- . - ( ). : , , .
. . . : , (, Fe) . - , ( ). , : F= U-TS; dU=T*dS-pdV; dF=dU-TdS = TdS-pdV-TdS-SdT = dF =-pdV-SdT,
[dF/dV]T =-p, [dF/dT]T =-S. (**) G=U-TS+pV, dG=dU-TdS-SdT+pdV=dU-pdV-dF=Vdp-SdT,
[dG/dp]T =V, [dG/dT]T =-S. (**): d^2F/dVdT = -[dp/dT]T.
, - => => [dP/dT]v=[dS/dV]T; P V, ..: [dP/dT]v=dP/dT. . DS, a DV: [dS/dV]T = DS/DV. DP/dT= DS/DV .. , DS=qT => dP/dT=q/(T*DV). - l
1. . l>0. DV=V2() - V1(.), DV>0 - t, .
2. l>0. DV=V2(.) - V1(.)
) DV>0 => c T.
) DV<0 => c T. .
37) . . .
(d lnKp)/dT = DH0/RT^2 (6.3)
(d lnKc)/dT = DU0/RT^2 (6.4)
(6.3) (6.4) , . , , ,
lg Kp = 1/2.3*ò DH0/RT^2 dT + I
I , - . , , . (5.3) dS=dq/T , . , . , . , , , DG0 = DH0 - TDS0. DG0 , , DH0 , , . DG0 = DH0 - TDS0 , , , DG0 =DH0, DS0 . , S=k*lnW, , , .
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(1906 .) , , DG0 DH0 , ().
, DG0 = DH0. DG0 DH0 , ( ) , , , , :
lim(dDH0/dT)T->0= lim(dDG0/dT)T->0
, :
lim(dDH0/dT)T->0= lim(dDG0/dT)T->0 = 0
I . [dG/dT]p=-S; , [dDG/dT]p=-DS. , , , , .. DS =0.
, : lim S = 0 Ү0 (8.1)
: , .
, , . .
, . , 0 . , , . , . III Cp Cv . , , Cv =[dU/dT]v =[dH/dT]p. , Cv . . , [dG/dT]p =0. , S = -[dG/dT]p =0
III : .
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III . , . , , .
: dS=dq/T , [dS/dT]v = Cv/T [dS/dT]p = Cp/T
Ү0 , . III , . , , . , , : 2, , NO . ( ) . () , () (W). S=k* ln W. 1 , , S . 0 . 0 , . , , , , . (O=C C=O). , . - , , , - . , , . , W = 2^Na ( ) S = k*ln (2**Na), S = R* ln 2. , R* ln 2 @ 1,37 /.
(8.1), , , , ( ): S0T = [T/0]òCp/TdT
: L, L , .
38. . .
. .
, , . (), . , , . , .
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, ..
- , ( ) : =n, , n , . = -DG, : DG= - RT ln Kp.
.
+2=3D.
:
1) ;
2) ;
3)
4) , (l)A, (l)B, (l)D, / (***A,B D ).
(*** .87)
(***.87)
-:
(DG) = (DH) T(DS);
(DG) = (***.88).
DG= - RTlnKp :
lg Kp = - DG/(2,3RT).
.
.
: D@0, .. DG=DH298-TDS298.
, , , .
: D=, .. D . : DG=DH298-TDS298+(-298)-T ln (T/298).
:
1) DHf298 DH298,
2) DS298 (*** f???) DS298 ,
3) , . ( 10**10(***10 10) 10**10), ,
4) 1 (.. 10**-3 10**3), DH DS .
Cu2O:
4CuO()=2Cu2O()+O2().
39. . . . .
.. (1861-1941)
- .
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.
: , ,t .
.
:
( ) , , .
N2()+3H2()2NH3()
= (p(NH3))**2 (**- )
p(N2)p(H2)**3
3 2 = 1
( ) = () .
, , .
, .
, (p,t .) .
,
: =-+2, = const, : =-+1.
, .
:
=1 =-+2=3-
max=3
()
-:
dp/dT=l/(TDV), l=q
: l>0, DV>0;
: l>0, DV>0;(***???????)
(dp/dT)>(dp/dT)>0
l>l
(dp/dT)>(dp/dT)
l>0; DV<0
(dp/dT)<0, (dT/dp)<0
40. : , .
(/).
.
(1) t1 t2
(2): - .
41. . .
, 1- :
- () .
: Pb-Ag, Cd-Bi, Au-Tl, KCl-LiCl, CaO-MgO.
: .
/ = xy/y (*** /y ).
42. . . , . (??? )
: , .
~10 . .
45. . .
()
(xy) .
AmBn .
, , - g
( g) .
2:
() .
( . . ).
, , . .
: 0.58: 54, 43, 32 ( ???) (*** )
, , .
PdHx Pd => PdHx . (***-)
:
- .
- .
- , , .
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