986 resultados para Barrès, Maurice (1862-1923)
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Sinopse dos trabalhos na Câmara dos Deputados, em 1923.
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909 p.
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No ano de 1923, o Clube de Regatas Vasco da Gama disputa pela primeira vez a Primeira Divisão do Campeonato Carioca de Futebol. A equipe conquista o título tendo, entre seus jogadores, homens negros e mulatos. Com vitórias expressivas, aquela trajetória passa a ocupar um lugar importante no imaginário construído sobre as primeiras décadas do futebol brasileiro. Toda esta construção está fundamentada na obra de Mario Filho, O Negro no Futebol Brasileiro. O livro relata o feito vascaíno como uma trajetória heróica, na qual um time formado por negros e mulatos precisou superar preconceitos raciais para alcançar seus objetivos. A proposta desta pesquisa é comparar a narrativa de Mario Filho com o que foi escrito nos jornais da época. O objetivo é verificar se há mais incoerências ou coincidências entre o que Mario Filho escreveu e o que os jornais noticiaram. Ao retomar os jornais da década de 1920, verificamos como a imprensa enxergava o acontecimento à época e, se o preconceito racial estava presente nas páginas dos jornais, assim como nos faz crer a obra de Mario Filho. A comparação revelou que, em alguns momentos, a narrativa de Mario Filho encontra respaldo integral nas notícias publicadas no ano de 1923. No entanto, em outras oportunidades o autor não encontra nenhum respaldo nas outras fontes consultadas.
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The aim of this study was to investigate the historical catch record from the Castle Fishery on the River Derwent over the period 1923 - 1989, to determine if changes had taken place in the composition of the catch and to examine the influence of flow on the performance of the fishery. The River Derwent is situated in West Cumbria, North West England. It flows from its source on Scafell Pike (NGR NY 229 089) westwards discharging into the Irish sea at Workington, a distance of 52 km. Over its length it receives water from an additional 214 km of stream, 5 large lakes and approximately 30 small tarns. The catchment drains a total area of 663 km2. The study concludes that through the time period there was considerable variation in catch between years. The trend was for the catch to increase steadily over the period 1923 - 1958, declining rapidly in 1959, after which catches increased steadily reaching a peak in the mid-sixties, before declining towards the end of the decade. During the seventies and eighties catches remained relatively stable at between 300 - 600 salmon per year until 1988 when over 2000 salmon were reported caught, the greatest number in any year over the study period.
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The effect of decreasing frost frequency on desert vegetation was documented in Grand Canyon by replication of historical photographs. Although views by numerous photographers of Grand Canyon have been examined, 400 Robert Brewster Stanton and Franklin A. Nims views taken in the winter of 1889-1890 provide the best information on recent plant distribution. In Grand Canyon, where grazing is limited by the rugged topography, vegetation dynamics are controlled by climate and by demographic processes such as seed productivity, recruitment, longevity and mortality. The replicated photographs show distribution and abundance of several species were limited by severe frost before 1889. Two of these, brittlebush (Encelia farinosa) and barrel cactus (Ferocactus cylindraceus), have clearly expanded their ranges up-canyon and have increased their densities at sites where they were present in 1890. In 1890, brittlebush was present in warm microhabitats that provided refugia from frost damage. Views showing desert vegetation in 1923 indicate that Encelia expanded rapidly to near its current distribution between 1890 and 1923, whereas the expansion of Ferocactus occurred more slowly. The higher frequency of frost was probably related to an anomalous increase in winter storms between 1878 (and possibly 1862) and 1891 in the southwestern United States.
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Sex ratio data of two species of penaeid prawns Metapenaues kutchensis George, George and Rao, 1963 and Parapenaeopsis sculptilis (Heller, 1862), occurring in the Gulf of Kachchh, were statistically analysed. A preponderance of females was observed in both the species and the ratio of male to female for both years combined for M. kutchensis and P. sculptilis was found to be 1:15 and 1:2.7, respectively. Chi-square analysis revealed significant difference in the sex ratio of the two species.
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A total of 38 Amiota (s. str.) species (about 40% of the world total) are reported from southern China, with descriptions of 23 new species, i.e. sinuata species-group: aculeata Chen and Aotsuka, sp. nov., subsinuata Chen and Aotsuka, sp. nov., xishuangbanna Chen and Aotsuka, sp. nov.; basdeni species-group: brevipartita Chen and Gao, sp. nov., curvispina Chen and Gao, sp. nov., lipingae Chen and Gao, sp. nov., huae Chen and Gao, sp. nov., longispina Chen and Gao, sp. nov.; taurusata species-group: asymmetrica Chen and Takamori, sp. nov.; femorata Chen and Takamori, sp. nov., yixiangensis Chen and Takamori, sp. nov.; alboguttata species-group: ailaoshanensis Chen and Watabe, sp. nov., arcuata Chen and Watabe, sp. nov., dehiscentia Chen and Watabe, sp. nov., jizushanensis Chen and Watabe, sp. nov., latitabula Chen and Watabe, sp. nov., luguhuensis Chen and Watabe, sp. nov., nozawai Chen and Watabe, sp. nov., paraspinata Chen and Watabe, sp. nov., shangrila Chen and Watabe, sp. nov.; and ungrouped: fuscicata Chen and Zhang, sp. nov., wangi Chen and Zhang, sp. nov., wuyishanensis Chen and Zhang, sp. nov. A key to all species from southern China is provided. The Amiota fauna of southern China at the species-group level is compared with that of six geographic regions. The subgenus Amiota is assumed to have originated and produced many species-groups in the Oriental region of East Asia, and then the basdeni, alboguttata and rufescens species-groups might have spread to Europe and North-Central America throughout the Palearctic region of East Asia and both the apodemata, sinuata and nagatai species-groups to tropical regions of South-East Asia.
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瘦尾细额溞是一种出现数量极其稀少的枝角类。关于它的生物学特征尚未见诸文献。本文测量了一次采自云南永胜一池塘的本种300个两性个体的体长和怀卵量,就其幼体与成体的数量、体长与怀卵量、雄性以及性比等问题探讨了种群的生物学状况。 详细观察比较了这个种的重要分类特征——雌体后腹部,并描述了变异范围。对卵鞍和雄体也作了描述。
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伯胺N_(1923)(RNH_2)是一种对许多金属具有优良萃取性能的萃取剂,因RNH_2为较强的Lewis碱,能以多种途径与金属离子结合,文献报道的一般为加合反应及阴离子交换机理,至于配位反应未见报道,故详细地研究RNH_2萃取不同金属离子的机理,发现新的萃取,分离体系,具有理论和实际意义。本文分别研究了RNH_2及其相应盐从不同介质中萃取Ag~+,Zn~(2+),Cd~(2+),Sc~(3+)的机理。提出了RNH_2能以配位反应萃取金属离子,并且发现对一些体系(如ZnCl_2, Zn(SCN)_2, CdCl_2等)RNH_2及其盐均具有较好的萃取行为。对有关体系详细研究了其萃取机理:1)RNH_2萃取AgNO_3的机理。在接近中性介质中,RNH_2是AgNO_3的优良萃取剂,其反应机理为:2RNH_(2(0)) + Ag~+ + NO_3~- <-> (RNH_2)_2AgNO_(3(0))考察了溶剂,温度等反应平衡的影响,其分配比基本随溶剂介电常数的增大而增大,并且该反应为放热反应,温度升高不利于萃取。我们还解析了该萃合物的IR及NMR。2,RNH_3NO_3萃取硫代硫酸银的机理。与上述AgNO_3体系不同,RNH_2不能萃取硫代硫酸银,但RNH_3NO_3能以阴离子交换反应萃取该体系中的Ag(I)。通过研究不同因素对分配比的影响,指出在该体系中Ag(I)同时以AgS_2O_3~-和Ag(S_2O_3)_2~(3-)两种形式萃入有机相。并且有机相中AgS_2O_3~-/Ag(S_2O_3)_2~(3-)比值随着NO_3~-浓度的增大,RNH_3NO_3、S_2O_3~(2-)浓度的减小而增大。萃合物的IR分析证明存在两种不同配位形式的S_2O_3~(2-)。3,RNH_2萃取ZnCl_2的机理及平衡规律。研究了RNH_2在不同酸度条件下萃取ZnCl_2的机理,在pH值较高时,RNH_2能以配位反应萃取ZnCl_2,其反应为:2RNH_(2(0)) + ZnCl_2 <-> (RNH_2)_2ZnCl_(2(0))并详细地研究了其平衡规律,得出数学模型:1/D = 2/(C_(RMH_(2(o)))) X + (1 + Σ from i = 1 to 4 of β_i C_(cl~-)~i)/(K C_(cl~-)~2 C_(RNH_(2(0))) (X为平衡水相Zn~(2+)总浓度) 在高酸度([HCl] = 2.8 M)条件下,RNH_2萃取ZnCl_2呈加成反应:(RNH_3Cl)_(3(0)) + ZnCl_2 <-> (RNH_3Cl)_2ZnCl_(2(0))求得了萃取过程的各热力学函数。4)RNH_2萃取ZnBr_2, ZnI_2的机理。研究RNH_2萃取ZnBr_2,ZnI_2的性能表明,在pH值较高时, RNH_2能以萃取ZnCl_2相同的机理萃取ZnBr_2, ZnI_2,其反应为:2RNH_(2(0)) + ZnX_2 <-> (RNH_2)_2ZnX_(2(0)) (x~- = Br~-, I~-) 计算了不同RNH_2浓度条件下反应的平衡常数,表明不是RNH_2浓度的函数,该平衡常数随温度升高而降低。同时我们在相同条件下,比较RNH_2萃取ZnX_2的能力为:ZnI_2 > ZnBr_2 > ZnCl_2 5,RNH_2及其硝酸盐萃取Zn(SCN)_2的机理 在Zn(SCN)_2体系中,RNH_2及RNH_3NO_3的均能较有效地萃取Zn(II),但其反应机理并不相同,RNH_2以配位反应萃取Zn(SCN)_2,相应的反应为:2RNH_(2(0)) + Zn(SCN)_2 <-> (RNH_2)_2Zn(SCN)_(2(0)) RNH_3NO_3则以阴离子交换反应萃取Zn(SCN)_4~(2-),其反应如下:(RNH_3NO_3)_(2(0)) + Zn(SCN)_4~(2-) <-> (RNH_3)_2Zn(SCN)_(4(0)) + 2NO_3~- 测定并计算了各反应的浓度平衡常数及热力学函数,两反应均为放热反应。同时,在相同条件下,RNH_2比RNH_3NO_3有更强萃取Zn(II)的能力。6,RNH_2萃取CdCl_2及其它Cd(II)盐的机理 RNH_2及RNH_3Cl能分别以配位反应及加合反应萃取CdCl_2,通过萃合物组成的测定,得出反应方程式为:3RNH_(2(o)) + CdCl_2 <-> (RNH_2)_3CdCl_(2(0)) (RNH_3Cl)_(3(o)) + CdCl_2 <-> (RNH_3Cl)_3CdCl_(2(0))计算了各反应的平衡常数及热力学函数。同时观察了RNH_2萃取CdBr_2, CdI_2, Cd(SCN)_2的性能,相应萃合物组成为(RNH_2)_2CdX_2 (X~- = Br~-, I~-, SCN~-)。在相同条件下,CdX_2的萃取率次序为:Cd(NO_2)_2 < CdCl_2 < CdBr_2 < Cd(SCN)_2 < CdI_2。并讨论了CdX_2的生成能,第二级累积稳定常数,X~-的半径等因素与Cd(II)分配比的关系。7,RNH_2硫酸盐萃取Sc_2(SO_4)_3的机理 研究了不同因素对其萃取性能的影响,指出在硫酸介质中,RNH_2是Sc~(3+)的优良萃取剂。通过萃合物组成的测定得到该萃取反应式为:1.25[(RNH_3)_2SO_4]_(2(0)) + Sc(SO_4)_3~(3-) <-> (RNH_3)_3Sc(SO_4)_3·(RNH_3)_2SO_(4(0)) + 1.5SO_4~(2-)测定并计算了该反应的平衡常数及热力学函数。通过详细解释萃合物的IR,证明在该萃合物中SO_4~(2-)是以双配位形式与Sc~(3+)相结合。在上述萃取机理研究了基础上初步探讨了用RNH_2回收银及进行Zn(II)-Cd(II)分离的可能性。
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伯胺由于其特殊的结构(R-NH_2),使它具有和仲、数胺不相同的一些性质。有较强的和矿物酸HX结合形成RNH_3X的能力,从而以离子交换机理萃取金属离子;也可以-NH_2上的氮、氢原子同以高价存在的过渡金属含氧酸以氢键方式相结合;另外,RNH_2也可通过氮原子以配位键形式与一些属于软酸类的过度金属离子形成配合物。通过伯胺萃取金属离子行为的研究,可发现新的萃取体系,扩大我国自行设计的伯胺N_(1923)萃取剂的应用领域,为金属离子的分离提纯工艺提供基本参数。我们实验室过去曾对伯胺N_(1923)萃取稀土(III)、Fe(III)、Zn (II)、Cd(II)、Ag(I)、Sc(III)等的机理进行了比较系统的研究。本工作是在此基础上,进一步完善及扩大N_(1923)对周期表中各族元素的萃取及应用。为此,我们选择了文献尚未报道的Ti(IV)、HgCl_2、Hg(CH_3COO)_2、Cu(CH_3COO)_2为研究对象,对它们的萃取机理进行了较详细的研究。结果表明,自由的N_(1923)或其盐对上述体系具有良好的萃取性能,并初步讨论了N_(1923)在金属离子萃取分离中的应用。一、伯胺N_(1923)萃取HgCl_2的机理 微量汞的萃取及分离对环境保护具有重要的实际意义。我们的研究结果表明,在pH值为3-4.5范围内,即使Cl~-浓度很低时,伯胺N_(1923)也能几乎定量地萃取HgCl_2,其盐酸盐亦能有效地萃取Hg(II),但两者的萃取机理不同。自由伯胺RNH_2可与HgCl_2形成配合物,其萃取机理为:RHN_(2(0)) + HgCl_2 <-> Hg(RNH_2)Cl_(2(0))对伯胺盐,实验证明其机理主要为加合反应,但当Cl~-浓度较高时,则为阴离子交换反应:加合反应:2RNH_3Cl_((0)) + HgCl_2 <-> (RNH_3Cl)_2HgCl_(2(0))交换反应:2RNH_3Cl_((0)) + HgCl_4~(2-) <-> (RNH_3)_2HgCl_(4(0)) + 2Cl~-通过考察温度对配位萃取反应的影响,求得反应的热效应ΔH = -48.82 KJ/mol,并分析了萃合物的IR、NMR谱。二、伯胺N_(1923)萃取Hg(CH_3COO)_2的机理 与HgCl_2体系相似,自由伯胺或其盐均能萃取Hg(CH_3COO)_2,萃取机理分别为:RNH_(2(0)) + Hg(CH_3CCO)_2 <-> Hg(RNH_2)(CH_3COO)_(2(0)) (CH_3COONH_3R)_(2(0)) + Hg(CH_3COO)_2 <-> (CH_3COONH_3R)_2Hg(CH_3COO)_(2(0))。在不同的萃取剂浓度下,上述反应的表观平衡常数基本不随萃取剂浓度的变化而改变,其对数值分别为:11.85、8.11。三、伯胺N_(1923)萃取Cu(CH_3COO)_2的机理 水相酸度对萃取反应的影响表明,RNH_2在近中性体系中具有很好的萃取性能,而在乙酸浓度较高的条件下,Cu(II)几乎不被RNH_2所萃取。说明自由伯胺能以配位机理的形式萃取Cu(Oh_3coo)_2,经确定,萃取反应式为:2RNH_(2(0)) + Cu(CH_3COO)_2 <-> Cu(RNH_2)_2(CH_3COO)_(2(0))并对该反应的表观平衡常数及热力学函数进行了计算。通过分析萃合物的IR谱,认为Cu(RNH_2)_2(CH_3COO)_2为平面型四配位的配合物。四、(RNH_3)_2SO_4从硫酸溶液中萃取Ti(IV)的研究 在低酸度(pH:0.84)的H_2SO_4溶液中,伯胺N_(1923)对Ti(IV)具有很强的萃取能力。用化学平衡法确定其反应式为:3(RNH_3)_2SO_(4(0)) + Ti(OH)_3~+ + SO_4~(2-) <-> 2(RNH_3)_3Ti(OH_3)(SO_4)_(2(0))我们用正十二胺代替N_(1923),合成了上述萃合物的模拟物,经元素分析确定了萃合物的分子式:(RNH_3)_3Ti(OH)_3(SO_4)_2。并较详细地分析了萃合物的NMR、IR谱。变温NMR的结果表明,萃合物中存在两种含有活泼氢的基团,用D_2O交换后的NMR的结果亦证明了这一点。从萃合物的IR谱中,可得到SO_4~(2-)是以单齿配位形式同Ti(IV)相结合的信息。这些结果为所提出的萃取机理提供了直接的证据。并求出了上述萃取反应的表观平衡常数,其对数值为10.15,该值基本不随萃取剂浓度的变化而发生改变。反应的热效应ΔH = 66.49 KJ/mol,由计算得出的ΔG值可知,上述萃取反应有很大的向右进行的趋势。五、伯胺N_(1923)在萃取分离中的应用 为了扩大N_(1923)的应用,通过上述研究,我们对其在萃取分离中的应用进行了讨论,认为在以下几方面有可能得到应用:1、从环境废水中除Hg(II);2、Hg(II)和Zn(II)、Cd(II)在CH_3COOH体系中的分离;3、CH_3COOH体系中Cu(II)、Co(II)、Ni(II)的萃取分离;4、在较高浓度的H_2SO_4体系中,应用(RNH_3)_2SO_4进行了Ti(IV)-Fe(II)的分离。
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胺类萃取剂具有其独特优点,特别是伯胺,因含有活泼氢,既能作为“阴离子交换剂”,又能与被萃的含氧金属络阴离了形成氢键而溶剂化,同时伯胺为一路易斯碱,可作为配体与某些金属离子形成配位键等,因而已广泛地用于金属离子的提纯与分离工业中。然而,1)为了寻找新的、更有效的萃取及协同萃取体系,以适应分析分离各种金属离子,改善金属离子的分离工艺;2)研究萃取和协同萃取的一般规律,探寻其内在规律性,充实完善萃取化学原理的内容;3)研究多元配合物的组成、结构和机理;4)系统地研究和比较不同结构胺类萃取剂与其它萃取剂对金属离子的萃取及协同萃取的相互作用,探讨多元配合物的形成条件等,因此,研究伯胺N_(1923)与其它萃取剂在不同酸度、不同条件,不同体系中对Zn(II)、Cd(II)、Re(III)的萃取及协同萃取具有一定意义。本文分别研究了伯胺N_(1923)与中性磷试剂对ZnCl_2、CdCl_2、Zn(SCN)_2的协同萃取;伯胺N_(1923)与HPMBP对RE(III)的协同萃取以及伯胺N_(1923)在不同介质中对Sc(III)的萃取机理等,并用得到了一些有意义的结果与结论。一、伯胺N_(1923)与中性磷萃取剂(TBP, DBBP)对Zn(II)、Cd(II)的协同萃取1. 伯胺N_(1923)与TBP、DBBP对ZnCl_2的协萃取 研究了伯胺N_(1923)与TBP、DBBP的正庚烷溶液从盐酸介质中对ZnCl_2的萃取机理,用斜率法、等摩尔系列法确定了协萃配合物组成为:(RNH_3Cl)_3·ZnCl_2·B、(RNH_3Cl)_2·ZnCl_2·B (B = TBP·DBBP)协萃反应为:ZnCl_2 + (RNH_3Cl)_3_((o)) + TBP_((o)) →~(K_(12)(TBP) (RNH_3Cl)_3·ZnCl_3·ZnCl_2·TBP_((o)) ZnCl_2+Z/3(RNH_3Cl)_(3(o)) + DBBP_((o)) → (RNH_3Cl)_2 · ZnCl_2·DBBP_((o))协萃配合物生成反应为:(RNH_3Cl)_3·ZnCl_(2(o)) + TBP_((o))→~(B_(12)(TBP) (RNH_3Cl)_3·ZnCl_2·TBP_((o)) (RNH_3Cl)_3·ZnCl_(2(o)) + DBBP_((o)) →~(B_(12)(DBBP) (RNH_3Cl)_2·ZnCl_2·DBBP_((o)) + RNH_3Cl_((o))同时发现,中性磷试剂对Zn(II)的协萃效应大小影响有下列关系:DBBP>TBP。并求得了协萃反应平衡常数和协萃配合物生成反应平衡常数。在研究溶剂对协同效应影响时发现,对芳香烃及其衍生物,分配比(D)与溶剂介电常数(ε)的关系为D_∝1/ε,而对芳香烃及其衍生物,分配比(D)与介电常数(ε)的关系为D_∝ε。讨论了温度对协萃反应的影响,对协萃配合物的IR、NMR谱也进行了研究。2.伯胺N_(1923)与TBP对Zn_(SCN)_2的协同萃取研究了伯胺N_(1923)与TBP的庚烷溶液从硝酸底液中对Zn(SCN)_2的萃取机理,用等摩尔系列法、斜率法确定了TBP和Zn(SCN)_2以及伯胺N_(1923)与TBP对Zn(SCN)_2的协萃配合物组成分别为:Zn(SCN)_2·3TBP. (RNH_3)_2Zn(SCN)_4·TBP,协谇反应为:Zn(SCN)_4~(2-) + (RNH_3NO_3)_(2(o)) + TBP_((o)) → (RNH_3)_2Zn(SCN)_4·TBP_((o)) + 2NO_3~-协萃配合物三种可能生成反应为(RNH_3)_2Zn(SCN)_(4(o)) + TBP_((o)) → ~(B'12) (RNH_3)_2Zn(SCN)_4·TBP_((o)) (a) (RNH_3NO_3)_(2(o)) + Zn(SCN)_2·3TBP_((o)) + 2SCN~-→~(β"12)→(RNH_3)Zn(SCN)_4βTBP_((o))+2TBP_((o))+2NO_3~- (b) (RNH_3NO_3)_(2(o)) + (RNH_3)_2Zn(SCN)_(4(o)) + 2SCN~- + Zn(SCN)_2.3TBP_((o)) →~(β"12)→R(RNH_3)_2Zn(SCN)_4.TBP_((o)) + 2NO_3~- + TBP_((o)) (c) 求得了协萃反应及生成反应的平衡常数,并由生成反应常数可知:β"'_(12) > β'_(12) > β"_(12),即反应(c)对协萃配合物的生成贡献最大,其次反应(a),最小的是反应(b),同时还发现,不同阴离子对协萃效应影响有下列关系:SCN~- > Cl~_。并对协萃配合物的IR谱进行了研究,讨论了温度对协萃反应的影响。3. 伯胺N_(1923)与TBP、DBBP对Cd(II)的协同萃取研究了伯胺N_(1923)与TBP、DBBP的正庚烷溶液从盐酸介质中对Cd(II)的协同萃取,用等摩尔系列法、斜率法确定了协萃配合物组成为(RNH_3Cl)_2·CdCl_2·B,协萃反应及协萃配合物生成的反应分别为:CdCl_2 + 2/3 (RNH_3Cl)_(3(o)) + B_((o)) →~(K_(12)) → (RNH_3Cl)_2·CdCl_2·B_((o)) (RNH_3Cl_3)·CdCl_2_((o)) + B_((o)) →~(BR)(RNH_3Cl)_2·CdCl_2·B_((o)) + RNH_3Cl_((o))求得了协萃反应及生成反应平衡常数,计算了协萃反应的热力学函数值,结果还发现与Zn(II)协同萃取比较,协同效应大小有下列关系:Zn(II) > Cd(II),由实验结果证实了“萃取效应大,则协萃效应小,反之,萃取效应小,则协同效应大”这一结论。并对协萃配合物的IR、NMR谱进行了研究。二. 伯胺N_(1923)与HPMBP对RE(III)的协同萃取研究了伯胺N_(1923)与HPMBP的二甲苯溶液在盐酸介质中对RE(III)的协萃机理(RE~(3+ = La~(3+), Pr~(3+), Eu~(3+), Gd~(3+), Tb~(3+), Er~(3+), Yb~(3+)和Y~(3+))用斜率法及等摩尔系列法确定了协萃配合物组成为RNH_3Ln(PMBP)_4。求得了关于Pr(III)的协萃反应及生成反应的平衡常数值,协萃反应及生成反应分别为:Ln~(3+) + 4HPMBP_((o)) + RNH_3Cl_((o)) → RNH_3LN(PMBP)_(4(o)) + 4H~+ + Cl~- Ln(PMBP)_(3(o)) + RNH_3Cl_((o)) → RNH_3Ln(PMBP)_(4(o)) + H~+ + Cl~- 结果还发现协萃系数(R)随稀土元素的原子序数(Z)递变而出现“双峰效应”(未见文献报道),而且随RNH_3Cl浓度增加到某一一出现反协同效应。同时研究了关于Pr(III)协萃配合物的IR、NMR谱。三、伯胺N_(1923)在硝酸盐及硫氰酸盐混合介质中对Sc(III)的萃取研究了RNH_3NO_3在硝酸盐和硫氰酸盐混合介质中萃取Sc(III)的机理,结果发现,钪是以Sc(OH)_2~+形式萃入有机相的,且SCN~-, NO_3~-对RNH_3nO_3萃取Sc(III)具有协同效应,并且斜率法、连续变化法及PH值测定确定了萃取反应为:Sc(OH)_2~+ + SCN~- + 2(RNH_3NO_3)_(2((o)) → (RNH_3nO_3)_4.Sc(OH)_2SCN_((o)) Sc(OH)_2~+ + SCN~- + NO_3~- + (RNH_3NO_3)_(2(o)) → (RNH_3NO_3)_2.Sc(OH)(SCN)NO_3 + OH~-求得了反应的平衡常数及热力学函数值。
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本文研究了甲基膦酸二甲庚酯(P_(350))与伯胺N_(1923)的正庚烷溶液在(Na,H)Cl介质中对Zn(Ⅱ)的协同萃取。用等摩尔系列法和斜率法以及IR和~1H NMR确定了协萃配合物的组成为(PNH_3Cl)_(3/2)·ZnCl_2·P_(350),协萃反应平衡常数1gK_(BC)=2.10,协萃配合物的生成常数1gβ=0.46,计算了协萃反应的热力学函数,还从萃取剂的结构探讨了中性磷酸酯在协萃过程中的作用。
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伯胺N1923(以下简称RNH_2)是分离钍和稀土的有效萃取剂。N1923对铁(Ⅲ)和稀土(Ⅲ)萃取热力学的研究表明,在硫酸体系中加入PO_4~(3-),可使稀土(Ⅲ)和铁(Ⅲ)的分离系数增大,本文研究了N1923从硫酸介质中萃取稀土(Ⅲ)和铁(Ⅲ)的动力学性质,以推动N1923在稀土工业中的应用。 N1923由上海有机化学研究所提供,伯胺含量>99%,用等当量浓度的硫酸平衡得到实验
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研究了HEH/EHP(HA)和伯胺N_(1923)盐酸盐(RNH_3C1)的正庚烷溶液从HC1介质中对Zn(Ⅱ)的萃取。发现当以RNH_3Cl为主体萃取剂时,添加HA有利于对Zn(Ⅱ)的萃取;当以HA为主体萃取剂时,添加RNH_3C1则抑制了对Zn(Ⅱ)的萃取。考察了温度对协萃平衡的影响,并计算了体系的热力学函数。