共查询到20条相似文献,搜索用时 31 毫秒
1.
H. F. Abbasov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2014,88(6):942-945
The aqueous solutions of polyethylene glycols with molecular masses of 600, 1000, 1500, 3000, 6000, and 20000 were studied by refractometry. The conformational polarizabilities, mean-square distances between the ends of the macromolecular chain, segment lengths, and the number of Kuhn segments in a macromolecule were determined using the Lorentz-Lorentz equation. The polarizability of a hydrated macro-molecule was represented as the sum of polarizabilities of the nonhydrated macromolecule with retained conformation and polarizabilities of the water molecules involved in hydration of macromolecules. The size of macromolecules stabilized starting from a certain concentration. It was concluded that the initial concentration of stabilization shifts toward low concentrations as the molecular mass of polyethylene glycol increases. The dependence of the mean-square distance between the ends of the macromolecular chain on the number of Kuhn segments was expressed as the exponential function with index 0.3. 相似文献
2.
《The Journal of chemical thermodynamics》2003,35(1):131-136
The isothermal and isobaric (vapour + liquid) equilibria for (cis-pinane + α-pinene) and (cis-pinane + 1-butanol) measured with an inclined ebulliometer are presented. The experimental results are analysed using the UNIQUAC equation with the temperature-dependence binary parameters with satisfactory results. Experimental vapour pressures of cis-pinane are also included. 相似文献
3.
《Journal of Saudi Chemical Society》2023,27(4):101676
This review is focused on recent achievements in bio-based self-healable elastomeric materials with special regard to elastomers made of natural rubber (NR) and its modified forms, including epoxidized natural rubber (ENR), oxidized natural rubber (oNR) or carbonated natural rubber (CNR). Besides natural rubber, also Eucommia ulmoides gum (EUG), which is an isomer of cis-1,4-polyisoprene, is a material of great interest to obtain bio-based self-healable elastomers. The paper attempts to describe the main classification of the most important intrinsic self-repairing mechanisms, including different types of reversible non-covalent interactions (such as hydrogen bonding, ionic interactions, metal–ligand coordination, shape-memory ability), dynamic covalent bonds (for instance Diels-Alder reversible bonds, dynamic sulfur-sulfur bonds, dynamic ester bonds, boronic-ester exchangeable bonds, dynamic imine bonds, silyl ether exchangeable bonds) and their combinations, which are found in self-healing elastomers. Furthermore, examples of NR-based elastomeric materials are provided and the potential applications proposed by researchers are also presented. 相似文献
4.
《Chemical physics》2005,308(3):199-200
The anisotropic rototranslational scattering spectra of nitrogen gas at high frequency up to 700 cm−1 for several temperatures and from low densities are analyzed in terms of new site–site (M3SV) intermolecular potential and interaction-induced pair polarizability models, using quantum spectral shapes computations. Our theoretical calculations take into account multipole contributions from the mean value and anisotropy of the dipole–dipole polarizability tensor α, two independent components of the dipole–octopole polarizability tensor E and dipole–dipole–quadrupole hyperpolarizability tensor B. The high-frequency wings are discussed in terms of the collision-induced rotational Rayleigh effect and estimates for the dipole–octopole polarizability |E4| are obtained and checked with recent ab initio theoretical value. Good comparison is found in the frequency range 0–400 cm−1 between the theoretical and experimental spectra. When an exponential contribution [exp(−ν/ν0)] with ν0 = 425 cm−1 is considered to model very short-range light scattering mechanisms at room temperature, good agreement is found over the whole frequency range. 相似文献
5.
《Journal of organometallic chemistry》2006,691(1-2):159-164
The dipole moments (μ) of the molecules, the dipole moments (μDA) and the length (dDA) of the Si ← N bonds, and the electrochemical oxidation potentials (Ep) of Si-substituted silatranes, the dipole moments (μhs) of the molecules of Si-substituted 3-homosilatranes as well as the enthalpies of formation (ΔH0) of the intermolecular complexes of SiF4 with aniline derivatives depend not only on the inductive and resonance effects, but also on the polarizability of substituents which can be characterized by the σα constants. 相似文献
6.
Optical properties of poly-1-trimethylsilyl-1-propyne (PTMSP) stereoisomers in solutions have been studied by means of flow birefringence method. Stereoisomers were chosen with various trans- and cis-configurations abundances of double CC bonds in monomeric units. The differences of main polarizabilities (α1 − α2) or statistical segments have been determined. Significant growth of (α1 − α2) values with increasing of the trans-isomer contents in chain molecule has been found. Optical anisotropy of monomeric segments, having cis- and trans-configurations, has been theoretically evaluated. It has been shown that observed significant increase of experimentally measured (α1 − α2) values cannot be sufficiently explained by only specific chain polarizability growth due to higher trans-isomers contents. It has been demonstrated that high (α1 − α2) value and it’s growth with increase of abundance of monomeric segments in trans-configuration has been caused by thermodynamical rigidity increase, i.e., higher number of monomeric units included into PTMSP statistical segment. 相似文献
7.
Subhash C. Bhatia Rachna Bhatia Gyan P. Dubey 《The Journal of chemical thermodynamics》2010,42(1):114-127
Densities and ultrasonic velocities of binary mixtures of decan-1-ol with 1,2-dichloroethane, 1,2-dibromoethane, and 1,1,2,2-tetrachloroethene have been measured over the entire range of composition at T = (293.15 and 313.15) K and at atmospheric pressure. From these results, the excess molar volumes, molar free volumes, excess molar isentropic compressibilities, limiting excess partial molar volumes, and isentropic compressibilities, intermolecular free lengths, and available volumes by three methods, thermal expansion coefficients, parameters related to space-filling ability, intermolecular free lengths, and molecular radii have been calculated. The experimental ultrasonic velocities have been analyzed in terms of the ideal mixture relations of Nomoto and Van Dael, Jacobson’s free length, Schaaff’s collision factor, Flory’s statistical, and Prigogine–Flory–Patterson theories and thermoacoustical parameters. 相似文献
8.
《The Journal of chemical thermodynamics》2006,38(4):455-460
Equilibrium tie line data have been determined for the two ternary liquid systems: {tetradecane, or heptadecane + pentylbenzene + N-methyl-2-pyrrolidone (NMP)} over a temperature range of (298 to 328) K. The two systems studied exhibit type I liquid + liquid phase diagram. The effect of temperature and n-alkane chain length upon solubility, selectivity, and distribution coefficients were investigated experimentally. 相似文献
9.
Keisuke Yoshida Atsushi Hirata Hisashi Hashimoto Ayumi Imayoshi Yoshihiro Ueda Takumi Furuta Takeo Kawabata 《Tetrahedron letters》2017,58(11):1030-1033
Predominant monoacylation of 1,n-linear disulfonamides took place in the presence of pyrrolidinopyridine-type organocatalysts when the chain length of the linear disulfonamides was n = 3, 4, or 5 (monoacylate/diacylate = up to 44). The chemoselectivity of the competitive acylation between N,N′-ditosyl-1,5-pentanediamine (n = 5) and N,N′-ditosyl-1,3-propanediamine (n = 3) was found to be 36, favoring the former substrate. Different chain length by only one carbon atom was discriminated in the competitive acylation between N,N′-ditosyl-1,5-pentanediamine (n = 5) and of N,N′-ditosyl-1,4-butanediamine (n = 4) with the relative acylation rate of 16 in the presence of the organocatalyst. 相似文献
10.
In this work, the thermal behavior of the regularity modes in Raman spectra of polyethylene with different densities and random ethylene/1-hexene copolymers with varying content of comonomer are studied. We demonstrate especially that the vibrational modes at 1062 and 2850 cm↙1 are related to a critical sequence length of trans-conformers of 6⬜8 CH2 groups, while the modes at 1130, 1170, 1295, and 2883 cm↙1 indicate a critical sequence length of trans-conformers of 18 CH2 groups. Upon increasing the 1-hexene content in the ethylene/1-hexene copolymers, the evolution of the intensities of the Raman modes at 1062, 1130, 1170, 1295, and 1417 cm↙1, normalized to the intensity of the band at 2850 cm↙1, is similar to the evolution of the intensities of the same modes in the Raman spectra of low density polyethylene at increasing temperature. This observation however contrasts with that in the Raman spectra of polyethylenes with middle and high densities. We suppose that these results can be explained by similarities in the structure of non-crystalline areas of low density polyethylene and the ethylene/1-hexene copolymers, which contain significant amounts of short sequences of trans-conformers. 相似文献
11.
《Polyhedron》2005,24(16-17):2165-2172
Five new hydrogen-bonded solvated iron(II) complexes of pyrazolyl- and imidazolyl-based N,N-chelating ligands have been synthesised. Water to ligand-NH hydrogen-bonded bridges occur in the pseudo-dimeric complexes {cis-[Fe(pypzH)2(NCX)2]2(μ-OH2)(H2O)2} · H2O · MeOH (where X = S or Se), and in the chain complex {cis-[Fe(pypzH)2(NCS)2](μ-OH2)}n. A “half” spin-crossover (Tc = 125 K) was observed in the dimeric X = Se complex by means of magnetic measurements and no thermal hysteresis occurred between 4 and 300 K. The crystal structure at 123 K showed Fe–N distances consistent with the magnetism. Each Fe in the dimeric unit was structurally equivalent in the HS–LS state. Removal of the solvate molecules led to HS–HS behaviour over the temperature range 4–300 K. The pseudo-dimer with X = S also showed HS–HS behaviour as did the monomeric analogue cis-[Fe(pypzH)2(NCS)2]H2O and a structurally different methanol-bridged dimer {cis-[Fe(pyimH)2(NCS)2]2(μ-MeOH)2} · 2MeOH (pypzH = 2-(1H-pyrazol-3-yl)-pyridine; pyimH = 2-(1H-imidazol-2-yl)-pyridine). 相似文献
12.
Biprajit Sarkar Thilo Schurr Ingo Hartenbach Thomas Schleid Jan Fiedler Wolfgang Kaim 《Journal of organometallic chemistry》2008,693(8-9):1703-1706
3,6-Bis(2-thienyl)-1,2,4,5-tetrazine (bttz) reacts with trans-Pt(dmso)2(mes)2, mes = mesityl = 2,4,6-trimethylphenyl, under twofold cyclometallation to yield structurally characterized (μ-bttz-2H+)[Pt(dmso)(mes)]2 with uncoordinated thiophene sulfur atoms and bttz deprotonated in the 3,3′ positions. The structural features include cis-positioned carbanionic ligands, twisted mesityl substituents, S-coordinated dmso ligands with the SO bonds lying in the molecular plane, shortened inter-ring bonds, and rather short Pt–C bonds at 1.998(9)/2.00(1) Å (Pt–Cmes) and 1.985(9)/1.99(1) Å (Pt–Cbttz-2H+). Reversible reduction to {(μ-bttz-2H+)[Pt(dmso)(mes)]2}? causes a high-energy shift of the charge transfer bands and the appearance of an unresolved EPR signal at g = 1.9905. 相似文献
13.
Urszula Domańska Kamil Paduszyński Zuzanna Żołek-Tryznowska 《The Journal of chemical thermodynamics》2011,43(2):167-171
(Liquid + liquid) phase equilibria (LLE) of binary mixtures containing hyperbranched polymer Boltorn® H2004 and n-alkanes (n-hexane, n-heptane, n-octane, and n-decane) were studied over the temperature range from about (260 up to 360) K. The polymer is partially miscible with n-alkanes and the solubility decreases with an increase of the chain length of the solvent. Corresponding LLE phase diagrams including spinodal and binodal (liquid + liquid) coexistence curves were calculated in terms of the statistical mechanics – based on the lattice-cluster theory, based only on the upper critical solution temperature, and the polymer chain architecture. The results show semi-qualitative agreement of predicted and experimental equilibrium compositions and temperatures. Boltorn® H2004 reveals complete miscibility in the liquid phase with alcohols (C1–C8), aromatic hydrocarbons (benzene, toluene, and thiophene), and ethers (methyl tetra-butyl ether, ethyl tetra-butyl ether, and tetrahydrofurane). 相似文献
14.
《Tetrahedron: Asymmetry》2007,18(1):123-130
Herein, the reactivity of chlorodeoxypseudoephedrine hydrochlorides with oxo-, thio-, and selenocyanate nucleophiles is reported. 1,3-Heterazolidine-2-iminium or ammonium salts were obtained stereoselectively in most cases. The hard–soft nature of the calcogen atom determines the mechanistic pathway via an SN2 (X = O), aziridine intermediate (X = Se), or both (X = S). A simple method to synthesize stereoselectively the trans-isomer of 3,4-dimethyl-5-phenyl-oxazolidine-2-iminium chloride and the cis-isomer of 4-methyl-5-phenyl-oxazoline-2-ammonium chloride, was also found. In addition, heterazolidine-2-imines or amines were liberated from the corresponding salts [Cl− or XCN− (X = O, S, Se)] with aqueous NaOH. Finally, cis-3,4-dimethyl-5-phenyl-oxazolidine-2-iminium chloride, cis-4-methyl-5-phenyl-oxazoline-2-amine, and trans-4-methyl-5-phenyl-selenazoline-2-amine compounds were studied by X-ray diffraction. 相似文献
15.
16.
The discrete phenolate Nd(2,6-di-tert-butyl-OC6H3)3 has been assessed as pre-catalyst for the polymerization of isoprene using various aluminum based co-catalysts. In combination with MAO and MMAO in toluene, the reaction is quantitative in 1 h at 60 °C, yielding activities comparable to neodymium versatate and isopropylate in similar conditions. In contrast with the abovementioned systems, the phenolate leads to a single site catalyst species in combination with MAO and MMAO. Increasing amounts of MAO in the reactive medium lead to a decrease of the number–average molecular weight of polyisoprene, highlighting the occurrence of chain transfer between neodymium and aluminum. The polymerization is modestly 1,4-trans selective, in the range 60–75%. Using pentane as a solvent and MMAO, ultra high activities up to 3000 kg PI/mol Nd/h can be reached at room temperature, as well as 85% 1,4-cis selectivity. Ternary systems with co-catalysts based on the chlorinated AlEt2Cl in combination with AliBu3 afford finally a 90–98% 1,4-cis stereoselective polymerization depending on the solvent used for the reaction. The SEC traces are in agreement with the presence of several active species for the latter systems. 相似文献
17.
Using a set of experimentally determined liquid chromatography column performance data, it has been investigated how a range of efficiencies can best be covered when using a multi-column system. Two main variants are considered: a serially-connected variant (realizing different column lengths by connecting a different number of column segments in series) and a parallel-connected variant (realizing different column lengths by simply switching between columns with a different length arranged in parallel). Both variants are compared for their ability to keep the average analysis time along a given range of efficiencies as close as possible to the intrinsic Knox & Saleem-speed limit. It was found that the serial connection mode offers a better compromise between average speed and amount of required silica (total required column length) than the parallel connection mode for all efficiency ranges running from 5000–10,000 plates up to 75,000–150,000 plates. Considering an ultra-high performance liquid chromatography (UHPLC) operation at 1200 bar, the best possible serial connection system can get within about within 15–25% of the Knox & Saleem-speed limit, whereas a three-column parallel system can only get to within 40–50% of the speed limit, while needing 50–100% more total column length. In absolute terms, the serially-connected system with individually optimized segment lengths should be able to cover a range of 5000–75,000 theoretical plates (dynamic range of 25) in an average analysis time of 14.3 min when using a 1200 bar instrument. At 400 bar, this would be 37.9 min, showing that the construction of wide-efficiency range systems would be one of the application areas where the advantages of UHPLC-conditions would be most fully realized. 相似文献
18.
Study on cloud points of Triton X-100-cationic gemini surfactants mixtures: A spectroscopic approach
Halide Akbaş Mesut Boz Çiğdem Batıgöç 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(2):671-677
This study investigates the effects of various cationic surfactants on the cloud point (CP) of the nonionic surfactant Triton X-100 (TX-100) in aqueous solutions. Instead of visual observation, a spectrophotometer was used for measurement of the cloud point temperatures. The values of CPs for Triton X-100 can be measured directly because TX-100 has an average number of oxyethylene units per molecule of p ≈ 9.5 and a CP = 66.0 °C. Quaternary ammonium dimeric surfactants (m-s-m, m = 10, 12, and 16, and s = 2, 6, and 10) were synthesized and used. The melting temperature TM and the Krafft temperature TK were measured for 1 wt% aqueous solutions of these synthesized surfactants. The melting temperature of the solid gemini surfactants increased with the carbon number of the alkyl chain. The results showed that additions of the gemini surfactants (which are infinitely miscible with water) to Triton X-100 increased the cloud point of the TX-100 solutions. All salts tested in these studies had a large effect on the CPs of nonionic surfactants due to their effect on water structure and their hydrophilicity. The effect of the alkyl chain length of the gemini surfactant on the CP of Triton X-100 is therefore more important than the spacer chain length. 相似文献
19.
Ionic liquids (ILs) and carbon dioxide (CO2) systems have unique phase behavior that has been applied to applications in reactions, extractions, materials, etc. Detailed phase equilibria and modeling are highly desired for their further development. In this work, the (vapor + liquid) equilibrium, (vapor + liquid + liquid) equilibrium, and (liquid + liquid) equilibrium of n-alkyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide ionic liquids with CO2 were measured at temperatures of (298.15, 323.15, 343.15) K and pressure up to 25 MPa. With a constant anion of bis(trifluoromethylsulfonyl)amide, the n-alkyl chain length on the cation was varied from 1-ethyl-3-methyl-imidazolium ([EMIm][Tf2N]), 1-hexyl-3-methyl-imidazolium ([HMIm][Tf2N]), to 1-decyl-3-methyl-imidazolium ([DMIm][Tf2N]). The effects of the cation on the phase behavior and CO2 solubility were investigated. The longer alkyl chain lengths increase the CO2 solubility. The Peng–Robinson equation of state with van der Waals 2-parameter mixing rule with estimated IL critical properties were used to model and correlate the experimental data. The models correlate the (vapor + liquid) equilibrium and (liquid + liquid) equilibrium very well. However, extrapolation of the model to much higher pressures (>30 MPa) can results in the prediction of a mixture critical point which, as of yet, has not been found in the literature. 相似文献
20.
We report density functional theory (DFT) studies of the dipole polarizabilities of nitrogen-containing octatetraene with a number of Π-electron donor substituent at the end parts. All geometries were optimized at the B3LYP/6-311++G(d,p) level of theory and polarizabilities were done at the same level of theory. The results indicate that for the NO2–(CHCH)4–Y systems we find group polarizabilities in the order: N(Me)2 > NBr2 > OCH3 > Br > NH2 > OH > CH3 > NF2 > H~F.Semi empirical AM1 and QSAR-quality empirical calculations show poor quantitative agreement with the DFT results, but give excellent statistical correlation coefficients with the DFT values. This implies that the results of such cheaper calculations can suitably scaled for predictive purpose. 相似文献