The Catalytic Decomposition of Isopropyl Alcohol Vapor on Manganese (II) Oxide

1971 ◽  
Vol 49 (23) ◽  
pp. 3778-3784 ◽  
Author(s):  
D. G. Klissurski ◽  
E. F. McCaffrey ◽  
R. A. Ross
Keyword(s):  
Partial Pressure ◽  
Isopropyl Alcohol ◽  
Catalytic Decomposition ◽  
Nitrogen Adsorption ◽  
Mesityl Oxide ◽  
Alcohol Vapor ◽  
Rate Limiting Step ◽  
Partial Pressures ◽  
Dehydration Reactions ◽  
Rate Limiting

The vapor phase decomposition of isopropyl alcohol has been studied from 210 to 365 °C on manganese(II) oxide. Rates of conversion to acetone and propylene were measured with partial pressures of isopropyl alcohol from 0.3 to 22 mm. The catalyst selectivity towards dehydrogenation was around 0.80 between 320 and 365 °C while at 306 °C it was somewhat less and depended on the alcohol partial pressure. Propylene and hydrogen additions had no effect on the reaction rate while the reaction order with respect to isopropyl alcohol partial pressure was 0.4 to 0.6 except at 306 °C when it decreased with increase in the alcohol partial pressure. The effects of acetone and water additions were shown respectively to be exerted mainly on the dehydrogenation and dehydration reactions while at acetone pressures above 4 mm, considerable amounts of by-products including mesityl oxide and heavier ketones were clearly detected. The apparent activation energy of the overall decomposition as calculated from the experimental rates was 26 ± 0.5 kcal mol−1. The results have been interpreted to be in general agreement with the concept that the rate-limiting step is linked to the direct interactions on the catalyst surface and it has been established that the reaction is significantly more complex than previously recognized. The physical properties of the manganese(II) oxide were determined by X-ray and nitrogen adsorption techniques while infrared, n.m.r., and gas chromatographic methods were used to analyze the products of catalysis.

scholarly journals Nitrogen Assimilation and Transport by Ex Planta Nitrogen-Fixing Bradyrhizobium diazoefficiens Bacteroids Is Modulated by Oxygen, Bacteroid Density and l-Malate

2020 ◽  
Vol 21 (20) ◽  
pp. 7542
Author(s):  
James K. Waters ◽  
Thomas P. Mawhinney ◽  
David W. Emerich
Keyword(s):  
Amino Acid ◽  
Partial Pressure ◽  
Chemical Nature ◽  
Glutamate Uptake ◽  
Ammonium Uptake ◽  
Acid Excretion ◽  
Partial Pressure Of Oxygen ◽  
Partial Pressures ◽  
Branch Chain Amino ◽  
Rate Limiting

Symbiotic nitrogen fixation requires the transfer of fixed organic nitrogen compounds from the symbiotic bacteria to a host plant, yet the chemical nature of the compounds is in question. Bradyrhizobium diazoefficiens bacteroids were isolated anaerobically from soybean nodules and assayed at varying densities, varying partial pressures of oxygen, and varying levels of l-malate. Ammonium was released at low bacteroid densities and high partial pressures of oxygen, but was apparently taken up at high bacteroid densities and low partial pressures of oxygen in the presence of l-malate; these later conditions were optimal for amino acid excretion. The ratio of partial pressure of oxygen/bacteroid density of apparent ammonium uptake and of alanine excretion displayed an inverse relationship. Ammonium uptake, alanine and branch chain amino acid release were all dependent on the concentration of l-malate displaying similar K0.5 values of 0.5 mM demonstrating concerted regulation. The hyperbolic kinetics of ammonium uptake and amino acid excretion suggests transport via a membrane carrier and also suggested that transport was rate limiting. Glutamate uptake displayed exponential kinetics implying transport via a channel. The chemical nature of the compounds released were dependent upon bacteroid density, partial pressure of oxygen and concentration of l-malate demonstrating an integrated metabolism.

Isotope effect studies of the decomposition of 2-propanol on hafnium(IV) oxide

1977 ◽  
Vol 55 (1) ◽  
pp. 153-157
Author(s):  
Ian M. Hoodless
Keyword(s):  
Hydrogen Bond ◽  
Isotope Effect ◽  
Catalytic Decomposition ◽  
Hafnium Dioxide ◽  
Small Extent ◽  
Dehydrogenation Reaction ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Major Reaction ◽  
Rate Limiting

The catalytic decomposition of 2-propanol on hafnium dioxide has been investigated over the temperature range 355–397 °C by a micropulse reactor technique. The major reaction is one of dehydration to propene but dehydrogenation also occurs to a small extent. Isotope effect measurements with deuterio-2-propanols indicate that the rate-limiting step in dehydration involves cleavage of the β-carbon-hydrogen while in the dehydrogenation reaction it is cleavage of the α-carbon-hydrogen bond.

A mechanistic study of the [La2(OCH3)2]4+- and [(1,5,9-triazacyclodo-decane):Zn:(OCH3)]+-catalyzed methanolysis of carbonates: possible application for the recycling of bisphenol A polycarbonates

2013 ◽  
Vol 91 (11) ◽  
pp. 1139-1146 ◽  
Author(s):  
Alexei A. Neverov ◽  
Leanne D. Chen ◽  
Sean George ◽  
David Simon ◽  
Christopher I. Maxwell ◽  
...  
Keyword(s):  
Bisphenol A ◽  
Metal Ion ◽  
Catalytic Decomposition ◽  
Nucleophilic Attack ◽  
Alkyl Derivative ◽  
Mechanistic Study ◽  
Tetrahedral Intermediate ◽  
Rate Limiting Step ◽  
Leaving Group ◽  
Rate Limiting

The kinetics of the methanolysis of seven methyl aryl carbonates (3) and two methyl alkyl carbonates (4) promoted by [12[ane]N3:Zn:(OCH3)]+ and [La2(OCH3)2]4+ catalysts (1 and 2, respectively) have been studied at 25.0 °C. Brønsted plots of the [Formula: see text] values for methanolysis versus aryloxy and alkoxy leaving group (LG) [Formula: see text] or [Formula: see text] values (the pKa values of the parent ArOH or ROH in methanol) for substrates 3 and 4 show an apparent downward break at [Formula: see text] ∼16.6 and 15.2 with [12[ane]N3:Zn:(OCH3)]+ and [La2(OCH3)2]4+, respectively. The breakpoint is not due to a change in rate-limiting step in a two-step process involving metal ion delivery of a coordinated methoxide to a transiently associated substrate and the subsequent breakdown of a tetrahedral intermediate to form product. The more satisfactory explanation is that the break arises when one correlates the rate constants for two dissimilar sets of substrates, namely aryloxy- and alkoxy-substituted 3 and 4. DFT calculations for the 1-promoted reactions of methyl 4-nitrophenyl carbonate (3b), which has a good aryloxy leaving group, and methyl isopropyl carbonate (4b), which has a relatively poor alkyl one, indicate that the catalyzed processes involve two steps. Accordingly, the methanolysis of all 3 having [Formula: see text] values for the parent phenols ≤15.3 involves rate-limiting nucleophilic attack and fast breakdown. For the isopropyl alkyl derivative (4b) having a [Formula: see text] > 18.13, the rate-liming step is the metal ion promoted breakdown of a tetrahedral intermediate. The catalytic system employing 2 has utility for the catalytic decomposition of poly(bisphenol A carbonate). In a semi-optimized system where 1000 mg of poly(bisphenol A carbonate), treated at 100 °C for 30 min in 2 mL of 60:40 chloroform−methanol containing La(OTf)3:NaOMe (5:7.5 mmol L−1), the reaction gave an 84% yield of bisphenol A, corresponding to >300 turnovers per catalyst.

Ornithine Decarboxylase Activity in Cultured Endothelial Cells Stimulated by Serum, Thrombin and Serotonin

1978 ◽  
Vol 39 (02) ◽  
pp. 496-503 ◽  
Author(s):  
P A D’Amore ◽  
H B Hechtman ◽  
D Shepro
Keyword(s):  
Endothelial Cells ◽  
Ornithine Decarboxylase ◽  
Decarboxylase Activity ◽  
Aortic Endothelial Cells ◽  
Ornithine Decarboxylase Activity ◽  
Rate Limiting Step ◽  
Bovine Aortic Endothelial Cells ◽  
Limiting Step ◽  
Rate Limiting ◽  
Serum Serotonin

SummaryOrnithine decarboxylase (ODC) activity, the rate-limiting step in the synthesis of polyamines, can be demonstrated in cultured, bovine, aortic endothelial cells (EC). Serum, serotonin and thrombin produce a rise in ODC activity. The serotonin-induced ODC activity is significantly blocked by imipramine (10-5 M) or Lilly 11 0140 (10-6M). Preincubation of EC with these blockers together almost completely depresses the 5-HT-stimulated ODC activity. These observations suggest a manner by which platelets may maintain EC structural and metabolic soundness.

Dynamics of hepatic and peripheral insulin effects suggest common rate-limiting step in vivo

Diabetes ◽  
1993 ◽  
Vol 42 (2) ◽  
pp. 296-306 ◽  
Author(s):  
D. C. Bradley ◽  
R. A. Poulin ◽  
R. N. Bergman
Keyword(s):  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting

Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation

2020 ◽  
Author(s):  
Chang-Sheng Wang ◽  
Sabrina Monaco ◽  
Anh Ngoc Thai ◽  
Md. Shafiqur Rahman ◽  
Chen Wang ◽  
...  
Keyword(s):  
Catalytic System ◽  
Lewis Acid ◽  
Hydrogen Transfer ◽  
Acid Catalysis ◽  
Rate Limiting Step ◽  
Site Selectivity ◽  
Set Up ◽  
Site Selective ◽  
First Time ◽  
Rate Limiting

A catalytic system comprised of a cobalt-diphosphine complex and a Lewis acid (LA) such as AlMe3 has been found to promote hydrocarbofunctionalization reactions of alkynes with Lewis basic and electron-deficient substrates such as formamides, pyridones, pyridines, and azole derivatives through site-selective C-H activation. Compared with known Ni/LA catalytic system for analogous transformations, the present catalytic system not only feature convenient set up using inexpensive and bench-stable precatalyst and ligand such as Co(acac)3 and 1,3-bis(diphenylphosphino)propane (dppp), but also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Mechanistic stidies including DFT calculations on the Co/Al-catalyzed addition of formamide to alkyne have suggested that the reaction involves cleavage of the carbamoyl C-H bond as the rate-limiting step, which proceeds through a ligand-to-ligand hydrogen transfer (LLHT) mechanism leading to an alkyl(carbamoyl)cobalt intermediate.

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