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Learning Outcome:

14.1 Ideal gas equation (1 hour)


At the end of this chapter, students should be able to:
Sketch and interpret the following graph of an ideal gas P-V graph at constant temperature V-T graph at constant pressure P-T graph at constant volume of an ideal gas. Use the ideal gas equation:

CHAPTER 14: Kinetic Theory of Gases (3 Hours)


1 2

PV = nRT

14.1 Ideal Gas Equation


14.1.1 Boyles law
a. P

Graphs of the Boyles law.


b. PV
T2 > T1

states : The pressure of a fixed mass of gas at constant temperature is inversely proportional to its volume.
P 1 V
if

T2 T1 T2 T1 V T2 T1

T = constant
OR

PV = constant
where

P 1V1 = P 2V2

0 c. P

d. PV

P 1 : initial pressure P2 : final pressure V1 : initial volume V2 : final volume


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T2 T1
1 V

14.1.2

Charless law

states : The volume of a fixed mass of gas at constant pressure is directly proportional to its absolute temperature.

V T

If

P = constant
V1 V2 = T1 T2

V = constant T
where

T1 : initial absolute temperature T2 : final absolute temperature V1 : initial volume V2 : final volume

Graphs of the Charless law.


a.

b. V

273.15

T(C)

T(K)

14.1.3

Gay-lussacs (pressure) law

Graphs of the Gay-lussacs (pressure) law.


a.

states : The pressure of a fixed mass of gas at constant volume is directly proportional to its absolute temperature. P T If V = constant
P = constant T
where

b. P

P P 1 = 2 T1 T2

T1 : initial absolute temperature T2 : final absolute temperature P 1 : initial pressure P2 : final pressure
273.15 0 T(C) 0 T(K)

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14.1.4 Equation of state for an ideal gas


An ideal gas is defined as a perfect gas which obeys the three gas laws (Boyles, Charless and Gay-Lussacs) exactly. Consider an ideal gas in a container changes its pressure P, volume V and temperature T as shown in Figure 15.1.

P 1 V1 T1
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1st stage

P2 V' T1

2nd stage

P2 V2 T2

Figure 14.1

In 1st stage, temperature is kept at T1 , Using Boyles law : PV P2V ' = P V '= 1 1 1V1 P2 In 2nd stage, pressure is kept constant at P2 , Using Charless law : V ' V2 VT = V '= 2 1 T1 T2 T2 Equating eqs. (1) and (2), thus
P1V1 P2V2 = T1 T2
Initial
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Consider 1 mole of gas at standard temperature and pressure (S.T.P.), T = 273.15 K, P = 101.3 kPa and Vm = 0.0224 m3 From equation (3),
(1)

R=

R = 8.31 J K 1 mol1
(2)

PVm 101.3 103 (0.0224) = T 273.15

where R is called molar gas constant and its value is the same for all gases. Thus PV
m

OR

PV = constant T

T
(3)

=R

where

Vm : volume of 1 mole gas

PVm = RT
For n mole of an ideal gas, the equation of state is written as

Final

PV = nRT
where n : the number of mole gas

n=

m M

where

m : mass of a gas M : molar mass of a gas

Example 14.1 :
The volume of vessel A is three times of the volume vessel B. The vessels are filled with an ideal gas and are at a steady state. The temperature of vessel A and vessel B are at 300 K and 500 K respectively as shown in Figure 15.2.

OR

n=

N where N : number of molecules N A N : Avogadro's constant A = 6.02 10 23 mol 1

A
(300 K) Figure 14.2

B
(500 K)

If the Boltzmann constant, k is defined as

R = 1.38 10 23 J K 1 NA then the equation of state becomes k=


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If the mass of the gas in the vessel A is m, obtain the mass of the gas in the vessel B in terms of m.

PV = NkT
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Solution :

VA = 3VB ; mA = m; T0A = 300 K; T0B = 500 K

Solution :

VA = 3VB ; mA = m; T0A = 300 K; T0B = 500 K

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Example 14.2 :
connecting tap

Solution :

Figure 14.3

V0A = V1A = 3.00 m 3 ; T0A = T1A = 250 K; P0A = 5.00 104 Pa;V0B = V1B = 7.20 m 3 ; T0B = T1B = 400 K; P0B = 2.00 104 Pa

Refer to Figure 15.3. Initially A contains 3.00 m3 of an ideal gas at a temperature of 250 K and a pressure of 5.00 104 Pa, while B contains 7.20 m3 of the same gas at 400 K and 2.00 104 Pa. Calculate the pressure after the connecting tap has been opened and the system reached equilibrium, assuming that A is kept at 250 K and B is kept at 400 K.

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Learning Outcome:
Exercise 14.1 : Given R = 8.31 J mol1 K1 and NA = 6.0 1023 mol1
1. Estimate the number of molecules in a flask of volume 5.0 104 m3 which contains oxygen gas at a pressure of 2.0 105 Pa and temperature of 300 K. ANS. : 2.41 1022 molecules 2. A cylinder contains a hydrogen gas of volume 2.40 103 m3 at 17 C and 2.32 106 Pa. Calculate a. the number of molecules of hydrogen in the cylinder, b. the mass of the hydrogen, c. the density of hydrogen under these conditions. (Given the molar mass of hydrogen = 2 g mol1) ANS. : 1.39 1024 molecules molecules; ; 4.62 g; 1.93 kg m3

14.2 Kinetic theory of gases (1 hour)


At the end of this chapter, students should be able to: State the assumptions of kinetic theory of gases. Apply the equations of ideal gas,
PV = 1 Nm < v 2 > 3
1 < v2 > 3

and pressure ,
P =

in related problems. Explain root mean square (rms) speed of gas molecules and use the equation,

vrms = < v2 > = 3


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kT m

14.2 Kinetic theory of gases


The macroscopic behaviour of an ideal gas can be describe by using the equation of state but the microscopic behaviour only can be describe by kinetic theory of gases. 14.2.1 Assumption of kinetic theory of gases All gases are made up of identical atoms or molecules. All atoms or molecules move randomly and haphazardly. The volume of the atoms or molecules is negligible when compared with the volume occupied by the gas. The intermolecular forces are negligible except during collisions. Inter-atomic or molecular collisions are elastic. The duration of a collision is negligible compared with the time spent travelling between collisions. Atoms and molecules move with constant speed between collisions. Gravity has no effect on molecular motion.
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14.2.2

Force exerted by an ideal gas

Consider an ideal gas of N molecules are contained in a cubical container of side d as shown in Figure 15.4.

Wall B

Figure 14.4

Wall A

Let each molecule of the gas have the mass m and velocity v. The velocity, v of each molecule can be resolved into their components i.e. vx, vy and vz.
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Consider, initially a single molecule moving with a velocity vx towards wall A and after colliding elastically , it moves in the opposite direction with a velocity vx as shown in Figure 15.5.
Wall Wall

The molecule has to travel a distance 2d (from A to B and back to A) before its next collision with wall A. The time taken for this movement is 2d
t = vx

B
Figure 14.5 Wall Wall

If Fx1 is the magnitude of the average force exerted by a molecule on the wall in the time t, thus by applying Newtons second law of motion gives P 2mvx m 2 Fx1 = x = Fx1 = v x t 2d d
m 2 m 2 m 2 Fx = v x1 + v x 2 + ....... + v xN d d d For N molecules of the ideal gas,
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B Therefore the change in the linear momentum of the molecule is given by P = mv (mv )
x x x
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v x

Px = 2mvx

Fx =

m 2 2 2 vx1 + v x 2 + ....... + v xN d

where vx1 is the x component of velocity of molecule 1, vx2 is the x component of velocity of molecule 2 and so on. The mean (average ) value of the square of the velocity in the x direction for N molecules is

v + vx 2 + ....... + vxN < v x >= x1 N 2 2 2 2 v x1 + vx 2 + ....... + v xN = N < v x >


2

Thus, the x component for the total force exerted on the wall of the cubical container is
Fx = m 2 N < vx > d
2 2 2

The magnitude of the velocity v is given by

then
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v 2 = vx + v y + vz 2 2 2 < v 2 >=< v x > + < v y > + < v z >


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Since the velocities of the molecules in the ideal gas are completely random, there is no preference to one direction or another. Hence 2 2 2 < vx >=< v y >=< vz > 2 < v 2 >= 3 < v x > < v2 > 2 < v x >= 3 The total force exerted on the wall in all direction, F is given by m 2 m < v2 > F = N < vx > F = N d d 3 2 N m<v > F= 3 d
where

< v 2 >: mean square velocity of the molecule

14.2.3 Pressure of an ideal gas


From the definition of pressure,
P= F A
where

Since the density of the gas, is given by


2

A = d2

and

F=

N m<v > 3 d

Nm V hence the equation (14.1) can be written as

1 Nm < v 2 > 3 and d = V P= 3 3 d 1 Nm < v2 > P= 3 V

1 P = < v2 > 3
(14.1) where

(14.3)

PV =
where
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1 Nm < v 2 > 3

P : pressure by the gas : density of the gas

(14.2)

< v 2 >: mean square velocity of the gas molecules

Nm : mass of an ideal gas in the container


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14.2.4 Root mean square velocity ( vrms)


is defined as

where vrms

vrms = < v 2 >

: root mean square velocity (speed) m : mass of a molecule gas

From the equation of state in terms of Boltzmann constant, k : PV = NkT (14.4)


1 Nm < v 2 > 3 3 kT < v 2 >= m NkT =

M : molar mass of a gas T : absolute temperature


3P 1 P = < v 2 > thus < v 2 >= 3

Since

vrms =

3P

By equating the eqs. (14.4) and (14.2), thus

vrms
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3kT = m

OR

vrms

3RT = M

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therefore the equation of root mean square velocity of the gas molecules also can be written as

Example 14.3 :
Eight gas molecules chosen at random are found to have speeds of 1,1,2,2,2,3,4 and 5 m s1. Determine a. the mean speed of the molecules, b. the mean square speed of the molecules, c. the root mean square speed of the molecules. Solution : N = 8 a. The mean speed of the molecules is given by

Solution :

N =8

b. The mean square speed of the molecules is given by

c. The root mean square speed of the molecules is

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Example 14.4 :
A cylinder of volume 0.08 m3 contains oxygen gas at a temperature of 280 K and pressure of 90 kPa. Determine a. the mass of oxygen in the cylinder, b. the number of oxygen molecules in the cylinder, c. the root mean square speed of the oxygen molecules in the cylinder. (Given R = 8.31 J mol1 K1, k = 1.38 1023 J K1, molar mass of oxygen, M = 32 g mol1, NA = 6.02 1023 mol1) V = 0.08 m3 ; T = 280 K; P = 90 103 Pa Solution : a. By using the equation of state, thus

Solution : a.

V = 0.08 m 3 ; T = 280 K; P = 90 103 Pa

b. The number of oxygen molecules in the cylinder is

c. The root mean square speed of the oxygen molecules is

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Exercise 14.2 : Given R = 8.31 J mol1 K1, Boltzmann constant, k = 1.381023 K1


1. In a period of 1.00 s, 5.00 1023 nitrogen molecules strike a wall with an area of 8.00 cm2. If the molecules move with a speed of 300 m s1 and strike the wall head-on in the elastic collisions, determine the pressure exerted on the wall. (The mass of one N2 molecule is 4.68 1026 kg) ANS. : 17.6 kPa 2. Initially, the r.m.s. speed of an atom of a monatomic ideal gas is 250 m s1. The pressure and volume of the gas are each doubled while the number of moles of the gas is kept constant. Calculate the final translational r.m.s. speed of the atoms. ANS. : 500 m s1 3. Given that the r.m.s. of a helium atom at a certain temperature is 1350 m s1, determine the r.m.s. speed of an oxygen (O2) molecule at this temperature. (The molar mass of O2 is 32.0 g mol1 and the molar mass of He is 4.00 g mol1) ANS. : 477 m s1
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Learning Outcome:
14.3 Molecular kinetic energy and internal energy
At the end of this chapter, students should be able to: Explain and use translational kinetic energy of gases,
K tr = 3 R 3 T = 2 kT N 2 A

State the principle of equipartition of energy. Define degree of freedom. State the number of degree of freedom for monoatomic, diatomic and polyatomic gas molecules. Explain internal energy of gas Relate the internal energy to the number of degree of freedom, and use the equation
U =
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1 fNkT 2

14.3.1 Molecular kinetic energy


From equation (14.1), thus 1 Nm < v2 P= 3 V
>
(14.5)

P=

2 N 1 2 m < v > 3 V 2
N increases V

2 1 N m < v2 > 3 2 1 1 3 m < v 2 >= kT and m < v 2 >= K tr 2 2 2 NkT =

This equation shows that


P increases () When

K tr =
where

3 3 R kT = 2 2 NA

1 2 m < v > increases 2

Rearrange equation (14.5), thus


PV =
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2 1 N m < v2 > 3 2

and

PV = NkT

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K tr : average translati onal kinetic energy of a molecule T : absolute temperature k : Boltzmann constant R : molar gas constant N A : Avogadro constant

For N molecules of an ideal gas in the cubical container, the total average (mean) translational kinetic energy, E is given by

Principle of equipartition of energy

E = NK tr 3 E = N kT 2 3 E = NkT 2
OR

States : the mean (average) kinetic energy of 1 every degrees of freedom of a molecule is kT .
2

Therefore

< K >=
OR

f kT 2 f RT 2

Mean (average) kinetic energy per molecule

E=
41

3 nRT 2
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< K >=
where

Mean (average) kinetic energy per mole

f : degrees of freedom
T : absolute temperatu re

Degree of freedom ( f )

is defined as a number of independent ways in which an atom or molecule can absorb or release or store the energy. Monoatomic gas (e.g. He, Ne, Ar) The number of degrees of freedom is 3 i.e. three direction of translational motion where contribute translational kinetic energy as shown y in Figure 15.6.

Diatomic gas (e.g. H2, O2, N2) The number of degrees of freedom is
y

Translational kinetic energy Rotational kinetic energy H

H Figure 14.7

vy
vz

3 2 5

vx

vy
He

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vz

vx
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Polyatomic gas (e.g. H2O, CO2, NH3) The number of degrees of freedom is Translational kinetic energy 3 Rotational kinetic energy 3

y
Figure 14.8

vy
O

Figure 15.6

vz

vx

Table 14.1 shows the degrees of freedom for various molecules.


Degree of Freedom (f) Molecule Monoatomic Kinetic Energy Per Molecule <K>

Degrees of freedom depend on the absolute temperature of the gases. For example : Diatomic gas (H2)
H H vibration Figure 15.9

Example Translational Rotational Total Translational Rotational Average He 3 0 3


3 kT 2 3 kT 2 3 kT 2

0
2 kT 2 3 kT 2

3 kT 2 5 kT 2 6 kT 2

Diatomic

H2 H2O

Polyatomic

(At temperature of 300 K)

Table 14.1

Hydrogen gas have the vibrational kinetic energy (as shown in Figure 15.9) where contribute 2 degrees of freedom which correspond to the kinetic energy and the potential energy associated with vibrations along the bond between the atoms. when the temperature, f =3 At 250 K f =5 At 250 750 K f =7 At >750 K
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Example 14.5 :
A vessel contains hydrogen gas of 2.20 1018 molecules per unit volume and the mean square speed of the molecules is 4.50 km s1 at a temperature of 50 C. Determine a. the average translational kinetic energy of a molecule for hydrogen gas, b. the pressure of hydrogen gas. (Given the molar mass of hydrogen gas = 2 g mol1, NA= 6.02 1023 mol1 and k = 1.38 1023 J K1) N Solution : = 2.20 1018 ; < v 2 >= 4.50 103 m s 1 ; T = 323.15 K a. The average translational kinetic energy of a molecule is

Solution :

b. The pressure of hydrogen gas is given by

N = 2.20 1018 ; < v 2 >= 4.50 103 m s 1 ; T = 323.15 K V

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14.3.2 Internal energy, U


is defined as the sum of total kinetic energy and total potential energy of the gas molecules. But in ideal gas, the intermolecular forces are assumed to be negligible thus the potential energy of the molecules can be neglected. Thus for N molecules,
U =N<K>
Example 14.7 :
Neon is a monoatomic gas. Determine the internal energy of 1 kg of neon gas at temperature of 293 K. Molar mass of neon is 20 g. Solution :

U=

f NkT 2

and

k=

R NA

OR

U=

f nRT 2

For N molecules of monoatomic gas ,

3 U = NkT 2
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OR

U=

3 nRT 2
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where

U : internal energy of the gas

THE END
Next Chapter
CHAPTER 15 : Thermodynamics

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