, , () . Δf0(), f ( - formation) , .
298,15 (250). () Δf0298 . /. (Cl2, H2, O2, S ) .
(Δ0298) ( . obustion - ) Δr0298 . , . 2(), 2(). , , N2(), - Cl, Br, I, - HCl(),, HBr(), HI(), SO2(). - .
1840 .. , , .
: , - , .. , ( ).
, V,T = const,
Qv = ΔrU0298, , = const,
Q = Δr0298
:
4NH3() + 5O2() = 4NO() + 6H2O(); Δr0298 = Δr1 = - 1166
: , :
4NH3() + 3O2() = 2N2() + 6H2O(); Δr0298 = Δr2 = - 1531,2
2N2() + 2O2() = 4NO() ; Δr0298 = Δr3 = 365,2
Δr1 = Δr2 + Δr3
-1166 = -1531,2 + 365,2
.
. .
:
v 1 1 + v 2 2 = v 3 3 + v 4 4; Δr0298
Δr0298 = [ v 3 Δf0298 (3) + v 4 Δf0298 (4) ] - [ v 1 Δf0298 (1) + v 2 Δf0298 (2)]
. .
, :
v 1 + v 2 = v 3 + v 4 D; Δr0298
Δr0298 = [ v 1 Δ0298 () + v 2 Δ0298 () ] - [ v 3 Δ0298 () + v 4 Δ0298 (D)]
.
.
( 298 ), . .
:
v 1 1 + v 2 2 = v 3 3 + v 4 4; Δr0()
i , 1 i,
Δr0() = (v 3 3 + v 4 4) - (v 1 1 + v 2 2)
:
(1.37)
(1.30), i . (1.37)
[Δr0()] (1.38)
[Δr0()] = Δ0 (1.38)
:
(Δr0()) = Δ0 (1.39)
d(Δr0()) = Δ0 d (1.40)
(1.39) (1.40) . (1.40),
Δr0() = Δ I + (1.41)
Δ I - 1 2.
1 = 298 , Δr0298
Δr0( ) = Δr0298 + (1.42)
. . Δ = 0, .. .
Δr0( ) = Δr0( ) = const, .. . , Δ0 = const; Δ0 (1.42) .
Δr0( ) = Δr0298 + Δ (2 - 298)
, , Δ 0 = + . Δ0 = f (T) : Δ0 = Δ + Δ, Δ = Σ v iai ( ) - Σ v jaj ( )
Δ. (1.42) :
Δr0( ) = Δr0298 +
:
Δr0( ) = Δr0298 + Δ (2 - 298) + (22 2982)
, .
1.
()
4() + 22() → 2() + 22()
.
: .
Δ0298 = - =
= -393,5 + 2(- 285,8) - (-74,9) - 0 = -890,2 < 0
2.
213() → 1() + 32(); Δ0298 = -75,4 .
: .
Δ0298 = 2 ,
,
0,5 (2 ,) = 0,5 [(2(-436,7) + 0 (-75,4)] =
= 0,5 (-873,4 + 75,4) = -399 /
3.
2NO() + 2() → 2NO2() (Q = Δ0298) (Qv = ΔU0298)
:
Q = Δ0298 = 2 * 34,2 2 * 91,3 - 0 = -114,2 =
= - 114200
Δ0298 = ΔU0298 + Δ V RT
Qv = ΔU0298 = Δ0298 - Δ V RT
Δ V = 2 (2+1) = - 1
Qv = ΔU0298 = - 114200 (-1) * 8,31 * 298 = - 111724 = - 111,7
4.
22() 66() 1300 3302 /. .
322() → 66()
:
Δ0298 = = 3 (- 1300) (- 3302) = - 598