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..

11

. ..

2004


, NO NO2
NO2 40% .


,
180C, 30C.
(%, .):
NO A; O2 B; N2 C; H2O D
, ,
30C. %. 100
.
: =9%; =7.1%; =69%; D=14.9%; X=2%.


..4
6
1. - ........ 6
1.1- ..6
1.2 (II)...10
1.3 ...11
2. .......14
3. ...17
.19
1. 19
2. ......20

.24

.
.
.
.
. .
.

.
..
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24

11



. , ,
.

,
.
.
,
,
.

,
, ,
, -
.

, ,
. : ;
; ;
.
.

,
.
.

.
.
,
. , 40%
;
,
, , ,
.
, .
.
. ,
( ).

.

, ,
.
-
.
. ,
, .
.

. , , ,
, .
. , ,
: ,
.
,
.


1. -


:

4NH3+5O2=4NO+6H2O

2NO+O2 2NO2

3NO2+H2O = 2HNO3+H2O

NH3+2O2 = HNO3+H2O
1.1 -

N 2 .

:
4NH3+5O2=4NO+6H2O+946
(1)
4NH3+3O2=2N2+6H2O+1328
(2)
4NH3+4O2=2N2O+6H2O+1156
(3)
(
) :
4NH3+6NO=5N2+6H2O
(4)
2NH3=N2+3H2
(5)
2NO=N2+O2
(6)

.

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

,
( ). , ,
, .
, ,
, ..
, (1) (II).


,
.
, .

.

NH3 ,
(II)
.
(1)
.
(II) 97 - 98% 95 - 96%
0.88 - 0.98 . (II)

, , ,
- ,
, .
.
(II). NO
, (
900 - 920C), .
,
.
195C. ,
.
(II) 300C.
(II) ,
96% 99% Pt Pd Rh.
,
(II), :
. .
650 900C 510-4
1.110-4 .
, ..
.
:
,
,C

0.1

0.304 0.51

0.71 1.011

780 800

850 870

880 920

780 850C
.

- .
, .
.
(II).

.
,
.

0.41 0.73 .
NO

( ). ,
(II) 98% 0.41 0.71
950C.

,
.

. , , , ,
,
NO
.
.
, , . NH3
-
. (1) 1
1.25 . ,
- :
21
21
1.25 : 100 + 1.25 100 = 14.4 . %

O2:NH3=1.25
(II) 60 80 %. ,
14.4% NH3
. 13.8 . % NH3.
.

1902 . . ,
,
NO ( 90%) .
,
~180C, , .


.
NO,
.

,
Pt Rh Pd; .

: Pt+4 . % Pd+3.5 . % Rh
Pt+7.5 . % Rh .
NH3
.
, ,

. 0.09 ,
0.22 32 1 , 1024 1 2.
( 1) (
5) ,
.
, , , ,
, , , .
.
,
.
-
,
. ,
, ,
.


.

, .
30 .
,
.
9

: 14 .,
0.73 8 9 .
1.2 (II)
, ,
(II), , .
(II) .
2NO+O2 2NO2+112.3 .
,
. ,

, .. NO2.
:
t, C
Kp

20
1.24103

100

200

1.82107 7.41103

300
45.5

500

700

8.510-2 2.1210-3

900
1.5110-4

, 100C
NO2.
700C
.
, , NO2
,
100C. (II)
.
.
:
wr = kC2NO CO

(7)

, .

,
,
(II)
NO NO2.
NO NO2 ,
.
,
, , , NO NO2
(II):
2NO (NO)2 + Q

10

O2 +(NO)2 2NO2 + Q
,
. ,
.
,
.

dn NO2
d

= k1 p( NO )2 pO2

(8)

P( NO ) . ,

,
.
, ,
92%, NO (
NO2) ,
.
10
50C. N2O4:
2

2NO2 N2O4 + 57

:

NO2

, C

200

100

70

30

- 20

, %..........

0.7

2.5

38

77.8

89

92

NO2 ,
NO2:N2O4 ,
.
,
N2O4.
, , NO2, N2O4, NO,
N2O, N2, N2O3, .
1.3 .
, NO, .
NO2, N2O4,

11

N2O3 .
,
(II) . :
2NO2 +H2O HNO3 + HNO2 +116

(9)

3HNO2 HNO3 + 2NO + H2O -76

(10)

NO2
3NO2 + H2O 2HNO3 + NO + 136 ,
. ,
NO2 2 HNO3 1 NO,
NO2:
2NO + O2 2NO2

(11)


. NO2 N2O4


.
NO2 . NO2
(9),
.

(10). NO
.
(11).

, .
,
, .
,

.

, , ,
.
.
65%
. 1
NO2 .
,
NO2 .

, NO NO2
,
.
, ,

.

, .
2
.

1
35C 0.1

2
72: 1 ; 2 ; 3

13
12

2.
72.

1.42
0.47 1.1 1.26 ;
60% - HNO3. 72
380 . / 1976 .

3. 25,
24, 23 0.42 ,
,
. ( ) 1
2, 10 16C 0.6 .

3 4,
80 120C .
22
20. -
9.6 10.0 . % NH3. ,
, -
,
. 840 860C
- 19,
, 40
440C. ,
17.
16, 150C, 18
- 21.
-
18, 15
14 55C.
40
45%- , 13.
.
, -
.
10,
12 11 12.6 , 210
230C. 16 155
165C, 11 60 65C
10.
.

14

3 -72:
1 ; 2; 3,24 ; 4, 15 ; 5
; 6 ; 7 ; 8 ; 9
; 10 ; 11, 14 ;
12, 23 ; 13 ; 16, 18
; 17 ; 19 -; 20 ;
21 ; 22 ; 25

15

(H2O) 40C. 58 60%-


; 9
.

( ) 8, 7
480C
6.
-2. ,
0.008 . % 750C,
5, .

0.95 1.05 . ,
,
12 13 ( ).

16

3.

.
4
. 2
- .
;
5, ,
; ,
,
. -.
48 50 HNO3 .

.
.

.
.
,
.

.
, ,
, ,
.
( )

85 90%.

17

4 , :
1 ; 2 ; 3 - ; 4 ; 5 ; 6

18

: = 9 %, = 7.1 %, = 69 %, D = 14.9 %, X = 2 %.
1.
100 .
:
H2O H2O.

(1)

2NO + O2 2NO2

(2)

3NO2 + H2O 2HNO3 + NO


___________________________

(3)

2NO + 1.5O2 + H2O 2HNO3

(4)

,
, :
NO 9.0 ; O2 7.1 ; N2 69.0 ; H2O 14.9
, ,

HNO3 40%- HNO3.
(3) ,
. S
H2O, , r
, . 40%- HNO3
:
(2 S 63) + 18 (r S) , (2S63)
100% HNO3. , S = 0.087r .
r
40%, 30C
2.7 [3,.530].
:
(14.9 r)P
100 1.3045r
: 101.3
2.7 ,

19

101.3 (14.9 r ) P
= 2.7 P ;
(100 1.3045 r )
1509.37 270 = (101.3 3.522) r ;

r =12.68
(2) (3), NO O2
. 1.
1

, %

, NO2
, O2
, N2
, H2O

9 0.17412.68 = 6.79
7.1 0.130512.68 = 5.45
69.0
14.9 12.68 = 2.22
100 1.304512.68 = 83.46

8.14
6.54
82.67
2.65
100

HNO3
(3) 2.2 HNO3, 2.263 = 138.6 .
40%- 346.5 . 100
, , 346.5 40%-
HNO3.
2.

2NO() + 1.5O2() + H2O() = 2HNO3()
/: HNO3 = +206000,
H2O= 242000, NO = -90500.
: Qp = Q Q
Qp = 2060002 (242000 905002) = 351000 .
2.2 HNO3 386100
.

298. (478 ),

20

.
, 180C
(478 ), :
Q1 = m c t,
180C (478 ), /C,
:
= 0 + 1 + 2/2
, ,
:
QNO = 9 29.4 180 = 47628 ;
QO2 = 7.1 30.0 180 = 38340 ;
QN2 = 69 28.9 180 = 358938 ;
QH2O = 14.9 33.7 180 = 90383 .
Q1 = Qi = 535289 .
:
Q2 = m1 r1;
m1 , ,
, , m1 = 209.7
r1 ( ), [3,c. 449] r1=2260
/.
, , :
Q2 = 209.7 2260 = 473922 .
:
Q = Qp + Q1 + Q2.
Q = 386100 + 535289 + 473922 = 1395311
, 30C
(330 ),
[1, c.38, ], :

21

Q'NO = 6.79 28.6 30 = 5826 ;


Q'O2 = 5.45 29.4 30 = 4807 ;
Q'N2 = 69.0 28.4 30 = 58788 ;
Q'H2O = 2.22 32.7 30 = 2178 .
Q'1 =Q'1i = 71599 .
, 40%- HNO3 30C (303 )
:
Q'2 = m c t,
40%- HNO3, [4, c.432] = 28.9 /C
Q'2 = 346.5 28.9 30 = 300416 .
, ,
:
Q = Qp = Q'1 + Q'2 + Q'3 + Q;
1395311 = 71599 + 300416 + Q'3 + Q;
Q'3 + Q = 1023296 .
(Q) 2% (
):
Q = 0.02 1395311 = 27906 .
, ,
:
Q'3 =1023296 27906 = 995390
2.

22

2 ( 100
)


535.289
, Q1
473.922
, Q2
386.100
40% HNO3, Q

1395.31

38.4
, Q'1
34.0 HNO3, Q'2
27.6 , Q'3
,
Q
100

71.599

5.1

300.416

21.6

995,390

71.4

27,906

1.9

1395,31

100

23


1.

. 2 / . .
, . . . : - , 2001.-39.
2. . . . .- .: .
, 1991.-448.
3. . . . .: . , 1996.520.
4. . .: , 1967.-.1.-936.

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