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BrCl crystallizes in the orthorhombic Cmc2_1 space group. The structure is one-dimensional and consists of two BrCl ribbons oriented in the (0, 0, 1) direction. Br is bonded in a linear geometry to two equivalent Cl atoms. There are one shorter (2.41 Å) and one longer (2.42 Å) Br–Cl bond lengths. Cl is bonded in a water-like geometry to two equivalent Br atoms.
BrCl is alpha carbon monoxide-like structured and crystallizes in the hexagonal P6_3mc space group. The structure is zero-dimensional and consists of two bromine chloride molecules. Br is bonded in a single-bond geometry to one Cl atom. The Br–Cl bond length is 2.17 Å. Cl is bonded in a single-bond geometry to one Br atom.
Rb2CuCl2Br2 is (La,Ba)CuO4-derived structured and crystallizes in the orthorhombic Cmce space group. The structure is three-dimensional. Rb1+ is bonded in a 9-coordinate geometry to five equivalent Br1- and four equivalent Cl1- atoms. There are a spread of Rb–Br bond distances ranging from 3.52–3.68 Å. All Rb–Cl bond lengths are 3.41 Å. Cu2+ is bonded to two equivalent Br1- and four equivalent Cl1- atoms to form corner-sharing CuBr2Cl4 octahedra. The corner-sharing octahedral tilt angles are 0°. Both Cu–Br bond lengths are 2.56 Å. There are two shorter (2.26 Å) and two longer (2.91 Å) Cu–Cl bond lengths. Br1- is bonded in a 6-coordinate geometry to five equivalent Rb1+ and one Cu2+ atom. Cl1- is bonded in a 6-coordinate geometry to four equivalent Rb1+ and two equivalent Cu2+ atoms.
Rb2CrCl2Br2 is (La,Ba)CuO4-derived structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Rb1+ is bonded in a distorted q6 geometry to five equivalent Br1- and four equivalent Cl1- atoms. There are four shorter (3.61 Å) and one longer (3.63 Å) Rb–Br bond lengths. All Rb–Cl bond lengths are 3.45 Å. Cr2+ is bonded to two equivalent Br1- and four equivalent Cl1- atoms to form corner-sharing CrBr2Cl4 octahedra. The corner-sharing octahedral tilt angles are 0°. Both Cr–Br bond lengths are 2.63 Å. All Cr–Cl bond lengths are 2.54 Å. Br1- is bonded to five equivalent Rb1+ and one Cr2+ atom to form distorted BrRb5Cr octahedra that share corners with five equivalent BrRb5Cr octahedra, corners with twelve equivalent ClRb4Cr2 octahedra, edges with eight equivalent BrRb5Cr octahedra, and faces with four equivalent ClRb4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 0–55°. Cl1- is bonded to four equivalent Rb1+ and two equivalent Cr2+ atoms to form distorted ClRb4Cr2 octahedra that share corners with two equivalent ClRb4Cr2 octahedra, corners with twelve equivalent BrRb5Cr octahedra, edges with two equivalent ClRb4Cr2 octahedra, faces with four equivalent BrRb5Cr octahedra, and faces with four equivalent ClRb4Cr2 octahedra. The corner-sharing octahedra tilt angles range from 0–55°.
We show that a nighttime profile of OClO in the Arctic vortex during the winter of 2000 is overestimated, by nearly a factor of 2, using an isentropic trajectory model constrained by observed profiles of ClOx (ClO + 2 X ClOOCl) and BrO. Calculated abundances of nighttime OClO are shown to be sensitive to the abundance of BrOx (BrO + BrCl), details of the air parcel history during the most recent sunrise/sunset transitions, and the BrCl yield from the reaction BrO + ClO. Many uncertainties are considered, and the discrepancy between measured and modeled nighttime OClO appears to be robust. This discrepancy suggests that production of OClO occurs more slowly than implied by standard photochemistry. If the yield of BrCl from the reaction of BrO + ClO is increased from 7% (JPL 2002 value) to 11% (near the upper limit of the uncertainty), good agreement is found between measured and modeled nighttime OClO. This study highlights the importance of accurate knowledge of BrO + ClO reaction kinetics as well as air parcel trajectories for proper interpretation of nighttime OClO. These factors have a considerably smaller impact on the interpretation of OClO observations obtained during twilight (90(deg) <=SZA <= 92(deg)), when photolytic processes are still active.
We report aircraft observations of extreme levels of HCl and the dihalogens Cl 2 , Br 2 , and BrCl in an industrial plume near the Great Salt Lake, Utah. Complete depletion of O 3 was observed concurrently with halogen enhancements as a direct result of photochemically produced halogen radicals. Observed fluxes for Cl 2 , HCl, and NO x agreed with facility-reported emissions inventories. Bromine emissions are not required to be reported in the inventory, but are estimated as 173 Mg year –1 Br 2 and 949 Mg year –1 BrCl, representing a major uncounted oxidant source. A zero-dimensional photochemical box model reproduced the observed O 3 depletions and demonstrated that bromine radical cycling was principally responsible for the rapid O 3 depletion. Inclusion of observed halogen emissions in both the box model and a 3D chemical model showed significant increases in oxidants and particulate matter (PM 2.5 ) in the populated regions of the Great Salt Lake Basin, where winter PM 2.5 is among the most severe air quality issues in the U.S. The model shows regional PM 2.5 increases of 10%–25% attributable to this single industrial halogen source, demonstrating the impact of underreported industrial bromine emissions on oxidation sources and air quality within a major urban area of the western U.S.
All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here we demonstrate CsPb(BrCl) 1.5 nanocrystals in metal-organic frameworks (MOF) thin films to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10~20 nm nanocrystals. This is revealed by X-ray scattering and transmission electron microscopy. Employing the CsPbX 3 - MOF thin films as emission layers, bright deep blue and sky-blue LEDs are demonstrated that emit at 452 nm and 476 nm respectively. The maximum external quantum efficiencies of these devices are 0.72% for deep blue LEDs and 5.6% for sky blue LEDs. More importantly, the device can maintain 50% of its original electroluminescence (T 50 ) for 2.23 hours when driving at 4.2V. Detailed optical spectroscopy and time-of-flight secondary ion mass spectroscopy suggest that the ion migration can be suppressed that maintains the emission brightness and spectra. Our study provides a new route for fabricating stable blue light emitting diodes with all-inorganic perovskite nanocrystals.
Previous observations of OClO over the Antarctic obtained in 1986 are used to constrain the stratospheric abundance of bromine. The observed diurnal variation is consistent with the production of OClO via the reaction of ClO with BrO if the branching ratio to the BrCl channel is between 3.5 and 14 percent. Otherwise, an additional source in twilight is indicated. The present results suggest a stratospheric bromine concentration of 16 + or - 4 pptv, a value which is consistent with independent measurements.
Discharge flow-mass spectrometry and flash photolysis-UV spectrometry were used to investigate the reaction of ClO with BrO over the temperature range of 220-400 K and the pressure range of 1-760 Torr. Rate constants were determined for: (1) Br + ClOO, (2) Br + OClO, and (3) BrCl + O2. It is found that the rate constants for the overall reaction and each reaction branch are inversely dependent on temperature and independent of pressure. For temperatures found in the Antarctic stratosphere, the rate coefficients for the channels yielding ClOO and OClO are a factor of 2-3 larger than previously estimated.
The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.
The reaction between BrO and ClO was studied over the pressure range 50-700 torr and temperature range 220-400 K, using the flash photolysis-ultraviolet absorption method described by Watson et al. (1979). In order to investigate the mechanism of the BrO + ClO reaction, the product branch reactions Br + Cl2O yielding ClO + BrCl and Cl2O + h(nu) yielding products were examined. The rate constant for the overall reaction and the Arrhenius expression for the Br + Cl2O reaction are given, as well as the quantum yield for the production of atomic oxygen from the Cl2O photolysis.
The kinetics and product branching ratios of the reaction between ClO and BrO were studied at 1 torr pressure over the temperature range 220-400 K, using the method of discharge-flow mass spectrometry. Three product channels were identified and quantified: Br + ClOO, Br + OClO, and BrCl + O2, indicating that the reaction mechanism of ClO + BrO involves metastable intermediates. The overall reaction rate coefficient and the rate coefficients for the three channel reactions are given.
Heat capacities of twelve different Lithium/BCX (BrCl in thionyl chloride) batteries in sizes AA, C, D, and DD were determined. Procedures and measurement results are reported. The procedure allowed simple, reproducible, and precise determinations of heat capacities of industrially important Lithium/BCX cells, without interfering with performance of the cells. Use of aluminum standards allowed the accuracy of the measurements to be maintained. The measured heat capacities were within 5 percent of calculated heat capacity values.
Mixing ratios of BrO have been measured in the Arctic lower statosphere with an instrument mounted on the NASA ER-2 aircraft. Observations from fourteen flights above the Arctic Circle in January and February of 1989 defined mixing ratios within the vortex of 4 + or - 2 parts per trillion by volume (pptv) at a potential temperature of 400 K, rising to 8 + or - 2 pptv at 470 K. These values are twice as large as values found at equivalent potential temperatures at lower latitudes, and are comparable to the mixing ratios found inside the antarctic polar vortex. Within the statistical uncertainty of the measurements, no BrO was observed in darkness at any time either inside or outside of the vortex, indicating that active bromine was sequestered in long-lived reservoirs, probably BrONO2 and BrCl. These measurements, in conjuction with measurements of ClO, demonstrate that the interaction of bromine and chlorine could represent a major sink for ozone in the presence of sunlight.
A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.
Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.