Volume 20 Preprint 8
Retardation of Stainless steel 314 dissolution in acidic medium
S.Karthikeyan, P.A.Jeeva, K.Raja
Keywords: Corrosion, Cetrizine, SS 314, Quantum Studies
The significance of an antihistamine drug viz., Cetrizine [CZN] on corrosion of Stainless steel 314 in 2N Sulphuric acid was studies using mass loss measurements, Tafel polarization studies and impedance measurements. The results indicated that CZN is a good inhibitor for SS 314 in 2N H2S04 and maximum efficiency obtained was 94 % at 450ppm concentration of CZN . Potentiostatic Polarization analyses showed that CZN acts as a mixed type of inhibitor. Quantum chemical studies were done for Cetrizine and its various quantum chemical parameters were calculated and discussed.
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Retardation of Stainless steel 314 dissolution in acidic medium
S.Karthikeyan, P.A.Jeeva*, K.Raja
Centre for Innovative Manufacturing Research, VIT University, Vellore -632014, India
Corresponding Author (firstname.lastname@example.org)
The significance of an antihistamine drug viz., Cetrizine [CZN] on corrosion of Stainless
steel 314 in 2N Sulphuric acid was studies using mass loss measurements, Tafel
polarization studies and impedance measurements. The results indicated that CZN is a
good inhibitor for SS 314 in 2N H2S04 and maximum efficiency obtained was 94 % at
450ppm concentration of CZN . Potentiostatic Polarization analyses showed that CZN
acts as a mixed type of inhibitor. Quantum chemical studies were done for Cetrizine
and its various quantum chemical parameters were calculated and discussed.
Keywords: Corrosion, Cetrizine, SS 314, Quantum Studies
The Stainless steel is widely used in aerospace /Auomobile industries because of its
ideal Massto strength ratio. The high strength of the SS 314 is owing to the presence
of alloying element predominantly chromium and Nickel and these make alloy more
disposed to to restricted corrosion due to sensitivity of the intermetallic particles in
grain boundaries [1-2].Generally Sulphuric acid is used for removing scales , chemical
and electrochemical etching of SS 314. Numerous methods are used to EXPLAIN the
corrosion rate of metals in acids, and in the among of different methods practice of
inhibitor is highest one. Many organic compounds were used as corrosion inhibitor . But currently use of antibiotics as corrosion inhibitors is increased tremendously
because of less toxicity and eco-friendly nature. Heterocyclic compounds holding hetro
atoms such as sulphur, nitrogen and oxygen atoms comprising multiple bonds adsorb
on the metal surface and thus act as active corrosion inhibitor for Stainless steel 314 in
acid medium [8-13]. A scrupulous examination was used to find
properties of Cetrizine. The corrosion inhibiting capability of Cetrizine might be due
to its arrangement of atoms. Various studies demonstrate that Cetrizine is prospective
corrosion inhibitor. Cetirizine is an antihistamine that reduces the natural chemical
histamine in the body. Histamine can produce symptoms of sneezing, itching, watery
eyes, and runny nose. It is used to treat cold or allergy symptoms such as sneezing,
itching, watery eyes, or runny nose.
Materials and methods
Materials employed for the analyses were SS 314 sheet of compositions (wt. %), Cr
(4.3), Mn (2), Ni(21) and appreciable amount of Si, C,P in addition to Fe balance. The
sheet was then cut into number of sample of each 4 x 1 x 2 cm dimensions were used
loss and electrochemical studies. Each sample was mechanically polished
followed by degreasing with acetone then washed with double distilled water and
finally dried. Electrochemical experiments were performed
in three electrode cell
assembly with SS 314 as working electrode. Platinum wire as counter and Ag/Agcl/kcl
(sat) as reference electrode.AR grade Hydrochloric acid and double distilled water are
used to make 0.1N HCl for all experimentations.
The antibiotic namely Citrizine was purchased from corresponding manufacturer and
used without further purification. The structure of Cetrizine is shown in fig 1.CZN
contains nitrogen atoms incorporated into the lactone ring, thus making the lactone
ring 5 membered. With this structure it is likely to act as good inhibitor.
FIG 1 Structure of Cetrizine
2.3 Mass loss studies
The inhibitor was initially screened by a Massloss method .various samples Al were
submerged in 0.1 N HCl solution comprising diverse concentrations of inhibitors
(CZN).Samples were weighed before and after immersion and Massloss was estimated.
The surface coverage (ϴ) and inhibition efficiency were determined by means of
following equations. Surface coverage (ϴ) = Wo-W/Wo
Inhibition efficiency (%) = Wo-W/Wo X 100
Where, Wo - Massloss without inhibitor
W - Massloss using varied concentrations of inhibitors
2.4 Tafel polarization studies
Tafel Polarization studies were carried out in a conventional three - electrode
cylindrical glass cell, using BAS-100 A electrochemical analyzer Before to computing
the polarization graphs the solution was deaerated for 20 min. and the working
electrode was sustained at its corrosion potential for 10 min for attaining a steady
state. The Al 2024 surface was bare to different concentrations of Cetrizine in 100mL
of 2N sulphuric acid
at room temperature. The inhibition efficiency (IE %) was
estimated using the equation
Inhibition Efficiency (IE %) = (I0 –I /I0) X 100
Where I0 and I are the corrosion current density in absence and presence of inhibitor
The current-potential curves were documented by altering the electrode potential from
-750mV to +150mV versus the open circuit potential. The resultant corrosion current
(I corr) was recorded. Tafel plots were made by plotting E versus log I. Corrosion
Potential (E corr), corrosion current density (I corr) and cathodic (βc) and anodic slopes
(βa) were intended from known procedures.
2.5.. Impedance studies
Impedance studies were carried out in the frequency range from 0.1 to 10000 Hz using
amplitude of 20 mV and 10 mV peak to peak with an AC signal at the open-circuit
potential .The impedance graphs were schemed in the nyquist representation. Charge
transfer resistance (Rct) values were acquired by subtracting the high-frequency
impedance. The inhibition efficiency was obtained from the equation:
Inhibition Efficiency (IE %) = (Rct - Rct / Rct) x 100
Where R’ct and Rct are the corrosion current of Aluminum 2024 with and without
treatment of inhibitor respectively.
2.7 Theoretical Analysis
Quantum studies were done using MOPAC 2000 program of CS Chemoffice packet
program. The highest occupied molecular orbital (HOMO)energy, lowest unoccupied
molecular orbital (LUMO) energy, Dipole moment (), hardness(η), absolute softness(σ)
and total energy of the molecule were intended with the above given software package.
3. RESULTS AND DISCUSSION
The values of inhibition efficiency (IE %) and the rate of corrosion from Massloss
studies at diverse concentrations of Cetrizine are presented in table-1. It showed that
the compound successfully inhibits the corrosion of SS 314 in 2N H2SO4 medium.
Extreme inhibition efficiency and declined corrosion rate is due to the influence of firm
adsorption and enlarged coverage of cetirizine on SS 314 with growth in the dosage of
The corrosion inhibition by cetirizine
may possibly be due to the following
1. The interaction between the lone pairs of electrons of the nitrogen atoms of the CZN
and the positively charged Fe surface.
2. The interactions between the +M effect of –Cl atom in inhibitor ring structure and
the positively charged metal surface.
3.2 Potentiodynamic polarization studies
Ewe/V vs SCE
FIG 2 Tafel curves of SS 314 alloy in 2N H2SO4 at various concentrations of Cetrizine
Tafel curves for Stainless steel 314 in H2SO4 medium at various concentrations of
Cetrizine are presented in figure-2. The parameters such as corrosion potential (E
current densities (I
anodic tafel slopes (βa) and cathodic tafel slopes (βc) and
inhibition efficiency were studied from Tafel polarization curves as a function Cetrizine
concentration are displayed in table- 2. It can be realized from the table that values of
Tafel slopes and I
are very much diminished in contrast to the metal surface without
inhibitor. It is also revealed that growing the concentrations of Cetrizine amplifies the
βa and βc in imbalanced fashion approving that the inhibition of corrosion of Al alloy in
HCl medium is in mixed control [14-16]. Values of Ecorr are progressed to less negative
values in the existence of different concentrations of CZN. This might be the cause for
developing resolutely adherent adsorbed film of CZN on the Aluminum alloy. It marked
that most of the values of inhibition efficiency found by Massloss procedures and Tafel
polarization method are with virtuous agreement.
3.4 Impedance studies
The Nyquist illustrations of impedance performance of SS 314 alloy 2024 in acidic
medium with and without Cetrizine is used to compute charge transfer resistance (Rt
)and double layer capacitance (Cdl) values which are tabularized in table-3. From the
table, it is found that values of Rct increases at the expenditure of double layer
capacitance with growth in CZN concentration . This contributes to the improved
adsorption of the CZN antibiotic on the Al alloy surface with intensification of drug
A plot of surface coverage (ø) against log C exhibited a straight line plot endorsing that
the adsorption of CZN on Al alloy surface from HCl medium followed Temkins
adsorption isotherm. This is main confirmation to corrosion inhibition of Cetrizine, as a
consequence of its adsorption on the aluminum surface.
3.5 Quantum chemical studies:
The quantum chemical aspects such as highest occupied molecular orbital (EHOMO)
energy, lowest unoccupied molecular orbital (ELUMO) energy, LUMO- HOMO, energy gap
(∆E), dipole moment (), [18-21] are summarized in table -4.
CZN revealed greater inhibition efficiency due to its improved softness values by
unshared electron pairs on nitrogen .The ionization potential (I) and electron affinity
(A) were resulting from Koopmans theorem
A= - ELUMO I=-EHOMO
The absolute hardness (η) and absolute electronegativity (x) of the inhibitor molecules
were studied from the following equations
η = I-A
The softness (σ) can also be specified as
Where, hardness and softness are the features of an inhibitor to define its stability and
reactivity. A hard molecule reveals large energy gap and a small gap prevailing in soft
molecule. Soft inhibitors are highly reactive than hard molecule because of its electron
donor nature to metal is high for prior. For the modest transfer of electrons,
adsorption might occur at the fragment of the molecule where (σ) which is a local
property, has the uppermost value.
1. Cetrizine performs as worthy inhibitor for corrosion inhibition of SS 314 alloy 2024
in acidic environment.
2. Tafel polarization investigation confirms that Cetrizine is a mixed kind of inhibitor.
3. The Cetrizine act as good inhibitor which is demonstrated from improved Rct and
diminished Cdl values.
5. The values of HOMO, LUMO, ∆E and resultant from quantum chemical studies
validated the outcomes of chemical and electrochemical studies.
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Table 1. Inhibition
efficiency, corrosion rate and surface coverage for the corrosion of
SS 314 alloy in 2N H2SO4 with different measures of Cetrizine gained from Mass loss
2. Electrochemical parameters of SS 314 alloy in 2N H2SO4 with different
concentrations of Cetrizine from Tafel polarization studies.
Tafel slopes in mV in dec-1
Table 3.Electrochemical impedance parameters and its inhibition efficiency for the
corrosion of SS 314 alloy in 2N H2SO4 with different dosages of Cetrizine.
Table 4: Quantum chemical data of Cetrizine