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Trace Level Determination of Low-Molecular-Weight Alcohols in Aqueous Samples Based on Alkyl Nitrite Formation and Gas Chromatography

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Trace Level Determination of Low-Molecular-Weight Alcohols in Aqueous Samples Based on Alkyl Nitrite Formation and Gas Chromatography ANALYTICAL SCIENCES MAY 2001, VOL. 17 639 2001 © The Japan Society for Analytical Chemistry Trace Level Determination of Low-Molecular-Weight Alcohols in Aqueous Samples Based on Alkyl Nitrite Formation and Gas Chromatography Ha Thi-Hoang NGUYEN, Norimichi TAKENAKA,† Hiroshi BANDOW, and Yasuaki MAEDA College of Engineering, Osaka Prefecture University, Gakuencho, Sakai, Osaka 599–8531, Japan A simple and sensitive method for the determination of liquid methanol and ethanol at trace levels by an alkyl nitrite formation reaction has been established. Alcohol was allowed to react with nitrous acid, which was yielded from sulfuric acid and sodium nitrite in the solution, to form the corresponding alkyl nitrite in the hexane organic phase. Alkyl nitrites in hexane were analyzed by a gas chromatograph with an electron capture detector (GC-ECD). The detection limits, which were determined at a signal-to-noise ratio of 3, were 1.1 and 0.7 µg/L for methanol and ethanol, respectively, by 1 µL injection. The relative standard deviations for n = 8 were 4.0 and 3.3% for methanol and ethanol, respectively. The method was applied to determine the alcohol concentration in a rice paddy, pond water, tap water, and well water. Those aqueous samples were also spiked with standard alcohols; the average recoveries of spiked methanol and ethanol were 98 and 91% with relative standard deviations of 6.1 and 4.0%, respectively. (Received August 17, 2000; Accepted October 2, 2000) these reagents are very unstable, overall, it is not simple to Introduction determine alcohols at the trace level. Alkyl nitrites were found to be a good derivatization for alcohol determination, and Alcohols are a group of important organic compounds popularly alcohol in the gas phase at the trace level was successfully used as solvents in laboratories, industries, and households.1 In quantitatively analyzed in an earlier study: alkyl nitrite in the the natural environment, plant and biological objects are a gas phase was formed from a reaction of alcohol and nitrogen variety emission sources of alcohols.2–4 Moreover, alcohols are dioxide on a Pyrex glass surface.11 Alkyl nitrite can also be widely found in beverages, foods, and pharmaceuticals.1,5 formed from an alcohol and nitrous acid reaction, which is Methanol and ethanol are the most popularly used alcohols. conveniently applied for alcohol determination in the aqueous Recently, the use of alcohol fuel as an alternative fuel has phase. In this study, we propose a method for the determination received much attention as a solution for many problems caused of liquid alcohols at µg/L concentrations using the alkyl nitrite by gasoline fuel.6 The determination of alcohol is an important formation reaction. GC-ECD was chosen for an alkyl nitrite subject in the field of analysis. Moreover, in an examination of analysis because of its high sensitivity. The simultaneous the alcohol level due to emission from a plant as well as the existence of many substances in environmental samples usually ambient level of alcohol due to an alcohol-fuel vehicle, a causes many problems in quantitative analysis. In most cases, quantitative-analysis technique at the trace level is required. chromatograms with many unexpected peaks as well as ghost However, the determination of alcohols at the trace level is still peaks might be obtained. These problems can easily be avoided a challenging problem.7 There are many methods reported for by using GC-ECD, which has high selectivity. alcohol determination, such as a conductometric method,8 an In this method, alcohols were allowed to react with nitrous electrochemical fuel-cell method,9 and an infrared absorption acid, which was formed by the reaction of sulfuric acid and method,10 which have detection limits at several ppm (parts per sodium nitrite to form the corresponding alkyl nitrites: million). A method using a dehydrogenase-based biosensor, which received much development for many years, was still H2SO4 + NaNO2 → HONO + Na2SO4, (1) found to have difficulty in measuring alcohols at the ppb (or µg/L) level. Gas chromatography and high-performance liquid ROH + HONO → RONO + H2O. (2) chromatography were also employed for alcohol determinations. In recent years, derivatization techniques for After the yielded alkyl nitrites were then analyzed by GC-ECD, HPLC analysis have received attention because of their highly the alcohol concentration was calculated using a calibrated sensitive detection characteristics. Several types of reagents, conversion factor of each alcohol to its nitrite. such as carbonyl azides and carbonyl chlorides, have been suggested as derivatizations of alcohols. However, the reactions for these derivatizations were under rather strict conditions, Experimental such as at high temperature in the dark etc. Moreover, because All analytical-grade chemicals including methanol, ethanol, † To whom correspondence should be addressed. sulfuric acid, sodium nitrite, and hexane, were obtained from 640 ANALYTICAL SCIENCES MAY 2001, VOL. 17 Wako Pure Chemicals Inc. (Osaka, Japan) and used without further purification. A commercially available ethanol solution of ethyl nitrite was used as its standard. Methyl nitrite standard was synthesized according to a procedure reported by Blatt.12 In order to make a calibration graph for alcohol determination, diluted alcohol standards were prepared by dissolved liquid alcohol (>99.5%) in Milli-Q water (resistance >18 MΩ cm). Liquid samples, such as water from a lake, and rice paddy were first filtered by a coarse filter, and then by a membrane filter. The liquid sample obtained through a membrane filter size of 0.45 µm was used for the analysis. After 3 g of sodium nitrite was dissolved in 30 mL of an alcohol sample, 2 mL of sulfuric acid was dissolved in a 20 mL alcohol sample solution; then 2 mL of hexane, which would be an organic solvent for any yielded alkyl nitrite, was added to the sodium nitrite/alcohol sample solution. All of the sulfuric acid/20 mL alcohol solution, which was set in a separating funnel, was slowly flowed into a sodium nitrite/alcohol sample solution, which was set in an Erlenmeyer flask while the reaction mixture (in Erlenmeyer flask) was being stirred by a stirrer. The flow rate into the sodium nitrite/alcohol sample was Fig. 1 Typical chromatogram of alkyl nitrites yielded from regulated by a screw of the separating funnel. Because alkyl alcohols in a rice paddy (enlarge 2:1). 1, peak of nitrous acid; 2, peak of methyl nitrite; 3, peak of ethyl nitrite; 4, peak of hexane. nitrites are harmful if inhaled continuously, the reaction should be run in a hood. After all of the sulfuric acid/alcohol solution had flowed completely into the sodium nitrite mixture, the reaction mixture was extracted, alkyl nitrite in the hexane phase Optimum concentrations of sulfuric acid and sodium nitrite for was washed with water, and the 1 µL hexane phase was injected alkyl nitrite formation reaction into GC-ECD. The yielded alkyl nitrites and that dissolved in The effect of the sulfuric acid and sodium nitrite hexane were analyzed by GC-ECD. A GC analysis was concentrations on the nitrite formation reaction was examined performed using a Shimadzu GC-4CM gas chromatograph fitted with a concentration range of sulfuric acid of 0.2 – 1.1 mM (Fig. with a Teflon column (3 mm inner diameter, and 4 m length). 3A) and a sodium nitrite concentration of 1 M (the sodium The carrier gas was nitrogen with a flow rate of 40 mL/min. nitrite concentration for the maximum yield of alkyl nitrite was The column was packed with tricresyl phosphate on a previously estimate). The results show that the yield of alkyl Chromosorb W-AW (60 – 80 mesh). The temperature of the nitrite reached the maximum value when the concentration of injection-port, detector, and column was 25˚C. A sulfuric acid was higher than 0.7 mM. The optimum chromatogram of the alkyl nitrites from alcohols from a rice concentration of sodium nitrite was also studied. The examined paddy is shown in Fig.1. concentration range of sodium nitrite was 0.2 – 1.8 M. The nitrite formation was recorded for the reaction of alcohols with a solution having a various sodium nitrite concentration and 0.7 Results and Discussion mM sulfuric acid. As shown in Fig. 3B, the optimum concentration of sodium nitrite was 0.9 M. Organic solvent for yielded alkyl nitrite We chose 0.7 mM sulfuric acid and 0.9 M sodium nitrite Several organic solvents, including isopropyl ether, 1-butyl concentrations for an alkyl nitrite formation reaction from ether, dimethoxy methane, hexane, cyclohexane, toluene, alcohol. benzene, and m-xylene, were examined for their applicability of alkyl nitrite solvent. After 60 and 40 pmol of methyl nitrite and Stable time of alkyl nitrite yielded ethyl nitrite standards, respectively, were injected to 2 mL of Figure 4 shows the stability of alkyl nitrite/hexane while it each organic solvent, 1 µL of the each solution was injected to was being stored from the time of extracting out of an the GC-ECD, and the peak area for each was recorded. The alcohol/nitrous acid reaction mixture. The alkyl nitrite dissolved efficiency was defined as the ratio of the peak area by concentrations were stable until 50 min of storage, and then 1 µL organic solvent added nitrites and the peak area by direct started to undergo decomposition. The result shows that alkyl injection to GC-ECD of 0.03 and 0.02 pmol of methyl and ethyl nitrites were stable in hexane sufficiently long for an analysis. nitrite standards, which contained the same amount of nitrites in 1 µL organic solvent injected if the alkyl nitrite completely Calibration graph, detection limit, and reproducibility of dissolved in the solvent.
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