give concentrations greater than the solubility of NaCl.

The chlorides are

precipitated in the form of silver chloride, in the presence of an indicator,
potassium chromate. The reaction occurs in two steps:
Cl- + AgNO3
AgCl (white precipitate) + NO3CrO4-- + 2Ag+ Ag2CrO4 (orange-red precipitate)
The end point is detected with Potassium Chromate.
The excess Ag+ ions present after all the Cl- ions have been removed from
solution, react with chromate to form silver chromate, an orange-red
precipitate. Since AgCl is less soluble than Ag2CrO4 the latter cannot form
permanently in the mixture until the precipitation of AgCl has reduced the
Cl- to a very small value.
Note: This titration must be carried out in a neutral medium because; in an acid
medium the silver chromate dissolves, and in an alkaline medium silver
oxide or silver carbonate precipitate. In practice, as the filtrate is neutral
or alkaline, it is first acidified with sulphuric or nitric acid, then neutralised
with calcium carbonate. The addition of the nitric acid has the advantage
of discolouring the filtrate (partially).
Numerous papers have been generated explaining different ways of reporting
salinity mg/l Cl-, ppm KCl etc. This has caused great confusion in the past
where apparently wildly different figures were in fact conveying exactly the
same salinity.
It is essential that salinity be always reported as mg/l chlorides. Remember
ppm is not the same as mg/l, (ppm x brine SG = mg/l)

equipment
Silver nitrate solution: 4.7910 g/l (0.0282 N or equivalent to 0.001 g chloride
ion/ml). Store in amber or opaque bottle.
Potassium Chromate Indicator solution: 5 g/100 ml water.
Sulphuric or nitric acid: standardised 0.02 N (N/50).
Phenolphthalein indicator solution: 1 g/100 ml of 60% alcohol in water
solution.
Calcium Carbonate: precipitated, chemically pure grade.
Distilled water: free of carbon dioxide by boiling.
Graduated pipettes: one 1 ml and One 10-ml.
Titration vessel: 100 - 150 ml preferably white.
Stirring rod.

procedures
1) Ensure the filtrate sample pipette doesnt have any crystallised salt on its
tip. Measure one ml of filtrate into a clean and dry 50 ml glass beaker.
2) Dilute with 25 mls of distilled water.
3) Add three drops of Phenolphthalein indicator. If the sample turns pink,
add 0.02N sulphuric acid drop by drop from a pipette while gently
stirring with a small magnetic bead on a hot/plate stirrer until the pink
colour just disappears.

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