钒(Ⅴ)催化偶氮胂(Ⅲ)褪色反应特性的研究

研究了在磷酸介质中,钒(Ⅴ)对KIO4氧化偶氮胂(Ⅲ)褪色反应的催化作用及柠檬酸的活化作用,测定了体系的动力学性质,确定了反应的最佳条件,建立了测定痕量钒的新方法.实验表明,无柠檬酸时体系为准一级反应,表观速率常量为3.7×10-4s-1,表观活化能为99.4kJ·mol-1,钒的量在0～9.0×10-5g·L-1范围内与log(A0/A)呈线性关系,检出限为1.3×10-7g·L-1.有柠檬酸时为准零级反应,表观速率常量为1.6×10-3s-1,表观活化能为82.9kJ·mol-1,钒的量在0～5.0×10-5g·L-1范围内与ΔA呈线性关系,检出限为7.8×10-8g·L-1.本法简单快速,灵敏度较高,用于钢样中痕量钒的测定,结果较满意.     

锰(Ⅱ)-二甲酚橙-高碘酸钾体系催化分光光度法测定痕量锰

在Na2B4O7-NaOH缓冲介质及加热条件下,锰(Ⅱ)对高碘酸钾氧化二甲酚橙褪色有明显的催化作用,据此建立了测定水样中痕量锰(Ⅱ)的新方法.该法的线性范围为0～32μg·L-1,检出限为4.8×10-6g·L-1.催化反应表观活化能为93.4kJ·mol-1,表观速率常量为1.76×10-3s-1.     

洛美沙星的吸附伏安特性及其应用

在Britton Robinson(pH8 80 ) 0 0 2mol·L- 1KCl底液中 ,洛美沙星 (Lomefloxacin ,简称LMF)在汞电极上有一线性扫描还原峰 ,峰电位Ep=- 1 4 0V (vs.Ag/AgCl) ,该峰具有明显的吸附性 .吸附粒子为LMF中性分子 ,测得LMF在汞电极上的饱和吸附量Гs=4 2 7× 10 - 11mol·cm- 2 ,每个LMF分子所占电极面积为 3 89nm2 ,LMF在汞电极上的吸附符合Langmuir吸附等温式 .测得吸附系数 β =2 2 9× 10 6,2 5℃时的吸附自由能ΔG =- 36 2 9kJ·mol- 1,电极反应电子数n =2 ,不可逆体系动力学参数αnα=1 84 ,表面电极反应速率常数ks=0 2 9s- 1,扩散系数D =7 38×10 - 7cm2 ·s- 1.建立了吸附溶出伏安法测定LMF的最佳条件 ,检出限为 5 0× 10 - 8mol·L- 1.     

2,4-二羟基二苯甲酮在硫酸介质中的极谱行为研究

用单扫示波极谱法研究了2,4-二羟基二苯甲酮在不同浓度H2SO4介质中的极谱行为。实验表明,在0.2mol·L-1的H2SO4介质中其二阶导数峰电位为-1.01V(vs.SCE),峰电流与其浓度在2.5×10-8mol·L-1～1.0×10-6mol·L-1范围内有线性关系,线性方程为ip″(nA·s-2)=116.3+4.559×108c(mol·L-1),(r=0.9985)。循环伏安研究表明,该极谱波为吸附波。     

雷酚内酯的极谱行为研究

研究雷酚内酯在多种体系中的极谱行为。实验表明 ,在不同体系和不同pH范围 ,雷酚内酯产生两个还原波 ,其峰电流和峰电位受酸度影响的情况不同 ,而在B -R缓冲体系条件下 ,峰电流明显受溶液酸度的影响 ,但峰电位基本上保持不变 ;在pH =6.1的B -R缓冲溶液中 ,雷酚内酯的两峰电位分别为 -0 .1 1V和-1 .1V(vs.SCE) ,两峰的峰电流与雷酚内酯的浓度在 3 .1 2 9× 1 0 - 6 mol·L- 1～ 3 .1 2 9× 1 0 - 5mol·L- 1的范围内成良好的线性关系 ,线性回归方程分别为iP′(nA·s- 1) =3 1 1 6+2 .447× 1 0 7c(mol·L- 1) (r =0 .9994)和iP′(nA·s- 1) =1 3 5 2 +4 .83 3× 1 0 7c(mol·L- 1) (r =0 .9993 ) ;循环伏安研究表明 ,两波都是不可逆吸附波     

顺酐均相加氢制备琥珀酸酐的反应动力学研究

对顺酐 (MA)均相加氢生成琥珀酸酐的反应动力学进行了研究 .结果表明 :当催化剂 Ru Cl3· 3H2 O浓度小于 1.2 5× 10 - 2 mol/L ,n(PPh3) /n(Ru) =6 ,MA浓度小于 3.12 5 mol/L和反应氢压小于 1.17MPa时 ,反应速率方程可表示为 :R0 =k1 · c(Ru)· c(MA )· p H2 ;当反应氢压 p H2 大于 1.71MPa时 ,反应速率方程可表示为 :R0 =k2 · c(Ru)· c(MA) .顺酐加氢生成琥珀酸酐的活化能 Ea 为 6 8.5 k J· m ol- 1 ,指前因子 A为4 .6 84× 10 1 0 L· m ol- 1 · h- 1 ,活化焓ΔH≠ 为 6 2 .5 k J· mol- 1 及活化熵Δ S≠ 为 - 5 8.2 J· m ol- 1 · K- 1 .     

羟胺二磺酸盐磺化水解生成铵盐的反应过程 I.羟胺二磺酸钾的磺化反应

针对湿法同时脱硫脱硝工艺 ,提出通过构造一个液相反应过程 ,将 NOx 和 SO2 溶解在溶液中生成的 NO2 -2 和 SO2 -3 经过一系列连续的液相离子反应生成有利用价值的 NH+4 ,实现资源的合理利用。在 35°C～ 74°C,离子强度为 0 .5 5 mol/L时对羟胺二磺酸钾磺化反应动力学进行了研究 ,得出反应的动力学方程为 :- dcHIDSdt =kc HON( SO3) 2 -2 · c HSO-3,其中 k=5 .5 0 9× 1 0 8· e-6.154× 10 4 / RT;在5 0°C、离子强度为 0 .31 mol/L～ 0 .65 mol/L时 ,研究了该反应的盐效应 ,结果表明该反应呈负盐效应 ,离子强度为零时 ,有最大的速率常数 k0 =0 .0 2 4 7L /( mol· min)     

分光光度法测定Fe(Ⅲ)-二甲酚橙显色反应的研究

在 5× 10 -2 mol·L-1HCl溶液中 ,二甲酚橙与Fe(Ⅲ )生成紫红色络合物 ,其最大吸收波长位于5 6 0nm处 ,表观摩尔吸光系数ε =2 .0× 10 4L·mol-1·cm-1.Fe(Ⅲ )含量在 0～ 2 .4mg·L-1范围内符合Beer定律 .用于水样中微量铁 (Ⅲ )的测定 ,结果较满意     

长链不饱和脂肪酸甲酯臭氧化反应速率常数的测定

用气相色谱-质谱联用仪(GC-MS)跟踪测定苯乙烯和β-蒎烯与长链不饱和脂肪酸甲酯混合物的臭氧反应过程,根据竞争反应动力学方法计算了二十四碳烯-15-烯酸甲酯(TAE),二十二碳-13-烯酸甲酯(DAE)和十八碳-9-烯酸甲酯(OAE)的速率常数。结果表明,3种长链脂肪酸甲酯的反应速度快于苯乙烯和β-蒎烯,TAE,DAE和OAE以苯乙烯为参比物在乙酸丁酯中的速率常数分别为2.082×107cm3·mol-1·s-1、2.143×107cm3·mol-1·s-1和2.229×107cm3·mol-1·s-1。     

无水钾镁矾类复盐K_2Zn_2(SO_4)_3的热化学研究

用具有恒定温度环境的新型的反应量热计 ,分别以二次蒸馏水和 3mol· L- 1 HNO3溶液作为量热溶剂 ,在 2 98.2 K条件下 ,测定了具有无水钾镁矾结构的硫酸复盐 K2 Zn2 (SO4) 3的标准摩尔生成焓变 ,其值为 :-34 0 6.85± 0 .2 3k J·mol- 1 .     

含1-氨基-1,2,3-三唑硝酸盐(ATZ-NO3)推进剂能量特性

研究新型氧化剂1-氨基-1,2,3-三唑硝酸盐(ATZ-NO₃)的引入对各类固体推进剂能量特性的影响. 利用国军标方法GJB/84-96及推进剂能量特性计算与CAD系统软件,在标准条件(P_c/P_e=70:1)下,计算了含1-氨基-1,2,3-三唑硝酸盐(ATZ-NO₃)推进剂的能量特性. 结果表明,ATZ-NO₃单元推进剂的比冲为2 413.96 N·s·kg-1,远高于AP单元推进剂,与RDX及HMX单元推进剂接近. 用ATZ-NO₃取代HTPB推进剂中的AP和RDX时,推进剂比冲和特征速度均降低;而用ATZ-NO₃取代GAP推进剂中的AP时,推进剂比冲和特征速度随ATZ-NO₃质量分数多呈抛物线形变化,最高比冲可达2 608.50 N·s·kg-1,固体填料存在最佳添加比. 同时由于ATZ-NO₃不含氯元素,因此将ATZ-NO₃引入GAP推进剂对提高GAP推进剂的综合性能是有益的.      

LiNiPO4前驱体固相反应合成动力学及电容性能

以氢氧化锂、磷酸二氢铵和醋酸镍为原料,以聚乙二醇PEG-400为表面活性剂,采用前驱体固相活化法制备LiNiPO4纳米晶材料.固相制备过程的活化能E=81.08 kJ·mol-1,过程动力学为二维相界面扩散反应机理.前驱体生成LiNiPO4的反应符合界面反应指数成核机理,活化能E1=11.82 kJ·mol-1,指前因子lnA=13.82;LiNiPO4晶体生长过程具有较小的活化能E2=17.73 kJ·mol-1;Li3PO4转化反应和反应体系物系晶化过程符合二维相界面扩散反应机理,其是制备过程可控制的重要步骤.材料复合电极LiNiPO4+Nafion/C在0.5 mol·L-1H2SO4中具有典型的电容性能,电极比电容为214 F·g-1,经1 000次循环,电极电容量不但没有衰减反而略有增加,是潜在的电容器材料.     

催化H2O2氧化吖啶黄固体基质室温磷光法测定痕量秋水仙碱

基于秋水仙碱(COL)能催化过氧化氢(H_2O_2)氧化吖啶黄(AY)的反应,导致AY的室温磷光信号(RTP)剧烈猝灭,据此建立了超灵敏催化H2O2氧化AY固体基质室温磷光法(SS-RTP)测定COL的新方法。此方法的量化限(LOQ)为0.12 fg/斑(对应浓度为3.1×10–13 g·m L–1),灵敏度高、简便、快捷、准确。用于血清中COL的测定,结果与UPLC-MS/MS相吻合。同时测定了动力学常数,其活化能(E)为40.53 k J·mol~(–1),速度反应常数(k)为3.97×10~(–4)·s~(–1)。     

Synthesis and structure determination of ruthenium and osmium complexes with 2,6-bis-(diphenylphosphinomethyl) pyridine

2,6-Bis (diphenylphosphinomethyl) pyridine (PNP) reaction with Na₂OsCl₆ · 6H₂O to give the five coordinated, sixteen-electron complex Os (PNP)Cl₂. In the presence of formaldehyde, the reaction between Na₂OsCl₆· 6H₂O and PNP proceeds rapidly in boiling ethanol to give the coordinately saturated Os(PNP)Cl₂(CO). The IR spectrum of Os(PNP)Cl₂(CO) shows a strong absorption band at 1 970 cm⁻¹ assignable tov _∞ stretch. PNP reacts with RuCl₂(PPh₃)₃ and RuCl₂(DMSO)₄ (DMSO=dimethyl sulfoxide) to give Ru(PNP)Cl₂ (PPh₃) and Ru(PNP)Cl₂ (DMSO) respectively. The average Ru−Cl, Ru−P and Ru−N bond distance in Ru(PNP)Cl₂(PPh₃) determineby X-ray crystallography are 0.242, 0.236 and 0.216 nm, respectively. Li Zhaoying: born in July 1949, associate professor     

Magnetoelectric and converse magnetoelectric res ponses in TbxDy1-xFe2-y alloy ＆ Pb（Mg1/3Nb2/3）（1-x）TixO3 crystal laminated composites

Measured results of magnetoelectric （ME） and converse magnetoelectric （CME） effects of TbxDy1-xFe2-y/ Pb（Mg1/3Nb2/3）（1-x）TixO3/TbxDy1-xFe2-y （TD/PMNT/TD） and PMNT/TD/PMNT laminated composites are presented. ME effect was determined by measuring laminate voltage output under a Helmholtz-generated AC field biased by a DC field （0-1 kOe） （1Oe = 79.58 A/m）. The CME effect was measured by recording the voltage induced in a solenoid encompassing the ME sample while exposed to a DC bias field and PMNT layer driven by a 10 V AC source. The ME and CME responses in the two laminated structure are linear. The highest values of ME coefficients in TD/PMNT/TD and PMNT/TD/PMNT composites are 384 mV/Oe and 158 mV/Oe, respectively, while the highest values of CME coefficients in the two composites are 118 mG/V and 162 mG/V （1 G=10^-4 T）, respectively.     

Syntheses and lyotropic liquid crystal properties of a series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30

A series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30, Na16[As4W30M4(H2O)2O112]·XH2O (M = Zn,Cu,Co,Ni,Mn and Cd), have been synthesized for the first time and structurally characterized by elemental analysis, IR and 183W NMR spectra. The crystal structure of Na16[As4W30Cu4(H2O)2O112]·63H2O was determined to be a triclinic system, of P1 symmetry, a = 1.2721(3) nm, b = 2.451 6(5) nm, c = 2.6450(5) nm, α= 89.90(3)°,β= 77.32(3)°, γ= 89.96(3)°, 2=2. Using tetrahepty lammonium bromide as a phase transfer reagent, [As4W30Cu4(H2O)2O112]16- was transferred from aqueous solution to organic phase (benzene), and the heteropolyanion lost the coordination water molecules to form the coordination-unsaturated ion. After lactic acid was added to the benzene solution, the coordination-saturation was recovered. By esterification reaction between lactic acid and cholesterin, the latter was attached to the heteropolyanion indirectly. Therefore, a new type of lyotropic liquid crystal was obtained, which was characterized by a polarimicroscope, DSC and variable temperature wide-angle X-ray diffraction.     

3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO<Subscript>2</Subscript> catalyst

Ammoxidation of 3,4-dichlorotoluene (DCT) to prepare 3,4-dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO₂ catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH₃/DCT in the feed gas and the space velocity (v ₁) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reactionT=673 K,n(DCT):n(NH₃):n(air)=1:7:30 andv ₁=250 h⁻¹. At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO₂ catalyst. Foundation item: Supported by Youth Chen-Guang Project of the Committee of Science and Technology of Wuhan (20015005042) Biography: Huang Chi(1972-), male, Ph D, Lecture, research direction: ammoxidation.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

The concentration quenching characteristics of 5D3-7FJ and 5D4-7FJ (J=0―6) transitions of Tb3+ in YBO3:Tb3+ phosphor

The photoluminescence quenching behaviors of ^5D3-^7Fj and ^5D4-^7Fj （J = 0—6） transitions of Tb^3＋ in YBO3：Tb under 130—290 nm excitation were systematically investigated. The results revealed that the quenching concentrations of both ^5D3-^7Fj and ^5D4-^7Fj transitions of Tb^3＋ in YBO3：Tb were mainly dependent on excitation wavelength. Particularly, the quenching concentrations of ^5D4-^7Fj transitions of Tb^3＋ under 130—290 nm excitation were correlated with excitation bands of YBO3：Tb. The quenching concentrations of ^5D3-^7Fj transitions remained at low concentration （2%） under 186—290 nm excitation and then increased gradually with energy of incoming excitation photon when excited at 130—186 nm. This dependence should be involved in their excitation mechanisms and quenching pathway in particular excitation region.[第一段]     

硫酸钛催化酯化反应动力学研究

根据硫酸钛催化合成乙酸正丁酯反应的特点导出非等温变体积条件下的反应速率方程,并导出用于计算动力学参数的理论公式。在此基础上对不同实验条件下的多组实验数据进行动力学处理,结果表明该反应服从二级反应动力学模型,表观活化能为１９７．９４ｋＪ·ｍｏｌ－１,指前因子为４．２６５１×１０２５ｄｍ３·ｍｏｌ－１·ｍｉｎ－１．