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ARTICLE pubs.acs.org/JPCA A Revisited Picture of the Mechanism of Glycerol Dehydration Teodoro Laino,* Christian Tuma, Alessandro
 

ARTICLE

pubs.acs.org/JPCA

A Revisited Picture of the Mechanism of Glycerol Dehydration

Teodoro Laino,* , Christian Tuma, Alessandro Curioni, Evan Jochnowitz, and Steen Stolz ,z

IBM Research Zurich, Saumerstrasse 4, CH-8803 Ruschlikon, Switzerland Philip Morris International R&D, Quai Jeanrenaud 5, CH-2000 Neuch^atel, Switzerland z University of Twente, Faculty EEMCS, P.O. Box 217, NL-7500 AE Enschede, The Netherlands

b S 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.

ABSTRACT: The dehydration mechanism of neutral glycerol in the gas phase was investigated by means of

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 mecha- nisms 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 combusted 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, 4 7 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 path- ways. 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. Glycerol pyrolysis has been the subject of several experimental studies. The formation of acrolein (2-propenal), formaldehyde,

1

8

and acetaldehyde depends on the temperature 6 and on the presence of water either as steam 6,9 or as supercritical liquid. 10,11 Recently, Paine et al. 7 investigated pyrolysis mechanisms using isotopic labeling and found that the decomposition pathway is entirely unimolecular in nature. They proposed three dierent, highly competitive mechanisms depending on the presence of catalysts or impurities. Two studies recently published 4,5 contributed to the under- standing of glycerol pyrolysis using theoretical approaches. Nimlos et al. studied the dehydration of neutral and protonated glycerol

4

reporting a high barrier for 1,2-dehydration (71 kcal/mol), which was lower for a pericyclic 1,3-dehydration (65 kcal/mol) and considerably lower in the case of the protonated glycerol. They concluded their study by stating that the decomposition of neutral glycerol can occur only at a relatively high temperature such as in pyrolysis or combustion. From a mechanicistic point of view, they inspected, based on chemical intuition, dierent reaction mecha- nisms: 1,2-dehydration and the pericyclic 1,3-dehydration for neutral glycerol and the formation of oxirane or oxetane inter- mediates for protonated species. Nimlos et al. 4 did not consider the possible formation of oxirane intermediates for the neutral glycerol decomposition. More recently, Sun et al. 5 investigated the possibi- lity for neutral glycerol to dehydrate into glycidol (an oxirane intermediate). The results of their calculations suggest a barrier of 59 kcal/mol, also requiring high temperatures for glycerol to decompose into glycidol.

Received: February 1, 2011

Revised:

March 17, 2011

Published: March 31, 2011

ARTICLE pubs.acs.org/JPCA A Revisited Picture of the Mechanism of Glycerol Dehydration Teodoro Laino,* Christian Tuma, Alessandro

r 2011 American Chemical Society

3592

dx.doi.org/10.1021/jp201078e | J. Phys. Chem. A 2011, 115, 35923595

The Journal of Physical Chemistry A

ARTICLE

In this article, we employ the metadynamics 12 technique in order to explore in a much more thorough way the potential energy surface related to the pyrolytic decomposition of glycerol in vacuum. This exploration provides an alternative reaction mecha- nism for glycerol pyrolysis based on the possibility of glycerol to dehydrate into glycidol. We discuss the thermodynamic and kinetic properties of the dierent reaction steps with particular attention to the eect of temperature, providing rate constants k(T) obtained from canonical transition-state theory. 13 17

METHODS

Metadynamics simulations, 12 in contrast to standard quantum chemical approaches where results strongly depend on the chemi- cal 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, PBE 18 ) Hamiltonian. Upon completion of the thermalization process, determined by the averages and the uctuations of the potential energy, we have started the metadynamics 12 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 CPMD 19 code is

sðO 1 , C 1 , C 2 , C 3 Þ

¼

8

>> >

R

O C

1

1

R 0

6

1

R

O C

1

2

R 0

6

R O 1 C 3

R 0

6

1

1

> <

>> >

: > 1

1

2

R

O C

1

1

R 0

1

R

O C

1

2

R 0

1

R O 1 C 3

R 0

12

12 þ

12 þ

9

>> >

= >

>> >

; >

ð1Þ

Here R O are the distances between a selected oxygen (i) and the

i

C j

carbon atoms (j) of the glycerol moiety. R 0 is the equilibrium distance of an oxygen carbon bond in glycerol, equal to 1.55 Å.

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 code 21 and a semiempirical PM6 22 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 PBE 18 and, subsequently, the PBE0 23 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 cutowas employed combined with norm conserving atomic pseudopotentials. Periodic images of the molecules were decoupled using a Poisson solver 26 with cubic computational

25

boxes of 15 Å edge length. Convergence was achieved in structure relaxations when all Cartesian force components became smaller than 2.0 10 5 atomic units. PBE0 force constant matrices (Hessians) were computed by numerical dierentiation of analy- tical forces. Translations and rotations were projected from the Hessian. Stationary points were characterized on the basis of corresponding vibrational frequencies. Reactants and products of each reactive step had no imaginary frequencies while transition structures had exactly one imaginary frequency. In addition, transition structures were inspected by intrinsic reaction coordi- nate (IRC) calculations 27 in both directions in order to retrieve either the reactants or the products. These calculations were performed using the CPMD code. 19 The evaluation of reaction rate constants k(T) was done within canonical transition-state theory formalism

kðT Þ ¼

k B h T exp

ΔG

RT

!

ð2Þ

where k B is the Boltzmann constant, T is the temperature (800 K), h is the Planck constant, ΔG is the activation Gibbs free energy of the reaction, and R is the gas constant. Finite tem- perature entropy and energy contributions were obtained from standard statistical mechanics approaches.

RESULTS AND DISCUSSION

In addition to the three decomposition pathways proposed by Nimlos et al., 4 we complete the picture with an energetic competitive scheme, leading either to acrolein or formaldehyde/ acetaldehyde. It is worth noting that in our simulations we sampled the free energy landscapes according a set of collective variables describing the elimination of water only; for this reason, although similar in transition state energies, we were sampling regions of the phase space dierent from the ones inspected by

Nimlos et al. 4 A similar reactivity 4 can be achieved by enforcing

a free energy sampling involving both water elimination and

the corresponding carbon carbon bond breaking. The new

decomposition mechanism of glycerol can be sketched into four

dierent reaction steps: formation of glycidol via 1,2-water elimination (i); conversion of glycidol into 3-hydroxypropanal (ii); decomposition of 3-hydroxypropanal into vinyl-alcohol

and formaldehyde (iii) or into acrolein and water (iv). In the

following paragraphs we will review these steps. Glycerol can form glycidol via 1,2-elimination of water (Scheme 1, reaction 1). This reaction path has been recently investigated by Sun et al. 5 who computed kinetics and thermo- dynamics for several structures with dierent relative congura- tions of the atoms involved. Rening the reactive trajectory using DFT, we computed the thermodynamic and kinetic quantities reported in Table 1 in good agreement with previously published results. With a Gibbs free energy barrier of 66.8 kcal/mol (T = 800 K), this reaction step is to be considered the rate limiting step. Upon opening of the epoxy ring, glycidol converts into 3-hydro- xypropanal via the transition structure depicted in Scheme 1, reaction 2. This reaction step is extremely fast; it proceeds via formation of a transient carbocationic species (secondary carbo- cation). Hydrogen present on atom C1 of glycidol is transferred to the secondary carbon atom concurrently to the formation of

5

the carbonyl group. Metadynamics runs provided no evidence of the possibility to form a keto group via formation of a primary

  • 3593 dx.doi.org/10.1021/jp201078e |J. Phys. Chem. A 2011, 115, 3592–3595

The Journal of Physical Chemistry A

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Scheme 1. Reaction Prole for the Pyrolysis of Glycerol

The Journal of Physical Chemistry A ARTICLE Scheme 1. Reaction Pro fi le for the Pyrolysis

Table 1. DFT (PBE0) Total Energy, ΔE , Zero-Point Vibrational Energy Corrected, ΔE 0 , Enthalpy, ΔH (T), and Gibbs Free Energy, ΔG (T), Barrier Heights (in kcal/mol) As Well As Rate Constants k(T) (in 1/s) Computed for the Dierent Reaction Steps of Glycerol Pyrolysis Shown in Scheme 1 (T = 800 K)

‡ step ΔE ‡ ΔE 0 ΔH ‡ (T) ΔG ‡ (T) k(T)
step
ΔE ‡
ΔE 0
ΔH ‡ (T)
ΔG ‡ (T)
k(T)

1

2

3

70.9

53.2

36.7

67.1

48.4

33.4

66.9

47.7

32.7

66.8

49.5

35.3

  • 4 53.9

58.3

53.8

54.0

9 10 6

5 10 1

4 10 þ 3

3 10 2

carbocation which is well-known to be less stable than a secondary carbocation. 3-Hydroxypropanal may decompose into two dierent paths. The most favorable in terms of barrier height is the conversion into formaldehyde and the enolic form of acetaldehyde (Scheme 1, reaction 3). This reaction represents the fastest process in the decomposition of glycerol and is driven by the acidity of the hydroxyl group. Although energetically less favorable, 3-hydroxypropanal can follow a dierent decomposition pathway. It can decompose into water and acrolein (Scheme 1, reaction 4). Because of the larger barrier height, the formation of acrolein should be observed only at high temperatures where this process competes with the decomposition into formaldehyde and vinyl-alcohol. The forma- tion of acrolein is driven by the acidity of the hydrogen atom at the R-carbon atom, which is known to be less acidic than a hydroxyl group. The pyrolytic studies of glycerol in steam 6,9 and supercritical water 10,11 cannot be directly compared to the present computa- tional results. In fact, either supercritical water or steam at high temperature may aect the decomposition pathways, because water itself is more acidic at high temperature. Only recently, Paine et al. 7 studied the decomposition of pure glycerol in the gas phase. Unfortunately, while investigating extensively the mechanisms they did not focus on any mea- surement of kinetic data. Interestingly enough, from a quanti- tative point of view, our ndings complete the energetics for

mechanism B proposed by Paine 7 in which the center carbon in glycerol ultimately ends up as the methyl group in acetaldehyde, thus providing strong support to their outlines.

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

b S

Supporting Information. A comparison between PBE/

PBE0 barrier heights, Cartesian coordinates, and vibrational frequencies obtained for the transition structures and intermedi- ates are available. This material is available free of charge via the

Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: teo@zurich.ibm.com. Phone: þ41 (0) 44 724 8933. Fax: þ41 (0) 44 724 8958.

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