Bubble Effects on the Solution IR Drop in a

Vertical Electrolyzer Under Free and

Forced Convection
Fumio Hine* and Koichi Murakami 1
Nagoya Institute of Technology, Nagoya 466, Japan

ABSTRACT
Effects of electrolytic bubbles on the IR drop of caustic soda solution i n a
vertical cell of one meter height were studied u n d e r both free and forced con-
vection. Three pairs of L u g g i n - H a b e r probes were positioned near the anode
and the cathode to determine the solution IR drop d u r i n g electrolysis. A sec-
tioned electrode having 10 segments was employed to obtain the c u r r e n t dis-
t r i b u t i o n from the bottom to the top of cell. The superficial resistivity of the
solution containing gas bubbles agreed well with the B r u g g e m a n n equation.
The solution IR drop decreased significantly w h e n adequate conditions or cell
geometry for solution circulation were provided. The anode-to-cathode gap was
found to be the most i m p o r t a n t p a r a m e t e r for reduction of the solution IR drop
i n a vertical cell.

A n i m p o r t a n t item in the voltage balance of an This paper is concerned with Item 2, the effect of
i n d u s t r i a l electrolytic cell is the IR drop in the electro- electrolyte circulation on the performance of gas-
lyte across the gap b e t w e e n the electrodes. When the evolving cells, p a r t i c u l a r l y with reference to c u r r e n t
electrode reaction evolves gas, the presence of gas distribution and voltage drop in the electrolysis gap.
bubbles dispersed i n the electrolyte m a y greatly i n - The experiments were designed to reveal f u n d a m e n t a l
crease the IR drop. This is p a r t i c u l a r l y true if the relationships, and thus to be useful in the design of
electrode is not perforated, in which case all the i n d u s t r i a l electrochemical cells.
evolved gas must pass through the electrolysis gap. I n the previous report, an empirical equation for the
There are several ways of m i n i m i z i n g the u n w a n t e d conductivity of the gas-solution m i x t u r e as a function
" b u b b l e effects." of the c u r r e n t density and the solution velocity in a
1. Use of perforated electrodes, which p e r m i t some, n a r r o w channel was presented (10). I n addition to the
if not all, of the evolved gas, to be removed from the articles quoted in Ref. (10), useful papers with respect
electrolysis gap. to the b u b b l e effects on the c u r r e n t distribution and
Thus, in a m a l g a m - t y p e chlorine cells equipped with the voltage balance i n electrolytic cells can be found
horizontal block anodes of graphite, these blocks m a y (11-13). F u n k and Thorpe studied the void fraction
be machined and perforated in various ways to m i n i - and the c u r r e n t distribution in a water electrolysis cell
mize accumulation of chlorine gas bubbles on the (11). They concluded that the slip ratio, UjUl, in this
underside of these blocks (1-4). Also, m o d e r n a m a l g a m case was nearly unity, which was of great importance
cells equipped with "spaghetti"-type metal anodes in defining the void fraction and in the analysis of
almost eliminate the b u b b l e effect. hydrodynamics or pressure drop i n electrolytic cell.
In m o d e r n d i a p h r a g m - t y p e chlorine cells equipped Although there is no doubt that the IR drop and the
with vertical dimensionally stable anodes (DSA), overvoltage near the electrode are affected by bubbles,
which are u s u a l l y perforated, a m a j o r part of the e n h a n c e m e n t of mass and heat transfer is also of i m -
evolved chlorine is removed from the electrolysis gap portance to electrolytic gas evolution. The thickness
by passing through the perforations. This also permits of the h y d r o d y n a m i c film or the b o u n d a r y layer along
closer spacing b e t w e e n anode and diaphragm. Thus the the electrode is reduced, and hence the heat transfer
IR drop can be minimized. coefficient i n the cell is increased by circulation of the
2. Recirculation of electrolyte decreases the gas void electrolytic solution (14-22). MacMullin et al. studied
fraction in the electrolysis zone, and thus improves the the e n h a n c e m e n t of heat transfer in a n electrolyzer,
conductivity of the two phase m i x t u r e of electrolyte where h y d r o g e n evolution took place at the cathode
and gas in the gap. (17). The gas evolution promotes rapid circulation of
Thus, in older d i a p h r a g m - t y p e chlorine cells, equip- the electrolyte resulting in a significant increase of
ped with solid graphite blade anodes, a r e t u r n path is the fluid film heat transfer coefficient, by a factor of
provided which allows the anolyte b r i n e to recirculate 2to3.
freely. The recirculation is d r i v e n by the gas lift effect Flow of the gas-electrolyte m i x t u r e along the verti-
i n the a n o d e - d i a p h r a g m gap (5, 6). cal electrode during cell operation is a "two-phase flow"
I n n e w e r d i a p h r a g m - t y p e chlorine cells, equipped or a "backmix flow" depending on the liquid flow
with b o x - t y p e DSA's, the inside of the DSA can be velocity and the void fraction of bubbles (23-25). I n
utilized as a downcomer for recirculating the anolyte. some cases, gas bubbles grow in size, and cover the
Box-type electrodes Can also be used in cells for electrode surface; thus the overvoltage becomes high.
water electrolysis, to improve the circulation of caustic On the other hand, some gas bubbles leaving the elec-
potash electrolyte, thus decreasing the void fraction trode disperse i n the solution, and the IR drop between
of hydrogen on one side of the diaphragm, and of oxy- two electrodes increases. That is, the "bubble effects"
gen on the other (7, 8). are classified into (i) the surface reduction of the work-
3. Miscellaneous, such as electrolysis u n d e r high ing electrode, and (it) increase i n the resistivity of
pressure, which decreases the volume of the gas b u b - the electrolytic solution.
bles, and improves conductivity (7, 9). Tobias and his collaborators published a series of
* Electrochemical Society Active Member. excellent papers on the effect of bubbles on the cur-
1 P r e s e n t a d d r e s s : R e s e a r c h L a b o r a t o r y , T h e J a p a n C a r l i t Com- rent distribution and the ohmic resistance (26-28).
pany, Sibukawa, Japan.
K e y w o r d s : g a s , cell, r e s i s t i v i t y , c o n v e c t i o n , They propose B r u g g e m a n n ' s e q u a t i o n

292
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 Vol. 127, No. 2
p/po = (1 - e)-3/2
to correlate the resistivity vs. gas void fraction i n
electrolytic cells. The gas void fraction is closely re-
lated to the b u b b l e size, i.e., the larger the b u b b l e size
the smaller is the void fraction in general. Bubbles
i n w a t e r grow i n size, b u t coalescence of electrolytic
bubbles is very limited, and is affected greatly by the
solution composition (29,30), for reasons that are u n -
clear at present.
The experiments described in this paper were con-
ducted in a vertical cell, one m e t e r high, to d e t e r m i n e
the b u b b l e effects on the operating conditions and the
cell geometry. Solution circulation b y gas lift action
a n d forced flow is also discussed.
Experimental Procedure
A vertical Lucite cell one m e t e r high, as shown in
Fig. 1, was fabricated. The anode and the cathode,
each 89 cm long a n d 3 cm wide, were made of 304
stainless steel (SS) plate 3 m m thick. Heavy copper
bus bars were employed to minimize the IR drop
in the SS electrodes. The anode-to-cathode gap was
adjusted b y the l e a d - i n shafts with P T F E spacers of
different lengths in the range 0.5-3 cm. A PVC back-
plate was positioned to provide a space of an adequate
size for the electrolyte. For e x p e r i m e n t s u n d e r forced
circulation, a shield plate was provided at the cell
bottom as shown i n Fig. lB. The electrolytic solution
was p u m p e d up from the i n l e t to the Cell top through
the interelectrode gap, and sent back to the reservoir.
Three pairs of the L u g g i n - H a b e r probes made of
P T F E were positioned at tile cell bottom, the center,
and at the top to obtain the solution IR drops at these
respective points. The potential was referred to the
Hg/HgO electrode. The L u g g i n probes were inserted
into the electrode plate from the back side so as to
avoid disturbance to solution flow. Because the outer
d i a m e t e r of the Luggin tip was thick (6 ram), an
equation proposed by B a r n a r t t was used to calibrate
the potential deviation (31).
A sectioned electrode with 10 segments, also made
of SS, was used to d e t e r m i n e the c u r r e n t distribution.
The distance of the segments from a flat plate counter-
electrode was adjusted carefully Lo equalize the elec-
[]
15
x For mode 1, b ---- 0, and the average gas void frac-
COUNTER
EL ECTROOE
BUS BAR ""
~ 36
K i
102 (:
36
s JJ.
r
E kaJ,-b-J
Fig. 1. A vertical cell. Drawing B shows a shield plate for ex-
periments under forced circulation.
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B U B B L E EFFECTS 293
[1] trode gaps prior to the experiment. This procedure
was i m p o r t a n t for obtaining reproducible results.
Each electrode segment had a s h u n t i n series, a n d
was connected to a common copper bus bar. The volt-
age drop i n a s h u n t was measured to obtain the c u r r e n t
passing. The gas void fraction and the solution re-
sistance increase with the level from the bottom to the
top of the cell. Therefore, the c u r r e n t d i s t r i b u t i o n along
the vertical electrode is demonstrated by the variation
of the currents carried by the different electrode seg-
ments.
Electrolytic solution, mostly 2N NaOH at 40~ was
circulated b e t w e e n the thermostated reservoir and the
space behind both electrodes to keep the t e m p e r a t u r e
constant, even in the case of blocked convection.
Oxygen and h y d r o g e n were liberated at the anode
and the cathode respectively, during electrolysis, and
were mixed because there was no separator i n the cell.
Thus, for one F a r a d a y passed, 1/4 mole 02 plus 1/2 mole
H2 were evolved.
The polarization curves on a small SS electrode were
obtained in a separate cell containing NaOH solution.
The potential vs. c u r r e n t density was found to be a
straight line over a wide range of c u r r e n t density
above 2 A / d m 2. The sum of the slopes of both anodic
and cathodic polarization curves was 0.340 ~ - c m 2 i n
2N NaOH at 40~
Results and Discussion
Solution resistivity vs. gas void fraction.--F~gure 2
illustrates three types of flow p a t t e r n i n a vertical cell:
blocked convection (mode 1), n a t u r a l circulation
(mode 2), and forced circulation (mode 3). I n mode 1,
the gas-liquid m i x t u r e rises to the cell top, a n d the
solution treed of gas bubbles comes down t h r o u g h a
part of the electrode gap, thus complicating the flow
pattern. I n mode 2, the gas-solution m i x t u r e rises
through the electrode gap b y gas lift action and the
solution flows down through the downcomer w h e n the
circulation path is provided. Separation of gas bubbles
from the solution is stimulated b y rapid flow, and
hence the gas void fraction decreases in this case. On
the other hand, w h e n the solution containing gas b u b -
bles is forced into the reservoir from the cell top by
pump, the gas void fraction m a y be still f u r t h e r re-
duced, as in mode 3.
I n Fig. 2, H represents the level of electrolyte before
the c u r r e n t is t u r n e d on. With c u r r e n t on, the level i n -
creases by AH, due to h o l d - u p of gas bubbles i n the
electrolyte.
tion ea is
ea = AH/[H + AH], a p p r o x i m a t e l y [2]
For mode 2
L
f
/ \1
,Itl /\ /
/\
- Ui \1
t\
1\;
ru
MODE I MODE 2 MODE 5
BLOCKED NATURAL FORCED
CONVECTION CIRCUI..ATION CIRCULATION
Fig. 2. Flow pattern in vertical cells
 294 ,I. EZectrochern. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y F e b r u a r y 1980

a § b ~H I.e
ea = - - - - , approximately [3]
a H-t-AH

I n this case, the solution in the downcomer is assumed

to be bubble-free. MODE I
Suppose that the gas void fraction at the center ELECTRODE GAP
level is ea. The c u r r e n t density at the center Luggin 1.6 o 2 . 5 0 GM
was confirmed to be almost average. Figure 3 shows >. A 1.50
the reduced resistivity p/po at the center Luggin as a v- = 0.97
function os ea calculated by Eq. [2] (open points for >__.
MODE 3
mode 1).
FLOW VELOCITY
The gas void fraction w i t h a cell i n mode 3 was 9 6 . 2 2 CM/SEO
also obtained. The solution level comes down b y AH =u 1.4
from the outlet w h e n the polarizing c u r r e n t a n d the o 9 9.11
J
p u m p are t u r n e d off, thus, ~a can be obtained b y a '" 9 I 0.00
O
similar m a n n e r . Although the e x p e r i m e n t a l results =)
r
fluctuated more in comparison w i t h mode 2, the solu- ,.,
MODE 2
tion resistivity vs. average gas void fraction fitted
CURRENT DENSITY:
roughly with Eq. [1] and was i n d e p e n d e n t of the flow
rate of solution. Therefore, B r u g g e m a n n ' s equation is 1.2 15 A/SQ.DM
valid for all cases. '~ 5 0
I n a previous work (10), we reported that the
B r u g g e m a n n relation m a y not work well, especially
u n d e r forced convection. That result differed from
the present conclusion, p r o b a b l y due to different m e t h -
ods of experimentation. The solution I R drop was ob- ~.o ~ I I J
0 0.1 0.2 0.5
tained from the voltage drop b e t w e e n the anode Luggin
a n d the cathode Luggin in the present study, whereas GAS VOID FRACTION
the potential difference b e t w e e n the w o r k i n g elec-
trode and the Luggin probe located on the front of Fig. 3. Relationship between the reduced resistivity and the gas
the counterelectrode was measured i n the previous void fraction under blocked convection and forced circulation.
work. The overvoltage of the working electrode was
calibrated by the c u r r e n t i n t e r r u p t i o n technique in this
case, b u t the I R drop through a thin layer in the vi- sity i n n a r r o w channels (0.5 cm gap), slug flow could
cinity of the w o r k i n g electrode was, of course, i n - be observed.
volved. A solution layer near the electrode might be It is evident that the reduced resistivity is related
crowded with electrolytic gas bubbles just leaving the to the c u r r e n t density and the flow velocity of the
electrode surface, and the condition i n this region electrolyte. The open points i n Fig. 6 show the ex-
differs from the b u l k of solution. This m a y be the p e r i m e n t a l results obtained i n the cell with forced
m a j o r reason for the different conclusions in the circulation. The closed points are the results obtained
two papers. with n a t u r a l circulation, mode 2. The flow velocity b y
gas lift action increases w h e n the gas void fraction i n -
C u r r e n t d i s t r i b u t i o n . - - F i g u r e 4 shows examples of creases at high c u r r e n t densities. F r o m Fig. 6, flow
the c u r r e n t distribution obtained with the sectioned velocity u n d e r n a t u r a l circulation, mode 2, can be
electrode. At small current, the c u r r e n t d i s t r i b u t i o n estimated to be about 14 cm/sec at 15 A / d m 2 and 20
is quite uniform, and solution circulation is not re- cm/sec at 37 A / d m 2, for example. These estimates are
quired because the gas void fraction is small. On the valid because the p/po vs. c curve is i n d e p e n d e n t of the
other hand, the local c u r r e n t density varies with solution flow as shown in Fig. 3. Figure 7 illustrates
height at high currents. Variation of the c u r r e n t den- the estimated velocity of solution circulation as a f u n c -
sity without solution circulation is very large com- tion of the c u r r e n t density and the gap, which is ob-
pared to that with circulation. Also, this figure shows tained by the method described above. The velocity
that the average c u r r e n t density is achieved at about increases with decrease of the electrode gap, b u t is
40-50% of the electrode height from the bottom end, limited in n a r r o w channels, less t h a n 1 cm gap. I n this
and is i n d e p e n d e n t of the total c u r r e n t and solution discussion, and i n Fig. 6-9, flow velocity is defined a s
circulation. the velocity of the gas-free electrolyte as it enters the
Tobias obtained a theoretical equation for the local gap; that is, it is the flow i n cm3/sec divided by t h e
c u r r e n t density ix (26). With his equation, we have area of the gap i n cm 2.
iz/ia -- 8 ( K -t- 2 ) 2 / ( K -t- 4) ( K X -t- 2) 3 [4]
1.0
where K is the gas effect parameter, a n d X is the di-
D o 37,2 A/dmr~,
mensionless vertical height, x / h . We confirm that this
22.7
equation can be fitted to our data, if we make suitable o.s
D 7.5
corrections for the h u m i d volume of the gas bubbles x NATURAL
at local estimated pressures. E q u a t i o n [4] is also valid o.e
for cells of different height as shown in Fig. 5, that is,
the iz/ia vs. x / h is almost i n d e p e n d e n t of the electrode >
height. The thick line shows the empirical equation =, o.4
obtained by the method of least squares with the data
plotted. The t h i n line is the curve calculated by Eq. 0.2
[4] with K --~ 0.6. However, in the experiments de-
scribed, K varied in the range 0.2-0.7 depending on
the electrode gap: the larger the electrode gap the o I ] I I i I I I I
0.8 1.0 1.2 1.4 1.6 0.8 I.O 1.2 1.4 1.6
smaller was the value of K.
CURRENT DENSITY, ix/J=
N a t u r a l circulation.--In most of these experiments,
the flow p a t t e r n was clearly a dispersion of gas bubbles Fig. 4. Current distribution curves under natural circulation end
i n flowing electrolyte. However, at high c u r r e n t d e n - blocked convection conditions. Electrode gap = 1.90 cm.

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 VoL I27, No. 2 BUBBLE EFFECTS 295
1.0
ELECTRODE

o•
GAP(CM)
UJ
ELECTRODE H E I G H T 2c 0.68
:E 0.97
0.8 o 88.0 CM o
t- )-
z~ 62.3 P- 1.47
[] 44.5
~" 0.6 W
> 1.97
tU
> z 2.50
o_ I0
W t--
_J .._1
0.4-
0
r
o 5

0.2
O"
J
0 I0 20 30 40
0
CURRENT DENSITY (A/din !)
0.5 1.0 1.5
Fig. 7. Circulation velocity as o function of the current density
CURRENT DENSITY, ix / l a and the electrode gap in a cell, mode 2.

Fig..5. Current distribution curve with electrodes of different

heights. Electrode gap ----- 3.90 cm. Avvrage ~eurrent density =
37.4 A/dm 2. Thin line calculated by Eq. [3] with K = 0.6. ~E=ET--Eo--~ [7]
w h e r e ET is the t e r m i n a l voltage, Eo the d e c o m p o s i t i o n
voltage, and Z~ is the sum of the o v e r v o l t a g e at a n o d e
The solution flow velocity ul is r e p r e s e n t e d b y and cathode. Suppose t h a t ET r e m a i n s c o n s t a n t from
the top to the b o t t o m of the cell because h e a v y c o p p e r
Ul : V~/ac (1 - ~) [5] bus bars are e m p l o y e d in both anode and c a t h o d e
sides, a n d Eo is, of course, constant. On the other hand,
Since the v o l u m e t r i c flow r a t e of solution, V1, r e m a i n s zn and ~E are functions of the c u r r e n t density. I n
constant, u, is only a function of ~. practical cells, however, ET is sometimes shown b y a
Now, the c u r r e n t d e n s i t y i is a function o f ,
simple equation
~E ~E ET= A-~B~n [8]
_ -- .... (I - ,)31s [6]
pa poa w h e r e A is the superficial decomposition voltage, B a n d
The voltage drop in the electrolyte, hE, is n are coefficients d e p e n d i n g on the o v e r v o l t a g e c h a r -
acteristics, the solution conductivity, and the cell g e o m -
1.8 etry. A l t h o u g h n is u n i t y in m a n y cases, sometimes w e
FLOW VELOCITY see values of n r a n g i n g from 1.0 to 2.0 in electrolytic
(CM/SEC) cells w h e r e gas evolution takes place. Generally, the
overvoltage and its i n c r e m e n t w i t h the c u r r e n t d e n -
8.6 sity are r e l a t i v e l y small c o m p a r e d to the IR drops in
the solution containing gas bubbles, as was shown in
>. Fig. 3 in the previous p a p e r (10). Thus, w e e s t i m a t e
I,- 1.6 --
t h a t Eo + Z~] in Eq. [7] is r o u g h l y equal to A in Eq.
>= [8], and hence, AE ~ B i n. S u b s t i t u t i n g it and Eq. [6]
i-
t.n into Eq. [5], we h a v e
1.
U) u = C im [9]
b.I
h.. 13.7
where
CI V1 ( B ~2/3 2('l%--1)
tu C --- - - ~-~oa/
=o 1.4 -
ac
and ~ =
3
r CIRCULATION
LU
iv Figure 8 shows the log-log plots of the flow velocity
vs. average current density in a cell, mode. 2, with dif-
ferent gaps. Straight lines with a slope of about 0.5
were obtained, and hence, u~ cc k/f Also, n ~ 1.75.
1.2 The flow velocity reaches a m a x i m u m at an electrode
gap of 0.75 c m as s h o w n in Fig. 9. The figure also
shows the effect of solution flow on the reduction of
the IR drop or the reduced resistivity of the solution
(center).
The terminal voltage was a m i n i m u m electrode gap
I.o I r ~ '~ I . I I [ of 5-7 ram. In a narrow channel, less than 5 ram, the
0 I0 20 3O 40 50 flow pattern becomes slug, and p/po is large. O n the
other hand, p/po is almost independent of the electrode
CURRENT DENSITY (A/din 2) gap w h e n the gap is larger than 10 ram. Consequently,
the solution IR drop and the terminal voltage at con-
Fig. 6. Reduced resistivity vs. current density curves as functions stant current density increases with the increase of
of the flow velocity with forced circulation. The dotted line is a the electrode gap (top figure).
curve abtained under natural circulation conditions. Electrode The reduced resistivity in a cell without circulation,
gap : 0~97 cm. m o d e I, is s h o w n by the closed points. Since convection
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 296 J. Etectrochem. Sac.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
-,,, ~0
r e t- / / o se CM
u,. | = .47
4~ A 1.97
3 [- o 2.50
2Lf f I fl .... I I I (
5 e e ,o 3o 4o
CURRENT DENSITY ( A / d r ~ )
Fig. 8. Log-log plots of the flow velocity
vs. current density at
different gaps between two electrodes. Natural circulation, mode 2.
occurs only i n the space b e t w e e n two electrodes, the
larger the electrode gap the smaller is the resistivity.
Also the p/po is affected greatly b y the c u r r e n t density,
which indicates difficulty of separation of gas bubbles
from the electrolytic solution.
I n this connection, the size of the downcomer seems
to be an i m p o r t a n t factor for n a t u r a l circulation. Ac-
cording to experiments, the gap of 12-15 m m was suffi-
cient for solution circulation.
A more exact m a t h e m a t i c a l approach to the p r o b l e m
of a priori calculation of the gas void fraction i n the
electrolysis gap, as a function of the various i n d e p e n -
dent variables, would no doubt be desirable. However,
this would depend on the ability to predict the gas
rise velocity relative to the local liquid velocity, for
swarms of b u b b l e s of v a r y i n g size, as generated at the
electrodes. The p r o b l e m is indeed complicated, and for
its proper solution, additional e x p e r i m e n t a l techniques
m u s t be developed. I n the meantime, the present sim-
plified approach has revealed interesting relationships
in cells with gas-evolving electrodes.
The experiments described i n this paper were con-
ducted with solid electrodes, and hence the electrolysis
zone was crowded with evolved gases. This was the
case for the old style d i a p h r a g m - t y p e chlorine cells
using graphite blade anodes. I n the n e w type cells
using DSA's, the anodes are perforated, so that the
evolved chlorine passes t h r o u g h the electrodes to the
outer space, and hence, the gas void fraction in the
electrode gap is reduced considerably, resulting in low
voltage drops. This, of course, is of great interest to us,
and will be investigated i n the future.
Conclusion
Effect of the electrolytic gas bubbles on the solu-
tion IR drop and the t e r m i n a l voltage of a vertical cell,
one m e t e r high, was studied. E x p e r i m e n t s were con-
ducted u n d e r blocked convection, n a t u r a l circulation,
a n d forced circulation conditions. The a n o d e - t o - c a t h -
ode gap, the space of the downcomer, and the electrode
height were varied. The superficial resistivity of elec-
trolytic solution c o n t a i n i n g gas bubbles was confirmed
to be a function of the gas void fraction, a n d agreed
well with the B r u g g e m a n n equation.
The average gas void fraction in the gap is a mea-
sure of the gas hold-up in the gap, and depends
strongly on the volumetric liquid flow rate in the gap.
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February 1980
6 / TE,~INAL VOLTA(3E
/ / I BLO EO\ 60
L
/
/ 2
6o ,s 20 I- ^ CIRCULATIONVELOCITY I
IO
0
I
I ~
ELECTRODE GAP (CM)
2
~
Fig. 9. Terminal voltage, reduced resistivity, and circulation
, I
velocity as functions of the electrode gap and the current. Average
current density: 37.2 A/dm2 at 100A, 22.7 A/dm 2 at 60A, and
7.5 A / d m 2 at 20A. Closed points ~ blocked convection (mode 1).
Other factors include the rate of rise of b u b b l e swarms
relative to the liquid rate, c u r r e n t density, overvoltage,
etc.
The gas lift effect m a y be utilized to promote n a t u r a l
circulation of liquid through the gap, and thus to im-
prove conductivity in the gap. The o p t i m u m area of
d o w n c o m e r used for recirculation should be about
twice the area of the electrode gap.
The anode-to-cathode gap is, of course, a major
component of the terminal cell voltage. The gas void
fraction in a narrow channel is large and it causes a
large increase in the solution IR drop. O n the other
hand, the solution IR drop increases with increase of
the electrode gap. A n o p t i m u m gap between anode
and cathode is about 5-7 m m depending on the operat-
ing conditions such as c u r r e n t density and solution
composition.
The local c u r r e n t density varies from the bottom to
the top of cell due to the change of the gas void frac-
tion along the electrode. But the c u r r e n t d i s t r i b u t i o n
is impl-oved significantly b y solution circulation. The
c u r r e n t density near the center of electrode then takes
the average value.
I n conclusion, design of the cell configuration and
choice of the operating conditions to yield sufficient
flow of solution b e t w e e n the two electrodes are useful
for reducing the gas void fraction, a n d thus the cell
voltage.
Acknowledgments
The authors wish to extend m a n y thanks to Mr. R. B.
MacMullin, Niagara Falls, New York, for his review
and suggestions, and also for p r e p a r a t i o n of the paper.
We t h a n k Dr. M. Yasuda for his discusMon.
M a n u s c r i p t submitted March 19, 1979; revised m a n u -
script received July 31, 1979. This was Paper 281 pre-
sented at the Boston, Massachusetts, Meeting of the
Society, May 6-11, 1979.
 Vol. 127, No. 2 BUBBLE EFFECTS 297

Any discussion of this paper will appear in a Dis- 5. R. B. MacMullin, Electrochem. TechnoL, 1, 5 (1963).
cussion Section to be published in the December 1980 6. R. B. MacMullin, Denki Kagaku, 38, 570 (1970).
JOURNAL. All discussions for the December 1980 Dis- 7. C. L. Mantell, "Electrochemical Engineering," p.
cussion Section should be submitted by Aug. 1, 1980. 308, McGraw-Hill, New York (1960).
Publication costs of this article were assisted by 8. "Denki Kagaku Binran" (Handbook of Electro-
Fumio Hine. chemistry), p. 732, Maruzen Publishers, Tokyo
LIST OF SYMBOLS (1964).
a anode-to-cathode gap (m) 9. Y. Hinonishi, "High Pressure Water Electrolysis,
b electrode-to-bacl(plate (size of downcomer) Kogyo Butsuri Kagaku" (Physical Chemistry
(m) of Chemical Industry), Vol. 4, p. 73, Corona
c e• width (m) Publishers, Tokyo (1949).
h electrode height (m) 10. F. Hine, M. Yasuda, R. Nakamura, and T. Noda,
i current density (A/m 2) This Journal, 122, 1185 (1975).
m number of charge transfer (--) 11. J. E. Funk and J. F. Thorpe, ibid., 116, 48 (1969).
m and n coefficients in Eq. [8] and [9], respectively 12. N. D. Koshel' and O. S. Ksenzhek, Soy. Electro-
u flow velocity ( m / s e c ) chem., 8, 436 (1972).
u,t flow velocity in electrode gap (see Fig. 2)
(m/sec) 13. P. A. Danna, This Journal, 121, 1286 (1974).
UB flow velocity in downcomer (see Fig. 2) (m/ 14. N. Ibl, Chem.-Ing.-Tech., 35, 353 (1963).
sec) 15. L. J. J. Janssen and J. G. Hoogland, Electrochim.
x level from the bottom end of electrode (m) Acta, 15, 1013 (1970); 18, 543 (1973).
A and B coefficients in Eq. [8] 16. N. Ibl, J. Venczel, E. Schalch, and E. Adam, Chem.~
C coefficient in Eq. [9] Ing.-Tech., 43, 202 (1971).
Eo decomposition voltage (V)
ET terminal voltage (V) 17. R. B. MacMullin, K. L. Mills, and F. N. Ruehlen,
~E voltage drop in electrolyte (V) This Journal, 118, 1582 (1971).
F Faraday (96,500 C/g-equiv.) 18. M. G. Fouad, G. H. Sedahmed, and H. A. EI-Abd,
H height of bubble-free solution (m) Electrochim. Acta, 18, 279 (1973).
AH increment of height due to dispersion of gas 19. M. G. Fouad and G. H. Sedahmed, ibid., 20, 615
bubbles (m) (1975).
K parameter in Eq. [4] [ = hix (~ -~ pxa)/ 20. I. Rousar and V. Cezner, ibid., 20, 289 (1975).
mFPpouga 2]
P pressure of gas (Pa) 21. I. Rousar, J. Kacin, E. Lipper, F. Smirous, and V.
V volumetric flow rate (m3/sec) Cezner, ibid., 20, 295 (1975).
X reduced height [_-- x/h] (--) 22. H. Vogt, ibid., 23, 1019 (1978).
#S slope of polarization curve (12-m~) 23. D. S. Scott, "Properties of Cocurrent Gas-Liquid
9 gas void fraction (--) Flow, Advance~ in Chemical Engineering," Vol.
p resistivity of gas-solution mixture (12-m) 4, T. B. Brew et al., Editors, p. 199, Academic
po resistivity of bubble-free solution (12-m) Press, New York (1963).
9~ sum of overvoltage at anode and cathode (V) 24. "Chemical Engineers' Handbook," J. H. Perry, Edi-
Subscripts tor, 4-21 and 5-38, McGraw-Hill, New York
(1963).
a average 25. T. Z. Fahidy, Can. J. Chem. Eng., 174, June 1966.
x local
g gas 26. R. E. De La Rue and C. W. Tobias, This JournaZ,
1 liquid 106, 827 (1959).
REFERENCES 27. C. W. Tobias, ibid., 106, 833 (1959).
1. F. Hine, S. Yoshizawa, S. Okada, and T. Uesugi, 28. R. E. Meredith and C. W. Tobias, ibid., 110, 1257
Kogyo Kagaku Zasshi, 58, 554 (1955). (1963).
2. F. Hine, S. Yoshizawa, and S. Okada, Denki 29. R. R. Lessard and S. A. Zieminski, Ind. Eng. Chem.
Kagaku, 24, 370 (1956). Fundam., 1O, 260 (1971).
3. S. Okada, S. Yoshizawa, F. Hine, and Z. Takehara, 30. F. Hine and T. Sugimoto, Paper 459 presented at
ibid., 26, 165, 211 (1958). The Electrochemical Society Meeting, Seattle,
4. S. Yoshizawa, F. Hine, Z. Takehara, and M. Yama- Washington, May 21-26, 1978.
shita, ibid., 28, 205 (1960). 31. S. Barnartt, This Journal, 99, 549 (1952).

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