2

5.1. GENERAL INTRODUCTION ISC CHEMISTRY PAR

In previous
elements, comp units, have we
learmt about the kinds of matter
mpounds, and certain nt DIPOLE-DIPOLE

olecularproperties mixtures. ATTRACTIONS

s. We have also learnt

paracle shape and such atomic size,

of matter
as
polarity, etc. ionizationto the
entn D
such as an atomwhich are related
ODservable properties of a material
or
molecule. However,
si
e.properties
Ons or associated with a
are bulk
properties
collection of large or
molecules. A few such number of
atoms
temperature, melting point. properties are pressure. volume
ension. etc. For boiling point, vapour
take a
certain example. to pressure, Surta
study the boiling point, we
molecule of a minimum amount of the
liquid because an have to Fig. 5.1 Dipole-dipole attraction between HF
water liquid does not boil but the individual
bulk boils. Collection molecules.
molecules have of
molecules do not wet. wetting properties. However, individual
1.e.. solid Water exists in three different The dipole-dipole interaction energy betwcen stan
(ice). physical states
states of water, iquid (water) and vapour state. In all the polar molecules (as in solids) is proportional to 1/ and that
chemical composition of three
where tbetwen
i.e.. H0. water remains the same. rotating polar molecules is proportional to 1/ where
Physical properties of a substance
state in which it r is
t
exists. depend upon the distance between polar molecules.
Chemical properties of a Proof for the existence of dipole-dipole attractions, ( dia
change of its physical state. substance do not change with the dipole attractions exist between the polar molecules, then
by the However, rate of reaction is affected
physical
state. should have higher boiling points and melting points as
comad
The aim of this unit is
to discuss
to non-polar molecules having same shape and same molecule
which govem the some
important aspects weight. This is actually found to be so. For example, the slioh
behaviour of matter in different
with. it is necessary to beginstates. To polar NO molecule has higher boiling point (-151°C)
understand the
molecular interactions and effect of nature of intermolecular forces, tonon-polar N2 (B.P. =-196°C) and O2 (B.P.=-183°C)as compa
particles thermal energy on the motion of
because the physical state in Dipole moments are the measure of polar
molecules
detemined by the resultant of the which a substance exists, is character o
molecules. Molecules having
and ordering effect of the disordering effect of thermal energy and have higher
higher dipole moments are more polr
cohesive forces of attraction. melting and boiling points indicating
dipole-dipole attractions. For example, H20 stronger
5.2. INTERMOLECULAR and NH,
having
FORCES (VAN DER the same
molecular weight, have dipole moments 1.85 D and neart
WAALS' FORCES) respectively. Thissuggests that attractive forces are
1.49p
Intermolecular forces are the forces of attraction water than ammonia and H20 is a stronger in
among the molecules of a substance (solid, existing The hydrogen bond
liquid while NH3 is a gas.
The
liquid or gaseous). HF, H20 and NH3 is a
found in highly
polar molecules suchas
magnitude of these forces is maximum in the solids and special case of dipole-dipole interaction.
decreases passing from solid to liquid and from liquid to gaseous
on
b) Lon-Dipole
These forces are purely electrostatic and Attractions. These forces
anion) and a polar molecule. Theexist between a
states. 1on (cation or
thus,
nature.Another name given to intermolecular forces is vanphysical in interaction depends strength
forces after the Dutch chemist who first
der Waals
the size and upon the charge and the size of the 1on of
these forces. It may be noted that the investigated the origin of
The charge magnitude of dipole moment of the and
meant to apply to the
intermolecular forces are not density cations is higher (due to their
on polar moec
purely electrostatic forces that exist between than on
oppositely charged ions. Likewise, they do not include the forces a cation
anions, smaller
therefore, these interactions are stronger
and a De
that hold atoms
together, covalent bonds or hydrogen bonds. dipole and an dipole as
compared to the
anion having same
eraction between
size. A
Types and Origin of Intermolecular Forces important example of the charge but biggern
different ions. In interaction of this type is the
(a) Dipole-dipole
Attractions (or Keesom forces). These Cl ions are
an
aqueous sodium chloride nya Nara
forces exist between
polar molecules like HF, H20, etc. Such molecules surroundedby opp soluuon.
Ppositely charged ends wa
molecules have a partial positive
charge
at one end and a
partial ike NaCi, having large dipole moment.
negative charge at the other end. They are called KCI, etc. dissolve When 10 compound

dipoles. The dielectric to in water, the 3

positive end of one dipole attracts the negative end of the other. In tetrachloride keep the ions apart. water
mo carde
HF molecule, fluorine (CCl4), being a On the other
being more electronegative acquires a to han
negative charge whereas the hydrogen end acquires the slight participate in ion-dipolenon-polar molecule, 1a c k s the :

amount of positüve
same
charge. The dipole-dipole interactions then tetrachloride
(or any other interactions.
herefore. carh
take place among the HF
molecules as shown in Fig. 5.1.
ionic compounds.
non-polar liquid) isThercnle
p a oor

(c)
Generally, dipole-dipole attractions are about 1% as strong
Dipole Lon-Induced Dipole Interaction
betweenInteractions
as a covalent bond and the and Dipole lndr

attractions between the opposite poles

are
greater than repulsions between the like an ion
or a (Debye forces). These inter.
molecules have net attraction poles. Thus, the
towards each other. These forces
dipole (non-polar polar molecule and
are also weaker than ion-ion and
ion-dipole attractions. interaction
induced dipole
molecules such
between an ion and the H. as
(e.g. H°
H. O. ctc) TCi

interaction and the

induced
attracti
 MATTER
STATESOFMA
: ASES AND LIQUIDs 5.3
F
and the induced dipole is called dipole-induce of stronger
p a r 2olecule gas, (at no. 10, b.pt. 27 K) which suggests the presence
l einteraction.
Magnitude of induced dipole depends not only attractive forces in argon.
ion or strength of the dipole but also on the molecular weight of
a
on the (i) Molecular weight. As the
thecharge

atom or lecule, i.e., the ease with which the increases, its molecular
of the
lityibution in atom (or molecule) an be distorted. Large Substance (or atomic weight of inert gases) Hence, these forces
increases. Also its surface area increases.
S1Ze
decu
o
ecules can be
polarized more easily than the smaller
les. A cation or positive end of a polar molecule
become stronger.
(CGH14).
than hexane
oms
Boiling point ofoctane (CgH1g) is m o r e
o r m o l e c u l e s

m o b i le
electronof the non-polar molecule towards
cloud
(114), large size and
the
le c
Octane molecule has large molecular weight
Tacts nolecules become polar due to induction Due to large surface
large surface area than hexane (mol. wt. 86).
non-polar
hus, the
is that the polar and non-polar molecules are octane than in hexane.
2). The result
F i5 2 ) area, the London forces are stronger in
dipole and induced dipole interactions. of octane is more than that of
hexane.
gether by Hence, boiling point
molecules have such a shape
sfracted

iii) Molecular shape. Certain

between them. These
which provides maximum chances of attraction
normal pentane, CsH12
molecules have high boiling point, e.g.,
309.1 K [Fig. 5.4 (a)].
has zig-zag shape and has boiling point,
NONPOLAR PERMANENT INDUCED which provides minimum
POLAR
DIPOLE DIPOLE
Certain molecules have such a shape low
These molecules have
chances of attraction between them.
5.2 Induced dipole-dipole interaction boiling points, e.g., Neo-pentane, C5H12 has closely packed
Fig. 282.5 K only [Fig. 5.4 (b)].
structure with boiling point,
( Instantaneous or temporarily dipole-induced dipole
Forces or Dispersion Forces). These forces
nteraction (or London
atoms like inert gases, He, Ne, Ar, etc.
egist between non-polar
between non- polar molecules, i.e., homonuclear
hese also exist
molecules H2, N2 etc. These are known as van der Waals' forces
name of the discoverer.
after the
These forces are always attractive and interaction energy
of the distance
is inversely proportional to the sixth power
between two 1 / wherer is the distance
interacting particles (i.e., (a) n-PENTANE (b.p.=309.1K) (b) neo-PENTANE (b.p.=282.5K)
short LESS INTERACTION IS
between the particles. These forces are important only at CLOSE INTERACTION IS
POSSIBLE
POSSIBLE.
distances (-500 pm).
centre. 5.4 Interaction in normal and neo-pentanes.
Origin. A non-polar atom or molecule has apositive these Fig.
n electron cloud moves around it symmetrically. Both of kinetic energy of
are in equilibrium (Fig. 5.3). It is supposed that symmetrical (iv) Temperature. Atlow temperature, the
for fraction
atoms (inert gases) or molecules decreases. Thus, the magnitude
unovement of the electron cloud becomes unsymmetrical
molecule gets poSitive
of London's forces increases.
01 a second. As a result, one end of atom or high pressure, the atoms (inert gases) or
Pressure. At
le the other end gets negative charge.
This dipole induces an (v)
atoms (or molecules) get molecules come close. The interaction between them increases.
santaneous dipole temporarily. The electrostatic force of of London's forces increases.
mild
is each other due to Thus, the magnitude
dCed towards and induced dipoles. (inert gases) and
urdction between instantaneous dipole (vi) Number of electrons in atoms
molecules. Atoms or molecules having large size have large number
Ihes orces are for the condensation of gases.
responsible
e number of electrons result in a greater diffusion
of electrons. Large
of electron clouds and greater polarizaton. As a result, thereis stronger
inter-atomic or inter-molecular interactions. This causes higher boiling
electrons.
points of atoms or molecules with large number of
INSTANTANEOUS
Dipole-dipole, dipole-induced dipole and dispersion forces
SYMMETRICAL INSTANTANEOUS
DIPOLE are collectively known as van der Waals' forces.
DISTRIBUTION OF INDUCED DIPOLE
(FIRST ATOM)
ELECTRON CLOUD (SECOND ATOM) Characteristics of van der Waals' forces
interaction. (a)These forces are much weaker than ionic and covalent
Ig. 5.3 Temporarily induced
bonds. Their strength is minimum among gases, more in liquids
contain
t since all molecules and maximum in solid state. Forexample
electr dy be pointed out that the However,
forces also exist in polar molecules.
in Case
se
ndon London forces are the only ) Energy required to dissociate Cl-Cl covalent bond is
non-polar molecules,
242.6 kJ mol-l
nlermolecular forces that exist. (i) Energy required to sublime crystalline chlorine (having
a London's forces
ecting the strength of van der Waals' forces) = 25 kJ mol-1
with
Atoms and molecules The magnitude of van der Waals' forces is indicated by the
and molecular size.
large siomic electron clouds thus become
melting and boiling points of substances. Higher the melting and
Tfused aand arge surface area. Their forces become stronger,
As result, these boiling points, stronger are these forces between them.
dstorted. a

g.Argonga s a t . no. 18) has higher boiling point

(873 K) than Ne
 5.4
ISC CHEMISTRY PAD
(b) These forces
atoms or molecules.
are not affected by the presence of other kinetic energy of the particles of the matter and is thus
us
ART
esponsibe
.

for movement of particles. The ement of

Applications. Following are a few consequences of van der thermal motion. particles
Waals' forces
(1) Physical state.The
physical state of a substance depends 5.4. THREE STATES OF MATTER
upon the magnitude of van der Matter exists in three different states. i.e..
of
Waals forces. For example, in case solids.
gases. According to the kinetic molecular theory. all fomea
halogens, the number of electrons as well as the size of the
molecules increases from fluorine to iodine. As a result, the are composed of small, rapidly moving particles. Th
magnitude of van der Waals' forces goes on increasing on passing substance can exist in three different states. For examnla
Irom F2 to I2. Since van der Waals' forces are weaker in F2 and Clh. temperature, water is in liquid state. On heating, it chan
these are gases. On the other
forces are much
hand, iodine, in which van der Waals water vapour. When cooled, it solidifies to give ice. changes iM
greater is a solid and Br2 having attractive forces Heat Heat
in between those of Ice Water
Clh and I2 is a liquid. Water Vapour (Steam)
(Solid) Cool liquid) Cool
(ii) Melting and boiling points. The existence of van der gas)
Waals forces is
The boiling of a
responsible for bringing the molecules closer. Intermolecular Forces Versus Thermal Enero
liquid
of heat to overcome the
or melting of a solid involves the
absorption According to kinetic theory. the physical state in which
molecular attractions and to pull the
substance exists, is determined by the resultant
molecules apart. Therefore, with the increase of the
magnitude of of
effect of thermal energy and ordering effect of thethe disorderin
van der Waals'
forces, the boiling points and the melting points of of attraction as follows: cohesive for
the substances increase. For
example, in case of noble gases, the
van der Waals' forces increase with
increase in number of electrons. () lf the thermal energy is much greater than
Hence, the b.p. of noble gases should increase from He to Rn and
the forces
attraction, then we have matter in the gaseous state.
this has been found to be true (i) If the forces of attraction
experimentally. are greater than the them
Noble gas He energy, matter exists in the liquid state.
b.p. (°C)
Ne
Arr
269 -246 186 152 - 107 - 62
Xe Rn
iii) lf the forces of atraction between molecules are
(ii) Liquefaction of gases. Liquefaction of gases takes
mui
greater than the thermal energy, the matter exists in
due to increase in inter-molecular forces. When a place solid state. t
gas is cooled to
a low The
temperature or subjected to a high pressure, molecules come physical state of a substance is largely determined
closer leading to increase in der Waals' forces and the temperature considerations.
gets liquefied.
van
gas the average kinetic
Temperature of matter
depends up
energy of its molecules. Average kineticenerg
(iv) Deviation of real gases from ideal gas behaviour. Gases increases with increase in
temperature. Due to the kinetic energ
associated with molecules, these are in motion.
deviate from ideal behaviour under conditions of Collisions betwe
and low
high pressure molecules result in their motion
temperature due to the presence of van der Waals' forces. of disorder. Increase in being random and leading to a sta
() Varied hardness of solids. Hardness of solids temperature increases the kinctic energy"
upon the attractive forces between the constituent units.
depends the particles,
resulting in an increase in randomness or disorc
the attractive forces, harder is the solid. For Stronger This increase in
temperature, changes solid into a liquid and
a
hard solid because the constituent atoms in
example, diamond is a liquid into gas. Conversely, decrease in temperature
a
diamond are held kinetic energy and reduces the lower
together by strong covalent bonds. On the other hand. dry ice This results in the degree of disorder amongst u
(solid CO) is a soft solid because CO2 molecules in it are held change of gascous state into a liquid and
state into solid state.
together by weak van der Waals' forces.
The cohesive forces which
(vi) Joule-Thomson effect. Joule-Thomson operate between ions in
observed when a gas passes cooling is compound are strong electrostatic forces. Therefore,an
of
through a porous
plug from a region compounds are generally solids. The forces which
high pressure to a region
of low pressure. molecules in a covalent operate
Intermolecular forces discussed so far are all der Waals' forces. The
compound are weak
intermolecula
attractive. attractive forces operating in
However, molecules also exert repulsive forces on one another.
On or molecules cac
of non-metallic elements are also van der Waa
bringing the two molecules into close contact with each other, the Thus. such substances exist as s
repulsion between the electron clouds and that between the nuclei gases. liquids or low melnn
of two molecules comes into n solid, particles (molecules) are closely packed
a
play and the magnitude of repulsive cohesive forces between them are
interaction rises rapidly with decrease in distance very strong in contrast
separating the where the
molecules. This is he reason that particles are widely
separated and the cohesi
liquids and solids are hard to are very small. As a
result of strong cohesive forces, the
compress. The molecules in liquids and solids are
contact therefore they resist already in close in a solid move very little. These have
hardly any tran
would result in the increase of further compression
because that rotatory motion although some vibratory motion 1
P
repulsive interactions. them. Therefore, the molecules in a solid possess
5.3. THERMAL ENERGY kinetic energy.
The energy of Liquid stateis an intennediate state betw een wd
a

body
molecules is called thermal arising
a
from
motion of its atoms In this state. the molecules are not
or very closcly pakod
energy and is directly The intermolecular cohesive forces arc ucak and the
the
temperature of the substance. It is the measure proportional to
move freely
of average These are asuriated with translator
 s OF ATTER:GASES AND LIQUIDS 5.5
i
to vibratory motion.
adation to
Thus, liquid state is much
the molecules are associated with greater kinetic Characteristic Properties of Gases
are not held in
o n t e r t da n d

1.
Shape and volume. Since particles of gases
Ixed positions and move ncither have definite shapes
frecly. gases
state is the least ordered state. As already space available
to them
eous state
nor definite volumes. They fill the wholc
*nlomeca, t h e
molecules in gases are separated from each other and take up the shape and volume of the vessel in
which they are

e distances
The intermolecular forces are the weakest in enclosed.
all three types of motion, i.e., the of a gas or a gaseous
gases
have
2. Homogeneous nature. All the parts
The and vibratory and possess high kinetic energy. mixture have similar composition throughout.
wlatory.
rotatory
can be
gases
the ree States of Matter in 5.Compressibility. On increasing pressure,
iating the of large empty spaces.
Point and Boiling Point readily compressed due to presence
are in a
e r n
ofMelting
s

of a substance is largely determined by 4. Random motion. The molecules or

atoms of a gas
The physical s t a t e all directions.
onsiderations. A substance exists in the solid state state of continuous zig-zag motion in of the
motion, the molecules
5. Pressure. Due to their random
is above the room temperature at the the container and thus
exert certain force on

melting point It exists as a liquid if its gas collide on the walls of

pressure. boiling point is unit area is called the gas pressure.
oheric but its walls of the container. This force per
room
t e m p e r a t u r melting point is lower with each other freely due
than the it is a if its 6. Diffusion. Gases mix (diffuse)
hether rature.
tempera Likewise, gas boiling molecules.
movement of their
room

han
the to the free have
temperature.
below the room of molecules, gases
pintis 7. Density. Due to large separation
densities.
FOURTH AND FIFTH STATES
OF MATTER large volume and thus low shown by all gases,
The above mentioned properties are
fourth state of matter is Besides these properties,
mentioned in unit 1, nature or composition.
already independent of their chemical nature of
As
state. In this state, all matter is present which depend upon the
ealled the plasma
electrons and positively charged
ions with there are some properties because
change from gas gas,
to
S a mixture of It is found at very high temperatures the gas molecule. These properties
molecules of different gases.
unusual properties.of s u n or stars in presence of strong of the distinct nature of
oxygen
Such as interiors in c a s e of discharge tube. About 99% of gases like hydrogen,
For example: (i) Odour.Some the such as
of gases
electrical fields this
as
state. odourless while s o m e
universe is present in and nitrogen are characteristic smell.
all matter in the fifth state of matter refers to ammonia, sulfur dioxide and chlorine have a
Another state known
as and nitrogen
their separate like oxygen, hydrogen
in which atoms lose
(i) Colour. Some gases have distinct
supercooled solid state behave like a single super atom. However, gases like nitrogen
dioxide
condensed and are colourless.
dentity, get is based upon
B o se-Einstein

existence of this state colour (brown). in water.

The developed in
1924.
Gases possess different
solubilities

Condensation (BEC) concept (iii) Solubility. soluble while

chloride are extremely
ammonia and hydrogen
e.g., extent.
dissolve to small
GASEOUS STATEE and hydrogen
55. THE of the three physical
states
oxygen
of Solids, Liquids
and
state is the simplest When a gas isS Comparing the Properties
ne gaseous behaviour.
in
SnoWs greatest regularity
and Gases
conditions like pressure attractive forces
external in the magnitude of
cied to change in laws known
as
Due to the difference are associated
to certain simple the three states of
matter

ure it
behaves according
it will be
useful to study and the nature of packing, below:
the gas laws, as described
4WS. Before studying with different properties
e characteristic properties of gases. Gases
Liquids
do not occupy fixed
Solids
Molecules do
not occupy
fixed | Molecules
and are widely separated.
Property occupy
fixed positions
Molecules
and a r e less
positions
closely positions

Particlearrangement Molecules

close together
packed. Maleal freely and
and are packed but slower Molecules move very
m o v e freely
Molecules
Molecules move associated with all the three
little
little| all the three are
T h e s e have all
These have
have very
than
than gases.
gases. types of motion.
Movement Molecules

and are
associated
only
ted only types o f motion.
energy
higner energy. | Molecules possess very high
o s s e s s higher
m o v e m e n t

with vibratory motion. Molecules possesS

Molecules p
inimum
minimum| energy.
Since, particles of gases are not

3Energy
possess
Molecules

to
the absence of I1xed| held in fixed positions and m o v e
of| Due have no definite |
energy. . h e fixed positions positions, Iliquids have definite
freely, gases neithervolumes.
4. Shap translatory Ho ver, liquids have| definite
and Volume lack of shape. shapes nor
and their shapes
definite volumes because the inter-
particles
have definite
solids though weaker,|
motion,
molecular forces the to prevent |
powerful enough
and volumes.
are from one

separation of molecules
another.
 ISC CHEMISTRY
5.6
Gases PART
Property Solids
Liquids
densities but | Due to large secpa
5. Density high
Due to close packing of molecules.||Liquids alsohave molecules, gases ha
Solids have small volume and thus, generally lower than
volumes and thus low larg
high density. diffuse very densites
6 Diffusion Solids do not diffuse readily. diffuse slowly than gases Uases
the free readily
movement
due
Liquids solids. ot
but more rapidly than molecules. the
compresscd| es Can be compresses
large eeadil
7. Compressibility also be due to the presence ot
oniy
be compressed Liquids can

under extremely high pressures due| only under high pressure spaces between the
to the absence of empty spaces.
cules
The earth is surrounded by an approNimate 8ookm t
towards the surface
5.6. The
MEASURABLE PROPERTIES OF GASES
important measurable properties of gases are mass.
blanket
force.
air
of air. This Therefore,
is pulled
1t cxerts a pressure on
carth
carh
gravitational pressure. It is measured ui
volume. pressure and temperature. These are described below This is called
atmospheric
barometer. A long glass tube a
(i) Mass. The mass of a gas can be measured as follows: of an instument called out
at one end,
is filled with pure mercury andin
First of all the container filled with the gas is weighed and long). sealed (Fig. S.5). The meneury level
mercury
then it is weighed after removing the gas. in an open containerof run out : the ore
it will not completely esure
the tube. However.
Let the mass of the container + gas = W1 kg. surtace of the mercury in the con
the atmosphere
on the ontaine
Mass of the empty container = W kg supports the column.
that is in level with
Mass of the gas, m = (Wi - W ) kg. a surface inside the tube
Imagine
outside the tube (dashed line in Fig. 55 n
Generally. in chemistry. the mass of the gas is expressed in surface of mercury
is related to the number of the mercury surface outside the th
terms of number of moles, n. The mass air molecules on striking
in the tube. However, at the sametm
moles as: push the mercury upwards line is pulled downwards by
the dashed
Mass in grams the mercury above
Moles of gas =
same
force which is pulling the
gravitational atmosphe
Molar mass the liquid merw
downwards. When the downwards force of

or
where M is the molar mass
equals the upwards force of mercury being pushed by t|
M
atmosphere, there will be no net flow of mercury.
Units of m a s s . In SI units. the mass is expressed in kilogram
1
(8), which is 1000 of a kilogram VACUUM
(kg). However, the gram 00
measurements.
NO WEIGHT
convenient unit for most laboratory OF AIR HERE)
(0.001 kg). is a more

substance is the space occupied

(i) Volume. The
volume ofa the MERCURY
the entire space available to them,
by it. Since gases occupy as the volume of the container in which GLASS TUBE-
volume ofa gas is the
same
volume of
Therefore, the m e a s u r e m e n t of the h 76 cm 760mm
the gas is enclosed. the volume of the vessel
measurement of
a gas simply requires the AIR AIR
containing the gas. MOLECULES MOLECULES
of volume is cubic
Units of volume.
In SI units. the unit
breadth and
cube of lm length. I m
metre (m). It is
the volume of a volume is
is very large. Therefore,
However, this unit
l m height. cubic centimetre (cm3).
cubic decimetre (dnm')
o r
also measured in
The three units
are interrelated as
Im=10*dm=10 cm3
=
10 L
used for the m e a s u r e m e n t of
unit of volume Fig.5.5. Barometer.
The traditional litre (L). In SI terms. a litre is
is the
liquids in the metric system foul
cubic
decimetre. Mercury is generally used as a liquid in a barometer due to
defined as one
reasons :
1L=1dm3 for most laboratory (i)Mercury being almost non-volatile at ordinary tempera
the litre is
even large
too
ver
However,
generally
used in ordinary
laboratory
Sure exertedby the vapours above the mercury column
and the unit can be neglected.
purposes o r ml).
praprn

is m i l l i l i t r e (mL (i) The beight of the column in a barometer is y

m e a s u r e m e n t s

ine w
thedensity of the liquid. ie.. denser the liquid.ssborter et
io
1L=1000mL the force per unit Hence
id.
hor

Pressure is defined a s meTcury being very dense is best for the bar
Pressure. Supports a column of convenient beight Howeve.
the force that the gas
exerts on
(iii)
of a gas is
Thus. the pressure the surface area of the difters very littde from atmospheric pressure. the dite
area. divided by
levels
the container is
correspondingly smal1 In such
the walls of ment suffers cascs, the F
container.
A T E S
O FM A T T A MATTER:GASESAND LIQUIDS 5.7
from the surface vessel. The device
ht of the mercury
column, measured Measurement of pressure of a gas in a a
container, is directly proportional to the used to measure pressure of a gas trapped
in a vessel is called
in the in fig. 5.6. The
On days when the
atmospheric pressure is manometer are shown
p r e s s u r e .
nanometer. Two types of consists of a U-shaped
eric the tube and the height of column and
nnury
is forced into
I sf o r c e irst is called an open end manometer
arm of
pressure drops, some mercury flows tube partly filled with a liquid, usually mercury. The right
he atmospheric Hence, atmospheric
When
theh
and height of the column drops. It is important the manometer is open to the atmosphere.
arm is
tube
in this arm. The left
e
is not very volatil at room temperature pressure is exerted on the mercury
he mercury sample exert
to
vapour in the space above the
of the mercury connected to a container of gas, allowing the gas
nount
in the tube is small. Hence the pressure exerted by pressure on the mercury. In Fig. 5.6(a),
it is clear that the entrapped
ndmercuryin
and that is why
can be easily neglected. gas exerts a larger pressure than the atmosphere
nuy vapours arm open to the air.
The difference
e pressureexpresse
in terms of height of mercury column the mercury is forced up in thein the two arms of this
manometer 1s
anverted into the units of force per unit area. Let a mercury in the height of the mercury
between the two sides.
in cross-section exerts a downward
'A' cm2 proportional to the difference in pressure
e m high The pressure of the
of column. The force per unit In fig. 5.6(a), this difference is 100 mm Hg.
| to the weight mercury than the atmospheric
trapped gas, therefore, is 100 torr larger torr with the help of a
ittqual

surtace is P, so that
be 750
g on
pressure which is separately found to
Force Mass XAcceleration barometer.
P=* Area 850 torr
Area torr=750 torr+ 100 torr=
Force= Mass x Acceleration] PgasPatm + 100
shown in is called closed-end
fig. 5.6(b)
The manometer
same way as a barometer.
AA
manometer. It is constructed in the
and its lower end is bent
A tube is completely filled with mercury
to a bulb where a gas
is the mass of mercury in the tube and g is the acceleration around into a U-shape and then connected
shete m the sealed end above the
is the density of the mercury, then mass is given by could be trapped. The space inside
ix lo gravity. Iip in barometer. In a closed end
mercury level is a vacuum, just
as a
:pV where V is the volume of the mercury in the tube. Since
manometer, the difference in the height mercury columns in the
of
okume is given by 150
two arms directly gives the gas pressure. Thus, in fig. 5.6(6),
P.A.h.g torr is the gas pressure.
V=Ah;P ="A= PA8 _
P atm=750 torr
The pressure of atmosphere changes from day to day at a
standard
ghen altitude and also changes with altitude itself. A
a column
pressure (atm) is defined as the pressure that will support
d mercury to a height of 76.00 cm at 0°C and sea level. It is VACUUM-
since the density
eSsary to specify the temperature and altitude,
d mercury varies with temperature and the i rce of gravity varies
in
ihaltitude; both these factors affect the height of mercury GAS GAS
150 mm
the column.
is an awkward- 100mm
For ordinary laboratory work, the atmosphere
milli-metre of mercury or
Unt. A more convenient unit is the column of mercury MERCURY
ng for short. This is the pressure exerted by a MERCURY
called 1 torr (after Torricelli-the
nm high at 0°C. This is also
(a) (b)
aventor of barometer). Thus,
(mm Fig. 5.6. Measurement of gas pressure.
am=76.0 cm of mercury (cm Hg)=760 mm ofmercury
Hg)= 760 torr*
(iv) Temperature. Temperature is a measure of the hotness
defined
as unit of pressure is pascal, which is or coldness of an object. Indeed, temperature determines the
pressure exerted with a force of 1 newton
(1e
AN) on 1 m2 area. direction heat flow ; heat always flows spontaneously from a
of
body at higher temperature to a body at lower temperature.
Pascal (Pa) = INm-2=1 kgmls The measurement of temperature is based on the fact that
pascal when h, d and 8 are
many substances expand on increasing the temperature. To actually
pressure is obtained in
cpressed in SI unit. measure the temperature, we use a thermometer-a long glass tube
is with a very thin bore connected to a reservoir containing a liquid,
BCheral84ses, pascal being a very small unit, the pressure
we have usually mercury. As the temperature rises, the liquid in the reservoir
yexpressed in terms of bar and expands and its length in the column increases.
bar 100 kPa= 10° Pa
of Temperature is a measure of kinetic energy. The SI unit for
he older unit ofpressure, i.e., atm is related to the SI unit
pressureas follows temperature is the Kelvin degree (K). It may be noted that the

098m1.01325 bar =1.01325 x 10[ Pa=101.325kPa or 1 bar degree sign is not used with Kelvin. On the Kelvin scale, the point
I atm. at which all molecules possess zero kinetic energy is called absolute
The International Com Measures has suggested
zero(OK). On Kelvin scale, freezing point of water is 273.15 Kand
Committee on Weights and
use nal
nethe use
at
of 'tor should be
boiling point of water is 373.15 K. Another commonly used scale is
droppea.
 5.8 ISC CHEMISTRY
the celsius scale (°C), on which f.p. of water is 0°C and
TO0C. Since both b.p. of water PV2 = constant
PART
1s scales contain 100 degree between the t.p. and From (1) and (2). PV =P2V2 (T constanty
b.p.. they can be inter-converted as
follows
K=0°C+273.15 (=273)
At a constant temperature. product of pressure

of a gas is constant.
eSSure and volu,
of a given mass
C=K-273.15 Thus, keeping the temperature
fixed, if pressu.
Composition of Gases volume is doubled. Similarly. if pressure is doubledh
value.
ed. volhalumevet
The composition of a reduced to one half of its original
gas is described in terms of the relative Illustration of the law. The Boyle's law can be il..
amounts of each
gas present in a mixture. In a mixture of non-
of volume for a given maseae
reacting gases, the amounts of constituent gases can be expressed determining the values of a
in terms of
number of moles. n; of each gas and the mole fraction, different pressures, temperature remaining constant. T"Ba
Xi of each
gas. In a mixture of gases, A. B and C having moles at 298 K is given in the Table 5.1.
of gas Th a
nA aofgivenmass
PV at different pressures proves the validity of Bovle
ng and nc respectively. s law
Table 5.1 Effect of Pressure on the Volume of a
Mole fraction of A. XA= ;nA + nA (Air) at ConstantTemperature ia Gas
nB +nC

B Pressure, P (bar) Volume, V(litre) PV (litre ba

XB
nA+nB +nc 0.20265 112.0
22.7
0.25331 89.2 22.6
Xc 56.25
nA+nB +nc 0.4053 22.80
Thus, XA +Xp+ Xc=1 37.40
0.60795 22.70
0.811 28.1 22.78
5.7. THE GAS LAWS
It has already been stated that the gaseous state is the 1.01325 22.4 22.70
simplest of all the states of matter and shows greatest regularity in Graphical representation of the law. The Boyle's law cah
behaviour and follows certain generalisations called gas laws. represcnted graphically in three different ways as describedbel
The important gas laws are discussed below: (1) On plotting a graph between pressure, P (along Xa
1.Pressure-Volume Law or Boyle's Law. (Robert Boyle, I1662). and volume, V (along Y-axis), a hyperbolic curve is obtainedF
5.7(a)]. Similar curves are obtained at different fixed temperature
It states thatgiven
"at a mass
constant temperature, the
volume of a of a gas is inversely The pressure volume curves obtained at constant temperatur
are known as isotherms. This graph illustrates that
proportional to the applied pressure" volume
inversely proportional to pressure.
That is:V P
(T constant) or PV =K (constant) (i) On plotting a graph between pressure (P) and lNoluz
For a gas having pressure Pi and volume V (1V), a straight line is obtained [Fig. 5.7(b)]. This also showsti
pressure and volume are inversely proportional to each othet
PiVi = constant ..1) (ii)If a graph is plotted between pressure, P (alog Xa
If the pressure changes from Pi to P2 and volume changes and PV
from V to V2, then
(along Y-axis), a horizontal line is obtained [Fig. 5.7c) |

T3 T2 T1
200
-T
1.0

150 0.8 -2
-0 --
100t 0.61
PV
0.4

0.2

PRESSURE ATMOSPHERES-
10 20 30 40 50
P(Atm) - PATM)
(a) (b)
(c)
Fig. 5.7. (a) Plot of V against P. (b) Plot of 1/V against P.
(c) Plot of PV versus P.
This indicates that PV remains constant even if we change
pressure. However. the value of PV increases with increase in Practical implications of
Boyle's law that gases are Boyle's ILaw. follo t
temperature.
gasis compressible. When a g
compressed, the same number of OCcupya
molecules