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11.
12.
The equilibrium volatilities at near infinite dilution of various solutes absorbed in molten polystyrene have been determined by a gas chromatographic technique. This method is much more rapid, although, with the present apparatus, probably less accurate than conventional static techniques. The primary parameters obtained from measurements of retention volumes are the Henry's law constants, from which are derived the weight and volume fraction activity coefficients, the Flory-Huggins interaction parameters, and the heats of dilution and solution. Of the solutes investigated, 2-butanone (MEK) was the least, and benzene the most compatible (highest and lowest volume fraction activity coefficients, respectively) with molten polystyrene. A small, but definite, variation of the activity coefficients with polystyrene molecular weight was observed. 相似文献
13.
This paper describes the synthesis of three neutral water soluble poly(amidoamine) (PAMAM) dendrimer derivatives. The ability of the two larger dendrimers to bind small acidic hydrophobic molecules is reported. Spectroscopic data and pH behaviour suggested that the acidic hydrophobes were forming stable ion pairs with the dendrimer's internal, basic tertiary nitrogens. With respect to forming 1:1 and 2:1 substrate/dendrimer complexes, both of the larger dendrimers were equally efficient at binding. All dendrimer/substrate complexes were completely miscible with water in all proportions (i.e. infinitely water soluble). When the bound substrates are drug moieties, then the resulting complexes could be considered as potential drug delivery systems. Flow calorimetry demonstrated that the dendrimers were able to release their hydrophobic guests when in contact with a biological cell. 相似文献
14.
The water gas shift reaction (CO + H2O = CO2+ H2) is catalyzed by aqueous metal carbonyl systems derived from simple mononuclear carbonyls such as Fe(CO)5 and M(CO)6 (M = Cr, Mo, and W) and bases in the 140–200 °C temperature range. The water gas shift reaction in a basic methanol-water solution containing Fe(CO)5 is first order in [Fe(CO)5], zero order in [CO], and essentially independent of base concentration and appears to involve an associative mechanism with a metallocarboxylate intermediate [(CO)4Fe-CO2H]–. The water gas shift reactions using M(CO)6 as catalyst precursors are first order in [M(CO)6], inverse first order in [CO], and first order in [HCO2
–] and appear to involve a dissociative mechanism with formatometallate intermediates [(CO)5M-OCHO]–.The Reppe hydroformylation of ethylene to produce propionaldehyde and 1-propanol in basic solutions containing Fe(CO)5 occurs at 110–140 °C. This reaction is second order in [Fe(CO)5], first order in [C2H4] up to a saturation pressure >1.5 MPa, and inhibited by [CO]. These experimental results suggest a mechanism where the rate-determining step involves a binuclear iron carbonyl intermediate. The substitution of Et3N for NaOH as the base facilitates the reduction of propionaldehyde to 1-propanol but results in a slower rate for the overall reaction.The homogeneous photocatalytic decomposition of the formate ion to H2 and CO2 in the presence of Cr(CO)6 appears to be closely related to the water gas shift reaction. The rate of H2 production from the formate ion exhibits saturation kinetics in the formate ion and is inhibited by added pyridine. The infrared spectra of the catalyst solutions indicate an LCr(CO)5 intermediate. Photolysis of the Cr(CO)6/formate system in aqueous methanol in the presence of an aldehyde RCHO (R =n-heptyl,p-tolyl, andp-anisyl) results in catalytic hydrogenation of the aldehyde to the corresponding alcohol RCH2OH by the formate ion. Detailed kinetic studies onp-tolualdehyde hydrogenation by this method indicates saturation kinetics in formate ion, autoinhibition by thep-tolualdehyde, and a threshold effect for Cr(CO)6 at concentrations >0.004 mol L–1. The presence of an aldehyde can interrupt the water gas shift catalytic cycle by interception of an HCr(CO)5
– intermediate by the aldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1539, September, 1994. 相似文献
15.
16.
A variety of simple alkyl and aryl isocyanides have been polymerized using 0.5% NiCl2 in ethanol as a catalyst. The resulting poly(iminomethylenes) have been characterized by carbon-13 NMR spectroscopy and their polystyrene-equivalent molecular weights have been determined by gel permeation chromatography. Straight chain aliphatic isocyanides having from three to ten carbon atoms in the chain form readily solyble polymers having molecular weights (Mw) in the general range 10,000 to 30,000. Neopentyl isocyanide unlike tert-butyl isocyanide forms an insoluble polymer. A number of new soluble aryl isocyanide polymers have been obtained. However, aryl isocyanides having a single alkyl substituent (CH3, C2H5, CF3) in the ortho position give only insoluble polymers, whereas aryl isocyanides having alkyl substituents in both ortho positions (e.g., 2,6-(CH3)2C6H3NC and 2,4,6-(CH3)3C6H2NC) fail to polymerize under these conditions. The highest molecular weight soluble aryl isocyanide homopolymer is obtained from 3-CH3OC6H4NC(Mw = 26,000). The trimethylsilyl substituted isocyanide (CH3)3SiCH2CH2NC has been obtained from LiCH2NC and (CH3)SiCH2Cl and gives a brown soluble homopolymer with a molecular weight (Mw) of 19,000. 相似文献
17.
King NC Dickinson C Zhou W Bruce DW 《Dalton transactions (Cambridge, England : 2003)》2005,(6):1027-1032
Mesoporous silicates are prepared by templating on the hexagonal (H1) mesophase of surfactant bipyridine complexes of ruthenium(II) using a true liquid-crystal templating approach. On calcination, the surfactant template is removed except for the central metal ion that is oxidised, forming nanoparticles of RuO2 that deposit within the pores. RuO2 is a known oxidation catalyst and, despite its anhydrous nature in these silicates, is found to be very active in catalyzing the oxidation of water by acidic CeIV. 相似文献
18.
King RB 《Inorganic chemistry》2003,42(26):8755-8761
The bismuth polyhedra in ternary transition metal-centered bismuth cluster halides may form discrete molecules or ions, infinite chains, and/or infinite layers. The chemical bonding in many of these diverse structures is related to that in deltahedral boranes exhibiting three-dimensional aromaticity by replacing the multicenter core bond in the boranes with two-center two-electron (2c-2e) bonds from the central transition metal to the nearest neighbor bismuth vertices. Examples of discrete molecules or ions include octahedral MBi(6)(micro-X)(12)(z)()(-) (X = Br, I; M = Rh, Ir, z = 3; M = Ru, z = 4) with exclusively 2c-2e bonds and pentagonal bipyramidal RhBi(7)Br(8) with a 5c-4e bond in the equatorial pentagonal plane indicative of M?bius aromaticity. The compound Ru(3)Bi(24)Br(20) contains a more complicated discrete bismuth cluster ion Ru(2)Bi(17)(micro-Br)(4)(5+), which can be dissected into a RuBi(5) closo octahedron and a RuBi(8) nido capped square antiprism bridged by a Ru(2)Bi(4)(micro-Br)(4) structural unit. In RuBi(4)X(2) (X = Br, I), the same Ru(2)Bi(4)(micro-Br)(4) structural unit bridges Bi(4) squares similar to those found in the known Zintl ion Bi(4)(2)(-) to give infinite chains of Ru(2)Bi(4) octahedra. The electron counts of the RuBi(5), RuBi(8), and Ru(2)Bi(4) polyhedra in these structures follow the Wade-Mingos rules. A different infinite chain structure is constructed from fused RhBi(7/2)Bi bicapped trigonal prisms in Rh(2)Bi(9)Br(3). This Rh(2)Bi(9)Br(3) structure can alternatively be derived from alternating Rh(2/2)Bi(4) octahedra and Rh(2/)(2)Bi(5) pentagonal bipyramids with electron counts obeying the Wade-Mingos rules. Related chemical bonding principles appear to apply to more complicated layer structures such as Pt(3)Bi(13)I(7) containing Kagomé nets of PtBi(8/2) cubes and Ni(4)Bi(12)X(3) containing linked chains of NiBi(6/3)Bi capped trigonal prisms. 相似文献
19.
The thermal unimolecular decomposition of hex-1-ene-3-yne (HEY) has been investigated over the temperature range 949–1230 K using the technique of very low-pressure pyrolysis (VLPP). One reaction pathway is the expected C5? C6 bond fission to form the resonance-stabilized 3-ethenylpropargyl radical. There is a concurrent process producing molecular hydrogen which probably occurs via the intermediate formation of hexatrienes and cyclohexa-1,3-diene. RRKM calculations yield the extrapolated high-pressure rate parameters at 1100 K given by the expressions 1016.0±0.3 exp(?300.4 ± 12.6 kJ mol?1/RT) s?1 for bond fission and 1013.2+0.4 exp(?247.7 ± 8.4 kJ mol?1/RT) for the overall formation of hydrogen. The A factors were assigned from the results of previous studies of related alkynes, alkenes, and alkadienes. The activation energy for the bond fission reaction leads to ΔH [H2CCHCC?H2] = 391.9, DH [H2CCHCCCH2? H] = 363.3, and a resonance stabilization energy of 56.9 ± 14.0 kJ mol?1 for the 3-ethenylpropargyl radical, based on a value of 420.2 kJ mol?1 for the primary C? H bond dissociation energy in alkanes. Comparison with the revised value of 46.6 kJ mol?1 for the resonance energy of the unsubstituted propargyl radical indicates that the ethenyl substituent (CH2?CH) on the terminal carbon atom has only a small effect on the propargyl resonance energy. © John Wiley & Sons, Inc. 相似文献
20.
The coulometric determination of thioacetamide (TAA) with electrogenerated silver is described. The titration is done in a solution 0.1M in both ammonia and sodium hydroxide, and the end-point is detected potentiometncally with a silver-silver sulphide electrode. On repeat analyses of approx. 2-mg samples of TAA an average error of -04% (relative standard deviation 0.25%) was obtained. Important steps in the procedure include cleaning the silver generating electrode in nitric acid before each titration, purging well with nitrogen to remove oxygen, and not using too large a sample. 相似文献