Gas-phase Formation Research Articles

Direct gas-phase formation of complex core–shell and three-layer Mn–Bi nanoparticles

STEM images and elemental maps of Mn and Bi showing formation of complex core–shell and three-layer structure.

Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner.

Polychlorinated naphthalenes (PCNs) are dioxins-like compounds and are formed along with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in thermal and combustion procedures. Chlorophenols (CPs) are the most important forerunners of PCNs. A comprehensive comprehension of PCN formation procedure from CPs is a precondition for reducing the discharge of PCNs. Experiments on the formation of PCNs from CPs have been hindered by PCN toxicity and short of precise detection methods for active intermediate radicals. In this work, PCN formation mechanism in gas-phase condition from 2-chlorophenol (2-CP) as forerunner was studied by quantum chemistry calculations. Numbers of energetically advantaged formation routes were proposed. The rate constants of key elementary steps were calculated over 600–1200 K using canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT) method. This study illustrates formation of PCNs with one chlorine atom loss from 2-CP is preferred over that without chlorine atom loss. In comparison with formation of PCDFs from 2-CP, PCN products are less chlorinated and have lower formation potential.

Quantum Chemical and Kinetic Study on Polychlorinated Naphthalene Formation from 3-Chlorophenol Precursor.

Polychlorinated naphthalenes (PCNs) are the smallest chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and are often called dioxin-like compounds. Chlorophenols (CPs) are important precursors of PCN formation. In this paper, mechanistic and kinetic studies on the homogeneous gas-phase formation mechanism of PCNs from 3-CP precursor were investigated theoretically by using the density functional theory (DFT) method and canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT). The reaction priority of different PCN formation pathways were disscussed. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600−1200 K. The mechanisms were compared with the experimental observation and our previous works on the PCN formation from 2-CP and 4-CP. This study shows that pathways ended with Cl elimination are favored over those ended with H elimination from the 3-CP precursor. The formation potential of MCN is larger than that of DCN. The chlorine substitution pattern of monochlorophenols has a significant effect on isomer patterns and formation potential of PCN products. The results can be input into the environmental PCN controlling and prediction models as detailed parameters, which can be used to confirm the formation routes of PCNs, reduce PCN emission and establish PCN controlling strategies.

Homogeneous gas-phase formation of polychlorinated naphthalene from dimerization of 4-chlorophenoxy radicals and cross-condensation of phenoxy radical with 4-chlorophenoxy radical: Mechanism and kinetics study

A direct density functional theory (DFT) calculation was performed for the formation of polychlorinated naphthalenes (PCNs) from dimerization of 4-chlorophenoxy radicals (4-CPRs) and cross-condensation of phenoxy radical (PhR) with 4-CPR, respectively. Several energetically feasible formation routes were proposed. The rate constants were computed by the canonical variational transition-state theory (CVT) with the small curvature tunneling (SCT) contribution over temperature range of 600–1200K. This study shows that PCN productions from the dimerization of 4-CPRs just contain DCNs. All the monochlorinated naphthalene (MCN) detected in the experiment from 4-chlorophenol (4-CP) as precursor are formed form the cross-condensation of PhR with 4-CPR.

Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCTA/DTs from 2,4-Dichlorothiophenol and 2,4,6-Trichlorothiophenol

Polychlorinated thianthrene/dibenzothiophenes (PCTA/DTs) are sulfur analogues compounds to polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs). Chlorothiophenols (CTPs) are key precursors to form PCTA/DTs. 2,4-DCTP has the minimum number of Cl atoms to form 2,4,6,8-tetrachlorinated dibenzothiophenes (2,4,6,8-TeCDT), which is the most important and widely detected of the PCDTs. In this paper, quantum chemical calculations were carried out to investigate the homogeneous gas-phase formation of PCTA/DTs from 2,4-DCTP and 2,4,6-TCTP precursors at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Several energetically feasible pathways were revealed to compare the formation potential of PCTA/DT products. The rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600–1200 K. This study shows that pathways that ended with elimination of Cl step were dominant over pathways ended with elimination of the H step. The water molecule has a negative catalytic effect on the H-shift step and hinders the formation of PCDTs from 2,4-DCTP. This study, together with works already published from our group, clearly illustrates an increased propensity for the dioxin formation from CTPs over the analogous CPs.

The in situ gas-phase formation of a C-glycoside ion obtained during electrospray ionization tandem mass spectrometry. A unique intramolecular mechanism involving an ion-molecule reaction.

This study examines the electrospray ionization mass spectrometry (ESI-MS), in-source collision-induced dissociation (CID) fragmentation and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) of a synthetic pair of β- and α-anomers of the amphiphilic cholesteryl polyethoxy neoglycolipids containing the 2-azido-2-deoxy-D-galactosyl-D-GalN3 moiety. We describe the novel and unique in situ gas-phase formation of a C-glycoside ion formed during all these gas-phase processes and propose a reasonable mechanism for its formation. The synthetic amphiphilic glycolipids were composed of the 2-deoxy-2-azido-D-galactosyl moiety (GalN3, the hydrophilic part) covalently attached to a polyethoxy spacer which is covalently linked to the cholesteryl moiety (hydrophobic part). The 2-azido-2-deoxy-α- and β-D-galactosyl-containing glycolipids were studied by in-time and in-space ESI-MS and CID-MS/MS in positive ion mode, with quadrupole ion trap (QIT), quadrupole-quadrupole-time-of-flight (QqTOF), and Fourier transform ion cyclotron resonance (FTICR) instruments. Conventional single-stage ESI-MS analysis showed the formation of the protonated molecule. During the single-stage ESI-MS analysis and the CID-MS/MS of the [M+H](+) and [M+NH4](+) adducts obtained from both glycolipid anomers, the presence of a series of specific product ions with different intensities was observed, consistent with the [C-glycoside+H-N2](+), [cholestadiene+H](+), 2-deoxy-2-D-azido-galactosyl [GalN3](+), [GalNH](+) and [sugar-Spacer+H](+) ions. The gas-phase formation of the [C-glycoside+H-N2](+) ion isolated from the glycolipid anomers was observed during both the ESI-MS of the glycolipids and the CID-MS/MS analyses of the [M+H](+) ions and it was found to occur by an intramolecular rearrangement involving an ion-molecule complex. CID-QqTOF-MS/MS and CID-FTICR-MS(2) analysis allowed the differentiation of the two glycolipid anomers and showed noticeable variation in the intensities of the product ions.

Gas-phase formation of the prebiotic molecule formamide: insights from new quantum computations

Abstract New insights into the formation of interstellar formamide, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction NH2 + H2CO → NH2CHO + H. Contrarily to what previously suggested, this reaction is essentially barrierless and can, therefore, occur under the low temperature conditions of intestellar objects thus providing a facile formation route of formamide. The rate coefficient parameters for the reaction channel leading to NH2CHO + H have been calculated to be A = 2.6 × 10−12 cm3 s−1, β = −2.1 and γ = 26.9 K in the range of temperatures 10–300 K. Including these new kinetic data in a refined astrochemical model, we show that the proposed mechanism can well reproduce the abundances of formamide observed in two very different interstellar objects: the cold envelope of the Sun-like protostar IRAS16293−2422 and the molecular shock L1157-B2. Therefore, the major conclusion of this Letter is that there is no need to invoke grain-surface chemistry to explain the presence of formamide provided that its precursors, NH2 and H2CO, are available in the gas phase.

Influence of water on the homogeneous gas-phase formation mechanism of polyhalogenated dioxins/furans from chlorinated/brominated phenols as precursors

Water is of great chemical importance due to its ability to form hydrogen bond. Polyhalogenated dibenzo-p-dioxin/benzofurans (PHDD/Fs) are notorious due to their persistence, bioaccumulation and extremely high toxicity. Water is ubiquitous, and a deep knowledge of its influence on the formation mechanism of PHDD/Fs is necessary. This work investigated the influence of water on the homogeneous gas-phase formation of PHDD/Fs from halogenated phenols (HPs) as precursors by using quantum chemical calculations with the aid of the MPWB1K theoretical approach in connection with the 6-31+G(d,p) and 6-311+G(3df,2p) basis sets. The schematic energy profile in the presence of water was constructed and compared with the situation without water. This study reveals for the first time that the introduction of water promotes the formation of halogenated phenoxy radicals (HPRs) from the H abstraction reactions of HPs with atomic H and OH radicals by lowering the reaction energy barriers and opening new low-energy pathways. Another intriguing finding of this work is that the inclusion of a water molecule produces a catalytic effect on the H-shift step involved in the formation of PHDFs and thus their formation potential is enhanced.

Distributive Characteristics of Gas Phase in a Liquid when Bottom Blowing

This paper provides the results of research into the structure of gas flow in a plume rayed by laser in barbotage zone. The technology of steel out-of-furnace treatment facing a number of challenges necessitates a quite clear view of mechanisms of structure formation and dynamics of liquid and gas phases in an upward gas-liquid flow (in a “plume”) above the gas-feeding nozzle. Gas phase distribution, plume height and cross-section distribution and values of liquid rates determine mainly the dynamics of a melt flow in other out-of-the-plume parts of the bath.

GAS PHASE SYNTHESIS OF (ISO)QUINOLINE AND ITS ROLE IN THE FORMATION OF NUCLEOBASES IN THE INTERSTELLAR MEDIUM

Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium, yet the formation mechanisms of even their simplest prototypes—quinoline and isoquinoline—remain elusive. Here, we reveal a novel concept that under high temperature conditions representing circumstellar envelopes of carbon stars, (iso)quinoline can be synthesized via the reaction of pyridyl radicals with two acetylene molecules. The facile gas phase formation of (iso)quinoline in circumstellar envelopes defines a hitherto elusive reaction class synthesizing aromatic structures with embedded nitrogen atoms that are essential building blocks in contemporary biological-structural motifs. Once ejected from circumstellar shells and incorporated into icy interstellar grains in cold molecular clouds, these NPAHs can be functionalized by photo processing forming nucleobase-type structures as sampled in the Murchison meteorite.

PBCDD/F formation from radical/radical cross-condensation of 2-Chlorophenoxy with 2-Bromophenoxy, 2,4-Dichlorophenoxy with 2,4-Dibromophenoxy, and 2,4,6-Trichlorophenoxy with 2,4,6-Tribromophenoxy

Quantum chemical calculations were carried out to investigate the homogeneous gas-phase formation of mixed polybrominated/chlorinated dibenzo-p-dioxins/benzofurans (PBCDD/Fs) from the cross-condensation of 2-chlorophenoxy radical (2-CPR) with 2-bromophenoxy radical (2-BPR), 2,4-dichlorophenoxy radical (2,4-DCPR) with 2,4-dibromophenoxy radical (2,4-DBPR), and 2,4,6-trichlorophenoxy radical (2,4,6-TCPR) with 2,4,6-tribromophenoxy radical (2,4,6-TBPR). The geometrical parameters and vibrational frequencies were calculated at the MPWB1K/6-31+G(d,p) level, and single-point energy calculations were performed at the MPWB1K/6-311+G(3df,2p) level of theory. The rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600–1200K. Studies show that the substitution pattern of halogenated phenols not only determines the substitution pattern of the resulting PBCDD/Fs, but also has a significant influence on the formation mechanism of PBCDD/Fs, especially on the coupling of the halogenated phenoxy radicals.

Competition between nucleophilic substitution of halogen (SN Ar) versus substitution of hydrogen (SN ArH)-a mass spectrometry and computational study.

The mechanism of intramolecular gas-phase reactions of N-(2-X-5-nitrophenyl)-N-methylacetamide carbanions (X=H, F, Cl) has been studied using negative ion electrospray mass spectrometry ((-)ESI-MS) technique and modelled computationally. It was proven that all three anions form cyclic σ(H) adducts, which undergo elimination of water. In the case of X=F, formation of the σ(F) adduct, leading to SN Ar reaction, was a competing process. This is the first proof that also in the gas phase formation of σ(H) adduct proceeds faster than σ(X) adduct and only when X=F, rates of these two processes are comparable. The experimental results are in full agreement with quantum chemical calculations.

Mechanistic studies on the dibenzofuran formation from phenanthrene, fluorene and 9-fluorenone.

We carried out molecular orbital theory calculations for the homogeneous gas‑phase formation of dibenzofuran from phenanthrene, fluorene, 9-methylfluorene and 9-fluorenone. Dibenzofuran will be formed if ∙OH adds to C8a, and the order of reactivity follows as 9-fluorenone > 9-methylfluorene > fluorene > phenanthrene. The oxidations initiated by ClO∙ are more favorable processes, considering that the standard reaction Gibbs energies are at least 21.63 kcal/mol lower than those of the equivalent reactions initiated by ∙OH. The adding of ∙OH and then O2 to phenanthrene is a more favorable route than adding ∙OH to C8a of phenanthrene, when considering the greater reaction extent. The reaction channel from fluorene and O2 to 9-fluorenone and H2O seems very important, not only because it contains only three elementary reactions, but because the standard reaction Gibbs energies are lower than −80.07 kcal/mol.

PM2.5 acidity at a background site in the Pearl River Delta region in fall-winter of 2007–2012

Based on field observations and thermodynamic model simulation, the annual trend of PM2.5 acidity and its characteristics on non-hazy and hazy days in fall-winter of 2007–2012 in the Pearl River Delta region were investigated. Total acidity ([H+]total) and in-situ acidity ([H+]in-situ) of PM2.5 significantly decreased (F-test, p<0.05) at a rate of −32±1.5nmolm−3year−1 and −9±1.7nmolm−3year−1, respectively. The variation of acidity was mainly caused by the change of the PM2.5 component, i.e., the decreasing rates of [H+]total and [H+]in-situ due to the decrease of sulfate (SO42−) exceeded the increasing rate caused by the growth of nitrate (NO3−). [H+]total, [H+]in-situ and liquid water content on hazy days were 0.9–2.2, 1.2–3.5 and 2.0–3.0 times those on non-hazy days, respectively. On hazy days, the concentration of organic matter (OM) showed significant enhancement when [H+]in-situ increased (t-test, p<0.05), while this was not observed on non-hazy days. Moreover, when the acidity was low (i.e., R=[NH4+]/(2×[SO42−]+[NO3−])>0.6), NH4NO3 was most likely formed via homogenous reaction. When the acidity was high (R≤0.6), the gas-phase formation of NH4NO3 was inhibited, and the proportion of NO3− produced via heterogeneous reaction of N2O5 became significant.

Destruction of cylindrical ampoules containing solid phase reaction mixtures under explosive loading

Peculiarities of solid-phase synthesis are experimentally and numerically investigated in the aluminum-sulfur and aluminum-teflon mixtures placed in cylindrical ampoules under explosive loading. In the experiments, the parameters of explosive loading are chosen close to those that are commonly used for explosive compaction of inert porous fillers in cylindrical ampoules. The experimental results show that cylindrical ampoules are damaged when a mixture capable of ultrafast exothermic reactions is used as filler under explosive loading. To find the reasons of ampoule damage, the numerical computations are carried out by the finite element method based on the model of a multicomponent medium. The synthesis reaction in the mixture is described using the phenomenological model of irreversible chemical reactions based on zero-order kinetics. Simulation of porous mixture compaction is carried out using the kinetic model of the active type, which determines the growth or collapse of pores continually changing the material properties and causing stress relaxation. The sharp increase in pressure is found in the bottom part of the ampoule after reflection of the shock wave from the bottom lid of the ampoule in the form of a compression wave, which is accompanied by increasing the rate of chemical reactions. The high rate of heat release during chemical reactions in the bottom part of the ampoule leads to the formation of gas phase, which leads to further increase in pressure and fracture of the ampoule.

Interstellar processes: Ortho/para conversion, radiative association, and dissociative recombination

The study of the ortho-to-para ratio of assorted gas-phase interstellar molecules such as H2 ,H 2O, NH3 ,a nd H2O + has gained interest in recent years, based partially on new spectral observations of light hydrides by the Herschel Space Observatory. Although these ratios can yield valuable information about the thermal history of the interstellar cloud where the molecules are found, an understanding of how the ratios are determined involves a number of often poorly studied processes, which can include both gas-phase and grain-surface reactions. In this article, we consider the processes that determine the ortho-to-para ratio of the molecular ion H2O + in diffuse interstellar clouds and attempt to reproduce an unusual observed ratio for this ion. In addition to the study of ortho-to- para ratios, we look carefully at current uncertainties in the gas-phase formation of large neutral molecules in cold dense interstellar clouds via ion-neutral radiative association and dissociative recombination, among other processes.

Heterogeneity‐enhanced gas phase formation in shallow aquifers during leakage of CO2‐saturated water from geologic sequestration sites

AbstractA primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

Development of a thermodynamic model of aqueous solution suited for foods and biological media. Part B: Prediction of standard formation properties

AbstractIn food and biological processes, aqueous complexes cover a wide diversity of species and the presence of several phases. The modelling of such processes must take into account these specificities, which require a generalization of the existing thermodynamic models of aqueous solutions.The chemical potential (the molar Gibbs free energy) of a given compound is an important variable to characterize the physical‐chemical properties at equilibrium. Its value depends on two parameters: the Gibbs free energy of formation and the activity coefficient. Both are linked to a chosen reference state. Then, the main thermodynamic modelling task consists in the prediction and/or the collection of formation properties data and in the development of a predictive model of activity coefficients.In this study, a method of prediction of the gas phase formation properties of several organic molecules of interest in foods and biological media using the same input data as those of the COSMO‐RS model (i.e., results of quantum DFT/COSMO calculations) is introduced. This kind of fully predictive approach allows the treatment of conformations. This is its main advantage compared to classical group contribution methods.For fifteen of the studied molecules, the Gibbs free energies of formation predicted at infinite dilution in water are also calculated and compared to experimental data.

Effects of humidity and [NO3]/[N2O5] ratio on the heterogeneous reaction of fluoranthene and pyrene with N2O5/NO3/NO2.

Atmospheric 2-nitrofluoranthene (2-NFL) and 2-nitropyrene (2-NPY) were two important nitro-polycyclic aromatic hydrocarbons (NPAHs). Especially, 2-NFL was recognized to be the most abundant particle-associated NPAH (Ramdahl et al., 1986). In previous studies, these two products were observed in the gas-phase reaction between N2O5/NO3/NO2 and their parent polycyclic aromatic hydrocarbons (PAHs), while the heterogeneous reaction generated other nitro-PAH isomers (1, 3, 7, 8-NFL and 1-NPY) (Atkinson et al. 1990). To clarify the possible reasons for this difference, the heterogeneous reactions of suspended fluoranthene (FL) and pyrene (PY) particles under different relative humidity (RH; 0.5%-43%) and [NO3]/[N2O5] ratios were carried out. Under low humidity (0.5% RH) or a relatively high ratio of [NO3]/[N2O5], 2-NFL and 2-NPY were observed as the major nitro-FL isomers for the first time in the heterogeneous reaction. Decreasing the humidity or increasing the [NO3]/[N2O5] ratio in the reaction essentially increases the concentration radio of [NO3(g)]/[NO2(+)(aq)] on the particle surface (NO2(+) is derived from the ionization of N2O5). Thus, it can be concluded that under different atmospheric conditions, the change of [NO3(g)]/[NO2(+)(aq)] in the particle surface has an influence on the product distribution of FL and PY in the atmosphere. The experimental results provide evidence for the heterogeneous formations of particle-bound 2-NFL and 2-NPY. However, relative to the gas-phase formation, they will be negligible in the real atmosphere. 2-NFL and 2-NPY observed in the ambient particles should mainly derive from deposition of gas-phase reactions. Additionally, this study also clarifies the reason for different nitro-PAHs isomers observed between gas and particulate reactions.

Understanding chitosan as a gene carrier: A DFT study

We described density functional study carried out in order to delve into the interaction between chitosan, a gene carrier and nucleobases. Our study asserts the pivotal role played by hydrogen bonding in chitosan–nucleobase adduct formation. Incorporation of aqueous medium is found to bring about a significant impact on the interaction between the two. Thermochemical analysis suggests the presence of strong thermodynamic driving force for adduct formation in gas phase while no such driving force is observed in aqueous phase. Moreover, except adenine, aromaticity of nucleobases is enhanced by adduct formation with chitosan. Protonation of the nucleobases leads to dissociation of the two constituents of the adducts.