Tobacco Pyrolysis. Kinetic Evaluation of Thermogravimetric - Mass Spectrometric Experiments

Supplementary Content for Article
Tobacco pyrolysis. Kinetic evaluation of

thermogravimetric mass spectrometric experiments.
Scope of this document: This work was based on the reaction kinetic evaluation of 10 TG-MS
experiments measured at different temperature programs. Altogether 10 DTG curves and 110 MS
intensity curves were evaluated. Due to space limitations, only the 10C/min experiments were shown in
the figures of the article.
This Supplementary Content shows the full versions of Figures 2 5 displaying 120 plots in total.
The plots were generated by the kinetic evaluation software and were upgraded by automated software
tools for the requirements of the present document.
The graphics include textual information that was also computer-generated. The first line beneath
each plot describes the given experiment. Here G0 stands for the initial sample mass. Another line
displays the quality of the fit calculated for the given plot (fit1) and for the series of experiments evaluated
together (fit10, fit20, or fit50), as described in the article. The rest of the lines below each panel list the
model parameters. Note that the parameter values have the same color as the corresponding partial curve
(calculated peak) in the plot.
Further information. Please address any question with this document to the corresponding author
(Gbor Vrhegyi, e-mail: varhegyi@chemres.hu or gvarhegyi@gmail.com , Tel. +36 1 4381148, Fax:
+36 1 4381147.)
Supplementary Content, Page 1
0.2
-1
-dm/dt [s ] 10
-1
-dm/dt [s ] 10
0.2
0.1
0.0
0.1
0.0
150
200
250
300
350
400
450
200
Temperature [C]
300
400
500
Temperature [C]
Virginia blend, G0=4.1mg, Ar, 4C/min

fit1= 2.48%; fit10= 2.45%
1: E0=117.9 log10 A=11.11 (E)=9.9
2: E0=202.1 log10 A=17.40 (E)=4.8
3: E0=204.8 log10 A=15.93 (E)=4.7
4: E0=252.3 log10 A=18.77 (E)=40.2
cj:
14.5
5.9
10.4
38.0
Burley blend, G0=4.0mg, Ar, 4C/min

fit1= 3.14%; fit10= 2.45%
1: E0=117.9 log10 A=10.47 (E)=9.9
2: E0=202.1 log10 A=17.60 (E)=4.8
3: E0=204.8 log10 A=16.13 (E)=4.7
4: E0=252.3 log10 A=18.59 (E)=40.2
cj:
6.4
6.9
11.8
37.6
0.6
-dm/dt [s ] 10
0.4
0.3
-1
-1
-dm/dt [s ] 10
0.5
0.2
0.1
0.5
0.4
0.3
0.2
0.1
0.0
0.0
200
250
300
350
400
Temperature [C]
Virginia blend, G0=4.1mg, 10C/min
fit1= 2.08%; fit10= 2.45%
1: E0=117.9 log10 A=11.11 (E)=9.9
2: E0=202.1 log10 A=17.40 (E)=4.8
3: E0=204.8 log10 A=15.93 (E)=4.7
4: E0=252.3 log10 A=18.77 (E)=40.2
cj:
14.5
5.9
10.4
38.0
450
500
200
300
400
500
Temperature [C]
fit1= 3.25%; fit10= 2.45%
1: E0=117.9 log10 A=10.47 (E)=9.9
2: E0=202.1 log10 A=17.60 (E)=4.8
3: E0=204.8 log10 A=16.13 (E)=4.7
4: E0=252.3 log10 A=18.59 (E)=40.2
cj:
6.4
6.9
11.8
37.6
Fig. 2. Evaluation of ten DTG curves assuming identical E0,j and j parameters for both samples. The
experimental data ( ), their simulated counterparts () and the calculated partial curves
() are shown. The stepwise temperature programs (- - -) are also displayed when appropriate.
2.5
-dm/dt [s ] 10
-1
1.5
-1
-dm/dt [s ] 10
2.0
1.0
0.5
2.0
1.5
1.0
0.5
0.0
0.0
200
250
300
350
400
450
500
200
300
Temperature [C]
400
500
Temperature [C]

fit1= 2.14%; fit10= 2.45%
1: E0=117.9 log10 A=11.11 (E)=9.9
2: E0=202.1 log10 A=17.40 (E)=4.8
3: E0=204.8 log10 A=15.93 (E)=4.7
4: E0=252.3 log10 A=18.77 (E)=40.2
cj:
14.5
5.9
10.4
38.0

fit1= 3.28%; fit10= 2.45%
1: E0=117.9 log10 A=10.47 (E)=9.9
2: E0=202.1 log10 A=17.60 (E)=4.8
3: E0=204.8 log10 A=16.13 (E)=4.7
4: E0=252.3 log10 A=18.59 (E)=40.2
cj:
6.4
6.9
11.8
37.6
300
250
0.1
450
0.3
400
-1
350
0.2
-dm/dt [s ] 10
-1
-dm/dt [s ] 10
400
500
350
0.2
300
250
0.1
200
150
0.0
0
25
50
75
100 125 150 175
200
150
0.0
0
Time [min]
Virginia blend, G0=4.0mg, Ar, stepwise T(t)
fit1= 1.92%; fit10= 2.45%
1: E0=117.9 log10 A=11.11 (E)=9.9
2: E0=202.1 log10 A=17.40 (E)=4.8
3: E0=204.8 log10 A=15.93 (E)=4.7
4: E0=252.3 log10 A=18.77 (E)=40.2
cj:
14.5
5.9
10.4
38.0
Temperature [C]
0.3
550
0.4
450
Temperature [C]
500
25
50
75
100
125
150
Time [min]
Burley blend, G0=4.1mg, Ar, stepwise T(t)
fit1= 2.41%; fit10= 2.45%
1: E0=117.9 log10 A=10.47 (E)=9.9
2: E0=202.1 log10 A=17.60 (E)=4.8
3: E0=204.8 log10 A=16.13 (E)=4.7
4: E0=252.3 log10 A=18.59 (E)=40.2
cj:
6.4
6.9
11.8
37.6
Fig. 2. (Continued.)
500
0.5
300
0.2
250
0.1
0.0
0
20
40
60
80
100
3
-1
-dm/dt [s ] 10
-1
-dm/dt [s ] 10
350
0.3
500
0.5
450
0.4
400
0.3
350
300
0.2
250
200
0.1
150
0.0
200
150
0
Time [min]
Virginia blend, G0=4.2mg, Ar, steps at higher T
fit1= 1.61%; fit10= 2.45%
1: E0=117.9 log10 A=11.11 (E)=9.9
2: E0=202.1 log10 A=17.40 (E)=4.8
3: E0=204.8 log10 A=15.93 (E)=4.7
4: E0=252.3 log10 A=18.77 (E)=40.2
cj:
14.5
5.9
10.4
38.0
Temperature [C]
400
Temperature [C]
450
0.4
550
0.6
25
50
75
100
125
150
Time [min]
Burley blend, G0=4.1mg, Ar, steps at higher T
fit1= 1.33%; fit10= 2.45%
1: E0=117.9 log10 A=10.47 (E)=9.9
2: E0=202.1 log10 A=17.60 (E)=4.8
3: E0=204.8 log10 A=16.13 (E)=4.7
4: E0=252.3 log10 A=18.59 (E)=40.2
cj:
6.4
6.9
11.8
37.6
Intensity of m/z 15 (arbitr. unit)
7
6
5
4
3
2
1
4
3
2
1
0
0
200
300
400
500
600
700
200
300
Temperature (C)
+
DAEM kinetics of intensity m/z 15 [CH3 (mainly from CH4)]
fit1= 4.58%; fit50= 6.18%
1: E0=211.5 log10 A=16.78 (E)=22.8 scalefactor=1.34
2: E0=265.7 log10 A=15.47 (E)=16.5
scalefactor*cj:
3283.
13666.
500
600
700

+
fit1= 4.47%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=14.1
scalefactor*cj:
3536.
8285.
18
16
14
12
10
8
6
4
2
0
12
10
8
6
4
2
0
200
300
400
500
600
700
Temperature (C)
+
fit1= 5.40%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=16.5
scalefactor*cj:
3314.
13793.
Fig. 3.
400
Temperature (C)
200
300
400
500
600
700
Temperature (C)
+
fit1= 4.67%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=14.1
scalefactor*cj:
3589.
8410.
Simultaneous evaluation of fifty MS intensity curves as described in Section 4.2.
The
experimental data ( ), their simulated counterparts () and the calculated partial curves () are
shown. The stepwise temperature programs (- - -) are also displayed when appropriate.
40
50
45
40
35
30
25
20
15
10
5
0
200
300
400
500
600
35
30
25
20
15
10
5
0
700
200
300
Temperature (C)
500
600

+
fit1= 6.34%; fit50= 6.18%
1: E0=211.5 log10 A=16.78 (E)=29.4 scalefactor=1
2: E0=265.7 log10 A=15.47 (E)=14.1
scalefactor*cj:
3007.
7045.
50
600
40
500
30
400
20
300
10
200
0
25
50
75
100
125
150
40
700
35
30
600
25
500
20
15
400
10
300
Temperature (C)
700
Temperature (C)
60
800
800
70
700
Temperature (C)

+
fit1= 4.10%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=16.5
scalefactor*cj:
2455.
10219.
400
200
0
0
Time (min)
25
50
75
100
125
150
Time (min)

+
fit1= 1.36%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=16.5
scalefactor*cj:
3700.
15403.

+
fit1= 0.83%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=14.1
scalefactor*cj:
3283.
7692.
500
400
300
200
0
0
25
50
75
100
125
700
600
3
500
2
400
300
200
150
Temperature (C)
600
700
4
Temperature (C)
25
50
Time (min)
75
100
125
150
Time (min)

+
fit1= 5.82%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=16.5
scalefactor*cj:
2438.
10150.

+
fit1= 6.86%; fit50= 6.18%
2: E0=265.7 log10 A=15.47 (E)=14.1
scalefactor*cj:
3655.
8564.
0
200
300
400
500
600
200
Temperature (C)
300
400
500
600
Temperature (C)

+
+
DAEM kinetics of intensity m/z 29 (CHO , C2H5 )
fit1= 8.51%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=13.5
scalefactor*cj:
4157.
2466.

+
+
fit1= 8.42%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=15.3
scalefactor*cj:
2299.
2267.
0
200
300
400
500
600
200
300
Temperature (C)
+
+
fit1= 7.69%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=13.5
scalefactor*cj:
3750.
2224.
500
600

+
+
fit1= 8.79%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=15.3
scalefactor*cj:
2415.
2381.
12
12
400
Temperature (C)
10
8
6
4
2
10
8
6
4
2
0
0
200
300
400
500
600
200
Temperature (C)
+
+
fit1= 9.44%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=13.5
scalefactor*cj:
2835.
1682.
300
400
500
600
Temperature (C)
+
+
fit1= 6.65%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=15.3
scalefactor*cj:
1918.
1891.
500
400
5
4
300
3
2
1
200
7
500
6
5
400
4
3
300
2
1
Temperature (C)
Temperature (C)
8
9
200
0
0
25
50
75
100
125
150
25
50
Time (min)
75
100
125
150
Time (min)

+
+
fit1= 1.91%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=13.5
scalefactor*cj:
3402.
2018.

+
+
fit1= 3.02%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=15.3
scalefactor*cj:
1597.
1575.
500
400
300
200
0
500
400
300
Temperature (C)
Temperature (C)
600
200
0
25
50
75
100
125
150
Time (min)
25
50
75
100
125
150
Time (min)

+
+
fit1= 5.44%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=13.5
scalefactor*cj:
2983.
1769.

+
+
fit1= 5.31%; fit50= 6.18%
2: E0=265.7 log10 A=16.33 (E)=15.3
scalefactor*cj:
2060.
2031.
0.5
0.0
3.0
2.5
2.0
1.5
1.0
0.5
0.0
200
300
400
500
600
200
300
Temperature (C)
+
+
DAEM kinetics of intensity m/z 30 [CH2O (with lower amounts of NO )]
fit1= 8.80%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=14.0
scalefactor*cj:
1883.
1482.
500
600

+
+
fit1= 6.15%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=19.6
scalefactor*cj:
3020.
1526.
2.0
400
Temperature (C)
1.5
1.0
0.5
0.0
6
5
4
3
2
1
0
200
300
400
500
600
200
Temperature (C)
300
400
500
600
Temperature (C)

+
+
fit1= 8.85%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=14.0
scalefactor*cj:
1527.
1201.

+
+
fit1= 6.22%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=19.6
scalefactor*cj:
2654.
1341.
22
6
5
4
3
2
1
0
20
18
16
14
12
10
8
6
4
2
0
200
300
400
500
600
200
300
Temperature (C)
+
+
fit1= 9.88%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=14.0
scalefactor*cj:
1188.
934.
500
600

+
+
fit1= 5.85%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=19.6
scalefactor*cj:
2223.
1123.
700
600
500
4
3
400
300
200
4.5
600
4.0
3.5
500
3.0
2.5
400
2.0
1.5
300
Temperature (C)
5.0
Temperature (C)
400
Temperature (C)
1.0
0.5
200
0.0
0
25
50
75
100
125
150
175
Time (min)
25
50
75
100
125
150
Time (min)

+
+
fit1= 2.98%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=14.0
scalefactor*cj:
1701.
1338.

+
+
fit1= 7.97%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=19.6
scalefactor*cj:
2527.
1277.
1.0
400
0.5
300
200
0.0
600
6
5
500
4
400
3
2
300
200
0
0
25
50
75
100
125
150
25
Time (min)
50
75
100
125
150
Time (min)
+
+
fit1= 3.57%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=19.6
scalefactor*cj:
2366.
1196.

+
+
fit1= 5.55%; fit50= 6.18%
2: E0=265.7 log10 A=16.03 (E)=14.0
scalefactor*cj:
1188.
935.
Temperature (C)
500
600
Temperature (C)
1.5
1.0
0.5
0.0
1.0
0.5
0.0
200
300
400
500
200
Temperature (C)
300
400
500
Temperature (C)

+
DAEM kinetics of intensity m/z 43 (C2H3O )
fit1= 9.78%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=16.8
scalefactor*cj:
2075.
1696.

+
fit1= 9.11%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=13.5
scalefactor*cj:
1566.
1672.
3.0
2.5
2.0
1.5
1.0
0.5
0.0
2.5
2.0
1.5
1.0
0.5
0.0
200
300
400
500
200
Temperature (C)
400
500
Temperature (C)

+
fit1= 8.17%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=16.8
scalefactor*cj:
1798.
1470.

+
fit1= 7.45%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=13.5
scalefactor*cj:
1631.
1741.
10
300
8
7
6
5
4
3
2
1
0
7
6
5
4
3
2
1
0
200
300
400
500
200
Temperature (C)
+
fit1= 7.31%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=16.8
scalefactor*cj:
1598.
1306.
300
400
500
Temperature (C)
+
fit1= 7.62%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=13.5
scalefactor*cj:
1391.
1485.
6
500
3.5
400
3.0
2.5
2.0
300
1.5
1.0
200
0.5
500
5
4
400
3
300
2
1
200
0.0
0
25
50
75
100 125 150 175
25
50
75
Time (min)
100
125
150
Time (min)

+
fit1= 3.82%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=16.8
scalefactor*cj:
2003.
1637.

+
fit1= 3.68%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=13.5
scalefactor*cj:
1526.
1629.
2.5
500
1.5
400
1.0
300
0.5
200
0.0
500
2.0
400
1.5
1.0
300
Temperature (C)
2.0
2.5
Temperature (C)
Temperature (C)
4.0
4.5
Temperature (C)
5.0
0.5
200
0.0
25
50
75
100
125
150
Time (min)
25
50
75
100
125
150
Time (min)

+
fit1= 4.53%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=16.8
scalefactor*cj:
1630.
1332.

+
fit1= 4.83%; fit50= 6.18%
2: E0=265.7 log10 A=16.95 (E)=13.5
scalefactor*cj:
1500.
1601.
25
20
15
10
5
0
200
250
300
350
400
450
500
22
20
18
16
14
12
10
8
6
4
2
0
150
550
200
250
Temperature (C)
350
400
450
500

DAEM kinetics of intensity m/z 44 (CO2)
fit1= 6.22%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=16.3
scalefactor*cj:
38687.
14547.
60
50

fit1= 4.18%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=19.3
scalefactor*cj:
54509.
15662.
45
40
35
30
25
20
15
10
5
0
200
300
Temperature (C)
250
300
350
400
450
500
550
50
40
30
20
10
0
150
Temperature (C)
200
250
300
350
400
450
500
Temperature (C)

fit1= 4.09%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=19.3
scalefactor*cj:
47094.
13531.

fit1= 6.25%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=16.3
scalefactor*cj:
45090.
16954.
200
160
180
140
120
100
80
60
40
20
0
200
180
160
140
120
100
80
60
40
20
0
250
300
350
400
450
500
550
200
300
Temperature (C)
fit1= 4.95%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=19.3
scalefactor*cj:
40301.
11580.
500

fit1= 7.28%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=16.3
scalefactor*cj:
37340.
14040.
60
40
500
400
25
20
15
300
10
5
0
200
0
25
50
75
100
125
150
500
50
40
400
30
300
20
10
Temperature (C)
30
Temperature (C)
35
45
400
Temperature (C)
200
0
0
Time (min)
25
50
75
100
125
150
Time (min)

fit1= 2.42%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=19.3
scalefactor*cj:
50407.
14483.

fit1= 2.78%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=16.3
scalefactor*cj:
38055.
14309.
25
400
20
15
300
10
5
200
0
0
25
50
75
100
125
150
50
500
45
40
400
35
30
25
300
20
15
10
Temperature (C)
30
500
35
Temperature (C)
55
40
200
5
0
0
Time (min)
25
50
75
100
125
150
Time (min)

fit1= 3.63%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=19.3
scalefactor*cj:
38486.
11058.

fit1= 3.77%; fit50= 6.18%
2: E0=265.7 log10 A=17.02 (E)=16.3
scalefactor*cj:
40036.
15054.
0
200
250
300
350
400
450
500
200
300
Temperature (C)
500
Temperature (C)

+
DAEM kinetics of intensity m/z 27 (C2H3 )
fit1= 6.73%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
3317.
2423.

+
fit1= 4.63%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
3268.
2328.
400
4
3
2
1
0
4
3
2
1
0
200
300
400
500
Temperature (C)
+
fit1= 6.90%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
2994.
2187.
Fig. 4.
200
250
300
350
400
450
500
550
Temperature (C)
+
fit1= 7.19%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
3020.
2151.
Simultaneous evaluation of twenty MS intensity curves as described in Section 4.4. The
experimental data ( ), their simulated counterparts () and the calculated partial curves () are
shown. The stepwise temperature programs (- - -) are also displayed when appropriate.
14
12
10
8
6
4
2
0
200
250
300
350
400
450
500
14
12
10
8
6
4
2
0
200
550
300
Temperature (C)
500
Temperature (C)

+
fit1= 7.69%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
2184.
1595.

+
fit1= 9.87%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
2159.
1537.
16
500
10
400
8
6
300
4
2
200
0
0
25
50
75
100
125
150
12
500
10
400
8
6
300
Temperature (C)
12
14
14
Temperature (C)
400
2
200
0
0
Time (min)
25
50
75
100
125
150
Time (min)

+
fit1= 1.11%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
3133.
2289.

+
fit1= 1.52%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
2765.
1970.
400
300
200
0
0
25
50
75
100
125
500
2
400
300
200
150
25
Time (min)
50
75
100
125
150
Time (min)

+
fit1= 5.73%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
3112.
2274.

+
fit1= 6.76%; fit20= 6.33%
2: E0=260.9 log10 A=15.83 (E)=10.9
scalefactor*cj:
3415.
2432.
1.5
1.5
Temperature (C)
500
Temperature (C)
1.0
0.5
0.0
200
300
400
1.0
0.5
0.0
500
200
Temperature (C)
300
400
500
Temperature (C)

+
+
DAEM kinetics of intensity m/z 41 (C2HO , C3H5 )
fit1= 7.03%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2597.
1368.

+
+
fit1= 6.73%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2869.
1163.
4.0
3.0
2.5
2.0
1.5
1.0
0.5
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.0
200
300
400
500
200
Temperature (C)
300
400
500
Temperature (C)

+
+
fit1= 7.10%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2046.
1078.

+
+
fit1= 6.18%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2971.
1204.
11
9
8
7
6
5
4
3
2
1
0
10
9
8
7
6
5
4
3
2
1
0
200
300
400
500
200
Temperature (C)
+
+
fit1= 5.60%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
1712.
902.
300
400
500
Temperature (C)
+
+
fit1= 9.01%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2236.
907.
500
400
5
4
300
3
2
1
200
500
6
5
400
4
3
300
2
1
200
0
0
25
50
75
100
125
150
175
25
50
75
Time (min)
100
125
150
Time (min)
+
+
fit1= 2.48%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2372.
961.
500
1.0
300
0.5
200
0.0
2.0
500
1.5
400
1.0
300
Temperature (C)
400
Temperature (C)
1.5

+
+
fit1= 1.34%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2436.
1283.
Temperature (C)
Temperature (C)
0.5
200
0.0
25
50
75
100
125
150
Time (min)
25
50
75
100
125
150
Time (min)

+
+
fit1= 4.80%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2019.
1064.

+
+
fit1= 8.38%; fit20= 6.33%
2: E0=260.9 log10 A=16.22 (E)=10.9
scalefactor*cj:
2786.
1130.
14
14
12
10
8
6
4
2
0
500
550
600
650
700
12
10
8
6
4
2
0
450
750
500
Temperature (C)
600
650
700
750
Temperature (C)

DAEM kinetics of intensity m/z 2 (H2)
fit1= 4.86%; fit10= 5.13%
scalefactor*cj:
58866.

fit1= 9.68%; fit10= 5.13%
scalefactor*cj:
53505.
55
45
50
550
45
40
35
30
25
20
15
10
5
0
40
35
30
25
20
15
10
5
0
550
600
650
700
750
Temperature (C)
fit1= 3.32%; fit10= 5.13%
scalefactor*cj:
86324.
550
600
650
700
750
Temperature (C)
fit1= 3.38%; fit10= 5.13%
scalefactor*cj:
68380.
Fig. 5. Evaluation of groups of ten MS intensity curves as described in Section 4.5. The experimental
data ( ), their simulated counterparts () and the calculated partial curves () are shown. The
stepwise temperature programs (- - -) are also displayed when appropriate.
140
160
140
120
100
80
60
40
20
0
550
120
100
80
60
40
20
0
600
650
700
750
550
600
Temperature (C)
fit1= 3.66%; fit10= 5.13%
scalefactor*cj:
68928.
700
750

fit1= 3.09%; fit10= 5.13%
scalefactor*cj:
55651.
150
100
600
50
0
160
140
120
700
100
80
60
600
Temperature (C)
700
Temperature (C)
200
800
800
250
650
Temperature (C)
40
20
0
Time (min)
Time (min)

fit1= 6.63%; fit10= 5.13%
scalefactor*cj:
106673.

fit1= 6.67%; fit10= 5.13%
scalefactor*cj:
68929.
140
700
100
80
60
600
40
20
0
120
100
80
60
10
20
30
40
50
600
40
20
500
0
700
60
500
0
10
Time (min)
20
30
40
50
60
Time (min)

fit1= 2.32%; fit10= 5.13%
scalefactor*cj:
69150.

fit1= 2.55%; fit10= 5.13%
scalefactor*cj:
62804.
60
Temperature (C)
120
140
Temperature (C)
160
50
40
30
20
10
50
45
40
35
30
25
20
15
10
5
0
0
200
300
400
500
200
Temperature (C)
300
400
500
Temperature (C)

DAEM kinetics of intensity m/z 18 (H2O)
fit1= 5.88%; fit10= 5.41%
2: E0=177.4 log10 A=13.82 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.95
scalefactor*cj:
73013.
65247.
86071.

fit1= 6.73%; fit10= 5.41%
2: E0=177.4 log10 A=13.71 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.55
scalefactor*cj:
39105.
34986.
59514.
120
120
100
80
60
40
20
0
100
80
60
40
20
0
200
300
400
500
200
300
Temperature (C)
500
Temperature (C)

fit1= 5.10%; fit10= 5.41%
2: E0=177.4 log10 A=13.82 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.95
scalefactor*cj:
66980.
59856.
78959.

fit1= 5.28%; fit10= 5.41%
2: E0=177.4 log10 A=13.71 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.55
scalefactor*cj:
39856.
35658.
60657.
400
400
350
300
250
200
150
100
50
0
400
350
300
250
200
150
100
50
0
200
300
400
500
200
Temperature (C)
fit1= 4.89%; fit10= 5.41%
2: E0=177.4 log10 A=13.82 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.95
scalefactor*cj:
54991.
49142.
64826.
300
400
500
Temperature (C)
fit1= 6.87%; fit10= 5.41%
2: E0=177.4 log10 A=13.71 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.55
scalefactor*cj:
39108.
34989.
59518.
90
500
70
400
60
50
40
300
30
20
200
10
0
80
70
500
60
50
400
40
30
300
20
10
200
0
0
25
50
75
100 125 150 175
25
50
Time (min)
75
100
125
150
Time (min)

fit1= 5.40%; fit10= 5.41%
2: E0=177.4 log10 A=13.82 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.95
scalefactor*cj:
76365.
68242.
90023.

fit1= 6.30%; fit10= 5.41%
2: E0=177.4 log10 A=13.71 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.55
scalefactor*cj:
45945.
41106.
69924.
600
100
500
90
400
60
50
300
40
30
20
200
10
0
120
500
100
80
400
60
40
300
20
200
0
0
25
50
75
100
125
150
Temperature (C)
70
Temperature (C)
80
110
Temperature (C)
80
100
Temperature (C)
110
Time (min)
25
50
75
100
125
150
Time (min)

fit1= 3.02%; fit10= 5.41%
2: E0=177.4 log10 A=13.82 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.95
scalefactor*cj:
56772.
50733.
66925.

fit1= 3.21%; fit10= 5.41%
2: E0=177.4 log10 A=13.71 (E)=10.8
(E)=31.2
3: E0=151.4 log10 A=8.55
scalefactor*cj:
41593.
37212.
63300.
10
8
7
6
5
4
3
2
1
0
300
400
500
600
700
9
8
7
6
5
4
3
2
1
0
800
300
400
Temperature (C)
DAEM kinetics of intensity m/z 28 [CO (+ C2H4 and N2)]
fit1=14.58%; fit10= 8.13%
2: E0=239.1 log10 A=14.36 (E)=5.6
3: E0=400 log10 A=17.77 (E)=30.1
scalefactor*cj:
4912.
4716.
24552.
600
700

fit1=12.17%; fit10= 8.13%
2: E0=239.1 log10 A=14.48 (E)=5.6
3: E0=400 log10 A=18.31 (E)=30.1
scalefactor*cj:
3835.
5123.
25995.
22
500
Temperature (C)
20
18
16
14
12
10
8
6
4
2
0
30
25
20
15
10
5
0
300
400
500
600
700
800
300
Temperature (C)
400
500
600
700
800
Temperature (C)

fit1= 6.90%; fit10= 8.13%
2: E0=239.1 log10 A=14.36 (E)=5.6
3: E0=400 log10 A=17.77 (E)=30.1
scalefactor*cj:
5250.
5040.
26239.

fit1= 8.16%; fit10= 8.13%
2: E0=239.1 log10 A=14.48 (E)=5.6
3: E0=400 log10 A=18.31 (E)=30.1
scalefactor*cj:
5643.
7537.
38246.
100
80
90
90
70
60
50
40
30
20
10
80
70
60
50
40
30
20
10
0
0
300
400
500
600
700
800
300
400
Temperature (C)
500
600
700

fit1= 9.59%; fit10= 8.13%
2: E0=239.1 log10 A=14.36 (E)=5.6
3: E0=400 log10 A=17.77 (E)=30.1
scalefactor*cj:
5335.
5122.
26666.

fit1= 8.37%; fit10= 8.13%
2: E0=239.1 log10 A=14.48 (E)=5.6
3: E0=400 log10 A=18.31 (E)=30.1
scalefactor*cj:
4349.
5809.
29478.
800
120
700
80
60
500
40
400
20
300
120
700
100
600
80
500
60
40
400
20
Temperature (C)
600
Temperature (C)
100
800
800
Temperature (C)
300
0
0
20
40
60
80
100
120
Time (min)
fit1= 2.82%; fit10= 8.13%
2: E0=239.1 log10 A=14.36 (E)=5.6
3: E0=400 log10 A=17.77 (E)=30.1
scalefactor*cj:
8189.
7862.
40928.
20
40
60
80
100
120
Time (min)
fit1= 2.27%; fit10= 8.13%
2: E0=239.1 log10 A=14.48 (E)=5.6
3: E0=400 log10 A=18.31 (E)=30.1
scalefactor*cj:
6000.
8014.
40667.
800
70
700
600
50
40
500
30
400
20
10
300
700
100
80
600
60
500
40
400
20
300
0
0
25
50
75
100
125
150
25
Time (min)
50
75
100
125
150
Time (min)
fit1= 1.57%; fit10= 8.13%
2: E0=239.1 log10 A=14.48 (E)=5.6
3: E0=400 log10 A=18.31 (E)=30.1
scalefactor*cj:
5372.
7176.
36412.

fit1= 2.89%; fit10= 8.13%
2: E0=239.1 log10 A=14.36 (E)=5.6
3: E0=400 log10 A=17.77 (E)=30.1
scalefactor*cj:
5062.
4860.
25300.
Temperature (C)
60
120
Temperature (C)
80
1.0
0.5
0.0
0.5
0.0
200
300
400
500
200
Temperature (C)
+
DAEM kinetics of intensity m/z 31 (CH3O )
fit1= 6.05%; fit10= 4.55%
2: E0=183.5 log10 A=14.07 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.37
scalefactor*cj:
1188.
661.
446.
300
400
500
Temperature (C)
+
fit1= 4.94%; fit10= 4.55%
2: E0=183.5 log10 A=14.32 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.60
scalefactor*cj:
350.
426.
366.
1.5
3.0
2.5
2.0
1.5
1.0
0.5
1.0
0.5
0.0
0.0
200
300
400
500
200
Temperature (C)
400
500
Temperature (C)

+
fit1= 3.38%; fit10= 4.55%
2: E0=183.5 log10 A=14.07 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.37
scalefactor*cj:
1200.
668.
450.

+
fit1= 2.99%; fit10= 4.55%
2: E0=183.5 log10 A=14.32 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.60
scalefactor*cj:
386.
470.
403.
11
10
300
9
8
7
6
5
4
3
2
1
0
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
200
300
400
500
200
Temperature (C)
+
fit1= 5.46%; fit10= 4.55%
2: E0=183.5 log10 A=14.07 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.37
scalefactor*cj:
988.
550.
371.
300
400
500
Temperature (C)
+
fit1= 5.62%; fit10= 4.55%
2: E0=183.5 log10 A=14.32 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.60
scalefactor*cj:
355.
432.
371.
400
300
0.5
200
0.0
500
0.5
400
300
200
0.0
25
50
75
100 125 150 175
25
50
Time (min)
75
100
125
150
Time (min)

+
fit1= 3.01%; fit10= 4.55%
2: E0=183.5 log10 A=14.07 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.37
scalefactor*cj:
1269.
706.
476.

+
fit1= 5.69%; fit10= 4.55%
2: E0=183.5 log10 A=14.32 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.60
scalefactor*cj:
331.
403.
346.
600
2.0
500
1.0
300
0.5
200
0.0
500
1.0
400
300
0.5
Temperature (C)
400
Temperature (C)
1.5
1.5
Temperature (C)
1.0
500
Temperature (C)
1.5
200
0.0
25
50
75
100
125
150
Time (min)
25
50
75
100
125
150
Time (min)

+
fit1= 2.21%; fit10= 4.55%
2: E0=183.5 log10 A=14.07 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.37
scalefactor*cj:
906.
504.
340.

+
fit1= 4.21%; fit10= 4.55%
2: E0=183.5 log10 A=14.32 (E)=5.7
(E)=13.1
3: E0=106.0 log10 A=5.60
scalefactor*cj:
363.
441.
379.

Tobacco Pyrolysis. Kinetic Evaluation of Thermogravimetric - Mass Spectrometric Experiments

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Tobacco Pyrolysis. Kinetic Evaluation of Thermogravimetric - Mass Spectrometric Experiments

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Supplementary Content for Article

Tobacco pyrolysis. Kinetic evaluation of

Supplementary Content, Page 1

Virginia blend, G0=4.1mg, Ar, 4C/min

Burley blend, G0=4.0mg, Ar, 4C/min

Supplementary Content, Page 2

Virginia blend, G0=1.0mg, Ar, 40C/min

Burley blend, G0=1.0mg, Ar, 40C/min

100 125 150 175

Supplementary Content, Page 3

Supplementary Content, Page 4

Intensity of m/z 15 (arbitr. unit)

Intensity of m/z 15 (arbitr. unit)

Intensity of m/z 15 (arbitr. unit)

Intensity of m/z 15 (arbitr. unit)

Burley blend, G0=4.0mg, Ar, 4C/min

Simultaneous evaluation of fifty MS intensity curves as described in Section 4.2.

Supplementary Content, Page 5

Intensity of m/z 15 (arbitr. unit)

Intensity of m/z 15 (arbitr. unit)

Burley blend, G0=1.0mg, Ar, 40C/min

Intensity of m/z 15 (arbitr. unit)

Virginia blend, G0=1.0mg, Ar, 40C/min

Intensity of m/z 15 (arbitr. unit)

Virginia blend, G0=4.0mg, Ar, stepwise T(t)

Burley blend, G0=4.1mg, Ar, stepwise T(t)

Supplementary Content, Page 6

Intensity of m/z 15 (arbitr. unit)

Intensity of m/z 15 (arbitr. unit)

Virginia blend, G0=4.2mg, Ar, steps at higher T

Burley blend, G0=4.1mg, Ar, steps at higher T

Intensity of m/z 29 (arbitr. unit)

Intensity of m/z 29 (arbitr. unit)

Virginia blend, G0=4.1mg, Ar, 4C/min

Burley blend, G0=4.0mg, Ar, 4C/min

Supplementary Content, Page 7

Intensity of m/z 29 (arbitr. unit)

Intensity of m/z 29 (arbitr. unit)

Burley blend, G0=4.1mg, Ar, 10C/min

Intensity of m/z 29 (arbitr. unit)

Intensity of m/z 29 (arbitr. unit)

Supplementary Content, Page 8

Intensity of m/z 29 (arbitr. unit)

Intensity of m/z 29 (arbitr. unit)

Virginia blend, G0=4.0mg, Ar, stepwise T(t)

Burley blend, G0=4.1mg, Ar, stepwise T(t)

Intensity of m/z 29 (arbitr. unit)

Intensity of m/z 29 (arbitr. unit)

Virginia blend, G0=4.2mg, Ar, steps at higher T

Burley blend, G0=4.1mg, Ar, steps at higher T

Supplementary Content, Page 9

Intensity of m/z 30 (arbitr. unit)

Intensity of m/z 30 (arbitr. unit)

Burley blend, G0=4.0mg, Ar, 4C/min

Intensity of m/z 30 (arbitr. unit)

Intensity of m/z 30 (arbitr. unit)

Virginia blend, G0=4.1mg, 10C/min

Burley blend, G0=4.1mg, Ar, 10C/min

Supplementary Content, Page 10

Intensity of m/z 30 (arbitr. unit)

Intensity of m/z 30 (arbitr. unit)

Burley blend, G0=1.0mg, Ar, 40C/min

Intensity of m/z 30 (arbitr. unit)