research article synthesis, characterization, and thermal decomposition kinetics...

Research ArticleSynthesis Characterization and ThermalDecomposition Kinetics of Manganese Complex ofMethionine Hydroxy Analogue

Mei-Ling Wang Zhi-Xian Wu Qing Zang and Guo-Qing Zhong

School of Material Science and Engineering Southwest University of Science and Technology Mianyang 621010 China

Correspondence should be addressed to Guo-Qing Zhong zgq316163com

Received 20 July 2015 Revised 8 September 2015 Accepted 10 September 2015

Academic Editor Donald L Feke

Copyright copy 2015 Mei-Ling Wang et alThis 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 manganese complex of methionine hydroxy analogue was synthesized with methionine hydroxy analogue and manganesechloride as main raw materials The composition and structure of the complex were characterized by elemental analyses infraredspectra and X-ray powder diffraction The formula of the complex was Mn(C

5H9O3S)2 The experimental results indicated that

the manganese ion was respectively coordinated by the carboxylic and hydroxyl oxygen atoms from the methionine hydroxyanalogue ligandThe crystal structure of the complex belonged tomonoclinic systemwith the lattice parameters of a= 12775 nm b=15764 nm c = 15764 nm and 120573 = 9406∘The thermal decomposition process of the complex was studied by thermogravimetry anddifferential thermal analysis The decomposition of the complex has taken place above 200∘C The residue was mainly manganesesulfide and the experimental and calculated percentagemass loss was also givenThe parameters of thermal decomposition kineticsfor the complex such as activation energy reaction order and preexponential factor were calculated by usingKissinger Flynn-Wall-Ozawa and Freeman-Carroll methods and the kinetic equations of the thermal decomposition were obtained

1 Introduction

DL-2-Hydroxy-(4-methylthio) butanoic acid which isknown as methionine hydroxy analogue (abbreviated asH2MHA) is equivalent to methionine in biological value In

the digestive tract the complexes of H2MHA are absorbed by

the amino acid pathway and the absorption speed is fast andthe absorption rate is high [1] The complexes of methioninehydroxy analogue can be used as feed additives which canprovide the essential trace elements and methionine sourcesfor animal growth and these complexes have the advantagesof stable chemical properties nontoxicity little stimulationto animals small side effects and so on [2] Many forms ofmetal complexes with amino acids and hydrolysed proteinsless commonly with other organic ligands molecules arecommercially available The functions of the complexes ofH2MHA are similar to that of the complexes of natural amino

acid and trace elements while they are easier to meet theneeds of themarket than the complexes of natural amino acidand trace elements [3 4] So far the complexes of H

2MHA

have been rarely reported [5ndash7] especially in the thermaldecomposition mechanism and the thermal decompositionkinetics of the complexes of H

2MHA Here we report the

synthesis characterization and thermal decompositionmechanism of a manganese complex of H

2MHA and the

thermal decomposition kinetic parameters of the complexare studied by using three different methods These resultscan provide reliable scientific basis for the further researchand the development of new products

2 Experimental

21 Materials and Physical Measurements All chemicals pur-chased were of analytical reagent grade and used without fur-ther purification Methionine hydroxy analogue (industrialproduct with water content of 12) was provided by XingjiaBio-Engineering Co Ltd Changsha and manganese chlo-ride tetrahydrate was purchased from Sinopharm ChemicalReagent Co Ltd Shanghai

Hindawi Publishing CorporationInternational Journal of Chemical EngineeringVolume 2015 Article ID 874340 7 pageshttpdxdoiorg1011552015874340

2 International Journal of Chemical Engineering

The elemental analyses for C H S and O in the complexwere measured on a Vario EL CUBE elemental analyzer andthe content ofmanganesewas determined byEDTAcomplex-ometric titration with eriochrome black T as indicator TheIR spectrum was obtained with KBr pellets on a Nicolet 5700FTIR spectrophotometer in the range of 4000ndash400 cmminus1Thepowder X-ray diffraction (XRD) pattern of the complex wasrecorded by a Dmax-II X-ray diffractometer with Cu 119870

1205721

radiation and Ni filter voltage of 35 kV current of 60mAand scanning speed of 8∘minminus1 at room temperature andthe XRD data were collected in the diffraction angle rangeof 3minus80∘ The thermal analysis data of the complex wereobtained by using a SDT Q600 thermogravimetry analyzerin the air atmosphere from room temperature to 600∘C andthe test sample mass was about 35mg

22 Synthesis of Mn(HMHA)2 88 of methionine hydroxyanalogue (20mmol 341 g) and manganese chloride tetrahy-drate (10mmol 198 g) were weighed and mixed in a beakerand heated to dissolve completely The solution of sodiumhydroxide (20mmol 080 g) was added to the above solutionby drops under stirring The pH of the solution was 6-7 afteradding and no precipitation was generated Continue to heatwith stirring until the solution was concentrated to about10mL then the pink precipitation was generated and thepH of the solution was about 6 After the solution coolingthe resultant was separated from the reaction mixture byfiltration and washed by a small amount of anhydrousethanol The resultant was placed in a silica gel desiccator for1 week The product was pink powder (274 g) and the yieldwas about 776

3 Results and Discussion

31 Composition and Property The results of elemental anal-yses for the complex are shown in Table 1 The experimentalresults coincide with the theoretical calculation and themolecular formula of the complex is Mn(C

5H9O3S)2(119872119903=

35330) namely its composition is Mn(HMHA)2 The solid

complex is stable in the air easily dissolved in water and noteasy to absorb moisture

32 X-Ray Powder Diffraction Analysis The XRD patternof the complex is shown in Figure 1 The background ofthe XRD pattern is small and the diffractive intensity isstrong and the result indicates that the complex has a finecrystalline state The index calculation of the XRD data isbased on the computer programs of least squares method[8 9] and the calculated results are shown in Table 2 AsTable 2 shows all the diffraction data can be verywell indexedby a set of cell parameters according to monoclinic systemthe calculated spacing values 119889cal are consistent with theexperimental spacing values 119889exp and the maximum relativeerror is less than 03 The result indicates that the complexis a single phase compound and the crystal structure of thecomplex belongs to the monoclinic system with the latticeparameters of 119886 = 12775 nm 119887 = 15764 nm 119888 = 15764 nmand 120573 = 9406∘

Table 1 Elemental analysis data of the complex Mn(HMHA)2

Element Mn C H S OExperimental result 1586 3405 537 1793 2679Calculated result 1555 3399 514 1815 2717

0

10000

20000

30000

40000

Inte

nsity

(au

)

20 30 40 50 60 70 8010

2120579 (∘)

Figure 1 XRD pattern of the complex Mn(HMHA)2

33 IR Spectroscopy Analysis The IR spectrum of the com-plex is shown in Figure 2 The peaks at 2914 1438 and1313 cmminus1 are attributed to the characteristic absorption peaksof the CH

3Sndash group The moderate intensity broad peak at

3434 cmminus1 is attributed to the stretching vibration absorptionpeak of the ndashOH group between 3650 and 3200 cmminus1 and thecharacteristic stretching vibration absorption peak originatedfrom the CndashO bond of the secondary alcohols can be foundat 1071 cmminus1 so we can infer that the ndashOH group participatesin the coordination with metal ion The absorption peaks at1633 and 1578 cmminus1 and 1383 cmminus1 are attributed respectivelyto the antisymmetric and symmetric stretching vibration ofthe COOminus group The difference values between ]as(COOminus)and ]s(COOminus) are 250 and 195 cmminus1 which is a sign thatthe carboxyl oxygen atoms are coordinated with manganeseion by the bridging coordination mode [10] As shown inthe spectrum there are two strong absorption peaks near1600 cmminus1 which are in accord with the absorption peaksat 1637 and 1580 cmminus1 of the zinc complex of H

2MHA

without water molecule [6] The result illustrates that thereis not any water molecule in the manganese complex ofH2MHA and it is in line with the thermal decomposition

process In the low-frequency region the absorption peaksat 572 500 and 445 cmminus1 in the complex are assigned tothe stretching vibration of the MnndashO bond In conclusionthe six oxygen atoms from two HMHAminus anionic ligands aredirectly coordinated to the manganese ion which shouldexhibit hexacoordination as occurs for the correspondingMn2+ glycolate complex [11]

34 Thermal Decomposition Mechanism Studying thermaldecomposition process of complexes is helpful in the under-standing of the coordination structure of the complexes

International Journal of Chemical Engineering 3

Table 2 Experimental data and calculated results for X-ray powderdiffraction pattern of the complex Mn(HMHA)

2

Number 2120579(∘) ℎ 119896 119897 119889expnm 119889calnm 1198681198680

1 5615 0 0 1 15726 15724 1002 11217 0 2 0 07882 07882 873 12804 1 0 minus2 06908 06913 174 13907 2 0 0 06363 06371 135 16846 0 3 0 05259 05255 586 17280 2 0 minus2 05127 05131 267 18309 1 3 0 04846 04858 298 18965 1 3 minus1 04676 04677 039 19366 2 1 2 04580 04581 0310 20855 3 0 0 04256 04248 3411 21627 3 1 0 04106 04101 3512 22503 0 4 0 03948 03941 3413 23827 1 1 minus4 03731 03725 1814 24487 3 0 2 03632 03631 0315 25379 2 2 3 03507 03506 0716 25772 2 0 minus4 03454 03457 0417 26407 1 4 2 03372 03368 0618 26771 1 2 4 03327 03337 0619 28816 1 3 minus4 03096 03097 1620 29882 3 3 2 02988 02987 0421 30332 3 1 minus4 02944 02940 0422 30690 2 0 minus5 02911 02903 0623 30987 4 0 2 02884 02882 0424 31754 3 4 1 02816 02817 0625 32930 2 2 minus5 02718 02724 0226 33594 1 5 minus3 02666 02663 0627 34059 3 2 4 02630 02629 1528 35371 1 6 1 02536 02534 0529 36490 0 5 minus4 02460 02460 0430 38285 0 6 minus3 02349 02349 0331 38768 4 0 minus5 02321 02322 0332 39439 1 3 6 02283 02281 0333 39865 5 2 minus3 02260 02260 0234 40538 0 1 7 02224 02224 0435 41485 1 5 5 02175 02175 0536 43360 3 2 6 02085 02086 0237 44085 5 0 minus5 02053 02052 0338 45485 4 5 minus4 01993 01990 0539 47266 1 0 8 01922 01922 0440 48169 5 5 minus3 01888 01889 0341 48961 3 5 minus6 01859 01860 0442 52047 5 6 minus3 01756 01755 0343 56053 4 6 minus6 01639 01639 0244 57115 3 7 minus6 01611 01611 0345 60051 7 1 minus6 01539 01540 0246 66347 2 9 6 01408 01408 02

[12 13]The TG-DTA curves of the complex of H2MHA from

room temperature to 600∘Cwith a heating rate of 10∘Cminminus1are shown in Figure 3 and the TG and the DTG curves

3434

2962

2914

1633

1578

1438

1383

1347

13131268

1171

1071

967

896

866

825

725

668

572

500

445

3600 3200 2800 2400 2000 1600 1200 800 4004000

120592 (cmminus1)

30

40

50

60

70

T(

)

Figure 2 FTIR spectrum of the complex Mn(HMHA)2

00

05

10

15

DTA

(∘C

mg)

129∘C

251∘C

352∘C

4326 458∘C

1842

974

20

30

40

50

60

70

80

90

100

110

TG (

)

200 300 400 500 600100

T (∘C)

Figure 3 TG and DTA curves of the complex Mn(HMHA)2

of the complex at the heating rates of 5 10 15 and 20∘Cminminus1 are presented in Figure 4 We can come to the conclu-sion from Figures 3 and 4 that the thermal decompositionprocess of the complex consists of three stages With theincreasing of the heating rate the DTG curves move to thehigh temperature and the decomposition peak temperature119879119901of every stage is also moving in the direction of high

temperature [14] This reveals that the change of the heatingrate has a slight influence on the temperature range of eachmass loss stage In the first stage the percentage of massloss at different heating rates is basically unchanged Butthe final residual mass of the thermal decomposition for thecomplex is decreased with the increasing of the temperatureThe percentage of the residual mass at the heating rate of15∘C minminus1 is 2460 and it is in good agreement withthe theoretical calculated value of the residue of manganesesulfide in 2462 Figure 3 shows that the complex is stablein the air and is decomposed over 200∘C and its thermalstability is very good The final residue is black and stablepowder after the complex undergoes three consecutive massloss stages Figure 3 shows that there are one endothermicpeak and three exothermic peaks in the DTA curve Firstthere is a very weak endothermic peak at 129∘C while there


Table 3 Calculated results for the complex kinetic parameters of thermal decomposition using Kissinger and F-W-O methods

Reaction stage 119864kJmolminus1 119903 ln119860sminus1

Kissinger F-W-O Average Kissinger F-W-O Kissinger1 23813 23453 23633 09986 09987 603123 17678 17962 17820 09891 09904 32468

Temperature (∘C)6005004003002001000

20

30

40

50

60

70

80

90

100

110

Mas

s (

) 1 rarr 4

(1) 5∘Cmin(2) 10∘Cmin

(3) 15∘Cmin(4) 20∘Cmin

(a)

00

05

10

15

20

25

30

250 300 350 400 450 500200

Temperature (∘C)

(1) Tp = 23232∘C(2) Tp = 23868∘C(3) Tp = 24194∘C(4) Tp = 24460∘C

(1) Tp = 43978∘C(2) Tp = 45794∘C(3) Tp = 46579∘C(4) Tp = 47204∘C

5∘Cmin10∘Cmin

15∘Cmin20∘Cmin

Der

iv w

eigh

t (middot∘

Cminus1)

1 rarr 4

(b)

Figure 4 TG (a) and DTG (b) curves of the complex Mn(HMHA)2at different heating rates

is no mass loss in the TG curve and it is a melting andendothermic process of the complex of H

2MHA At the

first mass loss stage there is a sharp exothermic peak at251∘C in the DTA curve and it is ascribed to the oxidativedecomposition of the ligand and the loss of one H

2MHA

molecule CH3SCH2CH2CH(OH)COOH The experimental

percentage mass loss of 4326 in the TG curve is close tothe calculated result of 4251 At this time the title complexis transformed into the complex [Mn(MHA)] of the chelateratio of 1 1 At the second and the third mass loss stagesthere are one very weak exothermic peak at 352∘C and onestrong exothermic peak at 458∘C in the DTA curve and itis considered to be the oxidation and decomposition of thedeprotonated MHA2minus ligand The percentage of the residualmass in the TG curve is 2858 and there is some differencein the theoretical residual mass of 2462 of manganesesulfide It can be explained that partial manganese sulfide isoxidized to produce manganese sulfate when the heating rateis low

35 Thermal Decomposition Kinetics Analysis In order toobtain the thermal decomposition kinetic parameters ofthe title complex two different dynamic analysis methodsnamely the Kissinger method and the Flynn-Wall-Ozawa (F-W-O) method which are utilized to calculate the activationenergy 119864 the preexponential factor 119860 and the correlationcoefficient 119903 at the first and the third mass loss stages ofthe complex and the related results are shown in Figures 5

and 6 and Table 3 The basic equations of the Kissingermethod [15ndash17] and the F-W-Omethod [18ndash21] are as follows

ln120573

1198792119901

= ln 119860119877

119864minus

119864

119877119879119901

ln120573 = lg 119860119864

119877119866 (120572)minus 2315 minus 04567

119864

119877119879

(1)

where 120573 is the heating rate (Kminminus1) 119860 is the preexponentialfactor (sminus1) 119877 is the gas molar constant (8314 J Kminus1molminus1)119864 is the activation energy (kJmolminus1) 120572 is the conversion rate()119879

119901is the thermal spectrum peak temperature of different

heating rates (K) and 119866(120572) is the integral mechanismfunction Both of the two methods require several kineticcurves to perform the analysis and thus are sometimes calledmulticurve methods [22]

The Kissinger method is a model-free method but itis not isoconversional method because it assumes constantactivation energy with the progress of conversion insteadof calculating activation energy at different constant extentsof conversion [23] According to Kissinger the maximumreaction rate occurs with an increase in the reaction tem-perature [16] As shown in Figures 5(a) and 6(a) the plot ofln(1205731198792

119901) versus 1119879

119901obtained from thermal curves recorded

at different heating rates is a straight line whose slope can beused to calculate the activation energy 119864 and the interceptcan be used to calculate the preexponential factor 119860 In the F-W-O method when the percentage mass loss of the complex


minus94

minus96

minus98

minus100

minus102

minus104

minus106

minus108

minus110

00019

8

00019

7

00019

6

00019

5

00019

4

00019

3

1Tp

ln(120573T

2 p)

r = 099858y = minus2864222857x + 4581323

(a) Curve of ln(1205731198792119901) versus 1119879119901

000156

000157

000158

000159

000160

000155

1T

07

08

09

10

11

12

13

r = 099657y = minus1427016072x + 2341193

lg 120573

(b) Curve of lg120573 versus 1119879

Figure 5 Linear relationship at different heating rates and 119879119901for the first stage

ln(120573T

2 p)

1Tp

00014

0

00013

8

00013

6

00013

4

minus116

minus114

minus112

minus110

minus108

minus106

minus104

minus102

r = 09891y = minus2126331402x + 1826734


000196

000195

000197

000198

000194

000193

07

08

09

10

11

12

13

r = 099866y = minus1288323883x + 2618235

1T

lg 120573


Figure 6 Linear relationship at different heating rates and 119879119901for the third stage

in different heating rates 120573 is 20 at the thermal spectrumpeak temperature 119879

119901 the conversion rate 120572 is approximately

equal The activation energy can be obtained from the plotof lg120573 versus 1119879

119901for a series of experiments at different

heating rates the data of which are linearly fitted by leastsquare method and the results are exhibited in Figures 5(b)and 6(b) From Table 3 the activation energy of the pyrolysisof the complex obtained by theKissingermethod is extremelyclose to the one by the F-W-O method

There are various possibilities to express the conversionfunction for the solid-state reactions Most of the previousauthors used the conversion function namely 119891(120572) =

(1minus120572)119899The equation which can be obtained by the Freeman-Carroll method [24ndash26] is as follows

ln d120572

d119905+

119864

119877119879= ln119860 + 119899 ln (1 minus 120572) (2)

The average value of the activation energy obtained fromthe above two methods is used as the activation energy ofthe thermal decomposition processes The preexponentialfactor 119860 can be obtained by Kissinger and Freeman-Carrollmethods As shown in Figure 7 according to the thermaldecomposition data with a heating rate of 5∘Cminminus1 the plotof ln(d120572d119905)+119864119877119879 versus ln(1minus120572) is obtained in the first and


Table 4 Calculated results for the complex kinetic parameters using Kissinger and Freeman-Carroll methods

Reaction stage ln119860sminus1 119903 119899

Kissinger Freeman-Carroll Average Kissinger Freeman-Carroll Freeman-Carroll1 60312 54034 57173 09986 09706 0913 32468 27187 29828 09891 09543 091

r = 097056

y = 090923x + 5403398

minus02minus04minus06minus08minus10minus12minus14minus16minus18

524

526

528

530

532

534

536

538

ln(1 minus 120572)

ln(d120572dt)+ER

T

(a)

260

262

264

266

268

270

272

r = 095425

y = 090561x + 2718743

ln(d120572dt)+ER

Tminus12 minus10 minus08 minus06 minus04 minus02minus14

ln(1 minus 120572)

(b)

Figure 7 Curves of ln(d120572d119905) + 119864119877119879 versus ln(1 minus 120572) at the first (a) and the third (b) stages of the thermal decomposition

the thirdmass loss stagesThe reaction order can be found outthrough the slope of the line and the preexponential factor 119860can be gotten by the intercept The results are displayed inTable 4 The kinetic equation for the thermal decompositionof the title complex can be obtained by the nonisothermalkinetic equation [17]

d120572

d119905= 119860 [exp(minus

119864

119877119879)] (1 minus 120572)

119899 (3)

The thermal decomposition kinetic parameters of 119864 119860and 119899 are substituted into (3) and the thermal decompositionkinetics equations of the title complex in the first and the thirdmass loss stages can be obtained as follows

d120572

d119905= 6760

times 1024 [exp(minus23633 times 103

119877119879)] (1 minus 120572)

091

d120572

d119905= 8998


119877119879)] (1 minus 120572)

091

(4)

4 Conclusion

The manganese complex of H2MHA was synthesized with

DL-2-hydroxy-(4-methylthio) butanoic acid and manganesechloride as main raw materials and the complex wascharacterized by elemental analyses FTIR XRD and

TG-DTA-DTG The index results of the XRD data show thatthe crystal structure of the complex belongs to monoclinicsystem with the cell parameters of 119886 = 12775 nm 119887 =15764 nm 119888 = 15764 nm and 120573 = 9406∘ The Mn(II) ionis hexacoordinated by the carboxylic and hydroxyl oxygenatoms from the H

2MHA ligand The thermal decomposition

processes of the complex in the air illustrate that the complexis stable at room temperature and is decomposed over200∘C and the final residue is mainly manganese sulfideThethermal decomposition kinetics equations and parametersof the complex in the first and the third mass loss stagesare obtained by nonisothermal kinetic theory and dynamicmethods The results are as follows the activation energy 119864

is 23633 and 17820 kJmolminus1 the reaction order 119899 is 091 and091 and the preexponential factor ln(119860) is 57173 and 29828respectively

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

This work was supported by the Scientific Research Fundsof Education Department of Sichuan Province (10ZA016)The authors are very grateful to Analytical and TestingCenter of Southwest University of Science and Technologyand Engineering Research Center of Biomass Materials ofEducation Ministry for the testing of elemental analysesXRD FTIR and TG-DTG-DTA


References

[1] G Predieri M Tegoni E Cinti G Leonardi and S FerruzzaldquoMetal chelates of 2-hydroxy-4-methylthiobutanoic acid inanimal feeding preliminary investigations on stability andbioavailabilityrdquo Journal of Inorganic Biochemistry vol 95 no 2-3 pp 221ndash224 2003

[2] Q J Sun Y M Guo T G Zhang and J L Wen ldquoEffects of 2-hydroxy-4-(methylthio)-butanoic acid chelated CuMnZn oneggshell quality enzyme activity and trace mineral retention inlaying hensrdquo Journal of ChinaAgricultural University vol 16 no4 pp 127ndash133 2011

[3] G Predieri L Elviri M Tegoni et al ldquoMetal chelates of 2-hydroxy-4-methylthiobutanoic acid in animal feeding part 2further characterizations in vitro and in vivo investigationsrdquoJournal of Inorganic Biochemistry vol 99 no 2 pp 627ndash6362005

[4] European Food Safety Authority ldquoScientific opinion of thepanel on additives and products or substances used in ani-mal feed-safety and efficacy of mintrex Cu (copper chelateof hydroxy analogue of methionine) as feed additive for allspeciesrdquoThe EFSA Journal vol 693 p 2 2008

[5] Z-X Wu C-C Li G-Q Zhong D Li M Tao and W-XZhang ldquoPreparation and characterization of copper chelate ofhydroxymethioninerdquo Journal of Synthetic Crystals vol 43 no2 pp 474ndash479 2014

[6] G Predieri D Beltrami R Pattacini et al ldquoStructural studies insolution and in the solid state on the zinc chelate of 2-hydroxy-(4-methylthio)butanoic acid an effective mineral supplementin animal feedingrdquo Inorganica Chimica Acta vol 362 no 4 pp1115ndash1121 2009

[7] H B Xu K H Cheng D D Shi and W Wang ldquoProgressof synthesis of 2-hydroxy-4-(methylthio) butyric acid and itscalcium saltrdquo Progress in Modern Biomedicine vol 9 no 7 pp1387ndash1389 2009

[8] G-Q Zhong Y-C Guo Y-R Chen X-S Zang and S-R LuanldquoSynthesis and crystal structure of the complex of thioglycollicacid and trivalent antimony ionrdquo Acta Chimica Sinica vol 59no 10 pp 1599ndash1603 2001

[9] D Li and G-Q Zhong ldquoSynthesis and crystal structure of thebioinorganic complex [Sb(Hedta)]sdot2H

2Ordquo Bioinorganic Chem-

istry andApplications vol 2014Article ID461605 7 pages 2014[10] G B Deacon and R J Phillips ldquoRelationships between the

carbon-oxygen stretching frequencies of carboxylato complexesand the type of carboxylate coordinationrdquo Coordination Chem-istry Reviews vol 33 no 3 pp 227ndash250 1980

[11] G G Melikyan F Amiryan M Visi et al ldquoManganese(II)(III)glycolates preparation X-ray crystallographic study and appli-cation in radical cycloaddition reactionsrdquo Inorganica ChimicaActa vol 308 no 1-2 pp 45ndash50 2000

[12] G Q Zhong J Shen Q Y Jiang Y Q Jia M J Chen and Z PZhang ldquoSynthesis characterization and thermal decompositionof SbIII-M-SbIII type trinuclear complexes of ethylenediamine-N N N1015840 N1015840-tetraacetate (M Co(II) La(III) Nd(III) Dy(III))rdquoJournal of Thermal Analysis and Calorimetry vol 92 no 2 pp607ndash616 2008

[13] X Liu N Liu and Y Zhang ldquoSynthesis characterization scav-enging free radical and bacteriostasis characteristics of calcium-genistein complexrdquoCIESC Journal vol 61 no 11 pp 3006ndash30132010

[14] N Punsuwan and C Tangsathitkulchai ldquoProduct characteri-zation and kinetics of biomass pyrolysis in a three-zone free-fall reactorrdquo International Journal of Chemical Engineering vol2014 Article ID 986719 10 pages 2014

[15] L-Q Duan C-F Qiao Q Wei et al ldquoStructures thermodec-omposition kinetics and luminescence properties of three lan-thanide-based supramolecular compounds with 1H-benzim-idazole-2-carboxylic acidrdquo Acta PhysicomdashChimica Sinica vol28 no 12 pp 2783ndash2789 2012

[16] H E Kissinger ldquoReaction kinetics in differential thermal anal-ysisrdquo Analytical Chemistry vol 29 no 11 pp 1702ndash1706 1957

[17] L Cheng B L Zhang L Xu C H Hou and G J Liu ldquoThermaldecomposition kinetics of humic acidrdquo CIESC Journal vol 65no 9 pp 3470ndash3478 2014

[18] R Z Hu S L Gao F Q Zhao Q Z Shi T L Zhang and J JZhangThermal Analysis Kinetics Science Press Beijing China2nd edition 2008

[19] D Zhan C J Cong K Diakite Y T Tao and K L J ZhangldquoKinetics of thermal decomposition of nickel oxalate dihydratein airrdquoThermochimica Acta vol 430 no 1-2 pp 101ndash105 2005

[20] S M Pourmortazavi I Kohsari M B Teimouri and S SHajimirsadeghi ldquoThermal behaviour kinetic study of dihydro-glyoxime and dichloroglyoximerdquo Materials Letters vol 61 no25 pp 4670ndash4673 2007

[21] J Zsako ldquoKinetic analysis of thermogravimetric datardquo TheJournal of Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968

[22] J H Flynn and L A Wall ldquoGeneral treatment of the thermo-gravimetry of polymersrdquo Journal of Research of the NationalBureau of Standards Section A Physics and Chemistry vol 70no 6 pp 487ndash523 1966

[23] A Khawam Application of solid-state kinetics to desolvationreactions [PhD thesis] University of Iowa Iowa City IowaUSA 2007

[24] E S Freeman and B Carroll ldquoThe application of thermoana-lytical techniques to reaction kinetics the thermogravimetricevaluation of the kinetics of the decomposition of calciumoxalatemonohydraterdquoTheJournal of Physical Chemistry vol 62no 4 pp 394ndash397 1958

[25] P Wang X Gong B Zhang E V Leng Z G Chen and M HXu ldquoCharacteristics of cellulose from ionic liquid regenerationrdquoCIESC Journal vol 65 no 12 pp 3799ndash4793 2014

[26] H-W Liao Y-M Pan and Y Zhou ldquoThermal decompositionkinetics of [Sr(C

6H4NO2)2 sdot 3H

2O]rdquo Journal of Chemical Engi-

neering of Chinese Universities vol 28 no 3 pp 472ndash476 2014

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The elemental analyses for C H S and O in the complexwere measured on a Vario EL CUBE elemental analyzer andthe content ofmanganesewas determined byEDTAcomplex-ometric titration with eriochrome black T as indicator TheIR spectrum was obtained with KBr pellets on a Nicolet 5700FTIR spectrophotometer in the range of 4000ndash400 cmminus1Thepowder X-ray diffraction (XRD) pattern of the complex wasrecorded by a Dmax-II X-ray diffractometer with Cu 119870

1205721

radiation and Ni filter voltage of 35 kV current of 60mAand scanning speed of 8∘minminus1 at room temperature andthe XRD data were collected in the diffraction angle rangeof 3minus80∘ The thermal analysis data of the complex wereobtained by using a SDT Q600 thermogravimetry analyzerin the air atmosphere from room temperature to 600∘C andthe test sample mass was about 35mg

22 Synthesis of Mn(HMHA)2 88 of methionine hydroxyanalogue (20mmol 341 g) and manganese chloride tetrahy-drate (10mmol 198 g) were weighed and mixed in a beakerand heated to dissolve completely The solution of sodiumhydroxide (20mmol 080 g) was added to the above solutionby drops under stirring The pH of the solution was 6-7 afteradding and no precipitation was generated Continue to heatwith stirring until the solution was concentrated to about10mL then the pink precipitation was generated and thepH of the solution was about 6 After the solution coolingthe resultant was separated from the reaction mixture byfiltration and washed by a small amount of anhydrousethanol The resultant was placed in a silica gel desiccator for1 week The product was pink powder (274 g) and the yieldwas about 776

3 Results and Discussion

31 Composition and Property The results of elemental anal-yses for the complex are shown in Table 1 The experimentalresults coincide with the theoretical calculation and themolecular formula of the complex is Mn(C

5H9O3S)2(119872119903=

35330) namely its composition is Mn(HMHA)2 The solid

complex is stable in the air easily dissolved in water and noteasy to absorb moisture

32 X-Ray Powder Diffraction Analysis The XRD patternof the complex is shown in Figure 1 The background ofthe XRD pattern is small and the diffractive intensity isstrong and the result indicates that the complex has a finecrystalline state The index calculation of the XRD data isbased on the computer programs of least squares method[8 9] and the calculated results are shown in Table 2 AsTable 2 shows all the diffraction data can be verywell indexedby a set of cell parameters according to monoclinic systemthe calculated spacing values 119889cal are consistent with theexperimental spacing values 119889exp and the maximum relativeerror is less than 03 The result indicates that the complexis a single phase compound and the crystal structure of thecomplex belongs to the monoclinic system with the latticeparameters of 119886 = 12775 nm 119887 = 15764 nm 119888 = 15764 nmand 120573 = 9406∘

Table 1 Elemental analysis data of the complex Mn(HMHA)2

Element Mn C H S OExperimental result 1586 3405 537 1793 2679Calculated result 1555 3399 514 1815 2717

0

10000

20000

30000

40000

Inte

nsity

(au

)

20 30 40 50 60 70 8010

2120579 (∘)

Figure 1 XRD pattern of the complex Mn(HMHA)2

33 IR Spectroscopy Analysis The IR spectrum of the com-plex is shown in Figure 2 The peaks at 2914 1438 and1313 cmminus1 are attributed to the characteristic absorption peaksof the CH

3Sndash group The moderate intensity broad peak at

3434 cmminus1 is attributed to the stretching vibration absorptionpeak of the ndashOH group between 3650 and 3200 cmminus1 and thecharacteristic stretching vibration absorption peak originatedfrom the CndashO bond of the secondary alcohols can be foundat 1071 cmminus1 so we can infer that the ndashOH group participatesin the coordination with metal ion The absorption peaks at1633 and 1578 cmminus1 and 1383 cmminus1 are attributed respectivelyto the antisymmetric and symmetric stretching vibration ofthe COOminus group The difference values between ]as(COOminus)and ]s(COOminus) are 250 and 195 cmminus1 which is a sign thatthe carboxyl oxygen atoms are coordinated with manganeseion by the bridging coordination mode [10] As shown inthe spectrum there are two strong absorption peaks near1600 cmminus1 which are in accord with the absorption peaksat 1637 and 1580 cmminus1 of the zinc complex of H

2MHA

without water molecule [6] The result illustrates that thereis not any water molecule in the manganese complex ofH2MHA and it is in line with the thermal decomposition

process In the low-frequency region the absorption peaksat 572 500 and 445 cmminus1 in the complex are assigned tothe stretching vibration of the MnndashO bond In conclusionthe six oxygen atoms from two HMHAminus anionic ligands aredirectly coordinated to the manganese ion which shouldexhibit hexacoordination as occurs for the correspondingMn2+ glycolate complex [11]

34 Thermal Decomposition Mechanism Studying thermaldecomposition process of complexes is helpful in the under-standing of the coordination structure of the complexes



2





3434

2962

2914

1633

1578

1438

1383

1347

13131268

1171

1071

967

896

866

825

725

668

572

500

445

3600 3200 2800 2400 2000 1600 1200 800 4004000

120592 (cmminus1)

30

40

50

60

70

T(

)


00

05

10

15

DTA

(∘C

mg)

129∘C

251∘C

352∘C

4326 458∘C

1842

974

20

30

40

50

60

70

80

90

100

110

TG (

)

200 300 400 500 600100

T (∘C)








Temperature (∘C)6005004003002001000

20

30

40

50

60

70

80

90

100

110

Mas

s (

) 1 rarr 4

(1) 5∘Cmin(2) 10∘Cmin

(3) 15∘Cmin(4) 20∘Cmin

(a)

00

05

10

15

20

25

30

250 300 350 400 450 500200

Temperature (∘C)

(1) Tp = 23232∘C(2) Tp = 23868∘C(3) Tp = 24194∘C(4) Tp = 24460∘C

(1) Tp = 43978∘C(2) Tp = 45794∘C(3) Tp = 46579∘C(4) Tp = 47204∘C

5∘Cmin10∘Cmin

15∘Cmin20∘Cmin

Der

iv w

eigh

t (middot∘

Cminus1)

1 rarr 4

(b)



2MHA At the


2MHA





ln120573

1198792119901

= ln 119860119877

119864minus

119864

119877119879119901

ln120573 = lg 119860119864

119877119866 (120572)minus 2315 minus 04567

119864

119877119879

(1)





119901) versus 1119879




minus94

minus96

minus98

minus100

minus102

minus104

minus106

minus108

minus110

00019

8

00019

7

00019

6

00019

5

00019

4

00019

3

1Tp

ln(120573T

2 p)

r = 099858y = minus2864222857x + 4581323


000156

000157

000158

000159

000160

000155

1T

07

08

09

10

11

12

13

r = 099657y = minus1427016072x + 2341193

lg 120573



ln(120573T

2 p)

1Tp

00014

0

00013

8

00013

6

00013

4

minus116

minus114

minus112

minus110

minus108

minus106

minus104

minus102

r = 09891y = minus2126331402x + 1826734


000196

000195

000197

000198

000194

000193

07

08

09

10

11

12

13

r = 099866y = minus1288323883x + 2618235

1T

lg 120573










ln d120572

d119905+

119864

119877119879= ln119860 + 119899 ln (1 minus 120572) (2)






r = 097056

y = 090923x + 5403398


524

526

528

530

532

534

536

538

ln(1 minus 120572)

ln(d120572dt)+ER

T

(a)

260

262

264

266

268

270

272

r = 095425

y = 090561x + 2718743

ln(d120572dt)+ER


ln(1 minus 120572)

(b)



d120572

d119905= 119860 [exp(minus

119864

119877119879)] (1 minus 120572)

119899 (3)


d120572

d119905= 6760


119877119879)] (1 minus 120572)

091

d120572

d119905= 8998


119877119879)] (1 minus 120572)

091

(4)

4 Conclusion









Acknowledgments



References





























6H4NO2)2 sdot 3H





RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











2





3434

2962

2914

1633

1578

1438

1383

1347

13131268

1171

1071

967

896

866

825

725

668

572

500

445

3600 3200 2800 2400 2000 1600 1200 800 4004000

120592 (cmminus1)

30

40

50

60

70

T(

)


00

05

10

15

DTA

(∘C

mg)

129∘C

251∘C

352∘C

4326 458∘C

1842

974

20

30

40

50

60

70

80

90

100

110

TG (

)

200 300 400 500 600100

T (∘C)








Temperature (∘C)6005004003002001000

20

30

40

50

60

70

80

90

100

110

Mas

s (

) 1 rarr 4

(1) 5∘Cmin(2) 10∘Cmin

(3) 15∘Cmin(4) 20∘Cmin

(a)

00

05

10

15

20

25

30

250 300 350 400 450 500200

Temperature (∘C)

(1) Tp = 23232∘C(2) Tp = 23868∘C(3) Tp = 24194∘C(4) Tp = 24460∘C

(1) Tp = 43978∘C(2) Tp = 45794∘C(3) Tp = 46579∘C(4) Tp = 47204∘C

5∘Cmin10∘Cmin

15∘Cmin20∘Cmin

Der

iv w

eigh

t (middot∘

Cminus1)

1 rarr 4

(b)



2MHA At the


2MHA





ln120573

1198792119901

= ln 119860119877

119864minus

119864

119877119879119901

ln120573 = lg 119860119864

119877119866 (120572)minus 2315 minus 04567

119864

119877119879

(1)





119901) versus 1119879




minus94

minus96

minus98

minus100

minus102

minus104

minus106

minus108

minus110

00019

8

00019

7

00019

6

00019

5

00019

4

00019

3

1Tp

ln(120573T

2 p)

r = 099858y = minus2864222857x + 4581323


000156

000157

000158

000159

000160

000155

1T

07

08

09

10

11

12

13

r = 099657y = minus1427016072x + 2341193

lg 120573



ln(120573T

2 p)

1Tp

00014

0

00013

8

00013

6

00013

4

minus116

minus114

minus112

minus110

minus108

minus106

minus104

minus102

r = 09891y = minus2126331402x + 1826734


000196

000195

000197

000198

000194

000193

07

08

09

10

11

12

13

r = 099866y = minus1288323883x + 2618235

1T

lg 120573










ln d120572

d119905+

119864

119877119879= ln119860 + 119899 ln (1 minus 120572) (2)






r = 097056

y = 090923x + 5403398


524

526

528

530

532

534

536

538

ln(1 minus 120572)

ln(d120572dt)+ER

T

(a)

260

262

264

266

268

270

272

r = 095425

y = 090561x + 2718743

ln(d120572dt)+ER


ln(1 minus 120572)

(b)



d120572

d119905= 119860 [exp(minus

119864

119877119879)] (1 minus 120572)

119899 (3)


d120572

d119905= 6760


119877119879)] (1 minus 120572)

091

d120572

d119905= 8998


119877119879)] (1 minus 120572)

091

(4)

4 Conclusion









Acknowledgments



References





























6H4NO2)2 sdot 3H





RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation













Temperature (∘C)6005004003002001000

20

30

40

50

60

70

80

90

100

110

Mas

s (

) 1 rarr 4

(1) 5∘Cmin(2) 10∘Cmin

(3) 15∘Cmin(4) 20∘Cmin

(a)

00

05

10

15

20

25

30

250 300 350 400 450 500200

Temperature (∘C)

(1) Tp = 23232∘C(2) Tp = 23868∘C(3) Tp = 24194∘C(4) Tp = 24460∘C

(1) Tp = 43978∘C(2) Tp = 45794∘C(3) Tp = 46579∘C(4) Tp = 47204∘C

5∘Cmin10∘Cmin

15∘Cmin20∘Cmin

Der

iv w

eigh

t (middot∘

Cminus1)

1 rarr 4

(b)



2MHA At the


2MHA





ln120573

1198792119901

= ln 119860119877

119864minus

119864

119877119879119901

ln120573 = lg 119860119864

119877119866 (120572)minus 2315 minus 04567

119864

119877119879

(1)





119901) versus 1119879




minus94

minus96

minus98

minus100

minus102

minus104

minus106

minus108

minus110

00019

8

00019

7

00019

6

00019

5

00019

4

00019

3

1Tp

ln(120573T

2 p)

r = 099858y = minus2864222857x + 4581323


000156

000157

000158

000159

000160

000155

1T

07

08

09

10

11

12

13

r = 099657y = minus1427016072x + 2341193

lg 120573



ln(120573T

2 p)

1Tp

00014

0

00013

8

00013

6

00013

4

minus116

minus114

minus112

minus110

minus108

minus106

minus104

minus102

r = 09891y = minus2126331402x + 1826734


000196

000195

000197

000198

000194

000193

07

08

09

10

11

12

13

r = 099866y = minus1288323883x + 2618235

1T

lg 120573










ln d120572

d119905+

119864

119877119879= ln119860 + 119899 ln (1 minus 120572) (2)






r = 097056

y = 090923x + 5403398


524

526

528

530

532

534

536

538

ln(1 minus 120572)

ln(d120572dt)+ER

T

(a)

260

262

264

266

268

270

272

r = 095425

y = 090561x + 2718743

ln(d120572dt)+ER


ln(1 minus 120572)

(b)



d120572

d119905= 119860 [exp(minus

119864

119877119879)] (1 minus 120572)

119899 (3)


d120572

d119905= 6760


119877119879)] (1 minus 120572)

091

d120572

d119905= 8998


119877119879)] (1 minus 120572)

091

(4)

4 Conclusion









Acknowledgments



References





























6H4NO2)2 sdot 3H





RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










minus94

minus96

minus98

minus100

minus102

minus104

minus106

minus108

minus110

00019

8

00019

7

00019

6

00019

5

00019

4

00019

3

1Tp

ln(120573T

2 p)

r = 099858y = minus2864222857x + 4581323


000156

000157

000158

000159

000160

000155

1T

07

08

09

10

11

12

13

r = 099657y = minus1427016072x + 2341193

lg 120573



ln(120573T

2 p)

1Tp

00014

0

00013

8

00013

6

00013

4

minus116

minus114

minus112

minus110

minus108

minus106

minus104

minus102

r = 09891y = minus2126331402x + 1826734


000196

000195

000197

000198

000194

000193

07

08

09

10

11

12

13

r = 099866y = minus1288323883x + 2618235

1T

lg 120573










ln d120572

d119905+

119864

119877119879= ln119860 + 119899 ln (1 minus 120572) (2)






r = 097056

y = 090923x + 5403398


524

526

528

530

532

534

536

538

ln(1 minus 120572)

ln(d120572dt)+ER

T

(a)

260

262

264

266

268

270

272

r = 095425

y = 090561x + 2718743

ln(d120572dt)+ER


ln(1 minus 120572)

(b)



d120572

d119905= 119860 [exp(minus

119864

119877119879)] (1 minus 120572)

119899 (3)


d120572

d119905= 6760


119877119879)] (1 minus 120572)

091

d120572

d119905= 8998


119877119879)] (1 minus 120572)

091

(4)

4 Conclusion









Acknowledgments



References





























6H4NO2)2 sdot 3H





RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation













r = 097056

y = 090923x + 5403398


524

526

528

530

532

534

536

538

ln(1 minus 120572)

ln(d120572dt)+ER

T

(a)

260

262

264

266

268

270

272

r = 095425

y = 090561x + 2718743

ln(d120572dt)+ER


ln(1 minus 120572)

(b)



d120572

d119905= 119860 [exp(minus

119864

119877119879)] (1 minus 120572)

119899 (3)


d120572

d119905= 6760


119877119879)] (1 minus 120572)

091

d120572

d119905= 8998


119877119879)] (1 minus 120572)

091

(4)

4 Conclusion









Acknowledgments



References





























6H4NO2)2 sdot 3H





RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










References





























6H4NO2)2 sdot 3H





RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation









research article synthesis, characterization, and thermal decomposition kinetics...

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