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The Noble Gases Rayleigh and Ramsay

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The Noble Gases Rayleigh and Ramsay Redoiscovery of the Dmens The Noble Gases Rayleigh and Ramsay P"''-A {.-_,Jj '}r, 1A1-1I''I' + - 3 ho -.+naw,I . , Jk. .. ~' ",I , " I s q7i -.4 ' t.~' ''wn ,, ''l F' h"-~."_ '- _ -r 1L ~ - j - -it, V.16 !i"As 'ic' ' . _ ' .4 . - I ,' '. 'a. l+q..F , r,, J i! ".;1 .k '_'i ~s a" 4.n'R 4' ", -.l 'r ~y , _i '. 1il ,:t' 9 y ' a,,++ / +Fy1 I' .+i- "3'- 1-i -''. : ' ".. 1"!1r' $' yJ'f y -. 'w r~ " James L. Marshall, Beta Eta I 97/, and r5,}-. 1." :,A yy 4.ri r^o rk Virginia R. Marshall, Beta Eta 2003, Department of Chemistry, University of North Texas, Denton,TX 76203-5070, [email protected] Figure 2. This is Terling Place, which was built 1770-1771, the home of the Rayleigh family. John Henry Cavendish (1731-1810), the discover- Strutt (1727-1816), and his family moved into er of hydrogen (phlogiston) in 1766, studied the house in 1773. His grandson was Lord atmospheric gases for many years. In 1785, he Rayleigh, John William Strutt, 3rd Baron wondered ". whether there are not in reality (1842-1919); when he retired from Cambridge many different substances confounded togeth- University (1884), he returned to continue er by us under the name of phogisticated air research in his private laboratory, the building to [nitrogen]."' By means of electrical sparking he the right, where he discovered argon. reacted phlogisticated air with dephlogisticated air (oxygen) to form nitrous air (nitrogen The discovery of argon was prompted by an oxides) and "continued to spark till no further attempt to corroborate the postulate of William diminution took place... only a small bubble of Prout (1785-1850), who had proposed 3 that the air remained unabsorbed, which certainly was atomic weights of the elements were multiples not more than 1/120 of the bulk of the phlogis- of the primary substance hydrogen. Rayleigh Figure 1. John William Strutt, Third Baron ticated air." accurately weighed samples of purified hydro- Rayleigh, painted by Sir George Reid, 1903. gen, oxygen, and nitrogen to determine if in The original hangs in the Royal Society, London, Lord Rayleigh. 2 John William Strutt, 3rd Carlton House Terrace, London (N51 30.36 fact hydrogen was a common denominator 0 Baron Rayleigh (1842-1919) (Figure 1) was the (Figures 2,3). He obtained reproducible values Woo 07.95); a copy resides in the Rayleigh second Cavendish Professor of Physics for hydrogen and oxygen, but with nitrogen he residence in Terling. He was President of the (1879-1884) at the University of Cambridge noticed a discrepancy: atmospheric nitrogen Royal Society 1905-1908. (following James Clerk Maxwell, 1831-1879). gas weighed more than artificially produced Rayleigh is well known for his publications on gas. He sent a letter to Nature4 where he and 2.2990 0.0006 grams for nitrogen synthe- Rayleigh scattering (explaining the blue color of queried: "I am much puzzled by some recent sized from ammonium nitrite and other inor- the sky) and Rayleigh waves (e.g., surface earth- results as to the density of nitrogen, and shall ganic precursors. Several persons responded, quake waves). He received the Nobel Prize in be obliged if any of your chemical readers can including James Dewar (1842-1923), inventor Physics in 1904 for "his investigations of the offer suggestions as to the cause...." Rayleigh's of the eponymous flask; William Crookes 5 densities of the most important gases and for data showed, for a 1800-cc flask, (1832-1919), discoverer of thallium ; and his discovery of argon." 2.3102 0.0002 grams for atmospheric nitrogen William Ramsay (vide infra). Crookes was the 36 THE HEXAGON/FALL 2012 I Figure 3. The critical experiment of Rayleigh was on this balance on a marble slab in the weighing room in the basement of his laboratory complex at Terling, where he noted the discrepency between "physical"nitrogen (from the atmosphere) and "chemical" nitrogen (synthesized from inorganiccompounds). PUI~ - 4 LII Figure 5. This is Slade Hall of University College, London, now the art building but previously the Science Building where Ramsay performed his research (Gower Court, N51 31.50 WOO0 08.03), 100 meters Figure 4. Portraitof Sir William Ramsay, painted southwest of the Ingold Laboratories. by Mark Milbanke in 1913. This hangs in the Ramsay Lecture Theatre Hall of the Chemistry resulting nitrogen oxides with caustic potash University College, London, in 1887 (Figure 5), Building (ChristopherIngold Laboratories), (KOH), measure the density; repeat until the replacing Alexander Williamson (1824-1904, University College, London, 20 Gordon Street, density does not change. 2 who had proved the divalency of oxygen in 0 London (N51 31.52 WOO 07.95). Ramsay was 1850.5b). Upon reading Rayleigh's publication in 6 perfectly fluent in German and French and could William Ramsay. Sir William Ramsay Nature, Ramsay asked him if he could carry out lecture expertly in these languages to scientific (1852-1916) (Figure 4), the co-discoverer of his own investigative studies on the problem. audiences who were spellbound by his eloquence. argon, won the 1904 Nobel Prize in Chemistry Both agreed that the discrepancy was probably simultaneously with Rayleigh for "the discov- due to a heavier impurity in the atmospheric only one with a specific suggestion, which ery of the inert [noble] gaseous elements in air, nitrogen, because all known lighter gases, such recalled Cavendish's earlier research: add oxy- and his determination of their place in the peri- as hydrogen, methane, ethylene, etc., had been gen to the nitrogen and spark, remove the odic system." Ramsay became professor at diligently removed (helium was not yet discov- FALL 2012/THE HEXAGON 37 I c n Y it ... n : w , 1 n ,M, h," « .. _ Y i I _ Y <,tl I NOON 1 1' Ili _ . I I I , _ . 4 a I tV Figure 7. This is a model of apparatus used by Ramsay and Travers, located in the Science Museum, Exhibition Road, South Kensington, London. There were many variations of apparatus, most including ballast air tanks; Figure 6. Rayleigh used this globe (1-foot diameter) to collect argon by sparking manometers; pumps; tubes to remove all chemically reactive gases-copper atmospheric nitrogen; it is on exhibit at the Royal Institution in London (21 0 to remove oxygen, copper oxide for hydrogen, soda-lime for carbon dioxide, Albemarle Street; N51 30.58 WO0 08.58). phophorous pentoxide for water, and finally magnesium to remove nitrogen. The tubes containing copper, copper oxide, and magnesium were heated by Bunsen burners. Exhibits such as this were ered5h). The two decided on different tacks: once on public display, but are now in storage to make way for more "modern, meaningful" exhibits. Rayleigh would remove nitrogen from air by sparking in the earlier fashion of Cavendish (Figure 6); Ramsay would remove nitrogen 0 from air by reaction with hot magnesium Figure 8. of the Royal Society was held at its Burlington (Figure 7). William Travers, House on Picadilly (today the home of the the colleague of Royal Society of Chemistry) with an audience The collaboration. Never was there a more Ramsay who was of 800. A complete review of the research by improbable partnership: the impatient Ramsay the co-discoverer Rayleigh and Ramsay was given, including a and the ultra-cautious Rayleigh. It was "not in of neon, krypton, determination of the ratio Cp/Cv (heat capaci- the character of Rayleigh to do things in a and xenon. ties at constant pressure and volume) of 1.67 hurry,"2 while Ramsay would "make hasty con- which indicated a monatomic gas.1a Then a clusions with a minimum of data." 2 Friends of report by Karol Stanislaw Olszewski Rayleigh resented Ramsay's aggressive style; (1846-1915) of Krakow, Poland7 was presented Lady Rayleigh in her private notes relates how showed that "X"was chemically unreactive and (by Ramsay) of the cold temperature behavior Lord Kelvin was "furious at Ramsay's interfer- suggested that it belonged to a new family in of the gas: specific values of the melting point (- ence" in the "greatest discovery of the century the Periodic Table. 7 189.60), boiling point (-187.0 ), critical temper- [argon]."2 It is true that Rayleigh and Ramsay At the 64th Meeting of the British ature (-121 ), and critical pressure (50.6 atm) could be irritated with each other; however, Association [for the Advancement of Science] were determined, establishing the gas as a sim- each respected the other and they understood at Oxford on August 13, 1894 the two scientists ple substancelob (the modern respective values that the collaborative approaches of a physicist presented a preliminary announcement of the are -189.2 , -185.7 , -122.40, 48.0 atm). Finally, 8 and a chemist could be beneficial. Rayleigh was existence of a new gas in the atmosphere. The William Crookes reported on the spectrum, impressed with Ramsay as an experimenter Chairman, Henry George Madan (1838-1901), which was characteristic and unique.1c and his prompt energetic attack on a problem,2 suggested the name "argon," from Greek argoz while Ramsay revered his elder, even declaring ("idle," "indolent") from its chemical inertness7 Helium and future plans. Barely two that "Rayleigh was the greatest man alive."2'' (Note 1). Considerable doubt existed regarding months after Ramsay's complete description of On August 4, 1894 Ramsay wrote the nature of this new gas -it was simply diffi- argon, 1a he announced (March 29, 1895)" his 2 7 Rayleigh: ' "I have isolated the gas at last... cult for people to believe that under their noses discovery of terrestrial helium.
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