Mechanisms of SNi Reactions. The Kinetics of the Decomposition of Aralkyl Carbonates

1972 ◽  
Vol 50 (11) ◽  
pp. 1770-1774 ◽  
Author(s):  
J. M. Prokipcak ◽  
T. H. Breckles
Keyword(s):  
Structural Changes ◽  
Elevated Temperatures ◽  
Ion Pair ◽  
Decomposition Rates ◽  
First Order ◽  
First Order Kinetics ◽  
Cyclic Mechanism ◽  
Alkyl Chloroformates ◽  
Kinetics Of ◽  
Oxygen Bond

Anisylic phenyl carbonates decomposed at elevated temperatures to give CO2 and the corresponding anisylic phenyl esters. The decomposition follows first order kinetics very similar to those found for alkyl chloroformates. The decompositions involve the heterolysis of the aralkyl oxygen bond followed by the breakdown of the subsequent ion pair via a cyclic mechanism. The dependence of the decomposition rates on the nature of the solvent and structural changes of the starting carbonates is discussed.

Mechanism of SNi reactions. The effect of the base strength of the anionic fragments

1978 ◽  
Vol 56 (19) ◽  
pp. 2582-2589 ◽  
Author(s):  
D. J. Verrinder ◽  
M. J. Hourigan ◽  
J. M. Prokipcak
Keyword(s):  
Thermal Decomposition ◽  
Optical Activity ◽  
Ion Pair ◽  
Decomposition Rates ◽  
First Order ◽  
First Order Kinetics ◽  
Cyclic Mechanism ◽  
Base Strength ◽  
Oxygen Bond ◽  
Anionic Fragment

The kinetics and stereochemical aspects of the thermal decomposition of aralkyl carbonates, thiocarbonates, and carbamates were examined. The rates for the decompositions as well as the rates of loss of optical activity followed first-order kinetics. The decompositions appear to involve the heterolysis of the aralkyl–oxygen bond followed by the breakdown of the subsequent ion pair via a cyclic mechanism. However, it was found that this ion pair could return to covalency without completely decomposing to products leading to the racemization of the starting materials. This type of racemization occurred more readily in the case of the carbamates than in the thiocarbonates and carbonates. The dependence of the decomposition rates and the loss of optical activity on the nature of the hetero atom of the anionic fragment of the starting material is discussed.

scholarly journals Polyethylene Glycols as Efficient Catalysts for the Oxidation of Xanthine Alkaloids by Ceric Ammonium Nitrate in Acetonitrile: A Kinetic and Mechanistic Approach

2013 ◽  
Vol 2013 ◽  
pp. 1-11 ◽  
Author(s):  
S. Shylaja ◽  
K. C. Rajanna ◽  
K. Ramesh ◽  
K. Rajendar Reddy ◽  
P. Giridhar Reddy
Keyword(s):  
Ammonium Nitrate ◽  
Elevated Temperatures ◽  
Ceric Ammonium Nitrate ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Mechanistic Approach ◽  
Enzymatic Model ◽  
Poly Ethylene ◽  
Kinetics Of

Kinetics of oxidation of xanthine alkaloids, such as Xanthine (XAN), hypoxanthine (HXAN), caffeine (CAF), theophylline (TPL), and theobromine (TBR), have been studied with ceric ammonium nitrate (CAN) using poly ethylene glycols (PEG) as catalysts. Reaction obeyed first order kinetics in both [CAN] and [Xanthine alkaloid]. Highly sluggish CAN-xanthine alkaloid reactions (in acetonitrile media even at elevated temperatures) are enhanced in presence PEGs (PEG-200, -300, -400, -600). An increase in [PEG] increased the rate of oxidation linearly. This observation coupled with a change in absorption of CAN in presence of PEG, [H–(OCH2–CH2)n–O–NH4Ce(NO3)4(CH3CN)] (PEG bound CAN species), is considered to be more reactive than CAN. The mechanism of oxidation in PEG media has been explained by Menger-Portnoy’s enzymatic model.

Kinetic of oxidation of methyl orange by vanadium(V) under conditions VO2+ and decavanadates coexist: Catalysis by Triton X-100 micellar medium

2019 ◽  
Author(s):  
Chem Int
Keyword(s):  
Methyl Orange ◽  
Solution Ph ◽  
Vanadium Concentration ◽  
Limiting Behavior ◽  
First Order ◽  
First Order Kinetics ◽  
Ph Range ◽  
Kinetic Pattern ◽  
Triton X ◽  
Kinetics Of

The kinetics of oxidation of methyl orange by vanadium(V) {V(V)} has been investigated in the pH range 2.3-3.79. In this pH range V(V) exists both in the form of decavanadates and VO2+. The kinetic results are distinctly different from the results obtained for the same reaction in highly acidic solution (pH < 1) where V(V) exists only in the form of VO2+. The reaction obeys first order kinetics with respect to methyl orange but the rate has very little dependence on total vanadium concentration. The reaction is accelerated by H+ ion but the dependence of rate on [H+] is less than that corresponding to first order dependence. The equilibrium between decavanadates and VO2+ explains the different kinetic pattern observed in this pH range. The reaction is markedly accelerated by Triton X-100 micelles. The rate-[surfactant] profile shows a limiting behavior indicative of a unimolecular pathway in the micellar pseudophase.

scholarly journals Comparative Study of Chemical Stability of Two H1Antihistaminic Drugs, Terfenadine and ItsIn VivoMetabolite Fexofenadine, Using LC-UV Methods

2019 ◽  
Vol 2019 ◽  
pp. 1-10
Author(s):  
Anna Gumieniczek ◽  
Anna Berecka-Rycerz ◽  
Rafał Pietraś ◽  
Izabela Kozak ◽  
Karolina Lejwoda ◽  
...  
Keyword(s):  
Comparative Study ◽  
Chemical Stability ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of Degradation ◽  
Effects Of Temperature ◽  
High Doses ◽  
Antihistaminic Drugs ◽  
Kinetics Of

A comparative study of chemical stability of terfenadine (TER) and itsin vivometabolite fexofenadine (FEX) was performed. Both TER and FEX were subjected to high temperature at different pH and UV/VIS light at different pH and then quantitatively analyzed using new validated LC-UV methods. These methods were used to monitor the degradation processes and to determine the kinetics of degradation for both the compounds. As far as the effects of temperature and pH were concerned, FEX occurred more sensitive to degradation than TER. As far as the effects of UV/VIS light and pH were concerned, the both drugs were similarly sensitive to high doses of light. Using all stress conditions, the processes of degradation of TER and FEX followed the first-order kinetics. The results obtained for these two antihistaminic drugs could be helpful in developing their new derivatives with higher activity and stability at the same time.

Kinetics of NO2 air space absorption in isolated rat lungs

1992 ◽  
Vol 73 (5) ◽  
pp. 1939-1945 ◽  
Author(s):  
E. M. Postlethwait ◽  
S. D. Langford ◽  
A. Bidani
Keyword(s):  
Steady State ◽  
Tidal Volume ◽  
Gas Phase ◽  
Initial Rate ◽  
Quasi Steady State ◽  
Closed Chamber ◽  
First Order ◽  
First Order Kinetics ◽  
Rat Lungs ◽  
Kinetics Of

We previously showed, during quasi-steady-state exposures, that the rate of inhaled NO2 uptake displays reaction-mediated characteristics (J. Appl. Physiol. 68: 594–603, 1990). In vitro kinetic studies of pulmonary epithelial lining fluid (ELF) demonstrated that NO2 interfacial transfer into ELF exhibits first-order kinetics with respect to NO2, attains [NO2]-dependent rate saturation, and is aqueous substrate dependent (J. Appl. Physiol. 71: 1502–1510, 1991). We have extended these observations by evaluating the kinetics of NO2 gas phase disappearance in isolated ventilating rat lungs. Transient exposures (2–3/lung at 25 degrees C) employed rebreathing (NO2-air) from a non-compliant continuously stirred closed chamber. We observed that 1) NO2 uptake rate is independent of exposure period, 2) NO2 gas phase disappearance exhibited first-order kinetics [initial rate (r*) saturation occurred when [NO2] > 11 ppm], 3) the mean effective rate constant (k*) for NO2 gas phase disappearance ([NO2] < or = 11 ppm, tidal volume = 2.3 ml, functional residual capacity = 4 ml, ventilation frequency = 50/min) was 83 +/- 5 ml/min, 4) with [NO2] < or = 11 ppm, k* and r* were proportional to tidal volume, and 5) NO2 fractional uptakes were constant across [NO2] (< or = 11 ppm) and tidal volumes but exceeded quasi-steady-state observations. Preliminary data indicate that this divergence may be related to the inspired PCO2. These results suggest that NO2 reactive uptake within rebreathing isolated lungs follows first-order kinetics and displays initial rate saturation, similar to isolated ELF.(ABSTRACT TRUNCATED AT 250 WORDS)

Kinetics and Mechanism of Oxidation of Dimethyl Sulphoxide by Mono- and Di-Substituted N,N-Dichlorobenzenesulphonamides in Aqueous Acetic Acid

2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi
Keyword(s):  
Acetic Acid ◽  
Benzene Ring ◽  
Dimethyl Sulphoxide ◽  
Aqueous Acetic Acid ◽  
Isokinetic Temperature ◽  
Free Energies ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.

scholarly journals Nanosized centers for mercury(II) ions adsorption on a surface of modified silica

2008 ◽  
Vol 6 (4) ◽  
pp. 581-591 ◽  
Author(s):  
Lyudmila Belyakova ◽  
Oleksandra Shvets ◽  
Diana Lyashenko
Keyword(s):  
Aqueous Medium ◽  
Batch Adsorption ◽  
Modified Silica ◽  
First Order ◽  
Chemically Modified ◽  
First Order Kinetics ◽  
Adsorption Data ◽  
Pseudo Second Order ◽  
Kinetics Of ◽  
Second Order Equations

AbstractThe present work investigates the adsorptive interactions of Hg(II) ions in aqueous medium with hydroxylated silica, aminopropylsilica and silica chemically modified by β-cyclodextrin. Batch adsorption studies were carried out with various agitation times and mercury(II) concentrations. The maximum adsorption was observed within 15–30 min of agitation. The kinetics of the interactions, tested with the model of Lagergren for pseudo-first and pseudo-second order equations, showed better agreement with first order kinetics (k1 = 3.4 ± 0.2 to 5.9 ± 0.3 min−1). The adsorption data gave good fits with Langmuir isotherms. The results have shown that β-cyclodextrin-containing adsorbent has the largest adsorption specificity to Hg(II): K L = 4125 ± 205 mmol−1. “β-cyclodextrin-NO3-” inclusion complexes with ratio 1: 1 and super molecules with composition C42H70O35 ⊎ 3 Hg(NO3)2 are formed on the surface of β-cyclodextrin-containing silica.

Chelating agents in high temperature aqueous chemistry. 1. The kinetics of the thermal decomposition of aqueous nitrilotriacetate (NTA), iminodiacetate (IDA), and N-methyliminodiacetate (MIDA)

1977 ◽  
Vol 55 (10) ◽  
pp. 1762-1769 ◽  
Author(s):  
Meindert Booy ◽  
Thomas Wilson Swaddle
Keyword(s):  
Chelating Agents ◽  
Nuclear Reactors ◽  
Rate Coefficients ◽  
Aqueous Mixtures ◽  
Hydrothermal Conditions ◽  
Good Thermal Stability ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of ◽  
Thermal Stability Of

Aqueous H3NTA, H2MIDA, H2IDA, and their anions decompose under hydrothermal conditions (400–580 K) according to first order kinetics by successive decarboxylations, oxidation by O2 being unimportant except at the highest temperatures. In the presence of added H+, the species H4NTA+ and, to a lesser extent, H3MIDA+ (but not H3IDA+), provide significant decomposition pathways through elimination of a —CH2COO— group (deacetylation). For HnNTA(3−n)−, first order rate coefficients kn for decomposition are k0 = 4.5 × 10−7, k1 ∼ 1 × 10−6, k2 ∼ 7 × 10−5, k3 = 2.1 × 10−4, and k4 = 1.0 × 10−2 s1, at 503 K and ionic strength 2.0 m, the spread in rates being due to differences in ΔS* rather than ΔH*. H2MIDA and H2IDA are comparable in reactivity to H3NTA, while their anions are much less reactive than the NTA species of the same charge. The good thermal stability of aqueous NTA commends it as a reagent for boiler servicing and for decontamination of water-cooled nuclear reactors. A potentiometric method for the estimation of mono-, di-, and tribasic aminoacids in aqueous mixtures of these is described.

The kinetics and the mechanism of oxidative decarboxylation of benzilic acid by acidic permanganate (stopped-flow technique) — An autocatalytic study

2004 ◽  
Vol 82 (9) ◽  
pp. 1372-1380 ◽  
Author(s):  
Sairabanu A Farokhi ◽  
Sharanappa T Nandibewoor
Keyword(s):  
Activation Parameters ◽  
Oxidative Decarboxylation ◽  
Two Stage ◽  
First Order ◽  
First Order Kinetics ◽  
Stage Process ◽  
Benzilic Acid ◽  
Reaction Constants ◽  
Kinetics Of ◽  
Good Agreement

The kinetics of the oxidation of benzilic acid by potassium permanganate in an acidic medium were studied spectrophotometrically. The reaction followed a two-stage process, wherein both stages of the reaction followed first-order kinetics with respect to permanganate ion and benzilic acid. The rate of the reaction increased with an increase in acid concentration. Autocatalysis was observed by one of the products, i.e., manganese(II). A composite mechanism involving autocatalysis has been proposed. The activation parameters of the reaction were calculated and discussed and the reaction constants involved in the mechanisms were calculated. There is a good agreement between the observed and calculated rate constants under different experimental conditions.Key words: oxidation, autocatalysis, benzilic acid, two-stage kinetics.

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