Use of multivariate curve resolution for determination of chromium in tanning samples using sequential injection analysis

We report a method for determining total chromium in tanning samples using sequential injection analysis (SIA) with a diode-array spectrophotometric detector. With a suitable analytical sequence CrO₄^2– is converted to Cr₂O₇^2– inside the tubes of the SIA system, after total oxidation of chromium(III). A data matrix is obtained and analysed by several chemometric techniques based on multivariate analysis: principal components analysis, simple-to-use interactive self-modelling mixture analysis, and multivariate curve resolution-alternating least-squares. We studied several samples from different stages of a tanning process. Two of these samples were easily oxidized but the others needed more extreme conditions. The analytical sequence prepared, which was based on obtaining a pH gradient and used H₂SO₄ as reagent, is valid and independent of the level of oxidation needed for the sample. We established a calibration model and evaluated the figures of merit. In some samples we found interferents. With this method the amounts of chromium in each sample were quantified and the results were statistically similar to those obtained by use of the reference method, atomic absorption spectrometry.     

Capillary electrophoresis speciation of chromium in leather tanning liquor

We present a method for the speciation of chromium by capillary electrophoresis. Cr(III) was complexed with diethylenetriaminepentaacetic acid (DTPA) to form a negatively charged complex. Using 20 mM phosphate buffer of pH 8 containing 0.5 mM tetradecyltrimethylammonium hydroxide (TTAOH) at a separation voltage of -15 kV, both forms of chromium CrDTPA(2-) and CrO(4) (2-) were separated in less than 6 min. Direct UV detection at 214 nm was used. The effect of the presence of interfering ions was investigated. The application of the developed method to speciation of chromium in tanning liquor is demonstrated. The obtained results have shown a good correlation with those of flame atomic absorbance spectrometry (FAAS), inductively coupled plasma-mass spectrometry (ICP-MS) and UV/VIS spectrophotometry.     

Factorial design for optimising chromium determination in tanning wastewater

A totally automatized procedure for determining chromium by sequential injection analysis (SIA) linked to multivariate curve resolution with alternating least squares (MCR-ALS) is proposed. With this system Cr(III) is oxidised to chromate (Cr(VI)) and this form is then converted to dichromate in order to obtain second order data. The experimental design method was used to establish the best conditions. The identification of the most influential factors was validated using ANOVA tests. We used this method to successfully analyse total chromium in several aqueous tannery samples from various steps of a tanning process. The results from this method and those from the atomic absorbance spectroscopy (AAS) method are comparable. Sample frequency was 30 samples h^− 1.     

制革废水中总铬的萃取光度法测定

研究了在含氯离子的酸性溶液中,用醋酸戊酯萃取二甲基吲哚二羰花青(DIDC)染料与Cr(Ⅵ)配合物,基于此,建立了一种测定Cr(Ⅵ)的新的光度法。结果表明在3 5mol/L～5 0mol/L的HCl介质中,醋酸戊酯对配合物的萃取率最高;最大吸收波长为640nm;摩尔吸光系数为3 6×105L·mol-1·cm-1,检出限为2 0×10-3mg/L,有色溶液的吸光度与Cr(Ⅵ)量在0 01mg/L～2 1mg/L范围内符合比尔定律,加标回收率为96 8%～104 5%(n=6),Cr(Ⅵ)∶Cl-∶DIDC的摩尔比为1∶1∶1。本法测定了制革废水中的总铬含量。     

Ascorbic acid as a potential masking agent in the tanning process. Olated chromium complexes involving ligating ascorbate and bridging sulfate groups

Two polynuclear complexes, a dimer and a tetramer, involving sulfate and hydroxo bridges and ligating ascorbate were isolated from aqueous solutions. Structural formulae are proposed on the basis of microanalytical and thermal analysis results, i.r., ¹³C-n.m.r., mass spectral data and magnetic measurements.     

改性三聚氰胺树脂鞣剂合成

本文采用一种全新的乙醇胺醚化－－助剂体系改性三聚氰胺树脂鞣剂，并通过研究单体，醚化剂，助剂用量，浓度，pH变化等工艺条件，获得了稳定性，水溶性良好的鞣剂产品。     

Standardization of a multivariate calibration model applied to the determination of chromium in tanning sewage

A multivariate standardization procedure was used to extend the lifetime of a multivariate partial least squares (PLS) calibration model for determining chromium in tanning sewage. The Kennard/Stone algorithm was used to select the transfer samples and the F-test was used to decide whether slope/bias correction (SBC) or piecewise direct standardization (PDS) had to be applied. Special attention was paid to the transfer samples since the process can be invalidated if samples are selected which behave anomalously. The results of the F-test were extremely sensitive to heterogeneity in the transfer set. In these cases, it should be taken as an interpretation tool.     

Synthesis and study of MPNS/SMA nano-composite tanning agent

The radical polymerization of maleic anhydride（MA）,styrene（ST）with the vinyl groups introduced onto the surface of the nano-sized silica via solution polymerization method was developed.The methacryloxypropyl nano-sized silica（MPNS）was used as macromonomer and polymerized with maleic anhydride and styrene by initiating with BPO in toluene.The structure and properties of MPNS/SMA nano-composite were characterized by FT-IR spectra and TEM.Meanwhile,it was applied as tanning agent compared with the traditional styrene-maleic anhydride copolymer in leather.It was found that the applied leather had better quality characteristics with the addition of the nano-sized silica.     

新型阻燃性氨基树脂鞣剂的合成

现有的阻燃剂产品多数分解温度低,难溶于水,不易渗透皮革纤维。本文合成的季戊四醇二氢酯羟甲基化三聚氰胺树脂具有高效的阻燃作用,又具有三聚氰胺树脂鞣剂独特的鞣革作用。本文考察其合成工艺条件及其对产品性能的影响因素。     

Use of t-butyllithium as a reducing agent

Details of the first reported use of an alkyllithium reagent for the reduction of a CO bond are presented.     

Use of diamond stock in chromium plating

Cathodic deposition of a chromium coating from the standard electrolyte in the presence of a diamond stock was analyzed. The microhardness and wear resistance of chromium diamond coatings and the effect of the diamond stock on the electrical conductivity and throwing power of the electrolyte were studied.     

Matrix effect in second-order data: determination of dyes in a tanning process using vegetable tanning agents

The aim of this paper is to determine the concentration of three dyes throughout the tanning process of leather using vegetable tanning agents with a sequential injection analyser with second-order data treatment. As the vegetable tanning agents used are highly absorbent species, we focus on three aspects: (i) difficulties with the resolution (ii) the reduction in the working concentration range; and (iii) matrix effects. Ideally, second-order instruments provide “second-order advantage”; i.e. calibration is possible in the presence of uncalibrated interfering species. However, if the interfering species change the instrumental response of the analyte (in scale or shape), standard additions must be used to ensure the accuracy of the estimated analyte concentration. Here we study the presence of matrix effects for three dyes in several samples in order to significantly improve the accuracy of predictions in the presence of such effects. We found that there were matrix effects in at least 80% of the samples with an alpha risk of 5%. We used this method to study the exhaustion of dyes in the dyeing process.     

Use of sodium diisobutylaluminum dihydride as a reducing agent

Summary It has been found that sodium diisobutylaluminum dihydride can be applied for the reduction of different functional groups of organic compounds. Both hydrogen equivalents of the complex are utilized.     

Use of matrix-modifiers in atomic-absorption determination of chromium in argillites

The direct atomic-absorption determination of chromium in argillites, without preliminary concentration and separation, has been studied. A map of selective flame zones for determining Cr in argillites has been designed. An express method for determining Cr in Estonian argillites has been suggested.     

Photolysis of glyoxal in air

The photolysis of glyoxal in synthetic air was investigated in a quartz cell at 298 K using three types of UV sources (TL/12 lamps (275–380 nm), TL/03 lamps (390–470 nm) and mercury lamps (254 nm)) and products were identified and quantitatively analyzed using long-path FTIR spectroscopy. For all light sources, the observed products were CO, HCHO and HCOOH. Absolute quantum yields were determined using Cl₂ and Br₂ as actinometers. Photolysis in the first absorption band of glyoxal, using TL/12 lamps, provided an overall quantum yield of Φ_T = 0.97 ± 0.05, independent of total pressure ranging from 100 to 700 Torr air. The absolute quantum yields obtained with the TL/03 lamps, covering the second absorption band of glyoxal, showed dependency on total pressure, ranging from Φ_T = 0.12 at 100 Torr to Φ_T = 0.042 at 700 Torr, which can be expressed as a Stern–Volmer-type equation 1/Φ_T = (6.80 + 251.8) × 10⁻⁴ × P (Torr).By combining the product yields with literature data, we deduced the detailed picture of glyoxal photolysis, including the dependency of the quantum yield of each particular channel: CHOCHO + hν → 2HCO (Φ₁); CHOCHO + hν → H₂ + 2CO (Φ₂); CHOCHO + hν → H₂CO + CO (Φ₃) on the applied wavelength. The product quantum yields indicate that dissociation into two HCO radicals is the most important pathway under atmospheric conditions. The mean photolysis rate was measured under solar radiation in the EUPHORE outdoor chamber to be J_obs = 1.04 ± 0.10 × 10⁻⁴ s⁻¹, corresponding to a mean effective quantum yield ϕ_eff = 0.035 ± 0.007. Although glyoxal has a very low effective quantum yield, photolysis remains an important removal path in the atmosphere.     

Fluorescence of glyoxal in supersonic jets

Fluorescence excitation spectra have been measured in helium supersonic jets for S₁—S₀ O⁰₀ and 8¹₀ transitions of glyoxal. The polarization of the 8¹₀ transition was determined. The corresponding bands of the glyoxal—He van der Waals complex are absent.     

Electrospun ZnO/TiO2 composite nanofibers as a bactericidal agent

Novel ZnO/TiO(2) composite nanofibers were fabricated by an electrospinning method and showed excellent antimicrobial activity against gram-negative Escherichia coli and gram-positive Staphylococcus aureus under UV irradiation and in the absence of light.