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EQUILIBRIA of ALUMINUM CHLORIDE with HYDROGEN CHLORIDE in AROMATIC HYDROCARBONS Dissertation Presented in Partial Fulfillment Of

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EQUILIBRIA OF ALUMINUM CHLORIDE WITH HYDROGEN CHLORIDE IN AROMATIC HYDROCARBONS Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By LEWIS DELMAR SWAN, B. A., M. Sc. The Ohio State University 1952 Approved by vxser/’ TABLE OF CONTENTS Page I. Purpose............................... 1 II. Historical............................. 2 Part A. The HX-AIX,- Aromatic Solvent . 2 Part B. The Catalytic Species in the Friedel-Crafts Reaction.... 3 III. Preliminary Observations............... 16 A. Benzophenone-Aluminum chloride Complex.......................... 16 B. Effect of repeated sublimation of aluminum chloride .............. 17 C. Catalytic couple with mercury salts. 17- D. Effect of moisture.......... 1 7 E. Preliminary studies with hydrogen chloride........................ IS IV. The Specific Problem............ .. 3 0 V. Experimental........................... 31 A. Apparatus........................ 31 B. Purification and Preparation of Reagents........................ 36 1. Aluminum chloride......... 36 2. Hydrogen chloride......... 38 3. Aromatic Hydrocarbons.... 42 a. b e n z e n e ......... 4 2 b. t o l u e n e ...............43 c. mesitylene............. 45 4. Benzophenone............... 4 5 5. Miscellaneous: 02> HgO, N2 . 46 C. Operational Procedures........... 47 D. Analytical Procedures............. 50 E. Summary of manipulatory difficulties encountered..................... 52 VI. D a t a .................................... 53 A. Benzene as Solvent...............53 ii 809682 iii TABLE OF CONTENTS (continued) Page a. No complex without promoter. 53 b. Complex with promoter, ..... 56 c. Equilibrium constant....... .. 56 B. Toluene as Solvent.................... 56 a. Toluene versus time. ..........56 b. Complex with promoter........ 62 c. Equilibrium constant........ 62 C. Mesitylene as Solvent................. 67 a. No complex without promoter .. 67 b. Complex...................... 67 c. Equilibrium constant........ 67 d. Effect of oxygen . ........... 72 VI. Discussion of Results...................... 74 a. No Hydrogen chloride-aluminum chloride addition compound . 74 b. High aluminum chloride-benzo- phenone ratios ................ 74 c. Inorganic catalytic couples. 75 d. Repeated sublimation of aluminum chloride.....................75 e. Importance of promoters...... 76 f . Relative basicity of solvent . 77 g. The role of water and oxygen . 7S h. Ternary complexes............ 79 i. Evidence for hydrates......... 79 j. Evidence for dimer ........... SO k. "Red oil” complications...... SO 1. Distribution of aluminum chloride Si 91. Effect of oxygen on aluminum chloride-mesitylene system . S2 VII. Future Problems............................ S3 VIII. Suranary............. S5 Autobiography. , , LIST OF TABLES No. I. Solubility of Aluminum Chloride in Benzene-Benzophenone Solutious at 20°C. (Molality xlo3) II. Effect of Repeated Sublimation on Solubility of Aluminum Chloride in Benzene at 20°C. III. Effect of Water on the Aluminum Chloride Benzophenone Ratio in Benzene at 20°C. IV. Effect of Aqueous Hydrogen Chloride on Aluminum Chloride Solubility in Benzene at 20°C. V. Effect of Hydrogen Chloride Atmosphere on Solubility of only Partially Pure Aluminum Chloride in Benzene at 20°C. VI. Promoting Effect of Water on Coordina­ tion of Aluminum Chloride with Hydrogen Chloride in Benzene at 20°C. VII. Co-ordination of Hydrogen Chloride with Aluminum Chloride in the Presence of Water in Benzene at 25°C. VIII. Effect of Water on the Solubility of Aluminum Chloride in Benzene with Subsequent Effects of Hydrogen Chloride and Water at 25°C. IX. Effect of Time on the Solubility of Aluminum Chloride in Toluene at 25°C. with Effect of Subsequent Water Addition. X. Co-ordination of Aluminum Chloride with Hydrogen Chloride in Toluene at 25°C. XI. The Solubility of Aluminum Chloride in Mesitylene Versus Time at 25°C. with Subsequent Air Admission, V LIST OF TABLES (continued) Page XII. Solubility of Aluminum Chloride in Mesitylene at 25°C. as Affected by Hydrogen Chloride Addition and Subsequent Removal by Pumping. 70 XIII. Effect of Oxygen on Aluminum Chloride- Mesitylene System at 25°C. 73 LIST OF FIGURES Page 1. Effect of Benzophenone on Solubility of Aluminum Chloride in Benzene at 20°C. 20 2. Effect of Water on Aluminum Chloride- Benzophenone Ratio in Benzene at 20 C., 23 3. Effect of Aque;ous Hydrogen Chloride on the Solubility of Aluminum Chloride in Benzene at 20'G. o c 4. Preliminary Run.Effect of Atmosphere of Hydrogen Chloride on the Solubility of - Aluminum Chloride in Benzene at 20°C. 27 5. Equilibration Flask used in Aluminum Chloride-Benzophenone System. 2S 6 . Equilibration Vessel. 1/2 Scale 32 7. Sampling Flask. Full Scale 34 S. Manifold for Introduction of Hydrogen Chloride to System. 35 9. Aluminum Chloride Sublimation Manifold. 37 10. Block Diagram for Filling Hydrogen Chloride Addition Bulbs. 39 11. Hydrogen Chloride Addition Bath. 41 (Shown in Filling Position) 1-/2 Scale 12. Block Diagram for Purification and Addition of Solvent to System. 44 13. Benzene, Aluminum Chloride, Hydrogen Chloride, with Subsequent Water Addition.25 C .55 14. Benzene, Aluminum Chloride, Hydrogen Chloride Showing Effect of Water and Oxygen.2$°C. 56 15. Effect of Water on Solubility of Aluminum Chloride in Benzene.Subsequent Addition of Hydrogen Chloride and Water at 25°C. 60 16. Solubility of Aluminum Chloride in Benzene at 25°C. as Influented'.by the Presence of Water. 61 vi vii LIST OF FIGURES (continued) No. Page 17. Effect of Time on the Solubility of Aluminum Chloride in Toluene at 25°C. with Subsequent Water Addition. 64 IS. Solubility of Aluminum Chloride in Toluene at 25°C. as Influenced by Hydrogen Chloride. 66 19. Aluminum Chloride in Mesitylene Versus Time at 25°C. with Subsequent Air Admission. 69 20. Aluminum Chloride in Mesitylene at 25°C. with Added Hydrogen Chloride, Followed by Pumping. 71 ACKNOWLEDGMENT Appreciation to Dr. Alfred B. Garrett for his suggestion of the problem and his guidance during the work is gratefully extended. Acknowledgment is also due the Office of Naval Research, United States Navy, and the du Pont Company for fellowships which enabled the completion of this work. The author also wishes to express his gratitude to his wife for her patience and understanding during the period of this study. viii EQUILIBRIA OF ALUMINUM CHLORIDE WITH HYDROGEN CHLORIDE IN AROMATIC HYDROCARBONS I. Purpose The purpose of this investigation was to study the equilibria of aluminum chloride with hydrogen chloride in aromatic hydrocarbons as solvents. This is part of a pro­ gram of elucidating the nature of Friedel-Crafts catalysis. Previously reported work has indicated that the true catalyst in those reactions ordinarily promoted by aluminum chloride might actually be tetrachloroaluminic acid formed in the equilibrium: AICI3 + HC1 HA1C14 . Although this substance has never been isolated and does not form in the absence of a solvent1, its salts of 1. H. C. Brown and H. W. Pearsall, J. Am.Chem.Soc., 73, 4631 (1951). 2 3 the form R+ AlCl^" are known (in the presence and absence of solvent). 2. E. Wertyporoch & T. Firla, Z.physik.chem., 162, 393-414 (1932). 3. Thomas, C. A., Anhydrous Aluminum Chloride in Organic Chemistry, Am. Chem. Soc. Monograph #37, New York, Reinhold Publishing Co., 1941, P 43-56. ------------- j----------------------------------- It was proposed: 1. To measure the solubility of aluminum chloride in aro­ matic solvents, specifically benzene, toluene, and mesit­ ylene, at 25° C.; 2. To measure the solubility of aluminum chloride in hydrogen chloride solutions of the same aromatic hydro­ carbons at several concentrations and at the same tempera­ ture; 3. To calculate equilibrium constants for the reaction indicated above if the reaction did not go to completion; and 4. To study the effect of moisture and oxygen on the equilibria involved. II. Historical Part A. Data on the hydrogen chloride-aluminum chloride- aromatic solvent systems. Brown and Pearsall^ studied the 4. H. G. Brown and H. ¥. Pearsall, J.Am.Chem. Soc., 74, 191 (1952). ~ system hydrogen chloride-aluminum chloride-toluene at -45.5° C. and -B0° C. Applying Henry’s law to their vapor pressure data they found co-ordination of hydrogen chloride and aluminum chloride in toluene. 5 Ipatieff and Komerewsky treated hydrogen chloride- 3 5. V. N. Ipatieff and V. I. Komerewsky, J.Am.Chem.Soc,, 56, 1926 (1934). saturated-benzene with aluminum chloride in a sealed bomb at 125° C. for twenty four hours and obtained about 1% biphenyl and ethylbenzene. The authors infer from these results that the catalyst induces destructive hydrogenation of benzene with formation of biphenyl and ethylenic frag­ ments. These ethylenic fragments then alkylate benzene under the influence of aluminum chloride to form ethyl­ benzene. They termed the process "destructive alkylation". Anschutz and Immersdorf^3, and Norris and Rubenstein^3, 6 . D. Nightingale, Chem. Rev. 2£, a.343, b.360 (1939). found that toluene, the xylenes, and mesitylene would similarly disproportionate to a small extent into higher and lower homologs under the influence of aluminum chloride. Part B. The catalytic species of the Friedel-Crafts reaction. Although the primary purpose of this investigation was not to elucidate the mechanism of Friedel-Crafts catalysis the results were such that they have a distinct bearing on. the catalytic species involved in such systems. A general dis­ cussion of aluminum
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  • “All in the Family” Properties of Halogens SCIENTIFIC Periodic Trends and the Properties of the Elements

    “All in the Family” Properties of Halogens SCIENTIFIC Periodic Trends and the Properties of the Elements

    “All in the Family” Properties of Halogens SCIENTIFIC Periodic Trends and the Properties of the Elements Introduction In every family there are similarities and differences. The same is true in chemical families as well. Elements that share similar chemical properties are arranged in vertical columns, called groups or families, in the modern periodic table. For example, the Group 17 elements, consisting of fluorine, chlorine, bromine, iodine, and astatine, are called the halogens. What are the similarities and differences in the chemical properties of the halogens and their compounds? Concepts • Halogens • Periodic table • Groups or families • Periodic trends Activity Overview The purpose of this demonstration is to explore the similarities and differences in the chemical properties of the halogens. The reactions of chlorine, bromine, and iodine with sodium chloride, sodium bromide, and sodium iodide will be inves- tigated in order to determine the periodic trend for the reactivity of the halogens. Chlorine, bromine, and iodine will be identified by their unique colors in water and hexane. Materials Bromine water, Br2 in H2O, 10 mL† Sodium thiosulfate solution, 4%, 500 mL§ Chlorine water, Cl2 in H2O, 10 mL† Water, distilled or deionized Iodine solution, I2, 0.04 M, 10 mL Bottles (with caps), square glass, 30-mL, 6 Hexanes, C6H14, 60 mL Graduated cylinders, 10- and 25-mL Sodium bromide solution, NaBr, 0.1 M, 10 mL Marking pencil or pen Sodium chloride solution, NaCl, 0.1 M, 10 mL Periodic table Sodium iodide solution, NaI, 0.1 M, 10 mL †Prepare fresh within one day of use—see the Preparation of Solutions section.
  • United States Patent Office Patented Use 1, 1965 1

    United States Patent Office Patented Use 1, 1965 1

    3,187,057 United States Patent Office Patented use 1, 1965 1. 2 3,187,057 substituents attached to the benzene ring may be ethyl TRECHL{ROMETHYL POLYMETHYL SENZENES groupings. The alkyl substituent may be an n-propyl-, Hugo H. Peter, The Hague, Netherlands, and Meivern C. isobutyl-, or tertiary butyl substituent, but with these Hoff, Highland, Ind., assignors to Standard Oil Com larger alkyl substituents only one such substituent may be pany, Chicago, Ill., a corporation of adiana present in the polyalkylbenzene in order to be useable in No Drawing. Filed May 19, 1958, Ser. No. 735,961 the process of this invention. To illustrate, 1,3-dimethyl 10 Claims. (CI. 260-651) 5-tertiary butyl benzene may be used in the reaction, but 1,3,5-tri tertiary butylbenzene is not useable in the proc This invention relates to reactions between polyalkyl ess. It is important that polyalkylbenzenes which contain benzenes and carbon tetrachloride and particularly con O their alkyl substituents in the 1,3,5-, 1,2,4,5-, 1,2,3,5-, or cerns a method for forming trichloromethyl polyalkyl in the 1,2,3,4,5-positions in the benzene nucleus be used. benzenes. The benzylic chlorines on the intermediate trichloro Prior workers have attempted to prepare trichloro methyl aromatic are far more reactive than the compet methylbenzene by reacting benzene with carbon tetrachlo ing halogens on the carbon tetrachloride. The polyalkyl ride in the presence of aluminum chloride. The reaction 5 benzenes which are substituted in the above defined posi did not stop at the desired stage, but instead continued tions provide steric protection and shelter the reactive and produced dichlorodiarylmethane and chlorotriary trichloromethyl grouping in such fashion as to prevent methane.