HCl-NaCl-C2H6O2-H2O体系中HCl热力学

在乙二醇和水为混合溶剂中加入HCl和NaCl组成四元系,在恒定溶液总离子强度I＝1.00mol•kg^-1,改变混合溶剂中乙二醇质量分数w（5%、15%和20%）的条件下,组成下列电池 Pt,H₂(10⁵Pa )│HCl(m), C₂H₆O₂(w), H₂O (1-w)│AgCl-Ag (A) Pt,H₂(10⁵Pa )│HCl(m_A), NaCl(m_B), C₂H₆O₂(w), H₂O (1-w)│AgCl-Ag (B) 根据测得电池(A)的电动势,确定混合溶剂中AgCl-Ag电极的标准电极电动势,讨论了HCl的迁移性质.利用电池（B）的电动势,计算出HCl 的活度系数γA.结果表明,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,lgγ_A是温度倒数1/T的线性函数,进一步讨论了混合物中 HCl的相对偏摩尔焓.     

293 K时YCl3在混合溶剂(DMF-H2O)中无限稀释摩尔电导率的测定

在293 K时测定了YCl3在混合溶剂(DMF-H2O)中的电导率,根据公式求得YCl3的摩尔电导率λ值,按Kohlraush经验公式作图,使用Origin软件进行线性拟合外推求得YCl3在混合溶剂(DMF-H2O)中的无限稀释摩尔电导率λ0=233.74 s·cm2·mol-1.     

连续滴加法快速测定混合溶剂中电解质的活度系数

改变通常的逐点称重配制溶液方法,用连续滴加的方法借助离子选择电极建立了混合溶剂中电解质较高浓度下活度系数的快速测定方法和装置。用以下电池: H~+玻璃电极|HCl(m),H_2O(1-x),MeOH(x)|AgCl-Ag电极测定了298.15K、溶剂比x=0,10,20,30,50,70,90％MeOH(wt)时的电动势,并用Pitzer方程关联出HCl的活度系数,同298.15K下的活度系数不同来源的文献值比较,表明本文测定方法和装置是可靠的,都能得到与之相一致的结果。     

电动势法确定水-丙酮-氯化钠-氯化镁体系热力学性质

采用自行设计的无液体接界电池测定了多组分电解质在水溶液和混合溶剂中不同组成时电池的电动势.利用Pitzer模型拟合实验数据,获得电池的标准电动势E(○)及电解质的活度系数.此外,计算了电解质从纯水到混合溶剂中的迁移吉布斯函数,求得了Pitzer模型的计算参数.获得了NaCl和MgCl2混合电解质的混合参数θ(NaCl)...     

用气液色谱法测定C_6—C_8烃在环丁砜中的热力学参数

本文在不同温度下,用气液色谱法测定了 C_6—C_s 烃在溶剂环丁矾中的无限稀释活度系数、分配系数和相对挥发度。计算了无限稀释时偏克分子混合焓、偏克分子溶介焓、偏克分子过剩混合自由能和偏克分子过剩混合熵。讨论了不同结构的溶质在极性溶剂中具有不同活度系数的原因,讨论了分子间引力和分子体积对活度系数的影响,并为设计苹取蒸馏塔提供基础数据。本文又研究了同系物比保留体积与分子中的碳数关系、异构体的比保留体积与沸点的关系,由此预测了同系物其它溶质与环丁砜系的无限稀释的活度系数。     

电解质混合溶剂体系汽液平衡的推算

本文建立了由混合溶剂中电解质活度系数推算汽液平衡的数值计算方法。在电解质活度系数测定的盐浓度范围内,NaBr(1)-H_2O(2)-MeOH(3)和HCl(1)-H_2O(2)-MeOH(3)两体系在101.3 kPa下的汽液平衡计算结果与文献值平均绝对偏差分别为:汽相摩尔分率,平衡温度和,对前一体系还能正确地推测出交叉的盐效应规律。     

用Naβ″-Al_2O_3固体电解质研究熔融硅酸盐的热力学

利用Naβ″-Al_2O_3组成的电池直接测量Na_2O-SiO_2、Na_2O-CaO-SiO_2、Na_2O-Fe_2O_3-SiO_2及Na_2O-CaO-Fe_2O_3-SiO_2系中Na_2O的活度。该方法简单,测量迅速、准确。其电池形式为: Pt|O_2,Na_2O(硅酸盐)|Naβ″-Al_2O_3|α+β-Al_2O_3,O_2|Pt测量温度范围为1243—1460K。二元硅酸盐中SiO_2的活度已从测量的Na_2O活度数据利用Gibbs-Duhem方程算得,Na_2O的超额偏摩尔热力学量及系统的超额摩尔自由焓亦从所测的Na_2O活度算得。文中还计算了CaO及Fe_2O_3对Na_2O活度系数的影响量γ_(Na_2O)~(CaO)和γ_(Na_2O)~(Fe_2O_3),并且用二元及三元系得到的各活度系数值计算四元系的γ_(Na_2O(4)),计算结果与测量值十分一致。     

电势法研究NaBr在甲醇-水混合溶剂中298.15K下的热力学性质

用Na离子选择性电极NaBr(m),MeOH(w),H_2O(100-w)Br离子选择性电极组成的电池测定NaBr在甲醇含量为0%、10%、20%、40%、60%、80%、90%和100%的甲醇-水混合溶剂,浓度在0.01～3.0mol/kg之间的平衡电势.用Pitzer方程关联实验结果得到每个实验点的NaBr的平均活度系数.结果发现,在一定的溶剂比例下,NaBr的平均活度系数先随它的浓度增加而下降,然后上升;当NaBr浓度固定时,它的平均活度系数随溶剂中甲醇含量增加而下降.NaBr在甲醇中有微弱的缔合.     

电势法研究NaBr在甲醇-水混合溶剂中298.15K下的热力学性质

用Na离子选择性电极NaBr(m),MeOH(w),H_2O(100-w)Br离子选择性电极组成的电池测定NaBr在甲醇含量为0%、10%、20%、40%、60%、80%、90%和100%的甲醇-水混合溶剂,浓度在0.01～3.0mol/kg之间的平衡电势.用Pitzer方程关联实验结果得到每个实验点的NaBr的平均活度系数.结果发现,在一定的溶剂比例下,NaBr的平均活度系数先随它的浓度增加而下降,然后上升;当NaBr浓度固定时,它的平均活度系数随溶剂中甲醇含量增加而下降.NaBr在甲醇中有微弱的缔合.     

微扰理论的应用研究(Ⅱ)——水-正丁醇-MX三元体系液液平衡的计算

在本文(Ⅰ)报基础上,应用微扰理论导出了带电离子流体混合物的过量Helmholty自由能计算公式.该公式考虑了体系中溶质—溶剂、溶剂—溶剂和溶质—溶质间所有作用能(包括分子色散能、排斥能、偶极定向能、诱导能、离子静电能、离子偶极能).计算了在25℃下3个加盐混合溶剂体系[H_2O-nC_4H_9OH-MX(NaCl、KCl、KBr)]液液平衡中溶剂的活度系数,并与实验值进行了比较.     

Studies of electrochemical reduction of dioxygen with RRDE

The electrochemical behaviors of dioxygen (O₂) were studied by using rotate ring-disk electrode (RRDE) and other electrochemical methods at bare glassy carbon electrode (GCE) and single-walled carbon nanotubes (SWNTs)-dihexadecyl hydrogen phosphate (DHP) film modified GCE. The results showed that the electrochemical reduction of dioxygen was considered to proceed by a two-step two-electron reduction pathway at both bare GCE and SWNTs-DHP film modified GCE in 0.1 mol/L air-saturated sodium hydroxide (NaOH). Maybe because each reaction rate for two cases was different the cyclic voltammograms measurements exhibited different behaviors. The detection of ring current confirmed the presence of middle product hydrogen peroxide (H₂O₂). Furthermore, larger current and more positive reduction potential indicated that SWNTs showed a catalytic effect towards the electrochemical reduction of dioxygen.     

Fabrication of a stable, switchable An/SAM-Au electrode with tunable electron transfer and excellent electrochemical properties

This paper describes the electrochemical properties, such as electrode reactivity, and interfacial capacitance of an anthracene/self-assembled monolayer (An/SAM) Au electrode prepared through controllable immersion of the dodecanethiol (C₁₂SH) SAM-Au electrode in a THF solution of anthracene (An). The C₁₂SH SAM almost totally blocks heterogeneous electron transfer between the bare Au electrode and Fe(CN)₆^3−/4− in solution, but adsorption of the An molecules onto the SAM-Au electrode restores electron transfer. The prepared An/SAM-Au electrode possesses good reactivity without a remarkable barrier to heterogeneous electron transfer. On the other hand, the electroactive form of the An/SAM-Au electrode can be converted back to the non-electroactive form by immersing the electrode into pure THF.     

Flow influenced electrochemical corrosion of nickel aluminium bronze – Part I. Cathodic polarisation

The cathodic polarisation behaviour of CA 104 nickel aluminium bronze (NAB) has been examined in fully characterised seawaters (filtered and artificial) using the rotating disc electrode (RDE) and the rotating cylinder electrode (RCE). Linear sweep voltammetry and a potential step, current transient technique were used to examine the charge transfer and mass transfer controlled cathodic response as a function of both laminar and turbulent fluid flow. For freshly polished surfaces, the rate of irreversible charge transfer controlled oxygen reduction is controlled by the exchange of a single electron and hydrogen evolution is only significant at potentials more negative than approximately –1.0 V vs. the saturated calomel electrode (SCE).     

Development of a novel electrochemical immuno-assay using a screen printed electrode for the determination of secretory immunoglobulin A in human sweat

This paper reports on the steps involved in the development of a novel electrochemical immunoassay for secretory immunoglobulin A (sIgA) determinations in human sweat. This novel immunoassay involves an initial step whereby sweat sIgA is adsorbed onto a polyvinylidene fluoride (PVDF) membrane (sweat patch). Following a wash step, a solution containing bovine serum albumin (BSA) is used to block any sites at which non-specific binding might occur. After a second wash step, the PVDF sweat patch is transferred to a second tube to which is added diluent and anti-sIgA antibody conjugated to horseradish peroxidase (HRP). Following an incubation step, an aliquot of supernatant containing unbound antibody is transferred to a well in a 96 well plate format which had been previously coated with sIgA. After a second incubation step and wash step, 3,3′,5,5′-tetramethylbenzidine (TMB) is added to the same well and left to undergo enzymatic oxidation. Finally a screen-printed carbon electrode (SPCE) is inserted into the well and any oxidised TMB is detected by chronoamperometry using an applied potential of +50 mV. The resulting reduction current is then referred to a calibration plot to deduce the unknown sIgA concentration. The optimisation of the steps involved in this assay is described in detail. Some preliminary data is presented on sweat sIgA levels collected from human volunteers who had undergone a controlled exercise regime on a bicycle (Ergociser). To our knowledge this is the first report where a sweat patch and a SPCE have been successfully incorporated into an immunoassay for sIgA.     

Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium

We investigated the effect of CoSe₂/C nanoparticle loading rate on oxygen reduction reaction (ORR) activity and H₂O₂ production using the rotating disk electrode and the rotating ring-disk electrode techniques. We prepared carbon-supported CoSe₂ nanoparticles with different nominal loading rates and evaluated these samples by means of powder X-ray diffraction. All the catalysts had an OCP value of 0.81 V vs. RHE. H₂O₂ production during the ORR process decreased with an increase in catalytic layer thickness. This decrease was related to the CoSe₂ loading on the disk electrode. H₂O₂ production also decreased with increasing catalytic site density, a phenomenon related to the CoSe₂ loading rate on the carbon substrate. The cathodic current density significantly increased with increasing catalytic layer thickness, but decreased with increasing catalytic site density. In the case of 20 wt% CoSe₂/C nanoparticles at 22 μg cm⁻², we determined that the transfer process involves about 3.5 electrons.     

Preparation and sensor properties of poly (o-toluidine) film

Summary An amperometric biosensor for glucose was constructed in a one-step procedure by the electropolymerization of o-toluidine in the presence of glucose oxidase on Pt substrates in KCl aqueous electrolyte at a potential of 0.5 V vs Ag / AgCl. The amperometric responses of the prepared polymeric biosensor to the glucose were measured at a potential of 0.7 V in PBS solution. Results showed that this polymeric sensor exhibited a fast amperometric response time (4–5 s) and a linear range up to 6 mM glucose with poor stability. Also, it was seen that biosensor responded successfully to glucose injections in the presence of some interfering species such as lactose, sucrose and urea. Received: 27 January 1999/Revised version: 18 May 1999/Accepted: 18 May 1999     

氟离子检测方法的改进及离子色谱法的应用

传统离子选择电极法分析氟离子容易被pH、金属离子和温度等因素所干扰,这样会使数据产生极大的误差。为了避免这些缺点,离子分离理论和高效液相色谱技术被应用在氟离子的分析-离子色谱法,离子色谱作为一种先进的检测手段在氟离子分析方面表现出优秀的准确性,重现性和可靠性。     

电极对微生物燃料电池同时处理有机废水和含铜重金属废水产电性能的影响

实验以有机废水为阳极底物,以活性污泥中的混合菌为阳极接种微生物,以含铜废水为阴极液,构建双室MFC,探讨电极对MFC同时处理有机废水和含铜重金属废水产电性能的影响.结果表明:MFC对阳极有机废水COD的去除率最高为79.1%,对阴极液中Cu²⁺的去除率最高为95.6%.活性炭/石墨棒电极MFC产电性能最优,开路电压最高为800mV,是石墨棒电极MFC的1.25倍,是活性炭/碳纸电极MFC的1.3倍,是碳纸电极MFC的1.5倍.当电极距离为2cm时,MFC开路电压580mV,内阻为181Ω,产电性能最优.电极表面积为75cm²时,MFC的开路电压470mV,是电极表面积为50cm²的MFC的1.1倍,是电极表面积为30cm²的MFC的2.1倍.当A_An/A_cat=0.4时MFC产能最佳,MFC的开路电压最高为600mV,最大功率密度48.2mW/m².     

Electrocatalytic oxidation of thioglycolic acid at carbon paste electrode modified with cobalt phthalocyanine: application as a potentiometric sensor

The voltammetric behavior of thioglycolic acid (TGA) was studied at a carbon paste electrode modified with cobalt phthalocyanine (CoPc). The CoPc-modified electrode shows high electrocatalytic activity toward oxidation of TGA, lowering substantially the overpotential of anodic reaction. Results of the cyclic voltammetry show that TGA undergoes a two-step oxidation (each step with one electron) resulting the dimer of thiol. Enhancement of the rate of electron transfer results in a near-Nernstian behavior of modified electrode to the concentration of TGA and makes it as a suitable potentiometric sensor for the detection of this compound. This electrode shows a near-Nernstian response in a wide linear range of the concentration TGA (4 orders of magnitude). The modified electrode was used successfully for the determination of TGA and its salts in hair-treatment products and also in culture media. The modified electrode exhibited a fast response time (<10 s), very good stability, and had an extended lifetime.     

细菌纤维素/碳纳米管/MnO2复合超级电容器电极

基于细菌纤维素(BC)的三维多孔及柔性支架结构和碳纳米管(MWCNT)的优良导电性,构筑起BC/MWCNT自支撑导电基底。其中,二者通过氢键紧密结合,协同赋予复合基底优良的电导率和机械性能。然后将二氧化锰(MnO₂)电沉积在该基底上,构建了一种新型的BC/MWCNT/MnO₂薄膜电极。BC/MWCNT复合膜的多孔结构、电解质吸收特性及蜂窝状活性MnO₂纳米片的桥连结构,赋予其出色的电化学性能(在1 mA cm_-2^{的电流密度下},其面积比电容和质量比电容分别达到1.17 F cm_-2^和200 F g_-1⁾和显著的循环稳定性(在20 mA cm_-2^{的电流密度下进行}10000次循环后,其比电容保留率稳定在96%)。这种无粘合剂的薄膜电极制备简便且成本低廉,在开发柔性储能器件方面具有巨大潜力。关键词：细菌纤维素(BC)；碳纳米管(MWCNT)；二氧化锰(MnO₂)；膜电极；电化学性能中图分类号：TQ630 文献标识码： A 文章编号：1003-5214 (2020) 01-0000-00