对偶氮水杨酸苯基萤光酮的研究及应用 Ⅱ.Ga-p-CHPA-PF-Tween80光度法测定痕量镓

自制的新显色剂2,3,7-三羟基-9-〔4-(3-羧基-4-羟基苯)-偶氮〕-苯基萤光酮,(简称p-CHPA-PF),在微碱性介质中,有表面活性剂存在下,与Ga(Ⅲ)显色,形成紫红色三元配合物。配合物λ_(max)=554nm,表观摩尔吸光系数ε＇_(554)=1.2×10~5L·mol~(-1)·cm~(-1),ε＇_(554-500)=1.79×10~5L·mol~(-1)·cm~(-1),Ga在0—10μg/25ml范围内符合比尔定律。用本法测定岩矿中痕量Ga,结果满意。     

水相中铋(Ⅲ)-碘化钾-乙基紫缔合反应的研究—分光光度法测定微量铋

在pH 3.0～4.5范围,水相中缔合物(EV)_2[BiI_5](λ_(max)=540nm)同试剂(λ_(max)=650nm)有较大的对比度。在完成缔合后的体系中加入适量酸,过量乙基紫阳离子质子化使对比度、灵敏度增高。用于微量铋的测定,0～24μg/25ml范围符合比尔定律,表观摩尔吸光系数为2.05×10~5。用于样品分析结果满意。     

2,4-二溴-6-羧基苯基重氮氨基偶氮苯与银显色反应的研究

作者合成的新显色剂2,4-二溴-6-羧基苯基重氮氨基偶氮苯,在pH 11.0的Na_2B_4O_7-NaOH缓冲介质中,有非离子表面活性剂Triton X-100存在下,可与Ag(Ⅰ)生成稳定的2:1红色配合物,配合物的λ_(max)=552nm,表观摩尔吸光系数ε_(552)=1.05×10~5 L·mol~(-1)·cm~(-1)。Ag量在0～400ng/ml范围内符合比尔定律。方法用于测定废水及矿石中的痕量Ag,结果满意。     

PMBP萃取分离桑色素荧光法测定地质样品中痕量钪

在磺基水杨酸存在下,以1-苯基-3-甲基-4-苯酰基吡唑酮-5(PMBP)萃取,5％HBr反萃取,桑色素荧光法可灵敏、快速、准确地测定地质样品中痕量Sc。λ_(ex)为420nm,λ_(em)为500nm,测定下限为0.02μg/ml,0—8μg Sc/10ml同相对荧光强度呈线性。     

新显色剂DBN-偶氮胂作为测定痕量钍的显色剂

在0.5—1.2mol·L~(-1)HCl中,新显色剂DBN-偶氮胂与钍形成紫色二元络合物.λ_(max)=630nm,ε_((?)30nm)=1.11×10~5L·mol~(-1)·cm~(-1),0—0.8μgTh/ml遵守比尔定律。在有酒石酸、草酸存在下,重稀土(Ⅲ)和大量铀(Ⅵ)不干扰。测定矿石中n·10~(-3)％级的钍,相对标准偏差为6.16％。     

二阶导数等值点荧光光度法同时测定岩矿中钨和钼

在W(Mo)-茜素磺酸钠荧光体系中,加入一定量乙醇后,可使W、Mo的荧光强度明显增加,Mo比W的灵敏度提高更加显著,为W、Mo在同一体系中进行测定提供了条件。在λ_(em)=603nm时,W的二阶导数荧光值不随含量变化而变化,成为W等值点,而Mo的二阶导数荧光值则有良好的线性关系。同时,λ_(em)=613nm时成为Mo等值点,而W的二阶导数荧光值有良好的线性关系。基于上述事实,提出用等值点法实现在导数荧光光谱仍相互重叠情况下同时测定W和Mo。方法经标准样品分析验证,结果与推荐值吻合。     

双波长等吸收点光度法同时测定矿石中铂和钯

在SnCl_2存在的1mol/LHCI溶液中,用双硫腙-四氯化碳(H_2D_2-CCl_4)溶液同时萃取Pd和Pt。选择参比波长λ_1=776.6nm,测定波长λ_2=638.0nm,双波长等吸收点光度法测定Pd;再选择Pt的λ_(max)(720nm)单波长法测定Pt。方法可用于矿石中Pt和Pd的同时测定。     

Ti—SAF—CTMAB树脂相光度法测定铁矿中微量钛

在0.05—0.15mol/LH_2SO_4介质中,Ti与水杨基萤光酮(SAF)、溴化十六烷基三甲胺(CTMAB)反应生成有色络合物,经724弱酸型阳离子交换树脂交换,在树脂相光度法测定微量钛。其λ_(max)=600nm,表观ε=8.0×10~6L·mol~ (-1)·cm~(-1)。0～2.5μgTi/250ml服从比尔定律。方法用于铁矿中微量钛的测定,结果满意。     

二溴羧基偶氮胂光度法测定钛酸铋烧结物中游离氧化铋

在0.04～0.16mol/LHClO_4介质中,Bi与二溴羧基偶氮胂发生显色反应,生成1:2的蓝色络合物,λ_(max)=625nm,ε=7.2×10~4L·mol~(-1)·cm~(-1),Bi量在0～0.5μg/ml范围内符合比耳定律。所拟方法已用于检测陶瓷电容钛酸铋烧结物中游离Bi_2O_3。     

邻氯苯基荧光酮—CTMAB荧光熄灭法测定痕量锡

本文研究了在溴化十六烷基三甲铵存在下,锡与邻氯苯基荧光酮(O-Cl-PF)形成三元配合物导致邻氯苯基荧光酮的荧光熄灭。结果表明:在pH3.8—4.5的NaAc/HCl介质中,产生荧光熄灭程度最大的激发波长为λ_(ex)=530nm,荧光波长为λ_(em)=550nm,当锡含量在20—120ppb范围内与荧光熄灭程度呈线性关系,藉以测定痕量锡。方法简便,稳定性好,应用于地质和合金样品中痕量锡的测定取得了令人满意的结果。     

岩石坚硬程度对核电厂地基-基础地震响应特征的影响分析

考虑核电厂地基-基础的动力相互作用,应用显式动力有限差分法分析了地震作用下极软岩、较软岩、坚硬岩上核电厂建筑结构基础的地震响应特征,比较了岩石坚硬程度对基础加速度反应谱的影响。研究表明：随着岩石坚硬程度的提高,核电厂建筑物结构基础的地震响应有增加的趋势;在周期轴上,基础处的加速度反应谱曲线会随着岩石坚硬程度的提高逐渐向短周期（高频段）方向移动。在高频段,建造于较坚硬岩石上基础结构的加速度反应谱值偏大;在中等频段,建造于较软岩石上基础结构的加速度反应谱值偏大;在低频段,岩石坚硬程度对加速度反应谱的影响不显著。     

Strains of scattering of near-field of a point source

Three dimensional scattering of near-field is studied for dilatation and rotation in the time domain. The perturbation method is applied to solve the equation of motion for the first order scattering from a weak inhomogeneity in an otherwise homogeneous medium. The inhomogeneity is assumed close enough to the point source so that the near-field intermediate wave is dominating over the far-field sphericalP andS pulses. The integral expressions are derived to relate dilatation and rotation of scattering to the radial fluctuations of velocities and density in the inhomogeneity. These integrals are solved to calculate the strains of scattering from (a part of) an inhomogeneous spherical shell of arbitrary curvature. Variable curvature may allow the shape of inhomogeneity volume element to change uniformly from spherical to rectangular. Rotation of scattering from a spherical shell is independent ofP wave velocity inhomogeneity. Dilatation of scattering does not involveS wave velocity inhomogeneity but its gradient. The back scattering results are obtained as a special case. Strains are computed numerically, for hypothetical models to study the effects of various parameters viz., velocity inhomogeneity, distance of source from inhomogeneity and from receiver, and thickness of inhomogeneity. The curvature of the spherical shell is varied to study the effects of the shape of inhomogeneous volume element on scattering.     

土石坝心墙水力劈裂分析

简要分析了水力劈裂的发生条件、力学机理。基于水压楔劈机理,利用有限元方法建立了一种水力劈裂的发生判定方法。该方法假定心墙预先存在局部渗透弱面（裂缝）,通过将裂缝位置的单元材料改为裂缝软材料,考虑库水进入裂缝后对裂缝周围土体的作用,建立水力劈裂分析的平面有限元模型,确定裂缝端部垂直于裂缝面的正应力,进而依据该正应力判断水力劈裂发生的可能性,该方法同时可模拟水力劈裂的发展过程。     

土钉支护失稳分析

某基坑采用复合土钉墙支护,开挖至坑底后,基坑北侧发生失稳事故。本文就其事故发生原因作一探讨。     

地震次生地质灾害风险评估集对态势分析

5．12四川汶川8级强震引发了大量次生地质灾害,加剧了灾情并严重影响抗震救灾。地震次生地质灾害受多重因素制约,其孕育与致灾过程具有不确定性。利用集对分析原理与方法,对地震次生地质灾害进行同异反态势分析,拟定了风险评估的集对分析同一度、差异度、对立度等指标体系的构建原则与赋值标准,对承灾体系统的不确定性及其作用作了刻画与分析,建立了不同风险分区代表性的集对分析联系度表达式,为地震灾害研究提供了可资借鉴的新思路和技术方法。     

Geochemistry of Thermal Waters of Continental Margin of Far East of Russia

Studied waters belong to warm(T=30-50℃),alkaline(pH=8.9-9.3),low mineralized(TDS235 mg/1)Na-HCO_3 or Na-SO_4-HCO_3 thermal waters with high content of SiO_2(up to 81 mg/l)and F(up to 3.9 mg/1),occur on modern volcano-tectonic rejuvenated areas of Eastern Sikhote-Alin orogenic belt.Low~3He concentration as well as N_2/O_2 and N_2/Ar ratios exclude influence of deep mantle fluid.New rare earth element data constrain our understandmg of water-rock interaction occurring in the water source region.Meteoric origin of waters is proved by stable isotope values varying from-71‰to-136.1‰and from-10.8‰to-18.8‰forδ~2U andδ~(18)O respectively.REE patterns reflect high pH,resultfing from water-rock interaction and oxidative conditions.Calculations of deep aquifer temperature using Na-K and quartz geothermometers show 116.8-131.1°C and 82.2-125.8℃respectively.Presence of deep faults both with abnormal thermal gradient(~45-50 K/km)define unique geochemical shape of thermal waters of Sikhote-Alin,area,where no present volcanic activity is registered.     

下扬子区三叠纪古地理演化

下扬子区在三叠纪期间接受了早-中三叠世海相碳酸盐沉积、中-晚三叠世海陆交互相和陆相湖沼沉积.沉积相带的空间分布和古地理格局的变迁明显地受到区域构造的控制.区内盆地发育与演化是在华南板块与扬子板块、扬子板块与华北板块相互作用的背景下进行的.早-中三叠世末期的印支运动是下扬子区构造-古地理格局改变的决定性因素,使下扬子海盆闭合,沉积类型由海相沉积变为陆相沉积.下扬子区三叠纪古地理的演化特征也为板块碰撞提供了沉积证据.     

多年冻土融沉性分类研究

在冻土工程中,冻土的融沉性评价是工程地质勘察的主要内容之一,融沉性分类是冻土地基基础设计施工的重要依据．根据345个冻土原状样品融沉压缩试验数据,提出了细砾、砂土、粉土、黏性土、泥炭化黏性土和泥炭质土等6类土的融沉系数一含水量或融沉系数一超塑含水量线性回归方程式,得到与各融沉性分级相应的界限含水量或界限超塑含水量．最后...     

Kinetics of dehydration of Ca-montmorillonite

Isothermal thermogravimetric experiments have been carried out to determine the reaction kinetics of the dehydration processes in fuller's earth, a natural Ca-montmorillonite. Dehydration in swelling clays is a complex reaction, and analysis of the thermogravimetric data using empirical rate equations and time-transformation analysis reveals that the nature of the rate controlling mechanism is dependent upon both the temperature regime of the sample as well as the extent of reaction. For fuller's earth, we find that the dehydration kinetics are dominated by a nucleation and growth mechanism at low temperatures and fractions transformed (stage I), but above 90 °C the last stages of the reaction are diffusion controlled (stage II). The activation energy for dehydration during stage I is around 35 kJ · mol⁻¹, whereas the removal of water during stage II requires an activation energy of around 50 kJ · mol⁻¹. These two stages of dehydration are associated with primary collapse of the interlayer (stage I) and movement of water that is hydrated to cations within the interlayer (stage II). Received: 28 August 1998 / Revised, accepted: 27 January 1999