Thermal Decomposition of Decalin:  An <i>Ab Initio</i> Study

Chae, Kyungchan; Violi, Angela

doi:10.1021/jo062324x

Cited by 32 publications

(19 citation statements)

References 40 publications

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“…Notably, our simulations show the complete absence of hydrogen abstraction reactions (1a, 2a, 3a in Fig. 4), which are indicate in the literature as the dominating pathways in such conditions [21]. However, by inspecting the free energy landscape as a function of the distance of the hydrogen between the carbon of the methyl radical and of the decalin (see supplementary material), one can observe that the abstraction reactions must overcome a barrier of at least 50 kcal/mol more than that needed for the unassisted C−H bond breaking and are therefore correctly not observed in a sample of a few hundred runs.…”

supporting

confidence: 63%

Fast exploration of chemical reaction networks

Elvati¹,

Violi²

2014

Preprint

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A variety of natural phenomena comprises a huge number of competing reactions and shortlived intermediates. Any study of such processes requires the discovery and accurate modeling of their underlying reaction network. However, this task is challenging due to the complexity in exploring all the possible pathways and the high computational cost in accurately modeling a large number of reactions. Fortunately, very often these processes are dominated by only a limited subset of the network's reaction pathways. In this work we propose a novel computationally inexpensive method to identify and select the key pathways of complex reaction networks, so that high-level ab-initio calculations can be more efficiently targeted at these critical reactions. The method estimates the relative importance of the reaction pathways for given reactants by analyzing the accelerated evolution of hundreds of replicas of the system and detecting products formation. This acceleration-detection method is able to tremendously speed up the reactivity of uni-and bimolecular reactions, without requiring any previous knowledge of products or transition states. Importantly, the method is efficiently iterative, as it can be straightforwardly applied for the most frequently observed products, therefore providing an efficient algorithm to identify the key reactions of extended chemical networks. We verified the validity of our approach on three different systems, including the reactivity of t-decalin with a methyl radical, and in all cases the expected behavior was recovered within statistical error.

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supporting

confidence: 63%

Fast exploration of chemical reaction networks

Elvati¹,

Violi²

2014

Preprint

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“…It underwent ring opening reactions. In other work, Chae and Violi [64] computed rate constants for the decomposition of decalin using density functional theory.…”

Section: Cycloalkanesmentioning

confidence: 99%

Recent progress in the development of diesel surrogate fuels

Pitz

Mueller

2011

Progress in Energy and Combustion Science

645

371

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There has been much recent progress in the area of surrogate fuels for diesel. In the last few years, experiments and modeling have been performed on higher molecular weight components of relevance to diesel fuel such as n-hexadecane (n-cetane) and 2,2,4,4,6,8,8-heptamethylnonane (iso-cetane). Chemical kinetic models have been developed for all the n-alkanes up to 16 carbon atoms. Also, there has been much experimental and modeling work on lower molecular weight surrogate components such as n-decane and n-dodecane that are most relevant to jet fuel surrogates, but are also relevant to diesel surrogates where simulation of the full boiling point range is desired. For two-ring compounds, experimental work on decalin and tetralin recently has been published. For multi-component surrogate fuel mixtures, recent work on modeling of these mixtures and comparisons to real diesel fuel is reviewed. Detailed chemical kinetic models for surrogate fuels are very large in size. Significant progress also has been made in improving the mechanism reduction tools that are needed to make these large models practicable in multidimensional reacting flow simulations of diesel combustion. Nevertheless, major research gaps remain. In the case of iso-alkanes, there are experiments and modeling work on only one of relevance to diesel: iso-cetane. Also, the iso-alkanes in diesel are lightly branched and no detailed chemical kinetic models or experimental investigations are available for such compounds. More components are needed to fill out the iso-alkane boiling point range. For the aromatic class of compounds, there has been no new work for compounds in the boiling point range of diesel. Most of the new work has been on alkyl aromatics that are of the range C7 to C8, below the C10 to C20 range that is needed. For the chemical class of cycloalkanes, experiments and modeling on higher molecular weight components are warranted. Finally for multi-component surrogates needed to treat real diesel, the inclusion of higher molecular weight components is needed in models and experimental investigations.

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“…Based on the analysis in section 3.1 and 3.2.1, we chose decalin as the most suitable solvent currently due to its best performance at a relatively low temperature. Besides, it is the most stable one among the listed solvents . Thus, decalin was used in following experiments.…”

Section: Resultsmentioning

confidence: 99%

“…Besides, it is the most stable one among the listed solvents. [41][42][43] Thus, decalin was used in following experiments.…”

Section: F I G U R Ementioning

confidence: 99%

Insight into thermal dissociation of tri‐n‐octylamine hydrochloride: The key to realizing CO₂ mineralization with waste calcium/magnesium chloride liquids

Dong

Song

Zhang

et al. 2018

Energy Science & Engineering

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A thermal dissociation process (ideally, 100% atom utilization) to regenerate the amine extractant and to produce gaseous HCl which is the key to realizing the CO2 mineralization with metal chloride waste liquids was investigated. Solvent effects on the thermal dissociation of tri‐n‐octylamine hydrochloride (TOAHCl) were predicted to be prominent via analyzing structure parameters, charge distribution, solvation free energy, apparent basicity, and N‐H frequency with the help of molecular simulation and experiments. Inert solvents with low polarity such as decalin, dodecane were favorable in thermal dissociation experiments. In particular, decalin enhanced the dissociation most effectively which is in agreement with the prediction. In dilute solutions, the thermal dissociation kinetics was shown to be first order. The apparent reaction rate (3.0 × 10−4−1.5 × 10−2 min−1) and activation energy (58.219‐121.827 kJ/mol) differ a lot at 180‐190°C in various solvents, confirming a strong solvent effect. A two‐stage reaction scheme in dilute solutions has been proposed from the experimental study. The overall process is entropically driven, with the removal of HCl into gas phase from the solvated state. The work could offer a fundamental direction for the further actual process.

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Thermal Decomposition of Decalin: An Ab Initio Study

Cited by 32 publications

References 40 publications

Fast exploration of chemical reaction networks

Fast exploration of chemical reaction networks

Recent progress in the development of diesel surrogate fuels

Insight into thermal dissociation of tri‐n‐octylamine hydrochloride: The key to realizing CO₂ mineralization with waste calcium/magnesium chloride liquids

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Thermal Decomposition of Decalin: An Ab Initio Study

Cited by 32 publications

References 40 publications

Fast exploration of chemical reaction networks

Fast exploration of chemical reaction networks

Recent progress in the development of diesel surrogate fuels

Insight into thermal dissociation of tri‐n‐octylamine hydrochloride: The key to realizing CO2 mineralization with waste calcium/magnesium chloride liquids

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Product

Resources

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Insight into thermal dissociation of tri‐n‐octylamine hydrochloride: The key to realizing CO₂ mineralization with waste calcium/magnesium chloride liquids