FirstOrderKineticsvsSecondOrderKinetics

Studentsmayreportthedyebleachingreactionwestudyinthelaboratorytobeeitherfirstorsecond
orderinthedye.Whyisitpossibletoobtaintheseambiguousresults?
Thecriterionweusetodistinguishtheorderisspecificandquantitative.Namely:

wemeasurethedyeconcentration(oritsabsorbance,towhichtheconcentrationisdirectly
proportional)asafunctionoftime.
Weplotthereciprocalofthedyeconcentrationvstime
Weplotthelogarithmofthedyeconcentrationvstime

Iftheplotofthelogarithmvstimegivesamorelinearplot,wededucethattheorderis1
Iftheplotofthereciprocalvstimeismorelinear,wededucethattheorderis2
OurmeasureoflinearityineachcaseisvalueofR2,thegoodnessoffitcriterionfortheleastsquares
linearfittotheexperimentaldata.
Theexperimentaldataaresubjecttoavarietyofsourcesoferror.Thesewillgenerallyproduceplots
thatdeviatesomewhatfromperfectstraightlineplots.I.e.,thevaluesofR2thatweobtainhavetwo
contributions.

Atheoreticalcontributionduetotheunderlyingidealmathematicalrelationshipsbetween
concentrationandtimethatmodelfirstandsecondorderkinetics
Acontributionduetoexperimentalerror

LetusignorethesecondcontributionstoR2andaskhowdifferenttheR2valuesareintheabsenceof
experimentalerror.
Todoso,weconsidertwocases:oneinwhichareactionistrulyfirstorder,andthesecondinwhichthe
reactionistrulysecondorder.Weaskhowfarfromlinearityistheplotfortheinapplicableorder(e.g.,
thesecondorderplotwhenthereactionistrulyfirstorder)ineachcase?
Whatothercharacteristicoftheexperimentmayhaveabearingonthisquestion?Weknowthatin
bothfirstandsecondorderkinetics,theconcentrationofthesubstancedecreasesinanonlinearbut
monotonicway.Thedistinctionbetweenthesetwowillcertainlydependonthetimeperiodover
whichtheyaremeasured.
Case1:Trulyfirstorderreaction.
Forsuchareaction,thetimedependenceofconcentrationisgivenby
c/c0=ekt

Intheexercise,wemakediscretemeasurementsofcatspecifiedintervalsoftime.Letusfixthe
numberofmeasurementswemakeatthatusedintheexperiment,namely,eight.Wefixthetotal
timeoverwhichwemakethemeasurementsbychoosingatimeincrement,t,betweenmeasurements
measuredinhalflivesofthereaction.(E.g.,ift=0.25,8measurementswillfollowthereactionfor2
fullhalflives.)Thehalflifeofafirstorderreac onisgivenbyt=ln2/k.Intermsof(c/c0)and(t/t),
thefirstorderconcentrationdependencebecomes:

c/c0=eln2(t/t)
WeexaminethevaluesofR2andtheslopesoftheplotsofthebest,leastsquares,linearplotsofthe
logarithmandthereciprocalofc/c0asafunctionoftime,t/t,andsummarizetheresultsasafunction
ofthenumberofhalflivesoverwhichwefollowthereaction.
Theresultsofsuchananalysis1areasfollows:

#halflives
1
2
3
4

ln(c/c0)
slope
0.693
0.693
0.693
0.693

R
1.000
1.000
1.000
1.000

1/(c/c0)
slope
0.995
1.470
2.233
3.484

R2
0.991
0.964
0.923
0.875

Ascanbeseenfromthetable,thevalueofR2doesnotchangeforthelogplotbutforthereciprocal
plot,itdependsonthenumberofhalflivesoverwhichwefollowthereaction.Ifourtotaltimeof
observationissmall,e.g.asinglehalflife,R2willmakeitdifficulttodistinguishfirstfromsecondorder
kinetics.Addingthelikelihoodthatsomeexperimentalerrorwillbeintroducedwouldconfoundthe
circumstancesevenmore.Onlyifwefollowthereactionformorethanthreehalflives,doesthe
intrinsicR2becomelessthan0.900.
Wenotealsothatwhiletheslopeofthelogarithmplotisconstantovertherange,theslopeoftheleast
squaresstraightlineapproximationtothereciprocaldatavariesoveralargerangeafactorofabout
3.5.
Whataboutthereversecase?
Case2:Trulysecondorderreaction.
Forsuchreactions,theconcentrationdependenceontimeisgivenby
c/c0=1/(1+c0kt)

Thesecalculationsarebasedonaspreadsheetavailableat:
http://www.ic.sunysb.edu/Class/che133/spreadsheets/1stvs2nd.xlsx

Asecondorderreactiondoesnothaveasingle,constant,halflife.Togetmeasuresoftimecomparable
towhatwehavedoneinCase1,wedefineavirtualsecondorderhalflifeasthetimeittakesforthe
initialconcentrationtofalltoofitsoriginalvalue.Thattimedependsonboththeoriginal
concentration,c0,andtherateconstantk,namelyt=1/c0k.Ifweagainusetasourscaleoftime,the
secondorderratelawgives:

1/(c/c0)=1+(t/t)
WeagaintabulatetheslopesandR2fordataspanninganumberofhalflives.
ln(c/c0)
slope
0.686
0.536
0.444
0.382

#halflives
1
2
3
4

R2
0.990
0.976
0.963
0.951

1/(c/c0)
slope
1.000
1.000
1.000
1.000

R2
1.000
1.000
1.000
1.000

Thetableshowsthat,unlikeinCase1,thegoodnessoffitcriterion,R2,degradesslowlyasthenumber
ofhalflivesincreases.FollowingthereactionforfourhalflivesstillgivesanR2of0.95.Basedonthe
goodnessoffitcriterion,wearelikelytointerpretwhataretrulysecondorderkineticsasfirstorder!
Again,wenotethattheslopeoftheappropriate,reciprocalplotisinsensitivetothenumberofhalflives
whiletheslopeoftheother,logarithmplotdecreasestoalmosthalfitsvalueasthetimescaleis
expandedto4halflives.
Oureffortstolinearizetheprocesscannothidethesimilarityintheinitialvaluesoftheearlypartsof
theunderlyinggraphsofexponentialsandreciprocals,ascanbeseeninthefigurebelow.
Concentrationvs Time

Concentration(c/c0 )

1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

SecondOrder
Reciprocal
FirstOrder
Exponential
0.0

0.5

1.0

1.5
2.0
2.5
Time(t/t1/2 )

3.0

3.5

4.0

Withthereminderthatintheaboveanalysis,wehaveignoredcontributionstoR2duetoexperimental
error,itiseasytoseewhythedeterminationofthecorrectrateorderrequiresconsiderablecareinthe
kineticsmeasurements.
Italsoshowsthat,excludinglargeexperimentaluncertainties,forshortobservationperiods,weare
morelikelytointerpretthekineticsasfirstorderthanassecondorder.
RFS07/13