Charles's law (also known as the law of volumes) is an experimental gas law which describes how gases tend to expand when heated. Gay-Lussac was the first to demonstrate that the law applied generally to all gases, and also to the vapours of volatile liquids if the temperature was more than a few degrees above the boiling point. His statement of the law can be expressed mathematically as:

where V₁₀₀ is the volume occupied by a given sample of gas at 100 °C; V₀ is the volume occupied by the same sample of gas at 0 °C; and k is a constant which is the same for all gases at constant pressure.

At constant pressure, the volume of a given mass of an ideal gas increases or decreases by the same factor as its temperature on the absolute temperature scale. which can be written as:

where V is the volume of the gas; and T is the absolute temperature. The law can also be usefully expressed as follows:

The equation shows that, as absolute temperature increases, the volume of the gas also increases in proportion.

In modern physics, Charles's Law is seen as a special case of the ideal gas equation, in which the pressure and number of molecules are held constant. The ideal gas equation is usually derived from the kinetic theory of gases, which presumes that molecules occupy negligible volume, do not attract each other and undergo elastic collisions (no loss of kinetic energy); an imaginary gas with exactly these properties is termed an ideal gas. The behavior of a real gas is close to that of an ideal gas under most circumstances, which makes the ideal gas law useful.

This law of volumes implies theoretically that as a temperature reaches absolute zero the gas will shrink down to zero volume. This is not physically correct, since in fact all gases turn into liquids at a low enough temperature, and Charles' law is not applicable at low temperatures for this reason.

The fact that the gas will occupy a non-zero volume - even as the temperature approaches absolute zero - arises fundamentally from the uncertainty principle of quantum theory. However, as the temperature is reduced, gases turn into liquids long before the limits of the uncertainty principle come into play due to the attractive forces between molecules which are neglected by Charles's Law.