Search Results
Heat of chemisorption of 1-propanol on α-Al2O3 at 25–200°C
A microcalorimetric study
Abstract
We have studied by means of differential microcalorimetry the adsorption process of 1-propanol on α-Al2O3 at the temperatures of 25, 50, 100, 150 and 200°C, respectively. Both amounts of adsorbed alcohol and heats released decrease as the temperature of adsorption increases. At very low coverage, the high value of differential heat shows a strong irreversible chemisorption on active sites (Lewis acid sites) (qdiff>200 kJ·mol−1). Moreover, we carried out some thermokinetic investigations on heat emission peaks at different coverage degree (different equilibrium pressure of 1-propanol vapour as a function of time) and at different temperatures of adsorption, at same coverage.
Abstract
Then-alkanes of different lengths were preadsorbed to selectively block part of the micropores of a MFI-type zeolite, Silicalite-I. The porosity available to argon and nitrogen was then studied by quasi-equilibrium adsorption microcalorimetry and volumetry at 77K and compared to what was found for the bare zeolite. Indeed, although partial adsorption ofn-alkanes does not alter the value of the differential enthalpies of adsorption for both argon and nitrogen, then-butane preadsorption diminishes the adsorption capacity by inducing inaccessible volumes in the micropore network. Moreover, the microcalorimetric experiments clearly show thatn-butane is not evenly distributed in the zeolite channel network while the longern-alkanes used are.
Abstract
The oxidation of substrates with various function groups (i.e., ortho-diphenol, ortho-aminophenol, p-aminophenol, ortho-phenylene diamine and p-phenylene diamine) catalyzed by Laccase have been studied using of LKB-2107 batch microcalorimetry system. The overall reaction enthalpy Δr H m, Michaelis constant K m, pseudo-first-order rate constant k 2 of the reactions and binding energy ΔG 0 of Laccase-substrate complex for each substrate have been determined at 298.15 K, pH 7.4. The binding enthalpy ΔH 0 and binding entropy ΔS 0 of LS complex, when the substrate is Gallic acid and 2,3-dicyan hydroquinone respectively, have been also determined. The rate constants of the reaction between Laccase and these substrates are essentially identical because the rate of Laccase-catalytic reaction is limited by the step of electron transfer from the type 2 Cu(II)-bound substrate to the less exposed type 1 copper site, and the intra-complex electron transfer rate mainly dependents on the amino residues conformational changes. But the rate of the reaction between Laccase and substrates with group -OH is slower than group -NH2, because of the higher energy of bounding electron. The stability of LS complex depends on ΔS 0, since ΔH 0>0, substrate distinguished by Laccase depends on the value of allosteric entropy of the amino acid residues induced by substrate. The relationship between Laccase and its substrates cannot be regarded as a simple relationship of lock and key, but an induce-fit relationship.
Abstract
Microcalorimetry was used to study the seasonal evolution over one year of the microbial activity in a humic-eutrophic Cambisol soil as a function of its forest cover. The study was carried out on three soils with identical origin but covered with different forest species: pine, eucalyptus, and a typical Atlantic-humid riverside forest. Some other physical, chemical and biological properties and environmental parameters, mainly humidity and environmental temperature, were considered to analyze their influence on soil microbial activity. The study was performed using a microcalorimeter Thermal Analysis Monitor 2277 in which the experiments were carried out with 1 g soil samples treated with 1.25 mg glucose g–1 soil. From the measured results it follows that pine forest soil is the least productive of the three, as it generates an average heat of 2.7 vs. 5.9 J g–1 generated by the eucalyptus forest soil and 3.1 J g–1 generated by the riverside forest soil. These results are dependent on the remaining physical, chemical and biological features analysed and because of this, pine forest soil, with a pH value 3.3 in spring, shows a small capacity to maintain a stable microbial population which is the lowest of the three (0.079108 to 0.46108 microorganisms g–1 soil) while riverside soil microbial population is in the range from 7.9108 to 17108 microorganisms g–1 soil.
Abstract
The polymorphic behaviour of the purine derivative MKS 492 was studied with investigations of suspensions of selected samples in different solvents and of samples obtained by crystallizations. The samples were analyzed by DSC, TG and X-ray diffraction. Six different crystalline modifications called A, B, B
, C, D and E and an amorphous form were identified. Four pure crystalline modifications, A, B, C and D have been manufactured and characterized by DSC, X-ray, IR, solubilities, densities, hygroscopicity and dissolution measurements. The four forms A, C, D and E are monotrop to the form B. The form B is enantiotrop to the form B, which revealed the highest melting point of all known polymorphs. This form B is only stable at high temperature. Temperature resolved X-ray diffraction was very helpful for proper interpretation of the thermal events. The melting peaks of the forms A and C and the endothermic peak corresponding to the enantiotropic transition B into B occur in a narrow range of temperature. The form B which is the most stable one at room temperature has been chosen for further development. Quantitative methods to determine the content of the forms A, C and D in samples of form B or to determine the content of form A, B and D in form C have been developed by using X-ray diffraction. Limits of detection are 1 or 2%. For the quantitative determination of the amorphous fraction, X-ray diffraction and microcalorimetry are compared. For high amounts of the amorphous fraction, the X-ray diffraction method is preferred because it is faster. Microcalorimetry is very attractive for levels below 10% amorphous content. The lowest limit of detection is obtained by microcalorimetry, about 1%.
Abstract
In this paper, a promoter-probe plasmid pKK232-8 was used as a vector, which functioned in Escherichia coli TG1 host. The plasmid DNA fragments from Pseudomonas maltophilia AT18 chromosome DNA active as promoter inEscherichia coli TG1, the promoter function was studied by means of microcalorimetry, the promoter is about 800 bp DNA, it can promote the chloramphenicol (Cm) gene in plasmid pKK232-8, the Cm resistance level is about 80 μg mL–1, the promoter activity is high. It implicates that there are probably many promoters in Pseudomonas maltophilia AT18 chromosome. All these information is readily obtained by an LKB 2277-204 heat conduction microcalorimeter. Microcalorimetry is a quantitative, inexpensive, and versatile method for microbiological genetic research.
Abstract
The exothermic decomposition of cumene hydroperoxide (CHP) in cumene liquid was characterized by isothermal microcalorimetry, involving the thermal activity monitor (TAM). Unlike the exothermic behaviors previously determined from an adiabatic calorimeter, such as the vent sizing package 2 (VSP2), or differential scanning calorimetry (DSC), thermal curves revealed that CHP undergoes an autocatalytic decomposition detectable between 75 and 90°C. Previous studies have shown that the CHP in a temperature range higher than 100°C conformed to an n th order reaction rate model. CHP heat of decomposition and autocatalytic kinetics behavior were measured and compared with previous reports, and the methodology and the advantages of using the TAM to obtain an autocatalytic model by curve fitting are reported. With various autocatalytic models, such as the Prout-Tompkins equation and the Avrami-Erofeev rate law, the best curve fit among models was also investigated and proposed.
Abstract
The antibacterial action of amoxicillin (AMPC) and the inclusion complexes of AMPC with α-, β- and γ-cyclodextrins (α-CD, β-CD and γ-CD, respectively) to Escherichia coli B (E. coli) was evaluated by isothermal titration microcalorimetry and by petri-dish bioassay method. The effects of the compounds on produced heat during the exponential phase of the E. coli growing were measured and the growing rate constants of the cells was calculated from the power-time (p-t) curve before and after the treatment with AMPC. Results from the both methods showed that the antibacterial activity became stronger in the following order: AMPC-βCD > AMPC-γCD ≈ AMPC-αCD > AMPC only.
Abstract
Cumene hydroperoxide (CHP) and its derivatives have caused many serious explosions and fires in Taiwan as a consequence of thermal instability, chemical contamination, and even mechanical shock. It has been employed in polymerization for producing phenol and dicumyl peroxide (DCPO). Differential scanning calorimetry (DSC) was used to analyze the thermal hazard of CHP in the presence of sodium hydroxide (NaOH), sulfuric acid (H2SO4), and sodium bisulfite (Na2SO3). Thermokinetic parameters for decomposition, such as exothermic onset temperature (T 0 ), maximum temperature (T max ), and enthalpy (ΔH), were obtained from the thermal curves. Isothermal microcalorimetry (thermal activity monitor, TAM) was employed to investigate the thermal hazards during CHP storage and CHP mixed with NaOH, H2SO4, and Na2SO3 under isothermal conditions in a reactor or container. Tests by TAM indicated that from 70 to 90 °C an autocatalytic reaction was apparent in the thermal curves. According to the results from the TAM test, high performance liquid chromatography (HPLC) was, in turn, adopted to analyze the result of concentration versus time. By the Arrhenius equation, the activation energy (E a ) and rate constant (k) were calculated. Depending on the process conditions, NaOH was one of the incompatible chemicals or catalysts for CHP. When CHP is mixed with NaOH, the T 0 is induced earlier and the reactions become more complex than for pure CHP, and the E a is lower than for pure CHP.
