1310 Ind. Eng. Chem. Res.

2008, 47, 1310-1317

Dynamic Measurement of Carbon Dioxide Volumetric Mass Transfer Coefficient

in a Well-Mixed Reactor Using a pH Probe: Analysis of the Salt and
Supersaturation Effects
M. Kordač and V. Linek*
Department of Chemical Engineering, Institute of Chemical Technology, Prague, Technická 5,
166 28 Prague 6, Czech Republic

This paper presents a new method for the evaluation of volumetric mass transfer coefficients (kLa) using a
pH probe response recorded during the absorption of carbon dioxide in a well-mixed reactor. For this method
of evaluation, it is not necessary to know the reaction equilibrium constant, the experiment start time, or the
initial and final steady-state pH probe readings. The experimental procedure is based on Hill’s recent publication
(Ind. Eng. Chem. Res. 2006, 45, 5796). Hill reported a decrease in kLa following the addition of salt during
carbon dioxide absorption in a well-mixed reactor and explained it as the result of ionic charge effects reducing
the ability of carbon dioxide molecules to diffuse away from the surface. Generally, oxygen absorption from
air is preferred because the solubility of oxygen is low and, thus, so will be the gas-phase depletion. In such
experiments, the mass transfer coefficients are less affected by gas-phase residence time distribution and by
bubble-size distribution. The solubility of carbon dioxide is 26 times higher than that of oxygen, which can
lead to significant gas concentration changes. Thus, the kLa values, measured using absorption of diluted
carbon dioxide, are more likely to be distorted by driving force errors caused by the use of an inappropriate
gas-mixing model. Using a stirred cell, the interfacial area of which is known, the mass transfer coefficients
of oxygen and carbon dioxide in water and in a salt solution were compared. The mass transfer coefficients
obtained for oxygen agreed with, or were slightly superior to, the coefficients obtained for carbon dioxide,
which corresponds with the lower molecular diffusivity of CO2. The mass transfer coefficients of carbon
dioxide obtained in salt solution were not significantly lower than those obtained in pure water, which is in
strong agreement with the literature but contradicts the results reported by Hill. It is shown that Hill’s findings
may be the result of his use of both an inaccurate gas-mixing model (no depletion of gas) and an imprecise
reaction term in his equations.

Introduction serious underestimation of kLa values in the case of carbon

The steady increase in carbon dioxide concentration in the
atmosphere, and the belief that it is a significant contributing
factor to global warming,1 has recently led to attempts (e.g.,
refs 1 and 2) to develop photobioreactors that use atmospheric
carbon dioxide as a source of carbon for cell cultures. Because
the solubility of carbon dioxide, compared with other substrates,
is not high enough to ensure an adequate carbon supply at the
start of fermentation, carbon dioxide must be continuously fed
into a fermentation broth by gas absorption. The rate of carbon
dioxide absorption is a limiting factor in the process, and thus,
the volumetric mass transfer coefficient is an important param-
eter in photobioreactor design. Typically, engineers estimate the
mass transfer rate of carbon dioxide using oxygen mass transfer
coefficients that factor in a different diffusion coefficient of
carbon dioxide. Recently, this procedure has been questioned
by Hill,3 who reported notably lower carbon dioxide mass
transfer coefficients compared to those of oxygen.
Hill3 used a dynamic method to measure carbon dioxide mass
transfer coefficients in a well-mixed reactor, with the coefficients
being evaluated from pH profiles of the aqueous phase after
the introduction of bubbles containing carbon dioxide. In this
procedure, Hill assumed that the gas-phase concentration of
carbon dioxide in the vessel was constant and equal to the inlet
concentration.
The aims of this paper are as follows: (i) to demonstrate
that the use of an incorrect absorption driving force results in
* Corresponding author e-mail: linekv@vscht.cz.
10.1021/ie0711776 CCC: $40.75 © 2008 American Chemical Society
Published on Web 01/08/2008
dioxide absorption, (ii) to propose a new method that allows
kLa to be calculated without knowledge of the experiment start
time or of the initial and final steady-state readings of the pH
probe (knowledge of which are essential to Hill’s method), and
(iii) to critically reassess the effect of salt on the absorption
rate of carbon dioxide presented by Hill.
Theory of the Method
Carbon dioxide is dissolved in the aqueous phase as four
different compounds (carbon dioxide, CO2; carbonic acid, H2-
CO3; bicarbonate ion, HCO3-; and carbonate ion, CO3)), the
equilibrium concentrations of which are pH-dependent. Assum-
ing equilibrium reactions to be instantaneous, Hill deduced how
to recalculate a pH profile into a profile of dissolved carbon
dioxide and, therefore, how to evaluate the volumetric mass
transfer coefficients of carbon dioxide.
The dissociation of carbon dioxide in water can be described
using the following relation set
K0 K1
H2O + CO2 798 H2CO3 798 H+ + HCO3- (1)
From the value of the dissociation constant K0 (7 × 10-7 M,
Danckwerts4), it follows that the concentration of dissolved CO2
greatly exceeds that of H2CO3 and, thus, that the dissolved CO2
and H2CO3, the neutral compounds, may be considered as one
component, which, following Hill’s notation, is called carbonic
acid, H2CO3, in the following text. Danckwerts and Sharma5
 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008 1311

provided the following expression for calculation of the solubil-
ity of carbon dioxide
(cH2CO3)/ ) pCO2/H ) pCO2 × 10-(5.3-1140/T)
where H is Henry’s coefficient, pCO2 is the partial pressure of
carbon dioxide above the aqueous phase, and (cH2CO3)* is the
concentration of physically dissolved CO2 and H2CO3 in
equilibrium with pCO2 in the gas phase. The same authors5 also
provided the following expression for the equilibrium constant
of the second reaction
cH+cHCO3-
K1 ) ) 10-(3404.7/T+0.03279T-14.832)
cH2CO3
By analyzing equilibrium reactions, Hill3 deduced that the
concentration of carbonate ion is insignificant and that, as the
solution becomes acidic (pH < 6), the concentration of
hydroxide ion may also be ignored. In this case, the principle
of electroneutrality requires that the concentrations of hydrogen
and bicarbonate ion be equal
cH+ ) cHCO3-
Danckwerts and Sharma5 also provided the following rate
equation of the hydrolysis (eq 1)
the interface. Assuming both an ideal mixing of the gas phase
and a negligible mass transfer resistance in the gas phase,
(cH2CO3)/2 is in equilibrium with the carbon dioxide concentra-
(2) tion in the gas leaving the vessel. The latter assumption holds
for the absorption of sparingly soluble gases, such as oxygen
and carbon dioxide, but the former assumption is questionable
at some situations when absorption takes place in a mechanically
agitated gas-liquid contactor. A detailed study7 on the correct
use of the dynamic method for the determination of kLa in
aerated agitated vessels has shown that these assumptions hold
for the measurement of low values of kLa (<∼200 h-1), which
was the case in Hill’s experiments. Furthermore, the same
authors have shown7 that, because it avoids mixing interchanged
(3) gases in a reaction vessel, a gas interchange start-up technique
considerably broadens the applicability of the dynamic method,
when used with an ideal mixing of the gas phase. The start-up
technique is as follows: after saturating the batch with a gas
(e.g., air or nitrogen), stirring and the gas supply are interrupted
for the time necessary for the bubbles to escape from the batch;
next, the stirring is restarted simultaneously with the introduction
of another gas containing the solute component (carbon dioxide).
In the subsequent evaluation, it is necessary to be aware of the
(4) fact that the instantaneous value of an interfacial area of gas
bubbles in a dispersion increases linearly over the start-up period
θ. The start-up period ends when gas holdup Hu reaches a steady
state at time θ ) VLHu/[QG(1 - Hu)].

( )
The bicarbonate concentration in relation 7 can be replaced
dcH2CO3 cH+cHCO3- using the differentiated eq 3 [dcHCO3- ) d(K1cH2CO3)0.5 )
B1 cH2CO3 -
) -k 0.5(K1)0.5(cH2CO3)-0.5 dcH2CO3] leads to
dt K1 (5)

[ ]
log B
k 1 ) 329.85 - 110.54 log T - 17265/T dcH2CO3 2
) kLa((cH2CO3)/2 - cH2CO3) (8)
For absorption from gas bubbles in dispersion, the lowest value
dt 2 + (K1/cH2CO3)0.5
estimated for the physical mass transfer coefficient koL is 2 ×
10-4 m/s (e.g., Calderbank and Moo-Young6). Using eq 5, Assuming a well-mixed gas phase, the molar fraction of carbon
together with the relation given in ref 4, the enhancement factor dioxide in the gas leaving the reactor, y2, can be deduced from
of absorption accompanied by a first-order irreversible chemical the mass balance of carbon dioxide. If changes in the rate of
reaction (eq 1) at 27.5 °C can be estimated as volumetric gas flow through the reactor, and CO2 accumulation
in the gas holdup, are both omitted, the balance has the following

E)
x(k ) o 2
L +B
k 1DCO2
)
form

koL p Q GH
QG (y1 - y2) ) ((cH2CO3)/1 - (cH2CO3)/2) )
x(2 × 10 -4 2
) + 0.0311 × 2 10 -9
) 1.000777 (6)
RT RT
kLa((cH2CO3)/2 - cH2CO3)VL (9)
2 × 10-4
This value is on the conservative side compared to the factor which can be rewritten as
for the reversible version of the same reaction. From this value
of E, it follows that the absorption of carbon dioxide in water A 1
(cH2CO3)/2 ) (c )/ + c
is not enhanced by a reversible reaction (eq 1). 1 + A H2CO3 1 1 + A H2CO3
Model of Instantaneous Reversible Reaction (Eq 1) Taking
Place in Bulk Liquid. In this model, it is assumed that carbon Q GH
dioxide is physically absorbed and, in bulk liquid, undergoes a A) (10)
kLaVLRT
reversible reaction (eq 1) that is sufficiently fast to keep the
bulk concentrations of carbonic acid, bicarbonate ion, and
By substituting (cH2CO3)/2 from eq 10 into eq 8, we obtain the
hydrogen ion in equilibrium. Assuming equilibrium (given by
following differential equation for describing the dynamic
reaction 1) is reached in bulk liquid, the differential balance of
response of the concentration of carbon dioxide in the liquid
carbon dioxide in the liquid phase during gas absorption is as
phase
follows
dcH2CO3 dcHCO3- dcH2CO3 A
kLa((cH2CO3)/2 - cH2CO3) ) + (7) ) kLa ((c )/ - cH2CO3) ×
dt 1 + A H2CO3 1

[ ]
dt dt
2
(11)
where (cH2CO3)/2 is the concentration of carbonic acid (i.e., the 2 + (K1/cH2CO3)0.5
sum of physically dissolved CO2 and H2CO3) in the liquid at
1312 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008
Model of Moderately Rate Reversible Reaction (Eq 1)
Taking Place in Bulk Liquid. In this model, it is assumed that
carbon dioxide is physically absorbed and undergoes a reversible
reaction (eq 1) in bulk liquid, the reaction rate of which is given
by eq 5. In this case, the balances have the following forms
dcH2CO3
) kLa((cH2CO3)/2 - cH2CO3) -
( ) ( )
dt
(cHCO3-)2 dcHCO3- (cHCO3-)2
k1 cH2CO3 - ) k1 cH2CO3 -
K1 dt K1
where (cH2CO3)/2 is given by eq 10 for a well-mixed gas phase in
a vessel.
Model of Absorption Presented by Hill.3 To factor in the
changes in carbonic acid concentration due to reaction system
1, Hill, instead of using the differential relation dcHCO3- )
d(K1cH2CO3)0.5, used a simple relation between the concentrations
of bicarbonic ion and carbonic acid cHCO3- ) (K1/cH2CO3)0.5cH2CO3,
which follows from eq 3 and is valid for steady-state concentra-
tions only. He presented the mass balance of dissolved carbon
dioxide in the following form
[ ]
dcH2CO3 1
) kLa((cH2CO3)/2 - cH2CO3)
dt 1 + (K1/cH2CO3)0.5
Comparison of Relations 11, 12, and 13
Equations 11, 12, and 13 were integrated to produce the
concentration profiles compared in Figure 1. Integration was
performed by applying the conditions presented in Figure 2 of
Hill’s paper: (cH2CO3)initial ) 1.38 × 10-5 M; (cH2CO3)/1 ) 2.81
× 10-3 M; K1 ) 8.15 × 10-7 M-1; QG ) 1.1 L/min; VL )
2.45 L; HCO2 ) 32.09 atm/M; and T ) 300.5 K. The
concentration profiles obtained from eqs 11 and 12 did not differ,
their agreement validating Hill’s assumption that reaction
equilibrium is instantaneously achieved in bulk liquid. However,
the profiles obtained from eqs 11 and 13 differed significantly;
the higher the kLa value, the greater the difference. This was
due to the following: (i) the different reaction terms used for
the conversion of carbonic acid into bicarbonate ion (compare
the terms in square brackets in eqs 11 and 13) and (ii) the use
of an incorrect driving force for absorption. A well-mixed gas
phase is assumed in models 11 and 12, and thus the outlet gas
concentration is used, but Hill assumed that the concentration
of carbon dioxide in the gas phase is constant during its
absorption and, consequently, used the inlet gas concentration
to determine the driving force in eq 13.
Because the solubility of carbon dioxide is relatively large,
changes in the concentration of carbon dioxide in the gas phase
due to absorption must be taken into account. This fact is
illustrated in Figure 2, in which outlet gas concentrations, for
the absorption of both 10% CO2 and oxygen (from air) into
water, are plotted as a function of kLa, as well of the saturation
(R) of the liquid phase with the solute gas. Saturation R is
defined as the ratio of dissolved gas concentration to saturated
solution (e.g., for carbon dioxide, R ) cH2CO3/(cH2CO3)/1). Pre-
cisely because the solubility of carbon dioxide is 26 times higher
than that of oxygen (ref 8: HO2 ) 819 atm/M), the reduction
for CO2 absorption remains large, even when the decrease in
gas-phase concentration for air absorption is insignificant. For
example, Figure 2 shows that, for kLa ) 60 h-1, the y2/y1 ratio
is 0.37 at the start of the dynamic experiment (R ) 0) and equals
0.68 at a saturation of R ) 0.5. Correspondingly, the concentra-
(12)
Figure 1. Concentration profiles obtained by integration of eqs 10 and
11. Conditions: (cH2CO3)initial ) 1.38 × 10-5 M; (cH2CO3)/1 ) 2.81 × 10-3
M; K1 ) 8.15 × 10-7 M-1; QG ) 1.1 L/min; VL ) 2.45 L; HCO2 ) 32.09
atm/M; T ) 300.5 K.
tions of CO2 gas in the vessel are only 3.8% and 6.9%,
respectively. However, in eq 13, Hill assumed that the concen-
tration of carbon dioxide in the gas phase was essentially
constant, equaling 10% during the whole experiment. Such an
overestimation of the absorption driving force leads to serious
underestimation of kLa.
(13)
Evaluation of pH Profiles
Hill reported problems in the evaluation of the pH profile
generated by each run of his experiment. To solve these
problems, caused by time delays after gas switching, Hill used
an empirical equation to estimate both “the time to the midpoint
of the rise in concentration” and “the span of the rising curve”,
thus allowing him to determine the experiment start time. To
avoid using this unnecessary procedure, another method of
evaluation is proposed here, in which it is not necessary to know
the initial and final steady-state readings of the pH probe nor
the start time.
In order to solve eq 11 analytically, it is necessary to analyze
the reaction term in square brackets. In Figure 3, this term is
plotted as a function of the equilibrium partial pressure of carbon
dioxide. The equilibrium constant K1 (given in ref 9) is as
follows,
pK1 ) 3670.7/T - 62.008 + 9.7944 ln T -
0.0118S + 0.000116S2 (14)
where salt concentration is defined by salinity S in units of g/kg.
From Figure 3, it follows that the reaction term is approximately
constant and equals 0.99 for pH < 5. Therefore, because pH is
usually <5 during the main part of carbon dioxide absorption
experiments, the following approximation can be used in the
evaluation of absorption experiments conducted in both water
and salt solution
[ ]
2
≈ 0.99 (15)
2 + K1/(cH2CO3)0.5
The differential eq 11 then can be reduced to
dcH2CO3 A
) kLa 0.99((cH2CO3)/1 - cH2CO3) )
dt 1+A
B((cH2CO3)/1 - cH2CO3) (16)
where

A caused by the fact that the diffusion coefficient of oxygen in
B ) k La 0.99
1+A
[ ]
-1
0.99 VLRT
kL a ) -
B QGH
Integration of eq 16 with the initial condition cH2CO3 (0) )
(cH2CO3)0 leads to the following time profile for the concentration
of H2CO3
cH2CO3(t) ) (cH2CO3)/1 - [(cH2CO3)/1 - (cH2CO3)0] e-Bt
Using the following rearrangements,
cH2CO3(t + ∆t) ) (cH2CO3)/1 - [(cH2CO3)/1 - (cH2CO3)0] e-B(t+∆t)
cH2CO3(t) - cH2CO3(t + ∆t) ) ∆cH2CO3 )
e-Bt[(cH2CO3)/1 - (cH2CO3)0](e-B∆t - 1)
we obtain
ln(K1∆cH2CO3) ) -Bt + const1
To determine the concentration of carbonic acid, we use the
following simple inverse relationship between the concentrations
of carbonic acid and hydrogen ion given by eqs 3 and 4
10-2pH
cH2CO3 )
K1
For K1∆cH2CO3, it can thus be deduced from eq 21 that
K1∆cH2CO3 ) 10-2pH(t) - 10-2pH(t+∆t)
For pH < 5, the volumetric mass transfer coefficient kLa can
be calculated from B in eq 20. Note that B is dependent neither
on the initial nor final steady-state values of the pH probe signal
nor on the equilibrium constant K1. Integrating eq 11 using kLa
) 110 h-1, the highest value measured by Hill, we obtained
the concentration profile presented in Figure 4. Evaluating the
profile using ∆t ) 30 s, we obtained B ) 0.00733 s-1. Using
eq 17, the volumetric mass transfer coefficient was calculated
as
[ ]
-1
0.99 VLRT
k La ) - )
B QGH
[ ]
-1
0.99 2.45 × 0.08205 × 300.5
- )
0.00728 0.018333 × 32.09
0.03002 s-1 ) 108 h-1
This agreement shows that the simplifications used have a
negligible effect on the resulting kLa value. Because the highest
value measured by Hill was used in this example, it can be
expected that this small difference may be valid in the whole
range of kLa values.
Comparison of Hill’s Data with Literature Data
Hill3 compared his kLa data with those of Robinson and
Wilke,10 who used a similar vessel to measure oxygen mass
transfer in both water and saltwater. While both studies used
similar mixing and aeration rates, Hill’s kLa data ranged from
20 to 120 h-1, whereas those of Robinson and Wilke ranged
from 40 to 200 h-1. Hill has explained that this difference is
Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008 1313
water being 20% higher that that of carbon dioxide. However,
(17) this does not fully explain a difference in kLa of ∼40% (relative
to the maximum value obtained by Robinson and Wilke10) at
(kLa)(13) 120 h-1. On the other hand, 40% corresponds well with
the difference between Hill’s model (eq 13) and the model
presented in this work (eq 11). We can use these equations to
estimate the kLa ratio as follows,
2A 1 + (K1/cH2CO3)
0.5
(kLa)(13)
(18) ) (23)
(kLa)(11) 1 + A 2 + (K /c )0.5
1 H2CO3
In Figure 5, this ratio is plotted as a function of kLa for the
experimental ranges described above. The experimental mean
value of cH2CO3 was calculated using [(cH2CO3)initial + (cH2CO3)/1]/2.
(19)
Other authors7,21-24 have reported lower kLa values in
noncoalescent batches at a significant depletion of solute
component in the gas phase, exactly the conditions described
by Hill for his experiments in salt solution. In all these cases,
it is likely that there was serious overestimation of the absorption
(20) driving force caused by the use of an incorrect gas-mixing
model. The increased likelihood of incorrectly estimating the
absorption driving force under such conditions is a result of
the following process. Each bubble, according to its size and
residence time in the batch, exhibits different gas-phase deple-
tion and, thus, a different absorption driving force. The
differences are more pronounced in dispersions in solutions of
(21) electrolytes and in viscous solutions, where the bubble coales-
cence rate and, thus, the mutual mixing of their contents are
hindered compared with dispersions in pure water. As a result,
estimates of the absorption driving force based on unstructured
(22) models (plug flow, perfect mixing) may differ from the real
situation by an order of magnitude. The consequent underesti-
mation of kLa based on these models is serious even for
sparingly soluble gases, such as oxygen.7,21,23
Analysis of the Salt and Supersaturation Effects
It is well-known7,10,11 that the addition of a structure-making
electrolyte (such as NaCl) reduces the rate of bubble coales-
cence, which, in turn, results in reduced bubble size and an
increase in kLa values compared to those measured in pure
water. However, while Hill visually observed bubble size to be
noticeably smaller when salt (2.85% solution NaCl in water)
was present, he actually reported a decrease in kLa values (e.g.,
from a mean value of 34 h-1 down to 28 h-1 at 375 rpm and
an aeration rate of 1.1 L/min). Hill3 explained this as follows:
“the ionic charge effect at the bubble surface may have reduced
the ability of carbon dioxide molecules to diffuse away from
the increased bubble surface area, resulting in no net change in
the overall volumetric mass transfer coefficient”.
To reach an unambiguous conclusion about the effect of salt
on the mass transfer coefficient of carbon dioxide, we measured
the mass transfer coefficients kL of oxygen and carbon dioxide
in water and in 2.85% NaCl solution in a stirred cell with a flat
gas-liquid interface (interfacial area and absorption driving
force well-defined). The cell was a cylindrical vessel (inner
diameter ) 0.117 m) equipped with six baffles, together with,
on a common shaft, a vaned disc impeller (diameter ) 0.06 m)
in the liquid phase and a two-paddle agitator in the gas phase.
The impeller shape enabled the liquid to be agitated without
appreciable surface wave motion. The surface remained flat
across the whole range of agitator frequencies used in our
experiments (100, 200, and 300 min-1). The temperature was
1314 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008
Figure 2. Molar fraction of solute gas component in outlet gas. Conditions: (cH2CO3)initial ) 1.38 × 10-5 M; (cH2CO3)/1 ) 2.81 × 10-3 M; K1 ) 8.15 × 10-7
M-1; QG ) 1.1 L/min; VL ) 2.45 L; HCO2 ) 32.09 atm/M; T ) 300.5 K.
Figure 3. Reaction term as a function of equilibrium partial pressure of carbon dioxide. Conditions: K1 from eq 14; T ) 300.5 K.
Figure 4. Concentration and pH profiles obtained by integration of eq 11
for kLa ) 110 h-1 and evaluated using eq 20. Conditions: (cH2CO3)initial )
1.38 × 10-5 M; (cH2CO3)/1 ) 2.81 × 10-3 M; K1 ) 8.15 × 10-7 M-1; QG
) 1.1 L/min; VL ) 2.45 L; HCO2 ) 32.09 atm/M; T ) 300.5 K.
maintained at 20 °C by circulating liquid through the cell jacket.
At the start of each experiment, the vessel was filled with 1/2 L
of liquid (i.e., specific liquid surface a ) 19.5 m-1). Experiments
were carried out batchwise in the liquid phase and continuously
in the gas phase. Pure oxygen, carbon dioxide, and nitrogen,
all taken from the cylinders, were used as the gas phase. A
membrane-covered polarographic probe of our own construction
(described in detail by Fujasova et al.12) and the glass pH probe
(Sentix 41, WTW) were used for monitoring solute gas
concentration in the liquid batch.
Mass transfer coefficients were evaluated from concentration
profiles of oxygen and carbon dioxide in the liquid batch during
absorption/desorption of the gas into/out of the batch. At the
beginning of each experiment, pure oxygen saturated with water
vapor was fed above the liquid surface until the gas saturated
Figure 5. Comparison of relative decrease in kLa values obtained using
Hill’s model (eq 13) and our model (eq 11), as follows from eq 23.
Conditions: K1 ) 8.15 × 10-7 M-1; VL ) 2.45 L; HCO2 ) 32.09 atm/M;
T ) 300.5 K.
the batch. Next, the oxygen atmosphere in the cell was quickly
flushed with nitrogen. After the interchanges, (O2 f N2)
followed by (N2 f O2), oxygen desorption and, subsequently,
absorption were monitored. Then, each experiment was repeated
using carbon dioxide instead of oxygen. In all experiments, a
gas flow rate of 100 mL/min was fed above the liquid surface
to ensure an insignificant concentration of the solute in the gas
above the agitated liquid. This implies that the value of A tends
to infinity, and thus, A/(1 + A) ) 1 in these experiments. In
the case of the linear dependence of probe signal G on the
oxygen concentration [G ) rcO2 + q; r and q are arbitrary
 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008 1315

Figure 6. Oxygen probe responses measured for oxygen absorption/desorption in stirred cell and evaluated according to eq 24. Batch: water, 20 °C.

Figure 7. pH probe responses measured for carbon dioxide absorption/desorption in stirred cell and evaluated using eq 20 for pH < 5. Batch: 2.85% NaCl
solution, 20 °C.

constants], oxygen absorption can be evaluated by reducing eq Table 1. Mass Transfer Coefficients of Oxygen and Carbon Dioxide
20 to in Water and in 2.85% Salt Solution Measured in a Stirred Cell at
20 °C; Values in Italic Were Measured in Conditions under Which
Supersaturation May Occur
ln(∆G) ) -kLa‚t + const2 (24)
kL × 105, m/s
Probe responses (pH and oxygen) evaluated using relations Agitator,
100 200 300 100 200 300
frequency,
20 and 24 are presented in Figure 6 for water and in Figure 7 rpm abs. des. abs. des. abs. des. ave.a ave.a ave.a
for 2.85% NaCl solution. ∆G represents the difference between
water, O2 2.09 2.14 3.57 3.48 5.67 5.39 2.18 3.50 5.29
oxygen probe readings measured at times t and t + ∆t (∆t ) 2.25 2.21 3.60 3.51 5.41 5.18
144 s). Using eq 22, K1∆cH2CO3 was calculated from pH probe water, CO2 4.63 4.65 2.06 3.21 4.69
readings measured at times t and t + ∆t (∆t ) 100 s). Table 1 2.15 1.93 3.27 3.44 3.95b 4.40
presents the mass transfer coefficients evaluated from the probe 1.97 2.06 3.14 3.37 4.75 4.87
responses during absorption and desorption. It also displays the kL,CO2 calculated from eq 25 1.98 3.19 4.81
2.85% NaCl, 2.22 2.15 3.57 3.48 5.49 5.31 2.12 3.45 5.21
kL values of carbon dioxide obtained by the recalculation of O2 2.18 2.09 3.49 3.41 5.24 5.11
oxygen mass transfer coefficients using the following ratio of 2.85% NaCl, 1.77 2.62 3.52 4.53 5.48 6.71 1.89 3.36 5.44
diffusion coefficients of the gases in water [ref 19 for O2, ref CO2 2.03 2.57 3.44 4.38 5.55 6.15
20 for CO2] 1.87 2.10 3.13 4.25 5.28 6.26
a Average values. b Not considered in the average value.
kL,CO2 ) kL,O2(DCO2/DO2)1/2 )
Our results show that the kLa of oxygen absorption (N2 f
kL,O2(1.90 × 10-9/2.30 × 10-9)1/2 ) 0.91kL,O2 (25) O2) and carbon dioxide desorption (CO2 f N2) (data in italic
in Table 1) are systematically higher (by 4% for oxygen and
Distortions of the responses, caused by the dynamics of the by up to 25% for carbon dioxide in the salt solutions) than the
pH probe, had negligible impact on the evaluation as, in both corresponding desorption (O2 f N2) and absorption (N2 f CO2)
this and Hill’s work, the time constant of the electrode was much values. Some authors13-17 have reported that, all other experi-
larger (see Figure 8, k > 3500 h-1) than the kLa (<110 h-1). mental conditions being equal, kLa measurement methods
1316 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008
Figure 8. Responses of pH probe measured for pH step changes: pH
differences are measured for time interval ∆t ) 1.03 s.
involving the temporary or permanent supersaturation of liquid
by dissolved gases produce higher kLa values than methods not
involving supersaturation. The supersaturation of liquid by gas
occurs if it holds that18
∑j pL j
s) -1>0 (26)
pt
i.e., the combined content of dissolved gases in the liquid
is higher than its complete saturation. Where simultaneous
physical absorption-desorption occurs, supersaturation may
occur at the constant total pressure of the system pt as a result
of the different component diffusivities. During an (N2 f O2)
interchange, oxygen has a higher diffusivity in the liquid
phase than nitrogen, whereas during a (CO2 f N2) inter-
change, nitrogen has a higher diffusivity in the liquid phase
than carbon dioxide (ref 19: DO2water ) 2.30 × 10-9 m2/s,
DN2water ) 2.0 × 10-9 m2/s; ref 20: DCO2water ) 1.90 × 10-9
m2/s, all at 20 °C). Oxygen, in the former case, and nitrogen,
in the latter case, enter the liquid faster than nitrogen and
carbon dioxide, respectively, are able to leave it. During these
interchanges, supersaturation (s > 0) develops in the liquid
phase, and, where supersaturation is followed by spon-
taneous bubble nucleation, this can increase the mass transfer
coefficients for these processes in comparison with the reverse
ones. Bubble creation enhances mass transfer but depends
on conditions that are not irreproducible, such as the presence
of trace contaminants that act as nuclei for new bubbles.
This explains why we found a more pronounced enhancement
in electrolyte solutions than in pure water (see Table 1), a
finding also reported in the literature.14,15 Therefore, in
what follows, we only consider the mass transfer coefficients
of oxygen and carbon dioxide for responses obtained from
gas interchanges unhampered by this almost irrepro-
ducible supersaturation effect, namely, (O2 f N2) and (N2 f
CO2).
A number of conclusions can be drawn from the results
presented in Table 1. The mass transfer coefficients obtained
for oxygen agree with, or are slightly superior to, the coef-
ficients obtained for carbon dioxide, which corresponds with
the lower molecular diffusivity of CO2. The mass transfer
coefficients of carbon dioxide obtained in salt solution
were not significantly lower than those obtained in pure water,
thereby contradicting Hill’s statement that the ionic charge
effect of NaCl at the bubble surface reduces the ability of
carbon dioxide molecules to diffuse away from the bubble
surface. We therefore conclude that the lower kLa values
reported by Hill in salt solution are an artifact caused by his
use of an incorrect model for calculating the absorption driving
force.
Conclusions
Relation 13, derived by Hill3 for the rate of carbon dioxide
absorption in water in a well-mixed reactor, gives substantially
lower kLa values than those evaluated using relation 11 in this
paper. We have shown that this is due to Hill’s use of an
incorrect absorption driving force in the model (eq 13), which
itself is a result of the omission of the concentration changes
induced by the absorption of highly soluble gases, such as
carbon dioxide.
A new method for the evaluation of kLa, based on pH
probe responses to the absorption of carbon dioxide, was
presented. The advantage of this method is that it is not
necessary to know the reaction equilibrium constant, the
experiment start time, or the initial and final steady-state pH
probe readings.
By comparing the mass transfer coefficients of carbon dioxide
in water and in a salt solution in a stirred cell, we have shown
that Hill’s finding that the addition of salt (NaCl) reduces kLa
values compared to those in pure water is not caused by ionic
charge effects at the bubble surface reducing the ability of
carbon dioxide molecules to diffuse away from the surface but
by the incorrect absorption driving force used by Hill to evaluate
kLa. Our experiments have shown that volumetric mass transfer
coefficients evaluated from responses occurring after CO2 f
N2 interchanges are enhanced by the effect of liquid supersatu-
ration.
Acknowledgment
Support from the Ministry of Education (MSM 6046137306)
and from the Grant Agency of Czech Republic through Project
No. 104/05/P203 is gratefully acknowledged.
Nomenclature
A ) QGH/(kLaVLRT)
c ) concentration (mol/L)
D ) coefficient of molecular diffusivity (m2/s)
E ) enhancement factor of absorption
G ) reading of oxygen probe (volt)
H ) Henry’s coefficient ((atm L)/mol)
Hu ) steady-state gas holdup, volumetric fraction of gas
K0,1 ) equilibrium constant (mol/L)
k1 ) first-order kinetic constant (s-1)
koL ) mass transfer coefficient for physical absorption (m/s)
kLa ) volumetric mass transfer coefficient (h-1 or s-1)
pt ) barometric pressure (atm)
pCO2 ) partial pressure of carbon dioxide (atm)
pLj ) equilibrium partial pressure of gas component j (atm)
QG ) aeration rate (L/s)
R ) gas constant ((atm L)/(mol K))
S ) salinity (g/kg)
s ) supersturation criterion defined by eq 24
T ) temperature (K)
t ) time (s)
VL ) liquid volume in reactor (L)
y ) molar fraction

R ) saturation of liquid phase with carbon dioxide [)cH2CO3/
(cH2CO3)/1]
θ ) start-up period [)VLHu/{QG(1 - Hu)}] (s)
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ReceiVed for reView August 30, 2007
ReVised manuscript receiVed October 26, 2007
Accepted October 30, 2007
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