The diffusion of CO2, CH4, C2H4, and C3H8 in polyethylene at elevated pressures

Diffusion and solubility coefficients have been determined for the CO₂^?, CH₄^?, C₂H₄^?, and C₃H₈-polyethylene systems at temperatures of 5, 20, and 35°C and at gas pressures up to 40 atm. Diffusion coefficients were obtained from rates of gas absorption in polyethylene rods under isothermal-isobaric conditions by means of a new diffusivity apparatus. The concentration dependence of the diffusion coefficients was represented satisfactorily by Fujita's free-volume model, modified for semicrystalline polymers, while the solubility of all the penetrants in polyethylene was within the limit of Henry's law. Semiempirical correlations were found for the free-volume parameters in terms of physicochemical properties of the penetrant gases and the penetrant-polymer systems. These correlations, if confirmed, should permit the prediction of diffusion and permeability coefficients of other gases and of gas mixtures in polyethylene as functions of pressure and temperature.     

Inverse-gas chromatography and the thermodynamics of sorption in polymers

In this review, the development of inverse gas chromatography (IGC) is briefly described, the role of A.A. Tager??s studies is indicated, and the principles of using the IGC method to solve problems of the thermodynamics of sorption of gases and vapors in polymers are formulated. The IGC method was originally developed by Guillet??s school to study the thermodynamics of sorption in polymers above their glass-transition temperatures; later, it was generalized and extended to the study of sorption processes below the glasstransition temperature in high-fractional free-volume polymers. These polymers exhibit specific features, such as strong exothermicity of mixing (??H _m ? 0), dependence of ??H _m on the size of the sorbate molecule, and high solubility coefficients. Chromatographic studies of sorption in the AF1600 amorphous perfluorinated polymer above and below its glass-transition temperature made it possible to test a new thermodynamic model that describes the sorption of gases and vapors in glassy polymers.     

Sorption of carbon dioxide in fluorinated poyimides

Sorption isotherms of CO₂ for ten fluorinated polyimides measured at 35°C and up to about 25 atm are analyzed according to the dual-mode sorption model. Sorption properties for these polyimides are compared with those for other glassy Polymers including unfluorinated polyimides. The glassy polymers with higher glass transition temperatures T_g tend to show greater CO₂ sorption. Introduction of a ? C (CF₃)₂? linkage into the repeat unit of the main chain increases the sorption by 20–80%. For glassy polymers, including the fluorinated and unfluorinated polyimides, the Langmuir affinity constant b and Henry's law solubility constant k_D are correlated with the content of functional (carbonyl or sulfonyl) groups [FG], and composite parameter reflecting the magnitude of both [FG] and free-space fraction V_F, respectively, with some exceptions. The Langmuir capacity constant C′_H is correlated with T_g, but there are two correlation lines; one for unfluorinated polyimides and a different one for other glassy polymers including fluorinated polyimides. The slope of the former group is smaller probably because of smaller differences in thermal probably because of smaller differences in thermal expansion coefficients in rubbery and glassy states. Most fluorinated polyimides show greater solubility of CO₂ than unfluorinated polyimides and other glassy polymers, because of their larger C′_H and k_D. © 1993 John Wiley & Sons, Inc.     

Effect of molecular weight on the diffusion coefficient of carbon dioxide in polystyrene

The permeability and time lag at pressures below 1 atm were measured for carbon dioxide in five polystyrene samples with different molecular weights at 25 to 40°C. The apparent permeability coefficient decreases with increasing carbon dioxide pressure and also decreases with increasing molecular weight of polystyrene, whereas the apparent diffusion coefficient calculated from time lag increases with pressure and is independent of molecular weight. Parameters for the partial-immobilization model were determined from the apparent diffusion and permeation coefficients by using a nonlinear least-squares optimization program without using sorption data. The results suggest that the void-saturation constant C′_H decreases as the molecular weight of the polymer increases or as the chain-end free volume decreases. The significance of these observation and their interpretation is discussed in terms of free-volume theory for glassy polymers.     

Sorption and transport of carbon dioxide in a polyimide from 3,3′4,4′-biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl sulfone

CO₂ sorption and transport were investigated for the polyimide prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-diaminodiphenyl sulfone (DDS). The morphology of films did not change on annealing above the glass transition temperature and remained amorphous unlike the polyimide prepared from BPDA and 4,4′-oxydianilline (ODA). This seems to be due to the strong hindrance to rotation of the sulfonyl linkage. Sorption and transport data were analyzed according to the dual-mode model. Solubility, diffusion, and permeability coefficients at 20 atm and 80°C for BPDA-DDS polyimide were substantially equal between as-cast and annealed films and were 1.7, 2.2, and 3.7 times greater, respectively, than for the as-cast films of the BPDA-ODA polyimide. The higher solubility was due to larger values of the Henry's law solubility constant k_D, Langmuir capacity constant C, and the Langmuir affinity constant b. The sorption and transport properties were compared with those for amorphous glassy aromatic polymers including other polyimides. The relation of k, C, b, and the diffusion coefficients in the Henry's law population and the Langmuir population (D_D and D_H) with other properties of the polymers were discussed. Values D_D and D_H for BPDA-DDS polyimide were much larger than expected from the estimated free-volume fraction.     

Polyurethane membrane for gas fractionation

Polyurethanes (PU) elastomeric membranes were synthetized using TDI reacted with bifunctional and polyfunctional polyols. In the case of bifunctional polyols, polypropyleneglycols of different chain length were used.Permeability, diffusion coefficient (D), solubility (S) were experimentally measured and solubility (S) was calculated with different gases (CO, H₂, CO₂, CH₄, C₂H₄, C₂H₆). The results show some possible practical applications. The diffusion coefficient D was found to depend upon the diameter of the permeating gas molecule and on the structure of the polymers, nevertheless no simple relation could be found with the free volume calculated with the W.L.F. theory.The solubility constant of the different gases in all the synthesized polymers could be interpreted on the basis of the regular solution theory founded on the solubility parameters of the gases and of the polymers.     

Addition-type polynorbornene with Si(CH3)3 side groups: Detailed study of gas permeation and thermodynamic properties

Polymerization of norbornene bearing Si(CH₃)₃ groups in the five position with the opening of double bonds was performed. By accurate selection of the ratios catalyst/co-catalyst and monomer/catalyst the samples with increased molecular mass (about 400,000) were obtained. Transport parameters of this, addition type poly(trimethylsilyl norbornene) (PTMSN) were measured using the gas chromatographic and mass spectrometric methods for different gases (H₂, He, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈ and n-C₄H₁₀). Temperature dependence of the permeability coefficients (P) indicated that low activation energies of permeation (E_P) and diffusion (E_D) are characteristic for PTMSN. In some cases (CO₂, C₂H₆) negative E_P values were observed. Thermodynamics of vapor sorption in this polymer was studied using the inverse gas chromatography method. It was shown that PTMSN is characterized by very large solubility coefficients S similar to those of poly(trimethylsilyl propyne) (PTMSP). The comparison of the P, D, and S values of these highly permeable polymers showed that the greater permeability of PTMSP is determined by the larger D values. Application of different approaches for the determination of the size of microcavities in PTMSN indicated that this polymer is characterized by large size of microcavity (800–1200 ?³).     

Ab initio study on the stability,geometry and electronic structure of the cyclopropenyl system

Results of an LCAO-MO-SCF investigation into the stability and geometry of the cyclopropenyl cation (C₃H₃⁺), anion (C₃H₃^?) and radical (C₃H₃^o) are presented. By independently varying the two relevant bond angles, the shape of the potential energy curves in the corresponding two-parameter space for these three species has been obtained. It is found that the cation is most stable in the D_3h nuclear configuration, while the anion has minimum energy in the C_s symmetry. In the specific case of the C₃H₃ radical, which exhibits an orbital, as well as spin-degeneracy, in the D_3h configuration, a strong Jahn-Teller effect is observed, leading to estimates for the non-symmetrical equilibrium configuration at C_2v and for the distortion energy of 12 kcal/mole from the D_3h symmetry. In terms of the population analysis and the contour diagrams, the electronic charge distribution has also been studied for these species in their most stable configurations.     

A study of electronic structures of some C9H9- carboanions

The electronic structures of five C₉H₉^-, carboanions have been studied by ab initio STO-3G calculations, and some general conclusions on related C₉H₉^- and C₉H₉⁺ structures are presented. Large antibonding interactions in one occupied MO make barbaral-9-yl anion (2) unstable as its cationic counterpart (8). The proposed D_9h-symmetrical cation and D_3h-symmetrical anion (3) do not exist due to Jahn-Teller distortions. A study of the MO correlations confirms that the two tetracyclic anions with C_2v symmetry (5 and 6) are the results of the Jahn-Teller distortions of 3. Anion 5 is identified as the proper intermediate of the Cope rearrangement of anion 2.     

Use of spherical coordinates for the 4-ring rotation-puckering problem

The rotational constants of eight typical 4-ring molecules represented by the semi-rigid model of type C_2v/C_s are analysed in terms of the kinetic coefficients of the rotation-puckering model formulated with spherical coordinates θ, φ as internal dynamic coordinates. It is shown that practically all 4-ring molecules may be considered as slightly perturbed D_4h/D_2d-type (cyclobutane, φ = π/4) semi-rigid models. The coordinate φ is practically independent of the puckering state and always lies in the range 40° < φ < 45°. The coordinate θ almost completely describes the puckering mode and its θ_v-values depend either monotonically (low barrier) or zig-zag (high barrier) on v.     

Infrared study of polymorphism of tert-butanol

Infrared absorption spectra of tert-butanol-OH, -OD and mixed crystals were measured in the temperature range of 96–305 K and the frequency range of 400–3600 cm^′-1. Two solid phases I and II were identified. The interpretation based on the C_2v chain polymer and D⁹_2h crystal structure was found to be appropriate for phase II. Experimental arguments in favour of a C_3h cyclic polymer structure of phase I were given.     

Chelating tendencies in the rows of polymeric sorbents and their copper(II) and lead(II) complexes

The physicochemical properties of chelating polymer sorbents (CPSs), derivatives of poly(styrene-2-hydroxy-〈1-azo-1′〉-2′-hydroxybenzene), are studied with respect to copper and lead ions. The following sorption parameters are determined: the optimum acidity, temperature, and duration; the sorption capacity of the sorbent (SCS); and stability constants of polychelates. Quantitative correlations are found between the dissociation constants (pK′ _a) of the analytical functional group (AFG) of the sorbent, and the pH₅₀ of chelation of the tested metals; between p K′ _a and the stability of the complexes (logβ); and between pK′_a and the charge of the oxygen atom of the complexing group (z); these correlations are intended for use in elucidating the effect of the structural features and acid-base properties of the AFG on the chemisorption parameters of copper(II) and lead(II). These correlations predict the physical-chemical properties of sorbents and the sorption parameters of trace elements for preconcentrating and separating them from biological, natural, and technical objects     

Magnetic criteria of aromaticity in a benzene cation and anion: how does the Jahn–Teller effect influence the aromaticity?

The aromatic/antiaromatic behavior of the Jahn–Teller (JT) active benzene cation and anion has been investigated using Density Functional Theory (DFT) calculations of Nuclear Independent Chemical Shifts (NICS) and magnetic susceptibility. NICS parameters have been scanned along the Intrinsic Distortion Path (IDP) for the benzene cation showing antiaromaticity which decreases with increasing deviation from D_6h to D_2h symmetry. Changes in NICS values along the IDP from D_6h to C_2v in the benzene anion revealed non-aromatic character.     

A physicochemical study of the sorption of lead: Correlations in a series of chelating polymer sorbents

The sorption properties of chelating polymer sorbents (CPSs), the derivatives of poly(styrene-2-oxy-azo-2′-oxybenzene), with respect to the lead ion are studied. The parameters of the sorption processes—optimum conditions of sorption (acidity, temperature, and time), the sorption capacities of sorbents, the possibility of desorption, and the stability constants of the chelated polymers—are determined. Quantitative correlations between p K′_OH of the functional analytical group (FAG) of the sorbent and σ _{o + p(p)} for ortho-and para-substituents, between p K′_OH and pH₅₀ for the formation of chelate complexes of lead, between p K′_OH and the stability of lead complexes (logβ), and between σ _{o + p(p)} and pH₅₀ for the formation of chelate complexes of lead are established with the aim of studying regularities of the influence of the structure and acid-base properties of FAGs on parameters of chemisorption of Pb²⁺. It is shown that the established correlations provide a means for quantitatively predicting physicochemical parameters of sorbents and the process of sorption of lead with the aim of targeted synthesis of CPSs and their use in the chemistry of polymer compounds and in the process of concentrating.     

Ab initio study of structures and energies of Al2H4 and Al2H 4 −

The low-lying isomers of Al₂H₄ and their anions are investigated with the hybrid density functional B3LYP, the coupled-cluster CCSD and CCSD(T) methods, and the electron propagator theory. The positive adiabatic electron affinities 5,798 and 10,112 cm⁻¹ are predicted for the neutral C_2v and D_2d symmetric isomers, respectively. The D_2h symmetric anion is more stable by 852 cm⁻¹ than the C_2v symmetric anion. The photodetachment spectra for Al₂H₄⁻ anions at the C_2v and D_2h symmetries are simulated on the basis of the Franck–Condon factor calculations, indicating a reasonable way to study the transition state of the intramolecular torsion process     

Gas permeation properties of phenylene oxide polymers

Gas permeability (P_i) and diffusion (D_i) coefficients in respect to several gases (H₂, O₂, N₂, CO, CO₂, CH₄) have been measured for poly(2,6-dimethylphenylene oxide) (PMPO), poly(2,6-diphenylphenylene oxide) (PPPO), and phenylene oxide copolymers containing methyl, phenyl, and allyl radicals as side groups. X-ray diffraction study shows that both homopolymers are semicrystalline materials, whereas all the copolymers are completely amorphous. The results show that a replacement of methyl by phenyl groups in PMPO/PPPO pair is accompanied by decrease in the P values. A transition from semicrystalline PMPO to amorphous copolymers results in a decrease in permeability and solubility coefficients and not in a growth of these parameters as can be expected on the basis of the behavior of other semicrystalline polymers (e.g. polyolefins). It is supposed that the crystallites of PMPO, and possibly of PPPO are packed loosely and, hence, take part in sorption and gas transport. This assumption is in agreement with numerous X-ray data as well as the results of positron annihilation study of these polymers.     

Quantum-chemical study of ytterbium fluorides and of complex F<Subscript>2</Subscript>YbF<Subscript>2</Subscript>CeF<Subscript>2</Subscript>

The structural parameters of the (²Σ⁺//C_∞v)-YbF, (¹A₁//C_2v)-YbF2, (²A₂^′//D_3h)-YbF₃, (¹Ag//D_2h)-YbF₂Yb, (¹Ag//C_2h)-FYbF₂YbF, (¹A₁//C_2v)-FYbF₂YbF, (¹A₁//C_2v)-YbF₂YbF₂, (³B_3u//D_2h)-F₂YbF₂YbF₂, (²A′//C_s)-FYbF₂YbF₂, and (³B₂//С_2v)-F₂YbF₂CeF₂ molecules have been determined. Disproportionation of ytterbium monofluoride (2YbF → YbF₂ + Yb + 0.46 eV) is less exothermic than dimerization (2YbF → YbF₂Yb + 2.10 eV). The bond energy of the ytterbium difluoride molecules in the trans dimer (2.93 eV) exceeds those in the cis dimer (2.86 eV) and the coaxial dimer (1.66 eV). Ytterbium trifluoride dimerizes exothermically (2.95 eV) without spin pairing. The dipole and quadrupole moments of the molecules as well as the charges and spin populations of the atoms and the valence electron configurations of the lanthanides have been calculated.     

Preparation and Crystalline Structure of Dihydrate of <Emphasis Type="Italic">hemi</Emphasis>-(Diazonium-18-crown-6) Isocyanurate of Isocyanuric Acid

Crystalline dihydrate of hemi-(diazonium-18-crown-6) isocyanurate of isocyanuric acid, 0.5[H₂DA18K6]²⁺?(C₃H₂N₃O₃)^??C₃H₃N₃O₃?2H₂O, was prepared and investigated by X-ray crystallography. In the given structure the dication DA18K6 is center-symmetric and possesses crown conformation of approximate D_3h symmetry. Molecule of isocyanuric acid and its anion are nearly planer. This molecule possesses approximate D_3h symmetry and its anion possesses approximate C_2v symmetry. With sufficient precision were determined geometrical parameters (bond lengths, bond angles etc.) of ions and molecules and was determined their packing in the given crystalline structure in which there is developed system of intermolecular (interion) hydrogen bonds.     

Bridged structures in multiply bonded silicon compounds: Disilyne,protonated disilyne and disilene

Ab initio SCF and electron correlation calculations are reported for the singlet ground state of the title compounds. These calculations confirm earlier findings that non-planar bridged Si₂H₂ is the most stable structure. For protonated disilyne (Si₂H³⁺) a bridged D_3h structure is the global mimimum. Two bridged structures of C_2v and C_2h symmetry are found in the case of disilene (Si₂H₄) which are only 14–17 kcal/mol above the D_2h structure.