VOLUMETRIC ANALYSIS

by:Kalyani A Gudadhe
TERMS USED IN VOLUMETRIC
ANALYSIS
⚫ Titration: When one of the solutions is taken in a conical
flask and the other is added carefully from the burette till
the chemical reaction between them is just complete, the
process is called titration.
⚫ » Titrant The solution of known strength is called titrant.
⚫ » End Point or Equivalence Point: It is the point at which
the chemical reaction involved in the titration is just
complete.
⚫ » Indicator: Any substance which indicates the end point
of the titration (by change of color) is called an indicator.
Strength: The strength of a solution is the amount of the
substance present in one liter of the solution .
⚫ Normality: The normality of a solution is the number of
gram equivalents of the solute present in one liter of the
solution. It is represented by N.
⚫ Normal Solution: The solution which contains one gm
equivalent of the solute in one liter of the solution
⚫ Molarity: Number of moles of the solute present per liter
of the solution. It is represented by M.
⚫ Standard Solution: A solution whose strength is known is
called a standard solution.
⚫ Error: It is defined as the difference between an
experimental value and the actual Value of a quantity.
⚫ Accuracy: Accuracy is the term which refers to the
correctness of a measurement in Comparison with
the true or accepted value of the quantity measured.
⚫ Precision: It is the degree of reproductively of a series
of measurement on the same property. Accuracy is
usually expressed in terms of error. Precision is the
degree of reproductivity of a series of measurement
on the same property.
⚫ Significant figure is defined as the number which
expresses the result of a measurement such that only
the last digit is in doubt.
Fundamental Volumetric analysis
⚫ Volumetric analysis is a widely-used quantitative
analytical method. This method involves the
measurement of volume of a solution of known
concentration which is used to determine, the
concentration of the analyte. If the strength of one
solution is known, then that of the other can be
calculated Since volume measurements play a key role in
titration.
⚫ in volumetric analysis, a standard solution of a particular
reagent is added in a glass Vessel called burette. This is
then gradually added drop by drop to the solution
containing the analyte until the end point is reached. This
operation is called titration.
⚫ The volume shown on the burette is read and
multiplied by the known titre. Then using the,
burette reading and using the reaction equation, we
can calculate the amount of substance in the
unknown solution
⚫ A standard solution is one of which the titre is known
accurately.
⚫ Volumetric or titrimetric analysis is quantitative
analytical techniques which employ , titration in
comparing an unknown with a standard. In a
titration, a volume of , standardized solution
containing a known concentration of reactant "A" is
added incrementally to a sample containing an
unknown concentration of reactant "B". The titration
proceeds until reactant "B" is just consumed This is
known as the equivalence point.
⚫ Regardless of the type of titration, an indicator is always used to detect the
equivalence point. Indicators added to the reacting solutions that undergo
an abrupt change in color ato near the equivalence point.
⚫ The basic requirements or components of a volumetric method are:
⚫ l. A standard solution (ie., titrant) of known concentration which reacts with
the analyte with a known and repeatable stoichiometry (i.e., acid/base,
precipitation, redox, complexation),
⚫ 2. A device to measure the mass or volume of sample (e.g., pipette, graduated
cylinder, volumetric flask, analytical balance).
⚫ 3. A device to measure the volume of the titrant added (i.e., burette).
⚫ 4, If the titrant-analyte reaction is not sufficiently specific, a pretreatment to
remove interferents,
⚫ 5. A means by which the endpoint can be determined. This may be an
internal indicator (e.g., phenolphthalein) or an external indicator (e.g., pH
meter).
⚫ Volumetric determinations can be subdivided into following types:
⚫ 1. Neutralization: This involves reactions in which acid is neutralized by
using alkal and vice versa
⚫ 2.Oxidation –Reduction method(Oxidimetetry)
⚫ Permaganatometry:based on reactions of oxidation with
potassium permanganate
⚫ Iodometry:Based on oxidation of action of free iodine.
⚫ Chromatometry:In this oxidation by the action of
potassium dichromate K2Cr2O7 is used.
⚫ Bromatometry:Based oxidation of potassium bromated
⚫ 3.Precipitation Titration:Involves precipitation of an
analyte using a precipitant
⚫ 4.Complexometry:Involves formation of complexex
Acid Base Titration
⚫ Acid base titration is base upon the neutralization reaction between
acid and base.Therefore it is also called neutralization titration.in acid
base titration ,the standard solution having known concentration of
acid is titrated against the unknown concentration of base.
⚫ Concept of acid and base
⚫ The concept of acid and base may be understood by three major
theories proposed for acid and base and these are
⚫ 1.Arrhenius acid base theory
⚫ 2. Brosted-lowry proton theory
⚫ 3.Lewis electron theory
⚫ Arrhenius theory of Acid and Base

⚫ Explain Arrhenius theory of Acid and Base

⚫ Acid :As per this theory, acid is a substance which gives Hydrogen ion [H+]
when dissolved in water (Aqueous medium).
⚫ Example : Aq. HCl ⇌ H+ Cl -
⚫ Medium Aq

⚫ HNOH ⇌ H+ + HNO3

⚫ Base: As per this theory, base is a a substance which gives Hydroxyl ion when
dissolved in water (Aqueous medium).
⚫ NaOH ⇌ Na2+ +OH-
⚫ Medium Aq.
⚫ KOH ⇌ K+ +OH-
 ⚫ Bronsted and Lowry concept
⚫ Acid :According to this theory, any substance which is capable of
⚫ donating proton [H+ ] in a chemical reaction is called as Acid.
⚫ eg. HCl+H2O ⇌ H 3O++CI-
⚫ H 2SO4, +H2O ⇌ H 3O+ +HSO 4-
⚫ In this reaction HCl and H2SO4 donate proton, therefore, they act as
⚫ acid.
⚫ Base: According to this theory, any substance which is capable of
⚫ accepting proton [H + ] in a chemical reaction is called as Base.
⚫ e.g. NH3 + H2O ⇌ NH4+ +OH -
⚫ H 2O+ HCI ⇌ H 3O + + CI -

⚫ In above reaction NH 3 and H2O accept Proton [ H 2O ] therefore they

⚫ act as Base.
 Lewis Theory of Acids and Bases
⚫ Though Bronsted-Lowry theory is widely
accepted it failed to take imo considersation
many other acids which do not have proton or
which can transfer proton. To overcome this G.N.
Lewis in 1923 proposed a definition of acid and
base in terms of electronic structure. According
to Lewis theory an acid is a molecule or ion that
can accept a lone pair of electrons; and base is a
molecule or ion that has a lone pair of electrons
which is donated. Thus, an acid may not have a
proton to donate. A substance can be called acid
provided it accepts electron pair.
⚫ eg in a reaction.
⚫ H+ +: NH3--> NH+ 4
⚫ H+accepts a pair of electron NH3 Thus, according to Lewis
concept H+ isan acid, known as Lewis acid and NH3 is a base or
known as Lewis base.
⚫ Similarly, in a reaction between metal ion copper Cu + + and
ammonia.
⚫ Cu + + +4(:NH3) →Cu (NH3)4 + +
⚫ Copper ion acceptselectrons from ammonia, forming
cupra-
⚫ ammonium ion. in this reactioncopper ion acts as
lewis acid and NH3 is lewis base.
⚫ In a reaction between Ag + and CN +, the Ag + acts as
Lewis acid and CN + as Lewis base.
⚫ According to this concept acid-base reaction
involves the formation of a coordinate covalent bond.
⚫ A reaction between ammonia and boron trifluoride is
given below BF3 +:NH3---> F3B : NH3
⚫ Boron trifluoride is a electron deficient
compound and it accepts 8 lone pair of electrons
frome ammonia forming covalent bond. The BF3
is a Lewis acid and NH3 a Lewis base. Lewis bases
are similar to Bronsted-Lowry bases. Several
examples of Lewis acid and bases are given
below :
⚫ Acid : H+, NH4+ ,: Na+, K+,Cu+ +, Al +++, C+ (Carbonium
ions etc.)
⚫ Bases: NH3 H2O, OH-, CI-, CN-, S--
NON AQUEOUS TITRATIONS
INTRODUCTION ;
⚫ Non aqueous titrations are the titrations which are
carried out in non aqueous solvents i.e. solvents other
than water. Non aqueous titrations are method of
choice when reactants of products are insoluble in
water, react with water or are too weak acids or bases
that cannot be titrated in water due to their poor
infliction in pH at end point in water. Commonly
used solvents in non aqueous titrations are acetone,
glacial acetic acid, formic acid, ethylene diamine,
acetic anhydride and chloroform etc.
⚫ CONCEPT OF NON AQUEOUS TITRATIONS
⚫ Non aqueous titrations are mainly based upon the
Bronsted - Lowry theory which suggest That an acid is a
substance which donates proton while base is a substance
which accept Proton. This theory is equally applied to non
aqueous titrations as in aqueous titrations.
⚫ Bronsted - Lowry theory states that an acid dissociates in
solution to give a proton and form conjugated base and a
base combine with the proton from dissociated acid to
produce a conjugate acid. An acid donates proton only
when a base is present to accept this proton .
⚫ in reaction below, B- is the conjugate base of acid HB and proton is
only difference between acid and its conjugate base. Any base can
combine with this proton to give a conjugate base.
⚫ HB H+ + B –
⚫ Acid Proton Conjugate base
⚫ Therefore, base B combines with proton and produced conjugate acid
of base B.
⚫ B + H+ HB+
⚫ Base Proton Conjugate acid
⚫ Advantages and disadvantages of non aqueous titrations are listed
here under:
⚫ Advantages: 1. Weak acids and base give poor end points in aqueous
titrations but in non aqueous titrations they give good end point.
⚫ 2. The substances which are poorly soluble in water but soluble in
non aqueous organic solvents can be determined by non aqueous
titrations.
⚫ 3. Mixture of two or more acids can be analyzed. The
individual acid can give separate end point in different
solvents.
⚫ Disadvantages:
⚫ 1. Temperature, moisture and carbon dioxide should be
controlled.
⚫ 2. Solvents used in non aqueous titrations are expensive.
⚫ 3.Volatile solvents such as Ammonia can pollute solvent,
4.Indicators need to be prepared in non aqueous medium,
5.some solvents are hazardous if mishandled such as
ammonia which if inhaled too much can prove to be fatal.
6. It is not an environment friendly method.
NON AQUEOUS SOLVENTS
⚫ Solvent play an important role in non aqueous titration
because the solvent supports the Dissociation of weak acid or
base and alter the behavior of analyte. Non aqueous solven,
Majorly classified into four types
⚫ :1 Amphiprotic solvents: These are the solvents which are able
to donate as well as accept protons ie. they posses both
protophilic and protogenic properties.
⚫ Examples of such solvents are water, weak organic acids and
alcohols. For example acetic acid acts as an acid by dissociation
to give protons.
⚫ CH3COOH CH3COO- + H+
⚫ While in the presence of a strong acid like perchloric acid it
acts as base and accepts protons,
⚫ CH3COOH + HClO4 CH3COOH2 + + ClO4-
⚫ 2. Aprotic solvents: These are the solvents which are
chemically inert and doesn't donate o accept protons
therefore they don't have any acidic or basic nature.
These type of solvent ‘ have low dielectric constant
for example toluene, chloroform, benzene and carbon
tetrachloride.
⚫ 3. Protophilic solvents: These are the solvents which have
high affinity for protons and are basic in nature. They
produce solvated protons by abstracting protons from
acids.
⚫ HB + S SH+ +B
⚫ Acid Solvent Solvated proton Conjugates base
⚫ Some examples of protopholic solvents are liquid
ammonia, ketones and amines etc.
⚫ 4. Protogenic solvents: These are the solvents which
readily donate protons and are acidic in nature. Sulphuric
acid and hydrogen fluoride are the examples of protogenic
solvents.
EFFECTS OF SOLVENTS
⚫ In non aqueous titrations, two types of effects of solvents
are seen which are:
⚫ 1. Leveling effect .
⚫ 2. Differentiating effect
⚫ 1. Leveling effect: Weak acids and bases are normally used
in the presence of strong protophilic (pyridine, liquid
ammonia) and strong protogenic solvents (HF, H2SO4)
because their strengths are enhanced by these solvents.
Weak acid acts like strong acid in the presence of strong
protophillic solvents as well as weak base act as strong
base in the presence of strong protogenic solvents. This
effect is called leveling effect and solvents called leveling
solvents.
⚫ 2. Differentiating effect: In less basic non aqueous
solvent like glacial acetic acid, the dissociation of
different acids varies ie. dissociation of perchloric
acid is more as compared to hydrochloric acid.
Therefore, in glacial acetic acid perchloric acid acts as
a strong acid as compared to hydrochloric acid. This
effect of differentiating between the strengths of
acids is called differentiating effect and the solvents
like glacial acetic acid etc, which show this effect are
called differentiating solvents.
⚫ ALKALIMETRY AND ACIDIMETRY
⚫ In non aqueous titrations generally weakly acidic and
basic substances are determined therefore in non aqueous
titrations alkalimetry is defined as titrations of weak bases
and acidimetry is defined as titrations of weak acids.
⚫ These titrations are described here under.
⚫ Titration of Weak Bases:Titration of weak bases is done
by using mainly perchloric acid as a standard acid. Acetic
acid is generally used as the solvent for dissolving weak
bases. Weak base dissolved in non aqueous solvent is
titrated with standard perchloric acid solution. Reactions
involved in the titration can be explained as follows.
⚫ When acetic acid is present alone, it behaves as a weak acid as
it is poorly dissociated and has very little tendency to donate
protons.
⚫ CH3COOH CH3COO + H+
⚫ But on the addition of perchloric acid (which is a strong acid)
to acetic acid, Onium ions are formed which have higher
tendency to donate protons.
⚫ HCIO4 + H+ + CIO4-
⚫ CH3COOH + H+ CH3COOH2 (Onium Ion) Furthermore,
on addition of pyridine (which is a weak base) to acetic acid,
following Reaction occurs:
⚫ C5H5N + CH3COOH C5H5N + + CH3COO
⚫ Acetate ions produced have higher tendency to accept protons.
⚫ Titration of weak acids:Titration of weak acids such
as barbiturates, benzoic acid etc can be done using
bases like alkali methoxides (sodium methoxide,
potassium methoxide, lithium methoxide) or
tetrabutylammonium hydroxide etc. Non aqueous
solvents used in titration are ethylenediamine,
Dimethyl formamide (DMF) etc. Reactions taking
place during titration of benzoic acid in dimethyl
formamide with sodium methoxide is as follows.
⚫ On Dissolving benzoic acid in Dimethyl
formamide(DMF),Following reaction takes place.
⚫ C6H5COOH+H-CON(CH3)2 HCON+H(CH3)2+C6H5COO
⚫ ionization of sodium methoxide take place as follows:
⚫ CH3ONa CH3O- +Na
⚫ From reaction 1 and 2 above,
⚫ HCON+ H(CH3)2 +CH3O- HCON(CH3)2+CH3OH
⚫ C6H5COOH+ CH3ONa C6H5COONa+CH3OH
PRECIPITATION TITRATIONS
⚫ INTRODUCTION
⚫ Precipitation titrations are the titrations that involve the formation of
precipitate, Silver nitrate is most important and mainly used precipitating
agent and titrations which use silver nitrate as a precipitating agent is called
Argentimetric titrations.
⚫ Precipitation titrations are mainly based on the principle of solubility
product. It is of following type
⚫ 1) MOHR’S METHOD
⚫ In mohars method, halides can be determined by titrating with AgNO3 using
K2CrO4 as an indicator and formation of colored precipitate takes place.
⚫ Silver nitrate titrated directly against sodium chloride and form white
precipitate silver chloride with sodium nitrate
⚫ AgNO3 + NaCl —> AgCl + NaNO3
⚫ Silver nitrate Sodium chloride Silver chloride (white ppt) Sodium nitrate
⚫ When all the chlorides of sodium chloride is
consumed . It reacts with potassium chromate and
end point can be detected with appearance of brick
red colour due to formation of silver chromate along
with potassium nitrate.
⚫ AgNO3 + K2CrO4 —> Ag2CrO4+ 2KNO3
⚫ (Silver nitrate) (Potassium chromate) Silver nitrate (Brick red colour)Potassium nitrate
⚫ 2) VOLHARD’S METHOD
⚫ In this, Silver salt is titrated with NH4SCN using ferric alum as
indicator. During the titration AgSCN is formed while at the end
point, excess NH4SCN reacts with Fe(II) to form deep red [FeSCN].
⚫ A precipitate of silver thiocyanate is produced on addition of
thiocyanate solution.
⚫ Reactions involved are:
⚫ Ag + SCN —> AgSCN
⚫ When even a slightest excess of thiocyanate is present,a reddish
brown coloration is produced due to the formation of a complex i0n.
⚫ SCN [FeSCNP with Fe + | vess and the excess is back titra Standard
silver nitrate solution is added in & standard thiocyanate solution.