Comparative Chemical Kinetic A

COMPARATIVE CHEMICAL KINETIC AND EXPERIMENTAL STUDY OF
METHANOL, ETHANOL, N -PROPANOL AND N -BUTANOL AUTO-IGNITION

DELAY TIMES
Khalid Emilio Noorani
Master of Engineering
Department of Mechanical Engineering
McGill University
Montreal, Quebec, Canada
2011-11-27
A thesis submitted to McGill University in partial fulfillment of the requirements of the

degree of a Master of Engineering
(c) Noorani 2011

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ACKNOWLEDGMENTS
Dr. Bergthorson has shown me the importance of passion and hard work in every
endeavour. He has always been enthusiastic and provided calm friendly guidance. I am
deeply grateful to him for having allowed me to join the alternative fuel laboratory four
years ago as an undergraduate as well as his constant encouragements.
Benjamin Akih-Kumgeh has given me immense help along the way: from my honour’s
thesis to my master’s thesis. He has proven, time and time again, the value of hard work
and passion. I am also very grateful to Ben for generously sharing his experimental set-up
with me. He is a good mentor and a great friend: for that, and much more, I am extremely
thankful.
I would like to thank Graeme Watson for emphasising the importance of clarity and
rigor; Sean Salusbury, Greg Chung and George-Philippe Gauthier for their insight, valuable
remarks and good humour during formal (and informal) presentations.
In addition, I would like to thank my fellow master’s candidates: Nabil and Zian for
their support and friendship.
Finally, I would like to thank my family: Mom, Dad, Rodrigo and Aysha. None of
this would have been possible without them.
ii
ABSTRACT
Much work has been done to model and understand alcohol oxidation individually.
Comparative studies of ignition delay times of alcohols, however, are limited. The thesis
presents a comparative study of their ignition delay times. Mixtures of methanol, ethanol,
n-propanol and n-butanol and synthetic air are ignited behind reflected shock waves at
high temperatures (1070K-1760K). The ignition delay times are measured in a shock tube
as equivalence ratio, argon to oxygen ratio (dilution) and pressure are changed to highlight
trends and similarities between the fuels. Experimental results have indicated that these
fuels have comparable ignition delay times, which may indicate similarities of the oxidation
pathways of the alcohols. The results are compared against simulations of chemical kinetic
models from the literature. The Marinov model is found to be the most accurate of the
models. Compared to one another, simulations of the ignition delay times of the various
models fail to show the experimental collapse at fixed equivalence ratio φ, argon to oxygen
ratio (dilution), D, and pressure, p. Reaction rate dependency analysis of kinetic models
indicate dominance of radical chemistry, H abstraction reactions of methanol and uni-
molecular fuel decompositions of n-butanol.
iii
ABRÉGÉ
Dans cette thèse, des mélanges de méthanol, éthanol, n-propanol et n-butanol avec
de l’air synthétique sont explosés derrière une onde de choc réfléchie à haute température
(1070K-1760K) où les temps de retard à l’allumage sont mesurés à différents taux d’équivalences,
dilutions, pressions et températures pour établir les points de similitaritées et différences en-
tre alcools. Beaucoup d’études ont été fait pour modéliser et comprendre l’oxydation de ces
derniers mais elles n’ont pas été réalisé de manière comparative. Ainsi, ce travail présente
une étude comparative des temps de retard d’allumage des alcools simples (C1 à C4 ). Les
résultats ont indiqué que ces combustibles ont des temps de retard d’allumage comparables,
ce qui indique une similitaritée des voies d’oxydation des différents alcools. Des modèles
cinétiques trouvés dans la littérature sont comparés aux résultats expérimentaux. Il se
trouve que le modèle de Marinov (1998) est le plus proches des valeurs mesurées. De plus,
des analyses de dépendance des taux de réactions sur les delais d’allumage sur ces modèles
indiquent la dominance des réactions à base de radicaux.
iv
CONTRIBUTIONS OF THE AUTHOR
The author has made the following contributions:
1. Establishing the research question for this thesis in conjunction with his supervisor
and Benjamin Akih-Kumgeh,
2. Performing the shock tube experiments,
3. Post-processing of the measured data,
4. Performing and interpreting the sensitivity studies of the chemical kinetic models,
5. Analysing the results in consultation with his supervisor and Benjamin Akih-Kumgeh,
6. Publishing of a paper “Comparative High Temperature Shock Tube Ignition of C1-
C4 Primary Alcohols” in Energy and Fuels (2010), Volume 24, pages 5834 to 5843
co-authored by Benjamin Akih-Kumgeh and his supervisor.
v
TABLE OF CONTENTS
ACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
ABRÉGÉ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
CONTRIBUTIONS OF THE AUTHOR . . . . . . . . . . . . . . . . . . . . . . . . . v
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Literature review of alcohol auto-ignition studies . . . . . . . . . . . . . . . . . 4
2.1 Shock tube studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.1.1 Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.2 Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3 n-Propanol and n-butanol . . . . . . . . . . . . . . . . . . . . . . 6
2.2 Low and high temperature comparative studies . . . . . . . . . . . . . . 7
2.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3 Experimental technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1 Background— shock tubes in chemical kinetics . . . . . . . . . . . . . . 11

3.1.1 Shock tube gas dynamics . . . . . . . . . . . . . . . . . . . . . . . 11
3.1.2 Ignition delay time correlations . . . . . . . . . . . . . . . . . . . 15
3.2 Experimental set-up and procedure . . . . . . . . . . . . . . . . . . . . . 17
3.2.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.2 Simulation of ignition . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2.3 Uncertainty analysis . . . . . . . . . . . . . . . . . . . . . . . . . 25
4 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

4.2 Simulation results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.3 Correlation parameters of ignition delay times . . . . . . . . . . . . . . . 37
vi
4.4 Reaction rate dependency analysis . . . . . . . . . . . . . . . . . . . . . 45
4.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
A Oxidation chemistry of primary alcohols . . . . . . . . . . . . . . . . . . . . . . 58
A.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
A.2 Methanol oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
A.3 Ethanol oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
A.4 n-Propanol and n-butanol oxidation . . . . . . . . . . . . . . . . . . . . 62
A.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
B Tabulated ignition delay times . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
C Supporting figures of simulated ignition delay times . . . . . . . . . . . . . . . 71
vii
LIST OF TABLES
Table page
1–1 Higher heating values of primary C1 -C6 alcohols and gasoline per unit mass. 2
2–1 Parameters of methanol shock tube studies. . . . . . . . . . . . . . . . . . . 5
3–1 Combustible mixtures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4–1 Experimental conditions for methanol (C1 : 1 carbon molecule) to n-butanol

(C4 : 4 carbons molecule) ignition delay times measurements. . . . . . . . 28
4–2 Experimental parameters of the correlation: τ = C · φα · Dβ · pζ · exp (Ea /RT ). 31
4–3 Details of mechanisms in this study . . . . . . . . . . . . . . . . . . . . . . . 35
4–4 Experimental and simulation parameters of the correlation: τ = C · φα · Dβ ·

pζ · exp (Ea /RT ). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4–5 Key reaction rates parameters obtained from the four models. Reaction rate
units are cm3 ·mol·s·cal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
B–1 Ignition delay times . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
viii
LIST OF FIGURES
Figure page
2–1 Ignition delay measurements from a hot air stream of primary alcohols
by Mullins (1953) at p = 1 atm. Legend: methanol (), ethanol (),
n-propanol (•), n-butanol (◦), n-pentanol (N), n-hexanol (△), n-decanol
(♦). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2–2 Ignition delay times of alkanes by Burcat et al. (1971) at φ = 1, p ≈ 10 ± 3

atm. Legend: Methane (N), ethane (+), propane (△), butane (•), pentane
(◦). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3–1 Shock tube gas dynamics: (a) Shock tube sections; (b) x-t diagram of the
wave system in an ideal shock tube and definition of the ignition delay
time, τ ; (c) Pressure distribution at t=t1 . . . . . . . . . . . . . . . . . . . 12
3–2 Experimental set-up (not to scale). . . . . . . . . . . . . . . . . . . . . . . . 20
3–3 Pressure traces at x = 0, 0.5, 1.0 and 1.5 m from the end wall driven section
where the arrival of the shock at the end wall marks the start of the
fuel/oxygen reaction i.e. t = 0. τ is the ignition delay time. . . . . . . . . 21
3–4 End wall pressure and CH radical chemilumescence measurements with

corresponding ignition delay time, τ , for a n-butanol/O2 /Ar mixture
with φ = 1.0, D = 10, p = 10 atm and T = 1173 K. The ignition moment
in this case is indicated by the star in the figure. . . . . . . . . . . . . . . 23
3–5 Species profiles in a zero dimensional adiabatic reactor with methanol and
air at φ = 0.22 where T = 1200 K and p = 1 atm using the Li et al. (2007)
methanol reaction mechanism. . . . . . . . . . . . . . . . . . . . . . . . . 25
3–6 Pressure gradient in a zero dimensional adiabatic reactor with methanol

and air at T = 1200 K and p = 1 atm using the methanol Li et al. (2007)
reaction mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3–7 Ignition delay times of n-butanol (Mix 1): φ = 1, D = 10, p = 10 atm with
temperature error bars (±15 K). . . . . . . . . . . . . . . . . . . . . . . . 27
ix
4–1 Alcohol ignition delay times, τ , at φ = 1, D = 10, p = 10 atm. Data:
methanol (+), ethanol (◦), n-propanol (△), n-butanol (), C2 -C4 corre-
lation line (black dash line). . . . . . . . . . . . . . . . . . . . . . . . . . . 29

methanol (+), ethanol (◦), n-propanol (△), n-butanol (), C1 -C4 corre-
lation line (black line). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4–3 Alcohol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

methanol (+), ethanol (◦), n-propanol (△) and the correlation prediction
bounds excluding scatter using a 95% confidence interval (dash lines),
n-butanol (), C1 -C4 correlation line (black line). . . . . . . . . . . . . . 30

methanol (+), ethanol (◦), n-propanol (△) and the correlation prediction
bounds excluding scatter using a 95% confidence interval (dash lines),
n-butanol (), C1 -C4 correlation line (black line), . . . . . . . . . . . . . 30

methanol (+), ethanol (◦), n-propanol (△), n-butanol () and the
correlation prediction bounds excluding scatter using a 95% confidence
interval (dash lines), C1 -C4 correlation line (black line). . . . . . . . . . . 32

methanol (+) and the correlation prediction bounds excluding scatter
using a 95% confidence interval (dot-dash lines), ethanol (◦), n-propanol
(△), n-butanol () and the correlation prediction bounds excluding
scatter using a 95% confidence interval (dash lines), C1 -C4 correlation
line (black line). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4–7 Upper and lower prediction bounds of the correlations at φ = 0.5, D = 10,
p = 10 atm of methanol (thin grey dash lines), ethanol (grey dot-dash
lines), n-propanol (black dash lines) and n-butanol (black solid lines). . . 34
4–8 Upper and lower prediction bounds of the correlations at φ = 1, D = 10,

4–9 Upper and lower prediction bounds of the correlations at φ = 2, D = 10,

4–10 Methanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

methanol (+). Simulations: methanol [1] (dot line). . . . . . . . . . . . . 36
x
4–11 Ethanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data: ethanol
(◦). Simulations: ethanol [2] (dash line) . . . . . . . . . . . . . . . . . . . 36
4–12 n-Propanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

n-propanol (△). Simulations: n-propanol [3] (thin solid line). . . . . . . . 36
4–13 n-Propanol ignition delay times, τ , at φ = 1, D = 20, p = 2 atm. Data:

4–14 n-Butanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

n-butanol (). Simulations: n-butanol [4] (thick solid line). . . . . . . . . 37

methanol (+), ethanol (◦), n-propanol (△), n-butanol (). Simulations:
methanol [1] (dot line), ethanol [2] (dash line), n-propanol [3] (thin solid
line), n-butanol [4] (thick solid line). . . . . . . . . . . . . . . . . . . . . . 38

4–17 Alcohol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:


4–19 Comparison between experimental and literature ignition delay times of

methanol. Legend: Fieweger et al. [5] (+) and methanol experimental
correlation from Table 4–4 (dash line) at φ = 1, D = 3.76, p = 13.2 atm. . 41

methanol. Legend: Natarajan and Bhaskaran [6] (+) and methanol
experimental correlation from Table 4–4 (dash line) at φ = 0.5, D = 12,
p = 12.5 atm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
xi
ethanol. Legend: Dunphy et al. [7] (), Akih-Kumgeh & Bergthorson [8]
(×) and ethanol experimental correlation from Table 4–4 (solid line) at
φ = 0.5, D = 12.2, p = 3.34 atm. Heufer and Olivier [9] (◦) and ethanol
experimental correlation (dash line) at φ = 1, D = 3.73, p = 19 atm. . . . 42
4–22 Comparison of correlations derived in this study with literature data on

n-propanol ignition. Legend: n-propanol Johnson et al. [3] (△) and
n-propanol experimental correlation from Table 4–4 (dot-dash line) at
φ = 2, D = 83, p = 1.1 atm. . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4–23 Comparison of correlations derived in this study with literature data

on n-butanol ignition. Legend: Black et al. [10] (△) and n-butanol
experimental correlation from Table 4–4 (thick solid line) at φ = 1,
D = 26.6, p = 8 atm. Heufer et al. [11] (◦) and current study correlation
(dot-dash line) at φ = 1, D = 3.73, p = 13 atm. Hanson et al. [12] ()
and n-butanol experimental correlation from Table 4–4 (thin solid line)
at φ = 0.5, D = 23.83, p = 19 atm. Hanson et al. [12] (+) and n-butanol
experimental correlation from Table 4–4 (dot line) at φ = 1, D = 3.76,
p = 22 atm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

ethanol and n-butanol. Legend: Heufer and Olivier [9] (◦) and ethanol
experimental correlation (dash line) at φ = 1, D = 3.73, p = 19 atm and
Heufer et al. [11] (△) and current study correlation (dot-dash line) at
φ = 1, D = 3.73, p = 13 atm. . . . . . . . . . . . . . . . . . . . . . . . . . 45
4–25 15 most important reactions from the reaction rate dependency analysis
(m = 0.01) of the methanol mechanism by Li et al. [1] for a stoichiometric
methanol/O2 /Ar mixture at 7 atm with argon/oxygen ratio, D, of 12 at
a temperature of 1200 K. The unperturbed ignition delay time is 330 µs. 47
(m = 0.01) of the ethanol mechanism by Marinov [2] for a stoichiometric
ethanol/O2 /Ar mixture at 7 atm with argon/oxygen ratio, D, of 12 at a
temperature of 1200 K. The unperturbed ignition delay time is 650 µs. . . 47
xii
(m = 0.01) of the iso-propanol/n-propanol mechanism by Johnson et
al. [3] for a stoichiometric n-propanol (n−C3 H7 OH)/O2 /Ar mixture at
7 atm with argon/oxygen ratio, D, of 12 at a temperature of 1200 K.
The unperturbed ignition delay time is 1692 µs. Note that reaction 1:
HO2 +HO2 ⇋ H2 O2 +O2 has a duplicate reaction with another set of rate
parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
(m = 0.01) of the n-butanol mechanism by Sarathy et al. [4] for a
stoichiometric n-butanol (or n−C4 H9 OH)/O2 /Ar mixture at 7 atm with
argon/oxygen ratio, D, of 12 at a temperature of 1200 K. The unperturbed
ignition delay time is 917 µs. . . . . . . . . . . . . . . . . . . . . . . . . . 49
4–29 Reaction rate constants, k of the reaction: H + O2 ⇋ O + OH from

methanol [1] (+), ethanol [2] (), n-propanol [3] (solid line), n-butanol
[4] (◦). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4–30 Reaction rates constants, k of the reaction: H2 O2 + O ⇋ OH + HO2 from

[4] (◦). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4–31 Reaction rates constants, k of the reaction: HO2 + HO2 ⇋ H2 O2 + O2 from

[4] (◦). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4–32 Reaction rates constants, k of the fuel-specific reactions of methanol Li et al.

[1] model (Reaction 1 in Table 4–5: +) and ethanol [2] model (Reaction
1 in Table 4–5: ). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4–33 Reaction rates constants, k of the fuel-specific reactions of propanol Johnson

et al. [3] model. Reaction 1 in Table 4–5: △, Reaction 2: ⋄ and Reaction
3: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4–34 Reaction rates constants, k of the fuel-specific reactions of butanol Sarathy

et al. [4] model. Reaction 1 in Table 4–5: dashed line, reaction 2: dotted
line, reaction 3: dashed-dotted line, and reaction 4: ⋄. . . . . . . . . . . . 53
A–1 Typical alcohol oxidation pathway (Adapted from Fig. 8 of Norton et al.,
1991). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
A–2 Primary oxidation pathways of methanol. . . . . . . . . . . . . . . . . . . . 60
xiii
A–3 Species profiles in a zero dimensional adiabatic reactor with methanol and
air at T = 1200 K and p = 1 atm using the methanol Li et al. (2007)
reaction mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
A–4 Pyrolysis of n-propanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
C–1 Methanol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

methanol (+). Simulations: methanol [1] (dotted line). . . . . . . . . . . . 72
C–2 Ethanol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

ethanol (◦). Simulations: ethanol [2] (dashed line) . . . . . . . . . . . . . 72
C–3 n-Propanol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

C–4 n-Butanol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

C–5 Methanol ignition delay times, τ , at φ = 1, D = 10, p = 2 atm. Data:

C–6 Ethanol ignition delay times, τ , at φ = 1, D = 10, p = 2 atm. Data: ethanol

(◦). Simulations: ethanol [2] (dashed line) . . . . . . . . . . . . . . . . . . 73
C–7 n-Propanol ignition delay times, τ , at φ = 1, D = 10, p = 2 atm. Data:

C–8 n-Butanol ignition delay times, τ , at φ = 1, D = 10, p = 2 atm. Data:

C–9 Methanol ignition delay times, τ , at φ = 1, D = 10, p = 10 atm. Data:

C–10Ethanol ignition delay times, τ , at φ = 1, D = 10, p = 10 atm. Data:

C–11n-Propanol ignition delay times, τ , at φ = 1, D = 10, p = 10 atm. Data:

C–12n-Butanol ignition delay times, τ , at φ = 1, D = 10, p = 10 atm. Data:

C–13Methanol ignition delay times, τ , at φ = 1, D = 20, p = 2 atm. Data:

xiv
C–14Ethanol ignition delay times, τ , at φ = 1, D = 20, p = 2 atm. Data: ethanol
(◦). Simulations: ethanol [2] (dashed line) . . . . . . . . . . . . . . . . . . 75


C–17Methanol ignition delay times, τ , at φ = 1, D = 20, p = 10 atm. Data:

C–18Ethanol ignition delay times, τ , at φ = 1, D = 20, p = 10 atm. Data:



xv
CHAPTER 1
Introduction
It is unquestionable that worldwide demand for fossil fuels will keep increasing over the
coming years. Without appropriate alternatives, oil will be prohibitively expensive and will
eventually be depleted. Some estimates suggest that in 2023, oil reserves will only be able
to meet half of worldwide demand [13]. Many methods have been proposed to reduce our
dependence on the fuel but focus here will be on bio-fuels produced from biomass. Unlike
conventional oil, bio-fuels can be derived from renewable sources which can be divided
into two types or “generations”. First generation bio-fuels are produced from consumable
feedstocks whereas the second generation ones use non-food feedstocks such as cellulosic
waste (e.g. bagasse, molasses) or micro algae [14]. Ethanol can be a second-generation
bio-fuel if it is produced without depleting food supplies or significantly reducing arable
land which are issues often highlighted by critics [15]. Beginning to investigate new fuels
is a necessary step to finding viable replacements to oil-derived fuels especially if they
mitigate climate change and reduce toxic emissions [16]. In 1987, Mills and Ecklund [17]
suggested that alcohols had the potential to “revolutionise” the fuel industry. Nearly two
decades later, even if alcohols like ethanol are used throughout the world (Canada, the
United States, Brazil, France, Germany, Sweden, China, etc...) they only constitute 5-10%
of what is in our gas tanks. Fossil fuels still remain our main source of transportation
energy.
Nevertheless, short-chain alcohols such as ethanol have received significant attention
but so have higher molecular weight alcohols (i.e., 1-pentanol or 1-hexanol) because of
1
Table 1–1: Higher heating values of primary C1 -C6 alcohols and gasoline per unit mass.
Fuel ∆Hc 0 [MJ/kg]
Methanol 23.6 [18]
Ethanol 29.7 [18]
n-Propanol 33.6 [18]
n-Butanol 36.0 [18]
n-Pentanol 37.8 [18]
n-Hexanol 39.1 [19]
Gasoline 44.4 [20]
their increased stability when blended with conventional fuels, lower hygroscopicity, lower
volatility and energy densities rivaling gasoline (Table 1–1).
To study the combustion of fuels, it is impractical to use gas-turbines or internal com-
bustion engines since they involve turbulent reactive flows that are difficult to analyse or
repeat under controllable conditions, i.e., temperature, pressure, mixture composition or
flow regime (laminar, transitional or turbulent). The challenges can be overcome by de-
signing repeatable, highly controllable experiments with simple or limited flow phenomena.
Jet-stirred reactors, flow reactors or stagnation flames meet this condition.
A shock tube can be used to generate shock waves such that auto ignition conditions are
reached behind the reflected wave at the end wall of the driven section. In effect, it removes
advection and diffusion in order to isolate oxidation chemistry from fluid interactions.
Generally, shock tubes have traditionally been used to obtain reaction rate parameters of
key reactions such as the hydrogen-oxygen chain branching reaction [21–23]. But these
are also used to measure ignition delay times, which characterise the ignition behavior of
investigated fuels under various conditions. The experimental measurements (flame speeds,
Su , ignition delay times, τ , species concentration profiles) from the various combustion
2
systems can be used as validation targets for reaction mechanisms that model the chemical
reactions occurring between fuel and oxidizer.
The present study focuses on methanol, ethanol, n-propanol and n-butanol ignition
delay times behind reflected shock waves in order to uncover trends in their relative be-
haviour. Reaction rate analyses of the chemical kinetic models of the fuels are presented
to discover the primary reactions of alcohol auto-ignition.
3
CHAPTER 2
Literature review of alcohol auto-ignition studies
The chapter below presents a literature review of previous ignition studies of alcohols
performed individually and comparatively.
2.1 Shock tube studies
2.1.1 Methanol
Cooke et al. [24] ignited methane, ethane, methanol and ethanol behind reflected shock
waves and found the following order of ignition delay times (from longer to shorter):
methane > methanol > ethanol > ethane. The higher propensity of ethanol to ignite, rel-
ative to that of methanol, seemed to be due to the higher reaction rates of chain-branching
reactions. Bowman [25] developed a 19 step reaction mechanism for methanol along with
measurements of ignition delay times at high temperatures. The model could not accu-
rately predict ignition delay times below 1800 K according to Natarajan and Bhaskaran
[6] who suggested an improved reaction mechanism. Cribb et al. [26] measured species
profiles using laser schlieren densitometry and dynamic mass spectrometry and identified,
via sensitivity analysis, the most important reactions of methanol auto ignition.
Fieweger et al. [5] measured deflagration (τdefl ) and detonation (secondary ignition,
τDDT ) types of ignition delay times of several hydrocarbons including methanol at lower
temperatures (down to 800 K) and engine relevant pressures (40 atm) to study engine
knock using shadowgraphs and CH-band emissions. The study concluded that methanol
and MTBE tended to deflagrate more readily than primary reference fuels. A summary
of methanol shock tube studies is presented in Table 2–1 along with the corresponding
4
conditions of each study where φ is the equivalence ratio, D is the diluent to oxygen molar
fraction ratio (ydiluent /yO2 ) and p is the post-reflected shock pressure.
Westbrook and Dryer [27] presented the first comprehensive methanol reaction mecha-
nism with 26 species and 85 elementary reactions. However, the reaction mechanism failed
to predict the “plateau” in energy release and species concentration profiles that occurred
with increasing equivalence ratio. To address the shortcomings of the model, another re-
action mechanism was proposed by Norton and Dryer [28]. Held and Dryer [29] improved
the model even further but it was enhanced again in the mechanism of Li et al. [1] which
included carbon monoxide and formaldehyde sub-mechanisms.
In this work, the Li et al. [1] model is chosen to simulate ignition delay times because
it is tested against a wider range of experiments and conditions than the Westbrook et al.
[27] and Held et al. [29] models.
Table 2–1: Parameters of methanol shock tube studies.

Author φ D,(= ydiluent /yO2 ) (Diluent) p [atm]
Cooke et al. [24] 1 31.7 (Ar) 0.26–0.40
Bowman [25] 0.375–6 23.5–98 (Ar) 1.2–4.7
Natarajan and Bhaskaran [6] 0.5–1.5 12–18 (Ar) 2.5–4.5
Cribb et al. [26] 0.22–1.33 48/98 (Ar) 0.4–0.9
Fieweger et al. [5] 1 3.76 (N2 ) 13–40
2.1.2 Ethanol
Natarajan and Bhaskaran [30] ignited ethanol in argon-oxygen mixtures at stoichiometric
conditions between 1100 K–1800 K at 0.26 atm–0.40 atm. An overall mechanism for the
oxidation was also proposed, which predicted the ignition delay times reasonably well.
Curran et al. [31] measured ignition delay times of the fuel at low pressures (1.8 atm–4.6
atm), argon-oxygen ratios (D) and equivalence ratios (φ) between 12 and 55, and from
0.25 to 2, respectively. Dunphy et al. [32] developed a reaction mechanism that agreed
5
well with their ignition delay measurements at lean, stoichiometric and rich equivalence
ratios [7]. The model contained 30 species and 97 elementary reactions. More recently,
Heufer and Olivier [9] ignited ethanol/air mixtures at 13, 19 and 41 atm. Marinov [2]
suggested the first comprehensive mechanism that predicted validation targets (ignition
delay times, intermediate species profiles, flame speeds) reasonably well at medium and
high temperatures. However, Li et al. [33] highlighted the inability of the Marinov model
to predict pyrolysis because of the use of incorrect rates of the uni-molecular reactions that
take part in the decomposition pathways of the fuel. Another comprehensive model was
thus developed that included their methanol sub-mechanism [33].
In this work, the Marinov [2] model is chosen to simulate ignition delay times instead
of the Li et al. [33] model even though both mechanisms capture the chemistry relatively
well. Comparisons of sensitivity analyses and ignition delay times would highlight key
differences between the two models. However, the study of modelling approaches (choice of
main decomposition pathway, reaction rate estimation rules, quantum calculations, etc...)
by different research groups is beyond the scope of the current work.
2.1.3 n-Propanol and n-butanol
Johnson et al. [3] studied the ignition of n-propanol and iso-propanol at 1 atm between
1300 K–2000 K and developed a comprehensive mechanism that agreed well with their ex-
perimental results. Frassoldati et al. [34] constructed a meta-model of n-propanol and
C1 to C16 hydrocarbons with 250 species and 7683 reactions. In their counterflow pre-
mixed flame set-up, Veloo et al. [35] measured laminar flame speeds and extinction strain
rates of n-propanol/air, iso-propanol/air and propane/air mixtures. A model was also
presented which predicted experiments accurately, with deviations at rich conditions of
n-propanol/air and propane/air flames. C3 alkane chemistry within the model seemed to
be the cause of the disagreement. Using sensitivity analyses, n-propanol was found to
6
follow a markedly different reaction pathway from iso-propanol. n-Propanol followed a
decomposition that led directly to formaldehyde. The aldehyde was found to be relatively
more reactive than propene, an important intermediate in iso-propanol oxidation.
In this work, the model by Johnson et al. [3] is chosen to simulate ignition delay times
instead of the Frassoldati et al. [34] mechanism since the latter demands larger computing
resources as it is a much larger mechanism.
n-Butanol shock tube experiments were performed by a number of researchers [10,
11, 36] from lean to rich equivalence ratios and pressures of 1 (Black et al.) to 18 atm
(Heufer et al.). Sarathy et al. [4] proposed a n-butanol model using flame speeds and
species profiles exclusively, to validate the model: no shock tube results were set as targets
for the model. More recently, Harper et al. [37] suggested a mechanism using the open-
source software package Reaction Mechanism Generator (RMG). The model was validated
against published data of auto ignition delay times and mole fraction profiles of jet-stirred
reactors and opposed-flow diffusion flames.
The n-butanol model by Sarathy et al. [4] is chosen to simulate ignition delay times as
it is the only model to operate without errors on the chemical equilibrium software package,
CANTERA [38]. Furthermore, the fundamental chemistry of the model is relatively similar
to that of Black et al. [10] and Harper et al. [37].
2.2 Low and high temperature comparative studies
The first comparative study of alcohol ignition can be traced back to Mullins [39] who
vaporized liquid fuels into a heated high speed air stream. The distance between the
injection location and the position of the flame could be translated into a time delay using
the average flow of the carrier fluid (air). Mullins studied a series of alcohols including
methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol and n-decanol. He found
that the activation energies increased with carbon chain length: from 41.3 kcal/mole for
7
5
10
4
10
τ [µs]
3
10
0.9 1 1.1 1.2 1.3

1000/T [1/K]
Figure 2–1: Ignition delay measurements from a hot air stream of primary alcohols by
Mullins (1953) at p = 1 atm. Legend: methanol (), ethanol (), n-propanol (•), n-
butanol (◦), n-pentanol (N), n-hexanol (△), n-decanol (♦).
methanol to 51.7 kcal/mole for n-decanol (Fig. 2–1). Methanol presented the longest
delays whereas n-decanol was relatively easy to ignite especially at high temperatures
(1000 K). In a general sense, as carbon content increased, ignition delay times decreased.
The experimental set-up of Mullins was designed to replicate as closely as possible the
steady, constant pressure deflagration of a liquid fuel in a gas turbine engine. Transport
properties of the flow, depending on the fuel, had a significant effect in the measured delay
times. Chemistry and fluid-flow interactions, being coupled in this set-up, did not allow
for a clear comparison of the auto-ignition chemical kinetics of the alcohols.
In a shock tube, it is assumed that the shock-heated gas is a rest and chemical reac-
tions evolve as in a constant volume reactor. Hence, ignition delay times behind a reflected
shockwave allow for a complete isolation of the combustion chemistry from transport con-
siderations. This added capability of the shock tube over the set-up of Mullins justifies
why the comparative study of Mullins should be investigated again with a different setup.
8
3
10
2
10
τ [µs]
1
10
0
10
0.5 0.6 0.7 0.8 0.9
1000/T [1/K]
Figure 2–2: Ignition delay times of alkanes by Burcat et al. (1971) at φ = 1, p ≈ 10 ± 3
atm. Legend: Methane (N), ethane (+), propane (△), butane (•), pentane (◦).
Burcat et al. [40] performed the first comparative study in a shock tube. He mea-
sured the ignition delay times of C1 -C5 alkanes in simulated air (argon-based) mixtures at
stoichiometry. With the exception of methane and ethane, the larger alkanes had similar
ignition delay times as seen in Fig. 2–2.
2.3 Conclusion
Individual studies of each of the four alcohols have been presented as well as the range of
conditions at which the experiments were carried out. Although the shock tube studies
compare certain alcohols to one another, they do not present comprehensive analyses of how
the alcohols ignite with respect to one another. The only study that performs a comparative
analysis of alcohol ignition is Mullins [39]. The shortcoming however, is that the author
9
investigates ignition indirectly via a experimental set-up that incorporates advection and
diffusion. The work presented in this thesis removes the latter effects to focus on the
chemistry of the four alcohols and presents a comparative analysis of the true ignition
characteristics of the alcohols by means of a shock tube whereby ignition delay times are
measured behind the reflected shock wave at fixed equivalence ratio (φ), dilution (D) and
post-reflected shock pressure (p).
Some would argue that this type of comparative study may not truly reflect the differ-
ent ignition processes of the alcohols due to large uncertainties inherent to the shock tube
technique. Burcat et al. [40], in his study of alkanes, did show that the smaller molecules of
methane and ethane ignited very differently from the larger alkanes that had very similar
ignition delay times. In this work, the objective is to clarify, in a single shock tube, that
the alcohols have ignition delay times that overlap with one another in contrast to their
alkane counterparts.
10
CHAPTER 3
Experimental technique
3.1 Background— shock tubes in chemical kinetics
A brief overview of the basic single pulse shock tube technique as well as the ignition delay
time correlations are presented.
3.1.1 Shock tube gas dynamics
The shock tube wave reactor has been used to study a range of phenomena from the
deflagration, detonation and ignition of gaseous mixtures to the effect of shock waves
on material systems. A review paper by Bhaskaran and Roth [41] evaluates the various
advances in shock tube experiments in the last century. The following text, describing the
single pulse shock tube technique, is inspired by [41] and [42].
A shock tube is composed of two long tubes separated by a mylar diaphragm. Initially,
the system is pumped down to vacuum and one section is filled with a combustible gas
to an initial pressure, p1 , as indicated on Fig. 3–1. This section is denoted as the driven
section, where the gas inside is, in effect, driven by the shock wave.
Thereupon, a shock wave is generated by over-pressuring the other section, denoted as
the driving section, with a driver gas to rupture the diaphragm. The bursting pressure is
denoted as p4 on Fig. 3–1. Helium is used as the driver gas since it produces strong shocks
due to its high sound speed resulting from its low molecular weight. The wave compresses
the low pressure combustible gas adiabatically and eventually reaches the end wall. At
which point, the reflected wave leaves behind a twice shocked region that is stationary
11
Figure 3–1: Shock tube gas dynamics: (a) Shock tube sections; (b) x-t diagram of the wave
system in an ideal shock tube and definition of the ignition delay time, τ ; (c) Pressure
distribution at t=t1 .
12
(ideally). The zone is indicated as Region 5 on the x-t diagram of Fig. 3–1. It is in this
zone that the auto ignition is expected to occur.
The reflected wave, now moving away from the driven end wall, eventually meets the
contact surface which separates the helium from the combustible gas. The moment of their
interaction governs what is know as the test time. The test time, as shown on Fig. 3–1,
is the available time interval for auto-ignition to occur without flow interactions caused
by the arrival of the re-reflected shock wave at the end-wall. The double reflection occurs
when both, contact surface and reflected shock wave, meet.
Behind the contact surface, a third wave system travels towards the driving section:
the expansion fan. It is composed of a series of infinite Mach waves centered at the point
of diaphragm rupture delimited by a head and tail. The expansion waves propagate away
from the driven section which, ensuingly, reflect from the driver end wall and propagate
towards the incoming reflected shock wave.
The equation below, derived from the mass, momentum and energy conservation across
the shock front1 links the ratio of initial pressures, p4 /p1 , to the shock Mach number, MS ,
assuming ideal gases with different sound speeds, a, and specific heat ratios, γ:
−2γ4
p4 1 2
a1 γ 4 − 1 1 γ4 −1
= 2γMS + 1 − γ1 1 − (MS − ) (3.1)
p1 γ+1 a γ1 − 1 MS
As seen in the above equation, the shock Mach number, MS , can be controlled by the
ratio, p4 /p1 . In addition, when changing the shock Mach number (or equivalently, the
shock velocity), the temperature behind the reflected wave, T5 , is also changed.
This post-reflection temperature, T5 , and the resulting pressure, p5 , are the initial
conditions for the evolution of chemical reactions at the end wall in Region 5 of Fig. 3–1.
1 A complete derivation of the state of the gas in region 5 is documented in [42].
13
A time interval is observed between the instant the shock wave reflects off the end wall and
the ignition of the combustible mixture at the end wall. It is this global reaction-dependent
time interval that is called the ignition delay time, τ (See Fig. 3–1).
Having presented the ideal behaviour of the shock tube technique, it is important to
stress the various deviations from theory observed in real shock tubes. Non-ideal effects
can indeed significantly affect the incident wave speed as well as the pressure jump across
the shock wave. The sudden rupture and boundary layer formation behind the shock
wave are the two most significant irreversibilities in a real shock tube [43]. Interaction
between the boundary layer behind the incident shock wave and the reflected wave may
be significant enough to perturb the twice shocked gas behind the reflected shock wave.
Consequently, it may lead to the breakdown of the no-flow assumption used in the modelling
and simulation of shock tube auto-ignition delay times as well as rendering ignition delay
time measurements unreliable.
In a real shock tube, the rupture of the diaphragm by overpressure is non-instantaneous.
The finite time required to rupture the mylar induces a stretching of the contact surface into
a region of mixing of the driven and driver gases. The contact surface eventually accelerates
and meets the reflected wave sooner than predicted by theory [44]. The earlier interaction
shortens the available test time. In this work, the experimentally determined test time is
2 to 3 milliseconds using end-wall pressure profiles of non-reactive argon mixtures instead
of combustible gas.
Viscous effects such as boundary layer formation behind the shock wave contribute to
the decay of the incident shock speed as it travels towards the end wall. An estimate of the
magnitude of this effect can be done by measuring the shock speed at different locations
near the end wall (See Section 3.2) thereby accounting for attenuation of the shock speed
as it hits the end wall.
14
3.1.2 Ignition delay time correlations
It has been suggested [45, 46] that experimental ignition delay times are well captured by
an empirical correlation relating the concentration of fuel, [F ], oxygen, [O], and inert gas,
[I], as well as post reflected shock temperature, T , to the ignition delay time, τ ,
τ = B · [F ]a · [O]b · [I]c · exp (Ea /RT ) (3.2)
where B and Ea are the empirically determined constant and overall activation energy of
the reaction, respectively.
The above correlation can be reformulated in terms of equivalence ratio, φ, dilution,
D, pressure, p, since the concentrations can be linked to molar fractions of the various
species using the ideal gas law. The correlation can then be written as
τ = C · φα · Dβ · pζ · exp (Ea /RT ) (3.3)
The equivalence ratio, φ is defined as
yfuel /yoxi
φ= (3.4)
ν
where y and ν are the species mole fraction and stoichiometric ratio of fuel to oxidizer,
respectively: ν = (yfuel /yoxi )st . The ratio is 2/3, 1/3, 2/9 and 1/6 for methanol, ethanol,
n-propanol and n-butanol, respectively.
The exponents α, β, ζ and Ea are obtained from multivariate linear regression of all the
experiments performed for a single fuel (See Appendix B for the list of all the experimental
ignition delay times). The regression consists of linearizing Eq. (3.3) by taking the natural
logarithm of the equation and re-casting the equation into the following form
ln τ = ln C + α lnφ + β ln D + ζln p + (Ea /R) × (1/T ) (3.5)
15
which can be rearranged into
ln τ = 1 × lnC + ln φ × α + ln D × β + ln p × ζ + (1/T ) × (Ea /R) (3.6)
When written in a matrix form, the correlation becomes

 
    lnC
lnτ 1 lnφ1 lnD1 lnp1 1/T1  
 1    α 

      
 lnτ2  1 lnφ2 lnD2 lnp2 1/T2   
    
 .  = . .. .. .. .. 
 ×  β 
 (3.7)
 .  .
 .   . . . . .    
     ζ  
lnτn 1 lnφn lnDn lnpn 1/Tn  
| {z } | {z } Ea /R
Yn×1 An×5 | {z }
X5×1
where n is the total number of experiments done on a single fuel. In a short form, the
equation is
Y = AX (3.8)
where A is the linearised set of condition parameters φ, D, p and T , Y is the vector of ln(τ )
and X is the vector of the optimized exponents obtained by the method of least-squares
so that
X = (AT A)−1 × AT × Y (3.9)
This approach allows the uncertainty in the fit parameters, and the prediction bounds of
the correlation, to be quantitatively assessed [47]. Specifically, the bounds are obtained
from the calculation of the 95% confidence interval of a student’s t-distribution where
t(αstat /2) = 2 and n varies from 60 to 80 depending on the fuel since each one has a finite
set of experimental data points used in the regression analysis.
In the case of a student’s t-distribution with n degrees of freedom and p parameters,
the non-simultaneous prediction bounds, which include scatter, for measurements is given
16
by [47]
q
Bn,o = ±tn−p (αstat /2) s2 + s2 x(XT X)−1 xT (3.10)
where s is the standard deviation, αstat = 0.05 since a 95% confidence interval is desired,
and x is a specified row vector of experimental conditions i.e. x = [1 ln(φ) ln(D) ln(p5 ) 1000/T5 ].
The subscripts on Bn,o mean that the bounds are non-simultaneous (n) and for new mea-
surement observations (o). To remove scatter from the prediction bounds of the correlation,
the s2 term inside the bracket is discarded. The bounds become

q
Bn,f = ±tn−p (αstat /2) s2 x(XT X)−1 xT (3.11)
The subscripts on Bn,f mean that the bounds are non-simultaneous (n) and for the func-
tion/correlation (f ).
3.2 Experimental set-up and procedure
3.2.1 Description
The physical shock tube is a 7.2 m stainless steel pipe of circular cross-section having a 5
cm inner diameter, with a 4.2 m driven section and a 3 m driving section. The device is
connected to a primary manifold (Manifold 1 on Fig. 3–2) meant to control the gaseous flow
into and out of the shock tube. A secondary manifold (Manifold 2 on Fig. 3–2) is used to
deliver oxygen and argon into the mixing vessel that will contain the combustible mixture.
Braided hoses, rated up to 350 psi, connect the manifold to oxygen, helium and argon
high pressure cylinders and shock tube via the primary manifold (Manifold 1). To reduce
leakages effectively, the secondary manifold (Manifold 2) and the vessel are connected with
stainless steel quarter inch tubing.
Alcohol/oxygen/argon mixtures are prepared manometrically using the secondary
manifold where the mixtures are stored in the 90 l stainless steel mixing vessel. The
vessel is vacuumed for 12 hours with an EDWARDS RV12 rotary vacuum pump until the
17
pressure read from an MKS BARATRON pressure transducer (0-1000 torr) is less than
1 torr. Fuel is then introduced into the mixing vessel via an air-tight HAMILTON syringe
by means of an ultra-torr fitting. From basic phase-change physics, it is assumed that the
initial near-vaccuum conditions (at 25◦ C) within the mixing vessel permit all of the inserted
fuel to be completely vaporis ed. After oxygen and argon are added, the mixture is left to
mix by molecular diffusion for 18–24 hours. The fuel mixtures, obtained in this study, are
presented in Table 3–1 where Xfuel and XO2 are the molar fractions, in percentage, of fuel
and oxygen, respectively.
Methanol, ethanol, n-propanol and n-butanol saturation vapour pressures are 125
torr, 66 torr, 25 torr and 6.6 torr at 25◦ C, respectively [48]. The final partial pressures of
the vaporised fuels are kept below saturation to avoid condensation. For instance, in the
limiting case of n-butanol, when φ was set to 2, the fuel partial pressure reaches 96% of
the saturation vapour pressure.
In addition to mitigating condensation, leakages into and out of the gas-tubing system
are reduced appropriately. The driver and driven sections are found to leak at a rate of
0.0127 and 0.188 torr per minute, respectively. Due to the higher leak rate in the driven
section, the residual gases of the section are mixed with a small amount of combustible gas
to effectively “flush” the driven section. However, the effect of this “flushing” on the final
ignition delay time is found to be insignificant when repeating a data point. The overall
amount of leaked air into the the section is further reduced by initiating the shock wave
within three minutes of introducing the combustible gas into the shock tube.
Furthermore, because initial combustible pressures, p1 , remain greater than 45 torr or
6 kPa (see Appendix B for listing of p1 values), air contamination can only constitute a
maximum of 2.5·10−3 % of p1 . The mixing tank leak rate is measured to be 1.25·10−4 torr
18
Table 3–1: Combustible mixtures.
Fuel φ D = yAr /yO2 Xfuel [%] XO2 [%]
Methanol 1.0 10 5.6 8.6
0.5 15 2.0 6.1
2.0 15 7.7 5.8
1.0 20 3.1 4.6
Ethanol 1.0 10 2.9 8.8
0.5 15 1.0 6.2
2.0 15 4.0 6.0
1.0 20 1.5 4.7
n-Propanol 1.0 10 2.0 8.9
0.5 15 0.67 6.2
2.0 15 2.7 6.1
1.0 20 1.0 4.7
n-Butanol 1.0 10 1.5 8.9
0.5 15 0.52 6.2
2.0 15 2.0 6.1
1.0 20 0.79 4.7
19
Legend:
: Valves : braided hose
signal conditioner
. : Pressure display : stainless steel pipe
pressure transducers Labview

D.A.S.
Polycarbonate diaphragm
photodiode sys.
Driver section Driven section
High Low Optical fibre
pressure pressure
transd. transd.
. . .
pressure
Manifold 2
Manifold 1
transducer
Mixing
.
Tank
Edwards RV12 Injection of

Vaccuum pump He Ar O2 liquid fuel
Exhaust
Figure 3–2: Experimental set-up (not to scale).
per hour. The rate is significantly lower because of the higher volume to opening surface
area ratio and better gas delivery connections.
Four fast-response pressure transducers (three PCB models 113A24 along the side wall
and one PCB model 113A26 at the end wall) are equidistant from each other along the
driven section between 0 and 1.5 m away from the end-wall and an optical fibre is mounted
on the flange of the driven section end-wall to track the progress of the shock wave and find
the instant of auto ignition, respectively. A data acquisition system (National Instruments
PCI 5105) collects the voltage outputs of the transducers and the optical fibre during a
“shot” at 10 MS/s. The pressure traces, shown in Fig. 3–3, are used to find the time
of arrival of the shock wave at the first pressure transducer, located at x = 1.5 m (light
grey line) from the end-wall. The time required for the shock to reach the second pressure
transducer at x = 1.0 m, ∆t, is used to calculate an average shock speed: Us = ∆x/∆t,
20
25
τ
20 Pressure
transducer
(PT) at x=0
Pressure [atm]
15
p5
10
PT at PT at PT at
x=1.5 x=1.0 x=0.5
5
p1
0
−2 −1.5 −1 −0.5 0 0.5 1 1.5 2
Time, t [ms]
Figure 3–3: Pressure traces at x = 0, 0.5, 1.0 and 1.5 m from the end wall driven section
where the arrival of the shock at the end wall marks the start of the fuel/oxygen reaction
i.e. t = 0. τ is the ignition delay time.
21
where ∆x = 0.50 ± 0.001 m. Values of Us are obtained again at x = 0.75 m and x = 0.25 m
to fit an attenuation rate of the incident shock wave (2–5% of Us ). The incident velocity is
extrapolated using a linear fit of the three shock velocities to the end-wall. The intercept
is then used to find the post-reflected shock wave temperature, T5 , using the normal shock
relations of the software GASEQ [49] as well as the initial combustible gas composition.
In order to obtain ignition delay times at different post-reflected shock temperatures,
the shock speed must be equally varied. Since shock velocity and post-reflected shock tem-
perature are intimately linked, by varying the shock speed the temperature can be changed
in the range of 1000 K to 1800 K. As seen in Eq. 3.1, the shock velocity may be controlled
by the pressure ratio, p4 /p1 across the diaphragm prior to rupture. Experimentally, the
ratio is varied solely by changing p1 . Occasionally, the flow into the driver section is slowed
to have a slightly higher p4 in order to strain the diaphragm gradually as opposed to im-
mediately introducing driver gas and causing a quick surge in pressure on the surface of
the diaphragm resulting in a premature break at a lower than desired bursting pressure.
This technique permits reaching the hotter conditions (1650–1800 K).
Behind the reflected shock wave, an auto ignition kernel is formed near the end wall
which releases intermediate species such as activated CH that emit light at wavelengths
λ=410–430 nm [50]. The emissions are captured with the optical fibre placed at the end
wall using an appropriate CH-emissions wavelength filter.
Ignition is defined as the intersection of the first derivative of the CH signal at its
inflection point (maximum gradient) and the reference line of zero emission. The annotated
Fig. 3–4 describes the method. The time delay between the reflection of the shock from
the end-wall and the ignition moment is the experimentally determined ignition delay time,
denoted as τ .
22
4
End wall pressure
3.5
3
τ = 361 µs
2.5
Relative signal
2
CH emission
1.5
0.5
0
0 200 400 600
Time [µs]
Figure 3–4: End wall pressure and CH radical chemilumescence measurements with cor-
responding ignition delay time, τ , for a n-butanol/O2 /Ar mixture with φ = 1.0, D = 10,
p = 10 atm and T = 1173 K. The ignition moment in this case is indicated by the star in
the figure.
23
3.2.2 Simulation of ignition
Studies by Fieweger et al. [5] suggest that the end-wall region behind the reflected shock
wave can be modelled as an ideal, constant volume, adiabatic zero-dimensional reactor
only when a strong, detonation-type ignition occurs (τDDT ) and not a deflagrative ignition
where the ignition is weak i.e. the pressure and CH profiles do not have sharp rises. If the
ignition is strong, then the associated model has initial conditions such that Tini = T5 and
pini = p5 where the initial composition is that of the manometrically prepared combustible
mixture. In terms of dilution and equivalence ratio the molar fractions are 2
φ
yfuel (t = 0) = (3.12)
ν(D + 1 + φ/ν)
1
yoxi (t = 0) = (3.13)
D + 1 + φ/ν
D
yinert (t = 0) = (3.14)
D + 1 + φ/ν
Finally, when the initial conditions are implemented, a constant volume homogeneous
reactor is simulated with CANTERA [38], a chemical kinetic package, and reaction mech-
anisms obtained from literature to extract the species evolution profiles and determine the
simulated ignition delay time.
Concentration profiles of species of interest can then be plotted. Figure 3–5 is an
example of the type of plot that can be extracted from a simulation. In this case, a
methanol/air mixture (φ = 0.22) was ignited at an initial temperature, Tini = 1200 K.
Typically, ignition is identified by the maximum gradient of the pressure evolution profile
(Fig. 3–6). For simulations, the time interval from the start of the simulation t = 0 to the
2 The initial composition equations are derived from the defining equations of φ, D and
from the conservation of species molar fractions where yfuel + yoxi + yinert = 1
24
0
10 300
CH3OH Max dp/dt
Molar Fraction, y
200
dP/dt [atm/ms]
CH O
2
100
−5 H
10 2 OH H
τ = 2.6 ms
CO 0
τ = 2.6 ms
−100
0 1 2 3 0 1 2 3
Time [ms] Time [ms]
Figure 3–5: Species profiles in a zero di- Figure 3–6: Pressure gradient in a zero di-
mensional adiabatic reactor with methanol mensional adiabatic reactor with methanol
and air at φ = 0.22 where T = 1200 K and air at T = 1200 K and p = 1 atm us-
and p = 1 atm using the Li et al. (2007) ing the methanol Li et al. (2007) reaction
methanol reaction mechanism. mechanism.
time of maximum pressure gradient is defined as the ignition delay time, τ . Experimentally,
the sharp pressure rise seen in simulations is akin to the intersection of the maximum slope
of CH-emissions with the baseline zero emissions line [5].
3.2.3 Uncertainty analysis
Uncertainties in the experimental technique may be divided into two categories. The first
category encompasses the inaccuracies that affect post reflected shock temperature, T . The
second category of uncertainties is the measurement of the experimental ignition delay time,
τ.
The primary factor affecting the post reflected shock wave temperature, T , is the
estimation of the incident shock wave velocity, Us−endwall , immediately before the wave is
reflected from the end-wall. The correct extrapolation at the end wall of shock velocities
at 0.25, 0.75 and 1.25 m (where x = 0 m is at the end-wall) is key to accurately obtaining
Us−endwall . Specifically, the uncertainty of the calculated Us is due to the uncertainty in
the measured distances between the pressure transducers, ∆x ± 10−3 m which results in a
25
velocity uncertainty of ±5 m/s. The latter value is calculated using ±10−3 /∆t where ∆t is
approximately 4 · 10−4 s for a relatively high shock speed of 880 m/s. Note that the error
in ∆t is negligible because of the rapid-response time of the pressure transducers which
captures the shock arrival at each pressure transducer within 10−7 seconds or 1.8 · 10−4 %
of ∆t which leads to a velocity uncertainty of ±0.2 m/s. Consequently, the global effect of
the uncertainty on temperature is then calculated from a velocity change propagated in the
temperature calculation of the GASEQ software package. The velocity-related uncertainty
is finally evaluated to be ±15 K as shown on Fig. 3–7.
A secondary source of uncertainty of T is the exact amount of vaporised fuel when
mixtures are prepared manometrically. The measured partial pressures of the gases, pfuel ,
poxi and pAr have an error of ±0.12% which corresponds to a negligible error in the final
molar fractions of the three compounds yfuel , yoxy and yAr (Order of 10−6 ).
Errors in the molar fraction of fuel may be introduced from condensation of fuel in
the mixing tank as was the concern of the author in the case of the least volatile alcohol,
n-butanol. Using a conservative estimate that 10% of fuel condenses, the new amount of
fuel (= 0.90 yfuel ) in the mixing vessel is inputed into the chemical equilibrium software
GASEQ to monitor the change in T . In the case of n-butanol, the resulting change in
temperature is found to be ± 5.8 K.
Having evaluated the uncertainties in T to be ±5.8 K and ±15 K for condensation and
velocity-related uncertainties, respectively, we may now address the uncertainty related to
measuring ignition delay time, τ .
The slope of the rise due to ignition of CH emissions is the governing issue that
influences the accuracy of the measured τ . The uncertainty comes from choosing which
section of the CH rise should be considered as the true marker of ignition. If there are
several steps or levels to the CH emission rise, then the sharpest rise must be chosen. In
26
3
10
τ [µs]
2
10
1
10
0.65 0.7 0.75 0.8 0.85
1000/ T [1/K]
Figure 3–7: Ignition delay times of n-butanol (Mix 1): φ = 1, D = 10, p = 10 atm with
temperature error bars (±15 K).
cases where the sharpest rise is difficult to notice, the uncertainty can vary from ±5 µs
for short ignition delay times to ±100 µs for larger values. Choosing which CH rise is the
sharpest is done at the discretion of the experimenter since parameters are changed in the
data-extracting MATLAB script.
For example, in Fig. 3–4, the second rise of CH emissions is not synchronized with
the first pressure jump. Choosing the associated tangent at maximum gradient would not
evaluate the same delay time indicated by the pressure trace in the shock tube.
Essentially, the ambiguous nature of certain weak CH signals or irregular CH ignition-
induced rises affect to different degrees the final τ value: from a 1% to 40% of the measured
value.
27
CHAPTER 4
Results and discussion
4.1 Experimental results
The experimental ignition results of the four primary alcohols are presented as semi-log
plots of τ against 1000/T at fixed equivalence ratio, φ, dilution (yAr /yO2 ), D, and approx-
imately constant post-reflected shock pressure, p. The 6 sets of conditions are presented
in Table 4–1.
Table 4–1: Experimental conditions for methanol (C1 : 1 carbon molecule) to n-butanol
(C4 : 4 carbons molecule) ignition delay times measurements.
Condition φ D p [atm]
1 1 10 2
2 1 10 10
3 1 20 2
4 1 20 10
5 0.5 15 12
6 2 15 2
The slight variations in pressure, which affect ignition delay times, are corrected by
scaling the delay times using the power law:
τ ∝ pζ (4.1)
where ζ is the pressure exponent (varies from −0.53 to −0.85) obtained from linear regres-
sion of the experimental data as presented in Table 4–4.
Figure 4–1 shows the ignition delay times of the alcohols at D = 10 and p = 10
atm. Methanol has the shortest ignition delay times the four alcohols. The correlation
28
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
Figure 4–1: Alcohol ignition delay times, Figure 4–2: Alcohol ignition delay times,
τ , at φ = 1, D = 10, p = 10 atm. Data: τ , at φ = 1, D = 10, p = 2 atm. Data:
methanol (+), ethanol (◦), n-propanol methanol (+), ethanol (◦), n-propanol
(△), n-butanol (), C2 -C4 correlation line (△), n-butanol (), C1 -C4 correlation line
(black dash line). (black line).
for the C2 -C4 alcohols lies above the methanol data. The extremely low level of scatter
of the methanol data in the figure indicate that the shorter ignition delay times of the
fuel relative to the other fuels are statistically significant. When the equivalence ratio is
reduced to φ = 0.5 (Fig. 4–3), the results portray a stronger similarity of the respective
alcohol delay times relative to when φ is 1. Indeed, the methanol values are not slightly
shorter as in the stoichiometric case. When the equivalence ratio is increased again to φ = 2
on Fig. 4–4, the ignition delay times of the alcohols distance themselves from each other,
particularly at high temperatures. Essentially, the collapse seen in lean and stoichiometric
conditions is not as apparent at rich conditions.
When the post-reflected shock pressure is reduced to 2 atm, as shown on Fig. 4–2, the
alcohols also possess similar delay times to one another. However, there are two differences
from the p = 10 atm case (Fig. 4–1).
29
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
τ , at φ = 0.5, D = 15, p = 12 atm. Data: τ , at φ = 2, D = 15, p = 2 atm. Data:
methanol (+), ethanol (◦), n-propanol (△) methanol (+), ethanol (◦), n-propanol (△)
and the correlation prediction bounds ex- and the correlation prediction bounds ex-
cluding scatter using a 95% confidence including scatter using a 95% confidence in-
terval (dash lines), n-butanol (), C1 -C4 terval (dash lines), n-butanol (), C1 -C4
correlation line (black line). correlation line (black line),
The first difference is that the delay times of all four alcohols are generally longer
and appear to be higher caused by the lower post-reflected shock pressure. Hence, since
pressure is directly related to molecular collisions of the gas on a unit surface area. The
collisions of oxidizer and fuel are thereby reduced which causes longer ignition delay times.
The second difference is that the delay times are shifted to the left because at lower
temperatures much higher delay times would be obtained. These higher delay times would
in fact be greater than the experimentally obtained test time of 2–3 milliseconds. By
obtaining ignition delay times in between 20 and 1500 µs, the corresponding temperatures
must be higher which creates the impression of a right to left shift of the data. The
result from this shift is the accessibility of higher temperatures; thereby permitting the
measurement of delay times within the narrow range of valid ignition delay times.
30
Table 4–2: Experimental parameters of the correlation: τ = C · φα · Dβ · pζ · exp (Ea /RT ).
1 φ D p [atm] T [K]
C α β ζ Ea [kcal/mol]
Experiments
Methanol 29×10−4 -0.82 ± 0.07 1.10 ± 0.08 -0.85 ± 0.04 25.3 ± 0.5
Ethanol 1.7×10−4 -0.36 ± 0.08 0.98 ± 0.09 -0.61 ± 0.04 32.1 ± 0.7
n-Propanol 0.55×10−4 -0.51 ± 0.14 1.50 ± 0.21 -0.53 ± 0.09 30.9 ± 1.2
n-Butanol 1.6×10−4 -0.53 ± 0.14 0.78 ± 0.07 -0.59 ± 0.07 33.3 ± 1.3
C1 -C4 alcohols 8.6×10−4 -0.58 ± 0.14 1.00 ± 0.21 -0.69 ± 0.09 28.0 ± 1.3
Ethanol overlaps with n-propanol and n-butanol at all six conditions except at high
dilutions/low pressures (Fig. 4–5).
The n-propanol prediction bounds on Figs. 4–3 and 4–4 reflect the bounds of the
correlation without accounting for scatter. Having obtained the confidence interval of the
n-propanol data, the relatively shorter delay times at lean and rich conditions are not
statistically significant, therefore indicating varying degrees of collapse of the delay times
of the alcohols at rich and lean conditions.
n-Butanol has an apparent activation energy (slope of the averaged data) that is higher
than that of the other fuels as seen in Table 4–2 but is still relatively close to C2 and C3
alcohols. The correlation parameters will be discussed with more detail in Section 3.1.2.
The effect of the argon to oxygen ratio D at φ = 1 on the relative ignition delay times
between the fuels is also investigated.
At D = 20 and p = 10 atm (Fig. 4–6), the alcohols overlap once again. Below
1000/T = 0.75, n-butanol seems to be the easiest to ignite but this observation is deemed
statistically insignificant since the data below 1000/T = 0.75 fall somewhat outside the
prediction bounds of the n-butanol correlation.
At the same dilution D = 20 but at a lower pressure, p = 2 atm, (Fig. 4–5) the ignition
delay times of the alcohols distance themselves from one another a little more. Methanol
31
3
10
3
10
τ [µs]
τ [µs]
2
10
2
10
1
10
1 0.6 0.7 0.8 0.9
10 1000/T [1/K]
0.6 0.7 0.8 0.9
1000/T [1/K] Figure 4–6: Alcohol ignition delay times,
τ , at φ = 1, D = 20, p = 2 atm.
Figure 4–5: Alcohol ignition delay times,
Data: methanol (+) and the correlation
τ , at φ = 1, D = 20, p = 10 atm. Data:
prediction bounds excluding scatter using
methanol (+), ethanol (◦), n-propanol
a 95% confidence interval (dot-dash lines),
(△), n-butanol () and the correlation
ethanol (◦), n-propanol (△), n-butanol
prediction bounds excluding scatter using
() and the correlation prediction bounds
a 95% confidence interval (dash lines), C1 -
excluding scatter using a 95% confidence
C4 correlation line (black line).
interval (dash lines), C1 -C4 correlation line
(black line).
and n-propanol have similar ignition delay times that are noticeably longer than those of
ethanol and n-butanol. In this case, the difference are statistically significant since the
points fall within the prediction bounds of methanol and n-butanol that are significantly
longer and shorter, respectively, at higher temperatures.
Since scatter is clearly visible in the above results, correlations obtained from linear
regression of the data remove this experimental scatter and help focus on the trends of each
fuel with respect to each other. In addition, when prediction bounds of the correlations
are included, the uncertainties of each correlation can be inspected. The bounds of each
fuel provide a visual indication of the level of confidence of the experimentally obtained
results.
32
Figure 4–7 plots the upper and lower prediction bounds of τ of the correlation of each
fuel at φ = 0.5, D = 10, p = 10 atm. The same line type for both bounds is used according
to alcohol. From the figure, it is observed that the prediction bounds of the four alcohols
collapse throughout most of the studied temperature range. The collapse of uncertainties
thereby confirm that the ignition delay times equally overlap at the mentioned conditions.
When the equivalence ratio is changed to stoichiometry, the prediction bounds are
somewhat larger but there is still an overlap of the latter as seen on Fig. 4–8. In both
figures however, the prediction bounds of n-propanol and n-butanol are noticeably larger
than those of methanol and ethanol thus making the uncertainty in the C3 -C4 results
relatively more significant. The reason for this sizable level of uncertainty in n-propanol
and n-butanol may be due to the nature of oxidation kinetics of larger molecules in general.
The presence of more breakable bonds as well as the increase in possible intermediates
generates a large number of oxidation pathways that the alcohols can take depending on
the pressure, temperature and flow conditions behind the shock. However, the true reason
for the uncertainty in the higher alcohols results remains challenging to uncover.
Figure 4–9 plots the prediction bounds at φ = 2, D = 10, p = 10 atm. The bounds of
n-butanol are again larger than those of the other fuels, making an overlap of the results still
visible, albeit a messier one compared to that of the lean predictions (Fig. 4–7). Specifically,
the methanol prediction bounds fall shorter at low temperatures (1000/T > 0.8), the n-
propanol ones stay in an intermediate region between the n-butanol and the methanol
bounds whereas the ethanol bounds are contained within those of n-butanol.
Consequently, having visualised the uncertainties in the ignition delay times at lean,
stoichiometric and rich conditions, there is conclusive evidence indicating stronger collapse
of all four alcohols at lean equivalence ratios. The collapse weakens as the equivalence ratio
is increased to φ = 1 and then φ = 2. These results are also enforced by the divergence of
33
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
Figure 4–7: Upper and lower prediction Figure 4–8: Upper and lower prediction
bounds of the correlations at φ = 0.5, bounds of the correlations at φ = 1, D =
D = 10, p = 10 atm of methanol (thin 10, p = 10 atm of methanol (thin grey dash
grey dash lines), ethanol (grey dot-dash lines), ethanol (grey dot-dash lines), n-
lines), n-propanol (black dash lines) and propanol (black dash lines) and n-butanol
n-butanol (black solid lines). (black solid lines).
3
10
τ [µs]
2
10
1
10
0.6 0.7 0.8 0.9
1000/T [1/K]
Figure 4–9: Upper and lower prediction bounds of the correlations at φ = 2, D = 10,
p = 10 atm of methanol (thin grey dash lines), ethanol (grey dot-dash lines), n-propanol
(black dash lines) and n-butanol (black solid lines).
34
Table 4–3: Details of mechanisms in this study
Mechanism Species Reactions Fuel reactions Fuel unimolecular reactions
Methanol by Li et al. [1] 21 93 18 3
Ethanol by Marinov [2] 58 383 19 4
Propanol by Johnson et al. [3] 237 2624 100 12 (8 reversible)
n-Butanol by Sarathy et al. [4] 117 884 66 6
the n-butanol prediction bounds to larger ignition delay times and the descent of methanol
bounds to shorter values at φ = 2.
4.2 Simulation results
The comparison of experimental results to simulations are first presented by fuel followed
by a discussion on the relative similarities and differences of ignition delay times of the
fuels. Simulated ignition delay times are obtained using the 0-D reactor; described in
Section 3.2.2 along with chemical kinetic models for each alcohol presented on Table 4–3.
It has been found that agreement between model and experiment does not change
significantly from one condition to another. Hence, only one condition (φ = 2, D = 15
and p = 2 atm) is presented to compare simulation to experiment. Figures 4–10 to 4–14
show the individual comparisons of experiments to simulation by fuel. The ethanol model of
Marinov [2] predicts experimental results with the highest level of accuracy where deviation
are by a factor of 1.5. The methanol model of Li et al. [1] is within a factor of 2.5 from
experiments. The n-butanol model of Sarathy et al. [4] performs relatively well compared
to the n-propanol model of Johnson et al. [3]. The models disagree with experiments by
factors of 6 and 10 for n-butanol and n-propanol, respectively. Nonetheless, at different
conditions the n-propanol model shows relatively good agreement to experiments as in
the stoichiometric case (Fig. 4–13) especially at higher temperatures where the level of
agreement is within a factor of 2.
Having seen the relative ignition behaviour of the alcohols in experiments, it is impor-
tant to evaluate how the models predict the collapse of C1 to C4 alcohols at φ = 1, D = 10,
35
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
Figure 4–10: Methanol ignition delay Figure 4–11: Ethanol ignition delay times,
times, τ , at φ = 2, D = 15, p = τ , at φ = 2, D = 15, p = 2 atm. Data:
2 atm. Data: methanol (+). Simulations: ethanol (◦). Simulations: ethanol [2] (dash
methanol [1] (dot line). line)
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
Figure 4–12: n-Propanol ignition delay Figure 4–13: n-Propanol ignition delay
times, τ , at φ = 2, D = 15, p = 2 atm. times, τ , at φ = 1, D = 20, p = 2 atm.
Data: n-propanol (△). Simulations: n- Data: n-propanol (△). Simulations: n-
propanol [3] (thin solid line). propanol [3] (thin solid line).
36
3
10
τ [µs]
2
10
1
10
0.6 0.7 0.8 0.9
1000/T [1/K]
Figure 4–14: n-Butanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:
n-butanol (). Simulations: n-butanol [4] (thick solid line).
p = 10 atm as plotted on Fig. 4–15. The figure is simply Fig. 4–1 with the addition of
simulation curves. From the plot, it is found that the models fail to show the overlap of
the experimental ignition delay times of the alcohols. In addition, the models, with the
exception of ethanol, over-predict the experimental data by factors of 3 to 8 where poorer
agreement is seen at low temperatures (1000/T ≈ 0.9) in the cases of the n-propanol [3] and
n-butanol [4] models. Nevertheless, the C3 -C4 alcohol models do overlap but significantly
over-predict their respective experimental data.
The lack of overlap of all four fuels, in the simulated delay times, is also seen when the
dilution is increased to D = 20 as seen on Fig. 4–16. Similarly at lean conditions where
D = 15 and p = 12 atm as well as at rich conditions where D = 15 and p = 2 atm as seen
of Fig. 4–17 and Fig. 4–18, respectively.
4.3 Correlation parameters of ignition delay times
The experimental data presented previously can be expressed in the empirical correlation:
τ = C · φα · Dβ · pζ · exp (Ea /RT ). By calculating the constants C, α, β, ζ and Ea through
37
3
10 10
3
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
τ , at φ = 1, D = 10, p = 10 atm. τ , at φ = 1, D = 20, p = 10 atm.
Data: methanol (+), ethanol (◦), n- Data: methanol (+), ethanol (◦), n-
propanol (△), n-butanol (). Simulations: propanol (△), n-butanol (). Simulations:
methanol [1] (dot line), ethanol [2] (dash methanol [1] (dot line), ethanol [2] (dash
line), n-propanol [3] (thin solid line), n- line), n-propanol [3] (thin solid line), n-
butanol [4] (thick solid line). butanol [4] (thick solid line).
linear regression (tabulated in Table 4–4), a quantitative assessment of the influence of ini-
tial fuel/oxygen/diluent composition and pressure on ignition delay time may be extracted
from ignition delay times measured at the six different conditions (Table 4–1).
The same correlation approach can be applied to chemical kinetic mechanisms. Mech-
anism correlation parameters are obtained from simulations in the constant volume, adi-
abatic reactor at initial conditions determined using a random number generator [51]. In
the simulations, equivalence ratio, φ, is varied between 0.2–2.5, argon/oxygen ratio, D,
from 3.76 to 25, pressure, p, from 1 to 20 atm, and temperature, T , from 1150 to 1500 K
corresponding to 250 simulations in total.
From the results of the regression, the correlation parameters C and Ea are the only
parameters that significantly alter ignition delay times. The effect of α, β, and ζ on ignition
38
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1
10 10
1
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
−1
1000/T [K ] 1000/T [1/K]
τ , at φ = 0.5, D = 15, p = 12 atm. τ , at φ = 2, D = 15, p = 2 atm.
Data: methanol (+), ethanol (◦), n- Data: methanol (+), ethanol (◦), n-
propanol (△), n-butanol (). Simulations: propanol (△), n-butanol (). Simulations:
methanol [1] (dot line), ethanol [2] (dash methanol [1] (dot line), ethanol [2] (dash
line), n-propanol [3] (thin solid line), n- line), n-propanol [3] (thin solid line), n-
butanol [4] (thick solid line). butanol [4] (thick solid line).
delay time, τ , compared to C and Ea , is relatively weak since the exponents are in the range
of −1 and 1.5 (Table 4–4).
Regression of methanol experiments reveal a relatively large C constant, 29×10−4 as
well as a low activation energy of 25.3 kcal/mol. Furthermore, the alcohol has the highest
sensitivity to equivalence ratio (α = −0.82) and pressure (ζ = −0.85).
The experimental ethanol Ea (32.1 kcal/mol) may seem to break the overall trend of
increasing activation energy with increasing alcohol size. However, the associated uncer-
tainty of ±0.7 is large enough to overlap the ethanol value with that of n-propanol and
n-butanol which are 30.9 ± 1.2 kcal/mol and 33.3 ± 1.3 kcal/mol, respectively. The similar
activation energies of C2 to C4 alcohols is also seen in the correlation parameters from the
mechanisms.
39
Table 4–4: Experimental and simulation parameters of the correlation: τ = C · φα · Dβ ·
pζ · exp (Ea /RT ).
1 φ D p [atm] T [K]
C α β ζ Ea [kcal/mol]
Experiments
Methanol 29×10−4 -0.82 ± 0.07 1.10 ± 0.08 -0.85 ± 0.04 25.3 ± 0.5
Ethanol 1.7×10−4 -0.36 ± 0.08 0.98 ± 0.09 -0.61 ± 0.04 32.1 ± 0.7
n-Propanol 0.55×10−4 -0.51 ± 0.14 1.50 ± 0.21 -0.53 ± 0.09 30.9 ± 1.2
n-Butanol 1.6×10−4 -0.53 ± 0.14 0.78 ± 0.07 -0.59 ± 0.07 33.3 ± 1.3
C1 -C4 alcohols 8.6×10−4 -0.58 ± 0.14 1.00 ± 0.21 -0.69 ± 0.09 28.0 ± 1.3
Simulations
Methanol [1] 12.0×10−4 -0.63 ± 0.00 0.86 ± 0.01 -0.93 ± 0.00 30.3 ± 0.1
Ethanol [2] 0.74×10−4 -0.34 ± 0.02 0.81 ± 0.02 -0.71 ± 0.02 35.9 ± 0.4
Propanol [3] 1.7×10−4 -0.33 ± 0.01 0.81 ± 0.02 -0.75 ± 0.02 35.8 ± 0.3
n-Butanol [4] 0.21×10−4 -0.27 ± 0.02 1.1 ± 0.07 -0.60 ± 0.07 38.3 ± 0.4
In addition, the models underpredict the effect of composition (φ, D) with respect to
the experimentally obtained α and β. For example, α (related to equivalence ratio, φ) of
the n-butanol mechanism is −0.27 ± 0.02 as opposed to the −0.53 ± 0.14 from experiments.
Having developed an empirical correlation that accounts for changes in φ, D and
p, we can compare results against ignition delay times from literature obtained at other
equivalence ratios, dilutions and pressures.
Fieweger et al. [5] studied methanol ignition delay times in air and reported two
different types of ignition delay times: deflagration and detonation. On Fig. 4–19, the
detonation results are compared against the current methanol experimental correlation.
Agreement between the two sets of data is limited where the values of the correlation are
lower by a factor of 3. The source of the discrepancy may originate from the relatively
low dilution (D = 3.76) and the use of nitrogen instead of argon as the diluent. Natarajan
and Bhaskaran also studied methanol and their results do not agree with the correlation
as shown on Fig. 4–20.
40
3
10
τ [µs]
2
10
1
10
0.8 0.9 1 1.1
1000/T [1/K]
Figure 4–19: Comparison between experimental and literature ignition delay times of
methanol. Legend: Fieweger et al. [5] (+) and methanol experimental correlation from
Table 4–4 (dash line) at φ = 1, D = 3.76, p = 13.2 atm.
The correlation over-predicts the Natarajan and Bhaskaran data by a factor 4 to
5. The two comparisons of the methanol correlation shows an underprediction and an
overprediction of previously obtained values. The lack of a systematic trend between
correlation and literature data indicates that the experimental results are not incorrect.
Ethanol ignition delay times have been reported previously in the literature as pre-
sented in the literature review (p. 5). On Fig. 4–21, the data of Dunphy et al. [7] and
Akih-Kumgeh and Bergthorson [8] at φ = 0.5, D = 12.2 and p = 3.5 atm are plotted
against the ethanol correlation. There is excellent agreement with the correlation since the
respective values differ only by a factor of about 1.1. The figure also shows the data of
Heufer and Olivier [9] at φ = 1, D = 3.73 and p = 19 atm which also agrees well with the
ethanol correlation, i.e., by a factor of 1.3.
n-Propanol results of Johnson et al. [3] are compared against the respective exper-
imental correlation at φ = 2, D = 83 (with argon as the diluent) and p = 1.1 atm as
41
3
10
τ [µs]
2
10
1
10
0.55 0.6 0.65 0.7 0.75
1000/T [1/K]
methanol. Legend: Natarajan and Bhaskaran [6] (+) and methanol experimental cor-
relation from Table 4–4 (dash line) at φ = 0.5, D = 12, p = 12.5 atm.
3
10
τ [µs]
2
10
1
10
0.6 0.8 1 1.2
1000/T [1/K]
ethanol. Legend: Dunphy et al. [7] (), Akih-Kumgeh & Bergthorson [8] (×) and ethanol
experimental correlation from Table 4–4 (solid line) at φ = 0.5, D = 12.2, p = 3.34 atm.
Heufer and Olivier [9] (◦) and ethanol experimental correlation (dash line) at φ = 1,
D = 3.73, p = 19 atm.
42
3
10
τ [µs]
2
10
1
10
0.5 0.6 0.7
1000/T [1/K]
Figure 4–22: Comparison of correlations derived in this study with literature data on n-
propanol ignition. Legend: n-propanol Johnson et al. [3] (△) and n-propanol experimental
correlation from Table 4–4 (dot-dash line) at φ = 2, D = 83, p = 1.1 atm.
seen in Fig. 4–22. The agreement is relatively good where differences in the values of the
correlation and literature experiments remains below a factor of 2.
n-Butanol ignition delay times from Black et al. [10] and Heufer et al. [11] obtained
at φ = 1, D = 26.6, p = 8 atm and φ = 1, D = 3.73, p = 13 atm, respectively, are
compared to the corresponding experimental correlation on Fig. 4–23. The correlation
performs relatively well in obtaining ignition delay times that match the two studies by
factors of 1.1–1.2.
The figure also plots the two conditions (lean and stoichiometric) studied by Hanson
et al. [12]. The correlation agrees well and slightly over-predicts the lean results by a factor
of 1.2–1.5. The stoichiometric data of Hanson et al. is in agreement with the correlation
only above 1000 K. Below 1000 K, the correlation is not extended because the correlation is
only valid in the experimentally limited 1000 K–1400 K range. Comparing the correlation
to the experimental data of Hanson et al. in an extrapolated temperature region would be
43
4
10
3
10
τ [µs]
2
10
1
10
0.6 0.8 1 1.2
1000/T [1/K]
Figure 4–23: Comparison of correlations derived in this study with literature data on n-
butanol ignition. Legend: Black et al. [10] (△) and n-butanol experimental correlation
from Table 4–4 (thick solid line) at φ = 1, D = 26.6, p = 8 atm. Heufer et al. [11] (◦) and
current study correlation (dot-dash line) at φ = 1, D = 3.73, p = 13 atm. Hanson et al.
[12] () and n-butanol experimental correlation from Table 4–4 (thin solid line) at φ = 0.5,
D = 23.83, p = 19 atm. Hanson et al. [12] (+) and n-butanol experimental correlation
from Table 4–4 (dot line) at φ = 1, D = 3.76, p = 22 atm.
incorrect. Furthermore, there is a noticeable change in activation energy below 1000 K as
seen by the dip in delay times.
By plotting the ethanol and n-butanol results of Heufer and Olivier [9] and Heufer
et al. [11] on a single figure (Fig. 4–24), it is seen that the respective ignition delay times
overlap as was observed in the present data. The similarity of the fuels showcases the
power of comparing fuels using only previously published data. The comparative approach
is inspired by the work of Akih-Kumgeh and Bergthorson [52] who evaluated the effect of
different functional groups on ignition delay times of bio-diesel surrogate molecules.
44
3
10
τ [µs]
2
10
1
10
0.6 0.8 1 1.2
1000/T [1/K]
ethanol and n-butanol. Legend: Heufer and Olivier [9] (◦) and ethanol experimental
correlation (dash line) at φ = 1, D = 3.73, p = 19 atm and Heufer et al. [11] (△) and
current study correlation (dot-dash line) at φ = 1, D = 3.73, p = 13 atm.
4.4 Reaction rate dependency analysis
Experimental results, having been described previously and validated against literature
results, must now be understood from a reaction-based study by performing reaction rate
dependency analyses of the chemical kinetic models of the fuels.
Dependency of a reaction, denoted Reaction i, on the ignition delay time is evaluated
by comparing a regular ignition delay time, τref to one obtained from a modified reaction
mechanism where the reaction is suppressed, τi . The suppression of Reaction i is accom-
plished by multiplying the rate, denoted kref , of Reaction i by a near-zero (0.01) constant
m1 . Using the updated reaction rate, ki (= m × kref ), an associated ignition delay time,
1 Using a multiplying coefficient, m, that is strictly equal to 0 occasionally causes simula-

tions to diverge if Reaction i is critical for the system to evolve. For example, the reaction
responsible for the consumption of ethanol in the Marinov model: C2 H5 OH + HO2 ⇋
C2 H4 OH + H2 O2 cannot be removed.
45
τi is obtained. Once τi and τref are simulated, the effect of removing Reaction i on τ is
expressed by the sensitivity coefficient
∂(log τ ) ∆τ k τi − τref 0.5(ki + kref )

Si = ≈ ≈ (4.2)
∂(log k) τ ∆k 0.5(τi + τref ) ki − kref
where k is the reaction rate expressed in the Arrhenius form: k = A · T n · exp(Ea /RT ).
Since ki = m × kref , Eq. (4.2) can be written as
τi − τref 0.5(m × kref + kref )

Si = (4.3)
0.5(τi + τref ) m × kref − kref
kref cancels out from Eq. (4.3) which yields
τi − τref m + 1
Si = (4.4)
τi + τref m − 1
The calculation is repeated for each reaction in the mechanism and a bar plot is drawn of
the 15 most important reactions as seen in Figs. 4–25 to 4–28.
For methanol (Fig. 4–25), hydrogen peroxide and fuel dehydrogenation reactions con-
trol ignition delay time where Si = −0.82 and −0.64, respectively. The negative sign of
the sensitivity coefficients indicate that “removing” (m ≈ 0) the reaction will reduce the
reactivity of the mixture, consequently increasing the ignition delay time.
Chain-branching and fuel-specific reactions control ethanol ignition (Fig. 4–26). Alka-
nes, which rarely appear in the analyses of the other models, take part in the oxidation
of ethanol as seen by their presence in the top 15 reactions i.e. C2 H3 +CH3 ⇋ C2 H2 +CH4
and C2 H2 +O2 ⇋C2 H3 +HO2 .
Similarly to the previous alcohols, the propanol model verifies the importance of radical
chemistry over fuel-specific reactions with are consistently ranked below chain-branching
reactions (Fig. 4–27).
46
H2O2 (+ M) <=> OH + OH (+ M)
CH3OH + HO2 <=> CH2OH + H2O2
CH3OH + O2 <=> CH2OH + HO2
HO2 + HO2 <=> H2O2 + O2
CH3OH + H <=> CH2OH + H2
CH3OH + OH <=> CH3O + H2O
H + O2 <=> O + OH
CH2O + HO2 <=> HCO + H2O2
HO2 + OH <=> H2O + O2
CH2O + OH <=> HCO + H2O
CH3O + M <=> CH2O + H + M
HCO + O2 <=> CO + HO2
H2O2 + OH <=> HO2 + H2O
HO2 + H <=> OH + OH
CH3OH + O <=> CH2OH + OH
−0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6
Si
Figure 4–25: 15 most important reactions from the reaction rate dependency analysis
(m = 0.01) of the methanol mechanism by Li et al. [1] for a stoichiometric methanol/O2 /Ar
mixture at 7 atm with argon/oxygen ratio, D, of 12 at a temperature of 1200 K. The
unperturbed ignition delay time is 330 µs.
H2O2 + O <=> OH + HO2

O + H2 <=> H + OH
CH2 + HO2 <=> CH2O + OH
C2H2 + OH <=> HCCOH + H
CH2 + O2 <=> HCO + OH
HCO + OH <=> CO + H2O
CH2 + O <=> HCO + H
H2O2 + H <=> H2O + OH
C2H3 + CH3 <=> C2H2 + CH4
HCO + O <=> CO2 + H
C2H4 + O2 <=> C2H3 + HO2
CO + HO2 <=> CO2 + OH
O + H + M <=> OH + M
CO + O2 <=> CO2 + O
HCCO + CH2 <=> C2H3 + CO
−0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6
Si
(m = 0.01) of the ethanol mechanism by Marinov [2] for a stoichiometric ethanol/O2 /Ar
mixture at 7 atm with argon/oxygen ratio, D, of 12 at a temperature of 1200 K. The
unperturbed ignition delay time is 650 µs.
47
HO2 + HO2 => H2O2 + O2
C3H6 + OH => C3H6OH−2
CH3O + OH => CH3 + HO2
C3H6OH−2 + H2O => NC3H7OH + OH
OH + O2 => HO2 + O
CH3 + CH3 (+ M) <=> C2H6 (+ M)
C3H6OH−2 + H2 => NC3H7OH + H
HO2 + HO2 => H2O2 + O2
CH2CHO => C2H3O1−2
C2H3O1−2 + CH3OH => C2H4O1−2 + CH3O
C3H5O + OH => AC3H5OOH
H + O2 => O + OH
C3H5−A + CH3 => C4H8−1
HCO + H2O => CH2O + OH
CH3 + H (+ M) <=> CH4 (+ M)
−0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6
Si
Figure 4–27: 15 most important reactions from the reaction rate dependency analysis (m =
0.01) of the iso-propanol/n-propanol mechanism by Johnson et al. [3] for a stoichiometric
n-propanol (n−C3 H7 OH)/O2 /Ar mixture at 7 atm with argon/oxygen ratio, D, of 12 at a
temperature of 1200 K. The unperturbed ignition delay time is 1692 µs. Note that reaction
1: HO2 +HO2 ⇋ H2 O2 +O2 has a duplicate reaction with another set of rate parameters.
48
OH + OH (+ M) <=> H2O2 (+ M)
CC4H8OH => CH2OH + C3H6
H + O2 <=> OH + O
AC4H8OH => CH3HCO + C2H5
HCO + O2 <=> CO + HO2
AC3H5 + H (+ M) <=> C3H6 (+ M)
CH3 + HO2 <=> CH3O + OH
AC4H8OH <=> DC4H8OH
C2H4 + H (+ M) <=> C2H5 (+ M)
C2H4 + OH <=> C2H3 + H2O
HO2 + HO2 <=> H2O2 + O2
C4H7OHZ => OH + MEALL
C2H3 + O2 <=> CH2HCO + O
CH2O + AC3H5 <=> HCO + C3H6
AC3H5 + HO2 <=> C3H5O + OH
−0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6
Si
(m = 0.01) of the n-butanol mechanism by Sarathy et al. [4] for a stoichiometric n-
butanol (or n−C4 H9 OH)/O2 /Ar mixture at 7 atm with argon/oxygen ratio, D, of 12 at a
temperature of 1200 K. The unperturbed ignition delay time is 917 µs.
49
The n-butanol model also exhibits strong radical chemistry dependence as well as fuel
specific decomposition reactions. For instance, as shown in Fig. 4–28, the reaction OH +
OH ⇋ H2 O2 appears as the most important. The latter is a pressure dependent reaction
that is extremely important in all alkane oxidation chemistry as well.
In summary of the rate analyses of the various models, radical chemistry governs
ignition and to a lesser extent, fuel-specific decomposition reactions of larger alcohols,
such as n-butanol, control the rate of consumption of fuel and the size of the pool of
intermediates.
A review of the reaction rate parameters included in the reaction mechanisms of the
alcohols reveals that there is agreement in the assignment of rate parameters of key reac-
tions between the models. Only very few rate constants appear to vary: for example, for
the reaction H2 O2 +O⇋OH+HO2 , the n-butanol model has a large A value of 2.80 × 1013
whereas the other models have an A equal to 9.55 × 106 . But the order of magnitude of A
and Ea values generally agree from one model to another as seen in Table 4–5.
The three most important radical-based reaction rate constants are visually investi-
gated to assess the level of agreement between the models. On Fig. 4–29, the reaction
rate constant of the reaction: H + O2 ⇋ O + OH is plotted against 1000/T from the pa-
rameters obtained from the four alcohol models. The curves mostly overlap in this figure
indicating a similar choice of rate parameters. Fig. 4–30 indicates a slightly lower rate
for the n-butanol model reaction: H2 O2 + O ⇋ OH + HO2 below 1000/T = 0.9. The
other rates however, still collapse onto each other. Fig. 4–31 plots the rate constants of
the reaction: HO2 + HO2 ⇋ H2 O2 + O2 . Only the Johnson et al. [3] propanol model has
a different rate constant curve which is attributed to the lower pre-exponential Arrhenius
constant, A (1.03 × 1014 versus 4.20 × 1014 ).
50
Table 4–5: Key reaction rates parameters obtained from the four models. Reaction rate
units are cm3 ·mol·s·cal.
Alcohol Reaction A n Ea [cal/mol]

Fuel-specific reactions
MeOH [1] CH3 OH + HO2 ⇋ CH2 OH + H2 O2 3.98×1013 0 19400
EtOH [2] C2 H5 OH + HO2 ⇋ C2 H4 OH + H2 O2 8.20×103 2.55 10750
PnOH [3] C3 H7 OH + HO2 ⇋ C3 H6 OH-4 + H2 O2 2.38×104 2.55 16490
C3 H7 OH + HO2 ⇋ C3 H6 OH-3 + H2 O2 2.30×10−3 3.37 466
C3 H7 OH + HO2 ⇋ C3 H6 OH-2 + H2 O2 6.00×1012 0 16000
BuOH [4] C4 H9 OH + HO2 ⇋ C4 H9 O + H2 O2 2.50×1012 0 24000
C4 H9 OH + HO2 ⇋ C4 H8 OH-4 + H2 O2 1.23 2.55 15750
C4 H9 OH + HO2 ⇋ C4 H8 OH-3 + H2 O2 4.00×1011 0 16000
C4 H9 OH + HO2 ⇋ C4 H8 OH-2 + H2 O2 4.00×1011 0 16000
Chain-branching reactions
MeOH [1] H + O2 ⇋ O + OH 3.55×1015 -0.406 16599
EtOH [2] H + O2 ⇋ O + OH 1.21×1017 -0.86 17300
PrOH [3] H + O2 ⇋ O + OH 3.55×1015 -0.406 16600
BuOH [4] H + O2 ⇋ O + OH 1.90×1014 0 16812
MeOH [1] H2 O2 + O ⇋ OH + HO2 9.55×106 2 3970

EtOH [2] H2 O2 + O ⇋ OH + HO2 9.55×106 2 3970
PrOH [3] H2 O2 + O ⇋ OH + HO2 9.55×106 2 3970
BuOH [4] H2 O2 + O ⇋ OH + HO2 2.80×1013 0 6400
Duplicate
MeOH [1] HO2 + HO2 ⇋ H2 O2 + O2 4.20 × 1014 0 11982
EtOH [2] HO2 + HO2 ⇋ H2 O2 + O2 4.20×1014 0 11982
PrOH [3] HO2 + HO2 ⇋ H2 O2 + O2 1.03×1014 0 11040
BuOH [4] HO2 + HO2 ⇋ H2 O2 + O2 4.20×1014 0 11982
Duplicate
MeOH [1] HO2 + HO2 ⇋ H2 O2 + O2 1.30×1011 0 -1629.3
EtOH [2] HO2 + HO2 ⇋ H2 O2 + O2 1.30×1011 0 -1629
PrOH [3] HO2 + HO2 ⇋ H2 O2 + O2 1.94×1011 0 -1409
BuOH[4] HO2 + HO2 ⇋ H2 O2 + O2 1.30×1011 0 -1630
MeOH [1] O + H2 ⇋ OH + H 5.08×104 2.67 6290

EtOH [2] O + H2 ⇋ OH + H 5.06×104 2.67 6290
PrOH [3] O + H2 ⇋ OH + H 5.06×104 2.67 6290
BuOH [4] O + H2 ⇋ OH + H 1.30×104 2.8 5922
MeOH [1] HO2 + O ⇋ OH + O2 3.25×1013 0 0

EtOH [2] HO2 + O ⇋ OH + O2 3.25×1013 0 0
PrOH [3] HO2 + O ⇋ OH + O2 3.25×1013 0 0
BuOH [4] HO2 + O ⇋ OH + O2 2.44×1013 0 -446
51
14 14
k [cm3 mol s cal] 10 10
k [cm3 mol s cal]

12 12
10 10
10 10
10 10
0.7 0.8 0.9 1 0.7 0.8 0.9 1
1000/T [1/K] 1000/T [1/K]
Figure 4–29: Reaction rate constants, k Figure 4–30: Reaction rates constants, k
of the reaction: H + O2 ⇋ O + OH of the reaction: H2 O2 + O ⇋ OH + HO2
from methanol [1] (+), ethanol [2] (), n- from methanol [1] (+), ethanol [2] (), n-
propanol [3] (solid line), n-butanol [4] (◦). propanol [3] (solid line), n-butanol [4] (◦).
Figure 4–32 illustrates the rate constants of the H-abstraction fuel specific reactions of
the methanol and ethanol models, CH3 OH + HO2 ⇋ CH2 OH + H2 O2 and C2 H5 OH + HO2
⇋ C2 H4 OH + H2 O2 , respectively. The rate constants are found to be somewhat different
where the ethanol model predicts a slower forward rate constant than the methanol model.
The two rates are however in the same order of magnitude.
Figure 4–33 shows the rate constants of the three H-abstraction fuel specific reactions
of n-propanol. The fastest rate constant is found to be: C3 H7 OH + HO2 ⇋ C3 H6 OH-2 +
H2 O2 corresponding to removal of a H atom from the α C—H bond which is the weakest
bond due to the electron withdrawing effect of the neighbouring hydroxyl group.
Figure 4–34 illustrates the four n-butanol H-abstraction forward rate constants. The
two reactions that have equally high rates are: C4 H9 OH + HO2 ⇋ C4 H8 OH-3 + H2 O2
and C4 H9 OH + HO2 ⇋ C4 H8 OH-2 + H2 O2 . The abstraction of the H atom from the
weakened α C–H bond can also partly explain these higher rates.
52
14
10
10
10
k [cm3 mol s cal]
k [cm3 mol s cal]

12
10
5
10
10
10
0.7 0.8 0.9 1 0.7 0.8 0.9 1
1000/T [1/K] 1000/T [1/K]
Figure 4–31: Reaction rates constants, k of Figure 4–32: Reaction rates constants, k of
the reaction: HO2 + HO2 ⇋ H2 O2 + O2 the fuel-specific reactions of methanol Li et
from methanol [1] (+), ethanol [2] (), n- al. [1] model (Reaction 1 in Table 4–5: +)
propanol [3] (solid line), n-butanol [4] (◦). and ethanol [2] model (Reaction 1 in Table
4–5: ).
10 10
10 10
k [cm3 mol s cal]
k [cm3 mol s cal]
5 5
10 10
0.7 0.8 0.9 1 0.7 0.8 0.9 1

1000/T [1/K] 1000/T [1/K]
Figure 4–33: Reaction rates constants, k Figure 4–34: Reaction rates constants, k
of the fuel-specific reactions of propanol of the fuel-specific reactions of butanol
Johnson et al. [3] model. Reaction 1 in Sarathy et al. [4] model. Reaction 1 in Ta-
Table 4–5: △, Reaction 2: ⋄ and Reaction ble 4–5: dashed line, reaction 2: dotted
3: . line, reaction 3: dashed-dotted line, and
reaction 4: ⋄.
53
4.5 Conclusion
In contrast to previous work [53], discrepancies in the assignment of rate constants may
not explain the lack of collapse seen in experiments. The true cause of the lack of collapse
of models is difficult to uncover due to the complexity of each model and the various rates
that affect ignition delay times. Even if differences in the fuel-specific reaction rates are
slight, they may have a significant effect on the size the pool of intermediates. Furthermore,
only an incremental, hierarchical approach of modelling from smaller to larger alcohols, as
done by the Princeton group [1, 33, 54, 55], can uncover the subtleties of alcohol chemistry
where other wave reactors are used along side shock tubes.
Ignition delay times of the fuels could have a weaker than expected dependency on
the carbon chain length of the molecules. One would thus assume that ignition delay times
of even larger alcohols to be comparable to those of methanol, ethanol, n-propanol and n-
butanol. In counter-flow flame set-ups, Veloo et al. [56] also report that the flame speeds for
methanol, ethanol and n-butanol are comparable under lean to stoichiometric conditions.
Results from the study suggest that similarities seen in shock tubes are also observed in
devices where advection and diffusion come into play as well as alcohol oxidation chemistry.
Oxidation similarities in another type of molecule have also been found: alkanes. In-
deed, Saxena and coworkers [57] suggest that there are only three main reactions that
control auto-ignition regardless of the size of the alkane (above 3 carbons): one fuel de-
composition reaction, Cm Hn +HO2 =Cm Hn−1 +H2 O2 and two chain-branching reactions,
H2 O2 +M=OH+OH+(M) and HO2 +HO2 = H2 O2 +O2 . In the study, the authors develop
an analytical solution to the ignition delay times of large alkanes which solely depends on
the three reaction rates. The analytical solution proved to be highly accurate in predict-
ing simulations and experiments within a factor of 2. In future work, a similar approach
54
could be applied to the alcohols since the same reactions have been found to govern alcohol
ignition.
As Norton and Dryer [58] discovered, the larger the alcohol the more it will behave like
an alkane where hydrogenation will dominate (See Appendix A for a brief description of
the oxidation chemistry of primary alcohols). The experimental results in this work do not
reflect the state of affairs described by Norton and Dryer [58] since the ignition delay times
were found to be similar for the first four primary alcohols. However, the comparative
study done by Norton and Dryer [58] did not look at the high temperatures which were
reached to obtain the delay times. Consequently, there are other types of reactions that
control ignition which may be found across the various fuel sub-mechanisms.
55
CHAPTER 5
Conclusion
A comparative study of the ignition of four primary alcohols is carried out in the framework
of this thesis to uncover trends. The comparison is carried out by keeping constant the
equivalence ratio, argon/oxygen ratio and the nominal pressure of each fuel to obtain
ignition delay times over a range of temperatures.
Specifically, ignition delay time measurements are obtained at pressures of 2, 10 and
12 atm with argon/oxygen ratios of 10, 15 and 20 under lean, φ = 0.5, stoichiometric,
φ = 1, and rich, φ = 2, conditions between 1000 K–1800 K. It is observed that the ignition
delay time data for methanol, ethanol, n-propanol and n-butanol are similar under leaner
conditions as shown by the prediction bounds of the correlations. The level of overlap
however does decrease at rich conditions indicating that mixture composition has a non-
negligible effect on the quality of the collapse of the delay times of the four fuels.
Uncertainty in the value of the post reflected temperature, present in all the data,
does not allow for a definite declaration of which alcohol is different from another at any
condition. However, by calculating confidence intervals of the correlations, the uncertainties
can be quantified and it is demonstrated that for methanol, there is a definite difference in
activation energy from the other fuels regardless of the 15 K uncertainty in post reflected
shock temperature.
The correlations are obtained to evaluate the overall effect of φ, D and p on ignition
delay times according to fuel by using a linear regression of the experimental data using
56
the method of least squares. The correlations are found to be
τMeOH = 29 × 10−4 · φ−0.82 · D1.10 · p−0.85 · exp (25.3/RT ) (5.1)
τEtOH = 1.7 × 10−4 · φ−0.36 · D0.98 · p−0.61 · exp (32.1/RT ) (5.2)
τPrOH = 0.55 × 10−4 · φ−0.51 · D1.50 · p−0.53 · exp (30.9/RT ) (5.3)
τBuOH = 1.6 × 10−4 · φ−0.53 · D0.78 · p−0.59 · exp (33.3/RT ) (5.4)
and for all the alcohols we get:
τROH = 8.6 × 10−4 · φ−0.58 · D1.00 · p−0.69 · exp (28.0/RT ) (5.5)
where R is the gas constant in kcal/(mol K) and p is the post-reflected shock pressure in
atmospheres. Methanol is found to have a lower apparent activation energy than the other
alcohols in both experiments and simulations.
Chemical kinetic model predictions are compared to the data for the four alcohols
under all conditions. The best overall agreement between experiment and simulation is
found for ethanol. The model also depends on alkane reactions to measure the ethanol
delay times. It is the fuel unimolecular decomposition rates as pointed out by Li et al. [33]
that renders the model chemically incorrect.
The experimental results also contribute to the database of shock tube validation
targets for improving alcohol kinetic models.
The similar ignition delay times of C1 to C4 alcohols could facilitate testing of larger
alcohols in gas turbines and internal combustion engines should these also have overlapping
ignition delay times. In addition, the alcohol correlations will provide a more direct method
of calculating ignition delay times instead of relying on complex chemical kinetic models
that may be computationally expensive.
57
APPENDIX A
Oxidation chemistry of primary alcohols
A.1 Introduction
Primary alcohols are organic compounds characterized by a hydroxyl functional group,
OH, attached to a carbon root, R.
The oxidation pathways an alcohol can take depends on which bond H-abstraction
occurs. The first three bonds away from the hydroxyl (OH) are designated by: α, β
and γ which refer to the first, second and third carbons away from the hydroxyl group,
respectively (see Fig. A–1). α H-abstraction create an aldehyde, β H-abstraction force
a double bond to form between carbons to produce an alkene and γ C—C scission forms
an alkane which is simply the carbon root R. Rupture of the O—H bond will lead to
the formation of the associated aldehyde i.e. formaldehyde (methanal) if the alcohol is
methanol, acetaldehyde (ethanal) if it is ethanol, propionaldehyde (propanal) if it is n-
propanol, and so on.
The reactions governing ignition delay time or chemical induction period combustion
can be broken down into three categories [59–61]:
1. Chain-initiating reactions: fuel is decomposed, usually by uni-molecular decomposi-
tion (pyrolysis).
2. Chain-branching reactions: intermediate species are formed and radicals (reactive
species with an unpaired electron) are released.
3. Chain-terminating reactions where the final products such as H2 O and CO2 are
formed.
58
Figure A–1: Typical alcohol oxidation pathway (Adapted from Fig. 8 of Norton et al.,
1991).
Chemical kinetic mechanisms such as GRI-MECH 3.0 [62] are constructed with sets of
reactions to form various sub-mechanisms of intermediate species.
A.2 Methanol oxidation
Methanol pyrolyses via the initiation bimolecular reaction [63]:
CH3 OH + M −→ CH3 + OH + M (A.1)
The formed radicals take part in chain-branching reactions (Fig. A–2) to produce hydrogen
gas, methane and water. Formaldehyde is formed from the dissociation of the intermediate
CH2 OH which reacts with hydrogen atoms to produce HCO [63].
When in the presence of an oxidizer, methanol completely reacts to form CH2 O, H2
and CO. According to Gardiner [63], it is these species, and not methanol, that ignite. Fig.
59
Figure A–2: Primary oxidation pathways of methanol.
A–31 presents a time evolution of the molar fraction of important species in a 0-D reactor
filled with methanol and air. Profiles of the intermediates CH2 O, H2 and CO illustrate that
their formation occurs during the induction period (τ =2.6 ms) while methanol is consumed
before ignition which occurs only because of the combustion of CH2 O, H2 and CO.
A.3 Ethanol oxidation
Ethanol pyrolysis occurs via the initiation reaction:
C2 H5 OH + M −→ CH3 + CH2 OH + M (A.2)
Where acetaldehyde, CH3 CHOH, may be produced by the following reactions [64]:
C2 H5 OH + X −→ CH3 CHOH + XH (A.3)
C2 H5 OH(+M) −→ CH3 CHOH + H(+M) (A.4)
1 Adapted from Fig. 1.33 p.69 of Gas-phase combustion chemistry (1999), W. J. Gar-
diner Jr.
60
0
10
CH OH
3
−2
10
Molar Fraction, y
CH2O
−4
10
H
2
OH
−6 CO H
10
τ = 2.6 ms
−8
10
0 0.5 1 1.5 2 2.5 3 3.5
Time [ms]
Figure A–3: Species profiles in a zero dimensional adiabatic reactor with methanol and air
at T = 1200 K and p = 1 atm using the methanol Li et al. (2007) reaction mechanism.
61
C2 H5 OH + O2 −→ CH3 CHOH + HO2 (A.5)
where X is any radical of the system. Ethene is not easily produced because of the strong
covalent bond energy between C—OH. Instead, it forms via the chain branching reaction:
C2 H5 OH + H −→ C2 H5 + H2 O (A.6)
The ethyl radical, C2 H5 releases an H to form the alkene.
A.4 n-Propanol and n-butanol oxidation
n-Propanol oxidation is initiated by cleavage of the β C—C bond (which is located two
carbons away from the OH-linked carbon). Barnard and Hughes [65], realising that propi-
onaldehyde could not be detected in their static heated reactor, assumed that it was not
an intermediate of ethanol pyrolysis. In diffusion flames, Smith and Gordon [66] found a
similar state of affairs: in terms of aldehydes; only formaldehyde and acetaldehyde could
be detected. Norton and Dryer [58] suggested that the apparent absence of the aldehyde
was due to its highly reactive nature and subsequent immediate consumption.
The largest of the alcohols in this study, n-butanol, has an oxidation chemistry that
is not nearly as well established as those of methanol or ethanol. Barnard [65] found that
pyrolysis began with β-scission since the β C—C bond was found to be relatively weak
due to the electron-withdrawing effect of the hydroxyl group (—OH). The trend was also
observed in ethanol and n-propanol in the oxidation study in a flow-reactor of primary,
secondary and tertiary alcohols of Norton and Dryer [58].
Recently, the bond strengths of n-butanol were calculated [10] using Gaussian 03, a
chemical element modeling software based on the fundamental laws of quantum mechanics.
Results from the software confirmed that the strength of the C3 H5 —CH2 OH bond (359
kJ/mol) was considerably weaker than the surrounding ones. Hence, β-scission would be
62
Figure A–4: Pyrolysis of n-propanol.
more likely to occur. McEnally and Pfefferle [67] indicated a similar decomposition pathway
for the fuel in their co-flowing methane/air flames doped with 3500 ppm of n-butanol.
A.5 Conclusion
Primary alcohols, although they all possess a hydroxyl group, oxidise differently. The small-
est alcohol undergoes dehydrogenation from C—H or OH bond to mostly yield formalde-
hyde. As the carbon content is increased, the alcohols become more susceptible to an α
C—H due to the electron withdrawing effect of the hydroxyl group. However, the larger
alcohols can also break at other locations consequently producing different intermediates
(such as alkenes) but eventually tend to produce aldehydes.
63
APPENDIX B
Tabulated ignition delay times
64
Table B–1: Ignition delay times
Methanol: φ=0.5, D=15, p5 ≈12 atm Methanol: φ=1, D=10, p5 ≈10 atm
p1 [kPa] p5 [atm] T5 [K] τ [µs] p1 [kPa] p5 [atm] T5 [K] τ [µs]
67.3 12.9 1075 1460 47.0 10.5 1069 777
62.3 12.8 1119 909 43.7 10.0 1081 673
61.3 12.9 1134 880 43.1 10.0 1090 613
59.6 12.9 1170 626 48.2 10.9 1092 632
55.3 12.5 1200 480 42.8 10.0 1109 503
50.3 11.7 1221 433 46.8 11.0 1109 485
45.8 11.5 1288 268 44.2 10.4 1110 531
41.8 11.2 1357 145 41.8 9.8 1142 316
35.8 9.9 1406 109 43.9 10.8 1154 271
30.3 9.8 1562 54 40.0 9.6 1156 282
30.3 9.8 1582 30 39.3 9.8 1163 263
39.8 10.1 1166 240
41.1 10.4 1171 230
Methanol: φ=1, D=10, p5 ≈2 atm 39.8 10.2 1188 200
p1 [kPa] p5 [atm] T5 [K] τ [µs] 36.0 9.4 1191 235
9.3 2.5 1229 402 41.2 10.6 1212 158
8.5 2.4 1258 554 33.6 9.5 1247 98
7.2 2.3 1363 236 34.8 9.6 1256 102
7.2 2.2 1371 179 34.7 9.7 1299 78
6.2 2.1 1447 128
6.2 2.1 1475 92
Methanol: φ=1, D=20, p5 ≈2 atm
5.2 2.0 1594 65
p1 [kPa] p5 [atm] T5 [K] τ [µs]
5.2 1.9 1609 56
4.2 1.7 1763 28 11.8 2.5 1149 1939
11.5 2.7 1215 1132
11.0 2.5 1223 975
8.8 2.4 1345 446
8.1 2.3 1413 303
5.9 2.0 1635 137
5.1 1.7 1717 61
5.1 1.7 1776 88
65
Table B-1: Ignition delay times (continued).
Methanol: φ=1, D=20, p5 ≈10 atm Ethanol: φ=0.5, D=15, p5 ≈12 atm
53.5 10.8 1068 1174 58.5 12.1 1119 1184
54.3 10.7 1123 865 53.7 11.2 1119 1255
52.3 11.1 1136 752 58.4 13.0 1177 740
51.2 11.5 1163 575 59.1 13.3 1196 531
45.6 10.4 1187 507 50.4 12.8 1268 265
45.4 11.5 1253 263 44.8 11.8 1321 202
36.8 10.4 1368 137 40.1 10.8 1384 91
29.0 8.7 1522 56 37.0 10.5 1449 55
23.4 7.0 1531 45 35.4 9.2 1512 26
23.0 7.3 1610 20
Ethanol: φ=1, D=10, p5 ≈2 atm

Methanol: φ=2, D=15, p5 ≈2 atm p1 [kPa] p5 [atm] T5 [K] τ [µs]
12.0 2.7 1100 1730
11.5 2.5 1082 1724 10.1 2.7 1232 490
10.6 2.5 1121 1123 9.1 2.4 1251 430
10.4 2.6 1131 975 8.5 2.4 1311 215
9.5 2.4 1176 773 8.1 2.4 1348 186
8.7 2.4 1230 422 7.9 2.2 1350 142
8.6 2.4 1262 335 7.7 2.4 1385 163
7.6 2.2 1310 233 7.5 2.1 1433 91
6.6 2.0 1406 140 7.1 2.1 1439 77
5.1 1.7 1514 89 6.5 2.2 1462 60
5.5 1.9 1530 74 5.9 1.9 1542 29
5.3 1.9 1566 75
4.5 1.7 1639 64
66
Ethanol: φ=1, D=10, p5 ≈10 atm Ethanol: φ=1, D=20, p5 ≈10 atm
41.1 9.9 1128 696 50.5 10.8 1138 1034
41.4 10.0 1130 604 50.5 10.7 1139 1128
40.8 10.2 1143 490 47.8 11.4 1221 450
41.5 10.9 1188 286 46.1 10.9 1228 423
37.3 9.8 1204 267 48.5 11.9 1265 238
36.2 9.8 1212 238 34.3 9.3 1367 119
39.9 10.8 1217 203 30.4 8.6 1413 86
40.7 11.3 1261 125 30.7 8.6 1480 58
30.6 8.7 1296 116 26.0 7.6 1518 26
31.0 9.0 1296 102 27.8 8.5 1572 21
34.9 10.1 1326 70
30.5 8.9 1361 54
10.9 2.5 1116 1571
9.9 2.6 1161 1011
10.9 2.4 1192 1341 10.1 2.5 1175 838
9.7 2.3 1245 837 9.4 2.4 1198 689
9.5 2.3 1311 586 9.1 2.4 1205 532
8.4 2.0 1342 348 9.9 2.7 1217 723
6.9 1.9 1489 111 8.8 2.3 1231 570
6.9 2.1 1521 87 8.6 2.3 1291 369
6.2 2.0 1575 41 8.7 2.5 1291 295
6.2 1.8 1584 37 8.5 2.4 1293 373
6.2 2.0 1623 46 8.1 2.4 1330 318
7.3 2.0 1370 172
7.2 2.1 1393 124
6.5 1.9 1460 89
6.0 2.0 1518 88
5.5 1.9 1578 33
67
n-Propanol: φ=0.5, D=15, p5 ≈12 atm n-Propanol: φ=1, D=10, p5 ≈10 atm
59.0 12.4 1144 937 44.3 10.1 1097 861
58.8 12.4 1155 871 42.4 10.0 1127 582
59.7 12.9 1171 739 42.5 10.7 1168 377
54.4 12.3 1208 517 43.0 10.3 1172 379
53.3 12.3 1228 369 40.0 10.3 1202 247
55.0 12.8 1234 337 38.5 10.5 1217 195
55.1 12.7 1242 385 33.0 9.3 1264 142
50.1 12.8 1306 187 31.0 9.0 1300 121
45.2 11.5 1320 213 28.5 8.5 1368 56
42.8 10.1 1331 190
41.6 10.8 1348 131
45.2 12.2 1364 100 n-Propanol: φ=1, D=20, p5 ≈2 atm
41.1 10.2 1377 61 p1 [kPa] p5 [atm] T5 [K] τ [µs]
39.8 10.5 1382 127 11.0 2.4 1155 1724
40.4 10.3 1399 63 10.5 2.3 1236 889
40.8 10.3 1406 48 9.0 2.2 1341 420
41.6 10.4 1415 57 8.0 2.1 1413 336
39.6 10.1 1427 36 7.6 2.2 1487 224
35.0 9.8 1447 71 5.6 1.8 1657 80
40.2 11.0 1491 21 5.0 1.5 1813 26
n-Propanol: φ=1, D=10, p5 ≈2 atm n-Propanol: φ=1, D=20, p5 ≈10 atm

10.1 2.5 1206 593 49.5 10.5 1136 1112
9.6 2.5 1241 515 48.2 11.4 1230 462
9.1 2.4 1278 249 44.8 10.5 1238 350
8.1 2.1 1287 336 37.7 9.4 1305 254
8.7 2.4 1315 212 42.0 11.0 1320 222
7.5 2.2 1404 136 44.0 11.9 1341 174
7.0 2.0 1412 144 32.9 9.4 1419 112
6.7 2.1 1435 120 27.0 8.1 1521 47
6.2 1.9 1515 48 35.8 10.5 1560 25
5.4 1.7 1557 55
5.3 1.6 1573 45
68
n-Propanol: φ=2, D=15, p5 ≈2 atm n-Butanol: φ=1, D=10, p5 ≈2 atm

10.9 2.5 1121 1558 10.5 2.5 1205 574
10.9 2.4 1123 1389 9.5 2.3 1214 593
10.5 2.4 1133 823 10.0 2.5 1226 520
10.7 2.5 1153 789 9.5 2.3 1304 285
10.6 2.6 1188 453 8.5 2.2 1326 264
8.6 2.2 1244 367 7.5 2.1 1367 153
8.1 2.2 1291 313 7.9 2.2 1374 132
7.8 2.3 1352 158 7.2 2.1 1457 87
7.4 2.1 1384 108 6.8 1.8 1492 35
6.9 2.0 1414 61 6.3 1.7 1495 57
6.5 2.0 1453 42 6.0 1.8 1557 19
6.1 1.7 1495 40
n-Butanol: φ=1, D=10, p5 ≈10 atm

N -butanol: φ=0.5, D=15, p5 ≈12 atm p1 [kPa] p5 [atm] T5 [K] τ [µs]
43.7 9.8 1109 844
56.7 12.2 1165 692 41.2 9.8 1145 513
58.0 12.4 1182 611 43.2 10.1 1146 514
51.9 12.1 1224 463 39.5 9.7 1173 362
54.9 13.0 1237 410 36.6 9.5 1223 235
45.9 11.2 1266 254 31.4 8.2 1244 199
42.5 10.8 1328 206 33.4 8.8 1249 168
37.8 10.3 1419 96 30.8 8.6 1334 73
33.0 9.0 1517 50 28.9 8.5 1351 71
31.0 8.9 1555 31 28.0 8.3 1370 60
26.4 8.1 1420 27
69
n-Butanol: φ=1, D=20, p5 ≈2 atm n-Butanol: φ=1, D=20, p5 ≈2 atm

11.0 2.4 1155 1724 10.6 2.4 1120 1584
10.0 2.2 1206 1146 9.2 2.2 1172 620
11.8 2.7 1211 898 9.7 2.5 1177 769
10.5 2.3 1236 889 9.6 2.3 1192 565
8.7 2.1 1321 322 10.4 2.9 1198 672
9.0 2.2 1341 420 9.1 2.4 1236 428
8.4 2.0 1344 329 7.5 2.1 1357 177
8.0 2.1 1413 336 6.5 2.0 1418 150
7.1 1.8 1435 119 5.3 1.7 1517 116
7.6 2.2 1487 224 5.5 2.9 1551 76
6.0 1.9 1618 31
5.6 1.8 1657 80
5.8 1.7 1664 16
5.0 1.5 1813 26
n-Butanol: φ=1, D=20, p5 ≈10 atm

46.9 10.4 1186 651
41.7 9.6 1203 556
43.9 10.3 1228 450
48.2 11.7 1251 307
40.3 10.4 1312 190
35.1 8.8 1335 93
33.3 9.2 1404 66
37.1 9.7 1459 21
70
APPENDIX C
Supporting figures of simulated ignition delay times
71
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
−1 −1
1000/T [K ] 1000/T [K ]
Figure C–1: Methanol ignition delay times, Figure C–2: Ethanol ignition delay times,
τ , at φ = 0.5, D = 15, p = 12 atm. Data: τ , at φ = 0.5, D = 15, p = 12 atm.
methanol (+). Simulations: methanol [1] Data: ethanol (◦). Simulations: ethanol
(dotted line). [2] (dashed line)
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
−1 −1
1000/T [K ] 1000/T [K ]
Figure C–3: n-Propanol ignition delay Figure C–4: n-Butanol ignition delay
times, τ , at φ = 0.5, D = 15, p = 12 atm. times, τ , at φ = 0.5, D = 15, p = 12 atm.
Data: n-propanol (△). Simulations: n- Data: n-butanol (). Simulations: n-
propanol [3] (thin solid line). butanol [4] (thick solid line).
72
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
τ , at φ = 1, D = 10, p = 2 atm. Data: τ , at φ = 1, D = 10, p = 2 atm.
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
73
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
τ , at φ = 1, D = 10, p = 10 atm. Data: τ , at φ = 1, D = 10, p = 10 atm.
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
74
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
Figure C–13: Methanol ignition delay Figure C–14: Ethanol ignition delay times,
times, τ , at φ = 1, D = 20, p = τ , at φ = 1, D = 20, p = 2 atm.
2 atm. Data: methanol (+). Simulations: Data: ethanol (◦). Simulations: ethanol
methanol [1] (dotted line). [2] (dashed line)
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
75
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
Figure C–17: Methanol ignition delay Figure C–18: Ethanol ignition delay times,
times, τ , at φ = 1, D = 20, p = τ , at φ = 1, D = 20, p = 10 atm.
10 atm. Data: methanol (+). Simulations: Data: ethanol (◦). Simulations: ethanol
methanol [1] (dotted line). [2] (dashed line)
3 3
10 10
τ [µs]
τ [µs]
2 2
10 10
1 1
10 10
0.6 0.7 0.8 0.9 0.6 0.7 0.8 0.9
1000/T [1/K] 1000/T [1/K]
76
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Comparative Chemical Kinetic A

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COMPARATIVE CHEMICAL KINETIC AND EXPERIMENTAL STUDY OF

METHANOL, ETHANOL, N -PROPANOL AND N -BUTANOL AUTO-IGNITION

Khalid Emilio Noorani

Department of Mechanical Engineering

Montreal, Quebec, Canada

A thesis submitted to McGill University in partial fulfillment of the requirements of the

(c) Noorani 2011

395 Wellington Street 395, rue Wellington

Our file Notre référence

The author retains copyright L'auteur conserve la propriété du droit d'auteur

In compliance with the Canadian Conformément à la loi canadienne sur la

years ago as an undergraduate as well as his constant encouragements.

remarks and good humour during formal (and informal) presentations.

their support and friendship.

this would have been possible without them.

indicate dominance of radical chemistry, H abstraction reactions of methanol and uni-

molecular fuel decompositions of n-butanol.

cinétiques trouvés dans la littérature sont comparés aux résultats expérimentaux. Il se

indiquent la dominance des réactions à base de radicaux.

The author has made the following contributions:

and Benjamin Akih-Kumgeh,

2. Performing the shock tube experiments,

3. Post-processing of the measured data,

6. Publishing of a paper “Comparative High Temperature Shock Tube Ignition of C1-

co-authored by Benjamin Akih-Kumgeh and his supervisor.

CONTRIBUTIONS OF THE AUTHOR . . . . . . . . . . . . . . . . . . . . . . . . . v

LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii

2 Literature review of alcohol auto-ignition studies . . . . . . . . . . . . . . . . . 4

2.1 Shock tube studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.1 Background— shock tubes in chemical kinetics . . . . . . . . . . . . . . 11

4 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

4.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

A Oxidation chemistry of primary alcohols . . . . . . . . . . . . . . . . . . . . . . 58

B Tabulated ignition delay times . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

C Supporting figures of simulated ignition delay times . . . . . . . . . . . . . . . 71

2–1 Parameters of methanol shock tube studies. . . . . . . . . . . . . . . . . . . 5

3–1 Combustible mixtures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4–1 Experimental conditions for methanol (C1 : 1 carbon molecule) to n-butanol

4–2 Experimental parameters of the correlation: τ = C · φα · Dβ · pζ · exp (Ea /RT ). 31

4–3 Details of mechanisms in this study . . . . . . . . . . . . . . . . . . . . . . . 35

4–4 Experimental and simulation parameters of the correlation: τ = C · φα · Dβ ·

B–1 Ignition delay times . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

2–2 Ignition delay times of alkanes by Burcat et al. (1971) at φ = 1, p ≈ 10 ± 3

3–2 Experimental set-up (not to scale). . . . . . . . . . . . . . . . . . . . . . . . 20

3–4 End wall pressure and CH radical chemilumescence measurements with

3–6 Pressure gradient in a zero dimensional adiabatic reactor with methanol

4–2 Alcohol ignition delay times, τ , at φ = 1, D = 10, p = 2 atm. Data:

4–3 Alcohol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

4–4 Alcohol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

4–5 Alcohol ignition delay times, τ , at φ = 1, D = 20, p = 10 atm. Data:

4–6 Alcohol ignition delay times, τ , at φ = 1, D = 20, p = 2 atm. Data:

4–8 Upper and lower prediction bounds of the correlations at φ = 1, D = 10,

4–9 Upper and lower prediction bounds of the correlations at φ = 2, D = 10,

4–10 Methanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

4–12 n-Propanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

4–13 n-Propanol ignition delay times, τ , at φ = 1, D = 20, p = 2 atm. Data:

4–14 n-Butanol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

4–15 Alcohol ignition delay times, τ , at φ = 1, D = 10, p = 10 atm. Data:

4–16 Alcohol ignition delay times, τ , at φ = 1, D = 20, p = 10 atm. Data:

4–17 Alcohol ignition delay times, τ , at φ = 0.5, D = 15, p = 12 atm. Data:

4–18 Alcohol ignition delay times, τ , at φ = 2, D = 15, p = 2 atm. Data:

4–19 Comparison between experimental and literature ignition delay times of

4–20 Comparison between experimental and literature ignition delay times of

4–22 Comparison of correlations derived in this study with literature data on