Semi-empirical and ab initio quantum chemical characterisation of pyridine derivatives as HCl inhibitors of aluminium surface

Quantum chemical methods are becoming ever more prevalent for assessing surface interactions of different molecules using cluster models and semi-empirical, ab initio Hartree–Fock and density functional theory (DFT) studies considering the standard potential energy surfaces. Examination of the efficacy of some pyridine derivatives to counter aluminium corrosion in hydrochloric acid using ab initio and semi-empirical quantum chemical deductions and its comparison with the available experimental data forms the basis of this research. It is believed that the inhibition efficiency has lucid correlation with the total energy of inhibitor molecules and highest occupied molecular orbital energy levels calculated by DFT study methods and thus the adsorption energy for the pyridine on Al₁, Al₅, Al₁₄, Al₁₈ and Al₂₆ clusters are determined to assess the convergence of the results with respect to size of the cluster. Subsequently, Al₂₆ is used for the inhibitor/aluminium cluster interface investigations. Results highlight the reaction between pyridine molecules and appropriately active sites such as corners and steps or kinks and screw dislocations towards which pyridine molecules are attracted as is evident from a three times rise in adsorption energy from (−35) to (−107) kJ mol⁻¹. Therefore, inhibition mechanism is primarily associated with local properties. Interactions take place between the surface defect and the nitrogen group of the pyridine molecule however, the possibility of ion pair formation between protonated pyridine and chloride ion and its influence on the general adsorption of pyridine on aluminium is also examined. The interaction energies of pyridine and aluminium cluster with the natural bond orbital are also reported.     

A New Approach for Optimization of Distributed Quantum Circuits

International Journal of Theoretical Physics - In the present work, a novel approach was proposed to optimize the teleportation cost in Distributed Quantum Circuits (DQCs) by applying a new...     

Dehydration of acetonitrile using cross-linked sodium alginate membrane containing nano-sized NaA zeolite

Pervaporation (PV) separation of water–acetonitrile mixture using sodium alginate (NaAlg) based mixed matrix membranes (MMM) comprising different amounts of nano NaA zeolite (10, 20 and 30 wt%) is investigated in various concentrations of water and temperatures. The prepared membranes are modified by sulfosuccinic acid (SSA) as a crosslinking agent. NaAlg-NaA/SSA membranes are synthesized by a solution casting technique. The process and membrane performance including separation factor, flux and activation energy of permeation are determined. Results reveal that adding of nano zeolite may lead to an increase in the flux and the separation factor of sodium alginate membrane up to 123 and 169%. In addition, using MMM in dehydration of a feed containing 30 wt% of water shows much better performance than alginate membrane. Furthermore, the activation energy of water permeation through MMM is predicted lower than sodium alginate membrane which reflects the facilitated permeation of water through MMM.     

DC-Pulsed Plasma for Dry Reforming of Methane to Synthesis Gas

The carbon dioxide reforming of methane to synthesis gas under DC-pulsed plasma was investigated. The effects of specific input energy and feed ratio on the product distribution and also feed conversion was studied. At the input energy of about 11 eV/molecule per methane and/or carbon dioxide the feed conversion of 38% for CH₄ and 28% for CO₂ and product selectivity of 74% has been attained for H₂ and CO at feed flow rate of 90 ml/min. The energy consumption in this work displays potential to further study and optimization of the process. The importance of the electron impact reactions in the process was discussed. The results show that by prudent tuning of system variables, the process be able to run in the way of synthesis gas, instead of hydrocarbon production.     

The thermal conductivities enhancement of mono ethylene glycol and paraffin fluids by adding β-SiC nanoparticles

Changes in the thermal conductivities of paraffin and mono ethylene glycol (MEG) as a function of β-SiC nanoparticle concentration and size was studied. An enhancement in the effective thermal conductivity was found for both fluids (i.e., both paraffin and MEG) upon the addition of nanoparticles. Although an enhancement in thermal conductivity was found, the degree of enhancement depended on the nanoparticle concentration in a complex way. An increase in particle-to-particle interactions is thought to be the cause of the enhancement. However, the enhancement became muted at higher particle concentrations compared to lower ones. This phenomenon can be related to nanoparticles interactions. An improvement in the thermal conductivities for both fluids was also found as the nanoparticle size shrank. It is believed that the larger Brownian motion for smaller particles causes more particle-to-particle interactions, which, in turn, improves the thermal conductivity. The role that the base-fluid plays in the enhancement is complex. Lower fluid viscosities are believed to contribute to greater enhancement, but a second effect, the interaction of the fluid with the nanoparticle surface, can be even more important. Nanoparticle-liquid suspensions generate a shell of organized liquid molecules on the particle surface. These organized molecules more efficiently transmit energy, via phonons, to the bulk of the fluid. The efficient energy transmission results in enhanced thermal conductivity. The experimentally measured thermal conductivities of the suspensions were compared to a variety of models. None of the models proved to adequately predict the thermal conductivities of the nanoparticle suspensions.     

Thermal analysis of CsH<Subscript>2</Subscript>PO<Subscript>4</Subscript> nanoparticles using surfactants CTAB and F-68

A study concerned to thermogravimetric analysis is performed in cesium dihydrogen phosphate (CsH₂PO₄) that was synthesized, using cetyltrimethylammonium-bromide (CTAB), polyoxyethylene-polyoxypropylene (F-68) and mixture of (F-68:CTAB) with two mole ratio 0.06 and 0.12 as surfactant. The dehydration behavior of particles was studied using thermal gravimetric analysis and differential scanning calorimetric. Subsequently, the experimental results indicated that the first dehydration temperature in the range of 237–239 °C upon heating, the second peaks occur at temperature range 290–295 °C and overlapping in the thermogravimetric events is observed. The mass loss values are obtained in the range of 6.62–6.97 wt% that is less than reported theoretical value 7.8 wt%. These values show well compatibility of reaction CsH₂PO₄ to Cs₂H₂P₂O₇ with 3.92 wt% whereas mass loss value of CsH₂PO₄ to CsPO₃ is less than theoretical value 7.8 wt%. The activation energy of two steps dehydration are calculated using Kissinger equation for the samples synthesized via CTAB and (F-68) with minimum value mass loss 6.62% and maximum value mass loss 6.97%, respectively. The calculation results reveal that the reaction rate in the first step (CsH₂PO₄ → Cs₂H₂P₂O₇) is faster than the second step (CsH₂PO₄ → CsPO₃). The weight loss values of the samples demonstrate that existence of CTAB can be considered as effective factor which prevents more weight loss during the dehydration process.     

A new dimensionless group model for determining the viscosity of nanofluids

Immobilization of lead contamination in soils by precipitation of non-assimilable for plants Pb-phosphate was considered. Glassy fertilizer of controlled release rate of the nutrients for plants as a source of phosphate anions was applied. Thermal analysis methods (TG/DTG/DTA) were used for the identification of components of Pb-precipitate, which being in statu nascendi have nonstoichiometric composition and disordered crystallographic structure difficult to identify by XRD method. Application of TA methods permits to demonstrate the negative role of Pb complexing citric acid solution simulating the natural soil conditions, which inhibits the Pb-phosphate of pyromorphite type formation.     

Electrocatalytic oxidation of nitrite at a terpyridine manganese(II) complex modified carbon past electrode

A carbon past electrode modified with [Mn(H₂O)(N₃)(NO₃)(pyterpy)], ( \textpyterpy = 4￠- ( 4 - \textpyridyl ) - 2,2￠:\text6￠,\text2￠￠- \textterpyridine ) \left( {{\text{pyterpy}} = 4\prime - \left( {4 - {\text{pyridyl}}} \right) - 2,2\prime:{\text{6}}\prime,{\text{2}}\prime\prime - {\text{terpyridine}}} \right) complex have been applied to the electrocatalytic oxidation of nitrite which reduced the overpotential by about 120 mV with obviously increasing the current response. Relative standard deviations for nitrite determination was less than 2.0%, and nitrite can be determined in the ranges of 5.00 × 10⁻⁶ to 1.55 × 10⁻² mol L⁻¹, with a detection limit of 8 × 10⁻⁷ mol L⁻¹. The treatment of the voltammetric data showed that it is a pure diffusion-controlled reaction, which involves one electron in the rate-determining step. The rate constant k′, transfer coefficient α for the catalytic reaction, and diffusion coefficient of nitrite in the solution, D, were found to be 1.4 × 10⁻², 0.56× 10⁻⁶, and 7.99 × 10⁻⁶ cm² s⁻¹, respectively. The mechanism for the interaction of nitrite with the Mn(II) complex modified carbon past electrode is proposed. This work provides a simple and easy approach to detection of nitrite ion. The modified electrode indicated reproducible behavior, anti-fouling properties, and stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Protic ionic liquid [TMG][Ac] as an efficient,homogeneous and recyclable catalyst for Boc protection of amines

An efficient and practical protocol for the chemoselective N-Boc protection of various structurally different aryl, aliphatic and heterocyclic amines was carried out with (Boc)₂O using protic 1, 1, 3, 3-tetra-methylguanidinium acetate (10 mol%) as recyclable catalyst under solvent free condition at ambient temperature. No competitive side reactions (isocyanate, urea and N, N-di-Boc) were observed. α-Amino alcohols afforded the N-Boc-derivative without oxazolidinone formation.