Kinetic analysis of DSC&ARC data: Manual
Contents
1. AKTS points ines ue AKTS Thermokinetics ca File Administration View Chat Zoom Maths Window f e m I m asex es b6zgej amp keuTa MS xeenhz Fig 17 8 d iE 1 90 BZ 4 A a sf E BR EE P A fein A O Eis Ec 4f C E sx co x T T ER Independent zones i 1 Kimin DSC 1Kmin 1 p T Len 8 Jmm E kKinati EJ Kinetic Results Customized AHr 15731J9 4 V w Reaction progress Untick All Subsignals V Reaction rate Differential isoconversional rv Activation energy Predictions 250 rv Customized DeltaHr 1573 Temperature Reaction Progress Reaction Rate rlv Experimental Tempera RR EE sanauty un wi Rename Hide XX Delete Coler B Bring Curve To Front i Send Curve To Back d Cutting 4X Baseline Integration M e e Experimental Temperature C e e 4 amp Subtraction B Derivation Temperature Segmentation fx Customizing Equation pexiA uonsipe4d VIO uone nuis 590 A Delta 0 5 10 Regression Time h e Customized DeltaHr 1573 12. qf AKTS Thermokinetics Customized DeltaHr 1573 1Jg 1 Predictions co 9 mom F File Administration View Chart Zoom Maths Window laglx a xe Hm l ECE 9 55 S IP m 42x E S amp amp Ht ug M i a o i E Fig 31 9 AEEA AERES Afsa ASAE S ca a Ru EM Independent zones dy 8 IB Z 1 Kimin DSC 1Kmin 1 Customized AHr 1573 1Jg 1 m EM Kinetic Results kd I v Reaction progress 350 i ry Reaction rate Ee Differential isoconversional bz ry Activation energy EZ BE Predictions 300 Er Customized DeltaHrs 1573 Temperature Untick All Subsignals Reaction Progress Properties Reaction Rate E 5 V41 Experimental Temg w Rename amp Iv4t1b Temperature M Q Hide Br Mixed Delet v Temperature Reaction Progress cs 7 v Reaction Rat SL i sscon te WE Bring Curve To Front d H c i Send Curve To Back 9 d Cutting M 4X Baseline Integration 2 A Subtraction 3 EZ Derivation A Temperature Segmentation 5 fx Customizing Equation E a A Delta E Regression m it Edit Prediction Time h e 4 m admin amp 9 40978 Rea Show Hide Annotation ARC Ye AKTS Thermokinetics Customized DeltaHrz 1573 1Jg 1 Predictions ca te File Administration View Chart Zoom Maths Window
3. Refresh qf AKTS Thermokinetics File Administration View Chat Zoom Maths Window Ea s e m m eec em 2 eee6zg 892 ja sug Plesx meus Fig 39 A amp d EE o0 6 EE uS A A sf ERR ER P fx in AO Es Ec d 9C P EE sx co a c G EM Independent zones me gt 1 X PI 1 Kimin DSC 1Kmin 1 Le E mem e Activation energy Kinetic Results m Kinetic Results k rV Reaction progress Reaction rate Differential isoconversional Ey rv Activation energy EZ EM Predictions A x amp o 5 0 0 2 0 4 0 6 Reaction progress alpha 0 pexi uoHolPald YJO 4 uonejuns i56 Heat 1 573 067 Jig T 94 52 and 173 85 C t 4 171 0 and 8 930 0 3 Experimental phi 3 B Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mV i Onset 152 791 C 7 564 s Offset 168 805 C 8 525 s Baseline Type Tangential Sigmoid Reaction progress 130 140 150 160 8n 100 120 140 Temperature C Temperature C Reaction progress DSC 1Kmin 1 100 110 120 4 m p admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan This procedure has to be continued as long as a good agreement between simulated and experime
4. zero th order kinetic model assumption certainly not the case at all if one examines the course of the DSC traces 0 DSC 0 Dhi factor correction for IMRad 24h prediction strongly depends on the kinetic model and therefore is incorrect if the wrong zero th order assumption is introduced TMRad24h p 0 w O 2014 AKTS AG Switzerland Palmetrics Japan Conclusion For all above mentioned reasons the superior procedure should be based on computing kinetic parameters from one ARC and at least one DSC experiment 1180 ARC 1 DSC
5. ARC DSC DSC gt ARC ARC It is obvious that a simulation depicting precisely both DSC and ARC traces is superior to a zeroth order kinetic analysis applied to one single ARC curve only which in no way will be able to describe the DSC curve properly DSC ARC 1 ARC 0 Therefore we strongly recommend our method which validates the simulation of the ARC curve using at least one separate DSC experiment something easy to perform AKTS 1 ARC DSC ARC
6. Fig 15 E AKTS Thermokinetics 6D mm File Administration View Chart Zoom Maths Window a semi m WW om8e m P z as 5 8 esum PI SX amp t pns 1s A amp dic dE o0 6 EE ACA ERE P feo In A O Bs Ec Af 9C E x ca ER Independent zones Sa m 1 Kimin DSC 1Kmin 1 oo Kinetic Results W customized AHr 15731J9 1 rv Reaction progress rv Reaction rate Differential izoconversional Hem Activation energy Predictions Er Customized DeltaHr 1573 emperature eaction Progress eaction Rate v Experimental Temperature TA s geury ogne sg gt e e on Rate s Reaction Progress PX uonoipe4d a YJO uonepuus i80 Temperature C Experimental Temperature C React ce JA gt e e 0 Time h i Customized DeltaHr 1573 1Jg 1 4 m admin 40978 Ready j SIEPO8 To display the whole experiment one has to click on button Reset chart view top of screen STEP08 Reset chart view E AKTS Thermokinetics ko 0 mcm File Administration View Chart Zoom Maths Window El a e MN T8 9h un m m a 5m asa Ps w ons Fig 16 S di EE eoo E IX
7. 2 Fig 28 Fig 30 Fig 28 DSC ARC ARC te AKTS Thermokinetics Mixed Predictions ca ue File Administration View Chart Zoom Maths Window amp X ja 3 m M fa W amp E a5 SP e tz m ja Hg NIS Ix mens Fig 28 ER Independent zones E d v 1 Kimin DSC 1Kmin 1 Kinetic Results rV Reaction progress 350 rV Reaction rate Differential izoconversional i Activation energy Predictions O Customized DeltaHr 1573 1J Temperature Reaction Progress Fr Reaction Rate rl Ex ntal Temperature 250 Ori Mixed Mixed R f amp e I E sopaupy v Temperature E Ls Reaction Frogress o Reaction Rate x 2007 o a wo sadi Cn e 100 PaXI uon ipaid YJO 4 uonelnuuls 5 Time h e 4 n Mixed admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan ARC ARC te AKTS Thermokinetics Customized DeltaHr 1573 1Jg 1 Predictions te File Administration View Chart Zoom Maths Window a y e M3 M a Wi e m ex WP ee 5izume ax a
8. DSC 0 5 K min 1 0 K min 1 DSC DSC DSC DSC Tangential Sigmoid we AKTS Thermokinetics 1 K min DSC 1Kmin 1 Independent zones 4 HA mw te File Administration View Chat Zoom Maths Window lx f x em CE 55x XP eld i o HEN Psx enz Fig 01 EN Independent zones rv 1Kimin DSC 1Kmin 1 EN GEEERUE eat 1 573 g XT at T 94 52 and 173 85 C kal HeatFlow c E HeatFlow e bs n V Subtracted Base w HeatFlow c bs n i Offset 168 805 C 8 625 s Baseline Type Tangential Sigmoid sonauny HeatFlow lc WW 120 Temperature C d DSC 1Kmin 1 4 admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEPO1 To perform a kinetic analysis it is necessary to select required curve by a right click on the name of the curve in the tree view and activate the option Enable for other data types Remark The kinetic evaluation based just on one curve is allowed only in the evaluations based on simultaneous application and combination of DSC and ARC or other techniques In the case of kinetic analysis based on DSC traces only it is necessary to
9. A LN Fig 40 ARC DSC ARC Fig 39 AKTS Thermokinetics l ca File Administration View Chart Zoom Maths Window Fa wo9 mH ICE PLECE mei ERES s amp uTmug Piet xumeonz Fig 40 te Activation energy Kinetic Results L Ie 23 beba ER Independent zones E Customized DeltaHr 1573 1Jg 1 Predictions 1 Kimin DSC 1Kmin 1 ES EM Kinetic Resutts SAV Customized AHre 1573 149 41 sa k v Reaction progress Reaction rate Differential izoconversional br rv Activation energy es EZ Ely Predictions z U E 300 w 2504 AZ 200 3 amp S 150 n 0 2 D 4 0 6 Reaction progress alpha 0 5 omized DeltaHrz 1573 1J9 1 Activation energy 5 m l2 1 KminDSC1Kmin 1 Independent zones e JL Lgs mu DI do Refresh Heat 1 573 067 Jig T 94 52 and 173 85 C t 4 171 0 and 8 930 0 3 Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mV etic constant 0 00024 1 perimental phi 3 0 8 w Right Limit T 1 Kimin 1573 067 Jg Onset 152 791 C 7 664 s Offset 158 805 C 8 625 s PaXI uon ipeld YJO 4m uone nuis D 04 Baseline Type Tangential Sigmoid c
10. AKTS O 2014 AKTS AG Switzerland Palmetrics Japan
11. Fig 10 Prediction Fig 11 1 Customized z 7 Y Z L 2 Open customized profile B5 ds E AKTS Thermokinetics lola mms File Administration View Chat Zoom Maths Window ja semm mw ome x Pzes ezsges ime umm meuxwens Fig 10 A amp d gE eoo 6 BE E AA sf E M ERE P feom In A GO Rs EE Hf 9 P EE sx co t a a Independent zones Na TET l y H 1 Kimin DSC 1Kmin 1 RENE ai EM Kinetic Results rv Reaction progress E ev Reaction rate Differential izoconversional V Activation energy Bf 1 K min DSC 1Kmin 1 Independent zones Heat 1 573 067 Jig T 94 52 and 173 85 C 1 Kimin 1573 067 Jig t 4171 0 and 8 930 0 3 Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mv Onset 152 791 C 7 564 s Offset 168 805 C 8 525 s Baseline Type Tangential Sigmoid oo o c co HeatFlow lc WW e M e Reaction progress DSC 1Kmin 1 C 100 110 120 130 140 150 80 100 120 140 Temperature C Temperature C Reaction progress DSC 1Kmin 1 qe Activation energy Kinetic Results dy 180 170 160 150 140 130 120 110 100 g0 Ln A alphay f alpha 1 S C Reaction rate DSC 1IKmin 1 C s n 0 2 0 4 0 6 2 100 110 120 130 140 150 160 Reaction progress alpha Temperature C Activation energy Reaction rate admin 9 40978 Ready O 2014 AKTS AG Switzerland Pal
12. s x a a em I DEADAR eton Hla ug As a n Fig 32 A amp d E o0 BEA A ae s E MEE I fx In A G Bis Ez d ei p ES Sx Co Ot aa Eh Independent zones l vo Customized AHr 1573 1Jg 1 E rv 1 Kimin DSC 1Kmin 1 Kinetic Results k rv Reaction progress 350 rv Reaction rate Differential izoconversional s E v Activation energy EZ Predictions 300 Customized DeltaHr 1573 Fr Temperature Reaction Progress ERAN rC Reaction Rate 5 v v 419 Experimental Temperat 250 amp rV di Temperature Mixed Mixed E rV Temperature o Reaction Progress x 200 o r Reaction Rate E 3 EJ 150 o m 100 P amp E 50 z x amp D 5 10 15 Time h d 4 m Customized DeltaHr 1573 1Jg 1 admin amp 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEP17 To continue the kinetic analysis based on simultaneous application of DSC and ARC data click on OEA STEP17 DSC ARC OEA y AKTS Thermokinetics Customized DeltaHr 1573 1Jg 1 Predictions c i m File Administration View Chart Zoom Maths Window i 3 e mi PELLO E HT SIMSIXwent Fig 33 g EX independent zones vo Customized amp Hrz 1573 1Jg 1 GN 1 KJmin DSC 1Km
13. 2 2 0 2 c 29 m 9 I I I I Lj I T f I 100 110 120 130 140 150 150 170 B 80 100 120 140 150 180 200 Temperature C e Temperature C qe zs z Reaction progress DSC 1Kmin 1 admin amp 9 40978 Ready o m 0098 2014 AKTS AG Switzerland Palmetrics Japan Fig 41 m TT AN Ub Em Fig 40 ARC DSC ARC T 2 kinetic constant phi factor te AKTS Thermokinetics ca File Administration View Chat Zoom Maths Window 3 eM ra W n 6 e KK arent Ahsan Fig 41 JA pe qt bO EM Independent zones rv 1 Kimin DSC 1Kmin 1 BM Kinetic Results rv Reaction progress Hr Reaction rate Differential izoconversional rv Activation energy Ely Predictions oA A FE a A fg am In ACG raeeEs olad X Cus EC WR te Activation energy Kinetic Results dy Customized AHrz 1573 14J9 1 0 ES Cn e 10088 RRE IEU cu
14. Such assumption will help in avoiding zero th order kinetic assumption which does not describe the DSC traces correctly DSC 0 avoiding wrong phi factor corrections based on zero th order kinetics simplified assumption 0 avoiding single curve analysis based on one ARC curve only 1 ARC checking the correctness of given phi factor by comparing the heat of reaction obtained by both techniques DSC and ARC It is obvious that for the same material the heat of reaction should be representative for the chemical reaction under investigation i e they should not dependent on the experimental procedure used such as DSC or ARC devices DSC ARC 2 ARC DSC ARC
15. the ARC is switching from the Heat Wait Search to adiabatic mode STEP12 Mixed ARC Heat Wait Search qf AKTS Thermokinetics ble fe File Administration View Chat Zoom Maths Window E x oe n II E EPILE dESDEEITY J fa HE I x meus Fig 23 A 8 d EE o0 6 EE E AL A sf EM ER D fem im ALGO Es Bc HC 9 EE Sx co oc aTa EM Independent zones Hey 1 K min DSC 1Kmin 1 Kinetic Results rv Reaction progress HNV Reaction rate H Differential izoconversional rv Activation energy Predictions Er Customized DeltaHr 1573 Temperature eC Reaction Progress w Reaction Rate gt M Experimental Temperature Customized AHrz 1573 1Jd9 1 M e e ieu onea R E em E ET Experimental Temperature C a e e e Qe duonsiposa 4 V3O uonejnuis 8 8 5 j 11 11 5 Time h Customized DeltaHrz 1573 1 49 1 m admin 9 40978 Ready l Fig 24 tracking mode qf AKTS Thermokinetics s Baiiia SL C 8 A A J wA A EH File Administration View Chart Zoom Maths Window E x etm Bt im eb m S e e
16. 155 005 C 8 389 s Einen Peak Height 3 974 cec ums Onset 152 791 C 7 564 3 s T Offset 158 805 C 8 625 s E m Baseline Type Tangential Sigmoid mi Ss I zZ a2 amp 8 130 Temperature C p Temperature C ction progress DSC 1Kmin 1 100 110 120 140 150 80 100 120 140 g Activation energy Kinetic Results a o Loops 100 Run undc ve ve fine constant 2e4 9 180 3B es gi tal phi ig z 1 Kimin 1573 067 Jig z Experimen i1 A min 186 x t gt Show Right Limit z ica 140 29 amp Oo 2 cn x 130 26 o w 120 24 Z 2 e oJ 110 22 s E 100 20 2 g0 ks S e m Us 0 0 2 0 4 0 6 100 110 120 130 140 150 1850 Reaction progress alpha e Temperature C Activation energy Reaction rate admin amp 9 40978 Ready SIEPO5 f the fit of experimental DSC curve by simulated traces is good the procedure can be continued by introducing the results of the ARC experiment which requires clicking on button Prediction choosing the temperature profile customized and selecting the corresponding ARC data STEP05 DSC ARC Prediction
17. 6 mg a tlak ant Asa SmE Fig 24 amp di ge o0 6 EE S A ae f E REIR P I feo n AO Es Ec Hf 9C E Sx co a a 8 ER Independent zones Sa 5 He 1 Kimin DSC 1Kmin 1 EM Kinetic Results rv Reaction progress rv Reaction rate Differential isoconversional rv Activation energy EM Predictions Er Customized DeltaHr 1573 Temperature Reaction Progress w Reaction Rate gt M Experimental Temperature Customized AHrz 1573 1Jg 1 nne jsa Xi BE ee B b Experimental Temperature C m e e 5 HaUI E e e paxiy uopaipaad a vjO uonelnus 90 8 8 5 j 11 11 5 Time h Customized DeltaHrz 1573 149 1 m admin amp 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan SIEP13 In the following window below which appears one has to select the option TMRad time to maximum rate under adiabatic conditions To continue the values of the heat capacity of the sample and the phi factor have to be introduced STEP13 Fig 25 TMRad time to maximum rate Cp 1 TMRad 2 Cp 3 te AKTS Thermokinet
18. AL Ae f E ME EE P 7 fx in AO B BE HF 9C EP co a a a EN Independent zones r 1 Kimin DSC 1Kmin 1 i rr BE Kinetic Resuts S f Reaction progress Customized AHrz 1573 1J9 1 BF Reaction rate Eer Differential isoconversional GN Activation energy BM Predictions Er Customized DeltaHr 1573 Temperature Reaction Progress Reaction Rate IV Experimental Temperature s3noury Experimental Temperature C H PoXI uonopead de YJO uone nuis Customized DeltaHrs 1573 1Jg 1 admin 40978 Ready Jj O 2014 AKTS AG Switzerland Palmetrics Japan STEPO9 To change the curve style and the properties of the ARC data one has to right click on the curve itself or on its name in the tree view and use the displayed option Properties It is recommended to use the option points instead of line to in order to present more clearly which data correspond to simulations or measurements Generally we recommend using curve style points for measured data and the lines for simulations STEPO9 ARC Properties tree view DZA Properties ine oints
19. C Temperature C DSC 1Kmin 1 1 Kimin 1573 067 Jig uogipaid Ww3O 4 uonenws alpha f alpha 1 s hb ec Ln A Reaction rate DSC 1Kmin 1 s 100 110 120 130 140 150 160 170 Reaction progress alpha Temperature C wv Reaction rate admin amp 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEPOA gt if NO one has to select the option OEA right margin and change the kinetic constant in the window displayed on the left side of the screen in this way that the fitting is good and the value of the activation energy is reasonable see above The values of the kinetic constant is generally chosen in the range of 1e 4 and 2e 4 STEP04 NO OEA right margin STEP03 kinetic constant Fig 07 Window OEA DSC simulation reasonable kinetic constant 1e 4 2e 4 Fig 09 E AKTS Thermokinetics c 9 mes File Administration View Chart Zoom Maths Window le mkaa Rale poB Ht anne aon Fig 08 EAEE E S E
20. amp ARC TMRad SADT Fig 01 Fig 42 E AKTS Thermokinetics aj File Administration View Chat Zoom Maths Window masuMi m o memu Ps es56 zmg9e 4ja s amp u PIOS x mes Fig 42 A d d Eo REA 4 EE A fxo im AG Bs EE M e P EE Sx co oc T T EM Independent zones rV 1 Kimin DSC 1Kmin 1 Kinetic Results rV Reaction progress Reaction rate Differential isoconversional rV Activation energy Predictions te Activation energy Kinetic Results TENES ee dy Customized AHrz 1573 14J9 1 e e Ln A alpha f alpha 1 s C 8 8 3 RUE EE co Cn e E kJ mol m 3 co ce cen m mn ce pm 5 I18UI Int Cn ce 5 D 0 2 0 4 0 6 Reaction progress alpha 0 Activation energy 0 5 210 15 2D 25 30 Loops n a 9e 1 K min DSC 1Kmin 1 Independent zones Loops 100 Run Undo Refresh Heat 1 573 067 Jig V Kinetic constant 0 0002428348607517 T 94 52 and 173 85 C t 4171 0 and 8 930 0 s Experimental phi 3 i TM 2 Peak Maximum 165 005 C 18 389 s z m Peak Height 3 974 m Show Right Limit Onset 152 791 C 7 B64 s Offset 168 805 C 8 525 s Baseline Type Tangential Sigmoid Heat
21. amp ofe o n A CO Bh EE HF C ES Sx cp at d T independent omm SANA p m E BE RU ff Reaction netic Result es I 6 om e K min DSC 1Kmin 1 Independent zones BR Kinetic Results v Reaction progress Hr Reaction rate S Differential isoconyersional Gi IV Activation energy Peak Height 3 974 mW Onset 152 791 C 7 554 s Offset 168 805 C 8 525 s Baseline Type Tangential Sigmoid Reaction progress DSC 1Kmin 1 C snau 100 110 120 130 140 100 120 140 Temperature C Temperature C Reaction progress Sf Activation energy Kinetic Results e mre iy 180 36 170 160 uonpe Vao d uone nuiis Ln A alpha f alpha 1 s C Reaction rate DSC 1Kmin 1 fs 0 4 0 6 130 140 Reaction progress alpha Temperature C Reaction rate admin amp 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan qf AKTS Thermokinetics I File Administration View Chat Zoom Maths Window FETT TM m W mex se e6zmas i enumm miM sxeens Fig 09 hfe nAGR EA ut S dic EE o0 S RE Independent zones D H 1 Kimin DSC 1Kmin 1 E a EEO EM Kinetic Results rlv Reaction progress rv Reaction rate Differential izoconversional sx cp a a G A A A dh E MaIE I 1 Heat 1 573 067 Jig i T 94 52 and 173 85 C i pu 1 Kimin 1573 067 J g t 4171 0 and 8 930 0 s f HF ss DSC 1Kmin 1 C 0 8 Peak Maximum
22. perform several DSC experiments at 0 5 1 2 4 and 8K min following the standard procedure STEP01 DSC tree view Enable for other data types activate 1 DSC ARC DSC AKTS Thermokinetics 0 5 1 2 4 8K min AKTS Thermokinetics 1 K min DSC 1Kmin 1 Independe deer mm WE File Administration View Chart Zoom Maths Window glx Ea oe MEN jm ewe muxPz e458z82 amp amp uUmS PB x eus Fig 02 S d Zt East E RE amp fx I A O f EE HF ei 9 E Sx cp CQ ceN depen ot on IY MINE t and 1 HeatFiow t 4 171 0 and 8 930 0 s i gt M HeatFlow lc Peak Maximum 165 005 C 8 389 s T EJ HeatFlow c bs n Peak Height 3 974 mW e V Subtracted Base Onset 152 791 C 7 664 s EC HeatFlow kc bs n Ji Of
23. Cn e E kJ mol Co c e 3 Cn e M e e i Ln iA calpha f alphay 1 s sopeupi cin 0 4 0 6 D Reaction progress alpha e 0 2 5 T T Activation energy 5 lt 10 d5 320 25 30 Loops Loops 100 1 573 067 Jig kinetic constant 0 0002428348607517 E T 94 52 and 173 85 C t 4 171 0 and 8 930 0 s E Experimental phi 3 B NE E A Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mW Show Right Limit i Onset 152 791 C 7 564 s Offset 168 805 C 8 625 s pexiA uonoipeidg 4 VIO uone nuls 90 HeatFlow lc rm E Baseline Type Tangential Sigmoid c o a c 2 8 100 110 120 130 140 150 150 170 60 80 100 120 140 Temperature C Temperature C e Reaction progress DSC 1Kmin 1 lt m admin 9 4 0978 Ready After finishing of optimization procedure one can begin the TMRad SADT etc calculations In these calculations the optimized parameters evaluated in the above described work flow will be applied TMRad SADT Prediction Prediction DSC TMRad SADT DSC
24. Cp ARC P Se AKTS Thermokinetics Mixed Predictions l E te File Administration View Chart Zoom Maths Window X ia 3 eM T zm e D e A FELLES OG BUSES m m Fig 27 EM Independent zones Mixed rV 1 Kimin DSC 1Kmin 1 m Kinetic Results rV Reaction progress 350 V Reaction rate Differential isoconversional z rv Activation energy b Predictions 300 Eev Customized DeltaHr 1573 1 Temperature Fr Reaction Progress Fr Reaction Rate K 250 rv Experimental Temperature a Orv Mixed s rl Temperature E Reaction Progress o Reaction Rate x 200 Uu d c ur o zt E i 150 o m 2 1004 i 1 Hb 1 1 Loo c peur EJ seine poe A 2 EAEN E a a EE i Hd T7 CO ck oi z x MM 3 T T T T D 2 4 B 8 10 Time h d 4 o Mixed admin amp 9 40978 Ready SIEP15 To compare the simulated and experimental ARC data one has to move the calculated temperature profile by drag and drop and merging both axis by selecting the y axis and doing a right click as shown below STEP15 ARC ARC y V Drag amp Drop
25. Flow lc mW p pax uopo 439 v3O uonejnuis Reaction progress 130 140 150 150 170 B gh 100 120 140 150 Temperature C e Temperature C Reaction progress DSC 1Kmin 1 100 110 120 lt 4 admin amp 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan DSC amp ARC TMRad24h TMRad 24h extracted by one ARC curve only is typically calculated based on zero th order kinetic assumption 1180 ARC TMRad24h 0 TAFT dT dt 1 phi dTad da dt dT dt 1 phi dTad A exp E R T In dT dt In 1 phi dTad A E R 1 T Y intercept slope X Therefore TMRad 24h prediction based on one ARC experiment contains several simplifying assumptions as e g 1 ARC TMRad24h only one ARC curve is taken into considerations what is characteristic for so called single curve methods because only one experimental signal in this case one T profile only the adiabatic one is considered 1 ARC 1
26. Jg 1 Edit Prediction lt m SFE 4 0978 Ready Show Hide Annotation E AKTS Thermokinetics o 5 File Administration View Chat Zoom Maths Window a a e Mi CE EELE IEAA E F Eh ug ISI Xx AE Fig 18 ASALE E Sas A EREE fenmlnmn ASC n EE HF ui E sx copola d a EM Independent zones 1 z em 1 Kimin DSC 1Kmin 1 Wf Customized Det Hrz dala E Kinetic Resuts k ry Reaction progress f BF Reaction rate rT Differential isoconversional Experimental Temperature bz mr Activation energy Lid Temperature B BE Predictions Customized DeltaHr 1573 Minimum Temperature Maximum Reaction Progress Number of points Reaction Rate E gt Experimental Tempera amp uv 5 2 Q gt i 3 3 z E amp 0 Customized DettaHrs 1573 1J9 1 lt m admin amp 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan The change of the curve colours can be also done in the option properties properties E AKTS Thermokinetics sw CN f 3 S o 3 File Administration View Chart Zoom Maths Mindan a x e MIN wk aala hl apoB ha ReH Aao mE Fig 19 A 3 dk EE 05 BE S A a Ai iR ES S fx in A O Fs EE Hf 9 eS cojat a E Independent zones ER 1 Kimin DSC 1Kmin t EN Kinetic Results kd S v Reaction progress i 8 V Reaction rate Ke Differential isoconversional BeF Activatio
27. Kinetic analysis of DSC amp ARC data Manual AKTS Thermokinetics amp Thermal Safety Version 4 0978 DSC ARC Version 1 02 2014 08 30 AKTS ARC TMRad24 ARC ARC 2014 08 28 version 4 0978 The following screen captures and notes present the work flow of kinetic analysis based on DSC and ARC traces DSC ARC STEPO1 The procedure requires performing single DSC experiment measured at e g 0 5 K min or 1 0 K min followed by construction of a baseline It is recommended to use the Baseline type Tangential Sigmoid as shown below STEPO1
28. S 00 DSC ARC save dais Hev Activation energy EE Organize v New folder Ft Favorites RE Desktop Downloads i Recent Places ES Documents HeatFlow lc WW 53 Libraries ij AKTS C Documents 2 Music i Pictures B Videos GRES dj Homegroup File name v Text files txt m IN paxil uon2ipaJd 4 YJO uoI1EInUJIG 130 140 action prog alpha Temperature C Activation energy Reaction rate admin 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEPOG Finally the time and temperature columns have to specified as shown below STEPO6 1 2 qf AKTS Thermokinetics File Administration View Chat Zoom Maths Window eaoemu BW 4 x ea tw5 mecj amp tmm Pisa Fig 13 d d orob E o 2 BEJ Independent zones 2e 8 v 1 Kimin DSC 1Kmin 1 SF Kinetic Results B Reaction progress y s ev Reaction rate E Differential isoconversio ex rv Activation energy BZ i Importation of customized temperature profiles F Show results in one plot E customized profe am at axes time min temp C 9 Repeating temperature profile A Number of cydes 1 8 mr 0 2 0 4 0 6 120 130 140 150 160 170 Reaction progress alp
29. Xx DE 7e 0 ER Independent zones 1 K min DSC 1Kmin 1 Kinetic Results V Reaction progress v Reaction rate Differential isoconversio rv Activation energy EM Predictions F Temperature r Reaction Progress C Reaction Rate n admin 8 40978 Ready Er Customized DeltaHr M Experimental Temperg EL mem se t p D x gt andi ea E e gt e B TE Predictions V Predictions Temperature Profiles Bl kms Fig 26 Iso Non Iso Step RE TER Safety Diagram TMRad SADT Automatic Report TMRad Time to Maximum Rate under adiabatic conditions Calculation of AT ad Remark AHr Heat of reaction J g Confidence interval Cp Spedfic heat Q g K ATO error can be used for calculation of the confidence interval initial Temp ATo error AHr Cp Phi ATad ATad error Underlying heating c C 0 9 0 9 GleK 0 AHr Cp Phi rate K min 112 82 amp o 1573 1 lo 2 3 2522 0 DO 11 5 Time hi O 2014 AKTS AG Switzerland Palmetrics Japan sopeupj oi paxiy uon2ipe4d 4m YO uoHelnulS i36 SIEP14 The AKTS software simulates now the ARC temperature profile based on the previously determined kinetic parameters and the provided Cp and phi factor values STEP14 AKTS
30. am sem s mwPeeeszgesojis amp uTsg Mi s xeeW nz Fig 34 A 8 dig o0 6 RES Aa E M ER DR feo in A LO hen s E ca a a Independent zones Ee 1 Kimin DSC 1Kmin 1 Kinetic Results Reaction progress H Reaction rate Differential isoconversional rv Activation energy Predictions vo Customized Hrz 1573 1Jg 1 300 sg 250 200 sro RUE e EE E kJ mol Ln A alpha f alpha 1 9 z 23 a m wu 10 0 0 2 0 4 0 6 0 8 Time h d Reaction progress alpha omized DeltaHr 1573 1J9 1 0 5 lO c progress Kinetic id Results Loops 100 Run Undo Heat 1 573 067 Jig Kinetic constant 2e 4 9 Fa is ie gis Cer 4171 0 and 8 930 0 s Experimental phi 3 Peak Maximum 155 005 C 8 389 s Peak Height 3 974 mW Onset 152 791 C 7 B64 s Offset 168 805 C 8 525 s HeatFlow lc mW wu c E 3 o m a o 3 z x fe Baseline Type Tangential Sigmoid m o z c o D u 100 110 120 130 140 150 160 B 80 100 120 140 150 180 Temperature C Temperature C Reaction progress DSC 1Kmin 1 E AKTS Thermokinetics e lola mmis File Administration View Chat Zoom Maths Window E x e m y t8 e 9 S P m e 5g a s amp amp HIT PIS x menz Fi
31. bolo CEKLL CEEE zob t stg e aem misxwen Fig 05 A 8 4 x SS LACE HRES Afam SEEPTIEITIDOEEE EM Independent zones gear cien ESSET rv 1 Kimin DSC 1Kmin 1 ot aii EM Kinetic Results V Reaction progress V Reaction rate Differential isoconversional rv Activation energy Heat 1 573 067 Jig T 94 52 and 173 85 C t 4171 0 and 8 930 0 s Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mv Onset 152 791 C 7 554 s Offset 158 805 C 8 525 s Baseline Type Tangential Sigmoid f d m EE ES Reaction progress DSC 1Kmin 1 C 100 110 120 130 140 150 60 80 100 120 140 160 180 Temperature C Temperature C Reaction progress DSC 1Kmin 1 qe Activation energy Kinetic Results dV 180 170 160 150 E 140 3 130 w 120 110 100 g0 pax uompaid Y30 Klopenn isao 4 amp 5mmu 00e in Reaction rate DSC 1Kmin 1 s D 0 2 0 4 0 6 100 110 120 130 140 150 160 170 Reaction progress alpha Temperature C E d Activation energy Reaction rate admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan DSC Fig 05 Fig 06 qf AKTS Thermokinetics ea File Administration View Chat Zo
32. eset View z eaction progress Kinetic Results l A i Kmin 1 Independent zones Autoscale HN 100 Undo Refresh Chart Margins Kinetic constant 2e 4 14 PaXI uoHolPald WO 4 uonejnuns Hi 7 Experimental phi 3 0 8 1 Kimin 1573 067 Jig zin 3 itles 0 6 Background 2 Ex 4 Axes E S Signals 5 X c aii C9 Themes B 0 Endo Exo E ow 100 110 120 130 140 150 160 170 EJ Tile 100 120 140 Temperature C Temperature C Reaction progress f Cascade admin 40978 Ready EJ Tile Kinetics SIEP20 Finally move the right limit as shown below and deselect option Show right limit by clicking on the corresponding tab STEP20 Fig 37 right limit Show right limit ES j ue Activation energy Kinetic Results qf AKTS Thermokinetics File Administration View Chat Zoom Maths Window CEKIT Bamar a e opoz Ba Hth aen Pisxeenz Fig 37 d di E o0 5 REL AC n E a ESfxo m AO f EE dL wi e E Sx co c gga EM Independent zones 1 Kimin DSC 1Kmin 1 Kinetic Results Reaction progress Reaction rate Differential izoconversional Activation energy Predictions JE EO
33. fset 168 805 C 8 625 s Baseline Type Tangential Sigmoi saur HeatFlow c mi uonenuiis 4 60 80 100 120 140 160 180 200 Temperature C 4 ii DSC 1Kmin 1 admin amp 9 40973 Ready te AKTS Thermokinetics 1 K min DSC 1Kmin 1 Independent zones ute File Administration View Chart Zoom Maths Window 8 x a moe aup cL ie E b CI IP E e 2 5 NICE a AAA Fig 03 A d 50 505 B8 A A d ERE fx In A C Eis E d e P ES sx cp EM Independent zones i d NN 1 Kimin DSC 1Kr A 45 rx Temperature P Save Heat 1 573 067 Jig mas i HeatFlow M Save As T 94 52 and 173 85 C l i ly HeatFlow t 4171 0 and 8 930 0 s f zz HeatFlo Pier En Peak Maximum 165 005 C 8 389 s 4 E rV Suk X Close Zone Peak Height 3 974 my HeatFll Onset 152 791 C 7 564 s m A Apply Set of Formats Offset 158 805 C 8 625 s E 3 35 E Baseline Type Tangential Sigmoid i mj Rename F le fi E Enable for Other Data Types 3 amp HE E 9 uu 5 o I 5 8 wI V pax uap 60 80 100 120 140 160 180 a Temperature C DSC 1Kmin 1 admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEPO2 To perform the kinetic evaluation one has to click on the button Kinetics placed on the rig
34. g 35 A amp d E v0 6 E t A A fh E MEE D A fx A In O Bs Ek d ei ES cp C G EM Independent zones 1 Kimin DSC 1Kmin 1 v M Kinetic Results s 41 rv Reaction progress 180 H Reaction rate 170 Hm Differential isoconversional 180 rv Activation energy e e 50 ci Predictions 140 zs n 130 120 110 100 8 0 5 10 0 0 2 0 4 0 6 Time h Reaction progress alpha i Activation energy wm RN c mE Ln A alpha f alphay 1 s C sonaupi E90 LL iac o _ ui eaction progress Kinetic Results F 1 K min DSC 1Kmin 1 Independent zones Loops 100 Run undo Refresh Heat 1 573 067 Jig Kinetic constant 2e 4 T 94 52 and 173 85 C t 4 171 0 and 8 930 0 5 Experimental phi 3 i 1 Kimin 1573 067 4g Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mV Onset 152 791 C 7 564 s Offset 158 805 C 8 525 s Baseline Type Tangential Sigmoid HeatFlow c rr la pax uonoipeig YJO 4m uone nuus Reaction progress 100 110 120 130 140 150 150 60 80 100 120 140 160 180 Temperature C Temperature C p een progress _ DSC 1kKmin 1 admin E 4 0978 Ready 2014 AKTS AG Switzerland Palmetrics Japan STEP19 Before setting it is useful to activate the function Sharp cursor which helps in easier selection of the required poin
35. gy Predictions rv Customized DeltaHr 1573 Temperature Reaction Progress Reaction Rate Fly Experimental Tempera r v Temperature Mixed Er Mixed rV Temperature Fr Reaction Progress Reaction Rate v Customized AHrz 1573 19 1 250 Merge With Remove Merge 4l Temperature Mixed Invert Labels Invert Axis M ce e Visible Axes Behind Curves Axis Title Labels Axis Line Font Numeric Format Experimental Temperature C e gt e e Grid Minor Grid 50 0 5 10 Time h Customized DeltaHrz 1573 1Jg 1 admin amp 9 40978 PressSHIFT to scroll the axis vertical 15 Temperature Mixed C RR m EE o nt soneupy gi pexix uonoipaid YJO 4s uonejnuis O 2014 AKTS AG Switzerland Palmetrics Japan STEP16 Itis also recommended to change the colour of the simulated curve to follow the rule that all simulated curves are displayed in black and all experimental curves are displayed in colour To do it right click on the name or directly on the curve and select the required colour STEP16 2
36. ha C Temperature C d admin 40978 Ready j y EN MR Jd 3s x OK ca 2 lt qf AKTS Thermokinetics E 3 File Administration View Chart Zoom Maths Window CELL O rA TENOREA lA amp di EE o0 6 8 IPIE NEU NEWER je u Tm MH een Fig 14 E Predictions Independent zones F rV 1 Kimin DSC 1Kmin 1 EE E Kinetic Results Ua p d s ti E Reaction progress re e le n S ii V Reaction rate Differential isoconversio Temperature Profiles Sample Controlled Thermal Analysis M Activation energy Iso Non Iso Step Modulated Shock a BE Safety Diagram TMRad SADT 2 E s Uu mi Importation of customized temperature profiles Show results in one plot 3 uu Combine all axes z 34 Open customized profile e time min temp C e Jer 18 Repeating temperature profile amp Number ofcydes 1 5 E D 0 2 0 4 0 6 i 100 110 120 130 140 150 160 170 Reaction progress alpha C Temperature C Activation energy Reaction rate admin amp 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEPO7 In the next steps of analysis only the experimental temperature is required so one should remove the ticks on temperature reaction progress and reaction rate as shown below STEP07
37. ht margin of the plot Thereafter by selecting the button Simulation right margin one gets the comparison between simulated data black curves and DSC experiment colour curves STEP02 Kinetics ZO Simulation right margin DSC E AKTS Thermokinetics 1 K min DSC 1Kmin 1 File Administration View Chart Zoom Window l X ja em lmumosemtxPszeeezg9ec s uqmI PM SIXxwenz Fig 04 ASEE PRAG d a EJ Xfxo In AO RE M e E sx co ac X UR CM Independent zones S 1 Kimin DSC 1Kmin 1 EEEN Un tede Re T 94 52 and 173 85 C t 4 171 0 and 8 930 0 s i gt M HeatFlow c Peak Maximum 165 005 C 8 389 s E E HeatFlow c bs In Peak Height 3 974 mW TT V Suktracted Base Onset 152 791 C 7 amp 64 s BA e HeatFlow kc bs n fi Offset 168 805 C 8 625 s Baseline Type Tangential Sigmoid o9 eu o c T E 60 80 100 120 140 160 180 200 Temperature C E d lt m DSC1Kmin 1 admin amp 9 40978 Ready Simulation right margin ue AKTS Thermokinetics
38. ics X File Administration View Chart Zoom Maths Window a e P9 B4 Fig 25 A d d 105 8 ER Independent zones v 1 Kimin DSC 1Kmin 1 ER Kinetic Results rV Reaction progress Reaction rate Differential izoconversio rv Activation energy ER Predictions Temperature Reaction Progress Reaction Rate lt admin amp 9 40978 Ready Er Customized DeltaHr FI Experimental Temper a D TE Predictions Predictions Temperature Profiles t Wh aaant e ez i a hla a HIER DN esla mE Iso RSR EU Safety Diagram Automatic Report TMRad Time to Maximum Rate under adiabatic conditions Calculation of AT ad Remark AHr Heat of reaction J g Confidence interval Cp Spedfic heat J g K ATO error can be used for calculation of the confidence interval Phi Thermal inertia factor initial Temp ATo error AHr Cp Phi ATad ATad error Underlying heating c Q o 0 9 GaK Q AHr Cp Phi rate K min 112 82 0 1573 1 0 CO NA X N A C 0 AES 8 4 TI Time h Customized DeltaHrz 1573 149 1 Cp OK te AKTS Thermokinetics sonauny pax UOP 4a YJO uone nuls 59 leg x File Administration View Chart Zoom Maths Window Ja 3 e M A ET
39. in 1 EX Kinetic Results rv Reaction progress 350 8 v Reaction rate Differential isoconversional ry Activation energy cM Predictions 300 BsF Customized DeltaHr 1573 gt Temperature Reaction Progress Reaction Rate RE Et sanau DRS d ID Experimental Temperal 250 rd1y Temperature Mixed Bev Mixed v Temperature Reaction Progress Reaction Rate Temperature C Uv e pax uopaipasd a0 PD uoneinuss 0 5 10 15 Time h Customized DetaHr 1573 1J9 1 admin 40978 Ready STEP18 The following screen captures shows the combination of DSC ARC and kinetic curves Coloured curves represent the experimental results and the black curves the corresponding simulations To continue with the kinetic analysis one has to click on Show right limit left down and has to set the required limit at the point where the runaway takes place STEP18 Fig 33 DSC ARC vette cites Fig 34 FO Show right limit Z 7 Y Z7 LCEEE OG 2014 AKTS AG Switzerland Palmetrics Japan ff AKTS Thermokinetis bola File Administration View Chat Zoom Maths Window _ E _ a wem f
40. metrics Japan e AKTS Thermokinetics File Administration View Chart Zoom Maths Window Fig 11 jeaemu m m4xX zesewzme ocj amp e um Sexe A 3 P3 Be 1 0 5 5E SNC VE NC Fem EM Independent zones Qf Predictions rV 1 Kimin DSC 1Kmin 1 EM Kinetic Results Hl ly Reaction progress P red ictio ns rV Reaction rate r _ Differential isoconversio Temperature Profiles Sample Controlled Thermal Analysis iv Activation energy Non Iso Step Modulated Shock SADT Show results in one plot Combine all axes j a Y Repeating temperature profile amp Number ofcydes 1 0 0 2 0 4 0 6 M 100 110 120 130 140 150 180 m Reaction progress alpha C Temperature C Activation energy Reaction rate admin amp 40978 Ready l Fig 12 ARC ARC_HWS txt 1 Open 2 ARC we AKTS Thermokinetics ca pa File Administration View Chart Zoom Maths Window leaemm m m294xtX eew me cj amp e zcmm ms xeson nz Fig 12 A b d orng di f RE II s aim Ai E LL i Eid Independent zones y Predictions rv 1 Kimin DSC 1Kmin 1 Efi Kinetic Results B Hev Reaction progress rv Reaction rate m Differential isoconversion AKT
41. mp ul Nix uwenz amp d gE o0 6 BE uS AL ae sh 8 MEE DR fx in AO Bis Ek Af ui P EE sx co oc c a T Wm MM Independent zones rV 1 K min DSC 1Kmin 1 EM Kinetic Results rl Reaction progress rv Reaction rate Differential isoconversional ri Activation energy EM Predictions rv Customized DeltaHr 1573 F Temperature r Reaction Progress Reaction Rate M Experimental Temperature Fly Temperature Mixed EM Mixed rV Temperature r Reaction Progress Reaction Rate admin amp 9 40978 Ready v Customized AHrz 1573 149 1 250 Cooom o oo DO M e e oo Experimental Temperature C e ce 50 0 5 10 Time h Customized DeltaHrz 1573 1Jg 1 Temperature Mixed C ne sg m f IE E sanaupy pexiA uonoipeid YJO 4m uone nus ARC ARC merge te AKTS Thermokinetics Customized DeltaHr 1573 1Jg 1 Predictions te File Administration View Chat Zoom Maths Window jg semiHi ADRE ES A A dh E ME P A feos m AO Es Ec dC 9 9 E sx o a t8 Wb e 9 eh GR S e A Eg e amp IDE GR BUCO EE ER Independent zones rV 1 Kimin DSC 1Kmin 1 SM Kinetic Results rV Reaction progress V Reaction rate Differential isoconversional rv Activation ener
42. n energy EZ Predictions Customized DeltaHr 1573 Temperature Reaction Progress Reaction Rate s v Experimental Tempera a a amp c o 3 o S 3 e i z x amp 10 Time h Customized DeltaHrz 1573 1J9 1 m Li admin 40978 Ready STEP10 One can also move the y axis if requested or block it by clicking on the green tick as shown below This is helpful if a zoom is required to find better out the starting point of the adiabatic conditions Remark All axes can be blocked in this way by using the scroll of the mouse one can just zoom in or out in one direction STEP10 y Fig 20 E AKTS Thermokinetics File Administration View Chat Zoom Maths Window f 3 e M madaan hle apona taaa nN lAs a mE Fig 20 A amp d E o0 6 BE E AL A f E RE P fx im A CO Bs Ec Hf C EE Sx c
43. nal Br rv Activation energy pE EM Predictions ds rv Customized DeltaHr 1573 gt Temperature E gt Reaction Progress pn Reaction Rate S gt V Experimental Temperature co 200 pt p a T D o e 5 150 Ei E J Z 3 S 8 100 pa z LI 2 e 3 zZ x amp Time h Customized DeltaHrz 1573 19 1 mm A admin amp 9 40978 Ready t fif AKTS Thermokinetics bolo File Administration View Chat Zoom Maths Window f FELIN jm o max seee zmgBec isenuma MMsxeenz Fg 22 A 8 di EE o0 6 RES ACA gh E IEEE P fx in A O Fs Ec df a A 8 sx cp ex a Independent zones Ele 1 Kimin DSC 1Kmin 1 Kinetic Results rv Reaction progress rv Reaction rate Differential izoconversional rv Activation energy EM Predictions rv Customized DeltaHr 1573 W Temperature w Reaction Progress w Reaction Rate gt V Experimental Temperature M e e Experimental Temperature C a e e I pax uon2ipe4d 4 YJO uoElnUIS 590 5 H8UIY one isg fem ET em E Er 0 10 Time h Customized DeltaHrz 1573 149 1 m admin 9 40978 Ready b a Fig 22 Fig 23 O 2014 AKTS AG Switzerland Palmetrics Japan STEP12 In the next step one has to click on Mixed right margin and to select the starting point when
44. ntal DSC and ARC curves is reached When the manual fit optimization is finished it is necessary to click on Run button to proceed with automatic optimization of kinetic constant and phi factor in order to achieve the best possible fit DSC ARC Fig 40 2 Rum kinetic constant AN Remark It is also possible to fix only one from two parameters kinetic constant and phi factor by removing the respective tick window left bottom If one from the two parameters is not selected it will not be optimized Q Fig 40 Window 1 2 kinetic constant phi factor 1 2 1
45. o ac a T ER Independent zones rV 1 Kimin DSC 1Kmin 1 EM Kinetic Results rV Reaction progress V Reaction rate Differential izoconversional V Activation energy EM Predictions rv Customized DeltaHr 1573 Temperature Reaction Progress Reaction Rate rv Experimental Temperature snsu cine sa 8T BRE ee BEL E Experimental Temperature C px uonoipeud 4 YJO uonepuis 190 D 10 Time h Customized DeltaHr 1573 1Jg 1 m admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan STEP11 Another option to select the requested area is to use the zoom function shown below STEP11 Calisto E AKTS Thermokinetics bola File Administration View Chart Zoom Maths Window 3 e MJ n a8 em olto Ba H amp ug P Sxe eethz Fig 21 3 d RE o0 5 E A A od E A fx m In A amp O fis E 41 e Sx Cp eag Independent zones z He 1 Kimin DSC 1Kmin 1 NE TUERBTESEE 19 3 1029 772 VPFEOICDORS Ed Kinetic Results Customized AHr 1573 1Jg 1 kd rv Reaction progress rv Reaction rate H Differential isoconversio
46. om Maths Window Jo semm j BE c m ex P ses esum atum MIS xuweng Fig 06 E Rfxro m AGE EE d e P EE sx oana Abk 1500 BE ZS AL a sh E ME EM Independent zones 7 r i 7 1 Kimin DSC 1Kmin 1 la Jm te 1 K min DSC 1Kmin 1 Independent zones m EM Kinetic Results rlv Reaction progress Z 1 Heat 1 573 067 Jig i SIX Fan als T 94 52 and 173 85 C id i jal i j 1 Kimin 1573 067 J t 4171 0 and 8 930 0 s pr Z ti 08 Peak Maximum 165 005 C 8 389 s f yl Activation energy 9 Peak Height 3 974 mW x 0 6 Onset 152 791 C 7 664 s f zx 9 Offset 168 805 C 8 525 s 204 Baseline Type Tangential Sigmoid E E S m n zZ 5 0 2 z PC a 100 110 120 130 140 150 60 80 100 120 140 Temperature C Temperature C Reaction progress DSC 1Kmin 1 uw E E ye Activation energy Kinetic Results Te Reaction rate Kinetic Results Ls o vq v EL 180 2 T9 F T 1 Kimin 1573 067 Ji g 1604 B d ES O7 00909 140 2 o 7 5E 4 ud ceo n ain ad 5E 4 3 E 110 s Ms 5 2 5E 4 EE o 80 2 0 v0 0 0 2 0 4 0 6 0 8 100 110 120 130 140 150 180 Reaction progress alpha C Temperature C Activation energy Reaction rate admin 9 40978 Ready STEPOS3 This approach is based on default values of kinetic parameters A and E which means that one has to check the following if the simulations black curves fit well the measurements colour curves and if a
47. re the provided values for activation energies are reasonable i e laying in the range of 100 500 kJ mol gt if YES one can directly continue with the step 5 STEP03 kinetic parameters A E default 1 simulations 2 reasonable 100 500kJ mol 1 2 YES step 05 E KTS Thermokinetics Le 6 en File Administration View Chart Zoom Maths Window i 398N maaalal apoB Ha ReH ByE Fig 07 456 BE Ez 7ofe In A CO B BE HF eC V E Sx Cp Ot GU Cp EX Independent zones I 1 KAmin DSC 1Kmin 1 2 sl L 1 K min DSC 1Kmin 1 Independent zones m CM Kinetic Results Reaction progress Heat 1 573 067 Jg i I fv Reaction rate T 94 52 and 173 85 C Differential isoconversional 1 K min 1573 067 Jg t 4 171 0 and 8 930 0 s Ex iem Activation ener Peak Maximum 165 005 C 8 389 s gr Peak Height 3 974 m Onset 152791 C 7 664 s Offset 168 805 C 8 525 s Baseline Type Tangential Sigmoid HeatF low e mv s2neury 120 130 140 150 160 60 80 100 120 140 Temperature
48. rogress alpha omized DeltaHrz 1573 149 1 A Ei o Loops 100 Run Undo Refresh Heat 4 573 067 Jig z n constant 2e 4 T 94 52 and 173 85 C 3 t 4 171 0 and 8 930 0 s J Experimental phi 3 1 Kimin 1573 067 Jig Peak Maximum 165 005 C 8 389 s z Peak Height 3 974 mW T Onset 152791 C 7 664 s pi amp Offset 168 805 C 8 625 s z 2 Baseline Type Tangential Sigmoid S t amp 100 110 120 130 140 150 160 170 60 80 100 120 140 Temperature C Temperature C 471 m admin 40978 Ready As presented below the simulation of the DSC curve fits quite well the experimental results however such a fit is not as good for the ARC data Improvement of the fit of ARC data can be achieved by modification of the kinetic constant window left bottom To observe the change of the fit quality after introduction of a new value it is necessary to click on Refresh button Fig 39 DSC ARC ARC ARC kinetic constant window kinetic constant
49. soneupi neisa 8 fT em I E 10 n 0 2 D 4 0 6 Time h e Reaction progress alpha omized DeltaHr 1573 1Jg 1 Activation energy 5 paxil uoHoIPald YJO 4m uonejnurs HO 9e 1 K min DSC 1Kmin 1 Independent zones Loops 100 Undo v Heat 1 573 067 Jig V Kinetic constant 2e 4 T 94 52 and 173 85 C t 4 171 0 and 8 930 0 s Experimental phi 3 1 Kimin 1573 067 Jig Peak Maximum 165 005 C 8 389 s Peak Height 3 974 mv Onset 152 791 C 7 564 s Offset 158 805 C 8 525 s Baseline Type Tangential Sigmoid HeatFlow lc WW Reaction progress 130 140 150 150 170 60 80 100 120 140 Temperature C i Temperature C Reaction progress DSC 1Kmin 1 100 110 120 m admin 9 40978 Ready O 2014 AKTS AG Switzerland Palmetrics Japan E AKTS Thermokinetics c File Administration View Chart Zoom Maths Window ja x 9 mI CE OLELE PzzeeBnmizgjs amp liug IS xuweWuz Fig 38 xxl Afzaln AG n EE H8 9 Zsx opl agd U 3 d4 5 i 0urbBEiXAaAas f a IE Independent zones He 1 Kimin DSC 1Kmin 1 Dass ono aloe EJ Kinetic Resuts dy ry Reaction progress S Reaction rate Hr Differential isoconversional ry Activation energy BM Predictions ha e Activation energy Kinetic Results IRELE z 2 amp 0 5 10 0 4 0 6 Time h Reaction p
50. t Right click on the plot and select Sharp cursor STEP19 Sharp cursor Sharp cursor ff AKTS Thermokinetics c5 m File Administration View Chart Zoom Maths Window E e M j ik Wh E db I m 4 Ho zh RE OA o amp nL Fig 36 A amp d E o0 6 BE E AL A f E RE DR fx in A C Bs Ec Hf 9 EE sx co at n a Lt gt 4 KA o ve fm O 4997 amp V7 LI L OM Up dmm Eid Independent zones Customized DeltaHr 1573118 1 Prediction r7 ES TA ER iiid f Customized DeltaHr 1573 1Jg 1 Predictions holm BE Activation energy Kinetic Results aaja s Ed Kinetic Results V Customized AHr 1573 1Jg 1 wv td k Reaction progress 180 dB zx H Reaction rate 350 1 34 E Differential isoconversional 300 7 32 br e Activation energy E p A Switch to Temperature 30 b T S ds E EM Predictions Ep Experiment Properties a 3 150 Zone Properties 24 100 Export Chart Data 22 s 20 50 J Show All Note i53 18 3 8 Fix Note 0 5 10 15 A 7 0 2 0 4 0 6 0 8 1 Time h Adjust Axes Horizontally Reaction progress alpha C v omized DeltaHrz 1573 19 1 Adjust Axes Vertically nee Ll R
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