!DATA FILE TO DESCRIBE Titanium Tetrachloride (TiCl4) OXIDATION OR PYROLYSIS ! !v1.0_20051103 ! !This file is formatted for use with the CHEMKIN EQUIL software (versions 3.7b !and earlier; see www.reactiondesign.com for more information). !Valid temperature range of polynomial fits: 298 - 3000 K ! !All heats of formation are given in kcal/mol. Entropies are given in !cal/mol/K ! !USES: This file provides thermodynamic data suitable for modeling the gas-phase !oxidation of TiCl4 from O2 (or air), including typical CVD pressures and !temperatures and with or without H2O. They may also be used to model the !thermal decomposition (pyrolysis) of TiCl4 in the absence of O2. However, the file !does not include species needed to model NOx formation. Inert carrier gases !(He, Ar, N2) are also not included. These may be obtained from the CHEMKIN !Thermodynamic Database. !This file uses thermochemistry for TiClx (x=1-3) species that corrects errors !in data published in the JANAF Tables (1985 edition). In particular, the data !of Hildenbrand (1996) are used, for which the heats of formation are !substantially different from those reported in JANAF (e.g., -128.9 kcal/mol for the !delHf298 of TiCl3 vs -118.9 kcal/mol in JANAF). ! !All heats of formation are given in kcal/mol. Entropies are given in !cal/mol/K ! ELEMENTS H O Cl Ti END SPECIES TiCl4 TiCl3 TiCl2 TiCl H2 O2 OH HOO H2O H2OO HOOH H O Cl Cl2 HCl END ! THERMO !TiCl: DELTA_H 45.3 kcal/mol !SO 62.6 cal/mol*K TiCl 40196Ti 1Cl 1 0 0G 300.000 2000.000 700.00 1 0.54005651E+01-0.75500616E-03-0.18307549E-07 0.25760144E-09-0.72498810E-13 2 0.21195063E+05 0.89596695E+00 0.42374363E+01 0.30856631E-02-0.17249985E-05 3 -0.48162478E-08 0.43059666E-11 0.21420799E+05 0.65626817E+01 4 !Data from D. L. Hildenbrand "Thermochemical Properties of Gaseous TiCl, !TiCl2, and TiCl3" High Temp. Mater. Sci. Vol. 35, p. 151, 1996. ! !TiCl2: DELTA_Hf -47.0 kcal/mol !S0 71.0 cal/mol*K TiCl2 40196Ti 1Cl 2 0 0G 300.000 2000.000 500.00 1 0.73957505E+01 0.32238199E-03-0.37277763E-06 0.18556560E-09-0.31996300E-13 2 -0.25894832E+05-0.64782686E+01 0.68304868E+01 0.28625240E-02-0.25691154E-05 3 -0.34222591E-08 0.46921612E-11-0.25811361E+05-0.38843935E+01 4 !Data from D. L. Hildenbrand "Thermochemical Properties of Gaseous TiCl, !TiCl2, and TiCl3" High Temp. Mater. Sci. Vol. 35, p. 151, 1996. ! !TiCl3: DELTA Hf-118.9 kcal/mol !SO 81.6 cal/mol*K TiCl3 40196Ti 1Cl 3 0 0G 300.000 2000.000 700.00 1 0.96783991E+01 0.51349140E-03-0.26299205E-06 0.22587961E-10 0.99088032E-14 2 -0.62773215E+05-0.14279404E+02 0.81944485E+01 0.55063856E-02-0.24422889E-05 3 -0.70140658E-08 0.61338100E-11-0.62492023E+05-0.70820851E+01 4 !Data from D. L. Hildenbrand "Thermochemical Properties of Gaseous TiCl, !TiCl2,and TiCl3" High Temp. Mater. Sci. Vol. 35, p. 151, 1996. ! !TiCl4: DELTA_Hf -182.4 kcal/mol !SO 84.8 cal/mol*K TiCl4 51596Cl 4Ti 1 0 0G 300.000 5000.000 800.00 1 0.12202298E+02 0.10031968E-02-0.47788586E-06 0.98778825E-10-0.74164655E-14 2 -0.95592891E+05-0.27433811E+02 0.90492020E+01 0.10305555E-01-0.50740919E-05 3 -0.73819519E-08 0.60543853E-11-0.94893984E+05-0.11671705E+02 4 !Data from M. W. Chase et al. J. Phys. Chem. Ref. Data Vol. 14, Suppl. 1. H 110203H 1 0 0 0G 300.000 4000.000 1000.00 0 1 0.25002636E+01-0.18249512E-16 0.17497303E-19-0.59119760E-23 0.64865579E-27 2 0.25461811E+05-0.46000672E+00 0.25002636E+01-0.26020852E-16 0.56806237E-19 3 -0.50744043E-22 0.16250734E-25 0.25461811E+05-0.46000672E+00 4 ! ! Comments for H 2s: ! ! delH(298.15 K) = 52.1 ! S^o(298.15 K) = 27.39 ! !Reference: Melius, C. F. and Binkley, J. S. 21st Symp. (Int.) on Combustion,3, The !Combustion Institute, 1986, 1953. ! ! OH 110203H 1O 1 0 0G 300.000 4000.000 1000.00 0 1 0.29134841E+01 0.90524853E-03-0.16263449E-06-0.24605143E-11 0.23525731E-14 2 0.38182328E+04 0.47601723E+01 0.35712585E+01-0.42177554E-03 0.76837334E-06 3 -0.51450160E-09 0.25263549E-12 0.35915882E+04 0.11860574E+01 4 ! ! Comments for OH: ! ! delH(298.15 K) = 9.2 ! S^o(298.15 K) = 42.60 ! !Reference: C. F. Melius, unpublished results. ! ! HOO 110203H 1O 2 0 0G 300.000 4000.000 1000.00 0 1 0.35284308E+01 0.32157656E-02-0.13123652E-05 0.25755227E-09-0.19701603E-13 2 0.56355046E+03 0.63528834E+01 0.34665987E+01 0.15117871E-02 0.44257758E-05 3 -0.58594655E-08 0.21249859E-11 0.66497516E+03 0.71177468E+01 4 ! ! Comments for HOO 2A": ! ! delH(298.15 K) = 3.6 ! S^o(298.15 K) = 54.58 ! !Reference: Melius, C. F.; in S. N. Bulusu (Ed.), Chemistry and Physics of Energetic !Materials, 1990, pp. 21-49. ! ! H2 110203H 2 0 0 0G 300.000 4000.000 1000.00 0 1 0.31896080E+01 0.27740389E-03 0.20118562E-06-0.88552371E-10 0.97193639E-14 2 -0.89069359E+03-0.24981142E+01 0.35893855E+01-0.62211460E-03 0.15289933E-05 3 -0.16447223E-08 0.73782262E-12-0.10398926E+04-0.46873674E+01 4 ! ! Comments for H2: ! ! delH(298.15 K) = 0.0 ! S^o(298.15 K) = 31.06 ! ! ! H20 110203H 2O 1 0 0G 300.000 4000.000 1000.00 0 1 0.26334960E+01 0.30924888E-02-0.91926140E-06 0.12407051E-09-0.59725634E-14 2 -0.29880452E+05 0.77207339E+01 0.43090803E+01-0.28955226E-02 0.85302367E-05 3 -0.75132288E-08 0.24942557E-11-0.30302584E+05-0.66982081E+00 4 ! ! Comments for HOH: ! ! delH(298.15 K) = -57.8 ! S^o(298.15 K) = 46.37 ! !Reference: Melius, C. F. and Binkley, J. S. 21st Symp. (Int.) on Combustion,3, The !Combustion Institute, 1986, 1953. ! ! H2OO 110203H 2O 2 0 0G 300.000 4000.000 1000.00 0 1 0.46804449E+01 0.43348645E-02-0.15555614E-05 0.27010821E-09-0.18458640E-13 2 0.60496392E+04 0.19685855E+00 0.22303988E+01 0.15486756E-01-0.20319178E-04 3 0.14141851E-07-0.38284306E-11 0.64723370E+04 0.11679673E+02 4 ! ! Comments for H2OO NONPLANAR: ! ! delH(298.15 K) = 15.2 ! S^o(298.15 K) = 56.07 ! !Reference: Melius, C. F.; unpublished data. ! ! HOOH 110203H 2O 2 0 0G 300.000 4000.000 1000.00 0 1 0.42481037E+01 0.42678084E-02-0.15274834E-05 0.26462419E-09-0.18049363E-13 2 -0.17773716E+05 0.26212778E+01 0.32989584E+01 0.81693450E-02-0.69788501E-05 3 0.32593293E-08-0.51377897E-12-0.17607747E+05 0.71275857E+01 4 ! ! Comments for HOOH: ! ! delH(298.15 K) = -32.5 ! S^o(298.15 K) = 55.87 ! !Reference: Melius, C. F.; unpublished data. ! ! O 110203O 1 0 0 0G 300.000 4000.000 1000.00 0 1 0.25002636E+01-0.18249512E-16 0.17497303E-19-0.59119760E-23 0.64865579E-27 2 0.29165937E+05 0.40926673E+01 0.25002636E+01-0.26020852E-16 0.56806237E-19 3 -0.50744043E-22 0.16250734E-25 0.29165937E+05 0.40926673E+01 4 ! ! Comments for O 3P: ! ! delH(298.15 K) = 59.4 ! S^o(298.15 K) = 36.44 ! ! O2 110203O 2 0 0 0G 300.000 4000.000 1000.00 0 1 0.30715933E+01 0.16557108E-02-0.79202103E-06 0.17408653E-09-0.14457201E-13 2 -0.10002600E+04 0.65815300E+01 0.37508882E+01-0.23577033E-02 0.67528791E-05 3 -0.55926514E-08 0.15414997E-11-0.10573216E+04 0.36633473E+01 4 ! ! Comments for O2 3SIG-: ! ! delH(298.15 K) = 0.0 ! S^o(298.15 K) = 48.85 ! ! HCl 122104H 1Cl 1 0 0G 300.000 3000.000 1000.00 0 1 0.27635017E+01 0.14507129E-02-0.49012747E-06 0.68635979E-10-0.24435937E-14 2 -0.11917380E+05 0.64209547E+01 0.35960159E+01-0.51377278E-03 0.52834001E-06 3 0.59510130E-09-0.41540490E-12-0.12156164E+05 0.20531541E+01 4 ! ! Comments for HCl: ! ! delH(298.15 K) = -22.1 ! S^o(298.15 K) = 44.54 ! !C. F. Melius, unpublished data. ! ! Cl2 122104Cl 2 0 0 0G 300.000 3000.000 1000.00 0 1 0.42731707E+01 0.32261999E-03-0.18757849E-06 0.50267983E-10-0.51261446E-14 2 -0.13240450E+04 0.22649829E+01 0.30117131E+01 0.59879471E-02-0.10068187E-04 3 0.78613337E-08-0.23394531E-11-0.10876159E+04 0.82336938E+01 4 ! ! Comments for Cl2: ! ! delH(298.15 K) = 0.0 ! S^o(298.15 K) = 53.24 ! !C. F. Melius, unpublished data. ! ! Cl 122104Cl 1 0 0 0G 300.000 3000.000 1000.00 0 1 0.25002636E+01 0.59111379E-16-0.57460282E-19 0.22686620E-22-0.30993637E-26 2 0.13837890E+05 0.48605641E+01 0.25002636E+01-0.21973164E-16 0.39421548E-19 3 -0.28492026E-22 0.68741088E-26 0.13837890E+05 0.48605641E+01 4 ! ! Comments for Cl 2P: ! ! delH(298.15 K) = 29.0 ! S^o(298.15 K) = 37.96 ! !C. F. Melius, unpublished data. ! END REACTIONS END