• Mass Spectrometry Letters
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• v.1 no.1
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• pp.9-12
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• 2010

Trimethylboroxine (TMB) is a six-membered ring compound containing Lewis acidic boron and Lewis basic oxygen atoms that can bind halide anion and alkali metal cation, respectively. We employed Fourier transform ion cyclotron resonance spectroscopy to study the gas-phase binding of $LiBrLi^+$ and $F^-(KF)_2$ to TMB. TMB forms association complexes with both $LiBrLi^+$ and $F^-(KF)_2$ at room temperature, providing direct evidence for the ditopic binding. Interestingly, the $TMB{\cdot}F^-(KF)_2$ anion complex is formed 33 times faster than the $TMB{\cdot}Li^+BrLi$ cation complex. To gain insight into the ditopic binding of an ion pair, we examined the structures and energetics of $TMB{\cdot}Li^+$, $TMB{\cdot}F^-$, $TMB{\cdot}LiF$ (the contact ion pair), and $Li^+{\cdot}TMB{\cdot}F^-$ (the separated ion pair) using Hartree-Fock and density functional theory. Theory suggests that $F^-$ binds more strongly to TMB than $Li^+$ and the contact ion-pair binding ($TMB{\cdot}LiF$) is more stable than the separated ion-pair binding ($Li^+{\cdot}TMB{\cdot}F^-$).

• Journal of the Korean Chemical Society
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• v.17 no.3
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• pp.154-162
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• 1973

The rates and activation parameters for the halide $(Cl^{-}, Br^{-}, I^{-})$TeX> exchange reactions of substituted benzenesulfonyl-chloride, $XC_6H_4SO_2Cl$(X:p-MeO, H, p-Cl, p-Br, p-NO$_2l$) in dry acetone at two temperatures have been determined. It was found that the ion-pair of metal halide,$M^{+}X^{-}$, have negligible reactivity compared to free halide ions. It was also found that the nucleophilic order is $Cl^{-}>Br^{-}>I^{-}$for electron-donating substituent, and $Cl^{-}>I^{-}>Br^{-}$ for electron-withdrawing substituents. These results and convex nature of the Hammett plot are interpreted in the light of simple $S_N2$mechanism with the bond breaking becoming important for compounds with the electron withdra-wing substituents.

• Corrosion Science and Technology
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• v.8 no.1
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• pp.1-10
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• 2009

The influence of Schiff bases on the corrosion inhibition of mild steel in 1 M $H_2SO_4$ have been investigated by weight loss, gasometry, impedance and polarization techniques. The results obtained reveal that these compounds act as good inhibitors. The inhibition efficiency of Schiff bases increased with concentration and synergistically increased on addition of chromate, sulphate and halide ions. Potentiodynamic polarization measurements clearly reveal that the investigated inhibitors are of mixed type but they are more cathodic in nature. The adsorption of these compounds on mild steel surface for both the acids were found to obey Langmuir adsorption isotherm. The surface morphology was studied by SEM and UV reflectance spectra.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.545-548
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• 2006

We investigated the Surface-enhanced Raman Spectroscopy (SERS) spectrum of ethephone (2-chloroethylphosphonic acid). We observed significant signals in the ordinary Raman spectrum for solid-state ethephone as well as when it was adsorbed on a colloidal silver surface, strong vibrational signals were obtained at a very low concentration. The SERS spectra were obtained by silver colloids that were prepared by the $\gamma$-irradiation method. The influence of pH and the influence of anion $(Cl^-,\;Br^-,\;I^-)$ on the adsorption orientation were investigated. Two different adsorption mechanisms were deduced, depending on the experimental conditions. The chlorine atom or the chlorine and two oxygen atoms were adsorbed on the colloidal silver surface. Among halide ions, $Br^-$ and $I^-$ were more strongly adsorbed on the colloidal silver surfaces. As a result, the adsorption of ethephone was less effective due to their steric hinderance.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.238-242
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• 1989

The relations between the repulsive interactions and the electron density overlaps are investigated for various closed shell-closed shell pairs, including the systems containing alkali and halide ions. It is found that the repulsive interaction($V_{rep}$) depends on the overlap of the electron density($S_{\rho}$) according to a simple exponential relation, $V_{rep}$ = $As_{\rho}\;^{\alpha}$. Furthermore, for most of the closed shell systems the $\alpha$ values are near unity and the A values do not vary much. The same tests are also performed for the open shell-closed shell, and the open shell-open shell pairs. Although the results for these systems also show exponential dependences of the repulsive interactions on the density overlaps, the details of the dependence differ greatly from those for the closed shell systems and also vary widely from one individual system to another.

• Corrosion Science and Technology
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• v.10 no.1
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• pp.13-23
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• 2011

The inhibitive action of thiadiazolopyrimidines on mild steel in 1 M $H_{2}SO_{4}$ has been studied using weight loss, gasometric studies and electrochemical polarization and AC impedance measurements. The effect of temperature on the corrosion behaviour of mild steel in 1 M $H_{2}SO_{4}$ with optimum concentration of inhibitors was studied in the temperature ranging from 313-333K The adsorption of the inhibitor on the surface of mild steel was found to be exothermic, spontaneous and followed the mechanism of physisorption. The adsorption of these compounds on mild steel surface was found to obey Langmuir adsorption isotherm. The protective film formed on the surface of mild steel by the adsorption of inhibitor in 1 M $H_{2}SO_{4}$ solution was confirmed by optical microscopic technique. Synergistic effect of halide ions on mild steel in 1 M $H_{2}SO_{4}$ was studied by weight loss technique.

• Journal of the Korean Chemical Society
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• v.19 no.1
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• pp.11-15
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• 1975

Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

• Journal of Soil and Groundwater Environment
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• v.12 no.2
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• pp.55-64
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• 2007

An analytical method using ion-exchange chromatography was developed for simultaneous quantification of low-molecularweight organic acids ($C_1-C_6$ aliphatic carboxylic acids) and inorganic anions, and then applied to the assessment of ground water contaminated by leachates from a municipal solid waste landfill. Peak interferences of halide ions to organic acids were removed by pretreatment of water samples with Ag-containing cartridges. This method allowed accurate detection of low-molecular weight organic acids (i.e., formate, acetate, propionate, pyruvate, succinate, and oxalateas) low as 0.5 mg/L with a linear dynamic range up to 20 mg/L within 11 min run time along with typical inorganic anions. High level of pyruvate and low level of formate and acetate were detected in groundwater and landfill leachates using the analytical method. Pyruvate concentration in groundwater showed a significant correlation with concentrations of $Cl^-$ and $HCO_3^-$, and pyruvate levels decreased along the downgradient from the landfill, indicating the sources of pyruvate are landfill leachate.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.1939-1945
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• 2009

Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

• Bulletin of the Korean Chemical Society
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• v.26 no.2
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• pp.309-311
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• 2005

Single crystals of the new pentanary thiophosphate, $K_{0.5}Ag_{0.5}Nb_2PS_{10}$ has been prepared through reactions of the elements with halide fluxes. The structure of $K_{0.5}Ag_{0.5}Nb_2PS_{10}$ has been analyzed by single crystal X-ray diffraction technique. The structure of $K_{0.5}Ag_{0.5}Nb_2PS_{10}$ is made up of one-dimensional ${^{\infty}_1}[Nb_2PS_{10}]$ chains along the [001] direction and these chains are separated from one another by $Ag^+$ and disordered $K^+$ ions. This chain is basically built up from bicapped trigonal prismatic [Nb2S12] units and tetrahedral [PS4] groups. The [$Nb_2S_{12}$] units are connected together to form the linear chain, ${^{\infty}_1}[Nb_2S_9]$ by sharing the S-S prism edge. Short (2.885(2) $\AA$ or 2.888(2) $\AA$) and long (3.743(1) $\AA$) Nb-Nb distances are alternating along the chain, and the $S_2{^2-}]\;and\;S^{2-}$anionic species are observed. The distorted octahedral coordination around the $Ag^+$ ion can be described as [2+4] bonding interaction.