Gravimetric Analysis
Lecture
By
Dr. Shariq Syed
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Introduction to Gravimetry
(Gravi + Metry) = Weigh +measure
Suitable for
element weighing
We want to
detect these,
know how Transformation Pure
much they are Ion Stable If Not
form
Treat
Chemically
Radical
Pure
Stable
form
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Introduction to Gravimetry
Process of producing and weighing a compound or element in as pure
form as possible after some form of chemical reaction is carried out
Transformation of element, ion or radical into pure stable compound
which is suitable for direct weighing or
conversion to another form that can readily quantified
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Gravimetric Analysis
Classification based on how the substance to be measured is created
Substance either
Precipitated from
solution
Gravimetric
Analysis or volatized and
absorbed
Precipitation Volatisaton
Methods Methods
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
STEPS INVOLVED IN GRAVIMETRIC PRECIPITATION
Preparation of the sample solution
Precipitation process
Digestion (or) Ostwald ripening
Filtration
Washing
Drying
Igniting
Weighing
Calculation
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Precipitate Formation Stages
First step of precipitation
Solute/Analyte conc >> Equilibrium solubility
Super-
saturation Extent of super-saturation determines particle size, filtrability
Formation of more stable phase
Aggregation of ions/elements to form sub-micro nuclei
Nucleation
Precipitation (Ppt) continues
Precipitate
Ion/elements added to nuclie leading to particle growth
Particle
Growth
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Factors determining successful Precipitation
Insoluble, No appreciable
loss on filtration
element
Physical Form such that
Ion Precipitated readily separated,
form washed free of impurity
Radical Can be converted to Pure
substance of definite chem comp
(Ignition or chem operation)
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Nature of Precipitate
Physical nature of Ppt will be determined by relative rates of nucleation and particle growth
Rate of Rate of
nuclei Particle
formation formation
Nature of
Precipitate
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Nature of Precipitate
Rate of Nuclei Rate of particle
Formation >> Formation
More number of nuclei formed
Smaller particle produced
Colloidal PPT formed (10 -7 10 -5 cm)
Adsorbs impurity
Increased chance of imperfection in the crystal & surface area of precipitate
increase this leads to easy trapping of impurities
Not easily filterable, do not settle
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Colloidal Precipitate
Solution to colloid formation
Rate of Nuclei Rate of particle
Formation >> Formation 1. Neutralise electrical double
2. Remove adsorbed ions by
heating/stirring
3. Process called coagulation or
agglomeration
- -
+ + + +
+ -+
+ + -
Colloidal Colloidal Colloidal
Particle Particle Particle +
+ + -
+ - AgCl surrounded
+ + + + by Ag or Cl ions
- -
Electrovalent colloids Double layer
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
attract common ions stabilized colloid
Relationship between particle sizes &
supersaturation
Von weimarn discovered that
Particle size of precipitate is inversely proportional to the relative super-saturation of
the solution during the precipitation process
(Von weimarn ratio) Relative supersaturation = (Q-S)
S
Q- concentration of mixed reagents before precipitation occurs(Degree of supersaturation)
S- solubility of precipitate at equilibrium
So in order to get particle growth instead of further nucleation we need to make
the relative super-saturation ratio as small as possible
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Relationship between
super-saturation & Nucleation
High relative supersaturation Low relative supersaturation
Increase nucleation Less nucleation
Many small crystals Fewer larger crystals
Colloidal particles form Crystalline particles form
High surface area Low surface area
More adsorption of impurities Less adsorption of impurities
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Nature of Precipitate
Rate of Nuclei Rate of particle
Formation << Formation
Coarse PPT formed
Particle diameter >10 -3 cm)
easily filterable
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Contamination of Precipitates
Post Precipitation:
Deposition of impurity after ppt
Ex. Ca-oxalate ppt in presence of Mg ions
After some time, Mg-oxalate formed, deposits on Ca-oxalate surface
Can be avoided by filtering within 1 2 hrs after ppt
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Contamination of Precipitates
Co-precipitation:
Inclusion of impurity during ppt formation
Adsorption:
Adsorption of impurities at surface
More for colloidal particles
PPt have to be washed to remove adsorbed impurity
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Contamination of Precipitates
Co-precipitation:
Inclusion of impurity during ppt formation
Mixed crystal contamination:
Substitution of impurity ions in cryst lattice
Impurity ions have similar crystallinity
Ex, Ppt of Ba as BaSO4 in presence of Pb ions
Separate analyte from contaminating ions before ppt
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Contamination of Precipitates
Co-precipitation:
Occlusion occurs when foreign ions get trapped in growing crystal
Mechanical Entrapment:
several crystals growing together come close
Traps portion of solution between pockets
Both occlusion and entrapment are at minimum when rate of ppt is low
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Solutions to problems in gravimetry
Process carried out in dilute solution
Reagents mixed slowly with constant stirring
Ppt carried in hot solutions if stability permits
Advantages of heating
Solubility increased, reduction in degree of supersat
Coagulation occurs
Velocity of crystallization increased
Crystalline ppt digested as long as possible
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Solutions to problems in gravimetry
PPt should be washed with dilute solution of electrolyte
If contamination high, re-dissolve in appropriate solvent & then rePPT for
purity
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Solutions to problems in gravimetry:
Digestion of precipitate
Digestion is a process keeping the precipitate within the
mother liquor (or solution from which it precipitated) for a
certain period of time to encourage densification of nuclei.
During digestion, small particles dissolve and larger ones Ostwald ripening improves the
purity and crystallinity of the
grow (Ostwald ripening). precipitate
This process helps produce larger crystals that are more
easily filtered from solution
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Precipitation Reagents
Mostly precipitation reagents are organic
Advantages of organic reagents
PPT products sparingly soluble
Colored
High molecular masses, so more ppt
Ideal reagent for precipitation should be specific, only ppt a specific ion
Precipitation product dried, weighed
If composition not definite then oxidised
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Applications
Assay of Nickel by Dimethylglyoximate (DMG):
1. Equation: Ni2+ + 2H2DMG = Ni(HDMG)2 + 2H+
Characteristic bright red ppt
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Applications
Assay of Nickel by Dimethylglyoximate (DMG):
1. DMG insoluble in water, added as 1% solution in 90% ethanol
2. 1 ml ppt 0.0025g of nickel
3. Reagent added to hot acidic solution of nickel salt
4. Only slight excess of reagent should be used
5. PPT washed with cold water, dried at 110-120 0C
6. Equation: Ni2+ + 2H2DMG = Ni(HDMG)2 + 2H+
For detailed process please refer to Vogel, pp 408
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Applications
Assay of Aluminium by Oxine (8-hydroxyquinoline):
Separates Al from beryllium & other earth metals
2 or 5 % solution of Oxime in 2M Ethanoic acid Al
1 ml sol can ppt 3 mg of aluminium
Procedure
1. Dissolve 0.4 g of Al ammonium sulphate in 100 ml of
water
2. Heat to 70 80 0C
3. Add appropriate volume of oxime reagent
4. Keep adding reagent to ensure complete ppt
5. Allow to cool, collect Al-oxinate
6. Wash with water, dry to constant weight at 110 0C
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014 Al-oxinate
Applications
Assay of Barium as Barium sulphate:
Slow addition of dilute solution of BaCl to hot solution of sulphate
Ba2+ + SO42- = BaSO4
Acidic solution prevent other salts formation (Chromate, carbonate,
phosphate)
Process carried out at boiling temp for lower supersat
Ba has strong tendency to carry down other salts
Barium chloride, Barium nitrate are co-precipitated
Nitrate can be converted to oxide by ignition
Slow addition of Ba to SO4 solution lowers formation of BaCl
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
Advantages & Disadvantages
Advantages
Extensive numbers of inorganic ions are determined with excellent
precision and accuracy.
Routine assays of metallurgical samples
Relative precision 0.1 to 1%
Good accuracy, relatively in-expensive
Disadvantages
Careful and time consuming
Scrupulously clean glassware
Very accurate weighing
Co-precipitation
AIKTC/SoP/S.Y.B.Pharm./Sem.IV/2014
