Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.inorg.chem.msu.ru/study/Seminary-I-semestr.pdf Äàòà èçìåíåíèÿ: Sun Nov 11 20:38:16 2012 Äàòà èíäåêñèðîâàíèÿ: Sat Feb 2 23:58:08 2013 Êîäèðîâêà: Ïîèñêîâûå ñëîâà: m 101

..


I

..

..

- 2010







, .. , I ( - , ). . , , , «» , , , . , , , , . , , - . , , -





(, , ). «», . , . , , , . , (, , , ), . . 2


, ( ), . , .

3




1. 2. 3. 4. . - 1 5. . - 2 6. 7. - - 1 8. - - 2 9. - 1 10. - 2 11. - 1 12. - 2 13. ­ 1 14. ­ 2 15. ­ 1 16. ­ 2 17. 18.

5 12 18 25 29 34 41 46 52 58 67 74 79 85 91 98 106 113 119

4


1. .
. 1. . 2. . . 3. . . 4. . 5. . 6. . . 7. .

1. . ( ) ­ , . 1.1. . + + + ­

() ­ ­

­ . ­ , . : ­ (, ); ­ (, , ).

5


­ , , . 1. . ? . ) . ) . ) . ) . ) .

2. . . 2.1. ­ . : Q = U + A : Q ­ , . U ­ . ­ , . , , , .

2.2. ­ , . , A = pV (p ­ , V ­ : V>0, V<0).

6


1.2. . p=const V=const Q=0 Qp=U + pV = H Qv=U ( V = 0) U= ­pV

: H ­ , H = U + pV, H ­ .

2.3. : ; , (U H).

3. . . 1. Qp - Qv = H ­ U = U + pV ­ U = pV = RT, - (>0, , <0, ). 2. Qp - Qv H2 () = 2H () 1000°. 2 ( ). , . 1.3. . (1) C + 1/2O2 = CO (2) CO + 1/2O2 = CO2 (3) C + O2 = CO2 H1 H2 H3

(1) + (2) = (3) H1 + H2 = H3 7


4. . : , , . : . (fH0T) ­ 1 , , 101325 (1 ). : - ; f ­ formation (); H ­ ;
0

­ , ;

T ­ , ( , 298 ). (fH0): 1) . 2) fH0>0, (Cl2O, C2H2), , fH0<0, (CO2, H2O). 3) fH0=0 (, ), fH0>0 (, ). 4) . 3. , fH0 4. . 1.4. . fH0
298 298

H2SO4.

, /

Fe3O4 () ­1118 CO () CO2 () ­110 ­394 8


rH0

298

Fe3O4 + 4CO = 3Fe + 4CO2

5. () ­ , 1 1 . : 1. . 2. , (cp) (V). 3. . 4. , . , , , .

6. . . 6.1. 5. . H-O (EH-O), fH0298 H2O () = ­242 /, H2 O2 H0298 () 436 495 / . . ­ ­ . : H2O() = 2H() + O() rH0298 = 2EH-O ( ) = H0298 () H2 + ½ H0298 () O2 ­ fH0298 H2O () ( H0 fH0 ). 2EH-O = H0298 () H2 + ½ H0298 () O2 ­ fH0298 H2O (), EH-O = [H0298 () H2 + ½ H0298 () O2 ­ fH0298 H2O ()]/2 = [436 / + + ½495 / ­ (­242 /)]/2 = 463 /

9


6.2. 6. ( -). U0() ­ ­ .

. 1.1. . H0 () K ­ ­ , . H0 () Cl2 ­ . I1 (K) ­ ­ . Ae (Cl) ­ ­ . : , , 1 (, ). : 1.1. U0 () KCl = ­fH0 KCl + H0 () K + 1/2H0 () Cl2 + I1 (K) + Ae (Cl) 10


7. . 1. U0() KCl ( 6), fH0 KCl = ­438 /, H0 () K = 89 /, H0298 () Cl2 = 244 / ( 1 Cl2), I1 (K) = 425 /, Ae (Cl) = ­355 /.

2. fH0 1.5.

298

SOCl2 ()

1.5. . 2P () + 5Cl2 () = 2PCl5 () 6PCl5 () + 2P2O5 () = 10POCl3 () 4P () + 5O2 () = 2P2O5 () S () + O2 () = SO2 () PCl5 () + SO2 () = POCl3 () + SOCl2 () rH0
298

, /

­892 ­308 ­2988 ­297 ­101

11


2. .
. 1. . 2. . 3. . 4. . 5. . 6. . 7. .

1. . , , (NH4NO3, NH4NCS), , .. . , ­ . 2.1. .

H S

. 1) S = Q/T ­ , . : ­ , , . , ,

12


, . 2) S = klnW k ­ , 1.3810
-23

/.

W ­ , . , .

2. . 2.1. . . : , . . ,

2.2. ( ): ; (S), (S).

2.3. : 0 (.. W = 1). : 0 , . 3. . . ( ). 1) . S () < S () < S (). S > 0, , ( ). 2) . , (, S Fe3O4 () > S FeO ()). 13


3) . , , (, S NO2 () ( ) > S O2 () ( )). 4) . , , (, S CBr4 () > S CF4 ()). 1. (> <0) : PBr5 () = PBr3 () + Br2 () NH3 () + H2O () = NH4+ () + OH­ () MoO3 () + 3H2 () = Mo () + 3H2O () H2 () + Cl2 () = 2HCl () 24H10 () + 13O2 () = 8CO2 () + 10H2O () 4. . : S = Q/T ) T = const ( ): S = H ../T .. , S > S , H > H («» - , «» - ). ) T const ( ), dS = Q/T (d - ), Q = cdT, dS = cdT/T. T1 T2 (T2>T1), , S =
T2

T1



cdT / T .
f(T) S = cln(T2/T1) = f(T)

. 2.1. S (T) . 14


(T1>T ):
T.

S(T1) = S(0) +


0

T

()dT / T + H /T +

T



( )dT / T + H /T +

T1

T



()dT / T

S(0) ­ 0 . 2. 1 . H () = 40.7 /.

5. . , , . F = U ­ TS. G = H ­ TS = U + pV ­ TS : ; ( U), (F G). 6. 2.2. T, p = const S S = Q/T G T, V = const F

G = H ­ TS F = U ­ TS

S > 0 S = 0, max S

G < 0 G = 0, min G

F < 0 F = 0, min F

­ , (T, p = const), . 15


, H f(T) S f(T), G = f(T) = H ­ TS , S = ­ tg ( ­ ). G0 = f(T) = H0 ­ TS0. , H0 S0 . 2.3. . H0 1 2 3 4 + ­ + ­ S + ­ ­ +
0





CaCO3 () = CaO () + + CO2 () 2H2O () + 4NO2 () + + O2 () = 4HNO3 () 2N2 () + O2 ()=2N2O ()

NH4NO3 () = N2O () + + 2H2O ()

: .

. 2.2. G0 = f(T), 1-4. 16


3. CdO CdO () + H2 () = Cd () + H2O () , , . . 1) ( ) ? 2) ( ) ? 3) G0 = f(T) , H0 f(T) S0 f(T). , . 7. . 1. : 1) NH4NO3 () = NH3 () + HNO3 () 2) NH4NO3 () = N2O () + 2H2O () , , . rG0298. 2.4. NH4NO3 . NH4NO3 () NH3 () fH0 S
0 298

HNO3 () ­135 267

N2O () 82 220

H2O () ­242 189

, /

­365 151

­46 193

298

, /

2. NO Cl2 2NO () + Cl2() = 2NOCl () , NOCl . . 1) ( ) ? 2) ( ) ? 3) G0 = f(T) , H0 f(T) S0 f(T). , . 4) Qp ­ QV 400°? 17


3. .
1. 1 2 . 2. . . 3. . . 4. . . 5. . 6. .

1. 1 2 . G = U + pV ­ TS ( ) 1: T = const G = U + pV + Vp ­ TS ­ ST = U + pV + Vp ­ TS (T = 0) (1) 1 : Q = U + pV 2 : Q = TS : U + pV = TS U = TS ­ pV

2. . . (1) G = U + pV + Vp ­ TS = TS ­ pV + pV + Vp ­ TS = Vp (2) - pV = RT 2. = 1 V = RT/p, (2), G = Vp = RTp/p , dG = RTdp/p = RTd(lnp) p0 ( ) p 18
1


p1

p



0

dG = RT d ln p
p
0

p1

G = G 0 + RTln(p1/p0)

G - ­ 1 (. 2) ­ .
p1/p0 = a ­ . = 0 + RTlna

:

0 ­ ,
(. 1 ­ T = const, .. ).



p0 = 1 ­ . = p1/p0 , , ( , 1 ). , ( /), 1.



3. . -. A, B, C, D ­ , . kA + lB mC + nD (k, l, m, n ­ ) : G = m (0C + RTlnaC) + n (0D + RTlnaD) ­ k (0A + RTlnaA) ­ l (0B + RTlnaB) = = (m0C + n0D ­ k0A ­ l0B) + RT ln (pCmpDn/p
k A

pBl)

(m0C + n0D ­ k0A ­ l0B) = G0 ( ), G = G0 + RT ln (p
C m

pDn/p

k A

pBl) ( -) 19


, .. G = 0, G0 = - RT ln ([pC(.)]m[pD(.)]n/[pA(.)]k[pB(.)]l) = -RTlnK K ­ : ­ . , ( ). () , () . , . () 1, . ­ , . ( 0). , !

. G0 = ­RTlnK = H0 ­ TS ln K = ­ H0/RT + S0/R , H0 f(T) S0 f(T), ln K = f(1/T) ­ , ­H0/R ­ () . 3.1. H0 . H0 tg ) ) + ­ ­ +
0

20


. 3.1. ln K = f(1/T) .

4. . . : , , , , , . 3.2. . H>0

, ,

: , . ( ) .

21


5. . . 1. : 3Fe () + 4H2O () Fe3O4 () + 4H2 () 950 , ( 1 ) 42.3 % . 1) . 2) G0 . 3) ( ) ? 4) ( ) ? 5) G0 = f(T) , H0 f(T) S0 f(T). , .

2. , 2SO2 ()+O2 () 2SO3 () 1000 , p(SO2) = 0.5 , p(O2) = 0.8 , p(SO3) = 0.9 . . , H0 f(T) S0 f(T) 3.3. . SO2 fH0 S
0 298 298

O2

SO3 ­396.1

, / ­296.8 0 248.1

, /

205 256.1

: -.

3. : ClF3 () ClF () + F2 () , 600° 1 , () ClF3 (.. ) 0.84. 22


1) . 2) ( ) ? 3) ( ) ? 4) ln K = f(1/T) , H0 f(T) S0 f(T). 5) Qp ­ QV ? : ClF3 1 . . 3.4. ,
ClF
3

ClF

F

2

1+

1 -



x

/(.)

1 1 1 (.) 1


1


1

1

p

xp()


1

p(.)


1

p(.)

p(.)

(1) K = p(ClF)p(F2)/p(ClF3) =

2 2 0.84 2 1 p(.) = p(.) = p(.) / p(.) = = 1 1 1 2 1 0.84 1 1 = 2.40.

2

2

=

4. 2NaHCO3 () = Na2CO3() + CO2 () + H2O () 1) . 2) T = 298 ? G0
298

.

3) , 1 . , H0 f(T) S0 f(T).

23


3.5. . NaHCO3 () Na2CO3() CO2 () H2O () fH0 S
0 298 298

, / ­947.7 102

­1131 136.4

­393.5 213.6

­241.8 188.7

, /

6. . 1. , , : ) , ) . 1) CO () + Cl2 () = COCl2 () 2) Ba2+ (-) + SO42­ (-) = BaSO4 () 3) N2 () + O2 () = 2NO () 4) N2 () + 3H2 () = 2NH3 () H<0 H<0 H>0 H<0

2. NH4Cl () = NH3 () + HCl () 1) . 2) T = 298 ? G0
298

.

3) , 1 . 4) ln K = f(1/T) , H0 f(T) S0 f(T). , . 3.6. . NH4Cl () NH3 () HCl () fH0 S
0 298 298

, / ­314.4 95.9

­46.2 192.6

­92.4 186.9

, /

24


4. . ­ 1.
. 1. . 2. . 3. . 4. .

1. . ­ () , , . ­ , , , . ( , , ), . , : ) ­ (); ) ­ ( ­ ), ( ­ ) ; ) ­ , ( ­ ), . ­ , . ­ . () = ­ ­ (, ­ .), , . () ­ , , (.. ). 2. . =+2­ 25


­ ­ ­ . : 2 . (, p = const), 1. 1. , : ) ; ) ; ) ; ) 2NaHCO3 () = Na2CO3 () + CO2 () + H2O () 3. . : = 1 = 1 + 2 ­ = 3 ­ , p T ()

. 4.1. ( ). 26


4.1. . 1 2 () 3 (), (), : 2 1 3 ­ () ­ () ­ (B) 3 0 1 ()

: OA, ­ , . OK, ­ , . OB, -, . O ­ , ( , ). (T, p) ­ . K ­ , ( ). . 1) ­ 1 , .. CO2 , (« »). , , . 2) - , -, , ( ).

27


3) ­ ( « » - «» ). 4) ­ ­ . 2. , , lgp = ­1347/T + 7.92, lgp = ­1660/T + 9.37 ( , ­ ). . 3. ? , ? ?

4. . 1. , : ) ; ) ; ) NH4Cl () = NH3 ()+ HCl (); ) , ( ) .

2. lg p = ­1629/T + 4.9, lg p , .

= ­2351/T + 7.6. ­ .

28


5. . ­ 2.
. 1. ­ . . 2. - . 3. . 4. .

1. ­ . . : = 2 = 2 + 2 ­ = 4 ­ , p, T, x ( ) ­ , (p = const, T = const), = + 1 ­ = 3 ­ . (p=const) ­ ( ) .

. 5.1. . : . (KRQN) ­ , ­ , .

29


(KLMN) ­ , ­ , . ( , ) ­ ( ). () ­ (QM), (S) . , () , (XB YB ). ( / = QS /SM). « » «» ­ . ­ , , . ­ , . ( ), = 3 ­ ­ 1 = 3 ­ 2 ­ 1 = 0

. 5.2. ( HCl ­ H2O).

2. -. (p=const) ­ ( ). 30


2.1. ­ . ­ ( ), ­ ( ). 2.2. ­ , .

. 5.3. .

2.3. ­ .

. 5.4. . 31


: ­ ( ) ­ , [ (), () L ()], = 3 ­ 3 = 0. ( ), - . ­ , ( ). 2.4. , . , . .

.5.5. ,

: ( ) ( ), = 3 ­ 2 ­ 1 = 0 ( ). , . ( , ). 32


3. . ­ . T ­ ( ­ ) . : ­ ( ). ­ ( , ). (, ), () (X) ­ .

4. . 1. Pb Mg PbMg2, . , (1 2). , . 1) Pb ­ Mg. 2) . 3) , . 4) . . 5) : ; 1. , PbMg2. , E2. .

33


6. .
. 1. . 2. . 3. . 4. . . 5. . 6. pH () . 7. . 8. .

1. . ­ , , . ­ , , . , ­ , ( , ). 2. . 6.1. . s m(..)/100 - m(..)/ m(-) -


x

(..)/[(..) + (-] (..)/V(-) (..)/ m(-)
34 / () /

m


: «..» - , «-» - , «-» - ; m(-) = m (.) + m(-); %. ( ) 1) = m(..)/ m(-) m(..)/ m(-) = M/V = Mc/ 2) = m(..)/ m(-) m(..)/ m(-) = M/ m(-) = Mm/1000 ( m(-) , (m) ). 3) Mc/ = Mm/1000, = m/1000 ( /). 1: KNO3 (M = 101 /) 31 100 . 1160 /. , KNO3. , .

3. ­ , , . 6.2. . p p0x Km m cRT

T T



35


: 1) . p0 ­ , p ­ . 2) p1 = p10x1 = p10(1­x2), x2 = (p10­p1)/p =p1/p10, «1» , «2» - .
0 1

=

3) K ­ ­ , . 4) - ­ , . 5) ­ , , . ! /3 ( /, 1 /3 = 1000 /). 6) , i ( ), . : p1/p10 = ix2 (. 2) T = iKm T = im

= icRT
i = (k­1) + 1, k ­ , . 2. 4% BaCl2 0.302°. , E(H2O) = 0.52

4. . . 4.1. 2H2O H3O+ + OH
­

= a(H3O+)a(OH­)/a(H2O)2 [H3O+][OH­] = Kw Kw - . T = 22C = 295 Kw = 10
­14

. 36


, , Kw . 4.2. pH = ­lg [H3O+] 6.3. pH . [H3O+] [OH­] pH pH = 7 pH < 7 pH > 7

[H3O+] = [OH­] [H3O+] > [OH­] [H3O+] < [OH­]

5. 6.4. «» «» .



H+


OH­


HCl = H+ + Cl­ () NaOH = Na+ + OH­ () HCl () + NH3 () = NH4+ + ClBF3 () + NH3 () = NH3BF3





- (.. - ). 1. . CH3COOH + H2O - 1 . 2 CH3COO­ + H3O+ . 1 - 2

Ka (CH3COOH) = a(CH3COO­)a(H3O+)/a(CH3COOH) = [CH3COO­][H3O+]/[CH3COOH] ( ) Ka ­ CH3COOH 37


2. - . CH3COO­ + H2O 1 - 2 CH3COOH + OH­ - 1 . 2

Kb (CH3COO­) = a(CH3COOH)a(OH­)/a(CH3COO­) = [CH3COOH][OH­]/[CH3COO­] Kb ­ CH3COO­ K


1. . KaKb=([CH3COO­][H3O+]/[CH3COOH])([CH3COOH][OH­]/[CH3COO­]) = = [H3O+][OH­] = const ( ) = Kw 2. () ( ). K = [CH3COOH][OH­] / [CH3COO­] = ([CH3COOH][OH­][H3O+])/([CH3COO­][H3O+]) = Kw/Ka ( ) K = Kw/Kb ( )

6. pH () . 3. pH 0.1 CH3COOH. Ka (CH3COOH) = 1.7510­ : CH3COOH + H2O CH3COO­ + H3O+
5

Ka (CH3COOH) = [CH3COO­][H3O+]/[CH3COOH] = [H3O+]2/(c(CH3COOH ­ [H3O+]) [H3O+]2/c(CH3COOH) ! , c(CH3COOH) >> [H3O+] [H3O+] =

K a c = 1.3210­3, pH = ­lg [H3O+] = ­lg (1.3210­3) = 2.88
5

4. pH 0.1 CH3COONa. Ka (CH3COOH) = 1.7510­ : CH3COO­ + H2O CH3COOH + OH­

K = w/Ka (CH3COOH) = [CH3COOH][OH­]/[CH3COO­] = [OH­]2/(c(CH3COONa) ­ [OH­]) [OH­]2/c(CH3COONa) ! , c(CH3COONa) >> [OH­] 38


. 6.5. pH . , K = Kw/Ka K = Kw/Kb pH pH > 7 pH < 7 Ka Kb pH = 7

K = Kw/(KaKb)

-

7. . AmBn (.) AmBn (p-p) mAn+ + nB
m­

K = [An+]m[Bm­]n/[AmBn(.)] = [An+]m[Bm­]n = AmBn ­ : AmBn (p-p) . ­ . [An+]m[Bm­]n > AmBn [An+]m[Bm­]n < AmBn ( ) [An+] = mc, [Bm­] = nc, AmBn = [An+]m[Bm­]n = (mc)m(nc)n = mmnnc c=
m n

m+n


m m *n
n

5. () Mg3(PO4)2, Mg3(PO4)2 = 10­13. . n = 2, m = 3. =
5

10

13
2

33 *2

= 9.8510­4 .

39


8. . 1) LiNO2 70 1.06 . % ? 2) , 0.98. K(H2O) = 1.86. 3) . 4) pH . 1010 /. a (HNO2) = 5.110­
4

5) , 0.03 NaF? LiF = 1.710­
3

40


7. ­ ­ 1.
. 1. . 2. . 3. - - . 4.

1. . ­ , . : ( ), . , ( ­ ) ( ) ­ , Fe+8/33O­24, S+2/55Cl­12, K+1I­1/33. . ­ ( ), ­ ( ). ­ , , ­ , . , . (.. - , ). ­ - , . : Cl20 + 2KOH = KCl­1 + KOCl+1 + H2O 41


- - , . : 2H2S­2 + S+4O2 = 3S0 + 2H2O

2. . : ­ , (F2, Cl2, O2). (HClO, SeO2, HNO3). , d- (KMnO4, K2Cr2O4, V2O5). , 6p - (PbO2, KBiO3). , (Cu2+, Ag+, Fe3+). (K2S2O8). : ­ ( , ). ­ (H2, C, Si). C (LiH, H2S, HI). ( ) (Na2S2O3, KH2PO2, CO). (Cr2+, Sn2+, Mn2+). , : ( ) ( ) (Na2SO3, NaNO2). d- ( 0 ) (Cr3+, VO2+). H2O2.

42


3. - - . - ( ) , , , , (, Mn+7 MnO4­, ). . 1) . 2) ( ) ( ). ! : , H+ , ­ OH­ . H+ OH­ - ! 3) . 4) , . 5) ( ), , , , , . 6) . 7) . 8) - . 9) ( ).

1. KMnO4 + FeSO4 + H2SO4 = MnSO4 + Fe2(SO4)3 + K2SO4 + H2O 5 10 2 MnO4­ + 8H+ + 5e = Mn2+ + 4H2O () 2Fe2+ ­ 2e = 2Fe3+ ()

2MnO4­ + 16H+ + 10Fe2+ = 2Mn2+ + 10Fe3+ + 8H2O 43


2KMnO4 + 10FeSO4 + 8H2SO4 = 2MnSO4 + 5Fe2(SO4)3 + K2SO4 + 8H2O : , Fe2(SO4)3 .

2. Zn + NaOH + H2O = Na2[Zn(OH)4] + H2 1 2 1 2H2O+ 2e = H2 + 2OH- () Zn + 4OH­ ­ 2e = [Zn(OH)4]2­ ()

Zn + 4OH­ + 2H2O = [Zn(OH)4]2­ + H2 + 2OHZn + 2OH­ + 2H2O = [Zn(OH)4]2­ + H2 Zn + 2NaOH + 2H2O = Na2[Zn(OH)4] + H2

3. Br2 + KOH = KBr + KBrO3 + H2O 1 10 5 Br2 + 2e = 2Br­ ()
­

Br2 + 12OH­ ­ 10e = 2BrO3­ + 6H2O ()

Br2 + 12OH­ + 5Br2 = 2BrO3­ + 6H2O + 10Br 3Br2 + 6OH­ = BrO3­ + 3H2O + 5Br
­

3Br2 + 6KOH = 5KBr + KBrO3 + 3H2O

4. . - -

1) K2Cr2O7 + FeSO4 + H2SO4 = Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 + H2O 2) HNO2 + KMnO4 + H2SO4 = HNO3 + MnSO4 + K2SO4 + H2O 3) K2Cr2O7 + H2O2 + H2SO4 = O2 + K2SO4 + Cr2(SO4)3 + H2O 44


4) KMnO4 + HCl = KCl + MnCl2 + Cl2 + H2O 5) KBr + MnO2 + H2SO4 = K2SO4 + MnSO4 + Br2 + H2O 6) Cu + HNO3 (.) = Cu(NO3)2 + NO + H2O 7) P + KOH = KH2PO2 + PH3 8) Al + NaOH + H2O = Na[Al(OH)4] + H2 9) Zn + NaNO3 + NaOH + H2O = Na2[Zn(OH)4] + NH3 10) Cu2S + HNO3 (.) = CuSO4 + Cu(NO3)2 + NO2 + H2O 11) K2Cr2O7 + H2S + H2SO4 = K2SO4 + Cr2(SO4)3 + S + H2O 12) Mn(NO3)2 + PbO2 + HNO3 = HMnO4 + Pb(NO3)2 + H2O 13) K3[Cr(OH)6] + Cl2 + KOH = K2CrO4 + KCl + H2O 14) Na2S2O3 + Cl2 + H2O = Na2SO4 + H2SO4 + HCl

45


8. ­ ­ 2.
1. . . 2. - . 3. . 4. . 5. (- ­ ). 6. .

1. . . . Mz+ (-) + ze M0 (.) () «-». . , . . () ­ , a(H+) = 1, 1 . , () = 0 . , .. () , , : = (Mz+/) ­ () = (Mz+/) ­ 0 = E0(Mz+/) ­ : 1) G0 = ­zFE0, z ­ , , F = 96500 / ­ . ­ - . 46


2) E0 ( G0) , , /, . 3) E0 , E0(Mz+/) Mz+ + ze = M0. 4) E0 > 0, G0 < 0, , . E0, - .

2. ­ . ­ , - (/). - : - 1 + - 2 - 1 + - 2

«-» ­ , «-» - . , E0 (- 1/- 1) > E0 (- 2/- 2). E0 () = E0 (- 1/- 1) - E0 (- 2/- 2) > 0. ! - 1 + z1e = - 1 - 2 + z2e = - 2 z1 z2 , E0 (- 1/- 1) E0 (- 2/- 2) - , E0 , (. .2 ). 1. E0 (Cu2+/Cu) = 0.337 , E0 (Zn2+/Zn) = ­0.763 . - , , E0. E0 (Cu2+/Cu) > E0 (Zn2+/Zn) ­ Cu2+ + Zn = Zn2+ + Cu Cu2+ ­ , Zn ­ . E0 () = E0 (Cu2+/Cu) ­ E0 (Zn2+/Zn) = 0.337 ­ (­0.763 ) = 1.1 : , ­ ­ ( ). 47


, ­ .

3. . G = G0 + RT ln (aCm aDn/aAk aBl) ­ - ( ) ­Fz: ­G/Fz = ­G0/Fz ­ RT [ln (a , G0 = ­zFE0, G = ­zFE, E = E0 ­ E = E0 +
C m

aDn/a

k A

aBl)]/Fz
k A

RT ln (aCm aDn/a Fz

aBl)

RT ln (aAk aBl/aCm aDn) ( ). , , Fz .
, . ! z z1 z2 . ­ -, . 1. MnO2 + 4H+ + 2Cl­ = Mn2+ + Cl2 + 2H2O (1) ? , pH ? ( +), , 1. E0 (MnO2/Mn2+) = 1.23 E0 (Cl2/Cl­) = 1.36 T = 298 : , E0 () = E0 (MnO2/Mn2+) ­ E0 (Cl2/Cl-) =1.23 ­ 1.36 = = ­0.13 , (1) . (1) : E = E0 + = E0 +

RT ln (a Fz

k A

aBl/a

C

m

aDn) =

RT 2 RT ln [a(H+)]4 = E0 + ln [a(H+)] 2F F

, E > 0, E0 + ln [a(H+)] > ­

2 RT ln [a(H+)] > 0, F

E0F , a(H+) > exp 2 RT

E0F 2 RT

, a(H+) > 12.575
48


pH = ­lg[H+], , , a(H+) = [H+], ­lg[H+] < ­lg 12.575 pH < ­1.10. 4. . ­ . : . (pH = 0), (pH = 14) . (, (­3) NH4+ NH3 ). A E10, z B 0 E3 , z3 = z1 + z
1

E20, z
2

2

C

G01 + G02 = G0

3

­z1E01F ­z2E02F = ­z3E03F z1E01 + z2E02 = z3E0
3

E03 = (z1E10 + z2E20) / z3 = (z1E10 + z2E20) / (z1 + z2) 1) Ei0 ( zi) ! 2) E20 > E10 (.. ), . : , - , .

2. (pH = 14), 1) E0 (NO3­/NO2­) 2) NO2­.

-0.86 NO3
­

0.88 NO2
­

-0.46 NO 49

0.76 N2O

0.94 N2

NO2


5. (- ­ ) ­ - (nE0) (n). .

: 1) . (, ) , , , . 2) . , , , , , .

. 8.1. . 1) 1, 2 3 (. 8.1.) : 2 > 1 > 3. , > > . 2) 1 0 2, 0 3. , 1 02, 03.

50


6. . 1. : K2Cr2O7 + NaI + H2SO4 Cr2(SO4)3 + Na2SO4 + K2SO4 + I2 + H2O,
0 ) r G298 , 8.1.

8.1. .

Cr2 O
0 f H298 ,

2 7 (-)

I

(-)

Cr(3) ­236.1

I

2 ()

H 2O

()

/

­1491.9

­55.9

0

­285.8

S

0 298

,

/(·)

270.6
0 Cr2O

109.4

­265.1

116.2
0 I2

70.1

) E

2 7 (-)

3 / Cr(+) -

, , E

()

/ 2I

( )

= 0.536 .

2. (pH=14), : ) E0 (BrO3­/Br2); ) Br2 Br­ BrO3­ ( ).

0.495 BrO3
­

0.455 BrO­ Br
2

1.065 Br
­

51


9. ­1.
. 1. . . 2. . 3. . 4. . 5. .

1. . . . ­ , . : (x, y, z); ; (.. ); : ||2 (x, y, z) . , 95%, . ­ , . H = E H ­ ( ­ , ). ­ . . (« », ). 52


2. . . 3 (n, l, m), (s) ­ . 9.1. , . 1, 2, 3, ... n En ­

1 n2

0, 1, ... , n­1 l l = 0 ­ s- () l = 1 ­ p- () l = 2 ­ d ­ () l = 3 ­ f ­ () l, l­1,...,0,..., ­l 1 s ­ 3 p ­ (px, py, pz) 5 d ­ (dxy, dxz, dyz, dx2-y2, dz2) 7 f ­ s +1/2, ­1/2



m

53


)
s
z z y x

y x

z

)

y x

y x

px

p

y

pz

z

z

z

y x x z

y

y x
z

)

d

yz

dxy

dxz

y
x x

y

dz2

d

x2-y2

. 9.1. s- (), p- (), d- () .

, , ­ , . 54


4. . 4.1. ­ , . 4.2. ­ . 4.3. ­ l , (.. s). 4.4. : 1. n + l. 2. n + l n. : 4s ­ 3d ­ 4p 1. 4s (n + l = 4 + 0 = 4). 2. 3d (n + l = 3 + 2 = 5, n = 3). 3. 4p (n + l = 4 + 1 = 5, n = 4). : 1) , «» : Cr 3d54s1 3d44s2, Cu 3d104s1 3d94s2. 2) d ­ s ­ (V2+ 3d34s0, 3d14s2). 3) , m = max. 1. 9.2. . 9.2. . nl m s 1/2 1/2 K [Ar]4s
1 1

Ca [Ar]4s

2 10 6

Sc [Ar]4s23d

... Zn [Ar]4s23d
1

Ga [Ar]4s23d104p

... Kr [Ar] 4s23d104p

322 220

3 2 ­3 ­1/2 410 0

55


1) , . 2) , . 3) .

4. . 4.1. . ­ , . (, , ). : ­ ( ). d- f- ( , ). ­ ( , ). d ­ (d ­ ) f ­ ( ). 4.2. () I ­ , . In+1 > In ( ). ­ , . 4.3. ( ) Ae ­ . , .. , . , , -. / .

4.4. () ­ , , . , : . ­ Fr, ­ F. ­ , ­ . ­ , ­ . ­ , ­ . . 56


4.5. ( .)­, . .



.

= 2 S ( S 1) =

n(n 2) ( ­ ).

S ­ , n ­ .

5. . 1. d ­ . Fe3+.

2. . . ) F­, Cl­, Br­. ) Cl­, Ar, K+. ) Nd3+, Gd3+, Ho3+, Yb3+. ) V2+, V3+, V4+, V5+.

57


10. -2.
. 1. (). 2. . 3. (). 4. . 5. , . 6. .

1. (). 1.1. () ­ ) . 1) , . 2) ( , ) , , .. . 3) , . 4) , . 5) , , .

1.2. . 1) s- p-. 2) . 3) «» : , , , .

58


4) , 6. 2. . AXnE A ­ . ­ . ­ . 10.1 . n+m 2 180° n 2 3 2 4 4 109.5° 3 2 5 5 120° 180° 4 3 2 6 6 90° 5 4 m 0 0 1 0 1 2 0 1 2 3 0 1 2 2 3 2 4 3 22 5 4 32 23 6 5 42 - BeCl BF3 SnCl CF4 NH3 H2O PF5 SF4 ClF3 XeF2 SF6 IF5 XeF4
2 m

2

3

120°

59


: , n + m = 5 , . , (120° 90°).

. 10.1. , . 60


m n: AXnE n ­ ,

m

n + m = [(N . e () + N . e () ± z) / 2] ­ d : N . e () ­ ( , ). N . e () ­ , . z ­ ( , «+», , «-»). d ­ . 1. , . CO2, Cl2O, BrF5, ICl2+, NF3, SOCl2. : SOCl n = 3 (O + 2 Cl) N . e () = 6 (S) N . e () = 4 (2(O) + 2(Cl)) z=0 d = 1 (S = O) m + n = [(6+4)/2] ­ 1 = 4 n = 3, m = 1: 3 ­ .
2

3. (). 1) () (), : ) ; ) . 2) , . 3) , . 4) , . 61


4. . 4.1.

. 10.2. 2. 1s ­ (1 2*). «» , , . «*» , ­ .

62


4.2.

. 10.3. 2. «» , , . 2p ­ ( ) ­ ­ . , 2p ­ (2px, 2py, 2pz), 2p ­ , , ­ ( , 2pz ­ ).

63


5. , . 5.1. N (O2) = (N . ­ N .) / 2 = (8­4) / 2 = 2. , ( , N . = N ., ). 5.2. , .
.

= 2 S ( S 1) =

n(n 2) =

8 = 2 2 = 2.83

5.3. , , ( ) (2p) , O2 (2*). . 10.2. O2 N
+ 1

O2 (2*) 2 2.83
2

O2

­ 3

(2*) 2.5

(2*) 1.5 1.73



.

,

1.73

O-O O-O

. (O2*) ­ .

. 10.4. (O2) (O2*) .

64


2. N2. : 1) . 2) . 3) N N2. . : 1 3 . .

. 10.5. N2.

65




2s 2p ­ , ( ) . , 2* ( 2s ­ ) 3 ( 2p ­ ) , 3 1 ( ).

6. . 1. , : XeO3, SO2, SO2Cl2, ICl2-, ICl4-, XeO3F-, IO2F4-.

2. 2 2+ 2-. : ) ; ) ;

3. 2 ) ; ) ?

+

2

2-

66


11. ­ 1
. 1. . 2. . 3. . 4. . 5. . 6. .

1. .
9

F

17

Cl

35

Br

53

I

85

At

[ ]ns2np

5

: ) ­ , , ( ), ­1; ) ; ) ­ ; ) , ; ) .

2. . - , . 67


: CaF2 , 3Ca3(PO4)2CaF2 : NaCl , KCl , NaClKCl , KClMgCl26H2O : , - ( ). : ,

11.1. KF 2KF = 2K + F2 F HF KFHF KF2HF NaCl Cl 2NaCl + 2H2O = 2NaOH + H2 + Cl2 tC 2CoF3 = 2CoF2 + F2 HCl (.) (KMnO4, MnO2, K2Cr2O7, PbO2, KClO3) MnO2 + 2H2SO4 + 2KX = X2 + + MnSO4 + K2SO4 + 2H2O (X=Br, I) 2CuSO4 + 4KI = 2CuI + I2 + + 2K2SO4

Br, I

2KX + Cl2 = 2KCl + X2 (X=Br, I)

68


3. ­ X2: 1, . 3.1. F2 Cl
2

Br

2

I

2

T (-- ) : F2 ­ -, Cl2 ­ -, Br2 ­ -, I2 ­ . 11.2. « ­ » (/) F Cl Br I

X-X 155 238 190 149 : 1) , - , , . 2) Cl-Cl, F-F - , .

3.2. : H2 + X2 = 2HX X = F ­ X = Cl ­ X = Br ­ 200°C X = I ­ ,

4. . 4.1. : (. ). HF HCl. 69


tC CaF2 (.) + H2SO4 (.) = CaSO4 + 2HF tC NaCl (.) + H2SO4 (.) = NaHSO4 + HCl tC KX (.) + H3PO4 (.) = KH2PO4 + HX (X = Br, I) ­ H2SO4 (.) KX X2 PX3 + 3H2O = H3PO3 + 3HX (X = Br, I) PX3 , , , . tC KHF2 = KF + HF H2S + I2 (aq) = 2HI + S 4.2. HF HCl HBr HI (HF ­ ) H ­ X H ­ X ( ) X­ ( )

4.3. HF: ) , , (HF)n (n=2-6 ).

70


. 11.1. .

) , HF ­ , : () (, , KHF2). HF.

. 11.2. pKa (pKa = ­lgKa)

) . Na2OCaO6SiO2 + 28HF () = NaF + CaF2 + 6SiF4 + 14H2O ( ) Na2OCaO6SiO2 + 36HF (aq) = Na2[SiF6] + Ca[SiF6] + 4H2[SiF6] + 14H2O ( ) 5. . : XYn, Y ­ , n ­ ; ­ ; ( , ); 71


BrF5 + 6NaOH = 5NaF + NaBrO3 + 3H2O 3ICl3 + 12NaOH = 9NaCl + NaI + 2NaIO3 + 6H2O [XY
n+1

]­ [XYn-1]+.

: K[ICl4] 2H2O : ICl3 + KCl + 2H2O = K[ICl4]2H2O ( ) KI + 2Cl2 + 2H2O = K[ICl4]2H2O I2 + 2KClO3 (.) + 12HCl (.) + 4H2O = 2(K[ICl4]2H2O) + 6H2O + 3Cl2 KIO3 (.) + 6HCl (.) = K[ICl4]2H2O + Cl2 + H2O

6. . 1000 1 ., ( ) 3.510­4 (Cl2), 2.310­3 (Br2), 2.810­2 (I2). . 1. H-X HF HI, : X2 X2, / H2 () 432 F2 () 155 I2 (.) 149

HX fH0
298

HF () , / ­268

HI () +26

62 /.

2. ( ): [IF2]­, BrF3, [IF4]­, I3­, ClF5, [IF4]+?

72


12. ­ 2.
. 1. . 2. 3. . 4. . 1. . 1.1. : ; , ; ( , ), ­ . 1.2. : OF2 ­ , - . 2F2 + 2NaOH (.) = OF2 + 2NaF + H2O OF2 + 2NaOH (.) = O2 + 2NaF + H2O 1.3. . 12.1. .
Cl2O - 2HgO + Cl2 = HgOHgCl2 + + Cl2O (0°C, CCl4) 2KClO3+SO2+H2SO4 = =2KHSO4 + 2ClO2 2KClO3+H2C2O4+H2SO4 = =K2SO4+2ClO2+2CO2+2H2O ClO2 + O3 = ClO3 + O2 (0°C) 2HClO4+P2O5 = Cl2O7+2HPO Cl2O + H2O = 2HOCl

ClO2

-

2ClO2 + H2O = HClO2 + + HClO3

ClO3 (Cl2O6) Cl2O7



2ClO3 + H2O = HClO3 + + HClO4
3

Cl2O7 + H2O = 2HClO4

73


1.4. ­ , . Br - O , . : 4p (Br) - 2p (O) , 3p (Cl) - 2p (O) - . , - I-O . 1.5. : I2O5 ­ . : 2HIO3 = I2O5 + H2O ( ) : I2O5 + 2NaOH = 2NaIO3 + H2O

2. 2.1. 12.2. . Cl Cl Cl Cl Br Br Br I I I I +1 +3 +5 +7 +1 +5 +7 +1 +5 +7 +7 HOCl HClO HClO HClO
2 3 4





HOBr HBrO HBrO HOI HIO3 HIO4 H5IO6
3 4

74


2.2. HOCl 2Cl2 + 2HgO + H2O = HgOHgCl2 + 2HOCl ( Cl2O) HClO
2

ClO2 + Ba(OH)2 + H2O2 = Ba(ClO2)2 + 2H2O + O2 Ba(ClO2)2 + H2SO4 = BaSO4 + 2HClO HClO
3 2

tC 6KOH + 3Cl2 = KClO3 + 5KCl + 3H2O ( : KClO3 , KCl - ) KCl + 3H2O = KClO3 + 3H2 () Ba(ClO3)2 + H2SO4 = BaSO4 + 2HClO HClO
4 3

tC 4KClO3 = KCl + 3KClO

4

KClO3 + H2O = KClO4 + H2 () tC KClO4 + H2SO4 = KHSO4 + HClO4 ( ) HBrO
3

Br2 + Cl2 + 12KOH = 2KBrO3 + 10KCl + 6H2O ( KClO3-KCl) Ba(BrO3)2 + H2SO4 = BaSO4 + 2HBrO HBrO
4 3

KBrO3 + XeF2 + H2O = KBrO4 + 2HF + Xe ( ) HBrO4 KBrO4 HIO3 tC I2 + 10HNO3 (.) = 2HIO3 + 10NO2 + 4H2O

75


HIO4 H5IO6 tC 5Ba(IO3)2 = Ba5(IO6)2 + 4I2 + 9O2 Ba5(IO6)2 + 5H2SO4 = 5BaSO4 + 2H5IO6 tC H5IO6 = HIO4 + 2H2O ( )

2.3. HOX H-O-X HXO2 H-O-X=O

HXO3:

HXO4

H5IO6

3. . 3.1. . : () , H - O, , , HOCl < HClO2 < HClO3 < HClO4 : , H - O, , .. , ­ . 3.2. . : , , , , , HOCl > HClO2 > HClO3 > , HClO4

76


: ( Br - O, . ). , : 2KBrO3 + Cl2 = 2KClO3 + Br2 2KBrO3 + I2 = 2KIO3 + Br
2

­ X = F: 2F2 + 2H2O = 4HF + O2 X = Cl ­ I: ) ; ) ­ , X2 (8Cl246H2O); ) X2 + H2O HX + HOX (1) ) HOX: 3HOX 2HX + HXO3 (2) (1) Cl > (1) I (2) Cl < (2) I

4. . . Cl2 (1), 0.76 % 25°C. 1) (1) , E0(Cl2/Cl­) = 1.36 , E0(HClO/Cl2) = 1.63 . 2) (1) : ) ; ) ; ) ; ) ? 3) pH . , = 1 /, HCl = 1.

77


. 1. . NaOH ClO2 KCl HCl Cl2 KClO3 K[ICl4]2H2O ...

2. , :

1.05 BrO4
­

0.54 BrO3
­

E0 BrO
­

x

1.07 Br
2

Br

­

0.52 1) (pH=0 pH=14) ? 2) E0x. 3) BrO­ Br2 BrO3­. E0.

78


13. ­ 1.
. 1. . 2. . 3. . . 4. . 5. . 6. .

1. .
8

O

16

S

34

Se

52

Te

84

Po

[ ]ns2np

4

: ) , ; ) 16 ( ) ­2 ; ) , ( ); ) ( ). 13.1. «-» (/) O X-X S Se Te

146 265 192 218

X=X 494 421 272 126 79


: 1) E(X=X) > 2E(X-X), E(X=X) < 2E(X-X): , ­ ( ...­X-X-X-...). , - ( ). 2) E(S-S) > E(Te-Te) > E(Se-Se): . 2. . , . : ( ), (O2), , , . : , , H2S . : , . : , . 13.2.
tC 2KMnO4 = K2MnO4 + MnO2 + O2 tC 2BaO2 = 2BaO + O2 2Na2O2 + CO2 = 2Na2CO3 + O2 ( ) 1) . 2) 2H2S + O2 = 2S + 2H2O , .

O

1) . 2) .

S

80


Se, Te



, .

3. . . 3.1. , , 13.3. O O2 (O=O) O O
3





S S



S8, S8, S

-

S Se Se



n

Se

8



Sen, Ten,

Te





Po



-

: 1) . 81


.

. 13.1. .

3.2. ( ) . O3 + 2KI + H2O = I2 + O2 + 2KOH :
tC 3X + 6NaOH = 2Na2X + Na2XO3 + 3H2O

, . Na2S2O3. :
tC S + 2H2SO4 (.) = 3SO2 + 2H2O tC S + 6HNO3 (.) = H2SO4 + 6NO2 + 2H2O

82


4. . 4.1. : H2 + X = H2X (X = O, S) FeS + 2HCl = FeCl2 + H2S Al2Se3 + 6H2O = 2Al(OH)3 + 3H2Se CnH2
tC () + (n+1)X = (n+1)H2X + nC (X = S, Se)

n+2

4.2. H2O H2S H2Se H2Te (H2O ­ ) H ­ X H ­ X ( , H2O - ) ( )

5. . ­ . 5.1. :
tC Fe + S = FeS


tC BaSO4 + 4C = BaS + 4CO, tC BaSO4 + 4H2 = BaS + 4H2O

Cu2+ + S2- = CuS

83


5.2. 13.4. . , , NH4 Mn2+, Fe2+, Zn2+ Cd2+, Co2+, Ni
2+ +

, MS + 2H2O = M(OH)2 + H2S - - « » (HNO3 . + HCl .)

Cu2+, Pb2+, Sn2+, Bi3+, Ag+ Hg2+

6. . , - . CuS + HNO3 (.) = CuSO4 + NO2 + H2O HgS + HNO3 (.) + HCl (.) = H2[HgCl4] + H2SO4 + NO + H2O

. 1. , : ) , , , , D, ? ) , , , ? 2. , , . , . .

84


14. ­ 2.
. 1. . 2. 3. . 4. . 5. . 1. . 1.1. SOn SeOn TeOn (n = 2, 3) ) (

1.2. 14.1. .
S + O2 = SO SO2
2





Na2SO3 + 2HCl = 2NaCl + SO2 + H2O tC Cu+2H2SO4 (.) = 2CuSO4+SO2+2H2O

SO2 + H2O = H2SO3

SeO

2



tC Se + 2NO2 = SeO2 + 2NO Te + O2 = TeO

SeO2 + H2O = = H2SeO3

TeO

2

2

85


SO3



tC 2SO2+O2 = 2SO3 ( V2O5) tC Na2S2O7 = Na2SO4 + SO3 H2SeO4 + P2O5 = SeO3 + 2HPO tC H6TeO6 = TeO3 + 3H2O
3

SO3 + H2O = H2SO4

SeO

3



SeO3+H2O = H2SeO4

TeO

3

2. 2.1. 14.2. S Se Te S Se Te +4 +4 +4 +6 +6 +6 H2SO3 H2SeO3 TeO2xH2O H2SO4 H2SeO4 H6TeO6

2.2. X(+4) XO2 + H2O = H2XO3 (X = S, Se) TeCl4 + (x+2)H2O = TeO2xH2O + 4HCl X(+6) H2SO4 ­ : ) : 2SO2 + O2 tC, p, V2O5 2SO3

86


SO3 + H2O = H2SO4 ( SO3 H2SO4, ) ) SO2 + NO2 + H2O = H2SO4 + NO , . H2SeO3 + H2O2 (.) = H2SeO4 + H2O Te + 3H2O2 (.) = H6TeO6

2.3.

H2XO3

H2XO4

2.4. . 14.3. .

H2S2O3





H2SnO6





H2S2O7





87


H2SO5

( )



H2S2O8





2.5. ­
tC Na2SO3 + S = Na2S2O3 ()

Na2S2O3 + H2SO4 = Na2SO4 + S + SO2 + H2O ( ) 2Na2S2O3 + I2 = Na2S4O6 + 2NaI ( ) Na2S2O3 + 4Cl2 + 5H2O = 2NaHSO4 + 8HCl ( ­ «», Br2) ­ 2KHSO4 = K2S2O7 + H2O (t1 C) K2S2O7 = K2SO4 + SO3 (t2>t1) ­ 2H2SO4 = H2S2O8 + H2 () 2KHSO4 = K2S2O8 + H2 () 2K2S2O8 + 2H2O = 2H2SO5 + 2K2SO4 () E0 (S2O82­/SO42­) = 2.01 ­

3. . : H2SO4 H2SO3, H2SO4 () .

88


: H2SO3 , H2SO4 ( H2SO3 ). , H2SO4 H2S, H2SO3 H2SO3 + 2H2S = 3S + 3H2O

4. . 14.4. .
( ) ( )




PCl5+SO2= = POCl3 + SOCl


SOCl2 + 4NaOH =
2

SOCl2

= Na2SO3+2NaCl+2H2O

SO2+Cl2 = SO2Cl2 ( )

SO2Cl2

SO2Cl2+4NaOH = = Na2SO4+2NaCl+2H2O

5. . . BaSO4, . . . 1. . ... S, tC FeS SO2 NO2, H2O X NaOH SOCl
2

K2S2O8

tC KHSO4 ... K2S2O7 ...

X ­ , . 89


2. , :

. 14.1. .

1) , , . 2) ­2 ? 3) ?

90


15. ­ 1.
. 1. . 2. . 3. . . 4. XH3. 5. 6. .

1. .
7

N

15

P

33

As

51

Sb

83

Bi

[ ]ns2np

3

: ) (N2) (Bi); ) , ; ) , , , . ) Bi(+5), 6s2 ­ . 15.1. «-» (/). N X-X P As Sb Bi

160 209 146 121 104

XX 942 480 380 295 192 91


: 1) E(XX) > 3E(X-X), E(XX) < 3E(X-X), .. ( N2 ), ­ . 2) , , -, P - O ( P - O 407 /, S - O 265 /).

2. . , . : N2 ( ), KNO3 ( ), NaNO3 ( ), (). : Ca3(PO4)2 (), 3Ca3(PO4)2CaA2 (A = F , = OH ). , , ­ X2S3. 15.2.
tC NH4NO2 = N2 + 2H2O N tC 2NaN3 = 2Na + 3N2 ) (

P

tC 2Ca3(PO4)2+6SiO2+10C = = P4 + 6CaSiO3 + 10CO tC 2X2S3 + 9O2 = 2X2O3 + 6SO2 tC X2O3 + 3C = 2X + 3CO

, . tC Sb2O3 + 3C = 2Sb + 3CO tC Bi2O3 + 3H2 = 2Bi + 3H2O

As, Sb, Bi

92


3. . . 3.1. , , 15.3. . N P P P As As Sb Bi N2 (NN) P
4

- -

P8 P9 P6 As
4

As6 Sb6

3.2. : tC P4 + 3KOH + 3H2O = PH3 + 3KH2PO2 : - P + 5HNO3 (.) = H3PO4 + 5NO2 + H2O Bi + 4HNO3 (.) = Bi(NO3)3 + NO + 2H2O ( . HNO3)

4. XH3. 4.1. : ­ tC, p, Fe N2 + 3H2 2NH3 ( ) 93


tC Ca(OH)2 + 2NH4Cl = 2NH3 + 2H2O + CaCl PH4I + KOH = PH3 + KI + H2O Mg3N2 + 6H2O = 3Mg(OH)2 + 2NH3 4Zn + NaNO3 + 7NaOH + 6H2O = 4Na2[Zn(OH)4] + NH3 (. ).

2

4.2. NH3 PH3 AsH3 SbH3 (BiH3 ) (NH3 ­ ) H ­ X H ­ X ( ) ( ) 4.3. XH3 1) NH3 NH3 + H2O NH3H2O NH4+ + OH ( «NH4OH» , NH3H2O).
­

2) PH3 (HI, HClO4). .

5.

5.1. N2H4

94


: 2NH3 + 2NaOCl = N2H4 + 2NaCl + H2O : «» : ) ; ) ­ , ; ) ( R2=O) R2=N-NH2 : . ) , , ( ), ( ) N2H4 + H2O N2H4H2O N2H5+ + OH­ ) - . , N2H4 + 4CuSO4 + 8NaOH = 2Cu2O + N2 + 4Na2SO4 + 6H2O : CuSO4 + 4NH3 = [Cu(NH3)4]SO4 ­ N2H6Cl2 + 2H3[TiCl6] = 2H2[TiCl6] + 2NH4Cl ) N2H4 + O2 = N2 + 2H2O (N2H4 ­ )

5.2. NH2OH

: 2NO + 3H2 + H2SO4 = (NH3OH)2SO4 (Pd ) (NH3OH)2SO4 + 2KOH = K2SO4 + 2NH2OH + 2H2O : ) , , ( ). 95


NH2OH + H2O NH3OH+ + OH­ ) - : ­ N2, N2O ( NH2OH N - O) ­ NH3 ) , tC 3NH2OH = NH3 + N2 + 3H2O

5.3. NH3 N2H4 NH2OH ( 3H > 2H+NH2 > 2H + OH) ( N2, )

5.4. HN3 : tC N2O + NaNH2 = NaN3 + H2O NaN3 + H2SO4 (.) = NaHSO4 + HN3 : ) ­ () ( ) HN3 H+ + N3­ ( ­ ) ) - : , «HN3-HCl» « » ) ­ N2 M(N3)x = M + 3x/2 N2 M ­ ­ . M ­ ­ ­ . 96


6. . . , : ­3.40 N2 N3
­

­2.88 NH2OH

0.73 N2H4

0.15 NH3

1) ( ) ? 2) E0 (N3­/N2H4). 3) ? , .

. 1. 2NH3OH+ + Cl2 = N2 + 4H+ + 2Cl­ + 2H2O 1) G0 . 2) , E0 (Cl2/Cl­) = 1.36 , E0 (N2/NH3OH+) N2 () Cl­ (-) NH3OH+ (-) Cl2 () H2O () fH0 S
0 298 298

, / 0 200

­167 57

­98 167

0 223

­286 70

, /

2. N - N , ­46.2 95.4 / . 431 950 / .

97


16. ­ 2.
. 1. . 2. . 3. . 4. . 5. . 6. .

1. . 1.1. : ( NO : , 2000); , , ; .

1.2. 16.1. .
N2O - tC NH4NO3 = N2O + 2H2O 3Cu + 8HNO3 (30%) = 3Cu(NO3)2 + + 2NO + 4H2O NO 2KNO2 + 2KI + 2H2SO4 = 2NO + + 2K2SO4 + I2 + 2H2O 4NH3 + 5O2 = 4NO + 6H2O ( Pt/Rh)

98


N2O

3



NO + NO2 N2O3 ( 0C) Cu + 4HNO3 (.) = Cu(NO3)2 + + 2NO2 + 2H2O

N2O3 + H2O = =2HNO2

NO2 (N2O4)

, ()

tC 2Pb(NO3)2 = 2PbO+4NO2+O2 2NO + O2 = 2NO2

2NO2 + H2O () = = HNO2 + HNO3

N2O

5



2HNO3 + P2O5 = 2HPO3 + N2O

5

N2O5 + H2O = =2HNO3 P2O3 + 3H2O = =2H3PO3 P2O5 + H2O = 2HPO
3

P2O3 (P4O6) P2O5 (P4O10)

P4 + 3O2 = 2P2O3 ( O2)

P4 + 5O2 = 2P2O

5

P2O5 + 3H2O = =2H3PO4

2. . 2.1. . 16.2. . N N P P P P P +3 +5 +1 +3 +5 +5 +5 HNO2 HNO3 H3PO2 H3PO3 HPO3 H3PO4 H4P2O7

99


2.2. , . 16.3. .
HNO
2

Ba(NO2)2+H2SO4 = BaSO4 + + HNO2 4NO2 + 2H2O +O2 = 4HNO
3

H-O-N=O

,

HNO

3

tC KNO3 (.) + H2SO4(.) = = KHSO4+HNO3 tC 2P4 + 3Ba(OH)2 +6H2O = = 3Ba(H2PO2)2 + 2PH3 Ba(H2PO2)2 + H2SO4 = = BaSO4 + 2H3PO2

,

H3PO2

,

H3PO3

P2O3 + 3H2O = 2H3PO3

,

P2O5 + 3H2O = 2H3PO4 H3PO4 tC Ca3(PO4)2 + 3H2SO4 = = 3CaSO4 + 2H3PO4

,

H4P2O

2H3PO4 = H4P2O7 + H2O
7

(200-250C)

,

HPO3 [(HPO3)n]

H4P2O7 = 2HPO3 + H2O (350-400C)

(n=3) (n=)

,

100


(HPO3)3 :

. 16.1. .

2.3. , - NO, N-O, 1.5. . , ( !) - P - H. :

NaH2PO2 + 4AgNO3 + 2H2O = H3PO4 + NaNO3 + 3HNO3 + 4Ag ( ) Na2HPO3 + 2AgNO3 = NaNO3 + Ag2HPO3 ( ) tC Ag2HPO3 = HPO3 + 2Ag ( ) Na2HPO4 + 3AgNO3 + NH3 = 2NaNO3 + NH4NO3 + Ag3PO4 ( ) Na2H2P2O7 + 4AgNO3 + 2NH3 = 2NaNO3 + 2NH4NO3 + Ag4P2O7 ( ) NaPO3 + AgNO3 = NaNO3 + AgPO3 ( ) HPO3 , H4P2O7 . : ) ; 101


) , ( ); ) : , . 2.4. 16.4. . 60% «» 20-60% «» <20% 10-20% <10% « » NO2 (Fe, Cr, Al, Bi .) ­



H2 H H
2

NO N2O N2 NH4NO3 , , Fe(NO3)2, Sn(NO3)2

2

: « H2» « H2» (S, C, P, As, Si) , , NO2. « » - HCl HNO3 . HNO3 , HCl ­ . HNO3 + HF.

102


3. . 3.1. NO2 (N2O4). , N2O4 N2O4NO+ + NO3­ NO3­, ­ NO+. (, ) N2O4 : Cu + 2N2O4 (.) = Cu(NO3)2 + 2NO .

3.2. 16.5. . , ( ) (Mg-Cu ) ( Cu) NH4
+

M(NO2)x + O2 MxOy + NO2 + O2 M + NO2 + O2 N2O ( )

: MxOy , , tC Sn(NO3)2 = SnO2 + 2NO2 4. . HNO2 ­ HNO3: HNO3 , HNO ( HOCl ­ HlO4 H2SO3 ­ H2SO4).
2



: . : P-H (.. 103


), . , : H3PO2 > H3PO3 > H3PO4. . , . H3POn , , ( ): H3PO2 (1) > H3PO3 (2) > H3PO4 (3) +5 : HPO3 (1) > H4P2O7 (2) > H3PO4 (3) : , , , ( , ).

5. . 5.1. ­ , , -. 5.2. Bi(OH)3 . Bi3+ : Bi3+ + H2O BiO+ + 2H+ 5.3. Bi(+5) ­ ( 6s2- ) . ­ . : Bi(OH)3 + 3KOH + K2S2O8 = KBiO3 + 2K2SO4 + 3H2O 6. . . : NaNO2, NaH2PO2, Na3PO4, NaNO3. , . . . 1. , . - .

104


... P
tC

KNO3

HNO3 (.)

NH4NO

3

... CuSO4, KOH

NH4NO3

NH3

N2H4

...

2. , :

. 16.1. . 1) : ) , ) ? 2) (+3) ? 3) ? (E0 Ni2+/Ni) = ­0.27 ). 105


17. .
. 1. . 2. . 3. . . 4. , . 5. . 6. . 7. . 8. .

1. .
6



14

Si

32

Ge

50

Sn

82

Pb

[ ]ns2np

2

: ) +2 +4, , ­ . ) , ( ). ) ­ ­ , -. - ­ . ) ­ Si-O ( ) Si-F. ) ­ , Pb(+4) ­ ( 6s2 ­ ).

106


2. . : CO2 ( ), (, ), , (, , , , ), (, ). : ( SiO2, ). : , : SnO2 (). : PbS (). : tC SiO2 + 2C = 2CO + Si ( SiC) tC SiCl4 + 2Zn = 2ZnCl2 + Si ( ) tC SnO2 + 2C = 2CO + Sn tC 2PbS + 3O2 = 2PbO + 3SO2 tC PbO + C = Pb + CO 3. . . 3.1. , , 17.1. , . , . . , 107 , .














60, 70 .. « », - =C=C=C=C=







-CC-CC , ( )



C Si Ge Sn Pb



- - - -

3.2. : Si + 4NaOH = Na4SiO4 + 2H2 tC Sn + 2NaOH + 2H2O = Na2[Sn(OH)4] + H2 : , - C + 4HNO3 (.) = CO2 + 4NO2 + 2H2O 3Si + 4HNO3 (.) + 18HF (.) = 3H2[SiF6] + 4NO + 8H2O ( HF - SiO2) Sn + 2H+ = Sn2+ + H2 ( , , E0 (Sn2+/Sn) = ­0.14 3Pb + 8HNO3 (30%) = 3Pb(NO3)2 + 2NO + 4H2O

108


4. , 4.1. : ) ; ) XnH2 . ) ­ . SinH2
n+2 n+2

n

­ ­

: 4Mg + SiO2 = Mg2Si + 2MgO () Mg2Si + 4HCl = 2MgCl2 + SiH4 4.2. : ) SiH4 + 2O2 = SiO2 + 2H2O ) SiH4 + 2H2O = SiO2 + 4H2 ) ­

5. . 17.2. .
- HCOOH = CO + H2O H2C2O4 = CO + CO2 + H2O CO tC H2SO4 (.) C + H2O = CO + H2 (-) 2 + O2 = 2CO ( ) CO C + O2 = CO2 CO2 + H2O CO2H2O H2CO3 H++HCO3

2

­

SiO

2



109


GeO2



tC Ge + O2 = GeO

2



Sn(OH)2 = SnO + H2O SnO - SnC2O4 = SnO + CO + CO2 tC Ar SnO2

PbO

tC 2PbS + 3O2 = 2PbO + 2SO2 3Pb + 2O2 = Pb3O4 (500C) PbO + NaOCl = PbO2 + NaCl Pb3O4+4HNO3 = PbO2+2Pb(NO3)2 + + 2H2O



Pb3O

4



PbO2



: CO , CO Mx(CO)y. CO2 , CO2 , SO2, . SiO2 (, , ..) PbO . Pb3O4 () Pb
2 +2

Pb+4O4

6. . : H2CO3 (SiO2nH2O) : ( ). 110


: , , .

: H2CO3: , H+ HCO3­, CO2H2O; (), () , 2NaHCO3 = Na2CO3 + H2O + CO2 SiO2nH2O: , , ; , ­ , , . 7. . 7.1. ­ , , -. 7.2. Pb(OH)2 . 7.3. Pb(+4) ­ , ( Bi(+5)). Pb(+4): 1) PbO2 (. ) ­ PbO2 + 4HCl = PbCl2 + Cl2 + 2H2O 2) (NH4)2[PbCl6] ­ Pb(+4) : 2NH4Cl + PbCl2 + Cl2 = (NH4)2[PbCl6] 3) Pb(CH3COO)
4

: Pb3O4 + 8CH3COOH = Pb(CH3COO)4 + 2Pb(CH3COO)2 + 4H2O ( «» ) : Pb(CH3COO)4 + 2H2O = PbO2 + 4CH3COOH 111


8. . . , , , . .

. 1. SnS 10 0.002 (II) 10 0.002 ? fG0 Sn2+ (-), S2­ (-) SnS () ­27.3, 92.5 ­108.3 /.

2. , . - . tC X1 HNO3 ...

Pb3O4

X2

Mn(NO3)2, HNO3 X1 HCl . ...

H2S

X3

PbO

Pb

Xi ­ , .

112


18. .
. 1. . 2. . 3. . . 4. . . 5. . 6. . 7. .

1. .
5

B ­ 13 , .
1

[He]2s22p :

) «» ­ ; ) +3; ) B - Si ­ , , .. , ; ) ( ), - ; ) .

2. . . . () Na2B4O710H2O Ca2B6O1111H2O. 113


tC Na2B4O710H2O = Na2B4O7 + 10H2O tC Na2B4O7 + 3Mg = 2B + 2NaBO2 + 3MgO ( MgB2) tC 2BI3 = 2B + 3I2 ( )

3. . . : , () B12. : , tC B + 3HNO3 (.) = H3BO3 + 3NO2 tC B + 4NaOH + 3O2 = 4NaBO2 + 2H2O

4. . . 4.1. : ) ; ) ­ ; ) ; ) . ­ - ([BnHn]2­), - (BnHn+4), - (BnHn+6), - (BnHn+8). 4.2. ­ B2H6. : 2BF3 + 6NaH = B2H6 + 6NaF ( ) : , B-H-B.

114


. 18.1. ) . ) B-H-B.

4.3. . ) : B2H6 + 3O2 = B2O3 + 3H2O ) : B2H6 + 6H2O = 2H3BO3 + 6H2 ) .

4.4. . , ( [BH4]­) BCl3 + 4NaH = Na[BH4] + 3NaCl ( ) [BH4]­ NH4+. ­ . 2Na[BH4] + H2SO4 = Na2SO4 + B2H6 + 2H2

5. . 5.1. B2O3: . tC 4B + 3O2 = 2B2O3 tC H3BO3 = B2O3+ H2O

115


: , . 5.2. ­ (SiO2nH2O). : , ; . ; . : HBO2 ( ), H3BO3 ( ), H2B4O7 ( ). 5.3. : (HBO2)n ­ HPO3. ­ , : H3BO3 + H2O H+ + [B(OH)4]­ 5.4. . Na2B4O710H2O ­ ­ Na2[B4O5(OH)4]8H2O

. 18.2. [B4O5(OH)4]2

­

: B4O72­ + 7H2O 4H3BO3 + 2OH

­

: , ,

116


tC 2(Na2B4O710H2O) + 2Co(NO3)2 = 2Co(BO2)2 + 4NaBO2 + 4NO2 + O2 + 20H2O

: tC 3(NaNH4HPO44H2O) + 2Cr(OH)3 = 2CrPO4 + Na3PO4 + 3NH3 + 18H2O

Na2B2O4(OH)46H2O : Na2B4O710H2O + 2NaOH + 4H2O2 + H2O = 2(Na2B2O4(OH)46H2O) : [B2O4(OH)4]2­ [B2(O2)2(OH)4]2
­

. 18.3. [B2(O2)2(OH)4]2

­

6. . BX3 6.1. p ­ p - ­ 2p ­ p ­ - ­ B-X . 6.2. ( BF3): BF3 + NH3 = BF3NH3. 6.3. BX3 + 3H2O = H3BO3 + 3HX (X = Cl - I) 6.4. H[BF4] ­ H2[SiF6], . H3BO3 + 4HF = H[BF4] + 3H2O 4BF3 + 3H2O = 4H[BF4] + H3BO3

117


7. . . , . . B2O3B2H6Na[BF4]

. 1. . , . 2. , . .

118




1. .. , .. , .. , .. . . . . 1, 2. ­ .: , «, 2007. 2. . . .. . . 1, 2. ­ .: , 2004. 3. .. , .. , .. , .. . . .. . . ­ .: , 2004. 4. .. , .. , .. . . .. . . ­ .: , 2008. 5. .. , .. , .. . 1 . http://www.chem.msu.ru/rus/teaching/thermo/archive/welcome.html 6. .. , .. , .. , .. . 1 . - http://www.chem.msu.ru/rus/teaching/kazin/kazin1.pdf 7. . . . . . .. . ­ .: , 1993. 8. . , . . . . . .. . ­ .: , 1992. 9. . . .. . . 1. ­ .: , 1964. 10. .. , .. , .. , .. , .. , .. , .. , .. . . . 1, 2. ­ .: , 1995. 11. .. , .. . . .: . , 2006.

119