NO2 Absorbant by H2SO4

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NASA TECHNICAL TRANSLATION

&

NASA TT F-17088

ABSORPTION OF NITROGEN OXIDE BY SULFURIC

ACID SOLUTIONS

A. V. Baranov, E. A. Liberzon and

T.

I

Popova

Translation of Pogloshcheniye Dvuokisi

Azota Rastvorami Sernoy Kisloty, Trudy Sibirskogo

Tekhnologicheskogo Instituta, Vol.

38,

1966,

pp.

77-86.

(HASA-TT-P-17Cee)

AEICBPTIOB OF NITBCGER B76-27388

OXIDE El SULFUBIC

AC IL SCLOTICXS (Kaaner

(Leo)

Associates,

Annapolis, a d . 12

p

HC

$3.50

CSCL

07C On c l a s

6 3 2 5 44592

*

. .

NATIONAL AERONAUTICS AND SPACE ADMINISTRATION

WASHINGTON,

D.

C. 20546

MAY 1976



.

A. V Baranov, E A. Liberzon, I 8 penform~ngOrgon*rot,on Report No.

1 ANIJLUT) TI11

F

PACE

T. I. Popova

. .. .

Government Access~onNo.

US - lT_F :17088

_

4

Totl* ond Subtatlc

ABSORPTION OF NITROGEN

CXIDE BY SULFURIC ACID SOLUTIONS

10. Work Un ~ t o

. .

3. Recep tmt s Cotoloy No

.

.

5 ~mpo rt ote

ay

_1_9_76

. _

6. Performang Ol go n~otaonCode

11 1. Controct or G ~ on t o.

9

P e r f o r m ~ n ~rganttotaon Nomo and Address

Leo Kanner Associates

13. Type 01

~~~~~t

ond Perood Covered

Annapolis, Maryland 21401

Translation

Asw-2790

2 Sponsor~ng gency Nome m d Address

NASA, Code KSI

Washington, D.

C.

20546

4. Spons or~ng gency Code

S Supplemen*oryN0t*~ Translation of Pogloshcheniye Dvuokisi Azota

astvorami Scrnoy Kisloty, Trudy Sibirskogo Tekhnologiches-

ogo Instituta, Vol. 38, 1966, pp. 77-86.

E

16. *bstroct A study is made of the composition of the liquid

phase formed upon absorption of nitrogen dioxide by sulfuric

acid as a function of the concentration of oxides in the gas,

temperature and ccncentration of sulfuric acid. It is found

that in the process of absorption of NO2, mixtures consisting

of HN03 HNOS04 + H2Sg4

+

H20 are formed, containing quite

_

definite maxin~urc concentrations of HNOS04, dependent on

temperature, NO, concentration in the gas and concentration

L

of absorbing sulfuric acid.

This'dependence is established.

An equation is produced for determination of the maximum con-

centration of HNOSO

.

The possibility is shown of producing

mixtures with high 4 ~ ~ 0 3ontent by absorption of nitrogen

oxides.

I

Unclassifjed. Unlimited

(of t h ~ seport)

Unclassified

20 Secur~tyC los s ~f . o f t h ~ soge)

Unclassified

21

No. of Poges

22 pr ice



ABSORPTION OF NITROGEN OXIDE

BY

SULFURIC

ACID SOLUTIONS~

A. V. Baranov, E.

A

Liberzon and

T. 1 Popova

Concentrated nitric acid is presently produced primarily

/77

y concentration of weak nitric acid in the presence of sulfuric

acid. One significant shortcoming of this process is the need

to concentrate large quantities of treated sulfuric acid, involv-

ing significant capital expenditures and operating costs.

Trinary mixtures of the necessary

composi: Jn can be pro-

duced by absorption of nitrogen oxides by aqueolls solutions of

sulfuric acid which, when distilled, produce concentrated

nitric acid. The treated sulfuric acid, it is suggested, can

be sent without preliminary concentration to an ordinary absorp-

tion installation to produce the trinary mixtures. The cumber-

some and expensive process of concentration of the spent sulfuric

acid is thus eliminated. Based on the literature data

[I-41,

we know that gaseous nitrogen dioxide is absorbed by sulfuric

acid at a rather high rate with the formation of nitrosyl sulfate

and nitric acid.

The kinetics of absorption of oxides of nitrogen by solutions

of sulfuric acid have formed the subject of a number of investiga-

tions [S-10). Particular attention has been given to the explan-

ation of the relative rate of absorption of oxides of nitrogen of

various compositions by sulfuric acid. When nitrogen dioxide

interacts with sulfuric acid, the following reaction occurs:

Equivalent quantities of nitrosyl sulfate and nitric acid are

formed only by absorption of nitrogen dioxide commercial

~e~orted t a conference of workers of nitric acid plants in

Dneprodzerzhinsk, 1953.

*Numbers in the margin indicate pagination in the foreign text.



s u l f u r i c a c id .

F ig u re 1 Diagram o f E x p e ri m e nt a l I n s t a l l a t i o n

I n aque ous s o lu t i o n s o f s u l f u r i c a c i d , n i t r o s y l s u l f a t e

i s

7 9

h y dr o l yz e d, a nd t h e n i t r i c a c i d for med i s decomposed, forming

n i t r i c a c i d and n i t r i c o xi de

Only when t h e s e r e a c t i o n s c o n t i n u e t o c o m p le tio n c a n th e y b e

r e p r e s e n t e d by t h e o v e r a l l e q u a t i o n:

N i tr o sy l s u l f a t e

i s

f u l l y h yd ro ly ze d o n ly i n d i l u t e a qu eo us

s o l u t i o n s o f s u l f u r i c a c i d a bo ut 5 7 ) . I n more concen t ra ted

s u l f u r i c a c i d , t h e d eg re e o f h y d r o l y s i s o f HNOS 4

depends on a

number o f f a c t o r s . The d a t a a v a i l a b l e do n o t a l l o w u s t o d e t e r -

mine th e compos it ion o f t he mix t u res p roduced upon ab sor p t ion o f

n i t r o g e n d i o x id e by s u l f u r i c a c i d .

In the p res en t work , we s t ud ie d the compos i t ion o f t he

l i q u id p h a s e fo rm ed upon a b s o r p t io n o f n i t r o g e n d io x id e by



s u l f u r i c a c i d a s a f u n c t i o n o f t h e c o n c e n t r a t i o n o f o x i d es i n

t h e g a s , t e m p er a t u re and c o n c e n t r a t i o n o f s u l f u r i c a c i d . The

s t u d i e s we re pe rf or me d o n t h e i n s t a l l a t i o n shown i n F i g u r e

1.

The n i t r i c ox i de f rom t h e gas met e r was s e n t t h r ough a d r ye r and

rheometer t o a mixer . Here oxygen was se n t from a cy l i nd er ,

a f t e r a l s o p a s s i n g t h ro u gh a d r y e r a nd r he om et er . A f t e r t h e

m ix er , t h e m i xt u r e o f g a s s e s p a s s e s t h ro u gh t h e o x i d i z i n g v o l -

ume, where

NO

i s p r a c t i c a l l y c om pl et el y o xi d i ze d t o N O 2

The

n i t r og en d i ox i de f or med i s l i q u e f i e d a t 10-12 C By th er mo st at -

i n g t h e v e s s e l w i t h l i q u i d o x i d e s o f n i t r o g e n a nd p a s s i n g a n

i n e r t ga s n i t r o g e n ) o r ox yg en t h ro u gh i t w e produce a mixture

o f g a s s e s o f t h e r e q u i r e d c o mp o si t io n . g a s o f t h e p r e d e t e r -

mined composit ion i s s e n t t hr ou gh a c o i l i n t h er mo s ta t t o a n

abs o r b i ng ves s e l .

F or b e t t e r a s s u r a n c e o f c o n t a c t o f t h e g a s m i x t u r e w i t h

th e l i qu id , we used the bubbl ing method. The gas mixture en t ere d

t he abs o r b ing ve s s e l f r om t h e bot tom t h r ough a po r ous g l a s s p l a t e

i n the form of t i ny bubbl es , forming a smal l foam la ye r above

t h e l i q u i d . To d e t e rm i n e t h e c o n c e n t r a t i o n o f n i t r o g e n o x id e s

i n t he incoming and outgoing gas ,

w e

used t h e method of absorp-

t i on by a l ka l i . The gas was drawn t h r ough t h e abs o r p t i o n ba t t e r y

by a n a s p i r a t o r . I n t h e l i q u i d p h as e , we d e te r mi n ed t h e c o n t e n t

o f n i t r i c a c i d, n i t r o s y l s u l f a t e and s u l f u r i c a c i d. I n one s pe -

c imen , by t he method o f back t i t r a t i o n ,

w e

d e t e r m i n e d t h e t o t a l

ac i d i t y o f t h e mi x t u r e . I n ano t he r s peci men we de t e rmi ned t h e

q u a n t i t y o f n i t r o s y l s u l f a t e by t h e m ethod o f Beskov a nd

Sl izkovskaya [ l l ] . Thi s method was used because the ord ina ry 80

perman ga nate t i t r a t i o n method y i e l d s u n s a t i s f a c t o r y r e s u l t s . I n

a sep ar a t e spec imen, us ing a Lunge t i t ro me te r , we de termined the

sum o f n i t r i c a c i d and n i t r o s y l s u l f a t e . With a l l d a t a i n gram

e q u i v a l e n t s p e r u n i t o f w e i gh t o f t h e m i x tu r e , i t

i s

e a s y t o

determine i t s compos i t ion in

5

The c o n t e n t o f n i t r o s y l s u l f a t e

i n t h e m i xt ur ew as c on ve rt ed t o n i t r i c a c i d .

The in f lu en ce of c ont ac t t ime on th e compos i t ion of th e mix-

t u r e formed by a b s o r p t i o n o f n i t r o g e n d i o x i d e w i t h s u l f u r i c a c i d



was s t u d i e d a t s u l f u r i c a c i d c o n c e n t r a t i o n s o f a b ou t 7 0% . The

c o n c e n t r a t i o n o f n i t r o g e n d i o x i d e i n t h e g a s was ma i n ta i n e d a t

41%. The ga s flow r a t e was 40 cm /min. The volume of ab so rb in g

3

s u l f u r i c a c i d was 1 60

cm

.

The tem pera ture was v ar ie d between

20 and 60 C The r e s u l t s p ro du ce d a r e p r e s e n t e d g r a p h i c a l l y i n

F igures 2 and

3 .

During t h e i n i t i a l p er i o d of

a b s o r p t i o n o f o x i d e s of n i t r o g e n b y

s u l f u r i c a c i d , e q u iv a l en t q u a n t i t i e s

of n i t r o s y l s u l f a t e a r e formed, c n r -

r e sp o nd i ng t o t h e e q u a t i o n o f r e a c -

t i o n ( 1 ) . A f t e r a c e r t a i n q u a n t i t y of

n i t r o s y l s u l f a t e i s a c cu m ula te d i n t h e

s o l u t i o n , t h e r e a c t i o n o f e q u at i o n ( 2 )

b e g in s t o o c c ur . With f u r t h e r

a b s o r p t io n o f t h e d io x id e , more

n i t r i c and l e s s n i t r o u s a c i d b eg i n s

Absorption Time hr t o fo rm , a c c o r di n g t o r e a c t i o n s ( 2)

F ig u re

2

Composition

and

3 ) .

of Mixtures Produced

a t 20 C

When a c e r t a in c o n c e n t r a t i o n o f

81

HNOS04

i s

a c hi e ve d i n t h e m i x t u re

rr

I - w e w i l l c a l l t t h e l im i t i n g c on -

\

c e n t r a t i o n f u r t h e r a b s or p t io n of

2 5

N O l e a d s t o an i n c r e a s e o nl y i n t h e

c o n t e n t of n i t r i c a c i d . The c o n t e n t

of HNOS04 remains co ns ta nt , re ga rd le ss

o f th e t ime o f passage o f ox id es oC

n i t r o g e n , t ho ug h t h e c o n c e n t r a t i o n o f

HN03 i n th e mix tu re con t in ues t o

i n c r e a s e .

Absorption Time hr

The r a t e o f t h e p r o ce s s of i n t e r -

F ig u re 3 . Composition

a c t i o n o f NO and H2S04 acc ord ing t o

o f M ixtu re s P ro du ce d fo rm u la (1) d e c r e a s e s a s n i t r i c a c id

a t 40

C

i s

formed.

A t

th e same t ime, th e

i n c r e a s e i n t h e c o n t e n t of HN03 l e a d s t o a d e c re a s e i n t h e q u a n t i t y



o f w a t er i n t h e m i x t u r e ,

w hi ch d e c r e a s e s t h e r a t e of h y d r o l y s i s

of HNS04 acco rdin g t o eq uat ion 2 ) .

A s a r e s u l t , t h e r a t e s o f t h e r e a c t i o n s a c co rd in g t o e qu a-

t i o n s ( I ) , ( 2) an d

3 )

become id e n t i c a l . The r a t e o f f o r m a t ion

of HNOS04 acco rdin g t o equ at i on (1) becomes equ al t o t h e r a t e

of i t s de com pos it i on a c c o r d ing t o e qua t i ons ( 2 ) a nd 3 ) .

The l i mi t i n g co nc en tr a t io n of HNOS04 i n t h e mixt ure depends

o n t h e t em pe ra tu re , c o n ce n t ra t i on of i n i t i a l s u l f u r i c a c i d a nd

c o n c e n t r a t i o n o f n i t r o g z n d i o x i d e .

A t 20

C ,

th e l i mi t i ng con cen t ra t io n of HNOS04

a s

HN02

i s

1 .4 5 g - e q , o r 6 .8 ( F i g u r e 2 ) . The r e a c t i o n ac c o r di n g t o e qu a-

t i on s (2) and (3) begi ns t o occur wi th an HNOS04 con cen t ra t io n

i n t h e mi xt ur e o f a b o u t 0.95 g ~ e q , r 4 .4 6

HNO Z .

T h e r a t e

g r a d ua l l y i n cr e a s e s u n t i l

i t

r ea ch es a v a l ue e qu al t o t h e r a t e

o f t h e r e a c t i o n a c co r d i n g t o e q u a t i o n ( 1 ) . The a c cu m ul a ti o n o f

HNO

i n t h e m i x t u r e o c cu r s a; a r e s u l t o f r e a c t i o n s a c co r di n g t o

3

equa t ions (1) and 3 ) .

A s t h e t e m p e r at u r e s i n c r e a s e t o 40

C ,

t h e l i m i t i n g c o n c e n -

t r a t i o n of HNOS04 reach es approxima te ly 4 HN02, wi t h an i n i t i a l

82

c o n c e n t r a t i o n o f s u l f u r i c a c i d o f ab o ut 70 ( F i g u r e 3 ) .

A t

60

C

th e l i mi t i ng con cen t ra t io n o f HNOS04

i s

2.8 HN02.

N a t u r a l l y ,

t h er e i s a l i m i t i ng c onc e n t r a t i on o f HN03 i n t b e m ix tu r e ,

c o r r es pond ing t o e qu i l i b r i um be tw ee n t h e ga s a nd l i qu id pha s e s .

The dependence of l i m i t i n g HNOS04 co nc en tr at io n on tempera-

t u r e i s s h ow n in F ig u re 4 . The n a t u r e o f t h e c u r v e s i n c o o r d i n a t e s

l i m 1

l e a ds t o a n e qua t i on o f t he f o l l ow ing f or m:

log

H N O ~

T

The appar ent energy

The apparent energy = 3,600.

1

m

I f we r e p r e s e n t t h e d a t a p r e s e n t e d i n c o o r d i n a t e s o f l o g

CHNO

2

vs . log

t

t h e n a t u r e o f t h e c u r v e s ca n b e r e p r e s e n t e d by t h e

e qua t i on



The i n f l u e n c e o f c o n c e n t r a -

\

t i o n of n i t r o g e n d i o x i de i n t h e

gas on com pos i ti on o f t h e m ix t u re

produced was s tu d i ed wi th an

ra

t

3

~

S

6

NO 2

c o n t e nt i n t h e g a s o f 4 1 ,

Temperature C

20.8 and 10. 8 . The tempera-

F i gu re

4 .

Limiting Concen-

t u r e was m a i n ta i ned e qua l t o 25,

t r a t i o n o f

HNOS04 a s a Func -

30, 40, 50 and 60

C.

The gas

t i o n of Temperature . Con-

t e n t o f

N O 2

:

1

40;

2

3

fl ow r a t e was 40 cm /min. The

c o nc e n tr a t i o n of t h e i n i t i a l

H

SO was 70 . The r e s u l t s of

2 4

t h e s e s t u d i e s a r e p r e se n t e d i n F ig u r e 5 i n t h e fo rm s o f i s o -

t he rns o f l i m i t i ng HNOSOj con cen t r a t i on s i n t he m i x t u re a s a

f u n c t i o n o f NO c o n c e n tr a t i on i n t h e g a s .

2

A s

t h e c o n t e n t o f NO 2 i n

83

Fi gu re 5. Limiging Concen-

t r a t i o n of HNOS04 as a Func-

t i on o f N i t rogen D i ox i de

Content i n t h e Gas a t Tem-

p e r a t u r e , C : 1 60; 2 40;

3

30;

4

25

g a s d e c r e a s e s , t h e l i m i t i n g c on -

c e n t r a t i o n of HNOS04 i n t h e mix-

t u r e d e c r e a s es a c co r di ng t o t h e

e q u a t i o n

The l i m i t i n g c o n c e n t r a t i o n o f

HNOS04 i n t he mi xtu re change s i n

p r o p o r ti o n t o t h e c o n c e n t r a t io n

o f

NO2

i n t h e gas w i t h an exponen t

of 0 .57 .

I n o r d e r t o p ro du ce t h e c u r ve s p r e s e nt e d i n F i gu r e 5 ,

w e

f i r s t f o un d t h e l i m i t i n g c o n c e n t r a t i o n o f HNOS04 d ur i n g a b s o r p t i o n

f o r v a r i o u s t e m p e r a tu r e s and c o n c e n t r a t i o n s o f NO 2 i n t h e g as .



For a temperatureof

25

C, these results were as shown in Figure

Y E

bsorption Time, hr

Figure 6. Concentration of

HNOS04 as a Function of

Absorption Time (Temperature

25 C, Initial H2S04 Concen-

3

tration 70 , = 40 cm /min)

Concentration of NO2 in

:

1, 14.8; 2, 25; 3, 40

(Bottom to Top)

In the mixture studied, an

exceptionally great role was

played by the process of hydroly-

sis of nitrosyl sulfate, the

occurrence of which depends on

the quantity of water in the

solution or the concentrction of

sulfuric acid. The literature 84

presents data on the hydrolysis

of dilute solutions of nitrosyl

sulfate, but no data for solu-

tions containing nitric acid.

The influence of concentration

of initial sulfuric acid on the

composition of the mixtures

formed has been studied upon absorption of nitrogen dioxide by

solutions of sulfuric acid with concentrations of 61, 69, 83.9

and 94.1 . In all experiments, the concentration of nitrogen

dioxide in the gas was about 40 . The temperature was mzintained

at 20 C. The results produced are presented in Figures 7 and 8.

As the concentration of initial sulfuric acid increases,

85

the content of nitric acid in the mixture decreases (Figure 7),

since in dilute acids HNOJ is converted due to the reactions of

equations (1) and 3 ) , while in concentrated acids it primarily

follows the reaction of equation

(1).

The content of nitrosyl

sulfate in the mixture increases with increasing concentration of

the initial sulfuric acid. XLen NO2 is absorbed by 61 sulfuric

acid, the limiting concentration of HNOS04 is 2.6 HN02.

In the

case of 6Q.1 sulfuric acid, the limiting concentration of

HNOS04 is 5.6 HNOr

In acid containing 83.9 H2S04 it is 12.8

HN02.

For 94.1 sulfuric acid, the limiting concentration of

nitrosyl sulfate is 18 HNOr



The dependence of limiting

bsorption Time hr

Figure 7. Change in Content

of Nitric Acid During Absorp-

tion by Various Concentrations

of Sulfuric Acid. H2S04 Con-

centration in : 1, 61; 2, 69;

3, 83.9; 4, 94

21

-

6 ,

.

C.5 5 2 1 5

bsorption

Time hr

HNOS04 concentration on initial

H2S04 concentration in the solu-

tion is presented in Figure 9

Mathematical processing of

these curves has shown that the

limiting concentration of

nitrosyl sulfate in the mixture

changes in proportion to the

concentration of sulfuric acid

with an exponent of 4 . 2 5 .

The

equation of this dependence

is:

The equation for determin-

ation cf the limiting concen-

tration in a mixture as a

function of the temperature,

concentration of initial

sulfuric acid and concentra-

tion of NO2 in the gas is as

follows

Figure 8. Change in Content

of HNOS04 During Absorption

with Various Concentrations of

Initial Sulfuric Acid. H2S04

lim

=

().1218.1010.

HNO~ 86

Concentration in : 1, 61; 2,

Conclusions

1.

The composition of mixtures formed upon abosrption of

nitrogen dioxide by sulfuric acid is studied as a function of



emperature, H2S04 concentra-

tion and concentration of NO2

in the gas.

2. It is found th i in

the process of absorptia~l f

NO2, mixtures consisting of

HN03 HNOS04 H2S04 H20

are formed, containing quite

definite limjting concentra-

tions of HNOS04, dependent on

the temperature, NO2 concen-

Figure

9

Limiting Concentra- tration in the gas and con-

tion of HNOS04 as a Function

centration of the absorbing

of Initial Concentrat.. n of

Sulfuric Acid in Solution.

sulfuric acid.

Content of NO2: 1, 40; 2,

30;

3, 20; 4, 10

3. The dependence of

the limiting concentration of

HNOS04 on temperature, NO2 concentration in the gas and H2S04

concentration is established.

4.

An equation is produced for determination of the limit-

ing concentration of HN0SO4 in the mixture and its dependence on

various factors.

5

The

possibility is shown of producing ~ixtures f HNOS04

HN03 H2S04 H with high HN03 content by absorption of

2

nitrogen oxides.



REFERENCES

Lunge, G . B e r l E Z t . angew. Chem., 19 , 807 , 1906.

Lunge,

G .

B e r l

Z t .

angew. Chem., 20, 17 13 , 190 7.

Rasch ig , F .

Z t .

andew. Chem., 20, 1907.

Canforche ,

A

and

L.

Rondier ,

B 1 .

Soc. Chim., 43, 1923.

F o e r s t e r , F. , B l i c h

Z t .

angew. Chem., 2017, 1910.

Gerb ert -Ge ybov ich , Kabanov, Kri vosh eye v, Ukr. Khim. Zh. ,2.

Szegu, L . and A Ma la gu li , Uspekhi Khirn. Prom.. 2 54, 1933.

Kuz minikh, I . N . Khim. Prom., 11 38, 1934.

Anakhov, I . N . Khim. Prom., 9, 7950.

Ganz, S.

N .

Khim. Prom., 7, 1956 .

Beskov, Sl iz ko vs ka ya , Khim. Prom.,

1 ,

1935.

NO2 Absorbant by H2SO4

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Transcript of NO2 Absorbant by H2SO4