Nghiên cứu động học quá trình chuyển hóa một số chất độc quân sự bằng dẫn xuất chloro isocyanurate trong môi trường nước tt tiếng anh

MINISTRY OF EDUCATION AND TRAINING MINISTRY OF NATIONAL DEFENSE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY CHU THANH PHONG RESEARCH OF THE KINETICS FEATURES OF DECONTAMINATION PROCESS OF SOME CHEMICAL WARFARE AGENTS WITH CHLORO- ISOCYANATE IN WATER Specialization: Theoretical and Physical chemistry Code: 440 119 SUMMARY OF CHEMICAL PH.D THESIS HANOI - 2020 The work has been completed at: Academy of Military Science and Technology Scientific: Doctor Vo Thanh Vinh Associate Professor, Doctor Tran Van Chung Reviewer 1: Professor, Doctor Nguyen Van Tuyen Reviewer 2: Associate Professor, Doctor Dinh Ngoc Tan Reviewer 3: Associate Professor, Doctor Nguyen Thi Cam Ha The dissertation war defended at the Doctoral Evaluatiny Council at the Academy of Military Science and Technology at …… h ., date month …….year 2020 The dissertation can be found at: - The Library of Academy of Military Science and Technology - Vietnam National Library INTRODUCTION 1.The urgency of the doctoral thesis With the efforts of the international community, the ussage and storage of mass destruction weapons in the world has changed in a positive way, however, other countries have been secretly researching and manufacturing them, also creating and storing a number of chemical weapons despite the international treaties In the world and in Vietnam, the research of finding out new decontamination agents for military toxic chemicals has been a matter of urgency for meeting the requirements in modern warfare Chloro-isocyanurate in aqueous media may be hydrolyzed to produce free chlorine to participate in reactions and to act as catalysts for decontamination of toxic chemicals In recent years, there have been a number of studies and published works on this hydrolysis process and the ability to detoxify military toxic agents possessed by chloro-isocyanurate in solutions In Vietnam, the research of the kinetics of decontamination using chloro- isocyanurate is just only at the initial stage and has not been explained clearly Therefore, there is barely enough theoretical basis to produce decontamination agents using these substances Topic “Research of the kinetics features of decontamination process of some chemical warfare agents with chloro- isocyanate in water” was aimed at explaining the kinetics conversion of some military toxic agents with chloro- isocyanurate From there producing a new decontamintion system used for training and combat readiness Scientific and practical meanings The thesis addressed two major issues involving the decontamination of CS, HD, and GB by chloro-isocyanurate: the reaction kinetics and determination thermodynamic parameters of the decontamination reactions to understand the substance of the reaction mechanism The obtained results of the thesis are a database for creating and completing the technology for producing synthetic decontamination agents basing on chloro-isocyanurate derivatives that have got functions and effectiveness similar to that of some new generation synthetic decontamination agents, so that not dependent on imports And saving exchange money Research object and scopes of thesis Testing, selecting, and determinating the suitable analytical methods for qualifying free chlorine concentration involving in chloro-isocyanurate solution Studying the effectiveness of the decontamination of CS, HD, and GB using chloro-isocyanurate; Determinating of some factors that affect the effectiveness of the CS, HD, and GB decontamination process Studing the kinetics of the decontamination of CS, HD, and GB with chloro-isocyanurate in aqueous media, calculation of some reaction kinetic and thermodynamic parameters Identifying products of the decontamination process; proposing the forecast diagrams about decontamination reactions between chloroisocyanurate and CS, HD, GB Carrying out experiments for the evaluation of the decontamination efficiency of the proposed synthetic decontamination solution and comparing with other decontamination solutions Research methods Determination of physical parameters of decontamination solutions such as: pH meter with HANNA 450 , Ohaus density meter, Analytical methods: Quantify concentrations of free chlorine, CS, HD, and GB using UV-Vis method; decontamination products analyzed with GC/MS method Calculating thermodynamic parameters carried out according to Eyring and Arrhenius equations The thesis structure The thesis includes 122 pages divided into three chapters: Chapter Overview (40 pages); Chapter Objects and research methods (17 pages); Chapter Results and discussion (65 pages); References include 117 items in both Vietnamese and English CHAPTER OVERVIEW The chapter showed the overview of CS, HD, and GB and their characteristics; the commonly used methods of decontamination concluding research situation and development trends of military toxic chemicals Chloro – isocyanurate compounds had been used to produce decontamination agents in several countries, such as Italy, the USA, and the UK The chloro-isocyanurate compounds studied (MCCA, NaDCC, and TCCA) were all capable of releasing free chlorine which might act as reactants or catalysts for the decontamination process To research the kinetics and thermodynamics of the decontamination of CS, HD, and GB with MCCA, NaDCC, and TCCA in aqueous solutions, using The Collision Theory with the Arrhenius Equation and the Activated-Complex Theory with the Eyring Equation were employed to calculate the kinetic and thermodynamic parameters In addition, the thesis presented the method of analyzing free chlorine in chloro-isocyanurate solutions CHAPTER OBJETIVES AND RESEARCH METHODS 2.1 Objectives The objectives of the thesis included the decontamination process of the military toxic agents of CS, HD, and GB with MCCA, NaDCC, and TCCA in aqueous media and the main affecting factors 2.2 Research methods Determining the physical parameters of the detoxifying solutions Analysizing free chlorine, CS, HD, GB, and decontamination products were performed according to the method of UV-Vis and GC/MS Thermodynamic parameters were calculated according to Eyring and Arrhenius equations CHAPTER RESULTS AND DISCUSSION 3.1 Method selection of analyzing free chlorine in solutions 3.1.1 Construction of analytic methods of CCl-free using UV-Vis- V530 2,5 y = a + b * x Pearson's r Adj R-Square Intercept Slope ABS 2,0 B 0,99925 0,998 0.1305 ± 0.02779 0.21205 ± 0.00475 1,5 1,0 0,5 10 12 C(mM) Figure 3.2 a: Maximum absorption Figure 3.3 b: Graph of calibration of free chlorine in a solution S1.1 of free chlorine The maximum absorption wavelength of free chlorine was 291nm; the linearity of the calibration curve was from 1.97 to 10.84 mM , Fig.3.3 b; the linear regression model fit the calibration data at 99.85% confidence level; LOD = 1.232 mM; LOQ = 3.887 mM; RSD = 0.107; H = 100.62% The results of determining CCl-free based on the calibration curve shown in figure 3.1 and determining CCl-active using the iodometric method in MCCA, NaDCC, and TCCA solutions with concentrations of 768 mg/L, 768 mg/L, and 768.007 mg/L, respectively, and in 200 ml of 14% NaOCl solution are shown in table 3.4 Table 3.4: Concentrations of free and active chlorine (mM) in C-MCCA, C-NaDCC, and C-TCCA solutions, and in NaOCl solution over time and at different pH levels pH Time (min.) 11 25 25 25 25 2.70 2.69 1.66 1.63 2.56 2.51 3.34 3.30 CCl-free-MCCA CCl-active-MCCA 4.62 3.71 4.62 4.15 4.62 3.92 4.62 3.82 4.66 4.62 3.96 3.93 4.88 4.84 5.53 5.51 CCl-free-NaDCC CCl-active-NaDCC 6.77 5.71 6.77 6.22 6.77 5.98 6.77 5.84 6.76 6.72 5.14 5.11 5.81 5.76 7.27 7.22 CCl-free-TCCA CCl-active-TCCA 9.50 8.59 9.50 8.92 9.50 8.74 9.50 8.68 17.05 10.49 17.1 11.94 17.12 14.01 17.15 13.52 CCl-free-NaOCl CCl-active-NaOCl 17.22 10.43 17.23 11.92 17.21 14.01 17.25 13.51 Table 3.4 shows that, although solutions with approximately similar concentrations were used, the concentrations of free chlorine and active chlorine in the solutions increased in the order of MCCA, NaDCC, and TCCA As pH level changed, the free chlorine concentration also was varied; the free chlorine concentration increased in the order of pH level of 7, 9, and 11 The concentration of free chlorine in MCCA, NaDCC, and TCCA solutions depended on the pH level of the solution and almost stayed the same over time, which is consistent with theory The concentrations of active chlorine in MCCA, NaDCC, and TCCA at the time of minute at different pH levels were the same, but were different at 25 minutes and varied depending on the pH level of the solution In contrast, in NaOCl solution, the free chlorine concentration was almost the same values as the active chlorine concentration at both minute and 25 minute 3.2 Research results of affecting factors and effectiveness of the decontamination reactions of CS, HD, and GB with MCCA, NaDCC, and TCCA 3.2.1 The influence of the time and pH to the effectiveness of decontamination reaction of CS, HD, and GB using MCCA, NaDCC, and TCCA 3.2.1.1 The effectiveness of decontamination reaction of CS with MCCA, NaDCC, and TCCA Table 3.5: The effectiveness of decontamination reaction CS in MCCA-CS, NaDCC-CS, and TCCA-CS at T= 298 K, t= 25 mins Effectiveness of decontamination (%) pH= pH= pH= pH= 11 MCCA-CS 88.22 42.29 99.11 99.99 NaDCC-CS 88.77 44.12 99.25 99.99 TCCA-CS 89.22 45.23 99.36 99.99 Table 3.5 shows that effectiveness of decontamination reaction CS from Reaction 88.22% to 89.22% at pH= 4, t= 25 mins; 42.29% to 45.23% at pH= 7; and greater than 99% (maxium 99.99%) at pH= and pH= 11 3.2.1.2 The effectiveness of decontamination reaction HD with MCCA, NaDCC, and TCCA Table 3.6: The effectiveness of decontamination reaction HD in MCCAHD, NaDCC- HD, and TCCA- HD at T= 298 K, t= 25 mins Reaction MCCA-HD NaDCC-HD TCCA-HD Effectiveness of decontamination (%) pH= pH= pH= pH= 11 99.97 88.20 99.96 99.99 99.96 88.32 99.97 99.98 99.96 89.36 99.95 99.99 Table 3.6 shows that effectiveness of decontamination reaction HD greater than 99.96% at t= 25 mins, pH= 4; 88.2% to 89.36% at pH= 7; and greater than 99.95% at pH= and pH= 11 3.2.1.3 The effectiveness of decontamination reaction GB with MCCA, NaDCC, and TCCA Table 3.7: The effectiveness of decontamination reaction GB in MCCAHD, NaDCC- HD, and TCCA- HD at T= 298 K, t= 25 mins Effectiveness of decontamination (%) pH= pH= pH= pH= 11 MCCA-GB 30.83 63.91 99.98 99.98 NaDCC-GB 36.43 64.62 99.98 99.96 TCCA-GB 37.73 65.57 99.98 99.97 Table 3.7 shows that effectiveness of decontamination reaction GB Reaction from 30.83% to 37.73% at pH=4; 63.91% to 65.57% at pH= 7; and greater than 99.96% at pH= and pH= 11 3.2.2 The influence of the MCCA, NaDCC, and TCCA concentrations to the effectiveness of decontamination CS, HD, and GB Decontamination CS, HD, and GB with MCCA, NaDCC, and TCCA has concentrations in table 3.8 Table 3.8: MCCA, NaDCC, and TCCA concentrations in the reactions Factor MCCA NaDCC TCCA 0 Concentration (mM) 0.235 0.376 0.705 0.175 0.279 0.524 0.165 0.264 0.496 1.879 1.397 1.322 4.697 3.492 3.305 3.2.2.1 The influence of the MCCA, NaDCC, and TCCA concentrations to the effectiveness of decontamination CS (a) (b) Figure 3.8: Graph of influence of the MCCA, NaDCC, and TCCA concentrations to the effectiveness of decontamination CS, CCS= 198.00 mg/L (1.050 mM), T=298 K, t=25 mins, and (a) pH= 4, (b) pH= Figure 3.8 shows that, without MCCA, NaDCC, and TCCA, effectiveness of decontamination CS about 5.7% at pH= and 82% at pH = The greater MCCA, NaDCC, and TCCA concentrations were, the higher the effectiveness became At the highest MCCA, NaDCC, and TCCA concentrations of 4.697 mM; 3.492 mM; and 3.305 mM, respectively, effectiveness of decontamination CS was 88.22%; 88.77%; 89.22% at pH= 4, and reached 99.11%; 99.25%; 99.36% at pH= 3.2.2.2 The influence of the MCCA, NaDCC, and TCCA concentrations to the effectiveness of decontamination HD Figure 3.9 shows that, without the presence of MCCA, NaDCC, and TCCA, HD decontamination success rate was about 8.6% at pH= and 89% at pH = The greater MCCA, NaDCC, and TCCA concentrations were, the higher the decontamination success rate became At the MCCA, NaDCC, and TCCA concentrations of 4.697 mM; 3.492 mM; and 3.305 mM, respectively, HD decontamination success rate was greater than 99.96% at pH= and greater than 99.95% at pH= 11 It can be seen in Figure 3.12 that the MCCA-HD, NaDCC-HD, and TCCA-HD reactions experienced an HD concentration reducing linearly over time (t), all, therefore, being apparent first-order kinetic law The rate constants (k) at pH = in all the three reactions were larger at pH = 3.3.1.3 Determination of the orders and rate constants of GB decontamination reactions using MCCA, NaDCC and TCCA (a) (b) Figure 3.13: Graphs of relationship (lnCGB-t) at T= 298 K, CGB= 21.6 mg/L and (a) pH= 4, (b) pH= As shown in Figure 3.13, the MCCA-GB, NaDCC-GB, and TCCAHD reactions experienced a GB concentration reducing linearly over time (t), all, therefore, being apparent first-order reactions 3.3.2 Study to determine thermodynamic parameters of decontamination Toxic agents with CS, HD and GB concentrations of 1.050 mM; 1.230 mM and 0.154 mM, were detoxified with MCCA, NaDCC and TCCA concentrations of 4.697 mM, 3.492 mM and 3.305 mM, at pH = or pH = and temperatures of 293 K, 298 K, 303 K, 313 K, to determine the reaction rate constants (k) at different temperatures 12 3.3.2.1 Determination of activation energy according to Arrhenius equation and certain thermodynamic parameters according to Eyring equation of CS decontamination with MCCA, NaDCC and TCCA From the graphs of the relationship (lnCCS-t), the reaction rate constants were determined at different temperatures and pHs as shown in Table 3.12 Table 3.12: Rate constants of MCCA-CS, NaDCC-CS TCCA-CS reactions and correlation coefficients at different temperatures No Reaction pH= pH= k (s-1) R2 k (s-1) R2 MCCA-CS-293 0.0013 0.9950 0.0014 0.9708 MCCA-CS-298 0.0014 0.9973 0.0030 0.9908 MCCA-CS-308 0.0016 0.9884 0.0043 0.9060 MCCA-CS-318 0.0023 0.9814 0.0067 0.9505 NaDCC-CS-293 0.0013 0.9956 0.0014 0.9685 NaDCC-CS-298 0.0015 0.9958 0.0030 0.9879 NaDCC-CS-308 0.0017 0.9884 0.0045 0.8816 NaDCC-CS-318 0.0025 0.9952 0.0068 0.9581 TCCA-CS-293 0.0014 0.9979 0.0014 0.9680 10 TCCA-CS-298 0.0015 0.9950 0.0031 0.9832 11 TCCA-CS-308 0.0019 0.9763 0.0043 0.8845 12 TCCA-CS-318 0.0026 0.9875 0.0069 0.9306 From table 3.12, the reaction rate constants in MCCA-CS, NaDCC-CS and TCCA-CS reactions all increased as the temperature increased, in consistence with the Arrhenius equation 13 The calculation results of Ea, ΔH*298, ΔS*298, and ∆G#298 are shown in table 3.13 Table 3.13: Thermodynamic parameters of MCCA-CS, NaDCC-CS and TCCA-CS reactions pH=4 Parameters Value pH= R2 Value R2 MCCA-CS Ea (kJ/mol) 23.88 0.9778 57.17 0.9237 ∆H#298 (kJ/mol) 21.36 0.9728 54.65 0.9169 ∆S#298 (kJ/mol.K) -0.23 -0.11 ∆G#298 (kJ/mol) 89.21 87.83 NaDCC-CS Ea (kJ/mol) 23.25 0.9789 57.59 0.9072 ∆H#298 (kJ/mol) 20.73 0.9740 55.07 0.8992 ∆S#298 (kJ/mol.K) -0.23 -0.11 ∆G#298 (kJ/mol) 89.07 87.78 TCCA-CS Ea (kJ/mol) 23.20 0.9678 57.65 0.9156 ∆H#298 (kJ/mol) 20.68 0.9601 55.13 0.9082 ∆S#298 (kJ/mol.K) -0.23 -0.11 ∆G#298 (kJ/mol) 88.92 87.78 In the MCCA-CS, NaDCC-CS and TCCA-CS reactions at pH = 4, Ea values were all approximately 23 kJ/mol.K and all roughly 57 kJ/mol.K at pH = Ea value of the TCCA-CS reaction was always the smallest In these reactions at different pH values, ∆H#298 and ∆G#298 were positive, 14 indicating that the reactions generating active complexes were endothermic; ∆S#298 values were all negative 3.3.2.2 Determination of activation energy according to Arrhenius equation and certain thermodynamic parameters according to Eyring equation of HD decontamination with MCCA, NaDCC and TCCA Table 3.14: Rate constants of MCCA-HD, NaDCC-HD and TCCA-HD reactions and correlation coefficients at different temperatures No Reaction pH= pH= k (s-1) R2 k (s-1) R2 MCCA-HD-293 0.0022 0.9522 0.0038 0.9738 MCCA-HD-298 0.0045 0.9043 0.0042 0.9550 MCCA-HD-308 0.0052 0.9179 0.0070 0.9569 MCCA-HD-318 0.0079 0.8994 0.0087 0.9774 NaDCC-HD-293 0.0023 0.9558 0.0038 0.9724 NaDCC-HD-298 0.0050 0.8711 0.0046 0.9450 NaDCC-HD-308 0.0060 0.8725 0.0069 0.9652 NaDCC-HD-318 0.0078 0.9092 0.0088 0.9769 TCCA-HD-293 0.0025 0.9661 0.0040 0.9741 10 TCCA-HD-298 0.0054 0.8606 0.0048 0.9579 11 TCCA-HD-308 0.0065 0.8745 0.0072 0.9668 12 TCCA-HD-318 0.0079 0.9409 0.0089 0.9777 From Table 3.14, at pH = and pH = 9, the reaction rate constants in MCCA-HD, NaDCC-HD and TCCA-HD reactions all increased as the temperature increased, in consistence with the Arrhenius equation The correlation coefficient of greater than 0.8606 indicated a reliable result 15 Using reaction rate constants given in table 3.14, Ea, ΔH*298, ΔS*298, and ∆G#298 values were obtained as shown in table 3.15 Table 3.15: Thermodynamic parameters of MCCA-HD, NaDCC-HD and TCCA-HD pH=4 Parameter Value pH= R2 Value R2 MCCA-HD Ea (kJ/mol) 33.81 0.9117 44.90 0.8986 ∆H#298 (kJ/mol) 31.29 0.8982 42.38 0.8873 ∆S#298 (kJ/mol.K) -0.18 - -0.15 - ∆G#298 (kJ/mol) 86.25 - 86.91 - NaDCC-HD Ea (kJ/mol) 32.78 0.9490 42.03 0.8228 ∆H#298 (kJ/mol) 30.26 0.9405 39.51 0.8036 ∆S#298 (kJ/mol.K) -0.19 - -0.16 - ∆G#298 (kJ/mol) 86.18 - 86.70 - TCCA-HD Ea (kJ/mol) 32.10 0.9381 40.13 0.7729 ∆H#298 (kJ/mol) 29.58 0.9276 37.61 0.7940 ∆S#298 (kJ/mol.K) -0.19 - -0.16 - ∆G#298 (kJ/mol) 86.10 - 86.53 - In the MCCA-HD, NaDCC-HD and TCCA-HD reactions at pH = 4, Ea values were all approximately 33 kJ/mol.K and all roughly 42 kJ/mol.K at pH = Ea value of the TCCA-HD reaction was the smallest MCCAHD, NaDCC-HD and TCCA-HD reactions at different pH values, ∆H#298 16 and ∆G#298 were positive, indicating that the reactions generating active complexes were endothermic ∆S#298 values were all negative, demonstrating a reducing number of particles in the reaction or the presence of active complexes 3.3.2.3 Determination of activation energy according to Arrhenius equation and certain thermodynamic parameters according to Eyring equation of GB decontamination with MCCA, NaDCC and TCCA Figure 3.16: Rate constants of MCCA-GB, NaDCC-GB and TCCA-GB peactions and correlation coefficients at different temperatures No Reaction pH= pH= k (s-1) R2 k (s-1) R2 MCCA-GB-293 0.00026 0.9661 0.0045 0.9116 MCCA-GB-298 0.00030 0.9440 0.0052 0.9381 MCCA-GB-308 0.00042 0.9531 0.0066 0.9620 MCCA-GB-318 0.00052 0.8947 0.0089 0.9837 NaDCC-GB-293 0.00027 0.9382 0.0046 0.9251 NaDCC-GB-298 0.00030 0.9177 0.0057 0.9360 NaDCC-GB-308 0.00040 0.9357 0.0068 0.9625 NaDCC-GB-318 0.00051 0.8669 0.0090 0.9844 TCCA-GB-293 0.00030 0.9502 0.0050 0.9370 10 TCCA-GB-298 0.00029 0.8054 0.0058 0.9346 11 TCCA-GB-308 0.00042 0.9220 0.0067 0.9102 12 TCCA-GB-318 0.00052 0.8287 0.0092 0.9892 Table 3.16 demonstrates that at pH = and pH = 9, the reaction rate constants in MCCA-GB, NaDCC-GB and TCCA-GB reactions all increased as the temperature increased This parameter at pH = was 17 larger than that at pH = and peaked in the TCCA-GB reaction at pH = The correlation coefficients of the graphs showing the relationship were greater than 0.8054, indicating a reliable result Using reaction rate constants given in table 3.16, Ea, ΔH*298, ΔS*298, and ∆G#298 values were obtained as shown in Table 3.17 Table 3.17: Thermodynamic parameters of MCCA-GB, NaDCC-GB and TCCA-GB pH=4 Parameter Value pH= R2 Value R2 MCCA-GB Ea (kJ/mol) 26.71 0.9566 26.31 0.9935 ∆H#298 (kJ/mol) 24.19 0.9474 23.79 0.9920 ∆S#298 (kJ/mol.K) -0.23 - -0.21 - ∆G#298 (kJ/mol) 92.94 - 85.94 - NaDCC-GB Ea (kJ/mol) 25.19 0.9755 24.99 0.9908 ∆H#298 (kJ/mol) 22.67 0.9689 22.47 0.9884 ∆S#298 (kJ/mol.K) -0.24 - -0.21 - ∆G#298 (kJ/mol) 92.94 - 85.82 - TCCA-GB Ea (kJ/mol) 23.56 0.8750 23.41 0.9993 ∆H#298 (kJ/mol) 21.04 0.8482 20.89 0.9992 ∆S#298 (kJ/mol.K) -0.24 - -0.22 - ∆G#298 (kJ/mol) 92.85 85.75 It is pointed out in Table 3.17 that in the MCCA-GB, NaDCC-GB and TCCA-GB reactions at pH = and pH = 9, Ea values were all 18 approximately 25 kJ/mol.K In the MCCA-GB, NaDCC-GB and TCCAGB reactions at different pH values, ∆H#298 and ∆G#298 were positive, indicating that the reactions generating active complexes were endothermic ∆S#298 values were all negative, demonstrating the presence of active complexes 3.3.3 Study to determine decontamination products Decontamination was carried out with CS, HD and GB concentrations of 1.050 mM, 1.230 mM and 0.154 mM, respectively, using MCCA, NaDCC and TCCA with concentrations of 4.697 mM, 3.492 mM and 3.305 mM for t = 25 minutes, at pH = and T = 298 K The solution obtained was analyzed by GC/MS with NIST Mass Spectra Library 2005 3.3.3.1 Products of CS decontamination with MCCA, NaDCC, TCCA From the chromatogram of the three solutions obtained, no pic with a retention time of t1R= 14.367 minutes for CS; some pics with a retention time of t1R= 8.152 minutes for 2-chloro benzaldehyde and t2R= 12.199 minutes for oxirane-2,2-dicarbonitrile, 3- (2-chlorophenyl) as the products of the CS decontamination Figure 3.23 d: Chromatogram of the solution after reaction TCCA-CS at pH= 9, T = 298 K, for t= 25 minutes 19 It can be predicted, at pH = 9, CS decontamination was two reactions: Hydrolysis reaction: H C CH CH HC C HC C H C N CH C C CH H O N + H2O CH HC C HC C O C CH C + H CH HC C HC C C N Cl CH Cl N C N C N – Cl CH Phức trung gian H O O CH CH HC C HC C CH C CH N + H2C Cl C N C N CH HC HC C HC C Cl CH N C Oxidation-reduction reaction: Cl O C CH HC CH CH C HC N + OCl C CH Cl CH HC C HC C Cl C N C C – + CH C C CH O N N CH HC C HC C CH Cl C N C N C Cl Phức trung gian O CH HC HC C HC C Cl- + CH C N C N C Cl 3.3.3.2 Products of HD decontamination with MCCA, NaDCC and TCCA From the chromatogram of the three solutions obtained, no pic with a retention time of tR= 8.928 minutes for HD; some pics with a retention time of tR= 13.156 minutes for 1,4-oxathiane, 4,4-dioxide as the products of the HD decontamination 20 Figure 3.25 d: Chromatogram of the solution after reaction TCCAHD at pH= 9, T = 298 K, for t= 25 minutes It can be predicted, at pH = 9, HD decontamination was two reactions: - Hydrolysis reaction O – O Cl CH CH Cl 2 S CH2 CH2 Cl CH2 CH2 Cl + OClS CH2 CH2 Cl – Cl CH2 CH2 Cl - Cl- CH2 CH2 Cl O S S CH2 CH2 Cl CH2 CH2 Cl Phức trung gian CH2 CH2 Cl + 2OH- O + OCl- O CH2 CH2 Cl O S S O CH2 CH2 Cl CH2 CH2 OH - H O O S S O CH2 CH2 Cl CH2 CH2 CH2 CH2 OH O O CH2 CH2 - Oxidation reaction: H H CH2 CH2 Cl Cl S CH2 CH2 S + O + HOH CH2 Cl- Cl CH2 CH2 S + ClCH2 CH2 CH2 CH2 Cl CH2 H H Cl O CH2 CH2 S + CH2 - HCl Cl- Cl CH2 CH2 CH2 S + CH2 CH2 OH CH2 OH- S CH2 CH2 CH2 Cl Phức trung gian CH2 CH2 OH - HCl CH2 CH2 OH + OCl- O - H2O S S S CH2 CH2 OH O CH2 CH2 O CH2 CH2 OH O O CH2 CH2 21 3.3.3.3 Products of GB decontamination with MCCA, NaDCC and TCCA From the chromatogram of the three solutions obtained, no pic with a retention time of tR= 3.688 minutes for GB; and one pics with a retention time of tR= 3.763 minutes for isopropyl methylphosphonic acid as the products of the GB decontamination Isopropyl methylphosphonic acid Figure 3.27 d: Chromatogram of the solution after reaction TCCA-GB at pH= 9, T = 298 K, for t= 25 minutes It can be predicted, at pH = 9, HD decontamination was a reactions: H3C H3C CH O H3C P H3C H3C CH O O + H3C OCl- F CH O O P H3C F O H3C – P – H3C Cl O O Cl F Phức trung gian H3C H3C CH O - FH3C CH O O + H2O P H3C O Cl H3C O + HOCl P H3C OH 3.4 Decontamination CS, HD, GB with solution based on chloroisocyanurate The TĐ17-1 sample was prepared with TCCA 7.7%, equivalent to 0.77 g of TCCA/01g of TĐ17-1 Toxic and decontamination samples were created with TĐ17-1 solution and BX24 solution for t = 25 minutes and at 22 T = 298 K The decontamination solutions were analyzed for the remaining CS, HD and GB concentrations The results show that TĐ17-1 solution was able to detoxify HD and GB on wood at a success rate of 99.58% and 99.59%, respectively, on unpainted metal at the success rate of 99.65% and 99, 68%, respectively, and CS in the soil at the success rate of 79.15% BX24 could detoxify HD and GB on wood at the success rate of 99.65% and 99.69%, respectively, on unpainted metal at the success rate of 99.7% and 99.8%, respectively, and CS in the soil at the success rate of 81.13% CONCLUSION According to the research results above, here are conclusions: An analytical method was chosen to analyze free chlorine in MCCA, NaDCC and TCCA solutions to participate in CS, HD and GB decontamination reactions on UV-Vis instruments with a LOD of 1.232 mM, a LOQ of 3.887 mM, a relative standard deviation of 0.107, and recovery of 100.62% The dynamic study was carried out to determine certain thermodynamic parameters of reactions occurring between MCCA, NaDCC and TCCA agents and CS, HD and GB toxic agent in liquid solution The reactions follow the apparent first-order law with thermodynamic parameters in accordance with the collision theory and activated complex theory The conversion reactions of CS, HD and GB in TCCA solution at 3,305 mM, pH = and T = 297 K for t = 25 minutes had rate constants of kTCCA-CS= 0.031 s-1; kTCCA-HD= 0.054 s-1 and kTCCA-GB= 0.058 s-1, respectively; the conversion reactions of CS showed Ea-CS= 57.65 23 kJ/mol, ∆H#298-CS= 55.13 kJ/mol, ∆S#298-CS= -0.11 kJ/mol.K, and ∆G#298CS= 87.78 kJ/mol; the transformation reactions of HD had Ea-HD= 40.13 kJ/mol, ∆H#298-HD= 37.61 kJ/mol, ∆S#298-HD= - 0.16 kJ/mol.K, and ∆G#298HD= 86.53 kJ/mol; And the transformation reactions of GB occurred with Ea-GB= 23.41 kJ/mol, ∆H#298-GB= 20.89 kJ/mol, ∆S#298-GB= -0.22 kJ/mol.K, and ∆G#298-GB= 85.75 kJ/mol The GC-MS method was used to analyze the product of CS, HD and GB decontamination in TCCA solution with concentration of 3,305 mM at pH = 9, T = 297 K, t = 25 minutes from which to predict the decontamination reactions of CS and HD are two oxidation and hydrolysis reactions occurring in parallel, and the GB decontamination reaction is the hydrolysis reaction with free chlorine as the accelerator TCCA was chosen as the most appropriate detoxifying agent at pH = 9, CTCCA = 768.01 mg/L (3.305 mM) from which TĐ17-1 detoxifying solution was prepared with HD and GB decontamination wood with a success rate of 99.58% and 99.59%, respectively, on unpainted metal with a success rate of 99.65% and 99.68%, and CS decontamination in soil with a success rate of 79.15% New contribution of the dissertation: - Formulating kinetic equations, calculating and determining kinetic parameters of the decotamination of CS, HD and GB with MCCA, NaDCC and TCCA; based on the results of determining the thermodynamic parameters, the reaction mechanism between MCCA, NaDCC, TCCA with CS, HD and GB 24 - Establishing several ingredients of TD17-1 decotamination solution based on TCCA agent, HD and GB decontamination on wood resulted efficiency of 99.58% and 99.59% respectively, on unpainted metal the efficiency of 99.65% and 99.68%, and CS decontamination in the soil at the efficiency of 79.15% Further Research: Studying the role of surfactants and catalysts in the CS, HD and GB decontamination using chloro-isocyanurate Studying the influencing factors and the decontamination rate on different surfaces in climatic conditions of Vietnam THE SCIENTIFIC PUBLICATIONS Lai Van Cuong, Nguyen Khanh Hung, Vo Thanh Vinh, Chu Thanh Phong, Tran Van Chung (2018) “Tested decontamination capability of the TD17 for the toxic agents” Journal of Military Science and Technology Vol 57 - October 2018 Chu Thanh Phong, Nguyen Khanh Hung, Vo Thanh Vinh, Tran Van Chung (2018) “Study on determination of free chlorine content in sodium dichloroisocyanurate solution by UV/VIS absorption spetrometry” International Journal of Development Research Vol 08, Issue, 11, pp.24206-24209, November, 2018 Chu Thanh Phong, Nguyen Khanh Hung, Vo Thanh Vinh, Tran Van Chung (2019) “Kinetic characteristics for reaction between trichloroisocyanuric acid (TCCA) with 2-chlorobenzylidene malononitrile (CS)” International Journal of Engineering Research & Science Vol-5, Issue-8, August- 2019 Chu Thanh Phong, Vo Thanh Vinh, Tran Van Chung, Nguyen Khanh Hung (2019) “Kinetic characteristics for reaction between trichloroisocyanuric acid (TCCA) with yperit-s (HD)” Journal of Military Science and Technology Vol 63 - October 2019 ... Vol 57 - October 2018 Chu Thanh Phong, Nguyen Khanh Hung, Vo Thanh Vinh, Tran Van Chung (2018) “Study on determination of free chlorine content in sodium dichloroisocyanurate solution by UV/VIS... November, 2018 Chu Thanh Phong, Nguyen Khanh Hung, Vo Thanh Vinh, Tran Van Chung (2019) “Kinetic characteristics for reaction between trichloroisocyanuric acid (TCCA) with 2-chlorobenzylidene malononitrile... military toxic chemicals Chloro – isocyanurate compounds had been used to produce decontamination agents in several countries, such as Italy, the USA, and the UK The chloro- isocyanurate compounds