CHAPTER

5
Complexometric Titration

1
 Syllabus
Topics to be Covered
1. Complex formation reactions.
Complexes of EDTA and metal ions.
Equilibrium calculation involving EDTA.
2. Stability of complexes-stepwise formation constants,
3. Titration with aminocarboxylic acids (chelating agents).
4. Complexes of EDTA and metal ions, Equilibrium calculation
involving EDTA. Conditional formation constants.
5 EDTA titration curves.
Effects of other complexing agents on EDTA titration.
6. Indicators for EDTA titration.
7. Titration methods employing EDTA.
Scope of EDTA titration.

•.

2
 Complex Formation Titration
COMPLEX FORMATION REACTIONS:
• These are the Lewis acid base reactions (Ligand donate electron/s pair to
the metal ion (an electron deficient species).
• Metal ion lies at the center called central metal atom. The number of bonds
formed with it is called coordination number of the metal.
An example is, Ag+ + 2CN- Ag(CN)2-
• Ligands: unidentate (NH3), bidentate (triethylenediamine, NH2CH2CH2NH2)
….tridentate, quadridentate, …, hexidentate.
• Heterocyclic rings formed by the interaction of metal ion with two or more
functional group of same ligand is called chelate rings/ such ligands are
chelating agents and the complex is called clelates or chelate compounds.
• Complexes which under go substitution reaction very easily and rapidly are
said to be labile, Cu(H2O)42+ + 4NH3 Cu(NH3)42+ + 4 H2O.
• On the other hand which donot readily undergo substitutuion reaction are
2+ 3+
non labile or+ inert complexes. eg. Almost all complexes
CH2 CH2
of Coinert
& Cr 3+
Co(NHare3)62+
Labile Ag(NH3)2
inert.Hg(Cl) NH2
Cu
NH2
Fe(CN) 6
3-
2 Cu2+ + 2NH2CH2CH2NH2
Cu(NH3)4 2+ NH2 NH2 Cr(CN)63-
Ethylenediamine
Ni(CN)42- CH2 CH2
3
STABILITY OF COMPLEXES:-
• Consider a general complex forming reaction.
M + nL MLn M metal ion, L is the ligand and MLn is the complex.
Eq. constant: [ML] stability constant or formation constant
K
[M][L]n Higher is K more stable is the complex.
The reciprocal of it is instability or dissociation constant
The magnitude of K will determine the feasibility of the reaction.
STEPWISE FORMATION CONSTANTS:-
• If combining molar ratio of L/M > 1, complex forming reaction occurs in a series
of steps. The equilibrium constant of each steps of reaction is shown below.
• Consider the complex of Cu2+ with NH3:-
¤ Cu2+ + NH3 CuNH32+ K1 = 1.9 ×104
¤ CuNH32+ + NH3 Cu(NH3)22+ K2= 3.6 × 103
¤ Cu(NH3)22+ + NH3 Cu(NH3)32+ K3= 3.6 × 103
¤ Cu(NH3)32+ + NH3 Cu(NH3)42+ K4= 3.6 × 103
• For overall reaction, Cu2+ + 4NH3 Cu(NH3)42+ KOverall= 8.1 × 1012
2+
[Cu(NH 3 ) 4 ]
K 2+ 4
 K1 K 2 K 3 K 4  8.11012 4
[Cu ][NH 3 ]
Q. The titration of HCl with ammonia: H3O+ + NH3 NH4+ + H2O K = 1.8 × 109 is feasible
but, Cu2+ with ammonia: Cu2+ + 4NH3 Cu(NH3)42+ is not? K= 8.1 × 1012
• The nature of the titration curve
among these two is different.
• The intermediate/lower complexes
are extremely stable and are present
in appreciable concentration.
• The reaction is not complete near to
the eq. point.
• For acid VS NH3: pH >> pM for Cu
VS NH3 (at the eq. point)
• Ammonia donot react in a single step Fig: Titration of 0.01 M HCl and 0.01 M
Cu2+ with ammonia (no vol. change)
to form complex Cu(NH3)4 2+
25% 75%
• [at 75% towards the eq. point [Cu2+]/[ Cu(NH3)42+] should be 1:3 and pCu will be
2.6 but in fact pCu = 4.5 (lower Cu2+ concentration); the reason that pCu is high,
because all the decrease in [Cu2+] is not involved in the formation of Cu(NH3)42+,
but also the lower complex species are formed].
• This kind of difficulties that arises from lower complexes can be removed by
the use of chelating agents as titrant, they form complex in a single step. 5
Q. The titration of Cu2+ with trien is feasible but its titration with
ammonia is not?
Cu2+(aq.)+ trien(aq.) Cu(trien) 2+(aq.)
Cu2+ + 4NH3 Cu(NH3)42+
[Cu(trien) 2+ ]
K 2+
 2.5  10 20 KOverall= 2.5 × 1020
[Cu ][trien]
• Single step reaction • No single step reaction
• pCu is large at the eq. point • The reaction is not complete
• Rapid completion near to the eq. point.
• Complex and complexing • pCu is small at the eq. point
agent both are soluble • Slow reaction: a number of steps
K1 [Cu(NH3)]2+
Cu2+ + NH2CH2CH2NHCH2CH2NHCH2CH2NH2 K2
Cu2+ + NH3
Triethylene tetramine [Cu(NH3)2]2+
2+
CH2 CH2 K3
NH2 NH CH2 [Cu(NH3)3]2+
Cu
NH2 NH CH2
K4
2+
CH2 CH2 [Cu(NH3)4]
6
  TITRATION WITH AMINOCARBOXYLIC ACIDS (CHELATING AGENTS),
COMPLEXES OF EDTA AND M-IONS:-

EDTA, (YH4) 2-
O
C
HOOCCH2 CH2COOH O
CH2
NCH2CH2N C CH2
HOOCCH2 CH2COOH Complex with Co2+
O
O N
CH2
Ethylene diamine tetraacetic acid Co
(Ethylene dinitrilo)tetraacetic acid CH2
O N
• Free EDTA or Na2H2Y C
CH2 CH2
are available. O
O
• Forms the complex with C
M-ion in 1:1 ratio O
• Hexadentate Ligand, four O and two N atoms can donate to Metal ion.
• In basic medium all oxygen are free but in acidic medium partial protonation of
EDTA leads to some complex like CuHY-,
• At very high pH, OH- ion may be penetrated into the co ordination sphere of the
metal and complex like Cu(OH)Y3- may exist. 7
EQUILIBRIUM CALCULATION INVOLVING EDTA,
• General M-EDTA reaction is:

Mn+ + Y4- MY-(4-n)

Absolute stability /formation constant
[MY -(4-n) ]
K abs 
[M n  ][Y 4- ]
• EDTA is acidic, possess four dissociation equilibria,
• The different forms of EDTA are:
H6Y2+, H5Y+, H4Y, H3Y-, H2Y2-, HY3- , Y4-

Strong acids Weak acids

8
 Distribution of EDTA species as a function of pH
• EDTA (H4Y), possesses four H= and also different dissociation constants:

 [H 3 Y - ][H  ]
H 4 Y  H 3Y  H
-
K a1   1.02  10 -2
[H 4 Y]
H 2 Y -  H 2 Y 2-  H  K a 2  2.14  10 -3
H 2 Y 2-  H Y 3-  H  K a 3  6.92  10 -7
HY 3-  Y 4-  H  K a 4  5.50  10 -11

• pH > 12 , most EDTA exists as Y4-

• At lower pH different other species predominates. In figure at pH 4 H2Y2- is in excess. In
this condition the complex reaction with Cu2+can be written as,
Cu2+ + H2Y2- CuY2- + 2H+,
• This reaction suggests that as pH decreases, the equilibrium will shift backward. Thus
we can say that below a certain pH the titration will not be feasible (the reaction will
be incomplete). This shows that magnitude of K abs only cannot explain feasibility9 of
Optimization of pH for a complexometric titration:
• pM value at various stage of titration can be calculated, but we have
to consider different equilibria: dissociation equilibria, and
complexation equilibria.
• The minimal pH for EDTA titration of metal can easily be calculated by
using Kabs and Ka values of EDTA.
• If cY represent the total molar concentration of uncomplexed EDTA,
cY = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]
• total fraction in Y4- is :
[Y 4- ]
4  or, [Y 4- ]   4 .c Y
cY
Using the dissociation constant expression,
[Y 4- ] K a1 K a 2 K a3 K a 4

cY [H 3O  ]4  [H 3O + ]3 K a1  [H 3O  ]2K a1 K a2  [H 3O  ] K a1 K a2 K a3  K a1 K a2 K a3 K a4

• The value of α4 at any desired pH can be calculated readily. So that10

Conditional formation constants (effect of pH), Keff of
• Effective or conditional formation constant is
constant only at a pH for which α4 is Known.
• Unlike Kabs, Keff varies with pH, depends on α4.
• The Keff measure the immediate tendency to form
complex. Therefore while determining the
feasibility of titration at a given pH, the conditional
[MY -(4- n) ]
formation constant is used. K abs 
[M n  ]  4 c Y
pH 4 Keff pH 4 Keff
[MY -(4 - n) ]
K abs 4  n
 K aeff
[M ] c Y
Q. Calculate [Y4-] on 0.02M EDTA buffered at pH 10,
α4 = 0.35
• - Keff values are not often tabulated, but can readily
be calculated from Kabs,
• Above pH 12 all cY is in the form of Y4-; Kabs = Keff. 11
 EDTA TITRATION CURVES:-
Q; 50mL 0.01M Ca2+…….. 0.01M EDTA (pH 10); Calculate pCa at various stage
of titration. [Kabs = 5X1010, α4 = 0.35→Keff = 1.8X1010 ]
• Before eq. point Mn+ is in excess, is used to calculate pM,.
• At and after eq. point conditional formation constant should be used.
Reaction
Start of titration:
Ca2+ + Y4- CaY2-
[Ca ] = 0.01→ pCa = 2.0
2+
[Ca2+] + CY [CaY2-]
Addition of 10 mL,
[Ca2+] = 0.4/60→ pCa = 2.17
At eq. point
2
[Ca ] =cY,
2+ [CaY ]
K eff
[Ca 2 ] C Y
[CaY ]=0.5/100,
2-
From,
[Ca2+] = 5.2X10-7, pCa = 6.28
Addition of 60 mL,
cY = 0.1/110, [CaY2-]=0.5/110, gives, [Ca2+] = 2.8X10-10, pCa = 9.55
• A plot of pCa sharply increases around the equivalent point
• The plot for pH 7, 8.5 & 10 are also shown in figure .
• As pH decreases Keff will be less so titration will not be feasible. 12
FEASIBILITY OF EDTA TITRATION:
• The magnitude of K i.e. Keff can be determined in the similar way as in the acid base
titrations.
• 50 mL of 0.01M titrant is titrated with 0.01 M EDTA . Calculate the value of K eff so that
when 49.95 mL of titrant is added the reaction is essentially complete and pM changes
by two units on addition of two more drops of2titrant. 4-
M  Y  MY 2-
solution:
i> one drop before equivalent point : 0.0005
[M 2 ]   5 10 6 M, pM  5.3
ii> After equivalent point: 99.95
pM  7.3 ,  [M 2 ]  5  10 8 M, After equivalent point
0.05  0.01
cY   5  10 6 M M 2   Y 4-  MY 2-
100.05
0.05 0.0005 0.5
[MY 2- ]   5  10 3 M  -
100 100.05 100.05
[MY 2- ]
K eff  K  2
 2  1010
[M ]  c Y

Now to determine the lowest pH (once Keff is selected to be feasible pH can be easily
calculated)
log Keff = log Kabs + logα4
For an example in the titration of Zn with EDTA, log Keff = at least 8 (to be), from table log
Kabs for ZnY2- is 16.5, At pH 4 log Keff is 8.06 and at pH 5 log Keff is 10.05. Thus the titration
13
 Minimum pH for Effective Titration
of Metal Ions

End Point becomes less distinct as pH is lowered,

limiting the utility of EDTA as a titrant
Note that the metal EDTA complex becomes less
stable as pH decreases

itration of each metal ionE

With decreasing pH, Kf decreases, [Fe3+] = 5.4× 10-7 at
pH 2.0 and [Fe3+] = 1.4× 10-12 at pH 8.0
In order to get a “complete” titration (Kf ≥ 106), EDTA
requires a certain minimum pH for the titration of each

DTA as a titrant
metal ion
Example:What is the concentration of free Fe3+ in a solution of 0.10 M Fe(EDTA) at pH
8.00?
EFFECTS OF COMPLEXING AGENTS ON EDTA TITRATIONS:-
• Substance other than EDTA may form complexes with M ion and
compete the desired titration reaction.

+ Y4- MY-(4-n)
Mn+
tartarate OH-

NH3

• As pH i.e. (H3O+) affects (lowers) the Keff of M-Y complex, presence of

other ligand also affects the Keff. It can be easily calculated if solubility
constant for the complex is known.
Eg, Zn-NH3 complexation and effect on Keff Zn-EDTA
15
 Zn-NH3 complexation and effect on Keff Zn-EDTA
• Zn2+ + NH3 ZnNH32+ K1 = 190 [Zn(NH3 )2+ ]
K1  2 
[Zn ] [NH3 ]
• Zn NH32+ + NH3 Zn(NH3)22+ K2= 210
 [Zn(NH3 )2+ ]  K1  [Zn 2 ] [NH 3 ]
• Zn(NH3)22+ + NH3 Zn(NH3)32+ K3= 250
• Zn(NH3)32+ + NH3 Zn(NH3)42+ K4= 110
• The total analytical concentration Zn species (cZn) not Zn-EDTA
2 2 2 2
c Zn  [Zn 2 ]  [ZnNH3 ]  [Zn(NH 3 ) 2 ]  [Zn(NH 3 ) 3 ]  [Zn(NH3 ) 4 ]

 [Zn 2 ] 1  K1[NH 3 ]  K1K 2 [NH 3 ]2  K1K 2 K 3 [NH 3 ]3  K1K 2 K 3 K 4 [NH 3 ]4 
[Zn 2 ] 1
The fraction of uncomplexed zinc  4   or [Zn 2 ]   4  c Zn
c Zn (1  .........)
for Zn 2 complexati on wth EDTA in presence of NH3
2 [ZnY 2- ] [ZnY 2- ]
Zn Y 4-
 ZnY 2-
K abs  
[Zn ][Y ]  4  c Zn   4  c Y
2 4-

[ZnY 2- ]
K abs   4   4  K eff 
c Zn  c Y
16
• Q. given K1k2K3 K4 for Zn with NH3 as above, Kabs with EDTA = 3.2X1016
calculate Keff for the reaction at pH 9 assume [NH3]= 0.1M , α4 = 5.1 X
10-2 (tabulated value) [Zn 2 ]
The fraction of uncomplexed zinc  4 
c Zn
1

1  K1[NH 3 ]  K1K 2[NH 3 ]2  K 1K 2K 3[NH 3 ]3  K 1K 2K 3K 4[NH 3] 4
1

{1  190  0.1  190  210  (0.1) 2  190  210  250  (0.1) 3 
190  210  250 110  (0.1) 4 }
• Here, β4 = 1/……. = 8.3X10-6,
• Keff = kabs X α4 X β4=1.4X1010.
• The break at equivalent point is small at
higher concentration of NH3 than at low conc..
• Q. Thus addition of too much buffer in
EDTA titration introduces common error if
buffer anion or neutral species also complexes
the M- ion. 17
Masking and its application:
EDTA and other ligands may be complexed with other
interfering M ions, such process is termed as masking.
Ni form complex with CN not the lead, thus in presence of CN lead
can be titrated with out interference (the stability constant NiY2- and
PbY2- are nearly same, log Kabs = 18.6 and 18.0).
For some M-ion that readily forms hydroxide, complexing agent
should be added to prevent hydroxides. In buffered solution buffer
anion or neutral molecule (acetate ion, NH3) can form complex.
 INDICATORS FOR EDTA TITRATIONS: A varieties of good indicators are
available.
Titration of Mg2+ by EDTA
These indicator changes the color when
pM changes abruptly at the equivalent
point in the similar way as acid base
indicator , when pH. Get changed.
These indicators are called
metallochromic indicators and responds
different metal ions as: pMg, pCa, pCu,
etc.
Eriochrome Black T Indicator
What are metallochromic indicators?
• Are colored organic compounds which themselves forms chelates with M-ion.
• The chelate in complexed and Free state has different color.
• They should readily release M-ion to EDTA in titration, at pM value very close to
eq.pt.
• Should have good indicator range.
• The determination of indicator range is some complex because it responds both
pH and pM. For an EDTA titration, the indicator must bind the metal ion
less strongly thanEDTA
1. Erichrome Black T OH
OH

H3In H2In-1 Hin2- In3- O3 S

-
N N

(pKa = 6.3) (pKa = 11.6) Yellowish

Red Blue orange Erichrome Black T
CH3
• Forms 1:1 complex with M ion (Mg, Ca, Zn, Ni)
• Between pH (8-10) where EDTA is used, it exists as HIn2-
• Unstable in aq. solution. so should be freshly prepared.
2. Calmagite: OH HO

-
O3 S N N

CH3
• Stable in aq. solution. Calmagite
• Represented
H3In H2In1- Hin2- In3-
(pKa = 8.1) (pKa = 12.5) Reddish
Red Blue orange
 The determination of indicator range in EDTA titration:
• The indicator range depends on both pH and pM.
• Let us consider calmagite indicator for titration of Mg2+.
• The pM vs pH curve is as shown in the figure.
• The equilibrium shows at different pH the color change between complex and
free is different.
pMg at eq. pt. is calculate using
reactions: (slide no 21)
M 2  Y 4-  MY 2-
• At pH 10, 4 = 0.35
• and Kabs=4.9×108

• The indicator range is obtained

5.268 Mg 2  HIn 2-  MgIn + H +
5 [H + ][MgIn]
K  5.2 10 
[Mg 2 ][HIn 2- ]

• The equilibrium shows at

different pH the color change
H2In1- Hin2- In3- between complex and free is
(pKa = 8.1) (pKa = 12.5) Reddish different.
Red Blue orange
• Q. Calculate the pMg at eq. pt. for titration of 50mL
0.01MMg2+ with 0.01M EDTA, pH=10
0.05
c Y  [Mg 2 ]  [MgY 2- ]   5 10 3 reaction: Mg 2  EDTA  Mg-EDTA
100
K eff  K abs   4  1.72 108 [K abs  4.9 108  4  0.35] [Mg 2 ] cY [MgY 2- ]
[MgY 2- ] 2 2 11 2 6
K eff   [Mg ]  2.9  10  [Mg ]  5.4  10
[Mg 2 ]  c Y
pMg  5.268

For Calmagite and Mg 2+ the indicator range at pH 10 [ 4.7-6.7]

2  [MgIn - ][H  ] 5
Mg  HIn 2-
 MgIn  H
-
K  5.2  10
[HIn 2- ][Mg 2 ]
[MgIn - ][H  ]
2
gives, [Mg ]   for Ca 2
[HIn 2- ] 5.2 105
Ca 2  HIn 2-  CaIn -  H  K  5.2 107
when ratio is unity and pH  10, pCa  3.7 (at pH 10),  in-range is 2.7-4.7.

2 1 1010 6
At eq. point: pCa  6.28.
[Mg ]  5
 1.9  10 , pMg  5.7  colour change occurs far before eq. point.
5.2 10
The interval is 5.7  1
This easily spans the eq. pt. for pMg  5.26
APPLICATION OF EDTA TITRATION:
• Replaces tedious gravimetric analysis. can be done normally for all common cation
• Direct titration: for≈25-40 cations complexing agent like citrate, tartarate, are
added to prevent precipitation of m-hydroxide. NH3/NH4Cl buffer is used for pH 9-
10. Total hardness of waterCa/Mg. erichrome black T or calmagite (Mg must be
present). A trace of Mg2+ can be added to EDTA before standardization/ MgY2-(Less
atable)< CaY2-(more atable)
– Limited to those M ions: slow reaction/ indicator not available.
• Back titration: if reaction with EDTA is slow No suitable indicator available. EDTA in
Excess. Cations should form very stable complex with EDTA.
• Replacement/Displacement titration: No suitable indicator for the M-ion. Excess
solution of Mg EDTA is added. M2+ displaces Mg,
M2+ + MgY2- MY2- + Mg2+.
The displaced Mg is titrated with EDTA using calmagite indicator
• Indirect determination: several are reported. Sulfate has been determined by
addingexcess Ba2+ ions to precipitate BaSO4. the excess Ba2+ is titrated with EDTA.
Phosphates …………… '' ………Mg2+ MgNH4PO4[Note M-EDTA are motvery stable
so consecutive reading may not be obtained. Fe(III), Cu(II0 are determined in a
single EDTA titration, using photometric detection of end point]
• Direct Titrations
Some Common Techniques used in these
• Analyte is buffered to appropriate pH and istitrations
titrated include:
directly with EDTA
a)Direct
• An auxiliary complexing agent may be required Titrationsb)Back
to prevent precipitation of metal
hydroxide Titrationsc)Displacement
Titrationsd)Indirect Titrationse)Masking
• Back Titrations Agents
• A known excess of EDTA is added to analyte
• Free EDTA left over after all metal ion is bound with EDTA
• The remaining excess of EDTA is then titrated with a standard solution of asecond
metal ion
Approach necessary if analyte:
• precipitates in the presence of EDTA
• Reacts slowly with EDTA-
• Blocks the indicator
• Second metal ion must not displace analyte from EDTA
• Displacement Titration
Used for some analytes that don’t have satisfactory metal ion indicators
Analyte (Mn+ ) is treated with excess Mg(EDTA)2-, causes release of Mg2+
Mn+ + MgY2- = MYn-4 + Mg2+
Amount of Mg2+ released is then determined by titration with a standard EDTA
solution. Concentration of released Mg2+ equals [Mn+]
• Indirect Titration
• Used to determine anions that precipitate with metal ions
• Anion is precipitated from solution by addition of excess metal ion
ex. SO42- + excess Ba2+ = Precipitate is filtered & washed
• Precipitate is then reacted with excess EDTA to bring the metal ion
back into solution

• The excess EDTA is titrated with Mg2+ solution

• Masking Agents
• A reagent added to prevent reaction of some metal ion with EDTA
• Al3+ + 6F- = AlF63- , Al3+ is not available to bind EDTA because of the complex
with F-

• Demasking: refers to the release of a metal ion from a masking

agent
SELECTIVITY OF EDTA TITRATION
pH dependence of EDTA makes it selective:
• Low pH ions giving very stable complex can be
analyzed with out interference by other. eg. FeY-
Keff = 11.7 (pH2), can be determined in the
presence of, Ca, Ba, Mg ….. low Keff.
• Ni2+ at pH 3.5, (in presence of alkaline earth
cations can be determined, but interference
occurs at pH 10[NH3/NH4Cl buffer]) same Keff
• Different stability of M-complexes is also the
criteria for the selectivity.
Q.
• 50.0mL solution which is 0.0100M Ca2+ and buffered at 10.0 is
titrated with 0.100M EDTA solution. Calculate the value of pCa at
various stage of titration and plot the titration curve. K abs for CaY2-
is 5.0X1010; α4 at pH 10.0 is 0.35. Hence Keff is 5.0X1010X0.35
=1.8X1010.
• 50.0 mL of 0.010M M2+ is titrated with 0.010M EDTA solution.
Calculate the value of Keff so that when 49.95mL of titrant has been
added the reaction is essentially complete and pH changes by 2.00
units on the addition of two more drops (0.10mL) of titrant.
• Given the four constanta K1, K2, K3 and K4 for the reaction of Zn2+
with NH3, [Zn2+ + NH3 = Zn(NH3)2+ K1 = 190; Zn(NH3)2+ + NH3 =
Zn(NH3)22+ K2 = 210; Zn(NH3)22+ + NH3 = Zn(NH3)32+ K2 = 250;
Zn(NH3)32+ + NH3 = Zn(NH3)42+ K4 = 110;]and the K abs for reaction of
Zn2+ with EDTA is 3.2X106, calculate the value of Keff for the reaction
of Zn with EDTA in a buffer of pH 9.0, Assume that the