Gas-phase molecular halogen formation from NaCl and NaBr aerosols: when are interface reactions important?

Unique interface reactions at the surface of sea-salt particles have been suggested as an important source of photolyzable gas-phase halogen species in the troposphere. Many factors influence the relative importance of interface chemistry compared to aqueous-phase chemistry. The Model of Aerosol, Gas, and Interfacial Chemistry (MAGIC 2.0) is used to study the influence of interface reactions on gas-phase molecular halogen production from pure NaCl and NaBr aerosols. The main focus is to identify the relative importance of bulk compared to interface chemistry and to determine when interface chemistry dominates. Results show that the interface process involving Cl-(surf) and OH(g) is the main source of Cl2(g). For the analogous oxidation of bromide by OH, gaseous Br2 is formed mainly in the bulk aqueous phase and transferred across the interface. However, the reaction of Br-(surf) with O3(g) at the interface is the primary source of Br2(g) under dark conditions. The effect of aerosol size is also studied. Potential atmospheric implications and effects of interface processes on aerosol pH are discussed.     

Determination of iodine and bromine compounds by ion chromatography/dynamic reaction cell inductively coupled plasma mass spectrometry.

An inductively coupled plasma mass spectrometer (ICP-MS) was used as an ion chromatographic detector for the speciation of iodine and bromine. Gradient elution using NH4NO3 at pH 10 allowed the chromatographic separation of ionic iodine (I- and IO3-) and bromine (Br- and BrO3-) species in less than 8 min. Effluents from the ion-exchange column were delivered to the nebulization system of ICP-MS for the determination of I and Br. The potentially interfering 38Ar40ArH+ and 40Ar40ArH+ at the bromine masses m/z 79 and 81 were significantly reduced in intensity (by approximately two orders of magnitude) by using 0.6 mL min(-1) O2 as a reactive cell gas in the dynamic reaction cell (DRC). Moreover, the signal-to-background ratio at iodine mass m/z 127 increased significantly when O2 was used as the reaction gas. The detection limits were in the range of 0.001-0.002 and 0.03-0.04 ng mL(-1) for various I and Br compounds, respectively, based on the peak height. The relative standard deviation of the peak areas for five injections of a 2 ng mL(-1) I-, IO3- and 20 ng mL(-1) Br-, BrO3- mixture was in the range of 3-4%. The concentrations of I and Br compounds have been determined in selected water and urine samples. The spike recoveries were in the range of 94-102% for all of the determinations. This method has also been applied to determine various I and Br compounds in an NIST RM 8435 whole-milk powder reference material and a seaweed sample obtained locally. A microwave-assisted extraction method was used to extract these compounds, which were quantitatively leached with a 10% mass/volume (m/v) tetramethylammonium hydroxide (TMAH) solution in a focused microwave field within a period of 6 min. The major components of I and Br in milk powder and seaweed were I- and Br-.     

Br2 production from the heterogeneous reaction of gas-phase OH with aqueous salt solutions: Impacts of acidity, halide concentration, and organic surfactants

This study reports the first laboratory measurement of gas-phase Br2 production from the reaction between gas-phase hydroxyl radicals and aqueous salt solutions. Experiments were conducted at 269 K in a rotating wetted-wall flow tube coupled to a chemical-ionization mass spectrometer for analysis of gas-phase components. From both pure NaBr solutions and mixed NaCl/NaBr solutions, the amount of Br2 released was found to increase with increasing acidity, whereas it was found to vary little with increasing concentration of bromide ions in the sample. For mixed NaCl/NaBr solutions, Br2 was formed preferentially over Cl2 unless the Br- levels in the solution were significantly depleted by OH oxidation, at which point Cl2 formation was observed. Presence of a surfactant in solution, sodium dodecyl sulfate, significantly suppressed the formation of Br2; this is the first indication that an organic surfactant can affect the rate of interfacial mass transfer of OH to an aqueous surface. The OH-mediated oxidation of bromide may serve as a source of active bromine in the troposphere and contribute to the subsequent destruction of ozone that proceeds in marine-influenced regions of the troposphere.     

Efficient eosin y dye-sensitized solar cell containing Br-/Br3- electrolyte

We found that Br-/Br3- is more suitable than an I-/I3- couple in dye-sensitized solar cells in terms of higher open-circuit photovoltage (Voc) production and higher overall energy conversion efficiency (eta) if the dye sensitizer has a more positive potential than that of Br-/Br3-. Under simulated AM1.5 one sun, an eosin Y dye-sensitized solar cell containing 0.4 M LiBr + 0.04 M Br2 electrolyte in acetonitrile yielded a short-circuit photocurrent (Jsc) of 4.63 mA cm(-2), Voc of 0.813 V, and fill factor (FF) of 0.693, corresponding to 2.61% of eta. Under the same conditions except for the electrolyte 0.4 M LiI + 0.04 M I2 in acetonitrile instead, the device produced 1.67% of eta (Jsc = 5.15 mA cm(-2), Voc = 0.451 V, FF = 0.721). Replacement of I-/I3- with Br-/Br3- in eosin Y dye-sensitized solar cells yielded a significant increase in Voc offset by slight decreases in Jsc and FF, leading to an increase in eta by 56%. The significant gain in Voc was attributed to the enlarged energy level difference between the redox potential of the electrolyte and the Fermi level of TiO2 and the suppressed charge recombination as well. The rate for charge recombination between bromine and the injected electrons was determined to be first order in bromine.     

Theoretical study on the structure of the BrO hydrates

The hydrates of bromine monoxide, BrO(H2O)n, n = 1-4, have been studied by means of ab initio calculations at the B3LYP/aug-cc-pVTZ level of theory. These systems could be formed in the troposphere and participate in chemical reactions involved in the depletion of ozone. Several conformations are obtained and discussed for each of the hydrates mentioned. Two rather different intermolecular interactions are found, namely, conventional hydrogen bonding and Br...O associations. In contrast with a more traditional point of view in which hydrogen bonds could be assumed as the preferential interaction for the formation of these complexes, it is the Br...O association which yields the most stable conformations. Equilibrium geometries, harmonic frequencies, and relative energies have been calculated for the bromine monoxide hydrates for the first time. The theoretical binding energies indicate that the stabilization of the hydrates increases with the number of water molecules added. Cooperative effects are suggested to play a significant role in this stabilization. An analysis of relevant properties depending on the electron density in the bond critical points of the Br...O associations has been done for the first time, showing characteristic features of this interaction in comparison with the hydrogen bonds formed.     

Toward understanding the Hofmeister series. 3. Effects of sodium halides on the molecular organization of H2O as probed by 1-propanol

We investigated the effects of NaF, NaCl, NaBr, and NaI on the molecular organization of H2O by a calorimetric methodology developed by us earlier. We use the third derivative quantities of G pertaining to 1-propanol (1P) in ternary 1P-a salt-H2O as a probe to elucidate the effects of a salt on H2O. We found that NaF and NaCl worked as hydration centers. The hydration numbers were 19 +/- 2 for NaF and 7.5 +/- 0.6 for NaCl. Furthermore, the bulk H2O away from the hydration shell was found unaffected by the presence of Na+, F-, and Cl-. For NaBr and NaI, in addition to the hydration to Na+, Br- and I- acted like a hydrophilic moiety such as urea. Namely, they formed a hydrogen bond to the existing H2O network and retarded the fluctuation nature of H2O. These findings were discussed with respect to the Hofmeister ranking. We suggested that more chaotropic anions Br- and I- are characterized as hydrophiles, whereas kosmotropes, F- and Cl-, are hydration centers.     

Problems connected with the analysis of halocarbons and hydrocarbons in the non-urban atmosphere

The problems connected with the measurement of hydrocarbons outside urban areas are considerable: The atmospheric mixing ratios of most of the hydrocarbons are very low--from a few ppb down to some ppt; the mixture of hydrocarbons is extremely complex, ranging from light n-alkanes to alkyl benzenes and terpenes; for measurements in remote areas the logistic conditions often restrict the instrumentation which can be used for sample collection or in situ measurements (such as lack of electric power supply, weight restrictions etc.). Nevertheless, sensitive and sufficiently reliable measurements of hydrocarbons in the non-urban atmosphere are important. Hydrocarbons are important factors in the tropospheric photochemistry (e.g. ozone formation) and can be used as valuable tracers for man-made atmospheric pollutants etc. Other useful tracers for anthropogenic emission are halocarbons such as dichlormethane, tri- and tetrachloroethen etc. The impact of man-made hydrocarbons on the chemistry of the troposphere can only be understood if the extent of natural (biogenic) contributions is known. From measurements of a large variety of hydrocarbons and halocarbons it is often possible to obtain information about the sources of the most important atmospheric hydrocarbon species, even for trace gases with both significant anthropogenic and biogenic sources. In this presentation some of the problems and their solutions connected with such measurements of atmospheric hydrocarbons and halocarbons are presented and discussed. Some of the results obtained by several series of measurements are described, indicating that man-made as well as biogenic hydrocarbons can be important factors for the chemistry of the atmosphere.     

Rapid detection of Rosa laevigata polysaccharide content by near-infrared spectroscopy

We have investigated surface-enhanced Raman spectroscopy (SERS) spectrum of Omethoate (O,O-dimethyl-S-methylcarbamoylmethylthiophosphate). It is found significant signals in the ordinary Raman spectrum for solid-state Omethoate as well as strong vibrational signals absorbed on the silver sol surface which is prepared by γ-irradiation technique at a very low concentration. Effects of pH and anions (Cl-, Br-, I-) on the adsorption orientation are investigated as well. Two different adsorption mechanisms are deduced, depending on the experimental conditions. The sulfur atom or the sulfur and two oxygen atoms are adsorbed onto the silver sol surface. Among halide ions, Br- and I- are more strongly adsorbed onto the silver sol surface. As a result, the adsorption of Omethoate is less effective due to their steric hindrance.     

纯固体配料体系中不同碱金属卤化物对ZSM－48沸石合成及性质的影响 Ⅱ．不同卤化钾的影响

纯固体配料体系中引入碱金属钾的不同卤化物ＫＸ（Ｘ＝Ｆ~－，Ｃｌ~－，Ｂｒ~－，Ｉ~－）对ＺＳＭ－４８沸石的晶化和性质有着显著的影响。ＸＲＤ测试结果表明：引入不同的卤化钾对合成沸石的结构基本没有影响，但均大大降低了沸石的晶化速率。通过等离子光谱和ＸＰＳ测试发现沸石的体相硅铝比基本相同，但沸石表面的硅铝比显著不同。合成体系中引入一定量的ＫＩ很难合成ＺＳＭ－４８沸石，或者需要很长时间才能合成，引入ＫＦ和ＫＢｒ不利于生成稳定的产物。ＴＧ／ＤＴＡ表明引入不同的卤化钾强烈影响着产物的热性质。ＳＥＭ测试表明产物的晶体形貌和晶粒大小与卤化钾的类型有关。     

A selective detection of fluoride ions in DMSO by fluorescent and colorimetry competition assays based on 4-bromo-2,6-bis-(hydroxymethyl)phenol

A novel and very simple colorimetric and fluorometric method for selectively sensing F^- was proposed based on 4-bromo-2,6- bis（hydroxymethyl）phenol（BBHMP）,which is a simple and available phenolic receptor the absence of any special chromophoric function and with over wide range of anions（Cl^-,Br^-,I^-,AcO^-,HSO₄^-,NO₃^- and BzO^-） in DMSO media.The colorimetric method is described for naked-eye detection of F^- in the presence of the BBHMP.The BBHMP was found to show selective and sensitive fluorescence quenching response toward fluoride over than Cl^-,Br^-,I^-,AcO^-,HSO₄^-,NO₃^- and BzO^-.     

Fluorescence quenching of coumarins by halide ions

Fluorescence quenching of 4-methyl-7-methoxy coumarin (1) and 4-methyl-5-ethoxy-7-methoxy coumarin (2) in aqueous solutions have been studied at different concentrations of halide ions (Cl-, Br-, I-), at room temperature approximately 20 degrees C. It is observed that the fluorescence intensity of both the coumarin compounds (1 and 2) decrease with increase in the concentration of Br- and I- ions but remains almost constant in case of Cl- ion. It is observed that the quenching due to halide ions proceeds via both a diffusional and static quenching processes. The rate constants for diffusional as well as static component of quenching process have been calculated using modified Stern-Volmer relation. It is further observed, that I- ion has very high quenching ability than Br- ion and Cl) ion almost behaves as a non-quencher. It is explained in terms of the sphere of action model by showing that the value of radius of sphere of action of the halide quencher is greater than the sum of the radii of the respective coumarin and quencher. Further, pattern of the quenching ability of the halide quenchers is found to be as I- > Br- > Cl- and interestingly this is in the same order as of their ionization energy. Finally, the present quenching process has been attributed to the electron transfer resulting between colliding species.     

Ion exchange at a surface monolayer

Total reflection total conversion electron yield X-ray absorption fine structure is applied to the evaluation of ion exchange occurring at the surface monolayer of two-tailed ammonium ions. X-ray absorption measurements at a Br K-edge allow us to detect ion-exchange equilibria between Br- and Cl- added in a subphase. The ion-exchange selectivity of Br- over Cl- basically increases as the monolayer is compressed, indicating that Cl- is selectively squeezed out by compression because of its larger hydrated ionic radius.     

Modeling Anion Adsorption on Kaolinite

Anion adsorption onto kaolinite was quantified using the triple layer surface complexation model. Fluoride adsorption data were described by both anion exchange and H-bonded complexation mechanisms. The outer-sphere complexation mechanism was used to describe the weak adsorption of Cl-, Br-, and I- on kaolinite. The F- adsorption in the presence of Br- or I- was decreased over a range of pH 4-5 whereas Cl- showed a negligible effect. Competition for binding sites appeared to be an important factor in determining the adsorptive behavior of F- in Br- or I- mediated systems. Copyright 1999 Academic Press.     

Suppressed electrostatic ion chromatography with tetraborate as eluent and its application to the determination of inorganic anions in snow and rainwater

Tetraborate is investigated as the eluent ion for suppressed electrostatic ion chromatography (EIC) using a zwitterionic stationary phase. Good separation of a range of inorganic anions (SO4(2-), Cl-, NO3-, Br-, NO3-, ClO3-, and I-) was obtained, with detection limits for highly conducting ions (SO4(2-), Cl-, NO2-, Br- , and NO3-) being less than 8 x 10(-8) M, and for weakly conducting anions (ClO3- and I-) being 2.7 x 10(-7) and 5.8 x 10(-7) M, respectively. Calibration curves were linear up to 1.8 mM of each analyte. Retention times were found to increase with increasing eluent concentration and a linear relationship was observed between log k' and log[Na2B4O7] for all analytes. This behaviour is attributed to the progressive formation of a binary electrical double layer at the surface of the zwitterionic stationary phase. Retention times of analytes could be manipulated by varying the concentration of the eluent. This new suppressed-EIC system was applied to the determination of inorganic anions (SO4(-2) , CI-, NO3-, NO2-, and Br-) in snow and rainwater samples.     

维生素B1-银胶体系SERS受卤离子竞争吸附的影响

利用傅里叶变换.表面增强拉曼光谱(FT-SERS)研究了卤素离子(Cl-、Br-、I-)对维生素B1(VB1)分子表面增强拉曼散射光谱(SERS)的影响.实验结果表明,在此体系中加入卤素离子则SERS效应减弱,且三种卤素离子在银胶上的吸附能力顺序为I->Br->Cl-.     

Observation of dihalide elimination upon electron attachment to oxalyl chloride and oxalyl bromide, 300-550 K

Rate coefficients have been measured for electron attachment to oxalyl chloride [ClC(O)C(O)Cl] and oxalyl bromide [BrC(O)C(O)Br] in He gas at 133 Pa pressure over the temperature range of 300-550 K. With oxalyl chloride, the major ion product of attachment is Cl2(-) at all temperatures (66% at 300 K); its importance increases slightly as temperature increases. Two other product ions formed are Cl- (18% at 300 K) and the phosgene anion CCl2O- (16% at 300 K) and appear to arise from a common mechanism. With oxalyl bromide, the Br2(-) channel represents almost half of the ion product of attachment, independent of temperature. Br- accounts for the remainder. For oxalyl chloride, the attachment rate coefficient is small [(1.8 +/- 0.5) x 10(-8) cm3 s(-1) at 300 K], and increases with temperature. The attachment rate coefficient for oxalyl bromide [(1.3 +/- 0.4) x 10(-7) cm3 s(-1) at 300 K] is nearly collisional and increases only slightly with temperature. Stable parent anions C2Cl2O2(-) and C2Br2O2(-) and adduct anions Cl- (C2Cl2O2) and Br- (C2Br3O2) were observed but are not primary attachment products. G2 and G3 theories were applied to determine geometries of products and energetics of the electron attachment and ion-molecule reactions studied. Electron attachment to both oxalyl halide molecules leads to a shorter C-C bond and longer C-Cl bond in the anions formed. Trans and gauche conformers of the neutral and anionic oxalyl halide species have similar energies and are more stable than the cis conformer, which lies 100-200 meV higher in energy. For C2Cl2O2, C2Cl2O2(-), and C2Br2O2(-), the trans conformer is the most stable conformation. The calculations are ambiguous as to the oxalyl bromide geometry (trans or gauche), the result depending on the theoretical method and basis set. The cis conformers for C2Cl2O2 and C2Br2O2 are transition states. In contrast, the cis conformers of the anionic oxalyl halide molecules are stable, lying 131 meV above trans-C2Cl2O2(-) and 179 meV above trans-C2Br2O2(-). Chien et al. [J. Phys. Chem. A 103, 7918 (1999)] and Kim et al. [J. Chem. Phys. 122, 234313 (2005)] found that the potential energy surface for rotation about the C-C bond in C2Cl2O2 is "extremely flat." Our computational data indicate that the analogous torsional surfaces for C2Br2O2, C2Cl2O2(-), and C2Br2O2(-) are similarly flat. The electron affinity of oxalyl chloride, oxalyl bromide, and phosgene were calculated to be 1.91 eV (G3), and 2.00 eV (G2), and 1.17 eV (G3), respectively.     

Hydrothermal and structural chemistry of the zinc(II)- and cadmium(II)-1,2,4-triazolate systems

Hydrothermal reactions of 1,2,4-triazole with zinc and cadmium salts have yielded 10 structurally unique materials of the M(II)/trz/Xn- system, with M(II)=Zn and Cd and Xn-=F-, Cl-, Br-, I-, OH-, NO3-, and SO(4)2- (trz=1,2,4-triazolate). Of the zinc-containing phases, [Zn(trz)2] (1), [Zn2(trz)3(OH)].3H2O (3.3H2O), and [Zn2(trz)(SO4)(OH)] (4) are three-dimensional, while [Zn(trz)Br] (2) is two-dimensional. All six cadmium phases, [Cd3(trz)3F2(H2O)].2.75H2O (5.2.75H2O), [Cd2(trz)2Cl2(H2O)] (6), [Cd3(trz)3Br3] (7), [Cd2(trz)3I] (8), [Cd3(trz)5(NO3)(H2O)].H2O (9.H2O), and [Cd8(trz)4(OH)2(SO4)5(H2O)] (10), are three-dimensional. In all cases, the anionic components Xn- participate in the framework connectivity as bridging ligands. The structural diversity of these materials is reflected in the variety of coordination polyhedra displayed by the metal sites: tetrahedral; trigonal bipyramidal; octahedral. Structures 3, 5, and 7-9 exhibit two distinct polyhedral building blocks. The materials are also characterized by a range of substructural components, including trinuclear and tetranuclear clusters, adamantoid cages, chains, layers, and complex frameworks.     

Application of ion chromatography to the determination of inorganic anions in foodstuffs.

A review on the applications of ion chromatography (IC) to the determination of inorganic anions in foodstuffs is presented. The anions were commonly determined in food, i.e., SO3(2-), NO3- and NO2-, and to a lesser extent Cl-, Br-, I-, SO4(2-), IO3-, BrO3- and phosphate, are considered. In comparison with standard methods for the determination of anions in food products, chromatographic methods are rapid, sensitive and precise. They also have the advantage of determining several ions simultaneously. The separation may be achieved by conventional IC, by ion interaction chromatography or by ion exclusion chromatography. IC has also been applied to the determination of Br, I, N and S in foods after oxidation or combustion of samples and conversion into anionic forms.     

Kinetics and mechanisms of aqueous ozone reactions with bromide, sulfite, hydrogen sulfite, iodide, and nitrite ions

Reactions of ozone with Br(-), SO(3)(2-), HSO(3)(-), I(-), and NO(2)(-), studied by stopped-flow and pulsed-accelerated-flow techniques, are first order in the concentration of O(3)(aq) and first order in the concentration of each anion. The rate constants increase by a factor of 5 x 10(6) as the nucleophilicities of the anions increase from Br(-) to SO(3)(2-). Ozone adducts with the nucleophiles are proposed as steady-state intermediates prior to oxygen atom transfer with release of O(2). Ab initio calculations show possible structures for the intermediates. The reaction between Br(-) and O(3) is accelerated by H(+) but exhibits a kinetic saturation effect as the acidity increases. The kinetics indicate formation of BrOOO(-) as a steady-state intermediate with an acid-assisted step to give BrOH and O(2). Temperature dependencies of the reactions of Br(-) and HSO(3)(-) with O(3) in acidic solutions are determined from 1 to 25 degrees C. These kinetics are important in studies of annual ozone depletion in the Arctic troposphere at polar sunrise.     

Benzimidazole-based tripodal receptor: highly selective fluorescent chemosensor for iodide in aqueous solution

We synthesized a novel tripodal fluorescent receptor bearing benzimidazole motifs as recognition sites in the pods of the receptor. The recognition behavior of the receptor toward various anions was evaluated in CH3CN/H2O (9:1, v/v) solution. The receptor showed changes in fluorescent intensity only with I-, but it showed no significant changes on addition of other anions such as F-, Cl-, Br-, HSO4-, NO3-, CH3COO-, and H2PO4-.