, . , . . . (- ), (- ), ..
. ( ). . ( ), ().
e CuSO4.5H2O, SO2.BCl3( SO2), [CoOH(H2O)5]2+, H3O+( H2O). , Cs+.8H2O, Cl‾.8H2O, S8 ..
. , , :
nH2O ↔ (H2)n ( );
2H2O ↔ H3O+ + OH‾ ( );
CdS → S2 + Cd2+ ( );
Cd2+ + H2O ↔ CdOH+ + H+ () .
, . . - .
. . , , , .
ΔGP,T( : ):
ΔG-= Σ(∆GP,T) Σ(∆GP,T) < 0.
. 1 . . . . Q, , , 45% 55% : , , .
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. 1.
, ∆UT,V( ∆T,P) S. , . -
∆G = ∆H T∆S.
∆H = QP,T.
, ,
Σ∆H Σ∆H> 0,
, ,
Σ∆H Σ∆H< 0.
, (∆H<0), 8% . , , (. 1).
P=const T=const, :
∆G = ∆H T∆S < 0.
, , , , .. ∆S > 0. , . , , .
- , , , ∆S < 0. ∆G , .
1
. | , | . | , | |||||||||
CH3COONaH2O | -4.7 | CaCl26H2O | -12.4 | |||||||||
NH4Cl | -5.1 | NH4NO3 | -13.6 | |||||||||
NaNO3 | -5.3 | KCNS | -23.7 | |||||||||
Na2S2O35H2O | -8.0 | |||||||||||
. | , | . | , | |||||||||
CaCl26H2O | -9.0 | NaNO3 | -18.5 | |||||||||
CaCl2 | -11.0 | (NH4)2SO4 | -19 | |||||||||
NH4Cl | -15.8 | NaCl | -21 | |||||||||
NH4NO3 | -17.3 | CaCl26H2O | -40.3 | |||||||||
: 100 ; , .
.
, , ∆H ≡ ∆U, .. ∆H . ∆H. : , , , .
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∆H = ,
∆H = ∆H + ∆H,
∆H = ∆H = .
∆H= 0 ∆H = ∆H, .. ∆H < 0, . , . -- . , , , (∆H < 0).
( → 0), ( → 0), (, I2 CCl4). .
∆H = 0 =
, , , . . > ∆H > 0, .
, . (∆V) . , , 1 1 , 2 , 1,93 (25). ( 3,5%) , .
:
↔ .
. , () (). , . , .
V ;
V , V.= V.
, , , , ,
V.= k
V.= k C.
= k / k , .. . , , , (∆G = 0).
T = const . , 100 . - . (, 65,2 KBr / 100 H2O 20 . , 70 100 20 , 65,2 ( ), 4,8 () .)
(k > k ), , .
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, .. , . , , .
(CH3COONa, Na2S2O3, Na2SO410H2O ), , . . XVIII . . . ∆G>0. () , , (, ..).