The anodic dissolution of iron—V. Some observations regarding the influence of cold working and of annealing on the two anodic reactions of the metal

Under conditions, where two anodic current regions, I₂ and I₂, were distinct in the Tafel plots of the iron electrode, the reaction orders with respect to pH were determined. In solutions containing chloride or bromid, pH ca 3–5, the reaction order for I₁(p_1,pH) was close to 1, while that for I₂(p_2,pH) assumed positive or negative values or even values changing from positive to negative over the pH-range. The numerical values were small, 0·2–0·3. Only lightly cold-worked iron was used in this group of experiments.

In another group of experiments only involving acetate containing solutions both cold-worked and annealed electrodes were employed. Until the influence of acetate became negligible at low pH, the effect of the treatment was largely limited to dissolution rates. The characteristic parameters at pH ca 4 were: for the I₁ reaction: b₁ = 30 mV, p_1,pH = 1·7 and p_1,Ac¹ (the reaction order for Ac) = −0·7; for the p₂ reaction: b₂ = 110 to 130 mV, p_2,pH = 0·2 and p_2,Ac = −0·2 to −0·3.

At lower pH the influence of acetate gradually disappeared, and higher values of b₁ and lower values of p_1,pH were then noted for the annealed metal. The I₂ reaction could not be followed here.

The transition between the I₁ and the I₂ reaction was studied at pH ca 4, and some deviation from earlier experience was noted for strongly cold-worked iron.     

Study of reversible electrode processes with unsymmetrical cyclic reciprocal derivative chronopotentiometry

In this paper, the theoretical study of cyclic reciprocal derivative chronopotentiometry (CRDCP) for totally reversible electrode processes with symmetrical and unsymmetrical programmed currents is presented. The main viewpoints are: (1) for symmetrical programmed current, the amplitudes of the successive currents are the same, i.e. I(t) = (−1)ⁱ⁺¹I₀, whereas the transition times of each current step, τ_i, have different values. The properties of the dt/dE-E curves corresponding to each current cycle also differ a lot. (2) For unsymmetrical programmed current proposed in this work for the first time, the applied current successively reversed at each transition time steps to different amplitude. The use of this unique programmed current is advantageous versus symmetrical programmed current since the transition times obtained are equal to each other anticipatively, and the dt/dE-E curves also coincide with each other for the successive cycles. In this case, the results obtained in CRDCP are almost similar to those of cyclic voltammetry (CV). The characteristic parameters obtained in the dt/dE-E curves in both cases are quantitatively related to the species concentrations adjacent to the electrode surface and afford simple diagnosis criteria to characterize the reversibility of electrode processes. Properties of reversible electrode processes have also been further studied through the use of more than one current cycle.     

Oxygen transport in zeolite Y measured by quenching of encapsulated tris(bipyridyl)ruthenium

This study deals with emission quenching of zeolite encapsulated trisbipyridyl ruthenium (II) (Ru(bpy)₃²⁺) by oxygen. Oxygen saturated solutions of Ru(bpy)₃²⁺ typically show about 70% quenching (I₀/I=3.3), where I₀ and I are the peak intensities of the emission in N₂ and O₂, respectively. However, an aqueous suspension of Ru(bpy)₃²⁺-zeolite Na–Y (Si/Al = 2.5) (abbreviated as Ru–Na–Y) showed no quenching at all. This observation motivated us to analyze how the transport of O₂ is occurring in the zeolite. Upon exposure of solid Ru–Na–Y (99% of intrazeolitic water) to N₂/O₂ dry gases, quenching in oxygen was found to be 5% (I₀/I=1.07). Partial dehydration at room temperature with loss of 33% of the water molecules from the zeolite led to 66% (I₀/I=2.96) quenching. Dehydration of Ru–Na–Y at 250 °C under vacuum overnight led to complete loss of intrazeolitic water and increased quenching to 90% (I₀/I=10.7). Nanocrystalline Ru(bpy)₃²⁺-zeolite Y upon vacuum dehydration lost 55% of the intrazeolitic water and showed 96% (I₀/I=25.3) quenching. The extent of quenching of Ru(bpy)₃²⁺ in zeolites by O₂ is by far the largest as compared to previously studied matrices, and is being attributed to confinement of O₂ in the supercages, which leads to increase in number of collisions with Ru(bpy)₃²⁺ and enhanced quenching. However, these samples showed complete lack of sensitivity (I₀/I=1) to oxygen upon exposure to water saturated gas or dissolved gas. Dealumination of zeolite framework by treatment with (NH₄)₂SiF₆ produced a framework of Si/Al = 9.5, and with SiCl₄ a framework of Si/Al > 100. With increasing dealumination, the extent of quenching by dissolved O₂ increased.     

用新的路径定位指数和神经网络研究多溴联苯醚理化性质

基于溴取代基及共轭母体的结构特征,定义一种新的路径定位指数^mP,并计算了209种多溴联苯醚分子的电性拓扑状态指数E₉和电性距离矢量M₂₆,这3个指数对有机污染物呈现出良好的结构选择性。采用多元回归方法对多溴联苯醚（PBDEs）的色谱保留时间（t_R）、正辛醇/空气分配系数（lgK_OA）、超冷流体蒸气压（lgP_L）及其毒性等性质与分子结构指数进行关联,建立的4个预测模型的相关系数分别达到0.991、0.997、0.998和0.904,标准偏差分别为0.031、0.104、0.100和0.358。将3个指数作为BP神经网络的输入层神经元,采用不同的网络体系结构,获得了令人满意的预测理化性质的神经网络模型,所得结果明显优于多元回归方法,结果显示多溴联苯醚的理化性质与⁰P、E₉和M₂₆具有良好的非线性关系。     

Determination of the optimum conditions for the cementation of cadmium with zinc powder in sulfate medium

The orthogonal array design has been used to determine the optimum conditions for the cementation of cadmium from a synthetic zinc sulfate solution and hence to achieve the highest cementation efficiency and the best robustness of the quantitation from the least number of trials in a laboratory scale. Cementation was performed using zinc powder. The orthogonal array L₉ (3⁴) that comprises four parameters at three levels was chosen. The parameters and their levels were as: zinc powder quantity (Z): 1, 1.2 and 1.5 times of stoichiometric quantity of cadmium; time (t): 4, 8 and 12 min; temperature (T): 25, 35 and 45 °C and zinc powder particle size distribution (R): nos. 1–3. The ultimate optimum cementation conditions were found to be Z₁ (equal to stoichiometric quantity of cadmium), T₁ (25 °C), R₃ (no. 3) and t₁ (4 min). Under these conditions, cementation percentages for cadmium and nickel were 95.83% and 6.63%, respectively.     

正弦波纹挡板式沉降器内流动特性

采用VOF模型对正弦波纹式入口挡板的重力非均相沉降器内流场进行数值模拟研究。对比了正弦波纹挡板与平挡板的平均流场分布情况，分析了沉降器的轴向流速均一程度（λ₁）随时间演化特性，探究了λ₁和面积加权平均湍流强度（I_a）在沉降器内空间分布特性；引入流场均稳指标USC，研究了冲击间距（L_b/D）对USC的影响。结果表明：正弦波纹挡板作为入口构件可以有效降低返混。在0.84＜L_b/D＜2.17范围内，正弦波纹板沉降器内流场的均一程度整体高于平面挡板；随着L_b/D减小，平挡板沉降器内流场的λ₁基本不变，但正弦波纹挡板沉降器内流场的λ₁降低，且对I_a的影响不明显。对比平挡板，正弦波纹挡板可以有效降低轴向速度的梯度，使返混区面积减小，流场稳定性提高。随着L_b/D增加，USC值呈现多峰值趋势，L_b/D=2.17时正弦波纹板沉降器的USC取得极大值为14.68，较平挡板提高了93.67%。     

The problem of correction for ohmic potential drop in linear potential sweep experiments and the derivation of s0 values for electrode surface processes

Rate constants or exchange current densities of electrode surface processes involving adatom arrays are conveniently evaluated by determining that sweep rate, s₀ (the reversibility parameter), in a linear potential sweep (LPS) experiment, below which the process just remains kinetically reversible, ie its overpotential is sensibly zero. Transition to irreversibility is characterized by peak potentials, E_p, becoming linear in the log of the sweep rate, s, following a region of independence of s for < s₀. A suitable extrapolation procedure enables s₀ to be evaluated. However, if s₀ is large and/or the resistivity of the solution is appreciable, the IR_u drop associated with uncompensated resistance in the measurement system can be comparable with the increase of E_p with log s, when s > s₀, rendering evaluation of s₀ inaccurate. While compensation or empirical correction for this may be made, it is desirable that the nature of the IR_u effect of the LPS I vs E profiles be understood in a more fundamental way. It is the purpose of this communication to provide such a treatment of this effect through evaluation of the actual time-dependent potential that becomes applied to the electrode, and to propose criteria based on the product of s₀, R_u and the reaction pseudocapacitance, C_φ for indicating the anticipated extent of the IR_u effect in the evaluation of s₀. While the transition in the E_p vs log s plot may be due to IR_u effects as well as to kinetic irreversibility, when the former are appreciable, it is shown that the corresponding transition in the value of C_φ with increasing log s can usually allow spurious IR_u and significant irreversibility effects to be distinguished.     

Determination of optimized membrane area from long-term flux decline data

Due to membrane fouling, long-term flux decline follows a general trend: it starts with a steep decline followed by a gradual decrease and approaches its final value asymptotically. Coupled with the concentration effect, our data indicate that this flux behavior can be represented with the equation F = f(t) (k₁ 1n r + k₂) with f(t) = a₀ + exp [a₁ + a₂t + a₃t²] where t is time, a₀, a₁, a₂, a₃, k₁, and k₂ are constants and r is the concentration ratio.

To take advantage of early high flux, ultrafiltration is usually discontinued after a period of time t_u, to be replaced by membrane cleaning period of time t_c. Only then the ultrafiltration cycle is repeated. The total membrane area required for multistage ultrafiltration can be shown as

Full-size image

where Q₀ is the ultrafiltration capacity, n is the number of stages, and rr_i is the concentration ratio at stage i. An optimization method can be utilized to determine minimum value of A_T. Results will be presented for the case of ultrafiltration of palm oil mill effluent.     

ETude cinetique des systemes Cd---Cd(II) et Fe(II)---Fe(II) en milieu aqueux par trace d'oscillogrammes lineaires au moyen de la methode de double impulsion potentiostatique

The principle and construction of a quadratic function generator are described. The voltage output, supplying the oscilloscope time-base, gives a linear i(√t) oscillogram and allows the transfer cd i_a to be read on the oscilloscope screen.

The kinetic parameters of the Cd---Cd(II0 and Fe(II)---fe(III) sytsems are determined in this way. In these two examples, the second Fick equation is solved numerically in order to establish the validity of the formula used to calculate T₀, the time corresponding to the cd i_a.

Zusammenfassung

Man beschreibt die Einstellung von einem Quadratischfunktiongenerator. Wenn die Klemmenspannung dieses Generators mit der Zeitablenkung des Oszillographes angeschaltet wird, erreicht man ein lineares Oszillogramm i(√t); die Durchtrittstromdichte i_a wird sofort auf dem Oszilloskopschrim gelesen.

Mann kann mit dieser Methode die elektrolytischen Konstanten der Reaktionen Cd---Cd(II) und Fe(II)---Fe(III) bestimmen. Jedenfalls integriert man die Zweite Diffusion differentialgleichung zahlenmässig und so, kann man die Richtigkeit der die Zeit gebenden Formel, welcher Zeit die Ordinate i_a auf die Linie i(√t) entspricht, bestätigen.     

Modelling formation and growth of H2SO4-H2O aerosols: Uncertainty analysis and experimental evaluation

An aerosol dynamics model, AERO2, is presented, which describes the formation of H₂SO₄-H₂O aerosol in a smog chamber. The model is used to analyse how the uncertainties on four input parameters are propagated through an aerosol dynamics model. The input parameters are: the rate of the reaction between SO₂ and OH (k₁), the ratio between the nucleation rate used in AERO2 and that derived from classical nucleation theory (t_n), the H₂SO₄ mass accommodation coefficient () and a measure of the turbulence intensity in the reactor (k_e). Uncertainties for these parameters are taken from the literature. One of the results of the analysis is that AERO2 and aerosol dynamics models in general can only predict upper bounds for the total number (N_tot) and total volume (V_tot) concentrations of the particles. The uncertainties on N_tot and V_tot are mainly due to the uncertainties on k₁, and t_n. An uncertainty factor of 20–100 still remains when the uncertainty on k₁, is reduced to ±5%. Aerosol measurements from three smog chamber experiments have therefore been used, in an attempt to reduce the uncertainty on k₁ and t_n. Values for k₁ are obtained in the reduced range 7.8 × 10⁻¹³ to 1.0 × 10⁻¹² cm³ s⁻¹, which is within the range found in the literature. For t_n, values in the range 10⁴–10⁷ are obtained, which is close to the upper bound of the range in literature. These values for t_n are in marked contrast with a recent set of experiments on nucleation in H₂SO₄-H₂O mixtures, which suggests a value for t_n of at most 10⁻⁵.     

An apparent kinetic model for the carbonation of calcium oxide by carbon dioxide

For the apparent kinetics of the carbonation reaction of calcium oxide by carbon dioxide, as a kind of noncatalytic gas–solid reaction, a model equation has been proposed as follows: X=kbt/(b+t), where X is the conversion of CaO; k, a kinetic rate constant (time⁻¹); b, a constant (time) equivalent to the time taken to attain half the ultimate conversion of CaO, and t, the time. As a result of analyses for some literature-reported data of CaO-carbonation conversion, it has been found that the rate of the carbonation can be well represented by dX/dt=k(1−X/X_u)², where X_u is the ultimate conversion of CaO, which is given by the product of two parametric constants, k and b. The constants k and b in the two rate control regimes of CaO-carbonation, chemical reaction control and diffusion control, have been determined as functions of temperature, respectively. The activation energy in the carbonation of surface CaO with CO₂ is estimated to about 72 kJ/mol regardless of the sources of CaO, however, that in the diffusion control regime appears differently as 102.5 (mesoporous CaO) or 189.3 kJ/mol (commercial-available CaO), possibly due to the morphological differences of the two CaO samples. From a practical point of view, the simple model equation proposed in this study deserves attention in that the CaO-carbonation behavior at working temperatures higher than 700 °C could be closely predicted.     

中煤级煤甲烷饱和吸附量的数值模拟计算

根据表征中煤级煤（镜质组最大反射率R_o,max=0.65%～2.50%）的系列等温吸附（20℃、30℃、40℃和50℃这4个实测温度）“煤变质程度-压力-吸附量”的三变量数学方程，建立一组“煤变质程度-温度-压力-吸附量”这4个共同存在并相互影响的四变量数学方程。该四变量数学方程用于预测1200m以浅的中煤级煤甲烷饱和吸附量。这种数学转换的平均相对误差在7.28%～9.49%之间。有处理中煤级煤甲烷饱和吸附量的数值模拟的软件著作。只要将5个实测数据：镜质组最大反射率R_0,max、温度梯度、压力梯度、埋深和恒温层温度，输入相应可编辑文本框中，就可以输出5个值：饱和吸附量V、温度-压力-吸附量方程中的参数（A、B、Δ、β）。还可以输出在自己感兴趣的镜质组最大反射率R_0,max、温度梯度、压力梯度、埋深和恒温层温度下，“R_0,max值时温压吸附曲面”和“吸附量随埋深变化图”。     

Interaction of ciprofloxacin hydrochloride with sodium dodecyl sulfate in aqueous/electrolytes solution at different temperatures and compositions

Interactions of ciprofloxacin hydrochloride(CPFH) with sodium dodecyl sulfate(SDS) were investigated by conductivity measurement in H_2O/electrolyte solutions(NaCl, Na_2SO_4 Na_3PO_4) over 298.15–318.15 K temperature range(with 5 K interval) considering the human body temperature. In all cases, two critical micelle concentrations(c~*) were observed which are increased in the presence of drug and decreased in the presence of salts enunciating the presence of interaction amongst the studied components. For(CPFH + SDS) system in the presence of salt, the c~*values at 303.15 K and I = 0.50 mmol·kg~(-1) followed the order: C_(NaCl)C_(Na_2SO_4)C_(Na_3PO_4). The ΔG_(1,m)~0 and Δ G_(2,m)~0values are found to be negative for all systems that show that the micellization process is thermodynamically spontaneous. For(CPFH + SDS) system in water, the Δ H_m~0 Δ S_m~0 values reveal that the micellization processes is both entropy dominated in almost all cases. In the occurrence of electrolytes, Δ H_m~0 and Δ S_m~0 values indicate that micellization processes are both entropy enthalpy restricted at upper temperature but it becomes totally entropy dependent at higher temperature. The higher positive Δ S_m~0 values indicate the enhanced hydrophobic interaction in presence of salts. The enthalpy-entropy compensation was determined from the linear relationship betweenΔ H_m~0 and Δ S_m~0 values in every state. Different transfer energies as well as compensation temperature and intrinsic enthalpy were also evaluated and the behaviors were comparable to other biological system.     

Cu-3-trz-PMo12的合成、结构及催化氧化碘离子性能

采用水热法合成了一例新的多酸基有机-无机杂化物,通过X射线单晶衍射、傅里叶变换红外光谱（IR）、热分析测试（TG）、X射线衍射分析（XRD）、扫描电子显微镜（SEM）、元素分析对化合物进行了表征。X射线单晶衍射分析结果表明,化合物的结构式为（PMo₁₂O₄₀） ［Cu₆（C₂H₄N₄）₆］（PMo₁₂O₄₀）?H₂O（简称为Cu-3-trz-PMo₁₂）,属于三方晶系,R-3空间群,晶胞参数a=1.756 66（3） nm、b=1.756 66（3） nm、c=2.303 24（6） nm、α=β=90°、γ=120°、V=6.155 2（3） nm³、Z=3、R₁=0.023 8、wR₂=0.059 2。化合物是由6个3-氨基-1,2,4-三氮唑、6个Cu⁺、两个经典的Keggin型［PMo₁₂O₄₀］^3-及一个间隙水分子组成的二聚体,两个这样的二聚体通过氢键交替相连形成次级单元,每个次级单元之间又通过氢键作用进而形成一个三维超分子结构。催化研究表明,该非均相催化剂在催化过氧化氢氧化碘离子中表现出较为优异的催化活性且具有较稳定的可重复性。     

POLYDISPERSITY IN FLUIDS, DISPERSIONS, AND COMPOSITES; SOME THEORETICAL RESULTS

We summarize some results of our theoretical study of polydispersity. After considering the effects of polydispersity on the structure of a solution or suspension of hard spheres in a continuum solvent, focusing on the pair distribution function g₂(r) we give some general relations between g₂(r) and thermodynamic quantities. For the log-normal and Shulz distributions, explicit analytic expressions are obtained for g₂(r) through first order in solute concentration, as well as corresponding expressions for the scattering function I(k). We also note the way hard-sphere polydispersity can be used to model monodisperse particles interacting via soft potentials and vice versa. Next we consider dispersions and composites consisting of a polydisperse distribution of particles or inclusions in a matrix (which can be a void or a solid or fluid continuum). Such systems include not only the solutions considered above but also a wide variety of solid porous and random media. Here we focus on the n-point matrix functions S_n, which give the probability that n points all lie in the matrix phase (as well as certain closely related functions), and consider transport and material properties (e.g., conductivity, modulii of elasticity) that can be expressed in terms of the S_n. We discuss in quantitative detail the (small) effects of polydispersity on such properties (via a study of S_n for n≤3rpar; for randomly centered spherical inclusions and parallel cylindrical inclusions with randomly placed axes. Finally, we discuss an application to gel size-exclusion chromatography, and consider some consequences of a polydisperse pore-size distribution.     

The electrochemistry of tellurium in methylene chloride

It was found that TeCl₄ in methylene chloride (containing tetrabutylammonium perchlorate as a supporting electrolyte) is reduced to TeCl₂, Te⁰ and Te⁻² in potential applied. Two reduction waves are observed during the reduction of TeCl₄ at a platinum rde (Ep₁ = 0.08 ± 0.02 V, Ep₂ = −1.10 ± 0.02 V) due to the reduction of TeCl₄ to Te and Te⁻² respectively. A cathodic deposition of tellurium from TeCl₄ is followed by anodic stripping wave (Ep₁ = 0.42 ± 0.02 V), corresponding to the oxidation of Te to TeCl₂. It has been shown that reduction of TeCl₄, or TeCl⁻²₆ to Te causes coating of the electrode with metallic tellurium, on whose surface chloride ions are strongly bonded. It was found that when the electrolysis solution contains excess of chloride ion with respect to Te^IV the peak potentials of the cathodic waves shift to more cathodic values (Ep₁ = 0.30 ± 0.02 V, Ep₂ = −1.25 ± 0.02 V). After cathodic deposition of at least a monolayer of tellurium from such a solution two anodic waves appear (Ep₁ = 0.12 ± 0.03 V, Ep₂ = 0.24 ± 0.03 V) which are both due to the oxidation of Te to Te^II.     

Organotin polymers: 6. Copolymerization parameters for tri-n-butyltin maleate, acrylate and methacrylate with some vinyl monomers

The monomer reactivity ratios for the copolymerization of methyl methacrylate (M₁), styrene (M₁), butyl acrylate (M₁) and acrylamide (M₁) with tri-n-butyltin maleate (M₂) have been found to be r₁ = 15.40, r₂ = 0.01; r₁ = 6.70, r₂ = 0.05; r₁ = 9.39, r₂ = 0.11; and r₁ = 122.44, r₂ = 0.06, respectively. Also, the copolymerization parameters of acrylamide (M₁) with tri-n-butyltin acrylate (M₂) or methacrylate (M₂) were as follows: r₁ = 0.11, r₂ = 0.82; and r₁ = 1.46, r₂ = 0.85, respectively. The Q and e values for the organotin monomers (tri-n-butyltin maleate, acrylate and methacrylate) were calculated from the monomer reactivity ratios determined in the present and previous studies. Copolymerization reactions were carried out in solution at 70°C using 1 mol% AIBN, and the copolymer compositions were determined by tin analysis. The structure of the tri-n-butyltin maleate and the prepared copolymers was investigated by i.r. spectroscopy.     

An experimental study of immiscible liquid–liquid dispersions in a pump–mixer of mixer–settler

Drop size distribution(DSD) or mean droplet size(d32) and liquid holdup are two key parameters in a liquid–liquid extraction process. Understanding and accurately predicting those parameters are of great importance in the optimal design of extraction columns as well as mixer–settlers. In this paper, the method of built-in endoscopic probe combined with pulse laser was adopted to measure the droplet size in liquid–liquid dispersions with a pump-impeller in a rectangular mixer. The dispersion law of droplets with holdup range 1% to 24% in batch process and larger flow ratio range 1/5 to 5/1 in continuous process was studied. Under the batch operation condition, the DSD abided by log-normal distribution. With the increase of impeller speed or decrease of dispersed phase holdup, the d32 decreased. In addition, a prediction model of d32 of kerosene/deionized system was established as d_(32)/D = 0.13(1 + 5.9φ)We~(-0.6). Under the continuous operation condition, the general model for droplet size prediction of kerosene/water system was presented as d_(32)/D = C_3(1 + C_4φ)We~(-0.6). For the surfactant system and extraction system, the prediction models met a general model as d_(32)/D = bφ~nWe~(-0.6).     

运用粒子图像测速仪研究双层桨搅拌槽内流体流动

The flow fields in a dual Rushton impeller stirred tank with diameter of 0.48 m （T） were measured by using Particle Image Velocimetry （PIV）. Three different size impellers were used in the experiments with diameters of D = 0.33T, 0.40T and 0.50T, respectively. The multi-block and 360° ensemble-averaged approaches were used to measure the radial and axial angle-resolved velocity distributions. Three typical flow patterns, named, merging flow, parallel flow and diverging flow, were obtained by changing the clearance of the bottom impeller above the tank base （C1） and the spacing between the two impellers （C2）. The results show that while C1 is equal to D, the parallel flow occurs as C2≥0.40T, C2≥0.38T and C2≥0.32T and the merging flow occurs as C2≤0.38T, C2≤0.36T and C2≤0.27T for the impellers with diameter of D=0.33T, 0.40T and 0.50T, respectively. When C2 is equal to D, the diverging flow occurs in the value of C1≤0.15T for all three impellers. The flow numbers of these impellers were calculated for the parallel flow. Trailing vortices generated by the lower impeller for the diverging flow were shown by the 10° angle-resolved velocity measurements. The peak value of turbulence kinetic energy （ k/V^2tip = 0.12-0.15 or above） appears along the center of the impeller discharging stream.