Травление стали в восстановительныхрасплавах

,
–
, . .o.,
!
,
"
. #
,
(Fe, Cr),
.
30 %
,
,
,
.
,
,
,
(
.
40-
-
.
.
'
1941
. ,
.
)
-
«$
!
»
)
'
(
[1]
)* +,
.
,
6
(
(
).
1913
'
(
.
. %
,
(
,
(
,
,
),
. !
(Fe2O3, Fe3O4, FeO, Cr2O3, NiO, SiO2)
(FeO⋅NiO, FeO.Fe2CrO3, NiFe2O4, FeCr2O4, Fe(Cr2O7), Fe2SiO4).
,
,
$
&
50 %
20 %
,
. %
)
370 – 390 °C.
). -
1,5
2,5
.%
.
,
..
'
..
,
,
'
,
.
'
!
(
,
$
).
. -
(
,
/
'
-
.
)* +
'
. 0
)
,
'
,
%
a)
NaOH + 2 Na = NaH + Na2O
b)
Na2O + H2 = NaH + NaOH
c)
2 Na + H2 = 2 NaH
.
:
,
,
..:
FeO + NaH = Fe + NaOH
Fe3O4 + 4 NaH = 3 Fe + 4 NaOH
NiO + NaH = Ni + NaOH
)
,
.%
'
Te
. .
KOH
42
!
'
,
.
,
.
[2]
– NaH. !
. % NaOH,
.
,
'
188 °C)
NaH
(58
.%
,
.
,
'
$
'
'
'
,
.
,
.
0
'
,
-1
.%
,
'
,
50 °C
.
,
'
,
'
.
,
,
.
$
.!
60
.
9
'
. )
,
,
,
–
,
. 1.
$
350, 400
(3,4,5,6). #
-
,
(
' ,
NaOH – Na2O – NaH. 3
,
'
(
'
' ,
'
NaOH – NaH – Na2O
-
,
.
.
∆Gor
-
GoT (B)
(
450 °C
-
,
O2-. 0 .1
,
2
'
2
NaOH – NaH – Na2O,
. $
,
,
o
∆G
r
. &
-
4 2, 3
)
.
-
,
.
-
,
[7,8]. +
2OH- = H2O + O2-
0
(1)
' ,
K(OH-) = a (H2O) . a (O2-)
'
-
'
'
.,
GoT(B)
'
(2)
9
. ,
5
.
O2..
6
$
'
Na2O(l) + H2O(g) = 2 NaOH (l)
(3)
400oC
.1
)
. 1011. /
r
p(H2O)/101325 a,
'
p(H2O),
(3)
K (NaOH) = a (Na2O).rp (H2O) = 7,1 . 10-12
)
(4)
(
(5)
(4)
K = 1,4
'
,
(Na2O) . x (H2O) = 2,5 . 10-13
(5)
x (Na2O) = x (H2O) = 5 . 10-7
(6)
!
r
p(H2O) = 1,4 . 10-5
/
«
»
2-
O
,
«
.
,
,
' ,
,
'
p(H2O) = 1,4 a.
,
». ,
NaOH-NaH-Na2O ,
( .
.1). /
,
.
(7)
'
2 NaH + 2 NaOH = 2 Na2O + 2 H2 (g)
(7)
NaH + Na2O = 2 Na + NaOH
(8)
(8)
' ,
,
.
.1.
,
NaH, Na, H2,
/
Na2O,
'
%
.
;
[10]
[11],
,
.
% . )
NaOH (
NaOH-NaH-Na2O-Na-H2
.4. 0
400 °C.
$
)
NaOH-NaH-Na2O-Na-H2
Na
Na2O. *
NaH
NaOH-NaH-Na2O-Na-H2
. 6
'
,
H2
. 0
,
H2 ( ) + 1/2 O2 ( ) = H2O ( )
(
. 1)
-
. (
-
,
.6
(
'
. ,
( . .
),
r
. ,
Na2O
NaH
p(H2) = 0,01
. )
(
. /
.
"
#
,
.#
'
.
,
.
,
)
),
(9)
. 1.
.2
$
NaH
'
,
$
.400o C
'
(3)
'
,
,
. 3
,
%
,
' .%
,
.
0
Na2O
Na2O.
%
,
.
'
'
'
NaOH-NaH-Na2O-Na
'
-
,
,
.
.-
:
,
'
SiO2 + Na2O = Na2SiO3
(10)
SiO2 + O2- = SiO32-
(11)
%
O2-
,
,
,
,
(
,
,
,
)
,
NaOH-Na2O
(13). 0
.
.
6
. ,
MeO + NaH = NaOH + Me
,
(Cr, Mn, V
. )
' ,
,
,
.
)
(12)
'
,
'
,
. #
,
. /
.,
(
Si, Mo, W, Ti). O
$
0
.
-
,
.).
'
.
,
. %
'
,
NaH
,
Na2O
'
,
(8). ,
,
.!
)
(
%
' ,
.
NaH
,
NaH
)
. .
.
,
,
,
NaH
(10),
'
'
Na2O. A
'
.0
.
'
$
./
,
2 NaH = 2 Na + H2
(13)
,
-
,
,
,
, . .
'
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
,
NaOH
,
.6
.
(12),
.
Na2O.
,
(8)
' (8) o
NaH
#
.
,
,
.
./
' . 6
.
,
Na2O (12). /
Gilbert H.N.: USP 2 377 876
Delille J.: Stahl u. Eisen,1964 ( 1865 – 1872)
Barin J., Knacke O.: Thermochemical Properties of Inorganic Substances, Berlin 1973
Landolt , Bornstein : Zahlenwerte und Funktionen II 4.T., Berlin 1961
#
O., /
E.: ,3
1954
, X, 1.
,3
1981
Goret J., Tremillon B.: Electrochim. Acta, 1967 (1065 – 83)
Goret J., Tremillon B.: Bull. Soc. Ch m., 1966 (2872)
Rahmel A., Kruger H.: Z. phys. Chem., 1967 (25)
Myles k.M., Caffaso F.A.: Journal of Nucl. Materials 67, 1977 (249)
7
!./.:
,
, .8
1985
[12] Danihelka P., Rychtá9 L., Vá:a P.: Hutnické listy 1988 (192 – 194)
,
T
' 4.1:
&.
.
1 2 NaH(1) = 2 Na(1) + H2(g)
(
'
#
∆GoT/ % .
400oC
350 C
-0,660
-6,371
o
-1
450oC
-12,244
2 NaH(1) + Na2O(1) = 2 Na(1) + NaOH(1)
-31,585
-32,703
-33,970
3 2 Na2O(1) + H2(g) = 2Na(1) + 2 NaOH(1)
-62,510
-59,035
-55,696
4 2 NaH(1) + 2 H2O(g) = 2 NaOH(1) + 2 H2(g)
-236,952
-234,694
-232,878
5 Na2O(1) + H2O(g) = 2 NaOH(1)
-149,401
-143,681
-138,165
6 NaH(1) + 0,5 O2(g) = NaOH(1)
-331,979
-328,262
-324,741
7 2 Na2O(1) + O2(g) = 2 Na2O2(1)
-133,153
-124,545
-115,963
8 Na2O2(1) + NaH(l) = NaOH(1) + Na2O(1)
-265,403
-265,990
-266,760
9 2 Na2O(1) + 2 H2(g) = 2 NaH(1) + 2 NaOH(1)
-61,850
-52,664
-43,452
10 2 Na2O2(1) + 2 H2O(g) = 4 NaOH(1) + O2 (g)
-165,649
-162,813
-160,367
11 Na2O2(1) + H2(g) = Na2O(1) + H2O(g)
-146,927
-148,643
-150,321
12 Na2O2(1) + 2 H2O(g) = 2 NaOH(1) + H2O2 (g)
+61,714
+66,425
+70,921
13 2 Na(1) + 0,5 O2(g) = Na2O (1)
-300,394
-295,560
-290,772
14 Na2O (1) + CO2(g) = Na2CO3(1)
-246,856
-238,990
-231,049
15 H2(g) + 0,5 O2(g) = H2O(g)
-213,503
-210,915
-208,302
16 Na2O2(1) + H2(g) = 2 NaOH(l)
-296,328
-292,322
-288,486
17 H2(g) + O2(g) = H2O2(g)
-68,965
-63,084
-57,198
18 0,5 Na2CO3(l) + NaH(l) = NaOH(l) + 0,5 C(s) + 0,5 Na2O(l)
-10,958
-11,121
-11,510
19 Na2CO3(l) + NaH(l) = Na2O (1) + NaOH(1) + CO(g)
+143,478 +134,917-
+126,106
20 2 Na + 2 H2O(g) = 2 NaOH(1) + H2 (g)
-236,291
228,323
-220,633
21 NaH(1) + H2O2(g) = NaOH(1) + H2O (g)
-476,518
-476,093
-475,846
22 2 NaH(1) + 0,5 O2(g) = Na2O(1) + H2 (g)
-301,056
-301,930
-303,016
23 0,25 Na2CO3(l) + NaH(l) = 0,75 Na2O (1) + 0,25 CH4(g)
+4,816
+3,711
+2,504
24 C(s) + 2 H2(g) = CH4(g)
-20,669
-15,577
-10,418
+175,063 +167,620
+160,076
25 2 Na(1) + Na2CO3= 2 Na2O (1) + CO(g)
26 0,5 Na2CO3(l) + 2 Na(l) = 1,5 Na2O (1) + 0,5 C(s)
+20,627
+21,582
+22,460
27 2 Na(1) + Na2O2(l)= 2 Na2O (1)
-233,818
-233,287
-232,790
28 Na2O (1) + H2(g) = H2O (g) + 2 Na(l)
+86,891
+84,644
+82,469
29 Na2O (1) + C(s) = CO(g) + 2 Na(l)
+133,809 +124,457
+115,157
30 Na2O (1) + 0,5 C(s) = 2 Na(l) + 0,5 CO2(g)
+102,801
+97,914
+93,065
31 2 NaH(1) + 0,5 C(s) = 0,5 CH4(g) + 2 Na(l)
-10,995
-14,160
-17,453
0,00
0
∆ GR
-1
(kJ.mol )
2NaH(1) = 2Na(1) + H2(g) (
. 1)
NaH(1) + Na2O(1) = 2Na(1) + NaOH(1) (
. 2)
2Na2 O(1) + 2H2(g) = 2NaH(1) + 2NaOH(1) (
. 9)
2Na2O(1) + H2(g) = 2Na(1) + 2NaOH(1) (
. 3)
-20,00
-40,00
-60,00
-80,00
350
400
450
t (°C)
0 . 1: ,
∆GR0
'
NaOH – NaH-Na2O
0 . 2: 0
NaOH-NaH-Na2O-Na-H2. *
.