Thermal Expansion

The familiar mercury thermometer operates on the principle that the mercury, its working fluid, expands when heated and contracts when cooled. In general, all substances expand and contract with changes in temperature. The zeroth law of thermodynamics guarantees that we can construct a comparative scale of temperatures that is independent of what type of thermometer we use. If a thermometer gives a certain reading when it's in thermal equilibrium with object A, and also gives the same reading for object B, then A and B must be the same temperature, regardless of the details of how the thermometers works.

What about constructing a temperature scale in which every degree represents an equal step in temperature? The Celsius scale has 0 as the freezing point of water and 100 as its boiling point. The hidden assumption behind all this is that since two points define a line, any two thermometers that agree at two points must agree at all other points. In reality if we calibrate a mercury thermometer and an alcohol thermometer in this way, we will find that a graph of one thermometer's reading versus the other is not a perfectly straight y = x line. The subtle inconsistency becomes a drastic one when we try to extend the temperature scale through the points where mercury and alcohol boil or freeze. Gases, however, are much more consistent among themselves in their thermal expansion than solids or liquids, and the noble gases like helium and neon are more consistent with each other than gases in general. Continuing to search for consistency, we find that noble gases are more consistent with each other when their pressure is very low.

A simplified version of an ideal gas thermometer. The whole instrument is allowed to come into thermal equilibrium with the substance whose temperature is to be measured, and the mouth of the cylinder is left open to standard pressure. The volume of the noble gas gives an indication of temperature.

As an idealization, we imagine a gas in which the atoms interact only with the sides of the container, not with each other. Such a gas is perfectly nonreactive (as the noble gases very nearly are), and never condenses to a liquid (as the noble gases do only at extremely low temperatures). Its atoms take up a negligible fraction of the available volume. Any gas can be made to behave very much like this if the pressure is extremely low, so that the atoms hardly ever encounter each other. Such a gas is called an ideal gas, and we define the Celsius scale in terms of the volume of the gas in a thermometer whose working substance is an ideal gas maintained at a fixed (very low) pressure, and which is calibrated at 0 and 100 degrees according to the melting and boiling points of water. The Celsius scale is not just a comparative scale but an additive one as well: every step in temperature is equal, and it makes sense to say that the difference in temperature between 18 and 28 °C is the same as the difference between 48 and 58.

The volume of 1 kg of neon gas as a function of temperature (at standard pressure). Although neon would actually condense into a liquid at some point, extrapolating the graph to zero volume gives the same temperature as for any other gas: absolute zero.

Absolute zero and the Kelvin scale

We find that if we extrapolate a graph of volume versus temperature, the volume becomes zero at nearly the same temperature for all gases: -273 °C. Real gases will all condense into liquids at some temperature above this, but an ideal gas would achieve zero volume at this temperature, known as absolute zero. The most useful temperature scale in scientific work is one whose zero is defined by absolute zero, rather than by some arbitrary standard like the melting point of water. The ideal temperature scale for scientific work, called the Kelvin scale, is the same as the Celsius scale, but shifted by 273 degrees to make its zero coincide with absolute zero. Scientists use the Celsius scale only for comparisons or when a change in temperature is all that is required for a calculation. Only on the Kelvin scale does it make sense to discuss ratios of temperatures, e.g., to say that one temperature is twice as hot as another.

Which temperature scale to use