Joseph A. Jarrell

Achieving quasi-adiabatic thermal environment to maximize resolution power in very high-pressure liquid chromatography: Theory, models, and experiments.

A cylindrical vacuum chamber (inner diameter 5 cm) housing a narrow-bore 2.1 mm×100 mm column packed with 1.8 μm HSS-T3 fully porous particles was built in order to isolate thermally the chromatographic column from the external air environment. Consistent with statistical physics and the mean free path of air molecules, the experimental results show that natural air convection and conduction are fully eliminated for housing air pressures smaller than 10(-4) Torr. Heat radiation is minimized by wrapping up the column with low-emissivity aluminum-tape (emissivity coefficient ϵ=0.03 vs. 0.28 for polished stainless steel 316). Overall, the heat flux at the column wall is reduced by 96% with respect to standard still-air ovens. From a practical viewpoint, the efficiency of the column run at a flow rate of 0.6 mL/min at a constant 13,000 psi pressure drop (the viscous heat power is around 9 W/m) is improved by up to 35% irrespective of the analyte retention. Models of heat and mass transfer reveal that (1) the amplitude of the radial temperature gradient is significantly reduced from 0.30 to 0.01 K and (2) the observed improvement in resolution power stems from a more uniform distribution of the flow velocity across the column diameter. The eddy dispersion term in the van Deemter equation is reduced by 0.8±0.1 reduced plate height unit, a significant gain in column performance.

Quasi-adiabatic vacuum-based column housing for very high-pressure liquid chromatography

A prototype vacuum-based (10(-6)Torr) column housing was built to thermally isolate the chromatographic column from the external air environment. The heat transfer mechanism is solely controlled by surface radiation, which was minimized by wrapping the column with low-emissivity aluminum tape. The adiabaticity of the column housing was quantitatively assessed from the measurement of the operational pressure and fluid temperature at the outlet of a 2.1mm×100mm column (sub-2 μm particles). The pressure drop along the column was raised up to 1kbar. The enthalpy balance of the eluent (water, acetonitrile, and one water/acetonitrile mixture, 70/30, v/v) showed that less than 1% of the viscous heat generated by friction of the fluid against the packed bed was lost to the external air environment. Such a vacuum-based column oven minimizes the amplitude of the radial temperature gradients across the column diameter and maximizes its resolving power.

Maximizing performance in supercritical fluid chromatography using low-density mobile phases.

The performance of a 3.0mm×150mm column packed with 1.8μm fully porous HSS-SB-C18 particles was investigated in supercritical fluid chromatography (SFC) with low-density, highly expansible carbon dioxide. These conditions are selected for the analysis of semi-volatile compounds. Elevated temperatures (>100°C) were then combined with low column back pressures (<100bar). In this work, the inlet temperature of pure carbon dioxide was set at 107°C, the active back pressure regulator (ABPR) pressure was fixed at 100bar, and the flow rate was set at 2.1mL/min at 12°C (liquefied carbon dioxide) and at an inlet column pressure close to 300bar. Nine n-alkylbenzenes (from benzene to octadecylbenzene) were injected under linear (no sample overload) conditions. The severe steepness of the temperature gradients across the column diameter were predicted from a simplified heat transfer model. Such conditions dramatically lower the column performance by affecting the symmetry of the peak shape. In order to cope with this problem, three different approaches were experimentally tested. They include (1) the decoupling and the proper selection of the inlet eluent temperature with respect to the oven temperature, (2) the partial thermal insulation of the column using polyethylene aerogel, and (3) the application of a high vacuum (10-5Torr provided by a turbo-molecular pump) in a housing chamber surrounding the whole column body. The results reveal that (1) the column efficiency can be maximized by properly selecting the difference between the eluent and the oven temperatures, (2) the mere wrapping of the column with an excellent insulating material is insufficient to fully eliminate heat exchanges by conduction and the undesirable radial density gradients across the column i.d., and (3) the complete thermal insulation of the SFC column under high vacuum allows to maximize the column efficiency by maintaining the integrity of the peak shape.

Bridging the gap between gas and liquid chromatography.

The rapid and complete baseline separation of both volatile (C5 to C16 alkanes in gasoline or terpenes in plant extracts) and non-volatile (>C20 alkanes) organic compounds was achieved by combining (1) low-density fluid chromatography (LDFC) using carbon dioxide at elevated temperature (>90°C) and low pressure (1500psi) designed to increase the retention of the most volatile compounds and (2) high-vacuum technology (<10-4Torr) in order to preserve the maximum efficiency of short analytical columns (3.0mm×150mm packed with 1.8μm fully porous HSS-SB-C18 particles) when used in LDFC. The volatile compounds are eluted first under isobaric conditions (1500psi) in less than a minute followed by a linear gradient of the column back pressure (from 1500 to 3500psi in 5min) for the elution of the non-volatile compounds up to C40. The experimental results demonstrate that LDFC performed with short 3.0mm i.d. columns packed with sub-2μm particles and placed under adiabatic conditions enables the analysts to deliver a single, fast, and high-resolution separation of both volatile and non-volatile compounds.