B MN: HA PHN TCH

GV: LI TH HIN
Email: h3u_8789@yahoo.com
Gii thiu hc phn
Tn hc phn Ha phn tch
Analytical chemistry

S tn ch 2
Muc tiu cua hc phn
Sau khi hon tt hc phn, sinh vin phi nm c
nhng kin thc v Ho phn tch, v phn tch nh
tnh v phn tch nh lng mt s cht c bn.

M ta vn tt ni dung hc phn
Hc phn ny nhm cung cp cho sinh vin nhng
kin thc c s, nhng nguyn l chung ca ha hc
phn tch, bao gm cc phn: chun axit-baz,
phc cht, oxy ha kh, ta, v mt s phng php
ha l khc.
Tai liu hc tp
Sch, gio trnh chnh
Gio trnh Ha phn tch, H Cng nghip TP.HCM.
Tai liu tham khao
[1] Nguyn Thc Ct, T Vng Nghi, o Hu Vinh (1985), C
s l thuyt ha hc phn tch, Xut bn ln 2, H Ni.
[2] Lm Ngc Th (2002), C s l thuyt ha hc phn tch,
Hu.
[3] Nguyn Tinh Dung (1991), Ha hc phn tch, phn I. L
thuyt c s , NXB Gio Dc.
[4] L Xun Mai, Nguyn Th Bch Tuyt (2000), Gio trnh phn
tch nh lng, NXB i hc quc gia Tp. HCM.
[5] Hong Minh Chu (2002), C s ha hc phn tch, NXB
Khoa hc k thut H Ni.
[6] T Vng Nghi (2000), Ha hc phn tch, NXB i hc quc
gia H Ni.
Gii thiu hc phn
PHN TH NHT: NH TNH
Chng 1. Cc khi nim v nh lut c bn
Chng 2. Phn tch nh tnh cation nhm 1
Chng 3. Phn tch nh tnh cation nhm 2
Chng 4. Phn tch nh tnh cation nhm 3
PHN TH HAI: NH LNG
Chng 1. Phn tch khi lng
Chng 2. Phn tch th tch
Chng 3. Phn tch axit baz
Chng 4. Phn tch oxy ha- kh
Chng 5. Phn tch phc cht
Chng 6. Phn tch kt ta
Ni dung hc phn
Nhp mn ha phn tch
Ni dung v yu cu ca ha hc phn tch
Phn loi cc phng php phn tch
Cc loi phn ng ha hc dng trong ha
phn tch
Cc giai on ca mt phng php phn tch
Cc loi nng dng trong ha phn tch
Nhp mn ha phn tch
Fields of chemistry
Physical chemistry
Analytical chemistry

Organic chemistry
Inorganic chemistry
Biological chemistry
Nhp mn ha phn tch
Ni dung v yu cu ca ha hc phn tch
HPT l khoa hc v cc phng php pt nh tnh v nh
lng, kim tra nhng qu trnh ha l v k thut ha hc
Pt nh tnh: xc nh s hin din ca cc cu t trong
mu, nh gi hm lng s b ca chng
Pt nh lng: xc nh chnh xc hm lng ca cu t
trong mu:
Pp ha hc
Pp vt l
Pp ha l
Phn loi cc phng php phn tch
Phn loi theo bn cht ca phng php:
PP ha hc: bng phh chuyn cu t cn xc nh thnh
hp cht mi c tnh cht c trng c th xc nh
s hin din v hm lng
PP vt l: xc nh bng nghin cu tnh cht quang, in,
t
PP ha l: kt hp PPVL v PPHH
- Cc pp ph
- Cc pp in ha
- Cc pp sc k
Phn loi cc phng php phn tch
Phn loi theo lng mu phn tch hay k thut phn tch
Phn tch th: s dng dng c 50 500 ml vi lng mu
1 10 g hoc 1 10 ml
Phn tch bn vi lng: dng c < 50 ml, lng mu 10
-3

1g hay 10
-1
1 ml
Phn tch vi lng: dng c < 1 ml, lng mu 10
-6
10
-3
g
hoc 10
-3
10
-1
ml
Phn tch siu vi lng: lng mu < 10
-6
g hoc 10
-3
ml
Cc loi phn ng ha hc dng trong HPT
Phn ng oxy ha kh:
nh tnh:
Cl
2
+ I
-

I
2
+ Cl
-
I
2
xut hin lm xanh giy tm h tinh bt
nh lng:
MnO
4
-
+ Fe
2+
+ H
+
Mn
2+
+ Fe
3+
+ H
2
O
Phn ng trao i:
P acid baz
P to ta
P to phc
Yu cu i vi thuc th dng trong HPT
tinh khit
Tnh chn lc
Tnh nhy
Gii hn pht hin: VD: gii hn pht hin Fe
3+

bng SCN
-
l 0,25 g/ml
Tr vi mi trng
C phn t lng ln gim sai s khi cn
Yu cu i vi thuc th dng trong HPT
Xy ra tc thi
Xy ra hon ton theo chiu mong mun
P theo t l xc nh, sn phm c thnh phn xc nh
C du hiu nhn bit r rng
Cc giai on ca mt phng php phn tch
Giai on chn mu: m bo tnh i din ca mu:
Chn mu ring: chn ngu nhin
Chn mu ban u: l mu c chn t mu ring
Mu trung bnh: mu ban u c trn u v nghin
nh
Giai on chuyn mu thnh dung dch: 2 cch
PP t: mu c ha tan bng dung mi thch hp
(acid, baz, nc, cht oxy ha mnh)

Cc giai on ca mt phng php phn tch
- Dd HCl: ha tan mu: CO
3
2-
, PO
4
3-
, SO
3
2-

- Dd HNO
3
: ha tan PbS, CuS, cc hp kim
- Dd H
2
SO
4
m c: ha tan cc hp kim
- Dd HF: ha tan SiO
3
2-
, SiO
2

Phng php kh: nung kh cc hp cht kh tan
(Al
2
O
3
, TiO
2
, Cr
2
O
3
) vi cc cht: NaOH, Na
2
CO
3
,
Na
2
O
2
trong chn Pt hoc Ni nhit cao; sau ha
tan bng dd thch hp
Yu cu: khng lm mt mu, bn mu

Cc giai on ca mt phng php phn tch
Chn pppt thch hp, thc hin phn ng
Yu cu:
o lp li nhiu ln :
Trnh sai s qu ln
tin cy ca php o





Kim chng kt qu, x l kt qu phn tch
Cc loi nng dng trong ha phn tch
chun (T): s g hoc mg cht tan trong 1ml dd
Nng phn trm C%
Nng mol C
M
: s mol cht tan trong 1000ml dd
Nng molan C
m
: s mol cht tan trong 1000g dung mi
Nng phn mol: N
i
= n
i
/N
Nng ng lng C
N

CHNG 1. CC KHI NIM V NH LUT CN BN
Khi nim v ha tan- tch s tan
4
nh ngha v s in ly, cht in ly
1
Tch s ion cua nc- thang pH
2
pH trong cc h axit- bazo
3
Khi nim c ban v phc cht
5

PHN 1: NH TNH

Phan ng thuy phn
6
Khi nim in ly
Hng s phn ly dung dch
Hot , nng , h s hot
Hng s bn v khng bn
in ly
Mi quan h gia in ly v hng s
phn ly


1.1. S in ly, cht in ly
1.1.1. Khi nim in ly
S in ly l qu trnh phn ly cc cht tan thnh nhng
ion mang in tch tri du, cc cht trong trng thi nng
chy hay trong dung dch, c kh nng phn ly thnh
nhng ion mang in tch tri du, lm cho h c kh nng
dn c in, gi l cht in ly
Phn loi: cht in ly gm hai loi:
Cht in ly mnh: l cht in ly c kh nng
phn ly hon ton, c biu th bng du ( )
Cht in ly yu: l cht in ly khng c kh
nng phn ly hon ton, c biu th bng du
( )


1.1.1. Khi nim in ly
1.1.1. Khi nim in ly
V d: dung dch HCl, NaCl... l nhng dung dch cht in ly
mnh c biu th trong dung dch nc l:
NaCl Na
+
+ Cl
-

Cn nhng dung dch FeCl
2
, Cu(OH)
2
... l nhng dung dch
cht in ly yu n rt yu, c biu th trong dung dch
nc l:
FeCl
2
Fe
2+
+ 2Cl
-

1.1. 2. Hng s phn ly dung dch
A
n
B
m
nA
m+
+ m B
n-

| | | |
| |
n m
m
n
n
m
cb
B A
B A
K
+ +
=
.
Gi l hng s in ly hay hng s phn ly A
m
B
n
. y l
mt i lng c trng cho cht in ly ho tan trong mt
dung mi nht nh.
1.1.3.. Hot , nng , h s hot
Hot :
a = f.C
C: nng (mol/L)
f: h s hot (ph thuc vo lc ion )
Lc ion :
Gi s dung dch c i cu t vi
in tch l Z
1
, Z
2
, , Z
i

nng ca tng cu t C
1
, C
2
, , C
i


1.1.3. Hot , nng , h s hot
Nu = 0 dung dch rt long, tng tc khng ng
k f = 1 a = C
Nu 0,02 th:


Nu 0,02 < 0,2 th:


Nu > 0,2 th:

(A: h s thc nghim)
V d: Tnh a ca Al
3+
v SO
4
2-
trong dung dch hn hp
Al
2
(SO
4
)
3
10
-3
M v (NH
4
)
2
SO
4
10
-3
M

2
2
1
log
i i
Z f =

+
=
1
5 , 0 log
2
i
i
Z
f

.
1
5 , 0 log
2
A
Z
f
i
i
+
+
=
1.1.4. Hng s bn, hng s khng bn
Hng s in ly K
cb
, cn gi l hng s phn ly hay hng
s khng bn (K
pi
)
V d:
CH
3
COOH CH
3
COO
-
+ H
+
c K
cb
= K
pi
= 1,82.10
-5

Qu trnh kt hp ion trong dung dch cht in ly
c xc nh nh lng theo hng s kt hp, cn gi
l hng s bn .
V d:
CH
3
COO
-
+ H
+
CH
3
COOH K
cb
= = 10
4,74

K
pi
. =1
1.1.5. in ly
L t s gia nng cht in ly b phn ly vi nng
cht in ly em vo ho tan.
0
n
n
= o
n l s mol ca cht in ly b phn ly
n
0
l s mol ca cht in ly em vo ho tan
1.1.6. Mi quan h gia in ly v hng s phn ly
1.2. Tch s ion ca nc - thang pH
H
2
O va l mt axit va l mt baz
H
2
O + H
2
O H
3
O
+
+ OH
-

Hng s cn bng:

V nc phn ly rt t nn coi [H
2
O] l hng s:
K.[H
2
O] = [H
3
O
+
].[OH
-
] = const = k
H2O

K
H2O
l hng s ion ca nc (ph thuc vo nhit )
25
0
C:
k
H2O
= 10
-14
pK
H2O
= -lg10
-14
=14
2
2
3
] [
] ].[ [
O H
OH O H
K
+
=
1.2.1. S ion ha ca nc
1.2.2. Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
Xt mt dung dch axit:
A + H
2
O B + H
3
O
+

Hng s cn bng:






Thng qua gi tr K
a
c th xc nh mnh, yu ca axit?
(1)
] ].[ [
] ].[ [
2
3
O H A
O H B
K
+
=
a
K
A
O H B
O H K = =
+
] [
] ].[ [
] .[ ) 1 (
3
2
K
a
l hng s axit; pK
a
= -logK
a

Tng t vi baz:


a axit: phn t cha nhiu hn 2 H phn ly nhiu nc,
mi nc c mt hng s
V d: axit H
3
PO
4

H
3
PO
4
+ H
2
O H
2
PO
4
-
+ H
3
O
+
pK
a1
= 2,12
H
2
PO
4
-
+ H
2
O HPO
4
2-
+ H
3
O
+
pK
a2
= 7,21
HPO
4
2-
+ H
2
O PO
4
3-
+ H
3
O
+
pK
a3
= 12,36

a baz: PO
4
3-
, c pK
b1
, pK
b2
, pK
b3
] [
] ].[ [
] .[
2
B
OH A
O H K K
b

= =
1.2.2. Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
Quan h gia K
a
v K
b
ca mt cp axit / baz lin hp
14
3
10
] [
] ].[ [
.
] [
] ].[ [
.
2
= = =
+
O H b a
K
B
OH A
A
O H B
K K
pK
a
+ pK
b
= 14
Nhn xt: Vi mt cp ax-bz lin hp, axit cng mnh th
baz cng yu v ngc li
1.2.2. Hng s axit (K
a
), hng s baz (K
b
) Mi lin h

1.3. pH trong cc h axit baz

1.3.1. iu kin proton
1.3.2. pH trong cc h acid - baz n chc
Kho st trong h n acid - baz mnh
Kho st trong h n acid yu - baz mnh hoc acid
mnh - baz yu
Kho st trong h n acid - baz yu
Kho st trong h hn hp acid - baz yu
Phng trnh bo ton proton:
Nguyn tc: S mol proton axit cho bng s mol
proton baz nhn
V d 1:
H
2
O + H
2
O H
3
O
+
+ OH
-

PTBT proton: [H
3
O
+
] = [OH
-
]
H
2
O
OH
-

H
3
O
+

- H
+
+ H
+

1.3.1. iu kin proton
V d 2: dung dch HCl c nng C(mol/L)
Trong dd tn ti 2 cn bng:
HCl + H
2
O Cl
-
+ H
3
O
+

H
2
O + H
2
O H
3
O
+
+ OH
-



HCl, H
2
O
- H
+

+ H
+

Cl
-
, OH
-

H
3
O
+

PTBT proton:
[H
3
O
+
] = [OH
-
] + [Cl
-
]
= [OH
-
] + C
1.3.1. iu kin proton
V d 3: dung dch hn hp HCl (C
1
) v CH
3
COOH (C
2
)
Cc cn bng trong dung dch
HCl + H
2
O H
3
O
+
+ Cl
-

CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+

H
2
O + H
2
O H
3
O
+
+ OH
-

HCl, CH
3
COOH, H
2
O
- H
+

+ H
+

H
3
O
+

Cl
-
, CH
3
COO
-
, OH
-

[H
3
O]
+
= [OH
-
] + [Cl
-
] + [CH
3
COO
-
]
C
2

= C
1

1.3.1. iu kin proton
V d 4: dung dch NH
3

Cc cn bng:
NH
3
+ H
2
O NH
4
+
+ OH
-

H
2
O + H
2
O H
3
O
+
+ OH
-

PTBT proton: (NH
3
, H
2
O)
[OH
-
] = [NH
4
+
] + [H
3
O
+
]
V d 5: dung dch CN
-
, CH
3
COO
-
Cc cn bng:
CN
-
+ H
2
O HCN + OH
-

CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-

H
2
O + H
2
O H
3
O
+
+ OH
-
PTBT proton: (CN
-
, CH
3
COO
-
, H
2
O)
[HCN] + [CH
3
COOH] + [H
3
O
+
] = [OH
-
]
1.3.1. iu kin proton
1.3.2.pH trong cc h axit- bazo n chc
pH ca dung dch axit mnh
Gi s dung dch axit mnh HA, nng C
a
:
HA + H
2
O A
-
+ H
3
O
+
H
2
O + H
2
O H
3
O
+
+ OH
-

Hoc vit di dng:
HA A
-
+ H
+
H
2
O H
+
+ OH
-

PT bo ton proton:
[H
+
] = [A
-
] + [OH
-
] = C
a
+ [OH
-
]

] [
] [
2
+

=
H
K
OH
O H
] [
] [
2
+
+
+ =
H
K
C H
O H
a
... ] [
0 ] .[ ] [
2
2
=
=
+
+ +
H
K H C H
O H a
(*)
Bin lun: [H
+
] = [A
-
] + [OH
-
] = C
a
+ [OH
-
]
Nu C
a
10
-6
[OH
-
] C
a
khi :
[H
+
] = C
a

Nu C
a
10
-8
C
a
[OH
-
] khi :
[H
+
] = [OH
-
] = 10
-7

Nu 10
-8
< C
a
< 10
-6
gii phng trnh bc 2
(*)

V d: Tnh pH ca dung dch HCl trong trng hp 10
-
3
M, 10
-7
M, 10
-9
M
pH ca dung dch acid mnh
BOH c nng C
b

Cn bng trong dung dch:
BOH B
+
+ OH
-

H
2
O H
+
+ OH
-

PT bo ton proton:
[OH
-
] = [H
+
] + [B
+
] = [H
+
] + C
b


] [
] [
2
+

=
H
K
OH
O H
... ] [
0 ] .[ ] [
2
2
=
= +
+
+ +
H
K H C H
O H b
(**)
pH ca dung dch bazo mnh
Bin lun:
Nu C
b
10
-6
pOH = -logC
b

Nu C
b
10
-8
pOH = 7
Nu 10
-8
< C
b
< 10
-6
gii pt bc 2 (**)

pH ca dung dch bazo mnh
Gi s dung dch axit yu HA, nng C
a

Dung dch c cn bng:
HA H
+
+ A
-

H
2
O H
+
+ OH
-
PT bo ton proton:
[H
+
] = [A
-
] + [OH
-
]
Pt bo ton khi lng:
C
a
= [HA] + [A
-
]
Pt hng s axit:
] [
] ].[ [
HA
A H
K
a
+
=
pH ca dung dch n axit yu
] [ ] [
] [ ] [
]. [
+
+
+
+

=
OH H C
OH H
H K
a
a
] [
] [
]. [
+
+
+

=
H C
H
H K
a
a
a
a
C
H
K
2
] [
+
=
Coi [OH
-
] [H
+
] (nc phn ly khng ng k)
Gi s [H
+
] C
a

a a
C K H . ] [ =
+
) log (
2
1
a a
C pK pH =
pH ca dung dch n axit yu
V d 1: Tnh pH ca dung dch CH
3
COOH
0,1M; pK
a
= 4,75

V d 2: Tnh pH ca dung dch NH
4
Cl
0,1M; bit NH
3
c pK
b
= 4,75

V d 3: Tnh pH ca dung dch axit
salixilic 10
-3
M c pK
a
= 3
pH ca dung dch n axit yu
Gi s dung dch baz B, nng C
b
Cc cn bng trong dung dch:
B + H
2
O BH
+
+ OH
-

H
2
O H
+
+ OH
-
Pt bo ton proton
[OH
-
] = [BH
+
] + [H
+
]
Pt bo ton khi lng:
C
b
= [BH
+
] + [B]
Pt hng s K
b


] [
] ].[ [
B
OH BH
K
b
+
=
pH ca dung dch n bazo yu
] [ ] [
] [ ] [
. ] [
+
+

+
=
H OH
H OH C
K OH
b
b
Tng t nh trng hp axit yu:
[H
+
] [OH
-
]
[OH
-
] C
b

b b
C K OH . ] [
2
=

) log (
2
1
b b
C pK pOH =
pH = 14 - pOH
pH ca dung dch n bazo yu
Hn hp 2 axit mnh: HA
1
(C
1
) v HA
2

(C
2
)
Trong dung dch:
[H
+
]
dd
= [H
+
]
HA1
+ [H
+
]
HA2
+ [H
+
]
H2O
= C
1
+ C
2
+ [H
+
]
H2O

Nu C
1
+ C
2
10
-6
[H
+
]
H2O
nh, b qua
pH = -log(C
1
+ C
2
)
Nu C
1
+ C
2
< 10
-8
[H
+
]
axit
nh, b qua
pH = 7
Nu 10
-8
C
1
+ C
2
< 10
-6

Gi nguyn v gii pt bc 2
pH ca dung dch hn hp 2 axit
Hn hp ca mt axit mnh HA
1
(C
1
) v mt axit
yu HA
2
(C
2
, K
a
):
[H
+
]
dd
= [H
+
]
HA1
+ [H
+
]
HA2
+ [H
+
]
H2O
Thng trong dung dch axit H
+
do nc
phn ly khng ng k b qua
[H
+
] = C
1
+ [H
+
]
HA2

Nu C
1
C
2
H
+
do axit yu phn ly khng ng
k b qua
[H
+
]
dd
= C
1

Nu C
1
C
2
khng b qua axit yu
pH ca dung dch hn hp 2 axit
V d 1: Tnh pH ca hn hp gm HCl 0,1M
v CH
3
COOH 0,1M; pK
a
= 4,75

pH ca dung dch hn hp 2 axit
1.4.1. Tch s tan
1.4.2. tan
1.5.3. iu kin kt ta
1.4. Khi nim v ha tan, tch s tan
Ag
+
+ Cl
-
AgCl
to ta
ha tan

1.4.1. Tch s tan

Tc phn ng to ta ph thuc vo yu t no?


Tc ha tan ta:



Phn ng t cn bng khi:

kt 1
Ag Cl
v K .S.a .a
+
=
ht 2
v K .S =
v
ht
= v
kt

Tng qut:
nA + mB A
n
B
m

1
Ag Cl
K .S.a .a
+
2
K .S
=
2
AgCl
Ag Cl
1
K
a .a const T
K
+
= = =
T ch ph thuc vo nhit
n m
A B
n m
A B A B
n n m m
T a .a
[A] .f .[B] .f
=
=

1.4.1. Tch s tan

V kt ta c tan nh nn coi f 1

n m
n m
A B
T [A] .[B] =
Tng qut:
nA + mB A
n
B
m

T ch ph thuc vo nhit

1.4.1. Tch s tan

| || | S K Cl Ag S K . . .
2 1
=
+
| || |
AgCl
T const
K
K
Cl Ag = = =
+
1
2
.
| | | |
m
n
n
m
B A
B A T
n m
+ +
= .
tan (S) ca mt cht l nng ca cht trong dung
dch bo ha ( mt nhit nht nh)
S v T l i lng c trng cho dung dch bo ha
V d 1: Tnh T
Mg(OH)2
20
0
C bit rng nhit 100ml
dung dch bo ha c cha 0,84 mg Mg(OH)
2
.
Giai
T gi thit v s mg cht tan trong dung dch bo ha
suy ra:
2
4
Mg(OH)
0,84 1000
S . 1, 4.10
1000.58 100

= =

1.4.2. tan

Mg(OH)
2
Mg
2+
+ 2OH
-

S S 2S
2
2+ - 2
Mg(OH)
3
4 3
11
T [Mg ].[OH ]
4.S
4.(1, 4.10 )
1,1.10

=
=
=
=
V d 2: Tnh tan ca CaSO
4
20
0
C bit T ca CaSO
4
ti
nhit l 9,1.10
-6


1.4.2. tan

Cc yu t nh hng s kt ta
Cht in ly l
Ion chung
Phn ng ph
Nhit
Kch thc kt ta

1.4.3. iu kin kt ta

n m
n m
A B
T [A] .[B] < Kt ta c to thnh
n m
n m
A B
T [A] .[B] =
Trng thi cn bng
n m
n m
A B
T [A] .[B] > Kt ta khng c to thnh
1.5.1. nh ngha Danh php
1.5.2. Hng s bn v hng s khng
bn ca phc cht
1.5.3. Nng cn bng ca cc cu
t trong dung dch to phc
1.5.4. Cc yu t nh hng n s
phn ly ca phc cht. Hng s bn
iu kin

1.5. Khi nim c bn v phc cht

nh ngha: Phc cht l nhng hp cht to bi cation
(ion trung tm) kt hp vi cc phi t (l cc phn t
hoc ion); n tn ti trong dung dch ng thi c kh
nng phn ly thnh cc ion n hay phn t.
[Ag(CN)
2
]
-

Ion trung tm
Phi t
S phi tr
Trong dung dch: [Ag(CN)
2
]
-
Ag
+
+ 2CN
-

1 phn

1.5.1. inh ngha Danh php

Danh php: Tn phi t + tn ion trung tm
Nu phi t l gc axit: thm o vo tn gc
SO
4
2-
: sunfato
NO
3
-
: nitrato
Nu phi t l halogen:
F
-
: floro
Cl
-
: cloro
Br
-
: bromo
I
-
: iodo
OH
-
: hidroxo
S phi tr: 1 (mono); 2 (i); 3 (tri); 4 (tetra); 5 (penta);
6 (hexa)

1.5.1. inh ngha Danh php

Hng s bn: i lng c trng cho kh nng to phc
Hng s khng bn: i lng c trng cho kh nng
phn ly phc cht
[Cu(NH
4
)
4
]
2+

phn ly
to thnh
Cu
2+
+ 4NH
3

2+ 4
3
2+
3 4
[Cu ].[NH ]
K
[Cu(NH ) ]
=
Hng s khng bn:
Hng s bn:
2+
3 4
2+ 4
3
[Cu(NH ) ] 1
[Cu ].[NH ] K
| = =
Da vo
K v c
th bit
c
phc
bn hay
khng

1.5.2. Hng s bn, hng s khng bn ca phc cht

Vi phc c nhiu phi t, s phn ly xy ra theo tng
nc:

Cd
2+
+ NH
3
Cd(NH
3
)
2+

1
, K
1

Cd(NH
3
)
2+
+ NH
3
Cd(NH
3
)
2
2+

2
, K
2
Cd
2+
+ 4NH
3
Cd(NH
3
)
4
2+
, K

+
, K: hng s bn v khng bn tng cng
=
1
.
2
.
3
.
4
=
1,4
K = K
1
.K
2
.K
3
.K
4
= K
1,4


1.5.2. Hng s bn, hng s khng bn ca phc cht

1.5.3. Nng CB ca cc cu t trong dd to phc
Gi s ion M c nng ban u C
m
to phc vi phi t L
M + L ML
ML + L ML
2

1
[ML]
[M].[L]
| =
(1)
2
2
[ML ]
[ML].[L]
| = (2)
T (1) [ML] =
1
.[M].[L]
Thay vo (2):
[ML
2
] =
1
.
2
.[M]
2
.[L]
Theo nh lut bo ton khi lng:
[M] + [ML] + [ML
2
] = C
m

[M] +
1
.[M].[L] +
1

2
.[M].[L]
2
= C
m

m
2
1 1 2
C
[M]
1 [L] [L]
=
+| +| |
m 1
2
1 1 2
C [L]
[ML]
1 [L] [L]
|
=
+| +| |
2
m 1 2
2
2
1 1 2
C [L]
[ML ]
1 [L] [L]
| |
=
+| +| |
1.5.3. Nng CB ca cc cu t trong dd to phc
Trng hp tng qut:

m
2 n
1 1 2 1 2 n
C
[M]
1 [L] [L] ... ... [L]
=
+| +| | + +| | |
m 1
2 n
1 1 2 1 2 n
C [L]
[ML]
1 [L] [L] ... ... [L]
|
=
+| +| | + +| | |

n
m 1 n
n
2 n
1 1 2 1 2 n
C ... [L]
[ML ]
1 [L] [L] ... ... [L]
| |
=
+| +| | + +| | |
1.5.3. Nng CB ca cc cu t trong dd to phc
V d: Tnh [Ag
+
] v [CN
-
] trong dung dch phc
Ag(CN)
2
-
0,1M; bit = 10
21

Gii
Cn bng trong dung dch
Ag(CN)
2
-
Ag
+
+ 2CN
-

Biu thc hng s bn:
- +
2
+ - 2 + + 2
[Ag(CN) ] 0,1 [Ag ]
[Ag ].[CN ] [Ag ].4[Ag ]

| = =
Gi s [Ag
+
] 0,1 [Ag
+
] = 2,9.10
-8

Vy gi thit l ng
[CN
-
] = 5,8.10
-8

1.5.3. Nng CB ca cc cu t trong dd to phc
V d 2: Tnh nng cn bng ca cc cu t trong
dung dch Ag(NH
3
)
2
+
10
-2
M, bit K = 6,8.10
-8

V d 3: Tnh nng cn bng ca cc cu t trong
dung dch CdCl
2
10
-2
M. Bit Cd
2+
to phc vi Cl
-
cc
phc: CdCl
+
, CdCl
2
, CdCl
3
-
, CdCl
4
2-
cc hng s bn
tng ng l 10
2,05
, 10
0,55
, 10
-0,2
, 10
0,5

V d 4: Tnh nng cn bng Cl
-
kt ta AgCl tan t
nht, bit Ag
+
to phc vi Cl
-
vi cc hng s sau:
AgCl
1
= 10
3,04

AgCl
2
-

1,2
= 10
5,04
AgCl
3
2-

1,3
= 10
5,05

AgCl
4
3-

1,4
= 10
5,3

1.5.3. Nng CB ca cc cu t trong dd to phc
1.5.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
Gi s trong dung dch c phc MY
2-
c mt ion L v H
+
.
Trong :
L c kh nng to phc ph vi M
H
+
c kh nng to phc ph vi Y
4-

Cc cn bng trong dung dch:
MY
2-
M
2+
+ Y
4-
( d theo di khng vit in
tch)
Biu thc HSB ca phc:

4-
[MY]
[M].[Y ]
| =
M to phc ph vi L:
M + L ML

ML + L ML
2


ML
n-1
+ L ML
n

H
+
to phc ph vi Y
4-
:
H
+
+ Y
4-
HY
3-
K
4

H
+
+ HY
3-
H
2
Y
2-
K
3
H
+
+ H
2
Y
2-
H
3
Y
-
K
2
H
+
+ H
3
Y
-
H
4
Y K
1
2
2
[ML ]
[ML].[L]
| =
1
[ML]
[M].[L]
| =
1.6.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
Gi [M] l nng ca M do phc phn ly, khi :
[M] = [M] + [ML] + [ML
2
] + + [ML
n
] (1)
Gi [Y
4-
] l nng ca Y
4-
do phc phn ly:
[Y
4-
] = [Y
4-
] + [HY
3-
] + [H
2
Y
2-
] + [H
3
Y
-
] + [H
4
Y] (2)
T (1):

2 n
1 1,2 1,n
[M]' [M] [M][L] [M][L] ... [M][L] = +| +| + +|
( )
2 n
1 1,2 1,n
[M] 1 [L] [L] ... [L] = +| +| + +|

M(L)

1.5.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
T (2):
2 3 4
4- 4-
4 4 3 4 3 2 1,4
[H ] [H ] [H ] [H ]
[Y ]' [Y ]. 1
K K .K K .K .K K
+ + + +
| |
= + + + +
|
|
\ .

Y(H)

4-
M(L) Y(H)
[MY] 1
' .
[M]'.[Y ]' .
| = = |
o o
Hoc
M(L) Y(H)
K' K. . = o o
1.5.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
V d 1: Tnh nng cc cu t c trong dung dch hn hp gm
MgY
2-
10
-2
M v Ca
2+
10
-2
M. Bit:
(MgY
2-
)

= 10
8,7

(CaY
2-
)

= 10
10,7
Giai
Nhn xt: t gi tr HSB ca 2 phc MgY
2-
v CaY
2-


2 2
CaY MgY

| >|
C phn ng:
Ca
2+
+ MgY
2-
CaY
2-
+ Mg
2+

T phn ng: [CaY
2-
] = [Mg
2+
]
1.5.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
2
2-
2 4-
CaY
[CaY ]
[Ca ].[Y ]

+
| =
2
2-
2 4-
MgY
[MgY ]
[Mg ].[Y ]

+
| =
2-
2- 2 4-
CaY
[CaY ] .[Ca ].[Y ]
+
=|
2-
2-
2
4-
MgY
[MgY ]
[Mg ]
.[Y ]
+
=
|
2
2
4-
4-
CaY
MgY
1
[Y ]
.[Y ]

| =
|
2- 2
4 9,75
CaY MgY
1
[Y ]= 10
.


=
| |
1.5.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
Theo nh lut bo ton khi lng:
[Mg
2+
] + [MgY
2-
] = 10
-2

[Mg
2+
] = 9,2.10
-3

[Ca
2+
] = 8,2.10
-4

V d 2: Tnh nng cn bng ca Mg
2+
, Y
4-
, MgY
2-
khi
trong dung dch c Mg
2+
10
-2
M, Y
4-
10
-2
M, pH = 11. Bit:
(MgY
2-
)

= 10
8,7

(MgOH
+
)

= 10
2,58
H
4
Y c pK
1
= 2; pK
2
= 2,67; pK
3
= 6,27; pK
4
=
10,95
1.5.4. Cc yu t nh n s phn ly ca phc. HSB
iu kin
1.6. Phn ng thy phn
Phn ng thu phn l phn ng tng tc gia nhng
cht khc nhau (mui, hydrua, cc hp cht oxy, halozen
v thioanhydric) vi nhng ion ca nc, km theo s ph
hu cn bng in ly ca nc v lm thay i pH ca
dung dch (k c s thay i mu sc ca dung dch )
V d: kho st s thu phn ca mui NH
4
Cl
Trong dung dch c s in ly: NH
4
Cl NH
4+
+ Cl
-
Trong dung mi nc: NH
4+
+ H
2
O NH
3
+ H
3
O
+

Nn: NH
4
Cl + H
2
O NH
3
+ Cl
-
+ H
3
O
+

V th dung dch thu c sau khi ha tan mui NH
4
Cl
trong nc l dung dch c tnh acid
Chng 2: Phn tch nh tnh cation nhm I
2.1. c tnh chung ca nhm
2.2. Thuc th chung cation nhm 1
2.3. Phn tch h thng nhm 1

Nhm 1 cation gm: Ag ; Hg
2+
; Pb
2+
, cc nguyn t ny
nm trong cc nhm khc nhau ca h thng tun hon.
Chng c hoc 18 electron lp ngoi cng hoc (18 +
2) electron 2 lp ngoi cng, l nguyn nhn ti sao
chng li tc dng ging nhau i vi cc ion halozenua.
2.1. c tnh chung ca nhm
2.2. Thuc th chung cation nhm 1
Vi thuc th HCl
To cc hp cht kt ta kh tan trong nc v trong cc
axit long vi tan khc nhau
Vi thuc th KI hay KBr
Dung dch ny phn ng vi cc cation nhm 1 to thnh
nhng kt ta tinh th c mu c trng
2.2. Thuc th chung cation nhm 1
Vi thuc th H
2
SO
4
long


H
2
SO
4
long v cc mui sunfat tan s phn ng vi cc
cation nhm 1 vi mc khc nhau. Cc cation Ag+ v
Hg
2
2+
mun to kt ta vi ion SO
4
2-
th nng ca
chng trong dung dch phi tng i ln so vi Pb
2+
to
kt ta PbSO
4
tan PbSO
4
l 0,00015 mol/ L.
2.2. Thuc th chung cation nhm 1
Vi thuc th NaOH hay KOH


Cc cation nhm I s phn ng vi thuc th to thnh cc hirxit
kt ta mu trng AgOH, Hg
2
(OH)
2
, Pb(OH)
2
nhng tnh cht ca cc
hirxit ny c khc nhau. AgOH v Hg
2
(OH)
2
rt khng bn, b phn
hy ngay khi to thnh v cho ra cc oxit tng ng Ag
2
O, Hg
2
O,
cn Pb(OH)
2
th li tan trong kim d.
Ag
+
+ OH = AgOH mu trng
AgOH b phn hy rt nhanh.
2 AgOH = Ag
2
O mu en +H
2
O
Ag
2
O khng tan trong kim d, nhng d tan trong HNO
3
, NH
4
OH v
b nh sng phn hy thnh Ag kim loi.
2.2. Thuc th chung cation nhm 1
Vi thuc th NH
3

| |
3 4
0
3 2 2 2 3 2 3
3 4 3 4 2 3
2 2 4 4 2
2 4 2 4
3 2
) ( 4 ) ( 2
) (
3 ) ( 2 2
2 2
NO NH Hg
NH O Hg NH O H NH NO Hg
NO NH PbOHNO OH NH NO Pb
O H OH NH Ag OH NH O Ag
O H NH O Ag OH NH Ag
+ + =
+ = + +
+ + = +
+ = +
+ + + = +
+
2Ag
+
+ CrO
4
2-
= Ag
2
CrO
4
mu nu
Phn ng ny tin hnh trong mi trng trung tnh (pH = 7).
Pb
2+
+ CrO
4
2-
= PbCrO
4
mu vng
2Pb
2+
+ Cr
2
O
7
2-
+ H
2
O = 2PbCrO
4
+ 2H
+

Vi thuc th K
2
CrO
4

2.2. Thuc th chung cation nhm 1
Vi thuc th H
2
S


O H NO PbSO HNO PbS
H PbS S H Pb
O H S NO Ag H NO S Ag
S Ag S Ag
H Hg HgS S H Hg
2 4 3
2
2
2 3 2
2
2
0
2
2
4 8 3 8 3
2
4 3 2 6 8 2 3
2
2
+ + + = +
+ + = +
+ + + = + +
+ = +
+ + + + = +
+ +
+ +

+ +
( ) | |
( ) | |
( ) | |
( ) | |
( ) | | O H SO SO S PbS H O S Pb
O S Pb O S O PbS
O PbS O S Pb
SO S Hg HgS O S Hg
O H S SO SO S Ag H O S Ag
O S H SO S Ag O H O S Ag
O S Ag O S O S Ag
O S Ag O S Ag
2
2
4 2
4
3 2
4
3 2
2
3 2 3 2
3 2
2
3 2
2
2
3
2
3 2
2
2
2 2
2
4 2
3
3 2
2
3 2
2
4 2 2
3
3 2
3
2 3 2
2
3 2 3 2 2
3 2 2
2
3 2
2 2 2
2
2 2
2 3 3 4 2
3 2 2
2 3
2
+ + + + + + = +
= +
+ = +
+ + + + + + = +
+ + + + + = +
+ + + + = +
= +
= +
+

+
+
+

+
Vi thuc th Na
2
S
2
O
3

2. 2. Thuc th chung cation nhm 1
Cc cation nhm 1: Ag
+
, Pb
2+
, Hg
2
2+

Thuc th Cation
Ag
+
Pb
2+
Hg
2
2+

HCl long AgCl trng, tc
dng v tan trong
NH
4
OH d
PbCl
2
tan
trong nc
nng
Hg
2
Cl
2
trng, tc
dng vi NH
4
OH
ha en
H
2
SO
4

long
- PbSO
4
trng Hg
2
SO
4
trng
KOH hoc
NaOH
Ag
2
O en Pb(OH)
2
trng,
tan trong kim
d
Hg
2
O en
NH
4
OH d To thnh phc
tan
Pb(OH)
2
trng [Hg
2
ONH
2
]NO
3
+
Hg en
Thuc th Cation
Ag
+
Pb
2+
Hg
2
2+

K
2
CO
3
hay
Na
2
CO
3

Ag
2
CO
3
trng Pb
2
(OH)
2
CO
3

trng
Hg
2
CO
3
HgO
+ Hg + CO
2
kt
ta xm
K
2
CrO
4
Ag
2
CrO
4
nu PbCrO
4
vng,
tan trong kim d
Hg
2
CrO
4

KI AgI vng PbI
2
vng, tan
trong nc nng
Hg
2
I
2
xanh lc
tc dng vi
thuc th d
HgI
4
2-
+ Hg
H
2
S v cc mui
Na
2
S, (NH
4
)
2
S
Ag
2
S en PbS en HgS + Hg en
Cu Ag trng - To hn hng
mu trng
2.2. Phn tch nh tnh cation nhm 1
Dung dch phn tch + HCl long; Li tm
Kt ta 1 + H
2
O

un si, lc nng
Nc lc 1
Nc lc 2 + KI (hoc K
2
CrO
4
) Kt ta 2 + NH
4
OH
PbI
2
vng (hoc PbCrO
4
vng)
Kt ta en
xm Hg +
NH
2
HgCl
Nc lc 3 + HNO
3

AgCl trng
2.3. Phn tch h thng cation nhm 1
Chng 3: Phn tch nh tnh cation nhm II
3.1. c tnh chung ca nhm
3.2. Thuc th chung cation nhm II
3.3. Phn tch h thng nhm II

3.1. c tnh chung ca nhm
Nhm 2 cation gm: Ca
2+
, Sr
2+
, Ba
2+
l nhng nguyn t thuc
nhm hai trong h thng tun hon, chng c y s
electron lp ngoi l 8, l c s chng c nhng tnh
cht inh tnh gn ging nhau. Hot tnh ho hc ca chng
tng t Ca n Ba. Cc ion ca chng trong dung dch nc
u khng ging nhau.
3. 2. Thuc th chung cation nhm 2
Dng thuc th H
2
SO
4
long v cc mui sunfat
To tinh th mu trng khng tan trong axit v kim
Dng thuc th Na
2
CO
3
hoc K
2
CO
3
hoc (NH
4
)
2
CO
3

To kt ta tinh th mu trng, t tan trong nc nhng
tan trong cc axit HCl, HNO
3

3. 2. Thuc th chung cation nhm 2
Dng thuc th K
2
CrO
4

Dng thuc th (NH
4
)
2
C
2
O
4

To kt ta tinh th mu vng BaCrO
4
, SrCrO
4
t tan
trong nc ( tan ca chng l S (BaCrO
4
) = 1,55.10-5
gmol/L; S (SrCrO
4
)= 4,0.10-4 gmol/L).
To kt ta Oxalat tinh th mu trng tan trong cc
acid HCl, HNO
3
, ring BaC
2
O
4
v SrC
2
O
4
tan c c
trong acid axetic.
Cc cation nhm 2: Ba
2+
, Sr
2+
, Ca
2+

Thuc th Cation
Ba
2+
Sr
2+
Ca
2+

H
2
SO
4
long
BaSO
4
trng SrSO
4
trng CaSO
4
trng, tan nhiu
trong nc
Nc thch cao
CaSO
4
bo ha
BaSO
4
SrSO
4
-
Na
2
CO
3
BaCO
3
trng SrCO
3
trng CaCO
3
trng
H
2
SO
4
c BaHSO
4
SrHSO
4
CaHSO
4

K
2
CrO
4

- Mi trng trung tnh BaCrO
4
vng SrCrO
4
vng -
- Mi trng axit axetic BaCrO
4
vng - -
(NH
4
)
2
SO
4
BaSO
4
SrSO
4
Ca(SO
4
)
2
2-

(NH
4
)
2
C
2
O
4
BaC
2
O
4
trng SrC
2
O
4
trng CaC
2
O
4
trng
Na
2
HPO
4
BaHPO
4
trng SrHPO
4
trng CaHPO
4
trng
Th mu la Ngn la mu vng lc Ngn la mu Ngn la mu gch
3. 2. Thuc th chung cation nhm 2
L
1
+ H
2
SO
4
long + ru etylic, li
tm, lc gn
Kt2 + MeSO
4
chuyn thnh MeCO
3
bng Na
2
CO
3
bo ha
Kt MeCO
3
+ CH
3
COOH n va tan ht +
K
2
CrO
4
, li tm, lc
Kt + NaOH lc k, li tm
L + Na
2
CO
3
SrCO
3
+ CaCO
3
, li tm, ly kt
ta, ra sch bng nc
BaCrO
4

vng
Nc lc +
Na
2
S
PbS en
Kt + CH
3
COOH n va tan ht, chia
thnh 2 phn
Phn t + CaSO
4

bo ha
Phn nhiu + (NH
4
)
2
SO
4
, li
tm, lc
SrSO
4
trng SrSO
4

trng
CaC
2
O
4

trng
3. 3.Phn tch h thng cation nhm 2
Chng 4 : Phn tch nh tnh cation nhm III
4.1. c tnh chung ca nhm
4.2. Thuc th chung cation nhm III
4.3. Phn tch h thng nhm III

4.1. c tnh chung ca nhm
Cation nhm 3 gm Al
3+
, Zn
2+
, Cr
3+
tng ng vi
nhng nguyn t l nhng kim loi lng tnh, khi tc
dng vi dung dch kim to thnh cc hydroxyt lng
tnh kt ta. Cc kt ta ny tan trong dung dch kim
c d.
4. 2. Thuc th chung ca cation nhm 3
Dng dung dch KOH hay NaOH d
Phn ng to ra cc hydroxyt kt ta. Cc hydroxyt ca nhm c tnh
cht lng tnh, tc l chng va c kh nng phn ly trong nc theo
kiu acid li va c kh nng phn ly theo kiu baz.
Tnh cht chung ca cc cation nhm III l chng u to thnh cc
mui tan trong mi trng kim d.
Ion cromit (CrO
2
-
) kt hp vi cc cation nh Mg
2+
, Mn
2+
, Fe
3+
, Zn
2+
to
thnh nhng kt ta kh tan Mg(CrO
2
)
2
, Zn(CrO
2
)
2
, Mn(CrO
2
)
2
v vy
tch Cr3+ cng vi nhm III, thng dng kim d v c mt H
2
O
2
oxi
ha Cr
3+
v CrO
4
2-
.V vy cho nn thuc th tch nhm III l NaOH
(hoc KOH) d v H
2
O
2
.
4. 2. Thuc th chung ca cation nhm 3
Dng dung dch NH
3

Amni hidrxit (NH
4
OH) tc dng vi cc cation nhm III to thnh
cc hidrxit khng tan, nhng ring Zn
2+
khi dung dch NH3 d s
lm kt ta ny v c ion ny chuyn thnh phc amoniacat tan
Zn(NH
3
)
4
2+

Cr(OH)
3
tan t trong NH
4
OH d, khi c mt NH
4
Cl to
thnh mui kp CrCl
3
.NH
3
mu tm
Al(OH)
3
kt ta hon ton khi dung dch c pH 7- 8
4. 2. Thuc th chung ca cation nhm 3
Dng dung dch Na
2
CO
3
hay K
2
CO
3

To thnh kt ta hidroxit, ring vi ion Zn
2+
to thnh mui cacbonat
bazo c thnh phn ph thuc nng dung dch v nhit :
Tt c kt ta trn u tan trong kim d, ring mui cacbonat baz
ca km tan c c trong amoniac v trong mui amoni.
4. 2. Thuc th chung ca cation nhm 3
Dng dung dch S
2-

Ion Zn
2+
trong mi trng trung tnh, kim yu hoc c mt
mui axetac natri th tc dng vi H
2
O hay (NH
4
)
2
S to thnh
kt ta sunfua km mu trng:
ZnCl
2
+ H
2
S + 2CH
3
COONa = ZnS + 2NaCl + 2CH
3
COOH
Ion Sn
4+
v Sn
2+
trong mi trng HCl tc dng vi H
2
S to
thnh cc sunfua kh tan:
Cc cation nhm 3: Al
3+
, Cr
3+
, Zn
2+
, Sn
2+
, Sn
4+
, As
3+
, As
5+
Thuc th Cation
Al
3+
Cr
3+
Zn
2+
Sn
2+
Sn
4+

NaOH d AlO
2
-
CrO
2
-
ZnO
2
2-
SnO
2
2-
SnO
3
2-

NaOH, Na
2
CO
3
khng d Al(OH)
3

trng
Cr(OH)
3
lc Zn(OH)
2
trng Sn(OH)
2

trng
Sn(OH)
4

trng
DD NH
3
Al(OH)
3
Cr(OH)
3
[Zn(NH
3
)
4
]
2+
Sn(OH)
2
Sn(OH)
4

Na
2
HPO
4
AlPO
4
trng CrPO
4
xanh
lc
Zn
3
(PO
4
)
2
trng Sn(OH)
2
Sn(OH)
4

H
2
S trong mi trng HCl - - - SnS nu SnS
2
vng
H
2
S trong mi trng
CH
3
COOH
- - ZnS trng - -
(NH
4
)
2
S trong mi trng
trung tnh hoc kim
Al(OH)
3
Cr(OH)
3
ZnS - -
Vi cc cht oxy ha: H
2
O
2
,
KMnO
4

- Cr
3+
Cr
6+
- Sn
2+
Sn
4+
-
Alizarin trong mi trng NH
3
Kt ta son

Kt ta nu
nht
Kt ta nht Kt ta vng
gch
Kt ta vng
nht
4.2. Thuc th chung cation nhm 3
L
2
+ NaOH d + H
2
O
2
, un k, li tm, b kt ta
L
3
+ NH
4
Cl, un si k, li tm
Kt
3,1

L
3,1
chia lm 2 phn
P1: + H
2
O
2
+ ru
amylic + H
2
SO
4

P2: + Na
2
S
Lp ru c mu
xanh ca H
3
CrO
8

ZnS trng
Lc mnh, un nng
vi (NH
4
)
2
S
Nc lc c
SnS
3
2-
+
CH
3
COOH
SnS
2

vng
Kt ra sch +
CH
3
COOH n
tan + alizarin +
NH
4
OH Kt
son
4.3. Phn tch h thng cation nhm 3