,,, ( ), (CIP) /. 4. :, ISBN X13 CIP ( 2004) (021) w ww.hdlgpress.co m.cn ( ) / 16

Transcription

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2 ,,, ( ), (CIP) /. 4. :, ISBN X13 CIP ( 2004) (021) w ww.hdlgpress.co m.cn ( ) / ISBN / O 121 : 38.00

3 , 4, 10,,,,,, : ( 1) ; ( 2) ; ( 3 ) ; ( 4),

4 ,,,,,,,,,,,, 40,,, ( ),,,,,,,,,,,,,,,,,,,,

5 20,,,, ( ),, ( ),,,,,,,,

6 (1989 ),,,,,,,,,, ( 1996 ),,, ( ) 10,,,,,,,,,,, ( ) 4

7 (1996 ) ; 1999 ;, 21,,,,,,,, 9,,, 3 4, :,,,,,,,

8 (1 ) 1.2 (5 ) 1.3 (9 ) ( 11 ) (12) ( 15 ) 2.2 ( 20 ) 2.3 ( 21 ) 2.4 ( 31 ) 2.5 ( 33 ) 2.6 ( 38 ) 2.7 ( 50 ) ( 52 ) 1. ( A PI) (53) 2. (57) ( 59 ) 3.2 ( 61 ) 3.3 ( 63 ) 3.4 ( 79 ) 3.5 ( 85 ) 3.6 ( 88 ) 3.7 (116 ) (119 ) 1. (121) 2. (122)

9 (124 ) 4.2 (125 ) 4.3 (130 ) 4.4 (132 ) 4.5 (133 ) 4.6 (138 ) (140 ) 1. (142) 2. DDT (144) (147 ) 5.2 (151 ) 5.3 (157 ) 5.4 (166 ) 5.5 (175 ) 5.6 (194 ) 5.7 (202 ) (203 ) 1. (205) 2. (209) (211 ) 6.2 (217 ) 6.3 (218 ) 6.4 (220 ) (223 ) 1. ( TOC ) (224) 2. (225) (227 ) 7.2 (242 ) 7.3 (254 ) 7.4 (272 ) (281 )

10 3 1. (283) 2. (286) (289 ) 8.2 (293 ) 8.3 (299) 8.4 (301) 8.5 (304) 8.6 (306) (309) 1. (309) 2. (312) (316 ) 9.2 (320 ) 9.3 (327 ) 9.4 (334 ) 9.5 (341 ) 9.6 (345 ) 9.7 (352 ) 9.8 (356 ) 9.9 (361 ) (366 ) 1. (369) 2. (371) A (375 ) B (389 ) B.1 (389 ) B.2 (390 ) B.3 (393 ) B.4 (401 ) (411) (412)

11 ,,,,,,,,,, km, kg, , ( )( ) ( ) ( ),,,,,,,,

12 2 1 1 / g / g ( 11 k m ) ( ) : 1 2 ( ) ( % ) ( ) ( % ) ( % ) ( ) ( % ) ( % ) Fe 35 N 75.5 O 85.8 O 46.6 O 53 O 29 O 23.2 H 11 Si 27.7 C 39 Si 14 Ar 1.3 Cl 1.94 Al 8.1 H 6.6 Mg 14 C Na 1.05 Fe 5.0 N 0.5 S 2.9 Ne Mg 0.13 Ca 3.6 Ca 0.4 Ni 2.4 Kr S 0.09 Na 2.8 K 0.2 Ca 2.1 H e Ca K 2.6 Si 0.1 Al 1.8 Xe K Mg 2.1 P 0.1 Na 0.3 H Br T i 0.57 Mg 0.1 P 0.2 S C H 0.22 S ,,,,, ( ),,, 70 km, 1.4 g/ cm 3, K, K, km,, 78.4%19.8% ( ), (h ) : H 4 2 H e e + h 4 0.7%, ( ) 6, W/ m 2,

13 W/ m 2 ( ) 99% 0.17 m4 m, 0.49m,, 1 2, 0.29 m4 m,, 1 2, 25, ,,,, 1 3, 19% ; 34% ; 47%, ; 0.1%, ;,,, ,, 10 (1), , 7, ; (2), km 2, 1 ; (3),, 40%,

14 4 ; (4), 1 100, ; (5), 19.6,2.5 ; ( 6), 0.8% ( ); (7), 100 ; (8 ), 2040, ; ( 9), ( ) , 12 ; (10), 1993,, , (3P + 3E), ( population) (poverty) ( pollution)(energy) (ecology) (environment), 1 4,, ( ),

15 1 5,,,,, (1 4) ,,,,, ( ),, ( ),, : ( ) - ( ) = () () ,, ; (),, (),,

16 6,,,,,,, ;,, ;,,,,,,,,, (),,,, 20,,,,,, :,,,,,,,, ,,,, : (1), Cd Cr Cu Hg Pb Zn As ; (2), CN - F - Cl - Br - S 2-4 ; ( 3 ), N H 4 + NO2 - NO3 - PO ; (4), 1978 (EPA) 129, SO ; (5), 3 H 32 P 90 Sr 131 I 144 Ce 232 Th 238 U H2 O CO2 : ( 1), SO2 ; (2 ), N2 O2 (NO x ) ; (3) ; (4), CO ; (5),,,, 1990 ( CAAA) 189 ( HAPs), 23 (),

17 ,, 1 000,,,, 2 000,, 67, 7 000, 10,,,, 3 000,, CO2, H 2, CO2,, CO ( ),, 21,, , ( 9.1), CO2 20%, , : ( 1), ( ), ( ),, (2),,, ( ) / 1 3,, - OH 8,,,, / PoctKow

18 ( ) / + ( / ) ; + ; : ; ; ; ; ; ; ;,, ;,, Fe2 ( SO4 ) 3, 410 gcr(), Cr();, As()As() ;, As2 O3 ( ), As2 S3 ();,,, 0.01 mg/ m 3,,

19 1 9,, ,, ,, (, ) -- ( PCDDs ) ( Pu ) ( MIC) ( F P s) ( sarin) ( U ) (, 1976 ) (, 1979 ) (, 1983 ) (,1984 ) (,1986 ) (, 1986 ) (, 1991 ) (, 1996 ) (, 1999 ) PCDD s,,, 8 PCDDs, 32.5, Pu, 46 MIC,, 20, 3 000,, 300, 4 000, 30 50, ,,,,, 5 500, 12, 78, , 20 70,,, ( )

20 10,,, ; ;,,,,,, : (1) ; (2 ) ; (3) ( ),,,, 1 6,,,,, (),,,, ; ; ;, : ( 1) ( ),,, () ; (2),,,,,,,,,,, (3 ),,,,

21 ,,, (4 ),,,,, ( ),,, 1.???,??

22 12 2.? 3.?,?? 4.?????? 5.,,? ( ),,,, 0.1 %, ; 2.7 %, ;,?? 7. CO 2 20%,?,,? 8.? 9.?,?? ( C H 3 SH ) t 1 = p 1 = k Pa, t 2 = - 7.9p 2 = kpa T b p = ( A - B/ T) ( Pa), A B,A B 2 4. = T 1.5 m T + b 10-6 [g/ (cms) ], T, m b CO 2 m b ,0 ( m b ) 5. 25,p H = 8.4, c T = 10-3 mol/ L, [ HCN ] [ CN - ] ( ,HCN )? 6. K h = min - 1, 5, 850, 60,,, 20, , 60 5 ( ) : ; 10.27; 2.78 ; , 1/ 5, 4/ 5, 7 800

23 / 10 / BC AD , :,,,, ( ) ; ( );( ), 12 1,12, 8.8, 2/ , 300,,, , 62, , % ( ) 2001 ( 7% ),, 366, ,2025, 60% 660, 30 %, 90 % 1 1

24 14 (3500 ), ( 100 / ),,,, 14,,, 1/ 4 23 % 28 % 400 : SA RS ,, 28 (W HO ), 5 050, 321,( )( ),,,,,,,, 1 = m 2 SAR S sev ere acut e res pira tory syndrom, W H O SA RS

25 , km3 000 km, ;, ; ;,, ( ),,,,, 2.1,,,, (),,,, , (, ),, :,,, 2 1

26 16 80 km (), : (1) ; ( 2), ; (3), 41, 1902 ( Marconi G.), 10 km,,, 10 m( 100 m), ; 300 m400 m( m2 000 m), ; 1 km 10 km( ),, 10 km50 km, 10 km40 km kpa, (O3 ) ( ), ) 2 1, 5 7,,,, 16 km 8 km, 1 km, - 50,, 50 km,,,, - 100,, 500 km, ,, ,,,,, ( 289 K),, () : 1.5m 2) 2 1, ( Pa), ( h) ph : ph = poe - Mgh/ RT (2 1) p 0 ( Pa) ; ( millib ar), 1 = 100 Pa

27 2 17 M (28.97 g/ mol) ; g ( 981 cm/ s 2 ) ; h / cm; R ( ergk - 1 mol - 1 ) ; T / K, ( ) , 77% : 90% 20 km, 99.9%50 km 100 km, 3),,, 3 km28 km 2 2 ( kg) ( g) ( RH), g/ cm 3 g/ m 3 4) ua, ua : ua = 8 R T M R ; T ; M (2 2 ) 2 2, 0.5 km1/ 16, 4, 11.2 km(,, ),,,,,,, ;,

28 18, 2 d : d= n = kt 2p ( 0.4nm 2 ) ; n ; k ( J/ K); T ; p 600 km, cm 1 (2 3) d,,,, d (p ),,, 5) 1 2,, : O3 O2 N2 h O2 + O (< nm) h O + O (< 242 nm) h N + N (< 127 nm) : H2O NO h H + HO(< 200 nm) h NO + + e (< nm) O2 O N h O e (< nm) h O + + e (< 91.0 nm) h N + + e (< 85.2 nm) h N2 N e (< 79.6 nm),,,, 0.3 m0.7 m (0.1m0.15m )70 km N2 O2 O3 H2O 2 3

29 ,, ( ),,,,,,, SO2 NO NO2 6), / gcm - 3 / - 1 / J( g ) - 1 / Jg - 1 / J( cms ) - 1 ( ) ( ) ( ) (25, kpa) (0, kpa ) (100, k Pa) ( , kpa) (0 ) ( 20,101.3 k Pa) (20, kpa) ( 20, k Pa) 2.1.2, 7, ( 2.3.5) / cm 2 / cm

30 20 2.2, : (1 ) ( ), ; ( 2),,,, ; (3), ; atm mmhg,, : % ( )mol/ L g/ L mg/ Lg/ m 3 / cm ( ) 10-9 ( ) ( ), ppm ppb ppt (SO2 NO x ), 10-6 ( ) g/ m 3 ; (H O ) ( ) / cm 3,, g/ m 3,, g/ g ng/ g, STP (cm/ km), ( STP, 273K ) (cm) 10-6 ( ) = 10-6 ( ) (2 4) 10-6 ( )= R T pm [g/ m3 ] (2 5) g/ m 3 = pm R T [10-6 ( )] (2 6) 298K Pa, ( ) = ( / cm 3 ) (2 7) 1 1.5% ( ), mg/ m 3? ( Pa ) (2 1.5% = [10-6 ( ) ] pmco 6), R T [10-6 ( )] = ( ) = g/ m 3, mg/ m HO, [[ H O]/ cm 3 ], [10-12 ( ) ]? ( Pa ), H O: V = ( ) = cm 3 [10-12 ( ) ] V V = = ( ) 3 (50km), 80Pa, 0,?

31 2 21 ([/ cm 3 ] ), : n V = p R T = = / cm 3 = mol/ m3 2.3, : (1 ) ; (2) ; (3) ; (4), 2.3.1,, % N2 O2 Ar 99% 99.96% % CO2 2 3 [ 10-6 ( ) ] ( ) N a O 2 Ar CO 2 Ne H e K r Xe a ( ) 5 10 a ( ) 10 7 a ( ) ( ) C H 4 CO H 2 N 2 O O a a 4 8 a 2.54 a 0.32 a H 2 S SO 2 N H d 24 d 56 d NO d ; ; %, 2 3 :

32 22, CO2,,,, CO2,, CO2, SO2 NH3 NO2,,, 2 3, ( ) ; ;, ( ) ( )( ), ( kg),, 10 ( 1) ( 2) (3) : ( rainout), (); (washout),, ( 4),, ( 5), : ps, Pa; T, K; Hv, Jmol - 1 ; R dln ps d T [ J/ (Kmol) ] Hv T,,,, : ps = e - H v/ RT (2 8 ), ps,,,, ; ( ) 2 = H v R T 2 (2 8) 4, ( )

33 , ( ), : (1) ; ( 2), ; (3) SO2 ; (4),,,,, 50 g/ m 3 ( 1952 ), 100,,, : (1) ; (2) ; (3) ; (4) (0.1 m1 m)(1 m100 m) 2, : (1),, (2 ), : ( 1) (2),, SO m10 m 2 5 NO3 - Cl - ; Ca 2 + Mg 2 +, ( IP) ( TSP ) 30m, ( ) 10 m, 2.5 m,2.5 m10 m,,, 0.1 m100 m 10m,,, IP PM 10 P M 2.5, P M 10

34 ( aerosol) ( mist ) ( dust ) ( smoke) ( fume) ( plume) ( fog) ( h aze) ( smog) ( ) sm ok e, smoke, ( fog) smoke fog , : H2 O h H+ HO,,, H2S NH 3 CH4,,,,, H2 SO4 HNO3 H2 CO3,,,, : (1), ( ); (2),, ; (3),, : Cl2 h 2Cl Cl+ CH4 HCl + CH3

35 2 25 CH3+ Cl2 CH3+ CH3 Cl CH3+ Cl Cl+ Cl Cl2 CH3+ CH3 CH3 Cl + Cl C2 H6 + Cl CH3 Cl C2 H6, H O RO H O2 RO2 O 2 -,,, HO, H O ( ), HO : 1 2,2 2, 3 2, 1 3, 2 p nm 4.62l ev(446 kj/ mol) 1.66 D O - H cm V( HO+ H + + e H 2O),,, H O (EPA) Models - 3/ CMAQ (), HO, ( PM2.5 ) 2 7 CM AQ Community Multiscale Air Q uality

36 26, (2 7), NO x,, [NO - 3 ( P) ], [ SO 2-4 ( P ) ], H O HO : H2 O HO: h HO+ H O3 h O( 1 D) + O2 O( 1 D) + H2 O 2 HO HO : HONO h HO+ NO H2 2H() H+ NO2 HO+ NO HO : H O, HO, : (1) H HO+ CH4 CH3+ H 2O (2) HO+ C2 H4 HOCH2 CH2 (3) : HO+ HO SO 2 NO x 9.3.3

37 2 27 (1 ) CH3 + O2 CH 3 O2 CH3 O2+ HO2 CH3 OOH + O2 HO ROX : ROXkHO [ C] [ HO] (2 9) kho; [ C] HO, HO kho HO(25) 10-9 k HO / Lmol - 1 s - 1 T 1/ 2 / d ( C 3 C 8 ) ( C 6 C 10 ) ( C 4 C 6 ) (1 3 ) ( ) ( C 2 C 6 ) ( ) ( C 2 C 7 ) ( C 2 C 5 ) ( - 4) ( - 3) , : (1) ; (2) ; (3) 4 HO, k2 = cm 3 / ( s), [ HO] = / cm 3, CH4 CH4 + HO k2 CH 3+ HOH k2 = cm 3 / (s), : = = 1 k2 [ H O] 1 ( )(510 5 ) = (7.6 ) H O HO, 1) : H2 O2 HCHO H2O O3 CO CH 4 NO,

38 28,, HO,, 10-6 ( ) NO x,,, HO 2) H O 2 8, HO, HO 2 8,,, nm, HO 309 nm, ( s) HO : s= An a F (2 10) A ; n HO; a HO; F 2 8 HO, HO, H O/ cm nm nm,, 10 km H O,,, HO 2.3.5,,, (),, , HO, : CH 3 CH3 HO CH3 CH2 O2 CH3 CH2 O2 H2 O HO, O2, : CH2 CH 2 HO H OCH2 CH2 O2 HOCH2 CH2 O2

39 2 29 : (1) ; ( 2) ; (3) NO,,, : CH2 CH2 O3 OO H (CH2 CH2O3 ) * HCHO + C H,,, ( C10 H 16 ) ( C5 H8 ) :,, CH4 N H3H2 H2 S CH3SCH3 CH3SSCH3 HO, SO2 H2 S HO : SO2 : H2 S HO HS O2 SO O2 SO2 H2 O HO O SO2 + HO2 SO2 + CH3 O2 SO2 + HO M SO3 + HO SO3 + CH3 O HSO3 SO3, H2 SO4 : SO3 + H 2O H2SO4 HSO3H2SO4 HNO , CO(), : CH3Cl HCl HO :

40 30 HCl CH3 Cl HO Cl H2 O HO CH2 Cl H2 O, HCl: CH4 + Cl H2 + Cl HO2+ Cl O3 + Cl CH3+ HCl H+ HCl O2 + HCl ClO+ O2 O3 ClO : ClO+ NO ClO+ NO2 Cl+ NO2 M ClONO2 NO NO2, ClO: HOCl ClO+ HO2 HOCl HOCl + O2 h HO+ Cl HOCH2 Cl, : CH2 Cl+ O2 CH2 ClO2+ NO CH2 ClO2+ HO2 CH2 ClOOH CH2 ClO+ O2 M CH 2 ClO2 CH2 ClO+ NO2 CH2 ClOOH + O2 h CH2 ClO+ HO HCl + CO + HO2, CH3 Cl HCl CH3 Cl,, NO CO SO2 (,, 8.2.1),,, :,,, HO,

41 2 31 HO, :, HO, : CH3 HO CH2 O2 CH2 O2 H 2 O NO 2 H O 2,, NO CH2O O2 CHO,, ,,, ( H2 CH 4 CO ) O3N2 O CO2,, 20, 20 CH4 CO CO2 H2CO, CH4 CO CO( ), CO2,, NH3 NO x NH3 HO : N H3 HO NH 2 H 2 O N H3 N H2 NO x,,,, ( )( ), (GB ),,,

42 32, 2 6 ( ) 2 6 ( 1 ) (1 ) ( 2 ) (2 ) ( 3 ) (3 ) [ ] (1 ) (2 ) ( NO 2 ) ( 1 ) Saltzma n ( 2 ) ( 1 ) Saltzma n ( 2 ) ( F ) (1 ) (2 ) TS P; I P P M 10 ; N O NO 2, NO x N O x ;, 2.4.2,,, (API),,, ,, (SO2 ) (NO2 )(IP), 2 7, ( i)ci I i : I i = ( c i - cn) ( cn cn) ( In+ 1 - In) + In ( 2 11) In I n+ 1 n( n+ 1); cn cn+ 1 n( n+ 1), ( ) ( ),,, ( )

43 / mgm - 3 A PI SO 2 ( ) NO 2 ( ) I P ( ) AP I > 300,,,,,,, A PI A PI , 2.5,, ; ;

44 34, : ( 1) ; ( 2) ; ( 3) ; ( 4) ; (5) ( ),,,,,, / (kg/ s) ( ) / ( ) [ kg/ ( s m ) ] ( ) / ( 2 ) [kg/ ( sm 2 ) ] ( ) / ( ) ,,,,,, ;, ( ) ;, ,,,,,, (), ( CO CO2 ) NOx SO x 2 10, ( ),

45 ( k m ) CO 2 C FCs SO 2 IP CO SO 2 NO x CO SO 2 NO x Pb O 3 Pb O 3 O 3 - ; ; ; , 2 11 NO NO 2 SO 2 SO 3 CO CO 2 H 2 SH FN H 3 H Cl O 3 (): SO x O3 NO x Pb CO x, SO SO , 2 12 ( ) 2 12 ( ) [10-9 ( ) ] SO H 2 S 1 CO C H NO 750 NO O 3 H NO 3 N H 3 H CH O H COO H H NO 2 P AN [ CH 3 C( O ) O 2 N O 2 ] NM H C( ) 1 200

46 , (),, : ( 1) ; (2) ; (3) ; ( 4) ; ( 5) 2 13, 2 13 / g ( kg ) - 1 / g( kg ) - 1 / g ( kg ) - 1 CO ( S O 2 ) ( 20 ) x ( 20 ) x ( 16) x ( NO 2 ) ( 7.5 ) y ( 2.8 ) y x = ; y =, 2 14 (, ),, 2 14 / % ( Fe 2 O 3 Fe 3 O 4 ) ( MgO ) ( CaO) ( Al 2 O 3 ) ( SO 2 ) ( T io 2 ) 02.8 ( CO 2-3 ) 02.6 ( SiO 2 ) ( P 2 O 3 ) ( K 2 O) ( Na 2 O )

47 2 37,, 2 6, () CON H 3 CO x SO x H 2 S ( CH 3 ) 3 N Cl 2 Hg ( ) H F Al 2 O 3 C H F SO 2 SO x N O x ( ) O 3 Cr NO x CO SO x NO x Cd CO [] H 2 S Se BaO,,, (), 2 10, 2 10, ;,,,, 96% 86% CO 56%NO x, (), ,,,, (2 16),

48 ( ) C 6 C 10 C 7 C 10 C 9 C 12 C 8 C 9 C 6 C 7 C 6 C 10 C 8 C 9 C 10 C 14 C 7 C 12 C ,,,,, SO2 NO2 O3,,,,,,, CO2,, 9 2.6,,,, , : (1), ; (2), () ; (3 ) ; ( 4),, ( )

49 2 39,,, m/ s,, 16 (), ,,,,,,,,,, rd (, rd = 1K/ 100m) r(, r 0.65 K/ 100m),,,, :, : pv = nr T p =R T ( ) ps = s R Ts pa = a R Ta ( s a ), s Ts = a Ta Ts < Ta, s > a,,, : (a) r < rd, ; ( b) r > rd,,, ; (c) r = rd,,,, : (1 ) r < rd, r> 0, ( ),,, (9.4. 1) ; (2) ( r > rd ) ; (3) ( r = rd ),,,,,,,,,, 2.6.2, ( ), /

50 40, / (), ; 30 m, (2, 6)1.5m100m,, () : ; 1; 2; g ; r u= 2( 1-2 ) gr 2 cm/ s ( 2 12) 9,, (), ( ), 0.1 m, ( ), 2 11,, 2 11,, O3 ( )

51 2 41, , :, : [ A(aq) ] = KHA pa ( 2 13) [A (aq) ] A ; pa KHA A ; A, KHA K H / mol( LPa) - 1 K H / m ol( LPa) - 1 O C 6 H 6 ( ) NO C 6 H 5 Cl ( ) O C 6 H 5 NO 2 ( ) NO 2 N 2 O C 6 H 5 C H 3 ( ) C 10 H 8 ( ) CO 2 H 2 S C 14 H 10 ( ) C 20 H 12 ( [] ) SO C 6 H 5 O H ( ) H O C 6 H 4 ClO H ( 2 ) H N O C 6 Cl 5 OH ( ) N H C 6 H 4 NO 2 OH (2 ) H O 2 HC l CHCl 3 ( ) CHBr 3 ( ) H 2 O H N O : (a),, SO2,, : ( SO2 ) aq H2 SO3 HSO3 - SO 2 3 -,, [ A(aq) ]( SO2 ) aq ( b),,, (c) 10-2, (d), : dln KH d T = H R T 2 ( 2 14),H H,,,, (e), (f), 5 30, SO2

52 42 p SO2 / k Pa kg ( SO 2 )/ 100kg( H 2 O ) KH = [ SO 2(aq) ],, pso 2 KH X = pso 2, Y = [ SO2(aq) ], KH : : KH = nx iyi - X iy i nx 2 i - (X i ) 2 X i Y i X 2 i X i Y i KH = = 0.09 kg(so 2 )/ 100kg( H2 O) kpa KH = / = mol/ ( LPa) 6 N H3 25: f H m / k Jmol - 1 S m/ J( molk ) - 1 N H 3 ( g) N H 3 ( aq ) ( K H ); ( Pa) ( KH ) : NH3 ( g) NH3(aq) r H m = ( ) - ( ) = kj/ mol r S m = = J/ (molk) Tr S m = 298( )10-3 = kj/ mol

53 2 43 ln K H = - R T r G m = r G m = ( ) = K H = 57.7 r H m - T r S m = ( ) - ( ) = kj/ mol, K H KH : KH = K H / ( ) = 57.7/ ( ) = mol/ ( LPa) SO2, ( ) 9.3 SO2,, : SO2 (g) + H2 O SO2H2O KHS = [ SO 2H2 O] p SO2 ( 2 15) SO2H2 O H + + HSO3 - KS 1 = [ H + ] [ HSO - [ SO2H2 O] 3 ] 3 ] HSO3 - H + + SO KS 2 = [ H + ] [ SO 2 - [ HSO - 3 ] ( 2 16) ( 2 17) KHSSO2, KS 1 KS 2 KHSKS 1 KS 2, : lg KHS = T lg KS 1 = 853 T lg KS 2 = T SO2 : [ SO2H2O] = KHSp SO2 [ HSO - 3 ] = K S 1 [ SO2H2 O] [ H + ] [ SO ] = K S 2 [ HSO - [ H + ] 3 ] = K HSKS 1 p SO2 [ H + ] = K HSKS 1 KS 2 p SO2 [ H + ] 2 [ H + ] = [O H - ] + [ HSO - 3 ] + 2[ SO 2-3 ] [ HSO3 - ] [ SO ], : [ H + ] 3 - ( KW + KHSKS 1 p SO2 ) [ H + ] - 2 KHSKS 1 KS 2 p SO2 = 0 ( 2 18) KW SO2,

54 44 ph [ H + ], [ HSO - 3 ][ SO 2-3 ] + 4 [ S() ] [ S() ] = [ SO2H2 O] + [ HSO - 3 ] + [ SO 2-3 ] = KHS p SO2 1 + K S 1 [ H + ] + K S 1 KS 2 [ H + ] 2 = K * HSp SO2 ( 2 19) [ S() ]K * HS KHS, SO2, [ S( ) ], ph p SO [ S() ], [ SO2 H 2O]pH [S() ], ph, [ S() ] S() : SO2 H 2 O = [ SO 2 H 2O] [ S() ] HSO - 3 = 1 + K S 1 [ H + ] + K S 1 KS 2 [ H + ] 2 = [ HSO - 3 ] [S() ] = 1 + [ H + ] KS 1 + K S 2 [ H + ] ( 2 20) ( 2 21) 2 - SO = [SO2 3 - ] 3 [ S() ] = 1 + [ H + ] + [ H + ] 2-1 ( 2 22) KS 2 KS 1 KS 2 S()pH ph p SO2 [ S( ) ] 2 13 S( ) p H ( T = 298K, p SO2 = Pa) S(), HSO - 3 SO 2-3, ph (NO)(NO2 )

55 2 45 NO ( g) NO2( g) NO( aq) NO2( aq) NO(aq) + NO2 (aq) 2 NO2( aq) N2 O4( aq) N2O3(aq) N2 O4(aq) 2H + + NO2 - + NO3 - N2 O3(aq) 2H + + 2NO - 2 : 2 2NO2(g) + H2O 2H + + NO2 - + NO3 - NO( g) + NO2(g) + H2 O 2H + + 2NO K, 2 [ NO3 - ] [ NO2 - ] = p NO 2 K 1 pno K2 18 (7) (8) : ( 2 23) 298K, K1/ K2 = , pno 2 / pno 10-5, [ NO - 3 ] >> [ NO - 2 ], NO2 (NO2 ), NO ( 298 K ) ( 1 ) NO ( g) NO ( aq ) ( 2 ) NO 2 ( g) NO 2 (a q) ( 3 ) 2 NO 2 (a q) N 2 O 4 ( a q) ( 4 ) NO ( aq) + N O 2 ( aq ) N 2 O 3 ( aq) ( 5 ) H NO 3 (a q) H + + NO - 3 ( 6 ) H NO 2 (a q) H + + NO - 2 ( 7 ) 2 NO 2 ( g) + H 2 O 2 H + + NO2 - + NO3 - ( 8 ) NO ( g) + N O 2 ( g ) + H 2 O 2 H + + 2NO - 2 K H = m oll - 1 Pa - 1 K H = m oll - 1 Pa - 1 K n1 = mol - 1 L K n2 = mol - 1 L K n3 = 15.4 moll - 1 K n4 = moll - 1 K 1 = mol 4 L - 4 Pa - 2 K 2 = mol 4 L - 4 Pa - 2 HNO3, NO - 3 ; H NO2, ph, NO 2 - H NO2(aq), pno 2 pno : [ H + ] = [O H - ] + [NO2 - ] + [NO3 - ], [ H + ][ NO3 - ], [ NO3 - ] = K2 1 p 3 NO 2 K2 p NO 1/ 4 ( 2 24) 2 18 (7 )NO - 2, NO - 2 (8 ), [ NO2 - ] = ( K2pNOpNO 2 ) 1/ 2 [NO - [ NO - 2 ] = K 3 2 p 3 NO K 2 1 p NO2 3 ] 1/ 4 ( 2 25)

56 46 HNO2 [ HNO2(aq) ] = [ H + ] [ NO - 2 ] Kn4 [NO 2 - ] [NO3 - ] [ H + ][ NO3 - ] 2 [ HNO2(aq) ] = K 2pNOpNO 2 K 2 ( 2 26) n4 14 pnopno 2 [ HNO3(aq) ] [ H NO2(aq) ],, HNO3(aq) ( )9.3 1/ p N O p N O2 H NO 3 ( ) H NO 2 ( ) ( m ol/ L ) ( SO2 NO x),, 2 cg; caq ; cp; 15, : cs, rain ( ) ; corg; (,,, ), 4 : (1),,,, ; (2), ; (3) ; (4),

57 , CO CH 4 NH3 H2S, NO SO2,, H2 CO3 HNO3 H 2SO4,, HOO3, 2 19, HO O3 2 20,, (10-13 s)( ) 2 19 H 2 S SO 2 H 2 S H O H 2 S SO2 H O SO 2 H2 SO 4 N H 3 N H 3 H 2 SO 4 ( N H 4 ) 2 SO 4 HN O 3 N H 4 NO 3 N H 3 H O N H2 ( ) O( 1 D) N N 2 O 2 + O 2 N 2 O NO NO NO 2 N O O 3 R O 2 NO 2 N O 2 NO N O 2 H O H N O3 CH 4 O( 3 P ) CH 4 CO + H2 CO CH 4 CO H O CO 2 C 2 H 4 ( NMHC) C 2 H 4 O 3 HCH O + HCOO H 2 20 N O 2 NO 2 + h NO + O H CH O HCH O + h H CO + H O 3 O 3 + h O ( 3 P ) + O 2 CO + H 2 O ( 1 D) + O 2 CH 3 CH O CH 3 C H O + h C H 3 + H CO H NO 2 H NO 2 + h N O + H O CH 3 C( O ) CH 3 CH 3 C( O) C H 3 + h CH 3 + CH 3 CO H 2 O 2 H 2 O 2 + h 2 H O CH 3 CH 2 C( O )C H 3 CH 3 C H 2 C( O) CH 3 + h C 2 H 5 + C H 3 CO N O 3 NO 3 + h NO + O 2 NO 2 + O CH 3 + C 2 H 5 CO,

58 (C ), : C ( ) h C * ( ) *, * *, ( ) C * * * * * H * * *,, ( A * ) : A * B1 + B2 + () A * + E D1 + D2 + (E, ) A * A + h() A * + M A + M (M ), A *,, ( ),, O2 O3, O2 O2 O3 h = 242nm O(3 P) + O( 3 P) h = 175nm O(3 P) + O( 1 D) h = 1 180nm O 2 ( 3 - g ) + O( 3 P)

59 2 49 O3 O3 O3 O3 h = 610nm O2 (1 g ) + O( 3 P) h = 463nm O 2 ( 1 + g ) + O( 3 P) h = 310nm O 2 ( 1 g ) + O( 1 D) h = 260nm O 2 ( 1 + g ) + O( 1 D),,,,,, : CH3 CHO h CH 4 + CO CH3 CHO h CH 3+ CHO CH4 + CO + H2 + C2 H6 A * ( ), A * ( )A *, A *, = A * ( 2 27),, > 1(10 6 );, < 1,, A * : 4 A * A, [ ] A ; : k i = 1 d[ A * ] dt i = 1 (2 28) = k[] ( 2 29) A *, A 1 2 A ( ka = 2 1 A (, T) A (, T)d F = 2 1 A (, T) A (, T) I( ) d ( 2 30), T) T, A, cm 2 ; A (, T) T, A, A *, A * ; F, (cm 2 s) - 1 ;

60 50 I( ), (cm 3 s) - 1 A A, 2 16 O3 NO2, 2 17 NO2 NO 2 16 O 3 NO NO 2 NO, (), ( ) NO2 NOO 301 kj/ mol, 400 nm NO2 2 17, 300 nm370 nm, NO2 100%, 370 nm,, 420 nm 7 290nm, NO2, NO? NO J/ mol Einstein 290nm E = h= hc, hplanck, Js, c, m/ s = m, E = ( ) ( ) = J ( )( ) = J/ mol NO,290nm NO 2.7,, : (1 ), ; ( 2)

61 2 51 ; (3) ; (4),, : ( 1 ) ( 2 ) ( 3 ) ( 4 ) : ( 1 ) ( 2 ) ( 3 ) : ( 1) ( 2) : ( 1) ( 2), (), (),, 2 21 () ()( ) ( ) 2 18,, ( ), ( ),, H2S HCN CO, ( ) 2 18, ( SO2 NO2 ) : SO2 H2S NO2 N H3 Cl2 HCl H F SiF4,

62 , 3.?,? 4.?? 5.? 6.? 0.1m? 7.?? HO? 8.?? 9.?, 10.?? 11.,?? 12.? 13.,?,? 14.,? 15.??? 16.?? 17. SO 2 N 2 O 2? SO 2? NH 3 SO ,NO x 19.,???? 20.??? 21.,? Pa? N 2 79%,O 2 21%,, Pa, H v = J/ mol, Pa 12.0 L, L,? 4., SO2 365 g/ m 3, [10-6 ( ) ] ( Pa )? km, 20 km40 km Pa,- 20( ), O g,o 3 [10-6 ( ) ]? g, 24h, g,

63 m 3 / min 1.0 m 3 / min, Pa, M ( g/ cm 3 ) b(l), V(cm 3 ), [ 10-6 ( ) ] t/ a, 2 d, ( t, 3.2) 9. HOO ( g) + H 2 O ( g ) 2 HO ( g), 27 k = km L / (mols),e = 77 kj/ mol, mg/ m 3, % C,5.2 % H,1.2% N,2.6 % S, 5.9 % O, 7.9 %, N2 12.,Cx H y ( N2/ O2 3.76), N2, 1 mol ( F )? ( M )? f [10-6 ( ) ] 1 mol, [10-6 ( ) ] FMf, kg 18 % ( ), 16 kg/ h, 6 % ( ), 2.5% ( ),? K 170 g/ (cms ) g/ cm 3, d = 1 m ( 2.0 g/ cm 3 ) 15., 40 cm 2,,, 20 mg,g/ ( m 2 a) ph = 8.0 H2 SO3, SO 2-3 [ S( ) ]? nm, SO2, SO? J/ mol 1. ( API), ( API) : (I P PM 10 ) ( SO 2 ) ( NO 2 ) IP IP 2 1 API IP,, IP,, : I = I 0 exp( - m X m ) (1)

64 54 2 1IP / gm - 3, , , , , , , , , , , , , , , I IP ; I0 ; m / cm 2 g - 1 ; X m IP / gcm - 2 Q, m 3 / min,t, min, A, cm 2,IP c,g/ m 3, IP :, IP : X m = Qtc A A c= m Qt (ln I 0 - ln I) (3) (2) 2 1IP ( ) 1 ; 2, 3 ; 4 ; 5 ; 6 ; 7 ; 8 ; 9 ; 10 ; 11 ; 12 ;13 ; 14 ; 15 ; 16,, IP 2 1, 2 2

65 C, ( Bq), ( ) 2 2 / MeV / cm 2 mg - 1 / mgcm C 5730y S 87 d P m 2.6y T l 3.8y Sr 28y SO2 SO 2 2, 3 AP I 2 3SO : H 2 O2 ( H 2 SO4 ), SO2 100 %, SO 2 + H 2 O 2 H 2 SO 4,, SO 2,, ; SO 2,,,,,, (1h),,, SO 2, SO 2 2 2,,,,,, 1min,,, 1, 1.6 %,,,,,,20

66 SO 2 1 ; 2 ; 3 ; 4 ; 5, 6 ; 7 ; 8 ; 9 ; 10 ; 11 ; 12 ; 13 ; 14 ; 15 ; 16 ;17 ; 18 NO 2 API,, NO, NO 2 NO O 3 NO ( 100Pa400 Pa) [ O 3 ]/ [ NO] 1, : NO + O 3 NO 2 + O 2 NO + O 3 NO * 2 + O 2 NO * 2 NO 2 + h 2 3 NO 2, NO: NO 2 + C NO + CO 2 3NO/ O 3 CO + NO 2 NO + CO NO ( NO + NO 2 ),NO NO 2 NO ( ), 25,110-9 ( )

67 NO x 2. ( ),, ( H F ) ( P A N ) ( O 3 ) 0.06 ( SO 2 ) 0.1 ( N O 2 ) 2.5 : 10-6 ( ) 2 5,

68 58,,, ( alfalfa) SO 2, SO 2 2 ( ), t(c ) = 0.94 t(c - 1.4) = 2.1 t(c - 2.6) = , ( ,), ( 0 % ), SO 2, ( 0.2h),,SO 2 2 6,, ( ) ( ),,, HF,SO 2, H F ( gladiolus ) H F h, ( 2 5 ) H F, HF,,,, H F ( Si - F )( Ca - F ),,,,,,,,,,, 2 6,,,,,

69 ,,, t,,,,,,,,, 3.1,,,, ,,,, 3.98,,,,,,,,,,,, ;,,,

70 60, HOH ( ) (a),,, kj/ mol, OH 1/ 20,, 3 1( b) 3 2 ( a) ( b) 3 1, 15%,,, : (1),, ; (2 ),,,,, 3.98 ( a) ( b ) 3 2,,, 3 1,

71 (46 ), ( ) 3 3,,, ;,, ( ), (),, i i : Mii ; i = M i Ri Ri i (, Pi ) (3 1), Ri = dm i d Pi = - dmi d i Pi + Ri = 0 (3 2) 3 3, 97%, 2%, 1%, 1%,

72 , kg cm 2, 90cm, (1.0g/ cm 3 ) (3 1) : = i = M i Ri = M i - Pi = ,, 83%, 70% ;,,,,, 60% 90%, : 66% 85%60% 10%,,,,,,,, ( ),, 1% 3% ( ),, ; ;,,, ;,,

73 ,,,,,, 3.3.2, (),,,,, ( ), 2 g/ L9 g/ L,, 10 8, (), (), 10-3 m,,,, 1 m,,

74 64,, ,, ()( ) ( ),,,,,,

75 () 3 4,, ( ng/ L)( mg/ L), ,, : Na + Ca 2 + Mg 2 + HCO 3 - SO Cl CO 2 H + H CO - 3 SO 2 SO 2-4 O 2 N 2 CO 2 Na +, K + Cl -, F - Ca 2 +, Mg 2 + S O 2 4 -, CO Fe 2 +, Mn 2 + H CO3 -, N O3 - PO 3-4, P 2 O 4-7 CO 2, O 2 H + Cl - N 2, H 2 S Na + H CO - 3 CH 4 N H + 4 NO ( )

76 66 3 6, ()3 5 ( ) 3 5 Li Li + K K + Mo MoO 2-4 Be BeO H + Ca C a 2 + Ag Ag + B H 3 BO 3, B( O H ) - 4 Cr Cr ( O H ) 3, CrO 2-4 Cd Cd 2 +, CdO H +, CdC l + C HCO - 3 Mn Mn 2 + Sn SnO( O H ) - 3 N N 2, NO - 3 Fe Fe( OH ) + 2 I IO - 3, I - F F - Co Co 2 + Ba Ba 2 + Na Na + Ni Ni 2 + H g Hg( O H ) 0 2, HgO HCl, HgCl 0 2 Mg Mg 2 + Cu CuCO 3, CuO H + T l Tl + Al Al( OH ) 4 - Zn ZnO H +, Zn 2 +, Z nco 3 Pb PbCO 3, Pb ( O H ) 3 - Si Si( O H ) 4 As H As O 2-4, H 2 A so - 4 Bi BiO +, Bi( O H ) + 2 P H PO Se SeO S SO 2-4 Br Br - Cl Cl - Sr Sr 2 +,,, ( CH3 Hg + ),, [ CH3 Hg(O H) ],, [ CH 3 HgCH3 ] [ CH3 Hg ][ CH3 HgS ],, CH3 HgCl,,,

77 3 67, (1 ),,, Al(O H) + 2,, ; (2) Cu 2 + CuCO3 ( OH ) x CuClx CuO HCl CuSO4, mg/ L, Cu 2 +,,, (3), CO2, [ CO2(aq) ] [ H2 CO3 ] [ HCO3 - ][CO ] CO2, CO2,, CO2 H2 O SO2 H 2O ( ), 3 6 CO2 KHCH2 CO3 KC 1 KC CO 2 ( aq) H 2 CO 3 HCO 3 - CO H 2 O + CO 2 ( g) K H C H 2 CO * 3 K C1 H + + HCO - 3 K C2 2 H + + CO 2-3 [ H + ] = [ HCO - 3 ] + 2 [ CO 2-3 ] + [ O H - ] ( 1 ) K H C = [ H 2 CO * 3 ] p CO2 ( 2 ) K C1 = [ H + ] [ H CO - 3 ] [ H 2 CO * 3 ] K C2 = [ H + ] [ CO 2-3 ] [ H CO - 3 ] ( 3 ) ( 4 ) C T = [ CO 2-3 ] + [ H CO - 3 ] + [ H 2 CO * 3 ] ( 5 ) ( ) [ Alk] = [ H CO - 3 ] + 2 [CO 2-3 ] + [ OH - ] - [ H + ] ( 6 ) ( ) [ Ac y] = 2 [ H 2 CO * 3 ] + [ H CO - 3 ] + [ H + ] - [ O H - ] ( 7 ) m ol[ H + ]/ L mol[ O H - ]/ L, mol[ CaCO 3 ]/ L m g[ CaCO 3 ]/ L 3 6 : (a) CO2 H2 CO3 : CO2( aq) + H2 O H2 CO3 CO2(aq), H2 CO3 25, [ H2 CO3 ]/ [ CO2(aq) ] = [ H2 CO 3 * ]

78 68 [ H2 CO * 3 ] = [ CO2(aq) ] + [ H2 CO3 ][CO2( aq) ] (3 3) [ H2 CO * 3 ][ CO2( aq) ], ( b) KC 1 [ H2 CO * 3 ] [ H 2 CO3 ], KC 1 (c) ;, ph poh, lg K HC - lg K C1 - lg K C [ H2 CO * 3 ],, [ H2 CO 3 * ] [ HCO3 - ] [ CO ] : H2 CO * HCO CO CT 3 = [ H 2 CO * CT 3 = [ HCO - CT 3 ] 3 = [CO2-3 ] 3 ] H2 CO * 3 ph HCO CO 3 3 7, ph, CO2 + H2 CO3, ph CO 2-3, HCO - 3 ph ph = 1 + K C 1 [ H + ] + K C 1 KC 2 [ H + ] 2 = 1 + [ H + ] KC 1 + K C 2 [ H + ] = 1 + [ H + ] KC 2 + [ H + ] 2 KC 1 KC (3 4) (3 5) (3 6) 7 ( C T = mol/ L, 25), ph, ph, ph 3 7, a b c d e f ph ph mol/ L [ H2 CO * 3 ] [NaHCO3 ] [Na2 CO3 ],

79 3 69 ph a c e ph, : a: [ H + ][ CTKC 1 ] 0.5 = , ph = 4.5 c : [ H + ][ KC 1 KC 2 ] 0.5 = , ph = 8.3 e : [ H + ] KC 2 KW CT bd ph : b: ph = p KC 1 = 6.3 d : ph = p KC 2 = = , ph = 10.8 f ph = 12.1f ph, [ CO 2-3 ] 99%, CO 2-3, : CO H2 O OH - + HCO mol/ L[Na2 CO3 ] ph e, : (a) ph , ph 4.5;, ph 10.8 (b) 3 7, ph = 8.3 cph 8.3, CO 2 3 -, ( CO2 + H2 CO3 )HCO 3 -, : [ H + ] = KC 1 [ H2 CO * 3 ] [ HCO - 3 ] ph = p KC 1 - lg[ H2 CO * 3 ] + lg[ HCO - 3 ] (3 7) ph > 8.3, [ H2 CO 3 * ], HCO 3 - CO 2 3 -, : [ H + [ HCO3 - ] ] = KC 2 [ CO 2 - (3 8) 3 ] ph = p KC 2 - lg[ HCO - 3 ] + lg[co 2-3 ] , pco 2 : [ H2 CO 3 * ][ CO2(aq) ] = KHC pco 2 (3 9) Ks = [ H 2 CO3 ] [ CO2(aq) ] = ( 3 10) 3 6 KC 1 KC 2, ph (, 25 CO2 pco 2 = 36 Pa) : lg[ H2 CO 3 * ]lg[co2(aq) ] = lg KHC + lg pco 2 = (0 ) lg[ H2 CO3 ] = lg[co2(aq) ] - lg Ks = lg[ HCO - 3 ] = lg KC 1 + lg[ H2 CO * 3 ] + ph (0 ) = ph (+ 1 ) lg[ CO ] = lg KC 1 + lg KC 2 + lg[ H2 CO 3 * ] + 2pH = pH (+ 2 )

80 70 lg[ H + ] = - ph lg[ OH - ] = ph ph CT ph,,, ph < 6 [ H2 CO * 3 ], ph = 610 [ HCO - 3 ], ph > 10.3 [ CO 2-3 ] : SO2 H2O ( ), ph [ H + ] 3 - ( KW + KHCKC 1 pco 2 ) [ H + ] - 2 KHCKC 1 KC 2 pco 2 = 0 ( 3 11) CO2 33 Pa(1972 ), 283 K, ph5.6ph, ph ( ), ( ), ( ),,, H + ph, ( N H3 C6 H 5N H2 ), ( ), ( ),, 3 8 : ( H + ) (OH - ) (HCO - 3 ),, ph < 4.5,,, (),, ph, (3 6),, mol/ L, 3 9, ph 4.5,

81 3 71 ph = 4.5( ),, ph = 8.3( ), CO2, H2 CO * 3 : H2 CO * 3 + OH - HCO H2 O CO2, ph = ph,,,,, : HCO OH - CO H2 O ph > 10.8, ph = 10.8,,,, ph = 8.3( ), : CO H + HCO3 -, ph = 4.5( ), : HCO3 - + H + H2 CO 3 *, (3 6 ),,, ( ) (O H - )( CO 2-3 ) ( HCO - 3 ), ph Alk 25, mol[caco3 ]/ L ph [ OH - ] = 10 ( ph - pk W ) ( ph ) = 10 mol[caco3 ]/ L :, KC 2 [Alk] = [CO 2-3 ] [ HCO - 3 ] [OH - ] [ H + ] ( 3 12) : [CO ] = K C 2 [ HCO - [ H + ] 3 ]

82 72 [ HCO - 3 ] = 2[ Alk] - [OH - ] + [ H + ] 2 KC 2 [ H + ] + 1 ( 3 13) [ CO 2-3 ] = 2[ Alk] - [OH - ] + [ H + ] 2 + [ H + ] KC 2 ( 3 14),,, 2 ( P44P46) 2 25, [ Alk] = mol[ H + ]/ L, ph = 7.0, ( HCO H2 O + h {CH2 O} + OH - + O2 ) ph 10.0, (1 ) ; (2)? : (3 13 ) (3 14), (3 12) : [ H2 CO 3 * ] = 2[ Alk] - [OH - ] + [ H + ] 2 KC 1 KC 2 KC 1 [ H + ] 2 + [ H + ] KC 1 = , KC 2 = , [ Alk] = ph = 10.0, = mol( CaCO3 )/ L ph = 7.0 p H = 7.0 p H = 10.0 [ H 2 CO * 3 ] [ HCO - 3 ] [CO 2-3 ] = = ,CT = ( ) - ( ) = mol/ L (2) {CH2 O}, CT M{CH 2 O} = 30, = 30( )1 000 = 15.6 mg/ L,, ph,, ( ) [ H + ] [O H - ],, ph ( ) : ph NaOH ( c B, mol/ L), HCl( c A, mol/ L),, : = dc B dph = - dc A dph ( 3 15) = c B ph = - c A ph ( 3 16),

83 3 73, ph, 2 [ HCO - 3 ], ph [ HCO - 3 ] / mgl - 1 C T / 10-3 M - c A p H ,,, ph, ph , 3.3.5, 3 10, 3 10 TS ; T DS ; SS ; SE TS ; FDS ; F SS ; VDS ; VSS ; TF S ; T VS TS TDS() SS( ),,,

84 74 (a), ( SiO2 ) ( Al2O3 ) ( Fe2 O3 ),, ;, ( b),,, (c),,, (d),,,, (e),, ; (), (),, (3.6.2),,,,, 3 11,, ( ) 3 11, (, g/ kg ) : 75% 95%(100600) ( 30200) (320 ) (13 ), (Fe, mg/ kg ): Fe 3.06% Cu 21.0 Pb 7.4 Zn 89.6 Cd 0.26 Co 16.0 Ni 24.0 As 5.91 Hg Cr 33.0Mn 539,,

85 %, m 2 (3 12), m, m 3, I 0.7,,, ,, 4, 35,, 3 13 ph , 7.8,,, 99% Cl - Na + Mg 2 + SO Ca 2 + K + ( HCO3 - + CO )

86 76,, ( HCO - 3 CO 2-3 ), ( ) ( ) = ( ) ( 3 17), ( ) 3 8, 3 9, 4 Cl - ; CO SO HCO 3 -, ( p K) H CO - 3 (0.68 ) CO 2-3 ( 0.20) SO 2-4 ( 0.12 ) K + ( 0.64 ) ( 0.68 ) Na + ( 0.76 ) ( 1.13) 1.27 (0.68) 0.72( 0.68 ) Ca 2 + ( 0.28 ) 1.26 (0.68 ) 3.2 ( 1.13 ) 2.31( 1.13 ) Mg 2 + ( 0.36 ) 1.16 (0.68 ) 3.4 ( 1.13 ) 2.36( 1.13 ) p K, ; / % / % K Na + Mg SO HCO CO 2-3 Ca Cl - SO 2-4 HCO - 3 CO Ca K + Mg Na SO 2 -, Cl - CO 2-4 3,,,, (DOC), 1 mg/ L5 mg/ L, 20 mg/ L, mg/ L 3 10

87 3 77 DOC, 3 10 DOC / mgl ,,, ( )10 13 m 3, 38.5, 32.5,, ;,,, : (1 ),, ; (2 ),, ; : (a) ; ( b), (c) ; (d), ; (e) ( ); (f) ,, () ( g/ kg ), ;, ( ),,, ( ), (3.3.4),, Na + Ca 2 +, HCO 3 - Cl - SO 2 4 -,,,,, ( Hg Cd Pb ),,

88 78,, ,,,,,, 3 14,,, ( 9.5),,,, H2S,,,, ph 5.5, ,,, (3 15) 3 15

89 3 79,,,, : ( 1), ; (2 ) ; (3),, Fe 2 + Mn 2 + ; (4 ) ; ( 5),,,,,,, ;,,,,,,,,,, ( ),,,, ,,,,,,,,,,, (, ) (),,, ( ) (), :

90 80 1) ( ) ) (a) ph,,, ( b), OH - CO HCO3 -,,, Fe 2 + Fe(OH)3,, Mn 2 +,,, H4 SiO4,,,,, 1 mg/ L, H2 S, (), NH + 4 N H3, N H3, Cl2, :,,,, p H

91 3 81 (c) (BOD) ( COD) ( PV) ( TOD) ( TOC) (d) 3) 4), ( ),,,,,, CH4 H2 S ( ) GB (GB ),, : ; ; ; ;, 24 3 : 11(, ) (, ); ;

92 / mgl ph ( ) , 9- -1, ( ) , ( ) ( ) ( ) ( ),, 1989

93 ,, 600 L/ d,,,, : (1) (BOD) ; (2 ) ( COD) ; (3 ) ( TOD) ; (4) ( TOC),, ( ThOD)( ThOC),, BOD COD 1 mg/ L, CO2 H 2O : 2K HC6 H4 ( COO)2 + 15O2 16CO2 + 5H2 O + K2 O, mg/ L, ThOD mg/ L, ThOC 0.47 mg/ L, 1 mg/ L, ThOD/ ThOC = 1.175/ 0.47 = 2.5, COD TOD TOC, ThOD ThOC,, C CO2 H H2 O N NO3 - S SO P PO 3 4 -,, BOD(5 BOD5 ) ;, COD(K2 Cr2O7, CODCr ) PV(KMnO4 ) ;, TOD, CO2 TOC : ThOD > TOD > CODCr > BOD5 COD BOD5, BOD5/ COD ,, 0.5,, BOD, BOD,, ( ),,, BOD COD TOD ;, TOC

94 84 BOD 1913, 65(18.3)5 BOD BOD,, 10,, BOD BOD, 5, ;, BOD,, BOD ;, BOD,, 15% ;, 5, BOD COD K2 Cr2 O7, Ag2SO4, (1 + 1) H2SO4 COD,, :,, TOC TOD, 3 1gCnH2 mthod : CnH2 m + n+ m 2 O2 nco2 + mh2 O : ThOD = = 32 n+ m 2 (12n+ 2 m) 8(2 n+ m) 6 n+ m g 4 1gCH3 COON H4 CH3 COONH4 (M = 77),, (1) CH3 COONH4 + 2O2 2CO2 + H2 O + NH OH - OD = = 0.83g (2) 2CH3 COONH O2 4CO2 + 7H2O + N2 OD = = 1.14g (3) 2CH3 COONH O2 4CO2 + 5H2O + 2NO H + OD = = 1.56g,, (3 ) OD 1gCH3 COONH4, ThOD = 1.56g

95 CODCr, Cl -, Cl - ; 1 000mg/ L Cl -, CODCr? : Cl - Cr2 O 2-7 : 14H + + 6Cl - + Cr2 O 2 7-2Cr Cl2 + 7H2 O 25mL, : = 0.025g, = mol 2 Cl - 2 O = g ( ) = 225.2mg/ L O 2 -,,, ( TDS) ( TH),,, 30,,, ( SS) (DO)(BOD) ( Amm - N) ( WQI), WQI = ( 3 18) WQI 010, 10 WQI = 10, WQI = 0 ( Water Pollution Control 76(1),113(1977) ) : (1) ( ), ; ( 2),,, 3 16

96 ,,, ( ) , , 28.8% ; ,,,,,,, ,,, 0.05% BOD 3 17

97 ,,,, / mgl - 1 / m gl - 1 BO D ( T N ) COD ( T P ) 4 15 ( Org N ) ( A mm N) 1250 SS ,,

98 88, ( 1), ( 2),,,,, ( 3),,,, () 3.6,,,, 5.5.5,,,,, 3.6.1,,,,,,,,,, () ( )3 18(a),, : ( ) 3 18( b ) 3 18 (a) ( b), 3.98, 4 ;, ;,,, (,

99 3 89 ) (),,, : ( 1) ; (2) ; (3) ; (4 ), , : 1), 5Ca O H - + 3PO 3-4 Ca5 OH( PO4 )3 2) CO2, Ca 2 +,, CO2 Ca HCO - 3 CaCO3+ CO2+ H2 O, Ca HCO h ( CH2 O) + CaCO3 + O2,, CaCO3 3),, Fe 2 + Fe( OH)3 : 4Fe H2O + O2 4Fe( OH)3+ 8H +, : FeS : Fe(O H)3 Fe 2 + SO 2-4 H2 S Fe H2 S FeS+ 2H +, H2 S, FeS CaCO3, nm100 nm,,,,,, (),,,,, (),,, (),,,,,,

100 90, ph, ph (3 19) SiO2 Al(O H)3 ( IEP) ph = 2 ph = , ph = 2 3, ph 69, 3 19, : (1) (2),, AB AB ( ), : q ; ; D = 4 q D 3 AB ( ) 19 ( 3 19) (a),, (),,,,, p H

101 3 91 ( ),,,,,, (3 20( b) ),, ( ),,,,, ( )() ;, , = ( 1-2 ) gd 2 18, cms - 1 ; (3 20) 1, gcm - 3 ; 2, gcm - 3 ; g,980 cms - 2 ; d, cm;, Pas m,, ;,,,, 2.6 g/ cm 3, 5 g/ cm 3 7 g/ cm 3, g/ cm 3 0.1g/ cm 3,,,,, ,,,,

102 92,, G ;, S, G = H - TS, H,,,, 40 kj/ mol,,,, 120 kj/ mol200 kj/ mol, 400 kj/ mol,,,,,,,, (), ( ), , BET() : y; 3 x; m ; cw ; 1 n ( c w, 1) ; Ka y = x m = K a c 1 n w ( 3 21) lg y = lg Ka + 1 n lgc w ( 3 22) 22, lg y lgcw,, Ka n cw y = a ym + c w ym cw/ y ; ( 3 23)

103 3 93 ym ; a y ym 100% cw/ y cw (3 23), ym a BET,, ,,, (, ), 1),,,,, : Fe 3 + Al 3 + H + Ba 2 + Sr 2 + Ca 2 + Mg 2 + Cs + Rb + N H 4 + K + Na + Li + H + (),, O OH, ( ) ( ) ;,,

104 94 2) ph, Cl - NO - 3, OH - H2 O : ( PO SeO MoO SiO AsO3 - AsO2 - )( SO F - ) Cl -, : F - ( H2 PO4 - )HCO 3 - H2 BO3 - CH3 COO - SCN - SO Cl - NO3 -,,,, OH - ( r = m m), 3),,,,,,, : (a), (M n+ ) : H R M n+ O H O C R ( b), ( C5 H4 N4 )(C5 H 7 N3 ) (c),, ,, HA, H A 0 = 1/ (1 + Ka/ [ H + ] ) = [ H + ]/ ( [ H + ] + Ka ) ( 3 24) ( 1-0 ) = Ka/ ( [ H + ] + Ka ) ( 3 25)

105 3 95, Ka Ka, ph, FeCl3, Fe 3 +,,, : Fe( H2 O) H2 O Fe( H2 O)5 OH H + Fe( H2 O)4 (OH) H + Fe(OH)3 ( H2 O)3( S) + 3 H + Fe(OH)4 ( H2 O) H + Fe 3 + OH - CN - CO 2 3 -,, : CN - + H2O HCN + O H - CO H2 O HCO OH - HCO3 - + H2 O H2 CO3 + OH - RCOCl,, RCOOH, K ph 3 24, K= K1 [ H + ] + K2 + K3 [OH - ] (3 26) p H, NO - 3 NO - 2 Cu( ) Cu( ) Fe( CN) Fe( ) Pb (C H 2 C H 3 ) 4 ClO - RX NO N O 2 + H O NO + H O Cu ( ) Cu ( ) Fe(CN ) CN - Fe( ), CO 2, H gh g C 2 H 6, Pb Cl - + O; Cl + O - R, X,,,,

106 96, :, 5% ( ), : c ; t ; - d[ c] dt ; ka, : = ka[ c] ( 3 27) d[ c] - =ka[ c] dt ( 3 28), ka = ka : t1/ 2 = d ka ( 3 29) ka ka: ka= Z d j - 1 ( 3 30), Z= Idsec+ 1.2 Is[ / (cm 2 s) ] ( 3 31), L(molcm) - 1 ; Id, (cm 2 s) - 1 ; Is, (cm 2 s) - 1 ; ; j, / mol Z W. J. Lyman :Handbook of Chemical Property Estimation Methods (1982) 3 15, NO3 -, HO ( ): NO - 3 h NO - * 3 NO O NO2 + O - H 2 O HO+ O H - O HO, O2 O3, NO ,,,, ( TiO2 ZnO Fe2O3 CdS ) CO2 HX,

107 3 97 CN -, TiO2 ZnO Fe2 O3, O - 2 O -,,, O2 O,, HO O, (HO), HO mol/ L, 10 9 Lmol - 1 s ,,,,, ;,, Cl - O H -, ; HCO 3 - SO ; N H3 PO F - S 2 -,,, ;, (), Cu( NH3 ) ( H2 O)4 Fe OH OH Fe( H 2 O)4 4 + ;,,,,, PO 3-4, O O O P O P O O O Ca 2+ 6 Cl mol/ L, HgCl2(aq) 10-8 mol/ L(

108 98 Hg ), Hg 2 + HgCl + HgCl3 - HgCl 2 4 -? Hg 2 + Cl - K1 = K2 = K3 = 7.1, K4 = 10 Ki : M L K1 ML L K2 ML2 L Ki ML i L Kn MLn Ki = [ ML i] [ ML( i - 1) ] [ L] : [ HgCl + ] = [ ( HgCl 2 ) aq ] K2 [ Cl - ] = [ Hg 2 + ] = [ HgCl + ] K1 [ Cl - ] = (10-8 ) (310 6 )(10-3 ) = mol/ L ( )(10-3 ) = mol/ L [ HgCl - 3 ] = K3 [ ( HgCl2 ) aq ] [Cl - ] = 7.1(10-8 )(10-3 ) = mol/ L [ HgCl 2-4 ] = K4 [ HgCl - 3 ] [Cl - ] = 10( )(10-3 ) = mol/ L, HgCl2(aq),Hg ,,,,, ph M n+, M(OH) n M n+ + noh - [ M n+ ] [O H - ] n = Ksp ( 3 32) [ M n + ] = Ksp/ [OH - ] n Kw, pm = nph + p Ksp - np Kw ( 3 33), Zn(OH )2 Ksp = , p Ksp = 17.15, ph = 7.0, [ H + ] = [ OH - ] = 10-7,, [Zn 2 + ] = / (10-7 ) 2 = mol/ L [Zn 2 + ] = 65.4( )10 3 = 46.4 mg/ L,,, : co = [Zn 2 + ] + [ZnOH + ] + [Zn(OH)2 ] + [Zn(OH) - 3 ] + [Zn(OH) 2-4 ] ( 3 34), ph

109 3 99 Zn(OH)2,, Zn : : : : : Zn(O H)2( s) Zn OH - Zn(O H)2( s) ZnOH + + OH - Zn(O H)2( s) Zn(O H)2(aq) Zn(O H)2( s) + OH - Zn( OH) - 3 Zn(O H)2( s) + 2OH - Zn(OH) 2-4 Zn O H - ZnOH + ZnO H + + OH - Zn(O H)2(aq) Zn(O H)2(aq) + OH - Zn( OH) - 3 Zn(O H) OH - Zn(O H) H2 O H + + OH - Ksp = [Zn 2 + ] [OH - ] 2 = lg Ksp = Ks 1 = [ZnO H + ] [O H - ] = lg Ks 1 = Ks 2 = [Zn(O H)2(aq) ] = lg Ks 2 = Ks 3 = [Zn(O H) 3 - ]/ [OH - ] = lg Ks 3 = Ks 4 = [Zn(O H) 2-4 ]/ [OH - ] 2 = lg Ks 4 = K1 = [ZnOH + ]/ ( [Zn 2 + ] [ OH - ] ) = lg K1 = 5.70 K2 = [Zn(OH) 2(aq) ]/ ( [ ZnOH + ] [O H - ] ) = lg K2 = 4.43 K3 = [Zn(OH) - 3 ]/ ( [Zn(OH)2( aq) ] [O H - ] ) = lg K3 = 4.10 K4 = [Zn(OH) 2-4 ]/ ( [Zn(OH) - 3 ] [O H - ] ) = lg K4 = 1.26 Kw = [ H + ] [OH - ] = lg Kw = , Ks 1 Ks 2 Ks 3 Ks 4 : Ks 1 = Ksp K1, Ks 2 = Ks 1 K2, Ks 3 = Ks 2 K3, Ks 4 = Ks 3 K4, ph :

110 100 - lg[zn 2 + ] = 2pH + p Ksp - 2p Kw = 2pH lg[zno H + ] = ph + p Ks 1 - p Kw = ph lg[zn(o H)2(aq) ] = p Ks 2 = lg[zn(o H) - 3 ] = - ph + p Ks 3 + p Kw = - ph lg[zn(o H) ] = - 2pH + p Ks 4 + 2p Kw = - 2pH , 3 25,,,, co,,, ph, 3 25,, ph, Cr 3 + Cu 2 + Fe 3 + Al 3 +, ph, ph,,, Cl - CN - S 2 -, ,, Al( H2 O) 3 + x H2 O * K1 Al( H 2O) x - 1 (OH) H3 O + H2 O * K2 Al( H2 O) x - 2 (O H) H3 O + H2 O * K3 Al( H2 O) x - 3 ( OH)3 + H3 O + H2 O * K4 Al( H2 O) x - 4 (OH) H3 O + p * K4 12.4, * K3 * K2 * K1 * Km, : p * Km = p * K4-3(4 - m) ( 3 35) ( m = 3,2, 1), H2 O, H 2O O H -

111 3 101, H +, ph,,,, : 2Al(OH) ( H2O) [ ( H2 O) 4 Al OH OH H2 O Al( H2 O)4 ] H2 O OH O H [ ( H2 O) 4 Al Al Al( H2 O)4 ] 5+ OH O H H2 O,,,,,,,, [ Al3 (OH)4 ( H2 O)10 ] 5 + [Al3 (OH) 5 ( H 2O) 9 ] H + [ Al4 (OH)6 ( H2 O)12 ] 6 + [Al4 (OH) 8 ( H 2O) 10 ] H +,,,, [Aln( OH)3n ] [ Al(O H)3 ] Fe 3 + Al 3 +, Zn 2 + Cu 2 + Mg 2 + Pb 2 + Hg 2 + Sn 2 +,, p H Al 2 ( SO 4 ) 3 18 H 2 O AlCl 3 6 H 2 O Al 2 ( SO 4 ) 3 ( N H 4 ) 2 SO 4 24 H 2 O Al 2 ( SO 4 ) 3 K 2 SO 4 24 H 2 O A S AC A A K A [ Al 2 ( O H ) n ( SO 4 ) 3 - n 2 ] m [ Al 2 ( O H ) n Cl 6 - n ] m BAS BAC FeSO 4 7 H 2 O Fe 2 ( SO 4 ) 3 2 H 2 O FeCl 3 6 H 2 O F S FC [ Fe 2 ( O H ) n ( SO 4 ) 3 - n 2 ] m [ Fe 2 ( O H ) n Cl 6 - n ] m BFS BFC MgO MgCO 3 MO MC

112 ) 1800,,,, : (1) (),, () ; (2 ), Cl2 (), ( THMs),, ; (3),,,,,,,, %30%, 100 g/ L300 g/ L XAD, : XAD 2 2, : : : : (1), ; (2), ; ( 3)

113 3 103, 2), ( ) 3 27 (a) 3 27( b),, 3 27 ( a) ( b ),, : (a), O, N ; ( b), ; (c), ; (d), ; (e) ;

114 104 3), ( Irving-William): Mg < Ca < Cd < Mn < Co < ZnNi < Cu < Hg K,,, 3 17 lg K Ca Mg Mn Co Ni Cu Zn Cd H g , 97 mg/ g150 mg/ g;,cu Zn Ni Co Mn 67.4 mg/ g,26.1 mg/ g,17.4 mg/ g,9.6 mg/ g,5.6 mg/ g, [ FA]/ [Me] > 2, ph = 68, Fe 3 + Cr 3 + Al 3 + Pb 2 + Cu 2 +, ph = 6 ph = 7 Fe Cr Al 100 Fe Al Cr Pb Cu > Pb( 82) Cu(83) > Hg(43) > Zn(17) Ni(16) Co(15) Mn(4) Cd(9) > Zn > H g > Ni > Co > Cd > Mn > ph = 8 Fe, Al, Cr, Pb, Cu, Ni, Co, Zn > Hg Cd Mn > ()

115 3 105 : O O O C C O C O M M O M + O C O O,, 3.6.6,,,,, : (1 ) ; (2 ) ; (3) 3.6.4, Cr() Fe() ; Fe() Mn() O H,,,,, ,,,, (H + OH - ),,,, : NH O 2 NO3 - + H2 O + 2 H + N H + 4 N(- 3)NO N(+ 5), O2 ( - 2 ), H +, e : O2 NO3 - NO2 - Fe 3 + SO S CO2HCO 3 - ( ) H2 O2 O3 HO HO2, 8 63

116 106 : H2S S FeS NH 4 + NO2 - ( ), ( N H + 4 ),,, C N S,, DDT DDD DDE : H ( + 1 ) CHCl2 H ( + 3 ) CCl3 H + + 2e C ( - 1 ) + Cl - C Cl DDD Cl Cl ( - 1 ) DDT Cl OH - Cl Cl C ( + 2 ) C ( 0 ) + H2 O + Cl - Cl DDE Cl, DDT C ( + 3) ( + 1), DDT ( ), DDT C ( - 1) (0) ( + 3) ( + 2), DDT, () 3 18 ()C N S 3 18 ( ) R COO H + 2H e R C HO + H 2 O O O + 2 H e H O O H C X ( X = Cl, Br, I ) + H e C H + X - C C ( X = Cl, Br, I) + 2 e C C + 2X - X X 2 C X ( X = Cl, Br, I) + 2 e C C + 2X -

117 3 107 R S S R + 2 H + + 2e 2R S H R O S R + 2 H e R SR+ H 2 O :,,, ;,,,, (),,,,,,, N H + 4 NO2 - NO3 -,,,,, ;,,, HCO 3 - NO3 - SO Fe(O H)3 ( ); CH4 NH 4 + SO Fe O x Red, : O x + ne (, ) ( Nernst) : Red

118 108 E, V; E, V; R (8.314 J/ Kmol) ; T, K; n ; F ( C); [ Red] [ O x] 25, (3 E = E - R T [ Red] ln nf [Ox ] ( 3 36), 36) : E = E lg [ Red] n [ O x], : K = [ Red] - lg[ e] = 1 n lg K - 1 n [Ox ] [e] n ( 3 37) lg [ Red] [Ox ] ( 3 38) [e], - lg[e] p E, [ Red] = [Ox] p E p E ( ), (3 p E = 1 n lg K ( 3 39) p E = p E - 1 n 36), p E = p E = E E lg [ Red] [Ox] ( 3 40) ( 3 41) ( 3 42) p E E, p E E ph ( ), p E ph, p E E, p E = EF/ ( 2.3RT) ( 25, pe = E/ ) : (1) ph, p E, p E,,,, p E, ; (2 ),, 1.0, p E = 0.0( 3) (25, 1), E p E 3 19

119 E p E E p E CH 3 COO - CO H 2 S (aq) SO Fe 2 + Fe N H + 4 NO H 2 O O 2( g ) Cl - Cl 2 ( aq) E p E, : + :2O2 + N H + 4 NO H2 O + 2H ,,,,,,,,,,,,,,,,,,,, E, 0.15 V, 0.6 V0.7 V;, E 0.4 V0.5 V,,,,, E 0.4 V, 0.15 V,,, (V 5 + V 3 +, Cu 2 + Cu + Cu 0 ), E, V- 0.6 V 2 g/ L,, ( ),,,,,,,, Cr2O 2-7

120 110 Cr 3 +,, HgS E ph p E ph,,,, E(pE) ph, lgc, p E, 1) E ph, E ph : : 2H2O O2 + 4 H + + 4e : [ H2O] = 1, 25, E = V, E = E + R T 4 F ln p O 2 [ H + ] 4 [ H2 O] 2 ( 3 43) E = lg p 4 O2 [ H + ] 4 = lg p O lg[ H + ] 0.21, E = lg(0.21) pH = pH (1), : : H + + e 1/ 2 H2 2 H2O + 2e H2 + 2OH - E = E lg [ H + ] P 1/ 2 H 2 (3 44) E = 0.00 V, p H Pa), : = 1 ( E = lg[ H + ] = pH (2) (1) (2), E, 3 28 ph CO2/ ph HCO - 3 / CO 2-3, 69 ( ), ph 4;,, ph 9 E V V, V+ 0.5 V 3 27 E ph 1 ; 2 ; 3 ; 4 ; 5 ; E ph p E

121 ) p E ph Fe 2 + Fe 3 +, pe ph p E ph,,, : (1 ) (OH - S ) O H - ; (2) Fe 2 + Fe 3 + Fe(OH)2 Fe(OH)3 ; ( 3) SO 2 - CO mol/ L, : : Fe e - Fe 2 + p E = lg [ Fe3 + ] [ Fe 2 + ] ( 3 45) : Fe( OH)2( s) + 2H + Fe H2 O Ks 2 = [ Fe2 + ] [ H + ] 2 = ( 3 46) Fe( OH)3( s) + 3H + Fe H2 O Ks 3 = [ Fe3 + ] [ H + ] 3 = ( 3 47) 3 29, pe ph (a) H2 O : pe = ph ( 1 ) ( b) H2 O : p E = - ph ( 2 ) (c) ( 3 pe = 13.03( 3 ) 45) [ Fe 3 + ] = [ Fe 2 + ] (d) Fe 2 + ph Fe(OH) 2 (3 [ H + ] 2 = [ Fe2 + ] Ks 2 46): [ Fe 2 + ] [ Fe 2 + ] = mol/ L, ph = 8.95 ( 4 ) (e) Fe 3 + ph Fe(OH) 3, ( d), ph = 2.99 ( 5 ) 3 29 p E ph (f) Fe 2 + Fe 3 + Fe(OH)3 (3 45) ( 3 47) p E = lg K s 3 [ H + ] 3 [ Fe 2 + ] p E = pH ( 6 ) (g) Fe(OH)2 Fe(OH) 3 (3 45) (3 47)

122 112 p E = lg [ Fe3 + ] [ Fe 2 + ] = lg K s 3 [ H + ] 3 Ks 2 [ H + ] 2 = ph ( 7 ) 3 29,, [ H + ],, Fe 2 + Fe 2 +, [ H + ],, Fe 3 +,, Fe( OH)3,, Fe(OH)2, ph 69 Fe 2 + Fe(O H)3, p E, Fe 2 +, p E, Fe(OH )3 7, Fe 2 + ( 1), (2), Fe 2 + 4Fe 2 (aq) + + O2( g) + 10H2 O(1) : Fe 3 + 4Fe(OH) 3( s) + 8H + (aq) Fe 2 + (aq) + 2HCO - 3(aq) + Cl2(g) + H 2O (1) Fe(OH) 3( s) + 2CO2( g) + 2Cl - (aq) + H + (aq) fg m/ kjmol - 1 : Fe 2 + ( aq) H CO - 3 ( aq) O 2 ( g) 0.0 Cl 2 ( g) 0.0 H 2 O ( 1) CO 2( g) Fe( O H ) 3( s) C l - (aq) H + ( aq) 0.0 Fe 2 + : (1) rg m = [4( ) ] - [4( ) + 10( ) ] = - 64kJ/ mol rg m lg K = R T = = 11.2 K = (2) rg m = [ ( ) + 2( ) + 2( ) ] - [ ( ) + 2( ) + ( ) ] = kJ/ mol rg m lg K = R T = = 43.4 K = ,, 3) p E lg c, p E lgc ph = 7.00, TN = mol/ L( NO 3 - NO2 - NH 4 +, N2 ) : (a) 1/ 6NO / 3 H + + e 1/ 6NH / 3H2O ( pe = 15.14)

123 3 113 p E = p E + lg [NO 2 - ] 1/ 6 [ H + ] 4/ 3 [ NH 4 + ] 1/ 6 = lg [ NO 2 - ] 1/ 6 [NH 4 + ] 1/ 6 ( 3 48) p E = 5.81, [NO - 2 ] = [ NH + 4 ] ( b) 1/ 8NO / 4H + + e 1/ 8NH / 8 H2O ( pe = 14.90) p E = p E + lg [NO 3 - ] 1/ 8 [ H + ] 5/ 4 [ NH 4 + ] 1/ 8 = lg [ NO 3 - ] 1/ 8 [NH 4 + ] 1/ 8 ( 3 49) p E = 6.15, [NO - 3 ] = [ NH + 4 ] (c) 1/ 2NO H + + e 1/ 2NO2 + 1/ 2H2 O ( p E = 14.15) p E = p E + lg [NO 3 - ] 1/ 2 [ H + ] [NO2 - ] 1/ 2 = lg [NO 3 - ] 1/ 2 [NO2 - ] 1/ 2 ( 3 50) p E = 7.15, [NO3 - ] = [ NO2 - ] 3 30 p E lgc : (a) pe < 5, [ NH 4 + ], [ NH 4 + ] = mol/ L, lg[ NH 4 + ] = p E ( 3 48) ( 3 49 ) : lg[no - 2 ] = pE ( 1 ) lg[no - 3 ] = pE ( 2 ) ( b) p E = 6.5 [ NO - 2 ], [NO - 2 ] = mol/ L, lg[no - 2 ] = p E ( 3 48) ( 3 50 ) : lg[n H + 4 ] = p E ( 3 ) lg[no - 3 ] = pE ( 4 ) 3 30 NH + 4, NO - 2 NO - 3 p E ( ph = 7.00, mol/ L ) (c) p E > 7 [NO 3 - ], [ NO3 - ] = mol/ L, lg[ NO3 - ] = p E (3 49) (3 50) : lg[n H + 4 ] = p E ( 5 ) lg[no - 2 ] = p E ( 6 ) 3 30, NO - 2 p E(67 ),, (3 43 )( p E = 6.50 ph = 7.0): p E = pe + lg{ p 1/ 4 O 2 [ H + ]} 6.50 = lg{ p 1/ 4 O } p O Pa, NO - 2 NO 2 - p E lgc : Org - N N H + 4

124 114 NO - 2 NO - 3, E pe lgc (), ,,,,,,,, 1), Fe( H2 O) V( H2 O) , 3 31 Fe( ) V ( ) ( L = H 2 O ) 3 32 Co( ) Cr ( ) ( L = N H 3, L= H 2 O ),,,,,,, 2) ( H, O ) (O H), Cr( H2 O) [CoCl(NH 3 )5 ] 2 + : [CoCl(N H3 )5 ] [ Cr( H2 O)6 ] H3 O + [ Co( H 2O) 6 ] [ Cr( H2 O)5 Cl] N H ,

125 3 115, Cl - Co Cr, Cl - Co(),,,, Cl -,,, (ArO H), : (a) : Mn()OH + ArO H ( b) : Mn()OAr (c) : Mn()OAr + H2 O [ Mn(), ArO] [ Mn(), ArO] + H2O Mn()OH2 + ArO (d) Mn() : Mn()OH2 Mn 2 + (aq) + ( ) Mn(), ArO,, ph,,,, : (a) () 0.6V ( b) ( 1 2),,, NO 3 - / NO2 - Fe 3 + / Fe 2 + ( Cu 2 + / Cu + Co 3 + / Co 2 + ), 2 1, (c),, : ClO - 4 < ClO - 3 < ClO - 2 < ClO - ClO4 - < SO < HPO 2 4 -, : ClO3 - < BrO3 - < IO3 -,,, 3.6.7,, ( )

126 116, ( )3, / / 10-6 N H N ( CH 3 ) H 2 S CH 3 S H ( C H 3 ) 2 S ( C H 3 ) 2 S CH 3 C H O C 6 H 5 C H = CH ( ) :,,,,,,,, Pa, ( ER): ER = 20 ( Pa) Pa ER ( 3 51), ER ER ( ),, 3.7 ( ),,, :,,

127 3 117, / 3 21, ( ),,,, ( RO) (NF) ( UF )(MF), ( ),,,, NO - 3,,,,, ()

128 118, 8, (Cl2 )1mg/ L, ph = 7.0 ph = 8.5,? HClO ClO :,, ClO -, HClO,, ph, Cl2 HClO H + + ClO -, p Ka = = [ H + ] [ H + ] +, 1 = Ka = 0.24; ph = 8.5,HClO = 0.09,ClO - = 0.91 Ka [ H + ] +, ph = 7.0 HClO = 0.76, ClO - Ka, =, ph = 7.0, = = 76 / ( mgl(cl2 ) ), ph = 8.5, = = 9.9 / (mgl( Cl2 ) ),, ph = 8.5, 76/ 9.9 = 7.7 ph = 7.0, 7.7mg/ L,, ( )

129 3 119, ph,,, :, :, 1.,? 2.?, 1, 20? 3.,,?? 4.? 5. 6.?? 7. p HpOH?,? 8. ( ), : ( a ) H Cl, ( b ) NaOH, ( c ) Na2 CO3, (d ) NaH CO 3, (e) CO 2, ( f) AlCl 3, ( g) Na 2 SO 4,? 9.?? 10., 11.? 12.?,,,? ?,? 15.? 16.?,??? 17. BOD? COD BOD?, COD, COD? 18.?? 19.?? ()? 20.??, 21.???

130 ? ? 25.??? 26.,? p E ph 27.? 28.? 1. V s, M V p, CaCO3 ( mg/ L) mol/ L HCl 100 ml, 3.00 ml H Cl,,12.00 ml HCl, (mg/ L CaCO 3 ) 3. [ Alk ] = mol[ H + ]/ L 25, ph = 7.00, [ CO 2 ( aq) ] [ H CO3 - ] [ CO 2-3 ] 4. : / mg L - 1 / mgl - 1 Ca H CO Mg SO Na + 14 Cl - 17 K + 2 p H ( 7.5 ) ( mol[caco3 ]/ L ) mg/ L,100 mg/ L, 40 mg/ L ( S 2 - ) 125 mg/ L, ThOD ThOC 6. COD 252 mg/ L, 25 ml, K 2 Cr 2 O 7? %,, 12,? mm, 2.5 g/ cm 3, ( Pas ), 9., 1 L, / g / mgl - 1 / g / m gl ,Fe( OH ) 3( s) Fe 3 + :