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81.
Harald Schfer 《无机化学与普通化学杂志》1974,410(3):269-273
The Chemical Transport of Platinum with Chlorine Experiments show that the chemical transport of platinum by means of chlorine within a temperature gradient at temperatures below ≈ 1000°K goes into the hot temperature region, but at higher temperatures in the reverse direction. From the thermodynamic discussion it can be seen, that the platinum content of the gas phase at low temperatures is governed by the exothermic formation of Pt6Cl12,g, and at higher temperatures by the endothermic formation of PtCl3,g and PtCl2,g. The platinum content of the gas phase passes a minimum at ≈ 1000°K, if P(Cl2) = 3.5 atm. This result is in agreement with the observed inversion of the transport direction. 相似文献
82.
Walter Purcell Andreas Roodt Stephen S. Basson Johann G. Leipoldt 《Transition Metal Chemistry》1990,15(3):239-241
Summary The crystal structure of the tetraethylammonium salt of [ReO(H2O)(CN)4]– has been determined from threedimensional x-ray diffraction data. The light blue crystals are monoclinic, space group P21/m witha=8.760(1),b=9.518(5),c=11.718(1) Å, =102.63(1)o with two molecules per unit cell. The final R value using 2009 observed reflections and anisotropic thermal parameters for all the non-hydrogen atoms was 0.038. The [ReO(H2O)(CN)4]– ion has a distorted octahedral geometry with the rhenium atom displaced by 0.30 Å out of the plane formed by the four carbon atoms of the cyano ligands towards the oxo ligand. Bond distances: Re=O=1.667(8), Re–OH2=2.142(7) and Re–C (average)=2.11(1) Å. 相似文献
83.
Mass Spectroscopic Observations and Chemical Transport Experiments with the Systems VCl3/Al2Cl6 and VCl2/Al2Cl6 By mass spectrometry the equilibrium VCl3,s + 0.5 Al2Cl6,g ? VAlCl6,g has been determined: ΔH°(298) = 25.6(±0.5) kcal; ΔS°(298) = 23.0(±3) cal/K, ΔCp (assumed) = ?4 cal/K. This is approximately in agreement with results determined by ligand field spectroscopy by ANUNDSKÅS and ØYE (A. and Ø.). For the dimerization of VCl3,g values for ΔH and ΔS have been derived. The molecule VAl2Cl9 assumed by A. and Ø. could not been observed by mass spectrometry. For the VCl2/Al2Cl6 complex, observed by chemical transport, A. and Ø. give the formula VAl3Cl11. This molecule could not been observed by mass spectrometry. This suggests a smaller concentration, compared with the results of A. and Ø. Stabilization of VCl2,s (by metal-nietal-bonds) shifts the reaction to the left, whith explains the lower complex concentration as well as the larger molecular weight of the complex. With chlorides stabilized by stronger metal-metal bonds (MoCl3, MoCl2, Nb3Cl8) AlCl3 complexes are not formed in observable concentrations. The chemical transport of VCl2 with Al2Cl6 needs relatively high temperatures (973 → 873 K). In this case the addition of SiCl4 hinders the attack of the quartz ampoule by Al2Cl6. Using a VCl3 + VCl2 mixture, VCl3 is transported by Al2Cl6 (673 → 623 K) into the colder region. If afterwords the ampoule is reversed, VCl3 again moves into the colder region, but the thermal decomposition of VCl3 at the same time causes that a VCl2-residue remains in the hot region. 相似文献
84.
Franz Andreas Mautner Harald Krischner Christoph Kratky 《Monatshefte für Chemie / Chemical Monthly》1988,119(11):1245-1249
[N(CH3)4]Ca(N3)3,M=240.29, was prepared from aqueous solutions of tetramethylammoniumazide with calciumazide at 298 K. The crystals are tetragonala=936.6(7) pm,c=694.7(5)pm, space group P4/nmm,Z=2, (x)=1.31Mgm–3. The crystal structure was determined by single crystal x-ray diffraction (234 Mo-K-reflections, =0.469 mm–1,R=0.064). Calcium is octahedrally coordinated to six azide groups. The octahedra are connected via azide groups to a threedimensional array with the complex ammonium ions between. The terminal nitrogen atoms of the azide groups and the methyl groups are considerably disordered. 相似文献
85.
Hydrolysis of Amides of Phospholinic Acid The acid catalysed hydrolysis of (= OAP, R = organic substituent) has been investigated kinetically. Provided the pH remains constant, the hydrolysis is a first order reaction. From the temperature dependance of the rate constant the activation energy Ea as well as the thermodynamic data ΔH* and ΔS* have been calculated. In comparison to the compound with R = H aromatic substituents and additional the t-butyl group enhance Ea whilst aliphatic substituents included the benzyl group diminish Ea. The first step of the reaction is a protonation at the oxygen or nitrogen resulting in the formation of an equilibrium. After the determination of the basicity constant KA of some OAPs it was possible to calculate the respective rate constants of the rate determining step of the reactions and the corresponding thermodynamic data EF, ΔH and ΔS. It is assumed that the mechanism of the hydrolysis takes place according to the same scheme which has been assumed for the hydrolysis of cyclic esters of the phosphinic acid by Ugi [1] and colaborators. 相似文献
86.
The purpose of this communication is to describe the preparation and some properties of the first two synthetic peptides containing D - and L -γ-carboxyglutamic acid. Use was made of N-protected γ,γ′-di-t-butyl-γ-carboxyglutamic acids (D , L , and DL ) described earlier [1 a]. Preliminary 1H-NMR. data (360 MHz) indicate a restricted rotation of the Gla side chain in the free amino acid as well as in the C-terminal Gla of Gla-Gla in H2O solution at acid pH. The proton dissociation from Gla and Gla-Gla was studied by potentiometric titration and NMR. methods. The pH titration in the presence of Ca2+ ions shows that Gla-Gla has a much higher association constant for this cation than Gla. It is almost as great as that of prothrombin (pCa2+ = 3.2 vs. 3.5). 相似文献
87.
Gas Molecules Pd2Al2Cl10 and PdAlCl5 as Accompanists of PdAl2Cl8 Mass spectrometric observations using a double cell showed that the reaction of gaseous Al2Cl6 with solid PdCl2 besides the known gaseous complex PdAl2Cl8 gives PdAlCl5 and the unexpected complex Pd2Al2Cl10. For the equilibrium (with ΔCp? ?1 cal/K) ΔH°(298) = 7.5 kcal/Mol and ΔS°(298) = 5.3 ± 2 cl have been obtained. 相似文献
88.
Flash vacuum pyrolysis (fvp) of some substituted [1,2,4]triazolo[3,4-c][1,2,4]benzotriazine derivatives (1a-d) has been studied between 450 and 600 °C. The only transformation observed up to 525 °C was the unexpected valence bond isomerization of the angularly fused starting compounds to the isomeric linearly fused [1,2,4]triazolo[4,3-b][1,2,4]benzotriazine derivatives (9a-d), whereas at higher temperatures fragmentation products such as aromatic nitriles were also formed. Kinetic measurements revealed negative entropies of activation in the isomerization process, which suggest a concerted ring closure reaction to an intermediate antiaromatic diazirine. Reversibiblity of the title isomerization reaction was also proved by FVP experiments. 相似文献
89.
Two different methods for the quantification of human tissue inhibitor of metalloproteinases-2 (TIMP-2) were developed using surface plasmon resonance (SPR) and gold nanoparticles for signal enhancement. The first method, a competitive assay, used TIMP-2 immobilized to the sensor surface and the inactive form of matrix metalloproteinase-2 (proMMP-2) (EC 3.4.24.24) adsorbed to gold nanoparticles. The sensor signals resulting from the interaction of MMP-2-gold nanoparticles with immobilized TIMP-2 were inversely proportional to the amounts of TIMP-2 of the sample. The measuring range for TIMP-2 was about 15–180 pM. The second method, a one-step sandwich assay, used proMMP-2 immobilized to the sensor surface and an anti-TIMP-2 monoclonal antibody coupled to gold nanoparticles. The lower detection limit of this assay format was 0.5 pM of TIMP-2. The binding signals were highly reproducible up to 100 pM of the inhibitor. The improvements obtained in TIMP-2 quantification over already existing tests could contribute to a better understanding and diagnosis of diseases like cancer. 相似文献
90.
The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener. 相似文献