本文選題：動(dòng)力學(xué)補(bǔ)償效應(yīng) + 絕熱模式�。� 參考：《物理化學(xué)學(xué)報(bào)》2016年02期

【摘要】：熱分析量熱儀主要包括動(dòng)態(tài)、等溫、恒溫及絕熱四種操作模式。很多學(xué)者基于動(dòng)態(tài)及等溫模式的測試結(jié)果,采用Arrhenius速率常數(shù)進(jìn)行動(dòng)力學(xué)計(jì)算,進(jìn)而發(fā)現(xiàn)了所謂的"動(dòng)力學(xué)補(bǔ)償效應(yīng)"。為了解絕熱模式下是否也存在動(dòng)力學(xué)補(bǔ)償效應(yīng),分別采用絕熱加速量熱法(ARC)及動(dòng)態(tài)差示掃描量熱法(DSC)研究了過氧化二異丙苯(DCP)、40%(質(zhì)量分?jǐn)?shù),下同)DCP溶液、葡萄糖、45%葡萄糖溶液的熱分解特性,在此基礎(chǔ)上基于Arrhenius公式計(jì)算了對(duì)應(yīng)的表觀活化能E和指前因子A,并對(duì)計(jì)算結(jié)果進(jìn)行了分析。結(jié)果表明:絕熱模式下,不同質(zhì)量的同種樣品及其溶液的最佳動(dòng)力學(xué)參數(shù),或者同一組數(shù)據(jù)采用不同的反應(yīng)級(jí)數(shù)獲得的lnA和E之間均存在明顯的線性關(guān)系。此外,盡管由動(dòng)態(tài)DSC數(shù)據(jù)計(jì)算獲得的E和lnA普遍小于絕熱模式的結(jié)果,但兩種模式下獲得的lnA和E之間仍然存在動(dòng)力學(xué)補(bǔ)償效應(yīng)。由此可以推斷,具有相同或類似反應(yīng)機(jī)理的反應(yīng),雖然實(shí)驗(yàn)?zāi)Ｊ讲煌?但其E和lnA之間存在明顯的動(dòng)力學(xué)補(bǔ)償效應(yīng)。
[Abstract]:Thermal analysis calorimeter mainly includes four operation modes: dynamic, isothermal, isothermal and adiabatic. Based on the test results of dynamic and isothermal models, many scholars use the Arrhenius rate constant to calculate the kinetics, and then find the so-called "dynamic compensation effect". In order to find out whether there is dynamic compensation effect in adiabatic mode, the dynamic differential scanning calorimetry (DSCC) and adiabatic accelerated calorimetry (ARC) were used to study the dicumyl peroxide (DCPP) solution. On the basis of the thermal decomposition characteristics of 45% glucose solution, the corresponding apparent activation energy E and preexponential factor A were calculated based on the Arrhenius formula, and the calculated results were analyzed. The results show that under adiabatic mode, the optimal kinetic parameters of the same sample and its solution of different mass, or the linear relationship between lnA and E obtained by different reaction order of the same group of data are obvious. In addition, although the results of E and lnA calculated by dynamic DSC data are generally smaller than those obtained by adiabatic mode, there is still a dynamic compensation effect between the lnA and E obtained by the two modes. It can be inferred that the reaction with the same or similar reaction mechanism has obvious kinetic compensation effect between E and lnA, although the experimental model is different.
【作者單位】： 南京理工大學(xué)化工學(xué)院安全工程系;常州出入境檢驗(yàn)檢疫局;
【基金】：國家自然科學(xué)基金(51204099) 江蘇出入境檢驗(yàn)檢疫局科技計(jì)劃(2014KJ59)資助項(xiàng)目~~
【分類號(hào)】：O643.1

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