Results and DiscussionWeight loss process Table 1 delivers thestandards of the inhibition efficiency and corrosion rate with differentconcentration (0.
2, 0.4 and 1.0) of few alkylsubstituted 2,6-diphenylpiperidin-4-ones with thiosemicarbazone 21 on mild-steelcorrosion in 1 N sulfuric acid media have been computed by a weightloss process at 303 K. Table 1Corrosion parametricquantity of Alkyl substituted 2,6-diphenyl piperidin-4-ones with thiosemicarbazoneon mild-steel in 1 N sulfuric acid from weight loss measurements (303K) SL NO. Name of the inhibitor and concentration Weight Loss (gram) Corrosion Rate (milli miles per year) Inhibition efficiency (%) Surface Coverage (?) 1 Blank 0.0890 79.96 2 01TS 0.
2 0.0177 15.9 80.11 0.8011 0.4 0.0091 8.
2 89.78 0.8978 1 0.0014 1.
26 98.43 0.9843 3 02TS 0.2 0.0233 20.
93 73.82 0.7382 0.4 0.0172 15.45 80.67 0.8067 1 0.
0061 5.48 93.15 0.9315 4 03TS 0.2 0.0245 22.01 72.47 0.
7247 0.4 0.0179 16.08 79.89 0.7989 1 0.0094 8.45 89.
44 0.8944 Theweight loss process indicates the inhibition efficiency (IE) raises with anincrement in inhibition concentration and also the corrosion rate of theinhibitor decreases than to blank solution, it conveys that the alkyl substituted2,6-diphenyl piperidin-4-one with thiosemicarbazones react as a corrosioninhibitor. The surface courage (?) of the corrosion inhibition raised to raise in the different concentrationof the inhibitor. The optimum inhibitionefficiency of these compounds achieved even at very low concentration.
The effectof concentration of alkyl substituted 2,6-diphenyl piperindin-4-one withthiosemicarbazones on weight loss processes disclose that the metal-loss gentlylowered with rising inhibitor concentrations. The structure of inhibitionefficiencies (IE) of these inhibitors at 303 K is (01TS) > (02TS) >(03TS). Examination of the inhibition efficiencies of inhibitors (01TS), (02TS)and (03TS) explains that inhibition efficiency, decrease when it is substitutedwith various groups at 3-position of the piperidin-4-one ring. This tendency can be suggested bythe conformations of substituted piperidin-4-ones and steric hindrance formedby the substitutes (20).
Potentiodynamic polarization method Figure 2 to 4indicates the potentiodynamic polarization plots of the alkyl substituted 2,6-diphenylpiperidin-4-ones of thiosemicarbazone in1N sulfuric acid at different concentrations at 303K. The kinetic parameters of inhibition of corrosion acquiredfrom these plots are disclosed in Table 2. Figure– 2 Potentiodynamic polarizationgraph for mild-steel in 1 N sulfuric acid in the before and after addition of(01TS) I (Ampere per square centimeter) Figure – 3 Potentiodynamic polarization graph for mild-steel in1 N sulfuric acid in the before and after addition of (02TS) I (Ampere per square centimeter) Figure– 4 Potentiodynamic polarization graph for mild-steel in1 N sulfuric acid in the before and after addition of (03TS) I (Ampere per Square centimeter) Table2 Potentiodynamic polarization parametricquantity of the mild-steel in 1 N sulfuric acid with and without Alkylsubstituted piperidin-4-ones with thiosemicarbazone SL NO. Name of the Inhibitor and concentration Icorr (in micro amper per cm2) x10-2 Ecorr (milliVolts vs Saturated calomel electrode) ba (milliVolts/Decade) Bc (milliVolts/Decade) Corrosion Rate (milli miles per year) Inhibition Efficiency (%) 1 Blank 4.57 -524 120 -137 104.71 2 01TS 0.
2 0.69 -547 46 -147 15.81 84.90 0.
4 0.35 -498 39 -131 8.02 92.34 1.0 0.
26 -469 35 -122 5.96 94.31 3 02TS 0.
2 1.30 -533 79 -136 29.79 71.
55 0.4 0.48 -532 55 -133 11.00 89.50 1.0 0.31 -495 32 -135 7.
10 93.22 4 03TS 0.2 1.07 -525 48 -139 24.52 76.57 0.
4 0.46 -494 30 -140 10.54 89.93 1.0 0.
39 -478 35 -116 8.94 91.47 Fromthe table 2, it can identify that as theinhibitor concentration increases, the Icorrvalue reduces and the inhibitor efficiency increases apparently and this showsthe inhibiting character of the inhibitor. The least corrosion rate inpotentiodynamic polarization examination exhibit that the inhibitor hasdefinitely performed on the mild-steel metal surface. A distinction in thevalues of Tafel constant of ba and bcconcluded the character of the inhibitor. An increment in the bc values in theconcentration of the organic inhibitor is a typical aspect of a cathodicinhibitor, which reveals a higher in the energy barrier for proton dischargeprominent to less gas evolution. The variation of ba and bcvalues in the several concentrations of inhibitor in 1 N sulfuric acid are presented in table 2. Examination ofthe results exposes that baand bc values do not shiftappreciably with the concentration of Alkyl substituted Piperidin-4-ones with thiosemicarbazoneand slight variation is observed.
TheEcorr value shifts in thedirection of less negative region whenthe concentration of the inhibitor is improved. This is associated to enhancedinhibitor adsorption on the mild-steel metallic surface. Thus, some alkylsubstituted 2,6-diphenyl Piperidin-4-ones with thiosemicarbazone may bemeasured as a mixed type character of organic inhibitors having more cathodiccharacter.AC impedance methodNyquist graphs for mild-steel metallic corrosioninhibition in 1 N sulfuric acid for alkyl substituted 2,6-diphenyl piperidin-4-onesof thiosemicarbazone exhibited in the figure 5 to 7.
The Impedancerange of the Nyquist plots is described by fitting the experimental data to asimple equivalent circuit model as exposed in Figure 4. It exists of thesolution resistance (Rs)and the double layer capacitance (Cdl)which is organized in parallel to the charge transfer resistance (Rct) (12). Table 3 providesthe significance of double layer capacitance (Cdl),charge transfer resistance (Rct) and inhibition efficiency.
Fig.4 Equivalent circuit model for fittingimpedance spectra TheCharge transfer resistance Rctvalues are determined from the variation in impedance at low and highfrequencies. The Rct valueis a determined of electron transfer over the surface of mild-steel, that isinversely proportional to the rate of the corrosion. The double layercapacitance Cdl isestimated at the frequency fmax at which the imaginary component of theimpedance is maximal using the equation (Ref.
18 and 20). Cdl = (5)Figure 5Nyquist graph of mild-steelcorrosion in 1 N sulfuric acid in the absence and presence of (01TS) Figure 6Nyquist group of mild-steelcorrosion in 1 N sulfuric acid in the absence and presence of (02TS) Figure 7Nyquist graph of mild-steelcorrosion in 1 N sulfuric acid in the absence and presence of (03TS) Z’ (ohm) Table 3Impedance parametricquantity of the mild-steel in 1 N sulfuric acid with and without Alkyl substitutedpiperidin-4-ones with thiosemicarbazone SL NO. Name of the inhibitor and concentration Rct (ohms) Cdl (µ faraday) Inhibition efficiency (%) 1 Blank 32.13 0.
14 2 01TS 0.2 167.75 0.19 80.85 0.4 332.
28 0.10 90.33 1.0 541.12 0.17 94.06 3 02TS 0.2 107.
52 0.48 70.12 0.4 161.49 0.15 80.10 1.0 356.
79 0.11 90.99 4 03TS 0.
2 89.82 0.17 64.
29 0.4 257.06 0.83 87.50 1.
0 341.22 0.71 90.58 The data fromTable 3 shows that Rct value rises with a rise in concentration of inhibitor. Theaddition of inhibitor decreases the Cdlvalues, because the absorption of inhibitors on the metal surface (expansion inthe surface courage of inhibitor). The impedance diagrams are almost semi-circular,illustrate that the corrosion of mild-steel is chiefly inhibited by a charge transfermethod, and the existence of inhibitor does not influence the dissolutionmechanism of mild-steel 1 and 3.
The data on inhibition efficiency attainedfrom impedance measurements are good agreements with the weight loss processand potentiodynamic polarisation measurementsThe inhibitor usingin the present research has two groups of anchoring sites, namely ring Nitrogenand thiosemicarbazone group. Usually, these types of compounds exist either ina boat or in chair conformation. The Alkyl substituted 2,6-diphenyl Piperidin-4-ones with thiosemicarbazonechair conformation is the preferred conformation as phenyl and alkylsubstitutions are in equatorial orientations. The inhibition efficiency ofthese compounds is higher. The interaction of these compounds with mild metalsurface could appear either over a carbonyl group or through ring nitrogen, butnot over both of carbonyl group ornitrogen as they are in para position to one another. The simultaneousparticipation of both the groups is ruled out, because it would be possibleonly through the attainment of boat conformation that is highly strained. Further,the less electro negativity of nitrogen than sulfur support, ring nitrogen tobe the inhibiting site 16 and 20. The inhibition efficiency is furtherincreased by converting carbonyl group to thiosemicarbazone group.
Here we alsoexpect the involvement of either thiosemicarbazone group or ring nitrogen becauseof the presence of substitutes. The high inhibition may be on account of theattraction between nitrogen and sulfur atom of thiosemicarbazone and metalsurface. The present investigation indicates that all the three corrosionmonitoring techniques complement with each other. Analysis of inhibitionefficiency of the three different inhibitors shows the following trends: (01TS)> (02TS) > (03TS)Adsorptionisotherm Organic molecules are helping toinhibit corrosion as they adsorbed on the metal-solution integrates.
Theadsorption anticipate on the chemical sharing of the solution, chemical skeletonof the inhibitor, temperature, the environment of the metal surface, andelectrochemical potential at the metal-solution integrates. The adsorption procedureprovides awareness about the adsorbed molecules themselves in addition to theircooperation with the metal surface. The standards of surface coverage (q ) equivalent to severalconcentrations of an inhibitor (C)are utilized to attain the finest adsorption isotherm. The qvalues have been computed using the following relationships q = (From weight loss process) and q = (From impedance method) TheLangmuir adsorption isotherm is indicated as q = WhereC is the concentration and K is the equilibrium constant for the adsorption procedure.The above equation might be modified as = + C Figure 8Langmuir isotherm forthe adsorption of compounds (01TS), (02TS), (03TS) on the surface of mild-steelin 1 N H2SO4 A straight line with slope equal to unit is obtainedwhen plotting C/? vs C when the experimental data followLangmuir adsorption isotherm.
The existing study Langmuir adsorption isothermwas observed throughout all the inhibitors on mild-steel in 1 N sulfuric acid.Langmuir plots are disclosed in Figure 8 for which ? values are attained from weight loss measurements. Equilibriumadsorption constants are intended from the Langmuir plot and specified in Table(4). The high value of K communicates that the inhibitor isfirmly adsorbed on mild-steel metallic surfaces.
Table 4Equilibriumconstants from Langmuir adsorption isotherms Sl.No Name of the inhibitor K 1 01TS 20.66 2 02TS 13.05 3 03TS 12.
50 Quantum chemical calculations Quantum chemical estimations wereshown from experimental results that it is possible to receive a betterperformance with inhibitors as a corrosion organic inhibitor. It had beenexpressed that the energy of highest occupied molecular orbital (EHOMO) regularly pooled withthe electron donating ability of the molecules. Greater values of EHOMOmark a type of the molecule to donate electrons to perform with acceptormolecules with empty molecular orbital or low energy unfilled.
Accordingly, the energy of lowest unoccupied molecular orbital (ELUMO) shows the intelligenceof the molecule to accept electrons. The least value of ELUMO suggests the molecule accepts electrons more possible. The electronic characteristics likeenergy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecularorbital (ELUMO), energygap (E) between EHOMO and ELUMOon the backbone atoms observed by optimization. The optimized molecularskeleton of inhibitor was given in figure 9. The HOMO and LUMO surfaces forinhibitor given in figure 10. The electronic properties are detailed in table 4Figure 9Optimized molecularstructure of the inhibitors · N-(amino-l2-methyl)nitrous amide compound with 1l3-ethane and 3-methyl-4-methylene-2,6- diphenylpiperidine (1:1:1) N-(amino-l2-methyl)nitrous amide compound with 1,3-dimethyl-4-methylene-2,6-diphenylpiperidine and 1l3-ethane (1:1:1) N-(amino-l2-methyl)nitrous amide compound with 3-methyl-4-methylene-2,6-diphenylpiperidine and l3-methane (1:1:1) Figure 10HOMO and LUMO surfaceof the inhibitors(01TS, 02TS and 03TS) Table 5Quantum parameters of(01TS), (02TS) and (03TS) Quantum chemical parameters 01TS 02TS 03TS EHOMO -0.28202 -0.28038 -0.
28200 ELOMO 0.10952 0.10774 0.10712 DE= (ELOMO – EHOMO) 0.39154 0.38812 0.
38912 I= – EHOMO (ev) 0.28202 0.28038 0.28200 A= -ELOMO -0.10952 -0.10774 -0.
10712 ? (Debye) 3.5729 3.4763 3.2728 The resultsseem to reveal that, charge transmission from the molecules of inhibitor takesplace during the adsorption of the inhibitor molecules to the metal surface. Whenthe chemisorption reaction appears, one among the reacting species perform as anelectron pair donor and the rest as an electron pair acceptor 22.
It is clearfrom Table 5 illustrates that the EHOMOof inhibitors are almost the same. The conclusions are in excellent concurrentwith that of the experimental values. The energy gap (?E) is a valuable parametric quantity as a function of inhibitormolecule reactivity in the direction of the adsorption on the metal face20. As the energy gap (?E)decreases, the reactivity of the molecule rises, dominant to rise in thepercentage (%) of inhibition efficiency (IE)of the molecule. The least value of the energy gap (?E) will be supported a enhanced inhibition efficiency, because theenergy essential for the rejection of an electron from the finally occupiedorbital will be low 23. The dipole moment? (Debye) is a further valueelectronic parameter in quantum chemical calculation studies that analysis fromnon uniformed sharing of charges on the a mixture of atoms in the molecule. Thelarger values of the dipole moment (?),possibly increases the absorption between chemical compounds and metal surface24. The energy of the deformability increases respectively, with the rise ofdipole moment ? (Debye) developing themolecule easier to adsorb on the mild-steel metal surface.
The inhibitormolecules volume further rises with the increase of Debye. This increases the approaching area surroundedby the molecule and the surface of the mild-steel in extension to the corrosioninhibition capability of inhibitors. CONCLUSION:1) The inhibition nature ofmild-steel metal in 1 N sulfuric acid by alkyl substituted 2,6-diphenyl piperidin-4-one with thiosemicarbazone has beenexamined by quantum chemical calculation, AC impedance spectroscopy, weightloss process and potentiodynamic polarization method.
2) The alkyl substituted 2,6-diphenyl piperidin-4-one with thiosemicarbazonespresent greatest efficiency towards inhibition of corrosion of mild-steel in 1 NH2SO4 medium. This has possibly induced by the progress of a complex on the mild-steelmetal surface at lower concentrations because adsorption on the surface.3) Thehigher value corrosion inhibition efficiency (IE) of these inhibitor compoundsgained even at very low concentration of the inhibitor. The rate of corrosion inhibition gets decreasedwith the increment in the inhibitor concentration.4) The adsorption of a number of alkyl substituted2, 6-diphenyl piperidin-4-one with thiosemicarbazones at mild-steel corrosion inacid solution (1 N H2SO4) pursued the Langmuir adsorptionisotherm model.5) The deviation of Tafel constants ba and bcand Ecorr values with therise in inhibitor concentration suggest that these compounds perform as an inhibitorof mixed characteristics with more cathodic character. This is attested by the electrochemicalAC impedance spectroscopy, which shows a transform in the charge transferresistance and double layer capacitance signifying the inhibitors adsorption on the mild-steelsurface.
The some alkyl substituted 2,6-diphenyl piperidin-4-one withthiosemicarbazone adsorb to the mild-steel surface mainly by chemisorptionmechanism.6) Even though thesecompounds containing ring nitrogen, the ultimate inhibition efficiency (IE) aredue to >N-NH-CS-NH2.7) Computed quantumchemical characteristics such as HOMO-LUMO energy gap (?E) and dipole moment (?) were formed in good correlation withexperimentally resolved corrosion inhibition efficiency.
8) Analysisof inhibition efficiency of the three distinctive inhibitors displays thesuccessive trends. (01TS) > (02TS) > (03TS).