British chemist Henry Cavendish, the discoverer of hydrogen in 1766, discovered that air is composed of more gases than nitrogen and oxygen. He recorded these findings in 1784 and 1785; among them, he found a then-unidentified gas less reactive than nitrogen. Helium was first reported in 1868; the report was based on the new technique of spectroscopy; some spectral lines in light emitted by the Sun did not match those of any of the known elements. Mendeleev was not convinced by this finding since variance of temperature led to change of intensity of spectral lines and their location on the spectrum; this opinion was held by some other scientists of the day. Others believed the spectral lines could belong to an element that occurred on the Sun but not on Earth; some believed it was yet to be found on Earth.
In 1894, British chemist William Ramsay and British physicist Lord Rayleigh isolated argon from air and determined that it was a new element. Argon, however, did not engage in any chemical reactions and was—highly unusually for a gas—monatomic; it did not fit into the periodic law and thus challenged the very notion of it. Not all scientists immediately accepted this report; Mendeleev's original response was that argon was a triatomic form of nitrogen rather than an element of its own. While the notion of a possibility of a group between that of halogens and that of alkali metals had existed (some scientists believed that several atomic weight values between halogens and alkali metals were missing, especially since places in this half of group VIII remained vacant), argon did not easily match the position between chlorine and potassium because its atomic weight exceeded those of both chlorine and potassium. Other explanations were proposed; for example, Ramsay supposed argon could be a mixture of different gases. For a while, Ramsay believed argon could be a mixture of three gases of similar atomic weights; this triad would resemble the triad of iron, cobalt, and nickel, and be similarly placed in group VIII. Certain that shorter periods contain triads of gases at their ends, Ramsay suggested in 1898 the existence of a gas between helium and argon with an atomic weight of 20; after its discovery later that year (it was named neon), Ramsay continued to interpret it as a member of a horizontal triad at the end of that period.
In 1896, Ramsay tested a report of American chemist William Francis Hillebrand, who found a stream of an unreactive gas from a sample of uraninite. Wishing to prove it was nitrogen, Ramsay analyzed a different uranium mineral, cleveite, and found a new element, which he named krypton. This finding was corrected by British chemist William Crookes, who matched its spectrum to that of the Suns helium. Following this discovery, Ramsay, using fractional distillation to separate the components air, discovered several more such gases in 1898: metargon, krypton, neon, and xenon; detailed spectroscopic analysis of the first of these demonstrated it was argon contaminated by a carbon-based impurity. Ramsay was initially skeptical about the existence of gases heavier than argon, and the discovery of krypton and xenon came as a surprise to him; however, Ramsay accepted his own discovery, and the five newly discovered inert gases (now noble gases) were placed in a single column in the periodic table. Although Mendeleevs table predicted several undiscovered elements, it did not predict the existence of such inert gases, and Mendeleev originally rejected those findings as well.