HSCChemistry使用手冊Eh-pHDiagram模塊中文

1、17.Eh - pH - DIAGRAMS (Pourbaix-diagrams)Eh-pH-diagrams show the thermodynamic stability areas of different species in an aqueous solution. Stability areas are presented as a function of pH and electrochemical potential scales. Usually the upper and lower stability limits of water are also shown in

2、the diagrams with dotted lines. Traditionally these diagrams have been taken from different handbooks12. However, in most handbooks these diagrams are available only for a limited number of temperatures, concentrations and element combinations.Eh-pH圖顯示不同物種在水溶液中的熱力學(xué)穩(wěn)定區(qū)。穩(wěn)定的地區(qū)作為一個潛在的尺度和電化學(xué)作用的pH值。通常上、水下

3、穩(wěn)定極限也與虛線圖所示。傳統(tǒng)上，這些圖已從不同的handbooks12。然而，在大多數(shù)手冊這些圖是只有數(shù)量有限的溫度，濃度和元素組合。The Eh-pH module of HSC Chemistry allows the construction of diagrams in a highly flexible and fast way, because the user can draw the diagrams exactly at the selected temperature and concentration.HSC化學(xué)Eh-pH模塊允許在一個高度靈活和快速的方式圖解，因為用戶可

4、以畫出圖形，在選定的溫度和濃度。The Eh-pH-module is based on STABCAL - Stability Calculations for Aqueous Systems - developed by H.H. Haung, at Montana Tech., USA9,10.Eh-pH模塊是基于stabcal穩(wěn)定性計算水系統(tǒng)由H.H.黃發(fā)達，蒙大納科技，usa9,10。17.1IntroductionEh-pH-diagrams are also known as Pourbaix Diagrams according to author of the famous

5、Pourbaix diagram handbook12. The most simple type of these diagrams is based on a chemical system consisting of one element and water solution, for example, the Mn-H2O-system. The system can contain several types of species, such as dissolved ions, condensed oxides, hydroxides, oxides, etc. The Eh-p

6、H-diagram shows the stability areas of these species in the redox potential-pH-coordinates.Eh-pH圖也稱作Pourbaix圖根據(jù)著名的Pourbaix圖handbook12作者。這些圖的最簡單的類型是基于化學(xué)系統(tǒng)組成的一個元素和水的解決方案，例如，在mn-h2o-system。該系統(tǒng)可以包含多種類型的物種，如溶解離子，濃縮的氧化物，氫氧化物，氧化物，等電位-pH圖顯示在氧化還原電位pH這些物種的穩(wěn)定區(qū)域的坐標(biāo)。Usually the redox potential axis is based on t

7、he Standart Hydrogen Electrode (SHE) scale designated Eh, but other scales can also be used. The redox potential of the system represents its ability to change electrons. The system tends to remove electrons from the species when the potential is high (Eh > 0). These conditions may exist near the

8、 anode in the electrochemical cell, but can also be generated with some oxidizing agents (Cu + H2O2 = CuO + H2O). In reducing conditions, when potential is low (Eh < 0), the system is able to supply electrons to the species, for example, with a cathode electrode or with some reducing agents.通常氧化還

9、原電位軸是基于標(biāo)準(zhǔn)氫電極（她）規(guī)模劃啊，但也可以使用其他表。該系統(tǒng)的氧化還原電位代表其改變電子的能力。系統(tǒng)會刪除電子從物種可能是當(dāng)高（EH > 0）。這些條件可能存在在電化學(xué)電池的陽極，但也可以與一些氧化劑（H2O2生成Cu +銅+ H2O =）。在還原條件下，當(dāng)為低電位（Eh0），該系統(tǒng)能夠提供電子的物種，例如，與陰極電極或與還原劑。The pH of the system describes its ability to supply protons (H(+a) to the species. In acid conditions (pH < 7) the concentra

10、tion of the protons is high and in caustic conditions (pH > 7) the concentration of protons is low.pH值的系統(tǒng)描述其提供質(zhì)子的能力（H（+）的種類。在酸性條件下（pH7）質(zhì)子的濃度較高，在堿性條件下（pH7）的質(zhì)子濃度低。Usually a large amount of different species exist simultaneously in the aqueous mixtures in fixed Eh-pH-conditions. The Pourbaix diagram

11、s 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 the equilibrium state. However, these species always exist in sm

12、all amounts on both sides of these lines and may have an effect on practical applications.通常一個大的不同物種的數(shù)量同時存在固定的Eh-pH條件水混合物。Pourbaix圖簡化這種情況很多只顯示優(yōu)勢種，內(nèi)容是每個穩(wěn)定性最高的地區(qū)。圖中的線代表Eh-pH條件下相鄰物種的內(nèi)容是在平衡狀態(tài)下相同。然而，這些品種都存在少量的這些線的兩側(cè)，可能對實際應(yīng)用的影響。The lines in the diagrams can also be represented with chemical reaction equat

13、ions. These reactions may be divided into three groups according to reaction types:圖中的線也可以用化學(xué)反應(yīng)方程式。這些反應(yīng)可分為三組，根據(jù)反應(yīng)類型：1.Horizontal lines. These lines represent reactions that are involved with electrons, but are independent of pH. Neither H(+a)-ions nor OH(-a)-ions participate to these reactions.1水平線。

14、這些線代表的反應(yīng)，涉及電子，但獨立的博士沒有H（+）離子和OH（-）-離子參與反應(yīng)。2.Diagonal lines with either positive or negative slope. These lines represent reactions that are involved with both electrons and H(+a)-and OH(-a)-ions.2。對角線或正或負(fù)的斜率。這些線代表的反應(yīng)，涉及電子和H（+）和（-）-離子哦。3.Vertical lines. These lines represent reactions that are involv

15、ed either with H(+a)- or OH(-a)-ions, but are independent of Eh. In other words, electrons do not participate with these reactions.3垂直線。這些線代表反應(yīng)，可能與H（+）或（-）-離子哦，但獨立的啊。換句話說，電子不參與這些反應(yīng)。The chemical stability area of the water is shown in the Eh-pH-diagrams with dotted lines. The upper stability limit of

16、 water is based on the potential when the oxygen generation starts on the anode. It is specified by the reaction:水的化學(xué)穩(wěn)定性區(qū)域是在虛線的Eh-pH圖所示。水上穩(wěn)定極限是基于勢當(dāng)氧代開始在陽極。它是由指定的反應(yīng)：2 H2O = O2(g) + 4 H(+a) + 4 e-2 H2O = O2（g）+ 4 H（+）+ 4The lower stability limit is based on hydrogen formation on the cathode. It is spe

17、cified by the reaction:較低的穩(wěn)定極限是基于陰極上氫的形成。它是由指定的反應(yīng)：2 H(+a) + 2 e- = H2(g)2 H（+）+ 2 E = H2（g）The construction of the diagrams with HSC Chemistry EpH module is quite a simple task. However, several aspects must be taken into account when specifying the chemical system and analyzing the calculation resu

18、lts, for example:用HSC-Chemistry弗模塊圖的建設(shè)是一個相當(dāng)簡單的任務(wù)。然而，幾個方面必須考慮指定化學(xué)系統(tǒng)分析計算結(jié)果，例如：1.A basic knowledge of chemistry, aqueous systems and electrochemistry or hydrometallurgy is always needed in order to draw the correct conclusions.1。一個基本的化學(xué)知識，水系統(tǒng)和電化學(xué)或濕法總是為了得出正確的結(jié)論。2.The EpH module carries out the calculati

19、ons using pure stoichiometric substances. In practice minerals may contain impurity elements and the composition may deviate slightly from the stoichiometric one.2。弗模塊進行計算，采用純化學(xué)物質(zhì)。在實踐中可能含有的雜質(zhì)元素和礦物組成可能稍微偏離化學(xué)計量。3.There are always some errors in the basic thermochemical data of the species. This may ha

20、ve 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 data used.3?？傆幸恍┪锓N的基本熱化學(xué)數(shù)據(jù)的一些錯誤。這可能會對結(jié)果有顯著的影響，特別是如果該反應(yīng)的化學(xué)驅(qū)動力小。通常小差異Pour

21、baix圖從不同的來源可以通過使用略有不同的基本數(shù)據(jù)的解釋。4.Sometimes data for all existing species is not available from the HSC database or from the other sources. This will distort the results if the missing species are stable in given conditions. The missing unstable species will have no effect on the results.4。有時數(shù)據(jù)中的所有現(xiàn)存的

22、物種是無法從數(shù)據(jù)庫或從其他來源的造血干細胞。這會扭曲結(jié)果如果丟失的物種是在特定條件下穩(wěn)定。失蹤的不穩(wěn)定的物種會對結(jié)果沒有影響。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 the possible reactions in aqueous solutions, especially if the driving force o

23、f the reactions is high.5。弗模塊沒有考慮到溶液的非理想行為。然而，在許多情況下，這些理想圖給出可能的反應(yīng)的一個相當(dāng)好的主意在水溶液中，特別是如果該反應(yīng)的驅(qū)動力是高。6.Thermochemical calculations do not take into account the speed of the reactions (kinetics). For example, the formation of the SO4(-2a) ion may be a slow reaction. In these cases metastable diagrams creat

24、ed by removing such species from the system may give more consistent results with the experimental laboratory results.6。熱化學(xué)計算不考慮反應(yīng)的速度（動力學(xué)）。例如，在形成SO4（2A）離子可能是一個緩慢的反應(yīng)。在這些情況下，亞穩(wěn)態(tài)圖，從系統(tǒng)中除去這些物種創(chuàng)造了可以提供更一致的結(jié)果與實驗結(jié)果。The HSC user must be very careful when drawing conclusions from Eh-pH-diagrams due to these li

25、mitations 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 kinetic or thermochemical theory available, which could entirely substitute traditio

26、nal experimental laboratory work with pure theoretical calculation models.HSC的用戶必須非常小心，當(dāng)?shù)贸鼋Y(jié)論Eh-pH圖由于這些限制和假設(shè)。然而，這些圖可以提供極有價值的信息時，將結(jié)果與實驗工作和與水化學(xué)知識好。有沒有通用的動力學(xué)、熱化學(xué)理論可用，可完全替代傳統(tǒng)的純理論計算模型實驗的實驗室工作。More information on Eh-pH-diagrams, calculation methods and applications can be found from different handbooks, fo

27、r example, from the Pourbaix Atlas12.在Eh-pH圖計算方法和應(yīng)用的更多信息，可以發(fā)現(xiàn)不同的手冊，例如，從兒atlas12。17.2Chemical System SpecificationsFig. 1. 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,

28、 which will be used to calculate the diagram in this form. Assume that system contains Cu, S and H2O. The following steps should be specified in order to create the diagram:在主菜單中選擇HSC弗圖將顯示弗形，圖1。用戶必須指定的化學(xué)系統(tǒng)，這將被用來計算這種形式的圖。假設(shè)系統(tǒng)含有Cu，S和H2O。以下步驟應(yīng)該被指定為創(chuàng)建圖表：1.Select Main Element: Select one element from the

29、 list. This element will be used as the “main” element in the first diagram, i.e. all species, 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.1。選擇的主要因素：從列表中選擇一個元素。

30、本單元將作為第一個圖的“主要”元素，即所有的物種，這是圖中所示，將包含此元素。用戶可以很容易地改變的主要元素的選擇，后來在圖的形式。銅已在本例中選擇。2.Select Other Elements: Select other elements to the system. Up to 7 elements can be selected but it is recommended to use less, because large amount of elements and species increase calculation time and could cause some oth

31、er problems. S has been selected in this example. Note: It is not necessary to select H and O, because these are always automatically included.2。選擇其他元素：選擇其他元素的系統(tǒng)。高達7的元素可以選擇但建議少用，因為元素和物種大量增加計算時間和可能引發(fā)的其他問題。已經(jīng)在本例中選擇。注：這是沒有必要選擇H和O，因為這些都是自動地包括。3.Search Mode: This selection specifies the type of species,

32、which will be collected from the database. It is recommended to use default selections. Note: Condensed = solid substances, Aqueous Neutrals =dissolved species without charge, Aqueous Ions = dissolved ions, Gases = gaseous species without charge, Gas Ions = gaseous ions, and Liquids = liquid species

33、.3。搜索模式：選擇指定物種的類型，它將被從數(shù)據(jù)庫中收集。建議使用默認(rèn)的選擇。注：凝結(jié)為固體物質(zhì)，水中立=溶解不收費，水離子=溶解離子，氣體=氣態(tài)物種沒有電荷，氣體離子=氣態(tài)離子，和液體=液體的種類。4.OK: Press OK to start the search from the database.4。好：按OK從數(shù)據(jù)庫開始搜索。5.Select Species: Usually you can select all species to the diagram by pressing All. In some cases, however, it is useful to remove

34、 unnecessary species from the system. 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.

35、 Load CUS25.IEP file to see the selected species of this example.5。樹種選擇：通常您可以選擇的所有物種的圖按所有。然而，在某些情況下，它是從系統(tǒng)中刪除不必要的物種有用。這將減少計算時間和簡化圖。注：a）按下Ctrl鍵，同時用鼠標(biāo)很容易做出什么樣的選擇點擊。B）雙擊物種有可能看到更多的物種信息。負(fù)載cus25.iep文件看這個例子的選擇種類。6.Temperature: The user must specify at least one temperature for the diagram. Up to four temper

36、atures may be specified in order 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。溫度：用戶必須指定至少一個溫度圖。高達四的溫度可以被指定為繪制組合圖，顯示溫度的影響。溫度25，50，75和100°C已在本例中選擇，無花果。1和2。7.Criss-Cobble: This optio

37、n enables HSC to extrapolate the heat capacity function of the aqueous species if this data is not given in the database11, see Chapter 28.4.7?？v橫交錯的卵石：此選項使HSC推斷水種的熱容量功能如果這個數(shù)據(jù)是不是在database11給出，見28.4章。8.EpH: Press EpH to start the File Save dialog and Calculation of the diagram. You can also press File

38、 Save in order to save the data for later use without running the calculation procedure.8。弗：按弗開始保存文件對話框的圖和計算。你也可以按文件保存為數(shù)據(jù)保存供以后使用無需運行的計算程序。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 di

39、agram.9。圖：按弗按鈕將顯示圖的規(guī)范形式，見17.3章圖2。按圖在圖2中你會看到默認(rèn)的圖。17.3Eh - 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

40、 default values and press Diagram for simple EpH diagrams 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

41、details of the diagram menu options are explained in the following paragraphs.Eph圖菜單顯示的化學(xué)系統(tǒng)規(guī)范總結(jié)以及選擇默認(rèn)值的圖表。走的最快的方法是接受所有默認(rèn)值，并按圖簡單弗圖或結(jié)合組合圖。通常在開始時，沒有必要為默認(rèn)值的修改。然而，它是理解這些設(shè)置的意義重要，因為他們可能在圖上強烈的影響。圖中的菜單選項的細節(jié)在下面解釋。1. File Open1。打開文件The EpH module can also be used as an independent application, in these cases t

42、he data for the diagram may be read from *.IEP files by pressing File Open. Normally the system specifications are automatically transferred from the system specification sheet to the diagram menu, Fig. 2.Eph模塊也可以作為一個獨立的應(yīng)用程序，在這些情況下，圖的數(shù)據(jù)可以讀自*。按IEP文件打開文件。通常的系統(tǒng)規(guī)格說明書由系統(tǒng)自動轉(zhuǎn)移到關(guān)系圖”菜單，如圖2所示。The diagram spec

43、ifications can be modified in the diagram menu. The selections can be saved for later use with File Save IEP selection from the menu. The IEP-files may also be edited by any text editor like Windows Notepad. Please be careful as any mistake may cause unpredictable results. The calculation results ma

44、y be saved to *.EPH file with File Save EpH selection and loaded back with File Open EPH selection which causes the diagram to be automatically recalculated.圖規(guī)格可以在關(guān)系圖”菜單修改。選擇可以保存供以后使用保存文件時選擇菜單。IEP文件可以使用任何文本編輯器如Windows記事本編輯。請小心，任何錯誤都可能導(dǎo)致不可預(yù)知的結(jié)果。計算結(jié)果可以保存到文件與文件保存。弗弗的選擇和裝回文件打開弗選擇使圖自動重新計算。2. Species and

45、DG-data workbook2。物種和DG數(shù)據(jù)手冊The selected species and calculated DG-data based on the enthalpy, entropy and 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 D

46、G-data as well as add or remove species in this sheet. The Species sheet makes it possible to use data and species which cannot be found in the HSC database, for example:選擇的種類和計算DG數(shù)據(jù)基于焓，熵和熱的HSC數(shù)據(jù)庫容量值在圖表工作簿的物種表所示，圖2。種類按要素和種類。用戶可以同時添加或刪除本片種DG數(shù)據(jù)修改。物種表可以使用數(shù)據(jù)和物種而不能在HSC的數(shù)據(jù)庫中找到，例如：A.The published Pourbaix

47、diagrams are often based on DG-data which is given in the original papers. This DG-data can be used in 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 1A.發(fā)表Pourb

48、aix圖往往是基于DG數(shù)據(jù)是原始文件。這DG數(shù)據(jù)可用于物種片代替默認(rèn)值基于HSC如果必要的數(shù)據(jù)庫。注意這些DG值也可以用公式1的標(biāo)準(zhǔn)電位值的計算,1， 1 where n is the charge 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 value

49、s are only available at 25 °C.其中n是細胞反應(yīng)的電荷轉(zhuǎn)移，F(xiàn)是法拉第常數(shù)（23045卡/（V *摩爾）和E是伏特的標(biāo)準(zhǔn)電極電位。注：為選定的溫度給DG數(shù)據(jù)，通常這些值在25°C.只有B.Sometimes all necessary species are not available in the HSC database. These missing species can be added to the chemical system specification if the user has the DG-values or chemic

50、al potential data for these species. The new species may be added by inserting empty row with Insert Row selection and typing formula and DG-values to this row.B.有時必要的物種沒有造血干細胞庫。這些失蹤的物種可以被用戶如果有DG值或化學(xué)這些物種潛在的數(shù)據(jù)添加到化學(xué)系統(tǒng)規(guī)范。新的物種可以被插入行的選擇和輸入公式和DG值這一行插入空行添加。The new species can be inserted into any location,

51、 but it is recommended to add the same type of species sequentially, because it makes the list easier to read and update. Note: A) Do not insert any new elements, new elements must be added in the EpH-element selection window, Fig. 1. B) Do not create empty rows.新的物種可以被插入到任何位置，但建議增加物種的相同類型的順序，因為它使列表

52、更容易讀取和更新。注：a）不要將任何新的元素，新的元素必須在弗元選擇窗口，如圖1所示。B）不要創(chuàng)建空的行。C.In some cases it is necessary to remove certain species from the system, e.g. if some kinetic barriers are found to slow down the reaction rate in the experiments. Such species can be removed by Delete Row selection.在某些情況下有必要從系統(tǒng)中刪除某些物種，如一些運動障礙明顯

53、減慢反應(yīng)速率的實驗研究。這樣的物種可以被刪除的行選擇。The Labels and Lines sheets are in the programs internal use and it is not necessary 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

54、 orientation. The Lines sheet contains format data of the equilibrium lines of the diagram: Species names, line area numbers, line endpoint coordinates, and line properties.標(biāo)簽和線路板在程序內(nèi)部使用，不需要這些表所做的任何修改。標(biāo)簽表包含的標(biāo)簽等格式的數(shù)據(jù)；文本，地區(qū)編號，坐標(biāo)，字體名稱和屬性，和標(biāo)簽的可見性和取向。線片包含了圖的平衡線格式數(shù)據(jù)：物種名稱，線數(shù)，線端點坐標(biāo)，和線的性能。3. Temperature3。溫度T

55、he Pourbaix-diagrams are drawn at a constant temperature. The user must select one temperature for the 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

56、 diagrams.Pourbaix圖繪制在一個恒定的溫度。用戶必須選擇從列表中的一個溫度溫度圖，圖2。實際溫度值只能從制度規(guī)范的形式，如圖1所示。沒有溫度的選擇是需要組合圖。The default DG-values in the Species sheet in columns 2 5 are calculated at the given temperatures. The DG-values at column 2 are calculated using the first temperature, column 2 using the second temperature, etc

57、.在2列5種表默認(rèn)的DG值在給定溫度下計算。在柱2 DG值用第一溫度計算，柱2使用第二溫度，等。4. Other parameters4。其他參數(shù)The default values for Dielectric Constant and DG of H2O are automatically calculated on the basis of the selected temperature and pressure. The calculation of Dielectric Constant is based on experimental values15 and water vap

58、or pressure16, which are valid from 0 to 373 °C, and from 1 to 5000 bar. Outside this range the Dielectric Constant will be extrapolated.介電常數(shù)和DG H2O的默認(rèn)值是在選定的溫度和壓力的基礎(chǔ)上自動計算。介電常數(shù)的計算是基于實驗和水蒸氣pressure16 cn，這是有效的從0到373°C，從1到5000巴。在這個范圍內(nèi)的介電常數(shù)將外推。The Ion Strength and Correction Factor constants ar

59、e automatically calculated by the program and usually they do not need to be modified by the user.自動計算的程序，通常他們不需要由用戶修改的離子強度和校正因子常數(shù)。5. Potential and pH scale ranges5. Potential and pH scale ranges5。電位和pH值的范圍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 settin