Precipitation titration

1. 1. Precipitation titration By
2. 2. Definition • A special type of titremetric procedure involves the formation of
precipitates during the course of titration. The titrant react with the analyte forming an
insoluble material and the titration continues till the very last amount of analyte is
consumed. The first drop of titrant in excess will react with an indicator resulting in a
color change and announcing the termination of the titration.
3. 3. • Quantitative precipitation can be used for volumetric determination. • The
titration involves precipitation are called precipitation titrations • Two type • Direct •
Indirect
4. 4. Reaction must satisfy this condition • Precipitate must be practically insoluble. •
Precipitation must be rapid. • Possible to detect equivalent point. • Method based on
precipitation of insoluble silver is known as Argentiometry. • Halogens can be
determined by precipitation as sparingly soluble mercurous salts HgCl2 and HgI2 is
called as mercurometry.
5. 5. Solubility product • Solubility product is the product of the concentration of ions in
the saturated solution of a sparingly soluble salt as AgCl is constant at a given
temperature.
6. 6. • When the ionic product exceeds the solubility products the solution is super
saturated and precipitation will occur. • When the ionic product is less than the
solubility product the solution is unsaturated. • In quantitative analysis excess
precipitating agent is always employed to ensure complete precipitation.
7. 7. • If little excess of H2SO4 is employed, the ionic product far exceeds the solubility
product and there is complete precipitation. • Oxalic acid cause complete precipitation
of calciumoxalate from solution of calcium acetate but not from calcium chloride and
calcium nitrate.
8. 8. • Acetic acid is a weak acid than oxalic acid thus it does not suppress the
dissociated oxalic acid. The concentration of oxalate ion is sufficient to keep ionic
product greater than solubility product of calcium oxalate. • In case of calcium
chloride HCl is formed which is strong acid and highly dissociated. It suppresses the
dissociation of oxalic acid by common ion effect. • The oxalate ion concentration falls
below the value required to exceed the solubility product of calcium oxalate. • The
precipitation is therefore incomplete. • This explains why calcium oxalate dissolves in
HCl but not in oxalic acid.
9. 9. Effect of acid upon the solubility of a precipitate • Sparingly soluble salt of a strong
acid, the effect of the addition of acid will be similar to that of any other indifferent
electrolyte but if the sparingly soluble salt of weak acid will have solvent effect upon
it.
10. 10. Effect of temperature upon solubility of a precipitate • The solubility of the
precipitate encountered in the quantitative analysis increases with rise of temperature
is small but with other it is quite appreciable. • The solubility of silver chloride at 10
C and 100 C is 1.72 mg and 21.1 mg respectively. • In case of barium sulphate at
these two temperature is 2.2 and 3.9 mg respectively.
11. 11. • Where ever possible it is advantageous to filter while the solution is hot; the rate
of filtration is increased. • The solubility of foreign substances, thus rendering their
removal from the precipitate more complete.
12. 12. Effect of solvent upon the solubility of the precipitate • The solubility of most
inorganic compound is reduced by the addition of organic solvent such as methane,
ethanol, propanol and acetone • Addition of 20 % ethanol renders solubility of lead
 sulphate negligible thus permitting quantitative separation. • Similarly calcium
sulphate a separates quantitatively from 50 % ethanol.
13. 13. Types Mohr’ method Volhard’s method Fajan’s method
14. 14. Mohr’s method Karl Friedrich Mohr (1806-1879)
15. 15. • In 1856 Mohr introduced it. • Determination of halide – chloride with silver
nitrate using potassium chromate solution as indicator. • It is especially useful for the
determination of chloride. • Precipitated silver chromate, through sparingly soluble in
water is more soluble than silver chloride and the red color due to silver chromate
does not appear until all the chloride has been precipitate as silver chloride
16. 16. • The sensitivity of indicator depends on concentration, temperature H+ ion
concentration, concentration of electrolyte and manner of observing the red coloration
17. 17. • This method utilizes chromate as an indicator. Chromate forms a precipilate with
Ag+ but this precipitate has a greater solubility than that of AgCl, for example.
Therefore, AgCl is formed first and after all Cl- is consumed, the first drop of Ag+ in
excess will react with the chromate indicator giving a reddish precipitate. 2 Ag+ +
CrO4 2-  Ag2CrO4
18. 18. Precaution • In this method, neutral medium should be used since, in alkaline
solutions, silver will react with the hydroxide ions forming AgOH. In acidic solutions,
chromate will be converted to dichromate. Therefore, the pH of solution should be
kept at about 7. There is always some error in this method because a dilute chromate
solution is used due to the intense color of the indicator. This will require additional
amount of Ag+ for the Ag2CrO4 to form.
19. 19. Limitation • Allowable PH range is 6.5 to 10 . • Below PH 6.5 there is increased
in solubility of silver chromate . • above PH 10 the end point comes too late and
Silver hydroxide is also precipitated. • If the solution is alkaline make it acidic with
nitric acid then neutralise it by adding sodium bi carbonate or borax
20. 20. Limitation • If appreciable amount of Ammonium salts are present the PH should
not exceed 7.2. • In reverse titration iodides and bromides cannot be titrated.
21. 21. Preparation of 0.1 M silver nitrate – weigh 17 g of silver nitrate dissolved it in
1000 ml of distilled water • Weigh accurately 0.1 g of sodium chloride dissolve in 5
ml of water, 5 ml of acetic acid , 50 ml of methanol, 0.15 ml of eosin stirr preferably
with magnetic stirrer and titrate with silver nitrate. End point appearance of pink
colour [ Rose milk colour ]
22. 22. Volhard Method : Jacob Volhard (1834-1910)
23. 23. • In 1874 volhard designed the method of estimation of silver ions [ AgNO3 ] in
dilute acid solutions by titrating against a standard thiocyanate solution in the
presence of ferric salt [ Ferric ammonium sulphate ] as indicator. • It has been
extended to estimate chloride, bromide and other several analysis.
24. 24. • Ammonium or potassium thiocyanate solution is used in conjunction with 0.1 M
AgNO3 in the assay of substances which react with nitrate but which cannot be
determined by direct titrations with silver nitrate solution. • In this method to the
halide solution, a known excess of silver nitrate is titrated with 0.1M ammonia or
potassium thiocyanate solution is called Volhard’s method. • In this method the
precipitate of Silver chloride is filtered off and the filtrate is titrated with standard
thiocyanate solution using ferric ammonium sulphate solution as indicator. At the
endpoint a permanent red colour is produced due to the formation of ferric thio
cyanate.
25. 25. • This is an indirect method for chloride determination 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 untill a red color is obtained
which results from the reaction: Fe3+ + SCN-  Fe(SCN)2+
26. 26. 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.
27. 27. Removal of precipitate of silver chloride • The reason for removing the precipitate
of silver chloride react with thiocyanate SCN to form the change in Titre value . • In
determination of iodide and bromide is not needed because the reaction is negligible.
28. 28. Modified volhard’s method cold well’s method • Especially NaCl or KCl are
determined. • In case of chloride it is usual to filter of the silver chloride or coagulate
the precipitate by means of either dibutyl phthalate preferred or nitro benzene. • The
excess of silver nitrate is back titrated with potassium or ammonium thiocyanate using
ferric alum as indicator.
29. 29. • The nitro benzene or dibutyl phthalate is added to coagulate the silver chloride
precipitate so that it will not interfere with the titration of excess of silver nitrate by
forming a layer over silver chloride and this avoids the need for filtration. •
Preparation of 0.1 M Ammonium thio cyanate Dissolve 7.612g of Ammonium thio
cyanate in 1000ml of distilled water.
30. 30. Procedure • Pipette 30 ml of silver nitrate into a flask dilute with 50 ml of water,
add 2 ml of nitric acid, 2 ml of ferric ammonium sulphate solution and titrate with
ammonium thio cyanate solution to the first appearance of reddish brown colour.
31. 31. Fajan’s method Kazimierz Fajans (1887-1975)
32. 32. • In 1923-24 Fajan introduced the method • Adsorption indicator is used • The
action of these indicators are based on the simple fact that the endpoint the indicators
get adsorbed by the precipitate [ AgCl] and during the process of adsorption, a change
in colour of the indicator will takes place which may result in a substance of different
colour
33. 33. • 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. • Ag+ + FI-  AgF • Among these methods, the Volhard
Method is widely used because we can detect the end point of precepitation titration
very well.
34. 34. Limitations of Precipitation Titration  A few number of ions such as halide ions
(Cl- , Br-, l-) can be titrated by precipitation method.  Co-precipitation may be
occurred.  It is very difficult to detect the end point.
35. 35. Determination of endpoint • Formation of coloured precipitate • In mohr’s method
a small quantity of potassium chromate is added as indicator. At the end point the
chromate ion combines with silver ion to form the sparingly soluble red silver
chromate. • Silver chromate sparingly soluble in water but more soluble in silver
chloride.
36. 36. • The red colour does not appear until all the chlorides are precipitated. • In
determination of neutral halide 0.5 ml of 5 % w/v of potassium dichromate is used. •
In acid solution potassium di chromate cannot be used as indicator because of
solubility of potassium dichromate in acid. • Acid solution neutralised with chloride
free calcium carbonate and sodium bi carbonate. • Alkali is acidified with acetic acid
and slight excess of calcium carbonate.
37. 37. • The solubility of silver chromate is increased with temperature then the titration
must be performed at room temperature. • Formation of soluble coloured compound •
 It is exemplified by Volhard for titration of silver in the presence of free nitric acid
with standard potassium or ammonium thiocyanate solution. • The indicator is ferric
nitrate or ferric ammonium sulphate.
38. 38. • Addition of thiocyanate produces first a precipitate of silver thiocyanate • When
this reaction is complete, the slight excess of thiocyanate produces reddish brown
colour due to formation of complex. • It is applied to the determination of chlorides,
bromides and iodides in acid solution.
39. 39. When excess of silver has reacted, thiocyanate may react with silver chloride,
since silver thiocyanate is less soluble. It will takes place before the reaction occurs
with Iron III ions which cause titration error
40. 40. • It is necessary to prevent reaction between the thiocyanate and silver chloride. •
Silver chloride is filtered off before back titrating since at this stage the precipitate
will be contaminated with adsorbed silver ions. • The suspension should be boiled for
a few minutes to coagulate the silver and then remove the most adsorbed silver ions
from its surface before filtration. The cold filtrate is titrated.
41. 41. • After the addition of silver nitrate , potassium nitrate is added as coagulant the
suspension is boiled for about 3 minutes, cooled and then titrated immediately. •
Desorption of silver ions occurs and on cooling re adsorption is largely prevented by
presence of potassium nitrate. • An immiscible liquid is added to coat the silver
chloride particles and thereby protect them from interaction with the thiocyanate.
42. 42. • The most sucessful liquid is • Nitro benzene – 1 ml for each 50 mg of chloride •
Or • Dibutyl phthalate • The suspension is well shaken to coagulate the precipitate
before back titration.
43. 43. Adsorption indicator • At the equivalence point the indicator is adsorbed by the
precipitate and during the process of adsorption a change occurs in the indicator
which leads to a substance of different colour. Thus they termed as adsorption
indicator. • Eg • Fluorescein , Eosin, Tatrazine , Rhodamine
44. 44. AgCl precipitated in the presence of excess of Chloride ions AgCl precipitated in
the presence of excess of silver ions
45. 45. • If fluorescein will strongly adsorbed than the nitrate ion will reveal its presence
on precipitate not by its own colour, which is that of the solution. • Another view is
adsorption of fluorescein ion a rearrangement of the structure of the ion occurs with
formation of coloured substance.
46. 46. Fluorescein • Important dye with phthalein group • Condensing phthalic anhydride
with resorcinol • 0.2% solution of sodium salt of fluorescein in water/ alcohol • Fajan
and wolff recommended 1-2 drops of indicator for 10 ml of neutral 0.1 N halide • It is
rapidly decomposed by light. • It can be used for chlorides bromides iodides and
thiocyanate. O OHOH O O
47. 47. Dichloro fluorescein • It is weakly acidic solution. • Condensing phthalic
anhydride and mono chloro resorcinol. • 0.1 % solution in 70% alcohol or 0.1%
solution as indicator.
48. 48. Eosin • It is orange colour powder dye sparingly soluble in alcohol. Bromide,
iodide and thiocyanate even in dilute solutions may be titrated accurately. O O Br Br
Br Br OH OH O
49. 49. Phenosafranine • It is good adsorption indicator for titration of chloride and
bromide solution. • The dye is green crystalline product which dissolves in water to
give a bright red solution. • During the titration of chloride or bromide with silver
nitrate most of the indicator is adsorbed on the precipitate in its red form, at the
equivalence point the colour suddenly changes to blue.
50. 50. Phenosafranine • It is not useful in the pressence of sulphuric acid because of
bleaching effect on the colour. • Good results obtained only when halogen is present
in the ionic form. • Undissociated compounds such as chromic chloride and mercuric
chloride cannot be analysed by this procedure. The same is of course true of any
adsorption indicator method.
51. 51. Diphenyl carbazone • 0.2% alcoholic solution of diphenyl carbazone is used as
adsorption indicator. • In titration of chloride a colour change from bright red to violet
is obtained. • With bromide and iodide the change is from yellow to green and with
thiocyanate from pink to blue. • Since no color change is obtained in the presence of
acid. • An acid solution must be first neutralised.
52. 52. What types of drug are analysed by this method Carbromal. KCl Infusion.
NaCl Infusion Thiamine Hydrochloride
53. 53. Indicator of Precipitation Titration  Potassium Chromate (K2CrO4)  Silver
Chromate (Ag2CrO4)
54. 54. Thank you