THEORY OF QUANTITATIVE

ANALYSIS
 QUANTITATIVE ANALYSIS
Definition
Quantitative analysis is determination of the Quantitative contents of individual elements or compounds
present in a substance.

Classification of Quantitative analysis

1. Volumetric analysis

2. Gravimetric analysis
 GENERAL TERMS USED IN VOLUMETRIC ANALYSIS

TITRATION

Titration, also known as titrimetry, is a quantitative analysis technique that can be used to calculate the
concentration of a given analyte in a mixture.
 STANDARD SOLUTION

• In analytical chemistry, a standard solution is a solution containing a precisely known concentration of an element

or a substance. A known weight of solute is dissolved to make a specific volume.

A primary standard has the following features.

•It is highly pure and cheaply available.
•It is highly soluble in water.
•It is neither deliquescent nor hygroscopic.
•It is highly stable.
Oxalic acid, Mohr's salt, potassium dichromate are some examples of primary standards.

Secondary standard
• Substances whose standard solutions cannot be prepared directly are called secondary standards.
Some examples are sodium hydroxide and potassium permanganate.
• It should be readily soluble.
•It should not effect the actual chemical reaction.
•It should give a different colors at different pH.
•One or two drops of indicator should be sufficient to produce the necessary color change. 
 VOLUMETRIC ANALYSIS

Volumetric Analysis measures volume of a reagent needed to react with an analyte

CLASSIFICATION OF VOLUMETRIC ANALYSIS

Acid-Base (or) Neutralization titration

Oxidation-Reduction (or) Redox titration

Complexometric titration

Precipitation Reactions
 ACID – BASE TITRATIONS/NEUTRALISATION TITRATIONS

•Acidimetry : In acidimetry the given alkali is estimated using standard acid solution.

•Alkalimetry : In alkalimetry the given acid is estimated using standard base solution.

•Indicator : It is a substance whose solution helps in locating the end point by undergoing colour change
SOME COMMON INDICATORS USED IN ACID – BASE TITRATIONS 

 
 

 
THEORY OF ACID - BASE INDICATOR

An acid base indicator is a substance which has one colour in acidic medium and a completely different colour in basic
medium.

There are two theories which explains the action of acid base
indicators

1.Ostwald theory

2.Quinonoid theory.
 OSTWALD THEORY 

•According to this theory an indicator is either a weak organic acid or a weak organic base
•The unionised compound has one colour and the ion produced has another colour.
•The indicator ionise in the following manner :
 ACTION OF PHENOLPHTHALEIN

•It is colourless organic compound which is a weak organic acid ,it dissolves in water and dissociates slightly to form
H+ ions (colourless) and ph – ions  (pink)

HPh ⇌ H+ + Ph-

Case1 : In Acidic medium 

•If the solution is made acidic for example when HCl is added to phenolphthalein then the increase in H+ ion
concentration supresses the dissociation of  phenolphthalein due to common ion effect, then the equilibrium
shifts towards left hand side of the equation and the solution remains colourless
Case 2 : In Basic medium 
•If the solution is made alkaline by adding few drops of NaOH to phenolphthalein OH- ions reacts with the H+ ions
to form unionised water molecules , the decrease  in the H+ ion concentration shifts the equilibrium towards right
thus more of the indicator ionises and solution becomes pink ( due to Ph- ions)
 ACTION OF METHYL ORANGE

It is organic compound which is a weak organic base and is soluble in water and dissociates to a very small extent.

MeOH ⇌ Me+ + OH-

Case1 : In Acidic medium 

•If the solution is made acidic for example when HCl is added to methyl orange then the increase in H+ ions
furnished by the acid combine with OH- ions to form unionized water molecule.Thus decrease in OH- ion
concentration shifts the equilibrium towards right.Hence the solution acquires a pink colour due to Me+ ions.

Case 2 : In Basic medium

•If the solution is made basic is added to Methyl orage then the increase in OH- ion concentration supresses the
dissociation of  MeOH due to common ion effect, then the equilibrium shifts towards left hand side of the
equation and the solution remains pale yellow.
Reddish pink in acidic Yellow in basic medium
 QUINONOID THEORY

According to this theory the colour change of an acid-base indicator arises as a result of structural change. It is supposed
that an indicator exists as an equilibrium mixture of two tautomeric forms namely, benzoid and quinonoid forms.
 
• One form exists in acidic solution and the other form in basic solution.

• The two forms possess two different colours and as the pH of the solution containing the indicator is changed, the
solution shows a change of colour.
 PHENOLPHTHALEIN

In acidic medium In basic medium

• colourless • Pink colour

• Stable in Benzenoid form • Stable in Quinonoid form

 METHYL ORANGE

In acidic medium In basic medium

• Pinkish red • Yellow colour

• Stable in Quinonoid form • Stable in Benzenoid form

 VARIATION OF pH DURING DIFFERENT TYPES OF TITRATIONS

In correct detection of end point will affect the titration calculation and thus it becomes very important to
select the correct indicator used in titration. The neutralization reactions are of the following four types:

•A strong acid versus a strong base.

•A weak acid versus a strong base.

•A strong acid versus a weak base. 

•A weak acid versus a weak base. 

• In order to choose a suitable indicator, it is necessary to understand the pH changes in the above four types
of titrations.

• The change in pH in the vicinity of the equivalence point is most important for this purpose.

• The curve obtained by plotting pH as ordinate against the volume of alkali added as abscissa is known as
Neutralisation or titration curve.

• In each case 25 mL of the acid (N/10) has been titrated against a standard solution of a base (N/10). Each titration
curve becomes almost vertical for some distance and then bends away again.

• This region of abrupt change in pH indicates the equivalence point.

• For a particular titration, the indicator should be so selected that it changes its colour within vertical distance of
the curve.
i)  Strong acid vs. strong base

pH curve of strong acid (say HCI) and strong base (say NaOH) is vertical over almost the pH range 4-10. So the
indicators phenolphthalein (pH range 8.3 to 10.5), methyl red (pH range 4.4-6.5) and methyl orange (pH range 3.2-4.5)
are suitable for such a titration.
(ii) Weak acid vs. Strong base:

pH curve of weak acid (say CH3COOH of oxalic acid) and strong base (say NaOH) is vertical over the approximate
pH range 7 to 11. So phenolphthalein is the suitable indicator for such a titration.
(iii) Strong acid vs. weak base:

pH curve of strong acid (say HCl or H2SO4 or HNO3) with a weak base (say NH4OH) is vertical over the pH range
of 4 to 7. So the indicators methyl red and methyl orange are suitable for such a titration.
(iii) Weak acid vs. weak base:

pH curve of weak acid and weak base indicates that there is no vertical part and hence, no suitable indicator can be
used for such a titration.
 II) REDOX TITRATIONS OR OXIDATION-REDUCTION TITRATIONS

Titrations involved in oxidation –reduction reactions are Redox Titrations.

Oxidation- Loss of electrons

• The following points describe a substance that has undergone oxidation.

• The addition of oxygen.
• Removal of hydrogen which was attached to the species.
• The donation/loss of electrons.
• An increase in the oxidation state exhibited by the substance.

Reduction – Gain of electrons

• A substance can undergo reduction can occur via:

• The addition of hydrogen.
• The removal of oxygen.
• The acceptance of electrons.
• A reduction in the overall oxidation state.
Oxidizing agent(oxidant)- The substance which gains electron i.e., which undergoes Reduction.
e.g: KMnO4, K2Cr2O7

Reducing agent(oxidant)-The substance which losses electron i.e., which undergoes Oxidation.
e.g: Mohr’s salt [Fe(NH4)2SO4.6H2O]

Oxidimetry-Determination of strength of Reducing agent by standard solution of oxidizing agent.

Reductimetry –Determination of strength of oxidizing agent by standard solution of reducing agent.

 Types of Redox Titrations

•Dichrometry –Estimation which involves in the use of Potassium dichromate

(K2Cr2O7 )

•Iodometry –Estimation involves in liberated iodine (I2).

•Permanganometry -Estimation which involves in the use of Potassium

permanganate(KMnO4)

• Bromometry uses a bromine (Br2) titrant.

• Cerimetry employs cerium(IV) salts

 Dichrometry

• Potassium dichromate unlike potassium permanganate is an excellent primary standard since it is

available in the pure form and its solutions are stable.

• Due to the green colour of Cr+3ions potassium dichromate cannot be used as self indicator. The suitable
indicators for this titration are Diphenylamine sulphonate

• E.g : Estimation of Fe(II) using Potassium dichromate

 IODIMETRIC AND IODOMETRIC TITRATIONS

The reduction of free iodine to iodide ions and oxidation of iodide ions to free iodine occurs in these titrations.
2I−→I2+2e ……………. (oxidation) (Iodometry)

I2+2e→2I− ……………. (reduction) (Iodimetry)

Free iodine is used in the iodimetric titration, while in the iodometric titration an oxidation agent is used to react to
liberate free iodine.

Iodine (I2) serves as oxidizing agent which may be employed to titrate sufficiently strong reducing agents.

• Iodide ion (I-) behaves as a mild reducing agent that may be used for the determination of strong oxidizing
agents.
In an Iodometric titration, a starch solution is used as an indicator since it can absorb the I2 that is released. This
absorption will cause the solution to change its color from deep blue to light yellow when titrated with standardized
thiosulfate( hypo) solution.

NOTE: PLEASE GIVE EXAMPLE OF Cu(II) ESTIMATION USING HYPO

 Permanganometry

• Potassium permanganate is a strong oxidising agent and in the presence of sulfuric acid it acts as a
powerful oxidising agent.

• Solution containing anion MnO4– ions are purple in color

•  KMnO4 serves as self indicator in acidic solution .

• E.g: Estimation of oxalic acid with KMnO4

• 2KMnO4 + 3H2SO4 + 5(COOH)2 → K2SO4 + 2MnSO4 + 8H2O + 10CO2↑

• In KMnO4 Manganese is in +7 oxidation state after titration Manganese is in +2

oxidation state.
 INDICATORS USED IN REDOX TITRATIONS (REDOX INDICATORS)

Redox Indicators are themselves an oxidant or reductant. Oxidized, form has one colour and reduced form
has other colour. When slight excess of oxidant is present, the Indicator changes its colour and is shown as
end point of the titration. There are different methods of detection point of redox titrations. They

1.Self indicators

2. External Indicators

3. Redox indicators
 SELF INDICATOR

The oxidised or reduced form of the titrant or the substance itself self indicating.

e.g:KMnO4

Note: Please refer Permanganometry

 EXTERNAL INDICATOR

The indicator which are not added to the solution are called external indicator. These do not take part in the reaction.

Example:
• Potassium Ferro cyanide K3[Fe(CN)6] can acts as external indicator during titration of ammonium or ferrous
sulphate (FeSO4) with Potassium dichromate (K2Cr2O7).

• K3[Fe(CN)6] gives blue colour with Ferrous salt solution but no colour with ferric salts.
 REDOX INDICATOR

A redox indicator is an indicator compound that changes color at specific potential differences. A redox indicator compound
must have a reduced and oxidized form with different colors and the redox process must be reversible. 

e.g : Diphenyl amine indicator has blue violet color in oxidized form and colorless in reduced form
 III) PRECIPITATION TITRATIONS OR ARGENTOMETRY

• A special type of titrimetric procedure involves the formation of precipitates during the course of titration.

• The titrant react with the analyte forming an insoluble material and the titration continues till the very last amount
of analyte is consumed.

Principle of Precipitation Titration

• The main principle of the precipitation titrations is that the quantity of the added precipitating reagent or
precipitant is equivalent to the substance being precipitated.
 TYPES OF PRECIPITATION TITRATION

According to end point detection method, three main procedures are widely used depending on the type of application.

They are:

• Mohr Method

• Volhard Method

• Fajans Method
 MOHR’S METHOD

• This method utilizes chromate as an indicator. Chromate forms a precipitate with Ag+ but this precipitate has a
greater solubility than that of AgCl in Nacl vs AgNO3 titrations.

• Therefore, AgCl is formed first and after all Cl- is consumed, the first drop of Ag+ in excess will react with the
chromate indicator giving a reddish precipitate.

• 2 Ag+ + CrO4-2 Ag2CrO4

 VOLHARD METHOD

In this method standard Potassium thiocyanate is titrated against Ag+ solution containing Fe3+ (Ferric alum
indicator).

• The excess Ag+ is then titrated with standard SCN- solution until a red color is obtained which results from the
reaction.
Ag+ + SCN-  AgSCN

• Fe3+ + SCN-  Fe(SCN)2(Red ppt)

 FAJAN’S METHOD

• Fluorescein and its derivatives are adsorbed to the surface of colloidal AgCl.(Reddish tinge on white ppt)

• After all chloride is used, the first drop of Ag+ will react with fluorescein (FI- ) forming a reddish color.

Ag+ + FI-  AgFI

NOTE:
Among these methods, the Volhard Method is widely used because we can detect the end point of precipitation titration
very well.