Research ArticleKinetics and Mechanistic Study of Permanganate Oxidation ofFluorenone Hydrazone in Alkaline Medium

Ahmed Fawzy12 Saleh A Ahmed12 Ismail I Althagafi1

Moataz H Morad1 and Khalid S Khairou1

1Chemistry Department Faculty of Applied Science Umm Al-Qura University Makkah 21955 Saudi Arabia2Chemistry Department Faculty of Science Assiut University Assiut 71516 Egypt

Correspondence should be addressed to Ahmed Fawzy afsaad13yahoocom and Saleh A Ahmed saleh 63hotmailcom

Received 27 April 2016 Revised 9 June 2016 Accepted 19 June 2016

Academic Editor Claudio Fontanesi

Copyright copy 2016 Ahmed Fawzy et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The oxidation kinetics of fluorenone hydrazone (FH) using potassium permanganate in alkaline medium were measured at aconstant ionic strength of 01mol dmminus3 and at 25∘C using UVVIS spectrophotometer A first-order kinetics has been monitoredin the reaction of FH with respect to [permanganate] Less-than-unit order dependence of the reaction on [FH] and [OHminus]was revealed No pronounced effect on the reaction rate by increasing ionic strength was recorded Intervention of free radicalswas observed in the reaction The reaction mechanism describing the kinetic results was illustrated which involves formationof 1 1 intermediate complex between fluorenone hydrazones and the active species of permanganate 9H-Fluorenone as thecorresponding ketone was found to be the final oxidation product of fluorenone hydrazone as confirmed by GCMS analysis andFT-IR spectroscopy The expression rate law for the oxidation reaction was deduced The reaction constants and mechanism havebeen evaluated The activation parameters associated with the rate-limiting step of the reaction along with the thermodynamicquantities of the equilibrium constants have been calculated and discussed

1 Introduction

Fluorene and its derivatives (FLs) are a unique class ofpolycyclic aromatic hydrocarbons (PAHs) which exist in thefossil fuels and petrogenic sources burning of gasoline [1 2]Recently studies on the exhaust emitting of different typesof reformulated diesel fuels showed presence of fluorene asa precedence compound and isomers of methyl fluorene asa hesitant compound in the exhaust [3] The fluorene unitis regularly employed in the growth of an assortment ofvisual devices with latent application as dye-sensitized solarcells [4] polymer light-emitting diodes [5 6] and otherelectroemissive materials [7] In addition fluorene basedsystems possess sole photophysical properties such as highfluorescent quantum yield huge photostability and excellenthole-transporting properties [8 9] Furthermore fluorene isone of the highest plentiful polycyclic aromatic hydrocarbons(PAHs) in the surroundings due to its high volatility Estab-lished to be a neurotoxicant through mouthful of air it was

also recognized as a contributive PAH to food contagionFluorene compounds with intrinsic rigid structures havebeen attracting much consideration as organic functionalmaterials because of their promising physical and chemicalproperties such as glass transition temperatures good solu-bility and their amorphous nature which make them verypromising as amove toward optic electricmaterials [10 11] Inaddition hydrazone derivatives were found to be biologicallyimportant class of compounds [12] Hydrazone derivativeswere found in natural and synthetic products of biologicalinterest [13] Literature studies revealed that hydrazones andthe different substituted derivatives showed a broad spectrumof biological activities Furthermore fluorenone hydrazonesare used as precursors for the synthesis of photochromicdi- and tetrahydroindolizines [14ndash16] and more recently asefficient corrosion inhibitors [17]

Potassium permanganate is extensively used as an oxidiz-ing agent for numerous organic molecules in various media[18ndash24]Theoxidation reactionmechanismsbypermanganate

Hindawi Publishing CorporationAdvances in Physical ChemistryVolume 2016 Article ID 4526578 9 pageshttpdxdoiorg10115520164526578

2 Advances in Physical Chemistry

O

Fluorenone hydrazone 9H-Fluorenone

NmdashNH2

+ 4MnO4minus

+ 4OHminus + 4MnO42minus

+ 3H2O + N2

Figure 1

are governed by pH of themedium [25] Among six oxidationstates of Mn(II) to Mn(VII) permanganate Mn(VII) isfound to be the most powerful oxidation state in both acidand alkaline media By using permanganate as oxidizingagent it is understandable that theMn(VII) in permanganateis reduced to a variety of oxidation states in acidic alkalineand neutral media

To the best of our knowledge there are no reports on thekinetics and mechanism of oxidation of fluorenone hydra-zone This motivates us to investigate the kinetics and mech-anism of oxidation of fluorenone hydrazone with perman-ganate ion in alkaline medium The objectives of the presentstudy aimed to shed more light and establish the most favor-able conditions affecting oxidation of such noteworthy com-pound and to elucidate a plausible oxidation reaction mech-anism

2 Experimental

21 Materials The chemicals used in the current workwere of Aldrich grades Fluorenone hydrazone was preparedaccording to the described procedures with some modifi-cations [26 27] The synthesized fluorenone hydrazone wasconfirmed by both spectroscopic and analytical tools Allsolvents used were of spectroscopic grade and used withoutfurther purification The solvents used were checked for theabsence of absorbing or any fluorescent impurities Potassiumpermanganate fresh solution was prepared and standardizedas reported [28] Sodium hydroxide and sodium perchloratewere used to vary the alkalinity and ionic strength of reactionmedium respectively

22 Kinetic Measurements The kinetic measurements werefollowed under pseudo-first-order conditions where fluo-renone hydrazone substrate (abbreviated by FH) existed ina large excess over that of permanganate Initiation of thereaction was done by mixing the formerly thermostatedsolutions of permanganate and substrate that also containedthe required amounts of NaOH and NaClO

4

The course ofthe reaction was followed up to not less than two half-lives bymonitoring the absorbance of permanganate as a function oftime at its absorption maximum (120582 = 525 nm) whereas theother constituents of the reaction mixture were not absorbedconsiderably at the determined wavelength The meltingpoints of fluorenone derivatives were recorded using Gal-lenkamp melting point apparatus NMR was recorded on

100

mz

80 90 100 110 120 130 140 150 160 170 180

90

102

125

152

180

182

Figure 2 GCMS analysis for detection of the oxidation product9H-fluorenone (mz = 180)

Bruker Avance 400MHz with CDCl3

and CDCl3

as sol-vent with tetramethylsilane (TMS) as the internal referenceChemical shifts were related to that of the solvent GC-Mass spectra were recorded on ShimadzuGCMS-QP1000 EXmass spectrometer at 70 eV The absorption measurementswere done in a temperature-controlled Shimadzu UV-VIS-NIR-3600 double-beam spectrophotometer The reactionstemperature was controlled to plusmn01∘C

First-order plots of ln(absorbance) versus time wererecorded to be straight lines up to at least 80 of the reactioncompletion and the observed first-order rate constants (119896obs)were calculated as the gradients of such plotsOrdinary valuesof at least two independent determinations of the rate con-stants were taken for the analysis The rate constants werereproducible to 2-3 The orders of the reaction with admi-ration to the reactants were calculated from the slopes of thelog 119896obs versus log(concentration) plots by varying the con-centrations of both substrate and alkali in turn while keepingother conditions constant

3 Results and Discussion

31 Stoichiometry and Product Analysis The stoichiometrywas analyzed periodically by both titrimetric and spectropho-tometric techniques at [OHminus] = 001 and 119868 = 01mol dmminus3 at25∘C The results indicate expenditure of four permanganateions for one molecule of fluorenone hydrazone to yield theoxidation products as shown in Figure 1

Figure 1 is in good agreement with the results of productsanalysis as confirmed by the head-space GCMS whichrevealed a molecular ion peak [M+ 100] at 180 relatedto 9H-fluoren-9-one (Figure 2) The mass spectrometryfragmentation pattern for 9H-fluoren-9-one showed the fol-lowing signals mz 18006 (1000) 18106 (142) 18206(11) 15223 (334) 12546 (1019) and 10235 (16)

Advances in Physical Chemistry 3

4000 3500 3000 2500 2000 1500 1000 500 0

0

10

20

30

40

50

60

Tran

smitt

ance

Fluoren-9-oneFluorenone hydrazone

1725NH2

(cmminus1)

Figure 3 FT-IR spectra of fluorenone hydrazone (red line) and theoxidized product 9H-fluorenone (black line)

Further assignment of the oxidation product was done bythe help of FT-IR spectra as represented in Figure 3 for flu-orenone hydrazone and its oxidation product 9H-fluoren-9-oneThe product 9H-fluoren-9-one showed a very strong sig-nal at 1725 cmminus1 corresponding to the (C=O) group with dis-appearance of amino group at signals at 3388 and 3316 cmminus1In addition the fingerprints of the oxidation product aredifferent than before oxidation process

32 Time-Resolved Spectra Time-resolved spectra during theoxidation of fluorenone hydrazone by alkaline permanganateare represented in Figure 4 The main characteristic featuremanifested in the figure is the gradual decay of permanganateband at its absorption maximum (120582 = 525 nm) as a resultof reduction of permanganate by fluorenone hydrazonederivatives

33 Effect of Permanganate Concentration Permanganate ionoxidant was diverse in the concentration range of 10 times 10minus4to 80 times 10minus4mol dmminus3 while the rest of the reactant con-centrations were kept constant Both pH and temperaturewere also kept constant It has been found that plots ofln(absorbance) versus time were linear up to about 80 ofthe reaction achievement Furthermore the increase in theoxidant concentration did not change the oxidation rate aslisted in Table 1 These results prove and confirm the first-order reaction with respect to the oxidant

34 Effect of Fluorenone Hydrazone Concentration Theobse-rved first-order rate constant (119896obs) was measured at diverseconcentrations of the reductant fluorenone hydrazone keep-ing others constant A plot of 119896obs versus [FH] was foundto be linear with a positive intercept on 119896obs axis (Figure 5)confirming less-than-unit order dependence with respect tothe reductant concentration

35 Effect of Alkali Concentration The influence of alkali onthe reaction rate was deliberated at various [OHminus] keeping

300 400 500 60000

02

04

06

08

10

FH

Permanganate

Abso

rban

ce

Wavelength (nm)

Figure 4 Time-resolved spectra during the oxidation of fluorenoneby alkaline permanganate [FH] = 80 times 10minus3 [MnO

4

minus] = 40 times 10minus4[OHminus] = 002 and 119868 = 01mol dmminus3 at 25∘C Scanning time intervalsare 1min

0 2 4 6 8 10 120

10

20

30

40105k

obs

(sminus1)

103 [FH] (mol dmminus3)

293K298K303K

308K313K

Figure 5 Plots of the observed first-order rate constants (119896obs)versus [FH] at different temperatures in the oxidation of fluorenonehydrazone by alkaline permanganate [MnO

4

minus] = 40 times 10minus4[OHminus] = 002 and 119868 = 01mol dmminus3

all other reactant concentrations constant An increase inthe rate constant with increasing alkali concentration wasachieved (Table 1) A plot of log 119896obs versus log[OH

minus

] wasfound to be linear with a slope of 075 (figure not shown) sug-gesting that the reaction order with respect to [OHminus] was lessthan unity

36 Effect of Ionic Strength The effect of the ionic strengthwas studied through varying the concentration of NaClO

4

inthe reaction medium at constant concentrations of perman-ganate fluorenone hydrazone and alkali It was found that

4 Advances in Physical Chemistry

Table 1 Effect of variation of [MnO4

minus] [FH] [OHminus] and 119868 on the observed first-order rate constants (119896obs) in the oxidations of fluorenonehydrazone by alkaline permanganate at 25∘C

104 [MnO4

minus] (mol dmminus3) 103 [FH] (mol dmminus3) 102 [OHminus] (mol dmminus3) 119868 (mol dmminus3) 104 119896obs (sminus1)

10 80 20 01 19820 80 20 01 20230 80 20 01 19240 80 20 01 19660 80 20 01 18380 80 20 01 18940 20 20 01 7340 40 20 01 12040 60 20 01 15840 80 20 01 19640 100 20 01 22840 120 20 01 25640 80 05 01 9840 80 10 01 14240 80 15 01 17440 80 20 01 19640 80 30 01 23640 80 40 01 27340 80 20 01 19640 80 20 02 18940 80 20 03 20740 80 20 04 19240 80 20 05 18940 80 20 06 202Experimental error is plusmn3

variation in ionic strength did not affect the oxidation rate asobserved from the data listed in Table 1

37 Effect of Temperature The oxidation rate was recordedat five different temperatures 293 298 303 308 and 313 Kunder varying the concentrations of fluorenone hydrazoneand alkali at constant ionic strengthThe activationparametersof the rate constant of the slow step (119896

1

) along with thermo-dynamic parameters of the equilibrium constants involved inthe reaction mechanism were evaluated using Arrhenius andEyring equations and were listed in Table 2

38 Polymerization Study To check the existence of freeradicals in the reaction under investigation the reactionsmixtures were mixed with identified quantities of acryloni-trilemonomer and stored for 6 hours under dry nitrogen con-dition On dilution with methanol white precipitates wereformed indicating the participation of free radicals in the oxi-dation reactions The blank experiments which were carriedout with either permanganate or every substrate with acrylo-nitrile did not induce polymerization under the same exper-imental conditions

39 Reaction Mechanism Permanganate ion is found to bea powerful oxidant in aqueous alkaline media and exhibits

some of oxidation states such as Mn(VII) Mn(V) andMn(VI) At pH gt 12 the reduction product of Mn(VII) isstable Mn(VI) and no further reduction is observed [29 30]The formation of a manganate(VI) intermediate was con-firmed by the green color observed as the reactions proceeded[31 32] which undergoes a slow decay to give rise to the finaloxidation products The yellow color persisted after achieve-ment of the oxidation reactions then finally discrete brownMnO2

sol was observed confirming that Mn(V) specieshypomanganate(V) formed and subsequently decomposedto Mn(IV) sol [33]The latter was coagulated by aging to givea colloidal precipitate of Mn(IV)O

2

It was reported [34 35] that permanganate ion in aqueous

alkaline media combines with alkali to produce an alkali-permanganate species [MnO

4

sdotOH]2minus in a preequilibriumstep as shown in Scheme 1 This is consistent with the appar-ent order of less than unity with respect to the alkali Theformation of [MnO

4

sdotOH]2minus in the present systems is furthersupported by the plots of 1119896obs versus 1[OH

minus] shown inFigure 7 which are linear with nonzero intercepts

Many investigators [18ndash24] have suggested that most ofthe permanganate ion oxidation reactions in neutral andalkaline media proceed through intermediate complexes for-mation between the oxidant and substrates The kineticevidence for such complex was established by the linearity ofthe plots between 1119896obs and 1[FH] Figure 6 in favor of

Advances in Physical Chemistry 5

Table 2 Values of 1198961

1198701

and 1198702

(at different temperatures)activation parameters associated with the slow step (119896

1

) and ther-modynamic parameters of the equilibrium constants (119870

1

and 1198702

)in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 [OHminus] = 002 and 119868 =01mol dmminus3

(a) Values of 1198961

1198701

and1198702

(at different temperatures)

Constant Temperature (K)293 298 303 308 313

104 1198961

(dm3molminus1 sminus1) 371 450 539 641 7411198701

(dm3molminus1) 1562 1748 2011 2474 290810minus2 119870

2

(dm3molminus1) 473 416 361 323 306

(b) Activation parameters associated with the slow step (1198961

)

Δ119878= Jmolminus1 Kminus1 Δ119867 = kJmolminus1 Δ119866 =

298

kJmolminus1 119864 =119886

kJmolminus1

minus10302 plusmn 41 2652 plusmn 12 5722 plusmn 04 2706 plusmn 13

(c) Thermodynamic parameters associated with the equilibrium constants(1198701

and1198702

)

Equilibriumconstant Δ119867

0 kJmolminus1 Δ1198660298

kJmolminus1 Δ1198780 Jmolminus1 Kminus1

1198701

2428 minus708 105251198702

minus1718 minus1494 minus751

0 100 200 300 400 5000

50

100

150

200

1[FH] (dm3 molminus1)

10minus2(1k

obs)

(s)

293K298K303K

308K313K

Figure 6 Plots of 1119896obs versus 1[FH] at different temperaturesin the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [OHminus] = 002 and 119868 = 01mol dmminus3

possible formation of a transient complex flanked by oxidantand substrate comparable with the well-known Michaelis-Menten mechanism [36] for enzyme-substrate reactionsTheobserved insignificant effect of ionic strength on the reactionrate implies the association of an ion and a neutral molecule

0 50 100 150 2000

40

80

120

160

293K298K303K

308K313K

10minus2(1k

obs)

(s)

1[OHminus] (dm3 molminus1)

Figure 7 Plots of 1119896obs versus 1[OHminus] at different temperatures

in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 and 119868 = 01mol dmminus3

[37] that is between neutral fluorenone hydrazone and neg-ative alkali-permanganate species

In view of the above arguments the reaction mechanismshown in Scheme 1 may be suggested This involves attackof the active species of permanganate [MnO

4

sdotOH]2minus on thefluorenone hydrazone substrate leading to the formation ofa complex (C) in a preequilibrium step In this complex oneelectron is transferred from the substrate to permanganateUnder slow cleavage of the complex the formation of afree radical intermediate derived from the substrate andmanganate(VI) transient species has been monitored Theintermediate radical is rapidly attacked by another alkali-permanganate species to yield the corresponding diazoderiv-ative which on further oxidation by two moles of perman-ganate species gives the corresponding ketone (fluorenone)as the final oxidation product

The relationship between reaction rate and substrate (FH)hydroxyl ion and oxidant concentrations can be deduced (seeAppendix) to give the following equation

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (1)

The rate law under pseudo-first-order condition can be exp-ressed by

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (2)

6 Advances in Physical Chemistry

(C)

Slow

Fast

(FH)

+

Fast

O

H

MnO4minus+ OHminus

K1[MnO4middotOH]2minus

[MnO4middotOH]2minus

2minus

[MnO4middotOH]2minus

NmdashNH2

K2

NmdashNmdashOMnO3

+ H2O

k1

H2O +

MnO42minus +

N+ Nminus NmdashNH∙

+ MnO42minus

2[MnO4middotOH]2minus

+ 2MnO42minus

+ H2O + N2

Scheme 1 Mechanism of oxidation of fluorenone hydrazone by alkaline permanganate

Comparing (1) and (2) andwith rearrangement we obtain thefollowing equations

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(3)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(4)

According to (3) and (4) with other conditions being con-stant plots of 1119896obs versus 1[FH] at constant [OHminus] and1119896obs versus 1[OH

minus] at constant [FH] should be linear withpositive intercepts on 1119896obs axes and are certainly found tobe so as shown in Figures 6 and 7 respectively The slopesand intercepts of such plots lead to calculation of values of1198961

1198701

and1198702

(at different temperatures) as listed in Table 2The obtained values of119870

1

are in a good agreement with those

reported in the literature [18ndash20] Also the activation para-meters of 119896

1

alongwith thermodynamic parameters of1198701

and1198702

were calculated and were listed also in Table 2It has been previously reported [38] that the entropy of

activation tends to be more negative for reactions of inner-sphere nature whereas the reactions of positive Δ119878 = valuesproceed via outer-sphere mechanism The obtained largenegative values of entropy of activation (Table 2) suggest thatone-electron transfer of inner-sphere nature is themore plau-sible mechanism for the current oxidation reaction On theother hand positive values of both Δ119867 = and Δ119866 = specifythat the formation of the complex is endothermic and non-spontaneous respectively

4 Conclusions

The kinetics of oxidation of fluorenone hydrazone by alkalinepermanganate has been studied The oxidation product offluorenone hydrazone was identified by GCMS and FT-IRanalyses as the corresponding ketone (9H-fluorenone) The

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

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Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

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Journal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

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CatalystsJournal of

2 Advances in Physical Chemistry

O

Fluorenone hydrazone 9H-Fluorenone

NmdashNH2

+ 4MnO4minus

+ 4OHminus + 4MnO42minus

+ 3H2O + N2

Figure 1

are governed by pH of themedium [25] Among six oxidationstates of Mn(II) to Mn(VII) permanganate Mn(VII) isfound to be the most powerful oxidation state in both acidand alkaline media By using permanganate as oxidizingagent it is understandable that theMn(VII) in permanganateis reduced to a variety of oxidation states in acidic alkalineand neutral media

To the best of our knowledge there are no reports on thekinetics and mechanism of oxidation of fluorenone hydra-zone This motivates us to investigate the kinetics and mech-anism of oxidation of fluorenone hydrazone with perman-ganate ion in alkaline medium The objectives of the presentstudy aimed to shed more light and establish the most favor-able conditions affecting oxidation of such noteworthy com-pound and to elucidate a plausible oxidation reaction mech-anism

2 Experimental

21 Materials The chemicals used in the current workwere of Aldrich grades Fluorenone hydrazone was preparedaccording to the described procedures with some modifi-cations [26 27] The synthesized fluorenone hydrazone wasconfirmed by both spectroscopic and analytical tools Allsolvents used were of spectroscopic grade and used withoutfurther purification The solvents used were checked for theabsence of absorbing or any fluorescent impurities Potassiumpermanganate fresh solution was prepared and standardizedas reported [28] Sodium hydroxide and sodium perchloratewere used to vary the alkalinity and ionic strength of reactionmedium respectively

22 Kinetic Measurements The kinetic measurements werefollowed under pseudo-first-order conditions where fluo-renone hydrazone substrate (abbreviated by FH) existed ina large excess over that of permanganate Initiation of thereaction was done by mixing the formerly thermostatedsolutions of permanganate and substrate that also containedthe required amounts of NaOH and NaClO

4

The course ofthe reaction was followed up to not less than two half-lives bymonitoring the absorbance of permanganate as a function oftime at its absorption maximum (120582 = 525 nm) whereas theother constituents of the reaction mixture were not absorbedconsiderably at the determined wavelength The meltingpoints of fluorenone derivatives were recorded using Gal-lenkamp melting point apparatus NMR was recorded on

100

mz

80 90 100 110 120 130 140 150 160 170 180

90

102

125

152

180

182

Figure 2 GCMS analysis for detection of the oxidation product9H-fluorenone (mz = 180)

Bruker Avance 400MHz with CDCl3

and CDCl3

as sol-vent with tetramethylsilane (TMS) as the internal referenceChemical shifts were related to that of the solvent GC-Mass spectra were recorded on ShimadzuGCMS-QP1000 EXmass spectrometer at 70 eV The absorption measurementswere done in a temperature-controlled Shimadzu UV-VIS-NIR-3600 double-beam spectrophotometer The reactionstemperature was controlled to plusmn01∘C

First-order plots of ln(absorbance) versus time wererecorded to be straight lines up to at least 80 of the reactioncompletion and the observed first-order rate constants (119896obs)were calculated as the gradients of such plotsOrdinary valuesof at least two independent determinations of the rate con-stants were taken for the analysis The rate constants werereproducible to 2-3 The orders of the reaction with admi-ration to the reactants were calculated from the slopes of thelog 119896obs versus log(concentration) plots by varying the con-centrations of both substrate and alkali in turn while keepingother conditions constant

3 Results and Discussion

31 Stoichiometry and Product Analysis The stoichiometrywas analyzed periodically by both titrimetric and spectropho-tometric techniques at [OHminus] = 001 and 119868 = 01mol dmminus3 at25∘C The results indicate expenditure of four permanganateions for one molecule of fluorenone hydrazone to yield theoxidation products as shown in Figure 1

Figure 1 is in good agreement with the results of productsanalysis as confirmed by the head-space GCMS whichrevealed a molecular ion peak [M+ 100] at 180 relatedto 9H-fluoren-9-one (Figure 2) The mass spectrometryfragmentation pattern for 9H-fluoren-9-one showed the fol-lowing signals mz 18006 (1000) 18106 (142) 18206(11) 15223 (334) 12546 (1019) and 10235 (16)

Advances in Physical Chemistry 3

4000 3500 3000 2500 2000 1500 1000 500 0

0

10

20

30

40

50

60

Tran

smitt

ance

Fluoren-9-oneFluorenone hydrazone

1725NH2

(cmminus1)

Figure 3 FT-IR spectra of fluorenone hydrazone (red line) and theoxidized product 9H-fluorenone (black line)

Further assignment of the oxidation product was done bythe help of FT-IR spectra as represented in Figure 3 for flu-orenone hydrazone and its oxidation product 9H-fluoren-9-oneThe product 9H-fluoren-9-one showed a very strong sig-nal at 1725 cmminus1 corresponding to the (C=O) group with dis-appearance of amino group at signals at 3388 and 3316 cmminus1In addition the fingerprints of the oxidation product aredifferent than before oxidation process

32 Time-Resolved Spectra Time-resolved spectra during theoxidation of fluorenone hydrazone by alkaline permanganateare represented in Figure 4 The main characteristic featuremanifested in the figure is the gradual decay of permanganateband at its absorption maximum (120582 = 525 nm) as a resultof reduction of permanganate by fluorenone hydrazonederivatives

33 Effect of Permanganate Concentration Permanganate ionoxidant was diverse in the concentration range of 10 times 10minus4to 80 times 10minus4mol dmminus3 while the rest of the reactant con-centrations were kept constant Both pH and temperaturewere also kept constant It has been found that plots ofln(absorbance) versus time were linear up to about 80 ofthe reaction achievement Furthermore the increase in theoxidant concentration did not change the oxidation rate aslisted in Table 1 These results prove and confirm the first-order reaction with respect to the oxidant

34 Effect of Fluorenone Hydrazone Concentration Theobse-rved first-order rate constant (119896obs) was measured at diverseconcentrations of the reductant fluorenone hydrazone keep-ing others constant A plot of 119896obs versus [FH] was foundto be linear with a positive intercept on 119896obs axis (Figure 5)confirming less-than-unit order dependence with respect tothe reductant concentration

35 Effect of Alkali Concentration The influence of alkali onthe reaction rate was deliberated at various [OHminus] keeping

300 400 500 60000

02

04

06

08

10

FH

Permanganate

Abso

rban

ce

Wavelength (nm)

Figure 4 Time-resolved spectra during the oxidation of fluorenoneby alkaline permanganate [FH] = 80 times 10minus3 [MnO

4

minus] = 40 times 10minus4[OHminus] = 002 and 119868 = 01mol dmminus3 at 25∘C Scanning time intervalsare 1min

0 2 4 6 8 10 120

10

20

30

40105k

obs

(sminus1)

103 [FH] (mol dmminus3)

293K298K303K

308K313K

Figure 5 Plots of the observed first-order rate constants (119896obs)versus [FH] at different temperatures in the oxidation of fluorenonehydrazone by alkaline permanganate [MnO

4

minus] = 40 times 10minus4[OHminus] = 002 and 119868 = 01mol dmminus3

all other reactant concentrations constant An increase inthe rate constant with increasing alkali concentration wasachieved (Table 1) A plot of log 119896obs versus log[OH

minus

] wasfound to be linear with a slope of 075 (figure not shown) sug-gesting that the reaction order with respect to [OHminus] was lessthan unity

36 Effect of Ionic Strength The effect of the ionic strengthwas studied through varying the concentration of NaClO

4

inthe reaction medium at constant concentrations of perman-ganate fluorenone hydrazone and alkali It was found that

4 Advances in Physical Chemistry

Table 1 Effect of variation of [MnO4

minus] [FH] [OHminus] and 119868 on the observed first-order rate constants (119896obs) in the oxidations of fluorenonehydrazone by alkaline permanganate at 25∘C

104 [MnO4

minus] (mol dmminus3) 103 [FH] (mol dmminus3) 102 [OHminus] (mol dmminus3) 119868 (mol dmminus3) 104 119896obs (sminus1)

10 80 20 01 19820 80 20 01 20230 80 20 01 19240 80 20 01 19660 80 20 01 18380 80 20 01 18940 20 20 01 7340 40 20 01 12040 60 20 01 15840 80 20 01 19640 100 20 01 22840 120 20 01 25640 80 05 01 9840 80 10 01 14240 80 15 01 17440 80 20 01 19640 80 30 01 23640 80 40 01 27340 80 20 01 19640 80 20 02 18940 80 20 03 20740 80 20 04 19240 80 20 05 18940 80 20 06 202Experimental error is plusmn3

variation in ionic strength did not affect the oxidation rate asobserved from the data listed in Table 1

37 Effect of Temperature The oxidation rate was recordedat five different temperatures 293 298 303 308 and 313 Kunder varying the concentrations of fluorenone hydrazoneand alkali at constant ionic strengthThe activationparametersof the rate constant of the slow step (119896

1

) along with thermo-dynamic parameters of the equilibrium constants involved inthe reaction mechanism were evaluated using Arrhenius andEyring equations and were listed in Table 2

38 Polymerization Study To check the existence of freeradicals in the reaction under investigation the reactionsmixtures were mixed with identified quantities of acryloni-trilemonomer and stored for 6 hours under dry nitrogen con-dition On dilution with methanol white precipitates wereformed indicating the participation of free radicals in the oxi-dation reactions The blank experiments which were carriedout with either permanganate or every substrate with acrylo-nitrile did not induce polymerization under the same exper-imental conditions

39 Reaction Mechanism Permanganate ion is found to bea powerful oxidant in aqueous alkaline media and exhibits

some of oxidation states such as Mn(VII) Mn(V) andMn(VI) At pH gt 12 the reduction product of Mn(VII) isstable Mn(VI) and no further reduction is observed [29 30]The formation of a manganate(VI) intermediate was con-firmed by the green color observed as the reactions proceeded[31 32] which undergoes a slow decay to give rise to the finaloxidation products The yellow color persisted after achieve-ment of the oxidation reactions then finally discrete brownMnO2

sol was observed confirming that Mn(V) specieshypomanganate(V) formed and subsequently decomposedto Mn(IV) sol [33]The latter was coagulated by aging to givea colloidal precipitate of Mn(IV)O

2

It was reported [34 35] that permanganate ion in aqueous

alkaline media combines with alkali to produce an alkali-permanganate species [MnO

4

sdotOH]2minus in a preequilibriumstep as shown in Scheme 1 This is consistent with the appar-ent order of less than unity with respect to the alkali Theformation of [MnO

4

sdotOH]2minus in the present systems is furthersupported by the plots of 1119896obs versus 1[OH

minus] shown inFigure 7 which are linear with nonzero intercepts

Many investigators [18ndash24] have suggested that most ofthe permanganate ion oxidation reactions in neutral andalkaline media proceed through intermediate complexes for-mation between the oxidant and substrates The kineticevidence for such complex was established by the linearity ofthe plots between 1119896obs and 1[FH] Figure 6 in favor of

Advances in Physical Chemistry 5

Table 2 Values of 1198961

1198701

and 1198702

(at different temperatures)activation parameters associated with the slow step (119896

1

) and ther-modynamic parameters of the equilibrium constants (119870

1

and 1198702

)in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 [OHminus] = 002 and 119868 =01mol dmminus3

(a) Values of 1198961

1198701

and1198702

(at different temperatures)

Constant Temperature (K)293 298 303 308 313

104 1198961

(dm3molminus1 sminus1) 371 450 539 641 7411198701

(dm3molminus1) 1562 1748 2011 2474 290810minus2 119870

2

(dm3molminus1) 473 416 361 323 306

(b) Activation parameters associated with the slow step (1198961

)

Δ119878= Jmolminus1 Kminus1 Δ119867 = kJmolminus1 Δ119866 =

298

kJmolminus1 119864 =119886

kJmolminus1

minus10302 plusmn 41 2652 plusmn 12 5722 plusmn 04 2706 plusmn 13

(c) Thermodynamic parameters associated with the equilibrium constants(1198701

and1198702

)

Equilibriumconstant Δ119867

0 kJmolminus1 Δ1198660298

kJmolminus1 Δ1198780 Jmolminus1 Kminus1

1198701

2428 minus708 105251198702

minus1718 minus1494 minus751

0 100 200 300 400 5000

50

100

150

200

1[FH] (dm3 molminus1)

10minus2(1k

obs)

(s)

293K298K303K

308K313K

Figure 6 Plots of 1119896obs versus 1[FH] at different temperaturesin the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [OHminus] = 002 and 119868 = 01mol dmminus3

possible formation of a transient complex flanked by oxidantand substrate comparable with the well-known Michaelis-Menten mechanism [36] for enzyme-substrate reactionsTheobserved insignificant effect of ionic strength on the reactionrate implies the association of an ion and a neutral molecule

0 50 100 150 2000

40

80

120

160

293K298K303K

308K313K

10minus2(1k

obs)

(s)

1[OHminus] (dm3 molminus1)

Figure 7 Plots of 1119896obs versus 1[OHminus] at different temperatures

in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 and 119868 = 01mol dmminus3

[37] that is between neutral fluorenone hydrazone and neg-ative alkali-permanganate species

In view of the above arguments the reaction mechanismshown in Scheme 1 may be suggested This involves attackof the active species of permanganate [MnO

4

sdotOH]2minus on thefluorenone hydrazone substrate leading to the formation ofa complex (C) in a preequilibrium step In this complex oneelectron is transferred from the substrate to permanganateUnder slow cleavage of the complex the formation of afree radical intermediate derived from the substrate andmanganate(VI) transient species has been monitored Theintermediate radical is rapidly attacked by another alkali-permanganate species to yield the corresponding diazoderiv-ative which on further oxidation by two moles of perman-ganate species gives the corresponding ketone (fluorenone)as the final oxidation product

The relationship between reaction rate and substrate (FH)hydroxyl ion and oxidant concentrations can be deduced (seeAppendix) to give the following equation

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (1)

The rate law under pseudo-first-order condition can be exp-ressed by

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (2)

6 Advances in Physical Chemistry

(C)

Slow

Fast

(FH)

+

Fast

O

H

MnO4minus+ OHminus

K1[MnO4middotOH]2minus

[MnO4middotOH]2minus

2minus

[MnO4middotOH]2minus

NmdashNH2

K2

NmdashNmdashOMnO3

+ H2O

k1

H2O +

MnO42minus +

N+ Nminus NmdashNH∙

+ MnO42minus

2[MnO4middotOH]2minus

+ 2MnO42minus

+ H2O + N2

Scheme 1 Mechanism of oxidation of fluorenone hydrazone by alkaline permanganate

Comparing (1) and (2) andwith rearrangement we obtain thefollowing equations

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(3)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(4)

According to (3) and (4) with other conditions being con-stant plots of 1119896obs versus 1[FH] at constant [OHminus] and1119896obs versus 1[OH

minus] at constant [FH] should be linear withpositive intercepts on 1119896obs axes and are certainly found tobe so as shown in Figures 6 and 7 respectively The slopesand intercepts of such plots lead to calculation of values of1198961

1198701

and1198702

(at different temperatures) as listed in Table 2The obtained values of119870

1

are in a good agreement with those

reported in the literature [18ndash20] Also the activation para-meters of 119896

1

alongwith thermodynamic parameters of1198701

and1198702

were calculated and were listed also in Table 2It has been previously reported [38] that the entropy of

activation tends to be more negative for reactions of inner-sphere nature whereas the reactions of positive Δ119878 = valuesproceed via outer-sphere mechanism The obtained largenegative values of entropy of activation (Table 2) suggest thatone-electron transfer of inner-sphere nature is themore plau-sible mechanism for the current oxidation reaction On theother hand positive values of both Δ119867 = and Δ119866 = specifythat the formation of the complex is endothermic and non-spontaneous respectively

4 Conclusions

The kinetics of oxidation of fluorenone hydrazone by alkalinepermanganate has been studied The oxidation product offluorenone hydrazone was identified by GCMS and FT-IRanalyses as the corresponding ketone (9H-fluorenone) The

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Advances in Physical Chemistry 3

4000 3500 3000 2500 2000 1500 1000 500 0

0

10

20

30

40

50

60

Tran

smitt

ance

Fluoren-9-oneFluorenone hydrazone

1725NH2

(cmminus1)

Figure 3 FT-IR spectra of fluorenone hydrazone (red line) and theoxidized product 9H-fluorenone (black line)

Further assignment of the oxidation product was done bythe help of FT-IR spectra as represented in Figure 3 for flu-orenone hydrazone and its oxidation product 9H-fluoren-9-oneThe product 9H-fluoren-9-one showed a very strong sig-nal at 1725 cmminus1 corresponding to the (C=O) group with dis-appearance of amino group at signals at 3388 and 3316 cmminus1In addition the fingerprints of the oxidation product aredifferent than before oxidation process

32 Time-Resolved Spectra Time-resolved spectra during theoxidation of fluorenone hydrazone by alkaline permanganateare represented in Figure 4 The main characteristic featuremanifested in the figure is the gradual decay of permanganateband at its absorption maximum (120582 = 525 nm) as a resultof reduction of permanganate by fluorenone hydrazonederivatives

33 Effect of Permanganate Concentration Permanganate ionoxidant was diverse in the concentration range of 10 times 10minus4to 80 times 10minus4mol dmminus3 while the rest of the reactant con-centrations were kept constant Both pH and temperaturewere also kept constant It has been found that plots ofln(absorbance) versus time were linear up to about 80 ofthe reaction achievement Furthermore the increase in theoxidant concentration did not change the oxidation rate aslisted in Table 1 These results prove and confirm the first-order reaction with respect to the oxidant

34 Effect of Fluorenone Hydrazone Concentration Theobse-rved first-order rate constant (119896obs) was measured at diverseconcentrations of the reductant fluorenone hydrazone keep-ing others constant A plot of 119896obs versus [FH] was foundto be linear with a positive intercept on 119896obs axis (Figure 5)confirming less-than-unit order dependence with respect tothe reductant concentration

35 Effect of Alkali Concentration The influence of alkali onthe reaction rate was deliberated at various [OHminus] keeping

300 400 500 60000

02

04

06

08

10

FH

Permanganate

Abso

rban

ce

Wavelength (nm)

Figure 4 Time-resolved spectra during the oxidation of fluorenoneby alkaline permanganate [FH] = 80 times 10minus3 [MnO

4

minus] = 40 times 10minus4[OHminus] = 002 and 119868 = 01mol dmminus3 at 25∘C Scanning time intervalsare 1min

0 2 4 6 8 10 120

10

20

30

40105k

obs

(sminus1)

103 [FH] (mol dmminus3)

293K298K303K

308K313K

Figure 5 Plots of the observed first-order rate constants (119896obs)versus [FH] at different temperatures in the oxidation of fluorenonehydrazone by alkaline permanganate [MnO

4

minus] = 40 times 10minus4[OHminus] = 002 and 119868 = 01mol dmminus3

all other reactant concentrations constant An increase inthe rate constant with increasing alkali concentration wasachieved (Table 1) A plot of log 119896obs versus log[OH

minus

] wasfound to be linear with a slope of 075 (figure not shown) sug-gesting that the reaction order with respect to [OHminus] was lessthan unity

36 Effect of Ionic Strength The effect of the ionic strengthwas studied through varying the concentration of NaClO

4

inthe reaction medium at constant concentrations of perman-ganate fluorenone hydrazone and alkali It was found that

4 Advances in Physical Chemistry

Table 1 Effect of variation of [MnO4

minus] [FH] [OHminus] and 119868 on the observed first-order rate constants (119896obs) in the oxidations of fluorenonehydrazone by alkaline permanganate at 25∘C

104 [MnO4

minus] (mol dmminus3) 103 [FH] (mol dmminus3) 102 [OHminus] (mol dmminus3) 119868 (mol dmminus3) 104 119896obs (sminus1)

10 80 20 01 19820 80 20 01 20230 80 20 01 19240 80 20 01 19660 80 20 01 18380 80 20 01 18940 20 20 01 7340 40 20 01 12040 60 20 01 15840 80 20 01 19640 100 20 01 22840 120 20 01 25640 80 05 01 9840 80 10 01 14240 80 15 01 17440 80 20 01 19640 80 30 01 23640 80 40 01 27340 80 20 01 19640 80 20 02 18940 80 20 03 20740 80 20 04 19240 80 20 05 18940 80 20 06 202Experimental error is plusmn3

variation in ionic strength did not affect the oxidation rate asobserved from the data listed in Table 1

37 Effect of Temperature The oxidation rate was recordedat five different temperatures 293 298 303 308 and 313 Kunder varying the concentrations of fluorenone hydrazoneand alkali at constant ionic strengthThe activationparametersof the rate constant of the slow step (119896

1

) along with thermo-dynamic parameters of the equilibrium constants involved inthe reaction mechanism were evaluated using Arrhenius andEyring equations and were listed in Table 2

38 Polymerization Study To check the existence of freeradicals in the reaction under investigation the reactionsmixtures were mixed with identified quantities of acryloni-trilemonomer and stored for 6 hours under dry nitrogen con-dition On dilution with methanol white precipitates wereformed indicating the participation of free radicals in the oxi-dation reactions The blank experiments which were carriedout with either permanganate or every substrate with acrylo-nitrile did not induce polymerization under the same exper-imental conditions

39 Reaction Mechanism Permanganate ion is found to bea powerful oxidant in aqueous alkaline media and exhibits

some of oxidation states such as Mn(VII) Mn(V) andMn(VI) At pH gt 12 the reduction product of Mn(VII) isstable Mn(VI) and no further reduction is observed [29 30]The formation of a manganate(VI) intermediate was con-firmed by the green color observed as the reactions proceeded[31 32] which undergoes a slow decay to give rise to the finaloxidation products The yellow color persisted after achieve-ment of the oxidation reactions then finally discrete brownMnO2

sol was observed confirming that Mn(V) specieshypomanganate(V) formed and subsequently decomposedto Mn(IV) sol [33]The latter was coagulated by aging to givea colloidal precipitate of Mn(IV)O

2

It was reported [34 35] that permanganate ion in aqueous

alkaline media combines with alkali to produce an alkali-permanganate species [MnO

4

sdotOH]2minus in a preequilibriumstep as shown in Scheme 1 This is consistent with the appar-ent order of less than unity with respect to the alkali Theformation of [MnO

4

sdotOH]2minus in the present systems is furthersupported by the plots of 1119896obs versus 1[OH

minus] shown inFigure 7 which are linear with nonzero intercepts

Many investigators [18ndash24] have suggested that most ofthe permanganate ion oxidation reactions in neutral andalkaline media proceed through intermediate complexes for-mation between the oxidant and substrates The kineticevidence for such complex was established by the linearity ofthe plots between 1119896obs and 1[FH] Figure 6 in favor of

Advances in Physical Chemistry 5

Table 2 Values of 1198961

1198701

and 1198702

(at different temperatures)activation parameters associated with the slow step (119896

1

) and ther-modynamic parameters of the equilibrium constants (119870

1

and 1198702

)in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 [OHminus] = 002 and 119868 =01mol dmminus3

(a) Values of 1198961

1198701

and1198702

(at different temperatures)

Constant Temperature (K)293 298 303 308 313

104 1198961

(dm3molminus1 sminus1) 371 450 539 641 7411198701

(dm3molminus1) 1562 1748 2011 2474 290810minus2 119870

2

(dm3molminus1) 473 416 361 323 306

(b) Activation parameters associated with the slow step (1198961

)

Δ119878= Jmolminus1 Kminus1 Δ119867 = kJmolminus1 Δ119866 =

298

kJmolminus1 119864 =119886

kJmolminus1

minus10302 plusmn 41 2652 plusmn 12 5722 plusmn 04 2706 plusmn 13

(c) Thermodynamic parameters associated with the equilibrium constants(1198701

and1198702

)

Equilibriumconstant Δ119867

0 kJmolminus1 Δ1198660298

kJmolminus1 Δ1198780 Jmolminus1 Kminus1

1198701

2428 minus708 105251198702

minus1718 minus1494 minus751

0 100 200 300 400 5000

50

100

150

200

1[FH] (dm3 molminus1)

10minus2(1k

obs)

(s)

293K298K303K

308K313K

Figure 6 Plots of 1119896obs versus 1[FH] at different temperaturesin the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [OHminus] = 002 and 119868 = 01mol dmminus3

possible formation of a transient complex flanked by oxidantand substrate comparable with the well-known Michaelis-Menten mechanism [36] for enzyme-substrate reactionsTheobserved insignificant effect of ionic strength on the reactionrate implies the association of an ion and a neutral molecule

0 50 100 150 2000

40

80

120

160

293K298K303K

308K313K

10minus2(1k

obs)

(s)

1[OHminus] (dm3 molminus1)

Figure 7 Plots of 1119896obs versus 1[OHminus] at different temperatures

in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 and 119868 = 01mol dmminus3

[37] that is between neutral fluorenone hydrazone and neg-ative alkali-permanganate species

In view of the above arguments the reaction mechanismshown in Scheme 1 may be suggested This involves attackof the active species of permanganate [MnO

4

sdotOH]2minus on thefluorenone hydrazone substrate leading to the formation ofa complex (C) in a preequilibrium step In this complex oneelectron is transferred from the substrate to permanganateUnder slow cleavage of the complex the formation of afree radical intermediate derived from the substrate andmanganate(VI) transient species has been monitored Theintermediate radical is rapidly attacked by another alkali-permanganate species to yield the corresponding diazoderiv-ative which on further oxidation by two moles of perman-ganate species gives the corresponding ketone (fluorenone)as the final oxidation product

The relationship between reaction rate and substrate (FH)hydroxyl ion and oxidant concentrations can be deduced (seeAppendix) to give the following equation

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (1)

The rate law under pseudo-first-order condition can be exp-ressed by

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (2)

6 Advances in Physical Chemistry

(C)

Slow

Fast

(FH)

+

Fast

O

H

MnO4minus+ OHminus

K1[MnO4middotOH]2minus

[MnO4middotOH]2minus

2minus

[MnO4middotOH]2minus

NmdashNH2

K2

NmdashNmdashOMnO3

+ H2O

k1

H2O +

MnO42minus +

N+ Nminus NmdashNH∙

+ MnO42minus

2[MnO4middotOH]2minus

+ 2MnO42minus

+ H2O + N2

Scheme 1 Mechanism of oxidation of fluorenone hydrazone by alkaline permanganate

Comparing (1) and (2) andwith rearrangement we obtain thefollowing equations

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(3)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(4)

According to (3) and (4) with other conditions being con-stant plots of 1119896obs versus 1[FH] at constant [OHminus] and1119896obs versus 1[OH

minus] at constant [FH] should be linear withpositive intercepts on 1119896obs axes and are certainly found tobe so as shown in Figures 6 and 7 respectively The slopesand intercepts of such plots lead to calculation of values of1198961

1198701

and1198702

(at different temperatures) as listed in Table 2The obtained values of119870

1

are in a good agreement with those

reported in the literature [18ndash20] Also the activation para-meters of 119896

1

alongwith thermodynamic parameters of1198701

and1198702

were calculated and were listed also in Table 2It has been previously reported [38] that the entropy of

activation tends to be more negative for reactions of inner-sphere nature whereas the reactions of positive Δ119878 = valuesproceed via outer-sphere mechanism The obtained largenegative values of entropy of activation (Table 2) suggest thatone-electron transfer of inner-sphere nature is themore plau-sible mechanism for the current oxidation reaction On theother hand positive values of both Δ119867 = and Δ119866 = specifythat the formation of the complex is endothermic and non-spontaneous respectively

4 Conclusions

The kinetics of oxidation of fluorenone hydrazone by alkalinepermanganate has been studied The oxidation product offluorenone hydrazone was identified by GCMS and FT-IRanalyses as the corresponding ketone (9H-fluorenone) The

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

4 Advances in Physical Chemistry

Table 1 Effect of variation of [MnO4

minus] [FH] [OHminus] and 119868 on the observed first-order rate constants (119896obs) in the oxidations of fluorenonehydrazone by alkaline permanganate at 25∘C

104 [MnO4

minus] (mol dmminus3) 103 [FH] (mol dmminus3) 102 [OHminus] (mol dmminus3) 119868 (mol dmminus3) 104 119896obs (sminus1)

10 80 20 01 19820 80 20 01 20230 80 20 01 19240 80 20 01 19660 80 20 01 18380 80 20 01 18940 20 20 01 7340 40 20 01 12040 60 20 01 15840 80 20 01 19640 100 20 01 22840 120 20 01 25640 80 05 01 9840 80 10 01 14240 80 15 01 17440 80 20 01 19640 80 30 01 23640 80 40 01 27340 80 20 01 19640 80 20 02 18940 80 20 03 20740 80 20 04 19240 80 20 05 18940 80 20 06 202Experimental error is plusmn3

variation in ionic strength did not affect the oxidation rate asobserved from the data listed in Table 1

37 Effect of Temperature The oxidation rate was recordedat five different temperatures 293 298 303 308 and 313 Kunder varying the concentrations of fluorenone hydrazoneand alkali at constant ionic strengthThe activationparametersof the rate constant of the slow step (119896

1

) along with thermo-dynamic parameters of the equilibrium constants involved inthe reaction mechanism were evaluated using Arrhenius andEyring equations and were listed in Table 2

38 Polymerization Study To check the existence of freeradicals in the reaction under investigation the reactionsmixtures were mixed with identified quantities of acryloni-trilemonomer and stored for 6 hours under dry nitrogen con-dition On dilution with methanol white precipitates wereformed indicating the participation of free radicals in the oxi-dation reactions The blank experiments which were carriedout with either permanganate or every substrate with acrylo-nitrile did not induce polymerization under the same exper-imental conditions

39 Reaction Mechanism Permanganate ion is found to bea powerful oxidant in aqueous alkaline media and exhibits

some of oxidation states such as Mn(VII) Mn(V) andMn(VI) At pH gt 12 the reduction product of Mn(VII) isstable Mn(VI) and no further reduction is observed [29 30]The formation of a manganate(VI) intermediate was con-firmed by the green color observed as the reactions proceeded[31 32] which undergoes a slow decay to give rise to the finaloxidation products The yellow color persisted after achieve-ment of the oxidation reactions then finally discrete brownMnO2

sol was observed confirming that Mn(V) specieshypomanganate(V) formed and subsequently decomposedto Mn(IV) sol [33]The latter was coagulated by aging to givea colloidal precipitate of Mn(IV)O

2

It was reported [34 35] that permanganate ion in aqueous

alkaline media combines with alkali to produce an alkali-permanganate species [MnO

4

sdotOH]2minus in a preequilibriumstep as shown in Scheme 1 This is consistent with the appar-ent order of less than unity with respect to the alkali Theformation of [MnO

4

sdotOH]2minus in the present systems is furthersupported by the plots of 1119896obs versus 1[OH

minus] shown inFigure 7 which are linear with nonzero intercepts

Many investigators [18ndash24] have suggested that most ofthe permanganate ion oxidation reactions in neutral andalkaline media proceed through intermediate complexes for-mation between the oxidant and substrates The kineticevidence for such complex was established by the linearity ofthe plots between 1119896obs and 1[FH] Figure 6 in favor of

Advances in Physical Chemistry 5

Table 2 Values of 1198961

1198701

and 1198702

(at different temperatures)activation parameters associated with the slow step (119896

1

) and ther-modynamic parameters of the equilibrium constants (119870

1

and 1198702

)in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 [OHminus] = 002 and 119868 =01mol dmminus3

(a) Values of 1198961

1198701

and1198702

(at different temperatures)

Constant Temperature (K)293 298 303 308 313

104 1198961

(dm3molminus1 sminus1) 371 450 539 641 7411198701

(dm3molminus1) 1562 1748 2011 2474 290810minus2 119870

2

(dm3molminus1) 473 416 361 323 306

(b) Activation parameters associated with the slow step (1198961

)

Δ119878= Jmolminus1 Kminus1 Δ119867 = kJmolminus1 Δ119866 =

298

kJmolminus1 119864 =119886

kJmolminus1

minus10302 plusmn 41 2652 plusmn 12 5722 plusmn 04 2706 plusmn 13

(c) Thermodynamic parameters associated with the equilibrium constants(1198701

and1198702

)

Equilibriumconstant Δ119867

0 kJmolminus1 Δ1198660298

kJmolminus1 Δ1198780 Jmolminus1 Kminus1

1198701

2428 minus708 105251198702

minus1718 minus1494 minus751

0 100 200 300 400 5000

50

100

150

200

1[FH] (dm3 molminus1)

10minus2(1k

obs)

(s)

293K298K303K

308K313K

Figure 6 Plots of 1119896obs versus 1[FH] at different temperaturesin the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [OHminus] = 002 and 119868 = 01mol dmminus3

possible formation of a transient complex flanked by oxidantand substrate comparable with the well-known Michaelis-Menten mechanism [36] for enzyme-substrate reactionsTheobserved insignificant effect of ionic strength on the reactionrate implies the association of an ion and a neutral molecule

0 50 100 150 2000

40

80

120

160

293K298K303K

308K313K

10minus2(1k

obs)

(s)

1[OHminus] (dm3 molminus1)

Figure 7 Plots of 1119896obs versus 1[OHminus] at different temperatures

in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 and 119868 = 01mol dmminus3

[37] that is between neutral fluorenone hydrazone and neg-ative alkali-permanganate species

In view of the above arguments the reaction mechanismshown in Scheme 1 may be suggested This involves attackof the active species of permanganate [MnO

4

sdotOH]2minus on thefluorenone hydrazone substrate leading to the formation ofa complex (C) in a preequilibrium step In this complex oneelectron is transferred from the substrate to permanganateUnder slow cleavage of the complex the formation of afree radical intermediate derived from the substrate andmanganate(VI) transient species has been monitored Theintermediate radical is rapidly attacked by another alkali-permanganate species to yield the corresponding diazoderiv-ative which on further oxidation by two moles of perman-ganate species gives the corresponding ketone (fluorenone)as the final oxidation product

The relationship between reaction rate and substrate (FH)hydroxyl ion and oxidant concentrations can be deduced (seeAppendix) to give the following equation

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (1)

The rate law under pseudo-first-order condition can be exp-ressed by

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (2)

6 Advances in Physical Chemistry

(C)

Slow

Fast

(FH)

+

Fast

O

H

MnO4minus+ OHminus

K1[MnO4middotOH]2minus

[MnO4middotOH]2minus

2minus

[MnO4middotOH]2minus

NmdashNH2

K2

NmdashNmdashOMnO3

+ H2O

k1

H2O +

MnO42minus +

N+ Nminus NmdashNH∙

+ MnO42minus

2[MnO4middotOH]2minus

+ 2MnO42minus

+ H2O + N2

Scheme 1 Mechanism of oxidation of fluorenone hydrazone by alkaline permanganate

Comparing (1) and (2) andwith rearrangement we obtain thefollowing equations

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(3)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(4)

According to (3) and (4) with other conditions being con-stant plots of 1119896obs versus 1[FH] at constant [OHminus] and1119896obs versus 1[OH

minus] at constant [FH] should be linear withpositive intercepts on 1119896obs axes and are certainly found tobe so as shown in Figures 6 and 7 respectively The slopesand intercepts of such plots lead to calculation of values of1198961

1198701

and1198702

(at different temperatures) as listed in Table 2The obtained values of119870

1

are in a good agreement with those

reported in the literature [18ndash20] Also the activation para-meters of 119896

1

alongwith thermodynamic parameters of1198701

and1198702

were calculated and were listed also in Table 2It has been previously reported [38] that the entropy of

activation tends to be more negative for reactions of inner-sphere nature whereas the reactions of positive Δ119878 = valuesproceed via outer-sphere mechanism The obtained largenegative values of entropy of activation (Table 2) suggest thatone-electron transfer of inner-sphere nature is themore plau-sible mechanism for the current oxidation reaction On theother hand positive values of both Δ119867 = and Δ119866 = specifythat the formation of the complex is endothermic and non-spontaneous respectively

4 Conclusions

The kinetics of oxidation of fluorenone hydrazone by alkalinepermanganate has been studied The oxidation product offluorenone hydrazone was identified by GCMS and FT-IRanalyses as the corresponding ketone (9H-fluorenone) The

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Advances in Physical Chemistry 5

Table 2 Values of 1198961

1198701

and 1198702

(at different temperatures)activation parameters associated with the slow step (119896

1

) and ther-modynamic parameters of the equilibrium constants (119870

1

and 1198702

)in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 [OHminus] = 002 and 119868 =01mol dmminus3

(a) Values of 1198961

1198701

and1198702

(at different temperatures)

Constant Temperature (K)293 298 303 308 313

104 1198961

(dm3molminus1 sminus1) 371 450 539 641 7411198701

(dm3molminus1) 1562 1748 2011 2474 290810minus2 119870

2

(dm3molminus1) 473 416 361 323 306

(b) Activation parameters associated with the slow step (1198961

)

Δ119878= Jmolminus1 Kminus1 Δ119867 = kJmolminus1 Δ119866 =

298

kJmolminus1 119864 =119886

kJmolminus1

minus10302 plusmn 41 2652 plusmn 12 5722 plusmn 04 2706 plusmn 13

(c) Thermodynamic parameters associated with the equilibrium constants(1198701

and1198702

)

Equilibriumconstant Δ119867

0 kJmolminus1 Δ1198660298

kJmolminus1 Δ1198780 Jmolminus1 Kminus1

1198701

2428 minus708 105251198702

minus1718 minus1494 minus751

0 100 200 300 400 5000

50

100

150

200

1[FH] (dm3 molminus1)

10minus2(1k

obs)

(s)

293K298K303K

308K313K

Figure 6 Plots of 1119896obs versus 1[FH] at different temperaturesin the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [OHminus] = 002 and 119868 = 01mol dmminus3

possible formation of a transient complex flanked by oxidantand substrate comparable with the well-known Michaelis-Menten mechanism [36] for enzyme-substrate reactionsTheobserved insignificant effect of ionic strength on the reactionrate implies the association of an ion and a neutral molecule

0 50 100 150 2000

40

80

120

160

293K298K303K

308K313K

10minus2(1k

obs)

(s)

1[OHminus] (dm3 molminus1)

Figure 7 Plots of 1119896obs versus 1[OHminus] at different temperatures

in the oxidation of fluorenone hydrazone by alkaline permanganate[MnO

4

minus] = 40 times 10minus4 [FH] = 80 times 10minus3 and 119868 = 01mol dmminus3

[37] that is between neutral fluorenone hydrazone and neg-ative alkali-permanganate species

In view of the above arguments the reaction mechanismshown in Scheme 1 may be suggested This involves attackof the active species of permanganate [MnO

4

sdotOH]2minus on thefluorenone hydrazone substrate leading to the formation ofa complex (C) in a preequilibrium step In this complex oneelectron is transferred from the substrate to permanganateUnder slow cleavage of the complex the formation of afree radical intermediate derived from the substrate andmanganate(VI) transient species has been monitored Theintermediate radical is rapidly attacked by another alkali-permanganate species to yield the corresponding diazoderiv-ative which on further oxidation by two moles of perman-ganate species gives the corresponding ketone (fluorenone)as the final oxidation product

The relationship between reaction rate and substrate (FH)hydroxyl ion and oxidant concentrations can be deduced (seeAppendix) to give the following equation

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (1)

The rate law under pseudo-first-order condition can be exp-ressed by

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (2)

6 Advances in Physical Chemistry

(C)

Slow

Fast

(FH)

+

Fast

O

H

MnO4minus+ OHminus

K1[MnO4middotOH]2minus

[MnO4middotOH]2minus

2minus

[MnO4middotOH]2minus

NmdashNH2

K2

NmdashNmdashOMnO3

+ H2O

k1

H2O +

MnO42minus +

N+ Nminus NmdashNH∙

+ MnO42minus

2[MnO4middotOH]2minus

+ 2MnO42minus

+ H2O + N2

Scheme 1 Mechanism of oxidation of fluorenone hydrazone by alkaline permanganate

Comparing (1) and (2) andwith rearrangement we obtain thefollowing equations

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(3)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(4)

According to (3) and (4) with other conditions being con-stant plots of 1119896obs versus 1[FH] at constant [OHminus] and1119896obs versus 1[OH

minus] at constant [FH] should be linear withpositive intercepts on 1119896obs axes and are certainly found tobe so as shown in Figures 6 and 7 respectively The slopesand intercepts of such plots lead to calculation of values of1198961

1198701

and1198702

(at different temperatures) as listed in Table 2The obtained values of119870

1

are in a good agreement with those

reported in the literature [18ndash20] Also the activation para-meters of 119896

1

alongwith thermodynamic parameters of1198701

and1198702

were calculated and were listed also in Table 2It has been previously reported [38] that the entropy of

activation tends to be more negative for reactions of inner-sphere nature whereas the reactions of positive Δ119878 = valuesproceed via outer-sphere mechanism The obtained largenegative values of entropy of activation (Table 2) suggest thatone-electron transfer of inner-sphere nature is themore plau-sible mechanism for the current oxidation reaction On theother hand positive values of both Δ119867 = and Δ119866 = specifythat the formation of the complex is endothermic and non-spontaneous respectively

4 Conclusions

The kinetics of oxidation of fluorenone hydrazone by alkalinepermanganate has been studied The oxidation product offluorenone hydrazone was identified by GCMS and FT-IRanalyses as the corresponding ketone (9H-fluorenone) The

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

6 Advances in Physical Chemistry

(C)

Slow

Fast

(FH)

+

Fast

O

H

MnO4minus+ OHminus

K1[MnO4middotOH]2minus

[MnO4middotOH]2minus

2minus

[MnO4middotOH]2minus

NmdashNH2

K2

NmdashNmdashOMnO3

+ H2O

k1

H2O +

MnO42minus +

N+ Nminus NmdashNH∙

+ MnO42minus

2[MnO4middotOH]2minus

+ 2MnO42minus

+ H2O + N2

Scheme 1 Mechanism of oxidation of fluorenone hydrazone by alkaline permanganate

Comparing (1) and (2) andwith rearrangement we obtain thefollowing equations

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(3)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(4)

According to (3) and (4) with other conditions being con-stant plots of 1119896obs versus 1[FH] at constant [OHminus] and1119896obs versus 1[OH

minus] at constant [FH] should be linear withpositive intercepts on 1119896obs axes and are certainly found tobe so as shown in Figures 6 and 7 respectively The slopesand intercepts of such plots lead to calculation of values of1198961

1198701

and1198702

(at different temperatures) as listed in Table 2The obtained values of119870

1

are in a good agreement with those

reported in the literature [18ndash20] Also the activation para-meters of 119896

1

alongwith thermodynamic parameters of1198701

and1198702

were calculated and were listed also in Table 2It has been previously reported [38] that the entropy of

activation tends to be more negative for reactions of inner-sphere nature whereas the reactions of positive Δ119878 = valuesproceed via outer-sphere mechanism The obtained largenegative values of entropy of activation (Table 2) suggest thatone-electron transfer of inner-sphere nature is themore plau-sible mechanism for the current oxidation reaction On theother hand positive values of both Δ119867 = and Δ119866 = specifythat the formation of the complex is endothermic and non-spontaneous respectively

4 Conclusions

The kinetics of oxidation of fluorenone hydrazone by alkalinepermanganate has been studied The oxidation product offluorenone hydrazone was identified by GCMS and FT-IRanalyses as the corresponding ketone (9H-fluorenone) The

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Advances in Physical Chemistry 7

reaction constants involved in the reaction mechanism havebeen evaluated The activation and thermodynamic parame-ters have been evaluated and discussed

Appendix

Derivation of the Rate Law Expression

According to suggested mechanistic scheme

Rate =minus119889 [MnO

4

minus

]

119889119905= 1198961

[C] (A1)

1198701

=[MnO

4

sdotOH2minus][MnO

4

minus

] [OHminus] (A2)

Therefore

[MnO4

sdotOH2minus] = 1198701

[MnO4

minus

] [OHminus] (A3)

1198702

=[C]

[FH] [MnO4

sdotOH2minus] (A4)

Thus

[C] = 1198702

[FH] [MnO4

sdotOH2minus] (A5)

Substituting (A3) into (A5) leads to

[C] = 1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A6)

Substituting (A6) into (A1) yields

Rate = 1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

] (A7)

The total concentration of fluorenone hydrazone is given by

[FH]T = [FH]F + [C] (A8)

where [FH]T and [FH]F stand for total and free concentra-tions of the substrate

Substituting (A6) into (A8) gives

[FH]T = [FH]F + 11987011198702 [FH] [OHminus

] [MnO4

minus

] (A9)

[FH]T = [FH]F (1 + 11987011198702 [OHminus

] [MnO4

minus

]) (A10)

Therefore

[FH]F =[FH]T

1 + 1198701

1198702

[OHminus] [MnO4

minus

] (A11)

Similarly

[MnO4

minus

]T = [MnO4

minus

]F + [MnO4

sdotOH2minus] + [C] (A12)

[MnO4

minus

]T = [MnO4

minus

]F (1 + 1198701 [OHminus

]

+ 1198701

1198702

[FH] [OHminus] [MnO4

minus

])

(A13)

[MnO4

minus

]F =[MnO

4

minus

]T1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A14)

Also

[OHminus]T = [OHminus

]F + [MnO4

sdotOH2minus] (A15)

[OHminus]F =[OHminus]T

1 + 1198701

[MnO4

minus

] (A16)

Substituting (A11) (A14) and (A16) into (A7) (and omit-ting ldquoTrdquo and ldquoFrdquo subscripts) we get

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

(1 + 1198701

1198702

[OHminus] [MnO4

minus

]) (1 + 1198701

[MnO4

minus

]) (1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus]) (A17)

In view of low concentration of [MnO4

minus] used both first andsecond terms in the denominator of (A17) approximate tounity Therefore (A17) becomes

Rate =1198961

1198701

1198702

[FH] [OHminus] [MnO4

minus

]

1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A18)

Under pseudo-first-order conditions the rate law can beexpressed as

Rate =minus119889 [MnO

4

minus

]

119889119905= 119896obs [MnO

4

minus

] (A19)

Comparing (A18) and (A19) the following relationship isobtained

119896obs =1198961

1198701

1198702

[FH] [OHminus]1 + 1198701

[OHminus] + 1198701

1198702

[FH] [OHminus] (A20)

And with rearrangement the following equations areobtained

1

119896obs= (1 + 1198701

[OHminus]1198961

1198701

1198702

[OHminus])1

[FH]+1

1198961

(A21)

1

119896obs= (

1

1198961

1198701

1198702

[FH])1

[OHminus]

+ (1

1198961

1198702

1

[FH]+1

1198961

)

(A22)

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

8 Advances in Physical Chemistry

Acknowledgments

The authors are highly indebted to the Chemistry Depart-ment UmmAl-Qura University for using of all instrumenta-tion facilities Saleh A Ahmed is highly indebted to ProfessorDr JochenMattay University of Bielefeld Germany for help-ing with some GCMS and NMR measurements

References

[1] T Thormann M Rogojerov B Jordanov and E W ThulstrupldquoVibrational polarization spectroscopy of fluorene alignmentin stretched polymers and nematic liquid crystalsrdquo Journal ofMolecular Structure vol 509 no 1ndash3 pp 93ndash104 1999

[2] R J Irwin and N P Service ldquoEnvironmental contaminantsencyclopedia fluorenerdquo July 1997

[3] E Borras L A Tortajada-Genaro M Vazquez and B Zielin-ska ldquoPolycyclic aromatic hydrocarbon exhaust emissions fromdifferent reformulated diesel fuels and engine operating condi-tionsrdquo Atmospheric Environment vol 43 no 37 pp 5944ndash59522009

[4] X Li H Lu S Wang J Guo and J Li ldquoSensitizers of dye-sensitized solar cellsrdquo Progress in Chemistry vol 23 no 2-3 pp569ndash588 2011

[5] Z Ma J Ding Y Cheng et al ldquoSynthesis and characterizationof red light-emitting electrophosphorescent polymers withdifferent triplet energy main chainrdquo Polymer vol 52 no 10 pp2189ndash2197 2011

[6] H-Y Wang Q Qian K-H Lin et al ldquoStable and good colorpurity white light-emitting devices based on random fluo-renespirofluorene copolymers doped with iridium complexrdquoJournal of Polymer Science Part B Polymer Physics vol 50 no3 pp 180ndash188 2012

[7] X H Yang F I Wu D Neher C H Chien and C F ShuldquoPolyfluorene-based semiconductors combined with variousperiodic table elements for organic electronicsrdquo Chemistry ofMaterials vol 20 pp 1629ndash1635 2008

[8] O A Kucherak P Didier Y Mely and A S KlymchenkoldquoFluorene analogues of prodan with superior fluorescencebrightness and solvatochromismrdquo Journal of Physical ChemistryLetters vol 1 no 3 pp 616ndash620 2010

[9] Y-J Cheng S-H Yang and C-S Hsu ldquoSynthesis of conjugatedpolymers for organic solar cell applicationsrdquo Chemical Reviewsvol 109 no 11 pp 5868ndash5923 2009

[10] X Xing L Zhang R Liu et al ldquoA deep-blue emitter withelectron transporting property to improve charge balance fororganic light-emitting devicerdquo ACS Applied Materials amp Inter-faces vol 4 no 6 pp 2877ndash2880 2012

[11] J Pina J S S de Melo A Eckert and U Scherf ldquoUnusual pho-tophysical properties of conjugated alternating indigondashfluorenecopolymersrdquo Journal of Materials Chemistry A vol 3 no 12 pp6373ndash6382 2015

[12] L Jin J Chen B Song et al ldquoSynthesis structure and bioac-tivity of N1015840-substituted benzylidene-345-trimethoxybenzohy-drazide and 3-acetyl-2-substituted phenyl-5-(345-trimethoxy-phenyl)-23-dihydro-134-oxadiazole derivativesrdquoBioorganicampMedicinal Chemistry Letters vol 16 no 19 pp 5036ndash5040 2006

[13] A John Maria Xavier M Thakur and J Margaret MarieldquoSynthesis and spectral characterisation of hydrazone based 14-membered octaaza macrocyclic Ni(II) complexesrdquo Journal ofChemical and Pharmaceutical Research vol 4 no 2 pp 986ndash990 2012

[14] S A Ahmed Th Hartmann and H Durr ldquoPhotochromism ofdihydroindolizines part VIII First holographic image record-ing based on di- and tetrahydroindolizines photochromesrdquoJournal of Photochemistry and Photobiology A Chemistry vol200 no 1 pp 50ndash56 2008

[15] S A-M Ahmed and J-L Pozzo ldquoPhotochromism of dihy-droindolizines Part IX first attempts towards efficient self-assembling organogelators based on photochromic dihydroin-dolizines and N-acyl-1120596-amino acid unitsrdquo Journal of Photo-chemistry and Photobiology A Chemistry vol 200 no 1 pp 57ndash67 2008

[16] S A-M Ahmed ldquoPhotochromism of dihydroindolizines PartII Synthesis and photophysical properties of new photo-chromic IR-sensitive photoswitchable substituted fluorene-91015840-styrylquinolinedihydroindolizinesrdquo Journal of Physical OrganicChemistry vol 15 no 7 pp 392ndash402 2002

[17] B A AL Jahdaly I L Althagafi M Abdallah K S Khairouand SAAhmed ldquoFluorenone hydrazone derivatives as efficientinhibitors of acidic and pitting corrosion of carbon steelrdquoJournal of Materials and Environmental Science vol 7 no 5 pp1798ndash1809 2016

[18] A Fawzy S S Ashour and M A Musleh ldquoBase-catalyzedoxidation of l-asparagine by alkaline permanganate and theeffect of alkali metal ion catalysts a kinetic and mechanisticapproachrdquo Reaction Kinetics Mechanisms and Catalysis vol 111no 2 pp 443ndash460 2014

[19] A Fawzy and M R Shaaban ldquoKinetic and mechanistic inves-tigations on the oxidation of 119873

1015840

-heteroaryl unsymmetricalformamidines by permanganate in aqueous alkaline mediumrdquoTransition Metal Chemistry vol 39 no 4 pp 379ndash386 2014

[20] A Fawzy I A Zaafarany J Alfahemi and F A TirkistanildquoBase-catalyzed oxidation of aminotriazole derivative by per-manganate ion in aqueous alkaline medium a kinetic studyrdquoInternational Journal of Innovative Research in Science Engineer-ing and Technology vol 4 no 8 pp 6802ndash6814 2015

[21] B H Asghar and A Fawzy ldquoKinetic mechanistic and spec-troscopic studies of permanganate oxidation of azinylfor-mamidines in acidic medium with autocatalytic behavior ofmanganese(II)rdquo Journal of Saudi Chemical Society 2014

[22] A Fawzy S S Ashour and M A Musleh ldquoKinetics andmechanism of oxidation of l-histidine by permanganate ions insulfuric acid mediumrdquo International Journal of Chemical Kinet-ics vol 46 no 7 pp 370ndash381 2014

[23] GAAhmedA Fawzy andRMHassan ldquoSpectrophotometricevidence for the formation of short-lived hypomanganate(V)andmanganate(VI) transient species during the oxidation ofK-carrageenan by alkaline permanganaterdquoCarbohydrate Researchvol 342 no 10 pp 1382ndash1386 2007

[24] I A Zaafarany A A S N AlArifi A Fawzy et al ldquoFur-ther evidence for detection of short-lived transient hypoman-ganate(V) and manganate(VI) intermediates during oxidationof some sulfated polysaccharides by alkaline permanganateusing conventional spectrophotometric techniquesrdquo Carbohy-drate Research vol 345 no 11 pp 1588ndash1593 2010

[25] K A Gardner L L Kuehnert and J M Mayer ldquoHydrogenatom abstraction by permanganate oxidations of arylalkanes inorganic solventsrdquo Inorganic Chemistry vol 36 no 10 pp 2069ndash2078 1997

[26] S A Ahmed ldquoPhotochromism of dihydroindolizines PartIII [1] Synthesis and photochromic behavior of novel pho-tochromic dihydroindolizines incorporating a cholesteryl moi-etyrdquoMonatshefte fur Chemie vol 135 no 9 pp 1173ndash1188 2004

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Advances in Physical Chemistry 9

[27] S A Ahmed K S Khairou B H Asghar H A MuathenN M A Nahas and H F Alshareef ldquoPhotochromism oftetrahydroindolizines Part XIV synthesis of cis-fixed con-jugated photochromic pyridazinopyrrolo[12-b]isoquinolinesincorporating carbon-rich linkersrdquo Tetrahedron Letters vol 55no 14 pp 2190ndash2196 2014

[28] RMHassan A Fawzy AAlarifi GAAhmed I A Zaafaranyand H D Takagi ldquoBase-catalyzed oxidation of some sulfatedmacromolecules kinetics and mechanism of formation ofintermediate complexes of short-lived manganate (VI) andorhypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganaterdquo Jour-nal of Molecular Catalysis A Chemical vol 335 no 1-2 pp 38ndash45 2011

[29] L I Simandi M Jaky and Z A Schelly ldquoShort-lived man-ganate(VI) and manganate(V) intermediates in the perman-ganate oxidation of sulfite ionrdquo Journal of the American Chemi-cal Society vol 106 no 22 pp 6866ndash6867 1984

[30] L I Simandi M Jaky C R Savage and Z A Schelly ldquoKineticsand mechanism of the permanganate ion oxidation of sulfitein alkaline solutions The nature of short-lived intermediatesrdquoJournal of the American Chemical Society vol 107 no 14 pp4220ndash4224 1985

[31] F A Cotton and G Wilkinson Advanced Inorganic ChemistryJohn Wiley amp Sons New York NY USA 1980

[32] R M Hassan A R Dahy S Ibrahim I A Zaafarany andA Fawzy ldquoOxidation of some macromolecules Kinetics andmechanism of oxidation of methyl cellulose polysaccharide bypermanganate ion in acid perchlorate solutionsrdquo Industrial andEngineering Chemistry Research vol 51 no 15 pp 5424ndash54322012

[33] R M Hassan ldquoAlginate polyelectrolyte ionotropic gels XIVKinetics and mechanism of formation of intermediate complexduring the oxidation of alginate polysaccharide by alkaline per-manganate with a spectrophotometric evidence of manganate(VI) transient speciesrdquo Journal of Polymer Science Part APolymer Chemistry vol 31 no 1 pp 51ndash59 1993

[34] R G Panari R B Chougale and S TNandibewoor ldquoOxidationofmandelic acid by alkaline potassiumpermanganate A kineticstudyrdquo Journal of Physical Organic Chemistry vol 11 no 7 pp448ndash454 1998

[35] L A De Oliveira H E Toma and E Giesbrecht ldquoKinetics ofoxidation of free and coordinated dimethylsulfoxide with per-manganate in aqueous solutionrdquo Inorganic and Nuclear Chem-istry Letters vol 12 no 2 pp 195ndash203 1976

[36] L Michaelis and M L Menten ldquoThe kinetics of invertaseactionrdquo Biochemistry Z vol 49 pp 333ndash369 1913

[37] A A Frost and R G Person Kinetics and Mechanism WileyEastern New Delhi India 1970

[38] K W Hicks D L Toppen and R G Linck ldquoInner-sphereelectron-transfer reactions of vanadium(II) with azidoaminecomplexes of cobalt(III)rdquo Inorganic Chemistry vol 11 no 2 pp310ndash315 1972

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of