A novel thermokinetic research method for determination of rate constants of simple-order reaction in batch conduction calorimeter
under isothermal condition, the characteristic parameter method, is proposed in this paper. Only needing the characteristic
time parameter tm obtained from the measured thermoanalytical curve, the kinetic parameters of reactions studied can be calculated
conveniently with this method. The saponifications of ethyl propionate and ethyl acetate in aqueous ethanol solvent, the polymerization
of acrylamide in aqueous solution, the ring opening reaction of epichlorohydrin with hydrobromic acid have been studied. The
experimental results indicate that the characteristic parameter method for simple-order reaction is correct.
The effects of bentonite density and fulvic acid on the sorption and diffusion of 90Sr2+in compacted bentonite were investigated by using a capillary method. The experiments were carried out at pH 7.0±0.1 in the
presence of 0.01M NaClO4. The results suggest that the sorption and diffusion of 90Sr2+in compacted bentonite decreases with increasing the density of compacted bentonite. The presence of FA enhances the sorption
of Sr2+, but reduces the diffusion of Sr2+in compacted bentonite. The porosity of the compacted bentonite plays an important role in the sorption and diffusion behavior
of 90Sr2+. Using the calculated effective diffusion coefficients the long-term relative concentration distribution of strontium was
evaluated in compacted bentonite.
Authors:Z. Chen, F. Xie, X. Wang, Y. Chang, and Z. Zhang
A method of efficiency calibration for the measurement of 88Kr and 138Xe by HPGe γ-spectrometer is proposed in the present paper. The question for the efficient calibration is, how to achieve
homogeneous sources of 88Kr-88Rb and 138Xe-138Cs. The fission product gases were obtained by irradiating a precisely measured amount of U3O8 (90% 235U) filled in a quartz glass ampoule. Source cell was first filled up with stearic acid, and then the fission product gases
were charged into it. Xenon and krypton are not adsorbed on stearic acid, therefore, homogeneous sources of 88Kr-88Rb and 138Xe-138Cs can be prepared. The results of the experiment demonstrate that the method is feasible and successful.
57Co was produced with high pure nature iron irradiated by 8.5MeV deuterons. TBP-benzene extraction method and anion-exchange method were used to separate and purify it. The purified57Co was prepared into standard solution of about 30 to 50 g Co2+/ml carrier concentration and about 0.1 mol/l HCl. The specific activity of the standard solution was measured with 4
(ppc)- coincidence counting method. The final result was 476.82(1±0.42%)Bq/mg.
According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of opposing reactions have been derived, and a novel thermokinetic research method, the characteristic parameter method for opposing reactions which taking place in a batch conduction calorimeter under isothermal condition, has been proposed in this paper. Only needing the characteristic thermoanalytical data corresponding to tm and 2tm from the same curve, the rate constants of forward and backward reactions and equilibrium constant can be calculated simultaneously with this method. In order to test the validity of this method, the proton-transfer reactions of nitroethane with ammonia at 15 and 25°C, and with trihydroxymethyl aminomethane (Tris) at 15 and 30°C have been studied, respectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in the literature. Therefore, the characteristic parameter method for opposing reaction is believed to be correct.
In order to enrich the thermokinetic research methods and enlarge the applicable range of the thermokinetic time-parameter
method, the integral and differential thermokinetic equations of consecutive first-order reaction have been deduced, and the
mathematical models of the time-parameter method for consecutive first-order reactions have been proposed in this paper. The
rate constants of two steps can be calculated from the same thermoanalytical curve measured in a batch conduction calorimeter
simultaneously with this method. The thermokinetics of saponifications of diester in aqueoushanol solvent has been studied.
The experimental results indicate that the time-parameter method for the consecutive first-order reaction is correct.
Authors:X. Chen, W. Feng, W. Miao, Y. Shen, and Y. Yu
Power-time curves and metabolic properties of Tetrahymena thermophila BF5 exposed to different Yb3+ levels were studied by ampoule method of isothermal calorimetry at 28°C. Metabolic rate (r) decreased significantly while peak time (PT) increased with the increase of Yb3+. These results were mainly due to the inhibition of cell growth, which corresponded to the decrease of cell number obtained
by cell counting. Compared with cell counting, calorimetry was sensible, easy to use and convenient for monitoring the toxic
effects of Yb3+ on cells and freshwater ecosystem. It was also found that cell membrane fluidity decreased significantly under the effects
of Yb3+, which indicated that Yb3+ could be membrane active molecules with its effect on cell membranes as fundamental aspect of
DSC and TG-DTA techniques were used to investigate micro-sized silver powder particles and the adsorption of ethyl cellulose
on these particles in a solution of ethyl acetate. The apparent specific heat of the silver particles was determined, and
the kinetics of temperature-programmed desorption (TPD) of these adsorbed silver particles was investigated. Results show
that the apparent specific heat and desorption kinetic parameters obtained by thermal analysis techniques could be used to
characterize certain physico-chemical properties of such a particulate system.
Thermal decomposition of N,N′-diphenylguanidine (DPG) was investigated by simultaneous TG/DSC-FTIR techniques under nonisothermal conditions. Online FTIR measurements illustrate that aniline is a major product of DPG decomposition. The observation that the activation energy depends on the extent of conversion indicates that the DPG decomposition kinetics features multiple processes. The initial elimination of aniline from DPG involves two pathways because of the isomerization of DPG. Mass spectrometry and thin film chromatography suggest that there are two major intermediate products with the major one of C21N3H17. The most probable kinetic model deduced through multivariate nonlinear regression method agrees well with the experimental data with a correlation coefficient of 0.9998. The temperature-independent function of conversion f(α), activation energy E and the pre-exponential factor A of DPG decomposition was also established through model-fitting method in this research.
Authors:S. Chen, Sh Gao, X. Yang, R. Hu, and Q. Shi
Solid complexes of M(His)2Cl2nH2O (M=Mn, Co, Ni, Cu) of MnCl26H2O, CoCl26H2O, NiCl26H2O, CuCl22H2O and L-α-histidine (His) have been prepared in 95% ethanol solution and characterized by elemental analyses, chemical analyses,
IR and TG-DTG. The constant-volume combustion energies of the complexes have been determined by a rotating-bomb calorimeter.
And the standard enthalpies of formation of the complexes have been calculated as well.