Liquid State

o A liquid has no definite shape and takes up the shape of the container in which it is
kept.
o A liquid has a definite volume due to weaker intermolecular force of attraction than
solids.
o They can flow from a higher lever to a lower level.
o A liquid is compressible due to larger distance between the neighbouring molecules
than solid but lesser than gas.
o They have lower density.
o A liquid can diffuse into another liquid due to fact that molecules move faster in a
liquid but is slower as compared to gases.
Intermolecular Forces
o Intermolecular forces can be described as the forces ofattraction and repulsion
existing between the interactingparticles of atoms and molecules in a compound.

o The attractive intermolecular forces are called van der Waals forceswhich
includedispersion forcesor London forces, dipole-dipole forces, anddipole-induced dipole
forces.
o Intermolecular forces in case of solids are very strong. The constituent particles are
closely packed thereby making the solids incompressible and of high density.

o Intermolecular forces in case of liquids keeps the particles tied to each other but
cannot keep them in fixed positions thereby making them easy to flow and have a definite
shape.

o Intermolecular forces in case of gases are extremely weak thereby allowing the
constituent particles to move freely.

The Liquid State

Liquids and Gases both are termed as fluids. The reason being their property to flow. But at the
molecular level, a liquid is different from a gas. From forces of attraction to the effects of
physical properties, liquids show different properties and behavior. Here we learn the
microscopic and macroscopic behavior of a liquid state.

At normal conditions of temperature, pressure, and volume liquids generally, show the above-
mentioned features. When the physical conditions change the basic characters of liquids also
undergo a drastic change. Apart from the above characteristics, liquids also show the following
properties:
Vapour Pressure

When a liquid is filled in a container, its walls are occupied by the vapors from that liquid.
Liquids show the unique property of turning into vapors, as soon as the temperature rises!
Generally, vapors from the aqueous substance occupy the walls of the unfilled part of the
container and exert a pressure on the walls of that container, this pressure is called the vapor
pressure.

Initially, the vapor pressure increases but after some time it becomes constant. Gradually, an
equilibrium between the liquid phase and the vapor phase is established. The vapor pressure at
the point of equilibrium is known as the equilibrium vapor pressure or saturated vapor pressure.
The whole phenomenon of vapor formation solely depends on the temperature and hence tends
to increase with the increasing temperature.

Boiling Point

Liquids when heated evaporate. In closed vessels, the heating produces vapors which exert
pressure on the container of the walls while when heated in open vessels, the vapors evaporate to
the surroundings from the surface. When bulk vapors evaporate to the surroundings at a specific
temperature, then that temperature is called the boiling point. At the boiling point, the vapor
pressure is equal to the liquid pressure.

The boiling temperature at 1 atm.pressure is called as the normal boiling point while the boiling
point at 1 bar is called the standard boiling point. The normal boiling point of water is 100° C
and the standard boiling point in 99.6° C.

The pressure directly affects the boiling point. In hilly areas liquids boil at the lower temperature
as compared to plains. The reason for this is that at higher altitudes the pressure is very low,
hence the boiling point is also comparatively low.

The boiling point is not a result of heating, rather it is the outcome of the increasing vapor
pressure. Initially, we can see a line between the liquid phase and vapor phase but as the
temperature increases, the speed of vaporization also increases leading to more and more
molecules entering the vapor phase. With the rising density of vapors, the density of liquids
decreases making the molecules move apart from each other.

Surface Tension

We already know that liquids do not have a shape of their own, they take the shape of the
container! Despite its undefined shape, we know that the drop of any liquid looks like a sphere.
Why is it so? The answer is due to surface tension of liquids.Surface tension is the property
specific to liquids.

The molecules in a liquid experience an equal intermolecular force from all the sides. The
intermolecular force between the molecules on the surface is exerted perpendicularly
downwards and this is called the surface tension of the liquid. The surface tension of a liquid
depends on the intermolecular forces directly, greater the force higher is the surface tension.

As compared to other molecules in the container, the surface molecules are the most active and
energetic. Despite being less in number than the other molecules their pressure and energy are
high and hence exert a downward force towards the liquid. Now if the surface is distorted and
the surface of the liquid pulls another molecule from the bulk, then it takes energy to rebuild the
surface area. The energy required to build the surface tension is called the surface energy. The
unit for surface tension is Jm-2 and it is denoted by γ.

Effect of Temperature

The surface tension depends on the surface area.The lower the surface area the lower shall be the
surface tension of the surface molecules towards downwards. Surface tension is also inversely
proportional to the temperature. The kinetic energy between the molecules tends to increase with
the increasing temperature but decreases the force of attraction between the molecules. This
decreases the surface tension of the liquid.

Viscosity

The viscosity of a liquid substance is a measure of resistance to flow. The intermolecular forces
and internal friction between the moving molecules in the liquids make them viscous to flow.
When a liquid flows, the molecules in contact with the surface are stationary, while the upper
layer tends to move, the velocity of this moving layer increases with the distance of layers from
the stationary layer.

This implies that the farther the moving layer, the faster it moves. This kind of increasing
velocity is termed as Laminar flow. The lower layer nearest to the surface retards the movement
of the layer above it, this results in viscosity in liquids.

Coefficient of Viscosity

As we already know that viscosity is the resistance to flow shown by molecules. Now, the flow
of layers requires force to get away with the resistance between layers. This force helps to
maintain the flow of molecular layers and is directly proportional to the area of contact of layers
and velocity gradient. The ratio of changed velocity (du) and original velocity (dx) is termed as
the velocity gradient.

Now, F ∝ A

F ∝ du/dx ( velocity gradient)

F ∝ A(du/dx)
⇒ F= η A(du/dx)

Here, η is the proportionality constant and is called as the coefficient of viscosity. The unit of η
in SI system is 1 Newton second per sq.metre (1 N sm-2 ) or Pascal-second (Pa s), while in the
CGS system the unit of η is Poise.

Effect of Physical Changes in Viscosity

The viscosity of the aqueous substance decreases with the increasing temperature. At high
temperature, the force of attraction between the molecules decreases and due to the high kinetic
energy in the molecules the intermolecular forces slip past each other in the layer. This results in
decreased viscosity.

Q: The magnitude of the force that controls the shape of the liquid is called the ____________.

a. Force of condensation b. Force of attraction c. Surface tension d. all of the above

Answer: c. Surface tension. The shape of the liquids is due to the surface tension. The larger the
intermolecular force the greater is the surface tension.

Guldberg’s Rule
Normal boiling point of the liquid is nearly two – third of its critical temperature when both
are expressed on the absolute scale. Tb = 2/3 Tc
Trouton’s Rule
The molar heat of vapourisation of a liquid expressed in Joules divided by normal b.p. of the
liquid on the absolute scale is approximately equal to 88. ΔHv / Tb.p. = 88 JK–1 mol–1
Molar refraction The index of refraction (n) and molar refraction (RD) are
indications of the manner in which a molecule interacts with light. The index of refraction is
the ratio of the speed of light in a vacuum (c) to the speed of light in the medium (v):

n = c/v

Vapour Pressure of Liquid solutions

Vapour pressure can be defined as pressure formed by the vapor of the liquid (or solid) over the
surface of the liquid. This pressure is formed in a thermodynamic equilibrium state in a closed
container at a certain temperature. Liquid’s evaporation rate is identified by the equilibrium
vapor pressure. Vapour pressure increases with the temperature. The boiling point of the liquid is
the point when the pressure exerted by surrounding equals to the pressure exerted by vapor. In
this chapter, we will study more about the Vapour Pressure on liquids and its characteristics.
What is Vapour Pressure?

You have read about pressure. It is the force that a mass exerts on another. But, do you know
vapour also exerts pressure, even if you can’t see it? You have of course felt it! Haven’t you?

We form a liquid Solution by dissolving a solid, liquid or gas in a specific liquid solvent. Vapour
Pressure of liquid solutions is the amount of pressure that the vapours exert on the liquid solvent
when they are in equilibrium and a certain temperature.

Vapour pressure changes with the temperature of the surroundings and the nature of the liquid.
Let us now have a look a some of the important characteristics of vapour pressure on liquid
solutions.

Characteristics of Vapour Pressure

 A pure liquid experiences a greater amount of vapour pressure as against a liquid’s

solution.

 It is inversely proportional to the forces of attraction existing between the molecules of

a liquid.
 It increases with a rise in the temperature. This is because the molecules gain kinetic
energy and thus, vapourise briskly.

A liquid solution might have a volatile solute and solvent as well. In the majority of the cases,
we can see that the solvent is volatile, while the solute is not. Based on this, we will study it in
two instances: Liquid-Liquid Solutions and Solid-Liquid Solutions.
Vapour Pressure of Liquid-Liquid Solutions

To evaluate this, we take two volatile liquid solutions. Let us name their liquid components as A
and B. After placing the volatile liquid with their components in a closed vessel, we find that
equilibrium establishes between the liquid phase and vapour phase.

Suppose Ptotal is the overall vapour pressure at an equilibrium state and let PA and PB be the
partial vapour pressures of components A and B respectively. Adding further, the mole fraction
of respective components is xA and xB respectively. To evaluate vapour pressure of
volatile liquids, we use Raoult’s Law.

Raoult’s Law

The law states that the partial pressure is directly proportional to the mole fraction of the solute
component. So, according to Raoult’s Law, the partial pressure of A will be

P A ∝ xA

PA = PA0 xA

where PA0 is the vapour pressure of pure liquid component A. Similarly partial pressure of B will
be

P B ∝ xB

PB = PB0 xB

where PB0 is the vapor pressure of pure liquid component B. Now, we will apply Dalton’s law of
partial pressures. This law tells us that the total pressure ( Ptotal) of the solution placed in a
container is the sum of partial pressures of its respective components. That is

Ptotal = PA + PB

Ptotal = PA0 xA + PB0 xB

Also since, xA + xB = 1 , we can write the relation as:

Ptotal = PA0 + (PB0 – PA0) xB

Vapour Pressure of Solutions of Solids in Liquids

Let us now look at the other type of solutions i.e. solids in liquid solution. Here we consider a
solid as the solute, while the solvent is a liquid. In these cases, the solute is non-volatile in
nature. The vapour pressure is less than the pure vapor pressure of the solution. Let us now see
how we can find the overall vapour pressure of such a solution.

We consider a solution in which A is the solvent and B is the solute. Applying the Raoult’s Law,
we know that partial vapour pressure of individual component (solute/solvent) is directly
proportional to its mole fraction.

Now, if we add a non-volatile solute, it is imperative that vapour pressure comes only from the
solvent part. This is because they are the only available component in the vapour phase. Hence,
if PA is the vapor pressure of the solvent, xA is its mole-fraction and PA0 is the vapor pressure of
the pure solvent, then by Raoult’s law, the relation will come out to be:

P A ∝ xA

PA = PA0 xA

When we plot a graph between mole fraction of solvent and vapour pressure, we find its nature
to be linear.

Raoult’s Law

In 1986, it was a French Chemist, Francois Marte Raoult who proposed a relationship between
partial pressure and mole fraction of volatile liquids. According to the law, ‘the mole fraction of
the solute component is directly proportional to its partial pressure’.

On the basis of Raoult’s Law, liquid-liquid solutions can be of two types. They are:
  Ideal Solutions

 Non-ideal Solutions

Ideal Solutions

The solutions which obey Raoult’s Law at every range of concentration and at all temperatures
are Ideal Solutions. We can obtain ideal solutions by mixing two ideal components that are,
solute and a solvent having similar molecular size and structure.

For Example, consider two liquids A and B, and mix them. The formed solution will experience
several intermolecular forces of attractions inside it, which will be:

 A – A intermolecular forces of attraction

 B – B intermolecular forces of attraction

 A – B intermolecular forces of attraction

The solution is said to be an ideal solution, only when the intermolecular forces of attraction

Characteristics of Ideal Solutions

Ideal Solutions generally have characteristics as follows:

 They follow Raoult’s Law. This implies that the partial pressure of components A and
B in a solution will be PA = PA0 xA and PB = PB0 xB . PA0 and PB0 are respective
vapour pressure in pure form. On the other hand, xA and xB are respective
mole fractions of components A and B

 The enthalpy of mixing of two components should be zero, that is, Δmix H = 0. This
signifies that no heat is released or absorbed during mixing of two pure components to
form an ideal solution
 The volume of the mixing is equal to zero that is, Δmix V = 0. This means that total
volume of solution is exactly same as the sum of the volume of solute and solution.
Adding further, it also signifies that there will be contraction or expansion of
the volume while the mixing of two components is taking place.
 The solute-solute interaction and solvent-solvent interaction is almost similar to the
solute-solvent interaction.

Examples of Ideal Solutions

 n-hexane and n-heptane

 Bromoethane and Chloroethane

 Benzene and Toluene
  CCl4 and SiCl4
 Chlorobenzene and Bromobenzene
 Ethyl Bromide and Ethyl Iodide
 n-Butyl Chloride and n-Butyl Bromide

Non-Ideal Solutions

The solutions which don’t obey Raoult’s law at every range of concentration and at
all temperatures are Non-Ideal Solutions. Non-ideal solutions deviate from ideal solutions and
are also known as Non-Ideal Solutions.

Characteristics of Non-ideal Solutions

Non-ideal solutions depict characteristics as follows:

 The solute-solute and solvent-solvent interaction is different from that of solute-solvent

interaction

 The enthalpy of mixing that is, Δmix H ≠ 0, which means that heat might have released
if enthalpy of mixing is negative (Δmix H < 0) or the heat might have observed if enthalpy
of mixing is positive (Δmix H > 0)
 The volume of mixing that is, Δmix V ≠ 0, which depicts that there will be some
expansion or contraction in the dissolution of liquids

Non-ideal solutions are of two types:

 Non-ideal solutions showing positive deviation from Raoult’s Law

 Non-ideal solutions showing negative deviation from Raoult’s Law

i) Positive Deviation from Raoult’s Law

Positive Deviation from Raoult’s Law occurs when the vapour pressure of the component is
greater than what is expected in Raoult’s Law. For Example, consider two components A and B
to form non-ideal solutions. Let the vapour pressure, pure vapour pressure and mole fraction of
component A be PA , PA0 and xA respectively and that of component B be PB , PB0 and
xB respectively. These liquids will show positive deviation when Raoult’s Law when:

 PA > PA0 xA and PB > P0B xB, as the total vapour pressure (PA0 xA + P0B xB) is greater
than what it should be according to Raoult’s Law.

 The solute-solvent forces of attraction is weaker than solute-solute and solvent-solvent

interaction that is, A – B < A – A or B – B
 The enthalpy of mixing is positive that is, Δmix H > 0 because the heat absorbed to form
new molecular interaction is less than the heat released on breaking of original molecular
interaction
 The volume of mixing is positive that is, Δmix V > 0 as the volume expands on the
dissolution of components A and B

Examples of Positive Deviation

Following are examples of solutions showing positive deviation from Raoult’s Law:

 Acetone and Carbon disulphide

 Acetone and Benzene

 Carbon Tetrachloride and Toluene or Chloroform
 Methyl Alcohol and Water
 Acetone and Ethanol
 Ethanol and Water

Negative Deviation from Raoult’s Law

Negative Deviation occurs when the total vapour pressure is less than what it should be
according to Raoult’s Law. Considering the same A and B components to form a non-ideal
solution, it will show negative deviation from Raoult’s Law only when:

 PA < PA0 xA and PB < P0B xB as the total vapour pressure (PA0 xA + P0B xB) is less than
what it should be with respect to Raoult’s Law

 The solute-solvent interaction is stronger than solute-solute and solvent-solvent

interaction that is, A – B > A – A or B – B
 The enthalpy of mixing is negative that is, Δmix H < 0 because more heat is released
when new molecular interactions are formed
 The volume of mixing is negative that is, Δmix V < 0 as the volume decreases on the
dissolution of components A and B
Different Types of Solutions

Solutions are of different types, based on a number of criteria, like the difference in the solute or
the solvent etc. Let us now look at the different types of solutions, based on different criteria.

On the Basis of Water as Solvent

Based on the whether the solvent is water or not, solutions are of two types.

 Aqueous solutions: These solutions have water as the solvent. Examples of such
solutions are sugar in water, carbon dioxide in water, etc.

 Non-Aqueous Solutions: These solutions have a solvent that is not water. It could be
ether, benzene, petrol, carbon tetrachloride etc. Common examples include sulfur
in carbon disulphide, naphthalene in benzene, etc.

On the Basis of the Amount of Solute Added

Based on the amount of solute present in the solution, we can classify them into the following
types.

 Unsaturated Solution: An unsaturated is one that can dissolve more solute at a

definite temperature. It means that we can still add more solute to the solvent.

 Saturated Solution: A solution is said to be saturated when we can’t add any more
solute to the solvent. This means that the solution can’t dissolve any more solute at a
definite temperature.
 Supersaturated Solution: A supersaturated solution is one where the solute is present
in an excess amount. This solute is dissolved forcefully by raising the temperature or
pressure of the solution. These generally crystal out in the bottom by the method called
crystallisation.

On the Basis of Amount of Solvent Added

 Concentrated Solution: A concentrated solution has large amounts of solute in the
given solvent. Examples include Brine solution, Orange juice, dark colour tea.

 Dilute Solution: A dilute solution has a small amount of solute in a large amount of
solvent. Examples include Salt solution, light colour tea.

On the Basis of Concentration of Solute in Two Solutions

Let us consider a cell placed in a solution in a beaker. Based on the concentration of solute in
two solvents( in the cell and in the beaker), we can have the following types of solutions:

 Isotonic Solution: These solutions have the same concentration of the solute in it.
Therefore, water moves across the cell from the solution in the beaker in both directions.

 Hypertonic Solution: The solution kept in beaker has a higher concentration of solute
in it so water comes out of the cell and into the solution in beaker causing the cell to
plasmolyze/shrink.
 Hypotonic Solution: The solution kept in beaker has a lower concentration of solute in
it so water moves into the cell causing cells to swell up and finally burst.

Expressing Concentration of Solutions

You know what is concentration, right? But, do you know how to express it? When there is too
much salt in your lemonade, you say that it is “too salty”. But in chemistry, there is nothing like
“too”. We have to define it. That is why we are going to study all about the concentration of
solutions in this chapter. We will look at the various methods of calculating the concentration of
solutions. So, let us start!

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Concentration of Solutions

We can calculate the concentration of solutions by various methods. Let’s study each method
and determine the formulas for this method.

1) Mass/Weight Percentage or Percentage by Mass/Weight

It is the amount of solute in grams present in 100 grams of the solution. Therefore, the formula
will be:

The ratio mass of solute to the mass of the solvent is the mass fraction. Thus, the mass
percentage of solute = Mass fraction × 100. 10% solution of sugar by mass means that 10 grams
of sugar is present in 100 grams of the solution, i.e., we have dissolved 10 grams of sugar in 90
grams of water.

2) Volume Percentage

It is the volume of solute in mL present in 100 mL solution. The formula will be:

10% solution of HCl by volume means that 10 mL of liquid HCl is present in 100 mL of the
solution.

3) Mass by Volume Percentage

It is the mass of solute present in 100 mL of solution. We can calculate the mass of the solute
using the volume percentage. The formula would be:

A 10% mass by volume solution means that 10 gm solute is present in 100 mL of solution.
4) Molarity

The molarity of a solution gives the number of gram molecules of the solute present in one litre
of the solution.

For example, 1 mol L-1 solution of KCl means that 1 mol of KCl is dissolved in 1 L of
water. Unit of molarity: mol L-1

Watch Videos on Molarity

5) Molality

Molality of a solution is the number of moles of solute dissolved in 1 Kg of the solvent.

Thus, if one gram molecule of a solute is present in 1 kg of the solvent, the concentration of
solutions is said to be one molal. The unit of molarity is mol kg-1. Molality is the most
convenient method to express the concentration of solutions because it involves the mass of
liquids rather than their volumes. It is also independent of the variation in temperature.

6) Normality

The normality of a solution gives the number of gram equivalents of the solute present in one
litre of the solution.

Thus, if one gram equivalent of a solute is present in one litre of the solution, the concentration
of solutions is said to be 1 normal.

 1N = Normal = One gram equivalent of the solute per litre of solution = Normality is
1

 N/2 = Seminormal = 0.5 g equivalent of the solute per litre of solution = Normality
is 0.5
 N/10 = Decinormal = 0.1 g equivalent of the solute per litre of solution = Normality
is 0.1
  N/100 = Centinormal = 0.01 g equivalent of the solute per litre of solution =
Normality is 0.01
 N/1000 = Millinormal = 0.001 g equivalent of the solute per litre of solution =
Normality is 0.001

Watch Videos on Normality

7) Mole Fraction

The mole fraction of any component in a solution is the ratio of the number of moles of that
component to the total number of moles of all components. The total mole fraction of all the
components of any solution is 1. For a binary solution of A and B

Mole Fraction of A (XA) =

Mole Fraction of B (XB) =

And, XA+XB = 1

8) Parts per million (ppm)

When a solute is present in trace quantities, it is convenient to express the concentration of

solutions in parts per million (ppm). The formula is as follows:

In case of mass, we may express it as: (Mass of solute/Mass of solution )× 106

In case of volume, we may express it as: (Volume of solute/Volume of solution) × 106

So, we can express the concentration of solutions in parts per million as mass to mass, volume to
volume and mass to volume form. Atmospheric pollution in cities is also expressed in ppm by
volume. It refers to the volume of the pollutant in 106 units of volume. 10 ppm of SO2 in the air
means 10 mL of SO2 is present in 106 mL of air.

9) Formality
It is the number of mass in grams present per litre of solution. In case, formula mass is equal to
molecular mass, formality is equal to molarity. Like molarity and normality, the formality is also
dependent on temperature. It is used for ionic compounds in which there is no existence of a
molecule. A mole of ionic compounds is called formal and molarity as the formality.

Where,

 w = weight of solute,

 f = formula weight of solute

 V= volume of solution
 nf = no. of gram formula weight

A Solved Example For You

Q: What is the weight percentage of urea solution in which 10 gm of urea is dissolved in 90

gm water.

Solution: Weight percentage of urea = (weight of urea/ weight of solution) 100

= 10/(90+10) 100 = 10% urea solution (w/W)

Distillation is a procedure that separates a mixture of liquids with different boiling points.
Distillation is a useful technique in chemistry labs, where chemists use it to purify a
compound, and also in industry, especially in the petrochemical and refining industry and in
the manufacture of ethanol. It is for this last that distillation is most famous--alcoholic
beverages are produced through a process of distillation.

Simple Distillation
If water is placed in a sealed container and allowed to evaporate, it will eventually reach an
equilibrium such that the water vapor is condensing just as fast as the water is evaporating.
The pressure of the vapor at this equilibrium is called the vapor pressure. Vapor pressure is
different for different substances and varies with temperature. In a mixture of two liquids
with different boiling points, the vapor will have more of the liquid that is more volatile,
i.e., evaporates more readily. In simple distillation, the liquid mixture is heated and the
vapor rises through a tube and is collected and recondensed. The recondensed liquid will
have a higher concentration of the more volatile component than the original mix. If the
two liquids in the original mix have widely different boiling points, a one-step evaporation
and recondensation process is all that is necessary. This process is called simple distillation.

Fractional Distillation

Fractional distillation is similar to simple distillation, except the same process is repeated in
successive cycles. Each cycle produces a mixture richer in the more volatile compound than
the mixture before it. Fractional distillation is necessary when the boiling points of the
liquids in the original mix are close enough to each other that simple distillation is not
enough to purify either compound.

Vacuum Distillation
Some liquids boil at such high temperatures that simple or fractional distillation using the
process described above would be impractical or dangerous. Vacuum distillation, however,
offers another alternative. The boiling point of a liquid falls when the pressure is reduced.
The boiling point of water, for example, is lower at high altitude than at sea level. By
reducing the pressure in the container, the boiling point of the liquids in the mixture can be
reduced and the mixture distilled at a lower temperature. This technique is called vacuum
distillation.

Conductance
The conductance is the property of the conductor (metallic as well as electrolytic) which
facilitates the flow of electricity through it. It is equal to the reciprocal of resistance i.e.,

Units of conductance : .

Specific Conductance or Conductivity

The resistance of any conductor varies directly as its length (l) and inversely as its cross-
sectional area (A), i.e.,

Mathematically
Where ρ is called the specific resistance.
l/A is known as cell constant.
If l = 1 cm and A = 1 cm2, then
R=ρ
The specific resistance is, thus defined as the resistance of one centimeter cube of a
conductor.
The reciprocal of specific resistance is termed the specific conductance or it is the
conductance of one centimeter cube of a conductor.
It is denoted by the symbo (kappa)l .
Thus,

Where kappa → the specific conductance

Specific conductance is also called conductivity.
Further,

or Specific conductance = Conductance × cell constant

In the case of electrolytic solutions, the specific conductance is defined as the conductance of
a solution of definite dilution enclosed in a cell having two electrodes of unit area separated
by one centimeter apart.
Unit of specific conductance:

Equivalent Conductance
One of the factors on which the conductance of an electrolytic solution depends is the
concentration of the solution.
In order to obtain comparable results for different electrolytes, it is necessary to take
equivalent conductance's.
Equivalent conductance is defined as the conductance of all the ions produced by one gram
equivalent of an electrolyte in a given solution.
It is denoted by A.
According to definitions,
Conductance = Specific conductance (K) = Equivalent conductance ( )
If the solution is diluted to say (9 cm 3) (9 mL), the conductance of the solution will be the
same but specific conductance becomes 1/9th as it contains nine cubes.
The conductance is also equal to the equivalent because the solution still has 1 g equivalent of
the electrolyte.
Equivalent conductance ( ) = 9 × k
In general,
=k×V
where V is the volume in mL containing 1 g equivalent of the electrolyte.
Unit of equivalent conductance:

Molar Conductance
The molar conductance is defined as the conductance of all the ions produced by ionization
of 1 g mole of an electrolyte when present in V mL of solution. It is denoted by .
Molar conductance μ = k ×V
where V is the volume in mL containing 1 g mole of the electrolyte. If c is the concentration
of the solution in g mole per litre, then
μ = k × 1000/c
Units of molar conductance:
Equivalent conductance = (Molar conductance)/n
where
n = (Molecular mass)/(Equivalent mass)
Electromotive Force (emf) OR Cell Potential

The potential difference between the two electrodes in a galvanic cell is called a cell potential
or emf of the cell. It is measured in volts.
emf of the cell = Potential of the half cell on the right hand side (Cathode) - Potential of the
half cell on the left hand side (Anode)
For example, emf of Daniell cell,

Determination of the emf of a cell: The Nernst Equation

Nernst equation relates the equilibrium potential of an half cell with the standard electrode
potential, temperature, activity and reaction quotients of the reacting species. It is named after
the German physical chemist Walther Nernst.

Nernst showed that for the electrode reaction; , the electrode

potential at any concentration measured with respect to SHE can be represented as:

Where, is the electrode potential of the half cell, is the standard electrode

potential, is the concentration of the metal, is the concentration of the metal

ion, is the universal gas constant (8.314 J/K/mole), is the temperature in kelvin, is the
number of electron involved in the reaction, and is the Faradays constant (96500 C/mole).
But the concentration of the solid M is taken as unity and substituting the values of R, F and
T=298 K (Room Temperature), the above equation reduces to:

Potentiometry
Potentiometry is one of the methods of electroanalytical chemistry. It is usually employed to
find the concentration of a solute in solution.

In potentiometric measurements, the potential between two electrodes is measured using a

high impedance voltmeter.

Use of a high impedance voltmeter in important, because it ensures that current flow is
negligible. Since there is no net current, there are no net electrochemical reactions, hence the
system is in equilibrium.
At its most fundamental level, a potentiometer consists of two electrodes inserted in two
solutions connected by a salt bridge (see diagram below). The voltmeter is attached to the
electrodes to measure the potential difference between them.

One of the electrodes is a reference electrode, whose electrode potential is known.

The other electrode is the test electrode.

The test electrode is usually either a metal immersed in a solution of its own ions, whose
concentration you wish to discover, or a carbon rod electrode sitting a solution which
contains the ions of interest in two different oxidation states.

What is Gravimetric Analysis?

Gravimetric analysis is a method in analytical chemistry to determine the quantity of analyte
based on the mass of a solid. Example: Measuring the solids suspended in the water sample –
Once a known volume of water is filtered, the collected solids are weighed.
The principle of Gravimetric Analysis:
The principle behind the gravimetric analysis is that the mass of an ion in a pure compound
and can be determined. Later, used to find the mass percent of the same ion in a known
quantity of an impure compound.
 Gravimetric Analysis Apparatus

Steps followed in the Gravimetric Analysis

1. Preparation of a solution containing a known weight of the sample.
2. Separation of the desired constituent.
3. Weighing the isolated constituent.
4. Computation of the amount of the particular constituent in the sample from the
observed weight of the isolated substance.

Types of Gravimetric Analysis

There are 4 fundamental types of gravimetric analysis. Of which, there are 2 common types
involving changes in the phase of the analyte to separate it from the rest of a mixture,
resulting in a change in mass.
Volatilization gravimetry

 Volatilization Gravimetry involves separating components of our mixture by heating

or chemically decomposing the sample.

Precipitation gravimetry

 Precipitation Gravimetry uses a precipitation reaction to separate one or more parts of

a solution by incorporating it into a solid.

Electrogravimetry

 Electrogravimetry is a method used to separate and quantify ions of a substance,

usually a metal.
Thermogravimetric

 Thermogravimetric is a method of thermal analysis in which changes in physical and

chemical properties of materials are measured as a function of increasing temperature
or as a function of time.

Advantages of Gravimetric Analysis

If the methods are followed carefully, it provides exceedingly precise analysis. It is used to
determine the atomic masses of many elements to six-figure accuracy. It provides a little
room for instrumental error and does not require a series of standards for calculation of an
unknown.

Disadvantages of Gravimetric Analysis

It usually provides only for the analysis of a single element, or a limited group of elements, at
a time. Comparing modern dynamic flash combustion coupled with gas chromatography with
traditional combustion analysis.

Examples of Gravimetric Analysis

Question:
An ore is analyzed for the manganese content by converting the manganese to Mn3O4 and
weighing it. If a 1.52g sample yields Mn3O4 weighing 0.126g, what would be the percent
Mn3O3 in the sample? The percent of Mn?
Solution
%Mn2O3=0.125gMn3O4×3Mn2O32Mn3O4(gMn2O3/gMn3O41.52gsample×100%
=0.126g×[3(157.9)/2(228.8)]1.52g×100%=8.58%
%Mn=0.126gMn3O4×3MnMn3O4(gMn/gMn3O4)1.52gsample×100%
=0.126g×[3(54.94)/228.8]1.52g×100%=5.97%

The volumetric analysis is an analytical method of estimating the concentration of a

substance in a solution by adding exactly same number of equivalents of another substance
present in a solution of known concentration.
This is the basic principle of titration. Volumetric analysis is also known as titrimetric
analysis.The substance whose solution is employed to estimate the concentration of unknown
solution is called titrant and the substance whose concentration is to be estimated is called
titrate.

The volumetric analysis is divided into following types:

 Simple titration
 Back titration
 Double titrations
Simple Titrations
The aim of simple titration is to find the concentration of an unknown solution with the help
of the known concentration of another solution.
Let us take a solution of a substance ‘A’ of unknown concentration. We are provided with
solution of another substance ‘B’ whose concentration is known (N 1). We take a certain
known volume (V2 litre) of ‘A’ in a flask and start adding ‘B’ from burette to ‘A’ slowly till all
the ‘A’ is consumed by ‘B’. This can be known with the aid of suitable indicator, which
shows colour change after the complete consumption of ‘A’. Let the volume of B consumed
is V1 litre According to the law of equivalents, the number of equivalents of ‘A’ would be
equal to the number of equivalents of ‘B’.
Hence N1V1 = N2V2,
where N2 is the concentration of ‘A’.
Thus using this equation, the value of N2 can be calculated.
There are four types of simple titration, namely
 Acid-base titrations
 Redox titrations
 Precipitation titrations and
 Complexometric titrations

Acid- Base Titrations

In this type of titration, the concentration of an acid in a solution is estimated by adding a
solution of standard base and vice versa.
The equivalence point is detected by adding a few drops of a suitable indicator to the solution
whose concentration is to be estimated.
An acid-base indicators gives different colours with acids and bases. The choice of indicator
in a particular titration depends on the pH-range of the indicator and the pH change near the
equivalence point.
For example,
Strong Acid - Strong Base Titration
In the titration of HCI vs NaOH, the equivalence point lies in the pH range of 4-10. Thus,
methyl red (pH-range 4.2 to 6.3), methyl orange (pH-range 3.1 to 4.4) and phenolphthalein
(pH-range 8.3 – 10) are suitable indicators of such titrations.
Weak Acid - Strong Base Titration
In the titration of CH3COOH and NaOH, the equivalence point lies between 7.5 and 10. Thus,
phenolphthalein is the suitable indicators.
Weak Base - Strong Acid Titration
In the titration of CH3COOH and NH4OH, the equivalence point lies between 4 to 6.5. Thus
methyl orange and methyl red are suitable indicators.
Weak Acid - Weak Base Titration
In the titration of CH3COOH and NH4OH, the equivalence point lies between 6.5 and 7.5 and
the pH change is not sharp at the equivalence point. Thus, no simple indicator can be
employed to detect the equivalence point.

Redox Titrations
In a redox titration, an oxidant is estimated by adding reductant or vice-versa.
For example, Fe2+ ions can be estimated by titration against acidified KMnO4 solution when
Fe2+ ions are oxidized to Fe3+ ions and KMnO4 is reduced to Mn2+ in the presence of acidic
medium.
KMnO4 functions as self-indicator as its purple colour is discharged at the equivalence point.
Mn + 8H+ + 5e– → Mn2+ + 4H2O
Fe2+ → Fe3+ + e–] × 5
Mn + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
(n=5) (n=1)
In addition to acidified KMnO4, acidified KCr2O7 can also be employed. Other redox titration
are iodimetry, iodometry etc.
Iodimetry
This titration involves free iodine. Such direct estimation of iodine is called iodimetry.
This involves the titration of iodine solution with known sodium thiosulphate solution, whose
normality is N. Let the volume of sodium thiosulphate used be V litre.
I2 + 2Na2S2O3 → 2NaI + Na2S4O6
(n=2) (n=1)

Equivalents of I2 = Equivalents of Na2S2O3 used = N × V

Moles of I2 =

Mass of free I2 in the solution = g

Iodometry
This is an indirect method of estimation of iodine. An oxidizing agent is made to react with
excess of solid KI. The oxidizing agent oxidizes I– to I2.
This liberated I2 is then made to react with Na 2S2O3 solution of normality N. Let the volume
of thiosulphate solution required be V litre.
Oxidising Agent (A) + KI I2 2NaI + Na2S4O6
+
Reduced form of oxidizing agent
Equivalents of ‘A’ = Equivalents of I2 = Equivalents of Na2S2O3 used = N × V
Equivalents of I2 liberated from KI = N × V
Equivalents of ‘A’ = N × V
Let the n-factor of ‘A’ in its reaction with KI be x, then

Mass of ‘A’ consumed = × MA (where MA is the molar mass of A)

Precipitation Titrations
In a titration of this kind, cations and anions combine to form a compound of very low
solubility. Thus, a solid residue separates out.
For example,
AgNO3 + NaCI → AgCI¯ (white) + NaNO3
BaCI2 + H2SO4 → BaSO4¯ (white) + 2HCI

Complexometric Titrations
In this type of titration, the titrate combines with the titrant to form complex salts. The
complex salts may or may not be soluble. For example,
CuSO4 + 4NH4OH → [Cu(NH3)4]SO4 + 4H2O
AgNO3 + 2KCN → K[Ag(CN)2] + KNO3
Refer to the following video for problem on acid-base titration

Back Titration
Let us assume that we have an impure solid substance ‘C’, weighing ‘w’ g and we are
required to calculate the percentage purity of ‘C’ in the sample. We are also provided with
two solutions ‘A’ and ‘B’, where the concentration of ‘B’ is known (N1) and that of ‘A’ is
unknown.
For the back titration to work, following conditions are to be satisfied
 Compounds ‘A’, ‘B’ and ‘C’ should be such that ‘A’ and ‘B’ react with each other.
 ‘A’ and pure ‘C’ also react with each other but the impurity present in ‘C’ does not
react with ‘A’.
 Also the product of ‘A’ and ‘C’ should not react with ‘B’.
Now we take out certain volume of ‘A’ in a flask (the equivalents of ‘A’ taken should
be > equivalents of pure ‘C’ in the sample) and perform a simple titration using ‘B’. Let us
assume that the volume of ‘B’ used be V1 litre.
Equivalents of ‘B’ reacted with ‘A’ = N1V1
Hence Equivalents of ‘A’ initially = N1V1
In another flask, we again take some volume of ‘A’ but now ‘C’ is added to this flask. Pure
part of ‘C’ reacts with ‘A’ and excess of ‘A’ is back titrated with ‘B’. Let the volume of ‘B’
consumed is V2 litre.
Equivalent of ‘B’ reacted with excess of ‘A’ = N1V1
Hence Equivalents of ‘A’ initially = N1V1
Equivalents of pure ‘C’ = (N1V1 – N1V2)

Let the n-factor of ‘C’ in its reaction with ‘A’ be x, then the moles of pure ‘C’ =

Hence Mass of pure ‘C’ = × Molar mass of ‘C’.

Hence Percentage purity of ‘C’ = × × 100

Double Titrations
The purpose of double titration is to determine the percentage composition of an alkali
mixture or an acid mixture. In the present case, we will find the percentage composition of an
alkali mixture. Let us consider a solid mixture of NaOH, Na 2CO3 and some inert impurities,
weighning ‘w’ g. We are required to find the % composition of this alkali mixture. We are
also given an acid reagent (HCI) of known concentration M 1 that can react with the alkali
sample.
We first dissolve this mixture in water to make an alkaline solution and then we add two
indicators, (Indicators are substances that indicate colour change of solution when a reaction
gets completed), namely phenolphthalein and methyl orange to the solution. Now, we titrate
this alkaline solution with standard HCI.
NaOH is a strong base while Na2CO3 is a weak base. So it is obvious that NaOH reacts first
with HCI completely and Na2CO3 reacts only after complete NaOH is neutralized.
NaOH + HCI → NaCI + H2O …..(i)
Once NaOH has reacted completely, then Na2CO3 starts reacting with HCI in two steps,
shown as
Na2CO3 + HCI → NaHCO3 + NaCI ……. (ii)
NaHCO3 + HCI → NaCI + CO2 + H2O …… (iii)
It is clear that when we add HCI to the alkaline solution, alkali is neutralized and the pH of
the solution decreases. Initially the pH decrease would be rapid as strong base (NaOH) is
neutralized completely.
When Na2CO3 is converted to NaHCO3 completely, the solution is still weakly basic due to
the presence of NaHCO3 (which is weaker as compared to Na2CO3). At this point,
phenolphthalein changes colour since it requires this weakly basic solution to show its colour
change.
When HCI is further added, the pH again decreases and when all the NaHCO 3 reacts to form
NaCI, CO2 and H2O the solution becomes weakly acidic due to the presence of the weak acid
(H2CO3). At this point, methyl orange changes colour as it requires this weakly acidic
solution to show its colour change.
Thus in general, phenolphthalein shows colour change when the solution contains weakly
basic NaHCO3 along with other neutral substances while methyl orange shows colour change
when solution contains weakly acidic H2CO3 along with other neutral substances.
Let the volume of HCI used up for the first and the second reaction be V1 litre (this is the
volume of HCI used from the beginning of the titration up to the point when phenolphthalein
shows colour change) and the volume of HCI require for the third reaction be V2 litre (this is
the volume of HCI used from the point where phenolphthalein had changed colour upto the
point when methyl orange shows colour change). Then,
Moles of HCI consumed by NaHCO3 = Moles of NaHCO3 reacted = M1V2
Moles of NaHCO3 formed from Na2CO3 = M1V2
Moles of Na2CO3 in the mixture = M1V2
Mass of Na2CO3 in the mixture = M1V2 × 106
% of Na2CO3 in the mixture =
Moles of HCI used in te reaction (i) and (ii) = M1V1
Moles of HCI used in reaction (ii) = M1V2
Moles of HCI used in reaction (i) = (M1V1 – M1V2)
Hence Moles of NaOH = (M1V1 – M1V2)
Mass of NaOH = (M1V1 – M1V2) × 40

% of NaOH in the mixture =

Here, we have determined the percentage composition of the mixture using mole concept, as
the balanced reactions were available. If we were to solve this by equivalent concept, then the
procedure adopted would be
NaOH + HCI → NaCI + H2O …….(i)
Na2CO3 + HCI → NaHCO3 + NaCI …….(ii)
(n=1) (n=1) (n=1)

Phenolphthalein shows end point after reaction (ii)

NaHCO3 + HCI → NaCI + CO2 + H2O ……...(iii)
(n=1) (n=1)
and methyl orange shows end point after reaction (iii).
At phenolphthalein end point,
(Equivalents of HCI)1 = Equivalents of NaOH + Equivalents of Na2CO3 (n=1) = M1V1
or (Equivalents of HCI)1 = Equivalents of NaOH +½ Equivalents of Na2CO3 (n=2) ..(iv)
At methyl orange end point,
(Equivalents of HCI)2 = Equivalents of NaHCO3 reacted (n=1) = Equivalents of
NaHCO3 produced (n=1) = Equivalents of Na2CO3 (n=1)
Hence M1V2 = Equivalents of Na2CO3 (n=1) = ½ Equivalent of Na2CO3 (n=2) ……..(v)
Subtracting equation (v) from equation (iv),
Equivalents of NaOH = (M1V1 – M1V2)
Hence Moles of NaOH = (M1V2 – M1V2) (since n-factor of NaOH is 1)

Hence % of NaOH in the mixture =

Equivalents of Na2CO3 (n=1) = M1V2
and moles of Na2CO3 = M1V2 (since n-factor of Na2CO3 is 1)
Hence % of Na2CO3 in the mixture =
In the above case, we have taken alkali mixture of NaOH & Na 2CO3. But other alkali
mixtures can also be taken.
Question 1: Which of the following types of titration is not a simple titration?
a. Acid-base titrations
b. Back titration
c. Precipitation titrations
d. Complexometric titrations
Question 2: According to the law of equivalents,
a.N2V1 = N1V2,
b.N1V2 = N2V1,
c.N1V1 = N
d. V = N2V2,
Question 3: Which of the following conditions is nor required for the back titration to
work ?
a. Compounds ‘A’, ‘B’ and ‘C’ should be such that ‘A’ and ‘B’ react with each other.
b. ‘A’ and pure ‘C’ also react with each other but the impurity present in ‘C’ does not react
with ‘A’.
c. Product of ‘A’ and ‘C’ should not react with ‘B’.
d. Product of ‘A’ and ‘B’ should be ‘C’.
Question 4: The titration in which an oxidizing agent is made to react with excess of solid
KI and the oxidizing agent oxidizes I– to I2 is known as
N2(g) + 3H2(g) → 2NH3(g) ?
a. Iodometry
b. Iodimetry
c. Double titration
d. Back titration

Types of Chromatography Techniques

Chromatography utilizes phase equilibrium partitioning principles to isolate proteins, nucleic
acids, or little particles in complex blends in view of their varying connections with a
stationary phase and a mobile phase. There are two main types of chromatography: Liquid
chromatography (LC) and gas chromatography (GC). Both LC and GC can be utilized for
either preparative or investigative applications. Chromatography strategies can likewise be
ordered by the chromatography media chemistry: the sorts of physicochemical associations
used to segment components into the stationary and mobile phases thus accomplish
separation.
 Industrial chromatography
 Column chromatography
 Planar Chromatography
 Gas Chromatography and Liquid Chromatography
 Size-exclusion chromatography
 Ion exchange chromatography

Applications of Chromatography
Chromatography plays an important role in many pharmaceutical industries and also in the
chemical and food industry. Environmental testing laboratories generally want to identify for
very small quantities of contaminants such as PCBs in waste oil, and pesticides. The
Environmental Protection Agency makes the method of chromatography to test drinking
water and to monitor air quality. Pharmaceutical industries use this method both to prepare
huge quantities of extremely pure materials, and also to analyze the purified compounds for
trace contaminants. The other applications of chromatography especially HPLC is used in
Protein Separation like Insulin Purification, Plasma Fractionation and Enzyme Purification.
These separation techniques like chromatography gain importance in different kinds of
companies, different departments like Fuel Industry, biotechnology, biochemical processes,
and forensic science. Chromatography is used for quality analyses and checker in the food
industry, by identifying and separating, analyzing additives, vitamins, preservatives, proteins,
and amino acids. Chromatography like HPLC is used in DNA fingerprinting and
bioinformatics.
 Assay & Content Uniformity
 HPLC in fingerprinting and Bioinformatics
 Petrochemicals and Catalysis
 Ebola Immunisation
  Polymer Synthesis
 Clinical diagnosis of diseases and disorder
 LC-NMR

High Performance Liquid Chromatography

High Performance Liquid Chromatography (HPLC) is different and another type of
column chromatography that pumps a sample mixture or analyte in a solvent at high pressure
through a column with chromatographic packing material. HPLC has the ability to analyse,
and separate compounds that would be present in any sample that can be dissolved in a liquid
in trace concentrations. Because of this advantage, HPLC is used in a variety of industrial and
scientific applications, such as pharmaceutical industry, environmental, forensic science, and
chemicals. High Performance Liquid Chromatography has brought lot of advantages in the
department of food analysis and also in the analysis of various fat soluble vitamins. HPLC is
also used in DNA fingerprinting and bioinformatics.
 Ultra high performance liquid chromatography
 Fast protein liquid chromatography
 HPLC-mass spectrometry
 Scope of High Performance Liquid Chromatography
 Characterization of HPLC stationary phases

Electrophoresis
Electrophoresis is used to characterize proteins, nucleic acid and any sub cellular
particles. Main principle is based on the charge of the particles. Charged particles migrate in
the applied electric field. Positively charged ions migrate towards a negative conductor and
negatively-charged ions migrate toward a positive conductor.
 Capillary Zone Electrophoresis
 Dielectrophoretic
 Blue-native polyacrylamide gel electrophoresis
 Electroblotting