Experimental Rate Constants Research Articles

Characterization of PFOA isomers from PFAS precursors and their reductive defluorination

Perfluorooctanoic acid (PFOA) including linear and branched isomers is one of only three PFAS included in the Stockholm convention on Persistent Organic Pollutants. Unfortunately, PFOA branched isomers have received less attention than the linear due to analytical difficulties and perceived lower environmental concentrations. In this study, we revealed a environmentally relevant pathway for the formation of branched PFOA from PFAS precursors. AFFF samples showed a doubling of branched PFOA concentrations (138 mg/L) after TOP assay oxidation (307 mg/L). These findings indicate that branched PFOA may be more pervasive in the environment than previously thought. Additionally, we investigated the reductive degradability of PFOA using vitamin B12 (VB12) (a naturally occurring electron shuttle) in combination with either zero-valent zinc (ZVZ) or zero-valent iron (ZVI). Linear PFOA, as well as two branched isomers (3-methyl PFOA and 5,5-dimethyl PFOA), resisted reductive defluorination under the experimental conditions. However, all other branched isomers degraded within 10 days in the ZVZ-VB12 system. The experimental rate constants for specific PFOA isomers generally correlate with their calculated reduction potentials, except for 6-methyl PFOA. A potential defluorination pathway was proposed based on high-resolution mass spectrometry (LC-Orbitrap) and density functional theory (DFT) studies.

Unraveling Chain Branching in Cool Flames.

In cool flames, autoxidation of organic compounds forms alkyl hydroperoxides and ketohydroperoxides, and this controls the critical rate of chain branching, but there have been large uncertainties in the decomposition rate constants. We synthesized a series of hydroperoxides and measured their decomposition rate constants in pyrolysis experiments by spray-vaporization jet-stirred-reactor synchrotron vacuum ultraviolet photoionization mass spectrometry. Structural variation of the hydroperoxides, including alkyl, cycloalkyl, aromatic, and heterocyclic functionalities, has only a slight effect on their decomposition rate constants. Calculated rate constants are in good agreement with the experiment. The rate constant of ketohydroperoxide decomposition was obtained by theoretical calculation of 3-hydroperoxy butanal and tested by the pyrolysis of synthesized 3-hydroperoxy-3-phenylpropionate. The rate constant of ketohydroperoxide decomposition is close to that of alkyl hydroperoxides. The new chain-branching rate constants improves the cool-flame kinetic model, which is essential for removing discrepancies in model predictions and for the design of high-efficiency and low-emission engines.

Towards reliable calculations of thermal rate constants: Ring polymer molecular dynamics for the OH + HBr [formula omitted] Br + H[formula omitted]O reaction

We combined Moment Tensor Potential (MTP) and Ring Polymer Molecular Dynamics (RPMD) for calculating the thermal rate constants of the OH + HBr system. We used the active learning (AL) algorithm for constructing a training set during RPMD. We compared the obtained RPMD-AL-MTP rate constants with the ones previously calculated using the quasi-classical trajectories (QCT) and the POTLIB potential energy surface, and with the experimental ones. We demonstrated that the RPMD rate constants were systematically closer to the experimental rate constants than the QCT ones at 200 K, 300 K, and 500 K.

Predicting Nonradiative Decay Rate Constants of Cyclometalated Ir(III) Complexes.

The theoretical calculation of the temperature-dependent nonradiative decay rate constant is fundamental for predicting the usefulness of transition-metal complexes for technological applications. Such a computation implies the determination of the barriers separating the emitting triplet state from metal-centered states, which are key mediators of this type of radiationless relaxation. We here do so for the two green-emitting cyclometalated Ir(III) complexes, [Ir(ppy)2(pyim)]+ and [Ir(diFppy)2(dtb-bpy)]+, of general formula [Ir(C∧N)2(N∧N)]+, performing DFT calculations with both B3LYP and PBE0 functionals. On the basis of the obtained results and the comparison with the experimental nonradiative decay rate constants, we conclude that B3LYP provides too low energy barriers to the metal-centered states, while the PBE0 provides reasonable values. We consequently recommend to avoid the use of the commonly employed B3LYP functional for the evaluation of such an energy barrier for cyclometalated Ir(III) complexes.

The Fe-MAN Challenge: Ferrates-Microkinetic Assessment of Numerical Quantum Chemistry.

Organometallic species, such as organoferrate ions, are prototypical nucleophiles prone to reacting with a wide range of electrophiles, including proton donors. In solution, the operation of dynamic equilibria and the simultaneous presence of several organometallic species severely complicate the analysis of these fundamentally important reactions. This can be overcome by gas-phase experiments on mass-selected ions, which allow for the determination of the microscopic reactivity of the target species. In this contribution, we focus on the reactivity of a series of trisarylferrate complexes toward 2,2,2-trifluoroethanol and 2,2-difluoroethanol. By means of mass-spectrometric measurements, we determined the experimental bimolecular rate constants kexp of the gas-phase protolysis reactions of the trisarylferrate anions FePh3- and FeMes3- with the aforementioned acids. Based on these experiments, we carried out a dual blind challenge, inviting theoretical groups to submit their best predictions for the activation barriers and/or theoretical rate constants ktheo. This provides a unique opportunity to evaluate different computational protocols under minimal bias and sets the stage for further benchmarking of quantum chemical methods and data-driven approaches in the future.

Development of an Elementary Reaction-Based Kinetic Model to Predict the Aqueous-Phase Fate of Organic Compounds Induced by Reactive Free Radicals.

ConspectusAqueous-phase free radicals such as reactive oxygen, halogen, and nitrogen species play important roles in the fate of organic compounds in the aqueous-phase advanced water treatment processes and natural aquatic environments under sunlight irradiation. Predicting the fate of organic compounds in aqueous-phase advanced water treatment processes and natural aquatic environments necessitates understanding the kinetics and reaction mechanisms of initial reactions of free radicals with structurally diverse organic compounds and other reactions. Researchers developed conventional predictive models based on experimentally measured transformation products and determined reaction rate constants by fitting with the time-dependent concentration profiles of species due to difficulties in their measurements of unstable intermediates. However, the empirical treatment of lumped reaction mechanisms had a model prediction limitation with respect to the specific parent compound's fate. We use ab initio and density functional theory quantum chemical computations, numerical solutions of ordinary differential equations, and validation of the outcomes of the model with experiments. Sensitivity analysis of reaction rate constants and concentration profiles enables us to identify an important elementary reaction in formating the transformation product. Such predictive elementary reaction-based kinetics models can be used to screen organic compounds in water and predict their potentially toxic transformation products for a specific experimental investigation.Over the past decade, we determined linear free energy relationships (LFERs) that bridge the kinetic and thermochemical properties of reactive oxygen species such as hydroxyl radicals (HO•), peroxyl radicals (ROO•), and singlet oxygen (1O2); reactive halogen species such as chlorine radicals (Cl•) and bromine radicals (Br•); reactive nitrogen species (NO2•); and carbonate radicals (CO3•-). We used literature-reported experimental rate constants as kinetic information. We considered the theoretically calculated aqueous-phase free energy of activation or reaction to be a kinetic or a thermochemical property, and obtained via validated ab initio or density functional theory-based quantum chemical computations using explicit and implicit solvation models. We determined rate-determining reaction mechanisms involved in reactions by observing robust LFERs. The general accuracy of LFERs to predict aqueous-phase rate constants was within a difference of a factor of 2-5 from experimental values.We developed elementary reaction-based kinetic models and predicted the fate of acetone induced by HO• in an advanced water treatment process and methionine by photochemically produced reactive intermediates in sunlit fresh waters. We provided mechanistic insight into peroxyl radical reaction mechanisms and critical roles in the degradation of acetone and the formation of transformation products. We highlighted different roles of triplet excited states of two surrogate CDOMs, 1O2, and HO•, in methionine degradation. Predicted transformation products were compared to those obtained via benchtop experiments to validate our elementary reaction-based kinetic models. Predicting the reactivities of reactive halogen and nitrogen species implicates our understanding of the formation of potentially toxic halogen- and nitrogen-containing transformation products during water treatment processes and in natural aquatic environments.

Unexpected high yield of acrolein underlies the importance of the hydrogen-abstraction mechanism in photooxidation of allyl methyl sulfide (AMS).

This work explores theoretically the gas phase oxidation of allyl methyl sulfide (AMS, H2CCHCH2SCH3) initiated by •OH radicals, focusing on the H-abstraction pathway at the M06-2X-D3/aug-cc-pVTZ and MN15/aug-cc-pVTZ levels of theory (m06Tz and mn15Tz). The formation of a prereactive complex (PRC) is involved in H-abstraction processes with two potential directions of approach for the OH radical, denoted as “α” and “β”. The PRCs, demonstrate increased reactivity, primarily due to the interaction between the sulfur atoms and the hydroxyl hydrogen. A scheme for the H-abstraction mechanism that supports the experimentally identified products and predicts the formation of some S-containing low volatility products is proposed. The comparison of the potential energy surface (PES) between the double bond addition and H-abstraction paths in the AMS molecule shows that at the m06Tz level of theory, the H-abstraction on C3 and the addition to C1 have nearly the same profile of energy, while at the mn15Tz level, the minimum energy channel is the addition to C1. The theoretical rate coefficient for each reaction channel was calculated, considering the formation of a PRC prior to reaching the transition state of each channel and assuming thermal equilibrium between reactants and the PRC. The rate constants were calculated in a multi-TS/multi-conformer way at the SVECV-f12/m06Tz and SVECV-f12/mn15Tz levels of theory. The SVECV-f12 method is consistent in its predictions in both systems and exhibits only minor deviations from the experimental rate constants. Despite some specific differences due to the DFT method supporting the SVECV-f12 calculations, both methodologies predict a significant H-abstraction contribution in the AMS + OH gas phase reaction, which explains the high formation yield for acrolein determined experimentally.

Ta+ and Nb+ + CO2: intersystem crossing in ion-molecule reactions.

The reactions of Ta+ and Nb+ with CO2 proceed only by a highly efficient oxygen atom transfer reaction to the respective oxide at room temperature in the gas phase. Although the product spin states are not determined, thermochemistry dictates that they must be different from ground state quintet Ta+ and Nb+, implying that intersystem crossing (ISC) has occurred. Recent reactive scattering experiments found dominant indirect dynamics for the reaction with Ta+ hinting at a bottleneck along the reaction path. The question on the nature of the bottleneck, whether it involves a crossing point or a transition state, could not be finally answered because theory located both close to each other. Here, we aim at shedding further light onto the impact of intersystem crossing on the reaction dynamics and ultimately the reactivity of transition metal ion reactions in the gas phase. We employ a combination of thermal kinetics for Ta+ and Nb+ with CO2 using a selected-ion flow tube (SIFT) apparatus and differential scattering cross sections for Nb+ + CO2 from crossed-beam velocity map imaging. The reaction with niobium again shows dominant indirect dynamics and in general very similar dynamics compared to Ta+ + CO2. At thermal energies, both reactions show sub-collisional rate constants with small negative temperature dependencies. Experiments are complemented by high level quantum chemical calculations of the minimum energy pathway. Statistical modelling well-reproduces the experimental thermal rate constants, and suggests that the Nb+ reaction is rate-limited by the intersystem crossing at thermal energies.

Reaction rate constant: a theoretical description from local temperature.

Application of various descriptors based on electron density and its associated quantities to quantify chemical reactivity within the conceptual density functional theory has recently come into spotlight. Among others and particularly relevant to our study, local temperature based on electron density as well as kinetic energy density, as a measure of the kinetic energy of an electron moving in the Kohn-Sham potential of systems, should be mentioned. In this work, we propose to use the local temperature for describing the reaction rate constant, where our main idea originates from the point that the smaller the local temperature at the reaction center, the easier the electron removal, leading to a larger rate constant. On the basis of theoretical considerations, it is proved that the rate constant variations caused by the substituent effects can well be proportional to the local temperature at the reaction center. In order to numerically validate our proposed approach, we have taken the phenol derivatives with the available experimental rate constants of their O-methylation reaction as working models. The reason for this choice is that one of the most versatile approaches for labeling biologically active compounds with the 11C nuclide for positron emission tomography (PET) is methylation by methyl iodide including 11C nuclide, [11C]MeI, where methylation of phenolic oxygen with [11C]MeI is utilized to label some important tracers for PET studies. Our results unveil that the local temperature changes at the reaction center of the aforementioned reaction are reasonably correlated with the rate constant variations. Hopefully, incorporating the proposed correlations between the local temperature and the kinetics data into a computer control algorithm not only provides a simple tool for predicting the rate constant of the O-methylation reaction for other substituted phenols, but also, as a part of the chemical artificial intelligence, the optimum [11C]MeI labeling conditions for a wide variety of phenol derivatives can be controlled.

Oxepin Derivatives Formation from Gas-Phase Catechol Ozonolysis.

Quantum chemical calculations are performed to explore all of the possible pathways for primary ozonide (POZ) formation from gas-phase ozonolysis of catechol. Canonical transition state theory has been used to calculate the rate coefficients of individual steps for the formation of POZ. The calculated rate coefficients for 1,3-cycloaddition of ozone at the (i) unsaturated C(OH)═C(OH) bond and (ii) CH═C(OH) of catechol, respectively, are in good agreement with the experimental rate constant. In general, subsequent decomposition of POZ leads to well-known Criegee Intermediates. This work reveals a parallel pathway by which the endo-addition of ozone at CH═C(OH) of catechol proceeds through oxepin derivatives along with the paths leading to Criegee Intermediates and peroxy acids. The 7-membered heterocyclic oxepin derivatives have lower energies than Criegee Intermediates but similar relative energies with peroxy acids.

Modeling the Fluorescence Quantum Yields of Aromatic Compounds: Benchmarking the Machinery to Compute Intersystem Crossing Rates.

The from-first-principles calculation of fluorescence quantum yields (FQYs) and lifetimes of organic dyes remains very challenging. In this article, we extensively test the machinery to calculate FQYs. Specifically, we perform an extensive analysis on the parameters influencing the intersystem crossing (ISC), internal conversion (IC), and fluorescence rate constants calculations. The impact of (i) the electronic structure (chosen exchange-correlation functional and spin-orbit Hamiltonian), (ii) the vibronic parameters (coordinate system, broadening function, and dipole expansion), and (iii) the excited-state kinetic models are systematically assessed for a series of seven rigid aromatic molecules. Our studies provide more insights into the choice of parameters and the expected accuracy for the computational protocols aiming to deliver FQY values. Some challenges are highlighted, such as, on the one hand, the difficulty to benchmark against the experimental nonradiative rate constants, for which the separation between the IC and ISC contributions is often not provided in the literature and, on the other hand, the need to go beyond the harmonic approximation for the calculation of the IC rates.

Absorption of Water Vapor by Bambus[6]uril and a Density Functional Theory Study of Its Aqua Complexes

The absorption/desorption of water vapor by bambus[6]uril (Bu[6]) has been studied. According to kinetic experiments, the absorption capacity of Bu[6] is 4 moles of water per 1 mole of Bu[6] with the absorption duration of 20 min and the complete desorption duration of 100 min. Experimental rate constants for water vapor absorption and desorption by Bu[6] have been determined to be 0.166 min−1 and 0.0221 min−1, respectively. The obtained results are in agreement with theoretical calculations using the DFT method. A hypothetical structure of bambus[6]uril tetrahydrate (Bu[6]·4H2O) has been proposed based on the experimental and DFT data.

Nucleophilicity of 4-(Alkylthio)-3-imidazoline Derived Enamines.

Imidazolidine-4-thiones (ITOs) are cyclic, secondary amines that were considered as potential prebiotic organocatalysts for light-driven α-alkylations of aldehydes by bromoacetonitrile (BAN). Recent studies showed that the initially supplied ITOs represent the pre-catalyst because they undergo S-alkylation with BAN to give 4-(alkylthio)-3-imidazolines (TIMs). Given that the same reagent mix that undergoes light-driven α-alkylations is also effective in the dark, we synthesized ten ITO- or TIM-derived enamines of aldehydes and characterized their nucleophilic reactivities by kinetic studies in acetonitrile. The experimental second-order rate constants k2 for reactions of enamines with benzhydrylium ions (reference electrophiles) were evaluated by the Mayr-Patz equation, lg k2 (20 °C)=sN (N+E). The determined nucleophilicities N (and sN ) reveal the reactivity profiles of these enamines under prebiotically relevant conditions as well as their potential for use in organocatalytic synthesis.

Time-resolved excited-state dynamics of star-shaped carbazole-based room temperature phosphorescent molecule by ultrafast absorption spectroscopy

Star-shaped room-temperature phosphorescent (RTP) molecules have attracted much attention due to high luminescence efficiency by inhibiting nonradiative transition of triplet excitons. In this work, the photophysical processes of 1,3,5-tri(9h-carbazol-9-phenyl)benzene (TCzP) and tri(4-carbazol-9-phenyl)amine (TCzTa), with benzene and triphenylamine (TPA) as central cores respectively and carbazole (Cz) as peripheral groups, are investigated. The excited state absorption (ESA) signal (625 nm) of TCzP reaches maximum intensity within 8.8 ps in the femtosecond (fs) transient absorption (TA) spectroscopy and then decays significantly with the enhancing of triplet-triplet absorption (TTA) signal (425 nm). These evolution processes of spectral signal and the appearance of isosbestic point at 450 nm together confirm the intersystem crossing (ISC) process within 5.1 ns. The TTA signal gradually disappears in the nanosecond (ns) TA spectroscopy with a phosphorescence lifetime (τph) of 2 μs. Compared to TCzP, TCzTa exhibits similar spectral evolution behavior with faster ISC of 2.1 ns and lower τph of 0.95 μs. The theoretical simulation shows that the nitrogen atoms in the TPA core of TCzTa leads to a significantly increased spin-orbit coupling constant of S1→Tn (0.86 cm−1) and T1→S0 (0.08 cm−1) than that of TCzP (0.25 cm−1 and 0.05 cm−1), resulting in the shorter experimental ISC rate constants (2.1 ns) and τph (0.95 μs). This work provides reasonable insights for understanding the real-time spectral signal evolution of star-shaped carbazole-based RTP molecules.

Optimizing molecular potential models by imposing kinetic constraints with path reweighting.

Empirical force fields employed in molecular dynamics simulations of complex systems are often optimized to reproduce experimentally determined structural and thermodynamic properties. In contrast, experimental knowledge about the interconversion rates between metastable states in such systems is hardly ever incorporated in a force field due to a lack of an efficient approach. Here, we introduce such a framework based on the relationship between dynamical observables, such as rate constants, and the underlying molecular model parameters using the statistical mechanics of trajectories. Given a prior ensemble of molecular dynamics trajectories produced with imperfect force field parameters, the approach allows for the optimal adaption of these parameters such that the imposed constraint of equally predicted and experimental rate constant is obeyed. To do so, the method combines the continuum path ensemble maximum caliber approach with path reweighting methods for stochastic dynamics. When multiple solutions are found, the method selects automatically the combination that corresponds to the smallest perturbation of the entire path ensemble, as required by the maximum entropy principle. To show the validity of the approach, we illustrate the method on simple test systems undergoing rare event dynamics. Next to simple 2D potentials, we explore particle models representing molecular isomerization reactions and protein-ligand unbinding. Besides optimal interaction parameters, the methodology gives physical insights into what parts of the model are most sensitive to the kinetics. We discuss the generality and broad implications of the methodology.

Ab initio model of choice for kinetics of OH-addition to CF2=CFCl

This work presents a thorough resolution for significant differences (ranging from 7.3 to 23.2 times) between theoretical and experimental rate constants for the atmospheric OH-addition to CF2=CFCl, commonly used for manufacturing fluoropolymers, drugs, and fire extinguishers. To correctly describe its kinetic behaviors, it is crucial to use the energy profile calculated at an accurate method CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ, together with a rigorous stochastic RRKM-based master equation rate model. The model reveals that corrections from hindered rotation and tunneling treatments play a minor role, and CTFE is not a persistent organic pollutant due to its newly-calculated shorter lifetime with OH radicals.

Reactions of a hydrogen atom with haloacetates in aqueous solutions: Computational evidence for proton-coupled electron transfer and competing mechanisms.

A computational study of the mechanisms and kinetics of the aqueous reactions of a hydrogen atom with haloacetates is presented. Several mechanisms in the close competition are observed, such as proton-coupled electron transfer (PCET), hydrogen atom transfer (HAT), and halogen abstraction (XA). Computations predict that dechlorination takes place via PCET mechanisms and not via XA, as stated earlier, while XA is the fastest mechanism for . The reaction rate constants are reasonably well predicted within the theoretically most reliable canonical variational transition state theory with small curvature tunneling corrections and compared with the experimental ones. To reproduce the experimental rate constants of the debromination process it is necessary to include the PCET and XA cumulative values. Small curvature tunneling corrections to the rate constants are the highest for HAT and PCET mechanisms, up to 70 times larger than the Wigner, while variational effects for XA mechanisms are very small.

Evaluating Analytical Expressions for Scanning Electrochemical Cell Microscopy (SECCM).

Scanning electrochemical cell microscopy (SECCM) maps the electrochemical activity of a surface with nanoscale resolution using an electrolyte-filled nanopipette. The meniscus at the end of the pipet is sequentially placed at an array of locations across the surface, forming a series of nanometric electrochemical cells where the current-voltage response is measured. Quantitative interpretation of these responses typically employs numerical modeling to solve the coupled equations of transport and electron transfer, which require costly software or self-written code. Expertise and time are required to build and solve numerical models, which must be rerun for each new experiment. In contrast, algebraic expressions directly relate the current response to physical parameters. They are simpler to use, faster to calculate, and can provide greater insight but frequently require simplifying assumptions. In this work, we provide algebraic expressions for current and concentration distributions in SECCM experiments, which are formulated by approximating the pipet and meniscus using 1-D spherical coordinates. Expressions for the current and concentration distributions as a function of experimental parameters and in various conditions (steady state and time dependent, diffusion limited, and including migration) all show excellent agreement with numerical simulations employing a full geometry. Uses of the analytical expressions include determination of expected currents in experiments and quantifying electron-transfer rate constants in SECCM experiments.

Unveiling the Mechanistic Singularities of Caspases: A Computational Analysis of the Reaction Mechanism in Human Caspase-1.

Caspases are cysteine proteases in charge of breaking a peptide bond next to an aspartate residue. Caspases constitute an important family of enzymes involved in cell death and inflammatory processes. A plethora of diseases, including neurological and metabolic diseases and cancer, are associated with the poor regulation of caspase-mediated cell death and inflammation. Human caspase-1 in particular carries out the transformation of the pro-inflammatory cytokine pro-interleukin-1β into its active form, a key process in the inflammatory response and then in many diseases, such as Alzheimer's disease. Despite its importance, the reaction mechanism of caspases has remained elusive. The standard mechanistic proposal valid for other cysteine proteases and that involves the formation of an ion pair in the catalytic dyad is not supported by experimental evidence. Using a combination of classical and hybrid DFT/MM simulations, we propose a reaction mechanism for the human caspase-1 that explains experimental observations, including mutagenesis, kinetic, and structural data. In our mechanistic proposal, the catalytic cysteine, Cys285, is activated after a proton transfer to the amide group of the scissile peptide bond, a process facilitated by hydrogen-bond interactions with Ser339 and His237. The catalytic histidine does not directly participate in any proton transfer during the reaction. After formation of the acylenzyme intermediate, the deacylation step takes place through the activation of a water molecule by the terminal amino group of the peptide fragment formed during the acylation step. The overall activation free energy obtained from our DFT/MM simulations is in excellent agreement with the value derived from the experimental rate constant, 18.7 vs 17.9 kcal·mol-1, respectively. Simulations of the H237A mutant support our conclusions and agree with the reported reduced activity observed for this caspase-1 variant. We propose that this mechanism can explain the reactivity of all cysteine proteases belonging to the CD clan and that differences with respect to other clans could be related to the larger preference showed by enzymes of the CD clan for charged residues at position P1. This mechanism would avoid the free energy penalty associated with the formation of an ion pair. Finally, our structural description of the reaction process can be useful to assist in the design of inhibitors of caspase-1, a target in the treatment of several human diseases.

Numerical sensitivity analysis of temperature‐dependent reaction rate constants for optimized thermal conversion of high‐density plastic waste into combustible fuels

AbstractThe use of experimental rate constants for producing a high yield of liquid fuels from the pyrolysis of plastic waste is not widely accepted owing to a lack of compatibility between the different kinetic rate constants responsible for successful conversion reactions. In R software, the Arrhenius law can forecast the ideal combination of reaction rate constants and frequency factors and then perform sensitivity analysis on individual rate constants to estimate the selectivity and quantity of primary pyrolysis products. Sensitivity analysis is a way of determining the effectiveness of individual rate constants in the reaction. This research element is currently lacking in the literature for the cost‐effective valorization of plastics into combustible fuels. We are the first to use R software to perform sensitivity analysis on specific rate constants by reducing or raising their initial values to a point where maximum oil yield is attainable in the temperature range of 340–370°C. The primary focus was to save time and cost of extracting empirical rate constants from experiments to produce commercial‐scale pyrolytic oil. The H‐abstraction, chain fission, polymerization, and scission reactions were chosen due to the high availability of free radicals for maximum oil production. The oil recovery rate improved drastically to 90% at the end of processing time, while the number of by‐products gradually decreased. The k8 rate constant driven reaction is the best‐suited condition for industrial‐scale pyrolysis of high‐density plastics into liquid fuels, with 74% improvement in oil production and 14% improvement in light wax during sensitivity analysis.