Ideal gas scale

When pressure approaches zero, all real gas will behave like ideal gas, that is, pV of a mole of gas relying only on temperature. Therefore, we can design a scale with pV as its argument. Of course any bijective function will do, but for convenience's sake a linear function is the best. Therefore, we define it as^[5]

${\displaystyle T={1 \over nR}\lim _{p\to 0}{pV}.}$

The ideal gas scale is in some sense a "mixed" scale. It relies on the universal properties of gas, a big advance from just a particular substance. But still it is empirical since it puts gas at a special position and thus has limited applicability—at some point no gas can exist. One distinguishing characteristic of ideal gas scale, however, is that it precisely equals thermodynamical scale when it is well defined (see § Equality to ideal gas scale).

International temperature scale of 1990

ITS-90 is designed to represent the thermodynamic temperature scale (referencing absolute zero) as closely as possible throughout its range. Many different thermometer designs are required to cover the entire range. These include helium vapor pressure thermometers, helium gas thermometers, standard platinum resistance thermometers (known as SPRTs, PRTs or Platinum RTDs) and monochromatic radiation thermometers.

Although the Kelvin and Celsius scales are defined using absolute zero (0 K) and the triple point of water (273.16 K and 0.01 °C), it is impractical to use this definition at temperatures that are very different from the triple point of water. Accordingly, ITS–90 uses numerous defined points, all of which are based on various thermodynamic equilibrium states of fourteen pure chemical elements and one compound (water). Most of the defined points are based on a phase transition; specifically the melting/freezing point of a pure chemical element. However, the deepest cryogenic points are based exclusively on the vapor pressure/temperature relationship of helium and its isotopes whereas the remainder of its cold points (those less than room temperature) are based on triple points. Examples of other defining points are the triple point of hydrogen (−259.3467 °C) and the freezing point of aluminum (660.323 °C).

Thermometers calibrated per ITS–90 use complex mathematical formulas to interpolate between its defined points. ITS–90 specifies rigorous control over variables to ensure reproducibility from lab to lab. For instance, the small effect that atmospheric pressure has upon the various melting points is compensated for (an effect that typically amounts to no more than half a millikelvin across the different altitudes and barometric pressures likely to be encountered). The standard even compensates for the pressure effect due to how deeply the temperature probe is immersed into the sample. ITS–90 also draws a distinction between "freezing" and "melting" points. The distinction depends on whether heat is going into (melting) or out of (freezing) the sample when the measurement is made. Only gallium is measured while melting, all the other metals are measured while the samples are freezing.

There are often small differences between measurements calibrated per ITS–90 and thermodynamic temperature. For instance, precise measurements show that the boiling point of VSMOW water under one standard atmosphere of pressure is actually 373.1339 K (99.9839 °C) when adhering strictly to the two-point definition of thermodynamic temperature. When calibrated to ITS–90, where one must interpolate between the defining points of gallium and indium, the boiling point of VSMOW water is about 10 mK less, about 99.974 °C. The virtue of ITS–90 is that another lab in another part of the world will measure the very same temperature with ease due to the advantages of a comprehensive international calibration standard featuring many conveniently spaced, reproducible, defining points spanning a wide range of temperatures.

Definition

Lord Kelvin devised the thermodynamic scale based on the efficiency of heat engines as shown below:

The efficiency of an engine is the work divided by the heat introduced to the system or

${\displaystyle \eta ={\frac {w_{\text{cy}}}{q_{H}}}={\frac {q_{\text{H}}-q_{\text{C}}}{q_{\text{H}}}}=1-{\frac {q_{\text{C}}}{q_{\text{H}}}}\qquad (1),}$

where w_cy is the work done per cycle. Thus, the efficiency depends only on q_C/q_H.

Because of Carnot theorem, any reversible heat engine operating between temperatures T₁ and T₂ must have the same efficiency, meaning, the efficiency is the function of the temperatures only:

${\displaystyle {\frac {q_{\text{C}}}{q_{\text{H}}}}=f(T_{\text{H}},T_{\text{C}})\qquad (2).}$

In addition, a reversible heat engine operating between temperatures T₁ and T₃ must have the same efficiency as one consisting of two cycles, one between T₁ and another (intermediate) temperature T₂, and the second between T₂ and T₃. This can only be the case if

${\displaystyle f(T_{1},T_{3})={\frac {q_{3}}{q_{1}}}={\frac {q_{2}q_{3}}{q_{1}q_{2}}}=f(T_{1},T_{2})f(T_{2},T_{3}).}$

Specializing to the case that ${\displaystyle T_{1}}$ is a fixed reference temperature: the temperature of the triple point of water. Then for any T₂ and T₃,

${\displaystyle f(T_{2},T_{3})={\frac {f(T_{1},T_{3})}{f(T_{1},T_{2})}}={\frac {273.16\cdot f(T_{1},T_{3})}{273.16\cdot f(T_{1},T_{2})}}.}$

Therefore, if thermodynamic temperature is defined by

${\displaystyle T=273.16\cdot f(T_{1},T)\,}$

then the function f, viewed as a function of thermodynamic temperature, is

${\displaystyle f(T_{2},T_{3})={\frac {T_{3}}{T_{2}}},}$

and the reference temperature T₁ has the value 273.16. (Of course any reference temperature and any positive numerical value could be used—the choice here corresponds to the Kelvin scale.)

Equality to ideal gas scale

It follows immediately that

${\displaystyle {\frac {q_{\text{C}}}{q_{\text{H}}}}=f(T_{\text{H}},T_{\text{C}})={\frac {T_{\text{C}}}{T_{\text{H}}}}.\qquad (3).}$

Substituting Equation 3 back into Equation 1 gives a relationship for the efficiency in terms of temperature:

${\displaystyle \eta =1-{\frac {q_{\text{C}}}{q_{\text{H}}}}=1-{\frac {T_{\text{C}}}{T_{\text{H}}}}\qquad (4).}$

This is identical to the efficiency formula for Carnot cycle, which effectively employs the ideal gas scale. This means that the two scales equal numerically at every point.