Precipitation Titrations

based upon reactions that yield ionic

compounds of limited solubility
a A + b T c Products (s)

one of the oldest analytical techniques

the slow rate of formation of most

precipitates, limits the number of
precipitating agents that can be used for
titrimetric analysis
 Titrants : Precipitating Agents

2. Number of Analytes
1. Nature Determined
Inorganic Precipitating
Specific Precipitating
Agents
Agents
AgNO3
Dimethylglyoxime
KSCN
Organic Prepicitating Selective Precipitating
Agents Agents
(C6H5)4B-Na+ AgNO3
8-Hydroxyquinoline KSCN
Dimethylglyoxime
 Titrants : AgNO3

available in primary- used for determining

standard grade purity, halide and thiocyanate
but it is expensive ions

titrants are prepared the stability of atomic Ag

from less pure AgNO3
can be standardized
with primary-standard
KCl
in cases where the
amount of silver ion
must be determined,
KCl is usually the titrant
makes Ag ion a good
reducing agent
certain proteins in skin
can reduce the Ag ion to
atomic Ag, leaving a
dark brown stain that is
unsightly and will
remain until replaced by
new skin
 Titrants

KSCN (C6H5)4B-Na+
obtainable in primary organic precipitating
standard quality but that forms salt-like
somewhat hygroscopic precipitate

ordinarily a near-specific
standardized against precipitating agent for
AgNO3 K+ and NH4+
stable indefinitely
 Indicator Example Colored Substance
(yields a ___ at or at End Point
near the

Indicators theoretical end

point)

usually colored Fe 3+ FeSCN 2+

specific complex ion

compound colored 2o K2CrO4 Ag2CrO4
formers, they precipitate
react colored HDCF AgCl.Ag+:DCF-
selectively adsorption
with the product
titrant to
form a
colored
substance
 Analytes

determination of determination of
halides, halide-like analytes involves
anions (SCN1- , CN1- , one or a
CNO1- ), mercaptans, combination of
fatty acids and titration methods
several divalent
inorganic anions
 Applications

1. Mohrs Method

Titrant AgNO3
Analyte/s Cl1- , Br1- , CN1-
Indicator Na2CrO4 / K2CrO4

Argentometric Method by Direct Titration

 Applications

2. Fajans Method
Titrant AgNO3
Analyte/s Cl1- , Br1- , CN1-
Indicator HDCF / HEs

Argentometric Method by Direct Titration

 Applications

3. Volhards Method
Titrants AgNO3 and KSCN
Analyte/s Cl1- , Br1- , CN1-
Indicator Fe 3+

Argentometric Method by Back-Titration

 Exercise 13

A 100-mL sample of brackish water was made

ammoniacal and the sulfide it contained titrated
with 8.47-mL of 0.01310-M AgNO3. The net
reaction is:
2 Ag 1+ + S 2- Ag2S (s)
Calculate the parts per million of H2S (mg H2S /L)
in the water.
Molar Masses:
AgNO3 = 169.9 H2S = 34.08
 Exercise 13

The phosphate in a 4.258-g sample of plant food

was precipitated as Ag3PO4 through the addition of
50.00-mL of 0.0820-M AgNO3:
3 Ag 1+ + HPO4 2- Ag3PO4 (s) + H 1+
The solid was filtered and washed, following which
the filtrate and washings were diluted to exactly
250.0-mL. Titration of a 50.00-mL aliquot of this
solution required a 4.64-mL back-titration with
0.0625-M KSCN. Express the results of this
analysis in terms of the percentage of P2O5.
Molar Mass: P2O5 = 141.9
 Exercise 13

After pretreatment to convert the arsenic to the +5 state, a

0.821-g sample of a pesticide was treated with 25.00-mL of
0.0800-M AgNO3. The Ag3AsO4 was filtered, washed free
of excess silver ion, and then redissolved by treatment with
nitric acid. The resulting solution required a 7.40-mL
titration with 0.0865-M KSCN.
(a) Express the results of this analysis in terms of
percentage As2O3 in the sample.
(b) If the analysis had been completed by titrating the
excess silver ion in the filtrate and washings, what
volume of 0.0865-M KSCN would have been used?
Molar Mass: As2O3 = 197.9