Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

热液成矿作用的地质地球化学动力学——以胶东牟平-乳山金矿带为例

通过对胶东牟平—乳山热液脉状金,铅锌矿床成矿动力学控制规律的研究,说明了建立热液成矿反应体系的方法,并得出以下认识:（1）区域断裂构造活动,通过影响成矿反应体系的热力学性质和条件,控制元素的富集和分散。（2）热液成矿过程中容矿断裂活动可划分为两种作用方式:脆性破裂和韧—脆性张开,构成热液成矿的两种构造动力学环境。（3）热液成矿反应体系是一种开放的动态的热力学体系。断裂的脆性破裂阶段,使体系处于强烈的过饱和状态,矿质在远离平衡状态下快速结晶,加剧物质分异;在脆—韧性张开阶段,矿质在接近平衡态体系中缓慢晶出。（4）热液演化晚期,金在残余溶液中富集;当断裂再次发生构造脉动震颤时,早期形成的块状黄铁矿矿石碎裂,富金溶液充填其中,形成含裂隙金和晶隙金的富矿石。成矿体系热力学演化与构造动力学条件有利的匹配控制着富矿石的形成。     

Na depletion in modern adakites via melt / rock reaction within the sub-arc mantle

Interaction between slab-derived melt and mantle peridotite and the role of slab melt as a metasomatizing agent in the sub-arc mantle is being increasingly recognized. Adakite, the slab melt erupted on the surface, usually exhibits anomalously high MgO, CaO, Cr and Ni contents that indicate interaction with mantle peridotitite. Here we note that Cenozoic adakites have Na₂O contents below 5.8 wt.% with ∼95% samples lower than 5.0 wt.%, and are generally depleted in this component relative to experimental basalt partial melts (mostly beyond 5.0 wt.% and up to 9.0 wt.% Na₂O) produced under 1.5-3.0 GPa conditions that are most relevant to adakite production. We interpret the adakite Na depletion to be also a consequence of the melt / rock reaction that takes place within the hot mantle wedge. During ascent and reaction with mantle peridotite, primary adakite melts gain mantle components MgO, CaO, Cr and Ni but lose Na₂O, SiO₂ and perhaps K₂O to the mantle, leading to Na-rich mantle metasomatism. Selective assimilation of predominately mantle clinopyroxene, some spinel and minor olivine at high T/P has been considered to be an important process in producing high-Mg adakites from primary low-Mg slab melts [Killian, R., Stern, C. R., 2002. Constraints on the interaction between slab melts and the mantle wedge from adakitic glass in peridotite xenoliths. Eur. J. Mineral. 14, 25-36]. In such a process, Na depletion in the assimilated melt is the result of dilution due to the increase in melt mass. Phase relationships in the reaction system siliceous melt + peridotite and quantitative calculation suggest that assimilation of mantle clinopyroxene, olivine and spinel and fractional crystallization of sodic amphibole and orthopyroxene, under conditions of moderate T/P and increasing melt mass, is also an important process that modifies the composition of adakites and causes the Na depletion.     

25～75℃酸性NaCl溶液中方铅矿的溶解动力学

在25～75℃、pH=0.43～2.45的1mol/LNaCl溶液中进行了方铅矿的溶解动力学实验。发现在远平衡条件下,方铅矿的溶解速率r与氢离子活度犤H+犦呈线性关系,溶解速率方程(速率定律)为:r=k犤H+犦,即对H+而言,溶解反应为一级。其中速率常数k为2.344×10-7mol/m2·s(25℃)、1.380×10-6mol/m2·s(50℃)、7.079×10-6mol/m2·s(75℃)。溶解反应的活化能为43.54kJ/mol,方铅矿的溶解机理为表面化学反应,速率决定步骤为表面配合物的离解。     

成矿流体演化与成矿物理化学

成矿流体是富含挥发分 (CO2 、CH4等 )是具有较高含盐度的特殊地质流体。本文讨论了在流体演化过程中挥发分的来源 ,指出主要来自水岩作用、有机质分解及地幔去气和岩浆 ;碱金属及卤素同样具有多来源的性质 ,以海水、含盐系淋滤、建造水为主要来源 ,含盐系重熔可以形成富含碱金属的成矿流体。流体演化过程中氢氧同位素、硫同位素的分馏主要与温度、水岩比值或硫源丰度有关。一个重要的结论是 ,成矿流体的形成主要与地质作用有关 ,而流体来源是次要的。海底热水流体的地球化学特征以高δ3 4 S值、中稀土富集及正铕异常为特征。本文总结了热水流体成矿物理化学条件 ,指出水热流体物相点 :1) 10 80℃ ,7.5× 10 8Pa水溶液与硅酸岩熔浆分熔点 ;2 )水溶液的第二个临界点是气水溶液的超临界点 (374.15℃ ,2 .2 1× 10 7Pa) ;3)水溶液的沸点 (≥ 10 0℃ ,≥ 1× 10 5Pa) ;4)水溶液的冰点 (≤ 0℃ ,1× 10 5Pa) ;5 )H2 O CO2 体系的不混溶温度点 (2 6 6℃ ,2 .15×10 8Pa[1 3 ] 等是重要的成矿相变点。     

高温高压下水岩界面反应与金的迁移富集

高温高压下水岩界面反应与金的迁移富集王玉荣阚小凤王志强（中国科学院广州地球化学研究所，广州５１０６４０）关键词水岩界面反应自发电池实验地球化学本实验以哈达门沟［１］及东坪金矿［２］为地质背景，研究钾长石岩中金矿化富集的物理化学条件。该区金矿既与早期变...     

岩盐及芒硝中各种化合物质量分数的计算

本文以等物质的量的反应规则建立了岩盐、芒硝中各种化合物的质量分数的计算公式。这些公式既符合法定计量单位的要求，又方便计算。