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Precipitation Titration: Determination of Chloride by the Mohr Method

by Dr. Deniz Korkmaz

Introduction

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.
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, bromide and cyanide ions by reacting with silver ions to form a brick­red silver
chromate precipitate in the equivalence point region.
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 (1). 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. This report describes experiments
aimed at determining the concentration of chloride in a solid sample
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 (2, 3). 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. A suitable pH was achieved by
saturating the analyte solution with sodium hydrogen carbonate.
Since the solubilities of silver chloride and silver chromate depend on temperature, all
tirations 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:
2AgCl ũ Ag(s) + ― Cl (g)

The silver ion concentration at chemical equivalence in the titration of chloride with
silver ions is given by:
[Ag ] =
=
= 1.35 x 10 M
+
­5

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:
4

[CrO ] =
=
= 6.6 Ũ10 M

­3

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 10­3 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. Calcium
carbonate was used to imitate the white silver chloride precipitate. Reagent volumes were
corrected for blank in the calculations.

CHLORIDE ION DETERMINATION
This test measures the soluble chloride Ion concentration in the mud filtrate. The Chloride can come from sodium chloride,
calcium chloride or potassium chloride. Also, for the titration to work correctly the pH of the filtrate needs to be only weakly
basic (pH = 8.3). This is the reason for the first step in the procedure. There are two chemical reactions
taking place simultaneously during the titration:
1.
Ag (+) + Cl ----------AgCL 2. 2 Ag
(+) + CrO4 ----Ag2CrO4
The first reaction, the formation of silver chloride, accounts for the appearance of the white specs or milky appearance during
the titration. The formation of the silver chromate, which is red, will not start until all the chloride Ions are tied up as silver
chloride. The silver nitrate will then react with the chromate from the potassium chromate indicator to form silver chromate.
So, for the above two reactions to occur, the filtrate needs to be weakly basic (pH = 8.3). High pH will precipitate silver oxide.

PROCEDURE
1.
2.
3.
4.

5. 6.

.0 ml of filtrate or sample to be tested into titration dish. Add 2 - 3 drops
of phenolphtahalein indicator to the filtrate.
If a pink color appears, titrate with N/50 sulfuric acid until the color changes from pink to that of the original
sample. If no pink color appears, the test can be continued.
If needed, add 25 - 50 mls of distilled water. This serves to dilute the dark color of a deeply colored filtrate. It does
not influence the test in any way if there are no chlorides present in the distilled water. If any water other than
distilled water is used, the chloride in it must be accounted for by titration before adding the filtrate to it.
Add 10 - 15 drops of potassium chromate indicator to give the filtrate a bright yellow color.
Add silver nitrate from a pipette dropwise, stirring continuously with a stirring rod, until the sample just turns
from yellow to an orange-red.

P
i
p
e
t
t
e
1

CALCULATION
1.
2.
3.

Parts per million (ppm) chloride = mls of silver nitrate used x 1,000 (If 0.0282N Silver Nitrate, lml = 1,000
ppm Cl is used)
Parts per million (ppm) chloride = mls of silver nitrate used x 10,000 (If 0.28N Silver Nitrate, lml = 10,000
ppm Cl is used)
ppm (NaCl) = ppm Chloride x 1.65

REMARKS
1.

The chloride test may be run on the same samples used in the Pf determination if the Mf test was not
performed.

2.

Avoid contact with silver nitrate. Wash immediately with water if silver nitrate gets on skin or clothing.

3.

4.
5.

The end point of the reaction is when the silver chromate is first formed. It is reddish in color. When using
the weak silver nitrate, the end point is approached very gradually. Therefore, the formation of the silver
nitrate can be seen by a color change from yellow to orange-red. If the strong silver nitrate is used, the end
point is approached much more rapidly. Hence the early formation of the silver chromate and its orange-red
color may be missed due to the larger amounts of silver nitrate being added. So the color change will go from
yellow to red, as soon as the red color is seen, the titration is complete.
White lumps of silver chloride form when titrating high concentrations of salt. This should not be taken for the
end point.
If the chloride Ion concentration is less than about 10,000 ppm, the weak silver nitrate solution should be used. If
it is greater than 10,000, the strong silver nitrate solution should be used.

ALKALINITY DETERMINATIONS
I.

MUD ALKALINITY (Pm)
This test measures the alkalinity of the whole mud. When used along with the filtrate alkalinity
determination, the amount of excess line present in lime muds can be determined.

PROCEDURE
1.
2.

3.
4.
5.
6.

Measure 1 ml of a freshly stirred sample of mud into a titration dish using a syringe.
The syringe should have a capacity of at least 3 mls. Draw at least two mls and preferably three mls of mud into
the syringe. Remove any air bubbles from the sample. Then inject a one ml sample by pushing the plunger from
the 3 ml graduation to the 2 ml graduation or the 2 ml graduation to the 1 ml graduation, but never from 1 ml to
the bottom of the syringe.
Dilute the mud in the dish with 25 - 50 mls of distilled water. Add no
more than 4 or 5 drops of phenolphthalein.
If the sample does not change color, report the Pm as 0.
If the sample turns pink, titrate rapidly with N/50 sulfuric acid until the pink color disappears.

CALCULATIONS
Report the phenolphthalein alkalinity of the mud, (Pm) as the number of mls of N/50 sulfuric acid added to discharge all the
pink color.

REMARKS
1.

If the mud sample is deeply colored from chemical thinners and the color change is hard to see, use ½ ml of
mud and report the Pm as the volume of N/50 sulfuric acid added to discharge the pink color doubled. 2.
If 0.1N sulfuric acid is used, the Pm is reported as volume of N/50 sulfuric acid added to 1 ml of mud
times 5.

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OFI Testing Equipment - 144-50 Instructions - Chloride and Alkalinity Determination

II.

Page 4 of 5

FILTRATE ALKALINITY (Pf, Mf)
These tests are designed to measure the alkalinity contributions from soluble mud constituents. The Pf and
Mf test together can be used to get an estimate of the hydroxide Ion (OH-), the bicarbonate Ion (HCO3-)
and the carbonate Ion (CO3 -2) concentration. Also the Pf can be used with the Pm to determine the excess
amount of lime present in a lime base mud.

PROCEDURE (Pf)
1.
2.

Pipette 1 ml of filtrate into a clean titration dish. (Do not dilute with distilled water.)
Add more than 2 - 3 drops of Phenolphthalein. If no color develops, the Pf is 0 (and pH is less than 8.3). If
a pink color develops, add N/50 sulfuric acid through a pipette until the color changes pink to that of the original
sample.

CALCULATIONS (Pf)
1.

The Pf is the amount of N/50 sulfuric acid required to discharge the pink color. 2.
Excess lime content, lb/bbl = Pm - Pf
4

PROCEDURE (Mf)
1.
2.

To the same sample used for the Pf determination, add 2 -3 drops of Brom cresol green-methyl red
indicator.
Again add N/50 sulfuric acid until the color changes from a blue-green to a light pink color.

CALCULATIONS (Mf)
1. Report the Mf alkalinity of the filtrate as the total volume of N/50 sulfuric acid required to reach the end point,
including the volume required to reach the Pf end point.
2. An estimation of hydroxide Ion, bicarbonate Ion and carbonate Ion concentrations can be determined using the
following table.

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OFI Testing Equipment - 144-50 Instructions - Chloride and Alkalinity Determination

Page 5 of 5

CALCULATIONS OF ALKALINITY
Test Results
Where Pf = Mf
(indicates OH only)
Where 2 Pf-Mf is a positive number
(indicates OH- & CO3-2)
Where 2 Pf = M
(indicates CO3-2 only)

Calculations
Pf x 340 = Mg/L OH-

(2pf-Mf) x 340 = Mg/L OH2(mf-Pf) x 600 = Mg/L CO3-2
Mf x 600 = Mg/L CO3-2

Where 2Pf-Mf is a negative number
(indicates CO3-2 & HCO3-)

2 Pf x 600 = Mg/L co3-2
(Mf-2Pf) x 1220 = Mg/L HCO3-

Where no Pf reading or very low Pf
(indicates HCO3 - only)

Mf x 1220 = Mg/L HCO3-

NOMENCLATURE
Pf = Pnenolphtbalein end point of the filtrate sample using N/50 sulfuric acid
Mf = Methyl Orange or Brom Cresol Green-Methy red end point of filtrate sample using N/50 Sulfuric Acid
OH = Hydroxide Ion
CO3-2 = Carbonate Ion
HCO3- = Bicarbonate Ion

Introduction
This method determines the chloride ion concentration of a solution by titration with silver nitrate. As the 
silver nitrate solution is slowly added, a precipitate of silver chloride forms.

Ag+ (aq) + Cl– (aq) → AgCl(s)

The end point of the titration occurs when all the chloride ions are precipitated. Then additional chloride
ions react with the chromate ions of the indicator, potassium chromate, to form a red­brown precipitate of
silver chromate.

2 Ag+ (aq) + CrO 4 2– (aq) → Ag2 CrO 4(s)
This method can be used to determine the chloride ion concentration of water samples from many sources
such as seawater, stream water, river water and estuary water. Seawater is used as the example here.
The pH of the sample solutions should be between 6.5 and 10. (Refer to the additional notes (3) for the
explanation). If the solutions are acidic, the gravimetric method or Volhard’s method should be used

Result Calculations
1. Determine the average volume of silver nitrate used from your concordant titres.
2. Calculate the moles of silver nitrate reacting.
3. Use the following reaction equation to determine the moles of chloride ions reacting.

Ag+ (aq) + Cl– (aq) → AgCl(s)

4. Calculate the concentration of chloride ions in the diluted seawater.
5. Calculate the concentration of chloride ions in the original undiluted seawater.
6. Calculate the concentration of sodium chloride in the seawater in molL−1, gL−1 and g/100 mL (%).

Additional Notes
1. Silver nitrate solution will stain clothes and skin. Any spills should be rinsed with water immediately.
2. Residues containing silver ions are usually saved for later recovery of silver metal. Check this with your
teacher.
3. The Mohr titration should be carried out under conditions of pH 6.5 – 9. At higher pH silver ions may be
removed by precipitation with hydroxide ions, and at low pH chromate ions may be removed by an acid­
base reaction to form hydrogen chromate ions or dichromate ions, affecting the accuracy of the end point.
4. It is a good idea to first carry out a “rough” titration in order to become familiar with the colour change at
the end point.
5. The Mohr titration is sensitive to the presence of both chloride and bromide ions in solution and
will not be too accurate when there is a significant concentration of bromide present as well as the
chloride. However, in most cases, such as seawater, the bromide concentration will be negligible. For this
reason, the method can also be used to determine either the total concentration of chloride and bromide
in solution, or the concentration of bromide when the chloride concentration is known to be negligible.
http://intro.chem.okstate.edu/ChemSource/Seawater/act2.htm
Activity 2: Determination of the Salinity of Seawater
Introduction
This method involves chemical volumetric analysis. A silver nitrate (AgNO 3 ) solution
of known concentration is used to precipitate out the chlorides in a seawater sample.
The procedure is complicated by the fact that the dense white precipitate, silver
chloride (AgCl), does not settle rapidly. It is impossible to tell when all the chlorides
have been removed from the seawater unless an indicator is used to signal complete
precipitation by a visual color change. The indicator in the analysis is chromate ion.
When all of the chloride ion is exhausted, the chromate ion reacts with silver ions and
produces silver chromate, which is red. The instant a permanent orange tinge
appears in the solution (one that doesn’t vanish with mixing), the addition of silver
nitrate is stopped. The final solution color should look like that of orange juice.
The chemical reactions are:
The titration is carried out in a 150­mL Erlenmeyer flask, using a white background
and good lighting, but away from direct sunlight. Constant but gentle stirring is
essential, since the silver chloride tends to form clots, which trap some of the
reagents. A magnetic stirrer is very helpful. The silver nitrate is added until the faint
reddish or orange tinge remains after stirring for 45 s. At this point one drop should
give the desired end point. Observable flocs of silver chloride will obscure the end
point, since the solutions that they contain in their interstices will leak out slowly
and cause the end point to be impermanent. A stirring rod left permanently in the
flask, especially if a magnetic stirrer is not used, will help to break up these curds.
Purpose
1. To determine the chlorinity (and thus the salinity, since they are directly
related) of a sample of seawater.
2. To use the titration technique with a reaction different from an acid/base
reaction.
Safety
Wear protective goggles throughout the laboratory activity. Avoid getting AgNO 3 on
hands since it stains the skin.
Procedure

1. With a pipet deliver 5.0mL seawater into a 150­mL Erlenmeyer flask.
2. Using a 10­mL graduated cylinder, add 5.0mL potassium chromate indicator
solution, and begin to add the silver nitrate solution from a buret while
constantly stirring.
3. When the solution turns orange, stop adding silver nitrate. The color should
persist for less than 20 sec. Continue adding silver nitrate dropwise, mixing all
the while, until orange color persists. Record the volume of silver nitrate added.
4. Thoroughly wash your hands before leaving the laboratory.
Data Analysis and Concept Development
From a simple algebraic proportion one can determine the chlorinity of the seawater
because it has been shown experimentally that the salinity is a constant 1.80655
times higher than the chloride level. Thus, the salinity (S) can be calculated (using
the equation S ppt = 1.80655 Cl ppt; the chlorinity (Cl) of the artificial seawater
should be about 19.05 ppt).
1. What is the number of moles of silver used in the titration (AgNO 3 is 0.2184 M)?
2. Determine the number of moles of chloride in the sample.
3. Determine the grams of chloride present in the sample.
4. What is the chlorinity of 10g of sample? (The density of seawater is about
1.05 g / mL 1 ).
5. What is the salinity of the sample in ppt?