.


:




:

































 

 

 

 


. .., ...

 

: ..

 

 

 

 

- . , , . , .

, , , , .

, , :

- , , , ;

- , , .

 

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 () 0 () + 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 + 25 = 325 + 2
,        
, 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 () - , 1000 .
CM () - , 1 .
C (.) - - , 1 .
N ( ) - , 1 .
T - , 1 .
P - , 100 .
A , 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 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 333,5´103 ¾¾ = ¾¾¾¾¾¾¾ = 134,8´105 / D 273(9,06´105)

, ( ) . , 1 134,8´105 ( 133 ), .. 134 .

:

D 1 ¾¾ = ¾¾¾¾¾ = 0,0074´105 /; D 134,8´105   D 1 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 m 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 (+)

0,02 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

 

63,54

= ¾¾¾ = 31,77 /

 

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

 

, 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 ().

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 .

: lg = f(lg ). :

lg 1,83 1,72 1,62 1,56 1,43
lg 2,72 2,99 3,24 3,36 3,66

:

           
   
 
   
 
   
 
 


, lg = 3,02; = 9,55´104. : 1/n = tga = bc/dc = 0,4/0,94 = 0,43. = 1/n

 

:

= /m = 9,55´104´30000,43 = 2,99´102 3/.

5

= m = 5´2,99´102 = 0,149 3 .

1/ = f(1/p). :

1/ 0,00188 0,00101 0,00058 0,00043 0,00022
1/ 67,11 52,36 41,32 36,63 27,17

.

             
   
 
   
 
 
 
   


:

D = 1/¥ = 26; = 2/¥ =

52 /3; = 1/b = 0,0011 1.

¥ b:

¥ = 1/26 = 0,0385 3/;

b = 1/0,0011 = 909 .

, :

3000 = ¥ ¾¾¾ = 0,0385 ¾¾¾¾¾ = 29,5´103 3/. b + 909 + 3000

, 5 5´29,5´103 = 0,148 3 .

8.

, BaCl2 Na2S4 .

:

:

BaCl2 + Na2S4 = 2 NaCl + Ba S4¯

, BaCl2 Na2S4, .

BaCl2, :

{[m Ba S4] × n Ba2+ 2(n x)Cl-}2x+2x Cl-

1 2 3 4

 

: 1 -

2 -

3 -

4 -

(1,2) - ; (1,2,3,) - , ;

(1,2,3,4,) -

 

( ) Ba2+ . : , , . Cl- - , ( ) :

nBaCl2 nBa2+ + 2n Cl-

9. , 250 0,15 / 50 .

: , . , (). γ . / /.

. × V. γ = ¾¾¾¾;

V + V.

 

.

V.

V -

( )

 

= ¾¾ /; γ 0,15 × 0,05 γ = ¾¾¾¾ = 0,025 /;

0,25 + 0,05

= ¾¾ = 40 /

0,025

 

 

10. D D 10 , 50 , 293, 103 ×.

:

D



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