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1.
B. Sourd P. André J. Aubreton M.-F. Elchinger 《Plasma Chemistry and Plasma Processing》2007,27(2):225-240
In this paper, the calculated values of the viscosity and thermal conductivity of nitrogen plasma are presented taking into
account five (e, N, N+, N2 and N2+) or eight (e, N(4S), N(2P), N(2D), N(R), N+, N2 and N2+) species. The calculations are based on the supposition that the temperature dependent probability of occupation of the states
is given by the Boltzmann factor. The domain for which the calculations are performed, is for p = 1 and 10 atm in the temperature range from 5,000 K to 15,000 K. Classical collision integrals are used in calculating the
transport coefficients and we have introduced new averaged collision integrals where the weight associated at each interacting
species pair is the probable collision frequency. The influence of the collision integral values and energy transfer between
two different species is studied. These results are compared which those of published theoretical studies. 相似文献
2.
N. Doca Gabriela Vlase T. Vlase G. Ilia 《Journal of Thermal Analysis and Calorimetry》2008,94(2):441-445
The thermal behavior of Cd2+ and Co2+ phenyl-vinyl-phosphonates was studied using two different experimental strategies: the coupled TG-EGA (FTIR) technique by
decomposition in nitrogen respectively air, and the kinetic analysis of TG data obtained in dynamic air atmosphere at four
heating rates. In nitrogen two decomposition steps were observed: the loss of crystallization water, respectively the decomposition
of the phenyl-vinyl radical. In air, the same dehydration was observed as the first step, but the second one is a thermooxidation
of the organic radical with formation of the pyrophosphoric anion.
The kinetic analysis of the TG non-isothermal data was performed by the isoconversional methods suggested by Friedman and
Flynn, Wall and Ozawa, as well as by the non-parametric (Sempere-Nomen) method. All processes put in evidence in TG curves
exhibit strong changes of the activation energy values with the conversion degree, which mean that these processes are complex
ones. Assuming that each of these processes consists in two steps, the application of non-parametric method leads to average
values of the activation energy close to the average values of this parameter obtained by isoconversional methods. 相似文献
3.
The structure and conformational dynamics of nonrigid cyclopropanecarbaldehyde (CPCA) molecule in the ground (Sb0) and lowest excited triplet (Tb1) and singlet (Sb1) electronic states were calculated using the MP2, DFT, CASSCF, CASPT2, and CCSD quantum chemical methods. According to ab initio calculations, in the Sb0 electronic state there are two symmetrical (cis and trans) conformers of the CPCA molecule. Excitation of the CPCA molecule to the ?1 and S1 electronic states causes significant structural changes: carbonyl CCHO fragment becomes nonplanar, cyclopropane fragment rotates around the C–C bond, thus changing the relative positions of the formyl and cyclopropane fragments. Using sections of the potential energy surfaces (PES) of the CPCA molecule in the Tb1 and Sb1 states, we calculated the torsion and inversion wave functions and vibrational transition energies. The results obtained suggest a strong coupling of the torsion and inversion motions in the Tb1 and Sb1 excited states. 相似文献
4.
T. Belgya 《Journal of Radioanalytical and Nuclear Chemistry》2008,276(3):609-614
The 14N(n,γ)15N reaction is a primary γ-ray source for high energy calibration of detectors. The relative γ-ray-intensities of 15N and the relative γ-ray detection efficiency function have been simultaneously determined up to 10 MeV from γ-peak areas
alone. Absolute γ-ray-intensities were obtained with proper renormalization to known absolute intensity. The influence of
these new intensity values are assessed for use in PGAA. Any consistently used set of calibration intensities applied in the
creation of library values and for analysis do not influence the concentrations. Contrary to this, quantities based on sums
of γ-ray cross sections may provide different answers with the new 15N intensities and they give means to validate them. 相似文献
5.
L. I. Tsikritzis 《Journal of Radioanalytical and Nuclear Chemistry》2005,264(3):651-656
Summary The distribution and origin of 40K, 226Ra, 228Ra and 137Cs has been investigated in trees, mosses and lichens in the basin of the West Macedonia Lignite Centre. In tree leaves 137Cs is negligible, while the 226Ra and 228Ra concentrations are affected by the fly ash particles. Concerning 226Ra and 228Ra values of mosses and lichens, which are systematically larger than those of unpolluted areas, the application of chemometrics proved that they originate mainly from the lignite fly ash. 相似文献
6.
V. V. Yanilkin N. V. Nastapova A. S. Stepanov A. A. Kalinin V. A. Mamedov 《Russian Chemical Bulletin》2009,58(1):89-94
The binding of cations Li+, Na+, K+, Cs+, Ag+, Zn2+, Ni2+, Co2+, NH4
+ (group I), H+, Mg2+, Al3+, Ga3+ (group II), and Ca2+, Pb2+ (group III) by 21,31-diphenyl-l 2,42-dioxo- 7,10,13-trioxa-l,4(3,1)-diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane (1), which contains two indolizine and two quinoxaline fragments and 3,6,9-trioxaundecanes spacer, and by its acyclic analog
(2) was studied using cyclic voltammetry in MeCN/0.1 M Bu4NBF4. It was concluded that the ions of group I are not bound by these compounds, the ions of group II exhibit the reversible
redox-switched binding by the carbamoyl groups of the quinoxaline fragments, whereas the ions of group III are bound not only
by the initial compounds and radical cations 1 and 2, but also by dication 1. This binding of the Ca2+ and Pb2+ ions stabilizes dication 1. 相似文献
7.
A. Gopalakrishna G. N. Kim H. Naik K. Kim B. K. Nayak Muhammad Zaman 《Journal of Radioanalytical and Nuclear Chemistry》2018,316(2):561-569
The production cross-section of the medical isotope, 99Mo from the enriched 100Mo(n,2n) reaction with the average neutron energies of 21.9 and 26.5 MeV has been determined for the first time by using an off-line γ-ray spectrometric technique. The average neutron energies were generated by using the 9Be(p,n) reaction with the proton energies of 35 and 45 MeV from the MC50 cyclotron of the Korea Institute of Radiological and Medical Sciences (KIRAMS) at Seoul, South Korea. The 100Mo(n,2n) reaction cross-section as a function of neutron energy was also calculated theoretically by using the computer code TALYS-1.8 and EMPIRE-3.2 Malta. The experimental results are in close agreement with the theoretical values from TALYS-1.8. However, the present data at the neutron energy of 21.9 MeV is slightly lower and at 26.5 MeV is higher than the values from EMPIRE-3.2 Malta. 相似文献
8.
Hui Zhang Xianjin Yu Lei Chen Jiaqiang Geng 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(1):249-258
The sorption of 63Ni(II) from aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. ZSM-5 zeolite
was characterized by point of zero net proton charge (PZNPC) titration. The sorption was investigated as a function of shaking
time, pH, ionic strength, foreign ions, humic acid (HA), fulvic acid (FA) and temperature. The results indicate that the sorption
of 63Ni(II) on ZSM-5 zeolite is strongly dependent on pH. The sorption is dependent on ionic strength at low pH, but independent
of ionic strength at high pH values. The presence of HA/FA enhances 63Ni(II) sorption at low pH values, whereas reduces 63Ni(II) sorption at high pH values. The sorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters
(i.e., ∆H
0, ∆S
0 and ∆G
0) for the sorption of 63Ni(II) are determined from the temperature dependent sorption isotherms at 293.15, 313.15 and 333.15 K, respectively, and
the results indicate that the sorption process of 63Ni(II) on ZSM-5 zeolite is spontaneous and endothermic. 相似文献
9.
The hydrolytic species of lanthanide ions, La3+ and Sm3+, in water at I = 0.1 mol·dm?3 KCl ionic strength and temperatures of 298.15, 310.15 and 318.15 K were investigated by potentiometry. The hydrolytic species were modeled by the HySS simulation program. From the results, the hydrolytic species of each metal ion at different temperatures were calculated using the program HYPERQUAD2013. The hydrolysis constants (log10 β) of [La(OH)]2+ and La(OH)3 were calculated as ?8.52 ± 0.46, ?26.84 ± 0.48, and log10 β values of [Sm(OH)]2+, [Sm(OH)2]+, Sm(OH)3 were calculated as ?7.11 ± 0.21, ?15.84 ± 0.25 and ?23.44 ± 0.52 in aqueous media at 298.15 K, respectively. The dependence of the hydrolysis constants on the temperature allowed us to calculate the enthalpy, entropy, and Gibbs energy of hydrolysis values of each species. 相似文献
10.
E. S. Zakaria 《Journal of Radioanalytical and Nuclear Chemistry》2005,264(3):629-635
Summary This paper reports the radiochemical study of the ion-exchange of Cs+, Na+, Sr2+ and Eu3+ ions with H+ by chromium hexacyanoferrate(II) which was prepared in a granular form using a gel method. The slow steps which determine the rate of exchange of these ions are directly proportional to the particle diameter and this is confirmed from the linearity test of Bt vs. t plots at different particle diameters. Boyed’s equation and Reichenberg’s tables were used for evaluating all the kinetic parameters. The results reveal that the effective particle radii are unchanged for both chromium hexacyanoferrate(II) dried at 60 and 120 °C. The obtained data were analyzed using McKay plots and Arrhenius equation and the kinetic and thermodynamic parameters, e.g., effective diffusion coefficient, activation energies and entropies of activation have been evaluated. The mobility of these ions inside the particles of chromium hexacyanoferrate(II) decrease in the order of Eu3+>Sr2+>Na+⊃Cs+. 相似文献
11.
IR-spectra of stable and metastable isomers of ruthenium nitrosocomplexes, [Ru(NO)Cl5]2? and [Ru(NO)(CN)5]2?, have been calculated within the frames of density functional theory. Frequency assignment was refined on the base of analysis of normal vibration in internal vibrational coordinates. Calculation results confirm that spectrally observed metastable states are bond isomers with ν1-ON and ν2-NO coordination. 相似文献
12.
Karin Popa Alexandru Cecal Doina Humelnicu Ioan Caraus Camelia L. Draghici 《Central European Journal of Chemistry》2004,2(3):434-445
This study concerns the removal of the 137Cs+ and 60Co2+ β+γ-radioactive ions in Azolla caroliniana Willd. water fern. The living fern and two different types of biosorbent prepared from Azolla caroliniana were tested to remove the above-mentioned radioactive ions from dilute solutions, in the absence and in the presence of the
ionic competition. Effective 137Cs+ and 60Co2+ ions removal from low radioactive wastewaters was demonstrated. The time dependent K
d
(t) values were calculated from the absorption data. These results indicate that removal process achieved equilibrium in about
120 min and that it involves two steps: rapid and slow absorption; the active process (metabolic bioaccumulation on the living
fern) was responsible for above one half of the total removal process. A thin layer radiochromatography study leads to the
conclusion that the biochemical components in which 137Cs+ and 60Co2+ place themselves are of a polysaccharide and lipoid fractions. 相似文献
13.
D. G. Kellerman S. P. Gabuda N. A. Zhuravlev A. S. Semenova T. A. Denisova R. N. Pletnev 《Journal of Structural Chemistry》2007,48(3):462-466
Within a temperature range of 120–330 K, 7Li NMR spectra in Li0.6CoO2 are obtained. It is shown that as the temperature increases, both smooth and stepwise variation of 7Li NMR contact shifts occurs. The observed effects are explained by the occupation of the excited levels of cobalt ions. The stepwise change of the resonance line width depending on the temperature is revealed. It is driven by the features of the diffusive motion of lithium ions. The calculation of the 1H NMR line shape provides the determination of the ratio of one-, two-, and three-spin proton clusters in Li0.6CoO2·xH2O. 相似文献
14.
Saeedeh Hashemian 《Russian Journal of Inorganic Chemistry》2011,56(3):397-401
The imidazol side group of histidine has two nitrogen atoms capable of being protonated or participating in metal binding.
Hence, histidine can take on various metal-bound and protonated forms in proteins. Because of its variable structural state,
histidine often functions as a key amino acid residue in enzymatic reactions. Ab initio (HF and MP2) calculations were done
in modeling the cation (H+, Li+, Na+, K+, Mg2+, Ca2+) interaction with side chain of histidine. The region selectivity of metal ion complexation is controlled by the affinity
of the side of attack. In the imidazol unite of histidine the ring nitrogen has much higher metal ion (as well as proton)
affinity. The complexation energies with the model systems decrease in the following order: Mg2+ > Ca2+ > Li+ > Na+ > K+. The variation of the bond lengths and the extent of charge transfer upon complexation correlate well with the computed interaction
energies. 相似文献
15.
2-Keto-D-gluconate (kG) is naturally produced in soils, sediments and rock faces through the microbial oxidation of glucose. Studies have qualitatively shown kG to enhance the dissolution of soil minerals. However, quantitative information, such as the log K values for the formation of metal–kG complexes, are not available. This paper presents the results of potentiometric titration studies that employ H+ and Ca2+ ion selective electrodes (ISEs) to determine the conditional ion association constants (log Q values) for the protonation and deprotonation of kG and the formation of Ca–kG complexes. The experimentally-determined log Q values were then converted to the corresponding ion association constants (the zero ionic strength condition; log K values) by employing a modified Davies equation for charged species and the Setchenów equation for neutral species. The log K values were determined by potentiometric titrations at constant kG concentration, varied ionic strengths, 25 or 22 ∘C, and in the absence of CO2. The computer model GEOCHEM-PC was used to determine the aqueous speciation of ions other than kG and the computer model FITEQL was used to estimate conditional log Q values for reactions in the various chemical models. Based on our evaluations, equilibrium constants for the following reactions were determined: H++ kG– ⇌ HkG0, log Ka1 = (3.00 ± 0.06), kG–⇌ H–1kG2–+ H+, log Ka–1 = –(11.97 ± 0.41), and Ca2++ kG–⇌ CakG+, log K101 = (1.74 ± 0.04). 相似文献
16.
Zhengjie Liu Jianwei Yang Zengchao Zhang Lei Chen Yunhui Dong 《Journal of Radioanalytical and Nuclear Chemistry》2012,291(3):801-809
Bentonite was investigated to remove Ni(II) from aqueous solutions because of its strong sorption ability. Herein, bentonite
was modified with sodium carboxymethylcellulose (CMC) and used as an adsorbent to remove Ni(II) from aqueous solutions. The
results indicated that CMC-bentonite had higher sorption capacity than bare bentonite in the sorption of Ni(II) from aqueous
solutions. Sorption of Ni(II) on CMC-bentonite was mainly dominated by ion exchange or outer-sphere surface complexation at
low pH values, but by inner-sphere surface complexation or surface precipitation at high pH values. The thermodynamic data
calculated from temperature dependent sorption isotherms indicated that the sorption of Ni(II) to CMC-bentonite hybrids was
an spontaneous process and enhanced with increasing temperature. 相似文献
17.
Robert Kandlbinder Robert Schupfner Otto S. Wolfbeis 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(1):69-73
The determination of 228Ra by means of γ-spectrometry, in material containing significant quantities of 40K and Ca2+ such as bone ash results in increased values of counting uncertainty and lower limit of detection (LLD) because of a significant
contribution from the Compton continuum of 40K. However, 40K is widely removed from bone ash if 228Ra is coprecipitated with barium sulfate. As a result, the counting uncertainty and LLD are significantly reduced. A method
is presented for determination of very low activity concentrations of 228Ra. Impurities introduced by precipitation are negligible when applying high resolution γ-spectrometry. 相似文献
18.
Together with recent improved potential-energy surface calculations for the ground (X) and first excited (Ã) electronic states of HeH2
+, the electric dipole moment surfaces for each state and the transition dipole moments connecting the two states were evaluated for the entire range of the energy calculations. Using these functions the linestrengths of all dipole-allowed transitions between the bound vibrational levels within each of the two states (XX) and (ÃÃ) as well as between them (ÃX) are evaluated here. These data are believed to be useful both in the experimental search for the yet unobserved molecular spectra of HeH2
+ and in evaluating theoretical rates for the radiative association or photodissociation processes involving the two lowest electronic states of the ion.Contribution to the Björn Roos Honorary Issue 相似文献
19.
J. J. LaBrecque P. R. Cordoves M. A. Cordoves K. Perez D. Palacios J. A. Alfonso 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(3):669-674
This work presents the results of 137Cs, 40K, 232Th and 238U concentration (Bq kg−1) values in coastal marine sediments collected from 38 sites along the coastline of the island of Margarita, Venezuela. The
purpose was to determine baseline values for these radionuclides in surface marine sediments and to detect if there were any
anomalously high concentration values. Only three of the 38 sediments analyzed had measurable values above the detection limit
of 0.9 Bq kg−1 for 137Cs and the highest only being 1.4 Bq kg−1. While, the concentration (Bq kg−1) ranges for the primordial radionuclides, 40K, 232Th and 238U were as follows: 12.2–211.7, <1.5–9.8 and <4.4–20.7, respectively. These concentration ranges for the primordial radionuclides
can be considered as baseline values for surface marine sediments for areas that are considered not polluted by man or contaminated
by nature. Finally, the concentration range of 137Cs can also be employed as baseline values, which only seem to have been the result of the atmospheric testing of nuclear
weapons in the past. 相似文献
20.
The present paper contains inspection of the improved corresponding states principle for transport properties of hydrogen and the binary mixtures of hydrogen with Ne, Ar, Kr and Xe. The set of corresponding states parameters has been defined by a complex numerical analysis of a carefully selected body of experimental data. The obtained correlations for the reduced orientation-averaged diffusion and viscosity collision integrals are restricted to low densities in a temperature range from T = ?/k to the onset of ionization. These equations have been inverted directly to give the isotropic and effective intermolecular potential energy curve for binary mixtures of H2 with Ne, Ar, Kr and Xe corresponding to the viscosity collision integrals. The results are then used to obtain the best Morse-Spline-Van der Waals (MSV) potential parameters. Our inverted potential energies have been compared with experimental intermolecular potentials that were obtained by molecular beam scattering and infrared spectroscopic measurements. In this research, the Chapman–Enskog and Wang Chang-Uhlenbeck-de Boer (WCUB) version of kinetic theory have been used in conjunction with our inverted potential energies to reproduce viscosity, diffusion, thermal conductivity and thermal diffusion factor of binary mixtures of H2 with Ne, Ar, Kr and Xe in a wide temperature range for equimolar composition. As the deviation plots illustrate, our obtained intermolecular potential energies (on the basis of the algorithm presented in the inversion process) represent the low-density transport properties of binary mixtures of H2 with Ne, Ar, Kr and Xe within their expected experimental uncertainties. Close agreement between the predicted values and the literature results of transport properties demonstrates the predictive power of the inversion scheme. 相似文献