分光光度法测定水样中铝

在ｐＨ＝ ５－３ 的ＨＡｃ ＮａＡｃ 缓冲介质中，铝与三氯偶氮胂形成量比为１∶２ 的络合物，最大吸收峰位于６２０ ｎｍ 处。该体系的表观摩尔吸光系数ε６２０ｎｍ ＝ ３－６５ ×１０４ Ｌ／（ｍ ｏｌ·ｃｍ） ，铝的质量浓度在０ ～０－４８ ｍｇ／Ｌ 范围内遵守比尔定律。本法用于水样中铝的测定，结果满意。     

催化剂中微量铂的催化极谱测定

本文研究并提出了催化极谱法测定催化剂中微量铂的体系。０．１５ｍｏｌ／Ｌ磷酸氢二铵－０．５ｍｏｌ／Ｌ硫酸４．０×１０＾－３ｍｏｌ／Ｌ六次甲基甲胺底液中,于－１．０２伏（ｕＳ．ＳＣＥ）产生一灵敏的催化波,线性范围１．０×１０＾－５－８．０×１０＾－３μｇ／ｍｌ。本体系选择性好,数十种常元素无干扰,可不经分离富集直接测定催化剂中微量铂。     

对甲基二溴偶氮胂直接光度法测定微量锆

本文研究了锆与新试剂对甲基二溴偶氮胂（ＤＢＭＡ）的显色反应。在０,８ｍｏｌ／Ｌ盐酸介质中,锆与该试剂形成蓝色配合物,它的最大吸收波长为６３８ｎｍ,表观摩尔吸光系数为５．２×１０￣４Ｌ．ｍｏｌ￣（－１）·ｃｍ￣（－１）,锆浓度在０～２０μｇ／２５ｍｌ时服从比尔定律。方法用于测定铝、镁、铜等合金中的锆,获得满意结果。     

钢中稀土的极谱测定

在ｐＨ９．３的１．４×ｌ０－２ｍｏｌ／Ｌ硼砂－５．３×ｌ０－２ｍｏｌ／Ｌ氨水底液中，稀土－百里香酚酞络合剂有一灵敏的极谱波，其二次导数波峰电位Ｅ″ｐ＝－１．０２伏（Ｓ．Ｃ．Ｅ）。波高与稀土离子浓度在４．０×１０－７～３．６×１０－６ｍｏｌ／Ｌ范围内有良好的线性关系。试验考察了影响极谱波的各种因素和共存离子的干扰，将此极谱波应用于钢中轻稀土的测定，结果准确。     

阳离子型微乳液介质中铜（Ⅱ）──苯基荧光酮的增敏试验

本文研究了在阳离子型微乳液介质中，用苯基荧光酮测定铜（Ⅱ）的吸光光度法。试验结果表明，以阳离子型Ｏ／ＷＣＴＭＡＢ／ｎ—Ｃ５Ｈ１１ＯＨ／ｎ—Ｃ７Ｈ１６／Ｈ２Ｏ微乳液为介质，Ｃｕ（Ⅱ）－ＰＦ的ε５７２＝１．３７×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，与以水为为介质ε５４０＝４．３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１及相同含量ＣＴＭＡＢ０／Ｗ胶束溶液为介质ε５７２＝８．９×１０４Ｌ·ｍｏｌ－１·ｃｍ－１比较，测定灵敏度显著提高，并且某些实验条件更加宽容。经投入使用，结果令人满意。     

P_（507）（煤油）／（Sm－Eu－Gd）Cl_3（EuCl_2）－HCl体

本文在选定的工艺条件下，在振动筛板柱中研究了Ｐ（５０７）（煤油）／（Ｓｍ－Ｅｕ－Ｇｄ）Ｃｌ３（ＥｕＣｌ２）－ＨＣｌ体系的两相流动特性和传质特性。结果表明，该体系在振动柱中有良好的流动特性。在流比２．５～４．０，振幅＝１０ｍｍ，频率＝３００～３５０ｍｉｎ（－１）条件下，两相总液泛通量达２２０Ｌ／ｄｍ２·ｈ，存留分数一般为１２～１５％。用分段近似计算法，估算了柱子的传质效率。对于较难萃取的组分Ｓｍ，平均传质单元高度为０．５２ｍ，平均理论级当量高度为１．８２ｍ。     

铋─4－（2－噻唑偶氮）间苯二酚络合吸附波研究

在０．１２ｍｏｌ／ＬＮａＯＨ底液中,Ｂｉ（Ⅲ）－ＴＡＲ络合物产生－灵敏吸附还原峰,用单扫示波极谱法测定,铋的浓度在３×１０￣（－８）～１×１０（－６）ｍｏｌ／Ｌ范围内与峰高呈良好的线性关系。将该法应用于矿石中痕量铋的测定,结果令人满意。并对络合吸除波的性质进行了初步研究。     

DBF－偶氮氯膦与锶显色反应的研究及应用

本文研究了新显色剂ＤＢＦ－偶氮氯膦与锶的显色反应。在１．２ｍｏｌ／ＬＨＣＬ介质中试剂与锶反应形成１：２的蓝色配合物,其最大吸收峰在６３０ｎｍ波长处,表现摩尔吸光系数为５．０×１０￣４Ｌ·ｍｏｌ￣－１·ｃｍ￣－１,锶量在０￣１４μｇ／２５ｍｌ范围内符合比尔定律。方法用于锶硅铁合金中锶的直接光度测定获得了满意结果。     

偶氮二安替比林光度法测定铝合金中镍

研究２,７－双［（安替比林）偶氮］－１,８－二羟基萘－３,６－二磺酸（偶氮二安替比林）与镍（Ⅱ）的显色反应条件。在ｐＨ９的硼砂－盐酸缓冲介质中,试剂与镍（Ⅱ）形成稳定的１：２的蓝色络合物,其最大吸收峰在６３２ｎｍ处,表观摩尔吸光系数为３．９６×１０４Ｌ·ｍｏｌ－１·ｃｍ－１,镍量在５～２μｇ／５０ｍｌ范围内符合比尔定律,用于铝合金中镍的测定获得了满意结果。     

MNA—TBP从盐酸介质中萃取Ir（IV）

对ＭＮＡ－ＴＢＰ从盐酸介质中萃取Ｉｒ（Ⅳ）作了研究。结果表明：ＭＮＡ－ＴＢＰ对Ｉｒ（Ⅳ）萃取有协同效应。当ＭＮＡ和ＴＢＰ在正辛烷中的浓度各为０．４５ｍｏｌ／Ｌ，待萃液中ＨＣｌ总浓度为４ｍｏｌ／Ｌ，铱浓度为１７３．１３μｇ／ｍｌ，相比为１时，协萃系数Ｒ为２．３３，协萃合物的组成为（ＭＮＡＨ）＾＋．ＩｒＣｌ６＾２－．（ＨＴＢＰ）＾＋。     

硫酸钴中铁的测定──萃取分离原子吸收光谱法

硫酸钴中铁的测定主要问题是存在钴基体对测定方法严重干扰。本文提出了在约7mol／L盐酸介质中，用乙酸乙酯萃取与钴分离，然后用水反萃取，在（1＋19）的盐酸介质中，以空气-乙炔火焰，于原子吸收光谱仪波长248．3nm处测定。本文还对方法的精密度和准确度等作了考查，结果令人满意。     

Kinetics of hydrochloric acid leaching of smithsonite

The dissolution kinetics of smithsonite ore in hydrochloric acid solution has been investigated. As such, the effects of particle size (−180 + 150, −250 + 180, −320 + 250, −450 + 320 μm), reaction temperature (25, 30, 35, 40, and 45°C), solid to liquid ratio (25, 50, 100, and 150 g/L) and hydrochloric acid concentration (0.25, 0.5, 1, and 1.5 M) on the dissolution rate of zinc were determined. The experimental data conformed well to the shrinking core model, and the dissolution rate was found to be controlled by surface chemical reaction. From the leaching kinetics analysis it can be demonstrated that hydrochloric acid can easily and readily dissolve zinc present in the smithsonite ore, without any filtration problems. The activation energy of the process was calculated as 59.58 kJ/mol. The order of the reaction with respect to HCl concentration, solid to liquid ratio, and particle size were found to be 0.70, −0.76 and −0.95, respectively. The optimum leaching conditions determined for the smithsonite concentrate in this work were found to be 1.5 M HCl, 45°C, −180 + 150 μm, and 25 g/L solid to liquid (S/L) ratio at 500 rpm, which correspond to more than 95% zinc extraction. The rate of the reaction based on shrinking core model can be expressed by a semi-empirical equation as:

Kinetic Study and Mathematical Model of Hemimorphite Dissolution in Low Sulfuric Acid Solution at High Temperature

The dissolution kinetics of hemimorphite with low sulfuric acid solution was investigated at high temperature. The dissolution rate of zinc was obtained as a function of dissolution time under the experimental conditions where the effects of sulfuric acid concentration, temperature, and particle size were studied. The results showed that zinc extraction increased with an increase in temperature and sulfuric acid concentration and with a decrease in particle size. A mathematical model able to describe the process kinetics was developed from the shrinking core model, considering the change of the sulfuric acid concentration during dissolution. It was found that the dissolution process followed a shrinking core model with “ash” layer diffusion as the main rate-controlling step. This finding was supported with a linear relationship between the apparent rate constant and the reciprocal of squared particle radius. The reaction order with respect to sulfuric acid concentration was determined to be 0.7993. The apparent activation energy for the dissolution process was determined to be 44.9 kJ/mol in the temperature range of 373 K to 413 K (100 °C to 140 °C). Based on the shrinking core model, the following equation was established: $$ 1.21\ln \left( {1 - 0.83x} \right) - \left[ {1.02\ln \frac{{0.35 + \left( {1 - x} \right)^{{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-0pt} 3}}} - 0.59\left( {1 - x} \right)^{{{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0pt} 3}}} }}{{0.35 + \left( {1 - x} \right)^{{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-0pt} 3}}} + 1.18\left( {1 - x} \right)^{{{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0pt} 3}}} }} + 3.52\arctan \left( {1.96\left( {1 - x} \right)^{{{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0pt} 3}}} - 0.58} \right)} \right] + 2.06 = 42,192.59{\text{e}}^{{ - \frac{44,900}{{{\text{R}}T}}}} t. $$      

甲醛-硫酸亚铁协同还原浸出低品位氧化锰矿

在硫酸介质中以甲醛-硫酸亚铁为还原剂协同还原软锰矿,考察了甲醛-硫酸亚铁摩尔比、温度、反应时间、转速、硫酸浓度等因素对锰、铝的浸出率及溶液中铁和有机残留甲酸的影响.采用单因素实验获得较佳的还原工艺条件,采用HPLC测定溶液中的甲酸.结果表明,在固定转速为200 r/min、液固比为8 ml/g时,最佳反应条件为:甲醛-硫酸亚铁摩尔比1∶3(甲醛1.5 mol)、浸出时间3 h、硫酸浓度3 mol/L、温度90℃.在该条件下重复实验,锰的平均浸出率为93.51%,铝的平均浸出率为33.08%,铁的浓度为23.07 mol/L,甲酸浓度为0.001 g/L.     

Determination of Gibbs Energy of Formation of Molybdenum-Boron Binary System by Electromotive Force Measurement Using Solid Electrolyte

The standard Gibbs energies of formation of Mo₂B, ??MoB, Mo₂B₅, and MoB₄ in the molybdenum-boron binary system were determined by measuring electromotive forces of galvanic cells using an Y₂O₃-stabilized ZrO₂ solid oxide electrolyte. The results are as follows: $$ \begin{aligned} \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{Mo}}_{2} {\text{B}}} \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 193100 + 44.10T \pm 700\left( {1198{\text{ K to }}1323{\text{ K}}\left( {925^\circ {\text{C to }}1050^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ (\alpha {\text{MoB}})/{\text{J}}\,{\text{mol}}^{ - 1} & = - 164000 + 26.45T \pm 700\left( {1213{\text{ K to }}1328{\text{ K}}\left( {940^\circ {\text{C to }}1055^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{Mo}}_{2} {\text{B}}_{5} } \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 622500 + 117.0T \pm 3000\left( {1205{\text{ K to }}1294{\text{ K}}\left( {932^\circ {\text{C to }}1021^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{MoB}}_{4} } \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 387300 + 93.53T \pm 3000\left( {959{\text{ K to }}1153{\text{ K}}\left( {686^\circ {\text{C to }}880^\circ {\text{C}}} \right)} \right) \\ \end{aligned} $$ where the standard pressure is 1 bar (100 kPa).     

极谱法测定铝合金中锆

利用锆（Ⅳ）在盐酸介质中能与水杨基荧光酮（SAF）形成非电化学活性络合物的性质,建立了以测定水扬基荧光酮的还原峰电流而间接测定锆的极谱新方法。该方法最佳底液组成为：0.24 mol/L的盐酸,8.0×10-5 mol / L的水杨基荧光酮乙醇溶液,2.4 mg/L的聚乙二醇（20 000）溶液。Zr（Ⅳ）在-0.68 V（vs.SCE）左右有一尖锐的极谱峰,峰电流与Zr（Ⅳ）浓度在0～840μg /L范围内成线性关系,检出限为0.004 2 μg /L。将该法与微波消解的溶样方法相结合测定了铝锆合金标准样品中锆,测定结果与认定值相符。用单扫描极谱法研究了锆的极谱行为,证明了电极反应物为水杨基荧光酮,极谱波为不可逆还原吸附波。本方法适用于铝锆合金中含量≤10%的锆测定。     

离子交换法回收废钨催化剂碱浸液中钨的研究

用201树脂离子交换回收废钨催化剂碱浸液中钨,研究了交前液流速、温度及所含阴离子杂质对钨吸附的影响和不同解吸剂解吸钨的影响。结果表明,交前液的流速从2．0mL／min增加到8．0mL／min,WO3的饱和交换容量从332．9mg／g减少到150．9mg／g。当交前液含10g／LAlO2、10g／L,CO3^2-和5g／L OH^-时．饱和交换容量相应减少为169．2、201．6和231．04mg／g。用2mol／LNaCl和1mol／LNaOH的混合液解吸效果好,解吸率可达98．2％。     

Interaction behavior of nitrogen in liquid niobium

The kinetics and mechanism of absorption/desorption of nitrogen in liquid Nb were investigated in the temperature range of 2470 °C to 2670 °C in samples levitated in a N₂/Ar stream with various nitrogen partial pressures. The nitrogen solution reaction in liquid Nb was found to be exothermic, with the standard enthalpy and entropy of solution of −236.4 ± 23.3 kJ/mol and −-5.3 ± 8.3 J/K · mol, respectively. Above the threshold flow rate of the N₂/Ar stream, the absorption process was determined to be second order with respect to nitrogen concentration, indicating that the rate-controlling step is either the adsorption of nitrogen molecules on the liquid surface or dissociation of adsorbed nitrogen molecules into surface-adsorbed atoms. The desorption process was found to be second order as well. At lower flow rates, however, the absorption rate was found to depend on the gas-phase mass transfer rate. The rate equation for nitrogen absorption in the range of 2470 °C to 2670 °C is given by with the value ofQ calculated to be −327.2 ± 20.6 kJ/mol, while nitrogen desorption at 2670 °C follows the relation      

强化目标管理 降低高炉煤气放散率

阐述了唐钢炼铁新区运用目标管理方法,使高炉煤气放散率从１９９５年的２５．４％,降到１９９７年的５．５％的显著效果,以及组织目标实施的具体做法。