Proceedings of PETROTECH-2003

January 9-12, 2003, New Delhi

CORROSION INHIBITOR QUALITY ASSURANCE BY ITS

CHARACTERIZATION
S.S.Bhat,* A.G.Sarkar, Sudhir Sinha, and A. K. Sonawane
IEOT, ONGC, Panvel 410221, India
E-mail: bhatsubrahmanya@hotmail.com

ABSTRACT
Corrosion Inhibitor injection to a producing oil field system is one of the most effective
corrosion mitigation technique for utilizing carbon steel as preferred material of construction
of pipeline and well tubular. Active ingredients of these formulations are compounds like
amines, fatty acids, reaction product of acids and amines, quaternary ammonium salts
and Imidazolines. Sophisticated state-of-the-art instrumental techniques of FT-IR, Carbon13 NMR of inhibitor samples gave fingerprinting spectra of active ingredients. Different
chemical environment are reflected in these spectra in the form of identifiable and unique
peaks. The most common active ingredients of oil field corrosion inhibitors viz: Quaternary
amines, Imidazoline derivatives, solvents and additive have specific peaks to aid the chemist
to establish conclusively their identity in a given formulation. The side chain alkyl length
that influences the strength of inhibitor bonding with metal could be assigned with the
number of peaks.
Structurally different GCI samples were tested for their performance by gravimetric weight
loss method and compared with the film persistency by Electrochemical Impedance spectra
(EIS). Although samples have equal inhibitor efficiency as per gravimetric corrosion tests,
they differ in their film persistency qualities as revealed by EIS. The film persistency
studies support in deciding the mode of inhibitor injection viz: Batch or continuous treatment.
As the inhibitor chemistry has interaction with test medium, screen tests are to be carried
out in actual produced water instead of synthetic water. An inhibitor treatment remains
effective all along the pipeline as long as its concentration remains higher than the critical
micellar concentration and it can be monitored by residual analysis using high-pressure
liquid chromatography.
An integrated approach of Characterization of inhibitor chemistry, its performance and
monitoring critical micellar concentration shall provide the optimum quality assurance.

KEYWORDS: FT-IR, C-13 NMR,HPHT autoclave, Electrochemical Impedance, HPLC,

Inhibitor structure, performance

INTRODUCTION
The basic raw materials for preparing inhibitors are fatty acids or synthetic long chain
aliphatic acids, naphthenic acids, oxidized petroleum fractions and ammonia or organic

amines. Once the proper molecules are selected or synthesized they are formulated into
a usable formulations. The amines are viscous liquids or solids and must be diluted with
a proper solvent. The solvent may be aqueous blend (water, alcohol or coupling agents) for
water solubility. The coupling agents include glycol ethers, alcohols, esters and ketones.
They are selected to form a stable solution of the amines and other additives, and have
the proper degree of water and brine solubility or dispersibility. A hydrocarbon solvent will
be used for an oil soluble or an oil soluble water dispersible inhibitor. Aromatic solvents
are preferred since they have much better solvating properties than aliphatic solvents.
Pure aromatics such as xylene and toluene are rarely used due to high cost. Hence
byproduct aromatic solvents containing polycyclic materials and anthracene were used.
In special cases, aliphatic such as diesel is used. The formulations contain special types
of additives like surface-active agents to aid in dispersing the inhibitor, preventing emulsions,
and reducing the time it takes for the amine to wet the metal surface. These include
sulphonic acids and sulphonates, oxyalkylated materials such as amines, alkyl phenols,
fatty acids and amides and amphoterics.
The level of protection that an inhibitor provides can vary greatly, depending on such
parameters as the type of ingredients used in the inhibitor, percent activity of the formulation,
and composition of fluids in the system. By understanding the process involved in corrosion
protection at a molecular level, there is much enhanced ability to predict potentially suitable
inhibitor. In this paper attempt was made for the characterization of corrosion inhibitors
by using the sophisticated instrumentation like 13 C Nuclear Magnetic resonance
spectroscopy, Fourier Transform Infrared Spectroscopy (FT-IR) and corrosion inhibitor
performance tests by gravimetric and electrochemical impedance spectra. HPLC run was
tested for its suitability for residual analysis.

EXPERIMENTAL DETAILS
A. Spectroscopy:
1) FT-IR spectra were obtained on a Nicolet Magna Spectrometer 515 instrument with a
liquid nitrogen cooled detector with a range of 400 cm-1 to 5000 cm-1 . Samples were run
neat on 25mm KBR plates. The infra red region of electromagnetic spectrum extends
from the red end of the visible spectrum out to the microwave region. The spectral range
of greatest use is in mid-infrared region, which covers the frequency range from 200 to
4000 cm-1. The infra red spectrometry involves the twisting, bending, rotating, and
vibrational motions of atoms in a molecule. The multiplicity of vibrations occurring
simultaneously produces a highly complex absorption spectrum, which is uniquely
characteristic of the functional groups comprising the molecule and of the overall
configuration of the atoms as well.
2) 13 C NMR spectra were taken on a Varian 300 MHz Spectrophotometer. The samples
were prepared in CD3OD solvent. The characteristic absorption of energy by certain
spinning nuclei in a strong magnetic field, when irradiated by a second and weaker field
perpendicular to it, permits identification of atomic configuration on molecules.
Total of 5-corrosion inhibitor samples viz.: 3 samples being used in Mumbai High Field
and 2 from other private suppliers were analyzed for spectroscopic characterization.
B. Inhibitor performance test:
Metal coupon : API 5LX 52 coupons surface finished to 800 SiC grit and cleaned with
Isopropanol and rinsed with acetone and dried.

Corrodant : (i) 3.0% NaCl solution deaerated by nitrogen purging and purged in CO2.
(ii) 2.8% NaCl solution purged in CO2.
(iii) Produced water (2.8% NaCl, 350ppm volatile fatty acids)
Inhibitors: Two samples of corrosion inhibitors which were found structurally different viz:
ONGC OCI (quaternary ammonium salt based) and a sample of private supplier (Imidazoline
based GCI) were tested at 10ppm dose.
1. Gravimetric corrosion rate:
The corrosion inhibitor efficiency by conventional weight loss method was carried out in
a high-pressure high temperature Autoclave (2).
2. Electrochemical impedance spectra:
EG&G Princeton Applied Research Potentiostat/Galvanostat and Solarton Frequency
Response Analyzer was used for electrochemical impedance spectral measurements.
EIS measurements were carried out at an open circuit potential with an amplitude of 5mv
in frequency range of 1mHZ to 10KHZ.The scanning was carried out at 2hours and 60
hours of coupon immersion in inhibited brine and at 24hours of coupon removal and
immersion in uninhibited brine.
3. HPLC for residual analysis of inhibitors(3):
Hewlett Packard HPLC with variable UV-Visible detector and HP CHEMSTATION software
for analyzing chromatogram were used. Inhibitor solution was injected into standard ODS
column with methanol as the mobile phase. Four samples of commercial inhibitors were
dissolved in mobile phase to get stock solution of known concentration and were run in
HPLC for the calibration. Then known concentration of very dilute solutions of corrosion
inhibitors prepared in brine(3% NaCl solution) were run in HPLC to get chromatogram.
From the peak area comparisons and finger printing of eluted peaks in HPLC spectra, the
concentration of inhibitors were determined and compared with the actual input value to
assess the accuracy of the technique.

RESULTS AND DISCUSSION

The different chemical environment of the carbon atoms in the components of corrosion
inhibitor are reflected in Carbon-13 NMR spectra with identifiable and sometimes unique
peaks(1). The Imidazoline molecule has peaks assignable to an amide, an Imine and
Imidazoline ring. The Imine of Imidazoline ring structure has peak at 126PPM. The
resonance at approximately 173PPM and 167PPM were shown by amide and Imidazoline
respectively. The normally used surfactants like ethoxylated alcohol has Carbon-13 NMR
peak at around 70 PPM and aromatic solvent at 120-145PPM. The number of methylene
in alkane chains have peaks at 14-50ppm range and therefore, by counting such marked
peaks one can determine the number of carbons on alkane side chain. FT-IR peaks at
1566 cm-1 and 1708 cm-1 and 3325 cm-1 are due to Imidazoline ring structure, imide ,
unsaturated 5 membered ring and Imine(C=N-H) respectively. FT-IR peaks at 3434
cm-1, and 1661 cm-1 are exhibited by quaternary ammonium salt. Carbon 13 NMR chemical
shift at around 47PPM is given by amine. The peaks in FT-IR spectra and Carbon-13 NMR
spectra and their inference for five samples of corrosion inhibitors are given in table 1. Out

of five samples, 3 were found to be quaternary ammonium salt based and 2 were imidazoline
based. Sample OCI-B has alkyl side chain length of 16 carbon atoms and all the remaining
4 samples side chain have 12 carbon atoms.
With the fast pace of change in todays marketplace and the need to remove higher
quantity of oil and gas from reservoirs more quickly, at higher shear rate conditions and a
vastly increased potential for corrosion, it is essential to develop techniques for
characterizing the suitable corrosion inhibitor with ground knowledge of molecular structure.
The global companies that are manufacturing inhibitors have already started R&D projects
to correlate the molecular structure with their performance in different corrosive conditions.
M/S Baker Petrolite of USA (4) established that the effectiveness of Imidazoline derivatives
with side chain carbon length exceeding 16 to 18. Also, they proved that the optimum
dose of inhibitor varies with the carbon chain length, i.e. while C18 retards corrosion at a
concentration of 10 ppm, the C16 inhibitor must be used at almost 20ppm dose and C12
requires more than 30ppm. When carbon chain becomes as short as eight or ten carbons,
the corrosion inhibitor effect is essentially nonexistent under the particular corrosive
conditions. The longer chain molecules bind more tightly to the metal surface. Understanding
of the molecular structure enables to identify suitable corrosion inhibitor for the oil and gas
production environment.
The results of corrosion inhibition studies conducted in synthetic brine and actual produced
water from Mumbai offshore oil field is given in table 2. It is observed that the performance
of inhibitor varies with the test medium. When discussing the corrosion inhibitor efficiencies,
at severe corrosive environment, it losses its focus as it is possible that the inhibited rate
still remains much above the acceptable corrosion rate. The inhibitor chemical interactions
with corrosive environment are so complex that it is not practicable to compare the screening
results obtained with synthetic brine and actual produced water. Of late some of the
produced water samples of Mumbai High field showed significant quantity of volatile fatty
acids, which enhances the CO2 corrosion by way of destabilizing the protective film on
metal surface. In the above study it can be seen that inhibitor dose of 50ppm are required
to maintain the corrosion rate within the acceptable limit of 5mpy when tested with produced
water. However the same inhibitors were effective even at 10ppm in the synthetic water
medium. Therefore, it is appropriate to use the actual produced water in place of synthetic
brine while conducting inhibitor screen tests.
Two corrosion inhibitors which are structurally different i.e. one being Quaternary ammonium
salt based (ONGC OCI) and another being Imidazoline based GCI (Private Supplier), were
tested for inhibitor efficiency tests both by conventional coupon weight loss technique and
Advanced Electrochemical impedance spectral method. An optimum dose of 10ppm of
corrosion inhibitor was treated into a corrodant media of 3% NaCl (de-aerated) and purged
with CO2 (partial pressure of CO2 =20psi, temperature=500C.) The corrosion rates with
ONGC OCI and private supplier GCI sample were 3.65mpy, 3.27mpy respectively against
the corrosion rate of 60.6mpy for the blank. Both the inhibitors are almost equally effective
in reducing the uniform corrosion. Thus both the quaternary ammonium salt-based inhibitor
and Imidazoline based inhibitors are equally effective to mitigate uniform corrosion. The
impedance values derived from semicircle diameters fitting from Nyquist plots at 2hrs and
60 hrs of immersion in inhibited brine and after immersion for 24 hours in uninhibited brine
for the two inhibitors are given in table3. The two types of inhibitors showed different film
strength build up. The OCI of ONGC being quaternary ammonium salt based, build up film
strength steadily and it is so strong that once the film is formed it is not desorbing easily
on interruption of treatment. The sample has 16 carbons in its alkyl side chain. Hence the

inhibitor is suitable for higher dose of batch treatment followed by low dose continuous
treatment. The Imidazoline based GCI inhibitor builds up film very fast. However, the alkyl
side chain length of this sample was only 12 carbons and hence film strength is poor and
gets peeled off once the treatment is interrupted. Therefore, this type of inhibitor is to be
treated continuously at an optimum dose and never to be interrupted due to any reasons,
as it will cause localized pitting and failures. Although the two types of inhibitors showed
nearly equal inhibition in conventional weight loss technique, which is a measure of uniform
corrosion, they differ in results of Electrochemical Impedance Spectral analysis, which
includes localized corrosion also. Thus it is better to run E.I.S. of inhibitors before
deciding on their mode of Field treatment.
The results of HPLC chromatogram are given in table 4. It is observed that in all the four
samples of inhibitors, there is an excellent matching of its estimated concentration with
that of actual input concentration. HPLC is extremely versatile technique and can be used
to determine virtually any non-gaseous analyte as long as it is soluble in an organic or
inorganic solvent. Hence HPLC technique can be an excellent tool for monitoring inhibitor
concentration in pipelines.
Inhibitor quality is a function of its performance. When inhibitor molecule is present at the
interface of a corroding metal surface, polar moiety gets adsorbed. By increasing the
concentration of inhibitor in bulk solution, hydrophobic groups of already adsorbed inhibitor
interact with the hydrophobic groups of on coming inhibitor molecule. This results in the
aggregation of hydrophobic groups at the interface, called hemi micelle formation. By
further increasing inhibitor concentration in the bulk solution, formation of micelles take
place. Micelles are spherical and /or lamellar aggregations of inhibitor molecules. In water
solutions, the hydrated hydrophilic groups are at the outside of the micelle, while their
hydrophobic groups are directed to the interior. The concentration at which the formation
of micellar aggregates starts is called critical micellar concentration (CMC) and
characterizes the kind of interactions between a given inhibitor and a given corrosive
environment. An inhibitor becomes very efficient only at concentrations higher than its
critical micellar concentration. An integrated approach to characterization of corrosion
inhibitor chemistry, its performance and monitoring critical micellar concentration shall
provide the optimum quality assurance.

CONCLUSIONS
Molecular structure elucidation of active ingredients of corrosion inhibitor formulations can
be carried out by spectroscopic techniques like FT-IR, Carbon-13 NMR. It is recommended
to conduct inhibitor screen tests in actual produced water instead of synthetic brines. The
uniform corrosion rate calculated based on conventional weight loss is to be studied along
with the results of Electrochemical Impedance spectra while assessing the film properties
of inhibitor formulation. Electrochemical Impedance spectral analysis helps to identify the
mode of application of inhibitor. The samples with inhibitor film remaining intact in spite of
interruption of treatment shall be suitable for combination of batch and continuous treatment.
The samples, with film strength breaking on interruptions are suitable only for continuous
treatment. HPLC run of produced fluids can be used for residual analysis of inhibitor in
pipelines to monitor critical micellar concentration.

REFERENCES
1. John R.Dyer., Application of absorption spectroscopy of organic compounds,
Publ. Prentice Hall of India, 1984
2. S. Papavinasam et.al .,Laboratory methodologies for corrosion inhibitor
selection MP, August,2000
3. J.A.Martin et.al.,The determination of corrosion inhibitor residual
concentrations.. MP, May,1986.
4. S.Ramachandran et.al., Understanding Interactions between corrosion
inhibitors and Iron carbonate films using Molecular modeling. Corrosion/99,
paper 7,NACE.

Table 1: FT -IR and Carbon-13 NM R peaks

No.

Sam ple

O CI-A

O CI-B

G CI-E

FT-IR
Peaks
Cm -1
1642
3460
1037
714
3434
1661
654
3434
1661
1195
662

3325
1708
1566
724
3325
1723
1572
662

Inference

13 C-NM R peaks

Inference

Q uaternary Am m onium
salt

No peaks at 127ppm
12 peaks in 14 to
50ppm range
129.7ppm
No peaks at 127ppm
16 peaks in 14 to
50ppm range

Im idazoline absent
Alkyl side chain has
12 carbons
Arom atic solvent
Im idazoline absent
Alkyl side chain has
16 carbons

No peaks at 127ppm
12 peaks in 14 to
50ppm range

Im idazoline absent
Alkyl side chain has
12 carbons

Peak at 127ppm
12 peaks in 14 to
50ppm range
129ppm
Peak at 127ppm
12 peaks in 14 to
50ppm range
Peak at 128.6ppm

Im idazoline present
Alkyl side chain has
12 carbons
Arom atic solvent
Im idazoline present
Alkyl side chain has
12 carbons
Arom atic solvent

Arom atic solvent

M ixtures of Am ines and
Q uaternary am m onium
salt
Arom atic solvent
M ixtures of Am ines and
Q uaternary am m onium
salt
Sulphonic acids
additive
Arom atic solvent
Im idazoline

Arom atic solvent

Im idazoline

Arom atic solvent

Table 2: Effects of test medium on Inhibitor perform ance

Partial pressure of C O 2 = 20psi,Tem perature = 70 deg.C , C oupon = API 5C T L-80 steel
C orrodant : (a) 2.8% N aCl solution (b) Produced water(2.8% N aC l, volatile fatty acids = 350pm )
N o.

Test
condition

Test m edium
Synthetic brine (2.8% NaC l)

1
2
3
4
5
6
7
8

Inhibitor, ppm
0 (blank)
O C I,10ppm
O C I,30ppm
O C I, 50ppm
G C I,10ppm
G C I, 30ppm
G C I, 50ppm

Produced W ater
(2.8% NaC l , Volatile fatty acid=350ppm )
C or.rate, m py ( % inhibition)
74.0(0% )
15.0(80% )
2.4(97% )
19(74% )
2.1(97% )

C or.rate, m py ( % inhibition)
48.0(0% )
3.7(92% )
2.9(94% )
-

Table 3: Impedance results from Nyquist plot sem icircle diam eter fitting, ohm s
M edium
Blank
Blank+
10PPM
O N G C O C I-B
(16 carbons
in side chain)
Blank+
10PPM
Im idazoline
based G C I
(12 carbons
in side chain)

2 hours
Inhibited
290
390

60 hours
inhibited
410
305X 10

273X 10

890X 10

24hours
uninhibited
690
573 X 10

950

R em arks

Slow & steady build up of inhibitor film

on m etal surface.

Very fast form ation of inhibitor film . But

peels off on interruption of treatm ent

Blank=3.0% N aC l deaerated, purged CO 2

Table 4: High pressure liquid chrom atography results
Sl.
No

Sam ple particulars

Inhibitor conc. In
stock solution, ppm

1
2
3
4

O C I-O N G C
Im idazoline based - 1
Im idazoline based - 2
Q uaternary am ine based

1000
100
1750
100

Inhibitor conc. in Brine (3% NaC l), ppm

H PLC Input
1ppm
1ppm
4ppm
4ppm

C hrom atogram output

0.78ppm
1.09ppm
3.96ppm
4.21ppm