The Inter-Relations of Hydrogen and Deuterium Molecules

Gould, A.; Bleakney, Walker; Taylor, Hugh S.

doi:10.1063/1.1749490

Cited by 49 publications

(13 citation statements)

References 25 publications

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“…The thermodynamic equilibrium constant for the three hydrogen isotopologues was calculated from molecular masses and internal partition sums, using the results of recent ab initio calculations of the energy levels of H 2 , D 2 and HD (Figure ). The uncertainty of this calculation is estimated at about 1‰ or smaller for the entire temperature range between 5 and 1000 K. Overall, our results agree well with previous experimental and theoretical results; the only possible difference is with Gould et al at −190°C. This lets us safely conclude that the equilibrium constant is well known at the uncertainty level of 1‰ all over the temperature range between 100 and 2000 K.…”

Section: Methodssupporting

confidence: 90%

H₂ clumped isotope measurements at natural isotopic abundances

Popa

Paul

Janssen

et al. 2019

Rapid Comm Mass Spectrometry

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Rationale Molecular hydrogen (H 2 ) is an important gas for atmospheric chemistry, and an indirect greenhouse gas due to its reaction with OH. The isotopic composition of H 2 (δD) has been used to investigate its atmospheric budget; here we add a new observable, the clumped isotopic signature ΔDD, to the tools that can be used to study the global cycle of H 2 . Methods A method for determining ΔDD in H 2 was developed using the high‐resolution MAT 253‐Ultra isotope ratio mass spectrometer (Thermo Fisher). The HH, HD and DD abundances are quantified at medium resolution (M/ΔM ≈ 6000), which is sufficient for HD + and DD + to be distinguished from H 3 + and H 2 D + , respectively. The method involves sequential measurement of isotopologues, and DD is measured using an ion counter. For verification, catalytic ΔDD equilibration experiments were performed at temperatures of up to 850°C. Results The typical precision obtained for ΔDD is 2–6‰, close to the theoretical counting statistics limit, and adequate for detecting the expected natural variations. Compatibility and medium‐term reproducibility are consistent with the precision values. The method was validated using temperature equilibration experiments, which showed a dependence of ΔDD on temperature as expected form theoretical calculations. Conclusions We have established a method for determining ΔDD in H 2 at natural isotopic abundances, with a precision that is adequate for observing the expected variations in atmospheric and other natural H 2 . This method opens the road to new research on the natural H 2 cycle.

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Section: Methodssupporting

confidence: 90%

H₂ clumped isotope measurements at natural isotopic abundances

Popa

Paul

Janssen

et al. 2019

Rapid Comm Mass Spectrometry

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“…The data of Rittenberg, Bleakney, and Urey [54] were obtained from measurements on hydrogen-deuterium mixtures prepared by the decomposition of mix-( tures of HI and DI, and those of Gould, Bleakney, and Taylor [55] were obtained with mixtures of hydrogen and deuterium that had been adsorbed on various catalysts or had been diffu sed t hrough palladium. Some of the obser vations of Gould , Bleakney, and Taylor plotted in figure 5 were not plotted by them in their published article.…”

Section: Journal Ofmentioning

confidence: 99%

“…G. Kannuluik [130], who obtained respectively, the values 0.7365 and 0.7324' By using the mean of th ese values with appropriate values of Cp and 7), one obtains for U ll in eq 6.7 for the thermal conductivity of D z at 0 0 C the value 1. 55. Archer also measured the thermal cond uctivity of various equilibrium mixtures of H 2, HD, and D z.…”

Section: Fjmentioning

confidence: 99%

Compilation of thermal properties of hydrogen in its various isotopic and ortho-para modifications

Woolley¹,

Scott²,

Brickwedde³

1948

J. RES. NATL. BUR. STAN.

445

119

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New developments in science and industry are aided by accurate knowledge of the behavio r of important substances. The great abundance of chemical processes and compounds in which hydrogen is involved make it of partipular interest. The experimental a nd derived data presented here for hydrogen extend over a large range of temperature. Lo,,' temperat ures are required for the liquid and solid, and moderate and high temperatures occur in chemical reac tions.The avai lable thermal data [or H 2, HD, and D~ in solid, liquid, and gaseous states have been brought together, includ in g the di s tinctive properties of ortho and para forms of H2 and D 2• Some data not previously publi~h ed have been added. The thermal data include thermodynamic functions for the ideal gas state, equilibrium constants, data of s tate, viscosity, and thermal conductivity with dependence on the pressure, vapo r pressure, solid-liquid equilibria, specific heats, and latent heats. Values of state derivatives useful in t hermod ynamic calculations have been given for normal hydrogcn, and the related differences between thermodynamic functions for real and ideal gas states havc been evaluated· A temperat ure entropy diagram for normal H 2 in the range of experimen tal data is al 0 given. The compiled thermal properties of hydrogen are presented in 38 tables, 33 graphs, and numerous equations. The sources of the data have been given in an exten sive bibliography.

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“…Similar carbon isotopic compositions of CH 4 and contents of C 2+ alkanes at Lost City, Lucky Strike, and Rainbow (as well as at other unsedimented fields studied to date), despite marked differences in geologic setting, fluid composition, and thermodynamic drive for CH 4 synthesis, are consistent with a common abiotic origin for methane at many, if not all, sediment-poor seafloor hydrothermal systems. (Crist and Dalin, 1933;Gould et al, 1934;Hall et al, 1934;Koepp, 1978;Lyon and Hulston, 1984;Lécluse and Robert, 1994;Campbell et al, 2009;. Reactions were assumed to be first order in CH 4 or H 2 .…”

Section: Decoupling Of Vent Fluid Chemistry and Temperatures From Conmentioning

confidence: 99%

“…Mid-ocean ridge hydrothermal systems Crist and Dalin, 1933;Gould et al, 1934;Hall et al, 1934;Koepp, 1978;Lyon and Hulston, 1984;Lécluse and Robert, 1994;Campbell et al, 2009; …”

mentioning

confidence: 99%

The geochemistry of methane isotopologues

Wang¹

2017

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This thesis documents the origin, distribution, and fate of methane and several of its isotopic forms on Earth. Using observational, experimental, and theoretical approaches, I illustrate how the relative abundances of 12 CH 4 , 13 CH 4 , 12 CH 3 D, and 13 CH 3 D record the formation, transport, and breakdown of methane in selected settings.Chapter 2 reports precise determinations of 13 CH 3 D, a "clumped" isotopologue of methane, in samples collected from various settings representing many of the major sources and reservoirs of methane on Earth. The results show that the information encoded by the abundance of 13 CH 3 D enables differentiation of methane generated by microbial, thermogenic, and abiogenic processes. A strong correlation between clumped-and hydrogen-isotope signatures in microbial methane is identified and quantitatively linked to the availability of H 2 and the reversibility of microbially-mediated methanogenesis in the environment. Determination of 13 CH 3 D in combination with hydrogen-isotope ratios of methane and water provides a sensitive indicator of the extent of C-H bond equilibration, enables fingerprinting of methane-generating mechanisms, and in some cases, supplies direct constraints for locating the waters from which migrated gases were sourced. Chapter 3 applies this concept to constrain the origin of methane in hydrothermal fluids from sediment-poor vent fields hosted in mafic and ultramafic rocks on slow-and ultraslow-spreading mid-ocean ridges. The data support a hypogene model whereby methane forms abiotically within plutonic rocks of the oceanic crust at temperatures above ca. 300• C during respeciation of magmatic volatiles, and is subsequently extracted during active, convective hydrothermal circulation. Chapter 4 presents the results of culture experiments in which methane is oxidized in the presence of O 2 by the bacterium Methylococcus capsulatus strain Bath. The results show that the clumped isotopologue abundances of partially-oxidized methane can be predicted from knowledge of 13 C/ 12 C and D/H isotope fractionation factors alone.: Shuhei Ono, Ph.D. Acknowledgments I fear that this section will not do justice to the people I have not the space to thank individually. Alas, here goes. To those whose names are not specifically listed here, thank you too. I wish first to thank Shuhei Ono. The work this thesis represents could not have happened without his bold vision and the license to explore and question that working in his lab afforded. His unbridled optimism, breadth of scientific curiosity, personal integrity, and accessibility to his personnel are traits I one day hope to emulate. I thank him for his nonjudgmental yet appropriately measured support of many of my ideas-even those that led nowhere-, for believing in me even when I found it difficult to do so myself, and for teaching me to change pump oil, build vacuum lines, and drink Icelandic vodka.I also wish to thank my thesis committee members Jeff Seewald, Roger Summons, and John Pohlman, for their in...

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The Inter-Relations of Hydrogen and Deuterium Molecules

Cited by 49 publications

References 25 publications

H₂ clumped isotope measurements at natural isotopic abundances

H₂ clumped isotope measurements at natural isotopic abundances

Compilation of thermal properties of hydrogen in its various isotopic and ortho-para modifications

The geochemistry of methane isotopologues

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The Inter-Relations of Hydrogen and Deuterium Molecules

Cited by 49 publications

References 25 publications

H2 clumped isotope measurements at natural isotopic abundances

H2 clumped isotope measurements at natural isotopic abundances

Compilation of thermal properties of hydrogen in its various isotopic and ortho-para modifications

The geochemistry of methane isotopologues

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H₂ clumped isotope measurements at natural isotopic abundances

H₂ clumped isotope measurements at natural isotopic abundances