In situ FTIR studies on the effect of temperature on the electro-oxidation of small organic molecules at the Ru(0001) electrode

The adsorption and electro-oxidation of formaldehyde, formic acid and methanol at the Ru(0001) electrode in perchloric acid solution have been studied as a function of temperature, potential and time using in situ FTIR spectroscopy, and the results interpreted in terms of the surface chemistry of the Ru(000 1) electrode and compared to those obtained during our previous studies on the adsorption of CO under the same conditions. It was found that no dissociative adsorption or electro-oxidation of methanol takes place at Ru(0001) at potentials < 900 mV vs. Ag/AgCl, and at all three temperatures employed, 10, 25 and 50 degrees C. However, both formaldehyde and formic acid did undergo dissociative adsorption, even at -200 mV, to form linear (CO(L)) and 3-fold-hollow (COH) binding CO adsorbates. In contrast to the adsorption of CO, it was found that increasing the temperature to 50 degrees C markedly increased the amount of CO adsorbates formed on the Ru(0001) surface from the adsorption of both formaldehyde and formic acid. On increasing the potential, the electro-oxidation of the CO adsorbates to CO2 took place via reaction with the active (1 x 1)-O oxide. Formic acid was detected as a partial oxidation product during formaldehyde electro-oxidation. At all three temperatures employed, it was found that adsorbed CO species were formed from the adsorption of both formic acid and formaldehyde, and were oxidised to CO2 faster than was observed in the experiments involving CO adsorbed from CO(g), suggesting a higher mobility of the CO adsorbates formed from the adsorption of the HCOOH and HCHO. At potentials > 1000 mV, both the oxidation of formic acid to CO2 and the oxidation of formaldehyde to both CO2 and formic acid were significantly increased, and the oxidation of methanol to CO2 and methyl formate was observed, all of which were attributed to the formation of an active RuO2 phase on the Ru(0001) surface.     

The excess enthalpies of (carbon dioxide + cyclohexane) at 308.15, 358.15, and 413.15 K from 7.50 to 12.50 MPa

The excess molar enthalpies H_m^E for (carbon dioxide + cyclohexane) were measured in the vicinity of their critical locus and in the supercritical region. Mixtures at 308.15 K and at 7.50 MPa show very exothermic mixing and a region where H_m^E varies linearly with mole fraction x while at 10.50 and 12.50 MPa they show only moderately endothermic mixing. Mixtures at 358.15 and 413.15 K and at all pressures studied except for 358.15 K and 12.50 MPa have an exothermic section in the cyclohexane-rich region, a linear section which starts at a mole fraction x corresponding very closely to that of the minimum value of H_m^E, and an endothermic section in the carbon-dioxide-rich region. The H_m^E results exhibiting a linear section allow the determination of values for the vapor and liquid equilibrium-phase compositions. The changes observed in the excess enthalpy with both pressure and temperature are discussed in terms of liquid-vapor equilibrium and critical constants for (carbon dioxide + cyclohexane).     

Experimental and computational studies of trialkylaluminum and alkylaluminum chloride reactions with silica

Reactions of trimethylaluminum, triethylaluminum, and diethylaluminum chloride and ethylaluminum dichloride with silica gel have been studied experimentally by infrared spectroscopy and elemental analysis. The silica gel was subjected to different pretreatments to alter surface functionalities prior to reaction. In all cases the extent of surface modification reaction follows the trend unmodified > 600 degrees C pretreated > hexamethyldisilazane (HMDZ) pretreated > 600 degrees C/HMDZ pretreated. All of the aluminum compounds studied completely react non-hydrogen-bonded silanols, while also reacting with hydrogen-bonded silanols and siloxanes. Primarily monomeric surface species result from the surface modification reaction. Ethylaluminum chlorides preferentially react with silanols through cleavage of the Al-C bond rather than the Al-Cl bond. Singly bonded Si(s)-O-AlCl(2) surface species are readily synthesized by reaction of ethylaluminum dichloride with HMDZ-pretreated silica gel. Bridged bonded (Si(s)-O)(2)-AlCl surface species are readily synthesized by reaction of diethylaluminum chloride with HMDZ-pretreated silica gel. Computational ab initio studies of the cluster Si(4)O(6)(OH)(4) as a model to study the reaction of monomeric and dimeric methylaluminum dichloride with a silica silanol are also described. Comparison of the potential energy surface (PES) of monomer and dimer indicates that the energetics favor monomer reaction, consistent with experimental results. The energy cost in the dimer reaction is primarily from cleavage of a bridged Al-Cl bond upon adsorption. This does not occur when the monomer adsorbs. A comparison of the PES for the two reaction pathways resulting from cleavage of either an Al-Cl or Al-C bond indicates that while the former reaction is slightly kinetically favored (E(a) = 23.1 kJ/mol for Al-Cl bond cleavage versus E(a) = 31.1 kJ/mol for Al-C bond cleavage), the latter is strongly thermodynamically favored with an overall free energy difference between the two reaction pathways of 135 kJ/mol favorable to Al-C bond cleavage. These reactions are thermodynamically controlled.     

Facilitated transport from ternary cation mixtures through water—chloroform—water membrane systems containing macrocyclic ligands

Cation fluxes were determined for various three-component, equimolar mixtures of alkali metal, alkaline earth, and Pb²⁺ cations in a H₂O---CHCl₃---H₂O liquid membrane system incorporating macrocyclic polyethers as carriers. Carrier ligands studied were 18-crown-6, dicyclohexano-18-crown-6, 1,10-diaza-18-crown-6, 21-crown-7, dibenzo-24-crown-8, and cryptand [2.2.2]. Correlations were found between transport and relative cation:polyether cavity radii, the type of substituents present on the polyether ring, and the type and number of donor atoms present. All the ligands studied transported Pb²⁺ at higher rates than the other Mⁿ⁺ in the mixtures. Transport behavior in these multi-cation systems can be predicted from Mⁿ⁺—polyether complex stability constant data in most cases.     

Direct determination of rate constants for coupling between aromatic radical anions and alkyl and benzyl radicals by laser-flash photolysis

Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A-.) have been obtained using a new laser-flash photolysis method. The radicals R. and the radical anions A-. were generated by a photoinduced electron transfer reaction between the aromatic compound A and the alkyl or benzyl triphenylborate anion RB(Ph)3-. For the first time the rate constants of the coupling reaction between methyl and benzyl radicals with aromatic radical anions have been obtained. For all the measured coupling rate constants an average value of k1 = 1.9 x 10(9) M-1 s-1 was found with a relatively small variation in the coupling rates (0.8-2.9 x 10(9) M-1 s-1). The results demonstrate that the coupling rate k1 is insensitive to changes in the steric and electronic properties of the radicals and the structure and standard potentials of the aromatic radical anions.