PHN II

IN HA HC
Ni dung
Tnh cht ca dung dch in ly
(DDL)
S chuyn vn in tch
trong DDL
Pin v in cc
ng hc ca qu trnh in ha
Chng 1:
Chng 2:
Chng 3:
Chng 4:
1.1. Dung dch cc cht in ly (DDL)
Chng 1: Tnh cht ca DDL
H
2
O
HCl H
3
O
+
+ Cl
-
T cao
NaCl Na
+
+ Cl
-
Cht in ly (cht in phn): l cc
cht c th to ra cc dung dch ion v
hn hp nng chy c cha cc ion.

V d: mui, axit, baz
l dung dch c tnh cht:
ng nht v tnh cht ho l mi im trong
th tch
Thnh phn c th thay i lin tc trong mt
gii hn
Tng im si
Gim im kt tinh
Tng p sut thm thu: t =i.C.R.T (do s phn
ly cht in ly thnh ion nn lm tng s ht
phn t trong dung dch

Dung dch cht in ly
m s s m dd dd
c K i T c K i T
T R C i T R n i V
, 2 , 2
= A = A
= H = H
p sut thm thu: t =i.C.R.T
Ap suat tham thau:
Ap suat can phai tac dung
len dung dch e dung moi
nguyen chat khong the tham
thau qua mang ban tham sang
dung dch .
1.1. Dung dch cc cht in ly (DDL) (tt)
S in ly (electrolysis):

l s phn ly ca cc cht in ly trong dung dch.
l mt qu trnh thun nghch



Hng s in ly (K
D
, electrolyte constant):



Chng 1: Tnh cht ca DDL

+
+ v v
v + v
+
z z
A M A M
| | | |
| |
+
+
v v
v

v
+
=
A M
A . M
K
z z
D
1.1. Dung dch cc cht in ly (DDL) (tt)
phn ly (o, electrolytic capacity):
Chng 1: Tnh cht ca DDL
o =
S phn t phn ly
S phn t ban u
+
+ +
v

v
+
v + v v + v
v v
o
o
= ) ( ) .(
) 1 (
. n
K
) ( ) 1 (
0
D
o ln ( 1) : Cht in ly mnh: Mui, acid v c, baz mnh
o nh ( 0) : Cht in ly yu: acid hu c, acid yu, baz yu
Khi v
+

= v
-

= 1
o
o
=
1
. n
K
2
0
D
n
0
= s mol cht
in ly (ban u)
Cht o
HCl 0.926
H
2
SO
4
0.60
H
2
C
2
O
4
0.50
HF 0.09
CH
3
COOH 0.014
H
2
CO
3
0.0017
HCN 0.0001
KOH 0.90
Ba(OH)
2
0.77
NH
3
0.014
KCl 0.862
MgCl
2
0.765
K
2
SO
4
0.722
MgSO
4
0.449
in ly o ca mt s cht in ly trong dung dch nc 0.1 N
S phn ly ca cht tan thnh ion thng xy ra yu trong dung mi c
cc yu (c b) v xy ra mnh trong dung mi c cc mnh (c ln)


in ly tng khi nng dung dch gim v ngc li in ly
gim khi nng dung dch tng.
(tng nng tng tng tc)
C
N
0.1 0.05 0.01 0.005 0.001
o 0.014 0.019 0.042 0.060 0.124
S thay i in ly ca axit axetic
H s Van tHoff i
H s Van tHoff i: l t s gia s phn
t sau phn ly (ion + phn t) so vi s
phn t trc khi phn ly (s phn t ho
tan)
v = v
+

+ v
-


0
0 0 0 0
n
. n . . n . ) . n n (
i
o v + o v + o
=
+
i = 1 + (v-1).o
1
1 i
v

= o
H s vant Hoff ca mt s cht
1.1. Dung dch cc cht in ly (DDL) (tt)
nh hng ca dung mi:

nh lut Coulomb:


Chng 1: Tnh cht ca DDL
2
2 1
. . . 4
.
r
q q
f
c t
=
q
1
, q
2
: in tch ca 2 ion
r: khong cch gia 2 ion
c : thm in mi: c= c
0
.D
c
0
= 8.85x10
-12
J.C/m (F/m)
D: thm in mi tng i
D nh f ln ion tri du t kt hp li hay khng to ra ion
o nh
Cng vi D, bn cht ca cht in ly v dung mi cng nh hng:
V d: Mt s cht ha tan v phn ly trong HCN (D=96) yu hn trong
H
2
O (D=81)
Cht c Cht c
HF 84.00 Aniline 7.00
Nc 80.00 Acit axetic 6.19
Ethanol 25.20 Clorofoc 4.72
Amoniac 25.00 Ete ietyl 4.10
Axetone 20.70 Benzen 2.30
SO
2
lng 15.35 CF
4
2.23
Hng s in mi ca mt s cht
c trng quan trng ca dung mi l hng s in mi c.
c ph thuc c cc, cu to v kch thc ca phn t dung mi.
c cc cng ln, c cng ln.
Da vo c c th d on c kh nng ca dung mi i vi s ha tan, phn
ly
1.2. Nc
Chng 1: Tnh cht ca DDL
O
H
H
104,523
o

0.276 nm
-Momen lng cc: 1,84 0.02D
-Lien ket cua moi phan t nc trung
bnh ln hn 2. Xung quanh mot phan t
nc co t nhat 4 phan t khac bao boc
(cau truc t dien eu).
-Nc a ket tinh dang luc phng.
Nc co cau truc gia tinh the, con goi
la bang ba chieu, hay claster. Cac claster bi
trong nc t do.
Nc v tnh cht ca n
1.3. Phn loi cht in ly
Chng 1: Tnh cht ca DDL
C 3 loi cht in ly
MNH
Copyright The McGraw-Hill Companies, Inc.
Permission required for reproduction or display.
YU
Copyright The McGraw-Hill Companies, Inc.
Permission required for reproduction or display.
KHNG IN LY
Copyright The McGraw-Hill Companies, Inc.
Permission required for reproduction or display.
ng ma, glucose, urea
H
2
CO
3,
CH
3
COOH,
NH
4
OH
HCl, H
2
SO
4
, NaOH, KOH
Cht in ly thc, th: da vo bn cht lin kt trong phn t, tinh th.
Lin kt ion: cht in ly thc (true electrolyte): v d: NaCl
Tng tac gia ion trong tinh the va phan t dung moi lng cc + chuyen ong nhiet
cua ion lien ket mang b t ion lien ket vi dung moi, tach khoi mang.

Cc loi khc: cht in ly th (potential electrolyte): v d: HCl
Tng tac lng cc - lng cc + chuyen ong nhiet Ph hy phan t co cc
thanh ion hydrat hoa ion tng tac nc tao ion H
3
O
+
(oxonium, hydronium).
* Dung mi khc nc:
- Dung mi proton: Cho H
+
, to lin kt hydro gia DM v cht tan c th
ha tan, phn ly, solvat ha cc ion.
- Dung mi aproton: C nhng cp e
-
dng chung c th solvat cc cation,
to cc dung dch ion.
1.4. S solvat ha cc ion
Chng 1: Tnh cht ca DDL
Qua trnh tac dung cua ion vi cac phan t dung moi to tap hp tng oi ben chac goi
la solvat hoa. Dung moi nc: hydrat hoa.
So cua cac phan t nc rang buoc trong hydrat (phc nc) goi la so cua hydrat hoa (so
phoi t).
Vi dung moi nc: (quan trong nhat) dung dch cua cation kim loai kiem, kiem tho tao ra do
tng tac tnh ien ion lng cc.Tng tac nay phu thuoc: ien tch, ban knh, khoi lng
cation
1.4. S solvat ha cc ion
Nguyen nhan cua s ien ly:
S solvat hoa, hydrat hoa giai phong nang
lng tinh the ran b pha v, lien ket hoa hoc b pha v.

lp hydrat hoa gan: lien ket cho nhan, do con obitan trong cua cation va cap ien
t ghep oi cua nc.
lp hydrat hoa xa: cac phan t dung moi nh hng khong hoan toan, do lien ket
long leo hn.
Cac ligand nc khong co nh trong phc nc ma co the thay oi v tr. Ligand
nay ra i, ligand khac vao the.
Dung dch l tng v dung dch thc
Dung dch l tng: Cation v
anion khng tng tc vi
nhau.

Dung dch thc: c s tng
tc tnh in.
Cc ion ngc du tp hp
gn nhau
-
-
-
-
-
+
+
+
+
+
+
-
-
-
-
-
-
+
+
+
+
+
+
-
Shaded region: Solvation
cage
L tng
Thc
1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL
NaCl Na
+
+ Cl
-
Th ha hc
+
+ =
Cl Na
NaCl

o
Cl
o
Na
o
NaCl
+
+ =
NaCl
o
NaCl NaCl
a RT ln + =
i i
o
i i
o
i i
m RT a RT ln ln + = + =
+
+ =
salt
+ + +
+ + + = + m RT m RT a RT
o o
salt
o
salt
ln ln ln
H s hot trung bnh ion
( )
+ + +
+ + = + m m RT a RT
o o
salt
o
salt
ln ln
o o o
salt +
+ =
( )
+ +
= m m RT a RT
salt
ln ln
2
+
=
i vi NaCl, m
+
= m
-
2 2

= m a
salt
Ti sao khng s dng nng mol m s dng nng molan ???
MgCl
2
Mg
2+
+ 2 Cl

+
+ +
+ + + = +
Cl
0
Cl Mg
0
Mg
salt
0
salt
ln 2 2 ln ln
2 2
m RT m RT a RT
2 2 0
Cl
0
Mg
salt
0
salt
ln 2 ln
2
+ +
+ + = +
+
m m RT a RT
+ +
=
2 2
salt
m m a
Ta c m
+
= m v m
-
= 2m
( )
3
1
2
+
=
nh ngha:
( )
3 3 3
2
salt
4 2

= = m m m a
+
+
z z
y x
yB xA B A
( ) ( ) ( ) ( ) ( )
( )
( )
y
B
x
A
y x y x
m y x ym xm m m a a
+
= = =
y
B
x
A
y
B B
x
A A
y
B
x
A
( )
( ) y x+

=
/ 1
y
B
x
A

( )
( ) ( ) y x y x y x
m y x a a
+

+
=
y
B
x
A
( )
3 3 3 3 2 1 2
Cl
4 2 1
-

= =
+
m m a a
Mg
Cho MgCl
2

: h s hot trung bnh ion l i lng quan trng,

c trng cho s sai lch nng dung dch mui so vi
khi trng thi l tng

1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL
H s hot trung bnh ion (tt)
*Ch :
- Tnh m
NaCl
trong dung dch c m
NaCl
= 0.1 v m
CaCl2
=
0.3 : m
NaCl
= (0.1
1

. 0.7
1
)
1/2

= 0.27

- H s hot trung bnh biu din cc loi nng
khc nhau:
a
c
=
c
.C

hoc a
x
=
x
.x

( ) ( )

+ + = v v ln . . ln . .
0
RT m RT
m
Vi: v.RT.ln(

) : Th ha d - thc o tng tc gia cc ion

vi nhau v vi phn t dung mi v c
cc phn t dung mi vi nhau
v.RT.ln(

) 0, tc

= 1;
dung dch
=
ly tng

Dung dch v cng long:
1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL
H s hot trung bnh ion (tt)
Th ha:
Trng thi chun
Trng thi chun l trng thi m m

=


= 1 tt c cc khong nhit v p
sut =
0
nhit bt k trng vi
dung dch v cng long.

ngha vt l ca

xc nh s khc bit gia dung dch thc v dung dch
l tng
C hai loi lc tc dng vo cc ion trong dung dch:
tng tc vi phn t dung mi
tng tc tnh in vi cc ion khc
Khi pha long dung dch tng khong cch gia cc
ion gim tng tc
Dung dch v cng long tng tc solvat ho l ch
yu dung dch v cng long ch l gn ng l
tng, xem nh nng lng solvat ho khng ph thuc
nng .

Lc ion (I)
Lc ion ca dung dch l mt na tng tch s nng ca mi
ion vi bnh phng s in tch (ha tr) ca tt c ion c
trong dung dch
I
m
= 0.5 Em
i
.Z
i
2


1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL
Nu biu din theo nng mol C
i
:
I
c
= 0.5 EC
i
.Z
i
2






Trong :
i: k hiu tt c cc ion trong dung dch

m
i
hay C
i
: l nng thc (khng k phn
khng phn ly)





Lc ion (I) (tt)
nh lut thc nghim Lewis v Randall:
Cht in ly mnh, vng nng long, cc dung
dch c cng lc ion h s hot trung bnh

nh nhau
1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL

=
i
i i
z m I
2
2
1
0.010 m HCl: m
H+
= m
Cl-
= 0.01 mol/kg,
( ) ( ) ( )
1 -
2 2
kg mol 01 . 0 1 01 . 0 1 01 . 0
2
1
= + + = I
0.10 m Na
2
SO
4

Cc phng php xc nh

Phng php nghim lnh:
o h nhit kt tinh ca dung dch AT vi cc
nng thp bit, ri xc nh
m

0
2 / 1
S
T
C
=

1.5. Tnh cht nhit ng ca DDL

Chng 1: Tnh cht ca DDL
Phng php da vo ha tan:
Khi bit tch s tan T, xc nh ha tan S
0
, ri tnh
c



PT Gibbs-Duhem: n
1
lna
1
+ n
2
lna
2
= 0
2
1
ln
RT dT
a d
=
mK
T d
a d
) (
ln
2
A
=
(*)
Phng php nghim lnh xc nh

1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL
PT Sreder :
Vi:
n
2
= m ; n
1
= 1000/M
1
;
AT=|T
0
-T| h nhit kt tinh
T
2
=T
0
2

K= R.T
0
2
M
1
/(1000) : hng s nghim
lnh
Do: a
2
= a

v
=

v
.m
v
(v
+
v+
. v
-
v-
)

Nn (*) tr thnh:

t :

Do : d(ln

) = -dj j.dlnm

Ly tch phn 2 v:
mK
T d
m d d
v

) (
ln ln
A
= +

dm
Km
T
mK
T d
dj
mK
T
j
2
) (
1
v v v
A
+
A
=
A
=
dm m j j
m
}
=

0
) / ( ln
Phng php nghim lnh xc nh

(tt)

1.5. Tnh cht nhit ng ca DDL
Chng 1: Tnh cht ca DDL
j/m
m
m
0
}
m
dm m j
0
) / (