Determination of Alkylphenols after Derivatization to Ferrocenecarboxylic Acid Esters with Gas Chromatography-Atomic Emission Detection

Abstract

A method is described for the rapid determination of alkylphenols in nonpolar matrixes. The alkylphenols are derivatized with ferrocenecarboxylic acid chloride so that every phenol molecule is labeled with one iron atom. The resulting esters are analyzed by gas chromatography with atomic emission detection (AED) in the iron-selective detection mode. This method utilizes the AED's low detection limit (0.05 pg/s) for iron and the high selectivity versus carbon (3.5 x 10(6)) for the detection of the alkylphenols. Because the derivatization is performed before the first step of sample preparation, the risk of analyte loss by adsorption or volatilization is minimized. The total recoveries in the lower ppm concentration range vary between 79 and 125%. The quantification of 20 C0-C3-alkylphenols in crude oils is demonstrated by analyzing a shale oil (SRM 1580) and a petroleum crude oil (SRM 1582). The complete workup is easily carried out in only 45 min/sample.

Ferrocenoyl piperazide as derivatizing agent for the analysis of isocyanates and related compounds using liquid chromatography/electrochemistry/mass spectrometry (LC/EC/MS)

“…The first step consisted of the reaction of the commercially available ferrocenecarboxylic acid to the respective ferrocenecarboxylic acid chloride (FCC) by using oxalyl chloride and catalytic amounts of N,Ndimethylaminopyridine. This procedure was introduced by Rolfes and Andersson [23,24], but for this work, a slightly modified version by Karst et al [40] was applied. FCC was then reacted with an excess of piperazine under formation of Fc-PZ.…”

“…Ferrocenecarboxylic acid chloride was prepared according to literature [23,24,40]: At room temperature, a solution of 1.43 mL (16.6 mmol) of oxalyl chloride in 30 mL of toluene was added to a stirred suspension of 3.0 g (13.0 mmol) of ferrocene carboxylic acid and catalytic amounts (3.5 mg) of DMAP in 35 mL of toluene. The reaction mixture was stirred for 1 h at room temperature.…”

“…Gas chromatography (GC) of ferroceneboronates of diols and related compounds with electron impact mass spectrometric detection was described by Brooks and Cole [22]. Rolfes and Andersson derivatized phenols with ferrocenecarboxylic acid chloride, separated the derivatives by GC, and used the highly selective atomic emission detector for quantification [23,24]. The majority of publications on ferrocene-based derivatizing agents, however, describes the use of LC with electrochemical detection [25][26][27][28][29][30][31][32][33].…”

Solid phase extractive preconcentration coupled to gas chromatography–atomic emission detection for the determination of chlorophenols in water samples

“…Many analytical methods, including capillary electrophoresis [10,11], high-performance liquid chromatography (HPLC) [12] and gas chromatography [1] are available for the determination of CPs in water samples. Gas chromatography (GC), usually after derivatization, with flame-ionization detection (FID) [13,14], electron-capture detection (ECD) [15], mass spectrometric detection (MS) or microwave-induced plasma atomic emission spectrometry (MIP-AES) [16][17][18][19] is a common tool for the determination of phenols because of its high separation power and low limits of quantification.…”

“…This element is easily introduced into phenols through their coupling with the acid chloride of ferrocenecarboxylic acid to yield the ferrocenecarboxylic acid esters (Fig. 1) [17][18][19].…”