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2 Experimental
R. Cui, N. Gu, C. Li
Department of Chemistry, Hebei Normal University, Shijiazhuang 2.1 Synthesis of the inhibitor (PASP)
050016 (P.R. China)
E-mail: gu_ning@tom.com
L-Aspartic acid and H2SO4 were of analytical grade acquired from
Working electrodes were cut from a carbon steel sheet (C: 0.49, Si: 3 Results and discussion
0.17, Mn: 0.50, Cr: 0.25, S: 0.035, Fe: balance; wt%). Measure-
ments were carried out on carbon steel electrode molded in 3.1 PASP characterization by FTIR
polyester leaving an exposed area of 0.28 cm2. The tests were
performed in a standard water-jacketed electrochemical cell with The viscosity average molecular weight (Mw) of PASP was
constant temperature control. The counter electrode was a determined to be 3100. In contrast to the linkage of aspartic acid
platinum electrode and the reference electrode was a saturated in native materials, PASP was obtained by the thermal
calomel electrode (SCE). The electrode surface was polished with polycondensing process containing a_ and b_ linked moieties
abrasive paper up to 1200 grade, degreased with acetone, washed in a constant molar ratio of 30:70 [27–29]. Figure 1 shows the
with double-distilled water, dried under compressed air, and structure of a_ aspartic acid and b_ aspartic acid.
placed in the test solution for 90 min prior to each experiment. All Proof of the sample’s nature was provided by FTIR spectra
potentials were referred to the SCE. shown in Fig. 2. In the spectra of PASP, the characteristic peaks at
1190 and 3411 cm1 correspond to the C–O and O–H stretching
2.3 Weight loss determinations of the –COOH, peak at 1390 cm1 is related to the C–N stretching
mode of the acylamide group, the peak at 1600 cm1 is assigned
Carbon steel specimens (50 25 2.0 mm3) were used for the to the bending of N–H. The band at 1793 cm1 is ascribed to the
weight loss experiment. Carbon steel specimens in triplicate were stretching vibration C – – O. Additionally, the wave number
immersed in 1600 mL of 0.5 M aerated H2SO4 containing various 3000 cm1 is assigned to the C–H stretching vibration. It is
concentrations of PASP at 20 8C. The weight of specimens was evident that the PASP is successfully synthesized.
determined before and after immersion. The immersion
experiments lasted 48 h. 3.2 Weight loss experiment
2.4 Electrochemical techniques Weight loss method can provide the reliable information toward
the inhibitory effect of a given compound. In this part of
Potentiostatic polarization measurements were carried out using experiment, corrosion parameters such as corrosion rate and
CHI660B electrochemical workstation (Chenhua Instrument, inhibitor efficiency were calculated for carbon steel in 0.5 M
Inc., Shanghai, China). The polarization curves were obtained aerated H2SO4 in absence and in the presence of different
from the corrosion potential (Ecorr) up to 300 mV at a potential
scan rate of 2.0 mV/s at 20 8C constant temperature. Impedance
measurements were carried out using AC signals of amplitude
5 mV peak to peak at open circuit potential in the frequency
range 0.05–105 Hz by a PAR potentiostat (EG&G, model 283) and
a PAR lock-in amplifier (EG&G, model 5208). The test was
performed at 10, 20, 30, 40, and 50 8C, respectively.
Table 2. The electrochemical parameters (Ec, bc, ba, ic, and h) associated with polarization measurements of carbon steel in 0.5 M H2SO4 in the
presence of different concentrations of PASP
Figure 4. Nyquist plots of carbon steel in 0.5 M H2SO4 (a) with different concentrations of PASP at 10 8C, (b) without PASP at different temperatures,
and (c) with 2.5 g/L PASP at different temperatures
3.4 Impedance measurements Mathematically, the impedance of a CPE can be defined as [40]:
Figure 5. (a) and (b) represent bode plots of carbon steel electrode in 0.5 M H2SO4 with 2.5 g/L PASP at different temperatures
parallel combination of CPE (Q) and Rp (polarization resistance). For example, an inhibitor’s apparent activation energy can be
For each set of experimental data the parameters Rt, Q, and Rp expressed as [46]:
were evaluated using a nonlinear least square fit procedure as
shown in Table 2. The data are found to be sufficiently well Ea
jcorr ¼ A exp (7)
fitted by a given equivalent circuit within the limits of RT
experimental error. Inhibition efficiency, represented by h(%)
[h ¼ (i0i/i0) 100%], can be determined by performing the where Ea is the activation energy. Taking the logarithm form of
calculation: Equation (7) and substituting jcorr with the well-known Stern–
Geary equation: jcorr ¼ ba bc 2:3ðba þ bc ÞRp , where ba ¼ 2:3 RT=
i Rp aa F and bc ¼ 2:3 RT=ac F, the following equation can be
from ¼ 0 (5)
i0 Rp deduced:
Rp Ea
the following equation is obtained [44, 45]: ln ¼ þ constants (8)
T RT
Table 3. Rt and h of carbon steel in 0.5 M H2SO4 with the existence of different concentrations of PASP at the designed temperatures
Substituting u with h (data shown in Table 1), the coverage The free energy of adsorption, DG0ads , can be determined
degree of u is found to increase with the increasing concentration with the help of adsorption constant K:
of the additive at the same temperature. Table 2 shows that the
experimental data can be well illustrated by the Freundlich 1 DG0ads
K¼ exp (11)
adsorption isotherm: 55:5 RT
Table 4. Activation energy (Ea) of carbon steel in 0.5 M H2SO4 solution The formation of the protective surface film of PASP on the
with the existence of different concentrations of PASP electrode surface was further confirmed by SEM observations of
the electrode surface. Figure 7a shows the SEM image of carbon
r (PASP) (g/L) 0.0 1.0 2.5 5.0 8.0
steel specimen before immersion, and Fig. 7b–d show the SEM
Ea (kJ/mol) 46.60 51.25 50.61 52.33 54.48
images for carbon steel samples exposed in 0.5 M H2SO4
4 Conclusions
5 References
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