4936 J. Phys. Chem.

1983, 87, 4936-4939

CINH, +0 - CH=C-CH2-NH2 -
does producing secondary and radical reactions as follows:
+O
directed toward identifying those intermediates or pre-
cursors present in our system. A t the moment our main
goal was to report the main experimental findings and to
CHEC-NH~
+CO + Hz
+co
- +
+O
CH* CN* + H2O
relate them with the basic chemical structure of the
reactant aromatic rings. In this direction work is in
progress with thiophene and other heterocyclics in our
Of course, a detailed mechanism of these complex re- laboratory.
actions would perhaps require not only more experimental
work, but also a different experimental technique mainly Acknowledgment. This work received financial support
from the Comision Asesora of Spain.
(8)Nicovich, J. M.; Gump, C. A,; Ravishankara,A. R. J.Phys. Chem.
1982,86,1684. Registry No. Pyridine, 110-86-1;atomic oxygen, 17778-80-2.

Gas Absorption with Instantaneous Chemical Reaction. Absorption of Sulfur Dioxide by

Aqueous Sodium Bisulfite

D. G. Lealst
Depertment of Chemlsby, University of Western Ontario, London, Ontario, Canada N6A 567 (Received December 9, 1982)

Equations are derived for estimating rates of absorption of gas by ternary absorbents. For semiinfinite,
convection-freeabsorbents, the rate of absorption equals Acl(D,/nt)1/2where Acl is the quantity of gas required
to saturate a unit volume of bulk absorbent to the partial pressure of gas at the surface of the absorbent, D,
is an apparent diffusion coefficient defined in terms of ternary diffusion coefficients in the absorbent, and t
is the time. This result applies to absorption by chemically inert systems, and to absorption with simultaneous
chemical reaction provided the reaction rates are sufficiently rapid to effectively guarantee local chemical
equilibrium. For purposes of illustration, absorption of sulfur dioxide by aqueous solutions of sodium bisulfite
is discussed. In this system ternary diffusion of the partially hydrolyzed dissolved gas yields a concentra-
tion-dependent apparent diffusion coefficient that varies between 1.5 X and 8.5 X m2 s-l at 20 OC.

Introduction departures from pseudobinary behavior are likely whenever

Efficient gas absorption often depends on chemical re-
action of the dissolved gas with an involatile component
in the absorbent. Reaction of oxygen with hemoglobin,
for example, plays a key role in respiratory processes. In
the chemical industry, aqueous solutions of acids or bases
are widely used to absorb gases such as ammonia, carbon
dioxide, hydrogen sulfide, and sulfur dioxide. So that the
rate of absorption with reaction can be estimated,'+ it is
common practice to assume that diffusion in the absorbent
is pseudobinary. In real systems, however, the solute fluxes
are coupled by nonideal thermodynamic behavior and by
chemical reaction.'^^ With absorption processes involving
electrolytes, there is the additional complication that fluxes
of ions are coupled to each other by the electric field they
produce, even a t very low concentrati~ns.~J~ Very large
(1)Danckwerta, P. V. Trans. Faraday SOC.1951,47,1014.
(2)Danckwerta, P. V. Ind. Eng. Chem. 1951,43,1460.
(3)Sherwood, T. K.; Pigford, R. L. 'Absorption and Extraction";
McGraw-Hill: New York, 1952;p 332 and Chapter 9.
(4) Crank, J. "The Mathematics of Diffusion"; Oxford University
Press: London, 1956;p 124.
(5)Bird, R. B.; Stewart, W. E.; Liahtfoot, E. N. "Transport
Phenomena"; Wiley: New York, 1960; p 599.
(6)Danckwerta, P. V. Chem. Eng. Sci. 1968,23,1045.
(7)Vitagliano, V. J. Phys. Chem. 1970,74,2949.
(8)Wendt, R. P. J.Phys. Chem. 1965,69,1227.
(9)Leaist, D. G.; Lyons, P. A. Aust. J. Chem. 1980,33,1869.
diffusivities of the various species are widely different.+14
How is gas absorption influenced by multicomponent
diffusion in the absorbent? To answer this question, we
derive equations to describe absorption with ternary dif-
fusion in the absorbent. For purposes of illustration, ab-
sorption of sulfur dioxide by aqueous sodium bisulfite is
discussed in detail. This system was chosen for several
reasons. First, are available to make reliable
estimates of the appropriate ternary diffusion coefficients.
Second, absorption of sulfur dioxide by aqueous solutions
is of importance to pollution studies. And finally, the
recent reportz4that the ternary diffusivity of acetic acid
(10)Leaist, D. G. J. Chem. SOC.,Faraday Trans. I 1982,78,3069.
(11)Revzin, A. J . Phys. Chem. 1972,76,3419.
(12)Kim, H.; Reinfelds, G.;Costing, L. J. J.Phys. Chem. 1973,77,934.
(13)Leaist, D. G.; Lyons, P. A. J. Phys. Chem. 1982,86,564.
(14)Leaist, D. G. Chem. Eng. Sci., submitted for publication.
(15)Campbell, W. B.; Maass, 0. Can. J.Res. 1930,2,42.
(16)Morgan, 0.M.; Maass, 0. Can. J. Res. 1931,5, 162.
(17)Eriksen, T. Chem. Eng. Sci. 1967,22,727.
(18)Robinson, R. A.; Stokes, R. H. "Electrolyte Solutions", 2nd ed;
Academic Press: New York, 1959;Appendix 6.2.
(19)Whitney, R. P.; Vivian, J. E. Chem. Eng. Progr. 1949,45,323.
(20)Groothius, H.;Kramers, H. Chem. Eng. Sci. 1955,4,17.
(21)Lynn, S.;Straatemeier, J. R., Kramers, H. Chem. Eng. Sci. 1955,
4, 49.
(22)Toor, H.L.; Chiang, S. H. AIChE J. 1959,5,339.
(23)Johnstone, H. F.;Leppla, P. W. J.Am. Chem. SOC.1934,56,2233.
(24)Leaist, D. G.; Lyons, P. A. J. Phys. Chem. 1981,85,1756.

0022-365418312087-4936~0~
.5010 0 1983 American Chemical Society
Gas Absorption with Instantaneous Chemical Reaction The Journal of Physical Chemistv, Vol. 87, No. 24, 1983 4937

in aqueous sodium acetate is substantially larger than its tration profiles are obtained
binary diffusivity in water led us to inquire whether Cl(Z,t) =
aqueous sulfur dioxide (sulfurous acid) diffuses more cl0 + Acl[All erfc(z/2(Dlt)1/2)+ A12 e r f ~ ( z / 2 ( D ~ t ) l / ~ ) ]
rapidly in bisulfite buffers. The addition of a substance
to the absorbent that increases the diffusivity of the dis- (9)
solved gas component would improve the performance of c2(z,t) =
gas absorption equipment. c20 + Acl[Azl erf~(z/2(D,t)/~)
+ A22e r f c ( ~ / 2 ( D ~ t ) / ~ ) ]
Theory (10)
Consider isothermal absorption of a single gaseous where erfc(y) is the complementary error function, Di
component by a semiinfinite, convection-free absorbent. denote eigenvalues of the diffusion coefficient matrix
Let it be assumed that the absorbent contains N + 1 Di = [(Oil + D22) + (Dii - Dz2) X
distinguishable chemical species (including solvent and [1 + 4D1@21/(D11 - D ~ z ) ~ I (11)
~I/~
dissolved gas species) with R independent,%.%homogenous
chemical reactions. To simplify matters, it is assumed that D2 = [(Oil + D22) - 0 1 1 - 4 2 ) X
the rates of the reactions are rapid compared to diffusi~n.~ + 4DnD21/(Dil - D22)211/21/2(12)
Hence diffusion is constrained by R local chemical equi- and parameters Aik are functions of the diffusion coeffi-
libria and by the Gibbs-Duhem equation. Under these cients
conditions, diffusion in the absorbent is described in terms
of N - R linearly independent fluxes of components. If A11 = (Dl - D22)2D21/2/B (13)
the absorbent contains ions, the requirement that the
electric current must vanish imposes an additional con- A12 = DlzD21D11/2B (14)
straint, and only N - R - 1 fluxes are independent.O -421 = (Dl - D z z ) D ~ ~ D ~ / ~ / B (15)
In the following, consideration is limited to the case of
ternary diffusion (two independent component fluxes) in -422 = (D22 - D I ) D ~ ~ D ~ ~ / ~ / B (16)
the absorbent of dissolved gas and one involatile solute. B = (DZZ - D1)2D21/2+ D12D21D11/2 (17)
The ternary diffusion equations
Differention of eq 9 and 10 provides
Ji(z,t) = -Dil(dci/az) - D12(ac,/az) (1)
(acl/az)lz=o= - [ ( A l l / ( ~ D l t ) ~+) ( A I Z / ( T D ~ ~ ) ~ / ~ ) I A ~ ~
J z ( ~ , t )= -D2,(aci/az) - Dzz(ac2/dz) (2) (18)
relate total molar fluxes (reacted plus unreacted forms) (acZ/az)l,=o = -[(A2i/(TDit)li2) + (Azz/(~D2t)/~)lAc,
of dissolved gas (component 1) and involatile solute (19)
(component 2) to gradients in volume-formal concentra-
tions. Dll and Dzzare the main diffusion coefficients. The It is interesting to note that although the flux of (involatile)
cross-coefficientsD12and D21describe interactions between component 2 is zero at the surface of the absorbent, the
fluxes of the components. gradient in concentration of that component at the in-
At time t = 0 the partial pressure of the gas in contact terface does not vanish (eq 19). Also, ternary diffusion of
with saturated absorbent is raised from p1to p1+ Apl. At the gas into the absorbent changes the surface concen-
the same instant the concentration of the dissolved gas at tration of component 2 from its bulk value c20 to
the surface of the absorbent (z = 0) is raised from its bulk cz(O,t) = ~ 2 + (A21 + A ~ J A c ~ (20)
value cl0 to c: + Acl, and subsequently held at this value.
The object is to determine Jl(O,t),the rate of absorption With eq 1, 18, and 19, the following expression is obtained
of gas expressed in moles per unit time per unit surface for the rate of absorption of the gas
area of the absorbent. Jl(0,t)= ACl(D,/Tt)/2 (21)
Provided Acl is not too large, the absorption process is
adequately described by time-dependent diffusion equa- where D,, the apparent diffusion coefficient describing
tions with constant coefficients absorption of the gas, is a complicated function of the
ternary diffusion coefficients

Boundary conditions with z = 0 and t >0
and initial conditions with z > 0 and t = 0
apply. Equations 3 and 4 may be integrated by standard
method^.^^,^^ The following expressions for the concen-
(25) Aris, R.; Mah,R. H.S. Ind. Eng. Chem. Fundam. 1963,2, 90.
(26) Denbigh, K. The Principles of Chemical Equilibrium, 3rd ed;
Should D12 and/or Dzl be zero, then D, = Dll and the
following well-known equations are retrieved for absorption
followed by pseudobinary diffusion in the absorbent:
D+
c ~ ( z , ~ ; D ~=~cl0 ~ ~Acl= e~r )f ~ ( z / 2 ( D , ~ t ) ~ ) (23)
J1(0,t;D12D2,=0)
= AC1(Dll/xt)/ (24)
It is worth emphasizing that rates of absorption with
ternary diffusion (eq 21) and with pseudobinary diffusion
(eq 24) are both proportional to t-lI2
Results
The general equations developed in the preceding sec-
tion are now applied to the particular case of absorption
~

Cambridge University Press: London, 1971; p 169. (28) Toor, H. L. AIChE J. 1964, 10, 448.
(27) Stockmayer, W. H. J. Chem. Phys. 1960, 33, 129. (29) Stewart,W. E.; Prober, R. Ind. Eng. Chem. Fundam. 1964,3,224.
4938 The Journal of Physical Chemistry, Vol. 87, No. 24, 1983 Leaist

t 1

100
1
0.
0 75
~ 050 t
0 25
-2- 00: I l 10
l I I l l 10 l l l 100
I J
0 10 (C, +C2)/10-3moldrn
, , 000 Flgure 3. Apparent diffusion coefficient D, describing absorption of
0.1 1.o 10 100 sulfur dioxide gas by SO, (c,) +
NaHSO, (c,) +
H20 absorbents at
(C,tC2)/10-3mol drn
20 OC plotted against total solute concentration c, +
c 2 for several
values of the ratio f , = c,/(c, +c,).
Flgure 1. Ternary diffusion coefficients for SO2 (c ,) NaHSO, (c,)+
+ H 2 0 at 20 OC plotted against total solute concentrations c c2 + ecules, there are four31 species: r n ~ l e c u l a r ~SO ~ - ~H+~ 27 9

for several values of the ratio f , = c,/(c,
c2). + Na+, and HS03- with respective d i f f ~ s i v i t i e s l ~of- ~1.45
~
X 8.40 x 1.17 X and 1.21 X m2 s-l.
Since N = 4 and R = 1, the fluxes of sulfur dioxide and
sodium bisulfite are independent. Ternary diffusion
coefficients of the components were estimated by the ex-
tended N e r n ~ t - H a r t l e f l ~method
~ ~ ~ used p r e v i o u ~ l y . ~ ~
The results are plotted in Figures 1 and 2 against total

1.01
t 099
LL

1
solute concentration c1 + c2 for several values of the ratio
+
fl = cl/(cl c2). The concentration dependence of the
diffusional properties of sulfur dioxide + sodium bisulfite
r
cn buffers is striking. As anticipated, diffusion in this system
w
is very similar to diffusion in acetic acid + sodium acetate
rnE
buffers (discussed in detail in ref 24). Values of the ap-
parent diffusion coefficient D, describing absorption of
sulfur dioxide gas by aqueous SO2+ NaHS03mixtures are
plotted against total solute concentration in Figure 3. In
Figure 1-3, the curves labeled 1.00 refer to solutions of
aqueous sulfur dioxide without added sodium bisulfite. In
this case the apparent diffusion coefficient describing
absorption of the gas is simply the binary diffusion coef-
ficient of aqueous sulfur dioxide. Because of hydrolysis,

-O
-0
4F 01 10
.
10
6
100
diffusion of the dissolved gas closely resembles diffusion
of a 1:l weak acid. Neglecting activity coefficient terms,
we haveW7-39
~
D,(f1=1) = Dll(fl=l) = -
2 - 8 [(l-P)D,+ 2 1
( C ~ + C ~ ) / l O - ~dm
rnol
Flgure 2. Ternary diffusion coefficients for SO, (c,) NaHSO, (c,) +
-tH,O at 20 OC plotted against total solute concentration c 1 c2 for +
several values of the ratio f , = c,/(c, c,). + (31) At extremely low concentrations (less than about mol dm-9
dissociation of bisulfite ion to sulfite and hydrogen ions (pK, = 6.9)17and
self-ionization of water32@must also be taken into account.
of sulfur dioxide gas by sulfur dioxide (cl) + sodium bi- (32) Woolf, L. A. J . Phys. Chem. 1972, 76,1166..
sulfite (c2) + H 2 0 absorbents at 20 C.In this system the (33) Passiniemi, P.; Liukkonen, S.;Noszticzius, A. J. Chem. Soc.,
dissolved gas is subject to rapidm hydrolysis. Bisulfite and Faraday Trans. 1 1980, 76, 2552.
(34) Falk, M.; GiguBre, P. A. Can. J . Chem. 1958, 36,1124.
hydrogen ions are produced (35) Cotton, F. A.;Wilkinson, G. Advanced Inorganic Chemistry,3rd
ed; Interscience: New York, 1972; p 447.
SOz + HzO HS03- + H+ (36) Small quantities of the hydrate species H,S03 may also be pres-
ent,17,34i35in which case the experimental value for the diffusivity of
withz3K = 0.0146 mol dm-3. In addition to solvent mol- molecular sulfur dioxide is the number-weighted average of the diffu-
sivities of unhydrated and hydrated molecular sulfur dioxide.37Because
these species are present in constant proportion, separate values of their
(30) Eigen, M.; Kustin, K.; Maas, G. Z . Phys. Chem. (Frankfurt a m diffusivities are not required for our purposes.
M a m ) 1961, 30, 130. (37) Leaist, D.G.Can. J. Chem. 1983, 61, 1494.
Gas Absorption with Instantaneous Chemical Reaction
where p is the degree of hydrolysis
[H+I
P= (26)
[H+l + [SO21
Do is the diffusivity of molecular sulfur dioxide (1.45 X 10-9
m2 s-l) and D, is the Nernst diffusion coefficient (2.12 X
m2 s-l)
for fully hydrolyzed ( p = 1) sulfur dioxide.
The addition of sodium bisulfite to aqueous sulfur di-
oxide produces a remarkable increase in both the diffu-
sivity of the dissolved gas component (Dll) and its ap-
parent diffusivity (D,) during the absorption process, es-
pecially at low total solute concentrations. This is inter-
preted as follows.24 In binary SO2 + H 2 0 mixtures, the
hydrogen ions and bisulfite ions produced by hydrolysis
diffuse at the same rate in order to maintain zero electric
current. In SO2 + NaHS03 + H20 mixtures, however, H+,
HSOf, and Na+ are present. In general, the three ions
diffuse at different rates. The highly mobile hydrogen ion,
no longer required to diffuse at the same rate as the slower
disulfte ion, diffuses rapidly into the bulk of the absorbent
at the expense of countercurrent flux of sodium ion to the
surface of the absorbent. (Note that values of &-the
coefficient determining the coupled flux of sodium bisulfite
produced by the flux of sulfur dioxide into the
absorbent-are large and negative.) In the limiting case
of absorption of trace amounts of sulfur dioxide by aqueous
sodium bisulfite (fl = 0), D, and Dll are equal, and are
number-weightedaverages of the diffusivities of molecular
sulfur dioxide and hydrogen
D,(fi=O) = Dll(fi=O) = (1 - P)Do + PDu+
At low sodium bisulfite concentrations where hydrolysis
is extensive, the apparent diffusion coefficient describing
absorption of trace amounts of gas approaches the diffu-
sivity of the hydrogen ion (8.45 X m2 d).
The mechanism described here for the increase in the
diffusivity of the sulfur dioxide component in aqueous
sodium bisulfite will increase the multicomponent diffu-
sivity of sulfur dioxide in other supporting electr01ytes.l~
Therefore, the rate of absorption of sulfur dioxide by
(38) Muller, G. T. A.; Stokes, R. A. Trans. Faraday SOC.1957,53,642.
(39) Holt, E. L.; Lyons, P. A. J.Phys. Chern. 1965,69, 2341.
The Journal of Physical Chemistry, Vol. 87, No. 24, 1983 4939
aqueous salt solutions (such as seawater) will be substan-
tially larger than the rate of absorption by water alone,
especially at low partial pressures of the gas. The ex-
ceedingly large diffusivity of the aqueous hydrogen ion is
responsible for this unexpected behavior. The effects of
multicomponent diffusion on absorption will also be sig-
highly mobile hydroxide ion (diffusivity 5.2 X
s-l at 25 "C).
-
nificant for aqueous alkaline absorbents containing the
m2
Discussion
Because several approximations were made, the ex-
pressions developed in this paper best describe absorption
processes with low rates of absorption. At high mass
transfer rates, the following points should be considered:
(a) Enthalpies of solution and reaction of the gas may cause
departures from isothermal conditions. (b) If transport
in the gas phase is a rate-limiting factor, the surface of the
absorbent may not be fully saturated with dissolved gas.
(c) In cases where the flux of dissolved gas is large, the
concentrations and hence diffusion coefficients may vary
appreciably along the diffusion path. (d) Large concen-
tration gradients may produce density inversions and
subsequent c o n v e ~ t i o n . ~ ~
The expressions derived in this study refer to absorption
by a convection-free absorbent. In practical absorption
processes, however, the absorbent is well-agitated in order
to increase the mass transfer rate. To describe absorption
with turbulent motion in the liquid phase, our result for
absorption by a quiescent, ternary absorbent may be
combined with the surface renewal theory developed by
Danckwerts1s2to obtain
Jl(O,t) = Acl(sD,)'/* (29)
where s is the fractional rate of surface renewal-an em-
(28) pirical measure of the degree of turbulence. If chemical
reactions accompany absorption of the gas, the reaction
rates must be rapid enough to ensure local chemical
equilibrium, otherwise eq 21 and 29 do not apply. Al-
though discussion has been confined to absorption pro-
cesses, the equations that have been derived can of course
be used to describe desorption processes (Acl < 0), such
as those used to regenerate spent absorbent. Also, the
analysis can be extended to more complicated geometries,
and to quaternary and higher-order diffusion.
Registry No. SOz, 7446-09-5; NaHS03, 7631-90-5.
(40) Wendt, R. P. J.Phys. Chern. 1962, 66, 1740.