˲ ҲͲ
. , . , . , . , , , . .
, :
( 10-6 );
, ;
, .
. . :
K+, Na+, NH4+, Mg2+, ;
Ca2+, Sr2+, Ba2+, (NH4)2CO3 (=9) ;
Al3+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Zn2+.
, 䳺 NiS, CoS, FeS, Fe2S3, MnS, ZnS Cr(OH)3, Al(OH)3 ( );
Hg2+, Cu2+, Bi3+, Cd2+, Sn(II), Sn(IV), As(III), As(V), Sb(III), Sb(V), ;
Ag+, , Pb2+, Cu+, , HCl, .
. , , . . H2S . , - -.
- , . :
Ag+, Pb2+, , ;
Ba2+, Sr2+, Ca2+, Pb2+, ;
Al3+, Cr3+, Zn2+, Sn(II), Sn(IV), As(III), As(V), , 䳿 NaOH H2O2;
Mg2+, Mn2+, Fe2+, Fe3+, Bi3+, Sb(III), Sb(V), , ;
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Cu2+, Cd2+, Hg2+, Ni2+, Co2+, , ;
K+, Na+, NH4+, .
- , 䳭. , ( ), . :
K+, Na+, NH4+, . ;
, - 䳺 . : 1) Ba2+, Ca2+, Sr2+, Mg2+, Mn2+, Fe2+, 2 ; 2) Fe3+, Al3+, Cr3+, Bi3+, 2 , ;
Cu2+, Cd2+, Hg2+, Co2+, Ni2+, Zn2+, ;
Sn(II), Sn(IV), Sb(III), Sb(V), As(III), As(V). HNO3 . (III) , ;
Ag+, , Pb2+, .
1.2. (K+, Na+, NH4+)
, , , . .
, , (, CrO42-, Cr2O72, MnO4-).
; , (HCl, HNO3, H2CO3 .).
1.2.1. +. () Na3[Co(NO2)6]. + K2Na[Co(NO2)6]:
2K+ +3Na+ + [Co(NO2)6]3 = K2Na[Co(NO2)6]¯ + 2Na+.
, , , - ()3:
[Co(NO2)6]3- + 3OH- = Co(OH)3¯ + 6NO2-.
:
[Co(NO2)6]3- + 6H3+ = Co3+ + 6HNO2 + 62.
, Na3[Co(NO2)6] , ( 2+). +.
NH4+ +, Na3[Co(NO2)6] , , .
. ( 5-7) 2-3 Na3[Co(NO2)6]. , H3+. + .
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̳ . + Na2PbCu(NO2)6 :
2K+ + PbCu(NO2)62- = K2PbCu(NO2)6¯.
; NH4+, .
. . ϳ . +, .
. - .
. l 쒿, . ( ), . . , - .
1.2.2. Na+. ̳ -- Zn(UO2)3(CH3COO)8. Na+ Zn(UO2)3(CH3COO)8 - :
Na+ + Zn(UO2)3(CH3COO)8 + CH3COO + 9H2O =
= NaZn(UO2)3(CH3COO)9×9H2O¯.
ֳ Na+ K+, NH4+, Mg2+, Ca2+, Sr2+, Mn2+, Ba2+, Al3+, Cr3+, Fe3+, Zn2+, Co2+, Ni2+, Cd2+, Bi3+, Cu2+, Pb2+, Hg2+. -
Ag+, , Sb(III), PO43-, AsO43-.
. . ϳ , , . Na+, - , .
. . . . 1.2.1.
1.2.3. NH4+. (NaOH KOH) :
NH4+ + OH- = NH3 + H2O.
. , , , , .
. () 3-5 . () . , . , .
() K2[HgJ4] KOH ( ) NH4+ - -m- () NH2Hg2J3:
NH4+ + 2[HgJ4]2- + 2OH- = [NH2Hg2J2]J¯+ 5J- + 2H2O.
NH4+ . Fe3+, Bi3+, Cu2+, Cd2+, Ag+, Pb2+, As(V) ., (Fe3+, Bi3+) J-.
. ("") . .
. 12 . NH4+-, - .
. :
(NH4)2CO3 = 2NH3 + CO2 + H2O;
NH4Cl = NH3 + HCl.
, , :
(NH4)2SO4 = NH3 + NH4HSO4.
:
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(NH4)3PO4 = 3NH3 + H3PO4;
H3PO4 = HPO3 + H2O;
2Mg NH4PO4 = Mg2P2O7 + 2NH3 + H2O.
. , , . . .
. ϳ 䳺 , . :
2NH4Cl + Na2CO3 = 2NH3 + 2NaCl + H2O + CO2.
1.3.
(Ba2+, Ca2+, Sr2+, Mg2+, Mn2+, Fe2+, Fe3+, Cr3+, Al3+, Bi3+)
. ϳ 䳺 NH3 (~10) Ba3(PO4)2, Ca3(PO4)2, Sr3(PO4)2, Fe3(PO4)2, FePO4, AlPO4, CrPO4, BiPO4. Mg2+ Mn2+ MgNH4PO4, MnNH4PO4:
3Ba2+ + 2HPO42- + 2NH3 = Ba3(PO4)2¯ + 2NH4+;
Mg2+ + HPO42- + NH3 = MgNH4PO4¯;
Cr3+ + HPO42- + NH3 = CrPO4¯ + NH4+.
. ( Ba2+, Ca2+, Sr2+, Mg2+, Mn2+, Fe2+) , ( Fe3+, Al3+, Cr3+, Bi3+) . 3 HPO42- H2PO4-. ,
3 ( =1,8×105) ( = 6,2×108, = 4,7×1013):
Ba3(PO4)2¯ + 4CH3COOH = 3Ba2+ + 2H2PO4 + 4CH3COO;
2MnNH4PO4¯ + 4CH3COOH = 2Mn2+ + 2H2PO4 + 4CH3COO + 2NH4+.
(HCl, HNO3):
Ba3(PO4)2¯ + 6H3+ = 2H3PO4 + 3Ba2+ + 62;
FePO4¯ + 3H3+ = H3PO4 + Fe3+ +32.
:
AlPO4¯ + 4OH = [Al(OH)4] + PO43.
䳺 , Cr3+ rO42:
2CrPO4¯ + 3H2O2 + 10OH = 2CrO42 + 2PO43 + 8H2O.
.
1.3.1. . ó , .
. 2-3 2 4-5 (NH4)2HPO4; . . l, 3 . , 2 3. .
( NaOH) , , ; () (); - ():
Mg2+ + 2OH- = Mg(OH)2¯.
, Al(OH)3 Cr(OH)3 , :
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Cr(OH)3¯ + 3OH- = [Cr(OH)6]3-.
, , :
[Cr(OH)6]3- = Cr(OH)3¯ + 3OH.
. ( Ba2+, Ca2+) . . 1-2 2 , 2 NaOH. .
(NH4)2CO3, Na2CO3 K2CO3 , , , () :
Ba2+ + CO32- = BaCO3¯.
, () (MgOH)2CO3, ³(OH)CO3 Fe(OH)CO3:
2Mg2+ + CO32- + 4H2O = (MgOH)2CO3¯ + 2H3+.
Al(OH)3, Cr(OH)3:
Al3+ + 3CO32- + 3H2O = Al(OH)3¯ + 3HCO3-.
, (BaSO4, CaSO4), . CaSO4 , CaSO4 . .
1.3.2. Ba2+. 2+ , , :
Ba2+ + CrO42- = BaCrO4¯;
2Ba2+ + Cr2O72- + 3H2O = 2BaCrO4¯ + 2H3+.
, , Cr2O72-, CrO42-, . , H3+, BaCrO4, . , CH3COONa. H3+ CH3COO-, , BaCrO4 .
Ba2+ , Ca2+.
. 3-5 K2Cr2O7 . 2 CH3COONa, ( ) . , .
BaCO3, :
Ba2+ + CO32- = BaCO3¯.
( H2SO4 BaSO4).
. 2-3 1-2 (NH4)2CO3. Ba2+, .
() BaSO4:
Ba2+ + SO42- = BaSO4¯.
, Ba2+ Sr2+ Ca2+, . , , . ³ , Ba(HSO4)2. , Na2CO3. BaCO3, :
BaSO4¯ + CO32 = BaCO3¯ + SO42.
BaCO3, , , BaSO4, , BaSO4 Na2CO3. , Na2CO3 . .
. 2-3 1-2 H2SO4. Ba2+, BaSO4.
1.3.3. Ca2+. Ca2+ :
Ca2+ + C2O42- = CaC2O4¯.
CaC2O4 , . Ca2+ Ba2+ Sr2+, (NH4)2C2O4 . ~3,0-3,5.
. 2-3 1-2 , . Ca2+, .
̳ . , 䳭 , CaSO4×2H2O. ֳ Ca2+ Ba2+.
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. 1 H2SO4 . Ca2+, CaSO4×2H2O, .
(NH4)2CO3 Ca2+ CaCO3. ϳ :
Ca2+ + CO32- = CaCO3¯.
.
. 23 12 (NH4)2CO3. Ca2+, CaCO3.
Ca2+ , CaSO4:
Ca2+ + SO42- = CaSO4¯.
, BaSO4 SrSO4. ³ (NH4)2SO4, :
CaSO4¯+ SO42 = [Ca(SO4)2]2.
1.3.4. Mg2+. ( ---) - . . , Mn2+, Ni2+, Co2+, Cd2+.
. 2-3 12 . .
Mg2+ NH4Cl MgNH4PO4:
Mg2+ + HPO42- + NH3 + 6H2O = MgNH4PO4×6H2O¯.
ѳ , Mg(OH)2. Ba2+, Ca2+ .
. 1-2 2-3 2 HCl 1-2 Na2HPO4. 2 NH3. ϳ . , NH4Cl. MgNH4PO4. (~9-10). , .
1.3.5. Mn2+. () , . Mn2+ 䳺 . Mn2+.
(NH4)2S2O8 ( Ag+) Mn2+ MnO4-. - :
2Mn2+ + 5S2O82- + 24H2O = 2MnO4- + 10SO42- + 16H3+.
. 23 (NH4)2S2O8 ( 1 50% ), 0,5 2 HNO3 23 0,1 AgNO3. ( ). , , ( 50) 1-2 . - . , , MnO(OH)2. AgNO3, , .
Mn2+ MnO4- :
2Mn2+ + 5BiO3- + 14H3+ = 2MnO4- + 5Bi3+ + 21H2O.
l, MnO4-.
. 1-2 3-4 HNO3, 5-6 NaBiO3. . Mn2+ - .
, Mn2+ MnO(OH)2 ( MnO2×2H2O) :
Mn2+ + Br2 + 4OH- = MnO(OH)2¯ + 2Br- + H2O.
. 5-7 . 쳭 . Mn2+ .
2.3.6. Fe2+. () K3[Fe(CN)6] Fe2+ Fe3[Fe(CN)6]2 :
3Fe2+ + 2[Fe(CN)6]3- = Fe3[Fe(CN)6]2¯.
Fe3[Fe(CN)6]2 , , Fe(OH)2.
. 2-3 (). Fe2+, - ( ~3).
1.3.7. Fe3+. () K4[Fe(CN)6] Fe3+ - Fe4[Fe(CN)6]3 :
4Fe3+ + 3[Fe(CN)6]4- = Fe4[Fe(CN)6]3¯.
Fe4[Fe(CN)6]3 ; Fe4[Fe(CN)6]3, Fe(OH)3:
Fe4[Fe(CN)6]3¯+ 12OH = 4Fe(OH)3¯ + 3[Fe(CN)6]4.
(-, -, - .), Fe3+ .
. 2-3 1-2 K4[Fe(CN)6]. Fe3+ . Fe3+ , , . ֳ Fe3+- . : , 2 HCl K4[Fe(CN)6]. Fe3+ .
(KSCN NH4SCN) Fe3+ : [FeSCN]2+, [Fe(SCN)2]+, [Fe(SCN)3] , [Fe(SCN)4]-. Fe3+ , , .
. 2-3 1-2 HNO3 2-3 . Fe3+ . : , HCl 2-3 . Fe3+, .
1.3.8. Cr3+. () CrO42-, Cr2O72-. Cr3+ Cr2O72- (H2O2, Na2O2, KMnO4, Cl2, Br2, (NH4)2S2O8, .)
() H2O2, . () (). :
2[Cr(OH)4]- + 3Br2 + 8OH- = 2CrO42- + 6Br- + 8H2O.
. 2-3 3-4 2 NaOH, 2-3 () 3% . CrO42- H2CrO6.
() KMnO4, (NH4)2S2O8 :
2Cr3+ + 2MnO4- + 11H2O = Cr2O72- + 2MnO(OH)2¯ + 6H3+.
MnO(OH)2.
. 2-3 2-3 1 H2SO4 HNO3, 10-15 KMnO4 . , . c Cr2O72- .
. 䳿 H2O2 H2CrO6 :
Cr2O72- + 4H2O2 + 2H3+ = 2H2CrO6 + 5H2O.
( Cr3+), ( ). , .
. 2-3 , (), 1 H2SO4 , 0,5 , 4-5 H2O2; , - . - Cr3+ Cr2O72-, .
1.3.9. Al3+. S ( 1,2---3-) Al3+ AlOH[C14H6O3(OH)]2, . . Fe3+, Bi3+, Cu2+ , , .
. 2-3 2 ( , ). 2-4 ( ) 2 CH3COOH ( ). .
. K4[Fe(CN)6], . , Al3+ . ϳ , , . , , 2 CH3COOH. Al3+ .
( ) Al3+ .
. 2-3 2 CH3COOH, 3-5 . NH3 ( ) 2-3 1 Na2CO3. , .
1.4.
(Cu2+, Zn2+, Ni2+, Co2+, Hg2+, Cd2+)
, , . ֳ NH3 . NH3, .
(, , , .) ( , , ).
1.4.1. . ó () , - . ,
Cu2+ + HPO42- = CuHPO4¯.
:
CuHPO4¯+ CH3COOH = Cu2+ + H2PO4 + CH3COO.
:
Zn3(PO4)2¯ + 12NH3 = 3[Zn(NH3)4]2+ + 2PO43-.
:
CuHPO4¯ + 5OH = [Cu(OH)4]2 + PO43 + H2O;
Zn3(PO4)2¯+ 12OH = 3[Zn(OH)4]2 + 2PO43.
. 2-3 . . , , .
(), :
Cu2++2OH-=Cu(OH)2¯;
Cu(OH)2¯ + 4NH3 = [Cu(NH3)4]2+ + 2OH-.
ij :
[Cu(NH3)4]2+ + 4H3+ = Cu2+ + 4NH4+ + 42.
. 2-3 , . , , . .
Cu(OH)2, Zn(OH)2, Hg(OH)2, Hg(OH)2 HgO:
Hg(OH)2¯= HgO¯ + H2O.
:
Zn(OH)2¯ + 2OH- = [Zn(O)4]2-.
Cu(OH)2, . , .
1.4.2. Cu2+. , , Cu2+ :
Cu2+ + 4NH3 = [Cu(NH3)4]2+.
. 2-3 , - , . Cu2+, .
() K4[Fe(CN)6] <7 - Cu2[Fe(CN)6]:
2Cu2+ + [Fe(CN)6]4- = Cu2[Fe(CN)6]¯.
NH3 ; , . Fe3+.
. 1-2
1-2 K4[Fe(CN)6]. Cu2+, - Cu2[Fe(CN)6].
Na2S2O3 Cu2+ Cu2S:
2Cu2+ + 3S2O32- + 3H2O = Cu2S¯ + S4O62- + SO42- + 2H3+.
Hg2+.
. 10-15 1 H2SO4 2 2-3 . . Cu2+, Cu2S.
1.4.3. Zn2+. (NH4)2[Hg(SCN)4] Zn2+ :
Zn2+ + [Hg(SCN)4]2- = Zn[Hg(SCN)4]¯.
. ( H2SO4) 1 . Fe2+, . Fe3+, . , Fe(SCN)3.
. 2-3 , ( 1 ) 2-3 . .
() ( ) Zn2+ - .
. 2-3 1 5 1-2 10% CCl4 ( CHCl3). Zn2+, . Ag+, Bi3+, Pb2+, Cu2+. , 4-5 0,5 .
1.4.4. 2+. ҳ- SCN Co2+ [Co(SCN)4]2 . 4-5. NH4SCN , :
Co2+ + 4 SCND [Co(SCN)4]2.
, .
. 23 12 2 3, 23 ( ) NH4SCN 0,5 . , , , . , .
1--2- 2+ - [Co10H6(NO)O]3Co, . 2+ 3+, . .
. 12 , ( ) . - .
2+ : , 2+, 1--2-. 2+ .
1.4.5. Ni2+. .. Ni2+ , :
5-10. Fe2+, u2+.
. - 1-2 NH3, - 1%- . Ni2+ .
1.4.6. d2+. [BiJ4] 䳺 Cd2+, - . ³J3:
d2+ + 2[BiJ4] "CdJ2 + 2BiJ3¯.
. [BiJ4]. d2+ BiJ3, J Na2S2O3.
[BiJ4] J BiJ3, J [BiJ4] :
Bi3+ + 3J " BiJ3$;
BiJ3 + J " [BiJ4].
- ( 2S Na2S) d2+ 3-10 .
d2+ + S2 = CdS$.
, , .
. - , . 1-2 譭Na2S, . CdS.
1.4.7. Hg2+. Hg2+ :
Hg2+ + u¯ = Cu2+ + Hg¯.
. , , . , . .
() SnCl2 () () Hg2Cl2 () , . SnCl2, () . :
2HgCl2 + SnCl2 = Hg2Cl2¯ + SnCl4;
Hg2Cl2 ¯+ SnCl2 = 2Hg¯ + SnCl4.
. Ag+, Pb2+, , Cl- .
. 3-4 Ⳮ SnCl2. Hg2Cl2, .
() ( 2) HgS, , HCl + H2O2 HCl + KJ:
Hg2+ + 3S2O32 + 2H3+ = HgS¯ + 2S¯ + SO42 + 2SO2 + 3H2O.
Ag+, Cu2+, Pb2+.
. 2-3 2-3 1 H2SO4 Na2S2O3. . HgS.
1.5. ϒ (Ag+, , Pb2+)
, AgCl, Hg2Cl2, PbCl2. . , . [Ag(NH3)2]+, [AgI4]3-, [PbI4]2-, [AgCl3]2-, [Ag(CN)2]- .; .
1.5.1. . , () :
2Ag+ + HPO42- = Ag2HPO4¯;
3Pb2+ + 2HPO42- + 2OH- = Pb3(PO4)2¯ + 2H2O.
; :
Ag3PO4 ¯ + 2CH3COOH = 2CH3COO +3Ag+ + H2PO4;
PbHPO4¯ + 2H3O+ = H3PO4 + Pb2+ + 22;
Ag2HPO4¯ + 5NH3 = 2[Ag(NH3)2]+ + NH4+ + PO43-.
:
Pb3(PO4)2¯+ 18OH = 3[Pb(OH)6]4 + 2PO43.
() 䳺 NH3 (HgNH2)3PO4×3Hg:
(Hg2)3(PO4)2¯+ 6NH3 = (HgNH2)3PO4¯ + 3Hg¯ + PO43- + 3NH4+.
. 2-3 , () 3-4 . , , .
Ag+, , Pb2+ AgCl, Hg2Cl2 PbCl2 . [Ag(NH3)2]+. PbCl2 . HCl [AgCl2]-, [PbCl3]-, [PbCl4]2-.
. 2-3 , 2-3 2 HCl . NH3, HCl .
Pb(OH)2, AgOH, Ag2O, Hg2O:
2Ag+ + 2OH- = 2AgOH¯;
2AgOH¯= Ag2O¯ + H2O.
[Pb(OH)6]4-:
Pb(OH)2¯ + 4OH- = [Pb(OH)6]4-.
. 2-3 , , () , . , , ; () . , Pb(OH)2 , () .
1.5.2. Ag+. Ag+ AgCl:
Ag+ + Cl- = AgCl¯.
, .
HCl Ag+, [AgCl2]-:
AgCl¯ + Cl- = [AgCl2]-.
, :
AgCl¯ + 2NH3 = [Ag(NH3)2]+ + Cl;
[Ag(NH3)2]+ + Cl + 2H3O+ = AgCl¯ + 2NH4+ + 2H2O.
. <7; >7 Ag2O. , Pb2+ .
. 2-3 2-3 2 Hl. Ag+ , HNO3 . , , , HNO3 ( ) 1-2 . AgCl.
Ag+ AgJ:
Ag+ + J- = AgJ¯.
. 2-3 2-3 . Ag+ , H2SO4 HNO3. ( (AgCl) =1,78×10-10), NH3 ( (AgJ) =8,3×10-17).
1.5.3. . Hl :
+ 2l- = Hg2Cl2¯.
Hg2Cl2, AgCl, Hl