3. 化学反応の熱力学 - akrmys.com

1 2011 ( ) 3-1 Copyright 2006 2011 by A. Miyoshi, All rights reserved. 3. [ ] ex.) (C7H16; fH 298 = 187 kJ mol 1) C7H16 + 11 O2 7 CO2 + 8 H2O(g) fH 298: 187 0 394 242 cH 298 = 7 ( 394) + 8 ( 242) ( 187) = 4507 kJ mol 1 ( ) Qc = cH 298 [H2O(g)] = 4507 kJ mol 1 1 1145072Oc nQ= 410 kJ mol 1 M ( ) = 12 7 + 16 = 100 1004507c MQ= kJ g 1 [= MJ kg 1] Qc / nO2 , Qc / M . fH 298[CO2] = 394 kJ mol 1, fH 298[H2O(g)] = 242 kJ mol 1 . fH 298 [kJ mol 1] a) C4H10 126 b) C4H10O 252 (C2H5OC2H5) a) C4H10 + 4CO2 + 5H2O cH 298 = 4 ( 394) + 5 ( 242) ( 126) = 2660, M = 12 4 + 10 = 58 nQ= 409 kJ mol 1, 582660c MQ= kJ g 1 b) C4H10O + 6O2 4CO2 + 5H2O cH 298 = 4 ( 394) + 5 ( 242) ( 252) = 2534, M = 12 4 + 16 + 10 = 74 625342Oc nQ= 422 kJ mol 1, 742534c MQ= kJ g 1 5 [CH3O-CH2-OCH3], [(CH3O)3CH] Qc Qc / nO2 , Qc / M.

2 * fH 298 NIST Chemistry WebBook ( ) . [ ] Qc / nO2 .. ( ) ( ) Tb .. ( ) ~ 2300 K = = (H, P ) a) . [ * fH 298(H2) 0 ] b) 298 K, 1 atm H2:O2 Tb , Cp,m = 2011 ( ) 3-2 Copyright 2006 2011 by A. Miyoshi, All rights reserved. J K mol 1 (298 K) . c) Cp,m Tb )298()(dmbm298m,cb HTHTCQTp . Hm (T ) Hm (298) Tb . d) 3500 K 2/1222)]O([)H()OH(ppp = atm 1/2 . H2:O2 3500 K p(H2O) = atm . p(H2), p(O2) . a) H2 + H2O, Qc = 1 0 + 0 1 ( 242) = 242 kJ mol 1 b) T = 242 1000 / = 7202, Tb = 298 + 7202 = 7500 K c) Hm (T ) Hm (298) = 242 kJ mol 1 ~5000 K d) x = p(O2) p(H2) = 2x, xx x x = p(H2) = atm , p(O2) = atm, = atm H2, O2 (H2, O2, H2O ) H ( : equil.

3 Mix.) (H, P ) ~ 3500 K = 3075 K ( ; OH, H etc. ) 6 a) NASA CEA2* - ( ) . C2H6 C5H10 C2H4O b) NASA CEA2* (CH4)- . ( ) [1] H2O(g), CO2 [2] H2O(g), CO2, CO, O2 [3] H2O(g), CO2, CO, O2, H2 [4] * NASA CEA2 ~miyoshi/nugc2011/ . [ ] , NASA CEA (~1993), Chemkin 7 CEA (1994~) 9 473625431221 TaTaTaTaaTaTaRCp ( ) H, S 2011 ( ) 3-3 Copyright 2006 2011 by A. Miyoshi, All rights reserved. TRCbTRTHpd11 ( ) TRTCbRSpd2 ( ) [ ] A + B +.

4 X + Y + .. pKRTGln ( ) RSRTHRTGKp expexp ( ) H = [H (X) + H (Y) + ..] [H (A) + H (B) + ..] S = [S (X) + S (Y) + ..] [S (A) + S (B) + ..] Kp ( ) )B()A()Y()X(ppppKp npcRTKccccK )()B()A()Y()X( ( ) n , R ( atm K 1 cm3 mol 1) [ ] A + B + .. X + Y + .. k X + Y + .. A + B + .. krev cKkk rev ( ) a) NASA CEA2 , 1000 K H2O + H H2 + OH ( 3) )H()OH()OH()H(22ppppKp.

5 (T = 1000 K) H / RT S / R H2O H H2 OH b) 1000 K , k3 = 109 cm3 mol 1 s 1 (H2 + OH H2O + H) k 3 . a) H / RT = [ + ] [ + ] = , S / R = [ + ] [ + ] = Kp = exp( + ) = 10 3 b) n = 0 Kc = Kp. ( ) k 3 = k3 / Kc = 109 / 10 3 = 1012 cm3 mol 1 s 1 2011 ( ) 3-4 Copyright 2006 2011 by A. Miyoshi, All rights reserved. , , etc. [ ] RCp m, = 1 .. RCCVp m,m, +23 .. 3 +23 .. 3 22 .. 2 ( ) + Nv.

6 : Nv = 3natom 6 ( ) 3natom 5 ( ) 0 (T 0), Nvib (T ) [ ] j j, TkhxjjB v122vib]1)[exp()exp(NjjjjxxxRC ( ) a) (C4H10) RCp m, T 0, T . b) N2 h / kB = 3354 K . T = 1000 K, 3000 K N2 RCp m, . a) T 0 Cp,m / R = 1 + + = 4. Nv = 3 14 6 = 36 T Cp,m / R = 4 + 36 = 40. b) T = 1000 K : x = 3354 / 1000 = , Cvib / R = , Cp,m / R = + = T = 3000 K : x = 3354 / 3000 = , Cvib / R = , Cp,m / R = + = 7 / (100 )