PV nrt p Pa R 8.314J/mol K p1v 1 p2v2 = T n 1 T 2 n, T p 1 V 1 p 2 V 2 n, P V 1 /T 1 V 2 /T 2 n, V P 1 /T 1 P 2 /T 2

Transcription

1 1 (2 ) 1 (chemicals)

2 PV nrt p Pa R 8.314J/mol K p1v 1 p2v2 = T n 1 T 2 n, T p 1 V 1 p 2 V 2 n, P V 1 /T 1 V 2 /T 2 n, V P 1 /T 1 P 2 /T 2 n m/m mrt M = pv M (g/mol) m (g) m/m pm ρ = RT ρ P 1 P 2 P 3 P P pi ni ni pi = p p xi p n n n i /n x i Dalton 2. 1

3 V V = x i = ni n i V i V ni Vi pi = p xi p p n V U1 ρ 2 M 2 = = U ρ M an ( p + )( V nb) = nrt a 2 V ( p+ )( Vm b) = RT 2 Vm a V 2 b a b a 1 3 T c P c V c 1mol 2-4 P ε = kt 2 k J/k Boltzmann 3 3 Em = N Aε = N A kt = RT 1mol 2 2 R 8.314J/mol K RT U1 ρ 2 M 2 Q Em = mυ = RT υ = = = 2 2 M U 2 ρ1 M 1 2 υ υ υ o (1) 2

4 E0 RT N i = Ne E 0 N i E 0 N E 0 N i 2 p2 H 1 1 lg = p R T2 T1 P T H T 2 T 1 3 H Pa

5 b c α β γ a c b α c β γ a c α β a b γ a b c a=b=c a=b c α β γ 90 o α β γ 90 o α β γ 90 o γ α β γ α β γ γ 120 o c b a a=b=c a=b c a b c α γ β 90 o α β =90 o α γ =90 o a b c γ 120 o γ 90 o α β γ 90 o P P P P P P I I I I F F F F C C C H R R H P42 2 4

6 Cs + Na + Cl Cl 1 8 = 1( ) CsCl 1 Cs + Cl = 4( ) ( ) NaCl Na + 4 Cl Cs + Cl Cl Na + CsCl Cs + Cl - NaCl Na + Cl - 5

7 3 1 s p d n l m ms Democritus, B C Leonhard Euler, Antoine L. Lavoisier J. B. Richter Joseph L. Proust John Dalton J. J. Berzelius

8 (Boyle. R ) 1661 (Priestley J ) (K W Scheele 1742 l786) % O) ( 17 8O) 0.204% 8 10 ( 18 8O) 109 ( 108 ) ( ) ( ) 1913 (Moseley Henry ) X ( ) X X X ( 1 1) 2

9 x ( ) (z) ( 1 2) a b 1920 (Chadwick James ) C C 16 O 17 O 18 O Na 23 Na (127.61) (126.91) (39.95) (39.09) (58.93) (58.69) (Crookes w ) (SoddyJ Frederickl ) 20 ( ) H( ) 2 1H( ) H ( ) 17 C C1 6 C C 6 C S 36 18Ar 36, 65 29Cu Zn 65 3

10 ( ) ( ) C 1 12 u ( amu mu ) 12 C 12u 200.6u ( ) 12 C 1 12 (u) 12 A r(hg) C C 1 12 C ( u ) Na u 4 1u 1 12 C (1979 ) 12 1 C mol 12 C 1 12 A r(e) A r E A r(cl)= mol C C 1/ ( g 250 ) 1mol H 1 ( ) 4

11 1826 O O O H 4 He 19 F 12 C O C 12 C C 12 C % (Ag C1 Br K Ar) C ( 460~370 ) 1741 (1711~1763) (l754~1826) : :2? ? 5

12 ( ) ( ) ( ) 19 (1778~1850) (continuous spectrum) 2. ( )(line spectrum) 3. 4 ( J. Balmer) (1885) :, (cm -1 ). n : 2, R H, m -1 n = 3, 4, 5, 6 Balmer H a H b H g H d (Rydberg) n 2 n 1, (s -1 ), R (Rydberg) s P = mc = h n / c = h / l 6

13 l = h / P = h /m u 2. (Louis de Broglie,1924) P = h / l = h / m u x u (1) n n = 1, 2, 3 (2) l l = 0, 1, 2, 3 n- 1 s p d f (3) m m = 0, 1, 2, 3... l, 2 l + 1 m ( ) (4) m s m s = 1/2, n l Mendeleev ( ) (1) (2) (1) 1869 (2) (3) 1913 (4) 20 7

14 (5) (6) (1) s ns 1 ns 2 IA IIA (2) p ns 2 np 1-6 A 0 (3) d ( n -1) d 1-9 ns 1-2, B (4) ds ( n -1) d 10 ns 1 ( n -1) d 10 ns 2 IB IIB (5) f ( n -2) f 0-14 ( n -1) d 0-2 ns s s 2 p s 3 p s 3 d 4 p s 4 d 5 p s 4 f 5 d 6 p s 5 f 6 d 7 p (1) = = n (2) = A 7 B s p ds ( ns + np ) d Fe Ru d Os ( n -1) d + ns f B He O Ca

15 -208 Pb EKPb SpPb s s 2 p s 3 p s 3 d 4 p s 4 d 5 p s 4 f 5 d 6 p s 5 f 6 d 7 p s 5 g 6 f 7 d 8 p s 6 g 7 f 8 d 9 p d 1 d d ns d ds d f 2 f 1 d f 5 6 Zr Hf Nb Ta Mo W d ds 9

16 N P As Zn Cd Hg (n-1)dns ~2.0 ~2.0 10

17 3-8-5 s d

18 VSEPR 2 VB 3 MO MO sp spd 4 - H 2 He O 2 F 2 N 2 NO HF KPa 298K 1molAB A B AB H 298 AB A B (g) =A (g) +B (g) H 298 AB F-F O-O N-N 1

19 H 2 O (g) =H (g) +OH (g) D (H-OH) =500.8KJ/mol OH (g) =H (g) +O (g) D (H-O) =424.7KJ/mol HCOOH (g) =HCOO (g) +H (g) D (HCOO-H) =431.0KJ/mol D (NH 2 -H) =431 D (NH-H) =381 D (N-H) =360 : D 1 >D 2 >D 3 > >D n, 2,, F 3 Si-Cl d=200pm H 3 Si-Cl d=205pm H 2 ClSi-Cl d=202pm Cl 3 Si-Cl d=201pm 3 ~90 ) 4 5 =q.d q d m, C.m CO 6 2

20 f H NaCl =-411KJ/mol S=106.5 D=247 I=495 E A =-376 H 1 =-526 H 2 =-243 f H NaCl =S+D/2+I+E A + H 1 + H 2 U = H 1 + H 2 - H H 2 U Z + Z - /(r + +r - ) -(I+E A + H 1 ) F=Z + Z - /d 2 100% 50% 1.7 ( Cs + F - ) 3

21 NaCl CsCl ZnS CaF 2 TiO 2 NaCl CsCl ZnS CaF 2 TiO NaCl CsCl ZnS CaF 2 8 1/ TiO r + /r ; ; ZnS NaCl CsCl 4-3 Lewis,G.N. 8e Heitler,W. London,F H 2 Pauling,L Valence Bond Theory (VBT) Milliken Hund,F H + 2 Molecular Orbital Theory (MOT) 4

22 1 s s S s S p d f Pauling 1s ns np ns np nd (n-1)d ns np (lone pair) (bonding pair) lp-lp>lp-bp>bp-bp lp,bp lp-lp lp-bp bp-bp 4-4 5

23 s p d f 2 H + 2,Li 2, Be 2, B 2, C 2, N 2, O 2, F 2 1s, 1s *, 2s, 2s *, 2p, 2 2p, 2 2p *, 2p * Li,Be,O,F 1s, 1s *, 2s, 2s *, 2 2p, 2p, 2 2p *, 2p * (B,C,N) BN CO HF CH 4, NH + 4, CCl 4 ; NH - 2, H 2 O, H 2 F + HF CO ~ : 6

24 3eV 5eV 100% 100% 100% >50% Cu(NH 3 ) 4 SO Van der Waals (orientation forces), Keesom H 2 O HF induction forces Debye dispersion forces London <40KJ/mol 10~100 pm 4-7 7

25 40KJ/mol N O F 4-8 d d d 1 2 d 8e<9-17e<18e,18+2e d

26 ZnO, ZnS AgF, AgCl, AgBr, AgI ZnS( ), CdS, HgS AgI (r + /r - =0.573), ZnS type. 9

27 IA H ( H) 2 1H ( D) 3 1H ( T) H 99.98% D 0.016%,T H H 74pm 273K 1dm dm K 2 1 HF 1

28 3273K N 2 H 2 + 2Na 2NaH H 2 + CuO Cu + H 2 O 3H 2 + WO 3 W + 3H 2 O (2) -66 CO (3) H 2 2 H H = 436kJ/mol 1s H Na K Ca H 1 208pm 2 H H 2 H HCl 3 H ZrH 1.30 LaH 2.87 B 2 H 6 H[Cr(CO) 5 ] 2 H F O N HF (1) 25% NaOH KOH (2) 2

29 1273K H 2 CO NaH + H 2 O NaOH + H 2 Si + 2NaOH + H 2 O Na 2 SiO 3 + 2H 2 1 LiH BaH 2 LiH 965K BaH K NaH + H 2 O NaOH + H 2 CaH2 H + + H - H 2 TiCl 4 + 4NaH Ti + 4NaCl + 2H 2 B 3+ Al 3+ Ga 3+ 2LiH + B 2 H 6 Li[BH 4 ] 4 LiH + AlCl 3 Li[AlH 4 ] + 3LiCl 2 p IIIA B Al B 2 H 6 8 B IVA C Si 4 CH 4 SiH 4 8 CH 4 SiH 4 V VI VIIA NH 3 H 2 O HF NH 3 H 2 O V HF 3

30 p C Ge Sn P As Sb Si B SiH 4 + 4H 2 O H 4 SiO 4 + 4H 2 N NH 3 S Se Te F H 2 S H 2 Se H 2 Te HF Cl Br I HCl HBr HI 3 d s Be Mg CrH 2 NiH VH 0.56 TaH 0.76 ZrH g, 4

31 3 5-2 ns np 8 1 He Ne Ar Kr Xe Rn s 2 2s 2 p 6 3s 2 p 6 4s 2 p 6 5s 2 p 6 6s 2 p 6 (pm) (kj/mol) (kj/mol) (K) (K) (K) (Pa) (cm 3 /dm 3 ) K 2.2K 5

32 6

33 :

34 1 ( ) P = 0 6 V = 0 7 T = 0 4. : 1 ( ) Q Q Q 2 W W W W = P V J kj ( ) 1. (U) (U) U U 2.. U 2 = U 1 + Q + W U = U 2 U 1 = Q + W Q W Q Q W W H 2

35 U = Q + W W = - P V = - p V 2 V 1 U = Q P + W = Q P p V 2 V 1 U 2 U 1 = Q P p V 2 V 1 Q P = U 2 + pv 2 - U 1 + pv 1 H U pv H Qp = H2 H1 = H H 3. Qp Q P p Q P = U - W W = - P V = - p V 2 V 1 Q P = U + p V = U 2 U 1 +p(v 2 V 1 ) = U2 + pv 2 - U1 + pv 1 Q P = H : Q P 4. V = 0 W = 0 Q V Q V = U Q V V, 5. H H H = U + p V (H): 6. 2H 2 g + O 2 g === 2H 2 O g r H O m (298) = kj mol-1 r r H O m m 1mol 3

36 O g- l- s- 3 r H O m 2H 2 g + O 2 g === 2H 2 O g r H O m (298) = kj mol-1 H2(g) +1/2 O2(g) = H2O (g), r H O m (298) = kj mol-1 2H 2 g + O 2 g === 2H 2 O g r H O m (298) = kj mol-1 2H 2 O g === 2H 2 g + O 2 g r H O m (298) = kj mol-1 8 a A + b B ==== c C + dd r H O m = ( fh O m )- ( fh O m ) 9 1mol fh O m kj mol-1 f H O m C = 0 kj mol ( ) S 2 3, T S O m J mol -1 K -1 (4) H 2 O: 298 H 2 O ( g ) > 298 H 2 O ( l ) J mol -1 K J mol -1 K -1 (5) 4

37 O 2 (g) < O 3 (g) N O ( g) < N O 2 ( g ) < N 2 O 4 ( g ) CHCH (g) < CH 2 =CH 2 (g) < CH 3 -CH 3 (g) (6) CH 3 Cl (g) < CH 2 Cl 2 (g) < CHCl 3 (g) (7) CuSO 4 (s) < CuSO 4 H 2 O (s) < CuSO 4 3H 2 O (s) < CuSO 4 5H 2 O (s) F 2 (g) < Cl 2 (g) < Br 2 (g) < I 2 (g) (8) NaCl (s) = Na + + Cl - HCl (g) = H + + Cl - (9) 4. aa + bb = cc + dd S O m > 0 S O m < 0 S O m = 0 S O m > 0 S O m < 0 2. O rs m = [ (S O m )] [ (SO m )] Gibbs 1. CH 4 (g) + 2O 2 (g) = CO 2 (g) + 2H 2 O (l) Zn + Cu 2+ = Zn 2+ + Cu U = Q + W U = Q r + W max Q r W max W max G = W max G G < 0 W max < 0, 5

38 G > 0 W max> 0, 2. f G O m 1mol f G O m kj mol -1 f G O m = 0 3. f G O m aa + bb === cc + dd O rg m = [ ( f G O m )] [ ( fg O m )] 4. - G = H - T S rg O m T = rh O m - T rs O m 5. rg rg < 0, rg 0, rg > 0, U 2 H 3 S 4 G 1. U = Q W Q W 2. Q V = U 3. Q P = H H = U + P V Q P = Q V + P V = Q V + nrt G r G O r G O m > 0 r G O m < 0 6

39 r G > 0 r G < 0 rg O m T = H O m- T S O m G T = H -T S K rg O m rg O m = [ ( f G O m )] [ ( fg O m )] rg O m rh O m rs O m 8.T K rg O m rg O m rh O m - T rs O m 7

40 aa + bb === gg + dd n B B r = n B / t r = c B / t r = dc B / dt Collision Theory 1

41 Z f p r = Z P f Z P f 2 ( ) Ea - Ea = rh k : k k k aa + bb = gg r B = k(c A ) a (c B ) b a + b A a B b 6 7 : r = k(c A ) 0-1 k mol dm -3 s :r = kc A k s -1 r = k(c A ) 2-1 k mol -1 dm s r = k(c A ) 3-1 k mol -2 dm 2 s Arrhenius( ) k = A rxp Ea /RT A A k Ea 2

42 -1 R J mol -1 K T 2 k K 0 2 CH 3 CHO CH 4 + CO E a = 190 KJ mol -1 CH 3 CHO CH 4 + CO E a = 190 KJ mol -1 I 2 CH 3 CHO CH 4 + CO E a = 136 KJ mol -1 CH 3 CHO + I 2 CH 3 I + HI + CO CH 3 I + HI CH 4 + I 2 2N 2 O === 2N 2 + O 2 E a = 250 KJ mol -1 N N Au 2N 2 O === N N ¾O Au 2N 2 + O 2 E a = 120 kj mol C 2 H 5 OH =CH 3 CHO + H 2 C 2 H 4 + 1/2O 2 =CH 2 ¾ CH 2 Ag 3

43 Van't Hoff 2 Van't Hoff Van't Hoff ( ) 3. ( ) CO + H 2 O = CO 2 + H 2 r G 0 m = aa + bb = ee + dd K c = ( [ D ]d [E ]e) / ( [A]a [B ]b) [A] [B] [E] [D] A B E D K c (mol m -3 ) n n = (e +d) (a+b) n = 0 K c n 0 K c 2. aa + bb = ee + dd Kp= ( [p D ]d [p E ]e) / ( [pa ]a [p B ]b) Kc = ( [ D ]d [E ]e) / ( [A]a [B ]b) K P K C Kp = Kc ( RT) n ( n = d + e - a - b) 1

44 p = crt K P = K C (RT) ( ) n = 0 K P = K c 3. K 4 ( ) ( ) a A + b B = ee + dd 1. a A(g) + b B(g) = ee(g) + dd(g) K 0 = (p E / p 0 ) e (p D / p 0 ) d / (p A / p 0 ) a (p B / p 0 ) b P 0 P 0 = Pa, 2. aa + bb = ee + dd K 0 = ([E] / C 0 ) e ([D]/C 0 ) d / ([A]/ C 0 ) a ([B]/ C 0 ) b C x mol dm -3 X C x /C 0 C 0 1 mol dm Zn (S) + 2H + (aq) = H 2 (g) + Zn 2+ (aq) K 0 = (p(h 2 )/ p 0 ) ([Zn 2+ ]/ C 0 )/([H + ]/ C 0 ) 2 4. ( ) G 0 < 0 G 0 > 0 G 0 = 0 2. : G > 0 G < 0 G = 0 G G 0 r G T = r G 0 T + RTlnJ T J 3.. r G = 0 J= K 0 r G 0 T = RTlnK 0 T r G 0 = RTlnK 0 4. J T = 1 lnj T = 0 r G T = r G 0 T 5. r G T r G T < 0 r G T > 0 r G T = 0 (1)J> K 0 T r G T > 0 (2) J< K 0 T r G T < 0 (3) J = K 0 T r G T = a A + b B= ee + d D, 2

45 rg = - RTlnK 0 T + RTlnJ RTln[J/K 0 T ] J rg < 0, r G 0 m - RTlnK T rh m - T r S m lgk 0 0 T - r H m /2.303RT + r S 0 m /2.303R H 0 S 0 T Y = - a1/t + B lgk 0 T - a/t + B lgk 0 0 T 1/T a = - rh m /2.303R H 0 > 0 < 0, T K 0 H 0 < 0 > 0 T K 0 Van t Hoof T 1 lnk 0 0 T1 - rh m /RT 1 + rs 0 m /R T 2 lnk 0 0 T2 - rh m /RT 2 + rs 0 m /R ln lnk 0 T1 / lnk 0 T2 rh 0 m [(T 2 - T 1 )/ T 2 T 1 ]/R H 0 > 0 T 2 > T 1 ( ) K 0 T2 > K 0 T1 H 0 < 0 T 2 > T 1 ( ) K 0 T2 < K 0 T

46 C : p (H 2 O) = Pa 0.5 mol kg -1 : p (H 2 O) = Pa 1.0 mol kg -1 : p (H 2 O) = Pa (1887 ) p 1

47 p : n B n A n B > > n A m mol / kg -1 ( K ) m 2 T b * T b K b K b m = 1 mol kg Van't Hoff ( ) V R n c T R = 8.314J mol -1 K -1 2

48 ph 4 ph ph ph ph ph 4 ph ph ph [ ] KNO 3 NaCl T f ( ) T f 2 T f T f ( ) 1

49 1923 Debye H ckel ionic atmosphere 1 c i i Z i i I 2 a activity f f < 1 f f Z 1 Z 2 m 10-2 ph 1 K w H 2 O + H 2 O = H 3 O + + OH - H 2 O = H + + OH - 298K [H 3 O + ] = [OH - ] = mol dm - 3 K w 2 K w H 2 O( l ) = H + ( aq ) + OH - ( aq ) kj mol - 1 > 0 K w HIn HIn = H + + In - K r = ([H + ]/c J [In - ]/c)/[hin]/cj c (HIn) > > c (In - ) c (HIn) < < c (In - ) [HIn] /[In - ] 10 [HIn] /[In - ] 0.1 [H + ] 0.1 ~ ( %) Ka Kb 1 % = ( / ) 100 = ( / ) 100 2

50 ( %) HAc = H + + Ac - c 0 0 c-c c c < 5% 1 - = 1 K a = c H 2 S = H + + HS - Ka1 = [H + ][HS - ]/[H 2 S] = HS - = H + + S 2- Ka2 = [H + ][S 2- ]/[HS - ] = Ka1 Ka2 = K = [H + ] 2 [S 2- ]/[H 2 S] = H 2 S HS - H + S 2 - ([H + ]/c ) 2 ([S 2- ]/ c )/([H 2 S]/c ) = H 2 S [H 2 S] = 0.1 mol dm - 3 ph [S 2- ] :, K1 > > K2 > > K3, K1 /K2 >10 2, [H + ],,,,,, mol dm -3 [H 3 PO 4 ], [H 2 PO - 4 ], [HPO 2-4 ], [PO 3-4 ], [H + ] 3 [Al(H 2 O) 6 ] 3+ + H 2 O = [Al(H 2 O) 5 (OH)] 2+ + H 3 O + Ka1 [Al(OH)(H 2 O) 5 ] 2+ +H 2 O = [Al(H 2 O) 4 (OH)] + + H 3 O + Ka2 [Al(OH) 2 (H 2 O) 4 ] 2+ +H 2 O = [Al(H 2 O) 4 (OH)] + +H 3 O + Ka 4. - NaH 2 PO 4, H 2 PO 4,. 5 Ka Kb 6 Ka Kb 1. (ph=7.0) ph HAc-NaAc ph 2. : ph 3. 3

51 HAc= H + + Ac - NaAc= Na + + Ac - HCl H + Ac - NaOH HAc OH - ph HAc c Ac- /c HAc ph Ac - c Ac- /c HAc ph 4 [H + ] 5 ph Ka ( Kb ) c /c c /c ph ph 6. : ph pk c /c 0.1~10 p H = p Ka 1 7 p H p H HAc = H + + Ac - NaCl 2 HAc= H + + Ac - NaAc NaAc = Na + + Ac - Ac - HAc NaAc Ac - 4

52 Ac - Ac - Na 3 PO 4 NaHCO 3, NaH 2 PO 4, Na 2 HPO 4 HCO - 3,H 2 PO - - 4,HPO 4 NaH 2 PO 4 H 2 PO - 4 H 2 PO 4 - NaH 2 PO 4 Na 2 HPO 4 4. NH 4 Ac NH + 4 Ac - NH 4 F NH 4 Ac NH 4 CN 5. 5

53 Al 2 S 3 (NH 4 ) 2 S Brinsred Lowry = [Al(H 2 O) 6 ] 3+ =H + + [Al(H 2 O) 5 (OH)] 2+ = + HPO 2-4 = PO H + HCl HAc NH + 4 H 2 SO 3 Al(H 2 O) + 6 OH - Ac NH 3 HSO 3 CO 3 1 HCl + H 2 O = H 3 O + + Cl HCl > H 3 O + H 2 O > Cl - 2 HAc + H 2 O = H 3 O + + Ac NH 3 + H 2 O = NH OH HAc < H 3 O + H 2 O < Ac - H 2 O < NH + 4 NH 3 < OH - 3 H 2 O + H 2 O = H 3 O + + OH Ac - + H 2 O = HAc + OH

54 5 6 HAc + H 2 O = H 3 O + + Ac - [H 2 O] Ka NH 3 + H 2 O = NH OH - K b (7) Ac - + H 2 O = OH - + HAc K a K b = K W 8 HCl + H 2 O = H 3 O+ + Cl HAc + H 2 O = H 3 O + + Ac H2O HCl + NH 3 = NH Cl HAc + NH 3 = NH Ac HAc + HF = H 2 Ac + + F A m B n = A m B n (aq) = ma + nb A m B n (aq) s=[a]/m=[b]/n s=[a m B n (aq) ]+[A]/m, [A m B n (aq) ] K sp =[A] m [B] n Ksp =m m n n s (m+n) Q i Q i >K sp Q i =K sp Q i K sp M(OH) n = M n+ + noh - ph =14-pKsp /n - lgc M MA + nh + = M n+ + HnA ph =( SpKai )/n - lg(cmchna ) - pksp /n 7

55 10-5 mol/dm 3 Ksp Ca F 2 KspCaF 2 = KspCaF 2 =11 22.s 1+2s= mol/dm 3 M 3 A mol/dm 3 Ksp [M]=3s= mol/dm 3 [A]=2s= mol/dm 3 Ksp =( ( ) 2 = mol/dm 3 Cu 2+,Fe 2+ H 2 S, [H 2 S]=0.1mol/dm 3 KspCuS = KspFeS = [S 2- ]= QCuS = >KspCuS QFeS = >KspFeS CuS Fe 2+ Cu 2+ [Cu 2+ ]= ( ) 0.1= mol/dm 3 Cu 2+ + H 2 S = CuS + 2H [S 2- ]=Ka1Ka2 [H 2 S]/[H + ] 2 = mol/dm 3 QFeS = <Ksp Cu 2+ Fe dm 3 1mol/dm 3 NH 4 Cl 0.50 mol Mg(OH) 2, 2 NH Mg(OH) 2 = 2NH 3.H 2 O + Mg 2+ : : 1-2 x 2x x (2x) 2.x/(1-2x) 2 = Ksp /Kb2 = /( ) 2 = x=0.1825mol/dm molMg(OH) 2. 8

56 H 2 Cl 2 Fe 2 (H 2 O 2 Na 2 O 2 ) 1 KO KO 3-1/3 OF 2 O +2 H +1 PH 3 NaH 1 = = = K 2 Cr 2 O 7 Cr +6 Fe 3 O 4 Fe +8/3 Na 2 S 2 O 3 S +2 Na 2 S 4 O 6 S 2.5 (2 S 0, S +5) CH 4 CH 3 Cl CH 2 Cl 2 CH 3 Cl :,, 1

57 , = + n e 10 HClO 3 + 3P 4 = 10HCl + 12H 3 PO 4 1. ( - H +, OH, H 2 O 11-1 HClO 3 + P 4 HCl + H 3 PO 4 Cl 5+ Cl 6 P 4 4PO HClO 3 + 3P 4 10HCl + 12H 3 PO 4 10 HClO 3 + 3P 4 +18H 2 O 10HCl + 12H 3 PO 4 36 H 18 O 18 H 2 O 11-2 As 2 S 3 + HNO 3 H 3 AsO 4 + H 2 SO 4 + NO 2As 3+ 2As S 2 3S N 5+ N As 2 S HNO 3 6H 3 AsO H 2 SO NO 28 H 84 O 36 H 88 O 8 H 4 O 3As 2 S HNO H 2 O 6H 3 AsO H 2 SO NO 2.. H +, OH -, H 2 O, H O H O O H O 2 H +, 1 H 1 H 2 O H + H O H 1 OH 1 O H 2 O 2 OH - OH, H Zn + Cu 2+ = Cu + Zn 2+ Zn 2e = Zn 2+ 2

58 Cu e = Cu Zn 2e = Zn 2+ Cu e = Cu ( )Zn Zn 2+ (c 1 / mol dm -3 ) Cu 2+ (c 2 /mol dm -3 ) Cu(+) ( ) (Pt),H 2 ( p q ) H + (1mol dm -3 ) Fe 3+ (1mol dm -3 ),Fe 2+ (1mol dm -3 ) Pt(+) H 2 2e = 2H + Fe 3+ + e = Fe 2+ H Fe 3+ = 2H Fe M = M n+ + n e : 2. ( ) 3. E θ = φ θ + - φ θ E θ θ V E θ E 4. ( )(Pt),H 2 ( 10 5 Pa) H + (1mol dm -3 ) Zn 2+ (1mol dm -3 ) Zn (+), KCl 5. ( ) Cu e = Cu 2Cu e = 2Cu φ θ E θ = φ θ + - φ θ > 0 r G θ = - nf E θ r G = - nf E F = mol 1 r G θ = - RTlnK - RT ln K = - nf Eθ 3. r G θ = - RTlnK 3

59 r G θ = - RTlnK r G θ < 40kJ mol 1 > 40kJ mol 1 r G θ = - nf E θ n = 1 > 0.41V, < 0.41 V n = 2 > 0.20V, < 0.20 V n = 3 > 0.138V, < V 4., > 0,. < 0,. = 0, (Nernst) r H θ m = - h H θ m E 1/2 D ph (Nernst) ( j ~c, j ~p, j ~p H ) E θ = φ θ + - φ θ Nernst ( ) x A( ) + m e y B( ) 298K Nernst (1) j [ ]/[ ] (2) 1 p / p (3) Nernst Nernst ph 2MnO SO 3 + 2OH = 2MnO ( ) + SO 4 + 2H 2 O 2MnO 4 + SO H 2 O = 2MnO 2 + 3SO 4 + 2OH 2MnO SO 3 + 6H + = 2Mn SO 4 + 3H 2 O OH H 2 O 6H + MnO 4 OH 2 H 2 O 6H + SO 3 Br + Cr 2 O H + = 3Br Cr H 2 O H 2 SO 4 HAc 11-3 j - ph O 2 (g) + 4H + + 4e = 2H 2 O =1.23V 2H 2 O + 2e = H 2 + 2OH - = V 4

60 - ph 1. A H 2 O O 2 F H 2 O = 4HF + O 2 2. A B H 2 O 2H 2 O + 2e = H 2 + 2OH - 3. B H 2 O H 2 2Na + 2H 2 O = 2NaOH + H 2 4. G / F-Z Latimer ClO ClO 3 HClO 2 HClO Cl 2 Cl - : ClO - 4 ClO - 3 ClO 2 - ClO - Cl 2 Cl G / F-Z

61 CaF % 1.9% 1/ % 3 10% NaIO 3, s 2 2p 5 3s 2 3p 5 4s 2 4p 5 5s 2 5p ,1,3,5,7-1,1,3,5,7-1,1,3,5,7 /pm X - /pm /(kj/mol) /(kj/mol) X - /(kj/mol) X 2 /(kj/mol) (Pauling ) φ θ /V 1

62 F 2 F Cl 2 Cl Br 2 Br I 2 I g/ml 1.513/85K 1.655/203K 3.187/273K 3.960/393K K (K) (KJ/mol) (K) (MPa) Xe 523K 3 1 X 2 + H 2 O = 2HX + 1/2 O 2 2 X 2 + H 2 O = HX + HXO X= F Cl Br I 1 X 2 + H 2 O = 2HX + 1/2 O 2 X 2 + 2e - 2X - φ A θ/ V F 2 /F - = 2.87 Cl 2 /Cl - = 1.36 Br 2 / Br - = 1.07 I 2 /I - = 0.54 O 2 + 4H + + 4e - 2H 2 O φ A θ O 2 /O 2 - = 1.23V F 2 Cl 2 ph>3 Br 2 ph>12 I 2 2 X 2 + H 2 O = HX + HXO X= F Cl Br I 2

63 ph 4 F Cl Br I F 2 Cl 2 Br 2 I 2 F - Cl - Br - I Cl 2 2NaBr Br 2 2NaCl Cl 2 2NaI I 2 2NaCl I 2 5Cl 2 6H 2 O 2IO Cl - 12H + Br 2 2NaI I 2 2NaBr K 2 PbF 6 BrF 5 F 2 HF KF SbCl 5 KMnO 4 K 2 MnF 6 SbF 5 K 2 MnF 6 SbF 5 MnF 4 MnF 4 F 2 2KMnO 4 2KF 10HF 3H 2 O 2 2K 2 MnF 6 8H 2 O 3O 2 SbCl 5 5HF SbF 6 5HCl 423K K 2 MnF 6 2SbF 5 ==== 2KSbF 5 MnF 4 2MnF 4 2MnF 3 F 2 F - 2F - = F 2 + 2e - 2HF 2 + 2e - = H 2 + 4F - KHF 2 HF 0.02% 373K 2KHF 2 = 2KF + F 2 + H 2 2 MnO 2 4HCl ==== MnCl 2 2H 2 O Cl 2 2KMnO 4 16HCl ==== 2KCl 2MnCl 2 8H 2 O 5Cl 2 2NaCl 2H 2 O ==== H 2 Cl 2 2NaOH 3

64 2NaCl( ) ==== 2Na Cl 2 3 (1) I - I 2 Cl 2 Br 2 MnO 2 Cl 2 2NaI 2NaCl I 2 2NaI 3H 2 SO 4 MnO 2 2NaHSO 4 MnSO 4 I 2 2H 2 O I 2 5Cl 2 6H 2 O 2IO 3-10Cl - 12H + (2) NaHSO 3 IO - 3 2IO HSO 3 3HSO 4 2SO 4 H 2 O I 2 NaHSO 3 IO HSO 3 I - 3SO 4 2-3H + IO I - 6H + 3I 2 3H 2 O HCl HBr HI HF HF HF HF HI HCl HBr HI F - Cl - Br - I - 4HI O 2 2I 2 2H 2 O 4HBr O 2 2Br 2 2H 2 O 4HCl O SiO 2 SiF 4 CaF 2 H 2 SO 4 ( ) CaSO 4 2HF 4HF SiO 2 SiF 4 2H 2 O 6HF CaSiO 3 SiF 4 CaF 2 3H 2 O 4

65 2 NaCl H 2 SO 4 ( ) NaHSO 4 HCl (3) HBr HI NaBr H 2 SO 4 ( ) NaHSO 4 HBr NaI H 2 SO 4 ( ) NaHSO 4 HI 2HBr H 2 SO 4 ( ) SO 2 Br 2 2H 2 O 8HI H 2 SO 4 ( ) H 2 S 4I 2 4H 2 O NaBr H 3 PO 4 NaH 2 PO 4 HBr NaI H 3 PO 4 NaH 2 PO 4 HI 2 HBr HI HBr HI 3Br 2 2P 6H 2 O 2H 3 PO 3 6HBr 3I 2 2P 6H 2 O 2H 3 PO 3 6HI (3.98 ) (3.44 ) 1 OF 2 OF 2 2% NaOH OF 2 2F 2 + 2NaOH = 2NaF + H 2 O + OF 2 OF 2 NaOH F - Cl 2 O ClO 2 Cl 2 O 7 2 Cl 2 O Cl 2 O Cl 2 O H 2 O 2HClO Cl 2 O O sp3 V 3 ClO 2 ClO 2 ClO 2 2ClO 2 2NaOH NaClO 2 NaClO 3 H 2 O ClO 2 ClO 2 ClO 2 V 4 Cl 2 O 7 Cl 2 O 7 (263K) HClO 4 P 2 O 5 Cl 2 O HOF Cl Br I sp 3 5

66 sp 3 2p nd d - p π HOF HOCl HClO 2 HClO 3 HClO 4 HOBr HBrO 2 HBrO 3 HBrO 4 HOI - HIO 3 HIO 4 H 5 IO 6 (1) HClO HClO 2 HClO 3 HClO 4 (2) +1 HClO NaClO +3 HClO 2 NaClO 2 +5 HClO 3 NaClO 3 +7 HClO 4 NaClO 4 6

67 % 89% 23% 0.045% FeS 2 CuFeS 2 PbS ZnS CaSO 4 2H 2 O Na 2 SO 4 10H 2 O φ A θ / V O 3 O 2 H 2 O 2 H 2 O φ B θ / V O 3 O 2 HO 2 - OH φ A θ / V S 2 O SO H 2 SO 3 S 2 O 3 S H 2 S φ B θ / V SO 4 SO 3 S 2 O - 3 S S

68 16 O 17 O 18 O 16 O 99.76% 17 O 0.04% 18 O 0.2% 18 O O 2 O 3 25km O 2 O O O 2 O 3 O 2 2O O + O 2 O 3 2O 3 3O 2 O 3 20km O 3 220~330nm O 3 O 2 O 3 O 2 1 2BaO 2 2BaO + O 2 2NaNO 3 2NaNO 2 + O 2 KClO 3 O 2 b.p. N 2 77 K, O 2 90 K H 2 O O 2 H 2 O 90 K 54 K 1 2 Mg + O 2 2 MgO S + O 2 SO H 2 S + O 2 2 S + 2 H 2 O 2 H 2 S + 3O 2 2 SO H 2 O 4 NH O 2 2 N H 2 O 4 NH O 2 4 NO + 6 H 2 O 3 2 CO + O 2 2 CO Sb 2 S O 2 2 Sb 2 O SO 2 2 O 3 O 3 O 3 O 3 O 2 161K 22K O 3 O 3 O sp 2 O O σ O O 3 π ( Π 4 ) π O 2 π O 1 π O O pm 2

69 3 O 3 Π 4 O p ψ 1 ψ 2 ψ 3 π O 3 O 3/2 O pm O pm O 3 O 2 (1) O 3 (MnO 2 PbO 2 ) 2O 3 3O 2 O 3 O 3 O 2 O 2 (2) O 3 O O 2 F 2 PbS + 2O 3 PbSO 4 + O 2 2Ag + 2O 3 2O 2 + Ag 2 O 2 XeO 3 + O 3 + 2H 2 O H 4 XeO 6 + O 2 O 3 I 2 O 3 O 3 + 2I - + H 2 O I 2 + O 2 + OH - O 3 CN - O 3 + CN - OCN - + O 2 2OCN - + 2O 3 2 CO 2 + N 2 + O 2 O 3 O 3 +CH 3 CH=CHCH 3 2CH 3 CHO O 3 O 3 20 km 40 km 20 km 0.2 ppm 3mm O 3 =O 2 + O SO 2 H 2 S Cl O Nobel π 1 O (1) O sp 3 H 2 O Cl 2 O OF 2 (2) O sp 3 H 3 O H 2 O O (3) O sp 2 HCHO( ) COCl 2 CO(NH 2 ) 2 O 3

70 (4)O sp CO NO (1) O 2p R 3 N O (2) O 2p H 3 PO 4 d-p P O 2 (1) O 2 O 2 - O 2 - O -1/2 KO (2) O 2 O 2 O O Na 2 O 2 BaO 2 H 2 O 2 H 2 S 2 O 4 K 2 S 2 O 8 + (3) O 2 O 2 O +1/2 O 2 + AsF 5 O 2 + [ AsF 5 ] O 2 + Pt + 3F 2 O 2 + [ PtF 6 ] O kJ/mol O O 112pm O 2 2+ O 2 (4) O N 1 N [HmFe] + O 2 [HmFe O 2 ] Hm 3 O 3 1 KO 3 2 O O O O 3 F H 2 O 2 O sp 3 H H O σ O O O σ O H O O O HOO O O 149pm H O 97pm O O O -1 O H H O 2 H 2 O 2 H 2 O H 2 O 2 H 2 O 3% H 2 O 2 4

71 H 2 O 2 O -1 H 22 H 2 O 2 H 2 O 2 H 2 O 2 H 2 O 2 + 2I - + 2H + = I 2 + H 2 O H 2 O 2 PbS PbSO 4 4H 2 O 2 + PbS = PbSO 4 + 4H 2 O H 2 O 2 H 2 O 2 + H 2 SO 3 = H 2 SO 4 + H 2 O H 2 O 2 NaCrO 2 3H 2 O 2 + 2NaCrO 2 + 2NaOH = 2Na 2 CrO 4 + 4H 2 O H 2 O 2 + Mn(OH) 2 = MnO 2 + 2H 2 O H 2 O 2 H 2 O 2 H 2 O 2 + Cl 2 = 2Cl - + O 2 + 2H + H 2 O 2 KMnO 4 H 2 O 2 5H 2 O 2 + 2MnO H + = 2Mn H 2 O + 5O 2 3H 2 O 2 + 2MnO 4 - = 2MnO 2 + 2H 2 O + 3O 2 + 2OH - H 2 O 2 426K(153C ) 2H 2 O 2 = 2H 2 O + O 2 H 2 O 2 (1) O 2 (2) H 2 O 2 (3) 320~380nm H 2 O 2 H 2 O 2 H 2 O 2 H 2 O 2 Na 2 SnO 3 Na 4 P 2 O 7 8- H 2 O 2 H 2 O 2, 3 H 2 O 2 (1) H 2 O 2 BaO 2 + H 2 SO 4 === BaSO 4 + H 2 O 2 (2) CO 2 BaO 2 BaO 2 + CO 2 + H 2 O = BaCO 3 + H 2 O 2 H 2 O 2 (1) - 5

72 2NH 4 HSO 4 ===== (NH 4 ) 2 S 2 O 8 + H 2 ( ) ( ) H 2 SO 4 H 2 O 2 H 2 SO 4 (NH 4 ) 2 S 2 O 8 + 2H 2 O ====== 2NH 4 HSO 4 + H 2 O 2 (2) 2- ( ) H 2 O 2 H 2 O 2 2- H O 2 2- H 2 O 2 2- H 2 O 2 20%~30% H 2 O 2 H 2 O 2 98% H 2 O 2 4 H 2 O 2 CrO(O 2 ) 2 (+6 ) 2-4H 2 O 2 + Cr 2 O 7 + 2H + == 2CrO(O 2 ) 2 + 5H 2 O CrO(O 2 ) 2 [CrO(O 2 ) 2 ((C 2 H 5 ) 2 O)] Cr(VI) O O O 2-2 π H 2 O α- β K 368.4K 368.4K CS 2 S 8 ( ) S sp 3 206pm K 392K 717.6K ( ) CS 2 CS 2 S 8 563K 717.6K S 8 S 6 S 4 S K S CS (1) (2) 6

73 (3) 6S + 6NaOH == 2Na 2 S 2 + Na 2 S 2 O 3 + 3H 2 O (4) S + 2HNO 3 ( ) == H 2 SO 4 + 2NO S sp 3 2 σ 2 V S -2 H 2 S 0.1% H 2 S H 2 S H 2 S H 2 S H 2 S 213K 187K H 2 S (1)H 2 S Ka 1 = Ka 2 = (2)H 2 S S -2 S H 2 S H 2 S φ A θ S/H 2 S = 0.14V φ A θ S/S 2- = -0.45V H 2 S I 2 Br 2 O 2 SO 2 S H 2 S + I 2 = 2HI + S H 2 S + 4Br 2 + 4H 2 O = H 2 SO 4 + 8HBr 2H 2 S + SO 2 = 3S + 2H 2 O 2H 2 S + O 2 = 2S + 2H 2 O (1) S H 2 S + H 2 = H 2 S (2) H 2 S FeS + H 2 SO 4 = H 2 S + FeSO 4 Na 2 S + H 2 SO 4 = H 2 S + Na 2 SO 4 H 2 S H 2 S 2 H 2 S H + S 2- [H + ] 2 [S 2- ]= H 2 S [H + ] [S 2- ] H 2 S [H + ] [S 2- ] H 2 S H 2 S Na 2 S + H 2 O NaHS + NaOH Na 2 S Al 2 S 3 CuS PbS 7

74 3 Na 2 S (NH 4 ) 2 S Na 2 S + (x-1)s = Na 2 S x (NH 4 ) 2 S + (x-1)s = (NH 4 ) 2 S x Na 2 S 2 CaS 4 S M 2 S x x=2 Na 2 S 2 (NH 4 ) 2 S 2 (1) H 2 S S S 2- x + 2H + H 2 S + x - 1 S (2) SnS + (NH 4 ) 2 S 2 = (NH 4 ) 2 SnS 3 As 2 S 3 + 3Na 2 S 2 = 2Na 3 AsS 4 + S SnS (II) (IV) (NH 4 ) 2 SnS 3 (III) As 2 S 3 (IV) SO 2 S sp 2 OSO pm SO SO 2 SO mg/L SO 2 263K 40L SO 2 10% SO 2 SO 2 S +4 SO 2 SO 2 I 3SO 2 ( ) + KIO 3 +3H 2 O = 3H 2 SO 4 + KI SO 2 + Br 2 + 2H 2 O = H 2 SO 4 + 2HBr II SO 2 + 2H 2 S = 3S + 2H 2 O 773K SO 2 + 2CO ===S + 2CO 2 III SO 2 SO 2 SO 2 8

75 SO 2 S + O 2 = SO 2 SO 2 3FeS 2 + 8O 2 = Fe 3 O 4 + 6SO 2 2ZnS + 3O 2 = 2ZnO + 2SO 2 SO 3 S 120 S O 143pm (S O 155pm) SO 3 (SO 3 ) n SO 3 S O 161pm O S 141pm S 4 σ 2 π SO 3 (SO 3 ) 3 S O S SO K 317.8K 263K 293K : SO 3 S +6 SO 3 5SO 3 + 2P = 5SO 2 + P 2 O 5 SO 3 + 2KI = K 2 SO 3 + I 2 SO 3 : SO 3 SO 2 V 2 O 5 V 2 O 5 2SO 2 + O 2 ===== 2SO 3 723K 2 SO 2 H 2 SO 3 SO 2 + H 2 O H 2 SO 3 H 2 SO 3 Ka 1 = Ka 2 = (M 2 SO 3 ) (MHSO 3 ) Na 2 SO 3 + H 2 O = NaHSO 3 + NaOH +4 : - MnO 4 Mn Cr 2 O 7 Cr 3+ - IO 3 I 2 I - Br 2 Cl 2 Br - Cl - ( H 2 S ) H 2 SO 3 + 2H 2 S = 3S + 3H 2 O SO 2 SO 2 SO 3 SO 3 + H 2 O = H 2 SO 4 H 2 SO 4 Ka 2 = H 2 SO K 611K 98.3% 9

76 1.854g /cm -3 18mol/L H 2 SO 4 H 2 SO 4 SO 3 H 2 SO 4 (SO3 H 2 O) H 2 S 2 O 7 (2SO 3 H 2 O) C 12 H 12 O 11 ==== 12C + 11H 2 O Cu + 2H 2 SO 4 = CuSO 4 + SO 2 + 2H 2 O C + 2H 2 SO 4 = CO 2 + 2SO 2 + 2H 2 O (93% ) H 2 SO 4 H + H Zn Mg Fe H 2 SO 4 + Fe = FeSO 4 + H 2 I CaSO 4 BaSO 4 II 18 CuSO 4 ZnSO 4 CdSO 4 ( ) III Ag 2 SO 4 PbSO 4 Hg 2 SO 4 IV K 2 SO 4 Na 2 SO 4 BaSO K 8 CuSO 4 Ag 2 SO 4 Al 2 (SO 4 ) 3 Fe 2 (SO 4 ) 3 PbSO 4 18 SO 3 CuSO 4 5H 2 O FeSO 4 7H 2 O Na 2 SO 4 10H 2 O CuSO 4 5H 2 O FeSO 4 7H 2 O ZnSO 4 7H 2O 10

77 + M 2 I SO 4 M SO 4 6H 2 O M I =NH 4 Na + K + (NH 4 ) 2 SO 4 FeSO 4 6H 2 O K 2 SO 4 MgSO 4 6H 2 O M 2 ISO 4 M 2 (SO 4 ) 3 24H 2 O MI =NH + 4 Na + K + (Li ) M =Fe 3+ Co 3+ Cr 3+ K 2 SO 4 Al 2 (SO 4 ) 3 24H 2 O Al 2 (SO 4 ) 3 Na 2 SO 4 10H 2 O H 2 S 2 O 3 Na 2 S 2 O 3 5H 2 O Na 2 S 2 O 3 (ph 4.6) Na 2 S 2 O 3 + 2HCl = 2NaCl + S + H 2 O + SO 2 2- S 2 O 3 Na 2 S 2 O Na 2 S 2 O 3 S 2 O 3 SO 4 2- O S S 2 O 3 S +2 S +6 S -2 Na 2 S 2 O 3 Na 2 S 2 O 3 Na 2 S 2 O 3 φ A θ S 4 O 2-6 / S 2 O 2-3 = 0.09V I Na 2 S 2 O 3 Na 2 S 4 O 6 2 Na 2 S 2 O 3 + I 2 = Na 2 S 4 O 6 + 2NaI II Na 2 S 2 O 3 Na 2 S 2 O 3 Na 2 S 2 O 3 + 4Cl 2 + 5H 2 O = Na 2 SO 4 + H 2 SO 4 + 8HCl Na 2 S 2 O 3 : AgX(X=Cl Br I) Na 2 S 2 O 3 AgX + 2S 2 O 2-3 [Ag(S 2 O 3 ) 2 ] 3- + X - Na 2 S 2 O 3 AgBr Na 2 S 2 O 3 Na 2 S 2 O 3 Na 2 S 2 O 3 + 2AgNO 3 = Ag 2S 2O 3 + 2NaNO 3 Ag 2 S 2 O 3 Ag 2 S 2 O 3 + H 2 O = H 2 SO 4 + Ag 2 S Ag 2 S Ag 2 S 2 O 3 Na 2 S 2 O 3 I. Na 2 S 2 O 3 S Na 2 SO 3 + S = Na 2 S 2 O 3 II. Na 2 S Na 2 CO 3 2:1 SO 2 2Na 2 S + Na 2 CO 3 + 4SO 2 = 3 Na 2 S 2 O 3 + CO 2 11

78 Na 2 S 2 O 3 S H O O H H H O O H H HSO 3 - H O O SO 3 H H HSO 3 O O SO 3 H O O O 1 O S +6 H 2 S 2 O 8 S K φ A θ S 2 O /SO 4 = 2.01V K 2 S 2 O 8 + Cu = CuSO 4 + K 2 SO 4 Ag + 5S 2 O Mn H 2 O MnO O H + Ag + 2- S 2 O 8 MnO(OH) 2 S 2 O Mn H 2 O MnO(OH) 2 + 2SO H + ( ) O -1-2 S +6 K2S 2 O 8 SO 3 O 2 2 K 2 S 2 O 8 ==== 2K 2 SO SO 3 + O K 490K Se 8, Se 2 Te H 2 Se H 2 Te H 2 S H 2 S H 2 Se H 2 Te H 2 S H 2 Se H 2 Te H 2 Se H 2 Te H 2 S H 2 S H 2 Se H 2 Te H 2 Se H 2 Te SeO 2 TeO 2 SO 2 SeO 2 TeO 2 SeO 2 TeO 2 SO 2 HI SeO 2 H 2 SeO 3 TeO 2 H 2 TeO 3 TeO 2 Se ( IV) Te ( IV ) Se ( VI ) Te ( VI ) 12

79 H 2 SeO 4 H 6 TeO 6 H 2 SO 4 H 2 SO 4 H 2 SeO 4 H 6 TeO 6 H 2 SeO 4 H 6 TeO 6 K 1 = 6 13

80 N P As Sb Bi s 2 2p 3-3,-2,-1,+1 +5 /pm 70 /(kj/mol) 1402 /(kj/mol) 7 (Pauling ) 3.04 /(kj/mol) -167 /(kj/mol) s 2 3p 3-3,0,+1,+3, s 2 4p 3-2,0,+2,+4, N σ π sp NH 3 NH 4 + 1

81 sp NO ClNO sp N 2 HCN L i3 N Ca 3 N 2 Mg 3 N φ A θ / V NO HNO 2 NO N 2 O N 2 NH φ B θ / V NO - 3 NO - 2 NO N 2 O N φ A θ / V H 3 PO 4 H 3 PO 3 H 3 PO 2 P PH φ B θ / V PO 3-4 HPO 2-3 H 2 PO - 2 P PH % N g dm -3, 63K, 75K 126K 283K 0.02 N 2 [KK(σ 2s ) 2 (σ* 2s ) 2 (π 2py ) 2 (π 2pz ) 2 (σ 2px ) 2 ] (π 2py ) 2 ( π 2 pz) 2 (σ 2px ) 2 π σ (σ 2s ) 2 (σ* 2s ) 2 N 2 N N N kJ/mol N 2 N 2 N 2 N 2 6 Li + N 2 === 2 Li 3 N N 2 Mg Ca Sr Ba 3Ca + N 2 === Ca 3 N 2 N 2 2B + N 2 === 2BN N K Pa 99.7% NH 4 NO 2 aq N H 2 O NH 4 Cl + NaNO 2 === NaCl + 2 H 2 O + N 2 2

82 2 NH 3 + 3CuO === 3 Cu + 3 H 2 O + N 2 8 NH Br 2 (aq) === 6 NH 4 Br + N NH 3 NH 2 -NH 2 N 2 H 4 NH 2 OH HN 3 1. NH 3 (NH 4 ) 2 SO 4 (s) + CaO(s) === CaSO 4 (s) + 2 NH 3 + H 2 O NH 4 NO 3 (NH 4 ) 2 Cr 2 O 7 NH 4 Cl Mg 3 N H 2 O === 3 Mg(OH) NH 3 NH 3 N sp 3 H N - H HNH NH C. m NH 3 273K 1dm dm g/ml NH 3 28% NH 3 NH 3 H 2 O K K kj/mol kj/mol K K K K (g/ml) kj/mol C? m NH 3 H 2 O NH 3 H 2 O NH 3 H + H 2 O 3

83 2Na + 2NH 3 2Na + + 2NH H 2 Na Na + + e - Na + + xnh 3 [Na(NH 3 ) x ] + e - + ynh 3 e[(nh 3 )y] - NH 3 NH 3 [Ag(NH 3 ) 2 ] + [Cu(NH 3 ) 4 ] 2+ BF 3 NH 3 NH 3 NH 3 NH 3 H 2 O 2NH 3 H 2 O NH + 4 OH - NH 4 OH 276pm 298K 0.1mol dm -3 NH % NH 3 H 2 O NH OH - NH 3 NH 3 H -NH 2 =NH N NH 4 Cl + 3Cl 2 === 4HCl + NCl 3 ( ) NH 3 + NH 2 Cl + OH - === N 2 H 4 ( ) + Cl - + H 2 O - NH 2 =NH COCl 2 + 4NH 3 === CO(NH 2 ) 2 ( ) + 2NH 4 Cl SOCl 2 + 4NH 3 === SO(NH 2 ) 2 ( ) + 2NH 4 Cl HgCl 2 + 2NH 3 === Hg(NH 2 )Cl ( ) + NH 4 Cl NH 3 NH 3 NH + 4 N -3 i. 4NH 3 + 3O 2 === 6H 2 O + 2N 2 NH 3 NO 4NH 3 +5O 2 === 4NO + 6H 2 O ii. Cl 2 Br 2 NH 3 2NH 3 + 3Cl 2 === 6HCl + N 2 Cl 2 NCl 3 NH 3 + 3Cl 2 === NCl 3 + 3HCl iii.nh 3 CuO N 2 2NH 3 + 3CuO === 3Cu + 3H 2 O + N 2 + iv. NH 4 NH 3 4

84 N N 2 HNO 3 HCl NH + 4 NH + 4 Na + + NH 4 +1 NH pm K + 133pm Rb + 148pm NH 4 Cl + H 2 O ==== NH 3 H 2 O + HCl NH 3 KOH + NH 4 + 2[HgI 4 ] OH - [OHgNH 2 ]I + 7I - + 3H 2 O NH 3 NH 4 NO 3 NH 3 N 2 O NH 4 NO 3 N 2 O + 2H 2 O 573K N 2 O N 2 O 2 NH 4 NO 3 2. N 2 H 4 NH 2 -NH 2 NH 3 H -NH 2 H 2 O 2 µ = C m N 2 H 4 N -2 NaClO NH 3 NaClO + 2 NH 3 === N 2 H 4 + NaCl + H 2 O N 2 H 4 N 2H 4 N H + NH 3 N 2 H 4 N 2 H 4 NH 3 [Pt(NH 3 ) 2 (N 2 H 4 ) 2 ]Cl 2, [(NO 2 ) 2 Pt(N 2 H 4 ) 2 Pt(NO 2 ) 2 ] N 2 H 4 AgNO 3 N 2 H 4 + 2X 2 === 4HX + N 2 N 2 H 4 H 2 O 2 N 2 H 4 + O 2 N 2 + 2H 2 O H θ = kJ/mol N 2 H 4 + H 2 O 2 N 2 + 4H 2 O H θ = kJ/mol 3. NH 2 OH NH 2 OH NH 3 H -OH N -1 N Zn(NH 2 OH) 2 Cl 2 2NH 2 OH + 2AgBr === 2Ag + N 2 + 2HBr+ 2H 2 O 5

85 2NH 2 OH + 4AgBr === 4Ag + N 2 O +4HBr +H 2 O 4. HN 3 HN 3 N 2 H 4 + HNO 2 ==== 2H 2 O + HN 3 HN 3 N H-N N-N-N H 1 N sp N sp N Π 3 4 π HN 3 N -1/3 N 3 - AgN 3 HN 3 HN N O N NO NO 2 1. NO NO N sp σ π π N +2 NO 11 NO NO NO 2 2 NO + O 2 ==== 2 NO 2 2 NO + Cl 2 === 2 NOCl NO Fe 2+ NO + FeSO 4 ==== [Fe(NO)]SO 4 NO NO 3 Cu + 8 HNO 3 ( ) === 3 Cu(NO 3 ) NO + 4 H 2 O 2. NO 2 NO 2 N sp 2 σ π N +4 NO 2 17 NO 2 N 2 O 4 2 NO 2 ==== N 2 O 4 NO 2 2 NO 2 + H 2 O == HNO 3 + HNO 2 2 NO 2 + 2NaOH === NaNO 3 + NaNO 2 + H 2 O NO HNO 3 NO 2 2 NO + O 2 ==== 2 NO 2 Cu + 4 HNO 3 ( ) === Cu(NO 3 ) NO H 2 O 3 NO NO 2 NaNO 2 + HCl HNO 2 + NaCl 6

86 NO 2 NO NO 2 H 2 O HNO 2 N sp2 σ π - NO 2 N +3 HNO 2 a HNO 2 HNO 2 H NO 2 K A = b N +3 - NO 3 - HNO 2 φ θ HNO 3 NO 2 I - - I 2 NO 3 I NO 2 NO 3 NO - 2 2HNO 2 + 2H + +2I - 2 NO + 2 H 2 O + I 2 c HNO 2 KMnO 4 Cl 2 5NO MnO H + 5NO Mn H 2 O NO Cl 2 + H 2 O NO 3 + 2H + + 2Cl NO 2 NO 2 NO 3 2NO O 2 2NO 3 - d NO 2 - NO 2 N O [Co(NO 2 ) 6 ] 3 - [Co(NO 2 )(NH 3 ) 5 ] 2+ K + K + 3 K [Co(NO 2 ) 6 ] 3 K 3 [Co(NO 2 ) 6 ] ( ) e Pb( ) + NaNO 3 ==== PbO + NaNO 2 AgNO 2 - NO 2 α - - NO NO 2 NO 2 4 a 1273K 90%Pt 10%Rh NH 3 O 2 NO NO O 2 NO 2 NO 2 HNO 3 50% HNO 3 H 2 SO 4 b 7

87 4273K 1473 K NO NO O 2 NO 2 N 2 O 2 c K HNO 3 N sp 2 σ O N N π O π sp 2 π Π 4 3 N +5 - NO 3 ONO 120 N sp 2 σ O Π 6 4 HNO 3 N +5 HNO 3 O 2 NO 2 4HNO 3 === 2H 2 O + NO 2 + O 2 NO 2 HNO 3 NO 2 + e - - NO 2 NO H + HNO 2 HNO 2 + HNO 3 H 2 O + 2NO 2 HNO 3 HNO 3 HNO 3 HNO 3 HNO 3 HNO 3 8HNO 3 + 3Cu 3 Cu(NO 3 ) 2 + 2NO + 4H 2 O HNO 3 NO 2 N Cl 2 O 2 HNO 3 2HNO 3 + S H 2 SO 4 + 2NO 5HNO 3 + 3P + 3H 2 O 3H 3 PO 4 + 5NO HNO 3 CO 2 HNO 3 HNO 3 NO a O 2 b Mg Cu ( K Na Mg Zn Fe Ni Sn Pb H Cu Hg Ag Au) c 8

88 2AgNO 3 2Ag + 2NO 2 + O 2 NH 4 NO 3 N 2 O + 2H 2 O d HNO 3 Fe 2+ NO 3 - NO Fe H + 3 Fe 3+ + NO+ 2H 2 O Fe 2+ + NO + SO 2-4 [ Fe(NO)]SO 4 ( ) % Ca 3 (PO 4 ) 2 H 2 O Ca 5 F(PO 4 ) 3 1. SiO 2 2Ca 3 (PO 4 ) 2 + 6SiO C 6CaSiO 3 + P CO P g P 4 P 4 P P 221pm PPP 60, P 4, P 3 p P p σ p P 4 P P 673K CS MPa Hg 493~643K 8 3. CS 2 313K 9

89 CuSO s 2 3p 3 3d 0 3d 1. P P 3-2. (1) P sp 3 3 σ 1 P PH 3 PCl 3 (2) P sp 3 4 σ P -3 + PH 4 PH 3 H + (3) P sp 3 4 σ 1 π P +5 H 3 PO 4 POCl 3 (4) P F O Cl P 3s 1 3d P 5 σ P +5 PCl P III PH 3 PR 3 NH 3 NR3 PR 3 P d CuCl 2PH 3 2 P d P sp 3 d 2-6 PCl NH 3 1 Mg 3 N N 2 H NH 3 PH 3 PR 3 P-H 142pm + + HPH 93 PH 3 NH 3 PH 4 NH 4 P-H 142pm HPH

90 3. PH 3 PH K K PH 3 NH 3 290K 100dm 3 26 dm 3 PH 3 PH 3 PH 3 H 2 O NH 3 H 2 O PH + 4 PH 3 1 PH 3 P -3 PH 3 PH 3 AgNO 3 Ag PH 3 CuSO 4 Cu 3 P Cu PH 3 423K 2 NH 3 PH 3 PR 3 NH 3 PR 3 d CuCl PH 3 PtCl 2 2P(CH 3 ) 3 3 PH 3 P 2 H 4 N 2 H P III P 4 O 6 P 4 O 6 P 4 P-P O 2 P O P 4 O 6 4 P 296.8K 446.8K 2. P 4 O 10 P +5 P 4 O 6 P O 2 P=O P 4 O K 573K P HNO P 1. 76% H 3 PO 4 P H 3 PO 4 82% 315.3K H 3 PO 4 H 3 PO 4 a H 3 PO 4 b H 3 PO 4 H 3 PO 4 c 11

91 d 2. a Ca(H 2 PO 4 ) 2 > CaHPO 4 > Ca 3 (PO 4 ) 2 b 3- H 3 PO 4 PO 4 HPO H 2 PO PO 4 HPO 4 H 2 PO 4 AgNO 3 ph Ag 3 PO 4 ph c 973K Graham (NaPO 3 )x ph 5.5~6.4 20~ AgNO 3 AgNO Bi 2 S 3 Bi 2 O K 1853K 3% Bi + 4HNO 3 ( ) === Bi(NO 3 ) 3 + NO + 2H 2 O 3 4 Bi 2 O 3 Bi 2 S 3 BiX 3 5 M 3 Bi Bi 2 O 3 Bi 2 O 5 12

92 +5 NaBiO 3 1 Bi 2 O 3 4Bi + 3O 2 == 2Bi 2 O 3 2Bi 2 S 3 + 9O 2 == 2Bi 2 O 3 + 6SO 2 Bi 2 O 3 Bi 2 O 3 K θ a = Bi 3+ BiO + Bi 2 O 3 Bi(OH) 3 2 Cl 2 +3 Bi(OH) 3 + Cl 2 + 3NaOH == NaBiO 3 + 2NaCl + 3H 2 O NaBiO 3 NaBiO 3 Mn 2+ - MnO 4 Bi 2 O 5 + 4H + + 2e - == 3BiO + + 2H 2 O φ θ A = 1.593V MnO H + + 5e - == Mn H 2 O φ θ A = 1.51V 5NaBiO 3 + 2Mn H + == 2MnO Bi Na + + 7H 2 O Mn 2+ NaBiO 3 MnO - 4 Mn 2+ 13

93 C s 2 2p 2 +2,+4 /pm 77 /pm M /(kj/mol) /(kj/mol) (Pauling ) 2.5 Si s 2 3p 2 0, s 2 2p 2 4 sp 3 4 δ CH 4 sp 2 3 δ 1 π C 2 H 4 sp 2 δ 2 π CO 2 HCN C 2 H 2 sp 1 δ 1 π 1 π 1 CO sp 3 4 δ π 3d sp 3 d δ SiF 6 PO 3-4 d-p π 2- SiO

94 0.027% 27.7% SiO 2 87% C Cr 9 Fe 4.5 Pb K sp C C 1100K CO K 3773K sp 2 sp 2 p p m m m π ( m m ) 3 (C 60 ) C Robert FCurl Jr( ) Harold WKroto( ) Richard ESmalley( ) C Rice Smalley Kroto N 20~25 60 C 60 sp 2 p C 60 Fuller Buckminsterfullerene C 60 C 60 Fuller 2

95 C 60 C 70 (Soxhlet) C 60 C 70 C 84 C 78 C 60 C 60 C CO % 0.014% CO 2 1 CO 2 sp C sp O δ C p sp p π 4 3 CO 2 C O ( H 3 CH 2 C OH ) 148pm CO ( CO )112.8pm CO 2 116pm C O C O sp CO 2 2 CO K CO 2 1.8% CO 2 CO 2 217K 25.1kJ mol -1 CO 2 CO K CO 2 Na 2 CO 3 NH 4 HCO 3 Pb(OH) 2 2PbCO 3 CO 2 CO 2 CO 2 2.5% CO 2 CO 2 CO 2 2Mg + CO 2 2MgO + C CO 2 CO 2 3 CO 2 CO CO CO sp C 2 p O 2 p δ π O p C 2p CO O C O C CO CO N

96 2 CO CO CO C C CO N 2 1 CO CO CO Fe 2 O 3 + 3CO 3CO 2 + 2Fe CuO + CO CO 2 + Cu CO CO CO CO + PdCl 2 + H 2 O CO 2 + 2HCl + Pd 2 CO Fe(CO) 5 Ni(CO) 4 Cr(CO) 6 3 CO O S H F 2 Cl 2 Br 2 CO CO 2 CO H 2 CO S CO F 2 Cl 2 Br 3 CO HCOOH CO + H 2 O H 2 C 2 O 4 CO 2 + CO + H 2 O NaOH CO 2 CO CO CO H 2 CO N 2 CO CO H 2 CH 4 CO CO 2 H 2 CO 3 ph 4 H 2 CO 3 C sp Li CO 2 Ca(HCO 3 ) 2 CaCO 3 + CO 2 + H 2 O Ca(HCO 3 ) 2 4

97 CO 2 NH 4 HCO 3 HCO 3-2 CO CO Ba 2+ BaCO 3 2 Cu 2+ Zn 2+ Pb 2+ Mg 2+ 2CO Cu 2+ + H 2 O Cu 2 (OH) 2 CO 3 + CO 2 3 Al Cr Fe 3CO Al H 2 O 2 Al(OH) 3 + 3CO 2 3 > > > H + > > , 2355, 2.32~2.34g/cm (1) Si F 2 F 2 SiF 4 SiO 2 SiC Si 3 N 4 SiS 2 (2) Si SiF 4 H 2 SiF 6 Si + 4HF SiF 4 + 2H 2 3Si + 18HF + 4HNO 3 3H 2 SiF 6 + 4NO + 8H 2 O (3) Si + 2NaOH + H 2 O Na 2 SiO 3 + 2H 2 (4) 3 Si SiO 2 + 2C Si + 2CO Si Si + Cl 2 SiCl 4 SiCl 4 SiCl 4 5

98 SiCl 4 + 2Zn Si + 2ZnCl % SiO 2 nh 2 O 1 SiO 2 SiO 2 Si-O Si sp 3 Si:O 2 1:2 SiO 2 CO 2 2 SiO 2 SiO 2 CO 2 SiO 2 Si-O CO 2 C Si C==O Si Si==O C==O SiO 2 H 2 SiO 2 + 2C Si + 2CO SiO 2 + 2Mg Si + 2MgO SiO 2 CO 2 SiO 2 CO 2 Si - O / 452 C - O / kj/mol Si=O / C=O / SiO 2 SiO 2 HF SiF 4 SiO 2 + 4HF(g) SiF 4 + 2H 2 O SiO 2 + 6HF(aq) H 2 SiF 6 + 2H 2 O SiO 2 + 2NaOH( ) Na 2 SiO 3 + H 2 O SiO 2 + Na 2 CO 3 Na 2 SiO 3 + CO 2 SiO xsio 2 yh 2 O SiO 2 H 2 SiO 3 K 1 = K 2 = SiO 2 SiO 2 SiO 2 SiO H + H 4 SiO 4 SiO H + + 2H 2 O H 4 SiO 4 H 4 SiO 4 6

99 H 4 SiO 4 CoCl 2 2 Na 2 SiO 3 8%~ 10% SiO 2 24h 333~343K 573K CoCl 2 CoCl 2 6H 2 O SiO 2 Na 2 CO 3 SiO 2 ~1600K Na 2 SiO 3 Na 2 O nsio 2 2 A Si - Si C - C SiH 4 SiH 4 88K 161K H C Si CH 4 SiH 4 H SiH 4 CH 4 Si d SiH 4 CH 4 1 SiH 4 CH 4 CH 4 SiH K SiH 4 CH 4 773K 1773K 7

100 SiH 4 Si + 2H 2 2CH 4 C 2 H 2 + 2H 2 SiH 4 CH 4 SiH 4 SiH 4 + O 2 SiO 2 + 2H 2 O SiH 4 + 2KMnO 4 MnO 2 + K 2 SiO 3 + H 2 O + H 2 SiH 4 + 8AgNO 3 + 2H 2 O 8Ag + SiO 2 + 8HNO 3 SiH 4 KMnO 4 SiH 4 CH 4 SiH 4 + (n+2)h 2 O SiO 2 H 2 O + 4H 2 2 H 2 SiO 2 SiO 2 + 4Mg Mg 2 Si + 2MgO Mg 2 Si + 4HCl SiH 4 + MgCl 2 SiH 4 LiAlH 4 SiH 4: SiCl 4 + LiAlH 4 SiH 4 + LiCl + AlCl 3 SiH 4 Si K ( ) 2 1 Ge + HCl Ge HCl Sn + 2 HCl ( ) SnCl 2 + H 2 Sn Pb + 2 HCl PbCl 2 + H2 PbCl 2 2 Pb + 6 HCl ( ) 2 HPbCl3 + 2 H2 2 Ge + 4 HNO 3 ( ) GeO 2 H 2 O + 4 NO 2 + H 2 O Sn + 4 HNO 3 ( ) H 2 SnO NO 2 + H2O Pb + 4 HNO 3 ( ) Pb(NO 3 ) NO H 2 O 3 Pb + 8 HNO 3 ( ) 3 Pb(NO 3 ) NO + 4 H 2 O Pb Pb + 2 OH - PbO H 2 Sn + 2 OH H 2 O Sn (OH) H 2 Ge + 2 OH - + H 2 O GeO H 2 Ge ( II ) Ge ( IV ) Ge, Sn, Pb Ge HCl Ge Sn Pb MO MO 2 MO MO 2. 8

101 . M OH - M (OH) 2 H + + HMO 2- M OH - M (OH) 4 H + + HMO 3- + H 2 O Pb(OH) 2 Ge(OH) Pb(IV) PbO 2 Pb(IV) :. PbO 2 : Tl(III) Hg(II) 2 Sn(II),. Sn : Hg:, : 3 1 PbO HNO 3 HAc Pb(II) Pb 3 O 4 Pb(II) 2 Pb(IV)O 4. Pb(NO 3 ) 2 PbCrO 4 ; PbO 2. 9

102 :? Pb(II), Ba(II), Ag(I),! 2 α- β- α-. SnCl 4 Sn(IV) α- β-, SnCl 4, α- β-. 10

103 16 [ ] Al(OH) 3 [ ] [ ] [ ] 3 [ ] B B B B 12 α α B 12 α σ B 2. (1) B N 2 O 2 X 2, B 2 O 3 BN, F 2 H 2 (2)B SiO 2 P 2O 5 H 2O B 2B + 6H 2 O(g) == 2B(OH) 3 + 3H 2 (3) B H 2 SO 4 HNO 3 2B + 3H 2 SO 4 ( ) == 2B(OH) 3 + 3SO 2 (4) 2B + 2NaOH + 3KNO 2 == 2NaBO 2 + 3KNO 2 + H 2 O (5) 1

104 B B 2 H 6 BH 3 BH 3 B 2 H 6 1 B 2 H 6 14 B 8 6 H 6 12 B 6 6 H 6 B 2 H 6 B 2 H B 2 H 4 B H σ 4 σ 4 2 B 2 H 2 1 H 2 B 2 H 2 B H 2 60 Lipscomb W. N ~ B 2 H B B (1) B H (2) (3) (4) (5) B 10 H 14 B 6 H 10 B 5 H 9 3 B 2 H 6 B 4 H 10 B 5 ~B 8 B 10 H 14 (1) B 2 H 6 (2) (3) B 2 H 6 H 2 (4) B 2 H 6 373K H 2 B 2 H 6 (5) B 2 H 6 LiH B 2 H 6 LiBH 4 LiBH 4 (6) B 2 H 6 + 2CO 2[H 3 B CO] B 2 H 6 4 B 2 H 6 (1) (2) (3) 2

105 B 2 H 6 90% 95% B 2 H B 2 O 3 H 3 BO 3 B 2 O B 2 O 3 2 (1) B 2 O 3 723K 2338K B 2 O 3 HBO 2 B 2 O 3 +3H 2 O l =2H 3 BO 3 aq (2) B 2 O 3 B 2 O 3 + CuO == Cu(BO 2 ) 2 B 2 O 3 + NiO == Ni(BO 2 ) 2 (3) B 2 O 3 NH 3 873K (BN) 2x x B 2 O 3 + 2xNH 3 == (BN) 2x + 3xH 2 O (4) B 2 O 3 873K CaH 2 CaB H 3 BO 3 B sp 2 O BO 3 B 2 O 3 O 1 B 1 H H 3 BO 3 H 2 (1) H 3 BO 3 273K 6.35g/(100gH 2 O) 373K 27.6 g/(100gh 2 O) (2) H 3 BO 3 Ka= B H 2 O O B P B(OH) 3 + H 2 O B(OH) H + (3) ph 5~6 ph 3~4 (4) H 2 SO 4 H 3 BO 3 + 3CH 3 OH B(CH 3 O) 3 + 3H 2 O (5) HBO 3 B 2 O 3 (6) ( P 2 O 5 ) H 3 BO 3 2B(OH) 3 + P 2 O 5 2BPO 4 + 3H 2 O 2B(OH) 3 + H 3 PO 4 2BPO 4 + 3H 2 O 3

106 3 xb 2 O 3 yh 2 O B 2 O 3 B sp 3 O BO 4 Na 2 B 4 O 5 (OH) 4 8H 2 O [B 4O 5 (OH) 4 ] 2-4 B BO 4 3 B BO 3 BO 3 BO 4 O Na 2 B 4 O 5 (OH) 4 8H 2 O Na 2 B 4 O 7 10H 2 O (1) (Na 2 B 4 O 7 10H 2 O) 650K 1150K (2) BO 3 Na 2 B 4 O 7 + CoO == 2NaBO 2 Co(BO 2 ) 2 (3) B 4 O H 2 O [HB 4 O 7 ] - + OH - [B 4 O 5 (OH) 4 ] H 2 O 2 H 3 BO 3 + 2B(OH) Al 3s 2 3p 1 +3 Al 3+ Al 3d 6 4 Na 3 [AlF 6 ] Na[AlCl 4 ] 2 1 2Al + 3H 2 SO 4 Al 2 (SO 4 ) 3 + 3H 2 HNO 3 H 2 SO 4 2Al + 6H 2 SO 4 ( ) Al 2 (SO 4 ) 3 + 3SO 2 + 6H 2 O NaAlO 2 2Al + 2NaOH + 6H 2 O 2Na[Al(OH) 4 ] + 3H 2 2 4

107 2Al + 3O 2 Al 2 O 3 rh θ = -3339kJ/mol 2Al + Fe 2 O 3 Al 2 O 3 + 2Fe (3273K) MnO 2 Cr 2 O 3 (3) 3 ( ) 1 Al 2 O 3 + 2NaOH + 3H 2 O 2Na[Al(OH) 4 ] Al 2 O 3 + Na 2 CO 3 2NaAlO 2 + CO 2 2 CO 2 2Na[Al(OH) 4 ] + CO 2 Al(OH) 3 + Na 2 CO 3 + H 2 O 2NaAlO 2 + CO 2 + 3H 2 O 2 Al(OH) 3 + Na 2 CO 3 3 Al(OH) 3 Na 2 CO 3 4 Al 2 O 3 Na 3 AlF K O 2 O 2 CO CO 2 F 2 CF 4 Al 2 O 3 5V 60000A 1 98%~99% Si Fe Ga 4 1 Al 2 O 3 α Al 2 O 3 γ Al 2 O 3 α Al 2 O 3 γ Al 2 O 3 α Al 2 O 3 6 O 2/3 Al α Al 2 O ± 15K 8.8 Cr 3+ Fe 2+ Fe 3+ Ti K α Al 2 O 3 γ Al 2 O 3 Al O 5

108 γ Al 2 O 3 α Al 2 O 3 2 Al 2 O 3 Al(OH) 3 Al(OH) 3. Al OH - Al(OH) 3 Al(OH) 3 + 3H + Al H 2 O Al(OH) 3 + OH - Al(OH) - 4 Al(OH) 3 NH 3 NH 3 Al(OH) 3 Na 2 CO 3 Na 3 AlF 6 2Al(OH) HF + 3Na 2 CO 3 2 Na 3 AlF 6 + 3CO H 2 O 5 1 Al 3+ Al 3+ [Al(H 2 O) 6 ] 3+ + H 2 O [Al(H 2 O) 5 (OH)] 2+ + H 3 O + [Al(H 2 O) 5 (OH)] 2+ Al(OH) 3 Al 3+ Al(OH) 3 [Al(H 2 O) 6 ] 3+ Al(OH) 3 + 3H 2 O + 3H + 2Al CO H 2 O 2 Al(OH) 3 + 3CO 2 2Al S H 2 O 2 Al(OH) 3 + 3H 2 S 2 Al 2 O 3 Al 2 O 3 + 2NaOH 2NaAlO 2 + H 2 O - NaAlO 2 KAlO 2 AlO 2 [Al(H 2 O) 4 ] - [Al(H 2 O) 6 ] 3+ Al(OH) 4 - Al(OH) 3 + OH - CO 2 Al(OH) 3 2NaAlO 2 + 3CO 2 + 3H 2 O 2 Al(OH) 3 + Na 2 CO 3 Al(OH) 3 Al 2 O 3 6 AlF 3 AlCl 3 AlBr 3 AlI 3 AlCl 3 1 AlCl 3 AlCl 3 Al Cl Al sp 3 Cl AlCl 3 Al 2 Cl 6 B 2 H 6 2 AlCl 3 AlCl 3 + H 2 O Al(OH)Cl 2 + HCl 6

109 AlCl 3 Al(OH) 3. Al(OH)Cl 2 + H 2 O Al(OH) 2 Cl + HCl Al(OH) 2 Cl + H 2 O Al(OH) 3 + HCl AlCl 3 Al(OH) 3 [Al 2 (OH) n Cl 6-n ]m 1 n 5 m 10 Al 2 (SO 4 ) 3 FeCl 3 Al 2 (SO 4 ) 3 FeCl 3 AlCl 3 BF 3 AlCl 3 AlCl 3 + Cl - - AlCl 4 AlCl 3 + NH 3 AlCl 3 NH 3 AlCl 3 3 AlCl 3 ( ) Cl 2 2Al + 3Cl 2 2AlCl 3 Cl 2 Al 2 O 3 + 3C + 3Cl 2 2AlCl 3 + 3CO AlCl 3 6H 2 O Ga In Tl m.p. Ga Ga b.p Hg Ga + 3H 2 SO 4 Ga 2 (SO 4 ) 3 + 3H 2 ( ) III (In ) 2Tl + H 2 SO 4 Tl 2 SO 4 + H 2 ( ) I Ga + 6HNO 3 Ga(NO 3 ) 3 + 3NO 2 + 3H 2 O (In ) Tl + 2HNO 3 TlNO 3 + NO 2 + H 2 O Tl Tl(III) 2Ga + 2NaOH + 2H 2 O--- 2NaGaO 2 + 3H 2 ( ) Ga 2 O 3 Ga(OH) 3 2 Ga(OH) 3 NH 3 H 2 O Al(OH) 3 NH 3 H 2 O Ga(OH) 3 Al(OH) 3 3 In 2 O 3 In(OH) 3, In 2 O 3,. 4 Ga(OH) 3, In(OH) 3, Tl(OH) 3,, : 2M(OH) 3 M 2 O 3 + 3H 2 O (In 2 O 3 ) Tl(OH) 3. 5 Tl 2 O 3 Tl 2 O 3 ( ) Tl 2 O( ) + O 2 ( ) 6 Tl 2 O TlOH Tl 2 O( ) + H 2 O 2TlOH( ) 7, TlOH ( KOH) Ga(OH) Tl(III) Tl (III) (I) Ga(I) In(I) Al(I) MF 3 b.p. Tl(III) 7

110 TlX AgX ; Tl(I) K + Rb + Tl 2 SO 4 8

111 Li Na K Rb Cs s s s s s /pm /pm /(kj/mol) /(kj/mol) M + /(kj/mol) φ θ / V Be Mg Ca Sr Ba s s s s s /pm /pm /(kj/mol) /(kj/mol) /(kj/mol)

112 M + /(kj/mol) φ θ / V % Na (S) + (x+y)nh 3 (l) Na(NH 3 ) + - x + e (NH 3 ) y Be 2s 2 89pm Be 31pm Be [Be(H 2 O) 4 ] O H [Be(H 2 O) 4 ] 2+ [Be(OH) (H 2 O) 3 ] + + H

113 Li 2 O Na 2 O 2 MO 2 M=K Rb Cs MO 2 -O-O- Na 2 O 2 Cr 2 O 3 3Na 2 O 2 2Na 2 CrO 4 Na 2 O MnO 2 Na 2 O 2 Na 2 MnO 4 Na 2 O 2 H 2 O 2 H 2 O 2 2Na 2 O 2 2CO 2 2Na 2 CO 3 O 2 5O MnO H + 2Mn O 2 + 8H 2 O 3 KO 2 RbO 2 CsO 2 2MO 2 2H 2 O == O 2 H 2 O 2 2MOH (M K Rb Cs) 4MO 2 2CO 2 == 2M 2 CO 3 3O 2 (M K Rb Cs) 4 3KOH (S) + 2O 3 (g) 2KO 3 (S) + KOH + H 2 O (S) + 1/3O LiOH 13g/100g NaOH BeO MgO Be(OH) 2 Mg(OH) 2 LiOH NaOH KOH RbOH CsOH (mol/dm 3 ) (293K) 3

114 Be(OH) 2 Mg(OH) 2 Ca(OH) 2 Sr(OH) 2 Ba(OH) (mol/dm 3 ) (293K) NaOH KOH Ca Sr Ba H 2 NaH NaH NaH LiH LiH + H 2 O = LiOH + H 2 1kg 2800L Li + Na + K + Rb + Cs Ca 2+ Sr 2+ Ba 2+ (nm) I - SO F - OH MgCl 2 987K 1685K 6 MgCl 2 6H 2 O 4

115 MgCl 2 6H 2 O ==== Mg(OH)Cl + HCl + 5H 2 O MgCl 2 MgCl 2 MgO 4 CaCO 3 CaCO g cm -3 (1) CaCO K (2) Na 2 CO 3 (3) CaCO 3 Ca(HCO 3 ) 2 Ca(HCO 3 ) 2 ==== CaCO 3 + CO 2 + H 2 O IA Li Na+ Mg Mg 5

116 18 1. Cu ( ) Cu( ) 2. ( ) Cu ( ) Cu( ) ( ) ( ) Cu O 2 CuO 2Cu + O 2 ( ) 2CuO( ) Cu 2Cu + O 2 + H 2 O + CO 2 Cu(OH) 2 CuCO 3 ( ) Au Ag O 2 2 Cu Ag Au H 2 O Cu Ag 2 Cu + 4HCl + O 2 2 CuCl 2 + 2H 2 O 4 Ag + 4HCl + O 2 4 AgCl( ) + 2H 2 O 2 Cu + 2H 2 SO 4 ( ) + O 2 2 CuSO 4 + 2H 2 O Cu 2 Cu + 8HCl ( ) 2H 3 [CuCl 4 ] + H 2 ( ) Cu KCN [CuCl 4 ] 3- [CuCN 4 ] 3-3 1

117 Cu HNO 3 H 2 SO 4 Ag Cu Au 4 Cu Ag Au NaCN ( %) ( ) - Zn Au(CN) 2 Au M(I) 1 1 Cu(I) Cu + Cu 2 O H 2 O Cu 2 O + H 2 SO 4 CuSO 4 + Cu + H 2 O Cu(I) 2 O CuO Cu(I) CuCl 4CuCl+O 2 +4H 2 O 3CuO CuCl 2 3H 2 O + 2HCl Cu(I) CuI( ) + 2Hg Hg 2 I 2 ( ) + Cu CuI 3 2 Ag(I) Ag + Ag 2+ Ag + Ag(I) Ag + H 3 PO 2 H 3 PO 3 N 2 H 4 NH 2 OH Ag(I) 2 Cu(OH) Cu(I) 2 O( ) Cu 2 O 1508 K AgOH 228 K 2AgOH ( ) Ag 2 O ( ) + H 2 O 2

118 AgCl AgBr Ag I 3 Cu(I) Ag ( I ) sp d 10 M + /M M Ag O 2 KCN Cu NaCN H 2 O H M(II) 1 CuCl 2 CuCl 2-4 CuCl 2 [Cu(H 2 O) 4 ]Cl 2 d-d Cu(NH 3 ) 2+ 4 Cu(CN) 2-4 Cu 2+ d 9 dsp 2 [ - ] CN - d-d 2 Cu 2+ I - CuI [Cu + ] Cu 2+ /Cu + I - I 2 Cu(I) Cu(II) 3. Cu(OH) 2 Cu(OH) 2 CuO + H 2 O CuO 4CuO 2Cu 2 O + O 2 ( ) ( >1273K) Cu 2 O CuO 4. Cu(OH) 2 Cu(OH) 2 Cu(OH) 2 + H 2 SO 4 CuSO 4 + 2H 2 O Cu(OH) 2 + 2NaOH Na 2 [Cu(OH) 4 ] CuSO 4 NH 3 H 2 O Cu 2 (OH) 2 SO 4 NH 3 H 2 O Cu + Cu 2+ Cu Cu(I)

119 IIA IB Zn Cd Hg Hg Zn Cd Hg Hg Na 2. IIB 1 Zn Cd Hg O 2 MO 2Zn + O 2 2ZnO 2Cd + O 2 2CdO ( ) 2Hg + O 2 2HgO ( ) Hg Zn Cd Hg Cd Hg Zn 4Zn + 2O 2 + CO 2 + 3H 2 O ZnCO 3 3Zn(OH) 2 2 Zn Cd H 2 Hg Hg Hg + 2H 2 SO 4 ( ) HgSO 4 + SO 2 (g) + H 2 O Hg + 8HNO 3 3Hg(NO 3 ) + 2NO 2 (g) + 4H 2 O 6Hg + 8HNO 3 3Hg 2 (NO 3 ) 2 + 2NO + 4H 2 O Zn H + Zn + 2NaOH + 2H 2 O Na 2 [Zn(OH) 4 ] + H 2 (g) Cd Hg Zn H + H + Cu Zn 3. Cu Zn Zn Cu Cu Zn :M(s) M 2+ (aq) : E Zn 2+ /Zn < 0 E Cu 2+ /Cu > 0 Zn M(s) M 2+ (aq) Zn G = H T S H Zn G Zn Cu 4. 4

120 ZnS ( CdS) 2ZnS + 3O ZnO(s) + 2SO 2 ( g) SO 2 ZnO + C --- Zn(g) + CO(g) (1000 ) Cd Zn Zn Cd Cd Zn Cd ZnO H 2 SO 4 Zn ( Cd 2+ ) 99.97% Zn M(II) 1. Zn(OH) 2 ZnO 2H + + ZnO 2-2 Zn(OH) 2 Zn 2+ +2OH - H + OH - Cd(OH) 2 Cd(OH) 2-4 HgO Ag 2 O Cd(OH) 2 2. Zn 2+ Cd 2+ Hg 2+ d 10 Zn(OH) 2 Cd(OH) 2 Hg(OH) 2 Hg OH - HgO ( )+ H 2 O HgO 2HgO 2Hg + O 2 ( ) (673K) ZnO CdO 3. Hg(NO 3 ) 2 HgCl 2 ( ) HgCl 2 + 2H 2 O Cl Hg OH(Hg(OH)Cl ) + HCl HgCl 2 HgCl 2 Cl Hg NH 3 ( ) ZnCl 2 H 2 O Zn(OH)Cl + HCl HCl 4. Zn(NH 3 ) 2+ 4 Cd(NH 3 ) 2+ 4 Hg HgCl 2-4 Hg(SCN) Hg(CN) 4 Hg 2+ Cl - Br - I - I - I - Hg 2+ HgI2( ) HgI42-( ) + K 2 [HgI 4 ] KOH (Nessler) NH 4 IIB M(II), d-d HgI M(I) Hg(I) 1. Ag(I) 5

121 1 AgCl( ) AgBr( ) AgI( ) Hg 2 Cl 2 ( ) Hg 2 Br 2 ( ) Hg 2 I 2 ( ) Hg 2 Cl 2 Hg 2 Cl 2 Hg + 5d 10 6s 1 Hg 2+ 2 Cu + 3d 10 Cu 2+ 2 ( HgCl 2 ) Ag(I) 1 NH 3 Ag NH 3 Ag(NH 3 ) 2 Hg 2 Cl 2 + 2NH 3 Hg( ) + Hg(NH 2 )Cl( ) + NH 4 Cl [Hg( ) + Hg(NH 2 )Cl( ) ] 2 Ag + Hg 2 Cl 2 + Cl 2 2HgCl 2 Hg 2 (NO 3 ) 2 + 4HNO 3 ( ) 2Hg(NO 3 ) 2 + 2NO 2 + 2H 2 O 3. Hg(I) Hg(II) Hg(0) Hg(I) Hg(II) Hg Hg(I) Hg(II) E E 0.1V Hg 2+ 2 Hg 2+ Hg(II) Hg(I) Hg(II) Hg 2 Cl 2 + Cl 2 2HgCl 2 Hg 2CO 3 Hg + HgO + CO 2 Hg 2 Cl 2 Hg + HgCl 2 6