-------
0.10
03
0.08
0.06
XK
DC
£ 0.04
111
o
x
m
u
0.02
Nk
0.00
70 140 210 280 350 420 490 560
TINE (MINUTES)
N02
0.44
+ + i- + +
0.33
0.22
Ui
o
o
0.11
0.00
70 140 210 280 350 420 490 560
TIHE (HINUTES)
ETH
2.40
2.20
ci
i.eo
1.60
70 140 210 280 350 420 4S0 500
TIHE (MINUTES)
FIGURE 33. SIMULRTI0N RESULTS F0R
UNCB 11078

-------
1.60
1.20
0.80
0.40
0.00
03 ¦
NB ~
N02 *

0 60 160 240 320 400 480 S60 640
TIHE (MINUTES)
2.80 -
2.10 -
1.40
u
0.70 -
0.00
0 80 160 240 320 400 480 S60 640
TIHE (MINUTES)
FIGURE 34 .
SIMULRTI0N RESULTS F0R
UNCR 6J67B
82

-------
1.60
1.20
-------
0-80 -
0.60 -
0.40 -
u
z
m
u
0.20
0.00
0 100 200 300 400 500 600 700 800
TIHE (MINUTES)
0.92
0.69
0.4S
o
z
o
0.23
0.00
1 1 1
1 1 1 1
ETH *
—


-
*mZ		
****
1 1 1
i i i i
0 100 200 300 400 500 600 700 800
TIHE (HINUTES)
1.20
0.90
mm
t-
fe 0.60
XXX X
u
0.30
o nri	J—lit.
0 100 200 300 400 500 600 700 800
TIME (HINUTES)
FIGURE 36 . SIMULATION RESULTS F0R
UNCR 70178
84
-------
1.25
1.00 -
0.75 "
u
0.25
0.50 -
0 90 180 270 360 450 540 630 720
TIME (MINUTES)
0.80 -
o.
a.
0.60
o
z
B
u
0.40 ~
0.20 -
0 90 180 270 360 450 540 630 720
TIME (MINUTES)
1.20 -
0.90 -
ui
u
x
u
I I
0.80 -
0.30 -
0 80 180 270 360 450 540 630 720
TIME (MINUTES)
FIGURE 37 . SIMULRTI0N RESULTS F0R
UNCR 73078
85
-------
1.20 -
0.90
0.80 -
UJ
o
0.30 -
0.00
I	1
0 60 120 180 240 300 360 420 400
TIME (MINUTES)
1.60
a.
a.
1.20
cc
0£
0.80
ui
u
0.40
0.00
1 1 I
ETH ¦
1 1 1
" 1
- *—

	
-
>x
—
-
m
¦ X
1 1 1
i i i
1
0 60 120 180 240 300 360 420 480
TIME (MINUTES)
FIGURE 38 . SIMULATI0N RESULTS F0R
UNCB 80678
0.44 -
0.33
0.22 -
£_)
3C
0.11
0.00
0 70 140 210 280 350 420 490 560
TIME (MINUTES)
0.88
0.51
0.34
u
z
a
u
0.17
0.00
I 1 -T-
ETH ¦
~r-
i i
i
M w


—



—
1 1 1
_ j
' <
i
TIME (MINUTES)
FIGURE 39. SIMULATI0N RESULTS F0R
UNCR 61078
86
-------
0.60
ac
o_
Q_
0.45
z
CB
h-
-------
1.25
ETH
1.00
z
flu
0.
0.75
z
m
M
H-
cr
oc
I—
z
UJ
0.50
CJ
o
0.25
0.00
80 160 240 320 400 480 560 640
T1HE (HINUTES)
1.25
03
N0
N02
1.00
o.
0.75
£ °'S°
u
0.25
0.00
80 160 240 320 400 480 S60 640
TIME (HINUTES)
2.50
2.00
1.50
1.00
CJ
m
u
0.50
0.00
1 1 1
1 1 1 1
00 ¦
—
-
K*
_
-
.

»« mi****
_
1 , 1 _i_
1 J	I	1	
0 80 160 240 320 400 480 560 640
TIME (HINUTES)
FIGURE 41 . SIMULATI0N RESULTS F0R
UNCB 81578
88
-------
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
1.25
1.00
0.73
0.S0
CJ
OB
CJ
0.25
0.00
t r
H0
N02
i—r
' i	I	!	l	I—
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
0.80
0.60 -
0.40 -
o
ac
m
u
0.20 -
0.00
I I
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
0.S0
0.72 -
0.54 -
t 0.36 -
u
*
s»
u
0.18
0.00
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
FIGURE 42 . 5IMULRTI0N RESULTS F0R
UNCR B217B
89
-------
0.80 -
0.60 -
0.40
0.20 -
0.00
2.SO
2.00 -
1.30
ex
az
0 70 140 210 280 350 420 490 560
TINE (HINUTES)
1.00 -
0.50 -
0 70 140 210 280 350 420 490 560
TINE CNINUTESI
1.60
1.20
cc
at
o.eo
u
at
u
0.40
0.00
1 1 1 1 1 1 1
0.005
I l i
1 1 1 —1	
CB ¦

PAN ¦

- —
0.004
X
-
—
- _
o.
fr.
~ 0.003
-
V IK m
¦ K
oc

" ™ 1

£ 0*002
IftJ
u
-
K ^

m
0.001
-
X _
i i t i i i i
n aoh
1 1 1

0 70 140 210 280 350 420 490 580
TINE (NINUTES)
0 70 140 210 260 350 420 490 S6Q
TINE (HINUTESI
FIGURE 43 . SIMULATION RESULTS F0R
UNCR 91578
90
-------
1.25
1.00 -
0.73 -
-------
1.25
1.00 -
z
a.
a.
0.75
£ 0.50 -
CJ
z
s
o
0.25 -
0.00
0.40
0 60 160 240 320 400 480 S60 640
TIME (MINUTES)
0.32 -
x
0-
0.24 -
cc
ae.
0.16 -
Li
Z
ea
o
0.08
0.00
0 80 160 240 320 400 480 560 640
TIME (MINUTES)
1.20
0.90
0.60
CJ
z
CD
l>
0.30
0.00
1 1 1 1 1
1 1
ETH *
-


**
X

1 1 l_ J—1—
1 1
* 0 80 160 240 320 400 480 560 640
TIME (MINUTES)
1.80 -
1.20
0.80
ID
CJ
0.40
0.00
1 1 1
1 1 1
i
ca >

—
-



m


y*
—
*

—
1 1 1
• i i
j- ,
0 80 160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 45 . SIMULATION RESULTS F0R
UNCR 92176
92
-------
1.20 -
o_
0.
0.90 -
a
at
Ui
u
z
OB
(J
0.60 -
0.30 -
0 65 130 195 260 325 390 455 520
TIHE (MINUTES)
0.40 -
a.
CL
0.30 -
t 0.20 -
u
z
a>
o
0.10 -
0 65 130 195 260 325 390 455 520
TIHE (MINUTES)
1.60
1.20
0.80
iu
u
0.40
0.00
1 1
1(111
ETH ¦
—
-

—
\* ~

\*

N. *
K

1 1
i i i i i
0 65 130 195 260 325 390 455 520
TIHE (HINUTES)
2.40 -
1.80 -
t 1.20 -
u
o
0.60 -
0.00
0 65 130 195 260 325 390 455 520
TIHE (HINUTES)
FIGURE 46 . SIMULRTI0N RESULTS F0R
UNCB 100276
93
-------
0.010
PRN
0.008
0.006
£ 0.004
UJ
o
0.002
0.000
65 130 195 260 325 390 455 520
TIME (MINUTES)
FIGURE 46 . (Concluded)
94
-------
0.05
0.04
a.
fL
0.03
-------
0.56 -
0.42 -
cc
0.20
u
a:
a
CJ
0.14
0.1
1.0 52.5105.aS7.S10.CB62.SIS.(867.920.0
TINE (MINUTES)
2.50
2.00
a.
a.
z
Ui
CJ
1.50
1.00
O.SO
¦°8
1 1
1 1 1 1
1 ~
ETH ¦

-
-
*
-


s,* -
1 •
_L	J	L_, 1
1
.0 52.5105.a57.S10.CE62.S15.IB67.a20.0
TINE (MINUTES)
0.60
0.45
0.30
hi
o
0.15
0.1
1 1 1
l I I l
F0RM *

-
*
—


< I
i
1 1 1 I
.0 52.5105.057.310.S62.915.067.920.0
TINE (NINUTES)
0.005
0.004
0.003
0.002
0.001 -
i—i—i—i—i—T
PAN
0.00Q<1111	I I
0.0 52.5105.Q57.£10.£62.5)15.(B67.912Q.Q
TINE (MINUTES)
FIGURE 48 . SIMULRTI0N RESULTS F0R
UNCB 101778
96
-------
1.25
1.00
0.73
t—
(E
ne
0.30
ul
cj
0.25
0.00
1
03
1
¦

1 1 1
1
N0
~



N02
X


—
-



** *»



/ *




/ *






—

/x
P<>x
—



/ * \




X ^

, .J.
u\~mJ



0 70 140 210 280 350 420 490 560
T1HE (MINUTES)
2.50
2.00 -
a.
1.30
fc 1.00 -
lli
u
z
0.50
0 70 140 210 280 350 420 490 560
TIHE CHINUTES)
0.90
0.72
0.54 -
fc 0.36 -
0.16 -
0.00
0 70 140 210 280 350 420 490 560
TIHE (HINUTES)
1.20 -
0.90 -
£ 0.60 -
ui
o
z
u
0.30
0.00

m
m
J	I	I	I	I	L
0 70 140 210 280 350 420 490 560
TIHE (HINUTES)
FIGURE 49 . SIMULATION RESULTS F0R
UNCR 101878
97
-------
0.005
PAN
0.004
0.003
0.002
0.001
0.000
70 140 210 280 350 420 490 560
TIME (MINUTES)
FIGURE 49 .
-------
0.96 -
0.72 -
z
UJ
<_>
z
00
u
0.40 -
0.24 -
0.00
0 80 160 240 320 400 480 560 640
TINE (MINUTES)
2.50
2.00 -
1.30 -
a
K
-------
appear to be the UV data and the initial reactivity. Thus there are clear
days that have low photolysis rates (e.g., 30 June 1978) and clear days that
have high photolysis rates (e.g., 18 October 1978). Then there are days
that have high initial reactivity (e.g., 1 July 1978) and days showing a
low initial reactivity (e.g., 18 October 1977).
For the interim report of last year (Whitten et al., 1979), we had
simulated six ethylene experiments in the UCR chamber. The same six experi-
ments were included this year, but the new chemistry has reversed the
problems we reported previously. Two sets of three experiments were per-
formed; the second set used about twice the concentration of precursors as the
first set, yet similar ozone maxima resulted. Last year the simulations showed
too much ethylene decay in the second set but correct decay in the first set
of experiments. Tables 15 and 16 show the initial conditions and results for
this year while Figures 51 through 56 present the graphical results. Note
that the simulations are now somewhat slow for ethylene decay in the first
set and agree closely with the measurements in the second set.
ETHYLENE/ACETALDEHYDE
This combination of precursors requires essentially the same set of
chemical reactions as a simulation of propylene, except for the numerical
values of the rate constants involving the olefin. The proper choice of
organic concentrations can control the rate of the smog chemistry so that the
two sides of a dual chamber experiment have equal reactivity. Two such dual
chamber experiments comparing propylene with ethylene/acetaldehyde were per-
formed at the UNC chamber; we then simulated these experiments using our
current chemical mechanisms. The initial conditions are provided in Table 17.
The results are given in Table 18 and are illustrated by Figures 57 through
60- (The mechanism used for propylene will be reported in the following seg-
ment.) The results show that PAN chemistry will require further developmental
work. The dual chamber experiment of 25 October 1978 shows that the acetalde-
hyde mechanism simulates too much PAN and, therefore, an additional pathway to
PAN production is probably needed in the propylene mechanism, since the
100
-------
TABLE 15. INITIAL CONDITIONS AND PHOTOLYSIS RATE CONSTANTS FOR
THE UCR ETHYLENE/NOx SMOG CHAMBER EXPERIMENTS
4 -r *
Initial concentration (ppm) 	Photolysis rate constant (x 10 m1n )
Run
number
Ethylene
NO
no2
H0N0
no2-no+o
03-^)(10)
o3-o(3p)
HONO^O+OH-
H202-*20H-
F0 RM-»-Products +
EC-142
0.92
0.322
0.158
0.010
0.33
10
107
990
4
16
EC-143
1.95
0.39
0.11
0.012
0.33
10
107
990
4
16
EC-156
1:95
0.376
0.124
0.018
0.32
5
104
600
5
16
EC-285
1.9
0.791
0.215
0.02
0.39
5
120
1100
5
1.1
EC-286
3.758
0.708
0.237
0.02
0.39
5
120
1100
5
1.1
EC-287
3.995
0.404
0.124
0.008
0.39
5
120
1100
5
1.1
* Rate constant In min"^ for N02.
t The relationship between FORM+Products and carbonyl photolysis rate constants 1s discussed elsewhere.
TABLE 16. UCR ETHYLENE EXPERIMENTS—SIMULATIONS AND MEASUREMENTS
InttUl TOil Dlf'ffce »•Vim"!Oil D1 ffertnce iNn,i D1ff*r*nc»	V«n»l niff^rpnc*
Initial Initial HC/NO, "* In 03 "V "T 1°}J In tlws to N0?J 1n no? Mjimw Ino?] (
tup. [*0,1 MOj/NO, r.tlo*	o3		tl'F-)		-("'""'"Ji.
np.
iv^ 1 nvjj	1 v v' v	m ^ »>*v
r»tlQ (pprcC/ppwi) Sla. Heas. (percent)*
EC-142
0.48
0.33
3.8
0.71
0.77
EC-143
0.50
0.22
7.8
0.87
1.07
EC-156
0.50
0.25
7.8
0.78
1.03
EC-ZB5
1.0
0.21
3.8
0.86
0.75
EC-286
0.95
0.25
7.95
1.17
1.06
EC-287
0.53
0.24
15.1
1.02
0.92
-19
-24
17
10
n
Sin.
Hcas.
^percent) f
Sim.
Heas.	
(percent^*
S im.
Meas^
_ Xpercfntjt
^300
a 310
9
0.38
o. in
?7
ion
100
0
170
170
n
0.1?
0.
11
65
60
8
170
1 SO
13
0.41
0.36
14
50
50
0
>360
>360
--
0.75
0.70
7
150
150
0
190
160
19
0.80
0.75
7
60
60
0
120
100
20
0.46
0.45
3
45
45
0
03 nailma; average difference • -2 percent, standard deviation - *17 p*rc#nt.
H02 mx1mi: average difference ¦ 12 percent, standard deviation » i8 percent
•
Haiifiun one-hour-iverage concentration.
+ [(Simulated value - Measured value)/Measured value] * 100.
* Tine from beginning of irradiation to beginning of the period during which the maximum one-hour-avorag? concentration occurred.
-------
1.25
1.00
ac
o_
a.
0.73
0.S0
cj
z
s
u
0.25
O.OO
- 1 1 1 1 1 1 1
03 *

1 1 1 1 1 l 1
NO "
ETH +

N02 ~
~
0.40
sc
— —

CL
~ 0.30
«a
/ 4
t / +++++ \
T / + +-l. \

—4
\ /+ +.\

4-
-------
1.20
a.
Q.
0.90
ca
i—
a:
z
i&j
o
z
(B
u
0.60
0.30
0.00
1
03
1 1 1 1 1 1
*
-
—
—
*
* **
**« -
* ' \ "I

/
f
'J
11 111 1 1
' 0 50 100 15Q_ 200 250 300 350 400
TIME (MINUTES)
0.48 -
x
a.
0.36
cc
QL
0.24
o
z
s
u

0.12 -
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
i—i—T
ETH ¦
2.40 -
1.80
1.20 -
CJ
3E
S
U
0.60 -
0.00
****
J	1	1	I	1	I 1
0 50 100 150 200 250 300 350 400
TIHE (MINUTES)
0.030
i—r
PAN ¦
RL02 ~
i—r
0.024 -
t
0.018 -
+ +
+ +
0.012 -
o
z
aa
u
0.006
0.000
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 52 . SIMULRTI0N RESULTS F0R
EC-1^3
103
-------
FBRM
1.20
0.90
i o.eo
o
o
0.30
0.00
50 100 150 200 250 300 350 400
TINE (MINUTES)
FIGURE 52 (Concluded)
104
-------
1.20 -
0.90 -
-------
1.20
0.90
ct
Of
0.60
-UJ
u
u
0.30
0.00
1 1 1 1
r i
-1 -
F0RH m

—
fQtfr	^

—
/ *


/ *


~ f X

—
1 1 1 1
i i..
1
" 0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FJGURE 53 . (Concluded)
106
-------
1.25
1.00 -
3C
BL
0.75
0.S0
cj
z
CB
u
0.25
0.00
X \ -
0 50 100 150.. 200 250 300 350 400
TIME (MINUTES)
u
z
CJ
ETH
2.00
1.60
1.20
0.60
0.40
* 0 50 100 150 200 250 300 350 400
TIME (MINUTES)
1.20
0.90
0.60
Ui
o
0.30
0.00
1 1
FARM m
i i i i
™T

'N.

/*
* *
J
X
~ y*
f ii
1 1 1 1
, L
0.025
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
i—i—i—i—T
RLD2 ¦
PAN +
0.020
t
0.015 -
£ 0.010 -
UJ
o
X *
m —
u
0.005 -
0.000
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 54 . SIMULHTI0N RESULTS F0R
EC-285
107
-------
0.0012
0.0009
O.OOOQ
•iLt .
u
s
u
0.0003
0.0000
t—i—1 r
MEN3
* * * -
X X
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 54 . (Concluded)
108
-------
ETH
*.00
a.
a.
3.20
z
M
t—
(—
z
Ul
2.40

z
CD
U
1.60
0.80
50 100 150 200 250 300 350 400
TIHE (MINUTES)
03
N0
NB2
1.60
1.20

^ 0.80
UJ
L)
0.40
0.00
50 100 15Q 200 250 300 350 400
TIHE (MINUTES)
0.025
0.020
0.015
j~ 0.010
UJ
o
o
0.005
0.000
50 100 150 200 250 300 350 400
TIHE (MINUTES)
FBRH
2.40
3C
a.
o.
1.80
a
4—t
»-
cr
~—
z
1.20
ui
u
ae
9
o
0.60
0.00
TIHE (MINUTES)
FIGURE 55 . SIMULRTI0N RESULTS F0R
EC-286
109
-------
0.0012
0.0009
-------
1.20 -
0.90 -
CC
DC
0.60 -
U1
o
0.30 -
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.60 -
0.45 -
0.30
a
u
fl.15
0.00
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
4.00
3.20 -
CE
0£
& 2.40 -
1.60 -
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.025
0.020
0.015
cc
te.
0.010
hi
o
0.005
0.000
i—i—i—T
PON ¦
RLD2 +
+ +
I—f>LD2
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 56 . SIMULflTJBN RESULTS F0R
EC-287
111
-------
2.40
1.80
1.20
0.60
°-°°0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 56
-------
TABLE 17. INITIAL CONDITIONS FOR UNC ETHYLENE/ACETALDEHYDE
EXPERIMENTS AND OTHER SIDE PROPYLENE/NO EXPERIMENT
X
Date
Chamber
Side
Sky
Conditions
Beginning
time of
simulation
CH^CHO-
Initial
Ethylene
Concentrations (ppm)
Propyl ene NO ^2
HONO
H2G
AID + hv
Constant
10/12/78
Red
Clear
7:24
.63
.0985
—
.364
.115
.004
2 x 104
1 .0*
10/12/78
Blue
Clear
7:24
--
—
.443
.364
.115
—
1.6 x 104
1 .0*
10/25/78
Red
Clear
7:14
.58
.0985
—
.341
.103
.002
2 x 104
1 .0*
10/25/78
Blue
Clear
7:14
—»
--
.408
.338
.104
.009
1.6 x 104
1.0*
UV data used in simulations instead of TSR.
TABLE 18. UNC ETHYLENE/ACETALDEHYDE AND PROPYLENE EXPERIMENTS-SIMULATIONS AND MEASUREMENTS

Chamber
Initial
[NO,]
Initial
no2/nox
Initial
HC/NOx
Maximum [0,]
Difference 1n
0^ maxima
Time to maxima
0^ (m1n)
Difference in
Time to
Og maxima
Date
Side
(ppmC/ppm)
S1m.
Meas.
S1m.
Meas.
10/12/78
Red
.479
.24
3.04
.25
.24
4
490
490
0
10/12/78
Blue
.479
.24
2.77
.34
.39
-13
450
>490
—
10/25/78
Red
.444
.23
3.06
.15
.14
7
490
490
0
10/25/78
Blue
.442
.24
2.77
.23
.23
0
480
>560

-------
0.48 -
a.
Q_
0.36
tz 0.21 -
u
z
0.12
1 MM	———
0 70 140 210 260 350 420 490 560
TIHE (MINUTES)
0.20
0.16
0.12 -
-------
03
N02
0.56
x
O-
0.42
cr
o*
£ 0.28
ui
u
0.14
0.00
TIME (HINUTES)
PR0P
0.56
x
D.
0-
0.42
z
s
M
I—
cr
£ 0.26
Ui
CJ
SK
s
o
0.14
0.00
70 140 210 280 350 420 490 560
TIME (MINUTES)
0.40
0.32
x
0.
Q-
0.24
£ 0.16
CJ
CJ
0.08
0.00
70 140 210 280 350 420 490 560
TIME (HINUTES)
FIGURE 58. SIMULATI0N RESULTS F0R
UNCB 30127B
115
-------
0.48
0.36
0.24
bJ
o
0.12
0.00
—,—r ,
03 m
N0 +
N02 x
.... j ,
1 1
+
X
X.
X X
-

—

\
^ *
, J
1

0 70 140 210 200 350 420 490 560
TIHE (MINUTES)
0.12 -
0.09 -
(_>
z
n
u
0.06 -
0.03 -
0 70 140 210 280 350 420 490 560
TIHE (HINUTES)
0.76 -
0.57

0.38 -
0.19 -
0 70 140 210 280 350 420 490 560
TIHE (HINUTES)
0.84 -
0.63
*Z 0.42 -
£
u
0.21 -
0 70 140 210 280 350 420 490 560
TIHE (HINUTES)
FIGURE 59 . SIMULRTI0N RESULTS F0R
UNCR 102578
116
-------
0.10
0.08
a.
0.06
OS
£ 0.04
iii
c_>
o
0.02
0.00
70 140 210 280 350 420 490 560
THE (HINUTESI
FIGURE 59 . (Concluded)
117
-------
0.60 -
G_
CL
0.45 -
cr
oc
0.30
m
u
0«15 -
0.00
0 60 160 240 320 400 480 560 640
TIHE (MINUTES)
0.52 -
0_
Q.
0-39 -
GC
DC
IU
O
CD
U
PR0P ¦
v.
0.26 -
0.13 "
'0 80 160 240 320 400 4o0 560 640
TIHE (HINUTES)
0.24 -
0.18 -
fc 0.12 -
CJ
z
m
o
0.08 -
0.00
0 80 160 240 320 400 480 S60 640
TIHE (HINUTES)
0.88
0.66
0.44
CJ
T.
m
o
0.22
0.00
I 1 1
C0 ¦
1 1 1
—1	
*
	

—
1 1 1
i i i
i
0 80 160 240 320 400 460 560 840
TIME (HINUTES)
FIGURE 60 . SIMULRTI0N RESULTS F0R
UNCB 102578
118
-------
0.10
PAN
0.08
z 0.06
*—<
t—
cr
a*
CJ
0.02
0.00
160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 60 . (Concluded)
119
-------
simulated PAN for the propylene side is too low. Involvement of the methyl -
substituted Criegee intermediate with N0X may be implicated, or at least some
species must be involved that does not exist in the ethylene/acetaldehyde
chemistry.
PROPYLENE
Most of the experiments for which we have smog chamber data have used
propylene either exclusively or in mixtures. Traditional mechanism develop-
ment has, in the recent past, concentrated on this molecule. However, our
own recent experience indicates that reactions in the inorganic, formalde-
hyde, and acetaldehyde parts of the propylene chemistry may require more
thorough validation before significant changes in the chemistry particular to
propylene can be justified. The present report demonstrates the performance
of the current propylene mechanism (Table 19) on 15 experiments in the UCR
chamber and 28 experiments in the UNC chamber. In the course of modeling
these experiments, four changes were made to the propylene mechanism reported
last year (Whitten et al., 1979). However, the main changes in the overall
chemistry used in the simulations were produced by the temperature and water
dependent PNA reactions. The four reactions that were changed are described
in the following subsections.
3
0( P) + Propylene
Previously, this reaction resulted in either radicals or propylene
oxide, in equal proportions. Currently, we have changed the ratio of these
products, adding pro
-------
TABLE 19. REACTIONS OF PROPYLENE*
ZD,


ij ~ CHjCHD - Hp <0^
CHgOj T wi^<
CHgOJ ~ HO •» »02 ~ HCHO
CHjOj ~ N02 »3 ~ HCHO
V™2
CHjCHOJ * CHjCHO - CWjO^^CHCHj
CH^CHOj ~ M02 - HGj ~ CHjCHO
Rate const-ant
(pp«t ^ a i n ^)
CKjCH-CMj ~ 0 —- CXjOj * CHjCIOJOj	1 * » 10
311
0l30(-CM? * t - CMjCH	Oj,	J * 10
CKjCH - CH? ~ 0 - CHjCHjCHO	1 X 103
°Z
CMjCH-tHj + OH- —. CH3CH(C'|CHjOH	4.2 I 10
7.82
CHjCH'CKj ~ Oj HCHO ~ CHjCHOj	7.5 x 10"3
i.7 x lO*1
l.» * 102t
9 * )01+
1*
CTjOj - HC{0)QH	6 > 10
2
x 103
2 * 103
121
-------
TABLE 19. (Concluded)
Reaction
com tint
02
?o2
CHjCHOj —• CMjOj ~ C02 « HCj
Oz
CH3CH0j CHjO- » CO ~ HO^
20,
CHjCHjCHO ~ OH- X CH3CH2C(0)0j + HjO
01
CHjCH2C(O)0j ~ NO — »02 * CHjCN^j ~ COj
CH}CH(OpCH2OH t NO - HOj ~ CMjCHfO-)CH?0M
CHjCHjO^ ~ NO - N02 ~ CHjCHjO-
CHjCHgOj ~ *0 • M3«20N02
CHjCHlO-lCHjOH -i. ChjCHO ~ HCHO * HOj
CHjCHjO- ~ Oj - CHjCHO ~ HOj
CHjCHjC(0)0- ~ HOj - CM3C«jC(0)0jH • o2
CHjCM(OJ)CH2OH * HOj - CHjCMIOjHJCHjOM + Oj
CHjCHjOj > HOj *• CMjCMjOjH « flj
CHjCH?C(0)0j ~ NOj ' CH3CH2C(0>02H02
CHjCNjCfOJOjNOj » «0j ~ CHjCtijClOJOj
CHjCHjO- » HQ2 - CMjCHjOWj
CHjCHjO- • N02 - CMjCHO t MHOj
CHjCH(0£)CH2OH ~ CHjCHlOpCHjOH - CHjCM(0-)CHjOH ~ CHjCHtO-(CHjOH ~ 0?
J.» « to"
4.25 x 10Jt
t.S » 101'
txpartmantal*
2.»	» 10*
3.e	* jo3
1.2 » 10*
1.2	* I04
1 * ID®
1	* 10S<
3.3
I.S » 103
1.5 « !03
l.S x I03
2	« 103
2.8 a 10'
,-2tl
l.S « 10
2.9 i 10'
S.O i 10'
*	Tha Irwrganlc, forriIdahyda, *rvd *c«tjld«hyd# ructions llstad
«trl1*r unit bo iddad to contract tlx tipllcH prop/lana aoclanlaa.
t	Ritt constant In »1n"'.
I	Activation cnargjr l> 12.500K; rata constant Is glvan at 2StK.
** Activation amrgy 1s -1M01; rata owtwl It |4vm at tMK.
tt	Activation an«r|y 1a 1000T; rat* camlnt 1a (Ivan at 2W.
II	Activation nnv It -1M0K; rata cmtMt I* |l«« at (MX.
122
-------
Another change involves the minor products of propylene oxide and pro-
prionaldehyde. Last year the proprionaldehyde was treated as an isomerization
product of the propylene oxide but the resulting time profiles did not reflect
the data reported from UCR. The present chemistry improves the simulation of
these minor products. The reactions of proprionaldehyde were taken to be the
same as those of acetaldehyde.
HORO^ + O3
The hydroxyl attack on propylene produces two additional products (one
terminal and one internal), which apparently add an oxygen molecule to produce
a peroxy radical with the hydroxyl group still attached (HORO^). In the interim
report (Whitten et al., 1979), we speculated that these special peroxy radicals
might react with ozone much faster than the known reaction of HO^ with ozone.
This reaction reduced the NO-to-NO^ conversions in propylene simulations at
the time when ozone increases rapidly. The need for such a reaction stemmed
from a tendency to generate too much ozone in simulations of propylene but
not in simulations of other species such as formaldehyde, acetaldehyde, and
ethylene. The chemistry associated with peroxynitric acid (PNA), particularly
the present speculative reactions of PNA in wet atmospheres, accomplishes
the same effect even though the reactions have been included in all the
explicit studies reported here. Propylene was singled out previously because
the problem of overprediction was associated primarily with a very rapid rise
in ozone which appeared only in propylene experiments. However, the report
last year did show one instance of a steep ozone rise for some formaldehyde
experiments at very high concentrations (12 ppm). In this case, PNA chemistry
was effective in reducing the ozone in the simulations. Nevertheless, the
speculative reaction of HORO^ with ozone has presently been eliminated from
the propylene chemistry.
Criegee Intermediate + NO2
The original estimates for the rate constants used for these reactions
were based on early measurements of the HC^ reaction with NOg at low pressures.
Current estimates for this reaction are much slower and we have lower rate
123
-------
constants to reflect this. However, study of the present computer simulations
indicates that this reaction is often the major pathway for the Criegee inter-
mediates; we therefore recommend that the products of this reaction and the
rate constant be measured in the near future.
CH30£ + HOg
The rate constant for this reaction was lowered to the value recom-
mended in the 1979 NASA review (DeMore et al., 1979). However, the reaction
is not very important in the present simulations and the recommended rate
constant is merely the geometric mean of the rate constants for the self re-
actions of CHgO^ and HOjj.
Propylene Simulations
The lighting, temperature, and humidity effects on propylene simulations
(like those on ethylene) require further study, but the present chemistry is
a substantial improvement over our first attempts to simulate the experiments
reported here. Tables 20, 21, 22, and 23 provide the initial conditions and
summaries of results for the two sets of simulations. Figures 61 through 102
provide the graphical results.
The simulations of UCR data show a consistant overprediction of ozone
when the propylene decay is closely simulated. Likewise, the NO-to-NO^ con-
versions per propylene molecule reacted seem to be overpredicted, as
demonstrated by the results for EC-256. This experiment had a very low HC/NO^
ratio so that the N0x crossover point, at which NO and N02 become equal, was
barely reached by the end of the six-hour experiment. However, the current
propylene mechanism appears to generate too much ozone in the UCR simulations,
indicating that the efficiency for ozone production should be much lower
than the NO-to-NO^ conversion rate, or that the N0X conversion rate itself
becomes limited when ozone builds up. Unfortunately, the latter effect can
not be tested easily because low N0X concentrations accompany the higher
ozone concentration. Under such conditions, accurate N0^ data are difficult
124
-------
TABLE 20. INITIAL CONDITIONS FOR UCR PROPYLENE/NOx EXPERIMENTS

Temperature
(Degrees K)
Initial
concentrations (ppm)


Photolysis rate
constant
(x 104
mi n 1) *
Exp. no.
Propylene
NO
no2
HONO
h2o
N02 + hv
03 + O'D
o3 - 0
HONO -
H2°2 ~*
FORM»radicalst
EC-230
303.
.546
.392
.128
.008
2.1 x 104
.3
13.
92.
870.
4.
14.
EC-256
304.
.109
.52
.044
.009
2.2 x 104
.3
6.9
90.
830.
3.6
10.
EC-257
304.
.112
.53
.032
.008
2.2 x 104
.3
6.9
90.
830.
3.6
10.
EC-276
303.
.510
.410
.106
.008
1.9 x 104
.35
9.9
108.
1000.
5.
13.
EC-277
303.
.564
.098
.010
.001
2 x 104
.35
9.9
108.
1000.
5.
13.
EC-278

1.016
.366
.128
.006
1.97 x 104
.35
9.9
108.
1000.
5.
15.
EC-279

1.10
.73
.244
.008
1.97 x 104
.35
9.9
108.
1000.
5.
15.
EC-314
303.
1.03
.684
.246
.009
2.4 x 104
.48
18.7
150.
1580
6.
18.
EC-315
290.
.967
.664
.276
.009
1.04 x 104
.48
18.7
150.
1580.
6.
11 .
EC-316
312.
1.07
.735
.246
.015
4.61 x 104
.51
20.
160.
1680.
6.
24.
EC-317
304.
.493
.256
.281
.016
2.54" x 104
.53
24.
165.
1750.
6.
24.
EC-3185
303.
.509
.172
.331
.014
3.8 x 104
.53
24.
165.
1750
6.
18.
EC-319**
303.
.502
.100
.430
.012
2.4 x 104
.53
24.
165.
1750.
6.
18.
EC-320tf

.536
.222
.290
.012
4.1 x 104
.55
25.
171.
1820.
6.2
18.
* Rate constant in min"^ for NO^.
t The relationship between HCHO Products and carbonyl photolysis rate constants are discussed in Section 4.
§ Initial PAN added = 0.072 ppm.
** Initial PaN added = 0.149 ppm.
tt Initial PAN added * 0.636 ppm.
-------
TABLE 21. UCR PROPYLENE EXPERIMENTS—SIMULATIONS AND MEASUREMENTS







Time to
Difference fn



Tine to
Dlffereect to

Initial
imtui
hlttel
nanta
u>
Difference In
mxIm
um ro*i
tlees to
Maxinua
Difference
•exl
mm
tlaes to

[HO,]
"V"°*
HC/1M,
[0,] (pf»)
Oj uxlmt
(minutes)
0j nxIm
[N0?)
(Pf*)
In tlM
[m2] (aln)
H02 ¦•sin
In. «o.
(ml
ratio
(mC/Doa)
SI*.
He«».
(peneflt)
Sim.
Meas.
(oercent)

Heas.
to NO2
S1*.
Meat.
(percent)
IC-IM
.520
.S
3.15
.48
.33
45
>420
>420
-
.39
.36
8
120
120
0.
EC-2M
.564
.08
.58
.01
.002
400
>360
>360
-
.23
.21
10
>360
>360
-
(C-257
.562
.08
•to
.093
.06
55
>360
>360
-
.35
.30
17
200
200
0.
IC-276
.516
.21
2.97
.43
.35
23
>360
>360
-
.39
.36
8
120
120
0.
EC-277
.108
.09
15.7
.37
.31
19
100
100
0.
.09
.065
6
30
30
0.
EC-278
.494
.28
6.2
.62
.62
0
180
160
13
.40
.38
5
60
60
0.
EC-279
.974
.25
3.39
.67
.67
0
>360
>360
-
.76
.7
9
120
100
20.
EC-314
.9)0
.27
1.32
.78
.72
a
300
>360
-
.72
.68
6
90
90
0.
EC-315
.940
.29
3.09
.36
.33
9
>360
>360
•
.66
.61
8
180
140
29.
EC-316
.981
.25
3.27
.93
.95
2
230
280
-
.79
.75
5
70
60
17
EC-317
. &37
.52
2.75
.68
.60
13
290
330
-12
.42
.39
8
60
60
0.
K-318
.503
.66
3.04
.64
.68
-6
240
240
0.
.43
.41
5
30
30
0.
EC-319
.$30
.81
2.84
.78
.75
4
200
220
-9
.47
.46
2
20
20
0.
tC-320
.512
.57
3.14
.60
.64
-6
250
240
4
.42
.40
5
40
40
0.
Oj average • 12 percent, standard deviation « ?I8 percent (excluding EC-256).
ttg	• ? parciat, tUndiH dmlatiM • t ] percent ¦
-------
TABLE 22. INITIAL CONDITIONS FOR UNC PROPYLENE/NO EXPERIMENTS
A
Beginning
Cliu£«r	Sky	tlae of	Initial concentrations (pf)	ALO ~
Dete
Side
Condition*
Simulation
Propylene
NO
NO?
HONO

Constant
10/24/77
Rod
Variable
clouds
7:16
1.21
.338
.129
.005
1.6
« 104
1.2
12/26/77
Red
Clear
8.08
.988
.281
.118
0.
1.5
x 103
1.0
1/10/78
Red
Clear
8:15
1.08
.323
.139
.015
1.5
x 103
1.0
2/27/78
Red
Clear
8:00
1.32
• 371
.125
0.
4 «
103
1.0
3/06/78
Red
Variable
clouds
7:36
1.25
.394
.117
.007
4 x
103
1.0
3/31/78
Red
Variable
clouds
6:48
1.27
.392
.091
0.
1 X
104
1.0
6/16/78
Blue
Clear
6:16
.667
.429
.211
0.
1 .6
x 104
1.0
6/30/78
Red
Variable clouds
1n afternoon
6:12
.503
.382
.062
.011
2.2
x 104
1.0
7/01/78
Blue
Spars* Clauds
1n afternoon
5:52
.503
.612
.323
.020
2.2
> I04
1.0
7/14/78
- ¦
Variable clouds
6.04
.99
.775
.184
.025
2.4
x !04
1.0*
7/24/78
Blue
Variable clouds
6:04
.49
.778
.174
.022
2.4
x 104
1.0*
7/30/78
Blue
Scattered
clouds
6:28
.417
.399
.084
.011
2.4
x 104
1.0*
8/05/78
Red
Scattered
clouds
6:16
.277
.196
.052
.008
2.4
x 104
1.0*
8/05/78
Blue
Scattered
clouds
6:16
.518
.423
.145
.012
2.4
x to4
1.0*
8/06/78
Red
Scattered
clouds
6:20
.563
.420
.141
.027
2.4
x 104
1.0*
8/15/78
Red
Scattered
clouds
6:23
.483
.434
.109
.015
2.2
x 104
1.0
8/21/78
Blue
Clear
6:31
.427
.798
.183
.003
1.6
x !04
1.0
10/17/78
Red
Overcast In
a f temoon
7:22
.450
.371
.125
.002
1.0
x 104
1.0*
10/18/78
Blue
Clear
7:28
.507
.340
.116
.002
1.6
x 104
1.0*
10/20/78
Red
Clear
7:30
.463
.336
.124
.003
1.6
x 104
1.0*
10/20/78
Blue
Clear
7:30
1.217
.329
.128
.004
1.6
x 104
1.0*
10/21/78
Red
Clear
7:27
1.167
.397
.100
.0015
1.6
x 104
1.0*
10/21/78
Blue
Clear
7:27
1.18
.395
.100
.002
8 x
I03
1.0*
10/22/78
Red
Clear
7:24
.467
.379
.111
.003
1.6
i 104
1.0*
10/22/78
Blue
Clear
7:24
.467
.373
.114
.002
1.6
x 104
1.0*
10/29/78
Red
Overcast In
¦orntng
7:28
.450
.374
.124
.011
1 X
104
1.0*
10/29/78
Blue
Overcast In
morning
7:28
1.227
.370
.125
.013
1 X
104
1.0*
11/07/78
Red
Overcast 1n
afternoon
7:40
.457
.301
.140
.005
1 X
104
1.0*
* UV data used In comwtar s(nutations. Instead of TSR.
127
-------
TABLE 23. UNC PROPYLENE EXPERIMENT--SIMULATION RESULTS AND MEASUREMENTS

Cluster
Initial
[NO,]
lalttel
Mj/NO,
Initial
HC/NOj
Ktiiaua [0j]
(««¦)
01ff*r«AC« In
Oj NailM
Tta* to
Nutan [0j]
(Minutes)
Difference «« tta*
to 0j Haitaa
Sit*
Side
I PI*)
Ratio
(ppaC/ppi)
Sl«.
HMS.
(P*rc*nt)
Sl«.
Meat.
(tenant)
101/24/77
M
.487

7.90
.48
.62
-21
>160
300
-
1Z/26/77
Md
.199
.30
7.43
.36
.38
-5
400
400
0.
1/10/78
8*4
.462
.30
7.01
.31
.36
-14
400
400
0.
J/27/78
Red
.496
.25
7.98
.80
.57
40
380
300
27
1/06/78
ted
.511
.23
7.40
.84
.63
33
380
300
27
V31/78
ted
.483
.19
7.89
.87
.78
12
360
2(0
29
VH/78
(In*
,M0
.33
3.13
.93
1.08
•14
>560
500
-
4/30/78
ted
.464
.18
3.25
.80
1.00
20
460
420
10
7/01/78
BIim
.935
.35
1.61
.35
.56
-17
600
600
0.
7/24/78
ted
.959
.19
3.10
.92
1.20
-23
>560
470
-
7/24/78
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FIGURE 66 . SIMULATI0N RESULTS F0R
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TIME (MINUTES)
FIGURE 74 . (Concluded)
152
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1.20
0.60
0.40
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0 50 100 150 200 250 300 350 400
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TIME (MINUTES)
FIGURE 75 . SIMULHTI0N RESULTS F0R
UNCR 102477
153
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154
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0 90 180 270 360 450 540 630 720
TIME (MINUTES)
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TIME (MINUTES!
1.60
1.20
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0 90 180 270 360 450 540, 630 720
TIME (MINUTES)
FIGURE 76 . SIMULA!"10N RESULTS F0R
UNCR 122677
155
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0.48
0.36
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0,0°O 70 140 210 280 350 420 490 560
TIME (MINUTES)
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0.80
UJ
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FIGURE 77 . SIMULATION RESULTS F0R
UNCR 11078
156
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TIME (MINUTES)
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0.90
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£ 0.60
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80 160 240 320 400 480 560 640
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0.28
0.21
a.
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80 160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 78 . SIMULATI0N RESULTS F0R
UNCR 22778
157
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1.60
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1.20
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90 180 270 360 450 540 630 720
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0.26
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80 160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 80 . SIMULATI0N RESULTS F0R
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TIME (MINUTES)
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TIME (MINUTES)
FIGURE 82 . SIMULATION RESULTS F0R
UNCR 63078
161
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162
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0.68
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£ 0.34
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110 220 330 440 550 660 770 880
TIME (MINUTES)
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0 110 220 330 440 550 660.770 880
TIME (MINUTES)
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0 110 220 330 440 550 660 770 880
TIME (MINUTES)
FIGURE 83 . SIMULHTI0N RESULTS F0R
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163
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TIME (MINUTES)
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0 80 160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 84 . SIMULRTI0N RESULTS F0R
UNCR 72478
165
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171
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UNCB 82176
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192
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193
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UNCR 110776
194-
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to obtain due to a combination of detection limits, interference from ozone
and secondary nitrogen compounds, and sample line problems.
Somewhat different problems appear in the UNC simulations. In these
simulations UV data were used rather than arbitrarily varying photolysis con-
stants to simulate propylene decay (as was done in the UCR simulations); therefore,
several days appear to have improper radical inputs, especially on cloudy
days when only TSR data were available. Nevertheless, several days show
rather close simulations of observed propylene decay, yet ozone may be either
underpredicted or overpredicted. On many days, a very rapid rise in ozone
occurs around 1200 hours which the present simulations cannot follow even if
the NO crossover is simulated too early. A drastic example of this is seen
A
in Figure 80 for the red side of the experiment performed on 31 March 1978.
One explanation for the overprediction/underprediction problem in the UNC
set of simulations may be an N0x loss reaction that changes between experiments
and has yet to be properly characterized. Candidates for future study are
the N20j- reaction with 1^0 and the loss rate of PNA to the walls.
PROPYLENE/ACETALDEHYDE
Differences between the PAN simulations in dual chamber experiments at
UNC, which compared ethylene/acetaldehyde on one side of the chamber to pro-
pylene on the other, were discussed earlier. Also, to support the use of a low
acetaldehyde photolysis rate, we indicated that successive experiments at
UCR (EC-216 and EC-217) should use similar photolysis constants; EC-217 con-
tained a large initial concentration of acetaldehyde added to propylene
while in EC-216 propylene was the only organic compound. Finally, the mixture
of acetaldehyde and propylene represents a means of using the hierarchical
concept to further test parts of the propylene and PAN chemistry. However,
a key experiment, EC-217, is poorly simulated by our current chemistry in an
unusual fashion: the decay of propylene and acetaldehyde cannot be simul-
taneously simulated as indicated in Figure 104. We requested that a similar
pair of experiments be performed in the dual facility at UNC and, on 12 June
1979, these experiments were carried out. Table 24 and 25 show the initial
conditions for the two UCR and two UNC experiments. Figures 103 through 106
195
-------
TABLE 24. INITIAL CONDITIONS FOR UCR PROPYLENE/ACETALDEHYDE
AND PROPYLENE/NO EXPERIMENTS
A
		Initial concentrations (ppm)			Photolysis rate constant (10*niin 	
Exp. Ho. Propylene Acetaldehyde HO NO; H5KCT H?Q	NO? + hi	O3 + h\> - O'D	O3 ~ h v -»• 0 HONO + hv 4 H70?~?Tw + " "Carbonyl ~ h •>
EC-216 .48 .002 .412 .104 .008	2.4 x 104 .43 35.3	135.	1280. 6. 15.
EC-217 .076 .16 .210 .238 .005	2.8 x 104 .43 35.3	135.	1280. 6. 15.
Rate constant 1n m1n~^ for NO^-
g	TABLE 25. INITIAL CONDITIONS FOR UNC PROPYLENE/ACETALDEHYDE
AND PROPYLENE/NO EXPERIMENTS
X

Chamber
Sky

Initial
Concentration (ppm)

Carbonyl + hv
Constant
Date
Side
Conditions
Propylene
Acetaldehyde
NO
NO? HONO
H?0
6/12/79
Red
CI ear
.218
-
.257
.243 .008
2 * 10A
1.0*
6/12/79
Blue
Clear
.178
.04
.254
.24 0
2 x TO4
1.0*
* UV data used in computer simulations instead of TSR data.
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197
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FIGURE 103.
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FIGURE 104. SIMULRTI0N RESULTS F0R
EC-217
,199
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90 180 270 360 450 540 630 720
TIME (MINUTES)
FIGURE 105. SIMULRTI0N RESULTS F0R
JJNCR 61279
.200
-------
1.25
1.00
z
Ol
Q.
0.73
cc
ae
0.30
is
u
0.25
0.00
1
03
1 1 1 1
¦
1 1
, .. 1 1

1 1
. !
,
1 1
0 90 180 270 360 450 540 630 720
TIME (MINUTES)
0.60 -
a.
a.
0.45
-------
present the graphical results. Surprisingly, the current chemistry appears
to predict the decay curves for acetaldehyde and propylene simultaneously in
the UNC experiment, but not in the UCR experiment.
A better test of the PAN chemistry would have been possible if the
propylene side of the dual chamber experiments had used more propylene so
that similar PAN could be predicted for both sides. Since the same instru-
ment is used to measure PAN, by alternating between both sides of the
chamber, a prediction and verification of equal PAN on both sides would con-
stitute a sensitive test of the PAN chemistry.
BUTANE
The butane mechanism published in our interim report (Whitten et al.,
1979) was modified to model the data from new experiments performed in both
the UCR and UNC chambers. Table 26 presents the current version of the
butane chemistry. The initial conditions and results from simulations of six
experiments in the UCR chamber and seven experiments in the UNC chamber are
presented in Tables 27 through 30 and Figures 107 through 120. The minor
changes made to the butane chemistry are briefly described in the following
subsections. The photolysis rate constants for butyraldehyde and methyl ethyl -
ketone are assumed to be the same as the formaldehyde photolysis rate constant
producing radicals.
R0£ + HO^
As described earlier for CH^O^ in the propylene chemistry, rate constants
for these reactions were reduced to the number recommended in the 1979 NASA review
(DeMore et al., 1979).
R0£ + NO
We have lowered the rate constant for the pathway to nitrate formation
-1 . -1
from the sec-butyl peroxy radical to 550 ppm min . Although this value
lowers the simulated nitrate to nearly half the values reported in the UCR
data, we feel the current number used is an upper limit for this particular
202
-------
TABLE 26. REACTIONS OF BUTANE*
ftate constant
R*KtlO*	 fpon M
°Z
CHjCl^Cl^Ckj « o —• CMjCH?CM(Op)CH3 « OH-
0,
CH3CH2CH2CH3 ~ OH. —• CHjCHjCHjtHjOj ~ H?0	5.74 > 10?tS
Oj,
CH3CH?CH?CH3 ~ OH- —• CH3CH?CH(Oj)CH3 * H;0
HOCH?CHjCW2C(0)Oj TO —• N0? t NOCMjCt^CHjO' * CG; 3.S « I03
HOCM2CH?t(O)0y * *0 -i. NOj ~ HOO^CKjOj « C0?	3.B J 10
3
CH3CHjCH?c(o)aj ~ wo — ck3ck2ch2q2 * no2 + cq?	3.8 * ioJ
o?	,
CHjCHjCtOJOj ~ MO — CHjCH^Cj + M} - C02	J.B X 10'
°?	i
WJCHjCHjCHjD^Oj + W —• *02 + HOj + HOCHjCXjCHjCHO 1.2 jt ID
CH3M(02WO)CN3 > *0 »j ~ HO- ~ W3C(0)£(0)OI3 t.2 ¦ 10*
CHjCHjOUOJIWj •»•«,* OjCKjCHfO-)W3	1.) x W*
OtjtHjCTfOpCWj * HO - £H3CH2CHCHj	B.s x I0?
~ M - Kflj ~ CHjCH^CHjO-	1.1 x 10*
CXjCHjCHjCHjOj « M * CHjCH^CHjONOj	1 x 103
®2	i
HOO^CHyCHjfl^ ~ *0 —»- M02 ~ HOJ * HOCH^CHjCHO	1.2 x 10
02	.
H0CH2ay>J + NO —» N02 ~ HO^ ~ HOCH?CHO	1,2 X ID4
OfjCMjOyi^ + NO - HOj + CHjCHjCH^-	1.2 > ID4
CHjO^CHjOj ~ » * CHjCHjOIjOKOj	1 x |o2
CHjOfjOJ + DO ~ *02 ~ CHjCHjO.	1x I04
CHjCKjOj 4 NO * CHjCHjfflBj	1 , JO2
203
-------
TABLE 26 (Continued)
Rate iortSt
-------
TABLE 26 (Concluded)
Rate con
ItMCtlOfl
(ppnT^jrin*')
HOCh^CHO ~ Oh- — hOfO » MOj ~ CO ~ H^O
HOOTCH.02C(0;0| * HCj - MPChjCHgO^Ct0)02V » 02
HOCM^ChjdOjOj ~ HOj - HOCMjCHjCIOJOjH < Oj
CH3CH?CH2C(0)0^ ~ HO2 - CH3CH2CH2C(0)02H ~ 02
CM3CHjC(0)0^ * HO- - CH3CH2C(0)02H + 0?
CH3CH(0^)C(0)CH3 « HO- ~ CH3CM(02H)C(0>CH3 ~ 02
CH3CH2CH(Oj)CH3 t HOj - CHjCHjCHICHjJOjH + 02
CHjCHjO^ •> HOj - CfcjCHjOjH ~ Oj
CH3CH2CH2C(0)0j ~ N02 - CHjCHjCHjCfOJOjNOj
CH3CH2C(0)0j ~ NOj * CHjCHjCiOlOjNOj
CH3CH2C(0)02H02 - *02 ~ tH3CH2C(0)0j
C«3CH2CH2C(0)02N02 - NOj ~ CHjCHjCHjCtOlOj
CKjCHjO- ~ KOj ¦> CHjCHjOHOj
CHjCHjO- ~ NO? - CHjCHO ~ HONO
CHjCHjCHjO- ~ NOj » CHjCHjCHjONOj
CHjCHjCHjO. t NOj CHjCHjCMO ~ HONO
ch3ch2ch2ch2o. ~ no2 - ch3ch2ch2ch2ono2
CHjCHjCHjCHjO- + H02 » CH3CHjCH2CH0 ~ HONO
CH3CH2CH(0-)CHj ~ NOj - CHjCHjCHtONOjJCHj
CH3CH2CH(0-)CHj ~ NOj • CHjCHjClOJCHj ~ HQNO
tint
1,
2.2 x 10
1.5 x IT
1.5 * 10
1.5 * 10
1.5 x 10
1.5 x 10
1.5 x 10
1.5 x 10
1.5 x 10
1.5 i 10
1.5 x 10
1	x 103
2	x 103
?.e x io"2t
2.8	x lO-2'1
1.5 x 10*
2.9	x 103
1.5 x 104
2.9 x 10J
1.5 x 104
2.9 x 103
1.5 x to4
2.9 > 10
The Inorganic, forwldahydt, and acetaldehyde reactions listed nrllir
mutt b» added to construct the explicit butane mechanism.
' Activation energy 1j 12.500K; rata constant Is given at 298K.
*' Activation energy ij 8800K; rate constant 1j given at ?9BK.
** Activation xr.rrgy is WOK; rate constant Is given at ??OC.
At.;.; vist 'on
'1/ c F.K; rite constant Is sf.-en it
205
-------
TABLE 27. INITIAL CONDITIONS FOR UCR BUTANE/NO EXPERIMENTS
A
Temperature 	Initial concentrations			 	Photolysis constants (x 104 min~^)*
Exp. no.
(Degrees K'
Butane
NO
NO?
HONO
H2O
no2 *
O3 -<•
O'D O3 - 0
HONO -
HpO?
FORM-Radl
EC-304
303.
4.22
.349
.117
.01
2.7 x 104
.43
5.
134.
1390.

10.
EC-305
303.
4.25
.078
.020
.005
2.73 x 104
.43
5.
134.
1390.

18.
EC-306
303.
6.33
.147
.04
.005
2.5 x 104
.43
10.
135.
1440.

10.
EC-307
304.
6.38
.082
.019
.005
3.0 x 104
.43
10.
135.
1440.

12.
EC-308
289.
4.00
.305
.178
.007
8.8 x 103
.44
10.
138.
1440.

12.
EC-309
312.
4.23
.203
.272
.018
2.3 x 104
.45
10.
141.
1480.
4.6
18.
* Rate constant in min"^ for NC^-
ro
o
CD
TABLE 28. INITIAL CONDITIONS FOR UNC BUTANE/N0x EXPERIMENTS
Chamber	Sky	Beginning time 	Initial concentrations (pprc)	ALD + hv
Date
side
conditions
of simulation
Butane
NO
NO?
HONO
H20
constant
10/24/77
Blue
Variable
cloudiness
7:16
2.0
.36
.13
.008
1 x 10*
1.2
7/21/78
Red
Clear
6:00
1.83
.189
.054
.008
2.4 x 104
1.0*
7/21/78
Blue
Clear
6:00
3.93
.186
.056
.006
2.4 x 104
1.0*
7/22/78
Red
Clear
6:12
2.09
.432
.116
.015
2.4 x 104
1.0*
7/22/78
Blue
Clear
6:12
4.37
.436
.121
.015
2.4 x 104
1 .0*
7/27/78
Red
Overcast
6:28
3.37
.189
.077
.017
O
X
CNJ
1 .0*
7/27/78
Blue
Overcast
6:28
3.30
.385
.124
.024
2.4 x 104
1 .0"
* UV data used 1n computer simulations Instead of TSR data.
-------
TABLE 29. UCR BUTANE EXPERIMENTS—SIMULATIONS AND MEASUREMENTS
Time to
T1m to Difference	maximum Difference

Initial
imj
Ultlal
Initial
HC/HOx
Maximum [0^]
(pp»)
Difference
1n Oj mx1m
Oj maximum
(minutes)
1n times to
0- maxima
Maximum [NOj]
(Pon>)
Difference
in NOg maxima
Cko2]
1 (minutes)
In tiroes to
NOj maxim
Cap. No.
tPP«)
ratio
I ppmC/ptw)
Sin.
Meas.
(percent)
S1n.
Meas.
Tpercent)
Sim.
Meas.
(percent)
Sim. Meas.
(percent)
EC-304
.466
.25
36.2
.46
.34
35
>450
>450
-¦
.24
.22
9
180
180
0.
EC-305
.098
.05
170.0
.45
.39
15
240
300
20
.080
.076
5
50
50
0.
EC-306
.287
.14
88.2
.60
.53
13
360
360
0.
.15
.14
7
100
100
0.
EC-307
.101
.19
252.7
.50
.42
19
280
280
0.
.06
.076
5
50
50
0.
EC-308
.483
.37
33.1
.066
.026
154
>360
>360
--
.21
.17
24
>360 >
360
-
EC-309
.475
.57
35.6
.66
.51
29
>360
>360

.39
.36
8
60
60
0.
Oj maxtaa: average difference " 22 percent; standard deviation * *9 percent (excluding EC-306).
N02 auxin*: average difference • 10 percent; standard deviation • *7 percent.
TABLE 30. UNC BUTANE EXPERIMENTS—SIMULATIONS AND MEASUREMENTS
Difference in
Date
Chamber
side
Initial
NO
X
(pH
Initial
NO,/NO
2' x
ratio
Initial
HC/NOx
(ppmC/ppm)
Maximum
[O3] (ppm)
Sim. Meas.
Difference in
O^ maxima
(percent)
Time to
maximum [Oj]
Sim. Meas.
times to 0^
maxima
(percent)
10/24/77
Blue
.49
.27
16.3
.012
.002
500.
>400
>400
--
7/21/78
Red
.243
.22
30.1
.78
.75
4
600
600
0.
7/21/78
Blue
.242
.23
65.0
1.04
.92
13
520
540
-4
7/22/78
Red
.548
.21
15.3
.25
.14
79
680
680
0.
7/22/78
Blue
.557
.22
31.4
.80
.75
7
680
680
0.
7/27/78
Red
.266
.29
50.7
.36
.49
-27
>480
>480
0.
7/27/78
Blue
.509
.24
25.9
.20
.23
-13
>480
>480
__
Oj maxima: average difference = 11 percent; standard deviation = ± 36 percent (excluding run performed on 10/25/77)
-------
0.40
Q_
Q.
0.30
ac
PC
0.20
u
z
ea
0.10
0.00

0 60 120 180 240 300 360 420 480
TIME (MINUTES)
0.05
0. 04
0.03
CJ
3E
m
CJ
0.01
0.00
1
PON
F0RH
l I l l i
¦
+
i
/ *
-
* J
/
-
// *
z
IB
(J
3.85 -
3.40
0 60 120 180 240 300 360 420 480
TIME (MINUTES)
0.20
0.16 -
0.12
0.08 -
z
CJ
0.04 -
0.00
HLD2
0 60 120 180 240 300 360 420 480
TIME (MINUTES)
FIGURE 107. SIMULflTI0N RESULTS F0R
EC-304
208
-------
0.0075
0.0060

0.0045
-------
0.40
a.
OL
0.30
0.20
Ui
CJ
z
Q>
o
0.10 ~
0.00

0 60 120 180 240 300 360 420 480
TIME (MINUTES)
0.05
0.04
0.03
cr
at
0.02
o
z
9
0.01
0.00
1
i i	i i i i
PAN
¦
F0RM
~
/ / "

+ y -

j *

~/ *
_
v -



4



"1 1 1 1 1 1
0 60 120 180 240 300 3GJ 420 480
TIME (MINUTES)
4.65
4.40
4.15
3.90
UJ
U
3.65 -
3.40
0 60 120 180 240 300 360 420 480
TIME (MINUTES)
0.20
0.16
0.12
0.06
u
2T
S .
U
0.04
1
RL02
MEK
1 1
¦
~
1 I I
1


/ **

-
<3^
_ x
x *
—

/ m*
+ + ^


J" jR
M
X
+ jp.


_/ X


—
' 1
1 !
I I I
t
TINE (MINUTES)
FIGURE 108. SIMULATION RESULTS F0R
EC-304 WITH NOo
CONVERSION
210
-------
0.60
CL
0.45
£ 0.S0
ui
c_>
**
X
m
o
0.15
0.00
TIME (MINUTES)
N0
N02
0.100
a.
0.075
IB
£ 0.050
u
0.025
+4
0.000
ituu j50 400
TIME (MINUTES)
4.65
4.40 -
4.15 -
b-
cc
U
u
3.90 -
3.65 -
0 50 100 150 200 250 300 350 400
TIHE mMWTESJ
0.05
0.04
0^03
OE
pe
0.02
ui
u
o.ot
0*00
1 1 T
PAN ¦
F0RH ~
i i t i
-
/ m __
/ *

' X
A * +
* *

	1"
i
:v
¦rfirtf ii
-J	 1 ' i 1
jtME (MINUTE31
FIGURE 109. 5IMULRTI0N RESULTS F0R
£C-305
211
-------
0.20
0.16
x
0L
Ok
0.12 -
cc
oe
H-
z
UJ
CJ
0.08
RLD2
0.0075
0.01 -
0 SO 100 150 200 250 300 350 400
TIHE (MINUTES)
i—i—r
RLD3 ¦
0.0060 -
a.
a.
0.0045
0.0030
0.0015 -
X X
0.0000
0 50 100 150 200 250 3C3 350 400
TIHE (MINUTES)
0.0125
0.0100 -
0.0075 -
0.0050 -
0.0025 -
0.0000
0.05
0.04
0.03
0.02
u
X
s
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.01
0.00
j 1
1 I I
l
SCN3 ¦

—
-

m

X


X
—

X

K



-sttva-—




II,
1 1 l
1
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 109. (Continued)
212
-------
0.0008 -
0.0006 -
0.0001 -
o
z
IS
o
0.0002 -
0.0000
i—i—T
X * X X X X X
' I I	I	I	I	L
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.005
0.004
ac
o.
ft.
0.003
0.002
u
z
ts
o
0.001
0.000
i—i—r
C4N3 ¦
i—r
0 50 100 150 200 250 3CC 350 400
TIME (HINUTES)
FIGURE 109. (Concluded)
213
-------
0.60 -
ac
Q.
a.
0.45 -
0.30
u
z
OB
<_>
0.15 -
0 60 120 180 240 300 360 420 480
TIHE (MINUTES)
0.20 -
0.15 -
a:
ae
0.10
UJ
u
O.OS
0.00

0 60 120 180 240 300 360 420 480
TIHE (MINUTES)
0.060 -
0.045 -
0.030 -
u
z
s
u
0.015 -
0.000
I I
0 60 120 180 240 300 360 420 480
TIME (MINUTES)
6.60 -
6.20
cc
tc
5.80 -
5.40 -
0 60 120 180 240 300 3E0 420 480
TIME (MINUTES)
FIGURE 110. SIMULATION RESULTS F0R
EC-306
214
-------
0.20
0. IS
0.10
o
z
0)
u
0.03
0.00
1 1 1
r i
1 1
RLD2 ¦
MEK ~
J
/
X
/
X X
X _
- / *
X

/ X*
/*
- / * *
/ *3^^
^ +
+
l^T *"



¦ • i '
I 1
1 •
0.05
0 60 120 180 240 300 360 420 480
TIME (MINUTES)
RL04 ¦
SCN3 +
0.04 -
0.03 -
-------
0.005
C4N3
0.004
0.
ft.
0.003
0.002
o
z
B
O
0.001
0.000
60 120 180 240 300 360 420 480
TIME (MINUTES)
FIGURE 110. (Concluded)
216
-------
0.60
0.00
i—r
03
0.30
J	I I
0 SO 100 150 200 2S0 300 350 400
TIME (MINUTES)
0.100
z
o.
Q_
* 0.075
cc
ae
0.050
o
z
u
0,023
0.000
1 1
N0 ¦
N02 +
1 1 1 1 1


I+ X

f +
*
V
V++ +
l*
\*+ ++++++_
\T**w w \
i kmhi i
0 50 100 150 200 250 3G0 350 400
TINE (MINUTES)
6.500
6.200
ac
cc
5.900
iu
o
5.600
5.S00
i
1 1
1 1 1 1
BUT
¦
-
-

—

X
* V.
I


x "Ns. -
1
1 1
X ^
X
1 1 1 1
0 50 100 ISO 200 250 300 350 400
TIME (MINUTES)
0.05
0.04 -
0.03 -
cc
ee
0.02
iu
u
0.01 -
0.00

0 SO 100 ISO 200 250 3CQ 3S0 400
TIME (MINUTES)
FIGURE 111. 51MULRT10N RESULTS F0R
EC-307
217,
-------
0.20
0.15 -
0.10
<_>
x.
o
0.03 -
0 50 100 150 200 250 300 350 400
TIHE (MINUTES)
0.005
0.004 -
Q.
Q.
0.003 -
0.002 -
u
z
CD
<_>
0.001
0.000
flLDS *
C4N3 ~
0 50 100 150 200 250 300 350 400
TIHE (MINUTES)
0.0125
0.0100
0.0075
-------
0.05
SCN3
0.04
cc
oc
h-
Z
0.02
u.i
o
z
s
u
0.01
0.00
TIKE (MINUTES)
FIGURE 111. (Concluded)
219
-------
0.060 -
o_
a.
0.045 -
-------
0.10
0.08
ac
a.
a.
0.06
0.04
UJ
o
0.02
0.00
1 1
i 1 1
i 1
RL02 ¦
MEK ~



+
+ _
-
+
+
'
1 1

K _
*
m
(* 1 I
1 1 1
I 1
0 50 100 ISO 200 250 300 350 400
TIME (MINUTES)
0.0012 -
a.
a.
0.0009 -
0.0006
o
CD
a
0.0003 -
0.0000
RLD3 "
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.005
RL04
0.004
0.003
z
m
0.002
CB
¦u
0.001
0.000
50 100 150 200 250 300 350 400
TIME (MINUTES)
C2N3
0.0004
z
Q_
a.
0.0003
x
to
~-
tc
ae
H
Z
bJ
0.0002
<_>
z
O
0.0001
0.0000
100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 112. (Continued)
221
-------
0.020
SCN3
0.016
0.012
0.008
0.004
0.000
50 100 150 200 250 300 350 400
T1HE (HINUTES)
C4N3
0.0016
x
a.
a.
0.0012
»-
as
UJ
0.0000
o
z
SB
CJ
0.0004
0.0000
50 100 150 200 250 300 350 400
TIME (HINUTES)
FIGURE 112. (Concluded)
222
-------
I I—I


0 SO 100 ISO 200 250 300 3S0 400
TIHE (MINUTES)
4.65
4.40
4.13
3.90
u
X
B
u
3.85
9.40
1 1 1 1 1
BUT ¦
1 1
Ss*

*



1 1 1 II
V"
1 1*
0 50 100 ISO 200 250 300 350 400
TIME (MINUTES!
0.060
PRN
F0RH
0.048
a.
0.036
a
£ 0.024
iu
o
0.012
0.000
SO 100 150 200 250 300 350 400
TIME (MINUTES)
0.24
0.18
fc 0.12
-K
0.06
0.00
SO 100 ISO 200 250 300 350 400
TIME (MINUTES)
FIGURE 113. SIMULATI0N RESULTS F0R
EC-309
223
-------
D.005
¦0.004
x
a.
a.
0.003
a
ac
0.002
S.001
0.000
i—T
RLD3 ¦
i—I—T

J	I	L
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.010
0.008
x
a.
0.006
a:
oe
0.004
*
a
o
0.002
0.000
1 1 1 1 1	-
1
RLD4 ¦
-
-
*
1
\
\
jr
M
- >5^ x

/I * *

f *

-.-J-	J, 1 1 1
1
0 SO 100 150 200 250 300 350 400
TIME (MINUTES)
0.0008
0.0006
0.0004
ui
o
0.0002
0.0000
1 1
1 1
1 I 1
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0.009
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CL.
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cc
cc
u
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0.24 ~
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 114. SIMULRTI0N RESULTS F0R
UNCB 102477
225
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1.25
03
1.00
x
0.73
i 0.30
o
u
0.25
0.00
90 180 270 360 450 540 630 720
TIME (HINUTES)
N0
N02
0.28
x
a.
a.
0.21
0.14
o
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0.07
0.00
90 180 270 360 450 540 630 720
TIHE (HINUTES)
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3C
2L
1.80
ae
m
M
£
1.60
3
1.40
1.20
90 180 270 360 450 540 630 720
TIHE (MIKUTES)
FIGURE 115. SIMULRTI0N RESULTS F0R
UNCR 72178
226
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1.60
O-
0.
1.20 -
a:
DC.
0.80 -
0.40
0.00
0 90 160 270 360 450 540 630 720
TIME (HINUTES)
0.28
a.
Q-
0.21
0.14
u
0.07
0.00
1 1
N0 ¦
1 1 1 1

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+


+


+

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/+ *\
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0 90 180 270 360 450 540 630 720
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AS
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2.80
2.40
i i i i
1 1 ™T—
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iTN.

* N



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at*** -

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_ 1 , 1	1, J,,„
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0 90 180 270 360 450 540 630 720
TIME (HINUTES)
FIGURE 116L SIMULATI0N RESULTS F0R
UNCB 72178
227
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BUT
2.20
x
0.
2.00
Ui
o
u
1.60
1.40
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
03
N0
N02
0.58
3C
a.
a.
0.42
ac
0.28
o
0.14
0.00
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
FIGURE 117. SIMULATI0N RESULTS F0R
UNCR 72278
1.25
1.00
0.73 -
fc 0.30 -
to)
CJ
0.25 -
0.00
0 100 200 300 400 500 600 700 800
TIME (MINUTES)
5.60
4.90
4.20
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i i i
1
BUT *

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m
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1 1 I
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0 100 200 300 400 500 600 700 800
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FIGURE 118. SIMULATION RESULTS F0R
UNCB 72278
228
-------
03
N0
N02
0.76
0.57
z
a
M
I-
-------
reaction. Larger numbers produce a decided "kink" in the NO profiles near
X
the crossover point in the UNC simulations. Hence we recommend that nitrate
data be taken in future UNC experiments to confirm corresponding data received
from UCR.
Sec-Butoxyl + 0^
In order to improve the overall product distribution, the reaction rate
constant was lowered to half the value used last year. However, we recommend
that future butane experiments at UNC include more data on the product of
this reaction, methyl ethyl ketone (MEK), so that the present distribution can
be confirmed.
The set of UCR experiments included a brief study of temperature varia-
tion. The changes in product data at these temperatures provided a
serendipitous confirmation of a crucial part of the butane mechanism. The
main products stemming from butane oxidation are acetaldehyde and MEK. The
ratio of these compounds varies from about 0.5 in the low temperature experi-
ment (289K) to about 2.5 in the high temperature experiment (312K). We are
encouraged by the agreement between our simulations and the observed changes
in this product ratio for two reasons: (1) the activation energy for the
decomposition of sec-butoxyl radicals to acetaldehyde is a key factor and the
value (8800K) we used appears to be correct (Batt, McCulloch, and Milne, 1975);
and (2) the use of rate constants, arbitrarily adjusted by us to provide a
close competition between the decomposition reaction and the reaction with
oxygen (which forms the MEK) has finally been justified. Estimates and
evaluations of the pertinent rate parameters for these two processes have
large combined uncertainty factors (Barker et al., 1977); in fact, the com-
bined uncertainty of the ratio could be as high as 100.
The results of the current butane simulations indicate a definite over-
prediction of ozone. In our interim report (Whitten et al., 1979), we had
mentioned a general observation in smog chamber modeling concerning the rate
of NO-to-NOg conversion. If the hydrocarbon decay is simulated to closely
230
-------
match the observed hydrocarbon decay, the function of any given mechanism is
then to provide the intermediate species that convert NO to N02> deplete N0x,
and act as sources and sinks for radical balance. We have assumed that a
proper conversion rate for NO to N02 would automatically generate the correct
ozone through the basic, well-established inorganic parts of the chemical
mechanism. However, the continuing problem is that an N0-to-N02 conversion
rate, which may follow experimental observations early in many smog chamber
simulations, is often too fast late in the simulation. These butane simula-
tions provide examples of this continuing problem.
Although we have yet to solve this problem, we have attempted to analyze
it. First, the observed ozone and ;N0 data are not adequate to reconcile the
problem. Early in virtually any smog chamber experiment the concentrations of
NO and N02 are high relative to their concentrations late in the experiment
when NO has been depleted. The early high NO concentrations apparently
A	A
provide the most reliable NO data and the late low concentrations seem to
A
be the least reliable. Previously we discussed a high N0X (and low formaldehyde)
concentration experiment in the UNC chamber regarding the problems with low
ozone data taken in the presence of high NO concentrations. The possible
problem was linked to decay?^>f ozone in the sampling system. The same reason-
ing explains the ozone data reported for EC-308. We estimate that an eight-
second sampling time would lead to the ozone values reported. Hence, there is
normally a problem verifying the N0-to-N02 conversion rate relationship to
ozone formation using observed data.
While preparing for the interim report (Whitten et al., 1979), we con-
sidered such reactions as H02 + N03 and R02 + N03, as well as R02 + 03> In
fact, we included R02 + 03 reactions in the propylene mechanism. All of
these speculative reactions have the characteristic of reducing the ozone
peak without substantial change to the N0-to-N02 conversion early in the
simulation. In general, the peroxy radicals increase in concentration as the
simulation proceeds because their rate of production changes very little yet
their destruction is typically determined by reaction with NO, which, of course,
is decreasing rapidly.
231
-------
On the other hand, 0^, PAN, and NO^ also increase rapidly when NO has
been depleted. Hence, a reaction involving one of these three species and/
or peroxy radicals appears to be missing from our mechanisms. To demonstrate
that a reaction with N03 provides a closer simulation to the observed ozone
profile for these recent butane experiments, we included a reducing reaction
for NOg to NOg of about 400 min"^. Figure 108 shows that ozone is reduced to
near the observed data for EC-304, yet the butane decay, NO behavior, and
A
product appearance profiles are essentially unchanged. A reducing species for
NOo is now under investigation. For an NO, reaction with formaldehyde, a value
-1-1	-1 -1
near 10000 ppm min , or for acetaldehyde a value near 2500 ppm min , would
produce similar results in these simulations.
The butane decay for UCR runs EC-305 and EC-307 could not be simulated
with our current chemistry. Typically, we increase the photolysis
constants until the hydrocarbon decay rate is matched. However, these two
runs have very high HC/N0 ratios which lead to rapid NO removal, producing,
in turn, very low concentrations for NO. The H02 reaction with NO
restores the OH radicals which, in turn, are responsible for the butane decay.
Hence some means of either maintaining NO in the simulation or of restoring
OH, other than reaction with NO, must be missing from our mechanism.
232
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SECTION 5
THE TOLUENE MECHANISM
Aromatic compounds form a significant fraction of the reactive hydrocarbons
in urban photochemical smog. Our approach to the treatment of aromatics oxi-
dation has involved two activities: (1) the preparation of empirical mechanisms
that replicate the behavior of ozone and nitrogen oxide during oxidation, and
(2) the explicit modeling of toluene chemistry. During the past year, these
two efforts have, to some degree, converged, and our toluene mechanism is
reasonably explicit as to the compounds involved; it also reproduces the
ozone and NO behavior well.
A
EMPIRICAL FEATURES OF AROMATICS OXIDATION
We have developed a series of empirical kinetic mechanisms to simulate
photochemical oxidant production in aromatic hydrocarbon systems (Whitten
and Hogo, 1977; Whitten et al., 1979). Our preferred method of mechanism
development is first to construct an explicit representation of all major
products and reactions in the hydrocarbon decay scheme. From this explicit
mechanism, we formulate a condensed mechanism, combining similar radicals,
products, and the like into generalized-state variables. It has been difficult
to apply this process for aromatic hydrocarbons, since explicit mechanisms that
give adequate simulations of hydrocarbon decay, N0V behavior, and ozone pro-
duction have been lacking. Thus, we have resorted to the use of empirical
mechanisms.
Several observable features differentiate aromatic hydrocarbon photochemistry
from that of such compounds as propylene and butane. The most noticeable of
these features is the inefficiency of N0-to-N02 conversions as compared with
233
-------
the hydrocarbon oxidized. Kopczynski, Kuntz, and Bufalini (1975) reported the
ratio of hydrocarbon consumption versus NO oxidized as 1.5 for a paraffin
mixture, 2.5 for olefins, and 4.1 for aromatics. Moreover, they noted that
the ratio of HC consumption to NO oxidation varied with NO concentration,
whereas the olefin and paraffin ratios remained constant. Cox, Derwent, and
Williams (private communication, 1979) have obtained similar results in high
OH (HONO-driven) hydrocarbon N0X systems.
In the UCR toluene smog chamber runs analyzed thus far, we have observed
a marked decline in the efficiency of N0-to-N02 conversions after the N02 peak
has been reached. This decline in efficiency for aromatic systems appears to
be even more pronounced than that observed for olefin and paraffin systems. Our
first empirical aromatics mechanism (Whitten and Hogo, 1977) reduced ozone
production efficiency by means of an NOj-aromatics reaction. This reaction
was given a rate constant considerably higher than the actual reaction rate
of NOg with toluene to represent the reaction of the highly unsaturated ring-
opened compounds formed in aromatics decomposition. In subsequent mechanisms,
we treated the hypothesized compounds more explicitly.
The product of the NO^ addition to propylene has recently been identified
as propylene glycol 1,2 dinitrate (Akimoto et al., 1978). Dinitrates are
highly toxic compounds, and their formation in aromatic systems would have
important implications in air quality management.
If NOg uptake is important in aromatic photochemistry, it may account
for another feature of the UCR toluene runs. Estimates of the 0H« concen-
tration in UCR smog chamber simulations EC-266 through EC-273 (see Figures
121 through 126) based on toluene decay rates seem inconsistent with the
rate of N0X consumption. More precisely, in these experiments N0X decay
is noticeably greater than can be explained by the observed nitrogen species
(PAN, PBN, and so on) and the formation of nitric acid by the reaction of
OH* plus NOg. This nitrogen balance discrepancy is not an obvious feature
of the propylene and butane runs that we have examined. We hypothesize
that some nitrated organic is being formed. Since any PAN-I1ke compound
would tend to register as NO (and thus would not appear as a discrepancy)
A
234
-------
0.60
o_
cu
0.45
tr
on
0.30
UJ
s
o
0.15 -
0 50 100 150 200 250 300 350 400
TIME (KINUTES)
PRN
0.100
0.075
£ 0.050
tu

0.025
0.000
TIME (MINUTES)
T0L
1.300
x
a.
a.
1.100
CD
%, 0.900
ui
o
ac
u
0.700
0.500
0 50 100 150 200 250 300 350 400
TINE (MINUTES)
FIGURE 121. SIMULRTI0N RESULTS F0R
EC-266
235
-------
0.60 -
0.45
0.30
o
z
oa
u
0.15 -
0.00

0.60
0.45
IX
at
0.30
m
o
0.15
0 50 100 150 200 250 300 350 400
TIHE (MINUTES)
0.00
—r
T0L
"i—i—r
-t—r
-fqw J 1
0 50 100 150 200 250 300 350 400
TIHE (MINUTES!
0.125
0.100
gO.050
c_>
ae
o
0.075
0.000
50 100 150 200 250 300 350 400
TIME (MINUTES!
FIGURE 122. SIMULRTI0N RESULTS F0R
EC-269
236
-------
T0L
0.60
0.45
£ 0.30
ui
o
s
o
0.15
0.00
50 100 150 200 250 300 350 400
TIME (MINUJES)
0.60
z
O-
0.
0*45
z
ca
ft<-4

cr
ee
0.30
o
0.15
0.00
TIME (MINUTES)
FIGURE 123. SIMULflTI0N RESULTS F0R
EC-270
1	T
1 ) V
0.60
0.45
03
N0
N02
*
+
x
cc
oc
tu
o
0.30
CJ
0.15
0.00.

********
I—i 11, |
50 100 150 200 250 300 350 400
TIME (MINUTES)
,..~r -1—-T	. -( 	(
T0L *
1.300 -
o.
a.
1.100
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TUL
0.60
0.60
0.45
0.45
a
CE
| 0.30
UJ
o
XXX
u
z
IS
s
«j
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0.15
0.15
0.00
0.00
50 100 150 200 250 300 350 400
TIME CHINUTES)
TINE (MINUTES)
0.125
0.100
S 0.075
oc
0.050
<_>
cj
0.025
0.000
100 ISO 200 250 300 3S0 400
TIME (MINUTES)
FIGURE 125. SIMULATION RESULTS F0R
EC-272
238
-------
i—i—i—r
03
************ at * ****** *
J	L
i-
50 100 150 200 250 300 350 400
TIME (MINUTES)
0.12
a.
a.
0.09
z
ui
o
0.06
0.03
0.00
NB
N02
%+ + + + ++
i—r

50 100 150 200 250 300 350 400
TIME (MINUTES)
T0L
0.60
ac
a.
a.
W
0.45
0.30
u
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0.15
0.00
50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 126. 5IMULRTI0N RESULTS F0R
EC-273
239
-------
we speculate that perhaps an oxygenated alkyl dinitrate is being formed.
Such a compound may be difficult to measure, which might account for the
poor nitrogen and carbon balances observed in aromatic systems.
The glyoxal compounds formed in the aromatic ring-opening process photolyze
more rapidly than formaldehyde. The radical production rate in toluene systems
cannot be explained on the basis of aldehydes alone, and therefore, the additional
radicals must come from species peculiar to aromatics systems, such as benzalde-
hyde and glyoxals. Since the addition of benzaldehyde to a photochemical system
actually retards the system (Kuntz, Kopczynski, and Bufalini, 1973), we now
believe the glyoxals to be the principal photolytic species.
We refer to the ratio of oxidizing radicals produced by a system to the
primary photolysis rate as "Q":
n _ Oxidation
^ " Photolysis
Factor Q appears to be an important measure of the ozone-forming capacity of
the system at high hydrocarbon-to-NO (HC/NOj ratios. A low Q system should produce
A	A
less ozone than a high Q system at high HC/NO ratios, because the NO
A
disappearance rate is faster at high HC/N0X ratios relative to the Og produc-
tion rate. Since aromatic systems have a demonstrably low oxidizing rate and
a high primary photolysis rate, the "Q" for aromatic systems is low. Further-
more, if our hypothesis of dinitrate formation is correct, the difference
between the ozone formed at high HC/NO ratios by aromatics as compared with
A
olefin-paraffin systems should be even more striking. Accordingly, we
designed several experiments to test this hypothesis. The first of these
experiments has been carried out and, as predicted, the addition of toluene
to a propylene system at high HC/N0Y ratios causes a reduction
in peak ozone concentration. We will discuss this experiment in greater
detail when we describe our simulations of the UNC outdoor smog chamber
results.
240
-------
the explicit photochemistry of aromatic compounds
The gas phase oxidation of an aromatic hydrocarbon molecule is initiated
by a hydroxy! radical. The hydroxy! radical attack may proceed through
either addition to the aromatic ring or hydrogen abstraction of side chain
groups. In toluene, for example, side chain abstraction gives
The aromatic radical then absorbs oxygen to form a peroxy radical that may, in
turn, effect an N0-to-N02 conversion and then yield benzaldehyde:
CH;
+ 0,
CH20£
(9)
CH20£
+ NO
ch2o-
+ N0o
(10)
h2o-
+ Or
CH0
+H0J
01)
Hydroxy! radical addition to the aromatic ring results in an energy-rich
adduct, which becomes stabilized:
*
CH.
OH +
CH.
Cf
OH
H
+ M
+ M .(12)
241
-------
3
According to an analogy with 0( P) atom reactions, hydroxy! attack at the ortho
position will probably predominate (Atkinson et al., 1978).
The thermalized OH-toluene adduct is unstable at temperatures >_ 380°K
(Perry, Atkinson, and Pitts, 1977). From extrapolation at high temperatures
[where only Reaction (8) is important] to lower temperatures, the ratio of
hydroxyl abstraction to addition was estimated by Perry, Atkinson, and
Pitts (1977) to be 0.16 (+0.07 or -0.05).
At low pressures (6 to 15 torr), the adduct radical reacts with Og:
yielding cresol at a ratio of seven times the yield of benzaldehyde (Hendry,
1978), a rate that agrees with the estimate of Perry, Atkinson, and Pitts (1977).
At higher 02 pressures, however, the product yield of cresol to benzal-
dehyde as observed at the UCR chamber and elsewhere (Hoshino, Akimoto, and
Okuda, 1978) is closer to 2 to 1. The destruction rate of cresol by OH is too
low to explain this discrepancy.
Atkinson et al. (1978) suggest that the OH-toluene adduct radical may
react with Og to form an oxygenated radical:
In the degradation of phenol by gamma-ray-Induced hydroxyl In aqueous
solution (Sato, Takimoto, and Tsuda, 1978), the secondary reaction with
is immediately followed by ring opening to yield dihydroxymucondlaldehyde:
(13)
242
-------
6-s-
Consistent with this reaction pathway is the work of Schwartz (1974),
who identified ring-opened compounds of six and seven carbon atoms in
toluene aerosol.
Smaller ring-opened fragments have also been observed in aromatics-OH
systems. Nojima et al. (1974) reported the formation of glyoxal, methylglyoxal,
and biacetyl, all of which would have been produced by the cleaving of rings in
the photooxidation of benzene, toluene, and xylene. Darnell, Atkinson, and
Pitts (1978) have determined that in the N0X photooxidation of o-xylene,
approximately 20 percent of the reaction of OH radicals leads to biacetyl.
Nojima et al. (1974) found that biacetyl production in an o-xylene system
was only half as great as methylglyoxal production. However, these experi-
ments were carried out using very high concentrations (1000 ppm) of hydro-
carbons. Glyoxal production was observed in all three aromatics systems.
For toluene, the principal oxygenated product observed was methylglyoxal.
Takagi et al. (1979) observed the ratio among glyoxal, methylglyoxal,
and biacetyl production to be 3.3:0.5:1. These ratios were estimated by
Nojima et al. (1974) to be 0.2:2.5:1. Although the variations in these data
are large, they suggest that over half of the products of the hydroxyl aro-
matic reactions are ring cleavage fragments.
The formation of glyoxal compounds might occur with the successive degra-
dation of the ring-opened compound. However, glyoxals seem to form immediately
after the initial hydroxyl reaction, suggesting that some fraction of the ring
cleavage reaction forms multiple fragments.
243
-------
One possible pathway Involves the oxygenated OH-toluene adduct radical
(Atkinson, 1979, private comnuni cation):
CH3	n	CH3^0-°"
(>" x Q*
+ 1,0 — n°2 +
Cleavage then occurs to give methylglyoxal (circled), HO^ and another
ring-opened fragment.
The complementary product to the glyoxals, produced either from further
degradation of a ring-opened compound or by cleavage of the ring at multiple
points, would be an Internally unsaturated dialdehyde (2 butene 1,4 dial for
the toluene system):
H 0
I II
H-C-C-C-C-H
!i i
0 H
The properties of unsaturated dialdehyde compounds such as this (called FOLE
in our toluene mechanism), are speculative. These compounds might photolyze;
the double bond might react with OH, Og, or NOgj the hydrogen atoms might be
abstracted to yield peroxyacyl-like radicals, which might form PANs and other
compounds. Such compounds might also form aerosols or adhere to the smog
244
-------
chamber walls. The latter effect is likely because dialdehydes have low vapor
pressures and high boiling points. Butanedial (succinaldehyde), for example,
has a boiling point of 170°C, and hexanedial has a vapor pressure of 3 torr
at 90°C (Rappoport, 1967).
The quantum yield for photolysis to radicals for the unsaturated
aldehydes is probably low. Acrolein, for example, on absorbing light, tends
to form an excited polymerizing molecule rather than decompose (Calvert and
Pitts, 1966). The inclusion of a photolysis reaction for the unsaturated
dialdehydes would make the simulation mechanism much too reactive.
Reactions involving 0H« are probably not important because the number of
N0-to-N02 conversions would become too large unless some other mechanism
exists to reduce the importance of that reaction. The low vapor pressure of
these dialdehydes could be responsible for a reduction of any 0H> importance.
As we have mentioned previously, Schwartz (1974) observed ring-opened com-
pounds in the analysis of toluene aerosols.
Recent measurements (01Brian, personal communication, 1979) indicate that
a substantial fraction of the carbon in toluene oxidation is lost from the gas
phase. For unsaturated dialdehydes leaving the gas phase, only a modest first-
order loss rate (^.05 min"1) is necessary to compete with hydroxy! attack
and to eliminate the excessive ozone production caused by the hydroxyl reaction.
This reasoning is speculation in support of a specific fact: our simula-
tions of toluene systems work better when the reaction of OH with these secondary
oxidation products is eliminated. Therefore,	we have eliminated the reaction,
noting that the overall behavior is likely to be complex.
The only reactions of the FOLE compounds that are contained in our toluene
mechanism are reactions with 0g and NO^. We have assumed that the internal
double bonds contained in these compounds react with 03 and NOg at rates simi-
lar to that of dimethylbutene. These rates are very fast; even if the FOLE
compounds are rapidly precipitating from the gas phase, they will tend to react
in our simulations with 0g and NOg before they encounter an aerosol particle or
a chamber wall.
-------
Fate of Benzaldehyde
Benzaldehyde is a known product of toluene oxidation, accounting for
11 to 23 percent of the overall reaction products (Perry, Atkinson, and Pitts,
1977; Hendry, 1978).
It has long been known that the addition of benzaldehyde to photochemical
mixtures tends to retard their photochemical activity (Kuntz, Kopczynski, and
Bufalini, 1973). One could explain this effect by suggesting that benzalde-
hyde is a radical scavenger. However, systems of air, benzaldehyde, and N0X
show increases in NO-to-NOg conversions when compared with air systems. Obvi-
ously, radical scavenging is balanced by some source of radicals as well.
Hendry (1972) suggests that the rate of decomposition of the benzoyloxy
radical is low, allowing it to react with oxides of nitrogen and the reactor
wall, thereby serving as a radical sink. This leads to the following reaction
sequence (Hendry et al., 1978):
0,
0.
0
0
6
°no2
246

-------
This sequence is primarily a scavenging mechanism: Used alone, it produces
too great a retardation of photochemical activity in UCR runs EC-337 and EC-339.
Counterbalanced by the scavenging effect is the effect of benzaldehyde photolysis:
H

,0
c
6^6
+ HCO
1/
6
+ H02 + CO
We assume that the carbon-phenyl bond is the bond that breaks upon
photolysis to reduce the number of N0-to-N02 conversions in the photolysis
pathway. We have also included a decomposition reaction for the benzoyloxy
radical:
Photolysis yields for benzaldehyde are not well known. At 313 nm, the
quantum yield at room temperature is low. However, a second absorbtion band
exists below 310 nm with a very high absorbtion peak (x max = 282 nm, e ¦ * 1600;
Calvert and Pitts, 1966). If benzaldehyde photolysis proves to be unimportant,
the decomposition rate of the benzoyloxy radical will have to be increased.
The chemistry of peroxybenzoylnitrate is from Hendry 1972.
Fate of Cresol
Cresol is a reaction product in the toluene system similar in magnitude
to that of benzaldehyde (Hoshino, Aktmoto, and Okuda, 1978; UCR toluene data). It
0
H0o + ring-opened compounds
This decomposition is assumed to be slow with a pseudo-first-order rate
constant of 2.0 min""\
247
-------
reacts with OH approximately six times faster than toluene (Perry, Atkinson,
and Pitts,1977). The products of this reaction are unknown; we have used
dihydroxy toluene as the reaction product.
Although cresol does not react with ozone, there is evidence of a strong
reaction with N03 (O'Brian, personal communication, 1979). It is possible
that cresol is responsible for the N03 loss in aromatic systems that we have
discussed previously. However, the yield of cresol from toluene oxidation
does not seem to be high enough for it to be the principal N03 uptake species.
The expected product of the NO^-cresol reaction would be a cresol nitrate.
MASS BALANCE IN THE TOLUENE MECHANISM
The toluene mechanism is given in Table 31. Subsequent to the initial
reaction of OH* with toluene, 16 percent of the reacted carbon mass goes to
cresol and 11 percent goes to benzaldehyde. Of the remaining 73 percent
carbon, 80 percent follows a pathway that leads to ring opening, fracture,
and the production of <*-dicarbonyls, here assumed to be methyl glyoxal. The
complementary product to the methyl glyoxal is labeled FOLE and is assumed to
react exclusively with 03 and NOj, to form dinitrates. The remaining 20
percent of the ring opening (15 percent overall) goes to a diolefinic compound
assumed to react as two FOLE groups.
There is some doubt as to the fate and precise reactions of the compounds
grouped as "FOLE." The overall stoichlometry of the toluene oxidation
sequence presented here mimics actual toluene oxidation too precisely to be
dismissed lightly. If the suggested FOLE reactions do not exist, then they
at least emulate reactions that are taking place.
DESCRIPTION OF TOLUENE SIMULATIONS FOR UCR
Initial conditions and photolysis rates for the UCR toluene experiments
are given in Table 32 There were minor variations in the solar simulator light
intensity during the second series, but we have made no attempt to correct for these
effects. Nitrogen dioxide photolysis varied only about 2 percent during the series.
248
/
-------
TABLE 31. THE DEVELOPMENTAL TOLUENE MECHANISM

Reactions
Rate Constant
Activation
energy
1
N02

= NO
0
*
-0.
2
0

= 03

4.400E+06
-5.100E+02
3
03
NO
= N02

2.660E+01
1.450E+03
4
0
N02
= NO

1.340E+04
-0.
5
03
NO 2
= N03

4.800E-02
2.450E+03
6
N03
NO
= N02
N02
2.800E+04
-0.
7
RX+

= OH

1.300E-01
-0.
8
N02
OH


1.400E+04
-0.
9
03
OH
= H02

1.000E+02
9.400E+02
10
03
H02
= OH

2.400E+02
5.800E+02
11
N03
N02 H20 =


1.560E-03
-0.
12
CO
OH
= H02

4.400E+02
-0.
13
H02
NO
= OH
N02
1.200E+04
-0.
14
H02
H02


7.500E+03
-0.
15
NO
NO
= N02
NO 2
1.500E-04
-0.
16
PAR
OH
= ME02

1.500E+03
-0.
17
PAR
0
= NE02
OH
2.000E+01
-0.
19
OLE
OH
= RAO 2

4.200E+04
-0.
20
OLE
0
= AC03
ME02 X
1.400E+03
-0.
21
OLE
0
= CARB

4.000E+03
-0.
23
OLE
03
= CARB
CRIG
8.000E-03
-0.
-------
TABLE 31 (Continued)
Activation
Reactions






Rate Constant
enerqy
24
OLE
03
= CARB
MCRG


8.000E-03
-0.
25
ETH
OH
= RB02



1.200E+04
-0.
26
ETH
0
= ME02
H02
CO

6.000E+02
-0.
27
ETH
0
= CARB



6.000E+02
-0.
28
ETH
03
= CARB
CRIG


2.400E-03
-0.
29
CARB
OH
= AC03
X


8.000E+03§
-0.
30
CARB
OH
= H02
CO


1.050E+04§
-0.
31
CARB

= X
ME02
H02

2.000E-04*§
-0.
32
CARB

= CO
H02
HC2

1.800E-03*§
-0.
33
CARB

= CO



3.600E-03*§
-0.
34
ME02
NO
= NO 2
HCHO
H02

3.700E+03
-0.
35
ME02
NO
= N02
CARB
HO 2

7.300E+03
-0.
36
AC03
NO
= N02
ME02
C02

3.800E+03
-0.
37
RB02
NO
= N02
CARB
CARB
H02
1.200E+04
-0.
38
RB02
03
= HCHO
CARB
HO 2

5.000E+00
-0.
39
RA02
NO
= N02
CARB
HCHO
H02
1.200E+04
-0.
40
RA02
03
= CARB
CARB
H02

2.000E+04
-0.
41
X
PAR
=



1.000E+05
-0.
42
CRIG
NO
= N02
CARB


1.200E+04
-0.
43
CRIG
N02
= NO 3
CARB


8.000E+03
-0.
44
CRIG
CARB
= OZD



2.000E+03
-0.
-------
TABLE 37 (Continued)
Activation
Reactions






Rate Constant
energy
45
CRIG

ii
o
o



6.700E+02
-0.
46
CRI6

=



2.400E+02
-0.
47
CRIG

= H02
H02
CO

9.OOOE+Ol
-0.
48
MCRG
NO
= N02
CARB


1.200E+04
-0.
49
NCRG
N02
= N03
CARB


8.000E+03
-0.
50
MCRG
HCHO
= OZD



2.000E+03
-0.
51
NCRG

=



1.500E+02
-0.
52
NCRG

= X
NE02
CO
OH
3.400E+02
-0.
53
NCRG

= X
NE02
H02

4.250E+02
-0.
54
NCRG

= H02
CARB
H02
X
8.500
-0.
55
NE02
NO
= NRAT



1.000E+02
-0.
56
NE02
03
= CARB
H02


5.000E+00
-0.
57
AC03
H02
=



4.000E+03
-0.
58
NE02
H02
-



4.000E+03
-0.
61
AC03
N02
= PAN



2.000E+03
-0.
62
PAN

= AC03
N02


2.800E-02
-0.
64
TOL
OH
= RARO



6.700E+03
-0.
65
TOL
OH
= CRE
H02


1.500E+03
-0.
66
TOL
OH
= B02



1.000E+03
-0.
67
RARO
NO
= N02
H02
C

1.200E+04
-0.
68
C

= FOLE
FOLE


2.000E+03
-0.
-------
TABLE 31 (Continued)
Activation
Reactions





Rate Constant
energy
70
C

« gly
FOLE
PAR
8.000E+03
-0.
71
GLY

= H02
CO
AC03 X
3.600E+01
-0.
73
RARO
03
= H02
AERO

2.000E+01
-0.
74
03




2.200E-04
-0.
75
FOLE
03
= AERO


1.500E+00
-0.
76
FOLE
N03
= NTO


3.500E+04
-0.
77
NTO
NO
= DNTR


5.000E+02
-0.
78
B02
NO
= BZA
H02
N02
1.000E+04
-0.
79
BZA
OH
= BZ02


2.000E+04
-0.
80
BZ02
N02
= PBZN


2.500E+03
-0.
81
BZ02
NO
= N02
PH02

3.700E+03
-0.
85
PBZN

= BZ02
N02

2.200E-02
-0.
86
PH02
NO
= PHO
N02

1.000E+04
-0.
87
PHO
N02
= PN03


6.000E+01
-0.
88
BZA

= H02
PHO 2
CO
2.000E-03*
-0.
89
CRE
OH
= H02
DHTL

5.000E+04
-0.
90
CRE
N03
= NCR


1.000E+04
-0.
91
PHO

= H02
C

2.000E+00
-0.
92
PH02
H02
=


4.000E+03
-0.
-------
TABLE 31 (Concluded)
Rate Constant
Activation
energy
8.000E+00
-4.200E-04
-0.
-0.
Reactions
93
63
OLE
H20
N03
= NTQ
ro
oi
u>
* Photolysis rates in min"1. Photolysis rates are as ratios to for natural sunlight.
+ Fractional splits between carbonyl groups (formaldehyde vs. higher aldehydes) vary when
there are coreactants with toluene. The table is for propylene and toluene. Toluene
alone is assumed to yield only formaldehyde.
-------
TABLE 32 UCR SIMULATION CONDITIONS
Exp. Ho. 	Initial concentration (ppm)		Photolysis rate constant (min"^)

NO
no2
Tol
HCHO
BZA
Acet
CO
V
no2
Mgly
HCHO -^Radicals
BZA
EC-266
0.432
0.059
1.196
0.01
0.
0.
0.
0.
0.35
0.0135
3.5
X
10"4
7.2
X
o
1
EC-269
0.398
0.074
0.566
0.003
0.
0.
0.
0.005
0.35
0.0135
3.5
X
10~4
7.2
X
10"4
EC-270
0.414
0.051
0.576
0.178
0.
0.
0.
0.
0.35
0.0135
3.5
X
10~4
7.2
X
10"4
EC-271
0.186
0.029
1.146
0.004
0.
0.
0.
0.008
0.35
0.0135
3.5
X
10"4
7.2
X
10"4
EC-272
0.398
0.08
0.58
0.
0.
0.378
0.
0.
0.35
0.0135
3.5
X
10"4
7.2
X
1
o
EC-273
0.096
0.014
0.587
0.003
0.
0.
0.
0.008
0.35
0.0135
3.5
X
10~4
7.2
X
M-J
o
1
EC-327
0.357
0.096
0.573
0.
0.
0.
0.
0.004
0.4
0.015
3.5
X
10~4
8.0
X
10"4
EC-336
0.342
0.097
1.008
0.303
0.
0.
0.
0.
0.4
0.015
3.5
X
10"4
8.0
X
10~4
EC-337
0.322
0.124
0.959
0.
0.172
0.
0.
0.0025
0.4
0.015
3.5
X
10"4
8.0
X
10"4
EC-339
0.341
0.102
0.537
0.
0.187
0.
0.44
0.
0.4
0.015
3.5
X
10~4
8.0
X
o
i
-fk
EC-340
0.333
0.096
0.537
0.
0.
0.
0.26
0.007
0.4
0.015
3.5
X
10"4
8.0
X
10"4
* Rx is an initial radical source having a photolysis rate 1/2 that of HONO (.0.03 min^)
to mimic HONO effects.
-------
The only general error seen in these runs is an overprediction of- PAN.
This is probably caused by our assumption that all of the <*-dicarbonyls formed
are methylglyoxal. If simple glyoxal comprised a significant fraction of the
^-dicarbonyls, then the production of peroxyacetyl radicals and" PAN formation
would be reduced.
A comparison of the toluene only runs with those runs having high initial
conditions of formaldehyde and acetaldehyde (runs EC-270, EC-271, and EC-336)
shows the need for the «-dicarbonyls as a radical source. Even if all of the
toluene that decays were to go immediately to formaldehyde, the photolysis
rate necessary to provide radicals for the toluene runs is twice that needed
to fit the formaldehyde-added runs. Clearly, some product having a high
photolysis rate is formed from toluene oxidation.
In the later series of experiments, EC-327 through EC-340, analysis of ben-
zaldehyde is begun (see Figures 127 through 131). Runs 337 and 339 contained high
initial conditions of benzaldehyde and exhibited the slower chemistry noted
previously. Benzaldehyde decay for these runs is slightly underpredicted, and
the benzaldehyde peak for the other runs is slightly overpredicted. These
factors suggest that the OH* rate constant for benzaldehyde is faster than
that used in these simulations or that benzaldehyde photolysis should be faster.
DESCRIPTION OF TOLUENE SIMULATIONS FOR UNC
Initial conditions for the UNC outdoor smog chamber experiments are given
in Table 33, and Figures 132 through 139 give the simulation results for these
same experiments. Simultaneous experiments involving ethylene and propylene
were simulated using the Revised Carbon-Bond Mechanism (CBM-II) given in Table 34.
The Influence of water on PNA chemistry, discussed in Section 3, was not included
in these simulations.
255
-------
The only modification of the mechanism from experiment to experiment was
a change in the fraction of formaldehyde and acetaldehyde used. For ethylene,
all aldehydes were assumed to be formaldehyde; for propylene, a 2:1 formaldehyde
acetaldehyde ratio was used.
The only noteworthy feature of the 1978 experiments is the very high Rx
values required to fit the 91878 runs. The value of 0.06 ppm for Rx is clearly
too great to be explained by H0N0. Yet without this value, the simulations
are greatly retarded, even though the production and decay rates reproduce
the data, albeit involving a time lag. One is tempted to consider the pos-
sibility that the data were somehow shifted by an hour or two. Otherwise,
we have no explanation for this curious feature.
THE PROPYLENE TOLUENE EXPERIMENT (62179)
In order to highlight the NO loss, which is one of the most important
features of toluene oxidation, we designed an NOx-limited experiment in which
the loss would have an effect upon ozone. As expected, a propylene toluene
mix gives a lower ozone peak (20 percent lower) than a propylene-only run,
despite a faster initial ozone production rate. Our simulations of these
experiments are shown in Figures 140 and 141. (In the 1979 experiment, unlike the
1978 series, PAN data were subtracted from the NOg data in order to correct
for the known PAN interference.) If our simulations are correct, the increased
N0X loss for the toluene system is equally divided between two mechanisms; one
is the loss of NOg to organic nitrates as previously described. However, if
the NOg reactions are removed, some difference still exists (the results are
given in Figure 142 with reactions 76 and 90 eliminated). This is because the
overall photolysis rate is substantially higher in the toluene-added system,
resulting in a higher OH concentration and a higher production rate of nitric
acid. The ozone formation rate is enhanced marginally and the ozone peak is
reached sooner, though at a lower concentration than in the propylene-only
system. This, therefore, is a graphic demonstration of the parameter "Q."
256
-------

0.10
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.08 -
x
(L.
tL.
0.06 -
t 0.04 -
tu
o
HCH0 +
0.02 -
0 50 100 150 200 250 300 350 400
TIME (MINUTESi
T0L
0.80
0.60
to
0.20
0.00
50 100 150 200 250 300 350 100
TIME (MINUTESl
FIGURE 127. SIMULATION RESULTS F0R
EC-327
257
-------
0.60 -
0.45
0.30
o
z
m
CJ
0.15
0.00
&»***„

0 50 100 150 200 250 300 350 400
TIME (HINUTES)
1.25
1.00
0.73 -
t 0.30 -
i—i—i—T
T0L ¦
F0RM ~
TO
u
0.25
-taw-
4 +
0.00
—L~-—)	 I t 'HCH01	T
0 50 100 150 200 250 300 350 400
TINE (HINUTES)
0.125
0.100
50.075
£ 0.050
u
u
0.025
0.000,
100 150 200 250 300 3S0 400
TIKE (MINUTES)
FIGURE 128. SIMULRTI0N RESULTS F0R
EC-336
258
-------

0 50 100 150 200 250 300 350 400
TIME (MINUTES)
1.2S
1.00
0.75
0.50
0.25
0.00
I
T0L
i i r—r—r~
j	L
r*i
J	1	!	L
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.20
^ u« 10

0.00
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 129. SIMULRTI0N RESULTS F0R
EC-337
259
-------
03
N0
N02
0.60
0.45
cc
ie
£ 0.30
bJ
u
u
0.00
50 100 150 200 250 300 350 400
TIME (MINUTES)
T0L
BZH
C0
0.60
x
a.
a.
-j. 0.45
(T
ae
i-
z 0.30
hi
U
Z
(B
O
0.15
0.00
50 100 150 200 250 300 350 400
TIME (MINUTES)
PAN
HCH0
0.060
0.045
cr
K
»-
ac
laJ
O
z
BB
U
0.030
0.015
0.000
SO 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 130. SIMULATION RESULTS F0R
EC-339
260
-------
0.60
x
a.
a.
0.45
ac
tfc
IU
o
9
o
0.30
0.15
0.00
1 1 1
1 1 1 1
03 »

Nil +

N02 *
—



*
* V


0 50 100 150 200 250 300 350 400
TIME (MINUTES)
0.60 -
0.60
a:
an
o
s>
t_>
0.40 -
0.20 -
0 SO 100 150 200 250 300 350 400
TIME (MINUTES)
5.00
4.00
3.00
2,00
0 50 100 150 200 250 300 350 400
TIME (HINUTES)
0.060
0.045
a.
ae
0.030
o
x
u
0.015
0.000
i
PAN
HCH0
BZfl
1 1 1 1 1
«
+
X
	"'1
-
+ /
(*
' *+¦
1

/ +/**

y
/ / K
/*
/£,		BZfl —-
y^Sfx* x x X X
1 1 ,1 1. 1
X X
,1
0 50 100 150 200 250 300 350 400
TIME (MINUTES)
FIGURE 131. SIMllLflT10N RESULTS F0R
EC-340
261
-------
TABLE 33. UNC SIMULATION CONDITIONS*
Experiment 	Initial conditions (pot)

NO
no2
TOL
PAR
OLE
ETH
CO
Rx
UNCR 91878(a)
0.4
0.1
0.
0.
0.
1.5
0.32
0.04
UNCB 91878(a)
0.39
0.166
0.6
0.
0.
0.
0.32
0.06
UNCR 91878(b)
0.4
0.1
0.
0.
0.
1.5
0.32
0.01
UNCB 91878(b)
0.39
0.166
0.6
0.
0.
0.
0.32
0.01
UNCR 91478
0.234
0.058
0.319
0.
0.
0.
0.24
0.002
UNCB 91478
0.232
0.062
0.
0.
0.
0.48
0.21
0.007
UNCR 81678
0.

0.
0.51
0.51
0.
0.293
0.004
UNCB 81678
0.606
0.081
0.56
0.
0.
0.
0.293
0.004
UNCR 61379
0.367
0.085
0.
0.93
0.93
0.
—
0.
UNCB 61379
0.36
0.083
0.413
0.91
0.91
0.

0.
* Photolysis rates for NO2 were calculated from TSR and UV data. The ratio
of other photolysis to iq were methylglyoxal = 0.036; benzaldehyde = 2 x 10
formaldehyde to radicals = 2.7 x IQ"3; formaldehyde to stable products =
5.4 x 10-3; acetaldehyde - 6 x 10-4.
-------
0.60
n.
0.45
0.30
o
2
B
O
0.15
0.1
'1 1 1
"i r—r i		
N0 *

N2>2 +

83 *
—
-
~"X * X
^ +
/*
\ +
* /

X /
p
-
/ \. +

Jf \ "+
si
fa \
i j—
, f —1 >*.. 1— -
0.80
0.60
s
i-
cr
0.40
liJ
o
o
0.20
,0 62. 5125. (187. S50. (312.975. (537.9500.0
TIME (MINUTES)
0.1
~t~	r
701 ¦
th—i—r
J	L
J	!	L	L
).0 62.5125.Q87.E25Q.® 12,375.(337.3500.0
TIME (MINUTES)
FIGURE 132, SIMULATION RESULTS FOR UNCB TOLUENE—9 18 78
1.20
0.90
K
K
?. 50
fc o.eof-
0.so I—
t. i I arii	¦	...III.	-J
.0 67.5135.(£02. 5270.(B37. S05.0172.$40.0
TIME (MINUTES)
2.00
5.0 62.5125.a87. $50.ffil2.375.K37."$00.0
TIME (MINUTES)
FIGURE 133. SIMULATION RESULTS FOR UNCR ETHYLENE—9 18 78
263
-------
1.20 -
s:
a.
a.
0.90
CC
oc
0.00
ui
o
o
u
0.30 -
>. 0 67. S135. (202. 370 - CB37- 305. (872.3540.0
TIME 1MINUTES)
2,50
2. 00
a.
a.
1.50
CE
a:
1.00
ui
CJ
S
u
0.50
o.og
ETH

I I
J	I	L
J	J.
0 62.5125. Q87.5250. ®12.375. 2.37. S500. 0
TIME (MINUTES)
FIGURE 134, SIMULATION RESULTS FOR UNCR ETHYLENE—9 18 78
N0
NB2
03
0.60
a.
a.
t 0.30
ss
cj
0.15
0,00 	1	T I fflrrrn	1	—
0.0 62.5125.087.250.012.575.<137.®00
.0 62, 5125.087.250,012. SB75.337.5600.0
TIME (MINUTES)
o.so
x
a.
0.
0.60
a
| 0.40
ui
o
0.20
0.1
i i i i	r I I
T0L *
* *
J	I	I	JL.
t
.~ 62.5125.087. E250. ©12.975. a37. 9500.0
TIME (MINUTES)
FIGURE 135, SIMULATION RESULTS FOR UNCB TOLUENE—9 18 78
264
-------
03
N0
N02
0.46
0.36
ct
te
0.24
o
0.12
0.00
TIME (MINUTES)
T0L
0.40
0.30
fc 0.20
u
o
0.10
0.00
TIME (MIMUTES)
	I	1	1	1	1	1	1	
ci ¦
0.60 -
£
£
Z 0.45 -	¦ Jf" '
§ *
I
i0-30^	^
0.15 -
n n * ¦ I	'	'	'	'	'	'
0 80 160 240 320 400 480 560 640
TIME (MINUTES)
0.01S
PRN
0.012
0.009
&
0.006
0.003
0.000
0 80 160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 136. SIMULRTI0N RESULTS F0R
UNCR 91476
265'
-------
0.60 -
0 80 160 240 320 400 480 560 640
TIHE (MINUTES!
0.56 -
0.42 -
t 0.20 -
Ui
u
0.14 -
0.00
J	I	¦ ' ¦ ' «
0 80 180 240 320 400 480 560 640
TINE (MINUTES)
0.84
0.63
s
I
0.42
0.21
0.00
	1 1 1
"i
T—'T 1
C0 ¦




* _


**


*y

***
/



' L-	J	i_
1
1 1 1
0 80 160 240 820 400 480 560 840
TIME (MINUTES)
0.005
0.004
0.003 -
t 0.002 -
0.001 -
Q.OOQ
0 80 160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 137. SIMULATION RESULTS F0R
UNCB 91476
266
-------
03
0.88
0.66
x 0.44
u
0.22
0.00
0 60 160 240 320 400 480 560 640
0 80 160 240 320 400 480 560 640
TIHE (NINUTESI
0.68 -
0.51
VlI

-

; x

P
M

-
,L_. L L	
1 1	1	"	
0.10
0.08
0.06
0.04
u
1
0.02
0.00
1 1 1 1™
PAN ¦
1 ' 1 	 1 "" 1		
-
—
-
1
X

/
	1	'
< , , ,
TINE CHINUTES)
0 80 180 240 320 400 480 560 640
TIHE (HINUTES)
FIGURE 138. SIMULRTI0N RESULTS F0R
UNCR 132678
,267
-------
0.90
T0L
0.72
0.54
z
m
0.36
o
(S
CJ
0.16
0.00
80 160 240 320 400 480 560 640
TIME (MINUTES)
03
N0
N02
0.76
a.
x 0.57
xx.
fc 0.36
o
z
u
0.19
0.00
TINE CMINUTES)
T I I I I I T
C0
0.68 -
0.51 -
0.94 -
u
s
u
* IK
MHK—M	*
.
in m
0.17 ~
0.00
J	I	I	1
J	L
0 80 160 240 920 400 480 580 840
TINE (MINUTES)
FIGURE 139. SIMULATI0N RESULTS F0R
UNCB 81676
268
-------
1
2
3
4
5
6
8
9
10
12
13
14
15
TABLE 34. THE CARBON-BOND MECHANISM
Activation
Rate Constant energy
N02

NO
0
*
-0.
0

03

4.400 E+06
-5.100E+02
03
NO
N02

2.660E+01
1.450E+03
0
N02 -
NO

1.340E+04
-0.
03
N02 =
N03

4.800E-02
2.450E+03
N03
NO
N02
N02
2.800E+04
-0.
N02
OH


1.400E+04
-0.
03
OH
H02

1.000E+02
9.400E+02
03
H02 =
OH

2.400E+00
5.800E+02
CO
OH
H02

4.400E+02
-0.
H02
NO
OH
N02
1.200E+04
-0.
H02
H02 =


7.500E+03
-0.
NO
NO
N02
N02
1.500E-04
-0.
PAR
OH
ME02

1.500E+03
-0.
PAR
0
ME02
OH
2.000E+01
-0.
(Continued)
-------
27
28
30
29
31
60
32
35
36
37
34
38
TABLE 34 (Continued)
Activation
Rate Constant energy
ETH
OH'
= RB02



1.200E+04
-0.
E1H
0
= ME 02
H02
CO

6.000E+02
-0.
ETH
0
= HCHO



6.000E+02
-0.
ETH
03
= HCHO
CRIG


2.400E-03
-0.
HCHO
OH
= H02
CO
X
AC03
9.500E+03
-0.
HCHO
OH
=



9.500E+03
-0.
HCHO

= H02
H02
CO

*
-0.
HCHO

= X
ME02
H02
CO
*
-0.
HCHO

= CO



*
-0.
ME02
NO
= N02
HCHO
H02

7.300E+03
-0.
AC03
NO
= N02
ME02
C02

3.800E+03
-0.
RB02
NO
CM
o
II
HCHO
HCHO
H02
1.200E+04
-0.
ME02
NO
= N02
HCHO
ME02
X
3.700E+03
-0.
RB02
03
= HCHO
HCHO
H02

5.000E+00
-0.
OLE
OH
= RAO 2



4.200E+04
-0.
(Continued)
-------
20
21
23
24
39
40
48
49
50
51
52
53
54
41
TABLE 34 (Continued)
Activation
Rate Constant energy
OLE
0
= AC03
ME02
X

1.400E+03
-0.
OLE
0
= HCHO



4.000E+03
-0.
OLE
03
= HCHO
CRIG


8.000E-03
-0.
OLE
03
= HCHO
MCRG


8.000E-03
-0.
RA02
NO
= N02
HCHO
HCHO
H02
1.200E+04
-0.
RA02
03
= HCHO
HCHO
H02

2.000E+04
-0.
MCRG
NO
= N02
HCHO


1.200E+04
-0.
MCRG
N02
= N03
HCHO


8.000E+03
-0.
MCRG
HCHO
= OZD



2.000E+03
-0.
MCRG





1.500E+02
-0.
MCRG

= X
ME02
CO
OH
3.400E+02
-0.
MCRG

= X
ME02
H02

4.250E+02
-0.
MCRG

= H02
HCHO
H02
X
8.500
-0.
X
PAR




1.000E+05
-0.
CRIG
NO
= N02
HCHO


1.200E+04
-0.
(Continued)
-------
TABLE 34 (Continued)
Activation
Reactions




Rate Constant
energy
43
CRI6
N02
= N03
HCHO
8.000E+03
-0.
44
CRIG
HCHO
= OZD

2.000E+03
-0.
45
CRIG

= CO

6.700E+02
-0.
46
CRIG



2.400E+02
-0.
47
CRIG

= H02
H02 CO
9.000E+01
-0.
55
ME02
NO
= NRAT

5.000E+02
-0.
56
ME02
03
= HCHO
H02
5.000E+00
-0.
57
AC03
H02


4.000E+03
-0.
58
ME02
H02


4.000E+03
-0.
61
AC03
N02 »
PAN

2.OOOE+03
-0.
62
PAN

AC03
N02
2.800E-02
1.250E+04
63
H20



-4.200E-04
-0.
* Experimental.
-------
0.80
0.60
£
g
m
o
0.40
0,20
0.00
	1 "
"T	1	 T
i r r
NO
N02
03
¦
~
X
r
xlr-x—k—k

/

-
ijt
—
- ,
\ /
-
1
X*, V*
-J	1	L	
0 75 150 225 300 375 450 525 600
TINE (HINUTES)
1.25
1.00
0.75 -
•u
u

0.30 -
0.25 -
0 50 100 150 200 250 300 350 400
TINE (HINUTES)
0.125
0.100
g 0.075
*0.050
u
0.025
0.000,
TINE (MINUTES)
FIGURE 140, SIMULATION RESULTS FOR UNCB TOL-PRO—6 21 79
273
-------
1.25
1.00 -
I
0.73 -
t 0.50 -
ui
CJ
z
0.25 -
0.00
0 75 ISO 225 300 375 450 525 600
TIME (MINUTES)
1.25
1.00 -
0.73 -
fc 0.30 -
CJ
z
s
u
0.25 -
0.00

0 50 100 150 200 250 300 350 400
TIME (MINUTES)
PAN
0.40
30
u
0.10
0.00' 1 1 m 
-------
1.25
1.00
a.
0.73
£ 0.S0
u
u
0.2S
0.00
50 100 150 ZOO 250 300 350 400
TIKE (MINUTES)
N02
0.80
XX X
0.80
at
*
M
~-
«c
ne
»-
0.40
u
0.20
O.OQ
0 75 150 225 300 375 450 525 600
TINE MINUTES)
0.125
0.100
0.075
0.050
0.025
0.000
TIME (MINUTES)
FIGURE 142. SIMULATION RESULTS FOR UNCB TOL-PRO—6 21 79
WITHOUT N03 LOSS (REACTIONS 76 AND 90 ELIMINATED)
275
-------
The toluene-propylene system has a greater photolysis rate and, hence, a
lower Q than a propylene-only system. In NO -limited circumstances, the ozone
A
peak is lower.
276
-------
SECTION 6
CARBON-BOND CHEMISTRY
The developments in explicit chemistry, reported in earlier sections, have
not been integrated into the Carbon-Bond Mechanism (CBM) because these develop-
ments came late in the contract year. Since insufficient time precluded the
use of the extensive comparisons with explicit chemistry (as presented in
Whitten and Hogo, 1977; Whitten et al., 1979), this section presents only a
few simulations with the CBM. Since the report last year, the principal change
in the CBM has been a further improvement in the chemistry of aromatics based
on the mechanism for toluene described in Section 5 of this report. This section
presents a brief review of the differences between the original CBM and its
current formulation, CBM-II, along with some simulation results using both
versions. A compendium of isopleth diagrams is included to demonstrate the
behavior of several species that occur in atmospheric chemistry as a function
of the HC and N0V precursor levels.
A
COMPARISON OF OLD AND NEW MECHANISMS
The original formulation of the CBM was published in two documents (Whitten
and Hogo, 1977; Whitten, Hogo, and Killus, 1979). Table 35 presents the version
of the old CBM used in the present study. The interim report of last year
(Whitten et al., 1979) presents an extensively revised version of the CBM
(CBM-II). Shortly after publication of that report some minor improvements
were added to the aromatics chemistry, bringing the mechanism to the level shown
in Table 36. Both versions of the CBM have been used in several atmospheric
studies. The present comparison study suggests that either version appears to
reproduce smog chamber experiments, though the newer version is more
scientifically relevant; the atmospheric studies previously performed
using the old CBM are probably still valid from the standpoint of the chemistry.
277
-------
TABLE 35. THE ORIGINAL FORMULATION OF THE CARBON-BOND MECHANISM
Reaction
late constant*
fppm"1 Bin"')
NOz 4 *v ~ HO ~ O*
3 * 10-,t
0* 4 02(* KJ 03 (4 M)
2.08 * 10"5
o3 ~ no - no2 * o2
25.2
o« ~ no2 ¦» *0 ~ 02
1.34 x 104
°3 * *°2 * w03 4 °2
5 x 10"2
KOj 4H0- «02 ~ *02
1.3 xlO4
K03 ~ *02 4 H20 -~ 2HH03
1.66 x 10*31
NO ~ N02 ~ H20 •*> 2HN02
2.2 x 10""
HN02 ~ hv - NO ~ OH
3 x 10"2t
N02 4 OH* ~ HN03
9 x 10*
NO 4 OK' •» HN02
9 x 103
CO 4 OH- ~ C02.4 HO^
2.06 x 102
OLE 4 0H-°£ HCHO 4 CH30£
3.8 x 104
PAR 4 CH.°I CH30j 4 «20
1.3 x 10S
m 4 OH-°l HCHO 4 CH302
8 x 103
OLE 4 .A HC(0)«2. 4 CH30j
5.3 x 103
PAR 4 0' ^ CH30£ 4 OK.
20
20. .
ARO ~ 0' -* HC(0}0j 4 CH30j
37
OLE 4 03°l HC{0)02 4 HCHO 4 OH.
0.01
(continued)
278
-------
TABLE 35 (Concluded)
Rate constant
	teaction		(pptn*^ gttT*)
°2
ARO ~ 03 * NC(0)0^ ~ HCHO * OH.	fl.002
OLE ~ Dj «• ozonlde	0.005
W2	-4+
HCHO ~ hv - HCCO)Oj ~ H05	4 * 10
HCHO ~ hv -~ CO ~ H2	4 k lO"4'
HCHO + 0H.°^ HC(0)02 ~ H20	1 x "I04
HOj + NO -~ OH. ~ H02	2 * 103
CHgOj + NO - N02 ~ HCHO ~ HO^	2 * 103
HC(0)0j + HO ->N02 ~ C02 + HO^	2 x 103
H202 ~ hv -»¦ OH* + 0H»	6.6 « lO"4*
H0$ + HOj - H£02 + 02	4 x 103
CH305 ~ HOg ¦* H3COOH + 02	4 x 103
HC(O)0g + H02 ¦* HC(0)00H + Og	1 x 104
HC(0)02 ~ N02 * PAN 50
PAN - HC(0)0g ~ H02 0.02t
ARO + NOj Prod*" 1*1
HO^ + «02 ~ HH02 20-
* Rate/constants are modified for the computer simulations of OCR smog
chamber experiments.
t Units of mln"1.
J9 .1
f Unfts of ppm mln .
279'
-------
TABLE 36. THE NEW CARBON-BOND MECHANISM (CBM-II)
•t
.1 .1 er.frrgj
	faction	 (pp* min }		
NOj ~ hv ¦» KO ~ 0	txper imtr.tal"
O ~ 02 < H - 03 ~ M	2,1 « 10"5'
03 ~ NO - W)2 ~ Oj	23.9	1,450
Oj ~ N02 - MOj ~ Oj	4.8 > 10"J	2,450
03 + OH - H0? ~ 0?	7.7 x 101	1,000
Qj ~ HC2 - OH + Z0Z	5.0	> .525
0?
" "u2
7.1 x 10-'°!
NO, ~ MO - 2N0,	2.8 * 104
2
2 ~ «u ¦» 01^2
H03 + KOj ~ HjO «• 2HW03	311 *	~ HjO)***	-10,600
MOj + NO ¦» HOj + OH	1.2 X 104
HOj ~ HOjj •»	l.S X 104
PAR + 0 - ME02 + OH	2 x 10
P«»OH»«Oz	1.5 X 103
OLE + 0 » *0j + ACO, + »	2.7 * )03
OLE + 0 » CMB	Z.7 * I03
OLE + OH * RM>2	4.2 x 10*
OLE ~ 03 - CMB ~ CMS	8 * lo'1
OLE ~ Oj * CMB + HCRS	8 X 10
ETH ~ 0 ~ HEOj ~ H0Z ~ CO	6 x 10'
ETH ~ 0 » CAM	6 a 10'
280
-------
TABLE 36 (Continued)
fctte Li>"ikUnt
«t /'-Br
	_	teacUoft	LpJ»lV\n-"-J	
CTN ~ OH - RBOj	1.2 » 10*
ETN ~ Dj ¦» URB ~ CM 6	2.4 » 10"3
ACOj ~ HO - NQj ~ HEOj + COj	3.8 > TO3
RB02 ~ NO - N0? ~ 2 CARB +	1.2 * ID4
RA02 NO - N02 ~ 2 CAaB •> HOj	1.2 * to4
*0Z 4 NO - NQ? 4 CA® + WOz ~ *	(1.2 x 10*)|A-1)/A
mz * TO » NOz ~ CARB + HOj	(1.2 x )0*)/A"
ICQj + NO ¦» Nitrite	5 * 10*
J»02 * Oj 2 CAffi + H0Z	5.0
AAOj ~ 03 - 2 CARB + KOj	2 * 102
«0? + Oj • CARB t HOj	5.0
CAW ~ OH * a(H02 ~ CO) + {1 - e)(ACOj * *)	I2.t - a) x 10*
CARB ~ hv « CO	«kf*t+
CARB ~ h\> •» (1 + »)H0Z + (1 - o)(HEOj + X) + CO
X ~ FAR ¦»	1 x 10*
ACOj ~ NOj * PAH	I « 103
MN * ACOj ~ m2	2.B i ID'*'
ACOj ~ HOj »	~ x W3
4.H03
CMS ~ HO * HOj ~ CA»	1.2 x Iff*
C*« ~ MOg * «#, ~ CMC	8 x I03
CMS ~ CARB -OieMtf*	2 , io3
MSG * NO -Mg t cm	1.2 x 10«
KK * HOj « »j CAM	8 « 103
281
-------
TABLE 36 (Concluded)
HLRO t URB - Orontde	2 1(T
CR1G - CO	6.7 x 102+
DUG •» Stable Product!	2.4 * 10?t
CR16 - 2H0? * C02	!> 101 +
MCRG - Stable Products	1.5 * l/t
MCRG - «02 * OH + CO	3.4 I 102<
MCRG - «02 -t HOj + C02	4.25 x 10?t
HCRG ¦» CARS ~ ZKOj ~ CO	8.5 x 101*
ARO * OH ARPI + ARPI + ARPI + H02	6 x ID3
ARO + OH - H02 < GLY + X	1.6 x 103
ARO * OH » OH + a* ~ K	1.5 * 104
H ~ CAM »	1.0 x 105
ARPI ~ NO -> NO ~ GARB + PAR	30
ARPI ~ HO "> H0Z + AEROSOL 15
ARPI ~ »3 * CARB + CARE	3.5 x 104
AW>1 + Oj » Aerosol	0.6
8LT ~ OH * HOj ~ AW! + ARPI ~ ARPI + CO 10*
GLY * HtOj + NOj + ARPI ~ ARPI ~ ARPI Kg^il
* The rate constant* shown art as used to model eleven expert menu
it UCR that used alxes of seven hydrocarbons. For that stu<(y the
default values, 0 ¦ 0.5 and A ¦ 1.1, were used.
t Units of Bin"1.
I Units of pp«f2»1n~'.
** A - A 1s the average number of ROJ-type radicals generated fro» .
* hydrocarbon between attack by OH- and generation of H0|
tt • 1» the friction of total aldehydes that represents formaldehyde
and ketones. kf Is the carboryl photolysis rate constant.
" *6L* " °-036 * HMOz + M
*** '(^Oj ~ HjO) * S * 10"S PP""'"'""1 for "W simulations.
282
-------
The main features that distinguish the two versions of the CBM are
briefly explained in the following discussion.
>	Aromatics Chemistry. Approximately one year ago, a semi-
empirical aromatics mechanism was constructed to simulate
the hydrocarbon decay, NO-to-NC^ conversion, N0X decay to
nitrates, PAN formation, and ozone formation seen in a series
of smog chamber experiments involving either nitrogen oxides
and pure aromatics or NO and mixtures of hydrocarbons con-
A
taining aromatics. This mechanism has been incorporated into
the SAI Airshed Model.
During the past year, we have been studying the fundamental
chemistry involving aromatics that has emerged from recent
laboratory kinetics studies. The CBM-II mechanism in Table
36 reflects our present thinking on the fundamental chemistry
of aromatics, yet is still compatible with the SAI Airshed
Mechanism, requiring only a modification of rate constants
and a relabeling of the aromatic photolytic species as GLY
(gl'yoxals). Approximately 73% of the oxidation pathway
leads to glyoxal photolysis in both the CBM-II mechanism
and the toluene developmental mechanism. Cresol and
benzaldehyde are neglected as unimportant in the CBM-II
mechanism. The overall rate constant for OH oxidation of
aromatics is taken to be an average of toluene and xylenes.
The aromatics mechanism in the CBM may be said to have
evolved to the state of being primarily a condensed mech-
anism of known fundamental chemistry.
>	PAN Chemistry. In the old CBM, the peroxyforrny] radical
(HCOp was used to generate PAN formation via reaction with
NOg using an empirical rate constant. In the CBM-II, the
HCOg has been eliminated, and a new species representing
peroxyacyl radicals (ACOj) is now used. ACO^ 1s fbrmed from
the hydroxy! radical (OH*) attack on carbonyl compounds
283
-------
(surrogate CARB). The amount of ACO^ formation is proportion-
al to 1-a, which represents the higher aldehydes. Hence, PAN
chemistry itself uses no empirical rate constants. Further-
more, the use of a in the new CBM has been carefully conceived
to ensure that ozone production is rather insensitive, yet PAN
production is sensitive, to the choice of a. In the old CBM and
in other mechanisms such as the well-known Hecht, Seinfeld, and
Dodge (HSD) mechanism, the parameter that governs PAN formation
significantly affects ozone production—if too much PAN is simu-
lated by the mechanism, then 0^ will be low and vice versa. CBM-
II eliminates this problem. A poor choice for a should only pro-
duce incorrect PAN simulations.
>	Organic Nitrates. The CBM-11 incorporates recent discoveries
concerning the formation of these compounds. Darnell et al.
(1976) have found that R02~type radicals having large R groups
can form organic nitrates via reaction with NO. The aromatics
chemistry also leads to nitrate formation. Unfortunately, at
present,the rate constant for R02 plus NO leading to nitrate
is empirically adjusted to provide proper organic nitrate
levels in the UCR smog chamber experiments used to validate
the new mechanism. Until smog chamber data are available for
a large variety of individual compounds and a variety of mix-
tures, this rate constant cannot be determined from the reac-
tivity of the hydrocarbon mix.
>	Large Paraffin Chemistry. Carter et al. (1976) have shown
that a cyclic intermediate could allow large RO radicals to
isomerize in air to HOROg radicals. The explicit mechanisms
for butane and 2,3-dimethylbutane show that, subsequent to
attack by hydroxyl radicals, on the average, more than one R02
intermediate form prior to the production of an H0£ radical.
The cyclic isomefcization reaction accounts for some of this
effect, and decomposition reactions for large RO radicals
account for the rest. In CBM-II, this complex chemistry is
284
-------
treated through a parameter, A, which is determined from the
average number of R02 intermediates between hydroxyl attack
on paraffins and generation of H02» which occurs in explicit
mechanisms via the 02 abstraction of RO intermediates.
>	Ozone Olefin Chemistry. CBM-II treats the diradical interme-
diates that, according to recent studies conducted by NBS,
Ford, and EPA, are formed during these reactions. Although
these intermediates—sometimes referred to as Criegee inter-
mediates—are known to react unimolecularly or in combina-
tion with NO, N02, aldehydes, and S02> the relative rates
between these various possibilities are not yet known.
>	Activation of Single Bonds. CBM-II accounts for the forma-
tion of R02 radicals from the chemistry of carbonyl compounds
other than formaldehyde. In order to maintain carbon mass
balance, a special species, x, is used that removes a carbon
group from the single bonded surrogate, PAR, whenever an extra
carbon group is generated. For example, if the surrogate
carbonyl species were to represent pure acetaldehyde (a =0),
hydroxyl attack would produce ACO^. However, the surrogate,
ACO^, in the new CBM has two carbon atoms and the precursor,
CARB, has but one carbon atom, so an x is formed along with
ACO^. Then, a fast reaction in the CBM-II between PAR and x
immediately removes one PAR from the system, thereby accounting
for the extra carbon generated in the AC0| radical.
>	Elimination of HONO. As. shown in Whitten et al. (1979), this
compound is rapidly photolyzed and re-formed in a "do nothing"
cycle in the atmosphere. These reactions lead to an average
steac(y-state value that is very small. Modeling studies at
SAI have confirmed that the elimination of this species leads
to trivial differences in computer smog simulations.
285
-------
> Explicit Treatment of the Olefin Hvdroxvl Addition Product. The
explicit chemistry of hydroxy! attack on olefins leads to the
formation of two aldehydes from the initial addition product,
which in air is a H0R02 radical. The old CBM treated this
radical as a typical R02 radical that produces but one aldehyde;
the extra aldehyde was added along with the R02 as a product
in the initial OH reaction. However, the present version of the
CBM-11 includes a special reaction of the HORQg addition pro-
duct with Oy Hence, the explicit treatment allows, the forma-
tion of two aldehydes from the H0R02 or reaction with Qg. The
03 reaction is still under investigation, and future versions
of the CBM may not require this reaction.
In addition to these changes, the use of carbon bond chemistry
has been improved and can be applied to either version of the
CBM. In one study it was found that the concentration-weighted
root-mean-square method of averaging the hydrocarbon rate con-
stants produced the best overall performance of the CBM in a
series of simulations of smog chamber experiments using mix-
tures of hydrocarbons. A related study showed that internal
olefins could be simulated as two carbonyls per double bond.
Thus, the CBM can treat three levels of reactivity for olefins:
Ethylene is treated as a separate species, terminal olefins,
are treated by the surrogate double-bond species OLE, and the
highly reactive internal olefins are treated as two CARBs per
olefin bond.
Performance of the CBM-II should not differ significantly
from the old CBM, according to the tests on several smog chamber
experiments reported below. However, the new mechanism incor-
porates an extensive range of recent information on smog chem-
istry. One notable difference has been a prediction, using the
new chemistry, that the addition of aromatics to a mixture of
olefins and paraffins at high hydrocarbon-to-NOx ratios would
286
-------
suppress ozone formation. A recent experiment at the outdoor
chamber at UNC has confirmed this prediction as shown in
Section 5.
To represent the performance of both the old and new versions
of the CBM, we have included two sets of results from simula-
tions of 11 smog chamber experiments. Figures 143 through 164 com-
pare the observed data with the computed simulations for each
version of the CBM. Tables 37, 38, and 39 present the initial
conditions.
Ozone formation is determined by the conversion of NO to NOg,
which in turn is determined from the decay of the hydrocarbons.
The decay rate of the hydrocarbons is primarily a function
of the hydroxyl radical level that is, in turn, determined by
a balance between radical sources and sinks. The sink reac-
tions in the old CBM are not controllable, but the organic
nitrate formation from ROg and NO in the CBM-II should be
adjusted within a factor of 2 from the default value of
500 ppm if nitrate data are available. The major adjustments
in these simulations were of the carbonyl photolysis rate,
but these adjustments were within the range of uncertainty
of the artificial light source used.
Before' judging the ozone performance of any mechanism, the
hydrocarbon decay and NO conversion and loss rates should
A
be correctly simulated. The basic function of a properly
assembled mechanism is then the correct maintenance of radi-
cals in generating ozone and nitrates.
Table 40 presents statistical evidence, based on the mechan-
isms of Tables 35 and 36, demonstrating the ability of both
versions of the CBM to simulate ozone. Bias for both versions
is slightly high, as indicated by the positive mean errors.
CBM-II shows only +3 ppb, or +2.8 percent, on an average
287
-------
relative to the observed data. Although both versions show
an average absolute error of about ±0.06 ppm, the newer ver-
sion appears to show a better relative error of ±18 percent,
compared to ±26 percent for the older CBM. This difference
is visually manifested in the simulation results figures;
the older version seems to produce ozone peaks with a notice-
able bulge.
288
-------
SIMULATION RESULTS OF UCR EXPERIMENTS USING
THE ORIGINAL CARBON-BOND MECHANISM
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0.015
o.ooo
80 160 240 320 400 480 560 640
TIME (MINUTES)
PAR
7.80
5C
a.
a.
7.00
6.20
ui
u
z
B
u
4.60
TIME (MINUTES)
FIGURE 163. 5IMULFITI0N RESULTS F0R
EC-246
318
-------
0.10
RR8
0.08
x
o.
a.
0.06
0.04
u
z
m
(j
0.02
0.00
80 160 240 320 400 480 560 640
TIME (MINUTES)
ETH
0.28
z 0.21
z
oa
o
0.07
0.00
TINE (MINUTES)
HCH8
0.60
x
A.
Ck.
0.45
z
a
0.30
o
0.15
0.00
160 240 320 400 480 560 640
TIME (MINUTES)
FIGURE 163. (Concluded)
319
-------
03
N0
N02
0.80
a.
0.60
CB
OC
£ 0.40
UJ
CJ
z
QB
O
0.20
XX
0.00
TIME (MINUTES)
PAN
0.12
x
ft.
a.
0.09
z
&
h*
H
a
h-
Z
UJ
o
z
0.06
CB
(J
0.09
0.00
TINE (MINUTES)
0.060 -
x
a.
a.
5
P
0.D45 -
0.030
0.015
0.000
40 80 120 160 200 240 280 320
TINE (MINUTES)
2.45
2.20 -
1.95 -
a:
oe
1.70 -
u
Z
(B
O
U45
1.20
I	1	1
0 40 80 120 160 200 240 260 '320
TIME (MINUTES)
FIGURE 164. SIMULATI0N RESULTS F0R
EC-247
320
-------
1.25
ETH
1.00
x
0.75
£ 0.50
fel
u
u
0.25
0.00
40 80 120 160 200 240 280 320
TIME (MINUTES)
0.40
x
o.
0_
0.30
0.20
ui
u
o
0.10
0.00
TIME (MINUTES)
HCHS
. 0.80
x
0.
0.60
£ 0*40
UJ
u
as
a
u
0.20
0.00
80 120 160 200 240 280 320
TIME (MINUTES)
FIGURE 164. (Concluded)
321
-------
TABLE 37. INITIAL CONDITIONS FOR THE SEVEN-HYDROCARBON/NO EXPERIMENTS
A
Initial concentration (ppm)	
Initial
Run
number
NO
CVI
§
Ethylene
Propylene
Butane
t-2-Butene
2,3-Dimethylbutane
Toluene
m-Xylene
HC/N0X
(ppcnC/ppm)
EC-231
0.44
0.052
1.051
0.108
1.13
0.055
0.715
0.121
0.108
26.8
EC-232
0.469
0.024
0.258
0.051
1.102
0.026
0.612
0.032
0.029
18.9
EC-233
0.096
0.007
0.260
0.051
1.085
0.025
0.648
0.034
0.033
92.2
EC-Z37
0.377
0.106
0.875
0.100
1.025
0.050
0.463
0.0E6
0.091
21.7
EC-238
0.718
0.234
0.982
0.093
0.966
0.047
0.420
0.083
0.084
10.6
EC-241
0.379
0.110
0.484
0.045
0.464
0.024
0.211
0.04
0.044
10.1
EC-242
0.377
0.125
2.014
0.109
0.558
0.108
0.203
0.306
0.306
25.5
EC-243
0.386
0.114
1.939
0.109
0.568
0.170
0.084
0.155
0.154
19.4
EC-245
0.743
0.259
2.055
0.104
0.534
0.102
0.185
0.321
0.317
13.0
EC-246
0.386
0.122
0.253
0.049
1.058
0.026
0.538
0.023
0.023
16.9
EC-247
0.38
0.125
1.025
0.054
0.273
0.053
0.080
0.145
0.145
12.2
-------
TABLE 38. NORMALIZED INITIAL CONDITIONS FOR THE SEVEN-HYDROCARBON/NO
EXPERIMENTS (ppmC) USED FOR CARBON-BOND I
Photolysis rate constant
Initial conditions (percent of total HC)	 	(min~^)	
nunber
(ppmC)
Hixture
1-Olefins*
Paraffins+
Aromatics1
Carbonyls**
HN02++
kl
HN02+hv
H202+hu
ALD+hu
EC-231
13.187
6
1.64
71.02
26.36
0.98
0.000
0.3
0.087
6.6 x ID*4
8 x 10~4
EC-232
9.323
A
1.10
88.77
9.46
0.67
0.002
0.3
0.087
6.6 x 10~4
8 x 10"4
EC-233
9.5
A
1.07
88.65
9.70
0.58
0.002
0.3
0.087
6.6 x 10"4
8 x 10"4
EC-237
10.463
B
1.91
70.25
26.87
0.97
0.006
0.3
0.087
6.6 x 10~4
8 x 10~4
EC-238
10.094
B
1.84
67.59
29.38
1.19
0.017
0.3
0.087
6.6 x 10"4
8 x 10"4
EC-241
5.141
B
1.75
67.22
28.64
2.39
0.004
0.3
0.087
6.6 x 10"4
8 x 10"4
EC-242
12.855
C
1.70
36.51
59.89
1.90
0.011
0.3
0.087
6.6 x 10~4
8 x 10"4
EC-243
9.743
C
2.24
36.65
58.83
2.28
0.009
0.3
0.087
6.6 x 10"4
8 x 10~4
EC-245
12.875
C
1.62
35.02
61.65
1.71
0.017
0.3
0.087
6.6 x 10"4
8 x 10"*
EC-246
8.566
A
1.14
89.11
9.13
0.62
0.007
0.3
0.087
6.6 x 10~4
8 x 10"A
EC-247
6.174
C
1.74
35.10
61.39
1.77
0.010
0.3
0.087
6.6 x 10"4
8 x 10"4
* Propylene only.
+ Butane, 2,3-diaethy1butane, and all single-bonded carbon atoms from the olefins, aromatics, and carbonyls.
i Toluene and *-Xylene, and ethylene.
** All aldehydes and internal olefin (trans-2-butene).
ft In ppa.
fs One-half to stable products.
-------
TABLE 39. NORMALIZED INITIAL CONDITIONS FOR THE SEVEN-HYDROCARBON/NO
EXPERIMENTS (ppmC) USED FOR CBM-II
Photolysis rate constant
Initial conditions (percent of total HC)	 	(min~^)	
nun
number
iui4i
(ppmC)
Mixture
1-Olefins*
Paraffins'*
Aromatics5
Ethylene
Carbonyls**
RX++
kl
RX+hv
ALfHhv55
BZA+hv
EC-231
13.187
B
1.64
71.02
10.42
15194
0.98
0.000
0.3
0.03
8.1 x 10"4
o.on
EC-232
9.323
A
1.10
88.77
3.93
5.53
0.67
0.003
0.3
0.03
8.1 x 10~4
0.011
EC-233
9.5
A
1.07
88.65
4.23
5.47
0.58
0.004
0.3
0.03
8.1 x 10"4
0.011
EC-237
10.463
B
1.91
70.25
10.15
16.72
0.97
0.004
0.3
0.03
8.1 x 10"4
o.on
EC-238
10.094
B
1.84
67.59
9.93
19.45
1.19
0.007
0.3
0.03
8.1 x 10~4
0.011
EC-241
5.141
B
1.75
67.22
9.80
18.84
2.39
0.001
0.3
0.03
8.1 x 10"4
o.on
EC-242
12.855
C
1.70
36.51
28.56
31.33
1.90
0.002
0.3
0.03
8.1 x 10~4
o.on
EC-243
9.743
C
2.24
36.65
19.02
39.81
2.28
0.004
0.3
0.03
8.1 x 10"4
0.011
EC-245
12.875
C
1.62
35.02
29.73
31.92
1.71
0.001
0.3
0.03
8.1 x 10"4
o.on
EC-246
8.566
A
1.14
89.11
3.23
5.90
0.62
0.012
0.3
0.03
8.1 x 10"4
o.on
EC-247
6.174
C
1.74
35.10
28.19
33.20
1.77
0.003
0.3
0.03
8.1 x 10"4
o.on
* Propylene only.
t Butane, 2,3-dimethylbutane, and all single-bonded carbon atoms from the olefins, aromatics, and carbonyls.
i Toluene and m-Xylene.
** All aldehydes and internal olefin (trans-2-butene).
ft In ppm.
i§ One-third to stable products.
-------
TABLE 40. STATISTICAL ANALYSIS OF THE ORIGINAL CBM AND CBM-II OZONE PREDICTIONS
COMPARED WITH MEASURED DATA
Mean
RMS Mean Relative absolute	Relative
error error mean error	mean abso-	Correlation
	(ppm) (ppm) error	(ppm)	lute error	coefficient
CBM-II 0.0854 0.0032 0.0277 0.0650	0.1819	0.9306
Original CBM 0.0839 0.0160 0.1790 0.0596	0.2605	0.9321
A COMPENDIUM OF ISOPLETH DIAGRAMS
As part of our analysis of the behavior of the CBM, we have prepared a
series of isopleth diagrams showing the formation of various smog constituents
as predicted by the CBM. The species included are:
>	Ozone
>	PAN
>	no2
>	hno3
>	NOJ
>	Carbonyls
>	HOg
>	h202
>	OH
>	Organic Nitrates.
The hydrocarbon mixture used in these isopleths consisted of the following
carbon fractions; 0.034 ethylene, 0.25 aromatic, 0,034 oleflnic, 0.65 parafinic,
0.034 carbonyl (i.e., these fractions are the amount of carbon in each bond
category). This hydrocarbon split represents an average automobile emissions
mixture combining both evaporative (40 percent) and exhaust emissions (60 per-
cent) (KilTus et al., 1977). The mixture has been wormallzed to remove unreac-
tive hydrocarbons.
325
-------
Standard OZIPP (or EKMA) conditions were used except that aldehyde photol-
ysis to stable products was changed to 0.35 of the nominal program value in
order to make it consistent with the values that we have been using for the
UNC outdoor chamber (Whitten and Hogo, 1978).
Ozone
The Carbon-Bond Mechanism (Figure 165) is somewhat more reactive than the
mechanism used by Dodge (1977) in the Empirical Kinetic Modeling Approach (EKMA)
(Figure 166). However, when used on a propylene-butane mix (Figure 167), the
shape of the curves are similar. The inclusion of the aromatic mechanism
alters the shape of the Carbon Bond isopleth diagrams for the automobile hydro-
carbon mix.
PAN
The PAN isopleths (Figure 168) are interesting for several reasons. They
are similar in shape to the ozone isopleths, yet the region of maximum effi-
ciency is broader and shifted slightly to the higher HC/NO ratios. The PAN
X
isopleths resemble the ozone isopleths of a propylene butane mix (Figure 167)
more closely than they resemble ozone from our simulated automobile emissions.
This suggests that the aromatics mechanism in some fashion distorts the ozone
chemistry while PAN chemistry is left unperturbed.
If we plot ozone formation as a function of increasing precursor concen-
tration at the HC/N0X ratio of maximum production efficiency, we obtain a
curve similar to the Appendix J rollback curve (Figure 169). Ozone production
efficiency declines at higher precursor concentration levels, while PAN produc-
tion efficiency increases at higher concentration levels (Figure 169), indicat-
ing that pollution control measures work more effectively on PAN than on ozone.
The isopleths of peak NO2 concentration (Figure 170) show an almost linear
dependence on N0X- Only at very low HC/N0x ratios (HC/N0x < 2) is the NOg
326
-------
0.2
0.6
0.B
1.0
IM
o
u>
o
0.3*
0.J2
o
¦0.20
o
0.10
0.12
,0»—
0.2
0.B
2.0
NMHC.PPHC
FIGURE 165. STANDARD OZONE ISOPLETH CONDITIONS
-------

HMHC. wiaC
FIGURE 166. OZONE ISOPLETH USED IN EKMA
-------
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
a
20
a
¦0.12
0.5
NHHC.PPHC
0.6
0.3
0.B
0.4
0.9
0.2
FIGURE 167. OZONE PRODUCED BY A 10/90 PROPYLENE BUTANE MIX
-------
FIGURE 168. PAN ISOPLETH
-------
1.1
o.c
o.s
O.OZ
0.4
ozone
0.2
0.01
MM
0.1
0-1
0.4
1.0
o.t
OS
0.6
0.8
0.9
0
HC (pp>0
FIGURE 169. OZONE AND PAN AT HC/NOx =6.7
-------
0.0
0.4
¦o.i«
N
tf>
-•.lo
-0.00
0.08
0.02
0.6
0.0
0.2
HMHC.PPMC
FIGURE 170. N02 ISOPLETH
-------
peak not reached. The NO2 recovery is surprisingly low, only about 60 percent
of total NO . Dilution is responsible for some of this NO loss, but the
X	X
majority seems to be in the form of organic nitrate, which is discussed below.
hno3
Nitric acid isopleths (Figure 171) show few surprises. Their linear rela-
tion to NO is nearly identical to the N0« isopleths, although most nitric
A	t
acid is formed after the NO2 peak. The bend in the HNOg isopleths occurs
at slightly lower HC/NO ratios than the ozone bend. Below this ratio,
A
nitric acid appears to be completely hydrocarbon limited.
N03
The NO3 isopleth diagram (Figure 172) is very similar to ozone isopleths.
However, NOg is destroyed rapidly at high N0X concentrations by the reaction
with NO and at high hydrocarbon concentrations by the reactions with aromatics
intermediates. Thus, the NOg isopleths bend sharply away from both axes.
Aldehydes
The aldehyde isopleths (Figure 173) show the effects of two factors.
Because aldehydes are emitted directly, they form a fractional part of the
hydrocarbons and the isopleths tend to run parallel to the hydrocarbon axis
at the lowest HC/N0Y ratios where the chemistry is slow. Aldehydes are also
efficiently produced at high HC/NO ratios. It appears that aldehydes can
r\
reach a maximum of 10 percent of the initial hydrocarbon concentration, or
roughly twice the emissions rate.
HOg and HgOo
HOg concentration (Figure 174) is maximized at very high HC/N0x ratios.
Hydrogen peroxide formation (formed by HOJj - HOg reaction) peaks
at a somewhat smaller HC/N0x ratio. Hydrogen peroxide isopleths (Figure 175)
look very similar to reported isopleths for aerosol formation (Miller and
333
-------
0.6
0.8
1.0
0.1
0.11
N
O
0.10
IO
o.oe
¦o.o«
o.o«
0.02
o
0.6
o.e
2.0
0.4
0.2
MNHC.PPHC
FIGURE 171. HN03 ISOPLETH
-------
0.8
D.S
0.2
IM
to
O
0.6
o.e
0.4
0.2
FIGURE 172.
no3 ISOPLETH (10000 X PPM)
-------
Of*
o
o
o
o
B.0« —
£e\#*c>*c
-------
ortr
T.H
IM
IM
X
o
0.6
0.2
FIGURE 174.
ho2 ISOPLETH (10000 X PPM)
-------
o
*C
0.6
0.B
0.2
NMHC.PPMC
FIGURE 175. H202 ISOPLETH
-------
Joseph, 1977). Wu, Bogard, and Brock (1978) have suggested that some particulate
formation is the result of ozonides that react with other ozonides to form
polymeric aerosols. Such a reaction sequence could well resemble hydrogen
peroxide formation.
OH-
Isopleths of 10-hour average OH- concentrations (Figure 176) seem to
depend almost solely on the HC/NO ratio, and have little to do with precursor
A
concentration. This is in keeping with elementary steady state analysis. To
a first approximation, at low HC/NO ratios, OH depends on the ratio of aldehyde
A
photolysis to N02 concentration. At high HC/N0X ratios, hydrogen peroxide
formation removes H0£ from the system before OH is reformed.
Organic Nitrates
Isopleths were generated for the ratio of organic nitrate production to
total nitrate (the remainder being HNO^) after 10 hours (Figure 177). Organic
nitrates are produced in the CBM in roughly equal amounts from two sources:
the R0,j reaction with NO and the reaction of NOg with an aromatics intermediate.
Smog chamber experiments with large paraffins or aromatics are predicted by the
new CBM to produce organic nitrates at high HC/N0x ratios. Future experiments
will be needed to confirm this prediction.
This set of isopleth diagrams can be used to assess the chemical reac-
tivity of chemistry secondary to ozone chemistry, such as S02 conversion to
sulfate. The OH* diagram indicates that if OH was responsible for the major
fraction of sulfate production then HC and NO control strategies aimed at
A
reducing sulfate would not be effective at constant HC/NO ratios even though
A
ozone and PAN would be reduced.
339
-------
0.0 1.0
NMHC.PPHC
FIGURE 176. OH ISOPLETH (1 X 10° X PPM)
-------
0.8
0.0
1.2
O
F)
O
o
o
in
N
in
O
CM
o
o
10
O
o
0.2
0.4
0.6
0.6
NMHC.PPMC
FIGURE 177. RATIO OF ORGANIC NITRATE TO TOTAL NITRATE AFTER 10 HOURS
-------
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Nojima, K., et al. (1974), "The Formation of Glyoxals by the Photochemical
Reaction of Aromatic Hydrocarbons in the Presence of Nitrogen Monoxide,"
Chemosphere, Vol. 5, pp. 247-252.
Perry, R. A., R. Atkinson, and J. N. Pitts, Jr. (1977), "Kinetics and
Mechanism of the Gas Phase Reaction of OH Radicals with Aromatics
Hydrocarbons over the Temperature Range 296-473K," J. Phys. Chem.,
Vol. 81, pp. 296-304.
Rappoport, Z. (1967), Handbook of Tables for Organic Compound Identification,
Third Edition (CRC Press, Cleveland, Ohio).
Sato, K., K. Takimoto, and S. Tsuda (1978), "Degradation of Aqueous Phenol
Solution by Gamma Irradiation," Environ. Sci. Tech., Vol. 12, p. 1043.
345
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Schere, K. L., and K. L. Demerjian (1977), "Calculation of Selected Photo-
lytic Rate Constants Over a Diurnal Range, A Computer Algorithm,"
EPA-600/4-77-015, Environmental Protection Agency, Research Triangle
Park, North Carolina.
Schwartz, W. (1974), "Chemical Characterization of Model Aerosols," EPA-
650/3-74-011, Chemistry and Physics Laboratory, Environmental Pro-
tection Agency, Research Triangle Park, North Carolina.
Takagi, H., et al. (1979), "Photooxidation of o-xylene in the NO-F^O-AIR
Systems," submitted for publication to J. Phys. Chem.
Whitten , G. Z., and H. Hogo (1978), "User's Manual for Kinetics Mode and
Ozone Isopleth Plotting Package," EPA-600/8-78-014a, U.S. Environ-
mental Protection Agency, Research Triangle Park, North Carolina.
Whitten, 6. Z., And H. Hogo (1977), "Mathematical Modeling of Simulated
Photochemical Smog," EPA-600/3-77-001Systems Applications,
Incorporated, San Rafael, California.
Whitten, G. Z., H. Hogo, and J. P. Kill us (1979), "The Carbon-Bond
Mechanism—A Condensed Kinetic Mechanism for Photochemical Smog,"
Systems Applications, Incorporated, San Rafael, California, submitted
for publication to Environ. Sci. Techno!.
Whitten, G. Z., et al. (1979), "Modeling of Simulated Photochemical Smog
with Kinetic Mechanisms, Vol. I: Interim Report," EPA-600/3-79-001a,
Systems Applications, Incorporated, San Rafael, California.
Whitten, G. Z., et al. {1978), "Modeling of Simulated Photochemical Smog
with Kinetic Mechanisms," Draft Interim Report - August, 1978,
Systems Applications, Incorporated, San Rafael, California.
Wu, M. S., J. M. Bogard, and J. R. Brock (1978), "Particle Formation in the
Ozone-Propylene Reaction," J. Environ. Sci. Health. A13(8), pp. 571-584.
346
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ADDENDUM
CORRECTIONS TO 1977 and 1978 UNC PAN DATA
Subsequent to submission of this report, corrections to the 1977 and
1978 UNC PAN data were transmitted to SAI, During 1977 and 1978 UNC used
three different PAN calibration procedures. The following corrections
serve to make the 1977 and 1978 PAN data set consistent with the 1979 data
set. These resulted from a comprehensive study of the calibration techniques
that had been used.

PAN CONCENTRATION

PAN CONCENTRATION
RUN DATE
TO BE MULTIPLIED BY
RUN DATE
TO BE MULTIPLIED BY
7/18/77
0.73
9/14/78
1.5
10/24/77
0.61
9/15/78
1.5
11/12/77
0.63
9/18/78
1.5
11/20/77
0.63
9/19/78
1.5
12/26/77
0.85
10/02/78
1.5
2/27/78
1.0
10/03/78
1.5
3/31/78
0.58
10/12/78
1.28
6/16/78
0.72
10/13/78
1.5
6/30/78
0.63
10/17/78
1.5
7/01/78
0.72
10/18/78
1.5
7/24/78
0.84
10/20/78
1.51
7/30/78
1.0
10/21/78
1.34
8/05/78
1.55
10/22/78
1.30
8/08/78
1.3
10/25/78
1.25
8/15/78
1.55
10/29/78
1.21
8/16/78
1.55
11/07/78
1.0
8/17/78
1.0


8/21/78
1.5


8/24/78
1.5


347
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TECHNICAL REPORT DATA
(Please read Inuructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/3-80-028a
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
MODELING OF SIMULATED PHOTOCHEMICAL SMOG WITH KINETIC
MECHANISMS
Volume 1. Final Report
5. REPORT DATE
Februarv 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
G. Z. Whitten, J.P. Killus, and H. Hogo
8. PERFORMING ORGANIZATION REPORT NO.
EF79-124
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Systems Applications, Incorporated
950 Northgate Drive
San Rafael, California 94903
10. PROGRAM ELEMENT NO.
1AA603 AC-054 (FY-79)
11. CONTRACT/GRANT NO.
Contract No. 68-02-2428
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory-RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final 7/78-9/79
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Mechanisms that describe the formation of photochemical smog are developed
using a computer modeling technique directed toward the simulation of data collected
in two smog chambers: an indoor chamber and a dual outdoor chamber. The results
of simulating 164 different experiments are presented in Vol. 1. Individual com-
pounds for which specific experiments were simulated and mechanisms developed
Include the following: formaldehyde, acetaldehyde, ethylene, propylene, butane,
and toluene. Experiments in both chambers were simulated for all these compounds.
The mechanisms reported describe the decay of the precursor organic compound,
formation and decay of secondary organic compounds, conversion of nitrogen oxides,
formation of nitrates, and the appearance and decay of ozone. Special emphasis is
given to the chemistry of toluene. Also included is a study of a generalized
smog-based or carbon-bond mechanism developed in a previous study. Volume 2
contains the user's manual and coding for a chemical kinetics computer program,
CHEMK.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
*	Air Pollution
*	Reaction kinetics
*	Photochemical reactions
*	Test chambers
*	Mathematical models
*	Computerized simulation

13B
07D
07E
14B
12A
09B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (TMskeport)
UNCLASSIFIED
21. NO. OF PAGES
362
30. SECURITY CLASS (ThUpage) " 	*
UNCLASSIFIED
22. PRICE
BPA form 2220-1 (••73)	248
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