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org
International Journal of Metallurgical & Materials
Science and Engineering (IJMMSE)
ISSN(P): 2278-2516; ISSN(E): 2278-2524
Vol. 4, Issue 2, Apr 2014, 9-18
TJPRC Pvt. Ltd.

SYNERGISTIC INHIBITION BETWEEN AMPICILLIN TRI-HYDRATE AND KI FOR
CORROSION OF CARBON STEEL IN 1M HCl SOLUTION
HAMEED HUSSEIN ALWAN
Department of Electrochemical Engineering, College of Engineering, Babylon University, Iraq

ABSTRACT
The effect of Ampicillin tri-hydrate C
16
H
19
N
3
O
4
S on the corrosion of carbon steel in 1 M HCl solution was
studied by weight loss and electrochemical polarization techniques at 30

C (313 K), Ampicillin tri-hydrate concentrations


used in the study were (0.001, 0.002, 0.003 and 0.004)M .The effect of KI addition on corrosion inhibition efficiency was
also studied. The results show that inhibition efficiency increased with Ampicillin tri-hydrate concentration and
synergistically increased in presence of KI. The adsorption of Ampicillin tri-hydrate and KI on carbon steel surface follows
Freundlich isotherm and, adsorption on surface of carbon steel is spontaneously due to adsorption free energies
calculation.The synergistic parameter values indicating that the enhancement of inhibition efficiency is due to synergism
caused by adding halides ions.
KEYWORDS: Corrosion, Corrosion Inhibitor, Adsorption Isotherm, Activation Energy, Synergistic Inhibition
INTRODUCTION
Carbon steel is widely used in various industrial operations and the study of corrosion of carbon steel and its
protection is a subject of practical significance. In efforts to mitigate electrochemical corrosion, the primary strategy is to
isolate the metal from corrosive agents. A useful method for achieving in this is addition of species to the solution in
contact with the surface in order to inhibit the corrosion reaction and reduce the corrosion rate. [1-3] Study of organic
corrosion inhibitors is an attractive field of research due to its usefulness in various industries. Most of the well-known acid
inhibitors are organic compounds that containnitrogen, sulphur, oxygen and multiple bonds in the molecules through which
are adsorbed on the metal surface. The protection of metals against the corroding action is accomplished by adding
chemical substances of small concentration to environment; these chemicals are called Inhibitors. So inhibitors are
chemical compounds that deposit on exposed metal surfaces from the corrosive environment. The inhibitor may form a
uniform film, which like a coating, acts as a physical barrier. Organic compounds which containing sulfur, phosphorus;
oxygen nitrogen and aromatic rings are most effective and efficient inhibitors for the metals in acidic medium due to their
molecular structure. [4-6] The presence of halide ions in solution has been found to stabilize the adsorption of someorganic
cations leading to improved inhibition efficiency. Synergism has become an increasing important phenomenon and serves
as the basis for most modern corrosion inhibitor formulation. Trials to enhance the performance of naturally occurring
substances by addition of small amount of halide ions have been reported by some authors. [3, 7-8]. In the present work it
was examined the synergistic corrosion inhibition between Ampicillin tri-hydrate and potassium iodide for inhibit
corrosion of carbon steel in 1M HCl solution in which Ampicillin tri-hydrate represented as cations while KI work as
anions. Adsorption mechanism was studied and synergism parameter was evaluated also.
10 Hameed Hussein Alwan

Impact Factor (JCC): 2.9076 Index Copernicus Value (ICV): 3.0
EXPERIMENTAL WORK
Materials
Tests were performed on a freshly prepared sheet of carbon steel (C0.16%, Mn0.5%Si, 0.25%, Cr0.02%).
Specimens were mechanically cut into (3.0 cm 3.0 cm 0.2 cm) dimensions for mass loss tests and 5-mm diameter
electrode embedded in polyester for polarization curves tests. The coupon was abraded with ambry paper abrasive
(400, grit) washed in absolute ethanol and acetone then dried in room temperature and stored in a moisture free desiccator
before their use in corrosion studies.
Inhibitor
Ampicillin Tri-hydrate was used with different concentration (0.001, 0.002, 0.003 and 0.004) M as inhibitor,
figure 1, shows the chemical formula and structure.

Figure 1: Ampicillin Tri-Hydrate Chemical Structures, the Chemical Formula
(C16H19N3O4S) and Molecular Weight 403.42

Solution
The aggressive solutions, 1 M HCl were prepared by dilution of analytical grade 98% HCl with distilled water.
In additional potassium iodide KI was used as additive in this study with concentration (0.001, 0.002and, 0.003) M.
Equipment
Glass equipment (Beaker, Flask, etc.) with different size , water bath (Thermo lab Industries Model H103 10
liter capacity Temp. range 30-90 C), digital balance (Sartorius Model TE214S with accuracy d=0.1 mg),
desiccator, multi-meter (UNI-T UT804), power supply(ZHAOXIN RXN3010D), resistance ( DECADE RESISTANCE
BOX), Calomel reference electrode, graphite electrode.
Gravimetric Measurements
Weight loss measurements were conducted under total immersion using 250 mL capacity beakers containing 200
mL test solution at 313 K maintained in a thermo stated water bath. The carbon steel coupons were weighed and immersed
in aggressive solution at different immersion time (1, 2 and 3) hours, after the adjusted time end, coupon was washed
thoroughly in 20% NaOH brush, rinsed severally in deionized water, cleaned, dried in, and re-weighed. The weight loss, in
grammars, was taken as the difference in the weight of the carbon steel coupons before and after immersion in different
test solutions.
Synergistic Inhibition between Ampicillin Tri-Hydrate and KI for Corrosion of Carbon Steel in 1M HCL Solution 11

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Electrochemical Measurements
Electrochemical polarization tests were carried out by using three-electrode cell arrangement which shown in
figure (2) The specimen was exposed to the solution after it was prepared by polished on a fine grade of ambry paper up to
400 grit and followed by washing with distilled water and finally dried. The circuit was manually composed and the values
of current as well as potential were recorded depending on the variable resistance value employed.
RESULTS & DISCUSIONS
Weight Loss Measurement
Weight loss investigations for carbon steel were done in 1M HCl solution in absenceand presence of inhibitor
(Ampicillin tri-hydrate) as well the additive (potassium iodide KI), The investigations done under add Ampicillin
tri-hydrate with different concentration with and without of Potassium iodide addition, the Ampicillin tri-hydrate
concentrations used are (0.001, 0.002, 0.003 and 0.004) M, while the concentrations of potassium iodide used are
(0.001,0.002 and 0.003) M. Table 1 show the corrosion rate for carbon steel in different solutions, while figure (3) show
weight loss of carbon steel versus time.

Figure 2: Show the Arrangement for the Devices are Used in Investigation
(Corrosion Engineering Lab. Electrochemical Engineering Department)

Figure 3: Vibration of Weight Loss for Carbon Steel with Immersion Time and Different Solution
Results for weight loss measurement show the increasing of corrosion rate with immersion time and decreasing it
by increasing of Ampicillin tri-hydrate concentration and decreased synergistically by increasing of KI concentration, it's
clear that there is a good effect for KI presence in the solution, in other meaning, there is a synergistic effect between
Ampicillin tri-hydrate and KI.
12 Hameed Hussein Alwan

Impact Factor (JCC): 2.9076 Index Copernicus Value (ICV): 3.0
Electrochemical Measurement
Experiments were conducted using a conventional three electrode cell system. The working electrode was carbon
steel sample exposing to corrosive media, a cylindrical graphite electrode and, saturated calomel electrode were used as
auxiliary electrode and reference electrode, respectively. The inhibition efficiency ( %) was evaluated from the obtained
i
corr
values using the following formula:
100 1 100 %

=
un
n i
un
n i n u
i
i
w
i i
(1)
Where i
un
, and i
in
are the corrosion current densities for uninhibited and inhibited condition respectively. For
surface coverage, it was calculated by:

=
un
n i
un
n i n u
i
i
w
i i
1 (2)
Table (2) shows, the polarization data (potential versus logarithmic current density) for carbon steel in HCl
solution in absence and presence of different concentration of inhibitor (Ampicillin tri-hydrate) and additive
(potassium iodide) at 313K, the inhibitor efficiencies were listed in table (2), which calculated according to equation (1),
while the values of surface coverage () are listed in the last column in table (2), which calculated according to
equation (2).
250
300
350
400
450
500
550
600
200 300 400 500 600
-
E

(
m

V
)
Log I ( mA /cm2)
Balnk
Amp 0.001 M
Amp 0.002 M
Amp 0.003 M
Amp 0.004 M

Figure 4: Polarization Curves of Carbon Steel in 1 M HCl Alone and Contained
Different Concentration of Ampicillin Tri-Hydrate at 313 K
200
250
300
350
400
450
500
550
600
200 250 300 350 400 450 500 550 600
-
E

(

m

V
)
Log I ( mA /cm 2)
Blank
0.001 M KI
0.002 M KI
0.003 M KI

Figure 5: Polarization Curves of Carbon Steel in 1 M HCl Alone and Contained
Different Concentration of KI at 313 K
Synergistic Inhibition between Ampicillin Tri-Hydrate and KI for Corrosion of Carbon Steel in 1M HCL Solution 13

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200
250
300
350
400
450
500
550
600
200 300 400 500 600
-
E

(

m

V
)
Log I ( mA / cm2)
Blank
Amp 0.003 M + 0.001 M KI
Amp 0.003 M + 0.002 M KI
Amp 0.003 M + 0.003 M KI

Figure 6: Polarization Curves of Carbon Steel in 1 M HCl Solution with 0.003 M Ampicillin
Tri-Hydrate and Different Concentrations of KI at 313 K
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7

%
KI concentration M
HCl solution + KI
HCl solution +Amp + KI
HCl solution + Amp

Figure 7: Increasing of Inhibition Efficiency by Synergistic Inhibition Effect
between Ampicillin Tri-Hydrate and Potassium Iodide
An increasing in Ampicillin tri-hydrate concentration shift the polarization curves towards more negative potential
for cathodic Tafel lines, and toward more positive potential for anodic Tafel lines , and this lead to decreasing in corrosion
current densities. It's clear from figure (7) there is an increasing in inhibition efficiency.
Absorption Isotherms
The inhibitor could form a thin layer on the metal surface and partly protect it. The protection action of organic
substances during metal corrosion is based on the adsorption ability of their molecules, where the resulting adsorption film
isolates the metal surface from the corrosive medium .Adsorption isotherms are used to understand the mechanism of
corrosion inhibition of metals and alloys. So adsorption isotherms are very important in determining the mechanism
organic electrochemical reaction. [9]
In order to test whether the inhibitor follows the one from adsorption isotherms, the collected data was fitted by
used adsorption isotherm equations. For this study we used the Freundlich adsorption isotherm, which is described by
equation.

n
ads
c K = (3)
C n K
ads
log log log + = (4)
Where C is additive concentration, K
ads
is the adsorptive equilibrium constant representing the interaction of the
14 Hameed Hussein Alwan

Impact Factor (JCC): 2.9076 Index Copernicus Value (ICV): 3.0
additive with the metal surfaceand, is the surface coverage and n is constant, to know the spontaneously of adsorption
process there is require to estimate adsorption free energy, G
ads
.
exp
5 . 55
1


=
RT
G
K
ads
ads
(5)
) K . ( -RT G
ads ads
5 55 ln =

(6)
Where R is universal gas constant; 8.314 J/ mol. K and, T is temperature in K.
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
-0.6 -0.4 -0.2 0 0.2 0.4
L
o
g

Log C ( g / l)
HCl + Amp

Figure 8: Freund Lich Adsorption Isotherms for Ampicillin Tri-Hydrate on
Carbon Steel in 1 M HCl Solution at 313 K
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
-1 -0.8 -0.6 -0.4
L
o
g

Log C ( g / l)
HCl + KI
HCl + Amp + KI

Figure 9: Freund Lich Adsorption Isotherm for KI Alone and with Ampicillin
Tri-Hydrate on Carbon Steel in 1 M HCl Solution at 313 K
From table (3) it is noted that G
ads
, values have negative sign indicating that adsorption process proceeds
spontaneously and increase as the percentage inhibition increase, the high values of adsorption constant K
ads
values suggest
that molecules are strongly adsorbed onto mild steel surface.
Synergism Parameter (Effect of Halide Ions)
The increase of inhibition efficiency of organic compounds in presence of some anions has been observed by
several investigations and was ascribed to synergistic effect. In generally accepted that the presence of halide ions in acidic
media synergistically increases that inhibition efficiency of some organic compounds. It is thought that halide ions are able
to improve adsorption of organic cations by forming intermediate bridge between the positively charged metal surface and
positive end of the organic molecule. [8]
Synergistic Inhibition between Ampicillin Tri-Hydrate and KI for Corrosion of Carbon Steel in 1M HCL Solution 15

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All the experimental results have revealed that the addition of halide ions to the inhibited solution enhances the
inhibition efficiency and the surface coverage, . This behavior is attributed to the synergistic effect between added KI and
Ampicillin tri-hydrate.
To determine the existence of the synergism phenomenon between Ampicillin tri-hydrate and the halide ions,
synergism parameter was evaluated using the equation initially proposed by the Aramaki and Hackermann in 1964 and
reported elsewhere[10]

+
+

=
2 1
2 1
I
1
1

S (7)
Where
2 1 2 1 2 1
+ =
+

+2 1

Measured surface for combination Ampicillin tri-hydrate and, halides ions,


1
and
2
are the surface
coverage for halides ions and Ampicillin tri-hydrate respectively.
S
I
values were greater than unity in all cases, indicating that the enhancement of inhibition efficiency is due to
synergism caused by adding halides ions.
CONCLUSIONS
Based on the above results the following conclusion can be drawn:
It can be considered that Ampicillin tri-hydrate as an efficient inhibitor for carbon steel in 1 M HCl solution and
the inhibitor efficiency increased with increasing Ampicillin tri-hydrate concentration.
The corrosion process is inhibited by adsorption of Ampicillin tri-hydrate on carbon steel surface following
Freundlich adsorption isotherm.
The negative values for free energy for adsorption indicate strong and spontaneous adsorption of Ampicillin
tri-hydrate on carbon steel.
The synergistic effect of KI results from increased adsorption of Ampicillin tri-hydrate.
AKNOWLEDGEMENTS
The author would like to thank the Electrochemical Engineering Department at Babylon University for supporting
and approving this research.








16 Hameed Hussein Alwan

Impact Factor (JCC): 2.9076 Index Copernicus Value (ICV): 3.0
Table 1: Variation of Corrosion Rate Calculated in MPY Unit with Immersion Time and Solution
Time (hrs.) Solution ( Corrosive Media) Corrosion Rate (mpy) 10
-3

1
1 M HCl 6.70
1 M HCl + 0.001 M KI 1.75
1 M HCl + 0.002 M KI 1.55
1 M HCl + 0.003 M KI 0.44
1 M HCl + 0.001 M Ampicillin tri-hydrate 4.56
1 M HCl + 0.002M Ampicillin tri-hydrate 1.55
1 M HCl + 0.003 M Ampicillin tri-hydrate 0.63
1 M HCl + 0.004 M Ampicillin tri-hydrate 1.02
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.001 M KI 1.99
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.002 M KI 1.17
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.003 M KI 1.60
2
1 M HCl 7.60
1 M HCl + 0.001 M KI 2.72
1 M HCl + 0.002 M KI 1.89
1 M HCl + 0.003 M KI 1.87
1 M HCl + 0.001 M Ampicillin tri-hydrate 3.28
1 M HCl + 0.002M Ampicillin tri-hydrate 1.89
1 M HCl + 0.003 M Ampicillin tri-hydrate 0.49
1 M HCl + 0.004 M Ampicillin tri-hydrate 1.70
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.001 M KI 1.72
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.002 M KI 0.56
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.003 M KI 0.41
3
1 M HCl 9.48
1 M HCl + 0.001 M KI 6.04
1 M HCl + 0.002 M KI 3.01
1 M HCl + 0.003 M KI 2.98
1 M HCl + 0.001 M Ampicillin tri-hydrate 9.05
1 M HCl + 0.002M Ampicillin tri-hydrate 2.93
1 M HCl + 0.003 M Ampicillin tri-hydrate 0.44
1 M HCl + 0.004 M Ampicillin tri-hydrate 1.78
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.001 M KI 0.81
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.002 M KI 0.76
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.003 M KI 0.66

Table 2: Polarization Data of Carbon Steel in 1 M HCl Solution in Absence and Presence
of Inhibitor (Ampicillin Tri-Hydrate) as Well Additive Additives (KI)
Solution
- E
corr

mV
I
corr
A/cm
2

c (mV /
dec)
a
(mV / dec)
%
1 M HCl 420 320 470.1 176.0 - -
1 M HCl + 0.001 M KI 415 285 430.1 166.8 11 0.11
1 M HCl + 0.002 M KI 410 253 398.0 136.4 21 0.21
1 M HCl + 0.003 M KI 402 202 392.0 108.8 37 0.37
1 M HCl + 0.001 M Ampicillin tri-hydrate 414 299 509.8 110.3 7 0.07
1 M HCl + 0.002M Ampicillin tri-hydrate 419 243 562.0 104.5 24 0.24
1 M HCl + 0.003 M Ampicillin tri-hydrate 416 211 596.0 113.3 34 0.34
1 M HCl + 0.004 M Ampicillin tri-hydrate 415 189 573.8 137.6 41 0.41
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.001 M KI 422 213 524.7 116.6 33 0.33
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.002 M KI 425 168 482.3 114.9 48 0.48
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.003 M KI 412 113 448.5 114.8 65 0.65









Synergistic Inhibition between Ampicillin Tri-Hydrate and KI for Corrosion of Carbon Steel in 1M HCL Solution 17

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Table 3: Inhibitor Adsorption Constant and Free Energy of Adsorption
for Ampicillin Tri-Hydrate, KI and Both of them on Carbon Steel, Founded
by Use Freund Lich Adsorption Isotherm
Solution
K
ads
Adsorption
Equilibrium
Free Energy
G
ads
kJ/mol
1 M HCl + Ampicillin tri-hydrate 0.255 -6.893
1 M HCl + M KI 1.108 -10.719
1 M HCl + Ampicillin tri-hydrate + M KI 1.209 -10.946

Table 4: Data for Calculation Synergism Parameter (SI), for Solution HCl Contained 0.003
M Ampicillin Tri-Hydrate and KI (Different Concentration)
Solution
1

2

+2 1

S
I

1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.001 M KI 0.34 0.11 0.33 1.43
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.002 M KI 0.34 0.21 0.48 1.78
1 M HCl + 0.003 M Ampicillin tri-hydrate + 0.003 M KI 0.34 0.37 0.65 2.49

REFERENCES
1. Jones Denny A, Principles and prevention of corrosion, 2nd Edition, (1996), Prentice Hall, New Jersey.
2. E. E. Oguzie, Y .Li, F. H. Wang. Studies on the inhibitive effect of Occimumviridis extract on the acid corrosion
of mild steel, Mater. Chem. Phys. 99 (2006) 441-446.
3. S. A. Umoren, I.B. Obot, E. E. Ebenso, N.O. Obi-Egbedi, Synergistic Inhibition between Naturally Occurring
Exudate Gum and Halide Ions on the Corrosion of Mild Steel in Acidic Medium, Int. J. Electro chem.
Sci., 3 (2008) 1029 1043.
4. Alan W. Armoura and Dennis R. Robitailleb, Corrosion Inhibition by Sodium Molybdate, J. Chem. Tech.
Biotechnol. 29 (1979) 619-628.
5. Hameed Hussein Alwan , Adsorption Mechanism for Corrosion Inhibition of Carbon steel on HCl Solution by
Ampicillin Sodium Salt ,IJARET, Vol. 4, Issue 7, November December (2013) 236-246.
6. N. Caliskan and E. Akbas, Corrosion Inhibition of Austenitic Stainless Steel by Some Pyrimidine Compounds in
hydrochloric Acid , Materials and Corrosion , 3 ( 2012), 63
7. A.S.EL-GABER, A.S. FOUDA, A.M. EL DESOKY, Synergistic Inhibition of Zinc Corrosion by Some Anions in
Aqueous media, Ciencia & Tecnologia dos materiais , 20 ( 2008) 3/4 , 71-77.
8. E.Ouzie , Y. Li , W.H. Wang, Corrosion Inhibition and Adsorption Behavior of Methionine on Mild Steel in
Sulfuric Acid and Synergistic effect of iodide ion , Journal of Colloid and Interface Science , 310 ( 2007) 90-98.
9. E.E. Ebenso, N.O. Eddy, A.O. Odiongenyi, Corrosion Inhibition and Adsorption Properties of Methocarbamol on
Mild Steel in Acidic Medium , Portugaliae Electro chimica Acta,27( 2009) 13-22
10. Nnabuk O. Eddy 1, Eno E. Ebenso. Adsorption and Quantum Chemical Studies on Cloxacillin and Halides for the
Corrosion of Mild Steel in Acidic Medium, Int. J. Electrochem. Sci., 5 (2010) 731 750.