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Ligand
Cation
or Complexing Agent
Complex-Formation Titrations
2. Chemical Masking
Ligand
donor
species
must have at
least one pair
of
unshared
electrons
available for
bond
formation
A.Nature
1. Inorganic
2. Organic
H2O, NH3, Cl1EDTA, NTA
B. Number of Electron Pair Donors
1. Unidentate
2. Polydentate or
Multidentate
H2O, NH3, Cl1EDTA, NTA
Complex-Formation Titrations
polydentate /
multidentate
generally react
more completely
with cations and
thus provide
sharper end points
ordinarily react
with metal ions in a
single-step process
NTA
Nitrilotriacetic acid
second most
common
complexing agent
used for titrimetry
tetradentate
ligand
Indicators
1. Xylenol
weak complexing
agents
exhibit different
colors in their
complexed and
uncomplexed form
Orange
Indicators
2. Eriochrome
Black T
oxidized slowly by
dissolved oxygen,
ascorbic acid is
sometimes added to
retard this reaction or
solid EBT is added
directly to the sample
prior to titration
Indicators
3.
Calmagite
structure is very
similar to EBT
more stable than
EBT in aqueous
solution
4.
Arsenazo I
Analytes
virtually every
metal cation
with the
exception of
the alkali
metal ions
determinations
of analyte or
mixture of
analytes involve
one or a
combination of
the titration
methods
Applications
1.
Applications
2. Back-Titration Method
Exercise 14
An antacid tablet weighing 15.476-g was dissolved in
acid and diluted to 500.0-mL.
A 25.00-mL aliquot of the solution was made
sufficiently basic to precipitate the Al as Al(OH)3. The
remaining Mg required 16.49-mL of 1.043 x 10 -2 M
EDTA for titration.
A second 25.00-mL aliquot was withdrawn from the
500-mL flask and treated with 50.00-mL of the EDTA.
This solution was made basic and the excess EDTA
back titrated with 11.73-mL of 5.594 x 10 -3 M MgCl2.
Calculate the percentage of both Mg and Al in the
sample.
Molar Masses: Al = 26.98 Mg = 24.31
Exercise 14
An antacid tablet weighing 15.476-g was dissolved in
acid and diluted to 500.0-mL.
A 10.00-mL aliquot of the solution was made
sufficiently basic to precipitate the Al as Al(OH)3. The
remaining Mg required 6.596-mL of 1.043 x 10 -2 M
EDTA for titration.
A second 25.00-mL aliquot was withdrawn from the
500-mL flask and treated with 50.00-mL of the EDTA.
This solution was made basic and the excess EDTA
back titrated with 11.73-mL of 5.594 x 10 -3 M MgCl2.
Calculate the percentage of both Mg and Al in the
sample.
Molar Masses: Al = 26.98 Mg = 24.31
Exercise 14
A 0.4085-g sample containing lead, magnesium and zinc
was dissolved and treated with cyanide to complex and
mask the zinc:
Zn 2+ + 4 CN 1- Zn(CN)4 2-