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. , . . Գ 㳿 . . . . . . . . . . - ó.
. . . , . . . Գ . . . .
. . 㳿 . , . . .
. . . . . . . .
. . . . 㳺 ó. , . -. , .
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쳿 . ճ 㳿 , .., , .
ᒺ . , 䳿, . . , . , .
. . , , .. . , .
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. , 1, 1 1 2, 2 2. 1 2 . ճ ( ) ( ) , , , , , , . ( ), ( ), ( ᒺ), ( ) .
ճ - ( = const; T = const). , .
(U) , , , . , , , , , . . , D U .
. , , , . 㳿 㳿 D U = U 2 U 1, U 2 U 1 .
㳺 Q . , . 㳿 .
㳿, . . 㳿, 䳺 - .
, , , . . .
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: , , 㳿 : Q = D U + (1). Q , (1) D U.
, , : = ¢+ D V ( = const) (2), ¢ , ; ; D V ᒺ (D V = V 2 V 1), V 2 ᒺ ; V 1 ᒺ .
, 2 = D V (3). Q = D U + D V (4), Q , . , D U = U 2 U 1 D V = (V 2 V 1), (4) : Q = U 2 U 1+ (V 2 V 1) = (U 2+ V 2)(U 1+ V 1) (5). (U + V) ﳺ . = U + V (6), Q = 2 1 = D , , , ﳿ . 㳿, ﳿ , , Q , ﳿ D . D ( 2 1) , , , .
㳺 U ﳺ (S), ó (G) (F).
( , V = onst), , , D V = 0, 㳿: Q V = D U (7).
( D V).
- ( = 0), 㳿 , , , : Q , = D U = U 2 U 1 (8), U 2 ; U 1 . - , ﳿ , , , : Q , = D = 2 1, 2 ; 1
쳿 |
= const = const ղ ..: , . , - - , .
, , 쳺. (Q > 0), , (Q < 0), .
г , , , . 쳿 :
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1) , , 66()+7 2 = 62+32()+3267,7 ; Q > 0 ; Q < 0 ;
2) ﳿ D , , 266()+152 = 122+62() D = 6535,4 ; D < 0 ; D > 0 .
1 , . ﳺ () D ﳿ , .
, 101 , , , .
, 1 /, , , .
ﳺ () ﳿ , . ﳿ .
() () . . , a+bB = cC+dD D = (cD .() +dD .(D))(D .()+bD .())
. , , . . : -, . .
, , , (xi,, yi,, zi) (v , v , v ). , . . , , W. W, ln W. /, k: k ln W = S. S ﳺ. . , ﳿ (/) R ln W = S, R = kN A ; N A . . ﳿ (D S) S 2 S 1, S 2 , S 1 .
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, . , ﳿ : D S > 0 (D S = S 2 S 1). , - , 㳺, (D < 0), , (D S > 0). , D = 0, ﳿ . , D S = 0, ﳿ. D D S . D = D S.
, V , T = const , T = const. 㳿, , , : = D U + D S = (U 2 U 1)+ (S 2 S 1) = [(U 2 S 2)(U 1 S 1)]. г (U S) 㳺 F: = D F.
= D + D S = ( 2 1)+ (S 2 S 1) = [( 2 S 2)( 1 S 1)]. г ( S) 㳺 ó G: = D G. ó G D G = D D S, D G = G 2 G 1, G 2 ó , G 1 ó .
,T = const , D G,T < 0. V,T = const , D FV,T < 0. C D G ,T = 0. D G ,T : D G = R ln k , R (/); ; k , .
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쳿, , . 䳿 .
, . , , . .
: I2 Þ 2I
: 2HI Þ H2+I2
: 2NO+H2 Þ N2O+H2O
. .
(v) . ᒺ. , : v = .
, , ( ). , a A+ b B = m M+ n N v = kC A aC B b, v ; k ( C A = C B = 1 / v = k); C a C B ; a b . (k) , .
, . , , . , H2+I2 Þ 2HI v = kC C v = k
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, . . , 䳿, , (/2 /2); S. . /2 /2.
, . , T = const Si (.)+O2 () Þ SiO2 (.) v = kCS (O2), v ; k ; CS (O2) , /2.
. , .
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.3.
ln k = / RT + ln A