General Chemistry IV: CHEM-224

Lecture 2: Titrimetric Methods of

Analysis

Part III: Complex Formation Titrations

Module Lecturer: Davies Mweta PhD

February, 2023
 Complex Formation Titration

• Complexation titration is a volumetric

method based on the formation of a slightly
dissociated soluble complex.
• A complexation titration is one in which a
soluble undissociated, stoichiometric
coordination complex is formed at the
equivalence point.

2
 Complexation Reaction
• Metal ions in solution are always solvated
i.e. a definite number of solvent molecules are
firmly bound to the metal ion
• A complexation reaction with a metal ion
involves the replacement of one or more of
the coordinate solvent molecules by other
nucleophilic groups, which may be either
molecules or ions.
M(H2O)n + L ↔ M(H2O)n-1L + H2O
 General Principles
• Most metal ions (cations) react with electron pair
donors to form complexes or coordination
compounds.
• For example
Cu2+ + 4NH3 ⇌ Cu(NH3)42+
Cu2+ + 4Cl- ⇌ Cu(Cl)42-
 The metal ion in the complex acts as an electron pair
acceptor and is called the "central atom".
 The group attached to the central atom is called the
"ligand" or "complexing agent".
 The chemical bond between the metal ion and the ligand
is called a "coordinate bond". 4
 Nature of Donor Atoms (Ligands)
• Unidentate ligands:
mostly inorganic, contain only one donor atom
per molecule,
e.g. NH3, H2O, OH-, SCN-
• Multidenate ligands:
organic ligands, contain two or more donor
groups per molecules
e.g. ethylendiamine (bidentate),
triethylenetetramine (quadridentate).
 Multidentate Ligands
• Multidentate ligands have several kinds of
coordinating groups
Ligands with N-containing groups as amines,
amides, nitroso, and CN-.
O-containing groups as : alcoholic, phenolic,
ether, keto group.
S-containing groups : thiols(SCN, CNS),
thiocarbonyl (CS).
Salt-forming group : group that contain an
ionisable H atom e.g. carboxyl, alcoholic,
phenols.
 Complex Formation Titrations
• The most useful complex-formation reactions
for titrimetry involve chelate formation
• Chelate effect - ability of multidentate ligands
to form more stable metal compounds than
those formed by monodentate ligands
A chelate is formed when a metal ion coordinates
with two of more donor groups of a single ligand
(forming a 5- or 6- membered heterocyclic ring)
 Examples of Chelating Agents
• Polyaminocarboxylic acid e.g. ethylenediamine
tetraaceticacid (EDTA)

• Polyamides e.g.triethylenetetraamine (trien)

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 Complex Formation Titration
• Recall: A complexation titration is one in which a
soluble undissociated, stoichiometric coordination
complex is formed at the equivalence point.
• Two factors determine the magnitude of the break
in the titration curve at the end point :
1. the stability of the complex formed: The greater the
stability constant for the complex formed. The
larger will be the break in the titration curve
2. the number of steps involved in the complex
formation. The fewer the number of steps
required in the formation of the complex, the
greater the break in the 9 curve.
 Complex Formation titration…
• Multidentate ligands (especially with 4 and 6
donors) are preferred for titrimetry.
react more completely with metal ion
usually react in a single step
provide sharper end-points
• E.g
 EDTA is a hexadentate ligand
 In EDTA a pair of unshared electrons capable of
complexing with a metal ion is located on each of the two
nitrogen atoms and each of the four ionised carboxyl
groups
 EDTA forms stable chelates10with most metal ions
 Titrations with EDTA
• EDTA forms chelates with practically most of the
metal ions and this fact is exploited in the
complexometric determination of these ions using
EDTA.
 Such titrations are called complexometric or chilometric
or EDTA titrations.
• EDTA is often represented as H4Y is a tetraprotic
weak acid with successive pKa values relating to the
four acid dissociation steps

11
 EDTA titration…
H4Y  H+ + H3Y- pKa1 = 2.0
H3Y-  H+ + H2Y2- pKa2 = 2.68
H2Y2- ⇌ H+ + HY3- pKa3 = 6.11
HY3- ⇌ H+ + Y4- pKa4 = 10.17
• The first two protons are easily removed,
while the third and fourth are weakly
ionized.
• The form Y4- is the unprotonated EDTA that
forms complexes with metal ion.
12
 EDTA titration…
• The species Y4- becomes the predominate
form of EDTA at pH > 10.17.
• At pH > 12, Y4- becomes the only form of
EDTA.
Thus complexation with EDTA is affected the
pH of the solution.
• H4Y has a very low solubility in water and
so the disodium salt [Na2 H2Y.2H2O] which
is soluble in water is usually used.

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 Metal-EDTA Formation Constants

• EDTA forms very stable soluble chelates with

many metals in a 1:1 stoichiometric reaction
Mn+ + Y4- ⇌ MY(n-4)
[MY( n 4 ) ]
K MY 
[Mn ][ Y 4  ]
• In EDTA titrations, a single stable chelate is
formed and the titration curve has a single
steep inflection region which provides sharp
and easily detected equivalence point
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 Formation Constants for EDTA Complexes

• Cation KMY Log KMY Cation KMY Log KMY

Ag+ 2.1 x 107 7.32 Cu2+ 6.3 x 1018 18.80
Mg2+ 4.9 x 108 8.69 Zn2+ 3.2 x 1016 16.50
Ca2+ 5.0 x 1010 10.70 Cd2+ 2.9 x 1016 16.46
Sr2+ 4.3 x 108 8.63 Hg2+ 6.3 x 1021 21.80
Ba2+ 5.8 x 107 7.76 Pb2+ 1.1 x 1018 18.04
Mn2+ 6.2 x 1013 13.79 Al3+ 1.3 x 1016 16.13
Fe2+ 2.1 x 1014 14.33 Fe3+ 1.3 x 1025 25.1
Co2+ 2.0 x 1016 16.31 V3+ 7.9 x 1025 25.9
Ni2+ 4.2 x 1018 18.62 Th4+ 1.6 x 1023 23.2
 Metal-EDTA Formation Constants
• The Y4– form of EDTA is the predominate form at
pH values greater than 10.17 and are the only
significant form for pH greater than 12.
• Since EDTA exists in different forms at a given pH,
the principle of mass balance requires that the total
concentration of EDTA should be equal to the sum
of the concentrations of all the forms of EDTA

[EDTA ]  [H4 Y]  [H3 Y  ]  [H2 Y 2 ]  [HY 3 ]  [ y 4  ]  CEDTA

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 Metal-EDTA Formation Constants
• Thus the generalised formation constant,
[MY( n 4 ) ]
K MY 
[Mn ][ Y 4  ]

is not a true formation constant because in the denominator it

reflects only one form of EDTA viz Y4-.
• Thus, to get a clearer picture of the formation constant we
define a parameter Y4− to be the fraction of EDTA present as
Y4-.
[ Y 4 ]
 Y4 
[H4 Y ]  [H3 Y  ]  [H2 Y 2 ]  [HY 3 ]  [ Y 4  ]
[ Y 4 ] [ Y 4 ]
 
[EDTA ] CEDTA 17
 Metal-EDTA Conditional Formation
Constants
• Substituting the value of Y4− in the formation constant
expression, we get
[MY( n 4 ) ]
K MY 
[Mn ] Y 4  CEDTA

• Since at a given pH, the value of Y4− is a constant it can

be combined with the formation constant, we get the
following:
[MY( n 4 ) ]
K MY  Y 4   K ' MY 
[Mn ]CEDTA
• The new constant, K’MY K is called apparent or
conditional stability constant
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 Example
• Calculate the concentration of free Ca2+ in a solution of 0.10
M CaY2- at pH 10 and pH 6. Kf for CaY2- is 5.0 x1010
Ca2  EDTA  CaY 2 K 'f   Y 4  K f
at pH  10.00, K 'f   Y 4  K f  ( 0.36)( 5.0  1010 )  1.8  1010
at pH  6.00, K 'f   Y 4  K f  ( 2.3  10 5 )( 5.0  1010 )  1.15  106

Ca2  EDTA  CaY 2

Conci 0 0 0.1
Conc f x x 0.1 - x

K '

CaY   0.1  x
2
 
x  Ca2  2.4  10 6 M @pH  10
f
Ca  EDTA  x
2 2
 3.0  10-4 M @pH  6

• At low pH, the metal-complex is less stable

Generic Titration Curve
Like a strong acid/strong base
titration, there are three
points on the titration curve
of a metal with EDTA: before,
at, and after the equivalence
point.
Lets consider a titration where
we have 50.0 mL of 0.040 M
Ca2+ (buffered at pH=10)
with 0.080 M EDTA.
 Solving for Volume of EDTA
• Equivalence volume
M Ca2 x VCa2 0.040M x 50 mL
VEDTA    25 mL
MEDTA 0.080 M

• At pH 10, Y4− =0.36

K 'f  ( 0.36)( 5.0  1010 )  1.8  1010
 Before the Equivalence Point
• What’s pCa2+ when we have added 5.0 mL
of EDTA?

Ca 
2

mol excess Ca2 (M Ca x VCa ) - (MEDTA x VEDTA )
total volume

Vca  VEDTA
(0.040 M x 50 mL) - (0.080 M x 5 mL)
  0.0291 M
50 mL  5 mL

pCa2   log( 0.0291)  1.54

 At the Equivalence Point
• What’s pCa2+ when we have added 25.0 mL
of EDTA?
At the equivalence point almost all the metal is in
the form CaY2-

CaY 
2

Initial mol Ca2 (M Ca x VCa )
total volume

Vca  VEDTA
(0.040 M x 50 mL)
  0.0267 M
50 mL  25 mL

Letting the variable x represent the concentration

of Ca2+ due to the dissociation of the CaY2–
complex, we have
 At the Equivalence Point…
Ca2  EDTA  CaY 2
Conci 0 0 0.0267
Conc f x x 0.0267 - x

K 'f 
CaY 2

0.0267  x
 1.8  10 10

Ca  EDTA 
2
x 2

6
x  1.2  10 M

pCa2   log(1.2  10 6 )  5.91

 After the Equivalence Point
• After the equivalence point, EDTA is in excess, and
the concentration of Ca2+ is
determined by the dissociation of the CaY2–
complex.
 Examining the equation for the complex’s conditional
formation constant, we see that to calculate Cca,
we must first calculate [CaY2] and CEDTA.
• What’s pCa2+ when we have added 26.0
mL of EDTA?
We have 1.0 mL excess EDTA
 After the Equivalence Point….

CaY  2

Initial mol Ca2 (M Ca x VCa )
total volume

Vca  VEDTA
(0.040 M x 50 mL)
  0.0263 M
50 mL  26 mL

mol excess EDTA (MEDTA x VEDTA ) - (M Ca x VCa )

CEDTA  
total volume Vca  VEDTA
(0.080 M x 26 mL) - (0.040 M x 50 mL)
  1.05 x 10-3 M
50 mL  26 mL
 After the Equivalence Point….

K 'CaY 2- 
CaY  2

2.63  10 2
 1.8  1010
Ca  EDTA  Ca (1.05  10
2 2 3
)

Ca  2

2.63  10 2
10 3
(1.8  10 )(1.05  10 )
 1.4  10 9
M

pCa   log 1.4  10 9  8.86

 Auxiliary Complexing Agents
• In aqueous solution, metal-hydroxide
complexes or precipitates can form, especially
at alkaline pH
• We often have to use an auxiliary complexing
agent
This is a ligand that binds strongly enough to the
metal to prevent hydroxide precipitation, but
weak enough to be displaced by EDTA
• Ammonia is a common auxiliary complex for
transition metals like zinc
 Metal Ion Indicators
• Usually metal ion indicators are used to detect the end
point
• Metal ion indicators change color when the metal ion is
bound to EDTA:
• The binding is pH dependent
• The indicator must bind less strongly than EDTA
• Over 200 organic compounds form colored chelates with
ions in a pM range that is unique to the cation and the
dye selected.
• To be useful, the dye-metal chelates usually will be visible
at 10-6-10-7 M concentration.
• The dye is selected such that the color change corresponds
to the pM at equivalence.
 Metal Ion Indicators: Examples
• Eriochrome black T (EbT) is an organic ion
 EbT is best used with Mg2+ and Zn2+ titrations
 Excess EDTA causes a red to blue color change at near
neutral pH.
MgEbT  EDTA  MgEDTA  EbT
(Red) (Clear) (Clear) (Blue)
 Eriochrome Black solutions decompose easily.

• Calmagite
 Similar in structure to EbTbut does not decompose as
easily.
Similar color behavior to EbTand more stable
Metal Ion Indicator Compounds
 EDTA Titration Techniques
• Direct titration:
analyte is titrated with standard EDTA with
solution buffered at a pH where Kf’ is large
 Many metals can be determined by direct titrations with
EDTA.

Example
A 100.0 mL drinking water containing Ca2+ was treated with
ammonia-ammonium chloride buffer solution to give pH about
10.0. Calgamite indicator was added and the solution was
titrated with 0.0050 M EDTA. It required 23.50 mL of the
titrant to achieve the end point. Calculate the water hardness in
terms of ppm calcium?
 Direct Titration Example
MEDTA x VEDTA
M Ca2 x VCa2  MEDTA x VEDTA  M Ca2 
VCa2
0.0050M x 23.50 mL
M Ca2   0.001175 M
100.0 mL

MEDTA x VEDTA
M Ca2 x VCa2  MEDTA x VEDTA  M Ca2 
VCa2
ppm  molarity x molar mass x 1000
 ppmCa  0.00175 mol/L x 40.08 g/mol x 1000
 47.1 ppm
 EDTA Titration Techniques…
• Back titration:
 Back titration can be performed for the determination of
several metal ions can not be titrated directly but form
stable EDTA complexes.
 Known excess of EDTA is added to analyte.
 Excess EDTA is back titrated with a standard solution 2nd
(weak) metal ion.
 The weak metal ion will not displace the analyte from its
EDTA complex.
• Example: 25.0 mL of an unknown Ni2+ solution was treated
with 25.00 mL of 0.05283 M Na2EDTA. The pH of the
solution was buffered to 5.5 and than back-titrated with 17.61
mL of 0.02299 M Zn2+. What was the unknown Ni2+ M?
 Back Titration Example

Zn 2  Y 4-  ZnY 2-
mol EDTA  (25.00 mL)(0.05283 M)  1.32 mmol EDTA

2 2
mol Zn  (17.61 mL)(0.02299 M)  0.4049 mmol Zn

Ni2  Y 4-  NiY 2-
2 2
mol Ni  1.321 mmol EDTA - 0.4049 mmol Zn
 0.916 mmol

M Ni2  ( 0.916 mmol)/(25.00 mL)  0.0366 M

 EDTA Titration Techniques…
• Displacement titration:
For metals without a good indicator ion
the unknown metal (analyte) is treated with
excess MgY2- or ZnY2- complex .
The analyte displaces Mg, and than Mg can be
titrated with standard EDTA
The unknown metal displaces the Mg2+ or Zn2+,
which is then back titrated.
The technique only works when the unknown
metal has tighter binding to EDTA than the Zn2+
or Mg2+.