A precipitation titration reaction occurs when solutions of two different ionic compounds are mixed and an insoluble solid separate out of solution that insoluble solid is known as a precipitate.
where AgCl = precipitate
where AgCl =precipitate
-In precipitation cation comes from one solution and anion from another hence precipitation is itself ionic.
-The fall under the category of determining the endpoint by the formation of coloured precipitate and is used for the determination of chlorides and bromides is a neutral solution.
– TITRANT:- AGNO3 ( SECONDARY STANDARD SOLUTION)
-INDICATORS:- 5% POTASSIUM CHROMATE K2CRO4)
which forms reddish-brown precipitate.
-Determination substance:- chloride, bromide
-PH range — 6.5 to 10.3
-iodides cant be determined by mohrs method because I- will also produce coloured precipitate with Ag+
the reaction is carried out in neutral medium for determination of Cl- & Br –
-Titration of 0.1 M NaCl by using 0.1M AgNO3 in the presence of K2CrO4
-AgNO3 (0.1M standard ) will be added from the burette into the solution containing NaCl & indicator ( K2CrO4)
-AgCl appears 1st because of concentration of Cl- ion is much higher as compared to
-At the endpoint all Cl- ions react with AgNO3 & form AgCl, after that addition of extra deep of AgNO3 leads to reacting with ion ( from indicator ) & it will form reddish-brown ppt of AgCrO4.
-At the endpoint reading is taken & cl ion concentration is determined.
-It is impossible to use titration in acidic solution otherwise it will produce silver hydroxide
-it is impossible to use titration in the presence of ammonia ions ( due to ligand formation)
-it is impossible to use titration in the presence of reducing which reduces chromate ions
– it is impossible to use titration in the presence of many anions ( etc ) which gives the painted precipitate of silver ions.
VOLHARD METHOD AND MODIFIED VOLHARD METHOD
-In this method formation of a soluble colour compared at the endpoint.
-it is used to determine halogenides , thiocyanates, cyamides, sulphides, chromate, oxalates, carbamates.
-it is a back titration method, so two titrants is used.
type 1 – standardized AgNO3
type 2 – KSCN OR NH4SCN
INDICATOR; Iron alum/ ferric ammonium sulphates
STEP 1; Standardization of AgNO3 by 0.1N NaCl
STEP 2; determination of analyte i.e. KCl
where, AgCl=precipitate, AgNO3=excess
In this reaction, AGNO3 is used in excess amount because of that reason the excess of AGNO3 remains in a reaction as it is after the formation of a precipitate (AGCH)
that excess AGNO3 used in next reaction
Then remain SCN i.e excess SCN react with
(REDDISH COLOUR END POINT)
1.take 0.1N NaCl standard solution in a conical flask, add 1 ml K2CRO4(5% SOLUTION) and titrate with AgNO3 solution.
2.at endpoint reddish brown/brick red colour ppt will form. reading will be taken and calculation will be done.
3.take sample solution (i.e. 10ml KCl ) & add an excess of standardized 0.1 N AgNO3 solution then add few drops of iron alum indicator solution.
4.titrate the above solution by using a standard solution of KSCN/NH4SCN (0.1N)
5.at the endpoint reddish colour precipitate of Fe(SCN)2+ will occurs due to completion of the reaction.
6.calculate the amount of KCl
-volhards method is carried out in acidic medium only because in basic medium Fe3+
may give Fe(oh)2
MODIFIED VOLHARDS METHOD
-step 1 is a common same as volhard method.
-chloroform /nitrobenzene or other wetting agents is added after addition of AgNO3 in step 2.
-these agents will form a layer surrounding the precipitate of AgCl prevents solubility of AgCl.
-K FAJONS introduced this method.
– K fajon introduce a useful type of indicator for precipitation titration.
-such indicators are adsorbed on the surface of the precipitation at the equivalence point and this absorption is accompanied by a colour change.
-types of indicators are as follows.
1.acid dyes eg, fluorescein, eosin etc,
2.basic dyes eg, rhodamine series
titrant – AgNO3 ( SECONDARY STANDARD SOLUTION ) so standardization a primary standard solution of NaCl (by measured volume)
medium :- PH- 6.5 -10.3 (FOR CHLORIDE)
PH- 2.0-10.3 (FOR BROMIDE AND IODIDE)
INDICATORS – dichlorofluorescein ( for chloride)
Eosine ( for bromide & iodide)
mechanism of indicator action
-the property of colloidal precipitate to absorb its own ions which are in excess is made use of the case.
-when a NaCl solution is titrated with AgNo3 the AgCl precipitate will absorb chloride ions which are initially in excess.
-this the primary adsorbed layer will be formed by chloride ions, which is taken will hold the secondary adsorbed layer of oppositely charged Na+
-at the equivalence point, Ag+ ion in excess & hence Agcl ions adsorb Ag+ ion as primary adsorb layer & No3 as secondary adsorb layer.
-now if the Na+ salt of fluorescein is also present in the solution then the -ve charged fluorescein ions would be adsorbed instead of NO3- as secondary layer & this adsorption occurs along with a change to pink coloured complex of Ag & fluorescein ions.
ESTIMATION OF NACl
(INDICATOR) (REDDISH BROWN / COLOURED PPT)
PREPARATION OF COLOURED REAGENTS
1.prepartion of 0.1N AgNo3
16.99 gm AgNo3= dissolved in 1000ml of distilled water.
2.prepartion of 0.1N NaCl
5.84 gm of NaCl = dissolved in 1000ml of distilled water.
3.preparation of 5% K2CrO4 indicator
5g of K2CrO4 =dissolved in 100ml of distilled water
STEP-1 Preparation & standardization of 0.1 N AgNo3
-take 10ml of 0.1 N NaCl, add 1ml of K2CrO4 indicator & titrate by using AgNo3 till the appearance of the reddish-brown colour precipitate.
-titration is done three or more times until we will not get precise reading (two or more reading should be same)
consider the reading are as follows
STEP 2. ESTIMATION OF NaCl
take 0.25g of NaCl & dissolve in 50ml of distilled water, add 1 ml of K2cro4 indicator & titrate against standardization AgNO3 solution till the appearance of reddish brown ppt.
let us consider
burette reading = 45ml
Sem 1 b pharm books of set
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