156 Chem. Eng. Techno].

I 1 (1988) 156- 162

Absorption of SO2 by Aqueous NaOH Solutions in the Presence of a

Surfactant
Gonzalo Vazquez, Gervasio Antorrena, Francisco Chenlo and Francisco Paleo*

A report is presented on the influence of liquid flow rate, NaOH concentration, column length
and presence of 5 x 10 - wt- % of the surfactant SLS on the rate of absorption of pure SO,
by aqueous NaOH solution in a sphere-and-cylinder column. The presence of sodium lauryl
sulphate (SLS) prevented axial turbulence which increased mass transfer in longer columns and
was almost independent of the flow rate. The enhancement factor due to the reaction between
SO, and NaOH with respect to the process of physical absorption was analyzed for the systems
with excess OH- in the outflow. The results obtained in the presence of a surfactant are satisfac-
torily explained by film theory with a single reaction plane model. Those obtained in the absence
of surfactant are best described by a two-plane model using renewal theory.

1 Introduction
Absorption of gases is of great importance and widely used in
the chemical industry. It is of particular interest when the ab-
sorbed gas reacts with a component of the liquid phase. In this
case, the overall rate of absorption is the product of the physical
absorption rate and an enhancement factor E , determined by the
corresponding mass transfer coefficient k,. E and k , were in-
vestigated during an absorption process with the liquid phase
containing a surfactant, which makes the hydrodynamic
behaviour of the system more uniform at the expense of the
overall absorption rate (Chenlo [ 11).
This contribution describes a study of absorption of pure
sulphur dioxide by water and aqueous solutions of sodium
lauryl sulphate (SLS), in the presence of various concentrations
of sodium hydroxide (including zero) in the liquid phase. The
contact system employed was a sphere-and-cylinder column
(Costa et al. [2]), a device which simulates the hydrodynamic
conditions prevalent in industrial columns; the number of col-
umn elements was varied. Since the hydrolysis of SO, occurs
in SO,-H,O systems, SO, was also absorbed into aqueous
solutions of HCl in which this reaction is inhibited.
Absorption of Sulphur Dioxide by Aqueous Sodium Hydroxide
Solutions: When sulphur dioxide is absorbed by alkaline
aqueous solutions, the following reactions must be considered:
SO2 + OH- * HSO; K , = 1.7 x lo', 1 g mol-',
(1)
HSO;+ OH- 2 SO:-+ H,O K, = 6.2 x lo6 1 g mol-',
(2)
where the equilibrium constants for 25" C and infinite dilution
(Dean [3]) show that, in the presence of excess OH - , both reac-
tions are practically irreversible. The kinetic constant of (1) is
* Dr. G. Vizquez, Dr. G. Antorrena, Dr. F. Chenlo and F. Paleo,
Chemical Engineering Department, University of Santiago de Com-
postela, 15706 Santiago de Compostela, Spain.
greater than lo9 1-g mol-' (Saal [4]) and that of the proton
transfer (2) is even greater. The overall reaction in systems with
excess OH - is thus
SO, + 2 OH- * SO:-+ H,O , (3)
and this reaction may be regarded as irreversible and instan-
taneous. In aqueous sulphite solutions, i.e. after the excess
OH- ions have been consumed, the SO:- present is hydrolyz-
ed by reverse reaction (2) and the overall reaction is
SO, + SO:- + H,O 2 HSO; (4)
giving rise to an SO:-/HSO; buffer solution. The direction of
reaction (2) and the kinetics of the overall reaction are determin-
ed by the relative proportion of OH- present.
Goettler [5], who studied the mechanism of the above process
using a contact device consisting of a single sphere, developed
a model based on the hypothesis that the dissolved sulphur diox-
ide and hydroxyl ions react in the liquid phase in two instan-
taneous steps taking place in two reaction planes. The ex-
perimental results of Onda et al. [6] on the displacement of reac-
tion planes agree with the two-plane model developed by Hikita
et al. [7] using penetration theory and corroborated experimen-
tally by Hikita et al. [8]. This model predicts that in such cases
the mechanism of chemical absorption depends on the ratio of
the equilibrium constants; in the limiting case when K11K2 -+
co, reactions (2) and (4)occur irreversibly in the liquid phase,
the latter in a reaction plane close to the gas-liquid interface and
the former in another, deeper plane. Since in the present case
K , / K , = 2.7 x lo', these considerations are applicable. When
all the OH - ions in the liquid phase have been consumed, reac-
tion (4) takes place irreversibly in a single reaction plane.
The absorption of SO, by aqueous sodium hydroxide solutions
has also been studied using a simpler, single-plane model fre-
quently quoted in literature (Danckwerts [9]).
The reaction steps occurring in SO, - NaOH systems, and con-
sequently the chemical species present, depend essentially on

0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1988 0930-7516/88/0306-0156 $02.50/0

Cliem. Eng. Technol. I 1 (1988) 156- 162 157

The solution given in this case by film theory (Olander [ 121) is

very similar, the difference lying in the application of the dif-
fusivities ratio instead of its square root; as Danckwerts [13]
pointed out, if diffusivities of both components are the same,
Reaction (3) the two equations reduce to the same solution.
lz Basic pH. excess OH-
0
m The stoichiometry of reaction (3) means that, according to sur-
u face renewal theory, its enhancement factor is given by
8
W 2nd equivalence point (reaction (3))
SO2-+ H20
3
HSO; + OH-
Basic pH, total consumption of OH- (7)

Reaction ( 4 ) In the equation predicted by the film theory, the ratio of the dif-
2-
Acid or basic pH, S03/HS0, buffer fusivities appears instead of its square root. Thus, according to
Eqs (5) and (7), the absorption flow rate is governed solely by
the gas-liquid equilibrium, the hydrodynamics of the system and
h
:: 1st equivalence point (reaction (1)) the concentration of the reactant in the liquid phase; as the reac-
m Acid pH, total absence of S
O
:
- tion involved in instantaneous, the flow rate is unaffected by
u chemical kinetics.
X
W

Another expression for the enhancement factor E was obtained

SO2 + H20 t HSO; + H+ by Hikita et al. [14] by applying surface renewal theory to a
Acid pH. acid dissociation reaction involving two steps occurring in two different reaction
planes in the liquid phase. Their approximate solutions of the
corresponding equations were applied by Hikita et al. [8].

Fig. 1. Regions of a sphere-and-cylinder column during absorption of SO,
by aqueous NaOH solution.
the relative concentrations of OH- and SO, in the liquid phase,
which are influenced by the rates of the diffusion processes in-
volved and hence by the nature of the contact systems. In the
case of the present contact system (Fig. l), these aspects have
been studied by monitoring the pH of the liquid phase (Vizquez
et al. [lo]).
2 The Enhancement Factor
3 Experimental
Absorption experiments were performed using the apparatus il-
lustrated schematically in Fig. 2 and described in detail
elsewhere (Chenlo [ 11). The 1300 x 28 mm column, which was
insulated with a vacuum jacket, was packed with spheres 18 mm
in diameter alternating on a nylon thread with cylinders 5.8 mm
in diameter and 6.8 mm long. The cylinders had concave ends
fitting onto the spheres.
The gas phase, pure SO,, flowed into the column at a rate of
300 llh. About 50% was absorbed. The rate of absorption was

The rate of absorption of pure sulphur dioxide by alkaline solu-

tions is given by

N=kLACeE , (5)

where k, is the mass transfer coefficient for physical absorption

by the liquid phase, A is the effective interfacial area, C' is the
concentration of SO, at physical equilibrium, and E is the
enhancement factor, which may be determined experimentally
in a suitable system. The value of E can also be predicted
theoretically. The most comprehensive study is that of Chang
and Rochelle [ 1 11 who applied the surface renewal theory to ob-
tain an approximate solution for the case of a very large
equilibrium constant of the reaction A + B C so that this
reaction could be regarded as irreversible and instantaneous:
Fig. 2. Experimental set-up. I sphere-and-cylinder column. 2,3 sources of
gas and NaOH solution, 4,5,6 flowmeters, 7thermostated gas humidifier,
(6) 8,9,10,11thermometers, 12.13 manometers, 14 liquid injection system, 15
liquid preheater, 16 thermostat.
158 Chem. Eng. Technol. I 1 (1988) 156- 1.62

calculated as the difference between the inflow and outflow
rates. The liquid phase consisted of sodium hydroxide solutions
with concentrations of up to 2 M with or without 5 x
wt-% of SLS, i.e. the lowest concentration which still had a
significant effect on the absorption rate (VAzquez et al. [15]).
The liquid phase entered the column at a temperature of 25 f
0.2" C. The outflow rate varied from 3 to 8.5 l/h; the outflow
temperature depended on the conditions of the experiment. Ex-
periments were also carried out with 1 M HCl solutions, in
which the hydrolysis following absorption of SO, into water is
inhibited.
In all experiments, the wetting of the column packing was
uniform and reproducible. The complete list of systems and
conditions tested is shown in Table 1.
Table 1. Investigated Systems.
according to Vinograd and McBain [ 191. The ratio of effective
OH- to SO, diffusivities in the liquid phase, according to Eq.
(7), was assumed to be independent of concentration and
temperature over the range of experimental conditions
employed, with a value of 1.94 (Hikita et al. [S]).
Surface tension of aqueous solutions of SLS was determined ex-
perimentally by Wilheimy's plate method using a Prolabo ten-
siometer. Since the surface tension of these solutions changes
with time, values for the stirred liquid were used (Navaza [20]).
Under the employed operating conditions, the addition of
NaOH or HCl has no significant effect on the surface tension
of SLS solutions (Weast [21]).
Other relevant physical properties of aqueous NaOH and HCl
solutions of various concentrations (density and viscosity) were
taken from literature (Weast [21]).

n (No. of elements) 5 Results

[mol/l] Without SLS With SLS

Conc. NaOH 5.1 Rate of Absorption

0.Ooo 3 4 10 19 3 4 10
0.125 - 4 - - - 4 - The rate of absorption of SO, in the various aqueous solutions
0.250 - 4 - - - 4 10 used was correlated with the liquid flow rate using a function
0.500 3 4 10 19 3 4 10 of the form
1.Ooo 3 4 10 19 3 4 10
1.500 3 4 - - 3 4 -

1.750 3 - - - - - - N=aqb
2.000 3 4 10 - - 4 -
The agreement was satisfactory in all cases. As an example,
Conc. HC1 Table 3 lists the experimental results for two of the studied
1.Ooo 3 4 10 - 3 4 10 systems. The difference between the outflow and inflow

Table 3. Absorption rate in SO,-NaOH systems with and without SLS in

4 Properties a 4-element column ([NaOH] = 1 M; a and b as in Eq. (8)).

The solubility of SO, in aqueous NaOH solutions at 25" C was Without SLS With SLS
estimated for each concentration of alkali, using the expression
4 N t 4 N t
of Van Krevelen and Hoftijzer [16] and taking the total ionic [I/hl [mol/h] ["C] Whl [mol/h] ["C]
strength into account. For other temperatures, solubility was
estimated assuming a temperature dependence similar to that 3.45 2.98 46.0 3.68 1.99 40.4
determined by Rabe and Harris [17] for SO, in water. Table 2 3.45 3.08 46.1 4.09 2.13 40.8
lists the calculated values. 3.85 3.25 46.0 4.12 2.06 39.8
3.91 3.19 45.5 4.62 2.16 39.9
4.67 3.44 45.0 4.68 2.17 39.9
The diffusivity of SO, in NaOH solutions at 25" C was deter- 4.67 3.39 45.0 5.09 2.20 39.9
mined using the expression given by Ratcliff and Holdcroft 4.81 3.56 45.2 5.27 2.24 38.3
[ 181. The diffusivity of OH - at infinite dilution was estimated 5.11 3.59 44.9 5.71 2.39 38.6
5.41 3.73 45.0 5.74 2.34 38.6
5.72 3.90 44.9 6.16 2.44 38.4
5.72 3.80 44.8 6.23 2.39 37.8
Table 2. Solubility of SO, in aqueous NaOH solutions. 5.82 3.88 44.8 6.61 2.49 37.3
6.34 4.01 44.5 6.64 2.44 37.0
Conc. NaOH Temperature ["C] 6.70 4.10 44.3 6.94 2.52 37.1
[mol/l] 25 30 35 40 6.79 4.07 44.3 6.96 2.56 37.1
6.97 4.13 44.2 7.12 2.63 36.9
0.000 1.17 1.OO 0.86 0.74 7.07 4.11 44.1 7.78 2.70 36.7
0.125 1.13 0.97 0.83 0.71 7.31 4.16 44.0 7.96 2.73 36.7
0.250 1.10 0.94 0.81 0.70 7.46 4.17 44.0 - - -
0.500 1.05 0.90 0.77 0.66 7.80 4.21 43.8 - - -

1.Ooo 0.952 0.81 0.70 0.60

2.000 0.781 0.67 0.57 0.49 a = 1.810 b = 0.423 a = 1.166 b = 0.404
Chem. Eng. Techno]. I 1 (1988) 156- 162 159

N
(mol/hl

A A 0.00
0.125
0 0.25
V V 0.50
1 0 + 1-00
4 4 1.50
0 b 2.00
I 1 I 1
Fig. 3. Influence of NaOH concentra-
4 5 6 7 8
tion on absorption rate in systems with q( I /h)
and without SLS in a 4-element column.

temperatures (25" C ) is proportional to the concentration of SO,
in the liquid phase, and is smaller in systems with SLS than in
those without the surfactant.
Fig.3 shows a log-log plot of all the results obtained using
alkaline solutions with or without SLS and a column with 4
spheres and 4 cylinders. The agreement between these results
and Eq. (8) is very good. Similar behaviour was observed in
other sphere-and-cylinder columns. Thus determined parame-
ters a and b are used in the following for the purpose of inter-
polation (within the limits of experimental conditions). The
slopes of these lines were observed to increase slightly with in-
creasing NaOH concentration, i.e. increasing [NaOH] enhanc-
ed the influence of the liquid flow rate. The reduction of the ab-
sorption rate by SLS also increased with increasing NaOH con-
centration in the absorbent solution. The influence of the surfac-
tant may be explained qualitatively in terms of its reduction of
surface turbulence and, hence, the rate at which the reactant is
renewed at the interface. The effect of sodium hydroxide con-
centration on the rate of SO, absorption in the presence or
absence of SLS is shown in Fig. 4 for three liquid flow rates and
interfacial area A for various liquid flow rates and in the
presence or absence of 5 x 10- wt-% of SLS was determined
by a chemical method in an earlier study (Vrizquez et al. [22]).
Since the hydrodynamic properties of aqueous solutions
employed on this occasion slightly differed from those of the
present solutions, the values of A obtained earlier may be
assumed as valid also in the present case. Fig. 5 shows the ab-
sorption rate per unit interfacial area plotted against the number
of sphere-and-cylinder units in the column, for various concen-
trations of NaOH in the absorbent liquid. Liquid flow rate was
the same in all these experiments, and SLS was absent (the
behaviour of systems with the surfactant and at other flow rates
was similar). Absorption is seen to be most intensive near the
first few column elements, the transfer rate per unit interfacial
area falling rapidly thereafter. This behaviour is particularly
pronounced in systems with no surfactant and with high sodium
10 - H20 SLS q(l/h)
N 0 . 4
(mol/hl1 O m 6
- A A 8

a 4-sphere-4-cylinder column. In the systems with SLS, the rate

of absorption increased linearly with [NaOH] and with the li-
quid flow rate. Both these variables exert larger effects in the 5
absence of SLS, with a change in the slopes of the N - [NaOH]
plots at NaOH concentrations of about 1 M. The fact that liquid
flow rate affects the absorption rate more in the absence than
in the presence of SLS reflects the high reaction rate and the
degree of surface renewal. Considerable turbulence occurs in
long columns so that the above considerations are valid, i.e. sur- 0 l a I I I I I I

face renewal favourable for turbulence is inhibited by SLS. 0 0.5 1 .o 1.5 2.0
INaOHl (mol/l)
The performances of various columns can be compared in terms Fig. 4. Influence of NaOH concentration on absorption rate in a 4-element
of absorption rates per unit packing surface area. The effective column.
160 Chem. Eng. Technol. I1 (1988) 156- 162

influence of liquid flow rate is observed in the longest columns

where axial turbulence is most intensive (and can even be seen
15 - t 0.00
0 0.25
by the naked eye during experiments).
!!10-2 0 0.50
A v 1.00
-
mOl 0 1.50
A 2.00 5.2 The Enhancement Factor
12 h
10 -
The variation of absorption rate per unit area with column
length (Fig. 5) indicates that it is related to the driving force and
according to Eq. (3, their ratio is in fact proportional to k,E.
5 -
The enhancement factor for the absorption of SO, by aqueous
solutions of sodium hydroxide is measured experimentally as
the ratio of the rate of absorption to either the rate of absorption
in aqueous HCl solutions or that in water when the enhancement
factor for the hydrolysis of SO2 is taken into account:
0
0 5 10 15 20 "aOH "aOH
n (No. of elements1 Eexp = ~ - ~

E' , (9)
NHCI NH20
F
ig.5. Influence of column length on absorption rate per unit area for a li-
quid flow rate of 6 Uh.
The value of E' was determined as 1.10 both experimentally,
by absorption of SO, into water and into 1 M aqueous HC1 solu-
tions (Vbquez et al. [23]), and theoretically (Chang and
"2O
-
N Rochelle [24]). It should be noted that Eexpis the overall value
NSLS for the entire column, and that the local enhancement factor will
depend on the state of reaction (3). It should also be borne in
mind that the absorption of SO2 in aqueous solutions of NaOH,
2.5
HCl and H,O takes place at different temperatures.

For the 4-sphere-and-cylinder column, the values of Eexpfor

2.0 systems with and without SLS at various liquid flow rates are
plotted in Fig. 7 against the concentration of sodium hydroxide
in the inflow. The rise in Eexpwith [NaOH] at low alkali concen-
trations was practically the same for all the systems but, at
1.5 higher concentrations, the increase was much greater in the
systems without SLS than in those with SLS which exhibited a
linear dependence over the whole range of NaOH concentra-
1.0
I I 1 I I tions. Increase in the liquid flow rate slightly increased Eexpin
0 0.5 1.0 1.5 2.0 all systems. The decrease in Eexpin the presence of surfactant
INaOHl (mol/l is attributed to the reduction of surface renewal. Similar
behaviour was observed in all the other systems tested, with
Fig. 6. Influence of surfactant. Eexpdecreasing with increasing column length.

hydroxide concentrations. When the same contact device is used #aOH

to absorb SO, into water with or without surfactant, a similar -
trend is shown by the SO, transfer rate, namely it decreases PC1
asymptotically to a limiting value (Chenlo [l]).
3
Absorption of SO, in the presence of surfactant is much lower
than in its absence. The effect of the presence of SLS is reflected
by the ratio of the absorption rates in absence and in presence
of SLS. This ratio is equivalent to the ratio of interfacial
resistances to absorption in the presence and absence of SLS. 2

Fig. 6 shows this ratio plotted against the NaOH concentration

for different liquid flow rates and column lengths. For NaOH
concentrations below 1 M, the degree of inhibition was prac-
tically constant, and only in the longest columns did it ap-
preciably increase on increasing the liquid flow rate. At high 0 0.5 1.0 1.5 2.0
[NaOH], the effect of alkali concentration predominates, caus- INaOHl (mol/l)
ing increases of up to 70% in NH201NSLS.This also supports Fig. 7. Ratio of absorption rates with and without reaction in a 4-element
the explanation in terms of an increase in turbulence, since the column.
 Chem. Eng. Technol. 11 (1988) 156-162 161

In order to compare the experimental enhancement factor with and outflow temperatures (which varied from one system to
those based on the assumption of a single reaction plane by another). The partial pressure of SO, was calculated by adding
renewal theory or film theory (Eq. (7) or a similar equation with the current atmospheric pressure to the inflow overpressure and
the square root removed), and with that based on assuming two substracting the pressure of water vapour at the mean
reaction planes by penetration theory (Hikita et al. [7]), the ex- temperature. These data yield the ratio C&oHIC~o,,which ap-
perimental conditions must be such that reaction (3) is irreversi- pears in Eq. (7) and is used in literature in the discussion of the
ble (OH- must be in excess of SOz) and the absorption pro- enhancement factor. The effect of temperature variation on the
cesses with and without reaction must be referred to the same absorption of SO, in water and in alkaline solutions was cor-
temperature. The systems in which the irreversibility of reac- rected for using the data obtained in a previous study of the rate
tion (3) is ensured by the presence of excess liquid phase reac- of absorption of SO, into water at 25, 30, 35 and 40°C in the
tant from inflow to outflow can be identified by consideration same contact system (Barros [25]). These data yielded the rate
of the relevant material balances and the stoichiometry of the of absorption of SO, into water at the mean temperature of the
reactions involved. The experimental absorption rate-liquid experiments with sodium hydroxide, and the experimental
flow rate data of Table 3 (and the corresponding data for other enhancement factor was calculated as the ratio of absorption
systems) allow the calculation of the total concentrations of ab- rates in NaOH solution and water at this temperature.
sorbed SO, in the liquid phase (molecular SO, + SO:- +
HSO,-). For the systems with SLS, the concentration of sodium
hydroxide in the inflow is plotted in Fig. 8 against the total ab- 3
sorbed SO, concentration for various column lengths and liquid
flow rates (the results for systems without SLS are similar). The E
broken straight lines indicate 1:2 and 1:1 stoichiometries, i.e.
the equivalence points of reactions (3) and (4),and together with
the proportions of the reactants determine the boundaries be-
tween the basic, buffer and acid regions of the column (Fig. 1). 2
In systems with SLS, it is much easier to maintain an excess of
NaOH than in systems without SLS, which once more shows
the influence of hydrodynamics on absorption rate and effective
interfacial area. The extensive contact between the phases in the
longer columns also makes it impossible to maintain an excess
1
of the reactant. This analysis thus identifies the experimental
-
systems with NaOH in excess of total absorbed SO,.
Penetration
theory
Liquid-film
I_____
TWO reaction-plane model
One reaction-plane model ---
In the contact systems employed, there is a large difference be- theory
tween the concentrations of OH - in the inflow and outflow, and
their mean was used in applying Eq. (7); the concentration in 0
the inflow was that of the prepared solution, and the concentra- 0 co -
1 2 OH
tion in the outflow was calculated from the stoichiometry of __
reaction (3). The solubility of SO, in the alkaline solutions is Ce
s02
given by Table 2 for each NaOH concentration and tempera- lc739]
ture; the temperature used was the mean of the inflow (25 "C)
Fig. 9. Enhancement factor for absorption of SO, by aqueous NaOH
solutions.

2.0 Fig. 9 shows the experimental enhancement factors obtained for

I NaOH I systems with and without SLS together with the values
( m u1 predicted by film theory (using a one-plane model) and by
1.5 penetration theory (using one-and two-plane models). The
enhancement factor in the systems without surfactant is larger
than in those with surfactant, which reflects the influence of tur-
1.0 bulence at the interface, i.e. in the presence of SLS, the ex-
perimental results agree quite well with the predictions of
penetration theory based on a single-plane model, whereas in
0.5 the absence of SLS they are more in accordance with the two-
plane model. The single-plane film theory model predicts
behaviour intermediate between these extremes. The presence
0.0
of interfacial turbulence could perhaps be taken into account by
0 0.25 0.50 0.75 1.00
modifying the diffusion coefficients.
lso21(mol/l)
Ezz$l
Fig. 8. States of the SO,-NaOH reaction in each of the systems with SLS. Received: July 21, 1987 [CET 731
162 Chem. Eng. Technol. 11 (1988) 162- 170

References [I31 Danckwerts, P.V., Chem. Eng Sci. 23 (1968) p. 1045.

[l] Chenlo, F., Thesis, Univ. Santiago de Compostela, Spain 1986.
[2] Costa, E., Lizaro, A., Borderia, J., An. R. SOC.ESP.Fis. Quim.,Ser.
B. 57 (1961) p. 321.
[3] Dean, J.A., Lunge’s HandbookofChemzstry, 1 Ith ed., McGraw-Hill,
New York 1973.
[4] Saal, R.N.J., Rec. Trav. Chim. 47 (1928) p. 264.
[5] Goetler, L.A., Thesis, Univ. Delaware 1967.
[6] Onda, K., Kobayashi,.T., Fujine, M., Takahashi, M., Chem. Eng
Sci. 26 (1971) p. 2009.
[7] Hikita, H., Asai, S., Takatsuka, T., Chem. Eng J. (Luusanne) 4
(1972) p. 31.
[8] Hikita, H., Asai, S., Tsuji, T., AIChEJ. 23 (1977) p. 538.
[9] Danckwerts, P.V., Gus-Liquid Reactions, McGraw-Hill, New York
1971.
[ 101 Vizquez, G., Antorrena, G., Chenlo, F., Afinidad 44 (1987) p. 504.
[ l l ] Chang, C.S., Rochelle, G.T., AIChE 88th National Meeting,
Philadelphia 1980.
[12] Olander, D.R., AIChEJ. 6 (1960) p. 233.
[14] Hikita, H., Asai, S., Takatsuka, T., Chem. Eng J. (Lausanne) I 1
(1976) p. 141.
[15] Vbquez, G., Antorrena, G., Chenlo, F., Afinidad44 (1987) p. 522.
[16] Van Krevelen, D.W., Hofiijzer, P.J., Chim. Ind. XXf” Congr. In?.
Chim. Id., SOC. Chim. Id., Bruxelles 1948.
[I71 Rabe, A.E., Harris, J.F., J. Chem. Eng Data 8 (1963) p. 333.
[I81 Ratcliff, G.A., Holdcroft, J.G., Trans. Inst. Chem. Eng. 41 (1963)
p. 315.
[19] Vinograd, J.R., McBain, J.W., J. Am. Chem. Soc. 63 (1941) p. 2008.
[20] Navaza, J.M., Thesis, Univ. Santiago de Compostela, Spain 1986.
[21] Weast, R.C., (Ed.), Handbook of Chemistry and Physics, 50th ed.,
Chemical Rubber Publishing Co., Cleveland 1969 - 70.
[22] Vbquez, G., Antorrena, G., Chenlo, F., Paleo, F., An. Quim. 82
(1986) p. 288.
[23] Vizquez, G., Chenlo, F., Antorrena, G., Paleo F., (unpublished
work) 1987.
[24] Chang, C.S., Rochelle, G.T., AIChE J. 27 (1981) p. 292.
[25] Barros, J., Thesis, Univ. Santiago de Compostela, Spain 1980.

A New Fluid Dynamic Model for Mixing of Newtonian and Power-law

Liquids in the Transient Regime*
Rolf Zeppenfeld and Alfons B. Mersmann**

In the description of mixing processes influenced by viscosity in pseudoplastic (power-law)

fluids, a definition of representative viscosity is normally used which takes into account the
variable flow behaviour of the stirred material as a result of different shear stresses. In this con-
text, the Metzner and Otto concept, which postulates that a representative shear rate is propor-
tional to stirring speed, has become widely known, although the power calculation is inaccurate,
particularly in the transient regime between the laminar and turbulent flow. A new model of fluid
dynamics in the mixing vessel is presented, based on the increase of the mean flow velocity stan-
darized with the stirrer’s tip velocity in the transition regime. It provides a physical explanation
for the above deviations. A suitable definition of representative viscosity substantially improves
the accuracy of calculations of the stirring power in power-law fluids.

1 Introduction The definition of a representative viscosity is used in the

Numerous fluids, which are stirred in the practice of process
engineering, have non-Newtonian flow characteristics, i.e. no
viscosity exists as a fluid property. Unit operations, for ex-
ample blending, heat transfer, dispersion with mass transfer
and, last but not least, the impeller’s power consumption de-
pend on these flow characteristics which, in turn, are influenced
by operational parameters.
* Modified version of a paper presented at the “GVC Working Party on
Mixing”, Trier, 4./5. May 1987.
** Dip1.-Ing. R. Zeppenfeld and Prof. Dr.-Ing. A. B. Mersmann,
Lehrstuhl B liir Verfahrenstechnik, TU Munchen, Arcisstr. 21, D-8000
Munchen 2.
qualitative and quantitative description of these physical pro-
cesses. This definition forms a link to the model concepts apply-
ing to Newtonian fluids. It is, thereby, accepted that the
representative viscosity defined in this way is only valid for the
operation for which it was postulated or ascertained (and is,
therefore, representative).
In spite of this, it often happens that the representative viscosity
for the power input in the laminar regime is also used for the
modelling of completely different mixing problems. This is
even more questionable since the real power characteristic fits
in with the usual concept less and less satisfactorily, the more
turbulent the regime becomes and many large scale stirring
operations occur in the turbulent flow regime. Several, more re-

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