Journal of Dispersion Science and Technology

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Corrosion of Copper in Presence of Acetic Acid

Derivatives

H. H. Abdel-Rahman

To cite this article: H. H. Abdel-Rahman (2010) Corrosion of Copper in Presence of Acetic

Acid Derivatives, Journal of Dispersion Science and Technology, 31:12, 1740-1751, DOI:
10.1080/01932690903543147

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Journal of Dispersion Science and Technology, 31:1740–1751, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690903543147

Corrosion of Copper in Presence of Acetic Acid

Derivatives
H. H. Abdel-Rahman
Faculty of Science, Department of Chemistry, Alexandria University, Alexandria, Egypt

The anodic corrosion of copper in presence of acetic acid derivatives were determined by measur-
ing the limiting current. It is found that the rate of corrosion increased by decreasing H3PO4
concentration and electrode height. The experimental results showed that the inhibition efficiency
increased with increasing concentration of the investigated compounds at a fixed temperature, but
decreases with increasing temperature. Values of activation energy indicate that the reaction is
diffusion controlled. The isotherm Langmuir, Temkin, and Flory Huggins are applied. The
values of free energy of adsorption (DGads) obtained indicate the spontaneous adsorption of the
inhibitor. The overall mass transfer correlations under the present conditions have been obtained
using dimensional analysis method. The results agreed with the previous studies of mass transfer
to rotating cylinder in turbulent flow.At the end of the corrosion process the morphology of the
specimens after experiment is monitored using scanning electron microscope (SEM). SEM exam-
ination of the copper surface revealed that these compounds inhibited copper from corrosion by
adsorption on its surface to form protective film. The presence of these organic compounds
adsorbed on the electrode surface was confirmed by SEM investigations.
Keywords Acetic acid derivatives, corrosion inhibition, electrodeposition, limiting current

INTRODUCTION and prevent transportation of water and corrosion on

The corrosion of materials in acidic solution causes
considerable costs. Corrosion of metals depends on the
kind of metal, the environmental conditions and the kind
of the ions present in the environment. Copper and its
alloys are used widely in industry, because of their good
thermal conductivity and mechanical properties. Copper
is a relatively noble metal. Nevertheless, it reacts easily
in ordinary oxygen containing environments.[1] Copper is
widely used in many applications in electronic industries
and communications as a conductor in electrical power
lines, pipe lines, for domestic and industrial water
utilities including sea water, heat conductors, heat
exchange, etc.[2–6]
In order to reduce the corrosion of metals, several
techniques have been applied. The use of inhibitors is
one of the most practical methods for the protection
against corrosion in acidic media. One of the most
important methods in the protection of copper against
corrosion is the use of organic inhibitors. To be effective,
an inhibitor must also displace the water from the metal
surface, interact with anodic or cathodic reaction sites to
retard the oxidation and reduction corrosion reaction
Received 5 August 2009; accepted 6 September 2009.
Address correspondence to H. H. Abdel-Rahman, Faculty of
Science, Department of Chemistry, Alexandria University,
Alexandria, Egypt. E-mail: hhabdelrahman10@yahoo.ca
active species to the surface.[7] Organic compounds con-
taining polar groups and heterocyclic compounds with
polar functional groups and conjugated double bonds
have been reported to inhibit copper corrosion.[8–12] The
inhibiting action of these organic compounds is usually
attributed to their interaction with copper surface via
their adsorption. Polar functional groups are regarded
as the reaction center that stabilizes the adsorption
process. In general, the adsorption of inhibitor on metal
surface depends on the nature and the surface charge of
the metal, the adsorption mode, its chemical structure
and the type of electrolyte solution.[12] The aim of the
present work is to study the effect of organic compounds
namely formic acid, acetic acid, mono-, di-, and trichlor-
oacetic acid as well as amino acetic acid on the rate of
corrosion of copper. Such investigation included changes
in temperature; speed of rotation cylinder (RCE) and
concentration of organic compounds Physical properties
of solution such as density, viscosity and diffusion coef-
ficient are studied to obtain a dimensionless correlation
among all these parameters. At the end of the corrosion
process the morphology of the specimens after experi-
ment is monitored using scanning electron microscope
(SEM). The study of the (SEM) to graphs support
the experimental measurements and give more light on
copper surface.

1740
 CORROSION OF COPPER WITH ACETIC ACID DERIVATIVES
MATTERIALS AND METHODS
All of the reagents and chemicals were of analytical
grade. Doubly distilled de-ionized water was used in the
preparation of solutions.
Apparatus and Procedure
Vertical parallel plate’s cell: The cell used in the present
work consists of rectangular container having the dimen-
sion of 5
10 cm with electrodes fitting the whole cross
section. The electrodes were rectangular copper sheets of
10 cm height and 5 cm width. Electrode separation was
5 cm; a porous PVC diaphragm was used to prevent the
stirring effect due to H2 bubbles. The electrical circuit
consisted of a 6 V D.C. power supply, a variable resistance
and a multi range ammeter connected in a series with cell.
A high impedance voltammeter was connected in parallel
with the cell to measure its potential. Five concentrations
(6, 8, 10, 12, and 14 M) of phosphoric acid were used
and organic acid compound named formic, acetic, mono-
, di-, and trichloroacetic acid as well as amino acetic acid
was used. The steady state anode potential was measured
against reference electrode consisted of copper wire
immersed in a cup of luggin tube filled with phosphoric
acid-organic solution similar to that in the cell, the tip of
the luggin tube was placed 0.5–1 mm from anode wall.
Polarization curves, from which the limiting current was
determined, were plotted by increasing the applied current
stepwise and measuring the corresponding steady-state
potential. Two minutes were allowed for reaching the
steady state potential. Before each run, the back of anode
was insulated with polystyrene lacquer and the active
surface was polished with fine emery paper, degreased with
trichloroethylene, washed with alcohol and finally rinsed in
distilled water. The temperature was regulated by placing
the cell in thermostatic water bath (Scheme 1).
The Rotating Cylinder Electrode
The anode consists of copper metal cylinder 1 cm
diameter and 7 cm length. The disc is insulated by epoxy
resin. The cathode is made of cylindrical copper metal
SCH. 1. Carboxylic acids.
1741
counter electrode 12 cm diameter; it is also acted as refer-
ence electrode by virtue of its high surface area compared
to that of the cathode.
Density and Viscosity Measurements
The density was measured by using DA-300 Kyoto
Electronics (Japan) density measurement equipment at
different temperatures. The viscosity was measured by
using Koehler viscosity Bath (Model K23400 Kinematic
bath) at different temperatures.
RESULTS AND DISCUSSION
Leveling Process
Leveling is the principle process in electropolishing[13]
and can be explained by mass transfer mechanism.[14] The
study of leveling is based on the classical current voltage
curves of electro dissolution. Cell with a diaphragm were
used to study the effect of hydrogen gas evolved at the
cathode on the limiting current. While a cell without dia-
phragm is used to study the effect of hydrogen gas evolved
at the cathode on the rate of mass transfer at the anode i.e.,
forced convection. Figure 1 shows the limiting currents Il
with and without diaphragm for blank solution at 298 K
as an example.
Effect of Electrolyte Concentration
Figure 2 shows the limiting current decreases with
increasing phosphoric acid concentration within the range
studied (6–14 M) at 298 K. This is agreement with the find-
ing of the other authors who worked within the same range
of concentration.[15] The decrease in the limiting current
with H3PO4 concentration is attributed two effects. (a)
The solubility of dissolved copper phosphate in ortho phos-
phoric acid, which is responsible for the limiting current,
decreases with increasing phosphoric acid concentration.
FIG. 1. The limiting current with and without diaphragm for blank
solution at 298 K.
1742 H. H. ABDEL-RAHMAN
FIG. 2. Effect of phosphoric acid concentration on the limiting cur-
rent at 10 cm height and 298 K.
(b) The viscosity of the solution increases with increasing
H3PO4 concentration with consequence decrease in the
diffusivity of Cu2þ according to Stokes-Einstein equation.
Dg=T ¼ constant;
where, D is the diffusivity of Cu2þ (cm2 S1), g is the viscosity
of the solution (poise), and T is the absolute temperature.
Also the increase in solution viscosity with increasing
the phosphoric acid concentration result in an increase in
the diffusion layer thickness which represent the resistance
to the rate of mass transfer of Cu2þ from anode surface to
the bulk solution.
The values of limiting current at the highest concen-
tration of inhibitor was lowest compared to other concen-
trations which shows that organic acid inhibited corrosion
reaction compared to blank (H3PO4) alone is shown in
Table 1. From the practical point of view, we can conclude
on the basis of above result that it is preferable to use
relatively high organic percentage to inhibit corrosion or
dissolution of metal at the same phosphoric acid concen-
tration. Apparently, corrosion rate linearly decreases with
increasing concentration of phosphoric acid, and corrosion
rate increases with increasing experimental temperature.
So, organic additive will make inhibition of copper cor-
rosion in phosphoric acids. Figure 2 gives the relationship
between corrosion rate (limiting current intensity) and con-
centration of phosphoric acid in presence of (amino acetic
acid). It is clear that at a certain experimental temperature,
corrosion rate of specimen sharply decreases with an
increase in concentration of phosphoric acid in the pres-
ence of (amino acetic acid) compared with phosphoric acid
without (amino acetic acid), it can be seen from Figure 2
that the corrosion rate of copper is more significantly
inhibited by phosphoric acid in the presence of amino
acetic acid.
As the organic compound is added to phosphoric acid
which has different concentration, the limiting current
decreases. This explains on the basis that, the viscosity of
organic -water- H3PO4 mixture is increased and this led
to: (a) decrease in diffusivity of Cu2þ; (b) the solubility of
copper phosphate in this solution is lower than in water
phosphoric acid mixture, so the saturation of solution is
attained and limiting current is small.
Effect of Electrode Height on Polishing Current
Figure 3 shows that the limiting current density
decreases with the increase in height. In anodic corrosion
and generally for anodic dissolution of metals, the direc-
tion of flow of the hydrodynamic boundary layer and the
diffusion layer increase in the downward direction, that
is, the resistance to mass transfer increases in downward
direction. The local limiting current density increases
in the upward direction of the anode. This explains why
corrosion is attained at the upper parts of the electrode
before the lower part at the limiting current region. This
was confirmed by the visual observation during corrosion.
The average limiting current density decreases with the
increase in the height according to the equation
Il ¼ Constant=ha ;
where h is the height, Il is the limiting current density, and
a is constant depends on type of solution used, where
a ¼ 0.39 for 6 M H3PO4 and 0.38 for acetic acid as an
example.
Effect of Concentration of the Inhibitor
The limiting currents obtained at the highest concen-
tration of inhibitors were lowest compared to other
concentrations which show that acids organic inhibited
corrosion reaction compared to blank [(H3PO4) alone]
show Table 1, which shown that the corrosion rate is

highest in the blank at different temperatures (25–40 C).
When we added organic acids the limiting current as well
as the corrosion rate decreased. It is recommended to use
relatively high concentration of organic additives to inhibit
dissolution of metal in phosphoric acid.[16] If the limiting
current in absence of organic compound Ib and in presence
of organic compound Iorg, the inhibition efficiencies (IE%)
listed in Table 1 were calculated according to the
equation.[17,18]
% inhibition ¼ ½ðIb  Iorg Þ=Ib 
100:
Table 1 also shows the calculated values of inhibition
efficiency at different temperatures. The percentage
 CORROSION OF COPPER WITH ACETIC ACID DERIVATIVES 1743

TABLE 1
The limiting current (mA) and % inhibition for all organic acids at different temperatures
Compound A Compound B Compound C Compound D Compound E Compound G

Temp. Conc.
104 % % % % % %

(K) (moll1) Il Inhibition Il Inhibition Il Inhibition Il Inhibition Il Inhibition Il Inhibition

0 950 0 950 0 950 0 950 0 950 0 950 0

0.5 860 9.47 900 5.26 670 29.5 680 28.4 850 10.5 600 36.8
1 820 13.7 870 8.4 650 31.6 650 31.6 820 13.7 580 38.9
1.5 780 17.9 840 11.6 630 33.7 620 34.7 790 16.8 560 41.1
298 2 760 20.0 810 14.7 610 35.8 600 36.8 780 17.9 530 44.2
2.5 740 22.1 770 18.9 590 37.9 580 38.9 760 20.0 500 47.4
3 700 26.3 740 22.1 560 41.1 560 41.1 730 23.2 450 52.6
5 660 30.5 700 26.3 550 42.1 530 44.2 700 26.3 400 57.9
0 970 0 970 0 970 0 970 0 970 0 970 0
0.5 880 9.3 930 4.1 690 28.9 700 27.8 870 10.3 620 36.1
1 840 13.4 900 7.2 670 30.9 670 30.9 840 13.4 600 38.1
1.5 810 16.5 870 10.3 650 33.0 640 34.0 820 15.5 580 40.2
303 2 780 19.6 840 13.4 630 35.1 620 36.1 800 17.5 550 43.3
2.5 760 21.6 800 17.5 610 37.1 600 38.1 780 19.6 520 46.4
3 730 24.7 760 21.6 585 39.7 580 40.2 760 21.6 480 50.5
5 700 27.8 720 25.8 570 41.2 550 43.3 730 24.7 420 56.7
308 0 990 0 990 0 990 0 990 0 990 0 990 0
0.5 905 8.6 960 3.0 710 28.3 720 27.3 900 9.1 638 35.6
1 860 13.1 930 6.1 690 30.3 695 29.8 870 12.1 615 37.9
1.5 840 15.2 895 9.6 670 32.3 660 33.3 840 15.2 600 39.4
2 800 19.2 865 12.6 650 34.3 640 35.4 820 17.2 580 41.1
2.5 790 20.2 830 16.2 630 36.4 625 36.9 800 19.2 560 43.4
3 750 24.2 780 21.2 610 38.4 600 39.4 780 21.2 520 47.5
5 730 26.3 740 25.3 600 39.4 580 41.4 750 24.2 450 54.5
0 1015 0 1015 0 1015 0 1015 0 1015 0 1015 0
0.5 930 8.4 990 2.5 740 27.1 740 27.1 930 8.4 700 31.0
1 890 12.3 960 5.4 710 30.0 720 29.1 900 11.3 670 34.0
1.5 860 15.3 920 9.4 700 31.0 680 33.0 865 14.8 620 38.9
313 2 830 18.2 890 12.3 680 33.0 660 35.0 850 16.3 610 39.9
2.5 810 20.2 855 15.8 660 35.0 650 36.0 830 18.2 590 41.9
3 780 23.2 710 20.2 645 36.5 620 38.9 810 20.2 550 45.8
5 760 25.1 760 25.1 630 37.9 600 40.9 770 24.1 480 52.7

inhibition efficiency of organic compounds decreased with

FIG. 3. Variation of limiting current with height in presence of 6 M
H3PO4 at 298 K.
temperature and increases with increasing concentration
of organic compound. This may attributed to the desorp-
tion of the inhibitor molecules at higher temperatures, thus
exposing the metal surface to further attack and this
suggests physical adsorption mechanism.[16] Addition of
organic compounds lowers the dissolution rate of copper
and the effect increases upon increase in the concentration
of organic compound. Perhaps, the adsorption of organic
molecules onto the copper surface plays an important role
in preventing copper from being corroded easily. This was
also confirmed by plotting the variation of the inhibition
efficiency (IE%) of the copper by organic compounds with
concentration Figure 4. This confirms again that organic
compound inhibits the corrosion process on the copper sur-
face and inhibitory effect is enhanced as its concentration is
1744 H. H. ABDEL-RAHMAN

FIG. 4. Effect of concentration for all organic compounds on %

inhibition.

FIG. 5. Langmuir isotherm for the adsorption on the copper surface

increased.[19] The data shows that IE% depends on the type
of organic compound and its concentration.
The decrease in limiting current with increasing the con-
centration of organic compounds is attributed to (a) the
decrease in solubility of dissolved copper phosphate in phos-
phoric acid, which is responsible for the limiting current, and
(b) the decrease in the diffusion layer thickness which is
represent the resistance to the rate of mass transfer of copper
ion from anode surface to bulk solution. The order of inhi-
bition was G > D > C > A > E > B. The results also suggest
that in case of (B, E) the adsorption of the inhibitor is
weaker and the adsorption of the inhibitor takes place.[20]
For G and to a certain extent for A also, the adsorption
bonds appear to be stronger and resist the adsorption.
Adsorption Isotherm
Adsorption isotherms are very important in determining
the mechanism of organo-electrochemical reactions. Data
related to the degree of surface coverage (H) were tested
graphically in order to determine the most suitable adsorp-
tion isotherm.
The Langmuir adsorption isotherm is applied to investi-
gate the adsorption mechanism by the following equation.[21]
C=H ¼ ð1=KÞ þ C;
where K is the equilibrium constant of adsorption process, C
is the inhibitor concentration and H is the surface coverage of
the metal surface.
The degree of surface coverage H at constant tempera-
ture was determined from this equation
of organic compounds in 6 M phosphoric acid.
not accord with the Langmuir adsorption isotherm. Then
the Temkin adsorption isotherm is employed, and it has
the form of equation,[22]
H ¼ ðln K=2aÞ þ ðln C=2aÞ;
where a is the lateral interaction term describing the mol-
ecular interactions in the adsorption layer and the hetero-
geneity of the metal surface. The regression between H
and ln C is dealt with; the linear correlation coefficients
and molecular interaction parameters are listed in
Figure 6. It is clear that the experimental data can be
explained using the Temkin adsorption isotherm. Table 3
shows that all the values of a are smaller than zero, indicat-
ing that the repulsion exists in the adsorption layer.[23]
The Flory-Hugins adsorption isotherm is employed, and
it has the form of this equation,[24]
log H=C ¼ log xK þ x logð1  HÞ;
where x is the number of inhibitor molecules occupying one
active site or the number of water molecules replaced by
TABLE 2
Some parameters of the linear regression between
C=h and C at 298 K
Organic Linear correlation
compounds Slope coefficient, R2

H ¼ ðIb  Iorg Þ=Ib : A 2.37 0.982

B 1.83 0.907
First, the regression between C=H and C is shown in C 2.21 0.996
Figure 5. It is apparent that the linear correlation coeffi- D 2.10 0.997
cients are good and all the slopes are not close to 1 is shown E 3.14 0.981
in Table 2, meaning that the adsorption of inhibitor does G 1.56 0.981
 CORROSION OF COPPER WITH ACETIC ACID DERIVATIVES
FIG. 6. The relation between surface coverage and ln C for organic
compounds at 298 K.
one molecule of inhibitor. The values of x are 3.9, 2.3, 8.03,
7.04, and 7.5, 2.67for A, B, C, D, E, and G, respectively. It
is clear that the surface coverage data are very useful for
discussing adsorption characteristics. The adsorption of
corrosion inhibitors at the metal solution interface may
be due to the formation of either electrostatic or covalent
bonding between the adsorbents and the metal surface.
If it is assumed that the inhibitor is adsorbed on the
metal surface in the form of a monomolecular film, cover-
ing at any instant a fraction H of the total surface in a uni-
form or random manner, then the heat of adsorption (Qads)
of the inhibitor can be calculated from the equation,[20]
Qads ¼ 2:303R½logðH2 =1H2 ÞlogðH1 =1H1 Þ
ðT1 T2 =T2 T1 Þ;
where H1 and H2 are the fractions of the total surface cov-
ered by the inhibitor at temperatures T1 and T2(K),
respectively. The values of free energy of adsorption
(DGads) were calculated with the help of the equation.[24,25]
DGads ¼ R T lnð55:5 KÞ:
TABLE 3
Some parameters of the linear regression between coverage
and ln C for organic compounds at 25 C
Organic Linear correlation
compounds A coefficient R2
A 5.62 0.974
B 5.15 0.947
C 5.11 0.958
D 6.94 0.993
E 7.14 0.958
G 5.56 0.940
1745
TABLE 4
Heat of adsorption Qabs and free energy of adsorption
DGads during corrosion of copper in 6 M Phosphoric acid
containing 0.5
104 mol ll organic compounds
Organic
compounds A B C D E G
Qabs 8.18 44.80 4.50 4.11 12.11 3.94
(25–35  C)
(kJmol1)
DGads 36.80 35.20 40.27 43.80 36.80 44.94
(kJmol1)
The value 55.5 in above equation is the concentration of
water in solution in mol l1.[26,27] The calculated adsorp-
tion free energies are listed in Table 4.
From Table 4, it is evident that in all cases, the Qads values
are negative shows that the adsorption and hence inhibition
efficiency decreases with rise in temperature.[28] The values
of DGads obtained indicate the spontaneous adsorption of
the inhibitor. Further, the Qads values are less negative while
the free energies of adsorption are more negative in the case
of very good inhibitors like (G, D) which suggest that there
is a strong interaction of the inhibitor molecules with
the metal surface resulting in the spontaneous adsorption.
For a relatively weak inhibitor like (E,B) the Qads values
are more negative and the free energies are less negative
resulting in a weakly bound inhibitor molecule. The negative
values of the free energy of adsorption indicate a
spontaneous adsorption of these inhibitors on copper.[29,30]
Effect of Temperature on the Performance of Inhibitors
The effect of temperature on %inhibition in 6 M phos-
phoric acid of 0.5
104 mol ll of all the investigated inhi-
bitors was determined in the temperature range 25, 30, 35,

40 C, and is illustrated in Figure 7. It was observed that the
FIG. 7. Variation of % inhibition in presence of 0.5
104 mol ll for
all organic compounds at different temperatures.
1746 H. H. ABDEL-RAHMAN

TABLE 5
The values of % inhibition for 0.5
104 mol ll of
different organic compounds and 6 M H3PO4 at
different temperatures
% Inhibition
SCH. 2. &.

T C A B C D E G

25 9.47 5.26 29.50 28.40 10.50 36.8 aluminum-copper alloy. They showed that inhibition
30 9.30 4.10 28.9 27.80 10.30 36.1 efficiency increases with concentration.
35 8.60 3.00 28.3 27.30 9.10 35.6 The presence of electron attracting group increases the
40 8.40 2.50 27.1 27.10 8.40 31.0 acid strength. All inhibitors contains COOH group which
may adsorb on the metal surface. Patr et al.[35] and Quar-
aishi et al.[36] were explained that the inhibitors inhibit cor-
corrosion rate increases with temperature for all the rosion of metal surface through their chlorine atom. Tri-,
studied system, indicating good inhibitive properties of di-, and monochloro acetic acids are strong inhibitors than
the studied the compounds under the studied conditions. others because the chlorine atom is electron attracting
Table 5 shows good corrosion inhibitors qualities as the group led to increase the ionization of COOH which
studies compound retain their protective properties even at adsorbed on metal.
relatively high temperature (40 C). The values of activation It is found that, the higher inhibition of trichloroacetic
energy (Ea) were calculated with the help of the Arrhenius acid is attributed to either their coordination type of bond-
equation,[31] ing to metal surface or to their electron attracting effect
leading to decrease the electron density at the functional
group site,[37] that is, strong coordination type bond with
Il ¼ AeEa=RT ;
copper. Acetic acid is less inhibitor than formic acid
because methyl group is electron releasing group, that is,
where A is a pre-exponential factor, R is the gas constant
it decrease the acidity of –COOH group and less adsorp-
and T is the absolute temperature. Which support that
tion takes place. Amino acetic acid is the least inhibitor
physical adsorption is proposed. The values are presented
in acidic medium, positive ion formed repel with copper
in Table 6 shows that all (Ea) values are lower than 40
anode and adsorption of amino acetic acid on anode
kJmol1; that is, diffusion processes are controlling the
decreases (Scheme 2).
corrosion reaction which is in agreement with other obser-
vation earlier published.[16,24,32,33]
Effect of Rotation
Effect of Chemical Structure on the Inhibition Efficiency The effect of the speed of rotation on the corrosion rate
can also be used to determine whether the corrosion
Anodic corrosion rate of copper in phosphoric acid
process is diffusion or chemically controlled process. If
decreases with addition of inhibitors as formic acid, acetic
the limiting current density increases by increasing the
acid, mono-, di-, and trichloro acetic acid and amino acetic
acid is shown in Table 1. The efficiency of inhibitors
increases by increasing concentration of inhibitors. The
order of decreased inhibition of corrosion of copper as
follow:
Trichloro acetic > dichloro acetic > monochloro acetic >
formic acid > acetic acid > amino acetic acid. Several
authors[34] have studied organic acid as inhibitors of

TABLE 6
The values of activation energy (Ea kJmol1) in 6 M H3PO4
with and without addition of organic compounds
Organic
compounds Blank A B C D E G

Ea (kJ mol1) 8.68 4.08 4.94 5.07 4.38 4.71 5.58 FIG. 8. Variation of the limiting current density Il, with the angular
velocity to a power 0.7, x0.7 for organic compounds used at 298 K.
 CORROSION OF COPPER WITH ACETIC ACID DERIVATIVES 1747

TABLE 7
Physical propertiesg, q and D used in calculated dimensionless groups
Conc.
104 Il D cm2 g gcm1 q Conc.
104 Il D cm2 g gcm1 q
mol l1 rpm mA sec1 sec 1
gcm 3
mol l1 rpm mA sec1 sec1 gcm3

A D
125 950 3.87
1006 125 750 2.26
1006
250 1020 2.04
1006 250 820 1.22
1006
0.5 375 1060 1.39
1006 4.97 1.46 0.5 375 870 8.65
1007 3.40 1.37
500 1120 1.11
1006 500 930 7.02
1007
625 1200 9.68
1007 625 1000 6.16
1007
125 900 3.56
1006 125 750 2.34
1006
250 940 1.79
1006 250 770 1.14
1006
1 375 960 1.19
1006 4.69 1.38 1 375 790 7.70
1007 3.65 1.38
500 990 9.15
1007 500 810 5.85
1007
625 1050 7.87
1007 625 840 4.86
1007
125 880 3.33
1006 125 730 2.38
1006
250 900 1.62
1006 250 750 1.17
1006
1.5 375 930 1.09
1006 4.4 1.38 1.5 375 770 7.85
1007 4.12 1.39
500 960 8.44
1007 500 790 5.97
1007
625 1020 7.27
1007 625 810 4.87
1007
125 860 3.36
1006 125 700 2.40
1006
250 860 1.64
1006 250 720 1.18
1006
2 375 920 1.13
1006 4.79 1.38 2 375 750 8.10
1007 4.70 1.39
500 950 8.68
1007 500 770 6.17
1007
625 1000 7.38
1007 625 790 5.04
1007
125 840 3.37
1006 125 650 2.17
1006
250 890 1.74
1006 250 700 1.14
1006
2.5 375 900 1.14
1006 5.10 1.36 2.5 375 720 7.69
1007 4.80 1.39
500 930 8.75
1007 500 750 5.99
1007
625 980 7.45
1007 625 765 4.85
1007
B E
125 1000 3.48
1006 125 930 3.08
1006
250 1080 1.84
1006 250 1000 1.62
1006
0.5 375 1100 1.22
1006 3.30 1.36 0.5 375 1040 1.11
1006 3.20 1.36
500 1200 1.02
1006 500 1080 8.60
1007
625 1320 9.32
1007 625 1160 7.54
1007
125 980 3.60
1006 125 930 3.29
1006
250 1010 1.77
1006 250 960 1.63
1006
1 375 1040 1.19
1006 3.71 1.37 1 375 990 1.09
1006 3.65 1.365
500 1060 9.01
1007 500 1020 8.43
1007
625 1100 7.49
1007 625 1060 7.02
1007
125 860 3.78
1006 125 900 3.33
1006
250 980 1.83
1006 250 930 1.65
1006
1.5 375 1020 1.25
1006 4.19 1.33 1.5 375 975 1.14
1006 4.10 1.370
500 1040 9.48
1007 500 1000 8.68
1007
625 1080 7.89
1007 625 1020 7.02
1007
125 930 3.75
1006 125 870 3.26
1006
250 960 1.85
1006 250 900 1.62
1006
2 375 990 1.25
1006 4.70 1.38 2 375 960 1.15
1006 4.40 1.38
500 1010 9.45
1007 500 980 8.71
1007
625 1050 7.88
1007 625 1000 7.05
1007

(Continued )
1748 H. H. ABDEL-RAHMAN

TABLE 7
Continued
Conc.
104 Il D cm2 g gcm1 q Conc.
104 Il D cm2 g gcm1 q
mol l1 rpm mA sec1 sec 1
gcm 3
mol l1 rpm mA sec1 sec1 gcm3

125 900 3.63
1006 125 840 3.16
1006

250 930 1.80
10-06 250 870 1.57
1006
2.5 375 960 1.21
1006 4.90 1.39 2.5 375 940 1.14
1006 4.60 1.382
500 990 9.34
1007 500 960 8.63
1007
625 1020 7.67
1007 625 980 6.99
1007
C G
0.5 125 730 2.13
1006 125 600 1.55
1006
250 800 1.15
1006 250 630 7.87
1007
375 850 8.18
1007 3.25 1.36 0.5 375 660 5.45
1007 3.17 1.363
500 900 6.54
1007 500 700 4.37
1007
625 960 5.67
1007 625 750 3.81
1007
1 125 710 2.17
1006 125 590 1.63
1006
250 730 1.06
1006 250 620 8.33
1007
375 770 7.46
1007 3.67 1.37 1 375 640 5.63
1007 3.71 1.369
500 800 5.79
1007 500 670 4.42
1007
625 850 4.99
1007 625 700 3.71
10-07
1.5 125 680 2.18
1006 125 580 1.70
1006
250 700 1.07
1006 250 600 8.46
1007
375 730 7.38
1007 4.21 1.37 1.5 375 620 5.73
1007 4.19 1.363
500 770 5.86
1007 500 640 4.40
1007
625 800 4.88
1007 625 680 3.79
1007
2 125 650 2.17
1006 125 550 1.63
1006
250 680 1.09
1006 250 580 8.35
1007
375 700 7.39
1007 4.79 1.38 2 375 600 5.66
1007 4.5 1.36
500 730 5.77
1007 500 620 4.36
1007
625 760 4.82 1007 625 650 3.68
1007
2.5 125 620 2.03
1006 125 520 1.55
1006
250 660 1.05
1006 250 550 7.95
1007
375 680 7.12
1007 4.90 1.39 2.5 375 580 5.56
1007 4.79 1.36
500 700 5.45
1007 500 600 4.28
1007
625 730 4.56
1007 625 630 3.63
1007

speed of rotation, then the reaction is diffusion controlled.
However, if the limiting current is independent of the
rotation, so the reaction is likely to be chemically con-
trolled. The angular velocity, x, is given by:
x ¼ ð2 rpmÞ=60:
Figure 8 shows the relation between the limiting current
density and the angular velocity to a power 0.7 at 298 K
and different organic compounds used. Straight lines were
obtained and the limiting current density increases by
increasing rotation, which indicates that the corrosion
process of copper is diffusion controlled reaction. The
diffusion coefficient of Cu2þ ions, D, in different solutions
was determined from the values of limiting current density,
as shown in Table 7, using Eisenberg equation,[38]
Il ¼ kn F Cb d0:3 n 0:344 D0:644 Ux ;
where k ¼ 0.097 and x ¼ 0.7, n is the number of electrons
involved in process, F is Faraday’s constant, U is the per-
ipheral velocity ¼ xr in cm rad s1(r is the radial distance in
cm) or U ¼ 2p xr in c m s1, d is the characteristic length
for the rotating cylinder in cm, and n is the kinematic
viscosity (n ¼ g=q, g is the viscosity in g cm1 s1 and q is
the density in g cm3).
The diffusion coefficient ;D, of Cu2þ ions in solutions
containing organic compounds decreases due to the
increase in the interfacial viscosity, g in accordance with
Stokes-Einstein equation.[39] The present results agree with
the polar graphic studies conducted in solution containing
surfactants and also solution containing organic solvent,
 CORROSION OF COPPER WITH ACETIC ACID DERIVATIVES 1749

where it was found that the diffusion current decreases in

the presence of surfactant and organic solvent.[39]

DATA CORRELATION
The mass transport to an inner rotating cylinder elec-
trode in turbulent flow system may be described by empiri-
cal dimension less

Sh ¼ a Scc Reb ;

where Sh, Re, and Sc are the Sherwood (Sh ¼ kl=D), k is

mass transfer coefficient, cm sec1 (k ¼ I=zFCCu2þ where
CCu2þ is saturation solubility of copper phosphate, z is the FIG. 10. The overall correlation for all organic compounds.
valance, F is Faraday’s constant in coulomb),l is length of
cylinder, cm and D is diffusion coefficient, cm 2 sec1,
Reynolds (Re ¼ l U =n), n is kinematic viscosity, cm2 Figure 10 gives the overall correlation for all organic
sec1, and U is rotation velocity ¼ xr, cm sec1,and compounds used which correlated by the equation
Schmidt (Sc ¼ n=D) numbers, respectively and a and b are
empirical constants, c ¼ 0.33 indicating forced convection Sh ¼ 0:431 Sc0:33 Re0:722 :
regime.[40] By plotting log (Sh=Sc0.33)against log (Re), a
straight line was obtained its slope gave the constant b while In our present study a forced convection mechanism is
the intercept gives the constant a. Figure 9 shows the mass obtained which agrees very well with similar relationships
transfer correlation for all parameters used. this Figure 9, reported before.[38,41,44]
the data can be correlated by the following equations:
Scanning Electron Microscopy Measurements
Sh ¼ 0:144 Sc0:33 Re0:722 Acetic acid The surface morphology of copper samples immersed in
Sh ¼ 0:142 Sc0:33 Re0:725 Formic acid acidic bath (H3PO4) with or without additives has widely
Sh ¼ 0:148 Sc0:33 Re0:723 Trichloro acetic acid studied. All experiments were made at the limiting current
Sh ¼ 0:143 Sc0:33 Re0:724 Dichloro acetic acid density determined for all solutions at 25 C and time of 5
Sh ¼ 0:148 Sc0:33 Re0:720 Monochloro acetic acid minutes.
Sh ¼ 0:131 Sc0:33 Re0:735 Amino acetic acid Figure 11a shows morphology of copper metal in 6 M
H3PO4 after 5 minutes in absence of organic additives.
We can note that under corrosion layer, the initial structure
of unexposed material can be observed.
Figures 11b through 11g) give the morphology of
polished copper in 6 M H3PO4 for 5 minute at 25 C in
presence of organic compounds as acetic acid, formic acid,
monochloro acetic acid, dichloro acetic acid, trichloro
acetic acid and amino acetic acid, respectively.
The outstanding corrosion protection by additives coat-
ing to copper surface may be due to the fact that, the
deposited organic substituent is strongly adherent and uni-
formly covers the entire electrode surface especially in tri-
chloro acetic acid, dichloro acetic acid and monochloro
acetic acid (Figures 11d, 11e, and 11f), which consider as
the strongest inhibitors; this verified by experimental
results in which the limiting current which consider as the
rate of corrosion is more smaller in presence of trichloroa-
cetic acid, dichloroacetic acid, and monochloroacetic acid.
In presence of other inhibitors, the adsorbed layer is less
uniform which verify by our results. amino acetic acid is
FIG. 9. The overall mass transfer correlation for all organic the less inhibitor give less adherent, less uniform layer
compounds. and does not cover the surface tightly enough and,
1750 H. H. ABDEL-RAHMAN
FIG. 11. Scanning electron microscopy of copper sheet in 6 M H3PO4
and presence of organic compounds.
therefore does not properly protect the Cu surface. Based
on corrosion protection mechanism Put forth by several
researchers,[45–47] the conducting additives accept electrons
from metal and give them to Hþ. This reaction generates
the formation of adsorbed layer at organic metal interface
which lower the corrosion rate. Figures 11f and 11h show
effect of temperature on the corrosion layer in presence
of trichloroacetic acid. It is obvious that the surface is
non- uniformly covered with a film and crystals continued
to increase in size,when temperature increased, this verify
by limiting current at 35 C is more than at 25 C. The cor-
rosion rate is rather uniform with small grains Figures 11d,
11e, and 11f. On contrast for higher concentration of
monochloro acetic acid, the layer is granular with big sized
grains, which also explains large decrease in currents as
concentration increases (Figure 1).
In case of the solution containing trichloroacetic acid
the protection film on the copper surface was the most
compact and protected the surface of copper better against
the attack of the aggressive environment. The results con-
firm that the protective film with trichloroacetic acid is
tighter than with dichloroacetic acid and monochloroacetic
acid.[1]
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