KEY CONCEPTS

KINETIC THEORY & THERMODYNAMICS

1. IDEAL GASES

Experiments have shown that all gases exhibit similar behavior at very low densities.
Such ideal gases, as they are known, follow certain relationships of temperature,
pressure and volume known as the gas laws:
Boyle’s Law: PV = constant at constant T
V
Charles’ Law: = constant at constant P
T
P
Gay-Lussac’s Law: = constant at constant V
T
The number of moles n contained in a sample of any substance can be determined
from the relationship:
m
n=
M
where m is the mass of the sample of the substance and M is the molecular mass of the
substance. The number of moles of gas is a more convenient measure of quantity than
its mass. For example, the volume of one mole of an ideal gas at a standard
temperature and pressure (273 K, 1 atm) is the same for all gases, 22.4 L. Using the
gas laws and the concept of moles a general relationship between pressure, volume,
temperature and quantity of gas can be derived which is known as the ideal gas law:
PV = nRT
where R is known as the universal gas constant.

The number of molecules in one mole of a substance is known as Avogadro’s

number, NA. Therefore, the number of moles of a gas can be written as:
N
n=
NA
where N is the number of molecules in the sample. The gas law then can be written as:
N
PV = nRT = RT = Nk B T
NA
where kB is known as the Boltzmann’s constant.
B
 KEY CONCEPTS
KINETIC THEORY & THERMODYNAMICS

According to the kinetic theory of gases, an ideal gas is made up of widely-

separated, randomly-moving molecules that obey the the laws of classical mechanics.
Collisions between two gas molecules or a gas molecule and the wall of some confining
container are assumed to be elastic. Therefore, the average kinetic energy of a gas
molecule is given by:
3
K avg = k BT
2
where kb is the Boltzmann’s constant and T is the temperature of the gas. This shows
that the average translational kinetic energy of a gas molecule is directly proportional to
its temperature. It follows that the root-mean-square speed of the molecule is given
by:
3k BT 3RT 3 RT
vrms = = =
m mN A M
where m is the mass of an individual gas molecule and M is the molecular mass of the
gas.

2. LAWS OF THERMODYNAMICS

The first law of thermodynamics states that when a system undergoes a change
from one state to another, the change in its internal energy is given by:
ΔU = Q + W
where Q is the heat flow into the system and W is the work done on a system. The
change in the internal energy of an ideal gas can also be written as:
3nRΔT
ΔU =
2
If the pressure is kept constant during some process involving an ideal gas, then the
work done on the gas is given by:
W = − pΔV
Two kinds of processes frequently occur in laboratory experiments with gases:
isothermal and adiabatic. By definition, an isothermal process is one that occurs at
constant temperature. For such a process the internal energy does not change:
ΔU = 0
For an adiabatic process, there is no heat into or out of the system:
Q=0
and therefore:
ΔU = W
One form of the second law of thermodynamics states that heat does not flow
spontaneously from a cold object to a hot object. A heat engine produces mechanical
work from thermal energy. This can only occur when heat flows from a hot reservoir to a
 KEY CONCEPTS
KINETIC THEORY & THERMODYNAMICS
cold reservoir. The net work done by a heat engine is equal to the heat input from the
hot reservoir, less the heat input to the cold reservoir as given by:
− W = QH − QC
The efficiency of a heat engine is determined by the absolute value of the net amount
of work done by the engine divided by the heat input from the hot reservoir as given by:
W QH − QC
e= =
QH QH
The theoretical limit for the efficiency of a heat engine is determined from the Carnot
cycle. This cycle consists of four reversible processes, isothermal expansion and
compression, and adiabatic expansion and compression. The efficiency of the Carnot
cycle depends only on the temperature of the hot and cold reservoirs between which it
operates and is given by:
T −T
eC = H C
TH
A heat pump operates in reverse of a heat engine. The theoretical coefficient of
performance of a heat pump can be expressed as:
TC
CPC =
TH − TC
Another form of the second law of thermodynamics is that natural processes tend to
move toward a state of greater disorder. The measure of disorder of a system is called
entropy. For an idealize, reversible process the entropy of the system can remain the
same. However, for all real processes, the entropy of the system always increases.