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Evaluation and Prediction of Latent Heat of Vaporization at Various Temperatures for Pure Components and Binary Mixtures

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Evaluation and Prediction of Latent Heat of Vaporization at Various Temperatures for Pure Components and Binary Mixtures Evaluation and Prediction of Latent Heat of Vaporization at Various Temperatures for Pure Components and Binary Mixtures A Thesis Submitted to the College of Engineering of Nahrain University in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemical Engineering by Mohammed Jabbar Ajrash B.Sc. in Chemical Engineering 2006 Jamad Al- awla 1430 May 2009 1 Abstract The prediction of latent heat of vaporization of pure compounds has at least sixteen methods to predict the latent heat of vaporization for pure compounds and three methods to predict the latent heat of vaporization for binary mixtures .All these methods has been evaluated in this work. There are at least nine methods available in literature for prediction of latent heat of vaporization at any temperature using either vapor pressure data or the law of corresponding states .These methods predict the latent heat of vaporization at various temperatures directly. The accuracy of these methods are different. Some of these methods have accurate results when dealing with non polar compounds but not so accurate when dealing with polar compounds . Halim and Stiel is the best method among these nine methods which is directly deal with polarity of compounds by introducing what is known polarity factor of polar compounds and it gives 1.552 absolute average deviation percent compared with experimental data for 18 pure non polar compounds with 446 data points .On the other hand it gives 2.8476 AAD% compared with experimental data for 6 polar compounds with 180 data points . The prediction of the latent heat of vaporization from normal boiling point have at least seven methods . The Riedel method at normal boiling has less absolute average deviation percent compared with experimental data .The AAD% is 1.271 for 32 pure non polar compounds while it gives 4.439 AAD% compared with experimental data for 29 polar compounds. To predict the value of latent heat of vaporization at any temperature from normal boiling point using a relation describe the change of latent heat of vaporization with temperature to give the estimated value at needed temperature ,the more accurate relation available is 2 Watson equation . It is found that the First Veter method has the less deviation from experimental data among these seven methods that predict the latent heat of vaporization at various temperature from normal boiling point .The AAD% is 1.344 for 18 pure non polar compounds and 446 data points. On the other hand the AAD% is 3.3426 compared with experimental data for 6 polar compounds and 180 data points. Generally ,all methods that estimate the latent heat of vaporization at normal boiling point don't have accurate results when dealing with polar compounds. This work modified Kistiakowsky method to give accurate results with both non polar and polar compounds . These two modifications are simple and easy to use .In both modifications the compounds are classified into three groups :non polar ,alcohols and polar compounds and the values of constants are given for each group. The first modification is the same as Kistiakowsky equation except the values of constant A are different vap n.b = (A+ R ln Tb ) Tb The AAD% obtained from this work for 34 compounds for alcohols and other polar compounds are 4.4036 and 3.38 respectively, in comparison with that of Kistiakowsky method which are 24.97 and 6.312 respectively. The second modification of Kistiakowsky method is as follows vap n.b = R.Tb (a + b ln Pc +c ln Tb ) In this equation the critical pressure is included and the values of the constants a,b,c for each groupe 3 The overall AAD% obtained from this work for 57 compounds for non polar compounds , alcohols and other polar compounds are 1.462 , 2.278 and 2.933 respectively , in comparison with that of Kistiakowsky method the AAD% are 2.2095 , 24.97 and 6.312 respectively. It is to be noted that this work have the least deviation from experimental data from all methods that predict the latent heat of vaporization at normal boiling point for pure polar compounds. This work also are applied at various temperatures by using Watson equation, the second modification has less deviation from experimental data than the first modification . The second modification has good results for both non polar and polar compounds whereas the AAD% of 24 non polar compounds is 1.462. On the other hand the AAD% of 33 polar compounds is 2.575 and it is the least deviation form experimental data for polar compounds results from the methods that are available in literature to predict the latent heat of vaporization at normal boiling point . For mixtures, there are three methods available in literature to predict the latent heat of vaporization of binary mixtures. The Teja method is the more accurate of them, it gives 2.261 AAD% for 4 mixtures and 46 data point . List of Contents 4 Contents pages Abstract i List of contents iv List of tables viii List of Figures xi Nomenclature xii Chapter One : Introduction Introduction 1 Chapter Two : Theory and literature review 2.1 Non polar and polar compounds 3 2.2 Critical properties 4 2.3 The law of Corresponding states of three parameter 5 2.4 The law of Corresponding states of four parameter 7 2.5 Vapor pressure 8 2.6 Latent heat of vaporization 9 2.7 The main principle methods that have been used to estimate the latent heat of 10 vaporization 2.8 Latent heat of vaporization from vapor pressure 10 2.8.1Lee –kesler 11 2.8.2 Antion 11 2.8.3 . wagnar equation 1 12 2.8.4. wagnar equation 2 . 12 2.8.5 Ambrose Walton equation 13 2.8.6 Riedel equation 14 2.9 Latent heat of vaporization at normal boiling point 15 2.9.1 calpeyron method 15 2.9.2 Riedel method 16 2.9.3 Kistiakowsky method 16 2.9.4 Fishtine method 16 2.9.5 Chen method 17 2.9.6 First veter method 17 2.9.7 Second veter method 2.10 Estimation of the latent heat of vaporization from law of corresponding states 19 2.10.1 Pitzer equation 19 2.10.2 HALM and STIEL 21 2.10.3 Carruth and Kobayashi 23 2.11 variation latent heat of vaporization with temperature 23 5 2.11.2 Sastri correlation 23 2.11.2 Kistiakowsky correlation 24 2.11.3 Watson correlation 24 2.12. latent heat of vaporization for mixture 2.12.1 Pitzer equation with suitable mixing rule 25 2.12.2. Carruth and Kobayashi with suitable mixing rule 25 2.12.3 Teja 25 2.13 Mixing rules : 26 2.14 Experimental Data 27 Chapter Three :Evaluation of various methods for calculating latent heat of vaporization 3.1. Evaluation of various methods of predicting the latent heat of vaporization of pure compounds at various temperatures. 3.1.1 Halm and Stiel method 31 3.1.2 pitzer method 32 3.1.3 Carruth and Kobayashi 32 3.1.4. first and second Wagnar methods 33 3.1.5. Lee keslar method 33 3.1.6. Antion method 34 3.1.7 . Ambrose Walton method. 34 3.1.8. Riedel method 34 3.2. Evaluation of various methods of predicting the latent heat of vaporization at normal boiling point of pure compounds . 3.2.1 Riedel method 38 3.2.2 Chen method 38 3.2.3 First Veter method 39 3.2.4 Fishten method 39 3.2.5 Calypyron method 39 3.2.6 Second Veter method 40 3.2.7 Kistiakowsky method 40 3.3 Evaluation of various methods of predicting the latent heat of vaporization at any temperatures from those at normal boiling point of pure compounds 3.3.1 Riedel method at normal boiling point 44 3.3.2 Fishten method . 44 3.3.3 Chen method 45 3.3.4 First Veter method 45 3.3.5 Second Veter method 46 3.3.6 Calpeyron method 47 6 3.3.7 Kistiakowsky method 47 3.4 Evaluation of various methods of calculating the latent heat of vaporization of mixture at any temperature 4.4.1 Teja method 51 4.4.3 Carruth Kobayashi method 51 4.4.2. pitzer method 51 Chapter Four: Modification of kistiakowsky method 4.1. First modification of Kistiakowsky method to predict the latent heat of vaporization at normal boiling point 53 4.2 .Second modification of Kistiakowsky method to predict the latent heat of 56 vaporization at normal boiling point 4.3. Application of first and second modified Kistiakowsky method at normal 60 boiling point to various temperatures Chapter Five :Discussion 5.1 Discussion 64 5.2 Sample of calculation 76 5.3 Conclusions 79 5.4 Recommendations 82 References Appendix A A-1 Appendix B B-1 Appendix C C-1 7 List of Tables Table Title Page Table 2-1 a The constants of second Veter method 18 Table 2.1.b The molecular weight contributions for second Veter method 18 Table 2.2 Pitzer Heat of Vaporization Parameters 20 Table 2.3 The values of the polarity factor 21 Table 2-4 The pure compounds latent heat of vaporization data 28 Table 2-5 The pure compounds latent heat of vaporization at normal boiling 29 point data Table 2-6 The mixtures latent heat of vaporization data 30 Table 3-1 Over all AAD% for predicting of latent heat of vaporization at 34 various temperatures for pure non polar and polar compounds Table 3-2 Over all AAD% for predicting of latent heat of vaporization at various temperatures for pure non polar compounds 36 Table 3-3 Over all AAD% for predicting of latent heat of vaporization at various temperatures for pure polar compounds 37 Table 3-4 Over all AD% for predicting of latent heat of vaporization at normal boiling point for pure non polar and polar compounds 4161 Table 3-5 Over all AD% for predicting of latent heat of vaporization at normal boiling point for pure non polar compounds 62 Table 3-6 Over all AD% for predicting of latent heat of vaporization at 4263 normal boiling point for pure polar compounds 68 Table 3-7 Over all AAD% for predicting of latent heat of vaporization
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