LABORATORY WORK

PRECIPITATION TITRATION.
MOHRS METHODS

Objective: Determination of chloride in solid and liquid samples by the Mohr

Method

Learning Outcome:
 Students understand the terms volumetric analysis, morarity, molality
normality and redox titration.
 Students acquire the skill to prepare standard solutions of silver nitrate and
sodium chloride.
 Students understand the apparatus used for a titration.
 Students acquire the skill to perform the precicpitation-titration in the real
lab after understanding the different steps.

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.
Classification of methods precipitation titration (on titrant):
1. Argentometry
2. Thiocyanatometry
3. Mercurometry
4. Sulphatometry
5. Hexacianoferratometry
Characteristics of Precipitation Titration:
 They are fast and the stoichiometry is known and reproducible, (no
secondary reactions of interference).
 They are complete or can be quantified depending on the amount of
solubility product (in general a precipitation titration is considered complete when
Ksp < 10-8)
 An indicator can be used to find the equivalence point or titration end point
which, for this type of titration, corresponds to when precipitation of the analyte
under analysis is complete.

The Solubility Product Constant

         When an ionic compound is dissolved in water, it usually goes into solution
as the ions. When an express of the ionic compound is mixed with water,
equilibrium occurs between the solid compound and the ions in the saturated
solution:
1
 KxAy = xK+ + yA-
The equilibrium constant for this solubility process can be written:
K eq =¿ ¿
         However, because the concentration of the solid remains constant (in
heterogeneous systems), we normally combine its concentration with K eq to give
the equilibrium constant Ks, which is called the solubility product constant:
K s =K eq ∙ [ K x A y ] =¿
         In general, the solubility product constant, Ks, is the equilibrium constant for
the solubility equilibrium of slightly soluble (or nearly insoluble) ionic
compounds. It equals the product of the equilibrium concentrations of the ions in
the compound, each concentration raised to a power equal to the number of such
ions in the formula of the compound.
At equilibrium in saturated solution of slightly soluble compound at given
temperature and pressure the value of Ks is constant and not depend on ions
concentration. The solubility product constant is thermodynamic constant and
depends on temperature and ions activity (ionic strength).
         The reaction quotient, Q, is an expression that has the same form as the
equilibrium constant expression Ks, but whole concentration values are not
necessarily those at equilibrium. Though the concentrations of the products are
starting values: Q=¿
       Here Q for a solubility reaction is often called the ion product, because it is
product of ion concentrations in a solution, each concentration raised to a power
equal to the number of ions in the formula of the ionic compound.
 Precipitation is expressed to occur if the ion product Q for a solubility
reaction is greater than Ks: Q > Ks.
 If the ion product Q is less than K s, precipitation will not occur (the solution
is unsaturated with respect to the ionic compound): Q < Ks.
 If the ion product Q equal K s, the reaction is at equilibrium (the solution is
saturated with the ionic compound): Q = Ks.
 
Calculation of solubility
Solubility, S, is the molar concentration of compound in saturated
solution.
Ks

II. Saturated solution of good soluble ionic compound.

√
I.   Saturated solution of slightly soluble ionic compound:  S= x+ y x
x ∙y
y
     

         This type of solutions not used in analytical practice. Such solutions are very
concentrated and have large ionic strength. Components of these solutions (ion,
molecules) can associate and form various polymers and colloids.
III. Saturated solution of slightly soluble compound with very small solubility:
 the substance have limited solubility but create ion pairs and various
molecular forms. The ionic strength of this solution is high and solubility
depends on common concentration of all molecular and ionic forms;

2
  slightly soluble compound takes part in protolytic reaction with water with
the pH change.  
The solubility is affected by pH. If the anion is the conjugate base of a weak
acid, it reacts with H+ ion. Therefore, the solubility slightly soluble compound to
be more in acid solution (low pH) than it is in pure water.
         In sour environment solubility of slightly soluble compounds is more than
more is its Ks and more is the hydrogen ion concentration:
S K A =¿
x y

when ¿

Factors which influence to solubility:

1. Temperature. Solubility for most of substances is endothermic process.
Increase temperature occurs decrease solubility. But crystal compounds at various
temperature form hydrates another structure (composition). Hydrates formation
may be exothermic reaction.
2. Ionic strength of solution. Increasing of ionic strength causes decreasing
of ions activity and, accordingly, Ks will increase. Because, solubility will increase.
An example of it is salting effect.
Salting effect is increase the solubility of slightly soluble compounds in
presence of strong electrolytes, which not have common ions with precipitate and
not react with precipitate ions.
3. Common-ion electrolytes. Completeness of precipitation.
         The importance of the solubility product constant becomes apparent when we
consider the solubility of one salt in the solution of another having the same cation
or anion. The effect of the common ion is to make slightly soluble salt less soluble
than it would be in pure water. This decrease in solubility can be explained in
terms of Le-Chatelier’s principle. It is example of the common-ion effect.
         Decrease of solubility of slightly soluble compounds in presence of
electrolyte with common ions called common-ion effect.
         But solubility of slightly soluble compounds decrease to moment when ionic
strength of solution will begin to influence to solubility.
         The ion is completely precipitated when its residual concentration (C min) is
less than 1×10-6 M (Cmin < 1×10-6 M). Amount of precipitant must be more at 20-50
% it is necessary to stoichiometry equation.
         If in solution are ions, which form slightly soluble compounds with
precipitant, the sequence of its precipitation determines (depends on) Ks value.
Fractional precipitation is the technique of separating two or more ions
from a solution by adding a reactant that precipitates first one ion, than another,
and so forth.
4. The pH value (see above).
5. Complex compound formation. Solubility increases with increasing
concentration of ligand, complex compound stability and Ks value.
6. Redox process. Redox reaction shift on equilibrium in heterogeneous
system and change solubility of slightly soluble compounds.
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 ARGENTOMETRY

The most important precipitating reagent is silver nitrate (AgNO 3).

Titrimetric methods based upon silver nitrate as titrant 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 brick-red silver chromate precipitate in the equivalence
point region.
Fields of argentometry application:
 The determination of the anions Cl-, I-, Br- and Ag+ is also common.
 Environment: Determination of chloride in water.
 Food and beverage: Determination of chloride in finished products (cooked
meats, preserves). Determination of chloride in dairy products.
 Precious metals: Determination of silver in various alloys (for jewellery).
 Pharmaceuticals: Titration of halides.
The reaction rates for the silver salt precipitation is rapid. The reaction ratio
is 1:1 and silver salts formed are generally quite insoluble. Table below gives the
solubility product, Ksp, for the silver salts that are involved in precipitation
titrations.
Table 1 Solubility products for silver salts
Anion Ksp Solubility (g/100mL)
-10
Cl- 1.8 x 10
Br- 5.2 x 10-13
I- 8.3 x 10-17
SCN- 1.1 x 10-12 0.00002
-12
CrO42- 2.6 x 10 0.0025

Endpoint Detection for Argentometric Titration. Another requirement of

titrimetric analysis is that there must be some method of determining when the
titration reaction has reached its equivalence point. In this experiment, you will
compare two methods of endpoint detection, one using a chemical indicator and
another using potentiometric detection. We will now describe the common
methods of endpoint detection for argentometric titrations.
Chemical Indicators. There are three common chemical indicators that are
associated with argentometric titrations:
1. The chromate ion, CrO42- (the Mohr method);
2. The ferric ion, Fe3+ (the Volhard method);
3. Adsorption indicators such as fluorescein (the Fajans method).
The curve for the titration of 100 cm3 of 0.0100 M KCl with 0.100 M AgNO3
is shown in Fig.1.

4
 You may note here that the titration curve is quite similar to the one for the
titration between a strong base and a strong acid. According to this curve there is a
sharp increase in the concentration of silver ions immediately after the equivalence
point. This is indicated by a sharp decrease in the value of pAg+ ( -ln(Ag+)). Such a
sharp increase in the concentration of silver ions can be detected in different ways
and accordingly there are three different methods of detecting the end point of the
titration.
According to end point detection method, three main procedures are widely
used depending on the type of application. These are:
1. Mohr’s Method
2. Volhard’s Method
3. Fajan’s Method
Table 2. Comparison of silver titration methods

1. The Mohr method uses chromate ions as an indicator in the titration of

chloride ions with a silver nitrate secondary standard solution (normality: 0.0141).
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This corresponds to 1 mL of 0.0141N AgNO 3 equals to 1 mg chloride in solution.
The silver nitrate solution is standardized against standard chloride solution,
prepared from sodium chloride (NaCl). During the titration, chloride ion is
precipitated as white silver chloride:
Ag+ + Cl- = AgCl (Ksp=3×10-10)

After all the chloride has been precipitated as white silver chloride, the first
excess of titrant results in the formation of a reddish-brown silver chromate
precipitate, which signals the end point. This stage is taken as evidence that all
chloride ions have been consumed and only excess silver ions have reacted with
chromate ions. The reaction is:
(Ksp=5×10-12)
2−¿=Ag 2 CrO4( s) ¿
+¿+CrO ¿
2 Ag 4

The solution needs to be kept around a neutral pH neutral: silver hydroxide

forms at high pH, and chromate will form H2CrO4 at low pH. This will reduce the
concentration of chromate ions, and delay the formation of the precipitate. In
addition, since carbonates and phosphates both precipitate with silver, they must be
eliminated from the reaction to prevent inaccurate results. The Mohr method is a
relatively simple and accurate method for chloride ion determination. As such, it
has many applications where the concentration of chloride in water or in food must
be determined.
By knowing the stoichiometry and moles consumed at the end point, the
amount of chloride in an unknown sample can be determined.

2. The Volhard’s method was first described by the Jacob Volhard, a

German Chemist, in 1874.
This is an indirect titration procedure, where an excess amount of
standard Ag+ is added to the chloride solution containing Fe3+ as an indicator. The
excess Ag+ is then titrated with standard SCN - solution until a red color is obtained
which results from the reaction:
Ag+ + Cl- = AgCl + Ag+excess
white ppt
+
Ag excess + KSCN -> AgSCN + K+
white ppt
At end point: Fe3+ + SCN-  Fe(SCN)2+
red brown ppt

Here, initially thiocyanate react with silver ions and forms precipitate at end point,
excess of thiocyanate (SCN-) react with Fe(III) and forms reddish brown complex
which indicate the end point of reaction.
The indicator system is very sensitive and usually good results are obtained.
The medium should be acidic to avoid the formation of Fe(OH)3.
However, the use of acidic medium together with added SCN - titrant
increase the solubility of the precipitate leading to significant errors. This problem
had been overcome by two main procedures.
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 Thiocyante is standardised against a standard silver solution, with the silver
solution being in the titration flask and the thiocyanate in the burette.
This Volhard method is used to determine the concentration of Ag + ions or
concentration of halide ions (i.e. Cl-, Br-, I-) indirectly i.e. by back titration.

3. Fajan’s Method (indicator adsorption method). The precipitation

titration in which silver ions is titrated with halide or thiocyanate ions in presence
of adsorption indicator is called fajan’s method.
Adsorption indicators function in an entirely different manner than the
chemical indicators and they can be used in many precipitation titrations.
Since the adsorption of indicator takes place at end point the method is also
called indicator adsorption method.
Table 3. Common adsorption indicators

The indicator, which is a dye, exists in solution as the ionized form, usually
an anion.
The method is generally used for the quantitative analysis of halide ions or
thiocyanate ions.
Silver chloride forms colloidal particles. Before the equivalence point, the
surface of the precipitant particles will be negatively charged due to the adsorption
of excess Cl− to the surface of the particles. When the equivalence point is reached,
there is no longer an excess of analyte Cl−, and the surface of the colloidal particles
are largely neutral. After the equivalence point, there will be an excess of titrant
Ag+, some of these will adsorb to the solid AgCl particles, which will now be
surrounded by a diffuse negative counterion layer.
Adsorption indicators are dyes, such as dichlorofluorescein, that usually
exist as anions in the titration solution. The doubly charged dichlorofluoroscein
anion is attracted into the counterion layer immediately following the equivalence
point, when the surface charge of the particles changes from negative to positive.
For reasons that are not fully understood, the closer proximity of the dye to the
particles changes the color of the molecule, providing a visual indication of the
titration endpoint. In the case of dichlorofluorescein, the indicator changes to a
pinkish color.
Fluorescein and its derivatives are adsorbed to the surface of colloidal AgCl.
After all chloride is used, the first drop of Ag+ will react with fluorescein (FI -)
forming a reddish color.
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 Ag+ + FI-  AgF
Among these methods, the Volhard Method is widely used because we can
detect the end point of precepitation titration very well.

1ST EXPERIMENT. Standardization of silver nitrate solution with sodium

chloride

Apparatus: Burette, conical flask, pipette, measuring cylinder.

Reagents: 5% K2CrO4 (indicator) solution, 0.1M silver nitrate titrant and solid
NaCl.

Aqueous silver nitrate is photosensitive and should not be exposed to light

any more than is necessary during this procedure. It should be stored in darkened
storage bottles, and be kept in your drawer except when being used.
Silver nitrate is an important precipitating reagent which can also be used for
thedetermination of the halogens, halogenlike anions, mercaptans, fatty acids, and
several divalentinorganic anions.
Silver nitrate solutions of known concentration can be prepared from known
mass of dried AgNO3. However, if we don't have access to the high purity reagent,
or if we have a solution of unknown concentration, we can easily standardize it
against sodium chloride.
Reaction taking place during titration is
AgNO3 + NaCl → AgCl↓ + NaNO3

Preparation of 5% K2CrO4 (indicator): 1.0 g of K2CrO4 was dissolved in 20 mL of

distilled water.
Preparation of AgNO3 solution: 9.0 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: Reagent-grade NaCl was dried overnight
and cooled to room temperature. Accurately weigh about 0.6g of sodium chloride
in a clean dry weighing bottle, and transfer the same to a clean volumetric flask of
100 cm3 capacity through a glass funnel. Add about 20 mL of distilled water and
swirl the contents of the flask until all the sodium chloride is dissolved. Make the
volume upto the mark by adding more distilled water. In order to adjust the pH of
the solutions, small quantities of NaHCO3 we are added until effervescence ceased.

PROCEDURE:
1. Take with pipette 25 ml NaCl standard solution in a conical flask. Measure
sample pH.
2. Then add 2.0 ml 5% K2CrO4 indicator solution.
3. Fill up the burette with AgNO3 solution up to the zero mark (bottom menisque).
4. Titrate the sodium chloride solution silver nitrate titrant solution. Although the
silver chloride that forms is a white precipitate, the chromate indicator initially
gives the cloudy solution a faint lemon-yellow colour. The endpoint of the titration
8
is identified as the first appearance of a red-brown colour of silver chromate
Ag2CrO4 and note down volume of titrant used. Also measure sample pH.
5. All titration processes are done in three trials.
6. Calculate concentration and titer of titrant AgNO3.

Results of titration:
 Volume of standard solution for titration: VNaCl= 10 mL
 Normality of standard solution for titration: NNaCl = 0,1N
 Equivalent weight of sodium chloride: Eq NaCl =
 Equivalent weight of potassium permanganate: Eq AgNO = 3

 Volume of titrant consumed for the 1st titration: V1AgNO3 =

 Volume of titrant consumed for the 2nd titration: V2AgNO3 =
 Volume of titrant consumed for the 3rd titration: V3AgNO3 =
V 1 +V 2 +V 3
 Average amount of titrant consumed for titration: V ¿AgNO = =¿
3
3

Calculation:
The result is expressed as mol-eq/l concentration and based on the following
formula:

V NaCl N AgNO V NaCl ∙ N NaCl

= 3
=> N AgNO =
V ¿AgNO
3
N NaCl 3
V ¿AgNO 3

N AgNO ∙ Eq AgNO
T AgNO = 3 3

3
1000

N AgNO ∙ Eq NaCl
T AgNO / NaCl = 3

3
1000

The calibration result can be accepted if 3 determinations give a result with a

relative standard deviation of less than 0.5%

2nd EXPERIMENT. Use Mohr’s method to determine the concentration of

chloride ion in solid sample.

Mohr method of determination of chlorides by titration with silver nitrate is

one of the oldest titration methods still in use - it was researched and published by
Karl Friedrich Mohr in 1856.
The Mohr Method uses silver nitrate for titration (normality: 0.0141)
(method applicability: 0.15 to 10 mg/L chloride ions). This corresponds to 1 mL of
0.0141 equals to 1 mg chloride in solution. The idea behind is very simple -
chlorides are titrated with the silver nitrate solution in the presence of chromate
anions. End point is signalled by the appearance of the red silver chromate.

9
 Initial point white ppt of AgCl End point of Titration

Intense yellow color of chromate may make detection of first signs of

formation of red silver chromate precipitation difficult. As some excess of silver
must be added before precipitate starts to form, if concentration of titrant is below
0.1M, we may expect significant positive error. To correct for this error we can
determine a blank, titrating a solution of the indicator potassium chromate with
standard silver nitrate solution. To make result more realistic we can add small
amount of chloride free calcium carbonate to the solution to imitate the white
silver precipitate.
Solution during titration should be close to neutral. The Mohr
method for determination of chloride in water is a pH sophisticated method. It
must be perform between the pH levels 6.5 – 9.0. It is better to carry out between
the pH ranges 7 – 8. At upper pH level, the silver ions react with hydroxide ions
and precipitated as silver hydroxide. In contrast, at lower pH level, potassium
chromate may be converted into potassium dichromate (K2Cr2O7) and mask the end
point. Consequently, accurate result cannot be obtained. If the water sample is
acidic, then gravimetric method or volhard’s method is appropriate.
Ag+(aq) + OH–(aq) → Ag(OH)(s)
CrO42-(aq) → Cr2O72-(aq)
Both processes interfere with the determination accuracy.
Exactly the same approach can be used for determination of bromides. Other
halides and pseudohalides, like I- and SCN-, behave very similarly in the solution,
but their precipitate tends to adsorb chromate anions making end point detection
difficult.

Most foods have sodium from dissolved salts, either naturally present or
added in cooking or processing. Table salt known as sodium chloride (NaCl) is the
most common source of sodium. It is made up of 40% sodium and 60% chloride
and often used in processed and packaged foods as flavour enhancer or
preservative. Other sources of sodium added in foods are monosodium glutamate
(MSG), sodium nitrite, sodium saccharin, baking soda (sodium bicarbonate), and
sodium benzoate.

10
 The sodium content of food has
implications on our health. Sodium is an
essential mineral required in small
amount by the body to control blood
pressure and help the nerves and
muscles to function properly. However,
high sodium intake can cause health
problems such as high blood pressure
and cardiovascular diseases, which
include heart, stroke, and blood vessel
disease. Thus, knowing the sodium
content in food and controlling the
intake are of utmost important to keep
diseases at bay.
The American Heart Association1 recommends consumption of less than
1,500 mg per day sodium for most American adults, which is the level with the
greatest effect on blood pressure. This level does not apply to people who lose
large amounts of sodium in sweat, such as competitive athletes, workers exposed
to extreme heat stress, or to those directed otherwise by their healthcare provider.

PROCEDURE
1. The chloride samples (NaCl) have been dried and stored in a desiccator. Take a
sample and record its number on your data sheet.
2. Zero (tare) the analytical balance with a clean dry, capped weighing bottle. Add
1.1 to 1.3g of your chloride sample (NaCl) to the bottle; replace the cap and weigh
as accurately as possible. Record on your data sheet.
3. Rinse a 250 mL volumetric flask with distilled water and quantitatively transfer
the chloride sample to the flask. Dissolve the sample and dilute to the mark. Mix
thoroughly.
4. Into each of three 200 - 250 mL erlenmeyer flasks carefully pipet 20.00 mL of
your chloride sample. (Remember to rinse the pipet with the sample solution
before the first transfer.) Use a graduated cylinder to add about 20 mL of distilled
water to each flask.
5. Add 2.0 mL 5% K2CrO4 indicator solution to the first sample flask.
6. Rinse and fill a 50 mL burette with standartized AgNO 3 titrant solution. Tap to
remove bubbles and make certain that the burette tip is filled with solution. Adjust
the solution level between 0 and 2 mL; read the burette to the nearest 0.01 mL. (Do
not try to set 0.00 mL!) Record the initial reading.
7. Titrate first flask to the first appearance of a persistent brown color. Read the
burette to the nearest 0.01 mL and record the value on your data sheet. Repeat the
procedure with the other samples. You should have three endpoint volumes within
a range of 0.1 - 0.2 mL. If this is not the case, prepare a few more sample solutions
and repeat the titrations.

11
8. Empty the contents of the titration flasks as well as any excess AgNO 3 solution
into a waste container. (There are large bottles in the fume hoods for this purpose.)
9. Rinse the burette, pipet and volumetric flask with several portions of distilled
water and put them away. Use a brush and soapy water to wash the Erlenmeyer
flasks.

Results of titration:
 Weight of NaCl salt sample: msample =
 Stock volume of NaCl salt solution: Vtotal NaCl = 250 mL
 Equivalent weight of Cl- ion in Mohr salt: EqCl = ¿ −¿

 Volume of NaCl salt solution for titration: VNaCl = 10 mL

 Normality of standardized AgNO3 solution for titration: NAgNO3 =
 Volume of titrant consumed for the 1st titration: V1AgNO3 =
 Volume of titrant consumed for the 2nd titration: V2AgNO3 =
 Volume of titrant consumed for the 3rd titration: V3AgNO3 =
V 1 +V 2 +V 3
 Average amount of titrant consumed for titration: V ¿AgNO = =¿
3
3

Calculation:
The result is expressed as mol-eq/l concentration and based on the following
formula:

V NaCl N AgNO N
= 3
=> −¿
Cl =
V AgN O ∙N AgNO
V ¿AgNO N Cl ¿
3 3
¿
−¿ V NaCl
3

T Cl −¿
=N Eq Cl−¿
¿¿
Cl−¿ ∙ ¿
1000

m¿

W Cl −¿
,% =m ¿ ¿¿

The calibration result can be accepted if 3 determinations give a result with a

relative standard deviation of less than 0.5%

3rd EXPERIMENT. Use Mohr’s method to determine the concentration of

chloride ion in liquid sample.

Apparatus: Conical flask, burette with stand, pipette, measuring cylinder,

volumetric flask, beakers, wash bottle.
Reagents: Deionized water, water sample, standard 0.1N silver nitrate solution,
pH test paper, sodium hydroxide solution, nitric acid, Indicator potassium
chromate solution.

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 Chloride in the form of chloride (Cl) ion is one of the major inorganic anions
in water and wastewater. The chloride concentration is higher in wastewater than
in raw water because sodium chloride is a common article of diet and passes
unchanged through the digestive system (Average estimate of excretion: 6 g of
chlorides/person/day; additional chloride burden due to human consumption on
wastewater: 15 mg/L). Along the sea coast chloride may be present in high
concentration because of leakage of salt water into the sewage system. It also may
be increased by industrial process. In potable water, the salty taste produced by
chloride concentration is variable and depends on the chemical composition of
water. Some waters containing 250 mg/L Cl may have a detectable salty taste if
sodium cation is present. On the other hand, the typical salty taste may be absent in
waters containing as much as 1000 mg/L when the predominant cations are
calcium and magnesium. In addition, a high chloride contents may harm metallic
pipes and structures as well as growing plants.
The measured chloride ions can be used to know salinity of different water
sources. For brackish water (or sea water or industrial brine solution), it is an
important parameter and indicates the extent of desalting of apparatus required. It
also interferes with COD determination and thus it requires a correction to be made
on the basis of amount present or else a complexing agent, such as HgSO 4 can be
added. Further, chloride ions are used as tracer ions in column studies to model
fate of different contaminants in soil and liquid media.

PROCEDURES:
1. Measure the pH of the water sample. Adjust the pH with nitric acid or
sodium hydroxide, if needed.
2. Take a 25 ml collected water sample into a conical flask.
3. Add 2-3 drops potassium chromate (K2CrO4) indicator. The color of the
water sample is turn into light yellow.
4. Add standard (normality: 0.0141N) silver nitrate solution from the burette
and shake well. Titrate until the light yellow color changes to permanent brownish-
red color (bricks-red color) precipitate with white color precipitate.
5. Note the volume of silver nitrate added.
6. Repeat the titration for concordant values.

Results of titration:
 Equivalent weight of Cl- ion: EqCl = ¿
−¿

 Volume of liquid sample solution for titration: Vsample = 10 mL

 Normality of standardized AgNO3 solution for titration: NAgNO3 =
 Volume of titrant consumed for titration: VAgNO3 =

Calculation:
Chloride ion concentration (mg/l): C ¿ ¿

Determination of Sodium chloride (salt content) in brine:

13
 Direct titration of NaCl in brine with standardized silver nitrate solution
based on the Mohr method is adequate for routine analysis.

Procedure:
Take 5 to 10 mg liquid portion from the drained weight determination. If it is
acidic, neutralize it with standard Sodium hydroxide using phenolphthalein as
indicator. Add 1 mL of 5% aqueous potassium chromate solution and titrate with
0.1 N AgNO3 solution to produce red-brown end point.
 Equivalent weight of NaCl: Eq NaCl =
 Weight of liquid saple solution for titration: msample = ______mg
 Normality of standardized AgNO3 solution for titration: NAgNO3 =
 Volume of titrant consumed for titration: VAgNO3 =

 Calculation: Equivalent weight of Cl- ion: EqCl = ¿ −¿

 Volume of liquid saple solution for titration: Vsample = 10 mL

 Normality of standardized AgNO3 solution for titration: NAgNO3 =
 Volume of titrant consumed for the 1st titration: V1AgNO3 =
 Volume of titrant consumed for the 2nd titration: V2AgNO3 =
 Volume of titrant consumed for the 3rd titration: V3AgNO3 =
V 1 +V 2 +V 3
 Average amount of titrant consumed for titration: V AgNO = ¿
=¿
3
3

Calculation:
V AgN O ∙ N AgN O ∙ 58,5
Sodium chloride concentration: W NaCl, %= 3 3
∙ 100 %
m sample ❑

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks

1. A mixture containing only KCl and NaBr is analyzed by the Mohr method. A
0.31720g sample is dissolved in 50 mL of water and titrated to the
Ag2CrO4 end point, requiring 36.85 mL of 0.1120 M AgNO 3. A blank titration
requires 0.71 mL of titrant to reach the same end point. Report the %w/w KCl
in the sample.
2. The %w/w I– ions in a 0.6712-g sample was determined by a Volhard titration.
After adding 50.00 mL of 0.05619 M AgNO 3 and allowing the precipitate to
form, the remaining silver was back titrated with 0.05322 M KSCN, requiring
35.14 mL to reach the end point. Report the %w/w I– in the sample.
3. In the Volhard titration of 25 mL of 0.05 M of AgNO 3 solution with 0.02 M
KSCN solution, calculate the molar concentration of Ag+ in the conical flask
solution after the following additions of titrant KSCN solution: (1) 30 mL (2)
at equivalent point (3) 100 mL. (Ksp (AgSCN) = 1.010-12)
4. The As in a 9.13-g sample of pesticide was converted to AsO43- and
precipitated as Ag3AsO4 with 50.00 mL of 0.02015 M AgNO3. The excess
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 Ag+ was then titrated with 4.75 mL of 0.04321 M KSCN. Calculate the % of
As2O3 in the sample.
5. 400 mg of butter was heated and some water was added. After shaking and
filtration, 10 ml 0.2 M AgNO3 solution, some HNO3, drops of Fe3+ solution and
some nitrobenzene were added to the filtrate. The excess Ag + in the aqueous
layer was titrated with 0.1 M NH4SCN standard solution. If the volume of
NH4SCN at the equivalent point was 15 mL. Calculate the percentage of NaCl
in the butter sample.
6. Calculate the concentration of salt in a soy sauce 5.0g of sample, which is
diluted accurately in 250 mL volumetric flask and its 10.25 mL aliquots of the
diluted sample are mixed with 25 mL aliquots of the 0.1025N silver nitrate
standard solution, and back titrated with an average of 14.6 mL of 0.1002N
ammonium thiocyanate standard solution.
7. A 0.32 g sample containing KCl is dissolved in 50 mL of water and titrated to
the Ag2CrO4 end point, requiring 16.9 mL of 0.1 M AgNO 3. A blank titration
requires 0.7 mL of titrant to reach the same end point. Report the %w/w KCl in
the sample.
8. The sulphide contents of 100 mL of a water sample was titrated with a standard
solution of 0.01 M AgNO3 according to the following reaction equation:
2Ag+ + S2- ↔ Ag2S
If the volume of AgNO3 solution at the equivalent point was 8.5 mL. Calculate
the concentration of H2S in the water sample.
9. 1.354 g sample of sodium nitrate contaminated with NaCl was dissolved in
small amount of water and filled to the mark in the 100 mL volumetric flask.
To titrate chlorides in 10.00 mL sample 35.70 mL of 0.01021 M AgNO3 was
used. What is the percent purity of the sample?
10.A 2.2380g sample of a mixture of NaCl and NaI was dissolved in 200.0 mL
and 25mL aliquots were titrated to endpoint, using fluorescein indicator with
an average of 24.8 mL. Further 25 mL aliquots were titrated, using
diiododimethylfluorescein indicator with an average of 10.3 mL. Calculate the
%w/w of each salt in the mixture.
11.50.0 mL aliquots of a bromide solution were titrated to endpoint with an
average of 12.3 mL of the silver solution which has been diluted accurately by
a factor of 10. Calculate the concentration of bromide in mg/L.
12.Calculate the percentage of silver in an ingot, if a 0.9023g sample was
dissolved in 100 mL and its 25 mL aliquots were titrated to endpoint with an
average of 17.9 mL of thiocyanate titrant.
13.A waste water sample from a gold processing plant is analysed for its cyanide
content by titration with silver nitrate. 50 mL aliquots of the sample are titrated
to endpoint with an average of 13.2 mL of silver nitrate, which has been diluted
five times. Does this sample contravene effluent regulations which limit
cyanide waste to 100 mg/L?

15
14.The organic matter in a 3.776-g sample of a mercuric ointment is decomposed
with HNO3. After dilution, the Hg2+ is titrated with 21.30 mL of a 0.1144 M
soln of NH4SCN. Calculate the percent Hg (200.59 g/mol) in the ointment.
15.What is the solubility of barium sulfate in pure water at 25 oC? (Ksp for barium
sulfate is 1.1 x 10-10)
16.Calculate the solubility product constant for pure PbSO4 in water. The
solubility of PbSO4 is 1.25 x 10-4 mol/L.
17.The solubility of CaF2 is 2.1 x 10 -4 mol/L. Find the Ksp of CaF2.

Questions for test self-check

1. What is the role of chromate ions in chloride determination?
2. As potassium chromate is an oxidizing agent, what would happen to chloride
determination if the sample were consists of organic matter (say 100 mg/L
glucose) as well.
3. Why pH range is important in chloride determination?
4. Would the analytical results by the Mohr method for chlorides be higher, lower
or the same as the true color value if any excess of indicator were accidentally
added to the sample? Why?
5. What is the solubility constant expression for: a) Zn 3(PO4)2; b) Ag3PO4, c)
Mg(OH)2?
6. In most titrations it does not really matter which solution is in the burette and
which is in the flask. However with Mohr’s method, it is critical that the silver is in
the burette and not in the flask. Explain why.
7. Why is a blank used in Mohr’s method?
8. What indicator would be suitable to analyse the concentration of iodide in the
presence of chloride?
9. How would you analyse the salt content of a sauce which contains a significant
level of ethanoic acid?
References:
1. Harris, Daniel Charles (2003). Quantitative chemical analysis (6th ed.). San
Francisco: W.H. Freeman. pp. 142–143.
2. James R. Fromm (1997). Precipitation Titrations
3. Yoder, Lester (1919). "Adaptation of the Mohr Volumetric Method to
General Determinations of Chlorine". Industrial & Engineering
Chemistry 11(8): pp.75.
4. Skoog D. A.; West D. M.; Holler F. J. Fundamentals of Analytical
Chemistry, 7th Edition, Thomson Learning, Inc, USA, 1996.
5. Sheen R.T. and Kahler H. L. Effects of Ions on Mohr Method for Chloride
Determination, Ind. Eng. Chem. Anal. Ed.; 1938; 10(11); 628-629.
6. Kraemer E. O. and Stamm A. J. Mohr’s Method for the Determination of
Silver and Halogens in other than Neutral Solutions, J. Am. Chem. Soc.;
1924; 46(12); pp. 2707- 2709.
7. Nielsen, Suzanne. Sodium Determination Using Ion Selective Electrodes,
Mohr Titration, and Test Strips. Chapter 10. Food Analysis Laboratory
Manual. 2nd Edition. USA: Springer. 2015
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