NOx Kinetics Calculations - CVODE starts at line 100 on EXCEL Sheet

a1

a2

a3

a4

N2

7.709928

-5.503897

13.12136

-11.67955

O2

7.361141

-5.369589

20.54179

-25.86526

NO

8.462334

-10.40669

27.54876

-30.28119

5.974134

-4.241883

7.931254

-7.94423

4.966526

0.01150479

-0.03333487

0.04616989

Only Change B11!!!

T initial (K)

298.15

0.29815

here we account

T final (K)

2300

2.3

for units in To and Tfinal

cal to kcal

0.001

following Prothero (1969)

hi0 (cal/mol)

si0 (cal/mol-K)

Gi0 (cal/mol)

hi0 (J/mol)

N2

16014.1266373358

61.4299473815

-125274.752340215

67047.9454051976

O2

16883.6477699937

65.4837175637

-133728.902626434

70688.4564834098

NO

38050.39198443

66.4849434232

-114864.977888936

159309.381160411

69589.2082615801

48.7706333788

-42583.2485096785

291356.097149584

122911.094383637

46.7643867315

15353.004901201

514604.169965411

Reaction

ln KR = -vi Gi0/RT

KR

Reaction

NO+N=O+N2

14.9550399033

3125297.08339049

R1

2.70E+13

N+O2=NO+O

8.5495566122

5164.4640590579

R2

9.00E+09

O+O+M=O2+M

10.6261144411

4.1197E+04

R3

1.20E+17

Temperature Out (K)

see (row 11, col 2)

Pressure Out (atm)

Copied

Residence Time (sec)

1.00E-01

Solution from the

Outlet Conditions

CVODE Code
see line 130 below

Initial guess for

mol fractions out

Solution from CVODE

[g-moles/cm ]

1.11268796068E-006

0.000001094

[O2]

4.18582613780E-006 4.16839753251E-006

[N2]

MW_Mixout

28.8343454704

CVODE MW_out

28.8343454704

3.02176762680E-008

[NO]

5.87269440725E-009

[O]

5.90690033012E-014

OUT

OUT

0.21

0.2064779136

0.79
0

[N]

N_out
Weight fraction Out

Molar Flowrate Out

yO2 / wO2

0.2291380419

0.0010940261

0.7867106617

yN2 / wN2

0.7643121455

0.0041683975

0.0057030473

yNO / wNO

0.0059348046

3.021767626802E-005

0.0011083663

yO / wO

0.0006150025

5.872694407249E-006

1.114822046E-008

yN / wN

sum yi or wi

R=

82.05746

5.4154091943E-009 5.906900330118E-011
1

0.0052985141

from CVODE

0.0052985141

Check Atomic B

cm3-atm/gmol-K

M (molar density) =

5.2985140984824E-006

mol/cm

Volume =

100

cm3

g-moles/cm^3-sec
Rate O2

-1.80E-07

O_2

Rate N2

-1.5108867668513E-007

N_2

Rate NO

3.0217676268023E-007

NO

Energy Balance AFTER

Rate O

5.8726944072498E-008

Material Balance is Solved

Rate N

5.9069003006622E-013

Q_Feed (cal/s)

Q_Out (cal/s)
Qadded (cal/s)
MW_O2

31.9988

MW_N2

28.0134

MW_NO

30.0061

MW_O

15.9994

MW_N

14.0067

Inlet Conditions
Set Feed Stream

Air (21% O2; 79%N2)

Tin (K)

650

Pin (Atm)

Set mole fraction in

Find mass fraction in

y_O2in

0.21

w_O2in

0.2329175115

y_N2in

0.79

w_N2in

0.7670824885

y_NOin

w_NOin

y_Oin

w_Oin

y_Nin

w_Nin

MW_Mixin

28.850334

Sum

Residence Time Set Above, see (row 30,col 2)

mass flow (g/s)

0.152779186

Here are Checks on the CVODE solution

g/s
Mass Balances
O2
0
N2
1.685934378E-017
NO
-7.914675859E-018
O
6.301925128E-018
N

-4.125827383E-018

Other Checks
Con_5
Con_8

0
0

Chemkin Solution
Chemkin Solution
Chemkin Solution

Tout = 2300 K
mol fraction
g-mol/cm3

g/s

g/s

Rate*MW*Volume

(P*MW_Mixout*Volume)/(R_gas*T*Res_time)

-0.0005774243
0.0005774243
-0.0004232508
0.0004232508
0.0009067146
-0.0009067146
9.3959586899E-005 -9.39595868993E-005
8.2736180441E-010 -8.27361808539E-010

O_2
O

Con_6
Con_9

Res time = 0.1 s

0.20656
1.09E-06
[O2]

0
0

Vol = 100 cm3

0.7868
4.17E-06
[N2]

5.52E-03

2.92E-08
[NO]

CVODE
NEQ
NOUT

5
15

RTOL

1.00E-06

T0

T1
TMULT

0.0000001
10

initial y components

Y1
Y2
Y3
Y4

Y5
NOx - Kinetics Results
1.00E-07
1.00E-06

/* number of equations */
/* number of output times */
/* scalar relative tolerance
/* initial time
/* first output time
/* output time factor

vector absolute tolerance components

1.112687961E-006
ATOL1
1.00E-18
4.185826138E-006
ATOL2
1.00E-18
0
ATOL3
1.00E-18
0
ATOL4
1.00E-18
0
ATOL5
1.00E-18

*/
*/
*/
*/

y components [g-mol/cm3]

[O2]
[N2]
[NO]
[O]
[N]

[O2]

[N2]

[NO]

[O]

1.11E-06
1.11E-06

4.19E-06
4.19E-06

2.32E-20
2.31E-18

7.9122825942771E-015
7.91222186231346E-014

1.00E-05
1.00E-04
1.00E-03
1.00E-02
1.00E-01
1.00E+00
1.00E+01
1.00E+02
1.00E+03
10000
100000
1000000
10000000

1.11E-06
1.11E-06
1.11E-06
1.11E-06
1.10E-06
1.09E-06
1.09E-06
1.09E-06
1.09E-06
1.09E-06
0.000001094
0.000001094
0.000001094

4.19E-06
4.19E-06
4.19E-06
4.19E-06
4.18E-06
4.17E-06
4.17E-06
4.17E-06
4.17E-06
4.17E-06
4.168397532509E-006
4.168397532509E-006
4.168397532509E-006

2.60E-16
2.64E-14
2.63E-12
2.47E-10
1.27E-08
3.02E-08
3.02E-08
3.02E-08
3.02E-08
3.021767626802E-008
3.021767626802E-008
3.021767626802E-008
3.021767626802E-008

7.91186462783134E-013
7.90827090719953E-012
7.87255409861457E-011
7.5174535763862E-010
4.58262798160468E-009
5.87269638732573E-009
5.87269440345473E-009
5.87269440724943E-009
5.87269440724944E-009
5.87269440724944E-009
5.87269440724944E-009
5.87269440724944E-009
5.87269440724944E-009

a5

a6

Hf0(cal/mol)

a7

Sf0(cal/mol-K)

5.233997

-1.173185

0.103883

45.77

15.94566

-4.85889

0.5861501

49.004

17.18511

-4.95726

0.5755281

21580

50.347

4.403357

-1.271341

0.1491408

59559

38.468

-0.03242073

0.01094605

-0.001373727

112965

36.614

cal to joules

si0 (J/mol-K)

4.1868

Gi0 (J/mol)

257.194903697 -524500.33309801
274.1672286955 -559896.16951635
278.3591611243

-480916.6894254

204.1928878304 -178287.54486032

R = 8.31J/mole-K

195.7931343674 64279.9609203482

R_gas = 82.05746 cm3-atm/gmol-K

cal/gmol

cm3/gmol-s

Here P0 = 1 atm

cm3/gmol-s

Ea

kfor = ATbexp(-Ea/RT)

KC = KR(P0/RT)c+d-a-b

krev = kfor/KC

355

24982257140279.6

3125297.08339049

7.993562E+06

6,500

4992758150746.4

5164.4640590579

9.667524E+08

-1

52173913043478.3

7775149915.3937

6710.3417440455

N_in

Weight fraction
wO2

Weight fraction IN

Molar Flowrate In

0.2329175115

0.0011120713

wN2

0.7670824885

0.0041835064

wNO

wO

wN

Sum

0.0052955777

from CVODE

0.0052955777

Check Atomic Balances

O Constraint

-1.2332799712E-018

N Constraint

-5.2476301871E-019

h_Feed (Cal/g)

561.405149597

save the h value

86.9947928214

cal/g at the T_feed

Tin = 650 K
Tout = 2300 K
13.2909936331

86.7828757369
73.4918821038

h_in (or h_feed) determined by

setting T
Cell B11 = T_in

Find concentrations in
[O2]

3.93720355318E-006

[N2]

1.48113847953E-005

[NO]

[O]

[N]

Con_7

Based on outlet
conditions

ut*Volume)/(R_gas*T*Res_time)*(w_O2in-w_O2)

O_2
N_2
NO
O
N

N_2
N

1.12E-03

1.12E-08

5.93E-09
[O]

5.93E-14
[N]

[N]
6.272690560E-021
3.533454415E-019

NO

4.681574937E-018
4.754536069E-017
4.741200268E-016
4.556825344E-015
3.591133902E-014
5.906900167E-014
5.906900315E-014
5.906900330E-014
5.906900330E-014
5.906900330E-014
5.906900330E-014
5.906900330E-014
5.906900330E-014

Hf0(J/mol)
0
0
90351.144

NO

249361.6212

472961.862

Reaction
R1
R2
R3

answer

5.00E-007
1.03E-009
0.0000001
1.25E-008
0.000000001
1.95E-008
0.068581226
0.015527921
0.231461637
0.000685812
4.2863E-005
0.000728676

Page 13