Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://chem.msu.ru/rus/olimpiad/russia/2006/reshvyb-inorg.pdf Äàòà èçìåíåíèÿ: Mon Jul 31 18:52:10 2006 Äàòà èíäåêñèðîâàíèÿ: Mon Apr 11 03:48:04 2016 Êîäèðîâêà:

V ­ ­

1. ( ­ .. ) 1. , D(H2):




19.0

B 71.0

61.0

104.0

66.0

53.0

, / 18.5

, , , , x, y, x·A + y·19 = 66, ­ . y 1 2 3 =1 A = 47 (?) A = 28 ­ SiF2(?) A = 9 (?) =2 A = 23.5 (?) A = 14 ­ N2F2(?) A = 4.5 (?) =3 A = 15.7 (?) A = 9.3 (?) A = 3 (?) =4 A = 11.75 - CF4(?) A = 7 (?) A = 1.25 (?)

CF4 SiF2 , - N2F2, = N. : ­ NF3, - FN3, ­ N2F4. , . , F, N, 53 = 14a +19b + c, (a, b, c ­ ) NHF2 ­ . , ­ F, N, H. NH2F 35, . ­ NH4F, HF NH3 = ½[(HF) + (NH3)] = 18.5 (NH4F), 2/3 HF 1/3 NH3, , = NH4HF2. AsF5 -, = [N2F]+[AsF6]-. : 2NH4F NH4HF2 + NH3 4NF3 + C 2N2F4 + CF4 N2F4 + 2C6H5SH 2NHF2 + (C6H5S) 2FN3 N2F2 + 2N2 -N2F2 + AsF5 [N2F]+[AsF6] 2. Kp: p(-N2F2) = p rG = ­2.303·RT·lg(Kp) =
· 2

3NH4HF2 2NF3 + 6H2 + NH3 N2F4 + Cu N2F2 + CuF2 2NHF2 + 2KF N2F2 + 2KHF2 -N2F2 -N2F2
-

[N2F]+[AsF6]- + NaF -N2F2 + Na+[AsF6]

(1-), p(-N2F2) = p·, ­ -N2F2 /(·)·373·lg(54.6) ­12402/ =

373 . Kp = p(-N2F2)/p(-N2F2) = /(1-) = 0.982/(1-0.982) 54.6. ­2.303·8.314 = ­12.4 /. 3. N2F+ N2O , , . FN3 , HN3. S ­ N-N-N F-N N-N: 1


V ­ ­

F
104
0

N

N+
171
0

N-

F - N-N, . 2. ( ­ .. ) 1. () () (III), . , : K2Cr2O7 2,5 0,0085 (0,017 Cr) 0,016 0,0595 1 2 7 K2C2O4H2O 3 H2C2O42H2O 7,5

: K2Cr2O7 + 7H2C2O4 + 2K2C2O4 = 2K3[Cr(C2O4)3] + 6CO2 + 7H2O , 1 ­ (III) . (VI) K2CrO4 K2CO3. , 1 K3[Cr(C2O4)3]3H2O ( , .. Cr(III) ­ 6, -). 1: 4K3[Cr(C2O4)3] 3H2O + 9O2 = 4K2CrO4 + 2K2CO3 + 22CO2 + 12H2O 46%. 2 ­ ( 2 : 1), . . , . - . K2CrO4 + BaCl2 = BaCrO4 + 2KCl K2CO3 + BaCl2 = BaCO3 + 2KCl 2BaCrO4 + 4HNO3 = 2Ba(NO3)2 + H2Cr2O7 + H2O BaCO3 + 2HNO3 = Ba(NO3)2 + CO2 + H2O 3 ­ . 4 ( ): C 11,70:12= 0,975 2


V ­ ­

H Cr La

3,15:1 = 3,15 8,15:51,996= 0,156 22,20:138,91=0,1598

La : Cr 0,156 : 0,1598 = 0,976 0,1598 : 0,156 = 1,02, . 1:1 La:C:H 1:(0,975:0,1598):(3,15:0,1598) = 1:6,10:19,7 Cr:C:H 1:(0,975:0,156):(3,15:0,156) = 1:6,25:20,2 LaCr(C2O4)310H2O LnCr(C2O4)310H2O. 4 - PrCr(C2O4)310H2O 5 - PrCrO4 ( ), 6 - PrCrO3. 2. K2Cr2O7 + 7H2C2O4 + 2K2C2O4 = 2K3[Cr(C2O4)3] + 6CO2 + 7H2O 4K3[Cr(C2O4)3] 3H2O + 9O2 = 4K2CrO4 + 2K2CO3 + 22CO2 + 12H2O K2CrO4 + BaCl2 = BaCrO4 + 2KCl K2CO3 + BaCl2 = BaCO3 + 2KCl Ln(NO3)3 + K3Cr(C2O4)3 + 10H2O = LnCr(C2O4)310H2O + 3KNO3 PrCr(C2O4)310H2O + 2O2 = PrCrO4 + 6CO2 + 10H2O 2PrCr(C2O4)310H2O + 3O2 = 2PrCrO3 + 12CO2 + 20H2O 3. 4. . 1 ­ Cr +3 (K +1)

2 - Cr +6 (K +1) 3 ­ Cr +6 (Ba +2) 4 - Cr +3, Ln +3 5 - Cr +4, Pr +4 6 - Cr +3, Pr +3 5. 6. K2CrO4 + 2AgNO3 = Ag2CrO4 + 2KNO3 K2CO3 + 2AgNO3 = Ag2CO3 + 2KNO3 ( S. Decurtins, M. Gross, H.W. Schmalle, S. Ferlag "Molecular Chromium(III) ­ Lantanide(III) Compounds (Ln = La, Ce, Pr, Nd) with a Polymeric, Pr(IV) ­ 1e; Cr(IV) ­ 2e. ­ 3. Pr(III) ­ 2e; Cr(III) ­ 3e. ­ 5.

3


V ­ ­

Ladder ­ Type Architecture: A Structural and Magnetic Study." J. Inorg. Chem., 37 (10) 2443 ­ 49 (1998).) 3. ( ­ .. ) 1. (1) ­ CaCO3; (2) ­ (.6) (3) ­ (4) ­ (5) ­ (NaCl) (6) ­ ( ) (7) ­ (8) ­ ( ­ ) (9) ­ , ( , ) (10) ­ , ( BiOCl) (11) ­ (12) ­ (13) ­ ( ). 2. 3. , , (..7) , . , . ­ , . ­ ( ­ ( ), ). : CaCO3 + 2HNO3 = Ca(NO3)2 + CO2 + H2O 4


V ­ ­

4. 5. 6.

(II) ( ). (II) .

( () ) , , , .

Co(II), -. ( ) ­ -, . : , . "" q , , " ". , , , . 4. ( ­ .. ) 1. F : Ti = (40,0 : 18,998) : (35,7 : 47,88) , : 142,5 ­ 134, , Ti(H2O)2F3. 6, , . , , , -. , 4 ( ) . 4 - ( ), -. [Ti(H2O)4F2/2][TiF4F2/2]. 2. 2Ti + 6HCl = TiCl3 + 3H2 ( , d-d , d- .) 3. - , - (III), (III) (IV) (II): 5 Ti(III), (III): = 2,105 : 0,7456 = 2,82 :1 3


V ­ ­ 2[Ti(H2O)6]3+ +6F

= [Ti(H2O)6] + [TiF6] + 6H2O

2+

2-

4.

(IV) ­ 4 -

(): [TiF4F2/2]. (II) ­ 4 2 -: [Ti(H2O)4F2/2]. ( ) (II). 5. 6. 7. Ti(IV) ­ 1s22s22p63s23p6(3d0); Ti(II) - 1s22s22p63s23p63d2. ­ , 2/3 ­ (II) (IV), 4Ti2+ + O2 + 4H+ = 4Ti3+ + 2H2O 4Ti3+ + O2 + 24HF = 4[TiF6]2- + 2H2O + 20H+ ( - (IV)- .) ( U. Kolle, P. Kolle, "Aqueous Chemistry of Titanium (II) Species", Angew. Chem. (Int. Ed.Engl.), 43 (37) 2003, p.4540-42.) 5. ( ­ . ., .. ) 1. (CuO), : 2CuO + 4NH4Cl = [Cu(NH3)4]Cl2 + CuCl2 + 2H2O Cu(II) Cu(I): [Cu(NH3)4]2+ + Cu = 2[Cu(NH3)2]+ (I) : 4[Cu(NH3)2]+ + O2 + 4NH3 + 4NH4+ = 4[Cu(NH3)4]2+ + 2H2O (II) (II) : [Cu(NH3)4]2+ + 4CH3COOH = Cu(CH3COO)2 + 2NH4CH3COO + 2NH4 (II): 2Cu + O2 + 4CH3COOH = 2Cu(CH3COO)2 + 2H2O , , . 2. : NH4+ + H2O NH3 + H3O+ CH3COO­ + H2O CH3COOH + OH­ Ka = 10
­14 +

, 1/3 ­ . (III):

" " ­

/1,7610

­5

= 5,6810

­10

Kb = 10 6

­14

/1,7410­5 = 5,7510

­10


V ­ ­ NH4+ + CH3COO­

NH3 + CH3COOH

K=Ka(NH4 )/Ka(CH3COOH)= 3,2610­5 +

, , NH3 CH3COOH . :

K=

[ NH 3 ][CH 3COOH ] [CH 3COOH ]2 = [ NH 4 + ][CH 3COO - ] CNH + CCH COO-
4 3

( ). [CH3COOH], Ka(CH3COOH) [H+]: [CH 3COOH ] = K C [H + ] =
NH
4 +

CCH

3

COO

-

K a (CH 3COOH ) [CH 3COOH ] K a (CH 3COOH ) K C = [CH 3COO - ] CCH COO-
3

NH

4

+

CCH

3

COO

-

=

= K a (CH 3COOH ) K C = 7,00

NH

4

+

/ CCH

3

COO

-

= 9,93·10­8

3. , 1 NH43COO 0,5 CH3COOH, . ( -), ( ). (Ka = 5,6810­10), . : [H + ] = pH = 5,05. , : NH4+ + CH3COO­ NH3 + CH3COOH K = 3,2610­5 -, , . : K a [CH 3COOH ] 1, 78 10-5 0, 5 = = 8, 9 10 [CH 3COO - ] 1
-6

K=

[ NH 3 ][CH 3COOH ] X (0, 5 + X ) = = 3, 39 10 [ NH 4 + ][CH 3COO - ] (1 - X ) 2

-5

= 6,5·10­5. , , . 4. (II) Cu(CH3COO)2, () Cu(OH)(CH3COO). 5. " " :
7


V ­ ­

Cu(OH)(CH3COO) = Cu + 2H2O + 2CO (I): 4Cu(OH)(CH3COO) + 3O2 = 2Cu2O + 4CO2 + 8H2O (II). 6. (, ) ­ . ( ): 2Cu + O2 + 2H2SO4 = 2CuSO4 + 2H2O , , , .
6 ( ..)

1. La

1.85Ba0.15CuO4

, : ZCu + 2·0.15 + 3·1.85 = 8, ZCu = +2.15; = +2.33.

, , . YBa2Cu3O7: 3·ZCu + 2·2 + 3·1 = 14, Z
Cu

2. = 0 La2CuO4, - +2, . = 2 «Ba2CuO4», - +4, , . 3. Y-123: Y2O3 + 4BaO2 + 6CuO 2YBa2Cu3O7 + 3/2O2 Y-211: Y2O3 + BaO2 + CuO Y2BaCuO5 + 1/2O2 Y2Cu2O5: Y2O3 + 2CuO Y2Cu2O5 4. ) Cu-O , , , (, , ). ) 2 ­ 180 ­ Cu2+ Cu3+, , 2- , . ) : 180°. 5. : . - Cu-O , . Ca ­ , Ca2+ , Cu-O. 8


V ­ ­

6. ) 1 = 9 ( ), 2 ­ ( ) 2 = 8 = 10. 7. , . >8, . 8. ­ ( = 10) , . 9. - , CuO BaO. 10. MgB2, (Ba,K)BiO3, (Sr,Ba)CuO2, HgBa2Ca2Cu3O8+, Bi2Sr2(CaxSr1-x)Cu2O8+ .. : .. , .. , . , , , - .

9