CORROSION ENGINEERING SECTION
A Study of Corrosion of Mild Steel in Mixtures
of Petroleum Distillates and Electrolytes
A. Groysman and N. Erdman*
ABSTRACT
Petroleum distillates are not corrosive unless water and some
other species are contained in them at particular concentra-
tions. It was not found in the literature what water concen-
tration and which species result in high corrosiveness of light
petroleum distillates. The purpose of this study was to
determine minimal (“critical”) water content and corrosive
species type resulting in high corrosiveness of petroleum
distillates. The study was conducted using mixtures of light
petroleum distillates (naphtha and gasoline) with water
content < 5 vol%, and in some cases with 10 ppm sodium
chloride (NaCl) solutions. The study confirmed the electro-
chemical origin of the corrosion mechanism and showed that
the main cause of corrosion in the petroleum distillates-
electrolyte mixtures was the presence of water and dissolved
oxygen. “Critical” water contents were obtained for naphtha-
water and gasoline-water mixtures. Salts (chlorides, sul-
fates, and nitrates) and organic acids (formic [HCOOH] and
acetic [CH3COOH]) were extracted from the naphtha and
gasoline by the aqueous phase and were responsible for the
severe corrosion of these petroleum distillates. Valuable data
regarding different types of corrosion attack (pitting or
uniform corrosion) on mild steel were acquired during the
study.
KEY WORDS: gasoline, mild steel, naphtha, petroleum
distillate-electrolyte mixture, water
Submitted for publication March 1999; in revised form, July
2000. Presented as paper no. 140 at CORROSION/99, April 1999,
San Antonio, TX.
* Oil Refineries Ltd., Haifa, Israel.
(1)
Based on the data collected at the Research and Development
Lab, Oil Refineries Ltd., Haifa, Israel.
0010-9312/00/000253/$5.00+$0.50/0
1266 © 2000, NACE International
INTRODUCTION
Crude oils consist of a variety of chemical sub-
stances, the majority of which are various organic
compounds (hydrocarbons). Some of these com-
pounds contain oxygen, sulfur, and nitrogen. One
can often find water, salts, hydrogen sulfide (H2S),
and other inorganic compounds in crude oils. All of
these corrosive species are withdrawn during various
technological processes such as desalting and
rectification of crude and treatment of petroleum
distillates (desulfurization, caustic treatment, etc.).
Petroleum distillates consist mainly of nonpolar
hydrocarbons that are not aggressive toward various
alloys under normal conditions. However, practice
shows that equipment that comes into contact with
petroleum distillates is being damaged. There are
leaks as a result of corrosion in storage tanks,
pipelines, pumps, and other equipment. The con-
struction material for most of the equipment is mild
steel. Hence, the focus of this work is the study of
reasons for corrosiveness of some petroleum distil-
lates (naphtha and gasoline) toward mild steel.
The presence of water and salts in petroleum
products is the main cause for corrosion during their
storage and transportation.1 The water content in
petroleum distillates manufactured at oil refineries is
generally very low (30 ppm in naphtha, 80 ppm in
gasoline).(1) These water quantities in petroleum
distillates are not able to make them corrosive. Water
vapors may ingress into petroleum distillates during
storage, transportation, and some other operations.
Water vapors may condense as a result of tempera-
CORROSION–DECEMBER 2000

ture changes, and water content in petroleum
distillates may reach more than 30 ppm to 80 ppm.
It is important to know the minimal (“critical”) water
concentration and corrosive species in petroleum
distillate that cause corrosion and the mechanism of
this process. This knowledge is vital while deciding a
prognosis for the lifetime of equipment, selecting
material of construction, or choosing preventive
measures. Most research in this area until now has
been carried out with hydrocarbon-water mixtures
with relatively high water content, ≥ 5 vol%.2-4 The
main lesson learned from these studies is that the
volume ratio of liquid water to liquid hydrocarbon
has a significant influence on the corrosion behavior
of metals. No one, however, has studied minimal
(“critical”) water content and which species, besides
water and oxygen, are responsible for corrosiveness
of light petroleum products.
The goal of this study was to examine mild steel
corrosion in hydrocarbon-electrolyte mixtures with
water content < 5 vol% (a concentration that is closer
to actual practice during transportation and storage
of petroleum distillates), determine minimal (“critical”)
water content, and discover corrosive species result-
ing in high corrosiveness of petroleum distillates.
CORROSION OF IRON
IN A HYDROCARBON-WATER ENVIRONMENT
In a hydrocarbon-water environment, a metal is
partially wetted by the water that creates a thin
water layer between the metal and organic phase. The
average thickness of the water layer is 3 ×10–4 cm.5
The oxygen solubility in the organic phase (60 ppm
to 70 ppm) is higher than in the aqueous phase
(8 ppm).6 One can imagine this two-phase system
being a differential aeration cell. Hence, the corrosion
processes proceed at the interface between the two
phases. An anodic area is formed in the water phase
and a cathodic area in the hydrocarbon phase
(Figure 1). Parameters that affect the corrosion
process in the hydrocarbon-water system are water
concentration in the mixture, conductivity, type and
concentrations of electrolytes in water, temperature,
and fluid velocity. There is an assumption that the
presence of salts and organic acids in the organic
phase (hydrocarbons) causes an increase in the
corrosion rate of mild steel. These components can
undergo extraction from the petroleum distillates into
the aqueous phase and result in a decrease in the pH
of the mixture.7
EXPERIMENTAL PROCEDURES
Two petroleum distillates were used: naphtha
(a light distillate with a boiling temperature range of
(2)
ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428.
CORROSION–Vol. 56, No. 12
CORROSION ENGINEERING SECTION
FIGURE 1. Corrosion of mild steel (cathodic and anodic areas) in
hydrocarbon-electrolyte environment.
25°C to 200°C) and a gasoline (a finished product
that consists of about 500 types of hydrocarbons
[C3-C12] with a boiling temperature range of 50°C to
220°C). A number of methods were used to examine
and evaluate the corrosion of mild steel in petroleum
distillates-electrolyte mixtures.
Gravimetric Method (ASTM G4)(2) — Mild steel
coupons were immersed in the petroleum distillates-
electrolyte mixture (water content varied from 0 vol%
to 5 vol%) over a period of 7 days. Deionized water
was used. The volume of the mixture was 450 mL.
The ratio of the coupon’s surface mixture was
1:22 (cm2/mL). The mixtures were agitated using a
magnetic stirrer at 25°C, atmospheric pressure,
and free contact with atmosphere. After testing, the
coupons were photographed, cleaned (using a
mixture of 5% hydrochloric acid [HCl] with organic
amine inhibitor), rinsed with distilled water, dried,
and weighed using an analytical balance. The corro-
sion rate of mild steel was calculated from the weight
loss of coupons over a period of 7 days. Three coupon
samples were used in one experiment. The error of
the experiments was 3% to 5%.
Karl-Fischer Method for Determination of Water
Concentration in Petroleum Distillates (ASTM D1744)
— The water concentration in the organic phase of
the mixture was determined before and after the
corrosion tests. The water content in the sample was
calculated from the amount of the reagent that
reacted with water. The accuracy of water concentra-
tion measurements was 0.8%.
Morphology and Chemical Composition of the
Corrosion Products by Scanning Electron Microscopy
(SEM) and Energy Dispersive Spectroscopy (EDS)
1267
CORROSION ENGINEERING SECTION
FIGURE 2. Corrosion rate of mild steel and water content in naphtha
vs added water to naphtha.
FIGURE 3. Corrosion rate of mild steel and water content in naphtha
vs added water to naphtha.
FIGURE 4. Corrosion rate of mild steel in naphtha + water mixture
with and without 10 ppm NaCl.
Methods — SEM gives a three-dimensional picture of
the surface (in other words, information about the
morphology of the corrosion products) using elec-
trons reflected from the surface. The chemical
composition of the corrosion products is determined
by measuring the energy of x-rays that are reflected
from the sample surface. A scanning microscope with
EDS was used.
Pitting Evaluation (ASTM G46) — Pitting evalua-
tion of the coupon surface (by criteria of size, shape,
depth, and density) was made after cleaning, visually
(unaided) and with an optical microscope.
†
Trade name.
1268
RESULTS AND DISCUSSION
Naphtha-Water Mixtures
Corrosion rate of mild steel and water concentra-
tion in the organic phase in naphtha-water mixtures
vs those with added water are presented in Figure 2.
The addition of small quantities of water (< 5 vol%) to
naphtha resulted in a drastic increase in the corro-
sion rate of mild steel in naphtha-water mixtures.
The corrosion rate of mild steel increased from
0.003 mm/y in “pure” (original) naphtha to
0.225 mm/y with the addition of 0.2% water content.
Water concentration (soluble water determined by
means of Karl-Fischer titration) in the naphtha
(organic phase of the mixture) increased from
35 ppm in “pure” naphtha to 80 ppm with the
addition of 0.1% to 0.4% water to the naphtha.
Figure 3 demonstrates that the “critical” concen-
tration of water in the mixture was 1,000 ppm. This
concentration caused a sudden increase in the
corrosion rate of mild steel from 0.02 mm/y to
0.105 mm/y. The sudden increase in the corrosion
rate was accompanied by a slow increase in the
water concentration in the organic phase (naphtha).
These results suggest that the corrosion process in
naphtha-water mixtures was caused by the dispersed
water drops at 1,000 ppm water in the mixture
(separate phase). When 1,000 ppm water was added
to naphtha, only 70 ppm to 80 ppm water was
soluble in naphtha (determined by the Karl-Fischer
method), and the separate water phase was
probably responsible for the sudden increase in
the corrosion rate.
The addition of 10 ppm sodium chloride (NaCl) to
the aqueous phase of the naphtha-electrolyte mix-
ture increased the corrosion rate of mild steel by 23%
when 0.1% electrolyte was added and 73% when
0.4% electrolyte was added (Figure 4). This fact
proves that the electrochemical mechanism occurred
in the two-phase hydrocarbon-electrolyte system.
Gasoline-Water Mixtures
The corrosion rate of mild steel and water
concentration in the organic phase in gasoline-water
mixtures vs added water are presented in Figure 5.
The addition of small quantities of water (< 5 vol%) to
gasoline resulted in an increased corrosion rate of
mild steel in gasoline-water mixtures. The corrosion
rate increased from 0.001 mm/y in “pure” (original)
gasoline to 0.414 mm/y with the addition of 200 ppm
water and to 0.66 mm/y with the addition of 4%
water to the gasoline. Water concentration (soluble
water) determined in the organic phase (gasoline) of
the mixture increased from 80 ppm in “pure” gaso-
line to 200 ppm to 300 ppm with the addition of
0.2% to 4% water to the gasoline.
Figure 6 demonstrates that the “critical” concen-
tration of water in the mixture is 200 ppm. This
CORROSION–DECEMBER 2000
 CORROSION ENGINEERING SECTION

concentration caused a sudden increase in the

corrosion rate of mild steel from 0.001 mm/y to
0.414 mm/y. The sudden increase in the corrosion
rate was accompanied by a considerable increase in
water concentration in the organic phase. When
200 ppm of water was added to gasoline, all of this
water was soluble (in the solution gasoline-water).
These results suggest that the corrosion process in
the gasoline-water mixtures was caused by the
soluble water in the gasoline (one phase).
FIGURE 5. Corrosion rate of mild steel and water content in gasoline
CHEMICAL COMPOSITION OF WATER AFTER vs added water to gasoline.
CONTACT WITH PETROLEUM DISTILLATES
The chemical composition of water was deter-
mined after 7 days of contact with petroleum distil-
lates while experiencing intensive agitation (magnetic
stirring) (Table 1). These results show a drastic
increase in water conductivity after contact with
petroleum distillates. This means that petroleum
distillates are the reservoir of anions (Cl–, SO4–2, NO3–)
and organic acids (formic [HCOOH] and acetic
[CH3COOH]) and that they are probably responsible
for the high corrosiveness of the fuels in the presence
FIGURE 6. Corrosion rate of mild steel and water content in gasoline
of water. Decrease of water pH after contact with
vs added water to gasoline.
petroleum distillates also confirms the presence of
acidic salts (chlorides) and weak organic acids.
uniform corrosion was more dominant, but pitting
Morphology and Chemical was deeper.
Composition of Corrosion Products
SEM and EDS results show that the corrosion ESTIMATION OF THE MINIMUM
products formed on the mild steel coupons from the WATER FILM THICKNESS
naphtha-water and from the gasoline-water mixtures
ON MILD STEEL IMMERSED IN PETROLEUM
consisted of iron and oxygen. The morphology of the
corrosion products is shown in Figure 7 and is DISTILLATES AND CORROSION MECHANISMS
similar to goethite (α-FeOOH).8 The present results
Equation (1) is based on the general chemical
suggest that the main cause of the corrosion in the
reaction of the corrosion process of mild steel in the
petroleum distillate-water mixtures is the presence
presence of water and oxygen:
of water and dissolved oxygen. These results support
the electrochemical mechanism of the corrosion of
mild steel in the petroleum distillates with small CO2 ( aq ) + OH − ↔ HCO3
−
(1)
quantities of water.
and based on the results from Figures 3 and 6, the
Pitting Evaluation minimum thickness of the water layer was estimated.
Pitting formed on the mild steel coupons im- The minimum thickness of the water layer at the
mersed in the naphtha-water mixture was evaluated. steel surface for the naphtha-water mixture was
A typical shape of pitting was “C”—wide and shallow 2 µm; for the gasoline-water mixture it was 10 µm.
pits of 0.18 mm in diameter.9 The examination These values are consistent with the results that
showed that pitting density was 1 × 104 m2 to 5 × describe atmospheric corrosion of mild steel under
104 m2 and pitting size was 0.5 mm2 to 2.0 mm2. The thin layers of electrolytes.10-12 These results suggest
maximum depth of the pitting formed on a coupon that the corrosion mechanism in the naphtha-water
immersed for 7 days in the mixture of naphtha with or gasoline-water mixtures was similar to the mecha-
3% water was 0.107 mm. Figure 8 shows that there nism of atmospheric corrosion under the wet film of
was no correlation between the pitting corrosion the electrolyte. In this case, naphtha or gasoline was
occurrence and the water concentration in the a reservoir of oxygen (instead of the atmosphere) and
organic phase (naphtha) of the mixture. Pitting corrosives such as chlorides, sulfates, nitrates, and
corrosion was dominant when the water concentra- organic acids. Another assumption is that the
tion in the mixture was < 0.1%. Above this value, corrosion mechanism in the two-phase system

CORROSION–Vol. 56, No. 12 1269

CORROSION ENGINEERING SECTION

TABLE 1
Chemical Composition of the Aqueous Phase after Contact with Petroleum Distillates (7 days, t = 25°C)
Deionized Water After Gasoline After Naphtha
Parameter Unit (Blank) Contact Contact

pH — 7 to 7.3 4.7 to 6.3 6.8 to 6.9

Conductivity µS/cm 8 to 18 74 to 79 51 to 57
Cl– ppm 0.4 to 0.5 1 to 5.5 1.5 to 1.9
SO42– ppm 0.3 to 0.4 1 to 1.9 1 to 2
NO3– ppm 0.02 to 0.08 0.8 to 3.1 2.1 to 3.8
HCOOH ppm 0 3 to 29 0.6 to 2.6
CH3COOH ppm 0 28 to 42 7 to 20

the air enter into tanks, vehicles, and pumps during

storage and transportation of petroleum distillates
and condense in them as a result of temperature
changes during day-night cycles. Oxygen also
dissolves in petroleum distillates during these
operations. Such corrosive species as salts and
organic acids remain in petroleum distillates after all
technological processes in oil refineries and then may
be extracted into the aqueous phase, which comes in
contact with petroleum distillates. Therefore, it is
very important to keep them “dry.”

FIGURE 7. SEM photograph of corrosion products on the mild steel
coupon immersed in the naphtha-water mixture (3 vol%) after 7 days.
FIGURE 8. Pitting factor, average corrosion rate of mild steel, and
water content in naphtha vs added water to naphtha.
petroleum distillate-electrolyte is similar to the
corrosion at the splash zone above high tide. In both
cases, the organic phase played the role of the
atmosphere that supplies water, oxygen, and other
corrosives.
The question is how water content may be
increased in petroleum products. Water vapors from
CONCLUSIONS
❖ “Pure” petroleum distillates containing 35 ppm to
80 ppm of water were not corrosive toward mild steel.
The addition of water to petroleum distillates re-
sulted in a drastic increase in the mild steel corro-
sion rate:
—Naphtha-water: 0.003 mm/y (35 ppm water),
0.1 mm/y (0.1% water), 0.23 mm/y (0.2%
water);
—Gasoline-water: 0.001 mm/y (80 ppm water),
0.4 mm/y (0.02% water), 0.66 mm/y (4%
water).
❖ “Critical” concentrations of water and the mini-
mum thickness of the water layer on mild steel in
petroleum distillates-water mixtures were deter-
mined:
—Naphtha-water: “critical” water concentration:
1,000 ppm; minimum thickness of water layer:
2 µm;
—Gasoline-water: “critical” water concentration:
200 ppm; minimum thickness of water layer:
10 µm.
❖ In naphtha-water mixtures, a pitting corrosion was
observed with the addition of up to 3% water. How-
ever, the pitting corrosion was dominant at low water
concentrations (< 0.1% water in naphtha). Above 3%
water, there was a uniform corrosion. In gasoline-
water mixtures, there was uniform corrosion. In a
mixture of gasoline with 200 ppm water, there was
pitting corrosion.
❖ In naphtha-water mixtures, the corrosion of mild
steel was caused by the dispersed (“free”) water

1270 CORROSION–DECEMBER 2000

 CORROSION ENGINEERING SECTION

(separate phase). In gasoline-water mixtures, corro- 2. W.P. Jepson, R. Menezes, “Effects of Oil Viscosity on Sweet
Corrosion in Multiphase Oil, Water/Gas Horizontal Pipelines,”
sion was a result of the dissolved water (one phase). CORROSION/95, paper no. 106 (Houston, TX: NACE Interna-
❖ Pitting corrosion was dominant when the water tional, 1995).
concentration in the naphtha-water mixture was 3. S.-L. Fu, M.J. Bluth, “Flow-Enhanced Corrosion and Chemical
Inhibition of Two-Phase Brine and Hydrocarbon Flowing
< 0.1%. Above this value, uniform corrosion was Systems,” CORROSION/95, paper no. 109 (Houston, TX: NACE,
more dominant. 1995).
4. L.M. Riekels, R.V. Seetharam, R.M. Krishnamurthy, C.F. Kroen,
❖ The main recommendation to diminish or prevent J.L. Pacheco, R.H. Hausler, V.A.W. Semerad, “Corrosion
corrosion in the petroleum distillates is to dry them Management in the Arun Field,” CORROSION/96, paper no. 24
down to values that do not exceed “critical” water (Houston, TX: NACE, 1996).
5. I.L. Rosenfeld, Dokl. Akad. Nauk SSSR 196 (1971): p. 1,379-
concentrations. 1,382.
6. R. Battino, ed., “Oxygen and Ozone,” vol. 7, in Solubility Data
Series (Oxford: Pergamon Press, 1981), p. 519.
ACKNOWLEDGMENTS 7. J.I. Bregman, Corrosion Inhibitors (New York, NY: MacMillan
Co., 1963), p. 320.
The authors acknowledge A. Raveh and N. 8. L. Engel, H. Klingele, An Atlas of Metal Damage (London, U.K.:
Wolfe Publications Ltd., 1981), p. 219.
Brodsky for valuable comments and J. Kalshtein and 9. ASTM G46-94, “Standard Guide for Examination and Evalua-
A. Besprozvanyi (Oil Refineries Water Lab) for the tion of Pitting Corrosion,” vol. 03.02 (West Conshohocken, PA:
chemical analyses of the aqueous phase. ASTM, 1996), p. 162-168.
10. N.D. Tomashov, Corrosion 20 (1964): p. 7t.
11. I.L. Rosenfeld, Atmospheric Corrosion of Metals (Russian)
REFERENCES (Moscow: AN SSSR, 1960), p. 372.
12. T. Tsuru, A. Nishikata, J. Wang, Mater. Sci. Eng. A198 (1995):
1. A. Groysman, Chem. Chem. Eng. (Hebrew) 32 (1998): p. 13-23. p. 161-168.

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2000
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2001
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CORROSION–Vol. 56, No. 12 1271