“…The less precise value obtained by conventional EIMS,14a IE(Cl 2 O) = 11.1 6 ± 0.1 eV, appears to be too high. The value reported by Alekseev et al,14b 10.52 ± 0.06 eV, was presumably perturbed by hot band effects since they generated Cl 2 O via pyrolysis of Cl 2 O 7 . 3 (a, top) Photoionization efficiency spectrum of Cl 2 O ( m / z = 86) between λ = 98.0 and 117.0 nm at a nominal resolution of 0.19 nm and 0.2 nm steps. (b, bottom) Photoionization threshold region of Cl 2 O ( m / z = 86) between λ = 112.0 and 116.0 nm at a nominal resolution of 0.17 nm and with 0.1 nm steps.…”
Section: Resultsmentioning
confidence: 77%
“…This PIMS value agrees well with the only previous precise measurement of 10.94 ± 0.01 eV, which was obtained by PES 14a IE(Cl 2 O) = 11.1 6 ± 0.1 eV, appears to be too high. The value reported by Alekseev et al,14b 10.52 ± 0.06 eV, was presumably perturbed by hot band effects since they generated Cl 2 O via pyrolysis of Cl 2 O 7 . 3 (a, top) Photoionization efficiency spectrum of Cl 2 O ( m / z = 86) between λ = 98.0 and 117.0 nm at a nominal resolution of 0.19 nm and 0.2 nm steps.…”
Section: Resultsmentioning
confidence: 97%
“…To date, three measurements of the adiabatic ionization energy of the ClO radical have been reported. Fisher 14a obtained a value of IE(ClO) = 11.1 eV while Alekseev et al14b report IE(ClO) = 11.08 eV, both obtained via EIMS. Bulgin et al …”
Section: Introductionmentioning
confidence: 99%
“…There have been three previous determinations of the adiabatic ionization energy (IE) of Cl 2 O , and several determinations of the enthalpy of formation of Cl 2 O. − A value for IE(Cl 2 O) = 10.94 eV was obtained via photoelectron spectroscopy 13 (PES), while less precise electron impact mass spectrometry (EIMS) measurements yield 11.16 14a and 10.52 eV 14b. Early measurements, mostly from the 1930s, yield Δ f H ° 298 (Cl 2 O) values of 89.5, 103.3, 87.9, , and 79.2 17,19 kJ mol -1 based on the heat of explosion 15,16 and heat of solution/formation measurements .…”
Section: Introductionmentioning
confidence: 99%
“…A more modern determination 14a is based on an EIMS measurement of the appearance energy (AE) of ClO + from the dissociative ionization of Cl 2 O. From AE 298 (ClO + , Cl 2 O) = 12.5 eV,14a a value of Δ f H ° 298 (Cl 2 O) = 99 kJ mol -1 may be derived. The most recent measurement 20 is based on the enthalpy of the reaction ClNO + Cl 2 O ↔ ClNO 2 + Cl 2 and yields Δ f H ° 298 (Cl 2 O) = 81.4 kJ mol -1 .…”
The photoionization efficiency (PIE) spectrum of Cl 2 O was measured over the wavelength range λ ) 98-117 nm by using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. A value of 10.90 9 ( 0.01 6 eV was obtained for the adiabatic ionization energy (IE) of Cl 2 O from analysis of the photoionization thresholds. The ClO radical was produced Via the reaction F + Cl 2 O f FCl + ClO and the PIE spectrum of ClO was measured over the wavelength range λ ) 105-117 nm. Analysis of the photoionization threshold yields a value of IE of ClO(X 2 Π 3/2 ) ) 10.88 5 ( 0.01 6 eV. The appearance energy (AE) of ClO + (from the dissociative ionization of Cl 2 O) was determined from the PIE spectrum of ClO + over the wavelength range λ ) 98-104 nm. Combining the AE 298 value, 12.29 6 ( 0.03 2 eV, with known thermodynamic quantities yields a value for ∆ f H°2 98 (Cl 2 O) ) 77.2 ( 3.4 kJ mol -1 . From the value for ∆ f H°2 98 (Cl 2 O) and the equilibrium constant for the reaction Cl 2 O + H 2 O T 2HOCl, a value for ∆ f H°2 98 -(HOCl) ) -76.8 ( 3.5 kJ mol -1 is obtained. These results for IE(Cl 2 O), IE(ClO), AE 298 (ClO + , Cl 2 O), ∆ f H°2 98 -(Cl 2 O), and ∆ f H°2 98 (HOCl) are compared with previous estimates or measurements.
“…The less precise value obtained by conventional EIMS,14a IE(Cl 2 O) = 11.1 6 ± 0.1 eV, appears to be too high. The value reported by Alekseev et al,14b 10.52 ± 0.06 eV, was presumably perturbed by hot band effects since they generated Cl 2 O via pyrolysis of Cl 2 O 7 . 3 (a, top) Photoionization efficiency spectrum of Cl 2 O ( m / z = 86) between λ = 98.0 and 117.0 nm at a nominal resolution of 0.19 nm and 0.2 nm steps. (b, bottom) Photoionization threshold region of Cl 2 O ( m / z = 86) between λ = 112.0 and 116.0 nm at a nominal resolution of 0.17 nm and with 0.1 nm steps.…”
Section: Resultsmentioning
confidence: 77%
“…This PIMS value agrees well with the only previous precise measurement of 10.94 ± 0.01 eV, which was obtained by PES 14a IE(Cl 2 O) = 11.1 6 ± 0.1 eV, appears to be too high. The value reported by Alekseev et al,14b 10.52 ± 0.06 eV, was presumably perturbed by hot band effects since they generated Cl 2 O via pyrolysis of Cl 2 O 7 . 3 (a, top) Photoionization efficiency spectrum of Cl 2 O ( m / z = 86) between λ = 98.0 and 117.0 nm at a nominal resolution of 0.19 nm and 0.2 nm steps.…”
Section: Resultsmentioning
confidence: 97%
“…To date, three measurements of the adiabatic ionization energy of the ClO radical have been reported. Fisher 14a obtained a value of IE(ClO) = 11.1 eV while Alekseev et al14b report IE(ClO) = 11.08 eV, both obtained via EIMS. Bulgin et al …”
Section: Introductionmentioning
confidence: 99%
“…There have been three previous determinations of the adiabatic ionization energy (IE) of Cl 2 O , and several determinations of the enthalpy of formation of Cl 2 O. − A value for IE(Cl 2 O) = 10.94 eV was obtained via photoelectron spectroscopy 13 (PES), while less precise electron impact mass spectrometry (EIMS) measurements yield 11.16 14a and 10.52 eV 14b. Early measurements, mostly from the 1930s, yield Δ f H ° 298 (Cl 2 O) values of 89.5, 103.3, 87.9, , and 79.2 17,19 kJ mol -1 based on the heat of explosion 15,16 and heat of solution/formation measurements .…”
Section: Introductionmentioning
confidence: 99%
“…A more modern determination 14a is based on an EIMS measurement of the appearance energy (AE) of ClO + from the dissociative ionization of Cl 2 O. From AE 298 (ClO + , Cl 2 O) = 12.5 eV,14a a value of Δ f H ° 298 (Cl 2 O) = 99 kJ mol -1 may be derived. The most recent measurement 20 is based on the enthalpy of the reaction ClNO + Cl 2 O ↔ ClNO 2 + Cl 2 and yields Δ f H ° 298 (Cl 2 O) = 81.4 kJ mol -1 .…”
The photoionization efficiency (PIE) spectrum of Cl 2 O was measured over the wavelength range λ ) 98-117 nm by using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. A value of 10.90 9 ( 0.01 6 eV was obtained for the adiabatic ionization energy (IE) of Cl 2 O from analysis of the photoionization thresholds. The ClO radical was produced Via the reaction F + Cl 2 O f FCl + ClO and the PIE spectrum of ClO was measured over the wavelength range λ ) 105-117 nm. Analysis of the photoionization threshold yields a value of IE of ClO(X 2 Π 3/2 ) ) 10.88 5 ( 0.01 6 eV. The appearance energy (AE) of ClO + (from the dissociative ionization of Cl 2 O) was determined from the PIE spectrum of ClO + over the wavelength range λ ) 98-104 nm. Combining the AE 298 value, 12.29 6 ( 0.03 2 eV, with known thermodynamic quantities yields a value for ∆ f H°2 98 (Cl 2 O) ) 77.2 ( 3.4 kJ mol -1 . From the value for ∆ f H°2 98 (Cl 2 O) and the equilibrium constant for the reaction Cl 2 O + H 2 O T 2HOCl, a value for ∆ f H°2 98 -(HOCl) ) -76.8 ( 3.5 kJ mol -1 is obtained. These results for IE(Cl 2 O), IE(ClO), AE 298 (ClO + , Cl 2 O), ∆ f H°2 98 -(Cl 2 O), and ∆ f H°2 98 (HOCl) are compared with previous estimates or measurements.
Das letzte unbekannte einkernige Chloroxid ist gefunden. ClO4 (im Bild rechts) läßt sich als gelbes Produkt der Vakuum‐Thermolyse von Cl2O6 oder Cl2O7 in einer Neon‐Matrix isolieren. Aus den IR‐Spektren des Radikals konnte geschlossen werden, daß es C3v‐Symmetrie aufweist und drei kurze (142 pm) und eine lange (153 pm) Cl‐O‐Bindung hat.
Magnesium perchlorate hexahydrate (Mg(ClO 4) 2 •6H 2 O) samples were exposed to energetic electrons to investigate the products of the decomposition of perchlorates in the Martian soil and to infer their role in the degradation of organics on Mars. The samples were monitored online and in situ via infrared spectroscopy as well as electron impact (EI-QMS) and reflectron time-of-flight mass spectrometry coupled with single photon ionization (PI-ReTOF-MS). Our study reveals that besides chlorates (-ClO 3) and molecular oxygen (O 2), the chlorine dioxide radical (ClO 2) was observed online and in situ for the first time as a radiolysis product of solid perchlorates. Chlorine dioxide, which is used on Earth as a strong oxidizing agent in water disinfection and bleaching, represents a proficient oxidizer-potentially more powerful than molecular oxygen-to explain the lack of abundant organics in the Martian soil.
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