. .. 51
: -
.. : , ..
:
1999 . . .. -1999
.
3
I. 1. 4
2. . 12
II. . 25
III. 28
IV. . 45
V. . 47
. , , .
, , . , , .
, , , .
, , , (, ).
.
I. 1. []
.
. , , , , , . . , - . . XVI .. 400 ! IV .. 300 , 5000 147-, .
, . , 10 . , .
- , . . , , . , , . . "" , .
. , , . , - "".
, . ; .
.
(4,7.10-3 % ) 26-. , . , 1957 420 . . . , .
. , , -CuFeS2, - - Cu2S, - CuS, - uCO3.u(OH)2, -
2uCO3.u(OH)2.
.
- , , -. -8,96 /3, -1083 0, - 2600 0. , , 2,5 (5 ). , .
, , .. . . , , . , , , , , .. , , , .
, , . (4-) s-, d-(3-) . s -, d-, . +2 (II) , , +1 (I). (III).
, . , . , , , , , - "". (), , (SO2), CuSO4 .3Cu(OH)2, - CuC12 . 3Cu(OH)2. , (75%). , , "" . , . . , .
: . . CuSO4 .3Cu(OH)2.
. -(I). CuO. u2O. , (, 4) Cu2O:
Cu2O + H2 = 2Cu + H2O (1)
Cu2O + CO = 2Cu + CO2 (2)
, . . ("").
(II) . , . , Cu(OH)2 , .
, , , , :
Cu + C12 = CuC12 (3)
:
2Cu + J2 = 2uJ (4)
:
Cu + S = CuS (5)
, . .
. , :
3Cu + 8HNO3 () = 3Cu(NO3)2 + 2NO + 4H2O (6)
:
Cu + 2H2SO4 () = CuSO4 + SO2 + 2H2O (7)
1.
.
, . , , , . , .
, .
1. []- u2O- 2, 2S, SO2 - NH4OH [Cu(NH3)4](OH)2- c KCN + O2 + H2O K[Cu(CN)2] 3[Cu(CN)4]- c HNO3 Cu(NO3)2 . n H2O- Cu2O uO- c F2, C12, Br2, J2 CuF2, CuC12, CuBr2, CuJ2- c S, Se, Te CuS, CuSe, CuTe- 2S CuS- P, As, Sb, C, Si Cu3P, Cu3P2, Cu3As2, Cu3As, Cu5As2, Cu2Sb, Cu3Sb,
- 1 u12- 2SO4 CuSO4 . H2O- c NH3 Cu3N- c NO2 NO Cu2O. , FeS2 FeS , CuS Cu2S. Cu2S.FeS, . : , , .
. (2SO4, NH4OH, NaCN, Fe2(SO4)) , (, ) .
- . , .. , (), (), ().
, , 93-98,5% , , , , , , , , , , , . , , , , - , , , , , , . , - . , . , , , , , , , , . (IV) , As2O3 Sb2O3, .
, Cu2O, Bi, Sn, Ag, Au, Pt . , .
, . - . . , . , , (Ag, Au, Pt, ), . , .
CuSO4 Cu2+ + SO42- (8)
H2O H+ +
OH- (9)
: Cu2+ + 2e Cu0
: 2O- - 2e 1/2O2 + H2O
2. .
, , () , , -. - , .
, . , , (0,05 /). , [].
pH [] . , . , , .. , . , Cu (I) Cu (II), - (I) (II). , . (), , , . NaC1. , Cu()2, -.
[] 1 3% , , 3 % NaC1 . (u+, CuCl2-, CuCl32-) .
=0,5, , [] , :
Cu + Cu2+ 2Cu+ (10)
. , (m) 10,01 []. c :
) u + nCl- CuCl + (11)
) Cu Cu+ + e (12)
Cu+ + nCl- CuCl
. -, NH3 NH4C1 [], : uC12, Cu2O, CuO (), CuC12.3Cu(OH)2 CuC12 . 2NH4C1.H2O, . , , . .
FeC12 , , CuC1 u2. . -, . u1 , , CuC12 -1- , , , , , . , Cu1 . FeC13 , FeC13 - Fe3+ .
, Fe3+ - 1- -, , -, CuC1, CuC1, CuC1, Cu2C1.
CuC12 FeC13 :
Cu + CuC12 2CuC1 (13)
Cu + FeC13 CuC1 + FeC12 (14),
, .., , :
u + C1- CuC1 + e (15)
CuC12 + C1- + CuC1 (16)
u1, , CuC1, CuC1, (II).
u (I) NaF-KC1 []. , u (I) . u (I) u+ /Cu u2+/Cu+. , (I) , Cu (II) . F - -.
u(NO3)2.3H2O () [] (II). (1) (2) () (-). 0,1. 6 /2 55 0.
(17). :
= 188,58 - 0,321 + 0,802 - 0,3312
, . , (17), , u - e Cu+ (18)
, (I), , , :
Cu+ + H2O CuOH + H+ (19),
2Cu+ + H2O Cu2O + 2H+ (20),
, .
[]. -, 20 u(NO3)2 . . , , u+ , . Cu+ , u+, .
, --2SO4, , []. , , , Cu+, . , , , (2SO4) 0,5 /t=25 0C.
, (i) 5 , . . 2. i, i2, , , - .
2, , :
2 + 2- (21),
2- + + 2 (22),
[10] :
u+ + O2 Cu2+ + O2- (23)
Cu Cu+ + e (24)
Cu2+ + e Cu+ (25)
:
HO2 + Cu+ Cu2+ + HO2- (26)
O2- + H+ H2O2 (27)
22 + u+ u2+ + - + (28)
+ u+ Cu2+ + OH- (29)
OH- + H+ H2O (30)
, , , 1.
, [13-17]. [] .
. 1 = 10-2-10-1 /. , 1. 1 10 , . , [13] ().
i. 10 .% 23+ + 23+ + 3(31)
. .
(Z), 1 , () . . uC12 Z0,6-0,8. . , , u2+ Cu+ (12), .. , , .
. . 10-20 . , .
, 1. 0,9. ii, .u2+ , . , [13], , , - (10). CuC12.
11 , .
1 [] (10). , Cu2+ u+ .
[14] 1 (0,4-10 .%), (0,1-3,0 /)
(10-2-10-1 /). 1. .
, . i(0,1-1,0 /) 2010 /2 955 /2 1. 2 10 .% 2.
11 , (i) 3 , , , . , Cu2+ , . u12 ii, . , 1Cu2+>10-2 /, (12) . , , 5.10-2 /Cu2+ .. 100 2500 /2. .
1. , 2. (1gK/ lgCHC1)Ci 0,15-0,20, . ( lgK/ lgCHC1)Ci 0 (lgi/lgCHC1)Ci= 0, , , 1 (10), , , Cu2+. (10).
[] , -. , , . lgi0 - lgCC1- 2. , CuC12 .
; , , , . , , - . i-1 - -1/2, , , . 60 .
, -2,4-: uC1, . -. :
[CuC1(ROH)n] + C1- [CuC12(ROH)n-1] + ROH (32)
, , .
, . . .
-3721, (0,2-10 .% ), (1-3), , []. , . . 60 . 20,2% nH+=1 2, n1- (1 2) (3). -nH+=0 , n1- =2.
:
u + mH+C1 + (33)
u + mC1 Cu(C1)-+ (33)
CuC1+ mH+ (34)
Cu(C1)-CuC1 (34)
n, 0(35)
((33-34), n=0, c, , n=m.
[] , ( (), , []) , 11.
. , , , , . Cu+ .
, .
, , . , , , . Cu2+ 51 -.
II. .
1 (99,94% u). :
1. + 51 + u12.
2. + 51 +10% 2+ u12,
10-4; 10-3; 10-2; 5.10-2; 10-1.
".." 0,2 .%. (.). , 2SO4 NaCl "..", [], :
NaC1 + H2SO4 NaHSO4 + HC1 (36)
10 .% , .
. (II) 100 0C.
, . -22 . . . 2-- 5.10-5 . () =Dm/(St) (37),
Dm - ,
t - ,
S - 2.
, k, 2,3881:
i= /k (38)
. , (5827, 20 ). (- ) , () - (i):
i = I [A] / S [2] (39),
S - . .
1,12 0,07749 18 0. 0,2 . () () :
= . , (40)
- ;
- .
, 18 0:
(41)
- ;
1 - ;
2 - .
III. .
, , 5.. 1 2,1.10-4 /(2.). , , . , u2+ , (12):
Cu2+ + e Cu+
, (10):
Cu + Cu2+ 2Cu2+
, Cu+ .. 1 (uC12) 10-4 /10% (. 1). u2+ .
, (.1) (II), 2-3 u2+ (. 1). , , Cu2+ .
.1. 51 + u12 ..
. . .
: 1-0; 2-10-4; 3-10-3; 4-5.10-2; 5-10-1.
.2. , CuC12 51 + u12 .. . .
. : 10-4;10-3;10-2; 5.10-2; 5-10-1.
1- i; 2- i,; 3 - i; 4 - ( i,- i0)
1.
Cu12 ,
5.. 1.
(. -2 .
.)
, CuC12, //2010-410-310-25.10-210-1i,8,79.10-59,63.10-51,00.10-41,55.10-41,60.10-42,09.10-4i6,90.10-53,98.10-56,31.10-56,31.10-58,70.10-58,70.10-5i2,50.10-42,50.10-43,61.10-44,20.10-45,00.10-41,00.10-3
, 5.. 1, , Cu12 , (. 1). . (i) - () Cu2+ (i,u2+):
i= + i,u2+ (42)
2 (i), , , 2,3881 (i,) u12. 2 , 2,5-5 iCu2+,
2.
/CuC12CuC121( lgi/ lgCCu2+)0,1210-4 10-1010-4 -10-20,8010-2 - 10-12( lgi,/ lgCCu2+)0,1210-4 10-1010-4 -10-20,9010-2 - 10-13( lgi/ lgCCu2+)0,2010-4 10-1010-4 -10-21,2010-2 - 10-14( lg(i,-i0) / lgCCu2+)0,5010-4 10-1010-4 -10-22,1010-2 - 10-15( lgia / lgCCu2+)-0,4610-4 10-1-1,410-4 -10-2, , -.
u12, 0,12; ii0,12 0,20 (. 2). 1 Cu2+, , , , - CuC12, , , :
i,= i0 + iCu2+, (43)
i0 - , , iCu2+ - Cu2+ .
, iCu2+ (i,Cu2+) (i):
iCu2+ = i,Cu2+ + i. (44)
, CuC12 ( lg(i,- i0)/ lgCCu2+) 0,5 (. 2, . 2).
Cu2+ . 5.. 1 (J).
J = 1/2 , (45)
i - ; Zi -.
J :
J = 1/2 (CH+ + CC1- + 4CCu2+), (46)
CH+ = CHC1; Cu2+ = ; C1- = CHC1 + 2
.3. ) 51 + u12 .. . . .
: 1-10-4; 2-10-3; 3-5.10-2; 4-10-1.
) . 3.
(46) :
J = CHC1 + 3. (47)
-, J:
J = J-J0, (48)
J0 - .
(5 /1), 10-4 -10-1 /J, , (. 3). , , , -:
lg f = - A (49)
3.
Cu12 51 .
CuC12, /10-410-310-25.10-210-1J = J-J0,3.10-43.10-33.10-21,5.10-13.10-1l = ,6.10-36.10-20,62,95,76-CuC12 3 . , Cu2+. 5.. . 3. 50 , [16] 1.
, (0,04 ) ia, lgia lgu2+ (. 3). , Cu2+, -0,46. ( lgi/ lgCCu2+) Cu2+ . , Cu12 , , Cu2+ (12).
10 .% , , . CuC12 (10-4 - 10-2) , CuC12 - (.4).
51 10 .% 2CuC12 , , , .. : (i,iCuC12 , .
4. 10 .% 2CuC12 10-4 - 10-2 /51, Cu2+ 10-2-10-1 /.
5. . , CuC12 ; 10