Sulfur anions and their derivatives have long been recognized for their high selectivity and reactivity toward Pb(2+) ions and formation of highly absorptive yet water-insoluble compounds with both acid and base media. This phenomenon has been used for qualitative analysis of lead ions in water. We demonstrate a new method to quantitatively determine the Pb(2+) concentration in the range of 0.5-500 ppm in water using colorimetric measurement, based on forming "soluble" lead sulfide in water enhanced with non-precious-metal nanoparticles. This method has inherent high selectivity for lead over other alkali-metal and alkaline-earth-metal ions. The colorimetric measurements of the absorptive solutions provide accurate determination of the lead concentration in water comparable to that measured using inductively coupled plasma mass spectrometry. To our knowledge, this is the simplest, lowest cost, and easiest-to-use method for detecting and determining the lead concentration in water.
Poly(vinylamme) complexes with cobalt chloride hexahydrate exhibit the largest glass transition temperature enhancements that have been measured in this laboratory. Tg increases from 56°C in the undiluted polymer to 193°C when the molar concentration of cobalt is only 3%, based on the moles of polymeric repeat units. This translates to a 45°C enhancement in Tg per mol% cobalt. Higher glass transition temperatures have been measured for other polymeric complexes with d‐block salts, but this study reports the largest ΔTg=Tg(complex)‐Tg(undiluted polymer) when transition‐metal catalyzed chemical crosslinking reactions do not occur. A plausible explanation for this effect is based on the fact that cobalt chloride hexahydrate maintains pseudo‐octahedral symmetry in the undiluted crystalline state and in an amorphous glassy complex with the polymer. The lone pair on nitrogen in the amino sidegroup is a strong base and, most likely, displaces all four waters of hydration that coordinate directly to the metal center. In fact, estimates of the ligand field splitting and the ligand field stabilization energy for octahedral cobalt complexes that contain methyl amine (CH3NH2) model ligands suggest that five or six amino sidegroups from several different chains might coordinate to each metal center, drastically reducing the mobility of the polymer. Both chloride anions remain near each divalent Co2+ center, but either one or two Cl− might not reside in the first‐shell coordination sphere of the transition metal. This bonding picture suggests that octahedral cobalt acts as a multi‐functional bridge between five or six amino sidegroups. Empirical ligand field stabilization calculations support the concept that octahedral Co2+ is a multi‐functional coordination crosslinking agent, and the inorganic literature provides experimental verification that similar small‐molecule complexes (i.e., [Co(NH3)6]2+) exist. It is proposed that the onset of Tg occurs when sufficient thermal energy is supplied to remove either x or (x‐1) amino sidegroup ligands from the coordination sphere of cobalt, where x is either 5 or 6. This is an endothermic process based on bond energies, as well as calculations which focus on the relative energies of the metal d‐electrons.
Conventional supercapacitors exhibit limitations that arise from various sources within the device such as the necessary incorporation of resistive additives to the electrode formulation. In the case of activated carbon (AC) electrodes, this constitutes the insulating binder, while for carbon nanotube (CNT) electrodes, the inclusion of appropriate surfactant is almost always necessary to promote stable dispersion for processing. This work discusses the use of surfactant-free and binder-free CNT electrodes for fabrication of supercapacitors. The performance characteristics from pouch cells containing such CNT electrodes in organic electrolytes were benchmarked against commercial-grade AC supercapacitor devices on both cell volume and cell weight bases. EDLC performance advantages realized from eliminating the additives of surfactant and binder were significantly lower a.c. impedance at low temperature operation (80% reduction at -30°C), higher capacitance retention after 100,000 cycles, and superior retention of capacitance at high temperature (95% of initial capacitance at 70°C) compared to commercial AC based EDLCs.
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