Effect of H/D-isotope substitution on the solubility and solvation thermodynamics of krypton in methanol solutions of carbamide

The solubility of gaseous krypton in CO(NH₂)₂—CH₃OH (CD₃OH) and CO(ND₂)₂—CH₃OD solutions with carbamide concentrations of up to 1.5 solvomolality units (0.026 mole fractions) was measured at 278, 288, 298, 308, and 318 K and at a partial gas pressure of 101325 Pa. The thermodynamic functions of dissolution (solvation) of krypton and the standard Setchenov coefficients were calculated. The solvation of Kr molecules increases upon deuterium substitution and with an increase in the temperature and carbamide concentration. In these solutions, specific contacts between the carbamide and methanol molecules play the predominant role.     

On the rate of oxidation of co on La2O3 doped NiO/Al2O3 catalysts: an artificial neural network approach

Summary The rate constants of the oxidation of CO on a number of pure and La₂O₃ doped NiO/Al₂O₃ solid catalysts were correlated with the mole percent of dopant, calcinations temperature, surface area, pore volume and pore mouth diameter by an artificial neural network simulator. The cross validation method had to be used due to the scarcity of the data. A three-layer network with 3 nodes in the hidden layer was found to simulate the system well.     

Synthesis of deuterium and tritium labelled phenyl glycine

A new method of synthesis of phenyl glycine labelled with deuterium and tritium was elaborated. Labelled phenyl glycine was obtained by isotope exchange method between phenyl glycine and deuterated or tritiated water at elevated temperature in hydrochloric acid medium using K₂PtCl₄ as a catalyst. 37 GBq /1 Ci/ HTO was used for the synthesis of tritiated phenyl glycine and labelled product with specific activity of 185 MBq/mole /5 mCi/mole/ was obtained.     

Determination of H2 and D2 content in metals and alloys using hot vacuum extraction

A hot vacuum extraction technique for the determination of hydrogen in metal and alloy samples has been standardised. After measuring the total pressure of the evolved gases, individual hydrogen and deuterium intensities are measured using an on-line quadrupole mass spectrometer. Synthetic mixtures of H₂ and D₂, in known concentrations, have been analysed by QMS and an analytical expression correlating the measured [D₂]/[HD] intensity ratio with the mole fraction of deuterium in the synthetic mixture has been arrived at. The precision and accuracy in the measurement of hydrogen is about 10% at 50 ppmw level.     

Mechanism of hydroformylation,part II Study of the formation of hydrocobalttetracarbonyl by the reaction of Co2(CO)8 and H2

The kinetics and the position of the equilibrium of the reaction Co₂(CO)₈+H₂2 HCo(CO)₄ were studied in the range of 80–160 °C and 50–100 atm. by means of in situ IR spectroscopy.The reaction is reversible first order with respect to CO₂(CO)₈ and HCo(CO)₄ and the energies of activation of the forward and the reverse reaction are found to be 17,3 cal/mole, and 11.0 kcal/mole resp.The reaction is slightly endothermic with H=6.6 kcal/mole and S=14.6 e.u. The heat of formation of HCo(CO)₄ and the bond strength between hydrogen and cobalt in HCo(CO)₄ were found to be—146.1 kcal/mole and 54.7 kcal/mole resp.With 8 FiguresPart of the Ph.D. Dissertation 1974.Part I see Ref.¹³     

Selective CO methanation over amorphous Ni-Ru-B/ZrO2 catalyst for hydrogen-rich gas purification

Amorphous Ni-Ru-B/ZrO₂ catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni₆₁Ru₉B₃₀/ZrO₂ catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230°C～250°C, and the CO₂ conversion was kept under the level of 0.9%.     

Heats of reaction of HMo(CO)3C5H5 with CCl4 and CBr4 and of NaMo(CO)3C5H5 with I2 and CH3. Solution thermochemical study of the MoX bond for X = H,Cl, Br,I and CH3

The heats of reaction of HMo(CO)₃C₅H₅ with CX₄ (X = Cl, Br) producing XMo(CO)₃C₅H₅ have been measured by solution calorimetry and are −31.8±0.9 and −34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)₃C₅H₅ with I₂ and CH₃I producing IMo(CO)₃C₅H₅ and H₃CMo(CO)₃C₅H₅ are −32.3± 1.3 and −7.7± 0.3 kcal/mole. Oxidation with Br₂CCl₄ yielding Br₃Mo(CO)₂C₅H₅ was measured for the following complexes: (C₅H₅(CO)₃Mo)₂, (−92.0±1.0 kcal/mole), BrMo(CO)₃C₅H₅ (−24.9± 2.0 kcal/mole) and HMo(CO)₃C₅H₅ (−60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo–X bond strength for X = H, Cl, Br, I, and CH₃. These bond strength estimates are compared to those reported for X₂Mo(C₅H₅)₂. Iodination of H₃CMo(CO)₃C₅H₅, reported in the literature to yield CH₃I and IMo(CO)₃C₅H₅, actually produces CH₃C(O)I and I₃Mo(CO)₂C₅H₅.     

Threshold energies for production of CH2(3B1) and CH2(1A1) from ketene photolysis. The CH2(3B1) ↔ CH2(1A1) energy splitting

By measuring the relative CO quantum yields from ketene photolysis as a function of photolysis wavelength we have determined the threshold energy at 25° for CH₂CO(¹A₁) → CH₂(³B₁) + CO(¹Σ⁺) to be 75.7 ± 1.0 kcal/mole. This corresponds to a value of 90.7 ± 1.0 kcal/mole for ΔH_f298⁰[CH₂(³B₁)]. By measuring the relative ratio of CH₂(¹A₁)/CH₂(³B₁) from ketene photolysis as a function of photolysis wavelength we have determined the threshold energy at 25°C for CH₂CO(¹A₁) → CH₂(¹A₁) + CO(¹Σ⁺) to be 84.0 ± 0.6 kcal/mole. This corresponds to a value of 99.0 ± 0.6 kcal/mole for ΔH_f298⁰[CH₂(¹A₁)]. Thus a value for the CH₂(³B₁) ? CH₂(¹A₁) energy splitting of 8.3 ± 1 kcal/mole is determined, which agrees with three other recent independent experimental estimates and the most recent quantum theoretical calculations.     

Removal of CO from reformed fuels by selective methanation over Ni-B-Zr-Oδ catalysts

The Ni-B-Oδ andNi-B-Zr-Oδ catalysts were prepared by the method of chemical reduction, and the deep removal of CO by selective methanation from the reformed fuels was performed over the as-prepared catalysts. The results showed that zirconium strongly influenced the activity and selectivity of the Ni-B-Zr-Oδ catalysts. Over the Ni-B-Oδ catalyst, the highest CO conversion obtained was only 24.32% under the experimental conditions studied. However, over the Ni-B-Zr-Oδ catalysts, the CO methanation conversion was higher than 90% when the temperature was increased to 220 oC. Additionally, it was found that the Ni/B mole ratio also affected the performance of the Ni-B-Zr-Oδ catalysts. With the increase of the Ni/B mole ratio from 1.8 to 2.2, the CO methanation activity of the catalyst was improved. But when the Ni/B mole ratio was higher than 2.2, the performance of the catalyst for CO selective methanation decreased instead. Among all the catalysts, the Ni29B13Zr58Oδ catalyst investigated here exhibited the highest catalytic performance for the CO selective methanation, which was capable of reducing the CO outlet concentration to less than 40 ppm from the feed gases stream in the temperature range of 230–250 oC, while the CO2 conversion was kept below 8% all along. Characterization of the Ni-B-Oδ and Ni-B-Zr-Oδ catalysts was provided by XRD, SEM, DSC, and XPS.     

Dynamics of dilute water in carbon tetrachloride

A dilute solution of water in a hydrophobic solvent, such as carbon tetrachloride (CCl4), presents an opportunity to study the rotational properties of water without the complicating effects of hydrogen bonds. We report here the results of theoretical, experimental, and semiempirical studies of a 0.03 mole percent solution of water in CCl4. It is shown that for this solution there are negligible water-water interactions or water-CCl4 interactions; theoretical and experimental values for proton NMR chemical shifts (deltaH) are used to confirm the minimal interactions between water and the CCl4. Calculated ab initio values and semiempirical values for oxygen-17 and deuterium quadrupole coupling constants (chi) of water/CCl4 clusters are reported. Experimental values for the 17O, 2H, and 1H NMR spin-lattice relaxation times, T1, of 0.03 mole percent water in dilute CCl4 solution at 291 K are 94+/-3 ms, 7.0+/-0.2 s, and 12.6+/-0.4 s, respectively. These T1 values for bulk water are also referenced. "Experimental" values for the quadrupole coupling constants and relaxation times are used to obtain accurate, experimental values for the rotational correlation times for two orthogonal vectors in the water molecule. The average correlation time, tauc, for the position vector of 17O (orthogonal to the plane of the molecule) in monomer water, H2(17)O, is 91 fs. The average value for the deuterium correlation time for the deuterium vector in 2H2O is 104 fs; this vector is along the OD bond. These values indicate that the motion of monomer water in CCl4 is anisotropic. At 291 K, the oxygen rotational correlation time in bulk 2H2(17)O is 2.4 ps, the deuterium rotational correlation time in the same molecule is 3.25 ps. (Ropp, J.; Lawrence, C.; Farrar, T. C.; Skinner, J. L. J. Am. Chem. Soc. 2001, 123, 8047.) These values are a factor of about 20 longer than the tauc value for dilute monomer water in CCl4.     

Ring expansion and hydrogen scrambling in the molecular ion of 3-methylthiophene

The ratio [M ? D]/{[M-D] + [M ? H]} in the 70 eV mass spectra of six deuterated 3-methylthiophenes has been determined. From these values the mole fractions of the molecular ions that lose hydrogen atoms specifically from the various positions of the molecule were calculated, as well as the mole fraction in which the hydrogen atoms are fully scrambled before hydrogen elimination. It appears that hydrogen atoms are mainly lost from a fully scrambled [C₅H₆S]⁺· ion and from the α-position of the original molecular ion. A deuterium isotope effect of 1·60 to 1·72 was calculated for the hydrogen elimination. The reaction was also studied at low electron energies. In order to determine the degree of scrambling in the [C₅H₅S]⁺ ions, some decomposition reactions of this ion were investigated.     

Katalytische Wirksamkeit van reinem und von CO-vergiftetem Platin bei der p-H2-Umwandlung

Catalysis of p-H₂ Conversation on Pure and CO-poisoned Platinum The reaction has been studied on a Pt foil using u. h. v. cleaning conditions. The rate of the conversion is extremely high on a clean Pt surface, the activation energy being 4.1 kcal/mole. CO/poisons reversibly. After preadsorption of CO on half of the Pt surface the activity descreases to 6% of the original value and the activation energy increases p to 8.4 kcal/mole. In the discussion a direct correlation between the activation energy and the lowest adsorption heats of hydrogen is proposed. The reaction occurs predominantly on centres with lowest bond strength.     

The roles of hetero atoms in solvolytic reactions—I: Preferential effect by nitrogen to facilitate carbonyl-oxygen cleavage of esters

3- and 4-Piperidinyl and 2-pyrrolidinylmethyl halides and p-nitrobenzoates were prepared. In the solvolysis, the remarkable difference in the effect of nitrogen on the two kinds of the leaving groups was observed. Halides underwent the solvolysis of S_N1 mechanism, whereas p-nitrobenzoates resulted in the preferential OCO cleavage. The results of IR absorption of ester-carbonyl group and kinetic deuterium isotope effect suggested that in the solvolysis of the esters, an initial solvation may be important for the cleavage of a OCO bond.     

Evidence for formation and different evolution of tertiary rhodium alkyl intermediates under rhodium-catalyzed deuterio-(hydro)formylation of 1-(n-pyridyl)-1-phenylethenes

Deuterioformylation of the vinylidenic substrates 1-(n-pyridyl)-1-phenylethenes, in the presence of phosphine modified Rh₄(CO)₁₂ as catalyst precursor, was carried out at 100 atm of CO and D₂ (1:1), 80 °C and at partial and complete substrate conversion.The direct ²H NMR analysis of the crude reaction mixture led to the conclusion that, under these conditions, the branched alkyl rhodium intermediate is formed almost exclusively. It can: (i) β-eliminate, (ii) undergo migratory insertion on CO or (iii) oxidative addition of deuterium to various extents depending on the position of the nitrogen atom with respect to the olefinic double bond, thus accounting for the observed different chemo- and regioselectivities.     

Aromatic ring favorable and efficient H-D exchange reaction catalyzed by Pt/C

An effective and applicable Pt/C-catalyzed deuteration method of aromatic rings using D₂O as a deuterium source under hydrogen atmosphere was developed. Five percent Pt/C would lead to quite effective H-D exchange results on the aromatic ring systems. The reaction is general for a variety of aromatic compounds including biologically active compounds.     

Synthesis and characterization of graft copolymers of methacrylonitrile/methacrylate mixtures onto amylomaize by the ceric ion method

Graft polymerizations of mixtures of methacrylonitrile with n-alkyl methacrylales onto amylomaize were carried out. The graft copolymers were characterized by both IR and ¹³C-NMR spectroscopies. The influence of the monomer feed on the grafting parameters has been studied. The variation of these parameters with the mole fraction of methacrylate in the feed for the first three systems studied, MAN/MMA, MAN/EMA and MAN/BMA, was similar: thus, percent grafting (%G, percent weight of grafted polymer with respect to grafted amylomaize), percent grafted amylomaize (%GA, percent weight of grafted amylomaize with respect to initial amylomaize), percent grafting conversion (%C_g, percent weight of grafted polymer with respect to initial monomer), and percent total conversion (%C_t, percent weight of total acrylic polymer with respect to initial monomer) were increased, but percent grafting efficiency (%GE, percent weight of graft copolymer with respect to total polymer) decreased. The system MAN/HMA presented values of grafting parameters lower than those of the previous systems. The optimum values were obtained at 0.6 HMA mole fraction in the monomer feed. When the number of carbon atoms of the n-alkyl group rises from 1 to 4, the increase of the n-alkyl group length gives rise to increases of the %G %C_g and %C_t values and decreases of the %GE and %GA values. For the largest methacrylate, the grafting reaction appears to be controlled by the lesser accessibility of the monomer to the active sites of the carbohydrate. © 1992 John Wiley & Sons, Inc.     

Oxidation of the [Rh(CO)2Cl2] anion in aqueous solution

The reaction of rhodium(I) carbonyl chloride, [Rh(CO)₂Cl]₂, with dichromate, cerium(IV) sulfate, hexachloroplatinic acid or p-benzoquinone in aqueous hydrochloric acid proceeds by consumption of 4 equivalents of oxidizing agent per mole or rhodium(I) in accordance with the equation Rh^I(CO)₂  4e + H₂O → Rh^III(CO) + 2H⁺ + CO₂A “cyclic” oxidation mechanism is suggested.     

Raman spectroscopic study of hydrogen bonding of N-alkyl-2-pyrrolidinones in heavy water

The Raman spectra of D₂O solutions of N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, and N-n-butyl-2-pyrrolidinone under diverse conditions were measured. Using a computer fitting of the band shape of the carbonyl stretching mode at various temperatures, an enthalpy difference for the inversion motion at the nitrogen atom due to hydrogen bonding with deuterium was estimated for these compounds. The enthalpy difference of hydrogen bond formation to the nitrogen atom of N-methyl-2-pyrrolidinone at 30 wt% in D₂O (mole fraction 0.080) was greater than that of N-methyl-2-pyrrolidinone in an aqueous solution at a mole fraction of 0.406. Furthermore, the enthalpy difference of N-alkyl-2-pyrrolidinones increased with the alkyl chain length. This is interepreted as a result of the change of the hydrophobic hydration of D₂O molecules around the solute molecules.     

Transfer processes of alkoxyl groups in iron carbonyl complexes

The mass spectra of Fe₂(CO)₆C₄(COOCH₃)₄ and Fe₂(CO)₆C₄(COOC₂H₅)₄ are reported. Transfer processes of alkoxyl groups and hydrogen rearrangements are observed, and confirmed by deuterium labelling and the observation of metastable transitions. Fe₃(CO)₈C₄(COOCH₃)₄ and Fe₃(CO)₈C₄(COOC₂H₅)₄ give similar breakdown patterns. Likely fragmentation schemes are suggested.     

Experimental measurement and prediction of hydrate forming conditions in the nitrogen-propane-water system

Experimental data on initial hydrate formation conditions have been obtained for the nitrogen-propane-water system in the L₁HG, L₁L₂H, and L₁L₂HG regions, where L₁ is the water rich liquid phase, L₂ is the hydrocarbon rich liquid phase, H is the hydrate and the G is the vapor phase. The measurements covered a range of temperatures from about 275 to 293 K and pressures from about 0.3 to 17.0 MPa. The concentrations covered for the L₁HG region extended from 0.94 to 75.0 mole percent propane in the gas phase, and for the L₁L₂H region they extended from 83.1 to 99.0 mole percent in the condensed liquid phase. Four-phase measurements were made at concentrations of propane from 18.1 to 71.1 mole percent in the gas phase.The experimental data were used to find a fitted binary interaction parameter for predicting hydrate formation in systems containing nitrogen and propane.