Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.inorg.chem.msu.ru/study/seminary_baku_2014_11.pdf Äàòà èçìåíåíèÿ: Thu Dec 18 14:10:13 2014 Äàòà èíäåêñèðîâàíèÿ: Sun Apr 10 01:48:45 2016 Êîäèðîâêà:

.. , .. , .. , ..


I
..
..



- 2014




, 2010 ..

.. , I ( - , ). . , , . , , .




1. .............................................................................. 1 2. ............................................................................... 9 3. ...................................................................................... 16 4. . ­ 1 ................................................................ 23 5. . ­ 2 ................................................................ 28 6. ............................................................................................................... 34 7. ­ ­ 1 ............................................... 41 8. ­ ­ 2 ............................................... 46 9. ­1 .......................................... 55 10. -2 ......................................... 61 11. ­ 1....................................................................................................... 70 12. ­ 2....................................................................................................... 77 13. ­ 1 .................................................................................................. 84 14. ­ 2 .................................................................................................. 91 15. ­ 1 .................................................................................................. 98 16. ­ 2 ................................................................................................ 106 17. ............................................................................................... 115 18. ....................................................................................... 122 pH ..................................... 128 ...................................................................................................................... 129

0


1.

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

1. . ­ ,

. ( ) . , , . 1.1. . + + +



() -

, . , : ­ ` (, ); 1




­ (, , ).

­ . , . 1. . ? . ) . ) . ) . ) . ) . 2. . 2.1. ­ , ­ , , . ­ . (U) (Q) (A). , , . U = Q A (1).

: (U ) , (Q), (A), . ­ () , . U ­ . , : , , , . . 2


­ . , , . , - - (, V, n). (1) , . (F) (S) A

F S . ,

() = P V, ­ , V ­ , () = ni, ­ , ni ­ . . Q ­ , . , , . . ­ - . () , (S) , Q = TS « ». , . () ­ (). 1 = 4, 184 . ­ . . 2.2. . . ( 1) (V = const, V = 0) (= const) , ( = PV ). U = Q


= Q V

(2)

V = const; V = 0, U = QV (3),

, , . QV U, . P = const.

U QP PV QP P(V2 V1)
. (4)

(4),

3


QP U P(V2 V1 ) U 2 U1 PV2 PV1 (U 2 PV2 ) (U1 PV1 )
H

(5)

H = U + V
. ­ . (5) (6) ,

(6),

QP H 2 H1 H

P

(7),

(P = const) QP . , , , , V , , . 2.3. : ; , (U H).

1. Qp - Qv = H ­ U = U + pV ­ U = pV = RT, - (>0, , <0, ). Qp - Qv H2 () = 2H () 1000°. 3. . . ­ , . , . . . . . .

4


: , . (1.3.).

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

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

­ , ;

T ­ , ( , 298 ). (fH0): 1) .

5


2) fH0>0, (Cl2O, C2H2), , fH0<0, (CO2, H2O). 3) fH0=0 (, ), fH0>0 (, ). 4) . 3. , fH0 4. . 1.4. . fH0
298 29 8

H2SO4.

, /

Fe3O4 () ­1118 CO () CO2 () rH0
298

­110 ­394

Fe3O4 + 4CO = 3Fe + 4CO2

5. (C) ­ , 1 1 . : 1. . 2. , (Cp) (CV). 3. . 4. , . , , , .

6


6. . 6.1. 5. H-O (EH-O), fH0298 H2O () = ­242 /, H2 O2 H0 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 ­ fH0 / ­ (­242 /)]/2 = 463 /
298

298

()

H2O ()]/2 = [436 / + + 1/2·495

6.2. 6. ( -). U0() ­ ­ . H0 () K ­ ­ , . H0 () Cl2 ­ . I1 (K) ­ ­ . Ae (Cl) ­ ­ . : , , 1 (, ). : 1.1. U0 () KCl = ­fH0 KCl + H0 () K + 1/2H0 () Cl2 + I1 (K) + Ae (Cl) 7


E
K () + Cl ()
I1 (K) + Ae (Cl)
+ -

K () + Cl ()
1/2H () Cl2
0

K () + 1/2Cl2 ()
H () K
0

U ()

0

K () + 1/2Cl2 ()
fH KCl
0

KCl ()
. 1.1. . 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.
29 8

SOCl2 ()

1.5. . 2P () + 5Cl2 () = 2PCl5 () 6PCl5 () + 2P2O5 () = 10POCl3 () 4P () + 5O2 () = 2P2O5 () S () + O2 () = SO2 () PCl5 () + SO2 () = POCl3 () + SOCl2 () H0
298

, / ­892 ­308

­2988 ­297 ­101

8


2.

1. . 2. 3. . 4. . 5. . 6. . 7. . 8. . 9. .

1. . , , . , , . . 2. , , , () ­ (S). (Q) U = Q F S A = F S: Q = T·S (1)

9


F , ­ , . - : , .. Q > 0, S > 0, . , , (NH4NO3, NH4NCS), , .. . ­ (.2.1.). 2.1.

U,H,F,G S



3. . . : S Q . S = Q /T . . . : Q = 0 , , S = 0. . . . - , .. : ­ , , . , , , . S ­ . S = k lnW, 10


k ­ , 1.38·10-23 /., W ­ , . , . , , .



4. : 0 (.. W = 1). : 0 , . ( ): ; (S), (S). 5. . ( ). 1) . S () < S () < S (). S > 0, , ( ). 2) . , : , S (Fe3O4 ()) > S (FeO ()). 3) . , , (, S (NO2 ()) ( ) > S (O2 () )( )). 4) . , , (, S (CBr4 ()) > S (CF4 ()). 1. (> <0) : PBr5 () = PBr3 () + Br2 () NH3 () + H2O () = NH4+ () + OH­ () MoO3 () + 3H2 () = Mo () + 3H2O () 11


H2 () + Cl2 () = 2HCl () 24H10 () + 13O2 () = 8CO2 () + 10H2O () 6. : S = Q/T ) T = const ( ): S = H ../T .. , > S , H > H («» - , «» - ). S

) T const ( ), dS = Q/T (d - ), Q = cdT, dS = cdT/T. T1 T2 (T2>T1), ,
T2

S =

T 1



pdT/T.

c f(T) S = cln(T2/T1) ( )
T2

c = f(T) S =
S

T 1



pdT/T ( )

T



T



T

. 2.1. S (T) . ), ­ ). (T1>T ):
T . T
T 1

S(T1) = S(0) +


0

p()dT/T + H /T +

T



p()dT/T + H /T +

T



p()dT/T

S(0) ­ 0 . 2. 1 . H () = 40.7 /. 12


7. V F = U ­ TS G = H ­ TS = U + pV ­ TS F = U ­ TS G = H ­ TS: TS- « « , , F = U ­ TS G = H ­ TS: F G, . ; ( U0 ), (F G). 8. 2.2. T, p = const S = Q/T S > 0 S = 0, max S G = 0, min G F = 0, min F G < 0 F < 0 G = H ­ TS F = U ­ TS S G T, V = const F

­ , = const), .

( T, p

, H f(T) S f(T), G = f(T) = H ­ TS , S = ­ tg ( ­ ). G0 = f(T) = H0 ­ TS0. 13


, H0 S0 . 2.3. . H0 1 + S +
0





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

2

­

­

3

+

­

2N2 () + O2 ()=2N2O () NH4NO3 () = N2O () + + 2H2O ()

4

­

+

: .

. 2.2. G0 = f(T), 1-4 . 2.3.. 3. CdO CdO () + H2 () = Cd () + H2O () 14


, , . . 1) ( ) ? 2) ( ) ? 3) G0 = f(T) , H0 f(T) S0 f(T). , . 9. 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) , H0f(T) S0 f(T). , . 4) Qp ­ QV 400°?

15


3.

1. I II . 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 ­ : Q = U + pV 2- : Q = TS : U + pV = TS U = TS ­ pV . , G= - TS (1)

2. . (1) G = U + pV + Vp ­ TS = TS ­ pV + pV + Vp ­ TS = V - pV = RT 2. = 1 V = RT/p, (2), G = Vp = RTp/p , dG = RTdp/p = RTd(lnp) 16 (2)


p0 ( ) p
p1 p1

1


p

0

dG = RT d ln p
p
0

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/pAk pBl) (m0C + n0D ­ k0A ­ n0B) = G0 ( ), G = G0 + RT ln (p
C

m

pDn/pAk pBl) ( -) 17

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









. G0 = ­RTlnK = H0 ­ TS0 ln K = ­ H0/RT + S0/R , H0 f(T) S0 f(T), ln K = f(1/T) ­ , ­ H0/R ­ () . 3.1. H0 . H0 tg ) ) + ­ ­ +

18

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

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

, ,

: , . ( ) .

19


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. . SO fH0 S0
298 2

O2

SO

3

, / ­296.8 0 248.1

­396.1

29 8,

/·

205 256.1

: -.

3. : ClF3 () ClF () + F2 ()

20


, 600° 1 , () ClF3 (.. ) 0.84. 1) . 2) ( ) ? 3) ( ) ? 4) ln K = f(1/T) , H0 f(T) S0 f(T). 5) Qp ­ QV ? : ClF3 1 . . 3.4. ,
ClF3 ClF F
2



1-





1+

X

/(.)

1 1 1 (.) 1

1
1
p(.)

1
1
p(.)

1

P

xp()

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

.

21

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

3.5. . NaHCO3 () Na2CO3() CO2 () H2O () fH0 S0
298 298

, / ­947.7 102

­1131 136.4

­393.5 213.6

­241.8 188.7

, /·

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

2. NH4Cl () = NH3 () + HCl () 1) . 2) T = 298 ? G0298. 3) , 1 . 4) ln K = f(1/T) , H0 f(T) S0 f(T). , . 3.6. . NH4Cl () NH3 () HCl () fH0 S
0 298

, / ­314.4 95.9

­46.2 192.6

­92.4 186.9

298,

/·

22


4. . ­ 1

. 1. . 2. . 3. . 4. .

1. ­ , . : pV = nRT ( - ): (p + n
a )(Vm - nb) = nRT, Vm -- , a b -- . 2 Vm

( ­ ): SdT ­ Vdp + , i -- .


i

ni di = 0, ni -- i-

+ , + , + )- . , . 2.



­ , . (. ). - , . - , . , - , , ; n. m-, , K = n ­ m . 23


, : NH3 HCl () = NH4Cl (). n = 3; m = 1 k = n ­ m = 3 ­ 1 = 2.

()

+

C ­ () c, , C=K+2­ - (1)

K -- , 2- ( ), - . (). , , , . (1), .. K = 1 ­.

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

24


. 4.1. . . , . : OA, ­ , . OK, ­ , . OB, -, . O ­ , ( + + ). (T, p) ­ .







25




K ­ , ( ).

1. . 4.1 ) , , ; ) OA, OB . ) O . 1) ­ 1 , .. CO2 , (« »). , , . 2) - , -, , ( ). 3) ­ ( « » - «» ). 4) ­ ­ . 2. , , lgp = ­1347/T + 7.92, lgp = ­1660/T + 9.37 ( , ­ ). . 3. ? , ? ? 4. . 1. , : ) ; ) ; ) NH4Cl () = NH3 ()+ HCl (); ) , ( ) .

26


2. lg p = ­1629/T + 4.9, lg p = ­2351/T + 7.6. , ­ . .

27


5. . ­ 2

. 1. ­ . . 2. -. 3. . 4. .

1. ­ . : = 2 = 2 + 2 ­ = 4 ­ , -, T, x ( ) --. (p = const, T = const), = + 1 ­ - = 2 + 2 ­ - . 1 = 3 ­ . ­ ( ) ( ­ ) - (p=const, .. = 1 ) .( 5.1.)

. 5.1. . : . 28




(KRQN) , . (KLMN) , . ( , ) ­ ( ). () ­ (QM), (S) . , () , () (XB, YB). ( / = QS /SM).







, , . . ­ , (V) , L : V = xL. ­ , .

- V = xL. , = 3 ­ ­ 1 = 3 ­ 2 ­ 1 = 0

. 5.2. ( HCl ­ H2O). 29


2. - ­ ( ) ( ­ ) - (p=const) . 2.1.

T
(L )

Tm , A
S+L

Tm , B
(S)

A

B

. 5.3. : EA-A = EB-B = E A-B ­ , (S), (L). ­ . (S), (L). 2.2. ( 5.3) ­ , .

. 5.3. . . 30


2.3. ­ .

T T A L

T

A + L B + L E A + B


T B

T

E

A

B

. 5.4. . : ( ) ­ , [ (), () L ()], = 3 ­ 3 = 0. ( . ­ , , , .



2.4. . () - () = const, 5.5. , .. TmA, TmB, m


-
mAE1

. T

, 1m,

m

2, 2TmB,

(L) (), S, S (S L) (S + L, S


S .

+ L S + L , S + S

,S



+S



) .

31


.4 ­ - 1 2.

Tm A SA + L SA + SAB SAB +L SAB +L SAB + SB SB + L

Tm Tm B A B

.5.5. ; - = - = - ; - - < - :



( ) ( x S= xL, .. =1) , , = 3 ­ 2 ­ 1 = 0 ( ). , , . ( , ). 3.



­ . T ­ ( ­ ) . .

2 ( 5.6.) ( ). 32




­ ( , : = 0). 1 3 () ;. = 0



T L
1 2 3 B+L A+L

T T
m, B

1

2

3

T

T b

m, A

m, A

E
A+B

T

E

A

x, %B

B







5.6 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.

2.1.

xi

ni ni

, ni ­ i- .

2.2. () ci ­ i- 1 :

ci

ni V

/

34


2.3. (

mi

ni G

/ ) ­ i- 1



mi

=

mi 1000 Mi G

2.4. w ( %):

w

mi m




m



mi m


.

mi V

, V- , -

. 1: KNO3 (M = 101 /) 31 100 . 1160 /. , KNO3. , .

3. ­ (. 6.1), . 6.3. . 1

p p0 n



n n




p i p0 n



in n



2



= =Kg1000/GMr = E =Eg1000/GMr





= i = iE

3



= nRT/V = CRT

=iCRT

: 1) : 35


p0 ­ , p ­ . 2) p1 = p10x1 = p10(1­x2), x2 = (p10­p1)/p10 = p1/p10, «1» , «2» - . 3) K ­ ­ , . 4) - ­ , . 5) ­ , , . ! /3 ( /, 1 /3 = 1000 /). 6) , i ( ), . 6.1: 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(H+)·a(OH­)/a(H2O)2 [H3O+]· [OH­] = K Kw - . T = 22C = 295 Kw = 10
­14

w

.

, , Kw : 1000C Kw = 10­12. 36


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 () = NH3·BF









3

- (.. - ). 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. . Ka·Kb=([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) = 1.75·10­5 : CH3COOH + H2O CH3COO­ + H3O+

Ka (CH3COOH) = [CH3COO­]· [H3O+]/[CH3COOH] = [H3O+]2/(c(CH3COOH ­ [H3O+]) [H3O+]2/c(CH3COOH) ! , c(CH3COOH) >> [H3O+] [H3O+] =
K a c = 1.32·10­3, pH = ­lg [H3O+] = ­lg (1.32·10­3) = 2.88
­5

4. pH 0.1 CH3COONa. Ka (CH3COOH) = 1.75·10 : CH3COO­ + H2O CH3COOH + OH­

:

38


K=

[CH 3 COOH][OH - ] . [CH 3 COO - ][H 2 O]

: K[H2O] = [CH 3 COOH][OH - ] . [CH 3 COO - ]

[H+]. [CH 3 COOH][OH- ][H ] K[H2O] = . , [CH 3 COO - ][H ] Kw = [OH-][H+] [CH 3 COO - ][H ] Ka = . [CH 3 COOH] K = w/Ka (CH3COOH). : K = w/Ka (CH3COOH) = [CH3COOH]·[OH­]/[CH3COO­] = [OH­]2/(c(CH3COONa) ­ [OH­]) [OH­]2/c(CH3COONa) ( , ) AlCl3 (NH4)2CO3 - ! , c(CH3COONa) >> [OH­] pH . 6.5. 6.5. pH . K = Kw/Ka pH pH > 7



K = Kw/Kb

pH < 7 Ka Kb pH = 7

,

K = Kw/(KaKb)



-

39


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 .

8. . I. 1) LiNO2 70 1.06 . % ? 2) , 0.98. K(H2O) = 1.86. 3) . 4) pH . 1010 /. a (HNO2) = 5.110­4 5) , 0.03 NaF? LiF = 1.710­3 II. 10% H2SO4 1,0661 /. .

40


7. ­ ­ 1

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

1.





,











, -. , . , , ,

KMnO4 +7, +0.7. - . - , . - , . : -

1. , , . 2. . 3. , . 4. , , -1 5. +1, +2 6. -2, , -1. 41


7. , , -1, , . , ClF +1. BrCl -1. 8. +1, , , , (NaH, NaBH4, LiAlH4), -1. (.. - , ). ­ - , . : Cl20 + 2KOH = KCl­1 + KOCl+1 + H2O - - , . : 2H2S­2 + S+4O2 = 3S0 + 2H2O

2. . : - (F2, Cl2, O2). (HClO, SeO2, HNO3). , d- (KMnO4, K2Cr2O4, V2O5). , 6s2- - ( (III), (IV) (V)). (K2S2O8).





: ­ ( , ). ­ (H2, C, Si). C (LiH, NaBH4, H2S, HI). 42






, , Na2S2O3, KH2PO2, CO. (Cr2+, Sn2+, Mn2+).



, : ( ) ( ) (Na2SO3, NaNO2). d- ( 0 ) (Cr3+, VO2+). H2O2.





: H2O2 ­ : Te + 3H2O2 =H6TeO
6 2

H2O2 ­ : H2O2 + Cl2 = 2HCl + O

3. - - - ( ) , , , , (, Mn+7 MnO4­, ). . 1) . 2) ( ) ( ). ! : , H+ , ­ OH­ . H+ OH­ - ! 3) . 4) , . 5) ( ), , 43


, , , . 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 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 + 2OH Zn + 2OH­ + 2H2O = [Zn(OH)4]2­ + H2

Zn + 2NaOH + 2H2O = Na2[Zn(OH)4] + H2 3. Br2 + KOH = KBr + KBrO3 + H2O 44


1 10 5

Br2 + 12OH­ ­ 10e = 2BrO3­ + 6H2O ()

Br2 + 2e = 2Br­ ()
­

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 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 (.) 1 . Mz+ (-) / M0 (.)0 , . , . , . () H+/ ½ H2, 46






+(.) + e 1/2 H 2 .

o

() ­ , , . , . , , 1 , +, 1 ( = 1 /) = 0 . , .. () , , : , , . () ,





( 0 ): E0(Mz+/) = = (Mz+/) ­ () = (Mz+/) ­ 0 : 1) G0 = ­zFE0, z ­ , , F = 96500 / ­ . - ­ - . 2) E0 ( G0) , , - , - . 3) E0 , E0(Mz+/) Mz+ + ze = M0. 4) E0 > 0, G0 < 0, , . E0, - . 5) E = f(T, ai), ai = ci . i ­, i - , ci ­ . 6) : , () ( ).

47


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. - ,

Cu2+ + Zn0 Cu 0 + Zn2+
, , E0r, E0 (Cu2+/Cu) = 0.337 , E0 (Zn2+/Zn) = ­0.763 . . 1) E0 (Cu2+/Cu) > E0 (Zn2+/Zn) , 2) Cu2+ - , Zn ­ . 3) E0r, () = E0 (Cu2+/Cu) - E0 (Zn2+/Zn) = 0.337 ­ (­0.763 ) = 1.1 : , ( ). , , - .. 3. . A, B, C, D ­ , . kA + lB mC + nD (k, l, m, n ­ )

48


G = G0 + RT ln (aCm aDn/aAk aBl) (1 )­ - ( ) (1 ) ­Fz. ­G/Fz = ­G0/Fz ­ RT [ln (aCm aDn/a
k A

aBl)]/Fz

, G0 = ­zFE0, G = ­zFE, E = E0 ­ ) E = E0 +

RT ln (a Fz

m C

aDn/aAk 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 (aAk aBl/a Fz

C

m

aDn) =

=

RT 2 RT ln [a(H+)]4 = E0 + ln [a(H+)] 2F F 2 RT ln [a(H+)] > 0, F

, E > 0, E0 + ln [a(H+)] > ­

E0F E0F , a(H+) > exp 2 RT 2 RT

, a(H+) > 12.575

pH = ­lg[H+], , , a(H+) = [H+], ­lg[H+] < ­lg 12.575 (...) pH < ­1.10. 49


4. ­ . : . (pH = 0), (pH = 14) . (, (­3) NH4+ NH3 ). E10, z1 A B E30, z3 = z1 + z2 ( ) ( ) () G01 + G02 = G0
3

E20, z2 C

( )

­z1E01F ­z2E02F = ­z3E03F z1E01 + z2E02 = z3E03.

(),() () , ) E03 = (z1E10 + z2E20) / z3 = (z1E10 + z2E20) / (z1 + z2) 1) , 0 G, : G3 = 0 G1 + G2 . Ei ( zi) ! 2) E20 > E10 (.. ), . : , - , .

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

50


-0.86 NO3
­

0.88 NO2
­

-0.46 NO

0.76 N2O

0.94 N2

NO2

5. ­ (nE0) (n). . r G = ­nF E 0r - 0 3+ + e = A2+ ()= n E r ­ A , , A3+ A2+.

5.1.

( . 1).

.1. : ­ = 0; ­ =14.

1. : nE = 0 Mn2+/ Mn0 n = 0. 2. « ­ », , . , Mn2+ - : ( Mn2+/ Mn0) = n x E0 ( Mn2+/ Mn0) = -1.18 x 2= -2.36

51


MnO2 ­ (MnO2 /Mn ) =n 0 = 0.025 4 =0.10 . - = 0 . 1. 3. « ­ », , . , Mn2+ - : ( Mn2+/ Mn0) = n x E0 ( Mn2+/ Mn0) = -1.18 x 2= -2.36 MnO2 ­ (MnO2 /Mn ) =n 0 = 0.025 4 =0.10 . - = 0 . 1.
o

o

1.

-



Mn Mn2+ Mn3+ MnO2 MnO42­ MnO4­

(n) 0 +2 +3 +4 +6 +7

Eo (Mn n + /Mn o )
0 1,18 0,283 0,025 0,77 0,74

nE

o

0 2,36 0,85 0,10 4,62 5,18

5.2. . ?1) , , Mn3+/ Mn2+ Mn4+/ Mn2+ . (tg . 1) . tg1 E (Mn /Mn ) , tg2 E0 (Mn4+/ Mn2+ ). Mn2+ Mn3+ , MnO2 . 2) . . (.1): ( -) . Mn+2. , 52
o 3+ 2+


Mno Mn+2. Mn2O3. Mn(OH)2 , Mn23 (. 1). 3) . , , , (.1), . ( -) , . , (), (), , () . 2.

.2 , (), (), , ()

53

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

8.1. .

Cr2 O
fH
0 298

2 7 (-)

I

(-)

3 Cr() -

I

2 ()

H 2O

()

,

/ , /(·)

­1491.9

­55.9

­236.1

0

­285.8

S

0 298

270.6
0 Cr2 O

109.4

­265.1

116.2

70.1

) E

2 7 (-)

3 / Cr(+ -

)

, , E

0 I2

( )

/ 2I

( )

= 0.536 .

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

0.495 BrO3
­

0.455 BrO­ Br
2

1.065 Br­

54


9. ­1

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

1. . . ­ ( ), . : (x, y, z); ; (.. ); : ||2 (x, y, z) . , 95%, .

­ , . E = H ­ , H ­ ( ­ , ). , . (« », ). 55







. , ( ­ ) . , , ­ . : , n, l m . 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 m 1 s ­ 3 p ­ (px, py, pz) 5 d ­ (dxy, dxz, dyz, dx2-y2, dz2) 7 f ­ s +1/2, ­1/2 56


. 9.1. s- (), p- (), d- () . , . , . 57


3. 3.1. ­ , . 3.2. ­ . 3.3. ­ l , (.. s). 3.4. : 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]4s1 Sc [Ar]4s23d1 Ga [Ar]4s23d104p1 Ca [Ar]4s2 Zn [Ar]4s23d
10

Kr [Ar] 4s23d104p6

322 220

3 2 ­3 ­1/2 410 0

58


1) , . 2) , . 3) .

4. 4.1. . ­ , . (, , ). : ­ ( ). d- f- ( , ). ­ ( , ). d ­ (d ­ ) f ­ ( ).



4.2. () I ­ , . In+1 > In ( ). ­ , . 4.3. ( ) Ae ­ . , .. , . , , -. / . 4.4. () ­ , , . , : . ­ Fr, ­ F. ­ , ­ . ­ , ­ . ­ , ­ . . 59


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+.

60


10. -2

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

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

1.2. . 1) s- d-. 2) . 3) : , , , . 4) , 6. 61


5) , , . . 2. . AXnEm A ­ . ­ . ­ . 10.1 . n+m 2 180° 2 3 2 4 3 2 5 4 3 2 6 5
2 3 2

n

m

-



2 3

0 0 1 0 1 2 0 1 2 3 0 1

BeCl2 BF3 SnCl2 CF4 NH3 H2O PF5 SF4 ClF3 XeF2 SF6 IF5

3

120° 2 4

4



109.5°

3 2 5

5



120° 180°

4 3 2 6 5

6



90°

4

2

4

2



XeF4

62


: , n + m = 5 , . , (120° 90°).

. 10.1. , . m n: AXnE n ­ , 63
m


n + m = [(N . e () + N . e () ± z) / 2] ­ d : N . e () ­ ( , ). N . e () ­ , . z ­ ( , «+», , «-»). d ­ . 1. , . CO2, Cl2O, BrF5, ICl2+, NF3, SOCl2. : SOCl2 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 ­ .

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

64


4. . 4.1.

E





2



2 * 1s 1 1s

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



65


4.2.

E O O
2

O

4 * 2* 2p 1 2p

3

2 * 2s 1 2s

. 10.3. 2. «» , , . 2p ­ ( ) ­ ­ . , 2p ­ (2px, 2py, 2pz), 2p ­ , , ­ ( , 2pz ­ ). 66


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*) ­ .

O

2

O2* 2* 2* 2*

. 10.4. (O2) (O2*) .

67

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

E N N2 4* 2* 2p 3 1 2* 2s 1 2s 2p N

. 10.5. N2. 68




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

6. 1. , : XeO3, SO2, SOCl2, ICl2 -, ICl4-, XeO3F-, IO2F4-.

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

3. 2 ) ; ) ?

+

2

2-

69


11. ­ 1

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

1.
9

F

17

Cl

35

Br

53

I

85

At

[ ]ns2np5 () - () () ()

0.064 0.099 0.114 0.133 0.144 0,133 0,181 0,195 0,220 0,230 17,42 12,97 11,81 10,45 9,20 3,5 3,6 3,5 3,3 -

: ) ­ , , ( ), ­1; ) ( ClO2); ) ­ ; ) , ; ) .

70


2. - , . : CaF2 , 3Ca3(PO4)2·CaF2 : NaCl , KCl , NaCl·KCl , KCl·MgCl2·6H2O : , - ( ). : ,

11.1. F KF KF*3HF 50100 2HF = H2 + F2 NaCl Cl2 2NaCl + 2H2O = 2NaOH + H2 + Cl2 (KMnO4, MnO2, K2Cr2O7, PbO2, KClO3) MnO2 + 2H2SO4 + 2KX = X2 + + MnSO4 + K2SO4 + 2H2O (X=Br, I) 2CuSO4 + 4KI = 2CuI + I2 + + 2K2SO4

F2

tC 2CoF3 = 2CoF2 + F2 HCl (.)

Br2, I

2

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

71


3. ­ X2: 1, . 3.1. F2 -219 -188 Cl2 -101 -34 Br -7 60
2

I

2

113,7 183

T (0) T (0)

: 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 ­ ,

72


4. . 4.1. : (. ).

, HI . 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 -83 19,5 0,1 -271 9 HCl -112 -84 HBr -84 -67 HI -51 -35 (0) (0)

0,127 0,141 0,162 H ­ X () -92 93 -34 93 +26 95 (/) 0,1 (%)

+3,05 +1,36 +1,07 +0,54 0 2/2- () 73

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

. 11.1. .

) , HF ­ , : () (, , KHF2). HF-.

. 11.2. pKa (pKa = ­lgKa)

) . Na2O·CaO·6SiO2 + 28HF () = NaF + CaF2 + 6SiF4 + 14H2O ( ) 74


Na2O·CaO·6SiO2 + 36HF (aq) = Na2[SiF6] + Ca[SiF6] + 4H2[SiF6] + 14H2O ( ) 5. : XYn, Y ­ , n ­ ; ­ ; ( , ); 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 ., 3.5·10­4 (Cl2), 2.3·10­3 (Br2), 2.8·10­2 (I2). . 1. H-X HF HI, : X2 X2, / HX fH0298, / 75 H2 () 432 HF () ­268 F2 () 155 HI () +26 I2 (.) 149

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

76


12. ­ 2
1. . 2. 3. . 4. . 1. 1.1. : ; , ; ( J2O5) ( , ), ­ .



1.2. : OF2 ­ - . 2F2 + 2NaOH (.) = OF2 + 2NaF + H2O OF2 + 2NaOH (.) = O2 + 2NaF + H2O 1.3. . 12.1. .
- 2HgO + Cl2 = HgO·HgCl2 + (0°C, CCl4) + Cl2O

Cl2O

Cl2O + H2O = 2HOCl

2KClO3+SO2+H2SO4 = =2KHSO4 + 2ClO2 ClO
2



2KClO3+H2C2O4+H2SO4 = =K2SO4+2ClO2+2CO2+2H2O 3KClO3 + 3H2SO4 = HClO4 + 3KHSO4 + H2O + 2ClO2

2ClO2 + H2O = HClO2 + + HClO3

77


ClO3 (Cl2O6) Cl2O
7



ClO2 + O3 = ClO3 + O2 (0°C)

2ClO3 + H2O = HClO3 + + HClO4 Cl2O7 + H2O = 2HClO
4

2HClO4+P2O5 = Cl2O7+2HPO3

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. . HOCl HClO2 HClO3 HClO4 HOBr HBrO3 HBrO4 HOI HIO
3





Cl Cl Cl Cl Br Br Br I I

+1 +3 +5 +7 +1 +5 +7 +1 +5



78


I I

+7 +7

HIO

4 6





H5IO

2.2. HOCl 2Cl2 + 2HgO + H2O = HgO·HgCl2 + 2HOCl ( Cl2O) HClO2 ClO2 + Ba(OH)2 + H2O2 = Ba(ClO2)2 + 2H2O + O2 Ba(ClO2)2 + H2SO4 . = BaSO4 + 2HClO2 HClO3 tC 6KOH + 3Cl2 = KClO3 + 5KCl + 3H2O ( : KClO3 , KCl - ) KCl + 3H2O = KClO3 + 3H2 () Ba(ClO3)2 + H2SO4 . = BaSO4 + 2HClO3 HClO4 KClO4 + H2SO .
4

= KHSO4 + HlO4 c tC 4KClO3 = KCl + 3KClO4

KClO3 + H2O = KClO4 + H2 () 70% , . HBrO3 Br2 + Cl2 + 12KOH = 2KBrO3 + 10KCl + 6H2O ( KClO3-KCl) Ba(BrO3)2 + H2SO4 = BaSO4 + 2HBrO3 HBrO4 KBrO3 + XeF2 + H2O = KBrO4 + 2HF + Xe ( ) HBrO4 KBrO4 . 79


HIO

3

tC I2 + 10HNO3 (.) = 2HIO3 + 10NO2 + 4H2O

HIO4 H5IO6 tC 5Ba(IO3)2 = Ba5(IO6)2 + 4I2 + 9O2 Ba5(IO6)2 + 5H2SO4 = 5BaSO4 + 2H5IO
6

t C H5IO6 = HIO4 + 2H2O ( )

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

HXO3:

HXO4

H

H O I O OH O H

H5IO

6

O HO

3. 3.1. . : () , H - O, , , HOCl < HClO2 < HClO3 < HClO4 : , H - O, , .. , ­ . 80


3.2. . : , , , , , , HOCl > HClO2 > HClO3 > HClO4 : ( Br - O, . ). , : 2KBrO3 + Cl2 = 2KClO3 + Br2 2KBrO3 + I2 = 2KIO3 + Br2 3.3. .

pH=0

pH=0 pH=0

pH=14

pH=14 pH=14

. 12.1. pH=0 pH=14. : , ; Br>Cl>I; +3 , +1 . 3.4. ­

81


X = F: , HF , . X = Cl ­ I: ) ; ) ­ , X2 (8Cl2·46H2O); . ) l2 + H2O HCl + HOCl (1) ) : 3HOl 2HCl + HClO3 (2) ) , : 2HClO = 2HCl +O2

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.

82

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

2. , :

1.05 BrO4
­

0.54 BrO3
­

E BrO
­

0

x

1.07 Br2 Br­

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

83


13. ­ 1

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

1.
8

O

16

S

34

Se

52

Te

84

Po

[ ]ns2np4 () 2- () () ()

0,068 0,104 0,114 0,132 0,138 0,182 0,193 0,211 13,62 10,36 9,75 1,47 2,08 2,02 9,01 2 8,43 1,35

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

146 265 192 218

X=X 494 421 272 126 84


: 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 O 1) . 2) . tC 2BaO2 = 2BaO + O2 2Na2O2 + CO2 = 2Na2CO3 + O2 ( ) 1) .

S

, .





85


2) 2H2S + O2 = 2S + 2H2O

Se, Te



, .

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



O O O



S



S8, S8,



S



-

S



S

n

Se



.

Se





Te Po



-

86


: 1) 16 ­ - . .

. 13.1. .

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

, . Na2S2O3. 87


:
tC

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

Se + 4HNO3 = H2SeO3 + 4NO2 + H2O Te + 2 H2O2 + xH2O = TeO2*xH2O + 2H2O

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

CnH2n+2 4.2. H2O -0 100 0,096 463 1,8·10
-16

H2S -85,6 -60,4 0,133 347 1·10
-7

H2Se -65,7 -41,4 0,146 276 1,7·10-4

H2Te -51 -2 (0) (0)

0,169 H ­ X () 238 1·10
-3

H ­ X (/) 1

5. . ­ . 5.1. : 88


tC Fe + S = FeS




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



Cu2+ + S2- = CuS

5.2. 13.4. . , , NH4 Mn2+, Fe2+, Zn2 Cd2+, Co2+, Ni2
+ +

, MS + 2H2O = M(OH)2 + H2S - « »

+

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

(HNO3 . + HCl .)

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

89

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

90


14. ­ 2

1. . 2. 3. . 4. . 5. . 1. . 1.1. C, , +4 -ChO2 +6 -- ChO3. . : H2TeO3/TeO2·xH2O K1 = 2.7·10-3 -9 K2 = 1.8·10-8 H6TeO6 -2 K1 = 2.45·10-8 K2 = 1.1·10-11 K3 = 1.1·10-15
-3

H2 K1 K2 H2 K2

SO3 = 1.4·10-2 = 6.2·10-8 SO4 = 1.15·10-2

H2 K1 K2 H2 K2

SeO3 = 1.8·10 = 3.2·10 SeO4 = 1.2·10

pH = 0 E0H2ChO3/Ch, E0H2ChO4/H2ChO3, B

S 0.5 0.158

Se 0.74 1.15

Te 0.57 0.93

( )

91

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







Na2SO3 + 2H2SO4 = 2NaHSO4 + SO2 + H2O tC Cu+2H2SO4 (.) = 2CuSO4+SO2+2H2O

SO2 + H2O = H2SO

3

SeO

2



tC Se + 2NO2 = SeO2 + 2NO

SeO2 + H2O = = H2SeO3

TeO

2

Te + O2 = TeO

2



SO

3



tC 2SO2 + O2 = 2SO3 ( Pt, V2O5) SO3 + H2O = H2SO tC Na2S2O7 = Na2SO4 + SO3 H2SeO4 + P2O5 = SeO3 + 2HPO3 tC H6TeO6 = TeO3 + 3H2O SeO3+H2O = H2SeO4
4

SeO

3



TeO

3



2. 2.1. 14.2. H2SO
3





S Se Te

+4 +4 +4



H2SeO3 TeO2·xH2O

92


S Se Te

+6 +6 +6

H2SO

4





H2SeO4 H6TeO
6

2.2. X(+4) XO2 + H2O = H2XO3 (X = S, Se) TeCl4 + (x+2)H2O = TeO2·xH2O + 4HCl X(+6) H2SO4 ­ : ) : tC, p, V2O5 2SO2 + O2 2SO
3

SO3 + H2O = H2SO4 ( SO3 H2SO4, ) ) SO2 + NO2 + H2O = H2SO4 + NO , . H2SeO3 + H2O2 (.) = H2SeO4 + H2O Te + 3H2O2 (.) = H6TeO
6

2.3. H2XO3 H2XO4
HO X HO O O

HO HO

XO

93


2.4. . 14.3. . H2S2O3 -78





HO

S S O

HS HO

O S O



HO



O H2SnO6 HO S O S
n

O S O OH

O H2S2O7 HO S O O

O S O OH

H2SO

5

( )

O HO S O O OH


O H2S2O8 HO S O O O

O S O OH

2.5.
tC, Na2SO3 + S =============== Na2S2O3 ()

Na2S2O3 + H2SO4 = Na2SO4 + S + SO2 + H2O ( ) ­ 2Na2S2O3 + I2 = Na2S4O6 + 2NaI ( ) 94


Na2S2O3 + 4Cl2 + 5H2O = 2NaHSO4 + 8HCl ( ­ «», Br2) ­ 2KHSO4 = K2S2O7 + H2O (t1 C) K2S2O7 = K2SO4 + SO3 (t2>t1) ­ 2H2SO4 = H2S2O8 + H2 () 2KHSO4 = K2S2O8 + H2 () H2S2O8 + 2H2O = 2H2SO5 + 2H2SO4 E0 (S2O82­/SO42­) = 2.01 ­ 2MnSO4 + 5K2S2O8 + 8H2O = 2KMnO4 + 8H2SO4 4K2SO
4

Mn2+ .

3. : H2SO4 H2SO3, H2SO () .
4





: H2SO3 , H2SO4 ( H2SO3 ). , H2SO4 H2S, H2SO3 H2SO3 + 2H2S = 3S + 3H2O 4. 14.4. .











Cl
SOCl2 ( )

S Cl

O

PCl5+SO2= = SOCl2 + 4NaOH = POCl3 + SOCl2 = Na2SO3+2NaCl+2H2O

95


SO2Cl2 ( )

Cl S Cl

O O

SO2+Cl2 = SO2Cl2 ( )

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

5. . BaSO4, . . . 1. . ... S, tC NO2, H2O FeS SO
2

K2S2O8

t C X NaOH SOCl2 ... KHSO4 K2S2O7 ...

X ­ , . 2. , :

96


nE

0

S (0.94)

2­

S2O3 (1.20)

2­

HS2O4 (2.07)

­

S2O6 (2.57) H2SO3 (2.00)

2­

SO4 (2.32)

2­

pH = 0

-2
H2S (­ 0.28)



2
S2O3 (­ 1.48)
2­

4

6

SO3 (­ 2.64)

2­

SO4 (­ 4.52)

2­

pH = 14

. 14.1. .

1) , , . 2) ­2 ? 3) ?

97


15. ­ 1

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

1.
7

N

15

P

33

As

51

Sb

83

Bi

[ ]ns2np3 (), ()

0,070 0,110 0,118 0,136 -0,146 14,53 10,484 9,81 8,639 7,287

: ) (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

98


: 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)2·CaA2 (A = F , = OH ). , , ­ 15.2.
tC NH4NO2 = N2 + 2H2O N
2



tC 2NaN3 = 2Na + 3N2 )

(

P

4

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

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

2

As, Sb, Bi tC X2O3 + 3C = 2X + 3CO

99

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



. P P6 As4 As6 Sb6

P





As As





Sb



- -

Bi



3.2. : tC P4 + 3KOH + 3H2O = PH3 + 3KH2PO : - P + 5HNO3 (.) = H3PO4 + 5NO2 + H2O Bi + 4HNO3 (.) = Bi(NO3)3 + NO + 2H2O ( . HNO3)

2

4. XH 4.1. : 100

3




­ tC, p, Fe 2NH3 ( )

N2 + 3H

2

tC Ca(OH)2 + 2NH4Cl = 2NH3 + 2H2O + CaCl2 PH4I + KOH = PH3 + KI + H2O



Mg3N2 + 6H2O = 3Mg(OH)2 + 2NH3



4Zn + NaNO3 + 7NaOH + 6H2O = 4Na2[Zn(OH)4] + NH3 3Zn + NaNO2+ 5NaOH + 5H2O = 3Na2[Zn(OH)4] + NH3



(. ).

4.2. NH3 -33 PH
3

AsH3 SbH3 -18

(BiH3 ) , H ­ X () H--, H ­ X, / ( )

-87,7 -62

0.102 0.144 0.152 0.171 107.3 93.3 380 323 92 281 91 256

4.3. XH

3

1) NH3 NH3 + H2O NH3·H2O NH4+ + OH­ Kb = 1,78·10-5 ( «NH4OH» , NH3·H2O). 2) PH3 (HI, HClO4). . .

101


5. 5.1. N2H4
H NN H H H

: 2NH3 + 2NaOCl = N2H4 + 2NaCl + H2O : «» : ) ; ) 2NH2Cl + NaOCl + 2NaOH = N2 + 3NaCl + 3H2O ( 90%). (CH3(C=O)C2H5): 2NH3 + H2O2 = N2H4 + 2H2O : . T = 1.5, = 113.5 ) , , ( -NH2). ( ) N2H4 + H2O N2H4·H2O N2H5+ + OH­ N2H5+ + H2O N2H62+ + OH
­

Kb1 = 3,0·10 Kb2 = 8,4·10

-6 -16

, N2H5Cl ­ N2H6Cl2. ) - . , N2H4 + 4CuSO4 + 8NaOH = 2Cu2O + N2 + 4Na2SO4 + 6H2O : CuSO4 + 4NH3 = [Cu(NH3)4]SO
4

­ N2H6Cl2 + 2H3[TiCl6] = 2H2[TiCl6] + 2NH4Cl 102


) N2H4 + O2 = N2 + 2H2O (N2H4 ­ )

5.2. NH2OH

H N H O H
: 2NO + 3H2 + H2SO4 = (NH3OH)2SO4 (Pd ) (NH3OH)2SO4 + 2KOH = K2SO4 + 2NH2OH + 2H2O : = 33.5 , = 56.5

. : 2HNO3 + 2HCl + 2H2O = 2[NH3OH]Cl + 3O2

) , , ( ). NH2OH + H2O NH3OH+ + OH
­

Kb = 2·10-

8

) - : ­ N2, N2O ( NH2OH N - O) 2NH2OH + I2 = N2 + 2H2O + HI NH2OH ­

2[NH3OH]Cl + 2I2 + 6KOH = N2O + 4KCl + 2KCl + 7H2O C ­ NH3: [NH3OH]Cl + H2S = S + H2O + NH4Cl 2NH2OH + 4FeSO4 + 3H2SO4 = 2Fe2(SO4)3 + (NH4)2SO4 + 2H2O 103


) , tC 3NH2OH = NH3 + N2 + 3H2O 5.3. NH3 N2H4 NH2OH

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 S0
298

, / 0 200

­167 57

­98 167

0 223

­286 70

298,

/·

104


2. N - N , ­46.2 95.4 / . 431 950 / .

105


16. ­ 2

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

1. 1.1. : ( NO : ); , As2O5, Sb2O5 (V) .



1.2. 16.1. .
N2 O - 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)





106


N2O3



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

N2O3 + H2O = =2HNO2

NO2 (N2O4)

, ()

2NO2 + H2O () = = HNO2 + HNO3 3NO2 + H2O () = = NO + 2HNO3

tC 2Pb(NO3)2 = 2PbO+4NO2+O2 2NO + O2 = 2NO2 2HNO3 + P2O5 = 2HPO3 + N2O 2NO2 + 1/3O3 = N2O5 P4 + 3O2 = 2P2O3 ( O2)

N2O5 P2O3 (P4O6) P2O5 (P4O10)



5

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

P4 + 5O2 = 2P2O

5

P2O5 + 3H2O = =2H3PO4

2. 2.1. 16.2. . HNO2 HNO3 H3PO H3PO HPO
2 3





N N P P P P P

+3 +5 +1 +3 +5 +5 +5



3 4

H3PO

H4P2O7

107


2.2. , . 16.3. .
HNO2 Ba(NO2)2+H2SO4 = BaSO4 + + HNO2 4NO2 + 2H2O +O2 = 4HNO HNO3
3

H-O-N=O

,

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

HON O

,

HO H P H

O

H3PO

2

,

HO
H3PO
3

P2O3 + 3H2O = 2H3PO3

H

P

O OH

,

P2O5 + 3H2O = 2H3PO4 H3PO tC
4

O H PO O OH H
O O H

Ca3(PO4)2 + 3H2SO4 = = 3CaSO4 + 2H3PO4

,

2H3PO4 = H4P2O7 + H2O H4P2O
7

H

O H

(200-250C)

POPO OH O

,

HPO3 [(HPO3)n]

H4P2O7 = 2HPO3 + H2O (n=3) (350-400C)

,

108


(HPO3)3 :
HO HO O P P O O P OH

O O O . 16.1. .

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







2.4. ( ) 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 ­ , . : 12(NH4)6Mo7O24 + 51HNO3 + 7H3PO4 = 7(NH4)3[PMo12O40]*nH2O + 51NH4NO3 + (36-7n)H2O 109


2.5. ) ; ) : , . 16.4. . 60% (Fe, Cr, Al, Bi .) ­

«» 20-60% «» <20% 10-20% <10% H « » H H

NO2

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

NH4NO3

: « H» « H» (S, C, P, As, B) , , NO2. « » - HCl HNO3 . HCl .



Au + HNO3 + 4HCl = H[AuCl4] + 2H2O + NO , NOCl. NO,

C HNO3 + HF , , .

3Ta + 5HNO3 +21HF = 3H2[TaF7] + 5NO + 10H2O 110


3Si + 4HNO3 + 18HF = 3H2[SiF6] + 4NO + 8H2O

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



3.2. 16.5. . , ( ) (MgCu ) ( Cu) NH4NO3 MNO2 + O2 MxOy + NO2 + O M + NO2 + O2 N2O ( )
2

: MxOy , , tC Sn(NO3)2 = SnO2 + 2NO2
Fe(NO3)2 = Fe2O3 + NO2 + O Cr(NO3)2 = Cr2O3 + NO2 + O Mn(NO3)2 = MnO2 + 2NO2
2 2

111


3.3. , ­ . t, C Na2HPO4 === Na4P2O7 + H2O t, C NaH2PO4 === NaPO3 + H2O

, ­ . t, C (NH4)2HPO4 = 2NH3 + H3PO4 t, C t, C

2H3PO4 == H4P2O7 + H2O 2H4P2O7 = 2HPO3 + H2O

, , (V).

4. HNO2 ­ HNO3: HNO3 , HNO2 ( ) ( HOCl ­ HlO4 H2SO3 ­ H2SO4). : . : P-H (.. ), . , : H3PO2 > H3PO3 > H3PO4. . , . H3POn , , ( ): H3PO2 (1) > H3PO3 (2) > H3PO4 (3) +5 : HPO3 (1) > H4P2O7 (2) > H3PO4 (3) : , , , ( , ).

112


5. 5.1. ­ , , -. 5.2. Bi(OH)3 . Bi3+ : Bi3+ + H2O BiO+ + 2H+ 5.3. Bi(+5) ­ ( 6s2- ) . (V) . : Bi(OH)3 + 3KOH + K2S2O8 = KBiO3 + 2K2SO4 + 3H2O Mn : 4MnSO4 + 10KBiO3 + 14H2SO4 = 4KMnO4 + 5Bi2(SO4)3 +3K2SO4 + 14H2O 6. . : NaNO2, NaH2PO2, Na3PO4, NaNO3. , . . . 1. , . - .

... P
tC

KNO3

HNO3 (.)

NH4NO3

...

NH4NO3

NH3

CuSO4, KOH N2H4 ...

2. , : 113


nE
PH3 (2.67)

0

PH3 (0.19) H3PO2 (­ 0.51) H2PO2 (­ 2.05)
­


H3PO3 (­ 1.51) H3PO4 (­ 2.06)

HPO3 (­ 5.19)

2­

PO4 (­ 7.43)

3­

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

114


17.

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

1.
6



14

Si

32

Ge

50

Sn

82

Pb

[ ] ns2np , ()

2

0.077 0.117 0.122 0.140 0.175


11.26 8.15 1.26 1.38

7.90 1.11

7.34 1.23

7.42 0.36

, ,

: ) -4, 0 +2 +4, ( ) , ­ . , . +2 (SiO, SiHCl3) ) , ( ). ) ­ ­ ) ­ Si-O ( )

115


) ­ , Pb(+4) ­ ( 6s2 ­ ).

2. : CO2 ( ), (, ), , (, , , , ), . : ( SiO2, ). : , : SnO2 (). : PbS (). : tC SiO2 + 2C = 2CO + Si ( SiC) t C SiCl4 + 2Zn = 2ZnCl2 + S i ( ) tC SnO2 + 2C = 2CO + Sn tC 2PbS + 3O2 = 2PbO + 3SO2 tC PbO + C = Pb + CO 3. . 3.1. , , 17.1. , . , . . 116





, .






, 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 Sn + 2H+ = Sn2+ + H2 ( , , E0 (Sn2+/Sn) = ­0.14 117


3Pb + 8HNO3 (30%) = 3Pb(NO3)2 + 2NO + 4H2O

4. , 4.1. : ) . ) - . ) . SinH2
n+2

­ ­

: 4Mg + SiO2 = Mg2Si + 2MgO () Mg2Si + 4HCl = 2MgCl2 + S iH4 4.2. : ) S iH4 + 2O2 = SiO2 + 2H2O ) SiH4 + 2H2O = SiO2 + 4H2 ) ­

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

118


CO

2



C + O2 = CO2

CO2 + H2O CO2·H2O H2CO3 H++HCO3­

SiO
2



SiCl4 + (4+x)H2O = SiO2xH2O + 4HCl SiO2xH2O = SiO2 + xH2O tC Ge + O2 = GeO



GeO

2


2

Sn(OH)2 = SnO + H2O SnO - SnC2O4 = SnO + CO + CO2 tC Ar SnCl4 + (4+x)H2O = SnO2xH2O + 4HCl tC 2PbS + 3O2 = 2PbO + 2SO2

SnO

2

PbO



Pb3O4

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



PbO

2



: CO , CO Mx(CO)y. CO2 , CO2 , SO2, .



119




SiO2 (, , ..) PbO . Pb3O4 () Pb2+2Pb+4O4





6. . : H2CO3 (SiO2·nH2O) : ( ). : , , .

: H2CO3: , H+ HCO3­, CO2·H2O; (), () , 2NaHCO3 = Na2CO3 + H2O + CO2



SiO2·nH2O: , , ; , ­ , , . 7. . 7.1. ­ , , -. 7.2. Pb(OH)2 ­ Pb(OH)2 + 2HNO3 = Pb(NO3)2 + 2H2O Pb(OH)2 + 4NaOH = Na4[Pb(OH)6] 120




7.3. Pb(+4) ­ , ( Bi(+5)). Pb(+4): 1) PbO2 (. ) ­ PbO2 + 4HCl = PbCl2 + Cl2 + 2H2O 2) (NH4)2[PbCl6] : 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 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

Mn(NO3)2, HNO3 X2 HCl . ... Xi ­ , . X1

H2S X3 PbO Pb

121


18.

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

1.
5

B ­ 13 , .
1

[He]2s22p () 0.088.

8.298 : ) « » ­ . ) +3; ) B - Si ­ , , .. , ; ) . - ; ) .

122


2. . . () Na2B4O7·10H2O Ca2B6O11·11H2O. tC B2O3 + 3Mg = 2B + 3MgO tC 2BI3 = 2B + 3I2 ( ) tC 2BBr3 + 3H2 = 2B + 6HBr

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. 123


: 2BF3 + 6NaH = B2H6 + 6NaF ( ) 4BCl3 + 3Li[AlH4] = 2B2H6 + 3 LiCl +3AlCl3 : , B-H-B.

. 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

124


5. 5.1. B2O3: tC 4B + 3O2 = 2B2O3 tC H3BO3 = B2O3+ H2O : , . B2O3 + 3H2O = 2H3BO3 5.2. ­ (SiO2·nH2O). : , ; . ; . : H3BO3 ( ), 5.3. : (HBO2)n ­ HPO3. ­ , : H3BO3 + H2O H+ + [B(OH)4]­



5.4. . Na2B4O7·10H2O ­ ­ Na2[B4O5(OH)4]·8H2O

. 18.2. [B4O5(OH)4] 125

2­


: B4O72­ + 7H2O 4H3BO3 + 2OH­ : , ,

tC 2(Na2B4O7·10H2O) + 2Co(NO3)2 = 2Co(BO2)2 + 4NaBO2 + 4NO2 + O2 + 20H2O

: tC 3(NaNH4HPO4·4H2O) + 2Cr(OH)3 = 2CrPO4 + Na3PO4 + 3NH3 + 18H2O

Na2B2O4(OH)4·6H2O : Na2B4O7·10H2O + 2NaOH + 4H2O2 + H2O = 2(Na2B2O4(OH)4·6H2O) : [B2O4(OH)4]2­ [B2(O2)2(OH)4]2
­

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

2­

6. BX3, X = F, Cl, Br, I 6CaF2 + Na2B4O7 + 8H2SO4


= 4BF3 + 2NaHSO4 + 6CaSO4 +7H2O
4

B2O3 + 6NaBF4 + 3H2SO

= 8BF3 + 3Na2SO4 + 3H2O

B2O3 + 3C + 3Cl2 = 3CO + 2BCl3 AlBr3 + BF3 = AlF3 + BBr 126
3


6.1. p ­ p - ­ 2p ­ p ­ - ­ B-X . 6.2. ( BF3): BF3 + NH3 = BF3·NH3. 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

7. . , . . B2O3B2H6Na[BF4]

1. . , . 2. , . .

127


pH
1. 4.8 NaNO3, 1.053 /, 0.509 . . 2. 14% . 1,0675 / 3. 1.088 /. 20 4.352 H2O2. . 4. ( 100 ) : 14,3 (0) 39,5 (60). CuSO45H2O 0 500 , 60? 5. 200 40%- , 15%? 6. (..) 200 6%- (II), 4%- ? 7. 0.5 0.1 HCl NaOH 0.3M. pH , . 8. pH 3 . Ka = 1.76·10­5. 9. pH 2% 25°. 1.035 .3. Ka2 H2CO3 = 4.8·10­5. 10. pH 0.1 HCN? Ka = 6.2·10­10. pH , 500 4 KCN?

128




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

129