Corrosion Science 52 (2010) 152–160

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Effect of Cefazolin on the corrosion of mild steel in HCl solution

Ashish Kumar Singh, M.A. Quraishi *
Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi, Uttar Pradesh 221 005, India

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption and inhibition effect of Cefazolin on mild steel in 1.0 M HCl at 308–338 K was studied by
Received 22 May 2009 weight loss, EIS, potentiodynamic polarization and atomic force microscopy techniques. The results
Accepted 26 August 2009 showed that inhibition efficiency increased with inhibitor concentration. The adsorption of Cefazolin
Available online 31 August 2009
on mild steel surface obeys the Langmuir adsorption isotherm equation. Both thermodynamic (enthalpy
of adsorption DHads , entropy of adsorption DSads and free energy of adsorption DGads ) and kinetic param-
Keywords: eters (activation energy DEa and pre-exponential factor A) were calculated and discussed. Polarization
A. Mild steel
curves showed that Cefazolin acted as mixed-type inhibitor controls predominantly cathodic reaction.
B. AFM
B. Weight loss
Ó 2009 Elsevier Ltd. All rights reserved.
C. Acid inhibition
C. Kinetic parameters

1. Introduction
The damage by corrosion generates not only high cost for
inspection, repairing and replacement, but in addition these consti-
tute a public risk, thus the necessity of developing novel sub-
stances that behave like corrosion inhibitors especially in acid
media [1]. There always exists a need for developing new corrosion
inhibitors. Acid solutions are widely used in industry such as acid
pickling of iron and steel, chemical cleaning and processing, ore
production and oil well acidification. The use of hydrochloric acid
in pickling of metals, acidization of oil wells and in cleaning of
scales is more economical, efficient and trouble-free, compared
to other mineral acids [2].
The corrosion inhibition efficiency of organic compounds is re-
lated to their adsorption properties. Studies reported that the
adsorption of organic inhibitors mainly depends on some physio-
chemical properties of the molecule, related to its functional
groups, to the possible steric effects and electronic density of donor
atoms. Adsorption also depends on the possible interaction of p-
orbital of the inhibitor with d-orbital of the surface atoms, which
induces greater adsorption of the inhibitor molecules on the sur-
face of mild steel [3–6].
A large number of organic compounds including heterocyclic
compounds [7–12] were studied as corrosion inhibitors for mild
steel [13–15]. Most of them are toxic in nature. This has led to
the development of non-toxic corrosion inhibitors such as Trypt-
amine [16], L-ascorbic acid [17], Sulfamethoxazole [18], and Cefa-
trexyl [19], Ceftriaxone [20], Cefotaxime [21], sulfa drugs [22],
antibacterial drugs [23], antifungal drugs [24], rhodanine azosul-
pha drugs [25]. Prabhu et al. [26] reported the inhibitor activity
of tramadol on mild steel in HCl and H2SO4.
Cefazolin is a first generation cephalosporin antibiotic [27]. It is
mainly used to treat bacterial infections of the skin. It can also be
used to treat moderately sever bacterial infections involving the
lung, bone, stomach, blood, heart valve [28]. It is clinically effective
against infections caused by Staphylococci and Streptococci of
Gram positive bacteria [29]. Cefazolin is the commercial name of
(6R,7R)-3-{[(5-methyl-1,3,4-thiadiazol-2-yl)thio]methyl}-8-oxo-7-
[(1H-tetrazol-1-ylacetyl)amino]-5-thia-1-azabicyclo[4.2.0]oct-2-
ene-2-carboxylic acid. It is a first generation cephalosporin
antibiotic.
In the present work, we have investigated the inhibitive action
of Cefazolin on corrosion of mild steel in 1 M HCl solution at 308 K
using weight loss, polarization resistance, Tafel polarization and
electrochemical impedance techniques. The effects of temperature,
acid concentration, immersion time were also studied. Several iso-
therms were tested for their relevance to describe the adsorption
behaviour of the compound studied.
2. Experimental
2.1. Materials

Tests were performed on mild steel having composition (wt.%)

* Corresponding author. Tel.: +91 9307025126; fax: +91 542 2368428.
C = 0.17, Mn = 0.46, Si = 0.26, S = 0.017, P = 0.019 and balance
E-mail addresses: maquraishi@rediffmail.com, maquraishi.apc@itbhu.ac.in (M.A. Fe were used for weight loss as well as electrochemical studies.
Quraishi). The aggressive solution of hydrochloric acid (AR grade) of 1 M

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.08.050
 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160
concentration was used for all studies (except in the study of effect
of acid concentration).
2.2. Inhibitor
Cefazolin was purchased from medicine shop as a trade name
Cefacidal powder injection (m.p.  463 K) and used without fur-
ther purification. Fig. 1 shows the molecular structure of Cefazolin.
Cefazolin is a N–S heterocyclic compound containing eight nitro-
gen atoms which could be easily protonated in acid solution, and
a great deal of p-electrons exists in this molecule.
2.3. Solutions
The aggressive solutions, 1.0 M HCl, were prepared by dilution
of AR grade 37% HCl in distilled water. The stock solution of Cefaz-
olin was diluted to a certain conc. of Cefazolin. The inhibitor con-
centration in the weight loss and electrochemical study was in
the range of 2.19  104 M to 10.95  104 M and 4.76  104 M
to 8.76  104 M, respectively.
2.4. Weight loss measurements
The mild steel strips of 2.5 cm  2.0 cm  0.025 cm sizes were
abraded with a series of emery paper (grade 600–800–1000–
1200) and then washed with distilled water and acetone. After
weighing accurately, the specimens were immersed in 100 ml of
1.0 M HCl with and without addition of different concentrations
of Cefazolin. After 3 h, the strips were taken out washed, dried
and weighed accurately. Duplicate experiments were performed
in each and the mean value of the weight loss was reported. The
inhibition efficiency ðgW% Þ and surface coverage (h) was deter-
mined by using following equation:
Wo  Wi
gW% ¼  100
Wo
Wo  Wi
h¼
Wo
where Wi and Wo are the weight loss values in the presence and in
the absence of inhibitor, respectively.
2.5. Electrochemical measurements
The electrochemical studies were carried out using a three-elec-
trode cell assembly at room temperature. Mild steel coupons of
1 cm  1 cm (exposed area) with a 7.5 cm long stem (isolated with
commercially available lacquer) were used for electrochemical
measurements. A platinum foil of 1 cm2 was used as counter elec-
trode and saturated calomel electrode as reference electrode. The
working electrode was polished with different grades of emery pa-
pers, washed with water and degreased with acetone. All electro-
chemical measurements were carried out using a Gamry
Fig. 1. Molecular structure of Cefazolin.
153
Potentiostat/Galvanostat (Model G-300) with EIS software Gamry
Instruments Inc., USA. Prior to the electrochemical measurement,
a stabilization period of 30 min was allowed, which was proved
sufficient to attain a stable value of Ecorr.
For linear polarization resistance measurements, the potential
of the electrode was scanned from 0.02 to +0.02 V vs. corrosion
potential at scan rate of 0.5 mV/s. From the measured polarization
resistance value, the inhibition efficiency was calculated using the
relationship;
R0p  Rop
gRp % ¼  100 ð3Þ
R0p
where Rop and R0p are the polarization resistance in the absence and
in the presence of inhibitor, respectively.
The Tafel polarization curves were obtained by changing the
electrode potential automatically from (+250 mV to 250 mV) at
open circuit potential with a scan rate 0.5 mV s1 to study the ef-
fect of inhibitor on mild steel corrosion. The linear Tafel segment
of cathodic and anodic curves were extrapolated to corrosion po-
tential to obtain the corrosion current densities (Icorr).
The inhibition efficiency was evaluated from the calculated Icorr
values using the relationship;
Iocorr  I0corr
gP% ¼  100 ð4Þ
Iocorr
where Iocorr and I0corr are the corrosion current in the absence and in
the presence of inhibitor, respectively.
The impedance studies were carried out using ac signals of
10 mV amplitude for the frequency spectrum from 100 kHz to
0.01 Hz. The charge transfer resistance values were obtained from
the diameter of the semi circles of the Nyquist plots. The inhibition
efficiency of the inhibitor was obtained from the charge transfer
resistance values using the following equation:
ð1Þ R0ct  Roct
gRct % ¼  100 ð5Þ
R0ct
ð2Þ where Roct and R0ct are the charge transfer resistance in the absence
and in the presence of inhibitor, respectively.
The values of interfacial double layer capacitance (Cdl), were
estimated from the impedance value using bode plot by the
formula;
1
jZj ¼ ð6Þ
2pfC dl
2.6. Atomic force microscope
The mild steel strips of 1.0 cm  1.0 cm  0.025 cm sizes were
prepared as described in section 2.4. After immersion in 1.0 M
HCl with and without addition of 8.76  104 M of Cefazolin at
308 K for 3 h, the specimen was cleaned with distilled water, dried
and then used for AFM.
154 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160

3. Results and discussion inhibitor in acid solution at the studied concentration of the acid
solution.
3.1. Weight loss measurements
3.1.5. Adsorption isotherm
3.1.1. Effect of inhibitor concentration Basic information on the interaction between the inhibitor and
The corrosion rate values of mild steel with the addition of the mild steel surface can be provided using the adsorption iso-
Cefazolin in 1.0 M HCl at various temperatures are presented in Ta- therm. For this purpose, the values of surface coverage (h) at differ-
ble 1. From Table 1, it can be seen that corrosion rate values in ent concentrations of Cefazolin in 1 M HCl acid in the temperature
1.0 M HCl solution containing Cefazolin, decreased as the conc. of range (308–338 K) were calculated to explain the best isotherm to
inhibitor increased. This result is due to fact that the adsorption determine the adsorption process from the experimental data
amount and coverage of inhibitor on mild steel surface increases obtained.
with inhibitor concentration. Attempts were made to fit these h values to various isotherm
including Frumkin, Langmuir, Temkin, Freundlich isotherms. By
3.1.2. Effect of temperature far, the experimental data the results were best fitted by Langmuir
The values of inhibition efficiencies obtained from weight loss adsorption isotherm equation [31]:
measurement for the different inhibitor concentrations in 1.0 M
C 1
HCl are shown in Fig. 2a. From Fig. 2a, it can be seen that inhibition ¼ þC ð7Þ
h K
efficiency decreased with increasing temperature, which indicates
desorption of inhibitor molecule [30]. However, this decrease in Fig. 3 shows the relationship between C/h and C at temperature
gW% is small at higher inhibitor concentration. ranges studied. These results show that all the linear correlation
coefficients (R2) are almost equal to unity and all the slopes are
3.1.3. Effect of immersion time very close to unity, which indicates that the adsorption of Cefazolin
Fig. 2b shows the effect of immersion time (3–12 h) at 308 K on follows Langmuir adsorption isotherm.
the inhibition efficiency of Cefazolin at different concentrations.
Fig. 2b shows that Cefazolin inhibits the corrosion of mild 3.1.6. Thermodynamic parameters of Cefazolin on mild steel surface
steel for all immersion times. At lower concentration (2.19– Thermodynamic parameters are important to study the inhibi-
6.57  104 M), gW% decreased continuously with immersion time tive mechanism. The thermodynamic functions for dissolution of
but at higher concentration, gW% was almost constant for different mild steel in the absence and in the presence of various concentra-
immersion times. tions of Cefazolin were obtained by applying the Arrhenius equa-
tion and the transition state equation [32–35]:
3.1.4. Effect of acid concentration Ea
The effect of acid concentration on corrosion behaviour of mild logðrÞ ¼ þ log A ð8Þ
2:303RT
steel in the presence of 8.76  104 M inhibitor concentration was
   
studied and the results are shown in Fig. 2c. It is clear that change RT DSa DHa
in acid concentration from 0.5 to 2.5 M results in the inhibition r¼ exp exp  ð9Þ
Nh R RT
efficiency varying from 93.76% to 88.9%. This change in the
inhibition suggests that the compound is an effective corrosion where Ea apparent activation energy, A the pre-exponential factor,
DHa the apparent enthalpy of activation, DSa the apparent entropy
Table 1 of activation, h the Planck’s constant and N the Avogadro number,
Corrosion rate and Inhibition efficiency (%IE) values for the corrosion of mild steel in respectively.
aqueous solution of 1 M HCl in the absence and in the presence of different
The regression between log(r) and 1/T was calculated and the
concentrations of Cefazolin from weight loss measurements at different temperatures.
parameters were calculated and presented Table 2. Arrhenius plots
Inhibitor concentration Temperature Corrosion rate gW% of log(r) vs. 1/T for the blank and different concentrations of Cefaz-
(M  104) (K) (mm/y)
olin are shown in Fig. 4a, and from the Table 2, it can be seen that
Blank 308 40.4 – apparent activation energy increased with increasing concentra-
318 58.2 –
tion of Cefazolin. The increase in apparent activation energy Ea
328 100.9 –
338 174.5 – may be interpreted as physical adsorption [36]. Szauer and Brand
[37] explained that the increase in activation energy can be attrib-
2.19 308 12.6 68.8
318 22.7 60.9 uted to an appreciable decrease in the adsorption of the inhibitor
328 49.1 51.2 on the mild steel surface with increase in temperature and a corre-
338 114.3 34.4 sponding increase in corrosion rates occurs due to the fact that
4.38 308 8.5 78.9 greater area of metal is exposed to the acid environment.
318 17.5 69.8 According to Eq. (8), corrosion rate (r) is being effected by both
328 39.4 60.8 Ea and A. In general, the influence of Ea on the mild steel corrosion
338 91.1 47.8
was higher than that of A on the mild steel corrosion. However, if
6.57 308 5.5 86.3 the variation in A was drastically higher than that of Ea , the value
318 12.3 78.8
328 30.9 69.3
of A might be the dominant factor to determine the mild steel cor-
338 72.6 58.4 rosion. In the present case, Ea and A increased with concentration
8.76 308 2.5 93.7
(the higher Ea and lower A led to lower corrosion rate). As it can
318 9.5 83.7 be seen from Table 1, the corrosion rate of steel decreased with
328 25.9 74.3 increasing concentration; hence, it was clear that increment of Ea
338 58.1 66.7 was the decisive factor affecting the corrosion rate of mild steel
10.95 308 2.4 93.9 in 1.0 M HCl.
318 9.3 82.8 Fig. 4b shows a plot of log(r/T) vs. 1/T. A straight lines were ob-
328 24.9 75.2
tained with a slope equal to ðDH =2:303RÞ and intercept equal to
338 56.5 67.5
½logðR=NhÞ þ ðDS =2:303RÞ, from which the values of DHa and DSa
 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160 155

(a) 100 (b) 95

90 90 5
4
85
80
80
70 75 3

η W%
η W%
70
60 65
50 60 2
55
40 50
45 1
30
2 4 6 8 10 12 2 4 6 8 10 12
-4
Inhibitor concentration (M x 10 ) Immersion time (h)

(c) 97.5

95.0
ηW%

92.5

90.0

0.5 1.0 1.5 2.0 2.5

Acid concentration (M)

Fig. 2. Variation of inhibition efficiency in 1 M HCl on mild steel of surface area 10 cm2 with (a) different conc. of Cefazolin inhibitor at different temperatures, (b) immersion
time at different conc. and (c) different acid conc. at optimum inhibitor conc. (8.76  104 M).

18 are higher than in the absence of inhibitor. The positive sign of

2
308 K (R = 0.9966)
2
enthalpies reflect the endothermic nature of steel dissolution pro-
16 318 K ( R = 0.9990 )
cess meaning that dissolution of steel is difficult [38].
2
328 K (R = 0.9988)
14 338 K
2
(R = 0.9987) On comparing the values of the entropy of activation ðDSa Þ gi-
ven in Table 2, it is clear that entropy of activation increased pos-
Cinh/ θ (10 M)

12 itively in the presence of Cefazolin than in the absence of

-4

inhibitor. The increase of DSa reveals that an increase in disorder-

10
ing takes place on going from reactant to the activated complex
8 [39].
The constant of adsorption, Kads, is related to the standard free
6 energy of adsorption, DGads from the following equation:
 
4 1 DGads
K ads ¼ exp ð10Þ
2 55:5 RT
2 4 6 8 10 12
-4 The value 55.5 in the above equation is the concentration of water
C inh (10 M)
in solution in mol l1 [40]. The standard free energy of adsorption
Fig. 3. Langmuir’s adsorption isotherm plots for the adsorption of Cefazolin at
ðDGads Þ were calculated and the negative values of DGads obtained
different conc. in 1 M HCl on the surface of mild steel. indicates the spontaneity of the adsorption process and stability
of the adsorbed layer on the mild steel surface. Generally values
of ðDGads Þ up to 20 kJ mol1 are consistent with the electrostatic
were calculated and listed in Table 2. Inspection of these data re- interactions between the charged metal (physisorption) while those
veals that the thermodynamic parameters ðDHa and DSa Þ of disso- around 40 kJ mol1 or higher are associated with chemisorption
lution reaction of mild steel in 1 M HCl in the presence of Cefazolin as a result of sharing or transfer of unshared electron pair or

Table 2
The values of activation parameters Ea , DHa and DSa for mild steel in 1 M HCl in the absence and in the presence of different concentrations of Cefazolin.

Inhibitor conc. (M  104) Ea (kJ mol1) DHa (kJ mol1) DSa (J mol1 K1) A (mg cm2) Linear regression coefficient (R2)
8
1 M HCl 42.72 39.55 86.75 5.31  10 0.9881
2.19 63.13 60.47 28.82 5.66  1011 0.9900
4.38 67.71 65.06 16.90 2.37  1012 0.9970
6.57 74.02 71.37 0.0103 1.81  1013 0.9985
8.76 89.41 86.76 44.60 3.87  1015 0.9918
10.95 89.24 86.59 43.83 3.53  1015 0.9911
156 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160

-0.2
(a) (b) -0.4
2.0 -0.6

log r/T(mmy K )
-0.8

-1
log r (mmy )
-1
-1.0

-1
1.5
-1.2
Blank
Blank -1.4 -4
-4 2.19 x 10 M
1.0 2.19 x 10 M
-4 -1.6 -4
4.76 x 10 M
4.76 x 10 M -4
-4 6.57 x 10 M
6.57 x 10 M
-4
-1.8 -4
8.76 x 10 M
8.76 x 10 M -4

0.5 -4
10.95 x 10 M -2.0 10.95 x 10 M

-2.2

2.95 3.00 3.05 3.10 3.15 3.20 3.25 2.95 3.00 3.05 3.10 3.15 3.20 3.25
3 0 -1 3 0 -1
[(1/T).10 ] K [(1/T).10 ] K

(c) -93
-96
Δ Gads /T(JK mol )
-1

-99
-102
-1

-105
-108
-111
-114
-117
2.95 3.00 3.05 3.10 3.15 3.20 3.25
3 0 -1
[(1/T).10 ] K

Fig. 4. (a) Adsorption isotherm plot for log (CR) vs. 1/T; (b) adsorption isotherm plot for log (CR/T) vs. 1/T; (c) adsorption isotherm plot for DG/T vs. 1/T.

p-electrons of organic molecules to the metal surface to form a co- This equation can be rearranged to give the following equation.
ordinate type of bond (chemisorption) [41,42].
DGads DHads
Free energy of adsorption ðDGads Þ was calculated using the fol- ¼ þk ð14Þ
lowing equations and listed in Table 3. T T
The variation of DGads =T with 1/T gives a straight line with a slope
DGads ¼ RT lnð55:5 KÞ ð11Þ that equals DHads (Fig. 4c). It can be seen from the figure that
DGads =T decreases with 1/T in a linear fashion. The calculated values
h
K¼ ð12Þ are depicted in Table 3. The adsorption heat could be approximately
Cð1  hÞ regarded as the standard adsorption heat ðDHads Þ under experimen-
tal conditions [33,46]. The negative sign of DHads in HCl solution
where h is degree of coverage on the metal surface, C is concentra-
indicates that the adsorption of inhibitor molecule is an exothermic
tion of inhibitor in mol l1, R is the molar gas constant and T is tem-
process. Generally, an exothermic adsorption process signifies
perature. The DGads value of the inhibitor was found
either physisorption or chemisorption while endothermic process
35.54 kJ mol1 indicated that it is adsorbed on the metal surface
is attributable unequivocally to chemisorption [47]. Typically, the
by both physical and chemical process [43–45]. The negative values
enthalpy of physisorption process is lower than that 41.86 kJ mol1
of DGads indicated the spontaneous adsorption of inhibitor on sur-
while the enthalpy of chemisorption process approaches
face of mild steel.
100 kJ mol1 [48]. In the present study, the absolute value of enthal-
The enthalpy of adsorption was calculated from the Gibbs–
py is 57.04 kJ mol1, which is an intermediate case. Then the
Helmholtz equation:
standard adsorption entropy ðDSads Þ was obtained using the thermo-
  dynamic basic equation:
@ðDGads =TÞ DHads
¼ ð13Þ
@T T2 DHads  DGads
P
DSads ¼ ð15Þ
T
The DSads values in the presence of inhibitor are large and neg-
ative, meaning a decrease in disordering on going from reactants to
Table 3 the metal adsorbed species.
Thermodynamic parameters for the adsorption of Cefazolin in 1 M HCl on the mild
steel at different temperatures.
3.2. EIS measurements
Temperature K DGads DHads DSads
(K) (mol1) (kJ mol1) (kJ mol1) (J mol1 K1) Electrochemical impedance measurements were performed
308 19,379 35.54 57.04 69.80 over the frequency range from 100 kHz to 0.01 Hz at open circuit
318 6594 33.85 57.04 72.90 potential. The simple equivalent randle circuit for studies is shown
328 3719 33.35 57.04 72.20
in Fig. 5, where RX represents the solution resistance, Rct the charge
338 2576 33.34 57.04 70.11
transfer resistance and double layer capacitance (Cdl). Nyquist plots
 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160 157

frequencies. The fact that this semicircle can not be observed after
the addition of higher concentration of Cefazolin supports our
view. Inhibition efficiencies and other calculated impedance
parameters are given in Table 4. As it can be seen from Table 4,
the Rct values increased with increasing the concentration of the
inhibitor and the values of Cdl decreased with an increase in the
inhibitor concentration. This situation was the result of an increase
in the surface coverage by this inhibitor, which led to an increase in
the inhibition efficiency. The thickness of the protective layer, dorg,
Fig. 5. Electrical equivalent circuit (RX, uncompensated solution resistance; Rct, is related to Cdl by the following equation [53]:
polarization resistance; Cdl, double layer capacitance).
eo er
dorg ¼ ð16Þ
C dl
where eo is the dielectric constant and er is the relative dielectric
15 Blank
-4
constant. This decrease in the Cdl, which can result from a decrease
-Z im ag ( Ω cm 2 )
1 = 4.38x10 M
250 -4 10 in local dielectric constant and/or an increase in the thickness of the
2 = 6.57x10 M
-4 5 electrical double layer, suggested that Cefazolin molecules function
3 = 8.76x10 M
by adsorption at the metal/solution interface. Thus, the change in
0
200 Cdl values was due to the gradual replacement of water molecules
0 5 10 15
2
Zreal(Ω cm ) by the adsorption of the organic molecules on the metal surface,
-Z imag ( Ω cm )

decreasing the extent of metal dissolution [54].

2

150

3.3. Tafel polarization

100
Polarization curves for mild steel in 1.0 M HCl at various con-
centration of Cefazolin are presented in Fig. 7. The values of corro-
sion current densities (Icorr), corrosion potential (Ecorr), the anodic
50
Tafel slopes (ba), cathodic Tafel slopes (bc) and inhibition efficiency
ðgP% Þ as function of Cefazolin concentration were calculated from
the curves of Fig. 7 and presented in Table 4. It reveals that the cor-
0 1 2 3 rosion current (Icorr) decreased prominently and inhibition effi-
ciency increased with inhibitor concentration. The presence of
0 50 100 150 200 250 300 Cefazolin does not remarkably shift the corrosion potential (Ecorr)
2 and hence, can be said to be a mixed-type inhibitor in 1.0 M HCl.
Zreal (Ω cm )
The anodic Tafel slopes changes slightly whereas the change in
Fig. 6. Nyquist plots of mild steel in 1 M HCl with different concentration range of cathodic Tafel slopes are larger which means that Cefazolin
Cefazolin.

-200 1 = Free Acid Solution

of mild steel at various concentrations of Cefazolin in 1 M HCl solu- 2 =
-4
4.38x10 M
Potential (mV vs SCE)

-4
3 = 6.57x10 M
tion are presented in Fig. 6. The impedance spectra for mild steel in -300 4 =
-4
8.76x10 M
1 M HCl are similar in shape with a high frequency (HF) capacitive
loop and low frequency (LF) inductive loop (except at -400
8.76  104 M). The HF capacitive loop can be attributed to the
charge transfer reaction and time constant of the electric double -500
layer. The time constant at high frequencies may be attributed to
formation of surface film [49,50]. On the other hand, the inductive -600
loop has been attributed to a surface or bulk relaxation process or
to a dissolution process [51,52]. We have correlated the low fre- -700
4 1
quency inductive loop seen in the free acid solution with a surface 3 2

dissolution process. The low frequency inductive loop in inhibited -800

0.000 0.001 0.010 0.100 1.000 10.000 100.000
acid solution containing lower concentration of Cefazolin might be -2
Current density (mA cm )
attributed to the relaxation process obtained by adsorption of spe-
cies as Hads þ and Cl on the electrode surface. It might be also Fig. 7. Tafel Polarization behaviour of mild steel in 1 M hydrochloric acid with
attributed to the re-dissolution of the passivated surface at low different concentration range of Cefazolin.

Table 4
Electrochemical parameters for corrosion of mild steel in 1 M HCl in the presence of different concentrations of Cefazolin.

Conc. of inhibitor (M  104) Tafel data Impedance data Linear polarization

2
Ecorr (mV vs. SCE) Icorr (lA cm 2
) ba (mV/dec) bc (mV/dec) gP% Rct (X cm ) Cdl (lF cm 2
) gRct % Rp (X cm2) gRp %
Blank HCl Inh 469 730 73 127 – 17.3 1006 – 18.7 –
4.38 487 124 54 152 83.0 87.3 118 80.1 101.8 81.6
6.57 480 85 62 152 88.3 126.5 109 86.3 128.9 85.5
8.76 481 39 67 186 94.7 262.6 81 93.4 256.6 92.7
158 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160
Fig. 8. Atomic force micrographs of mild steel surface (a) polished mild steel, (b) mild steel in 1 M HCl and (c) inhibited mild steel (1 M HCl + 8.76  104 inhibitor).
molecules are adsorbed on both sites but under prominent catho-
dic control resulting in inhibition of anodic dissolution and catho-
dic reduction reaction.
3.4. Linear polarization resistance
The polarization resistance (Rp) values of mild steel in 1 M HCl
increases from 18.7 X for the blank to 256.6 X for 8.76  104 M
concentration of Cefazolin (Table 4). The increase in the Rp value
suggests that the inhibition efficiency increases with the increase
in the inhibitor concentration.
3.5. Surface characterization: AFM study
The atomic force microscope provides a powerful means of
characterizing the microstructure. The three-dimensional AFM
images are shown in Fig. 8a–c. As it can be seen from Fig. 8a the
mild steel surface before immersion seems smooth compared to
the mild steel surface after immersion in uninhibited 1.0 M HCl
for 3 h. The average roughness of polished mild steel (Fig. 8a)
ðFeCl Þads
and mild steel in 1.0 M HCl without inhibitor (Fig. 8b) was calcu-
ðFeClÞads þ e
lated to be 66 and 395 nm, respectively. It is clearly shown in
Fig. 8b that mild steel sample is getting cracked due to the acid at-
tack on mild steel surface. However in the presence of optimum
Fe2þ þ Cl
concentration of inhibitor, the average roughness was reduced to
167 nm (Fig. 8c).
ðFeHþ Þads
4. Mechanism of inhibition
ðFeHÞads
A clarification of mechanism of inhibition requires full knowl-
edge of the interaction between the protective compound and
the metal surface. Many of the organic corrosion inhibitors have
at least one polar unit with atoms of nitrogen, sulphur, oxygen
and in some cases phosphorous. It has been reported that the inhi-
bition efficiency decreases in the order to O < N < S < P. The polar
unit is regarded as the reaction centre for the chemisorption pro-
cess. Furthermore, the size, orientation, shape and electric charge
on the molecule determine the degree of adsorption and hence
the effectiveness of inhibitor. On the other hand, iron is well
known for its co-ordination affinity to heteroatom bearing ligands.
Increase in inhibition efficiencies with the increase of concen-
tration of Cefazolin shows that the inhibition action is due to
adsorption on the steel surface. Four types of adsorption may take
place by organic molecules at metal/solution interface namely.
(1) Electrostatic attraction between the charged molecules and
charged metal.
(2) Interaction of unshared electron pairs in the molecule with
the metal.
(3) Interaction of p-electrons with the metal.
(4) Combination of (1) and (3) [55].
In HCl solution the following mechanism is proposed for the
corrosion of iron and steel [56].
According to this mechanism anodic dissolution of iron follows:
 
Fe þ Cl

ðFeCl Þads
þ
ðFeClÞads ! ðFeCl Þ þ e
þ 
ðFeCl Þ
The cathodic hydrogen evolution follows:
Fe þ Hþ
ðFeHþ Þads þ e
ðFeHÞads þ Hþ þ e ! Fe þ H2
In acidic solution, carbonyl group, secondary amine group as well as
nitrogen atoms in tetrazole ring (Fig. 9) and adjacent carbonyl
group (O23) can be protonated easily because they all are planar
and having greater electron density (N20, N25, N27, N28 and N29).
Physical adsorption may take place due to electrostatic interaction
between protonated molecule and (FeCl)ads species. Co-ordinate
 A.K. Singh, M.A. Quraishi / Corrosion Science 52 (2010) 152–160
Fig. 9. Three-dimensional representation of Cefazolin molecule.
covalent bond formation between electron pairs of unprotonated S
atom and two N-atoms in thiadiazole ring (S4, N1 and N2) and metal
surface can take place. Further, Cefazolin molecules are chemically
adsorbed due to interaction of p-orbitals with metal surface follow-
ing deprotonisation step of the physically adsorbed protonated mol-
ecules. In the presented case, the value of DGads is 35.54 kJ mol1,
hence, indicated that adsorption of Cefazolin on the surface of mild
steel involves both physical and chemical process. But, as it can be
seen from Table 3, the values of DGads decreased with increasing
temperature hence, indicated that adsorption of Cefazolin does
not favour at higher temperature, indicating that Cefazolin ad-
sorbed predominantly physically on the surface of mild steel.
5. Conclusion
(1) Cefazolin acts as a good inhibitor for the corrosion of mild
steel in 1.0 M HCl.
(2) The inhibition efficiency of Cefazolin decreased with tem-
perature, which leads to an increase activation energy of cor-
rosion process.
(3) The adsorption of Cefazolin obeys Langmuir adsorption iso-
therm. The adsorption process is a spontaneous and exother-
mic process accompanied by an increase of entropy.
(4) Potentiodynamic polarization curves reveals that Cefazolin
is a mixed-type but predominantly cathodic inhibitor.
(5) The results obtained from weight loss, impedance and polar-
ization studies are in a good agreement.
Acknowledgement
One of the author A.K.S. is thankful to University Grant Com-
mission (UGC), New Delhi, for Senior Research Fellowship.
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