Fast thermal desorption spectroscopy study of morphology and vaporization kinetics of polycrystalline ice films

Fast thermal desorption spectroscopy was used to investigate the vaporization kinetics of thin (50-100 nm) H(2)O(18) and HDO tracer layers from 2-5 microm thick polycrystalline H(2)O(16) ice films at temperatures ranging from -15 to -2 degrees C. The isothermal desorption spectra of tracer species demonstrate two distinct peaks, alpha and beta, which we attribute to the vaporization of H(2)O(18) initially trapped at or near the grain boundaries and in the crystallites of the polycrystalline ice, respectively. We show that the diffusive transport of the H(2)O(18) and HDO tracer molecules in the bulk of the H(2)O(16) film is slow as compared to the film vaporization. Thus, the two peaks in the isothermal spectra are due to unequal vaporization rates of H(2)O(18) from grain boundary grooves and from the crystallites and, therefore, can be used to determine independently the vaporization rate of the single crystal part of the film and rate of thermal etching of the film. Our analysis of the tracer vaporization kinetics demonstrates that the vaporization coefficient of single crystal ice is significantly greater than those predicted by the classical vaporization mechanism at temperatures near ice melting point. We discuss surface morphological dynamics and the bulk transport phenomena in single crystal and polycrystalline ice near 0 degrees C.     

Diffusion of HDO in pure and acid-doped ice films

In these experiments, a few bilayers of D(2)O were vapor-deposited on a pure crystalline H(2)O ice film or an ice film doped with a small amount of HCl. Upon deposition, H/D isotopic exchange quickly converted the D(2)O layer into an HDO-rich mixture layer. Infrared absorption spectroscopy followed the changes of the HDO from the initial HDO mixture layer to HDO isolated in the H(2)O ice film. This was possible because isolated HDO in H(2)O ice has a unique, sharp peak in the O-D stretch region that can be distinguished from the broad peak due to the initial HDO mixture layer. The absorbance of isolated HDO displayed first-order kinetics and was attributed to diffusion of HDO from the HDO-rich mixture layer into the underlying H(2)O ice film. While negligible diffusion was observed for pure ice films and for ice films with HCl concentrations up to 1 x 10(-4) mole fraction, diffusion of HDO occurred for higher concentrations of (2-20) x 10(-4) mole fraction HCl with a concentration-independent rate constant. The diffusion under these conditions followed Arrhenius behavior for T = 135-145 K yielding E(a) = 25 +/- 5 kJ/mol. The mechanism for the HDO diffusion involves either (i) molecular self-diffusion or (ii) long-range H/D diffusion by a series of multiple proton hop and orientational turn steps. While these spectroscopic results compare favorably with recent studies of molecular self-diffusion in low-temperature ice films, the diffusion results from all the ice film studies at low temperatures (ca. T < 170 K) differ from earlier bulk ice studies at higher temperatures (ca. T > 220 K). A comparison and discussion of the various diffusion studies are included in this report.     

Electrochemical determination of activation energies for methanol oxidation on polycrystalline platinum in acidic and alkaline electrolytes

The oxidation pathways of methanol (MeOH) have been the subject of intense research due to its possible application as a liquid fuel in polyelectrolyte membrane (PEM) fuel cells. The design of improved catalysts for MeOH oxidation requires a deep understanding of these complex oxidation pathways. This paper will provide a discussion of the literature concerning the extensive research carried out in acidic and alkaline electrolytes. It will highlight techniques that have proven useful in the determination of product ratios, analysis of surface poisoning, anion adsorption, and oxide formation processes, in addition to the effects of temperature on the MeOH oxidation pathways at bulk polycrystalline platinum (Pt(poly)) electrodes. This discussion will provide a framework with which to begin the analysis of activation energy (E(a)) values. This kinetic parameter may prove useful in characterizing the rate-limiting step of the MeOH oxidation at an electrode surface. This paper will present a procedure for the determination of E(a) values for MeOH oxidation at a Pt(poly) electrode in acidic and alkaline media. Values from 24-76 kJ mol(-1) in acidic media and from 36-86 kJ mol(-1) in alkaline media were calculated and found to be a function of applied potential and direction of the potential sweep in a voltammetric experiment. Factors that influence the magnitude of the calculated E(a) include surface poisoning from MeOH oxidation intermediates, anion adsorption from the electrolyte, pH effects, and oxide formation processes. These factors are all potential, and temperature, dependent and must clearly be addressed when citing E(a) values in the literature. Comparison of E(a) values must be between systems of comparable electrochemical environment and at the same potential. E(a) values obtained on bulk Pt(poly), compared with other catalysts, may give insight into the superiority of other Pt-based catalysts for MeOH oxidation and lead to the development of new catalysts which lower the E(a) barrier at a given potential, thus driving MeOH oxidation to completion.     

蜂窝催化剂上甲醇自热重整制氢的动力学研究

400 ℃～460 ℃,400 h－1～1 600 h－1,O2/CH3OH(mol ratio)=0.10～0.25,H2O/CH3OH (mol ratio) =1.0～1.8下,通过正交实验设计方法,用BSD-2A型内循环无梯度反应器研究了Zn-Cr/CeO2-ZrO2蜂窝催化剂上甲醇自热重整制氢反应的宏观动力学。以甲醇水蒸气重整反应、甲醇分解反应和甲醇完全氧化反应为独立反应进行了研究,得出了幂指数型反应速率表达式,并根据实验结果,利用最小二乘法求解了动力学参数值。F检验表明该动力学模型是高度显著的。该多重反应动力学方程的得出为蜂窝反应器的进一步模拟、优化和设计提供了数据。     

Continuous-distribution kinetics for degradation of polybutylene terephthalate (PBT) in supercritical methanol

The depolymerization of polybutylene terephthalate (PBT) in supercritical methanol was investigated by using a batch autoclave reactor. Continuous kinetics analysis was applied to experimental data. It was observed that PBT could dissolve into supercritical methanol quickly and decompose completely in a homogeneous phase. PBT with average molecular weight of about 29 700 was converted to oligomer with that of 4200 within 10 min and with that of 2700 in 15 min at 513 K and converted into monomer completely within 22 min. The main reaction products decomposed of PBT were dimethylterephthalate (DMT) and 1, 4-butanediol (BG) by methanolysis. The yields of monomer components of the decomposition products, including byproducts were measured. The yields of DMT and BG could reach 94.5% and 70.1%, respectively, at 563 K for 75 min. Based on the qualitative and quantitative analyses of the products, a depolymerization-reaction scheme was proposed to explain the reaction mechanism, i.e. the degradation of PBT in supercritical methanol mainly includes random scission and chain-end scission reactions and side reactions for monomer components. With the process of degradation, some oligomers could be decomposed into small molecular products by side reactions. Continuous-distribution kinetics theory was developed to analyze the decomposition behavior. The energy of activation for the random scissions of PBT in the supercritical methanol was 86.53 kJ/mol.     

Diffusion of methanol in zeolite NaY: a molecular dynamics study

Molecular dynamics simulations were performed in order to obtain a detailed understanding of the self-diffusion mechanisms of methanol in the zeolite NaY system. We derived a new force-field term to describe the interactions between the methanol molecules and the extraframework cations. From the simulations, we show that diffusive behavior in the high-temperature range consists of a combination of both short- and long-range motions at low and intermediate loadings. This type of motion is characterized by an activation energy that decreases as the loading increases. At low loadings, we also observe short-range diffusive behavior based on a surface-mediated mechanism. The short-range behavior corresponds to motion only on the length scale of an FAU supercage, whereas the long-range behavior involves intercage diffusion. For the saturation loading corresponding to 96 methanol molecules per unit cell, only short-range motions within the same supercage predominate. Finally, the preferential arrangement of the adsorbate molecules around the extraframework cations are examined and compared with those previously deduced from experimental data.     

Diffusion of ferrocene methanol in super-cooled aqueous solutions using cylindrical microelectrodes

The diffusion of ferrocene methanol in super-cooled aqueous solutions containing sucrose has been studied, using disk and cylindrical microelectrodes, over a wide viscosity range. The solution viscosity and the reduced temperature T/T_g (T_g being the glass transition temperature) were varied by changing the sucrose concentration and the temperature of the system. The voltammetric limiting current obtained with a disk microelectrode and the i(t) response on a cylindrical microelectrode after a potential step were used to determine diffusion coefficients from 7 × 10⁻⁶ cm² s⁻¹ down to 2 × 10⁻¹¹ cm² s⁻¹. The electrochemical procedure described in this work allows a simple and accurate measurement of the dynamics of electroactive solutes in glass-forming liquids.     

Kinetics of proton transfer in ice via the pH-jump method: Evaluation of the proton diffusion rate in polycrystalline doped ice

The value of the proton diffusion coefficient D_H⁺ in ice was extracted from the diffusion-controlled rate k_D of the proton recombination reaction RO⁻ + H₃O⁺ → k_D ROH + H₂O in polycrystalline doped ice. At −10°C, D_H⁺ was estimated to lie between 3.5×10⁻⁶ and 1.3×10⁻⁵ cm² s⁻¹, well below the corresponding value of (4.1 ± 0.1)×10⁻⁵ cm² s⁻¹ found in supercooled water.     

Chemical kinetics of reactions in the unfrozen solution of ice

Some reactions are accelerated in ice compared to aqueous solution at higher temperatures. Accelerated reactions in ice take place mainly due to the freeze-concentration effect of solutes in an unfrozen solution at temperatures higher than the eutectic point of the solution. Pincock was the first to report an acceleration model for reactions in ice,1 which successfully simulated experimental results. We propose here a modified version of the model for reactions in ice. The new model includes the total molar change involved in reactions in ice. Furthermore, we explain why many reactions are not accelerated in ice. The acceleration of reactions can be observed in the cases of (i) second- or higher-order reactions, (ii) low concentrations, and (iii) reactions with a small activation energy. Reactions with a buffer solution or additives in order to adjust ion strength, zero- or first-order reactions, or reactions containing high reactant concentrations are not accelerated by freezing. We conclude that the acceleration of reactions in the unfrozen solution of ice is not an abnormal phenomenon.     

Effect of water density on methanol oxidation kinetics in supercritical water

We oxidized methanol in supercritical water at 500 degrees C to explore the influence of the water concentration (or density) on the kinetics. The rate increased as the water concentration increased from 1.8 to 5.7 mol/L. This effect of water density on the kinetics observed experimentally was quantitatively reproduced by a previously validated mechanism-based, detailed chemical kinetics model. In this model, reactions of OH radicals with methanol were the fastest methanol removal steps. The rates of these removal steps increased with water density at 500 degrees C because the OH radical concentration increased. The OH radical concentration increased with density because the rates of the steps H + H2O = OH + H2 and CH3 + H2O = OH + CH4, which produce OH radicals, increased. Thus, the main role of water in accelerating methanol oxidation kinetics at 500 degrees C is as a hydrogen donor to a radical (R) in steps such as R + H2O = OH + RH. This system provides a striking example of SCW being involved on the molecular level in the free-radical oxidation as a reactant in elementary steps.     

Photodissociation of polycrystalline and amorphous water ice films at 157 and 193 nm

The photodissociation dynamics of amorphous solid water (ASW) films and polycrystalline ice (PCI) films at a substrate temperature of 100 K have been investigated by analyzing the time-of-flight (TOF) mass spectra of photofragment hydrogen atoms at 157 and 193 nm. For PCI films, the TOF spectrum recorded at 157 nm could be characterized by a combination of three different (fast, medium, and slow) Maxwell-Boltzmann energy distributions, while that measured at 193 nm can be fitted in terms of solely a fast component. For ASW films, the TOF spectra measured at 157 and 193 nm were both dominated by the slow component, indicating that the photofragment H atoms are accommodated to the substrate temperature by collisions. H atom formation at 193 nm is attributed to the photodissociation of water species on the ice surface, while at 157 nm it is ascribable to a mixture of surface and bulk photodissociations. Atmospheric implications in the high latitude mesopause region of the Earth are discussed.     

Electrooxidation of CO(ad) intermediated from methanol oxidation on polycrystalline Pt electrode

The poisonous intermediate of methanol oxidation on a Pt electrode was validated to be CO(ad) by electrochemical method. An approximate treatment to bimolecular elementary reactions on an electrode was advanced and then was applied to the stripping normal pulse voltammetry (NPV) for complex multistep multielectron transfer processes on plane electrodes to study the kinetics of completely irreversible process of CO(ad) oxidation to CO2. The kinetic parameters for this process, such as standard rate constant (k0) and anodic transfer coefficient (alpha) for this irreversible heterogeneous electron-transfer process at electrode/solution interface and apparent diffusion coefficient (D(app)) for charge-transfer process within the monolayer of CO(ad) on electrode surface, were obtained with stripping NPV method. The effect of the approximate treatment on the kinetic parameters was also analyzed.     

Reaction kinetics of lactic acid with methanol catalyzed by acid resins

The esterification of aqueous lactic acid solution with methanol and its reverse reaction catalyzed by acidic cation exchange resins in the H⁺ form were carried out in a batch system. The inhibiting effects of water and methanol on the resins were evaluated. The experimental data were correlated by a kinetic model that the inhibition by methanol and water was included. The reaction rate constants and the adsorption coefficients were determined from the experiments. The activity of acidic resin was compared with that of sulfuric acid as catalyst. © 1996 John Wiley & Sons, Inc.     

Diffusion kinetics of the ion exchange of benzocaine on sulfocationites

The theory of the ion exchange kinetics on strong acid cationites with the participation of weak electrolytes is discussed. The kinetics of desorption of benzocaine in the protonated and molecular forms from strong acid cationites, sulfonated polycalixarene, and KU-23 30/100 sulfocationite, is studied experimentally. It is shown that the flow of protonated benzocaine from cationite upon desorption proceeding by the ion-exchange mechanism is more intense than upon desorption of nonionized benzocaine molecules. It is established that the diffusion coefficient of benzocaine cations is (1.21 ± 0.23) × 10^?12 m²/s in KU-23 30/100 sulfocation and (0.65 ± 0.06) × 10^?13 m²/s in sulfonated polycalixarene, while the diffusion coefficient of benzocaine molecules is (0.65 ± 0.15) × 10^?14 m²/s in sulfonated polycalixarene.     

Isoconfigurational molecular dynamics study of the kinetics of ice crystal growth

Spontaneous self-assembling, such as formation of molecular crystals, is a fascinating topic for investigation. Ability to initiate and control such transformations promises numerous benefits, but our knowledge of underlying mechanisms of such processes is rather limited. The process of freezing of water is an excellent testing ground for such studies. In this paper we report the results of a systematic molecular dynamics study of ice growth at three different temperatures below the melting point initiated from a number of initial interface structures within the isoconfigurational ensemble. It is shown that a specific structure at a growing ice-water interface is able to affect the growth process over a time scale of 1-2 ns. This structural effect can be characterized in terms of relative growth propensities. On the basis of the differences in the shape between isoconfigurational rate distributions and the rate distribution typical of the specific temperature several different kinds of relative growth propensities have been identified. The initial interfacial configurations employed in this work have been assigned using the proposed classification and possible mechanisms of propensity realization have been suggested for selected cases. Results reported in this paper clearly indicate that local structure effects can have significant impact on tendency for a particular ice surface to grow (or melt). The structural effect on ordering propensities is, most probably, a more universal behaviour and might be expected to be seen in other similar problems such as, for example, protein folding.     

Isothermal ice crystallization kinetics in the gas-diffusion layer of a proton-exchange-membrane fuel cell

Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. A validated rate expression is now available for predicting ice-crystallization kinetics in GDLs.