Supplementary files S1

Laminar Flame Speeds of Pentanol isomers: an Experimental and

Modeling study 1D. Nativel,

2M. Pelucchi,

2A. Frassoldati,

1A.Comandini,

2A. Cuoci,

2E. Ranzi,

1N. Chaumeix and

2T.

Faravelli

1 ICARE, CNRS-INSIS, Orléans, France

2 Department of Chemistry, Materials and Chemical Engineering “G.Natta”, Politecnico di Milano,

Piazza Leonardo da Vinci 32, 20133 Milan, Italy

Table S1 : summary of the experimental unstretched laminar flame speeds and Markstein lenghts obtained for iso-pentanol/air mixtures initially at 1 bar

(NL for non-linear; ER for Equivalence ratio)

Iso-pentanol/air flames - air : "air liquide" alphagaz 2 (20.9% O2 ; 79.1% N2) ; - iso-pentanol : Sigma Aldrich anhydrous 99%

N° exp ER T (K) Sigma Sl° linear (cm/s) R² linear Lu linear (mm) Sl° NL (cm/s) R² NL Lu NL (mm)

353 K

M_001 0.756 353.3 6.014 33.29 0.99999984 0.4736 31.61 0.999875 0.2679

M_011 0.791 352.7 6.188 36.26 0.99999961 0.4145 34.89 0.999936 0.2531

M_002 0.831 353.0 6.377 39.22 0.99999960 0.3619 37.88 0.999945 0.2258

M_003 0.889 353.1 6.627 42.89 0.99999934 0.3105 41.64 0.999823 0.2013

M_010 0.897 353.3 6.660 43.55 0.99999940 0.3081 42.26 0.999827 0.1985

M_006 0.961 353.0 6.888 46.69 0.99999906 0.2732 45.47 0.999809 0.1809

M_005 1.006 353.3 7.011 47.93 0.99999918 0.2442 46.83 0.999829 0.1659

M_004 1.049 353.4 7.090 48.75 0.99999886 0.2247 47.71 0.999831 0.1543

M_009 1.095 352.8 7.128 48.84 0.99999917 0.2001 47.94 0.999854 0.1409

M_008 1.141 353.3 7.126 48.19 0.99999909 0.1757 47.43 0.999906 0.1269

M_012 1.191 352.9 7.102 46.94 0.99999932 0.1381 46.45 0.999944 0.1056

M_007 1.241 353.0 7.066 44.13 0.99999874 0.1114 43.73 0.999926 0.0868

M_014 1.289 353.3 7.027 40.87 0.99999922 0.0828 40.64 0.999957 0.0676

M_013 1.339 353.1 6.983 37.44 0.99999920 0.0526 37.19 0.999956 0.0392

433 K

M_001 0.754 433.1 5.015 47.72 0.99999844 0.4518 46.25 0.999819 0.2889

M_005 0.763 433.6 5.052 49.04 0.99999986 0.4345 47.51 0.999967 0.2777

M_002 0.800 433.2 5.197 52.90 0.99999971 0.3933 51.55 0.999858 0.2617

M_029 0.831 433.4 5.303 57.71 0.99999795 0.3833 55.96 0.999774 0.2456

M_030 0.882 433.5 5.477 61.86 0.99999901 0.3444 60.23 0.999806 0.2273

M_031 0.889 433.3 5.502 62.13 0.99999953 0.3264 60.77 0.999857 0.2245

M_032 0.897 433.4 5.526 63.31 0.99999891 0.3443 61.65 0.999831 0.2277

M_006 0.938 433.3 5.648 64.59 0.99999972 0.3112 63.16 0.999865 0.2125

M_033 0.961 432.7 5.710 66.68 0.99999485 0.2954 64.86 0.999825 0.1923

M_034 0.961 433.2 5.704 66.73 0.99999810 0.3052 65.12 0.999802 0.2051

M_035 1.006 432.8 5.805 68.51 0.99999882 0.2852 67.11 0.999816 0.1978

M_036 1.049 433.3 5.865 69.32 0.99999832 0.2610 67.79 0.999797 0.1773

M_010 1.076 433.6 5.896 69.51 0.99999844 0.2527 68.24 0.999840 0.1785

M_037 1.095 433.3 5.904 69.60 0.99999875 0.2378 68.51 0.999851 0.1729

M_038 1.141 433.4 5.913 69.51 0.99999875 0.2319 68.34 0.999857 0.1658

M_039 1.191 433.3 5.903 67.58 0.99999879 0.2015 66.56 0.999891 0.1459

M_040 1.241 433.4 5.878 64.35 0.99999860 0.1595 63.91 0.999957 0.1277

M_016 1.299 433.7 5.850 60.24 0.99999969 0.1196 59.97 0.999958 0.1018

M_041 1.339 432.8 5.825 55.05 0.99999860 0.1010 54.71 0.999948 0.0816

M_017 1.430 433.8 5.761 46.68 0.99999876 0.0382 46.36 0.999953 0.0222

473 K

M_014 0.733 472.4 4.575 55.70 0.99999835 0.5032 53.76 0.999781 0.3121

M_015 0.783 472.7 4.756 62.24 0.99999804 0.4336 60.39 0.999793 0.2786

M_035 0.831 473.7 4.911 67.44 0.99999932 0.3708 65.85 0.999861 0.2509

M_036 0.889 473.4 5.088 73.74 0.99999715 0.3525 71.75 0.999783 0.2298

M_050 0.897 473.9 5.109 74.95 0.99999843 0.3500 73.02 0.999802 0.2316

M_011 0.931 472.6 5.215 77.06 0.99999877 0.3314 75.25 0.999822 0.2234

M_049 0.960 473.8 5.265 79.41 0.99999812 0.3342 77.18 0.999779 0.2158

M_048 1.006 473.7 5.353 81.05 0.99999914 0.3012 79.24 0.999843 0.2049

M_047 1.047 473.1 5.413 82.01 0.99999934 0.2791 80.15 0.999940 0.1888

M_046 1.095 473.5 5.455 82.46 0.99999799 0.2607 80.93 0.999821 0.1836

M_045 1.141 473.2 5.469 82.14 0.99999782 0.2516 80.63 0.999821 0.1770

M_044 1.191 474.0 5.464 80.97 0.99999838 0.2367 79.66 0.999882 0.1702

M_043 1.241 473.3 5.445 76.61 0.99999864 0.1821 75.81 0.999910 0.1392

M_042 1.339 473.1 5.395 67.65 0.99999934 0.1358 67.13 0.999940 0.1082

M_030 1.419 472.6 5.352 56.77 0.99999869 0.0622 56.38 0.999938 0.0442

Table S2 : summary of the experimental unstretched laminar flame speeds and Markstein lenghts obtained for n-pentanol/air mixtures initially at 1 bar

(NL for non-linear; ER for Equivalence ratio)

n-pentanol/air flames

- air : "air liquide" alphagaz 2 (20.9% O2 ; 79.1% N2) ; - 1-pentanol : Sigma Aldrich Reagentplus 99%

N° exp ER T (K) Sigma Sl° linear (cm/s) R² linear Lu linear (mm) Sl° NL (cm/s) R² NL Lu NL (mm)

353 K

M_002 0.809 352.1 6.275 40.29 0.99999974 0.3448 39.08 0.999841 0.2219

M_010 0.859 352.7 6.502 44.39 0.99999964 0.3244 43.13 0.999831 0.2111

M_008 0.859 353.3 6.502 44.46 0.99999920 0.3192 43.16 0.999811 0.2063

M_003 0.886 352.8 6.615 46.10 0.99999933 0.3013 44.79 0.999837 0.1961

M_016 0.914 352.7 6.725 47.38 0.99999920 0.2649 46.22 0.999825 0.1777

M_004 0.941 353.0 6.825 49.18 0.99999920 0.2711 47.95 0.999804 0.1812

M_009 1.006 353.3 7.012 51.88 0.99999830 0.2519 50.54 0.999793 0.1666

M_011 1.022 353.3 7.047 52.05 0.99999918 0.2328 50.99 0.999841 0.1617

M_017 1.050 353.2 7.093 52.27 0.99999865 0.1986 51.27 0.999845 0.1385

M_014 1.079 353.0 7.121 52.63 0.99999893 0.2013 51.64 0.999848 0.1412

M_019 1.108 353.2 7.133 52.86 0.99999903 0.1914 51.91 0.999853 0.1353

M_007 1.137 353.1 7.131 52.32 0.99999913 0.1830 51.50 0.999897 0.1325

M_018 1.169 353.2 7.118 52.08 0.99999877 0.1691 51.26 0.999894 0.1217

M_013 1.201 353.2 7.098 50.77 0.99999911 0.1457 50.14 0.999923 0.1086

M_015 1.261 352.6 7.054 47.65 0.99999851 0.1012 47.23 0.999928 0.0786

M_006 1.313 352.9 7.010 43.26 0.99999896 0.0716 42.98 0.999954 0.0564

433 K

M_002 0.756 433.7 5.034 51.64 0.99999901 0.4047 50.16 0.999817 0.2625

M_047 0.809 433.3 5.245 59.91 0.99999934 0.3609 58.42 0.999847 0.2417

M_048 0.859 433.4 5.423 64.58 0.99999865 0.3242 63.11 0.999800 0.2207

M_049 0.914 432.8 5.598 68.87 0.99999871 0.3147 67.18 0.999807 0.2104

M_050 0.941 432.8 5.672 70.98 0.99999855 0.3036 69.27 0.999807 0.2038

M_051 1.006 433.1 5.820 73.91 0.99999855 0.2747 72.38 0.999832 0.1899

M_052 1.050 433.2 5.888 75.28 0.99999845 0.2696 73.70 0.999823 0.1856

M_053 1.079 432.7 5.917 75.25 0.99999720 0.2552 73.67 0.999784 0.1752

M_026 1.124 433.4 5.936 74.62 0.99999959 0.2349 73.47 0.999892 0.1709

M_054 1.169 433.0 5.934 74.24 0.99999871 0.2115 73.10 0.999885 0.1531

M_055 1.200 433.0 5.924 72.88 0.99999875 0.1921 71.92 0.999900 0.1421

M_012 1.257 433.3 5.896 69.40 0.99999942 0.1673 68.71 0.999927 0.1288

M_056 1.313 433.1 5.863 64.12 0.99999822 0.1292 63.62 0.999917 0.1027

M_022 1.368 433.0 5.826 58.45 0.99999936 0.0894 58.26 0.999965 0.0776

M_021 1.484 433.6 5.744 43.40 0.99999968 -0.0318 43.09 0.999990 -0.0525

473 K

M_016 0.750 472.9 4.650 62.00 0.99999858 0.4289 60.31 0.999818 0.2810

M_025 0.784 473.1 4.772 66.77 0.99999895 0.4039 64.99 0.999811 0.2660

M_029 0.809 473.3 4.856 70.78 0.99999885 0.3798 68.95 0.999995 0.2512

M_030 0.859 473.4 5.015 76.59 0.99999844 0.3529 74.63 0.999810 0.2335

M_031 0.914 473.6 5.168 81.67 0.99999808 0.3367 79.60 0.999789 0.2228

M_032 0.941 473.7 5.234 83.15 0.99999869 0.3105 81.39 0.999816 0.2133

M_035 1.006 473.8 5.365 86.30 0.99999855 0.2974 84.44 0.999837 0.2033

M_042 1.050 473.7 5.429 87.95 0.99999764 0.2776 86.02 0.999810 0.1878

M_048 1.079 473.8 5.457 88.13 0.99999849 0.2681 86.51 0.999827 0.1890

M_046 1.124 473.8 5.480 87.75 0.99999710 0.2595 85.98 0.999846 0.1782

M_021 1.153 472.9 5.492 86.22 0.99999932 0.2265 85.02 0.999906 0.1675

M_041 1.169 473.5 5.485 86.01 0.99999829 0.2042 84.80 0.999904 0.1491

M_039 1.200 473.8 5.476 84.81 0.99999910 0.1900 83.89 0.999921 0.1450

M_024 1.228 473.1 5.476 83.68 0.99999879 0.2077 82.61 0.999914 0.1545

M_015 1.228 472.8 5.475 83.73 0.99999906 0.2156 82.60 0.999912 0.1592

M_045 1.256 473.7 5.456 81.75 0.99999753 0.1842 80.88 0.999931 0.1397

M_026 1.266 473.1 5.459 80.91 0.99999739 0.1989 79.86 0.999901 0.1469

M_017 1.303 473.1 5.440 77.11 0.99999874 0.1696 76.38 0.999907 0.1329

M_040 1.313 473.7 5.427 75.33 0.99999899 0.1315 74.94 0.999942 0.1101

M_027 1.377 473.1 5.398 68.08 0.99999849 0.1253 67.53 0.999930 0.0977

Table S3 : Rate constant parameters for high temperature oxidation reactions of n- and i- butanol, n- and iso-pentanol. Units are cm3 mol s cal.

Reaction Classes i-butanol n-butanol i-pentanol n-pentanol

Site A n Ea A n Ea A n Ea A n Ea

H-abstractions

by H·

O 5.00E+06 2.00 6526 5.00E+06 2.00 6526 5.00E+06 2.00 6526 5.00E+06 2.00 6526

α 1.60E+07 2.00 3951 1.60E+07 2.00 3951 1.60E+07 2.00 3951 1.60E+07 2.00 3951

β 2.41E+06 2.00 2663 9.00E+06 2.00 3951 9.00E+06 2.00 3951 9.00E+06 2.00 3951

γ 2.24E+07 2.00 6526 1.00E+07 2.00 3951 2.41E+06 2.00 2663 1.00E+07 2.00 3951

δ

1.12E+07 2.00 6526 2.24E+07 2.00 6526 1.00E+07 2.00 3951

ε

1.12E+07 2.00 6526

by ·OH

O 3.99E+05 2.00 -474 3.99E+05 2.00 -474 3.99E+05 2.00 -474 3.99E+05 2.00 -474

α 1.38E+06 2.00 -2260 1.38E+06 2.00 -2260 1.38E+06 2.00 -2260 1.38E+06 2.00 -2260

β 3.99E+05 2.00 -3153 7.20E+05 2.00 -2260 7.20E+05 2.00 -2260 7.20E+05 2.00 -2260

γ 1.90E+06 2.00 -474 8.00E+05 2.00 -2260 3.99E+05 2.00 -3153 8.00E+05 2.00 -2260

δ

9.50E+05 2.00 -474 1.90E+06 2.00 -474 8.00E+05 2.00 -2260

ε

9.50E+05 2.00 -474

by HO2·

O 1.07E+05 2.00 15026 1.07E+05 2.00 15026 1.07E+05 2.00 15026 1.07E+05 2.00 15026

α 7.40E+05 2.00 11888 7.40E+05 2.00 11888 7.40E+05 2.00 11888 7.40E+05 2.00 11888

β 5.39E+04 2.00 10319 1.94E+05 2.00 11888 1.94E+05 2.00 11888 1.94E+05 2.00 11888

γ 5.20E+05 2.00 15026 2.15E+05 2.00 11888 5.39E+04 2.00 10319 2.15E+05 2.00 11888

δ

2.60E+05 2.00 15026 5.20E+05 2.00 15026 2.15E+05 2.00 11888

ε

2.60E+05 2.00 15026

R+Fuel→RH+R'

O 1 primary hydrogen 1 primary hydrogen 1 primary hydrogen 1 primary hydrogen

α 3 secondary hydrogens 3 secondary hydrogens 3 secondary hydrogens 3 secondary hydrogens

β 1 tertiary hydrogen 2 secondary hydrogens 2 secondary hydrogens 2 secondary hydrogens

γ 6 primary hydrogens 2 secondary hydrogens 1 tertiary hydrogen 2 secondary hydrogens

δ

3 primary hydrogens 6 primary hydrogens 2 secondary hydrogens

ε

3 primary hydrogens

Unimolecular Ci-Cj

O↔Cα 1.50E+16 0.00 93200 1.50E+16 0.00 93200 1.50E+16 0.00 93200 1.50E+16 0.00 93200

Cα↔Cβ 2.00E+16 0.00 85000 2.00E+16 0.00 85000 2.00E+16 0.00 85000 2.00E+16 0.00 85000

Cβ↔Cγ 7.00E+16 0.00 88000 2.00E+16 0.00 85000 3.00E+16 0.00 85000 6.00E+16 0.00 85000

Cγ↔Cδ 2.00E+16 0.00 86000 7.00E+16 0.00 88000 8.00E+16 0.00 85000

Cδ↔Cε 6.00E+16 0.00 86000

H·+R·↔ROH 5.00E+13 0.00 0 5.00E+13 0.00 0 5.00E+13 0.00 0 5.00E+13 0.00 0

Dehydration 5.00E+13 0.00 65600 1.00E+14 0.00 67600 1.00E+14 0.00 67600 1.00E+14 0.00 67600

Dehydrogenation 5.00E+13 0.00 69500 5.00E+13 0.00 69500 5.00E+13 0.00 69500 5.00E+13 0.00 69500

Radical Decomposition

Cn-Oxy_R → CH2O + Cn-1alkylrad 3.00E+13 0.00 15000 3.00E+13 0.00 15000 6.00E+13 0.00 15000 6.00E+13 0.00 15000

Cn-Oxy_R → Cnaldehyde + H 3.00E+13 0.00 26000 3.00E+13 0.00 26000 3.00E+13 0.00 26000 3.00E+13 0.00 26000

Cn-α_R → Cnaldehyde + H 3.00E+13 0.00 37000 3.00E+13 0.00 37000 3.00E+13 0.00 37000 3.00E+13 0.00 37000

Cn-α_R → enol + alkylrad 3.00E+13 0.00 32500 3.00E+13 0.00 31000 3.00E+13 0.00 31000 3.00E+13 0.00 31000

Cn-β_R → OH + olefin 3.00E+13 0.00 33000 3.00E+13 0.00 33000 4.50E+13 0.00 33000 3.00E+13 0.00 33000

Cn-β_R → enol + alkylrad 3.00E+13 0.00 37000 3.00E+13 0.00 32500 4.00E+13 0.00 32500 3.00E+13 0.00 30000

Other are based on Curran et al. (2006), Dente et al. (2007)

Radical Isomerization

γ ↔ O 1.00E+11 0.00 21500 1.00E+11 0.00 23000 1.00E+11 0.00 23600 1.00E+11 0.00 23000

δ ↔ O

1.60E+10 0.00 16000 1.60E+10 0.00 16000 1.60E+10 0.00 17000

ε ↔ O

5.00E+09 0.00 16000

δ ↔ α

2.00E+11 0.00 19600 2.00E+11 0.00 19600 2.00E+11 0.00 20600

ε ↔ α

3.20E+10 0.00 13500

ε ↔ β

2.00E+11 0.00 19600

Tautomerization (enol=aldehyde), from Heufer et al., 2012

8.60E+11 0.32 55900 8.60E+11 0.32 55900 8.60E+11 0.32 55900 8.60E+11 0.32 55900

HO2 catalyzed Tautomerization (enol=aldehyde), from Sarathy et al., 2013

1.50E+05 1.67 6810 1.50E+05 1.67 6810 1.50E+05 1.67 6810 1.50E+05 1.67 6810

HCOOH catalyzed Tautomerization (enol=aldehyde), from Sarathy et al., 2013

2.80E-02 3.29 -4509 2.80E-02 3.29 -4509 2.80E-02 3.29 -4509 2.80E-02 3.29 -4509

Front view Side view

Exploded view Top view

Figure S1 : Exploded, top, front and side views of the spherical bomb

high speed

camera

screen

Knife or spot

pressure sensor

tungsten

electrodethermocouple

white light source

focus lens

pin hole

mirror

(a) (b)

Electrodes

Voltage probe

Cu

rre

nt

pro

be

Electrodes

Figure S2 : (a) Z-shape Schlieren configuration for the spherical flame imaging and recording; (b)

Experimental setup scheme with the ignition system.

Figure S3 : Typical propagation of the flame with the correponding radius of the flame as a function

of time and the evolution of the pressure during the post-processing at 433K and 1bar.n-pentanol-air

mixtures at three equivalence ratio, lean, rich and close to the maximum flame speed are represented

n-pentanol / air flames

Figure S4: Typical propagation of the flame with the correponding radius of the flame as a function

of time and the evolution of the pressure during the post-processing at 433K and 1bar. Iso-pentanol-

air -air mixtures at three equivalence ratio, lean, rich and close to the maximum flame speed are

represented.

Iso-pentanol / air flames