铜矿物相分析研究——次生铜矿与原生铜矿之分离

在铜矿物相分析中,一般只分析铜的氧化物(包括硫酸盐、碳酸盐、氧化物及硅酸盐等),次生硫化物(包括铜蓝、辉铜矿及斑铜矿等),和原生硫化物(包括黄铜矿、方黄铜矿)。基本上已能满足生产上的要求。其中氧化矿的浸出是用5%H_2(?)O_4为浸取剂,在一般情况下均能普遍适用。而关于作氰化钾溶液浸出次生硫化铜这方法从质量上来讲也是能满足要求的,但氰化钾为一剧毒之化学试剂,应尽可能避免使用,况且当浸取过程结束以后,在定量步骤上也产生繁复而危险的过程,在破坏氰化钾时将产生剧毒之氰化氢气体等,这     

多金属硫铁矿铜锌物相分析

有关岩石试样中铜锌物相分析,国内外已有许多研究,确定了不少常规分析流程。其中氧化铜与硫化铜的分离方法有H_2SO_(4~-)Na_2SO_3法、乙二胺法、(NH_4)_2CO_(3~-)NH_4OH法、HAc-Na_2SO_3法等。经作者试验,上述方法应用于含铜、铅、锌等元素的多金属黄铁矿试样,特别是含有较多活性硫化物(辉铜矿、斑铜矿、磁黄铁矿等)的试样时存在一定的问题。当用含有铵盐的试剂浸取氧化铜时,由于辉铜矿及斑铜矿的部分被浸取,使氧化铜的结果严重偏高;若采用H_2SO_4—Na_2SO_3酸法浸取时,则因各种共存活性硫化物的电化作用,使氧化铜的结果也徧高,在强酸介质中,由于会发生Cu~(2+)+ZnS(PbS)(?)CuS↓+Zn~(2+)的反应,使结果偏低。为克服上述问题,本文提出用50毫升15％乙酸-1毫升饱和氯化汞-1.2克无水     

遗传算法用于地质样品中钴、镍五种相态的同时测定

根据地质样品中钴、镍硫酸盐、镍黄铁矿、橄榄石、磁铁矿、菱铁矿5种相态不同的化学性质,选择了浸取剂,确定了最佳浸取条件,获取了各相态稳定的浸取率常数,并将遗传算法与钴、镍的化学物相分析相结合,建立了地质样品中钴、镍的五种相态同时测定的方法。方法简便、快速。其钴、镍的RSD(%)分别为:硫酸盐1.2、0.5,镍黄铁矿3.0、0.7,橄榄石1.0、0.25,磁铁矿2.9、2.4,菱铁矿5.5、2.4。平均相对误差小于5%。     

四川拉拉铜矿中辉铜矿、黄铁矿和黄铜矿的分离

本文研究了四川拉拉铜矿中辉铜矿、黄铁矿和黄铜矿的分离。采用硫酸(5+95)加氟化物溶解总氧化铜,及用硫脲-盐酸溶解次生硫化铜(辉铜矿等)后,提出用硝酸(1+1)溶浸黄铁矿而与黄铜矿分离。     

遗传算法用于地质样品中铁的相态分析的研究

采用遗传算法 ( GA)进行地质样品中铁的五种相态同时测定 ,建立了反映各相态浓度、浸取率与总浸取量之间关系的数学模型及六种浸取剂对铁的五种相态的最佳浸取条件 ,讨论了遗传算法中目标检验函数对铁的相态分析的影响 ,并验证了方法的准确度和精密度 ,证明此方法简便、快速、实用。     

电解重量法测定混合铜矿中自由氧化铜

建立了用于混合铜矿石中自由氧化铜测定的方法。试样用含亚硫酸钠(6g/L)的硫酸(10%)溶液浸取2h,选择性溶解铜氧化物,过滤并煮沸滤液,用去离子水稀释后电解。溶液中的铜离子电积至阴极铂网上。用火焰原子吸收光谱法检测残余于电解后液中的铜离子;同时用硝酸(1+1)溶解铂网上的铜,并用火焰原子吸收光谱法检测与阴极铜共电积的杂质元素含量,用铂阴极差重加上电积后液残余铜含量并减去共电积的杂质元素含量可计算出氧化铜矿中酸溶铜含量。与碘量法相比,不用肉眼观察颜色变化确定终点,人为误差小,结果稳定、准确。通过对加拿大氧化铜矿标准物质AMIS0050进行测定(n=12),方法准确度可靠。并选取15批次的氧化铜矿检测,与经典碘量法比对,结果令人满意。     

电重法测定混合铜矿中自由氧化铜的方法研究

本方法用于混合铜矿石中自由氧化铜的测定。试样用含0.6%（m/v）亚硫酸钠的10%(v/v)硫酸溶液浸取两小时,选择性溶解铜氧化物,过滤并煮沸滤液,用去离子水稀释后电解。溶液中的铜离子电积至阴极铂网上。用火焰原子吸收分光光度法检测残余于电解后液中的铜离子;同时用1 1硝酸溶解铂网上的铜,并用火焰原子吸收分光光度法检测与阴极铜共电积的杂质元素含量,用铂阴极差重加上电积后液残余铜含量并减去共电积的杂质元素含量可计算出氧化铜矿中酸溶铜含量。此方法相比国标碘量法,用肉眼观察颜色变化确定终点,人为误差小,结果稳定、准确。通过对加拿大氧化铜矿标准物质AMIS0050进行测定(n=12),方法准确度可靠。并选取十五批次的氧化铜矿检测,与经典碘量法比对,结果令人满意。     

系统聚类法及其在铅形态分析中的应用

针对常规化学形态分析方法对浸取剂高选择性要求及严重串相问题等缺点,在浸取常数稳定的前提下,以常规化学形态分析方法为基础,确定了建立标准样本的方法,将系统聚类法用于模拟地质样品中各形态铅的同时测定。克服了串相问题及降低了对浸取剂高选择性的要求,用此法对模拟样品进行了分析,相对误差小于±11%,结果优于常规化学形态分析方法。     

离子吸附型稀土矿中浸出相稀土元素含量的浸取方法研究

将风化壳离子吸附型稀土矿原矿样品加工至0.149 mm,使用35 g/L硫酸铵溶液(pH为4.0)作为浸取剂,提取浸出相稀土元素.考察了提取浸出相稀土元素时,样品粒度、浸取剂浓度及用量、浸取剂酸度、浸取方式、浸取时间等条件的影响,确定最佳试验条件,利用电感耦合等离子体质谱法(ICP-MS)测定样品溶液中浸出相稀土的总量...     

配位化合物中的线性热力学函数关系——Ⅱ.离子选择电极研究α-氨基酸与铜(Ⅱ)配合物在混合溶剂中的线性热力学函数

用铜离子选择电极测定五种α-氨基酸(对氟苯丙氨酸、丝氨酸、缬氨酸、丙氨酸及α-氨基异丁酸)的铜(Ⅱ)配合物在25.0±0.1、35.0±0.1和45.0±0.1℃,μ=0.16mol L~(-1)KNO_3时于水中及30%(V/V)和50%(V/V)的乙醇-水中的稳定常数.用pH电位法测定了各配体在混合溶剂中的离解常数.实验表明用铜离子选择电极研究上述配合物在混合溶剂中的线性自由能、线性焓和线性熵关系,得到了较好的结果.     

硫化铜精矿物相分析及氧化机理研究

在海轮运输及样品的制备过程中,进口硫化铜精矿氧化的现象普遍存在,使得货物的重量和铜品位发生变化,但该种现象的机理研究不多。针对硫化铜精矿的物相进行分析,并对硫化铜精矿的氧化机理进行研究。首先,利用显微镜、扫描电子显微镜、X射线荧光光谱(XRF)、X射线衍射(XRD)等方法对两个硫化铜精矿进行物相分析,并对其中的主要元素和含铜主要物相进行定量化学分析。再次,利用热重分析(TGA)研究这两个硫化铜精矿发生氧化反应的温度,结果表明在400℃时铜精矿样品重量开始增加,在约650℃重量达到顶峰,随后重量开始下降。最后,分别在400、650和900℃对两个铜精矿样品进行灼烧,并利用XRF和XRD方法进行测定,从而研究铜精矿的氧化机理,结果表明在400℃时,出现了铁的氧化物和铜的硫氧化物,说明黄铜矿和黄铁矿开始氧化,但还没有完全氧化,在650℃时,化合物中的氧含量继续增加,硫含量逐步减少,在900℃时,铜和铁的化合物只剩氧化物,硫已全部被氧化。结果表明,硫化铜精矿中的铜、铁等元素在温度和时间的作用下逐步氧化,硫氧化物的产生为中间态,氧化物的产生为最终态。实验解释了进口硫化铜精矿氧化的原理,有助于贸易双方减少分歧,有助于海关技术中心更规范地制备样品,降低数据误差。     

氧化与还原条件下伊通河长春区段沉积物重金属形态特征的对比研究

利用改进的Tessier连续萃取法研究了伊通河长春市自由大桥处不同深度沉积物样品在氧化及还原条件下Cu,Pb,Zn和Ni的形态变化规律,同时分析了沉积物样品中酸可挥发性硫(Acid volatile sulfide,AVS)和同时提取重金属(Simultaneous extract metals,SEM)的含量. 实验结果表明，样品经干燥、研磨处理后,Cu有机/硫化物结合态比例减少40%,锰氧化物结合态的比例显著增加; Pb,Zn和Ni 3种元素有机/硫化物结合态比例均略有下降,变化幅度小于Cu,并重新分配到不同的化学相中. 通过SEM中各金属含量与有机/硫化物结合态中金属含量的对比可知,还原性沉积物中Cu除了与硫化物结合外,很大一部分是以有机物形态存在的,Pb,Zn,Ni,Fe和Mn则主要以硫化物形态存在,各元素形态分析均不同程度地受到萃取剂的影响.     

Mechanism of Passive Layer Formation during Electrochemical Oxidation of Copper(I) Sulfide

Russian Journal of Electrochemistry - The structure and phase composition of synthesized copper(I) sulfide are studied. It is shown that, both chalcocite (Cu2S) and jarleite (Cu31S16) phases can...     

Sequential atomic absorption spectrometric determination of nitrate and nitrite in meats by liquid-liquid extraction in a flow-injection system

Sequential determinations of nitrate and nitrite based on continuous liquid-liquid extraction, and suitable for their routine determinations in meats, are reported. Nitrate reacts with bis(2,9-dimethyl-1,10-phenanthrolinato)copper(I) to form an ion-pair which is extrated into 4-methyl-2-pentanone in a flow-injection manifold. In one aliquot of sample, nitrite is oxidized by cerium(IV), so that total nitrate is determined. In another, nitrite is converted to nitrogen with sulfamic acid, so that only the original nitrate is determined. By measuring the atomic absorption signal of copper in the organic phase, mixtures of these anions can be determined at μg ml^?1 levels for nitrate/nitrite ratios from 10:1 to 1:10, with a sampling frequency of ca. 20 h^–1.     

Effect of mixing ratios of natural inorganic additives in removing ammonia and sulfide in the liquid phase during anaerobic digestion of slaughterhouse waste

In this study, the efficacy of inorganic additives in the removal of total ammonia nitrogen (TAN) and sulfide in the aqueous phase of slaughterhouse waste undergoing anaerobic digestion in the batch reactor was investigated. A mixture of natural inorganic additives processed from the anthill and red rock soil samples collected from Arusha, Tanzania were used as adsorbents in different ratios. These materials were chosen in regard to their abundance in the local environment, surface properties, and elemental composition. Before analysis, the materials were pulverized and calcined at 700 and 900 °C for 2 h in a furnace and then sieved to 250 μm fine particle size. XRD analysis revealed that the anthill soil sample is endowed with major mineral phases of quartz and hematite while red rock soil contains albite, pyroxene, and quartz as predominant phases. The anthill and red rock soil samples calcined at 900 °C displayed higher BET surface areas of 815.35 and 852.35 m²/g, respectively. The mixture of anthill soil and red rock soil in a ratio of 3:1 had a higher TAN removal efficiency of 92% at a contact time of 30 min compared to other ratios. On the other hand, a ratio of 1:2 showed a higher sulfide removal efficiency of 79% at a contact time of 60 min. Adsorption isotherm studies revealed that the Jovanovich model fitted better to the experimental data than the Langmuir and Freundlich models. The results demonstrated further that inorganic additives have a synergistic effect on stimulating methanogenesis as well as eliminating ammonia and sulfide during anaerobic digestion of slaughterhouse waste. Our findings demonstrate that anthill and red rock soils can be exploited as affordable, ecofriendly, and efficient adsorbents for mitigation of TAN and sulfide from the liquid phase and sustenance of methanogenesis.     

Determination of tin in titanium alloys

Tin-titanium alloys are becoming increasingly important; consequently a good method is needed for the determination of tin in this type of material. In this paper an accurate iodometric procedure is proposed for the determination. The sample is dissolved in sulfuric acid and the titanium oxidized with potassium permanganate. Tartaric acid is added and the tin precipitated with hydrogen, sulfide. The sulfide precipitate is dissolved in a mixture of sulfuric, perchloric and nitric acids and the solution evaporated to fumes of sulfuric acid. Water and hydrochloric acid are added, and the tin is reduced with lead and antimony trichloride and titrated with iodine. A study was made of the interfering elements that might be found in titanium alloys. The effect of antimony trichloride in reducing interference from copper was investigated. The method is recommended for titanium alloys containing 0.05 to 5.0 per cent. tin.     

A facile electrochemical synthesis of covellite nanomaterials at room temperature

A novel method for the electrochemical synthesis of covellite (CuS) nanoparticles (NPs) in aqueous phase was developed. In this experiment, thioglycerol (TG) is used as the catalyst for the hydrolysis of sodium thiosulfate, the sulfur source for the synthesis of CuS. Cu foil, which acts as the sacrificing anode, is oxidized to Cu²⁺ by applying a potential of 0.5 V while OH^- was produced on the cathode surface at the same time. The production of OH^- facilitates the reaction between Cu²⁺ and thiosulfate under the catalysis of TG. The evolution of hydrogen bubbles effectively prevents the deposition of copper sulfide on the cathode. Copper sulfide sols of “golden-brown”, and “dark-green” forms can be obtained by varying the concentration of TG. The “golden-brown” copper sulfide sols are also observed to convert to the green form with time, and the rate of this conversion process is faster at higher temperatures. X-ray diffraction (XRD) and chemical analysis indicate that the “dark-green” form of product is pure hexagonal phase CuS. The obtained CuS NPs were covered by a layer of TG as suggested by Fourier transform infrared (FTIR) data. The size and morphology of the particles are studied by transmission electron microscope (TEM).     

Comparison of active and passive environmental sampling for safeguards applications

Towards development of electrical conductivity based sensors for online detection of formation of third phase during reprocessing of Pu rich spent nuclear fuels, laboratory studies were carried out using U⁴⁺ solutions in various experimental conditions. Third phases were generated by extracting U⁴⁺ from nitric acid medium by 1.09 M TBP at different A/O (A: aqueous, O: organic) ratios. The results of this study indicate that the third phase is nearly 100–300 times more conducting than lean organic phase and saturated phase. The higher conductivity of third phase as compared to that of other two phases is explained based on the principle of reverse micelle formation and charge movement between the micro emulsion globules by percolation phenomenon.     

Resolution of matrix effects on analysis of total and methyl mercury in aqueous samples from the Florida Everglades

 Aqueous samples from the Florida Everglades present several problems for the analysis of total mercury (HgT) and methyl mercury (MeHg). Constituents such as dissolved organic carbon (DOC) and sulfide at selected sites present particular challenges due to interferences with standard analytical techniques. This is manifested by 1) the inability to discern when bromine monochloride (BrCl) addition is sufficient for sample oxidation for HgT analysis; and 2) incomplete spike recoveries using the distillation/ethylation technique for MeHg analysis. Here, we suggest ultra-violet (UV) oxidation prior to addition of BrCl to ensure total oxidation of DOC prior to HgT analysis and copper sulfate (CuSO₄) addition to aid in distillation in the presence of sulfide for MeHg analysis. Despite high chloride (Cl^-) levels, we observed no effects on MeHg distillation/ethylation analyses. Received: 24 September 1996/Revised: 12 February 1997/Accepted: 19 February 1997