Hydrolysis of Sarin(GB) in Aqueous NaOH Solution

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1 Korean Chem. Eng. Res., Vol. 45, No. 2, April, 2007, pp { khi (GB)m mk Çmpz Ç l re o o n~ 35-1 (2006 8o 16p r, o 19p }ˆ) Hydrolysis of Sarin(GB) in Aqueous NaH Solution Yong-Han Lee, Jong-Chol Lee and Deasik Hong Agency for Defense Development, P.. Box 35-1, Yuseong-gu, Daejeon , Korea (Received 16 August 2006, accepted 19 ctober 2006) k e qnrp psp p (GB)p v r o e s p } o l n kp m. pp q p p l circulator l l n 2.05 p nkl 10 wt%p p tp p pm (50, o C)l p p pn l m l GB 99% p n e p m m. e GB 90 o Cl 1.2 e p 99.99% p lp tn p isopropyl methylphosphonatepl. h Abstract The hydrolysis reaction of sarin(gb), one of the nerve agents was studied in aqueous sodium hydroxide(nah) solutions to find the experimental conditions which can convert GB into the less toxic compounds. 10 wt% of GB was added into the aqueous NaH(2.05 eq) in a small-scale jacket-attached reactor connected to a circulator. The reaction rate constants were measured at three temperatures(50, 70 and 90 o C) and the reaction times required to degrade the material to > 99% were calculated at different temperatures. In this study, 10 wt% of GB was degraded to 99.99% in 1.2 hr at 90 o C by the aqueous NaH solution. The major hydrolysate of GB was isopropyl methylphosphonate. Key words: Sarin(GB), Chemical Warfare Agent, Hydrolysis, Mass Spectrometry 1. (isopropyl phosphonofluoridate GB)p rp e q nr(nerve agent) p~p p e p v t e e l p v p. GB qnr(p qnr ) o v k(chemical weapons convention : CWC)l kl vr l k [1, 2], s qnr kr prp } o k l lm [3-5]. qnrp p t vr t vp l m. kp p qnr nl v p p l pl p t kr l pl r k qnr vp mr pv p v p rn p. To whom correspondence should be addressed. jcleeadd@hanafos.com, s qnr tp p s qnr k l vr p rp }ˆ Š p 4 vll e p nm pp qnr rl o vp l qlq vl t p krp o ql l m p p ~m vl t p tq l mr vll ~ p r l e p nm mrp [6]. ~ l p qnr 2 } p }n pp 1 } r(r} )l r qnr, vp 2 ( } ) p rp } p n p }ˆ m. ~ r e lp rk qnr } p r} (pretreatment) p t p } m [6]. pm p t p r p np rrp t q~ p o vp p rp pp l l qnr } p k pn p. 172

2 qnr mm vp r (decontamination) o evr p l p l e rp l mp [7-9] l np qnr mm p~ q / qp r l trp lp k qnr mr v r qnr p p ~ rp v v kk. p CWC, qnrp } p n l t l p qnr r l q s, p p rrp r} p pe l. qnr t p rp vl lr kl r v[1, 2] k o qnr s l p mp o l pl p v mr } p } } v vp r r p p qnr v p n l. t l p GBp p t vp } l t r NaH, KHm p m nkp [7, 8] k k k nkp pn o [10] n p. nkl p GBp l 90 e q lp, l GB(7.2 wt%) isopropyl methylphosphonate(impa) s } o l rp l methylphosphonic acid(mpa) eˆ p r pn l p nk t MPA r [11], p e mr e p t p ( ˆ t, Blue Grass) } ( t, Pueblo) p pn mrp [12]. vp, k m pe vp r p p lv vl H + H pp qnrp r t. qnr t (v, r ) r1 r p k p qnr v o l l lp l l o v, qnrp l en p. lp e qnrp (pinacolyl methylphosphonofluoridate, GD soman) VX(o-ethyl-s-[2-(diisopropylamino)ethyl]-methylphosphonothiolate) m mp nk(m; Na 2 C 3, NaH KH)l p r l p p mp r [7, 13, 14]. p l p l r n l pv kp 1:1l ve nkp e (1) p p [6]. v, ( CH P F+2NaH ( CH P + 2Na + +H 2 +F (1) p pp p p e mr p p o p H n. GB nkl s o ss k ( ˆm lˆm)p tp, ph ov o l pp KH n. GBl sq r rp p diester p s nkp ph 7 p p diester pm p l GB q pp p p p n p k v p. GB mr e (GB)p 173 ˆ o pp n v o p ph 9 p ov k., l s r vp pn qnrp l pp NaH GB p ˆr l o m [15]. om p p p q v k v e qnr qnr r vp r t e Š prp e vrp GBp s p o l q m. p p, p GB(10 wt%) nkp l GBp Ž pp 99.99% p p rr m m p n e p m l GBp rl rn p p l rp p. e p l m p tn pq m p e p r pl pp Š, GB GB vp e e rp r p l v p r l l p trp l m k h e qnr q~ r np GC GC-MS pn l vr r pp qnr s l kˆ MPA rp n l MPA r. GBp IMPA MPA GBp v r p p. s vp MPA p p HPLC, IC, CE, HPLC-MS, CE-MS o ~ l p HPLC GC-MS, ion mobility spectroscopy(ims) k p pn pp [14, 16-18], m ˆ p sp GC-MS q rr r k v p. p l l GBp vp GC/MSD LCQ(Ion trap) n l el r p nkl kp GB GC/ FID GC/FPD r mp t(internal standard : I.S.) vp dodecane(fid) triethylphosphate(fpd) n m. q nm s p Table 1. e l n GBm p IMPA 99% p p p n m. p nkl kp GB chloroform(aldrich)p o n l sq p r o l sr magnesium sulfate n m. p n GB qnrp 73~93% p ql v o l krr ~ p. er rn qnr l nl k v p p m l p m p rp r o l ekp vp n m m m ~o GBm NaH nkp pp e (1) p p n l 1.0 : 2.05p m. e l n q Fig. 1 p q p p n (p q p ) circulatorl l l p m pr ov p nk 9 ml(gbl l 2.05, mmol) p n l k 10 m e. p 1.0 ml gas-tight syringe(leur type) Korean Chem. Eng. Res., Vol. 45, No. 2, April, 2007

3 174 pn Ëps~Ë e Fig. 1. Experimental Apparatus. l 10 cm needlep l l GB(1.0 ml, 7.87 mmol) p l t p m. p GB n p tp l v k needle p p v p tp l l. p m p n(90 o C) nkl GB p p tp lk. pl n q r p n mp p 3 mm p stirring bar pn l l e m. v l p rp gas-tight syringe pn l pr e p e 500 µl j } l 20 mlp viall l. pl n p chloroformp k 2ml 30 I.S. nkp 150 µl j 2~3 e p 1 m. p n I.S. vp dodecane(73.7 mg/20 ml ethyl acetate) triethyl phosphate nk(12.6 mg/10 ml ethyl acetate)pl. nkp k p chloroform p vial m magnesium sulfate l p r chloroform nkp } l GC/FPD FID pn l p GB r m sm m p e GBp vp k m p GC/MSDm LCQ (ion trap) m. Table 1. Analytical equipments and their operating conditions Analytical equipments perating conditions Ë GC/MS(sector): Micromass autospec ultima with agilent 6890 plus GC Ë GC/MS: Agilent 5973N with 6890 GC LCQ(ion trap): Finnigan LCQ GC(FPD): Agilent 6890(dual FPD) GC(FID): Agilent 6890 o45 o k Injector temp ven temp Detector temp Column Ionization mode Electron energy GC/MSl p p nkl sq o p p o l 90 o C l e GB nk t k 1.0 ml l 20 ml o l chloroform 10 ml l. Vialp k 30 k kr e nk p o nk p vial m sr l p r GC/MSD(EI) m., nkl sq p p p p m. 90 Cl p o GB nkp ph r k 7 plp t v k e k 0.1 ml l V- viall p 50 Cp o sand bathl v }} tp l p v eˆ k 500 µlp tetrahydrofuran(thf) bis (trimethyl)- trifluoroacetamide(bstfa) 100 µl 60 o C m l 1 e k e o ~ m. p s oe pn l p nkp p GC/MSD(EI) r m. p GC/MSDp s p solvent delay timep 7.5 p sr l BSTFAl p MSp mmp v m LCQ(IT) l p p pnk k 1.0 ml l 0.45 µm membrane filter l v k vp r Table 1p LCQ e s l l r m. 3. y 3-1. GC/FID FPDi m GBm o ~o e l n GB 10 wt% f p p v k nkl sq GB r o l GB l l p op v p r q p n m. p o l t v(i.s.) p pn mp, I.S. v dodecane(dd) triethyl phosphate(tep) n m GBp r pp r o r GBl l p sp p } p tn. GBp r GC/MSD GBp p m/z = 99 ˆ l SIMp 250 o C 40 o C(1 min), 10 o C/min, 280 o C(5 min) 280 o C SE54 (HP 5) : 5% Diphenyl/95% dimethylsiloxane Electron impact(ei) 70 ev Infusion Sample flow : 10 ml/min, Solvent flow(split mode): 10 µl/min LC Solvent A 0.5% formic acid/water (90%) LC Solvent B 0.5% formic acid/methanol (10%) Ionization ESI Injector temp 250 o C ven temp 40 o C(1min), 10 o C/min, 280 o C(5 min) Detector temp 250 o C Column SE54 (HP5) perating conditions for the injector, column and detector are the same as GC/MS

4 r mp k ppb v p, GC/FPD n nl k 77 ppb v r p mp e l GBl l sp GC/FPD pn m GBp r q GC(FPD) n GB l r p v o qp GBp Š r mlp l r p q m. r o(76.8 ppb~9.8 ppm)l FPD n mp, (9.8 ppm~314.5 ppm)l p ol l v p FID pn m. r p I.S. v(fpd TEP, FIDp nl DD) pn p n l q r mll y = x , γ 2 = y = x , γ 2 = f v p n k m GBp p r t p GBp r r p o nk l kp GB rp p o n rp n tn. r n r o l 20 ml o l GB k 5~6 mg r p n l v 5ml vial l p ve n 5ml k 30 l. pl I.S. v(dodecane nk)p t pr viall l 2~3 1 r m. n chloroform ethyl acetate nk p o nk p vial m sr l p r nkp GC/FID l nk l kp GBp pp m. e n ethyl acetate n nl Table 2 m p GB k 74% mp chloroformp n 91% l pp 17% p v l chloroformp n ˆ m GBm m (GB)p 175 plp p 10% pp nkp ph 11 ~ 12p o l [6]. l GB p 10 wt% v v e p vp s} l p } m p (2.05 )p nkp n l p m l p l m p e l p 1 r l rp GBp kr o r s p p ml m v o m l p e l pp p tn m. m 50, C r m l e o pp e (2) p m. GBp p = ( GB - p GB )/ GB 100 (2) e GBp pp Fig. 2m p m v l d mp 90 Cl 1e k o 99.99% p l. p el p l m o l 1 pp t, - dc/dt = k[c] (3) e (3) r - lnc/c 0 =kt (4) oel C 0 C, t p ~ e p k m l p p Arrheniusep p. v, k(t) = Aexp(-E a /RT) (5) e (5) p p. lnk = lna - Ea/R(1/T) (6) GBp GBp l n k e (1)l GBp leaving groupp fluoride l P-F p l q p p vl ps. Beaudry p 7.2 wt%p GB NaH nkp n l p IMPAp m p r l. l php m p n GB o p ov o l ph 9 p ov lk m [11]. l r m p ph p GB q pp tn p IMPA r vp q} k. e rrp r p NaF p, l NaFp n k 4% r rp. } r p o l r e e r p v o l n nk(gbl 5% NaH nkp k 4.6 ) Fig. 2. Hydrolysis efficiency of GB depending on reaction temperatures and times. Table 2. Comparison of recovery efficiency for GB by two extraction solvents (GB i ; Initial weight of GB, GB r ; Weight of GB recovered) Solvents used GB i (mg) Peak area (GB/DD) DD (mg) Wt. ratio (GB/DD) GB r (mg) Recovery efficiency (%) Ethyl acetate Chloroform Korean Chem. Eng. Res., Vol. 45, No. 2, April, 2007

176 pn Ëps~Ë e Fig. 4. Analytical methods used in this study for the GB hydrolysate. Fig. 3. Reaction rate constant depending on reaction temperatures.

5 176 pn Ëps~Ë e Fig. 4. Analytical methods used in this study for the GB hydrolysate. Fig. 3. Reaction rate constant depending on reaction temperatures. GB pp n 1 ep rn l p m l ps p Arrhenius el p l e Fig. 3 p v p k (y = 7.162*10 3 x , γ 2 = 0.999) mp e (5)l e rn Table 3 p m p m l GB 99% p n p e p m p. p GBp m(25 o C) m (90 C)l k 90 p e p n qnr rl o e n 1~2e p l 99.99% p pp 80 o C p p m mll rp nm p v GB sm nkl p vp o l Fig. 4m p r k p vp GB IMPA l GC/MSDl p p GB e vp pp o n p chloroformp k~-k~ nk q~ v seˆ e o ~ l GC/MS p m. n kp s ph k 7 plp ph sr v kkp o n kp chloroformp l GB GBp vp IMPA e p l p m l bis (1-methylethyl) dimethylphosphonate (C 8 H 10 5 P 2 )p pyro p v kk., nk p v d seˆ BSTFA o ~ l lp mass spectrum p GBl fluoride lr IMPA(TMS) op p l. ( CH P F ( CH P H (7) Sarin IMPA LCQ(IT)l p p LCQl p v p r, nkp k 10 ppm v SCX(kpm v) n l nkl s q kpmp r p LC p v k vr pm eˆ infusion p m. GB nkp LC dž positive model Table 4m p IMPAp M+1 (peak) r m/z=139 2M + 1 p m/z=277 p m. IMPApp p o l m/z=139 MS 2 eˆ IMPA isopropyl groupp l m/z=97 p m. m/z=277 MS eˆ IMPAp 2 M+1 p m/z = 139 r p m/z = 277 IMPAp 2M + 1 pp pl., Table 5 negative model lp ion p e p, IMPAp M-1 r m/z = 137 M-1+HC 2 Hp m/ z = 183 pl. m/z = 137p MS e p 2 Table 3. Reaction times required for the destruction of GB(>99%) by NaH solution depending on the reaction temperatures Times(h) Temp ( o C) 1/T(K) 10 3 ln k k(min -1 ) % 99.99% o45 o k

6 (GB)p 177 Table 4. Ions observed from GB hydrolysate (Infusion, Positive mode) Ions observed(m/z) [2M+1] [M+1] Fragmentation Table 5. Ions observed from GB hydrolysate (Infusion, Negative mode) Ions observed(m/z) [M-1+HC 2 H] [M-1] Fragmentation negative model IMPA isopropyl groupp lr p m/z=95 lp pl. m/z = 183p 2eˆ MS m/z = 137 r p m/z = 183p IMPAm buffer nk tl o formic acid M-1+HC 2 Hl pp r pl. o s positive modep n M+1 p m/z=139 m negative p n M-1p m/z = 137p p plp, n MS eˆ 2 m/z = 139(positive) m/z=97 r lp, m/z = 137(negative) m/z=95 r l. p alkylphosphonatep C-P l carbonp methyl p lr p pp ˆ o GBp vp IMPA pp p pl. 4. (isopropylphosphonofluoridate, GB)p r kr o l GB 10 wt% nk(2.05eq)p p m (50, C)l l pp o r, m l GB p pp 99% p o m n e p m., p l p e vveˆ o l vp k p k m p p ll. (1) GBp pm dl v mp, 90 Cl k o 1.2 e p 99.99% p l. p vp isopropyl methylphosphonate (IMPA) pl. (2) vl o l p p GB nl GBp n chloroformp n p ethyl acetate pp 17% p v m. (3) nkl sq GBp r p GC/FID GC/FPD n mp, t v l p GBp 70 ppb pl. (4) GC/MS(SECTR)m LCQ pn l vp GB IMPA mp methylphosphonic acid(mpa) pyro p p v kk. y 2. Row, K. H. and Park, Y. K., Chem. Ind. & Technology, 15(2), (1997). 3. NAT Advanced Research Workshop, Destruction of Chemical Weapons: Report of the NAT Advanced Research Workshop on Destruction of Military Toxic Waste, Naaldwijik, Netherlands, May(1994) Workshop on Advances in the Alternative Demilitarization Technologies, Reston, Virginia, USA(1995). 5. Lee, J. C., Chemical Weapons Destruction Technology(II), Kor. Sol. Was. Eng. Soc., 16(3), (1999). 6. U.S. National Research Council, Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons, National Academic Press, Appendix D, Washington D.C., U.S.A., (1999). 7. Yang, Y.-C., Baker, J. A., and Ward, J. R., Decontamination of Chemical Warfare Agents, Chem Rev., 92, (1992). 8. Yang, Y.-C., Chemical Reactions for Neutralizing Chemical Warfare Agents, Chemistry and Industry, 9, (1995). 9. Wagner, G. W. and Yang, Y.-C., Rapid Nucleophillic/xidative Decontamination of Chemical Warfare Agents, Ind. Eng. Chem. Res., 41(8), (2002). 10. Miller, P. L., Ammonia Fluid Jet Cutting in Demilitarization Process Using Solvated Electrons, U.S. Patent 6,080,909(2000). 11. Beaudry, W. T., Analysis of Decontamination solutions of G Agents to Detect Reformation of Agent, ERDEC-TR-005, APG, U.S.A.(1993). 12. U.S. National Research Council, Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant, National Academies Press, Washington D.C.. U.S.A.(2005). 13. Lee, J. C., Lee, Y. H., Park, H. and Choi, S. J., Hydrolysis of Methylphosphonic Difluoride and HF Recovery from the Hydrolysate, HWAHAK KNGHAK, 41(4), (2003). 14. D Agostino, P. A., Hancock, J. R. and Provost, L. R., Determination of Sarin, Soman and Their Hydrolysis Products in Soil by Packed Capillary Liquid Chromatography Electrospray Mass Spectrometry, J. Chromatogr A, 912, (2001). 15. Yoon, Y., Choi, H. H., Chung, S.-T. and Choe, S., The Resolving Effect of Hydroxides, xides and Chelate Cu(tmen) Compounds on Toxic Chemicals, J. Kor. Ind. Eng. Chem. 14(8), (2003). 16. Read, R. W. and Black, R. M., Rapid Screening Procedures for the Hydrolysis Products of Chemical Warfare Agents Using Positive and Negative ion Liquid Chromatography-mass Spectrometry With Atmospheric Pressure Chemical Ionisation, J. Chromatogr A, 862, (1999). 17. Kanu, A. B., Haigh, P. E. and Hill, H. H., Surface Detection of Chemical Warfare Agent Simulants and Degradation Products, Analytica Chimica Acta, 553, (2005). 18. Lebedev, A. T., Mass Spectrometry in Identification of Ecotoxicants Including Chemical and Biological Warfare Agents, Toxicol. and applied pharmacy, 207, S451-S458(2005). 1. Chemical Weapons Convention, rganization for the Prohibition of Chemical Weapons, Home page, Korean Chem. Eng. Res., Vol. 45, No. 2, April, 2007

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