Post by Anders Hoveland on Mar 9, 2013 2:05:45 GMT -8
Some russian investigators reported a successful preparation of anhydrous aluminum perchlorate:
"...we obtained for the first time anhydrous Al(ClO4)3 from AlCl3 and Cl2O6 in liquid ClO2."
They had to use cryogenically liquified ClO2 in their procedure?! Seems like a very bad idea...
"It was found that Al(ClO4)3 does not dissolve in noncoordinating organic solvents - saturated hydrocarbons and their derivitives - but reacts with them. ...
Treatment of Al(ClO4)3 with THF leads to formation of a poorly soluble solvate of the composition Al(ClO4)3 • 3C4H8O; its IR spectrum does not display bands of the ClO4- ion, but it has bands of the ClO4 coordinated group: 920, 1040,and 1200 cm-1. Aluminum perchlorate dissolves in considerable amounts in CH3NO2; removal of the solvent leaves the poorly crystallizing complex Al(ClO4) • 3CH3NO2.
The inorganic solvents investigated were liquid SO2, N2O4, NOCl, and anhydrous HClO4. ... In NOCl and N2O4 we observe complete solvolysis of Al(ClO4)3 to nitrosyl perchlorate and aluminum chlorido or nitrato complex."
"Solvation, Solvolysis, and Complexing of Anhydrous Aluminum Perchlorate in Anhydrous Media", Z.K. Nikirina, V. Ya. Rosolovskii, Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1223–1227, June, 1980.
Apparently anhydrous aluminum perchlorate is a fairly reactive oxidizer:
"Addition of solid Al(ClO4)3 to CH3OH at [around] 20 °C leads to a flash."
In another paper by the same researchers, the enthalpy of formation of anhydrous aluminum perchlorate was experimentally determined to be -136.5 ±0.5 kcal/mole.
Anhydrous titanium perchlorate also exists:
Nonsolvated titanium perchlorate was produced by the action of TiCl4 on anhydrous perchloric acid (containing up to 2% Cl2O7). Titanium perchlorate possesses an appreciable intrinsic vapor pressure and can be repeatedly sublimed at 70 °C under vacuum. The properties of sublimed Ti(ClO4)4 differ from the properties of the starting material.
It was established by the method of differential thermal analysis that Ti(ClO4)4 melts with partial decomposition at 85–95 °C, and above 110°C under vacuum it decomposes to TiO2, O2, and oxides of chlorine. The heating of Ti(ClO4)4 at atmospheric pressure ends in explosive decomposition at ∼130 °C.
Ti(ClO4)4 dissolves vigorously in water, it dissolves with decomposition in nitromethane and acetonitrile - the solution turns yellow. It is insoluble in CCl4 but above 25 °C it reacts, forming a yellow solution.
Titanium perchlorate is a colorless hygroscopic crystalline substance. ... The density of Ti(ClO4)4 ... is equal to 2.35 g/cm3.
"Volatile titanium perchlorate", V. P. Babaeva, V. Ya. Rosolovskii,
Bulletin of the Academy of Sciences of the USSR, Division of chemical science, November 1974, Volume 23, Issue 11, pp 2330-2334
"...we obtained for the first time anhydrous Al(ClO4)3 from AlCl3 and Cl2O6 in liquid ClO2."
They had to use cryogenically liquified ClO2 in their procedure?! Seems like a very bad idea...
"It was found that Al(ClO4)3 does not dissolve in noncoordinating organic solvents - saturated hydrocarbons and their derivitives - but reacts with them. ...
Treatment of Al(ClO4)3 with THF leads to formation of a poorly soluble solvate of the composition Al(ClO4)3 • 3C4H8O; its IR spectrum does not display bands of the ClO4- ion, but it has bands of the ClO4 coordinated group: 920, 1040,and 1200 cm-1. Aluminum perchlorate dissolves in considerable amounts in CH3NO2; removal of the solvent leaves the poorly crystallizing complex Al(ClO4) • 3CH3NO2.
The inorganic solvents investigated were liquid SO2, N2O4, NOCl, and anhydrous HClO4. ... In NOCl and N2O4 we observe complete solvolysis of Al(ClO4)3 to nitrosyl perchlorate and aluminum chlorido or nitrato complex."
"Solvation, Solvolysis, and Complexing of Anhydrous Aluminum Perchlorate in Anhydrous Media", Z.K. Nikirina, V. Ya. Rosolovskii, Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1223–1227, June, 1980.
Apparently anhydrous aluminum perchlorate is a fairly reactive oxidizer:
"Addition of solid Al(ClO4)3 to CH3OH at [around] 20 °C leads to a flash."
In another paper by the same researchers, the enthalpy of formation of anhydrous aluminum perchlorate was experimentally determined to be -136.5 ±0.5 kcal/mole.
Anhydrous titanium perchlorate also exists:
Nonsolvated titanium perchlorate was produced by the action of TiCl4 on anhydrous perchloric acid (containing up to 2% Cl2O7). Titanium perchlorate possesses an appreciable intrinsic vapor pressure and can be repeatedly sublimed at 70 °C under vacuum. The properties of sublimed Ti(ClO4)4 differ from the properties of the starting material.
It was established by the method of differential thermal analysis that Ti(ClO4)4 melts with partial decomposition at 85–95 °C, and above 110°C under vacuum it decomposes to TiO2, O2, and oxides of chlorine. The heating of Ti(ClO4)4 at atmospheric pressure ends in explosive decomposition at ∼130 °C.
Ti(ClO4)4 dissolves vigorously in water, it dissolves with decomposition in nitromethane and acetonitrile - the solution turns yellow. It is insoluble in CCl4 but above 25 °C it reacts, forming a yellow solution.
Titanium perchlorate is a colorless hygroscopic crystalline substance. ... The density of Ti(ClO4)4 ... is equal to 2.35 g/cm3.
"Volatile titanium perchlorate", V. P. Babaeva, V. Ya. Rosolovskii,
Bulletin of the Academy of Sciences of the USSR, Division of chemical science, November 1974, Volume 23, Issue 11, pp 2330-2334