I II II 1
dw = pd = 0 1 U = Q (4.10) 1K (heat capacity) (mole heat capacity) ( dq / d ) = ( du d C = / ) (4.11) du = C d U = C d (4.1) 1 1 du = dq + dw dw = pd
dq = du + pd (4.13) p dq = d( U + p ) p (4.14) ( U + p ) enthalpy H H U + p (4.15) (4.14) dq = dh p (4.16) Q = dh = H H1 1 = H (4.17) ( dq / d ) = ( dh d ) C = / p (4.18) dh = C d H = C d p (4.19) 1 1kg(specific heat capacity) (specific heat) cmkg t 1 t Q Q mc ( t t 1 ) [J] (4.0) m[kg] c [J kg -1 K -1 ] ( t t 1 ) [K] 3
[ 4.3] 10mol 373.K 473.K C v 6.43J mol -1 K -1 [ ] U = 1 C d ( 1 U = nc ) 10 6.43 473.-373. 6430 J 6.43 kj [ 4.4] 30 15g 0 J 094 4187 J kg -1 K -1 0 0 1 kg 335 kj [ ] 30 43.15K 0 73.15K ( 73.15-43.15 ) 094 0.015 = 94.3 J 0 73.15K 0 93.15K (93.15 73.15) 4187 0.015 = 156.1 J 0 0 335000 0.015 = 505 J 94.3 + 156.1 + 505 = 73.4 J [ 4.5] C C nr [ ] (4.11) (4.18) C C C H (1) C = ( ) ( ) H = U + p () C (1) () ( U + p ) ( p )] ( (3) C = [ ] ( ) = ( ) + [ ) U du = ( ) d + ( ) d (4) (4) 4
( ) = ( ) ( ) + ( ) (5) (3) (5) C ( p ) (6) C = ( ) ( ) + [ ] = [( ) + ]( ) (4.11) ( ) = 0 (7) nr = (8) p (8) nr ( ) = (9) p (6) (7) (9) nr C C = [ 0 + p] ( ) = nr (10) p 1mol C C = R (11) Cp Cp a1 a a3 a4 3 (1) a1 a a3 a4 4-1 1 H (4.18) (1) 3 H = ( a + a + a + a d () 1 1 3 4 ) Cp C C (3) CpCp 5
C = ( C ) (0) ( C ) (1) (4) Cp Csat C 3 Cp Csat C [ 4.7] p C p C v [ ] 1 dq 0 dq=d+pd= C v d + pd = 0 (1) pv=r pd + dp = Rd () (1) ()d pdv + dp = R pdv C v ( v v = (3) C + R) pd + C dp 0 (4) C pdv + C dp 0 (5) p v = (5) C p p Cp d dp + = 0 (6) p C v C p C v (6) dv dp + = 0 (7) p d dp + = K K (8) p ln + ln p = K ln p K p K (9) 6
[ 4.8] 0 [ C] 1[ gr] 80 [ cal gr] [ ], S = = dq = 1 dq 1 1 Q Q 1 [gr] Q 80 S = = = 0.9 [ cal K] 73 0[ C] [ C] 0.9[ cal gr] 0 1 [gr] [ 4.9] 1 0 [ C] [ C] CO 100 3 6 ( CO ) = 7.7 + 5.3 10 0.83 [ cal mol C] C 10 4.9 S = 1 C d S = 373 73 3 6 [ 7.7 + 5.3 10 0.83 10 ] d = 373 73 7.7 + 5.3 10 3 0.83 10 6 d 0.83 = 7.7 73 73 10 373 3 373 6 [ lm ] + 5.3 10 [ ] [ ] 373 73 7
= 6 373 3 0.83 10 ( 7.7) (.3) log + 5.3 10 ( 373 73) ( 373 73 ) [ ] =. 90 cal C 73 Excel lnp 17 1 SI SI m kg s K mol A cd SI SI SI SI N m kg s- a m-1 kg s- (=N m-) J m kg s- W m kg s-3 (=J s-1) C A s m kg s-3 A-1 (=J A-1 s-1) m kg s-3 A- (= A-1) S m- kg s-1 A (= -1) F m- kg s-1 A s4 (=A s -1) Hz s-1 8
3 SI 10-1 10-9 10-6 10-3 10-10 -1 10 3 10 6 10 9 p n m c d k M G 9
4 3.141593 F 9.6485456 104 C mol-1 K 1.38066 10-3 J K-1 R 8.31441 J K-1 mol-1 8.056 10- dm3 atm K-1 mol-1 1.9870 cal K-1 mol-1 L 6.005 103 mol-1 H 6.6618 10- J s G 9.80665 m s-1 C.99795 108 m s-.41383 10- m3 mol-1 5 3) B ln p = A p [ ka ] [ K ] ( + C) A B C [K] 16.56989 3984.93 39.74 73.15 373.15 13.99869 696.49 46.918 63.15 333.15 n- 13.85871 911.319 56.510 70.15 400.15 16.5914 3643.314 33.44 88.15 357.15 16.66404 3667.705 46.966 93.15 366.15 n- 17.786 4117.068 45.71 58.15 371.15 n- 14.94047 3005.39 99.73 36.15 399.15 13.76108 778.000 50.014 80.15 354.15 13.8650 755.64 53.989 81.15 353.15 13.98998 3090.783 53.963 46.15 384.15 p- 14.08130 3346.646 57.840 300.15 389.15 14.3784 787.498 43.486 60.15 38.15 Gmehling J.et al. DECHEMA Chemistry Data Series.ol.1,art1-8(1977-1984) 10
6 8) c [Ma] c [K] c [cm 3 mol] (CO) 3.491 13.91 93.5 0.049 (CO ) 7.38 304. 94.4 0.5 (H O).1 647.30 57.11 0.344 (NO ) 10.1 431 8 0.86 (SO ) 7.884 430.8 1 0.51 (HF) 6.48 461 69 0.37 (HCl) 8.31 34.6 81 0.1 (HBr) 8.55 363. 110 0.063 (HI) 8.31 44.0 135 0.05 (HCN) 5.39 456.8 139 - (H S) 8.94 373. 98.5 0.100 (NH 3 ) 11.8 405.6 7.5 0.50 (CH 4 ) 4.595 190.55 98.9 0.008 (C H 4 ) 5.076 8.65 18.68 0.085 (C H 6 ) 4.871 305.3 147 0.098 (C 3 H 8 ) 4.50 369.8 03 0.15 (C 6 H 6 ) 4.898 56.16 59 0.1 (C 6 H 1 ) 4.07 553.4 308 0.443 (C 6 H 5 CH 3 ) 4.109 591.79 316 0.57 (C 10 H 8 ) 4.11 748.4 408 0.30 (CH 3 OH) 8.10 51.58 118 0.559 (C H 5 OH) 6.38 516. 167 0.635 (C 6 H 5 OH) 6.13 694. 64 0.440 (CH 3 CHO) 5.54 461 168 0.303 ((CH 3 )CO) 4.70 508. 09 0.309 (CH 3 COOH) 5.79 594.45 171 0.454 (CH 3 COOCH 3 ) 4.69 506.8 8 0.34 (CH 3 COOC H 5 ) 3.83 53. 86 0.363 (CH 3 ) O 5.37 400 190 0.19 (C H 5 ) O 3.638 466.70 80 0.81 (C 6 H 5 NH ) 5.31 699 79 0.38 (CCl 4 ) 4.56 556.4 76 0.194 11
4-1 8) Cp,m = a1 + a + a3 + a4 3 ( Cp,m [JK 1 mol 1], [K] ) a1 a 10 3 a3 10 5 a4 10 8 CO 30.87 1.85.789 1.7 CO 19.80 73.44 5.60 1.715 CS 7.44 81.7 7.666.673 Cl 6.93 33.84 3.869 1.547 F 3. 36.57 3.613 1.04 H 7.14 9.74 1.381 0.7645 HCl 30.67 7.01 1.46 0.3898 HF 9.06 0.6611 0.03 0.504 HO 3.4 1.94 1.055 0.3596 HS 31.94 1.436.43 1.176 I 35.59 6.515 0.6988 0.834 N 7.016 58.1 0.89 NH3 7.31 3.83 1.707 1.185 NO 9.35 0.9378 0.9747 0.4187 NO 4.3 48.36.081 0.093 O 8.11 0.003680 1.746 1.065 SO 3.85 66.99 4.961 1.38 SO3 19.1 1374 11.76 3.700 3.48 31.57.985.300 11.71 135.8 8.411.017 19.5 5.13 1.197 1.13 3.806 156.6 8.348 1.755 7.716 18.3 10.07.380 4.840 54.9 17.53 4.949 5.409 178.1 6.938 0.8713 9.014 14.1 8.390 0.1373 6.301 60.6 1.53.038 4.4 306.3 15.86 3.15 33.9 473.9 30.17 7.130 R. C. Reid, J. M. rausnitz and B. E. oling, he roperties of Gases and Liquids, 4th edit., Appendix, McGraw Hill (1987) N( ) ( ) p.ii-39(1984) 1
4-93K 4) J mol -1 K - CH3 CH CH C =CH = C H = C C H C CH C = C CH = CH Cl 1 Cl 3 4 Br 36.8 30.4 1.0 7.36 1.8 1.3 15.9 4.7 4.7 18 1 6 36 5 38 C = O O C OH O C O CHOH CHOH CCOH OH ONO H H N H N N N= C N SH C H 53.0 79.9 60.7 73. 76.1 111.3 44.8 119. 58.6 43.9 31 19 58. 44.8 33 15 F I O > O = H 17 36 35 53.0 13
1 50 A 16.56989 B 3984.93 C 39.74 1 atm=101.35 ka B ln p [ka] = A ( [K] + C) B 3984.93 ln p [ka] = A = 16.56989 =.510 ( [K] + C) (50 + 73.15) 39.74 p 0 =1.31 ka = 0.115 atm -1. atm A 16.56989 B 3984.93 C 39.74 -. 3984.93 ln(.0 1.0135 10 ) = 16.56989 ( 39.74) = B 3984.93 = A ln p C 16.56989 ln(.0 1.0135 10 ) + 39.74 393.67 K 10.5 14
3 4.00 atm 4.0 1.0135 10 ka A 16.66404 B 3667.705 C 46.966 p o [ka] [K] atm 4.00atm ln p [ ka] = B A ( + C) = B 3667.705 = A ln p C 16.66404 ln(4.0 1.0135 10 ) + 46.966 391.05 K 117.9 15