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1.
本文应用Corning一价阳离子选择电极与氯离子选择电极组成无液接可逆电池,测定电池在283.15K~318.15K间七个温度下的标准电动势及其温度系数,计算KCl从纯水到相应的DMF-H_2O混合溶剂的标准转移Gibbs自由能ΔG_t~0和标准转移熵ΔS_t~0,得出ΔG_t~0和ΔS_t~0随混合溶剂中DMF的摩尔分数x_(DMF)及温度T的变化规律.发现KCl的ΔS_t~0随x_(DMF)变化的趋势和NaCl的相反.从离子溶剂化作用及其对溶剂结构的影响作了讨论. 相似文献
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本文应用Corning一价阳离子选择电极与氯离子选择电极组成无液接可逆电池,测定电池在283.15K~318.15K间七个温度下的标准电动势及其温度系数,计算KCl从纯水到相应的DMF-H~2O混合溶剂的标准转移Gibbs自由能ΔG 和标准转移熵ΔS ,得出ΔG 和ΔS 随混合溶剂中DMF的摩尔分数x~DMF及温度T的变化规律.发现KCl的ΔS随x~DMF变化的趋势和NaCl的相反.从离子溶剂化作用及其对溶剂结构的影响作了讨论. 相似文献
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本文应用Corning一价阳离子选择电极与氯离子选择电极组成无液接可逆电池,测定电池在283.15K~318.15K间七个温度下的标准电动势及其温度系数,计算KCl从纯水到相应的DMF-H~2O混合溶剂的标准转移Gibbs自由能ΔG 和标准转移熵ΔS ,得出ΔG 和ΔS 随混合溶剂中DMF的摩尔分数x~DMF及温度T的变化规律.发现KCl的ΔS随x~DMF变化的趋势和NaCl的相反.从离子溶剂化作用及其对溶剂结构的影响作了讨论. 相似文献
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本文应用钠离子玻璃电极及氯离子选择性电极组成无液界可逆电池, 即Cl^-选择电极|NaCl(m), w或s|Na^+玻璃电极测定电池的标准电动势, 计算NaCl从纯水到DMF-H2O混合溶剂的标准转移Gibbs自由能ΔGt°, 测定相应的电池在5℃至45℃九个温度下的电动势温度系数, 求得标准转移熵ΔSt°. 得出ΔGt°及ΔSt°随有机组份含量及温度变化的规律. 对NaCl由纯水至混合溶剂的溶剂化作用的变化, 及DMF和水的液体结构作了讨论. 相似文献
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本文应用钠离子玻璃电极及氯离子选择性电极组成无液界可逆电池,即Cl~-选择电极|NaCl(m),w 或 s|Na~+玻璃电极测定电池的标准电动势,计算 NaCl 从纯水到 DMF-H_2O 混合溶剂的标准转移 Gibbs 自由能ΔG°_t,测定相应电池在5℃至45℃九个温度下的电动势温度系数,求得标准转移熵ΔS°_t.得出ΔG°_t及ΔS°_t随有机组份含量及温度变化的规律.对 NaCl 由纯水至混合溶剂的溶剂化作用的变化,及 DMF和水的液体结构作了讨论. 相似文献
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RbCl在H2O-DMF混合溶剂中活度系数的测定 总被引:2,自引:0,他引:2
应用Corning-价阳离子选择电极(M~+-ISE)和Orion氯离子选择电极组成可逆电池,CI~--ISE|RbCl(m),H2O(1-x),DMF(x)M~ -ISE.测量该电池标准电动势E_m,运用扩展的Debye-Hckel公式,计算RbCl在283.15至318.15K七个温度下由H2O至H2O-DMF混和溶剂的标准迁移自由能ΔG和在不同组成(H2O-DMF)混合溶剂中平均离子活度系数γ±,并对迁移自由能及活度系数随混合溶剂有机物组份的摩尔分数的变化进行了讨论。 相似文献
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生物体液可看作是由多种离子与氨基酸、蛋白质组成的混合电解质溶液,研究电解质或离子与这些氨基酸、蛋白质间的相互作用对了解生物体液内复杂的作用机理,揭示许多生命现象具有重要意义。1978年以来,Kelley采用有液体接界的电池研究了几种氨基酸或肽与一些碱金属氯化物的相互作用自由能,为研究电解质与氨基酸、蛋白质间的相互作用奠定了基础。研究溶质的迁移热力学性质是了解溶质-溶剂间相互作用以及溶液微观结构的常用手段。以氨基酸水溶液作为含水离子溶剂,用电动势法研究电解质从水到该溶液中的迁移热力学性质,进而研究电解质与氨基酸间的相互作用是可行的,目前这方面的研究工作很少见文献报导。本文通过测定电池: 相似文献
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在恒定丙三醇质量分数x=0.1的条件下,测定了无液接电池(A)和电池(B)的电动势根据电池(A)电动势确定了丙三醇和水混合溶剂中的Ag-AgCl电极的标准电极电势,讨论了HCl的迁移性质;由电池(B)测得的电动势计算了HCl在该体系中的活度系数γA,计算的结果表明,对于所讨论的体系,在溶液中总离子强度保持恒定,HCl的活度系数服从Harned规则.在溶液组成恒定时,IgγA是温度倒数1/T的线性函数,讨论了混合物中HCl的相对偏摩尔焓及介质效应. 相似文献
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四苯硼铵从H2O到H2O-TBA的ΔGΘt和介质效应 总被引:1,自引:0,他引:1
Solubilities of ammonium tetraphenylborate (NH4BPh4) in water-t-butyl alcohol (TBA) mixed solvents at 283.15,293.15,298.15,303.15 and 308.15K have been determined by spectrophotometry.The standard Gibbs energy of transfer (ΔGΘt) of NH4BPh4 from water to H2)-TBA mixtures and the primary medium effect of NH4BPh4 from 283.15 to 308.15K were studied.The results show that-ΔGΘt exhibits a complicated variation pattern with the increase in the mole fraction of TBA [x(TBA)] at the same temperature.When x(TBA)<0.06,-ΔGΘt increases very slowly with x(TBA),the-ΔGΘt increases rapidly with x(TBA) when x(TBA) from 0.06 to 0.2.For x(TBA)>0.2,the -ΔGΘtdecreases with increasing x(TBA).The largest value of -ΔGΘt occurs at x(TBA)=0.2.The main reason for this variation was analyzed and discussen. 相似文献
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硫酸溶液中Ce3+在铂电极上阳极氧化动力学 总被引:4,自引:0,他引:4
用分解极化曲线法研究了铂电极上Ce(Ⅳ)阳极形成动力学与机理.实验结果表明,电位在1.7—1.9V(vs.SCE)的高极化区,分解得到的O2和Ce(Ⅳ)的极化曲线Tafel斜率分别为2.303RT/βF和2×2.303RT/βF,两者的动力学方程可分别用下式表示:
i(O2)=k1aw4exp(βφF/RT)
i(Ce4+)=k2aw2[Ce3+]exp(βφF/2RT)
假设了Ce3+是通过反应中间基MCe(OH)3•Oad氧化的机理.由此所导出的动力学方程与实验结果相符. 相似文献
i(O2)=k1aw4exp(βφF/RT)
i(Ce4+)=k2aw2[Ce3+]exp(βφF/2RT)
假设了Ce3+是通过反应中间基MCe(OH)3•Oad氧化的机理.由此所导出的动力学方程与实验结果相符. 相似文献
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在303.15 K、313.15 K、323.15 K、333.15 K温度下,0-6 MPa压力范围内测定了甲烷在水-叔丁醇混合溶剂中的溶解度.溶剂中叔丁醇的摩尔分数(x_(TBA))从0到1.结果表明,在温度和溶剂组成一定条件下,甲烷的溶解度随其分区的增加而增大,随x_(TBA)的增加,在富水区内,甲烷的溶解度变化较缓慢,当x_(TBA)超过某值时,甲烷的溶解度随x_(TBA)的增加而增大,并且幅度较大;在x_(TBA)约为0-0.045范围内,甲烷的溶解度随温度增加而减小,x_(TBA)约在0.045-0.15范围内,溶解度随温度增加而增加,x_(TBA)约在0.15~1.0范围内,溶解度随温度增加而减小.根据溶解度与温度和溶剂组成的关系可以推测,在303.15-333.15 K、0-6 MPa范围内,水-叙丁醇混合溶剂中仍存在笼合物结构.根据溶解度与温度、压力的关系讨论了甲烷在此混合溶剂中的亨利常数、偏摩尔体积、标准溶解自由能、标准溶解焓和标准溶解熵. 相似文献
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In the previous paper(Ⅲ), the following equation of solvent effect in organic chemistry was suggested:
Ei=a﹒Ai(1-Va﹒VAi)+d﹒Di(1-Vd﹒VDi)+E0
Where Ei is a physical or chemical property of the substrate in the solvent i and E0 is that in n-hexane. Ai and Di are constants of electron acception and donation effect of the solvent i respectively. VAi and VDi are constants of electron acception and donation space effect of the solvent i respectively, a and d are the sensitivities of E of the substrate vs the change of Ai and Di. Va and Vd are the constants of electron acception and donation space effect of the substrate respectively. In IR spectra E could be substituted by the wavenumber(ν). Ai and VAi have been established for 18 organic solvents (n-C6H14, n-C7H16, cyclohexane, CCl4, Ph-Me, ClCH:CCl2, Et2O, CHCl3, C6H6, CH2Cl2, ClCH2CH2Cl, Ph-NO2, THF, 1,4-dioxane, Et-NO2. MeCO2Et, Me-NO2, Me-CN).
In this paper Di and VDi have been established for these solvents. The equation also has been tested by the νC-X(X=Cl, Br) of five alkylhalides (t-BuCl, n-C5H11Cl, t-BuBr, Et-Br, EtC(H)BrMe) and νC=O of three carboxyl compounds (t-BuCOMe, Me2CO, MHB) and seven organotin compounds [(Ph2MeSiCH2)3SnO2C-C6H4-X-p(X=H-, CH3-, CH3O-, NO2-, F-. Cl-, I-)].
The relationship (ν=ρ﹒σ+ν0) between νC=O of organotin compounds and Hammett constants(σ) of the substituted groups in different solvents was studied and a relationship betweenρ and Ai, VAi, Di, VDi of the solvents was found. 相似文献
Ei=a﹒Ai(1-Va﹒VAi)+d﹒Di(1-Vd﹒VDi)+E0
Where Ei is a physical or chemical property of the substrate in the solvent i and E0 is that in n-hexane. Ai and Di are constants of electron acception and donation effect of the solvent i respectively. VAi and VDi are constants of electron acception and donation space effect of the solvent i respectively, a and d are the sensitivities of E of the substrate vs the change of Ai and Di. Va and Vd are the constants of electron acception and donation space effect of the substrate respectively. In IR spectra E could be substituted by the wavenumber(ν). Ai and VAi have been established for 18 organic solvents (n-C6H14, n-C7H16, cyclohexane, CCl4, Ph-Me, ClCH:CCl2, Et2O, CHCl3, C6H6, CH2Cl2, ClCH2CH2Cl, Ph-NO2, THF, 1,4-dioxane, Et-NO2. MeCO2Et, Me-NO2, Me-CN).
In this paper Di and VDi have been established for these solvents. The equation also has been tested by the νC-X(X=Cl, Br) of five alkylhalides (t-BuCl, n-C5H11Cl, t-BuBr, Et-Br, EtC(H)BrMe) and νC=O of three carboxyl compounds (t-BuCOMe, Me2CO, MHB) and seven organotin compounds [(Ph2MeSiCH2)3SnO2C-C6H4-X-p(X=H-, CH3-, CH3O-, NO2-, F-. Cl-, I-)].
The relationship (ν=ρ﹒σ+ν0) between νC=O of organotin compounds and Hammett constants(σ) of the substituted groups in different solvents was studied and a relationship betweenρ and Ai, VAi, Di, VDi of the solvents was found. 相似文献
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水-醋酸体系中HCl的热力学性质研究 总被引:1,自引:0,他引:1
人们对混合溶剂中的电解质热力学性质虽然已进行了较广泛的实验研究,并提供了许多实验数据,为理论研究提供了方便,但还很不全面,即使象水-醋酸这样的混合溶剂体系,至今尚未见较全面的报道,为此,本文设计了如下电池:玻璃电极(H+)|HCl(m),HAc+H2O|AgCl-Ag并测定该电池的电动势,以了解HCl在水-醋酸中的热力学行为及离子-溶剂相互作用特点。 相似文献
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The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H3TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)phenyl-s-triazine (H3TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H3TPB-3tz with CuCl2.2H2O affords the noncatenated compound Cu3[(Cu4Cl)3(TPB-3tz)8]2.11CuCl2.8H2O.120DMF (2), while the reaction of H3TPT-3tz with MnCl2.4H2O or CuCl2.2H2O generates the catenated compounds Mn3[(Mn4Cl)3(TPT-3tz)8]2.25H2O.15CH3OH.95DMF (3) and Cu3[(Cu4Cl)3(TPT-3tz)8]2.xsolvent (4). Significantly, catenation helps to stabilize the framework toward collapse upon desolvation, leading to an increase in the surface area from 1120 to 1580 m2/g and an increase in the hydrogen storage capacity from 2.8 to 3.7 excess wt % at 77 K for 2 and 3, respectively. The total hydrogen uptake in desolvated 3 reaches 4.5 wt % and 37 g/L at 80 bar and 77 K, demonstrating that control of catenation can be an important factor in the generation of hydrogen storage materials. 相似文献
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在278.15-318.15 K范围内DMF-H2O体系的超额摩尔体积及DMF的表观摩尔体积和偏摩尔体积的测定与研究 总被引:1,自引:0,他引:1
本文应用振动管式密度计, 测定了278.15—318.15 K范围内10个温度下, DMF-H_2溶液的密度随组成的变化. 根据密度值求出溶液的超额体积VE; 在全部浓度的范围内不同组成下DMF的表观摩尔体积φv及偏摩尔体积V_(DMF); 及VE、φv和V_(DMF)随组成变化的规律. 发现V_(DMF)随x_(DMF)的变化与NaCl由水至DMF-H_2O溶液的转移熵有对应的变化规律, 均在x_(DMF)≈0.075处有极值, 从而进一步对DMF-H_2O的液体结构进行了讨论, 认为当x_(DMF)=0.075时, 单个DMF分子可能嵌入12个水分子组成的分子笼中, 从而形成最紧密结构。 相似文献
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IntroductionTherehasbeenanincreasedinterestinthethermodynamicbehaviorofternarymixtures(water+nonaqueoussolvent+electrolyte)[1].However,therehasbeenashortageofinvestigationsonsuchmixtures,especiallyonaromaticsolutesthatcontainthesubstituent.Littleiskn… 相似文献