NACE Paper No.

MECCOCT18-12340

EFFECT OF IODIDE IONS ON PERFORMANCE OF QUATERNARY AMINE CORROSION

INHIBITORS WITH VARIABLE HYDROCARBON CHAIN LENGTH

Ali A. Al-Taq Yahya T. Al-Janabi

Saudi Aramco/EXPEC ARC Saudi Aramco/R&DC
Dhahran Bolivar Dhahran Bolivar
Dhahran, Eastern Province, 31311 Dhahran/Eastern Province, 31311
Saudi Arabia Saudi Arabia

Shaikh A. Ali Hussain A. AlAbbas

King Fahd University of Petroleum and Mineral Saudi Aramco/EXPEC ARC
Chemistry department Dhahran Bolivar
Dhahran-Jubail Dhahran, Eastern Province, 31311
Dhahran/Eastern Province, 31261 Saudi Arabia
Saudi Arabia

ABSTRACT

The inhibition of coiled tubing steel corrosion in different hydrochloric (HCl) acid concentrations by
quaternary amine with variable hydrocarbon chain lengths ranging from 10 to 16 carbons and having
multiple adsorption sites was examined using a gravimetric method and electrochemical techniques
(Tafel plot). The effect of iodide ions on the performance of these corrosion inhibitors was investigated
as a function of acid concentration and temperature. Weight loss tests were conducted in 5 and 28 wt%
HCl acid at different temperatures and soaking times. The temperatures examined ranged from 86 to
194 oF. Tafel plot measurements were conducted for mild steel in inhibited/uninhibited 1 M HCl acid
solutions with and without iodide ions, and at temperatures of 86 and 194 oF. The results showed that
the inhibition efficiency (IE) of quaternary amine corrosion inhibitors increased significantly in the
presence of iodide ions at high acid concentration/temperature (28 wt% HCl and 194oF), indicating
synergistic effects. Minimum impact (no synergism) was observed for iodide ions at mild conditions (at
a temperature of 86 oF and HCl acid concentration of 5 wt%). Tafel plot measurements showed that the
quaternary amine corrosion compounds inhibit acid attack by either anodic or mixed-type mechanism.
This paper will present in detail the performance of quaternary amine corrosion inhibitors with/without
iodide ions as a function of acid concentration and temperature; and will discuss the potential inhibition
mechanisms.

Key words: Synergistic, Quaternary amine, Corrosion inhibitors, HCl acid, Iodide ions, gravimetric,
electrochemical.

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 INTRODUCTION

Organic compounds with heteroatoms, such as sulfur, oxygen and nitrogen are effective corrosion
inhibitors for low carbon steel in acidic media. These organic compounds usually contain multiple bonds
and hydrophobic tail to enhance their IE. Inhibition of these compounds can be enhanced significantly
using halide ions. This type of interaction is called synergism. Synergistic inhibition is an effective mean
to improve the inhibitive force of the inhibitor, to decrease the amount of usage and to diversify the
application of the inhibitor in acidic media.1 Ridhwan et al., (2012)2 investigated the inhibitive effect of
mangrove tannin in presence/absence of halide ions on mild steel corrosion in 0.5 M hydrochloric acid.
They found that the synergistic effect increased in the order of Cl<Br<I. Solmaz et al., (2008)3 attributed
the different behavior of halide ions to the difference in radii. For example, the iodide ion with a radius
of 2.2 Å is more predisposed to adsorption than the bromide ion with a radius of 1.96 Å or the chloride
ion with a radius of 1.81 Å. Because of the larger ionic radius, the iodide ion has higher hydrophobicity
as compared to the other two halide ions. The adsorption of iodide ions onto the metal surfaces will
decrease the hydrophilicity of the metal surfaces, which is likely to promote the adsorption of organic
molecule in place of the water molecules.4 Al-Taq et al., (2011)5 found that iodide ions exhibited the
best synergism with a diamine inhibitor compared to bromide and chloride ions. They found that the
chloride ions tended to induce more corrosion at high temperature/acid concentration (HCl = 28 wt%
and T = 220 oF).

Coiled tubing (CT) is used typically during matrix or acid frac treatments to inject highly corrosive fluids
(e.g., HCl up to 31 wt%) directly into the target zones/formations bypassing casing and completion
hardware. Tubing internal diameters normally range from ¾” to 4” and single reel tubing lengths in
excess of 9 km are available commercially.6 Lack of an efficient inhibitor will result in deterioration of CT
steel and generation of huge amounts of iron ions which may precipitate as iron
oxides/hydroxide/sulfide and thus damaging formation permeability. The coupons used in the weight
loss part of this study were machined from a CT piece.

The objective of this work was to assess the performance of synthesized quaternary ammonium salts
as corrosion inhibitors in presence/absence of iodide ions. The synergistic effect was assessed
between these inhibitors and iodide ions as a function of temperature (86 and 194 oF) and HCl acid
concentration (5 and 28 wt%) using gravimetric and electrochemical methods.

EXPERIMENTAL STUDIES
Materials
The primary starting materials used in the synthesis of these compounds of interest in this study were:
1,dodecylamine,1-bromodecane and propargyl bromide. Hydrochloric acid solutions of 28 wt. % were
prepared from ACS concentrated HCl using distilled water. All glassware were cleaned using distilled
water.

Physical Methods for Structural Characterization

An elemental analyzer (Perkin Elmer Series II Model 2400) and a Fourier transform infrared (FTIR)
spectrometer (Perkin Elmer 16F PC) were utilized for elemental analyses and IR spectroscopy,
respectively. The nuclear magnetic resonance (NMR) spectra were recorded using a 500-MHz JEOL
LA spectrometer obtained from JEOL, JAPAN. The 1H signal of tetramethylsilane (TMS) at 0 ppm in
CDCl3, 1H peak at 4.65 for the residual H in D2O were used as internal standards. The dioxane 13C
peak at 67.4 ppm in D2O was used as external standard.

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Synthesis and Characterization
N,N-diallyldodecylamine (3b) and N,N-diallyltetradecylamine (3c) were synthesized as described by Ali
et al., 20117.7 Table 1 shows the entries, structures and molecular weights of synthesized corrosion
inhibitors (Figure 1: 5a, 5b and 5c).

Table 1: Name, structure and molecular weight of the examined corrosion inhibitors

Entry Structure Name Molecular Weight, (g/mole)

N,N-diallyl-N-
5a:C10 propargyldecylammonium bromide 356.39

N,N-diallyl-N-
5b:C12 propargyldodecylammonium 358.40
bromide

N,N-diallyl-N-
5c:C16 propargylhexadecylammonium 362.44
bromide

N,N-diallyldecylamine (3a)
A solution of 1-bromodecane (22.1 g, 0.100 mol), diallylamine (17 g, 0.175 mol) in toluene (20 cm3) was
refluxed under N2 for 24 h. After completion, the reaction mixture was cooled and stirred with a solution
of NaOH (8 g, 0.2 mol) in water (75 mL) and extracted with diethyl ether (2×50 mL). The organic layer
was dried (Na2SO4), concentrated, and distilled to obtain the diallyl derivative 3a (21 g, 88%) as a
colorless liquid, b.p.0.05 mbarHg 88 ºC.

max (KBr) 8676, 2928, 2856, 2796, 1642, 1458, 1353, 1263, 1153, 1094, 993, 917, 860 and 724 cm-1;
H (CDCl3) 0.88 (3H, t, J 7.0 Hz), 1.26 (14H, m), 1.44 (2H, m), 2.40 (2H, t, J 7.3 Hz), 3.08 (4H, d, J 6.4
Hz), 5.13 (4H, m), 5.85 (2H). C (CDCl3) 14.07, 22.65, 26.86, 27.48, 29.31, 29.57 (2C), 29.60, 31.88,
53.38, 56.83 (2C), 117.13 (2C), 135.86 (2C) (CDCl3 middle C at 77.00).

N,N-diallyl-N-propargyldecylammonium bromide (5a)

To a solution of a diallyl derivative 3a (9.5 g, 40 mmol) 1.20 g; 5.99 mmol) in acetone (20 mL) propargyl
bromide (4) was added. (7.4 g, 60 mmol; utilized as 9.25 g of 80 wt% propargyl bromide in toluene) and
these were stirred under N2 in a closed vessel at 60 oF for 16 h. After removal of the solvent the
residual liquid was washed with diethyl ether (3×25 mL) after stirring, followed by decantation to give a

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quaternary salt 5a as a liquid, which was dried under vacuum at 55°C until constant weight (13.3 g,
93%).

max (neat) 3463, 3866, 3182, 2851, 2117, 1637, 1462, 1367, 1221, 1166, 950, 847, and 737 cm-1;
(Found: C, 63.8; H, 9.7; N, 3.8. C19H34BrN requires C, 64.03; H, 9.62; N, 3.93%); H H (D2O) 0.80 (3 H,
t, J 7.0 Hz), 1.26 (14 H, m), 1.77 (2 H, m), 3.26 (2 H, m), 3.35 (1 H, s), 4.00 (4 H, m), 4.18 (2 H, s), 5.71
(4 H, m), 5.99 (2 H, m); C (D2O) 14.01, 21.96, 22.69, 26.22, 28.97, 29.43, 29.51, 29.56, 31.97, 49.01,
58.60, 61.22 (2 C), 71.12, 82.23, 123.97 (2 C), 129.60 (2 C).

N,N-diallyl-N-propargyldodecylammonium bromide (5b)

The compound 5b was prepared using the same procedure as described in the preparation of the
compound 5a except that N,N-diallyldodecylamine (3b) was used instead of N,N-diallyldecylamine (3a).
A similar work up procedure was applied, which in this case yielded quaternary 5b salt holding 91%
purity with a visual appearance as a faint yellow liquid, which was dried under vacuum at 55°C until no
loss of the solvent was shown (a constant weight) (91%).

max (neat) 3411, 3866, 3155, 2955, 2859, 2117, 1632, 1457, 1364, 1223, 1159, 996, 953, 847, and
786 cm-1; (Found: C, 65.4; H, 10.0; N, 3.5. C21H38BrN requires C, 65.61; H, 9.96; N, 3.64%); H H (D2O)
0.80 (3 H, t, J 7.0 Hz), 1.26 (18 H, m), 1.77 (2 H, m), 3.26 (2 H, m), 3.35 (1 H, s), 4.01 (4 H, m), 4.18 (2
H, s), 5.70 (4 H, m), 5.99 (2 H, m); C (D2O) 13.96, 22.02, 22.71, 26.86, 29.07, 29.56, 29.65, 29.77,
29.88, 29.94, 32.04, 49.03, 58.60, 61.25 (2C), 71.13, 82.25, 123.99 (2 C) 129.59 (2 C).

N,N-diallyl-N-propargylhexadecylammonium bromide (5c)

The compound 5c was prepared using the same procedure as described in the preparation of the
compound 5a except that N,N-diallylhexadecylamine (3c) was used instead of N,N-diallyldecylamine
(3a). A similar work up procedure gave the quaternary salt with an 88% yield as a white solid. MP (48-
51°C).

max (KBr) 3447, 3165, 2912, 2848, 2119, 1625, 1463, 1364, 1159, 1039, 999, 951, 845, 774, 716, and
672 cm-1; (Found: C, 67.9; H, 10.4; N, 3.1. C25H46BrN requires C, 68.16; H, 10.52; N, 3.18%); H (D2O)
0.77 (3 H, t, J 7.0 Hz), 1.23 (26 H, m), 1.75 (2 H, m), 3.23 (2 H, m), 3.35 (1 H, s), 3.99 (4 H, m), 4.19 (2
H, s), 5.68 (4 H, m), 5.98 (2 H, m); C (D2O) 13.96, 22.20, 22.74, 26.44, 29.20, 29.63 (2C), 29.98 (3C),
86.18 (4C), 32.09, 49.21, 58.75, 61.39 (2C), 71.31, 82.46, 124.23 (2 C), 129.56 (2 C).

CH3(CH2)nBr
Br
2 4 Br
N N N
H (CH2)n
(CH2)n
CH3
CH3

1 3 a, n= 9 5
b, n = 11
c, n = 15

Fig. 1— Synthesis of diallylpropargylammonium salts

Gravimetric (Weight-Loss) Tests

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Gravimetric experiments were carried out in glass cells containing high HCl acid solutions of 5 and 28
wt% in the presence and absence of corrosion inhibitors and iodide ions. The glass cells were placed in
a constant temperature bath, maintained at the required test temperature of 86 or 194 oF. Coiled tubing
(CT) steel coupons with dimensions of 1.175 x 0.57 x 0.10 inch and a surface area of 1.69 in2 were
used in the weight loss tests. The elemental composition of the CT steel coupons is given in Table 2.

Table 2: Chemical Composition of Coiled Tubing Steel

Element Fe Mn Cr Si Cu Ni C Al Se
Wt% 97.4 0.8 0.58 0.33 0.279 0.204 0.14 0.041 0.039
Element N Ta P Ti W Co Sn S As
Wt% >0.019 0.018 0.016 0.015 0.013 0.01 0.0091 0.0083 0.0066

In a typical weight loss experiment, the steel coupon was polished with 120, 240 and 480-grit silicon
carbide papers, then washed with distilled water, cleaned in ultrasound water bath, degreased with
acetone, washed with distilled water and finally, dried. The initial weight of the coupon was then
measured. After that, the coupon was soaked in 400 cm3 of the above described acid solution with and
without corrosion inhibitor for a fixed time of 2, 4 or 24 hours and at the temperature of interest (86 or
194 oF). Then the weight-loss was determined from the initial and final weights. The IE of the corrosion
inhibitors was calculated using Eq. 1:
IE. (%) = 100 (W o – W)/Wo ……………. (1)
Where W o and W are the weights in absence and presence of corrosion inhibitors in the acid,
respectively. Corrosion rates (C.R.) in g/cm2 and lb/ft2 were calculated using Eq. 2:
C.R. = W.L/S.A …………………………. (2)
Where W.L is the weight-loss in either gram or pound and S.A is the surface area of CT coupon
surfaces in either cm2 or ft2.

Iodide salt in the form of potassium iodide (KI) was examined to enhance performance of organic
corrosion inhibitors. Potassium iodide was examined at different concentrations ranging from 0.0001 to
0.1 M (0.166 to 16.60 g/L).8-11 In this study, KI salt was used at a concentration of 2.41 x 10-2 M which is
equivalent to 4 g/L. The aging time of coupons in acid solutions ranged from 2 to 24 hours depending
on the acid concentrations.

Electrochemical Methods
Electrochemical measurements were conducted in a conventional three-electrode cell of capacity 1,000
mL. Carbon steel 1018 coupons with the elemental composition given in Table 3 were used as a
working electrode while a Saturated Calomel Electrode (SCE) and a graphite electrode were used as
reference and counter electrodes, respectively. The potentiodynamic polarization analysis was carried
out using “GAMRY Instruments Interface 1000 E” and the data was analyzed using “Gamry Instrument
Framework version 1.5 software”.

Table 3: Chemical Composition of Carbon Steel 1018

Element Fe Mn Cr Si Cu Ni C Al Se
Wt% 98.54 0.772 0.0599 0.22 0.0605 0.0232 0.186 0.0393 0.00094
Element Mo Zn P Ti W Co Sn S As
Wt% >0.0040 0.0017 0.0363 0.0020 0.00096 0.0051 0.0042 0.0047 0.0036

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The acid solutions were stirred using a magnetic stirrer at 860 rpm during the testing period, to
eliminate accumulation of generated hydrogen gas at the working electrode. The electrode was allowed
to corrode freely for 86 minutes to provide sufficient time for the electrode to attain a steady-state
corrosion potential (Ecorr) following the open circuit potential (Eocp). The polarization measurements were
carried out by sweeping from a cathodic potential of -0.25 V to an anodic potential of +0.25 V with
respect to Ecorr at a rate of 1 mV s-1. The linear segments of anodic and cathodic Tafel curves (-0.25 to
+0.25 V vs Eocp) were extrapolated to Ecorr to obtain the corrosion current density (icorr). The IE was
obtained from the measured icorr using the following relationship (3):
IE = 100 × (io - i)/io……………. (3)
Where i and io are the inhibited and uninhibited corrosion current densities, respectively.

RESULTS

Performance of Iodide Ions in Uninhibited HCl Acid Solutions

As a baseline, the effect of potassium iodide at a concentration of 0.4 g/100 mL on inhibiting/retarding
the corrosivity of 5 and 28 wt% HCl as a function of temperature and soaking time was assessed.
Figure 1 shows IE of iodide ions for CT coupons exposed to 5 and 28 wt% HCl acid as function of
temperature (86 and 194 oF) and a soaking time ranging from 2 to 24 hours. The results showed that
the IE of iodide ions decreased inversely as a function of temperature, acid concentration and soaking
time. At a temperature of 86 oF (Figure 1-a), the IE of iodide ions decreased from more than 93% in 5
wt% HCl to nearly 76% when the soaking time was increased from 4 to 24 hours. Similarly, at an acid
concentration of 28 wt% the IE of iodide ions was nearly 84% after a soaking time of only 2 hours.
Figure 1-b shows that the impact of temperature was significant on 28 wt% HCl acid (IE = 5%)
compared to 5 wt% HCl acid (IE = > 85%). The results showed that iodide ions acted as acid corrosion
inhibitor/retarder for CT coupons, especially at mild conditions (low temperature/low acid
concentration). At more severe conditions (high acid concentration/high temperature) iodide ions acted
as poor acid corrosion inhibitor/retarder for CT steel.

Figure 1: Performance of iodide ions at the two temperatures 86 and 194o C as a function of HCl
acid concentration, and soaking time

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Synergistic Effect of Iodide Ions with N,N-diallyl-N-propargyl (C10; C12 or C16) Ammonium
Bromide
Synergism is a combined action of compounds greater in total effect than the sum of the individual
effect.12 Synergism of corrosion inhibitors is either due to the interaction between components of the
inhibitor composition or due to interaction between the inhibitor and one of the ions present in the
aqueous solution.13 Synergistic inhibition is an effective means to improve the inhibitive force of an
inhibitor, to decrease the amount of usage, and to diversify the application of inhibitors in acidic media14
(Geethanjali et al., 2013). To determine the existence of synergy between the synthesized quaternary
amines and the halide ions, a synergism parameter was evaluated using the equation initially proposed
by the Aramaki and Hackermann in 1964 and reported in several papers (e.g., Aramaki and Hakerman
(1969), Abdallah et al., 2013):15,16

1  12
S1  …………………. (4)
1  1'2

Where ϑ1+2 = ϑ1 + ϑ2 - (ϑ1•ϑ2); ϑ1 = the surface coverage by the halide ions; ϑ2 = the surface coverage by
the synthesized quaternary amines and ϑ’1+2 = the measured surface coverage by combination of the
inhibitor and halide ions. In our study, the halide ions are the iodide ions.

The synergism of iodide ions with the three synthesized corrosion inhibitors was examined as a
function of acid concentration (5 and 28 wt%) and temperature (86 and 194 oF). Tables 4-7 show the
synergism parameters calculated from the IEs obtained for iodine ions, inhibitors alone, iodide ions with
inhibitors, and combination of iodide ions with the inhibitors. For low acid concentration (5 wt%), there
was no synergism observed (Tables 4 and 5) since the obtained synergism parameters is less than 1
at the two examined temperatures (86 and 194 oF). The results showed that the temperature was not
the dominant factor to have a synergism between iodide ions and the synthesized inhibitors at HCl acid
concentration of 5 wt%.

Table 4: Synergism parameters for the synthesized inhibitors and iodide ions in 5 wt% HCl acid
at 86 oF and for a soaking time of 24 hours
Surface Coverage, Inhibition Efficiency (%)/100
Synergism
Inhibitor Iodide Inhibitor Inhibitor with Iodide
parameter
θ1 θ2 θ1+2' S1
C10 0.762 0.2571 0.971 0.635
C12 0.762 0.211 0.895 0.659
C16 0.762 0.154 0.867 0.720

Table 5: Synergism parameters for the synthesized inhibitors and iodide ions in 5 wt% HCl acid
at 194 oF and for a soaking time of 4 hours
Surface Coverage, Inhibition Efficiency (%)/100
Synergism
Inhibitor Iodide Inhibitor Inhibitor with Iodide
parameter
θ1 θ2 θ1+2' S1
C10 0.85331 0.653 0.9937 0.7839
C12 0.85331 0.7817 0.9886 0.7733
C16 0.85331 0.9571 0.919416 0.7417
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The effect of a high acid concentration (28 wt%) was investigated at the two examined temperatures
(86 and 194 oF). Iodide ions exhibited synergistic behavior with all examined corrosion inhibitors (C10,
C12 and C16) at 194 oF where the obtained synergism parameters were above 1 and it was more
pronounced in the case of the C16 inhibitor (S1 = 2.379, Table 7). At a low temperature of 86 oF both
C10 and C12 exhibited synergism with iodide ions with S1 of 1.7709 and 1.664, respectively (Table 6).
The results revealed that both acid strength and temperature have influence on synergism of iodide
with examined inhibitors. Indeed, more influence was observed for the acid strength compared to
temperature for the examined temperature. These results suggest the need to use iodide ions to
enhance protection performance of examined inhibitors at high acid strength/high temperature
conditions.

Table 6: Synergism parameters for the synthesized inhibitors and iodide ions in 28 wt% HCl acid
at 86 oF and for a soaking time of 2 hours
Surface Coverage, Inhibition Efficiency (%)/100
Synergism
Inhibitor Iodide Inhibitor Inhibitor with Iodide
parameter
θ1 θ2 θ1+2' S1
C10 0.836983 0.67234 0.96875 1.709
C12 0.836983 0.782979 0.97874 1.664
C16 0.836983 0.804255 0.968668 0.864

Table 7: Synergism parameter for the synthesized inhibitors and iodide ions in 28 wt% HCl acid
at 194 oF and for a soaking time of 2 hours
Surface Coverage, Inhibition Efficiency (%)/100
Synergism
Inhibitor Iodide Inhibitor Inhibitor with Iodide
parameter
θ1 θ2 θ1+2' S1
C10 0.050147 0.2571 0.8686 1.021
C12 0.050147 0.211 0.389 1.227
C16 0.050147 0.154 0.662 2.378

Adsorption Isotherms
The establishment of adsorption isotherms that describe the adsorption of a corrosion inhibitor can
provide important clues to the nature of the metal-inhibitor interaction.17 The surface coverage of
different concentrations of the synthesized inhibitors in acidic media has been evaluated from weight
loss measurements and attempted to fit these values to different sorption isotherms. The Temkin,
Freundlich, Frumkin Langmuir and Langmuri-Freundlich adsorption isotherms were used to examine
the adherence of the synthesized inhibitors on low carbon steel surfaces. The best fit was obtained for
El-Awadi and Frumkin models where a linear regression value of more than 0.95 was obtained. The El-
Awadi adsorption isotherm model is represented by Eq. 5.18
  
log   log K  y logC inh ……. (5)
1 

Where Cinh is the concentration of the synthesized inhibitor and θ is surface coverage value which is
evaluated from IE obtained from weight loss using the following Equation:

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 𝑊1
𝜃 =1− …….. 6
𝑊𝑜

W1 = weight loss experienced by low-carbon steel coupon in an inhibited acid.

Wo = weight loss experienced by low-carbon steel coupon in the acid alone.

K is related to the Kads by the following relation:

K ads  K 1/ y ………………….….. (7)

and Kads is related to the Gibb’s free energy of adsorption ΔGads by the equation:
1   Gads
o

K ads  exp   …….… (8)
55.5  RT 
It is generally accepted that values of ΔGºads in the order of -20 kJ mol-1 or less negative are associated
with an electrostatic interaction between the charged inhibitor molecules and the charged metal surface
(physisorption); whereas, those of -40 kJ mole-1 or more negative involve charge sharing or transfer
from the inhibitor molecules to the metal surface to form a co-ordinate covalent bond (chemisorption).
19-20
As an example, Figure 2 shows a plot of log (θ /1- θ) versus log Cinh for the synthesized corrosion
inhibitors. The calculated average free energy of adsorption values (-30 to -33 KJ/mole) for the
synthesized corrosion inhibitors is given in Table 8. The negative value of ∆Gads indicates spontaneous
adsorption of the corrosion inhibitors on the low-carbon steel. The result suggests that the adsorption
mechanism of the synthesized corrosion inhibitors on the low-carbon steel surface in HCl solution is
combination of chemical and physical interaction.

Table 8: The parameters of Langmuir, Frumkin and Al-Awadi isotherm models at the adsorption
of the synthesized corrosion inhibitors on mild steel (28 wt% HCl at 86 oF)

Langmuir Frumkin El-Awadi

∆G ∆G ∆G
n KJ/ Kads R2 a KJ/ Kads R2 y KJ/ Kads R2
mol mol mol
C10 0.5807 -33.0 2500 0.974 0.7087 -30.1 3600 0.9956 1.4538 -31.8 7248 0.9993
C12 0.7978 -30.9 5000 0.916 1.35375 -29.1 2444 0.9238 2.0211 -32.3 8877 0.9246

C16 0.9518 -30.9 5000 0.9535 1.46895 -29.1 2452 0.9708 2.2164 -32.6 10129 0.9472

Potentiodynamic Polarization Measurements

Potentiodynamic polarization studies were carried out to evaluate the inhibition mechanism of C10, C12
and C16 corrosion inhibitors. The corrosion behavior of carbon steel 1018 in 1 M HCl acid in the
absence and presence of the synthesized corrosion inhibitors was investigated by Gamry Instrument
Framework version 1.5 software for 30 minutes at 86 oF. Tafel plots of carbon steel 1018 in uninhibited
and inhibited acid solutions generated at 86 oF are presented in Figure 3. The introduction of the
inhibitors into the acidic solutions shifted the corrosion potential (Ecorr) to more positive and reduced the
corrosion current density. The results show that the C12 and C16 inhibitors suppressed/retarded anodic
reactions and thereby reduced steel dissolution. Figure 3 shows no shift in the corrosion potential in
the presence of C10 inhibitor and a decrease in both anodic and cathodic current density, which
indicates the C10 inhibitor, acts as a mixed-type inhibitor in acidic media.
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Figure 2: El-Awadi’s isotherm for the synthesized corrosion inhibitors (C10, C12 and C16) at 86
o
F

Fig. 3: Potentiodynamic polarization curves for carbon steel 1018 in 1M HCl (blank) and 1M HCl
acids containing 50 ppm of the corrosion inhibitors at 86 oF

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The values obtained from polarization measurements support the data obtained from the weight-loss
method. Table 9 gives the Tafel plot results obtained for blank (1M HCl acid) and inhibitors + HCl acid
solutions with 50 ppm of C10, C12 and C16 inhibitors at 86 oF. The IE increased in the order of
C10<C12<C16.

Table 9: Results of Tafel Plots of carbon steel in 1 M HCl Solutions without/with 50 ppm of the
Inhibitors at 86 oF
Ecorr (V) βa (V/decade) βc (V/decade) icorr (mA/cm2) IE%
Blank -4.76E-01 7.94E-02 1.35E-01 3.04
C10 -4.74E-01 6.51E-02 3.21E-01 9.49E-01 68.78
C12 -4.52E-01 8.38E-02 3.52E-01 8.81E-01 71.02
C16 -3.81E-01 5.67E-02 2.25E-01 4.89E-01 83.91

CONCLUSIONS

 Three quaternary ammonium salts with multiple adsorption sites and variable hydrocarbon chain
lengths ranging from 10 to 16 carbon atoms were synthesized and characterized using an
elemental analyzer, NMR and FTIR.
 The behavior of the synthesized compounds as a function of acid strength and temperature was
examined using both gravimetric and electrochemical methods (Tafel).
 The corrosion rate of steel increases with temperature in all examined acid concentrations in the
presence and absence of the inhibitors.
 The synergism between synthesized inhibitors and iodide ions is more dominant at high
HCl/temperature conditions (28 wt% and 194 oF); synergism parameters (S1 >1).
 At mild conditions (HCl = 5 wt% and T = 86 oF), there was no synergism between the synthesized
corrosion inhibitors and the iodide ions as indicated from the calculated synergism parameters (S1
<1).
 A free energy of adsorption of -30 to -33 KJ/mole was calculated for the synthesized corrosion
inhibitors on the CT steel; hence, combined physisorption/chemisorption mechanism is expected.
 The values of corrosion potential (Ecorr.) were shifted to less negative values in the presence of C12
and C16 inhibitors and remained unchanged for C10 inhibitor. Tafel plot results indicate that both
C12 and C16 inhibited corrosion of carbon steel in 1 M HCl acid by suppressing/retarding the
anodic reaction while C10 inhibitor exhibited a mixed-type mechanism (suppressing/retarding both
anodic and cathodic reactions).

NOMENCLATURE
A = Arrhenius frequency factor.
C.R = Corrosion rate.
cm = centimeter.
CT = Coiled Tubing.
Ea = Activation energy (J mole-1).
Ecorr = Corrosion potential.
EoFp = Open Circuit Potential.
IE = Inhibition efficiency.
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lb /ft2 = pound per square feet.
in = inch.
R = Molar gas constant (8.314 J mole-1 K).
S.A = Surface Area in ft2 or cm2.
SCE = Saturated Calomel Electrode.
S = Synergism parameter.
T = Absolute temperature (K).
θ = Surface coverage.
∆Gads = Adsorption energy (KJ/mole).
W1 = weight loss of CT steel in the presence of inhibitor.
Wo = weight loss of CT in the absence of the inhibitor.

ACKNOWLEDGEMENTS

The authors would Abdullah Alrustum from EXPEC ARC/Saudi Aramco and Abduljalil Al-Rasheed from
R&DC/Saudi Aramco for their support in conducting gravimetric and electrochemical measurements.

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