Abstract
The heavy element volatility instrument (HEVI), an on-line isothermal gas chromatography system, has been used to separate the volatile bromide compounds of the group 4 elements Zr and Hf and the transactinide Rf according to their volatilities, and to provide data on the gas phase chemical properties of very short-lived isotopes in amounts as low as a few atoms. For these studies {sup 261}Rf was produced via the {sup 248}Cm({sup 18}O, 5n) reaction. {sup 165-167}Hf was produced via the reaction {sup nat}Eu({sup 19}F, xn), and {sup 85}Zr was produced via the {sup nat}Cu({sup 28}Si, 3p3n) reaction. The half-life for {sup 261}Rf was measured to be 75 {+-} 7 seconds. A Monte Carlo code was used to deduce the enthalpy of adsorption ({delta}H{sub a}) from the observed volatility and parameters of the chromatography system. The resulting adsorption enthalpies for the Zr, Hf, and Rf tetrabromides are: -108 {+-} 5 kJ . mol{sup -1}, -113 {+-} 5 kJ . mol{sup -1} and -87 {+-} 7 kJ . mol{sup -1}, respectively. Volatilities of the group 4 bromides support the conclusion from previous results for the group 4 chlorides that Rf deviates from the trend expected by simple extrapolation of the properties of its
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Sylwester, E R;
Adams, J L;
Lane, M R;
Shaughnessy, D A;
Wilk, P A;
Hoffman, D C;
[1]
California Univ., Berkeley, CA (United States). Dept. of Chemistry];
Gregorich, K E;
Lee, D M;
Laue, C A;
McGrath, C A;
Strellis, D A;
[1]
Kadkhodayan, B;
[2]
Tuerler, A;
[3]
Kacher, C D
[4]
- Lawrence Berkeley National Lab., CA (United States)
- Lam Res. Corp., Fremont, CA (USA)
- Paul Scherrer Inst. (PSI), Villigen (Switzerland)
- W.M. O'Neil and Co., Inc., Los Angeles, CA (United States)
Citation Formats
Sylwester, E R, Adams, J L, Lane, M R, Shaughnessy, D A, Wilk, P A, Hoffman, D C, California Univ., Berkeley, CA (United States). Dept. of Chemistry], Gregorich, K E, Lee, D M, Laue, C A, McGrath, C A, Strellis, D A, Kadkhodayan, B, Tuerler, A, and Kacher, C D.
On-line gas chromatographic studies of Rf, Zr, and Hf bromides.
Germany: N. p.,
2000.
Web.
doi:10.1524/ract.2000.88.12.837.
Sylwester, E R, Adams, J L, Lane, M R, Shaughnessy, D A, Wilk, P A, Hoffman, D C, California Univ., Berkeley, CA (United States). Dept. of Chemistry], Gregorich, K E, Lee, D M, Laue, C A, McGrath, C A, Strellis, D A, Kadkhodayan, B, Tuerler, A, & Kacher, C D.
On-line gas chromatographic studies of Rf, Zr, and Hf bromides.
Germany.
https://doi.org/10.1524/ract.2000.88.12.837
Sylwester, E R, Adams, J L, Lane, M R, Shaughnessy, D A, Wilk, P A, Hoffman, D C, California Univ., Berkeley, CA (United States). Dept. of Chemistry], Gregorich, K E, Lee, D M, Laue, C A, McGrath, C A, Strellis, D A, Kadkhodayan, B, Tuerler, A, and Kacher, C D.
2000.
"On-line gas chromatographic studies of Rf, Zr, and Hf bromides."
Germany.
https://doi.org/10.1524/ract.2000.88.12.837.
@misc{etde_20148183,
title = {On-line gas chromatographic studies of Rf, Zr, and Hf bromides}
author = {Sylwester, E R, Adams, J L, Lane, M R, Shaughnessy, D A, Wilk, P A, Hoffman, D C, California Univ., Berkeley, CA (United States). Dept. of Chemistry], Gregorich, K E, Lee, D M, Laue, C A, McGrath, C A, Strellis, D A, Kadkhodayan, B, Tuerler, A, and Kacher, C D}
abstractNote = {The heavy element volatility instrument (HEVI), an on-line isothermal gas chromatography system, has been used to separate the volatile bromide compounds of the group 4 elements Zr and Hf and the transactinide Rf according to their volatilities, and to provide data on the gas phase chemical properties of very short-lived isotopes in amounts as low as a few atoms. For these studies {sup 261}Rf was produced via the {sup 248}Cm({sup 18}O, 5n) reaction. {sup 165-167}Hf was produced via the reaction {sup nat}Eu({sup 19}F, xn), and {sup 85}Zr was produced via the {sup nat}Cu({sup 28}Si, 3p3n) reaction. The half-life for {sup 261}Rf was measured to be 75 {+-} 7 seconds. A Monte Carlo code was used to deduce the enthalpy of adsorption ({delta}H{sub a}) from the observed volatility and parameters of the chromatography system. The resulting adsorption enthalpies for the Zr, Hf, and Rf tetrabromides are: -108 {+-} 5 kJ . mol{sup -1}, -113 {+-} 5 kJ . mol{sup -1} and -87 {+-} 7 kJ . mol{sup -1}, respectively. Volatilities of the group 4 bromides support the conclusion from previous results for the group 4 chlorides that Rf deviates from the trend expected by simple extrapolation of the properties of its lighter homologs in the periodic table. The group 4 bromides are also observed to be less volatile than their respective chlorides, as predicted by relativistic calculations. (orig.)}
doi = {10.1524/ract.2000.88.12.837}
journal = []
issue = {12}
volume = {88}
journal type = {AC}
place = {Germany}
year = {2000}
month = {Jul}
}
title = {On-line gas chromatographic studies of Rf, Zr, and Hf bromides}
author = {Sylwester, E R, Adams, J L, Lane, M R, Shaughnessy, D A, Wilk, P A, Hoffman, D C, California Univ., Berkeley, CA (United States). Dept. of Chemistry], Gregorich, K E, Lee, D M, Laue, C A, McGrath, C A, Strellis, D A, Kadkhodayan, B, Tuerler, A, and Kacher, C D}
abstractNote = {The heavy element volatility instrument (HEVI), an on-line isothermal gas chromatography system, has been used to separate the volatile bromide compounds of the group 4 elements Zr and Hf and the transactinide Rf according to their volatilities, and to provide data on the gas phase chemical properties of very short-lived isotopes in amounts as low as a few atoms. For these studies {sup 261}Rf was produced via the {sup 248}Cm({sup 18}O, 5n) reaction. {sup 165-167}Hf was produced via the reaction {sup nat}Eu({sup 19}F, xn), and {sup 85}Zr was produced via the {sup nat}Cu({sup 28}Si, 3p3n) reaction. The half-life for {sup 261}Rf was measured to be 75 {+-} 7 seconds. A Monte Carlo code was used to deduce the enthalpy of adsorption ({delta}H{sub a}) from the observed volatility and parameters of the chromatography system. The resulting adsorption enthalpies for the Zr, Hf, and Rf tetrabromides are: -108 {+-} 5 kJ . mol{sup -1}, -113 {+-} 5 kJ . mol{sup -1} and -87 {+-} 7 kJ . mol{sup -1}, respectively. Volatilities of the group 4 bromides support the conclusion from previous results for the group 4 chlorides that Rf deviates from the trend expected by simple extrapolation of the properties of its lighter homologs in the periodic table. The group 4 bromides are also observed to be less volatile than their respective chlorides, as predicted by relativistic calculations. (orig.)}
doi = {10.1524/ract.2000.88.12.837}
journal = []
issue = {12}
volume = {88}
journal type = {AC}
place = {Germany}
year = {2000}
month = {Jul}
}