Quantitative study of the acidity of HCl in a molten chloroaluminate system (AlCl3/1-ethyl-3-methyl-1H-imidazolium chloride) as a function of HCl pressure and melt composition (51.0-66.4 mol % AlCl3)
The acidity of HCl in Lewis acid mixtures of AlCl{sub 3} and 1-ethyl-3-methyl-1H-imidazolium chloride (EMIC) has been determined as a function of HCl pressure (P{sub HCl}) and melt composition at ambient temperatures. The equilibrium constant (K{prime}{sub b}) for the protonation of arene bases (B)...
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Published in | Journal of the American Chemical Society Vol. 111; no. 14; pp. 5075 - 5077 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
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Washington, DC
American Chemical Society
05.07.1989
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Abstract | The acidity of HCl in Lewis acid mixtures of AlCl{sub 3} and 1-ethyl-3-methyl-1H-imidazolium chloride (EMIC) has been determined as a function of HCl pressure (P{sub HCl}) and melt composition at ambient temperatures. The equilibrium constant (K{prime}{sub b}) for the protonation of arene bases (B) according to the reaction HCl + B {r reversible} BH{sup +} + Cl{sup {minus}} was determined from the relation log K{prime}{sub B} = H{prime} + log ((BH{sup +})/(B)) with the protonation ratio measured spectrophotometrically and the acidity function, H{prime} = log ((Cl{sup {minus}})/P{sub HCl}), evaluated by using the thermodynamic model of Dymek et al. to calculate (Cl{sup {minus}}). Values of log K{prime}{sub B} were determined for chrysene, fluorene, 2-methylnaphthalene, and mesitylene over a range of HCl pressures and melt compositions, while estimates for benzene, toluene and naphthalene were obtained at a single pressure and composition (1 atm, 66.4 mol % AlCl{sub 3}). The correlation between log K{prime}{sub B} for these arenes in HCl/AlCl{sub 3}-EMIC and log K{sub B} for the same arenes in HF/BF{sub 3} suggests that H{prime} {minus} H{sub 0} {approx equal} 0.4, where H{sub 0} is the Hammett acidity function. According to this criterion H{sub 0} for 0.01 atm HCl in 51 mol % AlCl{sub 3} has a value of {minus}12.6 (a superacid comparable to 100% H{sub 2}SO{sub 4}). At 1 atm HCl, a melt saturated with AlCl{sub 3} at ambient temperatures ({approximately} 67 mol % AlCl{sub 3}) is a much stronger superacid with a value of H{sub 0} on the order of {minus}18. |
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AbstractList | The acidity of HCl in Lewis acid mixtures of AlCl{sub 3} and 1-ethyl-3-methyl-1H-imidazolium chloride (EMIC) has been determined as a function of HCl pressure (P{sub HCl}) and melt composition at ambient temperatures. The equilibrium constant (K{prime}{sub b}) for the protonation of arene bases (B) according to the reaction HCl + B {r reversible} BH{sup +} + Cl{sup {minus}} was determined from the relation log K{prime}{sub B} = H{prime} + log ((BH{sup +})/(B)) with the protonation ratio measured spectrophotometrically and the acidity function, H{prime} = log ((Cl{sup {minus}})/P{sub HCl}), evaluated by using the thermodynamic model of Dymek et al. to calculate (Cl{sup {minus}}). Values of log K{prime}{sub B} were determined for chrysene, fluorene, 2-methylnaphthalene, and mesitylene over a range of HCl pressures and melt compositions, while estimates for benzene, toluene and naphthalene were obtained at a single pressure and composition (1 atm, 66.4 mol % AlCl{sub 3}). The correlation between log K{prime}{sub B} for these arenes in HCl/AlCl{sub 3}-EMIC and log K{sub B} for the same arenes in HF/BF{sub 3} suggests that H{prime} {minus} H{sub 0} {approx equal} 0.4, where H{sub 0} is the Hammett acidity function. According to this criterion H{sub 0} for 0.01 atm HCl in 51 mol % AlCl{sub 3} has a value of {minus}12.6 (a superacid comparable to 100% H{sub 2}SO{sub 4}). At 1 atm HCl, a melt saturated with AlCl{sub 3} at ambient temperatures ({approximately} 67 mol % AlCl{sub 3}) is a much stronger superacid with a value of H{sub 0} on the order of {minus}18. |
Author | ZINGG, S. P SMITH, G. P DWORKIN, A. S PAGNI, R. M |
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Keywords | Lewis acid Chemical equilibrium Hydrogen Chlorides Metal Compounds Trivalent metal Compounds Aluminium III Chlorides Medium effect Content Protonation Pressure |
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Snippet | The acidity of HCl in Lewis acid mixtures of AlCl{sub 3} and 1-ethyl-3-methyl-1H-imidazolium chloride (EMIC) has been determined as a function of HCl pressure... |
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SubjectTerms | 400000 - Chemistry 400201 - Chemical & Physicochemical Properties ALKYLATED AROMATICS AROMATICS BENZENE CHEMICAL ANALYSIS CHEMICAL REACTION KINETICS Chemistry CONDENSED AROMATICS DATA DATA ANALYSIS Exact sciences and technology EXPERIMENTAL DATA HYDROCARBONS HYDROCHLORIC ACID HYDROGEN COMPOUNDS INFORMATION INORGANIC ACIDS Inorganic chemistry and origins of life INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY KINETICS Kinetics and mechanism of reactions LEWIS ACIDS MEASURING INSTRUMENTS MEASURING METHODS NAPHTHALENE NUMERICAL DATA ORGANIC COMPOUNDS QUANTITATIVE CHEMICAL ANALYSIS REACTION KINETICS TOLUENE |
Title | Quantitative study of the acidity of HCl in a molten chloroaluminate system (AlCl3/1-ethyl-3-methyl-1H-imidazolium chloride) as a function of HCl pressure and melt composition (51.0-66.4 mol % AlCl3) |
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