Thermometer - Physical Principles of Thermometry

Physical Principles of Thermometry

Thermometers may be described as empirical or absolute. Absolute thermometers are calibrated numerically by the thermodynamic absolute temperature scale. Empirical thermometers are not in general necessarily in exact agreement with absolute thermometers as to their numerical scale readings, but to qualify as thermometers at all they must agree with absolute thermometers and with each other in the following way: given any two bodies isolated in their separate respective thermodynamic equilibrium states, all thermometers agree as to which of the two has the higher temperature, or that the two have equal temperatures. For any two empirical thermometers, this does not require that the relation between their numerical scale readings be linear, but it does require that relation to be strictly monotonic. This is a fundamental character of temperature and thermometers.

As it is customarily stated in textbooks, taken alone, the so-called "zeroth law of thermodynamics" fails to deliver this information, but the statement of the zeroth law of thermodynamics by James Serrin in 1977, though rather mathematically abstract, is more informative for thermometry: "Zeroth Law – There exists a topological line which serves as a coordinate manifold of material behaviour. The points of the manifold are called 'hotness levels', and is called the 'universal hotness manifold'." To this information there needs to be added a sense of greater hotness; this sense can be had, independently of calorimetry, of thermodynamics, and of properties of particular materials, from Wien's displacement law of thermal radiation: the temperature of a bath of thermal radiation is proportional, by a universal constant, to the frequency of the maximum of its frequency spectrum; this frequency is always positive, but can have values that tend to zero.

There are several principles on which empirical thermometers are built, as listed in the section of this article entitled "Primary and secondary thermometers". Several such principles are essentially based on the constitutive relation between the state of a suitably selected particular material and its temperature. Only some materials are suitable for this purpose, and they may be considered as "thermometric materials". Radiometric thermometry, in contrast, can be only very slightly dependent on the constitutive relations of materials. In a sense then, radiometric thermometry might be thought of as "universal". This is because it rests mainly on a universality character of thermodynamic equilibrium, that it has the universal property of producing blackbody radiation.