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A. CHUN ACD BAZ
. ACD - BAZ
1. nh ngha acid - baz
a. Thuyt Arhenius:
AH
n
B(OH)
m
H
2
O
H
2
O
*Dm = H
2
O
*Acid n chc
* Baz m chc
* C
H+
=> dd c tnh acid
* C
OH-
=> dd c tnh baz
Td: HCl(k) + NH
3
(k) NH
4
Cl(r)
Khng phi l phn ng acid-baz v khng
c H
2
O.
A
n-
+ nH
+
B
m+
+ mOH
-
b. Thuyt Bronsted:( Thuyt proton)
AH
n
A
n-
+ nH
+
B + mH
+
(BH
m
)
m+
* Dm bt ky
* Acid n chc
* Baz m chc
* AH
n
H
+
=> Tnh acid
* B + H
+
=> Tnh baz
Td: HCl(k) + NH
3
(k) NH
4
Cl(r)
H
+
Acid Baz
Xem pu:
AH + BOH A
-
+ BOH
2
+
H
+
H
+
Acid
1
baz
2
Baz
1
acid
2
AH A
-
+ H
+
;AH/A
-
:cp acid/baz lin hop(1)
BOH
2
+
BOH + H
+
; BOH
2
+
/BOH: Cp acid
/baz lin hop(2)
Trong 1 cp acid/baz lin hop:
Dang acid => dang baz lin hop
Dang acid => dang baz lin hop
2. pH ca dung dch (dung mi l H
2
O)
Trong dd/H
2
O ta lun lun c:
K
n
= C
H+
.C
OH-
= 10
-14
25
o
C
pK
n
= pH + pOH = 14 25
o
C
pK
n
= - lgK
n
; pH = -lgC
H+
; pOH = -lgC
OH-
a. pH ca dd acid - baz
d. pH ca dd acid
* Dd acid manh
AH
n
A
n-
+ nH
+
t
o
C
A
(M) 0 0
t
0 C
A
nC
A
=> C
H+
= nC
A
Ta c C
N
= nC
A
C
H+
= C
N
= nC
A
=> pH = -lgC
H+
= -lg(nC
A
)
* Dd acid yu on chc
AH A
-
+ H
+
t
o
C
A
0 0
t
cb
C
A
- x x x
K
a
=> acid
pH = (pK
a
lgC
A
)
t pK
a
= -lgK
a
K
a
=> pK
a
Td: dd CH
3
COOH(0,1M) ; K
a
= 10
-5
c:
pH = (-lg10
-5
lg0,1) = 3
#0
# 0
K
a
+
=
Xt cp acid/baz lin hop:
AH A
-
+ H
+
A
-
+ H
2
O AH + OH
-
=> K
a
.K
b
= K
n
= 10
-14
25
o
C
K
a
=> K
b
K
a
=> K
b
+
=
#0
# 0
K
a
+
=
=
#
,0 #0
K
b
*Acid yu a chc :Xem 1 acid yu 3 chc:
AH
3
AH
2
-
+ H
+
K
a1
= [AH
2
-
][H
+
]/[AH
3
]
AH
2
-
AH
2-
+ H
+
K
a2
= [AH
2-
][H
+
]/[AH
2
-
]
AH
2-
A
3-
+ H
+
K
a3
= [A
3-
][H
+
]/[AH
2-
]
Thung:K
a1
>>K
a2
>>K
a3
Nu:K
a1
/K
a2
/K
a3
< 10
4
Xem AH
3
nhu acid yu on chc viK
a
=K
a1
=> pH = (pK
a1
lgC
A
)
Td:dd H
3
PO
4
(0,1M);c K
a1
=10
-2,1
,K
a2
=10
-7,2
K
a3
=10
-7,3
:K
a1
/K
a2
/K
a3
=10
5
=>pH= (-lg10
-2,1
lg0,1) = 1,55
)Dd baz: *Dd baz manh
B(OH)
n
B
n+
+ nOH
-
t
o
C
B
0 0
t
0 C
B
nC
B
C
OH-
= nC
B
C
N
= nC
B
=>C
OH-
= C
N
= nC
B
pH = 14 pOH =14 {-lg(nC
B
)}
Td: dd NaOH
0,1N: C
OH-
=C
N
=0,1=>pH=14- (-lg0,1) = 13
0,1M:C
OH-
=C
N
=C
M
=0,1=> pH= 13
Td:dd Ba(OH)
2
0,1N:C
OH-
=C
N
=0,1 => pH = 13
0,1M:C
OH-
=C
N
=2C
M
=0,2=>pH=14-(-lg0,2)=13,33
*Dd baz yu on chc:
BOH B
+
+ OH
-
C
0
= C
B
(M)
pK
b
= -lgK
b
K
b
=>pK
b
, baz
pH = 14 (pK
b
lgC
b
)
Td:dd NH
4
OH(0,1M); pK
b
= 5 c:
pH = 14 (5 lg0,1)=11
* Trung hop dd baz yu a chc
Nu: K
b1
/K
b2
/K
b3
<10
4
, Ta cng xem nhu
1 baz yu c K
b
= K
b1
",0
,0 "
K
b
+
=
b) Dd mui
Mui uoc xem l sn phm ca pu gia
acid vi baz
Acid + baz Mui + H
2
O
m
y
m
y
4 loai mui
d)Dd mui ca acid manh v baz manh:
mAH
n
+ nB(OH)
m
A
m
B
n
+ m.nH
2
O
A
m
B
n
mA
n-
+ nB
m+
A
n-
v B
m+
l gc ca acid, baz manh
=> Khng b thy phn
=> pH = 7
) Dd mui ca acid yu v baz manh:
AH + BOH AB + H
2
O
AB A
-
+ B
+
A
-
+ H
2
O AH + OH
-
pH > 7
pH=(pK
n
+pK
a
+lgC
m
)
y) Dd mui ca acid manh v baz yu:
AB A
-
+ B
+
B
+
+ H
2
O BOH + H
+
pH < 7
pH= (pK
n
-pK
b
-lgC
m
)
) Dd mui ca acid yuv baz yu:
AB A
-
+ B
+
A
-
+ H
2
O AH + OH
-
B
+
+ H
2
O BOH + H
+
pH ty thuc vo su
so snh gia K
a
v K
b
pH=(pK
n
+pK
a
-pK
b
)
* Trung hop mui lung tnh ;
Xem mui AH
2
-
ca acid yu AH
3
AH
3
AH
2
-
+ H
+
AH
2
-
AH
2-
+ H
+
=> [H
+
] = (K
a1
.K
a2
)
1/2
pH = (pK
a1
+ pK
a2
)
pH = (-lgK
a1
lgK
a2
)
>
>
>
.
:
>
> b
0
#0
#0 0
#0
#0 0
K K
a a
+
=
+
+
=
:
>
b
#0
#0 0
K
a
+
=
>
>
>
#0
#0 0
K
a
+
=
Xem mui AH
2-
ca acid yu AH
3
:
AH
2
-
AH
2-
+ H
+
K
a2
AH
2-
A
3-
+ H
+
K
a3
Tuong tu , ta c:
pH = (pK
a2
+ pK
a3
)
Td: H
3
PO
4
cK
a1
=10
-2,1
;K
a2
=10
-7,2
;K
a3
=10
-12,3
Dd H
3
PO
4
(0,1M): pH=(-lg10
-2,1
-lg0,1)=1,55
NaH
2
PO
4
(0,1M) pH=(-lg10
-2,1
-lg10
-7,2
)=4,65
Na
2
HPO
4
(0.1M)
pH=(-lg10
-7,2
-lg10
-12,3
)
= 9,75
c) Dd n:
Dd n l dd c pH thay i khng ng k
khi ta thm vo dd 1 luong nh H
+
hoc OH
-
Dd n {acid(y) v mui ca n vi baz(m)}
(CH
3
COOH + CH
3
COONa)
H
2
O
Dd n acid
CH
3
COONa CH
3
COO
-
+ Na
+
CH
3
COOH CH
3
COO
-
+ H
+
pH < 7
+H
+
=>
+OH
-
;OH
-
+ H
+
H
2
O=>
=> OH
-
pu ht
Vy: pH dd khng i.
/
/
pK p0
m
a
a
lg
=
+
0
/
=>cb=>nghch=> H
+
pu ht
+
0
/
=>cb=> thun
Dd n {baz(y) + mui ca n vi baz(m)}
NH
4
OH
+ NH
4
Cl
H
2
O
Dd dn baz
NH
4
Cl NH
4
+
+ Cl
-
NH
4
OH NH
4
+
+ OH
-
pH > 7
+H
+
:H
+
+ OH
-
H
2
O =>cbthun
=>H
+
pu ht => pH khng i
+ OH
-
=> =>cbnghch =>OH pu ht
=> pH khng i
4 lg / bv
/
/
pK p0
m
b
b
=
,0
/
,0
/
. NGUYN TC:
1. Phn ng:
Acid
Baz
C
0
?
V
0
+ Baz
C
V
Mui + H
2
O
C
0
?
V
0
+ Acid
C
V
Mui + H
2
O
Dd cn chun
c th
manh hoc
yu
Dd chun:
lun manh
2. Cht ch th mu:
Cht ch th mu acid baz thung l acid
hoc baz yu,mu ca dd ph thuc vo pH
ca dd.
Xem cht ch th mu l 1 acid yu Hind:
Hind
H
2
O
H
+
+ ind
-
0in1
in1 0
K
a
+
=
.
in1
0in1
K
0
a
=
+
lg lg
in1
0in1
K p0
a
=
lg
in1
0in1
pK p0
a
=
*[Hind] <10[ind
-
] =>dd c mu ca dang Hind
=> pH pK
a
lg 10 pK
a
- 1
*[ind
-
]<10[Hind] =>dd c mu ca dang nd
-
=> pH < pK
a
lg1/10 < pK
a
+ 1
=> pH = pK
a
1 l khong pH i m ca
cht ch th
pK
a
pK
a
+ 1 pK
a
- 1
Mu ca ind
-
Mu ca Hind
pH
lg
in1
0in1
pK p0
a
=
Cc cht ch th acid baz thung dng:
* Mi c.c.t c 1 gi tr pT xc nh
pT=pK
a
=pH
dd
m tai c.c.t i mu r nht
3.ung cong chun :
xc nh cht ch mu dng trong php
chun .Ta phi v ung biu din pH
ca dd chun , theo th tch dd chun
thm vo dd chun (hoc theo ) cc
thi im khc nhau.
Td: chun dd AH bng dd BOH
AH + BOH AB + H
2
O
C
o
V
o
CV
: phn chun
& /
/&
'
e e
=
. Chun dd acid baz manh
1. Chun dd acid manh
AH
n
+ nNaOH Na
n
A + nH
2
O
* Chua chun :
CV = 0 => = 0
Dd ch c AH
n
( acid manh) => pH
o
= -lgC
o
* 0 < CV
< C
o
V
o
=> 0 < < 1 => Truc t
Dd
AH
n
:
Na
n
A
& &
/& & /
/
+
=
e
e e
b
& &
/& & /
p0
+
e
e e
b
lg
AH
n
+ nNaOH Na
n
A + nH
2
O
*C
o
V
0
= CV => = 1: t
Dd ch c Na
n
A => pH = 7
* C
o
V
o
> CV => > 1: Sau t
Dd gm
NaOH(cn tha)
Na
n
A
pH tnh theo
NaOH
AH
n
+ nNaOH Na
n
A + nH
2
O
AH
n
+ nNaOH Na
n
A + nH
2
O
& &
& / /&
/
.a,0
+
=
e
e e
lg
bv
e
e e
>
& &
& / & /
p0
+
ung cong chun
Td: chun 100ml dd HCl 0,1N bng dd
NaOH 0,1N
HCl + NaOH NaCl + H
2
O
C
o
V
o
CV
* CV = 0 => = 0
pH
o
= - lg0,1 = 1
* C
o
V
o
= CV => = 1
pH
td
= 7
=100ml
b N e
b N e . bee
=
&
t
* V
1
= 99,9ml
= 4,3
* V
2
= 100,1ml
= 9,7
||| N e
b N e . bee
b N e . | N ||
b
= =
'
| N ||
bee
b N e . | N || b N e . bee
lg
b
+
=
p0
eeb N b
b N e . bee
b N e . b N bee
>
= =
'
b N bee
bee
b N e . bee b N e . b N bee
lg
bv
>
+
=
p0
Nhn xt:
* ung cong chun
i xng ua t
* Cc cht ch th c pT
nm trong buc nhy
pH u c th dng
lm cht ch th
* Buc nhy pH cng
ln khi nng cht
cn chun cng ln
2.Chun dd baz manh bng acid manh
B(OH)
n
+ nHCl BCl
n
+ nH
2
O
* CV = 0 => = 0 => Dd ch c B(OH)
n
=> pH
o
= 14 (-lgC
o
)
* CV < C
o
V
o
=> < 1
( truc t)
Dd gm =>pH tnh theo B(OH)
n
B(OH)
n
BCl
n
lg
bv
e
e e
b
& &
& / & /
p0
+
B(OH)
n
+ nHCl BCl
n
+ nH
2
O
* CV = C
o
V
o
=> = 1 (t)
B(OH)
n
+ nHCl BCl
n
+ nH
2
O
Dd ch c BCl
n
=> pH = 7
* CV > C
o
V
o
=> > 1 (sau t)
B(OH)
n
+ nHCl BCl
n
+ nH
2
O
Dd gm
HCl
BCl
n
pH tnh
theo HCl
& &
& / & /
p0
+
e
e e
>
lg
& &
& / & /
/
0/l
+
e
e e
ung cong chun
Td: chun 100ml dd NaOH 0,1N bng dd
HCl 0,1N
NaOH + HCl NaCl + H
2
O
C
o
V
o
CV
* V
o
= 0ml => =0 =>pH
o
= 14-(-lg0,1) = 13
* CV= C
o
V
o
=> =1
pH
td
= 7
= 100ml
* V=99,9ml => = 0,999
= 9,7
b N e
b N e . bee
=
&
t
| N ||
bee
b N e . | N || b N e . bee
lg
bv
b
+
=
p0
* V = 100,1ml => = 1,001
= 4,3
b N bee
bee
b N e . bee b N e . b N bee
lg
>
+
=
p0
V. Chun dd acid- baz yu
1. Ch. dd acid (y) a. Dd acid (y) on chc:
AH + NaOH NaA + H
2
O
*CV = 0 => = 0
Dd(AH)
pH
o
= (pK
a
+lgC
o
)
*CV < C
o
V
o
=><1
Dd
AH:
NaA:
/
/
pK p0
m
a
a
lg
b
=
AH+NaOH NaA +H
2
O
& &
/& & /
/
a
+
=
e
e e
& &
/&
/
m
+
=
e
'
'
pK
/&
/& & /
pK p0
a a
=
=
b
lg lg
e e
b
* CV = C
o
V
o
=> = 1
AH + NaOH NaA + H
2
O
Dd (NaA): :Mui b thy phn
* CV > C
o
V
o
=> > 1
Dd
AH + NaOH NaA + H
2
O
NaOH
NaA
& &
/& & /
/
m
+
=
=
e
e e
4 lg /
e
e e
>
b
& &
/& & /
pK pK p0
a n t
+
=
+ + =
4 lg / bv
e
e e
>
& &
& / /&
p0
+
=
ung cong chun
Td : Chun 100ml dd CH
3
COOH 0,1M
(pK
a
= 4,) bng dd NaOH 0,1M
CH
3
COOH + NaOH CH
3
COONa + H
2
O
* = 0 => pH
o
= (4, - lg0,1)= 2,9
*=1
= 100ml
=,75
* = 0,5
=pK
a
= 4,
w N e
w N e b
lg
w N e
=
pK p0
a
b N e
b N e . bee
=
&
t
4 lg /
bee bee
b N e . bee
N v bv
>
b
+
+ + =
p0
t
* V= 99,9ml => = 0,999
= 7,
* V = 100,1ml => = 1,001
= 9,7
V(ml) pH Ghi ch
0 0 2,9 Chua chun
50 0,5 4,
99,9 0,999 7, n cn truc
100 1 ,75 im tuong uong
100,1 1,001 9,7 n cn sau
4
||| N e
||| N e b
lg /
N v
b
=
p0
4
b N bee bee
b N e . bee b N e . b N bee
lg /
bv
>
+
=
p0
Buc nhy pH p.p
Nhn xt
im tuong uong nm
trong mi trung kim (pH >
)
=
b
lg 4 lg/
b
e e
b b
AH
3
+ NaOH NaH
2
A + H
2
O
& &
/& & /
/
a
+
=
e
e e
& &
/&
/
m
+
=
e
C
0
(M)
* CV = C
o
V
o
=> = 1(t 1)
AH
3
+ NaOH NaH
2
A+H
2
O
* C
o
V
o
< CV < 2C
o
V
o
=> 1 < < 2
Dd
NaH
2
A + NaOH Na
2
HA + H
2
O
NaH
2
A:
Na
2
HA:
Dd n 2
b
>
lg
>
lg
>
e e
e e
> >
=
'
'
pK
& / /&
/& & /
pK p0
a a
4 /
> b
>
b
b a a t
pK pK p0 + =
& &
/& & /
/
a
+
=
e
e e
>
& &
& / /&
/
m
+
=
e
e e
* CV = 2C
o
V
o
=> = 2 (t 2)
NaH
2
A + NaOH Na
2
HA + H
2
O
pH
t2
= (pK
a2
+ pK
a3
)
* 2C
o
V
o
< CV < 3C
o
V
o
=> 2 < < 3
Na
2
HA + NaOH Na
3
A + H
2
O
Dd
Na
2
HA:
Na
3
A:
Dd n 3
>
:
lg
>
:
lg
:
e e
e e
: :
=
'
'
pK
& / /&
/& & /
pK p0
a a
& &
/& & /
/
a
+
=
e
e e
:
& &
& / /&
/
m
+
=
e
e e
>
* CV = 3C
o
V
o
=> = 3 (t 3)
Na
2
HA + NaOH Na
3
A + H
2
O
C
o
V
o
(CV= 3C
o
V
o
) C
o
V
o
Dd (Na
3
A):
pH
t3
= ( pK
n
+ pK
a3
+ lgC
m
)
4 lg/
e
e
: >
b
:
& &
& /
pK pK p0
2
a n t +
+ + =
& &
& /
/
m
+
=
e
e e
AH
3
(C
o
V
o
)
CV=C
o
V
CV=2C
o
V
o
CV=3C
o
V
o
ung cong chun :
Td: chun 50ml dd H
3
PO
4
0,1M
(pK
a1
=2,1; pK
a2
=7,2;pK
a3
=12,3) bng dd
NaOH 0,1M
* K
a1
/K
a2
/K
a3
= 10
5
C th chun tng
chc ring bit
H
3
PO
4
+ NaOH NaH
2
PO
4
+ H
2
O (1)
NaH
2
PO
4
+ NaOH Na
2
HPO
4
+ H
2
O(2)
Na
2
HPO
4
+ NaOH Na
3
PO
4
+ H
2
O (3)
* CV = 0 => = 0 (chua chun )
Dd ( H
3
PO
4
)
=> pH
o
= (pK
a1
-lgC
o
)
= (2,1-lg0,1) = 1,55
* CV= (C
o
V
o
) => = 0,5
=pK
a1
= 2,1
* CV = C
o
V
o
=> = 1
(t 1)
pH
t1
= (pK
a1
+pK
a2
)= (2,1+7,2) = 4,65
* CV= 1,5C
o
V
o
=> = 1,5
=pK
a2
=7,2
w N e
w N e b
lg
b
w N e
=
pK p0
a
b w N b
w N b >
lg
>
w N b
=
pK p0
a
* CV= 2C
o
V
o
=> =2 (t 2)
pH
t2
= (pK
a2
+pK
a3
)= (7,2+12,3) = 9,75
* CV= 2,5C
o
V
o
=> = 2,5
=pK
a3
=12,3
* CV=3C
o
V
o
=> =3 (t 3)
= [14+ 12,3 + lg(0,1/4)] = 12,34
> w N >
w N > :
lg
:
w N >
=
pK p0
a
4
bwe we
we . b N e
lg bv /
: >
b
:
+
+ + =
pK p0
a
Cng thc tnh pH pH Ghi ch
0 pH
o
= (2,1-lg0,1) 1,55 Chua chun
0,5 pH
1/2
= pK
a1
= 2,1 2,1
1 pH
t1
= (pK
a1
+pK
a2
) 3,65 t 1
1,5 pH
3/2
= pK
a2
7,2
2,0 pH
t2
= (pK
a2
+pK
a3
) 9,75 t 2
2,5 pH
5/2
= pK
a3
12,3
3,0 pH
t3
=(14+pk
a3
+lg0,1/4) 12,34 t 3
Metyl da cam
p.p
Metyl da cam
p.p
2. Chun dd baz yu
a. dd baz yu on chc
BOH + HCl BCl + H
2
O
* CV = 0 => = 0
(chua chun )
Dd ( BOH) =>pH
o
=14- (pK
b
lgC
o
)
* 0 < CV < C
o
V
o
=> 0 < < 1
BOH + HCl BCl + H
2
O
Dd
BOH:
BCl:
Dd n baz yu
4
b
lg / bv 4 lg / bv
e e
b
'
'
/&
/& & /
p0
=
=
& &
/& & /
/
b
+
=
e
e e
& &
/&
/
m
+
=
e
* CV = C
o
V
o
=> = 1
BOH + HCl BCl + H
2
O
Dd (BCl)
* CV > C
o
V
o
=> > 1
BOH + HCl BCl + H
2
O
Dd
HCl:
BCl
4 lg /
e
e e
>
b
& &
& /
pK pK p0
b n t +
=
& &
& / /&
p0
+
=
e
e e
>
lg
& &
/& & /
/
m
+
=
=
e
e e
& &
& / /&
/
a
+
=
e
e e
ung cong chun :
Td: Chun 10ml dd NH
4
OH 0,1 M
(pK
b
= 4,) bng dd HCl 0,1 M
NH
4
OH + HCl NH
4
Cl + H
2
O
C
o
V
o
CV
Cng thc tnh pH pH Ghi ch
0,0 pH
o
= 14- (4,-lg0,1) 11,1 Chua c.
0,5 pH
0,5
=14-(pK
b
-lgC
a
/C
m
) 9,2
1,0 pH
t
= [14-4,-lg(0,1)/2] 5,25 t
1,5 pH
2
= -lg[(15.0,1-10.0,1)/(10+15)] 1,6
Nhn xt
im tuong
uong tai min
axit
Cht ch th
thch hop nht
cho php chun
ny l metyl
da cam, metyl
b. Chun dd baz yu a chc:
Cc baz yu a chc thung l cc mui
trung ha ca acid yu a chc
Xem baz yu A
3-
(l mui trung ha ca AH
3
)
Khi ha tan A
3-
vo nuc:
A
3-
+ H
2
O AH
2-
+ OH
-
K
b1
=K
n
/K
a3
AH
2-
+ H
2
O AH
2
-
+ OH
-
K
b2
=K
n
/K
a2
AH
2
-
+ H
2
O AH
3
+ OH
-
K
b3
=K
n
/K
a1
Nu: K
b1
/K
b2
/K
b3
< 10
4
=> C th chun
tng chc ring bit
* A
3-
+ HCl AH
2-
+ Cl
-
* CV = 0 => = 0 (chua chun )
Dd (A
3-
) =>pH
o
= (pK
n
+ pK
a3
+ lgC
o
)
* 0 < CV < C
o
V
o
=> 0 < < 1
A
3-
+ HCl AH
2-
+ Cl
-
Dd
AH
2-
:
A
3-
:
Dd n 1
'
'
pK
/& & /
/&
pK p0
a a
=
b
lg lg
:
e e
: b
& &
/&
/
a
+
=
e
& &
/& & /
/
m
+
=
e
e e
* CV = C
o
V
o
=> = 1 (t 1)
A
3-
+ HCl AH
2-
+ Cl
-
Dd (AH
2-
) => pH
t1
= (pK
a2
+ pK
a3
)
* C
o
V
o
< CV < 2C
o
V
o
=> 1 < < 2
AH
2-
+ HCl AH
2
-
+ Cl
-
Dd
AH
2
-
:
AH
2-
:
Dd n
'
'
pK
/& & /
& / /&
pK p0
a a
=
>
b
lg
>
lg
>
e e
e e
> >
& &
& / /&
/
a
+
=
e
e e
& &
/& & /
/
m
+
=
e
e e
>
* CV = 2C
o
V
o
=> = 2 ( t 2)
AH
2-
+ HCl AH
2
-
+ Cl
-
Dd (AH
2
-
) => pH
t2
= (pK
a1
+ pK
a2
)
* 2C
o
V
o
< CV < 3C
o
V
o
=> 2 < < 3
AH
2
-
+ HCl AH
3
+ Cl
-
Dd
AH
3
:
AH
2
-
:
Dd n
'
'
pK
/& & /
& / /&
pK p0
a a
=
:
>
lg
:
>
lg
b
e e
e e
b :
& &
& / /&
/
a
+
=
e
e e
>
& &
/& & /
/
m
+
=
e
e e
:
* CV = 3C
o
V
o
=> = 3 (t 3)
AH
2
-
+ HCl AH
3
+ Cl
-
Dd (AH
3
)
4 lg /
e
e e
b >
b
:
& &
& /
pK p0
a t
+
=
A
3-
(C
o
V
o
)
CV=C
o
V
o
CV=2C
o
V
o
CV=3C
o
V
o
ung cong chun
Chun 10ml Na
3
PO
4
0,1M bng HCl
0,1M .H
3
PO
4
(K
a1
=10
-21,1
;K
a2
=10
-7,2
;K
a3
=10
-12,3
=> Na
3
PO
4
c: K
b1
=10
-14
/10
-12,3
=10
-1,7
K
b2
=10
-14
/10
-7,2
=10
-6,
;
K
b3
=10
-14
/10
-2,1
=10
-11,9
=> K
b1
/K
b2
/K
b3
=10
-1,7
/10
-6,
/10
-11,9
=10
5
=> C th chun ring tng chc
*=0: Na
3
PO
4
+ HCl Na
2
HPO
4
+ NaCl
=> pH
o
= (14 + 12,3 + lg0,1) = 12,34
* = 0,5
'
'
pK p0
a
=
b
lg
: w N e
: : w N e
w N e b
w N e
lg
a a
pK pK p0 =
=
=12,3
* = 1 => pH
t1
= (7,2+12,3)= 9,75
* =1,5: Na
2
HPO
4
+ HCl NaH
2
PO
4
+ NaCl
'
'
pK p0
a
=
>
b
lg
> w N b
> >
w N b >
b w N b
lg
a a
pK pK =
=
=7,2
* = 2 =>pH
t2
= (2,1+7,2) = 4,65
* = 2,5:
= 2,1
* = 3 => pH
t3
= [2,1 lg(0,1/4)] = 1,5
NaH
2
PO
4
+ HCl H
3
PO
4
+ NaCl
'
'
pK p0
a
=
:
>
lg
b w N >
b b
w N > :
> w N >
lg
a a
pK pK =
=
bv
b:
b>
bb
be
|
z
{
w
v
:
>
b
e
e eNw bNe bNw >Ne >Nw :Ne
. .
.
.
.
.
.
Na
2
HPO
4
NaH
2
PO
4
Metyl da cam
p.p
8
pH
Td: chun 10ml dd Na
2
CO
3
0,1M bng dd
HCl 0,1M. H
2
CO
3
(K
a1
=10
-6,35
;K
a2
=10
-10,33
)
* Na
2
CO
3
c K
b1
=10
-14
/10
-10,33
=10
-3,67
K
b2
= 10
-14
/10
-6,35
= 10
-7,65
=> K
b1
/K
b2
= 10
-3,67
/10
-7,65
= 10
4
=> C th chun tng chc ring bit
Na
2
CO
3
+ HCl NaHCO
3
+ NaCl
C
o
V
o
CV
* =0=>pH
o
= (14 + 10,33 + lg0,1) =11.65
* =0,5=>pH
0,5
= pK
a2
= 10,33
* =1=>pH
t1
= ( 6,35+10,33) = ,34
=> pH
1,5
= pK
a1
= 6,33
* = 2 => pH
t2
= dd bo ha CO
2
/H
2
O= 4
* = 1,5
NaHCO
3
+ HCl CO
2
+ H
2
O + NaCl
t1
p.p
t2
Metyl da cam
V. Chun dd hn hop
1. Dd hn hop nhiu acid
a. dd hn hop acid manh
AH
n
A
n-
+ nH
+
BH
m
B
m+
+ m+
-
C
H+
= nC
a1
+ mC
a2
Tai t cc acid u chun ht
b. dd ( acid manh + acid yu)
Acid manh chun truc:
AH
n
+ nNaOH Na
n
A + nH
2
O
Khi ht acid manh, acid yu mi chun
Td: Chun dd hn hop HCl(C
01
) v
CH
3
COOH(C
02
) bng dd NaOH(C)
HCl + NaOH NaCl + H
2
O (1)
C
o1
V
o
CV
1
CH
3
COOH + NaOH CH
3
COONa +H
2
O(2)
C
o2
V
o
CV
2
Tai t:
=> C(V
1
+V
2
)= CV =(C
o1
+C
o2
)V
o
* Khi va ht HCl: (1) => C
01
V
0
= CV
1
(2)=> C
02
V
0
= CV
2
Chun dd {HCl(C
o1
) + H
3
PO
4
(C
o2
)} bng
dd NaOH(C)
HCl + NaOH NaCl + H
2
O
C
o1
V
o
CV
1
H
3
PO
4
+ NaOH NaH
2
PO
4
+ H
2
O
C
o2
V
o
CV
2
t 1
(metyl
da
cam)
NaH
2
PO
4
+ NaOH Na
2
HPO
4
+ H
2
O
C
o2
V
o
CV
3
t 2
(p.p)
*Metyldacam: CV
t1
=C(V
1
+V
2
)=(C
o1
+C
o2
)V
o
* p.p: CV
t2
=C(V
1
+V
2
+V
3
)=(C
o1
+2C
o2
)V
o
2)Chun dd hn hop baz :
B(OH)
n
B
n+
+ nOH
-
C(OH)
m
C
m+
+ mOH
-
C
OH-
= nC
01
+mC
02
=> Tai t:tt c cc baz u chun
b) Chun dd hn hop baz manh v baz
yu on chc
NaOH + HCl NaCl + H
2
O
NH
4
OH + HCl NH
4
Cl + H
2
O
C
o1
V
o
CV
1
C
o2
V
o
CV
2
t,
(metyl
da cam)
CV = C(V
1
+V
2
) = (C
o1
+ C
o2
)V
o
a) Chun dd hn hop baz manh:
c) Chun dd hn hop baz manh v baz
yu a chc
NaOH + HCl NaCl + H
2
O
Na
2
CO
3
+ HCl NaHCO
3
+NaCl
C
o1
V
o
CV
1
C
o2
V
o
CV
2
t 1,p.p
NaHCO
3
+HCl CO
2
+H
2
O + NaCl
C
o2
V
o
CV
3
t 2,
(metyl
da cam)
*p.p:
C(V
1
+V
2
)=(C
o1
+C
o2
)V
o
*metyl da
cam
C(V
1
+V
2
+V
3
)=(C
o1
+2C
o2
)V
o
V. Sai s ch th:
Acid + Baz Mui + H
2
O
C
o
V
o
CV
t: CV = C
o
V
o
: xc nh t dng ch.ch.th
* Ch.ch.th c pT = pH
t
=> S= 0
* Ch.ch.th c pT < pH
t
=> S < 0 SS(-)
=> dng chun truc t
* Ch.ch.th c pT > pH
t
=> S > 0 SS(+)
=> Dng chun sau t
Cng thc tnh sai s ch th:
CV: luong ch.
C
o
V
o
: luong ban u
* CV < C
o
V
o
=> < 1 => S < 0: SS(-)
* CV > C
o
V
o
=> > 1=> S > 0: SS(+)
be 4 b /
be s
>
>
e e
e e
=
'
& /
& / /&
3
1. Chun acid manh bng baz manh:
AH + NaOH NaA + H
2
O
C
o
V
o
CV
a. pT < pH
t
(CV C
o
V
o
)= -C
H+
(V
o
+V)= -10
-pT
(V
o
+V)
CV = C
o
V
o
=>
pT=pH
c
= -lgC
H+
=> C
H+
= 10
-pT
be s
>
e e
e e
& /
& / /&
3
=
&
&
/
/
e
e
= b b
e
e
+ = +
&
&
/
/
&
& &
/
/ /
e
e e
+
=
+
&
/
& &
/ /
/ /
e
e
e
e
e
+
=
+
be
4 /
be
be
4
/
be
s
>
e
e
>
e e
e
/ /
/
/
& /
&
&
3
p4
p4
0
+
+
=
=
+
b. pT > pH
t
=> > 1 => S > 0;SS(+)
>
be . s
/2&2
/2&2 /&
3
=
pOH= 14 pH= 14 - pT
=>C
OH-
=10
pT-14
Dd (NaOH) tha
be
4 /
be
be
4
/
be
s
>
e
e
bv
>
e e
bv
e
/ /
/
/
& /
&
&
3
p4
p4
,0
+
+
+ =
+ =
2.Chun dd baz (m) bng dd acid (m)
a. pT
c
< pH
t
= 7 => < 1 =>Dd( BOH tha)
B(OH)
n
+ nHCl BCl
n
+ nH
2
O
b. pT
c
> pH
t
= 7 => > 1 => dd(HCl tha)
be
4 /
be
s
>
e
e
bv
/ /
/
/
3
p4
,0
+
be
4 /
be
s
>
e
e
/ /
/
/
3
p4
0
+
+ =
+
3. Chun dd acid yu on chc
AH + NaOH NaA + H
2
O
C
o
V
o
CV
a. pT
c
< pH
t
=> < 1=> dd(AH tha)
:(CV-C
o
V
o
)=-[AH](V
o
+V)
AH A
-
+ H
+
C
o
V
o
=[AH](V
o
+V)+[A
-
](V
o
+V)={([AH]+[A
-
])(V
o
+V)}
be s
>
e e
e e
& /
& / /&
3
=
#0
0 #
K
a
+
=
#0
#
0
K
a
=
+
b
b
+ = +
+
#0
#
0
K
a
#0
#0 #
0
0
K
a
+
=
+
+
+
#0
#
#0
0
K
0
a
+
=
+
+
+
be
4
4/ /
4 /
s
>
e
e
& & # #0
&
&
#0
3
#0
+ +
+
=
be
s
>
# #0
#0
3
#0
+
=
be
be
be
s
> >
0
K
0
K
0
3
a
p4
a
#0
+
=
+
=
+
+
+
b.pT>pH
t
=>>1; Sau t=> dd tha NaOH
be
4 /
be
s
>
e
e
bv
/ /
/
/
3
p4
,0
+
b. pT<pH
t
=> >1; dng chun sau t
=>Dd tha HCl
be
4 /
be
s
>
e
e
/ /
/
/
3
p4
0
+
+ =
+
m.)HQ H *H) )H
S. *hc cht
W
:
89/)Q4
{
: phc cht
cW
>
x<
v
cW
:
89/)Q4
{
H
>
<
:W
;
; 89/)Q4
{
:=
89/)Q4
{
:=
89
:;
; {)Q
=
@A89/)Q4
{
:=
: i"n phc
Y5 gi%a 89
:;
v {)Q
=
: lin 52t ph6i t!
H
>
<
>W
;
; x<
v
>=
x<
v
>=
x
{;
; v<
>=
' : x<
v
>=
5hhng phn l[
Y5 gi%a x
v v< l lin 52t cIng ha t!
x<
v
>=
:5hhng ph3i l i"n phc
W
>
x<
v
: 5hhng ph3i l phc cht
]9# i"n phc tKng Mut:
nY
n
J;
[
n: i"n t!ung t#/cc i"n 5i# l"Ci t?
)W : t!B ln4
Y: ligan+/t!ung hqaN i"n/;4 ha[ i"n/=4
J;N [= : iGn tch ca i"n phc
nY
n
/5hhng chg F 2n iGn tch i"n phc4 l cht
iGn l[ [2uN t!"ng ++ nY
n
iGn l[:
nY
n
n ; nY @A W
5.
@
n
n
$5
5 $
n ; nY nY
n
@A @
n
n
5 $
$5
:h- 5hhng .jn
: h- .jn
@A .W
5.
@ b
DANH PHAP
Cach goi ten phuc chat
+ Goi ten cac ligand truoc theo thu tu
*ligand goc acid ligand phan tu.
+ sau cung goi ten cac ion trung tam kem
theo so la ma viet trong dau ngoac ch hoa tri
cua no(cation).
+ Neu ion phuc la anion thi them duoi at
truoc khi them so la ma
+ Q2u ligan+ l g6c ca aJi+ th& th# uhi < v"
tn g6c aJi+.
p +,: x<
v
>=
: -unat" Q<
:
=
: nit!at".
; Q2u ligan+ l i"n hal"g9n th& th# < v" tn
hal"g9n.
p +,: 8
=
: l"!" )l
=
: cl"!" m!
=
: .!"#" S
=
: i"+"
nIt -6 i"n 5hc gi th9" tn !ing.
p +,: Q<
>
=
: nit!" x
>=
: -un" x
>
>=
:p9-un"
x6 ph6i t! c gi .ng tn chD -6 H[ YCp t t!ac
tn ph6i tD
b : #"n" >: +i :: t!i v : t9t!a w: p9nta
{: h9Ja z: h9pta : "cta | : n"na be: +9ca
p +, :
lg/QH
:
4
>
)l +ia#in" .Cc /S4 cl"!ua
W
:
)"/Q<
>
4
{
: Wali h9Janit!" c".anat /SSS4
II. Nguyen tac chung va phan loai
1. Nguyen tac chung
Dua tren phan ung tao thanh cac phuc tan hay cac
muoi phuc t phan ly
M + nL ML
n
2. Phan loai
a.Phuong phap do bac (chuan do cyanua)
2CN
-
+ Ag
+
lg/)Q4
>
=
e nhan biet diem tuong duong : cho du 1 giot
Ag
+
se lam dung dich van duc do xuat hien ket tua
trang Ag[Ag(CN)
2
]
Ag(CN)
2
-
+ Ag
+
lglg/)Q4
>
b. Phuong phap thuy ngan
Dua tren phan ung tao phuc giua Hg
2+
voi ion
halogenua (Cl
-
, Br
-
, I
-
) va SCN
-
>)l
=
; Hg
>;
Hg)l
>
e nhan biet diem tuong duong dung ch thi:
- Diphenyl Carbazit (pH = 1,5 2,6)
-Diphenyl Carbazon (pH = 2,0 3,5)
-Tai diem tuong duong du mot giot Hg
2+
se tao voi
ch thi mot phuc mau xanh tm
c. Phuong phap Comlpexon
Dua tren p.u tao phuc giua cac ion kim loai voi mot
nhom thuoc thu huu co co ten chung la complexon.
III. Phuong phap chuan do complexon
1. Gioi thieu chung ve cac complexon
Complexon la ten goi chung ch mot nhom cac thuoc
thu huu co la dan xuat cua acid amino polycarboxylic
+ Complexon 1:
Acid Nitrylotriacetic (NTA) hay con goi la Chelaton I
EDTA
ethylenediaminetetraacetic acid H
4
Y
+ Complexon II: (chelaton II)
+ Complexon III
Muoi cua EDTA : Na
2
H
2
Y 2H
2
! "o#i la$ T%ilon &
+ Complexon I'
V du lg
;
; _
v=
lg_
:=
Hg
;>
; _
v=
Hg_
>=
89
;:
; _
v=
89_
=
n
;n
; _
v=
n_
/n=v4
2 ()# ta#o ph)*c cua Coplexon III +,*i ca*c ion -im
loa#i
Trong dung dich nuoc complexon III dien ly
Na
2
H
2
Y 2Na
+
+ H
2
Y
2
H
2
Y
2-
2H
+
+ Y
4-
Me
n+
+ Y
4
MeY
(n 4)
Me
n+
+ H
2
Y
2-
MY
(n-4)
+ 2H
+
V/ da : Phuc calci complexonat (CaY
2
)
* Anh huong cua pH den do ben cua cac complexonat
Me
n+
+ H
2
Y
2
MeY
(n 4)
+ 2H
+
pH cua .un" ./ch : anh huong den cac dang ton tai
cua H
4
Y va su tao phuc hydroxo kim loai.
O pH cang cao th su tao phuc hydroxo kim loai cang
manh => su tao phuc complexonat cang kem.
Nhung pH cang cao th dang Y
4
ton tai cang lon =>
tang kha nang tao phuc complexonat.
Hai yeu to anh huong trai nguoc =>moicomplexonat
ch ben trong mot khoang pH nhat dinh.
+ Cac ion kim loai hoa tri 3,4 bi thuy phan rat manh
cho cac phuc hydroxo ngay ca trong moi truong acid.
=>complexonat cua chung ch ben trong moi truong
rat acid.
V du: FeY
,ScY
de che Al
3+
, Ca
2+
, Fe
3+
khi chuan do
Zn
2+
, Cd
2+
, .
+ Tach cac ion can tro bang cach ket tua phan doan .
. .
3 Chat ch4 th/ dng t%on" ph),n" pha*p chua1n 0o5
complexon
Ch4 th/ ma$u -im loa#i la cac thuoc thu huu co co kha
nang tao voi cac cation kim loai cac phuc co mau va
ban than ch thi cung co mau.
Ch t ch thi mau kim loai cung la nhung da axit hay
da baz huu co yeu thuoc loai thuoc nhuom nen tuy
theo pH cua moi truong ma co the ton tai duoi nhieu
dang khac nhau co mau khac nhau.
mau sac cua ch thi thay doi tuy theo pH cua dung
dich.
'6 .u#: Chuan do truc tiep ion kim loai Me
n+
dung ch
thi mau kim loai HInd. ion kim loai se tao phuc mau
voi ch thi :
Me
n+
+ HInd MeInd
(n1)+
+ H
+
Khi nho tu tu dung dich chuan Trilon B vao:
Me
n+
+ H
2
Y
2-
MeY
(n-4)
+ 2H
+
Khi h t Me
n+
, Trilon B s p v i MeInd
(n-1)+
.
MeInd
(n1)+
+ H
2
Y
2
MeY
(n4)
+ HInd + H
+
(1)
Lam the nao de nhan b/et daac t?
78 0ie1m t),n" 0),n": dung dich chuyen tu mau cua
dang MeInd sang mau cua dang ch thi tu do HInd.
9e1 nha5n %a 0ie1m t),n" 0),n" mo5t ca*ch %o: %a$n"
-Phan ung (1) phai xay ra hoan toan :
phuc cua ch thi va kim loai phai kem ben hon
nhieu so voi phuc complexonat kim loai.
Ch thi phai co do nhay cao
Phuc ch thi voi kim loai cung phai tuong doi
ben Thuong chon ch thi thoa man yeu cau :
10
4
<
MeInd
10
4
MeInd
<
MeY
Chon pH sao cho
Phuc MeY ben
Mau cua phuc MeInd phai khac han mau cua ch
thi tu do HInd.
MOT SO CHAT CH THI THONG DUNG
+ Er/ocrom -T- b/ack ( ET-00 hay NET)( H
3
Ind)
Cong thuc phan tu : C
20
H
13
N
3
O
7
S.
ET 00 thuong dung duoi dang muoi Natri co cong
thuc phan tu C
20
H
12
N
3
O
7
NaS; M = 461,39
Trong dung dich nuoc: H
3
Ind = H
+
+ H
2
Ind
H
2
Ind
HInd
2
Ind
3
Ch thi NET
duoc dung o
pH=7 11
V/ da :
NET duoc dung lam ch thi khi chuan do Mg
2+
,
Zn
2+
, Pb
2+
. . . trong moi truong co pH = 9 10.
iem tuong duong : dung dich chuyen tu mau do
nho sang mau xanh biec.
+ Marex/d : C
8
H
8
N
6
O
6
.H
2
O; M = 302,21.
Murexid la axit 4 nac (H
4
Ind
-
)
H
4
Ind
H
3
Ind
2
H
2
Ind
3
Xac dinh Ca
2+
o pH 12. td ung voi khi dung
dich chuyen tu mau do ( CaInd
3
) sang mau tm
xanh ( ch thi tu do H
2
Ind
3
).
Xac dinh Ni
2+
, Co
2+
, Cu
2+
o pH = 8 9. td ung
voi khi dung dich chuyen tu mau vang ( MeInd
3
)
sang ma tm do ( ch thi tu do H
4
Ind
).
; 9),$n" con" chua1n 0o5 complexon
Ch.d V
0
dd ion M
n+
C
0
(M) bang dd dichTrilon B C(M)
Goi
MY
la hang so ben cua phuc MY.
V(Trilon B) cho vao trong tung thoi diem.
F: muc do dd ion M
n+
da duoc chuan do
e e
.
.
& /
& /
' =
P.U M
n+
+ H
2
Y
2-
MY
(n-4)
+ 2H
+
M + Y MY
+ Khi (V=0, F=0):
pM duoc quyet dinh boi dd M
n+
ban dau.
e
lg) pn =
uong cong chuan do la duong bieu dien pM = f(F)
+ Truoc diem tuong duong ( V
0
C
0
> CV, F<1)
pM duoc quyet dinh boi dung dich M
n+
du
p p
p.) .) p
e
e e
+
= $
p p
p.) .) p
lg pn
e
e e
+
=
+ Tai diem tuong duong (V
0
C
0
= VC, F=1)
pM duoc quyet dinh boi dung
dich phuc MY
>
$
$6
6 $
$6
$6
= =
& &
& /
$6
+
=
e
e e
4 /
e
e e
& &
& / $6
$
$6 $6
+
= =
&7 8 9& :
& /
;
t
$6
p$
e
e e
lg
+ Sau dtd (V
0
C
0
<VC, F>1)
pM duoc quyet dinh boi Trilon B du
p p
.) p p.)
e
e e
+
= 6
4 / 4 4/ /
4 /
e e
e e
e e e
e e e
& / /&
& /
& & & / /&
& & & /
6
$6
$
$6 $6 $6
=
+
+
= =
& &
& /
$6
+
=
e
e e
4 / lg
e e
e e
7 & / 9/& :
& /
; p$
$6
< (ai =o chua1n 0o5
4 /
e
e e
& &
& /
$
$6
+
=
=
4 /
lg
e
e e
& &
& /
; p$
$6
+
4 /
lg
e e
e e
& / /&
& /
; p$
$6
e e >
)ha ch.I
bee b
wNw Ht
we
|e
||
eNw
eN|
eN||
>Nv
:N>
vN:
xs@=bs
beb
bbe
bwe
>ee
bNeb
bNb
bNw
>
{Nz
zNz
Nv
Nz
xs@ ;bs
pMg
T
=5,5
Buoc nhay pMg=4,36,7
(ai =o chua1n 0o5 -hi -et thu*c chua1n 0o5 ta#i pM" > ?
w N w
e
e e
be
4 /
=
+
=
& &
& /
$
$6
4)
=
s > N e bee .
be be
b
bee .
b
xxs
{ z N
_
= = =
% $
$6
pM > <@<
III. Cac phuong phap tien hanh
chuan do complexon
Chuan do truc tiep
Chu n I ngc
)huin I tha[ th2
Chuan do truc tiep: Su dung khi:
+ Phan ung chuan do xay ra nhanh.
+ Chat ch thi doi mau ro rang.
V du:
Chuan do Mg
2+
bang Trilon B o pH = 9 - 10 voi ch
thi NET
Chuan do Ca
2+
bang Trilon B o pH 12 voi ch thi
Murexit
Chuan do Fe
3+
bang Trilon B o pH = 2 - 3 voi ch thi
acid sunfosalisilic
2. Chuan do Nguoc: Su dung khi:
+ Khong co chat ch thi thch hop.
+ P.u giua ion kim loai voi Trilon B xay ra qua cham.
+ O pH ch.d,ion kim loai ket tuaduoi dang hydroxyt
V du : Xac dinh M
1
M
1
+ H
2
Y
2-
(du) M
1
Y + 2H
+
H
2
Y
2-
+ M
2
M
2
Y + 2H
+
Lam the nao de nhan b/et daac d/em cao/?
iem cuoi : chuyen mau tu mau ch thi tu do HInd sang
mau cua phuc MInd.
V du: Xac dinh Pb
2+
o pH = 9 - 10 bang ch.d nguoc
Pb
2+
+ Trilon B (du)
pH : NH
4
Cl + NH
3
; ch thi NET
Trilon B du + Zn
2+
iem cuoi:
HInd
2-
ZnInd
-
xanh biet do nho
3. Chuan do thay the
M
1
+ M
2
Y M
1
Y + M
2
M
2
+ H
2
Y
2-
M
2
Y + 2H
2+
: 10
7
<
M2Y
<<
M1Y
iem cuoi : chuyen mau tu M
2
Ind sang mau Hind
VD: Xac dinh Pb
2+
o pH = 9 -10 bang ch. gian tiep
Pb
2+
+ ZnY
2-
PbY
2-
+ Zn
2+
Zn
2+
+ H
2
Y
2-
ZnY
2-
+ 2H
+
: Ch thi Net
iem cuoi : chuyen tu mau do nho (ZnInd
-
) sang
xanh biec (HInd
2-
)
). )HQ H <]_ Hl WH
1. )ht "J[ ha v cht 5hD:
89
>;
; nn<
v
=
; H
;
89
:;
; nn
>;
; H
>
<
89
>;
89
:;
; 9
nn<
v
=
; w9 ; H
;
nn
>;
; vH
>
<
@A w89
>;
; nn<
v
=
; H
;
w89
:;
; nn
>;
; vH
>
<
89
:;
89
>;
: 89
:;
; 9 89
>;
/cp "J[ ha 5hD b4
nn<
v
=
nn
>;
: nn<
v
=
; w9 ; H
;
nn
>;
; vH
>
<
/cp "J[ ha 5hD
>4
e
<JWh
: iGn th2 "J[ ha 5hD tiu chuin @bnN
p@ bat#N @ >w
"
) ca cp "J[ ha 5hD
2.The oxy hoa khu-Phuong trnh Nerst
The oxy hoa - khu cua mot cap oxy hoa - khu
lien hop cang cao th chat oxy hoa cua cap ay
cang manh va chat khu cang yeu
xem c p: <J ; n9 Wh
e
: iGn th2 B iju5iGn chuin/ bn b at#4
: iGn th2 B iju 5iGn 5hhng chuin
lg
ew| N e
e
Kh
,%
n
> > + =
V DU
'iet Aie1u th)*c the oxB ho*a C -h) cua ca*c
caDp oxB ho*a C -h) =au , 2<
E
C
a. Cu
2+
/Cu
b. MnO
4
-
/ Mn
2+
* Cu
2+
+ 2e Cu
* MnO
4
-
+ 5e + 8H
+
Mn
2+
+ 4H
2
O
lg
>
ew| N e
> e
> >
+
+ =
+ +
/u > >
/u /u /u /u
lg
w
ew| N e
>
v
e
>
v
>
v
+
+
+ =
+ +
$n
0 $n,
> >
$n $n, $n $n,
Pu oxy ha kh xy ra theo chiu no?
Cho 2 cp oxy ha kh:
Ox
1
+ be Kh
1
1
Ox
2
+ ae Kh
2
2
Dang Ox ca cp c
ln hon s pu vi
dang kh ca cp c
nh hon
Td:
1
>
2
=> aOx
1
+ bKh
2
aKh
1
+ bOx
2
Td: Trn ln 2 cp: Cu
2+
/Cu(
1
= + 0,7v) v
Zn
2+
/Zn(
2
= - 0,77v) ta c:
Cu
2+
+ Zn Cu + Zn
2+
II. Nguyen tac chung
aOx
1
+ bKh
2
aKh
1
+ bOx
2
Phan ung phai thoa man yeu cau sau:
-Phai xay ra hoan toan : Kc lon.
- Phan ung xay ra nhanh.
- Khong xay ra phan ung phu.
nd
khoang the chuyen mau cua ch thi
oxy hoa - khu
V.d: Ferroin:phuc cua Fe
2+
voi1,10 phenantrolin
Mau do Mau xanh
E
Ind
= 1,14 0,06 (V)
n
>
Kh 2%
?n1 ?n1
?n1
>
ew| N e
e
=
Mot so chat ch thi oxy hoa khu
Chat ch4 th/
Ma$u
E
E
(') ta#i
pH > E
In.
!x
In.
Nh
Diphe*nBlamin T6m Nh ma$u E@P?
Natri Diphenylamin
Sulfonat
9o t6m Nh ma$u
E@Q;
Acid
Phenylanthranilic
T6m 0o Nh ma$u
F@EQ
Re%%oin Hanh nha#t
9o F@E?
Hanh Me*tBlen
Hanh 0a5m
Nh ma$u
E@<3
2. ng cong chun 9K7SNL
CHTAJN 9!U TV!NL WHEGW CHTAJN
9!U XHY H!GA CNHK8
aKh
1
+ bOx
2
aOx
1
+ bKh
2
<J
b
; .9
Wh
b
lg
ew| N e
b
b
e
b b
Kh
,%
b
> >
Kh ,%
+ =
lg
ew| N e
>
>
e
> >
Kh
,%
a
> >
Kh ,%
+ =
e e
& /
/&
' =
<J
>
; a9 Wh
>
)
e
v ): /)
Q4
Trc t: Tnh the dung dich theo cap Ox
1
/ Kh
1
'
'
b
+ =
b
lg
ew| N e
e
b
lg
ew| N e
b
b
e
b
@h
2%h
b
> > + =
& &
/&
2%h
+
=
e
b
& &
/& & /
@h
+
=
e
e e
b
/& & /
/&
b
> >
+ =
e e
e
b
lg
ew| N e
Ti t: The cua hai caDp (F) +a$ (2) caMn AaYn"
neMn t6nh the .un" ./ch theo ca hai caDp
lg
ew| N e
b
b
e
b
Kh
,%
b
> > + =
lg
ew| N e
>
>
e
>
Kh
,%
a
> > + =
lg ew| N e
>
>
e
>
Kh
,%
a> a> + =
lg ew| N e
b
b
e
b
Kh
,%
b> b> + =
b
.
> b
> b
=
Kh Kh
,% ,%
. a
a .
e
>
e
b
+
+
=
4)
>
aKh
1
+ bOx
2
aOx
1
+ bKh
2
Wh
b
@ <J
>
<J
b
@ Wh
>
Sa t:T6nh the .un" ./ch theo caDp !x
2
ZNh
2
4 b lg/
ew| N e
e
>
+ = '
a
lg
ew| N e
>
>
e
>
@h
2%h
a
> > + =
& &
& / /&
2%h
+
=
e
e e
>
& &
& /
@h
+
=
e
e e
>
e e
e e
e
>
lg
ew| N e
& /
& / /&
a
> >
+ =
V DU
Ve duong chuan do khi chuan do 20 ml dung
dich Fe
2+
0,1N bang dung dich KMnO
4
0,1N trong moi truong H
2
SO
4
co pH = 0 .
4 / zz N e
e
89 89
> :
& =
+ +
4 / wb N b
e
nn nn<
>
v
& =
+
Phan ung chuan do :
MnO
4
-
+ 5Fe
2+
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
* Fe Fe
3+
+ e
MnO
4
-
+ 5e + 8H
+
Mn
2+
+ 4H
2
O
lg
b
ew| N e
>
:
e
> :
+
+
+ =
+ +
'-
'-
> >
'- '-
lg
w
ew| N e
>
v
e
>
v
+
+
+ =
+
$n
0 $n,
> >
$n $n,
pH@e @A H
;
@ bn
lg
w
ew| N e
>
v
e
>
v
+
+ =
+
$n
$n,
> >
$n $n,
V
KMnO
4
F Cong thuc tnh the E E (Volt) Ghi chu
'
'
b
+ =
b
lg
ew| N e
e
b
. a
a .
e
>
e
b
+
+
=
4)
>
4 b lg/
ew| N e
e
>
+ = '
a
4 b lg/
w
ew| N e
e
N
>
v
+ =
+ +
' > >
$n 0 $n,
'
'
> >
'- '-
+ =
+ +
b
lg
b
ew| N e
e
> :
be
eNw eNzz
b eN| eN:
b|N eN|| eN|
b|N| eN||| eN|w x s @ =eNbs
>e b bN:|
>eNe> bNeeb
bNv
xs @ ;eNbs
>eN> bNeb
bNv|
:e bNw bNwb
Ht
Cach chon chat ch thi
Dua vao khoang the doi mau va buoc
nhay
+ Khoang the doi mau nam trong buoc
nhay
Chon chat ch thi nay
Dua vao the E
0
cua chat ch thi
+ Neu E
0
cua chat ch nam trong buoc
nhay Chon chat ch thi nay
+ Neu E
0
E
T
0
: Chon chat ch thi nay
NHAN XET
Truoc va sau dtd E cua dd thay doi cham.
Tai 0,999 < F < 1,001 : E
cua dd tang dot ngot
tao thanh buoc nhay the cua duong chuan do
Trong ch.do, buoc nhay the khong phu thuoc
vao nong do cua dd chuan va dd can ch.do
ma phu thuoc vao do chenh lech the cua 2
cap oxy hoa khu tham gia phan ung ch.do.
Chenh lech the giua 2 cap ohk cang lon th
do chnh xac cua phuong phap ch.d cang cao.
=
V DU
Tnh sai so khi chuan do dung dich
Fe
2+
bang dung dich KMnO
4
0,1N
trong moi truong H
2
SO
4
co nong do ion
H
+
khong doi bang 1 mol/ lit va ket
thuc chuan do o E
c
= 0,87V
4 / zz N e
e
89 89
> :
& =
+ +
4 / wb N b
e
nn nn<
>
v
& =
+
GIAI
p :z N b
{
zz N e wb N b . w
=
+
=
4)
>
E
c
= 0,87V < E
T
= 1,387 V
Ket thuc chuan do truoc diem tuong duong
/
/
'
'
b
+ =
b
lg
ew| N e
e
b
SS = 1,96
V DU
Cr
2
O
7
2-
+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
mau do cam E
0
= 1,33V
e nhan biet diem tuong duong:
Ch thi Diphenylamin
iem cuoi : mau xanh la cay xanh tm dam
Co the dung HCl lam moi truong
4. Phuong phap chuan do I
2
- Na
2
S
2
O
3
Nguyen tac
I
2
+ 2e >S
=
e
@ eNwv p
x
v
<
{
>=
; >9 2S
2
O
3
2-
"
@eNbp
Chuan I
2
+ Na
2
S
2
O
3
I
2
+ 2Na
2
S
2
O
3
2NaI + Na
2
S
4
O
6
Chat ch thi : Ho tinh bot
iem cuoi : mau xanh tm ( 5hong mau
+ I
2
I
2
+ 2Na
2
S
2
O
3
= 2NaI + Na
2
S
4
O
6
Chu y: de tranh su hap phu I
2
tren tua CuI lam tua
co mau vang tham khong xac dinh duoc diem
cuoi.
SCN
-
+ CuI = CuSCN
trang
+ I
-
D. CHUN KT TA
S. )n .ng hqa tan ca cht 5h tan/tch -6 tan4
b. ch -6 tan.
H9# hqa tan cht 5h tan l
#
m
n
/!4 v" nac:
lng o hqa tan !t nhN 0+ !t l"ong:
phn o hqa tan J9# nh +iGn l[ h"n t"n: c c.
l
#
m
n
#l
n=
; nm
#;
: ++ .o" hqa l
#
m
n
H
>
<
Q~ng I ca ++ .o" hqa
gi l I tan/x4 ca l
#
m
n
.
t
e
a e e
t
c.
=x #x nx
W
c
@ l
n=
#
m
n;
n
@ /#x4
#
/nx4
n
@ #
#
n
n
x
/#;n4
W
c
@
l#mn
@ #
#
n
n
x
/#;n4
x
l#mn
@
4 / n m
n m
#m"n
n m
4
+
c
l#mn
k x
l#mn
k
c
)c cht c chng thc tng t nhau/l
#
m
n
)
#
0
n
4
cht n" c k x k
+: lg]
lg]
x
lg]
@ /
lg]
4
b>
/n4
lg)l
lgm!
lgS
be
=be
be
=b:
be
=b{
be
=w
be
={Nw
be
=
c
)c cht c chng thc 5hhng tng ng/l
#
m
n
v )
p
0
M
4N ph3i tnh c, th7
+: lg)l
lg)l
@ be
=be
x
lg)l
@ be
=w
lg
>
)!<
v
@ v.be
=b>
x@
@be
=v
c
*ha l"ong ++tan nhiju hn
c
Hun -hi:H
>
< .a[ hi)/i"n4k 52t ta nhiju hn
:
b >
b>
b >
be . v
>. 0iju 5iGn 7 c 52t ta
a. Hqa tan b lng Jc +nh cht 5h tan l
#
m
n
c
l
#
m
n
( #l
n=
; nm
#;
t
=)
u
e
#)
u
e
n)
u
e
pai )
u
e
@ #
e
n
l#mn
u
l#mn
@ /#)
u
e
4
#
./n)
u
e
4
n
x" -nh
u
l#mn
v
l#mn
: ta c
u
d ++ cha .o" hqa: tan h2t
u
@ ++ .o" hqa: tan h2t
u
A ++ Mu .o" hqa: tan b phnN c /! l4
+: hqa tan be
=:
#"l lg
>
)!<
v
/!4 v" nac ( bl ++
)
u
e
@be
=:
n
u
@/>.be
=:
4
>
./be
=:
4 @v.be
=|
Atan b phn
lg
>
)!<
v
( >lg
;
; )!<
v
>=
.. !In l$n > ++:
++/b4l
n=
)
b
Np
b
; ++/>4m
#;
)
>
Np
>
( ++/:4 c'
xau 5hi t!In l$n nhng chua p:
)
u
b
@
)
u
>
@
#l
n=
; nm
#;
( l
#
m
n
u
l#mn
@ /l
n=
4
#
./m
n;
4
n
-" -nh vai
l#mn
u
d ++ cha .o" hqa cha c
u
@ ++ .o" hqacha c
u
A ++ Mu .o" hqa c
++/:4)
u
b
N)
u
>
Np
:
@p
b
;p
>
4
n
b
@)
b
p
b
@n
u
b
@)
u
b
p
:
n
>
@)
>
p
>
@n
u
>
@)
u
>
p
:
be#l ++/b4 lgQ<
:
/>.be
=:
n4 ;be#l ++/>4 Qa
>
)!<
v
/>.be
=:
n4
)
u
lg;
@ >.be
=:
.be>e @ be
=:
n )
u
)!<v
@ >.be
=:
.be>e @ be
=:
n
u
lg>)!<v
@ /be
=:
4
>
./be
=:
4 @ be
=|
A
lg>)!<v
c
&
& /
:
b b
&
& /
:
> >
*Co hnh thanh ket tua khong khi cho 2l dd 0,2 M
NaOH tac dung voi 1. l dd 0,1 M CaCl
2
?
Cac ion ton tai trong dung dich la Na
+
, OH
-
, Ca
2+
, Cl
-
.
Ch co the hnh thanh ket tua Ca(OH)
2
.
Khi
C
Ca2+
= 0,1/3 M; C
OH-
= (2.210
-1
)
/3 M
T
Ca(OH)2
= .0 x 10
-6
=[0,1.(4.10
-1
)
2
]
/27=[1,6.10
-2
]
/27
T > T
hnh thanh ket tua
>
>
4 /
>
4 t ./ t t
,0 /a
,0 /a
4 / / 4 > =
+ @A )a/<H4
>
>
4 t ./ t t
> +
=
,0 /a
/ / 4
Anh huong cua ion chung den do tan
T = 7.7 x 10
-13
s
2
= T
s = . x 10
-7
lg
;
@ -u
m!
=
@ be
=:
; A be
=:
4 @ be
=:
. A
A @ z.z . be
=be
Tnh do hoa tan cua AgBr trong
a.Nuoc nguyen chat.
b. dung dich 0,001M NaBr.
lgm! lg
;
; m!
=
a4 H
>
< .4 ++ Qam! be
=:
n
Qam! Qa
;
; m!
=
)u
m!=
@ be
=:
n
lgm! lg
;
; m!
=
Anh huong cua pH den do tan
<H
=
@ > @ >. J be
=v
$
p<H @ :Nww @A pH @ beNvw
Tai pH < 10.45
[OH
-
]
OH
-
+ H
+
(aq) H
2
O (l)
=> lam k do tan cua Mg(OH)
2
Tai pH >10.45:[OH
-
] k=> lam do tan cua Mg(OH)
2
c x hiGn +iGn ca i"n chung l# gi3# I tan
c ma 5hhng tan hqa tan t!"ng ++ aJit
c lJit 5hhng tan hqa tan t!"ng ++ .a
]9#: ng/<H4
>
ng
>;
; ><H
=
be . v N b
be . > N b
> b
v
:
bb
:
> b
> 4 /
> 4 /
v
= = =
4
3
,0 $g
,0 $g
ng
>;
@ bNv.be
=v
n
I. NGUYEN TAC VA PHAN LOAI
1. Nguyen tac
Phuong phap chuan do ket tua dua tren phan
ung tao thanh cac hop chat t tan
Cac p.u ch.d ket tua phai thoa man:
P.u ket tua phai x.r hoan toan (T < 10
-10
).
P.u xay ra nhanh.
P.u xay ra theo mot he so ty luong nhat dinh.
P.u phai chon loc, ngha la cac qua trnh phu
nhu cong ket. . . phai khong dang ke.
Phai co ch.ch.th thch hop de xac dinh dtd.
2 WHA]N ^!A_I WHK7NL WHAGW CHTAJN 9!U NE[T TT8A :
a. Phaang phap bac : Dua tren phan ung chuan do :
X
+ Ag
+
AgX
e ch.d (Cl
, Br
, I
) va SCN
bang dd AgNO
3
.
b. Phaang phap thay ngan : su dung dd Hg
2+
de ch.d
(Cl
, I
) theo p.u: 2X
+ Hg
2+
= Hg
2
X
2
(Cl
, Br
, I
hay SCN
) co
nong do C
0
(mol/l) bang dung dich AgNO
3
co nong
do C (mol/l).
Goi V la the tch AgNO
3
cho vao tai moi thoi diem
cua qua trnh chuan do.
F: muc do ion X
-
da duoc chuan do
e e
& /
/&
' =
P.u chuan do : X
+ Ag
+
= AgX
uong ch.d la duong bieu dien su thay
doi pX (hoac pAg) theo the tch cua dd
chuan AgNO
3
them vao : pX = f(V)
Nhi ch)a chua1n 0o5 (V = 0, F = 0)
pX duoc quyet dinh boi dd X
-
co nong
do la C
0
=> pX = lgC
0
.
* T%),*c 0t0 (V
0
C
0
> VC), F<1 :
pX duoc quyet dinh boi dd X
con du :
& &
/& & /
p*
+
=
e
e e
lg
Ta#i 0t0 ('
E
C
E
> 'C@ R>F) : AgX
Ag
+
+ X
-
T
AgX
= [Ag
+
].[X
] =>[Ag
+
] = [X
]
#g*
4 * =
#g* t
p4 p*
>
b
=
(au 0t0 ('
E
C
E
` 'C@ RaF) :
pX duoc quyet dinh boi luong AgNO
3
du
T
AgX
= [Ag
+
].[X
]
+
=
#g
4
*
#g*
& &
& / /&
p4 p*
#g*
+
+ =
e
e e
lg
V/ da : Ve duong chuan do 50 ml dung dich NaCl
0,1M bang dung dich AgNO
3
0,1M.
Biet rang T
AgCl
= 1,0.10
10
Phan ung chuan do:
Ag
+
+ Cl
-
AgCl
=
e
e e
lg
#g*
p4 p*
>
b
=
& &
/ & &/
p4 p*
#g*
+
+ =
e
e e
lg
Sa/ so chaan do
bee .
p )
p ) )p
s
e e
e e
= 33
Tai diem tuong duong
#g*
p4 p*
>
b
=
]
xs
>
e e
e
be .
4 / be
s
& /
/ /
3
p*
*
+
=
Neu -et thu*c , pH a pH
T9
:
Ket thuc chuan do sau diem tuong duong (du dd
AgNO
3
). Phep chuan do mac sai so thua SS% > 0 va
duoc ky hieu +
g l
xxs
>
e
e
p p]
.be
) )
4 / be
s
lg]
/ /
3
#g
+
+ =
+
V/ da : Chuan do 100ml dung dich NaI 0,1M bang
dung dich AgNO
3
co cung nong do.
a) Tnh sai so cua phep chuan do tren neu ket
thuc chuan do o pAg = 11.
b) e sai so chuan do khong vuot qua 0,02%
th phai ket thuc chuan do trong khoang pI bang bao
nhieu ?
Cho biet : T
AgI
= 10
16
Gii
Na + AgNO
3
Ag + NaNO
3
pH
t
= pT = (-lg10
-16
) =
a) pAg
c
= 11 => p
c
= -lg10
-16
11 = 5
p
c
< p
t
=> < 1 ; dd tha Na
10
p-16
= 10
-5
=> p = 11
& /
/ /
3
p?
?
s e> N e be .
be . be
4 be be / be
be .
4 / be
s
>
b b
b b b{
>
e e
e
b{
+ =
+
+ =
+
+ =
+
p? p?
#g
& /
/ /
3
; CAGC WHK7NL WHAGW HAGC 9INH 9IEJM CT![I TV!NL
WHK7NL WHAGW 9! &A_C
Nguyen tac cua phuong phap la them vao dung dich
chuan do mot ion co kha nang tao voi ion Ag
+
mot
ket tua co mau dam o gan diem tuong duong.
a. Phaang phap Mohr
Mohr de nghi dung ion CrO
4
2-
lam ch thi
2Ag
+
+ CrO
4
2-
Ag
2
CrO
4
(do gach)
|w N bb
be
v >
=
/r, #g
4
Qua trnh chuan do ion halogenur X
theo phuong
phap Mohr xay ra nhu sau :
X
+ Ag
+
AgX
C
o
V
o
CV
Khi vua du mot giot ion Ag+ th :
CrO
4
2-
+ 2Ag
+
Ag
2
CrO
4
(do gach)
Khi thay hon hop chuyen tu mau vang sang mau hoi
do cua ket tua Ag
2
CrO
4
th ngung chuan do.
T i t: C
o
V
o
= CV
A Precipitation Titration
Dd mu
vng
dd
AgNO
3
Kt ta
t!ng
Ag"#
tong dd
mu
vng.
Kh$ "#
%
&
' ht
Kt ta
Ag
2
"O
(
mu )
g*ch.
Pp Mohr duoc dung de dinh luong Cl
, Br
-
nhung khong dung de dinh l ng I
, SCN
v
AgI va AgSCN hap phu manh ion do do se
quan sat thay su chuyen mau truoc t rat xa,
phep chuan do mac sai so lon.
*.* n"h cn ti2n ti2n hnh t!"ng #hi t!rng c
pH @ {Nw Nw v&:
c !"ng #hi t!rng aJit th& n~ng I i"n gi3#
nhiju +" tha# gia ph3n ng:
H
;
; )!<
v
>=
H)!<
v
=
0" - Ki #u J3[ !a B -au v Ja t/-ai -6
lan4
c Qgc lCi t!"ng #hi t!rng 5ij# #Cnh - J3[
!a ph3n ng:
>lg
;
; ><H
=
>lg<H
>lg<H lg
>
</ 9n4 ; H
>
<
b. Phaang phap Fajans
Dua tren kha nang thay doi mau cua 1 loai
ch thi ac biet khi hap phu len be mat ket tua
tch dien(ct hap phu).
Ch thi hap phu la cac acid hoac baz huu co
yeu
HInd H
+
+ Ind
Hay IndOH Ind
+
+ OH
* Sau dt tao he keo duong AgCl/AgNO
3
{ }
+
: :
4 / N 4 / %., ., % n n#g m#g/l
Hat ket tua tch dien duong nen hap phu anion
Ind
-
do do hat ket tua co mau.
)h.I )l
=
.ng lg
;
vai ch th hp ph, HSn+
lg
;
; )l
=
lg)l
c !ac t tC" hG 59" #:
+ +
Ag
2
O
(den)
+ H
2
O
tot nhat la chuan do o pH = 6,5 10.
8lu"!9-c9in +ung t!"ng chuin I cc i"n )l
=
Nm!
=
N
S
=.
t ++ - chu[7n t? #u l,c / c nh hunh
Muang4 -ang #u h~ng/52t ta h~ng t!"ng ++
5hhng #u4.
= <9-9in +1ng 7 chuin I cc i"n:m!
=
N S
=
N x)Q
=
B pH @ > be. t: ++ chu[7n t? #u 5,c
-ang #u th#.
C. Phaang phap Vo/hard
Ngayen tac : Dua vao phan ung chuan do ion Ag
+
bang ion SCN
voi ion Fe
3+
lam ch thi :
Ag
+
+ SCN
AgSCN
(trang)
Khi do du 1 giot SCN
FeSCN
2+
*Cho mot luong du, chnh xac dd AgNO
3
vao dd X
(Cl
, Br
, I
) : Ag
+
+ X
AgX
chuan do Ag
+
du bang dung dich chuan SCN
voi
Fe
3+
lam ch thi nhu tren :
Ag
+
+ SCN
AgSCN
2Fe
2+
+ I
2
Khi xac dinh Cl
AgSCN
+ Cl