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Xenon difluoride
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Xenon difluoride
Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2, and one of the most stable xenon compounds. Like most covalent inorganic fluorides, it is moisture-sensitive. It gradually decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.
It has a nauseating odour and low vapor pressure.
Xenon difluoride is a linear molecule with an Xe–F bond length of 197.73±0.15 pm in the vapor stage, and 200 pm in the solid phase. The packing arrangement in solid XeF
2 shows that the fluorine atoms of neighbouring molecules avoid the equatorial region of each XeF
2 molecule. This agrees with the prediction of VSEPR theory, which predicts that there are 3 pairs of non-bonding electrons around the equatorial region of the xenon atom.
At high pressures, novel, polymeric forms of xenon difluoride can be obtained. Under a pressure of ~50 GPa, XeF
2 transforms into a semiconductor consisting of XeF
4 units linked in a two-dimensional structure, like graphite. At even higher pressures, above 70 GPa, it becomes metallic, forming a three-dimensional structure containing XeF
8 units. A 2011 theoretical study cast doubt on these experimental results, suggesting that xenon difluoride remains stable up to 200 GPa, at which point it dissociates into an ionic solid.
The Xe–F bonds are weak. XeF2 has a total bond energy of 267.8 kJ/mol (64.0 kcal/mol), with first and second bond energies of 184.1 kJ/mol (44.0 kcal/mol) and 83.68 kJ/mol (20.00 kcal/mol), respectively. However, XeF2 is much more robust than KrF2, which has a total bond energy of only 92.05 kJ/mol (22.00 kcal/mol).
Synthesis proceeds by the simple reaction:
The reaction needs heat, irradiation, or an electrical discharge. The product is a solid. It is purified by fractional distillation or selective condensation using a vacuum line.
The first published report of XeF2 was in October 1962 by Chernick, et al. However, though published later, XeF2 was probably first created by Rudolf Hoppe at the University of Münster, Germany, in early 1962, by reacting fluorine and xenon gas mixtures in an electrical discharge. Shortly after these reports, Weeks, Chernick, and Matheson of Argonne National Laboratory reported the synthesis of XeF2 using an all-nickel system with transparent alumina windows, in which equal parts xenon and fluorine gases react at low pressure upon irradiation by an ultraviolet source to give XeF2. Williamson reported that the reaction works equally well at atmospheric pressure in a dry Pyrex glass bulb using sunlight as a source. It was noted that the synthesis worked even on cloudy days.
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Xenon difluoride
Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2, and one of the most stable xenon compounds. Like most covalent inorganic fluorides, it is moisture-sensitive. It gradually decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.
It has a nauseating odour and low vapor pressure.
Xenon difluoride is a linear molecule with an Xe–F bond length of 197.73±0.15 pm in the vapor stage, and 200 pm in the solid phase. The packing arrangement in solid XeF
2 shows that the fluorine atoms of neighbouring molecules avoid the equatorial region of each XeF
2 molecule. This agrees with the prediction of VSEPR theory, which predicts that there are 3 pairs of non-bonding electrons around the equatorial region of the xenon atom.
At high pressures, novel, polymeric forms of xenon difluoride can be obtained. Under a pressure of ~50 GPa, XeF
2 transforms into a semiconductor consisting of XeF
4 units linked in a two-dimensional structure, like graphite. At even higher pressures, above 70 GPa, it becomes metallic, forming a three-dimensional structure containing XeF
8 units. A 2011 theoretical study cast doubt on these experimental results, suggesting that xenon difluoride remains stable up to 200 GPa, at which point it dissociates into an ionic solid.
The Xe–F bonds are weak. XeF2 has a total bond energy of 267.8 kJ/mol (64.0 kcal/mol), with first and second bond energies of 184.1 kJ/mol (44.0 kcal/mol) and 83.68 kJ/mol (20.00 kcal/mol), respectively. However, XeF2 is much more robust than KrF2, which has a total bond energy of only 92.05 kJ/mol (22.00 kcal/mol).
Synthesis proceeds by the simple reaction:
The reaction needs heat, irradiation, or an electrical discharge. The product is a solid. It is purified by fractional distillation or selective condensation using a vacuum line.
The first published report of XeF2 was in October 1962 by Chernick, et al. However, though published later, XeF2 was probably first created by Rudolf Hoppe at the University of Münster, Germany, in early 1962, by reacting fluorine and xenon gas mixtures in an electrical discharge. Shortly after these reports, Weeks, Chernick, and Matheson of Argonne National Laboratory reported the synthesis of XeF2 using an all-nickel system with transparent alumina windows, in which equal parts xenon and fluorine gases react at low pressure upon irradiation by an ultraviolet source to give XeF2. Williamson reported that the reaction works equally well at atmospheric pressure in a dry Pyrex glass bulb using sunlight as a source. It was noted that the synthesis worked even on cloudy days.
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