Imperial Journalof Interdisciplinary Research (JIR)
Vol-2, Issue-11, 2016
ISSN: 2454-1362, http://www.onlinejournal.in
2-Amino-5-Mercapto-1,3, 4-Thiadiazole
as Corrosion Inhibitor for Stainless
Steel in 1.0m SulphuricAcid Solution
Dr. Abhay Singh
Associate Professor., Department Of Chemistry
K.L.P. College, Rewari -123401 (India)
Abstract: 2-Amino-$- mercapto-1, 3, 4-thiadiazole
(AMTD) has been investigaled as inhibitor for the
corrosion of 304 stainless steel in 1.0M sulphuric
acid solution. Weight loss, electrochemical
polarization, scanning electron microscopy (SEM)
and Auger electron microscopy (AES) echniques
have been used.Experiments have been carried out
using 100, 200 and 400 ppm concentrations of the
investigated inhibitor at 20. 30 and 40C
lemperatures .Corrosion rates have been
calculated using Stern-Geary equation . Inhibition
efficiency increases with the increase in
concentration of the inhibitor and decreases with
the increase in lemperalure. AMTD is physically
adsorbed on the surface of 304 stainless steel and
acts as a cathodic inhibitor.
Keywords: Stainless steel, Corrosion inhibitor,
SEM, AES, AMTD.
INTRODUCTION
Nitrogen and sulphur containing organic
compounds are easily and quickly adsorbed on
metal surface forming a proactive layer on the
Element C Mn S P
%(w/w) 0.045 1.47 0.008 0.06
For the electrochemical studies the specimens had a
working area of 1xl cm. Weight loss experiments
were caried out using 100, 200 and 400ppm of
AMTD 1.0 Msulphuric acid solution at 20°,30° and
40°C. The clectrochemical studies were carried out
using a potentiostat/galvanostat (Model CL-95,
Elico Make). The surface morphology was studied
by scanning electron microscope (Model JSM-840,
JEOL Make). AES analyses were carried out using
Scanning electron microscope (SAM) (PHI Model
590A, U.S.A.). The specimens were exposed to
1.0M sulphuric acid for 12 hours for studying their
surface characteristics.
Imperial Journal of Interdisciplinary Research (JIR)
surface of metal and have been extensively used for
the inhibition of different kind of steels
corrosion
by acids (1-10) .Since 304 stainless steel has
applications in acidic medium in a varietymanyof
industries, the corrosion inhibition of this steel in
acidic environment is of great interest.
In the present investigation AMTD has been
studied as a corrosion inhibitor towards the
corrosion of 304 stainless steel in 1.0 M sulphuric
acid solution at 20, 30 and 40°C
Weight loss and electrochemical temperatures.
polarization
techniques have been employed to find out various
corrosion parameters .SEM and AES techniques
have been used for investigating the surface film
present on the surface of 304 stainless steel in
presence of the inhibitor.
EXPERIMENTAL
All chemicals used were of AR grade and double
distilled water was used for preparing solutions.
Rectangular specimens of 304 stainless steelof size
2x4 cm of the following composition were used
for weight loss experiments.
Si Ni Cr Fe
0.37 7.98 17.04 Balane
RESULTS AND DISCUSSION
Table 1 shows the percentage inhibition efficiency
data calculated by using weight loss method
and
linear polarization resistance method for 304
stainless steel in presence of 100, 200 and 400 ppm
concentrations of AMTD at 20, 30 and 40C
temperature. AMTD provides good inhibition
efficiency towards the corrosion of 304 stainless
steel in 1.0 M sulphuric acid solution.
The
inhibition efficiency of AMTD increases with
increase in its concentration from 100 to 400 ppm
and decreases with the rise of
to 40C .When the temperature from 20
concentration of AMTD is
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Imperial Journal of Interdisciplinary Research (JIR)
Vol-2, Issue-11, 2016
ISSN: 2454-1362, http://www.onlinejournal.in
increased from 100 to 200 ppm the inhibition
efficiency increases rapidly but only a slight
change in efficiency is observed when the
concentration of the inhibitor is further increased to
400 ppm . Percentage inhibition effenciency data
obtained from polarization technique are in good
agreement with those obtained from weight loss
experiments The variation of open circuit potential
(OCP) with concentration of AMTD at 20, 30 and
40°C are also recorded in Table 1. Addition of
AMTD in 1.0 M sulphuric acid solution causes a
shift in OCP values in positive direction. The OCP
values shifted in the negative direction with the
increase in temperature from 20to 40°C.
Fig. 1 shows anodic polarization curves recorded
potentiostaticaly for 304 stainless steel in 1.0M
sulphuric acid solution in absence and presence of
100, 200 and 400 ppm of AMTD. The addition of
AMTD increases the critical current density (I.).
This indicates that a higher concentration of Fe*
and Cr is required for passivation to occur in
presence of AMTD. The Lc value increases with the
increase in the concentration of the inhibitor.
Trabanelli and co-workers (11) have also reported
that sulphur containing organic inhibitors may
inhibit both anodic and cathodic reactions on steel
or may stimulate the anodic dissolution of steel but
decreasing the rate of cathodic reaction. The
behavior of AMTD is also in accordance with the
later possibility.
Cathodic polarization curves for 304 stainless steel
in 1.0M sulphuric acid solution in absence and in
presence of 100, 200 and 400 ppm concentrations
of AMTD have been plotted in Fig 2. Cathodic
polarization curves shifted considerably towards
lower current density values in presence of AMTD
Thus AMTD reduces cathodic reaction only and
acts as a cathodic inhibitor.
V. Pandit Rao and co -workers (12) have also
studied 2-amino-S-mercapto-1,2,4-thiadiazole as
corrosion inhibitor for copper in sulphuric,
hydrochloric and nitric acids and reported that it
acts as a good inhibitor in all the three acids
Chaudhary et. al (13) have reported similar results
using 4-amino-5-H-3-mercapro-1,2,4-triazole, 4
amino-5-metyl-3-mercapto-1, 2, 4-triazole and 4
amino-5-ethyl-3-mercapto-1, 2, 4-triazole for the
corrosion of Fe-Cr-Ni steel in sulphuric acid
solution AlI the three mercaptotriazole
compounds investigated are reported to be cathodic
in nature and have tendency to stimulate the anodic
reaction on Fe-Cr-Nisteel.
Heat of adsorption and activation energy values for
304 stainless steel in 1.0 M sulphuric acid solution
in presence of AMTD have been summarized in
Imperial Journal of Interdisciplinary Research (UIR)
Table 2. Lower values of heat of adsorption for
AMTD Shows that the adsorption of AMTD on the
surface of 304 stainless steel in 1.0 M sulphuric
acid solution is physical in nature .Heat of
adsorption values increases with the increase in
concentration of AMTD, thus indicating greater
adsorption with higher concentration of AMTD
which in turn explains the higher inhibition
efficiency at higher concentration of inhibitor.
The activation energy for the inhibited system is
higher than that of uninhibited system and it
increases with the increase in concentration of the
inhibitor. Increase in the value of activation energy
with increase in concentration of AMTD clearly
indicates that the inhibition efficiency increases
with increase in concentration of AMTD.
Fig 3 and Fig 4 shows the SEM micrographs of 304
stainless steel in 1.0 M sulphuric acid solution in
absence and presence of 200 ppm of AMTD
respectively. It is clear from the micrographs that
the surface of 304 stainless steel in presence of 200
ppm of AMTD has improved remarkably than in
absence of AMTD. The surface of 304 stainless
steel appears to be covered with a protective film of
the inhibitor which acts as a barrier for the access
of aggressive ions to the bare surface.
Fig 5and Fig 6 shows the AES spectra of 304
stainless steel exposed to 1.0 M sulphuric acid
solution for 12 hours in absence and presence of
200 ppm of AMTD respectively . It is clear from
the spectra that along with the peaks of elements
like O, Ct, Fe, Cand s, a small pcak of N is also
observed in AES spectra in presence of AMTD
which is not observed in absence of AMTD (Fig. 5)
Presence of nitrogen on the surface of 304
stainless steel suggests that some inhibitor
molecules are present on the surface of 304
stainless steel even though the inhibitor
has been found to adsorbed physically on surface
of 304 stainless steel.
CONCLUSIONS
1 AMTD is an excellent corrosion inhibitor for
the protection of 304 stainless steel in 1.0 M
sulphuric acid solution and provides an efficiency
as high as 91.3% at 20c.
2 The inhibition efficiency increases with the
increase in concentration of AMTD from 100 to
400 ppm and decreases with the increase in
temperature from 20 to 40°c.
3. AMTD acts as a cathodic inhibitor.
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 Imperial Journalof lnterdisciplinary Research (UIR)
Vol-2, Issue-11, 2016
ISSN: 2454-1362, http://www.onlinejournal.in
4. Activation energy for the inhibited system 6 S. H. Sanad, Surface Technology,
higher than that of uninhibited system and it 22(1984)20.
increases with the increase in concentration of the 7. M. N. Desai and M. B. Desai, Journal of
inhibitor. Electrochemical Sociaty of India,
30(1981)351 .
5. Lower values of heat of adsorption suggest that 8 Ehteram A. Noor, Aisha H. AI
adsorption of AMTD on the surface of 304 Moubaraki, Materials Chemistry and
stainless steel is physical in nature. Physics, 110(2008)145.
9. Lin Wang, Corrosion Science,
REFERENCES 43(2003)2281 .
10. Tambi Ramde, Stefano Rossi, Caterina
1 G. Shmitt, British Corrosion Journal, Zanella, Applied Surface Science
19(1984)165. 307(2014)209
2. E. Stupnisek-Lisac, K. Salajster and J. 11. A. Frignani, M. Tassinari, C., Monlecelli
Furac, Corrosion Science, 28(1988) 1189. and G. Trabanelli, Corrosion Science,
3. N.O. Obi-Egbedi, IB. Obot, Corrosion 27(1987)27
Science, 53(2011)263. 12. V, Pandit Rao, T. A. Sreenivasa Rao and
4. S. Arab and B Abd-El Nabey, M. C. Ganorkar, Transaction of SAEST,
International Journal of Chemistry, 27(1992)222.
2(1991)23. 1. 13 Ashutosh Kumar and R. S. Chaudhary,
5. P.N.G. Shanker and K. I.Vasu, Journal of Presented at Symposium on Emerging
Electrochemical Society of India, Frontiers in Corrosion and Its Control,
32(1983)47. Rohtak, India (1992)

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 Imperial Journal of Interdisciplinary Research (JIR)
Vol-2, Issue-11, 2016
ISSN: 2454-1362, http:l/www.onlinejournal.in
Table 1
Percentage Inhibition Efficiency of AMTD for the Corrosion of 304Stainless Steel in 1.0 MSulphuric
Acid Solution by Weight Loss and Linear Polarization Resistance Method
Concentration of Temperature Inhibition Efficiency (%) OCP
AMTD (ppm) c) By Weight Loss By Polarization (mV)
20 460
Nil 30 445
40 435
100 20 71.9 68.8 -424
200 20 91.6 87.3 409
400 20 94.8 91.3 -398
100 30 67.7 65.3 430
200 30 83.1 82.5 421
400 30 88.5 86.8 408
100 40 64.8 62.8 434
200 40 77.2 80.2 430
400 40 84.7 83.5 422
Table 2
Heat of Adsorption and Activation Energy Values for 304 Stainless Steel in 1.0 M Sulphuric Acid
Solution in Presence of Different Concentrations of AMTD.
Concentration of AMTD Heat of Adsorption (-AH) Activation Energy (E)
(ppm) (K.Cal.) (K.Cal.)
Nil 8.3
100 2.4 9.8
200 4.5 12.4
400 6.5 14.3

200 PP

Fig. 1Anodic polarization curves of 304stainless steel in 1.0 M sulphuric acid

solution in absence and presence
of AMTD,

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Imperial Journal of Interdisciplinary Research (UIR)
vol-2, Issue-11, 2016
sSN: 2454-1362, http://www.onlinejournal.in

7minoS nrota,9/4-thàoae

0000

Fig. 2 Cathodic polarization curves of304 stainless steel in 1.0 Msulphuric acid solution in absence and
presence of AMTD.

Fig. 3SEM micrograph of 304 stainless steel surface exposed to 1.0M sulphuric acid solution for 12 hours
(X800).

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20 15KU
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Fig 6 AES specra of 394 stairless steel exposed so 15 M aipiurk cid soistin in preeace of 20 pys af
AMTID o 12 hos.

Snperal iornal of interdisciplinary Research (UIR) Page 259