Anaerobic Digestion of Sugarcane Vinasse Through a Methanogenic UASB Reactor Followed by a Packed Bed Reactor

The anaerobic treatment of raw vinasse in a combined system consisting in two methanogenic reactors, up-flow anaerobic sludge blanket (UASB) + anaerobic packed bed reactors (APBR), was evaluated. The organic loading rate (OLR) was varied, and the best condition for the combined system was 12.5 kg COD m^?3day^?1 with averages of 0.289 m³ CH₄ kg COD r^?1for the UASB reactor and 4.4 kg COD m^?3day^?1 with 0.207 m³ CH₄ kg COD r^?1 for APBR. The OLR played a major role in the emission of H₂S conducting to relatively stable quality of biogas emitted from the APBR, with H₂S concentrations <10 mg L^?1. The importance of the sulphate to COD ratio was demonstrated as a result of the low biogas quality recorded at the lowest ratio. It was possible to develop a proper anaerobic digestion of raw vinasse through the combined system with COD removal efficiency of 86.7% and higher CH₄ and a lower H₂S content in biogas.     

Structure and formation of gaseous [C4H6O]+˙ ions: 1—The enolic ions [CH2C(OH)?CHCH2]+˙ and [CH2CH?CHCH(OH)]+˙ and their relationship with their keto counterparts

The [C₄H₆O]^+˙ ion of structure [CH₂?CHCH?CHOH]^+˙ (a) is generated by loss of C₄H₈ from ionized 6,6-dimethyl-2-cyclohexen-1-ol. The heat of formation ΔH_f of [CH₂?CHCH?CHOH]^+˙ was estimated to be 736 kJ mol^?1. The isomeric ion [CH₂?C(OH)CH?CH₂]^+˙ (b) was shown to have ΔH_f, ? 761 kJ mol^?1, 54 kJ mol^?1 less than that of its keto analogue [CH₃COCH?CH₂]^+˙. Ion [CH₂?C(OH)CH?CH₂]^+˙ may be generated by loss of C₂H₄ from ionized hex-1-en-3-one or by loss of C₄H₈ from ionized 4,4-dimethyl-2-cyclohexen-1-ol. The [C₄H₆O]^+˙ ion generated by loss of C₂H₄ from ionized 2-cyclohexen-1-ol was shown to consist of a mixture of the above enol ions by comparing the metastable ion and collisional activation mass spectra of [CH₂?CHCH?CHOH]^+˙ and [CH₂?C(OH)CH?CH₂]^+˙ ions with that of the above daughter ion. It is further concluded that prior to their major fragmentations by loss of CH₃˙ and CO, [CH₂?CHCH?CHOH]⁺˙ and [CH₂?C(OH)CH?CH₂]^+˙ do not rearrange to their keto counterparts. The metastable ion and collisional activation characteristics of the isomeric allenic [C₄H₆O]^+˙ ion [CH₂?C?CHCH₂OH]^+˙ are also reported.     

A Robust 3D Cage‐like Ultramicroporous Network Structure with High Gas‐Uptake Capacity

A three‐dimensional (3D) cage‐like organic network (3D‐CON) structure synthesized by the straightforward condensation of building blocks designed with gas adsorption properties is presented. The 3D‐CON can be prepared using an easy but powerful route, which is essential for commercial scale‐up. The resulting fused aromatic 3D‐CON exhibited a high Brunauer–Emmett–Teller (BET) specific surface area of up to 2247 m² g^?1. More importantly, the 3D‐CON displayed outstanding low pressure hydrogen (H₂, 2.64 wt %, 1.0 bar and 77 K), methane (CH₄, 2.4 wt %, 1.0 bar and 273 K), and carbon dioxide (CO₂, 26.7 wt %, 1.0 bar and 273 K) uptake with a high isosteric heat of adsorption (H₂, 8.10 kJ mol^?1; CH₄, 18.72 kJ mol^?1; CO₂, 31.87 kJ mol^?1). These values are among the best reported for organic networks with high thermal stability (ca. 600 °C).     

Computational study on the mechanism for the gas‐phase reaction of dimethyl disulfide with OH

The mechanisms for the reaction of CH₃SSCH₃ with OH radical are investigated at the QCISD(T)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) level of theory. Five channels have been obtained and six transition state structures have been located for the title reaction. The initial association between CH₃SSCH₃ and OH, which forms two low‐energy adducts named as CH₃S(OH)SCH₃ (IM1 and IM2), is confirmed to be a barrierless process, The S? S bond rupture and H? S bond formation of IM1 lead to the products P1(CH₃SH + CH₃SO) with a barrier height of 40.00 kJ mol^?1. The reaction energy of Path 1 is ?74.04 kJ mol^?1. P1 is the most abundant in view of both thermodynamics and dynamics. In addition, IMs can lead to the products P2 (CH₃S + CH₃SOH), P3 (H₂O + CH₂S + CH₃S), P4 (CH₃ + CH₃SSOH), and P5 (CH₄ + CH₃SSO) by addition‐elimination or hydrogen abstraction mechanism. All products are thermodynamically favorable except for P4 (CH₃ + CH₃SSOH). The reaction energies of Path 2, Path 3, Path 4, and Path 5 are ?28.42, ?46.90, 28.03, and ?89.47 kJ mol^?1, respectively. Path 5 is the least favorable channel despite its largest exothermicity (?89.47 kJ mol^?1) because this process must undergo two barriers of TS5 (109.0 kJ mol^?1) and TS6 (25.49 kJ mol^?1). Hopefully, the results presented in this study may provide helpful information on deep insight into the reaction mechanism. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Theoretical study of the structure and unimolecular decomposition pathways of ethyloxonium, [CH3CH2OH2]+

Ab initio molecular orbital calculations with split-valence plus polarization basis sets and incorporating valence-electron correlation have been performed to determine the equilibrium structure of ethyloxonium ([CH₃CH₂OH₂]⁺) and examine its modes of unimolecular dissociation. An asymmetric structure (1) is predicted to be the most stable form of ethyloxonium, but a second conformational isomer of C_s symmetry lies only 1.4 kJ mol^?1 higher in energy than 1. Four unimolecular decomposition pathways for 1 have been examined involving loss of H₂, CH₄, H₂O or C₂H₄. The most stable fragmentation products, lying 65 kJ mol^?1 above 1, are associated with the H₂ elimination reaction. However, large barriers of 257 and 223 kJ mol^?1 have to be surmounted for H₂ and CH₄ loss, respectively. On the other hand, elimination of either C₂H₄ or H₂O from ethyloxonium can proceed without a barrier to the reverse associations and, with total endothermicities of 130 and 160 kJ mol^?1, respectively, these reactions are expected to dominate at lower energies. A second important equilibrium structure on the surface is a hydrogen-bridged complex, lying 53 kJ mol^?1 above 1. This complex is involved in the C₂H₄ elimination reaction, acts as an intermediate in the proton-transfer reaction connecting [C₂H₅]⁺ +H₂O and C₂H₄ + [H₃O]⁺ and plays an important role in the isotopic scrambling that has been observed experimentally in the elimination of either H₂O or C₂H₄ from ethyloxonium. The proton affinity of ethanol was calculated as 799 kJ mol^?1, in close agreement with the experimental value of 794 kJ mol^?1.     

Phospholipid/Polydiacetylene Vesicle-Based Colorimetric Assay for High-Throughput Screening of Bacteriocins and Halocins

Multi-phase anaerobic reactor for H₂ and CH₄ production from paperboard mill wastewater was studied. The reactor was operated at hydraulic retention times (HRTs) of 12, 18, 24, and 36 h, and organic loading rates (OLRs) of 2.2, 1.5, 1.1, and 0.75 kg chemical oxygen demand (COD)/m³ day, respectively. HRT of 12 h and OLR of 2.2 kg COD/m³ day provided maximum hydrogen yield of 42.76?±?14.5 ml/g COD_removed and volumetric substrate uptake rate (?rS) of 16.51?±?4.43 mg COD/L h. This corresponded to the highest soluble COD/total COD (SCOD/TCOD) ratio of 56.25?±?3.3 % and the maximum volatile fatty acid (VFA) yield (Y_VFA) of 0.21?±?0.03 g VFA/g COD, confirming that H₂ was mainly produced through SCOD conversion. The highest methane yield (18.78?±?3.8 ml/g COD_removed) and ?rS of 21.74?±?1.34 mgCOD/L h were achieved at an HRT of 36 h and OLR of 0.75 kg COD/m³ day. The maximum hydrogen production rate (HPR) and methane production rate (MPR) were achieved at carbon to nitrogen (C/N) ratio of 47.9 and 14.3, respectively. This implies the important effect of C/N ratio on the distinction between the dominant microorganism bioactivities responsible for H₂ and CH₄ production.     

Interaction of zinc oxide clusters with molecules related to the sulfur vulcanization of polyolefins ("rubber")

The vulcanization of rubber by sulfur is a large‐scale industrial process that is only poorly understood, especially the role of zinc oxide, which is added as an activator. We used the highly symmetrical cluster Zn₄O₄ (T_d) as a model species to study the thermodynamics of the initial interaction of various vulcanization‐related molecules with ZnO by DFT methods, mostly at the B3LYP/6‐31+G* level. The interaction energy of Lewis bases with Zn₄O₄ increases in the following order: CO62H₄3H₆2S₂<1,4‐C₅H₈2O2S3N?CH₃COO^?. The corresponding binding energies range from ?57 to ?262 kJ mol^?1. However, Brønsted acids react with the Zn₄O₄ cluster with proton transfer from the ligand molecule to one of the oxygen atoms of Zn₄O₄, and these reactions are all strongly exothermic [binding energies [kJ mol^?1] in parentheses: H₂O (?183), MeOH (?171), H₂S (?245), MeSH (?230), C₃H₆ (?121), and CH₃COOH (?255)]. The important vulcanization accelerator mercaptobenzothiazole (C₇H₅NS₂, MBT) containing several donor sites reacts with the Zn₄O₄ cluster with proton transfer from the NH group to one of the oxygen atoms of ZnO, and in addition the exocyclic thiono sulfur atom and the nitrogen atom coordinate to one and the same zinc atom, resulting in a binding energy of ?247 kJ mol^?1. A second isomer of [(MBT)Zn₄O₄] with a strong O? H???N hydrogen bond rather than a Zn? N bond is only slightly less stable (binding energy ?243 kJ mol^?1). The NH form of free MBT is 36 kJ mol^?1 more stable than the tautomeric SH form, while the sulfurized MBT derivative benzothiazolyl hydrodisulfide C₇H₅NS₃ (BtSSH) is most stable with the connectivity >CSSH.     

The structure and dissociation pathways of protonated methanol: An ab initio molecular orbital study

Ab initio molecular orbital calculations with moderately large polarization basis sets and including valence-electron correlation have been used to examine the structure and dissociation mechanisms of protonated methanol [CH₃OH₂]⁺. Stable isomers and transition structures have been characterized using gradient techniques. Protonated methanol is found to be the only stable isomer in the [CH₅O]⁺ potential surface. There is no evidence for a tightly-bound complex, [HOCH₂]⁺…?H₂, analogous to the preferred structure [CH₃]⁺…?H₂ of [CH₅]⁺. Protonated methanol is found to possess a pyramidal arrangement of bonds at the oxygen atom with a barrier to inversion of 8kJ mol^?1. The lowest energy fragmentation pathways are dissociation into methyl cation and water (predicted to require 284 kJ mol^?1 with zero reverse activation energy) and loss of molecular hydrogen (endothermic by 138 kJ mol^?1 but with a reverse activation barrier of 149 kJ mol^?1). The results offer a possible explanation as to why production of [CH₂OH]⁺ from the reaction of methyl cation with water is not observed. Other dissociation processes examined include loss of a hydrogen atom to yield the methylenoxonium radical cation or methanol radical cation (requiring 441 and 490 kJ mol^?1, respectively) and loss of a proton to yield neutral methanol (requiring 784 kJ mol^?1).     

The ethyl halides: Stable neutral and radical cation isomers [C2, H2, X] where X = F,Cl, Br,I

The following isomers of the ethyl halide molecular ions have all been shown to be stable species in the gas phase: [CH₂CH₂FH]⁺˙; [CH₃ClCH₂]⁺˙ (ΔH_f° = 1012 kJ mol^?1); [CH₃CHClH]⁺˙ (ΔH_f° = 971 kJ mol^?1); [CH₂CH₂ClH]⁺˙; [CH₃BrCH₂]⁺˙ (ΔH_f° = 1058 KJ mol^?1); [CH₃CHBrH]⁺˙ (ΔH_f° = 995 kJ mol^?1) and [CH₂CH₂BrH]⁺˙. Neutralization–reionization mass spectrometry, employing Xe as the electron transfer target gas and O₂ as the target gas for reionization, indicated that the ylides CH₃ClCH₂ and CH₃BrCH₂ could not be generated by such means. However, the species CH₃CHClH, CH₂CH₂ClH and CH₂CH₂BrH (and possibly CH₃CHBrH) were unambiguously identified.     

Linking Performance with Microbial Community Characteristics in an Anaerobic Baffled Reactor

The performance and microbial community characteristics of a laboratory scale anaerobic baffled reactor (ABR) with four compartments (C1–C4) treating sugar refinery wastewater were investigated. The COD removal was 94.8 % with a CH₄ yield of 0.21 L?g^?1 COD_removed at total organic loading rate (OLR) of 5.33 kg COD/m^?3?day^?1. Fermentative bacteria were dominant in C1 and C2, while syntrophic acetogens and methanogens were dominant in C3 and C4. Some acid-tolerant methanogens were enriched in acidogenic phase. The present of the acid-tolerant methanogens could improve the efficiency and stability of the ABR as the most of the methanogens are vulnerable to low pH. In addition, high functional redundancy of the fermentative bacteria implicated that the microbial communities in acidogenic phase were stable functionally and allowed the ABR to balance perturbation. It was also found that syntrophic acetogenesis might be a weakness in the ABR as syntrophic acetogens were poor as compared with fermentative bacteria and methanogens.     

Synthesis,structure, and kinetic studies on [RuCl2(NCCH3)2(cod)]

[RuCl₂(NCCH₃)₂(cod)], an alternative starting material to [RuCl₂(cod)] _n for the preparation of ruthenium(II) complexes, has been prepared from the polymer compound and isolated in yields up to 87% using a new work-up procedure. The compound has been obtained as a yellow solid without water of crystallization. The complexes [RuCl₂(NCR)₂(cod)] spontaneously transform into dimers [Ru₂Cl(μ-Cl)₃(cod)₂(NCR)] (R?=?Me, Ph). ¹H NMR kinetic experiments for these transformations evidenced first-order behavior. [RuCl₂(NCPh)₂(cod)] dimerizes slower by a factor of ten than [RuCl₂(NCCH₃)₂(cod)]. The following activation parameters, ΔH ^#?=?114?±?3?kJ?mol^?1 and ΔS ^#?=?66?±?9?J?K^?1?mol^?1 for R?=?CH₃CN (ΔG ^#?=?94?±?5?kJ?mol^?1, 298.15?K) and ΔH ^#?=?122?±?2?kJ?mol^?1 and ΔS ^#?=?75?±?6?J?K^?1?mol^?1 for R?=?Ph (ΔG ^#?=?100?±?4?kJ?mol^?1, 298.15?K), have been calculated from the first-order rate constants in the temperature range 294–323?K. The kinetic parameters are in agreement with a two-step mechanism with dissociation of acetonitrile as the rate-determining step. The molecular structures of [Ru₂Cl(μ-Cl)₃(cod)₂(NCR)] (R?=?Me, Ph) have been determined by X-ray diffraction.     

Application of halo polyhydroxy polyurethane foam for the extraction of cobalt from cobalamin drugs and urine

Polyhydroxy polyurethane sorbent was modified by the addition of halogen atoms to its matrix to produce a new sorbent distinguished by high surface polarity, enhanced capacity, and improved stability in both acidic and alkaline media. Halo polyhydroxy polyurethane foam (X-PPF) was characterized by NMR, FTIR, UV–Vis, Raman spectroscopy, pH_ZCP values, and scanning electron microscopy images. Experimental studies have proven that X-PPFs have a great potential for the extraction and recovery of cobalt ions and this was attributed to the presence of halogen, phenolic, and urethane groups. The pH_ZCP value of X-PPFs was determined to be 0.91 and the maximum metal recovery was achieved at a pH range of 6–7. The kinetics of the process was best described by pseudo-second-order model (R²?=?1). ΔH, ΔS, and ΔG values were calculated to be ?57.2?kJ?mol^?1, ?172.6?J?K^?1?mol^?1, and ?5.8?kJ?mol^?1, respectively. A perfect isotherm curve with zero intercept (0.002), good correlation (R²?=?0.999), and capacity of 246.8?mg?g^?1 was obtained.     

A theoretical study of the condensation reactions of methyl cation with ammonia,water, hydrogen fluoride and hydrogen sulphide

Ab initio molecular orbital calculations have been used to study the condensation reactions of CH₃^? with NH₃, H₂O, HF and H₂S. Geometry optimization has been carried out at the Hartree—Fock (HF) level with the split-valence plus d-polarization 6-31G* basis set and improved relative energies obtained from calculations which employ the split-valence plus dp-polarization 6-31G** basis set with electron correlation incorporated via Moller—Plesset perturbation theory terminated at third order (MP3). Zero-point vibrational energies have also been determined and taken into account in deriving relative energies. The structures of the intermediates CH₃XH^? (X = NH₂, OH, F and SH) have been obtained and dissociation of these intermediates into CH₂X⁺ + H₂ on the one hand, and CH₃^? + HX on the other, has been examined. It is found that for those species for which the methyl condensation reaction is observed to have an appreciable rate (X = NH₂ and SH), the transition structure for hydrogen elimination from CH₃XH^? lies significantly lower in energy than the reactants CH₃^? + HX (by 75 and 70 kJ mol^?1 respectively). On the other hand, for those species for which the methyl condensation reaction is not observed (X = OH and F), the transition structure for H₂ elimination lies higher in energy than CH₃^? + HX (by 6 and 87 kJ mol^?1 respectively).     

Barrier to 1,3-sigmatropic shift in odd electron ions. A MINDO/3 study of H,OH, CH3 and C6H5 migration

Critical energies for 1,3-R sigmatropic migrations (R?H, OH, CH₃ and C₆H₅) have been calculated by means of the MINDO/3 method. This investigation was carried out for the system [RCH₂CH?CH₂]^+˙ and the results indicated that hydroxyl group migration is energetically favoured (critical energy = 53 kJ mol^?1). Calculations are also presented for [3-buten-2-ol]^+˙ isomerizations. The lowest energy pathway is related to the [2-buten-1-ol]^+˙; the corresponding critical energy for OH migration is equal to 33 kJ mol^?1 in this case.     

A dynamic column breakthrough apparatus for adsorption capacity measurements with quantitative uncertainties

A dynamic column breakthrough (DCB) apparatus was used to study the separation of CH₄+N₂ gas mixtures using two zeolites, H⁺-mordenite and 13X, at temperatures of (229.2 and 301.9)?K and pressures to 792.9?kPa. The apparatus is not limited to the study of dilute adsorbates within inert carrier gases because the instrumentation allows the effluent flow rate to be measured accurately: a method for correcting apparent effluent mass flow readings for large changes in effluent composition is described. The mathematical framework used to determine equilibrium adsorption capacities from the dynamic adsorption experiments is presented and includes a method for estimating quantitatively the uncertainties of the measured capacities. Dynamic adsorption experiments were conducted with pure CH₄, pure N₂ and equimolar CH₄+N₂ mixtures, and the results were compared with similar static adsorption experiments reported in the literature. The 13X zeolite had the greater adsorption capacity for both CH₄ and N₂. At 792?kPa the equilibrium capacities of the 13X zeolite increased from 2.13±0.14?mmol?g^?1 for CH₄ and 1.36±0.10?mmol?g^?1 for N₂ at 301.9?K to 3.97±0.19?mmol?g^?1 for CH₄ and 3.33±0.12?mmol?g^?1 for N₂ at 229.2?K. Both zeolites preferentially adsorbed CH₄; however, the mordenite had a greater equilibrium selectivity of 3.5±0.4 at 301.9?K. Equilibrium selectivities inferred from pure fluid capacities using the Ideal Adsorbed Solution theory were limited by the accuracy of the literature pure fluid Toth models. Equilibrium capacities with quantitative uncertainties derived directly from DCB measurements without reference to a dynamic model should help increase the accuracy of mass transfer parameters extracted by the regression of such models to time dependent data.     

Equilibrium investigation of complex formation reactions involving copper(II), nitrilo-tris(methyl phosphonic acid) and amino acids,peptides or DNA constitutents. The kinetics,mechanism and correlation of rates with complex stability for metal ion promoted hydrolysis of glycine methyl ester

The complex formation reactions of [Cu(NTP)(OH₂)]^4? (NTP?=?nitrilo-tris(methyl phosphonic acid)) with some selected bio-relevant ligands containing different functional groups, are investigated. Stoichiometry and stability constants for the complexes formed are reported. The results show that the ternary complexes are formed in a stepwise mechanism whereby NTP binds to copper(II), followed by coordination of amino acid, peptide or DNA. Copper(II) is found to form Cu(NTP)H _n species with n?=?0, 1, 2 or 3. The concentration distribution of the various complex species has been evaluated. The kinetics of base hydrolysis of glycine methyl ester in the presence of copper(II)-NTP complex is studied in aqueous solution at different temperatures. It is proposed that the catalysis of GlyOMe ester occurs by attack of OH^? ion on the uncoordinated carbonyl carbon atom of the ester group. Activation parameters for the base hydrolysis of the complex [Cu(NTP)NH₂CH₂CO₂Me]^4? are, ΔH^±?=?9.5?±?0.3?kJ?mol^?1 and ΔS^±?=??179.3?±?0.9?J?K^?1?mol^?1. These show that catalysis is due to a substantial lowering of ΔH^±.     

Synthesis,crystal structures,and magnetic properties of methoxido-bridged dinuclear MnIII complexes derived from tri-dentate chelating ligands

Two new doubly methoxido-bridged Mn^III dinuclear complexes, [Mn^III(mphp)(μ-OCH₃)(CH₃OH)]₂·2CH₃OH (1) and ([Mn^III(ahbz)(μ-OCH₃)(CH₃OH)]₂·2CH₃OH (2), have been synthesized by using the tridentate ligands H₂mphp (H₂mphp = 2-methyl-6-(pyrimidin-2-yl-hydrazonomethyl)-phenol) and H₂ahbz (H₂ahbz = N-(2-amino-propyl)-2-hydroxy-benzamide). The complexes have been characterized by single-crystal X-ray diffraction analysis and magnetic measurements. Complexes 1 and 2 have a similar dimeric molecular structure. Two [Mn(L)(CH₃OH)]⁺ moieties (L^2? = mphp^2? or ahbz^2?) are bridged by two μ-OCH₃^? groups in the axial-equatorial asymmetric manner. The coordination geometry of Mn^III is an axially elongated octahedron with two oxygens of a methanol ligand and a methoxido ligand situated at the axial positions. Magnetic measurements indicate that 1 and 2 exhibit antiferromagnetic behavior with the fitting parameter of J = ?1.49(3) cm^?1, D = ?1.3(1) cm^?1, g = 1.98(1) and zJ′ = ?0.18(4) cm^?1 for 1, and J = ?1.6(2) cm^?1, D = 4.5(3) cm^?1, g = 2.06(1) and zJ′ = 1.4(1) cm^?1 for 2 on the basis of the spin Hamiltonian ? = ?2J?_Mn1?_Mn2.     

Interaction of the Benzenium Ion with Inert Ligands: IR Spectra of C6H7+?Ln Cluster Cations (L=Ar,N2, CH4, H2O)

IR photodissociation spectra of mass‐selected clusters composed of protonated benzene (C₆H₇⁺) and several ligands L are analyzed in the range of the C? H stretch fundamentals. The investigated systems include C₆H₇⁺? Ar, C₆H₇⁺? (N₂)_n (n=1–4), C₆H₇⁺? (CH₄)_n (n=1–4), and C₆H₇⁺? H₂O. The complexes are produced in a supersonic plasma expansion using chemical ionization. The IR spectra display absorptions near 2800 and 3100 cm^?1, which are attributed to the aliphatic and aromatic C? H stretch vibrations, respectively, of the benzenium ion, that is, the σ complex of C₆H₇⁺. The C₆H₇⁺? (CH₄)_n clusters show additional C? H stretch bands of the CH₄ ligands. Both the frequencies and the relative intensities of the C₆H₇⁺ absorptions are nearly independent of the choice and number of ligands, suggesting that the benzenium ion in the detected C₆H₇⁺? L_n clusters is only weakly perturbed by the microsolvation process. Analysis of photofragmentation branching ratios yield estimated ligand binding energies of the order of 800 and 950 cm^?1 (≈9.5 and 11.5 kJ mol^?1) for N₂ and CH₄, respectively. The interpretation of the experimental data is supported by ab initio calculations for C₆H₇⁺? Ar and C₆H₇⁺? N₂ at the MP 2/6‐311 G(2df,2pd) level. Both the calculations and the spectra are consistent with weak intermolecular π bonds of Ar and N₂ to the C₆H₇⁺ ring. The astrophysical implications of the deduced IR spectrum of C₆H₇⁺ are briefly discussed.     

Rate constants and transition‐state geometry of reactions of alkyl,alkoxyl, and peroxyl radicals with thiols

Enthalpy, activation energy, and rate constant of 9 alkyl, 3 acyl, 3 alkoxyl, and 9 peroxyl radicals with alkanethiols, benzenethiol, and L ‐cysteine are calculated. The intersection parabolas model is used for activation energy calculations. Depending on the structure of attacking radical, the activation energy of reactions with alkylthiols varies from 3 to 43 kJ mol^?1 for alkyl radicals, from 7 to 9 kJ mol^?1 for alkoxyl, and from 18 to 35 kJ mol^?1 for peroxyl radicals. The influence of adjacent π‐bonds on activation energy is estimated. The polar effect is found in reactions of hydroxyalkyl and acyl radicals with alkylthiols. The steric effect is observed in reactions of alkyl radicals with tert‐alkylthiols. All these factors are characterized via increments of activation energy. Quantum chemical calculations of activation energy and geometry of transition state were performed for model reactions: C^?H₃ + CH₃SH, CH₃O^? + CH₃SH, and HO₂^? + CH₃SH with using density functional theory and Gaussian‐98. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 284–293, 2009     

Spectroscopic studies of 4-substituted pyridinium 2-pyridylcarbonylmethylide-rhodium(I) complexes and x-ray molecular structure of (1,5-cyclooctadiene) (4-methylpyridinium 2-pyridylcarbonylmethylide)rhodium(I) perchlorate

(1,5-Cyclooctadiene) (4-substituted pyridinium 2-pyridylcarbonylmethylide)- rhodium(I) perchlorates, [Rh(COD)(C₅H₄NC(O)C?H₊C₅H₄X-4)]ClO₄ [COD = 1,5-cyclooctadiene; X = CH₃C(O), CH₃OC(O), C₆H₅, CH₃, and H], have been prepared. They are shown to have the geometry with coordination by the pyridyl nitrogen and carbonyl oxygen atoms of the ylide ligands and to exhibit intramolecular rearrangement of coordinated COD in chloroform, methanol, and dimethyl sulphoxide based on IR and ¹H NMR spectroscopies. Although the ylides have exhibited fluorescence bands due to an intramolecular charge-transfer transition and phosphorescence bands due to a carbonyl ³(n?π^*) transition, the complexes have given emission bands due to the metal-to-ylide ligand charge-transfer transition. A.single crystal X-ray crystal structure has been determined for [Rh(COD)(C₅H₄NC(O)C?H₊C₅H₄CH₃-4)]ClO₄. The crystals are monoclinic, space group P2₁/n with cell dimensions a = 14.887(3), b = 20.274(4), c = 6.966(1) Å, β = 96.13(1)°, and Z = 4. The structure has been refined by a block-diagonal least-squares method to final R = 0.060 for 2997 independent reflections with |F_o| > 3σ(F). The ylide carbon-pyridinium nitrogen bond distance is 1.420(10) Å. The bonded distances from rhodium to the midpoints of the double bonds of COD are 1.982(11) and 2.014(12) Å.