CHNG 1

AI CNG VE HOA PHAN TCH

Ha phn tch: nghin cu cc phng php phn

tch nh tnh v nh lng thnh phn ha hc
ca cc cht.
Trong
mu
p.t
c
p.t nh tnh:
nhng
cht
g?
Ha phn tch:
p.t nh lng: Hm lng cc
cht trong mu
Khi nghin cu thnh phn mt cht cha
bit:phn tch nh tnh trc, phn tch nh
lng c tin hnh sau.

CAC GIAI OAN TIEN HANH PHAN TCH

Lay mau ai dien.
Bao quan mau phan tch.
Tao mau di dang thch hp.
Tien hanh phan tch nh tnh.
La chon qui trnh phan tch nh lng.
Co lap hoac loai bo bt mot so cau t can
tr.
Tien hanh nh lng.
Tnh toan ket qua.

Cc phng php phn tch nh lng

Phn tch ha hc v phn tch dng c
Ham lng
Ky thuat phan tch
1 10mg :vi lng

Phan tch dung cu

10-3mg :siu vi lng
10- 100mg :bn vi lng
Phan tch hoa hoc
> 100mg:a lng

P.P ha hc
(Dng thit b n gin)

PP khi lng
PP th tch

PP khi lng
TD: Phn tch hm lng Fe3+ trong mu
Fe3+ + OH- Fe(OH)3 Fe2O3
T khi lng Fe2O3 => hm lng Fe3+
+ Chuan o acid baz
PP th tch
+ Chuan o phc cht
(Cc cht p
+ Chuan o oxy ha - kh.
trng thi dd)
+ Chuan o kt ta.

 pht x
PP vt l:Tn hiu vt l Ph pht x

PP dng c: PP ha l
PP quang, pp in
(P ha hc + PP in th
tn hiu vt l) PP hp thu phn t

CHNG II
PHNG PHP PHN
TCH KHI LNG

I. Nguyn tc:
lc
R
ra,
sy
Y
Z (dng cn)
X (dd)
nung
(dng kt ta)
II. Cc yu cu i vi dng kt ta v dng cn
1. Dng kt ta:
* TY < 10-10 ,tinh khit v d lc
* Y Z d dng v hon ton
2. Dng cn:
* c thnh phn ng vi cthh xc nh.
* Khng (ht m, hp th CO2, b phn hy).
* mZ > mng.t cn phn tch cng nhiu => chnh xc

III. Cch tnh kt qu trong phn tch khi lng

1. H s chuyn K: Nu dng cn:AmBn
m.M A
K=
M Am Bn

MA: nguyn t gam ca cht

cn phn tch A
Trng hp tnh % A di dng AxDy t AmBn
M Ax D y m
K=
.
M Am Bn x

2. H s pha long:
*Vm:Th tch dd (X) sau khi a gam
Vm cht cn phn tch ha tan.
F=
Vx *Vx: Th tch dd(X) ly em phn
tch

3. Tnh kt qu:
a: lng cn ban u ca
b
% X = K . .100 mu cha X cn phn tch
a

b: khi lng dng cn.

Nu em a gam ha tan v nh mc n Vm:

Vm
% X = K.
.100
Vx

* xc nh m ca mu:

a a'
(a: lng mu cn
%.m =
.100 li sau khi sy kh)
a

Td1:
H+ Fe(OH) .xH O Lc Fe O
2 3
1,1245g(X) OH3
2
Sy, 0,3412g
a) Hm lng Fe di dng Fe

mFe2O3
2.Fe 2.56
.100
K=
=
= 0,7 % Fe = K .
mX
Fe2O3 160
% Fe = 0,7.

0,3412
1,1245

b) Di dng Fe3O4
Fe3O4 2
K=
.
Fe2O3 3

.100 = 21,24%

232 2
K=
. = 0,9666
160 3
0,3412
% Fe3O4 = 0,9666.
.100 = 29,33%
1,1245

CHNG III

PHN TCH TH TCH

I. Nguyn tc
A
+ B
C
A v B u trng thi dung dch
Dung dch A c nng C0 cha
bit
Dung dch B c nng C bit
Dng dd B xc nh nng dd A :
php chun .
Dd A: dd cn chun .
Dd B: dd chun.

Dd
chun

Dd cn
chun

TIN TRNH CHUN

Ly chnh xc V0 ml dd A (c
nng C0(CN) cho vo bnh
(erlen)
Bit : Th tch dd mu
Khng bit: nng dd mu

Qu trnh nh t t dd B t Buret vo dd A :
qu trnh chun (nh phn)
Bit:Nng ca dd B.
Th tch dd B tiu tn.
DD B : dd chun
im tng ng ca qu
trnh : thi im m B tc
dng va ht vi A
Nhn bit im tng
ng: Cht ch th

Cht ch thi :nhng cht c

kh nng thay i mu sc
hay to mt kt ta c mu
gn im tng ng
im cui ca qu trnh
chun : thi im kt
thc qu trnh chun .

IM TNG NG

DIM CUI

Cht chun tc dng

Thi im kt thc
va ht vi cht cn
qu trnh chun
phn tch
S khc nhau gia im tng ng v im
cui .
Sai s chun :

S = Vc Vt

im tng ng im cui S = 0
Thc t : im cui im tng ng sai s
thiu;S(-); sai s tha;S(+)

II. YU CU CA PHN NG DNG TRONG PHN

TCH TH TCH

Cht cn chun phi phn ng vi

thuc th theo mt phng trnh phn
ng xc nh.
Phn ng phi xy ra nhanh , hon ton.
Thuc th ch phn ng vi cht cn
chun m thi.
Phi c cht ch th xc nh im tng
ng

III. PHN LOI CC PHNG PHP PTTT

Da vo bn cht ca phn ng chun :
3.1. Phng php trung ha (axit-baz )
H+

OH

H2 O

3.2. Phng php to phc

Ag+ + 2CN- [Ag(CN)2]*3.3: Phng php oxy ha kh
aOxh1 + bKh2

aKh1

3.4. Phng php kt ta

A

bOxh2

IV.CCH TNH KT QA TRONG PHN TCH TH TCH

1. Chun trc tip.

Chun V0 ml dung dch A phi dng ht V ml

dung dch B c nng C(N). Tnh nng
dung dch A v khi lng A c trong V0 ml
Theo nh lut ng lng : V0.C0 = V.C

C0 =

CV ( N )
V0

=>S mg ca A bng : C0V0 .A

S gam ca A bng : a = C0V0.A/1000

V d: Tnh nng v khi lng ca NaOH,

bit rng khi chun 20ml dung dch NaOH,
phi dng ht 22,75ml dung dch HCl 0,106N.
Gii:
p dng LL :

CNaOH. VNaOH = CHCl. VHCl

CNaOH = (22,57 x 0,106)/20=0,1206N

Khi lng ca NaOH
mNaOH= (0,1206x20 x40)/1000= 0,09648 g

2.CHUN NGC
Cht cn chun A tc dng vi thuc
th B d. Lng B cn tha c chun
bg thuc th X .
S dng khi:
im cui ca chun ngc r hn dim
cui ca chun trc tip.
Dung dch chun cho d ban u phi phn
ng hon ton vi cht phn tch.

Ban u: HA +
C0.V0

BOH BA + H2O (1)

C V1

Sau cho lng chun d phn ng vi mt

cht chun th hai theo phn ng:
BOH +
C.V2

HX BX + H2O (2)
C.V

T (1) v (2)
C.V= C(V1+V2) = C0.V0 + C.V
C V - CV
C0 =
V0

3. CHUN THAY TH

Cho A tc dng vi cht MY theo phng trnh:

A + MY
MA + Y (1)
C0V0
CYVY=C0V0
Sau chun Y thot ra bng thuc th B
Y
+ B
C (2)
C YV Y
CV
(1) V (2) => C0V0 = CYVY = CV

A. CHUN ACID BAZ

I. ACID - BAZ
1. nh ngha acid - baz
a. Thuyt Arhenius:
HO
*Dm = H2O
AHn An- + nH+
H O m+
B(OH)m B + mOH- *Acid n chc
* Baz m chc
* CH+ => dd c tnh acid
* COH- => dd c tnh baz
Td: HCl(k) + NH3 (k) NH4Cl(r)
Khng phi l phn ng acid-baz v khng
c H O.
2

b. Thuyt Bronsted:( Thuyt proton)

AHn An- + nH+
* Dm bt k
*
Acid
n
chc
B + mH+ (BHm)m+ * Baz m chc
* AHn H+ => Tnh acid
* B + H+ => Tnh baz
H+

Td: HCl(k) + NH3(k) NH4Cl(r)

Acid
Baz

Xem p:

H+

Baz1 acid2
AH + BOH A- + BOH2+
Acid1 baz2
H+
AH A- + H+ ;AH/A-:cp acid/baz lin hp(1)
BOH2+ BOH + H+; BOH2+/BOH: Cp acid
/baz lin hp(2)
Trong 1 cp acid/baz lin hp:
Dng acid => dng baz lin hp
Dng acid => dng baz lin hp

2. pH ca dung dch (dung mi l H2O)

Trong dd/H2O ta lun lun c:
Kn = CH+.COH-= 10-14 25oC
pKn = pH + pOH = 14 25oC
pKn = - lgKn ; pH = -lgCH+ ; pOH = -lgCOH-

a. pH ca dd acid - baz
. pH ca dd acid
* Dd acid mnh

to
t

AHn An- + nH+

CA(M) 0
0
0
CA nCA

=> CH+ = nCA

CH+ = CN = nCA

Ta c CN = nCA
=> pH = -lgCH+ = -lg(nCA)

* Dd acid yu n chc
AH
to CA
tcb CA - x

A +

0
x

0
x

[
H
][
A
]
Ka =
[ AH ]
Ka => acid

t pKa = -lgKa Ka => pKa

pH = (pKa lgCA)
Td: dd CH3COOH(0,1M) ; Ka = 10-5 c:
pH = (-lg10-5 lg0,1) = 3

Xt cp acid/baz lin hp:

[
H
][
A
]
=
K
+
a
AH A + H
[ AH ]

A- + H2O AH + OH+

[
AH
][
OH
]
Kb =

[A ]

[
H
]
[
A
]
[
AH
][
OH
]
+

=
*
=
[
H
][
OH
]
K a Kb

[ AH ]
[A ]
=> Ka.Kb = Kn = 10-14 25oC
Ka => Kb Acid cng mnh => baz lin
Ka => Kb hp cng yu; v ngc li

*Acid yu a chc :Xem 1 acid yu 3 chc:

AH3 AH2- + H+ Ka1 = [AH2-][H+]/[AH3]
2+
2+
K
=
[AH
][H
]/[AH
AH2 AH + H
a2
2]
3+
223+
K
=
[A
][H
]/[AH
]
AH A + H
a3
Thng:Ka1>>Ka2>>Ka3 Nu:Ka1/Ka2/Ka3 104
Xem AH3 nh acid yu n chc viKa=Ka1
=> pH = (pKa1 lgCA)
Td:dd H3PO4(0,1M);c Ka1=10-2,1,Ka2=10-7,2
Ka3=10-7,3:Ka1/Ka2/Ka3=105
=>pH= (-lg10-2,1 lg0,1) = 1,55

)Dd baz: *Dd baz mnh

B(OH)n Bn+ + nOH- COH- = nCB
to CB
0
0
CN = nCB
t 0
CB nCB
=>COH-= CN = nCB
pH = 14 pOH =14 {-lg(nCB)}
Td: dd NaOH
0,1N: COH-=CN=0,1=>pH=14- (-lg0,1) = 13
0,1M:COH-=CN=CM=0,1=> pH= 13
Td:dd Ba(OH)2
0,1N:COH-=CN=0,1 => pH = 13
0,1M:COH-=CN=2CM=0,2=>pH=14-(-lg0,2)=13,33

*Dd baz yu n chc:

BOH B+ + OH- C0 = CB(M)
+

[
B
][
OH
]
pKb= -lgKb
=
Kb
[ BOH ]
Kb=>pKb, baz
pH = 14 (pKb lgCb)
Td:dd NH4OH(0,1M); pKb = 5 c:
pH = 14 (5 lg0,1)=11
* Trng hp dd baz yu a chc
Nu: Kb1/Kb2/Kb3104,

Ta cng xem nh
1 baz yu c Kb = Kb1

b) Dd mui
Mui c xem l sn phm ca p gia
acid vi baz
Acid + baz Mui + H2O
m
m
4 loi mui
y
)Dd
y mui ca acid mnh v baz mnh:
mAHn + nB(OH)m AmBn + m.nH2O
AmBn mAn- + nBm+
An- v Bm+ l gc ca acid, baz mnh
=> Khng b thy phn => pH = 7

) Dd mui ca acid yu v baz mnh:

AH + BOH AB + H2O
pH > 7
AB A- + B+
A- + H2O AH + OH- pH=(pKn+pKa+lgCm)
) Dd mui ca acid mnh v baz yu:
pH < 7
AB A- + B+
B+ + H2O BOH + H+ pH= (pKn-pKb-lgCm)
) Dd mui ca acid yuv baz yu:
AB A- + B+
pH ty thuc vo s
A- + H2O AH + OH- so snh gia Ka v Kb
+
+ pH=(pKn+pKa-pKb)
B + H O BOH + H
2

* Trng hp mui lng tnh ;

Xem mui AH2- ca acid yu AH3

+
[ H ][ AH 2 ]
AH3 AH2- + H+ K a1 =
[ AH 3 ]
+
2
[ H ][ AH ]
=
2+
K
a
2
AH2 AH + H

[ AH 2 ]
+
2

+
[H ][ AH 2 ] [ H ][ AH ]
+ 2
=
.
=
[
H
]
K a1 K a2

[ AH 3 ]
[ AH 2 ]
=> [H+] = (Ka1.Ka2)1/2
pH = (pKa1 + pKa2)
pH = (-lgKa1 lgKa2)

Xem mui AH2- ca acid yu AH3:

AH2- AH2- + H+ Ka2
AH2- A3- + H+
Tng t , ta c:

Ka3

pH = (pKa2 + pKa3)
Td: H3PO4 cKa1=10-2,1;Ka2=10-7,2;Ka3=10-12,3
Dd H3PO4(0,1M): pH=(-lg10-2,1-lg0,1)=1,55
NaH2PO4(0,1M) pH=(-lg10-2,1-lg10-7,2)=4,65
Na2HPO4(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 lng nh H+ hoc OHDd n {acid(y) v mui ca n vi baz(m)}
HO
(CH3COOH + CH3COONa) Dd n acid
CH3COONa CH3COO- + Na+
pH < 7
+
CH3COOH CH3COO + H
+H+=> C H + =>cb>nghch=> H+ p ht
+OH-;OH- + H+ H2O=> C H + =>cb> thun
=> OH- p ht
Ca
Vy: pH dd khng i. pH = pK a lg C
2

Dd n {baz(y) + mui ca n vi baz(m)}

HO
NH4OH + NH4Cl Dd dn baz
NH4Cl NH4+ + ClpH > 7
+
NH4OH NH4 + OH
+H+:H+ + OH- H2O COH =>cbthun
=>H+ p ht => pH khng i
2

+ OH- => COH =>cbnghch =>OH p ht

=> pH khng i

Cb
pH = 14 ( pK b lg
)
Cm

II. NGUYN TC:

1. Phn ng:
C
?
0
Acid
V0

+ Baz C
V

Mui + H2O

C
?
0
Baz
V0

C
+ Acid
V

Mui + H2O

Dd cn chun Dd chun:
c th
lun mnh
mnh hoc
yu

2. Cht ch th mu:
Cht ch th mu acid baz thng l acid
hoc baz yu,mu ca dd ph thuc vo pH
ca dd.
Xem cht ch th mu l 1 acid yu Hind:
HO
Hind H+ + ind+

[
Hind
]
[
H
][
ind
]
+
[H ] = K .
Ka =
a

[ Hind ]
[ind ]
2

[
Hind
]
pH = lg K a lg
pH

[ind ]

[
Hind
]
pK a lg

[ind ]

 pH

[
Hind
]
pK a lg

[ind ]

*[Hind] 10[ind-] =>dd c mu ca dng Hind

=> pH pKa lg 10 pKa - 1
*[ind-]10[Hind] =>dd c mu ca dng Ind=> pH pKa lg1/10 pKa + 1
=> pH = pKa 1 l khong pH i m ca
cht ch th
pK
a
Mu ca Hind
Mu ca indpH
pK - 1
pK + 1
a

Cc cht ch th acid baz thng dng:

* Mi c.c.t c 1 gi tr pT xc nh
pT=pKa=pHdd m ti c.c.t i mu r nht

3.ng cong chun :

Td: chun dd AH bng dd BOH
AH + BOH AB + H2O
Co V o
CV

CV
: phn chun
F =
C0 V 0
xc nh cht ch mu dng trong php
chun .Ta phi v ng biu din pH
ca dd chun , theo th tch dd chun
thm vo dd chun (hoc theo F) cc
thi im khc nhau.

III. Chun dd acid baz mnh

1. Chun dd acid mnh
* Cha chun : CV = 0 => F = 0
AHn + nNaOH NanA + nH2O
Dd ch c AHn( acid mnh) => pHo = -lgCo
* 0 < CV < CoVo => 0 < F < 1 => Trc t
AHn + nNaOH NanA + nH2O
AHn: C1 =
Dd

NanA

C 0 V 0 CV
V0 + V

C 0 V 0 CV
pH 1 = lg
V0 + V

*CoV0 = CV => F = 1: t
AHn + nNaOH NanA + nH2O
Dd ch c NanA => pH = 7
* CoVo > CV => F > 1: Sau t
AHn + nNaOH NanA + nH2O
pH tnh theo
NaOH(cn
tha)
Dd gm
NaOH
Na A
n

C NaOH

C V C0 V 0
CV C 0 V 0
= 14 [ lg
=

pH
]
2
V0 + V
V0 + V

ng cong chun
Td: chun 100ml dd HCl 0,1N bng dd
NaOH 0,1N
HCl + NaOH NaCl + H2O
Co V o
CV
pHo = - lg0,1 = 1
* CV = 0 => F = 0
pHtd = 7
100
.
0
,
1
* CoVo = CV => F = 1
=
=100ml

V t

0,1

* V1 = 99,9ml F1 =

99,9.0,1 =
0,999
100.0,1

100.0,1 99,9.0,1
pH 1 = lg
= 4,3
+
100 99,9
100
,
1
.
0
,
1
* V2 = 100,1ml F 2 = 100.0,1 = 1,001

100,1.0,1 100.0,1 = 9,7

pH 2 = 14 [ lg
]
100 + 100,1

Nhn xt:
* ng cong chun
i xng qua t
* Cc cht ch th c pT
nm trong bc nhy
pH u c th dng
lm cht ch th
* Bc nhy pH cng
ln khi nng cht
cn chun cng ln

2.Chun dd baz mnh bng acid mnh

* CV = 0 => F = 0 => Dd ch c B(OH)n
B(OH)n + nHCl BCln + nH2O
=> pHo = 14 (-lgCo)
* CV < CoVo => F < 1 ( trc t)
B(OH)n + nHCl BCln + nH2O
Dd gm

B(OH)n
=>pH tnh theo B(OH)n
BCln

C0 V 0 C V
pH 1 = 14 [ lg
]
V0 + V

* CV = CoVo => F = 1 (t)

B(OH)n + nHCl BCln + nH2O
Dd ch c BCln => pH = 7
* CV > CoVo => F > 1 (sau t)
B(OH)n + nHCl BCln + nH2O

C V C 0 V 0 pH tnh
HCl C HCl =
theo HCl
Dd gm
V0 +V
BCln

C V C0 V 0
pH 2 = lg
V0 + V

ng cong chun
Td: chun 100ml dd NaOH 0,1N bng dd
HCl 0,1N
NaOH + HCl NaCl + H2O
Co V o
CV
* Vo = 0ml => F=0 =>pHo= 14-(-lg0,1) = 13
pHtd= 7
* CV= CoVo => F=1
100
.
0
,
1
V t = 0,1 = 100ml
* V=99,9ml => F= 0,999

100.0,1 99,9.0,1
= 9,7
pH 1 = 14 [ lg
]
+ 99,9

* V = 100,1ml => F = 1,001

100,1.0,1 100.0,1
= 4,3
pH 2 = lg
100 + 100,1

IV. Chun dd acid- baz yu

1. Ch. dd acid (y) a. Dd acid (y) n chc:
*CV = 0 => F = 0 Dd(AH)
AH + NaOH NaA + H2O
pHo= (pKa+lgCo)
*CV < CoVo =>F<1 AH+NaOH NaA +H2O
C0V0 CV
C
AH: Ca =
a
V
+
V
Dd
pH 1 = pK a lg
0
CV
Cm
NaA: Cm =
V0 + V
C0V0 CV
1 F
pH 1 = pK a lg
= pK a lg
CV
F

* CV = CoVo => F = 1
AH + NaOH NaA + H2O
C 0 V 0 = CV
Dd (NaA):C m =
:Mui
b
thy
phn
V0 + V

pH t =

1
2

C0V0 = CV
( pK n + pK a + lg
)
V0 + V

* CV > CoVo => F > 1

AH + NaOH NaA + H2O
Dd NaOH
NaA

CV C0V0
pH 2 = 14 ( lg
)
V0 + V

ng cong chun
Td : Chun 100ml dd CH3COOH 0,1M
(pKa= 4,8) bng dd NaOH 0,1M
CH3COOH + NaOH CH3COONa + H2O
* F = 0 => pHo= (4,8 - lg0,1)= 2,9
*F = 0,5

*F=1

pH 0,5 =

1 0,5
pK a lg
=pKa= 4,8
0,5

100
.
0
,
1
= 100ml
V t = 0,1
1
pH t = 2 ( 14 + 4,8 +

lg

100.0,1
)
=8,75
100 + 100

* V= 99,9ml => F = 0,999

1 0,999
pH 1 = 4,8 ( lg
) = 7,8
0,999
* V = 100,1ml => F = 1,001
100,1.0,1 100.0,1
pH 2 = 14 ( lg
) = 9,7
100+ 100,1
V(ml)
0
50
99,9
100
100,1

0
0,5
0,999
1
1,001

pH
2,9
4,8
7,8
8,75
9,7

Ghi ch
Cha chun

Ln cn trc
im tng ng
Ln cn sau

p.p

Bc nhy pH

Nhn xt
im tng ng nm
trong mi trng kim (pH >
8)

Bc nhy ca ng
chun ngn hn nhiu so
vi khi chun axit(m)
bng baz(m)

Nng cc cht cng ln

th bc nhy cng di

Cht ch th thch hp l PP

b. Dd acid yu a chc:
Td: xem acid yu AH3:Nu: Ka1/Ka2/Ka3 104
C th chun ring tng chc
AH3 + NaOH NaH2A + H2O C0(M)
* CV = 0 => F = 0 => pHo = (pKa1 lg Co)
* 0 < CV < CoVo => 0 < F < 1 (trc t 1)
AH3 + NaOH NaH2A + H2O
C0V0 CV
AH
:
3 Ca =
Dd
Dd n 1
V0 + VCV
NaH2A: Cm =
V0 + V
C0V0 CV
1 F
pH1 = pK a1 lg(
) = pK a1 lg
CV
F

* CV = CoVo => F = 1(t 1)

AH3+ NaOH NaH2A+H2O

pH t 1 = 12 ( pK a1 + pK a 2 )

* CoVo < CV < 2CoVo=> 1 < F < 2

NaH2A + NaOH Na2HA + H2O
2C0V0 CV
NaH2A: Ca =
V0 + V
Dd
Dd
n
2
CV C0V0
Na2HA: Cm =
V0 + V
2C0V0 CV
2 F
pH 2 = pK a 2 lg
= pK a 2 lg
CV C0V0
F1

* CV = 2CoVo => F = 2 (t 2)
NaH2A + NaOH Na2HA + H2O
pHt2 = (pKa2 + pKa3)
* 2CoVo < CV < 3CoVo => 2 < F < 3
Na2HA + NaOH Na3A + H2O
3C0V0 CV
Na2HA: Ca =
V0 + V
Dd n 3
Dd
CV 2C0V0
Na3A: Cm =
V0 + V
3C0V0 CV
3 F
pH 3 = pK a 3 lg
= pK a 3 lg
CV 2C0V0
F 2

* CV = 3CoVo => F = 3 (t 3)
Na2HA + NaOH Na3A + H2O
Co V o

(CV= 3CoVo) CoVo

C0V0
Dd (Na3A): Cm =
V0 + V
pHt3= ( pKn + pKa3 + lgCm)
1
pH t 3 = 2 [ pK n +

C0 V o
pK a3 + lg(
)]
V0 + V

CV=CoV

CV=2CoVo

AH3(CoVo)

CV=3CoVo

ng cong chun :
Td: chun 50ml dd H3PO4 0,1M
(pKa1=2,1; pKa2=7,2;pKa3=12,3) bng dd
NaOH 0,1M
C
th
chun

tng
5
* Ka1/Ka2/Ka3 = 10
chc ring bit
H3PO4 + NaOH NaH2PO4 + H2O (1)
NaH2PO4 + NaOH Na2HPO4 + H2O(2)
Na2HPO4 + NaOH Na3PO4 + H2O (3)

* CV = 0 => F = 0 (cha chun )

Dd ( H3PO4) => pHo= (pKa1-lgCo)
= (2,1-lg0,1) = 1,55
* CV= (CoVo) => F = 0,5

pH 0,5 =

1 0,5
pK a1 lg
=pKa1= 2,1
0,5

* CV = CoVo => F = 1 (t 1)
pHt1 = (pKa1+pKa2)= (2,1+7,2) = 4,65
* CV= 1,5CoVo=> F = 1,5

pH 1,5 =

2 1,5
pK a 2 lg
=pKa2=7,2
1,5 1

* CV= 2CoVo=> F=2 (t 2)

pHt2= (pKa2+pKa3)= (7,2+12,3) = 9,75
* CV= 2,5CoVo=> F = 2,5

pH 2,5 =

3 2,5
pK a3 lg
2,5 2

=pKa3=12,3

* CV=3CoVo=> F=3 (t 3)
1
pH 3 = 2 (14 +

0
,
1
.
50
pK a3 + lg
)
50+ 150

= [14+ 12,3 + lg(0,1/4)] = 12,34

F
0

Cng thc tnh pH

pHo= (2,1-lg0,1)

pH
1,55

0,5 pH1/2= pKa1= 2,1

2,1

3,65

pHt1= (pKa1+pKa2)

1,5 pH3/2= pKa2

7,2

2,0 pHt2= (pKa2+pKa3)

9,75

2,5 pH5/2= pKa3

12,3

Ghi ch
Cha chun
t 1
t 2

3,0 pHt3=(14+pka3+lg0,1/4) 12,34 t 3

p.p

Metyl da cam

p.p

Metyl da cam

2. Chun dd baz yu
a. dd baz yu n chc
* CV = 0 => F = 0 (cha chun )
BOH + HCl BCl + H2O
Dd ( BOH) =>pHo=14- (pKb lgCo)
* 0 < CV < CoVo => 0 < F < 1
BOH + HCl BCl + H2O
Dd

C0V0 CV
BOH: Cb = V + V
0
CV
BCl: Cm =
V0 + V

Dd n baz yu

C0V0 CV
1 F
pH1 = 14 ( lg
) = 14 ( lg
)
CV
F

* CV = CoVo => F = 1
BOH + HCl BCl + H2O
C0V0 = CV
Dd (BCl) Cm =

pH t =

1
(
pK
n
2

C0 V 0
pK b lg
)
V0 + V

V0 + V

* CV > CoVo => F > 1

BOH + HCl BCl + H2O
CV C0V0
HCl:
Ca =
Dd
V0 + V
BCl

CV C 0 V 0
pH 2 = lg
V0 + V

ng cong chun :
Td: Chun 10ml dd NH4OH 0,1 M
(pKb= 4,8) bng dd HCl 0,1 M
NH4OH + HCl NH4Cl + H2O
CoVo
CV
F
Cng thc tnh pH
0,0 pHo= 14- (4,8-lg0,1)

pH
Ghi ch
11,1 Cha c.

0,5 pH0,5=14-(pKb-lgCa/Cm)

9,2

1,0 pHt = [14-4,8-lg(0,1)/2]

5,25 t

1,5 pH2= -lg[(15.0,1-10.0,1)/(10+15)] 1,6

Nhn xt
im tng
ng ti min
axit

Cht ch th
thch hp nht
cho php chun
ny l metyl
da cam, metyl

b. Chun dd baz yu a chc:

Cc baz yu a chc thng l cc mui
trung ha ca acid yu a chc
Xem baz yu A3- (l mui trung ha ca AH3)
Khi ha tan A3- vo nc:
A3- + H2O AH2- + OH- Kb1=Kn/Ka3
AH2- + H2O AH2- + OH- Kb2=Kn/Ka2
AH2- + H2O AH3 + OH- Kb3=Kn/Ka1
Nu: Kb1/Kb2/Kb3 104 => C th chun
tng chc ring bit

* CV = 0 => F = 0 (cha chun )

* A3- + HCl AH2- + ClDd (A3-) =>pHo= (pKn + pKa3 + lgCo)
* 0 < CV < CoVo=> 0 < F < 1
A3- + HCl AH2- + ClCV
2AH : Ca =
V0 + V
Dd
Dd
n
1
C
V

CV
A3-: Cm = 0 0
V0 + V

CV
F
pH1 = pK a 3 lg
= pK a 3 lg
C0V0 CV
1 F

* CV = CoVo => F = 1 (t 1)
A3- + HCl AH2- + ClDd (AH2-) => pHt1= (pKa2 + pKa3)
* CoVo < CV < 2CoVo => 1 < F < 2
AH2- + HCl AH2- + ClCV C0V0
AH2 : Ca =
V0 + V
Dd
Dd n
2C0V0 CV
2AH : Cm =
V0 + V
CV C0V0
F1
pH 2 = pK a 2 lg
= pK a 2 lg
2C0V0 CV
2 F

* CV = 2CoVo => F = 2 ( t 2)
AH2- + HCl AH2- + ClDd (AH2-) => pHt2 = (pKa1 + pKa2)
* 2CoVo < CV < 3CoVo => 2 < F < 3
AH2- + HCl AH3 + ClCV 2C0V0
AH3: Ca =
V0 + V
Dd
Dd n
3C0V0 CV
AH2 : Cm =
V0 + V

CV 2C0V0
F 2
pH 3 = pK a1 lg
= pK a1 lg
3C0V0 CV
3 F

* CV = 3CoVo => F = 3 (t 3)
AH2- + HCl AH3 + ClDd (AH3)

pH t 3 =

1
(
pK

a1
2

C0 V 0
lg
)
V0 + V

CV=CoVo

A3-(CoVo)

CV=2CoVo

CV=3CoVo

ng cong chun
Chun 10ml Na3PO40,1M bng HCl
0,1M .H3PO4(Ka1=10-21,1;Ka2=10-7,2;Ka3=10-12,3
=> Na3PO4 c: Kb1=10-14/10-12,3 =10-1,7
-14
-7,2
-6,8 K =10-14/10-2,1=10-11,9
Kb2=10 /10 =10 ; b3
=> Kb1/Kb2/Kb3=10-1,7/10-6,8/10-11,9=105
=> C th chun ring tng chc

*F=0: Na3PO4 + HCl Na2HPO4 + NaCl

=> pHo = (14 + 12,3 + lg0,1) = 12,34

F
* F = 0,5 pH 0,5 = pK a 3 lg
1 F
0,5
pH 0,5 = pK a 3 lg
= pK a 3 =12,3
1 0,5

* F = 1 => pHt1= (7,2+12,3)= 9,75

*F =1,5: Na2HPO4 + HCl NaH2PO4 + NaCl
F1
pH1,5 = pK a 2 lg
2 F
1,5 1
= pK a 2 lg
= pK a 2 =7,2
2 1,5

* F = 2 =>pHt2= (2,1+7,2) = 4,65

* F = 2,5: NaH2PO4 + HCl H3PO4 + NaCl

pH 2,5

F 2
= pK a1 lg
3 F
2,5 2
= pK a1 lg
= pK a1 = 2,1
3 2,5

* F = 3 => pHt3 = [2,1 lg(0,1/4)] = 1,85

pH
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0

.
p.p .

Na2HPO4
.

Metyl da cam

0,5

1,0

1,5

2,0

NaH2PO4
.

2,5

3,0

Td: chun 10ml dd Na2CO3 0,1M bng dd

HCl 0,1M. H2CO3(Ka1=10-6,35;Ka2=10-10,33)
* Na2CO3 c Kb1=10-14/10-10,33=10-3,67
Kb2 = 10-14/10-6,35 = 10-7,65
=> Kb1/Kb2 = 10-3,67/10-7,65 = 104
=> C th chun tng chc ring bit

Na2CO3 + HCl NaHCO3 + NaCl

Co V o
CV
* F =0=>pHo = (14 + 10,33 + lg0,1) =11.65
* F=0,5=>pH0,5= pKa2 = 10,33
* F=1=>pHt1= ( 6,35+10,33) = 8,34
* F = 1,5
NaHCO3 + HCl CO2 + H2O + NaCl
=> pH1,5= pKa1 = 6,33
* F = 2 => pHt2 = dd bo ha CO2/H2O= 4

p.p

t1

Metyl da cam

t2

V. Chun dd hn hp
1. Dd hn hp nhiu acid
a. dd hn hp acid mnh
AHn An- + nH+
CH+ = nCa1 + mCa2
m+
BHm B + m+
Ti t cc acid u chun ht
b. dd ( acid mnh + acid yu)
Acid mnh chun trc:
AHn + nNaOH NanA + nH2O
Khi ht acid mnh, acid yu mi chun

Td: Chun dd hn hp HCl(C01) v

CH3COOH(C02) bng dd NaOH(C)
HCl + NaOH NaCl + H2O (1)
Co1Vo CV1
CH3COOH + NaOH CH3COONa +H2O(2)
Co2Vo
CV2
* Khi va ht HCl: (1) => C01V0= CV1
Ti t: (2)=> C02V0 = CV2
=> C(V1+V2)= CV =(Co1+Co2)Vo

Chun dd {HCl(Co1) + H3PO4(Co2)} bng

dd NaOH(C)
HCl + NaOH NaCl + H2O
t 1
Co1Vo CV1
(metyl
H3PO4 + NaOH NaH2PO4 + H2O da
cam)
Co2Vo
CV2
NaH2PO4 + NaOH Na2HPO4 + H2O t 2
(p.p)
Co2Vo
CV3
*Metyldacam: CVt1=C(V1+V2)=(Co1+Co2)Vo
* p.p: CVt2=C(V1+V2+V3)=(Co1+2Co2)Vo

2)Chun dd hn hp baz :
a) Chun dd hn hp baz mnh:
B(OH)n Bn+ + nOHm+
- COH-= nC01+mC02
C(OH)m C + mOH
=> Ti t:tt c cc baz u chun
b) Chun dd hn hp baz mnh v baz
yu n chc
NaOH + HCl NaCl + H2O t,
(metyl
Co1Vo
CV1
NH4OH + HCl NH4Cl + H2O da cam)
Co2Vo
CV2
CV = C(V1+V2) = (Co1 + Co2)Vo

c) Chun dd hn hp baz mnh v baz

yu a chc
NaOH + HCl NaCl + H2O
Co1Vo
CV1
t 1,p.p
Na2CO3 + HCl NaHCO3 +NaCl
Co2Vo
CV2
t
2,
NaHCO3+HCl CO2+H2O + NaCl
(metyl
Co2Vo
CV3
da cam)
*p.p: C(V1+V2)=(Co1+Co2)Vo
*metyl da
C(V1+V2+V3)=(Co1+2Co2)Vo
cam

VI. Sai s ch th:

Acid + Baz Mui + H2O
CoVo CV
t: CV = CoVo : xc nh t dng ch.ch.th
* Ch.ch.th c pT = pHt => S%= 0
* Ch.ch.th c pT < pHt => S% < 0 SS(-)
=> dng chun trc t
* Ch.ch.th c pT > pHt => S% > 0 SS(+)
=> Dng chun sau t

Cng thc tnh sai s ch th:

CV C 0 V 0 2
2
S %=
10 = (F 1)10
C0 V 0
CV: lng ch.
CoVo: lng ban u
* CV < CoVo => F < 1 => S% < 0: SS(-)
* CV > CoVo => F > 1=> S% > 0: SS(+)

1. Chun acid mnh bng baz mnh:

AH + NaOH NaA + H2O
CoVo CV
CV C 0 V 0 2
S %=
10
a. pT < pHt
C0 V 0
pT=pHc= -lgCH+ => CH+ = 10-pT
(CV CoVo)= -CH+(Vo+V)= -10-pT(Vo+V)
C0 V
CV = CoVo=> C = V
0

C0
V
+1=
+1
C
V0

C0 + C V + V 0
C 0 +C V +V 0

=
=
C0 C
C 0V 0
C
V0

S %H

10

pT

pT

(V 0 + V )
10
2 =
10
C0 V 0

(C 0 + C )
2
10
C0 C

b. pT > pHt => F > 1 => S% > 0;SS(+)

CV CoVo 2
.10
Dd (NaOH) tha S % =
CoVo
pOH= 14 pH= 14 - pT =>COH-=10pT-14
pT 14
)
(V 0 + V
(C 0 + C )
10
10
2= +
2
= +
10
10
C0 V 0
C0 C
pT 14

S %OH

2.Chun dd baz (m) bng dd acid (m)

B(OH)n + nHCl BCln + nH2O
a. pTc < pHt = 7 => F < 1 =>Dd( BOH tha)

S %OH

10

pT 14

(C 0 + C )
2
10
C0 C

b. pTc > pHt = 7 =>F > 1 => dd(HCl tha)

pT

S %H

= +

10

(C 0 + C )
2
10
C0 C

3. Chun dd acid yu n chc

AH + NaOH NaA + H2O
CoVo CV
a. pTc < pHt => F < 1=> dd(AH tha)
CV C 0 V 0 2 :(CV-C V )=-[AH](V +V)
o o
o
S %=
10
C0 V 0
CoVo=[AH](Vo+V)+[A-](Vo+V)={([AH]+[A-])(Vo+V)}

AH A- + H+
Ka

[
A
][
H
]
K a = [ AH ]

Ka
[
A
]
[
A
]
=

+
1
=
+
1
+
+
[ AH ]
[ H ] [ AH ]
[H ]

K a + [H ]
+

[H ]

[ A ] + [ AH ]
=
[ AH ]

[ AH ]
[H ]

+ =
K a + [ H ] [ A ]+ [ AH ]
[
AH
](
+
V
)
V
0
2

S % AH =
10

([ AH ]+ [ A ])( V + V 0 )
[
AH
]
2

S % AH =
10
[ AH ]+ [ A ]
+

pT
[H ]
10
2
2
S % AH =
+ 10 =
+ 10
K a + [H ]
K a + [H ]

b.pT>pHt =>F>1; Sau t=> dd tha NaOH

pT 14
(C 0 + C )
10
2
=

S %OH
10
C0 C

4.Chun baz yu n chc

BOH + HCl BCl + H2O
Co V o
CV
a. pT>pHt => F<1; dng chun trc t
=> Dd tha baz yu

pT 14
[OH ]
10
2
2
S %OH =
10 =
10
K b + [OH ]
K b + [OH ]

b. pT<pHt=> F>1; dng chun sau t

=>Dd tha HCl
pT

S %H

= +

10

(C 0 + C )
2
10
C0 C

B.CHUN PHC CHT

I. Phc cht
HO
*K3[Fe(CN)6] 3K+ + [Fe(CN)6]3[Fe(CN)6]3- Fe3+ + 6CNLk gia Fe3+ v 6CN-: lin kt phi tr
=>[Fe(CN)6]3- : ion phc;K3[Fe(CN)6]: phc cht
HO
*K2SO4 2K+ + SO42SO42- S6+ + 4O2-? : SO42- khng phn ly
Lk gia S v 4O l lin kt cng ha tr
SO42-:khng phi l ion phc
K2SO4 : khng phi l phc cht
2

Xem ion phc tng qut:

x+ M: ion trung tm(cc ion kim loi t
y_
CK 3 tr ln)
MLn
L: ligand(trung ha, ion(+) hay ion(-)
x+, y- : in tch ca ion phc
MLn (khng ch n in tch ion phc) l cht
in ly yu, trong dd MLn in ly:n
[ M ][ L]
MLn M + nL => Kkb = [ ML ] :hs khng bn
n

[ MLn ]
M + nL MLn => =
n : hs bn
[ M ][ L]
=> .Kkb = 1

DANH PHAP

Cach goi ten phc chat

+ Goi ten cac ligand trc theo th t
*ligand goc acid ligand phan t
+ sau cung goi ten cac ion trung tam kem
theo so la ma viet trong dau ngoac ch hoa tr
cua no(cation).

+ Neu ion phc la anion thi them uoi at

trc khi them so la ma

+ Nu ligand l gc ca axid th thm ui O vo

tn gc axid.
V d: SO42-: sunfato; NO3- : nitrato.
+ Nu ligand l ion halogen th thm O vo tn
halogen.
V d: F- : floro; Cl-: cloro; Br- : bromo; I- : iodo
Mt s ion khc gi theo tn ring.
V d: NO2-: nitro; S2-: sunfo; S22-:pesunfo

S phi tr c gi bng tn ch s Hy Lp t trc

tn phi t
1 : mono 2: di

3: tri

4 : tetra

5: penta

6: hexa

8: octa

9 : nona

10: deca

7: hepta

V d :
[Ag(NH3)2]Cl diamino bc (I) clorua
K3[Co(NO2)6] : Kali hexanitro cobanat (III)

II. Nguyen

tac chung va phan loai

1. Nguyen tac chung
Da tren phan ng tao thanh cac phc tan hay cac
muoi phc t phan ly
M +
nL MLn
2. Phan loai
a.Phng phap o bac (chuan o cyanua)
2CN- + Ag+
Ag(CN)2e nhan biet iem tng ng : cho d 1 giot
Ag+ se lam dung dch van uc do xuat hien ket tua
trang Ag[Ag(CN)2]
Ag(CN) - + Ag+

Ag[Ag(CN) ]

b. Phng phap thuy ngan

Da tren phan ng tao phc gia Hg2+ vi ion
halogenua (Cl-, Br-, I-) va SCN2Cl- + Hg2+ HgCl2
e nhan biet iem tng ng dung ch th:
- Diphenyl Carbazit (pH = 1,5 2,6)
-Diphenyl Carbazon (pH = 2,0 3,5)
-Tai iem tng ng d mot giot Hg2+ se tao vi
ch th mot phc mau xanh tm
c. Phng phap Comlpexon
Da tren p. tao phc gia cac ion kim loai vi mot
nhom thuoc th hu c co ten chung la complexon.

III. Phng phap chuan o complexon

1. Gii thieu chung ve cac complexon
Complexon la ten goi chung ch mot nhom cac thuoc
th hu c la dan xuat cua acid amino polycarboxylic
+ Complexon 1:
Acid Nitrylotriacetic (NTA) hay con goi la Chelaton I

+ Complexon II: (chelaton II)

EDTA

ethylenediaminetetraacetic acid H4Y

+ Complexon III
Muoi cua EDTA : Na2H2Y. 2H2O goi la Trilon B

+ Complexon IV

2. S tao phc cua Coplexon III vi cac ion kim

loai
Trong dung dch nc complexon III ien ly
Na2H2Y 2Na+ +
H2Y2
H2Y2-

2H+

Y4-

Men+ + Y4
MeY(n 4)
Men+ + H2Y2- MY(n-4)
+ 2H+
V du
Ag+ + Y4- AgY3Hg+2 + Y4- HgY2Fe+3 + Y4- FeYM+n + Y4- MY(n-4)

V du : Phc calci complexonat (CaY2)

* Anh hng cua pH en o ben cua cac complexonat

Men+
+
H2Y2
MeY(n 4)
+
2H+
pH cua dung dch : anh hng en cac dang ton tai
cua H4Y va s tao phc hydroxo kim loai.

pH cang cao th s tao phc hydroxo kim loai cang

manh => s tao phc complexonat cang kem.
Nhng pH cang cao th dang Y4 ton tai cang ln =>
tang kha nang tao phc complexonat.

Hai yeu to anh hng trai ngc =>moicomplexonat

ch ben trong mot khoang pH nhat nh.

+ Cac ion kim loai hoa tr 3,4 b thuy phan rat manh
cho cac phc hydroxo ngay ca trong moi trng acid.
=>complexonat cua chung ch ben trong moi trng
rat acid.
V du: FeY,ScY. . . ben trong khoang pH = 1 2.
+ Cac ion kim loai nhom B co hoa tr 2 va Al3+ b
thy phan yeu hn cac ion hoa tr 3, 4 nen phc cua
chung ben pH cao hn mot t : pH = 2 5.
+ Cac complexonat kim loai nhom IIA lai ben trong
moi trng kiem hn. Cac phc nay ben trong
khoang pH = 8 10.

V du : ch. Pb2+ bang ph.ph complexon, can tien

hanh ch. trong moi trng kiem co pH = 9 10.
Trong m.t nay Pb2+ Pb(OH)2, do o can cho vao
dd chat tao phc phu vi Pb2+ nh muoi tartrat
(KHC4H4O6) hay Trietanolamin
*
e nga
n ng
a )a.n.h. hng cua cac ion can tr
(N(CH
CH
OH)
2
2
3
+ Chon pH thch hp sao cho EDTA ch tao phc
ben vi ion kim loai can chuan o.
V du : ch. ring ion Ca2+ khi c mt Mg2+,
Tien hanh moi trng kiem manh (pH = 12).
Mg2+ se ket tua di dang Mg(OH)2
Ca2+ ton tai dang CaY2.

+ Dung chat che thch hp e tao phc vi cac ion

can tr
V du : Dung CN e che cac ion Cu2+, Co2+, Ni2+ khi
chuan o Ca2+, Mg2+ trong hon hp co cha cac ion
tren.
Dung F e che Al3+, Ca2+, Fe3+ khi chuan o
Zn2+, Cd2+,
+ Tach cac ion can tr bang cach ket tua phan oan .
..

3. Chat ch th dng trong phng phap chuan o

complexon
Ch th mau kim loai la cac thuoc th hu c co kha
nang tao vi cac cation kim loai cac phc co mau va
ban than ch th cung co mau.
Cht ch th mau kim loai cung la nhng a axit hay
a baz hu c yeu thuoc loai thuoc nhuom nen tuy
theo pH cua moi trng ma co the ton tai di nhieu
dang khac nhau co mau khac nhau.
mau sac cua ch th thay oi tuy theo pH cua dung
dch.

V du: Chuan o trc tiep ion kim loai Men+ dung ch

th mau kim loai HInd. ion kim loai se tao phc mau
vi ch th :
Men+
+ HInd MeInd(n1)+
+ H+
Khi nho t t dung dch chuan Trilon B vao:
Men+ + H2Y2- MeY(n-4) + 2H+
Khi ht Men+, Trilon B s p vi MeInd(n-1)+.
MeInd(n1)+ + H2Y2 MeY(n4) + HInd + H+ (1)
Lam the nao e nhan biet c t?
iem tng ng: dung dch chuyen t mau cua
dang MeInd sang mau cua dang ch th t do HInd.

e nhan ra iem tng ng mot cach ro rang

-Phan ng (1) phai xay ra hoan toan :
phc cua ch th va kim loai phai kem ben hn
nhieu so vi phc complexonat kim loai.
Ch th phai co o nhay cao
Phc ch th vi kim loai cung phai tng oi
ben Thng chon ch th thoa man yeu cau :
104 < MeInd
104MeInd< MeY
Chon pH sao cho
Phc MeY ben
Mau cua phc MeInd phai khac han mau cua ch
th t do HInd.

MOT SO CHAT CH TH THONG DUNG

+ Eriocrom -T- black ( ET-00 hay NET)( H3Ind)

Cong thc phan t : C20H13N3O7S.
ET 00 thng dung di dang muoi Natri co cong
thc phan t C20H12N3O7NaS; M = 461,39
Ch th NET
c dung
pH=7 11

Trong dung dch nc: H3Ind

H2Ind
HInd2

H+ + H2Ind
Ind3

V du :
NET c dung lam ch th khi chuan o Mg2+,
Zn2+, Pb2+ . . . trong moi trng co pH = 9 10.
iem tng ng : dung dch chuyen t mau o
nho sang mau xanh biec.

+ Murexid : C8H8N6O6.H2O; M = 302,21.

Murexid la axit 4 nac (H4Ind-)

H4Ind

H3Ind2

H2Ind3

Xac nh Ca2+ pH 12. t ng vi khi dung

dch chuyen t mau o ( CaInd3) sang mau tm
xanh ( ch th t do H2Ind3).
Xac nh Ni2+, Co2+, Cu2+ pH = 8 9. t ng
vi khi dung dch chuyen t mau vang ( MeInd3)

4. ng cong chuan o complexon

Ch. V0 dd ion Mn+ C0(M) bang dd dchTrilon B C(M)
Goi MY la hang so ben cua phc MY.
V(Trilon B) cho vao trong tng thi iem.
F: mc o dd ion Mn+ a c chuan o
P. Mn+ +
H2Y2-
MY(n-4) + 2H+
C.V
M
+ Y

MY
F=

C 0 .V0

ng cong chuan o la ng bieu dien pM = f(F)

+ Khi (V=0, F=0):
pM c quyet nh bi dd Mn+ ban au.

pM = lgC 0

+ Trc iem tng ng ( V0C0 > CV, F<1)

pM c quyet nh bi dung dch Mn+ d
V0 .C 0 V.C
V0 .C 0 V.C
pM = lg
[M ] =
V0 + V
V0 + V
+ Tai iem tng ng (V0C0 = VC, F=1)
C0V0
pM c quyet nh bi dung
[ MY ] =
V0 + V
dch phc MY
MY

[ MY ] [ MY ]
=
=
[ M ][Y ] [ M ]2

[M ] =

pM t = lg

[ MY ]
=
MY

C0V0
MY (V0 + V)

C0V0
MY (V0 + V )

+ Sau t (V0C0 <VC, F>1)

pM c quyet nh bi Trilon B d
C0V0
V.C V0 .C 0
[ MY ] =
[Y ] =
V0 + V
V0 + V

C0V0 (V0 + V )
C0V0
[ MY ]
[M ] =
=
=
MY [Y ] MY (CV C0V0 )(V0 + V ) MY (CV C0V0 )
pM = lg (

C0V0
)
MY (CV C0V0 )

5. Sai so chuan o

[M ] =

C0V0
MY (V0 + V )

+ Neu Ket thuc chuan o tai pM > pMT : Ket thuc

chuan o sau t. Tha dung dch chuan Trilon B
1
gay sai so tha : SS% Y

S%Y =

MY [M]

.100

+ Neu chuan o tai pM < pMT : Ket thuc chuan o

trc t. Phep chuan o mac sai so thieu SS% M n +

[ M ](C0 + C )
S % n+ =
100
M
C0C

V du: Chuan o 100ml dung dch Mg2+ 0,1M bang

dung dch Trilon B 0,1M. Biet MgY = 108,7.
a)Ve ng cong chuan o
b)Tnh sai so cua phep chuan o neu ket thuc chuan
o pM =6
Phan ng chuan o:
Mg

Y =

MgY

Tai iem tng ng VY chuan o het

VY = Vt

0,1.100
=
= 100ml
0,1

VY

Cng thc tnh pH

0
50
90
99

pM = lgC0
0
0,5
V0 .C0 V.C
pM
=

lg
0,9
V0 + V
0,99

pM

2 Cha ch.
2,48
3,28
4,3 S%=-1%

C0V0
5,5
pM = lg
MY (V0 + V )

100

101
110
150
200

1,01
C0V0
1,1 pM = lg
MY (CV C0V0 )
1,5
2

Ghi ch

6,7 S%= +1%

7,7
8,4
8,7

Bc nhay pMg=4,36,7

pMgT=5,5

Sai so chuan o khi ket thuc chuan o tai pMg = 6

[ M ]TD =

C0V0
= 10 5,5
MY (V0 + V )

pM = 5,5
+ Neu Ket thuc chuan o tai pM=6 > pMT=5,5 : Ket
thuc chuan o sau iem tng ng. Tha dung
dch chuan Trilon B gay sai so tha :

1
SS% Y =
.100
MY [ M ]
1
1
SS% Y =
.100 = 8, 7
.100 = 0,2%
6
MY [ M ]
10 x10

III. Cac phng phap tien hanh

chuan o complexon
Chuan o trc tiep
Chun ngc
Chun thay th

Chuan o trc tiep:

S dung khi:

+ Phan ng chuan o xay ra nhanh.

+ Chat ch th oi mau ro rang.
V du:
Chuan o Mg2+ bang Trilon B pH = 9 10 vi ch
th NET
Chuan o Ca2+ bang Trilon B pH 12 vi ch thi
Murexit
Chuan o Fe3+ bang Trilon B pH = 2 3 vi ch th
acid sunfosalisilic

2. Chuan o Ngc: S dung khi:

+ Khong co chat ch th thch hp.

+ P. gia ion kim loai vi Trilon B xay ra qua cham.
+ pH ch.,ion kim loai ket tuadi dang hydroxyt
V du : Xac nh M1
M1

H2Y2- +

H2Y2- (d) M1Y

2H+

M2

2H+

M2Y

Lam the nao e nhan biet c iem cuoi?

iem cuoi : chuyen mau t mau ch th t do HInd san

V du: Xac nh Pb2+ pH = 9 10 bang ch. ngc

Pb2+ +

Trilon B (d)

pH : NH4Cl + NH3 ; ch th NET

Trilon B d

Zn2+

iem cuoi:
HInd2xanh biet

ZnIndo nho

3. Chuan o thay the

M1

+ M 2Y

M1Y + M2

M2

+ H2Y2- M2Y +

2H2+: 107 < M2Y << M1Y

iem cuoi : chuyen mau t M2Ind sang mau Hind

VD: Xac nh Pb2+ pH = 9 10 bang ch. gian tiep
Pb2+ + ZnY2- PbY2Zn2+

+ Zn2+

+ H2Y2- ZnY2- + 2H+ : Ch th Net

iem cuoi : chuyen t mau o nho (ZnInd-) sang

xanh biec (HInd2-)

C. CHUN OXY HA KH

I. Phn ng oxy ha kh
1. Cht oxy ha v cht kh:
Fe2+ + MnO4- + H+ Fe3+ + Mn2+ + H2O
5 Fe2+ Fe3+ + e
1 MnO4- + 5e + 8H+ Mn2+ + 4H2O
=> 5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
Fe3+/Fe2+ : Fe3+ + e Fe2+ (cp oxy ha kh 1)
MnO4-/Mn2+ : MnO4- + 5e + 8H+ Mn2+ + 4H2O
(cp oxy ha kh
2)
=> p oxy ha kh phi c 2 cp oxy ha kh trn
ln vo nhau.

Xem phn ng oxy ha kh tng qut

Ox1 + Kh2 Kh1 + Ox2
a Ox1 + be Kh1
b Kh2 Ox2 + ae
aOx1 + bKh2 aKh1 + bOx2
Ox1/Kh1: Ox1 + be Kh1 Cp oh-kh(1)
Ox2/Kh2: Ox2 + ae Kh2 Cp oh-kh(2)

Mi cp oxy ha kh iu kin( nng , p

sut, nhit ) xc nh c gi tr in th oxy
ha kh xc nh: E0Ox/Kh(Volt)
E0Ox/Kh: in th oxy ha kh tiu chun{[ ]=1M,
p= 1atm, T = 25oC} ca cp oxy ha kh

2.The oxy hoa kh-Phng trnh Nerst

The oxy hoa - kh cua mot cap oxy hoa - kh
lien hp cang cao th chat oxy hoa cua cap ay
cang manh va chat kh cang yeu
xem cp: Ox + ne Kh
E0 : in th iukin chun( 1M ; 1 atm)
E : in th iu kin khng chun

0,059 [Ox]
E= E +
lg
n
[ Kh]
0

V DU
Viet bieu thc the oxy hoa - kh cua cac
cap oxy hoa - kh sau 250C
a. Cu2+/Cu
b. MnO4-/ Mn2+
* Cu2+ + 2e Cu

ECu 2+ / Cu = E

0
Cu 2+ / Cu

0,059
2+
+
lg[Cu ]
2

* MnO4- + 5e + 8H+ Mn2+ + 4H2O

EMnO / Mn 2+ = E
4

0
MnO4 / Mn 2+

+ 8

0,059 [ MnO ][ H ]
+
lg
2+
5
[ Mn ]

P oxy ha kh xy ra theo chiu no?

Cho 2 cp oxy ha kh: Dng Ox ca cp c
Ox1 + be Kh1 E1
E ln hn s p vi
Ox2 + ae Kh2 E2 dng kh ca cp c
E nh hn
Td:E1> E2 => aOx1 + bKh2 aKh1 + bOx2
Td: Trn ln 2 cp: Cu2+/Cu(E1= + 0,7v) v
Zn2+/Zn(E2= - 0,77v) ta c:
Cu2+ + Zn Cu + Zn2+

II. Nguyen tac chung

aOx1 + bKh2 aKh1 + bOx2
Phan ng phai thoa man yeu cau sau:
Phai xay ra hoan toan : Kc ln.
Phan ng xay ra nhanh.
Khong xay ra phan ng phu.
Phai nhan biet c iem tng ng.

1. CACH XAC NH IEM TNG NG

1. Them mot chat ch th co kha nang
tao mau manh va ac trng vi mot
dang nao o cua cac cap oxy hoa kh trong phan ng.

2. Dung chat ch th oxy hoa - kh

3. Khong can dung ch th.

Ch th oxy hoa kh
Chat ch th oxy hoa - kh la nhng
chat hu c co tnh oxy hoa hay kh
mau cua dang oxy hoa khac han vi
mau cua dang kh lien hp.
khi the cua dung dch thay oi th mau
sac cua ch th cung thay oi

Khoang the oi mau cua chat ch th

IndOx + ne

EInd 0 x / Ind Kh = E

0
Ind ox / Ind Kh

IndKh

0,059 [Ind Ox ]
+
lg
n
[Ind Kh ]

0,059
[Ind
dung
Ox ] dch co mau cua dang0 Ind Ox khi:
10 EIndox / Ind Kh EIndox / Ind Kh +
[Ind Kh ]
n
[Inddung
1 co mau cua dang0 IndKh khi 0,059
Ox ] dch

E Ind / Ind E Ind / Ind

ox
Kh
ox
Kh
[Ind Kh ] 10
n

 Khoang the :

E Ind =

0
Ind ox / Ind Kh

0,059

EInd khoang the chuyen mau cua ch th

oxy hoa kh
V.d: Ferroin:phc cua Fe2+vi1,10 phenantrolin

Mau o
EInd = 1,14 0,06 (V)

Mau xanh

Mot so chat ch th oxy hoa kh

Chat ch th

Mau
IndOx

IndKh

E0(V) tai
pH = 0

Diphenylamin
Tm
Natri Diphenylamin o tm
Sulfonat

Kh mau
Kh mau

0,76
0,84

Acid
Phenylanthranilic

Tm o

Kh mau

1,08

Ferroin

Xanh nhat

1,06

2. ng cong chun NG

+ bOx2 aOx1 + bKh2

CHUAN O TRONG PHEP CHUAN
Ox1 + be
O QXY HOA -KH
Kh1
Ox2 + ae Kh2
aKh1

0,059 [Ox1 ]
E= E
+
lg
b
[ Kh1 ]
0,059 [Ox2 ]
0
E = EOx2 / Kh2 +
lg
a
[ Kh2 ]
0
Ox1 / Kh1

CV
F=
C0V0

C0 v C: (CN)

 Trc t: Tnh the dung ch theo cap Ox1/ Kh1

0,059 [oxh1 ]
E= E +
lg
b
[kh1 ]
CV
C0V0 CV
[oxh1 ] =
[kh1 ] =
V0 + V
V0 + V
0,059
CV
0
E = E1 +
lg
b
C0V0 CV
0
1

0,059
F
E = E +
lg
b
1 F
0
1

Ti t: The cua hai cap (1) va (2) can bang

nen tnh the dung dch theo ca hai cap
0,059 [Ox1 ]
0,059 [Ox2 ]
0
0
E = E1 +
lg
E = E2 +
lg
b
[ Kh1 ]
a
[ Kh2 ]
[Ox1 ]
[
Ox
]
0
2
bE = bE + 0,059 lg
aE = aE2 + 0,059 lg
[ Kh1 ]
[ Kh2 ]
0
1

aKh1

+ bOx2

aOx1 + bKh2

[Kh1] = [Ox2] ; [Ox1] = [Kh2]

[Ox1 ][Ox2 ]
bE
+
aE
= 1 ETD =
[ Kh1 ].[ Kh2 ]
a+ b
0
1

0
2

Sau t:Tnh the dung dch theo cap Ox2/Kh2

0,059 [oxh2 ]
E= E +
lg
a
[kh2 ]
C0V0
CV C0V0
[kh2 ] =
[oxh2 ] =
V0 + V
V0 + V
0
2

0,059 CV C0V0
E= E +
lg
a
C0V0
0
2

0,059
E = E +
lg( F 1)
a
0
2

V DU
Ve ng chuan o khi chuan o 20 ml dung
dch Fe2+ 0,1N bang dung dch
KMnO4
0,1N trong moi trng H2SO4 co pH = 0 .

0
Fe3+ /Fe 2+

0
MnO 4 /Mn 2+

= 0,77(V )
= 1,51(V )

 Phan ng chuan o :
MnO4-+ 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
* Fe
E = E

0
Fe 3+ / Fe 2+

Fe3+ + e
3+

0,059 [ Fe ]
+
lg
2+
1
[ Fe ]

MnO4- + 5e + 8H+ Mn2+ + 4H2O

+ 8
0,059 [ MnO 4 ][ H ]
0
E = EMnO / Mn 2+ +
lg
2+
4
5
[ Mn ]
pH=0 => [H+] = 1M

0,059 [ MnO 4 ]
0
E = EMnO / Mn 2+ +
lg
2+
4
5
[ Mn ]

V
KMnO4

10

0,5

18

0,9

19,8

0,99

19,98

0,999

20

20,02

1,001

20,2

1,01

30

1,5

Cong thc tnh the E E (Volt)

E = E10 +
E =E

0
Fe3+ / Fe 2+

0,059
F
lg
b
1 F
0,059 F
+
lg
1
1 F

0,77
0,83
0,89
0,95

ETD

bE10 + aE 02
=
a+ b

E = E 02 +

0,059
lg( F 1)
a

0
E = EMnO
+

,8 H + / Mn 2+
4

0,059
lg( F 1)
5

Ghi chu

1,39
1,48
1,49

1,51

S % = -0,1%
t
S% = +0,1%

Cach chon chat ch thi

Da vao khoang the oi mau va bc
nhay
+ Khoang the oi mau nam trong bc
nhay
Chon chat ch th nay
Da vao the E0 cua chat ch th
+ Neu E0 cua chat ch nam trong bc
nhay Chon chat ch th nay
+ Neu E0 ET0 : Chon chat ch th nay

NHAN XET
Trc va sau td E cua dd thay oi cham.
Tai 0,999 < F < 1,001 : E cua dd tang ot ngot
tao thanh bc nhay the cua ng chuan o
Trong ch.o, bc nhay the khong phu thuoc
vao nong o cua dd chuan va dd can ch.o
ma phu thuoc vao o chenh lech the cua 2
cap oxy hoa kh tham gia phan ng ch.o.
Chenh lech the gia 2 cap ohk cang ln th
o chnh xac cua phng phap ch.d cang cao.
Chon chat ch th: 0,95 (V) E0 1,48(V)

IV. SAI SO CH TH

CV C 0 V0
SS% =
100 = (Fc 1).100
C 0 V0

V DU
Tnh sai so khi chuan o dung dch
Fe2+ bang dung dch KMnO4 0,1N
trong moi trng H2SO4 co nong o ion
H+ khong oi bang 1 mol/ lit va ket
thuc chuan o Ec = 0,87V

Fe3+ /Fe 2+

0
MnO 4 /Mn 2+

= 0,77(V )
= 1,51(V )

ETD

GIAI
5.1,51 + 0,77
=
= 1,387 V
6

Ec = 0,87V < ET = 1,387 V

Ket thuc chuan o trc iem tng ng

FC
0,059
E = E +
lg
b
1 FC
0
1

SS% = 1,96%

V DU

Tnh sai so khi chuan o dung dch Fe2+

0,1M bang dung dch Ce4+ 0,1M. Biet rang
het thuc chuan o Ec = 1,257 V

0
3+

Fe /Fe

2+

= 0,77(V )

0
E Ce 4+ /Ce3+

= 1,44V

ETD

GIAI
1,44 + 0,77
=
= 1,105V
2

Ec = 1,257V > ET = 1,105 V

Ket thuc chuan o sau iem tng ng

0,059
E = E +
lg( F 1)
a
0
2

SS% = 0,08%

V. CAC PHNG PHAP CHUAN O

OXY HOA KH

1. Phng phap chuan o oxy hoa kh

bang KMnO4
2. Phng phap chuan o bang Ce(SO4)2

3. Phng phap chuan o oxy hoa kh bang

K2Cr2O7
4. Phng phap chuan o oxy hoa kh theo
phng phap Iot - Thiosulfat

1.Phng phap chuan o oxy hoa

kh bang KMnO4
Nguyen tac
MnO4- + 8H+ + 5e Mn2+ + 4H2O E0 =1,51V
Khong dung HNO3 va HCl lam moi trng
* E0Cl2/2Cl-< E0MnO4-/Mn2+ =>
2MnO4- + 10Cl- +16H+ 2Mn2++ 5Cl2+ 8H2O
* E0NO3-/NO E0MnO4-/Mn2+
HNO3 cng oxy ha cht kh

ng dung cua phng phap chuan

o oxy hoa kh bang KMnO4
Chuan o trc tiep cac chat kh
Xac nh H2C2O4
5H2C2O4 + 2KMnO4 + 8H2SO4 2MnSO4 +
10CO2 + K2SO4 + 8H2O
Xac nh Fe2+
Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
Xac nh H2O2
5H2O2 + 2MnO4- + 6H+ 2Mn2++ 5O2 + 8H2O

ng dung cua phng phap chuan

o oxy hoa kh bang KMnO4

Chuan o thay the

Ap dung oi vi : Chat kh de b khong kh
oxy hoa
Chat kh + Fe3+ Fe2+
Chuan o Fe2+ bang KMnO4

+ Xac nh RCHO
RCHO + 2Cu(OH)2RCOOH + Cu2O + 2H2O
Cu2O + Fe3+ = Cu2+ + Fe2+
5Fe2+ + MnO - + 8H+ = 5Fe3+ + Mn2+ + 4H O

 + Xac nh cac ion tao c tua oxalat

Ca2+,Cd2+, Zn2+, Pb2+, Co2+, Ni2+,
- Dung (NH4)2C2O4 e ket tua cac ion kl tren
Ca2+ + C2O42- CaC2O4
- Loc ra tua oxalat thu c bang H2SO4 (l)
CaC2O4 + H2SO4 CaSO4 + H2C2O4
- Chuan H2C2O4 sinh ra bang KMnO4
5H2C2O4 + 2KMnO4 + 8H2SO4 2MnSO4 +
10CO2 + K2SO4 + 8H2O

 Chuan o ngc
Ap dung oi vi:Chat kh phan ng cham vi
MnO4Chat kh + MnO4- d
Chuan o KMnO4 d bang chat kh khac
+ Xac nh S2Cho S2- tac dung vi KMnO4 lay d
5S2-+8MnO4-d +24H+ 5SO42-+8Mn2++12H2O
Chuan lng KMnO4 d bang Fe2+
5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O

2. Phng phap chuan o

Ce(SO4)2
Ce4+ + e Ce3+ Eo = + 1,44V
Mau cam
Phep chuan o Ce4+ phai dung chat ch th
Thng dung ch th Feroin.
Tai iem tng ng: mau xanh nhat
mau o.

ng dung cua ph.ph chuan o Ce(SO4)2

Chat PT

ieu kien TH
Phan ng
Sn
Sn2+ + 2Ce4+ Sn4+ + 2Ce3+ Kh Sn4+ = Zn
Fe
Fe2+ + Ce4+ Fe3+ + Ce3+ Kh Fe3+ bang
Zn , SnCl2
Mg, H2C2O4+2Ce4+2CO2+2Ce3+ cac ion di
dang MC2O4.
Ca, Zn,
+2H+
Loc, ra ket
Co, Pb,
tua, hoa tan
Ag

HNO2 HNO2+2Ce4++H2ONO3-+
2Ce3++3H+

bang H2SO4 l

3. Phng phap chuan o oxy hoa kh

bang K2Cr2O7
Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O
mau o cam
E0 = 1,33V
e nhan biet iem tng ng:
Ch th Diphenylamin
iem cuoi : mau xanh la cay xanh tm am
Co the dung HCl lam moi trng

4. Phng phap chuan o I2- Na2S2O3

Nguyen tac
E0 = 0,54 V
I2 + 2e 2IS4O62- + 2e 2S2O32- Eo =0,1V
Chuan I2 + Na2S2O3
I2 + 2Na2S2O3 2NaI + Na2S4O6
Chat ch th : Ho tinh bot
iem cuoi : mau xanh tm khong mau

 Chu y: Khi chuan o I2 bang Na2S2O3 nen:

+ Tien hanh nhiet o thng
V : T0 cao I2 b thang hoa va o nhay cua
ho tinh bot b giam i
+ Chuan o trong moi trng acid yeu hoac
trung tnh 5 < pH < 7
V: Trong moi trng acid manh
S2O32- + 2H+ H2SO3 + S
Trong moi trng kiem
I2 + 2OH- IO- + I- + H2O

ng dung cua phng phap chuan o

I2- Na2S2O3

Chun trc tip:

I2 + 2Na2S2O3 2NaI + Na2S4O6

C0V0 = CV
Chun ngc: Cht Kh + I2 d
CoVo
CV1
Chun I2 d bng Na2S2O3
I2 + 2Na2S2O3 2NaI + Na2S4O6
CV2
CV

* Chuan o thay the

Chat oxy hoa + KI d I2
Chuan I2 tao ra bang Na2S2O3
+ Xac nh Cu2+: tien hanh pH = 4 (CH3COOH)
2Cu2+ + 4I- = 2CuI + I2
I2 + 2Na2S2O3 = 2NaI + Na2S4O6
Chu y: e tranh s hap phu I2 tren tua CuI lam tua
co mau vang tham khong xac nh c iem
cuoi.
SCN- + CuI = CuSCNtrang + I-

D. CHUN KT TA

I. Cn bng ha tan ca cht kh tan(tch s tan)

1. Tch s tan.
em ha tan cht kh tan AmBn(r) vo nc:
lng ha tan rt nh, Dd rt long:
phn ha tan xem nh din ly hon ton: c cb
AmBn mAn- + nBm+ : dd bo ha AmBn/H2O
t0 a
0
0
Nng ca dd bo ha
tcb -S
mS
nS
gi l tan(S) ca AmBn.
Kc = [An-]m[Bn+]n = (mS)m(nS)n = mmnnS(m+n)
Kc= TAmBn = mmnnS(m+n)

SAmBn =

( m+ n)

T
mn

AmBn
m
n

TAmBn SAmBn
* Cc cht c cng thc tng t nhau(A mBn CmDn)
cht no c T S
Td: AgX
TAgX
SAgX = (TAgX)1/2 (M)
AgCl
10-10
10-5
AgBr
10-13
10-6,5
AgI
10-16
10-8
* Cc cht c cng thc khng tng ng(A mBn
v CpDq), phi tnh c th
Td: AgCl
TAgCl = 10-10 SAgCl = 10-5
*

12

Ag2CrO4 T = 4.10-12 S= 3 4.10

2 1
=10-4
21
Pha
long
ddtan
nhiu
hn
*
* un si:H2O bay hiC(ion) kt ta nhiu hn

2. Diu kin c kt ta
a. Ha tan 1 lng xc dnh cht kh tan A mBn
* Nu tan ht:
AmBn mAn- + nBm+
t -C0
mC0
nC0 Vi C0 = m0/MAmBn
TAmBn = (mC0)m.(nC0)n
So snh TAmBn v TAmBn: ta c
T < T dd cha bo ha: tan ht
T = T dd bo ha: tan ht
T > T dd qu bo ha: tan 1 phn, c (r l)
Td: ha tan 10-3 mol Ag2CrO4(r) vo nc 1l dd
Ag2CrO4 2Ag+ + CrO42C0=10-3M T=(2.10-3)2.(10-3) =4.10-9 >Ttan 1 phn

b. Trn ln 2 dd:
dd(1)An-{C1,V1} + dd(2)Bm+{C2,V2} dd(3) c?
mAn- + nBm+ AmBn dd(3){C1,C2,V3=V1+V2)
Sau khi trn ln nhng chua p:
n1=C1V1=n1=C1V3
C 2V 2
C
1V 1

;C2=
C1=

V3
n2=C2V2=n 2=C 2V3
V3
TAmBn = (An-)m.(Bn+)n ; so snh vi TAmBn
T < T dd cha bo ha cha c
T = Tdd bo hacha c
T > Tdd qu bo ha c
10ml dd(1) AgNO3(2.10-3 M) +10ml dd(2) Na2CrO4(2.10-3M)
CAg+ = 2.10-3.10/20 = 10-3M
;CCrO4 = 2.10-3.10/20 = 10-3M
TAg2CrO4 = (10-3)2.(10-3) = 10-9 > TAg2CrO4 c

*Co hnh thanh ket tua khong khi cho 2l dd 0,2 M

NaOH tac dung vi 1. l dd 0,1 M CaCl2?
TCa(OH)2 = 8.0 x 10-6
Cac ion ton tai trong dung dch la Na+, OH-, Ca2+, Cl-.
Ch co the hnh thanh ket tua Ca(OH)2.
2
Khi T ' = C 'Ca 2+ .(C 'OH ) > TCa ( OH ) 2 => Ca(OH)2
CCa2+ = 0,1/3 M; COH- = (2.210-1) /3 M

T ' = C 'Ca 2+ .(C 'OH ) =[0,1.(4.10-1)2] /27=[1,6.10-2] /27

2

T > T hnh thanh ket tua

Anh hng cua ion chung en o tan

Tnh o hoa tan cua AgBr trong
a.Nc nguyen chat.
b. dung dch 0,001M NaBr.
AgBr Ag+ + Bra) H2O
b) dd NaBr 10-3M
+
NaBr

Na
+
Br
T = 7.7 x 10-13
-3
C
=
10
M
2
Brs =T
+
AgBr

Ag
+
Br
s = 8.8 x 10-7
[Ag+] = s
[Br-] = 10-3 + s 10-3
T = 10-3 . s
s = 7.7 . 10-10

Anh hng cua pH en o tan

* S hin din ca ion chung lm gim tan

* Baz khng tan ha tan trong dd axit
* Axit khng tan ha tan trong dd baz
Xem: Mg(OH)2 Mg2+ + 2OH-

Mg ( OH ) 2

T
12

Mg ( OH ) 2
1 2

11

1,2.10
4

= 1,4.10

[Mg2+]= 1,4.10-4M
[OH-] = 2s = 2.8 x 10-4 M
pOH = 3,55 => pH = 10,45
Tai pH < 10.45 OH- + H+(aq)
H2O (l)
[OH-] => lam o tan cua Mg(OH)2
Tai pH >10.45:[OH-] => lam o tan cua Mg(OH)2

I. NGUYEN TAC VA PHAN LOAI

1. Nguyen tac

Phng phap chuan o ket tua da tren phan

ng tao thanh cac hp chat t tan
Cac p. ch. ket tua phai thoa man:
P. ket tua phai x.r hoan toan (T < 10-10).
P. xay ra nhanh.
P. xay ra theo mot he so ty lng nhat nh.
P. phai chon loc, ngha la cac qua trnh phu
nh cong ket. . . phai khong ang ke.
Phai co ch.ch.th thch hp e xac nh td.

2. PHAN LOAI PHNG PHAP CHUAN O KET TUA :

a. Phng phap bac : Da tren phan ng chuan o :

X + Ag+

AgX

e ch. (Cl, Br, I) va SCN bang dd AgNO3.

b. Phng phap thuy ngan : s dung dd Hg2+ e ch.
(Cl, I) theo p.u:

2X + Hg2+

Hg2X2

c. Phng phap chuan o kem : Cho phep xac nh

ion Zn2+ bang dd K4[Fe(CN)6] theo p. :
3Zn2+ +2K [Fe(CN) ] = K Zn [Fe(CN) ] +

6K+

3. PHNG PHAP O BAC

Gia s tien hanh chuan o V0 ml dung dch

cha ion halogenur X (Cl, Br, I hay SCN) co
nong o C0(mol/l) bang dung dch AgNO3 co nong
o C (mol/l).
Goi V la the tch AgNO3 cho vao tai moi thi iem
cua qua trnh chuan o.
F: mc o ion X- a c chuan o

CV
F=
C0V0

P. chuan o : X + Ag+ =
AgX
ng ch. la ng bieu dien s thay
oi pX (hoac pAg) theo the tch cua dd
chuan AgNO3 them vao : pX = f(V)
Khi cha chuan o (V = 0, F = 0)
pX c quyet nh bi dd X- co nong
o la C0 => pX = lgC0.
* Trc t (V0C0 > VC), F<1 :
pX c quyet nh bi dd X con d :

C0V0 CV
pX = lg
V0 + V

Tai t (V0C0 = VC, F=1) :

AgX Ag+ + X-

TAgX = [Ag+].[X] =>[Ag+] = [X]

[X ] =

TAgX

pX t =

1
2

pTAgX

Sau t (V0C0 < VC, F>1) :

pX c quyet nh bi lng AgNO3 d
TAgX = [Ag+].[X]
T

[X ] =

pX = pTAgX

AgX
+

[ Ag ]

CV C0V0
+ lg
V0 + V

V du : Ve ng chuan o 50 ml dung dch NaCl

0,1M bang dung dch AgNO3 0,1M.
Biet rang TAgCl = 1,0.1010
Phan ng chuan o:
Ag+ +

Cl-

AgCl

Tai iem tng ng the tch AgNO3 bang:

VDTD = V AgNO3

50 x0,1
=
= 50ml
0,1

0,1

1,09 8,91

25

0,5

1,48 8,52

45

0,9

49,5

0,99

49,95

0,999

50

50,05

1,001

50,5

1,01

75

1,5

100

Cong thc tnh pCl

pX = lgC0

V 0C0 VC
pX = lg
V0 + V
pX =

1
2

pTAgX

pCl

pAg

GHI CHU

1,00 9,00

2,28 7,72
3,30 6,70
4,30 5,70

SS% = 0,1%

5,00 5,00 iem tng ng

5,70 4,30 SS% = + 0,1%

pX = pTAgX

VC V0C0
6,70 3,30
+ lg
V0 + V
7,79 2,21
8,70 1,30

Sai so chuan o

CV C 0 V0
SS % =
.100
C 0 V0

Tai iem tng ng

pX =

1
2

pTAgX

Neu ket thuc pX < pXT :

Ket thuc chuan o trc iem tng ng (d

dung dch NaX ). Phep chuan o mac sai so thieu SS

S% X
% < 0 va c ky hieu

S%X =

10

pX

(C0 + C ) 2
.10
C0V0

Neu ket thuc pX > pXT :

Ket thuc chuan o sau iem tng ng (d dd
AgNO3). Phep chuan o mac sai so tha SS% > 0 va
SS% +
c ky hieu
Ag

S % Ag + = +

10

pX pTAgX

(C0 + C ) 2
.10
C0C

V du : Chuan o 100ml dung dch NaI 0,1M bang

dung dch AgNO3 co cung nong o.
a) Tnh sai so cua phep chuan o tren neu ket
thuc chuan o pAg = 11.
b) e sai so chuan o khong vt qua 0,02%
th phai ket thuc chuan o trong khoang pI bang bao
nhieu ?
Cho biet : TAgI = 1016

Gii

NaI + AgNO3 AgI + NaNO3

pHt = pT = (-lg10-16) = 8
a) pAgc = 11 => pIc = -lg10-16 11 = 5
pIc< pIt => F < 1 ; dd tha NaI

10 pI (C0 + C ) 2
10 5 (10 1 + 10 1 ) 2
S %I =
.10 =
.10 = 0,02%
1
1
C0V0
10 .10

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

S % Ag +

10 pI 16 (C0 + C ) 2
10 pI 16 (10 1 + 10 1 ) 2
= +
.10 = +
.10 = + 0,02%
1
1
C0V0
10 .10

10pI-16 = 10-5 => pI = 11

4. CAC PHNG PHAP XAC NH IEM CUOI TRONG

PHNG PHAP O BAC

Nguyen tac cua phng phap la them vao dung dch

chuan o mot ion co kha nang tao vi ion Ag+ mot
ket tua co mau am gan iem tng ng.
a.Phng phap Mohr
Mohr e ngh dung ion CrO42- lam ch th
2Ag+ + CrO42- Ag2CrO4 (o gach)
11, 95
Ag 2CrO4

= 10

Qua trnh chuan o ion halogenur X theo phng

phap Mohr xay ra nh sau :
X
CoVo

+ Ag+

AgX

CV

Khi va d mot giot ion Ag+ th :

CrO42- + 2Ag+

Ag2CrO4 (o gach)

Khi thay hon hp chuyen t mau vang sang mau hi

o cua ket tua Ag2CrO4 th ngng chuan o.

A Precipitation Titration
dd
AgNO3
Dd mu
vng

Kt ta
trng
AgCl
trong dd
mu
vng.

Khi Cl-
p ht

Kt ta
Ag2CrO4
mu
gch.

Pp Mohr c dung e nh lng Cl, Brnhng khong dung e nh lng I, SCN v

AgI va AgSCN hap phu manh ion do o se
quan sat thay s chuyen mau trc t rat xa,
phep chuan o mac sai so ln.

P.P Moh cn tin tin hnh trong mi trng c

pH = 6,5 8,5 v:
* Trong mi trng axit th nng ion gim
nhiu do tham gia phn ng:
H+ + CrO42- HCrO4Do s i mu xy ra sau v xa t(sai s
ln)
* Ngc li trong mi trng kim mnh s xy
ra phn ng:
2Ag+ + 2OH- 2AgOH
2AgOH Ag2O( en) + H2O

b. Phng phap Fajans

Da tren kha nang thay oi mau cua 1 loai
ch th ac biet khi hap phu len be mat ket tua
tch ien(ct hap phu).
Ch th hap phu la cac acid hoac baz hu c
yeu
HInd H+ + Ind
Hay IndOH Ind+ + OH

Ch. Cl- bng Ag+ vi ch th hp ph HInd

Ag+ + Cl- AgCl
* Trc t to h keo m:

+
+
[(mAgCl )nCl , (n x) Na ]xNa

Ht kt ta m nn khng hp ph Ind- => dd c

mu ca ch th t do.
* Sau t tao he keo dng AgCl/AgNO3

{[(mAgCl )nAg

, (n x) NO ]xNO

Hat ket tua tch ien dng nen hap phu anion
Ind- do o hat ket tua co mau.

Cc cht ch th thng dng l:

Fluorescein : la mot acid yeu(Ka=108) nen
phai ch. trong m.t kiem e ch th phan ly
manh th mi thay ro mau.
pH mt 10 trnh xy ra p
2Ag++ 2OHAg2O (en) + H2O
tot nhat la chuan o pH = 6,5 10.

Fluorescein dung trong chun cc ion Cl-,Br-,

I-. t dd s chuyn t mu lc ( c nh hunh
quang) sang mu hng(kt ta hng trong dd
khng mu).
- Oesein; dng chun cc ion:Br-, I-, SCN pH = 2 10. t: dd chuyn t mu kc
sang mu thm.

C. Phng phap Volhard

Nguyen tac : Da vao phan ng chuan o ion Ag+
bang ion SCN vi ion Fe3+ lam ch th :
Ag+ + SCN AgSCN (trang)
Khi o d 1 giot SCN th xuat hien mau o mau cua
phc Fe(SCN)2+ : Fe3+ + SCN FeSCN2+
*Cho mot lng d, chnh xac dd AgNO3 vao dd X
(Cl, Br, I) : Ag+ + X AgX
chuan o Ag+ d bang dung dch chuan SCN vi
Fe3+ lam ch th nh tren :
Ag+ + SCN
AgSCN
Ngng chuan o khi thay mau cua dung dch chuyen
sang mau hong.

Lu y : Pp nay can thc hien trong m.t acid e tranh

s thuy phan cua ion Fe3+ ( HNO3 vi C > 0,3M)
Khi xac nh I bang pp nay can cho AgNO3 d
trc e ket tua het I roi mi them ch th Fe3+ e
tranh phan ng : 2Fe3+

2I

2Fe2+

I2

Khi xac nh Cl bang pp nay iem cuoi se xay

ra p : AgCl +

SCN AgSCN + Cl