Фізична та колоїдна хімія
.pdf
d(lnCa |
)P d(lnCa )Ï |
|
d(lnCb |
)P d(lnCb )Ï , |
(8.4) |
+ $ $ :
d(ln Ca )
d(ln Cb )
PÏ
|
d(ln Ca |
) |
. |
(8.5) |
|
|
|||
|
d(ln Cb ) |
|
||
& + . & ) +-% –b, -
– . ]: X |
|
nb |
, |
||||
na |
nb |
||||||
|
|
na |
|
|
|||
%: 1 X |
|
. |
|
|
|
||
n |
n |
|
|
|
|||
|
|
|
|
|
|||
|
a |
b |
|
|
|
|
|
0 (, ; -( " * ), + , ; $ -, ; + +’" , +’" % .
0$/ , (8.5) ( -) :
d[ln(1 x)] |
|
d(ln pa ) |
+ |
|
d(ln pa ) |
|
|
|
d(ln pb ) |
|
. |
(8.6) |
|
|
|
|
|||||||||
d(ln x) |
d(ln pb ) |
|
|
|
|
|
|
|||||
|
d[ln(1 x)] |
d(ln x) |
|
|||||||||
|
|
|
|
|
|
, ; " $ " , +
d(ln pa ) |
|
d(ln pb ) |
|
k . |
|
d[ln(1 x)] |
d(ln x) |
||||
|
|
||||
J :
d (ln pa ) k d[ln(1 x)]; d (ln pb ) d(ln x); k – .
I ) ) " : ln pa ln(1 x )k ia ;
ln pb ln xk ib .
) $ )$ :
(8.7)
(8.8)
(8.9)
151
|
|
|
, = 0 ia = lnpA, |
|
|
|
|
|
, = 1 ib = lnpB. |
(8.10) |
|
|
@ |
|
0 |
/ ( $ |
|
% ]. |
|
|
|
|
|
, $ + , ; $ |
|||||
+$ k = 1 |
|
||||
|
p |
p |
+1 x, |
(8.11) |
|
|
|
a |
A |
||
|
|
|
pb pB x |
|
|
– |
. |
||||
g |
|
- |
|||
|
. |
|
|||
D ; ] ( – ) ", " (.
g ?( %) ! -
( |
]): |
||
X |
pA pa |
. |
(8.12) |
|
|||
|
pA |
|
|
0 (8.11) (8.12) $ - +$ . & + $ $ -( % " %, % ) -" $/, -, ) %+- $ +’" $( %, -) –( % " % ( +- , ; $ :
FA A FB B FA B , |
(8.13) |
, = 0 ia = lnpA, FA–A, FB–B, FA–B – - ( % " % ( , -
( .
C $/ " , "% ( ) ./ % ]
152
y, / % (1 – ); /(8.11), " :
y |
|
pB |
x |
|
. |
(8.14) |
|
1 y |
pA(1 x ) |
||||||
|
|
|
|||||
@ ) ", ; ;$ (@ = 0), % %. ! $ ) ) (- , + – ).
0 / ; $) (8.11), $ $ -$ ( :
p pa pb pA(1 x ) pB x |
(8.15) |
p pA ( pB pA ) x |
(8.16) |
, ; – $. 0 / ) / , ; ] + , ( ) /( . 15). D ; % ; , (], 3 + ) - " .
"(.) |
"(") |
3
21
. "
=0 =1
; . 15. F"#% # !" "! #* ) $ ;# ):
1 – = .(1– ); 2 – b = pB.x;
3 – p = pa + pb.
153
8.3. #$ ;# ) ) "!# " &
D ; " , + -) / , +’" , ( $ ( % " % (FA–
A ‹ FB–D; FA–B ‹ FA–A ‹ FB–B), " $ -( . 11 12). ( % +-
% $ $ , (a = f(x), pb = f(x) p = f(x) ( -$, $ $ + - ( .
( $ - : ( .16) ) ( . 17). ,$ " , ;) " ) , -+$ $ ( -). + - ) % % + ) $, / +$, ) / $ . * +- /" ; ( %) -( %).
) $ $ -" . *+ +$ +$. G / ( $, ) - / $ , ; + /" $ $ pA = f(x), pB = f(x) p= f(x) ( % . 17).
? , ; " + /, + " + ( / " / /$" ( " / (, ; " .
154
" "
3
"(B)
"(A)
2 |
|
1 |
|
|
|
|
|
||
|
|
|
|
B |
Ax = 0 |
|
x = 1 |
||
; . 16. ( & ! ! )$ ;# )
" "
"(B)
"(A)
3
2
1
A x = 0 x = 1B
; . 17. !'# ! ! )$ ;# )
8.4. #$ -# #
& " ( $ $ -$ , $ $,) " - , ( – + .
0 $. * , ( % + /-$ $ , $ . J / ) , -) %$ . ) -( %% . @ ", ; - % ( - % ( ), ) + % - . J + % ) + % -/ .
) ( ( . 0-% – ] , ;] ; %. C$ -$ " + $ .% ) , ; " ( -
155
% % % [p = f(x, y)],. 18. : 1 – ( - % % (); 2 – ( % -) + % ( ).
+ / ; ) – ) ) ( (P) (()) ) ) (;+(). !-+ CD 1 2 / -% ( 1) % (Y1) .
" |
T = const |
" |
T |
! |
|
p = const |
T |
|
|
|
|
||||||
|
1 |
|
"(B) |
T(A) +! |
1 |
|
|
|
|
; |
|
|
|
L |
N |
K |
|
|
|
D |
|
|
|
|
|
|
|
+ ! |
|
|
|
2 |
|
T(B) |
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
"(A) |
2 |
! |
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
X1 |
Y1 |
|
X1 |
X |
Y1 |
|
|
|
|
|
||
x = 0 |
(") |
x = 1 |
x=0 |
( " ) |
x=1 |
|
y = 0 |
( ) |
y = 1 |
y=0 |
( ) |
y=1 |
|
|
; . 18. + #'"# # |
|
; . 19. + #'"# # |
|||
« $ # – $ # ! #" » |
« $ # – ! !"# "# $ )» |
|||||
C . 19 ) « – » , + ($ .18, + , / +$ +". 1 " (% ( ), 2 – (( ).
, / -$ . &) !"K $ - -
# #:
) K ,K ! ,
156
? ! K ;
) K ( ) ! K.
0 / ) , ) « – » ( .19), (($ , + / - . ) / *, ) ) " ( .19). C$ " ,% ( N. -/ ( , + ) 1 2 $ K L - . ! ( ( ) ) :
L , ! |
|
||||
, , LN |
|||||
NK: |
|
|
|
|
|
|
m Ï |
|
LN |
. |
(8.17) |
|
m Ð |
|
|||
|
|
N K |
|
||
? ( , ; , $ " -, ( /$ %.
? , $ $ " + ) $ -, / ) , + ) .18 19, ( ) $. D- ; / ( $ ( )- ), / +$ )$ ( . 20 21). ( + /- / . B ) . 20 21 / ; -].
, $ ) $ . 20 21, ( , / 2-, $ - #-
#.
157
' |
|
|
||||||
|
|
, - |
||||||
|
K . |
|
|
|
||||
p |
T = |
|
p |
|
|
|
|
|
|
|
|
! |
|
||||
|
|
|
|
|
||||
A |
|
|
|
|
|
|||
|
|
|
|
|
|
+! |
||
|
|
+! |
|
p(") |
(. |
|
||
|
|
|
|
+! |
|
|||
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
p(.) |
! |
|
|
|
|
@ |
(" |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
x=0 |
( " ) |
x=1 |
|
x=0 (") |
x=1 |
|||
y=0 |
( ) |
y=1 |
|
y=0 |
( ) |
y=1 |
||
; . 20. + #'"# # |
|
|
|
; . 21. + #'"# # |
||||
«$# – $ # ! #" » |
«$# – ! !"# "# $)» |
|||||||
) ! & &- |
) ! & &- |
|||||||
! ) $ ;#- |
! ) $ ;#- |
|||||||
, / ) , - / . E . 21 , ; , $ - " ) , ($ %, + % ] ) . ! (( , %) , + " -% ]. * + , ; % - % , ( (.
158
T |
p=const |
|
T |
T |
|
p=const |
|
T |
||
|
|
|
|
|
|
|
|
T(B) |
||
T(A |
! |
|
|
|
|
|
|
|
||
|
T(B) |
T(A |
|
|
|
|
||||
|
!+P1 |
!+P2 |
|
|
|
|
|
|||
|
|
|
|
|
|
|
P2+! |
|
|
|
|
P1 |
P2 |
|
|
|
|
P1+! |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
P1+P2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
P1+P2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
. |
|
|
|
|
. |
|
|
" |
||
|
|
" |
|
|||||||
; . 22. + #'"# # |
|
|
|
|
; . 23. + #'"# # |
|
|
|||
«$# – ! !"# "# $ - |
«$# – ! !"# "# $ - |
|||||||||
)» ) ! & ? !9! H |
)» ) ! , $! |
|||||||||
|
" & H " |
|
|
|
|
)$ L |
|
|
||
|
|
|
|
|
|
|
! " & )H ) |
|
|
|
C ; ) + ( / - / ( . 22) , $ " / ( . 23). J ( . 22)/ ) ) ( - ) + (P1 P2), + + (P1 + P2). -( / / / ( -( .
) ( .23) " $ -$, ) ( ,"% ( , ( -. J $ $ /$ . ! % -( , ( % . -) / " "
K m0 , mi
m0 – % ; mi – .
159
8.5. # " & !" "! " #
% $ " ( ( .
' ? , ?.
& % ( % " %, ( , % ( "+’" , ; / ) ( " , ( - % ) + / .
( 0, ( % , % , . ! , /, ( :
X |
p0 p |
, |
(8.18) |
|
|||
|
p0 |
|
|
– % % .
& ( " ( + , ; -) ; ) .
p( )
p‚ = 1,013·105 = 1
p0=f(T) p=f(t)
12
0$ $ T, K
; . 24. + #'"# # «$ # ! #" – ! !"# "# $)».
#" # !" " & ! "!
) ) « –!» « - % – » ( .24). 1 " - ( % $/ -
160