( ) .
a , , . .
a =1 ( ) . , , (HCl, HBr, HI, HClO4, HNO3, H2SO4, H2SeO4 ).
a <1 . , ( NH2NH2, NH2OH, .), , HNO2, H3BO3, H2CO3, CH3COOH, H2SO3, HOCl, HCN, H2S ).
, . , .
.
:
⇆ + + .
= ,(2.5.1)
;
;
α .
α <<1,
(2.5.2)
, , , . :
a=f × C,
f , , , , ;
.
:
, (2.5.3)
f , .
.
( 0,5 /) , , :
, (2.5.4)
i ;
zi .
i , , , .
|
|
f . 298 - :
, . (2.5.5)
. 2.5.1 + - .
2.5.1
0,001 | 0,002 | 0,005 | 0,01 | 0,02 | 0,05 | 0,1 | 0,2 | |
+ | 0,975 | 0,967 | 0,950 | 0,923 | 0,914 | 0,880 | 0,860 | 0,830 |
- | 0,975 | 0,964 | 0,946 | 0,926 | 0,900 | 0,855 | 0,810 | 0,760 |
, .
.
:
(2.5.6)
, . +, -.
. :
2 D + + -,
-.
:
. (2.5.7)
220 1,810-16. 55,56 /. (2.5.7) :
(2.5.8)
. 220 W=10-14.
(=7).
>10-7 / (<7).
<10-7 / (>7).
, -.
(2.5.9)
-1 (2.5.8) :
+= 14 (2.5.10)
, , α =1. . .
, , , , , , . , - , . , . .
:
|
|
mBn mAn++nBm-.
, .
. .
(2.5.11)
, .
, . . :
. (2.5.12)
, , , .
, , , , . . , , (2.5.12), . , .
, :
. (2.5.13)
- , . . , (2.5.12).
, :
. (2.5.14)
1
0,01 HNO3.
, . . .
2.5.1.
:
2.5.1 I =0,01 fH+ =0.923.
:
+ = 0,920,01 = 9,210-3/;
= -lg9,210-3 = 2,04.
, = 14 - .
2
0,01 .
(α <1).
NH3H2O ⇆ NH4+ +OH
H+ , , .
, :
=α,
- , /.
, .
|
|
, (2.5.2) α> 0,1, (2.5.1).
, , .
NH32 0,01 :
=
NH32, , -:
=α = 4,2 10-2 10-2 = 4,210-4 /,
C- = = 4,210-4 /.
0,01 :
= -lg - = -lg 4,210-4 = 3,33
= 14 - 3,33 = 10,67.
3
HCN 6,2·1010. -, 0,1 0,1 /.
HCN . , 100,
.
.
-:
4
0,01 . Na2SO4 ?
1/2 Na2SO4. , 0,005 /.
Na2SO4 -,
C (Na +)=2 C (Na2SO4)=0,01 /;
C (SO42- -)= C (Na2SO4)=0,005 /.
.
: 0,015.
5
Ag2CrO4, /, 1,3∙10-12?
Ag2CrO4 ⇆ 2Ag+ + CrO42
= [ Ag+ ]2 · [ CrO42 ]
Ag2CrO4 x, [ CrO42 ]= x; [ Ag+ ]=2 x.
1,3∙10--12 = (2 x)2· x
1,3∙1012 = 4 x 3
C (Ag2CrO4)= x =
/, Ag2CrO4:
6,9·10--5 / ·332 / =0,023 /
: Ag2CrO4 0,023 /.
6
(III), 1 0,006 (III) 0,125 0,0001 ? (III) 3,8×10-38. .
(III)
Fe(OH)3 ⇆ Fe3++3OH-,
, , :
=[Fe3+][OH-]3.
(III), - . , , (III) 1 + 0,125 = 1,125 .
,
[Fe3+][OH-]3= 0,0053×(1,11×10-5)3 = 7,2×10-18.
<[Fe3+][OH-]3, (2.5.13) , (III).
, .
|
|
, , 3 3Na, , , NH4OH NH4Cl.
, , 34 NaH2PO4
NaH24 Na2HPO4.
, , (2.6.1):
= - lg , (2.6.1)
, /;
.
(2.6.1) , ( ). , .
= =1 lg =0, , = .
, , (2.6.2):
=14 - + lg (2.6.2)
, , 1 , . ./ ./.
, . ( ) ( ), . , .
, b (Cl) (NaOH), (2.6.3) (2.6.4):
(2.6.3)
, (2.6.4)
;
C(HCl) C(NaOH) , ./ ;
VHCl, VNaOH, Vb , , ;
1000 , ./.
1
[+], [-] , 30 0,1 3 50 0,3 3.
V = 30+50=80 .
:
[ 3 ] = /,
[ 3 ] = /.
, , , , :
[ 3 ] = (0,0375 ) /;
[+]= /;
[ 3 -] = (0,188+ ) /.
:
<< 0,0375 .
= [H+] = 1,7510-50,0375: 0,188= 3,510-6 /;
[OH-] = 10-14: 3,510-6 =2,910-9 /;
= -lg(3,510-6) = 5,46.
, (2.6.1):
= - lg = - lg (1,7410-5) - lg = 4,76 (-0,7) = 5,46.
2
, 0,12 3 3.
= = 0,12/2=0,06 /
= - lg = -lg(1,7410-5 ) - lg = 4,76 lg1 = 4,76 - 0 = 4,76.
3
0,25 3 50 1,0 3, =3?
(2.6.1):
= - lg ;
lg = = 4,76 - 3=1,76;
= 101,76 = 57,5
, 57,5 , . 0,051,0=0,05 . , 57,5 , 0,05:57,5=0,00087 .
0,25 :
V =0,00087/ 0,25 = 0,00348 = 3,48 .
4
, 24 24 16:1. .
|
|
24 (2= 6,210-8 = 7,2).
= lg ,
= 7,2 lg16= 6,0
5
, 0,2 NH4Cl 0,2 NH4.
(2.6.2), =14 - + lg .
(NH4) = 4,755, = 14 - 4,755 + lg = 9,25.
6
100 0,5 Na 440 0,1 . =3,8.
, , 1 , .
.
, , .
:
HCOONa + HCl = HCOOH + NaCl
/ (0,0018+ ) /, / (0,0014 ) /, 2,8.
(2.6.1), :
.
, . 0,075 /.
. .
:
HCOOH + NaOH = HCOONa + H2O
/, /, 4,8.
(2.6.1), :
.
, = 0,067 /. , 0,067 /.
( (.)) . , .
, . , . , :
¾ , ( ), , N4CI, Cu(N03)2, Fe13;
¾ , ( ), , 3Na, Na2CO3, NaHCO3;
¾ , ( ), , CH3COON4, I2S3, (NH4)2S.
, (NaCI, KNO3, NaCIO4 ), , +, .
- F13. F()3 H1, , Fe3+.
Fe3++HOHD[FeOH]2++H+ (2.7.1)
͗ , [FeOH]2+, K(FeOH2+)=1,41012. + .
FeCl3+HOHDFeOHCl2+HCl. (2.7.2)
(2.7.1) (2.7.2) FeCl3. , (Cu(NO3)2, 113 ), , (Na2S, 3O4 ), , .
, .
:
[FeOH]2++D[Fe()2]+++
FeOHCl2+HOHDFe(OH)2Cl+HCl; (2.7.3)
:
[F()2]++DF()3++
F()21+DF()3+1. (2.7.4)
, , , . , , : 1> 2> 3 ( 2.7.1). [FeO]2+, 3, , , .
, , , Fe3++2=Fe(H)3+3H+, ( [Fe]2+).
(Na2S, Na23, Na2S3, NaN, NaNO2, CH3COONa ), , .
Na2S.
:
S2+DS+ (2.7.5)
S , 2(S)=41014, (2.7.5) . , (>7).
(2.7.5) :
Na2S+HOHDNaHS+NaOH.
:
S+D2S+NaOH (2.7.6)
NaS+D2S+NaOH.
1(2S)=10-7, , (2.7.6) , (2.7.5), , Na2S S, Na+ NaHS NaOH.
(C3NH4 ), :
3+NH4++D3H+N32. (2.7.7)
( ). .>., , .>., , .=., .
2.7.2.
2.7.1 25
HN2 | 4,610 4 | |
HCN | 7,91010 | |
H2SO3 | K1=1,6102 2=6,2108 | |
H2S | K1=1107 K2=41014 | |
23 | K1= 4,5107 K2=4,71011 | |
3 | 1,75105 | |
34 | 1=7,1103 2=6,3108 3=51013 | |
HCIO | 5108 | |
NH4H N32 | 1,75105 | |
1()3 | 3=109 | |
(III) | F()3 | K1=4109 2=61011 3=41012 |
g()2 | K2=1,5103 | |
(II) | u()2 | K2=107 |
()2 | K2=2101 | |
Zn(OH)2 | 1=105 2=5107 |
, , . , , , , >7, , <7.
, , , , .
2.7.2
h | [H+] [O] | ||||
, ( ) | p< 7 | [H+]= | |||
C, ( ) | p>7 | []= = [H+]= = | |||
, ( ). | , p 7 | , : | [H+]= = | ||
, | p>7, (K>K I); <7, (K<K I) | [H+]= = |
, F13 Na2S, , , (2.7.1) (2.7.5).
:
+ + - = 2,
(2.7.1) (2.7.5) , . , :
FeCl3 + 3Na2S + 6H2 = 2Fe(OH)3¯ + 3H2S + 6NaCl
Fe3+ + 3S2-+ 6H2 = 2Fe(OH)3¯ + 3H2S
, , , l3+, Cr3+, Fe3+ c . .
1
- K2SO3.
. . .
1 : 2S3 + H2O D KHSO3 +
SO32- + 2 D HSO3+OH
2 : KHSO3 + 2O D 2S3 +
HSO3+ 2O D 2S3 +
2
- (II)
. . .
1 : Pb(NO3)2 + 2 D (PbOH)NO3 + HNO3
2+ + 2 D + +
2 : ()N3 + 2 D Pb(OH)2 + N3
b + 2 D Pb(OH)2 + +
3
NH4CN. ?
, , :
NH4CN + 2 D NH4OH + HCN
NH4+ + CN + 2 D NH4OH + HCN
NH4OH HCN ( 2.7.1). , , . , , .
4
0,5 Na2S, , .
- :
S2- + 2 D S + OH
Na2S o HS .
- H2S , 2.7.1.
=
:
h =
:
[H+]=
pH = - lg[H+] = - lg (2.8310 14 ) = 13,55
: , , , , . , , .
, Ca2+ Mg2+, Fe2+.
. . , , , , , .
, :
2C17H35COONa + CaSO4 = (C17H35COO)2Ca ¯ + Na2SO4.
.
, . .
Ca2+ Mg2+ . -. ( ) .
- 7 ./. ( 4 ./), (4 8 ./), (8 12 ./) ( 12 ./).
() (). , ,
(II). :
Ca(HCO3)2 CaCO3 ¯ + H2O + CO2
Mg(HCO3)2 MgCO3 ¯ + H2O + CO2 ;
2MgCO3 + H2O (MgOH)2CO3 ¯ + CO2
(MgOH)2CO3+H2O 2Mg(OH)2 ¯ +CO2
Fe(HCO3)2 Fe(OH)2 ¯ + 2CO2 ;
4Fe(OH)2 + O2 + 2 H2O 4Fe(OH)3.
, , , , .
, . , . , , .
:
Ca(HCO3)2 + Ca(OH)2 2CaCO3 ¯ + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 Mg(OH)2 ¯ + 2CaCO3 ¯ + 2H2O.
, . .
:
MeSO4 + Na2CO3 MeCO3 ¯ + Na2SO4.
. , , , Na+, H+, . , , , .
+ - , Na+ - .
: , , - .
1
( ./), 0,15 16,2 , 2,92 , 11,10 9,50 .
( ) :
,
m1, m2, mi , , , , ;
M1, M2, Mi , , , , /;
V , .
, , :
,
z , 2;
.
(HC3)2 | Mg(HC3)2 | Cl2 | MgCl2 | |
, / | 55,5 |
:
=
=2,56 ./
2
, 0,1 , , 7,2∙10-3 0,14 . HCl.
:
Mg(HCO3)2 + 21 = MgCl2 + 22 + 22
(8.1):
=10,08 ./
3
- 7,4 () 2 5,3 Na2CO3. .
()2 , Na2CO3 . :
Ca(HCO3)2 + Ca(OH)2 2CaCO3 ¯ + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 Mg(OH)2 ¯ + 2CaCO3 ¯ + 2H2O.
Ca(N3)2 + Na2CO3 = MeCO3 ¯ + 2NaNO3
Mg(N3)2 + Na2CO3 = MeCO3 ¯ + 2NaNO3
, , .
M(1/2()2) = 74/2=37 /;
M(1/2Na2CO3) = 106/2=53 /;
7400/(37∙50) = 4 ./;
5300/(53∙50) = 2 ./
:
= + = 4 + 2 = 6 ./