Фізична та колоїдна хімія
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0 , ;
QP – QV = H – U = nRT,
n – % -$ ) + :
n = 10 – 12 = –2.
! " :
QP – QV = (–2)·8,315·298 = –4955,7 (/ .
# # # 9. 0 % )- + ) ) / "/:
2 ;:4 + CO2 = ;:3;);:3( ) + :2)( )
% + . &- ( " $ $ % -( :
;P = a + b' + c'2; CP = a + bT + c// T2
;! # |
H0f ·10–6 |
#·10–3 |
b |
c/·10–8 |
·103 |
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+9/$ |
+9/ |
+9/ |
+9/ |
+9/ |
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( ·-) |
( ·-) |
( ·-) |
( ·-) |
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C2 ()) |
–242,000 |
30,146 |
11,305 |
— |
— |
?C3? ?C3 |
–216,796 |
22,489 |
201,926 |
— |
–63,576 |
()) |
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CO2 |
–393,796 |
44,173 |
9,044 |
–8,541 |
— |
CH4 |
–74,901 |
17,484 |
60,502 |
— |
–1,118 |
) ’. & ( ) % -" $) :
HT H 2980 |
a (T 298) b (T 2 2982 ) |
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c (T 3 2983 ) c/ ( |
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& ( " $ , ; + %:
121
CP,H2O 30,146 103 11,05 T ;
CP,CH3COCH3 22,489 103 201,926 T 63,576 10 3 T 2 ;
CP,CO2 44,173 103 9,044 T 8,5412108 ; T
CP,CH 4 17,484 103 60,502 T 1,118 103 T 2 .
& a, b c:
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$ $ "-( " :
a = [(30,146 + 22,489) – (44,173 + 2·17,484)]·103 = 26,512·103 (/( · )
b/2 = 1/2[(11,305 + 201,926) – (9,044 + 2·60,502)] =
41,591 (/( · )
/3 = 1/3(–63,576 + 2·1,118)·10–3 = –20,446·10–3 (/( · )
c/ = –(–8,541)·108 = 8,541·108 (/( · ).
0 " % 298 , -/ ' :
H2980 H 0f , H 0f , ;
H2980 ( H 0f ,H2O H 0f ,CH3COCH3 ) ( H 0f ,CO2 2 H 0f ,CH4 );
H2980 [(–242,0 – 216,796) – (–393,796 – 2·74,901)]·106 = = 84,802·106 (/ .
) % HT 500( " :
122
H500 H2980 26,512 103 ( 500 298 ) 41,591 ( 5002 2982 )
20,446 10 3 ( 5003 2983 ) 8,841 108 ( |
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ŠH500 = 92,176·106 "?/ .
# # # 10. " % % ) " 10 %. C( ; , ; )-) /" 1200 , $ $ ) 400 ?
* ’ . 0 ) " % % ( ( ) ) ( $ /:
) T1 T2 1200 400 100% 66,67% . T1 1200
& ( " , ; ( ;
) = (66,67 – 10) = 56,67 %.
# # # 11. 0 % $ 2,7 ) , % 1 = 1,013·105 !1 = 293 , 2 = 0,50665·105!2 = 373 . Cp = CV = 4,187·103(/( )· ).L0 = 2260,98·103 (/ ). 0 ( -) .
) ’. & ( - $ $( , / -%% . ! + +- $, ; "-$ +$ . !/ (%.
, ; " $ +$ -
:
1 – ) 1 = 1,013·105 !1 = 293 !2 = 373 ;
2 – ( -!2 = 373 ;
3 – !2 = 373 12.
123
& ) %% ( % % %, + S = S1 + S2 + S3. 0 ( $ %.
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& % S1 |
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373 |
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2,7 |
4,187 10 |
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2,303 |
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3,525 |
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293 |
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& % S2 |
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m L |
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2,7 2260,98 103 |
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16,366 103 |
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S2 |
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& % S3 |
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p |
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2,7 |
8,315 103 2,303 lg |
1,013 105 |
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0,855 103 (/ . |
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S3 |
nR ln |
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& ) % $ )-$ :
S = 3,525·103 + 16,366·103 + 0,855·103 = 20,756·103 (/ .
# # # 12. 0 G0 $ %
?2C2 +2C2 ( ) = ?C3? C( ) + C2:
G0f ,H2 O 237,245 106 (/ ,
G0f ,C2 H2 209,350 106 (/ ,G0f ,CH3COOH 392,741 106 (/ .
) ’. & ) % ' ++ $ % " :
G0 G0f ,k G0f ,n [( 392,741) ( 209,350 2 237,245 )] 106
127,251 106 (/ .
124
# # # 13. J $ "$ % ( 3 3)$ 28 ) 64 ) /. ! . & % % $ " . 0 ( ) .
* ’ . &$ % % ( ) ) ( S1 S2). , "% :
S S1 S2 n1R ln |
V |
n2R ln |
V |
; V V1 V2 |
; n |
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S 1 8,315 103 ln 2 2 8,315 103 ln 2 17,287 103 |
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# # # 14. 0 ( |
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+ % , ; + ) " 550 °?, , ; + , /" 25 °?.
) ’. $ "
) T1 T2 ,
T1
'1 = 550 + 273 = 823 , '2 = 25 + 273 = 298 . (
) 823 298 0,6379 9 63,8 % . 823
# # # 15. E , /" +-400…1200 ,( + 93,02 (. 0 - , ; " / .
) ’. 0 " % :
) T1 T2 1200 400 0,667 . T1 1200
&$ % Q1 -
) W :
Q1
125
Q1 W ; Q1 93,02 139,5 (. ) 0,667
+ , " , "W = Q1 – Q2, Q2 = Q1 – W.$ ( " :
Q2 = 139,5 – 93,02 = 46,48 (.
# # # 16. / 12 ) $( / 20 °? – 40 °?. ; / 1 60 + . < - /" %, ; + " / /" 29,2 (/( · )?
* ’. & % ) $ :
S n (R ln |
p1 |
C p |
ln |
T2 |
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12 |
2,303 (lg |
1 |
29,2 lg |
233 |
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p2 |
T1 |
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293 . |
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15,28 "? / L
# # # 17. ) % ? + C2 = ?2 + C2 1080 /" . 0$ 2 CO 3 . 0 ( % ($ $).
* ’. ) % $% % -) :
K nCO2 nH2 .
C$ )?2. ! / ) ( . / (3 – ),CO – (2 – ):
nCO2 nH2 x; nCO 2 x, nH2O 3 x;
/ ( - ) , ( " :
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x2 |
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(2 |
x)(3 x) |
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= 1,2.
! + nCO2 nH2 1,2 ; nCO 0,8 ; nH 2O 1,8
) /" 5, --( % + :
n |
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1,2 100 |
24 %; |
n |
H |
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1,2 100 |
24 %; |
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CO |
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n |
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0,8 100 |
16 %; n |
H |
2O |
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1,8 100 |
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36 %. |
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# # # 18. % 3 Fe2O3( ) = 2 Fe3O4( ) + ½ O2())kH0298 = 223,3 ( G = 195,3 (. $ -) "% % : ) ! = 298 +) ! = 398 , ; 298…398 H ( - .
* ’ . ) $% % ( "-
:
G = –RT lnKP,
lg KP |
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195,3 |
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34,1; KP 8 10 35 . |
2,303 |
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2,303 8,31 10 |
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+) + $% %:
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lg KT2 lg KT1 |
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dT . |
2,303 R |
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& % ( -299…398 K, %% ( )- . ) $ -$ ( " :
lg KT |
lg KT |
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H (T2 T1) |
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2,303 RT1T2 |
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lg K398 34,1 |
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223,3 100 |
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8,31 10 3 |
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398 |
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KP 1,3 10 24.
# # # 19. ) %
CH3COOH + C2H5OH • CH3COOC2H5 + H2O
127
/" 4. 0 % , ; / 1 2 .
) ’. 0 " - ) % ) KC.( ; ( -$ %. - ) (1 – ), – (2 –). 0$/ , ( :
K |
CCH3COOC2H5 |
CH2O |
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x x |
4 |
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C |
CCH |
CC H OH |
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( " 3 2 – 12 +8 = 0,
) : 1 ™ 3,153, 2 ™ 0,847. " , + " . ! ,) :– 0,847 , – 0,847 , % – 0,153 , – 1,153 .
# # # 20. ) % N2 +3 H2 = 2 NH3350 °? /" 2,32·10–13. + ? )
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$ n: n = 2 – 1 – 3 = –2. |
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K |
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(RT )2 2,32 10 13 (8,315 103 623)2 |
6,624 |
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(RT ) n |
(RT ) 2 |
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# # # 21. 0 ) %
? + 2 = ?2, ; 1573 %% ) /"
0,289.
* ’. ’ "% - ) ) / ( $. - ( " / ) +$ $ ( n = 0), = ?.
128
+’" ( %) )- / , $/ , ; ) %$ +’" , :
KC |
Kp |
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CCO2 |
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pCO2 |
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x |
0,289 . |
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CO |
pO |
100 x |
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& = 22,42. ( , ( 1573 -22,42 % ) ) ) 77,58 % /.
# # # 22. $% ) %
?2C5C()) + ?C3? C()) = ?C3? ?2C5()) + C2 ()) /" 9,0 300 °?, 150 °? – 30,0. 0%.
* ’. & + ) - ) $ $ ( " -$ H ) :
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ln |
KPT2 |
T1 T2 R |
lg |
30 |
573 423 8,315 2,3 |
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KPT |
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573 423 |
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T2 ) |
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# # # 23. ) -/" 887,644·103 (/ ). ! % -!1 = 373 /" 0,721·105 . 0!2 = 353 .
) ’. , ; -" / /. !2 ) ) -– :
lg |
p2 |
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T2 T1 |
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2,303 R |
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0 R 1 , -+ "% ( .
129
) /" 46 )/ , = 887,644·103·46 ( (/ ). & $ ) ( " :
lg p |
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T2 T1 |
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2,303 |
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$ "-
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lg p2 |
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887,644 103 46 (373 353) |
lg0,721 105 4,8755; |
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2,303 8,315 103 353 373 |
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p2 0,75 105 @a |
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# # # 24. ! ) = 363,3 /" 148,639·103 (/ ). &1,0133·105 , ; +’" V = V – V = 0,146·10–3 3/ ).
) ’. & – ( -
:
dT T@A V dp H@A
& -kT kp, ( " :
T T@A V ,
p H@A
T p T@A V .
H@A
/ , ; $ / , ( " :
T 10133, 105 363,3 0146, 10 3 0,0351 K. 148,639 103
# # # 25. 0 / .1, : ) + $ +, , L;
+) " 0 / /0 80 % 250 °?;
130