Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media

1993 ◽  
Vol 71 (12) ◽  
pp. 2155-2159 ◽  
Author(s):  
Subrata Mukhopadhyay ◽  
Swapan Chaudhuri ◽  
Rina Das ◽  
Rupendranath Banerjee
Keyword(s):  
Free Radicals ◽  
Rate Constant ◽  
Decomposition Rate ◽  
Rate Constants ◽  
Kinetics And Mechanism ◽  
Unimolecular Decomposition ◽  
Decomposition Rate Constant ◽  
Mixed Complexes ◽  
Ph Range ◽  
Oxalate Ion

In the pH range 6.6–8.6, [MnL2(H2O)2]+ and [MnL2(H2O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox2−) to CO2 through the inner-sphere intermediates [MnL2(ox)]− and [MnL2(OH)(ox′)]2−, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10−4 s−1 and 11.2 × 10−2 M−1 s−1 at 30 °C and at I = 1.0 M (NaClO4). Decomposition of these mixed complexes produces free radicals, presumably CO2−, which is further oxidized to CO2 by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)3]3− is produced quantitatively when [ox]0 ≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10−4s−1 at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10−4 s−1 at 25 °C and I = 1.0 M).

Decomposition rate constants of Picea abies logs in southeastern Norway

1999 ◽  
Vol 29 (3) ◽  
pp. 372-381 ◽  
Author(s):  
Erik Næsset
Keyword(s):  
Picea Abies ◽  
Rate Constant ◽  
Cross Sections ◽  
Decomposition Rate ◽  
Rate Constants ◽  
Initial Density ◽  
Decomposition Rate Constant ◽  
Negative Exponential Function ◽  
Standing Trees ◽  
Negative Exponential

Decomposition rate constants were estimated from 384 cross sections of Norway spruce (Picea abies (L.) Karst.) logs with base diameter >7.0 cm collected in open areas at five different study sites in southeastern Norway. Fresh wood core samples were taken from 95 standing trees adjacent to the logs to estimate the initial density of these cross sections. Based on this chronosequence, a simple negative exponential function of time showed an average decomposition rate constant for all cross sections of 0.033 per year. Cross-section diameter, ground contact, soil moisture, and aspect were all found to have significant impacts on the decomposition rate constant. For different combinations of these characteristics the decomposition rate constant ranged from a minimum of 0.0165 per year to a maximum of 0.0488 per year.

Anharmonic effect of the decomposition reaction of the CF3CCl2O radical

2012 ◽  
Vol 90 (2) ◽  
pp. 186-194 ◽  
Author(s):  
Qian Li ◽  
Wenwen Xia ◽  
Li Yao ◽  
Ying Shao
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Decomposition Reaction ◽  
Unimolecular Decomposition ◽  
Anharmonic Effect ◽  
Canonical Systems ◽  
Bond Scission

The rate constant of the unimolecular decomposition reaction of the CF3CCl2O radical was calculated by using the method proposed by Yao and Lin (YL method). Two important channels of decomposition occurring via C–C and C–Cl bond scission were investigated. The results show that C–Cl bond scission is the dominant channel during the decomposition of the CF3CCl2O radical. Especially, the reasonable anharmonic effect on the decomposition reaction was investigated. The results show that the harmonic rate constants are higher than those of the anharmonic case in both microcanonical and canonical systems. The anharmonic effect is more evident with increasing energy.

The thermal unimolecular decomposition rate constants of ethoxy radicals

1999 ◽  
Vol 1 (12) ◽  
pp. 2935-2944 ◽  
Author(s):  
oise Caralp ◽  
Pascal Devolder ◽  
Christa Fittschen ◽  
Nathalie Gomez ◽  
Horst Hippler ◽  
...  
Keyword(s):  
Decomposition Rate ◽  
Rate Constants ◽  
Unimolecular Decomposition

Kinetics and mechanism of covalent addition of S(IV) species to the acridinium cation

1996 ◽  
Vol 74 (3) ◽  
pp. 365-370 ◽  
Author(s):  
Maria P. Ros ◽  
Jesus Thomas ◽  
Guillermo Crovetto ◽  
Juan Llor
Keyword(s):  
Rate Constants ◽  
Carbonyl Compounds ◽  
Nonlinear Least Squares ◽  
Kinetics And Mechanism ◽  
Experimental Conditions ◽  
Ph Profile ◽  
First Order ◽  
Constant Ph ◽  
Ph Range ◽  
Experimental Values

The reaction of acridine with S(IV) species (SO2•H2O, HSO3−, and SO32−) to form the adduct acridine–S(IV) has been studied spectrophotometrically throughout the pH range 2.6–8 in aqueous solutions. The observed pseudo-first-order rate constants, kobs, were determined at 25 °C and ionic strength I = 0.11 M, and the pH profile of the rate reached a maximum at pH ≈ 6.1. At constant pH the kobs values were a linear function of the total S(IV) concentration with slopes that increased significantly with pH. These data are consistent with the rate-determining attack of SO3H− and SO32− upon the C-9 of the acridinium cation. A nonlinear least-squares fitting of the experimental values to the model equation, within the overall pH region studied, yields the pH-independent rate constants k1 = 3.7 ± 0.1 and k2 = (6.24 ± 0.04) × 104 M−1 s−1 for the attack of these two species, respectively. The experimental results agree very well with the kinetic model. Due to the experimental conditions used we did not detect any possible pseudobase formation in the pH range studied. The reactivity of the S(IV) species with acridine follows the order: [Formula: see text] The value obtained for the ratio k1/k2 is similar to the results given for other addition reactions of S(IV) species to the double bond of carbonyl compounds such as benzaldehyde and formaldehyde. Key words: covalent addition, acridine, acridine – S(IV) adducts, kinetics and mechanism.

scholarly journals Leaf-litter decomposition and nutrient dynamics of five selected tropical tree species

2020 ◽  
Vol 30 (1) ◽  
pp. 32-38
Author(s):  
S. Bhattarai ◽  
B. Bhatta
Keyword(s):  
Weight Loss ◽  
Leaf Litter ◽  
Litter Decomposition ◽  
Rate Constant ◽  
Decomposition Rate ◽  
Tree Species ◽  
Nutrient Dynamics ◽  
Decomposition Rate Constant ◽  
Tropical Tree Species ◽  
One Year

Leaf-litter decomposition in terrestrial ecosystems has a major role in recycling the nutrients to the soil. Nutrient dynamics is the way nutrients cycle in an ecosystem. The present study was conducted for five selected tropical tree species viz. Shorea robusta, Ficus hookeri, Mallotus philippensis, Artocarpus lakoocha and Dillenia pentagyna at Hetauda, Makawanpur. This paper aims to determine the litter decomposition rate-constant and nutrient mineralization pattern of the selected species. The litter-bag method was used to assess the decomposition and nutrient dynamics for one year. Both decomposition rate-constant and weight loss were highest for M. philippensis (% weight loss = 73.49; k = 0.33) and lowest for S. robusta (% weight loss = 54.01; k = 0.18). In general, weight remaining showed a strong negative correlation with N and P concentration but a slightly negative with K. However, the remaining weight of litter showed a strong positive correlation with C : N ratio, thus indicating a good predictor of mass loss and mineralization. The study showed that there was no net release of nitrogen during the one-year study period; however, the net P release was found to be highest for S. robusta followed by D. pentagyna and the net K release was highest in F. hookeri followed by A. lakoocha.

scholarly journals Modelling the temperature of a compost microreactor in isolation

2020 ◽  
Author(s):  
◽  
Mitchell Hawse
Keyword(s):  
Rate Constant ◽  
Decomposition Rate ◽  
Dry Mass ◽  
Small Scale ◽  
Conductive Heat ◽  
Wood Biomass ◽  
Decomposition Rate Constant ◽  
Plastic Container ◽  
Waste Wood ◽  
Municipal Biosolids

A mixture of waste-wood biomass and municipal biosolids waste was composted in a plastic container inside of an insulated chamber. The mixture of biomass and biosolids was approximately 50:50 and weighed 82.6 kg. The peak temperature of the compost was 32.4◦C. The small scale of the compost system allowed the lower limit of the compost decomposition rate to be studied. A model was successfully developed to predict the core temperature of the compost using the ambient temperature in the insulated chamber. A literature review was conducted to determine literature values for the overall convective and conductive heat transfer coefficient, the dry mass fraction, and heat of combustion for both biomass and biosolids. The model used an optimization algorithm to calculate the rate constant for the experimental setup. The calculated decomposition rate constant was 0.0525 Day−1.

scholarly journals Patterns of Leaf Litter Decomposition as Related to Litter Traits in the Sudano-Guinea Savannahs of Ngaoundere, Cameroon

2019 ◽  
pp. 1-19
Author(s):  
A. Ibrahima ◽  
P. Souhore ◽  
A. A Mang A Menick
Keyword(s):  
Phenolic Compounds ◽  
Leaf Litter ◽  
Litter Decomposition ◽  
Plant Species ◽  
Rate Constant ◽  
Decomposition Rate ◽  
Dry Mass ◽  
Specific Mass ◽  
Decomposition Rate Constant ◽  
Litter Mass

Litter decomposition processes are poorly studied in the savannahs. Leaf litter decomposition of the twenty-four contrasting plant species including trees, shrubs and grass species, was studied in the sudano-guinea savannahs of Ngaoundere, Cameroon. The litterbag technique was used to assess litter mass loss and single exponential model was adopted to estimate decay rate constants. Initial litter thickness varied from 0.02 to 1.11 mm, area from 4.27 to 245.89 mm2, sclerophyllous index from 0.01 to 1.75 mg.mm-2, density from 0.21 to 87.50 mg.mm-3, and specific mass area from 0.57 to 185.46 mm2.mg-1. Litter cellulose content varied from 3.79 to 11.84%; lignin from 2.84 to 8.12%, NDF from 21.35 to 80.41%, and total phenolic compounds from 0.47 to 17.76%. During the 52 weeks of the field experiment, mean dry mass remaining of litter samples was significantly between 8.05 and 75.22% of initial litter dry mass for C. papaya and C. regidus respectively. Litter decomposition rate constant (k) significantly ranged from 0.003 (C. regidus) to 0.121 %.week-1 (C. papaya). Litter mass remaining (LMR) was positively related to thickness (R2 = 0.605, P<0.01), Sclerophyllous index (R2 = 0.446, P<0.05), Specific mass area (R2 = 0.569, P<0.001), lignin (R2 = 0.631, P<0.01) and phenolic compounds (R2 = 0.618, P<0.001). The litter decomposition rate constant (k) was negatively related to thickness (R2 = 0.602, P<0.01, n=12), Sclerophyllous index (0.542; P<0.05), Specific mass area (0.419; P<0.05) and phenolic compounds (0.530; P<0.01). It can be concluded that litter decomposition is affected by plant species diversity, plant groups and physico-chemical traits of litters in the sudano-guinea savannahs of Ngaoundere, Cameroun. These preliminary results would contribute to understanding the mechanism of litter decomposition in general and in these savannahs in particular.

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