Investigation of the solid samples evaporation from the auxiliary DC arc discharge in the atomic emission spectroscopy

Efficiency of the suggested tandem technique of Marinkovi? burner was studied in terms of the influence of the PC-controlled DC arc of the different intensities (10 A, 15 A, 20 A, 25 A) on the evaporation process. Higher intensities than 25 A did not allow to use the given experimental equipment since they cause plasma instability and periodic plasma quenching. The suggested method was evaluated by the determination of the half (t _50%) and total (t _100%) evaporation time and by determination of the signal/background ratio for the chosen elements (Al, Ca, Cr, Fe, Mg, Ni, Si, and V) in the model graphite matrix.     

Transport of uranium free particles in a d.c. arc plasma burning in air at atmospheric pressure

The transport parameter ψ was calculated for the free particles of uranium in a d.c. arc plasma burning in air. Using the “wire method” the volatilization rate (Q_w), the total concentration of free particles (_nt), the axial velocity (_vj) of uranium particles and the plasma cross section (S) were measured. The transport parameter was calculated for cylindrical symmetry of the arc. The total particle concentration calculated by the wire method was compared to values obtained by absolute intensity measurements of ion and atom spectral lines of uranium. This led to an estimate of the molecular concentration of uranium in the d.c. arc plasma.     

True detection limit of rare earth elements in atomic emission analysis with an arc two-jet plasmatron

The “true detection limit” C_L,true was measured by a method proposed by Boumans et al. for 10 prominent lines of La, Ce, Pr, Nd and Sm, the most abundant rare earth elements (REEs) in geological samples. It is demonstrated how spectral interferences can increase of C_L,true. The spectra were excited in an argon arc plasma jet with evaporation powders of five complex natural samples. The data show that there is a significant increase of C_L,true in real samples containing large concentrations of such elements as Ti, Zr, Cr, Nb, Ta and REEs emitting complex spectra. Received: 17 June 1997 / Revised: 20 October 1997 / Accepted: 26 October 1997     

Dyeless optical detection of ammonia in the gaseous phase using a pH-responsive polymer – characterization of the sorption process

pH-responsive polymers enable the dyeless optical detection of acidic or basic pollutants in air. The characterization of the sorption process and the optimization of the response time of the sensitive layers were highlighted. The swelling of a pH-responsive polysiloxane induced by sorption of gaseous ammonia was investigated by measurement techniques such as spectroscopic ellipsometry (SE) and infrared spectroscopy (IR). Furthermore, the pH-responsive polymer was applied for the detection of gaseous ammonia using the LED-based reflectometric interference spectroscopy set-up (RIfS_4λ). A limit of detection of 0.30 mg/m³ ammonia and a response time (t_90%) of 35 s could be verified. The application of pH-responsive polymers can be a powerful alternative to dye-based optical sensing, since photobleaching or leaching of the sensitive functional unit cannot occur applying this approach, and since the properties of the sensitive layer proved to be very promising.     

Electrochemical impedance spectroscopy analysis for oxygen reduction reaction in 3.5% NaCl solution

The electrochemical impedance spectroscopy (EIS) at different potentials has been used to study the oxygen reduction reaction (ORR) in 3.5% NaCl solution on glassy carbon (GC) electrode in this work. Results show that ORR consists of three two-electron reaction steps and both superoxide ion (O₂ ^–) and hydrogen peroxide (H₂O₂), which are produced by ORR, obstruct the diffusion of oxygen to the surface of the electrode and make the EIS results change into a transmissive finite diffusion process with the real part contraction and a reflective finite diffusion process from a semi-infinite diffusion process. The values of electron transfer resistance (R _t) and diffusion resistance (R _d) were calculated from EIS. O₂ ^– influenced strongly on the R _t values and induced a maximum at −0.45 V.     

Kieselgelstandards für die Bestimmung von Spurenelementen in pulverförmigen Proben mit leichter Matrix durch Röntgenfluorescenzanalyse

The paper deals with homogeneous magnetic fields and added chemical substances both affecting the spectrochemical results obtained in arc excitation studies. The influence of a homogeneous magnetic field on the total intensity of lines of various analysis elements (Hg, Zn, Ga, Tl) in graphite has been examined. Furthermore, the axial and radial distributions of line intensities in arc plasma were determined. Parameters used were the magnetic field strength (0, 0.01, 0.02, 0.04 T) and the physical data of the analysis elements. It was found that the effect of the magnetic field varies with the ionization potential of the elements involved, their atomic mass and the strength of the magnetic field applied. A non-destructive method of measuring was introduced for studying the effects of a homogeneous magnetic field on the rates of evaporation. The results showed increased evaporation rates in presence of magnetic fields as a function of the evaporation heat of the elements involved. Effects of Ga₂O₃ additive on the line intensities of impurity elements are governed by the Ga₂O₃ concentration and the ionization potential of the elements examined.     

Bioluminescent Analysis. The Action of Toxicants: Physical-Chemical Regularities of the Toxicants Effects

Abstract

The physical-chemical regularities of aromatic compounds' effects in luciferase toxicity biotesting have been studied. The structures and physical-chemical characteristics of the toxicants and of the bioluminescent emitter were taken into account. The inhibition constants of bioluminescence intensiy (I) were calculated and interpreted from the viewpoint of the energy (electron) transfer processes. The induction period (P) and the increase of the time of the maximum light intensity (t_M) which take place in the quinones' presence, have been shown to deal with hydrogen transfer processes. The values of I, P and t_M have been shown to be connected with a size of the quinones' aromatic and aliphatic parts. P- and t_M-dependencies on quinone's redox potential have been demonstrated.     

Multielement trace determination in SiC powders: assessment of interlaboratory comparisons aimed at the validation and standardization of analytical procedures with direct solid sampling based on ETV ICP OES and DC arc OES

The members of the committee NMP 264 “Chemical analysis of non-oxidic raw and basic materials” of the German Standards Institute (DIN) have organized two interlaboratory comparisons for multielement determination of trace elements in silicon carbide (SiC) powders via direct solid sampling methods. One of the interlaboratory comparisons was based on the application of inductively coupled plasma optical emission spectrometry with electrothermal vaporization (ETV ICP OES), and the other on the application of optical emission spectrometry with direct current arc (DC arc OES). The interlaboratory comparisons were organized and performed in the framework of the development of two standards related to “the determination of mass fractions of metallic impurities in powders and grain sizes of ceramic raw and basic materials” by both methods. SiC powders were used as typical examples of this category of material. The aim of the interlaboratory comparisons was to determine the repeatability and reproducibility of both analytical methods to be standardized. This was an important contribution to the practical applicability of both draft standards. Eight laboratories participated in the interlaboratory comparison with ETV ICP OES and nine in the interlaboratory comparison with DC arc OES. Ten analytes were investigated by ETV ICP OES and eleven by DC arc OES. Six different SiC powders were used for the calibration. The mass fractions of their relevant trace elements were determined after wet chemical digestion. All participants followed the analytical requirements described in the draft standards. In the calculation process, three of the calibration materials were used successively as analytical samples. This was managed in the following manner: the material that had just been used as the analytical sample was excluded from the calibration, so the five other materials were used to establish the calibration plot. The results from the interlaboratory comparisons were summarized and used to determine the repeatability and the reproducibility (expressed as standard deviations) of both methods. The calculation was carried out according to the related standard. The results are specified and discussed in this paper, as are the optimized analytical conditions determined and used by the authors of this paper. For both methods, the repeatability relative standard deviations were <25%, usually ~10%, and the reproducibility relative standard deviations were <35%, usually ~15%. These results were regarded as satifactory for both methods intended for rapid analysis of materials for which decomposition is difficult and time-consuming. Also described are some results from an interlaboratory comparison used to certify one of the materials that had been previously used for validation in both interlaboratory comparisons. Thirty laboratories (from eight countries) participated in this interlaboratory comparison for certification. As examples, accepted results are shown from laboratories that used ETV ICP OES or DC arc OES and had performed calibrations by using solutions or oxides, respectively. The certified mass fractions of the certified reference materials were also compared with the mass fractions determined in the interlaboratory comparisons performed within the framework of method standardization. Good agreement was found for most of the analytes.     

A study on the evaporation of cadmium for the recovery of actinides from a liquid cathode

The distillation behaviour of cadmium at a reduced pressure was investigated to develop an actinide recovery process from a liquid cadmium cathode in a laboratory scale cadmium distiller. The apparent evaporation rate of cadmium increased with an increasing temperature whereas the rate decreased with an increasing vacuum pressure. The evaporation rate of cadmium varied within 9.7–40 g/cm²/h in the temperature range of 500–650 °C and pressure range of 0.5–10 Torr (0.0667–1.33 kPa). The theoretical values calculated by the Hertz–Langmuir relation were much higher than experimentally measured values. The deviation was compensated by an evaporation coefficient (α) obtained empirically. About 0.02–0.20 wt% of residue was left in the crucible after distillation and found to be CdO. It could be concluded that the temperature range of 500–650 °C is favourable for the cadmium distillation process if residual eutectic salt does not exist in the cadmium alloy surface.     

全谱直流电弧发射光谱法同时测定钼样品中17种杂质元素

为了解决现有测定方法中样品前处理复杂、测定过程繁琐的问题,研究了直流电弧发射光谱法测定钼样品中Al、Bi、Ca、Cd、Co、Cr、Cu、Fe、Mg、Mn、Ni、Pb、Sb、Si、Sn、Ti、V等17种元素的方法。用石墨粉(98%)、碳酸钠(1%)和氟化钠(1%)作为光谱缓冲剂抑制基体元素蒸发、稳定弧焰、促进杂质元素的蒸发;采用样品装满电极后下压2 mm和滴加蔗糖乙醇水溶液(2%)的方式,防止喷溅的发生,稳定激发过程,减小基体干扰;对挥发难易程度不同的元素采用信号分段采集的方式,提高各元素信噪比。方法灵敏度高、分析速度快、操作简便,加标回收率为85%~120%,各元素分析精密度均小于15%。     

Stress-optical behavior of poly(cis/trans-1, 4-cyclohexane dimethanol-alt-formaldehyde) (PCDO) networks

Two samples of poly(cis/trans-1,4-cyclohexane dimethanol-alt-formaldehyde), having fractions of trans configuration of cyclohexylene rings F_t = 0.1 and 0.7, were synthesized by polycondensation of the appropriate mixtures of glycols with paraformaldehyde. These two samples were crosslinked by a chemical reaction using 2,4-bis(p-isocyanatebenzyl) phenylisocyanate as the crosslinking agent. The stress-optical behavior of the resulting networks was studied at several temperatures in the range 10–80°C. The values of the optical configuration parameter Δα were 9.9 and 7.2 in units of 10^?24 cm³ for F_t = 0.7 and 0.1, respectively. The temperature coefficient of this quantity was roughly zero. Theoretical analysis, performed using the rotational isomeric state model, proved that the only parameters that have an appreciable effect on the calculated values of Δα are those concerning the cyclohexane ring (i.e., F_t and the optical parameter Γ_CC = Δα_CC ? 2Δα_CH). Conformational energies, geometrical parameters, and contributions to the optical anisotropies from the oxymethylene oxide have no noticeable effect on the value of Δα calculated for the polymer. In fact, values of Δα calculated for the polymer at F_t = 0 and 1 are very close to those obtained, respectively, for cis and trans cyclohexane dimethylene. The theoretical values of Δα are roughly one order of magnitude lower than the experimental results; however, the theory reproduces satisfactorily both the variation of Δα with F_t and its temperature coefficient.     

Photophysical properties of the extract of endometallofullerenes La@C2n inortho-dichlorobenzene. Picosecond laser photolysis

The kinetics of relaxation of optical anisotropy induced by polarized light in endometallofullerenes La@C_2n inortho-dichlorobenzene was studied by picosecond laser photolysis. Decay of the optical absorption signal due to the excited states of La@C_2n follows the biexponential law with two values of relaxation time:t ₁=35±3 ps andt ₂=1100±200 ps. The lifetimet or decay of the optical anisotropy is 19±5 ps and determined by the orientational diffusion of La@C_2n . The experimentally determined lifetime of optical anisotropy agrees satisfactorily with the value yielded by the theoretical model of orientational diffusion under slip boundary conditions at the interface of the La@C_2n molecule with the solvent. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 10, pp. 1921–1923, October, 1999.     

Thermodynamic equilibrium study of mineral elements evaporation in O2/CO2 recycle combustion

The facility for the analysis of chemical thermodynamics method (F*A*C*T) based on the Gibbs energy minimization principle, was used to characterize the evaporation of mineral elements of coal in O₂/CO₂ recycle combustion. The effects of atmosphere and temperature on the speciation of mineral species were discussed. The results show that Na(K)Cl(g), FeO(g), and SiO(g) are the dominant gaseous species of the mineral elements. The dominant species of mineral elements in flue gases depend on both the combustion conditions (reducing or oxidizing) and the atmosphere. In O₂/CO₂ mixture combustion, the evaporation rate of mineral elements is much lower than that in air combustion, especially under reducing atmosphere. The total evaporation of mineral elements in O₂/CO₂ atmosphere and air combustion under reducing conditions is 4.46% and 9.65% respectively, up to the temperature of 2400 K. The calculation values are consistent with the experiment values. The decrease in the mineral element evaporation is helpful to suppress the tendency to form fine particle matter and the tendency of initial ash deposition.     

Time-resolved spectral investigations of laser light induced microplasma

The dynamical and spectral properties of an optical breakdown microplasma created by pulses of different lasers on surfaces of insulators (KCI), metals (Cu) and semiconductors (V₂O₅), have been investigated. Experiments were carried out in air and vacuum using different wavelengths (λ = 0.694μm, type OGM-20,λ = 1.06μm with a home-made laser based on neodymium glass crystal, and λ = 10.6μm, similarly home-made) and pulse durations (Q-switched and free-running regimes). To follow the integral, dynamical and spectral characteristics of the luminous spot of microplasma we have used fast cameras (SFR-2M, IMACON-HADLAND), a high speed spectral camera (AGAT-2) and a spectrograph (STE-1). It has been shown that the microplasma consists of two parts: fast front (peak) with τ≈100 ns and slow front (tail) with τ≈1μs durations. The detonation front speed is of the order of ≈10⁵ cm s⁻¹ and follows the temporal dependence of to t^0.4. It depends on the composition of the surrounding gas and its pressure and could be connected with quick evaporation of the material investigated (peak) and optical breakdown of the ambient gaseous atmosphere (tail). From the delay in appearance of different characteristic spectral lines of the target material and its gaseous surrounding we have shown that the evolution of the microplasma involves evaporation and ionization of the atoms of the parent material followed by optical breakdown due to the incident and absorbed laser light, together with microplasma expansion.     

Kinetic analysis of experimental intensity curves obtained during zeolite a synthesis using <Emphasis Type="Italic">in situ</Emphasis><Superscript>27</Superscript>Al NMR spectroscopy

Intensity curves obtained by in situ ²⁷Al NMR spectroscopy during zeolite A synthesis have been used as a method for comparative kinetic investigation of zeolite crystallization. Based on inflection point analysis of intensity curves, the times of t _sed for process of sedimentation, t _start for initiation, and t _finish for completion of process in liquid phase connected to crystallization were evaluated. Obtained values for t _start and t _finish indicated that the rate of processes in liquid phase, connected with gel dissolution and growth of zeolite crystal, decreases with the increase of SiO₂/Al₂O₃ molar ratio for the same Na₂O concentration. On the other hand, increase of Na₂O concentration for any of specified SiO₂/Al₂O₃ molar ratio increases the rate of the same processes. The article is published in the original.     

Solution thermolysed tungsten oxide-based electrochromic devices: thickness-dependent step potential analysis

The characterisation of electrochemical behaviour of electrochromic (EC) devices based on solution thermolysed (ST) tungsten oxide (WO₃) thin films was carried out using the step potential excitation method. The method, based on generating plots of current density (J) as a function of passed charge (ΔQ), has been applied for the characterisation of EC-WO₃ thin films in proton-containing aqueous electrolyte. EC devices have been fabricated by employing WO₃ thin films with variable thickness (T) ranging from 0.04 to 0.52 μm. The J vs time (t) responses (chronoamperometry) of these devices were recorded at a fixed applied potential (±0.7 V vs S.C.E.) and values of total passed H⁺ charges (ΔQ) into the WO₃ host lattice during the coloration process are calculated. The J-ΔQ curves corresponding to films of different thickness were plotted as a function of the passed charge volume density, ΔQ /T, and an intercalatable film thickness is calculated to be 0.13 μm. The modulation in optical transmittance after coloration and bleaching was studied in the wavelength range between 350 and 850 nm and an optical efficiency (ξ_λ) is calculated at λ=700 nm. It is found that the ξ_λ wanes with increasing intercalation. Electronic Publication     

Investigation of correlation between impact sensitivities and bond dissociation energies in some triazole energetic compounds

In this article, density functional theory has been utilized to study on the correlation between impact sensitivities h _50% and the bond dissociation energies (BDEs) of nine triazole energetic explosives. By employing B3LYP and B3P86 method with the 6-311G** basis set, all the molecules have been fully optimized. The BDEs for removal of the NO₂ group in these compounds have also been calculated at the same level. Computed results show that BDEs calculated by B3LYP method are all less than those by B3P86 method. The relationship between the impact sensitivities and the weakest C–NO₂ bond dissociation energy (BDE) values have been investigated. The results indicate a good linear correlation between the impact sensitivity h _50% and the ratio (BDE/E) of the weakest BDE to the total energy E.     

Synthesis and identification of endohedral metallofullerenes La@C82

The effect of the procedure of preparation of lanthanum-graphite electrodes and the regime of their evaporation in the electric arc on the yield of endometallofullerene La@C₈₂ has been studied. La@C₈₂ was identified by ESR spectroscopy, optical spectroscopy, and mass spectrometry. The fractional extraction of the fullerene-containing soot witho-xylene makes it possible to separate La@C₈₂ from higher fullerenes containing no metal atorns and to obtain fullerene extracts enriched in La@C₈₂. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 254–258, February, 1997.     

A Mathematical Model of the Carbon Arc Reactor for Fullerene Synthesis

A mathematical model of the carbon arc process for the synthesis of fullerenes (C ₆₀ , C ₇₀ ) is developed. The two-dimensional model solves for the velocities, temperature, and total concentration of carbon species. The net emission coefficient method is used for the radiation term. The carbon species conservation equations consider the evaporation of carbon from the anode, cathode surface deposition, and carbon condensation. The thermodynamic and transport properties are calculated as a function of temperature and carbon mass fraction, using the method of Chapman–Enskog. Erosion rates used by the model are determined experimentally. Calculated fields of the velocities, temperatures, carbon mass fraction and current intensity are presented. Comparison is made of the behavior of the arc at 1 and 4 mm interelectrode gaps, and between operation in argon and in helium. The results of simulations provide a justification for the higher yields observed in helium compared to the argon case.     

Study of kinetics and thermodynamics of the dehydration reaction of AlPO<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

The kinetics and thermodynamics of the thermal dehydration of aluminum phosphate monohydrate, AlPO₄ · H₂O were studied using thermogravimetry (TG-DTG-DTA) at four heating rates in dry air atmosphere. The activation energies of the dehydration step of AlPO₄ · H₂O were calculated through the methods of Friedman (FR) and Flynn–Wall–Ozawa (FWO) and the possible conversion function has been estimated through the Achar and Li–Tang equations. The independent activation energies on extent of conversions and the better kinetic model of the dehydration reaction for AlPO₄ · H₂O indicate single kinetic mechanism and the F _2.05 model as a simple n-order reaction of “chemical process or mechanism no-invoking equation”, respectively. The positive values of ΔH^# and ΔG^# for the dehydration reaction show that it is endothermic and non-spontaneous process and it is connected with the introduction of heat. The kinetic and thermodynamic functions calculated for the dehydration reaction by different techniques and methods were found to be consistent.