PresentationSlides

for

Chapter12
of

FundamentalsofAtmosphericModeling
2ndEdition
MarkZ.Jacobson
DepartmentofCivil&EnvironmentalEngineering
StanfordUniversity
Stanford,CA943054020
jacobson@stanford.edu
March29,2005

InitialValueProblems
Valuesareknownataninitialtimeanddesiredatafinaltime
Concentrationofspeciesiisknownattimeth=0

(12.2)

Ni,th =Ni,0
Vectorofconcentrationsattimet

= N ,N ,...,N ,...,N
N
t [ 1,t 2,t
i,t
K,t ]

(12.1)

PropertiesofGoodODESolvers
Accuracy
Massconservation
Positivedefiniteness
Speed

Normalizedgrosserror

1
NGE =
Ntim

Ntim

1
K
s,t j
j=1

(12.3)
Ks,t j

Ni,t j Ei,tj

100%

Ei,t j

i=1

AnalyticalSolutiontoODEs
Nitrogendioxidephotolysis
NO

+h

(12.4)

TimerateofchangeofNO2concentration

(12.5)

d[NO2]
=J [NO2]
dt
Analyticalsolution

Jh
NO
=
NO
e
[ 2]t [ 2]th

Example:
[NO2]th=1010molec.cm3
J=0.02s1
> [NO2]t=1010e0.02t

(12.6)

TaylorSeriesSolutiontoODEs
ExplicitTaylorseriesexpansionforonespecies
2

(12.7)
3

dNi,th h2 d Ni,th h3 d Ni,th

Ni,t =Ni,th +h
+
+
+...
2
3
dt
2
6
dt
dt
TaylorseriesexpansionforNO2

(12.8)

d[NO]th h2 d2[NO]th h3 d3[NO]th

[NO]t =[NO]th +h
+
+
+...
2
3
dt
2
6
dt
dt

TaylorSeriesExample
2

d[NO]th h2 d [NO]th h3 d [NO]th

[NO]t =[NO]th +h
+
+
+...
2
3
dt
2
6
dt
dt
Assume

NO+O

NO

+O

d[NO]
=kb [NO][O3]
dt
d[O 3]
d2[NO]
d[NO]
2 =kb dt [O 3] kb [NO] dt
dt
d3[NO]
dt

=kb

d2[NO]
dt2

d2[O 3]
d[NO] d[O3]
kb[NO]
[O3 ] 2kb
dt
dt
dt2
(12.812.12)

TaylorSeriesSolution
NO+O

NO

+O

d[O3]
d[NO2] d[NO]
=
=
dt
dt
dt
d2[O3]
dt2

d3[O3]
dt

Disadvantages
Unstableunlesssmalltimestepisused
Highderivativescomputationallydemanding

d2[NO2 ] d2[NO]
=
=
2
dt
dt2
=

d3[NO2 ]
dt

d3[NO]
dt3

(12.13)

ForwardEulerSolutiontoODEs
ExplicitforwardEulersolutionforanindividualspecies

(12.14)

dNi,th
Ni,t =Ni,th +h
dt
Examplesetofthreeequations
NO+O

NO

NO

NO

+O

+h

FirstderivativeofNO2

NO

+O

(12.1517)

+O

(k1)
(k2)
(J)
(12.18)

d[NO2]th
=k1[NO]th[O3]th k2[NO2]th[O3]th J [NO2]th
dt

ForwardEulerSolutiontoODEs
FirstderivativeofNO2

(12.18)

d[NO2]th
=k1[NO]th[O3]th k2[NO2]th[O3]th J [NO2]th
dt
ForwardEulerequation

(12.19)

[NO2]t =[NO2]th +h(k1[NO]th[O3]th k2[NO2]th[O3]th J [NO2]th )

ForwardEulerSolutiontoODEs
ForwardEulerequation

(12.19)

[NO2]t =[NO2]th +h(k1[NO]th[O3]th k2[NO2]th[O3]th J [NO2]th )

Rewriteintermsofproductionandloss

(12.2022)

[NO2]t =[NO2 ]th +h(Pc,NO2,th Lc,NO2,th)

Pc,NO2,th =k1[NO]th[O3]th
Lc,NO2,th =k2[NO2]th[O3]th +J [NO2]th
Advantages
Massconserving,easytocalculatederivatives
Disadvantage
Unconditionallyunstable

MassConservationofForwardEuler
Requirementformassconservationofnitrogen

(12.28)

([NO2] +[NO])t =([NO2] +[NO])th

ForwardEulerconcentrationsofnitrogenspecies

[NO2]t =[NO2]th +hk1[NO]th [O3]th

[NO]t =[NO]th hk1[NO]th [O3]th

(12.24,6)

MassConservationofForwardEuler
Requirementformassconservationofoxygen
(2[O2] +3[O3] +2[NO2] +[NO])

(12.29)

=(2[O2] +3O
[ 3] +2[NO2] +[NO])th
ForwardEulerconcentrations

(12.247)

[O2]t =[O2]th +hk1[NO]th [O3]th

[O3]t =[O3]th hk1[NO]th [O3]th
[NO2]t =[NO2]th +hk1[NO]th [O3]th
[NO]t =[NO]th hk1[NO]th [O3]th

BackwardEulerSolutiontoODEs
LinearizedbackwardEulersolutionforonespecies
dNi,t,th
Ni,t =Ni,th +h
dt

(12.30)

Examplesetofthreeequations

(12.1517)

NO+O

NO

NO

+O

+h

FirstderivativeofNO2

d[NO2]t,th
dt

NO

NO

+O

+O

(k1)
(k2)
(J)
(12.31)

=k1[NO]th[O 3]th k2[NO2 ]t[O3 ]th J [NO2 ]t

BackwardEulerSolutiontoODEs
FirstderivativeofNO2

d[NO2]t,th
dt

(12.30)

=k1[NO]th[O 3]th k2[NO2 ]t[O3 ]th J [NO2 ]t

LinearizedbackwardEulerequation

(12.32)

[NO2]t =[NO2]th +h(k1[NO]th[O3]th k2[NO2]t[O3]th J [NO2]t )

BackwardEulerSolutiontoODEs
LinearizedbackwardEulerequation

(12.32)

[NO2]t =[NO2]th +h(k1[NO]th[O3]th k2[NO2]t[O3]th J [NO2]t )

Rewriteintermsofproductionandloss

(12.36)

[NO2]t =[NO2]th +h(Pc,NO2,th c,NO2,th [NO2]t )

Productionterm

(12.33)

Pc,NO2,th =k1[NO]th[O3]th
Lossterm
(12.34)
Lc,NO2,t,th =k2[NO2]t [O3]th +J [NO2]t
Implicitlosscoefficient

c,NO2,th =

Lc,NO 2,t,th
[NO2 ]t

(12.35)

=k2 [O 3]th +J

BackwardEulerSolutiontoODEs
[NO2]t =[NO2]th +h(Pc,NO2,th c,NO2,th [NO2]t )
Rearrange

(12.37)

[NO2]t (1+hc,NO2,th ) =[NO2]th +hPc,NO2,th

[NO2 ]th +hPc,NO2,th
[NO2 ]t =
1+h c,NO ,th
2

Advantages
AlwaysgivespositivesolutionstochemicalODEs
Disadvantages
Requiresasmalltimestepforaccuracy
Notmassconserving

BackwardEulerSolutiontoODEs
Requirementformassconservationofnitrogen

(12.28)

([NO2] +[NO])t =([NO2] +[NO])th

Exampleofmassnonconservationofnitrogen

(12.39)

[NO2]t =[NO2]th +hk1[NO]th [O3]th

[NO]t =[NO]th hk1[NO]t [O3]th

SimpleExponentialSolutiontoODEs
Obtainedbyintegratingalinearizedfirstderivative.

Advantages
AlwaysgivespositivesolutionstochemicalODEs
Easytoimplement
Disadvantages
Requiresasmalltimestepforaccuracy
Notmassconserving

SimpleExponentialSolutiontoODEs
LinearizedfirstderivativefrombackwardEulerexample(12.31)

d[NO2]t,th
dt

=k1[NO]th[O 3]th k2[NO2 ]t[O3 ]th J [NO2 ]t

Rewriteintermsofproductionandloss
(12.43)
d[NO2]t
=Pc,NO2,th c,NO2,th[NO2]t
dt
Integrate

(12.44)
h c,NO2,t h

[NO2 ]t =[NO2 ]th e

Pc,NO2,th

c,NO2,th

h c,NO2,th
1e
(
)

SimpleExponentialSolutiontoODEs
Genericsolution

(12.45)

hc,i ,th

Ni,t =Ni,the

Pc,i,th
hc,i ,th
+
1e
(
)
c,i,th

Whentheimplicitlosscoefficientiszero(nolossterm),
Ni,t =Ni,th +hPc,i,th
Whentheproductiontermiszero,

Ni,t =Ni,thehc,i,th

Whentheimplicitlosscoefficientislarge(shortlivedspecies),

Pc,i,th
Ni,t =
c,i,th

(steadystatesolution)

QuasiSteadyStateApproximation
QSSA
UseforwardEulerforlonglivedspecies
Usesimpleexponentialformediumlivedspecies
Usesteadystatesolutionforshortlivedspecies

(12.46)

Ni,th +h(Pc,i,th Lc,i,th )

Pc,i,th
hc,i ,th
Ni,t =Ni,the
+
1ehc,i,th )
(
c,i,th

Pc,i,th c,i,th

h c,i,th <0.01
0.01h c,i,th 10
hc,i,th >10

MultistepImplicitExplicit(MIE)
Solution
Premises:
TheforwardEulerandlinearizedbackwardEulersolutionsconvergetoeachotheruponiteration.
SincetheconvergedbackwardEulerisalwayspositive,soistheconvergedforwardEuler.
SincetheconvergedforwardEuleralwaysconservesmass,sodoestheconvergedbackwardEuler
>TheMIEsolution,whichrequiresiteration,conservesmassandispositivedefinite.

MultistepImplicitExplicitSolution
1)Setinitialestimatestoinitialconcentrations

(12.49)

Ni,B,1 =Ni,th
2)Setinitialmaximumestimatestoinitialvalues
(12.50)
MaximumestimatesareusedtoboundthebackwardEulerduringtheinitialiterationsteps.

Ni,MAX ,1 =Ni,th
3)EstimatereactionratesfrombackwardEulervalues (12.51)
Theseequationapplyforanyiterationnumberm

Rc,n,B,m =kn Ni,B,mN j,B,m

Rc,n,B,m =J n Ni,B,m

MultistepImplicitExplicitSolution
4)Sumproduction,loss,implicitlossterms
N prod,i

(12.53)

Rc,nP (l,i),B,m

Pc,i,B,m =

l =1

(12.55)
N loss,i

Lc,i,B,m =

Rc,nL (l,i),B,m

l =1

L c,i,B,m
c,i,B,m =
Ni,B,m

(12.57)

MultistepImplicitExplicitSolution
Examplereactions

(12.47)

NO+O

NO

+O

k1
(12.48)

+h

Estimatereactionrates.

Rc,1,B,m =k1[NO]B,m[O3]B,m
Rc,2,B,m =J [O3]B,m

(12.52)

MultistepImplicitExplicitSolution
Summedproductionterms
Pc,O,B,m =J [O3]B,m

(12.54)

Pc,NO2,B,m =k1[NO]B,m[O3]B,m
Summedlossterms

(12.56)

Lc,NO,B,m =k1[NO]B,m[O3]B,m
Lc,O3,B,m =k1[NO]B,m[O3]B,m +J [O3]B,m

MultistepImplicitExplicitSolution
Summedimplicitlosscoefficients

c,NO,B,m =k1[O3]B,m
c,O3,B,m =k1[NO]B,m +J

(12.58)

MultistepImplicitExplicitSolution
5)EstimateconcentrationswithbackwardEuler

(12.59)

Ni,th +hPc,i,B,m
Ni,B,m+1 =
1+h c,i,B,m

6)EstimateconcentrationswithforwardEuler

Ni,F,m+1 =Ni,th +h(Pc,i,B,mLc,i,B,m)

(12.60)

MultistepImplicitExplicitSolution
7)Checkconvergence

(12.61)

F ,m+1 0 nP =nP +1

Ni,F ,m+1 <0 nP =0

Method1:
Each iteration, check whether all concentrations from forward
Euler zero. If so, update a counter, nP by 1. If one
concentration<0,resetnPto0.
When nP=NP (all concentrations from forward Euler exceed 0
forNPiterationsinarow),convergencehasoccurred
NP =5forlargesetsofequations

=30forsmallsetsofequations

MultistepImplicitExplicitSolution
7)Checkconvergence
(12.62)
F ,m+1 0 for specieswith hc,i,B,m <L T nP =nP +1
N

Ni,F ,m+1 <0 and h c,i,B,m <LT nP =0

Method2:
Each iteration, check whether all concentrations of medium
and longlived species (those for which hLc,I,B,m<LT) from
forwardEulerzero.Ifso,updatethecounter nPby1.Ifone
suchconcentration<0,resetnPto0.
WhennP=NP,convergencehasoccurred
LT=102106

MultistepImplicitExplicitSolution
8)Uponconvergence,setfinalconcentrations

Ni,B,m+1

Ni,t =
Ni,F ,m+1

(12.63)

(backwardEuler)

h c,i,B,m LT

(forwardEuler)

h c,i,B,m <LT

9a)Recalculatemaximumfornextiteration

(12.64)

Ni,MAX ,m+1 =maxN

( i,B,m+1, Ni,th)
9b)BoundbackwardEulerfornextiteration
(12.65)
NotethatthisequationusestheMAXconcentrationfromthepreviousiteration,notfromthevaluejustcalculated.

Ni,B,m+1 =min{Ni, B,m+1,Ni,MAX ,m}

MultistepImplicitExplicitSolution
DemonstrationthatiteratedforwardEulersolutionsconvergetoiteratedbackwardEulersolutionsandto
positivenumbers.

ConvergedbackwardEulerequation

(12.66)

Ni,B,m+1 =Ni,th +h(Pc,i,B,m c,i,B,mNi,B,m+1)

ConvergedforwardEulerequation

(12.64)

Ni,F,m+1 =Ni,th +h(Pc,i,B,m c,i,B,mNi,B,m)

where

c,i,B,mNi,B,m =Lc,i,B,m

Thus,convergenceofforwardtobackwardEuleroccurswhen
Ni,B,m+1 =Ni,B,m
whichoccursuponiterationofbackwardEuler

(12.68)

ConvergenceofForwardEuler(FE)to
BackwardEuler(BE)UponIteration
h=10seconds.
)

15

1x10

10
NO

(FE)
2

13

NO

14

10

(BE)
O(FE)

5x10

11

10

O(moleculescm
10

1x10

andO

10
14

O(BE)

5x10

(FE)
5
3

NO

O(molec.cm3)

(moleculescm

15

NO2andO3(molec.cm3)

10

(BE)
3

15

1x10

1000

10

Iterationnumber

100

Fig.12.1

ComparisonofMIEWithExactSolution
Concentration(molec.cm3)

leculescm

MIEsolution(circles);exactsolution(lines);h=10seconds.
)

12

3x10

12

2.5x10

12

2x10

12

1.5x10

O
3

12

1x10

HNO
11

5x10

1x10

12

16

20

24

Hoursfromstartofsimulation

Fig.12.2

No.ofiterationsrequired

Timestepsizesof2,10,100,500,and1000secondsarecompared.Resultsinallcasesare
shownafter10,000s.

110

0.4

0.35
4

810

0.3

0.25
4

610

0.2
Averageerrorperspecies(%)

0.15
4

410

0.1

0.05
4

210

10

100

Timestep(s)

Averageerrorperspecies

nsrequired

EffectsofTimeSteponMIESolution

1000

Fig.12.3

GearsMethod

DiscretizeODEtimederivativeovermanypaststeps
dNi,t
dt

Ni,t s,1Ni,th s,2Ni,t2h... s,s Ni,tsh

hs

Rearrangeforanindividualspecies
s

0 =Ni,t +

s, j Ni,tjh +hs
j =1

andforasetofspecies

+
0 =N
t

(12.69)
s

Ni,t s, j Ni,tjh
j=1

hs

dNi,t

(12.70)

dt

d
N
s, j Ntjh +hs t
dt

(12.70)

j =1

Setuppredictorequation

Pt( N
t,m+1 Nt,m) =Nt,m +

s, j Ntjh +hs
j =1

(12.71)
dNt,m

dt

GearsMethod
Simplifyto

(12.72)

PtNt,m =Bt,m

N
=
N

N
t,m
t,m+1
t,m

where

Bt,m =N
t,m +

s, j Ntjh +hs
j =1

Predictormatrix

Pt I hs J t

Jacobianmatrixofpartialderivatives

2 N
i,t,m K,K

J t =
Nk,t,mt
i,k=1

dNt,m
dt

(12.73)

(12.77)
(12.78)

GearsMethod
Solve

for

PtNt,m =Bt,m

N
t,m

thenupdateconcentrationwith

+N
N
=
N
t,m+1
t,m
t,m

Iterateuntil

N
t,m 0

(12.74)

ErrorTests
Localerrortest

NRMSt,m =

(12.75)

1 K
K

Ni,t,m

R
N
+A
tol i,t,1
tol,t

i=1

Globalerrortest

(12.76)

Ni,t,m

NRMSt =

RtolNi,t,1 +Atol,t
K

i=1
1 K

ExampleReactionsand1stDerivatives
Examplereactions

(12.79)

NO+O

NO

+O

(12.80)
O+O

+M

+M

(12.81)
NO

+h

ExampleReactionsand1stDerivatives
FirstderivativesofNO,NO2,O,andO3

d[NO]
=J [NO2] k1[NO][O3]
dt
d[NO2]
=k1[NO][O3] J [NO2]
dt
d[O]
=J [NO2] k2[O][O2][M ]
dt
d[O3]
=k2[O][O2][M ]k1[NO][O3]
dt

(12.82)

PartialDerivatives
PartialderivativesofNO

2[NO]
=k1[O3]
[NO]t

(12.83)

2[NO]
=J
[NO2 ]t

2[NO]
=k1[NO]
[O3]t
PartialderivativesofNO2
2[NO2 ]
=k1[O3]
[NO]t

(12.84)

2[NO2 ]
=J
[NO2 ]t

2[NO2 ]
=k1[NO]
[O3]t

PartialDerivatives
PartialderivativesofO

2 [O]
=J
[NO2 ]t

(12.85)

2[O]
=k2[O2 ][M ]
[O]t

PartialderivativesofO3

2[O3]
=k1[O3]
[NO]t
2[O3]
=k1[NO]
[O3]t

(12.86)

2[O3]
=k2[O2 ][M ]
[O]t

PredictorMatrix
NO
NO
NO2
O
O3

[NO]
1hs
[NO]t
2

[NO2 ]
hs
[NO]t
2[O]
hs
[NO]t
2[O3]
hs
[NO]t

NO2

O3

[NO]
hs
[O3 ]t
2
2
2

[NO2 ]
[NO2 ]
[NO2 ]
1hs
hs
hs
[NO2]t
[O]t
[O3 ]t

2[O]
2[O]
2[O]
hs
1hs
hs
[NO2]t
[O]t
[O3 ]t

2[O3]
2[O3]
2[O3]
hs
hs
1hs
[NO2]t
[O]t
[O3]t
2

[NO]
hs
[NO2]t

[NO]
hs
[O]t

(12.87)

SubstitutePartialDerivativesInto
PredictorMatrix
NO
NO
NO2
O
O3

NO2

O3

1h k O
hs (J )
0
hs (k1[NO])
s( 1[ 3])

hs (k1[O3 ]) 1hs(J )
0
hs (k1[NO])

0
hs (J ) 1hs (k2[O2 ][M ])
0

hs (k1[O3 ])
0
hs (k2[O2 ][M ]) 1hs (k1[NO])

(12.88)

MatrixEquation
PtNt,m =Bt,m
1h (k [O ])
hs (J )
0
hs (k1[NO])
s
1 3

hs (k1[O3 ]) 1hs(J )
0
hs (k1[NO])

0
hs (J ) 1hs (k2[O2 ][M ])
0

hs (k1[O3 ])
0
hs (k2[O2 ][M ]) 1hs (k1[NO])

[NO]
t,m BNO,t,m

[NO2 ]t,m BNO2,t,m

=
[O]
t,m BO,t,m

[O3 ]t,m BO3,t,m

(12.89)

ReorderedMatrix
Placespecieswithmostpartialderivativesatthebottomand
fewestpartialderivativesatthetopofthematrix

1h k O [M ]
hs(J )
0
0
)
s( 2[ 2 ]

0
1hs (J )
hs (k1[O3])
hs (k1[NO])

0
hs(J ) 1hs(k1[O3]) hs (k1[NO])

hs (k2[O2 ][M ])
0
hs (k1[O3]) 1hs (k1[NO])

[O]
t,m BO,t,m

[NO2 ]t,m BNO2,t,m

=
[NO]

BNO,t,m
t,m

[O3 ]t,m BO3,t,m

(12.90)

EffectofSparseMatrixReductionson
MatrixFillinandNumberofMultiplies
1427Gases,3911Reactions
Quantity
Orderofmatrix
Initialfillin
Finalfillin
Decomp.1
Decomp.2
Backsub.1
Backsub.2

Without
Reductions
1427
2,036,329
2,036,329
967,595,901
1,017,451
1,017,451
1,017,451

With
Reductions
1427
14,276
17,130
47,596
9,294
9,294
6,409

Percent
Reduction
0
99.30
99.16
99.995
99.09
99.09
99.37
Table12.2

VectorizationofInnerNestedLoop
Vectorizedinnerloop
NestedLoopA
DO105NK
JSP1=JPROD1(NK)
JSP2=JPROD2(NK)
DO100K
TRATE(K,NK)
*CONC(K,JSP2)
100 CONTINUE
105CONTINUE

=1,NBIMOLEC

=1,KTLOOP
=RRATE(K,NK)*CONC(K,JSP1)

VectorizationofInnerNestedLoop
Nonvectorizedinnerloop
NestedLoopB
DO105K
=1,KTLOOP
DO100NK
=1,NBIMOLEC
JSP1 =JPROD1(NK)
JSP2 =JPROD2(NK) TRATE(K,NK)
100 CONTINUE
105CONTINUE

=RRATE(K,NK)*CONC(K,JSP1)

*CONC(K,JSP2)

StiffnessPredictor
Sp =

2
K dN

1
i,t dt

K N

(12.91)

+A
tol,t
i=1 i,t

No.ofbacksubstitutioncalls

No.ofbacksubstitutioncalls

Numberofbacksubstitutioncallsasafunctionofthestiffnesspredictor.Themorecalls,the
greaterthestiffnessofequations.

200

150

100

50

0
14

10

12

10

10

10

10

10

10

0.01

Predictorvalue(s

Fig.12.4

FamilyMethod

Organizeshortandlonglivedspeciesintofamilies,whicharelonglived,solveforfamily
concentration,thenpartitionfamilyconcentrationsintoindividualspeciesconcentrations

Oddoxygenfamily
[OT ] =[O]+[O(1D)]+[O3] +[NO2]

(12.92)

Oddhydrogenfamily

(12.93)

[HOT ] =[OH]+[HO2] +[H2O2]

Oddnitrogenfamily

(12.94)

[NOT ] =[NO]+[NO2] +[NO3]

Oddchlorinefamily

[ClT ] =[Cl]+[ClO]+[ClO2]

(12.95)

FamilyMethod
Exampleofspeciescyclingwithinoddoxygenfamily (12.96)
O

+h

+h

O(

O+O

+M

+M

SolutionwithFamilyMethod
(1)Calculatereactionratesandfirstderivativesofallspecies
(2)Sumproductionandlosstermsofeachfamily
(3)ApplyforwardEulertofamilyconcentration
(4)Repartitionspeciesconcentrationsinthefamily

Examplewith4totalspeciesand2families
[Fam1] =[A] +[B]+[C]
Reactionsinthesystem

[Fam2] =[D]

AB

ka

B C

kb

C D

kc

(12.97)

(12.98)

SolutionwithFamilyMethod
FirstderivativesofA,B,C,andD

d[A]
=ka [A ]
dt
d[B]
=ka[A] kb[B]
dt
d[C]
=kb[B]kc[C]
dt
d[D]
=kc[C]
dt

(12.99)

ExampleFamilySolution
Firstderivativesofeachfamilyasawhole
(12.100)
d[Fam1] d[A ] d[B] d[C]
=
+
+
=kc[C]
dt
dt
dt
dt
d[Fam2] d[D]
=
=kc[C]
dt
dt
ApplyforwardEulertofamilyconcentrationwith

[Fam]t =[Fam]th +h
Forexample,

(12.101)

d[Fam]th
dt

[Fam1]t =[Fam1]th hkc[C]th

[Fam2]t =[Fam2]th +hkc[C]th

(12.102)

PartitionSpeciesinFamily
ConcentrationofDequalssecondfamilyconcentration

[D ]t =[Fam2]t =hkc[C]th
Relatespeciestofamilyconcentration

(12.103)

[B ]
[C]t
t
+
[Fam1]t =[A]t +[B]t +[C]t =[A ]t 1+

[A ]t [A ]t

RepartitioningSpecies
SolveforA,B,andC,respectively

(12.104)

[Fam1]t
[A ]t =
[B]t [C]t
1+
+
[A]t [A]t
[B]t
[B]t =[A ]t
[A ]t

[C]t
[C]t =[A]t
[A ]t

[B]t
[C]t
Manywaystoobtainpartitioningratios,and.
[A ]t
[A ]t

EstimatingPartitioningRatios
1)Assumeeachspeciesinsteadystate

(12.105)

d[B]
=ka[A] kb[B] =0
dt
d[C]
=kb[B]kc[C] =0
dt
>PartitioningratiosofBandCare

(12.106)

[B]t [B] ka

=
[A ]t [A ] kb
[C]t [C] [C] [B] kb

=
=
[A ]t [A ] [B ] [A ] kc

ka ka
=
kb kc

EstimatingPartitioningRatios
>Finalspeciesconcentrations

(12.107)

ka
[Fam1]t
kb
[B]t =
ka ka
1+ +
kb kc

[Fam1]t
[A ]t =
k
k
1+ a + a
kb kc

ka
tk
c
k
+ a
kc

[Fam1]
[C]t =
k
1+ a
kb

EstimatingPartitioningRatios

2)FirstlinearizetheODEofeachspecies

(12.108)

d[A]t
d[B]t
=ka[A ]t
=ka [A ]th kb[B]t
dt
dt
d[C]t
=kb[B]th kc[C]t
dt
thenintegratewithsimpleexponentialmethod
(12.109)
k h
[A ]t [A ]th e a
kbh

[B ]t [B ]th e

ka[A ]th
kbh
+
1e
(
)
kb

kb[B ]th
kch
[C]t [C]th e
+
1e
(
)
kc
>plugresultsintopartitioningratios
kch

EstimatingPartitioningRatios
3)FirstwriteeachspeciesODEinfinitedifferenceform (12.110)

[A ]t [A]th
h

[B]t [B]th
h

[C]t [C]th
h

=ka[A]t

=ka[A]t kb[B]t

=kb[B]t kc[C]t

EstimatingPartitioningRatios
thenrearrangefinitedifferenceequationsintoamatrix (12.111)

1+hka
0
0 [A ]t [A]th

hk

1+hkb
0 [B]t =[B]th
a

0
hkb 1+hkc[C]t [C]th
>thensolvethematrixfor[A]t,[B]t,and[C]tandplugresultsintopartitioningratios

Example
Addbimolecularreactiontothesystem

A +C B +D
Linearized,finitedifferenceformsofA,B,andC

(12.112)

[A ]t [A]th
=ka[A]t kac[A]t [C]th
h
(12.113)
[B]t [B]th
=ka[A]t kb [B]t +0.5kac([A ]t [C]th +[A ]th[C]t )
h
(12.114)

[C]t [C]th
=kb[B]t kc[C]t kac[A]th [C]t
h

ExampleWithBimolecularReaction
Resultingmatrix

(12.115)

1+hka +hkac[C]th
[A ]t [A]th
0
0

0.5(hkac[A ]th ) [B]t = [B]th

hka 0.5(hkac[C]th ) 1+hkb

0
hkb 1+hkc +hkac[A ]th [C]t [C]th

>thensolvethematrixfor[A]t,[B]t,and[C]tandplugresultsintopartitioningratios