Planck's law
In physics, Planck's law (also Planck radiation law[1]: 1305 ) describes the spectral density of electromagnetic radiation emitted by a black body in thermal equilibrium at a given temperature T, when there is no net flow of matter or energy between the body and its environment.[2]
Not to be confused with Planck relation or Planck's principle.At the end of the 19th century, physicists were unable to explain why the observed spectrum of black-body radiation, which by then had been accurately measured, diverged significantly at higher frequencies from that predicted by existing theories. In 1900, German physicist Max Planck heuristically derived a formula for the observed spectrum by assuming that a hypothetical electrically charged oscillator in a cavity that contained black-body radiation could only change its energy in a minimal increment, E, that was proportional to the frequency of its associated electromagnetic wave. While Planck originally regarded the hypothesis of dividing energy into increments as a mathematical artifice, introduced merely to get the correct answer, other physicists including Albert Einstein built on his work, and Planck's insight is now recognized to be of fundamental importance to quantum theory.
History[edit]
Balfour Stewart[edit]
In 1858, Balfour Stewart described his experiments on the thermal radiative emissive and absorptive powers of polished plates of various substances, compared with the powers of lamp-black surfaces, at the same temperature.[9] Stewart chose lamp-black surfaces as his reference because of various previous experimental findings, especially those of Pierre Prevost and of John Leslie. He wrote "Lamp-black, which absorbs all the rays that fall upon it, and therefore possesses the greatest possible absorbing power, will possess also the greatest possible radiating power."
Stewart measured radiated power with a thermo-pile and sensitive galvanometer read with a microscope. He was concerned with selective thermal radiation, which he investigated with plates of substances that radiated and absorbed selectively for different qualities of radiation rather than maximally for all qualities of radiation. He discussed the experiments in terms of rays which could be reflected and refracted, and which obeyed the Helmholtz reciprocity principle (though he did not use an eponym for it). He did not in this paper mention that the qualities of the rays might be described by their wavelengths, nor did he use spectrally resolving apparatus such as prisms or diffraction gratings. His work was quantitative within these constraints. He made his measurements in a room temperature environment, and quickly so as to catch his bodies in a condition near the thermal equilibrium in which they had been prepared by heating to equilibrium with boiling water. His measurements confirmed that substances that emit and absorb selectively respect the principle of selective equality of emission and absorption at thermal equilibrium.
Stewart offered a theoretical proof that this should be the case separately for every selected quality of thermal radiation, but his mathematics was not rigorously valid. According to historian D. M. Siegel: "He was not a practitioner of the more sophisticated techniques of nineteenth-century mathematical physics; he did not even make use of the functional notation in dealing with spectral distributions."[48] He made no mention of thermodynamics in this paper, though he did refer to conservation of vis viva. He proposed that his measurements implied that radiation was both absorbed and emitted by particles of matter throughout depths of the media in which it propagated. He applied the Helmholtz reciprocity principle to account for the material interface processes as distinct from the processes in the interior material. He concluded that his experiments showed that, in the interior of an enclosure in thermal equilibrium, the radiant heat, reflected and emitted combined, leaving any part of the surface, regardless of its substance, was the same as would have left that same portion of the surface if it had been composed of lamp-black. He did not mention the possibility of ideally perfectly reflective walls; in particular he noted that highly polished real physical metals absorb very slightly.
Gustav Kirchhoff[edit]
In 1859, not knowing of Stewart's work, Gustav Robert Kirchhoff reported the coincidence of the wavelengths of spectrally resolved lines of absorption and of emission of visible light. Importantly for thermal physics, he also observed that bright lines or dark lines were apparent depending on the temperature difference between emitter and absorber.[49]
Kirchhoff then went on to consider bodies that emit and absorb heat radiation, in an opaque enclosure or cavity, in equilibrium at temperature T.
Here is used a notation different from Kirchhoff's. Here, the emitting power E(T, i) denotes a dimensioned quantity, the total radiation emitted by a body labeled by index i at temperature T. The total absorption ratio a(T, i) of that body is dimensionless, the ratio of absorbed to incident radiation in the cavity at temperature T . (In contrast with Balfour Stewart's, Kirchhoff's definition of his absorption ratio did not refer in particular to a lamp-black surface as the source of the incident radiation.) Thus the ratio E(T, i)/a(T, i) of emitting power to absorption ratio is a dimensioned quantity, with the dimensions of emitting power, because a(T, i) is dimensionless. Also here the wavelength-specific emitting power of the body at temperature T is denoted by E(λ, T, i) and the wavelength-specific absorption ratio by a(λ, T, i) . Again, the ratio E(λ, T, i)/a(λ, T, i) of emitting power to absorption ratio is a dimensioned quantity, with the dimensions of emitting power.
In a second report made in 1859, Kirchhoff announced a new general principle or law for which he offered a theoretical and mathematical proof, though he did not offer quantitative measurements of radiation powers.[50] His theoretical proof was and still is considered by some writers to be invalid.[48][51] His principle, however, has endured: it was that for heat rays of the same wavelength, in equilibrium at a given temperature, the wavelength-specific ratio of emitting power to absorption ratio has one and the same common value for all bodies that emit and absorb at that wavelength. In symbols, the law stated that the wavelength-specific ratio E(λ, T, i)/a(λ, T, i) has one and the same value for all bodies, that is for all values of index i. In this report there was no mention of black bodies.
In 1860, still not knowing of Stewart's measurements for selected qualities of radiation, Kirchhoff pointed out that it was long established experimentally that for total heat radiation, of unselected quality, emitted and absorbed by a body in equilibrium, the dimensioned total radiation ratio E(T, i)/a(T, i), has one and the same value common to all bodies, that is, for every value of the material index i.[52] Again without measurements of radiative powers or other new experimental data, Kirchhoff then offered a fresh theoretical proof of his new principle of the universality of the value of the wavelength-specific ratio E(λ, T, i)/a(λ, T, i) at thermal equilibrium. His fresh theoretical proof was and still is considered by some writers to be invalid.[48][51]
But more importantly, it relied on a new theoretical postulate of "perfectly black bodies", which is the reason why one speaks of Kirchhoff's law. Such black bodies showed complete absorption in their infinitely thin most superficial surface. They correspond to Balfour Stewart's reference bodies, with internal radiation, coated with lamp-black. They were not the more realistic perfectly black bodies later considered by Planck. Planck's black bodies radiated and absorbed only by the material in their interiors; their interfaces with contiguous media were only mathematical surfaces, capable neither of absorption nor emission, but only of reflecting and transmitting with refraction.[53]
Kirchhoff's proof considered an arbitrary non-ideal body labeled i as well as various perfect black bodies labeled BB. It required that the bodies be kept in a cavity in thermal equilibrium at temperature T . His proof intended to show that the ratio E(λ, T, i)/a(λ, T, i) was independent of the nature i of the non-ideal body, however partly transparent or partly reflective it was.
His proof first argued that for wavelength λ and at temperature T, at thermal equilibrium, all perfectly black bodies of the same size and shape have the one and the same common value of emissive power E(λ, T, BB), with the dimensions of power. His proof noted that the dimensionless wavelength-specific absorption ratio a(λ, T, BB) of a perfectly black body is by definition exactly 1. Then for a perfectly black body, the wavelength-specific ratio of emissive power to absorption ratio E(λ, T, BB)/a(λ, T, BB) is again just E(λ, T, BB), with the dimensions of power. Kirchhoff considered, successively, thermal equilibrium with the arbitrary non-ideal body, and with a perfectly black body of the same size and shape, in place in his cavity in equilibrium at temperature T . He argued that the flows of heat radiation must be the same in each case. Thus he argued that at thermal equilibrium the ratio E(λ, T, i)/a(λ, T, i) was equal to E(λ, T, BB), which may now be denoted Bλ (λ, T), a continuous function, dependent only on λ at fixed temperature T, and an increasing function of T at fixed wavelength λ, at low temperatures vanishing for visible but not for longer wavelengths, with positive values for visible wavelengths at higher temperatures, which does not depend on the nature i of the arbitrary non-ideal body. (Geometrical factors, taken into detailed account by Kirchhoff, have been ignored in the foregoing.)
Thus Kirchhoff's law of thermal radiation can be stated: For any material at all, radiating and absorbing in thermodynamic equilibrium at any given temperature T, for every wavelength λ, the ratio of emissive power to absorptive ratio has one universal value, which is characteristic of a perfect black body, and is an emissive power which we here represent by Bλ (λ, T). (For our notation Bλ (λ, T), Kirchhoff's original notation was simply e.)[7][52][54][55][56][57]
Kirchhoff announced that the determination of the function Bλ (λ, T) was a problem of the highest importance, though he recognized that there would be experimental difficulties to be overcome. He supposed that like other functions that do not depend on the properties of individual bodies, it would be a simple function. That function Bλ (λ, T) has occasionally been called 'Kirchhoff's (emission, universal) function',[58][59][60][61] though its precise mathematical form would not be known for another forty years, till it was discovered by Planck in 1900. The theoretical proof for Kirchhoff's universality principle was worked on and debated by various physicists over the same time, and later.[51] Kirchhoff stated later in 1860 that his theoretical proof was better than Balfour Stewart's, and in some respects it was so.[48] Kirchhoff's 1860 paper did not mention the second law of thermodynamics, and of course did not mention the concept of entropy which had not at that time been established. In a more considered account in a book in 1862, Kirchhoff mentioned the connection of his law with "Carnot's principle", which is a form of the second law.[62]
According to Helge Kragh, "Quantum theory owes its origin to the study of thermal radiation, in particular to the "blackbody" radiation that Robert Kirchhoff had first defined in 1859–1860."[63]
Empirical and theoretical ingredients for the scientific induction of Planck's law[edit]
In 1860, Kirchhoff predicted experimental difficulties for the empirical determination of the function that described the dependence of the black-body spectrum as a function only of temperature and wavelength. And so it turned out. It took some forty years of development of improved methods of measurement of electromagnetic radiation to get a reliable result.[64]
In 1865, John Tyndall described radiation from electrically heated filaments and from carbon arcs as visible and invisible.[65] Tyndall spectrally decomposed the radiation by use of a rock salt prism, which passed heat as well as visible rays, and measured the radiation intensity by means of a thermopile.[66][67]
In 1880, André-Prosper-Paul Crova published a diagram of the three-dimensional appearance of the graph of the strength of thermal radiation as a function of wavelength and temperature.[68] He determined the spectral variable by use of prisms. He analyzed the surface through what he called "isothermal" curves, sections for a single temperature, with a spectral variable on the abscissa and a power variable on the ordinate. He put smooth curves through his experimental data points. They had one peak at a spectral value characteristic for the temperature, and fell either side of it towards the horizontal axis.[69][70] Such spectral sections are widely shown even today.
In a series of papers from 1881 to 1886, Langley reported measurements of the spectrum of heat radiation, using diffraction gratings and prisms, and the most sensitive detectors that he could make. He reported that there was a peak intensity that increased with temperature, that the shape of the spectrum was not symmetrical about the peak, that there was a strong fall-off of intensity when the wavelength was shorter than an approximate cut-off value for each temperature, that the approximate cut-off wavelength decreased with increasing temperature, and that the wavelength of the peak intensity decreased with temperature, so that the intensity increased strongly with temperature for short wavelengths that were longer than the approximate cut-off for the temperature.[71]
Having read Langley, in 1888, Russian physicist V.A. Michelson published a consideration of the idea that the unknown Kirchhoff radiation function could be explained physically and stated mathematically in terms of "complete irregularity of the vibrations of ... atoms".[72][73] At this time, Planck was not studying radiation closely, and believed in neither atoms nor statistical physics.[74] Michelson produced a formula for the spectrum for temperature: