Paper No.

07618

DEVELOPMENTS IN THE LABORATORY EVALUATION OF CORROSION INHIBITORS:

A REVIEW

Adelina J. Son, Ph.D

Champion Technologies
P.O. Box 450499
Houston, Texas 77245-0499

ABSTRACT
Numerous laboratory methods have been developed to evaluate the concentration of various
corrosion inhibitors in oil and gas production fluids. The laboratory evaluation, often referred
to as residual analysis, provides quick monitoring of the adequacy of treatment levels of
corrosion inhibitors in different applications, time of dispersion or travel through fluids as well
as efficiency of the inhibitor.
The review will discuss procedures, varying from the simple wet techniques to the
sophisticated and expensive instrumental procedures, from bulk analysis to specie-specific
techniques. Establishing mass balance using analytical techniques with batch samples of
corrosion inhibitors as standards can be tricky. Factors such as partitioning, chemical
reactions with other chemical species, adsorption onto solids, solubility changes, etc. must be
understood and considered in the calculations. The utility and applicability of the methods will
be compared with respect to cost and ease of setup, range of applications, selectivity, accuracy,
detection limit, reproducibility and limitations. The review will include analysis of the industry
needs and challenges facing the researchers developing new procedures.
Keywords: analysis of corrosion inhibitors, review of methods, determination of imidazolines,
quaternary amines, phosphonates in production waters, spectroscopy, solid phase extraction,
chromatography, surface analysis
Copyright
2007 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

INTRODUCTION
This review is a compilation from the open literature and covers the most useful laboratory and
field methodologies pertaining to the measurement of corrosion inhibitors in oilfield-related
samples. To the analysts, who are new to the field of corrosion inhibitor analysis, the review can
serve as an introduction and a guide to the subject. To the experienced chemists, it points out
the current limitations and may inspire some needed innovations. The review is concentrated
on the phase of the oilfield industry that uses the most corrosion inhibitors, i.e. production and
transportation of produced fluids. However, the methods reviewed are also applicable to the
drilling and refining areas. Some reference to the chemistry of the sample involved is presented
to understand rationale behind the choice of methods and allow improvements to be put in
place, as the analyst sees fit.
A few methods for characterization of phosphonates are included because phosphonates are
components in some corrosion inhibitor formulations.
Why is accurate determination of the concentration of corrosion inhibitors important?
1. Residual corrosion inhibitor analysis confirms adequate inhibitor transport and
protection in operations related to drilling, production, plant processing, transmission
through pipelines and refining.
2. Effectiveness of the inhibition programs is generally monitored by corrosion probes,
coupons and increases in the iron content of the water1,2. In the absence of an effective
monitoring program, residual inhibitor analysis guides adjustment of treatment levels to
prevent corrosion problems and expensive hardware replacements. For example, a
tubing failure occurred in an offshore production system in Northern North Sea.
Residual analysis showed the absence of inhibitor. The cause was poor location of the
inhibitor injection nozzle3.
3. In some locations, corrosion control programs are linked to set inhibitor concentrations.
The operator mandates constant monitoring and adjustment of the inhibitor
concentration to the predefined value. Such practice has resulted in lower cost of
treatment and generally less hardware and maintenance problems.
4. Government regulations set allowable chemical discharge levels for oilfield chemicals
due to concern over adverse biological effects. Accurate determination of residual
inhibitor concentrations in water and solids for disposal is required to ensure that they
are within safe levels for discharge, particularly in environmentally sensitive areas
(North Sea, Gulf of Mexico, etc.). In the U.S., monitoring is a responsibility of the
Materials Management Service (MMS). In the North Sea, regulations are defined by the
Oslo and Paris Commission (OSPAR) Harmonized Mandatory Control Scheme (HMCS).
Chemical usage and discharge are regulated according to the hazard quotients
calculated by the Chemical Hazard Assessment and Risk Management (CHARM) model.
Chemical companies are required to submit an estimation of fraction released to the
Centre of Environment, Fisheries and Aquaculture Science (CEFAS), Burnham-onCrouch, England as part of the HMCS submissions. Theoretical calculations are often
not backed by actual data due to lack of suitable analytical techniques to assay the
discharges4.
5. Multiphase systems, where condensation of water and/or hydrocarbon occurs, are
difficult to treat. Conventional treatment is based on the gas volumes where what is
really needed is treatment based on the liquid phase volumes5. Corrosion inhibitor
measurements can complement multiphase modeling for systems where condensation
occurs for improved corrosion control.
Corrosion inhibitors in the oilfield industry are usually complex mixtures, which present
difficulties in analyzing for concentrations of the inhibitors in oilfield waters. The film-forming
components of the corrosion inhibitors are mixed with surfactants and solvents to control
2

dispersion, flow properties and prevent emulsion problems6. Some of the components of
corrosion inhibitors are shown in Figure 1. Many corrosion inhibitors are formulated with 2 or
more of these components: quaternary amines, amides, imidazolines, phosphate esters and
surfactants7,8. Quaternary ammonium compounds (quats) are of particular interest because
they function as surfactants, corrosion inhibitors and biocides in the petroleum and gas
production industry. Many of the published residual techniques were developed for quats and
are now routinely applied in analysis of samples. The corrosion inhibitor concentration is
calculated based on the quat content.
In addition to the complex chemical environment, partitioning of the components to the different
phases and adsorption on the metal occur. This results in low concentrations of the chemical
specie(s) in the monitored phase. In developing analytical methods, it is important to
understand not only the chemistry of the inhibitor and the chemical environment but also
physical properties such as solubility and partitioning behavior.
The aqueous phase is the more commonly monitored phase. The active ingredients of watersoluble or water dispersible corrosion inhibitors partition to the water which tends to migrate
toward the oil/water interface. The location of the sampling point can be critical, particularly if
the objective is to be able to relate corrosion inhibitor concentrations to corrosion protection.
Current analytical techniques can monitor one or more of the components. The utility of a
procedure depends on the accuracy, speed, sensitivity, selectivity and precision of the method9.
This is a lofty demand considering that many treating chemicals are combination of corrosion
inhibitors, emulsion breakers, scale inhibitors and other surface-active agents.
The
requirements to qualify as a good method are serious challenges to chemists who need to work
with difficult and constantly changing matrix interferences in oilfield samples.
The accuracy of any analytical investigation is also dependent on the sample integrity.
Acidizing of field samples is commonly done to prevent formation of insoluble iron compounds
and other solids and potential loss of corrosion inhibitors through adsorption. Matrix matching
eliminates or minimizes interferences present in the sample. The practice can be critical when
employing certain spectroscopic techniques.
The choice of analytical technique depends on many factors. Ideally, the analysis is carried out
as close to the lease or treatment facilities as possible. The burden and the challenge, then fall
on the district laboratories for decision on what method to use, based on the number of
samples, the technical experience of personnel and available equipment. Most district
laboratories use titration and UV-Visible spectroscopic methods, which use simple low cost
equipment. Procedures, which are more sophisticated, have been reported and are useful for
problem solving associated with large and critical accounts and to meet government and
environmental regulations. Some require expensive equipment and well-trained personnel who
are typically available only in the companys main analytical laboratories.
VISIBLE SPECTROSCOPY
Analytical techniques, which are based on development of colors (methyl orange, bromophenol
blue, bromocresol purple), are run routinely in many laboratories because they are easy and
inexpensive to set-up and can be run by personnel with minimal training. In the oilfield
industry, they are commonly referred to as Dye Transfer methods. In general, these methods
lack specificity, sensitivity and are prone to interferences, including matrix interference.
Common interferents are polar organic compounds from crude oil and other chemicals, some of
which exist in higher concentrations relative to the corrosion inhibitor.
With training and

experience, many analysts are able to overcome the difficulties and report accurate and precise
data.
The use of chloroform with the bromocresol purple and methyl orange extraction techniques
presents safety concerns for the analysts. Toluene, used with the bromophenol blue extraction
method, is a less toxic solvent.
Dye transfer methods are based on the reaction of cationic surface-active agents with the basic
form of many dyes to form salts or complexes10. Skadhauge and Fogh11,12 discovered the
reaction of quats with bromocresol purple forming a blue complex and led to the development
of an analytical method for quantitative analysis of quaternary ammonium compounds. In the
procedure, the inhibitor/dye complexes, are extracted with solvents and monitored by Visible
Spectrophotometry at 620 nm to read the absorbance. The bromocresol purple complex
formation has been used extensively in the oilfield for determination of quaternary ammonium
compounds in corrosion inhibitors9,13,14,15. Figure 2 shows spectra for bromocresol purple
complexes for a set of corrosion inhibitor standards. The linear range achieved in the analysis
depends on the corrosion inhibitor blend.
Fortenberry et. al.16 utilized the methyl orange dye transfer method to analyze field brine
samples. Limitations with this dye-extraction technique included interferences from other
treating chemicals present in the brine sample and adsorption of the quaternary amine/dye
complex onto the glass container. Lower than expected concentrations were measured, based
on treating rates. This was attributed to loss of the quat to clays, scales and iron precipitates
and partitioning processes.
Another dye extraction method uses bromophenol blue as complexing agent17,18. The complex
is non-polar and can be extracted from the aqueous phase (brine) using toluene. Absorbance of
the blue complex is read at 600 nm.
In all the dye extraction techniques, matrix interference is a big problem. Matrix matching by
preparing the standards in clean untreated brines similar to the sample matrix minimizes this
problem. Synthetic brines of the same composition maybe substituted if there is difficulty in
obtaining sufficient volumes of untreated field brines. In situations where synthetic brines of
similar composition are not available, matching the chloride content of the water used to
prepare the standards with the chloride content of the sample(s) improves accuracy. Error is
reduced, but not completely eliminated14. A brief description of the procedures is found in
Appendix A.
Another acceptable analysis is the phosphomolybdenum blue method for phosphates,
phosphonates and phosphate esters19,20. Phosphonates and phosphate esters are used as
scale and corrosion inhibitors and are known to form synergistic mixtures with other
components of corrosion inhibitor formulations7,8. The procedure involves: a) digestion of the
sample with sodium or potassium persulfate to convert all the P-containing compounds to
orthophosphates, b) treatment with molybdate solution which converts the orthophosphates to
a yellow complex of phosphomolybdic acid (PO3Mo12O36)21, c) reduction with ascorbic acid or
stannous chloride to the blue complex, and d) analysis at 650 700 nm. In the field labs, Hach
kits are used quite extensively due to the convenience of having pre-weighed reagents.
Kan et. al.20 modified the classic colorimetric technique for phosphonate with the use of a
pressure cooker for the persulfate digestion. Methyl isobutyl ketone (MIBK)/cyclohexane
solvent extracts the phosphomolybdate complex before reducing with stannous chloride to the
phosphomolybdenum blue complex. The modification resulted in detection limits of 0.1 mg/L
and improved accuracy. The MIBK/cyclohexane solvent eliminated the common interferences
to the orthophosphate determination.
4

STATIC ULTRAVIOLET SPECTROSCOPY

Izawa22 used ultraviolet spectroscopy to characterize surface-active agents and published the
wavelength of maximum absorption of cationic surfactants including alkylpyridinium halides
(max = 259.5 nm) and alkylbenzyldimethylammonium chloride (max = 263 nm), two commonly
used components of water-soluble corrosion inhibitors.
Fortenberry et. al. 16 used UV absorbance at 260 - 280 nm to analyze brines from six pipelines
from various areas in the U.S. treated with water-based corrosion inhibitors. The same samples
were analyzed using the methyl orange extraction method. Relative to the dye extraction
technique, UV spectroscopy was found to be more accurate, sample preparation was much
simpler and interferences were overcome using the spectra subtraction feature of the UV
spectrometer software. The UV calibration curve was linear over a much wider range of
concentration (350 ppm) compared to the dye extraction method (50 ppm).
UV spectroscopy was employed for monitoring residual corrosion inhibitors in a pipeline and
also for a number of leases in Alberta, Canada. The presence of other treating chemicals and
the high salinity (some close to saturation with inorganic salts) of the brines, which changed
with time, challenged the skills of the analytical chemists14. The chemists realized that solubility
and partitioning characteristics of the corrosion inhibitor change with the salinity of the water
and remedial measures were put in place. This included multiple and frequent sampling,
information on the production volumes (oil and water), calibration curves with matched
matrices and standards bracketing. A dynamic chart for each location showed the trend and
indicated when adjustment of inhibitor level was necessary. Lab data in the running chart were
corrected for partitioning. A description of the procedure is found in Appendix B.
STATIC FLUORESCENCE SPECTROSCOPY
Quaternary amines fluoresce and are easily detected in low concentrations2. Fluorescence is a
more selective technique, requiring the use of two wavelengths (excitation and emission). It is
more sensitive compared to the UV method. The fluorescence method is equally simple to set
up but with improved accuracy over UV analysis. For quats, the procedures consist or
separating the oil phase from the brine, filtration of the brine phase, dilution as needed and
reading the fluorescence intensity with 325 nm as excitation wavelength and 400 nm as
emission wavelength9.
Analysis for imidazolines or amidoimidazolines by fluorescence spectroscopy, involves
complexation with fluorescamine and detection using excitation wavelength of 275-280 nm and
emission wavelength of 460 - 490 nm. Depending on the type of imidazoline and sample matrix,
the author found that using 390 5 nm for excitation gave sharper and more intense
fluorescence signals. The procedure is described in Appendix B and Figure 323.
AUTOMATED FLUORESCENCE SPECTROSCOPY
In 1977, Gatlin et. al.2 used fluorescence as a field method to continuously monitor inhibitor
residual in water flood projects. The inhibitors were Inhibitor A, which was a quaternary
ammonium compound, and Inhibitor B, which was a combination of quaternary ammonium
compound and an organic liquid oxygen scavenger. The fluorescing component was the
quaternary ammonium compound. They used 315 - 335 nm excitation wavelength and 380 - 410
nm emission wavelength. In-line monitoring provided an instantaneous recording of chemical
residual, used to control corrosion inhibitor injection. Dependence of emission intensity on pH

and temperature was observed and addressed, but did not affect the accuracy of the analysis.
Concentration of two ppm of inhibitor was detected continuously in the flow system.
The test procedure consisted of setting up the flow system, standardizing the fluorescence
spectrometer and then initiating the flow. The chemical pump, downstream from the sampling
point, injected inhibitor when the corrosion inhibitor level fell below the preset level.
The flow system consisted of two turbine/centrifugal injection pumps (capacity of 20,000
22,000 barrels/day). A 30-ft. tubing was run upstream of one of the pumps to the flow cell of the
fluorescence spectrometer. The fluid exited from the flow cell to a disposal pit.
Son and Chakravarty9 discussed the successful use of an automated fluorescence spectrometer
in the field. The spectrometer was equipped with an auto-sampler and was programmed to
serve the districts need to analyze a high number of samples in the field using technical
personnel with no training in corrosion inhibitor determination. Part of the instrument setup
entailed generation of calibration curves for each of the corrosion inhibitors used in the
different locations. After the initial set-up, a chemist checked the calibration curves and
performed maintenance on the system on a regular basis. The fluorescence spectrometer was
programmed to do sample pickup, dilution of sample, mixing, delivery to fluorescence cell,
rinsing, analysis and calculation. The field personnel collected the sample, filtered the sample
when turbidity was observed, poured the sample to a test tube in the auto-sampler, chose the
calibration curve and pushed a button. Within minutes, the results were obtained and any
treatment adjustment was made.
Dye extraction methods and static spectroscopy methods monitor one component of the
corrosion inhibitor. It is well documented that the individual components partition between the
oil and aqueous phases. In the field, as soon as the corrosion inhibitor is injected into the
system, the inhibitor partitions to the different phases. Gough24 observed that higher molecular
weight quats are very much depleted relative to the lower molecular weight quats in field brine
samples. Higher molecular weight quats either partitioned to the oil phase or have been lost to
the metal surfaces25. This phenomenon is demonstrated in Figure 4. It can be seen from the
two emission spectra (before and after partitioning to brine and condensate phases) that the
concentrations of the partitioned standards are lower relative to the non-partitioned standards.
The emission wavelength used in the analysis was 460 nm and the excitation wavelength was
390 nm.
The use of partitioned standards is highly recommended14,17 for a closer simulation of how
much corrosion inhibitor is actually in the aqueous phase that is providing the protection to the
system being treated and monitored.
THIN LAYER CHROMATOGRAPHY
Buck, et.al.5,26 used thin layer chromatography (TLC) because the simplicity of the method and
inexpensive instrumentation make it suitable for field analysis. Silica gel layer was chosen as
adsorption medium because it readily separated non-polar diluent oils from the more polar
nitrogen-based corrosion inhibitors.
The field procedure is patented26. Buck et. al. used a thin layer of adsorbent (silica gel)
mechanically bound to a 20 cm2 or smaller glass support. A weakly absorbent material, such as
kieselguhr, was coated near one edge of the plate where the sample of formation fluid can be
applied. A sample of produced fluid was applied 2-4 cm from one edge of the plate. Standards
were applied on both sides of the sample (horizontally aligned). Solvent was dried off and then
the plate was placed in a container that can be closed, with the sample application edge closest
6

to the bottom of the container. An eluting solvent was added to the container just below the
sample zone. The plate was exposed to the solvent vapor and was allowed to equilibrate. The
sample plate was suspended, not touching the solvent during the solvent equilibration phase.
After equilibration, the plate was lowered into the solvent. The solvent traveled up the plate via
capillary action. After a predetermined time for the solvent to travel beyond the sample and
standard spots, the plate was removed, dried and sprayed with a suitable visualization agent.
The sample spot size and intensity was compared to the standards. When the inhibitor
concentration read below the standards, it was an indication that additional inhibitor needed to
be added to the production system.
TLC can also be used to identify, qualitatively, unknown corrosion inhibitors in a sample. In
TLC, as the solvent passed through the sample zone, the components compete for the
adsorption sites on the layer with the solvent, and those that are less strongly adsorbed to the
layer than the solvent are carried further up the vertical plate, while those more strongly
adsorbed are retained closer to the original spot point. Hence, the components of the sample
become spatially separated on the adsorbent. When separation is complete, derivatization
reagents can be sprayed onto the adsorbent and each derivative viewed with both visible and
UV light. In the method development studies, 224 corrosion inhibitors were chosen by Buck et.
al.5 to represent a range of polarity and compound types. The solvents and derivatizing
reagents were identified for each corrosion inhibitor type.
TLC was found to be sensitive up to 1 ppm. Detection limit was found to be dependent on the
compound of interest, matrix interference and the ability to load sufficient material on the
adsorbent layer5.
FOURIER TRANSFORM INFRARED (FTIR) SPECTROSCOPY
Martin, Valone and Haltmar used FTIR and 13C NMR (nuclear magnetic resonance) spectroscopy
to accurately determine residual corrosion inhibitor concentrations in inhibited diesel
solutions27. 13C NMR is the reference method for FTIR analysis. FTIR is a rapid and precise
technique for determining inhibitor concentration and has the advantage of providing
information on the composition or decomposition of inhibitors.
The inhibitor was a reaction product of an amine with a dimer-trimer acid and blended with an
ethoxylated surfactant in an aromatic solvent. The reaction product, as used in the diesel
solutions, was a mixture of imidazoline and amide. Peaks in the FTIR spectrum, 1740 cm-1 and
1550 cm-1 for the ester and amide functionalities, were used for the analysis. These peaks were
unique to the inhibitor and not found in the diesel. For both 13C NMR and FTIR techniques, the
ester peak was easily characterized. Initially, it was assumed, that all amine functionality in the
corrosion inhibitor was in the amide form.
The solutions were divided into two portions. Half was kept at ambient temperature while the
other half was heated at 240oF for 24 hours to simulate downhole temperatures. The heated
imidazoline solutions partially hydrolyzed to the amide form, converting to a mixture of
secondary and tertiary amides. Using the 1550 cm-1 peak for analysis, the heated samples gave
consistently lower concentrations relative to the calculated starting concentration. FTIR does
not have the sensitivity to measure ppm levels of corrosion inhibitors. The detection limit for
the inhibitor/diesel solution was approximately 10-20%27.
Reverse-phase solubility was
observed.
Martin and Valone investigated the utility of FTIR and 13C NMR techniques for a quality
assurance program 28,29. In the FTIR method, the weight ratios of the amine to acid for 28

neutralized imidazoline formulations gave a linear correlation with a correlation coefficient of

0.92.
The FTIR method is useful for hydrocarbon-based systems but generally not applicable to
aqueous samples.
In the oilfield industry, FTIR is used for quick identification of unknown
inhibitors and not for residual analysis. It continues to be a popular quality control method,
particularly in the manufacture of imidazolines and amides.
HPLC/ULTRAVIOLET SPECTROSCOPY/FLUORESCENCE
High performance liquid chromatography (HPLC) is a separation technique. It is suitable for
analysis of corrosion inhibitors, which are mixtures of different components. In an HPLC
analysis, the components separate by differences in polarity. The separation occurs as a
flowing mobile phase passes through the column. The flow of the mobile phase can be gradient
or isocratic. In gradient flow, two or more solvents are mixed in a programmed manner to effect
the best separation of the components in a mixture. In addition to variable composition, the
flowrate can vary during the analysis. In isocratic flow, the mobile phase is premixed (constant
composition) and the flowrate is kept constant. During method development, conditions are
optimized (flowrate, type and temperature of column, mobile phase composition and pH) to get
the best separation and peak shapes.
The basic parts of the HPLC system are the pump, injector, column and detector. The pump
delivers a programmed flow of solvent. The injector introduces the sample into the flowing
mobile phase. The column has a finely divided packing, which slows the rate of travel of
different chemicals according to their affinity for the packing. The chemical is qualitatively
defined by the time of arrival at the detector.
In 1993, Cossar and Carlile introduced a new method for determination of quaternary
pyridinium salts13. They used gradient flow, mixing acetonitrile and a pH 5 aqueous acetate
buffer and flowing through a C-18 Bondapak column (15 cm x 3.9 cm) to separate the
components. UV absorbance at 280 nm was utilized to monitor the major components of
corrosion inhibitors. HPLC was shown to overcome the interference problem with the dye
transfer method.
Linear response was obtained for 1 1000 ppm range. The computercontrolled operation allowed identical treatment of the samples. The time versus absorbance
trace for any number of samples could be directly compared, even if they were acquired on
different days.
With the HPLC method, Cossar and Carlisle showed that every corrosion inhibitor formulation
has its own fingerprint of characteristic peaks. The authors found that 25-minute runs
produced acceptable confidence for greater than 95% of field water samples analyzed. At a
flowrate of 2 mL/minute, all the quaternary amines were eluted in 12 minutes. A column wash
and column equilibration for 13 minutes prepared for the next sample injection. The area under
the peak was directly proportional to the amount of inhibitor in the sample. Standard
concentrations were made to bracket the recommended treating rate. Hence, sample from a
pipeline being treated at 300 ppm is analyzed using 100, 300, 500 ppm standards prepared in
distilled water.
For the two pyridine quats in the study, the authors found detection limits of 0.3 and 3 ppm. In
contrast, the dye transfer method had detection limits of 5 and 10 ppm for the same samples.
McKerrell and Lynes30 developed a HPLC method to analyze nitrogen-containing corrosion
inhibitors in a mixed hydrocarbon/glycol solvent. The method was used to analyze two
corrosion inhibitors. Inhibitor A was imidazoline in triethylene glycol. Inhibitor B consisted of a
8

mixture of fatty acid, alkylamine salts, polyol ester and fatty acid ester in an aromatic solvent.
The inhibitors were used in oil pipeline fluids to provide protection to the well risers and to the
pipeline in the Far North Liquids and Associated Gas Systems (FLAGS) pipeline at St. Fergus in
Scotland.
Samples were taken at the slug catcher and consisted of the production brine, condensate,
diesel oil, triethylene glycol, Inhibitor A and Inhibitor B. The samples were dispersed in a
methanol/dichloroethane solution. Separation of the two inhibitors was done using a mobile
phase of water, methanol, dichloroethane and acetic acid. The dichloroethane produced
sharpened peak shapes, improved retention time reproducibility and promoted column
regeneration. Acetic acid (0.1% v/v) was found to be the key to successful and reproducible
regeneration of the ODS 2 column. For detection, McKerrell and Lynes derivatized the inhibitors
with fluorescamine. Detection limits were 0.02% (200 ppm) for the imidazoline (Inhibitor A) and
0.1% (1000 ppm) for Inhibitor B. Automation of the HPLC allowed unattended analysis around
the clock.
Son and Chakravarty9 used isocratic flow of premixed mobile phase components (55% sodium
heptanesulfonic acid, buffered at pH 2 2.5 and 45% acetonitrile) to separate quaternary
amines. Using a Spherisorb C-18 column (25 cm x 4.6 mm), the quats were detected using both
UV and fluorescence, installed in series. At 1.25 mL/minute, flow, the analysis time was 30
minutes. Peaks of interest eluted within 10 minutes and the other components eluted later. A
column wash and regeneration followed. The UV monitoring wavelength was 270 nm while for
fluorescence measurements, excitation wavelength was 320 nm and the emission wavelength
was 400 nm. The column was maintained at 40C, which promoted lower viscosity of the mobile
phase and lower column pressures. The simplicity, improved signal to noise ratio and lower
pump maintenance, are desirable features for running the method in small district laboratories.
The investigation9 showed that HPLC/fluorescence was less sensitive to common interferents
such as dodecylbenzene sulfonic acid (DDBSA) and salinity of the production water.
Matherly, et. al.15 analyzed imidazoline and amine-based corrosion inhibitors in production
fluids from the North Slope, Alaska using HPLC/fluorescence. Solid phase extraction (SPE) was
used to process the samples. The method was used for analyzing corrosion inhibitors in both
aqueous and crude oil samples, as well as solids from corrosion coupons and production
pipes. For crude oil samples, the SPE (silica gel columns) trapped the desired corrosion
inhibitor species and allowed crude oil and non-polar solvents to pass through. After column
clean-up with o-xylene and methanol, complexation of the trapped chemical with fluorescamine
and extraction of the complex with methanol was accomplished, using a secondary pump
circulating at 10 mL/minute at pressures less than 500 psi.
The corrosion
inhibitor/fluorescamine complex was eluted with methanol and then injected into the
chromatograph.
The complexation, with the fluorescamine/methanol solution circulated
through the SEP column, was complete in 30 minutes.
On injection of the
inhibitor/fluorescamine complex in methanol into the HPLC column, the peaks of interest eluted
within 3-7 minutes for imidazolines and 9-20 minutes for amines.
A standard calibration curve was generated using corrosion inhibitor batches. Standards were
processed the same way as the samples. Brine samples were processed using C-18 bonded
silica gel and washing with D. I. Water.
The HPLC procedure used by Matherly et. al. employed isocratic solvent flow at 2 mL/min,
excitation wavelength of 278 nm and emission wavelength of 476 nm. The detection limit for
imidazolines, amides and amines was 0.2 mg/L or ppm.

With data from the HPLC/fluorescence method on concentrations of imidazoline and amidoamines in both oilfield water and crude oil samples, they were able to estimate the lifetime of the
corrosion inhibitor treatments in the well and hence, to estimate when the next well treatment
was needed. Analytical data corresponded very well with the data from the corrosion probes
placed on similar wells.
Matherly, et. al. extended the use of the technique to determine corrosion inhibitors that filmed
on metal surfaces or that were adsorbed on solids. The pipes and solid samples were
substituted for the SPE column and the inhibitor extracted using recirculation of
fluorescamine/methanol solution.
With the component separation feature of HPLC, the corrosion inhibitor concentration can be
determined several times (based on each component) from the same sample run, providing an
internal check on the accuracy of the analysis (assuming components have similar partitioning
characteristics). HPLC methods are laboratory procedures that are suitable to district or plant
laboratories due to easy set-up and ease of automation. Unattended 24-hour analysis has been
setup in many applications.
GAS CHROMATOGRAPHY /MASS SPECTROMETRY
In 1995, Gough, Haslegrave and Hedges3 compared Fast Atom Bombardment Mass
Spectrometry (FAB-MS), Gas Chromatography-Mass Spectrometry (GC-MS) and Liquid
Chromatography with diode array detection (LC-DAD) for the analysis of quaternary ammonium
compounds. They preferred the superiority of the GC-MS for its sensitivity (<1 mg/L or ppm
detection limit), molecular specificity (alkyl chain length and degree of branching), selectivity
and ease of operation in the analysis of production fluids from around the world. In comparison,
they concluded that the FAB-MS instrumentation was more expensive and the data produced
was only semi-quantitative. They found the LC-DAD method lacking in sensitivity and suffered
from interferences even after extensive cleanup of real sample extracts.
The GC-MS procedure consisted of preparing standards in 3% NaCl, addition of an internal
standard solution (C18 quat), pre-concentration through SPE columns under slight vacuum,
extraction of the quats with solvent and injection into the GC-MS. An internal standard was
added to monitor extraction efficiency, which was found to vary for different brine solutions.
Both calibration standards and samples were pre-concentrated from about 100 mL brine by SPE
columns. Oilfield quats are usually coco-based with chain lengths from C8 to C18. The quats
analyzed by Gough et. al.3 were benzalkonium chloride quats of even alkyl chain length (C12, C14
and C16), benzalkonium quats of odd alkyl chain length (C13 and C15), and ethyldimethylalkyl quat.
Detection limit was < 1 mg/L (1 ppm). With the GC/MS, the quats are differentiated not only by
the length of the carbon chains in the molecule but also the degree of branching.
Due to environmental considerations, many of the toxic aromatic amines and salts have been
replaced with more acceptable long-chain aliphatic amines or their salts in a number of
applications. Kusch et. al.31, for example, developed a sensitive GC technique for the
identification and determination of long-chain primary alkyl amines in boiler water, steam and
condensate. For these applications, detection limits in ug/L (parts per billion) levels are
required. The limit of detection for current analytical methods is higher than the residual amines
in these samples. The difficulty in amine analysis is due to the high polarity of the amines,
which makes them not easily extractable from the polar water matrix. Kusch found solid-phase
extraction using an octadecyl polymerically-bonded and end-capped SPE (the most
hydrophobic silica-based SPE) effective in concentrating the residual amines. SPE was used to
concentrate and isolate the amines and to separate the co-extracted interferents. The amines
10

were eluted from the SPE cartridge with n-hexane/THF (95/5) solution, then the eluting solvent
was evaporated using a stream of nitrogen or a vacuum pump.
The concentrated amine sample was then reacted with trifluoroacetic acid (TFAA) in THF or nhexane and analyzed by GC/FID, GC/NPD and GC/MS. Derivatization with TFAA prevented
nonlinear adsorption effects. Adsorption causes the formation of strong tailing peaks in a
chromatogram. Standards were prepared with an internal standard of dicyclohexylamine in nhexane and derivatized the same way.
The GC was equipped with a split/splitless injector, a flame-ionization detector (FID) and a
nitrogen-phosphorus detector (NPD), both operated at 320C. Helium was the carrier gas. The
fused silica capillary column had a film thickness of 0.25 um of DB-5. The splitter allowed the
simultaneous detection using FID and NPD. This technique is applicable to refinery samples.
The GC/FID/NPD (without the MS detector) equipment can be found in many refinery facilities.
ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ES-MS)
The number of publications on ES-MS in the oilfield industry demonstrates the high level of
interest and the success of research scientists in extending the use of this technique to more
chemical products and to lower concentrations. Extensive development work has keyed on
detection, qualitatively and quantitatively of quaternary ammonium compounds and
imidazolines. The extensive use of quats and imidazolines in corrosion inhibitor formulations is
due to their proven strong adsorption to surfaces. They coat metal and metal oxide surfaces
acting as a barrier to water and other corrodents. Imidazolines are sufficiently strong Lewis
bases to displace water from the Lewis acid sites of the oxide surfaces32. Moreover, their
strong adsorption properties carry over to solids in the production system phases (crude oil
and brine) as well as to the analytical determination, i.e. to the surfaces encountered in the
various processing steps.
The imidazoline is preferentially oil soluble, sparingly soluble in the water and tends to
accumulate at the oil/surface interface. A mechanism that makes imidazoline inhibit corrosion
is that water droplets roll off the imidazoline-coated surfaces leaving them completely oil-wet32.
Many corrosion inhibitor formulations include additives to make imidazolines partition more to
the brine.
In addition to GC/MS, Gough, Mothershaw and Byrne also used LC/Electrospray Mass
Spectrometry (ES-MS) to analyze oilfield chemicals24. Quats are permanently positively charged
molecules and are very responsive to electrospray ionization. Detection is in the sub-ppm
levels. With soft ionization, the individual quat molecules have little or no fragmentation.
With the LC column separating the individual quat components of corrosion inhibitors,
quantitative analysis of the individual components can be obtained in a single analysis. This
information is very useful for troubleshooting.
ES-MS is easy to automate and interface with LC and has superseded traditional soft
ionization techniques such as Fast Atom Bombardment (FAB) and Chemical Ionization (CI).
With such a sensitive analytical tool, the authors were able to observe that quat molecules
partitioned to the water phase >98%. Only 1% of the C18 quat partitioned to the oil phase.
Partitioning occurs on injection of the corrosion inhibitor to the production fluid. The dominant
mechanism that controls redistribution of quaternary ammonium actives in field systems
appeared to be surface adsorption. The longer and more linear the quat, the higher the extent of
surface adsorption.

11

Gough, et. al.33 extended the use of ES-MS to various quat corrosion inhibitors, imidazoline
corrosion inhibitors, emulsion breaker intermediates (alkylphenol, linear alcohol, alkylamine
ethoxylates and phenol/formaldehyde resins), chelants and phosphonate scale inhibitors. For
emulsion breakers, the ES-MS clearly showed the oligomeric series of ethoxylated alkylphenols
with 3-9 moles of ethylene oxide (EO) for a product made with four moles EO.
For this work, Gough et. al. analyzed a combination of benzalkonium chloride coco quat (5%),
DETA imidazoline (35%) and an EB package (5%) and 55% solvent. Two types of imidazolines
were analyzed TOFA (tall oil fatty acid)-DETA (diethylenetriamine) and a palm oilaminoethylethanolamine imidazoline. With this technique, the presence of both amides and
imidazolines, common in industrial imidazolines, was clearly shown. This is advantageous
when troubleshooting problems in the field. The ratio of amides to imidazolines in a formulation
can affect solubility and partitioning of the imidazoline in a formulation and hence, the
performance in particular applications. In the manufacture of industrial imidazoline, the quality
control of imidazolines usually includes specifications for amide to imidazoline ratios. The ESMS technique is superior to the classical infrared technique for this particular quality control
test. With the ES-MS developments, changes in the molecular composition of inhibitor
formulations as the product is distributed throughout oilfield systems can now be monitored.
Solid phase extraction (SPE) was used as part of the sample preparation process by
McCormack et. al.34. LC/ electrospray ionization multistage mass spectrometry (LC/ESI-MSn)
allowed the determination of individual imidazolines (2-alkyl-1-ethylalkylamide-2- imidazolines
and 2-alkyl-1-ethylamine-2-imidazolines) in crude oils with detection levels <10 ppm. This
technique has the potential of increasing the understanding of the mechanisms of industrial
imidazoline synthesis. Once perfected, it can be a monitoring tool for downhole and topside
oilfield operations and for environmental fate determination of imidazoline-based oilfield
corrosion inhibitors and surfactants.
Gough found that the standard deviation in ES-MS analysis of a mixture of quats and
imidazolines was high (12-15%). The use of an internal standard brought the standard deviation
to a more acceptable level of <5% and <10% for quats and imidazoline, respectively.
ES-MS is a sophisticated instrumental technique and hence, requires a trained
technician/chemist to interpret the spectra. Some materials, particularly those with high
molecular weight, can produce multiply charged ions. For example, Gough32 observed that the
nonylphenol ethoxylate formed adducts with ammonium (NH4), sodium or potassium adducts
that would add 17, 22 and 39, respectively, to the molecular weight. A nonylphenol ethoxylate
with nine moles of EO gave a spectrum with two overlapping sets of molecular ion signals, one
set of singly charged ions and another set of doubly charged ions. There were also ammonium
and sodium adducts.
Another chemical ionization technique, Atmospheric Pressure Chemical Ionization (APCI)
reduces the production of multiple ions and formation of ammonium, sodium or potassium
adducts and may be preferred, if the samples for analysis are predominantly high molecular
weight products.
Gough described how ions are produced in electrospray ionization techniques. The sample, in a
flowing liquid stream, passes through a fine stainless steel capillary, at the end of which is
applied a high positive or negative electric potential (3-5KV). Around the capillary is a tube that
directs a flow of nitrogen gas past the droplets of liquid that form at the capillary tip. The
combination of high voltage and gas produces a fine spray of ionized liquid droplets containing
both solvent and sample. The spray is directed to a high voltage lens and to a series of
sampling cones and skimmer lenses. The solvent vapor is separated from the charged sample
molecules in a process called ion evaporation. Sample ions are directed to a high vacuum
12

region where they separate and are detected. Various mass spectrometers will differ in
equipment design for ion formation and detection.
Langley35 also published an LC-ESI-MS work on imidazoline and quaternary ammonium salt.
Collective information on different corrosion inhibitor components is providing the industry
with more insight into the detailed molecular composition of corrosion inhibitors and improved
understanding of performance.
Grigson et. al.4 used electrospray ionization tandem mass spectrometry (ESI-MS/MS) to study
the composition of proprietary oilfield chemicals such as corrosion inhibitors and demulsifiers
and measure their residues in produced waters and marine sediments collected near two oil
production platforms (Thistle and Magnus) in the North Sea.
ESI/MS work has generated much useful and needed information for the industry on corrosion
inhibitors and other products. The soft ionization technique, as pointed out earlier, produces
molecular ions with little or no fragmentation patterns. Background ions from the instrument or
the solvent, and additional peaks from the samples themselves sometimes presented difficulty
in analysis of complex mixtures. Grigson used tandem MS to get additional specificity to
analyze complex samples such the marine sediments. In ESI/MS/MS, the parent ions of the
quats and the imidazolines were subjected to a collision-induced dissociation (CID) with argon.
The daughter ions were then analyzed by mass analysis. Grigson combined selective ion
recording (SIR) with the ESI/MS and improved the sensitivity of detection to parts per trillion
levels with low coefficient of variations (0.65 1.09%).
To process marine sediments, freeze-drying, followed by methanol extraction for quaternary
ammonium salts and dichloromethane extraction for imidazolines, both using an ultrasonic
bath, gave >90% recoveries. SPE procedures to remove salts from the sample and to
concentrate the analyte were developed and resulted in good recoveries for imidazolines and
benzalkonium quaternary ammonium salts. Octadecyl (C-18) bonded silica cartridges were
found adequate.
Grigsons work to analyze for quaternary amines and imidazolines in produced water samples
and marine sediments assisted in the validation of the CHARM predictions of concentrations of
oilfield chemical residues in produced water samples4.
Phosphate esters are also used in corrosion inhibitor blends33,36. Field brine samples from a
lease treated with a blend of phosphate ester, imidazoline and amides were analyzed using
LC/ESI-MS. Selective ion chromatograms of corrosion inhibitor standards are shown in Figure
5. Three components are shown phosphate ester, imidazoline and amide, identified by their
masses and fragmentation patterns. Calibration curves for the phosphate ester and imidazoline
were generated. The amide peak was not used, because when the field water samples were
analyzed, the amide peak was missing, indicative of the loss of the amide through partitioning
and adsorption processes.
Calibration curves were for corrosion inhibitor concentrations of < 1 ppm to 50 ppm and were
linear with excellent correlation coefficients for both the phosphate and the imidazoline
components (Figure 6). Field samples were analyzed to contain 1.1 to 1.4 ppm of corrosion
inhibitor, using either calibration curve37. For accuracy and precision, field samples with
concentrations lower than 1 ppm should be pre-concentrated through solid phase extraction or
even through simple evaporative techniques.

13

NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY

NMR spectroscopy is a powerful tool in the structural determination of organic compounds.
Compared to other spectroscopic techniques where the spectral response varies with the
chemical compound, in NMR spectroscopy, the spectral response (intensity vs. number of
species producing the signal) is independent of the compound. With this technique, absorption
coefficients are the same for the different organic substances, as long as the same nuclei are
analyzed. A widely used material, cocoamidopropyl betaine, is used in the oilfield industry as a
component of corrosion inhibitors and foamers. The compound gives specific signals in 1H
(proton) and 13C-NMR. The signal position at 3.3 ppm is a very specific one and usually no other
chemical group appears in this part of the spectrum. Interferences are usually identified with
signals in other areas of the spectrum38.
As in other quantitative analytical techniques, the signal intensity related to an internal standard
corresponds to the concentration. For cocobetaines, Gerhards, et. al.38 found 0.5% (500 ppm)
solutions can be directly identified with either proton or carbon 13 NMR. For lower
concentrations, specific pre-concentration steps should be considered. The betaine-specific
signal has the advantage of an eight-fold degeneracy, increasing the intensity of the signal by
this factor.
In proton NMR, the signal most suited for the quantification of betaines is produced by an
overlap of the signals of the hydrogens in the two methyl groups attached to the quaternary
nitrogen and of the signal of the two hydrogens in the methylene group in the alpha position of
the amide structure. This signal appears at 3.3 ppm38.
In NMR spectroscopy, it is necessary to add an internal standard to the sample, which produces
a signal in a spectral region, which is free of signals from sample molecules. For the analysis of
betaines, Gerhards used sodium trimethylsilyl propionate (TSP) which produces a strong signal
that is not split by coupling effects (i.e., a single peak is observed at 0 ppm chemical shift).
NMR has the added advantage that it produces other structural information that allows the
detection of unusual components in the betaine test solution. NMR spectroscopy for betaines
is relatively quick (30 minutes or less) and hence, may be applied to quality control operations.
However, NMR spectroscopy, similar to LC/ESI-MS, requires expensive instrumentation and
special training for chemist operators. Even when utilized in quality control operations, the
instrument needs to be kept in a specially designed and well-maintained laboratory.
Carbon 13 NMR and FTIR spectrometers were used to study hydrolysis of imidazolines to
amides27, 28,39 in corrosion inhibitor formulations and to determine substitution of materials in
the formulation and addition of correct ratios of ingredients. Both techniques showed that the
imidazoline/amide molar ratios decreased more than 20-fold within 20 days of inhibitor
synthesis. Substitution of different dimer-trimer acid in the corrosion inhibitor and addition of
correct ratios of ingredients were easily detected.
From the Valone 13C NMR study, the peaks of interest were the dimer-trimer acid at
approximately 180 ppm, the amide at approximately 174 ppm, the ester at approximately 173
ppm and the imidazoline at about 167 ppm. Due to signal to noise problems, only the peak
heights could be measured, rather than the preferred method of peak area integration. The
latter gives more accurate results since the peaks are not single sharp peaks but rather closely
spaced multiplets. To improve the accuracy, an internal reference standard, Trimethylsilane
(TMS) of known concentration was added to each sample. TMS is used as a reference for
chemical shifts.

14

The investigations by Valone et. al. 27, 28,39 showed that Carbon 13 NMR and Fourier Transform
Infrared (FTIR) spectroscopic techniques complement each other in the qualitative and
quantitative analysis of corrosion inhibitors.
McMahon36 used 31P NMR to monitor the mechanism involved in the use of sodium
alkylethoxyphosphate (NaAEP) as a corrosion inhibitor in a crude oil pipeline. The NaAEP had
phosphate monoester and diester components and a small amount of phosphoric acid. It was
demonstrated that the phosphate ester was preferentially water-soluble in an oil/water system
with tendency to migrate to the oil/water interface.
The application of NMR for analysis of corrosion inhibitors in both aqueous and oil samples is
demonstrated in Figures 7 940. In Figure 7, the top spectrum is for a crude oil dissolved in
deuterated chloroform and the lower spectrum is the crude oil treated with an imidazolinecontaining product. The crude oil 1H spectrum was clean in the chemical shift range of 3.5 to
6.8 ppm. The additive is evident in the bottom spectrum. Figure 8 is the enlarged spectra of the
crude with the imidazoline-containing product. The regions are identified, with the imidazoline,
amide and amine peaks close to 3 ppm.
Figure 9 is a spectrum of a produced brine with 0.5% (v/v) corrosion inhibitor blend containing
imidazoline and phosphate ester. 1H data was collected at 750 MHz using a PRESAT (presaturation) experiment to suppress the water signal. The water signal suppression is through
selective excitation of water protons resulting in significantly reduced intensity.
Methanol and acetate salts, common in corrosion inhibitor formulations, give quite distinct
signals as in Figure 9. The integrated ratio of the (CH2)n and the terminal CH3 (see region
labeled Aliphatic) peaks can be used to identify the fatty acid used to produce the imidazoline.
From preliminary data, it is estimated that the detection limit would be around 100 ppm for the
additive. Data was collected using 64 acquisitions. Increasing the number of acquisitions will
improve the signal to noise ratio and allow lower concentrations to be determined.
ION CHROMATOGRAPHY
Ion chromatography (IC) is a separation technique for chemical compounds in either anionic or
cationic forms, in aqueous samples. IC is similar to HPLC, using a gradient pump to push the
buffer through the column. The ions separate in the column by a difference in polarity and on
elution are monitored by the detector of choice. Different columns are used for cations and for
anions.
In the oilfield industry, its application has expanded to analysis of anions (chlorides, fluorides,
nitrates, sulfates, etc.) in water samples, organic acids, scale inhibitors (phosphonates) and
cations such as quats. For environmental discharge samples, ICP is able to determine low
levels of organic acids. A conductivity detector is widely used for monitoring the concentrations
of the ionic species in a sample. With the introduction of mass detectors to replace the
conductivity cells, the technique will see an explosion of applications. The mass detector has
the advantage of both qualitative and quantitative identification of the unknown samples.
Aminotrimethylenephosphonic acid (ATMP) is used as a component of scale and corrosion
formulations. Commercial ATMP usually contain ATMP, hydroxymethylenephosphonic acid
(HMPA), n-methylaminodimethylenephosphonic acid (n-MADMP), phosphate and phosphite. In
1985, Pacholec, et. al.41 published the first report on identification and quantification of ATMP
phosphonates by ion chromatography. Using two detectors - conductivity and a post column
reaction with Fe(III) followed by UV/Vis detection at 330 nm, they were able to separate and

15

quantify all components in ATMP. The detection limits for the components ranged from 0.4 to
2.0 ppm.
Figure 10 is an overlay of ion chromatograms of two scale/corrosion inhibitor formulations from
a scale problem troubleshooting project42. The lack of performance in the product was
attributed to a decrease in Component A.
Spectra were generated using a conductivity
detector and hence, the individual phosphonate components were not identified in the same
experiment. With a mass detector, the components would have been identified by their
molecular weights.
INDUCTIVELY COUPLED PLASMA SPECTROSCOPY
For corrosion control programs in the oilfield industry, inductively coupled plasma
spectroscopy (ICP) is an important analytical technique. In developing treatment programs,
scale predictions, troubleshooting, problem-solving, and produced water composition is
needed. ICP, for its, simplicity, speed, accuracy, precision and multi-range capability is
preferred over atomic absorption, UV-Visible and titration techniques. In addition to cations,
ICP is also used for analysis of sulfur (for sulfates) and phosphorus (for phosphonates and
phosphates) in water samples.
ICP involves very simple sample preparation filtration and dilution with acid and deionized
water to the linear range for a particular analyte. The equipment is easily automated, which is
almost a requirement for the number of water samples that have to be analyzed in the
laboratories on any given day. One drawback is that the ICP spectrometer is a laboratory
equipment, not field equipment.
In laboratory development experiments and performance evaluations, it is often the case that
not enough field brine can be sampled from the production system. The brine composition is
established using ICP spectrometry and the required volume of synthetic brines of similar
composition is easily prepared to do the particular testing.
In scale squeeze projects, ICP is used by many laboratories to determine residuals where the
concentrations are in the low ppm to ppb levels. Graham et. al.43 effectively monitored ppb
levels of phosphonate and phosphino-polycarboxylate (PPCA) scale inhibitors in oilfield waters
using ICP. The difficulty associated with low levels of scale inhibitors (ppm to ppb) was
overcome with the choice of the right analytical line (177.499 nm P line) and matching the matrix
of the standards with the produced brine. Concentrations <1 ppm are easily achieved with ICP.
The use of a Sep-Pak C18 cartridge can help improve accuracy and precision by minimizing
organic interferents in water samples.
RADIOACTIVE TRACER TECHNIQUE
In 1966, a radioactive tracer technique was successfully used by Continental Oil Co. to test the
concentration of corrosion inhibitor in pipelines44. The analysis used a modified tritium labeling
technique based on the catalytic exchange of tritide with the hydrogen at unsaturation positions
of the molecules. For the 540 mile-pipeline from Billings, Montana to Spokane, Washington, 20
ppm of inhibitor injected at one terminal was found adequate to protect against corrosion
throughout the length of the pipeline.

16

GEL PERMEATION CHROMATOGRAPHY

Most of the components used in corrosion inhibitor formulations are small molecules.
However, polymeric molecules, such as the emulsion breakers and acid corrosion inhibitors,
are also routinely used in the industry. Gel permeation chromatography (GPC), also known as
size exclusion chromatography (SEC), is for characterization of high molecular weight
compounds, such as emulsion breakers, water clarifiers and flow improvers, rather than
identification and quantification.
GPC was used to analyze for conversion products of acid corrosion inhibitors, including
surface films formed on N80, J55 and 1026 stainless steel coupons, exposed to 15% HCl for up
to 6 hr at 65C (121F)45. The inhibitors included 1-octyne-3-ol and a commercial formulation
containing 4-ethyl-1-octyn-3-ol, a nonionic ethoxylated surfactant and a reaction product of
acetophenone, formaldehyde and an amine with and without inhibitor aids (formic acid or
potassium iodide). The inhibitor aids are used to improve adherence of the protective film. By
GPC, the film formed from the corrosion inhibitors was found to be polymeric ketones from 4002000 molecular weight.
CAPILLARY ELECTROPHORESIS/DAD
Amines are widely used as corrosion inhibitors in refineries. GC and HPLC are widely used for
analysis of aliphatic and cyclic amines. Another applicable technique applicable is capillary
electrophoresis (CE)46. In CE, application of an electric field separate amines as cationic
species and are detected indirectly using low pH electrolyte systems containing UV-absorbing
additives.
SURFACE ANALYSIS TECHNIQUES
The focus of this review is on determination of corrosion inhibitors and related oilfield
chemicals in solution. However, surface analysis techniques are often used with solution
techniques to characterize performance of corrosion inhibitors. A few are briefly described
here, more to direct researchers to some potential tools that can complement difficult problemsolving, and definitely to aid in the development of better and greener inhibitors. The demands
of new regulations make it mandatory to develop improved performance, reasonably-priced and
environmentally-friendly chemicals. Where the corrosion inhibitor concentration is measured in
solutions and protection is related to a set of minimum dissolved concentration, surface
analysis measures how much corrosion inhibitor comes out of solution. These techniques
measure the thickness of the coating that is deposited on the metal.
Surface analysis techniques, such as X-ray Photoelectron Spectroscopy (XPS) and Time of
Flight Secondary Ion Mass Spectrometry (ToFSIMS), were used after electrochemical testing to
determine the surface composition and chemical state of the quaternary amine inhibitor. There
was no evidence of chemical reaction of the quaternary ammonium compound with the steel
surface. Adsorbed quaternary amine inhibitor was observed and measured at different
concentrations. The lowest concentration detected for the amine quat was 20 ppm25. XPS and
ToFSIMS surface analysis were used to monitor the adequacy of coverage, and hence,
corrosion protection. It was concluded that adsorption of the quat was due to a simple ionic
interaction of the quat with the steel surface. Longer chain quats were preferentially absorbed.
Another surface analysis technique is surface-enhanced Raman spectroscopy (SERS)47. The
strength of adsorption of quaternary compounds was found dependent on the steel used.

17

Transmission Mossbauer Spectroscopy, complemented by FTIR, was used to study the effects
of corrosion inhibitors on the corrosion of steel surfaces48. Actually detected were various
forms of iron oxides, -FeOOH and superpara-magnetic (SPM) -FeOOH. In the presence of
nitrite corrosion inhibitors, the corrosion product formed on mild steel showed nonstoichiometric magnetite (Fe3-xO4) along with oxyhydroxides. Phosphate inhibitors showed the
presence of ferrous phosphate. It was noted that sodium hexametaphoshate inhibited corrosion
by hydrolysis and subsequent formation of the barrier film. The protection mechanism of
phosphate was by iron phosphate formation, along with oxyhydroxides.
Electronic impedance spectroscopy is widely used in the evaluation of oilfield corrosion
inhibitors. However, the technique evaluates performance, rather than concentration and is
outside of the scope of the intended review. Papavinasam49 et. al.s paper discusses the
various performance methodologies for corrosion inhibitors in oil and gas pipelines.
DISCUSSION
Exploration for oil and gas is more challenging than ever. The search has taken the oil
companies to more remote, undeveloped areas on land and into deep waters. The challenge to
operators include low temperatures, high pressures, sweet and sour gases, miles of umbilical
tubing to bring chemical treatments where they are needed, long pipelines to transport
production fluids to processing plants, and more rigid state and federal regulations. Cost of
hardware (tubulars, pipelines, pumps, etc.) constitute a significant percentage of production
operations. Preservation of hardware integrity is closely linked to good corrosion control.
When corrosion problems occur that require replacement of tubulars, the cost of replacements
plus lost production during downtime is significant.
There are many monitoring techniques (electrochemical, ultrasonic, radioactive tracers,
coupons, etc.) available, some of which are very expensive, but there is no guarantee of 100%
protection year round. Residual corrosion monitoring provides added assurance of protection.
With remote sampling areas, the transport of samples can be problematic and can result in loss
of sample integrity. Low maintenance and low cost of production operations can be promoted
by not only preventing corrosion but also through early detection of the initiation of a corrosion
problem. Usually, catching the problem early results in a quick and more effective solution,
preventing need for tubular or pipe replacements. Residual analysis on location is definitely an
advantage. A challenge to the operator, and chemical and service providers is to provide
simple, fast and accurate analysis in the platforms or sampling stations. Automation with
rugged, inexpensive equipment circumvents the lack of trained technical personnel. The
analyzer must be able to operate under uncontrolled environment and unstable, sometimes
teetering or swaying remote production facilities.
Some development work to impart
ruggedness to the automated fluorescence method, successfully employed as a field method in
a lease in North America9 is needed. Development of a robotic version of the dye transfer
methods with improved accuracy and precision will appeal to, and help small district labs and
field personnel.
With the demands for more cost effective chemicals, lower chemical treatments per barrel of
produced fluids and more restrictive environmental policies made into laws, lower and lower
residual concentrations, (low ppms to ppb) need to be determined. A challenge to the industry
is to develop more sensitive analytical methods. Elimination of matrix interference and
development of easy and quick sample preparation will continue to challenge the analytical
chemists and need to be continuously addressed. Development of more reasonably priced
analytical instruments would promote acquisition and use in district laboratories.

18

Extensive research is underway to address the demands for greener chemicals. New chemicals
are designed and synthesized every day. New chemistries for corrosion inhibitors may need
new or drastically improved analytical techniques. LC/ESI/MS and NMR spectroscopy are
excellent for qualitative identification but will need more development work to analyze low
concentrations (parts per billion or lower). The tandem MS technique, capable of parts per
billion sensitivity, needs more development work. The second MS module makes the
instrument more expensive and beyond the reach of most district laboratories.
SUMMARY AND CONCLUSIONS
Spectroscopic techniques (UV/Visible) provide specificity, low detection limits and portable
analytical solutions for the analysis of oilfield chemicals. These techniques may sometimes be
hindered by interferences. In some situations, advanced analytical techniques such as
fluorescence spectroscopy, can be applied with improved accuracy. When needed, analytes
can be chemically modified through derivatization procedures to provide the necessary
detection mechanism.
For complex mixtures, often encountered with oilfield samples, hyphenated techniques using
separation techniques are needed and required for analytical accuracy. Examples are thin layer
chromatography (TLC) and high performance liquid chromatography (HPLC).
The
chromatographic techniques can be coupled with various detection methods: UV, Visible,
Fluorescence, Mass Spectrometry, etc. FTIR, a workhorse for organic chemicals analysis has
the advantage of sensitivity and specificity. It is applicable for hydrocarbon-based matrices but
is not applicable for direct analysis of aqueous-based systems. NMR offers the capability of
analysis of aqueous systems but may lack the required detection limits.
Existing analytical methods for determination of residual corrosion inhibitors are discussed and
compared in the paper to give the analyst a choice of methods depending on the number of
samples, the technical ability of personnel and laboratory instrumentation available. The
sensitivity, ease and cost of set-up are compared (Table 1) for the different methods. Challenges
in the industry that need to be addressed with more research and developments have also been
discussed.

ACKNOWLEDGEMENTS
The author wishes to thank Claire Conboy, Nellie Chu, George Cunningham, Kathy Eddlemon,
Henry Fisher, Danielle McGowen, Sabrina Miller, Mark Nace and Rupi Prasad for their invaluable
help in the preparation of the manuscript and Champion Technologies for permission to publish
the paper.

REFERENCES
1. Joosten, M., Buck, E., Kolts, J., Erickson, D. and Mai, M., Paper No. 9, Corrosion 92.
2. Gatlin, L. W., Hudman, J. D. and Williams, D. C., Oilfield Subsurface Injection of Water,
ASTM STP 641, C.C. Wright, Dennis Cross, A. G. Ostroff and J. R. Stanford, Eds., ASTM,
1977, pp. 57-68.
3. Gough, M.A., Haslegrave, J. A. and Hedges, W. M., 6th International Oilfield Chemicals
Symposium, Geilo, Norway, 1995.
19

4. Grigson, S. J. W., Wilkinson, A., Johnson, P., Moffat, C. F. and McIntosh, A. D., Rapid
Communications in Mass Spectrometry 14, 2210-2219 (2000).
5. Buck, E., Allen, M., Sudbury, B. and Skjellerudsveen, B., Paper No. 99, Corrosion 93.
6. Son, A. J., Proceedings, NACE Northern Area Western Conference, Saskatoon,
Saskatchewan (March 2000).
7. Naraghi, A., U.S. Pat. 5,611,991, March 1997.
8. Naraghi, A. and Grahmann, N., U.S. Pat. 5,611,992, March 1997.
9. Son, A. J. and Chakravarty, J., Paper No. 344, Corrosion 96.
10. Rosen, M. J. and Goldsmith, H. A., Systematic Analysis of Surface-Active Agents, 2nd
Edition, Wiley-Interscience (1972), pp. 459-463.
11. Skadhauge, K. and Fogh, J., Acta Path. Microb. Scan., 32, 290 (1952).
12. Fogh, J., Paul, O., Rasmussen, H and Skadhauge, K., Analytical Chemistry, 26, No. 2
(1954), pp. 392-395.
13. Cossar, J. and Carlile, J., Paper No. 98, Corrosion 93.
14. Son, A. J., Paper No. 04373, Corrosion 2004.
15. Matherly, R., Jiao, J., Blumer, D. and Ryman, J., Paper No. 543, Corrosion 95.
16. Fortenberry, C., Jr., Grahmann, N., Miller, C., and Son, A., SPE 26607, 68th Annual
Technical Conference and Exhibition of the Society of Petroleum Engineers, Houston,
Texas, Oct. 1993.
17. Son, A. J. and Muckleroy, B. S., Materials Performance, Sept. 1997, pp. 38-47.
18. Siggia, S. and Hanna, J., Quantitative Organic Analysis via Functional Groups, 4th
Edition, John Wiley & Sons (1979), pp. 690-693.
19. Clesceri, L.S., Greenberg, A. E. and Trussell, R. R., Standard Methods for the
Examination of Water and Wastewater, American Health Association, Washington, D.C.
(1989), pp. 4-139 to 4-147.
20. Kan, A. T., Varughesse, K., and Tomson, M. B., SPE 21006, Feb. 1991 (Anaheim,
California).
21. Javier, A., Crouch, S. and Malmstadt, H., Analytical Chemistry 40, No. 13 (1968), pp. 1922
1925.
22. Izawa, Y., J. of Japan Oil Chemist Society, Vol. 11 (1962), pp. 627-630.
23. Guilbault, G., Editor, Practical Fluorescence, Marcel Dekker, Inc. (1990) pp. 265-269.
24. Gough, M. A., Mathershaw, R. A. and Byrne, N. E., Paper No. 33, Corrosion98.
25. Palmer, J. W., Piercey, A. R., Hibbert, S., Mitchell, R., Swift, A. J., Turgoose, S., Paper No.
40, Corrosion 95.
26. Buck, E. and Sudbury, J., U.S. Pat. 5,152,177 (Oct. 1992).
27. Martin, J. and Valone, F., Paper No. 232, Corrosion 84.
28. Martin, J., Valone, F. W. and Haltmar, W. C., Paper No. 378, Corrosion 85 (Boston).
29. Martin, J. and Valone, F., Paper No. 233, Corrosion 84.
30. McKerrell, E. H. and Lynes, A., Chemicals in the Oil Industry International Symposium, 3rd
Royal Society Special Publication No. 67 (1988), pp. 212 -222.
31. Kusch, P., Knupp, G., Hergarten, M., Kozupa, M. and Majchrzak, M., J. of
Chromatography A, Vol. 1113, Issues 1-2, (April 2006), pp. 198-205.
32. McMahon, A. J., Colloids and Surfaces 59 (1991) pp. 187-208.
33. Gough, M.A., Langley, G. J., Hedges, W. M. and Byrne, N.E., 8th International
Oil Field Chemical Symposium, March 1997, Geilo, Norway.
34. McCormack, P. Jones and Rowland, S. J., Rapid Communications in Mass
Spectrometry 2002, 16: 705-712
35. Langley, G. J., Chemicals in the Oil Industry (Special Publication, Royal Society
of Chemistry), V 211, 190-197 (1998).
36. McMahon, A. J., Proceedings of the 7th European Symposium on Corrosion Inhibitors
(7SEIC) Ann. Univ. Ferrara, N.S., Sez. V, Suppl. N9, 1990.
37. Chu, N., Internal Report, Champion Technologies, Nov. 2005.
38. Gerhards, R., Jussofie, I., Kaseborn, D., Keune, S. and Schulz, R., Tenside Surfactants
Determination, 33 (1996), 1, pp. 8-14.
20

39. Martin, J. A. and Valone, F.W., Paper 232, Corrosion 84 (New Orleans).
40. Conboy, C., Unpublished Report, Champion Technologies, Sept. 2006.
41. Pacholec, F., Rossi, D., Ray, L. and Vazopolos, S., Organic Analytical Chem., Vol.3, No.
12 (1985).
42. Son, A. J. and Sitz. C., Proceedings, International Symposium for Ion Chromatography,
San Diego, California (2003).
43. Graham, G., Sorbie, K., Johnston, A. and Buck, L., 7th NIF International Symposium on
Oilfield Chemicals, Geilo, Norway (March 1996).
44. Riggs, O. L., Jr., Hutchison, M. and Gant, P.L., Material Protection, V.5, No. 11
(Nov. 1966), pp. 27-29.
45. Frenier, W. W. and Iob, A., Paper No. 150, Corrosion 88 (St. Louis).
46. Pereira, E. A., and Tavares, M. F. M., J. of Chromatography A, Vol. 1051, Issues 1-2, pp.
303 308 (Oct. 2004).
47. Oblonsky, L., Divine, T. and Chestnut, G., Corrosion, Volume 51, No. 12, pp. 891-900 (Dec.
1995).
48. Ramesh Kumar, A. V., Nigam, R. K., Monga, S. S. and Mathur, G. N., Anti-Corrosion
Methods and Materials, Vol. 49, No.2, pp. 111-117 (2002).
49. Papavinasam, S., Revie, R. W., Attard, M., Demoz, A. and Michaelian, K., Corrosion, Vol.
59, No. 10, pp. 897 912 (2003).

APPENDIX A
DYE EXTRACTION METHODS6,9-17
Sample Preparation and Standards Preparation are similar for the different dye extraction
methods and consist of the following:
1. Separate the oil phase from the brine phase.
2. Acidify, as needed, using hydrochloric acid or nitric acid to pH 2.
3. Filter the aqueous sample (Whatman #2 filter paper, 0.45-micron filter, etc.) to remove
any suspended solids.
4. Obtain untreated brine from the lease or prepare synthetic brine similar to the sample
matrix. Acidify and filter, if needed.
Standards Preparation
1. Prepare 1% solution of water-soluble or water-dispersible corrosion inhibitor in the clean
untreated or synthetic brine. If not completely clear, treat with methanol.
2. Prepare 3 5 standards with the concentrations bracketing the expected sample(s)
concentration(s) in the clean brine.
Note: standards are prepared from a sample of the corrosion inhibitor, preferably from the
same batch used to treat the system in the field. Turn on the spectrometer while the
standards are being prepared.
Complexation with Bromocresol Purple
1. Prepare 3 phosphate buffers, pH 5.7, 4.2 and 9.7 (Buffers A, B and C).
2. Process standards and samples according to the following extraction procedures.
3. To a known volume of standard (or sample) in a separatory funnel, add bromocresol
purple, Buffer A and chloroform. Shake well.
4. Separate the chloroform (bottom) layer and add Buffer B and shake well.
5. Separate the chloroform (bottom) layer and add Buffer C. Mix well.
6. Extract the chloroform layer a third time, add ethanol and mix well.
7. Read and record absorbance at 590-600 nm.

21

8. Generate the calibration curve (standard concentration vs. absorbance) and calculate
concentration of the corrosion inhibitor in the sample(s). Correct for any dilution of the
sample(s).
Complexation with Bromophenol Blue
1. To a known volume of standard or sample in a separatory funnel, add sodium carbonate
solution. Shake well.
2. Add bromophenol blue solution. Shake well.
3. Add toluene and shake well.
4. Extract the top toluene layer and measure absorbance of standards and samples at 580600 nm.
5. Generate the calibration curve (standard concentration vs. absorbance) and calculate
concentrations of corrosion inhibitor in the samples from the calibration curve. Correct
for any dilution.
Complexation with Methyl Orange
1. To a known volume of standard or sample in a separatory funnel, add borax buffer
solution, adjust pH to 8-9.
2. Add methyl orange and shake well.
3. Add chloroform and extract the inhibitor/methyl orange complex with chloroform (bottom
layer).
4. Measure absorbance of methyl orange complex in the chloroform at 425 nm.
5. Generate calibration curve (concentration vs. absorbance and calculate concentration(s)
of inhibitor in the brine sample(s) by comparison to calibration curve (absorbance vs.
concentration of standards). Correct for any dilution.

APPENDIX B
STATIC ULTRAVIOLET AND FLUORESCENCE SPECTROSCOPY METHODS FOR
CORROSION INHIBITORS IN OILFIELD WATERS2,9,14
Sample(s) Preparation and Standards Preparation are the same as given in Appendix A.
Turn on the spectrometer while preparing the standards and the sample(s).
Static Ultraviolet Spectroscopy
1. Read absorbance of the standards at desired wavelength, single or range (for quats, 270
nm, 260-280nm) and generate the calibration curve.
2. Read absorbance of the sample and compare to the calibration curve to determine
concentration. Dilute the sample, as needed. Correct concentration results using the
dilution factor.
Static Fluorescence Method
1. To monitor the quat component, set excitation wavelength at 325 nm and emission
wavelength at 400 nm. The fluorescence intensities of standards and samples are read
directly.
2. To monitor the imidazoline or amine components, they need to be complexed with
fluorescamine. While the fluorescence spectrometer is warming up, add fluorescamine
solution to standards and samples. Mix well.
3. Allow color development for 15-30 minutes. Use the same time for both standards and
samples.
4. Set the excitation wavelength at 275-280 nm and the emission wavelength at 460 480
nm. Read the fluorescence intensities of the standards and generate calibration curve.
Read the fluorescence intensities of the samples. Calculate sample(s) concentration from
22

the calibration curve (concentration vs. fluorescence intensity. Correct for dilution, as
needed.
Both UV and fluorescence methods can be easily automated by adding an auto-sampler and
building the automation into the program that comes with the spectrometer.
Automated Fluorescence Spectrometry as a Field Method
1. Turn on fluorescence spectrometer lamp and stabilize for 30 minutes.
2. Load the undiluted field samples into the carousel. Acidify and filter sample, if turbidity
is detected, before loading sample into the carousel.
3. Load the proper calibration curve (each corrosion inhibitor has a different calibration
curve, set-up by a chemist initially and rechecked at monthly intervals).
4. When oil or emulsion is visually detected, a methanol sample is run before and after the
brine sample.
5. Equipment goes through the following steps: sample pickup, dilution, mixing, delivery to
fluorescence cell, rinsing and analysis.
6. Deionized water is inserted after every 10 samples to check the lamp intensity and
methanol wash every 15th sample to prevent problems from oil, solids and emulsions.
7. Check calibration curves at programmed intervals by running a few standards and
comparison to the stored calibration curves.

APPENDIX C
SPE/HPLC/FLOURESCENCE FOR ANALYSIS OF CORROSION INHIBITORS IN CRUDE OIL15
1. Prepare a series of standards in o-xylene. Pipet a known volume of each standard into a
silica gel cartridge.
2. Wash cartridge with o-xylene and methanol until clear solution comes out.
3. With a recirculating pump, circulate a fixed volume of fluorescamine solution in methanol
through the cartridge for 30 minutes. Make up to volume with methanol and mix well.
4. Inject solution of fluorescamine complex to HPLC. Read fluorescence intensity using
excitation wavelength of 278 nm and emission wavelength of 476 nm.
5. Generate calibration curve of concentration vs. fluorescence intensity.
6. Analyze crude oil samples as above, calculating the inhibitor concentration by
comparison with the calibration curve.
7. For aqueous samples, a C-18 cartridge is used. Washing is done with D.I. water, followed
by the fluorescamine complexation and extraction with methanol.
Note: solids and corrosion inhibitor on the surface of the pipe may be analyzed by putting
the solid or pipe in a small beaker, cover with enough fluorescamine solution and circulate,
using recirculation pump, for 30 minutes.
APPENDIX D
NMR SPECTROSCOPY PROCEDURE FOR BETAINES28
1. Weigh 40 mg of betaine sample. Add 1 g of 0.75% propyl-deuterated NaTSP in D2O into
NMR tube. The deuterated water acts as lock substance in the NMR experiment. The
deuterated propyl group prevents additional signals in the high field part of the 1H-NMR
spectrum observed from ordinary propyl groups which could interfere with signals in
that spectral region.
2. Record spectrum.
3. Check spectrum for unexpected signals to identify unusual components.

23

4. Integrate the signal intensities of the betaine-specific signal at 3.3 ppm and the TSP
signal.
5. Calculation of Betaine Concentration:
% Betaine = mTSP /mBET* IBET/ITSP * MBET/MTSP* nHTSP/nHBET* 100
Where m = weighed mass
I = intensity
M = average molecular weight
n = number of hydrogens producing the betaine specific signal and in the
trimethylsiloxy group of TSP
Table 1. Comparison of Analytical Procedures for Analysis of Corrosion Inhibitors
Method

Analyzed
Component

Methyl Orange
Quats*
Complexation
Bromocresol
Quats
Purple
Complexation
Bromophenol Blue
Quats
Complexation
Visible
Phosphonates,
Spectroscopy
phosphate esters
Static UV
Quats, amines,
Spectroscopy
imidazolines
Static Fluorescence Quats, amines,
imidazolines
TLC
Quats, amines,
imidazolines
HPLC/UV
Quats, amines,
imidazolines
HPLC/Fluorescence Quats, amines,
imidazolines
GC/MS
Quats
HPLC/ES/MS
Quats,
imidazolines,
phosphate esters
LC/ES/MS/MS
Imidazolines
NMR
Imidazolines
*quaternary ammonium compounds

Detection
Limit
1 ppm

No

Relative
Ease/Cost of
Set-up
Easy/Low

< 1 ppm

No

Easy/Low

<1 ppm

No

Easy/Low

0.1 ppm

Yes

Easy/Low

1 ppm

Yes

Easy/Low

1 ppm

Yes

Easy/Low

1 ppm

No

Easy/Low

0.3 ppm

Yes

Medium

0.1 ppm

Yes

Medium

< 1 ppm
<1 ppm

Yes
Yes

High
High

300 ppt
100 ppm

Yes
Yes

High
High

24

Automation

Figure 1. Typical Components of Corrosion Inhibitors

CH 3
H2
C N R

H
HN

H
NCOR
1
Diamide, where R = predominantly C18

CH 3

Coco Quat where R = C8 C18

H
NCOR

N 2 N

COR
N
2

N 2 N

NH 2

Amidoimidazoline, where R = predominantly C18

Imidazoline, where R = predominantly C18
O
R(OCH 2CH2) xO P OH
OH

R(OCH2CH 2)x O

O
P

R(OCH2CH 2)xO

(Mono)- Phosphate Ester,

where R = alkyl group

OH

(Di)- Phosphate Ester, where R = alkyl group

Figure 2. Absorbance Spectra of Bromocresol Purple/Quaternary Amine Complexes

1.2

Absorbance (AU)

1
0.8
0.6
0.4

FIGURE 2. Absorbance Spectra of Bromocresol Purple

Complexes of Corrosion Inhibitor Standards

0.2

0
200

400

600

25

Wavelength (nm)

Figure 3. Reaction of Fluorescamine with Primary Amines

O
O

NH2

OH

C OO H

Fluorescamine

Primary Amine

Pyrrolidine

Figure 4. Emission Spectra of Corrosion Inhibitor, Before and After Partitioning

26

API-ES, Pos, SIM,

API-ES, Pos, SIM,
API-ES, Pos, SIM,
API-ES, Pos, SIM,
API-ES, Pos, SIM,
API-ES, Pos, SIM,

Frag: 70 (TT),
Frag: 70 (TT),
Frag: 70 (TT),
Frag: 70 (TT),
Frag: 70 (TT),
Frag: 70 (TT),

"MSD
"MSD
"MSD
"MSD
"MSD
"MSD

Positiv e"
Positiv e"
Positiv e"
Positiv e"
Positiv e"
Positiv e"
1 3 . 9 56 1270

MSD1 TIC, MS File (F:\DATA\2005912\NC591202.D)

MSD1 TIC, MS File (F:\DATA\2005912\NC591203.D)
MSD1 TIC, MS File (F:\DATA\2005912\NC591204.D)
MSD1 TIC, MS File (F:\DATA\2005912\NC591205.D)
MSD1 TIC, MS File (F:\DATA\2005912\NC591206.D)
MSD1 TIC, MS File (F:\DATA\2005912\NC591207.D)
Norm.

Figure 5. Selective Ion Chromatograms of

Corrosion Inhibitor Standards

175000

Amide

150000

125000

7.746

100000

Phosphate
Ester

13.616

50000

7.738

75000

Imide

25000

0
6

10

12

14

min

Figure 6. Calibration Curves for Corrosion Inhibitor Components (LC/ES/MS)

Amidoimidazoline, MSD1 TIC

Area = 10199.0006*Amt -8176.4925
Area

Phosphate Ester, MSD1 TIC

Area = 22136.0228*Amt +12786.805

Rel. Res%(1): 634.370

Area

Rel. Res%(1): -19.290

1000000

400000
800000

300000

600000

5
200000

400000
4
200000

100000

12

3
12

Correlation: 0.99923

Correlation: 0.99757

0
0

20

Amount[ng/ul]

27

20

Amount[ng/ul]

Figure 7. Crude Oil with Product

Containing Amidoimidazoline

TMS

NaTSP

Acetate

MeOH

-(CH2CH2O)-

Residual water

Figure 8. Crude Oil Sample with Additive

aromatic

vinyl

Ethers Amines
Amides
Acids

28

Aliphatic

aromatic

Ethers Amines
Amides
Acids

vinyl

NaTSP

Acetate

MeOH

-(CH2CH2O)-

Residual water

Figure 9. Corrosion
Inhibitor in Produced
Brine

Aliphatic

Figure 10. IC Chromatograms of Good and

Poor Performing Scale Inhibitors

Poor
Performer

29