Voltammetric Determination of Sulfide Ions

Procedures were proposed for the voltammetric determination of S^2– at a mercury-film electrode. They are based on the oxidation of S^2– at –0.79 to –0.80 V and on the reduction of HgS, the product of the oxidation of S^2–, at –0.76 to –0.96 V in a 1 M NaOH solution. The anodic and cathodic currents are linear functions of S^2– concentration in the ranges from 1 × 10^–5 to 1 × 10^–4 M and from 2 × 10^–6 to 1 × 10^–4 M, respectively.     

Determination of131I,134Cs,137Cs in plants and cheese after Chernobyl accident in Roumania

Various samples from the south-east region of Roumania/greens, fodder, cheese/were analyzed for¹³¹I,¹³⁴Cs and¹³⁷Cs concentrations in May and July 1986 by -ray spectrometry. The concentrations are reported in nCi. kg^–1 wet weight. For greens, a considerable decrease was observed for¹³¹I/to 3.0–7.0 nCi. kg^–1/,¹³⁴Cs/to 0.5–2.0 nCi.kg^–1/ and¹³⁷Cs /to 1.0–4.0 nCi. kg^–1/ from the first half /5–15 May/ till the end of May 1986. For cheese, maximum values were measured between 5 and 15 May /sheep cottage cheese: 500–800 nCi.kg^–1 for¹³¹I, 25–50 nCi. kg^–1 for¹³⁴Cs, 40–80 nCi. kg^–1 for¹³⁷Cs/; at the beginning of July a considerable decrease /to 5–10 nCi. kg^–1 for¹³¹I, 1.2–2.0 nCi.kg^–1 for¹³⁴Cs, 2.2–3.0 nCi. kg^–1 for¹³⁷Cs/ was observed. In autumn 1986 a small increase up to 2.0–3.0 nCi. kg^–1 for¹³⁴Cs and 3.4–5.0 nCi. kg^–1 for¹³⁷Cs /in November/ was reported. The population's internal possible contamination was strongly limited by the authorities' severe control of the food-stuff.     

Negative ion formation in compounds relevant to SF6 decomposition in electrical discharges

Dissociative and nondissociative electron attachment in the electron impact energy range 0–14 eV are reported for SOF₂ SOF₄, SO₂F₂, SF₄, SO₂, and SiF₄ compounds which can be formed by electrical discharges in SF₆. The electron energy dependences of the mass-identified negative ions were determined in a time-of-flight mass spectrometer. The ions studied include F^– and SOF ₂ ^–* from SOF₂; SOF ₃ ^– and F^– from SOF₄; SO₂F ₂ ^–* , SO₂F^–, F ₂ ^– , and F^– from SO₂F₂; SF ₄ ^–* and F^– from SF₄; O^–, SO^–, and S^– from SO₂; and SiF ₃ ^– and F^– from SiF₄. Thermochemical data have been determined from the threshold energies of some of the fragment negative ions. Lifetimes of the anions SOF ₂ ^–* , SO₂F ₂ ^–* , and SF ₄ ^–* are also reported.     

Extraction of actinium with di (2-ethylhexyl) phosphoric acid from hydrochloric and nitric acid solutions

The extraction of actinium with HDEHP from Cl^– and NO ₃ ^– systems has been investigated. It was found that extraction of actinium from HCl solutions is much better than from HNO₃ solutions. Stability constants of the actinium complexes Ac(X^–)²⁺, X^–=Cl^– or NO ₃ ^– , were determined. Our results show that actinium formed less stable complexes with Cl^– than with NO ₃ ^– ligands.     

Effect of preparation pH on pore structure of silica gels

Surface characterization of silica gels prepared at different gelation pH from water glass and sulphuric acid were made by argon adsorption at 77 K using continuous volumetric method. While microporous silica gels prepared in the pH range of 1–3 had BET surface areas of 504–571 m² g^–1, total pore volumes of 0.26–0.31 cm³ g^–1 and micropore volumes of 0.16–0.23 cm³ g^–1, mesoporous silica gels prepared in the pH range of 3.36–0.65 had BET surface areas of 374–530 m² g^–1 and pore volumes of 0.61–0.79 cm³ g^–1.     

Radiation dose assessment for137Cs from fish in the Aegean Sea before and after the Chernobyl accident

The effective doses from fish in the Aegean Sea have been calculated for the nuclide¹³⁷Cs covering the period 1975–1982. The effective dose varies between 3×10^–5 and 10×10^–5 mSv y^–1 for adults and 14×10^–5 to 56×10^–5 mSv y^–1 for children, while the cumulative effective dose for the period 1975–1982 equals to 40.86×10^–5 and 229.57×10^–5 for both adults and children of 10 y old, respectively. When compared to doses derived from the Chernobyl accident /May 1986/ it was found that the additional dose incurred by Greek individuals in May 1986 was approximately equal to the cumulative dose of 8 y contribution period /1975–1982/ for adults and to a year's contribution for children of 10 y old.     

Determination of131I,134Cs,137Cs in grass and cheese after Chernobyl accident in Austria

Various samples from Styria /grass/ and Salzburg /cheese/ were analyzed for¹³¹I,¹³⁴Cs and¹³⁷Cs concentration during April–July 1986 by -ray spectrometry. The concentrations are reported in nCi kg^–1 wet weight. The concentration values found for¹³¹I 0.2–17.2 nCi kg^–1 /grass/, 0.1–0.5 nCi kg^–1 /cheese/, for¹³⁴Cs 1.1–6.2 nCi kg^–1 /grass/, 0.2–1.3 nCi kg^–1 /cheese/, for¹³⁷Cs 1.6–15.7 nCi kg^–1 /grass/, 0.3–2.2 nCi kg^–1 /cheese/. While radioactivity of¹³¹I,¹³⁴Cs and¹³⁷Cs in cheese samples increases from May to June, it decreases in grass samples from May to July 1986.     

The effect of high pressure on the ion pair equilibrium constant of alkali metal fluorides: A spectrophotometric study

Bromophenol blue indicator was used in UV-visible spectrophotometric measurements to study ion association constants of alkali metal fluorides. The equilibrium constants for the ion pair formation of the alkali metal fluorides were determined as a function of ionic strength at one atmosphere pressure and 25°C. The effect of pressure on these association constants was measured at a constant total ionic strength of 1.0 mol-kg^–1 over a pressure range of 1 to 2000 atmospheres at 25°C. The pressure dependences of the stoichiometric association constants of the alkali metal fluorides are given by: lnK _LiF ^* =0.77–2.47×10^–4P–2.12×10^–8P²; lnK _NaF ^* =0.53–1.08×10^–4P–1.66×10^–8P²; lnK _KF ^* =0.24–4.41×10^–5P–7.15×10^–8P²; lnK _RbF ^* =–0.17–8.65×10^–5P–4.51×10^–8P²; and lnK _CsF ^* = –0.37–1.14×10^–4P–6.82×10^–8P², where P is the pressure in atmospheres. The stoichiometric molar volume and compressibility changes for ion pair formation of the alkali metal fluorides were evaluated from the pressure dependence of K _MF ^* data. The thermodynamic association constants were also calculated making use of activity coefficient data from the Pitzer equations. The partial molal volume and compressibility changes for ion pair formation of each alkali metal fluoride are reported.     

Determination of226Ra and uranium in fish samples from waters of the Grand Canyon by alpha spectroscopy without electrodeposition

A previous paper reported the application of a method for determining²²⁶Ra by -spectroscopy. This paper presents important improvements which permit the determination of²²⁶Ra in the presence of large amounts of Ca. The method was applied to the analysis of²²⁶Ra and U isotopes in fish samples from the waters of the Grand Canyon.²²⁶Ra ranged from 0.05 Bq kg^–1 /1.4 pCi kg^–1/ to 0.17 Bq k^–1 /4.7 pCi kg^–1/.²³⁸U values ranged from 0.13 Bq kg^–1 /3.5 pCi kg^–1/ to 0.52 Bq kg^–1 /14 pCi kg^–1/ and²³⁴U values were between 0.23 Bq kg^–1 /6.2 pCi kg^–1/ and 12 Bq kg^–1/ /326. pCi kg^–1/.     

Voltammetric Determination of Rubeanic Acid

Procedures for the voltammetric determination of rubeanic acid (RA) at a mercury-film electrode were proposed. They are based on the oxidation of RA at –0.70 to –0.80 V or on the reduction of mercury sulfide, the product of RA oxidation, at –0.82 to –0.85 V (versus a saturated silver–silver chloride electrode) in a 1 M NaOH solution. The oxidation and reduction currents are linear functions of RA concentration in the ranges from 9 × 10^–6 to 3 × 10^–4 M and from 5 × 10^–6 to 3 × 10^–4 M, respectively.     

Mercury-free sono-electroanalytical detection of lead in human blood by use of bismuth-film-modified boron-doped diamond electrodes

We report the electroanalytical determination of lead by anodic stripping voltammetry at in-situ-formed, bismuth-film-modified, boron-doped diamond electrodes. Detection limits in 0.1 mol L^–1 nitric acid solution of 9.6x10^–8 mol L^–1 (0.2 ppb) and 1.1x10^–8 mol L^–1 (2.3 ppb) were obtained after 60 and 300 s deposition times, respectively. An acoustically assisted deposition procedure was also investigated and found to result in improved limits of detection of 2.6×10^–8 mol L^–1 (5.4 ppb) and 8.5×10^–10 mol L^–1 (0.18 ppb) for 60 and 300 s accumulation times, respectively. Furthermore, the sensitivity obtained under quiescent and insonated conditions increased from 5.5 (quiescent) to 76.7 A mol^–1 L (insonated) for 60 s accumulation and from 25.8 (quiescent) to 317.6 A mol^–1 L (insonated) for 300 s accumulation. Investigation of the use of ultrasound with diluted blood revealed detection limits of the order of 10^–8 mol L^–1 were achievable with excellent inter- and intra-reproducibility and sensitivity of 411.9 A mol^–1 L . For the first time, electroanalytical detection of lead in diluted blood is shown to be possible by use of insonated in-situ-formed bismuth-film-modified boron-doped diamond electrodes. This method is a rapid, sensitive, and non-toxic means of clinical sensing of lead in whole human blood.     

The210Pb and137Cs profiles in sediment cores from Bay of Quinte,Lake Ontario

²¹⁰Pb,²²⁶Ra and¹³⁷Cs profiles have been measured for sediment cores from three locations in Bay of Quinte, Lake Ontario, Canada. Compaction of the sediment with depth of burial is taken into account in calculating recent sedimentation rates and age profiles at these locations from the excess²¹⁰Pb profiles. The rates are 1.803+0.592 cm·y^–1 (0.254±0.083 g·cm^–2·y^–1), 0.101±0.017 cm·y^–1 (0.036+0.006 g·cm^–2·y^–1), and 0.795±0.218 cm·y^–1 (0.076±0.021 g·cm^–2·y^–1). The corresponding fluxes of excess²¹⁰Pb to sediment/water interface are determined to be 1.652, 0.253, and 1.123 pCi·cm^–2·y^–1, respectively. The anomalies observed in the radionuclide concentration profiles are attributed to physical mixing. It is postulated that the significantly higher flux of²¹⁰Pb observed at one of the locations is due to inputs from Trent River which joins the Bay near this location.     

Study of a bis-furaldehyde Schiff base copper(II) complex as carrier for preparation of highly selective thiocyanate electrodes

A new highly selective thiocyanate electrode based on N,N-bis-(furaldehyde)-1,2-phenylenediamine-dipicolyl copper(II) complex [Cu(II)-BFPD] as neutral carrier is described. The electrode has an anti-Hofmeister selectivity sequence: SCN^–>I^–>Sal^–>ClO₄ ^–>Br^–>NO₂ ^–>Cl^–>NO₃ ^–>SO₄ ^2–>SO₃ ^2–>H₂PO₄ ^– and a near-Nernstian potential linear range for thiocyanate from 1.0×10^–1 to 5.0×10^–6 mol L^–1 with a detection limit 2.0×10^–6 mol L^–1 and a slope of 57.5 mV decade^–1 in pH 5.0 of phosphate buffer solution at 20 °C. The response mechanism is discussed on the basis of results from A.C. impedance measurement and UV spectroscopy. The anti-Hofmeister behavior of the electrode results from a direct interaction between the central metal and the analyte ion and a steric effect associated with the structure of the carrier. The electrode has the advantages of simplicity, fast response, fair stability and reproducibility, and low detection limit. The selectivity of electrodes based on [Cu(II)-BFPD] exceeds that of classical anion-sensitive membrane electrodes based on ion exchangers such as lipophilic quaternary ammonium or phosphonium salts. Application of the electrode for determination of thiocyanate in waste water samples from a laboratory and a gas factory, and in human urine samples, is reported. The results obtained were fair agreement with the results obtained by HPLC.     

Electrokinetic properties of mixed solutions of dodecyldimethylamine oxide and sodium dodecyl sulfate: specific adsorption effects of small ions

Electrophoretic light-scattering measurements and potentiometric titrations were carried out on aqueous mixtures of dodecyldimethylamine oxide and sodium dodecyl sulfate. The electrophoretic mobility and the surface charge density of the micelles were always negative, ranging from –2.5 to –3.1×10^–4 cm²V^–1s^–1, and –0.033 to –0.045 cm^–2, respectively, for all surfactant mixing ratios, indicating the specific adsorption of Cl^–, in addition to Na⁺, on micelles. The solution pH, as well as the aggregation number previously reported, displayed maxima at intermediate surfactant mole fractions, that is, the non-ideal behavior. The fractional adsorption of Na⁺ per surfactant molecule in the micelles increased gradually with mixing fraction up to 0.82 atX=[SDS]/([SDS]+[C₁₂DAO])=1, while that of Cl^– decreased from 0.25 atX=0 to zero atX>0.4.     

Determination of subnanomolar concentrations of cobalt by adsorptive stripping voltammetry at a bismuth film electrode

Procedures for trace cobalt determinations by adsorptive stripping voltammetry at in situ and ex situ plated bismuth film electrodes are presented. These exploit the enhancement of the cobalt peak obtained by using the Co(II)–dimethylglyoxime–cetyltrimethylammonium bromide–piperazine-N,N-bis(2-ethanesulfonic acid) system. The calibration graph for an accumulation time of 120 s was linear from 2 × 10^–10 to 2 × 10^–8 mol L^–1. The relative standard deviation from five determinations of cobalt at a concentration of 5 × 10^–9 mol L^–1 was 5.2%. The detection limit for an accumulation time of 300 s was 1.8 × 10^–11 mol L^–1. The proposed procedure was applied to cobalt determination in certified reference materials and in tap and river water samples.     

Buffer Standards for the Physiological pH of Zwitterionic Compounds,MOBS and TABS from 5 to 55°C

The values of the second dissociation constant, pK₂, and related thermodynamic quantities of 4-(N-morpholino)butanesulfonic acid (MOBS) and N-tris(hydroxymethyl)-4-aminobutanesulfonic acid (TABS) have already been reported over the temperature range 5–55°C including 37{°}C. This paper reports the pH values of twelve equimolal buffer solutions at designated pH (s) with the following compositions: (a) mixtures of MOBS (0.05 mol-kg^–1) + NaMOBS (0.05 mol-kg^–1); (b) MOBS (0.08 mol-kg^–1) + NaMOBS (0.08 mol-kg^–1); (c) MOBS (0.08 mol-kg^–1) + NaMOBS (0.08 mol-kg^–1) + NaCl (0.08 mol-kg^–1); (d) TABS (0.05 mol-kg^–1) + NaTABS (0.05 mol-kg^–1); and (e) TABS (0.08 mol-kg^–1) + NaTABS (0.08 mol-kg^–1); and (f) TABS (0.08 mol-kg^–1) + NaTABS (0.08 mol-kg^–1) + NaCl (0.08 mol-kg^–1). Two buffer solutions have ionic strengths I= 0.05 mol-kg^–1, another two have I=0.08 mol-kg^–1, and the remaining two buffer solutions have I= 0.16 mol-kg^–1, which is close to that of the clinical fluids (blood serum). These buffers have been recommended as a useful pH standard for the measurements of physiological solutions. Conventional pH values of all six buffer solutions from 5–55°C, as well as those obtained from the liquid junction potential correction at 25 and 37{°}C have been calculated. The flowing-junction calomel cell has been utilized to measure E_j, the liquid junction potential.     

The first ionization constant from 25 to 200°C and 2000 bar for orthophosphoric acid

The ionization constant of orthophosphoric acid, determined by conductivity measurements, decreased from 7.11×10^–3 at 25°C to 6.2×10^–4 mol-kg^–1 at 200°C. The pressure effect to 2000 bar was also measured and the ratio K₂₀₀₀/K₁ is 2.7 at 25°C and 3.7 at 200°C. The standard partial molar volume change for the ionization at 1 bar, , changes from –16.1 at 25°C to –33.3 cm³-mol^–1 at 200°C. The partial molar compressibility change for the ionization, , varies from –3.8×10^–3 to –8.3×10^–3 cm³-mol^–1 bar^–1 over the same temperature range.     

Synthesis and absorption spectra of 3,5-diaryl-1,2,4-triazoles

1,2,4-Triazoles with symmetrical tolyl substituents were obtained from the corresponding 1,3,4-oxadiazoles by reaction with formamide and subsequent hydrolysis of the resulting formyl derivatives; 1,2,4-triazoles with unsymmetrical substituents were obtained from iminoesters and hydrazides of acids. A set of bands of the triazole ring at 1470–1480, 1390, 1270–1290, 1140–1150, and 725–750 cm^–1 and of NH vibrations at 2400–3200, 1580–1620, and 830–900 cm^–1 are characteristic for the IR spectra of these triazoles. The UV spectra of the triazoles are characterized by phenyl ring absorption at about 200 nm and a band of electron transitions between the phenyl and triazole rings at 230–290 nm.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1682–1685, December, 1977.     

A field-desorption study of thermal stability in potassium pentacyanocobaltates(III)

Field desorption has been applied to research the thermal stability of the compounds K_n[Co(CN)₅X], where X=SO₃ ^2–, CN^–, NO₂ ^–, NO^–, Cl^–, Br^–, I^–, and H₂O. A likely mechanism is proposed for the thermal decomposition. There is a correlation between the tetragonal-distortion parameters and the temperature of onset of destruction for the [Co(CN)₅X]^n– anion.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 111–115, January–February, 1985.     

Diels-Alder reaction volumes in the solid state and solution

The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm³ mol^–1), and slightly different from the reaction volumes (–8±1 cm³ mol^–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm³ mol^–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004.