水溶液中合成羟基磷灰石的实验研究

羟基磷灰石（HA）是一种生物活性陶瓷材料，为目前齿科和骨科所常用的替代材料，采用中和反应和复分解反应制备HA，并分析讨论了温度，pH值，加料方式，加料速率及超声波等因素对合成HA的影响，制得样品均用化学分析法测定Ca/P值，部分采用X射线衍射法（XRD）和电镜照相（SEM）来鉴定样品HA的纯度。     

硫化物矿物氧化反应动力学实验研究

硫化物矿床和含硫化物矿床（如中高硫煤）在开发过程中由于氧化作用向环境释放大量的酸、硫酸盐、重金属及其它有害物质,造成一定范围内的次生地球化学异常和环境污染;而中国大陆硫化物的排放量2010年将达到39．1×10 6 t。因此,人们对硫化物矿物在表生环境下的氧化行为日益重视。硫化物矿物的氧化速率受矿物本身物理化学特性（组成、结构、表面性质）和介质条件（溶解氧DO、Fe 3＋浓度、pH、Eh、温度及微生物）等多种因素的控制。在全面分析近年来国内外文献的基础上,系统介绍了硫化物矿物氧化动力学实验研究方法、实验参数的选择、反应机理、反应产物及反应速率等的研究现状。指出今后应加强对初始阶段的氧化反应速率、反应中间产物、多因素的综合作用、分子水平上的反应机理解释等方面的研究。     

地下水与玄武财反应趋势分析

通过建立水化学平衡反应模型,计算地下水组分的各种可能存在形式的浓度和活度,并求得各种矿的饱和指数,再用饱和指数分析水－岩相互作用过程中矿物的溶解与沉淀反应趋势。本文采用该方法对盱眙玄武岩土区水－岩间反应趋势进行了分析。     

矿物反应与变形关系研究——以糜棱岩高温高压实验为例

矿物反应和变形局部化在中下地壳普遍存在,两者相互影响和促进。实验研究表明,矿物反应与变形关系非常复杂。本文在糜棱岩高温高压流变实验的基础上,分析了实验变形样品中的矿物反应分布特征以及矿物反应引起的化学成分变化,讨论了矿物反应与变形的相互影响。微观结构分析表明,实验变形后的糜棱岩样品在温度800~890℃时,角闪石和黑云母出现脱水反应,生成微晶角闪石和黑云母,并伴有局部熔融。受应变局部化控制,脱水反应产物主要出现在黑云母、角闪石条带边缘。微晶和熔体的成分分析表明,不仅脱水反应形成的微晶与熔体的SiO 2含量非常低,而且黑云母周围的反应产物和熔体主要来自于黑云母的脱水,角闪石边缘的反应产物和熔体主要来自于角闪石脱水,石英、钾长石和斜长石没有参与反应与熔融。本研究中的脱水反应产物中,没有发现辉石和石榴石,这种脱水反应与文献中报道的无局部化的均匀样品在静高压和高熔融比例条件的脱水反应产物和熔体的成分有很大差别。黑云母和角闪石的局部化分布和脱水程度低,可能是造成脱水反应产物有差别的巨大原因。在本实验结果中,脱水反应对变形的影响主要体现为,脱水反应产生了细粒混合矿物相,使得在局部化的剪切带内变形机制从位错蠕变转变为扩散蠕变,导致样品出现应变弱化。另外脱水反应还引起了局部脆性破裂。变形引起晶体塑性变形,增加了位错密度和矿物细粒化,促进了晶体内部成核和黑云母与角闪石的脱水分解;差应力作用增加了局部的正应力和平均应力,增加了黑云母和角闪石能够稳定存在的压力范围,这可能是反应产物以微晶黑云母和角闪石为主,而没有转化为辉石的原因。     

性能优异的Rh改性的Pd/Al2O3密偶催化剂（英文）

采用等体积浸渍法制备了Pd/Al2O3和Rh-Pd/Al2O3密偶催化剂,运用H2程序升温还原、CO化学吸附和X射线光电子能谱等手段对催化剂进行了表征,并考察了催化剂对丙烷总包反应和单反应的转化活性.总包反应结果表明,Rh的添加使起燃温度和完全转化温度分别降低了23和18 oC.单反应结果证明,添加Rh能提高各单反应丙烷的转化活性,尤其是有NO参与的反应.表征结果证明,掺杂Rh不仅可以抑制活性组分PdOx的烧结,提高PdOx的分散度,而且可以改变其电子状态     

变质动力学

变质动力学是运用化学动力学方法来研究岩石变质反应的速度和结晶作用动力学的一门新的边缘性交叉学科。在本世纪70年代的变质岩石学研究中,Winkler(1976)和Mueller等(1977)首先提出将化学热力学和化学动力学的理论及方法用于变质岩石学的研究中。自1983年以来,已有若干论文明确提出变质体系中物质的迁移机制和扩散作用(Brady,1983)。Cygam和Lesaga(1985),Elphick等(1985)和Loomis等(1985)的研究追索了石榴子石的扩散现象,是变质动力学较为成功的研究实例,Tracy在1987年较为系统地     

安徽铜陵层控夕卡岩型铜矿床的成矿作用动力学

本文应用输运反应耦合过程动力学模型研究了安徽铜陵层控夕卡岩型铜矿床的成矿作用动力学机制。研究指出:(1)成矿流体的盐度梯度和流速均可促进岩浆水与地层水的混合和反应,透水层是二者发生强烈混合输运反应与成矿作用的有利场所;(2)在顺层方向上发生等温输运反应时,成矿流体与岩石接触界面处形成的移动输运反应前锋顺透水层从上游向下游缓慢推进,形成了与地层整合的层伏夕卡岩体与层状矿体;(3)在穿层方向上发生穿越等温线的梯度输运反应结果使矿物成分从镁夕卡岩向硫化物矿体发生渐变过渡。     

地下水有机污染控制及就地恢复技术研究进展（三）

本文是关于地下水有机污染控制及其就地恢复技术进展概况的第3篇文章，文中主要介绍渗以应格栅中的氧化－还原反应格栅和生物降解反应格栅。     

五氯苯酚在氧化物和粘土矿物表面吸附:表面反应模式及其环境意义

石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线已用批量平衡技术进行研究。所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5~6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,研究提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则既包含表面络合反应,又包含表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1~3个…     

雄黄与光反应的研究进展

矿物晶体收藏近年来成为一大热点,雄黄晶体艳丽,是地质类博物馆和矿物收藏家收藏的矿物种类之一,然而光照下雄黄不稳定,雄黄与光的反应倍受关注。因硫砷化合物的光化学灵敏度,硫砷化合物是一种重要的光学材料,国外开展了雄黄与光作用的反应产物和机理研究工作,雄黄与光的反应产物有副雄黄、砷华和χ-物相,在光照下雄黄通过As_4S_5分子间接地转变为副雄黄。作为药用矿物,As_2O_3是药用雄黄的组成部分,又是毒性成分,As_2O_3的来源与受到的高热和光照等有关,国内中医药界加强了对雄黄的物质成分的研究,还需加强光照对药用雄黄成分影响的研究。     

极化曲线反应极限电流强度确定矿体表面积的实验研究

本文简单了极化曲线反应极限电流强度确定矿体表面积的基本原理，阐述了单矿体和多矿物极化曲线反应极限电流强度确定矿体表面积的实验研究方法和结果，并说明极化曲线反应极限电流强度确定矿体表面积是有可能的。     

非接触极化曲线视反应电位差区分矿体矿物成分及确定其边界的实验研究

本文用非接触极化曲线视反应电位差区分矿体矿物成分和确定矿体边界的基本原理，着重阐述矿物非接触极化曲线视反应电位差特征的实验研究方法和结果，并指出非接触极化曲线视反应电位差区分矿体矿物成分和确定矿体边界是有可能的。     

Glaucophane and pyroxene breakdown reactions in the Pennine units of the Eastern Alps

Abstract New occurrences of crossite and jadeitic pyroxene are described from a thick metabasite unit within the upper levels of the Peripheral Schieferhülle in the Tauern Window, Austria. Unusual textures are preserved which provide evidence for the reactions and mechanisms involved in the breakdown of crossite and jadeitic pyroxene. Zones of albite and chlorite, produced by reaction between crossite and paragonite, have been preserved due to sluggish reaction kinetics during decompression from the blueschist to the greenschist facies. The zonal sequence is interpreted in terms of chemical potential gradients in Na, Mg and Al, which have been established by overstepping the equilibrium boundary. Breakdown textures of jadeite-acmite pyroxene to a symplectite of albite + hematite + actinolite, and of crossite to talc and actinolite are also described.
The occurrence of crossite and jadeitic pyroxene at high levels within the Peripheral Schieferhülle implies that even upper levels of the structural sequence have undergone blueschist facies metamorphism with pressures in excess of 8 kbar during the Alpine collisional event.     

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.     

紫硫镍矿交代镍黄铁矿的水热反应机理及动力学

本工作首次在实验室条件下对浅生区紫硫镍矿(Ni,Fe)3S4交代镍黄铁矿(Ni,Fe)9S8水热反应的机理及动力学进行了研究。起始反应矿物采用高纯自然镍黄铁矿,合成纯镍黄铁矿或合成镍黄铁矿-磁黄铁矿集合体。反应pH值采用0.2M醋酸-醋酸纳缓冲溶液控制在3～5的范围内。反应进程由X-射线衍射物相定量分析及扫描电镜观察进行跟踪。结果表明,当反应温度恒定在80℃时,交代20(4)%的镍黄铁矿需792h。相同条件下加入少量H2S可将反应速率提高一倍。当反应在125℃饱和蒸汽压水热环境下进行时,完全交代纯镍黄铁矿需约168h。此过程由于磁黄铁矿的存在而被催化,交代集合体中的镍黄铁矿仅需68h,进一步反应磁黄铁矿被交代成白铁矿。磁黄铁矿的催化作用可能源于溶解产生的微裂纹加速了流体的传质过程。当反应温度升高至145℃时,速率反而下降,不遵循Arrhenius经验规律。动力学分析得80℃速率常数介于5.8×10-8～3.0×10-7/s之间,125℃及145℃速率常数分别介于2.8×10-6～2.08×10-5/s及1×10-6～5.1×10-6/s之间,远高于同温度下固相扩散反应的速率常数,表明该反应在地质时标上为一快速反应。此外,用背散射电子显微技术对矿物表面形貌进行了分析,发现交代产物紫硫镍矿具有颗粒细小及存在微裂纹等特征,与自然界浅生矿床中的紫硫镍矿非常相似;电镜实验还表明该交代作用是一个典型的耦合溶解-再沉淀反应。其耦合机制的驱动力可能与反应界面处微空隙对流体饱和度的控制有关。     

低温酸性条件下白钨矿的不一致溶解动力学

在75℃和pH=1.04～2.46时采用间歇型实验方法测定了天然白钨矿在HCl溶液中的溶解速率,揭示了溶解反应的动力学机理。结果表明,Ca的释放速率随反应时间保持稳定,并随pH降低而增大。W的释放行为则更为复杂,在反应初期与Ca呈一致溶解,之后由于钨酸表面层(中间产物)的形成,W的释放量和释放速率明显下降。这说明白钨矿的溶解作用由早期的表面化学反应转变为化学反应-扩散控制过程,从而导致W、Ca呈不一致溶解。pH越小,不一致溶解出现的时间越早。酸性溶液中白钨矿的溶解速率方程为v=k[H+]n,以W和Ca计算的速率常数k分别为0.65×10-5mol/m2s和1.04×10-5mol/m2s,反应级数n则分别为1.20和1.26。结合他人研究结果,白钨矿的溶解反应相对于H+可能为一级反应。     

直流电弧放电中的高温化学反应

本文对近年来国内外关于直流电弧放电中的高温化学反应的应用进展进行了综述。附参考文献72篇。     

Petrological consequences of variations in metamorphic reaction affinity

The extent to which kinetic barriers to nucleation and growth delay the onset of prograde metamorphic reaction, commonly known as overstepping, is related to the macroscopic driving force for reaction, termed reaction affinity. Reaction affinity is defined in the context of overstepping as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming reactions, have a higher entropy/volume change, and therefore a higher reaction affinity per unit of temperature/pressure overstep, than those which release little or no H₂O. The former are expected to be overstepped in temperature or pressure less than the latter. Different methods of calculating reaction affinity are discussed. Reaction affinity ‘maps’ are calculated that graphically portray variations in reaction affinity on equilibrium phase diagrams, allowing predictions to be made about expected degrees of overstepping. Petrological consequences of variations in reaction affinity include: (i) metamorphic reaction intervals may be discrete rather than continuous, especially in broad multivariant domains across which reaction affinity builds slowly; (ii) reaction intervals may not correspond in a simple way to reaction boundaries and domains in an equilibrium phase diagram, and may involve metastable reactions; (iii) overstepping can lead to a ‘cascade effect’, in which several stable and metastable reactions involving the same reactant phases proceed simultaneously; (iv) fluid generation, and possibly fluid presence in general, may be episodic rather than continuous, corresponding to discrete intervals of reaction; (v) overstepping related to slowly building reaction affinity in multivariant reaction intervals may account for the commonly abrupt development in the field of certain index mineral isograds; and (vi) P–T estimation based on combined use of phase diagram sections and mineral modes/compositions on the one hand, and classical thermobarometry methods on the other, may not agree even if the same thermodynamic data are used. Natural examples of the above, both contact and regional, are provided. The success of the metamorphic facies principle suggests that these kinetic effects are second‐order features that operate within a broadly equilibrium approach to metamorphism. However, it may be that the close approach to equilibrium occurs primarily at the boundaries between the metamorphic facies, corresponding to discrete intervals of high entropy, dehydration reaction involving consumption of hydrous phases like chlorite (greenschist–amphibolite facies boundary) and mica (amphibolite–granulite facies boundary), and less so within the facies themselves. The results of this study suggest that it is important to consider the possibility of reactions removed from equilibrium when inferring the P–T–t evolution of metamorphic rocks.     

Can a reaction be written between a set of minerals within error?

Determining whether a reaction can be written between a set of minerals within error is an example of the more general problem of determining whether a set of compositions are coplanar within error. Generally if the compositions are of minerals, ‘within error’ should allow the minerals to maintain stoichiometry. The problem is addressed via the addition of a ‘bogus’ composition to the set, and calculating the reaction coefficients for a reaction between the compositions in this augmented set. A reaction can be written if a confidence interval on the reaction coefficient of ‘bogus’ includes zero. The reaction coefficients can be solved for directly when the problem is posed in terms of least squares with equality constraints. The confidence interval is determined with a bootstrap method, allowing the result to depend on the scatter of the data around the solution of the least squares problem, not on the data uncertainties