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EDTA Titrations: Quantitative Chemical Analysis Eighth Edition
EDTA Titrations: Quantitative Chemical Analysis Eighth Edition
EDTA Titrations: Quantitative Chemical Analysis Eighth Edition
Chapter 11:
EDTA Titrations
Daniel C. Harris
* Some figures from Quantitative Chemical Analysis (7th Ed.) with the permission of W.H. Freeman & Company
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
Metal-Chelate Complexes
EDTA (ethylenediaminetetraacetic acid, hexaprotic H6Y2+)
Complexometric metal titrations forming strong 1:1 complexes
Industrial processes, soaps, cleaners, food additives,
environmental processes,…
HNCH2CH2NH
HO2CH2C CH2CO2H
H6Y2+
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
Metal-Chelate Complexes
Lewis acid; electron-pair acceptor Lewis base; electron-pair donor
Monodentate ligands bind through one donor atom only.
-Therefore they occupy only one coordination site.
Multidentate ligands (or chelating agents) bind through more than one donor
atom per ligand.
-Example, ethylenediamine (en), H2NCH2CH2NH2.
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
Metal-Chelate Complexes
Fig 11-1 Mn-EDTA complex; hexadentate
Metal-Chelate Complexes
Fig 11-4 Aminocarboxylic chelating agents
1:1 complex with all metals (except Li+, Na+, K+)
Complexometric titration
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
EDTA
Virtually every element can be analyzed with EDTA (directly or indirectly)
Forms stable water soluble complexes
High formation constants.
A primary standard material – a highly purified compound that serves as a
reference material.
Acid-Base Properties
EDTA: hexaprotic system (H6Y2+, H5Y+, H4Y, H3Y-, H2Y2-, HY3-, Y4-)
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
EDTA
Fractional Composition of EDTA Solutions
Fig 11-7 ; Fractional composition of EDTA as a function of pH
EDTA
Formation Constant (Stability Constant)
4-
One mole of EDTA (in the form Y ) reacts with one mole of Metal ion.
n+
M +Y ↔ 4-
� MY n-4 [MY n-4 ]
K f = n+ 4-
[M ][Y ]
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
EDTA
[Y 4 - ] = a Y 4- [EDTA]
Consider EDTA complex formation as if the uncomplexed EDTA is in one form.
' [MY n- 4 ]
K = a Y 4 - K f = n+
f
Conditional formation constant: at a given pH
[M ][EDTA]
At any fixed pH, find a Y 4- and evaluate Kf’
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
EDTA
x2 1 3+
ìï1.6 x 10-9 M at pH 4.00
= ® x( = [Fe ]) = í -5
F - x Kf ' ïî7.4 x 10 M at pH 1.00
EDTA
Effect of pH on EDTA Titration of Ca 2+
Less distinct
end point
Region 2
Equivalence point: [Mn+] = [EDTA]
Some free Mn+ generated by MYn-4 Û Mn+ + EDTA
Region 3
Excess EDTA. Virtually all metal in MYn-4 form.
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
50.00
[MgY 2- ] = 0.0500 M ( ) = 0.0248 M
50.00+51.00
' [MgY 2- ]
K = a Y4- K f =
f 2+
® [Mg2+ ] = 2.6 x 10-7 M ® pMg2+ = 6.58
[Mg ][EDTA]
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
Beware
Complications due to formation of MOH+, M(OH)2(aq), M(OH)2(s), M(OH)3-,…
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
Left: 0.02 M CuSO4 before titration. Center: Color of Cu(II)-ammonia complex after
addition of ammonia buffer, pH 10. Right: End point color when all ammonia ligands
have been displaced by EDTA. In this case, the auxiliary complexing agent
accentuates the color change at the end point
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
Indirect Titration
Anions that form precipitates with certain metal ions (CO32-, CrO42-, S2-, SO42-…)
Ba2+ + SO42- à BaSO4(s) with excess Ba2+ at pH 1
Precipitation
Filtered, washed, and then boiled with excess EDTA at pH 10
à BaSO4(s) into Ba(EDTA)2-
Excess EDTA is back-titrated with Mg2+ BaSO4 precipitate
Filtration filter
Ba2+
The precipitate is filtered and washed. filtrate
à Excess metal ion in the filtrate is titrated with EDTA.
Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory
masking à Selectivity