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Synopsis :
1.
2.
3.
4.
5.
Anything which has mass and occupies some space is called matter.
Matter exists in three different physical states known as solids, liquids and gases.
Depending on the temperature and pressure a substance can exist in either of the 3 states and
these 3 states are inter convertible by changing P and T.
Both liquids and gases are termed as fluids as they have flowing ability.
Of these three states, gaseous state is the simplest because of uniformity in behavior.
Comparison of these 3 states:
Property
Gases
Liquids
Solids
1. Shape
No definite shape No definite shape
Have definite shape
2. Volume
No definite volume Have definite volume Have definite
volume
3.Randomness
Complete
In between that of gases Orderly
molecular
and solids
arrangement of
randomness
molecules
4. Density
Very low
Inter mediate
Very high
5. Compressibility
Highly
Slightly compressible Incompressible
compressible
6. Diffusion
Diffuse rapidly
May diffuse slowly
Will not diffuse
7.Inter molecular forces Very weak
Intermediate
Strong
8. Inter molecular
Very large
Intermediate
Very small
distances
6. The standard conditions for a gas are also known as S.T.P conditions or N.T.P conditions
7. S.T.P conditions
Temperature
Pressure
0
t=0 C
P = 1 atm
T = 273 K
P = 76 cm of Hg
P = 760 mm of Hg
8. The weight of one litre of a gas is known as its density. The density of a gas depends on its
temperature and pressure.
9. The units for the density of a gas are gm/lit.
10. Mass, Volume, Pressure and temperature are the measurable properties of a gas.
11. Mass (m):
1. The mass of a gas is expressed in gms (or) kilograms.
2. The mass of 6.023 1023 molecules of a gas is known as gram molar mass.
m
M
1.
2.
3.
4.
1) A = C+ 273 2) K = C+ 273
T = t + 273
4. At absolute zero,
1. Molecular motion in the gas ceases.
2. Pressure of the gas becomes zero.
3. Volume of the gas becomes zero.
4. Kinetic energy of the gas becomes zero.
15. Gas Laws: The behaviour of gases and the relation between variables like, m, V, T, P etc are
explained by certain laws known as gas laws.
BOYLE'S LAW:
1. For a given mass of a gas at constant temperature, the volume is inversely proportional to
the pressure.
2. For a given mass of a gas at constant temperature, the product of its volume and pressure is a
constant value.
3. According to Boyle's law for a given mass of a gas at constant temperature the density of the
gas is proportional to the pressure of it.
4. For a given mass of gas at constant temperature.
V
1
P
1.
PV = constant;
2. dP
d/P = constant
3. P1V1 = P2 V2
T1T2
T2 > T1
P
V
4.
V
P1 P2
=
d1 d 2
PV
1/ P
1
2) d T
4)
V1 V2
=
T1
T2
5) dT=constant
V
V
T
V
3) T Constant
6) d1T1 = d2T2
P3
P2 P1>P2>P3
P1
tC
4. For a given mass of a gas at constant pressure the volume of the gas increases or decreases
by 1/273th part of its volume at 0C for every 1C raise or fall in temperature
Vt = V0 (1 + t)
3
( is volume coefficient)
17. AVOGADRO'S LAW:
At constant temperature and pressure, the volume of a gas is proportional to the number of
v1
n
= 1
v 2 n2
n1
n2
P n;
=
21. IDEAL GAS EQUATION (OR) PERFECT GAS EQUATION (OR) EQUATION OF
STATE:
By combining Boyle's law and Charles laws we get
1. PV = nRT ; PV = RT for 1 mole
m
m
RT n =
M
M
2. PV =
M d 2 p 2 T1
3. P =
d = density of the gas
hdgV
4. R = nT
(P = hdg)
d = density of mercury (13.6gm/c.c)
g = gravity (980 cm/ sec2)
h = height of mercury column (76 cm)
22. For a given mass of a gas, "nR' is constant. So
PV
= constant
1. T
P1V1 P2 V2
=
T1
T2
2.
d1T1 d 2 T2
=
P1
P2
3.
23. Numerical Values of R:
4
The value of 'R' is independent of the nature of the gas and amount of gas but it depends on
units of expression.
22.4
lit atm / k / mole
1. R = 273
24.
25.
26.
27.
28.
29.
PV
30. For ideal gases; RT =Z; Z = compressibility factor; for ideal gases, Z = 1; for real gases Z>1 or
<1
31. GRAHAMS LAW OF DIFFUSION:
1. The spontaneous inter mixing of gases to form a homogeneous mixture is known as the
diffusion.
2. Gases diffuse from high pressure to the low pressure.
3. The Volume of gas (V) that diffuses in unit time is known as the rate of diffusion (r) of the
V
r = t ; unit of rate of diffusion: c.c /sec
gas
Graham's law:
4. At constant temperature and pressure the rate of diffusion of a gas is inversely proportional
to the square root of its density (or) molar mass (or) vapour density.
1
1) r d
2) r M
3) r V.D
5. For two gases diffusing under similar conditions of temperature and pressure.
5
d2
=
d1
v.D2
v.D1
M2
v
t
= 1 2
M1
v 2 t1
=
1)
6. Under similar conditions of temperature and pressure if the time of diffusion is same for two
r1
v
= 1
r2
v2
different gases.
7. Under similar conditions of temperature and pressure if equal volumes of two gases diffuse.
r1 t 2
=
r2
t1
r1
p
M2
= 1
r2 p 2
M1
M1 t 1
M2 t 2
If two or more gases are at different pressures and occupying different volumes are forced in to
a vessel of volume 'V' ;
p v + p 2 v 2 + ...
PTotal = 1 1
V
then
If two different gases with equal masses are present in the mixture, the gas with less molecular
weight has more partial pressure.
If two different gases with different masses and different molecular weights but same volumes
are mixed together, their partial pressures are same.
Dalton's law of partial pressures is applicable the mixture of non reacting gases.
Ex: CO+CO2, N2+O2 H2+N2, H2+O2, SO2+O2,
NO2+O2
Dalton's law of partial pressures is not applicable for reacting gases
The pressure exerted by water vapour which is in equilibrium with liquid water is called
aqueous tension.
It is denoted by "f"
Aqueous tension increases with temperature.
Water insoluble gases are collected over water and they become moist gases. Pdry gas = Pmoist gas
f
Water insoluble gases are generally collected over water. A gas collected over water is
saturated with water vapour. Such a gas is called moist gas.
The volume of a moist gas is generally measured at atmospheric pressure. So pressure of moist
1. CO and Cl2
2. NO and Cl2
3. NO and O2
4. H2 and Cl2
5. SO2 and Cl2
6. NH3 and HCl
low temperatures.
i) Actual volumes of gas molecules are negligible at low P and high T but considerable at high
'P' and low 'T'
ii) Gases are not liquefiable at very low P and high T but they can be liquefied at high 'P' low T.
Thus kinetic theory is applicable for ideal gases and not applicable for real gases.
Kinetic gas Equation:
Based on the assumptions of kinetic theory of gases, kinetic gas equation is derived.
1
3 mnc2
1.
Boyle's law: PV =
2
3 KT (at
constant 'T')
V 2K
=
T 3 P (at
constant 'P')
2. Charles' law:
3. Avogadro's law: n1 = n2 or
1
1
m2 n2 c 22
m1 n1 c12
3
3
=
1
1
m2 c 22
m1 c12
2
2
5.
m1 n1 c 12
1
3
m 2 n 2 c 22
v
or P = P1 + P2
P=
Graham's law of diffusion:
v
3p
1
or r
d
d
C=
Kinetic energy:
(at constant P)
3
2
nRT
3
2 RT
Ek =
3
3 RT
or E k = KT
2
2 N
R
N
16
Fraction of molecule
Average kinetic energy of any gas is directly proportional to the absolute temperature and
independent of nature of gas. This is called Maxwell's generalization.
Two different gases at same temperature will posses same average K.E.
If two different gases present at same temperature are mixed with each other there will not be
Though the velocities change so frequently, the ratio of certain number of molecules with
certain velocity to the total number of molecules remains constant.
T2 > T1
T2
T1
Velocities
With increase in temperature, the number of molecules possessing higher velocities is increased
and the number of molecules possessing low velocities and the number of molecules possessing
most probable velocity is decreased.
As the velocities of the molecules increase, the fraction of the molecules possessing a particular
temperature
2RT
=
M
2PV
=
m
2P
d
Cp =
M = mass of given gas
Cp = 0.8166 RMS velocity
The average of the velocities of all the molecules in the gas at any temperature is known as
average velocity.
It is represented by C
C=
C1 + C 2 + C 3 + ... + C n
n
C=
8RT
=
M
8PV
=
M
8P
d
C12 + C 22 + C 32 + .......C n2
3PV
=
m
T1
T2
velocity
ii) For two different gases at the same temperature,
C1
=
C2
3P
d ; C = 1.58
T
x10 4 cm / sec
M
n
C=
;C=
=
For a gas at two different temperature the ratio of its RMS velocities is given by
C1
=
C2
3RT
M
M2
M1
> C > nc
Ratio between molecular velocities
1) Cp:
3)
C:C = 2 :
Cp : C : C =
8
: 3
0.8166: 0.9213: 1
C p : C : C = 2 : 2.55 : 3
2)
Cp : C : C =
4)
11
1: 1.128: 1.224
Intermolecular forces generates as the result of the neutral attractions of unlike charges (or)
repulsions of like charges.
Ion - dipole interactions :
The magnitude of interaction energy depends on the charge on the ion (z), its dipole moment
( )
and on the inverse square of the distance (r) between the ion and the dipole
E = Z . / r 2
Ion - dipole forces are mainly important in aqueous solutions of ionic substances
Ex: NaCl in water
Dipole - Dipole forces
These forces are due to electrical interactions among dipoles on neighbouring molecules
These forces are generally weak, are in the order of 3-4 KJ/mol. and significant only when
molecules are in close contact
The strength of a given dipole - dipole interaction depends on the sizes of the dipole moments
involved
As the molecule is more polar, dipole-dipole interactions are more and boiling point of
substance will be more
1
3
1
6
b) Dipole- Dipole interactions between rotating molecules is proportional to r here r is the
distance between polar molecules.
London dispersion forces:
Instantaneous dipole on one atom can affect the electron distributions in neighbouring atoms
and induce temporary dipoles in those neighbours. As a result weak attractive forces develop
known as london forces or dispersion forces.
A smaller molecule (or) atom is less polarisable and has smaller dispersion forces
12
1
6
These are always attractive forces and proportional to r , here r is distance between the
two interactive particles.
More spread out shapes posses higher dispersion forces than those compact molecules which
minimise molecular contact hence posses lower dispersion forces
Ex: n - pentane, b.p is 309.4k( long chain)
2,2 - dimethyl propane, b.p is 282.7k (compact chain)
Dipole - Induced forces:
Permanent dipole of the polar molecule induces dipole on the electrically neutral molecule by
deforming into electric cloud and attractive forces develop.
1
2
This interaction range is proportional to r here r is the distance between the molecules.
The magnitude of induced dipole moment also depends on the magnitude of the dipole
moment of permanent dipole and polarisability of neutral molecule.
These repulsive forces between the particles (atoms, molecules or ions) are due to electron electron repulsions (or) nucleus - nucleus repulsions.
Thermal Energy
The energy due to the motion of the atoms or molecules of the substance.
If thermal energy predominates over inter molecular forces the substances would change from
solid liquid gas
If intermolecular forces predominate over thermal energy then substance change from
gas liquid solid.
Molecular collisions and mean free path :
Mean free path( ) : The average distance that a molecule travels between two successive
collisions is called as Mean free path( )
In gases the mean free paths of molecules are several hundred molecular diameters, where as
in liquids it is less than the diameter of molecules.
RT
=
2.N A . .P
Collision Freequency (Z) : The average rate of collisions made by a molecule is known as
collisoin frequency(Z)
(or)
The average number of collisions one molecule makes in a time interval divided by the length
of the interval.
1
Time of flight : Z
13
= z
1
C= Z
Real gases :
In perfect gas, molecules move independently of one another here mean free path >>r
(the radius of the molecule).
Perfect gas has energy only from kinetic energy but not any contribution from potential
energy.
In real gases the intermolecular attractions are important . At large separation of molecules,
the energy lowering attractions are dominant, but at short distances the energy raising
repulsions dominate
Isotherms of CO2 and critical temperature:
The isotherms of CO2 have shapes different from those implied by Boyles law particularly at
high pressure and low temperature
Experimental isotherms of CO2 resemble the perfect gas isotherms at high temperature and
low pressure.
0
At 31.04 C (304.19K) ( 30.98OC as per CBSE text book) the gaseous state of transforms
continuously into the condensed state and there is no stage between the liquid and gas. This
temperature is known as critical temperature (Tc )
Critical temperature of a gas is the highest temperature at which liquefaction of gas first
occurs
At critical temperature liquid phase passes into gaseous state imperceptibly and continuously
A gas below the critical temperature can be liquefied by applying pressure and is called
vapour of the substance.
A gas can not be liquefied by the application of only pressure without cooling it below the
critical temperature.
The isotherm at critical temperature is critical isotherm.
At critical temperature, density of vapour phase equal to density of liquid phase
The dense fluid obtained by compressing a gas above its critical temperature is not a true
liquid but behaves as liquid in many aspects called as super critical fluid.
Super critical fluid can be used as ( i) solvent
ii) It does not have a surface which separates it from vapour phase
Ex: Super critical CO2 is used to extract caffeine in the manufacture of decaffeinated coffee.
(P )
Pressure required to liquefy a gas at its critical temperature is called critical pressure c .
The volume occupied by 1 mole of the gas at critical temperature and critical pressure is
(V )
critical volume c .
14
Compression factor is the ratio of the actual molar volume of a gas to the molar volume of a
perfect gas under the same conditions.
Molar volume of the gas ( Vm )
(Z ) =
molar volume of perfect gas ( Vm perfect )
compression factor
V
( Z ) = real
Videal
(V
perfect
m
) = RT
P
a
bR
For the gas molecules the available volume for free travel is not equal to the volume of the
container.
At low pressure, the volume is large compared with the volume excluded by the molecules i.e.
V >> nb V
(Vmol ) = 4 / 3. r 3
n
Reduction in pressure V
an 2
Reduction pressure = v 2
where a is the proportionality constant.
vander Waals equation of state is
an 2
P + 2 (V nb ) = nRT
V
n2
nRT
a 2
P=
V nb
V
P + 2 (V b ) = RT
V
for 1 mole
PC =
a
8a
,VC = 3b, TC =
2
27b
27 Rb
Reduced pressure is P / Pc
Reduced volume is V / Vc
Reduced temperature T / Tc
Conditions of liquifaction of gases :
Gases which have very low b.p are liquified by using Joule-Thomson efect:
Joule - Thomson effect:
Cooling of gas by expansion from high pressure side to low pressure is called Joule Thomson effect .
Hydrogen gas under normal conditions, it warms up in Joule- Thomson expansion. (Since
Z>1).
Hydrogen gas also cooled by Joule - Thomson effect if it cooled first to its inversion
temparatureand then allowed to expand.
LIQUID STATE
Liquids , a) possess strong intermolecular forces
b) less compressable
c) more denser
d) has definite volume
e) can flow like gases
Vapour pressure:
The pressure exerted by vapours when there is an equilibrium state between the liquid phase
and vapour phase is called equilibrium vapour pressure (or) saturated vapour presure.
At 1 atmosphere pressure boiling temparature is called normal boiling point and at 1 bar
pressure it is called standard boiling point of the liquid.
Standard boiling point of a liquid is slightly less than the normal boiling point since 1 bar is
less than 1 atm.
Ex: normal b.p. of water is 373k and standard b.p. of water is 372.6k
At high altitude as the atmospheric pressure is less, the liquids boil at low temperature.
In a closed vessel a liquid on heating doesnt boil but its vapour pressure increases and at a
critical temperature, density of liquid and density of vapour is going to be equal.
Surface tension: (r):
The force acting along the surface of a liquid at right angles to any line of 1 unit length .
The energy required to increase the surface area of the liquid by 1 unit is called surface
energy.
2
(in dynes/cm )
Diethylether
16.9
Acetone
23.7
Carbon tetra chloride
26.9
Ethanol
22.3
Water
72.8
Viscosity:
Strong intermolecular forces between the molecules of successive layers of liquid holding
them together show resistance to the flow and create friction between the layers of fluid. The
measure of this resistance to the flow of liquid is viscosity.
The regular gradation of velocity for layers in passing from one layer to the next layer is
called Laminar flow.
A force (F) is required to maintain the flow of layers is proportional to the area (A) of contact
dv
and velocity gradient dx .
dv
dv
F = A.
dx
dx
1 1
1 poise = 1 g cm .s
1
1 1
= 10 Kgm s
12.0
12.2
19.9
8500
19