Chapter Five Corrosion inhibitors

5.1 General
Corrosion of metallic surfaces can be reduced or controlled by the
addition of chemical compounds to a metal surface or to its corrosive
environment. This process of corrosion control called inhibition and the
compounds added are known as corrosion inhibitors. Usually inhibitors can
reduce the rate of either anodic oxidation or cathodic reduction, or both, by
forming a protective film on the surface of the metal. It has been postulated
that the inhibitors are adsorbed into the metal surface either by physical
(electrostatic) adsorption or chemisorption (91).

Physical adsorption is the result of electrostatic attractive forces between the

ions of inhibitor and the electrically charged metal surface. While
Chemisorption is the transfer, or sharing of the inhibitor molecule’s charge to
the metal surface, forming a coordinate-type bond. The efficiency of these
inhibitors depends on the nature and the state of the metallic surfaces,
chemical composition and structure of the inhibitor. Thus polar organic
compounds are adsorbed on the metal surface (M) forming a charge transfer
complex bond between their polar atoms and the metal. The size, orientations,
shape and electric charge on the molecule can be determine the degree of
adsorption and hence the effectiveness of the inhibitor(92). In the present
study, the prepared compounds D, E, F, G and H were evaluated as corrosion
inhibitors by using two technique Tafel plot and Electrical Impedance
Spectroscopy.

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5.2 Experimental
5.2.1 The Composition of Alloys

Two types of alloys were used in this study, the first was carbon steel
(C1010) standard strips obtained from Alabama company, and the second was
Aluminum alloy 2024,T4 standard sheet which was obtained as square pieces
taken from Michigan state university, the composition of those alloys are
illustrated in Table (5-1).

Table (5-1) Chemical Composition of Carbon Steel and Aluminum Alloys

Alloy Composition % w/w

Carbon C Mn P S Si Ni Cr Cu As Fe
steel 0.0 0.0 0.
0.13 0.3 0.37 0.3 0.1 0.08 Residue
(C1010) 4 5 3
Aluminum Ti Mn Fe Zn Si Mg Cr Cu other Al
2024,T4 0.2 3.
0.15 0.3 0.5 0.5 1.8 0.1 0.15 90.7-94.7
5 8

5.2.2 Preparing the Metal Specimen for Test

A standard strips of carbon steel (C1010) is shown in Figure (5-1A) with

dimensions of 3cm length, 1.24cm widths and 0.14 cm thicknesses. The total
area of immersed strip is 8.45cm2. Carbon steel strips were used to evaluate
the prepared compounds as corrosion inhibitors. The faces of each specimen
were grind and polished by emery cloth paper to 400µ. Then specimens
degreased with acetone, and washed with distilled water and ethanol. Hot air
were used to dry the sample and stored in a desiccators containing silica gel
during the period in between polishing and Tafel measurements.

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The specimens of Aluminum alloy 2024, T4 are shown in Figure (5-1B), they
cuts to small square pieces (1cm × 1cm). Before the corrosion tests each
specimen was grind and polished by 1500 grade resin paper, then ultrasonic
water bath used to clean samples before they re-polished with 0.3μm Micro
Polish Alumina powder until the metal surface become glossy an shiny.
Afterward the specimens immersed in distilled water in ultrasonic bath for 10
mint and dried with nitrogen gas. The specimens were stored under nitrogen
in a desiccator.

Figure (5-1): The Specimens Alloys; (A) Carbon Steel, (B) Aluminum

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5.2.3 The Corrosive Environments

In The present study, the corrosion inhibiter efficiency of new amine

compounds on carbon steel was measured by using formation water from
Iraqi Southern Oil Company as corrosive environment. The compositional
analyses of formation waters carried out in south oil company /Basrah , as
shown int ables (5-2) and (5-3).Tafel plot technique was used for this purpose,
these measurements carried out in Chemistry department / Collage of science
/ University of Basrah. Also the corrosion inhibiter efficiency of the new
amine compounds had been tested on Aluminum alloy in slain medium by
using a standard 0.5M Sodium thiosulfate solution. EIS Impedance used for
these measurements at Chemistry department / Michigan State University.

Table (5-2): Analysis for the Formation Water

Total suspended Salinity Conductivity TDS pH

Solid TSS (ppm) (Ω-1) (ppm)
(ppm)
160.8 374000 4340000 217000 6.6

Table (5-3) Ions Concentration (ppm) in Formation Water

Ca+2 Mg+2 Na+ K+ Cl- HCO3- SO4-2

150 2975 471 110 11260 82 200

5.2.4 The Electrochemical Cells

For Tafel method, the electrochemical test cell was arranged as shown in
Figure (5-2A). The cell consists of 50mL vessel connected with three types of
electrodes as following:

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1- The working electrode (carbon steel specimen).
2- The Reference electrode (Silver in AgCl solution)

3- Counter electrode (Platinum)

For EIS Impedance method, the arrangement of the test cell is shown in
Figure (5-2B). The cell consists of 25mL Pear-shaped vessel with three necks
as following:

1- The working electrode (polished Aluminum specimen).

2- The Reference electrode (Silver in AgCl solution)

3- Counter electrode (Platinum )

Figure (5-2) Electrochemical Cells; (A) Tafel Plot , (B) Impedance

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5.3 Experimental Procedure for Tafel Plot Method

Tafel experiment set up is shown in Figure (5-3). A potentiostat was used
to measure current density vs electric potential in order to calculate the
corrosion rates. The instrument performs different techniques such as
potentiodynamic polarization scan, Tafel plots, linear polarization scan and
other specialized measurements techniques.

Figure (5-3): Corrosion Measurements Instrumentation Set up

5.3.1 Corrosion Rate of Formation Water

The "Tafel plots" experiment used to measure the corrosion rates of

formation water by determined the open Circuit Potential (OCP) value and
then determined Linear Sweep Voltammetry (LSV) by added ±0.5V to OCP
value and then recording potential vs. log current functional at stagnant
condition. Corrosion cell kept at constant temperature (room Temp). by
placing it in a thermostatic water bath. the Tafel plots choose for evaluation of
inhibitors because they quickly present corrosion rate information. The linear

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portion of anodic or cathodic polarization log current vs. potential plot is
extrapolated to linear sector of the corrosion potential line. This permits rapid
and high accuracy measurements of the extremely low corrosion rates
(0.001mpy).

From table (5-3) and figure (5-4) ,the formation water causing corrosive of
carbon steel due to contained the ions as shown in table (5-3), this ions made
the formation water behaves as a saline electrolyte causing corrosion of
carbon steel alloy with corrosion rate 9.5078 mpy.

Figure (5- 4): Tafel Plot of Formation Water without Inhibiter

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5.3.2 Corrosion Rates of Carbon Steel in Formation Water as a Function

of Inhibitor Concentrations at Constant Temperature.

The electrochemical results obtained from polarization experiments

through "Tafel plots" performed in corrosive environment (formation water)
in the absence and presence of different additives at the specified
concentration (from 5ppm to 30ppm) are showed in Tables (5-3) to (5-7) .
The corrosion rate of formation water with adding different concentrations
of compounds (D, E, F, G and H) had been measured at the same method in
section (5.3.1) at constant temperature 260C. Corrosion rate (CR) was
measured in (mm/y) units, and to convert corrosion rate (CR) from (mmy) to
(mpy), equation (5-1) were used (120):

CR/mpy = 0.0254 mm/y ……………. (5-1)

5.4 Results and Discussion

Tafel plots employed for rapid evaluation inhibitors in order to

determine their effectiveness on the corrosion rates of carbon steel.From
Tables (5-4) to (5-7) and figures (5-5) to (5-9), the prepared compounds (D,
E, F, G and H) shown high inhibition efficiency for corrosion rate, Ecorr and
Icorr of carbon steel in formation water after added various concentrations.
From this results, the inhibition efficiency was different from one compound
to other due to different in their structures and the inhibition efficiency was
different in the same compound due to different in the concentrations .

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5.4.1 The Effect of Inhibitors Structures on Corrosion Rate of Carbon
Steel

The organic inhibitors affect the entire surface of a corroding metal when
present in sufficient concentration. Organic inhibitors will be adsorbed
according to the ionic charge to the inhibitor and the charge on surface.
Cationic inhibitors such as amines will be adsorbed preferentially depending
on the metal if charged positively. The strength of the adsorption bond is the
dominant factor for soluble organic inhibitors(107). Organic compounds
containing polar groups including nitrogen, sulfur, oxygen that inhibit the
metal surface due to their interaction with the metal surface via their
adsorption. Polar functional group is regarded as the reaction center that
stabilizes the adsorption process. The adsorption of an inhibitor on a metal
surface depends on many factors such as the nature as well as the surface
charge of the metal, the adsorption mode, its chemical structure and type of
electrolyte solution. In present study the inhibitors compounds divided into
two groups ; the first group belong to (EDA) like (D, F, H ). belong to (EA)
like ( E, G).

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The corrosion inhibition effect of compounds ( D, E, F, G, H) can be

attributed to chemisorption effect which can be identifying by the presence of
double bond (C=O), N-atom and O-atoms of hydroxyl groups in (H)
compound. Those factors made the inhibitors compounds ready to chelat with
Fe atom in CS surface via the lone pairs of both N and O atoms and π-
electrons of double bond of the new inhibitors bonded with Fe atoms by their
interaction with d-orbital of Fe atoms to form film which induce great
adsorption of the inhibitor molecules onto the surface of CS, leading to the
formation of a corrosion protecting film (108). From Table (5-9) the higher
efficiency value among those five inhibitors were equal to 98% and 97%of
compounds (F) and (D) respectively this due to the structure dendrimers
polymer with four amino end group lead to presence of more electron donor
groups of (N) atoms in the molecular structure. The presence of more free
electron pairs lead to increasing the adsorption of compounds (F) , (D) and
increasing inhibition efficiency . The compound (H) have polymeric structure
and have more of amino groups, but showed less inhibition efficiency thane
with compounds (F) and (D) due to steric effect leads to decreasing the
adsorption efficiency and decreasing the polarization resistance (Rp) lead to
increasing Icorr and decreasing inhibition efficiency.

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5.4.2 The Effect of Inhibitors Concentrations on Corrosion Rate

The corrosion rates of CS studied as a function of concentrations by using

different concentrations of inhibitors (5ppm- 30ppm) as shown in tables (5-4)
to (5- 8) . From these results, the corrosion rate reduced as concentration
increases.

For compound (D), Table (5-4) shows the optimum inhibition concentration is
20 ppm with efficiency 97% as in Table (5-9), whereas at lower (D)
concentration a decrease in efficiency can be observed due to its chemical
structure, in 5-15ppm (D) has lower solubility and that leads to a less
adsorption of (D) on metal surface lead to increasing Icorr then reduce its
efficiency. In high concentration (25-30ppm) the increasing of (D) molecules
which have a large chain that caused a steric hindrance on metal surface leads
to a difficulty in its adsorption process lead to increasing Icorr then reduce its
inhibition efficiency(133).For other compounds (E, F, G, H) followed the same
discussion to explain the concentration on inhibition efficiency. On the other
hand , the βc of compound (D) (Table(5-4) ) is larger than βc of Blank this
shows that compound (D) behaves as mixed inhibitor. The other inhibitor
compounds (E,F,G,H) acting as cathodic inhibitor resembles comound (D) as
showed in tables (5-6) to(5-7).

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Table (5-4) Corrosion Inhibiter for Compound D

Conc. Ecorr Icor CR CR βc βa Rct

(ppm) ( V) ( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
E-6 E-3 E+3
0 -0.94 224.0 241.5 9.5078 -9.191 7.117 0.1147
5 -0.50 7.823 8.436 0.3321 -6.566 4.732 3.284
10 -0.46 9.963 10.74 0.4228 -6.385 5.225 2.579
15 -0.47 6.182 6.667 0.2624 -5.854 5.092 4.156
20 -0.50 5.862 6.322 0.2488 -6.517 3.690 4.383
25 -0.44 16.45 15.80 0.6220 -6.091 4.671 1.753
30 -0.43 13.00 14.02 0.5519 -6.954 4.514 1.977

Figure (5-5) Tafel plot with Optimum Value (20ppm) of Inhibitor D

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Table (5-5) Corrosion Inhibitor for Compound E

Conc. Ecorr Icorr CR CR βc βa Rct

(ppm) ( V) ( A) E-6 (mm/year) (mpy) (A/V) (A/V) (ohm)
E-3
0 -0.94 224.0 241.5 9.5078 -9.191 7.117 0.1147
5 -0.5 28.64 30.88 1.2157 -5.819 5.638 0.897
10 -0.46 20.75 22.38 0.8811 -5.997 5.759 1.238
15 -.047 34.06 36.73 1.4460 -5.987 5.655 0.754
20 -.047 26.82 28.92 1.1385 -5.888 5.502 0.958
25 -0.52 14.67 15.82 0.6228 -5.879 6.056 1.752
30 -0.43 13.28 14.33 0.5641 -6.918 5.890 1.934

Figure (5- 6): Tafel plot with Optimum Value (30ppm) of Inhibiter E

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Table (5-6) Corrosion Inhibiter for Compound F

Conc E corr Icorr CR CR βc βa Rct

(ppm) ( V) ( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
E-6 E-3 E+3

0 -0.94 224.0 241.5 9.5078 -9.191 7.117 0.1147

5 -0.5 4.468 4.818 0.1896 -5.369 5.060 5.750

10 -0.44 15.09 16.28 0.6409 -6.265 5.879 1.702

15 -0.44 12.89 13.90 0.5472 -6.324 5.234 1.994

20 -0.44 12.65 13.64 0.5370 -6.480 5.208 2.032

25 -0.49 3.138 3.383 0.1331 -6.337 6.367 8.189

30 -0.47 8.668 9.347 0.3679 -7.100 5.277 2.964

Fig (5-7) Tafel plot with Optimum Value (25ppm) of Inhibiter F

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Table (5-7) Corrosion Inhibiter for Compound G

Conc E corr Icorr CR CR βc βa Rct

(ppm) ( V) ( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
E-6 E-3 E+3

0 -0.94 224.0 241.5 9.5078 -9.191 7.117 0.1147

5 -0.407 16.08 17.34 0.6826 -5.907 5.857 1.598
10 -0.36 17.06 18.39 0.7240 -6.009 5.656 1.506
15 -0.33 14.98 16.15 0.6358 -5.954 5.268 1.716
20 -0.349 20.57 22.18 0.8732 -5.909 5.432 1.249
25 -0.51 44.74 48.24 1.8992 -5.888 5.525 0.574
30 -0.38 22.01 23.74 0.9346 -6.068 5.486 1.167

Figure (5-8) Tafel plot with Optimum Value (15ppm) of Inhibitor G

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Table (5-8) Corrosion Inhibiter for Compound H

Conc E corr Icorr CR CR βc βa Rct

( V) ( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
(ppm) E+3
E-6 E-3

0 -0.94 224.0 241.5 9.5078 -9.191 7.117 0.1147

5 -0.5 21.03 22.68 0.8929 -7.955 2.242 1.222

10 -0.5 29.12 31.40 1.2362 -6.802 6.340 0.882

15 -0.5 7.819 8.432 0.3319 -5.598 6.474 3.286

20 -0.42 8.315 8.967 0.3530 -7.281 5.853 3.090

25 -0.44 15.61 16.83 0.6625 -6.110 5.268 1.646

30 -0.55 15.09 16.27 0.6405 -6.388 5.926 1.703

Figure (5-9) Tafel plot with Optimum Value (15ppm) of Inhibiter H

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Table (5- 9) The Optimum Values and Corrosion Efficiency of Inhibitors

Comp Optimum Optimum Optimum CR efficiency Rct

conc CR CR % (ohm)
(ppm) (mm/y) (mpy) E+3
E-3
D 20 6.32 0.2488 97 4.383
E 30 14.33 0.5641 94 1.934
F 25 3.383 0.1331 98 8.189

G 15 16.15 0.6358 93 1.716

H 15 8.432 0.3319 96 3.286

5.5 The effect of Increasing Temperature on Corrosion Rate

The effect of temperature on inhibition efficiency of the inhibitors on both

CS alloy can be studied depending on two principles, the first principle
include that increasing the efficiency as decreasing in temperature this due to
physical adsorption mode for the inhibitor on the surface of metal or alloy,
and the second principle include that increasing the efficiency as temperature
increase result from chemical adsorption mode for the inhibitor on the surface
of metal or alloy.

The effect of temperature on the corrosion rate of CS in presence of this

group as corrosion inhibitors were studied in the temperature range (10-40ºC)
using Tafel plot measurements. In this study the effect of temperature on
inhibitor properties and corrosion inhibitor for CS and alloy was studied at
range (30-50ºC) as shown in tables (5-10) to (5-14) and Figures (5-10) to (5-
14).

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Those tables show that these inhibitors have some effects on both, the
cathodic and anodic processes. This indicates a modification of the
mechanism of cathodic hydrogen evolution as well as anodic dissolution of
iron, which suggests that the above inhibitors can be, inhibited the corrosion
process of CS, and their suppression of cathodic process by the covering of
CS surface with monolayer due to the adsorbent of inhibitors molecules. It
can also be that anodic Tafel constant (βa) slopes has variation values
between increasing and decreasing values whereas the decreasing may be
described to the changes in charge transfer resistance. From figure (5-10) and
table(5-10), the compound D shown that the increasing corrosion rate with
increasing the temperature as well as increasing in Icorr lead to decreasing Rct
and decreasing inhibition efficiency and decreasing in both βa and βc with
increasing temperature refers to increasing in both anodic and cathodic
reactions respectively. The decreasing in inhibition efficiency as temperature
decreased can be interpreted due to that desorption is aided by increasing the
corrosion . Also decreasing in efficiency as temperature increased result from
decreasing in viscosity of the inhibitor solution then increasing the diffusion
of ions in solutions and decrease the stability of protective film on metal
surface that leads to decrease the activity of the inhibitor(119). Increasing
temperature also increase the diffusion of ions in solutions and decrease the
stability of protective film on metal surface which leads to decrease activity of
the inhibitor(119). The increasing efficiency with increasing temperature can be
observed in Figure (5-10) at 45C₀, the adsorbed by chemical mode due
increasing efficiency with increasing temperature, where CR decreased as
temperature increased due to chemical adsorbed for inhibitor(D). the shifting
in Ecorr value toward positive direction can be shown in Figure (5-
10).Inhibitor (D), has increasing in efficiency as temperature increased, where
CR decreased as temperature increased due to chemical adsorbed for inhibitor
(D). These results would indicate that hydrogen evolution reaction was

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controlled, but the addition of the inhibitor did not modify the mechanism of
proton discharge reaction.

Table (5-10) Effect temperature on Corrosion Rate of Compound D at

Optimum Value (20ppm)

Temp E corr Icorr CR CR βc βa Rct

(C₀ ) ( V) ( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
E-6 E-3 E+0 E+0 E+3

30 -0.47 8.293 8.943 0.3520 -6.480 5.070 3098

35 -0.45 20.71 22.33 0.8791 -6.006 5.494 1.241

40 -0.49 20.92 22.56 0.8881 -5.999 5.699 1.228

45 -0.39 4.512 4.866 0.1915 -5.71 5.717 5.694

50 -0.41 12.09 13.03 0.5129 -6.363 5.674 2.126

Table (5-11) Effect temperature on Corrosion Rate of Compound Eat

Optimum Value (30ppm)

Temp Ecoor Icorr CR CR βc βa Rct

( V) ( A) (mm/year (mpy) (A/V) (A/V) (ohm)
(C₀ ) E+3
E-5 ) E-2 E+0 E+0

30 -0.45 2.485 2.680 1.0551 -6.164 5.448 1.034

35 -0.41 2.356 2.541 1.0003 -6.049 5.107 1.090

40 -0.40 1.396 1.506 0.5929 -6.395 5.758 1.840

45 -0.455 2.068 2.230 0.8779 -5.814 5.625 1.242

50 -.0328 2.163 2.333 0.9185 -6.022 5.446 1.188

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Table (5-12) Effect Temperature on Corrosion Rate of Compound F at
Optimum Value (25ppm)

Temp E corr Icorr CR CR βc βa Rct

( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
(C₀ ) ( V) E+3
E-5 E-2 E+0 E+0

30 -0.46 0.9178 0.9897 0.3896 -6.356 4.016 2.800

35 -0.448 2.537 2.736 1.0771 -5.888 5.515 1.013

40 -0.413 2.604 2.808 1.1055 -5.832 5.486 0.986

45 -0.388 1.089 0.9534 0.3753 -6.146 5.923 2.906

50 -0.409 2.128 2.294 0.9031 -6.331 5.567 1.208

Table (5-13) Effect Temperature on Corrosion Rate of Compound G at

Optimum Value (15ppm)

Temp E corr Icorr CR CR βc βa Rct

( V) ( A) (mm/year) (mpy) (A/V) (A/V) (ohm)
(C₀ ) E+3
E-5 E-2 E+0 E+0

30 -0.432 1.300 1.402 0.5519 -6.954 4.514 1.977

35 -0.454 1.439 1.552 0.6110 -5.919 5.233 1.786

40 -0.595 1.653 1.783 0.7019 -5.956 5.890 1.553

45 -0.520 1.467 1.582 0.6228 -5.879 6.056 1.752

50 -0.856 29.07 31.35 12.3425 -3833 1.084 0.088

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Table (5-14) Effect Temperature on Corrosion Rate of Compound H at
Optimum Value(15ppm)

Temp E corr Icorr CR CR βc βa Rct

( A) (mm/year) (A/V) (A/V) (ohm)
(C₀ ) ( V) (mpy) E+3
E-5 E-2 E+0 E+0

30 -0.443 0.7449 0.8032 0.3162 -6.406 5.021 3.449

35 -0504 2.802 3.022 1.1897 -6.069 5.388 0.916

40 -0.626 4.264 4.598 1.8102 -5.760 5.494 0.6026

45 -0.438 1.851 1.996 0.7858 -5.888 5.587 1.388

50 -0.592 3.150 3.397 1.3374 -5.842 5.536 0.8156

Figure (5-10) Effect of the Temperature on Corrosion Rate for

Compound D

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Figure (5-11) Effect of the Temperature on Corrosion Rate for

Compound E

Figure (5-12) Effect of the Temperature on Corrosion Rate for

Compound F

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Figure (5-13) Effect of the Temperature on Corrosion Rate for

Compound G

Figure (5-14) Effect of the Temperature on Corrosion Rate for

Compound H

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5.6 Experimental Procedure for EIS Impedance Method

Potentiostat/Galvanostat/ - Reference 600 supplied by GAMRY
instruments company in USA at chemistry department – Michigan state
university showed in Figure (5- 15) was used to determined corrosion
efficiency by measured the impedance.

Fig (5-15) EIS Impedance Instrumentation

Fig (5-17) Electrical Equivalent Circuit Used to fit the Impedance data

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5.6.1 Measured EIS Impedance for Corrosive Environment without
Inhibitor

The EIS impedance measured by adding 25mL of 0.5M sodium

thiosulfate as corrosive environment to the electrochemical cell with
Aluminum alloy 2024, T4 as working electrode, as showed in Figure (5-2, B).
The measurement of the open Circuit Potential (OCP) was the first step and
then linear EIS impedance selected as shown in Figure (5-15).

Impedance measurements of the Aluminum alloy were conducted at the

respective corrosion potentials after 2.0 h of immersion in uninhibited and
inhibited aerated solutions of 0.5M Na2S2O3. Figure (5-16) is shown the
impedance plots (Bode plots) for Aluminum alloy in aerated 0.5M Na2S2O3
solutions in the absence of inhibitor at 25oC. The impedance parameters of the
charge-transfer resistance (Rct), the maximum frequency (fmax) and the double
layer capacitance (Cdl) have been calculated.

The principle of EIS impedance depends on the charge-transfer resistance

of the interfacial corrosion reaction (Rct),. When (Rct), value is high it leads to
decreasing in the corrosion current Icorr and corrosion rate, but when (Rct)
value small it was rising to Icorr and subsequently the corrosion rate according
to following equation(138) :

Z = E/I ………. (1-2)

Figure (5-16) shows that the Aluminum alloy has Rct of about (0.09E-4Gohm)
which is reveals it has a highly corrosion rate.

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Figure (5-16) EIS Impedance for 0.5M Sodium Thiosulfate

5.6.2 The effect of adding Different Concentrations ofInhibitors on EIS

Impedance for Corrosive Environment.

The effect of inhibitors concentration of compounds (D, E, F, G and H),

and the inhibitors efficiency were studied by added (5ppm -30ppm) of those
inhibitors to the corrosive environment (0.5M sodium thiosulfate) in the
electrochemical cell then Impedance measurements of the Aluminum alloy
were conducted at the same procedure in section (5.4.1). The results are listed
in Table (5-15). The inhibition efficiency (IE) was estimated from the
measured charge-transfer resistance, Rct values using the relation (140):

(%) = × 100 ……… (5-3)

Where ( R0ct) and (Rct) are the charge-transfer resistance values in the absence
and presence of the inhibitor, respectively.
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Figures (5-18) to (5-22) showed impedance plots recorded for Aluminum
alloy in aerated 0.5M Na2S2O3 solutions in the presence of optimum inhibitor
concentration in compered with the blank. The inhibition efficiency was
evaluated by Rct of the impedance. The more densely packed the inhibitor
surface film, the larger the diameter of the Bode plots related to Z mode in
ohm, which results in higher Rct with low Icorr and corrosion rate lead to high
inhibition efficiency.

From Table (5-15) compound D, indicate that the values of Rct increase by
increasing the inhibitor concentration. At 5ppm, compound D has the highest
Rct value of 1Gohm with 99.99% inhibition efficiency. Also Figure (5-18)
shows that clearly in compare with the blank.

Compound E has also inhibition effect on the Aluminum alloy in aerated

0.5M Na2S2O3 solution in different concentrations as shown in Table (5-16).
The optimum inhibition occurs at 15 and 20ppm with 98.87% in efficiency.
Figure (5-20) is representing the comparison between the presence of 15ppm
of compound (E) and the blank.

The results of compound (F) are listed in Table (5-17) and Figure (5-20)
shows the plot of the optimum concentration of compound (F) 10 ppm with
efficiency of 99.9%.

Compound (G) showed maximum inhibition efficiency of 99.88% in Table

(5-18) and this result was plotted in Figure (5-21).

EIS study of compound (H) as inhibitor for Aluminum alloy in aerated 0.5M
Na2S2O3 solution is summarized in Table (5-19). The optimum concentration
of compound (H) was at 10ppm with 99.85% efficiency. Figure (5-22) is
representing the comparison between the presence of 10ppm of compound
(H) and the blank.

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 Chapter Five Corrosion inhibitors
From the above results it can be notice that the all prepared compounds has
great inhibition efficiency on Aluminum alloy in aerated 0.5M Na2S2O3
solution and the optimum concentrations of those compounds are listed in
Table (5-20).

Compounds (D) have highest inhibition efficiency at low concentration of

5ppm and this due to the adsorption of compound (D) in small portion on the
metal surface that leads to the formation of double layer between the charged
metal surface and the solution, this double layer work as an electrical
capacitor. The adsorption of compound (D) on the electrode surface decreases
its electrical capacity because they displace the water molecules and other
ions originally adsorbed on the surface (140). The thickness of this protective
layer increases with increase in inhibitor concentration, since more (D)H+
cations electrostatically adsorb on the electrode surface resulting in a

noticeable decrease in Cdl . The values of electrochemical double layer

capacitance Cdl were calculated at the frequency fmax, at which the imaginary
component of the impedance is maximal (−Zmax phase) by the following
equation(140):

= ……….. (5-4)

But some time found that when increasing concentration of the other
compound it was leads to decreasing in Rct and inhibition efficiency, as
showed in Table (5-15) of compound D at concentration 10ppm the Rct is 3E-
4 Gohm, and at 25 ppm is 5E-4 Gohm. This was happened due to a high
concentration of compound (D) cause increasing in compound molecules
which have a large chain that might caused a steric hindrance on metal
surface, and leads to a difficulty in its adsorption process and then reduce the
double layer (protective layer) between the charged metal surface and the
solution. Also it will increases its electrical capacity and increase in Cdl

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 Chapter Five Corrosion inhibitors
subsequently decreasing Rct , decreasing inhibition efficiency and increasing
corrosion rate(141).

Table (5-15)The Effect Increasing Concentration of Inhibitor D on EIS

Impedance

Conc Rct (Gohm) E-4 R₀ct(G ohm) E-4 IE (%)

(ppm)
0 - 0.09 -
5 20000 - 99.99
10 3 - 97.00
15 8 - 98.87
20 10 - 99.10
25 5 - 98.20
30 10 - 99.10

Figure (5-18) EIS for D Inhibitor at Optimum Value (5ppm)

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 Chapter Five Corrosion inhibitors
Table (5-16) The Effect Increasing Concentration of Inhibitor E on EIS
Impedance

Conc(ppm) Rct (Gohm) E-4 R₀ct(G ohm) E-4 IE (%)

0 - 0.09 -

5 1 - 91.00

10 0.9 - 90

15 8 - 98.87

20 8 - 98.87

25 1 - 91.00

30 1 - 91.00

Figure (5-19) EIS for E Inhibitor at Optimum Value (15ppm).

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 Chapter Five Corrosion inhibitors
Table (5-17) The effect of increasing Concentration of Inhibitor F on EIS
Impedance

Conc (ppm) Rct (G ohm) E-4 R₀ct( G ohm) E-4 IE (%)

0 - 0.09 -

5 6 - 98.5

10 1000000 - 99.99

15 1000000 - 99.99

20 0.8 - 88.75

25 100000 - 99.99

30 0.7 - 87.14

Figure (5-20) EIS for F Inhibitor at Optimum Value (10ppm)

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 Chapter Five Corrosion inhibitors
Table (5-18) The effect of Increasing Concentration of Inhibitor G on EIS
Impedance

Conc (ppm) Rct (G ohm) E-4 R₀ct (G ohm) E-4 IE (%)

0 0.09 -

5 3 - 97.00

10 80 - 99.88

15 7 - 98.71

20 7 - 98.71

25 10 - 99.10

30 10 - 99.10

Figure (5-21) EIS for G Inhibitor at Optimum Value (10ppm)

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 Chapter Five Corrosion inhibitors
Table (5-19) The effect of Increasing Concentration of Inhibitor H on EIS
Impedance

Conc (ppm) Rct (G ohm) E-4 R₀ct (G ohm) E-4 IE (%)

0 0.09 -

5 9 - 99.00

10 70 - 99.85

15 0.9 - 90

20 0.7 - 87

25 0.3 - 70.00

30 10 - 99.10

Figure (5-22) EIS for H Inhibitor at Optimum Value (10ppm)

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Chapter Five Corrosion inhibitors

Table (5-20 ) Optimum Inhibition Efficiency of Inhibitor Compounds

Comp Optimum Optimum Rct Optimum Cdl

Conc (ppm) ( G ohm) E-4 IE % µF, E-7

D 5 20000 99.99 0.265

E 15 8 91.00 39800

F 10 1000000 99.99 0.398

G 10 10 99.10 3980

H 10 70 99.85 1590

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