Experiment No.

Determination of chlorides in tap water

Sources of chlorides in drinking water

The sources of chloride in water may be natural or human beings. The presence of chloride in
groundwater can result from a number of sources including the weathering of soils, salt-bearing
geological formations, deposition of salt spray, salt used for road de-icing, contributions from
wastewaters and in coastal areas, intrusion of salty ocean water into fresh groundwater sources.

Generally, chloride ions are present in water as a different form of salts. The most common salts are
NaCl, KCl, MgCl2 and CaCl2. They are extremely soluble in water. The presence of chlorine residual in
drinking water indicates that: 1) a sufficient amount of chlorine was added initially to the water to
inactivate the bacteria and some viruses that cause diarrheal disease; and, 2) the water is protected from
recontamination during storage. The presence of free residual chlorine in drinking water is correlated with
the absence of disease-causing organisms, and thus is a measure of the potability of water.

Disinfection

Many of the diseases that affect traumatized communities are caused by micro-organisms carried in
drinking water. Hence the reference to waterborne diseases. Disinfection is the process of destroying
these organisms to prevent infection. There are a number of methods of disinfecting water, but
chlorination is by far the most common.

Disinfection by chlorine

Chlorine in one form or another is by far the most commonly used chemical for the disinfection of water
supplies. It is also active for other purposes associated with water treatment and supply, such as
prevention of algal, bacterial and general slime growths in treatment plants and pipe works, control of
tastes and odors, and removal of iron, manganese and colour. Chlorination of public water supplies has
been practiced for almost 100 years in the United States. Although the pros and cons of disinfection with
chlorine have been extensively debated, it remains the most widely used chemical for disinfection of
water in the U.S.

Chlorine usually is added to water as the gaseous form or as sodium or calcium hypochlorite. Chlorine
gas rapidly hydrolyzes to hypochlorous acid according to the following equation:
Similarly, aqueous solutions of sodium or calcium hypochlorite will hydrolyze according to:

The two chemical species formed by chlorine in water, hypochlorous acid (HOCl) and hypochlorite ion
(OCl -), are commonly referred to as “free available” chlorine. Hypochlorous acid is a weak acid and will
disassociate according to:

In waters with pH between 6.5 and 8.5, the reaction is incomplete and both species (HOCl and OCl -) will
be present. Hypochlorous acid is the more germicidal of the two.

Advantages

 It comes in several forms: powder, granules, tablets, liquid and gas.

 It is usually readily available in one form or another and relatively inexpensive.
 It dissolves easily in water.
 It provides residual disinfection.
 It is effective against a wide range of disease-causing micro-organisms.
 The main diseases can be controlled (to varying extents) by chemical disinfection include typhoid
fever, cholera, amoebic dysentery, bacterial gastroenteritis, shigellosis, salmonellosis, campylobacter
enteritis, Yersina enteritis, Pseudomonas infections, schistosomiasis, giardiasis and various viral
diseases, such as hepatitis A.

Disadvantages

 It is a powerful oxidizing agent which must be handled with care and breathing chlorine fumes must
be avoided.
 It does not effectively penetrate silt and organic particles suspended in the water.
 It can give an unpleasant taste if slightly overdosed, which can dissuade people from using the
supply.
 Its effectiveness against some organisms requires higher concentrations of chlorine and longer contact
times.
 Is ineffective in removing cryptosporidium and where this pathogen is a concern other methods
should be used in combination with chlorine (i.e. filtration).
When and where to test water

Continuous chlorination is most commonly used in piped water supplies. Regular chlorination of other
water supplies is difficult and usually reserved for disinfection after repair and maintenance. It is common
to test for chlorine residual at the following points:

 Just after the chlorine has been added to the water to check that the chlorination process is working.
 At the outlet of the consumer nearest to the chlorination point to check that residual chlorine levels
are within acceptable levels (should be between 0.2 and 0.5 mg/L)

Testing Methods

Titration

Titration is a process by which the concentration of an unknown substance in solution is determined by

adding measured amounts of a standard solution that reacts with the unknown. Then the concentration of
the unknown can be calculated using the stoichiometry of the reaction and the number of moles of
standard solution needed to reach the so called end point.

Iodometric Titration

The starch-iodide titration method, one of the oldest methods for determining chlorine, is very non-
specific for oxidants and generally is used for total chlorine testing at levels above 1 mg/L Cl 2. The
method is based on reaction with thiosulfate solution:

The end point of the titration is indicated by the disappearance of the blue-colored, starch-iodide complex.

The titration usually is performed at a sample pH, 3-4.

Amperometric Titration Methods

Amperometry is an electrochemical technique that applies a small electrical voltage across two electrodes
and measures the change in current resulting from chemical reactions taking place. Amperometric
titration measures the current change as a function of titrant added.
Precipitation Titration Methods

Precipitation titrations are based upon reactions that yield ionic compounds of limited solubility. The
most important precipitating reagent is silver nitrate. Titrimetric methods based upon silver nitrate are
sometimes termed argentometric methods. Potassium chromate can serve as an end point indicator for the
argentometric determination of chloride, by reacting with silver ions to form a brick-red silver chromate
precipitate in the equivalence point region.

1. Volhard’s Method

This method uses a back titration with potassium thiocyanate to determine the concentration of chloride
ions in a solution. Before the titration an excess volume of a silver nitrate solution is added to the solution
containing chloride ions, forming a precipitate of silver chloride. The term ‘excess‘ is used as the moles
of silver nitrate added are known to exceed the moles of sodium chloride present in the sample so that all
chloride ions present will react.

The indicator Fe3+ (ferric ion) is then added and the solution is titrated with the potassium thiocyanate
solution. The titrate remains pale yellow as the excess (unreacted) silver ions react with the thiocyanate
ions to form a silver thiocyanate precipitate.

Once all the silver ions have reacted, the slightest excess of thiocyanate reacts with Fe 3+ to form a dark
red complex.

The concentration of chloride ions is determined by subtracting the titration findings of the moles of
silver ions that reacted with the thiocyanate from the total moles of silver nitrate added to the solution.
This method is used when the pH of the solution, after the sample has been prepared, is acidic. If the pH
is neutral or basic, Mohr’s method should be used.
2. Mohr’s Method

The Mohr method uses chromate ions as an indicator in the titration of chloride ions with a silver nitrate
standard solution. After all the chloride has been precipitated as white silver chloride, the first excess of
titrant results in the formation of a silver chromate precipitate, which signals the end point. The reactions
are:

By knowing the stoichiometry and moles consumed at the end point, the amount of chloride in an
unknown sample can be determined.

Materials and Methods

Materials

Methods

Preparation of standard AgNO3 solution (0.1 M): 8.5 g of AgNO3 was weighed out, transferred to a
500 mL volumetric flask and made up to volume with distilled water. The resulting solution was
approximately 0.1 M. This solution was standardized against NaCl.

Preparation of standard NaCl solution (0.1 M): Reagent-grade NaCl was dried overnight and cooled to
room temperature. 5.844 g portions of NaCl were weighed into Erlenmeyer flasks and dissolved in about
1000 mL of distilled water.

Preparation of indicator (5 % K2CrO4): 1 g of K2CrO4 was dissolved in 20 mL of distilled water

Procedure

 Wash the burette with distilled water and small amount of (0.1 M) of AgNO 3
 Fill the burette with (0.1 M) of AgNO3
 Take 10.0 mL of NaCl by pipette and put it in a conical flask.
 Add (5) drops of K2CrO4 indicator to the conical flask and mix well.
 Titrate with AgNO3 until the appearance of red-brown precipitate.
 Repeat the titration 3 times and take the average.

Result

Discussion

The well-known Mohr’s method in which alkaline or alkaline earth chlorides react with silver nitrate in
the presence of a few drops of potassium chromate solution as indicator is a simple, direct and accurate
method for chloride determination.

In this experiment, the amount of chloride in an unknown sample was determined by Mohr titration. The
titration was carried out at a pH between 7 and 10 because chromate ion is the conjugate base of the weak
chromic acid. Therefore, when the pH is lower than 7, chromate ion is protonated and the chromic acid
form predominates in the solution. Consequently, in more acidic solutions the chromate ion concentration
is too low to produce the precipitate at the equivalence point. If the pH is above 10, brownish silver
hydroxide forms and masks the end point.

Since the solubilities of silver chloride and silver chromate depend on temperature, all titrations were
carried out at about the same temperature. Good stirring during the addition of the silver nitrate is also
required for a sharp and reproducible end point; otherwise, silver chromate that forms locally before the
endpoint can become occluded in the silver chloride precipitate instead of redissolving.

Standard silver nitrate solution and the silver chloride precipitates formed were protected from light at all
times because silver chloride decomposes according to:

The silver ion concentration at chemical equivalence in the titration of chloride with silver ions is given
by:

The chromate ion concentration required to initiate formation of silver chromate under this condition can
be computed from the solubility product constant for silver chromate:
In principle, an amount of chromate to give this concentration should be added, in order to develop the
red precipitate after the equivalence point. However, a chromate ion concentration of 6.6 x 10 -3 M imparts
such an intense yellow color to the solution that formation of the red silver chromate is not readily
detected. Thus, lower concentrations of chromate ion are generally used. An excess of silver nitrate is
therefore required before precipitation begins. An additional excess of the reagent must also be added to
produce enough silver chromate to be seen over the heavy white precipitate of silver chloride.

These two factors create a positive systematic error in the Mohr method that becomes significant in
magnitude at reagent concentrations lower than about 0.1 M. A correction for this error was made by a
blank determination. In a blank determination, all steps of the analysis are performed in the absence of the
analyte. In this experiment, blank was determined by titrating a solution of a small amount of chloride
free calcium carbonate and indicator potassium chromate with standard silver nitrate solution.