• Korean Chemical Engineering Research
• /
• 제45권2호
• /
• pp.172-177
• /
• 2007

신경작용제의 일종인 고농도의 사린(GB)을 무해한 물질로 전환하기 위한 실험 조건을 찾기 위하여 가성소다 수용액으로 가수분해 하였다. 가수분해 반응은 쟈켓이 부착된 소형 반응기에 circulator를 연결하여 사용하고 2.05 당량의 가성소다 용액에 농도 10 wt%의 사린을 주입한 후 각각의 반응온도(50, 70 및 $90^{\circ}C$)에서 반응 속도 상수를 구하고 이를 이용하여 각 온도에서 GB를 99% 이상 분해하는데 소요되는 가수분해 시간을 예측하였다. 가수분해 실험 결과 GB는 $90^{\circ}C$에서 1.2 시간 반응하면 99.99% 이상 분해되었으며 주요 분해생성물은 isopropyl methylphosphonate이었다.

• 한국군사과학기술학회지
• /
• 제3권1호
• /
• pp.164-175
• /
• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• 한국화재소방학회:학술대회논문집
• /
• 한국화재소방학회 2013년도 추계학술대회 초록집
• /
• pp.115-116
• /
• 2013

본 연구에서는 유기인 유도체 중 생리활성이 커서 독성이 있는 화합물의 구조를 분석하였다. 5-[(b-monoaza-15-crown-5)ethyloxy]-2iodosbenzoic acid의 IBA 촉매를 합성하여 그 반응성을 p-nitrophenyldiphenylphosphate (PNPDPP)와 Isopropyl methylphosphonofluoridate (Sarin GB), Pinacolyl methylphosphonofluoridate (Soman, GD)를 기질로 하여 연구하였다. PNPDPP 가수분해 반응에서는 긴 알킬작용기로 친유성을 증가시킨 촉매가 더 상전이 촉매로 작용함이 확인되었다.(t1/2 = 5 sec, pH = 8.07)

• 한국군사과학기술학회지
• /
• 제10권1호
• /
• pp.123-129
• /
• 2007

A 2-step process for the safe destruction of chemical wafare agents(agent hydrolysis followed by supercritical water oxidation) was studied to obtain kinetic data for the pilot plant design. This process is simple to operate by using commercial equipments and could be applied as an alternative technology to incineration. Sarin(GB) and sulfur mustard(HD) were hydrolysed in sodium hydroxide and water respectively and their hydrolysates and OPA, which is binary agent for GB were oxidized in a continuous flow supercritical water oxidation system. Destruction efficiencies of the materials were above 99.99% in supercritical water.

• 한국군사과학기술학회지
• /
• 제11권4호
• /
• pp.133-140
• /
• 2008

The purpose of this study is to provide response methods to minimize the damage from chemical terrorism in a naturally ventilated indoor system using several types of dispersion simulations. Three chemical warfare agents such as sarin(GB), phosgene and chlorine gas which have high potential to be used in terror or to be involved with accidents were selected in this simulation. Fire dynamic simulation based on Large Eddy Simulation which is effective because of less computational effort and detailed expression of the dispersion flow was adopted to describe the dispersion behavior of these agents. When the vent speed is 0.005m/s, the heights of 0.1 agent mass fraction are 0.9m for sarin, 1.0m for phosgene and 1.1m for chlorine gas, and the maximum mass fraction are 0.27 for all three agents. However, when the vent speed is increased to 0.05m/s, the heights of 0.1 agent mass fraction become 1.6m for all three agents and maximum mass fraction inside the room increase to 0.70 for sarin, 0.58 for phosgene and 0.53 for chlorine gas. It is shown that molecular weight of the agents has an important role for dispersion, and it is important to install ventilation system with height less than 1.6m to minimize the damage from chemical toxicity.

• 한국군사과학기술학회지
• /
• 제10권1호
• /
• pp.116-122
• /
• 2007

A 2-step process for the safe disposal of chemical warfare agents(agent hydrolysis followed by incineration In the submerged-quench incinerator) was studied to obtain basic data for the design of pilot plant in the future. Sample materials used for the hydrolysis reaction were sarin(GB), sulfur mustard (HD), and methylphosphonic difluoride(DF). The hydrolysates of these materials were thermally destroyed in a submerged-quench incineration system. Experimental conditions for achieving destruction efficiency of 99.99% in both steps were established and phosphoric acid was recovered from the waste water when destroying DF hydrolysate in the incinerator. Treated water could be reused as process water for the agent hydrolysis.

• 공업화학
• /
• 제26권1호
• /
• pp.17-22
• /
• 2015

2013년 시리아 내전 간 사용되어 1,300명 이상의 사망자를 발생시킨 사린(GB) 등의 화학무기로 인해 화학무기에 대한 국제적 관심이 다시 한번 높아지게 되었다. 화학작용제는 자연환경에 노출이 되면 가수분해(hydrolysis) 또는 광분해(photodegradation) 과정을 거쳐 분해물질로 분해된다. 화학작용제 및 분해물질(가수분해 또는 산화된 생성물)은 통상수 ppb 정도의 낮은 농도로 존재하기 때문에 정확한 샘플분석을 위해서는 화학작용제 및 분해물질을 환경샘플로부터 분리, 추출, 농축시키는 전처리 과정이 필요하다. 용매추출법(LLE), 고체상 추출법(SPE) 등이 화학작용제의 전처리 방법으로 많이 사용되나 최근에는 사용되는 용매의 양은 줄이면서 분석효율은 높일 수 있는 liquid phase microextraction (LPME)이 개발 적용되고 있다. 본 리뷰에서는 화학작용제 및 그 분해물질의 전처리에 활용된 LPME 전처리 기법에 대해 살펴보고자 한다.