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EDTA Titrations

CHM 112

MAPUA Institute of Technology

Metal-chelate complexes
• Lewis acids – accepting electron pairs such as
metal ions
• Lewis bases – electron donating ligands

• Cyanide ion – monodentate ligand; binds to a

metal ion through only one atom

• Multidentate ligand or chelating ligand – a ligand

that attaches to a metal ion through more than
one ligand atom

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• Ethylene diamine – bidentate
• Adenosine triphosphate – tetradentate
• Aminocarboxylic acids – synthetic chelating agents

• Complexometric titration – a titration based on

complex formation

• Formation constant or stability constant – the

equilibrium constant for the reaction of a metal with a

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EDTA Titration Curves
• Mn+ + EDTA = MYn-4
• Graph of pM (= - log [M]) versus the volume of
added EDTA
• Region 1: Before the Equivalence point
– There is excess Mn+ left in solution after the EDTA
has been consume. The concentration of free
metal ion is equal to the concentration of excess,
unreacted Mn+

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• Region 2: At the Equivalence point
– There is exactly as much EDTA as metal in the
– Some free Mn+ is generated by the slight
dissociation of MYn-4
– MYn-4 = Mn+ + EDTA
– EDTA – total concentration of free EDTA in all of its
– At the equivalence point, [Mn+ ] = [EDTA]

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• Region 3: After the Equivalence point
– Excess EDTA
– All the metal ion is in the form MYn-4
– The concentration of free EDTA can be equated to
the concentration of excess EDTA added after the
equivalence point

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Titration Calculations
• Calculate the shape of the titration curve for
the reaction of 50.0 mL of 0.0500 M Mg2+
(buffered to pH 10.00) with 0.0500 M EDTA
• K’f = 2.2 x 108
• Equivalence volume is 50.0 mL
• Region 1: before the equivalence point
– Determine [Mg2+] = fraction remaining x original
concentration of metal x dilution factor

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• Region 2: at the equivalence point:
– [MgY2-] = original concentration of metal x dilution
– K’f = 2.2 x 108 = [MgY2-] / [Mg2+][EDTA]

• Region 3: After the equivalence point

– [EDTA] = original concentration of EDTA x dilution
– [MgY2-] = original concentration of metal x dilution
– K’f = 2.2 x 108 = [MgY2-] / [Mg2+][EDTA] to determine

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Metal ion indicators
• A compound whose color changes when it
binds to a metal ion

• End point detection methods

– Metal ion indicators
– Mercury electrode
– Glass (pH) electrode
– Ion selective electrode

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• MgIn (red) + EDTA = MgEDTA + In (blue)

• Common metal ion indicators – EBT,

calmagite, murexide, xylenol orange,
pyrocatechol violet

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EDTA Titration Techniques
• Direct titration – analyte is titrated with
standard EDTA. The analyte is buffered to an
appropriate pH at which the conditional
formation constant for the metal-EDTA
complex is large and the color of the free
indicator is distinctly different from that of the
metal-indicator complex.

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• Auxiliary complexing agent prevents the metal
ion from precipitating in the absence of EDTA.

• Example: ammonia, tartrate, citrate or


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• Back titration – a known excess of EDTA is
added to the analyte. The excess EDTA is then
titrated with a standard solution of a second
metal ion.

• A back titration is necessary if the analyte

precipitates in the absence of EDTA, if it reacts
too slowly with EDTA under titration
conditions or if it blocks the indicator.

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• Displacement titration – the analyte is treated
with excess Mg(EDTA)2- to displace Mg2+,
which is later titrated with standard EDTA.

• Hg2+ determination

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• Indirect titration – anions that precipitate with
certain metal ions can be analyzed with EDTA

• Sulfate can be analyzed by precipitation with

excess Ba2+ at pH 1. The BaSO4(s) is washed
and then boiled with excess EDTA at pH 10 to
bring Ba2+ back into solution as Ba(EDTA)2-.
The excess EDTA is back titrated with Mg2+.

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• An anion can be precipitated with excess
metal ion. The precipitate is filtered and
washed, and the excess metal ion in the
filtrate is titrated with EDTA.

• Anions such as CO32-, CrO42-, S2- and SO42- can

be determined by indirect titration with EDTA.

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• Masking agent – a reagent that protects some
component of the analyte from reaction with

• Fluoride masks Al3+, Fe3+, Ti4+ and Be2+

• Triethanolamine masks Al3+, Fe3+ and Mn2+
• 2,3-dimercapto-1-propanol masks Bi3+, Cd2+,
Cu2+, Hg2+ and Pb2+
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• Demasking releases metal ion from a masking
agent. Cyanide complexes can be demasked
with formaldehyde.

• Thiourea masks Cu2+ by reducing it to Cu+ and

complexing the Cu+. Copper can be liberated
from the thiourea complex as Cu2+ by
oxidation with H2O2.

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