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CHUONG 1

AI CUONG VE HOA PHAN TCH


Ha phn tch:
p.t nh tnh:
p.t nh lng:
Ha phn tch: nghin cu cc phng php phn
tch nh tnh v nh lng thnh phn ha hc
ca cc cht.
!"ng #$u p.t c
nh%ng cht g&'
H# lng cc
cht t!"ng #$u
Khi nghin cu thnh phn mt cht cha
bit:phn tch nh tnh trc, phn tch nh
lng c tin hnh au!

CAC GIAI OAN TIEN HANH PHAN TCH
( Lay mau dai dien.
( Bao quan mau phan tch.
( Tao mau duoi dang thch hop.
( Tien hanh phan tch dinh tnh.
( Lua chon qui trnh phan tch dinh luong.
( Co lap hoac loai bo bot mot so cau tu can
tro.
( Tien hanh dinh luong.
( Tnh toan ket qua.

Ham luong Ky thuat phan tch
1 - 10mg
Phan tch dung cu
10
-3
mg
10- 100mg
Phan tch hoa hoc
> 100mg
)c phng php phn tch nh lng
*hn tch ha hc v phn tch +,ng c,
:vi lng
:-iu vi lng
:.n vi lng
:a lng

*.* ha hc
/01ng thi2t . n gi3n4
** 5h6i lng
** th7 tch
** 5h6i lng
0: *hn tch h# lng 89
:;
t!"ng #$u
89
:;
; <H
=
89/<H4
:
89
>
<
:
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>
<
:
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:;
** th7 tch
/)c cht p B
t!Cng thi ++4
+ Chuan do acid - bazo
+ Chuan do ph c ch t
+ Chuan do oxy ha = 5hD.
+ Chuan do k t t a.

** +,ng c,:
** vEt lF:
** ha lF
n hiGu vEt lF
HI pht JC
*hK pht JC
LL
** MuangN pp iGn
** hp thu phn tD
** iGn th2 /* ha hc ;
tn hiGu vEt lF4

)HOPQR SS
*HOPQR *HT* *HUQ
V)H WHXS YOZQR

S. Qgu[n t\c:
] /++4
^
_
lc
!DaN -[
nung
` /+Cng cn4
/+Cng 52t ta4
SS. )c [u cu 6i vai +Cng 52t ta v +Cng cn
b. 0Cng 52t ta:
c
_
d be
=be
Ntinh 5hi2t v +f lc
c _ ` +f +ng v h"n t"n
>. 0Cng cn:
c c thnh phn gng vai cthh Jc nh.
c Whhng /hgt i#N hp th, )<
>
N . phn h[4.
c #
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A #
ng.t6 cn phn tch
cng nhiju @A I chnh Jc
k

SSS. )ch tnh 52t Mu3 t!"ng phn tch 5h6i lng
b. HG -6 chu[7n W: Q2u +Cng cn:l
#
m
n
n m
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$
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K
.
=
n
l
: ngu[n tD ga# ca cht
cn phn tch l
>. HG -6 pha l"ong:
%
m
&
&
' =
cp
#
:h7 tch ++ /]4 -au 5hi a ga#
cht cn phn tch hqa tan.
cp
J
: h7 tch ++/]4 l[ 9# phn
tch
!rng hp tnh s l +ai +Cng l
J
0
[
t? l
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m
n
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m
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$
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n m
( %
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) #
. =

:. nh 52t Mu3:
bee . . s
a
b
K * =
a: lng cn .an u ca
#$u cha ] cn phn tch
.: 5h6i lng +Cng cn.
bee . . s
%
m
&
&
K * =
Q2u 9# a ga# hqa tan v nh #c 2n p
#
:
c H7 Jc nh I i# ca #$u:
bee .
t
. s
a
a a
m +

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)HOPQR SSS
*HUQ V)H H} V)H
l ; m )
l v m ju B t!Cng thi +ung +ch
0ung +ch l c n~ng I )
e
cha
.i2t
0ung +ch m c n~ng ) o .i2t
01ng ++ m 7 Jc nh n~ng ++ l :
php chuin I.
0+ l: ++ cn chuin I.
0+ m: ++ chuin.
0+ cn
chuin
I
0+
chuin
S. Qgu[n t\c
SQ ^QH )HQ H
Y[ chnh Jc p
e
#l ++ l /c
n~ng I )
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Q
4 ch" v" .&nh
/9!l9n4
mi2t : h7 tch ++ #$u
Whhng .i2t: n~ng I ++ #$u
u t!&nh nh t? t? ++ m t? mu!9t v" ++ l :
Mu t!&nh chuin I /nh phn4
mi2t:Q~ng I ca ++ m.
h7 tch ++ m tiu t6n.
00 m : ++ chuin
Hi7# tng ng ca Mu
t!&nh : thri i7# # m tc
+,ng v?a h2t vai l
QhEn .i2t i7# tng
ng: )ht ch th
Hi7# cu6i ca Mu t!&nh
chuin I: thri i7# 52t
thgc Mu t!&nh chuin I.
)ht ch thi :nh%ng cht c
5h3 nng tha[ Ki #u -\c
ha[ tC" #It 52t ta c #u
B gn i7# tng ng
HS}n OPQR HOPQR
)ht chuin tc +,ng
v?a h2t vai cht cn
phn tch
hri i7# 52t thgc
Mu t!&nh chun I
x 5hc nhau gi%a i7# tng ng v i7#
cu6i .
xai -6 chuin I: S = V
c
V
t
i # tng ng Hi7# cu6i x @ e
hc t2 : Hi7# cu6i Hi7# tng ng -ai -6
thi2ux/=4 -ai -6 th?ax/;4
0S}n )XS
II. _ ) )l *HQ QR 0QR ^<QR *HUQ
V)H H} V)H

)ht cn chuin I ph3i ph3n ng vai


thu6c thD th9" #It phng t!&nh ph3n
ng Jc nh.

*h3n ng ph3i J3[ !a nhanh N h"n t"n.

hu6c thD ch ph3n ng vai cht cn


chuin I # thhi.

*h3i c cht ch th Jc nh i7# tng


ng
0a v" .3n cht ca ph3n ng chuin I :

:.b. *hng php t!ung hqa /aJit=.a 4


H
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H
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:.>. *hng php tC" phc


lg
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=
c:.:: *hng php "J[ ha 5hD
a<Jh
b
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:.v. *hng php 52t ta


l ; m )


SSS. *HUQ Y<S )T) *HOPQR *HT* *
Sp.)T)H VQH W l ^<QR *HUQ V)H H} V)H
h9" nh luEt ng lng : p
e
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b. )huin I t!c ti2p.
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p +,: nh n~ng I v 5h6i lng ca Qa<HN


.i2t !ng 5hi chuin I >e#l +ung +ch Qa<HN
ph3i +1ng h2t >>Nzw#l +ung +ch H)l eNbe{Q.
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xD +,ng 5hi:

Hi7# cu6i ca chuin I ngc ! hn +i7#


cu6i ca chuin I t!c ti2p.

0ung +ch chuin ch" + .an u ph3i ph3n


ng h"n t"n vai cht phn tch.
man u: Hl ; m<H ml ; H
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pu
b
xau ch" lng chuin + ph3n ng vai #It
cht chuin th hai th9" ph3n ng:
m<H ; H] m] ; H
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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

Acid cng manh => baz lin


hop cng yu; v nguoc lai





c
,0 0
#
,0 #0
#0
# 0
K K
b a
+
=

+
=


#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 >
)

Buc nhy ca ung


chun ngn hon nhiu so
vi khi chun axit(m)
bng baz(m)

Nng cc cht cng ln


th buc nhy cng di

Cht ch th thch hop l PP



b. Dd acid yu a chc:
Td: xem acid yu AH
3
: Nu: K
a1
/K
a2
/K
a3
< 10
4
C th chun ring tng chc
AH
3
+ NaOH NaH
2
A + H
2
O
* CV = 0 => = 0 => pH
o
= (pK
a1
lg C
o
)
* 0 < CV < C
o
V
o
=> 0 < < 1 (truc t 1)
Dd
AH
3
:
NaH
2
A:
Dd n 1
'
'
pK
/&
/& & /
pK p0
a a

=

=
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
+

4.Chun baz yu on chc


BOH + HCl BCl + H
2
O
C
o
V
o
CV
a. pT>pH
t
=> <1; dng chun truc t
=> Dd tha baz yu
be

be
be


s
>
bv
>
,0
K
,0
K
,0
3
b
p4
b
,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

. . . ben trong khoang pH = 1 2.


+ Cac ion kim loai nhom B co hoa tri 2 va Al
3+
bi
th y phan yeu hon cac ion hoa tri 3, 4 nen phuc cua
chung ben o pH cao hon mot t : pH = 2 5.
+ Cac complexonat kim loai nhom IIA lai ben trong
moi truong kiem hon. Cac phuc nay ben trong
khoang pH = 8 10.

V/ da : H7 ch. *.
>+
bang ph.ph complexon, can tien
hanh ch. trong moi truong kiem co pH = 9 10.
Trong m.t nay Pb
2+
Pb(OH)
2
, do do can cho vao
dd chat tao phuc phu voi Pb
2+
nhu muoi tartrat
(KHC
4
H
4
O
6
) hay Trietanolamin
(N(CH
2
CH
2
OH)
3
) . . .
* 0e1 n"a2n n")$a anh h),n" cua ca*c ion can t%,
+ Chon pH thch hop sao cho EDTA ch tao phuc
ben voi ion kim loai can chuan do.
V/ da : ch. ring ion Ca
2+
khi c mt Mg
2+
,
Tien hanh o moi truong kiem manh (pH = 12).
Mg
2+
se ket tua duoi dang Mg(OH)
2
Ca
2+
ton tai o dang CaY
2
.

+ Dung chat che thch hop de tao phuc voi cac ion
can tro
V/ da : Dung CN

de che cac ion Cu


2+
, Co
2+
, Ni
2+
khi
chuan do Ca
2+
, Mg
2+
trong hon hop co chua cac ion
tren.
Dung F

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
+
=

+ Neu Ket thuc chuan do tai pM > pM


T
: Ket thuc
chuan do sau dtd. Thua dung dich chuan Trilon B
gay sai so thua :
_
xxs
.bee
b
xs
<$= :
;
$6
6
+ Neu chuan do tai pM < pM
T
: Ket thuc chuan do
truoc dtd. Phep chuan do mac sai so thieu
+ n
n
xxs
bee
4 /
s
e
e
/ /
/ 8 / $
; 3
8 n
$


'6 .u#: Chuan do 100ml dung dich Mg
2+
0,1M bang
dung dich Trilon B 0,1M. Biet
MgY
= 10
8,7.
a)Ve duong cong chuan do
b)Tnh sai so cua phep chuan do neu ket thuc chuan
do o pM =6
Phan ung chuan do:
Mg + Y = MgY
Tai diem tuong duong V
Y
chuan do het
ml ; ; & ; &
t 6
bee
eNb
eNb.bee

p
_
Cng thc tnh pH pM Ghi ch
e
lg) pn =
p p
p.) .) p
lg pn
e
e e
+

=
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)

+ Neu Ket thuc chuan do tai pM=6 > pM


T=5,5
: Ket
thuc chuan do sau diem tuong duong. Thua dung
dich chuan Trilon B gay sai so thua :
bee .

b
xxs
_
$
$6

=
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

@A p "J[ ha 5hD ph3i c > cp "J[ ha 5hD t!In


l$n v" nhau.
S. *h3n ng "J[ ha 5hD
w
b

<J
b
; Wh
>
Wh
b
; <J
>
<J
b
; .9 Wh
b
Wh
>
<J
>
; a9
a
b
a<J
b
; .Wh
>
aWh
b
; .<J
>
<J
b
Wh
b
: <J
b
; .9 Wh
b
)p "h=5h/b4
<J
>
Wh
>
: <J
>
; a9 Wh
>
)p "h=5h/>4
]9# ph3n ng "J[ ha 5hD tKng Mut
ni cp "J[ ha 5hD B iju 5iGn/ n~ng IN p
-utN nhiGt I4 Jc nh c gi t! iGn th2 "J[
ha 5hD Jc nh:
e
<JWh
/p"lt4

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.

Phai nhan biet duoc diem tuong duong.



F CAGCH HAGC 9INH 9IEJM TK7NL 9K7NL
F TheMm mo5t chat ch4 th/ co* -ha na2n"
ta#o ma$u ma#nh +a$ 0aDc t%)n" +,*i mo5t
.a#n" na$o 0o* cua ca*c caDp oxB ho*a C
-h) t%on" phan )*n"
2 Du$n" chat ch4 th/ oxB ho*a C -h)
3 NhoMn" caOn .u$n" ch4 th/.


Ch thi oxy hoa khu
Chat ch thi oxy hoa - khu la nhung
chat huu co co tnh oxy hoa hay khu
mau cua dang oxy hoa khac han voi
mau cua dang khu lien hop.
khi the cua dung dich thay doi th mau
sac cua ch thi cung thay doi

Nhoan" the 0o1i ma$u cua chat ch4 th/
nd
Ox
+ ne nd
Kh
dung dich co mau cua dang Ind
Ox
khi:
dung dich co mau cua dang Ind
Kh
khi
Sn+
Sn+
lg
ew| N e
Wh
<J
e

e
n
> >
Kh 2% Kh %
?n1 ?n1 ?n1 ?n1
+ =
be
Sn+
Sn+
Wh
<J
n
> >
Kh 2% Kh 2%
?n1 ?n1 ?n1 ?n1
ew| N e
e

+

be
b
Sn+
Sn+
Wh
<J
n
> >
Kh 2% Kh 2%
?n1 ?n1 ?n1 ?n1
ew| N e
e



Khoang the :

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.

Chon chat ch thi: 0,95 (V) E


0
Ind
1,48(V)

I' (AI (![ CH\ THI
b4.bee 8 / bee
p )
p ) )p
xxs
c
e e
e e
=

=

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

Tnh sai so khi chuan do dung dich Fe


2+

0,1M bang dung dich Ce
4+
0,1M. Biet rang
het thuc chuan do o E
c
= 1,257 V
4 / zz N e
e
89 89
> :
& =
+ +
p vv N b
e
)9 )9
: v
=
+ +

GIAI
p bew N b
>
zz N e vv N b
=
+
=
4)
>
E
c
= 1,257V > E
T
= 1,105 V
Ket thuc chuan do sau diem tuong duong
4 b lg/
ew| N e

e
>
+ = '
a
SS = 0,0

' CAGC WHK7NL WHAGW CHTAJN 9!U
!HY H!AG NHK8
1. Phaang phap chaan do oxy hoa kha
bang KMnO
4

2. Phaang phap chaan do bang Ce(SO
4
)
2

3. Phaang phap chaan do oxy hoa kha bang
K
2
Cr
2
O
7

4. Phaang phap chaan do oxy hoa kha theo
phaang phap Iot - Th/osa/fat

1.Phaang phap chaan do oxy hoa
kha bang KMnO
4
Nguyen tac
MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O E
0
=1,51V
Khong dung HNO
3
va HCl lam moi truong
* E
0
Cl2/2Cl-
< E
0
MnO4-/Mn2+
=>
2MnO
4
-
+ 10Cl
-
+16H
+
2Mn
2+
+ 5Cl
2
+ 8H
2
O
* E
0
NO3-/NO

e
nn<v=nn>;
HQ<
:
cng "J[ ha cht 5hD

Ung dang caa phaang phap chaan
do oxy hoa kha bang KMnO
4
Chuan do truc tiep cac chat khu
Xac dinh H
2
C
2
O
4
5H
2
C
2
O
4
+ 2KMnO
4
+ 8H
2
SO
4
2MnSO
4
+
10CO
2
+ K
2
SO
4
+ 8H
2
O
Xac dinh Fe
2+
Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
Xac dinh H
2
O
2
5H
2
O
2
+ 2MnO
4
-
+ 6H
+
2Mn
2+
+ 5O
2
+ 8H
2
O

Ung dang caa phaang phap chaan
do oxy hoa kha bang KMnO
4
Chuan do thay the
Ap dung doi voi : Chat khu de bi khong kh
oxy hoa
Chat khu + Fe
3+
( 89
>;
Chuan do Fe
2+
bang KMnO
4
+ Xac dinh RCHO
RCHO + 2Cu(OH)
2
(^)<<H ; )u
>
< ; >H
>
<
)u
>
< ; 89
:;
@ )u
>;
; 89
>;

w89
>;
; nn<
v
=
; H
;
@ w89
:;
; nn
>;
; vH
>
<

+ Xac dinh cac ion tao duoc tua oxalat
Ca
2+
,Cd
2+
, Zn
2+
, Pb
2+
, Co
2+
, Ni
2+
, .
-
Dung (NH
4
)
2
C
2
O
4
de ket tua cac ion kl tren
Ca
2+
+ C
2
O
4
2-
CaC
2
O
4
-
Loc rua tua oxalat thu duoc bang H
2
SO
4
(l)
CaC
2
O
4
+ H
2
SO
4
CaSO
4
+ H
2
C
2
O
4
-
Chuan H
2
C
2
O
4
sinh ra bang KMnO
4
5H
2
C
2
O
4
+ 2KMnO
4
+ 8H
2
SO
4
2MnSO
4
+
10CO
2
+ K
2
SO
4
+ 8H
2
O

Chuan do nguoc
Ap dung doi voi:Chat khu phan ung cham voi
MnO
4
-
Chat khu + MnO
4
-
du
Chuan do KMnO
4
du bang chat khu khac
+ Xac dinh S
2-
Cho S
2-
tac dung voi KMnO
4
lay du
5S
2-
+8MnO
4
-
du

+24H
+
5SO
4
2-
+8Mn
2+
+12H
2
O
)huan luong KMnO
4
du bang Fe
2+
w89
>;
; nn<
v
=
; H
;
w89
:;
; nn
>;
; vH
>
<

2. Phuong phap chuan do
Ce(SO
4
)
2
Ce
4+
+ e Ce
3+
E
o
= + 1,44V
Mau cam
Phep chuan do Ce
4+
phai dung chat ch thi
Thuong dung ch thi Feroin.
Tai diem tuong duong: mau xanh nhat
mau do.

Ung dung cua ph.ph chuan do Ce(SO
4
)
2
Chat PT
Phan ung
ieu kien TH
Sn Sn
2+
+ 2Ce
4+
Sn
4+
+ 2Ce
3+
Kh Sn
4+
= Zn
Fe Fe
2+
+ Ce
4+
Fe
3+
+ Ce
3+
Kh Fe
3+
bang
Zn , SnCl
2
Mg,
Ca, Zn,
Co, Pb,
Ag
H
2
C
2
O
4
+2Ce
4+
2CO
2
+2Ce
3+
+2H
+
cac ion duoi
dang MC
2
O
4
.
Loc, rua ket
tua, hoa tan
bang H
2
SO
4
l
HNO
2
HNO
2
+2Ce
4+
+H
2
ONO
3
-
+
2Ce
3+
+3H
+

3. Phuong phap chuan do oxy hoa khu
bang K
2
Cr
2
O
7

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

Chu* B*: Khi chuan do I


2
bang Na
2
S
2
O
3
nen:
+ Tien hanh o nhiet do thuong
V : o T
0
cao I
2
bi thang hoa va do nhay cua
ho tinh bot bi giam di
+ Chuan do trong moi truong acid yeu hoac
trung tnh 5 < pH < 7
V: Trong moi truong acid manh
S
2
O
3
2-
+ 2H
+
H
2
SO
3
+ S
Trong moi truong kiem
I
2
+ 2OH
-
IO
-
+ I
-
+ H
2
O
+ Ch cho ho tinh bot vao o gan cuoi chuan do
Dd co mau vang nhat chuan do den mat mau

Ung dung cua phuong phap chuan do
I
2
- Na
2
S
2
O
3

)huin I t!c ti2p:



S
>
; >Qa
>
x
>
<
:
>QaS ; Qa
>
xv<
{
)
e
p
e
@ )p
)huin I ngc: )ht WhD ; S
>
+
)
"
p
"
)up
b
)huin S
>
+ .ng Qa
>
x
>
<
:
S
>
; >Qa
>
x
>
<
:
>QaS ; Qa
>
x
v
<
{

)up
>
)p
Ht: )
"
p
"
; )p @ )upu @ )u/p
b
;p
>
)


* Chuan do thay the
Chat oxy hoa + KI du I
2

Chuan I
2
tao ra bang Na
2
S
2
O
3
+ Xac dinh Cu
2+
: tien hanh pH = 4 (CH
3
COOH)
2Cu
2+
+ 4I
-
= 2CuI

+ 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

c. Phaang phap chaan do kem : Cho phep xac dinh


ion Zn
2+
bang dd K
4
[Fe(CN)
6
] theo p.u :
3Zn
2+
+2K
4
[Fe(CN)
6
] = K
2
Zn
3
[Fe(CN)
6
]
2
+ 6K
+

3 WHK7NL WHAGW 9! &A_C
Gia su tien hanh chuan do V
0
ml dung dich
chua ion halogenur X

(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

Tai diem tuong duong the tch AgNO


3
bang:
ml
%
& &
#g., )4)
we
b N e
b N e we
:
= = =

V
F Cong thuc tnh pCl
pCl pAg GHI CHU
0
0 pX = lgC
0
1,00
9,00
5
0,1 1,09
8,91
25
0,5 1,48
8,52
45
0,9 2,28
7,72
49,5
0,99 3,30
6,70
49,95 0,999 4,30 5,70 SS% = - 0,1%
50
1
5,00 5,00 iem tuong duong
50,05
1,001
5,70
4,30
SS% = + 0,1%
50,5
1,01
6,70
3,30
75
1,5
7,79
2,21
100
2
8,70
1,30
& &
&/ / &
p*
+

=
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
=

Neu ket thuc o pX < pX


T
:
Ket thuc chuan do truoc diem tuong duong (du
dung dich NaX ). Phep chuan do mac sai so thieu SS
% < 0 va duoc ky hieu

]
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

b) S= + 0,02 => >1 dd tha Ag


+

10
p-16
= 10
-5
=> p = 11

=> buc nhy p = 5 11


s e> N e be .
be . be
4 be be / be
be .
4 / be
s
>
b b
b b w
>
e e
e
=
+
=
+
=

& /
/ /
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" #:

+ +

%.a .a % n n/l m#g/l 4 / N 4 /


HCt 52t ta # nn 5hhng hp ph, Sn+
=
@A ++ c
#u ca ch th t +".

)c cht ch th thrng +1ng l:
Fluorescein : la mot acid yeu(K
a
=10
8
) nen
phai ch.I trong m.t kiem de ch thi phan ly
manh th moi thay ro mau.
pH mt be 7 t!nh J3[ !a p
2Ag
+
+ 2OH

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

th xuat hien mau do mau cua


phuc Fe(SCN)
2+
: Fe
3+
+ 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

Ngung chuan do khi thay mau cua dung dich chuyen


sang mau hong.

^)u B* : Pp nay can thuc hien trong m.t acid de tranh
su thuy phan cua ion Fe
3+
( HNO
3
v i C > 0,3M)
Khi xac dinh I

bang pp nay can cho AgNO


3
du
truoc de ket tua het I

roi moi them ch thi Fe


3+
de
tranh phan ung : 2Fe
3+
+ 2I

2Fe
2+
+ I
2
Khi xac dinh Cl

bang pp nay o diem cuoi se xay


ra p : AgCl

+ SCN

AgSCN

+ Cl