Miles Eckles April 14, 2011

Chemistry 101 Ch 10 (cont’d)

Gases (cont’d)

Expressed another way

χ = n1 / nTot

P1 (V/RT)
=
P1 (V/RT) + P2 (V/RT) + P3 (V/RT) + …

Example:

 The mole fraction of N2 in air is 0.78, and the mole fraction of O2 in air is 0.21. What are

the partial pressures of these two gases at 760 torr?

 PN2 = PTot x χN2 = (760 torr)(0.78) = 590 torr

 PO2 = PTot x χO2 = (760 torr)(0.21) = 160 torr

Collecting Gases over Water

 When a gaseous product is collected in a closed vessel over water, the total pressure is

the sum of the partial pressures of the gas collected and the pressure of water.

o Ptot = Pgas + PH2O

Kinetic-Molecular Theory
  The ideal gas equation describes how gases behave, but not why. A model to explain the

why, kinetic-molecular theory, has been developed.

o Kinetic-molecular theory can be summarized by the following statements:

1. Gases consist of large numbers of molecules and atoms in constant, random motion.

2. The volume of all the molecules of the gas is negligible compared to the total volume in

which the gas is contained.

3. Attractive and repulsive forces between gas molecules are negligible.

4. Energy can be transferred between molecules during collisions, but the average kinetic

energy of the molecules does not change with time as long as the temperature of the

gas remains constant. Therefore, the collisions are perfectly elastic.

5. The average kinetic energy of the molecules is proportional to the absolute

temperature. At any given temperature. At any given temperature the molecules of all

gases have the same average kinetic energy.

 Provides for a molecular level view of pressure and temperature. Pressure is caused by

collisions of gas molecules and atoms with the walls of the container. Temperature is a

measure of the average kinetic energy of the molecules and atoms in the gas.

Root-mean-square speed

 This is the speed, u, of a molecule in a gas at the average kinetic energy (remember the

gas molecules individually cover a range of kinetic energy).

 Average kinetic energy, ε, is related directly to u:

o ε = ½ mu2
Application to Gas Laws

1. Effect of volume increase at constant temperature. Molecules must move longer

distance between collisions, and fewer collisions with container walls per unit time, so

pressure decreases.

2. Effect of temperature increase at constant volume. An increase in kinetic energy and u.

With no volume increase, more collisions with walls per unit time, so pressure increases.

Molecular Effusion and Diffusion

u = (3RT / M )1/2

Effusion – the escape of gas molecules through a tiny holr into an evacuated
space.

Diffusion – the spread of a substance throughout a space or throughout a space

or throughout a second substance.

Graham’s Law of Effusion

Rate of effusion for gas 1 (r1)

= (M2 / M1)1/2
Rate of effusion for gas 2 (r2)

Example:

 What is the rate of effusion ration of ammonia (NH 3) vs. carbon dioxide (CO2)?

Rate of effusion for gas 1 (r1) (44.0)1/2

= = 1.61
1/2
Rate of effusion for gas 2 (r2) (17.0)

Mean Free Path

  The mean free path is the average distance traveled by a molecule or atom between

collisions. The higher the density of the gas, the smaller the mean free path.

o The mean free path for air molecules at sea level is about 60 nm, but is 10 cm at

an altitude of 100 km, where the earth’s atmosphere is much thinner (less

dense).

Real Gases: Deviations from Ideal Gas Behavior

Real gases do not follow PV = nRT perfectly. The van der Waals equation corrects for the non-

ideal nature of real gases.

(P + n2a/V2) (V – nb) = nRT

 van der Waals equation corrects for the non-ideal nature of real gases.

a corrects for interaction between atoms

b corrects for volume occupied by atoms

 each gas has its own value of a.