盐酸对硝酸铵热分解的影响

利用C80微量量热仪测定了纯硝酸铵、混有盐酸的硝酸铵在热分解过程中的反应和放热特性.比较了纯硝酸铵热分解反应和加入盐酸后硝酸铵发生热分解反应的不同机理.根据实验测得的热分解反应热流速计算得到热分解反应的化学动力学和热力学参数.结果表明,盐酸对硝酸铵的热分解具有催化作用,其反应活化能小于纯硝酸铵的反应活化能.根据热爆炸理论,利用反应的化学动力学和热力学参数计算得到混有盐酸的标准包装硝酸铵的自加速分解开始温度.     

纳米碳酸钙的粒度对热分解活化能的影响

利用热分析仪测定了不同粒径纳米碳酸钙的热分解曲线,分别采用Achar方程和Coats-Redfern方程对热重数据进行了拟合,得到了不同粒径纳米碳酸钙的表观活化能,讨论了粒度对表观活化能的影响规律.研究结果表明,纳米碳酸钙热分解反应属于Avrami-Erofeev的成核与生长为控制步骤的反应机理,其热分解反应的表观活化能随着粒径的减小而降低,并且表观活化能与粒径的倒数呈线性关系.     

替硝唑的非等温热分解动力学及热稳定性研究

报道了用热重法(TG)研究替硝唑（Tinidazole,TNZ）原药及片剂中替硝唑热分解非等温动力学以及药物的稳定性,并对用热重分析仪测定片剂含量的方法进行了探讨.推断出原药热分解过程为零级反应,其动力学方程为dα/dt=Ae-(Ea)/(RT),热分解反应活化能Ea为99.7kJmol-1,指前因子A为3.60×107s-1;片剂中替硝唑的热分解过程为三维扩散级反应,其动力学方程为dα/dt=Ae-(Ea)/(RT)3/2(1+α)2/3/［(1+α)1/3-1］,活化能Ea为105.1kJmol-1,指前因子A为1.08×106s-1.实验表明替硝唑原药具有较高的热解活化能,热稳定性较好;在片剂中热分解机理和分解活化能发生改变,说明赋形剂对药物的热稳定性有一定影响.根据得到的热分解反应的机理函数和动力学参数,得到片剂有效存贮期与贮存温度的关系曲线,估算出在室温（25℃）下,分解率为10%时药物的存贮期为26.7年,分解率为5%时所需要的时间约为6.9年.     

聚亚苯基苯并二唑的热分解行为

用热失重方法分析了聚亚苯基苯并二唑（PBO）纤维在不同气氛中的热分解行为,采用Ozawa法计算了PBO纤维在氮气和空气两种气氛中的热分解活化能.结果表明升温速率对PBO纤维的热分解温度有较大影响;氧气作为热分解反应的引发剂,大大降低了分解反应的活化能;由IR光谱对不同温度裂解产物结构的分析,推测了热氧化降解对PBO纤维分子结构的影响;在不同失重率时几乎相同的热分解活化能,表明无论热分解的气氛如何,PBO纤维的热分解均是一个无规引发的单阶段过程;结合PBO纤维在两种气氛中的热分解机理,解释了分解气氛对残碳率的影响.     

米力农的热稳定性研究

利用热重分析技术研究了米力农药物在氮气气氛下的热分解动力学,采用Flynn-Wall-Ozawa法和Kissinger法,计算了该药物的热分解反应活化能E和指前因子lnA,并进行了比较.结果表明,Flynn-Wall-Ozawa法和Kissinger法计算所得活化能比较接近,米力农药物的平均活化能为165.69 kJ/mol,指前因子lnA为32.44 s-1,热解反应级数为n=1.00.并推断了米力农药物在室温298.15 K下的存放有效期为4年.热重分析法可以便捷、科学、经济地预测药物的稳定性和贮存期,为该药物的生产与评价提供参考依据.     

基于可视化热重分析技术的宣纸热分解特性研究及动力学分析

为了解宣纸的劣化机理,本文利用可视化热重分析技术对宣纸在氮气与空气中的热分解过程进行了实验和分析,结果表明其过程主要阶段为发挥性成分的析出过程,宣纸样品经历快速失重、面积收缩且颜色加深,其中空气气氛可促进热分解反应并在反应后期氧化前期生成的炭化物;然后以高斯分布函数对微商热重(DTG)曲线进行拟合得到三组分,并且三组分的反应区间符合生物质的热分解特性且受气氛影响;此外,本文还基于Lab色彩空间对实时观察热分解图像进行了分析,其结果相比热失重数据在反应起始和中止阶段灵敏度更高,并可对热失重数据进行补充;同时,本文以Friedman法、FWO法计算宣纸在氮气与空气中的表观活化能E,得到氮气与空气气氛中的结果分别为195.4 kJ/mol、162.98 kJ/mol;最后通过Malek法对宣纸样品的热分解数据进行最概然机理函数的选择,并得到氮气中的热分解活化能E为245.60 kJ/mol,指前因子的自然对数ln A为37.39 s^-1;空气中活化能E在150.18～305.41 kJ/mol, ln A在49.13～20.18 s^-1。     

N,N′-二苯基顺丁二甲酰胺β晶型成核剂的热分解动力学

以TG/DTG/DTA为手段, 研究了N,N′-二苯基顺丁二甲酰胺β成核剂在空气气氛中的热分解动力学,利用Kissinger法、Flynn-Wall-Ozawa(FWO)法对N,N′-二苯基顺丁二甲酰胺β成核剂进行了动力学分析,求出了该物质的热分解动力学参数,同时利用Satava-Sestak法研究了该物质的热分解机理.用等温TG法得到失重10%的寿命方程.结果表明,Kissinger法所求的活化能为113.01 kJ·mol-1,指前因子lg A =9.83;Flynn-Wall-Ozawa法所求得的活化能为112.46 kJ·mol-1.N,N′-二苯基顺丁二甲酰胺β成核剂的热分解机理为相边界反应,圆柱形对称,反应级数n=(1)/(2),其动力学方程为G(α)=1-(1-α)1/2.寿命方程为:ln τ＝ -36.646+1.9117×104/T.     

ZrxCe1-xO2的制备及其氢氧化物前驱体的热分解过程研究

采用共沉淀法制备了不同铈锆比的ZrxCe1-xO2(x=0,0.1,0.3,0.5,0.7,0.9,1.0)固溶体.利用热分析方法研究了Zrx(OH)4x.Ce1-x(OH)4(1-x)体系的热分解过程,并运用XRD对其热分解产物进行了表征.实验表明Zrx(OH)4x.Ce1-x(OH)4(1-x)在空气中的热分解是一步完成的,随着锆含量的增加分解温度逐渐提高.应用微分法和积分法相结合对该分解过程的分解机理进行了推测,得出了一系列分解反应的表观活化能E和指前因子A.发现其热分解反应遵循Zhuralev-Lesokin-Tempelman三维扩散机理,其动力学方程为:f(α)=3/2(1-α)4/3[(1-α)-1/3-1]-1;g(α)=[(1-α)-1/3-1]2,其表观活化能大小与样品中的锆含量有关.     

聚亚苯基苯并二(口恶)唑的热分解行为

用热失重方法分析了聚亚苯基苯并二唑(PBO)纤维在不同气氛中的热分解行为,采用O zaw a法计算了PBO纤维在氮气和空气两种气氛中的热分解活化能。结果表明升温速率对PBO纤维的热分解温度有较大影响;氧气作为热分解反应的引发剂,大大降低了分解反应的活化能;由IR光谱对不同温度裂解产物结构的分析,推测了热氧化降解对PBO纤维分子结构的影响;在不同失重率时几乎相同的热分解活化能,表明无论热分解的气氛如何,PBO纤维的热分解均是一个无规引发的单阶段过程;结合PBO纤维在两种气氛中的热分解机理,解释了分解气氛对残碳率的影响。     

AM1—法研究邻—氨基苯甲醇和邻—氨基苯甲胺的热分解反应

本文用AM1方法研究了邻-氨基苯甲醇和邻-氨基苯甲胺热分解生成6-亚甲基-2.4-环己二烯-1-亚胺的反应.结果表明.邻-氨基苯甲醇和邻-氨基苯甲胺的热分解活化能分别为206.890 kJ/mol和214.572kJ-mol.     

水蒸汽对碳酸锰热分解反应的影响

用热重及差热分析法研究了在空气流和氢气流中及有无水蒸汽存在的四种情况下碳酸锰热分解的历程,分别求出了不同情况反应的动力学方程和表观活化能。说明了水蒸汽的作用主要在于催化碳酸锰分解为氧化亚锰的过程。     

Thermal behavior of zirconia-dop ed mullite gel fibers

The zirconia-doped mullite gel fibers were prepared via a sol-gel method.The thermal behaviors of the gel fibers during pyrolysis were investigated by means of thermal gravitydifferential scanning calo...     

Mineralization of flue gas CO2 with coproduction of valuable magnesium carbonate by means of magnesium chloride

CO2 mineralization and utilization is a new area for reducing the CO2 emissions. By reacting with natural mineral or industrial waste, CO2 can be transformed into valuable solid carbonate （such as calcium carbonate or magnesium carbonate） with recovery of some products simultaneously. In this paper, a novel method was proposed to mineralize CO2 by means of magnesium chloride with small energy consumption. In this method, magnesium chloride was firstly transformed into magnesium hydroxide by electrolysis. The formed magnesium hydroxide showed high reactivity to mineralize CO2. In our study, even at low concentration, CO2 can be effectively mineralized by this method, which makes it possible to directly mineralize flue gas CO2, avoiding the expensive process of CO2 capture and purification. Moreover, valuable products such as hydromagnesite and nesquehonite can be recovered by this method. Because of the wide distribution of magnesium chloride in nature, largescale CO2 mineralization is potential by means of magnesium chloride.     

Correlation between the glass-forming ability and activation energy of crystallization for Zr75−x Ni25Al x metallic glasses

The thermal stability and the kinetics of glass transition and crystallization for Zr_75?x Ni₂₅Al _x (x = 8–15) metallic glasses were investigated using differential scanning calorimetry (DSC) under continuous heating conditions. The apparent activation energy of glass transition rises monotonously with the Al content increasing; the activation energy of crystallization increases with Al changing from 8at% to 15at%, and then decreases with Al further up to 24at%, which exhibits a good correlation to the thermal stability and the glass-forming ability (GFA). The Zr₆₀Ni₂₅Al₁₅ metallic glass with the largest supercooled liquid region and GFA possesses the highest activation energy of crystallization. The relation between the thermal stability, GFA and activation energy of crystallization was discussed in terms of the primary precipitated phases.     

甲酸钠热分解行为的实验研究

用差热—热重方法对甲酸钠的热分解过程进行了实验研究,采用滴定分析技术分析了甲酸钠在不同条件下热分解产物的组成。研究发现：在甲酸钠脱氢制草酸钠的工艺中,加热速率和反应温度是影响草酸钠收率的重要因素。纯甲酸钠在253℃熔融,在330℃左右缓慢分解为碳酸钠、氢气、一氧化碳和少量草酸钠;高于400℃发生激烈的放热反应,甲酸钠脱氢转化为草酸钠;高于440℃,草酸钠分解生成碳酸钠。因此,为了高收率的获得目的产物草酸钠,需要快速升温,生成草酸钠的最佳温度为400～420℃,过度加热将导致草酸钠深度分解。     

Kinetic calculations for the thermal decomposition of calcium propionate under non-isothermal conditions

Calcium propionate (CP) is shown to be useful for simultaneous SO2/NO reduction in coal-fired power plants and its thermal decomposition characteristics are measured by thermogravimetric analysis in a feasibility study into more complete reduction of these hazardous gases. Calcium carbonate (CC), which has been used primarily for in-furnace desulfuration, was used for comparison. The thermal decomposition of this organic calcium-based sorbent began at low temperature, i.e. the carboxylic radical was evaporated from 565 K to 759 K for CP and the corresponding mass loss percentage was 47.79%. The residual was subsequently decomposed to release carbon dioxide between 843 K and 1012 K. The latter phase of the process occurred more readily than with CC because of the loose structure of CP resulting from evaporation of the carboxylic radical in the low temperature zone, which could be seen directly by scanning electron microscope. The maximum mass loss rates of this phase occurred at temperatures of 972 K and 1012 K for CP and CC, respectively. The Ozawa-Flynn-Wall method was used to calculate the activation energy during the thermal decomposition process at heating rates of 5, 7.5, 10 and 15 K/min. The result further confirmed the multistage characteristic of CP thermal decomposition, which could be seen in differential thermogravimetry curves. The reaction orders of CP in the conversion range 20%-80%, calculated using the Avrami theory were from 0.061 to 0.608, smaller than those of CC, which were 1.647 to 2.084.     

头孢硫脒热分解动力学研究

采用TG-DTG(thermal gravity -differential thermal gravity)法研究了头孢硫脒的热分解过程动力学。头孢硫脒热分解为一步完成，开始失重时的温度为430~450 K。运用Flynn-Wall-Ozawa法、Kissinger-Akahira-Sunose法和Starink法计算了头孢硫脒热分解过程中的活化能值，发现活化能均随着热分解转化率的升高而降低。通过Málek 法得到头孢硫脒晶体的热分解动力学三因子分别为E_α=109 kJ/mol、ln A=30.60 s^-1、最概然动力学模型为SB(0.241 7, 0.658 9)。预测头孢硫脒在273.15 K以下时的理论贮存期为3年。     

Features of major greenhouse gases in loess, Shanxi Province, China

According to the investigations of five loess sections in Shanxi Province, China, it was found that the concentrations of the major greenhouse gases CO₂, CH₄ and N₂O in loess-paleosol sequences are generally high, even sometimes may be several times or scores of times higher than their atmospheric concentrations respectively. Although the CO₂ concentration in the same loess section shows poor regularity among different layers, it increases slowly from north to south in space. The CH₄ concentration in the layers under Malan Loess is much higher than that in the atmosphere, although it is not high in Malan Loess. Most of the δ¹³C values of CO₂ in loess are -11.14‰—15.48‰ (relative to PDB standard). Analysis of carbon isotopic compositions of CO₂ indicates that the main source of CO₂ in loess section is decomposition of ‘stable’ organic matters by microbes. The δ¹³C_g of CO₂ is a little heavier than organic source for exchanging carbon isotope with carbonate in loess. The abundant carbonate in loess not only makes the loess a huge carbon reservior but also adjusts     

阿斯匹林的热稳定性及其热解动力学

目的研究了阿斯匹林的热稳定性及热解动力学.方法采用TG热重仪测定药物的热解曲线,用多条升温速率法Freeman-Carrollde 法和 Ozawa 法处理热重数据并比较热解活化能和热解温度.结果计算出阿斯匹林的热解动力学参数活化能、指前因子、反应级数;热解动力学方程为dα/dt=1.15×108e-96.04/RT (1-α)1.91.结论阿斯匹林片剂的热稳定性大于原药.由于阿斯匹林对温度敏感,应低温储存.阿斯匹林在室温下分解10 %约需2.08 a.