Root Mean Square (R.M.

S) velocity

The R.MLS. velocity is the square root of the mean of the square of the individual velocities of the
molecules, i.e.
C=v(C2)
The R.M.S. velocity is quite different from the mean velocity of the gas molecules. If we consider n
molecules of the gas with respective velocities Ci, Co, Cs,..... Cy, the root mean square velocity

CZECZ+CE+ ACR
C=
n

And the mean velocity Cm is given by the relation

Cy = ab eat est Cn
n

In kinetic theory the mean velocity is of no practical importance and it is the R.M.S. velocity that counts
much.

Problem 1: Find the R.M.S. velocity of the molecules of oxygen at 0°C and atmospheric pressure. The
density of oxygen at N.T.P = 1.43 gm/litre.

Solution: Here, P = 76x13.6x981 dynes/cm?

p = 0.00143 gm/cc

e)
cVeveee0.00143
= 4.61x10* cm/sec

Problem 2: At what temperature, pressure remaining unchanged, will the r.m.s. velocity of hydrogen be
double of its value at N.T.P.?

Solution: The r.m.s. velocity is given by

— {BRP
c= M
CxvT
Let the r.m.s. velocity at Tp be C and at T be 2C, then

Or —=
Or, T =4To= 4x273 = 1092 K= 819°C.
Kinetic interpretation of Temperature

The pressure exerted by a gas is

P=—1y¢2pC 2=37 £ 72
“PV = SMC?
Let us consider 1 gm molecule of the gas at a temperature T K
PV =RT
= MC? =RT
+MC? ==RT............
2
(1)

This equation gives a physical meaning to the gas constant R and shows that it is equal to two-thirds of the
total translational energy of the molecules in one gm molecule of the gas.
Let the mass of each molecule be m and Avogadro’s number be N.
Then, M=mN
.+mNC2
2
=2RT
2

or,>mC?
2
===T==2kT
2N 2
.. .. ... (2)

Here k is the Boltzmann’s constant.

Thus from equation (2), the mean kinetic energy of a molecule is directly proportional to the absolute
temperature of a gas. When the temp. of the gas is increased, the mean kinetic energy of the molecules
increases. When heat is withdrawn from a gas, the mean kinetic energy of the molecules decreases. So, on
the standpoint of kinetic theory of gases, at absolute zero temperature, the molecules are in a perfect state
or rest and have no kinetic energy. But Kelvin’s thermodynamic interpretation of the absolute zero does not
require that the molecular motion should cease at that temperature.

Problem 3: Calculate the average kinetic energy of molecule of a gas at a temperature of 300 K.

Solution: Average K.E of a molecule = <mC 2 = = kT

Here k is Boltzmann constant, k = 1.38x10-16 erg/molecule-K

Average K.E. ofa molecule = 7 x 1.38 x 10716 x 300

= 6.21x10™ erg

Note: The average kinetic energy of a molecule of any gas ie., hydrogen, oxygen, helium, nitrogen, air
etc., is the same at the same temperature.
Equation of state for Perfect gas

The equation of state for Perfect gas is PV = RT

Derivation of gas equation
From kinetic theory, P = ; pc?
p=-"4¢2
3V
PV => MC?
Consider one gram molecule of a gas at an absolute temperature T.
The mean energy of the molecules = ; Mc?
==2 Nmc?
PV= = NmC?
3
2 1
= 3 N= 2 mc?
Mean kinetic energy of a molecule = ; mC?
== kT
Hence PV = : N= kT

PV = NkT

But Nxk=R

- PV=RT

where P is in dynes/sq. cm., R = 8.31x10’ erg/g mole.K, Tis in K, Vis the volume in cc per gram molecule.

Derivation of gas laws

(i) Boyle’s law

According to the kinetic theory,
1 1M
P= =pC? = =—C?
3 3V
PV=5MCFO in, (1)
At a constant temperature T, C’ is constant. Therefore at a constant temperature
1
sMc 2 = constant

Hence PV = constant — at constant temperature

“PX < , when the temperature is constant. This is Boyle’s law.

(ii) Charles’ law

According to the kinetic theory,

P=—-1yr22-1!@¢2
gpl =37£

PV = =MC?
Consider one gram molecule of a gas at absolute temperature T.
 M=mN

PV = SNMO? eee eeeen (1)

The mean kinetic energy of a molecule

<mC?
2
= =kT
2
mC? = 3kT
Substituting this value in equation (1)
PV=NkT, where N is the Avogadro’s number and k is the Boltzmann’s constant. If P 1s constant,
Va T. This is Charles’ law.

(iii) Avogadro’s law

Consider two gases A and B at a pressure P and each having a volume V.

Mass of each molecule of the first and second gases = m1, m2

No. of molecules of the first and second gases = m1, nz

Mean square velocities of the molecules of the first and second gases = C? , C2

For the first gas, P = = pC?

1 MN, c2
=3- (1)
Similarly for the second gas,
1
P= Pa Cy
_ Lmgn,CZ
=3 (2)
From equations (1) and (2), we get
LmyniG? _ 1 myn2C3
3 Vo 38 9
mn CP = mzn2CZ (3)
If the two gases are at the same temperature T, the mean kinetic energy of the molecules of both the
gases is the same
1 21 2
sm = 5 Male

mCi = mC; (4)

From (3) and (4), m1 = n2

i.e., equal volumes of two gases at the same temperature and pressure contain the same number of
molecules. This is Avogadro’s hypothesis.