Die γ-Radiolyse und Pulsradiolyse des Schwefelkohlenstoffs in wäßriger Lösung / The γ-Radiolysis and Pulse Radiolysis of Carbon Disulfide in Aqueous Solution

1973 ◽  
Vol 28 (1-2) ◽  
pp. 12-22 ◽  
Author(s):  
W. Roebke ◽  
M. Schöneshöfer ◽  
A. Henglein
Keyword(s):  
Rate Constant ◽  
Carbon Disulfide ◽  
Second Order ◽  
Γ Irradiation ◽  
Electrolytic Dissociation ◽  
First Order ◽  
A Value ◽  
Diffusion Controlled ◽  
Polymer Pyrolysis ◽  
Hydrolysis Of

A polymer (CHS2)n and sulfate are formed in the γ-irradiation of deaerated aqueous carbon disulfide solutions. The G-values are 3.6 and 0.41, respectively. In the presence of N,O, G (polymer) is decreased while G(SO4-) is increased. G(SO4-) can be decreased by isopropanol. G(polymer) is increased by H+ ions and reaches a value of 5 below pH = 2. Formic acid, hydrogen sulfide and carbonate are formed in the hydrolysis of the polymer. Pyrolysis at first leads to a red oil consisting of oligomer (HCS2)n and finally to H2S, CS2 plus a residue containing much carbon. The structure of the polymer is discussed.Pulse radiolytic experiments show that CS2 reacts with eaq (3.1 × 1010M-1s-1) and OH(7.4 × 109M-1s-1) in a diffusion controlled manner. The first product of the reaction with OH is SC(OH)S. The pK of the electrolytic dissociationSC(OH)Ṣ ⇄ SC(O-)S + H+is 4.4. The absorption spectra of SC(OH)S and SC(O-)S were measured. SC(OH)S disappears by second order with 2k = 1.6 × 109M-1s-1 at pH = 6. The product is a bivalent acid, the spectrum of which was measured. The second pK of this acid is 5.7, its first pK is lower than 4.Both eāq and H react with CS2 to form SCS-. The absorption spectrum of this radical anion was measured. The pK of the equilibriumSCSH ⇄SCS- + H+is about 1.6. In solutions of low H+-concentration, SCS- disappears by second order with 2k = 6.4 × 109M-1s-1. The structure of dithioformic acid is attributed to the resulting product. In solutions of high H+-concentration, SCS- (or SCSH) disappears by a fast first order process, the rate constant of which increases with H+-concentration. The carbeniat neutralizationis believed to be responsible for this process. The rate constant is 5.1 × 107M-1S-1. The spectrum of SC(H)S was measured. This radical disappears by second order with 2k = 7.4 × 109M-1s-1. The spectrum of the resulting product was also determined.It is concluded that the formation of the polymer and of SO4- occurs in processes in which the first products from the attack of eāq, H and OH on CS2 as well as molecules which were built up from these products are involved.

scholarly journals Kinetics and Mechanistic Study of Hydrolysis of Adenosine Monophosphate Disodium Salt (AMPNa2) in Acidic and Alkaline Media

2019 ◽  
Vol 17 (1) ◽  
pp. 544-556
Author(s):  
Yoke-Leng Sim ◽  
Beljit Kaur
Keyword(s):  
Rate Constant ◽  
Adenosine Monophosphate ◽  
Disodium Salt ◽  
Second Order ◽  
Information Storage ◽  
Alkaline Media ◽  
Basic Medium ◽  
Mechanistic Study ◽  
Phosphate Ester ◽  
Hydrolysis Of

AbstractPhosphate ester hydrolysis is essential in signal transduction, energy storage and production, information storage and DNA repair. In this investigation, hydrolysis of adenosine monophosphate disodium salt (AMPNa2) was carried out in acidic, neutral and alkaline conditions of pH ranging between 0.30-12.71 at 60°C. The reaction was monitored spectrophotometrically. The rate ranged between (1.20 ± 0.10) × 10-7 s-1 to (4.44 ± 0.05) × 10-6 s-1 at [NaOH] from 0.0008 M to 1.00M recorded a second-order base-catalyzed rate constant, kOH as 4.32 × 10-6 M-1 s-1. In acidic conditions, the rate ranged between (1.32 ± 0.06) × 10-7 s-1 to (1.67 ± 0.10) × 10-6 s-1 at [HCl] from 0.01 M to 1.00 M. Second-order acid-catalyzed rate constant, kH obtained was 1.62 × 10-6 M-1 s-1. Rate of reaction for neutral region, k0 was obtained from graphical method to be 10-7 s-1. Mechanisms were proposed to involve P-O bond cleavage in basic medium while competition between P-O bond and N-glycosidic cleavage was observed in acidic medium. In conclusion, this study has provided comprehensive information on the kinetic parameters and mechanism of cleavage of AMPNa2 which mimicked natural AMP cleavage and the action of enzymes that facilitate its cleavage.

The homogeneous decomposition reactions of gaseous formic acid

1960 ◽  
Vol 255 (1283) ◽  
pp. 444-455 ◽  
Keyword(s):  
Formic Acid ◽  
Kinetic Parameters ◽  
Rate Constant ◽  
Ion Pairs ◽  
Order Rate Constant ◽  
Second Order ◽  
Unimolecular Decomposition ◽  
Order Component ◽  
First Order ◽  
Homogeneous Decomposition

By use of reaction vessels with specially treated surfaces the homogeneous decomposition of formic acid has been studied kinetically in the range 436 to 532°C. Neither of the two simultaneous reactions ( a ) HCOOH = CO 2 + H 2 , ( b ) HCOOH = CO + H 2 O, is retarded by the usual inhibitors of chain processes. Each appears to be molecular. Reaction ( a ) is of the first order in the range 3 to 650 mm, the first-order rate constant being given by k CO 2 = 10 4⋅8 exp (–30600/ RT )s -1 . It is suggested tentatively that the abnormal kinetic parameters might be explained by regarding the reaction as a decarboxylation of (H + ) (HCOO¯) ion pairs present in minute concentration. Reaction ( b ) shows a pressure dependence most simply explained by a superposition of a predominant second-order component with a small first-order component. The most satisfactory interpretation of the second-order reaction is that it represents the unimolecular decomposition of dimer molecules, known to be present in formic-acid vapour. On this basis the rate constant is given by k CO dimer = 10 13⋅58 exp (–42600/ RT )s -1 , the kinetic parameters thus being in the normal range. The various alternative interpretations are discussed.

Studies on Sulphamic Acid and Related Compounds. II. Kinetics and Mechanism of Hydrolysis of Trimethylamine- and of Triethylamine Sulphur Trioxide Addition Compounds

1962 ◽  
Vol 15 (2) ◽  
pp. 251 ◽  
Author(s):  
BE Fleischfresser ◽  
I Lauder
Keyword(s):  
Rate Constant ◽  
Order Rate Constant ◽  
Aqueous Acetone ◽  
Second Order ◽  
Fluoride Ions ◽  
Order Rate ◽  
Mechanism Of Hydrolysis ◽  
Reaction With Water ◽  
Sulphamic Acid ◽  
Hydrolysis Of

The kinetics of hydrolysis of trimethylamine- and of triethylaminesulphur trioxide addition compounds have been studied in water and in aqueous acetone. Reaction occurs according to the equation,������������� f - + R,N.SO,+H,O-tR,XH+HSO~.The solvolysis reactions are first-order and are not catalyzed by acids. The halide ions, Cl', Br', and 1', show only a normal salt effect on the rate of hydrolysis of + - (CH,),N.SO, but in the presence of fluoride ions, the rate constant for the production + - of acid from (C,H,),N.SO, in water at 95 OC is about one-seventh of that in the absence of fluoride under the same conditions. It is suggested that the fluorosulphonate ion is formed rapidly, and that this ion then undergoes slow hydrolysis :�In the presence of alkali, using water as the solvent, second-order kinetics are observed, the equation for the reaction being,�������������� + - R,N.SO,+~OH-+R,X+SO~= +H,O. Assuming the reaction with water is bimolecular, the ratio of the (bimolecular) rate constants at 35 OC, ko~-/k~,o is approximately lo8 for each complex. In aqueous acetone, at low water concentrations, the hydrolysis reactions of the trialkylaminesulphur trioxide complexes show second-order kinetics. At 35 OC for the hydrolysis of + - (CH,),N.SO, the ratio of the second-order rate constant in aqueous acetone to the + - (calculated) second-order rate constant in water is approximately 550 ; for (C,H,),N.SO, the same ratio is 6900. It is considered that hydrolysis occurs in water and in aqueous acetone via a bi- molecular attack at sulphur.

scholarly journals Kinetika Reaksi Hidrolisis Pati Biji Alpukat (Persea americana Mill) dengan Katalis HCl

2020 ◽  
Vol 4 (1) ◽  
pp. 120-131
Author(s):  
Sitti Rahmawati ◽  
Asnila Asnila ◽  
Suherman Suherman ◽  
Paulus Hengky Abram
Keyword(s):  
Reaction Order ◽  
Second Order ◽  
Hydrolysis Reaction ◽  
Starch Hydrolysis ◽  
First Order ◽  
Graph Method ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Avocado Seed

One of the plants that can be used as raw material for making sugar is plants that contain starch content such as avocado seeds. This study aims to determine the reaction order, the reaction rate constant from the hydrolysis of avocado seed starch using HCl. The method of this research is to determine the optimum concentration of HCl hydrolysis reaction from avocado seed starch using various concentrations of HCl (0.5 M; 1 M; 1.5 M; 2 M; 2.5 M) at the optimum temperature and stirring time (90oC for 70 minute). The hydrolysis process was followed by neutralization using 5 M NaOH solution and evaporated to obtain concentrated glucose, glucose was analyzed qualitatively and quantitatively by the Benedict method and the phenol sulfuric acid method. Based on the results of the maximum glucose levels obtained from the hydrolysis of variations in the concentration of HCl avocado seed starch, HCl 1.5 M. Furthermore, determine the kinetics of the starch hydrolysis reaction using time variations (30, 40, 50, 60 and 70) minutes at 90oC and concentrations The HCl 1.5 M. reaction order is determined by the intral method and the graph method. Determination of the first order graph method is done by plotting the value of ln [A] versus time, while the second order by plotting the value of 1 / [A] versus time. The first order with a 93% confidence level was obtained from the value of R2 = 0.9312, while the second order was 85% obtained from the value of R2 = 0.8581. Determination of the order of the integral method k value tends to remain in the first order formula with an average of k = 0.01962 minutes-1. Based on the two methods, it can be determined that the kinetics of the avocado seed starch hydrolysis reaction follows a first-order reaction.

On the Interaction Between Human Plasma Kallikrein and C1-Esterase Inhibitor

1983 ◽  
Vol 49 (03) ◽  
pp. 193-195 ◽  
Author(s):  
Torbjörn Nilsson
Keyword(s):  
Dissociation Constant ◽  
Human Plasma ◽  
Rate Constant ◽  
Enzyme Inhibitor ◽  
Order Rate Constant ◽  
Second Order ◽  
Plasma Kallikrein ◽  
First Order ◽  
Order Rate ◽  
Esterase Inhibitor

SummaryThe kinetics of the reaction between human plasma kallikrein and CĪ-esterase inhibitor was studied in a purified system. By monitoring the inhibition reaction for extended periods of time, it was found to proceed in two consecutive steps, a fast reversible second-order binding step followed by a slower, irreversible first-order transition. The rate constants in this reaction model were determined, as well as the dissociation constant of the initial, reversible enzyme-inhibitor complex. Thus, at 37° C the second-order rate constant was found to be 5 · 104 M -1 · s-1, the first order rate constant was 5 · 10-4 s-1 and the dissociation constant K was 1.5 · 10-8 M. Heparin (28 U/ml) and 6-aminohexanoic acid (10 mM) had no effect on the k1 of the of the reaction.

Kinetics and mechanism of the reaction of dimethyl acetylphosphonate with water. Expulsion of a phosphonate ester from a carbonyl hydrate

1978 ◽  
Vol 56 (13) ◽  
pp. 1792-1795 ◽  
Author(s):  
Ronald Kluger ◽  
David C. Pire ◽  
Jik Chin
Keyword(s):  
Rate Constant ◽  
Electronic Effect ◽  
Order Rate Constant ◽  
Ion Concentration ◽  
First Order ◽  
Cleavage Reactions ◽  
Ph Range ◽  
Rapid Hydrolysis ◽  
Hydrolysis Of ◽  
Mechanism Of The Reaction

Dimethyl acetylphosphonate (DAP) is rapidly cleaved in water to acetate and dimethylphosphonic acid. The half time for reaction at pH 7, 25 °C is estimated to be 3 s. The reaction is first order in hydroxide ion concentration and first order in DAP concentration. Rates of reaction were measured over the pH range 3.8 to 6.5 at 25 °C, 6.5 and 7.0 at 5 °C, 4.5 to 6.5 at 35 °C, and 4.5 to 6.0 at 45 °C. The average observed second-order rate constant at 25 °C is 2.4 × 106M−1 s−1. DAP is converted rapidly to a hydrated carbonyl adduct. The mechanism for the formation of the observed products is proposed to be analogous to cleavage reactions of other carbonyl hydrates, proceeding from a monoanion conjugate in this case. The estimated rate constant for the unimolecular cleavage of the carbonyl hydrate anion is 2 × 103 s−1. The rapid hydrolysis of DAP results from energetically favourable formation of a hydrate due to the electronic effect of the phosphonate diester. This effect also promoles ionization of the hydrate. The ionized hydrate readily expels the phosphonate diester to achieve the overall rapid hydrolysis.

Nucleophilicity and ionization of dihydrolipoamide

1990 ◽  
Vol 68 (3) ◽  
pp. 669-673
Author(s):  
Christie L. Hunter ◽  
Michael J. Danson ◽  
Kenneth J. Stevenson
Keyword(s):  
Rate Constant ◽  
Thioglycolic Acid ◽  
Order Rate Constant ◽  
Iodoacetic Acid ◽  
Second Order ◽  
Addition Reactions ◽  
Order Rate ◽  
A Value ◽  
Constant Versus ◽  
Dominant Influence

The reactivity of dihydrolipoamide has been studied at pHs 6 and 8 with a series of haloalkyl acids, iodoacetamide, and N-phenyl-α-bromoacetamide. The electron-withdrawing capability of the R group in these reagents (X—CH2—R) has the dominant influence on their reactivity with the thiolate. Thus, 3-bromopyruvic acid greatly exceeds N-phenyl-α-bromoacetamide, iodoacetamide, iodoacetic acid, and three bromoalkyl acids. A plot of the second-order rate constant of iodoacetamide with dihydrolipoamide supports a value of pK1, in the vicinity of 10.5. The second pKa of dihydrolipoamide cannot be deduced by this method, since reaction of the first thiol with iodoacetamide greatly alters the influences which the vicinal (normally unmodified) thiol has on the other. Potentiometric titration of dihydrolipoamide was not definitive, but the curve obtained was comparable to the titration curve of dihydrolipoamide (followed spectrophotometrically) which accommodated a pK1of 9.35 and pK2 of 10.65. As a control, a plot of the second-order rate constant versus pH for the alkylation of thioglycolic acid revealed a pKa of 10.5 in agreement with the titrated pKa of 10.4.Key words: dihydrolipoamide, nucleophilic addition reactions, ionization of thiols, iodoacetamide.

Formation and reactivity of the aminothiyl and iminothiyl radicals by means of flash photolysis

1978 ◽  
Vol 56 (8) ◽  
pp. 1080-1083 ◽  
Author(s):  
Osamu Ito ◽  
Minoru Matsuda
Keyword(s):  
Rate Constant ◽  
Flash Photolysis ◽  
Second Order ◽  
Thiyl Radical ◽  
Weak Band ◽  
Diffusion Controlled ◽  
Hydrogen Donors ◽  
Organophosphorous Compounds

Flash photolysis of bis[piperidyl-1] disulfide gave a clear transient band at 340 nm and a weak band around 525 nm, which were assigned to the piperidyl-1-thiyl radical. In a similar manner, bis[diphenylimino] disulfide gave a transient band at 420 nm, which could be assigned to the diphenyliminothiyl radical. These radicals disappeared in various solvents according to second-order kinetics with rate constant 0.8–7.2 × 109 M−1 s−1 showing that the radicals decay predominantly by recombination with diffusion controlled rates. These radicals were not reactive toward oxygen, olefins, organophosphorous compounds, and hydrogen donors in agreement with the results given by the kinetic epr study reported by Maillard and Ingold.

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