New Procedure for Linear Sweep Voltammetric Determination of Catalytic Reaction Rate Constant. Oxidation of Some Aliphatic Alcohols with Electrolytically Generated Os(VIII)

1995 ◽  
Vol 60 (5) ◽  
pp. 795-801
Author(s):  
Dušan Bustin ◽  
Štefan Mesároš ◽  
Peter Tomčík ◽  
Miroslav Rievaj
Keyword(s):  
Catalytic Reaction ◽  
Oxidation Rate ◽  
Reaction Rate ◽  
Reaction Rates ◽  
Reaction Rate Constant ◽  
Sufficient Accuracy ◽  
Aliphatic Alcohols ◽  
Catalytic Reactions ◽  
Linear Sweep

Oxidation rate of methanol, ethanol and 2-propanol by Os(VIII) in 1 M KOH was determined by evaluating anodic voltammograms of Os(VI) in the presence of the aliphatic alcohols. The proposed method is based on the evaluation of the change of voltammogram shape by catalytic process and on the assumption of its approximation by fractionally integrated voltammograms. This assumption has been confirmed empirically for k'f /a in the interval of <0.04,1>. The rate constants from this interval could be determined with sufficient accuracy. The method is suitable for evaluation of reaction rates slow and moderately fast catalytic reactions. It was compared with other evaluation methods from the literature.

Automated Enzymatic Determination of L-Lactate in Serum, with Use of a Miniature Centrifugal Anlyzer

1976 ◽  
Vol 22 (12) ◽  
pp. 2038-2041 ◽  
Author(s):  
T P Hadjiioannou ◽  
S I Hadjiioannou ◽  
S D Brunk ◽  
H V Malmstadt
Keyword(s):  
Lactate Dehydrogenase ◽  
Reaction Rate ◽  
Enzymatic Reaction ◽  
Reaction Rates ◽  
Enzymatic Determination ◽  
Analytical Recovery ◽  
Rate Method ◽  
Relative Errors ◽  
Lithium Lactate

Abstract We describe an automated enzymatic reaction-rate method for spectrophotometric determination of lactate in serum with a miniature centrifugal analyzer. The L(+)-lactate is selectively oxidized in the presence of lactate dehydrogenase (EC 1.1.1.27) and NAD+ to from NADH, whitch is measured from its absorption. Reaction rates are determined automatically, and unknown concentrations are calculated from a computer0generated calibration curve with aqueous lithium lactate standards. Lactte concentrations in the range 0.32-1.6 µg/4 µl (80-400 mg/liter) of sample were determined with relative errors and coefficient of variation of 4.8%. Analytical recovery of lactate added to pooled serum was 89-112% (average, 101%). Comparison with a kit ("Rapid Lactate") method gave a correlation coefficient squared of 0.979 over a concentration range of 39-779 mg/liter.

Bisulfite Degrades Aflatoxin: Effect of Temperature and Concentration of Bisulfite

1978 ◽  
Vol 41 (10) ◽  
pp. 774-780 ◽  
Author(s):  
M. P. DOYLE ◽  
E. H. MARTH
Keyword(s):  
Rate Constant ◽  
Aflatoxin B1 ◽  
Reaction Rate ◽  
Reaction Rates ◽  
Reaction Rate Constant ◽  
Effect Of Temperature ◽  
Kcal Mole ◽  
First Order ◽  
Potassium Acid Phthalate ◽  
Acid Phthalate

Bisulfite reacted with aflatoxin B1 and G1 resulting in their loss of fluorescence. The reaction was first order with rate depending on bisulfite (or the bisulfite and sulfite) concentration(s). Aflatoxin G1 reacted more rapidly with bisulfite than did aflatoxin B1. In the presence of 0.035 M potassium acid phthalate-NaOH buffer (pH 5.5) plus 1.3% (vol/vol) methanol at 25 C, the reaction rate constant for degradation of aflatoxin G1 was 2.23 × 10−2h− and that for aflatoxin B1 was 1.87 × 10−2h− when 50 ml of reaction mixture contained 1.60 g of K2SO3. Besides bisulfite concentrations, temperature influenced reaction rates. The Q10 for the bisulfite-aflatoxin reaction was approximately 2 while activation energies for degrading aflatoxin B1 and aflatoxin G1 were 13.1 and 12.6 kcal/mole, respectively. Data suggest that treating foods with 50 to 500 ppm SO2 probably would not effectively degrade appreciable amounts of aflatoxin. Treating foods with 2000 ppm SO2 or more and increasing the temperature might reduce aflatoxin to an acceptable level.

Determination of the reaction rate constant and activation energy for pressure-induced 2+2 cycloaddition of the C60 fullerene

2002 ◽  
Vol 44 (3) ◽  
pp. 557-559 ◽  
Author(s):  
V. A. Davydov ◽  
L. S. Kashevarova ◽  
A. V. Rakhmanina ◽  
V. M. Senyavin ◽  
N. N. Oleinikov ◽  
...  
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Reaction Rate ◽  
Reaction Rate Constant ◽  
C60 Fullerene

scholarly journals Impacts of electronically photo-excited NO<sub>2</sub> on air pollution in the South Coast Air Basin of California

2010 ◽  
Vol 10 (3) ◽  
pp. 1171-1181 ◽  
Author(s):  
J. J. Ensberg ◽  
M. Carreras-Sospedra ◽  
D. Dabdub
Keyword(s):  
Particulate Matter ◽  
Rate Constant ◽  
Reaction Rate ◽  
Control Strategies ◽  
Reaction Rates ◽  
Reaction Rate Constant ◽  
South Coast ◽  
Nox Emissions ◽  
The South ◽  
South Coast Air Basin

Abstract. A new path for hydroxyl radical formation via photo-excitation of nitrogen dioxide (NO2) and the reaction of photo-excited NO2 with water is evaluated using the UCI-CIT model for the South Coast Air Basin of California (SoCAB). Two separate studies predict different reaction rates, which differ by nearly an order of magnitude, for the reaction of photo-excited NO2 with water. Impacts of this new chemical mechanism on ozone and particulate matter formation, while utilizing both reaction rates, are quantified by simulating two summer episodes. First, sensitivity simulations are conducted to evaluate the uncertainty in the rate of reaction of photo-excited NO2 with water reported in the literature. Results indicate that the addition of photo-excited NO2 chemistry increases peak 8-h average ozone and particulate matter concentrations. The importance of this new chemistry is then evaluated in the context of pollution control strategies. A series of simulations are conducted to generate isopleths for ozone and particulate matter concentrations, varying baseline nitrogen oxides (NOx) and volatile organic compounds (VOC) emissions. Isopleths are obtained using 1987 emissions, to represent past conditions, and 2005, to represent current conditions in the SoCAB. Results show that the sensitivity of modeled pollutant control strategies due to photoexcitation decreases with the decrease in baseline emissions from 1987 to 2005. Results show that including NO2 photo-excitation, increases the sensitivity of ozone concentration with respect to changes in NOx emissions for both years. In particular, decreasing NOx emissions in 2005 when NO2 photo-excitation is included, while utilizing the higher reaction rate, leads to ozone relative reduction factors that are 15% lower than in a case without photo-excited NO2. This implies that photoexcitation increases the effectiveness in reducing ozone through NOx emissions reductions alone, which has implications for the assessment of future emission control strategies. However, there is still disagreement with respect to the reaction rate constant for the formation of OH. Therefore, further studies are required to reduce the uncertainty in the reaction rate constant before this new mechanism is fully implemented in regulatory applications.

A Much-Needed Mechanism and Reaction Rate for the Oxidation of Phenols with ClO2: A Joint Experimental and Computational Study

2013 ◽  
Vol 66 (7) ◽  
pp. 814 ◽  
Author(s):  
Carlos Alberto Huerta Aguilar ◽  
Jayanthi Narayanan ◽  
Mariappan Manoharan ◽  
Narinder Singh ◽  
Pandiyan Thangarasu
Keyword(s):  
Oxidation Rate ◽  
Density Functional ◽  
Reaction Rate ◽  
Computational Study ◽  
Reaction Rate Constant ◽  
Oxidation Products ◽  
Gas Chromatography Mass Spectrometry ◽  
Activation Barriers ◽  
Oxidation Of Phenols ◽  
The Right

The oxidation of phenols with chlorine dioxide, a powerful means to eliminate phenol pollutants from drinking water, is explored. Kinetic experiments reveal that 2,4,6-trichlorophenol exhibits a lower oxidation rate than other phenols because the chlorine atoms (σ = 0.22) at ortho and para-positions decrease the benzene’s electron density, in agreement with the Hammett plot. The oxidation of phenol was found to be second order with respect to phenol and first order with respect to ClO2 and a possible mechanism is proposed. The phenol/ClO2 oxidation was found to be pH-dependent since the reaction rate constant increases with increasing pH. The oxidation rate was also significantly enhanced with an increasing methanol ratio in water. The oxidation products, such as benzoquinones, were analysed and confirmed by liquid chromatography and gas chromatography–mass spectrometry. Density functional theory computations at both the B3LYP/6-311+G(d,p) and M06-2X.6-311+G(d,p) levels with the SCRF-PCM solvation model (i.e. with water) further supported the proposed mechanisms in which activation barriers predicted the right reactivity trend as shown by the kinetic experiments.

scholarly journals Determination of Surface Reaction Rate Constant by Using Micro-Trench Method in APCVD.

1991 ◽  
Vol 17 (6) ◽  
pp. 1175-1178 ◽  
Author(s):  
Hee Joon Kim ◽  
Yasuyuki Egashira ◽  
Hiroshi Komiyama
Keyword(s):  
Rate Constant ◽  
Reaction Rate ◽  
Surface Reaction ◽  
Reaction Rate Constant

scholarly journals Enzymatic Kinetics of Solvent-free Esterification with Bio-imprinted Lipase

2020 ◽  
Vol 33 (4) ◽  
pp. 495-499
Author(s):  
M. Matsumoto ◽  
Y. Hasegawa
Keyword(s):  
Carboxylic Acids ◽  
Propionic Acid ◽  
Catalytic Reaction ◽  
Reaction Rate ◽  
Isoamyl Alcohol ◽  
Reaction Rate Constant ◽  
Solvent Free ◽  
Enzymatic Esterification ◽  
Catalytic Activities ◽  
Kinetics Of

To avoid the use of compounds that burden the environment, a solvent-free enzymatic<br /> reaction was the focus of this study. Investigated were the catalytic activities and kinetics of lipases that were pretreated with carboxylic acids for the solvent-free esterification of propionic acid with isoamyl alcohol. The enhancements of the esterification yields and rates by the bio-imprinting effects of carboxylic acids were observed. We found no inhibition of isoamyl alcohol on the solvent-free enzymatic esterification, and obtained a large imprinting effect under a largely excessive amount of isoamyl alcohol to propionic acid. From the kinetic analysis, the imprinting of lipases mainly enhanced the catalytic reaction rate constant rather than the affinity between lipase and propionic acid compared with untreated lipase. The bio-imprinting treatment of lipase is found to be very effective for the yield and kinetics in solvent-free esterification.

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