Kinetics of degradation of sulphur mustard on impregnated carbons

Kinetics of degradation of sulphur mustard (HD) on the surface of NaOH/CrO3/C, NaOH/CrO3/EDA/C and RuCl3/C systems has been examined by using gas chromatography technique by extracting and analyzing the residual HD periodically. The carbons were prepared by impregnating activated carbon with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA) and 5% ruthenium chloride by using their aqueous solutions. Obtained carbons were characterized for surface area analysis by BET conventional method. Kinetic plots reveal that the observed reactions are fast at the initial stages, slow at the later stages and progress to a steady state indicating the first order behavior. Effect of moisture on kinetic rate is also observed. In the case of NaOH/CrO3/C system the rate constant is decreased from 13.36 to 5.53 x 10(-2) h(-1) and half life is increased from 5.2 to 12.54 h while moisture content is increased from 1.9% to 11.2%. Whereas, the rate constant of HD degradation reaction is decreased from 10.4 to 4.14 x 10(-2) h(-1) and half life is increased from 6.7 to 16.72 h while moisture content is increased from 2.1% to 10.8% on NaOH/CrO3/EDA/C. Reaction on RuCl3/C system also behaves in the similar manner. Extracted reaction products were characterized by GC/MS and it is found that on NaOH/CrO3/C, HD degrades to hemisulphur mustard, thiodiglycol and 1,4-oxathiane. Whereas, on NaOH/CrO3/EDA/C, HD is degraded to 1,4-thiazane and it is degraded to divinyl sulphone on RuCl3/C. All these investigations reveal that above mentioned carbons can be used in nuclear, biological and chemical (NBC) filtration systems for protection against sulphur mustard.     

Sulphur mustard vapor breakthrough behaviour on reactive carbon systems

Breakthrough behaviour of sulphur mustard, the deadliest of persistent chemical warfare agents, on carbon systems such as NaOH/CrO(3)/C, NaOH/CrO(3)/EDA/C and RuCl(3)/C has been studied and the data were compared with that of active carbon. Effects of bed lengths of carbons on breakthrough time have also been correlated. Thereafter, the effects of flow rate of air-sulphur mustard mixture, concentration and temperature on the kinetic parameters such as rate constant (k(v)) and kinetic saturation capacity (W(e)) were analyzed and interpreted by means of modified Wheeler equation. Rate constant was found to be increasing while W(e) was found to be invariable with the increase in air flow rate. Both k(v) and W(e) decreased with the increase of temperature, however, no significant effect on W(e) and k(v) was observed due to concentration change (0.3-0.6 mg/l). The values of kinetic saturation capacity were used to predict the service lives/breakthrough times of carbon beds (when used in filtration systems).     

Impregnated silica nanoparticles for the reactive removal of sulphur mustard from solutions

High surface area (887.3m(2)/g) silica nanoparticles were synthesized using aerogel route and thereafter, characterized by N(2)-Brunauer-Emmet-Teller (BET), SEM and TEM techniques. The data indicated the formation of nanoparticles of silica in the size range of 24-75 nm with mesoporous characteristics. Later, these were impregnated with reactive chemicals such as N-chloro compounds, oxaziridines, polyoxometalates, etc., which have already been proven to be effective against sulphur mustard (HD). Thus, developed novel mesoporous reactive sorbents were tested for their self-decontaminating feature by conducting studies on kinetics of adsorptive removal of HD from solution. Trichloroisocyanuric acid impregnated silica nanoparticles (10%, w/w)-based system was found to be the best with least half-life value (t(1/2)=2.8 min) among prepared systems to remove and detoxify HD into nontoxic degradation products. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of HD over prepared sorbents. The study also inferred that 10% loading of impregnants over high surface area and low density silica nanoparticles enhances the rate of reaction kinetics and seems to be useful in the field of heterogeneous reaction kinetics.     

In-situ degradation of sulphur mustard and its simulants on the surface of impregnated carbon systems

Bis-2-chloroethyl sulphide (sulphur mustard or HD) is an extremely toxic and persistent chemical warfare agent. For in situ degradation of HD and its analogues (simulants), i.e., dibutyl sulphide (DBS) and ethyl 2-hydroxyethyl sulphide (HEES), different carbon systems such as 11-molybdo-1-vanadophosphoric acid impregnated carbon (V(1)/C), ruthenium chloride impregnated carbon (Ru/C) and combination of these two (V(1)/Ru/C) were prepared. These carbons were characterized for cumulative micropore volume and surface area by N(2) BET. The kinetics of the in situ degradation of HD and its simulants were studied and found to be following the first order kinetics. Kinetic rate constants and t(1/2) values were determined. Products were characterized using NMR, IR and GC-MS. Reaction products were found to be sulphoxide and sulphone. The combined system, i.e., 11-molybdo-1-vanadophosphoric acid plus ruthenium chloride (V(1)/Ru/C) was found to be best for in-situ degradation of HD and its simulants. In-situ degradation by polyoxometalate based system was found to be stoichiometry based while Ru/C oxidized HD in presence of chemisorbed oxygen. In combined system of V(1)/Ru/C ruthenium worked as a catalyst and polyoxometalate acted as a source of oxygen. Effect of moisture was also studied in combined system. Rate of degradation of HD was found to be increasing with increased percentage of moisture content.     

Breakthrough behavior of diethyl sulphide vapor on active carbon systems

Breakthrough behavior of diethyl sulphide vapors on carbon systems such as active carbon, NaOH/CrO3/C, NaOH/CrO3/EDA/C and RuCl3/C has been studied by using modified Wheeler equation and the same was used to calculate the pseudo-first-order rate constant (kv) and kinetic saturation of capacity (W(e)) values. Effects of various parameters such as bed height, air flow rate, concentration and temperature on the above parameters have also been studied. Rate constant was found to be increasing with air flow rate, while W(e) was found to be invariable. Both kv and W(e) decreased with the increase in temperature, however, no significant effect on W(e) and kv was observed due to concentration change. The values of kinetic saturation capacity were used to predict the service lives/breakthrough times of carbon beds (when used in filtration systems).     

Kinetics of the degradation of sulfur mustard on ambient and moist concrete

The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using (13)C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 degrees C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 degrees C ranged from 75 to 350h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 degrees C and weeks to months on concrete at 35 degrees C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane.     

Mesoporous titanium–manganese dioxide for sulphur mustard and soman decontamination

Titanium(IV)–manganese(IV) nano-dispersed oxides were prepared by a homogeneous hydrolysis of potassium permanganate and titanium(IV) oxo-sulphate with 2-chloroacetamide. Synthesised samples were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy (SEM). These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (HD or bis(2-chloroethyl)sulphide) and soman (GD or (3,3′-dimethylbutan-2-yl)-methylphosphonofluoridate). Mn⁴⁺ content affects the decontamination activity; with increasing Mn⁴⁺ content the activity increases for sulphur mustard and decreases for soman. The best decontamination activities for sulphur mustard and soman were observed for samples TiMn_37 with 18.6 wt.% Mn and TiMn_5 with 2.1 wt.% Mn, respectively.     

Effect of calcinations temperature of CuO nanoparticle on the kinetics of decontamination and decontamination products of sulphur mustard

Present study investigates the potential of CuO nanoparticles calcined at different temperature for the decontamination of persistent chemical warfare agent sulphur mustard (HD) at room temperature (30 ± 2 °C). Nanoparticles were synthesized by precipitation method and characterized by using SEM, EDAX, XRD, and Raman Spectroscopy. Synthesized nanoparticles were tested as destructive adsorbents for the degradation of HD. Reactions were monitored by GC-FID technique and the reaction products characterized by GC-MS. It was observed that the rate of degradation of HD decreases with the increase in calcination temperature and there is a change in the percentage of product of HD degradation. GC-MS data indicated that the elimination product increases with increase in calcination temperature whereas the hydrolysis product decreases.     

Physical and chemical properties and adsorption type of activated carbon prepared from plum kernels by NaOH activation

Activated carbon was prepared from plum kernels by NaOH activation at six different NaOH/char ratios. The physical properties including the BET surface area, the total pore volume, the micropore ratio, the pore diameter, the burn-off, and the scanning electron microscope (SEM) observation as well as the chemical properties, namely elemental analysis and temperature programmed desorption (TPD), were measured. The results revealed a two-stage activation process: stage 1 activated carbons were obtained at NaOH/char ratios of 0-1, surface pyrolysis being the main reaction; stage 2 activated carbons were obtained at NaOH/char ratios of 2-4, etching and swelling being the main reactions. The physical properties of stage 2 activated carbons were similar, and specific area was from 1478 to 1887m(2)g(-1). The results of reaction mechanism of NaOH activation revealed that it was apparently because of the loss ratio of elements C, H, and O in the activated carbon, and the variations in the surface functional groups and the physical properties. The adsorption of the above activated carbons on phenol and three kinds of dyes (MB, BB1, and AB74) were used for an isotherm equilibrium adsorption study. The data fitted the Langmuir isotherm equation. Various kinds of adsorbents showed different adsorption types; separation factor (R(L)) was used to determine the level of favorability of the adsorption type. In this work, activated carbons prepared by NaOH activation were evaluated in terms of their physical properties, chemical properties, and adsorption type; and activated carbon PKN2 was found to have most application potential.     

Sulphur mustard degradation on zirconium doped Ti-Fe oxides

Zirconium doped mixed nanodispersive oxides of Ti and Fe were prepared by homogeneous hydrolysis of sulphate salts with urea in aqueous solutions. Synthesized nanodispersive metal oxide hydroxides were characterised as the Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) microanalysis, and acid-base titration. These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (chemical warfare agent HD or bis(2-chloroethyl)sulphide). The presence of Zr⁴⁺ dopant tends to increase both the surface area and the surface hydroxylation of the resulting doped oxides in such a manner that it can contribute to enabling the substrate adsorption at the oxide surface and thus accelerate the rate of degradation of warfare agents. The addition of Zr⁴⁺ to the hydrolysis of ferric sulphate with urea shifts the reaction route and promotes formation of goethite at the expense of ferrihydrite. We discovered that Zr⁴⁺ doped oxo-hydroxides of Ti and Fe exhibit a higher degradation activity towards sulphur mustard than any other yet reported reactive sorbents. The reaction rate constant of the slower parallel reaction of the most efficient reactive sorbents is increased with the increasing amount of surface base sites.     

Detoxification reactions of sulphur mustard on the surface of zinc oxide nanosized rods

Detoxification reactions of sulphur mustard, a deadliest chemical warfare agent were studied on the surface of zinc oxide nanorods at room temperature (32+/-2 degrees C) and the data was compared with that of the bulk ZnO. Prior to the reaction, the nanorods of zinc oxide were synthesized by the hydrothermal method and subsequently characterized by XRD, SEM, TG, N(2) BET, FT-IR. The data revealed the formation of nanorods with diameter ranging from 100 nm to 500 nm with length in microns. Obtained nanomaterial along with bulk ZnO were tested as reactive sorbent for the detoxification of sulphur mustard. Reaction was monitored by GC-FID technique and the reaction products were characterized by GC-MS. Data explores the role of hydrolysis and elimination reactions in the detoxification of sulphur mustard and it also reveals that zinc oxide nanorods and bulk ZnO show the half lives of 8.48 h, 24.75 h in the first 12h and 122.47 h, 177.29 h from 12h to 48 h of the reaction.     

The adsorption of chromium (VI) from industrial wastewater by acid and base-activated lignocellulosic residues

This study deals with the adsorption of Cr(VI) from synthetic and industrial wastewater, produced by a sewage plant. The activated carbons were prepared from a lignocellulosic raw material by thermal treatment at 450 and 650 degrees C in the presence of acid (AlCl(3), HCl, H(3)PO(4) and H(2)SO(4)) and base (NaOH) agents. To optimize the adsorption of Cr(VI), the chemical modifications caused by each activating agent (related to the capability of Cr(VI) removal), and the optimal experimental conditions of the pH, Cr(VI) concentration, adsorbent dose and residence time, were studied. Thus, treatment with H(3)PO(4) gives rise to carbons with a high surface area and high efficiency for Cr(VI) removal at short equilibrium times. In contrast, the generation of active surface sites by means of NaOH requires longer equilibrium times, the adsorption being less effective than in the former case. The adsorption isotherms obey the Langmuir equation only in the first stages of the reaction but fit the Freundlich equations over the whole range studied, so the heat of adsorption can be easily calculated. The results also show that the activated carbons obtained can be recovered by filtration with an efficiency of 30% in the third cycle.     

椰壳纤维基高比表面积中孔活性炭的制备

以椰壳纤维为原料,制备高比表面积中孔活性炭.采用正交试验设计实验方案,研究KOH和NaOH复合活化法制备活性炭的实验方案与工艺条件.考察了活化剂配比、炭化温度、活化温度、时间和升温速率对所制活性炭吸附性能的影响.在最佳工艺条件下,所制活性炭的比表面积达到2032m2/g,中孔发达,特别是2nm～4nm的,中孔比例达到28%.活性炭对的碘吸附值为1435mg/g,亚甲基蓝吸附值为495mg/g,产率为49%.     

NaOH活化法中碱炭比对孔结构和电化学性能的影响

采用沥青焦为原料,以NaOH化学活化法制备出不同碱炭比(R)系列活性炭.用氮气吸附和脱附等温线计算出BET比表面积、DFT孔径分布及孔容,并且通过直流循环充放电、循环伏安等表征方法研究了其电化学性能.实验结果表明,R值对活性炭的BET比表面积、DFT孔径分布及孔容有良好的调控作用:当R=5时,其最大BET比表面积为1089m2/g,孔容达0.53cm3/g,当R=3时,其孔径分布在1.0-2.0nm百分比达36.2%;其直流循环充放电曲线较好,循环伏安曲线也近似矩形,表明具有良好双电子层电容器电极材料特性,在3mol/L的KOH电解液体系中,最大质量比电容、体积比电容、单位面积比电容分别达202F/g、143F/cm3、32.9μF/cm2;在1mol/L(C2H5)4NBF4/Propylene Carbonate(PC)电解液体系中,最大质量比电容、体积比电容、单位面积比电容分别达149F/g、107.3F/cm3、20μF/cm2.对KOH和(C2H5)4NBF4/PC电解质吸附的最佳孔径分别为1.3nm,1.5nm左右.     

A preliminary study on sorption, diffusion and degradation of mustard (HD) in cement

A preliminary study has been done to examine the sorption, diffusion and degradation of mustard (HD) in cement. The sample of dried cement paste is a meso-porous adsorbant with a BET surface area around 40.8 m2/g, which is able to adsorb vapor of HD at room temperature and to result in a multiple-layer isotherm of II type. The molecule of HD seemed to chemically adsorb onto cement surface. Droplet of HD contaminating cement was able to be degraded into less toxic products, but in a very low rate of k = 4.8 x 10(-5) min(-1) and t(1/2) = 16 x 10(4) min at room temperature. Droplet of HD is able to penetrate through the layer of cement, but a cement plate of 8mm can protect against HD droplets over 48 h. A decrease of thickness for cement layer or addition of sand in cement would lead to lower the protection time against HD droplets. The diffusion coefficient of HD molecule in cement was determined, about 1.3 x 10(-4) cm2/min and of a typical diffusion in solid.     

孔结构对煤基活性炭电极材料电化学性能的影响(英文)

以太西无烟煤为前驱体,NaOH为活化剂制备电化学电容器电极材料。采用N2吸附法及电化学测试对活性炭的孔结构和电化学性能进行了表征。在1mol/L(C2H5)4NBF4/碳酸丙烯酯有机电解液体系中,研究了孔结构对活性炭电极材料的电化学性能的影响。结果表明:以NaOH为活化剂可制备出比表面积943mol/L～2479mol/L、比电容57F/g～167F/g的活性炭电极材料。活性炭电极材料的比电容不仅取决比表面积,而且与活性炭的孔径分布有关。孔径为2nm～3nm的中孔的存在可以有效降低电解液的扩散阻力,提高电极材料比表面积的利用率,从而使电容器的电化学性能得到增强。     

Hexavalent chromium in tricalcium silicate: Part I Quantitative X-ray diffraction analysis of crystalline hydration products

The hydration products of CrVI-doped tricalcium silicate (C3S) have been investigated. C3S is the main constituent of Portland cement responsible for the strength and stability of hardened Portland cement paste. Chromium trioxide (CrO3), added as a dopant to C3S, simulates hexavalent chromium waste that may be stabilized in ordinary Portland cement. X-ray diffraction was used to monitor the development of the hydration reaction products from the early stages to the late reaction stages. Leaching studies were carried out to evaluate the stability of the CrVI-containing phases in the hydrated C3S matrix.In monolithic waste forms containing hexavalent chromium, CaCrO4·2H2O was found to form within a few minutes of the hydration reaction. With increasing concentration of Ca2+ in the pore solution, Ca2CrO5·3H2O became the stable species. The chromium in this phase was found to be very mobile in a standard acetic acid leaching test.     

模拟太阳光下锗掺杂纳米TiO2对化学毒剂的降解性能

采用均匀沉淀法制备不同锗掺杂浓度的纳米二氧化钛(TiO₂); 为了研究掺杂浓度与粉体活性之间的关系, 针对化学毒剂(CWAs)模拟剂2-氯乙基乙基硫醚(2-CEES)和甲基膦酸二甲酯(DMMP)开展光催化消毒实验, 并用动力学方程拟合实验结果; 通过XRD、UV-Vis、BET、BJH、SEM和TEM等技术对样品进行表征, 分析锗掺杂对TiO₂结构及性能的影响; 综合考虑溶剂的毒性、挥发性、可燃性和溶解性等因素, 以氢氟醚(HFE)作为分散溶剂, 研究模拟太阳光下Ge-TiO₂和HFE混合体系对芥子气(HD)、梭曼(GD)和维埃克斯(VX)的消毒性能。结果表明: 适量锗掺杂不会改变纳米TiO₂的晶型结构, 可以减小晶粒尺寸, 增大比表面积, 增强光利用率, 提高消毒活性; 相较于直接使用粉体消毒, 混合体系的消毒效率明显提高; 在模拟太阳光下, 最佳锗掺杂浓度(6.24wt%)样品与HFE-458 (HCF₂CF₂CH₂OCF₂CF₂H)组成的混合体系与三种化学毒剂反应60 min的降解率分别为: HD 98.73%、GD 100%、VX 100%。     

Performance of electrical double layer capacitors with porous carbons derived from rice husk

The porous structure and electrochemical double layer capacitance of porous carbons prepared from rice husks by using alkali hydroxide as activating agents were investigated. Three samples of carbons prepared by NaOH-activation, three samples prepared by KOH-activation and two samples of commercial carbons have been studied. The porosity of the carbons was characterized by nitrogen adsorption isotherms at 77 K and electrochemical constant current cycling method was used to measure the double layer capacitance. The specific capacitance of the carbons is not linearly proportional to the surface area. Additionally, the double layer capacitance strongly depends on the pore structure and the functional groups. A specific capacitance larger than 200 F g⁻¹ was achieved by using the porous carbon prepared with NaOH (activation temperature: 750 °C; activation time: 30 min). All the carbons prepared with rice husk in this study have larger double layer capacitance (125–210 F g⁻¹) than the commercial grade carbons (78–100 F g⁻¹).     

The reactions of sulfur mustard with the active components of organic decontaminants

Reactions of sulfur mustard with active components of decontaminants ORO and C9 (Polish abbreviations of organic decontaminating solutions) were studied and their products were identified by GC/AED. Quantitative determinations of individual products in the reaction mixtures allowed to evaluate the kinetic parameters of the mustard reactions. The major decontamination product was divinyl sulfide, the product of the elimination reaction. At certain proportions of mustard to the decontaminant's active component, substitution products were also formed.