EDTA Titration

Analytical Chemistry
Lecture Outline
 Complex-Formation Titration
• Lewis acid – electron pair acceptor e.g. Ca2+,
Mg2+, Zn2+
• Lewis base – electron pair donor (ligand);
must have at least a lone pair of electrons e.g.
NH3
• Chelate – a cyclic complex formed when a
cation is bonded by two or more donor groups
contained in a single ligand
• Dentate – means having tooth-like projections
 Complex-Formation Titration
• Coordination number – number of covalent
bonds that a cation tends to form with
electron donors

Multidentate ligands are preferred over

unidentate ligands because
• Reacts more completely with cations
• React with metal ions in a single step process
Properties of EDTA
 Preparation of EDTA titrant
• Commonly available: Free acid (H4Y) and
disodium salt (Na2H2Y); not available in
primary standard-grade
• H4Y is not very soluble in water and must be
dissolved in dilute NaOH soln.
• Dilute solution is stable; must be stored in
reagent bottle washed with 1:1 HNO3:H2O.
Determining the Equivalence Point
Equivalence points in complexation titrations
have been determined using color changes of
chemical indicators.
Theory of Complexation Indicators
• Indicators are weak complexing agents that
exhibit different forms in their complexed and
uncomplexed form.
MIn + Y ↔ MY + In
(color A) (color B)
 Common Indicators
Eriochrome Black T (EBT)
– Workable at pH 7-11
– Blue (uncomplexed form), red (complexed form)
– Used for direct titration of Mg+2, Ca+2, Cd+2, Zn+2,
and Pb+2.
– Presence of dissolved O2 and ascorbic acid
oxidized EBT
– Also forms chelates with metal ions
• Order of stability: CaY2- > MgY2- > MgIn- > CaIn-
 Common Indicators
Calmagite
– Exhibits identical indicating properties with EBT
– More stable than EBT
 EDTA Titration Techniques
• Direct Titration
– The analyte is buffered to a 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 the metal-indicator
complex
– Auxiliary complexing agents such as NH3, tartrate,
citrate and triethanoloamine may be employed to
prevent metal ion from precipitating in the
absence of EDTA.
 EDTA Titration Techniques
• Back Titration
– Excess EDTA is then titrated with a standard
solution of a second metal ion.
– A back titration is necessary if analyte precipitates
in the absence of EDTA, if it reacts too slowly with
EDTA, or if it blocks the indicator
– The metal ion for the back titration must not
displace analyte from EDTA
 EDTA Titration Techniques
• Displacement Titration
– Hg2+ is treated with excess Mg(EDTA)2- to displace
Mg2+ which is titrated with standard EDTA.

– Ag+ will displace Ni2+. The liberated Ni2+ can then

be titrated with EDTA.
 EDTA Titration Techniques
• Indirect Titration
– Anions that precipitate with certain metal ions can
be analyzed with EDTA
• Masking
– A reagent that protects some component of the
analyte from reaction with EDTA
 Sample Problem 1
• Calculate the volume of 0.0500 M EDTA
needed to titrate
– 26.37 mL of 0.0741 M Mg(NO3)2
– The Ca in a 0.4397-g mineral specimen that is
81.4% brushite, CaHPO4∙2H2O (172.09 g/mol)
 Sample Problem 2
• The Zn in a 0.7556-g sample of foot powder
was titrated with 21.27 mL of 0.01645 M
EDTA. Calculate the percentage of Zn in this
sample.
 Sample Problem 3
• What weight of CaCO3 must be dissolved in
250.0mL of a solution if a 50.00mL aliquot is
to require about 30.00mL of 2.0 x 10—2M EDTA
for titration?
 Sample Problem 4
• A sample of powdered milk weighing 1.450g
was mixed with an aqueous buffer of pH 11.5.
A few drops of Calmagite indicator were
added and the solution required 31.62mL
1.538 x 10—2M EDTA to reach the endpoint
color change. Calculate the percentage Ca in
the milk.
 Sample Problem 5
• Titration of Ca+2 and Mg+2 in a 50.00mL sample of
hard water required 23.65mL of 0.01205M EDTA.
A second 50.00mL aliquot was made strongly
basic with NaOH to precipitate Mg+2 as Mg(OH)2.
The supernatant liquid was titrated with 14.53mL
of same EDTA solution. Calculate the ff:

a. The total hardness of water sample

b. Concentration in ppm CaCO3 in the sample
c. Concentration in ppm MgCO3 in the sample