RESUMO
This work details a simple and original approach for the generation of linear gradients inside straight cylindrical microchannels such as a capillary column. The concept takes advantage of an oft-overlooked regime of dispersion of flowing liquids inside narrow channels: the ballistic regime. The ballistic regime is a pure convective regime and is produced by imposing a high velocity flow in a pre-filled capillary thus limited diffusion takes place. This is obtained by forcing the injection of a plug of solution on a short time scale t, much shorter than t<110×D/r2, D is the diffusion coefficient and r the capillary radius. The result is a stretched solution of a given length or depth of penetration, inside the capillary column. This leads to a linear mean concentration field through the mixing zone forming a linear gradient. In miniaturized systems, this transient regime is followed by mainly radial diffusion of the solution inside the capillary due to the short characteristic diffusion time of narrow channels. A convection-diffusion simulation was used to model the gradient formed under this ballistic regime. A specific experimental prototype set-up was designed to investigate this ballistic regime and the formation of a linear gradient of titrant NaOH solution inside a capillary tubing of 500 µm inner diameter and 35-cm total length pre-filled with nitric acid solution. With this prototype, the linear gradient was then pushed in a non-ballistic regime over a confocal fluorescence point detection system in order to measure the fluorescence emission of a fluorescent dye added to the solutions. Considering strong acid-base reaction, fluorescein was used due to its strong fluorescence dependency with pH near its pKa, i.e 6.4. A first set of experiments was realized to demonstrate the validity of such an approach and to determine the optimal condition for the formation of a linear gradient over 300 mm of the 350-mm capillary length. An injection pressure of 1000-mbars over 0.75 s was chosen. The first result was the stability of the system in its ability to produce reproducible linear gradients. As further proofs of feasibility, samples of different nitric acid concentrations were titrated with a 0.25 M NaOH solution. The result was rapid and reproducible titration curves obtained with a fully automated system that consumes less than approximately 70 µL of sample solution.
RESUMO
A miniaturized and automated approach for the determination of free acidity in solutions containing uranium (VI) is presented. The measurement technique is based on the concept of sequential injection analysis with on-line spectroscopic detection. The proposed methodology relies on the complexation and alkalimetric titration of nitric acid using a pH 5.6 sodium oxalate solution. The titration process is followed by UV/VIS detection at 650nm thanks to addition of Congo red as universal pH indicator. Mixing sequence as well as method validity was investigated by numerical simulation. This new analytical design allows fast (2.3min), reliable and accurate free acidity determination of low volume samples (10µL) containing uranium/[H(+)] moles ratio of 1:3 with relative standard deviation of <7.0% (n=11). The linearity range of the free nitric acid measurement is excellent up to 2.77molL(-1) with a correlation coefficient (R(2)) of 0.995. The method is specific, presence of actinide ions up to 0.54molL(-1) does not interfere on the determination of free nitric acid. In addition to automation, the developed sequential injection analysis method greatly improves the standard off-line oxalate complexation and alkalimetric titration method by reducing thousand fold the required sample volume, forty times the nuclear waste per analysis as well as the analysis time by eight fold. These analytical parameters are important especially in nuclear-related applications to improve laboratory safety, personnel exposure to radioactive samples and to drastically reduce environmental impacts or analytical radioactive waste.