( ) ( ] 1 . [
2 2

= |
.
|

\
|
=

kT
e Z n
e Z n
kT
e Z
e Z n
o i io
o i io
o i
o i io
E(n
io
Z
i
e
o
) = 0
Dung dch trung ha v in

|
|
.
|

\
|
=

) (
2
2
i
o
i
o
Z n
kT
e
24

V
=
i
i i io
o
o
z n
kT
e

cc

2
2
2 1

= ) (
2
2
i io
o
o
Z n
kT
e
cc
_
_

2
2
2
2 2
= + = =
V
dr
d
r dr
d
r
e
A
r
e
A
r r _ _

2 1
+ =

0 =
r
iu kin bin:
Nghim chung
0
2
= A
r
e
A
r _

=
1
o
o i
e Z
A
tcc 4
1
=
t:
ion l cc in tch im
25
r
e e Z
r
o
o i
_
tcc

=
4

a
= [ -
i
]
r 0

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

i
: th ca in trng do ion trung tm
r
e Z
o
o i
i
tcc

4
=
0
1
4

=
r
r
o
o i
a
r
e e Z
_
tcc

o
o i
a
e Z
tcc
_

4
=
1/_ : bn knh bu kh
quyn ion
26
r
e Z
o
o i
i
tcc

4
=
o
o i
a
e Z
tcc
_

4
=
tng tc gia ion trung tm vi bu kh quyn ion = tng
tc tnh in gia hai ion c in tch tri du, Z
i
e
o
v Z
i
e
o
,
nm cch nhau mt khong 1/_.
d
q q
U
o
tc 4
2 1
= A
o
o i
e Z
U
tcc
_
8
2 2
= A
Nng lng tng tc tnh cho 1 ion
-
-
- -
- -
-
+
+
+
+
+
+
+
1/_
Z
i
e
o
Z
i
e
o
-Z
i
e
o
Z
i
e
o
1/_
2.3 Thuyt Debye- Hckel v h s hot
27
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
-
= =
i i
lt
i
thuc
i
g RT ln
o
o i
A A i
e Z
N U N RT
tcc
_

8
ln
2 2
= A =

= ) (
2
2
i io
o
o
Z n
kT
e
cc
_
I N
kT
e Z
Z n
kT
e Z
A
o
o i
i io
o
o i
i
3
2 / 3
2 2
2
2 / 3
2 2
10 . 2
) ( 8
) (
) ( 8
ln
cc t cc t
= =

k = R/N
A

2
2
1
i
i
i
Z C I

=
11
C
+
= C

= C

I = C

28
I h Z
i i
2
lg =
2 / 3 2 / 1
2 / 3
6
2 / 3 2 / 3 23 11
2 / 1 3 23 3 19
. ) / (
) (
10 . 825 , 1
) (
1
.
) 10 . 3807 , 1 . 10 . 88542 , 0 .( 1416 , 3 . 8 . 3026 , 2
) 10 . 10 . 022 , 6 . 2 ( ) 10 . 6022 , 1 (

= = K mol l
T T
h
c c
H s hot ca mi ion ph thuc vo in tch ca ion ,
nhit , hng s in mi ca dung mi v lc ion.
) lg lg (
1
lg
+ +
+ = v v
v

Khng kim chng bng thc nghim c h s hot trung bnh

v v v

/ 1
) . (
+
+
=
+
+ +

+
+
=
v v
v v

2 2
. lg
Z Z
I h
I h Z Z
+
= lg
(xem trong ti liu)
nh lut gii hn Debye-Hckel
29
C C 507 , 0
) 293 . 1 , 80 (
10 . 825 , 1
lg
2 / 3
6
= =

Nc, cht in ly 1-1, 20

o
C, dd long :
/l GH Debye-Hckel
C f 5 , 0 lg =

Pt TN Brnsted
Nc, cht in ly 1-1, 20
o
C:
I h Z Z
+
= lg
H s hot ca cc dung dch c cng lc ion phi bng nhau
ph hp vi nh lut TN ca Lewis-Randall
30
2.4 Phn tch u, nhc im ca thuyt Debye-
Hckel 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 AH
pha long
dung dch in ly (khi pha long tng tc gia
cc ion gim). Theo thuyt Debye- Hckel: nng nh, AH
pha long

dung dch phi t l thun vi C
1/2
thc nghim xc nhn.
nh lut gii hn Debye-Hckel khng cha cc
thng s thc nghim
Gii hn
Ch ph hp vi thc nghim khi nng dung dch s 0,01 m
Z
i
cng ln sai lch gia thc nghim v l thuyt cng tng
31
m 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
Gi tr h s hot thc nghim v tnh theo nh lut gii hn Debye-
Hckel cho dung dch NaCl
Ti sao ?
32
Nguyn nhn
B qua kch thc ion so vi khong cch gia cc ion.
Z
i
e
o
<< kT
Khng tnh n s thay i c
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
33
lim[ -
i
]
ra

) 1 ( 4
1
a
e e Z
A
a
o
o i
_ tcc
_
+
=
I aB
I h Z Z
a
I h Z Z
+
=
+
=
+ +

1
.
1
.
lg
_

B = _/I
1/2
)
Dd nc NaCl 0,1 m, 25
o
C a = 4,8
I
I h Z Z
+
=
+

1
.
lg
Guntenberg
1-1, nc 25
o
C
a ~ 3,04 , a.B ~ 1
34
m 0,001 0,005 0,010 0,050 0,100

log

TN

0,0155 0,0327 0,0445 0,0859 0,072
log

LT
0,0154 0,0325 0,0441 0,0844 0,077
So snh gi tr h s hot thc nghim v tnh theo php gn ng bc hai
Debye Hckel cho dd nc ca NaCl 25
o
C vi a = 4,8 .
gn ng bc ba Debye Hckel:
CI
I aB
I h Z Z
+
+
=
+

1
.
lg
C - hng s thc nghim
m = 1 2