Mechanism and Rate of Dilute Iodine Vapor Absorption by Aqueous Sodium Hydroxide Solution

The rates of absorption of iodine vapor contained in air by aqueous sodium hydroxide solutions were measured at 298 K using a liquid jet column that established a contacting time between 0.006 and 0.025 sec.

The overall mass transfer coefficient varies in a complex manner depending on the concentrations of both iodine in the feed gas and sodium hydroxide in the absorbent solution. This results from the variation of the rate controlling step in the chemical reactions taking place in the liquid film. It was concluded from the present experimental work that the mechanism of iodine vapor absorption is as follows: Iodine in air dissolves into the aqueous phase through the gas liquid interface in conformity with Henry's law. This iodine in the aqueous phase forms hypoiodous acid and iodide ions through base catalytic hydrolysis, and then the resulting iodide ions react with the iodine to generate tri-iodide ions. The instantaneous dissociation reactions of water and of sodium hydroxide have to be taken into account. Iodate slowly forms from the hypoiodous acid, but this reaction has no influence upon the overall absorption rate under the conditions prevailing in the present instance.     

Dissolution of Gaseous Methyl Iodide into Aqueous Sodium Hydroxide Solutions

Absorption process of gaseous methyl iodide by water or sodium hydroxide solutions was investigated using a semi-flow type experimental apparatus by measuring the concentration of all measurable chemical species in both the gas and the liquid phase. The experimental temperature ranged from 288 to 311 K and the gaseous methyl iodide and aqueous sodium hydroxide concentrations were approximately 0.6×10^?3 to 7×10^?3 and 0 to 0.2 mol/dm³, respectively. It is estimated that the dissolution of methyl iodide into the sodium hydroxide solution proceeds according to the following steps.

Step (1) Methyl iodide in air dissolves physically into the aqueous phase. Physical dissolution process obeys Henry's law.

Step (2) Methyl iodide dissolved into the aqueous phase is decomposed by a base catalytic hydrolysis and produces methyl alcohol and iodide ion.

The equilibrium constants of physical dissolution were obtained from the steady concentration in both the gas and the liquid phases in the semi-flow type experiment because the hydrolysis reaction rate of methyl iodide is very slow in comparison with the physical dissolution in this experimental conditions. The obtained value of the standard heat of solution of methyl iodide into water was 7.2kcal/mol.

Salting-out effect was observed when the concentration of sodium hydroxide in the absorbent was over 0.01 mol/dm³.     

超强吸水树脂吸收模拟去污废液的初步研究

针对凝胶、泡沫、铈．硝酸、氢氧化钠和硝酸等模拟去污废液,进行了超强吸水树脂类型的筛选和吸液性能的初步研究。结果表明：HH、ND和SJ3种树脂的吸液比较大、吸液速率较快、耐酸性较好;吸液比、硝酸浓度和实验时树脂包裹的表面积均对吸液性能有影响,吸液速率随吸液比和硝酸浓度的增加而降低。     

Neutron Fluctuations in a Multi-Point Reactor

The effect of the presence of carbon dioxide on the partition equilibrium of iodine between air and aqueous sodium hydroxide solutions was investigated using a semiflow- and a batch-type experimental apparatus. The concentrations of all measurable chemical species were measured. The overall partition coefficient of iodine decreased significantly with the increase in the concentration of carbon dioxide in the gaseous phase. The concentration distributions of the participating iodine species in the aqueous phase varied significantly with the variation in the concentration of carbon dioxide. It was found that these experimental results are explained by considering the chemical reactions participated in the partition equilibrium and that the concentration dependency of overall partition coefficient is clarified with use of an approximate theoretical analysis.     

Analysis of hydrogen isotopes absorption between liquid lithium and yttrium under dynamic conditions

The use of D–Li stripping reaction to generate multiple neutron is expected in the International Fusion Materials Irradiated Facility (IFMIF). Tritium generated by its side reaction needs to be recovered from liquid Li for safety. Y hot trap is expected as an effective purification system to recover tritium from the liquid Li loop. In IFMIF, since liquid Li circulates in a loop, it is important to trace tritium behavior in Y and liquid Li under dynamic conditions. In this study, the authors investigate the effectiveness of tritium recovery from liquid Li under dynamic conditions of Y hot trap. Hydrogen absorption in Li instead of tritium is investigated under dynamically fluidized conditions by stirring liquid Li with an arbitrary rotational rate. The experimental results prove that the hydrogen absorption rate from liquid Li to Y is independent of the rotational rate. This means that the rate-determining step is hydrogen diffusion in Y.     

Analysis for iodine release from unit 3 of Fukushima Dai-ichi nuclear power plant with consideration of water phase iodine chemistry

The accident at unit 3 of the Fukushima Dai-ichi nuclear power plant was analyzed with THALES2 for the progression of severe accident coupled with Kiche for the iodine chemistry in aqueous phase. The analysis indicated that, compared with the analysis without the aqueous phase iodine chemistry, a significantly larger amount of iodine was released from the water pool of the suppression chamber (S/C) with forms of molecular iodine and organic iodine due to the repeated operation of the containment venting system. It was also implied in the sensitivity analysis that the late phase release of the volatile iodine species was largely influenced by the pH of the S/C water and gas–liquid mass transfer coefficient under a gas–liquid two-phase flow condition.     

碘硫循环中Bunsen反应液-液相分离影响因素的实验研究

Bunsen反应液-液相分离是整个碘硫循环的枢纽,H₂SO₄相与HI_x相分离效果直接影响整个循环系统的热效率。为提高两相分离效果和循环效率,对Bunsen反应平衡时液 液相分离特性进行研究。配制H₂SO₄、HI、I₂、H₂O混合溶液,研究实验条件对溶液分离效果的影响。研究结果表明,当n(H₂O)/n(H₂SO₄)小于18时,分层所需碘量随温度变化不大,之后随着溶液温度升高和水量增大,分层所需碘量明显增加;在提升温度和增加碘量的同时减小水量可有效提高溶液分离效果;增大水量可减小副反应进行程度,随着温度升高,抑制作用越明显。通过实验研究最终得到较好的分离条件。     

大平板上液膜冲击附板行为的数值模拟研究

利用FLUENT内的EWF模型对大平板上液膜冲击附板时发生的一系列流动行为进行了三维数值模拟研究。分析了不同工况下大平板上不同流量下降液膜冲击不同宽度和厚度附板后的液膜损失,并对比了一定高度返回槽收集水量的实验值和模拟计算值,两者吻合程度较为良好。分析了液膜冲击附板的流动行为的4个过程,并通过分析附板尺寸和液膜流量对液膜冲击附板行为的影响,得到了液膜损失率与受附板高度影响的液膜溅射空间数和液膜冲击附板时的韦伯数之间的关系,发现EWF模型在模拟降液膜冲击不同焊缝高度的附板时存在不足。     

Two-phase countercurrent flow in a model of a pressurized water reactor hot leg

The onset of flooding or countercurrent flow limitation (CCFL) determines the maximum rate at which one phase can flow countercurrently to another phase. In the present study, the experimental data of the CCFL for gas and liquid in a horizontal pipe with a bend are investigated. The different mechanisms that lead to flooding and that are dependent on the liquid flow rate are observed. For low and intermediate liquid flow rates, the onset of flooding appears simultaneously with the slugging of unstable waves that are formed at the crest of the hydraulic jump. At low liquid flow rates, slugging appears close to the bend; at higher liquid flow rates, it appears far away from the bend, in the horizontal section. For high liquid flow rates, no hydraulic jump is observed, and flooding occurs as a result of slug formation at the end of the horizontal pipe. The effects of the inclination angle of the bends, the liquid inlet conditions and the length of the horizontal pipes are of significance for the onset of flooding. A mathematical model of Ardron and Banerjee is modified to predict the onset of flooding. Flooding curves calculated by this model are compared with present experimental data and those of other researchers. The predictions of the onset of flooding as a function of the length-to-diameter ratio are in reasonable agreement with the experimental data.     

Degradation and mineralization of ciprofloxacin by gas–liquid discharge non-thermal plasma

A typical quinolones antibiotic ciprofloxacin(CIP) in aqueous solution was degraded by a gas–liquid discharge non-thermal plasma system. The discharge plasma power and the emission intensity of the excited reactive species(RS) generated in the gas phase were detected by the oscilloscope and the optical emission spectroscopy. The effects of various parameters on CIP degradation, i.e. input powers, initial concentrations addition of radical scavengers and p H values were investigated. With the increase of discharge power, the degradation efficiency increased but the energy efficiency significantly reduced. The degradation efficiency also reduced under high concentration of initial CIP conditions due to the competitive reactions between the plasma-induced RS with the degradation intermediates of CIP. Different radical scavengers(isopropanol and CCl_4) on ·OH and H· were added into the reaction system and the oxidation effects of ·OH radicals have been proved with high degradation capacity on CIP.Moreover, the long-term degradation effect on CIP in the plasma-treated aqueous solution proved that the long-lived RS(H_2O_2 and O_3, etc) might play key roles on the stay effect through multiple aqueous reactions leading to production of ·OH. The degradation intermediates were determined by the method of electrospray ionization(+)-mass spectroscopy, and the possible degradation mechanism were presented.     

A paradigm study for assessment of phenylalanine’s damage under arc-discharge irradiation

Energetic ions induce important biological effects and the research into radiolysis of amino acids can help to clarify radiolysis of proteins. For this purpose, arc-discharge induced radiolysis of the benzyl-containing aromatic amino acid phenylalanine in aqueous solution was studied and the damage was assessed quantitatively. The energetic ions were produced by arc-discharge in nitrogen and argon atmosphere. The arc-discharge induced chemical reactions of the biomolecule in aqueous solution were detected and analyzed by means of UV-Vis absorption, fluorescence, Fourier transformation infrared (FTIR) spectroscopy and high performance liquid chromatography (HPLC). Based on the multiple spectroscopic approach, the damage can be evaluated in a more reliable and convenient way. The fluorescence analysis in this case appears to be a more direct indicator for the assessment of damage, where it reveals that the damage increases with the irradiation time exponentially. On the contrary, the ‘plateau region’ or ‘saddle-shape’ apparently shown both in our rough absorption analysis and ninhydrin reaction test, similar to the previously reported feature of the dose effect for low-energy-ion induced damage, may be just a consequence with varied reactions and processes involved at different stages. This work thus demonstrated that application of appropriate combination of spectroscopic tools can effectively dissect the diversity of the radiolysis reaction system and assess the biomolecular damage properly.     

二甲基羟胺水溶液的脉冲辐解研究

利用脉冲电子束进行二甲基羟胺(DMHAN)水溶液的脉冲辐解研究,对其瞬态光谱中的主要吸收峰作了归属,并初步考察了这些瞬态物种的生长、衰减等行为。研究结果表明,·OH与DMHAN反应生成(CH3)2NO·自由基,测得速率常数为(4.5±0.3)×109mol-1·L·s-1;eaq-与DMHAN反应生成(CH3)2N·自由基,测得速率常数为(1.3±0.04)×109mol-1·L·s-1。     

Laser photolysis of ionic liquid [bmim][PF6]

Photoinduced chemical reactions of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF_6]) were studied by laser photolysis at a wavelength of 266 nm.Excited triplet state ~3[bmim]~ was observed,radical cation [bmim]~(2 ) and neutral [bmim] radical via photoionization were also formed.Energy transfer from ~3[bmim]~ toβ-carotene was confirmed.Oxidation via one electron transfer from TMPD to ~3[bmim]~ was also observed and the rate constant was determined to be 1.2×10.5 L.mol~(-1).s~(-1).The reaction of [bmim][PF_6] with hydrated electron (e_(aq)) was confirmed by laser photolysis in aqueous solution.     

气提泵在喷嘴板脉冲萃取柱中的应用

以30%TRPO/煤油溶液和1mol/LHNO3溶液为体系,研究气提泵在柱径100mm喷嘴板脉冲萃取柱中的应用规律。实验结果表明：设计的水相进料气提泵、有机相进料气提泵和水相出料气提泵的液体流量和气体流量均满足线性操作;特别是脉冲萃取柱分散相存留分数与水相吹口气提泵的浸没度之间也呈线性关系,并结合吹气法在线测量技术,可实现对脉冲萃取柱稳定操作进行有效控制。     

A model of silver–iodine reactions in a light water reactor containment sump under severe accident conditions

Metallic silver and iodine form insoluble AgI in the containment sump which has a major impact on iodine volatility and hence on the source term to the environment. Resistance-in-series models are developed and validated against separate-effects tests. The reaction between I₂ and Ag is limited by mass transfer in the liquid. The rate does not follow a parabolic law for the duration of the experiments. The extent of oxidation of the silver sample seems to play a decisive role for reactions with I⁻ which proceed via a two-step process. The initial, rapid step is controlled by the reaction with the surface silver oxide with a contribution of mass transfer in the liquid. The subsequent, slow step is limited by reaction between I⁻ and Ag⁺ at the solid–liquid interface. The reaction is probably negligible for pH > 7 and in the absence of oxidising conditions.     

Reaction rate of Na-based titanium nanofluid with water

Suppression of chemical reactivity in reaction between sodium (Na) and water by Na-based titanium nanofluid (NaTiNF) was verified by measuring the difference between the H₂ generation rates of NaTiNF–water reaction and sodium–water reaction (SWR). H₂ generation at the beginning of the reaction was slower in NaTiNF–water reaction than in SWR. To determine the effect of temperature on the reaction rate, NaTiNF–water reactions were conducted at 104 °C, 120 °C and 150 °C. At 104 °C, the reaction rate of SWR was twice as fast as NaTiNF–water reaction. This result demonstrates that the chemical reactivity of liquid Na is suppressed by the presence of Ti nanoparticles in liquid Na. The reaction rate of NaTiNF–water reaction increased with reaction temperature. The activation energy of NaTiNF–water reaction was obtained using the Arrhenius equation.     

Onset Criterion for Liquid Entrainment in Reflooding Phase of LOCA

Reflooding tests were conducted in a rod bundle geometry at the maximum pres- sure of 12 MPa to investigate thermal-hydraulic behavior during a small break loss-of-coolant accident (SBLOCA) in a nuclear reactor. The test conditions ranged 0.6 ～ 12 MPa for pressure, up to 920 K for rod surface temperature, up to 20 cm/s for bundle inlet flow velocity and up to 2 kW/m for linear power input. The principal objective of this paper is to investigate the onset condition for liquid entrainment by steam flow in the relatively high pressure reflooding phase. Experimental results showed a tendency that the liquid entrainment decreased with increase in pressure when the other parameters such as an inlet flow rate and rod temperature were fixed. A new correlation for the onset criterion for liquid entrainment was derived from the experimental results and an analysis of a force balance for a liquid droplet. Effects of pressure on liquid entrainment in the reflooding phase were made clear from the experimental and analytical results.     

Deformation and Fracture Behavior of Zircaloy-2 Deformed at Constant Strain Rate in Iodine Environment, (I)

The relation between strain rate and iodine stress corrosion cracking (SCC) was studied on Zircaloy-2 subjected to uniaxial stress under constant extension rate in an iodine partial pressure of 4 Torr and at a temperature of 350°C. The specimens were machined from actual fuel cladding tube. In iodine environment, the tangentially directed specimens registered sharp decreases in stress beyond maximum point; this is attributed to crack initiation and propagation. Fracture ductility diminished with decreasing strain rate. Severe SCC was observed at strain rates below 2×10^?3min^?1. At high strain rates, the mechanism governing the rate of SCC appeared to be the time-dependent corrosion process. The axially directed specimens showed no signs of embrittlement due to gaseous iodine; this is attributed to the particular texture of the Zircaloy. Fracture surface observations indicated that transgranular cleavage fracture along the basal plane appeared to play a significant role in the stages of SCC initiation and propagation.     

空气脉冲对吹气法测量脉冲萃取柱下澄清段压力的影响

本工作实验考察在吹气条件下空气脉冲对脉冲萃取柱下澄清段所测量的柱重、有机相密度、两相界面和水相密度的时均压降影响。实验结果表明：在无空气脉冲且流速为零、有空气脉冲且单相流流速为零和有空气脉冲且单相流流速不为零的条件下，吹气法所测量的有机相密度、水相密度及两相界面的时均压降是一致的，而在有空气脉冲且两相流速均不为零的条件下，吹气法所测量的水相密度、有机相密度和两相界面的时均压降误差依次增大。对于有机相，吹气法所测量的柱重时均压降随着空气脉冲振幅的增加而减小，随着流速增加而增大；对于水相，由于其流动方向与有机相相反，柱重时均压降随流速的增加而减小。     

Thermodynamic Evaluation of Liquid Cd Cathode Containing U and Pu

In our previous study, a mixture of U and Pu was recovered in liquid Cd cathode from molten salt under various conditions of the U:Pu ratio. Two important things were observed. The first was that three kinds of precipitated phase had been detected in the saturated liquid Cd cathode, such as a U metal and two kinds of U-Pu-Cd compound. The compositions of the compounds were roughly (U+Pu):Cd = 1:11 and (U+Pu):Cd = 1:6. The second was that the U metal had selectively precipitated in the saturated liquid Cd cathode under the condition that the U:Pu ratio is higher than about 0.8 in the liquid Cd phase. In the present study, phase diagrams were evaluated by the CALPHAD method on the liquid Cd cathode containing U and Pu. The U-Pu-Cd compounds were modeled as MCd11-type and MCd6-type, respectively, based on the reported binary phase diagrams of U-Cd and Pu-Cd. The calculated result reasonably agreed with the experimental observations. The variations in the U and Pu activities were estimated along with the U:Pu ratio, which is related to the precipitation of various phases in the liquid Cd cathode.