QUANTITATIVE ANALYSIS

Presented By:
A Madhavi
Kameswari
Assistant Professor
Lecture Details: Chemistry
QUANTITATIVE ANALYSIS GIET Degree College
Chemistry/III-B.Sc (MPC & FS),VI-Semester.
Chemical Analysis:
It is the study of chemical composition and structure of
the substances.
Types of chemical analysis :
1.Qualitative analysis :
It deals with the detection and identification of the
constituents of chemical substances
2.Quanitative analysis :
It deals with the determination of the respective
amounts of any of the constituents of chemical
substances.
• Importance of chemical analysis in different fields of
science:
Analytical chemistry can help us in putting a check on quality
and quantity control of a product
Importance of analytical chemistry in pharmacy:
1. To determine the self life of a compound.
2. To determine adulterants.
3. Drug dissolution studies.
Applications in agriculture:
1. soil testing
2. Water testing
3. Harvested crop testing
What can be the cause of Eluru disease?
Excessive amounts of heavy metals such as lead and nickel
were found in the blood samples of patients.
• In environmental studies:
For studying air condition, water and soil contents
in a particular locale.
In medical technology and research:
Simple tests like serum cholesterol , urine
ketones, blood glucose level depends on
analytical chemistry.
Steps involved in chemical analysis

1.Sampling
2.Dissolution of sample
3.Conversion of the analyte to a measurement
form
4.Measurement
5.Calculation and interpretation of the results.
1) Sample collection:
 Before carrying out an analysis a sample that is representative
of all the compounds and their amount is to be selected.
 In the case of solid sample, the sample is ground and
systematically mixed and reduced in size.
 The sampling process in the liquid Is straight forward process.
 In the collection of gaseous samples the volume taken , rate
and duration of sampling are the important factors.
2) Dissolving sample:
 Many of the sample dissolve in water. If they
are not water soluble , special treatment must
be given to affect their solubility.
 common method used for dissolving samples
are:
i. Treatment with the HCl , HNO3, H2SO4 , HClO4
ii. Fusion of the sample in the acid or basic flux
and then treatment in water sample.
3) Conversion of the analyte to a measurable form:
 Before make the physical and chemical
measurement it is necessary to solve the
problem of interference.
1) Copper in a sample using KI (to liberate
iodine and titrate against hypo): The sample
solution should be free form fe+3 ion.
Because fe+3 Ion oxidize, I- to I2. The
interference of fe+3 ion can be prevented by
adding require amount of NaF solution.
Ex: In the analysis of Mg in a sample by the
precipitation as it oxalate fe+3 ion
interfere. So fe+3 ion is precipitated as its
hydroxide at pH of 6.5.
4) Measurement:
In this step analysis is carried out by the chemical, physical (or) by biological
means, laboratory techniques like volumetric analysis, gravimetric analysis,
instrumental analysis etc are used.

5) Calculation and interpretation of the measurement:

This is final step of analysis.
The interpretation of the results obtained is not always simple.
 After the assays have been completed, quantitative results are mathematically
noted, and both qualitative and quantitative results are presented in a meaningful
manner.
 In most cases, two values are reported for quantitative analyses
The first value is an estimate of the correct value for the analysis, and the second
value indicates the amount of random error in the analysis.
 Quantitative analysis
• In quantitative analysis the amount of substance
present in the given solution is determined.
• The quantitative analysis is further classified into 2
types.
• 1. Volumetric analysis.
• 2. Gravimetric analysis
• The volumetric analysis is also known as titrimetric
analysis that involves the process of titrations.
 Terminology used in
volumetric analysis
Titrant : The substance of known concentration
Analyte : The substance to be titrated
Titration : the volume of titrant for a known
volume of analyte is noted at the completion of
reaction. By knowing the volumes of both these
solutions and strength of one of them, the strength
of other can be estimated. This process is called
titration.
Indicator :
The substance which helps in the visual detection of the completion of
the titration is called an indicator.
Indicators are 3 types.
1.Internal indicator
2.External indicator
3.Self indicator
End point:
The point at which the colour change of the indicator is apparent to the
eye .
Titration error: In the ideal titration the visible end point will coincide
with the stoichiometric or theoretical end point. However in practice a
very small difference usually occurs which is known as titration error.
• Standard solution:
the solution whose concentration known accurately is known as
standard solution.
Primary standard substance:
A substance is known as primary standard if its solution is used to
standardize the solution of other substance.
Secondary standard substance:
A substance is known as a secondary standard substance which may be
used for standardization and its concentration is found by the
comparison against a primary standard.
1.
Types
Acid base titrations
of titrations :
2. Oxidation reduction reactions
3. Complexometric titrations
4. Precipitation titrations

Acid base titrations :

These titrations are based on neutralization reactions in which the acid
and react with each other to form salt and water .These are of 2
types.
1.Acidimetry :
It is based upon the determination of concentration of acids by means of standard
alkali solution.
2.Alkalimetry:
It is based upon the determination of concentration the alkali by
means of standard acid solution.
Indicators used in acid base titrations:
•In addition to the sample ,an appropriate indicator is added to reflect
the pH range of the equivalence point.
•The acid base indicator indicates the end point of the titration by
changing colour.
•Some examples are
indicator pH range
1.Methyl orange 3.1 - 4.4
2.Methyl red 4.2 – 6.3
3.Phenolphthalein 8.3 - 10
• Theory of acid base indicators:
2 theories have been proposed to explain the change of colour of acid –
base.
1.Ostwald theory
2.Quinonoid theory
a) Ostwald Theory:
• All indicators are weak organic acids and bases. The undissociated
indicator has a different color from that of its ion.
Phenolphthalein indicator:
Phenolphthalein is colorless. But it is a weak acid and ionizes in the
solution to give pink colored ions.
• In acidic solution in presence of excess of H+ ions ,the ionization of the
indicator will be suppressed due to common ion effect . The concentration of
the ion is very small therefore the color will be that of the molecule.
• In alkaline medium the H+ ions are removed by the OH- ions .This will result in
further ionization of the indicator , which increases the concentration of ion .so
the color will be that of the ion.
• Methyl orange indicator:
methyl orange is yellow colored indicator which can be ionized to red colored
ion. but the color change depends upon the pH of the solution.
in acidic medium : it gives red colored ion
in basic medium :it gives the color of the molecule i.e yellow
 2)Quinonoid theory :
• Acid base indicators are complex aromatic molecules which are
capable of existing in two tautomeric forms in equilibrium with
each other.
• One of the forms is called benzenoid form and the other form is
quinonoid form which are having different colors.
• Benzenoid form have lighter color than quinonoid form.
• One form is stable in acidic medium and other form is stable in
basic medium.
• The color of the indicator changes according to the change in the
medium of the solution.
Phenolphthalein indicator:
Methyl orange indicator
color change of indicators
 Red –Ox titrations
• The titration in which a reducing agent is estimated by titrating with
a standard oxidizing agent is called red ox titration.
• In this type of titrations oxidation and reduction takes place
simultaneously.
• Oxidizing agents used in red ox titrations are KMnO4 ,K 2Cr2O7 ,
and I2
• Types of red ox titrations:
1. Permanganometry
2. Dichrometry
3. Iodometry
 Permanganometry
• The red ox titrations which involves the use of KMnO 4 as an oxidizing agent are
called permanganometric titrations.
• KMnO4 acts as an oxidising agent in presence of sulphuric acid.
• Can be titrated against reducing agents like ferrous salts, oxalates , oxalic acid etc.
• Red ox titration of Feso4 with acidified KMnO4 :
• The colour change is due to reduction of Mn+7 ion to Mn+2 ion which are having
different colours.

purple colour
MnO4- + 8H+ + 5 e- Mn+2 + 4 H2O
colour less
 Red ox titration of Feso4 with
acidified KMnO4
10FeSO4 + 2KMnO4 + 8H2SO4 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + 8H2O
 Dichrometry
• The red – ox titration which involves the use of potassium
dichromate as an oxidizing agent are called dichrometric
titrations.
• Initial reduction equation:
• Cr2O72+ 14H+ + 6 e-  2Cr3+ + 7H2O
• Initial oxidation equation:
• 6Fe2+ -6e 6Fe3+
Complete balanced equation :
Cr2O72+ 6Fe2+ + 14H+  6Fe3+ + 2Cr3+ + 7H2O
 Indicators used in dichrometry:
• Two types of indicators used in dichrometry.
1 ) External indicator :potassium ferricyanide
2) Internal indicator :
indicator color change
a) N-phenyl anthranilic acid --- green to violet
b) 1% diphenyl amine in conc H2SO4 --- bluish green to purple
c) 1% diphenyl benzidine in conc H2SO4 ---bluish green to purple
 IODOMETRIC
•
TITRATIONS
The titrations which involve iodine as an oxidizing agent are called iodometric
titrations.
• Iodine ,in aqueous solution acts as a mild oxidizing agent .
• Strong reducing agents like hypo, H2S, SnCl2 etc. . react rapidly and completely
with iodine even in acidic solution.
• Comparatively weaker reducing agents like arsenates and antimonates react
completely only in neutral or faintly acidic medium.
• Types of iodometric titrations :
These are 2 types
1. Iodimetry
2. iodometry
• IODIMETRY : (direct iodometry)
• Estimation of reducing substances by the use of standard iodine is called
iodimetry.
• In iodimetry ,a solution of iodine in KI is employed and the reactive species is the
tri iodide ion, I−3.
• Iodine is soluble in aq KI solution, and forms brown coloured I−3.
• This ion liberates iodine so readily during the titration that the solution behaves as
if it has the dissolved iodine .
• KI + I2 I−3.
• violet colour brown colour

2S2O3-2 + I 2 S4O6-2 + 2I-

 Indicators in iodimetry :
• The end point in all titrations involving iodine may be
detected in presence of starch indicator.
• reducing agent + I 2 I-
• released from I−3. color less
brownish yellow

• reducing agent + starch – I2 I- + starch

deep blue . color less

 IODOMETRY: (Indirect iodometry)

• This method involves the titration of liberated iodine

in a reaction
• In iodometric titrations ,an oxidizing agent such as
potassium dichromate is used to liberate iodine
quantitatively.
• Now the liberated iodine is titrated with a standard
sodium thio sulphate
 COMPLEXOMETRIC
TITRATIONS
• The titrations involving the use of complexing agents (complexone)
as titrants are known as complexometric titrations.
• These are useful in the estimation of metals.
• The compexone coordinate with metals through several donor
atoms simultaneously forming several chelate rings and giving rise
to very stable complex.
• Generally 5 or 6 membered chelate rings are formed.
• Some important complexones are
1. Di sodium salt of EDTA [Na2 H2Y]
2. EDTA or H4Y
Structure of EDTA
 Types of EDTA titrations :
• 1) Direct titration :
• The metal ion is buffered to the desired pH and titrated directly with the
standard EDTA solution.
• In order to prevent the precipitation of hydroxide of the metal, suitable
reagent is added.
• 2 ) Back titration:
• In this method an excess of the standards solution of EDTA is added to the
metal solution being determined so as to complex all metal ions present in
the solution.
• The excess of EDTA left after the complex formation is back titrated with a
standard solution of a second metal ion like ZnCl2,ZnSO4,MgCl2and MgSO4
• 3) displacement titration:
• When the metal ion do not react with the metal indicator or react
unsatisfactorily, substitution titrations are employed.
• The metal cation to be estimated is treated with Mg –EDTA complex.
• The analyte ion displaces EDTA from the metal, the amount of Mg set
free is estimated .
• 4) Alkalimetric titrations:
• A solution of Na2EDTA is added to a solution containing metal ions.
• A complex is formed with the liberation of hydrogen ions, which are
titrated against a standard alkali solution.
• Indicators used in complexometric titrations:
• metal ion indicators are used as indicators. these are organic dyes capable
of forming intensely colored compounds with the metal ions.
• Since these indicators are stable at a certain pH ,buffer solutions are added.
• Ex: 1.Eriochrome Black-T , 2.Murexide
• EBT indicator has blue colour in the pH range 7-11 in which The
Indicator is stable.
• On addition of metallic salts (Mg+2 ,Ca +2 ), it gives red color .
• At the end point of the titration, EDTA combines with the metal ion of the
indicator and releases the free dye stuff to show its color is blue.

Metal –indicator + EDTA metal –EDTA + indicator

red blue
 Precipitation Titration
The titration
in which precipitate is formed are known as precipitative
titrations.
Conditions for precipitative titrations :
•The precipitate formed is practically insoluble.
•The precipitate is rapid.
•The titration values are not disturbed (or) changed due to
absorption effect even when co precipitate occur.
•The end point is easily detectable.
Theory of precipitative
titration :
• The end point in these titration can be identified by three methods
1) Mohr’s method
2) Volhard’s method
3) Fajan’s method.
(a)Mohr’s method:
Silver ion of Agno3 combine with the chloride ion in the given solution to
form Agcl precipitate .
At the end of the titration chromate ions combine with silver to form
silver chromate.
The white ppt of Agcl will be covered with the red precipitate of silver
chromate giving red coloration to AgCl ppt
Ag+ + Cl- AgCl (white)
2 Ag+ + CrO4 2- Ag2CrO4 (red)
(b) Volhard method :
• In this method of titration, silver is estimated with standard thio cyanate ions
in presence of Fe (III) ion indicator in acidic medium.
• Ag+ + SCN- AgSCN
• At the end of the titration, excess of thio cyanate in the solution react with
Fe(III) and produces a reddish brown colour complex
• Fe+3 + 3 SCN- Fe(SCN) 3
• reddish brown color
• FAJANS METHOD : (INDICTOR ADSORPTION METHOD ):
• It is based on the properties of colloids.
• When the chloride ion solution is titrated with a solution of silver
nitrate, AgCl is precipitated and adsorbs chloride ions which is
termed as primary absorbed layer.
• At the equivalence point ,the excess of Ag+ ions in the AgCl
solution adsorb the negatively charged nitrate ions. (secondary
adsorbed layer)
• When the titration is carried in the presence of fluorescein
indicator (negatively charged) ,its ions are preferentially adsorbed
more strongly than that of the nitrate ions.
• Hence the precipitate gives red color at the end point.