1. , , , (e), (p) , , . ( (p) , , : ) . , 2002 , . (Nature 419, 456 (2002)). (p p ). 1-1. , pp , . 1-2. ? 2. [18] C18H18 (Acta Cryst. 19, 227 (1965)). : –3 1 e⋅Å . H H H H H H H H H H H H H H H H H H . « , En = h– , : , me – ,L– 0, ±1, ±2, ±3, ; h2n2 , 2me L2 ,n– . ». n …, , , . 2-1. , 1.40 Å, , . 3. O22+ . O22+, , . , + O, , . 1960- O22+ , . , , O+ : [O≡O]2+. . , pO22+, « - ». 3-1. O+, O22+? 3-2. 3-3. 3-4. 3-5. O22+ O22+ ? ( )? 2+ O2 ? , O2 2+ . , 2+ O2 ? 3-6. 3-7. O+−O+? O+, O22+? 4. . Ni-Cd (« : ») , , , , . . 2000 : . - Cd(OH)2( ) + 2e– → Cd( ) + 2OH– E1° = –0.809 2NiO(OH)( ) + 2H2O + 2e– → 2Ni(OH)2( ) + 2OH– E2° = –0.490 E1° E2° – 4-1. 25 . ? . ? 4-2. . , 4-3. . 4-4. 4-5. E 25 . 700 ⋅ . 5. ( 116 4 3 . . , , – 0.73 / 5-1. ). 3 43000 / , . , : ( ) 5 ; ( ) 2.2 ; ( ) 2.1 . 5-2. CO2 ? ( ) 300 ; ( ) 1 ; ( ) 5 ; ( ) 10 ; ( ) 30 . ; ( ) 12 ; ( ) 3.3 6. . 80 NH4NO3 1 0 . : 6.01 25.69 ⋅ ⋅ –1 6-1. H2O. ⋅ 76 ⋅ –1 –1 ⋅ –1 ⋅ –1 , , , 1.86 . : ( ) 1.86 ; ( ) 3.72 ; ( ) 3.72 ; ( ) 1.86 ; ( ) –3.72 ; ( ) –3.72 ; ( ) –1.86 K; ( ) –1.86 ; ( ) –3.83 . 6-2. :( ) ; ( ) ;( ) ;( ) ; ( ) ; ( ) ; ( ) . 6-3. ( ): ; ; ; ; , ; ; ; ; ; ; ; . 6-4. : ( ) ∆S > 0; ( ) ∆S = 0; ( ) ∆S < 0; ( ) ∆S . 7. , CO2 CO2: – Pc = 73.75 5.1850 , T3 = 216.58 . 7-1. 1 . , Tc = 304.14 ; 25 . , CO2? ( ) 2 ( ) 20 ; ( ) 73.8 ;( ) 7-2. 5.1850 ;( ) 100 ;( ) 20 – P3 = ;( ) 63 ; ( ) 5.185 . , CO2? ( ) ; ( ) 73.8 . 2 ;( ) ; ;( ) 8. – α-Fe – 2.87 Å. 7.86 / 3 . 25 – γ-Fe – , 3.59 Å. α-Fe 8-1. , α-Fe , . γ-Fe 8-2. γ-Fe, γ-Fe , . , 8-3. ( ) α-Fe ( . ., (1/2, 0, 1/2)), , . ? , 8-4. , γ-Fe. , 8-5. . 8.3 , 8.4? 0.077 , (200) 8-6. . ( , α-Fe, 32.6 . . . , ). 9. – : α-, β-, γ- , 6, 7 , 8 . β( , – . , : Dacus Oleae , , ; , . , ) . , C42H70O35⋅C12H12N2⋅12H2O. P21. ( ): a = 15.394(7) Å, b = 31.995(12) Å, c = 15.621(7) Å, o β = 103.738(15) , α = γ = 90o. 4 (2 – ). 3 9-1. ( Å) . 10. : CO, H2O, , : ( ) 1; ( ) 30; ( ) 54; ( ) 120; ( ) 174; ( ) 720; ( ) 10-1. C60? 2; ( ) 3; ( ) 4; ( ) . 10-2. . XY , WZ. ? (1) XY WZ – (2) XY (3) XY (4) . , WZ. , WZ. XY , WZ. : ( ) 1; ( ) 2; ( ) 3; ( ) 4; ( ) 1 2; ( ) 1 3; ( ) 1 4; ( ) 2 3; ( ) 2 4; ( ) 3 4; ( ) 1, 2 3; ( ) 1, 2 4; ( ) 1, 3 4; ( ) 2, 3 4; ( ) 1, 2, 3 4; ( ) . 11. 11-1. (1) « » « » : γ? (2) 83? (3) 82? (4) ? (5) ? 12. 14 C – β- t1/2 = 5700 . . , 14 , 14 . 12 C . 13 C C C CO2 , 14 12 C/ C . , 12 14 . C , 14 C. 0.277 C (1 ). , 12-1. 0.25 14 12 , , C / . , 14 12-2. 12-3. C 14 C, ? 12-4. 14 C ? ( .), C/ 14 14 C, 18.5%. C 75 , , 13. U (Z = 92) – 238 U (99.3%, t1/2 = 4.47⋅109 α. (Z = 82). 235 ) , U (0.7%, t1/2 = 7.04⋅108 α- (4He2+) ( ). β– 206 Pb ) , , Pb . γ- 207 , . 235 U 238 , U, ; , . 235 : U + n → U* → + 2-3 n + 200 α- 13-1. β- 235 / U. , ( 238 U → 206Pb 235 U → 207Pb). , 13-2. . 13-3. , (235U : , . . 238 U = 1 : 1), , . ( 13-4. ), , 1 : C + O2 → CO2 + 393.5 / ( 4.1 / ). 235 U. 14. (Pb(NO3)2) (KI) (PbI2). , 5.000 . : , . : , , 1 0.500 0.692 2 1.000 1.388 3 1.500 2.093 4 3.000 2.778 5 4.000 1.391 PbI2 ( ), 5,00 4,00 3,00 2,00 1,00 0,00 0,00 1,00 2,00 3,00 4,00 5,00 Pb(NO3)2 ( - ), : 14-1. . . 14-2. PbI2 Pb(NO3)2. 15. IV 1 2 9 d , d , …, d ML62+ (L – : » M( )2+; , « . 15-1. ). « » , , t2g ( , ) ∆, eg , P, . : . 16. . , , . 100 ( 1913 .) , , Co(NH3)63+, , , . , , CoCl3⋅4NH3, 450-200 . Rh(py)3Cl3 (py – . –1 ). . , ≡ σ, - S2 ≡ i , . [Co(NH3)4Cl2]Cl, , ) S1 , [Co(en)2Cl2]Cl (en – , . 16-1. 16-2. Co(NH3)63+. Co(NH3)63+ NH3 3– CoF6 ? F– . 16-3. . Rh(py)3Cl3. 16-4. , 16-5. . [Co(en)3]I3? 17. 4- , , - . , . MA2B2, . sp , – dsp Ni 17-1. 4p 2 3 sd . 2+ [Ar]3d 8. NiCl42–, Ni(CN)42–. 3d, 4s – . 3 18. . (PC) – . . , PC , PC Cu(I) Cu(II). PC : ( http://www.rcsb.org/, : 1PNC). 18-1. 18-2. 18-3. Cu, Cu(I), Cu(II). PC, PC, ? 10500 / PC –1 « 597 3 ⋅ –1). 0.700. ⋅ . (PC »), . . ( 4500 PC PC ( 1 ) Cu(II) 5 3 . , 18-4. – . Ni(II), Zn(II) , , Cd(II), . - ? Co(II), , 19. , , 10 (100 Å). , , . « » . : (1) ; (2) ; (3) ; (4) . , . ), ( ( ) , . . , ( , . 1 ). . , ( . 1. . 1 ). :( ) ( ) . . « , y, », n- , . : y = 10n + 2 (n = 1, 2, 3, …) ( 2 , « » 1 2 3 4 5 . 2). . 2. « » . , . (TEM), – (HR-TEM). , – , , . . 3. ( ) Pd(0), . ( ) Pd(0) . Pd(0) ) 19-1. Pd(II)- (1 : nPd(II) + nH2 → Pd(0)n + 2nH+. , Pd(0)n , , 2.05 . (N) . (n) ρ = 12.02 / . 3 ? . Pd(0)n, 19-2. , , : + H2 Pd(0)n Pd(0)n, 3 50 ; 3 400 50 5 3 H2 Pd(0) . 4 H2 . 30 . . 4. . 4. . 30 (%) . , 50 Pd(0), 5 3 . i ii , Pd(0), , : ( ) (TON): TON = Pd(0) ( 19-3. H2 ( Pd(0) ( H2 ( ( ). )/ Pd(0)n, ) / (TOF):TOF = ); ( ) ) / C6H10: ρ = 0.81 / , 3 . -1. Pd(0)n CH3(CH2)3CH CH2 + H2 CH3(CH2)4CH3 , . -1 30 ). , Pd(0)n . . 5. ( . . 5. 1H (300 ): ) -1; ) 30 . ,δ/ . . -1 ( ( .5 ) .5 ) 0.88-0.96 3 1.15-1.32 4 1.99-2.08 2 4.85-4.98 2 5.65-5.79 1 0.88-0.96 9 1.12-1.37 12 1.99-2.08 2 4.85-4.98 2 5.65-5.79 1 -1 30 . 20. , . , . [A]s – , [A]s. , , [A]b. [A]s 20-1. d[A]b/dt. 75% [A]s 20-2. [A]s . ? 21. Br2 + CH4 : Br2 + CH4 → CH3Br + HBr. : k1 Br2 + M → 2Br + M Br + CH4 → CH3 + HBr Br2 + CH3 → CH3Br + Br HBr + CH3 → CH4 + Br 2Br + M → Br2 + M M– , k3 (1) (2) (3) (4) (5) k2 k3 k4 k5 k4 . : 21-1. CH3 Br. , . . : d[CH3] / dt = 0 , d[Br] / dt = 0. CH3Br k1 – k5 . 21-2. . , , CH3 Br . k11 / 2 k 2 [Br2 ]1 / 2 [CH 4 ] ⋅ k 4 [HBr] k 51 / 2 +1 k 3 [Br2 ] (I) k11 / 2 k 2 v' = 1 / 2 ⋅ [Br2 ]1 / 2 [CH 4 ] k5 (II) k11 / 2 k 2 k 3 [Br2 ]3 / 2 [CH 4 ] ⋅ v' ' = 1 / 2 [HBr] k5 k 4 (III) v= , . (I), (II) 21-3. , (III) , . : 22. , CH3COOH/CH3COO–) . ( , , NH3/NH4+). ( . , . pH , pH = pK a + lg Ka – A–, HA : [A − ] [HA] HA, . pH 22-1. –4 2.1×10 ) , 0.150 M , 22-2. 0.200 M . pH . 0.01000 M , 0.200 M 22-3. 100.0 3 (Ka = , (CH3COOH, Ka = 1.8×10–5), 0.150 M pH = 5.00. 22-4. pH (C6H5COOH, Ka =6.6×10–5) 4.18; ( ) 9.82; ( ) 9.00. , 0.0100 M 0.0100 M . A B. 22-5. A: 0.100 M CH3COOH (Ka = 1.8×10 ), B: 0.0500 M NaOH. : i : ( ) ; ( ) ;( ) ;( ) ii pH : ( ) 3.02; ( ) 4.74; ( ) 3.17; ( ) 7.00. 22-6. A: 0.100 M CH3COOH (Ka = 1.8×10–5), B: 0.150 M NaOH. : i : ( ) ; ( ) ;( ) ;( ) ii pH : ( ) 12.00; ( ) 12.70; ( ) 13.18; ( ) 12.40. 22-7. A: 0.150 M CH3COOH, B: 0.100 M NaOH. i : ( ) ; ( ) ;( ) ;( ) ii pH : ( ) 3.17; ( ) 7.00; ( ) 5.05; ( ) 13.00. 22-8. A: 0.100 M CH3COOH, B: 0.100 M NaOH. : ( ) 5.00; ( ) –5 ; ; : ; : : ( ) i ;( ) ii pH ; ( ) ;( ) : ( ) 7.00; ( ) 13.00; ( ) 8.72; ( ) 3.02. ; 23. ( ). 250 ( 3 ). , . pH . – , . . - - . , 23-1. 3 50.00 0.1000 M Ka =1.8×10–5) 1. , (CH3COOH, 0.1000 M ; 1. , pH 3.2 – 4.4 4.2 – 6.2 6.0 – 7.6 6.8 – 8.2 8.0 – 9.8 9.3 – 10.5 ( 23-2. - C, C6H8O6) – , : C6H8O6 ς C6H7O6– + H+ C6H7O6– ς C6H6O62– + H+ Ka1 = 6.8×10–5 Ka2 = 2.7×10–12 , . 50.00 3 0.1000 M . i ii : : ( ) 7.00; ( ) 2.58; ( ) 4.17; ( ) 1.00. pH ( ) 50.00 iii pH ( ) 4.58. iv pH v 0.2000 M 3 , ; ( ) 35.00 : 3 3 ; ( ) 25.00 ; ( ) 20.00 12.5 3 3 . : ( ) 4.17; ( ) 2.58; ( ) 7.00; : ( ) 7.00; ( ) 8.50; ( ) 8.43; ( ) 8.58. ( . 1): ( ) ;( ) ;( ) ;( ) . vi pH ( ) 11.42. 26.00 3 : ( ) 13.30; ( ) 11.30; ( ) 11.00; 24. – . , , . – – , , , , . , . S 1 2, : KD (S)1 , KD – (S)2 a S : KD = ( aS ) 2 ( aS )1 (1) S, . . 1. ( . . 1). (1) , . S , , , KD D: D= CS – ( (CS ) 2 (CS )1 (2) ) S , – . , (2) , D– S ( , , S S, S V1 V2 n , . ). W0 1 – , pH 1, 2, , S Wn S, : n V1 W0 Wn = DV2 + V1 (3) V1 W f n = n = W0 DV2 + V1 fn – S, n (4) n 1 . (3) , (4) , . (3). 24-1. 24-2. D = 3.2. S S, 50 S: ( ) 3 100 3 25 3 ;( ) . 99% 24-3. 3 100 , 25.0 3 0.500 X, KD = 9.5? Ka ( ) , HA 24-4. X . , HA ( KD), . + D . [H ] . – 24-5. 6.6×10 –5 1×10–10, . . D / KD i ii , 24-6. 8, C9H6(OH)N ( + C9H6(OH)NH (OxH2+), . . OxH) – K1 C9H6(O–)N (Ox–). K2 N H pH N N O- OH OH OxH2+ Ox- OxH : K1 = 1×10–5, K2 = 2×10–10. KD = 720. , [H ] i D 8- + ii iii . D pH, D pH . . 25. - - - , . . (m/z) , z = 1, . - , R = m / ∆m, ∆m – , m – , C2H4+ CH2N+, (28.0313 28.0187, , R = 28 / (28.0313 – 28.0187) ≈ 2200. (R ≈ 300-1000) . 28), . , (m = ), - , , 15 (12C1H3+) . , CH3+ 19 (13C2H3+). , , : 98.90% 12C (M = 15) (M + 1 = 16) 13 2 C H3+, . 1.10% 13 : 99.985% 1H 0.015% 2H. 12 1 C H3+, : 13C1H3+ 12C1H22H+, , . . C, , M + 4, . CH2Cl+ C, H Cl (75.77% 35Cl 24.23% 37Cl). C1H235Cl: 0.989×(0.99985)2×0.7577 = M + 1 = 50 13 C1H235Cl: 12 2 1 35 C H H Cl: 12 1 2 35 C H H Cl: 0.011×(0.99985)2×0.7577 = 0.00833 0.989×0.00015×0.99985×0.7577 = 0.00011 0.989×0.99985×0.00015×0.7577 = 0.00011 0.00855 M + 2 = 51 13 0.011×0.00015×0.99985×0.7577 = 1.25×10–6 0.011×0.99985×0.00015×0.7577 = 1.25×10–6 0.989×(0.99985)2×0.2423 = 0.240 0.240 M = 49 12 C2H1H35Cl: 13 1 2 35 C H H Cl: 12 1 C H237Cl: 0.7491 M + 3 = 52 13 C2H235Cl: 13 1 C H237Cl: 12 1 2 37 C H H Cl: 12 2 1 37 C H H Cl: 0.011×(0.00015)2×0.7577 = 0.011×(0.99985)2×0.2423 = 0.989×0.99985×0.00015×0.2423 = 0.989×0.00015×0.99985×0.2423 = M + 4 = 53 13 C2H1H37Cl: 13 1 2 37 C H H Cl: 12 2 C H237Cl: 0.011×0.00015×0.99985×0.2423 = 4.0×10–7 0.011×0.99985×0.00015×0.2423 = 4.0×10–7 0.989×(0.00015)2×0.2423 = 5.4×10–9 8.1×10–7 13 0.011×(0.00015)2×0.2423 = M + 5 = 54 C2H237Cl: M 1.9×10–10 0.00266 3.59×10–5 3.59×10–5 0.0027 6×10–11 M + 5 , . , . , ( CH2Cl+), ( M = 49 100%). M = 49: M + 1 = 50: M + 2 = 51: M + 3 = 52: M + 4 = 53: M + 5 = 54: : 100% (0.00855/0.7491)×100% = 1.14% (0.240/0.7491)×100% = 31.98% (0.0027/0.7491)×100% = 0.36% (8.1×10–7/0.7491)×100% = 1×10–4% (6×10–11/0.7491)×100% = 8×10–9% ( , http://www.chem.uoa.gr/applets/appletMS/appl_MS2.html) 25-1. – : 35 Cl, 37 , : 28Si, 29Si, 30Si, Cl. + 25-2. SiCl2 ? : 10B 19.9%, 11B 80.1%, (A – E) : 35Cl 75.77%, 37Cl 24.23%. BCl+? : ( ) N2+, ( ) CO+, ( ) CH2N+, ( ) C2H4+ 25-3. M = 28 . , M + 1, . H: C: N: O: M+1 H: 99.985% 12 C: 98.9% 14 N: 99.634% 16 O: 99.762% 1 1.15%. H: 0.015% 13 C: 1.1% 15 N: 0.366% 17 O: 0.038% , : 2 18 O: 0.20% 26. – , , . . 26-1. . A, B, C. 26-2. 1. CH3I ( . ) A (C10H21N) 2. Ag2O, H2O, ∆ 1. CH3I ( . ) A 1,4- + 1,5- 2. Ag2O, H2O, ∆ C6H5CH2OCOCl o NaOH, 0 C B KMnO4 ∆ C H2 / Pd / C (S)-5- - 27. . . . – : OH 8 HO 1 3" 1' O 6' 5 OH 4" 4 O : 27-1. 1. NaH / B 2. MeI ( .) C , 27-2. C-5, 1 , C-4 H- . C-5 : ( ) ;( ) 2M 27-3. D ;( ) NaOH . , , E: NaOH 2M D+E D (C6H6O3) (C9H12O2) FeCl3, ( FeCl3. : , ( II). D E. 1 1 I). H- HE , 27-4. 13 C B. C- , 28. – L( α- , ) S- . L- 28-1. L- ? . , 28-2. ( N- ). . ROCO-, . ( ) - ? . H. . . - . . . 28-3. . . 28-4. (1) (2) (3) (4) (5) C- ), ( (1) (2) (3) (4) (5) , ( C6H5CH2OCOCNH2 C6H5CH2OCO2CH3 C6H5CH2OCO2C(CH3)3 C6H5CH2OCOCl C6H5OCOCl. - )? . , 28-5. , R OCO NH : H+ : [R+] + CO2 + H2N O O O N O N C. A. O O2N O O B. H N D. CH3O CH3O O N 29. - , - . , , , (A), (R – ): COOCH3 O R O O O O OH HO OH OH A , 29-1. – ( ) (A1), : , , – (A2). , , A1; ( ) - , . - 29-2. 154. A1 1 H- A1 . : 1 - - A1: OH OH OH HO OH CH3 HO CH2OH OH CH3 OH C B A A1 29-3. a, b, c d , 1 H- . 30. , - C Br Br2 / CCl4 C : C C Br 30-1. . . H C à) C C Br H C á) CH3 H H C Br C C H CH3 C H Br H H3C H C C ã) H Br H H3C C â) C H CH3 Br H3C H3C H C H C H3C Br H 34. 2,5- -1- . , . – . - 1,4. 2,5- , (1) (N- 2,5- -1- ). 3 . . : 2,5- . , . . . – 1. , , 1: . 2,5- -1- : , , 2,5- , . HCl, 0.5 M HCl . , 25 3 , , , 10 3, 5 3, 5 , , , 10 5 , , , ( 1c , 10 c ), 100 3 , , (254 ), ( - 1:3), . . 2,5- -1- ) 228 1 (2.0 HCl. 186 (2.0 3 , 0.5 ) 2,5- 15 . . 5.0 3 0.5 M HCl, 3 1 / 1 - . . 3 . . . ( 3-5 ) (~5) . . ( 1:3. (254 ) - ). . . . I. II. III. IV. : . . . . . . . Rf . 1 . H(CDCl3) : = 2.04 ( , 6H), 5.91 ( , 2H), 7.22 ( , 2H) 7.44 ( , 3H) δ, , . . . II. III. IV. . : : : : : 178 342 : 52% 48°C ( . 50-51°C) . . Rf : 0.85 H(CDCl3) : = 2.04 ( , 6H), 5.91 ( , 2H), 7.22 ( , 2H) 1 7.44 ( , 3H) 35. DEET . DEET – N,N- - , . DEET, , , , 1957 . . 230 DEET DEET. 70 . , . DEET • : N,N• - - : (25oC) 0.996 , (1 19 DEET DEET , - - ( - - ). . (NaOH) : ) , 111 C ) (160oC) . , - (SOCl2); . ) . , . , , : . (0.55 (0.5 , 3.7 3 , 7.6 ), 3 (0.2 ) ), (2 ) 99.5% SOCl2 8 3 5 . . 3 (1.3 25 ) , 12 . . 10% NaOH (5 3 1 MgSO4 Na2SO4 ) SOCl2 0 oC. 15 , 3 . 3 1 , . . . I. II. III. DEET . : . . . . - 3 [ ]: ; , , , ; , 50% - . , ; , 50% - 3, - , , I. II. III. 1763 C− H C− H C=O –1 1720 –1 . [ ]. . ~3065 ~2987-2880 : : ; –1 ; ~ –1 I. II. III. : 0.68 0.70 : 97% : . - 3 [ ]: ; , , ; , 50% - . - , 50% . 1763 . –1 –1 1720 , C=O 36. . . . ( 1984 α- .) - . K. 2- , , . , , , . Fmoc- , N-α . , . , C, ). ( , . . 1. 2- , , . – 1% . H2N-Ser-Ala-OH , Fmoc- , . . 2. 2- . 2 . H2N-SER-ALA-OH Fmoc- 2- H2N-SER-ALA-OH .2 . ( 1). ( 2-5). Fmoc- 2. 11. . . 2. 2 Fmoc- 3 20% 3. 2-3 . 5. (3 ) . (Asample) , 3 3 . , 4. 6. . 20% (Ablank) 290 . n– Fmoc- ( ), ( ), ,m– . . Fmoc-Ala-OH (62 , 0.2 ) (139 , 0.8 ). 1. (N,N- ) 3 CH2Cl2 (2 ) DIPEA , , (200 30 , 0.2 ; Cl 1.0 2- / ), 1 CH2Cl2. . 3 0.2 « » , – 3 CH2Cl2 , . 20% Fmoc. . , 5 ( 3 2 Fmoc-Ser(O-t-Bu)-OH (383 . 20 . : 3. 1 , 1 ( , , ) ) HOBt (135 DIC (156 3 . 2 3 3 2 CH2Cl2 ( , 1 , ). 15 . CH2Cl2/MeOH/DIPEA=17/2/1, KOH. , 3 3 3 2 2 2. 3 3 3 ) , 3 ). , 1 , 1 ) ) CH2Cl2 ( ( 2 ). : : 1. 5 2. 80 3. 2 100 3 EtOH. 3 20 3 0.001 M EtOH. KCN 98 3 . 4. 2 . 5. 5 ( ) ( 4. 5. . , ). Fmoc- , ( 2. 2 3 ) - 10 (3 . 2 3 ) ( (5 3 3 . 0.5% TFA/CH2Cl2) , ). . . 5 . Ala-OH 3 . . 10 , H2N-Ser- – . : I. : 8 II. ( : 12.3 0.35) III. : 65% IV. : 210-213°C . ( CHCl3/MeOH=9/1) i) Fmoc-Ala-OH, ii) Fmoc-Ser(O-t-Bu)-OH, iii) H2N-Ser-Ala-OH . Rf : i) 0.25, ii) 0.40, iii) 0. α . [α t– /100 (25 3 ]Dt. : ), D HCl. : α = 1.91° , [α ]Dt = –31.8° (589.0 –1⋅ –1⋅ 3 . ), l = 1 , c=6 37. . - , , . . . , , 1 . = 101 325 (= 1.013 ). ( ). , ( , , , ), . dP ∆H = , dT T∆V , ∆H – dP / dT – , ∆V – – , . , - : ) , ) . : d ln P ∆H =− . d (1 / T ) R ln P , 1/ . , . (100-200 0-20 ), ), 0-200 °C, ( – , , H2O. : ) ( . . . 16 , , 180 °C. , . 80 ( , , . , ), ( ). P ( ), . ln P, T, 1/T. ) ln P, T, 1/T. ( ln P 1/T. . – , . – . . , 6 . 3 38. . –1 +7, , . +7 +5 +3 +1 0 –1 HClO4, ClO4– HClO3, ClO3– HClO3, ClO2– HClO, ClO– Cl2 HCl, Cl– F2 HF, F– HBrO3, BrO3– H5IO6, IO4– HIO3, IO3– HBrO, BrO– Br2 HBr, Br– HIO, IO– I2 HI, I– , . , . . . . . . 13×100 , II . – 1-2 3 5 . , , . 3-4 – . : , I2 , . , , . I. . 2 I– 3 0.1 KI AgNO3. 0.1 . . 2 3 3 . 2 3% H2O2. KI 5 3 (5% NaOCl). , ? 3 KI 5 . 0.1 . 0.1 II. . 1. 3 3 3 . . 0.1 M KI , ? , 2. 3 ? 3. H2SO4 3-4 5 IO3– 5 . 3 III. . 3 2 3 6M I2 ( 10 , 0.5 ) 6 M KOH. , KOH. 6 M KOH. 0.1 M Na2SO3, 2 ? . . . . 0.1 M KI 3 3 KIO3 2 3 6 M H2SO4. . . , 6M . . , 6 HNO3 (10 ), . . ? . KOH. , , , 6M , . . . , . . , . , . (2). (1). 2 3 , 6M H2SO4 5 3-4 . 3 . 3 5 . 1M . Na2SO3, . . II . (2). AgNO3, 5-10 . , 0.1 M .I . 1. 2. . , .I ,I ,I . , . III (1) , . II . . 0.1 M , AgNO3 . III (2) .I . . , KOH I2 6M . III ? 3. . , . 4. ? . 5. ? , . 6. , – – – 5– ClO2 , ClO4 , BrO3 , IO6 . 1. I : I– (aq) + Ag+ (aq) → AgI↓ ( ). – – + – I : 2I (aq) + OCl (aq) + 2H (aq) → I2 + Cl (aq) + H2O . I2 + OCl (aq) + H2O → IO3– (aq) + 5Cl– (aq) + H+ (aq). NaOCl – . 2I– (aq) + H2O2 + 2H+ (aq) → I2 + 2H2O. I : . 2. . 2– .II SO3 KIO3) . – 2– – 2– IO3 + 3SO3 → I + 3SO4 , 5I– + IO3– + 6H+ → I2 + 3H2O. ( . III . . - IO3– - : - - : IO3– + 3SO32– → I– + 3SO42–, 5I– + IO3– + 6H+ → I2 + 3H2O, 3I2 + 3SO32– + 3H2O → 6I– + 6H+ + 3SO42–. – . , . . III (2) ( ) , .I : – + I (aq) + Ag (aq) → AgI↓. I2 6 M KOH ( . III ) . 3. : 3I2 + 6OH → 5I + IO3 + 3H2O. : – – + 5I + IO3 + 6H → 3I2 + 3H2O. (–1). – 2 5 : ns np . – 4. . X– – – 5. F2 , KF KF + HF → F2 + H2 ( 6. ClO2–: IO65–: . HF: ) 2F– → F2 + 2e 2H+ + 2e → H2 E° = –2.87 E° = 0.00 2F– + 2H+ → F2 + H2 ∆E = 2.87 , ClO4–: ; BrO3–: ; 39. Cu(NH3)4SO4·H2O . (Cu(H2O)4(H2O)22+, . . , . Cu2+(aq) : 2+ Cu(H2O)6 , CuSO4⋅5H2O, Cu(H2O)4SO4⋅H2O, NH3 Cu2+ (aq) + 4NH3 → Cu(NH3)42+ + 2 0.01 Cu2+(aq)) - . 5M 2+ Cu(NH3)4 . 2+ 2+ Cu(NH3)3(H2O) , Cu(NH3)2(H2O)2 Cu(NH3)(H2O)3 5M Cu(NH3)5(H2O)2+. Cu(NH3)42+. [Cu(NH 3 ) 24+ ] K form = 2+ [Cu aq ][ NH 3 ] 4 NH3, . : 2+ NH3 , , Kinst = Kform 1 / Kform, . Cu(NH3)42+ , . . , . Cu(NH3)42+ , . . . . , Cu(NH3)42+ NH3, 2+ Cu , NH3, ( , ). 1. 6.25 CuSO4⋅5H2O NH3 6 3 2. , 3 10 . Cu(NH3)4SO4⋅H2O ( , , Cu(NH3)42+. ). 10 . 3 – – - ? 3. :( ) ,( ) ( ) . 4. . NH3, , CaCl2, - . CaO. , 5. : 0.3 , NH3, Cu(II) NH3 CuSO4⋅5H2O Na2CO3 2 CuCO3. Cu(NH3)4SO4⋅H2O Cu(NH3)42+. , 10 2 3 , Na2CO3 Cu(II) CuCO3 , Cu(NH3)4SO4·H2O? Cu(NH3)42+ → Cu2+ (aq) + 4NH3. NH3: ( ) ( ) ( ) , CaCl2, HCl. (- ) (- ). , ? 40. , . : 2HCO3– ς H2O + CO2↑ + CO32–, Ca2+ + CO32– = CaCO3↓. . , , . – . o , D ), 3 H2O ( ( CaCO3 / 1000 3 CaO / 100 3 CaCO3 / 100 H2O ( H2O , Fo) ). . ( 1. 3 50 ) « H2O. » 2+ 2+ , Mg Ca . NH3 – NH4Cl pH = 10 3-4 0.5%T( ). Mg2+ , 2. 1). Ca 2+ 0.01 F ( Mg2+ 1 . 3 , . 1:1. Ca Mg CaCO3 / 3 2-3 2+ 2+ Mg , 2+, . . pH = 10 , . V– , CaCO3, 50 , 3 1 CaCO3 / 100 3 . 3 H2O Fo = 2VC. = 0.01 F ~ 1 CaCO3 / 1 3 , Fo = 2V. – 1. CaCO3 , 1 0.01 F 3 1 . 2. 3. 25 Do F°, CaCO3 / 3 3 ? H2O. 4. , 2+ Ca , Mg 2+ ? ? 5. . 1 1.0×10–3 M CaF2 1.7×10–10. (1 ppm) CaF2?