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1.
应用修正的BET热力学模型对Mg(NO3)2-NH4NO3-H2O三元体系和LiNO3-Mg(NO3)2-NH4NO3-H2O四元体系在273~320 K的相图进行预测,并找到一个相变温度较低的四元共晶点Mg(NO3)2.6H2O-LiNO3.3H2O-NH4NO3,其质量百分数组成为:25.5%的硝酸铵,28.4%的硝酸锂,13.8%的硝酸镁和32.3%的水,通过实验对共晶点组成材料的吸放热行为进行测定,发现其熔化温度为286.3 K,且DSC测试其相变热焓为192.7 J.g-1,表明该材料可用作潜在的低温相变储能材料。  相似文献   

2.
Me-NaHCO3-NH3-H2O体系和Me-NaOH-NaHCO3-H2O体系的热力学分析   总被引:1,自引:0,他引:1  
通过对Me(Fe2+,Ni2+,Cu2+,Zn2+)-NaHCO3-NH3-H2O体系以及Me-NaOH-NaHCO3-H2O体系的热力学分析,得到各金属离子总浓度cMe与pH值的关系,确定了2种体系的完全共沉淀区域.热力学分析结果表明:在Me-NaHCO3-NH3-H2O体系中,Ni2+,Cu2+,Zn2+这3种离子和氨的配位能力很强.当总碳的浓度cC=1 mol·L-1且总氮的浓度cN=0.01 mol·L-1时,在pH=7.5~11范围内可实现完全共沉淀:当cN=0.05 mol·L-1且cC=3 mol·L-1时,在pH=70.5时可实现完全沉淀,但共沉淀范围较窄,不利于铁氧体组分的精确控制.在Me-NaOH-NaHCO3-H2O体系中,共沉淀区域由cC决定,当cC=1 mol·L-1,pH=7.5~11时可实现完全共沉淀.  相似文献   

3.
4.
马修臻  胡斌 《化学通报》2018,81(10):939-943,938
本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li2SO4 + Na2SO4 + H2O和 Li2SO4 + K2SO4 + H2O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg–1,混合溶液中Na2SO4和K2SO4的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θV和 ψV,模型的计算值与实验值的偏差在±0.002 g.cm3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。  相似文献   

5.
通过调变HAuCl4溶液的pH值和Au负载量,用沉积-沉淀法制备了一系列Au/Co3O4催化剂,并采用AES、BET、XRD、SEM、XPS和H2-TPR等技术对催化剂的结构和组成进行了表征,考察了制备条件对其在有氧气氛中催化N2O分解反应性能的影响规律,得到了催化剂最佳制备条件:HAuCl4溶液pH值为9,Au负载量为0.29%。催化测试结果表明:虽然ZnCo2O4的催化活性优于Co3O4,但0.31%Au/ZnCo2O4的活性和稳定性低于0.29%Au/Co3O4。500℃、在含氧气氛中连续反应10 h, 两者均可完全分解N2O,但在含氧、含水气氛中0.29%Au/Co3O4和0.31%Au/ZnCo2O4上的N2O转化率分别为92%和63%。究其原因,发现Au/Co3O4中Au和Co组分间存在协同效应,而Au/ZnCo2O4中Au和Co组分间则没有协同效应。  相似文献   

6.
张爱芸  姚燕 《化学学报》2006,64(6):501-507
测定了298.15 K下, 无液接电池Li-ISE│Li2B4O7 (mA)(aq.), MgCl2(mB)(aq.)│AgCl/Ag的电动势, 利用测定结果计算了Li2B4O7-MgCl2-H2O体系离子强度在0.05~3 mol•kg-1范围内, 不同MgCl2离子强度分数的溶液中LiCl的平均活度系数, 并给出了其随离子强度I, B4O72-和Mg2+浓度的变化规律. 结合以往关于该体系和Li2B4O7-LiCl-H2O, Li2B4O7-H2O体系的等压研究结果, 用迭代和多元线性回归方法对Li-Mg2+-Cl-B4O72--H2O体系的离子相互作用模型进行了研究. 具体方法为考虑了该体系在不同的总硼浓度范围H3BO3, B(OH)4, B3O3(OH)4和B4O5(OH)42-四种含硼化合物的存在以及各硼化合物间的化学平衡, 以修正了的Pitzer渗透系数方程和活度系数方程为基础, 对该体系的等压法和电动势法研究结果进行最小二乘拟合, 拟合的标准偏差为0.0167, 用该模型计算的该体系的渗透系数、活度系数与实验值基本一致.  相似文献   

7.
商用SCR脱硝催化剂K2O中毒后再生:(NH4)2SO4溶液   总被引:1,自引:0,他引:1  
利用(NH4)2SO4溶液对K2O中毒后烟气SCR (selective catalytic reduction)脱硝商用催化剂活性进行再生。采用湿法浸渍法使催化剂表面负载不同质量K2O,前驱体为KNO3溶液。经过再生工艺处理后,在不同模拟烟气空速及氧浓度条件下均具有良好的活性。进一步利用离子色谱(IC)、N2吸附脱附分析(BET)、扫描电镜及其元素能谱分析(SEM-Maps, EDX)、红外光谱分析(FT-IR)等技术对再生前后催化剂进行表征。结果表明,再生工艺对K2O去除效果明显,有效地恢复了催化剂表面活性位V=O。此外,再生过程没有导致催化剂表面物质的流失及机械强度的降低。  相似文献   

8.
测定了298.15 K下, 无液接电池Li-ISE│Li2B4O7 (mA)(aq.), MgCl2(mB)(aq.)│AgCl/Ag的电动势, 利用测定结果计算了Li2B4O7-MgCl2-H2O体系离子强度在0.05~3 mol•kg-1范围内, 不同MgCl2离子强度分数的溶液中LiCl的平均活度系数, 并给出了其随离子强度I, B4O72-和Mg2+浓度的变化规律. 结合以往关于该体系和Li2B4O7-LiCl-H2O, Li2B4O7-H2O体系的等压研究结果, 用迭代和多元线性回归方法对Li-Mg2+-Cl-B4O72--H2O体系的离子相互作用模型进行了研究. 具体方法为考虑了该体系在不同的总硼浓度范围H3BO3, B(OH)4, B3O3(OH)4和B4O5(OH)42-四种含硼化合物的存在以及各硼化合物间的化学平衡, 以修正了的Pitzer渗透系数方程和活度系数方程为基础, 对该体系的等压法和电动势法研究结果进行最小二乘拟合, 拟合的标准偏差为0.0167, 用该模型计算的该体系的渗透系数、活度系数与实验值基本一致.  相似文献   

9.
用等压法研究了298.15 K下LiCl-Li2B4O7-H2O体系在不同LiB4O7质量摩尔浓度时的等压平衡浓度,  水活度; 计算了LiCl和Li2B4O7混合盐溶液的渗透系数等热力学性质. 用298.15 K下的实验数据对Pitzer离子相互作用模型进行了参数化研究, 拟合求取了298.15 K下Pitzer离子相互作用参数, 用获得的参数计算了LiCl和Li2B4O7在LiCl-Li2B4O7-H2O体系中的活度系数. Pitzer模型计算的渗透系数值与实验结果一致.  相似文献   

10.
三元体系Na2SO4-CuSO4-H2O 25 ℃活度系数的研究   总被引:1,自引:1,他引:1  
用自制的Hg-Hg_2SO_4电极和Na离子选择性电极, 在25 ℃和离子强度分别为1.0和2.0的条件下, 测定了Na_2SO_4在Na_2SO_4和CuSO_4混合水溶液中的平均活度系数。对所使用的电极组的热力学响应、重现性等性能进行了检验。根据文献提供的Pitzer方程, 推导了计算Na_2SO_-CuSO_4-H_2O体系中Na_2SO_4和CuSO_4平均活度系数的表达式, 求出了Pitzer混合参数和Harned方程系数, 计算了CuSO_4在该体系中的平均活度系数。  相似文献   

11.
氨基酸-BrO-3-Mn2+-H2SO4-丙酮体系的振荡反应   总被引:7,自引:3,他引:7  
This paper, Using potentiometric method, first reports the oscillating behavior of five amino acids (L-methionine, L-cystine, L-tryptophan, L-serine, L-tyrosine) in a new oscillating system of amino acid-BrO_3~--Mn~(2+)-H_2SO_4-acetone. The effect of many factors on oscillation have been investigated. According to Arrhenius equation, the apparent activation energy of the oscillatary induction period and oscillation period of five oscillating systems are obtained within temperature range of 20~37 ℃.  相似文献   

12.
Chaotic oscillations in redox potential have been observed in thiophenol-KIO3-H2SO4 system in batch reactors. These occur in a concentration and temperature range. Bifurcation from a stable regime to a chaotic regime occurs in a straight way in the entire concentration and temperature range. Oscillations were also studied in continuously stirred tank reactors. These oscillations are deterministic chaos. It is tentatively suggested that chaos in the system is due to a time delay caused by a large number of intermediates.  相似文献   

13.
Solubility of the ternary system LiCl-LiNO3-H2O was measured at 273.15 K and 323.15 K by analyzing the equilibrated phase composition. Experimental result shows that there are three solubility branches at 273.15 K, corresponding to the solid phases LiCl·2H2O,LiNO3 and LiNO3·3H2O, respectively, while there are two solubility branches at 323.15 K, corresponding to the solid phase LiCl·H2O and LiNO3. The invariant point compositions are (1) 33.68wt% LiCl, 14.32wt% LiNO3 and (2) 27.70wt% LiCl, 20.60wt% LiNO3 at 273.15 K and (3) 39.07wt% LiCl, 16.89wt% LiNO3 at 323.15 K. Also, the experimental results show that the solid phases in equilibrium with the solution {x(2.8LiCl+LiNO3)-(1-x)H2O} are LiNO3·3H2O or LiNO3 at 273.15 K and LiNO3 at 323.15 K.  相似文献   

14.
The objectives of this study were to address uncertainties in the solubility product of (UO2)3(PO4)2⋅4H2O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO2)3(PO4)2⋅4H2O(c) and (PuO2)3(PO4)2⋅4H2O(am) solubilities for long-equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001–1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products. The U(VI)-phosphate data for the most part agree closely with thermodynamic data presented in Guillaumont et al.,(1) although we cannot verify the existence of several U(VI) hydrolyses and phosphate species and we find the reported value for formation constant of UO2PO4 is in error by more than two orders of magnitude. A comprehensive thermodynamic model for (PuO2)3(PO4)2⋅4H2O(am) solubility in the H+-Na+-OH-Cl-H2PO4-HPO2−4-PO3−4-H2O system, previously unavailable, is presented and the data shows that the U(VI)-phosphate system is an excellent analog for the Pu(VI)-phosphate system.  相似文献   

15.
Chromium(III)-phosphate reactions are expected to be important in managing high-level radioactive wastes stored in tanks at many DOE sites. Extensive studies on the solubility of amorphous Cr(III) solids in a wide range of pH (2.8–14) and phosphate concentrations (10–4 to 1.0 m) at room temperature (22±2)°C were carried out to obtain reliable thermodynamic data for important Cr(III)-phosphate reactions. A combination of techniques (XRD, XANES, EXAFS, Raman spectroscopy, total chemical composition, and thermodynamic analyses of solubility data) was used to characterize solid and aqueous species. Contrary to the data recently reported in the literature,(1) only a limited number of aqueous species [Cr(OH)3H2PO4, Cr(OH)3(H2PO4)2–2), and Cr(OH)3HPO2–4] with up to about four orders of magnitude lower values for the formation constants of these species are required to explain Cr(III)-phosphate reactions in a wide range of pH and phosphate concentrations. The log Ko values of reactions involving these species [Cr(OH)3(aq)+H2PO4⇌Cr(OH)3H2PO4; Cr(OH)3(aq)+2H2PO4⇌Cr(OH)3(H2PO4)2–2; Cr(OH)3(aq)+HPO2–4⇌Cr(OH)3HPO2–4] were found to be 2.78±0.3, 3.48±0.3, and 1.97±0.3, respectively.  相似文献   

16.
The binary phase diagram of KNO3-KClO3 is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO3)1−x(ClO3)x (0<x<0.20) and K(NO3)1−x(ClO3)x (0.90<x<1.0), were formed in the KNO3-based solid solutions and KClO3-based solid solutions phase, respectively. For KNO3-based solid solutions, KNO3 ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO3 by ClO3-radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO3-based (α) phase and KClO3-based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent.  相似文献   

17.
丙炴醇聚合膜对铁在酸性溶液中的缓蚀作用   总被引:3,自引:0,他引:3  
The formation of polymer film of propargyl alcohol(PA) and its protective ability against corrosion in Fe/H_2SO_4 and Fe/H_2SO_4+H_2S systems have been investigated using impedance measurement. The composition and morphology of the corrosion surface of iron, on which PA polymerized at different bines, were obtained with the aid of SEM and AFM as well as EDX. The results showed that PA polymerized into compact polymer film in Fe/H_2SO_4 and Fe/ H_2SO_4 + H_2S systems, which made iron surface smooth and have a morphologies of regular square structure in microscopic level. In Fe/H_2SO_4 system, macroscopic continuous polymer film of PA was not formed leading to local corrosion on electrode surface. In Fe/H_2SO_4 +H_2S system, the adsorption of H_2S and HS - on electrode surface slowed down the formation of polymer film of PA. However, the iron sulfide, produced after a longer time, increased the continuity of the polymer film of PA and therefore, the polymer film could perform its long-te...更多rm inhibition action.  相似文献   

18.
Two solid-state coordination compounds of rare earth metals with glycin, [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O melted at 342.90 K, while [ErY(Gly)6(H2O)4](ClO4)6·5H2O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol−1 and 53.9 J K−1 mol−1 for [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O, 1.82 kJ mol−1 and 5.5 J K−1 mol−1 for [ErY(Gly)6(H2O)4](ClO4)6·5H2O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.  相似文献   

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