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1. Trial3 52 Compounds OHC L Fig 3 18 Calculation results in gem 34 3 4 4 Minimization Minimization calculations will be made by selecting the Run menu After finishing each trial the color of the trial will be changed Results are given in the tabsheets of Results and Activities In the Result tab sheet the molar based results will be given and the activities will be given in the Activities tab sheet 3 4 5 Graphics and Tables The values given in tables can be copied to clipboard after the choosing the select all submenu and the copy menu in the edit main menu A part of tables can be also copied to clipboard by selecting the range by mouse down moving 3 5 Chemical Potential Diagram MALT for Windows provides the computer program CHD for constructing chemical potential diagrams Compared with chemical equilibrium calculations utilization of chemical potential diagrams is not so popular Even so chemical potential diagrams are quite convenient for materials thermodynamics Here explanation will be made on only how to construct the chemical potential diagram by using the thermodynamic data stored in MALT The thermodynamic meanings of the chemical potential diagram will be explained in user s manual for CHD 1 prepare the thermodynamic data for a selected chemical system 2 run the computer program CHD 3 specify the conditions to construct the chemica
2. Not determined yet _X Cancel 7 Help X Cancel Help Fig 3 22 Specification of Two Dimension Diagram Determination of coordinates To specify the diagram type drop the list of the combobox for the diagram type When 2D Chemical Potential Diagram is selected the sample diagram in the right hand side changed to an example for this diagram type The coordinates for the two dimensional diagram has to change on your preference The default coordinates are selected from the dimensional variables In Fig 3 22 these are the elemental chemical potentials for O C and Ca Although the target diagram is two dimensional three elemental chemical potentials are displayed This is because the three dimensional polyhedron is constructed in the three dimensional space and will be projected on a plane to show the two dimensional diagram To change the default coordinates double clicking will be made on the coordinate or select that coordinate by moving cursor and clicking the change button Then the coordinate form will appear like at the bottom right 4 CHD Win MALT Direct lt The kK T In P Pa O G Ga system gt AE mj x File F Edit E Project P View V Run R Diagram D Window W Help H 7 1000 00 K O BJ Q bo ok pO ly Fr oll 426 155 lt Ve18 E 27 F 11 gt Fig 3 23 Two Dimension Diagram for the Ca C O system at 1000K co
3. 126 160 161 162 163 164 165 166 167 168 169 170 171 172 173 Inorg Chem 24 583 1979 Volkov V L Rus J Phys Chem 52 1411 1978 Vlach K C You Y Z Chang Y A Thermochim Acta 103 361 370 1986 Schaefer S C Gokcen N A High Temp Sci 24 63 69 1987 Jacob K T Kale G M Iyengar G N K J Mater Sci 21 2753 2758 1986 Scolis Yu Ya Levitskii V A Lykova L N Kalinina T A J Solid State Chem 38 10 18 1981 Warhus U Maier J Rabenau A J Solid State Chem 72 113 125 1988 Asano M Kou T J Chem Thermodyn 20 1149 1156 1988 21 837 845 1989 Kou T Asano T High Temp Sci 24 1 19 1987 Wyers G P Cordfunke E H P Ouweltjes W J Chem Thermodyn 21 1095 1100 1989 Beyer R P Bennington O Brown R R J Chem Thermodyn 17 11 17 1985 Kohli R Lacom W Thermochim Acta 84 391 395 1985 Cordfunke E H P Ouweltjes W Van Vlaanderen P J Chem Thermodyn 19 1117 1120 1987 Vahlas C Chevalier P Y Blanquet E CALPHAD 13 273 293 1989 Schlesinger M E Chem Rev 90 607 628 1990 Kale G M Jacob K T Metall Trans 20B 687 691 1989 Barsoum M J Mater Sci 25 4394 4400 1990 Chirico R D Westrum E F Jr J Chem Thermodyn 12 71 85 1980 12 311 327 1980 13 519 525 1981 13 1087 1094 1981 Chirico R D Westrum E F J
4. or can be inserted in 67 the file When change is made inside the MALT for windows the comment line will be inserted to give the date of changes or modifications 4 3 6 Data Format Conversion MALT for Windows provides a function of MALT Direct environment to transfer the thermodynamic data retrieved to user s application programs see Chapter 6 for details In some software it is needed that compounds should be organized to give information of gaseous mixture aqueous solution and other mixtures The compound system in MALT for Windows only treat stoichiometric compounds Thus MALT for Windows provides a special function of converting data format to include mixture phases in the Data Format Conversion submenu in the Tools main menu This converted format is saved in a normal compound file so that when such a compound file is read from the folder the converted data format can be also reinstalled MALT for Windows also provides another format of the file which has the structure to descrive the mixture phase this file is called MALT Data file or compound data file Unlike the compound file this file cannot be read from MALT for Windows this means that this file cannot be modified any more Instead this file can be read from the user s application program or gem CHD In this explanation we use the term MALT Data file as a data converted compound system having the structure
5. CaCO CaO CO 3 1 When mode of searching compound in the top right corner in Fig 3 3 is specified as Compounds consisting a combination of elements this leads to retrieval of those compounds which consist of any of these three elements out of the database For details about retrieval mode see 4 3 The text string in the Edit Display Elements field is always saved in a combobox after input so that a list of the previously input string will be available on clicking the pull down button of the field To examine the thermal decomposition reaction of calcium carbonate please click the OK button without any correction the command of get a set of compounds in Ca C O with the mode 1 will be executed Immediately after retrieval is done the form changes to show results like Fig 3 4 At this stage the number given in the status bar in the MALT Main form changes from 0 to mpounds by Element Edit Display Elements 9 5 03 v O Selected Remove H D i Be O F Ne ns sam K BI Ti Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Sr Y Zr Ib Mo Te Ru Rn Pala ca in Sn sb Te 1 xe s Ba i Hr Ta w Re os ir Pe Au Hg TI Pb Bi Po At Rn Fr Ra La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu E SDS SSE Bets i x Cancel 7 Help Fig 3 3 Search Compounds by Element form for getting compound system Search Co Mode of Searching
6. Default setting is based on the gaseous mixture and stoichiometric compounds Verify the components for respective phases and correction can be made if necessary Save the set up compound data file in a selected file The application programs gem and CHD can be started from the above menus although these programs can be run outside MALT for Windows 4 2 7 On line help in MALT for Windows MALT for Windows has on line help systems as listed in Table 4 12 Table 4 12 Items and Functions of submenus in Help menu Item Accelerator key MALT Help M gem Help g CHD Help C Kagaku Gijutsu Sha Home Page K About MALT A Function MALT help file Gem help CHD help Make access to the home of Kagaku Gijutsu sha to know the updated information on the MALT and related software Version Number of MALT for Windows is shown Pressing PFl key always gives the help content correspondingly to the situation 39 4 2 8 Tool buttons Tool buttons are prepared for several submenus as listed in Table 4 13 These tool buttons are displayed differently depending on their ability When a tool button cannot be used in the absence ofthe satisfied conditions the tool button is displayed in the halftone and will not response to any clicking actions Table 4 13 Tool Buttons and Corresponding menu Tool buttons corresponding menu File Close Search Compound Append Compounds by Compound S
7. Under the thermodynamic environment that is realized by MALT Direct these handles are used in obtaining the thermodynamic and related properties of compounds specified by these numbers Compound File This is a file which stores the information on compound handles of what are retrieved and edited in the MALT for Windows and which can reproduce the compound handles in the memory later This file is particularly convenient when a certain set of compounds will be repeatedly used in the thermodynamic calculations This is not in the text format so that it cannot be used from other programs This has the extension of mcf Compound Data File Delimiter Extension Form GEF This is a file which stores the phase organization information This file cannot be read from the MALT for Winodws but from the user s application program This has the extension of med When several data are stored in one string division into respective data can be made by using delimiter character Usually space comma will be adopted ce 99 The name for three characters which is added after in the file name In the MALT for Windows mcf is used for the compound file mcd for the Compound Data file MALT Data file This is the Window graphic control which can be moved as a whole Usually forms have rectangular frame This is the Gibbs Energy Function in other wards the Free Energy Function FEF and define
8. real transition temperature dHtr real transition enthalpy PhaseTrans string 3 symbol of phase transition end The array for the phase data is defined as 20 to store the data in the present MALT for Windows data just 8 array elements are enough The rest are for the future use procedure GetThermoDataAtTemperatures Handle integer PhaseNo integer NTemp integer Temps MTRealarrayType var Results MtResultArrayType var ErrorCode byte virtual Function number 1 11 Thermodynamic functions of a selected compound at several temperatures This obtains the thermodynamic functions of a selected compound at several temperatures A compound handle to be calculated should be given in Handle A number of temperatures to be used in calculations should be set in NTemp a number of temperature region to be used in calculation being in PhaseNo This latter number should be less than the NumberOfPhases in MTCompoundType The total number of temperature regions phase its valid temperature range can be obtained in the MtPhaseINfoType which is given by procedure GetCompoundData When PhaseNo is set as zero calculations will be made by using the thermodynamic data of the stable phase at the selected temperatures Even so ifthe selected temperature is beyond the temperature range ofthe stored data it will be an error When PhaseNo is given by a non zero value the extrapolated values are given even for t
9. 11NO F11 OF1 NFO zi Thermodynamic constants lt lt lt CaCO3 calcite s gt gt gt Save Print Exit Fig 3 5 Thermodynamic Table of calcium carbonate Gibbs energy function gef standard enthalpy change for formation dfH and standard Gibbs energy change for formation dfG The present standard enthalpy and Gibbs energy changes for ormation provide values for the formation reaction from the elements at their reference state at respective temperatures In addition selection can be made about units of the thermodynamic functions temperature range and a step of temperature increment option for whether or not the thermodynamic constants are output This is selected in the Define Calc Condition submenu in the Calculate Equilibrium constant menu The same option can be selected through the Tab sheet name as Computation in MALT Options which can be selected through the Customized MALT setting submenu of the Tools main menu See 3 4 3 for details in these selections 18 During the Thermodynamic Table Form is shown the menu Calculate cannot be seen in the main menu bar To appear the Calculate menu you have to exit the Thermodynamic Table Form and to show the Compound Table Form The Tools menu is always available regardless what type of form is displayed 3 2 5 calculation of equilibrium constants The procedure for calculation of the equilibrium constants can be summarize
10. 13 King E G Mah A D Pankratz L B Thermodynamic Properties of Copper and its Inorganic Compounds INCRA monograph 2 1973 International Copper Research Association Inc 14 Mah A D Pankratz L B Contribution of the Data on Theoretical Metallurgy XVI Thermodynamic Properties of Nickel and Its Inorganic Compounds Bulletin of U S Bureau of Mines 668 1976 U S Government Printing Office Washington 15 Pankratz L B Thermodynamic Properties of Elements and Oxides Bulletin of U S Bureau of Mines 672 1982 U S Government Printing Office Washington Pankratz L B Stuve J M Gokcen N A Thermodynamic Data for Mineral Technology Bulletin of Bureau of Mines 677 1984 U S Government Printing Office Washington 16 Chang Y Austin Ashmad Nazeer Thermodynamic Data on Metal Carbonates and Related Oxides 1982 The Metallurgical Society of AIME Warrendale Pa US 17 Chart T G High Temp High Pressures 5 241 252 1973 18 Haas J L Jr Robinson G R Jr Hemingway B S Thermodynamic Tablations for Selected Phases in the System CaO A1 03 SiO2 H20 at 101 325 Pa 1 atm between 273 15 and 1800 K J Phys Chem Ref Data 10 3 575 669 1981 19 The Chemical Thermodynamics of Actinide Elements and Compounds Part 1 Oetting F L Rand M H Ackermann R J The Actinide Elements 1976 IAEA Vienna Part 2 Fluger J Oetting F L The Actinide Aqueous Ions 1976 IAEA Vie
11. Calculate menu will be available Note however that the Calculate menu is only available when the compound table form is shown in screen Submenus in the Calculate menu are shown in Table 4 5 The JANAF Type Table and the Equilibrium Constant have submenus and their contents are shown in Tables 4 6 and 4 7 The detailed explanation will be made in 4 4 Table 4 4 Items and functions of submenus appearing after selecting the menus of Get A Compound System or Append Compounds Item Function Search by Compound C Retrieve by inputting chemical formula Search by Element E Retrieve by inputting elements with specification of retrieve mode Table 4 5 Items and functions in the Calculate menu Item Accelerator key Function JANAF Type Table J Create a thermodynamic table in JANAF style Equilibrium Constants E Define a chemical reaction and calculate its equilibrium constant Table 4 6 Items and functions of the submenu JANAF Type Table Item Accelerator key Function Select Compound S Select the compound which you want to make the table Define Calc Conditions D Set up the conditions of calculation and the format of the table Calculate C Execute the calculation 49 Table 4 7 Items and functions ofthe submenu of Equilibrium Constants Item Accelerator key Function Define Reaction R Define a new reaction Modify Reaction M Modify or correct the
12. D J Chem Thermodyn 19 461 466 1987 Knights C F Phillips B A Special Publication No 30 High Temperature Chemistry of Inorganic and Ceramic Materials eds Glasser F P Potter P E 1977 The Chemical Society London 135 145 125 149 150 151 152 153 154 155 156 157 158 159 Ito Y Maruyama T Yoshimura M Saito Y J Mater Sci Letters 8 456 458 1989 Katsura T Kitayama K Sugihara T Kimizuka N Bull Chem Soc Japan 48 1809 1811 1975 Sugihara T Kimizuka N Katsura T Bull Chem Soc Japan 48 1806 1808 1975 Kimizuka N Katsura T Bull Chem Soc Japan 47 1801 1802 1974 Kitayama K Katsura T Bull Chem Soc Japan 49 998 1001 1976 Kimizuka N Katsura T J Solid State Chem 13 176 181 1975 15 151 157 1975 Sekine T Katsura T J Solid State Chem 17 49 54 1976 Katsura T Sekine T Kitayama K Sugihara T Kimizuka N J Solid State Chem 23 43 57 1978 Kitayama K Nojiri K Sugihara T Katsura T J Solid State Chem 56 1 11 1985 Piekarczyk W Weppner W Rabenau A Mat Res Bull 13 1077 1083 1978 Z Naturforsch 34a 430 436 1979 Tretyakov Yu D Kaul A R Portnoy V K High Temp Sci 9 61 70 1977 Myers C E Graves D T J Chem Eng Data 22 4 436 439 1977 440 445 1977 Bettonville S Goudiakas J Fuger J J Chem Thermodyn 19 595 604 1987 Xiang
13. Dokiya M Kato S Ota K Denki Kagaku 58 1 57 62 1990 Godshall N A Raistrick I D Huggins R A Mater Res Bull 15 561 1980 Takeshita H Ohmichi T Nasu S Watanabe H Sasayama T Maeda A Miyake M Sano T J Nucl Mater 78 281 1978 Hsu H S Devan J H J Electrochem Soc 133 2078 1986 Denielou L Petitet J P Tequi C J Chem Thermodyn 7 901 902 1975 Kohli R Lacom W Thermochim Acta 57 155 160 1982 81 327 333 1984 O Hare P A G Johnson G K J Chem Thermodyn 17 391 400 1985 Fredrickson D R Johnson G K O Hare P A G J Chem Thermodyn 12 801 805 1980 Venugopal V Iyer V S Agarwal R Roy K N Prasad R Sood D D J Chem Thermodyn 19 1047 1051 1987 Kim K Y Johnson G K Johnson C E Flotow H E Appelman E H O Hare P A G Phillips B A J Chem Thermodyn 13 333 344 1981 Kim K Y Johnson G K O Hare P A G Phillips B A J Chem Thermodyn 13 695 698 1981 Brittain R D Lau K H Hildenbrand D L J Electrochem Soc 134 2900 2904 1987 Sirousse zia D Thermochim Acta 19 244 246 1977 Konings R J M Cordfunke E H P Thermochim Acta 124 157 162 1988 Crouch Baker S Davies P K Dickens P G J Chem Thermodyn 16 273 279 1984 Dickens P G Neild D J J Less Common Metals 54 273 281 1977 Gvelesiani G G Nadiradze A A Abashidze T
14. EBI 3 2 4 calculation of a thermodynamic table of calcium carbonate Calculation of a thermodynamic table of calcium carbonate is made in the following sequence 1 get a compound system According to the method described in 3 3 2 you get a compound system for Ca C O with the first mode of Compounds consisting of combination of the elements 2 selection of a menu of JANAF Type table Next select the Calculate in the main menu and then select the JANAF Type Table in the submenu of Calculate 16 3 Selection of the compound Select the Select Compound in the submenu of JANAF Type Table and then the Compound Table form appears like Fig 3 4 The first line in the list is in highlighted This is a one line cursor By moving the cursor with the upward or the downward arrow keys select the compound of CaCO3 calcite and then click the Selection button at the bottom ofthe Compound Table Form 4 Calculation Immediately after selection of the compound the buttons in the Compound Table Form disappears The name of selected compound appears in the status bar of the MALT main menu The Calculate submenu of JANAF Type Table becomes available and correspondingly the tool button for Calculate JANAF Type Table becomes available like J F P You then select the Calculate by clicking on the submeu or on the tool bar After those procedures a thermodynamic table is calcul
15. as those in MALT2 Compound Handle The thermodynamic environment realized in MALT is based on the idea of compound handle in the retrieved compound system This is in the compound system just the number of the compound in the list However by using this number communication between the MALT system and other application programs can be made By specifying the compound handle number you can make access to the thermodynamic functions at a given temperature The units of the thermodynamic functions which are obtained by MALT 86 Direct are fixed as Joule J for energy Kelvin K for temperature and mole mol for mass If you need to use these values in different units you have to convert in your application programs 5 2 2 Preparation and some notice for the operational conditions The followings should be of note to create the thermodynamic environment in MALT for Windows and to utilize it from applications 1 get the compound handles As described in the previous section it is necessary to have compound handles in order to make accessible to the thermodynamic data of compound from applications What are accessible from applications are limited only those compounds existing in the current compound system For doing a similar work under the same thermodynamic environment repeatedly you need to have the same compound system having the same compound handles For this purpose saving the compound file is part
16. retrieval of compounds is always targeted to the user database in addition to the main MALT database In the list of compounds the name of user database is given after the name of the compound User Data File This is a file that stores user data in the text format To utilize in MALT for Windows this file should be compiled to create a user database Compilation cannot be completed when the text does not follow the format specified by 117 MALT for Windows User Program From a program developed by users the thermodynamic data in MALT for Windows can be directly used To do so you have to run MALT for Windows and then to run one user program and to call MALT Direct procedure To utilize the MALT data and the calculation functions it is necessary to use the special procedure called by MALT Direct Window Meta File One of the formats in which graphics is stored in a compact manner This is not common format But it is still one of the basic graphic formats which can be treated in many graphic software 118 Appendix 2 References which were mainly used in establishing MALT Database 1 Wagman D D Evans W H Parker V B Schumm R H Halow I Bailey S M Churney K L Nuttall R L The NBS tables of chemical thermodynamic properties selected values for inorganic and C and C2 organic substances in SI units J Phys Chem Ref Data Vol 2 Supplement No 2 1982 2 JANAF Thermochemical
17. 1 ElementsStr is a string variable that uses as separator for respective element symbol For charge Q is used for representing hypothetical element for positive charge This procedure corresponds to the procedure GetStoichiometryB that provides the stoichiometric number for elements given in the present procedure procedure GetStoichiometryB Handle integer var StoichiometryB string var ErrorCode byte virtual This procedure is similar to the procedure GetStoichiometry The difference is the sequence of the elements This follows the sequence of elements obtained by the procedure GetElements The StoichimetryB variable contains the stoichiometric numbers in this sequence procedure GetTransitionInfo Handle integer var PhaseNo integer var TransitionDataStr string virtual Function number 1 2 Obtaining transition information of selected compound handle This procedure obtains the transition information of compound specified by 93 handle number Results are given in TransitionDataStr in the sequence of phase symbol transition temperature enthalpy change for transition and transition symbol from the low temperature phase The meanings of the symbols obtained are given in 6 2 procedure GetThermoData Handle integer Temperature Real PhaseNo integer var ThermoDataStr string virtual Function number 1 3 calculation of thermodynamic functions of compound handle When 0
18. 119E 00 8 843 4 756E 00 8 820 4 428E 00 8 796 4 130E 00 8 772 3 360 E 00 8 748 3 614E 00 8 724 3 390E 00 8 700 3 184E 00 8 676 2 997E 00 8 652 2 824E 00 8 629 2 666E 00 Thermodynamic constants Unit cal lt lt lt H20 g gt gt gt Fig 3 11 Equilibrium constants for shift reaction between 500 C and 600 C 26 Malt Options O x Options on tabulation Quantities to Tabulate Tabulatable Quantities OK Cancel Help Fig 3 12 Selection of Tabulation in Define calculation conditions Option for extrapolation of valid temperature range can be made in the same part MALT default assumption on the temperature range is determined by the valid range for all compounds involved in the reaction For example in such a case where there is one compound which valid temperature range is small calculation will be made only within this valid range If you want to extend the temperature range to those you selected in this tab sheet you should check the option for extrapolation The calculation results will be given as in Fig 3 11 The columns in the thermodynamic results can also be selected in the Tabulation tab sheet in the MALT Options As given Fig 3 12 the thermodynamic quantities which can be listed in the table will appear Selection of the quantities can be made by using mouse clicking or arrow keys the clicking lt or gt button to change the option Th
19. 2nd ed 1986 Chapman and Hall London 25 Naumov G B Ryzhenko B N Khodakovsky I L Handbook of Thermodynamic Data 1971 Moscow Atomizdat translated by Soleimani G J 1974 U S Geological Survey 26 Barin I Thermochemical Data of Pure Substances 1989 VCH Weinheim 27 Domalski Eugene S Evans William H Hearing Elizabeth D Heat Capacities and Entropies of Organic Compounds in the Condensed Phase J Phys Chem Ref Data 13 Supplement No 1 1984 28 Stephenson R M Malanowski S Handbook of the Thermodynamics of Organic Compounds 1987 Elsevier New York 29 High Temperature Vaporization Behavior of Oxides 1 Lamoreax R H Hildenbrand D L I Alkali Metal Binary Oxides J Phys Chem Ref Data 13 1 151 173 1984 2 Lamoreax R H Hildenbrand D L Brewer L II Oxides of Be Mg Ca Sr Ba B Al Ga In Tl Si Ge Sn Pb Zn Cd and Hg J Phys Chem Ref Data 16 3 419 443 1987 30 Wilhoit R C Zwolinski B J Physical and Thermodynamic Properties of Alphastic Alcohols J Phys Chem Ref Data Vol 2 Suppl 1 1973 31 Cook L P McMurdie H F ed Phase Diagrams for Ceramists Vol 7 1989 The Am Cera Soc 32 Pedley J B Rylance J Sussex N P L Computer Analysed Thermochemical Data Organic and Organometallic Compounds 1977 University of Sussex 33 Cordfunke E H P and Konings R J M ed Thermochemical Data for Reactor Materials and Fis
20. Compound Compounds consisting of combination of the elements Compounds combined with other elements C Compounds consisting of the elements Periodic Table T r a gt O 14 MALT Materials oriented Little Thermodynamic Database File Search Compounds Edit CGalclate Tools Help 23 This shows that 23 compounds are retrieved out of the MALT database The chemical formulae are displayed below the title of the Compound Table form the notation of representing the chemical formulae is given in Table 4 11 The different columns in Fig 3 4 show information about the compounds that is the chemical formula its commonly used name of compounds if necessary to distinguish its phase symbol and its temperature range Here the phase symbol given in square brackets indicates phases covered in oo 0 Jo oO fF U WN RE a oe e wo NY r O 15 16 I 298 2500 298 2500 298 2500 298 2500 298 2500 298 2500 298 2500 298 2500 298 2500 co2 298 2500 cco radical 298 2500 C302 298 2500 298 2500 298 2500 298 2500 C graphite 298 2500 C diamond 298 1200 Fig 3 4 a Main Form after retrieving compounds b List of compounds obtained by search by element of Ca C O with mode 1 15 a given temperature range s stands for solid 1 g being liquid and gas respectively When a compound covers more than two phase
21. IDCO g 298 2500 11 cco radical g 298 2500 12 c302 g 298 2500 13 Ca g 298 2500 14 Caz g 298 2500 15 Cao g 298 2500 16 C graphite s 298 2500 17 C diamond s 298 1200 18 Ca sl 298 1752 20 Cao2 s 298 427 21 Cac2 s 298 1275 22 CaCO3 calcite s 298 1150 E 602 Gad Ga603 Select Dispose Cancel OK Hit compounds included in the reaction Fig 4 11 Compound Table Form for Selecting Chemical Reaction To select compounds the following should be considered 1 All compounds in a reaction must exist in the current compounds list 2 The number of the elements in a reaction must not be larger than 8 That is the number of the compounds cannot be larger than 9 3 Users must select the compounds with which one completed chemical reaction can be made For example the compounds Fe FeO cannot make any chemical reactions The compounds CO CO H2 H20 can make a completed chemical reaction in which all compounds have some interaction with other compounds but the compounds CO O2 H2 H20 78 is not the case The compounds H2 H2S H20 S2 O2 cannot be accepted because two reactions can be made with using the compounds 2H2 O2 2H2O 4 3 2H2 S2 2H2S 4 4 MALT for Windows examines the selected compounds and shows an error message when users selected inadequate compounds 4 To construct a reaction from the selected compounds users must
22. Table Form by clicking exit Then you can see the Calculate menu in the menu bar You can select the Define Calc Conditions submenu of Equilibrium Constant The MALT Options form like Fig 3 10 will appear It is possible to set options for calculation conditions and output of results In the Computation tab sheet in the MALT Options Form selection can be made among respective radio group boxes for radio group box see Appendix 1 When selection is made in Temperature unit the correspond numerical values given in the edit fields for the high temperature limit and the low temperature limit will be altered automatically Energy unit affects only on the thermodynamic result table Unit of materials can be defined only when the JANAF type table is concerned For Equilibrium Constant moles are always used S04 lt 25 Malt Options Tabulation Temperature unit Temperature Range on calculation s ge Low limit 500 00 c High limit Q 600 00 Eragon Temp wiano cal Options on calculation and tabulation Unit of Materials V Make extraporation of phase data on calcula Lars soo J Show thermodynamic params in table C kg I Show phase transition data in table BEST re pr ee ee Cancel Help Fig 3 10 Define calculation conditions Equilibrium constant H20 e COle CO2 e H2le 2002 08 09 Fre oe en cao cal mat Keane evomi 9 837 1 027E 05 8 867 5
23. The command JANAF Type Table makes a JANAF type thermodynamic table and the command Equilibrium Constant calculates the change of thermodynamic functions for reactions and related equilibrium constants 4 4 1 Functions in MALT for Windows MALT for Windows makes the user free from the complicated and boring processes to calculate a thermodynamic table for a reaction which needs manual reading and extrapolating a data set from a database and from possible troubles such as misreading data or mistakes in calculations MALT for Windows makes JANAF type tables The JANAF Joint committee of Army Navy Air Force NASA Thermochemical Tables are the database created by the national project of the United States concerning the collection and evaluation of high temperature thermodynamic data they have been regarded as one of the best databases with very high quality A table consists of standard heat capacity standard entropy standard enthalpy Gibbs energy function GEF standard formation enthalpy and standard Aa formation Gibbs energy There are two methods to examine the chemical equilibrium one is calculating the equilibrium constant and the other is minimizing or maximizing the thermodynamic functions under a certain reaction condition For the latter case some application programs have been successfully developed and widely used one example is ChemSage MALT for Windows has a function for the former approach that is calc
24. The thermodynamic function above To is given as follows T H T H T JC dT 6 3 To T S T S Ty C T dT 6 4 To The enthalpy of formation and the Gibbs energy which are given in the thermodynamic environment are different from the commonly used definition that the standard enthalpy change and the Gibbs energy change for formation isothermally from the elements in the reference state at a selected temperature These MALT values are given as A sH T AsH Tog H T H To 6 5 A sG T ArG To G T G To 6 6 To 298 15 K Here these quantities are given as a sum of the quantities for formation at the standard temperature 298 15 K and the increment of the function from the standard temperature This definition gives enthalpy and Gibbs energy change for formation from the elements at the standard temperature This may make it a little bit hard to understand its physical meanings 112 The reason why these quantities can be adopted is given as follows In representing the thermodynamic potential functions any reference point can be adopted if the internal consistency is hold In the commonly used definition the reference state to represent the formation quantities is different for respective temperatures whereas the above definition adopts the only one reference state at the standard temperature The most important reason of adopting this definition is that this requires
25. Yun W Zhu J T Goudiakas J Fuger J J Chem Thermodyn 20 1195 1202 1988 Petzel T J Less Common Metals 108 241 247 1985 Cordefunke E H P Konings R J M Westrum E F Jr Thermochim Acta 128 31 38 1988 Johnson G K Tasker I R Howell D A J Chem Thermodyn 19 617 632 1987 Kitayama K J Solid State Chem 73 381 387 1988 Kitayama K J Solid State Chem 76 241 247 1988 Kitayama K J Solid State Chem 77 366 375 1988 Sepp nen M Kyt M Taskinen P Scand J Metall 8 199 204 1979 Petrov A N Cherepanov V A Zuyev A Yu Zhukovsky V M J Solid State Chem 77 1 14 1988 Petrov A N Kropanev A Yu Zhukovsky V M Rus J Phys Chem 58 26 1984 Cherepanov V A Petrov A N Grimova L Yu Rus J Phys Chem 59 1267 1985 Beyer R P Johnson E A J Chem Thermodyn 16 1025 1029 1984 Chekhovskoy V Ya J Chem Thermodyn 3 289 296 1971 Furukawa G T Douglas T B Saba W G Victor A C J Res Natl Bur Stands 69A 423 438 1965 Rard J A Chem Rev 85 555 582 1985 Fegley M B Jr J Am Ceram Soc 64 C124 1981 Kaufman L CALPHAD 3 275 291 1979 Moon K A Kant A Croft W J J Am Ceram Soc 63 698 1980 Konings R J M Cordfunke E H P Shaviv R Westrum E F Jr Thermochim Acta 157 307 314 1990 Volkov V L Rus J Inorg Chem 23 98 1978 Volkov V L Rus J
26. are given in Table 6 1 Any symbol can be used for user s data Basically heat capacity data of gaseous species are given up to 2500 K That temperature does not mean phase transition but just the maximum temperature limit below which the heat capacity and related functions are correctly reproduced Extrapolation can be made to higher temperatures but it should be done with special care because of a great possibility of giving rise to an enormous error The most important concern which users may have on data books and or databases will be how to recognize the reliability of given data The thermochemical tables and equilibrium constant tables given in MALT for Windows provide the numerical values with the precision of 0 01 J K mol for C and S and of 0 01 kJ mol for AyG and A H however there is no description about how to interpret these values On the other hand from the viewpoint of editors of databases it is quite hard to give the limit of the reliability for different compounds This is because it cannot be specified in what chemical reactions under what conditions users will use data of a particular compound In addition MALT for Windows allows users to extrapolate the data beyond the valid temperature region Thus MALT for Windows adopts like the first and second versions of MALT a way of showing rough information of reliability in terms of references cited Needless to say the stored data in MALT for Windows are judged as
27. compiled file User database can be also targeted when the command get a compound system or append compound will be done There can be several databases depending on the user s convenience However only one user database can be targeted This is made by the submenu Load user database here users have to specify one among the compiled databases The compilation procedure of the ASCII type user data file can be made by the submenu Compile User data file Editing this user data file can be made by the following three ways 1 Edita file by using other editors Since the structure of the user data file is determined strictly and they are given below users can make such a file by themselves 2 Input thermodynamic data and related information by using MALT for Windows providing the add new compound submenu in the User Data menu in the Tools main menu Input of the thermodynamic data is made with an aid of the submenu so that you do not need to worry about the format and other details of the user data file 3 Use of Function of edit compound value Any compound in the list of the compound system can be selected as the compound of which those thermodynamic values can be modified in the menu This means that users can modify the thermodynamic data stored in the MALT database and save the modified values as one of the user s data You cannot modify the values of the database itself 61 In above the secon
28. consists of the followings temperature standard enthalpy change for reaction dH standard entropy change dS standard Gibbs energy change dG logarithmic equilibrium constant log Kp equilibrium constant Kp and change in the Gibbs energy function dGEF Here the standard enthalpy change and the standard Gibbs energy change are used in the conventional definition in which the quantities for the isothermal process are given for details see chapter 6 The definition of Gibbs energy function is given in Appendix 1 ie Input Compounds Hit chemical formula to search Example CO2 CaO CaGO3 Fig 3 dpput Copapopnd Forms gs7 6 144E 08 159 068 174 289 152512 67 487 9 207E 06 158 273 172 884 150 639 52 331 3 830E 04 157 434 171 386 148 875 37 356 6 791 E 03 156 580 169 798 147 203 22 553 6 637E 02 155 726 168 119 145 603 7913 f 4 210E 01 154 878 166 346 144 061 6 570 1 932E 00 154 040 164 473 142563 20 901 i 6 915E 00 153 215 149 ANA 141 907 IR NOA 3n9 Lani 169 AN1 Thermodynamic constants lt lt lt CaCO3 calcite s gt gt gt Print Fig 3 7 Equilibrium constants for the thermal decomposition of CaCO3 3 3 Shift reaction As a second example the shift reaction CO H20 CO H 3 2 will be considered here 3 3 1 Get compound system by means of chemical formulae For the case of the thermal decomposition of CaCOs selection of compounds was made using a set of elements wi
29. determine which compounds will be reactant or products and its stoichiometric coefficient in the reaction note that any chemical reaction is extensive so that you have to specify the molar number MALT automatically asks you the stoichiometric coefficient of one compounds See Fig 4 12 for selecting one compound to determine the stoichiometric coefficient of the reaction The stoichiometric coefficient must be integer and is negative value for reactants and positive for products The constructed chemical reaction will be displayed in the status bar of the main form Reaction Form R Select a compound to define stoichiometric coefficients in your reaction CaO lime sl oe 298 4 CaCO3 aragonite s E f 298 1 Select Cancel O Stoichiometric coef Reac Prod 9 1 Fig 4 12 Select the compound to determine the stoichiometric coefficient of the reaction 79 4 5 Set up working environment This chapter explains about each item of the Customize MALT setting menu All set up parameters are saved on ending MALT for Windows 4 5 1 Default This option is displayed in the lower part of the general tab sheet MALT provides the default setting for respective items Whenever you like you can recall this setting Your personal selections for respective options can be saved as User default by clicking the Set current options as User default This user default can be recalled by clicking th
30. for selected commands given in the menus The status line is located in the bottom of the Main form The main menu consists of Files Edit Project View Run Diagram Windows and Help 3 5 3 Specification of calculation conditions In order to construct a chemical potential diagram many parameters should be defined In the CHD program such parameters are given as default values in many cases In the situation given in Fig 3 19 the CHD is ready to construct a diagram by using default values given for this system Even so users have to have some idea what kinds of diagrams they want to construct This is made in the submenu of specify diagram in the Project main menu as given in Figs 20 a and b 36 In the upper part of Fig 3 20 a the information of the current system is given to make a proper selection of the parameters The current Ca O C system is the 5 component dimension system including temperature and pressure For a system which has 5 or more dimensions default setting of the fixation is made to fix temperature and pressure Usually pressure is set as 1 atm whereas temperature is set at 298 15 K In Fig 30 20 a There are 3 tabsheets for specification of conditions The first tab sheet of Dimension is for determination of temperature and pressure Since default temperature is 298 15 K this value is changed to 1000 K in Fig 3 20 a In the second tab sheet of Fixation is f
31. heat capacity data of only the selected compound to calculate the high temperature thermodynamic functions and their integration can be given by the above equations On the other hand to derive the quantities given by the commonly used definition it is necessary to integrate the difference in heat capacity between the compound and its constituent elements This may give rise to additional possibility of introducing calculation errors In a calculation for the thermodynamic function change for a particular chemical reaction the same values are given by both methods so that quantities for any chemical reaction at any temperature can be obtained by using the present definition Even so special care has to be taken not to use the values of the different definition in the same calculation The special care should be exercised in handling the Gibbs energies As described in the previous section the thermodynamic consistency given by the following relation is not necessarily satisfied in the MALT database ArG To AtH To To AsS To 6 7 This means that it is better and more reliable to use the value of AG To instead of the value calculated as AH To To AS To According to this feature the high temperature Gibbs energy in MALT is calculated as follows A G T ArG To H T H To TS 1 T0 To 6 8 AG T ArG To AH T AH To TAS T To To 6 9 This makes it possible to have the high t
32. hydrocarbons In the MALT for Windows the carbons number can be specified when retrieval will be made This can be made by selecting the customize MALT Gem Project MALT Direct Temperature k Gibbs Pressuretatm H _protonium H2 OH Co 002 CCO radical GH GH2 CH3 CH4 G2H G2H2 G2H3 C2H4 G2H5_ethyl radical Fig 3 15 gem main form after performing MALT Direct which transfer the compound system from the MALT for Windows to gem 30 setting submenu in the Tools main menu In the General tab sheet there are options for setting the carbon number limit Here the carbon number should be set as two or less as shown in Fig 3 14 Then clear the current compound system and select the get a compound system The search mode is selected as mode 1 to collect all compounds in the system In the Search a Compound System Form the C H O system with the mode ofthe compounds consisting of combinations of elements will be selected 52 species will be retrieved in the C H O system 3 4 2 Run the computer program gem Here it is ready to run the gem program Easiest way of running gem is the selection of the gem command in the Tools main menu This command is to execute the following command gemWin exe md Here the switch md means that MALT Direct command will be performed as the first command Fig 3 15 shows the
33. input title will be displayed in the status bar in the main form Define phase You can define Gas mixture Aqueous mixture Liquid mixture or Solid mixture To make a Gas mixture you have to have gaseous compounds in the list of compound system Otherwise this function will be terminated Candidate compounds for respective mixtures are collected in terms of the Evaluated phases in the compound data as shown in Fig 4 4 After you select Gas mixture the phase name of the mixture can be edited A default name will appear so that you can edit this phase name in a normal editing procedure 69 After this the list of gaseous compounds appear in the upper form and in the lower form the selected compound are to be displayed Selection for components of a mixture can be made by the following ways 1 clicking the All button All candidates displayed in the upper form will be selected and moved to the lower form 2 clicking mouse on one compound and pressing the select button as a result that compound move from the candidates to selected one 3 double clicking on one compound to move to another part from the candidate to selected for clicking the compound in the upper form or from the selected to the candidate for clicking the compound in the lower form 4 clicking the All clear button Eile Search Compounds Galclate Tools Help SE User1 l L i M
34. knowledge However the thermodynamic functions outside the stable temperature range are not available Executing efficiency is poorer than that in levels 2 or 3 level 2 It is needed to handle the record type variables level 3 the executing efficiency is the best It is needed to handle untyped variables MALTDATAfile PAS explains the type declaration of variables and functions of procedures necessary to use MALTDATAfile dcu As an appropriate textbook to learn Turbo Pascal Delphi from the beginning the following is recommended 5 4 3 Sample programs Sample programs are given in the MALT for Windows These programs should be compiled in Delphi 5 104 mode integer ss string begin mode 0 mode 0 retireve without data structure FMALT Free Destroy the previously used data if any FMALT MAL TDirect self The Form self will be owner of the Datacomponent mode Returncode if FMALT lt nil then begin ClearCells ShowCompounds ShowStoichiometry end else begin if returncode 1 then ss MALT is not running else if returncode 2 then ss No retreived data available Retrieve compounds first else ss Error StatusBar1 panels 0 text ss end end procedure TForm1 ClearCells var i j integer begin with StringGrid1 do begin for i 0 to Colcount 1 do for j 0 to Rowcount 1 do Cells i j end end procedure TForm1 FormCreate Sender TObject begin FMALT ni
35. mixtures Such phases should not be included X Cancel Help H 2 Default Setting Default setting will make the following procedures 1 if there are gaseous compounds in a compound system the gaseous mixture consisting of all gaseous compounds will be created 2 Ifthe aqueous species and water are simultaneously included the aqueous solution will be created to include water as solvent and aqueous species as solutes Note however that this solution is an ideal dilute solution 3 Ifthere are condensed compounds all condensed compounds are included in the invariant condensed phase sD x Since this type of default setting can be easily reproduced for any kinds of compound system no prompt will be given when a compound system will be changed and the MALT data file based on the compound system will be destroyed 3 Verify compounds You can verify the mixtures selected If you want to change it you can do it 4 Save MALT Data File As After pressing this option MALT for Windows starts writing in a selected file according to the selected information The format of the MALT data file is not open However this type of file can be read from the MALT related software gem and CHD The same expression is also available in the MALT Direct environment which will be explained in Chapter 6 4 4 Thermodynamic tables and equilibrium constant MALT for Windows can make thermodynamic tables and calculate equilibrium constants
36. of doing like a batch job procedure can be available instead of performing the MALT Direct command on each time in addition to running MALT for Windows from the command line reading a data file and running an application will be made at the same time This function will be quite useful when using those application program that have been already debugged a series of calculations will be made for a system consisting of selected compounds For example when the application program APPL1 will be used with the compound file DATAF1 names of the data file and the application should be input as the command parameters as follows MALTWIN EXE DATAFI APPLI This kind of command line can be stored in the property of a short cut Here MALT for Windows is first run the compound file DATAF 1 is then read and finally the application APPLI is run from the MALT for Windows with command parameter of md The application APPL1 makes access to MALT for Windows to get the thermodynamic data needed When the task is ended the ending procedure of the application and MALT for Windows are done sequentially and the control is finally back to Windows This is a quite appropriate function for calculations in which the same data are used under various calculation conditions Data files can contain user data COM files or EXE files can be used as applications Since applications will be run under the control of the MALT for W
37. out of the data stored in the MALT database For resulting data the compound handles are given respectively Status bar Status line Usually the status bar is located at the bottom of the form to provide message upon request from the software Stoichiometric Coefficient A coefficient of a compound in a chemical reaction For example in the following chemical reaction CO 0 5 O2 CO2 1 for CO 0 5 for O2 1 for CO are the stoichiometric coefficients Stoichiometric Number A mole number of an element in a compound For example in CaCOs 1 for Ca 1 for C and 3 for O are the stoichiometric number Tab sheet Some windows control has page control which consists of several pages Each page is called as Tab sheet 116 Temporary File This is a file which will used temporary and finally disappear after necessary job will be done MALT for Windows creates automatically temporary files on respective occasions and erases at the end of operation of MALT The folder for temporary files can be specified in MALT Options in the Tools menu Text format This is the format of a file which consists only of ASCII codes shift JIS codes for KANJI Files stored in this format can be edited in editors for general purpose Thermodynamic Environment When we want to make the thermodynamic considerations on practical problems it will be troublesome to run a calculation program after reading the thermodynamic data in
38. reaction Define Calc Condition D Set up the conditions of calculation and the format of the table Calculate C Execute the calculation 4 2 5 Submenus of the Edit menu When the Thermodynamic Results form is displayed to show the calculation results for the JANAF type Table or for the Equilibrium Constants several modes of copy of such a list of results can be made to clipboard Separator for adjacent rows can be selected in the MALT Options form files which can be selected in the Customize MALT setting submenu in the Tools menu Table 4 8 Items and functions of the submenus of Edit menu Item Accelerator key Function Copy Selected Area S Copy an area selected by clicking mouse Copy Current Row R Copy a Row in which the focused field is included Copy Current Column C Copy a Column in which the current field is included Copy All the Table A Copy all data in the table 4 2 6 Submenus of Tools menu The Tools menu contains submenus which provides many useful functions and facilities The Customize MALT settings menu provide the MALT Options Form consisting four tab sheets The detailed explanation is given in 4 5 50 Table 4 9 Items and functions ofthe submenus of Tools Main menu Item Accelerator key Function Customize MALT Settings MALT options can be specified for general S matters computation files and tabulation User Data U Edit and compile use
39. the fundamental numbers for the currently available compound system There are three similar initialize procedures in which the different number of variables are required 1 var Ncompound integer 2 var NT NG NC integer 3 var NT NG NC NA integer The first procedure provides just the total number of the compound handles The third procedure provides the total number of the compound handles NT the total number of gaseous compound handles NG the total number of condensed compound handles NC and the total number of aqueous species handles NA The second procedure provides NT NG and NC Here if there are aqueous species handles these are counted in NC This procedure is prepared only to 9 1 be consistent with the interrupt procedure in MALT2 When the MALT for Windows is not running the initialization is failed Errorcode is set as 1 Asa result variables Ncompound NT NG NC and NA will be set as zero No other procedures or functions can be succeeded in such a case In any procedure Errorcode 1 is returned When no retrieved compound is available Errorcode 2 is returned procedure GetNameRangePhase Handle integer var CompoundNameStr string var NameOfDatabaseStr string var TemperatureRangeStr string var PhaseStr string var ErrorCode byte virtual Function number 1 0 Selection of compound handle When the selected compound handle number is correctly given the following variables are retur
40. the thermodynamic tables and calculating the thermodynamic functions at a selected temperature In an ideal situation it is hoped to realize that a program can provide automatically the thermodynamic function just after specifying the compound and temperature We call such a computer environment for realizing this function the thermodynamic environment MALT for Windows realizes it by making MALT Direct available Thermodynamic Table User Data The thermodynamic data which are formatted like JANAF Thermochemical Tables Heat capacity entropy enthalpy Gibbs energy are given as a function of temperature This is the thermodynamic data that users have evaluated by themselves In MALT for Windows calculation can be made by combining the MALT database and user data All user data should be stored in a file as text format After compilation of the test file MALT for Windows manages the users database in a similar manner to the main database to ensure a high speed in retrieval and calculation The thermodynamic data to be stored in user data files can be edited 1 by using a text editor for general purpose 2 by using the input menu for thermodynamic data in MALT for Windows 3 by modifying the values of compounds retrieved from the MALT database User Data Base This is a file to be created after the compilation of a user data file One of the user databases can be loaded in MALT for Windows When this is loaded the
41. where MtCalcResultType record Errorcode byte errorcode Value real thermodynamic function end Here mm is the total number of thermodynamic functions The maximum number of temperature is 255 so that the maximum size of this record should 98 be 255 x 5 1275 bytes procedure GetThermoDataForCompounds Temperature Real NComp integer Comps MtMultiCompoundType var Results MTResultArrayType virtual Function number 1 12 Thermodynamic functions of several compounds at a selected temperature This calculates the thermodynamic functions at one selected temperature for several compounds On calling the data buffer region should be filled by the information of temperature and a selected number of compound handle and temperature region which should be give in the following data structure Ist 6th bytes selected temperature real 7th a compound number of 2 bytes compound handle word 1 byte number of temperature region byte These data correspond to the following record MtMultiCompoundType MtMultiCompoundType record Temperature real temperature Compounds array 1 mm of MtGivenCompoundType end Here mm is the total number of compounds to be used in calculations that is Ncomp MtGivenCompoundType is given as MtGivenCompoundType record Handle word compound handle Phasenumber byte number of temperature region end When the invalid number of
42. with mixture phases this is to distinguish from the editing procedures of the compound system itself described in 4 3 3 to 4 3 4 1 Set up Compounds The MALT Data file is based on a system consisting of mixtures and invariant condensed compounds Mixtures mean a solution phase that allows change in composition This is expressed in terms of the concentration of various compounds forming a mixture Invariant compounds mean no change in composition On the other hand the compounds in the MALT database are based on invariant compounds To create a MALT Data file therefore mixtures should be defined on the basis of the compounds which are retrieved in the main memory These will be done as follows 68 MALT Data File Form Mixture phase Header Title Ca 0 G pystem Stoichiometric condensed Phases for selection Gas x Phase Name aas jovio 1 1 296 2500 2 02 g 1 298 2500 3 03 g 1 298 2500 4 C g 1 298 2500 5 65 g 1 298 2500 6 CCO radical a 1 298 2500 7 C302 g 1 298 2500 8 Ca g 1 295 2500 9 Caz g 1 298 2500 10 Cao g 1 298 2500 All Select Dispose All Clear New Phase Prey Phase Next Phase Save Default Fig 4 7 Edit of MALT DATA File Enter a title After selecting the Set up Compounds submenu you are prompted to enter a title of the data file You need to type some thing Otherwise you will go back to the previous menu The
43. 00 209 1986 Brewer L Ebbinghaus E E Thermochim Acta 129 49 55 1988 Leonov A I Shvaiko Shvaikovskii V E Keler E K Rus J Inorg Chem 14 3 334 336 1969 Yokokawa H Sakai N Kawada T Dokiya M J Am Ceram Soc 73 3 649 658 1990 Taylor R W Schmalzried H J Phys Chem 68 9 2444 2449 1964 Keneshea F J Cubicciotti D D J Chem Phys 40 177 1964 Yokokawa H Sakai N Kawada T Dokiya M Denki Kagaku 58 561 563 1990 Yokokawa H Kawada T Dokiya M J Am Ceram Soc 72 11 2104 2110 1989 Yokokawa H estimated and evaluated values during 1989 1991 Yokokawa H Sakai N Kawada T Dokiya M J Solid State Chem 94 1 106 120 1991 Kellogg H H Metal Trans 20B 77 1989 Kuselev A I Karnov I K Physicochemical modeling in geology 1988 Academy Nauk SSSR Siberian Branch Hubbard W N Rawlins P L Connick P A Stedwell R E Jr O Hare P A G J Chem Thermodyn 15 785 798 1983 Ohlendorf D Flotow H J Less Common Metal 73 25 32 1980 Wilhoit R C Chao J Hall K R J Phys Chem Ref Data 14 1 1 1985 Chao J Hall K R Marsh K N Wilhoit R C J Phys Chem Ref Data 15 4 1369 1436 1986 Lyman J J Phys Chem Ref Data 18 2 799 1989 Pedley J B Marshall E M J Phys Chem Ref Data 12 14 967 1983 Akila R Jacob K T Shukla A K Metal Trans 18B 163 1987 Dwivedi
44. 1984 O Hare P A G Hubbard W N Johnson G K Flotow H E J Chem Thermodyn 16 45 59 1984 Skudlarski K Kapala J J Chem Thermodyn 16 91 100 1984 Smith J F Bull Alloy Phase Diagrams 2 1 42 48 1981 Pamidimukkala K M Rogers D Skinner G B J Phys Chem Ref Data 11 1 83 99 1982 Chao J Zwolinski B J J Phys Chem Ref Data 7 1 363 377 1978 Chen S S Wilhoit R C Zwolinski B J J Phys Chem Ref Data 6 1 105 112 1977 Chao J Zwolinski B J J Phys Chem Ref Data 5 2 319 328 1976 Chao J Rodgers A S Wilhoit R C Zwolinski B J J Phys Chem Ref Data 3 1 141 162 1974 Chao J Wilhoit R C Zwolinski B J J Phys Chem Ref Data 2 2 427 437 1973 Chen S S Wilhoit R C Zwolinski B J J Phys Chem Ref Data 4 4 859 869 1975 Chao J Zwolinski B J J Phys Chem Ref Data 4 3 251 261 1975 Chen S S Kudchadker S A Zwolinski B J J Phys Chem Ref Data 4 3 251 261 1975 Kudchadker S A Kudchadker A P Wilhoit R C Zwolinski B J J Phys Chem Ref Data 7 2 417 456 1978 Kudchadker S A Kudchadker A P 123 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 Wilhoit R C J Phys Chem Ref Data 8 2 519 526 1979 Tirtowidjojo M Pollard R J Cryst Growth 77 2
45. 2 repeat inc Colno Cells Colno i GetNextStr StoichioStr GetNextStr StoichioStr until Stoichiostr or Colno 7 Cells CoINo 1 i Stoichiostr end end end end procedure TForm1 ShowThermoDataAt A Value Real var NCompound i integer PhaseNo integer ThermoDataStr string begin if FMALT nil then exit with FMALT StringGrid1 do begin initialize NCompound if NCompound lt gt 0 then begin Cells 3 0 H T H298 Cells 4 0 dH T Cells 5 0 Cp Cells 6 0 S Cells 7 0 dGf T for i 1 to NCompound do begin GetThermoData i AValue PhaseNo ThermoDataStr Cells 3 i GetNextStr ThermoDataStr Cells 4 i GetNextStr ThermoDataStr Cells 5 i GetNextStr ThermoDataStr Cells 6 i GetNextStr ThermoDataStr Cells 7 i GetNextStr ThermoDataStr 106 end end end end procedure TForml actExitExecute Sender TObject begin Close end procedure TForm1 sbTemperatureChange Sender TObject begin FTemperature sbTemperature position stTemperature caption IntTostr sbTemperature position actRunExecute self end procedure TForm1 actRunExecute Sender TObject begin ShowThermoDataAt FTemperature end 107 Chapter 6 Thermodynamic Database and High Temperature Thermodynamic Calculations 6 1 Consistency of the thermodynamic data Thermodynamic functions form a complete and close system within themselves so that any data book
46. 59 when it is not focused the green color is used with yellow character You can select several compounds to be deleted by moving cursor and hitting select button or by double clicking on the compounds to be deleted If you mistake the selection of the compound hitting the dispose button or double clicking again and the compound will be shown with a normal color Deletion is made when you hit the OK button or carriage return Cancellation is made by hitting the cancel button or the ESC key 4 3 4 Compound file It is highly recommended for users to save the compound system whenever they made some editing procedure after retrieval using a normal procedure For examples 1 When you append compounds several times 2 When you delete compounds after searching compounds 3 When you add your own user data or you modify the data and saved it in the user data file 4 When you made data format conversion without using default setting Save the compound system can be made by the Save Compound file menu or the Save Compound file as menu in the File menu The saved compound system is stored in the specially formatted file This is called Compound File This compound file is not an ASCII format and can be opened only by the command Read compound file in the File menu in MALT for Windows On reading a new compound file the compound system previously loaded on the working space will be clea
47. Chapter 1 Introduction This chapter describes how to use this user s manual outline ofthe MALT for Windows system will be given in the following sequence 1 What is MALT System 2 How to use this manual 3 Commands 4 Flow oftasks in MALT for Windows 5 How to recover from Errors 1 1 What is MALT System User data file User database MALT database Data management A compound system i Thermodynamic Table Calc Equilibrium constant MALT Direct Compound File mcf Compound Data File mcd Application Program chapter 1 chapter 2 chapter 3 chapter 4 chapter 5 chapter 6 MALT for Windows provides database and related software to make thermodynamic calculations on personal computers To make an effective use of MALT for Windows users are highly recommended to read carefully this manual and understand the flow of tasks to be done This manual has been prepared by assuming that users are able to do the followings without any problems 1 With adequate knowledge about Windows and related software to start Windows 2 to have ability of writing computer programs in one or two computer languages 3 to have proper knowledge about the thermodynamics to convert their own materials problems to thermodynamic problems Even so the Chapter 3 is prepared for beginners in both applying thermodynamics and handling personal computers This manual consists of the
48. Compound Data File As D Save Calculated Result in File F Print Calculated Result P End E Function Clear the work space and retrieve a new compound system from a compound file Save the current compound system into the same file Save the current compound system into a selected file Save the current MALT Data file into a selected file Results given in the Thermodynamic Results Form is saved in a selected file Print results given n the Thermodynamic result Form End the MALT for Windows with doing End procedure 4 2 3 Submenus of Search Compounds menu Table 4 3 Items and functions of the submenus in the Search Compound menu Item Accelerator key Function Get Compound System G Clear the work space and retrieve a new compound system Append Compounds A Add another compound system to the Delete Compounds D Clear Compounds C Show Compound Table S Hide Compound Table H current compound system Delete selected compounds from the compound system Delete all compounds and clear the work space Show the current compound system listed in the compound table Hide the compound table form 48 Submenus of the Search Compounds menu are shown in Table 4 3 The Get Compound System submenu and the Append Compounds submenu have their own submenus which will be given in Table 4 4 4 2 4 Submenus in Calculate main menu When retrieved compounds are available the
49. Evaluated Phases can be also selected out of the listed items to be dropped This data will be used when the conversion of data format will be made 64 The standard enthalpy change for formation the standard Gibbs energy change for formation and the standard entropy at 298 15 K should be input in unit of kJ mol kJ mol and J K mol respectively No other units will be allowed The standard entropy values for respective element at the reference state are stored inside the MALT system By using those values the standard entropy change for formation can be evaluated Since three values enthalpy Gibbs energy and entropy should satisfy the following relation ArG A T AgS 4 2 one value can be calculated from other two input values This allows to check the consistency between three values This can be made by clicking the consistency check button Result is given as shown in Fig 4 5 The consistency check button will appear only when one of three values is edited DefUsrDataForm HGS_2982 Phase 1 Comments M Thermodynamic Data at 298 15 K in Joule Compound Name and State Chemical Formula E 63003 calcite Phase symbol at 298 15 KT e 1 7 Evaluated Phases U s Functions at 298 K Standard Enthalpy of For mation 1206920 kJ mol Standard Gibbs Enerey of For m 1128 84 kJ mol Gonsistenct Check k Standard Entropy iS 92 900 JZK mol rHieh Temperature Phases Number of Temperatu
50. Handle word T real var Ht real var ErrorCode byte procedure MtGetDeltaH Handle word T real var dH real var ErrorCode byte procedure MtGetHeatCapacity Handle word T real var Cp real var ErrorCode byte procedure MtGetEntropy Handle word T real var SO real var ErrorCode byte procedure MtGetGibbsEnergy Handle word T real var G real var ErrorCode byte 101 procedure MtComplnit Handle word var CompoundData MtCompoundType var ErrorCode byte procedure MtMultiTemps Mode PhaseNum TempNum byte Handle word var Calculated word var Temps MtRealArray var Results MtResultArrayType var ErrorCode byte procedure MtMultiComps Mode NumberOfComps byte Temp real var Calculated word var Comps MtGivenCompoundArray var Results MtResultArrayType var ErrorCode byte function MtCalcMultiTemps PhaseNum TempNum byte Handle Size word var Calculated word var Temps Results var ErrorCode byte boolean function MtCalcMultiComps NumberOfComps byte Temp real Size word var Calculated word var Comps Results var ErrorCode byte boolean 5 3 5 Error codes 0 OK 1 MALT is not running There is no retrieved compound currently No initialization has been done before the present procedure Any Compound Handle has not been specified yet 3 4 5 6 Invalid Compound Handle is specified 7 Different Compound Handle from the initialization is specified 8 Invalid Temperature Value is specified 9 Specified Te
51. JANAF type table or on the reaction will not be saved At present screen saver will not work 4 5 4 Compounds Order This command sets the order of compounds list which affect the compound numbering You can choose the NBS or the JANAF order In what follows explanation of two orders in MALT for Windows will be given In both cases all chemical formulae are converted into compositional index for example a compound CuSO4 5H gt 0O is regarded as CuSH1009 1 NBS order All chemical elements are indexed as shown in Figure 4 14 The elements in a compound are arranged according to the index in which the element with the larger index comes earlier for example CuSHO for a hydrated cuprous sulfate The compounds are arranged according to the index in which the compound having smaller index comes earlier Between the compounds which have the same elements the compound having smaller stoichiometric number of the larger index element comes earlier for example CuO comes earlier than 81 Cu20 but MnO comes earlier than MnO 2 JANAF order All chemical elements are indexed in the alphabetical order The elements in a compound are arranged in alphabetical order for example CuHOS for a hydrated cuprous sulfate All compounds are arranged in the alphabetical order Although the original JANAF thermochemical tables have some exceptions MALT omits them In the JANAF thermochemical tables carbon and hydrogen if any are ind
52. R K Kay D A R Metal Trans 15B 523 1984 Fukatsu N Shidawara N Kozuka Z J Electrochem Soc 132 9 2258 1985 Takahashi Y Sakamoto R Kamimoto M Int J Thermophys 9 6 1081 1988 Robie R A Russell Robinson S Hemingway B S Thermochim Acta 139 67 1989 Filippov V K Kalinkin A M Vasin S K J Chem Thermodyn 19 185 1987 Abello L Chhor K Pommier C J Chem Thermodyn 19 797 1987 J Chem Thermodyn 17 1 23 1985 Cordfunke E H P Cluistra R van Miltenburg J C J Chem Thermodyn 17 1079 1985 124 136 137 138 139 140 141 142 143 144 145 146 147 148 Meisingset K K Gr nvold F J Chem Thermodyn 18 159 1986 Beyer R P Ferrante M J J Chem Thermodyn 18 365 1986 O Hare P A G Johnson G K J Chem Thermodyn 17 593 1985 Levitskii V A Balak G M Rus J Phys Chem 56 5 668 1982 Levitskii V A Klimenko A N Marin V P Chentsov V N Men shenin Yu V Rus J Phys Chem 58 6 1350 1354 1984 Klimenko A N Levitskii V A Marin V P Rus J Phys Chem 60 10 2402 2409 1986 Lindemer T B Besmann T M Johnson C E J Nucl Mater 100 178 226 1981 Yamaguchi S Kaneko Y Iguchi Y Trans JIM 28 12 986 993 1987 Seetharaman W D S Staffansson L I Metal Trans 15B 319 327 1984 Yokokawa H Sakai N Kawada T
53. T von Goldbeck O Nowontny H Seifert K Ferro R Dragoo A L Niobium Physico Chemical Properties of its Compounds and Alloys 1968 International Atomic Energy Agency Vienna No 3 Gerassimov Ya I Lavrentev V I von Goldbeck O Livey D T Ferro R Dragoo A L Tantalum Physico Chemical Properties of its Compounds and Alloys 1972 IAEA Vienna No 4 Spencer P J von Goldbeck O Ferro R Girgis K Dragoo A L Beryllium Physico Chemical Properties of its Compounds and Alloys 1973 IAEA Vienna No 5 Rand M H von Goldbeck O Ferro R Girgis K Dragoo A L Thorium Physico Chemical Properties of its Compounds and Alloys 1975 IAEA Vienna No 6 Alcock C B Jacob K T Zador S Kubaschewski von Goldbeck Ortrud Nowontny H Seifert K Kubaschewski O Zirconium Physico Chemical Properties of its Compounds and Alloys 1976 IAEA Vienna No 7 Spencer P J Kubaschewski von Goldbeck O Ferro R Marazza R Girgis K Kubaschewski O Hafnium Physico Chemical Properties of its Compounds and Alloys 1981 120 IAEA Vienna No 8 Brewer L Lamoreaux R H Ferro R Marazza R Girgis K Molybdenum Physico Chemical Properties of its Compounds and Alloys 1980 IAEA Vienna No 9 Kubaschewski O Kubaschewski von Goldbeck Ortrud Rogl P Franzen K L Titanium Physico chemical Properties of its Compounds and Alloys 1983 IAEA Vienna
54. T for Windows monitor version is compacted in a one file MALTForMonitos zip This can be developed in the following files malt CHDWin cnt CHDWin hlp CHDWind exe CHDWin ini GemWin exe Glen dat Malt dat Malt exe Malt PRM Maltmes str MaltWin cnt MAL TWin hlp User ini TempDirect UserDB Userl txt Userl udb users CompoundFile MAL TDataFile Output Samples The samples folder contains source programs and related executing codes for helping users to develop their own application programs to be used under a MALT Direct environment MALTINST EXE is a utility for unpacking files Since these files were packed in a specialized way there is no other way of unpacking the packed files Installing MALT for Windows Monitor version is made by the following way 1 Confirmation of Work Area 2 Making a Directory for MALT to Be Installed 3 Move the current drive 4 starting MALTINST 5 Selection of drive to be installed 6 Unpacking files and install of key code 7 Copy of sample files Chapter 3 Instruction Let s Run MALT for Windows In Chapter 3 the fundamental methods of running MALT for Windows will be described by using typical chemical reactions as examples that is the thermal decomposition reaction of calcium carbonate and the shift reaction formation of carbon dioxide and hydrogen from carbon monoxide and water vapor The environmental conditions of running MALT for Windows are assumed to be the s
55. Tables a Stull D R Prophet H 2nd ed 1971 NSRDS NBS 37 b Chase M W Jr Curnutt J L Hu A T Prophet H Syverud A N Walker L C J Phys Chem Ref Data 3 311 1974 c Chase M W Jr Curnutt J L Prophet H McDonald R A Syverud A N J Phys Chem Ref Data 4 1 1975 d Chase M W Jr Curnutt J L McDonald R A Syverud A N J Phys Chem Ref Data 7 793 1978 e Chase M W Jr Curnutt J R Downey J R Jr McDonald R A Syverud A N Valenzuela E A J Phys Chem Ref Data 11 695 1982 f Chase M W Jr Davies C A Downey J R Jr Frurip D J McDonald R A Syverud A N J Phys Chem Ref Data 14 Supplement No 1 1985 3 Kubaschewski O Alcock C B Metallurgical Thermochemistry Sth ed 1979 Pergamon Oxford 4 Mills K C Thermodynamic Data for Inorganic Sulphides Selenides and Tellurides 1974 Butterworths London 5 Hultgren R Desai P D Gleiser M Kelley K K Selected Values of the Thermodynamic Properties of the Elements 1973 The American Society for Metals Metals Park 6 Barin I Knacke O Thermodynamic Properties of Inorganic Substances 1973 Verlag Stahleisen Berlin 7 Barin I Knacke O Kubaschewski O Thermodynamic Properties of Inorganic Substances Supplement 1977 Verlag Stahleisen Berlin 8 Robie R A Hemingway B S Fisher J R Thermodynamic Properties of Mine
56. acteristic to respective compounds but a set of self closing values and therefore editing of data books and databases should not be made like making collected data from different sources into one book or one data file This MALT database has adopted the following convenient way of keeping the consistency among data 1 Among data books the NBS tables are the best in the sense that they have paid extensive and intensive attention to the consistency described above Thus as far as the values at 298 15 K are concerned the MALT database is based first on the NBS tables if available although there are some problems even in the NBS tables 2 For the high temperature data only the coefficients of the heat capacity equation are stored and the thermodynamic functions H G and S are calculated using the thermodynamic analytical equations This provides the consistency between heat capacity and other functions H G and S 3 Even so in practical applications the enthalpies and Gibbs energies are more important than the heat capacities so that the coefficients of heat capacity equation were determined so as to reproduce the values of 109 enthalpies and Gibbs energies rather than the heat capacities themselves Particularly the heat capacities given in this database are different from true heat capacities in the phase transition vicinity 6 2 Data which are stored in MALT for Windows The thermodynamic data stored in MALT for Window
57. ained in elsewhere Computation Explanation is given in 4 4 2 with Fig 4 10 Files Explanation is given in 4 1 2 with Fig 4 1 Tabulation Explanation is given in 3 3 3 with Figs 3 12 and 3 13 83 Chapter 5 Applications in the MALT Direct Environment Chapter 5 describes details ofthe MALT Direct environment and about how to make full use of this function It is implicitly assumed that user s application programs to be used in the MALT Direct environment will be developed on the basis of the Delphi 5 as computer language and compilers This chapter also describes some notices on how to use these compilers 1 Role of the thermodynamic environment 2 realization of the thermodynamic environment 3 procedures for the thermodynamic environment 4 developing application programs 5 1 Role of the thermodynamic environment MALT for Windows provides the most reliable thermodynamic data as the thermodynamic table and also calculates the equilibrium constants for examination of chemical equilibria Even so this provides only the fundamental numerical values necessary for applications of the thermodynamic data it will be required to make further calculations to apply to practical problems For example to make calculation of chemical equilibria of a complicated multicomponent system in which several reactions occur simultaneously it is necessary to solve the mass actions law as non linear equations or to minimize the total Gibbs energy
58. ame as given in Chapter 2 Thus the drives and the directories given in text should be corrected according to your particular environment When this is your first time to use MALT for Windows it is recommended to operate MALT for Windows by following the procedures given in this chapter This chapter consists of the followings 1 Starting up ending of MALT for Windows and main menu 2 Thermal decomposition reaction of calcium carbonate 3 Shift reaction 4 Chemical Equilibrium Calculation 5 Chemical Potential Diagram For advanced users of the thermodynamic analyses MALT for Windows provides the generalized calculation programs namely gem for calculating chemical equilibria and CHD for construction chemical potential diagram For such users a simple introduction will be given for how to utilize these software Sections 3 4 and 3 5 can be skipped for users who are not familiar with the advanced thermodynamic analysis 3 1 Starting up ending MALT for Windows and main menu start To start the MALT for Windows it is essential to have the Dongle in the current computer For the Dongle system please read carefully chapter 1 and chapter 2 10 I Fig 3 1 the first screen that appears after MALT for Windows is started MALT Materials oriented Little Thermodynamic Database File Search Compounds Tools Help a hell Ca m Fig 3 2 The Main form of MALT for Windows No 1 After the first sc
59. amic data and application programs and their standardization Furthermore it will be useful to facilitate the utilization of the thermodynamics to solve practical problems Such a thermodynamic database has been first realized some ten years ago in MALT2 that was the second version of MALT for Japanese users We developed it with a hope that this will give some ideas about to which direction thermodynamic database should be developed In MALT for Windows the same concept is adopted but by a different way 5 2 Realization of thermodynamic environment 5 2 1 Method of Making thermodynamic environment in MALT for Windows Even though we want to treat the thermodynamic functions like the mathematical functions there raises some dependence on compilers to be used for the application development Actually even for the case of the mathematical functions their representation precision of calculation and methods of calling depend on compilers Note on the other hand the situation in personal computers in Japan The dissemination of personal computers in Japan is due largely to the development and dissemination of the front end processor for Japanese characters This front end processor for converting between KANA and 85 KANJI stays as memory resident program and transfers what is input to DOS after the conversions to the KANJI by using interrupt from input routine The conversion from KANA to KANJI is done by the p
60. anation of the functions Help will appear on hitting the F1 key or clicking the help button which is installed in some Forms MALTWin help will appear by selecting MALT help submenu in the Help main menu 46 4 2 1 Main menu Table 4 1 shows the items available as the main menu The main menus are shown in the menu bar ofthe MALT Main Form The selection of menu can be made by 1 clicking mouse on the menu or by 2 pressing the Alt key with the accelerate keys for respective menus for example F for Files Help is instruction for users to do better operations For details of these functions see 4 2 5 Table 4 1 Items in the main menu and their functions Items Functions File Open or save MALT files Print Exit Search Compounds Get data of compounds or compound systems Edit Editing tables for results This menu appears only when the Thermodynamic Table Form is Calculate shown Calculate thermodynamic tables equilibrium constants This menu appears only when the Compound Table Form is shown Tools Set up the working conditions Some facilities for handling user own data Help Show the functions and the instruction 47 4 2 2 Submenus of File menu Submenus of the File menu are shown in Table 4 2 Table 4 2 Items and functions of the submenus in the File main menu Item Accelerator key Open Compound File O Save Compound File S Save Compound File As A Save
61. art of the MALT for Windows system file was accidentally rewritten In such a case MALT for Windows if normally operating will stop by giving the following message KKK K K K K K 24s 2s 3K K K 2 2K ok Anomalous end due to Error Error Code 201 33 1234 ABCD Range check error When there is a possibility that a part of the files were rewritten install again for details see 2 2 When the same procedure results in the same error even after reinstalling please write details of what you did and what happened and send it together with the system disk to the Kagaku Gijutsu sha attention to MALT for Windows Kagaku Gijutsu sha Yushima Tokyo 113 Japan TEL 81 0 3 3815 3988 FAX 81 0 3 3815 8489 e mail malt kagaku com Chapter 2 Installing Chapter 2 describes requirements for hardware and software to run MALT for Windows and also describes method of installing MALT for Windows 2 1 Hardware requirements for MALT for Windows The following hardware is needed to run MALT for Windows computers hard disk A hard disk is required with more than 3Mb free space Display printer 2 2 Software environments for MALT for Windows MALT for Windows runs under Windows 98 Windows 2000 or its later versions In addition MALT for Windows needs environments in which MALT EXE and MALT DAT can be made access to For details read 3 1 and related chapters 2 3 Installing MALT for Windows Monitor version The MAL
62. ase field that accepts no input The lower limit cannot be edited This is set as 298 15 for the first phase and the higher limit of the previous phase for other phases 66 DefUsrDataForm HGS 2982 Phase 1 Comments Heat Capacity Data Phase No 1 1 Name of the Phase Symbo fc1 Heat Capacity Temp_Coef r Temperature Range Coefia 104 520 J K mol lower limit 298 15 Coet b 21 920 E 3 J K mol higher limit 1150 00 Ooefe 25 940 E 5 JK2 mol Transition Goef d 0 0 E 6 J K2 mol gelta HR 0 0 kJ mol Coete 0 0 E 8 JK3 mol Symbol fr Move amp Insert Copy ove gt Delete J Paste OK Cancel Help Fig 4 6 Input for Thermodynamic Data No 2 Cp data The Copy and the Paste buttons can be valid only for the strings which appear in this form It is recommended to check the validity of the input thermodynamic functions by creating the JANAF type table for the compound Edit User Data file in other editors When you make a text file for user data by using an ordinary editor you must code the parameters according to the following format 1 The first line begins with the string UserData 2 A file can include several data sets of compound Each data set consists of the thermodynamic data at T 298 15 K with one line and the coefficients of the heat capacity two lines per temperature range as described above 3 Remark lines which begin with the character
63. ated and is displayed as shown in Fig 3 5 The Thermodynamic Table Form consists of 1 title for displaying compound formulae name if any molecular weight and date of creating the table 2 Thermodynamic table at selected temperatures 3 Thermodynamic constants list which gives sources of data the reference number and the thermodynamic constants As shown in Fig 3 5 the thermodynamic functions are given for the standard temperature 298 15 K and selected temperatures Next to the temperature column the following functions are given from the left hand column standard heat capacity Cp standard entropy S0 standard relative enthalpy to the standard temperature H T H TO 17 Thermodynamic Table GaCO3 calcite s Molecular weight 100 0869 2002 0809 r o TD en 81 874 92 900 0 000 92 900 1206 920 1128 840 82 274 93 408 0 152 92 902 1206 914 1128 356 97 076 119 363 9 209 96 340 1205 942 1102 296 105 104 141 960 19 351 103 259 1204 413 1076 561 110 466 161 623 30 144 111 384 1202 698 1051 155 114 570 178 971 41 403 119 824 1200 865 1026 045 118 003 194 499 53 036 128 205 1200 341 1001 079 121 046 208 577 64 991 136 365 1199 107 976 249 123 846 221 477 77 237 144 240 1197 965 951 552 126 488 233 406 89 755 151 810 1196 907 926 965 129 023 244 521 102 531 159 078 1203 377 901 835 131 481 254 946 115 557 166 056 1201 022 876 803 199 OOF IRA TIO 190 09F 179 746n
64. be made of function Sizeof for providing a size of the Turbo Pascal variables instead of directly giving as a numerical value procedure Initialize var NT NG NC integer var ErrorCode byte virtual Function number 0 2 Initialization of Pascal mode The initialize procedure is the same as the general mode procedure GetCompoundData Handle integer var CompData MTCompoundType var ErrorCode byte virtual Function Number 1 10 Get information of compound handle This gets information about chemical formula stoichiometric numbers molecular mass information of transition and other information as given below Ist 2nd bytes compound handle word 3rd 43rd chemical formula string type string 40 chemical formula space compound name 44th 56th name of data source string type string 12 name of the user file for user data or MALT for MALT for Windows data 57th 60th symbol of phase of stored data string 3 6lst 64th symbol of phase at 298 K string 3 65th number of component elements byte 66th 89th symbols of component elements array 1 8 of string 2 90th 137th array of stoichiometric numbers array 1 8 of real 138th 143rd charge 144th 149rd the lower limit of temperature range real 150th 155th the upper limit of temperature range real 156th 161st molecular mass real 162nd number of phase data byte 95 163rd information of p
65. be stored in a combobox and can be displayed by clicking the pull down button at the right phases The customized order is saved automatically at the end of each operation and will be realized in a next operation Each compound in the retrieved compound system is numbered in the order of the JANAF table type sequence or of the NBS table sequence and this number can be named as a compound number MALT for Windows itself uses the compound number fo make access to a set of thermodynamic functions Users can make access to those data by choosing a compound number from an application program in the MALT Direct environment The order of the compounds in user data file cannot be modified See section 4 3 4 for more information 4 3 2 Get compound system Append Compounds A compound system can be obtained by selecting the Get compound system submenu or the Append compounds submenu in the Search Compounds menu The command Get Compound System creates a new compound system and gives newly compound numbers All previous data on the memory are deleted You can append another compound system or delete some compounds from the system by using the Append Compounds submenu or the delete compounds menu When new compounds are appended in the system MALT for Windows automatically verifies whether the compounds are not redundant The compound number will be renumbered after some compounds are appen
66. by i double clicking on the element panel ii selecting the element as the currently focused state and then clicking the Remove button or hitting R key 5 Although the selection can be made by directly editing the element set field in the combobox it is not recommended On each inputting one character the input text will be checked whether the input text is valid Whenever the input text has errors proper correction will be made Selection of Search Compounds mode MALT for Windows provides three searching modes 58 1 Compounds consisting of combination of the elements 2 Compounds with other elements 3 Compound consisting of the all elements 1 Compounds consisting of combination of the elements lt A B C gt For convenience this mode is sometimes expressed by using the parentheses lt gt The mode means that all compounds which consist of all or some of the elements A Band C will be retrieved That is lt Fe O gt represents all iron oxides with polymorphism in addition to element Fe and oxygen gases The set lt Fe S O gt includes all iron sulfides iron sulfates iron iron oxide sulfur oxides and sulfur This mode is frequently used to make chemical equilibrium calculations with the MALT direct function together with gem for doing chemical equilibrium calculations It is also recommended to use this mode when use is made of CHD for constructing generalized chemical potential diagrams 2 Compound
67. c params in table Show phase transition data in table OK Cancel Help Fig 4 10 Customize MALT Setting Computation Joule J or Calories cal are available 3 Mass unit For thermodynamic tables users can choose a unit among molar unit mol weight kg and capacities of gases at 0 C latm mx The unit of m is available only for gaseous species and the compound is assumed to be ideal gas For the calculation of equilibrium constant only molar unit is available If you choose another unit MALT for Window shows an error message but executes the calculation with molar units 2 Setting calculation parameters The default value of the temperature range and step are from 300 to 2500 K with 100 K step Ifthe upper limit of the data set is below 2500 K the table will end at that temperature Note the following points 75 1 The lower limit of the temperature cannot be set under 298 15 K in principle 2 The upper limit must be higher than lower limit The temperature step must be positive value and smaller than the temperature range 3 MALT for Windows always calculates the value at T 298 15 K regardless of the temperature setting and then begins the calculation from the lower temperature limit If the upper limit of the temperature exceeds the upper limit of the data set MALT for Window terminates the calculation at the upper limit of the data set 4 With turning the option Temperatu
68. cified elements with selected mode This retrieval will be made through the Search Compounds by Element form shown in Fig 4 3 Selection should be made on a set of elements and the mode ofthe search compounds 56 earch Compounds by Element Edit Display Elements OSFe v S Selected Mode of Searching Compound Compounds consisting of combination of the elements Compounds combined with other elements C Compounds consisting of the elements Periodic Table HJD T He Li Be B C NRE F Ne ac misi e Slam ca Se Ti V Cr Mn Co Ni Cu Zn Ga As Se Br Kr Rb er oe eT aufm paaa a in en r 1 fre cs Ba Hr ta w Re os ir Pt aul Hg T1 Po Bi Po At Rn Fr Ra E Ce Pr Na Pm sm Eu Gal Tb Dy Ho Er tm Yb Lu BEER 2c te Pa U Np Pu Am Cm Bk cf Es Fm Md No Lw oS OK x Cancel 7 Help Fig 4 3 Search Compounds by Element Form for retrieving compounds Selection is made by specifying elements and the mode of Search Comnounds Selection of Elements Selection of elements is made in several ways 1 The combobox in the upper left corner of the Form is for edit and display elements This stores the previous inputs By Clicking the drop down button at the right side a list of the previously selected element sets will be displayed Alternatively when the element combobox is focused the Alt key also drops the list W
69. contains user s original data User data base udb compiled from user data file User application file exe Output files for thermodynamic calculation results Temporary files User program the applications created by users Bs OOS SL ON Ne Eg Parameter files which stores the operation codes for the devices User data files and output files are text files which can be read or re written in the ordinary text editor The other files are not text style and they can only be modified inside MALT for Windows Whenever MALT for Windows needs to know the name of a file or directory prompting will be made to select a file name in a given folder directory This folder directory can be specified in the MALT Options form with a tab sheet of Files as shown in Fig 4 1 To add a new directory folder click button Then the open file dialog will appear You can select any file in the proper directory folder Although the file name instead of the directory name is given in the field only the directory part will be utilized 4 2 The User Interface of MALT for Windows MALT for Windows has a classified command menu system and you can move among submenus by moving clicking mouse or hitting keys such as arrow keys lt gt 7 Selection of menus can be made also by keying accelerate keys In addition tool buttons are equipped for selected commands It also has an on line help system including the theoretical expl
70. cted compounds this compound is to be used in determination of stoichiometric coefficient of the reaction considered Fig 3 6 shows the Reaction Form to determine the stoichiometric coefficient for the selected reaction By manipulating the one line cursor in a similar way to that described above you should select one compound by moving one line cursor using the upward and the downward keys or by using mouse The default compound is the first line among the selected compounds Subsequently you are expected to input a stoichiometric coefficient of the selected compound the default value is always 1 Fig 3 6 shows that the value of 1 is input as the stoichiometric coefficient of CaCO3 The negative value regards the selected compound as reactant the positive being as product In the present thermal decomposition reaction of CaCOs CaCO is a reactant so that a value of 1 should be input 20 P Select a compound to define stoichiometric coefficients in your reaction Stoichiometric coef Reac Prod G4 Fig 3 6 Selection of stoichiometric coefficient of the reaction 4 Execution of calculation In the submenu of Equilibrium Constant select the Calculate or click the tool button for Calculate Equilibrium Constant After this procedure the table of the equilibrium constants for the thermal decomposition reaction of CaCO appears as given in Fig 3 7 Fig 3 7 shows that the table of the equilibrium constants
71. d as follows 1 get compounds according to the procedure given 3 3 2 2 select Calculate in the main menu 3 select Equilibrium Constant in the submenu of Calculate 4 select Define Reaction in the submenu of Equilibrium Constant or click the tool button for Define Reaction EE 5 seta target chemical reaction by manipulating the Compound Table Form with a mode of define reaction 6 go back to the submenus of Equilibrium Constant and then select calculate or click the tool button for Calculate Equilibrium Constant E 3 2 6 Calculation of equilibrium constants for the thermal decomposition reaction of calcium carbonate As an example for the above procedure the equilibrium constants of the thermal decomposition reaction of calcium carbonate are calculated here The compounds obtained according to the procedure given in 3 2 4 will be also used here To calculate the equilibrium constant it is necessary to define the target chemical reaction In MALT for Windows the chemical reaction is set up by two steps First you select all compounds involved in the reaction and then set a stoichiometric coefficient mole number of compounds related to the reaction 1 selection of equilibrium constants in the calculation menu After selecting the Calculate in the main menu select the Equilibrium Constants in the submenu of Calculate 2 select compounds to be involved in reaction To set a
72. d and the third methods the user data file should be specified before this command will start Newly input data will be stored in this text file in addition to the compiled user database file Table 4 16 Example of User data file UserData mydatal The first line is for title which begins with UserData MALT style This is an example for TiO Note that name of phases is distinguished Tio c sl 519 7 495 0 50 3 only condensed phases dH dG so No of Cp data alpha cl 42 10 17 62 6 59 0 0 0 0 the first line of Cpdata a b c d e 298 1265 4 2 tp the second line lower and upper limit of temp dH trans name of transition beta c2 42 10 17 62 6 59 0 0 0 0 1265 2023 42 mp 1 66 9 0 0 0 0 0 0 0 0 2023 2500 example of TiO2 Note difference between anatase and rutile TiO2 anatase cl s 939 7 884 5 49 92 1 anatase cl 78 07 0 13 31 84 0 0 3 43 298 1949 58 mp TiO2 rutile c2 sl 944 7 889 5 50 33 2 rutile c2 75 40 2 09 29 79 0 0 3 35 298 2130 69 mp 1 100 0 0 0 0 0 0 0 0 2130 2500 an Example of Fe Fe cs sl 0 0 0 0 27 28 5 alpha cl 39 606 38 915 6 57 48 16 0 0 298 1042 0 75 mtp beta c2 166 5 33 72 3703 7 0 0 2970 1042 1184 0 9 tp gamma c3 23 97 8 0 0 0 0 0 0 1184 1665 0 837 tp delta c4 166 5 33 72 3703 7 0 0 2970 1665 1809 13 81 mp 1 46 02 0 0 0 0 0 0 0 0 1809 3136 345 34 bp 62 Format of User Data File An example of user data file is provided under the UserDB folder in the MALT system This is a
73. d as G T H T T where To is the reference temperature 115 Usually 0 K or 298 15 K is adopted Here 298 15 K is adopted in MALT for Windows Interruption One of command sets which are equipped in Intel 16 or larger bit microprocessors This was widely used when functions of DOS and BIOS will be utilized in the program When use is made of the computer languages C Turbo Pascal Quick Basic having a function of utilizing interruptions it is not needed to code with assembler This technique was first used to realize the thermodynamic environment in the MALT2 version In the present MALT for Windows this is not used anymore JANAF Order This is the order of the compounds which is adopted in the JANAF Thermochemical Tables This is essentially given as follows rearrange elements in compounds in the alphabetical order and then sort compounds as in the dictionary Strictly speaking the JANAF Table is based on the Hill method which carbon and hydrogen are first picked up in addition to the alphabetical sequence However in MALT for Windows only alphabetical order is adopted MALT Data File See Compound Data File NBS Order This is the order of the compounds which is adopted in the NBS Tables of Chemical Thermodynamic Properties This is the same as those of NBS Circular 500 or NBS Technical Note 270 For details see manual 4 5 4 and Fig 4 14 Retrieval This is a job to get the required data
74. ded to the system You can use chemical formulae or a set of elements to get a compound system 1 Retrieval in terms of chemical formulae 2552 An example of inputting chemical formulae is shown in Fig 4 2 The formats of the chemical formulae or sets are determined by MALT for Windows In each case the maximum number ofthe element in chemical formulae and sets must not be larger than 8 The following formats are allowed to use in MALT for Windows Below elements are represented as A B D In the Input Compound Form the input text should be input like AB3 DC If you enter for example FeO Fe304 O2 MALT takes all compounds which have the same chemical formula as either of FeO Fe304 or O2 You cannot specify the phase solid liquid gas nor one of polymorphs a Al 03 B AlO The chemical formulae must follow the formats shown in Table 4 15 Since MALT for Windows searches all compounds which have the same stoichiometric numbers you can have some variation to pick up one compound For example K20 4B203 is the same as K2B8013 Note however that this compound is not retrieved by KB406 5 There is no restriction about the order of element in a chemical formula Table 4 15 Formats of chemical formula in MALT Chemical Formula Format in MALT Fe304 Fe304 B2 OH 4 B2 OH 4 K 0 4B 204 K20 4B204 CaSO 91 2H2O CaSO4 1 2H2O Feo 9470 Fe0 9470 Fe Fe 3 2 Retrieval in terms of spe
75. e Phase name at T 298 15 K The symbol of the phases a combination of the characters s P ee Standard formation enthalpy at 298 15 K kJ mol Standard formation Gibbs energy at 298 15 K kJ mol Standard entropy at 298 15 K J K mol The number of the temperature ranges and The coefficients of the heat capacity in each temperature range Only the units of Joule K and mol are allowed to use and the coefficient of heat capacity a b c d e are defined in the following equation Cp at bx 10 T cx 10 T dx 10 T ex 10 T 4 1 where Cp is given in J mol K and T is given in K The temperature ranges must be continuous that is the upper limit of a temperature range must be the lower limit of the next one Edit A Compound in MALT for Windows MALT for Windows provides a convenient facility of editing the thermodynamic data fora compound This can be started from the Add a New Compound submenu in the Tools User data menu or from the Edit Compound value menu The Edit Thermodynamic Data Form will appear as shown in Fig 4 4 This form has several sheets to be fully input 1 Data at 298 15 K Compound Name should be carefully input by considering the notation specified in MALT When decoding of the input chemical formula was failed the message will be given to correct the compound name Phase symbol at 298 K can be selected from the listed items given in the dropped list
76. e Use user defined default as current option Language Order of Compounds display Japanese NBS table JANAF table arbon number limits on retrieve I English Lowest limit fo Highest limit 2 ere Control VW Display compounds of last session ptions in searching V Show MALT screen saver Including Ionized gas Wait time before execution 3 i Including Aqueous species p Default MALT defaul Set up hhitial setting of MALT system Save Set current options as User default User Opt Use user defined default as current option Fig 4 13 MALT Options for General matter in MALT for Windows 80 4 5 2 Language Message will be given in two different ways One is based on Operation System When English Windows is running the Windows derived message will be given in English When Japanese Windows is running the same message will be given in Japanese Other message will be provided from MALT For such messages and promptings users can select English or Japanese After change the language option you have to end the MALT and restart the MALT 4 5 3 Screen control What users made on a compound system in the current session can be saved and recalled in the next session When the option for display compounds in last session is checked the compound system is saved In the same file the arrangement on the MALT Data file can be also saved Specification on the compound for the
77. e thermodynamic quantities listed in the left hand side will appear as given in Fig 3 13 3 4 Chemical Equilibrium Calculations 27 Equilibrium constant H20 e COle CO2 e H2le 2002 08 09 SS eS ee Se ee kcal mol cal C mol kcal mol ee 9 89 1 027E 05 8 867 5 119E 00 8 843 4 756E 00 8 820 4 428E 00 8 796 4 130E 00 8 772 3 360 E 00 8 748 3 614E 00 8 724 3 390E 00 8 700 3 184E 00 8 676 2 997E 00 8 652 2 824E 00 8 629 2 666E 00 Thermodynamic constants Unit cal Fig 3 13 Thermodynamic results with selected tabulation items MALT for Windows provides the computer program gem for calculating chemical equilibria on the basis ofthe Gibbs energy minimization technique To utilize this program a compound system should be set up Here we consider again the shift reaction CO H20 CO H2 3 3 In addition to the above reaction other chemical reactions can proceed between CO and H20 The Gibbs energy minimization gives the equilibrium state in the C H O system which contains many other species than these listed above To obtain the equilibrium state for a mixture of CO and H20 the following should be made 28 1 prepare the compounds to be involved in the chemical reactions 2 run the computer program gem 3 specify the calculation conditions such as the starting amount of reactants temperature and pressure 4 Do the minimization calculation 5 Treat the equilibrium resu
78. earch Compound Append Compounds by Element Tools User Data Load User Data Tools Customize MALT Settings Search Compound Clear Compound System Search Compound Delete Compounds Search Compound Show Compound Table Search Compound Hide Compound Table Calculate JANAF Type Table Select Compound Calculate JANAF Type Table Calculate Calculate Equilibrium Constants Define Reaction Calculate Equilibrium Constants Calculate Edit Copy Selected Area Edit Copy Current Row Edit Copy Current Column Edit Copy Allthe Table 4 2 9 Function keys for editing Table 4 14 shows the function keys for one line coding when you enter for example a chemical formula and so on The JANAF Type table and the result of equilibrium constant calculation can be edited by users by selecting some of fields parts or all of the listed values can be copied to clipboard 53 Table 4 14 function keys for one line coding Key Function Insert Switch the insert and overwrite mode Back Space Delete one character at the nearest left of the cursor Carriage return Finish the coding and execute the process Delete Delete one character at the cursor Esc Cancel the coding and exit the process Ctrl V Paste a string in clipboard at the cursor position Ctrl Z Undo ctrl A means hitting the ctrl key and A at the same time The sentences given in the low
79. emperature values which can be smoothly connected to the values at 298 15 K 113 Appendix 1 Important Technical Terms This manual and the menu screens in MALT for Windows frequently use the technical terms associated with the thermodynamics and also with the personal computers Some important terms will be explained below Accelerator key ANK ASCIIZ Menus and buttons can be selected by using accelerator keys These keys are usually indicated by one character with underline The Alt key and the character key should be hit simultaneously For example F can be made by simultaneous hitting Alt and F keys This is abbreviation of Alpha Numeric Kana and means those characters such as alphabet numerical number and Katakana which can be expressed terms of the Hankaku one byte characters This is one of methods for representing ASCII codes by string One zero code Chr 0 is placed as delimiter for separating strings and two zero codes are used as terminator for the end of the string data On the other hand BASIC interpreter of Microsoft and Turbo Pascal recently Delphi adopt the way of placing one byte information on the length at the top of the string this cannot be used for strings longer than 255 bytes There is no limitation about the length in ASCIIZ Child Process During running the MALT for Windows another program can be run by keeping the original program in memory This newly r
80. er part of the Thermodynamic Result Form can be edited This can be however printed out to printer or written to a file 4 3 Compound system 4 3 1 Definition of compound system MALT for Windows stores the thermodynamic data for 4931 chemical species Users have to retrieve desired compounds out of such database by themselves To do this in a rather simplified and effective way MALT for Windows adopts the retrieval method in terms of chemical formula or a set of elements Retrieval in terms of chemical formula is not practically the best way because in many cases one compound specified by the chemical formula may have many isomers or polymorphs and the thermodynamic functions are different among them Even so this is quite simple to input Two ordering ways for displaying retrieved compounds are adopted in MALT for Windows the JANAF tables type and the NBS table type You can customize and select one of them at the submenu Customize MALT Setting in the Tools menu the option for order of compounds is selected in the General tab sheet See the section 4 5 2 for details The default is the NBS table type in addition all gaseous compounds appear prior to other 54 Input Compounds Hit chemical formula to search Example CO2 CaO GaCO3 MeCo3 MgO 02 v CaCO3 Ca0 02 CO CO2 H2 H20 H20 H2 00 002 Fig 4 2 Input Compound Form for retrieving respective compounds Input texts will
81. exed first For this reason C4Al3 and B4C will appear after C whereas in MALT for Windows those compounds appear before C In both cases MALT always arranges all gaseous compounds earlier than other compounds This is useful to utilize the data for the calculation using other application like gem for calculating the chemical equilibria 4 5 5 Carbon numbers to retrieve Since MALT database stores many hydrocarbons it would be useful if user can set the lower and upper limit of the carbon numbers to avoid picking up too many compounds The option for Carbon Number Limit to retrieve is prepared for that purpose The restriction of carbon numbers is actually canceled if you set 1 for the lower limit and above 22 for the upper limit 22 because the compound which has the largest carbon number is C22H44 Input O 80009 OO OCO DO QA QHAHAAHOAAAOO OOOE OO OD OOOOOOOOOOOOO ee 0O w NOOOOO000000000 GO000009000990099 Figure 4 14 Order of chemical elements in the NBS table 82 0 for both limits indicates no limit in carbon number The default setting of this option is 0 for the lower limit and 0 for the upper limit 4 5 6 Options in searching This option is for future work ofthe MALT database At present the MALT database does not include the gaseous ionic species or the aqueous species These species will be included in the near future 4 5 7 Other Options The following options are already expl
82. f equilibrium constants for Shift reaction Above procedure makes it possible to calculate the equilibrium constants for the shift reaction by following the same procedure given above Fig 3 9 shows results for the shift reaction 3 3 3 Optional selection of calculation conditions The information given in Fig 3 9 can be obtained in another way for example by using the data book of the JANAF thermochemical tables instead of the database Even so if you want to obtain similar information at any temperature you have to do some interpolation procedure In MALT for Windows you can use the optional selection of calculation conditions without any difficulties 23 Equilibrium constant H20 e COle CO2le H2le 2002 08 09 a aw ae E a T a rm 1 027E 05 42 083 9275E 04 42 083 1 534E 03 41 895 1 366E 02 41 427 2 823E 01 40 816 9 414E 00 40 149 4 221 E 00 39 470 2 300E 00 38 802 1 434E 00 39 158 9 845E 01 37 543 7 260E 01 36 958 5 650E 01 36 404 vv aannnan 4RORC 11 oF oon z Thermodynamic constants lt lt H20 g gt gt gt Save Print Exit Fig 3 9 Equilibrium constants for the shift reaction As an example for setting additional conditions calculation will be made for a temperature region from 500 C to 600 C by a step increment of 10 C in the unit of calorie First of all confirm that the Compound Table Form appears in screen If not exit from the Thermodynamic
83. following chapters introduction installing installing procedure of MALT for Windows and the related dongl system are described in this chapter Please read carefully before you will first install MALT for Windows even if you are familiar with handling software for personal computers Instruction Let srun MALT for Windows This chapter describes the most fundamental way of using MALT for Windows in an appropriate sequence Please run MALT for Windows according to the instruction given in chapter 3 It needs only about one hour to learn the menu system of MALT for Windows For full use of MALT for Windows functions This chapter describes details of MALT for Windows menus and functions including those which are not described in chapter 3 These are customizing MALT for Windows combining user s data with data in database etc Applications in the MALT Direct This chapter describes details of the MALT Direct to provide the thermodynamic environments which was realized first in MALT2 and has been taken over in MALT for Windows Some remarks are also given to make full use of this powerful function Thermodynamic database and thermodynamic calculations This describes the thermodynamic properties stored in the MALT for Windows database their characteristic features methods of calculating thermodynamic functions inside MALT for Windows and important points in utilizing these data and writing computer programs for their applications Abbre
84. hase transitions will be given in the following sequence from the lowest temperature phase symbol of phase 4 bytes string 3 transition temperature 6 bytes real transition enthalpy 6 bytes real symbol of transition 4 bytes string 3 Note that the string variable in Turbo Pascal uses one byte for number of string so that it needs for example 41 bytes for a 40 byte string The above data structure is realized by the following record type MtCompoundType MtCompoundType record Handle CompoundName DataSource PhaseID Phase298 NumberOfElms Element Stoi_Coef Charge T_low T_high limits MolWeight NumberOfPhases PhaseData end word compound handle string 40 chemical formula compound name String 12 name of data source string 3 symbol of phase of stored data string 3 symbol of phase at 298 K byte number of component elements array 1 8 of string 2 array of element symbol array 1 8 of real stoichiometric numbers real charge real lower amp upper temperature real molecular weight byte number of phases array 1 20 of MtPhaseInfoType phase data The 9 variable charge real is newly introduced from MALT for Windows In MALT2 this variable is missed Here MtPhaselnfotype is the record type in the following structure MtPhaselnfoType record 96 Phase string 3 symbol of phase TransTemp
85. he reactants among the compounds involved in the chemical system Fig 3 16 shows the input field for temperature This form will appear on clicking the mouse on the column for temperature Two values combined with comma like 1000 100 should be input in the initial step field The first value is for the value for Trail 1 and the second value will be added on the following trials Fig 3 17 shows similar input forms for pressure CO and H20 239 Gem Project Eile Edit View Run Tool ojej e 2 elel am gt 52 Ela A T Trials Results A Activities Trial 1 Trial 2 rial a 1 0446E 07 1 2847E 06 25626 00 1 6485E 36 6 4829E 31 1 0503E 26 0503E 26 24899E 35 2 0921 E 30 1 01 81 E 26 9 3247E 69 1 3221 E 59 9 2366E 53 1 16626 171 1964E 14 21763612 41626E 02 1 1 4103E 01 on 2641 01 2 7874E 21 45145E 18 1 SBSE 3 4790E 39 65688E 34 54386E 30 7 2698E 01 62708E 01 a 4 1 6000E 30 8111 2E 27 4 1654 6 9695 E 55 6 3608E 46 35520E 39 rm 5 6453E 63 1 4486E 5 52 9 8054E 45 i 2887E 03 1 6196E 02 h 1 0953E 01 sa 6 3586E 01 6 7838E 01 698 9871 E 0 1 3940E 36 1 5981 E 30 6 7097E 26 5 7097E 26 ER Se TE 2 5863E 47 1 2586E 39 721 75E 34 4 4262E 33 31 0181E 27 9 97597E 24 4 2898E 1 6 1 509E 13 H La 79191 E44 1 TI64E 36 5 SBa9E 51 8 6018E 19 1 B696E a 54956 13 Ethyl rad GAS GAS nn sAai6E 075 E 7 6438E 20 1 3339E 16 3 33923614 14 ASRS ME
86. he case where the selected temperature is out of the temperature range Temperatures to be used in calculations should be stored as an array of real in 97 the data buffer area On returning from this call these temperature data were destroyed so that it is recommended to store these data in another variable Results of calculations are given in the real type structure for respective functions as follows Ist byte error code byte 2nd 7th bytes thermodynamic function real These data are stored in the order of the selected temperatures If there is any error the examination should be made for respective functions to find where the error occurred When this call should be made it needs 6 bytes for one selected temperature To store the returned thermodynamic functions it needs 7 bytes for each thermodynamic function This means that 35 bytes are needed for one temperature otherwise there would be no enough room to store the thermodynamic data to be required Results of the calculated thermodynamic functions are given in the following sequence as in the procedure GetThermoData Function number 1 3 unit ArH T H T H 298 kJ mol A H T A H 298 H T H 298 kJ mol Cp T JK mol S T JK mol A sG T ArG 298 G T G2 298 kJ mol This data structure is represented by the following record type MtResultArrayType MtResultArrayType Array 1 mm of MtCalcResultType
87. he previous MALT2 version as the normal procedures In MALT for Windows procedures of the same name and the same function are prepared as the public procedures of TMALTCompoundsComponent function MtNumberOfCompounds word 100 function MtNumberOfGas word function MtNumberOfCondensed word function MtNumberOfAqueous word procedure MtInitHandle Handle word var ErrorCode byte procedure MtGetCompoundName Handle word var CName string var ErrorCode byte procedure MtGetDataSource Handle word var SName string var ErrorCode byte procedure MtGetPhaseID Handle word var Phases string var ErrorCode byte procedure MtGetPhase298 Handle word var Phase_298 string var ErrorCode byte procedure MtGetNumberOfElms Handle word var Number byte var ErrorCode byte procedure MtGetElement Handle word var ElemArray MtElementArray var ErrorCode byte procedure MtGetStoi_Coef Handle word var StoiCoef MtStoichioNumArray var ErrorCode byte procedure MtGetLowTemp Handle word var T real var ErrorCode byte procedure MtGetHighTemp Handle word var T real var ErrorCode byte procedure MtGetMolWeight Handle word var Weight real var ErrorCode byte procedure MtGetNumberOfPhases Handle word var Num byte var ErrorCode byte procedure MtGetPhaseData Handle word var Symbol Trans MtPhaseSymbolArray var TrTemp deltaH MtPhaseTransArray var ErrorCode byte function MtCompoundExpr Handle word var ErrorCode byte string procedure MtGetEnthalpy
88. hen you select by moving with the Arrow keys f or the text of the combobox correspondingly change whereas the text does not change when you move cursor with mouse 2 The elements shown in the text field of the combobox are also shown in the periodic table The current status of the selection is identified in terms of color of the element panel and the character as follows non selected state 57 E selected Ca selected and currently focused state cu currently focused state The dark blue and the light blue with red character indicate the selected elements When the element set is recalled from the previous list the element of the last position in the element set field is defined as the selected and currently focused state The currently focused element can be changed by the following ways i clicking mouse ii pressing the Fn key and arrow keys simultaneously Fn move to the next element having the increased atomic number Fn lt move to the previous element having the decreased atomic number Fn move down inside the row of the displayed periodic table Fn T move up inside the row of the displayed periodic table 3 Add an Element to a Selected Element Set can be made by i double clicking on the element panel ii selecting the element as the currently focused state and then clicking the Select button or hitting S key 4 Remove the Element in Selected Elements Set can be made
89. his case three dimensions mean the elemental chemical potentials of Ca O and C By surface it means that the three chemical potentials have one relation like uCa u C 340 4P CaCO3 3 5 for CaCO This indicates that each stable compound has its own plane having the slope corresponding to its stoichiometry Such planes form one polyhedron as shown in Fig 3 21 This shows why this approach is called the polyhedron approach 3 5 5 Graphics and Tables To construct the usual two dimensional diagram it is needed to specify the diagram type and the diagram coordinates 40 CHD Win MALT Direct lt The kK T DE lol xi File E Edit E Project E Viem Y Run R Discran D Window Bidani gt o EL gt pi y ug a pa mA Al Determine Coefficient of Diagram Specification Diaeram 2 x Current System Reenter R fio The kK T In P Pa O C Ca system rt 5 Total Dimension Numbef Number of Fixation 2 3D Surface Diagram 2D Chemical Potential J OK CoordinateForm Coorinate Type T C Dimension Wariable D Compound Type C Diagram Type Dimension Selection Fixation Diagram Selection Function Type Diagram Type T floe Activity j2D Chemical Potential Diagram xl Candidates A Coordinates selection N DC D Ca Ze gt c Chanee C Default F
90. icated technique so that beginners can easily follow it will be a good instruction for user to develop their own applications 5 4 2 Additional comments on Turbo Pascal Turbo Pascal was selected in the development of MALT for Windows because of its ability of compiling separately for respective units its fast compiling 103 speed its availability of useful procedures to make is possible to realize the MALT Direct environment among them its creating executing codes which are compact and effective This is also appropriate for user to learn the structured language To make full use of the Pascal mode procedures in the MALT Direct from applications it is needed to handle a record type variable which can be accessed in more way than one Even so this is beyond beginner s levels To facilitate the utilization of the Pascal mode by users MALTDATAfile dcu is provided this collects procedures and functions which are useful to develop applications by Turbo Pascal Delphi The definitions of the procedures and functions included in MALTDATAfile dcu are given in MALTDATAfile PAS these are divided into four levels so that users can use them depending on users level There is no problem when functions in the different levels are used simultaneously level 0 initialization routine It is needed to call once before other procedures will be called level 1 it can be used with only the fundamental
91. ichiometric compounds After the selection of phases mixtures the stoichiometric condensed phases should be defined After pressing the New Phase button the stoichiometric compound radio button should be checked All condensed phases will appear regardless whether they are selected as one of components of mixture phases When you select some compounds whose phases were already used for other phases the Phase Selection Form appears to prompt to select phases for invariant stoichiometric compounds The The Rest button provides a function to select those phases which are not selected for other mixtures It should be noted that in many calculation programs such as gem and CHD it is not appropriate to have the two different phases that has the same thermodynamic properties It should be avoided to include the same state into different mixtures Sb MALT M terials oriented Little Thermodynamic Database 3 y loj x File Search Compounds Galclate Tools Help 298 3200 4 mp I 3200 4000 lt c Selected 20 Cao2 21 Cac2 22 CacO3 aragon 23 CacO3 calcite X Cancel Help 17 C diamond s 1 All 18 Ca sl 3 lt 1 2 gt A Select Dispose All Clear New Phase Prev Phase Next Phase Save Default AS OK Fig 4 9 Selection of stoichiometric compounds Phase Selection for candidate invariant compounds Some phases are already selected and used for other
92. icularly convenient 2 MALT Direct using MALT object with Data The MALT Direct allows to make data transfer of the compound system to users application programs This data are stored in the object called TMALTDataCompoundComponent Although this object is not fully open the important property and procedures are open to MALT users To make access to the data stored in this object users can call one of the procedures like in the interrupt technique in the previous MALT2 version 5 2 3 Data Transfer Due to the MALT Direct To realize the thermodynamic environment from the main menu you select the User s application in the Tools main menu When the user program is successfully run the MALT Direct command is ready to perform Since this user program is run under the control of the MALT for Windows it will be terminated when MALT for Windows will be ended The compounds to be used in calculations should be retrieved as parts of the selected compounds When you want to run an application program APPLI which uses the thermodynamic data of compounds stored in a compound file CompF 1 first read the compound file CompF1 from the Read Compound File submenu in the File main menu of the MALT for Windows and then make the MALT Direct 87 5 2 4 running thermodynamic environment from the command line When the same data file and the application are used to make some calculations a function
93. iled by Delphi Mode is to distinguish between two modes Mode 0 Data transfer of compound system 89 Procedures Mode 1 Data transfer of MALT Data file Retruncode 0 normal end 1 MALT is not running 2 No retrieved compounds 3 Unexpected error occurred during the preparation of data 1 Fatal error occurred Results are TMALTCompoundsComponent for mode 0 TMALTDATAComponent for mode 1 When this function is succeeded the message of Sent MaltDirect mode appears in the status bar of the MALT main form In order to use MAL TDirect MALT for Windows should be running Application programs alone cannot use of MAL TDirect of TMALTCompoundComponent It should be noted that the enthalpies and the Gibbs energies obtained by this technique are defined below ArH T H T H 298 5 1 A H T ApH 298 H T H 298 5 2 A G T A G 298 G T G 298 5 3 and these values are different from those standard enthalpy change for formation or the standard Gibbs energy change for formation as given in the thermodynamic tables This will be fully described in 6 3 Note however that when the sum or difference are calculated by using these functions given above they are the same as those calculated from the standard functions for formation In the thermodynamic environment it is possible to use the temperature coefficients of heat capacity even for the phase that is not stable at se
94. indows there is no special thing to be prepared When names of the application and of the data file are not given with the full path these files are searched in the following sequence as described in 4 1 2 1 the current directory 2 the directory specified for compound file and user application file The first found file is used 88 Furthermore when the same application and data file as before are to be used you can use as wild card as given below MALT The previously used compound file and user application in this command line parameters are stored If the previously used compound file is not available the stored compound system if any will be called When the user application file has to run without specifying compound file the following switch nonmcf can be used MALT nonmcf APPL1 When the user application can use a command parameter this parameter can be specified just after the application name The following is an example MALT nonmcf gemWin Sample gem where Sample gem is the file for gem project that is supposed to be saved in the previous run of gemWin 5 3 MALT Direct call from Delphi 5 Application 5 3 1 Procedure MALT Direct The procedure MALTDirect is defined as follows function MALTDirect Aowner TComponent Mode integer var Returncode integer TMALTCompoundsComponent Aowner is supposed to be the main form of the application program which is comp
95. is enthalpy change for formation with the values in the database do not give correct values 108 This means that the thermochemical data forms a net work A change of value in such a network inevitably gives rise to the change to all possible chemical reaction Thus modification of values should be made carefully by considering the major network characteristics This closeness of the thermochemical network is the consistency concerning chemical reactions The consistency among the thermodynamic functions means that given thermodynamic functions should meet the thermodynamic relations This requirement is quite obvious but it is quite hard to realize it Particularly the following relation about the Gibbs energy is important in practical applications of the thermodynamic data AG AHP T AS 6 1 The reason why this relation is hard to be met can be explained as follows a value of AG is determined mainly by equilibrium measurements AH is determined by reaction calorimetry and AS is derived from the S values which is determined from the low temperature heat capacity measurements It is not easy that those values determined from the different experimental techniques can satisfy the above relation Even so it is troublesome from the users point of view if these relations were not satisfied Considerations on these problems lead to the following understanding the thermodynamic data are not merely a simple set of values char
96. ito K Takeshita T J Solid State Chem 88 579 583 1990 Skolis Yu Ya Pashin S F Kovba M L Kitsenko S V Rus J Phys Chem 65 13 17 1991 Pashin S F Skolis Yu Ya Rus J Phys Chem 65 256 259 1991 128
97. ixture phase Stoichiometric conden Compound Oa lime States Lv select X Cancel Help All Select Dispose All Clear New Phase Prev Phase Next Phase Save Default X Cancel Help H Fig 4 8 Phase Selection for liquid mixture 70 All selected compounds displayed in the lower form will be canceled and moved to the upper form 5 Clicking one compound in the lower form and then pressing the dispose button to move that compound to the upper form Selection of liquid mixture When you select Liquid mixture the compounds which contain the liquid state will appear as candidates To select a liquid mixture first the New Phase button should be pressed In the upper left corner the Mixture Phase radio button should be checked and the liquid should be selected in the middle combobox at the upper part of the form For a given Ca O C system only Ca and CaO have the liquid state in their compound data stored in the MALT database Both compounds have more than two phases at high temperatures In sucha case the Phase Selection Form appears to prompt to select the proper phases for the given mixture In Fig 4 8 the liquid state of Ca was already selected and the Phase Selection Form prompts to select for CaO After defining mixtures in this function those mixtures are treated as ideal gaseous mixture or ideal mixture in gem or CHD Selection of sto
98. l FMALT initial set is given as nil FTemperature 300 FTemperature is initialized as 300 K end procedure TForm1 FormDestroy Sender TObject begin FMALT free This is needed to clear the memory used end procedure TForm1 ShowCompounds var NCompound i integer CompoundNameStr string TemperatureRangeStr string PhaseStr string begin if FMALT nil then exit with FMALT StringGrid1 do begin initialize NCompound if NCompound lt gt 0 then begin Rowcount NCompound 1 Cells 0 0 Name Cells 1 0 Temp Range Cells 2 0 phase for i 1 to NCompound do begin GetNameRangePhase i CompoundNameStr TemperatureRangeStr PhaseStr Cells 0 i CompoundNameStr Cells 1 i TemperatureRangeStr Cells 2 i PhaseStr end end end end function GetNextStr var ss string string 105 var i integer begin Result i Pos ss if i lt gt 0 then begin Result Copy ss 0 i 1 ss Copy ss i 1 length ss i end else begin Result ss ss 5 end end procedure TForm1 ShowStoichiometry var NCompound i integer CoINo integer StoichioStr string begin if FMALT nil then exit with FMALT StringGrid1 do begin initialize NCompound if NCompound lt gt 0 then begin Cells 3 0 Element 1 Cells 4 0 Element 2 Cells 5 0 Element 3 Cells 6 0 Element 4 Cells 7 0 Element 5 for i 1 to NCompound do begin GetStoichiometry i StoichioStr ColNo
99. l potential diagram for the selected system 4 Do calculation based on the polyhedron approach for constructing the generalized chemical potential diagrams 5 Display the obtained diagram 6 Manipulate the diagram upon some requirements for dissection touch etc 3 5 1 Preparation of the compound system in MALT for Windows As an example to construct the chemical potential diagram we will use the Ca O C system To retrieve the thermodynamic data you can do the same 2352 procedure given as Section 3 3 that is select the Get a Compound System menu with the option of Selection by Elements Ca O C should be selected together with the mode of compounds consisting of combination of elements This retrieval mode is very convenient for the construction of chemical potential diagrams 3 5 2 Run the computer program CHD Here it is ready to run the CHD program Easiest way of running CHD is the same as the gem that is the selection of the CHD command in the Tools main menu This command is to execute the following command CHDWind exe md The meaning of the switch md is the same as before Fig 3 19 shows the resulting CHD main form after executing the MALT Direct command In the title line of the Main Form it is indicated that data are obtained by MALT Direct for the Ca O C system The next line is the menu bar whereas the second line indicates the tool buttons
100. lected temperatures This is needed in examination of phase relations in which the chemical potentials of compounds are needed even for their unstable temperature range In such a case it is needed to specify which phase should be used Temperature range number means a parameter of indicating this phase number that is given by heat capacity data number the room temperature phase is defined as number 1 and this number increases at each 90 transformation 5 3 2 MALT Direct in the general mode In MALT2 the general mode was provided for any compiling systems However MALT for Windows has not prepared the same availability for any compiling systems However to keep the compatibility the procedures corresponding to the general mode were prepared in the Delphi 5 environment alone When the user program is written in Pascal in the Delphi 5 environment we suggest to use the Pascal mode instead of the following general mode procedure Initialize var NCompound integer var ErrorCode byte overload virtual procedure Initialize var NT NG NC integer var ErrorCode byte overload virtual procedure Initializel var NT NG NC NA integer var ErrorCode byte overload virtual Function number 0 1 initialization of general mode This procedure is to initialize the MALT object to response to the inquiries Without initializing with this procedure no access can be allowed At the same time this initializing procedure gives
101. lso shown in Table 4 16 Table 4 17 The line which contains the thermodynamic data at T 298 15 K Columns 1 40 Columns 41 44 Columns 45 48 Columns 49 58 Columns 59 68 Chemical formula and name of compound if necessary A space must be placed between the chemical formula and the compound name The phase name at T 298 15 K The symbol of the phases a combination of the characters s I and g Standard formation enthalpy kJ mol Standard formation Gibbs energy kJ mol Columns 69 78 Standard entropy J Kmo Columns 79 80 The number of temperature ranges Table 4 18 a The lines for the heat capacity data Ist line Columns 1 25 Column 25 30 The symbol of the phase s I or g Column 31 40 The name of the phase The coefficient a Column 41 50 Column 51 60 Column 61 70 Column 71 80 The coefficient b The coefficient c The coefficient d The coefficient e Table 4 18 b The lines for the heat capacity data 2nd line Column 1 25 Space Column 26 35 The lower limit of the temperature range Column 36 45 The upper limit of the temperature range Column 46 55 The enthalpy change at the upper limit of the temperature range kJ mol Column 56 65 The symbol of the phase transition at the upper limit of the temperature range 63 Those thermodynamic data for one compound which are stored in the user data file consist of the followings Compounds nam
102. lts as graphs or tables 3 4 1 Preparation of the compound system in MALT for Windows To make an appropriate equilibrium calculation at high temperatures it is essential to guess the chemical species to be involved in the equilibrium Since the recent computer program for calculating the equilibrium state becomes very power full it becomes not so severe to limit the number of the chemical species to be involved in calculations In this sense it is safe to include many species in the equilibrium calculations Even so the present case is the reactions in the C H O system where a lot of higher order hydrocarbons are O x j Computation Eiles Language Order of Compounds display Japanese O NBS table JANAF table Carbon number limits on retrieve English Lowest limit fi Highest limit 2 IV Display compounds of last session Options in searching Screen Control IV Show MALT screen saver Including Ionized gas Wait time before execution 3 min Includine Aqueous species Default MALT defaul Set up Initial setting of MALT system Save Set current options as User default User Opt Use user defined default as current option OK Cancel Help Fig 3 14 Setting the Carbon number limit in retrieval of carbonaceous compounds in the Customize MALT setting menu 29 essentially available In such a case it isbetter to exclude some high order
103. mperature is out of valid range 10 Given Phase Number is out of range 11 This is Invalid Number 12 Invalid Size for Data Buffer 13 High Temperature Data are not available for the specified compound 102 14 Invalid Phase Number 5 4 Development of applications This section describes some instructions for developing applications by using the MALT Direct and related procedures 5 4 1 General instructions An application has generally the following structure 1 Initialization Procedure MALT Direct is called and the thermodynamic environment should be started 2 Obtaining the compound information When necessary the information of compound should be taken Chemical formula commonly used name phase information stoichiometric information temperature range are necessary to confirm whether the aimed compounds are correctly taken 3 Set of calculation conditions Target thermodynamic functions calculation temperature phase data to be used are determined and set 4 Run calculations The procedure of calculating thermodynamic functions is called to get data needed 5 Calculations in applications Calculations necessary in applications are made using the obtained thermodynamic functions To show these procedures and the fundamental functions in the general mode sample programs SAMPLE are provided in the source program and the compiled codes for Delphi 5 or Delphi7 These programs do not use sophist
104. ned Var CompoundNameStr string Var NameOfDatabaseStr string Var TemperatureRangeStr string Var PhaseStr string e Compound Name is stored as a form of chemical formula space name of common use space and spaces are added so as to form 40 byte as total e Name of database is MALT or a name of the user data file e Temperature range is given with parenthesis as the temperature range valid for the compound e Phase is given as phase symbol for the state at 298 15 K When specified handle is not available Errorcode 2 is returned procedure GetStoichiometry Handle integer var StoichiometryStr string var ChargeStr string virtual Function number 1 1 Obtaining the stoichiometric information 032 of selected compound handle Return the stoichiometric information of compound specified by Handle number Results are stored in string variables Element symbol stoichiometric number are stored in this sequence and finally the molecular mass is stored example A1203 is given as O 0 3 0 Al 0 2 0 101 96128 0 0 Fe0 9470 is given as O 0 1 0 Fe 0 0 947 0 66 88651 0 0 procedure GetElements var Nelement integer var ElementsStr string Nelement is the total elements in the present MALTCompoundscomponent When charged species are included in the system property Lcharge is set as true Insuch a case Nelement is set as the total number of elements
105. nna Part 3 Cordfunke E H P O Hare P A G Miscellaneous Actinide Compounds 1978 IAEA Vienna Part 4 Gr nvold F Drowart J Westrum E F Jr The Actinide Chalcogenides Excluding Oxides 1984 IAEA Vienna Part 5 Chiotti P Akhachinskij V V Ansara I Rand M H The Actinide Binary Alloys 1981 IAEA Vienna Part 6 Holley C E Rand M H Storms E K The Actinide Carbides 1984 IAEA Vienna Part 8 Fuger J Parker V B Hubbard W N Oetting F L The Actinide Halides 1983 IAEA Vienna 121 Part 9 Flotow H E Haschke J M Yamauchi S The Actinide Hydrides 1984 IAEA Vienna Part 13 Hildenbrand D L Gurvich L V Yungman V S The Gaseous Actinide Ions 1985 IAEA Vienna 20 Kelley K K Contributions to the Data on Theoretical Metallurgy XIII High Temperature Heat Content Heat Capacity and Entropy Data for the Elements and Inorganic Compounds Bulletin of U S Bureau of Mines 584 1960 U S Government Printing Office Washington 21 Kubaschewski O High Temp High Pressures 4 1 12 1972 22 Cox D J Pilcher G Thermochemistry of Organic and Organometallic Compounds 1970 Academic Press London 23 Martin J F Specialist Periodical Reports Chemical Thermodynamics Vol 1 pp 133 161 1973 The Chemical Society Burlington House London W1V OBN 24 Pedley J B Naylor R D Kirby S P Thermochemical Data of Organic Compounds
106. nter or file The result of calculations can be exported to a file or printer Thermodynamic constants are shown on screen or printed out however they cannot be exported to a text file by any means Users must verify that the control codes are set up correctly MALT for Windows has a couple of sets of the control codes for general printers and users can customize the codes See section 4 5 3 for further information 4 4 4 Definition of the reaction Users have to first define a reaction for the calculation of equilibrium constants The compounds are selected by choosing compound handles which can distinguish different phases of a compound With the command Define reaction in the submenu Equilibrium Constant users can select compounds from the compound list without any complicated procedure and MALT for Windows sets a reaction automatically The following points must be noted The selection of compounds to be involved in a reaction can be selected by the following ways 1 double clicking on the compound to be selected 2 moving one line cursor to the compound and pressing the select button To remove the selected compound 3 double clicking the selected compound 4 moving the one line cursor and pressing the dispose button The selected compounds are displayed in green color or in blue color when the compound is focused 297 2 Compound Table Selection ofReactions 9 E g 298 2500
107. o step approach for utilization of the thermodynamic data This is to make full use of a limited amount of memory and to ensure high speed performance simultaneously 1 the first step is retrieving data of a set of compounds This corresponds to the data transfer from the database in a hard disk to the main memory A set of compounds can be called a compound system 2 the second step is utilizing retrieved data in thermodynamic calculations In this step therefore no access is made to a hard disk At the first glance this two step approach appears to be complicated However it seems to be the most convenient method for extracting target compounds out of the more than 4900 species in our database We adopt a way of retrieving data by selecting a set of compounds in terms of jr chemical formula or combination of elements Selection in term of chemical formula without specifying states collects gaseous species condensed species and all polymorphs with the same formula at the same time In many cases this gives rise to no serious problems If you do not need some of them you can delete them from the list of compounds Thus MALT for Windows provides functions of editing a list of compounds retrieved before use in calculations and of saving a list of selected compounds The procedure of getting compounds can be summarized as follows 1 Select Search Compounds in the main menu 2 Select Get compound system when the current comp
108. of a system like gem does Furthermore to make exergy analysis of a chemical process it is quite important to prepare the thermodynamic properties of mixtures as functions of composition as well as temperature When the thermodynamic functions of many compounds at many selected temperatures are to be utilized in MALT for Windows it will be convenient to save these values in files this allows application programs to read such files Even so it will be tedious and troublesome with increasing a number of compounds to be treated 84 First the number of such files increases Secondly the thermodynamic functions to be truly used in applications should be collected to make one file by using an editor Thirdly this kind of data transfer is quite dangerous because of a great possibility of introducing many mistakes In view of this there should be another way of handling these numerical values Ideally speaking it is highly desired to obtain a thermodynamic function just by specifying a compound temperature and state in an application program in a similar way to mathematical function calls To realize this it will be needed to combine the computer environment with the thermodynamic data This can be called thermodynamic environment This will make it easy to utilize the thermodynamic data in application programs and also will provide the fundamental basis of stepping further for the future common interfaces between the thermodyn
109. or database system should keep the internal consistency among the thermodynamic data to be collected Particularly the thermodynamic data have to meet two requirements for consistency one is the consistency concerning thermochemical reactions the other being the consistency among the thermodynamic functions The consistency concerning thermochemical reactions means the following requirement thermodynamic functions are usually derived using the thermodynamic data of other species In such a case the thermodynamic data of other species should be given in the same data book For example the enthalpy change for formation of benzene is derived from the experimental value for the combustion heat of benzene and the enthalpy changes for formation of water and carbon dioxide CoH 8 5 O2 6CO 3H2O Acombustion 6A H CO 3 A H H20 a AtH C6H6 8 5 A H QO2 AtH C6H6 Acombustion ss 6A H CO 3 AH H20 8 5 A H O There is no certificate whether those values of enthalpy changes for formation of water and carbon dioxide which were used to derive the enthalpy change for formation from the experimental combustion heat are in good agreement with those stored in database If different values are adopted for AgH CO2 and AgH H20 in database and the enthalpy change for formation of benzene remained without correction since its determination from measured combustion heat calculation results obtained by using th
110. or further fixation of component dimension properties In the current system we have three free dimensions that is the appropriate number for constructing the chemical potential diagram CHD Win MALT Direct lt The kK T In P Pa O C Ca system gt File Edit E Project F View v Run Diceram D Window W Help pre Libixning aaae a Froml fioo 2 Seroug Tol zooo xt 500 Ei 500 jut i Hs En Fig 3 19 CHD Main form after selecting CHD in the Tools menu 37 for the Ca O C system We do not need to specify in this tab sheet for the current system The tab sheet of Select Diagram is to specify the diagram type to be constructed The default diagram type for the current system is the 3D surface diagram Diagram Specification Dimension Selection urrent System The kK T InfP Pa O Ga system Terms Total Dimension Numbel 5 Number of Fixation 2 2 3D Surface Diagram 3D Surface Diagram el Dimension Selection Fixation Diagram Selection Diagram Type r Temperature T Fixed fi 000 C Not Fixed rPressure P Fixed fi 0000 Not Fixed X Cancel 7 Help Fig 3 20 a Diagram Specification for giving the selected values for temperature and pressure 38 Diagram Specification 3 2 x Current System The kK T In P Pa O C Ca system Total Dimension N
111. ound system should be deleted and a new compound system retrieved Select Append compounds when you do no want to delete the current compound system but add new compounds to the system 3 Selection should be also made between Search by Compound and Search by Element To select an item in pull down menus 1 use a mouse to move to the proper menu and then do left click 2 or press the Alt key to have a focus on the menu bar and move to the item to be selected i by using the upward or the downward arrow keys and then press the carriage return key or ii by inputting the specified accelerator key co 99 4a Input a number of chemical formulae by using as separators 4b or input a selected number of elements with specification of one searching mode out of three modes See 4 3 for details Examples are given in 3 3 2 for a set of elements and in 3 4 1 for chemical formulae 3 2 2 get compound system by using a set of elements When you are going to do Get compound system Search by Element just after the MALT for Windows installation the following Search Compounds by Element form will appear as Fig 3 3 with Edit Display Elements field which shows the following text Ca C O This is a default text string which was given at the install procedure This default is set just because this set of compounds are necessary to examine the thermal decomposition reaction of calcium carbonate 13
112. quilibrium constants 5 System setup 4 1 MALT for Windows and Windows environment 4 1 1 Directories in MALT for Windows In order to run MALT for Windows and related software gem and CHD properly it is essential for MALT exe can find out the necessary files for starting up The following files usually are stored in the same directory as MALT exe file Malt dat Glen dat MaltMes str MALT PRM User ini MAL TWin hlp MAL TWin cnt MAL TManual pdf CHDWin exe CHD2DlIgs cnt CHD2DlIegs hlp CHDWin ini CJHDManual pdf 44 GemWin exe GemWin hlp An error message will be given when it failed to find these files 4 1 2 Files in MALT for Windows In addition to the MALT system files described above MALT for Windows uses many types of files which can be categorized into several groups Directories for such files can be defined in the Customize Malt settings submenu of the Tools main menu After selecting this menu the MALT options form appears This form consists of several tabsheets A tab sheet of Files is given as Fig 4 1 Malt Options E A E GemWin exe v E Users Output txt ha a TempDirect E PA Fig 4 1 MALT options for files directories 45 Those files which are used in MALT for Windows can be categorized into the following groups Compound File mcf MALT Data file mcd in which the compounds system is stored User data file txt which
113. r Gruber J B Warmkessel J J Chem Thermodyn 11 835 850 1979 Morss L R Haar C M J Chem Thermodyn 21 1079 1083 1989 Helgeson H C Delaney J M Nesbitt H W Bird D K Am J Sci 278A 1 220 1978 Hemingway B S Barton M D Robie R A Haselton H T Jr Am Mineralog 71 557 568 1986 Hildenbrand D L Lau K H Russell T D Zubler E G Struck C W J Electrochem Soc 137 3275 3287 1990 Shaviv R Westrum E F Jr Gr nvold F St len S Inaba A Fujii H Chihara H J Chem Thermodyn 21 631 651 1989 Lvova A S Feodosev N N Zh Neorg Phys 9 2251 1964 Alcock C B Li B J Am Ceram Soc 73 1176 1180 1990 Shaviv R Westrum E F Jr Yang T L Alcock C B Li B J Chem Thermodyn 22 1025 1034 1990 Skolis Yu Ya Khramtsova L A Rus J Phys Chem 64 1681 1683 1990 Kovba M L Skolis Yu Ya Khramtsova L A Rus J Phys Chem 64 1684 1686 1990 Hwang N M Roth R S Rawn C J J Am Ceram Soc 73 2531 2533 1990 Tretyakov Yu D Kaul A R Makukin N V J 127 Solid State Chem 17 183 189 1976 Suzuki R O Okada S Oishi T Ono K Mater Trans JIM 31 1078 1084 1990 Skolis Yu Ya Kitsenko S V Rus J Phys Chem 63 1132 1133 1989 Morss L R Sonnenberger D C Thorn R J Inorg Chem 27 2106 2110 1988 Atake T unpublished work Matsui T Fujita T Na
114. r data Data Format Conv C Create a compound data file in which mixture phases can be included gem g Start the gem program for calculating chemical Equilibria CHD H Start the CHD program for constructing chemical potential diagram The user data menu consists of many submenus as listed in Table 4 10 Similarly the data format conversion menu also has several submenus listed in Table 4 11 Table 4 10 Items and Functions of submenus in the User Data menu Item Accelerator key Function Compile User Text File C Make the data set for MALT for Windows from the user defined data file Load User Database L Load user data to the work space Unload User Database U Remove user data from the work space Add New Compound N Add new user data for a compound in a given user database Edit Compound Value E Edit one compound listed in the compound table and save in a user database Save User File S Save the current available user data after adding or editing compound as user text file Save User File As A Save the current available user data after adding or editing compound as a selected user text file 5 Table 4 11 Items and Functions of submenus in the Data Format Conversion menu Item Accelerator key Set up Compound S Default Setting D Verify Compounds V Save in the Format As A Function Set up phases by selecting comstituent compounds for respective phases
115. rals and Related Substances at 298 15 K and 1 Bars 10 Pascals Pressure and at High Temperatures 1978 US Government Printing Office Washington 119 9 10 11 12 Stull D R Westrum E F Jr Sinke G C The Chemical Thermodynamics of Organic Compounds 1969 John Wiley amp sons New York Stull D R Sinke G C Thermodynamic Properties of the Elements Advances in Chemistry Series 18 1956 American Chemical Society Washington Glushkov V P Gurvich L V Bergman G A Veitz I V Medvedev V A Khachkuruzov G A Yungman V A Thermodynamic Data for Individual Substances High temperature Institute State Institute of Applied Chemistry National Academy of Sciences of the U S S R Moscow Vol 1 The elements O H F Cl Br I He Ne Ar Kr Xe Rn S N and P and their compounds 1978 Vol 2 The elements C Si Ge Sn and Pb and their compounds 1979 Vol 3 The elements B Al Ga In Tl Be Mg Ca Sr and Ba and their compounds 1981 Vol 4 The elements Cr Mo W V Nb Ta Ti Zr Hf Sc Y La Th U Pu Li Na K Rb and Cs and their compounds 1982 Atomic Energy Review Special issues No 1 Rand M H Livey D T Feshotte P Nowontny H Seifert K Ferro R Plutonium Physico chemical Properties of its Compounds and Alloys 1966 International Atomic Energy Agency Vienna No 2 Lavrentev V I Gerassimov Ya I Feschotte P Livey D
116. re Extrapolation on you can expand the temperature range below 298 15 K or beyond the upper limit of the data set However you must note that the reliability of the data will be lost at the temperature below 250 K At temperatures above the upper limit of the data set MALT for Windows extrapolates the data set of the highest temperature phase 4 4 3 Output the result of calculation Clipboard Users can utilize the result of calculation at their own will One way is to copy to the clipboard 1 H Selected area 2 H selected columns 3 H selected rows 4 H all the table Except for all the table the selected area should be specified by manipulating mouse or arrow keys before doing these commands Since these copied data are in table style the format can be selected for delimiter Usually tab code is inserted between rows and the carriage return crlf will be used for the end of on column data For the delimiter choice can be made in the Customize MALT setting Files menu see Fig 4 1 1 The same format as screen 2 Comma as delimiter 3 Space as Delimiter 4 Comma with quotation zoz You can select one ofthese options according to your software to be used with the data in clipboard For example Excel can accept the data in the same format as screen whereas for Origin to accept the data in the same format as a screen the number of rows should be increased more than that of the data Pri
117. re Ranged Define Phase Data OK Cancel Help Fig 4 4 Input for Thermodynamic Data No 1 Data at 298 15 K 65 The value based on internal consistency calculation Confirm Gibbs Energy consistency Given value Calculated value Jf OK X Cance Help TARGET delta HkJ mol 1206 920 1206 897 Kai delta Hl 1128 840 1128 863 Zi delta 92 900 92 822 a gt gt Fig 4 5 Consistency check among the enthalpy Gibbs energy and Entropy In Fig 4 5 the originally input data are displayed in the left row the calculated values from other two values being in the left row If you find some errors in your input data and want to change the input value to the calculated value you can press the change button then the right half of the form will appear to provide the exchange to the calculated value for enthalpy Gibbs energy or entropy High Temperature Phases is a number of high temperature ranges According to this number the same number of sheets for input high temperature heat capacities will be prepared 2 High Temperature Phases The number of the high temperature phases can be changed 1 by correcting the input number in the HGS298 tab sheet 2 by clicking the insert button in the Heat Capacity tab sheet 3 or by clicking the delete button On each heat capacity tab sheet each edit field should be filled except for the name of ph
118. reaction to be calculated you first select the Define Reaction in the submenus of Equilibrium Constant available compounds appear 19 in a selected sequence in the Compound Table Form At this stage the Compound Table Form shows the buttons for Select Dispose Cancel and OK at the bottom ofthe Form Compounds are selected as follows moving the one line cursor to compounds of CO2 CaO CaCO3 calcite and clicking the Select button or double clicking on the compound line The color of the cursor changes to blue When the one line cursor moves from the selected compound the color of the selected compound change to green A newly focused line will be displayed in blue if the line is selected or in dark blue if the line is not selected Changing the selected compound to the non selected one can be made by clicking Dispose button or by double clicking on the selected compound After selecting all compounds to be involved in a chemical reaction the OK button can be clicked At this stage it is needed to satisfy the condition under which the selected compounds can form a meaningful reaction without ambiguity If any reaction cannot be set up uniquely an error message will appear to prompt the re selection of compounds See details in 4 4 4 3 Set a coefficient of the stoichiometry What to be done as a next step is to select one particular compound out of the sele
119. red New compound system is developed in the working space and respective areas The user s customized compound file also contains the order ofthe compound namely the JANAF order or NBS order If the current order is different from the order of the data file it will be changed to that of user data file Such a user customized compound file is convenient when the user treat the thermodynamic data by their own application program or gem CHD in the MALT Direct environment For just saving the current status of the compound system you do not need to save the compound file on every ending procedure In the MALT options form appearing after selecting the customize MALT setting submenu in the Tools menu the display compounds in last session option can be checked 60 In the option checked the current status will be restored in the next session 4 3 5 User data Some expert users may prefer to modify the thermodynamic data in the database or want to add new sets of thermodynamic functions Such data management is necessary for applications of the thermodynamic database although careful and skillful management is required in view of the complicated nature of the thermodynamic functions that form a loose thermochemical network see details Chapter 6 This is made by a use of User data files There are two different kinds of files related with user data One is the ASCII type file other being the
120. reen like Fig 3 1 appears the Main form of the MALT for Windows Fig 3 2 will appear The Main form consists of the following 1 Title bar 2 Menu bar 3 Tool button bar 4 Status bar The first menus available at the beginning have four menu items that is file search compounds tools 11 help Each menu has submenus end To end MALT for Windows you can select one of the following ways 1 Select the Exit submenu in the File menu 2 Click the tool button exit W on the left side of the tool bar 3 Click the close button X on the upper right corner of the Main form 4 Click the MALT logo mark amp on the upper left corner of the Main form and then select the close option in the system menus Note that in Exit command the normal ending procedures such as saving the current status of a set of compound compound data etc will be made whereas in Close command such ending procedure will not be made When you want to restart the same circumstance as when you finished select the exit command 3 2 Thermal decomposition of calcium carbonate This section describes the procedure to create a thermodynamic table similar to the JANAF Thermochemical Tables Calcium carbonate is selected as an example Then the decomposition reaction of calcium carbonate will be taken as an example for calculating the equilibrium constant 3 2 1 Get compound system MALT for Windows adopts a tw
121. resulting gem main form after executing the MALT Direct command The first line is the menu bar whereas the second line indicates the tool buttons for selected commands given in the menus The main form consists of the three tab sheets that is Trial Results Activities In the status line in the bottom of the form the current system is indicated as the C H O system containing 52 species Furthermore the first line of the second row of the Trial tab sheet indicates MALT Direct as data source 3 4 3 Specification of calculation conditions 31 MALT Direct Temperatureik D gt gt om Oo i E S GAS S D D A a n D gt oo CCO radical CH CH2 CH3 CH4 G2H G2H2 G2H3 g gt on Fig 3 16 Input for Temperature Before doing chemical equilibrium calculations the following should be specified 1 Number of calculation Default value is 3 which is shown in the third line I in Fig 3 16 In the Trial tab sheet the rows for N trials will be prepared for the respective trials This is indicated in the first column in the string grid 2 Temperature The second line is for selecting temperatures for respective rows 3 Pressure The Gibbs energy minimization needs to specify the pressure whereas the Helmholtz energy minimization needs to specify the volume 4 Initial amount of elements this can be made by selecting the amount of t
122. rner of Fig 3 23 The coordinate type can be selected from the Dimension variables and the Compound type When the Dimension Variables is selected you have to select among the given variables for inverse temperature logarithmic pressure and elemental chemical potentials When the Compound type is selected a list of available compounds is given In this case a linear combination of logarithmic activity of compounds can be selected For the coefficient of each compound in such a linear combination can be specified in the Coefficient Form as shown in Fig 3 22 where a coefficient 1 which is default value for 243 the first selected compound is selected for log p O gt atm After selecting log p COz2 atm as the y axis the two dimension diagram can be constructed by selecting the Calc submenu Figure 3 23 shows the two dimension diagram for the Ca C O system at 1000 K Phase relations appearing in Fig 3 23 are the same as those in Fig 3 21 43 Chapter 4 For full use of MALT functions In this chapter the following functions are explained in details to make full use of the powerful functions of MALT for Windows The explanation of MALT Direct to utilize the thermodynamic data in user s environments will be given in Chapter 5 1 MALT for Windows and Window environment 2 The user interface of MALT for Window 3 The compound system 4 The thermodynamic tables and the e
123. rocedure called software interrupt under MS DOS The same procedure is installed even in Windows environment MALT Direct Under the Windows operation system it becomes easy to make communication between the MALT system and other application programs By using such a new environment the MALT Direct is prepared in the MALT for Windows Although there are several different ways to realize such a concept we first consider the convenience of those users of MALT2 that realized first the thermodynamic environment Such users have already written their own programs for their purpose In the MALT2 in Japanese version a stay resident technique was adopted with interrupt procedure based on DOS Since MALT2 was coded by Turbo Pascal the interruption from the Pascal programs can be well organized In the MALT Direct therefore those application programs compiled by Delphi are first considered from the viewpoint of compatibility MALTDataCompoundcomponent In MALT2 interrupt is based as the direct access to the MALT management system and the interrupt asks to send back the necessary data In MALT for Windows a similar process is done by using the special object created by MALT namely MALTDataCompoundComponent This process consists of two stages 1 Transfer the thermodynamic data in the form of the MALTCompoundComponent by means of MALT Direct 2 Access to the individual thermodynamic data based on the same idea of Compound handle
124. s their combination will be given for example sl means that both solid and liquid are included in its data Within this screen you can check any compounds by moving the cursor by use of the upward and the downward arrow keys Since only about 20 lines can be displayed for compounds Fn key upward and Fn downward can be used for changing the displayed compounds by page up or page down When scroll bar is used to move the list the cursor selected item is not moved together 3 2 3 procedure for calculating thermodynamic tables As a next step a thermodynamic table of calcium carbonate will be calculated This procedure can be summarized as follows 1 get compounds according to the procedures descried in 3 3 2 2 select Calculate in the main menu 3 select the JANAF Type Table in the submenu of Calculate 4 select the Select Compound in the submenu of the JANAF Type Table Or click the tool button for Select compound ERED At this stage the appearance of the Compound Table Form changes to show the buttons for selection and cancel at the bottom of the Form 5 select a compound to be calculated by manipulating a one line cursor and clicking the Selection buttons or pressing s key 6 The calculate submenu of JANAF Type Table becomes available its tool button change its appearance then select Calculate or click the tool button for calculate JANAFtype Table
125. s are those necessary and sufficient to make thermodynamic calculations at high temperatures namely ApG ApH S C at 298 15 K temperature coefficients of heat capacities transition temperature transition enthalpy Units of J for energy K for temperature and mol for mass are used when numerical values are stored As described in 6 1 the thermodynamic data at 298 15 K were taken mainly from the NBS Tables Note however that the NBS Tables adopted 1 bar 0 1 MPa as the standard state all values of the Gibbs energy change for formation and entropy of gaseous related substances including condensed phases having the elements having the gaseous reference state were converted to those at 1 atm 101 325 Pa by assuming the ideal gas Heat capacities were taken from JANAF Thermochemical Tables Thermodynamic Properties of Minerals and Related Substances and others after making the least square fitting to the following equation atb10 T el0 d10 e 10 7 6 2 These coefficients have different values for respective phases when there are phase transitions Information about the phase transitions includes phase transition type Table 6 1 Symbols of phase transition Symbol Meaning mp Melting bp Boiling tp solid solid transition ltp lambda type transition mtp magnetic transition sp sublimation dp dissociation 110 transition temperature and transition enthalpy Symbols to represent phase transition types
126. s with other elements A B C For convenience this mode is sometimes expressed by using the brackets This means that all compounds which contain the element A B and C simultaneously S O represents all sulfur oxides thionyls sulfates and bisulfates Usually many compounds can be retrieved in this mode when a small number of elements are specified When O is selected in addition to oxygen element all oxygen compounds are retrieved When O Al Si is selected all aluminum silicon oxides are retrieved 3 Compound consisting of all elements A B For convenience this mode is sometimes expressed by using the braces This means that all compounds which consist of only the element A and B are taken That is Fe O represents all iron oxides and C H means all hydrocarbons The maximum number of compounds to be retrieved is limited to 1800 and MALT for Windows shows the error message if you try to pick up more than 1800 compounds Generally ca 20 100 compounds are recommended to establish the best working condition 4 3 3 Delete compounds When you want to delete some compounds in a compound system you can use the Delete compounds submenu in the Search Compounds menu You move a highlighted line with dark blue on the compound to be deleted and hit select button The compound will be shown with the different background color when the line is focused the blue is used with white characters whereas
127. sion Products 1990 North Holland Amsterdam 122 34 35 101 102 103 104 105 106 107 108 109 110 Loewenschuss A Maycus Y Chemical Review 84 2 89 115 1984 112 113 111 114 Gurvich L V Veyts I V Alcock C B Thermodynamic Properties of Individual Substances Fourth Ed See also 11 Volume 1 O H D T F Cl Br I He Ne Ar Kr Xe Rn S N P and Their Compounds 1989 Hemisphere New York Volume 2 C Si Ge Sn Pb and Their Compounds 1991 Hemisphere New York Knacke O Kubaschewski O Hesselmann K ed Thermochemical Properties of Inorganic Substances 2nd ed 1991 Springer Verlag Berlin Verlag Stahleisen m B H Dusseldorf Gr nvold F J Chem Thermodyn 5 525 531 1973 Motzfeldt K Sanberg B Chemical Investigations Concerning Carbothermic Reduction of Alumina pp 411 428 in Light Metals 1979 Peterson W S ed 1979 AIME Warrendale Pa Takahashi Y Kadokura H Yokokawa H J Chem Thermodyn 15 65 81 1983 Margrave J L Houge R H Fredin L Thermophysical Properties 4 Proceeding of The Fourth Japan Symposium on Thermophysical Properties p 107 1983 Gr nvold F Samuelsen E J J Phys Chem Solids 36 249 256 1975 Gr nvold F Sveen A J Chem Thermodyn 6 859 872 1974 Flotow H E Osborne D W J Chem Thermodyn 6 135 140 1974 Johnson G K J Chem Thermodyn 16 295 300
128. th convenience Even so use of Search by Elements for the present case of the shift reaction leads to many hydrocarbons and carbon hydrogen oxygen compounds that is more than 600 compounds when no limit was set for carbon number see 4 5 5 In order to examine the shift reaction only four compounds are needed It will be quite troublesome to set up the reaction out of a large number of compounds almost all of which are not necessary in the present case In MALT for Windows compounds can be retrieved by inputting just the oD chemical formulae for necessary compounds Chemical formulae should be input according to the notation given in Table 4 11 Chemical formulae of no more than 8 compounds can be input at once by using comma as delimiter When input chemical formulae were incorrect in the light of the MALT for Windows notation errors will occur on retrieval When more than 8 compounds are needed use the Append compounds in the sub menu of the Search Compounds In the submenus of Get compound system or Append compounds in Search Compounds main menu select the Search by Compound The input Compound From appears like in Fig 3 8 After editing the text field to specify the compounds to be retrieved click the button Selection Then these compounds are obtained The once input data are stored in the combobox and can be displayed by clicking the pull down button of the input field 3 3 2 Calculation o
129. the best available values for respective compounds Even some are containing estimated values in the absence of reliable experimental data and some may not have a good consistency with other data Such data should be regarded as lower reliable data The reference numbers for data sources are given in appendix The followings are the ranks in terms of the reliability Rank A the most reliable thermodynamic data Reference number 1 2 5 8 9 113 114 Rank B Usable without special care despite that the reliability is not highest Reference number 11 13 16 18 19 101 112 Rank C There would be great possibility of containing a big error due to a wrong estimate 111 Reference number 3 4 6 7 10 12 17 Note the followings about the above ranks These ranks are not for the reliability of the data sources themselves These should be limited to the compounds which are collected in MALT for Windows For example those compounds whose thermodynamic data were determined in the most reliable manner were taken from the data source ranked by A The same compound in the data book ranked by C is essentially the same as those in the data book ranked by A and their data are of course the most reliable 6 3 Calculation of high temperature thermodynamic functions It is needed to make integration of heat capacity to obtain the high temperature thermodynamic functions in MALT for Windows For simplicity 298 15 K is represented by To
130. the temperature region is detected an error code is set and the calculation on the compound stops and the next compound will be proceeded 99 When PhaseNumber is set as zero calculations will be made on the stable phase of the compound If the selected temperature is out of the valid temperature range it will be an error When it is set as non zero value calculation is always made regardless whether or not the selected temperature is inside the stable temperature region Comparison between interrupt function call used in MALT2 and procedures of MALTCompoundComponent Name MALT2 MALTCompoundCo interrupt mponent procedures initialization of general mode 0 1 Initialize Selection of compound handle 1 0 GetNameRangePhase Obtaining the stoichiometric 1 1 GetStoichiometry information of selected compound handle GetStoichiometryB Obtaining transition information of 1 2 GetTransitionInfo selected compound handle calculation of thermodynamic functions 1 3 GetThermoData of compound handle Initialization of Pascal mode 0 2 Initialize Get information of compound handle 1 10 Thermodynamic functions of a selected 1 11 GetThermoDataAtTe compound at several temperatures mperatures Thermodynamic functions of several 1 12 GetThermoDataForC compounds at a selected temperature ompounds 5 3 4 Other procedures The following functions were available in the Pascal mode in t
131. ulation of changes ofthe enthalpy entropy Gibbs energy of a reaction and equilibrium constants at some temperatures As a Gibbs energy minimization program MALT for Windows has the gem program which can be run in the MALT Direct environment In Addition MALT for Windows provides a powerful tool CHD for constructing generalized chemical potential diagram This program can be categorilzed as a dual relation with the Gibbs energy minimization This program will be explained in a separate book although brief explanation is given in Chapter 3 4 4 2 Customize parameters for calculating table in a selected format The command Customize MALT setting Computation customizes the parameters for the calculation concerning the unit of temperature mass and energy temperature range and step and the format of the result table The modified setting is saved when you quit MALT for Windows 1 Customize the units 1 Temperature unit Absolute temperature unit K or Celsius unit C are available In English message C instead of C is displayed for convenience 2 Energy unit sd Malt Options Enerey unit 10 x General Computation Files AmA Temperature Range on calculation 2 g Low limit 500 00 High limit Q 600 00 Temp width fi 0 00 cal Unit of Materials 7 MV Make extraporation of phase data on calcula mol C ke ptions on calculation and tabulation C Nm3 22 V Show thermodynami
132. umbe Number of Fixation 2 3D Surface Diagram 3D Surface Diagram Dimension Selection Fixation Diagram Selection Diagram Type Diagram Type 3D Surface Diagram xf Coordinates selection N D G D Ga ze gt c Default F Gancel E Cancel 7 Help Fig 3 20 b Diagram Specification for giving the selected values for Diagram selection 3 5 4 Polyhedron approach to construct chemical potential diagram By selecting the Calc submenu in the Run main menu calculation starts and a diagram is shown if available Fig 3 21 shows the three dimensional surface diagram for the Ca O C system Three dimensional indicates that there are three dimensions which can be 39 CHD Win MALT Direct lt The kK T In P Pa O Ca system gt File F Edit E Project P View Run R Diagram D Window W Help H Fer rxe O BEA BE Aa Are fio Fromf fioo sero f 3 frel pooo a poo Yt poo ur e The C Ca system at P 1 0 atm 7 1000 00 K a ORT 90 570 50 30_ 10 5 0 5 10 15 20 25 5 30 4 35 Cao ifa 9 cpfeit 40 05 45 50 55 60 C42 65 30 at por u u En Cad ORT 91 4329 K Ve14 E 21 F 9 gt Fig 3 21 Three dimensional surface diagram for the Ca O C system at 1000 K This is the default type diagram changed In t
133. unning program can be called child process MALT for Windows provides several ways of running such a process the first one is to run MALT for Windows with other program as batch job using command line such as MALT nonmcf gemWin The second way is to use the User s Application submenu in the Tools menu Combobox One of Windows controls which are used in editing the text strings Combobox consists of list and text editing field and can provides a list of pre selected information in it Users can select one of listed items or directly input text string in the text field Command Parameters When a command will be executed in the DOS Windows the Command 114 parameters are strings that are input after the command Similar parameters can be used even in the Windows environment For example a short cut for executing a program has a property in which the name of the program to be run is given like Link to c MALT MALT CHDWIN EXE md Here the command parameters can be added after the file name to be executed In the above example md is a parameter indicating MALT Direct command The command parameters for the user s application program can be edited in the User s application menu in the Tools main menu Compound Handle When a number of compounds are retrieved numbers beginning with one are given for respective compounds sequentially This is called compound handle
134. viations In this manual and the menu screen the following abbreviations will be used for convenience of description PF ESC CHRO 1 2 Commands indicates the function key for example PF2 shows the second function key which is the same as Fe2 indicates the escape key indicates that other keys will be input together with the control key for example C means that C and the control key are pressed simultaneously indicates the number which is represented by hexadecimal for example FF means 255 in decimal number means the function which converts the number in one byte into the character type MALT for Windows adopts a menu driven system which makes it easy to operate this system Any command can be selected by the following ways 1 clicking mouse on a menu or a given button 2 Input the proper key corresponding to selecting menus or buttons Selection of menus or buttons can be made by using Tab key or arrow keys for left lt right gt up or down The escape key can be used for those cases 1 when you pressed a wrong item 2 when you want to go back to the previous state 3 when you want to step back to the upper menus 1 3 Flow of Tasks in MALT for Windows The objectives of MALT for Windows can be summarized as follows a calculate the thermodynamic table for a particular compound b calculate the equilibrium constant for a particular reaction c pro
135. vide the thermodynamic data to user s programs by means of MALT direct Tasks in MALT for Windows can be made according to the following sequence as shown in Fig 1 There are three stages 1 Select a set of compounds by retrieving the thermodynamic database MALT for Windows See 3 3 1 4 3 for details 2 Calculate the thermodynamic table or the equilibrium constants by using the retrieved data See 3 3 3 3 3 4 4 4 for details 3 Make the MALT Direct available to provide the thermodynamic data for user s application programs See chap 5 1 4 How to Recover From Errors When running the MALT for Windows many errors can happen for various reasons One of the major sources of errors is due to simple mistakes in typing for example typing roman characters instead of numerical characters to be input or misspelling in chemical formula For those errors which can be recovered easily MALT for Windows gives a prompting message to correct the input information Stage 1 Select Retrieve of compounds or a set of compounds a calculation of thermo table b calculation of equil const c MALT Direct MALT gem CHD Figure 1 1 Schematic flow of task in MALT for Windows Stage 3 j In the initialization of MALT for Windows check will be made to ensure whether the MALT environment is proper If a message is given follow the instruction Fatal errors may happen for example a p
136. was set for PhaseNo the calculation will be made by using the thermodynamic data of the stable phase at a selected temperature In this case when the temperature given is beyond the valid temperature range it will be an error When the PhaseNo value is other than 0 the calculation will be made by regarding that the extrapolation to the selected temperature was set despite that the selected temperature is beyond the valid temperature range The calculation temperature should be given at the Real value The calculation results are given in the variable ThermodataStr in the form of ASCCIZ in the following sequence unit A7H T H T H 298 kJ mol A pH T AgH 298 H T H 298 kJ mol C T JK mol S T JK mol A NG T ApG 298 G T G 298 kJ mol 5 3 3 Procedures in Delphi mode In the Delphi mode data exchange will be made in the data structure of Turbo Pascal and this provides the most convenient circumstance for users to develop their application programs Since the data is stored as the record type in the buffer area it will be required to define the same record type variable and also to keep an enough data area to store the return data If the buffer area is too small it will be an error without calculation If the actually reserved area was lower than that specified by MALT there is a great possibility that the 94 system will be out of control To avoid it use should

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