Brilliant STUDY CENTRE LT.
2023 - RESIDENTIAL (ONLINE LECTURE NOTE A)
CHAPTER - 05
STATES OF MATTER
• Matter - Anything which has mass and occupies space is called matter.
• Matter is mainly classified into three
1. Solid
2. Liquid
3. Gas
• This classification is mainly based on the intermolecular force.
• Intermolecular force is the force act between the constituent particle.
• There are mainly 2 types of intermolecular forces that are attractive and repulsive.
• Attractive intermolecular forces are known as van der Waal’s forces.
Van der Waals forces
1. Dispersion force of London force
Suppose we have two neutral symmetrical atoms ‘A’ and ‘B’ in the close vicinity of each other. It may
so happen that momentarily electronic charge distribution in one of the atom say ‘A’ become
unsymmetrical ie, the charge cloud is more on one side than the other. This result in the development
of instantaneous dipole on the atom ‘A’ or a very short time. This instantaneous dipole cause to induce
the dipole on B. Then the temporary dipoles on atom ‘A’ and ‘B’ attract each other.
2. Dipole-Dipole force
This type of force act between the molecules possessing permanent dipole. (Eg : HCl). This interaction
is stronger than London force but is weaker than ion-ion interaction. Dipole-dipole interaction energy
1
between stationary polar molecule (as in solids) is proportional to and that between rotating polar
r3
1
molecule is proportional to
r6
3. Dipole-Induced dipole force
This type of force operate between molecule having permanent dipole and the molecule lack of
permanent dipole. Permanent dipole of the polar molecule induces dipole on the electrically neutral
1
molecule by deforming its electronic cloud. In this case also interaction energy is proportional to .
r6
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4. Hydrogen bond
This is special case of dipole-dipole interaction. This is found in the molecule in which highly polar
N–H, O–H, H–F bonds are present
THE GASEOUS STATE
Properties of gas
1. Highly compressible
2. Extent pressure equally in all direction
3. Much lower density than solid and liquid
4. Volume and shape is not fixed
5. If mix evently and completely in all proportions.
In periodic table only eleven elements exist as gases under normal conditions.:-
H, N, O, F, Cl, He, Ne, Ar, Kr, Xe, Rn
The gas Laws
1. Boyles law (P-V relationship)
At constant temperature, the pressure of a fixed amount of a gas varies inversely with its volume.
1
P
V
1
PK K proportionality cons tan t
V
PV K
It means at constant temperature the product of pressure and volume is constant for a fixed amount
of gas.
If a fixed amount of gas at constant temperature T occupying volume V1 at pressure P1 undergoes
expansion, so that volume become V2 and pressure become P2 then according to Boyle’s law
P1V1 = P2V2
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PV
2. Charles law (T–V relationship)
At constant pressure volume of a fixed amount of gas is directly proportional to the temperature.
VT
V KT
K proportionality cos tan t
V
K
T
V1 V2
T1 T2
1
Charles also found that for each degree rise in temperature, volume of a gas increases by of
273.15
the original volume of the gas at 0°C. Thus if volume of the gas at 0°C and t°C are V0 & Vt respectively
then
1
Vt V0 V0
273.15
t
Vt V0 1
273.15
273.15 t
Vt V0
273.15
At this stage we define a new temperature scale called Kelvin temperature scale or absolute scale.
Thus 0°C on the celsius scale is equal to 273.15 K at absolute scale. Thus we add 273.15 to the
celsius temperature to obtain temperature at Kelvin scale.
If we write = Tt = 273.15 + t and T0 = 273.15 then modify the above equation.
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T
Vt V0 t
T0
Vt Tt
V0 T0
Graph of V vs T is a straight line and on extenting to zero volume each line intercept the temperature
axis at –273.15°C this temperature is called absolute zero. In fact all the gases get liquefied before
this temperature is reached.
3. Gay Lussac’s Law (P–T relationship)
At constant volume pressure of a fixed amount of gas varies directly with the temperature.
P T
P KT K proportionality cons tan t
P
K
T
P1 P2
T1 T2
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4. Avogadro law (V - n relationship)
Equal volume of all gases under the same conditions of temperature and pressure contain equal
number of molecule.
V n n number of moles of the gas
V Kn
MOLAR VOLUME OF GAS
1. When STP conditions taken are 0°C and 1 atm molar volume of a gas = 22.4 L
2. When STP conditions are taken as 0°C and 1 bar molar volume of the gas = 22.7 L
3. When SATP conditions are used 25°C and 1 bar molar volume = 24.8 L
Ideal gas equation
A gas that follows Boyles law, Charles law and Avogadro law strictly is called an ideal gas. Such a gas
is hypothetical. This three laws combined together in a single equation which is known as ideal gas
equation.
1
At constant T & n; V Boyles law
P
At constant P & n; V T [Charles law]
At constant P & T; V n [Avogadro law]
nT
V
P
nT
VR
P
where R is the proportionality constant called universal gas constant. PV nRT
Unit of P Unit of V Value of R
3 -1 -1
atm L (or) dm 0.0821 L atm K m ol
3 3 -1 -1
atm cm 82.1 cm atm K m ol
-2 3 -1 -1
dynes cm cm 1.987 cal K m ol
-2 3 -1 -1
Nm (or) Pa m 8.314 JK m ol
3 3 -1 -1
kPa dm 8.314 kPa dm K m ol
3 3 -1 -1
bar dm 0.083 bar dm K mol
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If, temperature, volume, pressure of a fixed amount of gas vary from T1, V1, P1 to T2, V2, P2 then we
can write
P1V1 PV
nR & 2 2 nR
T1 T2
P1V1 P2 V2
T1 T2
DENSITY AND MOLAR MASS OF A GASEOUS SUBSTANCE
From the ideal gas equation PV = nRT
W W
PV Rt |n
M M
PM W
RT V
PM W
d |d
RT V
Dalton’s law of partial pressure
The total pressure exerted by the mixture of non reactive gases is equal to the sum of the partial
pressures of individual gases. In a mixture of gases the pressure exerted by the individual gases is
called partial pressure. Ptotal = P1 + P2 + P3 + ...............
Where Ptotal is the total pressure exerted by the mixture of gases and P1, P2, P3 .............. are the partial
pressures of gases.
Partial pressure in terms of mole fraction
Suppose at the temperature T, three gases enclosed in the volume V, exert partial pressure P1, P2, P3
n1RT n RT n RT
respectively then, P1 ; P2 2 ; P3 3
V V V
n1, n2, n3 are the number of moles of gases
n1RT n 2 RT n 3 RT RT
Ptotal = P1 + P2 + P3 = n1 n 2 n 3
V V V V
n1RT
P1 V
On dividing P1 by Ptotal we get Ptotal RT
n1 n 2 n 3
V
P1 n1
x1
Ptotal n1 n 2 n 3
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P1
x1
Ptotal
P1 X1 Ptotal
P2 X 2 Ptotal
P3 X 3 Ptotal
Partial pressure = mole fraction × total pressure
KINETIC MOLECULAR THEORY OF GASES
Postulates
1. Every gas is made up of large number of small particles called molecule all the molecules of a particular
gas are identical in mass and size.
2. The molecules of a gas are separated from each other by large distance so that the actual volume of
the molecule is negligible as compared to the total volume of the gas.
3. The force of attraction or repulsion between them are negligible.
4. The force of gravitation on the molecule is also supposed to be negligible.
5. The molecules are moving continuously in different direction with different velocity.
6. The pressure exerted on the walls of the containing vessel is due to the bombardment of the molecules
on the walls.
7. Molecules are supposed to be perfectly elastic hard spheres so that no energy is wasted on collision.
8. Average KE is directly proportional to absolute temperature.
Kinetic gas equation
1
Based on the above postulates a mathematical equation has been derived. PV = mnc 2
3
P Pr essure
V Volume
M Mass of each molecule
n Total number of molecule
c Total mean square speed (RMS)
Molecular speed
8RT
1. Average speed =
M
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3RT
2. RMS =
M
2RT
3. Most probable speed =
M
T Temperature
M Molecular mass
AVERAGE KINETIC ENERGY
1
From kinetic gas equation PV mnc 2 for 1 mole of gas m n M, molar mass
3
1
PV Mc 2
3
2 1
PV Mc 2
3 2
2 1
PV K.E. | K.E Mc 2
3 2
3
K.E. RT..............(1)
2
From ideal gas equation PV RT
3
K.E. PV...........(2)
2
To calculate average K.E.per molecule
3 RT
K.E. ...........(3)
2 NA
3 R
K.E. KT | K
2 NA
K Boltzmann cons tan t 1.38 10 23 JK 1
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MAXWELL-BOLTZMANN DISTRIBUTION CURVE
Fraction of the molecule possessing particular speed are plotted against their corresponding speed at
particular temperature.
Observations
1. Fraction of molecule having too low or too high speed are very small.
2. The peak of the curve corresponds to the speed possessed by maximum fraction. This is called most
probable speed.
Maxwell - Boltzmann curve at different temperature
1. Most probable speed increases on increase in temperature.
2. Fraction of the molecule possessing most probable velocity decrease on increase in temperature.
3. Fraction of the molecule having higher speed increase on increase in temperature.
4. Fraction of the molecule having lower speed decreases on increasing temperature.
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Ideal and Real gases
A gas which obey the ideal gas equation PV = nRT under all conditions of temperature and pressure
is called ideal gas. The gases are found to obey gas laws fairly well if pressure is low or the temperature
is high, such gases are real gases.
To study the deviation from ideal behaviour, let us study how real gases show deviation from Boyle’s
law. According to Boyles law pV = K at constant temperature. Hence the plot of PV vs P should be a
straight line parallel to x-axis. However real gases do not show such a behaviour.
The extent to which a real gas deviates from ideal behaviour can be conveniently studied in terms of
PV
‘Z’ called compressibility factor. Z =
nRT
1. For ideal gas Z = 1
2. For real gas Z 1
a. Z > 1, gas show positive deviation
b. Z < 1, gas show negative deviation
Vander Waals equation
To explain the behaviour of real gas van der Waals modified the ideal gas equation by applying
corrections. That are volume correction and pressure correction.
an 2
P V nb nRT
V2
a and b are van der Waals constants.
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Significants
1. Greater the value of van der Waals constant ‘a’ larger are the intermolecular attraction.
2. Value of ‘b’ is a measure of effective size of the gas molecule. Its value is equal to four times the actual
volume of the gas molecule. It is called excluded volume or co-volume.
Units.
‘a’ atm L2 mol–2 (or) bar dm6 mol–2
‘b’ L mol–1 (or) dm3 mol–1
Van der Waals equation at different conditions
a
1. At low pressure P V RT
V2
2. At high pressure P V b RT
CAUSE OF DEVIATION FROM IDEAL BEHAVIOUR
Two postulates of the kinetic theory of the gas not hold good in all cases.
1. Volume occupied by the gas molecule is negligible as compared to the total vol. of the gas.
2. The force of attraction or repulsion between the gas molecules are negligible.
This assumptions true only if the pressure is low and temperature is high so that the distance between
the molecule is large.
Liquefaction of gases and critical temperature
A gas can be liquefied by cooling or by application of pressure or the combined effect of both.
Critical temperature (TC) of a gas may be defined as that temperature above which it cannot be
liquified however high pressure may be applied on the gas.
The pressure required to liquify the gas at the critical temperature is called critical pressure (PC).
Volume occupied by one mole of the gas at critical temperature and critical P is called critical volume
(Vc). These three are called critical constant.
Critical constant in terms of van der Waals constant
a
PC
27b 2
8a
TC
27Rb
VC 3b
Boyle temperature (TB)
The temperature at which real gases behave like an ideal gas called boyle temperature.
a
TB =
Rb
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Relationship between critical constants
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PC VC RTC
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Grahams law of diffusion/effusion
Spreading of the molecules of a gas throughout the available space is called diffusion. Gaseous
molecules escaping through a small hole called effusion.
Under similar conditions of temperature and pressure, the values of diffusion/effusion of different
gases are inversely proportional to the square root of their densities.
For two gases having densities d1 and 2 and rate of diffusion r1 and r2
r1 d2
r2 d1
Vol / Amount / no.of mole diffused
Rate of diffusion
Time taken
Molecular mass = 2 × density
r1 M2
r2 M1
If two gases taken at different pressure, then greater the pressure greater is the rate of diffusion.
r1 P1 d 2 P1 M2
r2 P2 d1 P2 M1
r1 Td TM
If two gases diffuse at different temperature, 1 2 1 2
r2 T2d1 T2 M1
LIQUID STATE
1. Vapour pressure
Vapour pressure of a liquid at any temperature may be defined as the pressure exerted by the vapour
present above the liquid in equilibrium with the liquid at that temperature.
Vapour pressure and temperature are directly proportional.
2. Boiling point
It is defined as the temperature at which the vapour pressure of the liquid become equal to the external
pressure.
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3. Surface Tension
It is the force acting at right angles to the surface along one cm length of the surface.
Unit dynes per cm
OR
Nm 1
4. Viscosity
It is the resistance to flow viscosity decreases on increasing the temperature.
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