Electrochimica

Acta, 1971,Vol. 16,pp. 1477to 1487.Persamon

m. Printedin NorthemInland

A STUDY OF MASS TRANSFER IN ELECTROPOLISHING

OF COPPER*
M. G. FOUAD, F. N. ZEIN and M. I. ISMAIL
Chemical Engineering Department, Faculty of Engineering,
University of Alexandria, Egypt, U.A.R.

Abstract-Limiting current was measured for the anodic polishing of vertical copper electrodes in
u-H~PO~ acid using: (a) a cell with diaphragm where the effect of Ha evolved at the cathode on the
rate of mass transfer at the anode is eliminated. A general correlation of the data may be represented
by the equation Nu = 0.72 (ScGr)“.‘3, where Nu is the Nusselt number, SC the Schmidt number and
Gr the Grasshof number. The experimental range used in the correlation was 6.49 x lO*l < ScGr <
2.9 x 1014; (b) a cell without diaphragm, where the effect of H, evolved at the cathode on the anodic
limiting current and the rate of mass transfer was studied. It was found that H, evolved at the
cathode increases the rate of mass transfer and the anodic limiting current by a value ranging from
2.8-28.4x depending on the operating conditions.
The effect of initial roughness on the rate of mass transfer and limiting current was also studied;
it was found that surface roughness (within the limits studied) has no substantial effect.

R&sum&On a ttudie le courant limite dans le polissage anodique d’electrodes en cuivre verticales
dans des solutions d’acide o-phosphorique. Deux types de cellules ont et&utilis& (a) Une cellule avec
diaphragme oti l’intluence dei’hydrogkne d&gage ?t la cathode Ctait elimine. Dans le domaine etudit
(6,49 x IOL1< ScGr < 2,9 x lo’*) les resultats peuvent &re representc5spar la correlation Nu =
0,72 (ScGr) 0s3 oh Nu est le nombre de Nusselt, SC le nombre de Schmidt et Gr le nombre de Grasshof.
(b) Une cellule sans diaphragme avec laquelle on a Ctuditl’influencedel’hydrogene d&gage & la cathode
sur le courant limite anodique. L’hydro&ne d&gage a la cathode augmente la vistesse du transport de
mat&e de 2,8 & 28,4% selon les conditions.
On a aussi 6tudiCl’influence de la rugositt initiale. Dans le domaine Btudie celle-ci n’a pas d’effet
appreciable sur la vitesse du transport de matiere.

Zusammenfassung-Es wurden die Grenzstrijme beim anodischen Polieren von sekrechten Kup-
ferelektroden in OrthophosphorsPure gemessen. Dabei wurden 2 Typen van Zellen verwendet (a)
Zelle mit Diaphragma, bei der kein Einiluss des an der Kathode entwickelten Wasserstoffs aufden
Stofftransport vorhanden awr. Die Ergebnisse konnen durch die Korrelation Nu = 0,72 (ScGr)“*Ba
dargestellt werden, wobei Nu die Nusselt’sche, SC die Schmidt’sche turd Gr die Grasshof’sche Zahl
bedeutet. Der untersuchte Bereich war 6,49 x 1Ol1 < ScGr < 2,9 x 1014. (b) Zellemit Diaphragma,
wobei der Einfluss des an der Kathode entwickelten Wasserstoffs auf den anodischen Grenzstrom
untersucht wurde. Es wurde gefunden, dass der Wasserstoff die Geschwindigkeit des Stofftransports
urn 2,8 bis 28,4 oA vergriissert, je nach den Arbeitsbedingungen.
Es wurde such der Einfhrss der Initialrauhigkeit untersucht. Im untersuchten Bereich hatte
letztere keinen wesentlichen Einlluss auf die Geschwindigkeit des Stofftransports.
INTRODUCTION
THE OBJECT of this investigation was to make a quantitative study of the electro-
polishing of metals using large electrodes. Electropolishing of metals usually takes
place at current which is determined by the physical properties of the
polishing solution, the initial roughness of the electrode and geometric and hydro-
dynamic factors. As polishing solutions are usually acidic the cathodic reaction
results in evolution of Ha, which reaches the anode and affect the rate of mass transfer_
In this work an attempt was made to study the effect of this hydrogen on the enodic
limiting current and the rate of mass transfer.

EXPERIMENTAL TECHNIQUE
The apparatus consisted essentially of an electrolytic cell and auxiliary equipment
for measuring the total current and anode potential. The electrodes (anode and
* Manuscript received 28 November 1969.
1477
1478 M. G. FOUAD, F. N. ZEIN and M. I. ISMAXL

cathode) were vertical electrodes of electrolytic copper plates 5-cm wide, 60-cm high
and 3-mm thick, fitting exactly into the rectangular Plexiglass electrolytic cell, so that
the whole cross-section of the cell was filled with the electrode. The cell design allowed
adoption of cathode-anode distances of 5, 10, 15 and 20 cm_ The height of the
electrodes was varied from 10 to 55 cm.
The anodic limiting currents were measured by determining the current/voltage
curve obtained by increasing the voltage applied to the cell stepwise. About 20-30

64

60

56

52

48

44

40

36

32

28

24

20

16 o Cell with diaphragm

12 x Cell without dio

0
0 100 300 500 700 900 I100 1300

Anode polarization . mV

FIG. 1. Typical current/potential curves obtained during ekctropolishing.

ElectroIyte height 50 cm; electrode spacing 5 cm; 14 M H,PO,; 30°C.

points were taken for each curve. Figure 1 shows a typical current/potential curve.
In order to ensure steady state conditions an interval of 1 min was allowed at each
step before the current corresponding to a given voltage was read. The anode po-
tential was measured against a reference calomel electrode. The end of the capillary
connecting the reference electrode to the cell was located at mid-height of the anode.
The capillary was in intimate contact to the surface of the anode. Before each run,
smooth electrodes were prepared by polishing them with emery papers, rinsing in
distilled water, washing with alcohol then acetone and finally drying before dipping
in the cell.
The solution was aqueous o-H,PO, of various concentrations ranging from 6 to
14 M. A new solution was used for each experiment. C.P. chemicals were used for
preparation of all solutions. For each set of experimenta conditions the determina-
tion of the current/voltage curve was repeated two to three times with freshly pre-
pared electrodes and solution.
 Mass transfer in electropolishing of copper 1479

A synthetic fibre diaphragm was introduced between electrodes to prevent the H,

evolved at the cathode from reaching the anode. To study the effect of H, evolved
at the cathode on the rate of mass transfer at the anode, a cell without diaphragm was
used.
RESULTS
(a) Cell with diaphragm
The results of the anodic limiting current measurements using a smooth anode are
summarized in Table 1. Figure 2 shows the dependence of the limiting current
density on electrode height. The currents are mean values averaged over the whole
electrode surface. The last three coIumns in Table 1 show the dimensionless groups

20 30 40 5055

Electrode height ,h , cm

FIG. 2. Effect of electrode height on limiting cd,

Concentration of electrolyte, &Pod: l ,14M; x,12M; 0,lOM; q l,SM;
A,6M.

commonly employed in natural convection problems, Nusselt number Nu, Schmidt

number SC and Grasshof number Gr, defined by the relations

SC = ;,

Gr = @(pi - PO)
Pi@ .
The meaning of the symbols is as folows:
K,, mass transfer coefficient, cm/s,
f, transference number,
X,, fiIm factor = unity,
z, valency of cation = 2,
F, faraday, 96,500 C,
ci, concentration at interface, of Cu,(PO,),, g-ion Cu/cm3,
D, diffusion coefficient of Cu2+ in H,PO,, cma/s,
.u, average dynamic viscosity in poise, g/cm.s,
p, average density, g/cmS,
 TABLE 1. CELL WITH DIAPHRAGM.
ELECTRODE SPACING 5 cm. 30°C

MEiS
Concentration Limiting transfer
Electrode of current coefficient Average Average
height WO, density x10* viscosity ci x 10’ densit pi - PO SC Nu ScGr
cm M mA/cmD cm/s CP g-ion/cma g/cm r g/Pm’ g/cm’ x10-8 x 10-18

10 14 56.7 3.055 2,519 9-63 1.554 l-615 0,122 2.25 423 0.0649
12 76.5 3.015 2.210 13.05 1,513 I.595 0.165 2.03 423 o-0955
10 75.5 2.750 1.767 14.22 1.450 1.540 0,180 1.69 382 0.1318
8 96.0 3.490 1.330 14.22 1,390 1*480 0.180 1.33 484 0.1740
6 86.5 3.545 0.879 12.63 1-380 0.160 0.94 491 o-2340

20 14 43.5 2.340 2.519 9.63 a615 0,122 2.25 648 0.5200

12 61.0 2,410 2.210 13.05 a595 0.165 2.03 673 0.7640
10 66.5 2.240 1.767 14.22 a540 0*180 1.69 671 O-6120
8 62.2 2.265 1.330 14.22 a480 0.180 1.33 627 l-3900
6 81.0 3.320 O-879 12.63 ,380 0.160 0.94 920 1.8700

30 14 39.8 2.140 2.519 9.63 1.554 1.615 0.122 2.25 890 1.7500
12 50.3 1,980 2.210 13.05 1.513 1.595 0.165 2.03 833 2.5800
10 57.3 2.090 1,767 14.22 1.450 I.540 0.180 I.69 870 3.5400
8 61.1 2.222 1.330 14.22 1.390 1.480 0.180 1.33 928 4.7000
6 72.7 2.980 0,879 12.63 1.300 1.380 0.160 0.94 1240 6.3200

40 14 37.1 2000 2.519 9.63 1.554 1.615 0,122 2.25 1106 4*1500
12 42.3 I.666 2.210 13.05 I.513 1,595 0.165 2.03 938 61100
10 53.1 1.935 1.767 14.22 1.450 1a540 0.180 1.69 1074 8.3700
8 56.0 2*040 1.330 14.22 1,390 1a480 0,180 1.33 1133 11*1300
6 65.8 2700 0.879 12.63 1a300 1.380 0.160 0.94 1500 15@000

50 14 33.0 1.780 2.519 9,63 1,554 1,615 0.122 2.25 1233 8.1200
12 39.6 1.560 2.210 13-05 1.513 I.595 O-165 2.03 1096 11.9200
10 50.7 1.850 1.767 14.22 1.450 1,540 0.180 I.69 1280 16.3500
8 53.8 l-980 1.330 14.22 1.390 1.480 0.180 l-33 1353 21.8000
6 58.0 2,380 @879 12.63 1,300 1,380 0.160 0.94 1650 29.3000

55 14 32.2 1,735 2,519 9.63 1.554 1.615 0.122 2.25 1320 10.8000
12 41.6 1640 2.210 13.05 I.513 1.595 0.165 2.03 1266 15.8500
10 50.6 1,840 1.767 14.22 1.450 1,540 0.180 1.69 1400 21*8000
8 52.9 l-925 1,330 14.22 1,390 1.480 0.180 1.33 1470 29.0000
 Mass transfer in electropolishing of copper 1481

g, gravitational acceleration, cm/sa,

pi, p,,, density of solution at interface and in the bulk, respectively, g/cm3,
Y, f = kinematic viscosity, cmz/s,

h, electrode height, cm,

I,, limiting current density, A/cm2.
The physical properties of the solutions used in computations of Nu, SC and Gr
are shown in Table 1. The viscosities were measured with an Ostwald viscometer and
densities were measured with a pycnometer. The value of the diffusion coefficient of
Cua+ adopted for calculation in this work is taken as the average of the theoretical
and experimental values. l The average viscosities and densities in Table 1 were
evaluated as the arithmetic mean composition between bulk solution and anode/
solution interface. The interficial concentrations,* densities, and viscosities were
measured at 30°C for the saturated solution of Cus(PO& in the aqueous phosphoric
acid used in the polishing bath. The saturated solution of Cu,(PO& in the different
concentrations of o-HsP04 was prepared by dissolving solid Cu3(PO& in the par-
ticular concentration of H,PO, at an elevated temperature; the solution thus ob-
tained was allowed to cool to 30°C and kept at this temperature long enough to
ensure that equilibrium was reached. Cu2+ was determined in o-HgP04 acid by
iodometry.
Figure 3 is a log/log plot of Nu USScGr. Within the range studied, 6.49 x 101’ <
ScGr ( 2.9 x IO’*, the results can be represented by the relation NU = 0.72 (SCG~)~~~.
Statistical analysis of the data in Table 1 led to Nu = O-725 (SCG~)O’~~,with the 95 %
confidence limit f0.015 for the exponent.

3 30

3-20

3 IO

s 300

_o
m 290

2 80

2 70

260

250
II 8 12-o 122 12.4 12-6 12-e 13 0 13.2 13-4 13-6 13.8 14.0 14-2 14.4 14-6

log ScGr

FIG. 3. General correlation of natural convection data.

Electrode spacing 5 cm; 30°C.
Concentration of electrolyte, M,PO,: 0, 14 M; x , 12 M; 0, 10 M; 0, 8 M;
A,6M.
Limiting currents calculated from the above equation are nearly in agreement
with those calculated from the theoretical finding of 0strach,2 Nu = 0.67 (SCG~)~~~.
The exponent 0.23 reveals that the flow of the hydrodynamic boundary layer is
laminar. The importance of the above equation in electropolishing is that it makes it
possible to predict the polishing current (limiting current) from the physical pro-
perties of the polishing solution and the geometry of the electrode.
* C was taken as equal to the saturation concentrations of Cu*+ determined experimentally.
1482 M. G. FOUAD, F. N. ZEIN and M. I. ISMAIL

TABLE 2. EFFECT OF INITIAL SURFACE ROUGHNESS ON THE LIMITING

CURRENT

CELL WITHOUT DIAPHRAGM ELECTRODE w~c~tvci 3.5 cm

ELECTRODE HEIGHT 8 cm 30°C

Initial surface Average

Concentration roughness, limiting
of peak-to-valley Diffusion layer current
&PC’, height thickness density
M mm mm mA/cms

14 Smooth 0.243 55
14 0.04 0.243 55
14 0.08 0.243 55
14 0.12 0.243 55
14 0.16 0.243 55
14 0.23 0.243 55

12 Smooth 0.241 75
12 O-04 0.241 75
12 0.08 O-241 75
12 o-12 0.241 75
12 0.16 0.241 75
12 O-23 O-241 75

10 Smooth 0.233 85
10 0.04 0.233 85
10 0.08 0.233 85
10 0.12 0.233 85
10 0.16 0.233 85
10 O-23 o-233 85

: Smooth
0.04 O-198 100
8 0.08 O-198 loo
8 O-12 O-198 100

: 0.23
0.16 O-198
0.198 100

6 Smooth 0.160 110

6” 0.08
0.04 O-160
0.160 110

z 0.16
0.12 o-153
0.153 115
6 0.23 0.153 115

E#ect of initial roughness. Table 2 shows the effect of initial roughness of the anode
on the limiting current. Six electrodes having different grades of artificial roughness
were used. The roughness studied was horizontal parallel grooves of triangular pro-
file.3 The results show that the limiting current (based on the projected area) is not
affected by the initial roughness for most of the cases studied. This is explained by the
fact that the diffusion layer thickness shown in Table 2 and calculated by
zFc$
8N =I
L
is larger than the maximum height of the protrusion, ie the electrode behaves as a
smooth electrode.3 Accordingly, the equation iVu = O-725 (SCG~)~~~ is valid for rough
electrodes (within the limits studied here). In practice, the roughness encountered lies
mostly within the range used in this investigation.
 Mass transfer in ekctropolishing of copper 1483

In the case of dilute polishing solutions, eg 6 M HsPOo, deviation from smooth

electrode behaviour takes place, especially for electrodes of high degree of roughness
(see Table 2). The limiting current and the rate of mass transfer increase by about
4.5% over that of a smooth electrode for electrodes of O-12, 0.16, 0.23 mm pro-
trusion height. In these cases, the height of the peaks is larger than the diffusion-
layer thickness. This results in an increase in the effective cross-sectional area for
diffusion, with a consequent increase in the rate of mass transfer and limiting current.

(b) Cell without diaphragm

In absence of a diaphragm between the cathode and anode, Hz gas evolved at the
cathode reaches the anode along with the displaced solution* and results in an increase
in the rate of mass transfer and limiting current. Tables 3-6 show the extent of this
increase under different conditions ; it ranges from 2.8 to 28.4 %.

TABLE 3. CELL WITHOUT DIAPHRAGM.

ELE~RODE SPACING SCIXI.30°C.

Increase
in mass
Mass & gas transfer
Concentration Limiting transfer discharge due to gas
Electrode of current coefficient velocity stirring
height &PO, density x 104 x 103 ANu Re at anode
cm M mA/cma cm/s cm8/cm9.s %

10 14 71.0 3.825 9-1s 107.0 5-65 25-4

12 90-o 3.545 11.60 74.5 7.97 17.7
10 94-5 3 -440 12-22 96-O 10.30 25-O
8 120-o 4-365 15-50 121.4 16-20 25-o
6 108-O 4-420 13-93 122.5 20-45 24.6

20 14 52.0 2*800 9-70 127.2 S-30 19.5

12 73-o 2-875 9-41 132-S 12.90 19.7
10 80.0 2.915 10-33 136.3 16-98 20.3
8 75-o 2-725 9.66 129-3 20-22 20.5
6 99-o 4.060 12.78 205-5 37.60 22-2

30 14 46-O 2.480 5-93 138-O 11-00 15-6

12 58-O 2.285 7-48 128-O 15.42 15.3
10 67.0 2440 8-65 147-o 21-30 16-9
8 71-o 2.585 9.15 150-O 28-75 16-l
6 85.0 3.490 10.98 210-o 48.50 17.0

40 14 42.0 2-260 s-41 147.0 1340 13.2

12 48-O l-890 6-20 126 0 17.08 13.5
,lO 60-O 2-182 7.74 139.5 25.40 13-o
8 64-O 2-330 8-25 162-O 34.60 14-3
6 75.0 3-080 9-66 232-O 55.50 15.5

50 14 37.0 2.000 4-77 150-o 14.75 12-l

12 44-O 1.733 6-67 121.5 19.50 11.1
10 55.0 2GOl 7-10 117-o 29 -20 8.5
8 59.0 2-148 7-60 131.3 39.80 9.7
6 65-O 2-665 8-38 199.5 61.70 12-o

55 14 35-o l-885 4.51 115-o 15-35 8.7

12 45-o l-770 5-80 103-3 22GO S&2
10 55.0 2GoI 7.10 122.0 32-00 8.7
8 58-O 2.110 7.48 142-O 42.90 9.6
1484 M. G. FOUAD, F. N. ZEIN and M. L ISMAIL

TABLE 4. CELL wrrrrowr DUwm.4oM.

ELECTRODE SPACING 10 cm. 30°C
Mass J& gas Increase in
Concentration Limiting transfer discharge mass transfer
Electrode of current coefficient velocity due to gas
height HsFO~ density x 10’ x10’ ANu Re stirring at anode
cm M mA/cmz cm/s cma/cm2.s %
10 14 72-O 3.880 9-30 108.2 5-72 25.2
12 92.2 3-630 11.90 102-5 8-15 25-O
10 94.0 3.420 12.12 96-O 9.95 25.3
8 115-o 4.190 14.82 120.2 15.50 26.1
6 126.0 5.160 16-25 141.4 24.95 24.5
20 14 50-o 2.690 6.45 127.2 7.96 20.5
12 75-o 2.950 9.67 138.1 13.30 20.0
10 80-O 2.915 10.33 139.0 16-98 20.8
75-s 2.750 9.73 131-3 2040 20.8
z 100-O 4.100 12.90 207-S 38-00 22.2
30 14 45.0 2.420 5.80 131-5 10.75 15*1
12 56-O 2.210 7.20 152.8 1490 19.3
10 65.0 2.365 8.38 133-5 20.70 15.9
8 64-O 2-335 8.25 148.5 25.95 18-O
6 85-O 3.480 1O-98 224-O 48.40 18.3
40 14 40.0 2.155 5-15 137.8 12.78 13.0
12 47-o l-850 6.06 128.0 16.70 14-l
10 58.0 2.115 7.47 129-3 2460 12-4
8 63.0 2-295 8.12 1644-o 3400 14-8
6 76.0 3.120 9.80 216-5 5615 14.3
50 14 36-O I-940 464 142-2 14.35 11-8
12 46-O 1.810 592 110.5 20-40 9.5
10 54.4 1.980 7.01 111-l 28.85 8.8
8 57-o Z-075 7.35 134.0 38.50 10.3
6 65-O 2.665 8.45 214-O 61.60 12.9
55 14 36-O I-940 464 148-O 15.80 11-l
12 44-o l-733 5-67 137-o 21-50 11.4
10 53.4 l-940 688 102.8 31.1 7.5
8 59.0 2-150 7-60 183.5 43 -70 12.5

TABLE 5. CELL WI-I-HOUT DIAPHRAGM.

ELECTRODE SPACING 15cm. 30°C
Mass Hz gas Increase in
Concentration Limiting transfer discharge mass transfer
Electrode of current coefficient velocity due to gas
height KJ’O, density x10’ x103 ANu Re stirring at anode
cm M mA/cmz cm/s cmS/cm”.s %
10 14 72.8 3.920 9.40 110-O S-80 25.3
12 92-8 3.650 1 l-95 103-o 8-20 25-l
IO 93-3 3.400 12-02 95-o 9.90 25-2
119-o 4-340 15-35 121.0 16.05 25-2
: 119.0 4.870 15.35 131-o 22-60 24.0
20 14 50.5 2.720 6.50 125-8 8.05 19.9
12 76-O 2-995 9.80 141-4 13-45 20-3
10 80.0 2-915 1O-32 166.3 16-98 24.8
8 79-o 2.880 1o-20 140-5 21.35 21.3
6 102.0 4.180 13.15 128-O 38.80 24.4
30 14 46-O 2-480 5-94 131.5 1100 14-7
12 57-o 2-242 7-35 129-5 15-16 15.8
10 66-O 2.402 8-50 135-o 21-00 15-6
74-o 2-695 9-55 165.0 3000 17.2
: 86-O 3-520 11.10 222-o 4900 17-8
 Mass transfer in eiectropoiishing of copper 1485

Table 5 (con&Y)

Mass Ha gas Increase in

Concentration Limiting transfer discharge mass transfer
Electrode of current coefficient velocity due to gas
height HJQ density x 100 x 10’ ANu Re stirring at anode
cm M mA/cma cm/s cm’/cm’.s %
40 14 41.0 2-210 5.29 150-O 13.10 13-9
12 48-O l-890 6.20 150-3 17.10 16.5
10 61.0 2.220 7.86 157.8 25.80 16.5
8 63-O 2.295 8.12 159-5 34xlO 14.3
6 76-O 3.115 9.80 205-O 56.15 13-4

50 14 38.0 2.045 4.90 150-O 15-15 11-8

12 44.0 I.730 4.67 108-O 19.50 9.7
10 57-o 2.080 7.55 123.7 30-20 9.4
8 59.0 2-150 760 146.5 39.85 10.9
6 64.0 2.625 8.25 199.5 60-70 12.3

55 14 37.0 1 a990 4.77 41-l 16.20 2-8

12 45-o 1.970 5.80 176.5 22-W 14.8
10 54.0 l-970 6.96 136-O 31-50 9-9
8 58.0 2.115 7.48 164-o 43-W 11-3

TABLE 6. CELL WITHOUT DIAPHRAGM

ELECTRODE SPACING 20cm. 30°C

Mass Ha gas Increase in

Concentration Limiting transfer discharge mass transfer
Electrode of current coefficient velocity due to gas
height I&IQ density x10’ x 103 ANu Re stirring at anode
cm M mA/cm* cm/s cmalcmB.s %
10 14 72.9 3.920 9-40 110-o 5-80 25.3
96-O 3.780 12.35 107.0 S-50 25.2
:z 95.0 3.460 12.25 96.0 1 O-05 25-O
8 123.0 4.480 15.90 131-o 1660 26.7
6 131-o 5.360 16.95 165.2 24.85 28-4
20 14 52.0 2-800 6.85 133.3 S-30 20.2
12 78.0 3.070 10.05 142.5 13.80 19.9
10 81-O 2-950 lo-44 141-2 17-20 20-9
8 81-O 2.950 1 O-44 139.2 2190 203
6 104 4.260 13.45 228-O 39.60 23 -8
30 14 46.5 2-500 6-W 140-5 11.12 15-7
12 58-O 2.285 7.50 124.5 1544 14-9
10 67.0 2440 8.65 147.0 21.30 16.9
8 76-O 2-765 9.80 171-o 30-80 17.5
6 87.0 3.565 1 l-20 222-o 49.60 17-6
40 14 42.0 2-260 5-42 171.0 13.40 15-3
12 49.0 l-930 6.32 141.3 17.40 15.0
10 61.0 2-220 7.89 139-5 25.80 12.8
8 65-O 2-365 8.40 157-S 35.10 13.6
6 77-o 3.160 9.95 205.0 37.00 13.3
50 14 39.0 2.100 5.05 168.5 15.55 13.0
12 45-o l-772 5.80 160.5 19.93 14.8
10 58-O 2-110 7.50 139-O 30.70 10.5
8 62.0 2.260 8-00 169-O 41.85 12.1
6 65.0 2-660 8.40 199.5 61-60 12-l
55 14 36-O 1.940 4.65 135.5 15.80 10-l
12 44-O l-731 5.68 118-S 21-50
10 56-O 2xl40 7.25 158.3 32-60 1Z
8 59-o 2-145 7.60 192-O 43-70 13.3
1486 M. G. FOUAD,F. N. ZEIN and M. I. ISMAIL

Figure 4 shows the dependence of the increase in the rate of mass transfer
(expressed as A Nu, where A Nu = NU cell without diaphragm - Nu,,,, with diepw~& On

b 5 IO 15 20 25 30 35 40 45 50 55 60 65 70
ffe

no. 4. Effect of hydrogen evolved at cathode on the rate of mass transfer at anode.
El&rode spacing 5 cm; electrode height 10-55 cm; 30°C.
Concentration of electrolyte, HSPOI: 1, 14 M; 2, 12 M; 3, 10M; 4, 8 M; 5,
6, M.

the gas discharge velocity, height of the electrode and the physical properties
of the soIution, these variables can be combined in a modified Reynolds number;

Re
--, p0J-f
-

where p,, is the density of the solution, g/cm 3, Vthe gas discharge velocity, cms/cmas at
the limiting current, H the electrode height, cm, and ,X the viscosity of the solution,
g/ems .
With increase of Reynolds number, the increase of the rate of mass transfer
initially increases, reaches a maximum and then decreases. This decrease can be
explained by the fact that as the height of the electrode increases, the action of the gas-
displaced solution at the anode is confined to the upper part of the electrode. This
may be attributed to the possibility that the stream of the gas-displaced solution is
unable to go deeper due to the increased solution resistance.4
Figure 5 shows the effect of distance between the electrodes on the incremental
increase in the rate of mass transfer due to Hz discharge. At small electrode spacing,
the effect of hydrogen in increasing the limiting curent at the anode becomes more
pronounced.
It is worth mentioning that the electropolishing in both types of cell resulted in a
highly polished anode surface. In practice it is recommended, therefore, to use a cell
 Mass transfer in electropolishingof copper 1487

230

210

I30

I80

I60

150

130

120

IO

100
2 4 8 JO 14 16 20 22 26
.Qe

5. Effect of electrode spacing on rate of mass transfer.

Concentration of electrolyte, HBP04, 12 M; 30°C.
Electrode spacing 0, 20 cm; x, 15 cm; 0, 10 cm; 0, 5 cm.

without diaphragm in electropolishing processes as this will increase the rate of

electropolishing without affecting the quality of the polished surface.
AcknowCec&ement-We wish to express our thanks to Prof. N. Ibl for valuable discussions.

REFERENCES
1. N. IBL, in Advances in Electrochemistry and Electrochemical Engineering, ed. P. DELAHAY and C.
W. TOBIAS, Vol. 2, p. 108. Interscience, New York (1962).
2. S. OSTRACH, Nat. Advisory Comm. Aeronaut. Tech. Notes, No. 2635 (1952).
3. M. G. FOUAI) and A. A. ZATOUT, Electrochim. Acca 14, 909 (1969).
4. G. H. SEDAHMED, Thesis, University of Alexandria (1969).