Effects of ortho-Substituents in Protonolysis of Arylmercuric Chlorides with Hydrochloric Acid

2000 ◽  
Vol 65 (1) ◽  
pp. 35-46 ◽  
Author(s):  
Yulan Wang ◽  
Yangjie Wu
Keyword(s):  
Hydrochloric Acid ◽  
Rate Constant ◽  
Sodium Iodide ◽  
Underlying Mechanism ◽  
Experimental Results ◽  
Fixed Temperature ◽  
First Order ◽  
Kinetics Of Reaction ◽  
Kinetics Of

The kinetics of reaction of ortho-substituted phenylmercuric chlorides, 2-R-C6H4HgCl (R = H, CH3, CH3O, C2H5O, CF3, COOC2H5, Cl, Br, F, NO2), with hydrochloric acid in absolute ethanol in the presence of sodium iodide has been studied. The reaction is of the overall second order, first order with respect to each reactant. The rate constant determined at a fixed temperature decreases in the order of R: C2H5O > CH3O > CH3 > H > COOC2H5 > F > Cl > Br > CF3 > NO2. The role of inductive, resonance and field effects of the ortho-substituents, and the relation between steric demands of the ortho-substituents and volume of attacking species are discussed. The underlying mechanism is proposed on the basis of experimental results.

Formation of hexacyanomanganate(II) in cyanide medium and kinetics and mechanism of its oxidation by chromate

1989 ◽  
Vol 67 (2) ◽  
pp. 279-283
Author(s):  
Guillermo López-Cueto ◽  
Mlguel Duarte
Keyword(s):  
Reaction Mechanism ◽  
Complex Formation ◽  
Rate Constant ◽  
Equilibrium Constants ◽  
Formation Rate ◽  
Experimental Results ◽  
First Order ◽  
Hydroxo Complexes ◽  
Monomolecular Decomposition ◽  
Kinetics Of

The rate of formation of hexacyanomanganate(II) is first-order in Mn(II) and depends on both the cyanide and hydroxide concentrations. The experimental results agree with a reaction mechanism which involves manganese(II) cyano- and hydroxo-complexes. Chromate slowly oxidizes hexacyanomanganate(II). The kinetics of this reaction is first-order on hexacyanomanganate(II), and the experimental rate constant depends on the chromate concentration according to the equation kexp = 3kK[Cr(VI)]/(1 + K[Cr(VI)]). The effect of both the CN− and the OH− ions is slighter. A tentative mechanism is proposed which involves a pre-equilibrium with the formation of a hexacyanomanganate(II)–chromate complex, followed by a monomolecular decomposition. By comparing this reaction mechanism with that of other one-electron chromate reductions, it appears that hexacyanomanganate(II) behaves like octacyanomolybdate(IV) rather than like hexacyanoferrate(II) and other substitution-inert reductants. Both the equilibrium constants for the complex formation and the rate constant for its decomposition are evaluated, and voltammetric evidence of the formation of hexacyanomanganate(III)–chromate complexes is also presented. Keywords: hexacyanomanganate(II), formation rate, oxidation with chromate, kinetics, mechanism.

Spectrochemical Behavior of Carcinogenic Polycyclic Aromatic Hydrocarbons in Biological Systems. Part II: A Theoretical Rate Model for BaP Metabolism in Living Cells

1996 ◽  
Vol 50 (11) ◽  
pp. 1352-1359 ◽  
Author(s):  
Ping Chiang ◽  
Kuang-Pang Li ◽  
Tong-Ming Hseu
Keyword(s):  
Rate Constant ◽  
Living Cells ◽  
Rate Model ◽  
Number Density ◽  
Order Process ◽  
Irreversible Reaction ◽  
First Order ◽  
Metabolism Rate ◽  
Polycyclic Aromatic ◽  
Kinetics Of

An idealized model for the kinetics of benzo[ a]pyrene (BaP) metabolism is established. As observed from experimental results, the BaP transfer from microcrystals to the cell membrane is definitely a first-order process. The rate constant of this process is signified as k1. We describe the surface–midplane exchange as reversible and use rate constants k2 and k3 to describe the inward and outward diffusions, respectively. The metabolism is identified as an irreversible reaction with a rate constant k4. If k2 and k3 are assumed to be fast and not rate determining, the effect of the metabolism rate, k4, on the number density of BaP in the midplane of the microsomal membrane, m3, can be estimated. If the metabolism rate is faster than or comparable to the distribution rates, k2 and k3, the BaP concentration in the membrane midplane, m3, will quickly be dissipated. But if k4 is extremely small, m3 will reach a plateau. Under conditions when k2 and k3 also play significant roles in determining the overall rate, more complicated patterns of m3 are expected.

scholarly journals Kinetics of thiamin cleavage by sulphite

1969 ◽  
Vol 113 (4) ◽  
pp. 611-615 ◽  
Author(s):  
J. Leichter ◽  
M. A. Joslyn
Keyword(s):  
Aqueous Solutions ◽  
Rate Constant ◽  
Sulphur Dioxide ◽  
First Order ◽  
Ph Values ◽  
Rate Of Reaction ◽  
Kinetics Of

Results are presented on the rate of thiamin cleavage by sulphite in aqueous solutions as affected by temperature (20–70°), pH(2·5–7·0), and variation of the concentration of either thiamin (1–20μm) or sulphite (10–5000μm as sulphur dioxide). Plots of the logarithm of percentage of residual thiamin against time were found to be linear and cleavage thus was first-order with respect to thiamin. At pH5 the rate was also found to be proportional to the sulphite concentration. In the pH region 2·5–7·0 at 25° the rate constant was 50m−1hr.−1 at pH5·5–6·0, and decreased at higher or lower pH values. The rate of reaction increased between 20° and 70°, indicating a heat of activation of 13·6kcal./mole.

Oxidation of Nickel(II) and Manganese(II) by Peroxodisulfate in Aqueous Solution in the Presence of Molybdate. Crystal Structure of the (NH4)6[NiMo9O32].6H2O Product

1992 ◽  
Vol 45 (12) ◽  
pp. 1943 ◽  
Author(s):  
SJ Dunne ◽  
RC Burns ◽  
GA Lawrance
Keyword(s):  
Rate Constant ◽  
Linear Dependence ◽  
Ph Dependence ◽  
Order Rate Constant ◽  
X Ray Diffraction ◽  
X Ray ◽  
First Order ◽  
Oxidant Concentration ◽  
Ph Range ◽  
Kinetics Of

Oxidation of Ni2+,aq, by S2O82- to nickel(IV) in the presence of molybdate ion, as in the analogous manganese system, involves the formation of the soluble heteropolymolybdate anion [MMogO32]2- (M = Ni, Mn ). The nickel(IV) product crystallized as (NH4)6 [NiMogO32].6H2O from the reaction mixture in the rhombohedra1 space group R3, a 15.922(1), c 12.406(1) � ; the structure was determined by X-ray diffraction methods, and refined to a residual of 0.025 for 1741 independent 'observed' reflections. The kinetics of the oxidation were examined at 80 C over the pH range 3.0-5.2; a linear dependence on [S2O82-] and a non-linear dependence on l/[H+] were observed. The influence of variation of the Ni/Mo ratio between 1:10 and 1:25 on the observed rate constant was very small at pH 4.5, a result supporting the view that the precursor exists as the known [NiMo6O24H6]4- or a close analogue in solution. The pH dependence of the observed rate constant at a fixed oxidant concentration (0.025 mol dm-3) fits dequately to the expression kobs = kH [H+]/(Ka+[H+]) where kH = 0.0013 dm3 mol-1 s-1 and Ka = 4-0x10-5. The first-order dependence on peroxodisulfate subsequently yields a second-order rate constant of 0.042 dm3 mol-1 s-1. Under analogous conditions, oxidation of manganese(II) occurs eightfold more slowly than oxidation of nickel(II), whereas oxidation of manganese(II) by peroxomonosulfuric acid is 16-fold faster than oxidation by peroxodisulfate under similar conditions.

scholarly journals EFFECT OF DIATOMEAOUS EARTH TREATMENT USING HYDROGEN CHLORIDE AND SULFURIC ACID ON KINETICS OF CADMIUM(II) ADSORPTION

2010 ◽  
Vol 2 (2) ◽  
pp. 107-112
Author(s):  
Nuryono Nuryono ◽  
Narsito Narsito
Keyword(s):  
Aqueous Solution ◽  
Sulfuric Acid ◽  
Hydrogen Chloride ◽  
Rate Constant ◽  
Diatomaceous Earth ◽  
Adsorption Rate ◽  
Physical Interaction ◽  
First Order ◽  
Adsorption Rate Constant ◽  
Kinetics Of

In this research, treatment of diatomaceous earth, Sangiran, Central Java using hydrogen chloride (HCl) and sulfuric acid (H2SO4) on kinetics of Cd(II) adsorption in aqueous solution has been carried out. The work was conducted by mixing an amount of grounded diatomaceous earth (200 mesh in size) with HCl or H2SO4 solution in various concentrations for two hours at temperature range of 100 - 150oC. The mixture was then filtered and washed with water until the filtrate pH is approximately 7 and then the residue was dried for four hours at a temperature of 70oC. The product was used as an adsorbent to adsorb Cd(II) in aqueous solution with various concentrations. The Cd(II) adsorbed was determined by analyzing the rest of Cd(II) in the solution using atomic absorption spectrophotometry. The effect of treatment was evaluated from kinetic parameter of adsorption rate constant calculated based on the simple kinetic model. Results showed  that before equilibrium condition reached, adsorpstion of Cd(II) occurred through two steps, i.e. a step tends to follow a reaction of irreversible first order  (step I) followed by reaction of reversible first order (step II). Treatment with acids, either hydrogen chloride or sulfuric acid, decreased adsorption rate constant for the step I from 15.2/min to a range of 6.4 - 9.4/min.  However, increasing concentration of acid (in a range of concentration investigated) did not give significant and constant change of adsorption rate constant. For step II process,  adsorption involved physical interaction with the sufficient low adsorption energy (in a range of 311.3 - 1001 J/mol).     Keywords: adsorption, cdmium, diatomaceous earth, kinetics.

Study on Kinetics of Reaction between ZrNi5 and Water Vapor

2012 ◽  
Vol 581-582 ◽  
pp. 694-697
Author(s):  
Yong Yao ◽  
De Li Luo ◽  
Zhi Yong Huang ◽  
Jiang Feng Song
Keyword(s):  
Water Vapor ◽  
Reaction Rate ◽  
Arrhenius Equation ◽  
Tritiated Water ◽  
First Order ◽  
Order Chemical Reaction ◽  
First Order Chemical Reaction ◽  
Kinetics Of Reaction ◽  
Reaction Activation Energy ◽  
Kinetics Of

In order to evaluate the feasibility of tritium recovery from tritiated water by thermochemical decomposition using ZrNi5, the kinetics of reaction between ZrNi5 and water vapor was studied by thermogravimetric method in the temperature range from 673K to 823K. The result shows that reaction rate increased significantly with the increasing of temperature and H2O concentration; the reaction mechanism for ZrNi5 can be described by the first-order chemical reaction, and the reaction is first order for H2O concentration. The reaction activation energy of ZrNi5 is 55.8kJ/mol calculated from the Arrhenius equation.

scholarly journals What is the Role of Absorption Atelectasis in the Genesis of Perioperative Pulmonary Collapse?

1995 ◽  
Vol 23 (6) ◽  
pp. 691-696 ◽  
Author(s):  
C. J. Joyce ◽  
A. B. Baker
Keyword(s):  
Nitrous Oxide ◽  
Significant Role ◽  
Lung Volume ◽  
Underlying Mechanism ◽  
Gas Absorption ◽  
Experimental Results ◽  
Inspired Oxygen ◽  
Oxygen Concentrations

During anaesthesia the combination of breathing at low lung volume, the administration of nitrous oxide and high inspired oxygen concentrations produces conditions that favour absorption atelectasis. Measures such as adding nitrogen to the inspired mixture and avoiding high inspired oxygen concentrations would reduce the amount of perioperative atelectasis if gas absorption was important in the genesis of perioperative pulmonary collapse. Experimental results demonstrate that these measures do not protect against atelectasis. This indicates that absorption atelectasis does not play a significant role in the genesis of perioperative pulmonary collapse. Compression atelectasis may be the underlying mechanism.

Kinetics of reconstitution of apotyrosinase by copper

1990 ◽  
Vol 68 (2) ◽  
pp. 476-479
Author(s):  
Donald C. Wigfield ◽  
Douglas M. Goltz
Keyword(s):  
Rate Constant ◽  
Copper Concentration ◽  
Copper Ions ◽  
Copper Ion ◽  
Order Rate Constant ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Rate Limiting ◽  
Kinetics Of

The kinetics of the reconstitution reaction of apotyrosinase with copper (II) ions are reported. The reaction is pseudo first order with respect to apoenzyme and the values of these pseudo first order rate constants are reported as a function of copper (II) concentration. Two copper ions bind to apoenzyme, and if the second one is rate limiting, the kinetically relevant copper concentration is the copper originally added minus the amount used in binding the first copper ion to enzyme. This modified copper concentration is linearly related to the magnitude of the pseudo first order rate constant, up to a copper concentration of 1.25 × 10−4 M (10-fold excess), giving a second order rate constant of 7.67 × 102 ± 0.93 × 102 M−1∙s−1.Key words: apotyrosinase, copper, tyrosinase.

The Role of Starting Potential in the Kinetics of Chemical Reactions under Electrodeless Discharge

1970 ◽  
Vol 25 (11) ◽  
pp. 1772
Author(s):  
T.S.R Ao ◽  
A. Patil
Keyword(s):  
Gas Phase ◽  
Chemical Reactions ◽  
Electric Discharge ◽  
Specific Rate ◽  
Gas Phase Reactions ◽  
Electrodeless Discharge ◽  
First Order ◽  
Kinetics Of

Abstract It has been shown that in kinetically first order gas phase reactions occuring under electric discharge, such as the decomposition of N2O, the application, at various initial pressures, of the same multiple of the respective starting potential ensures that the reaction occurs at the same specific rate.

Voltammetric investigation of the kinetics of alkali metal cation reduction in N,N-dimethylformamide

1975 ◽  
Vol 28 (2) ◽  
pp. 237 ◽  
Author(s):  
JW Diggle ◽  
AJ Parker ◽  
DA Owensby
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Propylene Carbonate ◽  
Rate Constant ◽  
Alkali Metal Cation ◽  
Electrode Reaction ◽  
Amalgam Electrode ◽  
Kinetics Of ◽  
Dipolar Aprotic Solvents

The standard electron-transfer heterogeneous rate constant of lithium, potassium, sodium and caesium amalgams in N,N-dimethylformamide was ascertained employing cyclic voltammetry in an effort to relate the presence of a non-equilibrium electrode reaction at the dropping lithium amalgam electrode to the variation of the lithium amalgam electrode potential with amalgam electrode con- figuration, i.e. whether streaming, dropping or stationary. Such variations are not observed at other alkali metal amalgam electrodes. ��� In the dipolar aprotic solvents the standard electron-transfer heterogeneous rate constant for the Li(Hg) electrode increases as the solvating power for Li+ decreases, i.e. dimethyl sulphoxide < di- methylformamide < propylene carbonate. Water is a much stronger solvator of Li+ than is propylene carbonate, but the electron transfer is faster in water than in propylene carbonate; the important role of entropic contributions in ion solvation is discussed as an explanation.

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