Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(5), 1-12, May (2015)                      Res. J. Chem. Sci. International Science Congress Association       
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Pyrazole Methyl Substituted Compound used as a Corrosive Inhibitor for Mild Steel in Acidic EnvironmentEzhilarasi M.R., Prabha B. and Santhi T.Department of Chemistry, Karpagam University, Coimbatore, 21, INDIAAvailable online at: 
www.isca.in, www.isca.me
Received 8th March 2015, revised 24th April 2015, accepted 10th May 2015 AbstractThe inhibitive effect of compound on mild steel in 1M H2SO4 and 1M HCl was investicated by weight loss, Potentiodynamic polarization and electro chemical impedence studies. The synthesized compound of 1-acetyl-4,5-dihydro-5-phenyl-3-(thiophen-2yl) pyrazoles was characterized by FTIR, 1H NMR, 13C NMR. The structure are also elucidated and purity confirmed by TLC. The corrosion inhibition rate was increased in increasing the concentration of our synthesized inhibitor (1-acetyl-4, 5-dihydro-5-methyl phenyl-3-(thiophen-2yl) pyrazoles). The synergetic effect also studied and observed good correlation between halides and our inhibitor. The adsorption isotherm was also confirmed by langumuir adsorption isotherm. Keywords: Pyrazole, mild steel, inhibition efficiency, synergetic effect, adsorption isotherm, kinetics. Introduction Pyrazoles are important class of five membered heterocyclic compounds with two adjacent nitrogens in a five-membered ring system. Among the two nitrogen atoms; one is basic and the other is netural in nature. These are aromatic molecules due to their planar conjugated ring structures with six delocalized electrons. The aromatic nature arises from the four  electrons and the unshared pair of electrons on the �NH nitrogen. Heterocyclic compounds represent a potential class of corrosion inhibitors. Corrosion inhibition by N containing heterocyclic compounds has been widely reported. Heterocyclic compounds containing both N and S atoms are of particular importance as they often provide excellent inhibition compared to those containing only N or S. The planar  electrons and lone pair of electrons present on the heteroatoms are the important structural features that determine the adsorption of these molecules on the metal surface. Although a vast number of heterocyclic compounds have been reported as corrosion inhibitors, no work has so far been reported on the use of pyrazoles as corrosion inhibitors for the metals especially mild steel. pyrazole is a 5 membered ring system which contains two N atom in it. pyrazoles are very useful units in the field of medicinal chemistry and have been reported to exhibit a variety of biological activities. Stainless steel is widely used in many applications such as desalination plants, construction materials, pharmaceutical industry, thermal power plant, chemical cleaning and pickling process, due to their stability, good corrosion resistance, high strength, workability and weldability. Corrosion is the deterioration of essential properties of a material due to reactions with its surroundings. Millions of dollars are lost each year because of corrosion. Much of this loss is due to the corrosion of iron and steel although many other metals may corrode as well. Corrosion damage can cause leakage of fluids or gases. Even more dangerous is a loss of strength of the structure induced by corrosion and subsequent failure. The application of acid corrosion inhibitors in the industry is widely used to prevent or minimize material loss during contact with acid. It has been observed that the adsorption depends mainly on certain physico-chemical properties of the inhibitor molecule such as functional groups, steric factors, aromaticity, electron density at the donor atoms and P orbital character of donating electrons and also on the electronic structure of the inhibitor. It has been reported that many inorganic, organic and heterocyclic compounds containing hetero atoms like N, O, S and P have been proved to be an effective inhibitors for the corrosion of stainless steel in acid media2-54. Pyrazole compounds have a good inhibition effect on mild steel in acidic environment67. The aim of this work is to synthesize (1-acetyl-4, 5-dihydro-5-phenyl-3-(thiophen-2yl) pyrazoles) characterized by FT-IR, 13C NMR, H NMR, Elemental analysis and their inhibitive effect on mild steel in HCl and HSO environments determined by weight loss, potentiodynamic polarization and electro chemical impedence studies. Material and Methods The composition of the mild strip: C-3.15, Mn-0.61, P-0.07, S-0.049, Cu-0.5, Cr- 0.155,Sn-0.035 and reminder iron were used for weight loss method. Materials: Analytical grade chemical and triple-distilled water were used to prepare solution. The corrosion medium was an aqueous aerated solution 1 M H2SO4. The concentration of the inhibitors employed was 10,20,30 and 40 ml. The experiments 
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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were performed by triplicate and the average value of the weight loss and electrochemical tests were reported. For each test, freshly prepared solutions and a cleaned set of electrodes were used. In weight and electrochemical tests one size of specimens were used. The metallic coupons for the weight loss tests have dimension of 1cm x 5 cm x 0.33 cm, and the working electrodes for the electrochemical tests a surface area of 0.339 cm. Before each experiment the electrode was first mechanically abraded with various grades of grinding paper (up to 1200 grit) and then polished successively using emery sheets of 400 and 600 grades to remove adhering impurities. At the end they were cleaned with double distilled water and ethanol. Measurements and Equipments: The compounds were synthesised and characterized by 1H and 13C NMR and IR spectroscopy. Melting points (uncorrected) were determined using a Guna melting point apparatus. FT-IR spectra were carried out on a Perkin-Elmer1650 spectrophotometer and noteworthy absorption values (cm-1) alone are listed. H and 13C NMR spectra are recorded at 400MHz and 100 MHz respectively on Bruker AMX 400 NMR spectrometer using CDCl as solvent. Chemical shifts () were reported in ppm. The microwave- assisted reaction was performed using a controllable single- mode microwave reactor, CEM Discovery, designed for synthetic use. The reactor is equipped with a magnetic stirrer and device to control pressure, temperature (on-line IR detector) and power.   Synthesis of Compound: Chalcone, (0.01mol), hydrazine hydrate (0.01 mol), anhydrous sodiumacetate (0.01) and acetic anhydride taken in a round bottom flask and the reaction mixture flask was refluxed until the products are formed .The reaction is monitored by TLC. The reaction mixture is poured in to crushed ice and left overnight. The precipitate is separated by filtration. Washed well with water, dried and obtained solids are purified by column chromatography using toluene and etylacetate (1:1) mixture as eluent which afford the title compound in excellent yields55. From a chemical point of view, an important feature of chalcones is the ability to act as activated unsaturated system in conjugated addition reactions of carbanions in the presence of basic catalysts56. The effect of the structure of organic compounds on their inhibiting properties: Most organic inhibitors57 contain at least one polar group with an atom of nitrogen, sulphur, or in some cases selenium and phosphorus. According to Hackerman58, the inhibiting properties of many compounds are determined by the electron density at the reaction center. With an increase in the electron density at the reaction center, the chemisorption bonds between the inhibitor and the metal are strengthened. Hackerman established the protective properties of pyridine and its derivatives. He found that, the ability of these compounds to reduce corrosion, are actually enhanced at higher electron densities around the nitrogen atom, according to the sequence: pyridine  3-picoline  2-picoline  4- picoline. It is assumed that for organic compounds during the first ionization one of the electrons of the unshared pair is detached, then the ionization potential can serves as a measure of the electron density at the nitrogen atom. 
CHO
+
H3C
C
O
CH
Ethanol,NaOHIce bath stirring for 1H
O
CH
Thiophene-2-carbaldehydep-methyl acetophenone(2E)-1-methylphenyl-3-(thiophene-2-yl)prop-2-en-1-one
S
N
N
C
O
H3C
CH
Hydrazine hydrateAnhyd.CHCOONaAcetic anhydrousreflux 6-8 hoursScheme-1 1-acetyl-4, 5-dihydro-5-methylphenyl-3-(thiophen-2yl) pyrazole
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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 S
H
CH
C
O
X
Mechanistic Pathway via.,Michael Addition                NH.NH.H                (CHCO)          Anhyd.CHCOONaHeatingfor6-8 hrs.
CH
HN
H2C
N
O
H
H
X
S
N
N
H
OH
X
S
HN
N
X
In situ acetylation by acetic anhydride
N
C
O
CH
N
X
Scheme 2 Synthetic Reaction Pathway towards the synthesis of title compound via., Michal Addition PathwayX=CHScheme-2 Synthetic Reaction Pathway towards the synthesis of title compound via, Michal Addition Pathway 
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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Hackerman et al59,60 have been studied the adsorption of organic substances with a long hydrocarbon chain from organic solvents. These studies showed that the better the substance is adsorbed, the more effectively it protects the surface. Corrosion monitoring methods: Weight loss tests: Weight loss measurements were performed at 35�C and 45�C for 1 h by placing the carbon steel coupons into the acid solution (20 ml) with and without 10ml of inhibitor. At the end of the testing period, the specimens were cleaned according to ASTM G0141 and finally its weight loss were recorded. The corrosion rate (Vcorr mm/year), inhibition efficiency (IE,%) and surface coverage () were determined by the following equations. 
    (1) 
      (2) 
  (3) Where W is the weight loss(g), D is the steel density (g cm-3), A is the surface area (cm), T is the exposure time (h), and Vcorr,0 and Vcorr,i are the weight loss values in the absence and presence of inhibitors, respectively. Electrochemical tests: Electrochemical measurements were performed in a conventional three-electrode glass cell. Electrode potentials were measured against a saturated calomel electrode (SCE), the counter electrode was a mesh of Pt (purity 99.9%) and the working electrode was made of mild steel (0.339 cm).  The SCE was connected to a Luggin capillary, the tip of which was placed very close to the surface of the working electrode to minimize IR drop. Tests were performed at 25�1�C and thermostatically controlled. Electrochemical testing was performed in a potentio stat Instrument Model: CHI604D controlled by a PC through the general purpose electrochemical system (GPES); the software provided by AUTOLAB. The specimen was immersed in the test solution for 40 minutes at the open circuit potential (Eocp) to reach a steady-state condition. The polarization resistance measurements (Rp) were then performed in the potential range of �20 mV versus Ecorr  at a scan rate of 1.0 mVs-1. 
  (4) Where Rop and Rip are the polarization resistances in the absence and presence of inhibitor, respectively. Corrosion current densities (icorr) obtained by Tafel extrapolations were used to determine the inhibition efficiencies using the equation: 
 (5) Where: iicorr  and iocorr are the corrosion current densities values with and without inhibitor, respectively. Synergistic effect of halide ions: Effect of the addition of 0.1 N KI and KCl to different concentrations of inhibitors on the corrosion inhibition of iron in 1M HCl and HSO using weight loss technique was studied. This is called synergistic effect process.Results and Discussion Structural elucidation of synthesized organic compound: 1-acetyl-4,5-dihydro-5-methyl phenyl-3-(thiophen-2yl)pyrazoles are synthesis in excellent yields by the reaction of chalcones with hydrazine hydrate catalyzed by anhydrous sodium acetate/acetic anhydride under conventional method. In our present study, acetic anhydride is the best solvent for the facile synthesis of acetyl pyrazoles, in excellent yields without any solubility problem. In addition , insitu acetylation occurs in the course of the reaction due to solvent, acetic unhydride under the reaction conditions. An array of  compound namely 1-acetyl-4,5-dihydro-5-methylphenyl-3-(thiophen-2yl) pyrazoles was synthesized under classical thermal method. The structures of the synthesized 1-acetyl-4,5-dihydro-5-methylphenyl-3-(thiophen-2yl) pyrazoles was confirmed by FT-IR,MS.1HNMR and 13C NMR spectral studies and elemental analysis (scheme-1). FT-IR spectrum of compound shows characteristic absorption frequencies at 3086.11,3001.24 cm-1 due to aromatic CH stretching vibration. The absorption bands at 2885.51 cm-1 are attributed to the aliphatic CH stretching vibration. The absorption frequency at 1658.78 cm-1 is assigned to amide carbonyl stretching vibration. The absorption band at 1417.68cm-1 is assigned to C=N stretching vibration. The absence of carbonyl band clearly supported for the formation of the required compound, besides the disappearance of NH stretching vibration, which conforms the situ acetylation reaction due to acetic anhydride solvent. Elemental analysis of (Ccal 67.19, Cobs 67.13; Hcal  6.34, Hobs 6.29; Ncal 9.79,   Nobs 9.78; Scal 11.21, Sobs 11.18. m/z(M)+: 286 are consistent with the proposed molecular formula (C1516SO) of the compound. In the H NMR spectrum of1-acetyl-4,5-dihydro-5-methylphenyl-3-(thiophen-2yl) pyrazoles, the methylene protons (H-4a and H-4e) of the pyrazoline moiety appeared as two doublets of doublets due to multiple coupling involving both geminal and vicinal protons. The signals for H-4a and H-4e are observed at 3.35 and 3.71 ppm. The doublet of doublet at 3.35ppm (J4a,5a=17.5 Hz and J4a,4e=4.0 Hz) is assigned to H-4a proton of the pyrazoline moiety. Likewise, the doublet of doublet at 3.75 ppm (J4e,4a =17.5 and J4e,5a =11.5 Hz) is assigned to H-4e proton of the pyrazoline moiety. Similarly, the methine proton (H-5) of the pyrazole moiety is expected to give signal as a doublet of doublet due to vicinal coupling with the 
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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two magnetically nonequivalent protons of  the methylene group (H-4a-H4e) of the pyrazoline moiety and the signals are observed at 5.91 ppm (J5a,4a= 11.5Hzand J5a,4e =4.0 Hz).Also the acetyl methyl protons of pyrazoline moiety gives signal as a singlet at 2.43 ppm. The aromatic protons appear as a multiplet in the range of 6.93-7.68 ppm. In the 13C NMR specrum of 1-acetyl-4,5-dihydro-5-methylphenyl-3-(thiophen-2yl)pyrazoles, 13C resonance at 55.16 ppm is assigned to C-5 of pyrazole moiety. The 13C resonance observed at 42.07 ppm is due to C-4 of pyrazole moiety. The 13C resonance observed at 153.98 ppm is assigned to C-3 of pyrazole moiety. The aromatic carbons are observed in the region of 124.54-128.48 ppm.  The 13C resonance observed at 21.98 ppm is due to acetyl methyl carbon. The remaining 13C signal at 144.42,140.78 is due to ipso carbon. Weight Loss Method: The inhibition efficiency with different concentration of the inhibitor on the mild steel in 1M HSO and 1M HCl  has been evaluated by weight loss measurements and the results are summarized in table-1. 
N
N
C
O
H3C
CH
The data revels that inhibition efficiency increases with increase in concentration of the inhibitors. The behavior may be attributed to an increase in surface coverage () by the adsorption of inhibitor on the mild steel surface, in the aggressive solution, which restricts the dissolution of the metal. 
Figure-1 Plot of corrosion rate against inhibition efficiency of mild steel in IM H2SO4 and 1M HCl in presence of the inhibitors Table-1 Inhibition efficiency at various concentrations of pyrazole for the corrosion of mild steel in IM H2SO4 and 1M HCl obtained by weight loss measurements at 28�CMedium Inhibitor concentration in %
Weight 
loss in mg 
Inhibition 
efficiency in %
D
egree of 
coverage inC/
Corrosion rate 
in mpy�10-3 
HCl 
blank(10 ml) HCl
 
0.009
 
 
 
 
0.0115
 
HCl + 0.1 S
 
0.008
 
11.11
 
0.11
 
90.9
 
0.01028
 
HCl + 0.2 S
 
0.004
 
55.56
 
0.55
 
36.3636
 
0.00514
 
HCl + 0.3 S
 
0.005
 
44.44
 
0.44
 
68.181
 
0.0064
 
HCl + 0.4 S
 
0.006
 
33.33
 
0.3
3
 
121.2
 
0.0077
 
SO4 
blank(10 ml)H
2
So
4
 
0.035
 
 
 
 
0.0449
 
H
2
SO
4
 
+ 0.1 S
 
0.017
 
51.43
 
0.51
 
19.61
 
0.0218
 
H
2
SO
4
 
+ 0.2 S
 
0.012
 
65.714
 
0.66
 
60.6061
 
0.01542
 
H
2
SO
4
 
+ 0.3 S
 
0.008
 
77.1428
 
0.77
 
51.948
 
0.01028
 
H
2
SO
4
 
+ 0.4 S
 
0.01
 
71.4
 
0.71
 
42.2535
 
0.0128
 
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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Effect of temperature: The effect of temperature on the inhibited acid-metal reaction is highly complex because many changes occur on the metal surface such as rapid etchings, desorption of the inhibitor and the inhibitor may undergo decomposition and rearrangement. To evaluate the effect of temperature on the adsorption behavior as well as to determine the activation parameters of the corrosion of mild steel in 1M SO solution and 1M HCl solution containing the inhibitors, the weight loss measurements were carried out in the temperature range of (301-318K) and the results are presented in table-2. The data revel that as the temperature is increased the corrosion rate increased and the inhibition efficiency decreased. The decrease in the inhibition efficiency with increase in temperature may be attributed to the increase in the solubility of the protective film or the reaction products precipitated on the surface of the metal that might otherwise inhibit the reaction61,62. This is in accordance with Ergun et al63. The corrosion rate (CR) of the mild steel in acidic media is related to the temperature by the Arrhenius Equation,  Log CR = log A � Ea/ 2.303 RT (6) Where: CR is the corrosion rate, Ea is the apparent activation energy, R is the molar gas constant, T is the absolute temperature and A is the frequency factor. The plot of log CR vs 1/T is shown in figure-2. Linear plots were obtained. 
Figure-2 Arrhenius plot of corrosion rate of mild steel in IM H2SO4 and 1M HCl  in presence and absence of the inhibitors Table-2 Effect of temperature on inhibition efficiency of  pyrazole at 0.01 ml concentration in IM H2SO4  and 1M HClName of the medium Temperature (K) Weight loss (mg) Inhibition Efficiency % Corrosition Rate (mpy) 
Blank HCl 301 0.036  0.0462 
HCl + S 301 0.009 75 0.0116 
Blank HCl 308 0.04  0.0475 
HCl + S 308 0.016 60 0.02056 
Blank HCl 318 0.037  0.0514 
HCl + S 318 0.021 43.24 0.02698 
Blank HSO4 301 0.142  0.1824 
SO + S 301 0.018 87.32 0.0231 
Blank HSO4 308 0.034  0.0436 
SO + S 308 0.011 67.65 0.01413 
Blank HSO4 318 0.036  0.0462 
SO + S 318 0.007 80.56 0.00899 
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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Adsorption isotherm: Adsorption of the inhibitor molecules mainly depends on the charge and nature of the metal surface, electronic characteristics of the metal surface, temperature, adsorption of the solvent, ionic species and the electrochemical potential at the solution interface. The adsorption isotherm describes the adsorption behavior of organic compounds. The most frequently used adsorption isotherms are Langmuir, Tempkin, Frumkin and Freundlich. To obtain the adsorption isotherm, the degree of surface coverage () was calculated for various concentrations of pyrazoles from the weight loss data and listed in table-1. Adsorption behavior of thiazines is best explained by Langmuir adsorption isotherm. Langmuir isotherm is an ideal isotherm for physical or chemical adsorption where there is no interaction between the adsorbate and adsorbent64,65. Assumption of Langmuir relates the concentration of the adsorbate in the bulk of the electrolyte (C) to the degree of surface coverage () according to the equation,  C/ = 1/K + C (7) Where: �K� is the equilibrium constant of adsorption. Applicability of Langmuir adsorption isotherm to the adsorption of pyrazole on mild steel confirms the formation of multimolecular layer of adsorption where there is no interaction between the adsorbate and the adsorbent. Potentiodynamic polarization tests: In iron or steel corrosion, electrochemical reactions may take place as follows57: At the anodic areas Fe  Fe2 + 2e- (8) When iron corrodes, the rate is usually controlled by the cathodic reaction. There are several different cathodic reactions that are frequently encountered in metallic corrosion. The most common are: Hydrogen evolution: 2H   + 2e-  H Oxygen reduction (acid solution): O + 4 H+  + 4e- 2HO Oxygen reduction (neutral or basic solution):    + 4H O + 4e 4OHMetal ion reduction: M3+   + e-  M2+Metal deposition: M    + eM Hydrogen evolution is a common cathodic reaction since acidic media are frequently encountered. Oxygen reduction is very common, since any aqueous solution in contact with air is capable of reducing this reaction. Metal ion reduction and metal deposition are less common. All the above reactions are consuming electrons. Since the anodic and cathodic reactions occurring during corrosion are mutually dependent, it is possible to reduce corrosion by reducing the rates of either reaction. So, if the surface of the metal is coated with paint or other conducting film, the rates of both anodic and cathodic reactions will be greatly reduced and corrosion will be retarded. The corrosion behaviour of metals, and thus the corrosion-inhibiting processes as well, depend greatly on the anion composition of the electrolyte. The values of electrochemical parameters, i.e., corrosion current density (icorr), corrosion potential (Ecorr), Tafel slops (c) and inhibitor efficiency (IET,%) obtained as function of different  are measured. 
Figure-3 Langumuir adsorption isotherms after the addition of inhibitor used for carbon steel in 1 M HCl and 1M HSO
Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(5), 1-12, May (2015)                  Res. J. Chem. Sci.  International Science Congress Association            
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EI Q
q 3008 0 0 4 1084 4604 cm
BI
/CS/RGB
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EI Q
q 3008 0 0 4 1084 4604 cm
BI
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&E 	g�L�
EI Q
q 3008 0 0 4 1084 4572 cm
BI
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&E 	g�L�
EI Q
q 3008 0 0 4 1084 4572 cm
BI
/CS/RGB
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/H 1
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/DP\&#x/Pre;&#xdict;&#xor 1;&#x5
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/C;&#xolum;&#xns 7;&#x52
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&E 	g�L�
EI Q
q 3008 0 0 4 1084 4572 cm
BI
/CS/RGB
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/;&#xColo;&#xrs 3;��$�nI�
EI Q
q 3008 0 0 4 1084 4412 cm
BI
/CS/RGB
/W 752
/H 1
/BPC 8
/F/Fl
/DP&#x/Pre;&#xdict;&#xor 1;&#x5
/C;&#xolum;&#xns 7;&#x52
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/;&#xColo;&#xrs 3;''W6{��G�������e���zzz���!����@�����&���
MjY�bEdd�͛7���!�?~J
hʼn',--g͚�����4�#�@�[ZZ^�|&#x/Pre;&#xdict;&#xor 1;&#x5
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hʼn',--g͚�����4�#�@�[ZZ^�|&#x/Pre;&#xdict;&#xor 1;&#x5
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EI Q
q 3008 0 0 4 1084 4320 cm
BI
/CS/RGB
/W 752
/H 1
/BPC 8
/F/Fl
/DP&#x/Pre;&#xdict;&#xor 1;&#x5
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/;&#xColo;&#xrs 3;"7�
EI Q
q 3008 0 0 4 1084 4320 cm
BI
/CS/RGB
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/H 1
/BPC 8
/F/Fl
/DP&#x/Pre;&#xdict;&#xor 1;&#x5
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/;&#xColo;&#xrs 3;"7�
EI Q
q 3008 0 0 4 1084 4320 cm
BI
/CS/RGB
/W 752
/H 1
/BPC 8
/F/Fl
/DP"7�
EI Q
q 3008 0 0 4 1084 4320 cm
BI
/CS/RGB
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/H 1
/BPC 8
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/;&#xColo;&#xrs 3;&#x/Pre;&#xdict;&#xor 1;&#x5
/C;&#xolum;&#xns 7;&#x52
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/;&#xColo;&#xrs 3; Figure 4 Potentio dynamic polarization curves for carbon steel in 1M HSO4 and 1M HCl solution and after addition of inhibitor SKinetic-thermodynamic corrosion parameters: The effect of temperature (28�C, 35�C and 45�C) on the corrosion rate of iron in 1M HCl and HSO at different concentrations of inhibitors was studied using weight loss measurements. Plots of log k (corrosion rate) against 1/T (figure-5), for iron dissolution in at different concentrations of inhibitor, give straight lines. The values of the slopes obtained at different temperatures permit the calculation of Arrhenius activation energy (Ea*).  Activation parameters for corrosion of iron in 1M HCl and 1M H2SO4 were calculated from Arrhenius type plot66: k=A exp (-Ea*/RT) (9) and transition state type equation:  k=RT/Nh exp (S*/R) exp (-H*/RT) (10) The almost similar values of Ea* suggested that the inhibitors are similar in the mechanism action and the order of the efficiency may be related with the pre-exponential factor A in Equation 10(not shown). 
Figure-5 Log (corrosion rate/T) � (1/T) curves for dissolution in 1M HCl and 1M HSO in absence and presence of inhibitor 
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The presence of investigated derivatives increases the activation energy of iron indicating strong adsorption of the inhibitor molecules on the metal surface. The presence of these additives induce energy barrier for the corrosion reaction and this barrier increases with increasing the additive concentration. The values of H* are reported are positive. The positive sign of the enthalpy reflects the endothermic nature of Fe dissolution process. Also, the values of entropy of activation are negative. The negative values of entropy imply that the activated complex in the rate determining step represents an association rather than dissociation step, meaning that a decrease in disordering takes place on going from reactants to activated complex. A decrease in inhibition efficiency with rise in temperature, suggests a possible desorption of some adsorbed inhibitor molecules from the metal surface at higher temperatures. Such behaviour indicates that inhibitor molecules were physically adsorbed on the metal surface. Synergistic effect: The synergistic effect provided by the addition of halide ions such as I-,  and Cl to the solution containing 1M HSO and 1M HCl in the presence of inhibitors  was studied by weight loss method and the data are presented in table. Analysis of the data reveals that the addition of halides to the inhibitors increases the inhibition at each concentration of the inhibitor tested. This increase in inhibition efficiency shows that the mechanism of the synergistic action is due to the co- adsorption of halides and the inhibitor. The strong chemisorptions of halide ions on mild steel surface make the iron surface to a negatively charged one. Organic compounds containing nitrogen in aqueous acidic solutions may exist either as neutral molecules or cations. The positively charged propagated cations may then be absorbed by columbic attraction on the metal surface where halide ions are already adsorbed. This leads to more surface coverage and hence greater inhibition. The order of synergism of halide ions with the tested inhibitors has been found to be I- � Cl-1. The reason for better synergism with iodide ion is due to the large size and ease of polarisibility of I- ion, which facilitates chemisorptions on the iron surface. Conclusion Corrosion inhibition study on using mild steel in acidic environment with various concentration of inhibitors and additives at room temperature has been reviewed. Electro chemical studies like Polarization, AC impedance and surface morphology such as Fourier Transform infrared Spectroscopy,H1 NMR  and 13C NMR have also been analyzed for the synthesized pyrazole compound. References 1.Ajay Kumar K., Jayaroopa P., Int J Pharm Tech.,5(4), 1473-1486 (2013)2.Selvakumar P., Balanaga B. Karthik and Thangavelu C., Research Journal of Chemical Sciences,3(4), 87-95 (2013)3.Bockris J.O.M. and Reddy A.K.N., Modern Electrochemistry 2B, Electrodics in chemistry, Engineering, biology and Environmental Science, second ed., Kluwer Academic plenum publishers, New York, 1703 (2000)4.Ashassi Sorkhabi H., Asghari, Effect of hydrodynamic conditions on the inhibition performance of L-methionine as a green inhibitor, J. Electrochim Acta.,54, 162-167 (2008)5.Reeta Agarwal and Namboodhiri T.K.G., The inhibition of sulphuric acid corrosion of 410 stainless steel by thioureas, J.Corros. Sci,30, 37-52 (1990)6.Urgen M. and Cakir A.F., The Effect of Molybdate ions on the temperature dependent pitting potential of austenitic Stainless steel in neutral chloride solutions, J. Corros. Sci.,32, 841-852 (1991)7.Lu. Y.C. and Ives M.B., The improvement of the localized corrosion resistance of Stainless steel by cerium, J. Corros. Sci.,34, 1773-1785 (1993)Table-3 Synergistic effect of 1M KCl and KI on the inhibition efficiency of inhibitors in 1M HSO  and 1M HCl by weight loss method at 28�CName of the medium Inhibitor concentration in %Weight loss in mg Inhibition efficiency in %Degree of coverage in C/Corrosion rate in mpy�10-3 
HCl blank HCl 0.009    0.0115 
HCl+ S+ 0.1KI 0.005 44.44 0.44 22.95 0.0064 
HCl+ S+ 0.2KI 0.0024 73.33 0.73 27.39 0.0031 
HCl+ S + 0.3KI 0.003 66.67 0.67 44.776 0.00385 
HCl+ S+ 0.4KI 0.0032 64.44 0.64 62.5 0.0041 
SO4 blank H2SO4 0.035    0.0449 
H2SO4+ S+ 0.1KI 0.003 91.4 0.91 11.098 0.0038 
H2SO4+ S+ 0.2KI 0.009 74.28 0.74 27.027 0.0116 
H2SO4+S + 0.3KI 0.006 82.85 0.83 36.145 0.0077 
H2SO4+S+ 0.4KI 0.004 88 0.88 45.45 0.0054 
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Figure-6 Nyquist diagram for mild steel in IM H2SO4 and 1M HCl  in presence and absence of the inhibitor. 8.Zhou Mingpeng, Wang Kaiming, DiaoYuemin and Zhou Bensheng, Corrosion inhibition of methylenephosphonic acids with R-N-[CH2PO(OH)2]2 structure in sulpuric acid solution, J. Chinese Society of Corrosion and Protection,14, 283-290 (1994)9.Al Mayout A.M, Al Suhybani A.A., Al Ameery A.K., Corrosion inhibition of 304SS in sulphuric acid solutions by 2-methyl benzoazole derivatives, Desalination,116, 25- 33 (1998)10.Yang W.Z. and Zhou B.S., Study on corrosion inhibition by N-Sulfonic amino di methylenephosphonic acid, J. Chinese Society of Corrosion and Protection,20, 105-110 (2000)11.Gopi D. and Rajeswari S., Surface characterization and electrochemical corrosion behavior of 304stainless steel in aqueous media, J. Solid State Electrochemistry,, 194-202 (2002)12.Abdallah M., Rhodanine azosulpha drugs as corrosion inhibitors for corrosion of 304stainless steel in hydrochloric acid solution, J. Corros. Sci.,44, 717-728 (2002)13.Paul A. Kilmartin, Lissa Trier and Graham A Wright, Corrosion inhibition of polyaniline and poly (omethoxyaniline) on stainless steels, Synthetic metals,131, 99-109 (2002)14.Denise S., Azambuja Emilse M.A., Martini and Iduvirges L, Muller, Corrosion behavior of Iron and AISI 304 stainless steel in Tungstate Aqueous solutions containing chloride, J. Braz.Chem.Soc.,14, 570-576 (2003)15.Abdallah M., Corrosion behavior of 304stainless steel in sulphuric acid solutions and its inhibition by some substituted pyrazolones, Materials Chemistry and Physics,82, 786�792 (2003)16.Refaey S.A.M., Taha F and Abd El-Malak A.M., Inhibition of stainless steel pitting corrosion in acidic medium by 2- mercaptobenzoxazole, Applied Surface Sci.,236, 175�185 (2004)17.Celeste Rabacal Alentejano, Idalina Vieira Aoki, Localized corrosion inhibition of 304stainless steel in pure water by oxyanions tungstate and molybdate, Electrochemica Acta.,49, 2779-2785 (2004)18.Meltem Dudukcu, Birgul Yazici, Mehmet Erbil, The effect of indole on the corrosion behaviour of stainless steel, Materials Chemand Phy., 87, 138�141 (2004)19.Behpour M., Ghoreishi. S.M., Mohammadi N. and Salavati- Niasari, MN-[(Z)-1-Phenylemethyleidene]-N{2-[(2-{[(Z)-1phenylmethylidine]amino}phenyl) disulfanyl] phenyl} amine and its derivatives on the corrosion of stainless steel 304 in acid media, J. Corros. Sci.,53, 3380-3387 (2005)20.Galal A., Atta N.F., Al-Hassan M.H.S., Effect of some thiophene derivative on the electrochemical behaviour of AISI 316austenitic stainless steel in acidic solutions containing chloride ions, I. Molecular structure and inhibition efficiency relationship, Materials Chem and Phy., 89, 38-48 (2005)21.Narvaez L., Cano E. and Bastidas D.M., 3-Hydroxybenzoic acid as AISI 316Lstainless steel corrosion inhibitor in a H2SO4-HF-H2O2 pickling solution, J.Applied Electrochemistry,35, 499-506 (2005)
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22.Galal A., Atta N.F. and Al-Hassan M.H.S., Effect of some thiophene derivatives on the electrochemical behavior of AISI 316austenitic stainless steel in acidic solutions containing chloride ions II, Effect of temperature and surface studies, Materials Chem and Phy.,89, 28�37 (2005)23.Sourisseau T., Chauveaub E. and Barouxa B., Mechanism of copper action on pitting phenomena observed on stainless steels in chloride media, J. Corros. Sci.,47, 1097�1117 (2005)24.Refaey S.A.M., Taha F.and Abd El-Malak A.M., Corrosion and inhibition of 316Lstainless steel in neutral medium by 2-Mercaptobenzimidazole, Int. J.Electrochem. Sci.,, 80- 91 (2006)25.Silva A.B., Agostinho S.M.L., Barcia O.E., Cordeiro G.G.O. and E. D�Elia, The effect of cysteine on the corrosion of 304L stainless steel in sulphuric acid, J. Corros. Sci,48, 3668�3674 (2006)26.Gopi D., Manimozhi S., Govindaraju K.M., Manisankar P. and Rajeswari S., Surface and electrochemical characterization of pitting corrosion behaviour of 304stainless steel in ground water media, J. Applied Electrochemistry,37, 439-449 (2007)27.Fouda A.S. and El-Dafrawy H., Inhibitive effect of some pyrimidine derivatives on the cyclic stressed specimens of stainless steel type 304 in acidic media, Int. J. Electro chem. Sci.,, 721-733 (2007)28.Aziz Yagan Nuran Ozcicek Pekmez, Attila Yildiz, Poly (Nethylaniline) coatings on 304stainless steel for corrosion protection in aqueous HCl and NaCl solutions. Electrochemica Acta., 53, 2474-2482 (2008)29.Pardo A., Merino M.C., Coy A.E. and Viejo F., Arrabal R. And Matykina E., Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316stainless steels in HSO, Corros. Sci.,50, 780-794 (2008)30.Satpati A.K and Ravindran. P.V, Electrochemical study of the inhibition of corrosion of stainless steel by 1,2,3- benzotriazole in acidic media, Materials Chem and Phy., 109, 352�359 (2008)31.Pardo. A, Merino. M.C, Coy. A.E, Viejo. F, Arrabal. R and Matykina. E, Pitting corrosion behaviour of austenitic stainless steels: combining effects of Mn and Mo additions, J. Corros. Sci., 50, 1796�1806 (2008)32.Hosseini S.M.A. and Salari M., Corrosion inhibition of stainless steel 302 by 1-methyl-3-pyridine-2-yl-thiourea in acidic media, Indian J. Chemical technology,16, 480-485 (2009)33.Dubey R.S. and Yogesh Potdar, Corrosion inhibition of 304stainless steel in sodium chloride by ciprofloxacin and norfloxacin, Indian J. Chemical technology,16, 334-338 (2009)34.Matjaz Finsgar, Stefan Fassbender, Fabio Nicolini and Ingrid Milosev, Polyethyleneimine as a corrosion inhibitor for ASTM 420Stainless steel in near neutral saline media, J. Corros Sci.,51, 525-533 (2009)35.Behpour M., Ghoreishi S.M., Soltani N. and Salavati- Niasari M., The inhibitive effect of some bis- N,S-bidentate Schiff bases on corrosion behaviour of 304stainless steel in hydrochloric acid solution, J. Corros Sci., 51, 1073�1082 (2009)36.Matjaz Finsgar, Stefan Fassbender, Sabine Hirth and Ingrid Milosev, Electrochemical and XPS study of polyethyleneimines of different molecular sizes as corrosion inhibitors for AISI 430stainless steel in nearneutral chloride media, Materials Chem and Phy.,116, 198�206 (2009)37.Fouda. A.S and Ellithy. A. S, Inhibition effect of 4- phenylthiazole derivatives on corrosion of 304L stainless steel in HCl solution, J. Corros. Sci., 51, 868�875 (2009)38.Hosseini. S.M.A, Azim. A, Sheikhsoaei. I and Salari. M, Corrosion inhibition of 302Stainless steel with schiff base compounds, J. Iran. Chem. Soc., 7, 779-806 (2010)39.Samide A., Ciuciu A. and Negrila C., Surface analysis of inhibitor film formed by Poly(Vinyl Alcohol) on stainless steel in sodium chloride solution, Portugaliae Electrochemica Acta.,28, 385-396 (2010)40.Fouda A.S., Abdallahb M., Al-Ashreya S.M. and Abdel- Fattahb A.A., Some crown ethers as inhibitors for corrosion of stainless steel type 430 in aqueous solutions, Desalination,250, 538�543 (2010)41.Al-Nowaiser F.M., Corrosion Inhibition of Type 430Stainless Steel in HCl Solution by Dipyridinium Salts, J. King Abdulaziz University Sci.,22, 89-100 (2010)42.Azza EI and Sayed EI Shenway, Corrosion inhibition of lysine as basic amino acids on 316L stainless steel in 0.5M H2SO4 solution, J. American Sci., 7, 600-605 (2011)43.Nada F., Atta A.M., Fekry Hamdi and Hassaneem M., Corrosion inhibition, hydrogen evoluation and antibacterial properties of newly synthesized organic inhibitors on 316L stainless steel alloy in acidic medium, International J. Hydrogen energy.,36, 6462-6471 (2011)44.Herle R., Shetty P., Shetty S.D. and Kini U.A., Corrosion inhibition of 304SS in Hydrochloric acid solution by NFurfuryl N'-Phenyl Thiourea, Portugaliae Electrochimica Acta.,29, 69-78 (2011)45.James O.O., Ajanaku K.O., Ogunniran K.O., Ajani O.O. Siyanbola T.O. and John M.O., Adsorption Behaviour of pyrazolo [3, 4-b] pyridine on corrosion of stainless steel in HCl solution, Trends in Applied Sciences Research.,, 910- 917 (2011)
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46.Gonzalez. M.B and Saidman. S.B, Electrodeposition of polypyrrole on 316L stainless steel for corrosion prevention, J. Corros. Sci.,53, 276-282 (2011)47.Davoodi A., Pakshir M., babaiee M. and Ebrahimi G.R., A comparative study of 304L and 316L stainless steel in acidic media, J. Corros. Sci.,53, 399-408 (2011)48.Aysegul Oncul, Kerim Coban, Esma Sezer and Bahire Filiz Senkal, Inhibition of the corrosion of stainless steel by poly-N-vinylimidazole and N-vinylimidazole, Progress in Organic Coatings,71, 167�172 (2011)49.Necla Caliskan and Esvet Akbas, The inhibition effect of some pyrimidine derivatives on austenitic stainless steel in acidic media, Materials Chem and Phy.,126, 983�988 (2011)50.Ramadev Herle, Prakash Shetty, Divakara Shetty. S and Achutha Kini. U, Corrosion Inhibition of Stainless Steel in Hydrochloric Acid by N - (2-mercaptophenyl) -N' phenyl Thiourea, International J. Chemistry and Applications,, 151-158 (2011)51.Diwan Singh Rajan and Shiv Darshan Malik, Surfactants as Corrosion Inhibitors for Stainless Steel in HCl Solution, J. Pure and Applied Science and Technology, 1, 23-35 (2011)52.Hamza M.M., Abd El Rehim S.S and Magdy Ibrahim. A.M., Inhibition effect of hexadecylpyridinium bromide on the corrosion behavior of some austenitic stainless steels in H2SO4solutions, Accepted in Arabian Journal of Chemistry, Article In Press, (2015)  53.Abdel Ghanyl N.A., The Inhibitive Effect of some amino acids on the corrosion behaviour of 316L stainless steel in sulphuric acid Solution, Modern Applied Science, , 19 (2011)54.Nasrin Soltani, Nahid Tavakkoli, Maryam Khayatkashani, Mohammad RezaJalali and Ahmad Mosavizade, Green approach to corrosion inhibition of 304stainless steel in hydrochloric acid solution by the extract of Salvia officinalisleaves, J. Corros. Sci., 62, 122�135 (2012)55.Patric Raymond P., Peter Pascal Regis A., Rajendran S. and Manivannan M., Investigation of Corrosion Inhibition of Stainless steel by Sodium tungstate, Res. J. Chem. Sci.,3(2), 54�58 (2013)56.Sakari A.and Midorikawa H.; Bull. Soc. Japan, 41, 430 (1968); Chem. Abstr., 69, 18985 (1968)57.Abd B.A., El- Maksoud., Int. J. Electrochem. Sci.,, 528-555 (2008)58.Annand R.R., Hurd R.M. and Hackerman N., J. Electrochem. Soc.,112, 1965 (1968)59.Cook E.Z., Hackerman N., J. Phys. Chem.,55, 549 (1951)60.Abd S.A., Maksoud El, Int. J. Electrochem. Sci.,, 528�555 (2008)61.Ebenso E.E., Hailemichael Alemu, Umoren S.A. and Obot I.B., Int. J. Electrochem. Sci.,, 1325 (2008)62.Chitra S., Parameswari K., Vidhya M., Kalishwari M. and Selvaraj A., Int. J. Electrochem. Sci.,, 4593 (2011)63.Ergun U., Yuzer D. and Emregul K.C., Mater. Chem. Phy.,109, 492 (2008) 64.Shealty D.S., Shetly P. and Nayak H.V.S., J. Chilean Chem. Soc.,51, 849 (2006)65.Hemapriya V.*, Parameswari K. and Bharathy G., Rasayan J Chem.,5(4), 468-476 (2012)66.Fouda A.S.*, Abdallah M.and El-Badrawy Z., Afr. J. Pure Appl. Chem.,5(8), 224-236 (2011) 67.Ezhilarasi M.R., Prabha B. and Santhi T., Rasayan J chem., 8(1), 71-83 (2015)
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