, () , . , , ().
. (ΔS) ( ) , ( ) , :
S = Q./T
, S, , :
S > Q./T
S = Q./T
S < Q./T
, dq = 0, :
S > 0
S = 0
S < 0
, .
() . , .
. (1851): " , , "
. (1850): " " : " , , , "
, . . (1824) . . (1834) :
= (T1 T2)/T1
, . XIX , , , - .
: . ( .)
, : . , , .. , , . , , . - .
|
|
|
, . ( . S = 0 T = 0 .)
. . (. 6.3).
|
| .6.3. |
, , , , . , , , , .
, , , : , .. 
< 0, . , , , . . ( S > 0).
.
1. < 0, S > 0. .
2. > 0, S < 0. .
3. < 0, S < 0. , S . (, .)
4. > 0, S > 0. , S . ( .)
, , :
G = T S, T , .
ΔrG0 , , Δr0
ΔrG0 = 
Gf 0 (.) Gf 0 (.).
G < 0 , G > 0 . G = 0, ( ).
() :
| ΔH | ΔS | |
| + | - | |
| - | + | |
| - | - | ΔH TΔ S |
| + | + | ΔH TΔ S |
- (V, T = const) - ( ). G.
|
|
|
, . , ( = +400 /, ).
:
l262 + 6SOCl2 = CoCl2 + 6SO2 + 12HCl
: 1 18 (!) .
.
1 25 G 0 :
1 G 0 = 0 298 S 0.
2 , 25 , :
1 G = G 0 + RT ln K .
K ,
G = 0 
G 0 + RT ln K = 0
: 
.
- :
1 G 0 = nF 
0,
n , F (
96 500/),
0 . , .
4. ( G = 0) : 0 = T S.
= / S , .
, , (. 6.2).
6.2
| , /
| , , G = 0
| ||
| MnO2 + 2H2 = Mn + 2H2O | |||
| 1/2Fe2O3 + 3/2H2 = Fe + 3/2H2O | |||
| 1/2Cr2O3 + 3/2H2 = Cr + 3/2H2O | |||
| SiO2 + 2H2 = Si + 2H2O | |||
| CaO + H2 = Ca + H2O |
. .
VII.
. , ,
N2 + O2 = 2 NO ΔG0 = +176 ,
, . NO .
, , ΔG < 0, . ,
C + O2 = CO2 ΔG0 = -395
, , .
- .
( ) . .
, . .
|
|
|
V. = ((2 1) / (τ2 τ 1)) = (D / D τ)
1 2 τ 1 τ 2 ( (+) , () ).
V. = d / d τ, Δτ → 0
.
, .
. , . , .
, :
1) ;
2) ;
3) ;
4) ;
5) , : .
1. . . . , H2 N2 ; . (HCl, H2O) , . .
, .
, ; .
2. . ( ) - .
(. , ., 1867.) .
