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Products and Kinetics of the Reaction of Monomeric Target Bis-(Acetylacetonato) Copper(II) with Transmetalator Bis-(Diethoxydithiophosphato) Zinc(II) in Methylene Chloride 单体靶物双(乙酰丙酮)铜(II)与转金属物双(二氧基二硫代磷酸)锌(II)在二氯甲烷中的反应产物及动力学
Pub Date : 2015-05-08 DOI: 10.4236/OJPC.2015.52005
H. Abo-Eldahab
Reaction of bis-(acetylacetonato) copper(ΙΙ) (A) with transmetalator Zn((EtO)2PS2)2 (B2; Et = ethyl) in methylene chloride is a simple irreversible second-order process over a wide temperature range which is the first example of a second-order reaction of mononuclear target A with a transmetalator. The plots of kobsd vs [A] are linear, meaning that there is one A and one B2 in the activated complex of the slowest reaction step. The slowest step is precursor formation on the basis that B2 is an exceptionally weak complex. The product of the A/B2 reaction is the strong successor complex Zn(acac)2•Cu(ps)2. The data are compared with those for reactions of the same target (A) with S-methyle isopropylidenehydrazinecarbodithioate-carbodithioato-metal(II) complexes M(SN)2 (M=Ni (C1) and Zn (C2)). The reaction is not like that of A with Ni ((MeO)2PS2)2 (B1; Me=methyl), because it is irreversible and also consistent with the measured lower relative thermodynamic stability of B2 compared to B1.
双-(乙酰丙酮)铜(ΙΙ) (A)与转金属剂Zn((EtO)2PS2)2 (B2)的反应Et =乙基)在二氯甲烷中的反应是一个简单的、不可逆的、在宽温度范围内进行的二级反应,这是单核靶a与金属变性物二级反应的第一个例子。kobsd与[A]呈线性关系,即在最慢反应步骤的活化配合物中有一个A和一个B2。最慢的一步是前体的形成,因为B2是一种非常弱的复合体。A/B2反应的产物是强后继络合物Zn(acac)2•Cu(ps)2。并与同一目标(A)与s -甲基异丙基肼碳二硫代-碳二硫代-金属(II)配合物M(SN)2 (M=Ni (C1)和Zn (C2))反应的数据进行了比较。该反应不像A与Ni ((MeO)2PS2)2 (B1)的反应;Me=甲基),因为它是不可逆的,也与测量到的B2相对于B1较低的相对热力学稳定性相一致。
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引用次数: 0
Interconversion between Planar-Triangle, Trigonal-Pyramid and Tetrahedral Configurations of Boron (B(OH)3 -B(OH)4- ), Carbon (CH3+ -CH3X) and for the Group 15 Elements as Nitrogen (NH3-NH4+ ). A Modelling Description with Ab Initio Results and Pressure-Induced Experimental Evidence 硼(B(OH)3 -B(OH)4-)、碳(CH3+ - ch3x)和15族元素氮(NH3-NH4+)的平面三角形、三角金字塔和四面体构型之间的相互转化。具有从头算结果和压力诱导实验证据的模型描述
Pub Date : 2015-01-20 DOI: 10.4236/OJPC.2015.51001
H. Buck
Recently a mechanistic understanding of the pressure-and/or temperature-induced coordination change of boron in a borosilicate glass has been demonstrated by Edwards et al. In situ high-pressure 11B solid-state NMR spectroscopy has been used in combination with ab initio calculations in order to obtain insight in the molecular geometry for the pressure-induced conversion. The results indicate a deformation of the B(OH)3 planar triangle, under isotropic stress, into a trigonal pyramid that serves as a precursor for the formation of a tetrahedral boron configuration. From our point of view, the deformation controlling the out-of-plane transition of boron accompanied with a D3h into C3v geometric change is an interesting transformation because it matches with our molecular description based on Van’t Hoff modelling for the tetrahedral change of carbon in CH3X by substitution of X with nucleophiles via a trigonal bipyramid state in which the transferred carbon is present as a methyl planar triangle “cation”. Van’t Hoff modelling and ab initio calculations have been also applied on the dynamics of the out-of-plane geometry of a transient positively charged carbon in a trigonal pyramidal configuration into a planar trivalent carbon cation. Finally the same model is also used for the C3v trigonal pyramidal configurations as NH3 of the group 15 elements in their nucleophilic abilities.
最近,Edwards等人证明了硼硅酸盐玻璃中压力和/或温度诱导的硼配位变化的机理。原位高压11B固态核磁共振波谱与从头算计算相结合,以获得压力诱导转化的分子几何结构。结果表明,在各向同性应力作用下,B(OH)3平面三角形变形为三角形金字塔,为四面体硼结构的形成提供了前驱体。从我们的角度来看,控制硼的面外转变的变形伴随着D3h到C3v的几何变化是一个有趣的转变,因为它符合我们基于范霍夫模型的分子描述,即CH3X中碳的四面体变化是由亲核试剂通过三角双棱柱态取代X,其中转移的碳以甲基平面三角形“阳离子”的形式存在。范霍夫模型和从头计算也被应用于一个瞬态带正电的碳在三角形锥体结构中转变为平面三价碳阳离子的面外几何动力学。最后,同样的模型也用于C3v三角锥体构型,如15族元素的NH3的亲核能力。
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引用次数: 1
Thermochemical Parameters of Tetramethylthiourea Adducts of Certain Metal(II) Bromides 某些金属(II)溴化物四甲基硫脲加合物的热化学参数
Pub Date : 2015-01-20 DOI: 10.4236/OJPC.2015.51002
P. Dunstan
Complexes of the general formula [MBr2(TMTU)n] (where M is Mn, Fe, Co, Ni, Cu, Zn or Cd; TMTU is Tetramethylthiourea; n is 0.75, 2 or 3) were obtained by the reaction of salts and ligand in solution. The bromides were selected among several other salts because they had thermochemical data in the literature. Properties as capillary melting points; C, H, N, Br and metal contents; TG/DTG and DSC curves; and IR and electronic spectra were determined. The values of several thermodynamic parameters for the complexes were found by solution calorimetry. From them, the standard enthalpies of the metal-sulphur coordinated bonds were calculated. The standard enthalpies of the formation of the gaseous phase adducts also were estimated.
通式[MBr2(TMTU)n]的配合物(其中M为Mn、Fe、Co、Ni、Cu、Zn或Cd;TMTU是四甲基硫脲;N = 0.75,盐与配体在溶液中反应得到2或3)。溴化物之所以在其他几种盐中被选中,是因为它们在文献中有热化学数据。毛细管熔点性能;C、H、N、Br及金属含量;TG/DTG和DSC曲线;红外光谱和电子光谱的测定。用溶液量热法测定了配合物的几个热力学参数。由此计算了金属-硫配位键的标准焓。对气相加合物形成的标准焓也进行了估计。
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引用次数: 0
The Relation between the Heat of Melting Point, Boiling Point, and the Activation Energy of Self-Diffusion in Accordance with the Concept of Randomized Particles 基于随机粒子概念的熔点热、沸点热与自扩散活化能的关系
Pub Date : 2014-10-15 DOI: 10.4236/OJPC.2014.44019
V. P. Malyshev, A. Makasheva
On the example of typical metals, it’s found that the activation energy of self-diffusion is above of the melting heat and below of vaporization heat. This corresponds to the existence of liquid-mobile particle classification based on the concept of randomized particles. A formula for estimating the activation energy of self-diffusion by which it is approximately half of the heat of evaporation of the substance is recommended. We derive the temperature dependence for a fraction self-diffusion’s particles.
以典型金属为例,发现自扩散活化能大于熔化热,小于汽化热。这对应于基于随机粒子概念的液体移动粒子分类的存在。提出了一种估算自扩散活化能的公式,该公式约为物质蒸发热的一半。我们推导了部分自扩散粒子的温度依赖关系。
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引用次数: 4
Effect of Chloride Concentration on the Corrosion Rate of Maraging Steel 氯化物浓度对马氏体时效钢腐蚀速率的影响
Pub Date : 2014-10-15 DOI: 10.4236/OJPC.2014.44018
H. E. Desouky, H. Abo-Eldahab
The corrosion behavior of Maraging steel has been studied by using different techniques, including open circuit potential and polarization measurements in addition to microstructure examination such as optical microscopy and XRD (X-Ray Diffraction) investigation. The corrosion behavior of Maraging steel has been examined in sodium chloride solutions with different concentrations from 0.1 M to 2 M. It was found that the corrosion resistance of Maraging steel is inversely proportional with the concentration of sodium chloride solution. The corrosion resistance is directly proportional to the Mo and Ti content in the Maraging steel. Heat treatment of the Maraging steel improved its mechanical properties with no effect on the corrosion behavior as the precipitation of inter-metallic compounds leading to some galvanic action. However, sample IV having lower Mo content than sample V showed after heat treatment an improvement in the corrosion resistance.
马氏体时效钢的腐蚀行为通过不同的技术进行了研究,包括开路电位和极化测量,以及光学显微镜和x射线衍射(XRD)等显微组织检查。研究了马氏体时效钢在0.1 ~ 2m浓度氯化钠溶液中的腐蚀行为,发现马氏体时效钢的耐腐蚀性与氯化钠溶液浓度成反比。马氏体时效钢的耐蚀性与Mo、Ti含量成正比。马氏体时效钢经过热处理后,其力学性能得到改善,但由于金属间化合物的析出导致一定的电偶作用,对腐蚀行为没有影响。而Mo含量低于V的试样在热处理后的耐蚀性有所提高。
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引用次数: 10
Comparative Isotherms Studies on Adsorptive Removal of Congo Red from Wastewater by Watermelon Rinds and Neem-Tree Leaves 西瓜皮和尼姆树叶吸附去除废水中刚果红的比较等温线研究
Pub Date : 2014-10-15 DOI: 10.4236/OJPC.2014.44017
M. Ibrahim, Sadiq Sani
Equilibrium adsorption studies for detoxification of Congo Red (CR) dye from single component model wastewater by powdered watermelon rinds and neem leaves adsorbents were carried out with the view to test the applicability of the adsorption process to Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Harkins-Jura isotherm models. The values of correlation coefficient, R2 (0.9359 - 0.9998), showed that all the experimental data fitted the linear plots of the tested isotherm models. Dubinin-Radushkevich’s monolayer maximum adsorption capacity qD (20.72 - 26.06 mg/g) is better than Langmuir’s qm (18.62 - 24.75 mg/g) for both adsorbents with the capacities higher for adsorption on watermelon rind than on neem leaves. Values of Langmuir separation factor (RL) suggest unfavourable adsorption processes (i.e. chemisorption) of the dye on both the adsorbents, while Freundlich constant (nF) indicates unfavourable process only for CR adsorption onto neem leaves. The Dubinin-Radushkevich’s mean free energy of adsorption, E (0.29 - 0.32 kJ/mol), suggests physical adsorption processes. Values for Temkin’s heat of adsorption, bT (-0.95 to 0.74 kJ/mol), also show physical adsorption process.
采用西瓜皮粉和印楝叶吸附剂对单组分模型废水中刚果红(CR)染料进行了平衡吸附研究,以验证吸附过程对Langmuir、Freundlich、Temkin、Dubinin-Radushkevich和Harkins-Jura等温线模型的适用性。相关系数R2(0.9359 ~ 0.9998)表明,实验数据与所测等温线模型的线性图吻合良好。Dubinin-Radushkevich单层最大吸附量qD (20.72 ~ 26.06 mg/g)均优于Langmuir单层最大吸附量qm (18.62 ~ 24.75 mg/g),且对西瓜皮的吸附量大于对印楝叶的吸附量。Langmuir分离因子(RL)值表明染料在两种吸附剂上的吸附过程(即化学吸附)都是不利的,而Freundlich常数(nF)表明仅CR在印楝叶上的吸附过程是不利的。Dubinin-Radushkevich平均吸附自由能E (0.29 ~ 0.32 kJ/mol)表明吸附过程为物理吸附过程。Temkin吸附热bT值(-0.95 ~ 0.74 kJ/mol)也表现为物理吸附过程。
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引用次数: 72
The Even-Odd Rule on Single Covalent-Bonded Structural Formulas as a Modification of Classical Structural Formulas of Multiple-Bonded Ions and Molecules 单共价键结构式的奇偶规则作为多键离子和分子经典结构式的修正
Pub Date : 2014-10-15 DOI: 10.4236/OJPC.2014.44020
G. Auvert
In organic chemistry, as defined by Abegg, Kossel, Lewis and Langmuir, compounds are normally represented using structural formulas called Lewis structures. In these structures, the octet rule is used to define the number of covalent bonds that each atom forms with its neighbors and multiple bonds are frequent. Lewis’ octet rule has unfortunately shown limitations very early when applied to non-organic compounds: most of them remain incompatible with the “rule of eight” and location of charges is uncertain. In an attempt to unify structural formulas of octet and non-octet molecules or single-charge ions, an even-odd rule was recently proposed, together with a procedure to locate charge precisely. This even-odd rule has introduced a charge-dependent effective-valence number calculated for each atom. With this number and the number of covalent bonds of each element, two even numbers are calculated. These numbers are both used to understand and draw structuralformulas of single-covalent-bonded compounds. In the present paper, a procedure is proposed to adjust structural formulas of compounds that are commonly represented with multiple bonds. In order to keep them compatible with the even-odd rule, they will be represented using only single covalent bonds. The procedure will then describe the consequences of bond simplification on charges locations. The newly obtained representations are compared to their conventional structural formulas, i.e. single-bond representation vs. multiple-bond structures. Throughout the comparison process, charges are precisely located and assigned to specific atoms. After discussion of particular cases of compounds, the paper finally concludes that a rule limiting representations of multiplecovalent bonds to single covalent bonds, seems to be suitable for numerous known compounds.
在阿贝格、科塞尔、刘易斯和朗缪尔所定义的有机化学中,化合物通常用称为路易斯结构的结构式来表示。在这些结构中,八隅体规则用于定义每个原子与其相邻原子形成的共价键的数量,并且经常有多个键。不幸的是,刘易斯八隅体规则在应用于非有机化合物时很早就显示出了局限性:它们中的大多数仍然与“八隅体规则”不相容,而且电荷的位置也不确定。为了统一八隅体分子和非八隅体分子或单电荷离子的结构式,最近提出了一个奇偶规则,并提出了一种精确定位电荷的方法。这个奇偶规则引入了一个计算每个原子的与电荷有关的有效价数。有了这个数和每个元素的共价键数,就可以计算出两个偶数。这些数字用于理解和绘制单共价键化合物的结构式。本文提出了一种调整通常以多键表示的化合物的结构式的方法。为了使它们符合奇偶规则,它们将只用单个共价键来表示。然后,程序将描述键简化对电荷位置的影响。将新获得的表示与传统的结构公式进行比较,即单键表示与多键结构。在整个比较过程中,电荷被精确地定位并分配给特定的原子。在讨论了化合物的特殊情况后,本文最后得出结论,将多共价键表示为单共价键的规则似乎适用于许多已知化合物。
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引用次数: 11
Coherence of the Even-Odd Rule with an Effective-Valence Isoelectronicity Rule for Chemical Structural Formulas: Application to Known and Unknown Single-Covalent-Bonded Compounds 化学结构式偶奇规则与有效价等电子规则的相干性:在已知和未知单共价键化合物中的应用
Pub Date : 2014-07-29 DOI: 10.4236/OJPC.2014.43015
G. Auvert
Ions or molecules are said to be isoelectronic if they are composed of different elements but have the same number of electrons, the same number of covalent bonds and the same structure. This criterion is unfortunately not sufficient to ensure that a chemical structure is a valid chemical compound. In a previous article, a procedure has been described to draw 2D valid structural formulas: the even-odd rule. This rule has been applied first to single-bonded molecules then to single-charged single-bonded ions. It covers hypovalent, hypervalent or classic Lewis’ octet compounds. The funding principle of the even-odd rule is that each atom of the compound possesses an outer-shell filled only with pairs of electrons. The application of this rule guarantees validity of any single-covalent-bond chemical structure. In the present paper, this even-odd rule and its electron-pair criterion are checked for coherence with an effective-valence isoelectronic rule using numerous known compounds having single-covalent-bond connections. The test addresses Lewis’ octet ions or molecules as well as hypovalent and hypervalent compounds. The article concludes that the even-odd rule and the effective-valence isoelectronicity rule are coherent for known single-covalent-bond chemical compounds.
如果离子或分子由不同的元素组成,但具有相同数量的电子,相同数量的共价键和相同的结构,则称为等电子离子或分子。不幸的是,这个标准不足以保证一个化学结构是有效的化合物。在前一篇文章中,描述了绘制二维有效结构公式的过程:偶奇规则。这一规律首先应用于单键分子,然后应用于单电荷的单键离子。它涵盖了低价、高价或经典的路易斯八隅体化合物。奇偶规则的资助原理是化合物的每个原子都有一个只充满电子对的外壳。该规则的应用保证了任何单一共价键化学结构的有效性。在本文中,使用许多已知的具有单共价键连接的化合物,用有效价等电子规则检查了奇偶规则及其电子对准则的相干性。测试地址刘易斯的八隅体离子或分子以及低价和高价化合物。本文认为,已知的单共价键化合物的奇偶规则和有效价等电子规则是一致的。
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引用次数: 8
Characterization and Adsorption Study of Thymol on Pillared Bentonite 百里香酚在膨润土上的表征及吸附研究
Pub Date : 2014-07-29 DOI: 10.4236/OJPC.2014.43013
M. E. miz, S. Salhi, Ikrame Chraibi, A. Bachiri, M. Fauconnier, A. Tahani
Pillared clay (PILC) was prepared from Moroccan clay and characterized, and its aqueous thymol adsorption capacities were studied using a batch equilibrium technique. So, we tested the encapsulation of thymol by aluminum pillared clay (PILC). The PILCs displayed a total surface area of 270 m2/g, a total pore volume of 0.246 cm3/g and an average pore diameter of 8.9 A, which corresponds to the size of Al13 forming the pillars between the clay layers. The adsorption capacity shown by the PILCs for thymol from water is close to 319 mg?g-1 for low solid/liquid ratio (0.2%). This result suggests that the PILCs have both hydrophobic and hydrophilic characteristics, as a result of the presence of silanol and siloxane groups formed during the pillaring and calcination of the PILCs. The experimental data were analyzed by the Freundlich and the Langmuir isotherm types for low values of equilibrium concentration. The rise of the isotherm in this range of concentrations was related to the affinity of thymol for clay sites, and the equilibrium data fitted well with the Freundlich model with maximum adsorption capacity of 319.51 mg/g for a ratio RS/L = 0.2%. Pseudo-first and pseudo-second-order kinetic models were tested with the experimental data and pseudo-first order kinetics was the best for the adsorption of thymol with coefficients of correlation R2 ≥0.986, and the adsorption was rapid with 90% of the thymol adsorbed within the first 20 min.
以摩洛哥粘土为原料制备了柱状粘土(PILC),并对其进行了表征,采用间歇平衡法研究了其对百里香酚的吸附性能。为此,对百里香酚进行了铝柱粘土包封试验。PILCs的总表面积为270 m2/g,总孔隙体积为0.246 cm3/g,平均孔径为8.9 a,与形成粘土层间柱的Al13的大小相对应。PILCs对水中百里酚的吸附量接近319mg ?G-1为低固液比(0.2%)。这一结果表明,由于柱化和煅烧过程中形成的硅醇和硅氧烷基团的存在,PILCs具有疏水性和亲水性特征。实验数据用Freundlich和Langmuir等温线类型对低平衡浓度进行了分析。等温线在此浓度范围内的升高与百里香酚对粘土位点的亲和力有关,平衡数据符合Freundlich模型,当RS/L = 0.2%时,最大吸附量为319.51 mg/g。实验数据验证了拟一级和拟二级吸附动力学模型,拟一级吸附效果最好,相关系数R2≥0.986,吸附速度快,前20 min吸附90%的百里香酚。
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引用次数: 26
Comparative Study of Physical Properties of In-Use Surfactant-Grafted Polyacrylamides for Oilfield 油田用表面活性剂接枝聚丙烯酰胺物性比较研究
Pub Date : 2014-07-29 DOI: 10.4236/OJPC.2014.43016
Tingting Jiang, Haiyu Wang, Baohui Wang
Surfactant-grafted Polyacrylamide (S-PAM), as a new type of oil displacement agent in oilfield, integrates the advantages of both polymer and surfactant. The oil displacement experiments using S-PAM in multi-blocks reveal that in-use S-PAMs differ greatly from ordinary polymers and the physical properties remain unclear. This is unfavorable to production application and occupational health and safety. This research compared the physical properties of S-PAMs selected from two producing area, including specific gravity, particle size and viscosity. The compared results showed that specific gravity of Lianhua S-PAM was smaller than Haibo S-PAM; Lianhua S-PAM and Haibo S-PAM accounted for the 93.8% and 80.1% of the total amount via the particles with 40 mesh and 60 mesh; the viscosity of Lianhua S-PAM was higher than that of Haibo S-PAM in two S-PAM solutions with different concentrations.
表面活性剂接枝聚丙烯酰胺(S-PAM)是一种集聚合物和表面活性剂优点于一体的新型油田驱油剂。利用S-PAM进行的多区块驱油实验表明,使用中的S-PAM与普通聚合物有很大不同,其物理性质尚不清楚。这不利于生产应用和职业健康安全。本研究比较了两个产区的s - pam的物理性质,包括比重、粒径和粘度。对比结果表明,联华S-PAM的比重小于海波S-PAM;联华S-PAM和海博S-PAM分别占40目和60目颗粒量的93.8%和80.1%;在两种不同浓度的S-PAM溶液中,联华S-PAM的粘度均高于海波S-PAM。
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引用次数: 1
期刊
物理化学期刊(英文)
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