Synthetic and kinetic studies of the reversible addition of a bridging NSN fragment to the electron-rich heterocycles (R2PN)(SN)2 (R = Me, Ph, F)

1984 ◽  
Vol 62 (4) ◽  
pp. 712-715 ◽  
Author(s):  
Neil Burford ◽  
Tristram Chivers ◽  
Richard T. Oakley ◽  
Tom Oswald
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Nmr Spectroscopy ◽  
Kinetic Studies ◽  
Reductive Elimination ◽  
Membered Ring ◽  
High Yield ◽  
Kinetic Measurements ◽  
Bicyclic Compounds ◽  
Reversible Addition

The oxidative addition of Cl2 (using SO2Cl2) to the six-membered ring (R2PN)(SN)2 (R = Me, Ph) produces the mixed phosphazene–thiazyl heterocycles, (R2PN)(NSCl)2, which react with Me3SiNSNSiMe3 to give the bicyclic compounds R2PS3N5. The latter undergo thermal decomposition, at ca. 100 °C in toluene, via reductive elimination of an NSN unit to regenerate (R2PN)(SN)2 in high yield. Kinetic measurements of this process, using 31P nmr spectroscopy, yield an activation energy of 102.4 ± 6.0 kJ mol−1 for the release of the NSN fragment from Me2PS3N5. The thermolysis route has been used to prepare the thermally unstable (F2PN)(SN)2, characterized as a 1:1 adduct with norbornadiene.

scholarly journals Catalytic performance of Ce1-xLnxOy of nanocrystalline Ln (III-IV)-substituted ceria

2019 ◽  
Vol 2 (3) ◽  
Author(s):  
Eduardo Arístides Poggio-Fraccari1 ◽  
Mariño F1 ◽  
Sorbello C2 ◽  
Jobbagy M2
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Co Oxidation ◽  
Surface Segregation ◽  
Mixed Oxides ◽  
Catalytic Performance ◽  
High Yield ◽  
Good Activity ◽  
Reactor Operation ◽  
Surface Areas

The activity of several lanthanide promoted Ceria in CO oxidation was studied. Samples were obtained by a high yield and sustainable method by urea thermal decomposition. Precursors basic carbonates, Ce1-xLnx(OH)CO3, being Ln = La (III), Sm(III), Gd(III), Pr(III) were prepared in the range of compositions 0 to 30 at.%. These precursors were annealed to moderate temperature obtain Ln-Ce mixed oxides, at 450ºC. These exhibit large surface areas up to 120 m2/g. Their catalytic performance revealed good activity towards CO oxidation  (COOX) for all samples. However, a different behavior may be observed for Ln content higher than 20 at.%. By the reactor operation in differential conditions, the activation energy for COOX were obtained for all samples. The rise of activation energy as a function of Ln(III-IV) content is analyzed in the frame of phase stability and surface segregation.

PHOTO-INITIATED REACTIONS OF THIOLS AND OLEFINS: II. THE ADDITION OF METHANETHIOL TO UNCONJUGATED OLEFINS

1964 ◽  
Vol 42 (10) ◽  
pp. 2250-2255 ◽  
Author(s):  
D. M. Graham ◽  
R. L. Mieville ◽  
R. H. Pallen ◽  
C. Sivertz
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Rate Constant ◽  
Rate Constants ◽  
Kinetic Studies ◽  
Addition Product ◽  
Isomerization Reaction ◽  
Ethylene Propylene ◽  
Intermittent Illumination ◽  
Competing Reactions

Kinetic studies have been made of the addition of methanethiol to ethylene, propylene, and butene-2. The results obtained are consistent with the mechanism postulated for the isomerization reaction (1). The overall activation energy was found to be negative and could be explained in terms of two competing reactions of the adduct radical: thermal decomposition leading to [Formula: see text] and olefin and dehydrogenation of thiol yielding addition product. Only the ratio of the rate constants for these two reactions could be determined. The method of intermittent illumination was used to evaluate the termination rate constant for the combination of two [Formula: see text] radicals which was found to be (2.5 ± 0.7) × 1010 l mole−1 s−1.

scholarly journals A comparative thermal decomposition kinetics on 1,2-bis(imino-4'-antipyrinyl)ethane and 4-N-(4'-antipyrylmethylidene)aminoantipyrine Cu(II) complexes with varying counter anions

2018 ◽  
Vol 3 (2) ◽  
pp. 108-115
Author(s):  
Tesfay Gebretsadik Ashebr ◽  
Wolfgang Linert ◽  
Nayathuparambil Thomas Madhu
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Kinetic Studies ◽  
Decomposition Kinetics ◽  
Thermal Decomposition Kinetics ◽  
Ligand Field ◽  
Decomposition Kinetic ◽  
Exponential Factor ◽  
Entropy Of Activation ◽  
Thermal Decomposition Kinetic

A comparative thermal decomposition kinetic studies of Cu(II) complexes of 1,2-bis (imino-4-antipyrinyl) ethane(GA) and4-N-(4'-antipyrylmethylidene) aminoantipyrine (AA) with a variety of counter anions viz. ClO4-, NO3-, Cl- and Br- has been evaluated by TG analysis. The kinetic parameters activation energy (E), pre-exponential factor (A) and entropy of activation (∆S) were calculated by using Coats–Redfern equation. This study shows that the thermal decomposition kinetics has been controlled by the ligand field as well as the counter anions.

PHOTO-INITIATED REACTIONS OF THIOLS AND OLEFINS: I. THE THIYL RADICAL CATALYZED ISOMERIZATION OF BUTENE-2 AND 1,2-ETHYLENE-d2

1964 ◽  
Vol 42 (10) ◽  
pp. 2239-2249 ◽  
Author(s):  
D. M. Graham ◽  
R. L. Mieville ◽  
C. Sivertz
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Kinetic Study ◽  
Rate Constants ◽  
Reaction Rate ◽  
Kinetic Studies ◽  
Thiyl Radical ◽  
First Order ◽  
Thiyl Radicals ◽  
Simple Mechanism

Kinetic studies have been made of the isomerization of butene-2 and 1,2-ethylene-d2 catalyzed by thiyl radicals produced from the photolysis of methanethiol. The rate of isomerization was found to be first order with respect to both the olefin and [Formula: see text] concentrations. The lack of influence of pressure on the reaction rate, at pressures above about 4 mm, leads to a simple mechanism in which isomerization is considered to occur as a result of thermal decomposition of the collisionally stabilized adduct radical produced in the reaction [Formula: see text]. The rate constants for this attack step were found to be 2 × 107 and 4.8 × 106 l mole−1 s−1 for butene-2 and ethylene-d2, respectively. In both cases the activation energy for isomerization was found to be close to zero. From a kinetic study of the isomerization of cis-butene-2 in the presence of butadiene-1,3, which acts as a retarder, the attack constant for butadiene at 25 °C was found to be 4.5 × 108 l mole−1 s−1.

Analogues of the active and inactive sodium carbonate

1982 ◽  
Vol 47 (12) ◽  
pp. 3348-3361 ◽  
Author(s):  
Erich Lippert ◽  
Karel Mocek ◽  
Emerich Erdös
Keyword(s):  
Thermal Decomposition ◽  
Time Dependence ◽  
Water Vapour ◽  
Sulphur Dioxide ◽  
Atmospheric Pressure ◽  
Flow Reactor ◽  
Kinetic Measurements ◽  
Sodium Potassium ◽  
Alkaline Metals ◽  
Hydrogen Carbonates

The reactivity of the anhydrous carbonates of alkaline metals with sulphur dioxide has been studied experimentally in dependence both on the nature of the cation and on the way of preparation of the anhydrous carbonate. The carbonates were prepared either by thermal decomposition of hydrogen carbonates or by thermal dehydration of carbonate hydrates. The carbonates of lithium, sodium, potassium, rubidium and caesium have been investigated. Kinetic measurements were carried out in a flow reactor in the integral regime at 423 K under atmospheric pressure, with a gas containing 0.2 vol.% of sulphur dioxide and 2.0 vol.% of water vapour in the nitrogen as a carrier gas. The reactivities have been compared on the basis of time dependence of the conversion of carbonate to sulphite.

Ten-Vertex Polyhedral Monocarbaborane Chemistry. The Novel High-Yield Formation of the Ten-Vertex closo Compound [6-(PMe2Ph)-closo-1-CB9H9] from the Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11]

1993 ◽  
Vol 58 (12) ◽  
pp. 2924-2935 ◽  
Author(s):  
Jane H. Jones ◽  
Bohumil Štíbr ◽  
John D. Kennedy ◽  
Mark Thornton-Pett
Keyword(s):  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
High Yield ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
X Ray ◽  
Yield Formation ◽  
Boiling Toluene

Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11] in boiling toluene solution results in an elimination of the platinum centre and cluster closure to give the ten-vertex closo species [6-(PMe2Ph)-closo-1-CB9H9] in 85% yield as a colourles air stable solid. The product is characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Crystals (from hexane-dichloromethane) are monoclinic, space group P21/c, with a = 903.20(9), b = 1 481.86(11), c = 2 320.0(2) pm, β = 97.860(7)° and Z = 8, and the structure has been refined to R(Rw) = 0.045(0.051) for 3 281 observed reflections with Fo > 2.0σ(Fo). The clean high-yield elimination of a metal centre from a polyhedral metallaborane or metallaheteroborane species is very rare.

Study of aerobic oxidation of phenyl PtII complexes (dpms)PtIIPh(L) (dpms = di(2-pyridyl)methanesulfonate; L = water, methanol, or aniline)

2009 ◽  
Vol 87 (1) ◽  
pp. 110-120 ◽  
Author(s):  
Julia R Khusnutdinova ◽  
Peter Y Zavalij ◽  
Andrei N Vedernikov
Keyword(s):  
Aqueous Solution ◽  
Aerobic Oxidation ◽  
Reductive Elimination ◽  
High Yield ◽  
Ambient Conditions ◽  
Activation Barriers ◽  
Methanol Solutions ◽  
Anionic Species ◽  
Mechanism Of Oxidation ◽  
Solution Mechanism

Oxidation of phenyl PtII complexes K[(dpms)PtIIPh2], 1, (dpms)PtIIPh(MeOH), 2, (dpms)PtIIPh(OH2), 3, and methyl PtII complex (dpms)PtIIMe(NH2Ph), 6, with O2 in aqueous or methanol solutions under ambient conditions leads to corresponding (dpms)PtIVR(X)OH complexes (R = X = Ph, 7; R = Ph, X = OH, 8; R = Ph, X = OMe, 9; R = Me, X = NHPh; 11; dpms = di(2-pyridyl)methanesulfonate). Complexes 7–9 could be isolated in high yield. Complex 11 as well as its phenyl analogue (dpms)PtIVPh(NHPh)OH, 10 can be prepared in high yield by oxidation of corresponding (dpms)PtIIR(NH2Ph) with H2O2 in methanol. Phenyl PtII complexes (dpms)PtIIPh(HX) derived from HX = aniline and DMSO, 4 and 5, respectively, are inert toward O2. The rate of oxidation of 1–5 with O2 decreases in the order 1 > 3 ~ 2 » 4, and 5 is unreactive. Methyl analogues are significantly more reactive compared with their phenyl counterparts. Proposed mechanism of oxidation with O2 includes formation of anionic species (dpms)PtIIR(X)– responsible for reaction with dioxygen. Attempts at C–O and C–N reductive elimination from phenyl PtIV complexes 7–10 do not lead to phenyl derivatives PhX at 80–100 °C, consistent with the results of the DFT estimates of corresponding activation barriers, ΔG0 exceeding 28 kcal/mol.Key words: platinum phenyl complexes, oxidation, dioxygen, aqueous solution, mechanism.

Application of Calculus Equation in Solving Thermal Decomposition Kinetics Parameters of Flame Retardant Wood

2014 ◽  
Vol 983 ◽  
pp. 190-193
Author(s):  
Cai Yun Sun ◽  
Yong Li Yang ◽  
Ming Gao
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Thermal Degradation ◽  
Phosphoric Acid ◽  
Flame Retardant ◽  
Kinetic Parameters ◽  
Flame Retardancy ◽  
Decomposition Kinetics ◽  
Thermal Decomposition Kinetics ◽  
Kinetics Parameters

Wood has been treated with amino resins and amino resins modified with phosphoric acid to impart flame retardancy. The thermal degradation of samples has been studied by thermogravimetry (TG) in air. From the resulting data, kinetic parameters for different stages of thermal degradation are obtained following the method of Broido. For the decomposition of wood and flame retardant wood, the activation energy is found to decrease from 122 to 72 kJmol-1.

Sign in / Sign up

Export Citation Format

Share Document