NMR determination of the equilibrium constant for the liquid H2O–D2O mixture

Duplan, J.C.; Mahi, L.; Brunet, Jean L.

doi:10.1016/j.cplett.2005.07.005

Cited by 42 publications

(30 citation statements)

References 21 publications

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“…This in good agreement with the "best" theoretical value of 3.85 [23]. The two most recent liquid phase equilibrium constant measurements (at 298 K) are 3.86 Ϯ 0.07 [3] and 3.86 Ϯ 0.01 [27] [23] difference between liquid and gas-phase equilibrium constants is estimated to be only 0.03 [28]. Previous direct mass spectrometric measurements (carried out in the 1960s) have led to the values of K ϭ 3.75 Ϯ 0.07 [29] and 3.76 Ϯ 0.02 [26]; however, these measurements have been performed at electron accelerating voltages from 3 eV (H 2 O) [25] Se concentrations in the headspace.…”

Section: Quantitation Of Isotopologues Using the Reconstructed Mass Ssupporting

confidence: 76%

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Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

Meija

Mester

D’Ulivo

2006

J. Am. Soc. Mass Spectrom.

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Three conceptually different mathematical methods are presented for accurate mass spectrometric determination of H 2 O/HOD/D 2 O and H 2 Se/HDSe/D 2 Se concentrations from mixtures. These are alternating least-squares, weighted two-band target entropy minimization, and a statistical mass balance model. The otherwise nonmeasurable mass spectra of partially deuterated isotopologues (HOD and HDSe) are mathematically constructed. Any recorded isotopologue mixture mass spectra are then deconvoluted by least-squares into their components. This approach is used to study the H 2 O/D 2 O exchange reaction, and is externally validated gravimetrically. The H 2 O/D 2 O exchange equilibrium constant is also measured from the deconvoluted 70 eV electron impact GC/MS data (K ϭ 3.85 Ϯ 0.03). (J Am Soc Mass

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Section: Quantitation Of Isotopologues Using the Reconstructed Mass Ssupporting

confidence: 76%

“…Although seemingly simple system, estimates of the H 2 O/D 2 O isotope exchange equilibrium constant (in both gaseous and liquid phases) range between 3.41 and the geometric mean of 4.0 [3,26]. This value has been recently (re)estimated using IR and NMR techniques [3,27].…”

Section: Quantitation Of Isotopologues Using the Reconstructed Mass Smentioning

confidence: 99%

Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

Meija

Mester

D’Ulivo

2006

J. Am. Soc. Mass Spectrom.

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“…4 (the most recent NMR estimation gave the value 3.86 [35]). Accordingly, in the equimolar D 2 O/H 2 O mixture the proportion of H 2 O:HDO:D 2 O is approximately 1:2:1, as confirmed on the basis of infrared spectra [36].…”

Section: Introductionmentioning

confidence: 98%

Vibrational spectroscopy of semiheavy water (HDO) as a probe of solute hydration

Śmiechowski

Stangret

2010

Pure and Applied Chemistry

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Vibrational spectroscopy is an ideally suited tool for the study of solute hydration. Nevertheless, water is commonly considered by spectroscopists a difficult solvent to work with. However, by using the isotopic dilution technique, in which a small amount of D 2 O is introduced into H 2 O or vice versa with formation of semiheavy water (HDO), many technical and interpretative problems connected with measurement of infrared spectra of water may be circumvented. Particularly, the isotopic decoupling of stretching vibrational modes greatly simplifies interpretation of the spectra. Systematic studies conducted in several laboratories since the 1980s up to the present day have provided a vast amount of data, concerning mainly ionic hydration. Many of these experiments have been performed in our laboratory. The analysis method we applied is based on the quantitative version of the difference spectra technique and allows separation of the spectrum of solute-affected HDO from the bulk solvent. This review illustrates the development of vibrational spectroscopy of HDO and spectral analysis methods over the years, as well as summarizes the results obtained for ionic and nonionic solutes, including some general hydration models formulated on their basis.

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“…Molecular species in H2O/D2O mixture: In the residual water, there are mainly three molecular species such as H2O, D2O and HDO in the solution 7 . The dynamic reaction among H2O, HDO and D2O can be expressed by the following equation [8][9][10][11] . (1) In the case of H2O/D2O mixture, H2O is added to D2O solution containing residual water.…”

Section: Results Related To the Traces And The Characteristics Of Thementioning

confidence: 99%

Observation of Triplet Traces Obtained with Inversion Recovery Method in Both Residual Water- and H2O/D2O-Albumin Mixture by Using 400 MHz Proton NMR

Yılmaz¹,

Zengin²,

Korunur³

2013

Asian J. Chem.

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H 2 O/D 2 O mixtures are being used as solvent for proteins and some other chemical compounds 1-7 . In the mixture of H 2 O and D 2 O, there are three molecular species H 2 O, D 2 O and HDO in a dynamic equilibrium 8,9 . However, NMR spectrum of the mixture shows a single line at all static magnetic fields. Accordingly, the studies involving such solvents are mainly based on this single spectrum of water. The interpretation of the spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation data in H 2 O/ D 2 O mixture is known to be difficult 8,9 . The analysis of the equilibrium data among H 2 O, D 2 O and HDO was also reported to be difficult 10 . On the other hand, the small spin-spin splittings of H 2 O signal by deuterium (D) in H 2 O/D 2 O were studied by proton NMR for deuteriated water 10 . In addition, a triplet of 1 H NMR signals, which is the splitting of H 2 O signal by deuterium, was recently presented through a special free induction decay (FID) processing programme 11 . The splittings may be demonstrated further by the relaxation effects of the triplet components. The demonstration may be achieved by acquiring inversion recovery (IR) data of the triplet. It should contribute to the interpretation of NMR relaxation mechanisms NMR studies involving H2O/D2O mixtures are mainly based on a single spectrum of water. However, some recent papers have revealed the presence of an HDO triplet in H2O/D2O, which is caused by the splittings of H2O signal by deuterium (D). Observation of inversion recovery (IR) traces of this triplet should be very useful for analyzing relaxation data in such mixtures. In this work, in order to obtain the traces, inversion recovery signal intensities of residual water and a mixture of 0.10 H2O and 0.90 D2O were acquired versus a set of short delay times in the presence or absense of 0.2 g albumin. T1 and T2 curves of the same samples were also obtained by using different sets of much longer times for checking the effect of radiation damping on the traces. Experiments were carried out with a 400 MHz proton NMR spectrometer equipped with a topspin programme for relaxation measurements. Inversion recovery data of the traces and T1 curves were obtained with the inversion recovery method, while T2 curves were obtained with the Carr-Purcell-Meiboom-Gill method. Data was processed through an analysis programme of the topspin. Data showed that radiation damping is effectively reduced upon addition of albumin. Furthermore, the data of the residual water-and the mixture with albumin demonstrated the traces of the triplet at the initial part of a single inversion recovery line. Our results suggest that the splitting of water proton signal by deuterium can be detectable by the inversion recovery method for D2O-and the mixture containing albumin.

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NMR determination of the equilibrium constant for the liquid H2O–D2O mixture

Cited by 42 publications

References 21 publications

Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

Vibrational spectroscopy of semiheavy water (HDO) as a probe of solute hydration

Observation of Triplet Traces Obtained with Inversion Recovery Method in Both Residual Water- and H2O/D2O-Albumin Mixture by Using 400 MHz Proton NMR

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NMR determination of the equilibrium constant for the liquid H2O–D2O mixture

Cited by 42 publications

References 21 publications

Mass spectrometric separation and quantitation of overlapping isotopologues. H2O/HOD/D2O and H2Se/HDSe/D2Se mixtures

Mass spectrometric separation and quantitation of overlapping isotopologues. H2O/HOD/D2O and H2Se/HDSe/D2Se mixtures

Vibrational spectroscopy of semiheavy water (HDO) as a probe of solute hydration

Observation of Triplet Traces Obtained with Inversion Recovery Method in Both Residual Water- and H2O/D2O-Albumin Mixture by Using 400 MHz Proton NMR

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Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures