Die stabilen Isotope des Sauerstoffs in Forschung und Technik

Staschewski, D.

doi:10.1002/ange.19740861102

Angewandte Chemie

1974

DOI: 10.1002/ange.19740861102

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Die stabilen Isotope des Sauerstoffs in Forschung und Technik

D. Staschewski¹

Abstract: Die stabilen Sauerstoffisotope erweisen sich als leistungsfähige Instrumente der Forschung; die Verwendungsmöglichkeiten dieser Isotope sind jedoch erst zu einem geringen Teil untersucht. Im vorliegenden Fortschrittsbericht werden fünf Grundtypen von Isotopen‐Effekten herausgestellt, deren Untersuchung und Auswertung eine neue Art von Informationen über physikalische, chemische und biologische Systeme und Prozesse liefern.

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“…[14]). This is an anomalous behaviour [15] and has been explained by an isotope effect of hydrogen bonding in the solution, as in solid samples normal vibrational energies are measured [16]. It is interesting to know first, whether an isotope effect of the chemical shift of 31 P for the phosphate species P 10 O4 3-and P 18 04 3~ is observable at all and second, whether a lower Larmor frequency for the phosphate species containing heavier oxygen isotopes is found in spite of the anomalous vibrational energies or not.…”

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confidence: 95%

Oxygen Isotope Effect on ³¹P NMR Spectra in the Phosphate Ion

Lutz

Nolle

Staschewski

1978

Zeitschrift Für Naturforschung A

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By Fourier transform high resolution NMR spectroscopy the 31 P signals of the phosphate species 31 P 16 04 _ t! 18 Ow 3_ " (n = 0, 1, 2, 3, 4) have been resolved in aqueous solutions of potassium phosphate. An isotope effect on the Larmor frequency of <5 ( 31 P) = (0.019 ± 0.002) to lower frequency was found for the substitution of a 18 0 atom for a 16 0 atom in the phosphate ion.It is well known, that in a molecule the substitution of a certain isotope for another influences the molecular properties. For many molecules changes in the Larmor frequencies have been observed if isotopes are substituted (see f. e. Ref.[1]). By increasing the resolution of the NMR spectra such isotope effects of the chemical shift can be measured even if the mass differences of the different isotopes are small such as for 16 0 and 18 0 or 32 S and 34 S (Ref. [2 -11]). For some central nuclei in oxyanions oxygen induced isotope effects have been found [8, 9,].Following the theory of Benedek et al. (Ref. [12]) Lauterbur [6] derived a simple relation, which describes the observed oxygen induced isotope effects in oxyanions fairly well [9, 10,]. In this theory the isotope effect of the chemical shift depends on the vibrational energies of the respective molecule. The theory predicts a lower Larmor frequency, if in the molecule with the heavier isotope the vibrational energies are smaller than in the molecule with the lighter one. This correlation is veryfied for example in the case of 55 Mn in Mn04~ (Ref. [8,9,13]). For 95 Mo in Mo04 2~ -for these molecules to our knowledge no experimental values of the vibrational energies are known -also lower Larmor frequencies were observed [9,10] for the species containing heavier isotopes.For the P04 3~i on the vibrational energies are known to be higher in aqueous solutions for the P 18 04 3~ than for the P 16 04 3~ (Ref. [14]). This is an anomalous behaviour [15] and has been explained by an isotope effect of hydrogen bonding in the solution, as in solid samples normal vibrational energies are measured [16]. It is interesting to know first, whether an isotope effect of the chemical shift of 31 P for the phosphate species P 10 O4 3-and P 18 04 3~ is observable at all and second, whether a lower Larmor frequency for the phosphate species containing heavier oxygen isotopes is found in spite of the anomalous vibrational energies or not. Measurements about this problem are reported in the following. ExperimentalThe 31 P NMR signal was observed with a Bruker SXP 4-100 MHz spectrometer in a magnetic field of 2.11 T at 36.44 MHz. The magnetic field was internally stabilized by the 2 H lock B-SN 20. The free induction decays were accumulated and Fourier transformed by a B-NC 12 computer.Solid P205 with the natural abundance of 18 0 was dissolved in high-grade H2 18 0. The solution was concentrated by vacuum distillation until a syrup of phosphoric and diphosphoric acid remained which was rediluted by a bigger quantity of 99% H2 18 0. Sealed off in an ampoule the solution now was heated at 120 c C for 24 h...

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mentioning

confidence: 95%

Oxygen Isotope Effect on ³¹P NMR Spectra in the Phosphate Ion

Lutz

Nolle

Staschewski

1978

Zeitschrift Für Naturforschung A

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ChemInform Abstract: DIE STABILEN ISOTOPE DES SAUERSTOFFS IN FORSCHUNG UND TECHNIK

Staschewski¹

1974

Chemischer Informationsdienst

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Die stabilen Isotope des Sauerstoffs in Forschung und Technik

Cited by 2 publications

References 101 publications

Oxygen Isotope Effect on ³¹P NMR Spectra in the Phosphate Ion

Oxygen Isotope Effect on ³¹P NMR Spectra in the Phosphate Ion

ChemInform Abstract: DIE STABILEN ISOTOPE DES SAUERSTOFFS IN FORSCHUNG UND TECHNIK

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Die stabilen Isotope des Sauerstoffs in Forschung und Technik

Cited by 2 publications

References 101 publications

Oxygen Isotope Effect on 31P NMR Spectra in the Phosphate Ion

Oxygen Isotope Effect on 31P NMR Spectra in the Phosphate Ion

ChemInform Abstract: DIE STABILEN ISOTOPE DES SAUERSTOFFS IN FORSCHUNG UND TECHNIK

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Oxygen Isotope Effect on ³¹P NMR Spectra in the Phosphate Ion

Oxygen Isotope Effect on ³¹P NMR Spectra in the Phosphate Ion