1

2
Li ni u:
Thng qua cc t liu tham kho, chng em rt ra nhng chnh v
quan trng nht, cn nh nht trong cc phn sau y:
1. Cc nh lut c bn ca ha hc p dng cho h cc cht in li
2. Cn bng axit bazo
3. tan v tch s tan
T liu tham kho:
1. Sch Ha hc phn tch (cn bng ion trong dung dch) Tc gi:
Nguyn Tinh Dung
2. Sch????? Tc gi: Nguyn c Chung
3. Sch???? Tc gi: L Mu Quyn
4. Cng vi mt ti liu ti cc trang web: http://tailieu.vn/,
http://www.scribd.com/


















3
Mc lc:
A. CC NH LUT C BN CA HA HC P DNG CHO H CC
CHT IN LI
1. Cht in li v s in li 4
2. in li v hng s in li 4
3. Phn loi cht in li 6
4. D on nh tnh chiu hng phn ng xy ra gia cc cht
in li 6
B. CN BNG AXIT BAZO
1. nh nghi axit bazo theo thuyt in li 18
2. nh lut bo ton proton (iu kin proton) 18
3. Dung dch n axit n bazo 19
4. a axit v a bazo 27
5. Cc cht in li lng tnh 30
6. Dung dch m 32
7. Cn bng hidroxo cc ion kim loi 35
8. Danh php phc cht 37
9. nh gi cn bng to phc trong dung dch 40
C. TAN TCH S TAN 44












4
A.CC NH LUT C BN CA HA HC P
DNG CHO H CC CHT IN LI
I. Cht in li v s in li:
1. Th nghim:
Kt lun:
- Dung dch axit, mui, ba z dn in:
- Cc cht rn khan khng dn in
2. Cc khi nim:
- Cc cht c kh nng phn li thnh cc ion c gi l cht in
li
- Qu trnh phn li thnh ion c gi l qu trnh in li
- S in li c biu din bng phng trnh in li
3. Phng trnh in li:
- Cch vit phng trnh in li khi cho cht in li MX vo nc:
MX + (x+y)H
2
O M(H2O)
x
n+
+X(H
2
O)
y
n-
- Do ta khng bit chnh xc s phn t nc x, y trong cc ion
hadrat nn ngi ta thng biu din nh sau:
MX M
n+
+ X
n-

V d:
NaCl Na
+
+ Cl

HCl H
+
+Cl
-
NaOH Na
+
+OH
-

II. in li v hng s in li
1. in li:
- Khi nim: in li l t s gia s mol n ca cht phn li
thnh ion vi tng s mol n
o
ca cht tan trong dung dch
- Cng thc tnh:
=

Nu chia cho V ca dung dch th ta c:

5
V d: Ta c phng trnh :
MX M
n+
+ X
n-

Trong : [M
n+
] v [X
n-
] l nng tng ng ca hai ion do MX phn li ra
- nh gi : c cc gi tr dao ng t 0 n 1:
o i vi cc cht khng in li
o i vi cc cht in li hon ton
2. Hng s in li:
Xt phng trnh:
MX M
n+
+ X
n-

Khi K
c

Trong : [A] l nng ca cht / ion A ti thi im cn bng
Kc l hng s in li nng , ph thuc vo bn cht ca cht in li,
dung mi, vo nhit .
- i vi axit:
V d: CH
3
COOH CH3COO
-
+ H
+
K
a

- i vi ba- z:
V d: NH
3
+H
2
O NH
4
+
+ OH
-
K
b

Ch :
- K
a
cng ln th tnh axit cng mnh
- K
b
cng ln th tnh ba- z cng mnh
- K
a,
K
b
ch ph thuc vo nhit


6
III. Phn loi cht in li
1. Cht in li mnh v cht in li yu:
- Cn c vo in li v hng s in li m ngi ta quy c
phn bit ra cc cht in li mnh v cc cht in li yu
- Trong dung dch nc, cc cht in li mnh bao gm:
o Mt s axit v c: HCl, HBr, HI, HSCN, HNO
3
. HClO
4
.....
o Cc bazo kim v kim th: LiOH, NaOH, KOH, RbOH,
CsOH,...
o V hu ht cc mui tan
- Cht in li yu l cht khi tan trong nc ch c mt phn s
phn t phn li ra ion, phn cn li vn tn ti di dng phn t
trong dung dch.Bao gm:
o Cc axit yu: CH
3
COOH, H
2
S, HCN,...
o Cc bazo yu: Mg(OH)
2
, Bi(OH)
3

2. Biu din trng thi cht in li trong dung dch
- Cc cht in li mnh phn li hon ton, c biu din bng mt
mi tn hng t tri (ghi cng thc phn t ca cht in li)
sang phi (ghi cng thc cc ion tng ng).
- Cc cht in li yu phn li mt phn , c biu din bng du
cn bng thun nghch () gia cc phn t v cc ion ca cht
in li. c trng nh lng hn, ngi ta ghi thm g tr K
hoc lgK bn phi cn bng phn li
IV. D on nh tnh chiu hng phn ng xy ra
gia cc cht in li
1. Nguyn tc chung
- Khi tham gia phn ng, cc ion kt hp vi nhau (hoc tng tc
vi nhau) to thnh cc sn phm kt hp mi tng ng vi
gi tr xc nh ca hng s cn bng K ca phn ng. Nu K rt
ln th phn ng c coi l xy ra hon ton. Nu k v cng b
th coi nh phn ng khng xy ra
- Trong mi trng hp khc th mc xy ra ca cc phn ng
ph thuc gi tr cn bng v nng ca cc cht phn ng
2. Cc trng hp khng c phn ng xy ra
- Khi cc sn phm c th to thnh l cht in li mnh th phn
ng khng xy ra do cc sn phm kt hp ion s phn li hon
ton tr li thnh cc ion ban u.
V d: NaCl khng phn ng vi KNO
3

NaCl Na
+
+Cl
-


7
KNO
3
K
+
+ NO
3
-
V sn phm c th to thnh l KCl v NaNO
3
li phn li hon ton
thnh cc ion ban u
KCl K
+
+Cl
-
NaNO
3
Na
+
+ NO
3
-

3. Cc trng hp c phn ng xy ra
a. Phn ng to thnh cc cht t phn li
- Phn ng to thnh H2O t phn li:
V d: phn ng gia Axit v hidroxit, oxit bazo v axit, oxit axit v bazo
kim
Na
+
+OH
-
+Cl
-
Na
+
+Cl
-
+H
2
O
(NaOH +HCl NaCl +H
2
O)

- Phn ng to thnh cha cc axit t phn li
V d: Phn ng gia mt axit mnh v mt mui ca axit yu hn:
Na
+
+ CH3COO
-
+ H
+
+ NO
3
-
Na
+
+NO
3
-
+CH
3
COOH
(CH
3
COONa +HNO
3
NaNO
3
+CH
3
COOH)
- Phn ng to thnh cc phc cht t phn li
V d:
Cu
2+
+4NH
3
Cu(NH
3
)4
2+
(CuSO
4
+4NH
3
Cu(NH
3
)
4
2+
+ SO
4
2-
)
b. Phn ng to thnh hp cht t tan
V d:
AgNO
3
+KI AgI +KNO
3

AgNO
3
Ag
+
+NO
3
-

KI K
+
+ I
-

Ag
+
+I
-
AgI
Ag
+
+NO
3
-
+K
+
+I
-
AgI +K
+
+NO
3
-

c. Phn ng km theo s thot cht kh
V d:
2H
+
+2Cl
-
+SO
3
2-
2Na
+
+2Cl
-
+H
2
SO
3
(So
2
+H
2
O)
(2HCl +Na
2
SO
3
2NaCl +H
2
SO
3
)
d. Phn ng km theo s thay i trng thi oxi ha
- L phn ng xy ra c do s to thnh cc trng thi oxi ha
khc vi cc trng thi ban u


8
- nh gi nh lng mc xy ra gia cc phn ng cn
da vo cc nh lut c bn: nh lut hp thc, cc nh lut
bo ton vt cht v nh lut tc dng khi lng
V d:
Fe
3+
+ 3Cl
-
+Sn
2+
+2Cl
-
Fe
2+
+2Cl
-
+Sn
4+
4Cl
-
(FeCl
3
+SnCl
2
FeCl
2
+ SnCl
4
)
Sn
2+
Sn
4+
+2e
2 x | Fe
3+
+1e Fe
2+

Phng trnh phn ng ion: Sn
2+
+2Fe
3+
Sn
4+
+2Fe
2+

V. Cc nh lut c bn ca ha hc p dng cho h
cc cht in li
1. nh lut hp thc (T lng)
a. Ta phn ng
- i vi mt phn ng cho th t s gia bin i mol n
i

(hay bin i nng mol C
i
nu th tch hn hp phn ng
l khng i) vi h s hp thc ca cu t tng ng l ging
nhau i vi mi cht phn ng
- T s ny c gi l ta phn ng
=

(1)
Hoc
x=

(2)
T (1) v (2) ta rt ra
n
i
??v
i
C
i
xv
i
- Ta thy () cng ln khi ta phn ng cng ln. Nh vy
ta phn ng c trng cho mc hon ton ca phn ng
- Nu k hiu n
i
o
(hoc C
i
o
) l s mol (hoc nng ) ban u (trc
khi phn ng xy ra) th s mol n
i
(hoc nng C
i
) ca cht sau
khi phn ng xy ra:
n
i
n
i
o
+ n
i

C
i
C
i
o
+ C
i


9
- y, n
i
, C
i
< 0 i vi cc cht u v n
i
, C
i
> 0 i vi cc
cht to thnh sau phn ng
- cho thun li, ta quy c t v
i
c du m i vi cc cht
u v v
i
c du tng i vi cc cht cui
V d: Xt phn ng: Fe
3
O
4
+4CO 3Fe +4CO
2

T 0,2 mol Fe
3
O
4
v 0,5 mol CO to ra c 0,3 mol Fe. Hy tnh s mol
ca cu t khc ti thi im
Gii
Fe
3
O
4
+4CO 3Fe +4CO
2

H s hp thc, v

-1 -4 3 4
S mol ban u, no

0,2 0,5 0 0
S mol sau phn ng, n

? ? 0,3 ?
bin i s mol, n
i
-0,1.1 -0,14.4 0,3 0,1.4
- Ta phn ng:

(tnh i vi Fe)
- bin i s mol: n
Co2
0,1.4 0,4
n
Co
0,1.(-4) -0,4
b. Ta cc i
- i vi mt cu t phn ng hiu sut tham gia phn ng t cc
i khi s mol hoc nng (cn li) ca cu t ny trit tiu (n=
0 hoc C=0). Ta ni ta ca cu t t gi tr cc i
- i vi cu t i:
????

Khi ni 0 th ???i (???i)max

Hoc Ci 0 th xi (xi)max

i vi cc cht phn ng (cht u )Vi < 0 nn ??? v (xi)max u
dng. Ta c th vit:
???

||
| <0 hoc (xi)max

||
| <0


10
- Phn ng dng li khi nng ca mt trong cc cht phn ng
u bng khng. Nh vy ta cc i ca phn ng chnh l
gi tr b nht trong s cc gi tr cc i tnh i vi tng cht
phn ng
??? {

||
| } hoc (xi)max {

||
| }
V d: Xt hn hp cht phn ng gm Cr
2
O
7

2-
0,1 M, NO
2
-
0,12M, H
+
0,4M
3NO
2
+
Cr
2
O
7
2-
+8H
+
3NO
3-
+2Cr
3+
+4H
2
O
Vi
Cio

C
-3
0,12
-3x
0,12-3x
-1
0,1
-x
0,1-x
-8
0,4
-8x
0,4-8x
3
-
3x
3x
2
-
2x
2x








x ta phn ng
Nng H
2
O c coi l khng i, v nc l dung mi
Phn ng t hiu sut cao nht nn sau phn ng, nng cc cht u
c trit tiu.
i vi NO
2
-
0,12 -3x 0
i vi Cr
2
O
7
2-
0,1 x
i vi H
+
0,4-8x

Nh vy xmax x NO
2
0,04 v phn ng s din ra cho n khi ht ion
NO
2
-

c. Thnh phn gii hn
- Thnh phn gii hn (TPGH) l thnh phn ca h sau khi phn
ng xy ra vi toi cc i
2. nh lut bo ton vt cht
a. nh lut bo ton nng
a.1. Biu din nng ng trong dung dch:
- Trong dung dch cc cht in li, nng cc cht thng c
biu din theo nng mol. C mt s quy c:


11
o Nng gc C
o
l nng ca cht trc khi a vo hn
hp phn ng
o Nng ban u C
o
l nng ca cht trong hn hp,
trc khi phn ng xy ra
C
i
o

Trong : - V
i
l th tch ca dung dch cha cu t i, c
a vo hn hp phn ng
- V
j
l tng th tch ca hn hp
V d: Trn 10ml dung dch NaCl 0,012M vi 5,00 ml AgNO3 0,021M.
y, nng gc C
o
NaCl
0,012; C
o
AgNO3
0,021
Gii
Nng ban u: C
NaCl
o

Nng ban u ca AgNO3: C
AgNO3

NaCl Na
+
+Cl
-

AgNO
3
Ag
+
+NO
3
-
Ag
+
+Cl
-
AgCl
CNa
+o
CCl
-o

CAg
+o
CNO
3
-o
CAgNO
3
o

Phn ng:
Ag
+
+Cl
-
AgCl
Co 0,007 0,008
-0,007 -0,007
C 0,001
Cn bng:
AgCl Ag
+
+Cl
-

C 0,0001


12
[] x (0,001 +x)
Nng cn bng [Na
+
]
[NO
3
-
]
[Ag
+
] x < CoAg
+

[Cl
-
] > CCl-
a.2. nh lut bo ton nng ban u:
- Theo nh lut ny, nng ban u ca mt cu t bng tng
nng cn bng ca cc dng tn ti ca cu t c mt
trong dung dch
- Trong trng hp khi cu t ban u tn ti dng n phn,
cn trng thi cn bng li c dng lin hp (a phn) th trong
biu thc LBTN ban u, nng ca dng lin hp phi
nhn vi h s tng ng
V d: Biu din LBTN ban u i vi cc ion K+ v CrO42- trong
dung dch K
2
CrO
4
0,1M khi c mt axit mnh, bit rng trong dung dch,
crom tn ti di dng CrO
4
2-, HCrO
4
-, Cr
2
O
7
2-

Biu thc LBTN i vi K
+
:
C
K+
2C
K2CrO4
0,2 [K
+
]
Biu thc LBTN i vi ion CrO
4
2-
:
C
CrO4
2-
C
K2CrO4
0,1 [CrO
4
2-
] + [HCrO
4
-
] + 2[Cr
2
O
7
2-
]
b. nh lut bo ton in tch:
- nh lut bo ton in tch da trn nguyn tc cc dung dch c
tnh trung ha in: tng in tch m ca cc anion phi bng
tng in tch dng ca cc cation. in tch ca mi loi ion
bng in tch nng cn bng [i] vi in tch Z
i
ca ion tng
ng:
[i]Z
i
= 0
V d: Biu din LBTN i vi dung dch K
2
CrO
4
khi c mt axit HClO
4
.
Trong dung dch c mt cc ion H
+
, OH
-
(ca nc), ClO
4
-
, K
+
, CrO
4
2-
,
HCrO
4
-,
Cr
2
O
7
2-

[H
+
] +[K
+
] [OH
-
] +[ClO
4
-
] +[HCrO
4
] +2[CrO
4
2-
] +2[Cr
2
O
7
2-
]


13
Ngoi ra, cn mt s dng khc ca nh lut bo ton vt cht nh nh
lut bo ton proton, nh lut bo ton electron s c xt n trong cc
phn sau
a. nh lut tc dng khi lng
a.1.Cn bng v hot
- i vi phng trnh tng qut:
aA +bB dD +eE
khi t ti trng thi cn bng th ta c biu thc nh lut tc
dng khi lng
K =

Trong : - K l hng s cn bng nhit ng, ch ph thuc vo
nhit , bn cht ca cc cht phn ng v dung mi, hu nh
khng ph thuc p sut v thnh phn ca h
- (i) l hot ca cu t i
- Trong cc trng hp khc nhau, hot thng c chun
ha nh sau:
o Trong cc dung dch long hot ca cc ion v cc phn
t bng nng mol ca chng (mt cch nghim ngt
th hot ch bng nng dung dch v cng long)
o Trong cc dung dch long, hot ca dung mi bng
phn s ???? ca dung mi v bng n v
o Cc cht rn nguyn cht hoc cc cht lng nguyn cht
nm cn bng vi dung dch u c hot bng n v
o Cc cht kh nm cn bng vi dung dch u c hot
(hot p) bng p sut ring phn ca mi kh
o Hot ca mi cu t trong hn hp cht lng gn bng
phn s mol ca tng cu t
a.2.H s hot
- Hot lin h vi nng bi biu thc:
(i) [i ] f
i

- f
i
L h s hot ca cu t i. Trong ha hc phn tch, thng
biu din hot v nng theo thang mol/l v h s hot
bng f


14
- H s hot ca ion phn nh tng tc tnh in ca cc ion
vi nhau, v vy ph thuc s c mt ca ion trong dung dch, th
hin qua i lng lc ionI:
I

2

- [j] l nng ca ion j (bt k) vi din tch Z
j

- Trong cc dung dch long (I 0,001) c th nh gi h s hot
theo phng trnh gn ng ca bai _ Hucken:
lg f
i
-AZ
j
2

- A l hng s ph thuc vo bn cht ca dung mi v nhit .
Trong dung dch nc 25oC A 0,5115, v vy c th vit biu
thc dng gn ng:
- lg f
i
-0,5Z
j
2


- cc lc ion cao hn phi dng cc cng thc kinh nghim c
a thm cc s hng hiu chnh khc nhau. V d cng thc
Davies: lg f
i
-AZ
j
2
(

) c th p dng gn ng cho
n lc ion I 0,1 hoc cao hn mt t

V d: Tnh h s hot ca ion H
+
trong dung dch HCl 0,010M v
NaNO
3
0,090M.
HCl H
+
+ Cl
-

0,010 0,010
NaNO
3
Na
+
+ NO
3
-

0,090 0,090
Lc ion I = 0,5(0,01 + 0,01 + 0,09 + 0,09) = 0,10
Theo cng thc vit:
Lg f
H
+
= -0,5
(

+
10 , 0 . 2 , 0
10 , 0 1
10 , 0
= -0,11

lgf
H
+
= 0,776 ~ 0,78


15
b. Biu din nh lut tc dng khi lng i vi mt
s dng cn bng thng gp
b.1. Cn bng axit baz
- Cn bng phn li ca axit
HA H
+
+ A
-
K
a
=
( )( )
) (HA
A H
+


- K
a
l hng s phn li axit (hay gi tt l hng s axit)
B + H
2
O HB
+
+ OH
-
K
b
=
( )( )
( ) B
OH HB
+

- K
b
l hng s phn li baz ( hng s baz)
b.2.Cn bng to phc:
Ag
+
+ NH
3
AgNH
3
+
K
1
=
( )
( )( ) 3
3
NH Ag
AgNH
+
+

AgNH
3
+
+ NH
3
Ag(NH
3
)
2
+
K
2
=
( ) ( )
( )( ) 3 3
2
3
NH AgNH
NH Ag
+
+

- k
1
, k
2
l hng s to thnh tng nc ca cc phc cht AgNH
3
+

v Ag(NH
3
)
2
+

Fe
3+
+ OH
-
FeOH
2+
( )
( )( )
+
+
=
OH Fe
FeOH
3
2
1 |

Fe
3+
+ 2OH
-
Fe(OH)
2
+

( ) ( )
( )( )
2
3
2
2
+
+
=
OH Fe
OH Fe
|

- |
1
, |
2
l hng s to thnh tng hp ca cc phc cht
FeOH
2+
v FeOH
2
+

b.3.Cn bng to hp cht t tan
AgCl Ag
+
+ Cl
-
K
s
= (Ag)
+
(Cl)
- K
s
l tch s tan ca AgCl


16
b.4. Cn bng phn b
I
2
(nc) I
2
(benzen) K
D
=
( )
( )
nuoc
benzen
I
I
2
2

- K
D
l hng s phn b ca I
2
gia benzen v nc.
V d :
H
2
CO
3
H
+
+ HCO
3
-
K
1

HCO
3
-
H
+
+ CO
3
2-
K
2

H
2
CO
3
2H
+
+ CO
3
2-
K
K = K
1
.K
2
= 10
-6,35
.10
-10,33
= 10
-16,68

V d : nh gi hng s cn bng to phc hiroxo * |
1
ca Fe
3+

Fe
3+
+ H
2
O FeOH
2+
+ H
+
* |
1
(1)
Bit Fe
3+
+ OH
-
FeOH
2+
lg |
1
= 11,83
(2)
c c (1) cn t hp (2) vi cn bng phn li ca nc:
H
2
O H
+
+ OH
-
K
w
= 10
-14

Fe
3+
+ OH
-
FeOH
2+
|
1
= 10
11,83

Fe
3+
+ H
2
O FeOH
2+
+ H
+
* |
1

* |
1
= |
1
. K
w
= 10
11,83
.10
-14
= 10
-2,17

c. T hp cn bng:
- Trong cc bng tra cu , ngi ta cho gi tr hng s ca cc cn
bng n gin. Trong thc t, chng ta thng gp cc cn bng
phc tp hn c t hp t cc cn bng ring l.
c.1. Biu din cn bng theo chiu nghch
- Qu trnh thun: HA H+ +A-
- Qu trnh nghch: H+ +A- HA

17
- Nh vy hng s cn bng nghch bng gi tr nghch o hng s
ca qu trnh thun.
V d: Ag
+
+NH
3
AgNH
3
+
k
1
10
3,32

AgNH
3
+
Ag
+
+NH
3
K k
1
-1
10
-3,32

c.2. Cng cn bng
- Cho M + A MA k
1

MA +A MA
2
k
2

Tnh hng s cn bng ca M +2A MA
2

2
Cn bng thu c khi cng v theo v ca cc cn bng ng thi loi b
s hng MA cng c mt hai v
M + A MA k
1

MA +A MA
2
k
2
M + 2A MA
2

k
1
.k
2

Hng s cn bng t hp bng t hp khi cng cc cn bng vi nhau
bng tch cc hng s ca cc cn bng ring l.
V d 1:
H
2
CO
3
H
+
+ HCO
3
-
K1
HCO
3
-
H
+
+ CO
3
2-
K2
H
2
CO
3
2H
+
+CO
3
2-
K
K K
1
.K
2

V d 2: nh gi hng s cn bng to phc hidroxo
c.3. Nhn cn bng vi mt tha s n
B. CN BNG AXIT BAZO
1. nh ngha axit bazo theo thuyt in li
a. Thuyt axit-baz ca Bronsted v Lowry:
- Ngi u tin a ra cc nh ngha v axit v baz gn gi
vi quan im hin i l Svate Arrhnius (1859 - 1927). Da


18
trn cc kho st thc nghim v cht in li, ng cho rng:
- Axit l cht c kh nng phn li cho H
+
khi ha tan vo nc.
- Baz l cht c kh nng phn li cho OH
-
khi ha tan vo nc.
- Vo thi im , y l mt bc tin quan trng trong vic
nh lng axit baz. Nhng thuyt ny b gii hn ch ch
gii thch c tnh axit-baz ca cc hidro axit v cc hidroxit;
khng ni ln c vai tr ca dung mi.
- Mt nh ngha tng qut hn c ngh bi nh ha hc
an Mch: Jonhannes K.Bronsted v nh ha hc ngi Anh:
Thomas Lowry. Theo thuyt ny:
- Axit l cht c kh nng cho proton H
+

- Baz l cht c kh nng nhn proton H
+

- Thuyt axit baz ca Bronsted v Lowry bao hm thuyt
axit-baz ca Arrhenius, v m rng ra cho cc dung mi khc
nc cng nh cho cc phn ng xy ra trng thi kh.
V d: NH
3
+ HCl NH
4
Cl
- Trong phn ng ny NH
3
l cht nhn H
+
, HCl l cht cho H
+
v do NH
3
l baz, HCl l axit.
b. Thuyt axit-baz ca Lewis:
- Mt thuyt tng qut hn na v axit baz c G.N.Lewis
a ra. Theo thuyt Lewis:
- Axit l cht c kh nng nhn thm mt hay nhiu cp electron
ca cht khc hnh thnh lin kt cng ha tr mi.
- Baz l cht c kh nng nhng mt hay nhiu cp electron
cha lin kt cho cht khc to thnh lin kt cng ha tr
mi.
- Do , mt axit Lewis phi c t nht mt obitan ha tr trng
nhn cp electron, cn mt baz Lewis phi c t nht mt i
electron cha lin kt . T y ta thy nh ngha axit baz ca
Lewis bao hm nh ngha ca Bronsted v Lowry.
V d: H
+
+ NH
3
[H
3
N :H]
+

- Trong phn ng ny NH
3
l mt baz v l cht cho i electron,
H
+
l axit v l cht nhn mt i elcetron.
- Gi tr ca thuyt Lewis v axit-baz l ch gii thch c
cc phn ng axit baz theo quan im ca Bronsted v
Lowry, hn th na cn gii thch c mt s phn ng axit
baz m thuyt Bronsted v Lowry khng gii thch c.
V d : Phn ng gia Trifluorua bor v amoniac:


19
BF
3
+ NH
3
F
3
B-NH
3
- BF
3
l phn t thiu electron, xung quanh nguyn t Bo ch
mi c 6 electron, khi phn ng vi NH
3
, nguyn t Bo s t
c c cu 8 electron. BF
3
l mt cht c i lc mnh vi cc
cht cho electron v do l mt axit Lewis mnh.
- Thuyt axit-baz ca Lewis cng gii thch thnh cng qu trnh
hydrat ha ca ion kim loi.
V d : Al
3+
+ 6H
2
O Al(H
2
O)
6
3+

- Al
3+
l cht nhn electron t nguyn t oxi ca nc l axit v
nc l baz. Rng ra hn na phn ng gia mt oxit axit
v nc, theo thuyt Lewis cng l mt phn ng axit baz,
trong oxit axit l cht nhn mt i electron nn l axit,
nc l cht cho mt i electron nn l baz.
2. nh lut bo ton proton (iu kin proton)
- y l trng hp ring ca LBTN v LBTT p dng
cho cc h axit-baz:
- Pht biu nh lut:
Nu chn mt trng thi no ca dung dch lm trng thi chun
(mc khng) th tng nng proton ca cc cu t mc khng
gii phng ra bng tng nng proton m cc cu t thu vo t
n trng thi cn bng.
Ni cch khc, nng proton trong dung dch lc cn bng bng
hiu gia tng nng proton gii phng ra v tng nng proton
thu vo mc khng.

- Trng thi chun (mc khng) l trng thi ty chn (trng
thi ban u, trng thi gii hn, trng thi cn bng,...).
thun tin cho vic tnh ton, ngi ta thng chn mc
khng l trng thi nng ca cc cu t chim u
th.
V d : Vit biu thc KP cho dung dch KH
2
PO
4
nng C mol/l
Chn mc khng: H
2
PO
4
-
v H
2
O

V d : Vit biu thc KP cho dung dch CH
3
COOH C
1
M v
CH
3
COONa C
2
M.


20

Mc khng: CH
3
COOH v H
2
O

KP:

3. Dung dch ca n axit bazo
a. Axit mnh, Bazo mnh
- Axit mnh (k hiu l HY) l nhng cht trong dung dch c kh
nng nhng hon ton proton cho nc
HY + H
2
O H
3
O
+
+ Y
-
n gin: HY H
+
+ Y
-

- Bazo mnh (k hiu XOH) l nhng cht trong dung dch c kh
nng nhn hon ton proton ca nc:
XOH + H
2
O X
+
(H
2
O) + OH
-
n gin: XOH X
+
+ OH
-

V d: Trn 200ml dung dch HCl c pH=2 vi 300ml dung dch HNO3 c
pH=3.Tnh pH dung dch thu c.
Gii
Dung dch gc: C
0
HCl
= 10
-pH
= 1,0.10
-2
M; C
0
HNO3
= 10
-pH
= 1.10-3M
V
0
HCl
= 200ml; V
0
HNO3
= 300ml
Sau khi trn: C
HCl
=

= 4.10
-3
M
C
HNO3
=

= 6.10
-4
M
HCl H
+
+ Cl
-



21
Vn nu ra: Trong mt bi ton
nh lng th lm sao bit c
tnh mnh yu ca axit ?
HNO
3
H
+
+ NO
3
-

H
2
O H
+
+ OH
-

V C
HCl
, C
HNO3
>> 10
-7
nn c th khng cn k n s phn li ca nc.
KP: [H
+
] = [Cl
-
] +[NO3
-
] = C
HCl
+ C
HNO3
= 4.10
-3
+ 6.10-
4
= 4,6.10
-3

pH= -lg4,6.10
-3
= 2,33
b. Axit yu, Bazo yu (thng c mt trong cc k thi)
- n axit yu (k hiu HA) l nhng cht trong dung dch c kh nng
nhng mt phn proton cho nc v dung dch c phn ng axit.
Xt phn ng:
HA + H
2
O H
3
O
+
+ A
-
p dng nh lut tc dng khi lng vi gi
thuyt dung dch axit l long:
| || |
| | HA
O H A
K
a
+
=
3

- (K
a
l hng s cn bng ca axit) hay ch s hng s phn li axit pK
a
= - lgK
a

l hai i lng c trng cho mnh yu ca cc axit khi K
a
cng ln
hoc pK
a
cng b th axit cng mnh.
- Ngoi ra, mnh yu ca cc axit cng c phn nh qua in li o .
in li o l t s gia s mol n ca cht phn li thnh ion vi tng s
mol n
o
ca cht tan trong dung dch. Hoc o l t s gia nng cht
phn li vi tng nng cht in li. in li t l thun t l thun vi hng
s phn li K vi t l nghch vi nng . i vi n axit HA ta c lin h:
C
K
a
=
o
o
1
2

- Trong dung dch axit HA xy ra cc qu trnh sau:
HA H
+
+ A
-

H
2
O H
+
+ OH
-

- Nu K
a
C
HA
>> K
W
th c th b qua s phn li ca nc tnh thnh phn ca h
theo phng trnh (1)
- Nu K
a
C
HA
~ K
W
th phi k n s phn li ca nc
V d: Tnh pH ca dung dch axit formic 0,1 M bit K
a
= 1,7.10
-4



22

Gii:
Axit formic l axit n chc yu. Gi x l nng l nng H
+
trong dung dch lc
cn bng:
Do K
a
= 1,7.10
-4
>> 10
-14
phn li ca nc khng ng k
0 10 . 7 , 1 10 . 7 , 1 10 . 7 , 1
1 , 0
4 4 2 4
2
= + =

x x
x
x

{




4. Hn hp n axit v n bazo
a. Hn hp axit mnh v axit yu
- Trong dung dch axit mnh HY nng C
1
mol/l v axit yu HA c
nng C
2
mol/l c cc qu trnh sau:
- Phn li ca axit mnh HY: HY H
+
+ Y
-
(1)
- Ion ha ca nc: H
2
O H
+
+ OH
-
K
w
(2)
- Phn li ca axit yu HA: HA H
+
+ A
-
K
a

(3)

- y : C
HA
= C
2
; C
H+
= C
HY
= C
1

- Trong a s trng hp, do c mt ca cc axit HY v HA nn s
phn li ca nc xy ra khng ng k.Ta c th tnh nng ion
H
+
da vo cn bng (3) c k n s c mt ca ion H
+
do HY
phn li ra (1):

- Nu hng s phn li K
HA
tng i b v C
1
, C
2
khng qu nh
th c th coi x C
2
; x C
1
v ta c th nh gi gn ng.

V d:Trn 20,00ml HCl 0,0200M vi 30,00ml dung dch CH
3
COOH 0,150
M tnh pH ca hn hp thu c ?
C
HCl
= 20.0,02/(20+30) = 0,008 (M)


23
C
CH3COOH
= 30.0,15/(20+30) = 0,09 (M)
Cc cn bng xy ra trong dung dch:


Vi x 0,008 ta rt ra phng trnh gn ng:


Gi tr ny nh hn 0,008 khng nhiu .Nu coi x 0,090 th :
x
2
+8.10
-3
x 1,566.10
-6
= 0
tnh c: x = 1,912.10
-4
0,090
Vy x = [CH
3
COO
-
] = 1,912.10
-4
[H
+
] = 0,008 + x = 0,008 + 1,912.10
-4
= 8,19.10
-3

pH = 2,09
b. Hn hp baz mnh v baz yu
- Trong dung dch c qu trnh phn li hon ton ca baz mnh
(XOH) cn bng phn li ca nc, qu trnh proton ha ca baz
yu A
-
:




- C th coi qu trnh phn li ca nc xy ra khng ng k do
s c mt ca nng OH
-
sinh ra t hai qu trnh (4.28) v
(4.30)
- Ta c th nh gi nng OH
-
da vo cn bng (4.30) c tnh
n s c ca nng OH
-
do XOH phn li ra, vi C
OH-
= C
XOH

= C
1
v C
A-
= C
2
.


24





Vi x C
1
; x C
2
ta c gi tr gn ng:


V d :Tnh pH ca dung dch gm NaOH 1,0. 10
-4

M v NaNO
2
0,10 M



Vi x 1,0.10
-4

Vy x = [HNO
2
] = 10
-7,71
[OH
-
] = 1,0.10
-4
+ x = 1,0.10
-4
+ 10
-7,71
= 10
-4
pOH = 4,0 pH = 10
c. Hn hp n axit
- Trong dung dch cha cc n axit HA
1
, HA
2
, HA
3
c cc cn
bng


25

- Trong trng hp: K
a1
C
HA1
>> K
a2
C
HA2
>> K
a3
C
HA3
>> K
w
th c
th tnh nng ion H
+
theo cn bng (4.33) nh i vi dung
dch cha n axit.
- Trong trng hp K
a1
C
HA1
K
a2
C
HA2
K
a3
C
HA3
th biu thc KP
p dng cho h s l:

-
Sau khi t hp cn thit vi ch [H
+
] [OH
-
]
ta c:

- tnh gn ng c th coi
[H
A1
]
C
HA1
= C
1
;
[H
A2
]
C
HA2
= C
2
;

[H
A3
]
C
HA
= C
3
v:

-
kim tra ta tnh li:
[H
A1
] = C
1

1
; [H
A2
] = C
2

2
; [H
A3
] = C
3

3
vi:

V d : Tnh pH ca dung dch CH
3
COOH C
1
= 0,010 M v NH
4
Cl C
2
=
0,100M

Bi v K
a1
C
1
(10
-6,76
) K
a2
C
2
(10
-10,24
) > K
w
nn c th tnh [H
+
] theo
(3):


[H
+
] = 4,17.10
-4
M; pH = 3,38


26
T cn bng (1):
86 , 6 24 , 9
38 , 3 3
10 10 .
10
10 , 0

= = NH << 10
-3,38
, vy s phn li ca
NH
4
+
l khng ng k i vi axit axetic.
d. Hn hp n baz
- Vic tnh cn bng i vi hn hp cc n baz cng tng
t nh hn hp cc n axit.
- Trong dung dch: NaA
1
C
1
M ; NaA
2
C
2
M

Nu K
b1
C
1
K
b2
C
2
K
w
th php tnh c thc hin theo cn
bng (4.40).
Nu K
b1
C
1

K
b2
C
2

K
w

th phi tnh theo KP:
[H
+
] = [OH
-
] - [ HA
1
] - [HA
2
] (4.42)
Thay [HA
1
] = K
a1
-1
[H
+
][A
1
-
] v [HA
2
] = K
a2
-1
[H
+
][A
2
-
] vo (4.42) v khi t hp
cn thit ta rt ra:

Vi gi tr tnh gn ng :

V d : Tnh pH ca dung dch KCN C
1
= 0,100M ( pK
a1
= 9,35 ) v NH
3
C
2
= 0,100M ( pK
a2
= 9, 24 ).

K
b1
C
1

K
b2
C
2
K
w
. p dng (4.44) :


27

e. Hn hp n axit yu v baz lin hp
Xt dung dch n axit HA (C
a
mol/l) v baz lin hp (C
b
mol/l)

Hoc:
Cn bng (4.45) m t ng hin tng khi dung dch c phn ng
axit. Nu pH 7 th c th tnh [H
+
] theo (4.45):

Trong trng hp h << C
a
, C
b
th
b
a
a
C
C
K h = v ta c cng thc gn
ng tnh pH:

Nu pH 7 th cn bng (4.46) m t ng hin tng v c th da
vo tnh pH:

Khi x = [OH
-
] << C
a
, C
b
th [OH
-
] = x =
a
b
b
C
C
K v
a
b
C
C
lg pK pOH
b
=
(4.48)
-
Thay pOH = 14 pH v pK
b
= 14 pK
a
vo (4.48) ta li c
phng trnh tnh pH nh (4.47). phng trnh (4.47) c
gi l phng trnh Henderson Hasselbalch hay c dng
trong cc ti liu sinh hc v sinh ha tnh pH ca cc dung
dch m. Ch rng phng trnh ch ng khi pH khc nhiu
vi 7,0 v khi
[OH
-
], [H
+
] C
a
, C
b
.
- Khi khng th b cn bng phn li ca nc c th tnh gn


28
ng theo phng trnh KP p dng cho h HA (C
a
), A
-
(C
b
):

- Kt qu tnh theo phng trnh gn ng: h
2
+ C
b
h - (K
w
+ K
a
C
a

) = 0 s cho ta [H
+
] = h
V d :Tnh pH ca hn hp NH
4
+
C
1
= 0,050M v NH
3
C
2
= 0070M pK
a
= 9,24.

Tnh gn ng :
38 , 9
050 , 0
070 , 0
lg 9,24 pH = + =
;
pOH = 4,62
[OH
-
] = 10
-4,62

C
a
, C
b
vy gi tr pH tnh c l ng.
5. a axit v a bazo
a. a axit
- Phn t ca cc a axit c kh nng phn li cho n proton (n>1).
Nu n = 2 ta c iaxit, n= 3 ta c triaxit..... S phn li ca cc a
axit din ra theo tng nc. V d, s phn li ca triaxit H
3
A:


- i vi a s cc a axit nht l i vi cc axit v c th K
a1
K
a2
K
a3
...., ngha l s phn li ca a axit xy ra mnh nht nc
u v sau gim dn cc nc tip theo.
- iu ny d hiu v mt phn t khng mang in mt proton d
hn mt anion v anion mt in tch mt proton d nhin tng i
d hn anion hai in tch.....
-
Nu K
a1
K
a2
K
a3
ta c th coi a axit nh mt n axit v tnh
cn bng theo
nc phn li th nht ca axit .
V d:Tnh pH v nng ion S
2-
trong dung dch H
2
S 0,010M
Cc cn bng xy ra trong dung dch:


29


V K
a1
K
a2
K
w
nn cn bng (1) l ch yu

Vi x << 0,010 x= 10
-4,51
<< 0,010
Vy [H
+
] = [HS
-
] = 10
-4,51
pH = 4,51
tnh nng ca ion S
2-
ta dng cn bng 2 c k n nng
cc ion tnh c t trc :

Vi y 10
-4,51

y = K
a2
= 10
-12,9

10
-4,51
,vy [S
2-
] = 10
-12,9

bng
ng gi tr K
a2,
khng ph thuc nng a axit.
b. a baz
- Phn t a baz c kh nng nhn mt s proton .
- Qu trnh proton ha ca a baz l ngc li vi qu trnh
phn li ca a axit tng ng .V vy ng vi iaxit ta c ibaz
,ng vi triaxit ta c tribaz ....v ta c s phn ng sau y:
Phn li ca triaxit Proton ha ca tribaz

Khi K
a1
K
a2
K
a3

th K
a3
-1
K
a2
-1
K
a1
-1
v vy K
b1
K
b2

K
b3
. Nh vy s proton ha nc 1 l chim u th v ta c th
tnh cn bng ca a baz nh mt n baz:


30

V d:Tnh H
+
, HCO
3
-
, pH ca dung dch Na
2
CO
3

0,10M
Cc cn bng xy ra trong dung dch:

K
b1
K
b2
K
w
nn cn bng (2) l ch yu.

Kt qu tnh cho ta :[HCO
3
-
] = [OH
-
] = 4,62.10
-3
; pOH = 2,34 ; pH = 11,66
6. Cc cht in li lng tnh
- Cc cht va c tnh axit (cho proton) va c tnh bazo (thu
proton) c gi l cht in lng tnh. Thuc loi ny gm c:
a. Cc hidroxit ca mt s kim loi (nhm, crom,
km, thic,...)
V d: Pb(OH) PbOH +OH K 10
-4,8
(bazo)
PbOH Pb +OH K 10
-6

Pb(OH) +HO Pb(OH)
3
-
+H
+
Ka 10-
10,8
(axit)
Al(OH) Al
3+
+ 3OH
-
Kb 10
-32,4
(bazo)
Al(OH)
3
H
2
O + H
+
+AlO
2
-
Ka 4.10-13 (axit)
b. Cc aminoaxit:
- L nhng cht in li lng tnh do s c mt ng thi trong
phn t cc nhm amin c tnh bazo v nhm cacboxyl c tnh
axit
V d: axit aminnopropionic (C
3
H
7
O
2
N)


31
c. Cc mui axit:
- L cc mui c to thnh do s trung ha khng hon ton cc
a axit.
V d: NaH
2
PO
4
do H
3
PO
4
b trung ha ht nc 1. Na
2
HPO
4
do axit b trung
ha ht 2 nc u
Tng qut i vi mui NaHA trong dung dch c cn bng:
NaHA Na
+
+HA
-

H
2
O H
+
+OH
-
K
w

HA
-
H
+
+A
2-
K
a2

HA
-
+H
+
H
2
A K
a1
-1

HA va l axit va l bazo v vy mui axit NaHA l hp cht lng tnh
nh gi nh hng pH ca dung dch c th so snh K
a2
vi K
b2
c
t hp t cc cn bng
HA
-
+H
2
O H
2
A +OH
-
K
b2

Nu K
a2
> K
b2
th dung dch c phn ng axit, v ngc li
d. Mui ca axit v bazo yu:
- Cc mui ca axit yu v bazo yu cng l cht in li lng tnh,
v cc ion ca chng cng c kh nng cho proton v thu proton
V d: Dung dch NaHCO
3
c phn ng axit hay bazo? nh gi pH ca
dung dch NaHCO
3
0,02M
NaHCO
3
Na
+
+HCO
3
-
HCO
3
-
H
+
+CO
3
2-
Ka2 10
-10,33
(1)
HCO
3
-
+H
+
H
2
O +CO
2
Ka1
-1
(10
-6,35
)
-1
(2)
H
2
O H
+
+OH
-
Kw 10-
14
(3)
T hp (2) v (3) ta c:
HCO
3-
+H
2
O (H
2
O +CO
2
) +OH
-
kb2 (

32
K
b2
> K
a2
dung dch c phn ng bazo
Kim tra iu kin p dng cng thc
K
w
(10-14) < K
a2
C (2.10-12,33)
K
a1
(10-6,35) << C (2.10-2)
V vy c th p dng:
pH

7. Dung dch m
a. Thnh phn v tnh cht ca dung dch m
- Nhiu phn ng ha hc, sinh ha xy ra thun li pH xc nh.
duy tr pH thch hp khng i, ngi ta phi tin hnh phn
ng ha hc trong mi trng m
- Dung dch m l nhng dung dch c kh nng i chnh sao cho
pH ca h t thay i bt k qu trnh ha hc c gii phng hay
thu nhn hidron.
- Dung dch m l mt hn hp ca mt axit yu HA v bazo lin
hp. V d: CH
3
COOH +CH
3
COO
-;
HCOOH +HCOO
-
....
- Ngoi ra dung dch m c th l dung dch mui axit ca cc a
axit
- Bn cht ca tc dng m th hin r ch: khi thm vo h
mt lng axit mnh th bazo lin hp c mt s thu proton to
ra mt lng tng i nh HA so vi lng HA c sn, do
pH gim khng nhiu v ngc li
V d: nh gi s thay i pH ca hn hp m A gm CH
3
COOH 0,1M
v CH
3
COONa 0,1M
- Khi thm 0,001 mol HCl vo 1 lt dung dch A
- Khi thm 0,001 mol NaOH vo 1 lt dung dch A
Gii
CH
3
COONa Na+ +CH
3
COO
-

H
2
O H+ OH
-
(2) K
w

CH
3
COOH H+ +CH
3
COO
-
K
a

V Ka

>> 10
-7
nn c th coi qu trnh (2) l ch yu
CH
3
COOH H+ +CH
3
COO-
C 0,1 0,1
C -x x


33
[] 0,1 x 0,1 +x

Vi x << 0,1 ta c : x [H
+
] 10-4,76, pH 4,76
a. Khi thm 0,001 mol HCl vo 1 lt dung dch A
Phn ng xy ra:
CH
3
COONa + HCl CH
3
COOH +HCl
Co 0,1 0,001 0,1
C (0,1+0,001) - 0,101
TPGH : CH
3
COOH 0,101 M + CH
3
COO
-
0,099 M
Cn bng: CH
3
COOH H+ +CH
3
COO
-

C 0,101 0,099
[] 0,101 x 0,099 +x

Vi x << 0,099 ta c x [H
+
] , pH 4,75
b. Khi thm 0,001 mol NaOH vo 1 lt dung dch A
Phn ng: CH
3
COOH + NaOH CH
3
COONa +H
2
O
C
o
0,1 0,001 0,1
C 0,1-0,001 - 0.101
TPGH: CH
3
COOH 0,099 M, CH
3
COONa 0,101M
Cn bng: CH
3
COOH H+ +CH
3
COO-
C 0,099 0,101
[] 0,099-x x 0,101+x

X <<0,099 x , pH 4,77
Kt lun: Vic thm HCl l NaOH vo dung dch A ch lm thay i pH
trong gii hn 0,01 n v pH
b. Cng thc tnh gn ng pH ca dung dch m
pH pKa +lg

V d : 85


34
c. m nng
- m nng l s mol bazo mnh hoc axit mnh cn cho vo 1 lt
dung dch m lm tng hay gim pH 1 n v:

Trong : l m nng. db l s mol bazo mnh, da l s mol axit
mnh thm vo.
- T cho thy

- Khi [H+] , [OH- ] << C th c th tnh theo biu thc gn ng:

- m nng s cc i khi nng ca axit v nazo lin hp bng
nhau v c gi tr bng :


S ph thuc m nng vi t s lg Cb/Ca
- Nhn hnh ta thy max khi Ca= Cb; lg

gim d khi
lg

tng hoc gim

- i vi cc dung dch m l mui axit, v d NaHA th m nng
ph thuc vo nng ca mui, t s cc hng s phn li ca a
axit.
V d: i vi NaHA:
NaHA Na
+
+HA
-


35
C
HA- H
+
+A
2-
K
a2

HA
-
+H
+
H
2
A K
a1
-1
HA va ng vai tr lm axit , va l bazo.

Khi Ka2 << Ka1 th:

d. H s pha long:
- phn trn ni rng khi pha long dung dch m th t s

khng thay i do pH ca dung dch m t thay i. iu ny
ch l gn ng, bi v khi pha long th lc ion ca dung dch thay
i, h s hot ca cc cht thay i, do pH cng thay i t
nhiu
- Thc t, biu thc chnh xc nh gi pH ca dung dch m
pH

- c trng hiu ng pha long, ngi ta dng khi nim
pha long pH
1/2
l tng pH km theo s pha long dung dch
u c nng ng lng l Ci bng mt th tch bng nhau
ca nc nguyn cht:
pH
1/2
pH
c1/2
(pH)c
i

- Nu khi pha long pH tng th pH
1/2 > 0 v
ngc li
e. ng dng ca dung dch m:
- Cc dung dch m pH c ng dng rng ri trong thc t
phn tch
- Nhiu phn ng tch phi c thc hin pH xc nh, c
thit lp trong mi trng m thch hp
- Nhiu phn ng sinh ha (phn ng enzim) ph thuc rt nhiu
vo pH. V vy nghin cu ng hc ca cc qu trnh sinh
hc quan trng, ngi ta phi tin hnh trong cc h m c pH
xc inh. Cc h m ny phi tr v mt ha hc, ngha l
khng c phn ng ph
- pha ch dung dch m c max ng vi pH pKa, cn
kim ha hoc axit ha cc cht cho theo t l thch hp
- Mt s h m c khu vc pH rng hn (t 3 -8) c iu ch
t cc dn xut ca 2,6- imetylpiriin
8. Cn bng Hidroxo cc ion kim loi


36
- Trong dung dch nc cc ion kim loi tn ti di dng ion hidrat
ha. Chng l nhng axit c kh nng cho proton v to ra cc
phc hidroxo kim loi. c tnh axit ca ion kim loi ph thuc
vo bn cht ca ion kim loi, vo in tch ca chng.
- Cc ion kim loi kim khng th hin tnh axit v hidroxit ca
chng l nhng bazo rt mnh. Cc ion kim loi kim th l
nhng axit rt yu. Cc ion trng thi oxi ha cao c tnh axit
hn cc ion cng loi trng thi oxi ha thp hn.
- C th m t s to phc hidroxo ca ion Mn+ theo s tng
qut:
M
n+.
mH
2
O [MOH.(m-2H
2
O]
(n-1)+
+ H
3
0
+
*
1

M
n+
.mH
2
O [M(OH)
2
.(m-4)H
2
O]
(n-2)+
+ 2H
3
O
+
*
2

- Vit di dng n gin hn:
M
n+
+ H
2
O MOH
(n-1)+
+ H
+
*
1

M
n+
+ 2H
2
O M(OH)
2
(n-2)+
+ 2H
+
*
2

y, *
1
Kw. *
1 ;
*
2

Kw.
*
2

V d: trong nc ion Cu
2+
to cc phc hidroxo nh sau:
Cu
2+
+ H
2
O CuOH
+
+ H
+

Cu
2+
+ 2H
2
O Cu(OH)
2
+ 2H
+

Cu
2+
+ 3H
2
O Cu(OH)
3
-
+ 3H
+

Cu
2+
+ 4H
2
O Cu(OH)
42-
+ 4H
+
- Khi kim ha dung dch cha cc ion kim loi th xut hin cc
phc hidroxo bc cao cng vi kt ta hidroxit kim loi
- Nhiu ion kim loi a ha tr to c cc phc hidroxo nhiu
nhn
V d:
2Fe3+ +2H2O Fe2(OH)24+ +2H+ lg*22-2,85
2Al3+ +2H2O Al2(OH)24+ +2H+ lg* 22-14,56


37
- Vic nh gi thnh phn cn bng to phc hidroxo ni chung l
kh phc tp. Trong trng hp n gin khi dung dch c mi
trng axit r v c th b qua s to thnh cc phc hidroxo
bc cao th c th tinh gn ng theo LTDKL nh i vi h n
axit thng thng
V d: Tnh pH ca dung dch Fe(ClO
4
)
2
0,01M
Fe(ClO
4
)
2
Fe
2+
+2ClO
4
-

Fe
2+
+ H
2
O FeOH
-
+ H
+
* 10
-5,92

C 10-2
C -x x x
[] 10-2-x x x

- Trong trng hp cc qu trnh to cc phc cht hidroxo xy ra
vi mc tng ng th c th tnh lp theo iu kin proton
nh i vi cc hn hp axit, bazo thng thng
9. Danh php phc cht
a. Mt s khi nim chung v phc cht:
- Cc phc cht c to thnh t cc phn t hay ion, c kh
nng tn ti c lp. Cc phc cht c th trung ha in hoc
tch in m hay dng. Phc cht gm nhm trung tm (hay
cht to phc) lin kt vi phi t bng tng tc tnh in hay
lin kt phi tr. S phi tr ca phc ph thuc bn cht ca ion
trung tm, bn cht ca phi t v quan h nng gia chng.
Mi ion kim loi c mt s phi tr cc i N.
- Hng s to thnh (hng s bn) tng nc k
i
v hng s bn tng
hp
i
| c trng cho qu trnh to phc tng nc v tng hp.
Cc hng s k
i
v
i
| cng ln th phc cng bn
b. Phn ng to phc, tn ring ca cc cht tham gia
phn ng to phc


38
- Phn ng to phc l phn ng kt hp gia cc loi cht ring
bit to thnh ion hoc phn t phc tp c kh nng tn ti
c lp v phn li tr li cc loi cht ban u.
- Tn cc cht phn ng: trung tm phi tr v phi t. Cc trung
tm phi tr thng l cc ion kim loi (ion trung tm); phi t c
th l ion hoc phn t cha cc nhm c kh nng nhng mt
hoc nhiu cp electron to thnh lin kt vi ion trung tm.
c. S phi tr
- S phi t lin kt vi mt nhm trung tm gi l s phi tr ca
phc cht.
d. Phc cng
- Phc cng l mt phc vng cha ion kim loi v thuc th c
cha hai hoc nhiu nhm cho cc cp electron cc v tr to
c cu trc d vng
e. S tng qut ca phn ng to phc gia ion kim
loi v phi t
V d 1:
M + 2L ML
2

Hy biu din: hng s to phc tng nc k
i
hng s to thnh tng
hp
i
| v vit biu thc LTDKL p dng cho mi cn bng. Thit lp biu
thc lin h gia k
i
v
i
|
Li gii:
Hng s to phc tng nc k
i

M + L ML
| |
| || |
1
ML
k
M L
=
ML + L ML
2
| |
| || |
2
2
ML
k
ML L
=
Hng s to thnh tng hp
M + L ML
1 1
k | =
M + 2L ML
2

2 1 2
k k | =
V d 2:


39
. Vit cc qu trnh to phc tng nc v to phc tng hp gia
2
Cd
+
v Br
2
(c ghi km cc hng s cn bng tng ng). Vit biu thc
LBTKL cho cc cn bng xy ra.
Li gii:
Qu trnh to phc tng nc:
2
Cd Br CdBr
+ +
+
1
k
1
2
CdBr
k
Cd Br
+
+
(

=
( (


2
CdBr Br CdBr
+
+
2
k
| |
2
2
CdBr
k
CdBr Br
+
=
( (


2 3
CdBr B CdBr

+ k
3

| |
3
3
2
CdBr
k
CdBr Br

(

=
(


2
3 4
CdBr Br CdBr

+ k
4

2
4
4
3
CdBr
k
CdBr Br

(

=
( (


Qu trnh to phc tng hp:
2
Cd Br CdBr
+ +
+
1
|
1
2
CdBr
Cd Br
|
+
+
(

=
( (


2
2
2 Cd Br CdBr
+
+
2
|
| |
2
2 2
2
CdBr
Cd Br
|
+
=
( (


2
3
3 Cd Br CdBr
+
+
3
|
3
3 3
2
CdBr
Cd Br
|

+
(

=
( (


2 2
4
4 Cd Br CdBr
+
+
4
|
2
4
4 4
2
CdBr
Cd Br
|

+
(

=
( (


V d 3:
Hy m t cc qu trnh xy ra trong dung dch nc ca
( ) ( )
4
2 4
NH Hg CN (


Li gii:
( ) ( ) ( )
2
4 4
2 4 4
2 NH Hg CN NH Hg CN

+
( +


( ) ( )
2
4 3
Hg CN CN Hg CN

+
1
4
k

40
( ) ( )
3 2
Hg CN CN Hg CN

+
1
3
k

( ) ( )
2
Hg CN CN Hg CN
+

+
1
2
k

( ) ( )
+ 2
Hg CN CN Hg CN
+

+
1
1
k

4 3
NH NH H
+ +
+
a
K
2
H O OH H
+
+
10. nh gi cn bng to phc trong dung dch
a. Tnh nng cn bng ca cc phn t ca phc
cht:
- Vic tnh ton cn bng to phc thng rt phc tp do:
o S to phc thng xy ra theo tng nc v trong a s
trng hp cc hng s cn bng tng nc khng chnh
lch nhau nhiu
o Km theo phn ng to phc lun lun xy ra cc qu trnh
ph , c th lin quan n cu t tham gia to phc
o M t y cc cn bng xy ra
o nh gi mc ca cc qu trnh ph
o Nu s to phc xy ra tng nc th c th so snh mc
xy ra
- Nh vy, nh gi cn bng to phc thng i hi phi c
nhng iu kin gn ng hoc phi tin hnh bng nhng
phng php tnh gn ng thch hp. Di y s xt mt s
trng hp tnh gn ng n gin
a.1.Trng hp phi t rt d so vi ion
trung tm
- y l trng hp thng gp trong thc t phn tch. V d: khi
cn xc nh lng vt cc ion kim loi, ngi ta tho72ng dng
rt d thuc th chuyn ha hon ton kim loi thnh phc
cht,...
- Coi phc to thnh c s phi tr cao nht (v C
L
>> C
M
)
- Coi nng cn bng ca phi t bng nng ban u ([L]
C
L
)
a.2.Trng hp ion trung tm rt d so vi
phi t:


41
- Trng hp ny thng gp trong cc th nghim nhn bit cc
ion , khi ch cn cho mt lng t thuc th to thnh phn
ng dng vi kim loi, ngha l phn ng cho tn hiu r
pht hin ion nghin cu.
- y c th chp nhn cc phi t tham gia to phc ht vi
cc ion trung tm to thnh phc c s phi tr thp nht
b. Hng s cn bng iu kin:
b.1. nh ngha
- Hng s cn bng iu kin l biu thc LTDKL, trong t nht
hot ca mt phn t c thay th bng nng cn bng
hoc tng nng cn bng ca cc dng tn ti ca phn t
trong dung dch (tr dng to thnh trong phn ng chnh)
- Hng s cn bng nng Kc l mt trng hp ca hng s
iu kin, trong hot ca mi phn t c thay th bng
nng cn bng. Kc ch hng nh c lc ion khng i, v
vy iu kin y l lc ion c nh
- i vi phn ng to phc thuc loi:
M +nL ML
n

- Hng s to thnh iu kin c biu din nh sau:

y,

l tng nng cc dng phc gia M vi L bao gm ML

n
.
HML
n
, MOHL
n
,...

l tng nng cc dng tn ti ca M khng to phc vi L, v

d, M, MOH, M(OH)
2
,...

bng tng nng cc dng tn ti ca phi t khng to phc

vi M, v d: L, HL, H
2
L,...
Nu vit ta c th nh gi t s

hoc

l phn s ion kim

loi chuyn thnh phc cht trong iu kin cho
b.2. Tnh hng s to thnh iu kin
Ta xt trng hp n gin khi xy ra s to phc chnh gia M v L:


42
M +nL MLn (1)
Cc qu trnh ph:
- To phc hidroxo ca M
M +H2O MOH +H+ *
- Proton ha ca L
L +H HL K
a
-1

- To phc ph ca M vi phi t X
M +mX MXm
x

Biu thc hng s biu din iu kin i vi (1):

y [MLn] [MLn]
[M] [M] + [MOH] + [MXm]
[M] [M](1+ *-1 +
x
[X]m)
[L] [L] + [HL]
[L] [L](1+ K
a
-1
h) [L](

)
T hp ta rt ra:

l phn s nng [M], ch phn ca kim loi

khng to phc vi L, (

l phn s nng ca L, ch
phn ca phi t k to phc vii on kim loi .
Vit di dng n gin:

L
n



43
b.3. Tnh cn bng theo hng s bn iu
kin
- Nu bit hng s iu kin, c th tnh cn bng theo LTDKL
theo cch thng thng
V d: Tnh cn bng trong dung dch Pb 2+ 0,01M v CH3COO- 1M
pH 2
T cn bng:
Pb2+ + CH3COO- PbCH3COO-
C 0,01 1
Co 0,01 x 1-x x
Theo LTDKL:

Vi x<< 1x
Vy

M
[Pb2+] 0,01-x 6,4.10
-3
M
[Pb2+] [Pb2+] . 6,4.10
-3
M
[CH3COO-]
[CH3COOH-][CH3COO-]. CH3COO
-
1,73.10
-3
M
c. nh hng ca pH n s to phc
- Qu trnh to phc thng xy ra km theo s to phc hidroxo
ca ion kim loi v s proton ha ca phi t, v vy phn ng to
phc ph thuc vo pH
- Khi pH tng th mc to phc hidroxo ca ion kim loi tng,
nng ion kim loi gin, kh nng to phc gim v ngc li
- Thng thng mt trong hai yu t chim u th v quyt nh
kh nng to phc, chng hn, pH thp th s to phc gia Ag
+

v NH
3
xy ra rt km


44
- Trong mi trng axit, s to phc gia Fe
3+
v SCN
-
vn xy r
mnh, v ion SCN
-
khng b ion ha. Nhng khi tng pH th phc
khng to thnh c v s to phc hidroxo ca Fe
3+
xy ra rt
mnh
- i lng pH
opt
(gi tr pH ti u) c th c nh gi t biu
thc hng s iu kin
- i vi cc h phc tp th vic tnh pH
opt
i hi phi gii cc
phng trnh bc cao kh cng knh v pHopt thng phi c
xc nh thc nghim
C. TAN V TCH S TAN
I. Tch s tan:
- Tch s tan ca mt cht in li t tan c nh ngha l tch s
cc nng ion t do ca n trong dung dch bo ha mt nhit
nht nh vi cc s tng ng l cc ch s ca ion trong
phn t.
Xt : M
m
A
n (r)
mM
n
(dd)
+ nA
m
(dd)

- Tch s [M]
m
[A]
n
gi l tch s tan, k hiu T hay K
sp
. pT = -logT.
- n gin, khng ghi du in tch.
- Trong dung dch bo ha, mt nhit xc nh, tch s tan l
mt hng s.
- Khi dung dch khng cha ion no khc ngoi ion kt ta, xem
nh nng bng hot .
y ch xt n khi nim nng , xem nh hot bng nng .
[M]
m
[A]
n
< T
o vn tc ha tan > vn tc kt ta. Dung dch cha bo ha.
Khng c kt ta to thnh.Nu thm cht rn M
m
A
n
vo dung
dch, cht rn s tan thm n khi [M]
m
[A]
n
=T.
[M]
m
[A]
n
= T
o vn tc ha tan = vn tc kt ta. Dung dch bo ha. Kt ta
khng c to thm v cng khng tan vo dung dch.
c/ [M]
m
[A]
n
> T
o vn tc ha tan > vn tc kt ta. Dung dch qu bo ha. Kt
ta s tan thm cho n khi [M]
m
[A]
n
= T.
II. tan


45
M
m
A
n (r)
mM
n
(dd)
+ nA
m
(dd)
Gi S l tan ca M
m
A
n
. Ta c C
M
= mS, C
A
= nS.
T = [M]
m
[A]
n
= (mS)
m
.(nS)
n
= m
m
.n
n
.S
m + n
= T
Vy :
.
+
=
m n
m n
T
S
m n
(1)
Lu : c th da vo tch s tan xem coi mt cht no l tan t hay tan
nhiu nhng n ch ng trong trng hp c chung t l hp thc.
V d :
a) Tm tan ca CaSO
4
, bit tch s tan ca n 20
0
C l 6,1.10
-5
.
Gii
CaSO
4
Ca
2+
+ SO
4
2-
S S S (mol/L)
T = [Ca
2+
].[SO
4
2-
] = S.S = S
2

5 3
CaSO
4
S T 6,1.10 7,81.10 mol / L

= = =
b) So snh tan ca AgCl v Ag
2
CrO
4
cng iu kin. Cho bit :
T
AgCl
= 1,08.10
-10
,

=
12
Ag CrO
2 4
T 4,5.10 .
Gii
AgCl : AgCl Ag
+
+ Cl
-


= = =
10 5
AgCl
S T 1,08.10 1,33.10 mol / L
Ag
2
CrO
4:
Ag
2
CrO
4
2Ag
+
+CrO
4
2-

:

+
= = = = = =
12
2 2 2 3 4
3 3
4
T 4,5.10
T [Ag ] [CrO ] (2S) .S 4S S 1,64.10 mol / L
4 4

Ag
2
CrO
4
c tch s tan thp hn AgCl nhng li c tan nhiu hn.
Chng t ta khng da vo tch s tan suy on tan ln hn hay
nh hn khi chng khng c cng bc.
III. Cc yu t nh hng n tan
1. nh hng ion chung


46
- Nu thm ion chung c trong thnh phn kt ta s lm gim
tan.
- Nguyn nhn ny c gii thch l do khi thm ion chung vo,
tch s nng ion s vt qua tch s tan, do , kt ta s tch
ra (khng tan thm) t n trng thi bo ha (tch s nng
ion bng tch s tan).
- Chng minh cng thc :
M
m
A
n
mM + nA
Gi s thm ion A vo vi nng C
A
. Ta c : C
M
= mS, C
A
= nS + C
A

T = [M]
m
[A]
n
= (mS)
m
.(nS + C
A
)
n

thng : C
A
>> S, do : T = m
m
.S
m
.C
A
n

Vy : = m
m n
A
T
S
m .C

2. nh hng lc ion
- Nu trong dung dch c ion d khng phi ion chung, lm tng
tan ca kt ta.
- l nh hng ca h s hot ln tan.
-
m n m n m n m m n m n
M A M A M A
T a .a [M] [A] .f .f m .S .f .f
+
= = =
Thay
m n
M A
f .f bng
m n
f
+

vi f

l h s hot trung bnh.

Do :
(m n)
m n m n
T
S
m .n .f
+
+

=
- Ta thy : S t l nghch vi f

. Khi tng (lc ion), f

gi m. Vy
tan S tng theo lc ion ca dung dch.
3. nh hng ca pH
M
m
A
n
mM + nA
- Ion M
n+
thng l cation kim loi, ion A
m-
thng l anion ca mt
acid. Do , M
n+
c khuynh hng kt hp OH
-
, A
m-
c khuynh
hng kt hp H
+
.


47
- S kt hp ny lm gim nng M
n+
v A
m-
xung, lm cn
bng di sang phi, lm tng tan. nh hng cng mnh,
tan cng tng.
a) Tch s tan iu kin
- T gi l tch s tan iu kin, phn nh nh hng ca cc phn
ng ph ln tan ca kt ta.
- Phn ng ph l cc phn ng gia M v OH
-
hay A vi H
+
.
- Gi [M] l tng nng gm [M] t do v [M] kt hp vi [OH
-
] :
[M] = [M] + [MOH] + + [M(OH)
n
] =
M(OH)
[M]
o

Gi [A] l tng nng gm [A] t do v [A] kt hp vi [H
+
] :
[A] = [A] + [HA] + + [H
n
A] =
A(H)
[A]
o

v i :
2 3
M(OH)
4 4 3 4 3 2
[M] [M] [M]
1 ...
K K .K K .K .K
o = + + + +
2 3
A(H)
4 4 3 4 3 2
[A] [A] [A]
1 ...
K K .K K .K .K
o = + + + +
K
4
, K
3
, l cc gi tr hng s acid hay hng s phn ly ca phc cht.
b) Bin thin ca tan S theo pH
- T khng ch ph thuc vo T m cn ph thuc vo o
M(OH)
v
o
A(H)
.
- pH khng qu cao, phn ng kt hp gia M v OH khng
ng k (tr TH cc cation M c tnh acid qu mnh, vd nh Fe
3+
)
- pH > pK
m
: o
A(H)
~ 1, tan khng ph thuc pH T = T, S = S.
- pH < pK
m
: 1/o
A(H)
tng nhanh theo nng H
+
S tng nhanh
khi pH gim di pK
m
.
c) nh hng nng H
+
ln tan cc cht t tan
- Anion A c th tham gia cc phn ng ph :


48
A
-
+ H
+
HA K
m

HA + H
+
H
2
A K
m 1

.
H
m 1
A + H
+
H
m
A K
1
2
m m m 1 m m 1 1
2
m m m 1 m m 1 1
[H ][A] [H ] [A] [H ][A]
[A] ...
K K .K K .K .K
[H ] [H ] [H ]
[A] 1 ...
K K .K K .K .K
+ + +

+ + +

= + + + +
| |
= + + + +
|
\ .

Gi [A] l nng cc dng tn ti ca A trong dung dch :
[A] = [A] + [HA] + [H
2
A] + + [H
m
A]
2
m m m 1 m m 1 1
2 m
m m m 1 m m 1 1
[H ][A] [H ] [A] [H ][A]
[A] ...
K K .K K .K .K
[H ] [H ] [H ]
[A] 1 ...
K K .K K .K .K
+ + +

+ + +

= + + + +
| |
= + + + +
|
\ .

[A] = [A]o
A(H)

Nu A l anion ca n acid th :
A(H) a
1 [H ]
1
K
+
= +
o
, tan
A(H)
T
S =
o

Xt mt s TH sau :
- Tch s tan M
m
A
n
rt b : mui tan t, nng A phn ly ra rt b,
khng nh hng n pH ca nc. C th ly pH = 7,0.
- Tch s tan M
m
A
n
kh ln : kt ta tan kh nhiu. Phn ng thy
phn A rt ng k. suy ra c ph dung dch, p dng phng
php tnh gn ng.
Cc v d :
Vd1 : Tnh tan Ag
2
S trong nc. Bit Ag
2
S c tch s tan T = 6,3.10
-50
;
H
2
S c pK
a1
= 7, pK
a2
= 13.
Nhn xt : Ag
2
S rt t tan trong nc do T qu b. Xem pH = 7.
Gii


49
T = [Ag
+
]
2
[S
2-
] =
3
S(H)
T
4S =
o

2 7 14
6
13 13 7
S(H) 2 2 1
1 [H ] [H ] 10 10
1 1 2.10
K K .K 10 10 .10
+ +

= + + = + + =
o

Vy T = 6,3.10
-50
.2.10
6
= 12,6.10
-44

44
5
3
12,6.10
S 3,15.10 mol / L
4

= =
Vd2 : Tnh tan MnS trong nc, bit T
MnS
= 10
-11
.
Gii
MnS + H
2
O Mn
2+
+ HS
-
+ OH
-

2 2
2
2
11 14
12 MnS w
13
a2
[Mn ][S ][H ][OH ][HS ]
K [Mn ][HS ][OH ]
[H ][S ]
T .K 10 .10
10
K 10
+ +
+
+

= =
= = =

mt khc, [Mn
2+
] = [HS
-
] = [OH
-
] K = S
3

Vy
12 4 3 3
S K 10 10

= = =
tc [OH
-
] = 10
-4
[H
+
] = 10
-10

tnh ngc kim tra kt qu :
10 20
3
13 13 7
S(H)
1 10 10
1 10
10 10 .10


= + + =
o

d) nh hng ca pH ln tan cc hydroxid
Hidroxid ch c tnh baz:
- Cc hidroxid ny kt ta pH kh cao v tan tr li khi pH kh thp.
- Theo quy c, hidroxid M(OH)
n
bt u kt ta khi nng M bng nng
u C
M
v hidroxid gi l kt ta hon ton khi nng [M] bng 1/1000
nng u.


50

n
n
w
K
[M].[OH] T [M]
[H ]
+
| |
= =
|
\ .
14n
n
1 10
.T
[H ] [M]
+
=

0
M
1
pH 14 (logT logC )
n
= +
Gi pH
1
l pH bt u kt ta ng vi [M] = C
M
:

0
1 M
1
pH 14 (logT logC )
n
= +
Gi pH
2
l ph kt ta hon ton ng vi [M] = C
M
/1000 :

0
2 M
1
pH 14 (logT logC 3)
n
= + +

2 1
3
pH pH
n
= +
Hidroxid lng tnh
Kt ta khi thm baz nhng khi pH kh cao th tan tr li.
V d :
Vd
1
: Tnh khong pH kt ta hidroxid cadmi bit Cd(OH)
2
c T = 10
-14

v C
Cd
0
= 10
-2
M.
Gii

1
2 1
1
pH 14 ( 14 2) 8
2
3
pH pH 8 1,5 9,5
2
= + + =
= + = + =

Vd
2
: Tnh pH Al(OH)
3
tan hon ton khi C
0
Al
= 10
-2
M, Al(OH)
3
c T = 10
-
32,6
.
Gii
p dng cc CT tnh tng t nh trn, tnh c pH
1
= 3,8; pH
2
= 4,8
Al(OH)
3
bt u tan tr li khi [Al(OH)
4
]
-
= 10
-5
M, ng vi 1/1000 C
0
Al


13,9
8,9
5
10
[H ] 10
10

= =


51
Khi [Al(OH)
4
]
-
= 10
-2
M, Al(OH)
3
tan hon ton :

13,9
11,9
2
10
[H ] 10
10

= =
tc pH = 11,9
IV. nh hng ca phn ng to phc ln tan
1. Ligand to phc khc vi anion A
M
m
A
n
mM + nA
Gi s anion tham gia phn ng ph :
m n
T' [M'] [A] =
M( X)
[M]
[M'] =
o

M( X)
o c xem l h s phn nh nh hng ca s to phc
m n
M A m m
m n
M( X) M( X)
[M] [A] T
T' = =
o o

nu anion A ca kt ta cng tham gia phn ng ph, hay gp nht l vi
H
+

m n
m n
M A m n m n
m n
M( X) A(H) M( X) A(H)
[M] [A] T
T' [M'] [A']
. .
= = =
o o o o

Lun lun T > T : lm tng tan
2. Tnh lng tnh ca anion A
- Anion A to vi M kt ta t tan MA, ng thi cho cc phc tan MA
*
,
MA
2
, , MA
n

- Khi d A, do nh hng ion chung, tan kt ta gim xung.
Nhng khi tng A n mt gi tr no , tan li tng ln do s to
phc v kt ta c th tan hon ton
Phn ng kt ta : M + A MA+ (1)
Phn ng to phc : M + A MA
*
(2)


52
MA
*
+ A MA
2
(3)
MA
n-1
+ A MA
n
(4)
Gi [M] l tng nng ca cc dng M. Vy M chnh l tan S.
[M] = S = [M] + [MA*] + [MA
2
] + + [MA
n
]
(1) :
T
[M]
[A]
=
(2) : [MA*] = |
1
[M][A] = |
1
.T
(3) [MA
2
] = [MA*].[A] = |
1
. |
2
.T.[A] = |
1-2
.T.[A]
tng t : [MA
n
] = |
1
. |
2
|
n
.T.[A]
n 1
= |
1 n
.T.[A]
n 1

tan ca kt ta :
n 1
1 1 2 1 n
1
S T .T.[A] ... .T.[A]
[A]

= + | + | + + |
n 1
1 1 2 1 n
1
S T [A] ... [A]
[A]

| |
= + | + | + + |
|
\ .

n 1
n n n 1 n n 1 1
1 1 [A] [A]
hay S T ...
[A] K K .K K .K .K

| |
= + + + +
|
\ .

Nu phc cht to thnh c ch s phi tr 2 :
2 2 1
1 1 [A]
S T
[A] K K .K
| |
= + +
|
\ .
(
*
)
[A] tng i ln th tan tng t l thun vi s tng ca [A].
tan cc tiu khi
dS
0
d[A]
= , pt (
*
) :
2
2 1
dS 1 1
0
d[A] [A] K .K
= + =
Vy nng A ti gi tr c tan cc tiu l :
1 2
[A] K .K =
V d : Tnh tan ca AgCl c T = 10
-10
trong dung dch clorur 1M. Gi s
rng trong dung dch c acid b qua s to phc gia Ag
+
v OH
-
.
Hng s bn ca phc gia Ag
+
v Cl
-
ln lt l |
1
= 10
3,04
, |
2
= 10
2,0
, |
3

= 10
0
, |
1
= 10
0,26
.
Gii
AgCl Ag
+
+ Cl
-
T = 10
-10



53
Ag
+
+ Cl
-
AgCl
*
|
1
= 10
3,04

AgCl + Cl
-
AgCl
2
-
|
2
= 10
2,0

AgCl
2
-
+ Cl
-
AgCl
3
-
|
3
= 10
0

AgCl
3
-
+ Cl
-
AgCl
4
-
|
4
= 10
0,26

2 3
2 3 4
Cl
2 3
1 1 2 1 3 1 4
3,04 10 5,04 10 5,04 10 2 5,30 10 3
6,96
C 1 [Cl ] [AgCl] 2[AgCl ] 3[AgCl ] 4[AgCl ]
[Cl ] T 2 .T.[Cl ] 3 .T.[Cl ] 4 .T.[Cl ]
1 10 .10 [Cl ](1 2.10 .10 ) 3.10 .10 [Cl ] 4.10 .10 .[Cl ]
hay 1-10

= = + + + +
= + | + | + | + |
= + + + +
=
4,96 4,96 2 4,7 3
[Cl ](1 2.10 ) 3.10 .[Cl ] 4.10 .[Cl ]

+ + +

B qua 10
-6,96
v 10
-4,96
so vi 1 :
4,96 2 4,7 3
1 [Cl ] 10 [Cl ] 10 .[Cl ]

= + +
Gii pt, c [Cl
-
] = 1M
tan S :
2 3
AgCl
4 4 3 4 3 2 4 3 2 1
1 1 [Cl ] [Cl ] [Cl ]
S T
[Cl ] K K .K K .K .K K .K .K .K

| |
= + + + +
|
\ .

2 3
AgCl
4 4 3 4 3 2 4 3 2 1
10 3,04 5,04 2 5,04 5,3
5
1 1 [Cl ] [Cl ] [Cl ]
S T
[Cl ] K K .K K .K .K K .K .K .K
1
10 10 1.10 1.10 13.10
1
4,18.10 mol / L

| |
= + + + +
|
\ .
| |
= + + + +
|
\ .
=

tan cc tiu :
3,04 2 2,52
min
[Cl ] 10 .10 10

= =
2,52
10 7
min 2,52 3,04 5,04
1 1 10
S 10 1,75.10 mol / L
10 10 10

| |
= + + =
|
\ .

V. nh hng bi cc yu t vt l
1. Nhit
- Tch s tan thng tra trong cc s tay l hng s mt nhit xc
nh.
- tan thay i theo nhit , c lin quan n hiu ng nhit.
- ha tan ca kt ta ph thuc vo :
o Nng lng mng tinh th ion E
1
.


54
o Nng lng hydrat ha E
2
.
nu E
1
>> E
2
: phn ng ha tan thu nhit
E
2
> E
1
: phn ng ha tan ta nhit
2. Dung mi
- Ngoi s solvat ha ca dung mi, cn phi k n hng s in mi
c. Hng s ny cng ln th hp cht cng d ha tan.
- Do , nc (c = 78) l dung mi tt nht cho phn ln cc cht in
gii (nhng khng tt cho cc hp cht cng ha tr).
- lm kt ta hon ton vi nhng cht tan tng i nhiu trong
nc, cn phi lm gim hng s in mi xung bng cch thm
dung mi hu c nh methanol, ethanol, acetone,)
VI. S kt ta phn on
- S lm kt ta mt hoc hai nhiu ion bng mt ion chung gi l s
kt ta phn on. Hai phng php hay s dng l tch di dng
hidroxid v tch di dng sulfur.
- Tch di dng sulfur
H
2
S l mt thuc th kh quan trng, c cc c tnh sau :
- Sulfur c tan thay i vi khong chnh lch kh xa nhau t MnS
c T
MnS
= 10
-11
n HgS c T
HgS
= 3.10
-52
hay PtS c T
PtS
= 10
-72
. Do
vy, vic la chn pH thch hp lm kt ta mt sulfur hay mt nhm
sulfur l rt d dng.
- Dung dch H
2
S mang tnh acid nn vic tch cc sulfur gn lin vi
pH ca dung dch.
- tan trong dung dch bo ha l 0,1M. H
2
S c pK
1
= 7, pK
2
= 13.
2 2 2
20
1 2
2 2
[S ][H ] [S ][H ] [HS ][H ]
. K .K 10
[H S] [HS ] [H S]
+ + +

= = =
[H
2
S] = 0,1M nn
21
2
10
[S ]
[H ]

+
=


55
Trong dung dch bo ha :
21 21
2
2
[M].10 [M].10
T [M][S] [H ]
[H ] T

+
+
= = =
a. Khong pH kt ta MS
- Gi pH
1
l pH bt u kt ta MS khi [M] = C
M
:
( )
1 M
1
pH 21 logT logC
2
= +
- Gi pH
2
l pH kt ta hon ton MS khi [M] = 1/1000 C
M
:
( )
2 M 1
1
pH 21 logT logC 3 pH 1,5
2
= + + = +
b. Cch chn khong pH :

MS MS

pH
1
pH
2
pH
1
pH
2
- Vng pH kt ta cch xa nhau : nh s trn, TH ny MS kt
ta hon ton trong khi MS cha kt ta, TH ny cho php tch cc
MS chn lc, vng pH tng ng l :
pH
2
< pH < pH
1

- Vng pH kt ta chng ln nhau



MS
MS

pH
1
pH
1
pH
2
pH
2

Khng th tn ti vng pH thch hp tch cc sulfur ra khi nhau.


56
pH
1
< pH < pH
1
: M cha kt ta nhng MS cha kt ta hon ton.
pH
1
< pH < pH
2
: c 2 sulfur u kt ta.
pH
2
< pH < pH
2
: c 2 sulfur u kt ta.
V d : c th tch phn on cc cp ion kim loi sau y c khng ?
- Dung dch cha Zn
2+
v Mn
2+
vi nng u u bng 0,1M.
- Dung dch cha Cd
2+
v Sn
2+
vi nng u u bng 0,1M.
Bit T
ZnS
= 10
-21
, T
MnS
= 10
-11
, T
CdS
= 10
-28
, T
SnS
= 10
-26
.
Gii
1
2
1
2
1
2
1
2
1
pH (21 21 1) 0,5
ZnS: 2
pH 0,5 1,5 2,0
1
pH (21 11 1) 5,5
MnS: 2
pH 5,5 1,5 7,0
1
pH (21 28 1) 3
CdS: 2
pH 3 1,5 1,5
1
pH (21 26 1) 2
SnS: 2
pH 2 1,5 0,5

= + =

`

= + =
)

= + =

`

= + =
)

= + =

`

= + =
)

= + =

`

= + =
)

Trong trng hp u tin, chn vng pH tch l 2 < pH < 5,5
Trng hp th 2, khng th tm c mt pH thch hp tch ri hon
ton Cd
2+
ra khi Sn
2+
.











57