I. .
.
: .
, .
( ) , .
. : , , . , , . .
. , , , .
, , , (=nst), , (=nst), , (V=nst) , (q=nst). - (=nst, ==nst) - (V=nst, ==nst) .
, , .. . 298. 101,3 . , 1 /.
. , : U . , S , G F . , : r U, r H, r S, r G, r F.
2. .
( 120)
( ). , q. , , , , .
. , V=nst, qv = r U,
= nst qp = r H. , , . (, , ), r. r < 0, , r > 0, .
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, : () () .
: + b = + dD. :
r = (c r , + d r ,D) ( r , + b r ,) (2.1)
r ; r () , , D ; , d, , b , .
(2.1) () . () , 1 , 1). , , : 22() + 2() = 22 (). /.
, , , (2.1) :
r 298 = ( r 298,, + d r 298,,D) ( r 298,6,A + b r 298, ,) (2.2)
rͰ298 ( "") 298. rͰ 298,. () 298. rͰ298,. .2)
2.1. , : 3() =() + 2().
:
r 0298 = ( r 298,, + r 298,.2) r Ͱ 298,,3
:
r Ͱ298 = ((-635,1) + (-393,51)) (-1206) = 177,39 .
, r Ͱ298 >0, .
. .
:
3() = () + 2(); rͰ298 = 177,39 .
2.2. :
4NH 3() + 52() = 4NO() + 62().
3):
rͰ298 = (4rͰ298,.N + 6r298,,H2O) 4rͰ 298 ,,NH3
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, , :
rͰ298 = (4(90,37) + 6(-241,84)) 4(-4,19) = - 904.8 .
.
4NH3() + 52() = 4NO() + 62(); rͰ298 = - 904,8
_______________
1) : () , () , () , () , () .
2) , rͰ298,. .
3) Ͱ298,,2 .
, . , 2.2. r Ͱ298 = - 904,8 , , 4 N 5 2, 4 NO 6 2. , .
2.3. , . 2.2., :
) 2 2;
) 34. N;
) 11,2. NO.
, :
) : 2/5 = (-904,8). = 2(-904,8)/5 = - 361,92 .
b) 1 NH3 17. ( 1 ). , NH3, , :
= 34/17 = 2. : 2/4 = /(-904,8).
= 2(-904,8)/4 = - 452,4 .
) , 1 22,4 . NO , :
= 11,2/22,4 = 0,5. : 0,5/4 = /(-904,8). = 0,5(-904,8)/4 = -113,1 .
, . , , , , 5%. .
.
( 2140)
r G . = S, :
r G = r rS. (3.1)
.
, =nst). r G < 0, , r G > 0 , r G = 0, .
(3.1) r rS. r rS , .. :
r = rͰ298 rS = rS298. (3.2)
rͰ298 , (2.2), + b = + dD :
rS298= (S298, + dS298,D) (aS298, + bS298,B) (3.3)
rS298 /(), rS298 /.
3.1. ,
4NH3() + 52() = 4 NO() + 62() 202.6 500 (773).
, , (3.2), ..:
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r 773 = r 298 = - 904.8 = - 904800 . (. 2.2). r S 773 = r S 298. , (3.3), : r S298 =(4S298,N0 +6S298,H20) (4S298,NH3 + 5S298,2 )= (4*210,62 + 6*188,74) (4*1O92,5 + 5*205,03) = 179,77/
r Ͱ298 r S298 (3.1) :
r G773 = r 773 773 r S 773 = 298 773 r S 298 =
= 904800 773* 179,77 = 1043762 = - 1043,762
G773 , .
298, ( ) , , + = + dD, :
r G 298=( r G 298,, + dr G 298.,D) ( r G 298.A + b rG 298 , , ) (3.4)
r G 298. / ( ) , 298 1 , , , 4) , r G 298 .
3.2. :
4NH3+ 52 = 4 NO + 62
(3. 4) 5):
rG 298= (4 r G298,NO + 6 r G298,.H2O ) 4 r G29 8.,NH3
r G 298. :
r G298 = (4(86, 69) + 6(-228, 76)) 4 (-16, 64) = -184,56 .
, , 3.1, .
(3.1) .
rG (rG < 0), , , (r rS) < 0.
3.3. 3 () = () + 2 ().
r r S:
r = r Ͱ298 = 177,39 = 177 390 (. 2.1)
r S = r S298 = (S298. + S298. 2 ) S298. 3 = (39.7+213.6) 92.9=160.4 /K
r , r S :
177390 *160,4<0, 177390 < *160,4, > 1106. .. , 1 106, r G , , .
.
( 41 60)
, , .
() , . V = r/rt, rC rt, t, : V = d/dt. . , , .
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4) , .
5) r G298,O2 .
: , . + b = + dD , , :
V = kBb (4.1)
k , , A B , b . .
4.1. 22() + 2() = 22() :
V = kH2 2 2. .
. .
4.2. , 2() + 2() = 2(), : V = 2 .
, . *
4.3. 22() + 2 () = 22() 2 .
(4.1). V1 = kH2 2 /2, 2 :
V2 = k(H2/ 2)2 2 V2 / V1 = 1/4, .. 4 .
, , . , , , .
4.4. 22() + 2 () = 22() 2 .
V1 = kH2 2 /2 2 2 , 2 2 2, 22 : V2 = k(2H2) 2 2 2 V2 / V1 = 8, .. 2 8 .
: 10 2 4 . , .
:
V2 = V1y (2 T1)/10 k2 = k1y (2 T1)/10 (4.2)
V2 Vi, k2, k1 , 2 1 = 2 4 .
4.5. , 3, 30 .
(4.2). V2 / V1 = -30/10 = 1/27. .. 30 27 .
.
( 6180)
, , . + b ó cC +dD) , , D ( ), D , , ( ). , .. r G = 0, (V1) (V2) : V1 = V2
, , . . , , , , , , . , [2], [N] , .
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. , , , . + ó c+dD :
= ([1[D] d)/([][]) (5.1)
5.1. N2()+2() ó 2NH3()
(5.1) : =[ N]2/ ([N2][2]3).
, , , .
5.2. F304() + 4() ó F() + 42().
: = [2]4/[]4.
, 6).. "" "", "".
5.3. F304() + 4() ó F() + 42(), .
, : =2 4/4, 2 , 2 . .
i =iR, i i , i- , , , :
=(R) r n (5.2)
rn .
5.4. , :
N2()+2() ó 2NH3()
: = NH3 2/ N2 2 3);
r n = 2 (1+3) = -2, (5.2) =(R)-2 =(R)2.
________________
6) , .
:
rGº = -2, R lg (5.3)
rGº (3.1) (3.4).
(5.3) , . , (5.2), .
5.5. () ó () + 2() 500 (773).
(2 ) , (5.3). , r G0773 (3. 1): r G0773 = Ͱ773 773 r S773. G0773 773 r S773 (3.3), : r 0 773 = r 0 298 =177390 S773 = r S298 =160,4 /. r G0773 = 177390 773773160.4 =53401 . (5.3) : lg = -r G773/(2,R) = -53401/(2,3*8,314*773) = -3,6.
7) : =2=10 -3,6. , ( (3. 3).
(5.5) , : ()>> 1, , . , , ()<<1, .