Original Research Article DOI: 10.18231/2394-2797.2017.

0003

Application of expired drugs in corrosion inhibition of mild steel

Neeraj Kumar Gupta1, CSA Gopal2, Vandana Srivastava3, MA Quraishi4,*
1,2PG Student, 3,4Professor, Dept. of Chemistry, IIT-BHU Varanasi, Uttar Pradesh

*Corresponding Author:
Email: maquraishi.apc@itbhu.ac.in

Abstract
Present work deals with the investigation of corrosion inhibition of mild steel using two expired drugs namely Atenolol and
Nifedipine in 1 M HCl solution. Their inhibition properties were evaluated using electrochemical, scanning electron microscopy
(SEM) and DFT methods. Atenelol and Nifidipine showed efficiency of 91.30 and 93.91% at low concentration of 200 ppm
respectively. Polarization study reveals that the expired drugs inhibit corrosion of mild steel by suppressing both anodic and
cathodic reactions occurring on the mild steel surface thus acting as mixed type inhibitors. EIS study shows that the investigated
drug increases the polarization resistance by adsorbing on the metal/electrolyte interface. The electrochemical results were well
supported by SEM as well as DFT study.

Keywords: Expired Drugs, Mild steel, Acid corrosion, SEM, DFT

Introduction of expired drugs as a corrosion inhibitor can solve two

The global loss due to corrosion is about $2.5 major environmental and economical problems:
trillion, which is near 3.5% of the world's GDP (NACE limitation of environmental pollution with
March 2016). Thus Corrosion inhibition study is a pharmaceutically active compounds and reduction of
matter of theoretical as well as practical importance. the disposal costs of expired drugs.
Mild steel is commonly used for a wide range of In view of above observation, it is thought
applications in many industries due to its very good worthwhile to investigate the corrosion inhibition
mechanical property but it has poor corrosion resistance properties of two expired drugs namely Atenolol (ATL)
especially in acidic medium.(1) Hydrochloric acid is and Nifedipine (NDP) (Fig. 1) on mild steel in 1 M HCl
widely used for different applications like pickling, solution. Atenolol is a drug used for treating
descaling, acid cleaning, and oil well acidizing etc.(2) cardiovascular diseases (antagonist) whereas Nifedipine
During these applications when mild steel comes in is a medication used for managing angina, high blood
contact with HCl it suffers severe corrosion. To combat pressure, Raynaud's phenomenon, and premature labor.
his problem, use of organic corrosion inhibitor is Karthik et al. have studied the corrosion inhibition
regarded as the best technique due to its ease of property of fresh Atenolol drug and got 93.8%
application as well as cost effectiveness.(3) However, efficiency at 300 ppm concentration8 whereas no
most of the compounds that have been tested of being literature is present on the corrosion inhibition
used as inhibitor are either toxic in nature or very efficiency of Nifedipine drug. The corrosion inhibition
expensive. So there existed a need to identify such behavior of ATL and NDP was studied using
inhibitors which are non-toxic, cheap and shows good electrochemical, SEM and DFT techniques.
inhibition efficiency at low concentration.
In this view, drugs constitute a potential class of
corrosion inhibitors due to the presence of heteroatoms
in their structure and their green nature.(4) In a recent
review, Gece has described 17 classes of drugs that can
be used as corrosion inhibitors for various metals and
alloys in corrosive environments like HCl, H2SO4,
H3PO4 and NaCl.(5) However, most of the
pharmaceutical drugs are much more expensive than
Fig. 1: Chemical Structure of investigated drugs
the organic inhibitors which are currently used in
industries. Thus using fresh drug as a corrosion
inhibitor is not economically viable.(6) Therefore, it is Experimental section
thought worthwhile to investigate the corrosion Corrosion Inhibitor: Two of the expired drugs namely
atenolol and nifedipine were taken from the local
inhibition properties of expired drugs which are of no
market and used as inhibitor according to a method
use. It is well reported that drugs retain at least 90% of
described earlier.(2) The molecular structures of the
its original potency even after expiry date but their use
drugs are shown in Fig. 1.
for the medicinal purpose is restricted due to the
professional restrictions and liability concerns.(6,7) Use Materials and Chemicals: The Mild steel specimens
with chemical composition (wt %): C = 0.076, Mn =
International Journal of Pharmaceutical Chemistry and Analysis, 4(1):8-12 8
Neeraj Kumar Gupta et al. Application of expired drugs in corrosion inhibition of mild steel

0.192, P = 0.012, Si = 0.026, Cr = 0.050, Al = 0.023 0

icorr  icorr
i
and balance Fe. was used for chemical, electrochemical %  0
 100 (5)
and surface experiments. The specimens’ size was 8 × 1 icorr
× 0.025 cm for electrochemical experiments having
exposed area 1 cm2. The aggressive test solution of 1M where, and are the corrosion current
HCl was prepared by dilution of analytical grade HCl densities in absence and presence of drugs.
(37%) with double distilled water. SEM study: The mild steel was immersed in1M HCl
Electrochemical Experiment: Electrochemical solution in absence and presence of the optimum
measurements were performed by the method as concentration of the drugs for 3h immersion time.
described previously.(9) The electrochemical impedance Thereafter, the mild steel specimens were taken out,
measurements (EIS) were performed on mild steel washed with double distilled water, dried and finally
specimens in the frequency range of 100 kHz to analyzed by SEM and EDX method. The SEM study
0.00001 kHz under potentiostatic conditions using an was carried out using a Ziess Evo 50 XVP instrument at
AC at open circuit potential with amplitude of 10 mV an accelerating voltage of 5 kV and 500 ×
magnification.
peak to peak. The charge transfer resistance was
calculated from Nyquist plot from which corrosion
inhibition efficiency was calculated using following Result and Discussion
equation: Electrochemical measurements
Polarization study: The Tafel polarization curves
Rpi  Rp0 obtained for mild steel in absence and presence of
%  100 (4) expired drugs at optimum concentration are shown in
Rpi
Fig. 2(a). Table 1 list the important polarization
Where Rip and R0p are the polarization resistance in parameters i.e., corrosion potential (Ecorr), cathodic (βc)
presence and absence of expired drugs in 1 M HCl and anodic (βa) Tafel slopes, corrosion current density
solution respectively. (icorr), surface coverage (θ) and the inhibition efficiency
The Potentiodynamic polarization studied were (η %) for mild steel corrosion with and without
performed on mild steel specimens by automatically inhibitor. The results showed that in presence of
changing the electrode potential from −250 to +250 inhibitor corrosion current density is decreased due to
mV/ SCE versus open circuit potential at a scan rate of formation of protective film.(10) It is also observed that
1 mVs−1. The corrosion current density (icorr) was the addition of inhibitor retards both cathodic and
calculated by extrapolating the linear segments of the anodic reactions. However, the cathodic reactions are
cathodic and anodic Tafel slopes from which corrosion comparatively more affected than the anodic reactions
inhibition efficiency was calculated using following suggesting that investigated drugs are mixed type
equation: inhibitors and predominantly act as cathodic
inhibitors.(11)

Table 1: Tafel Polarization parameters for mild steel in 1 M HCl solution in absence and presence of
optimum concentration of expired drugs
inhibitor Ecorr icorr βa βc θ η(%)
(mV/SCE) (μAcm-2) (mV/dec) (mV/dec)
Blank -445 1150 70.5 114.6 ---- ----
ATL -492 103 97.8 187.4 0.9104 91.04
NDP -504 79 78.8 118.2 0.9314 93.13

Electrochemical impedance spectroscopic study: Fig. 2(b) represents the Nyquist plots for mild steel in 1M HCl
solution in absence and presence of optimum concentration of the drugs. From the Fig. 2(b) it could be observed that
Nyquist plots give similar appearance with and without inhibitors suggesting that studied drugs inhibits mild steel
corrosion without affecting the mechanism of corrosion process.(10) The Nyquist plot consists of a depressed
semicircle at high frequency region which is characteristics response of solid metal electrodes in the corrosion
process.(2) Impedance parameters such as Rp, n, Cdl, θ and η% were derived from Nyquist plot by implying
equivalent circuit shown in Fig. 2(c) and given in Table 2.

International Journal of Pharmaceutical Chemistry and Analysis, 4(1):8-12 9

Neeraj Kumar Gupta et al. Application of expired drugs in corrosion inhibition of mild steel

Fig. 2 (a-c): (a) Potentiodynamic polarization plots (b) Nyquist plots for mild steel in 1 M HCl solution in the
absence and presence of an optimum concentration of inhibitor (c) Equivalent circuit used to fit the EIS data
for mild steel in 1 M HCl solution

The result showed that addition of inhibitor causes significant increase in the Rp value suggesting that inhibitors
retard the charge transfer reaction and corrosion occurring on the mild steel surface by forming protective film on
the surface.(12) From the results it is also clear that values of Cdl is lower in the presence of inhibitors. The decrease
in Cdl value is due to decrease in local dielectric constant and/or an increase in the thickness of the electrical double
layer.

Table 2: Electrochemical impedance parameters obtained from EIS measurements for mild steel in 1 M
HCl solution in absence and presence of optimum concentration of expired drugs
Inhibitor Rs Rct Cdl n ϴ η%
(Ωcm2) (Ωcm2) (μFcm-2)
Blank 1.12 9.58 106.21 0.827 --- --
ATL 0.98 143.9 61.98 0.849 0.9329 93.29
NDP 1.17 219.6 50.76 0.839 0.9561 95.61

SEM analysis: The SEM micrographs for mild steel in absence and presence of drugs are shown in Fig. 3(a-c). Fig.
3(a), represents the SEM micrograph in absence of the drugs which is severely corroded due to attack of acid on
mild steel. However, in presence of drugs (Fig. 3(b-c)) the surface morphology of mild steel is remarkably
improved. This observation further supports the protection of mild steel by adsorption of ATL and NDP.

Fig. 3(a-c): SEM image of mild steel surface after 3h immersion (a) without inhibitor (b) with 200 ppm ATL
(c) with 200 ppm NDP

Quantum Chemical calculation: The optimized molecular structures and corresponding highest occupied frontier
molecular orbital (HOMO) and lowest unoccupied frontier molecular orbital (LUMO) obtained for neutral form of
studied expired drugs are given in Fig. 4. The quantum chemical calculations parameters are given in Table 3.

Table 3: Quantum chemical parameters of the investigated expired drugs

Inhibitor EHOMO ELUMO ΔE σ η
(Hartree) (Hartree) (Hartree)
ATL -0.17531 -0.00404 0.17127 0.0856 11.682
NDP -0.20467 -0.03477 0.1699 0.08495 11.771

International Journal of Pharmaceutical Chemistry and Analysis, 4(1):8-12 10

Neeraj Kumar Gupta et al. Application of expired drugs in corrosion inhibition of mild steel

Fig. 4: Optimized molecular structure and the frontier molecular orbitals HOMO and LUMO of ATL and
NDP

The HOMO frontier molecular electron distribution hardness and softness are in accordance to the order of
gives significant information about the sites or inhibition efficiency obtained experimentally.
segments of the studied molecules which can act as Conclusion
electron donor during the adsorption process.(13) The The studied expired drugs were found to act as
energy difference of frontier molecular orbitals (ELUMO effective and green corrosion inhibitors for mild steel in
- EHOMO) can be used to predict the theoretical reactivity 1M HCl solution and their inhibition efficiency related
and thereby their relative inhibition property of the with concentration and chemical structure. Among the
studied molecules. Obviously, a molecule with low studied drugs, the NDP shows the best inhibition
energy band gap (low ΔE) associated with high efficiency of 93.91% at 200 mgL-1 concentration. The
chemical reactivity and high inhibition efficiency.(14) In potentiodynamic study reveals that in presence of drugs
our case, the values of ΔE for NDP is lower than that of the cathodic reaction appears to be much affected than
ATL therefore associated with better adsorption on the anodic reaction suggesting that studied drugs act as
metal surface and thus higher inhibition efficiency. predominantly cathodic inhibitors. SEM analyses
Several other parameters such as global hardness (σ) validate the weight loss and electrochemical results.
and global softness (η) were calculated and discussed in The experimental and theoretical calculations were in
the present study in order to provide more insight about good agreement.
the interaction between inhibitor molecules and metal
surface. Generally, an inhibitor with lower value of Acknowledgment
global hardness and higher value of softness is Neeraj Kumar Gupta and CSA Gopal gratefully
associated with high chemical reactivity and thereby acknowledged Ministry of Human Resource
exhibits high inhibition efficiency.(15) In our present Development (MHRD), New Delhi (India) for support.
investigation, NDP has the lower global hardness and
higher value of softness than the ATL. This trend of

International Journal of Pharmaceutical Chemistry and Analysis, 4(1):8-12 11

Neeraj Kumar Gupta et al. Application of expired drugs in corrosion inhibition of mild steel

References
1. Odewunmi NA, Umoren SA, Gasem ZM. Utilization of
watermelon rind extract as a green corrosion inhibitor for
mild steel in acidic media. J Ind Eng Chem 2005;21:239–
247.
2. Gupta NK, Quraishi MA, Verma C, Mukherjee A K.
Green Schiff's bases as corrosion inhibitors for mild steel
in 1 M HCl solution: experimental and theoretical
approach. RSC Adv 2016;6:102076–87.
3. Ahamad I, Prasad R, Quraishi MA. Thermodynamic,
electrochemical and quantum chemical investigation of
some Schiff bases as corrosion inhibitors for mild steel in
hydrochloric acid solutions. Corros Sci 2010;52:933–42.
4. Ahamad I, Prasad R, Quraishi MA. Inhibition of mild
steel corrosion in acid solution by Pheniramine drug:
Experimental and theoretical study. Corros Sci
2010;52:3033–41.
5. Gece G. Drugs: a review of promising novel corrosion
inhibitors. Corros Sci 2011;53:3873–98.
6. Vaszilcsin N, Ordodi V, Borza A. Corrosion inhibitors
from expired drugs. Int J Pharm 2012;431:241– 4.
7. Gebhart F, Drug Topics, October 10, 2005.
8. Karthik G, Sundaravadivelu M. Studies on the inhibition
of mild steel corrosion in hydrochloric acid solution by
atenolol drug. Egypt J Petroleum 2016;25:183–91.
9. Gupta NK, Verma C, Quraishi MA, Mukherjee AK.
Schiff's bases derived from L-lysine and aromatic
aldehydes as green corrosion inhibitors for mild steel:
Experimental and theoretical studies. J Mol Liq
2016;215:47–57.
10. Verma C, Quraishi MA, Gupta NK. 2-(4-{[4-Methyl-6-
(1-methyl-1H-1,3-benzodiazol-2-yl)-2-propyl-1H-1,3-
benzodiazol-1-yl] methyl}phenyl) benzoic acid as green
corrosion inhibitor for mild steel in 1 M hydrochloric
acid. Ain Shams Eng J 2016; xxx, xxx–xxx.
11. http://dx.doi.org/10.1016/j.asej.2016.07.003.
12. Boumhara K, Tabyaoui M, Jama C, Bentiss F. Artemisia
Mesatlantica essential oil as green inhibitor for carbon
steel corrosion in 1 M HCl solution: Electrochemical and
XPS investigations. J Ind Eng Chem 2015;29:146–55.
13. Haque J, Srivastava V, Verma C, Quraishi MA.
Experimental and quantum chemical analysis of 2-amino-
3-((4-((S)-2-amino-2-carboxyethyl)-1H-imidazol-2-
yl)thio) propionic acid as new and green corrosion
inhibitor for mild steel in 1 M hydrochloric acid solution.
J Mol Liq 2017;225:848–55.
14. Yıldız R. An electrochemical and theoretical evaluation
of 4,6-diamino-2-pyrimidinethiol as a corrosion inhibitor
for mild steel in HCl solutions. Corros Sci 2015;90:544–
53.
15. Raja PB, Qureshi AK, Rahim AA, Osman H, Awang K.
Neolamarckia cadamba alkaloids as eco-friendly
corrosion inhibitors for mild steel in 1 M HCl media,
Corros Sci 2013;69:292–301.
16. Dasami PM, Parameswari K, Chitra S. Corrosion
inhibition of mild steel in 1M H2SO4 by thiadiazole Schiff
bases. Measurement 2015;69:195–201.

International Journal of Pharmaceutical Chemistry and Analysis, 4(1):8-12 12