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Secondary Reactions and Partial Rate Factors in the Sulfonation of Chlorobenzene and Toluene

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Secondary Reactions and Partial Rate Factors in the Sulfonation of Chlorobenzene and Toluene Brigham Young University BYU ScholarsArchive Theses and Dissertations 1967-08-01 Secondary reactions and partial rate factors in the sulfonation of chlorobenzene and toluene Ernest Arthur Brown Brigham Young University - Provo Follow this and additional works at: https://scholarsarchive.byu.edu/etd BYU ScholarsArchive Citation Brown, Ernest Arthur, "Secondary reactions and partial rate factors in the sulfonation of chlorobenzene and toluene" (1967). Theses and Dissertations. 8178. https://scholarsarchive.byu.edu/etd/8178 This Dissertation is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. SECONDARYREACTIONS AND PARTIAL RATE FACTORS IN THESULFONATION OF CHLOROBENZENEAND TOLUENE 'Y \ I v A Dissertation Submitted to the Department of Chemistry Brigham Young University In Partial F'ulfillment of th~ Requirements for the Doctor of Philosophy Degree by Ernest A. Brown August, 1967 l -~ This dissertation, by Ernest A. Brown, is accepted in its present form by the Department of Chemistry of Brigham Young University as sati.sfying the dissertation requirement for the degree of Doctor of Philosophy" ii \,. ACKNOWLEDGMENTS I wisn to extend my appreciation to the faculty and staff of Brigham Young Unive:r.sity for the assistance given during the course of this work~ and to the U.S. Department of Health, Education 9 and Welfare for the N. D. E. A. fellowship which helped support me while this work was being done. A special thanks is extended to Dr. K. L. Nelson for his encouragement and assistance and for providing an atmosphere conducive to indepem,dent. thought and individual achievement. My deepest gratitude is also expressed to my wife and sons who have supported me with their patience and understanding. iii TABLEOF CONrENTS Page ACI<NOWLEDGME~1TS•• . iii LIST OF TABLES. "' . Ct • • ,, • • .. • • vi LIST OF FIGURES ix . .• ✓ INTRODUCTION•.• 1 I. MECHANISMOF ELECTROPHILICAROMATIC SUBSTITUTION. 2 II. DIRECTIVEEFFECTS AND THE REACTIVITY-SELECTIVITY RELATIO?\"SH~P. • • • • • • • • • . • • •.• , • • 11 III. ELECTROPHILICSUBSTITUTION REACTIONS INVOLVIllG CRLOROBENZENE. • • . • . • • • 18 IV. MECHANISMOF AROMATICSULFONATION. • 25 V. PURPOSEAND PROCEDURE OF THE U~JESTIGATION. 34 VI. RESULTSAND DISCUSSION: •. O O O O •. • • o 36 Competitive. Sulfonation in the Benzene·· Chlorobenzene System Competitive Sulfonation in the Toluene- Benzene System Isomer Distribution for the Sulfonation of Chlorobenzene Isomer Distributions for the Competitive Sulfonaticm of Toluene and Benzene Partial Rate Factors for the Sulfonati.on o.f Toluene and Chlorobenze.ne VII. CONCLUSIONSA~'!O RECOMMENDATIONS. 85 VIII. EXPERIME:~'TALPROCEDURES. • • oooe•oooo 89 Preparation of Sodium£-,~- and E- Chlorobenzene:sulfon.stes Preparation 0£ Derivatives Prepa.ra.t.ion of :Radioacti.ve, Sulfor Di.oxide iv Page Preparation of Radioactive Benzene Purification of Benzene, Chlorobenzene, and Toluene Sulfonation Procedure Analysis of Reaction Products of Isomer Di.stri.bution Experiments Analysis of Products of Competitive Reactions IX. EXPERIMENTALDATA AND•CALCULATED RESULTS. 109 Isomer Distribution Data Competitive Sulfonation Data: Benzene- Chlorobenzene System Test of Thermodynamic vs, Kinetic Control Mole Fraction of BS as a Function of (Mole Fraction B1)_/ (S03) Product Composition as a Function of so3 Concentration Comparison of Actual BS and CS Values with Those Predicted for no Secondary Reactions -Sulfonation of Toluene-Benzene Mixtures Comparison of Predicted and Actual TS and BS Values in Constant Ti/Bi Experiments Relative Concentrations of Primary and Secondary Sulfonations Isomer Distribution in Competiti·11e Reactions APPENDIX. o O O O O e • • • • • 0 • • • • 0 140 I. COMPUTERPROGRAMS 140 A, Calculation of kB/kc B. Calculation of Mole Fraction Values C. Calculation of BS,CS, and R Assuming no Secondary Reactions D. Calculation of BS,CS, and R from Constant Bi/Ci. Experiments E" Calculation of BS,TS, and R from Constant Ti/Bi Experiments Fo Calculation of Relative Contributions of Primary and Secondary Reactions G. Isomer Distribution in Competitive Reactions II. RESEARCHPROPOSAL •• 151 LIST OF REFERENCES•••• , 157 V LIST OF TABLES Table Page 1. Electrophilic Aromatic Substitution Reactions on Chlorobenzene . 19 2. Typical Magnitudes for pf in Reactions on Toluene,, • • • . • . • • 23 -3. Relative Rates a,s a. Function of Initial Benzene- Chlorobenzene Ratio ..•.. 38 4. Test of Thermodynamic vs. Kinetic Control. 41 5. Relati,re Rates for Experiments with Varying so3 Concentrations 43 6. Product Composition as a Function of so3 Concentration at Constant Bi/Ci· .••• 44 7. Determination of kB/kc from Extrapolated Values of BS and CS....•.•...• 54 8. Comparison of Actt:1.al Values of BS and CS with Those Predicted for Sulfonation with no Secondary Reactions . 57 9. Comparison of Actual vs. Predicted BS,CS, and BS/CS Values for B1/Ci = 0.708 Data ...• 60 10. Competitive Sulfonations in the Toluene-..,__ Benzene System . • . • • • • • • • . • • • 64 11. Relat:l've Rates Calculated from Extrapolations in the Benzene=Toluene System. • • • • • • • 68 12. Comparison of Ac:t1.1alvs. Predicted Products from Ti/Bi~ 0.858 and T1/Bi ~ 0.279 Experiments • 69 13. Rel.ati•1e Con.t'.".'ibuti•ons of Primary and Secondary Reactioos on the Toluene-Benzene System. • , • . , 71 14. Isomer Dist:eibutic,n for the Sulfonation of ChlorobenzenE!. , , . • . • . 72 vi Table Page 15. Variation in Isomer Distribution with Percent Toluene·conversion in Cerfontain's Sulfonation of Neat Toluene with so3 at 2~5o Co ., o o • • • • • • • • • • • .. • • • 73 16. Isomer Distribution and Relative Rates for Cerfontain's Competitive Sulfonation of Benzene·~Toluen.e Mixtures at 25° C. 75 17. Ortho/Para Ratios for the Sulfonation of Chlo~obenzene and Benzene .••••••• . 77 18. Isomer Distribution as a Function of S03 Concentration in Toluene-Benzene Competitive Sulfonations. • . • • • . • • 80 19. Partial Rate Factors .• 81 20. Melting Points of S-Benzylisothiouronium Derivatives of the Isomeric Chlorobenzene- su:lfonates .. • . • . .. • . • . 92 ,. 21., Melting Points of _E-Toluidine Derivatives of the Isomeric Chlorobenzenesulfonates. • • 92 22. Experimental Conditions for Isomer Distribution Experiments . • • . • • • • • • . • • • • . 109 23. Conditions for Dilution of Isotopes • 109 2.4. Counting Data for Isomer Distribution Experiments • • • • • • • • • • . 110 25. Summary of Avexa.ge Values for Counting Data 0 ~ • • 113 26. Suumary of Isomer Distribution Results. 115 27. Experimental Conditions for Competitive Sulfonation of Benzene=Chlorobenzene Mixtures 116 28. Counting Data for Competitive Sulfonation l!:xperiments in Benzene-Chlorobenzene Mb:tures 118 29. Calculated Values for. Competitive Sulfonation Experiments i'r! Benzene-Chlo:robenzene Mixtures 120 30. Err.or Limits for Calculation of kB/kc . , . 121 vii Table Page 31. Data for Thermodynamic vs. Kinetic Control Test • • 0 • • . 122 32. Calculations of Mole Fraction Values for Fig. 7 . • o • • • • • • • • • o • • • 1l • • • 123 33. Data for Computer Program to Calculate BS and CS in the Absence of Secondary Reactions 127 34. Data for Comparison of BS and CS with Values Calculated on the Basis of no Secondary Reactions. OC100000••···•··· 128 35. Experimental Conditions for the Competitive Sulfonat.ion of Benzene-Toluene Mixtures. • • 129 36. Analyti.c:al Data for Experiments 21-P and 22-P. 130 37. Counting Data for Toluene-Benzene Competitive Sulfonation.s .. , . • . • . • • . • . • 131 38. Data Points from TS/BS vs. so Concentration Curves . • . • • . • • . 3. • . • • • . 132 39. Absorbance and Absorptivity Values for Standard UV Curves. • • • . • • • • • • • • • 138 40. Absorbance Values of Competitive Sulfon.ation Samples 4;11 " • • • • • • • e • • " • • • • o • 139 ' viii LIST OF FIGURES Figu:re Page L Nelson and Brown's Mechanism for Electrophilic Aromatic Substitution • • • . • . • • • • • • • . 6 2. Reaction Energy Profile for a Syrmnetrical Substitution Reaction in Which Formation of a ct' Complex is Rate Determining •.•. 7 3. Reaction Energy Profile for a Substitution Reaction in Which 71-Complex Formation is Rate Determining, ...••••.•..••. 9 4. The Selectivity Relationship for Toluene and Proposed E~tension to Other Monosubstituted Benzenes Q o .. ;) • • • • • • • o • • o • 15 s. Potential Energy Profiles for Substitutions Where (?""'-Complex Formation is Rate Determin-· ing (I) and ff-Complex Formation is Rate Determining (II). • • . • . • . 16 6. Relationship of log Pf to log pf/mf for a Series of Electrophilic Substitutions on ·chlorobenze:ne • . • . • . • • • o e O • 0 7. Apparent Relative Rates as a Function of Initial Benzene=Chlorobenzene Ratio •.• 39 8. Mole Fraction of BS as a Function of Mole Fraction Bi/(S03) .• • • • • • • • • • • 42 9. Ratio of Benzen.e-to Chlorobenzene-Sulfonates in Product at Constant Bf/Ci as a Function of Concentration. of S03. • • • • • • • • • . • . • 45 10. Moles of Product Formed as a Function of so3 Concentration ...•.••••• • • 0 • • 53 11. kT/kB as a :Pu.netion. of Bi/Ti for the Sulfonation of Benzene-Toluene Mixtures with _S03 in Liquid s02, T : -12.5° C. • • • • • • 62 ix F.igu:re Page 12. Apparent k.r/kB as a Function of T1/B1 for the Sulfonation of Benzene-Toluene Mixtures with so3 in Liquid so2 at T : -12.5° C. • • • • • • 63 13. Variation of TS/BS as a Function of so3
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