气体在固体表面吸附等温式的热力学理论

气体在固体表面吸附等温式的热力学理论李学良，林建新（合肥工业大学化工学院，２３０００９）气体在固体表面吸附的等温式通常可由动力学、热力学或统计力学等传统方法￣［１］导出。但通常都只针对具体模型作推导，而很少对方法作较完整的论述。本文运用热力学方法，在...     

Gibbs吸附公式在固-气和固-液界面吸附中的应用

Gibbs吸附公式本适用于各种界面的吸附研究 ,但由于有固体参与形成的界面界面能测定困难 ,至今Gibbs公式多只用于气 液界面的研究。本文讨论了Gibbs吸附公式在固 气和固 液界面吸附研究中的应用 ,主要是介绍将Gibbs公式与二维气体状态方程结合导出吸附等温式 ,因吸附而引起的固 气和固 液界面能变化规律 ,以及吸附过程中分子状态变化的有关信息     

气/液界面上十六烷基三甲基溴化铵水溶液的动态表面性质

用最大泡压法测定了不同温度下浓度低于cmc时十六烷基三甲基溴化铵水溶液的动态表面张力.发现当浓度低于0.10 mol·m-3时动态吸附量ΓT遵s从由Henry吸附等温式导出的动态表面状态方程.在浓度位于0.10至0.80mol·m-3的较大范围内,Tt遵从从Langmuir等温式导出的动态表面状态方程.在吸附的后期十六烷基三甲基溴化铵分子在溶液表面上的吸附遵从混合动力学控制机理.从表观扩散系数计算出吸附为混合动力学控制机理时吸附能垒为6.7～7.1 kJ·     

树脂吸附法豆腐柴叶果胶提取液脱色的研究(□)D3520树脂对色素的吸附性能

以大孔吸附树脂D3520对豆腐柴叶色素的吸附行为为研究对象,对色素的吸附平衡和吸附动力学进行研究,以Langmuir公式拟合25□下的吸附等温线,结果表明:D3520树脂对色素吸附规律较好的符合Langmuir吸附等温式.     

关于Gibbs吸附等温式的推导

Gibbs吸附等温式■是表面化学的一个重要公式,主要用于溶液的表面吸附,也用于两个溶剂互不相溶的溶液之间。但它是用热力学原理推出的,故原则上能用于任何两个平衡相之间,是具有普遍意义的吸附公式。通过Γ_i和Γ_i~1可以定量地说明什么是正吸附和负吸附。Gibbs公式表示组分i的吸附量与表面张力σ随体相中i的浓度的变化     

玉米麸质铁吸附六价铬的特性研究

玉米麸质铁对六价铬有较好的吸附能力,吸附等温式符合Langmuir公式:吸附动力学特性可以用下式描述:扩散活化能为21.85KJ/moL,表明吸附过程受颗枉扩散控制。     

沸石吸附钾离子的热力学研究

研究了沸石吸附钾离子的热力学行为,测定了不同温度下吸附等温线热力学性能的变化,对平衡常数及吸附热进行了计算.结果表明,Langmuir吸附等温式的曲线拟合能较好地描述不同温度下的实验数据,钾离子在K -Na 体系中的平衡常数与温度成负相关,△H为负值且较大,其吸附过程为自发的放热反应.     

吸附等温方程参数估算方法的分析

采用定容容量法,在温度6~60℃、平衡压力达106Pa的条件下,测得N2和O2在5A分子筛上系统的吸附相平衡数据。通过Langmuir和Toth等温方程关联这些相平衡数据,结果表明:线性化拟合的方法不可靠,其中用1/q~1/P形式线性化Langmuir方程,会得到误差很大的结果;用非线性法在各温度下单独拟合的等温方程和实验结果吻合很好,但是参数不符合其物理意义,进一步处理则误差较大。应当用非线性最小二乘法将所有温度下的相平衡数据一起拟合吸附等温方程。Langmuir和Toth方程都能用于描述体系的平衡吸附量随温度和压力的变化关系,而Toth方程的误差更小。     

两种大孔吸附树脂对麻黄碱和伪麻黄碱的吸附动力学和热力学研究

通过等温静态吸附实验研究大孔树脂AB-8和D101对麻黄碱及伪麻黄碱的等温吸附过程,根据Langmuir平衡吸附速率方程考察两种树脂对两种成分吸附的平衡速率常数,用Van’t Hoff公式计算各热力学参数(ΔHm,ΔGm及ΔSm)。结果表明麻黄碱、伪麻黄碱的吸附平衡数据符合Freundlich吸附等温方程和Langmuir平衡吸附速率方程,相关性良好。吸附的焓变(ΔHm)和熵变(ΔSm)均大于零,吉布斯自由能变(ΔGm)均小于零,表明麻黄碱及伪麻黄碱在树脂上的吸附属于自发的物理吸附过程。     

树脂吸附法豆腐柴叶果胶提取液脱色的研究 (Ⅰ) D3520树脂对色素的吸附性能

以大孔吸附树脂D3520对豆腐柴叶色素的吸附行为为研究对象,对色素的吸附平衡和吸附动力学进行研究,以Langmuir公式拟合25℃下的吸附等温线,结果表明:D3520树脂对色素吸附规律较好的符合Langmuir吸附等温式。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.