COMPLEXATION

TITRATION
 A complexation titration is a titration in which the reaction
between the analyte and titrant is a complexation reaction.
 Complex formation titrations are used to titrate cations via
complex formation reagents.
 Most often in complexometric titrations, the ligand is the titrant
and the metal ion the analyte,
 Molecules/anions that react with metal ions must donate an
unshared pair of electrons to form a coordinate covalent bond
 Here, a metal ion reacts with a suitable ligand to form a
complex, and the equivalence point is determined by an
indicator or a suitable instrumental method.
The complex can form only when…
1. The central atom (a metal ion (or cation) in a complex)
accepts an electron pair from one or more ligands
(ligand = electron-pair donating species).
2. The ligand possesses at least one electron pair to
donate.
3. The bonding (coordinate covalent bonding) occurs .
 A number of common anionic and molecular ligands can
form complexes:
1. Anionic ligands include halides, SCN1-, CN1-, OH1-
RCOO1-, C2O42- (oxalate), etc.

2. Molecular ligands include water, ammonia,

(ethlenediamine), etc.
 The atom gives electron pair is known as donor, while the
atom accept electron pair is known as acceptor.
 The bond is represented by an arrow () from donor to
acceptor.
NH3

NH3  Cu  NH3

NH3
 Types of complexing agents (( Classification of ligands according
to the no. of sites of attachment to the metal ion ))
 Unidentate (Monodentate) Ligand or "Simple Ligand"
 The ligand attached to metal at one site e.g. H2O , NH3 , CN - , Cl -
, I - , Br - , (i.e. forming one coordinate bond, or capable of
donating one unshared pair of electrons)
 Bidentate Ligand
 The ligand attached to metal at two sites.

NH2 NH2 H 2N
H2C H2C CH2
2 + Cu2+ Cu
H2C H2C CH2
NH2 NH2 H 2N

Ethylene diamine
 Tridentate Ligand:
The Ligand attached to metal at 3 sites

Diethylene triamine

 Tetradentate Ligand:
The Ligand attached to metal at 4 sites

Triethylene tetramine
 Chelation
 The most useful complex-formation reactions for titrimetry
involve chelate formation.
 Chelate : It is a complex formed between the ligand
containing two or more donor groups and metal to form ring
structure. (heterocyclic rings or chelate rings).
 Multidentate ligands complexed to metal ions are called
chelates.
 Chelating agents: organic molecules containing two or more
donor groups which combine with metal to form complex
having ring structure.
 Most common chelating agents belong to a group of
compounds called polyaminocarboxylic acids.

 The most useful complex-formation reactions for titrimetry

involve chelate formation

 Chelates always have a "chelate ring.

 The selectivity of a ligand for one metal ion over another

relates to the stability of the complexes formed.

 Most transition metals bind six (or more) ligand atoms.

 Ethylenediaminetetraacetic acid (EDTA)
 A also called ethylenedinitrilotetraacetic acid,

 Ethylenediaminetetraacetic acid, or EDTA, is an

aminocarboxylic acid.
 EDTA is the most widely used complexometric titrant.

 Fully protonated EDTA has the structure:

• EDTA is a hexadentate ligand that is represented by the formula H4Y .
 EDTA, which is a Lewis acid, has six binding sites (the four
carboxylate groups and the two amino groups), providing six pairs of
electrons.
 The EDTA molecule has six potential sites for bonding a metal ion:
 donating one electron pair from each of the two amine group and one
electron pair from each of the four carboxylates to the bound metal
ion.
 The resulting metal–ligand complex, in which EDTA forms a cage-
like structure around the metal ion, is very stable.
 like a spider grasping a fly.
 Note that only the fully ionized, -4-charged anion binds to metal ions.
 EDTA is a hexaprotic system, designated H6Y2+
 The Four pK values apply to carboxyl protons, and the two
are for the ammonium protons.
• The neutral acid is tetraprotic, with the formula H4Y.
 Usually, EDTA titrations are conducted in alkaline conditions
under which EDTA will be present in different forms including
H6Y2+, H5Y+, H4Y, H3Y-, H2Y2-, HY3-, and Y4-.

• Therefore, controlling the pH is one major factor that affects

complexation.
 All metal–EDTA complexes have a 1:1 stoichiometry.
 Being a weak acid, EDTA dissociates in solution and it is the
unprotonated form – abbreviated as Y4-
 For EDTA to react with a metal ion, the hydrogens attached to the
carboxylate groups must be removed.
 In strongly basic solution, these hydrogens are removed by
reaction with hydroxide ion.
 In more acidic solutions, metal ions must be able to displace the
hydrogen's if a complex is to be formed.
 Since metal ions differ significantly in their ability to displace the
hydrogen's, the solution acidity can be used to “regulate” the
reactivity of EDTA toward metal ions.
 For example, most metal ions react quantitatively with a
stoichiometric amount of EDTA at pH 10, but only a few, such as
Fe3+ and Hg 2+ , also react quantitatively at pH 2.
 In many transition metal complexes, EDTA engulfs the metal ion,
forming the six coordinate species.
 Larger metal ions require more ligand atoms.

 In some complexes, such as Ca(EDTA) (H2O)22-, the metal

ion is so large that it accommodates eight ligand atoms.
 Auxiliary complexing agent
 A second ligand in a complexation titration that

initially binds with the analyte but is displaced

by the titrant.

 To ensure consistent results of titrations, the pH

of the solutions must be controlled by using

buffer solutions.
 Metal EDTA Formation Constants
 EDTA combined with the metal ion (1 : 1) to form
complex.
For a +1 cation: Ag+ + Y4  Ag Y3
For a +2 cation: Hg2+ + Y4  Hg Y2
For a +3 cation: Fe3+ + Y4  Fe Y
For a + n ion: Mn+ + Y4  MY(n – 4)+

 where Y4 is a shorthand notation for the chemical form of

EDTA
 The equilibrium constant for the reaction of a metal with a
ligand is called the formation constant, Kf OR KMY , or the
stability constant:

 Formation constants for most EDTA complexes are large

and tend to be larger for more positively charged cations.
 Conditional Metal Ligand Formation Constants
 The formation constant (Kf) =

 Describes the reaction between Y and a metal ion.

 As seen in the fractional composition diagram, However, most

EDTA is not Y4- below pH 10.37.

 The species H2Y2- , HY3- and so on, predominate at lower pH.

 The species Y becomes the predominate form of EDTA at pH

levels greater than 10.37.

 It is only for pH levels greater than 12 that Y4-becomes the only

significant form of EDTA.
 For pH levels less than 12, however, Kf overestimates the
stability of the MY2+ complex.
 At any pH a mass balance requires that the total concentration
of unbound EDTA equal the combined concentrations of each
of its forms.

 Where [EDTA] is the total concentration of all free (non-

complexed) EDTA species in the solution.
 To correct the formation constant for EDTA’s acid–base
properties, we must account for fraction of dissociation,α, for
each species as the fraction of EDTA in that form.

 For example,
α Y4– is defined as

Where
α Y4– is fraction of dissociation for EDTA present as Y4–
Values of α Y4– for Selected pHs
 From the definition we can express the
concentration of Y4- as
 If the pH is fixed (e.g., buffer), then the are
combined into the conditional (or effective) formation
constant, which describes the formation of MYn–4 at
any particular pH.

 Note: we can also use a modified form of this equation

to treat situations where MYn–4 is not the dominant
species.
 The conditional formation constant allows us to look at
EDTA complex formation as if the uncomplexed EDTA is
all in one form.
 EDTA Titrations

 Substitute [Y4-] into Kf equation

4
]  aY 4  EDTA
[MY n- 4 ]
[Y Kf 
[M n  ][Y 4  ]

[MY n- 4 ] where [EDTA] is the total

Kf  concentration of EDTA
[M n  ]a Y 4- [EDTA] added to the solution not
bound to metal ions
If pH is fixed by a buffer, then aY4- is a constant that
can be combined with Kf
n- 4
Conditional or effective [ MY ]
formation constant:(at a given K f  K  K f a Y 4-  [ M n  ][ EDTA]
'

pH)
 Reagents for EDTA Titrations
 The dihydrate of the sodium salt, Na2H2Y.2H2O, are
commercially available in reagent quality.
 Standard solutions of EDTA are usually prepared by
dissolving the Na2H2Y.2H2O in a volumetric flask.
 (Note: Most Na2H2Y.2H2O at normal, atmospheric
conditions comes with 0.3% excess water in the crystal.

 The excess water must be taken into account when

preparing standard solutions.)
 Complexation Titrations
 The progress of a complexometric titration is generally
illustrated by a titration curve,

 which is usually a plot of pM = -log[M] as a function of the

volume of titrant added.

Three Regions of EDTA Titration

 The curves are easily calculated by dividing the curve up

into domains:

 The pM before equivalence.

 The pM at equivalence.

 The pM after equivalence.

 As titrants, multidentate ligands, particularly those having four or
six donor groups, have two advantages over their unidentate
counterparts.

 First, they generally react more completely with cations and thus
provide sharper end points.

 Second, they ordinarily react with metal ions in a single-step

process, whereas complex formation with unidentate ligands
usually involves two or more intermediate species.
 Complexation reactions involve a metal ion M
reacting with a ligand L to form a complex ML.
M+L ML
 Complexation reactions occur in a stepwise fashion,
and the reaction above is often followed by additional
reactions:
ML + L ML2
ML2 + L ML3

MLn-1 + L MLn
 Unidentate ligands invariably add in a series of steps.
 With multidentate ligands, the maximum coordination
number of the cation may be satisfied with only one or a
few added ligands.
 The Nature of EDTA Complexes with Metal
Ions
 Solutions of EDTA are valuable as titrants because
the reagent combines with metal ions in a 1:1 ratio
regardless of the charge on the cation.
Ag+ + Y4- AgY3-
Al3+ + Y4- AlY-
 EDTA is a remarkable reagent not only because it
forms chelates with all cation but also because most of
these chelates are sufficiently stable for titrations.
 This great stability undoubtedly results from the
several complexing sites within the molecule that give
rise to a cage like structure in which the cation is
effectively surrounded and isolated from solvent
molecules.

 The ability of EDTA to complex metals is responsible

for its widespread use as a preservative in foods and in
biological samples.
 Selecting and Evaluating the
End Point
 The equivalence point of a complexation titration occurs when
stoichiometrically equivalent amounts of analyte and titrant
have reacted.

 For titrations involving metal ions and EDTA, the equivalence

point occurs when CM and C EDTA are equal and may be located
visually by looking for the titration curve’s inflection point.
 Finding the End Point with a Visual Indicator

 Most indicators for complexation titrations are organic dyes

that form stable complexes with metal ions.

 These dyes are known as metallochromic indicators.

 metallochromic indicator is a visual indicator used to signal

the end point in a complexation titration.

 To function as an indicator for an EDTA titration, the metal–

indicator complex must possess a color different from that of the
uncomplexed indicator.
 The endpoint for an EDTA titration is usually found by using a
metallochromic indicator

 this is a dye that can act as a complexing agent to complex the

metal being titrated.

 The colour of the indicator depends on whether it is attached to

the metal ion or free.

 At the beginning of a titration, some of the analyte metal ion is

complexed by the indicator.
 As EDTA is added, the free metal ion concentration
decreases – but some metal ion remains complexed by the
indicator.

 If the correct indicator and conditions are chosen, at the

equivalence point the EDTA has complexed all of the free
metal ion and then removes the metal from the indicator
complex:

 Where MIn and In have different colours.

 Most metallochromic indicators also are weak acids or bases.

 The conditional formation constant for the metal–indicator

complex, therefore, depends on the solution’s pH.

 Both EDTA and murexide are weak, multiprotic acids, and

even at the high pH used during Ca2+ titration they are partially
protonated. To account for protonation we should use
conditional formation constants in our calculations.

 This provides some control over the indicator’s titration error.

 The metal-ind. complex should be less stable than the
metal-EDTA complex.

 The color of free form different than color of complex one.

 Changes its color according to the pH of the medium.

 Where MIn and In have different colours.

 Among the very important indicators that are routinely used,

you will encounter two indicators namely Muroxide and
Eriochrome Black T (solochrome Black).

 Probably most popular and universal indicator used in

complexometric titrations is Eriochrome Black T.

 For pH below 6, its color is red, between 7 and 11 - blue,

 above 12 - yellow-orange.

 Complexed form is always wine red.

Selected Metallochromic Indicators
 Summary……………..
 Indicators used in complexometric titration are to some extent
similar to those used in acid-base titrations.

 Their color changes depending on the concentration of metal ions,

just like color of pH indicators changes depending on the H+
concentration.

 Mechanism of this color change is different, as all

complexometric indicators are just complexing agents, changing
their color depending on whether they are free in the solution, or
ligands in the complex.

 In most cases they are also weak acids or bases, and quite often
their color depends on the solution pH.
 For a metal indicator to be useful, several conditions must be
met.

 First of all - its stability constant must be high enough so that the
free metal when present in the solution is easily complexed,

 but lower than the stability of the complex with titrant.

 Otherwise indicator will be not replaced in the complex and there

will be no color change of the solution.

 Secondly, both indicator complex creation and dissociation

reactions must be fast, so that the equilibrium in the solution is
achieved almost immediately after titrant addition.
Potentiometric Methods:

 Potential measurements can be used for end-point detection in

the EDTA titration of those metal ion for which specific ion
electrodes are available.

Spectrophotometric Methods:

 Measurement of UV/visible absorption can also be used to

determine the end points of titrations.

 In these cases, an instrument responds to the color change in the

titration rather than relying on a visual determination of the end
point.
 EDTA Titration Techniques
Direct Titration
 Many of the metals in the periodic table can be determined by
titration with standard EDTA solution.

 Many metals can be determined by direct titrations with

EDTA.

 Weak metal complexes such as Ca2+ and Mg2+ should be

titrated in basic solution using EBT and Calmagite as the
indicator.

 Some methods are based on indicators that respond to the

analyte itself, whereas others are based on an added metal ion.
 Back-Titration Methods
 Back titration can be performed for the determination of several
metal ions can not be titrated directly but form stable EDTA
complexes.

 Back-titrations are useful for the determination of cations that

form stable EDTA complexes and for which a satisfactory
indicator is not available;
 The procedure, a known amount of EDTA is added to the
analyte sample solution and the excess is back titrated with a
standard solution of “weak” metal ion, Mg2+.

 The weak metal ion will not displace the analyte from its
EDTA complex.

 Calgamite can be used as an indicator for the back titration of

the excess EDTA with standard magnesium ion solution.
 Displacement methods
 In displacement titrations, an unmeasured excess of a solution
containing the magnesium or zinc complex of EDTA is
introduced into the analyte solution.
 MgY2- or ZnY2- complex is added to the solution of the analyte
solution (metal ion).

 Analyte displaces the Mg2+ or Zn2+, which is then back titrated.

 If the analyte forms a more stable complex than that of
magnesium or zinc, the following displacement reaction
occurs:

MgY2- + M2+ MY2- + Mg2+

 where M2+ represents the analyte cation.
 The liberated Mg2+ or, in some cases Zn2+ is then titrated with
a standard EDTA solution.

 Displacement titrations are used when no indicator for an

analyte is available.
Example:

 A zinc supplement tablet containing (nominally) about 10

mg of zinc ion was added to water and titrated with
0.01000 M (= 0.01000 mmol / mL) EDTA solution. The
corrected titration volume of the EDTA solution was 14.65
mL. Calculate the zinc content of the tablet in mg units.
(Molecular weight of zinc 65.37 mg/mmol)
 2.) Example
 What is the value of [Mn+] and pM for 50.0 ml of a
0.0500 M Mg2+ solution buffered at pH 10.00 and
titrated with 0.0500 M EDTA when (a) 5.0 mL, (b)
50.0 mL and (c) 51.0 mL EDTA is added?

Kf = 108.79 = 6.2x108

aY4- at pH 10.0 = 0.30

mL EDTA at equivalence point:

Ve ( mL )0.0500 M   5.00 mL ( 0.0500 M )  Ve  50.00 mL

mmol of EDTA mmol of Mg2+

(a) Before Equivalence Point ( 5.0 mL of EDTA)

 Before the equivalence point, the [Mn+] is equal to the concentration of

excess unreacted Mn+. Dissociation of MYn-4 is negligible.

moles of Mg2+
originally present moles of EDTA added

2 [(0 .0500 M Mg2  )(0 .0500 L) - (0 .0500 M EDTA)(0 .0050 L)]

[Mg ]
[0.0500 L  0.0050 L]

Original volume Volume titrant

Dilution effect
solution added

[Mg 2  ]  0.0409 M  pMg 2    log [Mg 2  ]  1.39

b) At Equivalence Point ( 50.0 mL of EDTA)
 At the equivalence point, all the Mg 2+ initially present is
now present as MgY.

 The concentration of Mg 2+, therefore, is determined by

the dissociation of the MgY complex.

 To find p Mg we must first calculate the concentration of

the complex.
[MgY2-]= initial mole of Mn+ divided bytotal volume
= (Molarity of Mg ) Volume Mg / volume Mg + Volume EDTA
Virtually all of the metal ion is now in the form MgY2-
Original volume of
Original [Mn+] Mn+ solution Moles Mg+ ≡ moles MgY2-

(0 .0500 L)
[MgY 2  ]  (0 .0500 M )
(0.0500 L  0.0500 L)

Original volume Volume titrant

Dilution effect
solution added

[MgY 2  ]  0.0250 M
(b) At Equivalence Point ( 50.0 mL of EDTA)

The concentration of free Mg2+ is then calculated as

follows:

Initial Concentration (M) 0 0 0.0250

Final Concentration (M) x x 0.0250 - x

[Mg( EDTA)- 2 ]
K'f  K f aY 4  
[Mg2  ][EDTA]
8 ( 0.0250  x )
 ( 6.2  10 )( 0.30 ) 
( x )( x )
Solve for x using the quadratic equation:

 x  [Mg 2  ]  [EDTA ]  1.16  10 5  pMg 2   4.94

 (c) After the Equivalence Point ( 51.0 mL of EDTA)

Virtually all of the metal ion is now in the form MgY2- and
there is excess, unreacted EDTA. A small amount of free
Mn+ exists in equilibrium with MgY4- and EDTA.
Calculate excess [EDTA]: Volume excess
Original [EDTA] titrant Excess moles EDTA

(0 .0500 M )(0 .0010 L)

[EDTA] 
(0.0500 L  0.0510 L)

Original volume Volume titrant

solution Dilution effect
added

[EDTA ]  4.95  10 4 M
(c) After the Equivalence Point ( 51.0 mL of EDTA)

Calculate [MgY2-]:

Original volume of
Original [Mn+] Mn+ solution Moles Mg+ ≡ moles MgY2-

(0 .0500 L) Only Difference

[MgY 2  ]  (0 .0500 M )
(0.0500 L  0.0510 L)

Original volume Volume titrant

Dilution effect
solution added

[MgY 2  ]  0.0248 M
(c) After the Equivalence Point ( 51.0 mL of EDTA)

[Mg2+-] is given by the equilibrium expression using [EDTA]

and [MgY2-]:

[Mg( EDTA)- 2 ]
K f  K f aY 4  
'
[Mg2  ][EDTA]

8 ( 0.0248 M )
 ( 6.2  10 )( 0.30 ) 
( x )( 4.95  10  4 M )

 x  [Mg 2  ]  2.7  10 7  pMg 2   6.57

 Exercise
• The concentration of Cl– in a 100.0-mL sample of water drawn
from a fresh water acquifer suffering from encroachment of
sea water, was determined by titrating with 0.0516 M
Hg(NO3)2. The sample was acidified and titrated to the
diphenylcarbazone end point, requiring 6.18 mL of the titrant.
Report the concentration of Cl– in parts per million.
QUESTIONS???

68