(252c) Position Group Contribution Method for the Prediction of Critical Properties of Organic Compounds Containing Nitrogen

Knowledge of physicochemical properties of organic compounds is essential for predicting their behavior [1-6]. Critical properties are the most widely used of physical properties in chemical engineering design and experimental. Although many hundreds amount of experimental data are available in literature, but most components are not sufficiently stable at or near the critical temperature, and as a result experimental measurements of their critical properties, Tc and Pc, are extremely difficult. In such conditions, mathematical models could be used to provide a reasonable estimation of the properties. Some of the significant group contribution methods for estimation of melting points were developed by Joback-Reid, [2] Constantinou-Gani. [5] and Marrero-Gani. [6-7] Joback -Reid developed a first-order group contribution method with 40 groups for organic compounds containing halogens, oxygen, nitrogen and sulfur. Constantinou-Gani introduced a two-level group contribution scheme consisting of 63 first-order groups and 40 second-order groups. Marrero-Gani modified this model further using the third-order groups that could account for more complex heterocyclic and large polyfunctional alicyclic compounds. Quantitative Structure-Property Relationships (QSPR) methods also could be used to estimating of properties. [8-10] This method is based on specific families of compounds, such as alkanes (Charton et al [11]), aldehydes, amines, ketones [12], benzenes[10] and Pyridinium Bromides[13] are some of these families for which QSPR models have been developed. Katritzky [14] reviewed the QSPR methods range in accuracy from very well to similar accuracy as group contributions.

However, most of group contribution methods have a serious problem that they cannot distinguish among structural isomers, and QSPR method take an extremely complex calculation in its processing. To overcome this problem, a position group contribution method has been proposed and applied for the prediction of critical properties such as critical temperature or critical pressure of pure organic compounds [15-16].

The position group contributions for the critical temperature and critical pressure

The first step consisted in testing correlations to rep¬resent the properties. Only one-parameter contribution was considered for each group. The critical pressure function is constructed by all groups' contribution as well as position correction. The position corrections were used to take into account longer distance interactions, which could distinguish most isomer include cis- and trans- or Z- and E- structure of organic compounds for their thermodynamics properties.

Here, the critical temperature and critical pressure can be expressed as:

Parameter or stands for or group contributions, for the number of each group that carbon element forms the centre of the group in the molecular formula, for the number of each group that non-carbon element forms the centre, for total number of groups, for position correlation factor, and , for parameters of the model. The set of contributions that allowed to minimize the residual estimation difference was then computed by regression..

The sources of experiment data were from: a series of critical compilation reviews by the critical properties group of the IUPAC Ⅰ.2 on thermodynamics, the works were published in J Chem Eng Data by Ambrose,17-19 Tsonopoulous,18,19,23,24 Daubert,21 Gude,20 Kudchadker,23 and Marsh K.N. et al..25,26 Critical data was also obtained from a compilation of organic property data by Ma 27.

Conclusion

In this work, based on position group contribution method, a new method recently proposed for the estimation of the critical temperature is extended to the prediction of critical pressure. Contributions for compounds containing carbon, hydrogen, oxygen, nitro¬gen, sulphur, chlorine and bromine were reported, and that position compensation factor has been developed which could distinguish between the thermodynamic properties of most isomers of organic compounds including cis- and trans- or Z- and E- structures. It is shown that it is possible to use a similar framework to predict the two properties of organic compounds. The predicted results for 232 different of organic compounds critical temperature and critical pressure showed that the position group contribution method performs significantly better than other methods used for comparison.

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