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Content
AKTS - Themokinetics Software
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DETERMINATION OF THERMAL AGING,
THERMAL RUNAWAY, TMRad AND SADT
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Tableofcontents
AKTSELearningCasestudyWebinar....................................................................................9
ADVANCED KINETICSBASED SIMULATION METHOD THERMOKINETIC, THERMAL AGING
ANDSAFETY..............................................................................................................................53
1. IntroductionAnalysisProcess..................................................................................53
1.1. Applicationofthermokineticsforthedeterminationofmaterialsbehaviour....53
1.2. AnalysisProcess.....................................................................................................53
2. Experimentalpart(STEP1)........................................................................................53
2.1. Selectionoftheevaluationrangeanddeterminationofthebaseline.................53
3. Determinationofthekineticcharacteristics(STEP2)...............................................58
3.1. KineticAnalysisofThermallyStimulatedProcesses.............................................58
3.2. Remarksaboutisoconversionalmethods.............................................................65
4. KineticsandmilligramscaleShelflife(STEP3)........................................................67
4.1. Predictionofthereactionprogressunderanytemperaturemode.....................67
4.2. Isothermal,modulated,stepwiseandrealatmospherictemperaturemode......67
4.2.1. Isothermal.......................................................................................................67
4.2.2. NonIsothermal...............................................................................................69
4.2.3. Stepwise..........................................................................................................70
4.2.4. Modulated......................................................................................................71
4.2.5. Worldwide......................................................................................................72
4.2.6. STANAG2895..................................................................................................74
4.2.7. Customized.....................................................................................................75
4.2.8. SampleControlledThermalAnalysis..............................................................76
5. KineticsandscaleupSafetyanalysis(STEP3)........................................................78
5.1. Introduction...........................................................................................................78
5.2. ThekineticbasedapproachforthedeterminationofTimetoMaximumRate
underadiabaticconditions(TMRad)......................................................................78
5.2.1. Concept...........................................................................................................78
5.2.2. Heattransfermechanisms..............................................................................79
5.2.3. KineticbasedapproachDeterminationoftheTMRad.................................81
6. SelfAcceleratingDecompositionTemperature(SADT)(STEP3).............................92
6.1. Introduction...........................................................................................................92
6.2. Equivalentsphericalradius...................................................................................92
6.3. Theenergyequation.............................................................................................92
6.3.1. ForSOLIDSincontainers:...............................................................................94
6.3.2. ForLIQUIDSincontainers...............................................................................95
6.4. MethodforthecalculationofSelfAcceleratingDecompositionTemperature
(SADT)..................................................................................................................100
7. Conclusion................................................................................................................107
8. References................................................................................................................108
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Case study - Webinar
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ADVANCED
KINETICS-BASED
SIMULATION
METHOD
THERMAL AGING
THERMAL SAFETY
52
ADVANCED KINETICSBASED SIMULATION

THERMOKINETIC,THERMALAGINGANDSAFETY
METHOD
1. IntroductionAnalysisProcess
1.1.
Applicationofthermokineticsforthedeterminationofmaterialsbehaviour
ThemaingoalofAKTSThermokineticsSoftwarePackage[1]istofacilitatekineticanalysisof
anytypeofthermoanalyticaldata(DSC,DTA,TGA,TGMSorTGFTIR)forthestudyofraw
materials and products within the scope of research, development and quality. If DSC
monitors the evolution of the reactions, signals can be used not only for qualitative and
quantitativeanalysisbutalsoforkineticdescription.Themainchallengeisthepredictionof
thermal stability for substances submitted to extended temperature ranges and
temperature conditions for which experimentation is difficult or impossible. These
difficulties are prevalent at low temperatures (requiring a very long investigation time), as
well as under specific temperature fluctuations. The goal of this advanced numerical
approachis:
adeeperinsightintothereactioncourseofanymaterial
andanearlydetectionofthestability/reactivity
1.2.
AnalysisProcess
Afullkineticanalysisofasolidstatereactionhasatleastthreemajorsteps[18]:
(1)
experimentalcollectionofdata
(2)
computationofkineticparametersusingthedatafromstep1
(3)
prediction of the reaction progress for required temperature profiles applying

determinedkineticparameters.
UsingexperimentalDSCmeasurementsperformedontheexaminedsamples(step1)AKTS
Thermokinetics software determines kinetic characteristics of the reaction (step 2). The
calculatedkineticparametersaresubsequentlyemployedtopredictthereactionprogressof
theinvestigatedsamplesunderanygiventemperaturemode(step3).
2. Experimentalpart(STEP1)
2.1.
Selectionoftheevaluationrangeanddeterminationofthebaseline
For this examination the DSC data were used. The measured data were subsequently
exportedinASCIIformatforfurtherthermokineticinterpretationwithAKTSThermokinetics
Software. Experiments were performed in gold plated high pressure sealed crucibles at a
heatingrateof0.5,1,2,2,4and8K/min(nonisothermal)withasamplemassesbetween
6.66and11.28mg(AKTSrecommendstousethehighpressuresealedcruciblesoftheSwiss
Institute
for
the
Promotion
of
Safety
and
Security
http://www.swissi.ch/index.cfm?rub=1010). Figures 2.1 show DSC signals at different
heatingratesoftheexaminedmaterialusedforthermokineticevaluation.
53

Zone name:
Initial mass:
0.25
0.2
Curve 1
11.28 (mg)
Exo
Heat : -542.037 (J/g)
T : 80.42 and 173.91 (C)
Peak Maximum : 158.731 (C)
Peak Height : 0.273 (W/g)
Baseline Type : Tangential Sigmoid
HeatFlow (W/g)
0.15
0.1
0.05
-0.05
50
100
0-AKTS-WEBMINAR-E-LEARNING-WP / Curve 1
Zone name:
Initial mass:
0.5
0.45
0.4
0.35
150
Temperature (C)
200
Curve 2
7.56 (mg)
Exo
Heat : -585.003 (J/g)
T : 86.31 and 183.86 (C)
HeatFlow (W/g)
0.3
0.25
0.2
0.15
0.1
0.05
0
-0.05
50
54
100
150
Temperature (C)
200
250

Zone name:
Initial mass:
Curve 3
9.69 (mg)
Exo
0.8
Heat : -551.157 (J/g)

T : 92.37 and 194.23 (C)
HeatFlow (W/g)
0.6
0.4
0.2
50
100
Zone name:
Initial mass:
150
Temperature (C)
200
250
Curve 4
7.49 (mg)
Exo
1.4
1.2
Heat : -544.199 (J/g)

T : 98.65 and 205.11 (C)
HeatFlow (W/g)
1
0.8
0.6
0.4
0.2
0
-0.2
50
100
150
Temperature (C)
200
250
55

Zone name:
Initial mass:
Curve 5
6.66 (mg)
Exo
3.5
3
Heat : -551.636 (J/g)

T : 105.13 and 216.49 (C)
HeatFlow (W/g)
2.5
2
1.5
1
0.5
0
50
100
150
200
Temperature (C)
250
300
Figure2.1DSCcurveoftheexaminedmaterialrecordedat0.5,1,2,2,4and8K/min(blackcurves:simulations
afterdifferentialisoconversionalanalysis).
The selection of the evaluation range should contain the signal before and after the
occurrence of the measured thermal event as depicted in Figure 2.1 for the examined
substance.
Generallytheapplicationofstraightlineformforthebaselineisincorrect[9].Therecorded
signal results not only from the heat of the reaction but is additionally affected by the
change of the specific heat of the mixture reactantproducts during the progress of the
reaction.
With:
symbol
name
units
B(t)
Thebaseline
S(t)
Thedifferentialsignal
dt
thereactionrate
W

g
W

g
1

s
andthereactionprogress(t)()canbeexpressedas:
W W

g g 1
(S(t) B(t))
d
tend

dt
W
W
s
to (S(t) B(t))dt g g s
56
W W
s
g g
to
(t) tend

W
W
to (S(t) B(t))dt g g s
t
(S(t) B(t))dt

0 t 1 and Bt 1 t a1 b1 t t a2 b2 t
with
a1 b1 t : TangentatthebeginningofthesignalS(t).
a2 b2 t : TangentattheendofthesignalS(t).
where
Thetangentialareaproportionalbaselineisthemostuniversaltypebecauseofitscorrection
possibilities. It is created at (t) 0 and at (t) 1 by the appropriate tangents at the
beginning or the end of the measured DSC signal. It allows compensation of not only
changes in the size of cp of the reactant and product, but also of changes in their
temperaturedependency.Thistypeofbaselinescanbedescribedbythefollowingequation:
Bt 1 t a1 b1 t t a2 b2 t
with
a1 b1 t : TangentatthebeginningofthesignalS(t).
a2 b2 t : TangentattheendofthesignalS(t).
B(t) can be calculated iteratively. The convergence is achieved as soon as the relative
averagedeviationsbetweentwoiterationsaresmallerthananarbitrarilychosenvalue(for
example 1e6). An areaproportional baseline has been calculated using arbitrarily 300
iterationloopsinfig2.2.
Heat : -551.636 (J/g)
T : 105.13 and 216.49 (C)
2
1
0
HeatFlow |-bs |n |int (-)
Exo 7E-3
6E-3
5E-3
4E-3
3E-3
2E-3
1E-3
0
HeatFlow |-bs |n (-/s)
HeatFlow (W/g)
Exo
0.8
0.6
0.4
0.2
0
50
100
150
200
Temperature (C)
250
300
Figure2.2DSCcurveoftheexaminedsubstance,baselinecalculation,reactionrateandprogressillustratedfor
aheatingrateof8K/min.
Inadditiontothesigmoidbaselinetypes,AKTSThermokineticsVersion3enablesadvanced
baseline construction ten (10) different baseline types (tangential sigmoid, tangential first
point, tangential last point, sigmoid, spline, straight, horizontal first point, horizontal last
point, equal to zero baseline, staged) because the correct baseline selection is one of the
most critical parts of data treatment. Constructed baselines can be optimized numerically.
57

Standardbaselinetreatmentsarealsoaccessible,butthesoftwareoffersthemoreprecise
optionsforthetreatmentofthedata.
Itisobviousthatthebaselinedeterminationcansignificantlyinfluencethedeterminationof
thekineticparametersofthereaction.Moreover,thecorrectbaselinedeterminationshould
beintimatelycombinedwiththecomputationofthekineticparametersfortheinvestigated
reaction. Advanced mathematical procedures are therefore necessary for an objective
calculationofthemostappropriatebaselineforeachDSCsignal.
3. Determinationofthekineticcharacteristics(STEP2)
3.1.
KineticAnalysisofThermallyStimulatedProcesses
Chemical reaction rates are most often considered to be a function of only two time
dependent variables, temperature T and chemical conversion (which varies from 0 to 1
frominitiationtocompletion).TheusualrelationshipincorporatingtheArrheniusexpression
is:
d
E
f ( )
k (T ) f( ) Aexp
dt
RT(t)
Thisequationrelatesthereactionrated/dttothreedistinctkineticparameters:thepre
exponential factor A, the activation energy E, and the reaction model f(). As a set, these
threeparametersarereferredtoasthekinetictriplet.Determinationofthekinetictriplet
isacommonwaytoestablishamathematicalrelationshipbetweenthereactionrated/dt,
theextentofconversion,andthetemperature(ortime).
The extent of the conversion is determined experimentally as a fraction of the overall
changeinaphysicalquantitythatrepresentsthereactionprogressasafunctionoftimetor
temperatureT.Ifthereactionprocessisaccompaniedbyheatflow,suchasmeasuredina
DSCorotherheatflowdevice,thentheextentofconversionatTortisgivenastheratioof
the amount of evolved (or consumed) heat to the total amount of heat released (or
absorbed)intheprocess.Massloss/gain(forTG)istreatedinasimilarway.Foradiabatic
conditions the conversion can be related to the observed temperature rise relative to the
totaladiabatictemperaturerise.
A wide variety of the reaction models f() is applied in the solidstate kinetics, some of
whicharepresentedinTable3.
Reactionmodel
firstorder
secondorder
thirdorder
nthorder
powerlaw
powerlaw
powerlaw
powerlaw
powerlaw
Abbreviation:f()
F1:1
F2:(1)^2
F3:(1)^3
Fn:(1)^n
P1:^0
P2:2^(1/2)
P3:3^(2/3)
P4:4^(3/4)
Pn:n^(11/n)
Reactionmodel
AvramiErofeev
AvramiErofeev
AvramiErofeev
contractingcylinder
contractingsphere
1dimensionaldiffusion
autocatalytic
Abbreviation:f()
A1.5:1.5(1)[ln(1)]^(1/3)
A2:2(1)[ln(1)]^(1/2)
An:n(1)[ln(1)]^(11/n)
R2:2(1)^(1/2)
R3:3(1)^(2/3)
Rn:n(1)^(11/n)
D1:1/(2)
D2:[ln(1)]^1
D3:1.5[1(1)^(1/3)]^1(1)^(2/3)
(1)^n^m
Table0.1.Typicalreactionmodelsf()appliedinthesolidstatekinetics.
58

Although there is a significant number of various reaction models f(), they all can be
reducedtothreemajortypeswhenconsideringthedependenceofthereactionprogresson
the time: accelerating, decelerating and autocatalytic. Each of these types has a
characteristicreactionprofileorkineticcurve,thetermsfrequentlyusedtodescribea
dependenceoford/dtontorT.Suchprofilesarereadilyrecognizedforisothermaldata.
Therespectivevs.treactionprofilesareshowninFigure3.1.
Figure 3.1 Relationship of the reaction progress vs time for decelerating, autocatalytic and accelerating
reactionmodels.
(1)
Models of the decelerating typerepresent processes whose rate hasmaximum at

the beginning of the process and decreases continuously as the extent of
conversionincreases.Themostcommonexamplehereisareactionordermodel:
n
f 1
where n is the reaction order. Diffusion models (Table 3.1) belong also to the
deceleratingmodels.
(2)
Sigmoidal reaction models may be thought of as accelerating at the beginning

(wheniscloseto0)anddeceleratingattheend(wheniscloseto1)sothatthe
processratereachesitsmaximumatsomeintermediatevaluesoftheextentofthe
conversion. The ProutTompkins autocatalytic model is a typical example of
sigmoidalreactionmodels.Itcanbedescribedbythefollowingequation:
f 1 m
n
These reactions typically have a long induction period at the beginning, so that
thermalhistoryofthesamplemaydevelopsmallbutsignificantconversion prior
todetectionofasignal,apossibilitythatmustbeconsideredduringkineticanalysis.
Therefore, for such chemistries, beyond the usual kinetic triplet, it is necessary to
introduce the initial conversion 0 as an essential parameter in predictive
calculations.
59

(3)
Accelerating models represent processes whose rate increases continuously with

increasing the extent of conversion and reaches its maximum at the end of the
process.Modelsofthistypecanbeexemplifiedbyapowerlawmodel:
1
1
n
f n
wherenisaconstant.
Only those kinetic methods that allow considering all three types of the conversion
dependencies can be recommended as reliable methods. Sestak and Berggren (SB) have
introducedanempiricalmodel:
n
p
f m 1 ln 1
in which the values of the exponents m, n, and p characterize the contribution of the
different reaction models in the observed reaction rate. The SBmodel is generally used in
truncatedform(p=0)beingequivalenttothesocalledProutTompkinsautocatalyticmodel.
Themotivationforkineticevaluationofexperimentaldataisthepredictionofprocessrate
and reaction progress at arbitrarily chosen values of temperature T or time t under any
thermalmode (isothermal, nonisothermal, adiabatic,etc.). At lab scale the most common
nonisothermal mode is one with an imposed heating rate dT/dt = = constant, while for
longterm storage diurnal and seasonal temperature variations might be experienced.
Predictionsineithercasearereliableonlywhensoundkineticanalysismethodsareused.It
ishoweververyimportanttonotethatacommondifficultyinthecorrectinterpretationof
experimentaldataforsuchpurposesisthatevenanapparentlysimpleonestepprocessmay
in reality contain multiple steps and may require more complex elaboration of the
experimental results. This remark is illustrated in Figure 3.2 where unknown amount of
reactions can contribute to the observed, apparently simple, shape of the experimental
signal(boldline).
Figure3.2Thermokineticanalysisofheatflowsignals:thestagesandphysicochemicalreactionpathwaysare
generallyunknown.
60

With the approach proposed in AKTS software it is possible to analyze several observed
thermaleventsthatcanbethecombinationofnotalwaysknownchemicalsubstagesofthe
reaction.ForsimplestreactionslikeA Borforreactionsofseveralconsequentstepslike:
A B C D E
AKTS software uses so called unique advanced differential isoconversional techniques for
analysisandforpredictions.Thedifferentialisoconversionalapproachallowsdetermination
ofseveralvaluesofkineticparametersastheapparentactivationenergyasafunctionofthe
conversion. This unique feature enables to describe very precisely processes combining
parallel or consecutive steps because at each time point several elementary (usually
unknown) processes take place simultaneously. Therefore AKTS Software avoids
cumbersome, time consuming and sometimes very arbitrary approach introducing the
assumptionofexistenceofseveralreactionmodelsandactivationenergyvaluesnecessary
forthekineticanalysisoftheinvestigatedprocess.
More generally, the differential isoconversional method does not require an explicit
assumptionoftheformoff(),andadditionallydoesnotassumetheconstancyofAandE
during the course of the process. It is therefore generallymore precise than presupposing
knowledgeoff()andassumingthatAandEareconstantovertherangeof from0to1.
Since differential isoconversional methods do not make use of any approximations about
reaction models they are potentially very accurate and avoid the risk of wrong model
assumptionswhicharenotcorrectfromchemicalpointofviewandcanhaveverydangerous
consequencesfore.g.thermalageingorhazardsevaluation.Anotheradvantageisthatwith
the differential isoconversional approach it is possible to correctly describe kinetics of
complexreactionswithinfewminutesonly.
The isoconversional principle states that the reaction rate at a constant conversion (i.e.,
theisoconversionalrate)isonlyafunctionoftemperature.Thiscanbeeasilydemonstrated
bytakingthelogarithmicderivativeofthereactionrate(eq.1)at=constant:
d
d ln( dt )
d ln(k (T ))
d ln( f ( ))

d1
d1
d1
a
a
T
T
T a
where the subscript indicates isoconversional values, i.e., the values related to a given
extentoftheconversion .Becauseat =const,f()isalsoconstantthereforethesecond
termintherighthandsideofthepreviousequationiszero.Thus:
d
d ln( dt )
E ( )

R
d1
T a
It follows that the temperature dependence of the isoconversional rate can be used to
evaluate isoconversional values of the activation energy, E() without assuming or
determininganyparticularformofthereactionmodelf().Forthisreason,isoconversional
methods are frequently called modelfree methods. However, one should not take this
term literally. Although the methods do not need to identify the reaction model, they do
assumethattheconversiondependenceoftherateobeyssomef()model.Thisisvisible
61

withthemostcommondifferentialisoconversionalmethodofFriedman.Friedmanproposed
to apply the logarithm of the conversion rate d/dt as a function of the reciprocal
temperatureatanyconversion:
E ( )
d
f ( )
A( )exp
dt
RT(t)
ln(
d
E ( )
) ln( A( ))
ln( f ( ))
dt
RT (t )
f() is a constant in the last term at any fixed value of and the dependence of the
logarithmoftheconversionrated/dton1/Tshowsastraightlinewiththeslopem=E/R
andinterceptequaltoln(A()f())aspresentedinFigures3.3to3.5.Byextension:
ln(
d
E ( )
) ln( A' ( ))
dt
RT (t )
A' ( ) A( ) f ( )
with
Figure3.3Differentialisoconversionalanalysis.
-4
ln(Reaction rate(-/s)) (-)
-6
-8
0.8
0.90.7
0.30.2
0.4
0.95
-10
0.6
0.98
0.1
0.05
0.99
0.02
-12
0.5
2.2
2.4
1000/T (1000/K)
2.6
0-AKTS-WEBMINAR-E-LEARNING-WP / Differential isoconversional
Figure3.4Differentialisoconversionalanalysisoftheexaminedmaterial.
62
0.01
2.8

50
200
45
180
E (kJ/mol)
160
35
140
30
120
25
100
20
80
15
60
10
0
0.2
0-AKTS-WEBMINAR-E-LEARNING-WP / Activation Energy
0.4
0.6
Reaction progress alpha (-)
0.8
Ln(A(alpha)f(alpha)(1/s)) (-)
40
Figure 3.5. Activation energy and preexponential factor as a function of the reaction progress for
decompositionoftheexaminedmaterial.
Considerforexample =0.5.AseriesofDSCexperimentsmightbeperformedatdifferent
scanratesordifferentisothermaltemperatures.Atthepointineachexperimentwhen =
0.5 the corresponding isoconversional rate and temperature are measured. Thus from a
limited but sufficiently diverse set of small scale experiments one can establish the
temperature dependence of the isoconversional reaction rate. This can in turn be used to
evaluateisoconversionalvaluesoftheactivationenergyE()andamodifiedpreexponential
factorA()withoutexplicitlyassumingaparticularformofthereactionmodelf().Finally,
the differential isoconversional results can be applied to accurately simulate the reaction
rate d/dt and progress as illustrated in Figures 3.6 for the examined substance (or the
timettoreachagivenreactionprogress=thermalaging)usingtheexpressions:
t
E( )
d
t a dt
A' ( )exp
dt
RT(t)
0
0
d
E ( )

A' ( )exp
RT(t)
By extension above equation can be applied to calculate the reaction rate d/dt and
progress for milligram, kilo, and ton scales under any thermal conditions, where T(t) is
determinedbyapplyingappropriateheatbalanceequations(Figure3.7).
63
R = -0.99779
Heat = -554.8 17.4 J/g
-542 J/g
-585 J/g
-551.2 J/g
-544.2 J/g
-551.6 J/g
Reaction progress (-)
0.8
0.6
0.4
0.2
0
80
90
100
110
120
130
0-AKTS-WEBMINAR-E-LEARNING-WP / Reaction progress
140
150
160
Temperature (C)
170
180
190
200
210
220
190
200
210
220
0.007
0.006
Reaction rate (-/s)
0.005
0.004
0.003
0.002
0.001
0
80
90
100
110
120
0-AKTS-WEBMINAR-E-LEARNING-WP / Reaction rate
130
140 150
160
Temperature (C)
170
180
Figure 3.6 Reaction rates and progress (normalized DSCsignals after correctly calculated baselines and
kinetics) for the decomposition of the examined material. Experimental data are represented as color lines;
blacklinesrepresentthecalculatedsignals.Thevaluesoftheheatingratesaremarkedonthecurves.
64
Figure3.7.Frommg(shelflife)tokgandtons(thermalsafety)
Nomenclature
A
A
E
k(T)
R
t
T
DSC
3.2.
preexponentialfactor
modifiedpreexponentialfactorA()=A()f()
activationenergy
rateconstant
idealgasconstant
time
temperature
reactionprogress
initialreactionprogressatt=0
imposedheatingratedT/dt
DifferentialScanningCalorimeter
Remarksaboutisoconversionalmethods
A detailed analysis of the various isoconversional methods (i.e. the isoconversional

differentialandintegralmethods)forthedeterminationoftheactivationenergyhasbeen
reported in the literature by Budrugeac [10]. The convergence of the activation energy
values obtained by means of a differential method like Friedman method [6] with those
resultedfromusingintegralmethodswithintegrationoversmallrangesofreactionprogress
comesfromthefundamentalsofthedifferentialandintegralcalculus.Inotherwords,it
canbemathematicallydemonstratedthattheuseofisoconversionalintegralmethods(for
example: OzawaFlynnWall [78]) can yield systematic errors when determining the
activationenergies.Theseerrorsdependdirectlyonthesizeofthesmallrangesofreaction
progress overwhichtheintegrationisperformed.Theseerrorscanbeavoidedbyusing
infinitesimal ranges of reaction progress . As a result, isoconversional integral methods
turnbacktothedifferentialisoconversionalmethodsformerlyproposedbyFriedman[6].
Thedifferentialmethodsforthecalculationofthekineticparametersarebasedontheuse
ofthefollowingreactionrateequation:
d
E( )
A( ) exp
f( )
dT
RT
65

where is the heating rate, T the temperature, E() the activation energy, A() the
preexponentialfactorandf()isthedifferentialconversionfunction.
As far as isoconversional integral methods are considered, these techniques are based on
theequation:
g ( )
0
d
A( )
E( )
exp
dT
f( )
T 0
RT
T
whereg()istheintegralconversionfunction.
Theisoconversionalintegralmethodswiththeintegrationoverlowrangesofthedegreeof
conversionandrespectivelytemperature,arebasedontheequation:
g ( , )
d
A( )
E( )
exp
dT
T -
f( )
RT
whichisderivedbysupposingthatintherangeofthevariationoftheconversiondegree,
the activation energy E can be assumed constant. Obviously, the use of such an approach
leadstoaplotofEversusthedegreeofconversion .However,theactivationenergyasa
functionoftheconversionprogresslookslikeastairfunctioninwhichthelowrangesof
whereEkeepsaconstantvalueareclearlymarked.Thenumberofstairsdependsdirectlyon
thesizeof.
Inordertoevaluatetheintegralsfromthepreviousequation,onecanusethetheoremof
theaveragevalue,weobtain:
1
f( )
A( )
E( )
T
exp
RT

where
( ) x, (T T ) T T
and
T T T
Since the number of stairs (where the activation energy E is assumed constant in the
isoconversional integral methods) depends directly on the range of chosen , then an
unlimited number of stairs can be reached by making infinitesimal. For 0, we
haveT Tandf() f().Asaconsequence,thepreviousequationturnsbackintoits
differentialform:
d
E( )
A( ) exp
f( )
dT
RT
It means that the isoconversional integral methods return to isoconversional differential

method which corresponds to the Friedman approach that is described in the previous
chapter. The conversion rate expression can now be adapted to an arbitrary variation of
temperaturebyreplacing(d/dT)withd/dt.
66

4. KineticsandmilligramscaleShelflife(STEP3)
4.1.
Predictionofthereactionprogressunderanytemperaturemode
The DSC data collected during nonisothermal reaction of the examined materials with
differentheatingrateswereusedfordeterminationofthekineticparametersandthereafter
applied for rediction of the reaction extent. More generally, kinetic parameters calculated
fromthenonisothermalexperimentsmakepossiblethepredictionofthereactionprogress
foranyotherheatingrateandmoregenerallyforanytemperaturemode[1,1118]suchas:
4.2.
4.2.1.
isothermal
nonisothermal
stepwise
modulatedtemperatureorperiodictemperaturevariations
rapidtemperatureincrease(temperatureshock)
real atmospheric temperature profiles for investigating properties of e.g. low
temperaturedecomposedsubstancesunderdifferentclimates(yearlytemperature
profiles with daily minimal and maximal fluctuations. 50 climates available in the
defaultversion).
NATOnormSTANAG2895temperatureprofile:ZonesA1,A2,A3,B1,B2,B3,C0,C1,
C2,C3,C4,M1,M2,M3.
customizedtemperatureprofiles
SampleControlledThermalAnalysis
etc.
Isothermal,modulated,stepwiseandrealatmospherictemperaturemode
Isothermal
Kinetic parameters calculated from nonisothermal experiments allow prediction of the

reaction progress at any temperature mode: isothermal, nonisothermal and intermediate
intervals in the heating rate, expressed, e.g. in oscillatory temperature modes. The
prediction of the reaction progress in various temperature modes is for example given
below.
67
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
80
75
85
90
95
70
65
95
60
55
50
0.06
0.05
90
0.04
0.03
85
80
0.02
75
70
10
15
65 0.01
Reaction Rate (W/g)
Reaction Progress (-)
Iso ( Hr=-554.8Jg^-1)
60 50 0
55
20
T (h)
0-AKTS-WEBMINAR-E-LEARNING-WP / Iso (DeltaHr=-554.8Jg^-1)
Iso ( Hr=-554.8Jg^-1)
0.55
0.5
60
65
95
90
85
80
75
70
0.45
0.4
0.35
0.3
0.25
0.2
0.15
55
0.1
0.05
50
0
0.5
1.5
2.5
0-AKTS-WEBMINAR-E-LEARNING-WP / Iso (DeltaHr=-554.8Jg^-1)
3.5
T (day)
4.5
5.5
6.5
Figure4.1Calculatedreactionrateandprogress(normalizedsignals)ofthedecompositionoftheexamined
materialasafunctionoftimeunderisothermalconditions.ThevaluesofthetemperatureinCaremarkedon
thecurves.
68

4.2.2.
NonIsothermal
Ingeneral,nonisothermalscanswithdifferentheatingratesarecarriedoutwithinamuch
wider temperature range than is possible, for experimental reasons, in isothermal
conditions. This allows discernment between the different reaction paths involved in the
kinetic process because the data contain the necessary information on the time
temperature dependence of particular processes which is a prerequisite for the correct
identificationofthecomplexnatureoftheinvestigatedreaction.Computationsareusually
madewiththeresultsobtainedfromatleast5heatingratessuchas8,4,2, 1,0.5K/min.
Thismethodinsuresaratioof8/0.5=16betweenthehighestandlowestheatingrates.The
applicationofheatingratestooclosetoeachothershouldbeavoided.Iftheyareveryclose,
they become tantamount to a modelfitting analysis using single heatingrate methods.
Consequently, they may fail the required purpose as amply reported in the literature (see
international ICTAC kinetic project [25]). Our general tip for experimental data: start with
e.g. 4 K/min. It enables to rapidly examine the shape of the signals over the whole
temperature range. Then continue by 8 K/min and 2 K/min. If signal to noise ratio is not
goodfor2K/minaddmoresamplemassandcontinuewith1K/minandcontinuewith0.5
K/min. The information required for each scan is: Temperature, Time, Thermal property.
Pleasefindatthelinkbelowsuchanexampleofdataforabetterillustrationoftherequired
(ASCII
data
=
Notepad
format
=
*.txt
format):
measurements
http://www.akts.ch/faq/formatexample.zip . Note: the DSC data should be setup to
recordthemaximumnumberofdatapointspossible(i.e.donotlimitthedatacollectionin
anyway)
69

Non-iso (Tstart=30C, Hr=-554.8Jg^-1)
1
0.8
4
0.6
2
0.5
0.4
0.25
0.2
0
4
3
2.5
2
8
1.5
1
4
0.25 0.5
50
100
Reaction Rate (W/g)
3.5
0.5
0
150
200
Temperature (C)
0-AKTS-WEBMINAR-E-LEARNING-WP / Non-iso (Tstart=30C, DeltaHr=-554.8Jg^-1)
Figure 4.2 Calculated reaction rate and progress (normalized signals) of the decomposition of the examined
materialasafunctionoftimeundernonisothermalconditions.ThevaluesoftheheatingratesinK/minare
markedonthecurves.
4.2.3.
70
Stepwise
150
100
50
8E-4
6E-4
4E-4
2E-4
0
Reaction Rate (-/s)
Temperature (C)
Step (Hr=-554.8Jg^-1)
0.8
0.6
0.4
0.2
0
0
0-AKTS-WEBMINAR-E-LEARNING-WP / Step (DeltaHr=-554.8Jg^-1)
6
Time (h)
10
Figure4.3Stepwisemode.Reactionrateandprogress(normalizedsignals)oftheexaminedsubstanceasa
functionoftimeforcombinedisothermalandnonisothermaltemperaturemodes(stepwisemode).
4.2.4.
Modulated
Thekineticparameterscalculatedfromthenonisothermalexperimentsallowpredictionof
the reaction progress at any temperature mode: isothermal, nonisothermal and
intermediate intervals in the heating rate, expressed, e.g. in an oscillatory temperature
mode.Examplesofpredictionsofthereactionprogressinanoscillatorytemperaturemode
(widely applied in temperaturemodulated calorimetry) are given below. A temperature
modulated mode increases the basic understanding of the characterization of materials in
different ways. Presented examples indicate that the prediction of some of the thermal
decompositiondependsontheexacttemperatureprofileofthesample.
Inthenextfigures,thearithmeticmeantemperature(30C)oftheoscillatorytemperature
modes is the same for all calculations, however, the differences in the amplitudes greatly
influencethereactionprogressandrate.Thepredictionofthedecompositionat30Cwith
20Camplitudeand24hperiodispresentedbelow.
71

Modulated (24h, 0Kmin^-1, Hr=-554.8Jg^-1)
40
30
20
10
0.003
3020C
0.002
0.001
300C
0.5
3020C
0.4
Reaction Rate (W/g)
Temperature (C)
50
300C
0.3
0.2
0.1
0
0
0.5
1
Time (month)
0-AKTS-WEBMINAR-E-LEARNING-WP / Modulated (24h, 0Kmin^-1, DeltaHr=-554.8Jg^-1)
1.5
Figure4.4Calculatedreactionprogress(normalizedsignals)ofthedecompositionoftheexaminedsubstance
asafunctionoftimeunderisothermal(30C)andoscillatory(30C20C,24hperiod)temperatureconditions.
Presentedfigureillustratestheinfluenceoftheoscillatorytemperaturemodeonthereactionprogress.
4.2.5.
Worldwide
REALATMOSPHERICTEMPERATUREMODE:Predictionofthereactionrateandprogressfor
real atmospheric temperature profiles which allows the investigation of the properties of
lowtemperature decomposed substances under different climates (yearly temperature
profiles with daily minimal and maximal fluctuations). The important goal of the
investigation of thermal decomposition kinetics is the need to determine the thermal
stability of substances, i.e. the temperature range over which a substance does not
decompose with an appreciable rate. The correct prediction of the reaction progress of
materials which are unstable under ambient conditions (food, drugs, some polymers, etc.)
requiresaccurateapplicationinthecalculationsofboth:
thekineticparameters
theexacttemperatureprofileforagivenclimate
Calculations can be achieved for any fluctuation of the temperature which makes possible
thepredictionsofthermalstabilitypropertiesforvaryingclimates.Exactconsiderationinthe
calculations of daily minimal and maximal temperature variations of worldwide climates
provides very valuable insight when interpreting and quantifying the reaction progress of
materials subjected to atmospheric conditions. This feature is interesting for low
temperaturedecomposedsubstance.
72
30
25
20
15
10
5
0
6E-4
5E-4
USA (Miam i)
4E-4
3E-4
2E-4
Sw itzerland (Zurich)
1E-4
0
0.5
USA (Miam i)
Reaction Rate (W/g)
Temperature (C)
Worldw ide (Hr=-554.8Jg^-1)
Sw itzerland (Zurich)
0.4
0.3
0.2
0.1
0
0
0.5
1.5
2.5
3
3.5
Time (year)
4.5
5.5
6.5
0-AKTS-WEBMINAR-E-LEARNING-WP / Worldwide (DeltaHr=-554.8Jg^-1)
Figure4.5Top:Averagedailyminimalandmaximaltemperaturesrecordedforeachdayoftheyearbetween
1961and1990(ZurichandMiami).Middleandbottom:Reactionrateandprogress(DSC,normalizedsignals)of
theexaminedsubstanceasafunctionoftimefortheZurichandMiamitemperatureprofiles.
73

4.2.6.
STANAG2895
The application of kinetics makes possible the precise prediction of the reaction progress
undertemperaturemodecorrespondingtorealatmosphericchangesaccordingtoSTANAG
2895.Duringtheirproduction,storageorfinalusage,chemicalsoftenundergotemperature
fluctuations.Duetothefactthatthereactionratevariesexponentiallywiththetemperature
itisimportantthatpredictivetoolscouldenablethesimulationofthereactionprogressin
therealconditions,asasmalltemperaturejumpcaninduceasignificantincreasingreaction
rate. Since thermokinetics allows a precise description of the decomposition process, the
reaction rate can be predicted for any temperature profile, such as stepwise variations,
oscillatoryconditions,temperatureshock,orevenrealatmospherictemperatureprofiles.To
illustrate the importance of the influence of the temperature fluctuations on the reaction
rate, the simulations of the reaction progress can be carried out for climatic categories
according to STANAG 2895. This document describes the principal climatic factors which
constitute the distinctive climatic environments found throughout the world and provides
guidanceonthedraftingoftheclimaticenvironmentalclausesofrequirementdocuments.
ThetemperatureprofilesaccordingtoSTANAG2895areimportantforthepredictionofthe
influence of the temperatures on the slow decomposition of e.g. high energetic materials
such as propellants. The precise prediction of the reaction rate and progress requires the
knowledge of the diurnal and annual variations of the meteorological and storage /transit
temperatures. The meteorological temperature can represent e.g. the ambient air
temperaturemeasuredunderstandardconditions,whereasstorageandtransittemperature
representstheairtemperaturemeasuredinsidetemporaryunventilatedfieldsheltere.g.in
railway boxcar which is exposed to direct solar radiation. Applying the advanced kinetic
software it is possible to calculate the reaction progress using the kinetic parameters
determined from thermoanalytical signal and taking into account the dependence of the
temperature changes depicted in STANAG 2895. This feature is interesting for low
temperaturedecomposedsubstance.
74
Temperature (C)
STANAG (A2 diurnal seasonal, Hr=-554.8Jg^-1)
40
30
20
10
1.25E-3
1E-3
7.5E-4
5E-4
2.5E-4
0
0.5
Reaction Rate (W/g)
0.4
0.3
0.2
0.1
0
0
6
Time (month)
10
12
0-AKTS-WEBMINAR-E-LEARNING-WP / STANAG (A2 diurnal seasonal, DeltaHr=-554.8Jg^-1)
Figure4.6Predictionsofthereactionrateandprogressoftheexaminedsubstanceasafunctionoftimedueto
thetemperaturevariationsrepresentedbythediurnalstoragetemperatureprofilesofclimaticcategoryA2of
STANAG2895.
4.2.7.
Customized
TheexperimentaldatacollectedbymeansofDSCenablesthepredictionoftheshelflifeof
substancesatanytemperaturemodeandeventheprecisesimulationofthereactionatany
temperature profile close to the ambient temperature. To illustrate the importance of the
influence of the temperature fluctuations on the reaction course, the simulations of the
reaction progress can be carried out even for storage temperature profile corresponding
temperature fluctuations measured during the sample storage as presented in the next
figure.
75
30
25
20
15
10
5
4E-4
3E-4
2E-4
1E-4
Reaction Rate (W/g)
Temperature (C)
Customized (Hr=-554.8Jg^-1)
0.4
0.3
0.2
0.1
0
0
0.5
1.5
2.5
3.5
4
4.5
Time (month)
0-AKTS-WEBMINAR-E-LEARNING-WP / Customized (DeltaHr=-554.8Jg^-1)
5.5
6.5
7.5
8.5
Figure4.7 Example ofprediction of the reaction rate and progressof the examined substance formeasured
temperatureprofiles.
4.2.8.
SampleControlledThermalAnalysis
AKTSThermokinetics Software can optimize temperature program in such a way that it

allows obtaining the value of the reaction rate set by the user. It is often the case in
industrialapplications,thatinordertoachieveacertaincharacteristicprofile,highqualityor
specific sample properties, thermal reaction rates should be very carefully controlled, not
exceedinge.g.acertaincriticalvalue.Thismethodofcontrollingreactionrateisknownas
SampleControlledThermalAnalysis.
76

SignificantisthecontrolofareactionratebyconstantlyincreasingPartialAreabetweena
signalandthebaseline(forDSCandDTA),inordertoforcee.g.theuniformcuringofepoxy
resins.Therefore,aspowerfultoolforthesolutionofsuchproblems,AKTSThermokinetics
contains simulation through kinetic analysis of rate controlled mass change for
thermogravimetricsignals,ratecontrolledconversionand/orratecontrolledpartialareafor
DSC measurements. The target of this analysis is to provide such temperature profiles for
achievinge.g.TGAcurveswithconstantmasslossratesorDSCcurveswithratecontrolled
heatrelease(orconsumption).
200
SCTA Step
190
Temperature (C)
180
170
Temperature segmentation
160
150
140
130
120
0.1
1
0.8
0.095
0.6
0.4
0.09
0.2
0.085
0
0
20
40
60
80
Reaction Rate (W/g)
110
100
Time (min)
0-AKTS_WEBMINAR-E-LEARNING-WP / SCTA Step
SCTA Step
1
0.8
0.6
0.4
0.2
0
0.095
0.09
Reaction Rate (W/g)
0.1
0.085
100
120
140
160
0-AKTS_WEBMINAR-E-LEARNING-WP / SCTA Step
180
200
Temperature (C)
220
240
260
280
Figure 4.8 Example of prediction of rate controlled conversion (Sample Controlled Thermal Analysis) of the
examinedsubstance.
77

5. KineticsandscaleupSafetyanalysis(STEP3)
Calculationofadiabaticthermaltransformationandheataccumulationfromnon
isothermalDSCmeasurements
5.1.
Introduction
The precise prediction of reaction progresses in adiabatic conditions is necessary for the
safety analysis of many technological processes. Calculations of an adiabatic temperature
time curve for the reaction progress can also be used to determine the decrease of the
thermal stability of materials during storage at temperatures near the threshold
temperaturefortriggeringthereaction.Duetoinsufficientthermalconvectionandlimited
thermal conductivity, a progressive temperature increase in the sample can easily take
place,resultinginathermalrunaway.
Several methods have been presented for predicting reaction progress of exothermic
reactions under heat accumulation conditions [1432]. However, because decomposition
reactions usually have a multistep nature, the accurate determination of the kinetic
characteristics strongly influences the ability to correctly describe the progress of the
reaction.Theuseofsimplifiedkineticmodelsfortheassessmentofrunawayreactionscan,
ononehand,leadtoeconomicdrawbacks,sincetheyresultinexaggeratedsafetymargins.
On another hand, it can cause dangerous situations when the heat accumulation is
underestimated. For selfheating reactions occurring adiabatically, incorrect kinetic
descriptionoftheprocessisusuallythemainsourceofpredictionerrors.
5.2.
5.2.1.
The kinetic based approach for the determination of Time to Maximum Rate
underadiabaticconditions(TMRad)
Concept
Kinetic parameters calculated from DSC measurements are used for describing thermal
behavioroflargeramountofsubstancebecausethekineticsofanyreactionisthesamefor
tenmilligramsofsubstanceandforoneton.However,duringscaleuptwoimportantfactors
havetobeconsidered:
(i)
(ii)
the application of advanced kinetics, which properly describes the complicated,

multistagecourseofthedecompositionprocess,
theeffectofheatbalanceintheenergeticsystem,asthesamplemassisincreased
byafeworderofmagnitudecomparedtothethermoanalyticalexperiments.
Because decomposition reactions usually have a multistep nature, the isoconversional

analysis enables a more accurate determination of the kinetic characteristics compared to
simplified kinetic based approach that are essentially based on simplified kinetics
assumptionlikeletsassumethatthereactioniszeroorderetc
TheapplicationoftheDSCdataforthesimulationoftheadiabaticmeasurementsseemsto
be, for the first glance, not obvious. However, the closer look on the differences and
similaritiesoftheprocessesoccurringunderdifferentconditionsoftheheatexchangeallows
to understand that the adiabatic properties such as selfheating rate or time to maximum
ratecanbecorrectlydeterminedfromtheDSCresultsobtainedorisothermally,orbetter,at
different heating rates. The main difference between DSC run and fully adiabatic process
lays in the conditions of the heat exchange. Due to the fact that in the thermoanalytical
experimentstheheatevolvedduringreactionisfullyexchangedwiththeenvironments,the
heatingratesunderwhichtheexperimentarecarriedoutcanbearbitrarilychosen.Inturn,
78

afterdeterminationofthekineticparametersfromtheresultsoffewexperimentsdonewith
differentheatingrates,onecanpredictthereactionrateunderanytemperatureramp.
Duetothetotallydifferentheatexchangeconditionsinadiabaticconditionstheheatingrate
of the process (called now selfheating rate) cannot be controlled anymore, being
dependentonlyonthekinetics,adiabatictemperatureriseandfactor.However,evenin
this case we can simulate the reaction rate. The scheme of the general idea of this
procedureispresentedinthenextfigure.
Figure5.1Schemeofthepresentationoftheadiabatictemperatureriseintheformoffoursequencesofthe
timeperiodstinwhichtheheatingratesareconstantandamountinturnto1,2,3and4.
Letusassumethatthetemperatureincreaseunderadiabaticconditionsinthecoordinates
time temperature can be presented schematically as in Fig.5.1 in the form of four
sequences of the short periods of time t in which the heating rate is constant. In time
periods0t1,t1t2,t2t3and,finally,t3t4theheatingratesare 1, 2, 3and 4,respectively.
Asshownpreviously,onecaneasilypredictthereactionrateunderany value.Duringthe
temperaturechangeschematicallypresentedinFig.5.1,thereactioncoursecanthereforebe
calculated as a sequence of processes occurring at known heating rates 1 4. Using the
infinitesimal t values for the description of the selfheating rate one can predict the
reaction course under the adiabatic temperature change. The process occurring under
adiabatic temperature rise is expressed as a succession of an infinite number of processes
occurringatconstantheatingrateswhichcannowbeeasilycalculatedbydescribedmethod.
5.2.2.
Heattransfermechanisms
Heat transfer deals with systems that lack thermal equilibrium, and thus it is a non
equilibrium phenomenon. The basic requirement for heat transfer is the presence of a
temperaturedifference.Heatistransferredinthedirectionofdecreasingtemperature.The
temperaturedifferenceisthedrivingforceforheattransfer.Therateofheattransferina
certaindirectiondependsonthemagnitudeof thetemperaturegradientinthatdirection.
Thelargerthetemperaturegradient,thehighertherateofheattransfer.
Heatcanbetransferredinthreebasicmodes:
Conduction,
79
Convection,
Radiation.
Allmodesofheattransferrequiretheexistenceofatemperaturedifference.Allmodesare
fromthehightemperaturemediumtoalowertemperatureone.
5.2.2.1. Conduction
Conductionisthetransferofenergyfromthemoreenergeticparticlesofasubstancetothe
adjacent less energetic ones as a result of interactions between the particles. Conduction
can take place in solids, liquids, or gases. In gases and liquids conduction is due to the
collisionsanddiffusionofthemoleculesduringtheirrandommotion.Insolidsconductionis
duetothecombinationofvibrationsofthemoleculesinalatticeandtheenergytransport
byfreeelectrons.
Figure5.2Heattransferbyconductioninsolids,liquidsorgases.
Therangeofthermalconductivitiesisenormous.AsweseefromFig.5.2,variesbyafactor
of about 105 between gases (poor heat conductor or insulator) and diamond (good heat
conductor)atroomtemperature.Oneshouldstudyandremembertheorderofmagnitude
ofthethermalconductivitiesofdifferenttypesofmaterials.Thiswillbeahelpinavoidingin
futurecomputations,anditwillbeahelpinmakingassumptionsduringproblemsolving.
Figure 5.3 Thermal conductivities of materials. Pure crystals and metals have the highest thermal
conductivities,andgasesandinsulatingmaterialsthelowest.
5.2.2.2. Convection
Convectionisthemodeofenergytransferbetweenasolidsurfaceandtheadjacentliquidor
gasthatisinmotion.Convectioniscommonlyclassifiedintothreesubmodes:
80
Forcedconvection,
Natural(orfree)convection,
Changeofphase(liquid/vapor,solid/liquid,etc.)
5.2.2.3. Radiation
Radiationistheenergyemittedbymatterintheformofelectromagneticwaves(orphotons)
asaresultofthechangesintheelectronicconfigurationsoftheatomsormolecules.Heat
transferbyradiationdoesnotrequirethepresenceofaninterveningmedium.Radiationis
emittedbybodiesbecauseoftheirtemperature.
5.2.3.
KineticbasedapproachDeterminationoftheTMRad
Inheattransferproblemsitisconvenienttowriteaheatbalanceandtotreattheconversion
ofchemicalenergyintothermalenergyasheatgeneration.Theenergybalanceinthatcase
canbeexpressedas
.
Q in Q out
Net heat transfer
Qr
Heat generation
Q
t
Energy storage
The solution of the problem leads to a thermal stability diagram, i.e. for each starting
temperaturetheTimetoMaximumRateunderadiabaticconditions(TMRad)canbeobtained
easily.
5.2.3.1. Batchreactorincaseofcoolingfailure
The energy balance of an exothermic reaction taking place in a batch reactor can read as
follow
dT
dT
d
M s c p , s s M c c p ,c c
UA(Tenv Ts ) M s (H r )
dt
dt
dt
Net heat transfer

Heat generation
Energy storage
with M: mass, cp: specific heat, T: temperature, U: overall heat transfer coefficient, A:
contact surface between the sample and the container, Hr : heat of reaction, indices c, s
and env: container, sample and environment, respectively. In case of cooling failure the
overall heat transfer coefficient U=0 for achieving the adiabatic conditions. In a fully
operationally adiabatic environment all the heat release goes to heat the sample and the
container.Ifthereisthermalequilibriumwithinthesolutionandthewall
Tc (t ) Ts (t ) =>
dTc dTs
dt
dt
then the whole system will have the same temperature rise rate and we can simplify the
aboveequationto:
M s C p,s
dTs
(H r ) d
dt M c C p ,c M s C p , s C p , s dt
81

thatcanberewrittenas
dTs 1
d
Tad , true
dt
dt
with:
theadiabatictemperaturerise:
Tad , true
thephifactor:
thereactionrate:
dt
(H r )
C p,s
M c C p ,c M s C p , s
M s C p,s
Forbatchreactorwithlargesizes(>1m3),itcanbeassumedthatMs>>Mc(jacket)sothatwe
obtain
dTs
d
Tad ,true
dt
dt
Ts f (t , kinetics, H r , c p ,s )
(with 1)
Incaseofisoconversionalanalysiswehave:
E ( )
d
with A' ( ) A( ) f ( )
A' ( )exp
dt
RT(t)
Note,forcomparison,incaseofsimplifiedzeroorderkineticassumptionwewouldhave:
d
E

A exp
dt
RT(t)
It comes from the above equations that one can use the kinetic based approach for
predicting the reaction progress (t) and rate d/dt as well as the development of the
temperatures Ts(t) and dT/dt and adiabatic induction times at any selected starting
temperatures.
5.2.3.2. Adiabaticcalorimeter
There are several issues that need to be taken into consideration for the examination of
adiabaticconditionsorreconstructinganAcceleratingRateCalorimeterexperimentstarting
fromthekineticbasedapproach.Theenergybalanceincaseofanadiabaticcalorimetercan
beexpressedasbefore
dT
dT
d
M s C p , s s M c C p ,c c
dt
dtdt
Net heat transfer

Heat generation
Energy storage
Because the presence of a temperature difference leads to heat transfer, an adiabatic

calorimeter constantly attempts to achieve equilibrium states by keeping Tenv = Ts. As a
82

consequence there is no driving force for heat transfer and the chemical reactions run
adiabatically.Weobtainasbefore
dTs 1
d
Tad , true
dt
dt
Ts f (t , kinetics, H r , c p , )
However, one has to take into account the thermal inertia (or factor) to consider the
effectofthevesselsinertiai.e.thereactionheatthatistransferredinpartintoheatingof
the bomb. It can be observed that the factor influences the simulation of an ARC
experiment.Thefactorinfluences:
the
Tad ,measured
Tad ,measured
because
it
comes
from
above
description
that
1
Tad , true
andtheTMRadindifferentlevelsdependingonthetypeofdecompositionkinetics.
Usually, the standard method of correcting the time for the reaction under adiabatic
TMRad ,measured
conditionsis TMRad , true
.Thisishoweveranapproximation.
5.2.3.3. Dewar
In dewar tests we encounter walls that consist of layers of different materials. The
energy balance in that case can be handled just like exothermic reaction in the adiabatic
calorimeterorbatchreactorincaseofcoolingfailure.
dT
dT
d
UAd (Tenv Ts ) M s (H r )
M s c p , s s M c c p ,c c
dt
dt
dt
Net heat transfer

Heat generation
Energy storage
Thenetheatratethroughathreelayeredwall(glassvacuumglass)ofthicknessesL1,L2and
L3withconvectiononbothsidesispresentedinthenextfigure.
glass
glass
vacuum
T3
T4
air
h1
T1
3 h2
L2
L3
T2
L1
Rconv ,1
reaction
mixture
Rwall ,1
Rvacuum , 2 Rwall , 3
R conv , 2
83

Figure 5.4 Schematic description of a Dewar. The net heat rate through a threelayered wall (glassvacuum
glass)oflengthsL1,L2andL3withconvectiononbothsides.
Therateoftheheattransferbetweenairandthewallattheoutersurfaceisbyconvection.
Theheattransferthroughthethreelayeredwallisconduction.Ifthereactionmixtureisa
liquid,heattransferbetweentheliquidandthewallattheinnersurfaceisbyconvection.
Rateofheatconvectionintothewall,rateofheatconductionthroughthewallandrateof
heatconvectionfromthewallcanbeexpressedas:
.
T T3
T T4
T T2
1 A 1
2 A 2
3 A 3
L1, glass
L2,vacuum
L3, glass
Rate of heat convection into the wall
h1 A(Tenv T1 )
h2 A(T4 Ts )
rate of heat convection from the wall
rate of heat conduction through the wall
In an analogous manner to Newtons law of cooling it is sometimes convenient to express

heattransferthroughamedium UA(Tenv Ts ) usingthethermalresistanceconcept:
.
.
Q
(Tenv Ts )
Q Rtotal
UA
Where
Rtotal
L
L
L
1
1
1 2 3
h
A
A
h
A
1
1
2
3
2

Rconv ,1
Rglass ,1
Rvacuum, 2
Rconv , 2
Rglass , 3
Ash1<<h2,1<<2and3<<2(becausevacuum<<glass),itcanbeassumedthat
Rtotal
L
1
2
h1 A
2 A
Rconv ,1
Rvacuum, 2
Inaddition,Ms>>Mc(glass)sothatafterinsertionintotheenergybalance
dT
d
M s c p,s s
dt
dt
Net heat transfer

Heat generation
Energy storage
andsimplificationwecanwrite
dTs
UA
d
(Tenv Ts ) Tad ,true

dt M s c p , s
dt
Ts f (t , kinetics, H r , c p , s , M s , A, U )
UA
Notethat
1
Rtotal
1
L
1
2
h1 A 2 A
Rconv ,1
84
Rvacuum, 2

In case of large adiabatic temperature rise Tad and because the total resistance Rtotal is
importantbecauseofthevacuumwecanassumethat U Dewar 0 andweobtain
dTs
d
Tad ,true
dt
dt
whichleadsbasicallytothesameresultsasbeforeforexothermicreactionintheadiabatic
calorimeterorbatchreactorincaseofcoolingfailure.
5.2.3.4. Constructionofathermalsafetydiagram:runawaytimeasafunctionofprocess
temperature under adiabatic conditions (TMRad = f(T)) for the examined
substance
The decomposition of the examined substance follows an exothermal process. Using the
heatofreaction(Hr =554.817.4 J/g)andassumingaheatcapacityCp=1.5J/(gK),one
cancalculatethereactionprogressduetoselfheatingforanyTad=(Hr)/Cp/.Notes:
(i)
CpcanbeeasilydeterminedwithCalistoSoftware
http://www.akts.com/calistooverview.html
http://www.akts.com/livevideocalistoprocessingvideocpregression.html
(ii)
Cpvaluehasbeenassumed=1.5J/(gK)forFigure5.5.
As long as thermal safety analysis is concerned, adiabatic induction time is defined as the
timewhichisneededforselfheatingfromthestarttemperaturetothetimeofmaximum
rate(TMRad)underadiabaticconditions.DependingonthedecompositionkineticsandTad,
thechoiceofthestartingtemperaturesstronglyinfluencesthetimetorunawayandtherate
of the temperature evolution under adiabatic conditions. Figure 5.5 presents the starting
temperatureandcorrespondingadiabaticinductiontimeTMRadrelationship.
85

Safety diagram ( Hr=-554.817.4J/g, Cp=1.5J/g/K, Phi=1)
90
85
Temperature (C)
80
75
70
65
TInitial, Tad=369.9C
60
X : 24 Y : 52.78
55
TInitial+1C, Tad=381.5C
TInitial-1C, Tad=358.3C
50
0
10
15
20
Time (h)
25
30
35
0-AKTS-WEBMINAR-E-LEARNING-WP / Safety diagram (DeltaHr=-554.817.4J/g, Cp=1.5J/g/K, Phi=1)
Safety diagram ( Hr=-554.817.4J/g, Cp=1.5J/g/K, Phi=1)
90
85
Temperature (C)
80
75
70
65
TInitial, Tad=369.9C
60
X : 24 Y : 52.78
55
TInitial-1C, Tad=358.3C
TInitial+1C, Tad=381.5C
50
0
10
15
20
Time (h)
25
0-AKTS-WEBMINAR-E-LEARNING-WP / Safety diagram (DeltaHr=-554.817.4J/g, Cp=1.5J/g/K, Phi=1)
30
35
Figure 5.5 Thermal safety diagram: Starting temperature and corresponding adiabatic induction time TMRad
relationshipoftheexaminedmaterial.Thechoiceofthestartingtemperaturesstronglyinfluencestheadiabatic
inductiontime.Hr J/gandTad=(Hr)/CP/=Cfor=1andCP=1.5J/g/C.
86

Hr=(554.8)+(17.4)J/g
Temperature
(C)
(TProcess)
89
88
87
86
85
84
83
82
81
80
79
78
77
76
75
74
73
72
71
70
69
68
67
66
65
(*)64
Cp=1.5J/g/K
Time(h)
(TMRadforTProcess
andTad=369.9C)
0.95
1.03
1.12
1.21
1.32
1.43
1.55
1.69
1.83
1.99
2.17
2.36
2.57
2.8
3.05
3.33
3.63
3.97
4.34
4.74
5.18
5.67
6.21
6.8
7.46
(*)8.18
Tad=(Hr)/Cp=369.911.6C
Time(h)
(TMRadfor
TProcess+1CandTad=381.5C)
(pessimistic)
Time(h)
(TMRadfor
TProcess1CandTad=358.3C)
(optimistic)
0.87
0.94
1.02
1.1
1.19
1.29
1.4
1.52
1.66
1.8
1.96
2.13
2.32
2.52
2.75
3
3.27
3.57
3.89
4.25
4.65
5.08
5.56
6.09
6.67
(*)7.31
1.05
1.14
1.24
1.34
1.46
1.58
1.72
1.87
2.03
2.21
2.4
2.62
2.85
3.11
3.39
3.71
4.05
4.42
4.83
5.29
5.79
6.34
6.94
7.61
8.35
9.16
(*)Meansthatif =1andCp=1.5J/g/CthedeterminedTMRadisabout8hours(8.18h)foraninitialtemperatureof
about64C(forthattemperatureamoreconservativevalueforTMRadisabout7.31h)
63
62
61
60
59
58
57
56
55
54
(**)53
8.97
9.85
10.83
11.9
13.09
14.4
15.86
17.48
19.27
21.26
(**)23.47
8.02
8.8
9.66
10.61
11.66
12.82
14.11
15.53
17.11
18.87
(**)20.81
10.06
11.05
12.15
13.37
14.72
16.21
17.86
19.7
21.73
23.99
26.51
(**)Meansthatif =1andCp=1.5J/g/CthedeterminedTMRadisabout24hours(23.47h)foraninitialtemperatureof
about53C(forthattemperatureamoreconservativevalueforTMRadisabout20.81h)
52
51
50
25.92
28.65
31.69
22.97
25.37
28.03
29.3
32.42
35.88
Table 5.1 Thermal safety table: Starting temperatures and corresponding TMRad for the examined material
underadiabaticheataccumulationconditions.
87

Figure 5.6 illustrates the applications of the above equations for the simulation of the
thermal behaviour under adiabatic conditions. The simulated Ttime relationships are
presentedwithastartingtemperatureofabout52.78CleadingtoTMRadof24h.
TMRad (Hr=-554.817.4J/g, Cp=1.5J/g/K, Phi=1)
450
TInitial=52.78C, Tad=369.9C
400
Temperature (C)
350
300
250
200
150
100
50
10
15
Time (h)
20
0-AKTS-WEBMINAR-E-LEARNING-WP / TMRad (DeltaHr=-554.817.4J/g, Cp=1.5J/g/K, Phi=1)
25
Figure 5.6 Adiabatic runaway curves with Hr = 554.817.4 J/g and Cp = 1.5 J/g/C showing the confidence
intervalfortheprediction:Tbegin=52.781C.Tad=(Hr)/CP/=369.911.6Cfor=1.
Note that isothermal conditions can be numerically retrieved by setting an exceptionally

largevalueof tomaketheadiabatictemperaturerise Tadinsignificant.Ifthe isvery
highallheatreleasedbythereactionisdissipatedtothesurrounding.Asaconsequence,the
sampletemperatureremainsconstanti.e.isothermal:
dTs 1
d
Tad , true
dt
dt
forverylargevaluesofwehave
dTs
0 and Ts ( 0) Ts ( 1) Tisothermal
dt
88
TMRad (TInitial=52.78C, Hr=-554.8Jg^-1, Cp=1.5Jg^-1K^-1)
Phi=1, Tad=369.9C
350
300
250
200
Phi=2, Tad=184.9C
150
100
Phi=10000000, Tad=0C
50
Phi=1, Tad=369.9C
1
0.8
Phi=2, Tad=184.9C
0.6
Phi=10000000, Tad=0C
0.4
0.2
Temperature (C)
400
0
0
0.5
1.5
2.5
3.5
4
Time (day)
4.5
5.5
0-AKTS-WEBMINAR-E-LEARNING-WP / TMRad (TInitial=52.78C, DeltaHr=-554.8Jg^-1, Cp=1.5Jg^-1K^-1)
6.5
Figure 5.7 Comparison between the reaction progress and reaction rate under isothermal conditions
(T=52.78C,E)andtheadiabaticrunawaycurvewithastartingtemperatureof52.78Cwithand
1(TMRadof24h),respectively(Hr=554.817.4J/gandCp=1.5J/g/C).
The selfheat rate curves under adiabatic conditions can be calculated similarly (see figure
5.8).Itcanbeobservedthataselfheatrateof0.02K/min(with,whichcorresponds
tothetypicaldetectionlimitofadiabaticcalorimeters,occursafterabout17hours,itmeans
7 hours before TMRad of 24 h for an initial process temperature of 52.78C. It can be also
seenfromthesimulationthatatthattimethereactionprogressamountsalreadytoabout
0.022(about2.2%)(Fig.5.8).
89
400
350
300
250
200
150
100
50
1.00E+6
1.00E+5
1.00E+4
1.00E+3
1.00E+2
1.00E+1
1.00E+0
1.00E-1
1.00E-2
1.00E-3
t: 16.78 (h)
T: 60.9 (C)
y: 2E-2 (C/min)
Reaction Rate (C/min)
Temperature (C)
TMRad (TInitial=52.78C, Hr=-554.8Jg^-1, Cp=1.5Jg^-1K^-1, Phi=1, Tad=369.9C)
0.8
0.6
t: 16.78 (h)
T: 60.9 (C)
y: 0.022 (-)
0.4
0.2
0
0
10
15
20
25
Time (h)
0-AKTS-WEBMINAR-E-LEARNING-WP / TMRad (TInitial=52.78C, DeltaHr=-554.8Jg^-1, Cp=1.5Jg^-1K^-1, Phi=1, DeltaTad=369.9C)
Figure 5.8. Adiabatic runaway curve with TMRad = 24h and corresponding reaction progress and self heating
ratecurveasfunctionoftime(Hr=554.817.4J/gandTad=(Hr)/CP/=369.911.6Cfor=1andCP=1.5
J/g/C).
Similarcalculationscanbeperformedfordifferent factors(seefigures5.9)foraninitial
temperatureofabout52.78C.
90

Phi=1, Tad=369.9C
400
350
Phi=1.5, Tad=246.6C
Temperature (C)
300
250
Phi=2, Tad=184.9C
Phi=2.5, Tad=147.9C
200
150
100
50
0
10
15
20
25
Time (h)
30
35
40
45
50
1E+5
Reaction Rate (C/min)
1E+4
Phi=1, Tad=369.9C
1E+3
1E+2
Phi=1.5, Tad=246.6C
1E+1
1E+0
Phi=2, Tad=184.9C
1E-1
Phi=2.5, Tad=147.9C
1E-2
100
150
Temperature (C)
200
250
300
350
400
Figure5.8Thermalbehaviorofexaminedmaterialunderadiabaticconditionsfordifferentfactors.Adiabatic
runawaycurves(top)andselfheatratecurves(bottom)
Tbegin=18.04C,Hr=554.817.4J/gandCp=1.5J/g/C
Tad=(Hr)/cp/=369.9Cfor=1
Tad=(Hr)/cp/=246.6Cfor=1.5
Tad=(Hr)/cp/=184.9Cfor=2
Tad=(Hr)/cp/=147.9Cfor=2.5
91

6. SelfAcceleratingDecompositionTemperature(SADT)(STEP3)
6.1.
Introduction
Additionallytothepredictionofthereactionprogressatanytemperatureprofileinmgscale
andunderadiabaticconditions,thesimulationsofthermalpropertiesinkgscalesuchasSelf
Accelerating Decomposition Temperature (SADT) can be carried out. The DSC signals of a
materials decomposition are processed using AKTS Thermokinetics softwares unique
numericaltechniquestocreateanaccuratekineticmodel.Subsequently,thiskineticmodelis
used by the AKTSThermal Safety Software to predict the possible thermal runaway for a
specificcontainertypeandsizeunderanyglobaltemperatureenvironment.
The method for predicting the thermal behaviour of the energetic materials such as the
determinationofSADTstronglydependsonthesamplemassduetothesignificantinfluence
of the heat generated during the reaction course. At the mgscale, all the evolved heat
dissipatestothesurroundingsanddoesnotaffectthetemperatureoftheheatedmaterial.
Whereas at the tonscale, the system can be considered adiabatic, because almost all
generated heat remains in the sample and there is potential for a thermal runaway
decomposition.Fromapracticalperspectiveforthekgscale,thetemperaturechangeofthe
testmaterialresultsfromtwodifferentprocessesthattogetherdeterminetheheatbalance,
whichisdefinedbytheheatgeneratedduringthethermaldecompositionandheatlossto
theenvironment.Therateofheatgeneratedduringanexothermicdecompositionincreases
exponentially as the temperature rises but the rate of the heat loss remains in a linear
manner.Therefore,aclearunderstandingoftheheattransfermechanismisnecessaryforan
accuratedeterminationofSADT.
6.2.
Equivalentsphericalradius
SADT can be calculated for simple geometries such as spheres or infinite cylinders. These
sample holders applied for calculations do not exactly correspond to the real containers
geometries. However, the use of an equivalent radius representing all possible container
geometrieswithequivalentsphericalvolumesallowsinthefirstreasonableapproximationfor
thedeterminationoftheSADT:
1
Ms
3 3
rs,eq= V s
withVs=
s
4
Where: rs,eq
6.3.
= theequivalentsphericalradiuscorrespondingtothesamplevolumeinthe
container
Vs
= samplevolume
Ms
= samplemass
= sampledensity
s
Theenergyequation
Whenheatistransferredtosurroundingenvironmentthetemperatureprofilewithinasolid
bodyoraliquiddependsupontherateofheatgeneration,itscapacitytostorethepartof
thisheat,andtherateofheattransfertoitsboundaries.Theenergybalanceoveravolume
elementcanbeexpressedas
.
Q in Q out
Net heat transfer
92
Qr
Heat generation
Q
t
Energy storage

andfromFourierslaw
dT
s c p,s s
dt
Heat generation
heat
2Ts
qr
conduction
Energy storage
As the chemicals stored in containers can be solids or liquids, we must extend the heat
conduction equation to allow for the motion of the fluid. After some restrictive assumptions
[27],weobtaintheenergyequation:
.
T s
s c p,s
u s Ts s 2 Ts
qr
t
enthalpy heat
Heat generation
energy
convection
conduction
storage
where,,cp,T, u ,qrmean:thermalconductivity,density,specificheat,temperature,fluid
with a velocity field u s (x,y,z) and heat generated per unit volume by the decomposition
reaction
.
q r s (H r )
d
d
s c p ,s Tad
dt
dt
withd/dttherateofthedecompositionreactionexpressedbytheArrheniustypeequation
asthoseappliedinFriedmananalysisand Tadtheadiabatictemperatureriseexpressedby
theheatofreaction Hrandthespecificheatcp,s: Tad=(Hr)/cp,s.Theenergyequationis
the same as for a solid body, except for the enthalpy transport, or convection term
s c p , s u s T s .
Toperformtheexactheatbalancethenumericaltechniqueslikefiniteelementanalysis,or
finitedifferencesorfinitevolumescanbeappliedtosolvetheenergyequation.Thesample
is virtually divided into the set of adjoining elements (see Fig.6.1). These elements are
organized in a virtual mesh and described by the advanced thermokinetics based on the
Friedmananalysisineachnodeoftimeandspace.
Figure6.1Generalizedheatbalanceoveracontainerandavolumeelement.
93

(A) KineticparameterscalculatedfromDSCmeasurements,independentofthesamplemass,enablethe
determinationofthereactionraterequiredfortheheatbalance.
(B) Heatbalancedependsonthesamplemassandhastobecalculatedbynumericaltechniques.
6.3.1.
ForSOLIDSincontainers:
If the examined substance in a sample holder is a SOLID, the main resistance to the heat
transfer lies in the bulk of the substance. In SOLIDS, heat transfer occurs mainly by heat
conductionandnotbyconvection:
s , solid 2Ts s c p , s u s Ts
heat
conduction
because u s 0
enthalpy
convection
Ts
s
d
2Ts Tad
t
dt
s c p,s

Heat
generation
heat
conduction
Ts f (t , x, y, z, kinetics, H r , c p , s , s , s , boundary conditions)
Therefore,thepropertywhichquantifiestheeasewithwhichamaterialtransfersheatisthe
thermalconductivity.Aspreviouslymentioned,thermalconductivitydependsmainlyonthe
mediums phase, temperature, density and molecular bonding within a solid structure. It
meansthatincaseofsolids(andonlyinthatcase)thereisarelevanttemperaturegradient
within the solids from the center to the container wall depending on the surrounding
temperature.Thisbehaviourisillustratedbythecalculationofthetemperaturechangesina
sphere of polystyrene (PS) stored in a sample holder of polyethylene (PE) (Fig.6.2) in a
surroundingtemperatureof1C.
Afterconsideringcylindricalcoordinatesandsomesimplificationsfortheheatconduction,
Ts
T
2 Ts
2 Ts
s
r
z
r2
z 2
onecanwrite
Ts s , solid
s c p,s
t
2 Ts J Ts
r2 r r
d
Tad
dt
Ts f (t , r , kinetics, H r , c p , s , s )
where:
Jisageometryfactordependentonthetypeofthecontainer:J=0fortheinfiniteplate,J=1
fortheinfinitecylinderandJ=2forthesphereandda/dt=0(nodecompositionreaction).
94
Figure6.2Typicalcoolingcurvesforsolids:Temperaturechangeina50LsampleholderofPE(wallthickness:3
mm,c=0.5W/(mK),c=0.95g/cm3,cp,c=2.3J/(gK))containingasphereofPS(s=0.1W/(mK),s=1.05
g/cm3, cp,s = 1.42 J/(gK)) at 20C and exposed to surrounding temperature of 1C. Pink line indicates the
surroundingtemperature,bottomcurve(blue)representsthetemperatureatthesurfaceofthesphere,upper
curve(green)displaysthetemperatureofPSinthecenterofthesphere.
6.3.2. ForLIQUIDSincontainers
6.3.2.1. ForLIQUIDSwithhighviscosity
IncaseofLIQUIDS,heatistransferrednotonlybyconductionbutmainlybyconvection.In
convection,heatistransferredfromonepointtoanotherthroughamovingfluid,asaresult
of the mixing of different portions of the fluid. The concept of the Nusselt number (Nu) is
generally used to determine the heat transfer coefficient h. The Nusselt number is a
dimensionless number which measures the enhancement of heat transfer from a surface,
comparedtotheheattransferthatwouldbemeasuredifonlyconductioncouldoccur.Itis
calculatedby:
Nu
hs x
s , fluid
f ( Pr, Re, Gr )
where x is the position along the interface in the direction of fluid flow. The Reynolds
number(Re),Prandtlnumber(Pr)andGrashofnumber(Gr)aredimensionlesstermswhich
dependonthevelocityandonthephysicalpropertiessuchdensity,viscosityandexpansion
volumeofthefluid.Therearetwosubsegmentsofconvection,forcedandnatural.Inforced
convection,themotionofthefluidistheresultofsomemechanicalwork,suchasapump
movingthefluid.Forliquidsincontainers,convectioniscausedbybuoyancyforcesdueto
density differences caused by temperature variations in the fluid. At heating the density
changeintheboundarylayerwillcausethefluidtoriseandbereplacedbycoolerfluidthat
alsowillheatandrise.Thiscontinuesphenomenoniscalledfreeornaturalconvectionand
theGrashofnumberisgenerallyusedtoapproximatetheratioofthebuoyancyforcetothe
viscousforceactingonafluid.However,forchemicalreactionmixtures,physicalproperties
95

such as volume coefficient of expansion or viscosity are usually unknown. Therefore,
becauseheatistransferredmainlybyconvectionthefollowingsimplificationscanbemade:
s c p , s u s Ts s , fluid 2Ts
enthalpy
convection
or
heat
conduction
c p , s u s Ts N s , fluid 2Ts s ,eq 2Ts

s
enthalpy
convection
heat
conduction
with N s , fluid s ,eq
heat
conduction
wherethesizeofNincreaseswithlowerviscosityandtheboundaryconditionsread
T (t , interface)
Ts (t , interface)
c c
s , fluid
hinterface (Ts (t , interface dx ) Ts (t , interface)
dx dx
enthalpy
heat
conduction
heat
conduction
convection
Itcomesforabovethatforliquidswithhighviscositytheenergyequationleadsto
s ,eq
Ts
d
2 Ts Tad
c p,s
dt
t
s

Heat
generation
heat
conduction
Ts f (t , x, y, z, kinetics, H r , c p , s , s ,eq , s , boundary conditions)
Finallyconsideringcylindricalcoordinatesandsomesimplificationsfortheheatconduction,
onecanwrite
s ,eq
Ts
s c p,s
t
2 Ts J Ts
r2 r r
d
Tad
dt
Ts f (t , r , kinetics, H r , c p, s , s ,eq , boundary conditions)
The boundary conditions at the interface between the wall and the liquid can be
approximatedby
T (t , interface)
T (t , interface)
c c
s ,eq s
dx
dx
heat
conduction
heat
conduction
6.3.2.2. ForLIQUIDSwithlowviscosity
Forliquidswithlowviscositywehave
0
0
.
T s
s c p,s
u s Ts s 2Ts
qr
t
enthalpy heat
Heat generation
energy
convection
conduction
storage
96

Ts
d
Tad
t
dt
Heat generation
Ts f (t , kinetics, H r , c p , s , boundary conditions)
wheretheboundaryconditionsread
c
Tc (t , interface )
hs (Ts Ts (t , interface ))
dx
As a consequence for liquids with low viscosity, one can proceed with the following
approximation:
c
T
hs (Ts T (t , interface ))
x
Tc , 2 Tc ,1
Lc
hs (Ts Tc , 2 )
WhereLc,Tc,1andTc,2mean:thicknessofthecontainerwall,thetemperatureattheouter
andinnersurfacerespectively.
Thenetheatrateis
.
h1 Ac (Tenv Tc ,1 )
c Ac
Tc ,1 Tc , 2
L
c
Rate of heat convection into the wall
hs Ac (Ts Tc , 2 )
rate of heat convection from the wall
rate of heat conduction through the wall
andfinallyusingtheresistanceconceptonecanestimatetheresistanceofthecontainerwall
asfollow:
Rc ,total
L
L
1
1
1
c
c
h ,1 Ac c Ac hc , 2 Ac
h ,1 Ac c Ac
c
c

Rwall
Rconv
Rconv
Rconv
Rwall
ConsideringtheresistanceoftheDewarwall
Rd ,total
Ld ,vacuum
1
hd ,1 Ad d ,vacuum Ad

Rconv
Rvacuum
Ttresultsthatacontainerfilledwithaliquidchemicalhassimilarthermalbehaviorjustlikea
Dewariftheirheattransferissimilar:
q in q out
Tenv Ts Tenv Ts
V
A
Vc Rc ,total Rd ,total Vd c c
Rc,totalVc Rd ,totalVd
Vd Ad
1
1
Ld hd ,1
d
Lc hc ,1
Vc Vd 1 Bi d
Ac Ad 1 Bic
97

whereBidandBicaretheBiotnumbersoftheDewarandthecontainerrespectively.TheBiot
numberexpressestheratiooftheresistancewithinthewallbytheconvectionresistanceat
thesurfaceofthewall.
Theaboveconditionhastobefulfilledfordescribingthethermalbehaviorforliquidsinlarge
containersbasedonanexperimentperformedatDewarscale.Itresultsthata500mlDewar
vesselcancorrectlypredictsthermalbehaviourofa500Lpackagefilledwithaliquid.
Illustration:
TheliquidinDewarisinitiallyatatemperatureof50Candthesurroundingtemperatureis
20C.TakingtheheattransfercoefficientfromairtoDewarhd,1 =30.25W/(m2K),onecan
determinewhichpackagesizefilledwiththesameliquidhasthesamethermalbehaviouras
the Dewar. The Dewar of Vd=500 ml can be modelled as a 2.5 cm radius, 12.73 cmlong
cylinder. The thermal properties of Dewar, container and the heat transfer coefficient are
constant.ThepropertiesoftheDewarandcontainerareLd=2.5mm,d=0.01W(mK)and
Lc=3mm,c=1W(mK),respectively.
Fromtheabovewehave
Bid
Bic
Ld h1
Lc h1
0.0025 m 30.25
0.01
W
mK
0.003 m 30.25
W
mK
W
m 2 K 7.5625
W
m 2 K 0.09075
Ad 2rd ( rd hd ) 2 0.025 m (0.025 m 0.127 m) 0.0239 m 2
Vc 0.0005 m 3 1 7.5625
0.164m
Ac 0.0239 m 2 1 0.09075
Assumingasphericalcontainerwecanwrite
rc 3
Vc
0.492m
Ac
Andfinally
4
4
Vc rc3 0.4923 0.5m 3
3
3
This example is in accordance with other observation reported elsewhere [28]. A 500 ml
Dewar vessel can be used to correctly predict thermal behaviour of a 500 L package filled
withaliquid,butnotfilledwithasolidwhereconductiveresistanceoccursinthebulk!For
liquidsstoredinthecontainers,thereisnorelevanttemperaturegradientwithintheliquids
from the center to the wall (for reasonable container sizes). In such a situation, it can be
assumed that the main contribution to the resistance to the heat transfer is given by the
98

containerwallandthesurroundingconvectiveresistance.Dependingonthethicknessand
typeofcontainerwallsonecandistinguishtwocases:
If the wall thickness of the container is significantly large compared to the

equivalent radius of the containers, then the thermal properties of the container
wall(suchase.g.PE)playarelevantroleintermsofresistancetoheattransfer.
If the thickness of the wall is narrow compared to the equivalent radius of the
container, then the influence of the type of the wall (as long as it is not a good
insulator) in terms of resistance to heat transfer is much less significant. For
example,a3mmwallcanbeconsideredassmallcomparedto22.85cmbeingthe
equivalentradiusofa50Lsampleholder.
Resultsofthedeterminationoftemperatureprofileina50Lcontainerfilledbywaterwith
temperatureof20Candasurroundingtemperatureof1CispresentedinFig.6.4.Itcanbe
observedthatthereisnolongerrelevantconductiveresistancearisingfromtheliquidwith
e.g. s,eq =100 W/(mK). It means that one can still use the heat conduction equation to
approximatetheheattransferprocessforliquids.However,insteadofthetruevalueofthe
thermal conductivity (such as e.g. 0.6 W/(mK) for water) an equivalent value such as e.g.
100 W/(mK) should be used. It means also that the numerical applications of large
equivalent thermal conductivity values will no longer have influence on SADT in case of
liquidreactivechemicalswhereda/dt 0andTad 0(seenextchapter).
Figure6.3Typicalcoolingcurvesforliquids:Exampleofa50Lsampleholder(spherical)ofPE(wallthickness:3
mm,=0.5W/(mK),=0.95g/cm3,cp=2.3J/(gK))containingwaterat20C(=0.6W/(cmK),=1g/cm3,cp
= 4.2 J/(gK)) and exposed to a surrounding temperature of 1C. Because of convective mixing conductive
resistanceoftheliquidisnegligibleforanapparentthermalconductivityvaluesuchase.g.100W/(mK).An
apparentthermalconductivityvaluesuchase.g.100W/(mK)suppressesanyconductiveresistancefromthe
liquidsidebecauseofconvectivemixing.
99

Notethatinthepresenceofadecompositionreactionsuchasthereductionofanesterwith
a Lithium aluminium hydride solution (Fig.3.3) the more complicated and precise finite
elementanalysiscanalsobeusedtoretrievetheadiabaticbehavior(Fig.5.5).Theadiabatic
behavior can be easily achieved with a very low value of thermal conductivity for the
evacuated layer of container wall such as Dewar for simulating the behavior of a good
insulator.Forillustration,asampleholderwithawallthicknessof3mmhavingextremely
low values of c = 1010 W/(mK), c = 1010 g/cm3, Cp,c = 1010 J/(gK) insures numerically a
perfectinsulationfortheexaminedsubstance(Fig.6.4).Asaresulttheadiabaticconditions
arenumericallyretrievedandleadbasicallytothesamethermalrunwaycurveaspresented
inFig.5.5.
Figure 6.4 Simulation of the adiabatic runaway curve with TMRad = 24h for a 1 L sample volume.
Ts,begin=52C,Tad=(Hr)/cp,s=140C for cp,s = 1.75 J/g/C. To numerically achieve the adiabatic conditions the
followingparameterswereappliedforsampleholder:3mmwallthickness,c=1e10W/(mK),c=1e10g/cm3,
cp,c=1e10J/(gK)).Suchparametersinsureaperfectinsulator.Pinklineindicatesthesurroundingtemperature
whichcorrespondstothetemperatureatthesurfaceofthesampleholder,uppercurve(green)displaysthe
temperatureofthechemicalstoredinthesampleholder.Dotlinesrepresentthetemperaturevariationinside
the insulator from the surface in contact with the surrounding (pink line) to the surface in contact with the
examinedsubstance(greenline).
6.4.
Method for the calculation of Self Accelerating Decomposition Temperature

(SADT)
The SelfAccelerating Decomposition Temperature (SADT) is an important parameter that

characterizes thermal hazard possibility under transport conditions of selfreactive
substances.SADTisusedininternationaltransportationregulationsandisreferencedinthe
United Nations presented in Recommendations on the Transport of Dangerous Goods,
Manual of Tests and Criteria (TDG) [29]. Globally Harmonized System (GHS) [30] has
inherited SADT as a classification criterion for selfreactive substances. According to the
Recommendations on TDG, SADT is defined as the lowest temperature at which self
accelerating decomposition may occur with a substance in the packaging as used in
transport.AnimportantfeatureofSADTisthatitisnotanintrinsicpropertyofasubstance
100

but a measure of combined effect of ambient temperature, decomposition kinetics,
packagingsizeandheattransferpropertiesofthesubstanceanditspackaging[2832].
The Manual of Tests and Criteria of the United Nations regarding transport of dangerous
goods and on the globally harmonized system of classification and labeling of chemicals
indicatesthatthecharacterizationofmaterialsisbasedonheataccumulationstoragetests.
Theregulatorycompliancedefinitionsare:
(i)
SADTisthelowestenvironmenttemperatureatwhichoverheatinthemiddleofthe
specificcommercialpackagingexceeds6C( T6)afteralapseofasevendayperiod
(168 hours) or less. This period is measured from the time when the packaging
centertemperaturereaches2Cbelowthesurroundingtemperature.
(i)
SADT is the critical ambient temperature rounded to the next higher multiple of
5C.
Thefirstdefinitionisbasedontwoessentialparametersmaximalpermissibleoverheating
temperatureandminimalacceptableinductionperiod.Theseconddefinitionconsidersonly
one parameter: thecritical ambient temperature of thermal runaway rounded to the next
highermultipleof5Cwithoutintroducinganyfixedtransportationtimeintothedefinition.
BearinginmindtheabovementionedSADTdefinitions,severaladditionalfactorshavetobe
consideredfortheproperdeterminationofSADT:
the intrinsic properties of the test material such as, kinetic parameters of
decomposition(activationenergy,preexponentialfactorintheArrheniusequation)
and physicochemical properties such as thermal conductivity, specific heat and
density.
the external properties of the sample that can be changed arbitrarily, e.g. sample
mass,geometryandphysicalpropertiesofthesampleholder/container.
Fromtheabovefactors,especiallytwonamelythermalconductivityandsamplemassmay
influencethecalculationofSADTinasignificantway.Asthermalconductivitiesofchemicals
are not always exactly known and as both, container volume and sample mass, can be
arbitrarilychanged,theirinfluenceonSADTwasexaminedinbroadrangeoftheirchanges.
Simulationshavebeendonefor:
sampleholdersshapedassphereswithinternalvolumesof:5,10,25,50,100,250
and500L.
followingequivalentthermalconductivitiess,eq:0.1,1,10W/(mK).
Illustration of choice of possible parameters regarding container materials and chemical

substanceforSADTcalculationscanbefoundinTable6.1.
101
Density
SpecificheatCp
Thermalconductivity
Equivalentsphericalradius
HeatofreactionHr
Heattransfercoefficienth
1g/cm3(assumedvalue)
1.5J/g/K(assumedvalue)
0.1W/(mK)<eq<10W/(mK)
(throughnumericalvariations)
10.6cm<sphericalequivalentradius<49.2cm
(5L<sampleholdervolume<500L)
554.8J/g(measuredfromDSC)
5W/(m2K)
Table0.2Sampleholderillustrationandphysicochemicalpropertiesofexaminedsubstance.
102

Tab. 6.2 presents the results of the SADT simulation for eq values between 0.1 and 10
W/(mK)andsamplevolumesbetween5and500L.
SADT(C)
Samplevolume(L)/
Equivalentsphericalradius(cm)
s,eq
W/(mK)
5/
10.608
10 /
13.365
25 /
18.139
50 /
22.854
100 /
28.794
250 /
39.08
500 /
49.237
0.1
1
10
44C
45C
45C
43C
45C
45C
41C
44C
45C
39C
44C
44C
36C
43C
44C
31C
42C
43C
30C
40C
42C
Table 0.3 Dependence of SADT (C) on equivalent thermal conductivity s,eq and the amount of chemical
substanceexpressedbythesamplevolume(L)ortheequivalentsphericalradius(cm).
The results in table 6.2 and figures 6.5 clearly show that both, thermal conductivity and
samplevolumeinfluencesSADTvalues.Fora50Lsamplevolume,SADTforsolidsubstance
withanassumedthermalconductivity of0.1W/(mK)amountsto39C(seeTab.6.2and
Fig.6.5A)whereasunderassumptionoflargerheattransferforanapparentconductivity
term s,eqarbitrarilysetto1and10W/(mK),SADTamounttoabout44Crespectively(see
Tab.6.2andFig.6.5BC).Asensitivityanalysiscaneasilyshowthattwoparametersmostly
influenceSADT:
(i)
thethermalconductivityandsamplevolumethatismainlyresponsiblefortheheat
transfer(accumulation&release)
(ii)
the type of reactions (decelerating, autocatalytic,...) and heat of reactions

responsiblefortheheatsource.
Average Reaction Progress (-)
Note:Allsimulationswereperformedwithadensityof1g/cm3(assumption).
SADT=39C,50kg,1000kgm^-3,1.5Jg^-1K^-1,0.1Wm^-1K^-1,-554.8Jg^-1,5Wm^-2K^-1
0.06
0.05
0.04
0.03
0.02
0.01
0
48
44
overheat 6C
42
40
38
SADT = 39 C
T surrounding -2 C
7 day or less
time = 3.22 day

0
5
Time (day)
Temperature (C)
46
36
34
0-AKTS-WEBMINAR-E-LEARNING-WP / SADT=39C,50kg,1000kgm^-3,1.5Jg^-1K^-1,0.1Wm^-1K^-1,-554.8Jg^-1,5Wm^-2K^-1
103
SADT=44C,50kg,1000kgm^-3,1.5Jg^-1K^-1,1Wm^-1K^-1,-554.8Jg^-1,5Wm^-2K^-1
1
0.8
0.6
0.4
0.2
0
52
48
46
0.5
1.5
42
7 day or less
time = 6.15 day

0
44
SADT = 44 C
T surrounding -2 C
Temperature (C)
50
overheat 6C
40
2.5
3.5
4
4.5
Time (day)
5.5
6.5
7.5
0-AKTS-WEBMINAR-E-LEARNING-WP / SADT=44C,50kg,1000kgm^-3,1.5Jg^-1K^-1,1Wm^-1K^-1,-554.8Jg^-1,5Wm^-2K^-1
SADT=44C,50kg,1000kgm^-3,1.5Jg^-1K^-1,10Wm^-1K^-1,-554.8Jg^-1,5Wm^-2K^-1
1
0.8
0.6
0.4
0.2
0
52
48
46
0.5
1.5
42
7 day or less
time = 6.76 day

0
44
SADT = 44 C
T surrounding -2 C
Temperature (C)
50
overheat 6C
40
2
2.5
3.5
4
4.5
Time (day)
5.5
6.5
7.5
0-AKTS-WEBMINAR-E-LEARNING-WP / SADT=44C,50kg,1000kgm^-3,1.5Jg^-1K^-1,10Wm^-1K^-1,-554.8Jg^-1,5Wm^-2K^-1
Table0.4DeterminationofSADTofexaminedsubstance(pink:surroundingtemperature,blue:temperatureatthe
surfaceofthesubstance,green:sampletemperatureinthecenterofthesample).Basedonthefirstdefinition(i)we
obtain:
(A) Top:SADTof39Cfora50Lsamplevolumewith s,eq=0.1W/(mK).
(B) Middle:SADTof44Cfora50Lsamplevolumewith s,eq=1W/(mK).
(C) Bottom:SADTof44Cfora50Lsamplevolumewith s,eq=10W/(mK).
SADTisthelowestenvironmenttemperatureatwhichtheoverheatinthemiddleofthespecificpackagingexceeds6C
(T6)afteralapseofasevendayperiod(168hours)orless.Thisperiodismeasuredfromthetimewhenthepackaging
centertemperaturereaches2Cbelowthesurroundingtemperature.
104
Figure6.53Dplotillustrationofthermalexplosionillustration(50Lsamplevolumewiths,eq=1W/(mK)anda
surroundingtemperatureof50C).
105

Notobservingthedifferentoverallthermaltransportbehaviourbetweensolidorliquid,the
confusionsolidliquidfortheSADTdeterminationisstillacommonmistake.Wethinkthat
thistopicshouldbeevenbetteremphasizedinthecurrentUNRegulationsasstatedinthe
conclusionsofrecentstudiesattheSwissInstituteforSafetyandSecurity[28]:
1.
SADTtest using a 500 ml Dewar vessel correctly predicts thermal behaviour of a

500lpackagefilledwithaliquid,butitwillonlyberepresentativeforan8Lpackage
filledwithasolid(Thisisofcourseanexaggeratedstatement.WhentheauthorH.
Fierz [28] calculated it, he probably took rather extreme parameters to emphasize
thewarningstatement).
2.
The UNtest H.4 was obviously designed to make a direct scaleup to a

predetermined package size possible. This does not work for solids. Extrapolated
packagesizesforsolidsaredramaticallydifferentfromthoseforliquids.
3.
ForsolidstheUNtestH.4resultsareontheunsafesideandshouldthereforenot
beused.
4.
The concept of time constants and specific heat losses for cooling of solids are
misleading and should be abandoned. For solids the cooling characteristics of the
bulkinitspackagingshouldbedeterminedindividuallyforeachcaseorevenbetter:
thetheoryofFrankKamenetskiishouldbeapplied.(ormoregenerallytheproblem
of the heat conduction equation combined with the correct expression for the
decompositionkineticsshouldbesolved).
106

7. Conclusion
This study focuses on prediction of the reactivity of a substance both in extended
temperature ranges and under temperature conditions for which experimental data
collection is difficult. Adequate predictive examination of investigated reactions requires
about four DSC measurements carried out with different heating rates, generally in the
rangeof0.25to8K/min.Moreover,applyingtheresultsobtainedbyDifferentialScanning
Calorimetry (DSC) advanced numerical techniques enable prediction of the reactivity in
broadtemperaturerange.Infact,numericalsimulationscanbeusedtoreplaceexperiments
in situations, which are not directly accessible to measurement for example for timing
reasons. The examples of such modelling analysis can be helpful for guiding the screening
and development of new materials activities. If modelling proceeds in parallel with
experimentalstudies,thenitshouldresultinlowercostsinaprojectdevelopmentphase.
Theproposedmethodhasthereforeseveraladvantages:
It is fast: Reliable screening of candidate energetic materials by revelation of

potentiallyunstablemixturesatprolongedtimesandtemperatureexposurescanbe
donewithinfewhours.
It is economical: The determination of the kinetics offers very significant

time/expertise savings compared to real time analysis which can extend over
prolongedperiods,evenmonths.
Itisconvenient:DSCdevicesarewidelyavailableandonlyrequireasmallamountof
material.
It is versatile: With one set of measurements different scenarios can be calculated.

The method can be used to predict the rate of the reaction progress for any
temperatureprofile.
SafetythroughdesignnotbyAccidents
107

8. References
[1]AKTSAG,http://www.akts.com(AKTSThermokineticssoftwareandAKTSThermalSafetysoftware)
[2]M.E.Brownetal.Computationalaspectsofkineticanalysis.TheICTACKineticsprojectdata,methodsandresults.
Thermochim.Acta,355(2000)125.
[3]M.Maciejewski,Computationalaspectsofkineticanalysis.TheICTACKineticsProjectThedecomposition
kineticsofcalciumcarbonaterevisited,orsometipsonsurvivalinthekineticminefield.Thermochim.Acta,355
(2000)145.
[4]A.Burnham,Computationalaspectsofkineticanalysis.TheICTACKineticsProjectmultithermalhistorymodel
fittingmethodsandtheirrelationtoisoconversionalmethods.Thermochim.Acta,355(2000)165.
[5]B.Roduit,Computationalaspectsofkineticanalysis.TheICTACKineticsProjectnumericaltechniquesand
kineticsofsolidstateprocesses.Thermochim.Acta,355(2000)171.
[6]H.L.Friedman,J.Polym.Sci,PartC,PolymerSymposium(6PC),183(1964).
[7]T.Ozawa:Bull.Chem.Soc.Japan,38(1965)1881.
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[10]P.Brudugeac,J.Therm.Anal.,Vol.68(2002)131.
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[12]B.Roduit,Ch.Borgeat,B.Alonso,J.N.Aebischer,P.Pollien,A.RaemyandI.Blank,32ndNATASCONFERENCE,
WilliamsburgMarriott,Williamsburg,VAOctober46,2004.
[13]B.Roduit,W.Dermaut,A.Lunghi,P.Folly,B.BergerandA.Sarbach,J.Therm.Anal.Cal.,Vol.93(2008)1,163
173,
http://www.akts.com/cookoffthermalsafetyrunaway/processsafety.html
http://dx.doi.org/10.1007/s1097300788661
[14]B.Roduit,Ch.Borgeat,B.Berger,P.Folly,B.Alonso,J.N.AebischerandF.Stoessel,J.Therm.Anal.Cal.,ICTAC
specialissue,80(2005)229236.
[15]B.Roduit,Ch.Borgeat,B.Berger,P.Folly,B.Alonso,J.N.Aebischer,J.Therm.Anal.Cal.,ICTACspecialissue,80
(2005)91102.
[16]U.Ticmanis,G.Pantel,S.Wilker,M.Kaiser,Precisionrequiredforparametersinthermalsafetysimulations,32nd
InternationlAnnualConferenceofICTJuly,(2001),135.
[17]B.Roduit,Ch.Borgeat,U.Ticmanis,M.Kaiser,P.Guillaume,B.Berger,P.Folly,35thInternationalAnnual
ConferenceofICT,June29July2,2004,371.
[18]P.Folly,Chimia,58(2004),394.
[19]F.Stoessel,J.Steinbach,A.Eberz:Plantandprocesssafety,exothermicandpressureinducingchemical
reactions,In:Ullmann'sencyclopediaofindustrialchemistry.WeiseE(Eds),VCH,Weinheim(1995):343354.
[20]A.Keller,D.Stark,H.Fierz,E.Heinzle,K.Hungerbuehler:EstimationoftheTMRusingdynamicDSCexperiments.
JournalofLossPreventionintheProcessIndustries(1997)10(1):3141.
[21]D.A.FrankKamenetskii,DiffusionandHeatTransferinChemicalKinetics,PlenumPress,NewYork,London,
1969.
[22]J.M.Dien,H.Fierz,F.Stoessel,G.Kill:Thethermalriskofautocatalyticdecompositions:akineticstudy.Chimia
(1994)48(12):542550.
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[24]T.Grewer,Thermochim.Acta,225(1993)165.
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2008,WILEYVCHVerlagGmbH&Co.CGaA.
[27]AheattransfertextbookThirdEdition,JohnH.LienhardIV/JohnH.LienhardV,PhlogistonPress,Cambridge
Massachusetts,2008
[28]H.Fierz,JournalofHazardousMaterialsA96(2003)121126
[29]2003,RecommendationsontheTransportofDangerousGoods,ManualofTestsandCriteria,4revisededition,
UnitedNations,ST/SG/AC.10/11/Rev.4(UnitedNations,NewYorkandGeneva).
[30]2003,GloballyHarmonizedSystemofClassificationandLabellingofChemicals(GHS),UnitedNations,NewYork
andGeneva
[31]B.Roduit,P.Folly,B.Berger,J.Mathieu,A.Sarbach,H.Andres,M.RaminandB.Vogelsanger,J.Therm.Anal.
Cal.,93(2008)1,153161.
http://www.akts.com/cookoffthermalsafetyrunaway/dscsadt.html
http://dx.doi.org/10.1007/s1097300788652
[32]B.Roduit,L.Xia,P.Folly,B.Berger,J.Mathieu,A.Sarbach,H.Andres,M.Ramin,B.Vogelsanger,D.Spitzer,H.
MoulardandD.Dilhan,J.Therm.Anal.Cal.,Vol.93(2008)1,143152.
http://www.akts.com/cookoffthermalsafetyrunaway/dschfc.html
http://dx.doi.org/10.1007/s1097300788643
108
AKTS SOFTWARE
CD-ROM
110
AKTSSoftwareCDROM
Thermokinetics ThermalAging
Thermokinetics ThermalSafety
Calisto
SML
InserttheCalistoCDROMandwaitfortheinstallationsoftwaretostart.
NOTE:Ifthesoftwaredoesnotstartautomatically,browsetheCDandlaunchstart.exe
Forthelatestupgrade,pleasevisit:
ThermalAging
ThermalSafety
Calisto
SML
http://www.akts.com/thermalagingoverview.html
http://www.akts.com/thermalsafetyoverview.html
http://www.akts.com/calistooverview.html
http://www.akts.com/smloverview.html
111
AKTS
Advanced Kinetics and Technology Solution
For further information visit:

http://www.akts.com
AKTS AG
TECHNOArk
3960 Siders
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Phone +41 848 8002221
Fax +41 848 8002222
Email: support@akts.com
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ADVANCED KINETICSBASED SIMULATION

prediction of the reaction progress for required temperature profiles applying

Heat : -551.157 (J/g)

Heat : -544.199 (J/g)

Heat : -551.636 (J/g)

HeatFlow |-bs |n |int (-)

HeatFlow |-bs |n (-/s)

Models of the decelerating typerepresent processes whose rate hasmaximum at

Sigmoidal reaction models may be thought of as accelerating at the beginning

Accelerating models represent processes whose rate increases continuously with

ln(Reaction rate(-/s)) (-)

0-AKTS-WEBMINAR-E-LEARNING-WP / Differential isoconversional

0-AKTS-WEBMINAR-E-LEARNING-WP / Activation Energy

Reaction progress (-)

0-AKTS-WEBMINAR-E-LEARNING-WP / Reaction progress

Reaction rate (-/s)

0-AKTS-WEBMINAR-E-LEARNING-WP / Reaction rate

A detailed analysis of the various isoconversional methods (i.e. the isoconversional

It means that the isoconversional integral methods return to isoconversional differential

Kinetic parameters calculated from nonisothermal experiments allow prediction of the

Reaction Rate (W/g)

Reaction Progress (-)

0-AKTS-WEBMINAR-E-LEARNING-WP / Iso (DeltaHr=-554.8Jg^-1)

Reaction Progress (-)

0-AKTS-WEBMINAR-E-LEARNING-WP / Iso (DeltaHr=-554.8Jg^-1)

Reaction Rate (W/g)

0-AKTS-WEBMINAR-E-LEARNING-WP / Non-iso (Tstart=30C, DeltaHr=-554.8Jg^-1)

Reaction Progress (-)

Reaction Rate (-/s)

0-AKTS-WEBMINAR-E-LEARNING-WP / Step (DeltaHr=-554.8Jg^-1)

Reaction Progress (-)

Reaction Rate (W/g)

0-AKTS-WEBMINAR-E-LEARNING-WP / Modulated (24h, 0Kmin^-1, DeltaHr=-554.8Jg^-1)

Reaction Progress (-)

Reaction Rate (W/g)

Worldw ide (Hr=-554.8Jg^-1)

0-AKTS-WEBMINAR-E-LEARNING-WP / Worldwide (DeltaHr=-554.8Jg^-1)

STANAG (A2 diurnal seasonal, Hr=-554.8Jg^-1)

Reaction Progress (-)

Reaction Rate (W/g)

0-AKTS-WEBMINAR-E-LEARNING-WP / STANAG (A2 diurnal seasonal, DeltaHr=-554.8Jg^-1)

Reaction Progress (-)

Reaction Rate (W/g)

0-AKTS-WEBMINAR-E-LEARNING-WP / Customized (DeltaHr=-554.8Jg^-1)

AKTSThermokinetics Software can optimize temperature program in such a way that it

Reaction Rate (W/g)

Reaction Progress (-)

Reaction Progress (-)

Reaction Rate (W/g)

0-AKTS_WEBMINAR-E-LEARNING-WP / SCTA Step

the application of advanced kinetics, which properly describes the complicated,

Because decomposition reactions usually have a multistep nature, the isoconversional

Net heat transfer

Net heat transfer

Net heat transfer

Because the presence of a temperature difference leads to heat transfer, an adiabatic

Net heat transfer