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Lecture 03

Contents 1. The Kinetic Molecular Theory of Gases 2. The Meaning of Temperature 3. Root Mean Square Velocity 4. The Mean Free Path 5. Diffusion and Effusion 6. Real Gases and Van der Waals equation
1 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

The Kinetic Molecular Theory of Gases Four postulates could describe the behavior of molecules in a gas: 1. Gases consist of large numbers of particles, the volume of the particle can be neglected. 2. The particles are in constant motion. The pressure of the gas is due to the collision of the particles with the wall of the container. 3. No force of interaction exists between particles.
4. The average kinetic energy of a molecule is directly proportional to the Kelvin temperature.

KEavg T
2 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

The Kinetic Molecular Theory of Gases For a large number of molecules moving in random directions:
z
l

1 n NA m u2 PV = 3
where n = number of moles, y NA = Avogadros number m = the mass of molecules u = the velocity of molecules u = the average velocity of molecules 2 u = the average square velocity
3 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

The Kinetic Molecular Theory of Gases

1 2 1 2 nNA m u = n NA ( m u2 ) PV = 3 3 2 2 KE 2 KE n NA n = = avg 3 3 PV PV 2 KE = avg T n n 3 PV RT = n

Since the average kinetic energy of a molecule is directly proportional to the Kelvin temperature,
4 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

The Meaning of Temperature


The exact relationship between temperature and average kinetic energy is:

PV RT = n KEavg

PV 2 KE = avg n 3 3 RT = 2

The Kelvin temperature is an index of the random motions of the particles of the gas.
5 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Root Mean Square Velocity


The square root of the average speed is called the root mean square velocity.

Urms =
From the equations:

u2 KEavg = 3 R T 2

KEavg = NA ( 1 m u2 ) 2 u2
6

3R T = NA m
Lecture 3

Prof. Dr. Mamdouh A. Abdel Rahim

Root Mean Square Velocity

u2

3R T = NA m

u2

= Urms =

3R T NA m

m represents the mass in kilograms of a single gas particle.

Urms =

3R T M

meter s-1

M is the molecular weight of the gas. In this case R = 8.314 J K-1 mol-1
7 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Example: Calculate the root mean square velocity for the atoms in a sample of helium gas at 25C. Solution: M for helium = 4 g mol-1 = 4 10-3 Kg mol-1 T = 25 + 273 = 298 K R = 8.314 J K-1 mol-1
2s-2K-1 mol-1 3 298 K 8.314 Kg m Urms = M 4 10-3 Kg mol-1 Urms = 1.8610 6 m2s-2 = 1.3610 3 m s-1
8 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Root Mean Square Velocity At the same temperature, compare Urms H2 with Urms O2

Urms H2 = Urms O2

3R T MH2 3R T MO2

MO2 = MH2

32 = 4 2

Hydrogen molecules move 4 times faster than oxygen molecules.


9 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

The Mean Free Path It is the average distance a particle travels between collisions in a particular gas sample.
Relative number of molecules with given velocity

O2 gas

0
10

400

800
Lecture 3

Molecular velocity (m/s)


Prof. Dr. Mamdouh A. Abdel Rahim

The Mean Free Path


Relative number of molecules with given velocity

273 K

O2 gas N2 gas

1273 K 2273 K
1000 2000
Lecture 3

0
11

Molecular velocity (m/s)


Prof. Dr. Mamdouh A. Abdel Rahim

Diffusion and Effusion


Diffusion: Is the spread of one gas throughout a space or throughout a second gas. The movement of gas particles during mixing with another gas occurs from a higher to a lower concentration area. When gas molecules escape from their container through tiny holes in the container, the process is said to be Effusion
12 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Diffusion and Effusion


Thomas Graham found that, at a constant temperature and pressure the rates of effusion of various gases are inversely proportional to the square root of their masses. For gases 1 and 2:

Thomas Graham (1805-1869)

where is the rate of effusion and M is the atomic or molecular weight of the gas particles.
13 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

1 M1

and

1 M2

Diffusion and Effusion 1 = constant and M1

2 = constant
M2

1 = 2

M2 M1

or

1 = 2

M2 M1

This is called Grahams law of effusion.

14

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Diffusion and Effusion


Comparing the molecular velocities of nitrogen, hydrogen and helium gases: Molecular mass of nitrogen = 28 Molecular mass of hydrogen = 2 Atomic mass of helium = 4

15

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Diffusion and Effusion


Relative number of molecules with given velocity

N2 gas

Urms

He gas

Urms Urms

H2 gas

Molecular velocity (m/s)


16 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Diffusion and Effusion

Cotton witted with NH3(aq) 660 m/s

Cotton witted with HCl(aq) 450 m/s

White ring of NH4Cl(s)


17 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Diffusion and Effusion

NH4Cl

NH3 17 g/mol

HCl 36.5 g/mol

18

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Diffusion and Effusion NH3 (g) + HCl (g)

NH4Cl (s)

distance traveled by NH3 Urms for NH3 = distance traveled by HCl Urms for HCl Urms for NH3 = Urms for HCl MHCl MNH3 = 36.5 17

= 1.5
19 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Diffusion and Effusion


Problems: - What is the rate of effusion for H2 if 15.00 ml of CO2 takes 4.55 sec to effuse out of a container? - What is the molar mass of gas X if it effuses 0.876 times as rapidly as N2(g)?

20

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Real Gases
PV = nRT
2.0 N2 CH4 H2 CO2 Ideal Gas

n = PV = 1.0 RT

Repulsive Forces

PV RT

1.0

Attractive Forces
0 0

200

400

600

P (atm)

800

1000

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Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Van der Waals equation


The deviation from ideal behavior has been explained by the fact that: - molecules do occupy space. - there is a slight forces of attraction (Van der Waals forces) exist between molecules. The ideal gas equation is:

PV = n R T
The first step: the actual volume is the volume of the container V minus a correction factor for the volume of molecules nb.
22 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Van der Waals equation


This leads to: P (V nb) = nR T The second step: consider the attraction forces exist between molecules.

Pobs = P correction factor


No attraction forces exist between molecules.

The ideal behaviour

23

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Van der Waals equation


There is attraction forces exist between molecules.

The real behaviour


The Pobs decreases due to the attraction forces.

24

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3

Van der Waals equation


To determine the value of the correction factor: - The factor depends on the concentration of the gas molecules. The concentration of the gas molecules is: Moles of the gas per liter

(n / V)
- The number of interacting pairs of particles depends on the square of concentration,

(n / V)2
25 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Van der Waals equation


In a gas sample containing N particles, there is N 1 partners available for each particle.

45
For N particles, there are N(N 1)/2 pairs. N(N1)/2 = 10(10-1)/2 = 10(9)/2 = 90/2 = 45
26 Prof. Dr. Mamdouh A. Abdel Rahim

1 2 3 4 5 6 7

10 9 8

Lecture 3

Van der Waals equation


For N particles, there are N(N 1)/2 pairs. For large N, the value N(N 1)/2 could be: N2 / 2 Taking into consideration the attraction forces between gas molecules, the pressure is corrected in the form:

Pobs = P correction factor correction factor (concentration)2 (n / V)2 2 a (n / V) =


27 Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Van der Waals equation Pobs = P correction factor Pobs = P a


Therefor:

( (

n V n V

2 ) 2 )
Lecture 3

P = Pobs + a

28

Prof. Dr. Mamdouh A. Abdel Rahim

Van der Waals equation Pobs Van der Waals equation n 2 (V nb) nR T + a = V

( (

Pressure correction

Volume correction

Pobs

+ a

n V

2 ) (V nb) = nR T
Videal
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 3

Pideal
29

Thank you

30

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 3