HSCChemistry使用手册Eh-pHDiagram模块中文

1、1 /4717 0). These conditions may exist near the anode in the electrochemical cell, 2 /47but can also be generated with some oxidizing agents (Cu + H2O2 = CuO + H2O). In reducing conditions, when potential is low (Eh 0)。这些条件可能存在在电化学电池的阳极，但也可以与一些氧化剂(H2O2生成6 +铜+H2O=) o在还原条件下，当为低电位(EhVO),该系统能够提供电子的物种， 例

2、如，与阴极电极或与还原剂。The pH of the system describes its ability to supply protons (H(+a) to the species. In acid conditions (pH 7) the concentration of protons is low.pH值的系统描述其提供质子的能力(H ( + )的种类。在酸性条件下(pHV7)质子 的浓度较高，在碱性条件下(pH7)的质子浓度低。Usually a large amount of different species exist simultaneously in the aq

3、ueous mixtures in fixed Eh-pH-conditions. The Pourbaix diagrams simplify this situation a lot by showing only the predominant species which content is highest in each stability areas. The lines in the diagrams represent the Eh-pH-conditions where the content of the adjacent species is the same in th

4、e equilibrium state. However, these species always exist in small amounts on both sides of these lines and may have an effect on practical applications通常一个大的不同物种的数量同时存在固定的Eh-pH条件水混合物。Pourbaix图简化 这种情况很多只显示优势种，内容是每个稳定性最高的地区。图中的线代表Eh-pH条 件下相邻物种的内容是在平衡状态下相同。然而，这些品种都存在少量的这些线的两 侧，可能对实际应用的影响。The lines in t

5、he diagrams can also be represented with chemical reaction equations These reactions may be divided into three groups according to reaction types:图中的线也可以用化学反应方程式。这些反应可分为三组，根据反应类型：1 Horizontal lines These lines represent reactions that are involved with electrons,but are independent of pH Neither H(+

6、a)-ions nor OH(-a)-ions participate to these reactions1水平线。这些线代表的反应，涉及电子，但独立的博士没有H ( + )离子和OH ()- 离子参与反应。2.Diagonal lines with either positive or negative slope These lines representreactions that arc involved with both electrons and H(+a)-and OH(-a)-ions.2。对角线或正或负的斜率。这些线代表的反应，涉及电子和H ( + )和(-)-离子哦。3

7、.Vertical lines These lines represent reactions that arc involved either with H(+a)- or OH(-a)-ions, but arc independent of Eh. In other words, electrons do not participate with these reactions3 /473垂直线。这些线代表反应，可能与H ( + )或(J 离子哦，但独立的啊。换句话 说，电子不参与这些反应。The chemical stability area of the water is shown

8、 in the Eh-pH-diagrams with dotted lines. The upper stability limit of water is based on the potential when the oxygen generation starts on the anode It is specified by the reaction:水的化学稳定性区域是在虚线的Eh-pH图所示。水上稳定极限是基于势当氧代开始在 阳极。它是由指定的反应：2 H2O = 02(g) + 4 H(+a) + 4e-2 H20 = 02 (g) +4H ( + ) +4The lower

9、stability limit is based on hydrogen formation on the cathode. It is specified by the reaction:较低的稳定极限是基丁阴极上氢的形成。它是由指定的反应：2 H(+a) + 2 c- = H2(g)2H ( + ) +2E 二 H2 (g)The construction of the diagrams with HSC Chemistry EpH module is quite a simple task. However, several aspects must be taken into acco

10、unt when specifying the chemical system and analyzing the calculation results, for example:用HSC-Chemistry弗模块图的建设是一个相当简单的任务。然而，几个方面必须考虑 指定化学系统分析计算结果，例如：1 A basic knowledge of chemistry, aqueous systems and electrochemistry orhydrometallurgy is always needed in order to draw the correct conclusions1。一

11、个基本的化学知识，水系统和电化学或湿法总是为了得出正确的结论。2.The EpH module carries out the calculations using pure stoichiometric substances In practice minerals may contain impurity elements and the composition may deviate slightly from the stoichiometric one.2。弗模块进行计算，采用纯化学物质。在实践中可能含有的杂质元素和矿物组成可能 稍微偏离化学计量。3There are always

12、some errors in the basic thermochemical data of the species. Thismay have significant effect on the results, especially if the chemical driving force of the reaction is small. Usually small differences between Pourbaix diagrams from different sources can be explained by the slightly different basic

13、data used3。总有一些物种的基本热化学数据的一些错误。这可能会对结果有显著的影响，特别 是如果该反应的化学驱动力小。通常小差异Pourbaix图从不同的來源可以通过使用略 有不同的基本数据的解释。4 /474.Sometimes data for all existing species is not available from the HSC database orfrom the other sources. This will distort the results if the missing species are stable in given conditions. T

14、he missing unstable species will have no effect on the results.4。有时数据中的所有现存的物种是无法从数据库或从其他來源的造血干细胞。这会扭 曲结果如果丢失的物种是在特定条件下稳定。失踪的不稳定的物种会对结果没有影 响。5.The EpH module does not take into account the non-ideal behavior of aqueous solutions However, in many cases these ideal diagrams give a quite good idea of t

15、he possible reactions in aqueous solutions, especially if the driving force of the reactions is high.5。弗模块没有考虑到溶液的非理想行为。然而，在许多情况下，这些理想图给出可能 的反应的一个相当好的主意在水溶液中，特别是如果该反应的驱动力是高。6.Thermochemical calculations do not take into account the speed of the reactions (kinetics). For example, the formation of the

16、 SO4(-2a) ion may be a slow reaction. In these cases metastable diagrams created by removing such species from the system may give more consistent results with the experimental laboratory results.6。热化学计算不考虑反应的速度(动力学)。例如，在形成SO4 (2A)离子可能是一 个缓慢的反应。在这些情况下，亚稳态图，从系统中除去这些物种创造了可以提供更 一致的结果与实验结果。The HSC user

17、must be very careful when drawing conclusions from Eh-pH-diagrams due to these limitations and assumptions. However, these diagrams may offer extremely valuable information when combining the results with the experimental work and with a good knowledge of aqueous chemistry. There is no universal kin

18、etic or thermochemical theory available, which could entirely substitute traditional experimental laboratory work with pure theoretical calculation modelsHSC的用户必须非常小心，当得出结论臼卜pH图由丁这些限制和假设。然而，这些图 可以提供极有价值的信息时，将结果与实验工作和与水化学知识好。有没有通用的动 力学、热化学理论可用，可完全替代传统的纯理论计算模型实验的实验室工作。More information on Eh-pH-diagram

19、s, calculation methods and applications can be found from different handbooks, for example, from the Pourbaix Atlas 12.在EhpH图计算方法和应用的更多信息，可以发现不同的手册，例如，从儿atlas 12o5 /47f7 Criss-CobbleSelect Other Elements |Select Main Elementabcehilabcehilmm / / e e b b n n r r TTTTTTTTTTTTTTTUVWXYTUVWXYYZZYZZ : : ei

20、ei p p s s abdmortuabdmortuabehnabehn UHbUHb NMNM N N oooo p p pppp p p pppp p p pppp R R RRRR RRRasRRRas u u e e mm r r a a d d e e efgoefgo EFFFFGEFFFFGGGHHHGGHHHHHHH c c 9 9 mm I I s s t t u u a a e e i i LFLF CAACAacCAACAaclAIBBBBBlAIBBBBBc c eiei mm n n I I s s ssssss ssss rKrK 筈孟MgMnMONNaNbNdM

21、gMnMONNaNbNd k k I I adeflmorsuyrsadeflmorsuyrs BBCCCCCCCCCCCDEEBBCCCCCCCCCCCDEE雷盟匸盅uvwxeuvwxe丫YbznNYbznNmm I I AKAAKA A ABBaBeBiBkBrccacdceGDcmcocrcsBBaBeBiBkBrccacdceGDcmcocrcsBaBaDyErEsDyErEsC:HSC5EpHXCuS25.iepFile OpenHelpExit |17.2 Chemical System Specifications Eh-pH Diagram. Authors: H-H Haun

22、g K Anttila and A RoineFig. L Selecting elements and species for the Eh - pH - diagram.The EpH Diagram selection in the HSC main menu will show the EpH-form Fig. 1. The user must specify the chemical system, which will be used to calculate the diagram in this form. Assume that system contains Cu, S

23、and H2O. The following steps should be specified in order to create the diagram:在主菜单中选择HSC弗图将显示弗形，图1。用户必须指定的化学系统，这将彼用來 计算这种形式的图。假设系统含有Cu, S和H2O。以下步骤应该被指定为创建图表：1.Select Main Element: Select one element from the list. This element will be usedas the main” element in the first diagram, i.e. all species

24、, which are shown in the diagram, will contain this element. The user can easily change the main element selection later on in the diagram form. The Cu has been selected in this example.Io选择的主要因素：从列表中选择一个元素。本单元将作为第一个图的“主要”元 素，即所有的物种，这是图中所示，将包含此元素。用户可以很容易地改变的主要元 素的选择，后來在图的形式。铜已在本例中选择。2Select Other El

25、ements: Select other elements to the system. Up to 7 elements canSelect Species AllTemperature:T 1!25T 250T 3f75T 4JTOOFile Save |6 /47be selected but it is recommended to use less, because large amount of elements and species increase calculation time and could cause some other problems S has been

26、selected in this example Note: It is not necessary to select H and O because these arc always automatically included 2。选择其他元素：选择其他元素的系统。高达7的元素可以选择但建议少用，因为元 素和物种大量增加计算时间和可能引发的其他问题。已经在本例中选择。注：这是没 有必要选择H和0,因为这些都是自动地包括。3.Search Mode: This selection specifies the type of species, which will be collected

27、from the database It is recommended to use default selections. Note: Condensed = solid substances, Aqueous Neutrals =dissolvcd species without charge. Aqueous Ions = dissolved ions, Gases = gaseous species without charge. Gas Ions = gaseous ions, and Liquids = liquid species.3。搜索模式：选择指定物种的类型，它将彼从数据库

28、中收集。建议使用默认的选择。 注：凝结为固体物质，水中立二溶解不收费，水离子二溶解离子，气体二气态物种没有电 荷，气体离子二气态离子，和液体二液体的种类。4.OK: Press OK to start the search from the database4。好：按OK从数据库开始搜索。5.Select Species: Usually you can select all species to the diagram by pressing All In some cases, however, it is useful to remove unnecessary species from

29、 the systcm. This will decrease calculation time and simplify diagrams. Note: A) By pressing simultaneously Ctrl- key and clicking with the mouse it is easy to make any kind of selection B) By double clicking the species it is possible to see more information of the species Load CUS25.IEP sec the se

30、lected species of this example5。树种选择：通常您可以选择的所有物种的图按所有。然而，在某些情况下，它是从 系统中删除不必要的物种有用。这将减少计算时间和简化图。注：a)按下Ctrl键，同 时用鼠标很容易做出什么样的选择点击。B)双击物种有可能看到更多的物种信息。负 载cus25.icp文件看这个例子的选择种类。6.Temperature: The user must specify at least one temperature for the diagram. Up to four temperatures may be specified in order

31、 to draw combined diagrams, which show the effect of temperature The temperatures 25, 50. 75 and 100 C have been selected in this example, Figs 1 and 2.6。温度：用户必须指定至少一个温度图。高达四的温度可以彼指定为绘制组合图，显 示温度的影响。温度25, 50, 75和100 C己在本例中选择，无花果。1和2。7.Criss-Cobblc: This option enables HSC to extrapolate the heat capa

32、city function of the aqueous species if this data is not given in the database 115 see Chapter 28.4.7。纵横交错的卵石：此选项使HSC推断水种的热容量功能如果这个数据是不是在 database 11 给出，见 28.4 章。8.EpH: Press EpH to start the dialog and Calculation of the diagram. You can also7 /47press in order to save the data for later use withou

33、t running the calculation procedure8。弗：按弗开始保存文件对话框的图和计算。你也可以按文件保存为数据保存供以后 使用无需运行的计算程序。9.Diagram: Pressing the EpH button will show the Diagram specification form, see Chapter 17.3 and Fig 2. By pressing Diagram in Fig. 2 you will see the default diagram.9。图：按弗按钮将显示图的规范形式，见17.3章图2。按图在图2中你会看到默认的 图。173

34、 Eh - pH - Diagram MenuFig. 2. Default values for the Eh pH - diagram.The EpH-diagram menu shows a summary of the chemical system specifications as well as selected default values for the diagram. The fastest way to go forward is to accept all the default values and press Diagram for simple EpH diag

35、rams or Combine for combined diagrams Usually at the begining, there is no need for modifications to the default values. However, it is important to understand the meaning of these settings because they may have strong effect on the diagram. The details of the diagram menu options are explained in t

36、he following 8 /47paragraphs.Eph图菜单显示的化学系统规范总结以及选择默认值的图表。走的最快的方法是接受 所有默认值，并按图简单弗图或结合组合图。通常在开始时，没有必要 为默认值的修改。然而，它是理解这些设置的意义重要，因为他们可能 在图上强烈的影响。图中的菜单选项的细节在下面解释。1.1。 打开文件The EpH module can also be used as an independent application, in these cases the data for the diagram may be read from *.IEP files by

37、 pressing Normally the system specifications are automatically transferred from the system specification sheet to the diagram menu. Fig. 2.Eph模块也可以作为一个独立的应用程序，在这些情况下，图的数据可以读口按 IEP文件打开文件。通常的系统规格说明书由系统自动转移到关系图” 菜单，如图2所示。The diagram specifications can be modified in the diagram menu. The selections can

38、 be saved for later use with IEP selection from the menu. The IEP-filcs may also be edited by any text editor like Windows Notepad Please be careful as any mistake may cause unpredictable results. The calculation results may be saved to *.EPH EpH selection and loaded back with EPH selection which ca

39、uses the diagram to be automatically recalculated图规格可以在关系图”菜单修改。选择可以保存供以后使用保存文件时选择菜单。IEP 文件可以使用任何文本编辑器如Windows记事本编辑。请小心，任何错 误都可能导致不可预知的结果。计算结果可以保存到文件与文件保存。 弗弗的选择和装回文件打开弗选择使图自动重新计算。2. Species and DG-data workbook2。物种和DG数据手册The selected species and calculated DG-data based on the enthalpy, entropy and

40、 heat capacity values of the HSC database is shown on the Species sheet of the diagram workbook, Fig. 2. The species are arranged according to elements and species type. The user can modify the DG-data as well as add or remove species in this sheet. The Species sheet makes it possible to use data an

41、d species which cannot be found in the HSC database, for example:选择的种类和计算DG数据基于焙，爛和热的HSC数据库容量值在图表工作簿的物种 表所示，图2。种类按要素和种类。用户可以同时添加或删除本片种 DG数据修改。物种表可以使用数据和物种而不能在HSC的数据库中找 到,例如：A.The published Pourbaix diagrams are often based on DG-data which is given in the original papers This DG-data can be used in

42、the Species sheet to replace the default values based on the HSC database if necessary Note that these DG- values can also be calculated from the standard potential values using equation 19 /47A. 发表Pourbaix图往往是基于DG数据是原始文件。这DG数据可用丁物种片代替默认值基于HSC如果必要的数据库。注意这些DG值也可以用公式1的标 准电位值的计算， 1，1where n is the char

43、ge transferred in the cell reaction, F is the Faraday constant (23045 cal/(V*mol) and E is the standard electrode potential in volts Note: Give DG-data for the selected temperatures, usually these values arc only available at 25 C.其中n是细胞反应的电荷转移，F是法拉第常数(23045卡/ (V *摩尔)和E是伏特 的标准电极电位。注：为选定的温度给DG数据，通常这些

44、值在25 C. 只有B.Sometimes all necessary species are not available in the HSC database These missingspecies can be added to the chemical system specification if the user has the DG-values or chemical potential data for these species The new species may be added by inserting empty row with Insert Row sele

45、ction and typing formula and DG-valucs to this row.B. 有时必要的物种没有造血干细胞库。这些失踪的物种可以被用户如果有DG值或化学这些物种潜在的数据添加到化学系统规范。新的物种可以被插入行的 选择和输入公式和DG值这一行插入空行添加。The new species can be inserted into any location, but it is recommended to add the same type of species sequentially, because it makes the list easier to re

46、ad and update Note: A) Do not insert any new elements, new elements must be added in the EpH-clemcnt selection window. Fig. 1. B) Do not create empty rows.新的物种可以被插入到任何位置，但建议增加物种的相同类型的顺序，因为它使列表 更容易读取和更新。注：a)不要将任何新的元素，新的元素必须在弗 元选择窗口，如图I所示。B)不要创建空的行。C.In some cases it is necessary to remove certain spe

47、cies from the system, c.g. if somekinetic barriers are found to slow down the reaction rate in the experiments. Such species can be removed by Delete Row selection在某些情况下有必要从系统中删除某些物种，如一些运动障碍明显减慢反应速率的实 验研究。这样的物种可以被删除的行选择。The Labels and Lines sheets are in the programs internal use and it is not neces

48、sary to make any modifications to these sheets. The Labels sheet contains format data for the labels such as; text, area number, coordinates, font name and properties, and labels visibility and orientation. The Lines sheet contains format data of the equilibrium lines of the diagram: Species names,

49、line area numbers, line endpoint coordinates, and line properties标签和线路板在程序内部使用，不需要这些表所做的任何修改。标签表包含的标签等 格式的数据；文本，地区编号，坐标，字体名称和属性，和标签的可见 性和取向。线片包含了图的平衡线格式数据：物种名称，线数，线端点 10 /47坐标，和线的性能。3. Temperature3。温度The Pourbaix-diagrams are drawn at a constant temperature The user must select one temperature for t

50、he diagram from the list of temperatures, Fig. 2. The actual temperature values can only be changed from the system specification form. Fig. 1. No temperature selection is needed here for the Combined diagrams.Pourbaix图绘制在一个恒定的温度。用户必须选择从列表中的一个温度温度图，图2。 实际温度值只能从制度规范的形式，如图1所示。没有温度的选择是需 要组合图。The defaul

51、t DG-values in the Species sheet in columns 2 - 5 arc calculated at the given temperatures. The DG-values at column 2 are calculated using the first temperature, column 2 using the second temperature, etc.在2 列5种表默认的DG值在给定温度下计算。在柱2 DG值用第一温度计算，柱2 使用第二温度，等。4. Other parameters4。 其他参数The default values f

52、or Dielectric Constant and DG of H20 are automatically calculated on the basis of the selected temperature and pressure. The calculation of Dielectric Constant is based on experimental values 15 and water vapor pressure 16, which are valid from 0 to 373 C, and from 1 to 5000 bar. Outside this range

53、the Dielectric Constant will be extrapolated介电常数和DG H2O的默认值是在选定的温度和圧力的基础上口动计算。介电常数的 计算是基于实验和水蒸气pressure 16 cn,这是有效的从0到373 C,从 1到5000巴。在这个范围内的介电常数将外推。The Ion Strength and Correction Factor constants are automatically calculated by the program and usually they do not need to be modified by the user.口动

54、计算的程序，通常他们不需要由用户修改的离子强度和校正因子常数。5. Potential and pH scale ranges5. Potential and pH scale ranges5。电位和pH值的范围The user may change the default range (Max Eh and Min Eh) for the potential scale as well as the range of pH scale (Max pH and Min pH). The scale settings can also be changed by clicking the x-

55、or y-axis on the diagram form. The minimum difference between Min and Max values is 0.2 and there is no upper limit for the difference.用户可以更改默认的范围(最大和最小的EH EH)潜在规模以及pH值范围(最大的 pH值和最小值)。规模的设置也可通过点击X或Y轴上的图形式的改 变。最小和最大值之间的最小差异为0.2,差异有无上限。11 /476. Molality and Pressure6。 质量摩尔浓度和圧力The diagrams are calcula

56、ted using constant molalities (concentrations) for all the elements. The default values may be changed in the table in the bottom right corner of the diagram menu, see Fig. 2. Molality values are given in mol/kg H2O units.该图是使用恒定浓度计算(浓度)的所有元素。默认值可以在表图中菜单的右下角的 变化，见图2。质量摩尔浓度值在摩尔/千克水单位给予。The total pres

57、sure of the system is also given in the Molality table. The EpH module uses maximum value given in the Pressure column as the chemical system total pressure.1( is not possible to select a smaller pressure value than water vapor pressure at the selected temperature. In other words, the total pressure

58、 must always be bigger than the water vapor pressure at the selected temperature. The default value for the pressure is 1 bar.乂是系统的总压力表给出的质量摩尔浓度。Eph模块采用最大值在圧柱为化工系统总 压力了。这是不可能的选择在选定的温度比水蒸气压力较小的圧力值。 换句话说，总压力必须大于在选定温度的水蒸汽圧力。对于圧力的默认 值是1杆。7. Show Predominance Areas of Ions7。 表明离子的优势领域The Show Predominanc

59、e Areas of Ions selection causes the EpH-module to calculate two diagrams for the same system. The first one is a normal Eh-pH-diagram with all species, and the second one is the predominance diagram with only aqueous species. Both diagrams are drawn into the same figure; the first diagram in black

60、and the second one in blue This option is recommended for use only with normal Eh-pH-diagrams (see Chapter 17.4).“离子”的选择使弗模块计算同一系统中的两个图表显示的优势领域。第一个是一个 正常的臼)-pH图与所有物种，第二个是只有水种的优势图。两图绘制在 同一图：黑色和蓝色的二个第一图。建议使用此选项仅用于正常的Eh- pH图(见17.4章)。8. Diagram and Combine Buttons8。图并结合按钮Diagram starts the calculations