【摘要】：在已有的基團(tuán)貢獻(xiàn)法公式的基礎(chǔ)上,提出了一種新的基團(tuán)貢獻(xiàn)法公式,并通過(guò)擬合250種化合物(包括185種穩(wěn)定化合物臨界性質(zhì)的實(shí)驗(yàn)值和65種自由基臨界性質(zhì)的計(jì)算值)的臨界性質(zhì)得到了40種基團(tuán)的貢獻(xiàn)值,并用于預(yù)測(cè)未知化合物的臨界性質(zhì).選取了訓(xùn)練集以外的、有臨界性質(zhì)實(shí)驗(yàn)值的30種化合物作為獨(dú)立測(cè)試集,用于驗(yàn)證所建模型對(duì)臨界性質(zhì)的預(yù)測(cè)能力,T_C和P_C平均絕對(duì)偏差分別為8.52%和16.83%.結(jié)果表明,預(yù)測(cè)結(jié)果和實(shí)驗(yàn)值相吻合,該模型可以用于大分子化合物及自由基的臨界性質(zhì)預(yù)測(cè).根據(jù)臨界性質(zhì)與Lennard-Jones(L-J)系數(shù)的經(jīng)驗(yàn)關(guān)系式,預(yù)測(cè)了碳?xì)浠衔锶紵虚g體的L-J系數(shù),得到獨(dú)立測(cè)試集46種碳?xì)浠衔锏腖-J系數(shù),與文獻(xiàn)值接近,T_C和P_C的平均絕對(duì)偏差分別為9.88%和9.96%.比較了訓(xùn)練集中烷烴自由基·C_6H_(13)、烯烴自由基·C_5H_9和炔烴自由基·C_5H_7同分異構(gòu)體的L-J系數(shù),同時(shí),將己烷自由基·C_6H_(13)與相似的鄰近烷烴C_6H_(14)的L-J系數(shù)進(jìn)行比較,發(fā)現(xiàn)同分異構(gòu)體之間或相似化合物之間L-J系數(shù)有較大偏差.此外,對(duì)缺少L-J系數(shù)的114種常見(jiàn)碳?xì)浠衔镒杂苫M(jìn)行了預(yù)測(cè).這對(duì)于碳?xì)浠衔锏娜紵M及基元反應(yīng)中壓強(qiáng)相關(guān)的速率常數(shù)計(jì)算有重要意義.
[Abstract]:On the basis of the existing formula of group contribution method, a new formula of group contribution method is proposed, and the contribution values of 40 groups are obtained by fitting the critical properties of 250 compounds (including the experimental values of the critical properties of 185 stable compounds and the calculated values of 65 kinds of free radical critical properties), and they are used to predict the critical properties of unknown compounds. Thirty compounds with experimental values of critical properties outside the training set were selected as independent test sets to verify the prediction ability of the model for critical properties. The average absolute deviation of T 鈮，

本文編號(hào)：2500463