For this she was cast in a special heat-resistant nylon housing Brass poles made. The state of charge LED charge status display of each cell is via a built-in processor Balancer and ensures the highest safety standard for lithium batteries.
Due to the universal size of the lithium battery in conjunction with the included Adhesive adapter pads spacers , these batteries are versatile. Too bad, now we have to go back to the glass ball or read in the coffee grounds to understand our visitors Why do we have to do that? Quite simply, you have forbidden us to watch Your steps on our site with Google Analytics.
That sounds dramatically to You, we know. We do not know who You are, whether You are male or female, how old You are, how Your weight is - no idea. Nor do we pass this data on to Google, we don not have them not at all! Listed below are the chemicals we used in our study and corresponding purities and manufactures.
SF 6 NO 2 Purity of canola oil was not determined. Images of the film surfaces in Fig. The area around the dent reflects the smooth morphology of the film substrate before poking it. The slightly darker shades within the imaged area do not represent any morphology features but the unfocused scratches from the silver substrate holder beneath the film. The film flowed at an observable rate to restore a smooth surface, minimizing the surface energy of the system Fig.
The fragments have clear glass-like cracks, and no smoothing of the edges was observed over the course of the experiment. Based on our poke-flow experiments as shown in Figs. Table 1 Estimated T g of the applied substrate films. T g exp is the measured T g using the poke-flow technique. T g lit is the literature-reported T g. D is fragility. By monitoring the substrate surface morphology, we can estimate T g of the applied substrates as the highest temperature when shattering occurs.
All images of the poke-flow experiment are documented in Figs. Table 1 gives the estimated T g exp values of applied substrates compared to literature T g lit and predicted T g pred values. T g pred for substrate mixtures is derived from the Gordon—Taylor equation Gordon and Taylor, assuming literature T g values and no residual water present.
The uncertainties in T g pred values are derived by Gaussian error propagation. Except for the GLU substrate film, we achieve agreement or close agreement with either T g lit or T g pred. Since T g determination depends on cooling or drying rates, we do not expect agreement with literature values or predicted values.
This discrepancy is very likely due to our substrate film preparation process where under slow drying evaporation the outermost layers of the film contain less water than the deeper layers. Thus, the substrate surface represents the experimental conditions more closely. Furthermore, the microscope focus in our poke-flow experiments is on the substrate surface, thereby monitoring the substrate morphology that is governed by the film viscosity most closely representing the desired conditions.
The lines represent predicted viscosities as a function of T g exp and applied D values see Table 1. PF-shattered and PF-liquid blue circles indicate the conditions for which the poke-flow PF experiment detected a solid glassy and liquid phase state of the substrate, respectively.
The shaded areas represent predicted viscosities by using the VTF equation with modified D values as indicated in the panels based on the estimated viscosities derived from the poke-flow experiment. The temperature dependence of the substrate viscosity can be predicted by using the modified Vogel—Tammann—Fulcher VTF equation Angell, :. The fragility parameter, D , is defined in terms of the deviation of the temperature dependence of the viscosity from the simple Arrhenius behavior.
Therefore, the temperature dependence of substrate viscosity can be predicted using our measured T g exp as illustrated in Fig. For our calculations, we use literature D values for pure sugars and a mass-weighted interpolation of D values for the mixtures as shown in Table 1. In Fig. In contrast to our poke-flow experiments, Fig.
Capturing this phase transition with the modified VTF equation Angell, can only be achieved when using lower D values of 5. The addition of water increases the steepness of the glass transition and decreases D values by potentially reducing the thermal energy necessary to promote the cooperative chain motions Angell, ; Borde et al.
Furthermore, a study of the trehalose—water system corroborates that the presence of water lowers D values to 3. A D value between 4. Figure 5 Reactive uptake experiments showing the change in the normalized gas-phase oxidant signal as the reaction time is changed by pulling back the injector incrementally. The uptake coefficient is determined experimentally from the loss of the gas-phase oxidant to the organic substrate as the substrate area or corresponding reaction time is changed.
Open circles, triangles, squares, and diamonds correspond to uptake measurements at different temperatures. Lines represent the corresponding linear fits to the data and corresponding slopes. From these data, the observed first-order wall loss rate, k obs , is determined as the slope of the change in the natural logarithm of the oxidant signal as a function of reaction time, i. In the case of O 3 uptake Fig. As discussed in detail further below, the large difference in k obs between these two temperature regimes coincides with the CA substrates being in a liquid and solid phase state.
The change in concentration of oxidant X along the flow tube due to reactive uptake can be expressed using the effective uptake coefficient. N S h w eff is the effective Sherwood number which represents an effective dimensionless mass-transfer coefficient to account for changes in the radial concentration profile of the entry region Knopf et al.
The KPS method is advantageous over the correction approach by Brown since it accounts for entrance effects that can result in the overestimation of reactive uptake coefficients as outlined by Davis and discussed in more detail in the Appendix. This is crucial for fast uptakes involving the OH radical, however, less so for the uptakes involving O 3 and NO 3 radicals.
The method introduced by Fuller et al. To calculate the diffusion coefficient of an oxidant D X in a mixture of He and O 2 , we applied the following equation with P He and P O 2 representing pressures derived from experimental flow rates and pressure measurements Hanson and Ravishankara, :. The pressure in the flow reactor is maintained at less than 2. Diffusion limitation can be estimated by using the additivity formula for kinetic resistances as Gershenzon et al.
R is the radius of the flow tube. Gershenzon et al. As outlined in Sect. In other words, during the typical duration of a reactive uptake experiment, the oxidant exposure does not lead to complete oxidation of the substrate surface. The reactive uptake is determined under dry conditions in the presence of O 2.
Both methods yield the same results due to the slow uptake kinetics as further discussed in the Appendix. In this temperature regime, the bulk diffusion coefficients of both ozone and canola oil are expected to decrease by several orders of magnitude due to the transition from a viscous liquid to a solid Koop et al.
Our O 3 reactive uptake coefficients agree with previous literature data by de Gouw and Lovejoy and extend those to lower temperatures. A study by Berkemeier et al. Our results are consistent with previous studies Shiraiwa et al.
Figure 7 Reactive uptake coefficients of O 3 by canola oil as a function of temperature. See text for more details. As the temperature decreases and reactivity decreases, the desorption lifetime increases, potentially resulting in a compensating effect on the overall uptake kinetics.
Based on our poke-flow experiment, LEV substrates maintained a semisolid or solid phase state for all examined temperatures. Assessment of these various impacts on the observed uptake kinetics necessitates an in-depth analysis, e. Presence of water would render the film less viscous, thereby increasing reactivity.
The dashed line represents the glass transition temperature T g measured in the poke-flow experiment. Table 2 Comparison of uptake coefficients of NO 3 on liquid and solid substrates of saturated and unsaturated organics. Therefore, the significant change in NO 3 uptake reactivity in the investigated temperature range can be attributed to the transition of a solid or highly viscous substrate film to a liquid substrate film. As such, the underlying reaction mechanism changes; i.
As shown in Shiraiwa et al. T g is the glass transition temperature determined in the poke-flow experiment. Gross et al. Moise et al. This is in contrast to expectations derived from the gas-phase structure activity relationships SARs Atkinson, ; Kerdouci et al. Furthermore, considering that NO 3 concentrations are too low to saturate the substrate surface, the probability of collisions with the most reactive hydrogen may also be low.
In conclusion, our study demonstrates a strong positive correlation between temperature, substrate phase state, and NO 3 uptake reactivity for saturated alcohols. GLU substrates maintain a solid or highly viscous phase state for all examined temperatures. We also observe a decrease in reactivity Fig. This implies that other factors may also play a role in the observed heterogeneous reactivity. Since different chemical bonds have different reactivity and temperature dependence Kwok and Atkinson, , the reaction probability of OH radicals can be affected by the molecular orientation at the surface.
SAR suggests that tertiary C—H bonds contribute to this negative temperature dependency of the reactivity. Hence, if more C—OH bonds are exposed to the surface compared to tertiary C—H bonds, this negative temperature dependency of reactivity weakens. A similar steric argument was given by Nah et al. Also, the remaining amount of water in these substrates may impact the surface structure and the viscosity of the near-surface region, thereby potentially counteracting the decreasing reaction rate with increasing temperature predicted with the SAR method.
Judging by the morphology and the flow characteristics of the organic film, it experiences a glass phase transition within the investigated temperature range. Waring et al. X-ray diffraction studies on liquid oleic acid showed that the unsaturated acid molecules exist primarily as dimers through hydrogen bonding of the carbonyl oxygen and the acidic hydrogen Iwahashi and Kasahara, ; Iwahashi et al.
Lastly, gas-phase reaction kinetics suggest that unsaturated oxygenated organics e. Temperature varies greatly in the troposphere, in both the latitudinal and altitudinal directions. The zonal average surface temperature changes approximately 0. Globally, the temperature will greatly influence the phase state and the heterogeneous oxidation of OA particles, especially for SOA particles that can exist in a liquid phase state in the warmer planetary boundary layer but can be mostly solid in the colder middle and upper troposphere Shiraiwa et al.
N tot represents the concentration of reaction sites on the organic substrate surface. Here, we apply this idealized approach to assess the degree of surface oxidation of OA particles in a solid or highly viscous phase state and when the oxidation reactions are confined to the surface. However, given that the surface-active organics are ubiquitous in tropospheric aerosols and organic films can exist on aerosol surfaces with potentially significant effects on atmospheric chemistry and climate, e.
Figure 10 shows the effect of temperature on the surface species' lifetime for the different examined heterogeneous oxidation reactions. Oxidation of CA by O 3 proceeds within minutes to hours for typical tropospheric temperatures.
Thus, degradation of unsaturated fatty acids is expected to proceed efficiently, even at colder temperatures. Despite the OH radical being the most effective oxidizer, Fig. However, closer to the surface, degradation can proceed almost an order of magnitude faster. Degradation of the particle surface by NO 3 may proceed by about a factor of 2 slower at the coldest tropospheric temperatures compared to boundary layer conditions. Clearly, these datasets indicate that the topmost organic layers for most of the investigated OA surrogates can be oxidized within 1 week for lower- and middle-tropospheric conditions.
However, as soon as OA particles reach higher altitudes and lower temperatures by, e. For example, aerosol particles originating from extreme wildfires, like Australia bushfires, can circumnavigate the globe in weeks and can even reach the stratosphere, existing for weeks or months Ribeiro et al. Note the different scales on the time axis. We derive DF as a function of temperature and oxidant exposure time for oxidant concentrations given above. However, we note that this DF estimate is a simplified approach, since we assume that measured oxidation kinetics proceed throughout the entire particle with the same rate.
This ignores the slow gas diffusion in the condensed phase and the hindered internal mixing of organic species, particularly when the OA particle is in a solid or highly viscous phase state. For OH oxidation, previous studies indicate that the oxidation reaction is confined to near the surface of a liquid or solid organic substrate, even for longer OH exposure periods at lower OH concentrations Slade and Knopf, ; George and Abbatt, ; Lee and Wilson, ; Shiraiwa et al.
However, whether bulk processes may significantly change the reactivity under long oxidant exposure as encountered in the atmosphere still needs to be examined. In the case of O 3 and NO 3 oxidation of organic substrates, the results by Shiraiwa et al. Therefore, we probably underestimate the chemical lifetime. As such, the DF values at lower temperatures likely represent upper limits. In other words, degradation in ambient particles is expected to be less.
Keeping this limitation in mind, Fig. As expected, for the lowest temperatures, the DF values are lowest, implying the longest lifetimes. The stronger the particle viscosity change with temperature, the greater the change in DF; e.
This yields the largest change in DF over this temperature range compared to the other investigated systems considering the same exposure time period. This is consistent with previous aircraft observations reporting a large number of biomass burning aerosol particles in aged plumes at higher altitudes of the troposphere Cubison et al. This also supports the hypothesis that aerosol particles originating from large wildfires e. The presence of water vapor will significantly impact the phase state, in particular, of hygroscopic species such as LEV and GLU Zobrist et al.
Neglecting this effect will lead to an underestimation of DF. This discussion neglects the chemical complexity of ambient OA where different condensed-phase species can result in different reactivities and reaction pathways Zhang et al. Those in turn can change the multiphase kinetics and its dependency on temperature and particle phase state. Furthermore, heterogeneous particle composition and morphology can result in matrix effects or liquid—liquid phase separation, where, for example, more reactive organic species are shielded by less reactive species Lignell et al.
Those effects were not assessed in this study but necessitate additional experimental investigations. For the case of OH, this is the first low-temperature reactive uptake study of which the authors are aware.
The phase states of the organic substrate films were examined using the poke-flow technique, allowing for an estimation of T g and substrate flow characteristics to constrain the magnitude of the substrate viscosity at different temperatures using the VTF equation. The strongest changes in heterogeneous reactivity observed for the examined oxidant—substrate systems correlate with the largest change in organic substrate viscosity with temperature associated with a solid-to-liquid phase transition.
The largest reactivity occurs between O 3 and CA, exhibiting a change by a factor of 34, due to the phase transition of CA. In general, we attribute the faster heterogeneous kinetics in the semisolid and liquid phase states to surface and bulk reactions, the latter enabled by increased diffusion coefficients of gas and condensed species resulting from lower viscosity. Furthermore, once in the liquid phase, as temperature increases viscosity decreases and diffusivity increases, leading to potentially strong increases in reactivity.
As a result, the overall reactivity is lower compared to liquid substrate films and does not change significantly with temperature. Although viscosity in the semisolid phase regime can change substantially with temperature, viscosity can still be too high to allow for significant bulk processes to play a role. In this case, surface reactions likely dominate, and replenishment of unoxidized molecules to the surface is hindered. Application of organic substrate mixtures to control T g to induce a solid-to-liquid phase transition as temperature increases is accompanied by an increase in reactivity.
Our results are consistent with previous studies reporting the significance of particle phase state for the reactive uptake kinetics Arangio et al. A crucial aspect of this study is the interplay between the temperature dependence of the reaction kinetics and the desorption lifetime. At lower temperatures when an organic substrate is in the solid state, over a wide temperature range the reactivity does not change significantly. Desorption lifetime will likely increase significantly with decreasing temperature with subsequent effects on the reaction kinetics.
Changes in substrate viscosity with temperature may also play a role in the overall heterogeneous kinetics when the substrate is in a semisolid phase state. However, to what extent the particle viscosity will influence the diffusion and reaction kinetics is still not resolved.
The comprehensive dataset presented here will allow application of a more detailed kinetic multi-layer model to constrain the temperature dependency of reaction and transport parameters. This study did not address the role of water vapor acting as a plasticizer concurrent to phase changes induced by temperature changes Zobrist et al. The role of humidity in amorphous phase state and resulting multiphase kinetics has been studied at room temperature Shiraiwa et al. Most of these studies suggest that increasing humidity leads to faster reactive uptake kinetics.
However, at lower temperatures, diffusivity is slower, leading to kinetically hindered adjustments of the condensed-phase state Berkemeier et al. Future experimental studies should focus on how the coupled effects of ambient temperature and humidity on the amorphous phase state of OA particles modulate the multiphase oxidation kinetics. Our study demonstrates unambiguously that the chemical reactivity of organic matter towards atmospheric oxidants can vary significantly in response to ambient temperature, which, in turn, modulates the organic phase state.
Ambient OA, however, displays greater chemical and morphological complexity Laskin et al. Despite this caveat, due to lower temperatures at higher altitudes, we can expect OA particles during transport in the free troposphere to have significantly longer lifetimes with respect to chemical degradation.
This is important information for our understanding of the chemical evolution of OA particles and their impact on source apportionment, air quality, and climate. The KPS method Knopf et al. When considering the establishment of gas concentration profiles for correction of observed pseudo-first-order wall loss rates, slower uptake reaction kinetics e.
A1 Davis, However, reactive OH uptake exerts faster reaction kinetics and thus resembles conditions of a fast gas flow or a short flow tube Fig. A1 where N S h w eff can significantly depart from 3. A2 for the uptake of OH by glucose. Hence, for fast uptake kinetics, we recommend using either the KPS or CKD methods to derive accurate uptake kinetics when using a coated-wall flow reactor.
Figure A1 Dependence of the effective Sherwood number N S h w eff on the dimensionless axial distance of the flow reactor. Smaller dimensionless axial distance represents the scenario of a fast flow or short tube. Adapted from Davies and Knopf et al.
Red squares and blue diamonds represent the KPS and Brown methods, respectively. This flow condition can lead to a jet-like exit gas flow from the movable injector. The velocity profile and volume flow rate Q of a Poiseuille flow in the annular section can be described by the equations Rosenhead, Using the flow tube with a diameter of 1. Therefore, even when adjusting the gas flows in the injector and flow reactor to yield the same mean flow velocities, the difference in the maximum flow velocities can still differ significantly.
In the case of using a flow tube with a diameter of 1. For additional data related to this study, please contact the corresponding author. JL conducted the poke-flow experiments. JL performed all analysis of data. SMF conducted analysis of NO 3 uptake data and contributed to the writing of the manuscript.
JL led the writing of the manuscript. DAK oversaw the project, envisioned the analysis, and contributed to the writing of the manuscript. Support from the National Science Foundation and partial support from the U. This research has been supported by the U. National Science Foundation grant no. AGS and the U.
Abbatt, J. Abramson, E. Andreae, M. Angell, C. Arangio, A. Atkinson, R. Baetzold, R. Bai, J. Berkemeier, T. Bertram, A. Borde, B. Glass transition and fragility, Carbohyd. Brown, R. Brown, S. Charnawskas, J. Chenyakin, Y. Comunas, M.
Cooney, D. Cosman, L. Cubison, M. Davies, J. Davis, E. DeRieux, W. Deshler, T. Dette, H. Diogo, H. Edebeli, J. Elamin, K.
PubChem CID. Chemical formula. Solubility in water. Refractive index n D. Crystal structure. Space group. Coordination geometry. Heat capacity C. Std molar entropy S o Other anions. Other cations. Related lithium oxides. Chemical compound. Handbook of Inorganic Chemicals. Chemistry of the Elements. Oxford: Pergamon Press. ISBN Zintl ; A. Harder; B. Dauth Bellert, W. Breckenridge, J. Lithium compounds list. Oxides are sorted by oxidation state. Oxygen compounds. Categories : Oxides Lithium compounds Fluorite crystal structure.
Namespaces Article Talk. Views Read Edit View history. Coordination geometry. Heat capacity C. Std molar entropy S o Other anions. Other cations. Related lithium oxides. Chemical compound. Handbook of Inorganic Chemicals. Chemistry of the Elements. Oxford: Pergamon Press. ISBN Zintl ; A. Harder; B. Dauth Bellert, W. Breckenridge, J. Lithium compounds list. Oxides are sorted by oxidation state. Oxygen compounds.
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Chemical compound. Handbook of Inorganic Chemicals. Chemistry of the Elements. Oxford: Pergamon Press. ISBN Zintl ; A. Harder; B. Dauth Bellert, W. Breckenridge, J. Lithium compounds list. Oxides are sorted by oxidation state. Oxygen compounds. Categories : Oxides Lithium compounds Fluorite crystal structure. Namespaces Article Talk. Views Read Edit View history. Help Learn to edit Community portal Recent changes Upload file. Download as PDF Printable version.
Wikimedia Commons. Other names Lithia, Kickerite. Antifluorite cubic , cF Main hazards. Lithium sulfide Lithium selenide Lithium telluride Lithium polonide. Sodium oxide Potassium oxide Rubidium oxide Caesium oxide. Lithium peroxide Lithium superoxide. Y verify what is Y N? Infobox references. Chemical formulas. The oxide reacts slowly with water, forming lithium hydroxide. From Wikipedia, the free encyclopedia. CAS Number. Interactive image. PubChem CID. Chemical formula. Solubility in water.
Refractive index n D. Crystal structure. Space group. Coordination geometry. Heat capacity C. Std molar entropy S o Other anions. Other cations. Related lithium oxides. Chemical compound. Handbook of Inorganic Chemicals.
Chemistry of the Elements. Oxford: Pergamon Press. ISBN Zintl ; A. Harder; B. Dauth Bellert, W. Breckenridge, J. Lithium compounds list. Oxides are sorted by oxidation state.
Exploring the working mechanism of Li+ in O3-type NaLiNiMnO2 cathode materials for rechargeable Na-ion batteries†. Check for updates. Lithium was substituted on the alkali site of an O3-type layered structure as cathode material for sodium-ion batteries (SIBs). Role of Li in Na. Li (N O3) (H2 O)3 | H6LiNO6 | CID - structure, chemical names, physical and chemical properties, classification, patents, literature.