Teaching analytical properties

A new way of expounding analytical properties based on their mutual dependence (complementary and contradictory relationships) and their unequivocal connection with analytical quality facets is presented. To this end, the paper provides answers to the obvious questions that arise in dealing with the subject: why?, how?, when? and where to teach analytical properties in the Analytical Chemistry curriculum?     

DAC-FECS Affairs

DAC-FECS Affairs

The Division of Analytical Chemistry     

Indirect automatic atomic absorption determination of sulphate based on its precipitation with barium

A continuous precipitation flame atomization atomic absorption spectrometric method for the indirect determination of sulphate is proposed. By using a reversed flow-injection configuration for precipitation as barium sulphate, this anion was determined in the range 10–150 g/ml, with a relative standard deviation of 2.6%. The sensitivity was increased by a factor of seven by using a nitrous oxide-acetylene flame to measure barium.     

Coupling continuous flow systems to instruments based on discrete sample introduction

The interfaces between low-pressure continuous sample treatment systems and high-level information instruments such as gas chromatographs, capillary electrophoresis equipment and graphite furnace atomic spectroscopic instruments, which are characterized by conventional discrete sample introduction devices, are presented. The present and future developments are discussed of (directly) linking real samples and those analytical equipments with the main objective of avoiding or minimizing manually implemented preliminary operations of the analytical process. Received: 27 January 1998 / Revised: 5 March 1998 / Accepted: 7 March 1998     

Sequential atomic absorption spectrometric determination of nitrate and nitrite in meats by liquid-liquid extraction in a flow-injection system

Sequential determinations of nitrate and nitrite based on continuous liquid-liquid extraction, and suitable for their routine determinations in meats, are reported. Nitrate reacts with bis(2,9-dimethyl-1,10-phenanthrolinato)copper(I) to form an ion-pair which is extrated into 4-methyl-2-pentanone in a flow-injection manifold. In one aliquot of sample, nitrite is oxidized by cerium(IV), so that total nitrate is determined. In another, nitrite is converted to nitrogen with sulfamic acid, so that only the original nitrate is determined. By measuring the atomic absorption signal of copper in the organic phase, mixtures of these anions can be determined at μg ml^?1 levels for nitrate/nitrite ratios from 10:1 to 1:10, with a sampling frequency of ca. 20 h^–1.     

Automatic determination of total aliphatic amines by on-line photometric liquid-liquid microextraction

An automatic flow method for the determination of total aliphatic amines has been developed. Using an integrated micro extraction unit at the detection point that allows continuous on-line monitoring of small organic plug from which amines are extracted. It is based on the formation of ion-pairs between aliphatic amines and sodium 1,2-naphthoquinone-5-sulphonate that are subsequently extracted into chloroform. The gradual enrichment of the organic phase with the ion-pair is continuously monitored at 460 nm. Absorbance readings at a fixed time and the slopes of absorbance-time recordings are the measured parameters used for determination purposes. The proposed method has been applied to the determination of total aliphatic amines in both synthetic and real (food) samples.     

Screening and analytical confirmation of sulfonamide residues in milk by capillary electrophoresis-mass spectrometry

A new methodology is proposed to automate the monitoring of sulfonamide residues in milk samples. It combines a screening unit for the total amount of sulfonamide with capillary electrophoresis-mass spectrometry (CE-MS) equipment for processing the samples containing a detectable level of sulfonamide. The screening unit consists of continuous-flow system (CFS) to precipitate the proteins connected on-line to the CE-MS equipment, in which a common characteristic ion of all sulfonamides was monitored with the MS detector by flushing the sample through the capillary. The confirmatory method is based on the purification and preconcentration of sulfonamides in a CFS unit and posterior analysis by CE-MS. The sample treatment unit was also on-line connected to the CE-MS equipment. In order to increase sensitivity, the flow rate of the sheath liquid was diminished from 0.5 to 0.2 microL.min(-1) by increasing the content in water from 0 to 50% and the formic acid from 0.5 to 1.5% in this liquid and by applying an overimposed pressure of 5 mbar during the electrophoretic separation. The method allowed the analysis of 30 samples per hour.     

Rapid determination of aliphatic amines in water samples by pressure-assisted monolithic octadecylsilica capillary electrochromatography-mass spectrometry

A pressure-assisted capillary chromatography-mass spectrometry method based on the use of a monolithic octadecylsilica (ODS) capillary is proposed for the determination of aliphatic amines. A 25 mM citric acid buffer containing 10% methanol is used as running electrolyte. Separation is achieved by simultaneously applying a capillary electrophoresis (CE) voltage of 13 kV and an overimposed pressure of 8 bar. The use of pressure is required to ensure stable electrospray conditions. Analysis times are reduced by using a capillary column consisting of a 30 cm long monolithic silica capillary column bound with ODS and a fused-silica capillary column also 30 cm long. The proposed method was successfully applied to the determination of low-molecular-weight aliphatic amines in tap and river water. The analysis of real samples requires cleanup and preconcentration, which can be performed automatically by inserting a minicolumn in the replenishment system of the commercial instrument.     

On-line sorbent extraction, preconcentration and determination of lead by atomic absorption spectrometry

A method for the quantitative preconcentration of lead based on an existing batch process was developed for implementation in a flow system including a flame AAS detector. Lead can be quantitatively preconcentrated as pyrrolidinedithiocarbamate or dithizonate on an activated carbon minicolumn. The chelates are eluted in methyl isobutyl ketone and introduced directly into the nebuliser-burner. An enrichment factor of 50 is typically obtained for a preconcentration time of 2 min (lead can be determined at concentrations between 15 and 400 ng/ml), which results in a throughput of ca. 25 samples per hr. The sensitivity achieved with the two reagents is similar, but the selectivity provided by APDC exceeds that of dithizone. Based on the results obtained in the determination of lead in reference materials (minerals and skim milk), the proposed APDC method is applicable to real samples.     

Kinetic fluorimetric determination of nanogram amounts of manganese, based on its catalysis of the oxidation of 2-hydroxybenzaldehyde thiosemicarbazone with hydrogen peroxide

A kinetic method is described for the determination of trace amounts of manganese(II), based on its catalytic effect on the oxidation of 2-hydroxybenzaldehyde thiosemicarbazone by hydrogen peroxide. The reaction is followed by measuring the rate of change of fluorescence (lambda(ex) 365 and lambda(em) 440 nm). The calibration is linear over the manganese range 2-9 ng ml with a precision of +/-1%. The proposed method suffers from few interferences.