:- :-

1.

2.
3.
4.
5.
6.



(metal ions)
electron donor
complexing agent chelating agents
ligands

2



-
alkali metals
:- Al, Bi, Mg, Ca, Zn

 EDTA
(ethylenediamine tetraacetic acid)
chelating agent
- EDTA titration
Chelometric titration

 :-
- amperometric
titration, potentiometric titration
- Spectrophotometric detection

 :1.

2.

3.

6


:
1. spectrophotometry:


spectrophotometer

dithizone (chelating agent)
7

2. gravimetry:


nickel-dimethylglyoxime
3. fluorometry :

(fluorescence)
4. chromatography

1.
1.1 (complexes or
coordinating compounds or complex ion)
-
-
(anion) (ligands)

(Acid, electron acceptor)

(Base, electron donor)

Metal ligand complex

 copper (II)
(ammonia) :
-
hydrated form
2+

OH2

H2O
Cu
H2O

2+

OH2

hydrated copper (II)

(electron acceptor)

NH3

H3N
4NH3

Cu
H3N

electron donor

NH3

4H2O

copper(II)-tetrammine

11

 Cu (II)
Glycine (bidentate ligand)
Cu oxygen carboxyl
nitrogen amine
NH2 O
2+

Cu

C O

Cu

2H C C OH
H

H2C

N H2

O
+

2 H+

NH2 CH2

(bidentate ligand)

Glycine
12

1.2 (central atom or ion)

-

Cr3+, Fe3+
+
+
Na , K
13

1.3 (ligand, complexing agent

coordinating group)
- (anion)

- unshared electron pair

coordinate covalence bond (metal-ligand bond)
-
14

 :- donor atom

-
electronegativity
- Donor atoms:- halide ion, oxygen
atom, sulfur atom, nitrogen atom, phosphorus
atom
electron pair
15

 1 anions molecules

16


1. Unidentate ligands (Monodentate ligands)
2. Multidentate ligands (Polydentate
ligands)

17

1.3.1 Unidentate ligands (Monodentate ligands):- inorganic anions donor

atom
- electron pair

-

18

 2 Unidentate ligands

19

1.3.2 Multidentate ligands (Polydentate ligands):-

donor groups (atoms)
- electron pair 1

-

21

23

24

1.4 Chelates ( kee/late):

donor atoms 1
(multidentate ligands)
- Chelates chelate ring
structure heterocyclic ring
- Chelates
5 6 member ring
25

 Multidentate ligand chelates

Ligand

Type

Ethylenediamine

Bidentate

Glycine

Bidentate

Oxalate ion

Bidentate

Diethylenetriamine

Tridentate

N-hydroxyethylenediamine

Tridentate

Chelate

Triaminotriethylamine
Quadridentate
Ethylenediaminetetraacetic

Hexadentate
26

Chelates :-

- chelates

27

Chelates:-
:

Ligand
- Donor atom basic
nitrogen atom
proton

Chelate
-
Zinc(II)
Ethylenediamine,
Cu(NH3)42+

 Chelate Zinc (II) Ethylenediamine

Ligand

Chelates

- acidic donor atom

-
( 1 )
Zinc (II)
basic donor atom 1
8 -Hydroxyquinoline
1
acidic group proton
chelation charge
neutralization
30

 Chelate Zinc (II) 8- Hydroxyquinoline

N
2+

Zn

O
Zn

2
O

(8-hydroxyquinolate)

31

 basic group acidic group

1 Chelate :- 2:1 (2 ligand : 1 metal ion)
+2 cations
- 3:1 (3 ligand : 1 metal ion)
+3 cations
32

Ligand

acidic group 1

Chelates

chelate EDTA
divalent metal ion

 5 acidic groups basic nitrogen

NH

N and aromatic N
C
O
NH
aromatic N
CN=andNOH

O
CC =NOH

* anionic form acidic group

35

1.5 Chelons (sequestering agents):

1:1

- Ethylenediaminetetraacetic
acid (EDTA)

36

HOOCCH2

CH2COOH

:N

CH2 CH2 N :

HOOCCH2

CH2COOH ,
EDTA

(complexometric titration)
37

1.6 Coordination Number and Structure

Coordination number:
(covalent bonds)
(metal-ligand bonds)

39

- coordination number
2,4,6 1,3, 5, 7

- copper (II) ion
6 ammonia
tetraamminediaquo copper (II) ion
Cu(NH3)42+
Cu(NH3)4(H2O)22+
40

Coordination number (metal ion)

: -

Coordination no
2

Linear [H3N :

Ag

: NH3]

- univalent metal ion : silver (I),

copper (I) gold (I)
- Ligands:- cyanide, ammonia, halides
- Ag(CN)2-, Cu(NH3)2+ AuCl242

Coordination No

Tetrahedral, Square Planar

Divalent metal ions :- Ni(II), Co(II), Cu(II),

Ligands:- Halides, cyanide

Coordination no
6

Octahedral

Metal ions : Fe (III), Co (III), Cr (III), Cu (II), Ni (II),

Co (II) Ca (II) ions
Ligands: , Ethylenediamine, EDTA

 6 Coordination number

2.

ML M L :M+L
ML
(1)
ML + L
ML2
.(2)
ML2 + L
ML3
.(3)
;
MLn-1 + L
MLn
.(4)
M =
L =
n =

 equilibrium constant
formation constant stability constant
: [ML] ,
[ML3] , ........,
[ML2] ,
[MLn]
K1 =
K
K
=
=
3
n
[M][L] K2 = [ML][L]
[ML n - 1][L]
[ML2][L]

 equilibrium constant stability constant :Ks =

[ML n]
[M][L]

n = K1 x K 2 x K 3 ...... K n

. (5)

Ks = equilibrium constant stability constant

 Ks :-
-
- equilibrium

- stability constant (Ks)
pKs
pKs = - log [Ks]

3.
:



(free metal ion)
complexing agent

 EDTA:- pM,
EDTA, (pM = - log[M] )
- pM
pM free metal
ion
-

potentiometer

 titration curve
S plot graph pM
1

pM = - log [ M ]

3.1 : 2

3.1.1 (analyte)
(analyte- titrant
concentration)
3.1.2
(completeness of reaction)

3.1.1
-

:-

- :-
- 0.001M:- EDTA

 Titration curve

1x 10-6 M
1x 10-4 M
1x 10-2 M

3.1.2 :- formation constant:-

-

 pH Mg2+ EDTA (Y4- )

pH
Mg2+ + Y4MgY2H+
HY3-, H2Y2-, H3Y : Y4- Mg2+


3

4.
4.1
4.2 pH
4.3 complexing buffer

4.4
4.5

4.1 (choice of titrant)

complexing ligands
stability constant formation constant


multidentate ligands
4 6 donor groups
1 : 1

 multidentate ligands :1. Multidentate ligands

unidentate ligand

2. Multidentate ligands

formation constant
-

 :-

Zn (II) EDTA (multidentate ligand)

Zn2+ + EDTA2-

(Zn-EDTA)2- + 2H+, log Ks = 19.0

 unidentate ligands:-
- formation constant
formation constant
:-

Zn (II) ammonia:-

 Zn (II) ammonia (unidentate ligand)

4 :Zn2+ + NH3
Zn(NH3)2+,
log K1 = 2.3
Zn(NH3)2+ + NH3
Zn(NH3)22+, log K2 = 2.3
Zn(NH3)22+ + NH3
Zn(NH3)32+, log K3 = 2.4
Zn(NH3)32+ + NH3
Zn(NH3)42+, log K4 = 2.0
formation constant
Zn2+ + 4NH3
Zn(NH3)42+,
log Ks = 9.0


(M) ligands
5 overall
equilibrium constant 1020

Multidentate ligand

chelon (1:1)

1. Polyamines
2. Polyaminocarboxylic acids

1. Polyamines
Zn, Co, Hg (II), Cu (II) Ni
ethylenediamine, diethylene triamine,
triethylenetetramine (trien) tetraethylenepentamine
(tetren)
- Cu (II)
potentiometry
- polyamines-copper
copper

Polyamines
trien
Trien quardridentate ligand nitrogen 4

electron pair 4

- copper (II), mercury (II)
nickel (II)
- trien chelating
agent protonation nitrogen atoms

Trien : NH CH2

CH2

NH2

CH2

NH2

CH2
CH2
NH CH2

2.

Polyaminocarboxylic acids

- Ethylenediaminetetraacetic acid EDTA

- hexadentate ligand electron pair6
carboxylic acid 4 nitrogen 2
(bond)

- EDTA complexones, chelons,

sequestrene, versene, chelaton 3
EDTA

EDTA : HOOCCH2

CH2COOH

:N CH2 CH2 N:
HOOCCH2

CH2COOH

EDTA
- amino acid
- zwitterion 2
- 4 2 carboxylic
groups 2 amino groups
- zwitterion EDTA H4Y
deprotonated ion Y4- 6 (e)

 EDTA :Zwitter Ion, (a) H4Y

( b) H3Y( c) H2Y2-

(d) HY3-

(e) Y4-, Deprotonated ion

 EDTA
- H4Y, H3Y, H2Y2-, HY3- Y4-
6
- EDTA
pH
- : pH 3-6 H2Y2 pH 10 EDTA Y4-

 EDTA
1. EDTA

multidentate ligand

1:1

- transition metal
ions Fe, Co, Ni
Cu

2. EDTA
pH : pH 8-11 Mg2+, Ca2+,
pH 4-7 Mn2, Fe2+
pH 1-4 Bi, Hg, Fe3+

-
pH : :- Mg2+ Zn2+ pH = 7 Zn- EDTA
pH > 8.5
pH 3.5

Mg- EDTA

Zn- EDTA

3. EDTA

4.
EDTA
5.
6. EDTA ( disodium salt
EDTA)

 EDTA:- EDTA free

acid(H4Y) disodium 2
(Na2H2Y.2H2O)
- EDTA: Na2H2Y.2H2O


- Disodium EDTA pH ~ 4-5
H2Y293

 pH EDTA:- EDTA Multiprotic Acid (H4Y)

- 5 pH : H4Y, H3Y-, H2Y2-, HY3-, Y4-

 pH polyprotic acid: relative concentration, ()

- relative concentration ()
EDTA
: = EDTA (specie)

97

 Y4- :-

98

 equilibrium
constant, K1,K2, K3, K4, H3O+
(7-10) y4- :-

99

100

 EDTA
H3O+
pH
EDTA
plot graph
pH graph

101

 pH graph 8
HY3-

H2Y2-

H4Y

Y4-

H3Y-

10 12 14

pH EDTA
102

- EDTA
Y4- pH
pH 3-10 EDTA H2Y2 HY3-

EDTA pH 4-5
H2Y2104

 7 aY4- EDTA pH
4-

Y4-

105

 EDTA
(Complexes of EDTA and metal ions)

107


EDTA equilibrium constant:
Y4-
:n+
M +

4-

MY

n-

, K MY =

n-4
[MY
]
n+ 4 [M ][Y ]

109

 EDTA

hydrogens
carboxylate groups EDTA :Mg2+ + H2Y2MgY2- + 2H+
Al3+ + H2Y2AlY- + 2H+
Th4+ + H2Y2ThY + 2H+

110

 8 formation constants EDTA

112

4.2 pH
- EDTA
H2 EDTA

Mg2+ + H2Y2Al3+ + H2Y2Th4+ + H2Y2-

MgY2- + 2H+
AlY- + 2H+
ThY + 2H+

- buffer

pH

114

4.2.1 : (acidity)
hydrogen ions hydrogen ions
EDTA protonate EDTA
inactive EDTA (H3Y -, H4Y) EDTA

Mn+ + H2Y2- + 2H2O
MY(n-4) + 2H3O+
H+
H3Y-, H4Y (acidic EDTA)
(H2O + H+)
115

117

 :1. pM metal ion

Inactive
EDTA
2. Indicator metal ion
pH H+ indicator metal
ion indicator protonate
-
pH
118


-

- trivalent metals pH 1 2
- tetravalent
- divalent

119

4.2.2 pH :-

Metal ion EDTA

- pH :-Metal ion
- pH

121



pH buffer

- pH Ca2+ EDTA
- pH 6

 pH Ca2+ EDTA
123

Volume of 0.0100 M EDTA, ml

pH 6
125

Buffers
1. Ammonia-ammonium chloride buffers
auxiliary complexing agents
pH 10
hydroxide
2. Acetic acid sodium acetate buffer
pH 5
127

4.3 auxiliary complexing buffers :- EDTA

- hydroxide
pH
-
- (auxiliary complexing agents or
complexing buffer)

auxiliary complexing
EDTA

Auxiliary complexing agents:-

- Ammonia, triethylamine triethanolamine
ammonia

- Ammonia ammonium chloride
buffer

131

 Zinc (II) EDTA

ammonia-ammonium chloride
buffer auxiliary complexing agent :

Zn2+
Zn(OH)2
Zn2+ + 4NH3
Zn(NH3)42+( )
EDTA (HY3-):Zn2+ + HY3ZnY2- + H+
Zn(NH3)42+ + HY3ZnY2- + 3NH3 + NH4+
132

Ammonia buffer :-

- pH
EDTA
- Zn (OH)2
Zn(NH3)42+
-

EDTA
133

 ammonia weak complexing ligands

EDTA
(shift)
:Mn+ + H2Y2MYn-4 + 2H+
L L'
ML'
L' ammonia
/

135

 complexing buffers ligands

titration curve :-
pM

- auxiliary complexing agent
hydroxide
pM
(postequivalence)
136

 complexing buffer titration curve

13

auxiliary complexing buffer ( aM )=

(-----) (-----) aM =

 1 Cd2+
0.0100 M EDTA pH 9.0
ammonia 0.010 M, 0.10 M 1.0 M
ammonia
pCd2+
14

139

 14 ammonia
Cd2+ EDTA pH 9.0
140

 2 ammonia
50.0 ml 0.00500 M Zn2+ buffer pH 9.00
Eriochrome
Black T

141

5.

5.1 2
5.1.1 (Visual method):

5.1.2 potentiometric detection
electrodes
- 2 mercury pool electrode gold
amalgam electrode
- Mercury electrode

143

5.1.1 (Visual method):

: 1. Metal or metallochromic indicators
2. pH indicators
3. Redox indicator

144


1. Metal indicator metallochromic indicator:- dye chelating agent
- metal-indicator complex

- Metal-indicator complex
Metal-EDTA complex
-
hydrogen ions

Metal indicator
chromophore group

1. Triphenylmethane dyes
2. Phthalines substituted phthalines
3. Azo dyes
4. Phenolic compounds
5. Anthraquinone dyes
147


metal-indicators:1.

2. metal-indicator complex 1:1
metal-EDTAcomplex

3.

4. Metal-indicator complex
free indicator

5.

 :1. metal (M), indicator (I), EDTA

(direct titration) : 1:- metal-indicator

complex :M +
KMI

I
( )
=

[MI]
[M][I]

MI +
M
( ) ()

:-

- free metal EDTA

metal-EDTA complex :M + EDTA

( )
KS =

M - EDTA
[M-EDTA]
[M] [EDTA]

 :-

- free indicator :MI + EDTA

M - EDTA + I

( )

KS

( )
= [M-EDTA] [I]
[MI] [EDTA]

: MI + M + EDTA

M EDTA + I

2. metal M, indicator I EDTA

( Back or residual titration ): :- EDTA
:

- metal-EDTA complex EDTA

: M + EDTA
M EDTA + EDTA
()
( )

 :- :
EDTA
M/ magnesium zinc
sulfate M/-EDTA complex
- :EDTA + I
EDTA + I + M/
M/ - EDTA + I
( )
( )

 :- metal-indiator complex :-

- (M/)
metal (M/)-indicator complex
:-

M/

M/ I

( ind.)
(Exess)
( complex)
M/ = ZnSO4 MgSO4
I = indicator

5.3 (Metallochromic indicators)

:1. pH
2.
5.3.1 pH :- EDTA
- protonated species
- species

 Eriochrome black T (EBT):- triprotic acid H3In

-

H3In

H2In- + H3O+

( )

- - (acid-base)

(ionization)

 EBT

: EBT
OH

OH
-

O2S

OH
N

N
+

NO2

( H2In- ,red)

O2S
H2O

N
+

NO2

( HIn2- ,blue)

H3O

 pH (pH 11-12) :-

- HIn2-
In3-

(orange) (orange)

indicator :OH
-

O2S

O
N

pH 11-12
+

O2S

HIn (blue)

O
N

N
+

H2O

2-

NO2

H3O

3-

NO2

In (orange)
indicator

-EBT pH8-10:- Metal- EBT complex

- : -
-EBT pH(<6.3) :- EBT :- metal-EBT
complex
- pH (> 11.5):-EBT

5.3.2
-
:- EBT Mg, Zn, Cd, Pb
- Iron (III), Co Ca

 11 , pH
Indicator

Chemical type

Erio T

Azo

8-10

Erio R

Azo

8-12

Mg, Zn, Cd, Pb, (Mg +

Ca)
Mg, Zn (Mg + Ca)

CalRed

Azo

12-14

Ca

Calmagite

Azo

9-11

Mg, Zn, Cd (Mg + Ca)

PAN

Azo

2-11

Cu, Pb

Murexide

Purine

6-13

Ca, Cu, Co, Ni

Calcein Blue

Iminodiacetate

5-9, 13-14

Salicylic acid

2-3

Zincon

Hydrazo

Useful pH
range

5-10

Typical
determined

Cu, Ca

Fe

Zn, Cu, Ca

metals

 titrate Ca2+ EBT indicator

 :-

Eriochrome BlackT (Mordant Black 11,Solochrome Black T)

- EBT pH 8-10
- Metal- EBT pH 10
- (pH 10)
pH 6.3:- Metal- EBT EBT
pH>11.5:- EBT indicator

 Eriochrome Black T divalent

metals :O

OH
HO

O3S

O 3S

M
N

N
+

2+

NO2

NO2

Blue at pH 10
Free form at pH 10

Pink
Complex at pH 10

2 H+

Eriochrome Black T (EBT)

Direct titration back titration

- EBT indicator direct titration :Mg, Ca, Cd, Zn, Mn, Pb, La Hg (I)
- back titration :- Ba Sr

EBT :1. Co, Ni, Cu, Al, Ag, Ti Pt :- Metal- EBT Metal- EDTA

- EBT

masked

2. iron (III, Fe3+), cerium (IV, Ce4+)

vanadate ions :-
3. stannous, titanous :-

Eriochrome Black T azo (N=N) nitro (NO2)

groups :- :- reduced oxidized groups
redox oxidized


- :-
0.2%

Dithizone (1,5-Diphenylthiocarbazone) :
-

- Dithizone keto-enol tautomeric
system
-

Dithizone keto-enol tautomeric system

:S

OH

H
N
S

_
N

C
N

keto (primary)

OH

_
S

_
N

C
Enol (secondary)

 keto form
enol form
- mono
diprotic acid mono (enol)
di (ketone) dithizone pH
- dithizone
form form
- keto form
enol form

Dithizone :- mercury, silver, gold, zinc, cadmium, nickel

platinum
- Metal-Dithizone (
)


- Dried Aluminium
Phosphate (back titration)
ZnCl2

 dithizone :-

NH

HN

NH

2+

NH

2+

C
N

C
N

Dithizone
(green-violet)

Metal- dithizone complex

(rose pink)

2. pH indicator
divalent
polyvalent

EDTA 2
M2+ + H2Y2MY2- + 2H+


-

3. Redox indicator: :- redox

- oxidation states
2 (iron)
- EDTA
oxidized form
reduced form

6.

5 : -

1. (Direct titration)
2. (Back or Residual titration)
3. (Displacement or Replacement
titration)
4. (Indirect titration or Titration of anion)
5. (Alkalimetric titration)

1. (Direct titration)

buffer, masking agent indicator

EDTA
: -
metal-indicator complex free indicator
- blank (indicator blank)
-

 Indicator blank:-

1.
2. ( )
Titrant
3. blank


4.

EDTA
EDTA blank

 :1. :

Mn+ + I
MI
+ ( Mn+)
() ( ) ( )

2. EDTA (H2Y2-) :
EDTA:Mn+ + H2Y2-

MYn-4 + 2H+

3. : EDTA
metal-indicator complex free indicator

MI + H2Y2MY n-4 + I + 2H+
( )

( )

- Bi, Ca, Mg Zn

2. (Back or Residual titration)

- direct titration
:- hydroxide
-
- EDTA
- EDTA

 :- EDTA

- buffer

- ( Titrant back titration)

- Back titration:- Titrate EDTA
magnesium zinc sulfate

EDTA
= EDTA
Zinc magnesium sulfate
-

- Blank (volume relationship)

 : 1. EDTA
:Mn+ + H2Y2MYn-4 + 2H+
2. EDTA (H2Y2-)
zinc sulfate:H2Y2- + Zn2+
ZnY2- + 2H+
( )

3. :- zinc sulfate


Zn- indicator complex :Zn2+ + I
ZnI
( )

( )

aluminium
lead (II), mercury (II) nickel

3. (Displacement or
Replacement titration):-
direct back titration :-

-

 displacement titration :-
EDTA

- EDTA
-
- EDTA
< EDTA
-

 displacement titration:-

- Zn-EDTA
Mg-EDTA

- Titrate Zn Mg( ) EDTA

indicator
- EDTA
zinc
magnesium EDTA


1. : (Mn+) Mg2+
Mg-EDTA (MgY2-) Mg2+ Mg2+

MgI Mg2+
:Mn+ + MgY2MYn-4 + Mg2+
Mg2+ + I
MgI + Mg2+
(Ind )

( )

2. Mg2+ EDTA
(H2Y2-):Mg2+ + H2Y2MgY2- + 2H+
3. :- Mg2+ EDTA
Mg2+ MgI free
indicator, I
:MgI + H2Y2MgY2- + I + 2H+
( )
( )

4. (Indirect titration or titration

of anions ):- anions
complexing agent (titrant, EDTA)
- anions

:- Cation (
)


anions :-

Anions 2 :1. Cation

EDTA
2.
EDTA

- EDTA
Cation zinc magnesium sulfate
barbiturate sulfate

 1 barbiturates :Barbiturates EDTA

- barbiturates

mercuric ion 1 : 1 : 1. barbiturate (B- )

mercuric ion (Hg2+)
B- + Hg2+
(Barbiturate anion)

Hg - B complex+
()

2. Hg (II)
-
EDTA
- EDTA
zinc (II)
: -

Hg - B complex + H2Y2-

B- + HgY2- + H2Y2( )

3. EDTA Zinc sulfate:H2Y2- + Zn2+

ZnY2- + 2H+
( )
4. : Zn2+ + I
ZnI
- barbiturates Hg (II)
Hg (II) back titration
barbiturates indirect titration

 2 sulfate :- sulfate barium

- barium
EDTA
- blank (volume relationship) barium
- sulfate

1. sulfate barium
:SO42- + Ba2+
BaSO4 + Ba2+
(excess)
2. Ba2+
EDTA:Ba2+ + I
Ba2+ + H2Y2(excess)

BaI + Ba2+
BaY2- + 2H+

3. :BaI + H2Y2-

BaY2- + I + 2H+

Sulfate Barium
Sulfate

Barium
= Barium Barium

5. (Alkalimetric titration or
titration of hydrogen liberated)
- hydrogen ion

EDTA
- acid-base indicator

:- EDTA
( buffer)
Mn+ + H2Y2MYn-4 + 2H+
+
+
2H + 2NaOH
2Na + 2H2O

7. :1. pH
2. metal indicator

3.
4. masking agents

5. Reduce oxidize

1. pH :-
pH
-
pH
pH

 1:Trivalent cations divalent cations

pH 1

Trivalent metal
pH 1 divalent

- trivalent cations

 2: cadmium zinc magnesium

- Eriochrome Black T
- Magnesium :- Cadmium Zinc EDTA
pH 7
- Magnesium EDTA pH 7

2. metal indicator :

pyrocatechol violet selective metal

indicator bismuth ( pH 2-3)

- bismuth lead,
cadmium zinc
(EDTA)

 :- Bi Zn

- pyrocatechol violet selective metal

indicator :- bismuth: EDTA
(pH 2-3)

- Zn: ammonia buffer pH 10

EDTA
- pyrocatechol violet
pH

3. :-
( precipitating agents)

-


Precipitating agents
Metal
Oxalate
Ca
Sulfide
Heavy metals, Ex.
Pb Mg
Fluoride
Al
Hydroxide
Transition metals:Fe, Mg
Magnesium sulfate
Ba, Pb
Ferrocyanide
Zn, Cu

4. masking agents
:- Masking agents auxiliary complexing agents

-


- Masking agents

- masking agents

- (masked)

- masked

demasking agents

 12 Masking agent
Metal masked

Assay

Masking agent
Cyanide

Ni, Co, Zn, Cd, Cu, Fe(II), Pd

- Pb ammonical
tartrate Cu Co
- Ca, Mg pH 10
+2 Zn
- In ammonical tartrate
Cd, Co, Cu, Hg, Ni, Zn

Triethanolamine (TEA)
N(CH2CH2OH)3

Fe(III), Al, Mn

- Ni ammonia Al, Fe,

Mn mask
Metal-TEA complex ,

- Mg Al ammonia
pH 10
- Zn Cd Al
ammonia pH 10

Fluoride

Al, Mg, Ca

- Zn Al ( AlF63- ) Mg
Ca ammonia
- Ga Al glacial acetic acid
pH 2.8

2,3-dimercapto-1propan-1-ol (BAL)
CH2 CH CH2
OH SH SH

Tin, Sb, Cd, Hg, Zn

- Mg Bi, Cd, Cu, Hg, Pb

ammonia
- Th Bi Pb

Tiron (disodium catechol-3,5disulfonate)

Al, Ti, Fe (II)

Tartaric acid

Sb

Iodide

Hg(II)

 1:- masking demasking agents

Cu, Cd Ca
- : 1
EDTA
Cu + EDTA
Cu EDTA
Cd + EDTA
Cd EDTA
Ca + EDTA
Ca EDTA

 2:- Masked Cu Cd cyanide

Ca EDTA
Cu + Cyanide ion
Cu Cyanide complex
Cd + Cyanide ion
Cd Cyanide complex
Ca + Cyanide ion

EDTA:Ca + EDTA
Ca EDTA

 3:- Demasked cadmium (Cd): formaldehyde chloral hydrate

cyanide ( 2)
EDTA :OCd Cyanide complex + CH2O
Cd + CH2 - CN
Cu Cyanide complex + CH2O

EDTA:Cd + EDTA
Ca + EDTA

Cd EDTA
Ca EDTA

 3
EDTA
Cd, Ca Cu : EDTA = Cu = 1 3
EDTA = Cd = 3 2
EDTA = Ca = 2

 2 :-

Lead (Pb), Magnesium

(Mg), Zinc (Zn) :- EDTA
2
- Mg2+, 1

 1. Masked Zn NaCN
Zn
EDTA :Zn + 4CNZn(CN)42 EDTA (Y4-)
Pb2+ + Y4PbY2Mg2+ + Y4MgY2-

 2 : complexing agent BAL (2-3

dimercapto-1-propanol, CH2SHCHSHCH2OH)
R(SH)2 1
- R(SH)2 Pb2+
PbY2- : PbY2- + 2R (SH)2
Pb(RS)2 + 2H+ + Y4-

 3 :- Y4- 2
Mg2+
Y4- + Mg2+
MgY2()

4 :- Demasked zinc formaldehyde

Zn(CN)42- + 4HCHO + 4H2O

Zn2+ + 4HOCH2CN + 4OH-

 5 :- Zn2+ 4

EDTA:Zn2+ + Y4-

ZnY2-

:-

- Pb2+, Mg2+ Zn2+

EDTA
Mg2+ : 1. Pb2+ Mg2+ : EDTA
1
mmol[ Pb2+ + Mg2+] = mmol [EDTA]

2. Pb2+
Mg2+ Y4 2 ( 3 )
mmol Pb2+ = mmol Mg2+ 3
3. Mg2+ 1
3
mmol Mg2+= mmol [Pb2+ + Mg2+] - mmol Pb2+

2+
Zn

4.

EDTA 5:mmol Zn2+ = mmol EDTA 5


Pb2+, Mg2+ Zn2+
( 1 ) EDTA
0.02064 M 42.22
EDTA (Y4-)
BAL ( 2 ) Mg2+ 0.007657
M 19.35
( 5) Zn2+
formaldehyde ( 4) EDTA (Y4-)
0.02064 M 28.63

percent 3 0.4085 g

1. mmol Pb2+ Mg2+

:mmol (Pb2+ + Mg2+) = 42.22 x 0.02064 = 0.87142
2. mmol Pb2+
2:mmol Pb2+ = 19.35 x 0.007657 = 0.14816
3. mmol Mg2+:mmol Mg2+ = mmol (Pb2+ + Mg2+) - mmol Pb2+
mmol Mg2+ = 0.87142 - 0.14816 = 0.72326

 mmol Zn2+

mmol Zn2+ = 28.63 0.02064 = 0.59092

% Pb2+ =

0.014816mmolPb 0.2072 gPb / mmolPb 100

0.4085 g sample

% Mg2+ =

0.72326mmolMg 0.024305g Mg / mmolMg X 100

0.4085g sample

% Zn2+=

= 7.515

0.59095mmolZn 0.06539g Zn / mmolZn X 100

0.4085 g sample

= 4.303
= 9.459

 3:-

magnesium aluminium
triethanolamine masked
aluminium
triethanolamine-aluminium
EDTA

7.5 Reduce oxidize

reduce oxidize :-
EDTA : Fe3+ reduce Fe2+ + EDTA

Ascorbic acid

Hg2+ Ascorbic acid Hg0 + EDTA

Cr3+ oxidise
CrO42- + EDTA
H2O2



: -

1.
calcium, magnesium, copper
EDTA
deionized water

inactivate indicator

2.
primary standard chelometric
standard grade
3. EDTA
polyethylene soft
glass
hard glass
EDTA

8.

8.1 EDTA
(Standardization of 0.05 M EDTA solution)
0.05 EDTA
18.6 disodium ethylenediaminetetraacetic
acid 1000

 Complexometric
titration:1. 0.05 M.
EDTA :- Direct titration
- CaCO3 Primary standard
- Hydroxy naphthol blue indicator

 0.05 M EDTA : CaCO3 200

400
10 swirl slurry

2

Swirl CaCO3 ,

100
EDTA 30

 sodium hydroxide (NaOH TS)

15 hydroxy naphthol blue
300
EDTA

blank 100

 EDTA
:-

Molarity EDTA = W / 100.09 V

W CaCO3
V
EDTA
100. 09 CaCO3

 : : CaCO3 + 2 HCl
CaCl2 + H2O + CO2
EDTA : Ca2+ + H2Y2CaY2- + 2H+
NaOH :2 NaOH + 2 H+
2 Na+ + 2 H2O

 :Ca2+ + HIn2CaIn- + H+
( )

( )

EDTA : Ca2+ + HY3CaY2- + H+

: CaIn- + HY3CaY2- + HIn2( )
( )

 EDTA
- CaCO3 (primary standard)
CaCO3
CaCl2
EDTA pH
:- EDTA Ca2+
NaOH Ca2+
NaOH pH 13
Ca-EDTA complex pH
magnesium

8.2 (Calcium)

4

1. - EDTA
2.

3.
4.

1. :
100
50 2 3 swirl


100

 50.0
50
pH pH 12 1.0 N sodium
hydroxide 300 hydroxy naphthol
blue indicator

EDTA

1 0.1 M EDTA
4.008
-
0.05 M EDTA
-

2.
:
50.0
50
0.1 M MgSO4 2

 5 eriochrome black T
23

0.1 M EDTA

blank 0.1 M MgSO4 2

 0.1 M EDTA
:
0.1 M EDTA
( ) 0.1M EDTA
Mg2+ blank
1 0.1 M EDTA
4.008

 :Ca2+ + HIn2CaIn- + H+ ( )
Mg2+ + HIn2MgIn- + H+ ()
indicator :2+
2+
22+
+
Ca + Mg + HIn
Ca + MgIn + H

 :Ca2+ + HY3 : 3MgIn + HY

( )

CaY2- + H+
22MgY + HIn

( )

 Blank:Mg2+ + HIn2 :3MgIn + HY

( )

MgIn- + H+
22MgY + HIn

( )

3.

50.0 ml
50.0 0.1 M EDTA 23
eriochrome black T

0.1 M

 0.1 M EDTA
:
0.1 M EDTA 0.1 M
(
)

1 0.1 M
EDTA 4.008

 :Ca2+ + H2Y2CaY2- + 2H+ + H2Y2()

()
:H2Y2- + Mg2+
MgY2- + 2H+
( )
:Mg2+ + HIn2MgIn- + H+
( )
( )

4.
(Replacement titration)

Mg-EDTA

EDTA


Mg-EDTA

 : Ca, 50.0 ml(50mg/50 ml)

50 ml
Mg-EDTA 25 ml
ammonia buffer 5 ml eriochrome blackT 23
0.1 M EDTA

1 0.1 M
EDTA 4.008
Mg-EDTA

0.1M EDTA correction
MgCl2
MgSO4


:Ca2+ + MgY2CaY2- + Mg2+
Mg2+ :2+
2+
Mg + HIn
MgIn + H
( )

( )

2+
3 Mg EDTA (HY ) ,

Direct titration:Mg2+ + HY3 :MgIn- + HY3( )

MgY2- + H+
MgY2- + HIn2( )

 Mg-EDTA
1. Mg-EDTA (0.005 M)
0.01 M MgCl2
0.01 M EDTA (ratio)
reagent treat
buffer pH 10 eriochrome black T
0.01 M EDTA 1
0.01 M MgCl2
1
Mg-EDTA 2

8.3 (Lead)

250 100
50.0

acetate buffer 5 xylenol

orange 23

 0.1 M EDTA

1 0.1 M EDTA
20.72


Pb2+ :Pb2+ + H3In3PbHIn3- + 2H+
EDTA:Pb2+ + H2Y2PbY2- + 2H+
:PbHIn3- + H2Y2PbY2- + H3In3( )
( )

 (Magnesium): 75
100
50.0 ml
50 ml

 ammonium buffer 5 ml eriochrome

black T 23
0.1 M EDTA

1 0.1 M EDTA
2.432


Mg2+ :Mg2+ + HIn2MgIn- + H+
:Mg2+ + HY3MgY2- + H+
:MgIn- + HY3MgY2- + HIn2( )
( )

 (Zinc)
200
100 ml
50.0 ml
50 ml
acetate buffer 5 xylenol orange 23

 0.1 M EDTA
(Purple-yellow)
1 0.1 M EDTA
6.538


Zn2+ :Zn2+ + H3In3ZnHIn3- + 2H+
:Zn2+ + H2Y2ZnY2- + 2H+
:ZnHIn3- + H2Y2ZnY2- + H3In3( )
( )

 (Al2O3)
(Aluminum hydroxide gel)
: 25
15 ml
(Volumetric flask)
500 ml

 20.0 ml 250 ml

0.05 M EDTA 25.0 ml

acetic acid ammonium acetate buffer TS 20 ml
5

 50 ml Dithizone TS 2ml
0.05 M Zinc sulfate
(Green-violet)
(Rose-pink)
blank
1 ml 0.05 M EDTA
Al2O3, 2.549 mg


:Al(OH)3 + 3HCl
AlCl3 + 3H2O
EDTA:3+
2+
Al + H2Y
AlY + 2H
()

 :22+
2+
H2Y + Zn
ZnY + 2H
()
:Zn2+ + 2HInZn(HIn)2
( )

( )

 AL(OH)3, Mg(OH)2, CaCO3

Alumina, Magnesia, and Calcium Carbonate Tablets
:-

1. :-

20

600 mg 20
(3 N) 40


(volumetric flask)
200 ml


Al(OH)3 + 3HCl
AlCl3 + 3H2O
Mg(OH)2 + 2HCl
MgCl2 + 2H2O
CaCO3 + 2HCl
CaCl2 + CO2 + H2O

2. , Al(OH)3
10.0 ml
250 ml 20 ml
0.05 M EDTA 25.0 ml,
acetic acid ammonium acetate bufferTS.20 ml
~ 5

 alcohol, 50 ml dithizone TS. 2 ml

Titrate 0.05 M ZnSO4
(green
violet, Ind) (rose pink, complex)
1 0.05 M EDTA
3.900

 Al(OH)3
EDTA (H2Y2-):Al3+ + H2Y2AlY- + 2H+ + ( H2Y2-)
EDTA Zn2+ (
):H2Y2- + Zn2+
ZnY2- + 2H+

:Zn2+ + 2HIn( )

Zn(HIn)2
( )

 EDTA


masking agent
Al-EDTA Mg-EDTA Ca-EDTA
(KAlY2- = 1.3 1016 , KMgY2- = 4.9 108
CaY2- = 5.0 1010)
EDTA Al3+

3. ,
Mg(OH)2:
40 mg 400 ml
200 ml, trolamine 20 ml

ammonia-ammonium Chloride buffer TS , 5 ml

eriochrome black T 23

 3 - 4 C
ice bath
0.05 M EDTA

blank

 0.05 M EDTA
: 0.05M
EDTA
0.05 M EDTA

1 0.05 M EDTA
2.916

 Mg(OH)2:
:- trolamine masking
agent Al3+
- 3-4 C
Al-Trolamine
Al3+

 Mg(OH)2
Mg2+
Ca2+ eriochrome black T (HIn2-) :- Mg2+
EDTA
- Ca2+ eriochrome black T
EDTA Mg2+
- MgIn
-
- EDTA Mg2+
Ca2+

 Mg2+ Ca2+
: EDTA :Mg2+ + HIn2MgIn- + H+
( )

Mg2+ + HY3Ca2+ + HY3-

:MgIn- + HY3-

( )

MgY2- + H+
CaY2- + H+
MgY2- + HIn2( )

 , CaCO3: CaCO3
50 mg 400ml 200ml
NaOH (1 2) 5
hydroxy naphthol blue
250

 0.05 M EDTA

1 0.05 M EDTA
5.004

 CaCO3: EDTA:Ca2+ + HIn4CaIn3- + H+

Ca2+ + H2Y2CaY2- + 2H+
2NaOH + 2H+
2Na+ + 2H2O

 :CaIn3- + HY3( )

CaY2- + Hin4( )

sodium hydroxide
pH 13 Ca-EDTA