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Biographical Memoirs: Volume 69 (1996)

Chapter: WILLIAM FRANCIS GIAUQUE

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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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Suggested Citation:"WILLIAM FRANCIS GIAUQUE." National Academy of Sciences. 1996. Biographical Memoirs: Volume 69. Washington, DC: The National Academies Press. doi: 10.17226/5193.
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WILLIAM FRANCIS GIAUQUE May I2, IS95-March 2S, 1982 BY KENNETH S. PITZER AND DAVID A . SHIRLEY WILLIAM FRANCIS GlAUQUE IS remembered particularly for his discovery of adiabatic demagnetization as a means to reach very Tow temperatures as well as for his exhaustive en c! meticulous thermodynamic studies, over a lifetime of research, which utilizer! the thirc! law of thermodynamics while also developing a large body of evidence for its vaTid- ity. His "achievements in the field! of chemical thermocly- namics en c! especially his work on the behavior of matter at very Tow temperatures en c! his closely allies! studies of en- tropy" were cites! by the Nobel Committee for Chemistry in the aware! of the prize in 1949. Giauque was born May 12, IS95, in Niagara Falls, Ontario, Canada, the elclest of two sons en c! one daughter of Will- iam Tecumseh Giauque en c! Isabella Jane (Duncan) Giauque. His father was an American citizen, en c! thus William Francis Giauque was able to aclopt American citizenship although born in Canada. Neither of Giauque's parents completed a formal high school education, but both were convincer! of the value of education. His father was a skillet! carpenter en c! cabinetmaker en c! was aclept at mechanical procedures in general. He was employer! variously as a weighmaster ant! station agent for the Michigan Central RailroacI. 39

40 B I O G RA P H I C A L EMOIRS Giauque's mother was skillet! in sewing en c! tailoring en c! worker! in those occupations on occasion. His father flier! when Giauque was thirteen, leaving the family with meager financial resources that hac! to be supple- mentec! from part-time en c! summer jobs by all members. Among these jobs was part-time seamstress work by the mother for the family of Dr. John Woocis Beckman, assignee! to Niagara Falls by his employer, American Cyanamic! Com- pany. This connection hac! a pivotal role in William Francis Giauque's later education en c! career. To his mother's consternation, Giauque macle a youthful, headstrong decision upon entering high school that he wouIc! prepare for gainful employment as soon as possible, he electec! the two-year business course rather than the five- year college-preparatory course. Unable to change Giauque's mine! en c! distraught that he wouic! forego a college ecluca- tion because of financial pressure, Mrs. Giauque enlister! the help of Mrs. Gertrude Wheeler) Beckman. Giauque often clescribec! to his students the Tong walk he took with Mrs. Beckman in the course of which she contrasted! for him the experience of her brothers. One had foregone a college education, a second, Charles Stetson Wheeler, graclu- ated from the University of California with the class of ISS4, hac! a highly successful career as an attorney, en c! server! as a regent of the university from 1902 to 1907 (anc! later from 1911 to 1923~. Giauque switcher! to the college-prepa- ratory curriculum, with electrical engineering as his goal. His search for employment upon graduation from high school lee! Giauque, by chance, to the Hooker Electrochemical Company, in Niagara Falls, New York, where his new fasci- nation with chemistry changer! his career goal from electri- cal to chemical engineering. His supervisor, Mr. Burr H. Ritter, assisted this change by answering his questions about chemistry whether they were relater! to the work or not,

WILLIAM FRAN CI S GIAU QUE 41 en c! he fully supporter! Giauque's decision to leave Hooker after two years to continue his education. Mr. Ritter also promptly ant! permanently changer! Giauque's nickname from Frank to Bill, at least among chem- ists, to avoic! confusion with another employee. The thought of his having a nickname assignee! by someone else wouIc! have amazes! his students, who knew him in later years as "Giauque" en c! aciciressec! him as "Professor Giauque." They realizer! that he was caller! Frank by his family en c! Bill by his peers, but his stern demeanor en c! his practice of always aciciressing them by their last names, unaclornec! by moclifi- ers, cliscouragec! experimentation along these lines on their part. Again the Beckmans were to play a key role in cletermin- ing Giauque's future direction. While Giauque worker! at Hooker, Dr. Beckman, himself an electrochemical engineer with American Cyanamid, hac! been transferred to Berke- ley. When Giauque's mother wrote to Mrs. Beckman of Giauque's decision to enter chemical engineering, Mrs. Beckman wrote back about her husbancl's admiration for the work that G. N. Lewis and his colleagues, J. H. Hildebrand, W. C. Bray, en c! others, were cloing at the University of California. Giauque hac! been considering the Massachu- setts Institute of Technology en c! Rensselaer Polytechnic Institute, but Lewis's scientific reputation, the pleasant cTi- mate, en c! the fact that there was no tuition, even for out of-state students, at that time en c! only a total of $10 per semester in fees combiner! to persuacle him to move to Berkeley in August 1916 en c! enroll at the University of California. Giauque thus began an association with the College of Chemistry, University of California, that laster! for the re- maining sixty-six years of his life, as unclergracluate, graclu- ate student, faculty member, en c! professor emeritus, unin

42 B I O G RA P H I C A L EMOIRS terruptec! by sabbatical leaves en c! with few trips macle for any purpose except to receive major awards. He also per- suaclec! his family to move to Berkeley in 1919 when his brother en c! sister were really to enter the university. Motivatec! in part by the new! to support himself through part-time work throughout his student years, Giauque lee! a life style even as an unclergracluate that was orderly in the extreme. He neither smokes! nor cirank alcoholic bever- ages, by preference. Although while in high school he rarely passer! up an opportunity to play basketball, as an uncler- gracluate time constraints limiter! his participation in sports to the boxing team cluring his freshman year. He also cle- ciclec! at an early age to react no more fiction, regarding time thus spent as waste cI. As an unclergracluate Giauque continues! his interest in engineering as well as chemistry, en c! he receiver! very sub- stantial engineering training that servec! him well in plan- ning en c! carrying out his later scientific work. However, the faculty assemblec! by G. N. Lewis soon stimulates! his primary interest towarc! funciamental research. During his senior year Giauque pursued low-temperature research on the thirc! law of thermodynamics uncler the direction of G. E. Gibson research that was to evolve into his life's work. After graduation in 1920 with a B.S. in chemistry (with highest honors), Giauque was awarclec! a university fellow- ship to continue his education, earning a Ph.D. in chemis- try in 1922, with a minor in physics. His thesis research, also supervisec! by G. E. Gibson, was on the heat capacity of glycerol. It showed that the third law of thermodynamics cannot be applied directly to the disordered systems known as glasses. In later life, Giauque likes! to point out to his students the four-year gap between the publication of his thesis work in 1923 en c! his next publication, as proof by example that a large number of early publications are not

WILLIAM FRAN CI S GIAU QUE 43 essential for an academic career with tenure, if one's senior colleagues have enough patience. Giauque was informer! by G. N. Lewis early in 1922 that he wouic! be offerer! a faculty appointment upon comple- tion of his Ph.D. work, en c! he weighec! this offer for several months before accepting. He had planned to apply the fun- ciamental science that he hac! learner! to engineering prob- lems, en c! he also hac! clone no teaching in his two-year tenure as a graduate student, having been able to devote all his available time to his studies for the first time since en- tering college. The excellent research atmosphere in the College of Chemistry prevailed and Giauque accepted the offer, although his interest in engineering persistec! through- out his career en c! was often expressed by his tendency to clo research on a pilot-plant scale. He clesignec! en c! super- visec! the construction of the heavy equipment for the liq- uefaction of both hydrogen en c! helium, as well as for the procluction of the high, uniform magnetic fielcis neeclec! for his research. He was registered as a professional engi- neer in the state of California. During his graduate studies en c! in his early clays as a faculty member, Giauque interacted! extensively with Raymonc! T. Birge of the physics department. He thus acquirer! an unclerstancling of the applicability of quantum statistics to the calculation of thermodynamic quantities, in particular calculation of the absolute entropy of any gas of cliatomic molecules from spectroscopic ciata. Giauque realizer! that this would provide an absolute reference with which he coup! compare calorimetric values of entropy, thus achiev- ing a more definitive test of the thirc! law of thermoclynam- ics than hac! previously been possible. His stucly of the spectra of cliatomic molecules lee! to the discovery of the isotopes of oxygen. While the spectra of i60-~60 gave a calculated entropy in agreement with the

44 B I O G RA P H I C A L EMOIRS calorimetric measurements, some faint lines in the oxygen spectrum remainec! unexplainecI. With typical thoroughness, he explorer! several possibilities, conclucling finally that an isotopic molecule i60-~8O wouic! exhibit the unexplainec! lines. The worIc! authority on isotopes, Aston, hac! stucliec! oxygen with a mass spectrograph. He asserter! that only i60 existec! en c! thus that oxygen was an icleal atomic weight reference. Unciauntec! by Aston's authority, Giauque calcu- latec! the frequencies expecter! for the i60-~8O molecule en c! fount! agreement with the unexplainec! faint lines. How- ever, his calculations preclictec! a number of aciclitional lines that were not incluclec! in the ciata reporter! by Dieke en c! Babcock, whose spectra he was using. These authors hac! not reporter! faint lines that clic! not lie close to strong ones, believing that they were not associated with oxygen. At Giauque's request, Babcock proviclec! the unreported lines, most of which agrees! with Giauque's predictions. Further stucly iclentifiec! the i70 isotope as well. The discovery of the oxygen isotopes provided the first clear proof that mol- ecules retain zero-point vibrational energy at absolute zero temperature. It also revealer! that physicists en c! chemists hac! unknowingly been using different atomic weight scales, a situation that persistec! until the i2C scale was acloptec! in 1961. Giauque's discovery of adiabatic demagnetization was a consequence of his broac! scientific interests as well as his keen and innovative mind. In the fall of 1924 another young colleague, Nelson W. Taylor, invites! Giauque to join him in cleveloping a seminar on magnetism, which Taylor was stucly ing. Giauque agreed to present anything he could learn about the relationships of thermodynamics with magnetism. After following several lines of investigation in which the small effect of magnetism on total energy lee! to uninterest- ing results, Giauque came across a report from Leiclen on

WILLIAM FRAN CI S GIAU QUE the Tow-temperature 45 magnetic susceptibility of G]2(S04) 3 SH2O. Because of the eightfold spin degeneracy of the GcI+3 ion, a large resiclual entropy remainec! in this salt, in the absence of a magnetic fielcI, even at very Tow temperatures. Applying the thermodynamic equations that he hac! just clevelopecI, Giauque fount! that reaclily available magnetic fielcis conic! remove very substantial amounts of entropy from this or similar systems at very low but cur rently accessible temperatures. Given his engineering train ~ng, I, ~ with heat engines en c! refrigerating machines, en c! aclia- batic demagnetization became obvious to him as a means for achieving Tower temperatures than those available by the conventional use of cryogenic liquicis. Giauque sharer! his iclea for magnetic cooling, conceivec! late in 1924, freely with his colleagues en c! with visitors to Berkeley from European laboratories, en c! he publisher! it . it was natural for him to associate entronv changes in 1927, but over eight years passed before Giauque and MacDougall, his student, carrier! out the first adiabatic cle- magnetization experiment in March 1933. The Berkeley labo- ratory was ill equippec! to concluct the experiment when it was conceived, lacking a helium liquefier en c! an air-core magnet, which wouIc! be requires! for meaningful measure- ments of the final low temperatures reached upon demag netization. Characteristically, Giauque set out on a Tong- range program to clevelop the necessary equipment. Although he hac! the support of G. N. Lewis en c! W. M. Latimer, who favorer! him in the allocation of scarce resources, there was very little money available for research. Colleagues at bet- ter-funclec! low-temperature laboratories in Europe conic! have carried out the experiment earlier, but perhaps they lackey! Giauque's conviction. It was in 1933 that all of the equipment was completed and Giauque's first demagnetiza- tion experiment yielclec! 0.25 K.

46 B I O G RA P H I C A L EMOIRS In aciclition to lesser honors, Giauque was electec! to the National Academy of Sciences in 1936 en c! to the American Philosophical Society in 1940. He receiver! the Nobel Prize in chemistry in 1949. Muriel Francis Ashley, who earnec! a B.S. in chemistry at the University of California in 1922, hac! been a longtime frienc! of both Giauque's sister en c! mother, but it was only after she returnee! to Berkeley for her graduate work in physics that he displayed any interest in her. On the day that she filet! her Ph.D. thesis in 1932 she en c! Giauque were married. The union proclucec! two sons, William Francis Ashley Giauque en c! Robert Davic! Ashley Giauque, en c! four grancichiTciren. Muriel became an accomplishes! botanist, specializing in fern spores collectec! for her by a worIc~wicle network of friends. Although characteristically reserves! in direct praise, Giauque was clearly very prouc! of her accom- plishments. When the Giauques traveler! to Stockholm for his Nobel award, she receiver! almost comparable attention from her botanist friencis. Giauque's students remember pleasant Thanksgiving clinners at the Giauque home, with Muriel as cook en c! Frank (as she caller! him) as raconteur, with a keen sense of humor. The stories he most enjoyed telling were those in which the joke was on him. She precle- ceased him by eight months, on July 28, 1981. Although adiabatic demagnetization was a dramatic clis- covery, Giauque's primary interest was in entropy en c! the thirc! law of thermodynamics, which he explorer! by meticu- Tously accurate absolute measurements: in this context, mag- netic cooling was a means to an end. He eschewer! making approximate measurements and insisted on a target accu- racy of a tenth of I%, a tall order for thermodynamic ciata. He envisioned! builcling a 10-Tesla iron-free magnet large enough to produce a uniform magnetic field over a volume of 100 cubic centimeters or more, with an iron-free envi

WILLIAM FRAN CI S GIAU QUE 47 ronment over a lO-meter diameter. This project took over two more clecacles, reaching completion only in 1959, with the successful operation of a multiple-layer solenoic! of 3/4- inch by ~ /4-inch copper conductor carrying ~ 0,000 am- peres of current ant! dissipating 7 megawatts of power. Giauque insistec! that magnetic samples be accurately ellip- soicial, en c! he requires! that all calorimetric measurements, magnetic or not, be macle by clirect-current methods. Stan- ciarc! cells from the National Bureau of Stanciarcis were cle- liverec! first to his laboratory, where they were treater! with great respect. They were releaser! to the college only when the next shipment of stanciarc! cells arrived. After the Low- Temperature Laboratory (later the Giauque Laboratory) was completec! in 1954, en c! the first lO-Tesla magnet was fin- ishec! in 1959, Giauque en c! his colleagues proceeclec! with magnetic en c! thermodynamic studies of paramagnetic com- pounds as he had originally intended forty years earlier. Many of his later publications report careful en c! accurate ciata on these compounds, setting an enviable stanciarc! for future workers. Giauque's research interests were not restrictec! to mag- netic systems or to very Tow temperatures. Early in his ca- reer he measurer! the heat capacities en c! heats of transi- tion of the halogen acicis from very low temperatures upward. With his careful measurements the excitations of degrees of freedom "frozen in" at very low temperatures (e.g., mo- lecular rotation) were iclentifiec! as sharp anomalies in the heat capacity. In other molecular systems, accurate heat ca- pacity measurements allowed! him to identify random mo- lecular orientations that shower! up as resiclual entropies, such as S= Rind for the carbon monoxide molecule, which could be oriented as C-O or O-C. The structure of ordinary ice was of special interest in this regard. Giauque expecter! a molecular rotation degree of freedom, while Linus PauTing

48 B I O G RA P H I C A L EMOIRS proposer! a tetraheciral structure for the oxygen atoms, con- nectec! by random hydrogen bonds, leacling to a resiclual entropy S= RIn3/2. Giauque en c! Stout confirmed! this value experimentally, supporting PauTing's moclel. Giauque user! this example to convince his students of the new! for care- ful measurement as well as the superiority of fact over specu- lation. In aciclition to his interest in magnetic salts en c! simple molecules that illustrates! statistical thermodynamic prin- ciples, Giauque macle substantial contributions to instru- mentation en c! experimental techniques. He helpec! to re- fine low-temperature scales throughout his career. He wrote an amusing parable in Nature in 1939 as a plea to use a single fixed point in defining the size of the degree in the absolute temperature scale. He also stucliec! the chemically very important en c! clifficult systems of sulfuric acid en c! sodium hyciroxicle over a perioc! of years from 1950, using low-temperature calorimetry ant! other thermodynamic measurements to establish the properties of these compli- catec! en c! corrosive materials. Giauque's conservatism was legendary. He always appeared at the university ciressec! in an iron-gray twee c! suit. He re- countec! that one clay in 1924 he hac! sought clothing ap- propriate for a young faculty member en c! hac! a tailor make him a suit. He bought the suit en c! the bolt of cloth from which it was macle, en c! over the years he always owner! two iclentical suits. Whenever a jacket or pair of trousers shower! enough wear, he hac! another macle from that material, which laster! for over twenty years. He did not learn to drive an automobile and did not own one until after receiving the Nobel Prize in 1949. He liver! only seven blocks from the Berkeley campus en c! walker! each way, except in his later years. Then he suffered from arthritis, and his wife Muriel drove him to work and back.

WILLIAM FRAN CI S GIAU QUE 49 His conservatism was expressed in many ways in the labo- ratory. Giauque requires! that permanent metal joints be h are! soIclerecI, then coverer! with soft soIcler to ensure vacuum tightness. For many years his students user! "ball-vee" vacuum- tight seals to hoIc! sample chambers in place. Both surfaces in these seals were macle of clean stainless steel, en c! a torque wrench was user! to create a vacuum-tight seal without cle- forming the steel. It was through these en c! other meticu- lous but very clifficult techniques that Giauque en c! his stu- clents were able to make precise absolute measurements. Giauque's immunity to social facts hac! its counterpart in his scientific work. Although well versed in statistical me- chanics, he was comfortable with the more empirical per- spective of thermodynamics when he felt the situation war- rantec! it. He also enjoyoc! the role of iconoclast when he felt that a colleague's approach clicin't cleliver all that it acivertisecI. He jokingly referrer! to unusual g-factors as the "activity coefficients of magnetism," en c! he was very unen- thusiastic about the ease with which the concept of spin temperature was acloptec! en c! applier! to assign negative temperatures to systems with inverted populations, without also demonstrating the requisite rapic! internal "thermal" equilibrium. Giauque taught his research students to be the most cle- mancling critics of their own ciata, reasoning that once pub- lishec! their work wouIc! then stanc! the test of time. He conveyor! to them many of the practical aspects of experi- mental science, such as the improvement in accuracy on integrating, ant! loss on differentiating, a ciata set, the unreliability of the first point in a heat-capacity run be- cause of hysteresis, en c! the advantages en c! pitfalls of least- squares fitting procedures. A dominant personality himself, Giauque not only tolerated but respected students who dis

50 B I O G RA P H I C A L EMOIRS agrees! with him, en c! he was especially pleaser! when they conic! prove their point. The constancy of Giauque's commitment to classroom teaching was no less remarkable than his cleclication to re- search. Starting with his appointment as instructor in 1922, he taught a discussion laboratory section of the freshman chemistry class in every semester for thirty-four consecutive years. In 1926 G. N. Lewis assignee! him the responsibility for teaching the college's course in acivancec! physical chem- istry, taken mainly by graduate students. Giauque taught that course every spring semester thereafter until his nomi- nal retirement in June 1962. His classroom style was to lec- ture while using the blackboarc! to solve problems en c! prove points. His tests were problem basecI, en c! the problems were clesignec! to test the students' unclerstancling in depth. Over the years oic! problems recurrec! in somewhat alterec! forms, en c! students acloptec! the strategy of studying collec- tions of problems that Giauque hac! user! in previous years. Giauque must have regarclec! this as a goof! way to learn the material. In 1943 he also assumer! the responsibility for a section of chemical thermodynamics for graduate en c! un- clergracluate honors students, which he taught every fall semester through 1960. While eschewing administrative posts in the university, he unstintingly gave his time in helping students, serving as aciviser for unclergracluates in the Col- lege of Letters en c! Science who wisher! to major in chemis- try throughout the perioc! 1945-60. Giauque Tovec! his work en c! macle it the dominant part of his life, commenting on many occasions that he clicin't new! vacations because he spent the whole year cloing what he enjoyed most. His legacy is that of one of the later major figures in the clevelopment of chemical thermodynamics, specifically regarding the influence of atomic en c! molecu- lar structure on entropy en c! the thirc! law of thermocly

WILLIAM FRAN CI S GIAU QUE 51 namics. His work will Tong endure in the textbooks. His influence on colleagues en c! students, though largely unre- corclecI, will also endure.

52 B I O G RA P H I C A L S E L E C T E D EMOIRS B I B L I O G RAP H Y 1923 With G. E. Gibson. The third law of thermodynamics. Evidence from specific heats of glycerol that the entropy of a glass exceeds that of a crystal at the absolute zero. 7. Am. Chem. Soc. 45:93-104. 1927 A thermodynamic treatment of certain magnetic effects. A proposed method of producing temperatures considerably below 1° abso- lute. 7. Am. Chem. Soc. 49:1864-70. Paramagnetism and the third law of thermodynamics. Interpreta- tion of the low-temperature magnetic susceptibility of gadolinium sulfate. 7. Am. Chem. Soc. 49:1870-77. 1928 With R. Wiebe. The entropy of hydrogen chloride. Heat capacity from 16°K. to boiling point. Heat of vaporization. Vapor pres- sures of solid and liquid. 7. Am. Chem. Soc. 50:101-22. With H. L. Johnston. Symmetrical and antisymmetrical hydrogen and the third law of thermodynamics. Thermal equilibrium and the triple point pressure. 7. Am. Chem. Soc. 50:3221-28. 1929 With H. L. Johnston. An isotope of oxygen, mass 18. Interpretation of the atmospheric absorption bands. 7. Am. Chem. Soc. 51:1436- 41. With H. L. Johnston. The heat capacity of oxygen from 12°K to its boiling point and its heat of vaporization. The entropy from spec- troscopic data. 7. Am. Chem. Soc. 51:2300-2321. Isotope effect in spectra and precise atomic weights. Nature August 17. With H. L. Johnston. An isotope of oxygen, mass 17, in the earth's atmosphere. J. Am. Chem. Soc. 51 :3528-34. 1930 The entropy of hydrogen and the third law of thermodynamics.

WILLIAM FRAN CI S GIAU QUE 53 The free energy and dissociation of hydrogen. 7. Am. Chem. Soc. 52:4816-31. The calculation of free energy from spectroscopic data. 7. Am. Chem. Soc. 52:4808-15. 1931 Nuclear spin and the third law of thermodynamics. The entropy of iodine. 7. Am. Chem. Soc. 53:507-14. 1932 With T. O. Clayton. The heat capacity and entropy of carbon mon- oxide. Heat of vaporization. Vapor pressures of solid and liquid. Free energy to 5000°K. from spectroscopic data. 7. Am. Chem. Soc. 54:2610-26. With C. W. Clark. The conditions for producing temperatures be- low 1° absolute by demagnetization of Gd2(SO4~3~8H2O. Tem- perature-magnetic field isentropics. 7. Am. Chem. Soc. 54:3135-42. 1933 With M. F. Ashley. Molecular rotation in ice at 10°K. Free energy of formation and entropy of water. Phys. Rev. 43:81-82. With D. P. MacDougall. Attainment of temperatures below 1° abso- lute by demagnetization of Gd2(SO4~3~8H2O. Phys. Rev. 43:768. With T. O. Clayton. The heat capacity and entropy of nitrogen. Heat of vaporization. Vapor pressures of solid and liquid. The reac- tion 1/2N2 + 1/2 O2 = NO from spectroscopic data. 7. Am. Chem. Soc. 55:4875-89. 1936 With T. W. Stout. The entropy of water and the third law of thermo- dynamics. The heat capacity of ice from 15 to 273°K. 7. Am. Chem. Soc. 58:1144-50. 1937 With C. J. Egan. Carbon dioxide. The heat capacity and vapor pres- sure of the solid. The heat of sublimation. Thermodynamic and spectroscopic values of the entropy. 7. Chem. Phys. 5:45-54. With C. C. Stephenson. A test of the third law of thermodynamics by means of two crystalline forms of phosphine. The heat capac

54 B I O G RA P H I C A L EMOIRS ity, heat of vaporization and vapor pressure of phosphine. En- tropy of the gas. J. Chem. Phys. 5:149-58. 1938 With T. D. Kemp. The entropies of nitrogen tetroxide and nitrogen dioxide. The heat capacity from 15°K. to the boiling point. The heat of vaporization and vapor pressure. The equilibrium N204 = 2NO + O2. J. Chem. Phys. 6:40-52. 1939 With T. W. Stout and R. E. Baricau. Measurements of the viscosity of liquid helium II. 7. Am. Chem. Soc. 61:654-61. A proposal to redefine the thermodynamic temperature scale. A parable of measures to improve weights. Nature 143:623-32. With T. M. Powell. Propylene. The heat capacity, vapor pressure, heats of fusion and vaporization. The third law of thermodynam- ics and orientation equilibrium in the solid. 7. Am. Chem. Soc. 61 :2366-70. 1941 With T. W. Stout, C. T. Egan, and C. W. Clark. The measurement of adiabatic differential magnetic susceptibility near 1° absolute. The heat capacity of gadolinium phosphomolybate tridecahydrate from 0.17 to 4.7° absolute. 7. Am. Chem. Soc. 63:405-10. 1942 With W. R. Forsythe. The entropies of nitric acid and its mono- and tri-hydrates. Their heat capacities from 15 to 300°K. The heats of dilutions at 298.1°K. The internal rotation and free energy of nitric acid gas. The partial pressures over its aqueous solutions. J. Am. Chem. Soc. 64:48-61. Errata: 7. Am. Chem. Soc. 64:3069 (1942~; 65:2379 (1943~. 1949 With T. T. Fritz and D. N. Lyon. The measurement of magnetic susceptibility at low temperatures. 7. Am. Chem. Soc. 71:1657-64. Some consequences of low temperature research in chemical ther- modynamics. Nobel lecture, delivered in Stockholm, December 12, pp. 91-114.

WILLIAM FRAN CI S GIAU QUE 1953 55 With R. H. Busey. The equilibrium reaction NiCl2 + H2 = Ni + 2HC1. Ferromagnetism and the third law of thermodynamics. 7. Am. Chem. Soc. 75: 1791. Determination of thermodynamic temperatures near 0°K. without introducing heat below 1°K. Phys. Rev. 92:1339. 1959 With D. A. Shirley. The entropy of iodine. Heat capacity from 13 to 327°K. Heat of sublimation. 7. Am. Chem. Soc. 81:4778. 1960 With E. W. Hornung, J. E. Kunzler, and T. R. Rubin. The thermody- namic properties of aqueous sulfuric acid solutions and hydrates from 15 to 300°K. 7. Am. Chem. Soc. 82:62-70. Erratum: 7. Am. Chem. Soc. 83:5047 ~ 1962) . 1965 With G. E. Brodale. The heat of hydration of cobalt sulfate hexahy- drate to heptahydrate. Their solubilities and heats of solution. 7. Phys. Chem. 69:1268-77. 1967 With E. W. Hornung, R. A. Fisher, and G. E. Brodale. Thermody- namic temperature and heat capacity of NiSiF6~6H2O without heat introduction below 0.35°K. Magnetic moment and internal energy from 0.05° to 4.2°K. Fields 0-90 kG perpendicular to the c axis. 7. Chem. Phys. 47:2685-700. 1969 With R. A. Fisher, E. W. Hornung, and G. E. Brodale. Magneto- thermodynamics of a-NiSO4~6H2O. V. Proton spin polarization rate and activation enthalpy as a function of temperature and field to 90 kG along the or axis. J. Chem. Phys. 51:1959-65. 1970 With R. A. Fisher, E. W. Hornung, and G. E. Brodale. Magneto- thermodynamics of antiferromagnetic a-MnCl2~4H2O. IV. Reversibility

56 B I O G RA P H I C A L EMOIRS conditions in the a, b, and p regions with Hi ~ c axis. Spin Flop, an inappropriate term. 7. Chem. Phys. 53:1474-90. 1971 With R. A. Fisher, E. W. Hornung, and G. E. Brodale. Magneto- thermodynamics of CuK2(SO4~2~6H2O. V. Fields along the or axis. Thermodynamic temperature without heat introduction below 0.5°K. The freezing-in of magnetic structure in the lambda re- gion. J. Chem. Phys. 55:2859-67. 1972 With G. E. Brodale. The relationship of crystalline forms I, III, IV, and V of anhydrous sodium sulfate as determined by the third law of thermodynamics. 7. Phys. Chem. 76: 737-43. 1973 With R. A. Fisher, E. W. Hornung, and G. E. Brodale. Magneto- thermodynamics of Ce2Mg3 (NO3~2~24H2O. II. The evaluation of absolute temperature and other thermodynamic properties of CMN to 0.6 millidegrees. 7. Chem. Phys. 58:5584-5604. Erratum: 7. Chem. Phys. 61:3869 ~ 1974) . 1975 With R. A. Fisher, E. W. Hornung, and G. E. Brodale. Magneto- thermodynamics of Ce2Zn3 (NO3~2~24H2O. II. Determination of absolute temperature and other thermodynamic properties of CZN to 0.80 m°K. 7. Chem. Phys. 62:555-72. With G. E. Brodale, E. W. Hornung, and R. A. Fisher. Magneto- thermodynamics of gadolinium gallium garnet. III. Heat capac- ity, entropy, magnetic moment from 0.5 to 4.2°K, with fields to 90 kG along the t110] axis. 7. Chem. Phys. 62:4041-49. With R. A. Fisher, G. E. Brodale, and E. W. Hornung. Magneto- thermodynamics of single crystal CuSO4 5H2O. VI. Properties below 0.5°K by heat introduction with constant fields to 33 kG along the ~ axis. The initial T3 dependence of entropy and heat capac- ity for dipole-dipole magnetic interactions. J. Chem. Phys. 63:4817- 30. . .

WILLIAM FRAN CI S GIAU QUE 1978 57 With R. A. Fisher, G. E. Brodale, and E. W. Hornung. Magneto- thermodynamics of Nd (C2H3SO4) 3. 9H2O. IV. Determination of absolute temperature scales and other properties below 0.5°K with constant magnetic fields along the a crystal axis. 7. Chem. Phys. 68:169-84. With R. A. Fisher, E. W. Hornung, and G. E. Brodale. Magnetothermodynamics of antiferromagnetic, polarized ferro- electric, ferroelastic B-Gd2 (Moods. V. Thermodynamic temperature and other properties with heat introduction below 0.5°K. Fields to 5 kG along the b crystal axis. 7. Chem. Phys. 69:2892-2900.

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Biographic Memoirs: Volume 69 contains the biographies of deceased members of the National Academy of Sciences and bibliographies of their published works. Each biographical essay was written by a member of the Academy familiar with the professional career of the deceased. For historical and bibliographical purposes, these volumes are worth returning to time and again.

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