Corrosion inhibition performance of thiomalic acid-Zn2+ system for carbon steel in aqueous solution

M. Prabakaran, S. amesh! and ". Periasamy

Department of Chemistry, The Gandhigram Rural Institute, Deemed University, Gandhigram-624 !2, Dindigul, Tamil "adu, I"DI#$ %-mail& drsramesh'(6)yahoo$*om

#bstract
The iron/electrolyte interphase has been studied in the presence of dicarboxylic acid inhibitor with or without bivalent cation like zinc ions. A protective film has been formed on the carbon steel surface in aqueous solution using a synergistic mixture of an environmentally friendly dicarboxylic acid (thiomailc acid and zinc ions. The corrosion inhibition effect of thiomalic acid with zinc ions on carbon steel has been investigated by gravimetric studies and electrochemical techniques. !otentiodynamic polarization studies indicate that the inhibitor system is a mixed inhibitor. "mpedance studies show that a protective film is formed on the metal surface in the presence of the inhibitor formulation. #urface analytical techniques$ viz.$ %ourier transform infrared spectroscopy (%T"& and #canning 'lectron (icroscopy (#'( were used to investigate the nature of protective film formed on the metal surface. A plausible mechanism of corrosion inhibition is proposed.

$ntroduction
Car+on steel is the most ,orld,ide used material for industrial and domesti* appli*ations, +e*ause of its good me*hani*al properties, availa+ility and relatively reasona+le *ost$ In order to redu*e the *orrosion of metals, several te*hni-ues have +een applied$ The use of inhi+itors ,as one of the most pra*ti*al and effi*ient methods for prote*tion against *orrosion%$ %nvironmental restri*tions imposed on heavy metal-+ased *orrosion inhi+itors oriented s*ientifi* resear*hers to,ards the study of non-to.i* and environmentally friendly *orrosion inhi+itors 2$ The *orrosion inhi+itors are e.tremely effe*tive that even in very small *on*entrations they effe*tively redu*e the *orrosion rate&$ /ne of the main trends in inhi+itor resear*h is the study of *orrosion inhi+ition and s*ale resistan*e properties of organi* *ompounds$ Generally, organi* *ompounds having heteroatom /, ", 0 and 1 are found to have +asi*ity and ele*tron density, thus assist in *orrosion inhi+ition '$ Indeed, *ompounds ,ith fun*tional groups *ontaining hetero-atoms ,hi*h *an donate a lone pair of ele*trons are found to +e parti*ularly useful as inhi+itors for *orrosion of metals(-)$ These *ompounds are still *ontinuously investigated as inhi+itors for *orrosion of metals in industry$ The sele*tion *riteria for various inhi+itors in*lude lo, *on*entration, more adheran*e to environment regulations, environmentally friendly and *ost effe*tiveness$ The use of *ar+o.yli* and di*ar+o.yli* a*ids and salts thereof very ,idely used as *orrosion inhi+iting agents has +een the su+2e*t of various ,or3ers *-%+$ The appli*ation of *ar+o.yli* a*id inhi+itors is a ,idely used and ine.pensive ,ay to prote*t the metals from *orrosion$ Car+o.yli* a*id derivatives alone or +oth ,ith other additives *an effe*tively inhi+it the *orrosion of metals$ 4n 25 is used e.tensively as an anodi* inhi+itor for metalli* *orrosion prote*tion %%$ 1ynergism is one of the most important effe*ts in inhi+ition pro*ess and serves as the +asis for most of the modern *orrosion inhi+iting formulations %2$ 1ynergisti* effe*t e.isting among di*ar+o.yli* a*ids and 4n 25 on the inhi+ition of metals *orrosion of metals has already +een studied +y several authors%&, %'$ In this paper, an organi* *ompound namely di*ar+o.yli* a*id ,as investigated as a *orrosion inhi+itor for *ar+on steel$ In the present ,or3, the inhi+itive effe*t ,ith a ne, organi* inhi+itor vi6$, Thiomali* a*id 7T8#9 and 4n 25 ions in *ontrolling the *orrosion of *ar+on steel in neutral a-ueous environment has +een studied +y the gravimetri* studies$ The *orrosion inhi+ition ,as further investigated +y means of potentiodynami* polari6ation and ele*tro*hemi*al impedan*e spe*tros*opy 7%I19$ 1urfa*e analyti*al te*hni-ues, vi6$, :ourier transform infrared spe*tros*opy 7:T-IR9 and 1*anning ele*tron mi*ros*opy 71%89 ,ere used to investigate the nature of prote*tive film formed on the metal surfa*e$ # plausi+le me*hanism of inhi+ition of *orrosion is proposed$ :or all these studies, a-ueous solution of 6! ppm *hloride has +een *hosen as *ontrol +e*ause of the ,ater used in *ooling ,ater systems is generally either deminerali6ed ,ater or unpolluted surfa*e ,ater$

Material and Methods

Material, Thiomali* a*id 7T8#9 o+tained from #lderi*h Chemi*al Company In*$, U1#, ,as used as su*h in the present study$ The mole*ular stru*ture of the T8# is sho,n in -i.. %$ 4in* sulphate 74n1/4$;<2/9, sodium *hloride and other reagents ,ere analyti*al grade *hemi*als$ #ll the solutions ,ere prepared using triple distilled non-deaerated ,ater$

Preparation of specimens, Car+on steel spe*imens 7!$!2-!$! = 1, !$! -!$!> = 0, !$4-!$( = 8n, !$?-!$2 = C and the rest iron9 of dimensions $( *m . ?$( *m . !$2 *m, ,ere polished to a mirror finish ,ith ?@!, 2@!, @!, 4@!, (@!, and 6@! emery polishing papers respe*tively, degreased ,ith a*etone, dried and used for gravimetri* measurements, :T-IR and 1%8 for surfa*e studies$ The dimensions of the spe*imens ,ith ?$! *m . ?$! *m . !$2 *m ,as used for ele*tro*hemi*al studies$ /ra0imetric measurements, The polished spe*imens ,ere ,eighed and immersed in tripli*ate, in ?!! ml *ontrol solution 7*ontaining 6! ppm *hloride in a-ueous solution9 in the a+sen*e and presen*e of inhi+itor formulations of different *on*entrations, for a period of ; days$ Then, the spe*imens ,ere re,eighed after ,ashing and drying$ The ,eights of the spe*imens +efore and after immersion ,ere determined ,ith 8ettler ele*troni* +alan*e #% 24! model ,ith a reada+ility of !$? mg$ #**ura*y in ,eighing up to !$!!!? g and its surfa*e area measurement up to !$? *m2, as re*ommended +y #1T8, ,as follo,ed$ Corrosion rates of *ar+on steel in the a+sen*e and presen*e of various inhi+itor formulations are e.pressed in mdd$ The *orrosion rate ,as *al*ulated a**ording to the follo,ing e-uation

) CR7mdd9 = ?!! #t

7?9

Ahere BA 7mg9 is the ,eight loss, 1 7*m 29 is the surfa*e area and t 7days9 is the immersion period$ Inhi+ition effi*ien*ies 7I%9 of the inhi+itor ,ere *al*ulated +y using the formula

*& ! *&" I% g 7=9 = ?!! *& !

729

,here CR/ is the *orrosion rate in the a+sen*e of inhi+itor and CRI is the *orrosion rate in the presen*e of inhi+itor$ 1lectrochemical studies, %le*tro*hemi*al measurements ,ere *arried out in a *onventional three-ele*trode *ell *onsisting of *ar+on steel ,or3ing ele*trode 7A%9, a platinum *ounter ele*trode 7C%9 and a saturated *alomel ele*trode 71C%9 as referen*e ele*trode, using C< ele*tro*hemi*al ,or3station 78odel "o& C<I ;6!D, manufa*tured +y C< Instruments, #ustin, U1#9 at ! CC$ Defore starting the e.periments, the ,or3ing ele*trodes ,ere immersed in the test solution for ! min until a steady state potential rea*hed$ %I1 measurements ,ere *arried out ,ith a fre-uen*y range of ?!! E<6 to !$? <6 ,ith an a* amplitude of ( mF at /C0$ The impedan*e data ,ere analy6ed using %C-Ga+ soft,are$ :rom the "y-uist plots, the *harge transfer resistan*e 7R*t9, *onstant phase element 7C0%9 and *onstant e.ponent 7n9 ,ere o+tained$ The inhi+ition effi*ien*ies 7I%i9 ,ere *al*ulated using the e-uation$

&Hct &ct I%i 7=9 = ?! & H ct

7 9

,here R*t and RI*t are the *harge transfer resistan*e values in the a+sen*e and presen*e of the inhi+itor$ The potentiodynami* polari6ation *urves ,ere re*orded from *athodi* to anodi* 7/C0 J 2!! mF9 potential ,ith a s*an rate of ? mF@s$ :rom the Tafel polari6ation *urves, the *orrosion *urrent density values 7I *orr9 and *orrosion potential 7%*orr9 ,ere o+tained$ The values of inhi+ition effi*ien*ies 7I% p9 ,ere *al*ulated from I*orr values using the e-uation,

 "cor "Hcor I%0 7=9 = ?! "cor

749 ,here I*orr and II*orr are the *orrosion *urrent densities in *ase of *ontrol and inhi+ited solutions, respe*tively$ Surface e2amination studies, The *ar+on steel spe*imens ,ere immersed in various test solutions for a period of seven days$ Then, they ,ere ta3en out and dried$ The nature of the film formed on the surfa*e of the metal spe*imen ,as analy6ed +y :ourier transform infrared spe*tros*opy 7:TIR9 and 1*anning ele*tron mi*ros*opy 71%89$ -ourier transform infrared spectroscopy, :ourier transform infrared spe*tros*opy 7:TIR9 ,as *arried out ,ith a resolution of 4 *m-? over the range of 4!!!-4!! *m-? ,ave num+er using a K#1C/ 46! 0GU1 1pe*trophotometer$ The spe*tra of pure T8# and the surfa*e film formed on the metal surfa*e ,ere done using EDr pellet method$ Scannin. electron microscopy, 1%8 has +een used to investigate the surfa*e morphology$ The surfa*e features of *ar+on steel ,ere e.amined after e.posure to solution after ; days ,ith and ,ithout inhi+itor$ The 1%8 photographs of the surfa*es of the spe*imens ,ere o+tained using F%G# model ,ith a resolution of $( nm$

esults and discussion

/ra0imetric studies, The results of *orrosion rate and inhi+ition effi*ien*y 7I% =9, o+tained from gravimetri* method at different *on*entrations of inhi+itor for the *orrosion of *ar+on steel immersed in *ontrol solution, in the a+sen*e and presen*e of 4n25, are given in 3able %$ -i.. 2 sho,s the inhi+ition effi*ien*y as a fun*tion of *on*entration of T8#$ The *orrosion rate of *ar+on steel in *ontrol solution ,as a**elerated in the presen*e of T8# alone$ #lso, 6in* ions are found to +e *orrosive$ <o,ever, a *om+ination of T8# and 4n 25 ions e.hi+ited a higher *orrosion inhi+ition *apa*ity$ %ven at lo, *on*entrations of 4n 25 ions su*h as ?!, 2! and (! ppm in *om+ination ,ith T8# at 2(! ppm, an inhi+ition effi*ien*y of L4= ,as o+served$ Interestingly, the *om+ination *ontaining 4n25 ions at (! ppm and T8# at a lo, level su*h as ?(! ppm gave an inhi+ition effi*ien*y of L2=$ Dut, ,ith in*reasing *on*entration of 4n 25 ions from (! ppm to ;( ppm, 3eeping T8# *onstant at ?(! ppm, the ma.imum inhi+ition effi*ien*y ,as a*hieved$ This may +e e.plained as follo,s$ #t lo,er *on*entrations of 4n 25 ions, the T8# is pre*ipitated as T8#-4n 25 *omple. in the +ul3 of the solution$ T8# is not transported to,ards the metal surfa*e$ /nly on in*reasing the *on*entration of 4n 25 ions, the ma.imum inhi+ition effi*ien*y is o+tained$ # synergisti* effe*t is noti*ed +et,een T8# and 4n 25 ions$ Ahen ;( ppm of 4n 25 ions are added to T8#, T8#-4n 25 *omple. is in solu+ili6ed form$ It diffuses from the +ul3 of the solution to the metal surfa*e$ The M:e7III9@:e7II9N T8#-4n25O *omple. is formed$ # thin multi*olored film is o+served on the surfa*e of the inhi+ited metal during the gravimetri* studies$ The ma.imum inhi+ition effi*ien*y o+tained from the a+ove formulation is L;=$ It *an +e interpreted that at lo,er *on*entrations of 4n 25 ions, the 4n25 ions ,ere insuffi*ient to form a prote*tive film ,ith T8# on the metal surfa*e$ 1ffect of p4, The influen*e of p< on *orrosion rate of *ar+on steel in the presen*e of inhi+itor system and the ma.imum inhi+ition effi*ien*y o+tained in the gravimetri* measurements ,ere studied$ The effe*t of p< for the synergisti* formulation *onsisting of T8# 7?(! ppm9 5 4n 25 7;( ppm9, in the p< range of -?? is sho,n -i.. &$ The highest inhi+ition effi*ien*y *ould +e o+tained in the p< range (-;$ Dut, ,hen the p< is de*reased from (- , the inhi+ition effi*ien*y is redu*ed to 26= and on in*reasing p< range from ;-??, the inhi+ition effi*ien*y is redu*ed to >=$ The reasons for de*rease in inhi+ition effi*ien*y in more al3aline and a*idi* environments are e.plained under the me*hanisti* aspe*ts$ 1lectrochemical impedance spectroscopy 51$S6 measurements, %le*tro*hemi*al impedan*e spe*tros*opy is one of the simple and relia+le te*hni-ues for *orrosion measurements$ %I1 te*hni-ues *an provide valua+le 3ineti* parameters for ele*tron transfer rea*tions at the iron@ele*trolyte interfa*e %($ The *orrosion +ehaviour of *ar+on steel in *ontrol solution ,ith and ,ithout inhi+itor ,as also investigated +y %I1 measurements$ The *harge transfer resistan*e 7R*t9, *onstant phase element 7C0%9 and *onstant e.ponent 7n9 o+tained from the "y-uist plots and the

*al*ulated inhi+ition effi*ien*y values 7I% I9 are sho,n in 3able 2$ -i.. ' sho,s the impedan*e +ehaviour of *ar+on steel *orrosion in the form of "y-uist plots$ :rom "y-uist plots in -i.. ', it is found that the o+tained "y-uist plots are not perfe*t semi*ir*les due to fre-uen*y dispersion and this +ehaviour *an +e attri+uted to roughness and inhomogeneities of the ele*trode surfa*e%7, %)$ Ahen there is non-ideal fre-uen*y response, it is *ommon pra*ti*e to use distri+uted *ir*uit elements in an e-uivalent *ir*uit$ The most ,idely employed is the *onstant phase element 7C0%9$ In general, a C0% is used in a model in pla*e of a *apa*itor to *ompensate for inhomogeneity in the system$ Therefore, a *onstant phase element 7C0%9 is used instead of a *apa*itive element to get a more a**urate fit of e.perimental data sets using generally more *ompli*ated e-uivalent *ir*uits %*$ The impenden*e of C0% is defined as Po is the modulus, 2 is the imaginary rootQ is the angular fre-uen*y and n is the surfa*e irregularity $ Depending on the value of e.ponent n, 4 C0% represents a resistan*e ,ith RR P -?Q for nR -?, an indu*tan*e ,ith CRP 2+$ The value range of a real ele*trode of n is often +et,een ! and ?$ The smaller the value of n, the rougher the ele*trode surfa*e and the more serious the *orrosion of the ele*trode2%$ The ele*tri*al e-uivalent *ir*uit model sho,n in -i.. ( ,as used to analy6e the o+tained impedan*e data$ The model *onsists of the solution resistan*e 7R s9, the *harge-transfer resistan*e of the interfa*ial *orrosion rea*tion 7R *t9 and the *onstant phase angle element 7C0%9$ %.*ellent fit ,ith this model ,as o+tained ,ith our e.perimental data$ 1u*h an e-uivalent *ir*uit ,as also dis*ussed +y several resear*hers 22-2' ,ho o+tained similar depressed semi*ir*les ,ith single time *onstant$ In the present study, a small semi*ir*le ,ith an R *t value of L(> S is o+served for the *ontrol alone$ # similar semi*ir*le is also o+tained ,hen ;( ppm of 4n 25 is added to the *ontrol$ Due to 4n 25 ions, R*t is in*reased and C0% value is de*reased ,ith a slight in*rease in the value of n$ Dy the addition of ?(! ppm of T8# to the *ontrol, a single and slightly depressed semi*ir*le ,ith high R *t value is o+tained$ The *apa*itan*e value is de*reased and n value is in*reased$ These o+servations *an +e attri+uted to the presen*e of organi* inhi+itor mole*ules in the dou+le layer and *ontrol of the *orrosion pro*esses to some e.tent$ Ahen, the *om+ination of ?(! ppm of T8# and ;( ppm of 4n25 is *onsidered in the presen*e of the *ontrol, a large depressed semi*ir*le is o+served from high fre-uen*y to lo, fre-uen*y regions in the "y-uist plot, indi*ating that the *harge transfer resistan*e +e*omes dominant in the *orrosion pro*esses due to the presen*e of a prote*tive film on the metal surfa*e$ This result is supported +y the signifi*ant de*rease in C0% and an in*rease in n value$ The semi*ir*le o+tained in the presen*e of T8#@4n 25 represents an R*t value of ?2>(4 S, ,hi*h is greater than that o+served in *ase of the *ontrol$ The C0% value at the metal@solution interfa*e is found to de*rease from (>2 T:*m -2 in the *ase of the *ontrol to ?L> T:*m -2 in the *ase of the +inary inhi+itor formulation$ This is +e*ause of the repla*ement of ,ater mole*ules in the ele*tri*al dou+le layer +y the organi* mole*ules having lo, diele*tri* *onstants 2($ The value of n is *onsidera+ly in*reased to !$>6 in the presen*e of the +inary inhi+itor system, suggesting a de*rease of inhomogeneity of the interfa*e during inhi+ition pro*ess$ These results indi*ated that there is formation of a non-porous and prote*tive film in the presen*e of the +inary inhi+itor formulation$ The inhi+ition effi*ien*y o+tained from impedan*e studies is found to +e L =$ 1everal authors ,ho studied the inhi+itory effe*ts of *orrosion inhi+itors have also reported that there is formation of a thi*3 and less permea+le prote*tive film on the metal surfa*e 27, 2)$ They also *on*luded that the prote*tive film *onsists of *ar+o.ylate-metal *omple.es$ The results also imply the synergisti* a*tion operating +et,een T8# and 4n 25$ This is in agreement ,ith the inferen*es dra,n from gravimetri* studies and polari6ation studies$ Potentiodynamic polari9ation studies, The 0otentiodynami* polari6ation *urves of *ar+on steel ele*trode in *ontrol solution solution at p< ; in the a+sen*e and presen*e of various inhi+itor *om+inations are sho,n in -i.. 7$ Farious Tafel parameters, i$e$, *orrosion potential 7% *orr9, *orrosion *urrent density 7I*orr9, anodi* Tafel slope 7Ua9, *athodi* Tafel slope 7U*9 and the inhi+ition effi*ien*ies 7I% p9 are listed in 3able &$ #n e.amination of 3able & sho,s that the *orrosion potential 7%*orr9 in *ase of the *ontrol is -4>;$62 mF@1C% and the *orresponding *orrosion *urrent density 7I*orr9 is 22$6> T#@*m2$ Ahen of T8# alone ,as added to the *ontrol, the *orrosion potential is shifted to a more anodi* side and its *orrosion *urrent density is redu*ed to ?;$ ! T#@*m 2$ The anodi* Tafel 7U a9 slope for T8# has +een shifted more anodi*ally 7? mF@de*ade9 than the *athodi* Tafel 7U *9 slope 7L mF@de*ade9$ Ahen ;( ppm of 4n25 is added to the *ontrol, the *orrosion potential is shifted to the *athodi* side and the shift in *athodi* Tafel slope is greater$ Contrary to the result o+tained in the *ase of T8#, 4n 25 in*reased the rate of *orrosion as implied +y in*rease in *orrosion *urrent density$ In the presen*e of 4n 25, the in*rease in *orrosion *urrent density leads to an in*rease in *orrosion rate2*$ :rom the polari6ation *urves sho,n in -i.. 7, it is *lear that for the *om+ination of ?(! ppm T8# and ;( ppm 4n 25, the *orrosion potential is shifted to -((6$42 mF@1C% and its *orrosion *urrent density is also redu*ed ,hen *ompared to the *ontrol$ Thus, it is evident that this formulation a*ts as an effe*tive mi.ed type

4C0% = ,o 7 +9 n

769
%8

inhi+itor$ There is a slight shift in *orrosion potential to a more *athodi* side and the shift in *athodi* Tafel slope 7>? mF@de*ade9 is greater than the shift in anodi* Tafel slope 76( mF@de*ade9$ The *orrosion *urrent is signifi*antly de*reased from 22$6> T#@*m2 to ?$4? T#@*m2, *orresponding to an inhi+ition effi*ien*y of L4=$ Thus, the synergisti* mi.ture of ?(! ppm T8# and ;( ppm 4n 25 is proved to +e an effe*tive *orrosion inhi+itor for *ar+on steel$ These results indi*ate that the +inary inhi+itor formulation retards +oth the anodi* dissolution of *ar+on steel and o.ygen redu*tion at *athodi* sites in the *orrosion inhi+ition pro*ess$ 1imilar *ar+o.ylate-+ased formulations ,ere reported to +e mi.ed inhi+itors%+$ # signifi*ant o+servation related to the inhi+ition effi*ien*y values is to +e noted$ If the inhi+ition effi*ien*y values o+tained from gravimetri* 7I% g9, polari6ation 7I%p9, and %I1 7I%i9 studies are *ompared, slight differen*es are o+served$ It is suggested that the inhi+ition effi*ien*y values o+tained from various methods may not +e stri*tly *ompara+le ,hen the immersion times used in these methods are not the same 28$ -3-$ Studies, The :T-IR spe*trum of pure thiomali* a*id is sho,n in -i.. )a$ The CR/ stret*hing fre-uen*y of *ar+o.yl group appears at ?;!!$L? *m-?$ The C-1 stret*hing vi+ration has +een assigned to the region ;!!-6!! *m -l 7?49$ The pea3 that appeared at 6??$ 2 *m-? is assigned to the C-1 group and the other pea3 at 2(64$>6 *m -? is assigned to the 1N< group$ The :TIR spe*trum of the film formed on the metal surfa*e after immersion in *ontrol solution *onsisting of T8# 7?(! ppm9 and 4n 25 7;( ppm9 is sho,n in -i.. )b$ The CR/ stret*hing fre-uen*y has shifted from ?;!!$L? *m-? to ?(6L$;; *m-?$ This indi*ates that the T8# has *oordinated ,ith :e 25 on the metal surfa*e through o.ygen atom of CR/ group resulting in the formation of :e 25-T8# *omple.$ The pea3 at ? L2$ ( *m-? indi*ates the presen*e of 4n7/<92 on the metal surfa*e film&+$ The +road +and of the /< stret*hing and +ending modes of ,ater or hydro.ides ,ithin the prote*tive film appeared at ?>!$!4 *m -?$ There are many ,ea3 +ands in the region +et,een ?,2!! and 4!! *m-?$ The pea3 at 464$;( *m-? implies the presen*e of ferri* and ferrous o.ide and hydro.ide in the prote*tive film &%$ The :TIR spe*tra suggests that the prote*tive film may *onsist of M:e7II9@4n7II9N T8#O, 4n7/<92 and small amounts of o.ides and hydro.ides of iron$ Scannin. electron microscopy, 1%8 analysis ,as *arried out for *hara*teri6ing the inhi+itive film formed on the *ar+on steel surfa*e$ -i.. *a presents the mi*rograph o+tained for the *ar+on steel sample after e.posure to the *orrosive environment, and -i.. *b reveals the surfa*e on the *ar+on steel after e.posure to the *ontrol solution *ontaining the inhi+itor, ?(! ppm T8#, ;( ppm and 4n 25 ions$ The 1%8 pattern of the spe*imen immersed in the a+sen*e of the inhi+itor e.hi+its *orrosion and also the presen*e of different forms of iron o.ides$ $ It further sho,s that the *orrosion produ*ts appear very uneven and the surfa*e layer is too rough$ It is important to stress that ,hen the inhi+itor is present in the solution, the morphology of the *ar+on steel surfa*e are -uite different from the previous one$ 1%8 image of inhi+ited *ar+on steel spe*imen 7 -i.. 7b9 reveals that a good prote*tive adsor+ed film is formed on the *ar+on steel surfa*e, ,hi*h suppresses the rate of *orrosion &2, +eing responsi+le for the inhi+ition$ The film formed is distri+uted in a random ,ay on the ,hole surfa*e of the metal$ This may +e interpreted as due to the adsorption of the inhi+itor on the metal surfa*e in*orporating into the passive film in order to +lo*3 the a*tive sites present on the *ar+on steel surfa*e$ 1o, 1%8 analysis sho,s the prote*tive nature of the surfa*e film 28$ Mechanism of protection, In order to e.plain all the e.perimental results, the follo,ing me*hanism of *orrosion inhi+ition *an +e proposed& Ahen *ar+on steel is immersed in neutral a-ueous environment the anodi* rea*tion is 7;9 :e :e 2 + + 2e 25 :e further undergoes o.idation in the presen*e of o.ygen availa+le in the a-ueous solution M/2O 7>9 :e 2+ :e + + e and the *athodi* rea*tion is& 7L9 /2 + 2< 2 / + 4e 4/< Ahen the environment *ontaining *ontrol solution 76! ppm Cl - ions9@?(! ppm T8#@;( ppm 4n25 ,as prepared, a M4n25-T8#O *omple. ,as formed in the solution$ Desides this *omple., there is presen*e of free T8# and 4n 25 ions$ Ahen the metal ,as immersed in this environment, the M4n 25-T8#O *omple. diffused from the +ul3 of the solution onto the surfa*e of the metal and further *omple.es ,ith :e25@:e 5 ions availa+le due to initial *orrosion$ :ree T8# mole*ule diffuse from +ul3 of the solution to the metal surfa*e and form M:e 25@:e 5-T8#O *omple.es$ These *omple.es fill the pores of the film formed on the surfa*e and ma3e it prote*tive$ :ree 4n25 ions diffuse from the +ul3 of the solution to the metal surfa*e and form 4n7/<9 2 at the lo*al *athodi* sites$

Thus, the *orrosion is *ontrolled +y the prote*tive film *onsisting of 4n7/<9 2 and metal-inhi+itor *omple., vi6$, M:e25@:e 5-T8#O$ :ormation of 4n7/<92 *ontrols the *athodi* rea*tion and formation of 7metal-inhi+itor9 *omple.es *ontrols the anodi* rea*tion$ <en*e, the inhi+ition is under mi.ed *ontrol$ 1imilar reports of *omple. formation have +een o+served in the literature%%, %', 28, &2$

Conclusion
The present ,or3 sho,s an e.*ellent inhi+itive effe*t among T8# and 4n 25 in *orrosion *ontrol of *ar+on steel$ The inhi+itor system ?(! ppm T8# and ;( ppm 4n 25 is effe*tive and has L;= inhi+ition effi*ien*y$ The inhi+itor system is effe*tive in the p< range ( to ;$ The inhi+itor formulation a*ts as a mi.ed inhi+itor predominantly *athodi* in nature$ In presen*e of the inhi+itor, the *harge transfer resistan*e is signifi*antly in*reased and the presen*e of a prote*tive film on the metal surfa*e$ :TIR spe*tral data appear to indi*ate that the prote*tive film may *onsists of M:e 5@:e25@4n25-T8#O *omple., 4n7/<92$, hydro.ides and o.ides of iron$ The prote*tive film formation is also *onfirmed +y 1*anning ele*tron mi*ros*opi* study$ This inhi+itor formulation *onsisting of T8# and 4n 25 *an +e used as a potential inhi+itor to prevent the *orrosion of *ar+on steel in neutral a-ueous environment$

#ckno:led.ement
/ne of the authors 8$ 0ra+a3aran is grateful to the UGC for the fello,ship under Resear*h :ello,ship in 1*ien*es for 8eritorious 1tudents$ #uthors than3 the Co-ordinator, UGC-1#0, Gandhigram Rural Institute for his help and also than3 the authorities of Gandhigram Rural Institute for the en*ouragement$

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?($ 1ayed %l$ and 1herit 8$, %ffe*ts of (-7 -aminophenyl9-tetra6ole on the inhi+ition of unalloyed iron *orrosion in aerated $(= sodium *hloride solutions as a *orrosion inhi+itor, (ater. *hem. !hys$, %28, L6?L6; 52+%%6 ?6$ Kuttner E$, %le*tro*hemi*al impedan*e spe*tros*opy 7%I19 of *orrosion pro*esses on inhomogeneous surfa*es, 'lecrochim. Acta$, &(, ?(!?-?(!> 5%88+6 ?;$ Denali /$ Denmehdi <$ <asnaoui /$ 1elles C$ and 1alghi R$, Green *orrosion inhi+itor& inhi+itive a*tion of tannin e.tra*t of Chamaerops humilis plant for the *orrosion of mild steel in !$( 8 < 21/4, -. (ater. 'nviron. #ci$, ' 5%6, ?2;-? > 52+%&6 ?>$ 8a*donald K$R$ and Kohnson A$D$, "mpedance #pectroscopy$ Kohn Ailey and 1ons, "e, Por3, 5%8*)6 ?L$ Gi G$P$ 8a <$P$ Kiao P$G$ and Chen 1$<$, #n impedan*e investigation of *orrosion prote*tion of *opper +y self-assem+led monolayers of al3anethiols in a-ueous solution, -. #erb. *hem #oc$, 78, ;L?->!( 52++'6 2!$ 8a*donald K$R$, Impedan*e spe*tros*opy and its use in analy6ing the steady-state #C response of solid and li-uid ele*trolytes, -. 'lectroanal. *hem$, 22&, 2(-(! 5%8*)6 2?$ Ehaled E$:$ and <a*3erman "$, /rtho-su+stituted anilines to inhi+it *opper *orrosion in aerated !$( 8 hydro*hlori* a*id, 'lectrochim. Acta$, '8, 4>(-4L( 52++'6 22$ #lagta #$ :elhosi I$ Telegdi K$ Dertoti I$ and Ealman %$, %ffe*t of metal ions on *orrosion inhi+ition of pimeloyl-?,(-di-hydro.ami* a*id for steel in neutral solution, *orros. #ci$, '8, 2;(4-2;66 52++)6 2 $ Gunase3aran G$ and Chauhan G$R$, %*o friendly inhi+itor for *orrosion inhi+ition of mild steel in phosphori* a*id medium, 'lectrochim. Acta$, '8, 4 >;-4 L( 52++'6 24$ %+enso %$%$ Ea+anda 8$8$ 8urulana G$C$ 1ingh #$E$ and 1hu3la 1$E$, %le*tro*hemi*al and -uantum *hemi*al investigation of some a6ine and thia6ine dyes as potential *orrosion inhi+itors for mild steel in hydro*hlori* a*id solution, "nd$ 'ng$ *hem$ &es$, (%, ?2L4!N?2L(> 52+%26 2($ Aang C$T$ Chen 1$<$ 8a <$P$ and Aang "$X$, 1tudy of the sta+ility of self-assem+led "-vinyl*ar+a6ole monolayers to prote*t *opper against *orrosion, -. #erb. *hem.$ #oc$, 7), 6>(-6L6 52++26 26$ Gon6ale6 P$ Gafont 8$C$ 0e+ere "$ and 8oran :$, 1ynergisti* effe*t +et,een 6in* salt and phosphoni* a*id for *orrosion inhi+ition of a *ar+on steel, -. Appl. 'lectrochem$, 27, ?2(L-?26( 5%8876 2;$ 0e*h-Canul 8$#$ and Dartolo-0ere6 0$, Inhi+ition effe*ts of "-phosphono-methyl-gly*ine@4n 25 mi.tures on *orrosion of steel in neutral *hloride solutions, #urf. *oat. Technol$, %*', ? -?4! 52++'6 2>$ Ra2endran 1$ #ppaRao D$F$ and 0alanis,amy "$, Investigation of the inhi+iting effe*t of ethyl phosphoni* a*id -4n25 system, .ull. 'lectrochem$, %), ?;?-?;4 52++%6 2L$ #ppaRao D$F$ Fen3ates,araRao 8$ 1rinivasaRao 1$ and 1reedhar D$, Tungstate as a synergist to phosphonate-+ased formulation for *orrosion *ontrol of *ar+on steel in nearly neutral a-ueous environment, -. *hem. #ci$, %22, 6 L-64L 52+%+6 !$ 1e3ine I$ and <ira3a,a P$, %ffe*t of ?-<ydro.yethylidene-?, ?-Diphosphoni* #*id on the Corrosion of 11 4? 1teel in !$ = 1odium Chloride 1olution, *orrosion$, '2, 2;2-2;; 7?L>69

31. "a3ayama "$, Inhi+itory effe*ts of nitrilotris7methylenephosphoni* a*id9 on *athodi* rea*tions of steels in
saturated Ca7/<92 solutions, *orros. #ci$, '2, ?>L;-?L2! 52+++6 2$ 0ra+a3aran 8$ Fen3atesh 8$ Ramesh 1$ and 0eriasamy F$, Corrosion inhi+ition +ehavior of propyl phosphoni* a*idN4n25 system for *ar+on steel in a-ueous solution, #ppl$ 1urf$ 1*i$, 2;6, (L2-6! 52+%&6

-i.ure-% Molecular structure of thiomalic acid 53M;6

-i.ure-2 $nhibition efficiency as a function of concentration of 3M;

100 90 80 70
2+

60 50 40 30 20

10 ppm Zn 2+ 20 ppm Zn 2+ 50 ppm Zn 2+ 75 ppm Zn 2+ 100 ppm Zn 2+ 125 ppm Zn 2+ 150 ppm Zn

I.E (%)

10 9 8 7 6

50

100

150

200

250

Concentration of TMA (ppm)

I.E (%)

5 4 3 2 1 2 3 4 5

-i.ure-& 1ffect of p4

11

12

p!

-i.ure-' <yquist plots of carbon steel immersed in 0arious test solutions

7,500 7,000 6,500 6,000 5,500 5,000 4,500 ' Im ( # ) $% & m 4,000 3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 5,000 "e ( # ) $%& m 10,000

150 ppm TML + 75 ppm Zinc 150 ppm TML Control solution 75 ppm Zinc

-i.ure-( Potentiodynamic polari9ation cur0es of carbon steel immersed in 0arious test solutions

-1

-1.5

Control solution 75 ppm Zinc 150 ppm TML

-2

* o + ( , I$ m A ,)

-2.5

150 ppm TML + 75 ppm Zinc

-3

-3.5

-4

-4.5

0.3

0.4

0.5 ' E( e $ )

0.6

0.7

-i.ure-7 <yquist plots are fitted by the equi0alent electrical circuit

-i.ure-) -3$ Spectra of 5a6 pure 3M# 5b6 Surface film

-i.ure-* S1M ima.es of carbon steel immersed in 5a6 and 5b6 control solution, 5c6 and 5d6 presence of inhibitor

3able-% $nhibition efficiencies 5=6 obtained by .ra0imetric studies of carbon steel in absence and presence of inhibitor 53M#-Zn2+6 3M# 5ppm6 ?! CR ?! 2( (! ;( ?!! %(+ 2!! 2(! >$>4 >$6> >$( >$2( ;$L( ;$>? 6$;L >$66 I% 4 ( 6 > 4! 4? 4L ( 2! CR ;$>? 6$>L 4$LL $!L ?$>6 ?$44 ?$64 ?$ I% 4? 4> 62 ;; >6 >L >> L! (! CR >$?! 6$L? 4$;! 2$!6 ?$24 ?$! !$> !$>2 I% L 4> 6( >( L? L2 L4 L4 Zn2+ 5ppm6 )( CR >$42 6$2; 2$L? ?$(( !$(2 +.'% !$4? !$(2 ( ;> >> L6 8) L; L6 I% ; ?!! CR 6$>4 ($! $? ?$? !$4? !$4? !$ ? !$4? I% 4L 62 ;6 L? L; L; L> L; ?2( CR L$?> 6$>L 4$LL 2$4; ?$(( ?$! !$;? !$(? I% ? 4> 62 >? >> L2 L( L6 ?(! CR L$26 ($24 $(( ?$(4 ?$24 !$>2 !$;2 !$;2 I% ! 6? ; >> L? L4 L( L(

3able-2 Corrosion parameters of carbon steel immersed in the absence and in the presence of inhibitor obtained by potentiodynamic polari9ation studies Con*entration 7ppm9 T8# 4n25 ?(! ?(! ;( ;( %*orr 7mF@1C%9 -4>;$62 -4;;$2 -(>?$2L -((6$42 I*orr 7T#@*m29 22$6> ?;$ ! 4 $;! ?$4? Tafel parameters Ua U* 7mF@de*ade 7mF@de*ade 9 9 2!L 2?2 ?L6 2! 2 L 2(? 2;; 2L! I$%0 7=9 24 L4

3able-& #.C. impedance parameters of carbon steel immersed in the presence and absence of inhibitor obtained by #.C. impedance spectra Con*entration 7ppm9 Charge Transfer Resistan*e R*t 7S9 L(> ;L! ?24> ?2>(4 Constant phase element C0% 7T:@*m29 Constant e.ponent n !$;> !$>4 !$L2 !$L6

I$% 7=9

T8# ! ! ?(! ?(!

4n25 ! ;( ! ;( (>2 6>2 ;! ?L> 2 L