2—（5—溴—2—吡啶偶氮）—5—二甲氨基苯胺与铂显色反应的研究及应用

研究了显色剂２（５溴２吡啶偶氮）５二甲氨基苯胺（５ＢｒＰＡＤＭＡ）与Ｐｔ（Ⅱ）的显色反应。结果表明,在乙醇存在下,１０～３２ｍｏｌ／ＬＨ３ＰＯ４介质中,试剂与Ｐｔ（Ⅱ）１５ｍｉｎ即形成稳定的紫蓝色配合物,并至少稳定２４ｈ。该配合物的最大吸收波长位于６２８ｎｍ处,表观摩尔吸光系数为８７３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１,其组成为ｎＰｔ（Ⅱ）∶ｎ５ＢｒＰＡＤＭＡ＝１∶１,Ｐｔ（Ⅱ）的质量浓度在０～１０ｍｇ／Ｌ符合比尔定律。所拟方法用于二次合金管理样及催化剂中铂的直接测定,结果与推荐值相符,精密度好,ＲＳＤ＜０．５％（ｎ＝６）。     

2-〔2-(6-甲基苯并噻唑)偶氮〕-5-二乙氨基苯甲酸与钴的显色反应及其应用

在十二烷基硫酸钠存在下，于ｐＨ４８～７４的缓冲溶液中，２＿〔２＿（６＿甲基苯并噻唑）偶氮〕＿５＿二乙氨基苯甲酸（６＿Ｍｅ＿ＢＴＡＥＢ）与Ｃｏ（Ⅱ）发生显色反应，形成稳定的蓝紫色络合物，其组成为ｎＣｏ（Ⅱ）∶ｎ６＿Ｍｅ＿ＢＴＡＥＢ＝１∶２，最大吸收波长为６５０ｎｍ，ε为１３８×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，Ｃｏ（Ⅱ）质量浓度在０～０３２ｍｇ／Ｌ时服从比尔定律。方法可直接用于维生素Ｂ１２和含钴分子筛中微量Ｃｏ（Ⅱ）的测定，结果与原子吸收法相符。对于ｗ（Ｃｏ）＝０．８２％的含钴分子筛测定８次，其ＲＳＤ为１３４％。     

二安替比林基—（2—溴）苯基甲烷与铈的显色反应及应用

合成了二安替比林基＿（２＿溴）苯基甲烷（ＤＡｏＢＭ）。在Ｍｎ（Ⅱ）和吐温＿８０存在下，Ｃｅ（Ⅳ）与ＤＡｏＢＭ反应生成有色化合物，λｍａｘ为４８０ｎｍ，摩尔吸光系数为３１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。Ｃｅ（Ⅳ）的质量浓度为０００４～０２ｍｇ／Ｌ时符合比尔定律。方法已用于稀土矿石中微量Ｃｅ（Ⅳ）的测定，结果与ＩＣＰ＿ＡＥＳ法相符     

N-间甲苯基-N′-(对氨基苯磺酸钠)硫脲与铜的显色反应及应用

研究了新试剂Ｎ－间甲苯基－Ｎ′－（对氨基苯磺酸钠）硫脲（ＭＭＰＴ）与Ｃｕ２＋的显色反应。结果表明,在ｐＨ４．６～５．６的ＨＡｃ－ＮａＡｃ介质中,Ｃｕ２＋与ＭＭＰＴ形成的配合物至少稳定５ｈ,其λｍａｘ＝３７０ｎｍ,表观摩尔吸光系数为１．１２×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。Ｃｕ２＋的质量浓度在０．０８～１．４ｍｇ／Ｌ时符合比尔定律,相关系数ｒ＝０．９９９１。方法简便、快速,用于铅矿中铜的分析,测定结果与监控样推荐值相符,对ｗ（Ｃｕ）＝０．８％的试样测定６次,ＲＳＤ＝３．２％。     

邻羧基苯基重氮氨基—4—苯基—2—噻唑光度法测定微量铜的研究

研究了新试剂邻羧基苯基重氮氨基－４－苯基－２－噻唑与Ｃｕ＾２＋的显色反应,在非离子表面活性剂ＴｎｉｔｏｎＸ－１００存在下,于ＰＨ８．６的Ｎａ２Ｂ４Ｏ７－ＨＣｌ缓冲介质中,Ｃｕ＾２＋与该试剂生成１：１的红色配合物,其配合物的最大吸收波长为５１０ｎｍ,摩尔吸光系数为５．４＊１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。     

TritonX—100—5—Br—PADAP光度法测定铜和镍

研究了非离子型表面活性剂ＴｒｉｔｏｎＸ－１００存在下,用５－Ｂｒ－ＰＡＤＡＰ光度法测定铜镍的方法。结果表明：在ＰＨ９．０的硼砂缓冲介质中,５－Ｂｒ－ＰＡＤＡＰ与铜和镍生成紫红色络合物,λｍａｘ＾Ｃｕ＝５７５ｎｍ,εＣｕ＝１．０４×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,λｍａｘ＾Ｎｉ＝５７５ｎｍ,εＮｉ＝１．１４×１０＾５Ｌ·ｍｏｌ＾－１·ｎｍ＾－１。铜和镍的质量浓度分别在０￣５６０μｇ／Ｌ和０￣５     

铁（Ⅲ）—对硝基苯基荧光酮—CTMAB—吐温—60多元配合物显色反应研…

Ｆｅ－对硝基苯基荧光酮－ＣＴＭＡＢ在ｐＨ１０．０－１１．２的硼砂－ＮａＯＨ缓冲溶液中形成蓝色多元配合物，其组成为Ｆｅ：ｐ－ＮＰＦ：ＣＴＭＡＢ＝１：２：４。在吐温－６０下，λｍａｘ为１６０ｎｍ，ε６１０＝１．１２×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，Ｆｅ含量在０－０．２μｇ／ｍｌ范围内符合比耳定律。     

锌与meso—四（2—磺酸萘基）卟啉显色反应研究

研究了新合成的显色剂ｍｅｓｏ－四（２－磺酸萘基）卟啉与Ｚｎ＾２＋的显色反应。在ｐＨ９．４０的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ缓冲体系中,以Ｈｇ６２＋及咪唑共同催化,在室温下８ｍｉｎ即反应完全。配合物最大吸收波长为４３４ｎｍ,表观摩尔吸光系数为４．２６×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１,Ｚｎ＾２＋浓度在０－０．１４μｇ／ｍｌ范围内符合比尔定律。配合物组成为ＴＮＰＳ４：Ｚｎ＾２＋＝２：１。利用ＭＩＢＫ萃取     

1—（2—羟基—3,5—二硝基苯基）—3—[4—（苯基偶氮）苯基]—三氮烯与铜的显色反应

研究了新合成的１－（２－羟基－３,５－二硝基苯基）－３－「４－（苯基偶氮）苯基」－三氮烯（ＨＤＮＰＡＰＴ）试剂与铜的显色反应。在乳化剂ＯＰ存在下,ＰＨ１１．０的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ介质中,铜与ＨＤＮＰＡＰＴ形成的红色配合物,其组成比为１：２,λｍａｘ＝５４０ｎｍ,表观摩尔吸光系数ε５４０＝１．７３×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,铜的质量浓度在０￣３６０μｇ／Ｌ符合比尔定律。方法应用于大     

新试剂——QAI与钴（Ⅱ）显色反应的研究和应用

本合成了新显色剂２－（８－喹啉偶氮）－咪唑（ＱＡＩ）测定了试剂的离解常数。研究了ＱＡＩ与ＣＯ（Ⅱ）的显色反应，在ｐＨ３．０～７．０的缓冲介质中，ＱＡＩ与ＣＯ（Ⅱ）形成１：３的红色配合物，λｍａｘ＝５３０ｎｍ表面摩尔吸光系数ε＝３．６７×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，钴量在０～２５μｇ／２５ｍｌ范围内符合比耳定律，该法的优点是选择性高和操作简便，做了较大量的Ｃｕ（Ⅱ），Ｎｉ（Ⅱ），Ｆｅ（Ⅱ     

Internally-Consistent Thermodynamic Data for Minerals in the System Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2

Internally consistent standard state thermodynamic data arepresented for 67 minerals in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-TiO₂-H₂O-CO₂.The method of mathematical programming was used to achieve consistencyof derived properties with phase equilibrium, calorimetric,and volumetric data, utilizing equations that account for thethermodynamic consequences of first and second order phase transitions,and temperature-dependent disorder. Tabulated properties arein good agreement with thermophysical data, as well as beingconsistent with the bulk of phase equilibrium data obtainedin solubility studies, weight change experiments, and reversalsinvolving both single and mixed volatile species. The reliabilityof the thermodynamic data set is documented by extensive comparisons(Figs. 4–45) between computed equilibria and phase equilibriumdata. The high degree of consistency obtained with these diverseexperimental data gives confidence that the refined thermodynamicproperties should allow accurate prediction of phase relationshipsamong stoichiometric minerals in complex chemical systems, andprovide a reasonable basis from which activity models for mineralsmay be derived.     

Siderit-Magnesit-Mischkristallbildung im system Mg2+-Fe2+-CO 3 2− -Cl 2 2− -H2O

The formation of the solid solution series MgCO₃-FeCO₃ in the system Mg²⁺-Fe²⁺-CO ₃ ^2? -Cl ₂ ^2? -H₂O has been investigstad between 200° C and 500° C. The experimental results show that the composition of any of these carbonates strongly depends on the temperature: At high temperatures mixed crystals rich in MgCO₃ are formed and low temperatures lead to the formation of FeCO₃-rich carbonates. Thus, at 200° C a Fe-poor (Mg-rich) solution is in equilibrium with a Fe-rich carbonate. At temperatures higher than 350° C a Fe-rich (Mg-poor) solution coexists with a Fe-poor (Mg-rich) solid phase; see Fig. 1. At 350° C a solution with a mole fraction^mFe²⁺/(^mFe²⁺+^mMg²⁺) of 0.20 leads to the formation of magnesite very poor in Fe, whereas at 250° C the same solution is in equilibrium with sideroplesit, containing 80 Mol-% FeCO₃, see Figs. 2 and 3. The importance of the experimental results for the formation of deposits of magnesite and siderite is discussed.     

Electrochemical Evidence for Pentasulfide Complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+

A series of stable pentasulfide complexes of the common base metals, Mn, Fe, Co, Ni, Cu and Zn exist in aqueous solutions at ambient temperatures. Pure sodium pentasulfide was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at ambient temperature. The S52- complexes were found to exist as determined by voltammetric methods.Pentasulfide complexes with compositions assigned as [M(1-S5)] and [M2(- S5)]2+ occur for Mn, Fe, Co and Ni where only one terminal S atom in the S52- binds to one metal (1 = mono-dentate ligand or M-S-S-S-S-S, = ligand bridging two metal centers or M-S-S-S-S-S-M). Conditional stability constants are similar for all four metals with log 1 between 5.3 and 5.7 and log 2 between 11.0 and 11.6. The constants for these pentasulfide complexes are similar to the tetrasulfide complexes and are approximately 0.4–0.8 log units higher than for comparable bisulfide complexes [M(SH)]+ as expected based on the higher nucleophilicity of S52- compared to HS-. Voltammetric results indicate that these are labile complexes.As with the bisulfide and tetrasulfide complexes, Zn(II) and Cu(II) are chemically distinct from the other metals. Zn(II) reacts with pentasulfide to form a stable monomeric pentasulfide chelate, [Zn(1-S5)] with log = 8.7. Cu(II) reacts with pentasulfide to form a complex with the probable stoichiometry [Cu(S5)]2 with log estimated to be 20.2. As with the other four metals, these complexes are comparable with the tetrasulfide complexes. Discrete voltammetric peaks are observed for these complexes and indicate they are electrochemically inert to dissociation. Reactions of Zn(II) and Cu(II) also lead to significant breakup of the polysulfide.The relative strength of the complexes is Cu > Zn > Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(1- S5)] and both Cu and Zn displace Mn, Fe, Co and Ni from their pentasulfide complexes.     

Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Single crystal Raman spectra of pyrite-type RuS₂, RuSe₂, OsS₂, OsSe₂, PtP₂, and PtAs₂ are presented and discussed with reference to the energies of the X-X stretching modes _x-x (A _g, F _g) and the X₂ librations (E, 2F_g). The main results obtained are (i) strong Raman resonance effects, (ii) different sequences for _x-x (A _g) and (E _g), i.e., R_{x_2 } $$ " align="middle" border="0"> for PtP₂ and PtAs₂ and R_{x_2 } $$ " align="middle" border="0"> for OsS₂, owing to the interplay of intraionic and interionic lattice forces, (iii) greater strengths for the intraionic P-P and As-As bonds compared to the S-S and Se-Se bonds, respectively, and (iv) a strong influe_gnce of the metal ions on the strength of the X-X bonds.This is contribution LXI of a series of papers on lattice vibration spectra     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: representation,estimation, and high temperature extrapolation

A revised equation is proposed to represent and extrapolate the heat capacity of minerals as a function of temperature: C _P=k₀+k₁ T ^–0.5+k₂ T ^–2+k₃ T ^–3 (where k₁, k₂0).This equation reproduces calorimetric data within the estimated precision of the measurements, and results in residuals for most minerals that are randomly distributed as a function of temperature. Regression residuals are generally slightly greater than those calculated with the five parameter equation proposed by Haas and Fisher (1976), but are significantly lower than those calculated with the three parameter equation of Maier and Kelley (1932).The revised equation ensures that heat capacity approaches the high temperature limit predicted by lattice vibrational theory (C _P=3R+²VT/). For 16 minerals for which and have been measured, the average C _Pat 3,000 K calculated with the theoretically derived equation ranges from 26.8±0.8 to 29.3±1.9 J/(afu·K) (afu = atoms per formula unit), depending on the assumed temperature dependence of . For 91 minerals for which calorimetric data above 400 K are available, the average C _Pat 3,000 K calculated with our equation is 28.3±2.0 J/(afu·K). This agreement suggests that heat capacity extrapolations should be reliable to considerably higher temperatures than those at which calorimetric data are available, so that thermodynamic calculations can be applied with confidence to a variety of high temperature petrologic problems.Available calorimetric data above 250 K are fit with the revised equation, and derived coefficients are presented for 99 minerals of geologic interest. The heat capacity of other minerals can be estimated (generally within 2%) by summation of tabulated oxide component C _Pcoefficients which were obtained by least squares regression of this data base.     

Studies in the system KAlSiO4-BaAl2Si2O8-SiO2-H2O

Various members of the KAlSi₃O₈-BaAl₂Si₂O₈ feldspar series are hydrothermally synthesized. Cellparameters of these are calculated from diffractometer patterns and found to be similar to those of Gay and Roy. A variation diagram is constructed correlating Cn-content and values of Δ_FeKα(2θ₍₁₁₁₎CaF₂—2θ₍₀₀₄₎Fs_ss), which gives $${\text{Mol}}\% {\text{ Cn = 229}}{\text{.83}}\Delta {\text{2}}\theta ---{\text{190}}{\text{.81}}$$ by a least square regression fitting. Phase equilibria relation in the solidus-liquidus-region for the KAlSi₃O₈-BaAl₂Si₂O₈-H₂O system at 1000 kg/cm² are investigated. It is found to be a case of simple solid solution in a binary system, with reservations at the potassium-rich side of the system. Goranson (1938) gives a temperature of about 1000°C at 1000 kg/cm² \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) for the incongruent melting of sanidine, but the authors prefer a value around 930°C at the same \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) . Reaction products of starting materials on the join KAlSi₂O₆-BaAl₂Si₂O₈ and KAlSiO₄-BaAl₂Si₂O₈ gave no experimental hint for replacement of K⁺ by Ba⁺⁺.