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219
2N02 f Nz04
(V)
Henry coefflclents (HNzO, ) were calculated
from the total vapour pressure data of
Klemenc and Rupp [ 161 and the results are
@ven m Fig 9 and Fig 10 From these figures
It can be concluded that the Henry coefficient
is independent of the amount of N,04 m the
liquid phase At small N,04 contents some
deviations occur
I 01 I I I
0 5 10 15
- % N200 by w eqht 1,~ HN03
I
20
Fig 9 HN,o, as a function of the N204 content m
16N HNOs Data from Klemenc and Rupp [ 161
-, 0 C, o, 12 5 C, A, 25 C
30
c
0 I I I I I
0 5 10 IS 20 25
- 7. N*04 by welphl an HNO)
Fig 10 HN 0 as a function of the N204 content m
19N HNO,* data from Klemenc and Rupp [ 161
y0C,o,1250C,~,25C
From the total vapour pressure data measured
by Wemrelch [ 151 and Karavaev and Yarko-
vaya [ 171 Henry coefflclents were calculated
as a function of the temperature and the acid
strength (see Fig 11) Some experiments were
carned out to investigate the Henry coefh-
clent more directly Nitric acid of 75% was
saturated mth nitrogen gas contammg 5 - 20
volume % of NO2 by means of a saturator at
a pressure of 1 04 bar The gas phase was
analysed for its N204 content mth infrared
spectroscopy The N,O,-content m the hquld
phase was determined by rnjectmg a hquld
sample of 50 ~1 mto 10 cm3 of a 0 8 M
NaOH solution. After reaction the nitrite
content was determined wth a colonmetnc
method [20] It was found that the mea-
sured Henry coefficient was mdependent of
the partial pressure of N204 m the gas phase.
The expenmental results are summarized m
Table 5
TABLE 5
HN,o, m 75% mtrlc acid as a function of the temper-
ature
Temperature HN,o, Measured range bar
C kmol mm3 bar-l &(O,
20 3 70 00106-00611
25 2 63 0008 -0 05
35 2 49 0 006 -0 04
45 3 34 0 003 -0 007
From Fig 11 it can be seen that there 1s a
rather good agreement with the results
derived from the vapour pressure data
CONCLUSIONS
The absorption of NO,-N,O, gas mixtures
from a nitrogen gas stream mto rntnc acid
was mvestlgated m a wetted wall column
From the experimental results it can be con-
cluded that NO2 and N,O, are transferred
in contmuous equlhbnum with each other
from the gas phase to the gas-liquid interface
In the liquid phase N201 IS preferentially
absorbed In the experiments with diluted
nitric acid (25% and 40%) the absorption
1s accompanied by a rapid pseudo-first order
reaction between N204 and water Values of
HN,oamwere measured at 20 C in 25%
220
NOMENCLATURE
Fig 11 HN,-,, as a fun&Ion of the temperature and
mtrlc acid strength O, Wemrelch [ 151, 25% by
weight of Nz04 m 75% HNOs, +, Wemrelch [ 151,
20% by weight of Nz04 In 75% HN03, q Wemrelch
[lb], 10% by weight of Nz04 m 75% HN03, A,
Klemenc and Rupp [ 16 J , V, Karavaec and Yarkovaya
[ 171, l , This work
and 40% mtrlc acid and were found to be
respectively 0 49 and 0 16
In the expenments wth concentrated nitric
acid (63% - 78%) it can be concluded that the
reaction of N,O, mth water can be neglected
and that N,04 dissolves physically m the
llquld phase Further it can be concluded
that the Nz04 1s much more soluble m con-
centrated mtnc acid than NO2 The solublhty
of N204 m concentrated nitric acid was
calculated from total vapour pressure data of
the system N,O,-NO2HNOs-H,O It can be
concluded that wthm the considered condl-
tlons Henrys law 1s valid The solublhty of
N204 m concentrated nitric acid decreases
strongly Mth increasing temperature This 1s
caused by the influence of the temperature
on the Henry coefficient and the influence of
the temperature on the gas phase equlhbrlum
2N02 $ N,O,
which shifts to the left side
ACKNOWLEDGEMENT
The authors express their gratitude to
Mr A A M Pnusken and co-workers for
their technical assistance and Miss Cindy
Jacobs for typing out the manuscript
an
c
D
GZ
h
h
H
I
J
k
KP
p
PC
Q
R
T
w
z
roots of Bessel Function
concentration, kmol me3
diffusion coefficient m2 s-l
3
Graetz number
film height, m
effective film height corrected for the
end effect, m
Henry coefficient, kmol m-3 bar-
lomc strength klon mm3
absorption rate per unit of surface area,
kmol m- 2 s- l
reaction rate constant, s-l
equlhbrlum constant of the reaction
2N0 2 N204, bar-
=C
N104,1~CN201,8 = HN~o,/ RT
partial pressure, bar
pressure m the wetted wall column, bar
flctltlous component defined as CB =
CNO, + 2cN 0
gas law co&t&t, J kmol-l K-
temperature, C, K
mass flow rate, kg s-l
valency of ion
Greek symbols
P
density, kg mm3
;
contact time, s-l
quantity of gas absorbed per unit kmol
m-2 of surface area after contact time 7
Su bscrrp ts
C wetted wall column
g
gas phase
1
gas-liquid interface
liquid phase
0 inlet
Q NO2 + 2N201
Superscrrp ts
bulk average or mlsmg up value
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Nice, France, 1980, D 20
30 J B Lefers, F C de Boks, C M van den Bleek
and P J van den Berg, 6th I nternatI onal Sym-
posium on Chemical ReactI on Engineering,
Nice, France, 1980, D 19