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B MN: HA PHN TCH

GV: LI TH HIN
Email: h3u_8789@yahoo.com

Gii thiu hc phn

Tn hc phn

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.

Ha phn tch
Analytical chemistry

Gii thiu hc phn

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.

Ni dung 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

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 < 10-6g hoc 10-3ml

Cc loi phn ng ha hc dng trong HPT


Phn ng oxy ha kh:
nh tnh:
Cl2 + I- I2 + ClI2 xut hin lm xanh giy tm h tinh bt
nh lng:
MnO4- + Fe2+ + H+ Mn2+ + Fe3+ + H2O
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 Fe3+
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: CO32-, PO43-, SO32-
- Dd HNO3: ha tan PbS, CuS, cc hp kim
- Dd H2SO4 m c: ha tan cc hp kim

- Dd HF: ha tan SiO32-, SiO2


Phng php kh: nung kh cc hp cht kh tan
(Al2O3, TiO2, Cr2O3) vi cc cht: NaOH, Na2CO3,
Na2O2 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 CM: s mol cht tan trong 1000ml dd

Nng molan Cm: s mol cht tan trong 1000g dung mi

Nng phn mol: Ni = ni/N

Nng ng lng CN

PHN 1: NH TNH
CHNG 1. CC KHI NIM V NH LUT CN BN

nh ngha v s in ly, cht in ly

Tch s ion cua nc- thang pH

pH trong cc h axit- bazo

Khi nim v ha tan- tch s tan

Khi nim c ban v phc cht

Phan ng thuy phn

1.1. S in ly, cht in ly

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

1.1.1. 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

1.1.1. Khi nim 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


V d: dung dch HCl, NaCl... l nhng dung dch cht in ly
mnh c biu th trong dung dch nc l:
NaCl Na+ + ClCn nhng dung dch FeCl2 , Cu(OH)2... l nhng dung dch
cht in ly yu n rt yu, c biu th trong dung dch
nc l:
FeCl2

Fe2+ + 2Cl-

1.1. 2. Hng s phn ly dung dch

A nBm

nAm+ + m Bn-

A .B

m n

K cb

n m

Am Bn

Gi l hng s in ly hay hng s phn ly A mBn. 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 Z1, Z2, , Zi
nng ca tng cu t C1, C2, , Ci

1.1.3. Hot , nng , h s hot


Nu = 0 dung dch rt long, tng tc khng ng
k f = 1 a = C
1 2
Nu 0,02 th:
log f Z
i

Nu 0,02 < 0,2 th:

Nu > 0,2 th:

log f i 0,5

log f i 0,5

Z i2
1
Z i2
1

A.

(A: h s thc nghim)

V d: Tnh a ca Al3+ v SO42- trong dung dch hn hp


Al2(SO4)3 10-3M v (NH4)2SO4 10-3M

1.1.4. Hng s bn, hng s khng bn


Hng s in ly Kcb, cn gi l hng s phn ly hay hng
s khng bn (Kpi)
V d:
CH3COOH

CH3COO- + H+ c Kcb = Kpi = 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:
CH3COO- + H+

CH3COOH

Kpi . =1

Kcb = = 104,74

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.

n

n0
n l s mol ca cht in ly b phn ly
n0 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


1.2.1. S ion ha ca nc
H2O va l mt axit va l mt baz
H2O + H2O H3O+ + OH Hng s cn bng:
[ H 3O ].[OH ]
K
[ H 2O]2

V nc phn ly rt t nn coi [H2O] l hng s:


K.[H2O] = [H3O+].[OH-] = const = kH2O

KH2O l hng s ion ca nc (ph thuc vo nhit )


250C:
kH2O = 10-14 pKH2O = -lg10-14 =14

1.2.2. Hng s axit (Ka), hng s baz (Kb) Mi lin h


Xt mt dung dch axit:

A + H 2O B + H 3O +

Hng s cn bng:

[ B].[H 3O ]
K
[ A].[H 2O]

(1)

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

1.2.2. Hng s axit (Ka), hng s baz (Kb) Mi lin h


Tng t vi baz:

[ A].[ OH ]
K b K .[ H 2O ]
[ B]
a axit: phn t cha nhiu hn 2 H phn ly nhiu nc,
mi nc c mt hng s
V d: axit H3PO4
H3PO4 + H2O H2PO4- + H3O+
pKa1 = 2,12
H2PO4- + H2O HPO42- + H3O+
pKa2 = 7,21
HPO42- + H2O PO43- + H3O+
pKa3 = 12,36
a baz: PO43-, c pKb1, pKb2, pKb3

1.2.2. Hng s axit (Ka), hng s baz (Kb) Mi lin h


Quan h gia Ka v Kb ca mt cp axit / baz lin hp

[ B ].[ H 3O ] [ A].[ OH ]
K a .K b
.
K H 2O 10 14
[ A]
[ B]
pKa + pKb = 14

Nhn xt: Vi mt cp ax-bz lin hp, axit cng mnh th


baz cng yu v ngc li

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

1.3.1. iu kin proton


Phng trnh bo ton proton:
Nguyn tc: S mol proton axit cho bng s mol
proton baz nhn
V d 1:
H2O + H2O H3O+ + OH PTBT proton: [H3O+] = [OH-]

OH-

- H+

H 2O

+ H+

H3O+

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 + H2O Cl- + H3O+
H2O + H2O H3O+ + OHCl-, OH-

PTBT proton:
- H+

HCl, H2O
+ H+

H3O+

[H3O+] = [OH-] + [Cl-]


= [OH-] + C

1.3.1. iu kin proton


V d 3: dung dch hn hp HCl (C1) v CH3COOH (C2)
Cc cn bng trong dung dch
HCl + H2O H3O+ + ClCH3COOH + H2O CH3COO- + H3O+
H2O + H2O H3O+ + OHCl-, CH3COO-, OH- H+

HCl, CH3COOH, H2O


+ H+

H3O+

[H3O]+ = [OH-] + [Cl-] + [CH3COO-]

= C1

C2

1.3.1. iu kin proton


V d 4: dung dch NH3
Cc cn bng:
NH3 + H2O NH4+ + OHH2O + H2O H3O+ + OH PTBT proton: (NH3, H2O)
[OH-] = [NH4+] + [H3O+]
V d 5: dung dch CN-, CH3COO Cc cn bng:
CN- + H2O HCN + OHCH3COO- + H2O CH3COOH + OHH2O + H2O H3O+ + OH PTBT proton: (CN-, CH3COO-, H2O)
[HCN] + [CH3COOH] + [H3O+] = [OH-]

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 Ca:
HA + H2O A- + H3O+
H2O + H2O H3O+ + OH Hoc vit di dng:
HA A- + H+
H2O H+ + OH PT bo ton proton:
[H+] = [A-] + [OH-] = Ca + [OH-]

[OH ]

K H 2O

[ H ] Ca

[H ]

[ H ]2 Ca .[H ] K H 2O 0

[ H ] ...

K H 2O
[H ]
(*)

pH ca dung dch acid mnh


Bin lun: [H+] = [A-] + [OH-] = Ca + [OH-]
Nu Ca 10-6 [OH-] Ca khi :
[H+] = Ca
Nu Ca 10-8 Ca [OH-] khi :
[H+] = [OH-] = 10-7
Nu 10-8 < Ca < 10-6 gii phng trnh bc 2
(*)
V d: Tnh pH ca dung dch HCl trong trng hp 103M, 10-7M, 10-9M

pH ca dung dch bazo mnh


BOH c nng Cb
Cn bng trong dung dch:
BOH B+ + OHH2O H+ + OH PT bo ton proton:
[OH-] = [H+] + [B+] = [H+] + Cb

[OH ]

K H 2O
[H ]

[ H ]2 Cb .[H ] K H 2O 0

[ H ] ...

(**)

pH ca dung dch bazo mnh


Bin lun:
Nu Cb 10-6 pOH = -logCb
Nu Cb 10-8 pOH = 7
Nu 10-8 < Cb < 10-6 gii pt bc 2 (**)

pH ca dung dch n axit yu


Gi s dung dch axit yu HA, nng Ca
Dung dch c cn bng:
HA H+ + AH2O H+ + OH PT bo ton proton:
[H+] = [A-] + [OH-]
Pt bo ton khi lng:
Ca = [HA] + [A-]
Pt hng s axit:

[ H ].[ A ]
Ka
[ HA ]

pH ca dung dch n axit yu

[
H
]

[
OH
]
K a [ H ].
Ca [ H ] [OH ]

Coi [OH-] [H+] (nc phn ly khng ng k)

[
H
]
K a [ H ].
Ca [ H ]

Gi s [H+] Ca
[ H ]2
Ka
Ca

[ H ] K a .Ca

1
pH ( pK a log Ca )
2

pH ca dung dch n axit yu

V d 1: Tnh pH ca dung dch CH3COOH


0,1M; pKa = 4,75
V d 2: Tnh pH ca dung dch NH4Cl
0,1M; bit NH3 c pKb = 4,75

V d 3: Tnh pH ca dung dch axit


salixilic 10-3M c pKa = 3

pH ca dung dch n bazo yu


Gi s dung dch baz B, nng Cb
Cc cn bng trong dung dch:
B + H2O BH+ + OHH2O H+ + OH Pt bo ton proton
[OH-] = [BH+] + [H+]
Pt bo ton khi lng:
Cb = [BH+] + [B]
Pt hng s Kb
[ BH ].[ OH ]
Kb
[ B]

pH ca dung dch n bazo yu

[
OH
]

[
H
]

b
[OH ] K b .
[OH ] [ H ]

Tng t nh trng hp axit yu:


[H+] [OH-]
[OH-] Cb

[OH ]2 K b .Cb

1
pOH ( pKb log Cb )
2
pH = 14 - pOH

pH ca dung dch hn hp 2 axit

Hn hp 2 axit mnh: HA1 (C1) v HA2


(C2)
Trong dung dch:
[H+]dd = [H+]HA1 + [H+]HA2 + [H+]H2O
= C1 + C2 + [H+]H2O

Nu C1 + C2 10-6 [H+]H2O nh, b qua


pH = -log(C1 + C2)
Nu C1 + C2 < 10-8 [H+]axit nh, b qua
pH = 7
Nu 10-8 C1 + C2 < 10-6
Gi nguyn v gii pt bc 2

pH ca dung dch hn hp 2 axit


Hn hp ca mt axit mnh HA1 (C1) v mt axit
yu HA2 (C2, Ka):

[H+]dd = [H+]HA1 + [H+]HA2 + [H+]H2O


Thng trong dung dch axit H+ do nc
phn ly khng ng k b qua
[H+] = C1 + [H+]HA2
Nu C1 C2 H+ do axit yu phn ly khng ng
k b qua
[H+]dd = C1
Nu C1 C2 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 CH3COOH 0,1M; pKa = 4,75

1.4. Khi nim v ha tan, tch s tan

1.4.1. Tch s tan


1.4.2. tan
1.5.3. iu kin kt ta

1.4.1. Tch s tan

Ag+ + Cl-

to ta
ha tan

AgCl

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

vkt K1.S.a Ag .a Cl
Tc ha tan ta:

v ht K 2 .S
Phn ng t cn bng khi:

vht = vkt

1.4.1. Tch s tan

K 2 .S

K1.S.a Ag .a Cl =
a Ag .a Cl

K2

const TAgCl
K1

T ch ph thuc vo nhit
Tng qut:

nA + mB AnBm

TAn Bm a An .a Bm
[A]n .f An .[B]m .f Bm
V kt ta c tan nh nn coi f 1

TAn Bm [A] .[B]


n

1.4.1. Tch s tan

K .S .Ag Cl K .S

K2
Ag . Cl
const TAgCl
K1

T ch ph thuc vo nhit

Tng qut:
nA + mB AnBm

TAm Bn A

.B

m n

n m

1.4.2. tan
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 TMg(OH)2 200C 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:

SMg(OH)2

0,84 1000

.
1, 4.104
1000.58 100

1.4.2. tan
Mg(OH)2
S

Mg2+

2OH2S

TMg(OH)2 [Mg 2+ ].[OH - ]2


4.S3
4 3

4.(1, 4.10 )
1,1.1011

V d 2: Tnh tan ca CaSO4 200C bit T ca CaSO4 ti


nhit l 9,1.10-6

1.4.3. iu kin kt ta

TAn Bm [A] .[B]


TAn Bm [A]n .[B]m
n

TAn Bm [A] .[B]


n

Kt ta khng c to thnh
Kt ta c to thnh
Trng thi cn bng

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

1.5. Khi nim c bn v phc cht

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

1.5.1. inh ngha Danh php


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]

S phi tr

Phi t

Ion trung tm

Trong dung dch: [Ag(CN)2]-

1 phn

Ag+ +

2CN-

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
SO42- : sunfato
NO3- : 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)

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


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(NH4)4]2+

Hng s khng bn:

Hng s bn:

phn ly
to thnh

Cu2+

[Cu 2+ ].[NH3 ]4
K
[Cu(NH3 )4 2+ ]
[Cu(NH3 )4 2+ ] 1

2+
4
[Cu ].[NH3 ]
K

4NH3

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:

Cd2+ + NH3
+

Cd(NH3)2+

Cd(NH3)2+ + NH3

Cd(NH3)22+

1, K1
2, K2

Cd2+ + 4NH3

Cd(NH3)42+

, K: hng s bn v khng bn tng cng


= 1.2.3.4 = 1,4
K = K1.K2.K3.K4 = K1,4

, K

1.5.3. Nng CB ca cc cu t trong dd to phc


Gi s ion M c nng ban u Cm to phc vi phi t L

M + L
ML + L

ML

[ML]
1
[M].[L]

(1)

ML2

[ML 2 ]
2
[ML].[L]

(2)

T (1) [ML] = 1.[M].[L]


Thay vo (2):
[ML2] = 1. 2.[M]2.[L]

1.5.3. Nng CB ca cc cu t trong dd to phc


Theo nh lut bo ton khi lng:
[M] + [ML] + [ML2] = Cm

[M] + 1.[M].[L] + 12.[M].[L]2 = Cm


Cm
[M]
1 1[L] 12 [L]2
C m1[L]
[ML]
1 1[L] 12 [L]2

Cm12 [L]2
[ML2 ]
1 1[L] 12 [L]2

1.5.3. Nng CB ca cc cu t trong dd to phc

Trng hp tng qut:


Cm
[M]
1 1[L] 12 [L]2 ... 12 ...n [L]n
[ML]

Cm1[L]
1 1[L] 12 [L]2 ... 12 ...n [L]n

Cm1...n [L]n
[MLn ]
1 1[L] 12 [L]2 ... 12 ...n [L]n

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 = 1021

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

Biu thc hng s bn:


[Ag(CN) -2 ]
0,1 [Ag + ]

+
- 2
[Ag ].[CN ] [Ag + ].4[Ag + ]2

Gi s [Ag+] 0,1
Vy gi thit l ng

[Ag+] = 2,9.10-8
[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(NH3)2+ 10-2M, bit K = 6,8.10-8
V d 3: Tnh nng cn bng ca cc cu t trong
dung dch CdCl2 10-2M. Bit Cd2+ to phc vi Cl- cc
phc: CdCl+, CdCl2, CdCl3-, CdCl42- cc hng s bn
tng ng l 102,05 , 100,55 , 10-0,2 , 100,5
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 = 103,04
AgCl21,2 = 105,04
AgCl321,3 = 105,05
AgCl431,4 = 105,3

1.5.4. Cc yu t nh n s phn ly ca phc. HSB


iu kin
Gi s trong dung dch c phc MY2- c mt ion L v H+.
Trong :

L c kh nng to phc ph vi M
H+ c kh nng to phc ph vi Y4-

Cc cn bng trong dung dch:


MY2- M2+ + Y4- ( d theo di khng vit in
tch)
Biu thc HSB ca phc:

[MY]

[M].[Y 4- ]

1.6.4. Cc yu t nh n s phn ly ca phc. HSB


iu kin
M to phc ph vi L:
M + L

ML

ML + L

MLn-1 + L

ML2

[ML]
[M].[L]

[ML 2 ]
[ML].[L]

MLn

H+ to phc ph vi Y4-:
H+
H+
H+
H+

+
+
+
+

Y4- HY3HY3- H2Y2H2Y2- H3YH3Y- H4Y

K4
K3
K2
K1

1.5.4. 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] + [ML2] + + [MLn]

(1)

Gi [Y4-] l nng ca Y4- do phc phn ly:


[Y4-] = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]

(2)

T (1):

[M]' [M] 1[M][L] 1,2[M][L]2 ... 1,n [M][L]n

[M] 1 1[L] 1,2[L] ... 1,n [L]


2

M(L)

1.5.4. Cc yu t nh n s phn ly ca phc. HSB


iu kin

T (2):

2
3
4

[H
]
[H
]
[H
]
[H
]
[Y 4- ]' [Y 4- ]. 1

K 4 K 4 .K 3 K 4 .K 3 .K 2 K1,4

Y(H)

[MY]
1
'
.
4[M]'.[Y ]'
M (L) . Y(H)

Hoc

K ' K. M (L) . Y(H)

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
MgY2- 10-2M v Ca2+ 10-2M. Bit:
(MgY2-) = 108,7
(CaY2-) = 1010,7
Giai
Nhn xt: t gi tr HSB ca 2 phc MgY2- v CaY2-

CaY2 MgY2
C phn ng:

Ca2+ + MgY2- CaY2- + Mg2+


T phn ng: [CaY2-] = [Mg2+]

1.5.4. Cc yu t nh n s phn ly ca phc. HSB


iu kin
CaY 2

[CaY 2- ]

[Ca 2 ].[Y 4- ]

MgY 2

[MgY 2- ]

[Mg 2 ].[Y 4- ]

[CaY2- ] CaY2- .[Ca 2 ].[Y4- ]


2[MgY
]
2
[Mg ]
MgY2- .[Y 4- ]

1
CaY2 [Y ]
MgY2 .[Y 4- ]
4-

1
[Y ]=
10 9,75
CaY2- .MgY2
4

1.5.4. Cc yu t nh n s phn ly ca phc. HSB


iu kin
Theo nh lut bo ton khi lng:
[Mg2+] + [MgY2-] = 10-2
[Mg2+] = 9,2.10-3
[Ca2+] = 8,2.10-4
V d 2: Tnh nng cn bng ca Mg2+, Y4-, MgY2- khi
trong dung dch c Mg2+ 10-2M, Y4- 10-2M, pH = 11. Bit:
(MgY2-) = 108,7
(MgOH+) = 102,58
H4Y c pK1 = 2; pK2 = 2,67; pK3 = 6,27; pK4 =
10,95

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 NH4Cl
Trong dung dch c s in ly: NH4Cl NH4+ + Cl Trong dung mi nc: NH4+ + H2O
Nn: NH4Cl + H2O

NH3 + H3O+

NH3 + Cl- + H3O+

V th dung dch thu c sau khi ha tan mui NH4Cl


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

2.1. c tnh chung ca nhm

Nhm 1 cation gm: Ag ; Hg2+ ; Pb2+, 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.

2.2. 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 H2SO4 long
H2SO4 long v cc mui sunfat tan s phn ng vi cc

cation nhm 1 vi mc khc nhau. Cc cation Ag+ v


Hg22+ mun to kt ta vi ion SO42- th nng ca
chng trong dung dch phi tng i ln so vi Pb2+ to

kt ta PbSO4 tan PbSO4 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, Hg2(OH)2, Pb(OH)2 nhng tnh cht ca cc
hirxit ny c khc nhau. AgOH v Hg2(OH)2 rt khng bn, b phn
hy ngay khi to thnh v cho ra cc oxit tng ng Ag2O, Hg2O,
cn Pb(OH)2 th li tan trong kim d.
Ag+ + OH = AgOH mu trng
AgOH b phn hy rt nhanh.
2 AgOH = Ag2O mu en +H2O

Ag2O khng tan trong kim d, nhng d tan trong HNO3, NH4OH v
b nh sng phn hy thnh Ag kim loi.

2.2. Thuc th chung cation nhm 1


Vi thuc th NH3
2 Ag 2 NH 4OH Ag2O NH 4 H 2O

Ag2O 2 NH 4OH 2Ag( NH 4 ) 2 OH 3H 2O

Pb( NO3 ) 2 NH 4OH PbOHNO3 NH 4 NO3


2 Hg ( NO3 ) 2 4 NH 3 H 2O ( NH 2 Hg 2O) NH 3
2 Hg 0 3NH 4 NO3

Vi thuc th K2CrO4
2Ag+ + CrO42- = Ag2CrO4 mu nu
Phn ng ny tin hnh trong mi trng trung tnh (pH = 7).
Pb2+ + CrO42- = PbCrO4 mu vng
2Pb2+ + Cr2O72- + H2O = 2PbCrO4 + 2H+

2.2. Thuc th chung cation nhm 1


Vi thuc th H2S

Hg 2 H 2 S HgS Hg 0 2 H

2 Ag S 2 Ag2 S
3 Ag2 S 2 NO3 8 H 6 Ag 2 NO 3S 4 H 2O
Pb2 H 2 S PbS 2 H
3PbS 8 HNO3 3PbSO4 8 NO 4 H 2O

Vi thuc th Na2S2O3
2 Ag S 2O3

Ag2 S 2O3

Ag2 S 2O3 3S 2O32 2AgS 2O3 2

2 Ag S 2O3

2 Ag S 2O3

H 2O Ag2 S SO42 2 H 3S 2O32


4 H Ag2 S SO42 3SO2 3S 2 H 2O

Hg 22 2 S 2O32 HgS Hg S 2 SO32


Pb2 S 2O32 PbS2O3

PbS2O3 2 S 2O32 PbS 2O3

PbS 2O3 4 2 H

PbS 2 S 2 SO2 SO42 H 2O

2. 2. Thuc th chung cation nhm 1

Cc cation nhm 1: Ag+, Pb2+, Hg22+


Thuc th

Cation
Ag+

HCl long

H2SO4
long
KOH hoc
NaOH

Pb2+

AgCl trng, tc PbCl2 tan


dng v tan trong trong nc
NH4OH d
nng

Ag2O en

NH4OH d To thnh phc


tan

PbSO4 trng

Hg22+
Hg2Cl2 trng, tc
dng vi NH4OH
ha en

Hg2SO4 trng

Pb(OH)2 trng, Hg2O en


tan trong kim
d
Pb(OH)2 trng

[Hg2ONH2]NO3 +
Hg en

2.2. Phn tch nh tnh cation nhm 1


Thuc th

Cation
Ag+

Pb2+
Pb2(OH)2CO3
trng

Hg22+

K2CO3 hay
Na2CO3

Ag2CO3 trng

Hg2CO3 HgO
+ Hg + CO2 kt
ta xm

K2CrO4

Ag2CrO4 nu PbCrO4 vng,


Hg2CrO4
tan trong kim d

KI

AgI vng

PbI2 vng, tan


trong nc nng

Hg2I2 xanh lc
tc dng vi
thuc th d
HgI42- + Hg

H2S v cc mui
Na2S, (NH4)2S

Ag2S en

PbS en

HgS + Hg en

Cu

Ag trng

To hn hng
mu trng

2.3. Phn tch h thng cation nhm 1


Dung dch phn tch + HCl long; Li tm

Nc lc 1

Kt ta 1 + H2O un si, lc nng

Nc lc 2 + KI (hoc K2CrO4)

PbI2 vng (hoc PbCrO4 vng)

Kt ta 2 + NH4OH

Kt ta en
xm Hg +
NH2HgCl

Nc lc 3 + HNO3

AgCl trng

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: Ca2+, Sr2+, Ba2+ 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 H2SO4 long v cc mui sunfat
To tinh th mu trng khng tan trong axit v kim

Dng thuc th Na2CO3 hoc K2CO3 hoc (NH4)2CO3

To kt ta tinh th mu trng, t tan trong nc nhng


tan trong cc axit HCl, HNO3

3. 2. Thuc th chung cation nhm 2


Dng thuc th K2CrO4
To kt ta tinh th mu vng BaCrO4, SrCrO4 t tan
trong nc ( tan ca chng l S (BaCrO4 ) = 1,55.10-5

gmol/L; S (SrCrO4 )= 4,0.10-4 gmol/L).

Dng thuc th (NH4)2C2O4

To kt ta Oxalat tinh th mu trng tan trong cc


acid HCl, HNO3, ring BaC2O4v SrC2O4 tan c c
trong acid axetic.

3. 2. Thuc th chung cation nhm 2

Cc cation nhm 2: Ba2+, Sr2+, Ca2+


Thuc th

Cation
Ba2+

Sr2+

Ca2+

H2SO4 long

BaSO4 trng

SrSO4 trng

CaSO4 trng, tan nhiu


trong nc

Nc thch cao
CaSO4 bo ha

BaSO4

SrSO4

Na2CO3

BaCO3 trng

SrCO3 trng

CaCO3 trng

H2SO4 c

BaHSO4

SrHSO4

CaHSO4

- Mi trng trung tnh

BaCrO4 vng

SrCrO4 vng

- Mi trng axit axetic

BaCrO4 vng

(NH4)2SO4

BaSO4

SrSO4

Ca(SO4)22-

(NH4)2C2O4

BaC2O4 trng

SrC2O4 trng

CaC2O4 trng

Na2HPO4

BaHPO4 trng

SrHPO4 trng

CaHPO4 trng

Th mu la

Ngn la mu vng lc

Ngn la mu

Ngn la mu gch

K2CrO4

3. 3.Phn tch h thng cation nhm 2


L1 + H2SO4 long + ru etylic, li
tm, lc gn
Kt2 + MeSO4 chuyn thnh MeCO3
bng Na2CO3 bo ha
Kt MeCO3 + CH3COOH n va tan ht +
K2CrO4, li tm, lc
Kt + NaOH lc k, li tm

BaCrO4
vng

Nc lc +
Na2S

PbS en

L + Na2CO3 SrCO3 + CaCO3, li tm, ly kt


ta, ra sch bng nc
Kt + CH3COOH n va tan ht, chia
thnh 2 phn

Phn t + CaSO4
bo ha

SrSO4 trng

Phn nhiu + (NH4)2SO4, li


tm, lc

SrSO4
trng
CaC2O4
trng

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 Al3+, Zn2+, Cr3+ 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 (CrO2-) kt hp vi cc cation nh Mg2+, Mn2+, Fe3+, Zn2+ to
thnh nhng kt ta kh tan Mg(CrO2)2, Zn(CrO2)2, Mn(CrO2)2 v vy

tch Cr3+ cng vi nhm III, thng dng kim d v c mt H2O2 oxi
ha Cr3+ v CrO42- .V vy cho nn thuc th tch nhm III l NaOH
(hoc KOH) d v H2O2.

4. 2. Thuc th chung ca cation nhm 3


Dng dung dch NH3
Amni hidrxit (NH4OH) tc dng vi cc cation nhm III to thnh
cc hidrxit khng tan, nhng ring Zn2+ khi dung dch NH3 d s
lm kt ta ny v c ion ny chuyn thnh phc amoniacat tan
Zn(NH3)42+

Cr(OH)3 tan t trong NH4OH d, khi c mt NH4Cl to


thnh mui kp CrCl3.NH3mu 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 Na2CO3 hay K2CO3
To thnh kt ta hidroxit, ring vi ion Zn2+ 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 S2Ion Zn2+ trong mi trng trung tnh, kim yu hoc c mt
mui axetac natri th tc dng vi H2O hay (NH4)2S to thnh
kt ta sunfua km mu trng:
ZnCl2 + H2S + 2CH3COONa = ZnS + 2NaCl + 2CH3COOH

Ion Sn4+ v Sn2+ trong mi trng HCl tc dng vi H2S to


thnh cc sunfua kh tan:

4.2. Thuc th chung cation nhm 3

Cc cation nhm 3: Al3+, Cr3+, Zn2+, Sn2+, Sn4+, As3+, As5+


Thuc th

Cation
Al3+

Cr3+

Zn2+

Sn2+

Sn4+

NaOH d

AlO2-

CrO2-

ZnO22-

SnO22-

SnO32-

NaOH, Na2CO3 khng d

Al(OH)3
trng

Cr(OH)3 lc

Zn(OH)2 trng

Sn(OH)2
trng

Sn(OH)4
trng

DD NH3

Al(OH)3

Cr(OH)3

[Zn(NH3)4]2+

Sn(OH)2

Sn(OH)4

Na2HPO4

AlPO4 trng

CrPO4 xanh
lc

Zn3(PO4)2 trng

Sn(OH)2

Sn(OH)4

SnS nu

SnS2 vng

H2S trong mi trng HCl

H2S trong mi trng


CH3COOH

(NH4)2S trong mi trng


trung tnh hoc kim
Vi cc cht oxy ha: H2O2,
KMnO4
Alizarin trong mi trng NH3

Al(OH)3
Kt ta son

Cr(OH)3
Cr3+ Cr6+
Kt ta nu
nht

ZnS trng

ZnS

Kt ta nht

Sn2+ Sn4+
Kt ta vng
gch

Kt ta vng
nht

4.3. Phn tch h thng cation nhm 3


L2 + NaOH d + H2O2, un k, li tm, b kt ta

L3 + NH4Cl, un si k, li tm

L3,1 chia lm 2 phn

Kt3,1

Lc mnh, un nng
vi (NH4)2S
Nc lc c
SnS32- +
CH3COOH
SnS2
vng

Kt ra sch +
CH3COOH n
tan + alizarin +
NH4OH Kt
son

P1: + H2O2 + ru
amylic + H2SO4

P2: + Na2S

Lp ru c mu
xanh ca H3CrO8

ZnS trng

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