Competitive hydrogenation of olefinic substrates in multicomponent systems

1978 ◽  
Vol 43 (9) ◽  
pp. 2387-2394 ◽  
Author(s):  
Libor Červený ◽  
Dana Plecháčová ◽  
Vlastimil Růžička
Author(s):  
Dennis Maher ◽  
David Joy ◽  
Peggy Mochel

A variety of standard specimens is needed in order to systematically investigate the instrumentation, specimen, data reduction and quantitation variables in electron energy-loss spectroscopy (EELS). Pure single element specimens (e.g. various forms of carbon) have received considerable attention to date but certain elements of interest cannot be prepared directly as thin films. Since studies of the first and second row elements in two- or multicomponent systems will be of considerable importance in microanalysis using EELS, there is a need for convenient standards containing these species. For many investigations a standard should contain the desired element, or elements, homogeneously dispersed through a suitable matrix and at an accurately known concentration. These conditions may be met by the technique of implantation.Silicon was chosen as the host lattice since its principal ionization energies, EL23 = 98 eV and Ek = 1843 eV, are well removed from the K-edges of most elements of major interest such as boron (Ek = 188 eV), carbon (Ek = 283 eV), nitrogen (Ek = 400 eV) and oxygen (Ek = 532 eV).


Pharmaceutics ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 475
Author(s):  
Guijin Liu ◽  
Junjian Li ◽  
Shiming Deng

Solid multicomponent systems (SMS) are gaining an increasingly important role in the pharmaceutical industry, to improve the physicochemical properties of active pharmaceutical ingredients (APIs). In recent years, various processes have been employed for SMS manufacturing. Control of the particle solid-state properties, such as size, morphology, and crystal form is required to optimize the SMS formulation. By utilizing the unique and tunable properties of supercritical fluids, supercritical anti-solvent (SAS) process holds great promise for the manipulation of the solid-state properties of APIs. The SAS techniques have been developed from batch to continuous mode. Their applications in SMS preparation are summarized in this review. Many pharmaceutical co-crystals and solid dispersions have been successfully produced via the SAS process, where the solid-state properties of APIs can be well designed by controlling the operating parameters. The underlying mechanisms on the manipulation of solid-state properties are discussed, with the help of on-line monitoring and computational techniques. With continuous researching, SAS process will give a large contribution to the scalable and continuous manufacturing of desired SMS in the near future.


Author(s):  
Joseph W. Gregory ◽  
S. David Jackson

AbstractThe cascade reactions of phenylacetylene to ethylcyclohexane and 1-phenyl-1-propyne to propylcyclohexane were studied individually, under deuterium and competitively at 343 K and 3 barg pressure over a Rh/silica catalyst. Both systems gave similar activation energies for alkyne hydrogenation (56 ± 4 kJ mol−1 for phenylacetylene and 50 ± 4 kJ mol−1 for 1-phenyl-1-propyne). Over fresh catalyst the order of reactivity was styrene > phenylacetylene ≫ ethylbenzene. Whereas with the cascade hydrogenation starting with phenylacetylene, styrene hydrogenated much slower phenylacetylene even once all the phenylacetylene was hydrogenated. The activity of ethylbenzene was also reduced in the cascade reaction and after styrene hydrogenation. These reductions in rate were likely due to carbon laydown from phenylacetylene and styrene. Similar behavior was observed with the 1-phenyl-1-propyne cascade. Deuterium experiments revealed similar positive KIEs for phenylacetylene (2.6) and 1-phenyl-1-propyne (2.1). Ethylbenzene hydrogenation/deuteration gave a KIE of 1.6 obtained after styrene hydrogenation in contrast to the inverse KIE of 0.4 found with ethylbenzene hydrogenation/deuteration over a fresh catalyst, indicating a change in rate determining step. Competitive hydrogenation between phenylacetylene and styrene reduced the rate of phenylacetylene hydrogenation but increased selectivity to ethylbenzene suggesting a change in the flux of sub-surface hydrogen. In the competitive reaction between 1-phenyl-1-propyne and propylbenzene, the rate of hydrogenation of 1-phenyl-1-propyne was increased and the rate of alkene isomerization was decreased, likely due to an increase in the hydrogen flux for hydrogenation and a decrease in the hydrogen species active in methylstyrene isomerization.


2020 ◽  
Vol 153 (11) ◽  
pp. 114302
Author(s):  
Diletta Meroni ◽  
Angelo Monguzzi ◽  
Francesco Meinardi

2016 ◽  
Vol 70 (12) ◽  
Author(s):  
Leonid Serafimov ◽  
Anastasia Frolkova

AbstractA method for the determination of vapor–liquid phase diagram structure of five-component systems based on the analysis of types and Poincare indexes of singular points of the geometric scan and full structure of the concentration simplex is proposed. Validity of the proposed method was demonstrated by vapor–liquid equilibrium modeling in five-component mixtures: ethanol + water + toluene + butanol + chlorbenzene and acetone + chloroform + ethanol + cyclohexane + water.


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