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The classification of matter into three different states, namely solid, liquid and
gaseous state is termed as the physical classification of matter. Most properties of
solid, liquid and gases that can be observed with our sense organs are called as
'macroscopic' properties. The description of the behaviour of the three states of
matter in terms of atomic theory is called 'microscopic' description of matter. From
the study of the observable properties of different states of matter one can
understand the microscopic nature of matter in terms of the behaviour of constituent
particles.
The important characteristics of the three states are listed out below:
Solid state
A solid possesses a definite size (volume) and a definite shape under ordinary
conditions; and tends to maintain these even under deforming conditions. The
substances in solids are closely packed and bound by strong inter particle attraction,
making them rigid and geometrical. Some common examples of solids are iron, silver,
common salt, etc.
Liquid state
A liquid possesses a definite volume but not definite shape. The substances in liquids
have particles, which are loosely packed and bound to each other by forces weaker
than those of solids. This makes a liquid mobile and shapeless resulting in its taking
up the shape of the container in which it is placed. A liquid also has a tendency to
flow. For example, water, alcohol, milk, oil, etc.
Gaseous state
A gas neither possesses a definite volume nor a definite shape. The substances in a
gas have particles that are separated by great distance, having virtually no force of
attraction between them. A gas occupies the whole of the volume of the vessel in
which it is placed. It also takes up the shape of the container. For example, air,
carbon dioxide, oxygen, hydrogen, etc.
The three states of matter are inter-convertible. This can be done by heating or
cooling. Heating increases the inter particle spacing and kinetic energy of the
particles. So, a solid on heating gets converted into a liquid, and a liquid into a gas.
Gases maintain neither the volume nor the shape. They completely fill the
container in which they are placed.
Gases are highly compressible. The volume of the gas decreases when the
pressure increases.
All gases are colourless except a few e.g. chlorine (greenish yellow) bromine
(reddish brown), nitrogen dioxide (reddish brown)
The important fundamental properties of gases are mass, volume, pressure and
temperature. These are discussed below:
Measurement of mass
The mass of a gas can be measured by direct weighing. The container in which the
gas is enclosed is first weighed. Then the weight of the container, after removing all
the gas, is measured again. The difference between the two weights gives the mass
of the gas.
Units of mass
The most common unit for mass is expressed in grams (g) or kilogram (kg) (1 kg =
103g).
In chemical measurement, IUPAC prescribes that the mass of a gas (m) be expressed
in terms of the number of moles (n). The number of moles can be obtained from the
mass of the gas using the relationship
Measurement of volume
The volume of a substance is the space occupied by it. A gas occupies the entire
volume of the container available to it. The measurement of the volume of a gas only
requires the measurement of the volume of the container enclosing it.
Units of volume
1 mL= 1 cm3
1 L = 103 mL or 1 dm3
The SI unit of volume is m3. As this unit is too large, volume is generally expressed in
smaller units of cubic decimetre (dm3) or cubic centimetre (cm3). These are related to
each other as:
The volume of the gas depends upon its amount, temperature and pressure V = f
(amount, temperature, pressure).
Measurement of Pressure
Gases exert uniform pressure in all the directions on the walls of the container in
which they are confined. As pressure is force per unit area, the pressure of the gas is
the force exerted by the gas per unit area on the walls of the container.
Atmospheric pressure
Air is pulled towards the surface by gravity and this exerts pressure on the Earth's
surface. The pressure exerted by the gases of the atmosphere on the surface of the
Earth is called atmospheric pressure.
P = h. .g
A standard pressure of one atmosphere (1 atm) is defined as the pressure that will
support a column of mercury of 76 cm height at 0°C (density of mercury (13.5951
gcm-3) and at standard gravity
= 980.665 cm-2.
One atmosphere is also referred to as 760 torr. This unit is named after the scientist
Torricelli, who invented the Barometer. Thus
= 760 torr.
The S.I. unit of pressure is pascal (Pa), which is the pressure exerted when a force of
Newton (1 N) acts on 1m2 area. Pascal is related to atmosphere as:
= 101.325 kPa
However, for approximate work, one atmosphere is taken to be equal to 102 kPa or
105 Pa or Nm-2.
The pressure of gases are measured by a device known as manometer that can be
either open end manometer or closed end manometer. These manometers consist of
'U' tube partly filled with a non-volatile liquid like mercury. During measurement, the
difference in the levels of the mercury in the two limbs gives the difference in
pressure on the two sides.
Measurement of Temperature
Temperature is a measure of hotness or coldness of a body. It is a measure of kinetic
energy possessed by the molecules. A hot body is said to be at a higher temperature
and a cold body is said to be at a lower temperature. The devices used to measure
temperature are called Thermometers. The substance commonly used in the
thermometers is mercury.
Unit of temperature
The S.I. unit of temperature is degrees Kelvin (K) and this scale is known as Kelvin
scale. The zero point on the Kelvin scale is known as absolute zero, which is equal to
-273.15°C.
°C + 273.15 = K
The properties of a gas depends upon the temperature and pressure. Hence, it is
convenient to specify a particular temperature and pressure for comparison of
different gases. The standard conditions of temperature and pressure are abbreviated
as S.T.P. (Standard Temperature and Pressure) and N.T.P. (Normal Temperature and
Pressure).
Boyle's Law
Robert Boyle proposed this law in the year 1662, giving the relationship between
pressure and volume of given mass of a gas at constant temperature. This law states
that volume (V) of a given mass of gas is inversely proportional to the pressure (P) at
constant temperature.
or PV = k = constant
At a given temperature, when the pressure of the gas is changed from
P1 V1 = P2 V2 = constant
where, V2 is the new volume of the gas. The product of volume and pressure for a
given mass of a gas at constant temperature is constant. This aspect can be
experimentally verified by taking the pressure volume data for a gas like 10g of
oxygen at 25oC. It is observed that with the increase in pressure the volume
decreases and the product 'PV' remains constant. This data when plotted with 'P'
along the x-axis and 'V' long the y-axis gives a curve.
The curve shows the inverse relation of 'P' and 'V'. When the pressure is P1, the
volume is V1and when the pressure is increased to P2, the volume V2 is smaller than
V1. If the graph is plotted between 'P' and
1 / V, a straight line passing through the origin is obtained. On plotting the product
'PV' along y-axis and Pressure 'P' along x-axis, a horizontal line is obtained, indicating
'PV' to be constant even if we change pressure.
Fig: 2.3 - Plot of P versus 1/V
The P-V curve for a given gas is different at different temperatures. The plot of 'PV'
against 'P' at different temperature is known as Isotherms. The higher curve
corresponds to higher temperature. Boyle's law expresses the compressible nature of
gas, which gives a measure of its increased density.
Problem
Solution
P1 = 745 mm Hg V1 = 250 mL
P2 = ? V2 = 200mL
P1V1 = P2V2
Charles' Law
Charles formulated this law in 1787 giving the relationship between volume and
temperature of a gas. This law stated that at constant pressure, the volume of a
given mass of gas increases or decreases by 1/273 of its volume at 0oC for every one
degree rise or fall.
or
A plot of volume along x-axis and temperature along y-axis gives a straight line
intercepting the y-axis. When this line is extrapolated to lower temperature, it cuts
the x-axis, which represents the zero volume.
The temperature at which the volume of the gas becomes zero is found to be -273oC,
which is independent of the nature and pressure of the gas. The lowest temperature
below which volume does not exist (negative), is called the absolute zero.
Temperature measurements based on the absolute zero is known as absolute scale of
temperature or Kelvin temperature scale.
273 + t = T (K) and 273 =T0 which corresponds to 0oC on absolute temperature scale
The validity of Charles' law can be determined by measuring the volumes of a given
mass of a gas at different temperatures, at constant pressure. The value of V/T
remains to be constant in this study. The curves obtained by plotting volume
temperature ratio against different pressures are called isobars. Charles described
the expansive nature of gases with lower density.
Problem
2. A sample of helium has a volume of 520 cm3 at 100oC. Calculate the temperature
at which the volume will become 26cm3. Assume that pressure is constant?
Solution
or
T2 = 186.5 K
Avogadro's Law
The relationship between the volume of a gas to the number of molecules at constant
temperature and pressure is known as Avogadro's law. It states that equal volumes of
all gases under similar conditions of temperature and pressure contain equal number
of molecules. 22.4 litres of any gas at STP contains 6.023 x 1023 number of molecules
irrespective of its nature. Therefore, the volume of a gas is directly proportional to the
number of molecules N.
The number of moles 'n' of a gas is also proportional to the number of molecules.
n = N/No
n N,
V N or V n.
Thus, it can be concluded that the volume of gases at constant temperature and
pressure is directly proportional to their number of moles.
P = p1 + p2 + p3 + …….
Partial pressure is the pressure exerted by the gas if present alone in the vessel at
the same conditions of temperature.
For example,
A gas 'A' having a pressure of 300 mm Hg is contained in a vessel and another gas 'B'
with a pressure of 400 mm Hg is contained in another vessel, are mixed in the third
vessel at the same temperature. The total pressure in the third vessel is,
P = PA + PB
Problem
Solution
= 0.49 atm.
Graham studied the rate of diffusion of various gases and gave this law. It states that
under similar conditions of temperature and pressure, the rates of diffusion of gases
are inversely proportional to the square roots of their densities.
If r1 and r2 are the rates of diffusion of two gases 'A' and 'B' and 1 and 2 are their
densities, then
Molecular mass is twice the vapour density, substituting this in the above equation,
we have
where M1 and M2 are the molecular masses of the two gases. Thus, the rate of
diffusion of gases are inversely proportional to the square root of their molecular
masses.
Rate of diffusion is also equal to the volume of the gas, which diffused per unit time,
If V1 and V2 are the volumes of the gases diffusing in time t1 and t2 respectively, then
Therefore,
Then,
When the gases contained in a vessel are allowed to escape through a small
aperature, it is effusion.
Problem
4. An unknown gas diffuses four times as quickly as oxygen. Calculate the molecular
mass of the gas.
Solution
or
or
or
Now, if V1 is the volume of a gas at temperature T1 and pressure P1. V2 is the volume
of same amount of gas at temperature T2 and pressure P2, then
The above relationship is very useful for converting the volume of a gas from one set
of conditions to another.
The numerical value of the constant of proportionality (K) depends upon the quantity
of gas. The volume of a gas is directly proportional to the number of moles of gas at
constant temperature and pressure (Avogadro's law). This means that 'K' is directly
proportional to the number of moles, 'n', i.e.,
K n
or K = nR,
where 'R' is the universal gas constant of proportionality. The value of 'R' is same for
all gases.
However, the numerical value of 'R' varies with the units in which pressure and
volume are expressed. Therefore the Ideal gas Equation is derived as:
The Ideal Gas Equation is also known as the equation of state for gases as it
expresses the quantitative relation ship between the four variables that describe the
state of the gas. The word 'ideal' is used here because in reality no gas obeys the
above condition and the gases, which deviate from ideality are called as real gases.
The universal gas constant is a measure of energy change (work done) per mole of
the gas for one degree change in its temperature.
Numerical Value of R
The magnitude and unit of 'R' depends upon the units in which pressure, volume and
temperature are expressed.
P = 1 atm
T = 273.15 K
V = 22.414 L mol-1
This gives,
Here,
P = 1 atm
T = 273.15 K
V = 22414 mL mol-1
This gives,
When,
If 'R' is to be expressed in CGS units, the unit of pressure should be dyne cm-2 and
volume in cm3 mol-1. Then,
= 22414 cm3mol-1
Therefore,
Hence,
IV) In SI units
P = 101325 N m-2
T = 273.15 K
V = 22.414x10-3 m3
Therefore,
Problems
5. Calculate the number of moles of hydrogen (H2) present in a 500 cm3 sample of
hydrogen gas at a pressure of 760 mm of Hg and 27°C.
Solution
6. About 200 cm3of a gas is confined in a vessel at 20°C and 740 mm Hg pressure.
How much volume will it occupy at S.T.P.?
Solution
We are given
P1 = 740 mm Hg P2 = 760 mm Hg
V1 = 200 cm3 V2 = ?
= 181.4 cm3.
Solution
= 19.95 x 10-3m3=19.95dm3.
Effect of pressure
All gases are known to exist as real gases and show ideal behaviour only to some
extent under certain conditions. When PV = nRT for ideal gases, then the ratio
For real gases Z may be less or more than one. If Z<1 then it is called negative
deviation which means that the gas is more compressible. If Z>1 then the gas is less
compressible and it is called positive deviation. It is observed that the deviations are
low at low pressures. At high pressures the deviations depends on the nature of the
gas.
A plot of versus P for some common gases are shown in the figure.
For H2 and He, 'Z' is greater than one while for N2, CH4 and CO2 'Z' is lesser than one.
This means that these gases are more compressible at low pressures and less
compressible at high pressures than expected from ideal behaviour.
Effect of temperature
The effect of temperature on the behaviour of real gases is studied by plotting the
value of 'PV' against temperature. It is observed that the deviations from ideal
behaviour is less with the increase in temperature.
Thus, real gases show ideal behaviour at low pressures and high temperatures.
The assumption that the volume occupied by the molecular mass is negligible as
compared to the total volume of the gas is invalid. Although this volume is 0.1%
volume of the total volume of the gas, the volume of the molecules of gas remain
same as compared to the decrease in the total volume of the gas. The decrease in
volume occurs with the decrease in temperature and increase in pressure, but the
volume of the molecules cannot be neglected.
Hence, Van der Waal who incorporated the idea of finite molecular volume and
intermolecular forces modified the Ideal Gas Equation as follows:
Volume correction was made stating that the free volume of the gas is actually less
than the observed volume. A suitable volume term 'b' is subtracted from the
observed volume known as the excluded volume or correct volume. The correction
term, 'b' is a constant depending upon the nature of the gas. For 'n' moles of gas, the
correction term is 'nb' and so the corrected volume is given by,
Substituting these values for pressure and volume, the ideal gas equation can now be
written as:
This equation is Van der Waal's equation of state. Here, the constant 'a' measures the
forces of attraction between the molecules of the gas and 'b' relates to the
incompressible volume of the molecules, measuring the size of the gas molecules.
One can now summarize the differences between ideal and real gases as follows:
Kinetic Molecular Theory of Gases
In order to explain the observed behaviour of gases, a model was proposed based on
the molecular and kinetic concept of gas molecules. This model takes into account
the particulate nature of matter and the constant movement of particles.
All gases are made up of large number of minute particles called molecules.
Large distances separate the molecules so that the actual volume of the molecules
is negligible as compared to the total volume of the gas.
The molecules are in a state of constant rapid motion in all directions, colliding with
one another and also with the walls of the container.
The molecular collisions are perfectly elastic with no loss of energy and only
redistribution of energy during collision.
The pressure exerted by the gas is due to the bombardment of its molecules on the
walls of the container per unit area.
The average kinetic energy of the gas molecules is directly proportional to the
absolute temperature.
On the basis of these postulates an equation for the pressure of the gas is derived
as
This is called the Kinetic gas equation where 'N' is the number of molecules in
volume 'V', 'm' is the mass of the
molecule and 'u' is the root mean square velocity of the molecules.
Liquefaction of Gases
There are large empty spaces (voids) separating the tiny molecules of gases from one
another. Each molecule enjoys an almost independent existence. Molecules are in a
state of continuous rapid motion and have negligible attractive forces between them
due to wide separation. This is particularly so, when temperature is high and pressure
is low. When the temperature of the gas is lowered, both the volume of the gas and
the kinetic energy of the molecules decrease. The molecular motion becomes slow
and molecules become sluggish. The progressive decrease of temperature brings the
molecules closer and closer because they are unable to resist the attractive force that
starts operating between them. Ultimately, at sufficiently low temperature, the voids
between the molecules become less than 10-5cm and the gas changes into liquid
state.
This process of liquefaction by bringing gas molecules closer can also be achieved by
increasing the pressure of the gas: this also decreases the volume of the gas. For
example, sulphur dioxide can be liquefied at 265 K if pressure is 760 mm of Hg. It can
also be liquefied at 293K if the pressure is increased to 2470 mm of Hg.
For example,
Tc of CO2 = 304.1 K.
The pressure required to liquefy the gas at its critical temperature is called critical
pressure.
The volume of one mole of the gas at critical temperature and critical pressure is
called critical volume.
The parameters Tc, Pc and Vc for a gas are collectively called 'critical constants'.
Relationship between Critical Constant and Van der Waal's Constants
The relationship between critical constants of the gases and their Van der Waal
constants is as follows:
(i) Vc = 3b
(ii) Pc = a/27b2
(iii) Tc = 8a/27Rb
These relations have been derived from the calculations based on Van der Waal's
equation.
Boyle's Law
When the volume of the gas is reduced, the molecules move with the same speed but
in lesser space. As a result, the frequency of collisions with the walls of the container
increases and a pressure increase is noticed. This is the statement of Boyle's law and
this can be deduced from the kinetic gas equation,
Charle's Law
When a gas is heated the molecules move faster increasing the pressure. But to
maintain the pressure constant, the force of collision is compensated with an increase
in volume. So, at constant pressure the volume of the gas increases with
temperature. By kinetic gas equation we have,
substituting this we have,
Dalton's Law
When more than one type of molecule is present (at constant T) then, the total
pressure exerted by the mixture should be equal to the sum of their individual
pressures when present alone. The pressure exerted by each gas is
where 1 and 2 are the average molecular kinetic energies of the two gases
containing N1and N2 molecules per unit volume. Since the molecules behave
independent of each other,1 and 2 = , hence
= p1 + p2
The total pressure is equal to the sum of the pressures, which each gas would exert if
allowed to occupy the entire space. This is Dalton's law of partial pressures.
The rate of diffusion of a gas depends inversely on the square root of its density. This
is Graham's law of diffusion.
The fraction of molecules with very low or very high speeds is very small.
The fraction of molecules possessing higher and higher speeds goes on increasing
till it reaches a peak and then starts decreasing.
The increase in temperature of the gas results in increase in the molecular motion.
Consequently, the value of the most probable speed increases with increase in
temperature. It may be noted that as long as the temperature of a gas is constant,
the fraction having the speed equal to most probable speed remains the same but
the molecules having this speed may not be the same. In fact, the molecules keep on
changing their speed as a result of collisions.
The most probable speed of a gas is the speed possessed by the maximum fraction of
gas molecules at a given temperature denoted by .
Average speed
This is the average of speeds possessed by the molecules in a sample of any gas.
This is defined as,
The root mean square speed is commonly used and can be calculated from the
following relations:
Relation between most probable, average and root mean square speeds
Thus for gases, the root mean square speed is directly proportional to , and
inversely proportional to . Therefore heavier molecules move slower.
Therefore
The units of Ek depend upon the units of R. Hence the following point holds true:
The assumption of kinetic theory that the average kinetic energy or molecular
velocity of any gas is directly proportional to its absolute temperature.
K.E u2
or
Problem
Solution
= 683.9 ms-1
In terms of kinetic molecular model, the nature of the liquid state can be described as
follows:
Liquids are composed of molecules that are relatively closer than gases.
Due to weak intermolecular forces, the molecules are in constant random motion.
It may be noted that the nature and magnitude of intermolecular forces decide the
structure of a liquid and also its characteristic properties.
Properties of Liquids - I
The important properties of liquids are:
Volume
Liquids have a definite volume under given temperature and pressure conditions.
Though they take the shape of the container, they maintain their volume. The
intermolecular forces in liquids are strong and therefore, they do not expand to
occupy all the space available (as gases do). A given mass of liquid has a fixed
volume. For example, 10 cm3 of water always occupies 10 cm3 whether it is placed in
a beaker, a conical flask or a large round bottom flask.
Shape
Liquids have no shape of their own. The molecules in the liquid state are not rigidly
fixed to their own sites and take the shape of the container in which they are placed.
Density
The higher density of liquids compared to gases is due to the fact that molecules of
liquids are more closely packed than gases. In general, the density of liquids is higher
than gases and it decreases with increase in temperature. It has been found that the
densities of liquids are about 1000 times greater than the densities of gases under
similar conditions. For example, the density of water at 100oC and 1 atm is 0.958 g
cm-3 while the density of water vapours at the same temperature and pressure is
0.000588 gcm-3.
Compressibility
Liquids are 105 times less compressible than gases but are about 10 times more
compressible than solids. This is due to the fact that the molecules in liquid state are
not as closely packed as in solids but are closer to each other as compared to gases.
Moreover in the case of liquids, the repulsive forces between molecules prevent the
compressibility of liquids. Therefore, large pressure is needed to reduce the volume
of a liquid to a significant extent. For example, at 25oC, an increase in pressure from
1 atm to 2 atm decreases the volume of an ideal gas by about 50%, whereas the
same change in pressure decreases the volume of water by only 0.0045%.
Fluidity
Liquids flow with greater ease as compared to solids. The ease of flow of liquids
depends on the strength of the intermolecular attractive forces e.g. liquids with
hydrogen bonding are more viscous and therefore less fluid.
Surface tension
Due to strong intermolecular cohesive forces in the liquid, the interior of the liquid
holds the molecules on the surface inwards. This property is described in terms of
surface tension and the free surface of the liquid acts as a stretched membrane.
Like gases, liquids also diffuse but they diffuse slowly than the gases. The diffusion of
liquids is defined as the process of intermixing of the molecules of two or more
liquids to form homogeneous mixture solution. This is also the movement of solute
particles from higher concentration to lower concentration in a medium.
The rate of diffusion is much slower in liquids than in gases. In the liquid state,
molecules are quite close to each other. Therefore, a molecule of the liquid has to
undergo a number of collisions with the neighbouring molecules. Thus, there is more
obstruction for the movement of the molecules of a liquid. As a result, diffusion takes
place slowly. In contrast, in gases, there is very less obstruction to the moving
molecules because of large empty spaces available for their movement. Moreover, in
liquids there are forces of attraction between individual molecules which hold them
together. In other words, this slows down the process of diffusion. However raising
the temperature increases the kinetic energy of the molecules. This increase the rate
of diffusion of a liquid.
Quasilattice structure
The partially ordered structure of liquids is called the quasilattice structure. They do
not have a long-range order. Due to the cohesive forces between the molecules in
liquids, molecules appear to be under the influence of each other for short-range
order.
Different molecules in a liquid have different speeds and therefore, have different
kinetic energies. There is a certain fraction of the molecules at the surface, which
have very high kinetic energies. These molecules can readily overcome the attractive
forces in the liquid and escape from the liquid surface into vapours. This process of
escaping of molecules spontaneously from the surface of the liquid to vapour state is
called evaporation.
It may be noted that during the process of evaporation, cooling always occurs. This is
because during evaporation the molecules of higher kinetic energy escape. The slow
moving molecules are left behind and therefore, the average kinetic energy of the
molecules left in the liquid state is lowered, assuming that no heat is supplied from
some outside source. The lowering of the average kinetic energy results in a
temperature drop in the liquid.
The conversion of a liquid into its vapour at its boiling point is called as vaporization.
The tendency of molecules in the liquids to escape from its surface is called volatility.
The liquids whose molecules have very little tendency to leave the surface are called
non-volatile liquids. Conversely, the liquids whose molecules leave the surface easily
are volatile liquids. Volatile liquids evaporate faster.
Temperature
The ease of evaporation of a liquid is related to the strength of the attractive forces
between the molecules in the liquid. In polar liquids cohesive forces are strong while
in non-polar liquids the cohesive forces are very weak and the molecules escape
easily. For example, ether evaporates more rapidly than ethyl alcohol while ethyl
alcohol evaporates quicker than water.
Surface area
The larger the exposed surface area of the liquid the greater is the number of
molecules escaping from its surface.
Heat of vapoursation
For example, when one mole of water is completely vapourised at 25C, it absorbs
44.180 kJ of energy. This may be written as:
Thus, the molar heat of vapourisation of water at 25oC is 44.18 kJ. The heat of
vapourisation depends upon the strength of attractive forces between the molecules
of a liquid. The relatively high molar heat of vapourisation of water (44.18 kJ mol-1)
suggests strong attractive forces in liquid water.
Vapour pressure
If a liquid is placed in an open vessel, there is complete escape of molecules from the
liquid to the atmosphere. If a liquid is allowed to evaporate in a closed vessel, the
molecules escaping from the liquid surface are collected in a vapour state, above the
surface of the liquid within the container. Due to vapoursation the level of liquid
decreases. After some time, the level of liquid does not change further and becomes
constant.
This behaviour of liquid can be explained as follows. Initially, the system contains
only liquid, and air above it. The air above the liquid is completely evacuated and the
vessel is sealed, so there is nothing above the liquid. As evaporation starts, the
molecules from the surface of liquid escape into vapour state, in the confined space
above. Therefore, the level of liquid falls.
The state where the rate of evaporation becomes equal to the rate of condensation is
called a state of dynamic equilibrium. In such a state, although the amount of liquid
level in the vessel does not change, evaporation has not stopped and the system is
not at rest. In fact, the number of molecules, which escape from the liquid to the
gaseous phase (due to evaporation), becomes equal to the number of vapour
molecules that return to the liquid.
The molecules in the vapour phase begin to exert pressure. As evaporation reaches
the equilibrium state, the concentration of the molecules in the vapour state
becomes constant. The pressure exerted by the molecules in the gaseous phase in
equilibrium with its liquid is called equilibrium vapour pressure of the liquid or its
vapour pressure.
may be defined as 'the pressure exerted by the vapours in equilibrium with its liquid
at a given temperature'. Vapour pressure is a characteristic property of a liquid at a
given temperature. It does not depend upon the amount of the liquid or the vapour
phase. The magnitude of vapour pressure depends upon the following three factors:
Nature of liquid
The vapour pressure of a liquid depends upon the nature of the liquid. When
intermolecular forces are weak, the molecules tend to escape readily and therefore,
the equilibrium vapour pressure is high. Vapour pressure of liquids provides an
indication of the magnitude of intermolecular forces. Ether and alcohol evaporate
faster than water. Hence, ether and alcohol have higher vapour pressure than water
at a given temperature. The higher vapour pressure of ether and alcohol as
compared to water is due to the fact that there are weaker attractive forces in ether
and alcohol.
Presence of impurities
Properties of Liquids - II
Boiling
Vapour pressure measures the tendency for the molecules to escape from liquid to
the gas phase. At lower temperatures the vapour pressure of a liquid is much lower
than the pressure on the surface of the liquid. When the temperature of the liquid is
gradually increased, its vapour pressure also increases. Ultimately a stage is reached
when the vapour pressure of the liquid equals the pressure of the air above it. At this
point, molecules and vapours formed within the liquid can easily rise through the
liquid in the form of bubbles and escape into the air. This phenomenon is known as
boiling and the temperature at which this occurs is known as boiling point.
Boiling point is the temperature at which the vapour pressure of a liquid becomes
equal to the atmospheric pressure. The boiling point, therefore, depends upon the
atmospheric pressure and it changes with the change in the pressure above the
liquid. As the atmospheric pressure increases, it is necessary to heat the liquid to a
higher temperature to make its vapour pressure equal to atmospheric pressure. At
high altitudes like Ooty, having lower atmospheric pressure, water boils at a much
lower temperature than in the plains like Bangalore where atmospheric pressure is
higher.
Generally, boiling points for most of the liquids are specified as normal boiling points.
The normal boiling point of a liquid is the temperature at which the vapour pressure
of the liquid becomes equal to one atmospheric pressure (standard pressure).
It may be noted that once the boiling starts, the temperature of the liquid remains
constant, until the whole of the liquid has vaporized, even though heating is
continued.
Problem
10. Why does the temperature of the boiling liquid remains constant even though
heating is continued ?
Solution
When a liquid is heated, the heat supplied is consumed to pull the liquid molecules
apart against strong attractive forces, which hold them together in the liquid form.
The heat energy goes to compensate the loss of energy due to escaping molecules,
which have to overcome the attractive forces between the molecules of the liquid. As
a result, there is no change in the average kinetic energy of the molecules remaining
in the boiling liquid. Since the average kinetic energy is proportional to the
temperature (1/2mV2 T), therefore, the temperature of the liquid does not change
till the whole of liquid has been converted into the vapour state.
A liquid may be made to boil at any desired temperature by changing the external
pressure.
For example, a liquid may be made to boil at higher temperature by increasing the
pressure on its surface, as is done in a pressure cooker. It may be made to boil at a
lower temperature than the normal boiling point by reducing the external pressure on
it. It is observed that some substances decompose at their normal boiling points and
therefore, they cannot be heated up to their normal boiling points. They are made to
boil at reduced temperatures. This principle is used in purifying less stable liquids by
distillation under reduced pressure. This process is called vacuum distillation.
.
Surface tension
Surface tension is also related to the intermolecular forces in the liquid. The
molecules in liquids are held closely and hence attract each other. A molecule in the
bulk of the liquid is attracted equally on all sides so that the net attractive pull on the
molecule is zero. However, a molecule at the surface is subjected only to the
attractive forces of the molecules below it, as there are no molecules above it.
Therefore, surface molecules experience a resultant downward attractive force from
within the liquid, which tends to make the surface area of the liquid as small as
possible. This causes the molecules at the surface to be pulled inwards and so there
is always some residual imbalance force acting on the surface of the liquids. This is
called surface tension. Whenever we want to stretch the surface, work has to be done
against surface tension. Surface tension may be defined as:
'Force per unit length acting perpendicular to the tangential line on the surface'. It
may also be defined as 'the work done to increase the free surface area of any liquid
by one unit at constant temperature and pressure.'
The SI unit of surface tension or force per unit length is Nm-1. Since this unit is too big
for any practical purpose we use a smaller unit mN m-1 (millinewton meter-1).
Effect of temperature
Surface tension decreases with rise in temperature, almost linearly. The decrease of
surface tension with increase in temperature results because the kinetic energy (or
speeds) of the molecules increases. Thus, the strength of intermolecular forces
decreases resulting in the decrease of surface tension also. For example, clothes are
washed more efficiently in hot water than in cold water due to decreased surface
tension in hot water.
As 'T' approaches critical temperature, the surface tension becomes zero. At this
stage the meniscus between the liquid and vapour disappears.
Nature of liquid
Pressure
Increase of pressure on the surface of a liquid increases the surface tension. Such
effects are not large.
The liquid drops have nearly spherical shapes. Because of surface tension, the free
surface of a liquid tends to attain minimum surface area. Since the sphere has
minimum surface area for a given volume of liquid, the liquid tries to adopt spherical
shape. Examples are water droplets or mercury globules.
Capillary action
When one end of a capillary tube is put into a liquid that wets glass, the liquid rises
into the capillary tube to a certain height and then stops. The rise of liquid in a
capillary is due to the inward pull of surface tension acting on the surface, which
pushes the liquid into the capillary tube. This phenomenon is called capillary action.
The rise of liquid in the capillary is very important. For example, water below the
surface of the Earth rising to the plants through the roots, oil rising into the wick of an
oil lamp, ink rising in a blotting paper, are all examples of capillary action.
Viscosity
Certain liquids flow faster than others. Water and kerosene oil flow rapidly while
honey and castor oil flow slowly. The cause of different rates of flow of liquids may be
easily understood by considering flow of liquid in a beaker. If water is stirred in a
beaker with a rod and left undisturbed for some time, its swirling motion stops after
some time. The faster moving outer layer adjacent to the edge of the beaker comes
to stop first. The slower moving layer near the center, which stops last, is pulling it
back. Different layers in a liquid move over one another with different speeds in the
direction of the flow of the liquid. However, due to intermolecular forces, there is
resistance of one layer to the other layer. These internal self-governing forces tend to
oppose any free motion. This resistance to the flow of a liquid is termed as viscosity.
'The internal resistance to flow in liquids, which, one layer offers to another layer
trying to pass over it is called viscosity'.
The viscosities of liquids are compared in terms of coefficient of viscosity ( ). This is
defined as the tangential force per unit area required to maintain a unit difference in
velocities.
The units of viscosity are poise (P), where 1P = 1 g cm-1 s-1. In S.I. unit, 1P = 0.1 Nsm-
2
.
Viscosity is also related to the intermolecular forces in the liquid. If the intermolecular
forces are large, viscosity will be high. For example, water has higher viscosity than
methyl alcohol because intermolecular forces in water are more than that in methyl
alcohol.
With rise in temperature viscosity of a liquid decreases. This increases the average
kinetic energy and so the intermolecular forces can be easily overcome.
Liquids with extensive hydrogen bonding show higher viscosity due to an increase in
size and mass of the molecule.
For example, glycerol and sulphuric acid show higher viscosity than water due to
hydrogen bonding.
Problem
11. Which of the liquids in each of the following pairs has a higher vapour pressure.
Solution
Characteristics of Solids
Some of the common properties of solids, which distinguish them from other two
states of matter, are:
Solids have definite volume irrespective of the size or shape of the container in
which they are placed.
Many solids have a crystalline appearance and have definite pattern of angles and
planes.
Solids diffuse very slowly as compared to liquids and gases. Constituent particles
are very closely packed in solids permitting very little space for their movement.
Solids have a much higher density (mass to volume ratio) than that of gases and
liquids.
Most solids become liquids when heated. Some undergo sublimation on heating.
The temperature at which a solid changes into liquid is called the melting point and
the process is called as melting. Due to the varying natures of solids their melting
temperatures vary considerably.
Classification of Solids
The above properties suggest that the properties of the solids not only depend upon
the nature of the constituents, but also on their arrangements.
Based on their structural features solids can be classified into three categories:
Crystalline solids
Amorphous solids
Polycrystalline solids
Crystalline Solids
The substances whose constituents are arranged in definite orderly arrangements are
called crystalline solids. Many naturally occurring solid substances occur in the
crystalline form. Some common examples of crystalline solids are sodium chloride,
sulphur, diamond, sugar, etc.
Crystalline solids have sharp melting points, indicating the presence of a long
range order arrangement in them. The long-range order is due to the regular
arrangement of the constituents (molecules, atoms or ions) throughout the three
dimensional network of crystals. For example, experiments (X-ray diffraction method)
show that in a crystal of sodium chloride, the constituents Na+ and Cl- ions are present
at alternate sites as shown below:
Though shown in two dimensions this systematic long-range order is also found in
three dimensions, with each Na+ surrounded by six ions and vice versa. This order is
due to strong coulombic forces of attraction between Na+ and Cl- ions. Similar regular
arrangements are found in other solids too.
Crystalline solids are anisotropic by nature i.e., their mechanical, electrical and
optical properties depend upon the direction along which they are measured.
When cut or hammered gently they show a clean fracture along a smooth surface.
Amorphous Solids
Substances whose constituents are not arranged in an orderly manner are called
amorphous solids. They are also called pseudo solids and differ from crystalline solids
in many respects. The common examples of amorphous solids are glass, rubber,
fused silica, plastics, etc.
Their mechanical, electrical and optical properties do not depend upon the
direction along which they are measured. They are isotropic and in this respect
resemble liquids and are sometimes referred to as super cooled liquids.
Amorphous solids do not have sharp melting points. They have some orderly
arrangement but it is not extended to more than a few Angstrom units. Thus,
amorphous solids are said to have short-range order. On heating they melt and begin
to flow like liquids.
Polycrystalline Solids
These are crystalline solids, constituted of very fine crystals, not seen by the naked
eye. These solids appear amorphous but are not so because the fine crystals are
randomly oriented. Thus even though each individual crystal is anisotropic the
polycrystalline materials as a whole appear to be isotropic. Metal powders are
polycrystalline in nature.
Crystalline Solids
Crystalline substances have a definite rigid shape. The shape and size of crystals
(even of the same materials) differs depending upon the conditions under which they
are grown. Crystals of a given substance are bound by plane surfaces called faces.
The angle between any two faces is called interfacial angle. But the angles between
the faces of a given form always remains same. This important characteristic feature
of a given crystalline substance is known as law of constancy of interfacial angles.
Crystalline solids may be classified into four types depending upon the nature of
bonds present in them.
Molecular crystals
In molecular crystals, the constituent particles are molecules. These molecules are
held together by weak forces known as Van der Waal's forces. Common examples are
dry ice, wax, iodine, sulphur, etc.
Molecular crystals are soft, compressible and can be distorted very easily.
These are bad conductors of electricity and are regarded as electrical insulators.
They are volatile and have low heats of vaporization and low enthalpy of fusion.
Ionic crystals
The ionic crystals consist of positively and negatively charged ions arranged in a
regular fashion throughout the crystal. They form a network of positive and nagative
ions in three dimension in such a way that cations and anions occupy alternate sites.
These are held together by strong electrostatic forces.
They are poor conductors of electricity and therefore are insulators in the solid
state.
They have high heat of vaporization and so have low vapour pressure.
Covalent crystals
In covalent crystals, the constituent particles are atoms of the same or different kind,
which are bonded to one another by a network of covalent bonds. The important
characteristics of covalent crystals are:
They are extremely non-volatile and have very high melting points.
Metallic crystals
In metallic crystals the constituent particles are positive kernels i.e., nuclei where
inner electrons are dispersed in a sea of mobile valence electrons. The forces present
between the constituents are metallic bonds.
They are highly ductile and malleable i.e, they can be beaten into sheets and
drawn into wires.
The examples of metallic crystals are common metals such as nickel, copper and
alloys.
Problem
12. The melting point is a rough measure of the attractive forces in solids.
Arrange the following solids in the order of increasing strength of attractive forces.
Solution