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Thermal equilibrium

We use the term temperature casually, but what is it exactly? Roughly speaking, temperature is a measure of how concentrated the heat energy is in an object. A large, massive object with very little heat energy in it has a low temperature.

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But physics deals with operational definitions, i.e., definitions of how to measure the thing in question. How do we measure temperature? One common feature of all temperature-measuring devices is that they must be left for a while in contact with the thing whose temperature is being measured. When you take your temperature with a fever thermometer, you wait for the mercury inside to come up to the same temperature as your body. The thermometer actually tells you the temperature of its own working fluid (in this case, the mercury). In general, the idea of temperature depends on the concept of thermal equilibrium. When you mix cold eggs from the refrigerator with flour that has been at room temperature, they rapidly reach a compromise temperature. What determines this compromise temperature is conservation of energy, and the amount of energy required to heat or cool each substance by one degree. But without even having constructed a temperature scale, we can see that the important point is the phenomenon of thermal equilibrium itself: two objects left in contact will approach the same temperature. We also assume that if object A is at the same temperature as object B, and B is at the same temperature as C, then A is at the same temperature as C. This statement is sometimes known as the zeroth law of thermodynamics, so called because after the first, second, and third laws had been developed, it was realized that there was another law that was even more fundamental.

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 is 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=xy=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.

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 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°C28°C is the same as the difference between 48 and 58.

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°\textup{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.

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