Low solubility of unconjugated bilirubin in dimethylsulfoxide – water systems: implications for pKa determinations
BackgroundAqueous pKa values of unconjugated bilirubin are important determinants of its solubility and transport. Published pKa data on an analog, mesobilirubin-XIIIα, studied by 13C-NMR in buffered solutions containing 27 and 64 vol% (C2H3)2SO because of low aqueous solubility of mesobilirubin, were extrapolated to obtain pKa values in water of 4.2 and 4.9. Previous chloroform-water partition data on bilirubin diacid led to higher estimates of its pKa, 8.12 and 8.44, and its aqueous solubility. A thermodynamic analysis, using this solubility and a published solubility in DMSO, suggested that the systems used to measure 13C-NMR shifts were highly supersaturated. This expectation was assessed by measuring the residual concentrations of bilirubin in the supernatants of comparable DMSO-buffer systems, after mild centrifugation to remove microprecipitates.ResultsExtensive sedimentation was observed from numerous systems, many of which appeared optically clear. The very low supernatant concentrations at the lowest pH values (4.1-5.9) were compatible with the above thermodynamic analysis. Extensive sedimentation and low supernatant concentrations occurred also at pH as high as 7.2.ConclusionsThe present study strongly supports the validity of the aqueous solubility of bilirubin diacid derived from partition data, and, therefore, the corresponding high pKa values. Many of the mesobilirubin systems in the 13C-NMR studies were probably supersaturated, contained microsuspensions, and were not true solutions. This, and previously documented errors in pH determinations that caused serious errors in pKa values of the many soluble reference acids and mesobilirubin, raise doubts regarding the low pKa estimates for mesobilirubin from the 13C-NMR studies.
Nonsteroidal Antiinflammatory Drugs, XI:1) Thermodynamic Dissociation Constants of 3‐Substituted 3‐(4‐Biphenylyl)‐3‐hydroxypropionic Acids in Aqueous DMSO
The thermodynamic pKa* values of 3‐substituted 3‐(4‐biphenylyl)‐3‐hydroxypropionic acids 1a‐‐s were determined potentiometrically in DMSO/water (80:20). The mixed solvent was selected for chemical and pharmacological reasons. The results are discussed in terms of substituent effects and solute‐solvent interactions. The estimated pKa values in water are in the range of 3‐‐4, in accordance with data reported in the literature for similar nonsteroidal antiinflammatory agents.
Full-scale measurements of SO2 gas phase concentrations and slurry compositions in a wet flue gas desulphurisation spray absorber
Abstract Two measurement campaigns were carried out at ENERGI E2's Asnaes Power plant, unit 5. The unit has a capacity of 620 MW e and is equipped with a wet flue gas desulphurisation (FGD) plant employing a counter-current spray absorber with five spray levels. In the first campaign, the power plant was firing Orimulsion ® with 2.85 wt% S resulting in a flue gas concentration of SO 2 exceeding 2000 ppmv. In the second campaign, the fuel applied was a low-S blended coal and the SO 2 concentration in the raw gas was around 400 ppmv. A novel probe for in situ sampling of gas phase concentrations in wet FGD spray absorbers was developed and applied for measuring axial profiles of the SO 2 gas phase concentrations in the absorber. The expected decrease in SO 2 concentrations along the height of the absorber was found in the spray section (from height 26.5 to 36.2 m) whereas the SO 2 concentration above the holding tank and below the gas inlet was quite low probably due to long local residence times in the region. Horizontal variations, due to somewhat different flow conditions near the column wall were investigated and the SO 2 concentrations were found to be higher near the wall. Measurements at different gross loads showed that the SO 2 gas phase concentration at a given position inside the absorber was roughly linearly related to the L/G ratio in the measuring interval. Turning off one of the lower spray levels, while burning coal with low S content, did not lower the overall removal efficiency of the absorber. However, the SO 2 gas phase concentration inside the lower part of the absorber was increased by a factor of 2–3. Measurements of slurry pH at different positions showed a decrease of approximately 0.5 units from the upper to the lower part of the absorber. The full-scale measurements provide a detailed set of experimental data for validation of mathematical models of a wet FGD spray absorber.