Corrosion characteristics of mild steel in aqueous

solutions of fatty acids

E.F.OTTE The corrosion characteristics of mild steel in aqueous solutions of acetic, propionic, butyric,
W.SKINNER valeric, hexanoic, octanoic, decanoic, lauric, myristic, and palmitic acids were determined.
Acid concentrations used were those requiring 5, 12·5, and 25 mg of KO H per 1 g of solution
for neutralisation. Temperature was varied from 25 to 250°C; in the lower temperature
range corrosion rate increased with temperature while it decreased with temperature in the
higher temperature range.
© 1995 The Institute of Materials. Manuscript received 13 May 1994 ..in final form 24 June
1994. The authors are in the Department of Chemical Engineering, University of Pretoria,
Pretoria 0002, South Africa.

INTRODUCTION Because the autoclaves could not be fitted with electrodes,

In the !manufacture of liquid fuel using coal, air, and water
as raw materials, hydrogen and CO are formed as
intermediate products, which are then catalytically con-
verted to give an organic phase, containing a mixture of
Published by Maney Publishing (c) IOM Communications Ltd
electrochemical tests were conducted only at relatively low
temperatures. Values for electrochemically determined cor-
rosion rates were 10-200/0 lower than those obtained from
mass loss tests. This was most likely a result of the high

liquid hydrocarbons (the main product), and an aqueous electrolyte resistance of the solutions; no voltage drop
phase. Various fatty acids form as bypro ducts which are corrections were performed. The corrosion rates now
distributed as solutes between the two liquid phases. quoted were evaluated from mass loss tests.
The corrosion characteristics of carbon steel in the
organic phase containing different concentrations of vari-
ous fatty acids have been investigated in earlier work! RESULTS AND DISCUSSION
which showed that at concentrations below acid number All tests were at least duplicated and where calculated
(AN ~ amount of KOH required for neutralisation, mg per corrosion rates for the same system differed by more than
1 g of solution) = 5 corrosion rates were < 1000 J.lm/yearat 10% additional tests were conducted.
temperatures between 25 and 250°C. At higher concen- Results for acetic acid are shown in Fig. 1. At relatively·
trations corrosion rates »1000 J.lm/yearwere obtained with low temperatures corrosion rates increased with temper-
the elevated temperatures. ature, corrosion products were soluble, and no corrosion
T~e purpose of the present work was to investigate the product films could be detected on exposed specimen
characteristics of the aqueous phase. surfaces. At relatively high temperatures corrosion rates
decreased with temperature and- black corrosion product
films formed on the specimen surfaces.
EXPERIMENTAL All systems investigated showed similar correlations for
Specimens for exposure were prepared, according to corrosion rate as a function of temperature: increasing
ASTM G 1, from AISI 1020 steel plate and had dimensions corrosion rates at relatively low temperatures with no film
1·2 x 10 x 20 mm. A hole of size 0·8 mm was drilled near formation and decreasing corrosion rates at relatively high
the top of each specimen for mounting purposes. The fatty temperatures with the formation of black corrosion product
acids investigated are listed in Table 1 and the concen- films. Mixtures of fatty acids were also evaluated and no
trations used were AN = 5, 12'5, and 25. All chemicals used synergistic effects could be detected ..
were of analytical grade, the acid solutions being purged The increase of corrosion rate with temperature in the
with nitrogen to give a dissolved oxygen content of lower temperature range is typical of activation controlled
< 1·0 ppm. The temperatures investigated were 25, 60, 90, systems. The decrease of corrosion rate with temperature
130, 170, 210, and 250°C. Low temperature experiments in the higher temperature range, where film formation
were conducted in 250 mL glass vessels with plastic screw occurred, is associated with more effective film formation
tops, placed in water baths to regulate temperature. High at higher temperatures and pressures.2,3
temperature experiments were conducted in Parr autoclaves
manufactured from AISI 316 stainless steel with ratings of
3000 lb in-2 (2'069 x 107 Pa) at 350°C. To prevent electro- 100000
chemical contact between the specimens and the body of
the autoclave, test specimens were contained in 400 mL '-
co
Q>
glass cylinders which fitted into the autoclave body. <:- •
Exposure times were 72 h. E
:l.
10000
W
Table 1 Fatty acids investigated ~a: •
•
Z
acetic acid 0
propionic acid
en 1000
AN
0
butyric acid a:
a: --- C2 5
valerie acid 0 -+- C212.5
hexanoic acid u -A- C225
octanoic acid --1-.-_ )
100
decanoic acid 0 20 40 60 80 100 120 140 160 180 200 220 240
lauric acid TEMPERATURE, °c
myristic acid
palmitic acid 1 Variation of corrosion rates of mild steel in acetic acid solutions
with temperature

British Corrosion Journal- 1995 Vol. 30 NO.2 135

 136 Otte and Skinner Corrosion of mild steel i~ solutions of fatty acids

8500

m
~6500
8000
7500
7000 ..
.5
. . .. Acidl1umber

... [ZJ 12.5 U

o
240

220 .. ,
..

..
·1
.AN=5 IZJAN=12.5 ~AN=25

E6000 uJ200
:l.5500 Q25 a:. ;'
:J I
!

~ 5000 !d: 180

~ 4500 a:. . /
/
z 4000 ~ 160 ..:
. /
,.
03500 ~
UJ
•.....
140
~ 3000 / i
/ I
/
0: 2500 I

~ 2000 120 / I
I
I
u 1500- I
/ ....

/
1000 100 C'II C'? II) CD co o C'II co
500
o o o o 0
o o o
o ACID
C2 C3 C4 C5 C6 C8 C10 C12 C14 C16
3 Temperature of maximum corrosion rate as function of chain
(bf'

.5
90 length
Acid number
80
~cu lengths longer than ClO• This caused decanoic acid to be
(1) 70 012.5
<:- the most corrosive acid at 250°C, as shown in Fig. 2b.
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E CJ25
E 60
UJ' CONCLUSIONS
50
~0: For the conditions investigated corrosion rates are mostly
Z 40 too high for processing of the aqueous phase by itself in
0 mild steel equipment. However, mild steel is used for
U5 30 processing of the hydrocarbon-water two phase system.
0
0: The corrosivity of the two phase system will depend on
0:
0 20 variables such as temperature, types and concentrations of
U
dissolved fatty acids, and flowrates of the phases. Failures
10
of mild steel equipment in such applications are most likely
o to be associated with the more corrosive conditions, as
C2 C3 C4 C5 C6 C8 C10 C12 C14 C16 reported. For example, the presence of high concentrations
ACID of decanoic acid at 250°C in the water phase will render
the system very corrosive. A proper investigation of the
a at 90°C; b at 250°C
characteristics of two phase systems should be conducted,
2 Corrosion rates of mild steel in fatty acid solutions
introducing turbulence as a further variable.

In the lower temperature range corrosion rate decreased REFERENCES

with chain length of the acid (Fig. 2a), owing to ionisation
constants decreasing with chain length.4 In the higher
temperature range the correlation between cprrosion rate
and chain length was more complex (Fig.2b) and was
caused by a shifting of temperatures at which maximum
corrosion rates occurred (Fig. 3) and drasti~ decreases in
the maximum corrosion rates of fatty acids with chain
1. J. J. LIEBENBERGand w. SKINNER: Br. Corros. J., 1993, 28,
(2), 130-132.
2. E. C. POTTER and G. M. w. MANN: Br. Corros. J., 1965,1, (1), 26-35.
3. G. D. BENGOUGH and F. WORMWELL: cited in u. R. EVANS:
'Metallic corrosion passivity and protection', 2nd edn; 1946,
London, Edward Arnold.
4. E. HEITZ: 'Corrosion of metals in organic solvents, advances in
science and technology', Vol. 4; 1974, New York, Plenum Press.

British Corrosion Journal 1995 Vol. 30 NO.2