, , . , . , () . , , .
, .. 1758 . .. , ., . , . . :
, .
:
å = const,
, å - , const constans , .
, , . .
, - Q, W DU:
DU = W Q,
(U) (, , .) , . .
, .. (V = const), , V = const, DV = 0 , :
W = -P DV = 0
, . :
DU = Qn ,
Qv - (/ /), . , ..
U2 U1 = DU = Qn
, ( = const), , , .
DU = U2 U1 = W + Qp
Qp - (/ /), . , = const ,
W = -P (V2 - V1)
:
U2 U1 = Qp P(V2 - V1).
|
|
, = const Qp = U2 U1 + P× (V2 - V1)
Qp = (U2 + P×V2) (U1 + P×V1).
(U + P×V) . , , , .. (D = H2 1) 1 2 , (2) (1) . , , :
Qp = H2 1 = D
, - . , V = const, , P = const. D = DU, D ≠ DU.
, , , . , S.
, , , . , , .. . :
.
, . , , : .
:
, , .
, , , .
∆ S = ,
Q , . , DS = 0, . , .
, , :
∆ S >
, () , DS > 0.
,
∆ S <
. () .
|
|
() . , .
, .. , . ( ), ( , ). - (G).
G = H - T×S , - , . , , = const = const. () DG < 0, DG (DG > 0), . DG = 0.
- , . ,
+ = + dD.
U1, () () . , .. , U2, () (d) D. , D . , ( V = const, = onst), Qv = DU, Qp = D.
, , . = 1
= 298º, . , , D0298K.
, , Qp Qn:
Qp = Qv + Dn×RT.
(Qp D) (Qv DU), . Dn - , .. Dn = n n . ( ), , .. Dn = 0, D DU.
Qp = Qv DH = DU
, , . . . ,
2 + 3H2 + 1/2O2 = C2H5OH
, .
+ 2 = 2
, , .
1 .
|
|
, ( () = 0).
(Qp = DH) . : 1) . (). : 2) . (). , , 3) . D. , :
D0298K = å 298 () - å 298 ()
, . .
, , , .. , . , " - ", .. , . .. 1840 , .
:
1. -. .
:
+ 2 = + 634,71
= + 2 - 634,71
Q + (-Q ) = 0.
2. , , .
:
+ 2 = 2 + 409,20 (1)
+ ½ 2 = 2 + 284,93 (2)
(1) (2), :
+ ½ 2 = + 124,27
, , , .
3. , , .
:
+ 2 = 2 + 409,20
+ 2 = 2 + 393,51
, , 409,00 393,51=15,69 /.