Measured Stark widths and shifts of the neutral argon spectral lines in 4s–4p and 4s–4p′ transitions

We investigate the Stark widths (W) and the shift (d), of the seven neutral argon (Ar I) spectral lines from the 4s–4p and 4s–4p′ transitions. The line shapes are measured in a linear, low-pressure, optically thin pulsed arc discharge at about 16 000 K electron temperature (T) and about 7.0 × 10²² m^− 3 electron density (N). The new data separates the electron width (W_e) and ion width W_i from the total Stark width (W_t), as well the separation of electron total Stark shift (d_t) on electron (d_e) and ion (d_i) parts. There are no theoretical predictions for these lines. Comparison to theoretical predictions for other lines within the same multiplets finds that the experimental data exhibits stronger influence by the ion contribution to the measured Ar I line shape. We have also deduced the ion broadening parameters which describe the influence of the ion static (A) and the ion–dynamical (D and E) effect on the width and the shift of the line shape.Applying the line deconvolution procedure, the basic plasma parameters i.e. electron temperature (T) and electron density (N) are recovered. The plasma parameters (T and N) are measured using independent diagnostics techniques as well. Good agreement is found among two sets of the N and T plasma parameters obtained from deconvolution procedure and independent diagnostics techniques.     

Application of laser-induced plasma spectroscopy to the measurement of Stark broadening parameters

In this work, we have studied the main conditions that a laser-induced plasma must fulfill in order to be considered as adequate for the measurement of Stark broadening parameters. We investigated the effect of the temporal window, the self-absorption, the crater size, and the effect of the spatial inhomogeneity on the emission profiles coming from a laser-induced plasma. Starting from the spatially resolved values of the plasma parameters, obtained by emission spectroscopy, the error in the determination of the Stark electron width due to the spatial inhomogeneity has been estimated and, for the present experimental conditions, was found to be lower than 7%. As a test of the method, the Stark electron broadening constant of Fe I 381.58 nm has been measured using the Fe I 538.34 nm emission line as the reference to determine the electron density. The plasma was produced under a controlled atmosphere of argon at atmospheric pressure, on an iron–nickel alloy sample. The emission was collected by a system with high spectral resolution, for different temporal windows after the laser pulse. For time delays between 2.75 and 21 μs, the electron density showed an evolution in the range 2.0–0.13 × 10¹⁷ cm^− 3, while the temperature varied from 11 100 to 7100 K. The representation of the Stark electron width of Fe I 381.58 nm, measured for each temporal window, versus the Stark electron width of the reference line showed a linear behavior with a high correlation coefficient. From the slope of this linear fit and the Stark electron broadening constant of the reference line, the Stark width of Fe I 381.58 nm was obtained to be 1.10 ± 0.07 × 10^− 2 nm for an electron density of 10¹⁷ cm^− 3.     

Application of a laser produced plasma: Experimental Stark widths of single ionized lead lines

The optical emission spectroscopy from laser produced plasma generated by a 10,640 Å radiation, with an irradiance of 1.4 × 10¹⁰ W cm^− 2 on several lead targets, in vacuum and in an atmosphere of argon, was recorded and analyzed between 1900 and 7000 Å. The Local Thermodynamic Equilibrium conditions and plasma homogeneity have been checked. Stark widths for 31 lines of Pb II have been measured. These lines measured in this work correspond to the transitions 7s → 6p, n(n = 8, 9, 10)s → 7p, n(n = 7, 8)p → 7s, n(n = 7, 8)p → 6p², n(n = 7, 8)d → 7p, n(n = 5, 6)f → 6d, n(n = 5, 6)f → 6p². The population level distribution and the corresponding temperatures were obtained using Boltzmann plots. The plasma electron densities were determined using well-known Stark broadening parameters of spectral lines. Special attention was dedicated to the possible self-absorption of the different transitions. Temporal evolution of the plasma parameters was studied between 0.1 and 9 μs. Stark broadening parameters of the spectral lines were measured at 2.5 μs where the electron temperature was close to 11,300 K and the electron density to 0.8 × 10¹⁶ cm^− 3. The experimental results obtained have been compared with the experimental and theoretical values given by other authors. A systematic trend of this parameter versus temperature of 4244.9 Å Pb II line has been presented.     

Measurements of Stark widths and shifts of Ne I lines using degenerate four-wave mixing and Thomson scattering methods

We report on measurements of Stark widths and shifts of four prominent Ne I lines of the 3s,3s′-3p transition arrays. The measurements were performed in an atmospheric-pressure arc discharge operated in argon–neon gas mixture.Sub-Doppler degenerate four-wave mixing technique was used to measure the line profiles, while Thomson scattering yielded the plasma parameters: electron density, n_e = (0.53–1.33) × 10²³ m^− 3, and electron temperature, T_e = 10,200–20,900 K. The measured profiles are symmetric within the uncertainty limits. The experimental Stark widths and shifts are compared with results of other experiments and theoretical calculations.     

Stark broadening of Mg I and Mg II spectral lines and Debye shielding effect in laser induced plasma

We report Stark broadening parameters for three Mg I lines and one Mg II line in the electron number density range (0.67–1.09) · 10¹⁷ cm^− 3 and electron temperature interval (6200–6500) K. The electron density is determined from the half width of hydrogen impurity line, the H_α, while the electron temperature is measured from relative intensities of Mg I or Al II lines using Boltzmann plot technique. The plasma source was induced by Nd:YAG laser radiation at 1.06 μm having pulse width 15 ns and pulse energy 50 mJ. Laser induced plasma is generated in front of a solid state surface. High speed photography is used to determine time of plasma decay with good homogeneity and then applied line self-absorption test and Abel inversion procedure. The details of data acquisition and data processing are described and illustrated with typical examples. The experimental results are compared with two sets of semiclassical calculations and the results of this comparison for Mg I lines are not unambiguous while for Mg II 448.1 nm line, the results of Dimitrijević and Sahal-Bréchot calculations agree well with our and other experimental results in the temperature range (5000–12,000) K and these theoretical results are recommended for plasma diagnostic purposes. The study of line shapes within Mg I 383.53 nm multiplet shows that the use of Debye shielding correction improves the agreement between theoretical and experimental Stark broadening parameters.     

Atomic and molecular emissions in laser-induced breakdown spectroscopy

This article summarizes measurements and analysis of hydrogen Balmer series atomic lines following laser-induced optical breakdown. Electron number density on the order of 1 × 10²⁵ m^− 3 can be measured using H_α Stark width and shift in the analysis of breakdown plasma in 1 to 1.3 × 10⁵ Pa, gaseous hydrogen. The H_β line can be utilized for electron number density up to 7 × 10²³ m^− 3. The historic significance is elaborated of accurate H_β measurements. Electron excitation temperature is inferred utilizing Boltzmann plot techniques that include H_γ atomic lines and further members of the Balmer series. Laser ablation of aluminum is discussed in view of limits of application of the Balmer series. H_β and H_γ lines show presence of molecular carbon in a 2.7 and 6.5 × 10⁵ Pa, expanding methane flow. Diagnostic of such diatomic emission spectra is discussed as well. Laser-induced breakdown spectroscopy historically embraces elemental analysis, or atomic spectroscopy, and to a lesser extent molecular spectroscopy. Yet occurrence of superposition spectra in the plasma decay due to recombination or due to onset of chemical reactions necessitates consideration of both atomic and molecular emissions following laser-induced optical breakdown. Molecular excitation temperature is determined using so-called modified Boltzmann plots and fitting of spectra from selected molecular transitions. The primary interest is micro-plasma characterization during the first few micro-seconds following optical breakdown, including shadowgraph visualizations.     

Asymmetric Stark broadening of the Fe I 538.34 nm emission line in a laser induced plasma

In this work asymmetries along with shifts in the line profiles of neutral iron emission lines coming from a laser induced plasma have been detected. The plasma was produced in air at atmospheric pressure on a 50% Fe–Ni alloy and the emission was collected at a temporal window of (2.5, 3) μs. To avoid the effect of spatial inhomogeneity on the profiles, a deconvolution procedure was applied to obtain the spatially resolved emissivity. Asymmetric theoretical Stark profiles, which take into account the effect of static ions, were used to be fitted to the experimental data of the emission profile of the line Fe I 538.34 nm. The fitting of the theoretical profile to the experimental data was carried out by means of the least squares method using genetic algorithms to automatically solve the optimization problem. The correlation coefficient was higher for the asymmetric fits than for the symmetric ones. From the fit, the quasistatic ion broadening parameter α, the electron broadening parameter w_e, and the total shift of the maximum of the line d_t, were obtained. The ion parameter α varied in a range (0.2–0.3) for an electron density between (4–15) × 10¹⁶ cm^− 3. The ion influence on the total broadening was of 15–20%. The total shift varied in the range (0.01–0.06) nm and it was mainly given by the ion shift, the electron shift being negligible. For the electron density range in this work, approximated linear behaviors of the total width and shift with electron density have been obtained.     

On the Stark broadening in the Au I and Au II spectra from a helium plasma

The Stark FWHM (Full-Width at Half of the Maximal line intensity, W) of 5 neutral and 26 singly ionized gold (Au I and Au II, respectively) spectral lines have been measured in laboratory helium plasma at approximately 16,600 K electron temperature and 7.4 × 10²² m^− 3 electron density. Five Au I and ten Au II W values are reported for the first time. The Au II W values are compared with recent theoretical data, calculated based on a modified semi-empirical approach, and also with existing experimental W values. Our normalized Stark widths are six times higher than those measured in a laser-produced plasma. Possible explanation of this is recommended here. An agreement (within the accuracy of the experiment and uncertainties of the theoretical approach used) with the recently calculated W data was found in the 6p–7s Au II transition. The calculated hyperfine splitting for the five Au II lines in the 6s–6p transition is also presented. At the stated helium plasma conditions, Stark broadening has been found to be the dominant mechanism in the Au I and Au II line shape formation. A modified version of the linear low-pressure pulsed arc was used as a plasma source operated in helium, with gold atoms as impurities evaporated from the thin gold cylindrical plates located in the homogeneous part of the discharge, providing conditions free of self-absorption. This plasma source ensures good conditions for generation of excited gold ions due to Penning and charge exchange effects.     

New power source from fractional quantum energy levels of atomic hydrogen that surpasses internal combustion

Extreme ultraviolet (EUV) spectroscopy was recorded on microwave discharges of helium with 2% hydrogen. Novel emission lines were observed with energies of q·13.6 eV where q=1,2,3,4,6,7,8,9, or 11 or these lines inelastically scattered by helium atoms wherein 21.2 eV was absorbed in the excitation of He (1s²) to He (1s¹2p¹). These lines were identified as hydrogen transitions to electronic energy levels below the ‘ground’ state corresponding to fractional quantum numbers. Significant line broadening corresponding to an average hydrogen atom temperature of 33–38 eV was observed for helium–hydrogen discharge plasmas; whereas pure hydrogen showed no excessive broadening corresponding to an average hydrogen atom temperature of ≈3 eV. Since a significant increase in H temperature was observed with helium–hydrogen discharge plasmas, and energetic hydrino lines were observed at short wavelengths in the corresponding microwave plasmas that required a very significant reaction rate due to low photon detection efficiency in this region, the power balance was measured on the helium–hydrogen microwave plasmas. With a microwave input power of 30 W, the thermal output power was measured to be at least 300 W corresponding to a reactor temperature rise from room temperature to 900 °C within 90 s, a power density of 30 MW/m³, and an energy balance of about −4×10⁵ kJ/mol H₂ compared to the enthalpy of combustion of hydrogen of −241.8 kJ/mol H₂.     

Measurement of electron density utilizing the Hα-line from laser produced plasma in air

The electron density in a laser produced plasma experiment was measured utilizing the Stark broadening of the H_α-line at 656.27 nm. This line results from the interaction of the Nd:YAG laser at the fundamental wavelength of 1.06 μm with a plane solid aluminum target in a humid air. The measurements were repeated at several delay times (0–10 μs) and at a fixed gate time of 1 μs. The electron density from the optically thin Al II-line at 281.62 nm was measured in parallel from the same spectra. The electron density was found in the range from 10¹⁸ cm^− 3 down to 6 × 10¹⁶ cm^− 3 at longer delay time. The electron density from the H_α-line using the Griem's standard theory was compared with the predictions of other model due to Gigosos et al. The agreement between the measured electron density from both the H_α-line and the Al II-line would confirm the reliability of utilizing the H_α-line as an electron density standard reference line in LIBS experiments. Several important features characterize the H_α-line: it is a well isolated line, it gives large signal to background ratio, it lasts a long time after the termination of the laser (up to 10 μs), its Stark width is relatively large and does not exhibit self-absorption.     

Ammonia treatment of carbon cloth anodes to enhance power generation of microbial fuel cells

Changes in microbial fuel cell (MFC) architecture, materials, and solution chemistry can be used to increase power generation by microbial fuel cells (MFCs). It is shown here that using a phosphate buffer to increase solution conductivity, and ammonia gas treatment of a carbon cloth anode substantially increased the surface charge of the electrode (from 0.38 to 3.99 meq m⁻²), and improved MFC performance. Power increased to 1640 mW m⁻² (96 W m⁻³) using a phosphate buffer, and further to 1970 mW m⁻² (115 W m⁻³) using an ammonia-treated electrode. The combined effects of these two treatments boosted power production by 48% compared to previous results using this air-cathode MFC. In addition, the start up time of an MFC was reduced by 50%.     

The role of the He I and He II metastables in the population of the Sn II,Sn III and Sn IV ion levels

On the basis of the temporal evolutions of the singly, doubly and triply ionized tin (Sn II, Sn III and Sn IV, respectively) spectral line intensities, in the pulsed helium and nitrogen plasmas, the important role of the He I and He II metastables has been observed in the Sn II, Sn III and Sn IV ionization and population processes. According to these processes, one can expect realization of several laser levels in the Sn II (11.07, 11.20, 12.44 and 13.11 eV), Sn III (15.91, 17.82, 19.13 and 20.19 eV) and Sn IV (20.51 eV) spectra. The modified version of the linear, low-pressure, pulsed arc was used as a plasma source operated in helium with tin atoms, as impurities, evaporated from tin cylindrical plates located in the homogenous part of the discharge tube. This plasma source provides good conditions for a generation of the Sn III, Sn IV and Sn V ions at relatively low electron temperatures (below 18,000 K) providing low background radiation around the intense Sn IV and Sn III spectral lines in the helium plasma. The 222.613 ± 0.0005 nm Sn IV line, not observed up to now, has been identified. The marked, but not classified 243.688 nm Sn spectral line is sorted by ionization stages. The shapes of Sn III and Sn IV lines, ranged between 207 nm and 307 nm, have been obtained. At a 17,500 K electron temperature and 1.07 × 10²³ m^− 3 electron density the Stark broadening was found as the dominant mechanism in the mentioned lines broadening. The measured Stark widths of the prominent nine Sn IV and seven Sn III lines are the first data in the literature. The Stark widths of the intense 229.913 nm and 288.766 nm Sn IV lines can be used for the plasma electron density and temperature diagnostics purposes.     

Determination of the standard enthalpy of formation of paratungstate A ion

Enthalpy changes for the reaction of HCl(aq) withNa₂WO₄ (aq) were measured at T =  298.15 K in a HT-1000 calorimeter. The standard enthalpy of reaction for the formation ofW₇O₂₄^6 −  (aq) was calculated on the basis of the experimental results, Δ_rH_m^o(298.15K )  =  − (320.7  ±  1.0)kJ · mol ^− 1. Combining this with the values from the literature led to the standard enthalpy of formation of W₇O₂₄^6 − (aq),Δ_fH_m^o (298.15 K)  =  − 6689.8 kJ · mol ^− 1.     

Photographic plasma images and electron number density as well as electron temperature mappings of a plasma sustained with a modified argon microwave plasma torch (MPT) measured by spatially resolved Thomson scattering

In this work the determination of electron number densities and electron temperatures for the case of a modified microwave plasma torch (MPT) operated at 100 W with argon by means of spatially resolved Thomson scattering measurements and photographic records of the MPT at different working conditions are reported. With an internal gas flow of 500 ml min⁻¹ and an outer gas flow of 200 ml min⁻¹ electron number densities and electron temperatures are in the range of 10²⁰ m⁻³ to 10²¹ m⁻³ and of 16 000–18 000 K, respectively. When increasing the internal gas flow from 500 to 900 ml min⁻¹ the plasma becomes longer and the maximum electron number density increases by a factor of 2. An increase of the outer gas flow from 200 to 700 ml min⁻¹ leads to a lifting of the whole plasma from the burner edge with the maximum electron number density remaining unchanged. An increase of the power from 80 to 180 W was found to lead to higher electron number densities whereas the electron temperatures remain unchanged. The addition of 1.2 mg min⁻¹ of water vapor to the internal gas flow leads to a decrease of the electron number density from 4.7×10²⁰ m⁻³ to 2×10²⁰ m⁻³ and to an increase of the electron temperature from 16 000 to 22 000 K. In order to document the influence of the internal gas flow rate, water introduction and introduction of easily ionized elements on the visible plasma shape digitally recorded photos of the plasma are presented.     

Improved performance of anode with iron/sulfur-modified graphite in microbial fuel cell

The paper reports the operation of a new-design microbial fuel cell using compost leachate as a substrate, oxygen/electrodeposited MnO_x cathode and a new-anode concept with graphite modified by an iron/sulfur solid chemical catalyst which almost eliminates the starting delay time and gives very high current and power densities, I ~ 25 A m^− 3 at P_max ~ 12 W m^− 3 or I ~ 3.8 A m^− 2 at P_max ~ 1.8 W m^− 2.     

Solubilities of l-glutamic acid, 3-nitrobenzoic acid,p-toluic acid,calcium-l-lactate,calcium gluconate,magnesium-dl-aspartate,and magnesium-l-lactate in water

Solubilities of l -glutamic acid, 3-nitrobenzoic acid, p -toluic acid, calcium-l -lactate, calcium gluconate, magnesium- dl -aspartate, and magnesium- l -lactate in water were determined in the temperature range 278 K to 343 K. The apparent molar enthalpies of solution at T =  298.15 K as derived from these solubilities areΔ_solH_m (l -glutamic acid,m_sat =  0.0565 mol · kg ^− 1)  =  30.2 kJ · mol ^− 1,Δ_solH_m (3-nitrobenzoic acid, m =  0.0188 mol · kg ^− 1)  =  28.1 kJ · mol ^− 1, Δ_solH_m( p - toluic acid, m =  0.00267 mol · kg ^− 1)  =  23.9 kJ · mol ^− 1,Δ_solH_m (calcium- l -lactate tetrahydrate,m =  0.2902 mol · kg ^− 1)  =  25.8 kJ · mol ^− 1,Δ_solH_m (calcium gluconate, m =  0.0806 mol · kg ^− 1)  =  22.1 kJ · mol ^− 1, Δ_solH_m(magnesium-dl -aspartate tetrahydrate, m =  0.1469 mol · kg ^− 1)  =  11.5 kJ · mol ^− 1, andΔ_solH_m (magnesium- l -lactate trihydrate,m =  0.3462 mol · kg ^− 1)  =  3.81 kJ · mol ^− 1.     

The thermodynamic properties of DyBr3(s) and DyI3(s) from T=5 K to their melting temperatures

Low-temperature calorimetric measurements have been performed on DyBr₃(s) in the temperature range (5.5 to 420 K ) and on DyI₃(s) from T=4 K to T=420 K. The data reveal enhanced heat capacities below T=10 K, consisting of a magnetic and an electronic contribution. From the experimental data on DyBr₃(s) a C⁰_p,m (298.15 K) of (102.2±0.2) J·K⁻¹·mol⁻¹ and a value for {S⁰_m (298.15 K) − S⁰_m (5.5 K)} of (205.5±0.5) J·K⁻¹·mol⁻¹, have been obtained. For DyI₃(s), {S⁰_m (298.15 K) − S⁰_m (4 K)} and C⁰_p,m (298.15 K) have been determined as (226.9±0.5) J·K⁻¹·mol⁻¹ and (103.4±0.2) J·K⁻¹·mol⁻¹, respectively. The values for {S⁰_m (5.5 K) − S⁰_m (0)} for DyBr₃(s) and {S⁰_m (4 K) − S⁰_m (0)} for DyI₃(s) have been calculated, giving S⁰_m (298.15 K)=(212.3±0.9) J·K⁻¹·mol⁻¹ in case of DyBr₃(s) and S⁰_m (298.15 K) =(233.1±0.7) J·K⁻¹·mol⁻¹ for DyI₃(s). The high-temperature enthalpy increment has been measured for DyBr₃(s) in the temperature range (525 to 799 K) and for DyI₃(s) in the temperature range (525 to 627 K). From the results obtained and enthalpies of formation from the literature, thermodynamic functions for DyBr₃(s) and DyI₃(s) have been calculated from T→0 to their melting temperatures at 1151.0 K and 1251.5 K, respectively.     

The vapour pressures of saturated aqueous solutions of magnesium,calcium, nickel and zinc acetates and molar enthalpies of solution of magnesium,calcium, zinc and lead acetates

Vapour pressures of water over saturated solutions of magnesium, calcium, nickel and zinc acetates were determined as a function of temperature. The vapour pressures served to evaluate the water activities, osmotic coefficients and molar enthalpies of vaporization. Molar enthalpies of solution of magnesium acetate tetrahydrate,Δ_solH_m (T =  294.71K ;m =  0.01 mol · kg ^− 1)  =  − (15.65  ±  0.97)kJ · mol ^− 1; calcium acetate,Δ_solH_m (T =  297.18K ;m =  0.01 mol · kg ^− 1)  =  − (28.15  ±  0.28)kJ · mol ^− 1; zinc acetate dihydrate,Δ_solH_m (T =  297.36K ;m =  0.01 mol · kg ^− 1)  =  − (22.49  ±  0.90)kJ · mol ^− 1and lead acetate trihydrate,Δ_solH_m (T =  297.36K ;m =  0.0086 mol · kg ^− 1)  =  (22.46  ±  0.94)kJ · mol ^− 1, were determined calorimetrically.     

Fraunhofer-type absorption line splitting and polarization in confocal double-pulse laser induced plasma

Strong line splitting and polarization are observed in Fraunhofer-type absorption lines in Pb, Sn, Si, Cd, In, and Zn in confocal double-pulse laser induced plasma (DP-LIP) experiments. This effect is detectable using medium laser power densities: (~ 1–2) × 10¹³ W/m² for the first laser pulse and 1 × 10¹⁴ W/m² for the second laser pulse. Polarization and splitting effects exist only during the second laser pulse (~ 7 ns). Absorption line polarization and splitting phenomena may be explained by a high overall magnetic field and motional Stark effect caused by the second laser pulse inside the laser plasma created by the first pulse.     

Electron excitation coefficients of neutral and ionic levels of krypton in Townsend discharges

In this paper, we present experimental results for excitation coefficients of krypton atoms to several Kr and Kr⁺ excited levels for E/N (electric field to gas particle number density ratio usually in units of Townsend, 1 Td = 10^− 21 V m²) values from 7 × 10^− 20 V m² to above 1 × 10^− 17 V m². The data have been obtained in two different parallel plate self-sustained Townsend discharge drift tubes. The spatial distribution of the emission intensities were recorded and then normalized to give excitation coefficients at the anode, by using the electron flux at this point. The values of these coefficients are placed on an absolute scale by using a standard tungsten ribbon lamp calibrated against a primary blackbody radiation standard. The ionization rates at different E/N are obtained from the spatial emission profiles.The data for atomic krypton levels 2p₂, 2p₃, 2p₅, 2p₆, 2p₇, 2p₈, 3p₅ and 3p₆ (in Paschen notation) were converted to excitation coefficients by using quenching coefficients from the literature. The emission coefficients of eight 4s²4p⁴ (³P)5p levels of Kr⁺ have also been measured for E/N values from about 1 × 10^− 18 V m² up to nearly 8 × 10^− 18 V m².