The Kinetic Theory of Gases

The equation of state describes how a gas’s pressure, volume, temperature, and number of moles are related. These macroscopic properties help define the condition, or state, of the matter in a thermodynamics system.

The relationship between these quantities can be written as a simple mathematical expression. In some cases, it is too complex to express in a formula. Even then, the link between the quantities still exists.

When an equation of state cannot be written mathematically, scientists...

The ideal gas equation links pressure, volume, temperature, and amount of gas. It describes a hypothetical gas and is built from four empirical gas laws: Boyle’s law, Charles’s law, Avogadro’s law, and Gay-Lussac’s law.

When these proportionalities are combined, they give one constant called the universal gas constant. This gas constant has the same value for all real gases under certain conditions. In chemical calculations, that constant is used in the ideal gas equation.

The equation works...

Real gases often deviate from the ideal gas law, especially at low temperatures and high pressures. The van der Waals equation improves the ideal gas model by adding two corrections that account for these real-world effects.

One correction accounts for attractive forces between molecules. These forces become stronger at higher densities and lower the measured pressure, so the equation adds a pressure term based on the square of the molar density and a positive constant a.

The second...

pV curves show how gas pressure changes with volume. A pV diagram is a graph of pressure versus volume for the gas being studied. It helps describe how the substance behaves. When the gas acts like an ideal gas, the ideal gas equation gives the link between pressure and volume.

A common pV curve is an isotherm, which is a line drawn at fixed temperature and fixed number of molecules. For an ideal gas, pressure times volume stays constant. That means volume goes down as pressure goes up. The...

Avogadro's number and gas particle motion help explain how gases behave at the particle level. A mole is the amount of a substance that contains as many molecules as there are atoms in exactly 12 grams of carbon-12. This idea came from Amedeo Avogadro, who proposed that equal volumes of gas at the same pressure and temperature contain equal numbers of molecules, no matter what the gas is.

Avogadro's number is the number of molecules in one mole. Its value is 6.02 × 10^23 mol−1. This number...

Gas pressure comes from the motion of molecules in a container. The word gas came from a Flemish word meaning “chaos,” and J. B. van Helmont first used it to describe vapors. In a gas, molecules move in a continuous and random way.

When a molecule hits a container wall, its velocity changes. The part of the velocity parallel to the wall stays the same. The part perpendicular to the wall reverses direction, but its size does not change. If the molecule’s velocity changes in the x-direction, its...

Molecular speed curves show how the speeds of gas particles are spread out at a given temperature. For a gas with many molecules, this spread is predictable even though each molecule moves randomly in direction and speed. The pattern is called the Maxwell-Boltzmann distribution.

Liquids have a similar speed distribution, but it is not exactly the same as in gases. This difference helps explain boiling and vapor pressure. A molecule must reach at least a certain speed, v a, to escape from the...

The Maxwell-Boltzmann distribution describes how molecular speeds are spread in a gas. Even though individual molecules move in random directions, the whole gas has a predictable speed pattern. This distribution is written as f(v), where v is molecular speed.

The distribution function is used to find the expected number of particles with speeds between v1 and v2. Because N is dimensionless, f(v) has units of seconds per meter. The relationship can also be written in differential form for speed...

Water phase changes can be mapped on a pressure and temperature chart called a phase diagram. These plots show which phase a substance is in at different conditions. They also reveal where phase transitions happen, because the boundary lines mark the temperatures and pressures where two phases coexist.

The water phase diagram shows how pressure affects boiling. As pressure rises, the boiling temperature increases gradually until it reaches 374 °C at 218 atm. A pressure cooker works this way.

Gas collisions in a cylinder help explain the mean free path and mean free time. Gas molecules move in random motion. They collide with each other and change speed and direction. The mean free path is the average path length between collisions.

The mean free path depends on how many molecules are packed into a volume. It varies inversely with density. When more molecules are present, collisions happen more often, so the mean free path becomes shorter. It also depends on molecule size. Larger...

Heat capacity of gases depends on the gas type and the motion of its molecules. It is the amount of heat energy needed to raise the temperature of a unit mass of gas by one degree Celsius. This thermodynamic property is important in science and industry.

To solve heat capacity problems, first identify the gas. A gas's molecular structure affects its heat capacity because the molecules have different degrees of freedom. These values can be found from tables or from empirical equations.

Next,...

Gas mixtures have a total pressure that comes from the partial pressures of each gas. A partial pressure is the pressure one gas would make if it filled the whole container by itself. This idea helps explain how gases behave when they are mixed together.

When two or more gases share a container, their molecules move randomly and collide with one another. If the gases are at the same temperature, they reach thermal equilibrium. Their molecules then have the same average kinetic energy. In that...

Earth’s escape velocity is the speed an object needs to leave gravity behind. Near the top of the atmosphere, about 100 km above Earth, that speed is 11.1 km/s. Gas molecules can escape only if their speeds become high enough to reach that limit.

The chance of escape depends on gas temperature and molecular speed. According to kinetic theory, the average kinetic energy of gas molecules is proportional to temperature. As temperature rises, the rms speed, or root-mean-square speed, also rises.