Adsorption of gases on layered silicates at high pressures

Equilibrium adsorption of nitrogen, carbon dioxide, and argon was examined on the sodium and pyridinium forms of montmorillonite and on the hydrogen form of bentonite. The measurements were carried out at 303, 343, 373, and 400 K over pressure ranges of 0.1–90 MPa (Ar and N₂) and 0.1–6 MPa (CO₂). The amount of nitrogen vapor adsorbed was determined at 77 K and pressures from 0 to 0.1 MPa. The porous structure parameters of the studied samples were determined using adsorption isotherms of nitrogen, argon, and carbon dioxide vapors. At elevated temperatures and pressures >10 MPa, Ar and N₂ adsorption processes on the Na-form of montmorillonite and Ar adsorption on bentonite are activated, since the amounts of the gases adsorbed and adsorption volumes increase with temperature. No activated adsorption is observed for carbon dioxide adsorption on these adsorbents. A comparison of the excess adsorption isotherms of gases on the Py-form of montmorillonite and H-form of bentonite shows that adsorption in micropores predominates for the Py-form of montmorillonite, whereas for the Na-form of bentonite and H-form of bentonite adsorption occurs mainly in meso- and macropores.     

Adsorption of gases,vapors and liquids in zeolites at high pressures

The linearity of adsorption isotherms, which is well preserved independently of the state of aggregation of the equilibrium phase, the absence of discontinuities on adsorption isotherms on passing into the region of the liquid state, and the considerable differences in the behavior of the temperature dependence of the densities of the adsorbate and of the substance adsorbed along the saturation line; all these facts indicate that the adsorbate in the micropores of zeolites is in a special state of aggregation. The linearity of the isosteres and the maxima on the curves for the specific heat of the adsorbate at constant pressure when its concentration in the cavities is high probably indicate the presence of phase transitions of the second kind of the adsorbed substance.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 507–511, March, 1990.     

Double clathrate hydrates of cross-linked tetrabutylammonium polyacrylate and noble gases at high pressures

Temperatures of hydrate decomposition were measured by means of the differential thermal analysis at a pressures up to 800–900 Mpa in the systems: cross-linked tetrabutylammonium polyacrylate–water and cross-linked tetrabutylammonium polyacrylate–water–noble gas (He, Ne, Ar, Kr, Xe). The effect of the deformation of D- cavities of the hydrates on the temperature of their decomposition is discussed on the basis of the experimental data.     

Adsorption of gases on adsorbents of various nature and porous structure at high pressures

The isotherms of excess adsorption of argon, nitrogen, and carbon dioxide on adsorbents with various porous structures (active carbon AU-71, polymeric sorbent MN-200, and synthetic zeolite NaA) were measured on the precision volumetric-gravimetric device in the pressure range of 0.1—150 MPa and at temperatures 300—400 K. The results of determination of the adsorption volumes of the studied adsorbents were compared using two methods. The first method is based on the Dubinin-Radushkevich equation, whereas the second one involves a conditional division of the weight of the substance in an ampule into the adsorbed portion and the part existing in the gas phase. The behavior of the adsorbed substance is described by the equation of adsorption of complete content corresponding to the physics of the adsorption process. The relation of the parameters of the empirical Dubinin—Radushkevich equation to the energy characteristics of the system was established.     

A thermodynamic analysis of the solubility of gases in water at high pressures and supercritical temperatures

A one-parameter form of the Henry law is suggested to describe the solution of real gases in water over a fairly wide range of temperature and pressure variations. The thermodynamic derivation of the Henry law is based on the Van’t Hoff model of concentrated solutions of gases. The analytic approach developed in this work is a variant of rigorous thermodynamic theory that refines and generalizes the Krichevskii-Kazarnovskii equation. The thermodynamic theory suggested is compared with the experimental data on the solution of methane and nitrogen in water.     

Polarography at high pressures

A review of polarography at high pressures is presented.     

Grignard reaction at high pressures

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1937–1938, August, 1991.     

Liquid densities at high pressures

Aalto et al. recently proposed a model for compressed liquid densities. The model was found more accurate than the Hankinson–Brobst–Thomson (HBT) and Chang–Zhao models. However, the pressure region of the data studied was limited to 200 bar maximum. In this work, the recently developed liquid density model is extended to high pressures. The equation describing the pressure dependence of liquid density is reformulated and the required parameters are optimized using a database containing 7478 data points for 31 pure hydrocarbons; maximum pressure in this data set is 8000 bar. The average absolute deviation (AAD) between these data and the recommended model is 0.4636%. A comparison to the results obtained with the HBT and Chang–Zhao models for the same data set shows that the new model is clearly more accurate in the extended pressure range, as well. The revised model is also tested in predicting liquid densities for mixtures; 84 different combinations of mixing rules are studied. The evaluation of the mixing rules is carried out using two compilations of experimental data: the first one contains 6712 points for 47 binary and two ternary mixtures, and the second 3582 points for 11 methane+alkane mixtures. In addition, the predictions are tested with a data set of 1119 points for other miscellaneous mixtures. No binary interaction parameters are used. With the recommended mixing rules, the AAD percentage is 0.5824% for the first set of data. If one simply adopts the mixing rules recommended for the HBT model, the AAD value for the same data set becomes 0.7482%.     

Henry condensation at high pressures

The hitherto inaccessible nitroolefin (VII), which is the most convenient intermediate for the synthesis of the psychotropic amine (VIII), has been obtained by the direct condensation at high pressures (up to 1500 MPa) of piperonal (V) with 1-nitropropane (VI). The structure of (VII) was confirmed by direct synthesis from pyrocatechol (X). The amine (VIII) was obtained in three steps from (VII). This synthesis of (VIII) is shorter than that previously reported.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 829–832, April, 1990.     

Viscosities of carrier gases at gas chromatograph temperatures and pressures

Summary Equations are derived for viscosities of H₂, He, N₂ and Ar for use at chromatographic temperatures which are accurate to within 0.3% for H₂, and 0.1% for the other gases. The effect of pressure is usually negligible but may increase the viscosity of N₂ or Ar by as much as 0.5% at 25°C or lower and 5 atm or higher.     

Trimerization of perfluoroheptanonitrile at high pressures

Conclusions A study was carried out on the trimerization of perfluoroheptanonitrile under high pressure conditions at 110 and 124°C. This reaction obeys zero-order kinetics relative to the monomer and first-order kinetics relative to the catalyst.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1893–1895, August, 1987.     

Permeability of pure and mixed gases in silicone rubber at elevated pressures

The transport properties of silicone rubber are reported at 35°C for a series of pure gases (He, N₂, CH₄, CO₂, and C₂H₄) and gas mixtures (CO₂/CH₄ and N₂/CO₂) for pressures up to 60 atm. The effects of pressure and concentration on the permeability of various gases have been analyzed to consider plasticization and hydrostatic compression effects. Over an extended pressure and concentration range, both compression of free volume and eventual plasticization phenomena were observed for the various penetrants. In pure component studies, plasticization effects tended to dominate hydrostatic compression effects for the more condensible penetrants (C₂H₄ and CO₂) while the reverse was true for the low sorbing N₂ and He. These issues are discussed in terms of penetrant diffusion coefficients versus pressure to clarify the interplay between the opposing effects for the penetrants of markedly different solubilities. Additional insight into the somewhat complex interplay of the plasticization and hydrostatic compression effects are given by mixed gas permeation results. It was found that the permeability of nitrogen in a 10/90 CO₂/N₂ and a 50/50 CO₂/N₂ mixture was increased by the presence of CO₂ because the plasticizing nature of CO₂ is able to overcome nitrogen's compression effect.     

Materials by design at high pressures

Pressure, a fundamental thermodynamic variable, can generate two essential effects on materials. First, pressure can create new high-pressure phases via modification of the potential energy surface. Second, pressure can produce new compounds with unconventional stoichiometries via modification of the compositional landscape. These new phases or compounds often exhibit exotic physical and chemical properties that are inaccessible at ambient pressure. Recent studies have established a broad scope for developing materials with specific desired properties under high pressure. Crystal structure prediction methods and first-principles calculations can be used to design materials and thus guide subsequent synthesis plans prior to any experimental work. A key example is the recent theory-initiated discovery of the record-breaking high-temperature superhydride superconductors H₃S and LaH₁₀ with critical temperatures of 200 K and 260 K, respectively. This work summarizes and discusses recent progress in the theory-oriented discovery of new materials under high pressure, including hydrogen-rich superconductors, high-energy-density materials, inorganic electrides, and noble gas compounds. The discovery of the considered compounds involved substantial theoretical contributions. We address future challenges facing the design of materials at high pressure and provide perspectives on research directions with significant potential for future discoveries.

This work summarizes and discusses recent progress in the theory-oriented discovery of new materials under high pressure, including hydrogen-rich superconductors, high-energy-density materials, inorganic electrides, and noble gas compounds.     

Interaction of iodine species with glycogen at high concentrations of iodine

Glycogen–iodine (GI) complex formation has been studied at different concentrations of iodine and glycogen. For each glycogen concentration (0.25, 0.125, 0.0625, 0.0313 g/L), the iodine concentration was varied from 0.0317 to 1.59 g/L and the absorbance readings were taken at 453 and 560 nm (GI wavelengths of maximum absorbance). The 453 nm absorbance curves for the GI solution (GI complex and unreacted iodine), and that of the pure iodine solution (without glycogen) level off at a high iodine concentration, and give a peak in the subtracted curve. The 560 nm curves consistently increase in absorbance, and no peak is noticed in the subtracted curve. The spectra of concentrated iodine solutions in water and alcohol suggest the formation of neutral iodine clusters. We suggest that these iodine clusters do not react with glycogen, and that the GI complex formation takes place by the addition of I₂ molecules. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 927–931, 1997     

Infrared and Raman spectroscopy at high pressures

Pressure is accepted theoretically as a useful variable. However in a studies on liquid or solid samples, it is still relatively unusual for pressure to be used as an experimental variable. The reluctance of experimentalists to use this theoretically attractive variable is caused mainly by the technical difficulties associated with the use of sufficiently high pressures. In this talk I will try to show that in many cases the experimental limitations are no longer those introduced by the use of high pressures. High pressure spectroscopic studies clearly imply the use of high pressure spectroscopic cells. A brief account will therefore be given of the various types of high pressure optical cells which are currently being used for spectroscopic studies. Each individual high pressure spectroscopic study has its own special justification. However there are a few quite general observations that can be made which cover many of the specific objectives of individual high pressure spectroscopic studies. For example:(i) pressure induced frequency shifts carry unambiguous information about anharmonic terms in the relevant potential function (i.e. the potential V is a function of distance d. therefore pressure can be used to change d and study V.)(ii) all known materials undergo structural phase transitions if the form which is thermodynamically stable under ambient conditions is compressed to high enough pressures: these high pressure phases should be studied.(iii) as the application of pressure forces a material towards a phase transition, the spectroscopic study can be used to gain information about the approaching structural instability.(iv) virtually all infrared and Raman spectra contain examples of Fermi resonance which confuse the interpretation of the spectra and the effects of pressure are valuable aids to the correct assignment of the resonating levels.(v) pressure induced frequency shifts can often give extra information to help with the more reliable assignment of features within a spectrum.The above points will be discussed and illustrated by examples chosen mainly from recent work by members of the spectroscopy group at King's College London.