ABSTRACT
The formation of coexisting liquid phases out of aqueous aluminum polyphosphate solutions was previously suggested as an essential step in aluminum polyphosphate nanoparticle formation. This hypothesis could not be directly verified because the separation of the two phases is very difficult, but a different situation was found in the case of chromium (III) polyphosphate. The phase diagram of the sodium polyphosphate-chromium nitrate-water system at 25 degrees C presents an extensive region with two coexisting liquid phases (L-L), together with a single liquid phase (L) and a solid-liquid (S-L) domain. Within the L-L region, admixture of the reagents produces initially a turbid liquid, out of which two transparent liquid phases separate in a short time, under gravity: one is dense, dark, and viscous while the other has a light color and a lower density. The amounts of the separated phases were determined, as well as their viscosities, densities, pH, UV-vis spectra, and relevant molalities: P (from polyphosphate), Cr(3+), NO(-)(3+), and Na(+). The two liquid phases undergo significant color, pH, and viscosity changes with time. The calculated phase diagrams display the major features of the experimental phase diagram.
ABSTRACT
A new route was developed for preparing a series of trans nitrosyl complexes of general formula trans-[Ru(NH(3))(4)L(NO)](BF(4))(3), where L = imidazole, L-histidine, pyridine, or nicotinamide. The complexes have been characterized by elemental analysis, molar conductance measurements, UV-visible, infrared, proton nuclear magnetic, and electron paramagnetic resonance spectroscopies, and electrochemical techniques. The compounds possess relatively high nu(NO) stretching frequencies indicating that a high degree of positive charge resides on the coordinated nitrosyl group. The nitrosyl complexes react with OH(-) according to the equation trans-[Ru(NH(3))(4)L(NO)](3+) + 2OH(-) right arrow over left arrow trans-[Ru(NH(3))(4)L(NO(2))](+) + H(2)O, with a K(eq) (at 25.0 degrees C in 1.0 mol/L NaCl) of 2.2 x 10(5), 5.9 x 10(7), 9.7 x 10(10), and 4.6 x 10(13) L(2) mol(-)(2) for the py, nic, imN, and L-hist complexes, respectively. Only one redox process attributed to the reaction [Ru(II)(NH(3))(4)L(NO(+))](3+) + e(-) right arrow over left arrow trans-[Ru(II)(NH(3))(4)L(NO(0))](2+) was observed in the range -0.45 to 1.20 V for all the nitrosyl complexes. Linear correlations are observed in plots of nu(NO) versus E(1/2) and of E(1/2) versus summation operatorE(L) showing that the oxidizing strength of the coordinated NO increases with increase in L pi-acidity. The crystal structure analysis of trans-[Ru(NH(3))(4)nicNO](2)(SiF(6))(3) shows that the mean Ru-N-O angle is very close to 180 degrees (177 +/- 1 degrees ) and the mean N-O distance is 1.17 +/- 0.02 Å, thus confirming the presence of the Ru(II)-NO(+) moiety in the nitrosyl complexes studied.
