Sorption of chromium(III) and chromium(VI) on lead sulfide

The sorption of chromium(III) and chromium(VI) on lead sulfide has been investigated in dependence on pH, time of sorption and the concentrations of sorbate and sorbent. The mechanisms of the sorption of Cr³⁺ and CrO ₄ ^2– traces on lead sulfide are discussed; a difference between CrO ₄ ^2– sorption on PbS and -Fe₂O₃ has been found. Sulfates and molybdates affect the removal of chromates from aqueous solutions. Lead sulfide carrier prepared in this work was also used for the preconcentration of chromium(III) and chromium(VI) from tap water.     

Short-term measurements of acrolein in ambient air

Summary A method has been developed for the determination of acrolein in air samples collected by a high-volume aqueous scrubber. The aldehyde is collected as the bisulfite adduct, which is decomposed before determination of acrolein by DNPH (2,4-dinitrophenylhydrazine) derivatization and HPLC. Approximately 95% of the acrolein reacts with DNPH within 3 h at DNPH:HSO₃ molar ratios of up to 10. The method appears promising for short-term air sampling at 8 L min^–1, enabling the achievement of a detection limit of 0.2 g m^–3 for acrolein.     

Simultaneous measurements of formaldehyde and ozone in air by annular denuder-HPLC techniques

Summary A denuder sampling method combined with HPLC analysis for the simultaneous determination of formaldehyde and ozone in ambient air is described. It is based on the reactions of CH₂O and O₃ with 2,4-dinitrophenylhydrazine (DNPH) and 4-allyl-2-methoxyphenol (eugenol)_respectively, both acting as coatings of two annular denuders connected in series. Formaldehyde released from the ozonolysis of eugenol is quantitatively collected on a third downstream DNPH-coated denuder. The two DNPH denuders are then extracted and analyzed as hydrazone derivative by HPLC with UV absorbance detection.The stoichiometric factor of the eugenol-ozone reaction was found to be 2.0±0.1 moles of O₃ per mole of CH₂O. The limits of detection are 0.8gm^–3 CH₂O and 3gm^–3 O₃ for 100l air sampled, corresponding to 1-h sampling at 1.7l min^–1.     

Synthesis and structure investigation of the Pb3V(PO4)3 eulytite

Lead vanadium phosphate Pb₃V(PO₄)₃ was synthesized by solid state reaction and characterized by X-ray single crystal and powder diffraction, electron microscopy, and magnetic susceptibility measurements. The crystal structure model of Pb₃V(PO₄)₃ was refined using X-ray single crystal data (a=10.127(1)Å, S.G. Z=4). The compound has an eulytite-like structure and its average structure model may be presented as a three-dimensional network formed by strongly distorted mixed (Pb/V^III) metal-oxygen octahedra connected by edge sharing and forming corrugated chains. The octahedra are additionally linked by tetrahedral phosphate groups via corner sharing. Lead and vanadium atoms randomly occupy two close positions in the octahedra. The electron microscopy study revealed the presence of a rhombohedral superstructure with and indicating ordering in the structure. The same type of superstructure was found by us for two another lead-containing eulytite Pb₃Fe(PO₄)₃ where Fe⁺³ has an ionic radius close to that of V⁺³. Magnetic susceptibility measurements revealed Curie-Weiss behavior for the Pb₃V(PO₄)₃ compound.     

Low-background Germanium spectrometry the bottom line three years later

Three years ago, state-of-the-art low-background germanium spectrometry was discussed, and speculations were advanced as to the origin of the remaining background. Some of those speculations have been shown to the incorrect. Contemporary lead shielding contains 100 Bq/kg of²¹⁰Pb. Our 450-year-old lead was shown to contain <100 mBq/kg A high purity electroformed copper Marinelli shield was placed around the detector with no efffect on the background, which implied that the source is other than the 450-year-old shield. A new limit on the²¹⁰Pb in this old lead shield is <9 mBq/kg. Electroformed copper components were found to contain²²⁶Ra and²²⁸Th contaminations at levels of 3500 and 110 Bq/kg, respectively. High purity H₂SO₄, recrystallized CuSO₄, and a BaSO₄ scavenge in the electroforming bath have reduced these contaminations to <25 and 9 Bq/kg, respectively. In copper, cosmic ray induced nuclear reactions are now the dominant source of raioactivity. For example,⁵⁸Co can be readily measured after only a 24-hour exposure at sea level. A new germanium spectrometer containing 2150 grams of 87.44% enriched⁷⁶Ge has been fabricated to mitigate the effect of cosmogenic⁶⁸Ge in the background. Current background spectra are presented, and potential sources identified.     

Electrodeposition of lead on to a graphite probe for electrothermal atomic absorption spectrometry

A simple system for controlled potential electrodeposition on to a graphite probe electrode is described. Totally pyrolytic graphite was found to be better for electrodeposition than microporous glassy carbon or electrographite coated with pyrolytic graphite. Lead can be deposited by anodic and cathodic processes as PbO₂ and Pb, respectively. Potentials of + 1.2 to + 2.0 V were best for anodic deposition and – 0.8 to– 2.0 V were best for cathodic deposition. With an electrodeposition time of 120 s, AAS sensitivity gains of × 9 and × 3.5 were achieved for anodic and cathodic deposition, respectively, in comparison with the results obtained by direct injection of 20 1 sample volumes on to the probe. The lead cathodic process was unaffected by NaCl concentrations up to 10^–2 M, but only 10^–3 M NaCl could be tolerated by anodic deposition.     

Spektrophotometrische Bestimmung von Kobalt in Bleilegierungen

Zusammenfassung Die vorgeschlagene spektrophotometrische Methode beruht auf der Reaktion von Triphenyltetrazoliumchlorid (TTC) mit dem Thiocyanatokomplex des Kobalts(II). Bleilegierungen werden in Salpetersäure gelöst, das Blei mit Natriumchlorid gefällt und durch Abfiltrieren entfernt. Das Kobalt wird mit TTC und Thiocyanat in (TT)₂ [Co(CNS)₄] übergeführt, mit Chloroform extrahiert und unter Verwendung eines gelben Lichtfilters photometriert.Das Beersche Gesetz ist in den Grenzen 2–100g Co erfüllt. Die Bestimmung wird in Gegenwart von Ascorbinsäure und Thiosulfat durchgeführt und durch Ag⁺, Fe³⁺, Cu²⁺, Ni²⁺, Hg²⁺, Mo⁴⁺ und Zn²⁺ nicht gestort.Der mittlere Relativfehler der Methode ist 5,60%.

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The photometric determination of cobalt in lead alloys

Summary The proposed spectrophotometric method is based on the reaction of triphenyltetrazolium chloride (TTC) with the thiocyanato complex of cobalt(II). Lead alloys are dissolved in nitric acid, the lead is precipitated with sodium chloride and removed by filtration. The cobalt is converted into (TT)₂ [Co(CNS)₄] by means of TTC and thiocyanate, extracted with chloroform and photometrized with employment of a yellow light filter.Beer's law is valid between the limits 2–100g CO. The determination is conducted in the presence of ascorbic acid and thiosulfate and there is no interference by Ag⁺, Fe³⁺, Cu²⁺, Ni²⁺, Hg²⁺, Mo⁴⁺ and Zn²⁺.The mean relative error of the method is 5.60%.

     

Zur Kristallchemie der Blei-Lanthanoid-Oxoaluminate. Zur Kenntnis von Pb2HoAl3O8 und Pb2LuAl3O8

Crystal Chemistry of the Lead Lanthanide Oxoaluminates. On Pb₂HoAl₃O₈ and Pb₂LuAl₃O₈ . Single crystals of (I) Pb₂HoAl₃O₈ and (II) Pb₂LuAl₃O₈ were prepared by flux technique and investigated by X-ray methods. It crystallizes with cubic symmetry, space group O–P4₂/n 3 2/m, (I): a = 9.4164(13) Å, (II): a = 9.3486(8) Å, Z = 4. The new structure type shows AlO₄ tetrahedra, LnO₈ hexagonal bipyramids and one sided coordinated Pb²⁺ within heterocubane units. The crystal chemical relationships to other lead oxides containing heterocubane Pb₄O₄ units are discussed.     

Kinetics of Anodic Dissolution of Gold in Alkali–Cyanide Solutions: Effect of Lead Ions

Effective order of the gold dissolution reaction by cyanide ions, p, transfer coefficient , and exchange current i ₀are measured at constant coverages of the gold surface by lead adatoms, . Constancy of is ensured by maintaining the time period t, during which the electrode is in contact with solution after the renewal of its surface and before taking measurements, constant. Solutions under study contain (0.5–2) × 10^–5M lead acetate, 0.05–0.2 M KCN, 0.1 M KOH, and 0.01 M KAu(CN)₂. With increasing t, quantities p, , and i ₀increase from, respectively, 0.17, 0.1, and 10^–5A dm^–2(in 0.05 M KCN) to p 1.2, 0.45, and i ₀ 10^–4A dm^–2. The increase in psuggests that the limiting stage alters in the presence of lead adatoms: in addition to adsorbed cyanide ions, as is the case with pure alkali–cyanide solutions, it involves cyanide ions located outside the adsorption layer. A feasible mechanism for the acceleration of gold dissolution by lead adatoms is offered.     

Statistical evaluation of the influence of several sample pretreatment methods on the mercury content detectable by chemical analysis of contaminated soil samples under practical conditions

The estimation of the environmental risk of contaminated sites caused by hazardous components may be obtained, for instance, by means of a soil survey. There unavoidable errors by sampling, sample preparation and chemical analysis occur. Furthermore, in case of mercury contaminations, the mercury content detectable by chemical analysis can be falsified, if between sampling, on the one hand, and sample preparation and sample decomposition for chemical analysis, on the other hand, volatile components or elementary metallic mercury escape from the sample. Thus, in these cases, handling of samples such as air drying, storing in plastic bags or thermal evaporation, generally termed sample pretreatment, is a further source of error in evaluating a material. However, the measuring results are influenced not only by sampling, sample pretreatment, sample preparation by homogenization and splitting, and chemical analysis; they must also reflect the intrinsic properties of the soil sample subject to both global fluctuations and local heterogeneities. The present work shows by example of a non-uniformly contaminated site to what extent the analytically detectable mercury content is changed by the method of handling of soil samples in the period between sampling and chemical analysis. A hierarchical experimental design was realized in order to separately quantify the different sources of variation of the measured mercury contents, which are caused by global variations, local heterogeneities, sample preparation, sample pretreatment as well as chemical analysis. As turned out by variance analysis, the variance portion contributed to the total variance by sample pretreatment is highly significant and lies in the same order of magnitude as the variance caused by local heterogeneities of the soil. That means that the type of sample pretreatment influences the analytical results essentially. In order to quantify the effect of a definite pretreatment method in comparison with the mercury content of the unchanged original soil sample, the probable systematic error of a method was introduced. Investigations were only carried out at two sampling locations of the contaminated site because of the relatively high labour; the mean values and variances obtained cannot be immediately transferred to other sites. However, the general knowledge can be used as methodical basis for further investigations. Particularly, the consequence arises that the regulations existing for the treatment of mercury-contaminated samples between sampling and chemical analysis must be revised to obtain comparable criteria of evaluation.Symbols used level of error in statistical tests, - _i random effect of the i-th sampling location with respect to the mercury content, effect of global fluctuations - _ij random effect of the j-th primary sample (composite sample) at the i-th sampling location, effect of local heterogeneity, sampling error - _ijk random effect of the k-th subsample within the respective j-th primary sample (composite sample) at the i-th sampling location, sample preparation error - _ijkl random effect of the l-th pretreated sample belonging to the respective k-th subsample of the j-th primary or composite sample at the i-th sampling location, sample pretreatment effect - _1– probable relative systematic error of a pretreatment methods as compared with the original material at the coverage probability 1– - overall expected mercury content of the sampling results - _i expected mercury content of the i-th pretreated composite sample at a fixed location - û_{1.1 –} lower limit of a confidence interval for the unknown expected mercury content of unchanged original material at the confidence probability 1– - _i intraclass correlation coefficient - ² , ² , ² , ² , _Z ² variance components caused by global variability, local heterogeneity, sample preparation, sample pretreatment and analytical error, respectively - _total ² total variance of mercury content - D² operator of the variance of a random variable - E operator of the mathematical expectation of a random variable - F_i mean squared sum quotient of the Fisher's F-distribution - F_1–/2(fg_i, fg_j) critical value of the F-distribution at fg_i and fg_j degrees of freedom, respectively - fg_i degree of freedom of a (mean) sum of squared deviations - H_i hypothesis regarding a statistical law - I_1– confidence interval for the unknown expected value difference of two methods compared at the probability 1–, probable systematic error of a pretreatment method as compared with the unchanged original material at the coverage probability 1– - MQ_i, mq_i mean squared deviations as explained in the context - n_i number of sampling locations, primary samples per location, subsamples per primary sample, pretreatment methods and measuring values per pretreated sample, respectively - S _i ² , s _i ² variance estimation obtained by chemical analysis - SQ_i, sq_i sum of squared deviations - S(|Y₁–Y_i|) mean error of the absolute mean value difference |Y₁–Y_i|) - t_1–/2;m critical value of the Student's t-distribution at m degrees of freedom and the probability 1–/2 - Y_ijklm mercury content obtained on the m-th final sample of the l-th pretreated sample belonging to the k-th subsample of the j-th primary sample at the i-th sampling location - Y_i, y_i,... mean values obtained by sampling and chemical analysis - Z_ijklm random error of the ijklm-th measuring value (final sample value) Y_ijklm.     

Spectrophotometric determination of mercury with 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine by flow injection analysis

5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS₄) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min^–1 for Hg(II) withm-Cl-TPPS₄ in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 l), the method's relative standard deviation was 0.82% (n = 12) at 5.0 g ml^–1 mercury, with a linear range of 0–12.0 g ml^–1 and an analytical frequency of 60h^–1. The detection limit (3) was 0.025 g ml^–1. Interference studies showed that most metal ions co-existing with Hg²⁺ could be tolerated at 100-fold excess levels, but Zn²⁺, Cu²⁺ and Mn²⁺ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.     

Effect of Lead Ions on the Kinetics of Gold Deposition from Cyanide Electrolytes

The depolarization of the gold electrodeposition in the presence of lead ions depends on their concentration and the duration of electrode contact with solution preceding a potential scan in an extremum fashion. At constant coverages of the gold surface by lead adatoms , the process rate depends on the overvoltage in accord with the Tafel equation. Effective values of the exchange current i ₀ and transfer coefficient increase with from i ₀ 3 × 10^–5 A cm^–2 and = 0.23 in pure solutions to 3 × 10^–4 A cm^–2 and 0.53 at 0.4. The reaction order by cyanide ions is independent of and equals nearly –0.9. Effects of lead adatoms on the kinetics of cathodic and anodic processes are compared and the obtained data may be brought to conformance given that their mechanisms in pure solutions differ and converge in the presence of lead adatoms.     

Ab initio calculations of potential energy surface for reaction of nucleophilic addition of H− ion to methylacetylene

Within the framework of the Hartree-Fock-Roothaan Method, using double- basis sets 3-21++G and (6-31-H-G//3-21++G), the minimum energy paths (MEPs) have been calculated for reactions of nucleophilic addition of the hydride ion H^– to the methylacetylene molecule: CH₃-CCH+H^–[CH₃-CH=CH]^– (1) CH₃-CCH+H^–[CH₃-C=CH₂]^– (2). It has been established that the activation energy for reaction (2) is 7.02 kJ/mole lower than for reaction (1). An analysis has been made of the character of electron density distribution along the MEP of each reaction. It has been shown that distortion of geometry of the reactants plays an important role in intensifying the interaction of the frontier orbitals. The reasons for nonfulfillment of Markownikoff's rule for these reactions have been determined. The results from the calculations are compared with calculations reported in the literature for the related reaction of nucleophilic addition of the hydride ion H^– to the acetylene molecule: HCCH+H^–[CH₂=CH]^–.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 21, No. 3, pp. 303–309, May–June, 1985.     

The PVT properties of concentrated aqueous electrolytes. IV. Changes in the compressibilities of mixing the major sea salts at 25°C

The speed of sound of mixtures of the six possible combinations of the major sea salt ions (Na⁺, Mg²⁺, Cl^–, and SO ₄ ^2– ) have been determined at I=3.0 and at 25°C. The results have been used to determine the changes in the adiabatic compressibility of mixing K_m the major sea salts. The values of K_m have been fit to the equation K_m=y₂y₃I²[k₀+k₁(1-2y₃)] where y_i is the ionic strength fraction of solute i, k₀ and k₁ are parameters related to the interactions of like-charged ions. The Young cross-square rule is obeyed to within ±0.04×10^–6 cm³-kg^–1-bar^–1. A linear correlation was found between the compressibility k₀ and volume v₀ interaction parameters (10⁴k₀=–0.24+3.999 v₀, s=0.15) in agreement with out earlier findings. Estimates of the sound speeds for the cross square mixtures (NaCl+MgSO₄ and MgCl₂+Na₂SO₄) were made using the equations of Reilly and Wood. The estimated sound speeds were found to agree on the average with the measured values to ±0.36 m-sec^–1.     

Structures and EPR spectra of binary sulfur-nitrogen radicals from DFT calculations

The scattered electron paramagnetic resonance (EPR) spectroscopic data for binary sulfur-nitrogen (S,N) radicals have been compiled and critically assessed.Many of these are inorganic rings or cages.For each species, possible equilibrium structures in the gas phase and the EPR hyperfine coupling (hfc) constants have been calculated with DFT using the B3LYP functional and basis sets of triple-ζ (or better) quality.Good agreement is obtained between calculated and measured values for the well characterized [S₃N₂]⁺, a planar π-radical for which the s-component of the orbitals is likely to be reasonably independent of minor geometrical changes between gas-phase and condensed-phase states.The cage compounds [S₄N₄]⁻ and [S₄N₅]⁻², for which reliable experimental EPR spectra have been reported, show larger variation between calculated and measured hfc, as a consequence of the dependence of the s orbital content of the molecular orbitals on small structural changes.The very large disagreements between the DFT calculated and experimentally claimed hfc constants for [NS], [SNS] and [S₄N₄]⁻³ in condensed phases lead us to question their assignment.Among binary S,N radicals, ³³S hfc data has only been reported for [S₃N₂]⁺ (through isotopic enrichment).These values were essential for the correct identification of the EPR spectra of this important radical, which previously was misassigned to other species.Our results suggest that ³³S data will be equally important for the correct identification of the EPR spectra of other binary S,N species, many of which are cyclic systems, e.g.[S₃N₃], [S₄N₃] and[S₄N₅].     

Mixed halide complexes of lead. A comparison with theoretical predictions

Experimentally and theoretically derived formation constants of mixed lead halide complexes are compared at 25.0°C and one molar ionic strength. The formation constant of PbBrCl, ₁₁=79±10, is somewhat larger than the theoretical results, ₁₁=55, predicted using the formation constants of PbBr₂ and PbCl₂. The molar absorptivity of PbBrCl was observed to be intermediate in character between the molar absorptivities of PbBr₂ and PbCl₂. Determinations of the formation constants of PbBr₂Cl^– and PbBrCl₂ ^– are in reasonable agreement with the predictions based on the formation constants of PbBr₃ ^– and PbCl₃ ^–. Mixed ligand species dominated the complexation scheme of Pb(II) in our test media.     

Syntheses, characterizations and crystal structures of two lead(II) phosphonate-sulfonate hybrid materials

Hydrothermal reactions of lead(II) acetate with 5-sulfoisophthalic acid monosodium salt (NaH₂BTS) and N-(phosphonomethyl)-N-methylglycine, MeN(CH₂CO₂H)(CH₂PO₃H₂) (H₃L¹), or a new aminodiphosphonic acid, 3-Pyridyl-CH₂N(CH₂PO₃H₂)₂ (H₄L²), afforded two novel lead(II) phosphonate-sulfonate hybrids, namely, Pb₃[L¹][BTS][H₂O]·H₂O 1 and Pb₂[HL³][BTS]·H₂O 2 (H₂L³=3-Pyridyl-CH₂(Me)N(CH₂PO₃H₂)). H₂L³ was formed as a result of the decomposition of one phosphonate group in H₄L² during the reaction. Compound 1 crystallizes in the triclinic space group with a=9.9148(4) Å, b=10.4382(4) Å, c=10.6926(2) Å, α=96.495(2)°, β=110.599(2)°, γ=98.433(2)°, V=1008.31(6) Å³, and Z=2. The structure of compound 1 features a 3D network built from the interconnection of hexanuclear Pb₆(L¹)₂ units and 1D double chains of lead(II) carboxylate-sulfonate. Compound 2 crystallizes in the monoclinic space group P2₁/c with a=9.5403(7) Å, b=11.6170(8) Å, c=19.7351(15) Å, β=97.918(2)°, V=2166.4(3) Å³, and Z=4. Compound 2 has a 3D network structure built by the cross-linkage of 1D double chains of lead(II) phosphonates and 2D layers of lead(II) carboxylate-sulfonate.     

Redox reactions of basic fuchsin in homogeneous aqueous media

The pulse-radiolysis technique has been employed to understand the reaction mechanism and to characterize the transient species involved in the redox processes taking place in the radiation chemistry of basic fuchsin (BF⁺). One-electron reduction and oxidation reactions of BF⁺ have been carried out in homogeneous aqueous solutions employing various reducing (e _aq ^– , (CH₃)₂COH, CO ₂ ^– ) and oxidizing (N ₃, Br, Cl ₂ ^– Br ₂ ^– ) radicals. The absorption spectra of the transients formed in the above reactions have been attributed to semi-reduced and semi-oxidized species of BF⁺, respectively. The kinetic and spectroscopic properties of these transients have been evaluated. The reaction with H and OH radicals have also been performed and compared with those of specific one-electron reducing and oxidizing radicals. These reactions have been inferred predominantly by addition to BF⁺. Protolytic equilibria involving semi-reduced species of basic fuchsin have been studied over the pH range from 2 to 10 and the pK _a has been determined to be 3.9.