Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

Simulation of marine boundary layer characteristics using a 1-D PBL model over the Bay of Bengal during BOBMEX-99

The characteristic features of the marine boundary layer (MBL) over the Bay of Bengal during the southwest monsoon and the factors influencing it are investigated. The Bay of Bengal and Monsoon Experiment (BOBMEX) carried out during July–August 1999 is the first observational experiment under the Indian Climate Research Programme (ICRP). A very high-resolution data in the vertical was obtained during this experiment, which was used to study the MBL characteristics off the east coast of India in the north and south Bay of Bengal. Spells of active and suppressed convection over the Bay were observed, of which, three representative convective episodes were considered for the study. For this purpose a one-dimensional multi-level PBL model with a TKE-ε closure scheme was used. The soundings, viz., the vertical profiles of temperature, humidity, zonal and meridional component of wind, obtained onboard ORV Sagar Kanya and from coastal stations along the east coast are used for the study. The temporal evolution of turbulent kinetic energy, marine boundary layer height (MBLH), sensible and latent heat fluxes and drag coefficient of momentum are simulated for different epochs of monsoon and monsoon depressions during BOBMEX-99.The model also generates the vertical profiles of potential temperature, specific humidity, zonal and meridional wind. These simulated values compared reasonably well with the observations available from BOBMEX.     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

混合气体驱替煤层气技术的可行性研究

气体驱替煤层气技术是近年来发展起来的具有温室气体减排和提高煤层气采收率双赢效果的新兴技术,相关研究受到世界主要发达国家的广泛重视。对于温室气体减排的压力,发达国家的研究主要着眼于该技术在高渗透、不可采煤层中的应用,注入气体主要为CO2,目的是尽可能多地封存CO2,同时提高煤层气采收率。目前,国内在这方面的研究刚刚起步。国内煤层具有渗透率普遍较低、不开采煤层与要开采煤层难以界定的特点,注CO2气体驱替煤层气在这种煤层中的可行性值得商榷。针对国内煤层特点和煤矿瓦斯抽采率低的现状,建议采用富N2混合气体驱替煤层气技术,以提高煤层气产采收率。通过理论分析、数值模拟和现场试验研究分析了实施混合气体驱替煤层气技术的可行性。研究结果表明,混合气体驱替煤层气技术适用于国内低渗透、可开采煤层,可以提高煤层气采收率和单产量。     

东海陆架盆地伸展率和压缩率及构造跃迁

东海陆架盆地位于欧亚板块的东南缘和西太平洋活动大陆边缘,本文选取了东海陆架盆地主要凹陷的17条地震剖面,采用平衡剖面技术,计算了主要凹陷新生代不同演化阶段的伸展率和压缩率。分析表明,东海陆架盆地构造演化总体由西向东跃迁。晚白垩世至晚古新世东海陆架盆地裂陷中心在西部坳陷带,始新世东迁至东部坳陷带,上新世东迁至东海陆架盆地东侧的冲绳海槽盆地。古新世中后期东海陆架盆地西部坳陷带北侧昆山凹陷反转;中新世东部坳陷带的西湖凹陷反转。东海陆架盆地西部坳陷带与东部坳陷带构造演化不同,证明了东海陆架盆地的东西分带。西部坳陷带北部的长江坳陷和南部的台北坳陷构造演化不同,东部坳陷带北部的西湖凹陷和南部的钓北凹陷构造演化不同,证明了东海陆架盆地的南北分块。     

陇中黄土高原夏季陆面辐射和热量特征研究

利用兰州大学半干旱气候与环境观测站(SACOL)的观测资料,分析了陇中黄土高原夏季陆面辐射和热量收支的特征.通过研究不同典型天气条件对陆面过程微气象特征的影响,发现地表反射率在晴天会出现早晨偏大的不对称结构;晴天与多云天气相比不平衡量较大,而阴天时的阵性降水会使局地能量收支出现不平衡.利用最小二乘法(OLS)线性回归得到的夏季平均不闭合度是19.6%.在半干旱区云和降水对辐射和能量收支的影响不容忽视,达到约25%的削弱程度,比极端干旱的敦煌荒漠区要大,又进一步证明了半干旱区夏季的平均气候特征与云量较多的多云天气(5≤Mean total cloud amount<8)接近.另外,7月日平均波恩比最大是4.1,平均是1.95,比极端干旱区的敦煌波恩比小1个数量级,说明榆中所处的黄土高原半干旱区比敦煌所处的极端干旱区在气候上要湿润很多.     

岩体动力失稳终止点、能量释放量解析解与图解

以精确和近似突变模型方式,按Ⅱ体的步调,给出了岩体系统动力失稳弹性能释放量的解析解和图解;将地震、岩爆前后阶段岩体系统稳定性的定性认识提高到定量描述;严格确定了岩体系统弹性能瞬间释放终止点位置,为计算地震效率、研究释放的地震能量级、地震应力降、震后断层错距和围岩弹性应变恢复量提供了科学依据。系统失稳时具备对外界做功的本领,地震波能便是失稳的岩体系统以破坏性方式对环境做功。给出的弹性能释放量图解中蕴涵了丰富的信息量,为确定岩体动力失稳问题的数学模型是折迭突变模型给出有力佐证。     

对企业会计信息失真现象的探讨

针对企业会计信息失真的一些现象，分析了产生原因，阐述了给国家、社会甚至企业自身带来的危害性，并提出了建立惩处机制，监督约束机制，推行会计委派制，完善会计监督体系，提高职业道德等相应的治理建议。     

压密注浆的能量分析方法

为了能够从能量的角度分析压密注浆的力学机理,并给出注浆压力的理论解,将整个注浆过程视为无限土体中的圆孔扩张问题,根据注浆过程中能耗区土体在注浆压力和静止土压力作用下的应力、应变和体变关系以及注浆扩孔过程中的能量和体变守恒原理,推导出压密注浆极限注浆压力的理论解答。计算和分析表明,理论解的计算结果与工程实际比较吻合,而且球形扩孔的注浆压力比柱形扩孔的注浆压力要小得多,初步证实了理论解的可靠性。     

岩石中柱状装药爆炸能量分布

岩石中装药爆炸产生的爆破能量可分为爆炸冲击波能量和爆生气体膨胀能量。对爆炸能量分布的理论分析有助于改善爆破效果,提高爆破质量。在柱状耦合装药情况下,分析了冲击波作用下岩石变形和破坏的特点、爆生气体对爆腔的扩腔作用,考虑了在岩体的损伤情况下爆生气体对裂纹的驱裂作用。计算结果表明：埋深在临界深度以下时,岩石中柱状装药爆破冲击波做功消耗的能量约占爆炸总能量的40 %,剩余爆生气体能量中用于扩腔和扩展主要裂隙的能量约占总能量的23 %,剩余大约37 %的能量中有小部分能量用于新增裂纹数目,而大部分损失掉了。