SALT

(Volhard Method)
PRINCIPLE
To determine salt, an analysis is made for total chlorides and
the result is expressed as sodium chloride. The method involves
the digestion of the sample with concentrated nitric acid and
oxidation of any remaining organic matter with potassium
permanganate. The dissolved chlorides in the sample are
precipitated with excess silver nitrate as silver chloride, and
the excess silver ions backtitrated with thiocyanate using ferric
alum as the indicator. When all the excess silver ions have
reacted with thiocyanate, any slight excess of thiocycnate will
react with ferric alum to form a red-coloured complex (ferric
thiocyanate) at the end-point. An excess of thiocyanate may react
with the precipitated silver chloride, since the solubility
product of silver thiocyanate is 0.01 that of silver chloride.
The addition of nitrobenzene, diethyl ether or acetone overcomes
this difficulty by coating the precipitated silver chloride and
thereby withdrawing it from reaction with the thiocyanate
solution. Nitrobenzene is toxic and its use is best avoided.
APPARATUS
1. Pipettes and burettes.
2. Laboratory glassware.
REAGENTS
1. Ferric alum indicator: saturated aqueous solution of reagent
grade ferric ammonium sulphate (I2H2O).
2. Silver nitrate solution, 0.20 N - dissolve 17.04 g of silver
nitrate, (previously dried at 110C) in distilled water and
dilute to 1 litre. Standardize (using excess silver nitrate
solution) against 0.10 N sodium chloride (5.845 g per litre).
3. Potassium thiocyanate solution (0.100N) - dissolve 9.72 g of
reagent grade potassium thiocyanate in distilled water, and
dilute to one litre.
4.
5.
6.
7.

Concentrated nitric acid.

Nitric acid (1+1).
Nitrobenzene.
Potassium permanganate solution (5%).

PROCEDURE

Accurately weigh appropriate amount (about 2-3 g) of sample into

a 300 ml Erlenmeyer flask. (For shrimp paste or other highly
salted foods, weigh about 5 g into 250 ml volumetric flask and
digest for about one hour in water bath to dissolve the salt.
Filter through No. 1 filter paper. Take appropriate amount of
this filtrate) (e.g. for shrimp paste, take 10 ml). Add 25 ml of
0.100N silver nitrate solution, swirl flask until sample and
solution are in intimate contact. Add 15 ml of concentrated
nitric acid. (The silver nitrate solution must be added first,
followed by the concentrated nitric acid. The order of addition
ensures complete precipitation of the chlorides. If nitric acid
is added first, loss of chloride by volatilization as hydrogen
chloride could occur, since hydrogen chloride has a far greater
vapour pressure than nitric acid.)
Boil in a fume hood until dissolved and add potassium
permanganate solution (5%) until colour disappears and the
solution
becomes
colourless.
(Should
too
much
potassium
permanganate be accidently added, colour removal can be effected
by the addition of small quantities of sugar). Add about 15 to 25
ml of distilled water, boil for 5 mins. Cool and dilute to about
150 ml with distilled water. Add about 1 ml nitrobenzene, 2 ml of
ferric alum indicator and shake vigorously to coagulate the
precipitated silver chloride. Titrate the excess silver nitrate
with 0.100 N potassium thiocyanate solution to a permanent light
brown end-point. Carry out a blank titration containing 25.0 ml
of 0.100N silver nitrate solution, 2 ml ferric alum indicator and
15 ml of (1+1) nitric acid with 0.100N potassium thiocyanate.

For highly salted foods requiring dilution, multiply the above

calculation by 250/ml aliquot taken for analysis.

REFERENCE
Official Methods of Analysis of the AOAC, 1984, 32.033, and other
references under other commodity headings.