Thermodynamic Properties of Iron and Silicon P.D, Desai Center for Information ond Numerical Data Anais and Sth, Purdue Univers, We Lafaete, Indiana 47908 Recaved Api 15,1985 revised macuscrp recived September 2 195, ‘This work reviews and discusses the data on the vatious thermodynamic properties of iron and silicon available through March 1984. These include heat capacity, enthalpy, ‘enthalpies of transition and melting, vapor pressure, and enthalpy of vaporization. The recommended values for heat capacity, enthalpy, entropy, and Gibbs encray function cover the temperature range from 1 to 3200 K for iron and 1 to 3600 K for silicon. The recommended values for vapor pressure cover the temperature range from 298.15 to 3200 K foriron and from 298.15 to 3600K for silicon. These values are referred to temperatures ‘based on the International Practical Temperature Scale of 1968. The energy units used are Joules permol (J mol). The uncertainties inthe recommended valuesof the heat capac- ity range from + 1.5% to + 5%. Key words: critical evaluation; data analysis; eahalpy enthalpy of melting: enthalpy of transition; eathalpy of vaporization; Gibbs energy function; bet capacity; rom; vals sion, ‘vapor pressure Contents 1. Tntreduetion 967 2. Recommended high-temperature thermodyM@i- 2. Thermodynamic Properties of ron cweunene 968 ic properties of rom ww se Os 2.1. Phase and Structure 968 3. Recommended vapor pressure of iron 22. Low-Temperature Heat Capacity. 968 4 Recommended low-temperature heat capacity fg, 23, High-Temperature Heat Capacity (Solid) = 970 SEO nner os 2.4, High-Temperature Heat Capacity (Liguid) 972 5. Recommended high-temperature thermodyD8#"" yoy : _ 972 ie properties of silicon aoe 972 6 Recommended high-temperature thermodynas- 975 ic properties o Si(g) nd Si(8) "982 976 7. Recommended vapor pressure of 32: Low-Lemperature Heat Capacity 33. High-Temperature Heat Capacity (Solid) . 979 344. High-Temperature Heat Capacity (Liquid) 979 3S. Ideal Gas Properties. ot 3.6. Vapor Pressure Data wv 981 Ust of Figures | 3.7. Referenoes.. . 92 m 4. Acknowledgments... 983 974 ‘Heat capacity of ion een Low-temperature heat capacity of silicon ~~ Percent deviation in C; valves for silicon ~ Parrent deviation in» wales for silicon . Heat capacity of silicon... : 977 918 978 300 List of Tables 1. Reenmmende lawstompera paeeene heat eapeity af ' 968 other ther- 4. Introduction generate the recommended values of tas and othe thet ‘The principal objective of this work is to critically evaluate and analyze all the available data onthe heat capac- ity, enthalpy, and vapor pressure of iron and silicon and to © 1986 the US Serer of Commer on bebo the United Stas ‘The cro i agne so the Americ et f hye a the ‘Ameen Chena Society. Reprints valle om ACS see Reprints Lis at back of ie ‘odynamie properties from 1 K tothe melting PO above and "The dieunion ofthe thermodynamic OPTICS Sg the details of data analysis are reported in See. 2°00. inSee, 3 for silicon. The recommended values cover 5 SE, perature range from | to 3200 K for iron and from K for sicon esm0- “The temperatare dependence ofthe following 1,108 ye: Chem Rat Data Vol 18, NO"968 .D.DESAI «dynamic properties are covered (2) Low-temperature (7<298.15 K) heat capacity, Cy (2) High-temperature (7298.15 K) heat capacity, C3, (2)_ High temperstore (298.15K), and (4) Vapor pressure, P. ‘The details of the data analysis have been discussed else~ where! enthalpies, 2 (7) —F 2. Thermodynamic Properties of Iron 2.1. Phase and Structure Alpha-iron has a be structure isotypic with W below 185K, fee (y-Fe) structure isotypic with Cu between 1185, and 1667 K, and bec (8-Fe) structureisotypic with W above 167K. These transition temperatures are based on the stud- ies of Sale and Normanton.*Its atomic weight is 55.847. is focromagnetio at temporaturse below 1042 K and peremag netic above that temperature. Its melting point of 1811 43 K js based on the measurements of Treverton and Mar- rave,’ Cezairliyan and McClure“ and of Boulanger * These temperatures and thermodynamic properties reported here are based on the International Practical Temperature Seale of 1968 (IPTS-68). 2.2. Low-Temperature Heat Capacity ‘There have been numerous measurements of the lec- tronic specific heat coefficient 7 nnd the Nehye temperstore 6p. Some of them from which the recommended value is 40K) Roventand Minick” Bend andPeppeshot™ jc wall (> 80K) “Ro aO he (80K) ‘The recommended value of C; = 25.084 J mol~!K~? at 298.15 K isbased on the data of Stepakoff and Kaufmann," Grits and Grifiths,” and the lower end ofthe high-tem- perature data discussed inthe next section. Integration ofthe Pewimuneaded Cf values yields ZF (296.18 K) I7(O K) =4481 + 10} mol" and integration of C;/T values yields S* (298.15 K) = 27.085 + 0.08 J mol~! K. These values are tabulated in Table {and C: values are shown in Fig. along with the experimental data.‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON oo me RERRRARER TESS TEMPERATURE , K a a a a LOW-TEMPERATURE HEAT CAPACITY OF eg os pe ero) 14) lowe ‘ALIoVdvO LW3H Fic. . Lowtempratre heat sapaciy of con, 4: Phys, Chem. Ret. Data, ol. 16,No. 3, 1886970 P.D. DESAI 2.3. High-Temperature Heat Capacity (Solid) ‘There have been numerous measurements of the heat ‘capacity of a-iron, hese generally agree with one another upto 1000K. Near the Curie temperature, C; varies rapidly ‘with temperature. In ths region, from 100010 1060 K and in ome cage up to L185 K, comparativly large deviations in CC} occur which could be, in many cases, reconciled by cHianging the temperature only lightly. ‘The recommended C; values for a-Fe in general agree well (-£ 3%) except in the region near the Curie tempera ture region with the following measurements: Griffiths and Gifts,” Bendick and Peppethoff,* Pepperhoff and Bitwig.# Roger and Le Coze;* Kellie etal, Toushiya et al, Lyusternik,” Awbery and Griffiths,” Sykes and Ev- ans, Normanton eal, Palliser, Holetzko,"* Wallace et al,” Braun and Kohthaas,** Braun,” and of Kraftmakher and Romashina.§ Comparison of other measurements with the recommended values is as follows Source Devition % Sehode aud Maclaces* — 5300-4801), 12(40-1000%), 1451085) Lasko al 28 91 930K), ~3 (> 1070) 34 sp t06 (<1000K) 1 1070) 1<978K) 10 (> 1000 K) Bier Bette” 00) “26(S 070K) Kooy eral Varchenko eral” Curie temperature yield as much as 15% lower C values. ‘a-Fe tranforms to 7-Fe at 1185 K and then fo Fe at 1667 K. The recommended values of AH. and AH, « ate based on the following literature values: ee Me Me Semen sw Mean Beskmataetce Rerun oem ap Seren Be Baw Bowen 3 3 m Meter Sw ier mae Resaninniie 00a wT 4. Phys. Chem. Ret. Dats, Vol. 15, No.9, 1886, ‘There appears to be an excellent agreement between several measurements reported for 7-Fe inthe literature. ‘Tre evonuncindl values agice well (296) with the fol lowing measurements Sale and Normanton? Cezairiyan sand MeClure,* Dench and Kubaschewski* Normanton et ‘al. Wallace t a2” Shanks et al.** and Lapp. Other ‘measurements compare with the recommended values as follows: seers Deviation. endsk and Pepper ~Sw0—u4 Roger nt seo eae Lankor ral i Kalle 06 ‘Aster and Griihe™ a Pater Hie 0 Hotarto BT Braun” Siw -6 ‘Ores an Shrse™ a3 Koa speek Kourt™ +5 Varcesko eta to ‘The recommended C; value for5-Fe arebased onthe data of Cezairliyan and MeClure:* Data of Sale and Normanton? ‘and of Dench and Kubaschewski” are, respectively, 2% to 59% and 2.39% higher dun de recommended values, and those of Braun” and of Morris et al’ are up o7% and 99% Tower, respectively, while those of Holetzko"*are as much as 36% higher. “Assystematic plot of percent deviation (upto + 496) in CC values from various measurements is shown in Fig. 2. In addition to the direct C; measurements, there are several enthalpy studies reported in the literature. These ‘compare with the enthalpy values obtained by integrating the recommended C; values as follows: Sours Deviation, ‘deo an Huge” 213 Ferrand Otte” wpe -2 Moral" S03) Seger fal iis Rapes was Patton and Wilows” 3) Uniee™ = 4(<1185 x) BiGnsK), Uninc” = 25(cinssK) wast eral = Obert ad Grom!" Fi‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON, ort TT TTT Ysnasgsorresseeas a, 2 Percent eviaton in; vals fon. «4 Phys. Chem. Ref. Data, Vol 16,No. 3, 1886972 P.D. DESAI 2.4, High-Temperature Heat Capacity (Liquid) ‘The recommended value for the enthalpy of melting, Aig AP = 14810 4 300 T moll, was obtained hy exteapo- lating solid and Tiquid enthalpies to the melting point, Tro, = 1811 K. This compares with the following values re- ported inthe literature: Soure Bai Ima Bran and Kas” 14400. 300 Morn eral" brea Uniao™ 16170 Uninc 1530 West erat Hs (Oberle and Gres 15083 “Teveon sed Margrave! 1864300 ‘Mogetunor and Tomin'® br Vollmer eral” M3400 ‘The following investigators have reported constant values for the C; of molten iron from their enthalpy measurements inthe limited temperature range: source jdm Kt exo ‘ ‘oat “Treverton and Margrave? ‘3062 +021 ‘Mogutuaor and Toa 696 Walle ea 20 Marana teats Cheyne” no Recommended vac son 230 (Other quantition in Table 2 are oaloulated by integrating C3 values. The recommended enthalpy values for liquid iron agree within + 2% ofthe data of Ferrier and Olette.* Mor- riser al, Pattison and Willows,” Umino,” and of Trever- ton and Margrave. The data of Umino* are up to 696 high- cer than the recommended values. ‘The recommended C; values reported in Table 2 are shown in Pig. 3 along with Cnperimental date. Other quanti= tics in Table 2 were calculated using the procedure outlined earlier The estimated uncertainties in the heat capacity are 3% below 10K, 1.59% from 1010 298.15 K, + 29 from 298.15 to 1000 K, + 5% from 1060 t0 1185 K, + 2% from 1185 and 1667 K (7-Fe) and 1667 to 1811 K (6-Fe), and ++ 3% in the liguid region. However, uncertainty near the (Curie temperature is as much as + 10%. ‘Thermodynamic quantities for Fe(s) reported in Table 2 are calculated from C's (g) and S° (298.15 K) (g) values ‘reported in Chase eral ® 2.6. Vapor Pressure Data Application of the third law test tn the vapor pressure ‘measurements gave the following enthalpy of sublimation at 298.15 K. «4: Phys. Chem. Ret, Dat, Vol 15, No.9, 1996 Sth an Shateort ‘Nesmeyanov and Trapp 1327-1518 K, Knudsen tod Mylan Aldred 1481 1077 Kiwdeen method Sune” 1507-1657 K, ‘Kneden method Langmuir method “Torkdoan and Leake" 173K, “Transport method Spier eral.” 1725-1826 K, Calcltd fom Knudsen method for FeNialle ci a 07 urlako. 1302-1508 K, Tangmuie meted nama, anon 1360-1528 K, Taotpe exchange method Mortis eral," 1810-1889K, “Transport method Vien” 1400-1600 “Kandeca method ener” 464-165 K, ‘Knudsen method awards eral" 1356-1519 K, Wess" 1500-180, ‘Kndsen method Marshal a 1317-1579, Tangri method "Tang method Aleock and Kubik." 110-1895 K, ‘Kovdecn method Linsene ana Lange 1765-1870 K, Kaan method 17-1870 K tasioa method Syazhin of a, 199-2368 K ‘Gamer ps transportation method Karasey eta 197-2023 K, ‘Braporton method "Cate as transportation method ‘Chega 1273-2200 K, pmo method smasene aa Lane 1622-1878 K, Kawase method 162-1875 K, eson method Nemets and Nikole 1478-1655 K, ‘Ateorpton met Recommend vloe 3 efP (985K) KI mal“ smn07 21.26 s1797 4 1.09 aunsis0 exo aisg2 asda 66342 1667 2038 answer oss 18122096 os 2281 0s sono7 2236 416732013 41343 2428 sinay $28 270 040 sn1s6322 08 2 1.0 1309 4220 ‘1470228 03652252 sisa7 2128‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON 973 4 Phys, Chem. Ret Data, Vo. 15, No.3, 1006“won p Ope YH CoH > SunuvesanaL, (2091_o0s!_oov1_oott 001 006 008 202 00 005 00% 08 008, oa2e_0012 0002 _o0st_o P.D. DESAI *aLlovd¥o L3H ow e 4. Phys. Chem, Ret. Data, Vol. 15, No.3 1888‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON 975 Sigge s323 ta tne yg nF nt Ty nny ae ‘The values for AG", p, and AA” reported in Table 3 are caleulated using Ajo (298.15 K) and the Gibbs energy values for Fe(s1) and Fe(g) from Table 2. ‘Most of the measurements for the thermodynamic properties have been carried out on the International Pract cal Temperature Scale of 1948 or 1958 (IPTS-48 or IPTS- '58). It is worth noting that the effect of conversion ofthese properties to IPTS-68 is well within the uncertainty ofthese values. 2.7. References D. Dea. “Thermodvaamic Pronertis of Alsmioum. Nike. and tani "I Phys, Chom, Re Dats (tbe polished). FR Salesnd AS. Normasio, "A Sphere Adabalc Calorimeter, ”in ‘Metlluyieal Chemistry Spam 1971 (Nataal Phi Laborato. 'y, Teingon, England, 1972), pp 19-2 tev ante arene )Cnet tnermooye. 9873 191) “A, Cezailiyan and 3. MeClure, J Res, Natl Bur Stand Sect A, as) SC. Boulanger, CR. Aca Se. 24, 133 (1985). London Ser A 285,56 (1965). TCH. Cheng C-T. We snd PA. Beck, Phys Rev. 120, 426 (190). {58 Shino and A. Arrot, Phys.Rev. 182, 61 (1966). PA. Arrottand. Shinotali Ann: Acad. Se ean Se-A210, 3 (1966) "K Marklund, L- Hoel, K Spa and TLindgrt). Low Temp Pay, 21cm), "Wh Mazur and W. Zacharho, Acta Phy. Po. 32, SO (1967). ‘5. Arp D. Eémonds, and .Petere, Phy Rev. Lett, 212 (195). ‘SW. Kes el . Kasikoye, Physica The apie) 6 639 (1939) 4G. Duyeaets, Physica (The Hague) 6 40 (1938) "A, Baoten and H. Werth Z.Anorg All Chm 88, 152 (190), 5G. LStepak and L- Kaufman Acta Metall 16 13 (1968), PACK. Kalley. 1. Chem. Pigs HL 16 1965). YF Sion snd RC. Swain, Z Pips. Cham. AbB 28,19 (1938), EH. Gris and. Grits, Proc R Soe. London Ser. A 9, 587 cs, BP. N. Roddy and P.J. Rey, Phys. Stats Soli A 22,219 (197). 2K, Somoder and W- Me Melons, 3, Soh Instr Supp 3,3 99 (969) "2-H. Rodebashand J.C Michalek J. Am, Chem Sa. $,2117 (1928) 2p. Gunther, Ana Phys (Pars) 5, 28 (1916. 2. Benick and W. Peper, Acta Metall. 30679 (1982), ‘W. Popes and HH tig Z: Angew. Phy. 22, 96 (196), 24) Roger and. Le Cone, Ret. Pays. Appl 5,31 (158). PL Nitarko, Yo V. Uso, ad A.V. alos, Metlorika (75), 55 (om, 1.6, Kote D.L MCE, M. arbnl ana C.K. Brooks, ORNL ‘Report No. ORNL4380, 196, 3 pp. [N27239) Md. Touchva, M Tumijama, and Y. Lma J. Jp, Inst. Mt 38, £39 cm, 2V. Ye Lost Phys Met Metals (USSR) 19, 48 (3565). >. A, Deck and O:Kubsschewsk J ron Stel Ist. London 20,140 «1963, 21.H. Avery and. Grif, Pros R. Soe London Se. A141 (1940). 2G. Sykes and H. Eran Ton Sel ast London 138 125 (198) »K.8'Nommanton,P-E Bloomfield FR Sle abd BB. Arpt Mi Sl 13,310 1978) P.R.Pallse, J oe Sel las London 161, 87 (1949). MHL Hoek, dseration (Univesity of Koln, 1958); quoted by F. D.C. Wallac, PH. Soy and ©. C. Danian, J Ap. Phy. 31, 168 (1980) 2M Beacn and R.Kohthas, Phys. Stats Soi 12, $29 (196). 2M Beaen.Inaunaral digeraton (ninraty of Kon 060 ‘LOreotay and Ke Shvder, J Phys E389 (1970) "H.R. Shanks, AH Ken, and G,C. Danson, J. Appl: Phys. 38 2885 (6) ‘PT.G. Kalle, ORNL Repoct No. ORNL-TM-1187, 1955. *D.L Meloy, PD. hess (Unters of Tense Roast, 1997). “"Ya.A- Kraft and T- Ya Romain, Terd Tela. 7.2532 (195). ‘SH. Rlinkbard, An. Phys. (Par) 84 167 (1927), ‘SC. Lapp, Ann: Phys (Pais) 6 #261936) ‘2H Raneeand H. Boeck, Aso Bvehuteny. 1, 67 (194). “K. Kobaya. Ohmor and Y. Fujimura, High Temp-HighPresares 11,489 (1979), “A.A. Varcheako, Ya A. Krafimaer snd T Yu Pinca. High Temp, (USSR) 16,720 197. ME. L Lederman, MB. Salamon and L. W. Shaklee, Phy. Rev B9, 2oai (1978), P,D, Anderson and R. Huligte, ran. Metall. So. AIME 224, 842 (196), 8M Okt and A Ferien The Pye Chen o Mel: uations ‘and Inermerlc Componds (National Physical Laboratory, Teng fon, England, 1959), Spmposiam No 8, Pape 4, p. 100-103 ‘2A: Peer and M, Ot CR Acad. S264 222 (1962), Mins Rep inves. 6723 (196) ‘FM. Jeger, E-Rosnboin and A. .Zalhof,Ree. ray. Chim, Pap Bas 7, 1313 (1938), RL Ragen, M. 8 thesis (Ai Fore Iai of Technology, WPAFB, Tbe) (Senecio Epes Report No. GME/ME/OS-1) °K. Patison and P. W. Willows, J. ron Sel Ist. Lacon 13,390, 1956), 9S, Umino, Set Rep. Tohoku Imp. Univ Ser. 118 911929) 295 Unie Sat Rep. Panes p Une Boe} AF £27 (1930 r, Wos A. Meaibn, sR: Deer, Fench Oc. ngeicures.VDI- Forsch 204 (191). ‘SP. Obeoler and W. Gres, Sal Ese 7,76 192). (91.4 Tetrion an: Margrave Chem. Thermodya, 3,473 (197). ‘°B.M. Mogutusoy and L-ATomln Ie. Akad Nase SSSR Met 6,25 (i960) “0, Volt, R Kohan, nd M, Beau, 2. Natrorch Tl A21, 181 (1966) “6h LeManpiare Ric Univesity Repo Mu NT1-20542, 1970 “nt. W. Chae J, 3L. Cart 1.R Downey, J, RA: McDowall, A.N, Syverad;andE-A, Valenzuela, J Phys, Chem, ReData 1,695 (192). ‘°R Sith and RE Shutdeworh, Trus, Metal. Soe. AIMIE 233, 806 “IN: Nesmeyanov and G. Trapp, Zh. Fi Khim. 38293 (1964) [Rost J 4 Phys. Chem, Ret. Data, Vol 15, No.3, 1686976 P.D. DESAI Phys, Chem, 38 (12), 1883 (1964). SKM MylesaedA.T- Alte, Pigs. Chem. 6, 64 (1961) RK Suter, PRD. this (Oho State Universtiy, 1962) [Unw. Miro: fas No. 81. “°ELA Galbeansn and K.F Anew, Trans Metall Soc. AIME 21, 1247 36h), ELT. Torkdogun and LE, Leake, Trans Metall. Se. IME 218, 136 (1960). PR. spt, A 2 Deeb and JW Spsah Trane, Meal Soe. AME. 28 1851959), %C.L. MeCabe, R. G, Hudson, and H.W. Panton, Tras. Metall. Se AIME 21, 1021958), V.D. Burak. Fiz. Met. Meulloved £91 (1957) (Phys. Met. Met loge (USSR) 8,7 (1957). LLL Ivano, thesis (Meallrgy Instie, Academy of Sciences of te USSR, 1937), "1.P. Mom 6, R. Zell. Payneané RL Kipp, US. Bur Mines ep. vest. 384 (1997). ‘ME 7. Vintatin, Dokl Aka Navi SSR 117, 632 (1957) Ye. V-Komev, Probl. Metalloved. Fiz Met 32 (195), "3. dwar HL Johnon, and WE. Ditmas, Am, Chem So. 75, 1G, Wessel 2. Phys. 130,539 (188. ‘OL 8. Dasken and RW. Garry, J. Am. Chem. Soc. 6, 798 (1946). ‘AL. Marshall RW. Derm, andF. Noro, 5 Am. Chem, Soc 88, isi isan. MHA. Tones, L Langmuir, ae G.M. J. Mackay, Phy. Rev. 30, 201, 2m) CB. Alcock and A. Kubik, Tras, Is. Mining Met See. C77, 220 (4968), {ph neenea ano. Fangs 2. Meta 199970), "A.G.Sryahin, AF. Vihharer and V.1 Yor, Russ Mall 8,42 (968), ‘Yu. A Kersey, L. Sh Temekiman, and. Vaiburd, Rs. .Phs V.T Yavojl, AG. Seyzhin, A. F Vighare,N.K. Pi B.A. Ro- ‘asovih and G.M. Chain, Rass Mell 3,24 (197%). ALL, Chegoey, .L.Dubiia AL Tiofey, NA. Valli and V1. ‘Kapitan, Rus J: Phys, Che. 82 1229 (197). ‘pH Lindched and KW. Lange Z- Metal 66546 (1975) A.M, Nemes a6. Nokolacy, J Appl. Spasrose (USSR) 21, 145, Gore), PV. 1 Cetin LN Zed, and Ye. Vabur, lah i. Zh, 34,870 (0) 3. Thermodynamic Properties of Silicon 3.1. Phase and Structure Silicon has an fee (A4) crystal structure isotypic with diamond." Its atomic weight is 28.0855 and melting oint is 1687 2 K (IPTS-68). The melting point is based on the following measurements (IPTS-68) Soar Laas and Urtin? 68521 Kantor eral? lone Oust" sts Gaye e052 Hofinan and chute? as £2 4 Phys. Chem. Ref. Dats, Vol. 15, No.3, 1008 Pons, soe sess mamas tata 3.2. Low-Temperature Heat Capacity ‘The recommended values agree well with the data of ‘Keesom and Seide, Fubacher etal,” Kalishevich el," and of Anderson."' The data of Gultyaev and Petrov" are up to.4% lower and those of Russell” are up to 6% higher ‘near 300K. Additionally three datasets reported eraphical- ly in small igures which appeared tobe one-and-the-same investigation by Letun eal, Geld and Krentis,” and by Letun and Geld" are in fir agreement with the recom- ‘mended values. The data of Pearlman and Keesom'” are up 10309 higher below 4 K, 7% higher from S0to 100K, agree slightly higher from 12t0 50 K. The recommended valves of Cj arein agreement withthe values of Hultgren ot a¥ and of Glushko er al" Within the experimental uncertainty, the electronic specitic heat coeficint 7 is equal 0.000 mol" K~? and Debye temperature 6, = 631 K. Mertiget al" reportaval- ‘ue of $28 + 20 K for the Debye temperature of amorphous silicon. Integration of the recommended C values yield IF 29015 W) — IP OK) ~ 32143 mat" ead tegration of C3/T- values yield S* (298.15 K) = 18.806 (+ 0.08) Jmol! K~ which are in agreement with those recom ‘mended by the CODATA Task Grouo.” These values are reported in Table 4 and C; values are shown in Fig. 4 along with the experimental data‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON 977 J T T Ty 1 | 8 5 steanee g i— 8 = RS Ee rt zs g > gE ae) e©oz wos ago | 8 2&5 Wot | Foo 7 t 8 a< i 6 wi e 3 le | = 7 i ; | Ze 8 © 2 8 @ ee we 4 11 JOw er “ALIOVED L3H & 4 Phys. Chem, Ret Dats, Vol. 16, Ho. 9, 1886TT TT I | PERCENT DEVIATION IN Ch VALUES FOR 4 SILICON =) DEVIATION , % Fic. 5 Perent deviation nC; vals for sion, * rriritty 40 | PERCENT DEVIATION IN lene 7 y VALUES FOR 20 4 SILICON Xe \ Zz ] & oe B 00 3 yA NT | # +0 ll a 20 1 30 T t ae Tn 1687 K: -50 1 ! 1 200 800 1000 1200 1400 1600 TEMPERATURE , K‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON. 979 3.3. High-Temperature Heat Capacity (Solid) ‘There are only afew data sts availabe in this tempera ture range. The recommended C; values are generated by critically evaluating heat capacity and enthalpy data simul- taneously, Agreement between C; and enthalpy data avail- fable in te literatuse nd the reconnended values i 3 fo! lows: Source deviation, Kantoreral? spa Halen eal spo 08 (<700K) Spt — 10(> 1000) ‘Guba er al” ey ea0K North and Gleb!” wpe Diam ctal™ Yt 10 (cater cmidersby) Krona etal?” spo Geshe al wes Sotcee deviation, Kantor eral? aa —12 Ole! wre i0 Sercbremikovand Gt upto 35 (< 800K) spto ~ 10 (580K) Magnus” wpe ~ 10 ‘A systematic plot of percent deviation in C; values from various measurements i shown in Fig. 5. A systematic plot ‘of percent deviation in y valuee y= (E (1) — HF (298.15 K)/(T 298.15) from various measurements is shown in Fig. 6. 3.4. High-Temperature Heat Capacity (Liquid) ‘The recommended value for the enthalpy of melting, Sy = 30 230 00 J MOL * was oDtained oy extrapo- sans 500 in) tee 3t00 har.ete uasasy aaa aaa hissy wisn «4: Phys. Chem. Ret. Data, Vol. 15, No.3, 1986P.D. DESAI 980 on 001 __of9 008 00 _ 08 _o02,, wooys yo noes HL ot Jour ‘ALlovdvo 1v3H 4 Phys. Chem. Ret. Data, Vol 16, No.9, 1986‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON 981 146.398 note lating solid and liquid enthalpies to the melting. point, Tyg = 1687 K. This compares with the value of 50000 ++ 750 Jmol reported by Kantor et al:* and of 50 600 4: 400 Jmol given by Olette* C; (1) = 27.200 “1.603 mol! .~! was asoumed tbe constant to the boil {ng point based on the constant value 29.71 J mol" K' of Kantor et al, 25.52 mol” K~* of Olette,* and 26.20 Jmol~! K-" of Chetykhin eal ‘Other thermodynamic quantities reported in Table 5 recalculated from C; values, The recommended C; values are shown in Fig. 7 along with experimental data. ‘The cstimatea wawestaintins i the heat aponity ate about 3% below 10 K, + 2% from 10 to 298.15 K, + 3% from 298.15 to the melting point, and 4 5% in the liquid region. 35. Ideal Gas Properties Thermodynamic quantities for Si(g), Si(8),, and Si(g)reportedin Tables Sand 6arecaleulaed from Cand ‘5°(298.15 K) values reported by Glushko eral.” for Sig) and Siz and by Brower" for Si ‘Brewer's saloulation for f(s) was prefered since it provided a smaller vibrational parition function. This is ‘based on theoretical calculations indicating thatthe bending frequency, which s very anharmonic, should increase rapid- ly asthe end atoms start approaching one another more clo- sely with higher vibrational energies. 3.6. Vapor Pressure Data Various vapor pressure measurements were tested with the aid of the third nw At axporimantal tomparatinn the ‘vapors predominantly monatomic Si(g) (99% at 2000 K), ‘Thesenumerical third law calculations yielded the following SH? (298.15 K) values: Seer AMP CRIS) mal! Chegedaes ral.” T-203K, 4446432 Evaporation method Nanci 189-1527 K, ss1as 22 anemic method deen tod Greve and Akock"* 160-205, 44814444 “Tampon method stort and Sous" 178-100LK, ——45509:422 Tangri method 4: Phys. Chem. et. Data, VoL 15, No.3, 088982 P.D.DESAI Gufbransen eral, 1373-103K 810427 ‘cock and Grewson™ 1680-IT8SK, 481.01 4021 Knudsen method Drowart and De Maria ?* 1703-2160 K, 44737 4068 Mass spectrometer Bodeov el,” 1687-2085 K, ssras 14 "Ato lap tia ‘Teepyaea eral 1488-1893 K, smo7 Lt ‘Kondeen method ‘Bur apd Bruner,” 1980-2100K, 37419437 Boling pint metho Rufand Kontchak." 2163-2468 K, 36263 + 106 ‘Boling pint method “Transport metho : Recomended vale 4000340 ‘Stull etal indicated that earlier boiling point mea- surements yielded considerably lower A.A (298.15 K) values possibly due to decomposition of the alumina and silivou varbide wntaers. Recently Bodrov er af” potntea ‘out that these lower values might be due tothe formation of ‘SiO. Therefore, no weight was given to these low values. For completeness ofthis report. the values for? = Ported in Table 7 are calculated using 4... (298.13 K) and the Gibbs energy values for Sis) and Si(g) from Table Sand yp df' (298.15 K) = 294 972 mol for 1/2Siand Byedf” (298.13 K) = 212 0005 mot for 1/3 Sy, both val= ues taken from Stull eta? 4. Phys. Chem Ret. Data, Vol. 15, No.3, 1906, SiG =SiXg 1m) AogHP (29813 K) = 450000442 Paani TK SIU OK) = S664 a ae ATS OSBK) = 1093041 gw ay toot Biel) =1/284(6 atm) ae erry 0, eta] Ai Q9RISK) =294972263 alu (OK) = 73556, toss ee Sis!) = 1/3 Su(et atm) ie wo 208 ALIPOISK) =2004 160 10" 3a BL (0K) #21056, to! 2990 1 3490 ‘Most of the measurements for the thermodynamic properties have been carried out on the International Practi- cal Temperature Scale of 1948 or 1958. It is worth noting that the ettect of conversion ofthese properties to IPTS-68 well within the uncertainty ofthese values. 3.7. References “W.B. Person, A Hondbvok of Late Spaings and Siractre of Metals and Alay (Pergo, New York, 198), VoL 2 SLD. Laces and G. Urbain, CR. Acad. et 28, 24141962), PD Kantor, AN. Kis and N- Poin, Uhr PZ (Uh. BL) 5,388 (1960). {MOlete CR. Acad So. 244,103 1957 °M, Hansa, HUD. Keer, and DJ. MePhereo, Trans, Am. Soc. Met a sisci9s3) SLL. V Gaye, Nature (London) 142, 478 (1938) 2. Hofman and A. Schulze Ph 2.38, 91 (1938. {P-L Keesom nd G Sie, Phys Rev. 113,53 (1959), °. Flobacher, AJ. Ledbetter and JA, Morison Phils Mag 8,273, "9G:1 Kathie, .V.Gerd, and RP Kren Rost. J Phys. Chen. 38, 102 1965). CT. Anderson, J. Am. Chem. Sc. $2, 2301 (1930) AS. Rossl Ps. 2.1, 590912). SM. Letn, PV. Ge, and N,N, Serebremikoy, Russ. Metall. 6,97 (1968), RV, Geld and RP. Kent in Exorimentl Tchngus and Methads Sor bigh Tempera Measurements (Naka, Moscow, 1960), pp. 197= 2a, "EIN Lewd. VG Er Mara Atd Nev Go Sa Ce Se lugen be Lt Hooton Ge, K Kee, ‘dD nee Sn a Maden Pope Benn alt aa OH wend Wr Ran V VV A Mab Uo Revd. Yopan, Thomann Pope of nial Seance gh Tepe ate dey chateeUsa Moo,,Va “Rep te CODATA Tak Gro Chan, Tero. 18, 93 ha wt Nr an Kei Com Bal. 659 (98, 2p Dm ee Fn Re 9 ne Tel eR iD Rn ad F Sic, “Terme ae ‘Sr rine Cnrten RCA Lanter Qu ope Re pe bo taba 33‘THERMODYNAMIC PROPERTIES OF IRON AND SILICON 983 Pr, Koruna, R:Hasepe, and T. Yogic Tram, Nat, Re, Im. Mets (Teyo) 7,22 (1965). a Gove 8 Abn se Mil 1 Ap Phye 34,76 (1968) ™D,H. Dennison, lsitutfor Atomic Rescate, Ames, A’ gute by H. Shanks PD. Maycock, P. HS and GC Dario, Phy Rev. 230, 1743 198). NM Serbvenniiy and PV. Get Dot. Aka, Nauk SSR 7, 1021, (1933), A, Magn Amn. Phy. (Leis) 7,303 (1923) Ve M: Goleta and EG Maser, Rss Met (2), 1291968), AL Chega, E L Dain, AI Tole NA Vali, and VL ‘aptanan a 3. Dy Chern £3, 122 (197) 2Y, Nannich Jp J. APpL Ps 2386198). 28. G. Deis DF Antrop and A. W.Seary, J. Chem, Phy. 3,659 (i960, DP. Grieveson and CB. Alcoa in ctl Cras ete by P Popper {Geywood London, 1960), pp. 183208, DRL Bate an FM. SJ. Ap Phy. 30,259 (1989) ELA. Gulbraas KF Andrew. and. A Brass. Bketrochem, 13, 194 1860), 20 is lek ane neve, As MeL 90 1981) i. Deowar and G. De Marin Prceding ofthe Conference o Sion Carbide 3. O'Connor and), Sites (Pergamon, New York, 1960), pp 16-2. NV Boon G1 Nikaae, and A.M Nemets, Inorg. Meter (USSR) 18,639 198). AV. Tugyner, Yu.A. PslioyandV. V. Karin, Vestn, Mosk. Univ 18, 36198). 2*e Baur and R.Bruer, Hel, Chi, Aca 17, 958 (1934), ‘70. Rotfard M.Kensbal, Z Eerste, 3313 (1920) “HL Van Wareberg, 2. Erosion. 39, 482 (1913) “°D, R. Sul and H, Prophet JANAF Thermachemiel Tables, 2nd ed, (WS. GPO, Wasingoa, DC 1972), NSRDS.NBS 3. ‘OM Mee Poms and F Hogarth, Sd Ste Commie 48, 260 980, “L Brewer (pits communications, University of Cari, Betsey, ose) “VI. Chey, ILN. Zein, ond Ye Vaud Tah. i 2h, 3,870, sm, 4, Acknowledgments ‘This work was supported by the Ofce of Standard Ref ‘erence Data (OSRD) of the National Bureau of Standards (NBS), US. Department of Commerce. Part ofthe docu ‘mentary activity essential to this work was benefited from the comprehensive data base of the Thermophysical and Biectronic Propertis Information Anulysis Center (TE- IAC), whichis supported by the Defense Logistics Agency (DLA) of the US. Department of Defense. The author wishes to express appreciation to Dr.John R. Rumble, J. of| the NBS/OSRD for his guidance and (o Professor Leo Brewer of the University of California for calculating ther- ‘modynamie properties of Si, The assistance of Mr. S. T ‘MeDowell for graphics, and Mrs. D. M. Lenarts for yping is also acknowledged. 4. Phys. Chom, Re Data, Vo. 15, No.3, 1988