A basic theoretical understanding of stable isotope fractionations can help researczzzhers plan and interpret both laboratory experiments and measurements on natural samples. The goal of this chapter is to provide an introduction to stable isotope fractionation theory, particularly as it applies to mass-dependent fractionations of non-traditional elements and materials. Concepts are illustrated using a number of worked examples. For most elements, and typical terrestrial temperature and pressure conditions, equilibrium isotopic fractionations are caused by the sensitivities of molecular and condensed-phase vibrational frequencies to isotopic substitution. This is explained using the concepts of vibrational zero-point energy and the partition function, leading to Urey’s (1947) simplified equation for calculating isotopic partition function ratios for molecules, and Kieffer’s (1982) extension to condensed phases. Discussion will focus on methods of obtaining the necessary input data (vibrational frequencies) for partition function calculations. Vibrational spectra have not been measured or are incomplete for most of the substances that Earth scientists are interested in studying, making it necessary to estimate unknown frequencies, or to measure them directly. Techniques for estimating unknown frequencies range from simple analogies to well-studied materials to more complex empirical force-field calculations and ab initio quantum chemistry. Mossbauer spectroscopy has also been used to obtain the vibrational properties of some elements, particularly iron, in a variety of compounds. Some kinetic isotopic fractionations are controlled by molecular or atomic translational velocities; this class includes many diffusive and evaporative fractionations. These fractionations can be modeled using classical statistical mechanics. Other kinetic fractionations may result from the isotopic sensitivity of the activation energy required to achieve a transition state, a process that (in its simplest form) can be modeled using a modification of Urey’s equation (Bigeleisen 1949).

Theoretical estimates of isotopic fractionations are particularly powerful in systems that are difficult to characterize experimentally, or when empirical …

Applying Stable Isotope Fractionation Theory to New Systems

The single-stage separation factors for boron isotopes between an ion-exchange resin and an external solution were determined, using an ion-exchange breakthrough operation. The lighter isotope boron-10 was considerably enriched in the anion-exchange resin phase. The separation factor was very much influenced by the boric acid concentration in the external solution, but not as much influenced by the kind of the anion exchange resin used and operation temperature. The separation factor increased with a decrease in the boric acid concentration of external solution from 1.008 (0.501 mol/l) to 1.016 (0.010 mol/l). The value of the separation factors obtained experimentally were compared with those estimated on the basis of the theory of the two-phase distribution of isotopes.

Fundamental studies on the ion-exchange separation of boron isotopes

FT-IR and Raman spectroscopic study of hydrated borates

Indirect photometric chromatography

...................................................... Introduction...................................................................^ Basic Concepts ................................................................................................................................................2 Aclmowledgements...........................................^ Hydrogen...............................................................................................................................................^ Reference materials and reporting of isotope ratios......................................................................................5 Ranges in isotopic composition......................................................................................................................5 Water...................................................................................................................................... Silicates............................................................................................................................................^ Hydroxides...........:...............................................................................^ Organic hydrogen....................................................................................................................................8 Methane .................................................................................................................................................10 Hydrogen gas......................................................................................................................................... 10 Lithium................................................^ Reference materials and reporting of isotope ratios.................................................................................... 11 Ranges in isotopic composition.................................................................................................................... 11 Marine sources ......................................................................................................................................11 Non-marine sources............................................................................................................................... 13 Lithium in rocks.................................................................................................................................... 13 Phosphates............................................................................................................................................. 13 Silicates....... ... . ........... . .... . .. .. . . .... . ....... .._ Reagents............................ .. ..... ... . ... .. ... . . ..............J^ Boron......................................................................... Reference materials and reporting of isotope ratios.................................................................................... 15 Ranges in isotopic composition.................................................................................................................... 15 Marine sources ......................................................................................................................................15 Non-marine sources............................................................................................................................... 16 Igneous rocks......................................................................................................................................... 19 Metamorphic rocks................................................................................................................................ 19 Sediments............................................................................^ Organic boron........................................................................................................................................19 Carbon ......................................................................................20 Reference materials and reporting of isotope ratios....................................................................................20 Ranges in isotopic composition....................................................................................................................20 Carbonate and bicarbonate ...................................................................................................................20 Carbon dioxide......................................................................................................................................25 Oxalates...............................................................................26 Carbon monoxide..................................................................................................................................26 Organic carbon ......................................................................................................................................26 Elemental carbon...................................................................................................................................28 Ethane ....................................................................................................................................................28 Methane .................................................................................................................................................28 Nitrogen............................................................ Reference materials and reporting of isotope ratios....................................................................................29 Ranges in isotopic composition....................................................................................................................29 Nitrate................................................................................................................................ Nitrite............................................................................................ Nitrogen oxide gases.......................................................................................30 Nitrogen gas ................................................................................................30 Organic nitrogen....................................................................................................................................32 Nitrogen in rocks...................................................................................................................................34 Ammonium.................................................................................................................................^ Oxygen ........................................................... Reference materials and reporting of isotope ratios....................................................................................36 Ranges in isotopic composition....................................................................................................................37 Oxygen gas.............................................................................................................................................39 Water........................................................^ Carbon monoxide..................................................................................................................................41 Carbon dioxide ......................................................................................................................................41 Carbonates .............................................................................................................................................41 Nitrogen oxides.....................................................................................................................................42 Other Oxides..........................................................................................................................................42 Phosphates .............................................................................................................................................42 Silicates...................................................... Sulfates..................................................................................^ Plants and animals.................................................................................................................................43 Magnesium.....................................................................................................................................^ Reference materials and reporting of isotope ratios....................................................................................44 Ranges in isotopic composition....................................................................................................................44 Marine sources ......................................................................................................................................44 Elemental magnesium...........................................................................................................................46 SiHcon..............................................................^ Reference materials and reporting of isotope ratios....................................................................................46 Ranges in isotopic composition....................................................................................................................46 Igneous rocks.........................................................................................................................................47 Metamorphic rocks................................................................................................................................47 Vein quartz and silicified rocks ............................

/pdf/compilation-of-minimum-and-maximum-isotope-ratios-of-4zh3ha1cap.pdf

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

Seperation of Alkali Chloride from Ammonium Chloride using Anion Exchanger.

ジルコニウムと陽イオン交換体との反応に対する温度と,交換体の架橋度の影響を調査した。H形陽イオン交換体をカラムとし,これに1N硝酸1lにZrOSO4 10gを溶解した溶液を流下してZr形樹脂をつくったところ,Zr1原子あたりの最大電価はDowex50-X1は3.3,-X8は2.5,-X16は4.1,最小電価は-X1は0.39,-X8は1.24,-X16は1.51であった。また使用した樹脂のうち分配係数Kdに対する造錯剤の種類,温度の変化の影響が,Dowex50-X1ではあまり見られないが,Dowex50-X8,-X16では相当大きなKdの変化がある。またKdの価はこの3種の樹脂のうちDowex50-X8が最小であった。

/pdf/reaction-of-zirconium-with-ion-exchangers-4t0h9rdodk.pdf

Reaction of zirconium with ion-exchangers

イオン交換樹脂を発色の担体としてガリウムの微量検出法をこころみた。発色試薬としてアリザリンSを用い,これと網目構造の粗な陰イオン交換樹脂(Dowex1-×1)の[C2H3O2]形樹脂粒を用いて好結果が得られた。塩化アンモニウムとアンモニアでpHを6～7に調節したガリウム試料溶液中に,アリザリンSを吸収した前記樹脂粒を投入し,粒の呈色を空試験と比較観察する・ガリウムの存在量に比例して,赤～ 紫味赤色*1の発色を示し,空試験においては紫色を示す。本検出法において,検出限界量0.03γ,限界濃度1:106 を得た.アルミニウム,インジウム,チタン,ジルコニウム,トリウム,ビスマス,スズ,クロム,鉄,ウラニル,モリブデン酸,タングステン酸およびバナジン酸イオン等の共存は妨害する。

https://www.jstage.jst.go.jp/article/nikkashi1948/80/3/80_3_282/_pdf

Hidetake Kakihana

Papers

Seperation of Alkali Chloride from Ammonium Chloride using Anion Exchanger.

Reaction of zirconium with ion-exchangers

Microchemical Detection of Gallium with Ion-exchange Resin Particles

Numerical analysis of band development in multicomponent systems for chromatographic separation of isotopes

The Microdetection of Uranium with an Inorganic Cation Exchanger