Dl.

The dynamics of nitrous gas absorption

S. P. S. ANDREWand D. HANSON
ImperialChemicalIndustries Ltd., Billingham

Abstrati-The dynamics of the absorption of nitrous gases into water is explained as the result of
a number of separatereaction mechanisms. The relative importance of these mechanisms is primarily
dependent on the gas composition. Rate equations computed from basic diffusional kinetic and
equilibrium constants are in good agreement with the measured absorption et&iency of a sieve
plate over a wide range of gas strengths.

R&un16-La dynamique de l’absorption de gax nitreux dans de l’eau est expliq& comme la r&&at
dun nombre de m6canismes de &action s&pa&s. L’hnportancerelative de ces mecanismes depend
en premier lieu de la composition du gax. Les equations de vitesse calcuRes B partir de don&s
Umentaires relatives a des constantes de ditfusion et des constantes d%quilibresont en bonne concor-
dance avec l’effet dabsorption mesure dun plateau en forme de tamis et cela sur un grand trajet
de concentrations de gax.

Zusanunmfamung-Die Dynamik der Absorption nitroser Gase in Wasser wird als das Resultat
einer Anxahl einxeher Reaktionsmechanismen gedeutet. Die relative Redeutung dieser Mechanismen
wird xuni%chstdurch die Zusammensetxung des Gases bedingt. Geschwindigkeitsgleichungen, die
m Hand von elementaren diffusionskinetischen und Gleichgewichtskonstanten aufgestellt wurden,
entsprachen durchaus dem gemessenen Absorptionswirkungsgrad eines Siebbodens iiber einen
grossen Rereich von Gaskonzentrationen.

INT~00ut2~10N important absorption mechanism, at low gas

IN RECENTinvestigations [4, 10, 3,9] of the absorp-
tion of relatively strong NO2 into water there is a
large measure of agreement as to the intluence of
gas composition on the absorption rate. In the
most recent work, DEKKER, SNOECK and KRAMFW
[4] conclude that the rate controlling mechanism
is the diffusion across the gas film of NO2 and
N20, followed by solution of the N,O, in the water
accompanied by its rapid hydrolysis to
HNOs + HNO,. Furthermore, values are
obtained for the product of the N,O,, solubility
H1 and the square root of the hydrolysis rate
constant times the diffusion constant, &-Q).
Recent work by KRAMER~[S] confirms these
measurements.
CAUDLE [3], however, showed that at low NO2
concentrations a marked enhancement of its
absorption rate occurred in the presence of NO.
Although at high NOa concentrations the NaOl
solution plus hydrolysis mechanism is the most
concentrations in the presence of NO other
mechanisms must, therefore, be of equal, if not
greater, importance.
In this paper, rate equations are developed from
theoretical considerations for those absorption
mechanisms likely to be of importance at gas
strengths found in commercial absorbers, and these
equations are used to compute the performance of a
laboratory sieve plate. The necessary kinetic and
equilibrium constants are principally derived from
the literature, although a few of these constants
together with the contacting ability of the sieve
plate were measured in cormexion with the present
work. A comparison of the predicted plate
performances with an extensive series of measured
values confhms the validity of this approach and
shows that only a combination of several absorption
mechanisms acting in parallel is capable of explain-
ing the dynamics of nitrous gas absorption over a
wide range of gas strengths.

105
 s. P. s. ANDREW
and D. tiN

THE KINBTICSOF N,O, HYDROLYSIS
The decomposition of aqueous HNOa
The N,O, hydrolysis kinetics can be obtained by
measuring the rate of the homogeneous liquid
phase decomposition of aqueous HNOa solutions.
The overall reaction is
3HNOp --f HBO + HN08 + 2N0.
Measurements of the kinetics were made by
ABEL et al. [2] and confirmatory measurements
gives A G” for the reaction as - 2460 cal at 25 “C.
.Hence [NOJ [NO]/(HNO# = 2.6 x 10-s.
A rough confirmation of this value has been
obtained from measurements of the steady state
HNOa concentration in liquor being recirculated
over a plate absorber through which was bubbled
a gas mixture containing known concentrations
of NO and NOI, the gas being saturated with
water vapour. The apparatus is sketched in Fig. 1.
TO

were also made in connexion with the present work.

ACI
The rate equation is as follows
d/dt (HNOJ = A (HNO#/(NO)* (l)*
This rate equation suggests that the liquid phase
equilibrium 4HN08 Z 2H,O + 2N0 + NeO, is
maintained at all points in the liquid, and that the
rate of the N,O, hydrolysis reaction, N,O, +
H,O + HNOa + HNO*, is kinetically limiting the
decomposition process, and is given by
d/dt (HNOa) = r (N,O,) = rH, KI [NOa]* (2)
where HI is the solubility of N,O, and KI is the
gas phase equilibrium constant detied by
4 = [N,O,]/[NO$. K earranging equation (2)
d/dt (HNOJ = rH, Z&*Kl{[NOa]* [NO]*/(HNO&‘} FIG.1. Arrangement of experimental absorber.

(WOJ’ANOY} (3) 6'0

where Z& is the solubil& of NO. Equation (3) is

the same as the experimentally measured rate
equation, provided
A = PI& KI HsS [NO,]* wO]*/(HNOd)‘.

l’%e NS04 solubility and kinetic constant

At 25 “C and zero ionic strength, ABEL [2] gives
A/I-Z**= 0.43 in equation (1). From measurements
of the gas phase equilibrium between NOI and
N,O,, summarized by CAUDLE[3], at 25 “C KI
equals 1.716 x 1W. Thermodynamic data enable
the equilibrium constant [NOJ [NO]/(HNO$ to 16’6 16’5
be obtained at 25 “C. LATIMFR[7j computes a [N02][“3 (GMMOL~ ICiU
value of AG” for aqueous (HNOJ of - 13,020 cal.
FIG. 2. A comparison of measured with predicted hetero-
Taking A G” for gaseous NO, NO, and liquid Ha0 geneous equilibrium constant.
as 20720, 12390 and - 56690 respectively [9],

*curved brackets are used to denote liquid phase con- The results of these measurements are plotted in
centrations and square brackets to denote gas phase con- Fig. 2, from which it will be seen that this straight
centrations. line representing the heterogeneous equilibrium

106
 The dynamicsof nitrousgas absorption

constant of 2.6 x 10-s gives good agreement with
the measured points.
Substituting the above values for A, K1 and the
heterogeneous equilibrium constant in equation
(3) :
f& = 3,700 set-’
(4)
From the measurements of BLIND and KRAMEM
[5], H,&DJ = 2.0 cm/set, and taking D1 for The transportingspecies
NsO, in water at 25 “C!to be 1.4 x 10-s cm’/sec:
r’/s HI = 535 sect (5) feature that they all produce 2HNOs and also that
From equations (4) and (5) : r = 48 se& and
H1 = 77. It is theoretically possible to obtain the processes carrying higher oxide into the liquid
values of r purely from the results of absorption
studies. As the velocity constant is high this is
not easy in practice, because very short periods of
contact (circa 0.01 set) must be employed in the
experimental absorber. Using a jet absorber,
BLIND and KRAMIW [5] obtain r m 300 set-1 at
25 “C, six times the value obtained above.
POSSIBLBABSORPTIONMECHANISMS
The overall reaction
The overall steady state reaction occurring
during nitrous gas absorption in a commercial
nitric acid tower can be written as
gas liquid liquid
3NOI + HsO + 2HNOs + g (a)
It can equally be written in any of the following
ways, which each represent possible absorption
mechanisms
gas gas gas gas
3NOs + HsO -t 2HNOs + NO
gas liquid
.J?
either : 2HNOs + 2HNOs (0
‘13
g liquid liquid
1 gas gas
or : 2HNOs + H,O + mist + 2HNOs (k)
e
The eight mechanisms (a) to (h) have the common
there are two types of overall transfer process
occurring in all cases. These are firstly, transfer
phase either as NOs, N,O,, HNOs or N,Os, and
secondly, transfer processes carrying lower oxide
out of the liquid phase either as NO, NsOs or
HNOI. The total transfer of higher oxide into
the liquid phase is three times the total transfer of
lower oxide out of the liquid phase.
As the diffusion coefficients of the various mole-
cular species differ by only a small extent, the
relative ability of each species to effect transfer
of higher or lower oxide is roughly proportional
to the relative concentration of that species. Gas
phase equilibrium constants are available for all
the molecular species [3]. The solubilities of NO
and HNOs [l] are known and together with the
Table 1. Equilibrium concentrations in gas and
liquid phases (all concentrations expressed in
g mole/cm* x lo-3
Strong gas Weak gas

gas liquid liquid G0.T Liquid GaS Liquid

l&N,O, + H,O -+ 2HNOs + g (b) phe phase phe phase
3NsOs + H,O + 2HNOs + 4N0 (c)
NO, 3.9 3.9 1.0 x lo-8 1-o x lo-’
6HNOs --t 2HNOs + 4N0 + 2HsO (6)
N,O, 2.6 195 l-7 x 10-s 1.3 x lo-’
4NOs + 2HsO + 2HNOs + 2HNOs (e) N,O, 0.3 1100 0.9 x lo-6 3.5 x K-P
2NsOd + 2HsO --f 2HNOs + 2HNOs (f) HNO, l-3 1100 2.3 x Wa 2-O
4N0, + HsO --f 2HN0, + N,O, (g) NO 9.0 0.45 1.0 x 10-s 5.0 x 104
2Ns0, + Ha0 + 2HN0, + NsOs (h) dl

In addition there is the possibility of the gas
phase formation of HNOs followed by its sub-
sequent absorption into the liquid eithef: as a
vapour or by the scrubbing out of an acid mist.
This gives two mechanisms
previously calculated solubility of N,O, and the
solubilities of NsOs and NO* obtained by indirect
methods, a rough estimate of the equilibrium
composition of the gas and liquid phases can be
made. Table 1 has been drawn up giving equili-

107
 S. P. S. ANDREW and D. HANSON

brium concentrations for a weak and a strong
nitrous gas.
Table 1 shows that in gas phase at both gas
strengths, NO is the most important transporting
species for lower oxide and NO8 for higher oxide.
At the high gas concentration NaOd is of equal
importance to the NOB. In the liquid phase at
both gas strengths, there is a high relative concen-
tration of HNOa which can act either as a trans-
At high gas concentrations absorption mecha-
nisms (f) and (h) are favoured, being the only
mechanisms which simultaneously give high rates
of higher oxide and lower oxide transporting species
flowing in opposite directions. At low gas con-
centrations, mechanisms (d) and (e) are favoured.
Mechanisms (a), (b) and (g) are never favoured.
Because of the rapid attainment of equilibrium
between NaOB and HNOI, [3], mechanisms (/‘) and
(h) may be combined into a single mechanism in

T
GAS PHASE LIQUID PHASE which lower oxide is transported as 2HNOa + NaOC
-NO,1 Mechanisms (c) and (d) can be combined in a
similar manner. The detailed transfer and reaction
sequences associated with this mechanism are
shown diagrammatically in Fig. 3, and those
associated with mechanisms (e) and (f+ h) are
shown in Fig. 4.
NO H20 NOj+04
Mechanisms (i) and (k) depend on the existence
of a gas phase HNO,-forming reaction assumed to
FIG. 3. Absorption mechanisms(c) and (4.
be similar to that occurring in the liquid phase.
The transfer and reaction sequences for these
GAS PHASE 7 LIOUID PHASE
mechanisms are sketched in Fig. 5.

.NO
FIG. 4. Absorption mechanisms (e), (f) and (h).
GAS PHASE LIOUID PHG&
- NO+ t$04 Hz0
T venience called the “chemical NOp” and its
- [NO,]*=[NO,]+2[N,O,]+[N,O,]+~[HNO,]
FIO. 5. Absorption mechanisms(i) and (&).
porter of higher or lower oxide, as can NaOa
which is significant only at high concentrations.
Higher oxide is specifically transported by the
N,O, molecule at high concentrations and by the
NO, molecule at low concentrations.
RATE EQUATIONS
Hate eJiciency
In following sections, rate equations will be
developed for the five important absorption
mechanisms (c + d), (e), cf+ h), (i) and (k)
supposing that the absorption unit is a plate tower.
It is convenient to define a plate efficiency 1,
such that for absorption into water, the efficiency
is given by the ratio of higher oxide absorbed on
the plate divided by higher oxide entering the plate.
The total higher oxide concentration is for COD-
concentration is defined by
Hence
? = [NO,]* absorbed
(6)
[NO,]* entering
Absorption mechanism (f + h)
Referring to Fig. 4, this absorption mechanism
involves the transfer of higher oxide by diffusion
across the gas film (primarily as NOB and NaOJ
followed by its diffusion into the liquid as N,OI
with subsequent hydrolysis to form HNOI plus

108
 The dynamics of nitrous gas absorption
either HNOI or NaOg, which then diffuse out of
the liquid. A comparison of the relative concen-
trations of the transporting species shows that the
inward flow of higher oxide is the rate limiting
step. For transfer of higher oxide across the gas
film
Q,t,= kgWUe* - [NO&*) (7)
Q,* is the transfer rate of chemical NOz
due to this mechanism.
kg is the local value of the gas film
where transfer coefficient.
subscripts g and i refer to the bulk gas
1 and interface concentrations respectively.
At the interface the solubility relation for NaOl is
(X0& = HI [N,O& (8)
For transfer and reaction in the liquid 8lm
Qf,,= ; @J&h z{kn, W3”“) 69
The summation sign represents the combination
of simple diffusional transfer without reaction klI
together with a first order fast reaction (rD,)*.
A method of effecting this combination is given
by VAN KREWJXFJN [6]. Solving for Qrh from
equations (7), (8) and (9) gives :
where B = HI Z(ku, (r&)*/2}.
If the gas/liquid interfacial area on the absorp-
tion plate is a per unit floor area of plate, and if Qti =
the specific volume flow rate of gas is G, then the tk182/s(V/a)11s(2rHI H8sK31’3[NO~,“‘*[NO]d’s (17)
plate efficiency due to the cf + h) mechanism is The expression for the plate efficiency due to this
given by mechanism is
m (1 - Ilrh, = - QJY, a/G PGlg* (11)
Absorption mechanism (e)
With this mechanism, higher oxide is transported
by diffusion as NO2 across the gas and liquid films.
Lower oxide is evolved as H.NOB. Because of the
low solubility of NO2 its diffusion across the
liquid 8lm controls the over-all rate. The rate
equation is as follows
Q, = t ha H2 W’21r (12)
109
where H2 is the solubility of NOB. The expression
for the plate efficiency due to this mechanism is
In (1 - 73 = - Q, a/G [NO&* (13)
Absorption mechanism (c -I- a)
Referring to Fig. 3, higher oxide is transported
into the liquid phase by diffusion as an equilibrium
mixture of HN02 and N20a. The HN02 decom-
poses in the liquid phase to give HNO, and NO
which diffuses out of the liquid phase, acting as
the carrier of lower oxide. The rate of this
mechanism is jointly limited by the kinetics of
the homogeneous HNOB decomposition process
and by the rate of diffusion of NO out of the
liquid phase.
The rate of the homogeneous HN02 decomposi-
tion process is
Q, = 3r v(N,OMa (14)
where V is the liquor hold-up per unit floor area
of plate. The rate of the NO diffusion process is
Qti = Qkm[(No), - (NO),] (15)
The assumption of equilibrium between the gas
phase NO and NO2 and the liquid phase HN02
and also between the liquid phase HNO, and NO
and the liquid phase N201 leads to
(NaO& = Hi HZ Jr&WI,” W2lJWh2 (16)
where H, is the solubility of NO.
Solving equations (14), (15) and (16), ignoring
(NO)i in comparison with (NO), in (15) gives
ln (1 - rloa)= Qd a/G [NO&* 08)
Absorption mechanism (i) and (k)
Referring to Fig. 5, the initial step in both these
absorption mechanisms is the gas phase reaction
between N,O, and water vapour to form HNO,
+ HNO,. This reaction proceeds at a kinetically
determined rate but is halted, in the absence of a
liquid phase, by the gas phase HNOI formation
equilibrium. A liquid phase, however, is capable
 S. P. S. ANDREW and D. kiANSON
of being formed as a mist by the condensation of
HNO8 with water vapour. The condensation of
acid mist ceases when the available water vapour
is exhausted both through forming HNO, and by
condensation.
Measurements, described later, show that the
gas phase HNOI reaction is slow and occurs
almost entirely during the time that the gas is
passing from one plate to the next in the absorption
tower. An upper limit can be set to the effects of
mechanisms (i) and (k) by assuming that when the
gas passes through a plate, all the gas phase HNO,,
both vapour and mist, is scrubbed from the gas,
which is then re-saturated with water vapour. On
the above assumptions the upper limit to HNO,
formation as vapour is given by the gas phase
equilibrium
[HNO,], = KS [NOala’* [H,0]1’2/[NO]1’2 (19)
From vapour pressure data for aqueous HNOs it
can be shown that the upper limit of the acid mist
concentration is given, at 25 “C, by the expression:
WWA, =
= [H201,
(1~58-0~040ln W1,/PQl~Y t20J
(0.110 ln [NO]J[NO$ - 1.14)
where [H20],, is the water vapour concentration in
the gas immediately after passing through the
plate. A third equation gives the initial ratio of
increase in the gas phase HNO, concentration,
2. It is
d/dt [HNO,] = Z = R [H,O],, [N,O,], (21)
where R is the second order gas phase kinetic
constant.
Equations (19), (20) and (21) may be combined
in the following manner to give an approximate
value for the total HNO, both as mist and as
Table 2. Equilibrium, kinetic and transfer constants at 25 “C
kp = 39 cms/scccm* for NH,
kp = 0.28 cma/seccm*for CO2
H, = 1.0 Kl = 1.716 x K+
H, = OG46 K, = 16.0
110
vapour formed in a residence time T
n(P-IMU,, + N’Wo)
[HNos], = (ZT + [HNO&, + [HNO,]J (22)
The expression for the contribution to the plate
efficiency due to the (i) and (k) mechanisms is
EXPBRIMBNTAL
VERRTCATION
Physical and transfer constants
To use the plate efficiency prediction equations
it is necessary to have numerical values for the
appropriate equilibrium, kinetic and transfer
constants. The transfer constants, a, k, and kg
must be obtained for the particular design of
plate and for the gas rate, G, being considered.
The product kBa can be measured by ammonia
absorption from an air stream into dilute acid;
kl a can be measured by CO2 absorption into water
and the interfacial area, a can be obtained from
the results of absorbing very dilute CO2 from an
air/CO, mixture into weak NaOH solutions (a
process in which k, is known). Assuming that
kp and kl are proportional to the square roots of
the appropriate diffusion coefficients, the transfer
coefficients for NO and for NO2 and N,O, (in the
absence of chemical reaction) can be computed
from those measured for NH, and COP The
transfer constants listed in Table 2 were measured
on a small laboratory sieve plate.
The uncertainty in r, and hence H,, results in
an uncertainty in B in equation (10) and in (r&)1/8
in equation (17). Using VAN KREvEL&s curves
for effecting the summation in B, the change in r
from 50 to 300 makes only a 15 per cent change in
B and 30 per cent change in (rHJl’s. Both changes
are so small as to be undetectable when comparing
predicted and measured plate performances.
a=llcm~/cm~
V = 4.2 cma/cma
R w 4 x l@cms/gmokse-c
rur, = 535 sect
r = SOsed (Present work)
r = 300 set-1 (KMMERS)
 The dynamics of nitrous gas absorption

[Nod; CHEMICAL NO2 CONCEFClOTlON (GM.MCX/Ct& d)

FIG. 6. FVedicted component and total plate efficiencies.

Predicted plate e@ciencies greater. This increase in importance of mechanism

Using the above constants, the component
plate efficiencies have been calculated for the
laboratory plate over a wide range of chemical
NOa concentrations and with a constant higher
oxide/lower oxide ratio of 1.0. The values obtained
are plotted in Fig. 6, the total plate efficiency being
the sum of the four components TV,,,qe, qoa and rliP
From Fig. 6 it can be seen that at high gas
concentrations the ($+ h) mechanism determines
the overall absorption process. At low gas con-
centrations, mechanisms (e) and (c + d) are the
important processes. If the NO proportion in the
gas had been greater, 7a would also have been
(c + d) relative to mechanism (e) with increasing
proportion of NO is the effect noticed by CAUDLE
[3] and is also demonstrated in the experimental
measurements described in the next section. The
gas phase mechanisms (i + k) are not important
at any gas concentrations as they are kinetically
limited at low concentrations and limited by
exhaustion of the available water vapour at high
concentrations.
Measured plate eficiencies
An extensive series of measurements of the
overall plate efficiency were made using the

lOO%

IO%

I %l
001
,go
[N02G &tCAL N02CONCENiPATION (GKMOL/C& 106 )

FIG. 7. A comparison
of measmed with predicted plate efkkncies.

111
 S. P. S. ANDREWand D. HANSON

apparatus sketched in Fig. 1. Under steady-state At low gas concentrations, [NO,]* < 0.5 x lo-’
running conditions, the HNOz content of the g mole/cmr, the predominant absorption mech-
circulating liquor remains constant and the HNO, anism is dependent on the [NO]/[NO,] ratio in
content increases at a constant rate from which the the gas phase. When [NO]/pOa] < 0.5, the
overall plate efficiency can be calculated. predominant mechanism is the liquid film limited
Measured plate efficiencies are plotted in Fig. 7 solution of NOz. When [NO]/[NO,] > 5 the
as a function of chemical NO2 concentration in predominant mechanism is the absorption of
the feed gas, with and without the addition of NO. HNOa followed by its homogeneous liquid phase
In all the experiments of Fig. 7, the gas residence decomposition. Neither of these mechanisms have
time after mixing and before entering the plate been described previously.
was only about 3 seconds, though some experi- At all intermediate concentrations, more than
ments, not reported here, were performed with one absorption mechanism is of importance in
from 3 to 21 seconds residence time under con- determining the total absorption rate of NOa
ditions favourable to the formation of gas phase into water.
HNOt. The kinetic constant, R, for the gas phase
reaction was calculated from the influence of NOTATION
residence time on the plate efficiency.
A = rate constant defined by equation (1)
At the lowest gas concentrations in the absence cm3 g mole-’ se+
of NO, the plate efficiency approaches a constant a = interfacial area/unit plate floor area
value of about 3.2 per cent. This value was used B = rate constant detiued by equation (10) cm se&
to calculate the solubility of NOz in water, H,, as D, = liquid phase diEusion wefficient of component n
mechanism (e) is the controlling process under cm* se&
G = gas flow rate/unit plate floor area omseo-1
these conditions. H, = solubility constant for gas n
Also shown on Fig. 7 are two theoretical curves KI = equilibrium constant de&d by equation (2)
for the overall plate efficiency computed by the ems g mole-l
K, = equilibrium coustaut deftued by equation (19)
methods described above for the conditions of ems/* g mole-f
0.0 and 0.05 x 1O-6g mole/cm8 NO. Agreement k, = gas film transfer coe5kient for (NOa + 2N,OJ
is remarkably good between these and the measured cm So-1
values. k,, = liquid 6ltu transfer eo&cient for species n
out so.71
Q, = transfer rate of chemical NO, due to mechanism x
g mole cm-s se&
CONCLUSIONS
R = kinetic constant detiued by equation (21)
The theoretical rate equations have been derived cm* g mole-r soi+
r = kinetic coustaut for the hydrolysis of N,04 se&
for the important mechanisms leading to the T= gas residence time between plates !Soc
absorption of nitrous gases into water on a sieve V= plate hold-up per unit floor area cm
plate. Numerical agreement between the measured 2 = reaction rate defined by equation (2)
g mole cm-3 set-l
performance of a sieve plate, operating at 25 “C,
7X= plate efficiency due to me&auism x
and the performance calculated from the theoretical [] = concentrations in the gas phase g mole cn+
rate equations is good. [NO,]* = the chemical NO, in the gas phase g mole cm-s
( ) = concentrations in the liquid phase g mole cmes
At high gas concentrations, [NO,]* > 5-O x lo-’
g mole/ems, the predominant absorption mech- Subscripts
anism is the solution of N,O, in the liquid accom- g = concentrations in the bulk gas
panied by its rapid hydrolysis to HNO, + HN02. i = concentrations at the interface
This mechanism has been noted by previous I = concentration in the bulk liquid
1 = NsO,
workers [4, lo] employing laminar flow absorption 2=NO,
units. 3=NO

112
 The dynamics of nitrous gas absorption

[l] AeeL E. and Neuss~~ E. Monatsh. Chem. 1929 54 855.

[2] ABEL E., Scow, H. and BABAD S. 2. phys. Chem. 1928 136 430.
[3] CAUDLEP. G., Ph.D. Thesis, University of Cambridge 1951.
[4] D- W. A., SNOECK E. and KRMAERSH. Chem. Btgng. Sci. 1959 11 61.
[5] a H. Private communication. 1959.
[6] VAN lcREvBLBND. W. and Hopryze~ P. J. Chem. Engng Sci. 1953 2 41.
[7] LAIIMERW. M. Oxidation States of the Elements. Prentice-Hall, New York 1938.
[8] PeneRs M. S., Ross C. P. and ANLXBSON L. B. Technical Report of the University of Illiiois, 1953.
[9] Selected Values of Chemical Thermodynamic Properties. U.S. National Bureau of Standards 1952.
[lo] WENDELM. M. and PIOFORDR L. Amer. Imt. Chem. Engrs J. 1958 4 249.

113