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Laboratory Work Precipitation Titration
Laboratory Work Precipitation Titration
PRECIPITATION TITRATION.
MOHRS METHODS
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.
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;
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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 ¿
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
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
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.
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.
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
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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
Calculation:
The result is expressed as mol-eq/l concentration and based on the following
formula:
N AgNO ∙ Eq AgNO
T AgNO = 3 3
3
1000
N AgNO ∙ Eq NaCl
T AgNO / NaCl = 3
3
1000
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Initial point white ppt of AgCl End point of Titration
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.
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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.
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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 = ¿ −¿
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 ¿ ¿¿
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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 = ¿
−¿
Calculation:
Chloride ion concentration (mg/l): C ¿ ¿
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:
V AgN O ∙ N AgN O ∙ 58,5
Sodium chloride concentration: W NaCl, %= 3 3
∙ 100 %
m sample ❑
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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.