scholarly journals Kinetics and mechanism of the oxidation of disaccharides by CrVI

2002 ◽  
Vol 80 (12) ◽  
pp. 1676-1686 ◽  
Author(s):  
Viviana Roldán ◽  
Juan Carlos González ◽  
Mabel Santoro ◽  
Silvia García ◽  
Nieves Casado ◽  
...  

The oxidation of D-lactose, D-maltose, D-melibiose, and D-cellobiose by CrVI yields the corresponding aldobionic acid and Cr3+ as final products when an excess of reducing disaccharide over CrVI is used. The rate law for the CrVI oxidation reaction is expressed by –d[CrVI]/dt = kH [disaccharide][CrVI], where the second-order kinetic constant, kH, depends on [H+]. The relative reactivity of the disaccharides with CrVI is expressed as follows: Mel > Lac > Cel > Mal, at 33°C. In acid medium, intermediate CrV forms and reacts with the substrate faster than CrVI. The EPR spectra show that five- and six-coordinate oxo-CrV intermediates are formed, with the disaccharide acting as bidentate ligand. Five-coordinate oxo-CrV species are present at any [H+], whereas six-coordinate ones are observed only at pH < 2, where they rapidly decompose to the redox products. In the pH 3–7 range, where hexa-coordinate oxo-CrV species are not observed, CrV complexes are stable enough to remain in solution from several days to several months.Key words: chromium, saccharides, kinetics, EPR.

Author(s):  
Marta Lígia Pereira da Silva ◽  
Tellys Lins Almeida Barbosa ◽  
Meiry Gláucia Freire Rodrigues

Background: Region-based solutions for water cleaning could be critical to tackle the water challenges faced in enhancing the in the future. Brazilian Primavera clay is cheap, abundant, and an untested material that has the potential to be used for water cleaning. Objective: the objective of the present work was to thermally activate and characterize the Brazilian clay and then determine the potential to remove Cd2+ from an aqueous solution. Methods: Primavera clay was thermally activated at 300 oC and characterized using X ray diffraction, X-ray Spectroscopy Energy Dispersive, and N2 adsorption. Sorption equilibrium was determined using the following experimental conditions: constant pH 4.5, 5 h, and 27 oC. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherms models were applied in order to determine the efficiency of clay used as an adsorbent. Adsorption kinetics was analyzed using the pseudo-second-order kinetic model. Results: In this study, results revealed that even though the heat treatment did not cause profound alterations on the clay structure(smectite) and surface area (78 m2 /g), a pseudo-second-order kinetic constant of 0.5563 mg/g/min was found for the cadmium removal. Conclusion: The mathematical models of the Langmuir and Temkin showed a better fit to the experimental data. A high affinity between the cadmium and the thermally activated Primavera clay was found up to 88 % with removal efficiencies.


1999 ◽  
Vol 64 (11) ◽  
pp. 1877-1892 ◽  
Author(s):  
Vincenzo Frenna ◽  
Gabriella Macaluso ◽  
Giovanni Consiglio ◽  
Susanna Guernelli ◽  
Domenico Spinelli

The rate constants of the title reactions have been measured at various amine concentrations. The second-order kinetic constant for the amino substitution increases in a hyperbolic way as a function of the nucleophile concentration. The k3Am/k-1 ratio for each catalysed system is not a monotonic function of the X substituent. This result has been rationalized in the framework of the SB-GA (Specific Base-General Acid) mechanism of base catalysis.


2015 ◽  
Vol 4 (3) ◽  
pp. 302-309 ◽  
Author(s):  
Deepmala Pareek ◽  
Riya Sailani ◽  
Vinita Gupta ◽  
Chandra Khandelwal ◽  
Prem Sharma

2016 ◽  
Vol 4 (2) ◽  
pp. 105-112
Author(s):  
Lalchhing puii ◽  
◽  
Seung-Mok Lee ◽  
Diwakar Tiwari ◽  
◽  
...  

A mesoporous silica was synthesized by annealing (3-Aminopropyl) triethoxysilane grafted chitosan at 800˚C. The mesoporous silica was characterized by the XRD (X-ray diffraction) analysis. The BET specific surface area and pore size of silica was found to be 178.42 m2/g and 4.13 nm. The mesoporous silica was then employed for the efficient remediation of aqueous solutions contaminated with Cu(II) under batch and column reactor operations. The mesoporous silica showed extremely high per cent removal of Cu(II) at wide pH range i.e., pH ~2.0 to 7.0. Relatively a fast uptake of Cu(II) was occurred and high percentage removal was obtained at initial concentrations studied from 1.0 to 15.0 mg/L. The equilibrium state sorption data were utilized for the Langmuir and Freundlich adsorption isotherm studies. Moreover, the effect of an increase in background electrolyte concentrations from 0.0001 to 0.1 mol/L NaNO3 was assessed for the uptake of Cu(II) by mesoporous silica. The equilibrium sorption was achieved within 240 min of contact and the kinetic data is best fitted to the pseudo-second-order and fractal like pseudo-second-order kinetic models. In addition, the mesoporous silica was used for dynamic studies under column reactor operations. The breakthrough curve was then used for the non-linear fitting of the Thomas equation and the loading capacity of the column for Cu(II) was estimated.


2011 ◽  
Vol 396-398 ◽  
pp. 75-87
Author(s):  
Zai Fu Yang ◽  
Xiao Jing Yang ◽  
Li Hong Sun ◽  
Lian Lian Xu

ABSTRACT: Cation adsorbent was prepared from the Solidago Canadensis(which are abandoned agricultural land of alien invasive plants)by Sulfuric acid esterification modified , isoamyl alcohol as reaction medium. Design L934 orthogonal experiment, the Solidago canadensis cation exchange adsorbent, the optimal preparation conditions. Experimental results show that at 15°C, concentrated sulfuric acid and amyl alcohol volume ratio of 5:6 obtained under conditions of Solidago canadensis cation exchange adsorbent for Pb(II) exchange best. The experimental results of Pb(II) adsorption onto the Solidago Canadensis based cation adsorbent showed that the best conditions are: the initial pH 5, the concentration of Pb(II) 300mg/L,the dosage of cation adsorbent 1.2mg/L and adsorption time 3h. The adsorption data were analyzed by using pseudo-first-order and pseudo-second-order kinetic models were found to follow the pseudo-second-order kinetic model.


1987 ◽  
Author(s):  
Moideen P Jamaluddin

Platelet aggregation kinetics, according to the particle collision theory, generally assumed to apply, ought to conform to a second order type of rate law. But published data on the time-course of ADP-induced single platelet recruitment into aggregates were found not to do so and to lead to abnormal second order rate constants much larger than even their theoretical upper bounds. The data were, instead, found to fit a first order type of rate law rather well with rate constants in the range of 0.04 - 0.27 s-1. These results were confirmed in our laboratory employing gelfiltered calf platelets. Thus a mechanism much more complex than hithertofore recognized, is operative. The following kinetic scheme was formulated on the basis of information gleaned from the literature.where P is the nonaggregable, discoid platelet, A the agonist, P* an aggregable platelet form with membranous protrusions, and P** another aggregable platelet form with pseudopods. Taking into account the relative magnitudes of the k*s and assuming aggregation to be driven by hydrophobic interaction between complementary surfaces of P* and P** species, a rate equation was derived for aggregation. The kinetic scheme and the rate equation could account for the apparent first order rate law and other empirical observations in the literature.


Author(s):  
Mohamed Nasser Sahmoune ◽  
Krim Louhab ◽  
Aissa Boukhiar

Dead streptomyces rimosus was found to be an effective biosorbent for the removal of chromium from industrial tanning effluents. A sorption level of 65 mg/g was observed at pH 4.8 while the precipitation effect augmented this value at a higher pH range. Chromium desorption increased with decreasing desorption agents pH (including HCl and H2SO4) to a maximum value of 95% at approximately zero pH. The biosorption data of trivalent chromium by streptomyces rimosus has been used for kinetic studies based on fractional power, Elovich, pseudo-first order and pseudo-second order rate expressions. The time-dependent Cr (III) biosorption data were well-described by a pseudo-second-order kinetic model. The intraparticle diffusion is not the rate-limiting step for the whole reaction. It was found that the biosorption equilibrium data fit well with the Langmuir model.


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