II III
2005
: . .. , . . .. , . . ..
. .., . .., . ..,
. ..
,
..
: . , ,
... .. .
______________________2005 .
Ѡ ..
2,3 : , , 2002 .
- . , , . , .
, , , , .
, , :
- , , , ;
- , , .
1. D, DU, DG D0
22() = 2 () + 2 ()
, .
: , , :
Dr = Sni Dof Sni Dof =
= 2Dof CO + Dof O2 2Dof CO2 =
|
|
= [2(110,70) + 0] 2(393,51) = 565,62 /.
: DUor = DHor DnRT,
: Dn ,
Dn = 3 2 = 1;
R (8,314´10-3/);
= 298.
:
DU0r = 565,62 8,314´103 298 = 563,14 /.
DGor :
DSor = 2So + So2 2So2 =
= (2´197,48+205,03) 2´213,66 = 172,67 /.
T :
DGr = Dr DS0r = 565,62 298172,67´103 = 514,16 /.
:
Dor = DUor TDSor = 563,14298172,67´103 = 511,68 /
DGor Dor , .
2.
4 () = () + 22() + Δr
, ΔG0r298 ΔA0r298. ,
298 .
:
1)
(ΔG0 f 4 () = - 50,85; ΔG0 f () = 0; ΔG0 f 2 () = 0 /),
ΔG0r ( )
ΔG0r = åni ΔG0 f . - åni ΔG0 f . = ΔG0 f () + 2 ΔG0 f 2 () - ΔG0 f 4 () =
= 0 + 2× 0 (-50,85) = +50,85
2) ΔA0r ΔG0r ΔA0r:
ΔA0r = ΔG0r ΔnRT,
Δn ,
R -
Δn: Δn = ån. - ån. = 2 1 = 1
:
ΔA0r = 50,89 - 1× 8,314 × 10-3 × 298 = 48,41 ,
.. ΔG0r298 ΔA0r298 > 0, 298 .
3.
4 () = () + 22() + Δor
Δ0r, (/): Δ0 4 () = - 890,31; Δ0 () = -393,51; Δ0 2 () = -285,84
- .
: :
Δ0r = åni Δ0 . - åni Δ0 . =
= Δ0 4 () (Δ0 () + 2 Δ0 2 ()) =
= -890,31 - [-393,51 + 2× (-285,84)] = +74,88
.. Δ0r > 0, .
4. . ,
Δ0 = -890,31 /
(/)
Δ0f 2 () = -393,51; Δ0f 2 () = -285,84
:
4 () + 22 () = 2 () + 22 () + Δ0r
:
Δ0r = åni Δ0f . - åni Δ0f . =
|
|
= (Δ0f 2 () + 2 Δ0f 2 () ) (Δ0f 4 () + 2× Δ0f 2 ())
: Δ0r = Δ0 4 ()
: Δ0 4 () = (Δ0f 2 () + 2 Δ0f 2 ()) (Δ0f 4 () + 2 Δ0f 2 () );
-890,31 = (-393,51 + 2× (-285,84)) (Δ0f 4 () + 2 × 0);
- 890,31 = -393,51 571,68 - Δ0f 4 ()
Δ0f 4 () = -74,88 /.
5.
3()+3/22()=2()+22()
500 1,0133´105 .
: 298:
Dr 298 = (Dof CO2 + 2 Dof H2O) (Dof CH3OH +3/2Dof 2) =
= (393,512´241,8) (201,00 + 3/2´0) = 676,13 /.
Dr 298, 500:
Dr 2 = Dr 1 + D(2 - 1)
D . :
D = Snii . Snii . =
= (2 + 22) (3 3/2 2) =
= (37,11+2´33,56)(43,93/2´28,83) = 17,10 /
, 500 :
Dor 500 = Dor 298 + D(500298) =
= 676130 + 17,1´202 = 672676 / = 672,676 /.
6. DGor
3()+25()=325()+2()
3,434 /. . , 1 2 ?
: DGor = RTlnKp,
DGor - 3,434
lnKp= ¾¾¾¾ = ¾¾¾¾¾¾¾ = 1,386
RT 8,31410-3298
= 1,386 = 3,9989 4.
= (RT)Dn, Dn = 2 2 = 0, = = 4.
, , :
3 + 25͠ = 325 + 2 | ||||
, | 1 | 2 | 0 | 0 |
, | 1 | 2 |
:
= ¾¾¾¾¾ = 4 (1)(2-)
|
:
2=(1-)(2-)= 4; 2=(23+2)= 4; 2=812+42; 3212+8=0
D = Ö14496=6,928;
12 + 6,928 12 6,928 1 = ¾¾¾¾¾ = 3,15 ; 2 = ¾¾¾¾¾ = 0,845 . 6 6 |
= 3,15 . 1 ( 2 3 ) . , :
: 10,845 = 0,155 ,
: 20,845 = 1,155 ,
: 0,845 ,
: 0,845 .
7. 10 NaCl 100 () . :
1) ();
2) ();
3) ( );
4) () ;
5) ;
6) ;
7) 100 ( ).
:
|
:
- ;
M - ;
MP - ;
n - - 1 ;
p - , :
nNaCl= mNaCl/MNaCl=10/23+35.5=0.17 ;
nNaCl mH2O (1000 ) 0.17 1000
1) m = ----------------------------------- = -------------------- = 1,7 /1000 ;
mH2O 100
nNaCl 1000 렠 0.17 1000
2) CM = ---------------------------- = --------------------- = 1,7 /
100 (V H2O) 100
T 1000
3) N = ---------------- =; CN = 1,7 /
:
m X
N = -----------------,
100
m , ; X - , %; - , /-.
nNaCl nH2O (1 ) 0.17 1
4) N = --------------------------- = ----------------------; n- = nNaCl + nH2O; N = 0,033
n- 5+0.17
mNaCl VH2O (1 ) 10 1
5) = ----------------------- = ------------------------; = 0,1 /
V H2O 100
mNaCl 10
6) = ------------ = -------------; = 9,09 %
mH2O + mNaCl 100+10
7) = mNaCl / mH2O; = 0,1 /100
8. 100 1,53 . 298 3167,2 /2. : ) ; ) ; ) ; ) .
:
) :
D ¾¾¾¾ = ¾¾¾ = ,
|
.
= n/(n + n), n ().
n=100/18 = 5,555 ; n = 1,53/92 = 0,017 ;
|
, = 0,017/(0,017 + 5,555) = 0,003,
D/3167,2 = 0,03; D = 95,02 .
) :
m 1000 D = ¾¾¾¾¾, M a
|
( 0,52); m ; ;
.
0,52´1,53´1000 D = ¾¾¾¾¾¾¾¾ = 0,086. 92´100
|
, 100,0860.
|
|
) () :
m 1000 D = ¾¾¾¾¾, M a |
- ( 1,86):
1,861,531000 D = ¾¾¾¾¾¾¾ = 0,309 92100
|
, 0,309.
)
p = CRT,
.
/3. , :
1,531000 = ¾¾¾¾¾ = 0,17 / = 0,17´103 /3. 90100 |
p = 0,17´1038,314298 = 421187,2 ( 4,2 ).
9.
0,05 / 370.
() CaCl2 97%. : -, - ?
:
- :
p = iCRT,
i -
(/, /3)
R
,
i: i = 1 + a(n - 1),
a -
n - (),
l2 2+ + 2l-
(n = 3); i = 1 + 0,97(3 1) = 1 + 1,94 = 2,94
p = iCRT = 2,94 × 0,05 × 0,082 × 310 = 3,74 .
: p = 2,94 × 0,05 × 103 × 8,314 × 310 = 378868,98 p
.. p . l2 = 3,74 < p (7,6 )
.
10. 1 , 1 , . 0,0017. :
) , 40 ;
) , 4- 10 ;
) , () ();
) () ();
) 10 , , 97% .
.
) :
KV1 10,00171000 m1 = m0 ¾¾¾¾ = ¾¾¾¾¾¾¾ = 0,041 , KV1+V2 0,00171000+40 |
;
m0 () ;
m1 , ()
;
V1 ();
V2 () .
)
KV1 n 0,00171000 4 m = m0 -------- = 1 ---------------- = 0,00044 , KV1+V2 0,00171000+10 |
n - .
)
m = m0 - m = 1 - 0,00044 = 0,99956 .
KV1 4 0,00171000 4 m = m0 [1 ¾¾¾¾ ] = 1 [1 - ¾¾¾¾¾¾¾ ] = 0,99956 KV1+V2 0,00171000 + 10
|
:
) , , . :
a1 = (10,041)/1 = 0,959 95%;
:
a2 = 0,99956/1 = 0,99956 99,956%.
) V2=10 , , . ():
|
|
KV1 n a = m/m0 = 1 (¾¾¾¾); 0,97 = 1 0,145n; 0,03 = 0,145n. KV1+V2 |
lg 0,03 = n lg 0,145; n = lg 0,03/lg 0,145 = (-1,5229/-0,8386) =1,82.
.. (1,822).
11. , 1, , 1 . 0 333,5´103 /, 0,9998´103 /3, 0,9168´103 /3.
: :
D L ¾ = ¾¾¾ D T DV
|
D/D 1 ; L ; DV = (V V) .
, :
V=1/9,998´102=1,0002´103 3/;
V=1/9,168´102=1,0908´103 3/;
DV=1,0002´103 1,0908´103 = 9,06´105 3/;
D𠠠 333,5´103 ¾¾ = ¾¾¾¾¾¾¾ = 134,8´105 /ʠ D 273(9,06´105) |
, ( ) . , 1 134,8´105 ( 133 ), .. 134 .
:
DҠ 1 ¾¾ = ¾¾¾¾¾ = 0,0074´105 /; D 134,8´105
D 1 蠠 ¾¾ = ¾¾¾ = 0,0075 /; D 133
|
, 1 0,0075 -0,0075.
12. , 10 , 98,4. 94605 .
. m/m :
m ¾¾ = ¾¾¾¾, m
|
m m , ; .
:
= 101325 94605 = 6720 .
:
m⠠ 9460518 2,72 ¾¾ = ¾¾¾¾¾ = ¾¾¾ = 2,72 mࠠ 672093 1
|
, 1 2,72 , 10 27,2 .
13. , 0,8718 / , = 291, , 0,5 / NaCl.: ) ; ) .
:
) - : p1 = 1RT; NaCl : p2 = iC2RT, i - . , .. p1 = p2, 1RT = iC2RT.
ࠠ i = 1/2 = 0,8718/0,5 = 1,7436.
g:
g = i/n = 1,7436/2 = 0,8718,
n , .
) a , :
i = 1 + a(n 1);
a = (i 1)/(n1) = (1,7436 1)/(2 1) = 0,7436.
14. 20. , .
40660 /.
: :
2 D. (T2 T1) ln ¾¾ = ¾¾¾¾ ¾¾¾¾¾ 1 R T1T2
|
, T2 2 = 101325 100 (373), :
101325 40660 (373 353) ln ¾¾¾¾ = ¾¾¾¾ ¾¾¾¾¾¾ = 0,7428. 1 8,314 353373
|
ln1 = ln101325 0,7428 = 11,5261 0,7428 = 10,7832,
, 1 = e10,7832 = 48204 (0,47 .).
15. 0,1 , 20 = 4.
. , :
V.. .. = + lg ¾¾¾¾¾, V.. ...
|
, 4,74;
V.. V.. . .. = ..:
lg V../V.. = = 4 4,74 = 0,74; V../V.. = 100,74 = 0,18.
V.. = 20 V.., (20V..)/V.. = 0,18;
V.. = 16,95 , V.. = 20 16,95 = 3,05 .
16. 0,175 4,76´104 11. NH4+ 25 73,5 198,3 121. , , b, .
: À l
À 1000 l = ¾¾¾¾¾,
|
/, 1000 3.
l:
4,76´1041000 l = ¾¾¾¾¾¾¾ = 2,72 121 0,175
|
a a=l/l¥, l¥ , : l¥ = l+ + l (l+ l ):
l¥ = 73,5 + 198,3 = 271,8 121
a = 2,72/271,8 = 0,01.
= a2/(1a),
( = b
);
, /.
b: b = 0,0120,175/(10,01) = 1,77´105,
ࠠ b = lgb = 4,752.
a:
͖ = 0,010,175 = 0,00175 /.
= lg0,00175 = 2,76 , , pH = 14 2,76 = 11,24.
17. , , 0,01 , 0,02 .
: , :
Li K Ba Ca Na Mg Al Mn Cr Zn Fe Co Sn Pb H2 Cu Hg Ag Au
()
, , , . , . . , , . ( ) , , , . . . :
(-) Zn0 | Zn2+ || Cu2+ | Cu0 (+)
0,01
: , .
18. , ()Zn|ZnSO4 (c=0,5M)||CuSO4 (c=1M)|Cu(+), DG , (=250).
: :
RT 0,059 n+/ = n+/ + ¾¾ ln an+ = En+/ + ¾¾¾ lg an+, nF n
|
n+/ (. ); an+ ; n , ; F (96500 ).
= g g :
Cu2+ = 0,043´1=0,043 /; Zn2+ = 0,063´0,5=0,0315 /.
Cu2+/Cu= +0,337 + (0,059/2) lg 0,043 = +0,297 ;
Zn2+/Zn = 0,763 + (0,059/2) lg 0,0315 = 0,807 .
, ,
= + = +0,297(0,807) = 1,104 .
DG0 , , , : DG = nFE.
: = + .
= +0,337 (0,763) = 1,100 ,
DG = 2965001,100 = 212300 /.
( = )
DG0 = RTlnKp,
lnK = lnKp = DG0/RT = (212300)/[8,314(25+273)] =
= 85,6887 = = 85,6887 = 1,64´1037.
19. 25.
1 2 Zn | ZnS || ZnSO4 | Zn = C=0,5
|
0,276 .
: :
0,059 aZn2+, (2) = ¾¾¾ lg ¾¾¾¾¾. n aZn2+, (1)
|
, aZn2+, (1) () ZnS, . aZn2+, (2) = g= 0,063´0,5 = 0,0315 (. ).
aZn2+, (2) n E 0,2762 lg ¾¾¾¾ = ¾¾¾ = ¾¾¾¾ = 9,3559; x 0,059 0,059
aZn2+, (2) ¾¾¾¾ = 109,3559 = 2,2693´109;
|
: = aZn2+, (1) = 0,0315/(2,2693´109) = 1,391´1011.
,
1,39´1011 /, -
= Zn2+ CS2 = 2 = (1,39´1011)2 = 1,93´1022.
20. , 25 0,4185 . , , ?
:
= ¾¾¾¾¾; 0,059 |
( ).
= (0,41850,2415)/0,059 = 3;
+ = 10 = 103 = 0,001 /.
21. 10 2,38 1. , 90% , 1 0,05 . :
1)1 0,05 . N; 2) 1 0,1 . Na.
:
1) . :
1 x 1 x k = ¾ ¾¾¾, t1 = ¾ ¾¾¾, t1 a(ax) k a(ax) |
; t.
2 , ,
= 0,025 /, = 0,0250,9 = 0,0225 /.
1 0,0225 t1 = ¾¾ ¾¾¾¾¾¾¾¾¾¾ = 151,2 . 2,38 0,025(0,0250,0225) |
2. , :
1 b(ax) k = ¾¾¾ ln ¾¾¾¾¾ t2(ab) a(bx) |
- , b , = 0,1/2 = 0,05 /; b = 0,05/2 = 0,025 /; x = 0,025´0,9 = 0,0225 /.
t2:
1 0,025(0,050,0225) t2 = ¾¾¾¾¾¾¾¾ ln ¾¾¾¾¾¾¾¾¾¾ = 28,65 2,38 (0,05-0,025) 0,05(0,0250,0225)
|
22.
Cl2 = CO + Cl2
382 0,5´102 1, 482 - 67,6´102 1. : ) ;
) 425; ) , 382 100 , 1 /.
:
) * :
12 R k2 * = ¾¾¾¾ ln ¾¾, T2T1 k1 |
: k1 k2
1 2. :
6557558,314 67,6´102
*= ¾¾¾¾¾¾¾ln¾¾¾¾¾ = 201740,3 / 201,7 /
755655 0,5´102
) 425 *.
k3 * T3 T1 ln ¾¾ = ¾ ¾¾¾¾. k1 R T3T1 |
k3, :
201740 698655 ln k3 = ¾¾¾¾ ¾¾¾¾¾ + ln 0,5´102 = 3,016, 8,314 698´655 |
k3 = 3,016 = 0,049.
) . :
1 0
k = ¾¾ ln ¾¾¾¾,
t 0 -
0 ; C0x t; .
, , :
0,5´102 = (1/100) ln [1/(1-)];
ln [1/(1x)] = 0,5; ln(1x) = 0,5; 1x = -0,5 =0,6
, , x = 0,4 .
, 382 100 1 0,6 /, 0,4 .
23. 20 80? 2.
:
vT2/vT1 = kT2/kT1= g (T2T1)/10, g=2, T2=80o; T1=20:
Vt2/Vt1 = 26 = 64,
64 .
24. 10%, () 1,2´105 1 20o.
: 100%, 1-
1 a k = ¾ ln ¾¾, t ax |
:
1 100 0,1053 t = ¾ ln ¾¾¾¾ = ¾¾¾¾ = 8775 1 . k 10090 1,2´105 |
25. 1,5 , 6,4 . ?
: ( ) m = Jt/F,
J ()
t ()
F 96494 /- (¾¾¾) 96500 /-.
-⠠
, , 1 , .
= ¾,
n
; n
蠠 63,54
= ¾¾¾ = 31,77 /
2
mF 6,4 × 96500
t = ¾¾¾ = ¾¾¾¾¾¾ = 12959,8 = 216 = 3 . 36 .
J 31,77 × 1,5
1. s, 20o : n = 42, n=18. r=1,4´103 /3; s=72,75´103 /.
: :
n r 18 1,4´103 s = s ¾¾¾ = 72,75´103 ¾¾¾¾¾¾ = 43,65´103 /. n r 42 1´103 |
2. , : 11,8 × 102 /, 712 /.
200, s0 = 72,75 × 10-3 /
:
:
h - 712
s = s2 ¾¾¾ = 72,75´103 ¾¾¾¾¾¾ = 43,89´103 /.
h 2 11,8´102
3. (a = 12,6´10-3 b = 21,5), 0,104 / 273. s0 = 75,62´10-3 /.
:
Ds = s0 - s = a ln(1 + bC)
s:
s = s0 - a ln(1 + bC) = 75,62´10-3 -12,6´10-3(1 + 21,5´0,104) =
=60,82´10-3 /.
4. 6´108 . , 0,5 3 , , : ) (d) 6 × 10-8
) (ℓ) 10-6 .
: , ()
V = 4/3pr3 = 4/3 [3,14 (3´108)3] = 113,04´1024 3
V. . = ℓ3 = (10-6)3 = 10-18 3
:
n = V. /V = 0,5/113,04´1024 = 4,4´1021 ()
n = V. /V = 0,5/10-18 = 0,5 × 1018 ()
, ,
3 3 S= ¾ = ¾¾¾ =108 1; r 3´108 |
6 6
S. . = ¾ = ¾¾¾ = 6 ×106 1
ℓ 106
S , :
S = SV.. = 108´0,5 =5´107 2 (.); S. = 6´106´0,5 = 3´1062
:
S= nS = n4pr2 = 4,4´102143,14(6´10-8)2 = 4,97´107 5´1072.
5. ( /2) 10 , 50 / 817. 57´103 / 74,22´103 /.
Ds = ¾¾ ¾¾. D RT |
: :
/3:
= 0,05/158 = 3,164´104 / = 3,164´104 /3, (158 ).
(57´103 74,22´103) 3,164´104 = - ¾¾¾¾¾¾¾¾¾¾ ¾¾¾¾¾¾ = 7,32´109 /2. 3,164´104 - 0 8,314´103´283 |
6. , , , 30´1020 2, r = 978 /3.
: l
¥ l = ¾¾¾. r |
1
, S = ¾¾¾, ( NA- ,
¥ NA
6,02´1026 /), :
1 1
¥ = ¾¾ = ¾¾¾¾¾¾¾¾¾ = 0,055´107 /2.
S NA 30´1020´6,02´1026
(=88):
0,055´107´88 l = ¾¾¾¾¾¾¾ = 4,95´1010 5´1010 = 5 Å (). 978 |
7. :
´102, | 5,33 | 9,87 | 17,33 | 23,06 | 45,53 |
´103, 3/ | 14,9 | 19,1 | 24,2 | 27,3 | 36,8 |
( - , - ). . = 3000 . , , 5 .
: