EXPERIMENT 4: ASSAY OF NaCl

1. Volumetric Precipitimetry
 Reaction that requires the formation of relatively insoluble substances or precipitates to cause the
reactions to go to sufficient completion to be quantitative in nature.
 INSOLUBLE SUBSTANCES = must be sufficiently insoluble to ensure completion of the reaction
and to ensure a marked change in the concentration of the ions of precipitate at the equivalence point
of the titration.

a. Determination of the End Point

 Cessation of precipitation or the appearance of a turbidity
 Use of internal indicators
 Instrumental methods
b. Indicators (Volhard Method) = used in the analyses of halides by direct titration with AgNO3
solution
 Ferric Ammonium Sulfate TS (FeNH4(SO4)2)
- Used both in direct and residual titrations employing standard ammonium thiocyanate solution
 Potassium Chromate TS (the Mohr Method)
 Adsorption Indicators (Fajans Method)
- Dichlorofluorescein (DCF)
- Eosin YTS
- Tetrabromophenolphthalein ethyl ester (TEE)TS
c. Standard Solution
 0.1N AgNO3 = considered as the most precipitating reagent
 0.1N NH4SCN
2. Preparation & Standardization of Silver Nitrate
a. HCl = precipitant & continuous stirring of the heated solution aids in the formation of a precipitate
with large particles
NOTE: 1. Mixture is allowed to stand in the dark to minimize the reducing effect of the light on the
AgCl; free Ag is produced; 2. The purplish color which the precipitate acquires on exposure to light
is due to the free metal being found in the precipitate.
AgNO3 + HCl AgCl + HNO3
(169.87) (143.32)
3. Your amber bottle cap must be plastic & not aluminium-lined
4. Do not contact your skin with AgNO3 solutions. If you do, the moment you go into sunlight the
exposed skin will turn BLACK. This is harmless but prolong exposure may cause burns. The color
will last for about 10 days.
5. AgNO3 is toxic & corrosive, it is also very poisonous and can cause burns

SYNTHESIZED BY JRSG 2017

3. Preparation & Standardization of Ammonium Thiocyanate

- it is deliquescent, a slight amount in excess of the theoretical quantity is required in the preparation of
the solution

- AgNO3 + NH4SCN AgSCN (white) + NH4NO3

- As the endpoint is approached, the ppt becomes flocculent & settles readily at the end point, a drop of
NH4SCN solution produces a permanent reddish-brown color which does not disappear on shaking.

FeNH4(SO4)2 + 3NH4SCN Fe(SCN)3 (reddish brown) + 2(NH4)2SO4

- Nitric acid is employed to prevent hydrolysis that ferric salts undergo in heated solution
- Chlorides must be absent, since the chlorides of silver & mercury are more soluble than the
respective thiocyanate

4. Indicator (FeNH4(SO4)2)

- Iron Alum/FAS

NOTE: Oxides of nitrogen give colored salts with ferric alum solutions containing oxides of nitrogen & also the
nitric acid employed should be boiled prior to the addition of the indicator

- Is the choice of indicator since the endpoint is visibly detected by a deep red color (ferric
thiocyanate) due to the interaction of the Fe 2+ ions with a trace of SCN- ion

5. Assay of NaCl (Volhard Method)

a. Volhard Method

- an example of back titration, named after JACOB VOLHARD, involves the addition of excess silver
nitrate to the analyte; the AgCl is filtered & the remaining AgNO3 is titrated against NH4SCN with
FeNH4(SO4)2 as an indicator which forms blood-red at the end point.

b. Nitric acid

- added to prevent the precipitation of Ag as carbonate, phosphate, etc. & to prevent hydrolysis of the
ferric alum

c. Nitrobenzene

- a convenient alternative to filtration to form a film over the precipitated AgCl particles, thus preventing
rxn with the NH4SCN. This is so since AgCl is sufficiently soluble with NH4SCN and so the titrant will not
only be consumed by the excess AgNO3 present but also by AgCl unless removed

AgCl + NH4SCN AgSCN + NH4Cl

SYNTHESIZED BY JRSG 2017