Argentometric Methods

Analytical Chemistry
Lecture Outline
 Silver nitrate (AgNO3)
• most widely used precipitating agent
• for the determination of halides (Cl—, Br— & I—)
and halide-like anions (SCN—, CN— & CNO—)
• Available in primary-standard-grade purity, but
expensive
• Less pure can be standardized with primary
standard KCl
• Avoid skin contact; protein in skin can reduce Ag+
to AgO leaving dark brown stains
• Protect solutions from direct light or heat
 Mohr Method
• Developed for the determination of Cl—, Br— &
CN— ions.
• Titrant - AgNO3; Indicator – Na2CrO4
• Detection of endpoint: based on the
formation of colored secondary precipitate
Titration reaction Cl— + Ag+ → AgCl(s)
Indicator reaction CrO4—2 + Ag+ → Ag2CrO4(s)

Solubility of Ag2CrO4 is five times higher than AgCl; hence,

AgCl will precipitate first.
 Mohr Method
• Pale yellow color of CrO4—2 masks the
appearance of reddish-brown ppt resulting to
indicator error (correction can be made by
performing indicator blank)
• Limitations – titration must be carried out at pH
6.5-10.3
– Below 6.5 – Ag2CrO4 becomes excessively soluble,
increasing indicator error
CrO4—2 +2H+ → Cr2O7—2 + H2O
– Above pH 10.3, this reaction may occur:
Ag+ +OH— → AgOH(s)
 Mohr Method
• Limitations
– Interfering transition metal cations – form
insoluble hydroxides or basic salts in neutral or
alkaline solution; coprecipitate with Cl— and Br—
– Some hydroxides (i.e. Fe(OH)3) are highly colored
and will mask the indicator color change.
– Presence of interfering anions (PO4—3, AsO4—3,
CO3—2) – form insoluble silver salts in neutral or
alkaline solution
 Fajans Method
• Detection of endpoint: adsorption of indicator by the
electrostatically charged precipitate immediately after
equivalence point.
• Most common indicator used: Dichlorofluorescein
(HDCF)and Tetrabromofluorescein/eosin (HEs)

HDCF HEs
 Fajans Method
• Adsorption indicators have different colors in free
and adsorbed state.
• Free DCF— is greenish-yellow in solution that
turns pink when adsorbed on AgCl ppt.

Indicator reaction
AgCl•Ag+ + DCF— → AgCl•Ag+ :DCF—

DCF and eosin are strongly attracted to the counter-

ion layer after the equivalence point.
 Fajans Method
• Indicators must be adsorbed less strongly than
the analyte ion
– DCF – can be used for Cl—, Br—, I—, or SCN—.
– Eosin – not for Cl— analysis bec it is adsorbed more
strongly
• For adsorption indicators to function properly,
small portion of ppt must remain colloidal. But it
tends to coagulate just near the eq. pt.
– Vigorous shaking during titration or addition of
dextrin (as protective colloid to retard coagulation)
 Fajans Method
• DCF cannot be used below pH 6.5 (too little DCF—
exists in the soln)
• Eosin is stronger acid – used as low as pH 2.0
• Most ions that interfere in Mohr method also
interfere in Fajans method for Cl—
• Silver halide are light sensitive, unfortunately,
most adsorption indicators greatly increase this
light sensitivity. Titration must be performed
rapidly, with minimum exposure to light.
 Volhard Method
• Involves the addition of excess Ag+ to a halide
solution, followed by back titration of the excess
by SCN—.
• Detection of endpoint: formation of complex
compound
• Indicator – Fe+3

Analyte reaction Cl— + Ag+ → AgCl(s)

Titration reaction Ag+ + SCN— → AgSCN(s)
Indicator reaction Fe+3 + SCN— → FeSCN+2
 Volhard Method
• Advantage – can be carried out in strongly
acidic medium, eliminating interferences in
Mohr and Fajans
• AgCl is more soluble than AgSCN; hence, AgCl
ppt must be removed by filtration (or by
addition of nitrobenzene) before the back
titration of excess.
Ksp AgCl 1.8 x 10—10
AgSCN 1.1 x 10—12
 Sample Problem 1
• A silver nitrate solution contains 14.77 g of
primary-standard AgNO3 in 1.00 L. What
volume of this solution will be needed to react
with
– 0.2631 g of NaCl.
– 64.31 mg of Na3AsO4.
– 25.00 mL of 0.05361 M Na3PO4.
 Sample Problem 2
• A Fajans titration of a 0.7908-g sample
required 45.32 mL of 0.1046 M AgNO3.
Express the results of this analysis in terms of
the percentage of
– Cl—
– BaCl2 ∙ 2 H2O
– ZnCl2 ∙ 2 NH4Cl (243.28 g/mol)
 Sample Problem 3
• The salt content was extracted from a 12.0000
g junk food sample. The extract was diluted to
100.00 mL. From this solution, 15.00 mL was
taken and required 23.75 mL of a 0.08943 M
AgNO3 solution to reach the endpoint. What is
the percentage by mass of salt as NaCl (58.45
g/mol) in the junk food sample?
 Sample Problem 4
• A salt sample was analyzed for its purity. A
0.5000 g sample was dissolved in water and
diluted to 250 mL. From this solution, 25.00
mL was taken for analysis. To this aliquot,
20.00 mL of a 0.08735 M AgNO3 solution was
added to precipitate the chloride. The excess
AgNO3 required 12.45mL of a 0.09473M KSCN
solution for back-titration. Calculate the purity
of the salt sample as percent by mass of KCl
(74.55 g/mol).
 Sample Problem 5
• The arsenic in a 1.010-g sample of a pesticide was
converted to H3AsO4 by suitable treatment. Thee
acid was then neutralized, and exactly 40.00 mL
of 0.06222 M AgNO3 was added to precipitate the
arsenic quantitatively as Ag3AsO4. The excess Ag+
in the filtrate and in the washings from the
precipitate was titrated with 10.76 mL of 0.1000
M KSCN; the reaction was
Ag+ + SCN— → AgSCN(s)
Calculate the percent As2O3 in the sample.