Chapter 5: Gases

5.1 Pressure

A device to measure atmospheric pressure, the barometer, was invented in 1643 by an Italian scientist
named Evangelista Torricelli (1608-1647).

Atmospheric pressure results from the mass of the air being pulled toward the center of the earth by
gravity.
Atmospheric pressure varies with altitude.

Units of Pressure

1 atm = 760 mmHg (millimeters mercury)

= 760 Torr
= 101,325 Pa (Pascals)
= 101.3 kPa (KiloPascals)
= 0.1013 MPa (MegaPascals)
= 14.7 psi (Pounds per Square Inch)
= 14.7 lb/in2
= 29.92 in Hg

Pressure is defined as force per unit area: Pressure = force/area.

In the SI system, the unit of force is the newton (N) and the unit of area is meters squared (m 2); thus
the unit of pressure in the SI system is (N/m 2).

5.2 The Gas Laws of Boyle, Charles, and Avogadro

The first quantitative experiments on gases were performed by an Irish chemist, Robert Boyle (1627-
1691). Boyle studied the relationship between the pressure of the trapped gas and its volume.

Boyle’s Law

PV = k
Where P is pressure, V is volume, and k is a constant for a given sample of air at a specific temperature.
If temperature does not change, then:
P1V1 = P2V2
Boyle’s Law can be rearranged to give: V = k/P = k × 1/P
In a graph of P versus V: In a graph of V versus P:
(Inverse relationship) (Direct relationship)

Boyle’s law holds precisely only at very low pressures. Measurements at

higher pressures reveal that PV is not constant but varies as the pressure is varied.

A gas that strictly obeys Boyle’s law is called an ideal gas.

Charles’s Law

The volumes of all gases extrapolate to zero at the same temperature, -273°C. On the Kelvin
temperature scale this point is defined as 0 K, which leads to the following relationship between the
Kelvin and Celsius scales:
K = °C + 273
0 K is absolute zero, and there is much evidence that suggests that this temperature cannot be attained.

The volume of gas is directly proportional to temperature and extrapolates to zero when the
temperature is 0 K. This behavior is represented by:
V = bT
Where T is in Kelvins and b is a proportionality constant.
Therefore, if pressure is constant, then:
V1/T1 = V2/T2.

Avogadro’s Law

Equal volumes of gases at the same temperature and pressure contain the same number of “particles.”
This observation is called Avogadro’s Law.
V = an
Where V is the volume of the gas, n is the number of moles of gas particles, and a is a proportionality
constant.
This equation states that for a gas at constant temperature and pressure, the volume is directly
proportional to the number of moles of gas.
If temperature and pressure are constant, then:
V1/n1=V2/n2

5.3 The Ideal Gas law

Ideal Gas Law

We have considered three laws that describe the behavior of gases as revealed by experimental
observations:
Boyle’s law: V = k/P (at constant T and n)
Charles’s law: V = bT (at constant P and n)
Avogadro’s law:V = an (at constant T and P)
These relationships, which show how the volume of a gas depends on pressure, temperature, and
number of moles of gas present, can be combined as follows:
V = R (Tn/P)
Where R is the combined proportionality constant called the universal gas constant. When the pressure
is expressed in atmospheres and the volume in liters, then:
R = 0.08206 L × atm/K × mol
The combined gas law can be arranged to something more familiar:
PV=nRT
Or
P1V1/T1=P2V2/T2
Always convert the temperature to the Kelvin scale when applying the ideal gas law.
5.4 Gas Stoichiometry

Molar Volume and STP

The volume 22.42 liters is the molar volume of an ideal gas (at 0°C and 1 atm).
The conditions 0°C and 1 atm, called standard temperature and pressure (STP), are common reference
conditions for the properties of gases. At STP:
1 mol (Gas) = 22.42L

Molar Mass of a Gas

n = grams of gas/molar mass = mass/molar mass= m/molar mass

Substitution into the ideal gas equation gives:
P = nRT/V = (m/molar mass)RT/V = m(RT)/V (molar mass)
However, since m/V is the gas density d in units of grams per liter:
P = dRT/molar mass
Or
Molar mass = dRT/P

5.5 Dalton’s Law of Partial Pressures

Dalton’s Law of Partial Pressures

For a mixture of gases in a container, the total pressure exerted is the sum of the pressures that each
gas would exert if it were alone. This statement, known as Dalton’s law of partial pressures, can be
expressed as follows:
PTotal = P1 + P2 + P3 +… = n1RT/V + n2RT/V + N3RT/V +…
= (n1 + n2 + n3 + …)(RT/V)
= nTotal(RT/V)
Where nTotal is the sum of the numbers of moles of the various gases; thus, for a mixture of ideal gases,
it is the total number of moles of particles that is important, not the identity or composition of the
involved gas particles.

5.6 The Kinetic Molecular Theory of Gases

Kinetic Molecular Theory

The kinetic molecular theory (KMT) is a simple model that attempts to explain the properties of an ideal
gas. This model is based on speculations about the behavior of the individual gas particles (atoms or
molecules).
Postulates of the Kinetic Molecular Theory
1. The particles are so small compared with the distances between them that the volume of the
individual particles can be assumed to be negligible (zero).
2. The particles are in constant motion. The collisions of the particles with the walls of the
container are the cause of the pressure exerted by the gas.
3. The particles are assumed to exert no forces on each other; they are assumed neither to
attract nor to repel each other.
4. The average kinetic energy of a collection of gas particles is assumed to be directly
proportional to the Kelvin temperature of a gas.
The Meaning of Temperature

Kevin temperature indicates the average kinetic energy of gas particles. The exact relationship between
temperature and average kinetic energy can be obtained by combining the equations:
PV/n = RT = 2/3(KE)avg
Which yields the expression:
(KE)avg = 3/2RT

Root Mean Square Velocity

In the equation from the kinetic molecular theory, the average velocity of the gas particles is a special
kind of average. The symbol v2 means the average of the squares of the particle velocities. The square
root of v2 is called the root mean square velocity and is symbolized by v rms.
vrms = √ v 2
after deriving:
3 RT
vrms =
√
Where M is the mass of a mole of gas particles in kilograms.
M

R = 8.3145 J/K ×mol

5.7 Effusion and Diffusion

Diffusion is the term used to describe the mixing of gases. The rate of diffusion is the rate of the mixing
of gasses.
Effusion is the term used to describe the passage of the gas through a tiny orifice into an evacuated
chamber. The rate of effusion measures the speed at which the gas is transferred into the chamber.

Graham’s Law of Effusion

The relative rates of effusion of two gases at the same temperature and pressure are given by the
inverse ratio of the square roots of the masses of the gas particles:
Rate of effusion for gas 1/Rate of effusion for gas 2 = √ M2/√ M1
Where M1 and M2 represent the molar masses of the gases.