PRECIPITATION AND

COMPLEXATION
METHODS OF
ANALYSIS
Alexis C. Arellano, RPh
 Determination of the End Point
1. Cessation of precipitation or the appearance
of a turbidity
2. Use of internal indicators
3. Instrumental methods, i.e., potentiometric
of a turbidity
 Indicators
1. Ferric ammonium sulfate TS
• SCN + Ag or Hg2+ → AgSCN or Hg(SCN)2 (white)
• SCN + FeNH4(SO4)2 → Fe(SCN)3 (red)
2. Potassium chromate TS
• K2CrO4 + AgNO3 + NaCl → Ag2CrO4 (red) + AgCl +
NaNO3
3. Adsorption indicators
• Dichlorofluorescein (DCF) TS
• Eosin Y TS
• Tetrabromophenolphthalein ethyl ester (TEE) TS
Silver nitrate (AgNO3)
• Solvent
• Diluted HCl
• Notes:
• No need to standardize against a primary standard since
AgNO3 is a substance of high purity.
• Protect the silver chloride from _____ as much as
possible during the determination of the normality of the
AgNO3 solution.
• Allow to stand in the dark to minimize the reduction of
silver chloride → free silver is produced.
• The ________ color of the precipitate when exposed to
light is due to the free metal formed in the precipitate.
Silver nitrate (AgNO3)
Wt of AgCl AgNO3/AgCl
N=
40 mL 0.16987

• AgNO3 = 169.87 g/mol

• AgCl = 143.32 g/mol
Ammonium thiocyanate (NH4SCN)

• Solvent
• H2O
• Secondary standard
• 0.1 N AgNO3
• Indicator
• FeNH4(SO4)2
• Endpoint
• Red-brown color
Ammonium thiocyanate (NH4SCN)

• NH4SCN is deliquescent → a slight excess is

used during preparation.
• KSCN may be used if desired.
• Write the chemical reactions involved in the
standardization of NH4SCN.
1. ___________________________________
2. ___________________________________
Ammonium thiocyanate (NH4SCN)

• Oxides of nitrogen give colored salts with

ferric alum.
• Solutions containing oxides of nitrogen and
the HNO3 used in the preparation and
standardization should be boiled prior to the
addition of the indicator.
N1V1 = N2V2
Direct Titration
• Compounds of Ag and Hg that can be readily
converted into soluble Ag or Hg2+ salts may be
estimated by direct titration with standard
NH4SCN solution using FeNH4(SO4)2 as
indicator.
• Chemical reactions involved:
• _______________________________________
• _______________________________________
• _______________________________________
Direct Titration

• The solution must be acidified with HNO3 to

prevent the __________ that ferric salts
undergo in neutral solution.
• Chlorides must be ______, since the
chlorides of Ag and Hg are more soluble than
the respective SCN– .
Assay of Phenylmercuric Nitrate
for Mercury Content
• Solvent
• H2O
• CH3COOH + Zn dust → reduces the Hg2+ ion to free elemental
mercury → forms an _______ with the excess Zn metal →
dissolved in dilute HNO3 (1 in 2)
• CH4N2O + KMnO4 → permanent ____ color → decolorized with
____
• Indicator
• FeNH4(SO4)2
• Titrant
• NH4SCN
• Endpoint
• Red due to the formation of Fe(SCN)3
Assay of Phenylmercuric Nitrate
for Mercury Content
• Hg2+ ion does not yield a copious precipitate upon
titration with NH4SCN as does Ag+.
• The presence of halide ions (Cl, Br and I) will
interfere with the determination of Hg2+
• HgCl2 > HgBr2 > Hg(SCN)2 > HgI2 > Hg(CN)2
Assay of Sodium Lauryl Sulfate
for Sodium Chloride Content
• Solvent
• H2O
• Neutralize with dilute HNO3
• Indicator
• K2CrO4
Assay of Iopanoic Acid Tablets
• Chemical name of iopanoic acid
• _____________________________________________
• Solvent
• NaOH (1 in 20)
• React with powdered Zn + CH3CH2COOH
• Titrant
• AgNO3
• Indicator
• TEE
• Endpoint
• Yellow → green
Assay of Benzyltrimethylammonium
Chloride
• Titrant
• AgNO3
• Indicator
• DCF TS
• Notes:
• DCF is a weak organic acid whose ionization is
dependent on the pH of the titrated solution.
• pH < 4 → faint endpoint
• Azacyclonol (1 in 200) → pH 5-7
• Keeps AgCl in a colloidal state → sharper color change
Residual Titration (Volhard
Method)
• Excess AgNO3 solution
• Titrant
• NH4SCN
• Indicator
• FeNH4(SO4)2
Purity of a Soluble Chloride
• This may be determined thru residual titration
provided that other substances which form
precipitates with AgNO3 are absent.
• Substances other than chlorides that produce
slightly soluble silver salts are:
• ________, _______, ________, thiocyanates,
sulfides, __________, arsenates, __________
Assay of Sodium Chloride
• Solvent
• H2O + AgNO3
• HNO3 is added to prevent the precipitation of Ag as
CO3-, PO43-, and to prevent hydrolysis of the ferric
alum.
• C6H5NO2 forms a film over the precipitated AgCl
particles to prevent reaction with NH4SCN.
• Titrant
• NH4SCN
• Indicator
• FeNH4(SO4)2
Assay of Sodium Chloride
mlAg N − mlSCN N 0.05844 100
% NaCl =
Sample wt (g)