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The effect of water, sulphate and pH on the corrosion behaviour of

carbon steel in ethanolic solutions

Article in Electrochimica Acta · June 1987

DOI: 10.1016/0013-4686(87)87086-X

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 THE EFFECT OF WATER, SULPHATE AND pH ON THE
CORROSION BEHAVIOUR OF CARBON STEEL IN
ETHANOLIC SOLUTIONS

E. CAVALCANTI,* V.G. WANDERLEY,T. R. V. MIRANDA and L.ULLER

lnstituto National de Tecnologia, UPTM/Programa de Corroslo, Ave. Venezuela, 82/608, 20081,

Rio de Janeiro, Brazil

Abstract-The corrosion behaviour of carbon steel in ethanolic solutions containing different contents of
water and sulphate has been investigated by corrosion immersion tests. The influence of pH has also been
studied by adding different concentrations of sodium hydroxide to ethanolic solutions (ethanol p-a. + water
+ sulphate). The results have shown the detrimental effect of water on the corrosive behaviour of the carbon
steel electrodes, which have suffered localized attack in solutions with a water content 10 OX0 v/v and 4.8 Y0 v/v.
Sulphate was also found aggressive to carbon steel, which showed no corrosion when immersed in ethanol
p-a. In spite of the deleterious effect of these impurities, commonly found in ethanol fuels in Brazil, pH was
found to be the most important factor in determining the corrosivity ofethanolic solutions. For carbon steels,
a DH greater than 8.0 is required to guarantee corrosion immunity in solutions containing 1 .O mg I- ’ SO: -
and 4% ‘;/ v/v H LO.

INTRODUCTION Table 1. Characteristics of ethanol fuel in Brazil

With the introduction of ethanol as an alternative fuel Mean value f

Characteristics 1 standard deviation
to gasoline, the automotive and alcohol manufacturing
industries in Brazil have experienced a considerable
Ethanol content (% w/w) 93.2 f 0.3
number of corrosion problems in the use and handling Acidity (mg CH3COOH/100 ml) 1.2 * 0.3
of combustible alcohol produced from sugarcane. Aldehyde (mg/lOO ml) 4.0 f 6.0
Research efforts[l-21 have initially been concentrated Ether (mg/lOO ml) 9.0 + 2.0
on the evaluation of the corrosion resistance of several Higher alcohols (mg/lOO ml) 29.0? 31.0
alloys in the ethanol fuel, which is available for Sulphate (mg/l) 5.96 + 0.20
consumption according to the characteristics shown in Chloride (mg/l) 1.97f 1.58
Table 1[3]. PH 5.80 f 1.25
Further investigationsC451, carried out with
carbon steel, have related the corrosivity of the ethanol
fuel to the residual water content and the presence of
inorganic impurities introduced during the fermen- was weighted on analytical balance to an accuracy of
tation and distillation stages of production, storage & 0.01 mg and stored in a desiccator until immersion.
and transportation. With respect to the organic im- The test solutions used throughout the experimental
purities, such as aldehyde, ether and higher alcohols, work were made up with ethanol p.a. (water content:
no detrimental effect was noticed[6]. More recently, an 0.12 “/, v/v and acidity: 0.52 mg CH,COOH/lOO ml)
exploratory work using factorial planning[7], has and demineralized water (conductivity: 4.0 @cm - I;
stressed the influence of pH on the corrosion be- sulphate and sodium contents: < 0.1 mg 1 - ‘; chloride
haviour of carbon steel. The present work examines the content < 0.2 mgl-I). A step by step experimental
effect of water, sulphate and pH on the corrosivity of procedure was followed, in which the influence of
ethanolic solutions in relation to carbon steel. water was first evaluated by the addition of de-
mineralized water to ethanol p.a_ Two hydrated eth-
anol solutions were prepared: 4.8 y0 and 10 y0 v/v.
EXPERIMENTAL Sulphate was then introduced to the 4.8% v/v hy-
drated ethanol, as sulphuric acid (analytical grade), at
Rectangular specimens (20 mm x 30 mm x 2 mm) three different concentrations (0.5, 1.O and 2.0 mg 1 - I),
were cold cut from an AISI 1010 carbon steel sheet for examining the effect of sulphate. Finally, the
with the following composition (wt %): C 0.081, influence of pH, at a constant water content (4.8 oA v/v)
Mn 0.540, P 0.007, S 0.036, Si 0.027 and Fe bal. After and sulphate concentration (1.0 mg/l), was investi-
having a small hole drilled on the top, the specimens gated by the addition of sodium hydroxide (analytical
were prepared to a 220 grit Sic surface finish. Then grade) at three different concentrations for adjusting
they were washed in demineralized water, rinsed in the pH of the above-mentioned hydrated sulphate
acetone, dried in a warm air stream and stored in a containing ethanolic solution to 7.0, 8.0 and 9.0. The
desiccator for 45 min. Following this, each specimen test solutions had their pH measured by a conventional
pH meter with a glass electrode at 25°C and acidity
*Author to whom correspondence should be addressed. measured by potentiometry prior to immersion.

935
936 E. CAVALCANTIet al.

Triplicate corrosion immersion tests were carried

out in Erlenmeyer flasks (500 ml) for all test solutions.
These flasks had an inert rubber stopper with a small
hole allowing limited ingress of air. Each specimen was
sustained by a nylon thread and kept completely
immersed in 360 ml of solution for 78 days at 25°C. At
the end of this period, the specimens were removed
from solution, dried in warm air stream and visually
and/or optically examined when required. The speci-
mens were cleared according to the ASTM Gl-79
recommended practice and subsequently weighted.
When pitting attack was noticed, the ASTM G46-76
recommended practice for pitting corrosion evalu-
ation was followed, in which the extent of attack was
taken as an average value of maximum pit depth
measurements of three specimens.

RESULTS AND DISCUSSION

The results of the corrosion immersion tests ob-

served after 78 days of immersion are shown in
Table 2. No corrosion was noticed on the surface of
the specimens exposed to non-aqueous ethanol, whilst
pit colonies could be visually observed on the specimen
exposed to ethanol + 10 o/0v/v H,O. With reference to
the ethanolic solution containing 4.8 o/0v/v H20, a few
incipient pits could only be detected after examination
of the surface on the optical microscope at 50 x
magnification, which suggests a minor extent ofattack.
It is clear from the results shown in Table 2, that the
presence of water, at the concentration levels in-
vestigated, reduces the good corrosion resistance of
carbon steel observed in non-aqueous ethanol. As
suggested by Heitz[S], the greater solubility of corro-
sion products in hydrated ethanol may account for
_- _-_^-
such observed behaviour. One may also consider that, ‘L,’
as water is introduced to ethanol, there is an increase of
hydrated proton concentration and consequently a
ZBE?
VI00
greater tendency to iron dissolution than in water-free -_- 3’ c-i
d

ethanol. The detrimental effect of water observed in

the present work is in accordance with previous
investigations on carbon steel[9]. However, an op-
posite effect is observed in the case of more noble
ferrous alloys, such as stainless steel, where H,O in
methanol[ lo] and ethanol[ 1 l] was found to enhance
passivation and inhibit pitting corrosion. It is worth
mentioning that specimens exposed to water- ethanol
solutions have exhibited loss of brightness, which may
be associated with formation of a surface film. Recent
investigations by infrared absorption spectrometry
and X-ray diffraction[ 121, have detected an amorph-
ous film on the surface of carbon steel specimens
immersed in 6% v/v water-ethanol solution, in con-
trast with the observed presence of crystalline films
developed at higher concentrations of water.
Considering the greater corrosion resistance conferred
by amorphous films in relation to crystalline films, the
possible existence of an amorphous film on the surface
of the specimen exposed to 4.8% v/v water-ethanol
solution may also account for the relatively low extent
of corrosion verified in the latter case.
An increase of intensity of attack was noticed with
the introduction of sulphate to hydrated ethanol (4.8 y0
v/v H,O). The type of attack remained as pitting
corrosion, although the specimens have exhibited a
 The corrosion behaviour of carbon steel 931

more regularly distributed pit population and deeper solution during 78 days at 25”C, it was possible to
pits. The extent of attack, given in terms of maximum reach the following conclusions:
annual pitting rate, increased linearly with the sulphate 1. The presence of demineralized water, at the
concentration, which was varied from 0.5 mgl - ’ to concentration levels studied, ie 4.8 y0 and 10 “/, v/v
2.0 mgl- ‘. A previous study[6] also found sulphate H,O, enhances pitting corrosion, while no corrosion is
aggressive towards AISI 1020 carbon steel exposed to observed in anhydrous ethanol.
ethanolic solutions containing 5% v/v of water. 2. The corrosivity of water containing ethanolic
However, it must be emphasized that, in both cases, solution (4.8 o/0v/v H,O) is gradually raised, as the
sulphate was introduced as sulphuric acid and the sulphate concentration (in the form of sulphuric acid)
corresponding pHs of the solutions were restricted to is increased in solution from 0.5 to 2.0 mgl-‘.
the acid range (pH = LO-6.0), notably corrosive to- 3. For ethanolic solutions containing 4.8% v/v
ward carbon steel in aqueous solutions. It is note- Hz0 + 1.0 mg/l SOi- no corrosion attack could be
worthy that if the same sulphate concentration is noticed when the pH was adjusted to 8.0 and 9.0 by the
introduced as lithium sulphate, no corrosion is introduction of sodium hydroxide.
observed[ 131.
Finally, it can be seen from Table 2 that, as sodium
hydroxide is added to hydrated ethanol solution (4.8 %
v/v H 20), containing 1.O mg l_ ’ of sulphate, corrosion REFERENCES
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