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1.
制备了含3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)铅复合物(LCBTATZ)的双基推进剂和改性双基推进剂. 采用热重-微商热重法(TG-DTG)及差示扫描量热法(DSC)研究了其热分解行为和非等温分解动力学并在此基础上评价了其热安全性. 结果表明, LCBTATz-DB复合物中在350-540 K之间只存在一个放热分解峰, LCBTATz-CMDB复合物中存在两个连续的放热分解峰在390-540 K温度范围内, 其机理方程分别为: f(α)=α-1/2和f(α)=2(1-α)3/2. 计算了热加速分解温度(TSADT)、热爆炸临界温度(Tb)、热点火温度(TTIT)和绝热至爆时间(tTlad),其值分别为: DB001复合物TSADT=444.50 K, TTITT=453.96 K, Tb=471.84 K; tTlad=39.36 s; CMDB100复合物, TSADT=442.38 K, TTITT=452.89 K,Tb=464.13 K,tTlad=21.3 s,并以此来评价化合物的热安全性. 考察了LCBTATz-DB以及LCBTATz-CMDB的燃烧性能, 结果表明LCBTATZ 是一种高效的双基燃烧催化剂, 在较大的压力范围内可以显著的提高燃速并且大幅度的降低压力指数. 对于双基推进剂在2-8 MPa压力范围内出现了明显的超燃速现象, 8-12 MPa出现了“麦撒”效应, 对于改性双基推进剂的压力指数降到0.18.  相似文献   

2.
为应用热爆炸临界温升速率(dT/dt)Tb评价含能材料(EMs)的热安全性, 得到计算(dT/dt)Tb值的基本数据, 用合理的假设, 由Semenov的热爆炸理论和9 个自催化反应速率方程[dα/dt=Aexp(-E/RT)α(1-α) (I), dα/dt=Aexp(-E/RT)(1-α)n(1+Kcatα) (II), dα/dt=Aexp(-E/RT)[αa-(1-α)n)] (III), dα/dt=A1exp(-Ea1/RT)(1-α)+A2exp(-Ea2/RT)α(1-α) (IV), dα/dt=A1exp(-Ea1/RT)(1-α)m+A2exp(-Ea2/RT)αn(1-α)p (V), dα/dt=Aexp(-E/RT)(1-α) (VI), dα/dt=Aexp(-E/RT)(1-α)n (VII), dα/dt=A1exp(-Ea1/RT)+A2exp(-Ea2/RT)(1-α) (VII), dα/dt=A1exp(-Ea1/RT)+A2exp(-Ea2/RT)α(1-α) (IX)]导出了计算(dT/dt)Tb值的9 个表达式. 提出了从不同恒速升温速率(β)条件下的差示扫描量热(DSC)曲线数据计算/确定EMs自催化分解反应的动力学参数和自催化分解转向热爆炸时的(dT/dt)Tb的方法. 由DSC曲线数据的分析得到了用于计算(dT/dt)Tb值的β→0 时的onset 温度(Te0),热爆炸临界温度(Tb)和相应于Tb时的转化率(αb). 分别用线性最小二乘法和信赖域方法得到方程(I)和(VI)及方程(II)-(V)和方程(VII)-(IX)中的自催化分解反应动力学参数. 用上述基础数据得到了EMs的(dT/dt)Tb值. 结果表明: (1) 在非等温DSC条件下硝化棉(NC, 13.54% N)分解反应可用表观经验级数自催化反应速率方程dα/dt=1015.82exp(-170020/RT)(1-α)1.11+1015.82exp(-157140/RT)α1.51(1-α)2.51描述; (2) NC (13.54% N)自催化分解转向热爆炸时的(dT/dt)Tb值为0.103 K·s-1.  相似文献   

3.
以(S)-2-氨基丙醇为手性源与α-溴-3-氯苯丙酮反应, (R)-2-氨基丙醇为手性源与6-甲氧基-2-(2-溴丙酰基)萘反应, 分别合成了手性纯化合物(2R,3R,5S)-3,5-二甲基-2-(3-氯苯基)-2-吗啉醇盐酸盐(4a)和(2S,3S,5R)-3,5-二甲基-2-(6-甲氧基-2-萘基)-2-吗啉醇盐酸盐(4b), 利用X射线单晶衍射仪测定了两化合物的晶体结构和两化合物的空间结构, 并初步分析两化合物空间结构, 化合物4a晶体属正交晶系, 空间群为P21212, 晶胞参数为: a=0.8718(2) nm, b=0.7883(2) nm, c=2.0247(6) nm, Z=4, V=1.3915(7) nm3, Dc=1.328 g/cm3, F(000)=584, R1=0.0399, wR2=0.0797, S=1.042. 化合物4b晶体属正交晶系, 空间群为P212121, 晶胞参数为: a=0.71035 (9) nm, b=0.77703(10) nm, c=2.9820(4) nm, Z=4, V=1.6318(4) nm3, Dc=1.318 g/cm3, F(000)=688, R1=0.0520, wR2=0.1108, S=0.994.  相似文献   

4.
邓玉恒  刘娟  李宁  杨永丽  马宏伟 《化学学报》2007,65(24):2868-2874
在甲醇溶液中合成了一系列IIB过渡金属Zn(II), Cd(II)的二羟乙基二硫代氨基甲酸[(EtOH)2dtc]的配合物, 并对配合物M[(EtOH)2dtc]2L [M=Zn (1), Cd (2), L=2,2'-联吡啶; M=Zn (3), Cd (4), L=邻菲啰啉]进行了红外光谱、元素分析、热重分析表征工作. 热重分析表明配合物14中DTC配体比中性配体更易失去, 热分解最终产物为相应的氧化物. 对化合物1, 2做了X-ray单晶衍射分析, 1为单斜晶系, P21/c空间群, 晶胞参数a=0.72146(5) nm, b=2.61720(18) nm, c=1.59438(11) nm,b=97.899(2)°, V=2.9820(4) nm3, Z=4, m=1.133 mm-1, Dc=1.297 Mg•m-3; 2为三斜晶系, P-1空间群, 晶胞参数a=1.0075(2) nm, b=1.1580(2) nm, c=1.1777(2) nm, a=70.92(3)°, b=85.71(3)°, γ=81.02(3)°, V=1.2822(4) nm3, Z=2, m=2.118 mm-1, Dc=1.630 Mg•m-3.  相似文献   

5.
袁爱华  沈小平  周虎  陆路德 《化学学报》2005,63(19):1795-1801
将Ni(teta)(ClO4)2 (teta=5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)的DMF溶液和K3[Fe(CN)6]的水溶液在填充了琼脂冻胶的U型管中通过扩散反应, 得到了标题化合物(H2teta)2{[Ni(teta)][Fe(CN)6]2}•17H2O, 该化合物晶体属三斜晶系, 空间群P1, 晶胞参数为a=0.9998(2) nm, b=1.5514(3) nm, c=1.6647(4) nm, α=114.15(2)°, β=100.91(2)°, γ=93.42(2)°, V=2.2863(10) nm3, z=1, Dc=1.196 g•cm-3, F(000)=890, μ=5.84 cm-1, GOF=0.894, R1=0.0582, wR2=0.1446 [I>2σ(I)]. 该化合物的基本单元由2个[H2teta]2+阳离子、1个{[Ni(teta)][Fe(CN)6]2}4-阴离子和17个水分子组成, 它们之间通过N—H…N氢键而形成具有二维平面结构的超分子化合物. 1.8~300 K变温磁化率研究表明, 化合物中三核体系Fe (s=1/2)-Ni (s=1)-Fe (s=1/2)中心原子间通过氰基桥联而发生强的铁磁相互作用, 磁参数J=4.33 cm-1, g=2.6, θ=60 K. 通过TG-DTG测定了配合物的热稳定性.  相似文献   

6.
2,2,2-三硝基乙基-N-硝基甲胺的热安全性   总被引:1,自引:0,他引:1  
为评价2,2,2-三硝基乙基-N-硝基甲胺(TNMA)的热安全性, 得到计算TNMA热安全性参数用的基本数据, 用经验式估算了TNMA的比热容(Cp)和热导率(λ). 用键能贡献于生成热Qf的加和法, 估算了TNMA的标准生成焓ΔcHmθ(TNMA, s, 298.15 K). 用热力学公式计算了TNMA的标准燃烧焓ΔUmθ(TNMA, s, 298.15 K)和标准燃烧能ΔcHmθ(TNMA, s, 298.15 K). 用Kamlet-Jacobs 公式估算了爆速、爆压和爆热. 用经验式估算了分解热(Qd). 通过差示扫描量热(DSC)曲线和高灵敏度布鲁顿玻璃薄膜压力计测得的逸出气体标准体积(VH)-时间(t)曲线, 得到了TNMA放热分解反应的动力学参数. 用上述基本数据得到了评价TNMA的热安全性参数: 自加速分解温度(TSADT), 热爆炸临界温度(Tbe0和Tbp0), 绝热至爆时间(tTIad), 撞击感度50%落高(H50), 热点起爆临界温度(Tcr), 被300 K环境包围的半厚和半径为1 m的无限大平板、无限长圆柱和球形TNMA的热感度概率密度函数S(T), 相应于S(T)-T关系曲线最大值的峰温(TS(T)max), 安全度(SD), 临界热爆炸环境温度(Tacr)和热爆炸概率(PTE). 结果表明: (1) TNMA有较好的热安全性和对热抵抗能力, 与环三亚甲基三硝胺(RDX)相比, TNMA易从热分解过渡到热爆炸; (2) 不同形状大药量TNMA 热安全性降低的次序为: 球>无限长圆柱>无限大平板; (3)TNMA有高的燃烧能、高的爆轰化学能(爆热)和接近环四亚甲基四硝胺(HMX)的爆炸性能, 其对冲击敏感, 冲击感度与季戊四醇四硝酸酯(PETN)和特屈尔接近, 可用作混合炸药主组分.  相似文献   

7.
2,6-二氯-4-三氟甲基苯胺经重氮化后与2,3-二氰基丙酸酯反应合成了1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑(1), 1与乙酸酐、顺丁烯二酸酐、苯甲酰氯反应得到1的乙酰胺2a、顺丁烯酰亚胺2b和苯甲酰胺2c. 通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱、质谱等手段对其结构进行了表征. 用X射线单晶衍射测定了化合物2a, 2b2c的晶体结构. 2a属于单斜晶系, C2/c空间群, 晶胞参数a=1.88282(6) nm, b=0.86541(3) nm, c=1.90766(6) nm, β=95.5830(10)°, V=3.09362 nm3, Z=8, R=0.064, wR=0.170. 2b属于单斜晶系, P21/n空间群, 晶胞参数 a=1.28261(10) nm, b=0.89942(7) nm, c=1.46896(12) nm, β=104.217(1)°, V=1.6427(2) nm3, Z=4, R=0.055, wR=0.165. 2c属于三斜晶系, P-1空间群, 晶胞参数a=0.84613(11) nm, b=0.98923(13) nm, c=1.14305(15) nm, β=96.002(2)°, V=0.9326 nm3, Z=2, R=0.0684, wR=0.1795.  相似文献   

8.
 研究指出表观二级动力学方程可以很好地描述N-异丙基丙烯酰胺水凝胶的溶胀和消溶胀动力学.即溶胀动力学方程为dR/dt=k1(Re-R)2,消溶胀动力学方程为-dR/dt=kc(R-Re)2.把这种水凝胶用于分离高分子水溶液时可引入“单位溶张比分离循环的合理时耗”这样一个参量.它根据溶胀和消溶胀过程中的起始溶胀比、平衡溶胀比、表观溶胀动力学常数和表观消溶胀动力学常数求出.具体公式为△t1(Ts,Tc)=2/[Rc(Ts)-R0(Ts)]2ks(Ts)+15/[R0(Tc)- Rs(Tc)]2kc(Tc)1/2在理想情况下,分离过程的“总合理时耗”与△t_1成正比,比例系数为分离过程中的除水总量与干凝胶用量的比值,即△tr=WW/WG·△t1.当根据二个动力学方程求得的总时耗计算值处于(0.9△tr,1.1△tr)范围内时,表明所选干凝胶用量和循环溶胀比区段均合适.  相似文献   

9.
两种取代二茂铁基三甲基硅烷基氰醇醚的合成及晶体结构   总被引:1,自引:0,他引:1  
王晓丽  王艳学  边占喜 《化学学报》2007,65(16):1670-1674
通过两种取代的乙酰基二茂铁与三甲基氰硅烷的加成反应, 得到两种取代二茂铁基三甲基硅烷基氰醇醚的晶体: 1-(1-氰基-1-三甲基硅烷氧基乙烷基)二茂铁(1), 1,1'-二(1-氰基-1-三甲基硅烷氧基乙烷基)二茂铁(2), 用X射线单晶衍射、元素分析、红外光谱和核磁共振氢谱对分子结构进行了表征. 测试结果表明: 晶体1属正交晶系, Pbca空间群, a=1.1995 nm, b=1.2441 nm, c=2.2183 nm, Z=8, R1=0.0456, wR2=0.0880; 晶体2属正交晶系, Pna2(1)空间群, a=2.0715 nm, b=0.6440 nm, c=1.8411 nm, Z=4, R1=0.0485, wR2=0.0866. 晶体结构表明, 分子中都存在超共轭效应.  相似文献   

10.
合成了配体N-皮考林酰肼(简写为Hphz)及其双核钯配合物[Pd2(phz)2Cl2]. X射线衍射实验结果表明, 配体和配合物晶体均属于单斜晶系, 空间群分别为C 2/cP 21/c, 分子式分别为C6H7N3O和C12H12Cl2N6O2Pd2. 晶体学参数, Hphz, a=1.9245(2) nm, b=0.38927(2) nm, c=1.8073(2) nm, b=107.255(2)°, V=1.2931(2) nm3, Z=8, Dc=1.409 Mg/m3, F(000)=576, μ(Mo Kα)=0.102 mm-1, R=0.0541, wR=0.1762; [Pd2(phz)2Cl2], a=1.48274(9) nm, b=1.44797(9) nm, c=0.73951(5) nm, b=92.719(3)°, V=1.5860(2) nm3, Z=4, Dc=2.329 Mg/m3, F(000)=1072, μ(Mo Kα)=2.62 mm-1, R=0.0262, wR=0.0555. 在配合物[Pd2(phz)2Cl2]分子内, 两个钯(II)原子, 均呈畸变的N3Cl平面正方形配位构型, 晶体内通过分子间氢键N—H…Cl 作用形成一维链状结构, 分子间吡啶环存在相互作用. 量子化学从头算方法计算结果表明, 分子内及分子间的金属钯之间也存在相互作用. 红外光谱表明, 配体在形成配合物后, ν(C=O)和ν(C=N)红移, ν(C—N)蓝移, 荧光光谱表明, 配合物金属对配体n-π*激发(310 nm)引起的发射峰有较大的影响.  相似文献   

11.
微量热法测定细菌的临界生长温度   总被引:5,自引:1,他引:5  
In this paper, we have determined the multiplication rate constanis (k) of Shigella flexneri and E. coli. at different temperatures and in different culture media by means of a microcalorimeter. From these results a linear equation as k~(1/2)=a+bT can be established for the bacterial growth. The corresponding linear equation for S. flexneri is k~(1/2)=-1.2823+0.0047122 T(r=0.971), so its eritica lgrowth temperature T_0 is equal to 272.1 K. The linear equation for E coli is k~(1/2)=-1.6390+0.005948 T (r=0.994), T_0=275.5 K. The experimental results indicate that the critial growth temperature of E. coli. is nearly a constant (T_0=273.9 K) in different culture media, which is very informative for the study on microorganism growth.  相似文献   

12.
应用微量热学的方法,我们已能成功地测得细菌生长过程的热谱,这种热谱包含着有关细菌生长代谢过程的丰富信息,例如对热谱曲线的指数生长段进行解析,可得出细菌生长的速率常数、激活能和有关的热力学参数。故采用微量热法测定细菌在不同培养温度下的生长速率常数,利用计算机拟合出相应k(速率常数)和T(培养温度)的线性关系式后,若把生长速率为零的温度定义为临界生长温度时,就可以根据由上述实验所得的k~T线性关系式求得细菌的临界生长温度。本工作仍采用微量热法对福氏志贺氏菌(S. flexneri)和大肠埃希氏菌(E. coli)进行实验测定。按文献的方法求出它们在不同温度下的生长速率常数;对于大肠埃希氏菌还用几种不同的培养基分别进行实验测定。  相似文献   

13.
The adsorption isotherms of N(2) gas at 77 K and CCl(4) vapor at 283.1(5), 298.1(5), and 308.1(5) K were measured for six samples of the mesoporous silicas having uniform cylindrical pores (MCM-41). The pore radii of the six samples (r(p)), which were evaluated from the alpha(s) plots of the N(2) isotherms, were 1.13, 1.29, 1.50, 1.65, 1.90, and 2.53 nm. The CCl(4) adsorption isotherms show that the capillary condensation occurs at the very narrow P/P(0) range. The core radii of the six adsorbents (r(c)), which were estimated from a comparison plot of the CCl(4) isotherm, were 0.90, 1.01, 1.28, 1.37, 1.60, and 2.17 nm. In the comparison plot, the standard CCl(4) isotherm for nonporous silica was used as the reference isotherm. It has been clarified that the Polanyi adsorption potential of capillary condensation is proportional to the reciprocal of the core radii: RT ln(P(0)/P)=5.37r(c)(-1) nm(-1), ln(P(0)/P)=2.17r(c)(-1) nm(-1) at 298.1(5) K, [A]. The statistical thickness of adsorbed CCl(4) on the curved surface (t((pore))), which was estimated from the difference between the pore radii and the core radii, was given by Eq. [B]: t((pore))=0.188+0.336(P/P(0))+0.382(P/P(0))(2) nm [B], (0.08

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14.
本文利用DSC研究了热致液晶性序列嵌段共聚酯在不同升温速率时的多重熔融转变,和不同冷却速率对结晶与熔融过程的影响。发现T_(kn)和T_(ni)与热历史、升温速率及成形条件均无关,T_(kn)=425.86K,T_(nt)=480.60K;而T_(in)与T_(nk)随冷却速率增大而降低。  相似文献   

15.
Critical temperature(T b ) of thermal explosion for energetic materials is estimated from Semenov’s thermal explosion theory and the non-isothermal kinetic equation dα/dt=A 0 exp(bT)[1+(T–T 0 )b]f(α) deduced via reasonable hypotheses, where T 0 is the initial point of the deviation from the baseline of DSC curve. The final formula is (T b –T e0 ){1+1/[1+( T b –T 00 )b]}=1. We can easily obtain the initial temperature(T 0i ) and onset temperature(T ei ) from the non-isothermal DSC curves, the values of T 00 and T e0 from the equation T 0i or ei =T 00 or e0 +α 1 β i +α 2 β i2 +…+α L–2 β iL –2 , i=1,2,…,L, the value of b from the equation: ln[β i /(T ei –T 0i )]=ln[A 0 /G(α)]+bT ei , so as to calculate the value of T b . The result obtained with this method coincides completely with the value of T b obtained by Hu-Yang-Liang-Wu method.  相似文献   

16.
鉴于不等同球颗粒在胶体化学中的重要性,所以它一直引起人们在理论上的关注。Hogg、Healy和Fuerstenau(HHF)对Poisson-Boltzmann方程引用Debye-Hückl近似,得出不同平行平板型颗粒在恒电位表面时相互作用能计算公式,进而HHF用Derjaguin法得出不等同球颗粒相互作用能的表达式。虽然HHF的公式仅适用低电位的情况,但它的表达式特别简单,因而一直被广泛使用。Ohshima等(OCHW)对球颗粒做了曲率校正,Barouch等(BM)对Poisson-Boltzmann方程提出二维解法,使不等同球颗粒的相互作用能的计算有了改进和提高。本文根据我们提出的模型和方法,对HHF公式也做了曲率校正,结果表明它和OCHW的曲率校正结果相当,但它的表达式却要简单得多。  相似文献   

17.
The surface tension of adipic aqueous solutions was measured as a function of temperature (T=278-313 K) and adipic acid mole fraction (X=0.000-0.003) using the Wilhelmy plate method. A parametrization fitted to these data is presented. The evaporation rates of binary water-malonic and water-adipic acid droplets were measured with a TDMA technique at different temperatures (T=293-300 K) and relative humidities (58-80%), and the saturation vapor pressures of subcooled liquid malonic and adipic acids were derived from the data using a binary evaporation model. The temperature dependence of the vapor pressures was obtained as least-squares fits to the derived vapor pressures: ln(Psat,l) (Pa)=220.2389-22634.96/T (K)-26.66767 ln T (K) for malonic acid and ln(Psat,l) (Pa)=140.6704-18230.97/T (K)-15.48011 ln T (K) for adipic acid.  相似文献   

18.
Erythromycin sensitive electrodes have been proposed. Their selectivity toward quaternary ammoniums is described in terms of induction effect and steric hindrance effect: logKil=a_1I-a_2Z/R+a_0, where I is induction effect index, a_1,a_2 and a_0 are coefficients which depend on the electro-active material. A general formula has been suggested to relate the electrode selectivity to the carbon atom number (n) of the alkyl of the quaternary ammonium; logK_(ij)=A/2.7~R-B/(0.80+1.26n)+C, where A, B and C are coefficients which depend on the electro-actlve material, logK_(ij) tends to a limited value C when n increases.  相似文献   

19.
The adsorption isotherms of hydrogen on super activated carbon were measured systematically, covering a temperature range of 93-293 K at 20 K intervals and pressures up to 7 MPa. All the experimental data were linearized by adopting the coordinates ln ln(n) vs 1/(ln P). The results indicate that the adsorption limit (P(lim), n(lim)) exists virtually at high pressure and has a certain physical meaning. Based on the adsorption limit, further analyses were carried out by modeling the adsorption isotherms in the coordinates ln(n(lim)/n) vs ln(RT(ln(P(lim)/P) and a linear comprehensive adsorption model was proposed in the form n (lim)=n.exp(psi T+lambda/T-c/) (beta).[RT ln( P (lim)P )] (b) which can predict the adsorption isotherm of hydrogen on activated carbon in supercritical conditions.  相似文献   

20.
The perovskite type of compound [n-C_(11)H_(23)N_3]_2ZnCl_4(abr.C_(11)Zn)exhibits two solid-solid phasetransitions at T_(c1)=298.7 K and T_(c2)=360.1 K.A temperature dependence study of Raman spectra of C_(11)Znprovides the evidence of occurence of the structural phase transition related to the dynamics of thealkylammonium ions.The room temperature phase is ordered and contains the all-trans alkyl chains.Theintermediate temperature phase presents a partial conformational disorder and liquidlike state of allconformational disorder occurs at high-temperature phase.  相似文献   

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