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1.
The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation
and that for the latter 50% mass-loss of HNNC described by the reaction equations
and
This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

2.
In this work some calorimetric measurements were also carried out on the electrorefining silver by using different current densities with a Calvet type microcalorimeter at room temperature. The ratio (R) of the measured heat (
m) to the input electric energy (
in) and the excess heat (
ex), i.e., difference between
m and
in during the electrorefining process, were discussed in terms of general thermodynamics. It was found that the R and
ex for silver were related with the current density or cell voltage employed in the experiment. The results obtained here also indicate that the heat generation under different conditions, such as different currents or voltages may be caused partially by the irreversibility of the process or by some unknown processes.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

3.
The equilibrium constant for the hydrolytic disproportionation of I2
has been determined at 25°C and at ionic strength 0.2 M(NaClO4) in buffered solution. The reaction was followed in the pH range where the equilibrium concentration of I2, I, and IO3 are commensurable, i.e., the fast equilibrium
is also established. The equilibrium concentrations of I2and I3 were determined spectrophotometrically, and the concentrations of all the other species participating in process (1) were calculated from the stoichiometric constraints. The constants determined are \log K_1 = -47.61\pm 0.07 and \log K_2 = 2.86 \pm 0.01.  相似文献   

4.
The kinetics of osmium(VIII)-catalyzed oxidation of hypophosphite with hexacyanoferrate(III) in alkaline medium has been studied. The rate is independent of the concentration of the oxidant. The order with respect to hydroxide ion is variable. Rate law (1) conforms with the experimental observations.
The equilibrium constant 'K 1' for step (2)
has been evaluated kinetically to be (21 ± 5.0), (23 ± 5.0), (26 ± 6) and (32 ± 6) at 25, 30, 32 and 35 °C and I = 1.0 mol dm–3 respectively. The energy and entropy of activation were calculated to be (42 ± 2.0) kJ mol–1 and (82 ± 6.0) J K–1 mol–1 respectively. A plausible reaction mechanism has been suggested.  相似文献   

5.
The solubility of rhodochrosite (MnCO3) at 25°C under constant carbon dioxide partial pressure p(CO2) was determined in NaCl solutions as a function of ionic strength I. The dissolution of MnCO3(s) for the reaction
has been determined as a function of pH. From these values, we have determined the equilibrium constant for the stoichiometric solubility of MnCO3(s) in NaCl solutions
These values have been fitted to the equation
with a standard error of = 0.1 with Iand concentrations in molalities. The extrapolated value of log K o sp(–10.3) in water is in good agreement with literature data (–10.1 to 10.8) determined in solutions of different composition and ionic strength. The measured values of the activity coefficient, T(Mn2+) and T(CO3 2–), have been used to estimate the stability constant for the formation of the MnCO3ion pair, K *(MnCO3 0). The value of K 0(MnCO3 0) calculated from the values of K *(MnCO3) by the Pitzer equation ( = 0.1) in this study (4.8 ± 0.1) is in reasonable agreement with literature data.  相似文献   

6.
The example of the sequence of reactions
and the steady-state approximation are used to present a demonstration of the fact that the evolution of the reaction rates under non-isothermal conditions depends on the ratio of the activation energies and on the heating rate. At the same time, it is shown that, under isothermal conditions, the ratio of the activation energies plays no role. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

7.
The thermal decomposition of zirconium oxyhydroxides prepared by the mixture of aqueous zirconium oxychloride solutions and aqueous solutions of sodium hydroxide or ammonium hydroxide under various conditions has been examined by thermogravimetry, differential thermal analysis, X-ray diffraction study and infrared spectrophotometry. As a result, it is seen that the thermal decomposition of zirconium oxyhydroxide, in which the composition is ZrO2-x(OH)2xyH2O where x2 and 1y<2, proceeds according to the following process:
This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

8.
The Pitzer model is applied to simulate various single- and multistage modifications of the industrial conversion process
by repetitive thermochemical equilibrium calculations. In this work, good agreement between simulated values and operating data was found because the Pitzer model accurately predicts the solubility of the various salts involved in different stages of the process operating from 0 to 120°C.  相似文献   

9.
The determination of the second dissociation constant of carbonic acid K 2 in 5, 15, and 25 mass% ethanol—water mixed solvents has been made using cell of the type:
at 5 to 45°C. From these data, thermodynamic quantities, dissociation enthalpy, and dissociation entropy were determined. The dependence of pK 2 on dielectric constant of the mixed solvents is discussed in term of the Beveridge model.  相似文献   

10.
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