Determination of Trace Amount of Silver by Atomic-Absorption-Spectrometry-Coupled Flow Injection On-Line Coprecipitation Preconcentration Using DDTC–Copper as Coprecipitate Carrier

A flow injection on-line coprecipitation preconcentration system with diethyldithiocarbamate (DDTC) chelate of copper used as the coprecipitate carrier was coupled with flame atomic absorption spectrometry (FAAS) for the determination of trace silver. Silver was on-line coprecipitated with DDTC-Cu(II) in 0.5 moL · L⁻¹HCl, and the precipitate was collected in a knotted reactor. The precipitate was then dissolved by isobutyl methyl ketone and transported directly into the nebulizer–burner system of a flame atomic absorption spectrometer. A detection limit (3ς) of 0.6 μg · L⁻¹was achieved for a loading period of 30 s, a relative standard derivation of 2.0% was obtained for 11 determinations of 20 μg · L⁻¹Ag(I). Interference-free levels were 10 mg · L⁻¹for Cd²⁺, 50 mg · L⁻¹for Cu²⁺, 50 mg · L⁻¹for Mn²⁺, 25 mg · L⁻¹for Ni²⁺, 100 mg · L⁻¹for Pb²⁺, 50 mg · L⁻¹for Zn²⁺, 500 mg · L⁻¹for Fe³⁺, and 2000 mg · L⁻¹for Fe²⁺reduced from Fe³⁺by ascorbic acid. The developed method has been successfully applied to the determination of trace amount of silver in geological samples.     

Copper(II)-cetyltrimethylammonium chloride-chromal blue G ternary complex and its application to the spectrophotometric determination of copper(II)

A sensitive spectrophotometric method for the determination of copper(II) based on a ternary complex with chromal blue G, a triphenylmethane reagent in the presence of cetyltrimethylammonium chloride, is described. The sensitivity of color reaction between copper and chromal blue G has been greatly increased by the sensitizing action of cetyltrimethylammonium chloride, a cationic surfactant. The color development of the ternary complex can be utilized in the highly sensitive spectrophotometric determination of copper. The molar absorptivity of the binary complex between copper and chromal blue G ε_630nm = 9.56 × 10³liters · mol⁻¹ · cm⁻¹ is enchanced on ternary complex formation to ε_{542 nm} = 4.78 × 10⁴liters · mol⁻¹ · cm⁻¹. The ternary complex gave a maximal absorbance at 542 nm in the pH range 9.8–11. Beer's law is obeyed up to at least 1.2 ppm of copper. The maximal absorbance of the ternary complex was found to develop within 5 min and then it remains constant for several hours. The formation constant of the ternary complex is calculated to be 8.6 × 10¹⁰ under these conditions.     

Spectrophotometric determination of titanium (IV) with chlorpromazine hydrochloride

Spectrophotometric Determination of Titanium(IV) with Chlorpromazine HydrochlorideThe extraction of titanium(IV)-thiocyanate complex from hydrochloric acid with chlorpromazine (CPA) dissolved in chloroform has been studied. The composition of the extracted species was found to be (CPAH⁺)₂[Ti(CNS)₆²⁻]. This complex, dissolved in chloroform, has maximum absorbance at 417 nm and a molar absorptivity of 2.6 × 10⁴ mol⁻¹ · cm⁻¹ · liter. Titanium(IV) was determined spectrophotometrically in the organic phase. Beer's law is obeyed in the titanium concentration range 0.2-2.2 μg/ml.     

A study of the spectrophotometric determination of traces of cadmium(II) and copper(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in the presence of polyglycol octylphenyl ether

A spectrophotometric study of the Cd(II) and Cu(II) complex of a new reagent, 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol (5-Br-PADAP) in the presence of polyglycol octylphenyl ether (OP) is presented. A reddish binary complex is formed at pH 9 and shows maximal absorbance at 560 nm with molar absorptivity of 1.16 × 10⁵ · mol⁻¹ · cm⁻¹ liter (Cd), 1.5 × 10⁵ mol⁻¹ · cm⁻¹ · liter (Cu). Beer's law is followed over the range 0.0 to 20 μg cadmium(II) and 0.0–18 μg copper(II). The continuous variation method and molar ratio method showed that the metal ligand ratio is 1:2; ordinarily, most ions do not interfere with the determination and the method can be applied for direct spectrophotometric determination of cadmium(II) and copper(II) in actual samples and the results obtained are satisfactory.     

Voltammetry and electrochemical stripping analysis for antimony in aqueous and nonaqueous media after extraction

Cyclic voltammetry of antimony was studied in aqueous media (HCl-LiCl) and in nonaqueous media after extraction with 20% tri-n-butylphosphate in toluene, with a rotating glassy carbon disc electrode. Reduction of antimony to the element in aqueous media is nearly reversible, but irreversible in nonaqueous media. Anodic stripping voltammetric and chronopotentiometric determinations were also studied in nonaqueous media; methanol and LiCI, NH₄SCN or NH₄NO₃, were used as base electrolytes. In nonaqueous media, antimony can be determined down to concentrations of 1O⁻⁸ M by stripping voltammetry, and lO⁻⁷ M by stripping chronopotentiometry. Electrochemical stripping determinations of 10⁻⁶ M antimony(III) were not affected by Co²⁺, Ni²⁺, Cd²⁺, Zn²⁺ or As³⁺ (5 · 10⁻³ M), ag⁺ (4 · 10⁺⁴ M in stripping voltammetry or 10⁻³ M in stripping chronopotentiometry), Hg²⁺ (5 · 10⁻⁴M), Pb²⁺ (3 · 10⁻⁴ M), Cu²⁺ (1.5 · 10⁻⁴ M)Sn²⁺ and Sn⁴⁺ (7 · 10⁻⁴ M), Fe³⁺ (4 · 10⁻⁴ M), Au³⁺ (5 · 10⁻⁵ M) and Bi³⁺ (1.5 · 10⁻⁵ M). Thestripping chronopotentiometric determination showed better selectivity.     

Column Preconcentration of Aluminum and Copper(II) in Alloys, Biological Samples, and Environmental Samples with Alizarin Red S and Cetyltrimethylammonium-Perchlorate Adsorbent Supported on Naphthalene Using Spectrometry

A column method has been established for the preconcentration of aluminum and copper(II) with Alizarin Red S and a cetyltrimethylammonium-perchlorate ion pair supported on naphthalene, using a simple glass-tipped tube. Aluminum and copper(II) react with Alizarin Red S to form water-soluble colored chelate anions. These chelate anions form water-insoluble ternary complexes with the adsorbent on the inactive surface of naphthalene packed into a column. They are quantitatively retained in the pH ranges of 4.7-5.2 for aluminum and 5.0-10.0 for copper. The solid mass is dissolved out from the column with 5 ml of dimethylformamide (DMF) for aluminum and 5 ml of ethanol for copper and the absorbance was measured with a spectrometer at 525 nm for aluminum and at 529 nm for copper. The calibration curves were linear over the concentration ranges of 0.25-5.0 μg of aluminum in 5 ml of DMF solution and 0.50-12.0 μg of copper in 5 ml of ethanol solution. The molar absorptivities and Sandell′s sensitivities were respectively calculated to be 2.8 × 10⁴ liter · mol⁻¹ · cm⁻¹ and 9.62 × 10⁻⁴ μg · cm⁻² for aluminum and 2.5 × 10⁴ liter · mol⁻¹ · cm⁻¹ and 2.5 × 10⁻³ μg · cm⁻² for copper. Seven replicate determinations of sample solutions containing 2.5 μg of aluminum and 6.0 μg of copper gave mean absorbances of 0.520 and 0.480 with relative standard deviations of 1.67 and 0.33%, respectively. Interference due to various foreign ions has been studied and the method has been applied to the determination of aluminum in standard alloys, tea leaves, vehicle particulates, copper in coal fly ash, and commercial salt samples.     

Dynamical Spin Chirality and Magnetoelectric Effect of α-Glycine

Dynamical spin chirality of α-glycine crystal at 301−302 K was investigated by DC (direct current)-magnetic susceptibility measurement at temperatures ranging from 2 to 315 K under the external magnetic fields (H=±1 T) parallel to the b axis. The α-glycine crystallizes in space group P2₁/n with four molecules in a cell, which has centrosymmetric charge distribution. The bifurcated hydrogen bonds N⁺(3)−H(8)···O(1) and N⁺(3)−H(8)···O(2) are stacked along the b axis with different bond intensities and angles, which form anti-parallel double layers. Atomic force spectroscopy result at 303 K indicated that the surface molecular structures of α-glycine formed a regular flexuous framework in the b axis direction. The strong temperature dependence is related to the reorientation of NH³⁺ group and the electron spin flip-flop of (N⁺H) mode. Under the opposite external magnetic field of 1 T and −1 T, the electron spins of N⁺(3)−H(8)···O(1) and N⁺(3)−H(8)···O(2) flip-flop at 301−302 K. These results suggested a mechanism of the magnetoelectric effect based on the dynamical spin chirality of (N⁺H), which induced the electric polarization to produce the onset of pyroelectricity of α-glycine around 304 K.     

Rapid analysis of cation-exchangeable property in acidic soil : III. Sensitive spectrophotometric determination of microgram amounts of exchangeable magnesium with xylidyl Blue I in the presence of cetyltrimethylammonium bromide (CTAB)

A simple and sensitive procedure for Spectrophotometric determination of exchangeable magnesium has been developed. At 0.15 – 0.375 N ammonia, magnesium reacts with xylidyl Blue I in the presence of CTAB to form a colored ternary complex, which has an absorption maximum at 524 nm. The molar absorption coefficient is 2.2 × 10⁴ liters · mol⁻¹ · cm⁻¹. The Beer rule will be valid for concentrations from 0 to 8 μg/20 ml magnesium. The method has been used for rapid determination of microgram amounts of exchangeable magnesium in acidic soil with good reproducibility.     

A new Tb-selective fluorescent sensor based on 2-(5-(dimethylamino)naphthalen-1-ylsulfonyl)-N-henylhydrazinecarbothioamide

A novel fluorescent chemosensor 2-(5-(dimethylamino)naphthalen-1-ylsulfonyl)-N-phenylhydrazinecarbothioamide (L) has been synthesized, which revealed an emission of 530 nm and when excited at 360 nm. The fluorescent probe undergoes a fluorescent emission intensity quenching upon binding to terbium ions in MeCN solution. The fluorescence quenching of L is attributed to the 1:1 complex formation between L and Tb(III) which has been utilized as the basis for the selective detection of Tb(III). The linear response range covers a concentration range of Tb(III) from 4.0 × 10⁻⁷ to 1.0 × 10⁻⁵ M and the detection limit is 1.4 × 10⁻⁷ M. The association constant of the 1:1 complex formation for L–Tb⁺³ was calculated to be 6.01 × 10⁶ M⁻¹, and the fluorescent probe exhibits high selectivity over other common metal ions mono-, di-, and trivalent cations indicate good selectivity for Tb(III) ions over a large number of interfering cations.     

Extraction-spectrophotometric determination of vanadium with 5,5′-dithiodisalicylhydroxamic acid (DTDSHA)

A new method for the extraction-spectrophotometric determination of V(V) is proposed. The violet complex V(V)-5,5′-dithiodisalicylhydroxamic acid formed in aqueous medium (pH 5.0) is extracted into a solution of trioctylmethylammonium chloride (Adogen 464) in toluene, and its spectrophotometric characteristics are studied. The stoichiometry of the complexes formed is 1:1 and 2:1 (reagent:vanadium), and 1:3 for the ionic association complex (2:1):trioctylmethylammonium ion. The system follows Beer's law at pH 5.0 (λ = 550 nm) over the concentration range 0.4 to 2.0 ppm (ε = 7.34 × 10³ liter · mol⁻¹ · cm⁻¹). The method is applied for the determination of vanadium in steel.     

Solid substrate-room temperature phosphorimetry for the determination of trace protein using ion association complex [Cu(BPY)2]·[(Fin)2] as a phosphorescent probe

Fluorescein (HFin) emitted strong and stable room temperature phosphorescence (RTP) on filter paper after set at 50 °C for 10 min using Li⁺ as the ion perturber. HFin existed as Fin⁻ when the pH value was in the range of 5.45–7.36. Fin⁻ could react with [Cu(BPY)₂]²⁺ (BPY: α,α-bipyridyl) to produce ion association complex [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻, which could enhance the RTP signal of Hfin. In the presence of bovine serum albumin (BSA), the –COOH group of Fin⁻ in the [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻ could react with the –NH₂ group of BSA to form the ion association complex [Cu(BPY)₂]²⁺·[(Fin-BSA)₂]²⁻, which contained –CO–NH– bond. This complex could sharply enhance the RTP signal of Hfin and the ΔI_p was directly proportional to the content of BSA. According to the facts above, a new solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace protein had been established using the ion association complex [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻as a phosphorescent probe. This method had wide linear range (0.40 × 10⁻⁹–280 × 10⁻⁹ mg l⁻¹), high sensitivity (the detection limit (LD) was 1.4 × 10⁻¹⁰ mg l⁻¹), good precision (RSD: 3.4–4.9%) and high selectivity (the allowed concentration of coexistent ions or coexistent materials was high). It had been applied to the determination of the content of protein in 10 kinds of real samples, and the result agreed well with pyrocatechol violet-Mo (VI) method (P.V.M.M.), which indicated it had high accuracy. Meanwhile, reaction mechanism for the determination of trace protein with [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻ phosphorescent probe was also discussed. The academic thought of this research could not only be used to develop many kinds of ion association complex phosphorescent probes, but also provided a new way to promote the sensitivity of SS-RTP.     

Spectrophotometric determination of titanium in plants using 5,5′-thiodisalicylic acid

Titanium (IV) forms a yellow-colored chelate with 5,5′-thiodisalicylic acid, whose sensibility is pD = 6.1 between pH 4 and 6. The stoichiometry of the complex formed is 1:1 at pH 0.5. The system follows Beer's law at pH 4.9 (λ = 385 nm) over the concentration range 0.6–3.2 ppm (ε = 16000 liters · mol⁻¹ · cm⁻¹). The method can be suitably used for determination of titanium in plants.     

Synthesis, crystal structure and magnetic properties of oxo-bridged binuclear iron(III) complex [Fe(phen)2PhCOO]2OCl2·7H2O

An oxo-bridged binuclear iron(III) complex, [Fe(phen)₂PhCOO]₂OCl₂·7H₂O, was synthesized and the crystal structure indicated that two octahedrally coordinated iron(III) ions bridged with oxygen atoms formed a non-linear complex. The bond angle of Fe---O---Fe is 155.6°. The studies of magnetic properties showed that there was strong antiferromagnetic superexchange coupling (J = −80.8 cm⁻) between two S = 5/2 iron(III) ions.     

Equilibrium constant for the reaction Xe + 2Ar XeAr + Ar in the temperature range 150–300 k and the dissociation energy of XeAr

The equilibrium Xe + 2Ar has been investigated in the temperature range 150–300 K using a selected ion flow tube appratus. From the temperature variation of the equilibrium constant the standrad enthalpy change for the reaction is determined to be −25 ± 5 kj mol⁻¹ and the dissociation energy of XeAr⁺ is estimated to be 24 ±5 kj mol⁻¹ (0.25 ± 0.05 eV). At ≈ 150 K the approach to equilibrium is consistent with a rate coefficent of (5 ± 3) × 10⁻²¹ cm ⁶ s⁻¹ for the forward three-body association reaction.     

Flow Injection Chemiluminescence Determination of Isoniazid Using On-Line Electrogenerated Manganese(III) as Oxidant

A novel flow injection chemiluminescence (CL) system for the determination of isoniazid has been proposed. It is based on the direct CL reaction of isoniazid and Mn(III) in sulfuric acid medium. The unstable Mn(III) was on-line electrogenerated by constant current electrolysis. The CL emission intensity was linear with isoniazid concentration in the range 0.1–10 μg/mL; the detection limit was 3.2 × 10⁻² μg/mL. The whole process could be completed in 1 min with a relative standard deviation of less than 5%. The proposed method is suitable for automatic and continuous analysis and has been applied successfully to the analysis of isoniazid in pharmaceutical preparation.     

Kinetics of the R + HBr RH + Br (CH3CHBr, CHBr2 or CDBr2) equilibrium. Thermochemistry of the CH3CHBr and CHBr2 radicals

The kinetics of the reaction of the CH₃CHBr, CHBr₂ or CDBr₂ radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH₃CHBr (or CHBr₂ or CDBr₂) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH₃CHBr₂ (or CHBr₃ or CDBr₃). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH₃CHBr + HBr) and from 288 to 477 K (CHBr₂ + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student’s t values, units in cm³ molecule⁻¹ s⁻¹, no error limits for the third reaction): k(CH₃CHBr + HBr) = (1.7 ± 1.2) × 10⁻¹³ exp[+ (5.1 ± 1.9) kJ mol⁻¹/RT], k(CHBr₂ + HBr) = (2.5 ± 1.2) × 10⁻¹³ exp[−(4.04 ± 1.14) kJ mol⁻¹/RT] and k(CDBr₂ + HBr) = 1.6 × 10⁻¹³ exp(−2.1 kJ mol⁻¹/RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH₃CHBr and CHBr₂ radicals and an experimental entropy value at 298 K for the CH₃CHBr radical were obtained using a second-law method. The result for the entropy value for the CH₃CHBr radical is 305 ± 9 J K⁻¹ mol⁻¹. The results for the enthalpy of formation values at 298 K are (in kJ mol⁻¹): 133.4 ± 3.4 (CH₃CHBr) and 199.1 ± 2.7 (CHBr₂), and for α-C–H bond dissociation energies of analogous compounds are (in kJ mol⁻¹): 415.0 ± 2.7 (CH₃CH₂Br) and 412.6 ± 2.7 (CH₂Br₂), respectively.     

Effect of Cationic Micelles on the Kinetics of Interaction of [Cr(III)-Gly-Gly] with Ninhydrin

The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of chromium dipeptide complex ([Cr(III)-Gly-Gly]²⁺) with ninhydrin under varying conditions has been investigated. The rates of the reaction were determined in both water and surfactant micelles in the absence and presence of various organic and inorganic salts at 70 °C and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Cr(III)-Gly-Gly²⁺] and [ninhydrin]. Increase in the total concentration of CTAB from 0 to 40×10⁻³ mol·dm⁻³ resulted in an increase in the pseudo-first-order rate constant (kψ) by a factor of ca 3. Quantitative kinetic analysis of kψ−[CTAB] data was performed on the basis of the pseudo-phase model of the micelles. As added salts induce structural changes in micellar systems that may modify the substrate-surfactant interactions, the effect of some inorganic (NaBr, NaCl, Na₂ SO₄) and organic (NaBenz, NaSal, NaTos) salts on the rate was also explored. It was found that the tightly bound counterions (derived from organic salts) were the most effective.     

Extractive-spectrophotometric determination of trace amounts of potassium with cryptand 2.2.2 and methyl orange

A spectrophotometric study on the extraction of potassium into chloroform as an ion pair, formed between the cryptand 2.2.2-potassium complex and the highly colored methyl orange counterion, is described. Optimum conditions for extraction are established (potassium recovery 100.2 ± 3.5%) and a new spectrophotometric determination of trace amounts of potassium is proposed (linear working range: 0.3–3.5 ppm of K⁺; apparent molar absorptivity: 2.2 × 10⁴ liters · mol⁻¹ · cm⁻¹; precision, in terms of relative standard deviation: 1.9%). The actual possibilities of predicting relevant analytical performance characteristics (i.e., sensitivity, selectivity, and precision) of these methods in the light of known complexing ability of cryptands in aqueous phase are discussed. The results obtained in this study are compared with those previously obtained using crown ethers as ligands.     

Reaction of (±)-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate {(±)-phosH} with copper(II), cobalt(II) and iron(II) compounds; Identification by x-ray diffraction of [Co(CH3OH)4(H2O)2][(+)-phos][(−)-phos]. 2CH3OH·H2O

[Cu₂(μO₂CCH₃)₄(H₂O)₂], [CuCO₃·Cu(OH)₂], [CoSO₄·7H₂O], [Co((+)-tartrate)], and [FeSO₄·7H₂O] react with excess racemic (±)- 1,1′-binaphthyl-2,2′-diyl hydrogen phosphate {(±)-PhosH} to give mononuclear Cu^II, Co^II and Fe^II products. The cobalt product, [Co(CH₃OH)₄(H₂O)₂]((+)-Phos)((−)-Phos) ·2CH₃OH·H₂O (7), has been identified by X-ray diffraction. The high-spin, octahedral Co^II atom is ligated by four equatorial methanol molecules and two axial water molecules. A (+)- and a (−)-Phos⁻ ion are associated with each molecule of the complex but are not coordinated to the metal centre. For the other Co^II, Cu^II and Fe^II samples of similar formulation to (7) it is also thought that the Phos⁻ ions are not bonded directly to the metal. When some of the Cu^II and Co^II samples are heated under high vacuum there is evidence that the Phos⁻ ions are coordinated directly to the metals in the products.     

Piezoelectric Sensor in Situ Monitoring Adsorption of Fibrinogen and Surfactant onto a Self-Assembled Monolayer of Alkanethiols

This report describes the use of a piezoelectric quartz crystal (PQC) sensor to investigate the nonspecific adsorption of fibrinogen (FN) and sodium dodecyl sulfate (SDS) onto a self-assembled monolayer (SAM) of alkanethiols on gold. The change in adsorption mass was monitored in situ by the PQC sensor. A kinetics model was proposed to describe the adsorption of the FN and SDS on the hydrophobic SAM surface. The adsorption kinetics parameters were determined from the responses of the PQC. The adsorption and desorption rate constants of the FN on the SAM surface were estimated to be (6.18 ± 0.53) × 10³ M⁻¹ s⁻¹ and (6.74 ± 0.72) × 10⁻³ s⁻¹, respectively. The rate constants for the adsorption and desorption of SDS on the SAM are (24.3 ± 1.4 M⁻¹ s⁻¹) and (1.52 ± 0.11) × 10⁻² s⁻¹, respectively. The adsorption of SDS on the SAM was reversible. The fractional coverage of the FN on the SAM surface was estimated from kinetics analyses to be 42–86% for the FN concentration range 25–400 μg/ml. Over 80% of the FN is irreversibly adsorbed on the SAM surface with respect to dilution of the bulk phase. The fraction of FN reversibly adsorbed increases with the bulk concentration of FN.