Topic 1: General Principles of chemical analysis

• Why we performs chemical analysis ?/ Purposes of performing chemical analysis

• 1.To know exact quality of substance in terms of component/ ingredients present in it
• 2.To know exact composition of all ingredients in given substance/ required ingredients
• 3.Identifying unknown substances 4.Separation of ingredients 5.For determining structures
• This is possible with or without instrument depends on situation of sample & requirements
CHEMICAL ANALYSIS
• Definition: Resolution of a chemical substances/ material into its proximate or ultimate parts
• Different types of chemical analysis may be classified as follows
• Types of Chemical analysis
• A) Purposes of analysis:
• Qualitative and Quantitative analysis
• Qualitative: Def: It involves Identification of elements present in sample/Analyte
• Quantitative: Def: It invoves determination of exact amount of each ingredients/element/components.
• B) Types of information required:
• 1. Proximate analysis: Determination of amount of each element no concern as to the actual composition.
• 2. Partial analysis: Determination of amount of Selected/ specific constituent/ element/ ingredient
• 3. Trace: Determination of trace element in sample. e.g In water analysis estimation of carcinogenic
constituent such as Pb, Hg etc. which are present in trace amount Possible by Instrument
• 4. Complete: Proportion of each component of the sample is determine.
• On the basis of size of sample there are 5 types of quantitative analysis
• 1.Macro: size/ quantity of sample > 0.1 gm
•
2.Meso (semi micro) :size/ quantity of sample between 10 -1 to 10 -2--- 0.1 to 0.01 gm
• 3.Micro: size/ quantity of sample between 10 -2 to 10 -30.01 to 0.001gm
• 4.Sub micro: size/ quantity of sample between 10 -3 to 10 -4 0.001 to 0.0001 gm
• 5.Ultra micro:size/ quantity of sample below 10 -4gm
• On the basis of Method used for qualitative and quantitative of analyte, analysis is
• 1.Qualitative & 2.Quantitative analysis
• Qualitative of two types 1Semi Qualitative 2.Organic spotting
There are two Types of Quantitative Analysis
1. Non Instrumental methods of analysis. This is also called Classical method of analysis
There are two types : 1.Volumetry & 2. Gravimetry
a) Volumetry: Def: Quantitative analysis involving determination of quantity of analyte in terms of volume of
standard reagent reacted chemically with it.
On the basis of chemical reaction taking place during it they are further classified as
1. Neutralization/ Acid –Base titration
2. Redox/ Oxidation- Reduction Titration
3. Iodometric titration
4. Precipitation Titration
5. Complexometric titration
b)Gavimetry: Def: Qquantitative analysis involves, determination of ion/ element/ component/ingredients
by accurately weighing it into desirable compound having definite chemical composition.
Types: Precipitation gravimetry, Electro gravimetry, Volatilization gravimetry , Particulate gravimetry,
Thermogravimetry & Organic precipitation gravimetry
2. Instrumental methods of analysis. Here Quantity of analyte measured by measurement of appropriate
electrical properties (potentiometer) or measurement of optical properties ( absorption/ emission/ transmittion
spectra) in some cases measurement of combination of electric and optical (amperometric titration)
Electrical method of analysis: i) Voltammetry: measurement of current at a micro electrode at a specific voltage
2.Coulometry: : measurement of current and time needed to complete an electrochemical reaction
3. Potentiometry: measurement of potential of an electrode in equilibrium with an ion to be determine
4. Conductimetry: measurement of the electrical conductivity of a solution
Optical method of analysis: 1. Measurement of the amount of radiant energy of a particular wavelength
absorbed by the sample 2. Emission of radient energy emitted 3.Absorption may be Visible/ UV and IR
spectroscopy. On the basis of amount of light stopped or scattered by a suspended particles Turbidimetric and
Nephelometric analysis. Instrument like pH Meter Colorimeter/Spectrophotometer Conductometer, UV,IR,NMR,
Mass, Chromatography, etc
Quantitative: 1. Flame photometry: Used in inorganic chemistry to determine the conc. Of metal ion
 2. AAS: Atomic absorption spectroscopy: Determine metal elements using absorption of optical
radiation by free atom in gaseous state.
3. UV-Visible spectroscopy: Measured absorption of light in visible region.
4. EDAX: Energy dispersive X-ray : used for elemental analysis from X ray emitted by the matter in
response to being hit with the EMR.
Structure: 1.IR: Change in vibrational energy leads change in the dipole moment between atoms of molecule.
2. NMR: Many nuclei having spin & all nuclei are electrically charged if external magnetic field is
applied energy transfer is possible between the base energy to a high energy level.
Structure Solid: X ray Diffraction
Separation from complex mixture: Chromatography
Study of Surface morphology by microscope: 1. SEM(Scanning electron Microscope) Electron beam interact with
sample producing secondery electron, back scattered electron,
Auger electrons and can be converted to surface tropograpy image.
2. TEM(Transmission electron Microscopy) When beam of electron
passing through thin specimen electron are scattred after
interaction with atom. It is used to study the growth of layer,
composition and defects in semiconductors.
3. AFM ( Atomic force Microscope) Cantilever/ Tip assembly scan the
surface.
Volumetric analysis
• Quantitative analysis involving determination of quantity of analyte in terms of volume of standard reagent
reacted chemically with it.
• Basic principle of this analysis based on following reaction.
aA + t T → Product
Where ‘a’ is molecules of analyte A
‘ t ’ is molecules of reagent T
• E.g. 1L 1N KMnO4 = 52 gm of Fe
• Terminology in volumetry
• Titration: Process of adding titrant in titrand till chemical reaction between them completed
• Titrant: The reagent of known concentration i.e. standard solution used during titrimetry is called titrant.
• The reagent of known concentration, from his known volume consumed for chemical reaction quantity of
analyte is measured.
• Titrand: The substance being titrated i.e. sample under test is called titrand
• Indicator: Auxillery Substance added during titration which indicates termination of reaction by physical
change just after completion of reaction. i.e. coluor, ppt etc is called indicator.
• Equivalence point:
• This is a stage in titration at where the titrant &titrand are chemically equivalence is called equivalence point
• Theoretical end point:This is a stage in titration at where the reaction between titrant &titrand is just
completed is called Theoretical end point
• Stoichiometric End Point:This is a stage in titration at where the titrant &titrand are stoichiometrically
equivalence is called Stoichiometric point
• Practical end point/End point:Point during titration at which, indicator show physical change in solution,
visible to analyzer is called end point or visual end point or practical end point
• Titration error: The difference between theoretical & practical end point is called titration error
•
Advantages of Non Instrumental methods over Instrumental methods
1. Procedures are rather simple and accurate.2. Methods are based on absolute measurements.
3. No need of special training as such.4. Required apparatus are easy to available with low cost.
Disadvantages of Non Instrumental methods over Instrumental methods
1. Procedures are time consuming.2. Some time chemical conditions are very critical.
3. Colored, Colloidal, Complex, Diluted & Poisonous samples cannot estimated.
4. Accuracy of result decreases withdecreasing sample under test
Advantages of Instrumental methodsover Non Instrumental methods
i) They are highly sensitive ii) Colored, Colloidal, Poisonous & complex sample can be handled with ease
iii) Small amount of sample can be easily detected iv) Time saving analysis
v) Measurements are more accurate & reliable.
Disadvantagesof Instrumental methodsoverVolumetry
i) Before analysis, Calibration of instrument is requiredii) Initial cost & maintenance cost required is high
iii) Special training as such is requirediv) Accuracy & reliability of result depends on reference used for their
calibrationv) Clean & sizable space is required vi) Limits of Concentrations is always their. (Permissive &
Excessive limits of concentration of each instrument)

Standards (During Titrimetry)

• Definition: Standards are chemical substances used in the form of standard solution which undergo chemical
reaction with analyte
• Classification: They are classified on the basis of its purity as Primary standards & Secondary standards
Primary standards
• Definition: These are substance used in chemical analysis, which are extremely /high purity & not affected by
any type of weathering conditions. Hence used directly to prepare their standard solutions called primary
standards OR These are chemical substance with highest purity and stability, used direly to prepare their
standard solution. OR Certain chemical substances used directly to prepare their standard solution.
Apart from purity other Characteristics of primary standards are as follows

Beside purity primary standards must fulfill following requirements

1. Availability: It should be easily available in pure & dry form at a reasonable cost
2. Stability: It should be stable i.e. easy to dry (not hygroscopic)i.e. They should not lose weight on expose to air
while weighting. Or If unstable, they looses their purity & become secondary standard.
3 Molecular weight: It must bear high Molecular Weight. This parameter important while preparing very dilute
solution e.g. 0.01N, 0.001N etc. In case of high concentrated solution weight of primary standard required must
be weighted errorless. Hence High mole.wt. Ensure errorless weighing while preparing dilute solution.
e.g. LiOH 23& EDTA 336 (If mol.wt. is low, small amount of sub. Cannot be weighted accurately)
4. Solubility: Readily soluble in common or available solvent
5. Purification: Highly pure if impure can be purified by simple purification method like evaporation.
6. Reactivity: Completely react with analyte through stoichiometric reaction. Rate of reaction can be increased by
stirring or by catalyst.
Acids: Potassium hydrogen phthalate.C6H4 (COOK)(COOH), Benzoic acid C6H5COOH, Constant boiling HCl
• Bases: Sodium carbonate Na2CO3, Mercuric oxide HgO, Borax Na2B4O7
• Oxidizing agents: Potassium dichromate K2Cr2O7, Potassium bromate KBrO3, Potassium iodite KIO3,
• Reducing agents: Sodium Oxalate Na2C2O4, Arsanious Oxide As2O3, (KI)Iodine I2
• Others: NaCl, KCl
Secondary standards
• Definition: These are the chemical substances used in the form of solution, only after standardization by
suitable standard solutions
• Example: NaOH hygroscopic, low purity
• Acids: HCl, HNO3, HClO4,Sulphamic acid (HSO3NH2)
• Bases: NaOH,KOH
• Reducing agents: Na2S2O3, KMnO4

Comparison between primary and secondary standards

Primary Secondary
Available always with High purity Not always available high purity
Stable in all types ofWeathering conditions May or May not stableWeathering conditions
Can be purified by simple Means Cant purifiedby simple Means
Uses Exact wt. to prepare Standard solution Uses appox. Wt. to prepare solution (not standard)
Preserved unaltered form for longer time May or may not
Std. Solution directly used in titrimetry Their solution used in titrimetry after standardisation
e.g Constant boiling HCletc e.g.HCl, NaOHetc
 CONCENTRATIONS OF SOLUTIONS
Terminology in Concentration:
• Solution: A homogeneous mixture of two or more different ingredients which are evenly distributed in each
other OR A homogeneous mixture of two or more different ingredients which are present on molecular level
OR A homogeneous mixture of two or more different ingredients which are uniformly distributed
• OR A homogeneous mixture of two or more different ingredients which are forming single phase
• Solute: A component of solution present in lesser proportion/minor proportion.
• Solvent: A component of solution present Greater proportion/major proportion.
• Dilute solution: Solution containing negligible amount of solute w.r.t. solvent
• Concentrated solution: Solution containing considerable amount of solute w.r.t. solvent
• Saturated solution:Solution containing maximum possible amount of solute w.r.t. solvent
• Conc. In % term: Amt of solute in term of direct % compared to mass/ volume of solution e.g. ppm/ mg/lit
etc.
• Conc. of solution: Amount of solute per unit mass/ volume of solution
• 1. Conc expressed in molar term: It uses amount of solute as no.of moles
• Molar concentration: Amount of solute is measured as no. of moles of solute
• Moles of solute: Amont of solute equal to its mole.wt. in gm
• No.of moles of solute= Act.wt. of solute/Mo.wt of solute i.e. n = W/M
• Molarity (M): Number of mole of solute present in one liter of solution is called Molarity.
Number of mole of solute
Molarity= ---------------------------------
Volume of solution in liters
• e.g. 0.1 M KCl is prepared by dissolving 7.45 gm of it in 1 liter water
Molality (m): Number of mole of solute present in per kilogram of solvent is called Molality.
Number of mole of solute
Molarity= -----------------------------------
Weight of solvent in kilograms
• e.g. 0.1 m KCl is prepared by dissolving 7.45 gm of it in 1 Kg of water
• Conc expressed in Normal terms
• It uses amount of solute as no of gm equivalence wt.
• Gr. Eq. wt.: Amount of solute equals to its Eq. wt in gm
• Normal conc.: Amount of solute is measured as no. of gm. Equivalent of solute
• No. of gm Eq. wt (e) = Actual wt of solute/ Its Eq. wti.e. e= W/E
Normality (N):Number of gram equivalent of solute present in one liter of solution is called Normality.
Number of gram equivalent of solute
Normality = ----------------------------------------------
Volume of solution in liters
• e.g. When 5.6 gm of KOH is dissolved in 1 liter of water prepared solution is 0.1 N
• When 9.8 gm of H2SO4 is dissolved in water up 1 liter prepared solution is 0.05 N
• Expression of concentration during titrimetry
• During titrimetric analysis expressing conc of std. solution is decided on the basis of types of chemical
reaction and stoichiometry
• 1. During titration If N=M for T & D, concentration expressed either Normal or Molar term
• E.g. May be either molar or normal term HCl + NaOH→NaCl + H2O
• During titration If N not equal to M for T & D, concentration expressed in Normal term only
• E.g H2SO4+2NaOH → Na2SO4 +2H20
• When complexing agent react with metal ions, it is always expressed in terms of mole.
• E.g EDTA + CaCaEDTA
Desire requirements of standard solutions
• Following are desire requirements of standard solutions
• 1.Have long term stability in solvent 2. React rapidly with the analyte 3. React completely with analyte
• 4. Be selective to the analyte
Numerical on Concentrations
• 1.Calculate the molarity of a solution of KOH if 11% KOH is prepared ( Mo. Wt. 56)
• Solution: 11% by w/v means 11gm in 100ml solution.
• M=n/V, n= W/Mol.wt, & V = 100/1000
• M= 11/56 X 1000/100 = 1.964M
• 2. How much (NH4)2SO4 is req. to prepare 400cc of M/4 solution (132.1)
• Amt of (NH4)2SO4req = Strength X Mol. Wt X vol. of solution in Lit
• = ¼ X 132.1 X 400/1000 = 13.21gm
• 3. How many gm Equivalence are contain in a) 1 L of 2N soln. b) 1 L 0.5N soln. c) 0.5 L 0.02N soln.
• 2gm, 0.5gm, 0.01gm equivalence
• 4. What is molarity of a solution containing 20gm Cane sugar in 125 ml DW
• ( C12H22O11=342)
• n = 20/342 & V = 125/1000, M = 0.468
• 5.Calculate normality of each of following a) 7.88gm HNO 3/lit & 26.5gm Na2CO3/lit ( MW63& 106)
• a) 7.88/63 = 0.12N & b) 26.5/53 = 0.5N
• 6. The molarity of a solution of ethanol (C2H5OH) is 3.6M at 250C. Calculate the molality of a solution.
Density= 0.95gm/cc
• 1 Lit C2H5OH = 950gm, 950gm soln. contains 3.6M C 2H5OH, Thus wt of C2H5OH in 950 gm sol = 46X3.6 = 165.5
gm, Hence wt of solvent = 950 – 165.5 = 784.4gm
• Therfore m = 3.6/0.7844 = 4.5895 m
• 7.How many gms of 5% by wt NaCl is required to get 3.2gm NaCl.
• 5% means 5gm in 100ml soln., for 3.2gm solnreq = 3.2 X 100/5 = 64ml
• 8. How many cc of 2M Pb(NO3)2 will conatin 600mg of Pb ( MW pb =208.5, Pb(NO3)2 = 331.2)
• 2M Pb(NO3)2 = 662.4 gm/lit = 417gm/lit only Pb, Therfore 1 ml soln = 417mg of Pb, Therefore 0.6gm of Pb =
0.6/0.417 = 1.4388ml solution
• 9.Calculate molarity,Normality of 29.5% H2SO4(v/v) having density 1.216gm/cc (MW98.08)
• Wt of 29.5% H2SO4 = 29.5 X 1.216 = 35.872 ∆ n = W/M = 35.872/98.08 = 0.3657
• TF M = n/ Vol.in Lit = 0.3657/100 X1000 = 3.0657M,
• M = 3.0657/ (1.216-0.3587) = 4.266m
• 10. Calculate purity of Conc H2SO4 (1.8gm/cc) if 5.3 ml of it is neutralized by 84.6 ml of 2N NaOH
• 1N 1L NaOH = 40gm,2N 1L NaOH = 80gm, 84.6ml 2N NaOH = 6.768gm TF Eq. of NaOH = 6.768/40 = 0.1692,
HencEq of H2SO$ = 1.692 X 49.04 = 8.2975, Density of H2SO4 is 1.8 TF wt of 5.3 ml of H2SO4 is 9.54gm TF
Purity = 8.297 X 100/ 9.54 = 86.97
• Compute the volume of Conc. HNO3 having density 1.3748 gm/cc & containing 63% acid required to
prepared 15 Lit of 0.125N solution (MW 63)
• Normality = 13748 X 0.63 / 63 = 13.748 N
• N1V1 =N2V2, 13.748 X V1 = 15 X 0.125 = 0.13638Lit = 136.38ml
• 12.How many kg of wet NaOH containing 12% Moisture(H2O) are required to prepare 60 L of 0.5 N solution
1L 0.5 N NaOH solution= 0.5 X 40 = 20 gm thus 60 L 0.5 N = 20 X 60 = 1200gm = 1.2 Kg

12% Moist NaOH Means, 88gm of pure NaOH is present in 100gm wetNaOH

• Thus 1.2 X 100/88 = 1.36Kg of 12% wet NaOH required.13.Given the unbalanced equation
• 13. KMnO4 + KI + H2SO4 → K2SO4 + MnSO4 + I2 + H2O
• How many gram KMnO4 is needed to make 500cc 0.25N solution
• How many gm KI is needed to make 25 cc of 0.36N solution
• In this reaction OS of Mn changes from +7 to +2 hence eq. wt is = 158/5 = 31.6 gm
• Hence Wt. required = 0.5 X 0.25 X 31.6 = 3.95gm is required
• In this OS , Iodine changes from -1 to 0 hence mole.wt = eq. wt
• Hence weight req = 0.025 X 0.36 X 166 = 1.49gm
• 14.To what extent must a 0.5M BaCl2 solution be diluted to yield 20 mg Ba++/CC (Ba-137.3)
• Original solution contain 0.5 mole Ba++/L i.e 137.3/2 = 68.6 mg/cc
• C1V1 =C2V2, 1X 68.6/20 = 3.43 i.e each CC of OS diluted to 3.43 cc then each CC = 20mg of Ba++
15. Exact 4 gm solution of H2SO4 was diluted and excess of BaCl2 is added. The dried ppt of BaSO4 weighted
4.08gm. Find % of H2SO4 in original solution. ( Molewt H2SO4 = 98.08, BaSO4 = 233.4)
• H2SO4 + BaCl2 → BaSO4 + 2HCl,
• Mass of H2SO4 to get 4.08gm BaSO4 is =(4.08/233.4)X 98.08 = 1.72gm
• H2SO4 by weight = Mass of H2SO4/Mass of solution = 1.72/4 = 0.43 , % of H2SO4 = 0.43 X 100 = 43%
 Requirements of chemical reactions during volumetric analysis
a) Reaction must be simple & can be easily represented in the form of chemical equation HCl + NaOH → NaCl +
H2O Due to this quantitative relationship between reactant & product can be easily establish
b) The reaction must be sufficiently fast. High velocity/rate of reaction ensure errorless calculation of quantity
of analyte./ The std. reagent & analyte instantly form the product.
c) The reaction must be stoichiometric: For non-stoichiometric reaction it is not easy to establish quantitative
relationship bet. Reactant & product. HCl + NaOH → NaCl + H 2O is stoichiometric reaction
1M 1M1M1M
d) Their must be a suitable physical change (Colour,turbidity) in solution as soon as reaction completed.
e) Suitable reagent (Indicator) must be available to bring required physical change on completion of reaction.
Types of volumetric analysis
• Volumetric analysis classified on the basis of the nature of chemical reactions taking place during titrations.
• Acid Base titration
• Oxidation Reduction Or Redox titration
• Iodometric titration
• Precipitation titration
• Complexometric titration

1. Acid Base titration (Neutralization titration)

• Principle: It involves reaction between acid / base, with Standard Base/ Acid result formation of salt & water.
Here pH of mixture changes& approaches to 7 hence is called as neutralization titration or acid base
titration.
HA + BOH → AB + H 2O
Acid Base Salt Water
Uses: Use to determine strength of acids and bases
Objective: To determine exact volume of standard acid/base consume towards complete neutralization of
analyte present in known volume of sample
Acid Base reaction
HCl + NaOH→NaCl + H2O
Basic requirements: Standard acid/base, Suitable acid-base indicator.
Types of Acid Base titration
• On the basis of Std. soln taken in burette during acid base titration we have two types
• 1. Acidimetry:
• The neutralization reaction between analytebase& standard acid is called as acidimetry titrations e.g.
Alkalinity of water sample.
• 2. Alkalimetry:
• The neutralization reaction between analyte acid & standard base is called as alkalimetry titrations. E.g. Acid
value of an oil.

,
Indicator for acid base titrations :Acid Base indicators are certain organic weak acid or bases undergoes
visible colour change within specific pH range.(Def)
Criteria for good Acid Base indicators:1.They are organic compound of either weak acidic or basic in nature.2. They
are freely soluble & easily available3. They are non toxic in nature.4. It must not chemically react with analyte. i.e
sufficiently weak & not consuming analyte . 5. It undergoes visible colour change in definite pH range only.6.
Theirmust be sufficient colour contrast before & after Equivalence pt.7. Selection of indicators for different types of
acid base titration done by knowing pH range at Eq. pt.
Acid Base or Neutralization Type indicator: Def: Acid Base indicators are weak organic acid or bases which are
sensitive to concentration of H + & OH - e.g. PP. MO, MR

• .Applications of Acid Base titrations: 1.Determination of strength of acid base samples. 2.Determination of
Drug samples 3. Determination of caustic soda. 4. Determination of acidity & alkalinity of water samples.
• 5. Determination of Saponification value & Acid value of an oil sample. 6.Estimation of nitrogen by Kjeldahls’s
method.
2.Oxidation Reduction Titration or Redox titration
• Principle: In involves reaction between analyte Oxidizing/ Reducing agents with standard reducing/ oxidising
agents , result simultaneously exchange of electrons between them.
• Uses: To determine metal ions/ wide range of Inorganic analyte, electrically charged species, oxidation
reduction reactions, electrochemical reactions.
• Objective: To determine exact volume of standard reducing/ oxidising agent required to carry out reduction/
oxidation of anlyte present in known volume of sample using suitable/ self indicator.
Redox reaction
• When two suitable oxidizing & reducing agents are brought together, complete reaction is sum of
two half reaction
2Fe3+ +2e- → 2Fe2+ (Oxidation)
Sn2+ → Sn4+ + 2e- (Reduction)
______________________
2Fe 3+ + Sn2+ → 2Fe 2+ + Sn4+ (Redox reaction)
Requirements: Standard reducing/ oxidizing agent, Sitable Redox indicator.
Redox type Indicator: Def: These are generally organic compound, either Oxidizing or Reducing form, shows
different color within definite potential range
Application of Redox titrations: 1.Determination of COD in waste water K2Cr2O7 as oxidizing
agent.2.Estimation of ferrous &ferric iron present in given solution. 3. Determination of chromium in
chromate ore. 4.Estimation of calcium in lime stone by forming calcium oxalate by KMnO45.Estimation of
manganese dioxide in pyrolusite.

Iodometric Titration:
It is integrated part of Redox titration.
The reduction of free iodine to iodide ion and oxidation of iodide ion to free iodine occurs in these titrations

I2 + 2e- → 2I- (Reduction)

2I-→ I2 + 2e- (Oxidation)

Principle: Titration in which amount of analyte determine on the basis of the amount of reduction of free
iodine to iodide ion or oxidation of iodide ion to free iodine is Iodometric titrations.

These titrations are divided into two types

Iodimetric titration & Iodometric titration

Iodimetric titration: Standard solution of Iodine react with anlyte reducing agent. It is one step reaction

I2 + 2e- → 2I- This method is rarely used.

& Iodometric titration: In this titration Iodide ion react with analyte reducing agent and converted into
Iodine molecule which is directly titrated with standard reducing agent using starch indicator. It is commonly
used method. It two step reaction

Analyte Metal ion + 2I-(from KI) → I2 + 2e-

I2 (Liberated Iodine) + 2 S2O32-( from Burette) → 2I- + S4O62-

Indicator: Starch
In Iodometric titration freshly prepared starch solution is used. This indicator gives a deep blue colour with
iodine. Color change of titration is blue to colorless
 Comparision: Iodometry Iodimetry

• Iodometry • Iodimetry

Analyte oxidizing agent added to excess iodine to produce Analyte reducing agent is directly titrated with std.
iodine titrated with std. Na2S2O3 iodine solution

Indirect method Direct method

2redox rectionoccures 1 redox reaction occurs

Iodine gets oxidised first & then reduced by reducing agent Iodine only gets reduced
More common to titration less commonto titration
E.g Cu, DO, IV, free chlorine etc Sn2+ -Sn4+

Application of Iodometry: 1Determination of DO in water sample. 2.Determination of free chlorine in water

sample.3.Determination of iodine value of lubricating oil.4.Determination of copper in a given sample of
an alloy of copper. 5.Determination of available chlorine in the given sample of bleaching powder

Precipitation titration
• Principle: It involves reaction between analyte halides with standard precipitating agent result in
the formation of a precipitate or slightly soluble salt of analyte sample
• Uses: For determination of Halides in the sample.
• Objective:To determining exact volume of standard precipitating agent required to form stable
precipitate with component from sample, which is estimated in known volume using suitable
indicator
• Generally precipitation titrations are used to estimate halides ( Cl, Br, I ) by using standard silver
nitrate solution. This is also refereed as Argentimetry.
• Reaction:
• NaCl + AgNO3 → AgCl ↓ + NaNO3
• White ppt
• 2AgNO3 + K2CrO4 →Ag2CrO4 + 2KNO3
• Brick red
•
Requirements: Standard precipitating agent, Adsorption type of indicator.
Adsorption type Indicator: Chemical substance (Adsorbing) showing termination of reaction via visible
colour change through adsorption of its own ppt on surface of parent ppt.
• Application: Estimations of halides in water sample ( Cl, Br, I )
•
COMPLEXOMETRIC TITRATION
Complexometric titration is one in which a stoichiometric, undissociated, soluble complex is formed, during
the addition of suitable complexing agent to the sample containing metal ions
• Principle: It involves reaction between analyte metal ions with standard complexing agent solution, resulting
in the formation of stable complex of compound.
Objective: The objective is determining exact volume of standard complexing agent required to form
stable complex with component from sample, which is estimated. The completion of complex formation is
detected with suitable indicator.
Requirements: Suitable complexing agent, Buffer solution &Suitable Indicator
Reaction:
 • Complexing agent:Definition: It is substance capable of forming complex with metal ion
• EDTA: (Ethylene Di amine Tetra Acetic Acid) The most commonly used complexing agent in Complexometric
titration.
• It is powerful chelating agent & forms high stable water soluble complex with almost all the metals.
• The metals are generally held in 1:1 ratio. This complex having five member rings
EDTA as versatile complexing agent
• Complexometry is one of the prime method in titrimetric analysis. It requires suitable complexing agent to
prepare std. sol. EDTA is commonly used complexing agent in almost all complexometric titration because
• 1.It is readily available, available in sufficiently pure form and economical
• 2. Its disodium salt is readily soluble in water.
• 3. It form complex with almost all metal ions.
• 4. It is sensitive to very low concentration of metal ions
• 5. It is selectivity towards specific metal ions under suitable pH.
• 6. Suitable masking agent must be available to avoid interferences of metal ion
• 7. They are suitable to carry out different types of complexometric titration like Direct,Back, replacement etc
• 8. They are sensitive to suitable indicator.
Role of pH/Selection of metal ions with pH i.e. complexing agents form stable complexes with metal ions at
different pH levels
Metal ions pH range
Ca2+,Mg2+,Ba2+,Sr2+ 9- 10
Cu2+,Zn2+,Ni2+,Mn2+,Fe2+,Sn2+,Al3+ 4-6

Zr4+,Hf4+,Th4+,Bi3+,Fe3+ 1-3

Metal ion/ Metallochromic type Indicator: Coloured complexing agent forming coloured complex & showing
termination of reaction via colour change through dissociation of complex
e. g. Murexide, Eriochrome Black T, Pyrocatechol violet, Xylenol orange etc.
Requirements of metal ion indicators :1.It should be readily available, economical & soluble in common solvent
2.Indicator must have its own characteristic colour. 3.It must form complex (coloured) with almost all metal ions. 4. It
should be sensitive to metal ion even at very low concentration. 5. Their must be sufficient colour contrast between
free indicator & metal indicator 6.Stability of metal-indicator complex over parent complexing agent (EDTA) complex
is less. 7. It must show specific interest in different metal at different pH level for multiple metal ion in solution

Types of EDTA titrations

1. Direct titration: It is titration of buffered sample solution with standard EDTA
2. Back titration: In this titration excess, known & standard EDTA is added in sample & unused EDTA is back
titrated with standard metal ion solution.
3. Replacement titration: If any metal ion fail to form stable complex then it is replace by suitable ion & it is
titrated with standard EDTA solution.
4. Alkalimetric titration: If no suitable indicator is available, then known excess of EDTA is added to sample &
free H+ ions formed are determined by titrating with standard base solution.
Applications: 1.Determination of hardness of water sample.2.Estimation of Zn in an alloy of brass.3.Estimationof
Ca in limestone. 4. Estimation of Ca& Mg in dolomite

Appication: Estimation of hardness of water.

Advantages of Volumetry
1. It is generally cheap, requiring little in the way of equipment.
2. It does not require a high level of skill.
3. It can often be done rapidly.
4. Results are immediately available.
Disadvantages of Volumetry
1. It is a destructive method often using up relatively large quantities of the substance being analysed.
2. It requires reactions to occur in a liquid phase, often the chemistry of interest will make this inappropriate.
3. It can produce significant amounts of chemical waste which has to be disposed of.
4. It has limited accuracy.
 Gravimetric Analysis
Introduction The gravimetric analysis is type of quantitative analysis that deals with the determination of
an element or ion or a compound obtained from a sample by weighing a suitable form of it accurately. It is
one of the very important analytical technique that gives accurate and precise results.
Definition:This is quantitative analysis involves, determination of ion/ element/ component/ingredients by
accurately weighing it into desirable compound having definite chemical composition.
1Analyte in solution form + Precipitating Reagent → Analyte converted into insoluble part called ppt, along
with mother liquor → Filtration of ppt and washing of ppt with electrolyte having common ions
2→ Air drying → Drying in oven (100 to 200 oC) It is stable with weathering condition with fixed chemical
composition→ Weighing & according to chemical formula Calculation of quantity of analyte ---OR-----
2 → Air drying → Heating in oven (700 to 800 oC) till it converted into stable chemical composition →
Weighing & according to chemical formula Calculation of quantity of analyte -----OR----
2→ Filtered ppt dissolved into another solvent and reprecipitated by ppting agent. And followed above 2
process so that final substance have definite chemical structure.
Some Important Terms
1. Precipitate: It is a insoluble solid separated from the solution as a result of chemical reaction.
2. Precipitant: It is a chemical reagent that forms precipitate on addition to solution.
3. Precipitation: It is a process of forming a precipitate due to chemical reaction.
4. Peptisation: It is a phenomenon in which the electrolyte concentration in the supernatant liquid
may fall below the coagulation value and the precipitate may pass into colloidal solution again.
5. Coagulation: It is a process of forming gelatinous mass by complete or partial solidification of sol.
6. Super saturated solution: A solution containing greater concentration of solute is known a super
saturated solution.
7. Coagulation or flocculation value: It is the minimum amount of electrolyte necessary to cause
flocculation of the colloid.
8. Sol: It is a trerm used to distinguish the colloidal suspension from microscopic suspensions.
9. Co- precipitation: The simultaneous precipitation of more than one compound from a solution.
The gravimetric analysis includes formation of the precipitate, (digestion of precipitate if
necessary) filtration of precipitate. Washing of precipitate, drying and ignition of precipitate,
accurate weighing of residue and determination of constituents using relations.
Types of Gravimetric Methods:
Precipitation gravimetry : In this method analyte ions/element/ component converted into suitable
insoluble solid having fixed and stable chemical composition for accurate weighting. Thus from weight of
compound of analyte it estimated called precipitation gravimetry. e.g Determination of Cl–by precipitating
it into insoluble AgCl.
Electro gravimetry : In this method analyte deposited on an electrode i.e cathode in the form of film by
passing electric current and amount of element is direly determine by weighting it in the form of metal or
some time weighing the liberated gases at respective electrode called electrogravimetry. E.g The
deposition as PbO2 at a Pt anode is one example of electrogravimetry. The reduction of Cu2+ to Cu at a Pt
cathode is another example of electrogravimetry
Volatilization gravimetry : In this method thermal or chemical energy is used to remove a volatile
species,so weight difference is obtained called volatilization gravimetry.
It is possible simply by measuring weight of residue left after removal of volatile matter OR allowing to
absorb liberated volatile matter to some chemical substance, where increase in mass of absorbing
substance recorded.
In determining the moisture content of bread, for example, we use thermal energy to vaporize the water
in the sample. To determine the amount of carbon in an organic compound, we use the chemical energy of
combustion to convert it to CO2
Particulate gravimetry: In particulate gravimetry we determine the analyte by separating it from the
sample’s matrix using a filtration or an extraction. The determination of total suspended solids is one
example of particulate gravimetry.
Thermogravimetry:In this method analyte is subjected to thermal treatment and change in weight of
substance is recorded as function of temperature using thermogravimeter called thermo gravimetric
analysis. Determination of moisture content, volatile matter content, thermal decomposition of matter,
rusting of material where mass of sample increase or decrease measured by thermo balance.
Organic precipitation gravimetry: This method is similar to precipitation gravimetry but precipitating agent
used is organic substance e.g. Ni + DMG → *Ni-DMG]
Characteristics of precipitate
The accuracy and precision of gravimetric analysis mostly depended on the nature of precipitate
formed. So the precipitate should possess following characteristic properties- (factors that determine
a successful analysis by precipitation gravimetry)
1. The precipitate should have low solubility otherwise practically complete precipitation is not
possible.
2. The form of precipitate should be such as to allow rapid filtration and washing. Since it saves time
during analysis and give errorless quantity.
3. The composition of precipitate should be strictly according to its chemical formula. It should not
contain water of crystallization. Otherwise error occurs during analysis.
4. The precipitate should have adequate chemical stability and it should not absorb moisture or gases
from atmosphere. i.e inert to the weathering condition

Precipitation
A) Requirement for good precipitation / General rules for good result of precipitation
No universal rules can be given which are applicable to all cases of precipitation. However, there are
some general rules for good result of precipitation.

1. Precipitation should be carried out in dilute solution to avoid the chance for co precipitation (The
simultaneous precipitation of more than one compound from a solution). Of course the solubility of
the precipitate, the time required for filtration should not be ignored.
2. A suitable reagent should be mixed slowly and with constant stirring. This assists the growth of
crystals and keeps a low value of super saturation.
3. Precipitation is generally carried out in hot solutions, which decreases chance of super saturation as
solubility increases with rise in temperature and hot solution favours coagulation and rapid growth.
4. The precipitate should be digested for prolonged period to avoid co-precipitation.
5. The precipitate should be washed thoroughly with appropriate dilute solution of an electrolyte
containing common ions, instead of pure water which leads to cause peptisation.
 6. Many time precipitate is dissolved in suitable solvent and then reprecipitated to eliminate
contamination.
The solubility of precipitate, excess of precipitant, pH of the solution, temperature and the
nature of solvent, affect the yield of precipitate in gravimetric analysis.

B) Process of precipitate
The process of precipitation includes three stage viz, (1) Nucleation (2) Crystal growth and (3)
Ageing
i.e. recrystallization.

1. Nucleation: The nuclei provide centres at which subsequent growth takes place.
Nucleation possible by two ways
i) In dilute solution very fine suspended foreign matter in the solution (i.e dust) or impurities
adhering to the walls of the glass vessel.
Such nucleation processes are called as heterogeneous,
ii) In super saturated solution ions/ cluster/crystals of same substance provide centre.
This nucleation process is said to be homogeneous,

Hence it is possible to say that, nuclei were forming spontaneously in the solution in which
the precipitate was actually growing on invisible, additional nuclei that were already present.

2. Crystal growth : Once crystal nuclei are formed, crystal growth starts by the transport of
corresponding ions from the solution to the growth crystal. Crystal growth depends on
concentration of solution, temperature of solution, stirring of solution.

3. Ageing/ Digetionofprecipitate : After complete precipitation usually it is allowed to digest

before filtering. The particles become larger, more perfect and easier to filter as a result of
digestion. This results by the disappearance of smallest particles.
Since it is spontaneous process, result in decrease in free energy at constant temperature
and therefore all surfaces tend to become as small as possible. The solid can reduce it’s surface area
by aggregating to form a larger particles since the small particles have more surface area per unit
mass than larger one. But solid is rigid, hence martial goes into solution from the small particles and
redeposit on large particles.
During the process of digestion following changes take place.Effects of digestion
i) Originally irregular particles are converted in to more compact from
ii) Decrease in surface area result to reduce the surface adsorption.
iii) Decrease in co precipitation.
iv) Internal perfections may even occur simply by diffusion of atoms with the solid.
v) The colloidal particle may become cemented together by depositing solid between
them.
But the precipitate of AgC1 and hydrous Fe2O3 remain colloidal even after long
digestion. This may be because of too small value of surface energy.
In some cases the electric charge on the particle of precipitate may hinder Ostwald
ripening because of high electro kinetic potential of the particles.
If the impurities are less soluble than main precipitate, than digestion may increases amount of
co-precipitate? Under such circumstance responsible ions should be removed from the solution
or should be masked before precipitation.
Physical Nature of Precipitate
The Physical forms of precipitates can be classified as

(i) Crystalline ppt : The crystalline precipitates size 0.1 to 1 micron in diameter
(ii) Curdy ppt : The curdy have intermediate size 0.02 to 0.1 micron
(iii) Gelatinous ppt : Gelatinous precipitates have smaller particle size less than 0.02 micron
Gelatinous ppt is not possible to filter the curdy and gelatinous precipitates as they have
very fine particles which easily pass through filtering media . These precipitates are held together by
weak cohesive forces and get easily dispersed or peptized which can be prevented by washing with
an electrolyte instead of pure water as they carry indefinite amount of water
The physical form of these precipitates are inter-convertible. For example curdy precipitate
of AgCl is converted in crystalline from when it’s solution in aqueous ammonia is slowly evaporated.
Similarly gelatinous precipitate of Al(OH)3 is converted into crystalline form by slow evaporation of
it s solution with concentrated aqueous ammonia thus physical nature of precipitate largely
depends upon the size shape and electric charge on the particles of precipitate.

Purity of Precipitate
The greatest source of error in the gravimetric analysis is the impurity of the precipitate
which results due to co-precipitation & post precipitation.
Co-precipitation: The contamination of the precipitation by substances which are normally soluble
in the mother liquor during its formation is known as co-precipitation.
For example, the precipitation of nickel dimethylglyoxime requires a slightly basic pH. Under these
conditions, any Fe3+ in the sample precipitates as Fe(OH)3. In addition, because most precipitants
are rarely selective toward a single analyte, there is always a risk that the precipitant will react with
both the analyte and an interferent.
It may result by two ways a) by formation of solid solution b) by surface adsorption.
a) By formation of Solid Solution: The solid solution formation means the formation of
mixed crystal which result in actual entering the impurities in the crystal lattice of the precipitate.
Conditions required forming solid solution
i) The activities of the dissolved substance & precipitate should be equal.
ii) Both the solid should be isomorphism (i.e. they should be crystalline the same form.)

iii) The difference between ionic radii of like signs should not be more than 10 %
Since condition for solid solution formation is being very strict, this type of co-
precipitation is rarely observed. However it can be avoided simply by digestion of
precipitate.
b) By surface adsorption. : It results by the process of occlusion(prevention). The amount of
co-precipitation results by surface adsorption depends upon the physical nature of the
precipitate.
 Crystalline Precipitate: Freshly formed precipitate has large surface area either because if its
very small particle size or imperfectness. The electric charge is the origin of the surface
adsorption.
e.g. The crystal lattice of BaSO4 contains alternative arrangement of Ba +2 & SO4 -2 ions.
When it is placed in Na2SO4 solution its crystal lattice grows due to excess of SO4-2 ions by adsorbing
SO4-2 ions on the surface of it. This gives negative charge to the BaSO 4 crystal. This layer of adsorbed
SO4-2 ions called primary layer, which attracts the Na + ions from the solution, as a result SO 4-2
crystal lattice gate adsorbed with Na2SO4 layer as shown in the figures below

This type of co-precipitation can be removed by the digestion.

Curdy Precipitate: The surface adsorption results through same mechanism as in case of
crystalline precipitate. The difference between curdy & beyond colloidal size. They do not therefore
enclose impurities by growing around them & can be removed by washing with dilute solution of
suitable electrolyte.
Gelatinous Precipitate: Being smaller particle size it provides large surface area that results in
strong surface adsorption which can not be removed either by digestion or washing the precipitate.
The co precipitation in this case can be prevented by caring out the precipitation at suitable pH.
Post Precipitation: The appreciable errors may be introduced by post precipitation. This is
the precipitation which occurs on the surface of the first precipitate after its formation. It occurs
with sparingly soluble substances which form supersaturated solution; they usually have an ion in
common with the primary precipitate. Thus in the precipitation of calcium as oxalate in the
presence of magnesium, magnesium oxalate separate out gradually on the surface of calcium
oxalate. The longer the precipitate is allowed to stand in contact with the solution greater is the
error due to this cause. Similar effect is observed in the precipitation of copper or mercury (II)
sulphide in 0.3M HCI, in the presence of zinc ions, zinc sulphide is slowly post precipitated. This
error may be avoided by i) filtering the precipitate immediately after precipitation, ii) caring out
precipitation at critical pH iii) protecting the ions responsible for this error by masking.
Difference between post precipitation & co-precipitation
Post precipitation is distinguished from co-precipitation in the following ways-
i) The magnitude of contamination by post precipitation may be greater than in co-
precipitation.
ii) Rise in temperature increases rate of contamination by post precipitation.
iii) The contamination increases with time as the main precipitate is left in contact with the
mother liquor in post precipitation, while it decreases in co-precipitation.
Parameter Co precipitation Post precipitation
Definition The contamination of the The precipitation of a second (often
precipitation by substances which related) substance upon the surface of
are normally soluble in the mother an initial/parent precipitate.
liquor during its formation is
known as co-precipitation

Caused by Inclusion, Occlusion & Adsorption Surface adsorption

phenomenon
Degree of High Low
contamination
Time of During pption After pption
contamination
Digestion Decreases Increases
Re crystallization Decreases Decreases

Types of Impurities in ppt:

 One common impurity is an inclusion. A potential interfering ion whose size and charge is similar
to a lattice ion, may substitute into the lattice structure, provided that the interferent precipitates with
the same crystal structure (Figure 8.4a). The probability of forming an inclusion is greatest when the
concentration of the interfering ion is substantially greater than the lattice ion’s concentration. An
inclusion does not decrease the amount of analyte that precipitates, provided that the precipitant is
present in sufficient excess. Thus, the precipitate’s mass is always larger than expected.An inclusion is
difficult to remove since it is chemically part of the precipitate’s lattice. The only way to remove an
inclusion is through reprecipitation. After isolating the precipitate from its supernatant solution, we
dissolve it by heating in a small portion of a suitable solvent. We then allow the solution to cool, reforming
the precipitate. Because the interfer-ent’s concentration is less than that in the original solution, the
amount of included material is smaller. We can repeat the process of reprecipitation until the inclusion’s
mass is insignificant. The loss of analyte during repre-cipitation, however, can be a significant source of
error.
Occlusions form when interfering ions become trapped within the growing precipitate. Unlike
inclusions, which are randomly dispersed with-in the precipitate, an occlusion is localized, either along
flaws within the precipitate’s lattice structure or within aggregates of individual precipitate particles (Figure
8.4b). An occlusion usually increases a precipitate’s mass; however, the mass is smaller if the occlusion
includes the analyte in a lower molecular weight form than that of the precipitate.
We can minimize occlusions by maintaining the precipitate in equi-librium with its supernatant
solution for an extended time. This process is called a digestion. During digestion, the dynamic nature of
the solubility–precipitation equilibrium, in which the precipitate dissolves and reforms, ensures that the
occlusion is reexposed to the supernatant solution. Because the rates of dissolution and reprecipitation are
slow, there is less opportunity for forming new occlusions.
After precipitation is complete the surface continues to attract ions from solution (Figure 8.4c).
These surface adsorbates comprise a third type of impurity.
We can minimize surface adsorption by decreasing the precipitate’s available surface area. One
benefit of digesting a precipitate is that it increases the average particle size. Because the probability of a
particle completely dissolving is inversely proportional to its size, during digestion larger particles increase
in size at the expense of smaller particles. One consequence of forming a smaller number of larger particles
is an overall decrease in the precipitate’s surface area. We also can remove surface adsorbates by washing
the precipitate, although the potential loss of analyte can not be ignored.
Inclusions, occlusions, and surface adsorbates are examples of coprecipitat

Factors affecting precipitation:

1. Choice of precipitant: It produce completely insoluble ppt. easy to filter and wash. Organic ppt
have following advantages i) many chelating compounds are insoluble in water & metal ions are
quantitatively precipitated ii) It produce high molecular weight complex with small metal ion i.e. minimizes
weighing error. Iii) Organic precipitant are selective in nature under certain condition of pH & masking
agent. Iv) Organic precipitant forms Course & Bulky ppt. Hence can be easily handled. v) Organic precipitant
are anhydrous, hence their ppt dry quickly, wash quickly.
2. Amount of precipitant: When large excess amount used during pption, ppt formed re dissolved
by raising the solubility of ppt. When just enough amount is added then complete pption might not takes
place as some amount is required to reach the solubility product value. Hence reasonable excess amount is
added. It provides excess common ions and the solubility of ppt is decreases.
 3. Effect of temperature: Solubility of ppt increases with increase in temperature. Purity increases
with increase in temperature due to better crystal structure. Hence pption carried out at higher
temperature.
4. Effect of pH: Solubility of ppt changes with change in pH. Thus selectivity of organic reagent can
always be improved by the controlling pH. Smaller the dissociation constant for the acid higher is the pH
required. Salt of weak acid generally ppted in alkaline or neutral pH ranges.
5. Effect of complex formation: Unwanted ions & their interference removed by forming soluble
complex using masking agent. Now complexing agent forms complex which is insoluble.

GF: The gravimetric factor is the ratio between the grams of a compound and the grams of a single element that
forms that compound.

GF = [F.W of analyte (g/mol)/= F.W of ppt (g/mol)] X[number moles of analyte in ppt /number moles of analyte]

Numerical: following
1. A 0.7336-g sample of an alloy containing copper and zinc is dissolved in 8 M HCl and diluted to 100 mL in
a volumetric flask. In one analysis, the zinc in a 25.00-mL portion of the solution is precipitated as
ZnNH4PO4, and subsequently isolated as Zn2P2O7, yielding 0.1163 g. The copper in a separate 25.00-mL
portion of the solution is treated to precipitate CuSCN, yielding 0.2383 g. Calculate the %w/w Zn and the
%w/w Cu in the sample. FW= Zn=65.38,Zn2P2O7= 304.72, Cu= 63.54 CuSCN= 121.64

25ml, 0.7336g sample contain 0.1163g Zn2P2O7 25ml, 0.7336g sample contain 0.2383g CuSCN
100ml, 0.7336g sample contain 0.4652 g Zn2P2O7 100ml, 0.7336g sample contain 0.9534 g CuSCN
GF = FW Zn/ FW Zn2P2O7 X 2/1 = 65.38/304.72 X 2/1 GF = FW Cu/ FW CuSCN X 1/1 = 63.54/121.64 X 1/1
= 0.42911 = 0.5223
%Zn = Wt of Zn2P2O7/ Wt of Sample X GF X 100 %Zn = Wt of CuSCN/ Wt of Sample X GF X 100
= 0.4652/0.7336 X 0.42911 X 100 = 0.9534/0.7336 X 0.5223 X 100
= 27.21% Zn W/W = 67.86% Cu W/W
A conservation of mass requires that all the zinc in the alloy is found in the final product, Zn 2P2O7. We
know that there are 2 moles of Zn per mole of Zn2P2O7; thus

This is the mass of Zn in 25% of the sample (a 25.00 mL portion of the 100.0 mL total volume). The %w/w
Zn, therefore, is

For copper, we find that

2. A 2.00 gm sample of limestone was dissolved in hydrochloric acid and all the calcium present in the
sample was converted to Ca2+ ion. Excess ammonium oxalate solution, (NH 4)2C2O4(aq), was added to the
solution to precipitate the calcium ion as calcium oxalate, CaC2O4(s). The precipitate was filtered, dried
and weighted to a constant mass of 2.43gm. Determine the % by mass of calcium in the lime sample.(FW
CaC2O4= 128.097, CaCO3=100)
GF= 100/128.09 = 0.7807
% Calcium = Wt of ppt/wt of limestone X GF X 100
= 2.43 /2 X 0.7807 X100
= 94.85%
3. A 3.00 gm sample of an alloy (conaining only Pb and Sn) was dissolved in HNO3. H2SO4 was added to
this solution, which precipitated 1.69gm of PbSO4. Assuming that all of the Lead was precipitated, what
is the percentage of Sn in the sample?
GF = Pb/PbSO4 = 207.2/303.26 = 0.6832
% of Pb = Wt. of PbSO4/Wt of sample X GF X 100
= 1.69/3 X 0.6832 X 100
= 38.48
% of Sn = 100 - % of Pb
= 100 -38.48
= 61.52%
OR
3 gm of alloy (Pb&Sn) contain 1.69 gm of PbSO4 (MW 303.26)
Amount of Pb (MW 207.2) in PbSO4 = 207.2 X 1.69/303.26 = 1.1546gm
Hence Wt of Sn = 3.00 – 1.1546 = 1.8453
Hence % of Sn = 1.8453 X100 / 3 = 61.51%
4. An empty crucible has a mass of 12.770 gm. The crucible and hydrate have a mass of 13.26gm. After
heating, the crucible and anhydrous salt have a mass of 13.010 gm. What is formula of this hydrate of
MgSO4.?H2O? (MW MgSO4 = 120.366, Hydrated MgSO4 245.74)
Crusible weight = 12.770gm
Crusible + Hydrated MgSO4 wt = 13.26gm
Crusible + unhydrated MgSO4 wt = 13.01gm
Wt of Hydrated MgSO4 = 0.49gm
Wt of Unhydrated MgSO4 = 0.24gm
Wt of Moisture = 0.25gm
For 0.24 gmMgSO4 ,wt of moisted MgSO4 is 0.49gm
Then what is wt of 120.366 gm of MgSO4? = 120.366 X 0.49 / 0.24 = 245.7472 gm
Hence Amount of Moisture = 245.7472 gm - 120.366 gm = 125. 3812gm
18.01 gm H2O = 1 Mole
Hence moles of H2O in 125. 3812gm = 125. 3812gm /18.01 = 6.96 Appox 7.00
Hence formula for MgSO4. ?H2O = MgSO4. 7H2O
5. Purity of common salt is tested by gravimetry. 0.85g NaCl is dissolved in water to get 100ml solution
on treatment with AgNO3 gives 1.98g AgCl. Calculate purity of salt (FW AgCl-143.32, NaCl-58.5)
GF = 58.5/143.32 =0.4081 Therefore % W/W = 1.98 X 0.4081X100 / 0.85 = 95.081% Pure
6. Calcium tablets are tested gravimetrically for its calcium content. 30 tablets were randomly picked &
crushed to powder weighing 12gm. 4gm of powder is dissolved in acid & diluted to 100ml with
water.Calcium is isolated as CaC2O4 which on ignition gives 1.41gm CaO. Calculate amount of Calcium as
CaCO3per tablet. (FW- CaCO3-100,CaO-56)
GF= 100/56=1.7857 Mass of CaCO3 = 1.41 X 1.7857 = 2.517gm
4gm Sample = 10 tablets
Therefore CaCO3 per tablet = 2.517/10 = 0.2517 gm = 251 mg.
Advantages of Gravimetric:
1.It is accurate and precise when using modern analytical balance.
2. Possible sources of error are readily checked since filtrates can be tested for completeness of
precipitation and precipitates may be examined for the presence of impurities.
3. It is an absolute method; it involves direct measurement without any form of calibration being required.
4. Determination can be carried out with relatively inexpensive apparatus; the most expensive items are
a muffle furnace and sometimes platinum crucibles.
5. Gravimetric analysis was used to determine the atomic masses of many elements to six figure accuracy.
6. Gravimetry provides very little room for instrumental error and does not require a series of standards
for calculation of an unknown.
Disadvantages of gravimetry:
1.The chief disadvantage is that it requires meticulous time consuming.
2. The chemist often prefers modern instrumental methods when they can be used.
3. Gravimetric analysis usually only provides for the analysis of a single element, or a limited group of
elements, at a time.
4. Methods are often convoluted and a slight mis-step in a procedure can often mean disaster for the
analysis (colloid formation in precipitation gravimetry, for example).
5. Gravimetric analysis is based on the measurement of mass
FACTORS AFFECTING PRECIPITATION
1.Choice of precipitant: The precipitant should be such that it produces a precipitate which is completely
insoluble i.e. solubility product should not exceed 10 -6 mol. The structure of the precipitate formed should
be such so as to allow rapid filtration and washing. Organic reagents have a special place in inorganic
analysis (generally termed as organic precipitants) because of the following advantages offered by them.
i. Many of the chelate compounds are very insoluble in water, so that metal ions may be quantitatively
precipitated.
ii. The organic precipitant often has a high molecular weight. Thus a small amount of metal may yield a
large weight of precipitate, minimizing weighing errors.
iii. Some of the organic reagents are fairly selective, yielding precipitates with only a limited number of
cations. By controlling factors such as pHandthe concentration of masking agents, the selectivity of an
organic reagent can often be greatly enhanced.
iv. The precipitates obtained with organic reagents are often coarse and bulky and hence can be easily
handled.
v.Further, metal chelates are mostly anhydrous. Hence, the precipitates dry quickly. This can be
accelerated by washing the precipitate with alcohol.
2. Amount of precipitant: The amount of precipitant added is also of great importance. If a large excess of
precipitant is added, the precipitate formed redissolves as it raises the solubility of the precipitate and if
just enough amount is added then complete precipitation might not take place as some amount is required
to reach the solubility product value. Hence, in precipitating a substance, a reasonable, excess of
precipitant is invariably added to ensure completeness of precipitation. The excess precipitant provides
excess of common ions and the solubility of precipitate is decreased. For analogous reasons, the precipitate
is washed with a solution containing common ions.
3. Effect of temperature: The solubility product of a substance is constant only when its temperature is
unaltered. Usually the solubility increases with the increase in temperature. When the precipitation is
carried out at higher temperature, the precipitate formed is of high purity due to better crystal structure.
Hence, wherever possible, precipitation which is carried out at higher temperature is most advantageous
but then it should be cooled before filtration.
4.Effect of pH: The solubility of the precipitate with the change in pH of the solution is inevitable. The
effect depends on the type of precipitate. Generally, the precipitate of metal hydroxides and those of
sparingly soluble salts of weak acids are precipitated only in alkaline or neutral pH ranges. Smaller the
dissolution constant for the acid, higher is the pH required for practically complete precipitation of its salt.
The selectivity of organic reagents can always be improved by the control of pH.
5. Effect of complex formation: In the presence of certain ions, the desired component is likely to form
complex ions having higher dissociation constants and this will lead to incomplete precipitation. So the
unwanted ions should be prevented from getting precipitated out by masking them. Masking is the
procedure of forming soluble complexes with the unwanted ions and thus keeping them in solution.
CALCULATIONS
In the usual gravimetric procedure a precipitate is weighed, and from this value, the weight of the analyte
in the sample is calculated with the aid of a gravimetric factor (GF). The GF is the ratio of the formula
weight of the substance sought to that of the substance weighed.

Usually, the purpose of a quantitative analysis is to determine the percentage of a certain element or ion
(A)in a sample, which can be calculated as: