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Superheated Water Eluent Capillary Liquid Chromatography

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Superheated Water Eluent Capillary Liquid Chromatography Talanta 56 (2002) 977–987 www.elsevier.com/locate/talanta Superheated water eluent capillary liquid chromatography T. Scott Kephart, Purnendu K. Dasgupta * Department of Chemistry and Biochemistry, Texas Tech Uni6ersity, Lubbock, TX 79409-1061, USA Received 24 January 2001; accepted 12 February 2002 Abstract A capillary scale reverse phase liquid chromatography (LC) system using a super hot water eluent is described. The system, constructed in-house from readily available components, has been shown to operate at temperatures as high as 370 °C and pressures in excess of 10 000 psi. The capability of the system is demonstrated with the separation of a mixture of polar and non-polar benzene derivatives on polybutadiene and elemental carbon modified zirconia packings with or without temperature gradients. Six benzene derivatives can be separated in 2 min. © 2002 Elsevier Science B.V. All rights reserved. 1. Introduction Throughout the temperature range above its nor- mal boiling point up to the supercritical tempera- The environmental impact of organic solvents ture, liquid water exhibits a much lower dielectric and the consequent economics of their disposal constant than room temperature water and is has provided much impetus to limit their con- likely less aggressive than supercritical water. The sumption or to eliminate their use altogether. In dielectric constant, viscosity and hydrogen bond- 1995, Hawthorne et al. demonstrated that super- ing of water changes continuously from room critical water at 400 °C and 350 bar can be used temperature up to supercritical conditions; these to extract non-polar analytes such as polycyclic are the properties that are likely to influence the aromatic hydrocarbons (PAHs) and polychlori- behavior of water as a liquid chromatographic nated biphenyls (PCBs) from contaminated soil eluent. samples [1,2]. Under these extreme conditions, the Foster and Synovec were the first to explore the dielectric constant of water is greatly reduced [3]. reduction of the stationary/mobile phase ratio to Supercritical water is a very aggressive solvent exploit the use of pure water as an LC eluent with that readily oxidizes or decomposes many sub- highly polar stationary phases. Separations could stances; supercritical water treatment has been be accomplished at room temperature but efficien- studied as a method to decompose toxic waste [4]. cies for non-polar analytes were modest [5]. In the same year, the spectrometric advantage of a pure superheated water eluent, in that it was transpar- * Corresponding author. Tel.: +1-806-742-3067; fax: +1- 806-742-1289. ent even down to 190 nm was pointed out by E-mail address: [email protected] (P.K. Dasgupta). Smith and Burgess [6]. Miller and Hawthorne first 0039-9140/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved. PII: S0039-9140(02)00049-8 978 T. Scott Kephart, P.K. Dasgupta / Talanta 56 (2002) 977–987 used a traditional reversed phase (ina2mm to 400 °C and pressures up to 11,000 psi with column format) and utilized the temperature ef- water as an eluent. When no back pressure is fect on the solvent properties of water, with ther- applied at the column exit with an FID as a mal gradients to 175 °C to separate alcohols, detector, the effluent is obviously in the gas phase. polyhydroxybenzenes and amino acids [7]. About At what point does the liquid turn in to gas? the same time, Smith and Burgess separated phe- Early studies of gas chromatography with FID nols, barbiturates and parabens on traditional detectors that use steam as the mobile phase are PS-DVB and ODS-bonded silica columns with well known [16,17]. Do the present separations water as hot as 200 °C [8]. Yang et al. were the with FID detection represent gas, or liquid phase first to study the elution of non-polar aromatic separations, or both? hydrocarbons on traditional reversed phases using water up to 200 °C [9]. It has been shown that buffering components can also be put in the hot 2. Experimental section water eluent [10]. The absence of carbon containing compounds The pumping system shown in Fig. 1 is similar in a pure water eluent allows the use of detection to the home-built gradient pumping system de- methods that are difficult or impossible to use scribed in a previous paper [18], except that only with conventional eluents. The use of a flame a single pump is required in the present work. The ionization detector (FID) can be particularly at- output from the pumping system is connected tractive [7,11]. In addition to the traditional UV– with 0.25 mm i.d. stainless steel tubing to a high Vis detector, Smith et al. showed the facile pressure inline check valve CV (cartridge applicability of NMR and MS detectors to a CV3000; Upchurch scientific, Oak Harbor, WA). superhot D2O eluent LC system with tempera- The check valve housing was machined in-house tures to 190 °C [12]. They also authored a thor- out of poly(etheretherketone) (PEEK) to handle ough review documenting the manifold utility of a pressures over 10 000 psi. The high-pressure side water eluent as hot as 240 °C [13]. One particu- of the check valve is then connected to a pressure larly noteworthy aspect is that of many analytes sensor and gauge PG (0–10 000 psi with 50% investigated, very few actually decomposed under overranging capability, model SP70-A10000, the conditions of the separation. Senso-Metrics, Simi Valley, CA) to continuously A few questions remain: for thermally stable monitor system pressure. analytes, what is the practical upper limit of the separation temperature given the most thermally stable stationary phase currently available? How fast can such separations be carried out if one takes advantage of the decreased viscosity? We attempt to answer these questions using a capil- lary scale system. The low flow rates and the small thermal mass in the capillary scale allow rapid temperature ramps and greatly facilitate radial heat transfer, thus minimizing radial temperature gradients [14]. The complexity of interfacing to detectors that are intrinsically compatible with a low flow rate (e.g. mass spectrometers) is also reduced. Coupling of a capillary scale water elu- ent LC system to an FID was reported during the Fig. 1. Hot water chromatography system, schematically preparation of this paper [15]. We report here the shown. CV, check valve; PG, pressure sensor and gauge; SSC, capillary scale separation of hydrophilic and hy- silica saturation column; CH, column heater; BPC, back pres- drophobic benzene derivatives at temperatures up sure column. T. Scott Kephart, P.K. Dasgupta / Talanta 56 (2002) 977–987 979 A silica pre-saturator is used to minimize the For thermal gradient separations using an FID dissolution of silica from the capillary wall (not detector, the column was placed in a gas chro- the column, the packing is not silica based) by the matography oven (Model 4300SX, Varian Inc., superhot water, a silica saturator (4.6×40 mm controlled by Varian Star 4.5 software) with the stainless steel guard column packed with 200 column outlet being directly connected to the FID mesh silica gel) was placed ahead of the injector. inlet (held at 275 °C). Others have previously A separate siliconized band heater was used to looked into optimizing the hydrogen and air flows heat the pre-saturator. This column is heated to a to the FID for maximizing the signal to noise temperature approximately 50 °C lower than the ratio. We made only crude adjustments to obtain column temperature: overheating the pre-satura- reasonable signals, no detailed sensitivity opti- tor can result in dissolved silica subsequently de- mization was carried out since improving detec- positing in the injector which is cooler (vide tion sensitivity was not an objective of this work. infra). An electrically actuated injection valve No back pressure regulator was used after the equipped with a 20 nl internal sample loop (model column and no modifications were made to the C2XL, Valco Instruments, Houston, TX, rated at FID. 15 000 psi) was connected to the guard column Water used in the experiments was distilled and and used for sample introduction. To prevent the then further purified in a Barnstead Nanopure sample from boiling before injection, the injector system. Fused silica capillaries (Polymicro Tech- loop was cooled externally by closed-loop pump- nologies, Phoenix, AZ), hydrogen (ultrapure grade, Airgas, Lubbock, TX), benzene derivatives ing of cold ethanol from a 100 ml reservoir kept (reagent grade, Aldrich) were obtained as in an ice bath through 2.5 mm i.d. Tygon tubing, indicated. wrapped around the sample loop casing with a Fused silica capillary columns (360 and 180 mm variable-speed pump drive (Model 75225, Cole i.d., Polymicro Technologies, Phoenix, AZ) were Parmer). No deposition of silica in the injector packed in-house with frits made after Kennedy was noted, either the eluent does not stay long and Jorgenson as previously described [18]. For enough in the injector or any deposited material is use with the UV detector, the frit was placed 10 washed out during sample loading. m cm from the exit end of the capillary. With the The analytical column was inserted in a 450 m FID, the frit was placed at the very end. The bed i.d. stainless steel tube around which heating tape length was 13 cm for all reported results. Two was wrapped. A layer of aluminium foil, a 1-inch different 3 mm diameter zirconia based packing thick layer of glass wool and another layer of materials were used: (a) ZrO2 modified with aluminium foil, each tightly wrapped, completed polybutadiene; and (b) ZrO2 modified with ele- the column heating enclosure CH.
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