Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
pubs.acs.org/JPCA
bS Supporting Information
ABSTRACT: The dehydration mechanism of neutral glycerol
in the gas phase was investigated by means of metadynamics
simulations. Structures, vibrational frequencies, Gibbs free energy
barriers, and rate constants at 800 K were computed for the
dierent steps involved in the pyrolytic process. In this article,
we provide a novel mechanism for the dehydration of neutral
glycerol, proceeding via formation of glycidol with a barrier of
66.8 kcal/mol. The formation of glycidol is the rate limiting step
of the overall decomposition process. Once formed, glycidol
converts into 3-hydroxypropanal with a barrier of 49.5 kcal/mol.
3-Hydroxypropanal can decompose further into acrolein or into formaldehyde and vinyl-alcohol with barriers of 53.9 and 35.3 kcal/mol,
respectively. These ndings oer new insights to available experimental data based on glycerol pyrolysis studies performed with
isotopic labeling and on the interpretation of the chemistry of glycerol and sugars in pyrolytic conditions.
INTRODUCTION
Carbohydrates are the primary constituents of most biomass
materials and due to their ubiquitous presence their chemistry
is of paramount importance. However, while the reactivity of
sugars at ambient conditions was explored in the last century, the
understanding of the fundamental underlying reaction mechanisms involved in the pyrolysis of the sugars is still basically
undiscovered. The lack of knowledge about chemical processes
involved in the pyrolysis of carbohydrates is surprising since
thermal degradation processes occur widely wherever biomasses
are combusted1 or food is cooked at high temperatures,2 not to
mention its relevance in the formation of cigarette smoke.3 As
already outlined in several studies,47 the reason for such a lack
of understanding can be explained by the inherent diculties in
studying the combustion mechanisms in sugars due to the
complexity arising from the large number of adjacent hydroxyl
groups. Despite chemical dierences, glycerol (propan-1,2,3-triol)
has been largely established as the smallest compound possessing
much of the functionalities of a carbohydrate but still small
enough to make its behavior at high temperature more readily
understood. Moreover, since it is a small molecule, it allows the
application of high level and time-consuming potential energy
exploration tools to characterize thermal decomposition pathways. Last, it is worth noting that the thermal decomposition of
glycerol is an important topic itself. In fact, its wide presence
in animal fats and vegetable oils exposes glycerol contained in
food to possible thermal decomposition processes during heat
treatments.8
Glycerol pyrolysis has been the subject of several experimental
studies. The formation of acrolein (2-propenal), formaldehyde,
r 2011 American Chemical Society
ARTICLE
METHODS
Metadynamics simulations,12 in contrast to standard quantum
chemical approaches where results strongly depend on the chemical intuition employed to build the model, sample in a more
unbiased way the potential energy space with respect to a set of
internal (collective) variables. Therefore, it can be considered a
useful exploratory tool oering the advantage of providing reactive
trajectories that follow the minimum energy path projected in the
space of collective variables.
Free-energy surfaces were sampled according to the following
strategy: the dierent systems have been rst thermalized by
molecular dynamics in an NVT ensemble at the temperature of
800 K using a density functional theory (DFT, PBE18) Hamiltonian.
Upon completion of the thermalization process, determined
by the averages and the uctuations of the potential energy, we
have started the metadynamics12 exploration, employing a set of
appropriately chosen collective variables to sample the free energy
space of glycerol, glycidol, and 3-hydroxypropanal, searching for
low-barrier reactive events. Collective variables employed were
all related to the coordination of oxygen with hydrogens and
carbons, describing a water molecule either connected to the
glycerol moiety or a dehydrated glycerol. The functional form
employed to describe the coordination variable, as implemented
in the CPMD19 code is
sO1 , C1 , C2 , C3
8
9
>
RO1 C 1 6
R O 1 C2 6
R O 1 C3 6 >
>
>
>
>
1
1
1
=
1<
R0
R0
R0
12
12
12
>
2>
R O 1 C1
R O 1 C2
R O 1 C3
>
>
>
>
1
1
;
:1
R0
R0
R0
1
Here ROiCj are the distances between a selected oxygen (i) and the
carbon atoms (j) of the glycerol moiety. R0 is the equilibrium
distance of an oxygencarbon bond in glycerol, equal to 1.55 .
Reactive trajectories were optimized using a climbing image
nudged elastic band (NEB)20 approach with 20 images sampling
the reactive path. These calculations were performed using the
CP2K code21 and a semiempirical PM622 Hamiltonian.
Starting from selected points of the PM6 optimized reactive
paths, stationary points corresponding to reactants, transition
structures, and products were rened using density functional
theory (DFT) rst with the PBE18 and, subsequently, the PBE023
parameter free exchange-correlation functionals. The choice of
rening the PBE results with PBE0 is driven by the higher
systematic accuracy of hybrid functionals in estimating barrier
heights compared to pure gradient corrected functionals.24 In
these calculations a plane wave basis set with a 100 Ry kinetic
energy cuto was employed combined with norm conserving
atomic pseudopotentials.25 Periodic images of the molecules were
decoupled using a Poisson solver26 with cubic computational
!
2
ARTICLE
E0
H(T)
G(T)
k(T)
70.9
67.1
66.9
66.8
9 106
53.2
48.4
47.7
49.5
5 101
36.7
33.4
32.7
35.3
4 103
58.3
53.8
54.0
53.9
3 102
CONCLUSIONS
We have proposed a completely new decomposition pathway
for glycerol via formation of glycidol. The present computational
study shows that the mechanism is isoenergetic and therefore
highly competitive with the ones already published in literature
and oers a complete picture of its pyrolytic chemistry without
assuming any enol-type intermediate. Since no experimental
studies have ever hypothesized the pyrolytic decomposition of
glycerol via glycidol formation, this work provides a substantial
improvement to the interpretation of the chemistry of glycerol
and sugars in pyrolytic conditions.
ASSOCIATED CONTENT
bS
AUTHOR INFORMATION
Corresponding Author
REFERENCES
(1) Kaltschmitt,M.; Bridgewater, A. W. Biomass Gasication and
Pyrolysis: State of the Art and future prospects; CPL Scientic Limited:
Newbury, U.K., 1997.
(2) Tomasik, P.; Palasinski, M.; Wiejak, S. Adv. Carbohydr. Chem.
Biochem. 1989, 47, 203.
(3) Burton, H. R.; Childs, G., Jr. Beitr. Tabakforsch. 1975, 8, 174.
(4) Nimlos, M. R.; Blanksby, S. J.; Qian, X.; Himmel, M. E.; Johnson,
D. K. J. Phys. Chem. A 2006, 110, 61456156.
(5) Sun, W.; Liu, J.; Chu, X.; Zhang, C.; Liu, C. J. Mol. Struct.:
THEOCHEM 2010, 942, 3842.
3594
ARTICLE
(6) Stein, S. Y.; Antal, M. J., Jr. J. Anal. Appl. Pyrolysis 1983,
4, 283296.
(7) Paine, J. B., III; Pithawalla, Y. B.; Naworal, J. D.; Thomas, C. E.,
Jr. J. Anal. Appl. Pyrolysis 2007, 80, 297311.
(8) Landin, H.; Tareke, E.; Rydberg, P.; Olsson, U.; Tornqvist, M.
Food Chem. Toxicol. 2000, 38, 963.
(9) Antal, M. J.; Mok, W. S. L.; Roy, J. C.; Raissi, A. T.;
Anderson, D. G. M. J. Anal. Appl. Pyrolysis 1985, 8, 291.
(10) Buhler, W.; Dinjus, E.; Ederer, H. J.; Kruse, A. J. Supercrit. Fluids
2002, 22, 37.
(11) Ramayya, S.; Brittain, A.; Dealmeida, C.; Mok, W.; Antal, M.
J. Fuel 1987, 66, 1364.
(12) Laio, A.; Parrinello, M. Proc. Natl. Acad. Sci. U.S.A. 2002,
99, 1256212566.
(13) Eyring, H. J. Chem. Phys. 1935, 3, 492.
(14) Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1935, 31, 875.
(15) Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1937, 33, 448.
(16) Laidler, K. J.; King, M. C. J. Phys. Chem. 1983, 87, 2657.
(17) Truhlar, D. G.; Hase, W. L.; Hynes, J. T. J. Phys. Chem. 1983,
87, 2664.
(18) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,
77, 38653868.
(19) CPMD, Copyright Max Planck Institut fur Festkorperforschung
Stuttgart 19972001, Copyright IBM Corp. 19902011. http://www.
cpmd.org.
(20) Henkelman, G.; Uberuaga, B. P.; Jonsson, H. J. Chem. Phys.
2000, 113, 9901.
(21) The CP2K developers group, code released under GPL license,
freely available at http://cp2k.berlios.de.
(22) Stewart, J. J. P. J. Mol. Model. 2007, 13, 1173.
(23) Adamo, C.; Barone, V. J. Chem. Phys. 1999, 110, 6158.
(24) Zhao, J.; Gonzalez-Garcia, N.; Truhlar, D. G. J. Phys. Chem. A
2005, 109, 20122018.
(25) Troullier, N.; Martins, J. L. Phys. Rev. B 1991, 43, 1993.
(26) Martyna, G. J.; Tuckerman, M. E. J. Chem. Phys. 1999,
110, 2810.
(27) Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154.
3595