Mathematical and sensitivity analysis for chemical species in multistep dynamical system: A computational study.

This study presents a significant contribution to the field of chemical kinetics by providing a detailed analysis of a multi-step chemical kinetic process using ordinary differential equations (ODEs). The aim is to describe complex chemical processes' kinetics and the steady-state behavior of chemical species. The research employs reduction techniques to simplify the model by separating fast and slow processes based on their time scales, with a focus on a two-step reversible reaction mechanism. Special consideration is given to the phase flow of solution trajectories near equilibrium points, providing a clear depiction of system behavior. MATLAB simulations demonstrate the physical properties of observed data, while sensitivity analysis reveals parameters' impact on species behavior. Overall, this study enhances our understanding of chemical kinetics and offers insights into modeling complex reaction processes, with implications for various applications in chemistry and related fields.

Research on Hot Deformation Rheological Stress of Al-Mg-Si-Mn-Sc Aluminium Alloy.

The hot compression simulation testing machine was utilized to conduct compression experiments on an Al-Mg-Si-Mn alloy containing the rare earth element Sc at a deformation temperature ranging from 450 to 550 °C and a strain rate of 0.01 to 10 s-1. The study focused on the hot deformation behavior of the aluminum alloy, resulting in the determination of the optimal range of deformation process parameters for the alloy. The relationship between material flow stress, deformation temperature, and strain rate was described using the Arrhenius relationship containing thermal activation energy based on the stress-strain curve of hot compression deformation of aluminum alloy. This led to calculations for structural factor A, stress index n, and stress level parameters as well as thermal deformation activation energy to establish a constitutive Formula for hot deformation rheological stress of aluminum alloy and calculate the power dissipation factor η. Through this process, an optimized range for the optimal deformation process parameter for aluminum alloy was determined (deformation temperature: 490~510 °C; strain rate: 0.05 s-1) and verified in combination with mechanical properties and microstructure through hot extrusion deformation trial production.

Dielectric Modes in Antiferroelectric and Ferroelectric Liquid Crystals in a Pure Enantiomeric Version and a Racemic Mixture.

The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmCA*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmCA phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmCA* phase disappeared in the dielectric response of the racemic SmCA phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the PL mode existing in the racemic SmCA. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and PL modes, and discusses the full scheme of dielectric modes in enantiomer and racemate.

Exploring Bacillus species xylanases for industrial applications: screening via thermostability and reaction modelling.

CONTEXT: Xylanases derived from Bacillus species hold significant importance in various large-scale production sectors, with increasing demand driven by biofuel production. However, despite their potential, the extreme environmental conditions often encountered in production settings have led to their underutilisation. To address this issue and enhance their efficacy under adverse conditions, we conducted a theoretical investigation on a group of five Bacillus species xylanases belonging to the glycoside hydrolase GH11 family. Bacillus sp. NCL 87-6-10 (sp_NCL 87-6-10) emerged as a potent candidate among the selected biocatalysts; this Bacillus strain exhibited high thermal stability and achieved a transition state with minimal energy requirements, thereby accelerating the biocatalytic reaction process. Our approach aims to provide support for experimentalists in the industrial sector, encouraging them to employ structural-based reaction modelling scrutinisation to predict the ability of targeted xylanases. METHODS: Utilising crystal structure data available in the Carbohydrate-Active enzymes database, we aimed to analyse their structural capabilities in terms of thermal-stability and activity. Our investigation into identifying the most prominent Bacillus species xylanases unfolds with the help of the semi-empirical quantum mechanics MOPAC method integrated with the DRIVER program is used in calculations of reaction pathways to understand the activation energy. Additionally, we scrutinised the selected xylanases using various analyses, including constrained network analyses, intermolecular interactions of the enzyme-substrate complex and molecular orbital assessments calculated using the AM1 method with the MO-G model (MO-G AM1) to validate their reactivity.

Leaching behavior and kinetics of beryllium in beryllium-containing sludge (BCS).

Beryllium-containing sludge (BCS) is a byproduct of the physicochemical treatment of beryllium smelting wastewater. The pollutant element beryllium within BCS is highly unstable and extremely toxic, characterized by its small ionic radius and low charge density, resulting in a high risk of leaching and migration. This study is the first to investigate the leaching behavior, influencing mechanisms, and kinetic processes of beryllium in BCS under various environmental conditions. The results indicate that, under national standard conditions, beryllium exhibits a rapid leaching phase within the first 5 h, which then stabilizes after 10 h, with the total leached content significantly exceeding the leaching toxicity identification standards. Under mildly acidic (pH ≤ 5) or highly alkaline (pH = 14) conditions, beryllium demonstrates pronounced leaching and migration behaviors. Notably, in acidic conditions, the leaching rate exceeds 80% within 5 h. Combining the treatment process of beryllium-containing wastewater with analytical methods such as SEM, XPS, ToF-SIMS, and FTIR, it is revealed that due to the heterogeneous nature of BCS, the particle aggregates dissociate over time under acidic conditions. The particle surfaces become increasingly rough, leading to dissolution and the emergence of more reactive sites, resulting in a high proportion of beryllium leaching. Under these conditions, the gradual reaction of Be(OH)2 in BCS to form soluble Be2+ and its hydrolytic complexes is identified as the primary mechanism for extensive beryllium migration. The process encounters minimal diffusion resistance and is classified as reaction-controlled. In acidic conditions with pH = 4, the leaching rate of beryllium significantly increases with rising temperature. The leaching kinetics equation is [(1-x)-0.44]=e(18.26-53050RT)·t, with an apparent activation energy of 53.05 kJ mol-1.

Constraining Earth's nonlinear mantle viscosity using plate-boundary resolving global inversions.

Variable viscosity in Earth's mantle exerts a fundamental control on mantle convection and plate tectonics, yet rigorously constraining the underlying parameters has remained a challenge. Inverse methods have not been sufficiently robust to handle the severe viscosity gradients and nonlinearities (arising from dislocation creep and plastic failure) while simultaneously resolving the megathrust and bending slabs globally. Using global plate motions as constraints, we overcome these challenges by combining a scalable nonlinear Stokes solver that resolves the key tectonic features with an adjoint-based Bayesian approach. Assuming plate cooling, variations in the thickness of continental lithosphere, slabs, and broad scale lower mantle structure as well as a constant grain size through the bulk of the upper mantle, a good fit to global plate motions is found with a nonlinear upper mantle stress exponent of 2.43 [Formula: see text] 0.25 (mean [Formula: see text] SD). A relatively low yield stress of 151 [Formula: see text] 19 MPa is required for slabs to bend during subduction and transmit a slab pull that generates asymmetrical subduction. The recovered long-term strength of megathrusts (plate interfaces) varies between different subduction zones, with South America having a larger strength and Vanuatu and Central America having lower values with important implications for the stresses driving megathrust earthquakes.

Solubility of Hydrogen in a WMoTaNbV High-Entropy Alloy.

The WMoTaNbV alloy has shown promise for applications as a solid state hydrogen storage material. It absorbs significant quantities of H directly from the atmosphere, trapping it with high energy. In this work, the dynamics of the absorption of hydrogen isotopes are studied by determining the activation energy for the solubility and the solution enthalpy of H in the WMoTaNbV alloy. The activation energy was studied by heating samples in a H atmosphere at temperatures ranging from 20 °C to 400 °C and comparing the amounts of absorbed H. The solution activation energy EA of H was determined to be EA=0.22±0.02 eV (21.2 ± 1.9 kJ/mol). The performed density functional theory calculations revealed that the neighbouring host atoms strongly influenced the solution enthalpy, leading to a range of theoretical values from -0.40 eV to 0.29 eV (-38.6 kJ/mol to 28.0 kJ/mol).

Osmotic Dehydration Model for Sweet Potato Varieties in Sugar Beet Molasses Using the Peleg Model and Fitting Absorption Data Using the Guggenheim-Anderson-de Boer Model.

This study investigates the applicability of the Peleg model to the osmotic dehydration of various sweet potato variety samples in sugar beet molasses, addressing a notable gap in the existing literature. The osmotic dehydration was performed using an 80% sugar beet molasses solution at temperatures of 20 °C, 35 °C, and 50 °C for periods of 1, 3, and 5 h. The sample-to-solution ratio was 1:5. The objectives encompassed evaluating the Peleg equation's suitability for modeling mass transfer during osmotic dehydration and determining equilibrium water and solid contents at various temperatures. With its modified equation, the Peleg model accurately described water loss and solid gain dynamics during osmotic treatment, as evidenced by a high coefficient of determination value (r2) ranging from 0.990 to 1.000. Analysis of Peleg constants revealed temperature and concentration dependencies, aligning with previous observations. The Guggenheim, Anderson, and de Boer (GAB) model was employed to characterize sorption isotherms, yielding coefficients comparable to prior studies. Effective moisture diffusivity and activation energy calculations further elucidated the drying kinetics, with effective moisture diffusivity values ranging from 1.85 × 10-8 to 4.83 × 10-8 m2/s and activation energy between 7.096 and 16.652 kJ/mol. These findings contribute to understanding the complex kinetics of osmotic dehydration and provide insights into the modeling and optimization of dehydration processes for sweet potato samples, with implications for food processing and preservation methodologies.

Probing the ionic activation enthalpies in anionic polysaccharide xerogel-based single ion conductor for temperature sensing.

Ionic charge transport in polymer-based solid electrolytes is significantly affected by thermal perturbations, facilitating the detection of temperature variations. However, the impact of ionic interactions and molecular arrangements in polymeric single-ion conductors (SICs) has not been thoroughly investigated for temperature sensing. By probing the effect of the associated energies for ionic interactions and polymeric rearrangements, the thermal sensing characteristics of alginate have been studied. For the first time, alginate SIC interacting with multivalent ions (viz., Na+, Ca2+ and Fe3+) to form xerogel has been exploited as a temperature-sensing layer by fabricating a xerogel-based ionic thermistor (xIT) as a temperature sensor. The xIT has demonstrated stable functioning from 25 to 70 °C and unveiled enhanced sensing abilities in the physiological state of the human body (35-40 °C), exhibiting a monotonic linear response, high sensitivity (-3.77 % °C-1), and high accuracy (0.1 °C). The sensing characteristic is observed due to the inward ionic flux under thermal and electrical perturbations. The concentration of ionic charge carriers and ionic drift are assumed to be Arrhenius-activated processes. A general microscopic model of ion transport within polysaccharides has been elucidated via hopping mechanisms, and the effects of the associated activation energies on temperature sensitivity have been explained.

Formation of chlorophyll-anionic polysaccharide complex coacervates to improve chlorophyll color stability: Thermodynamic and kinetic stability studies.

Chlorophyll (Chl) is the predominant pigment in green plants that can act as a food color and possesses various functional activities. However, its instability and rapid degradation on heating compromise the sensory qualities of its products. This study aimed to enhance the heat resistance of Chl by forming complex coacervates with two negatively charged polysaccharides, sodium alginate (SA) and K-carrageenan (KC). Dynamic light scattering and scanning electron microscopy analyses confirmed the formation of coacervates between Chl and the polysaccharides, whereas Fourier-transform infrared spectroscopy revealed that hydrogen bonding and electrostatic attraction were the primary forces behind complex formation. Electron spin resonance and thermodynamic studies further revealed that these complexes bolstered the thermal stability of Chl, with a maximum improvement of 70.38 % in t1/2 and a reduction of 50.72 % in the degradation rate constant. In addition, the antioxidant capacity of Chl was enhanced up to 35 %. Therefore, this study offers a novel approach to Chl preservation and suggests a viable alternative to artificial pigments in food products.

Regulating Desolvation Activation Energy and Zn Deposition via a CTAB-Intercalated Mg-Al-Layered Double-Hydroxide Protective Layer for Durable Zn Metal Anodes.

While aqueous Zn-ion batteries (AZIBs) are widely considered as a promising energy storage system due to their merits of low cost, high specific capacity, and safety, the practical implementation has been hindered by the Zn dendrite growth and undesirable parasitic reactions. To address these issues, a unique hydrophobic-ion-conducting cetyltrimethylammonium bromide-intercalated Mg-Al-layered double-hydroxide protective layer was constructed on the Zn anode (OMALDH-Zn) to modulate the nucleation behavior and desolvation process. The hydrophobic cetyl group long chain can inhibit the hydrogen evolution reaction and Zn corrosion by repelling water molecules from the anode surface and reducing the desolvation activation energy. Meanwhile, the Mg-Al LDH with abundant zincophilic active sites can modulate the Zn2+ ion flux, enabling the dendrite-free Zn deposition. Benefiting from this interfacial synergy, a long cycle life (>2300 h) with low and stable overpotential (<18 mV at 1 mA cm-2) and excellent Coulombic efficiency (99.4%) for symmetrical and asymmetrical batteries were achieved. More impressively, excellent rate performance and long cyclic stability have been realized by OMALDH-Zn//MnO2 batteries in both coin-type and pouch-type devices. This low-cost, simple, and high-efficiency coordinated modulation method provides a reliable strategy for the practical application of AZIBs.

Accelerating Anhydrous Proton Transport in Covalent Organic Frameworks: Pore Chemistry and Its Impacts.

Proton conduction is important in both fundamental research and technological development. Here we report designed synthesis of crystalline porous covalent organic frameworks as a new platform for high-rate anhydrous proton conduction. By developing nanochannels with different topologies as proton pathways and loading neat phosphoric acid to construct robust proton carrier networks in the pores, we found that pore topology is crucial for proton conduction. Its effect on increasing proton conductivity is in an exponential mode other than linear fashion, endowing the materials with exceptional proton conductivities exceeding 10-2 S cm-1 over a broad range of temperature and a low activation energy barrier down to 0.24 eV. Remarkably, the pore size controls conduction mechanism, where mesopores promote proton conduction via a fast-hopping mechanism, while micropores follow a sluggish vehicle process. Notably, decreasing phosphoric acid loading content drastically reduces proton conductivity and greatly increases activation energy barrier, emphasizing the pivotal role of well-developed proton carrier network in proton transport. These findings and insights unveil a new general and transformative guidance for designing porous framework materials and systems for high-rate ion conduction, energy storage, and energy conversion.

Mechanistic study of the differences in lactic acid bacteria resistance to freeze- or spray-drying and storage.

Lactobacillus delbrueckii subsp. bulgaricus and Lactiplantibacillus plantarum are two lactic acid bacteria (LAB) widely used in the food industry. The objective of this work was to assess the resistance of these bacteria to freeze- and spray-drying and study the mechanisms involved in their loss of activity. The culturability and acidifying activity were measured to determine the specific acidifying activity, while membrane integrity was studied by flow cytometry. The glass transitions temperature and the water activity of the dried bacterial suspensions were also determined. Fourier transform infrared (FTIR) micro-spectroscopy was used to study the biochemical composition of cells in an aqueous environment. All experiments were performed after freezing, drying and storage at 4, 23 and 37 °C. The results showed that Lb. bulgaricus CFL1 was sensitive to osmotic, mechanical, and thermal stresses, while Lpb. plantarum WCFS1 tolerated better the first two types of stress but was more sensitive to thermal stress. Moreover, FTIR results suggested that the sensitivity of Lb. bulgaricus CFL1 to freeze-drying could be attributed to membrane and cell wall degradation, whereas changes in nucleic acids and proteins would be responsible of heat inactivation of both strains associated with spray-drying. According to the activation energy values (47-85 kJ/mol), the functionality loss during storage is a chemically limited reaction. Still, the physical properties of the glassy matrix played a fundamental role in the rates of loss of activity and showed that a glass transition temperature 40 °C above the storage temperature is needed to reach good preservation during storage. KEY POINTS: • Specific FTIR bands are proposed as markers of osmotic, mechanic and thermal stress • Lb. bulgaricus CFL1 was sensitive to all three stresses, Lpb. plantarum WCFS1 to thermal stress only • Activation energy revealed chemically limited reactions ruled the activity loss in storage.

DSC Derived (Ea & ΔG) Energetics and Aggregation Predictions for mAbs.

The Arrhenius energy of activation of unfolding Ea unfolding and Gibbs free energy of unfolding ΔG unfolding have been calculated utilizing DSC differential scanning calorimetry for 4 mAbs (1 biosimilar) in 3 formulations. DSC derived ΔTm melting temperature changes for each mAb domain (CH2, Fab, CH3) at calorimetric scan rates at 60 °C, 90 °C, 150 °C and 200 °C / hr. were utilized to calculate the kinetic Eaunfolding. The DSC derived Ea trend with observed aggregate formation and can be used to predict%HMW formation post 9-month storage at 5 °C and 40 °C for all formulations analyzed. Additionally, thermodynamic ΔG unfolding energies were also derived (Tm, ΔCp and ΔH measurements) for each mAb at every scan rate to observe scan rate dependence of ΔG and for extrapolation to 0 °C/hr. (to report ΔG at true equilibrium conditions). Both derived thermodynamic ΔG and kinetic Ea energies were combined to build full energetic landscapes for mAb unfolding and aggregation. Statistical multivariate analysis of kinetic (Ea CH2, Ea Fab, Ea CH3) energies, thermodynamic (ΔG5 °C and ΔG40 °C) energies and in-silico modeled surface properties was also performed. Analysis revealed key significant parameters contributing to aggregation. These parameters were utilized to build predictive aggregation models for 25 mg/mL mAb formulations stored 9-months at 5 °C and 40 °C.

Prediction of nanocomposite properties and process optimization using persistent homology and machine learning.

Physical property prediction and synthesis process optimization are key targets in material informatics. In this study, we propose a machine learning approach that utilizes ridge regression to predict the oxygen permeability at fuel cell electrode surfaces and determine the optimal process temperature. These predictions are based on a persistence diagram derived from tomographic images captured using transmission electron microscopy (TEM). Through machine learning analysis of the complex structures present in the Pt/CeO2 nanocomposites, we discovered that l2 regularization considering diverse structural elements is more appropriate than l1 regularization (sparse modeling). Notably, our model successfully captured the activation energy of oxygen permeability, a phenomenon that could not be solely explained by the geometric feature of the Betti numbers, as demonstrated in a previous study. The correspondence between the ridge regression coefficient and persistence diagram revealed the formation process of the local and three-dimensional structures of CeO2 and their contributions to pre-exponential factor and activation energies. This analysis facilitated the determination of the annealing temperature required to achieve the optimal structure and accurately predict the physical properties.

Hydrogen spillover inspired bifunctional Platinum/Rhodium Oxide-Nitrogen-Doped carbon composite for enhanced hydrogen evolution and oxidation reactions in base.

The poor activity of Pt-based-catalysts for alkaline hydrogen oxidation/evolution reaction (HOR/HER) encourages scientific society to design an effective electrocatalyst to develop alkaline fuel cells/electrolyzers. Herein, platinum/rhodium oxide-nitrogen-doped carbon (Pt/Rh2O3-CNx) composite is prepared for alkaline HER and HOR inspired by hydrogen spillover. The HER performance of Pt/Rh2O3-CNx is âˆ¼ 6 times higher than Pt/C. In HOR, Pt/Rh2O3-CNx possesses an exchange current density of 657.60 mA/mgmetal, which is âˆ¼ 3.4 times higher than Pt/C. Hydrogen and hydroxyl binding energy (HBE and OHBE) contribute equally to alkaline HOR/HER. The experimental and theoretical evidence suggests that the enhanced HER and HOR activity of Pt/Rh2O3-CNx may be due to hydrogen spillover from Pt to Rh2O3. Small work function difference [0.08 eV] of the system suggested hydrogen-spillover is feasible, which has been justified by reaction-free energy calculations. We proposed that the dissociation of hydrogen (H2) and water (H2O) occurs at Pt to form Pt-adsorbed hydrogen species (Pt-Had). Then, some Had moves to Rh2O3 through hydrogen spillover and reacts with neighboring Had or adsorbed hydroxyl species (OHad) to form H2 or H2O, which enhances the HER and HOR activity, respectively. The role of water-metal-hydroxyl species in the electrical double layer was also demonstrated on alkaline HOR/HER. This work may help to design the hydrogen-spillover-based catalysts for several renewable energy technologies.

Experimental and numerical study of temperature evolution and hydrogen desorption process on an amorphous alloy Mg50Ni50.

In the present study, we explored the temperature evolution and hydrogen desorption properties of the Mg50Ni50 alloy through both numerical simulation and experimental analyses. Desorption kinetics characterization was carried out using the volumetric method, specifically employing a Sievert's-type apparatus to investigate solid-gas reactions. The experiments covered a temperature range from 313 K to 353 K, with an initial hydrogen pressure of 12 bar. Simultaneously, a mathematical approach was employed to numerically investigate the temperature evolution within the hydride bed. Using COMSOL Multiphysics as a simulator, a numerical simulation was conducted based on experimental data. The study examined the impact of cooling temperature on hydride temperature evolution. Results revealed that hydrogen desorption kinetics of the amorphous Mg50Ni50 alloy are more significant compared to those of Mg2Ni compounds. Moreover, the effect of the warming temperature on the equilibrium pressure can also be observed in the hydrogen desorption isotherm curves. The experimental study of the Mg50Ni50 alloy provided activation energy data, along with determination of hydride formation enthalpy and entropy. On the other hand, we showed that the hydride temperature is maximum at the hydride-hydrogen interface within the hydride center.

Reliability Study of Metal-Oxide Semiconductors in Integrated Circuits.

This paper is devoted to the study of CMOS IC parameter degradation during reliability testing. The paper presents a review of literature data on the issue of the reliability of semiconductor devices and integrated circuits and the types of failures leading to the degradation of IC parameters. It describes the tests carried out on the reliability of controlled parameters of integrated circuit TPS54332, such as quiescent current, quiescent current in standby mode, resistance of the open key, and instability of the set output voltage in the whole range of input voltages and in the whole range of load currents. The calculated values of activation energies and acceleration coefficients for different test temperature regimes are given. As a result of the work done, sample rejection tests have been carried out on the TPS54332 IC under study. Experimental fail-safe tests were carried out, with subsequent analysis of the chip samples by the controlled parameter quiescent current. On the basis of the obtained experimental values, the values of activation energy and acceleration coefficient at different temperature regimes were calculated. The dependencies of activation energy and acceleration coefficient on temperature were plotted, which show that activation energy linearly increases with increasing temperature, while the acceleration coefficient, on the contrary, decreases. It was also found that the value of the calculated activation energy of the chip is 0.1 eV less than the standard value of the activation energy.

Thermogravimetric Analysis of Moisture in Natural and Thermally Treated Clay Materials.

Clays are a class of porous materials; their surfaces are naturally covered by moisture. Weak thermal treatment may be considered practical to remove the water molecules, changing the surface properties and making the micro- and/or mesoporosities accessible to interact with other molecules. Herein, a modulated thermogravimetric analysis (MTGA) study of the moisture behavior on the structures of five, both fibrous and laminar, clay minerals is reported. The effect of the thermal treatment at 150 °C, which provokes the release of weakly adsorbed water molecules, was also investigated. The activation energies for the removal of the adsorbed water (Ea) were calculated, and they were found to be higher, namely, from 160 to 190 kJ mol-1, for fibrous clay minerals compared to lamellar structures, ranging in this latter case from 80 to 100 kJ mol-1. The thermal treatment enhances the rehydration in Na-montmorillonite, stevensite, and sepiolite structures with a decrease in the energy required to remove it, while Ea increases significantly in palygorskite (from 164 to 273 kJ mol-1). As a proof of concept, the MTGA results are statistically correlated, together with a full characterization of the physico-chemical properties of the five clay minerals, with the adsorption of two molecules, i.e., aflatoxin B1 (AFB1) and ß-carotene. Herein, the amount of adsorbed molecules ranges from 12 to 97% for the former and from 22 to 35% for the latter, depending on the particular clay. The Ea was correlated with AFB1 adsorption with a Spearman score of -0.9. When the adsorbed water is forcibly removed, e.g., under vacuum conditions and high temperatures, the structure becomes the most important, decreasing the Spearman score between ß-carotene and Ea to -0.6.

Quantum information scrambling and chemical reactions.

The ultimate regularity of quantum mechanics creates a tension with the assumption of classical chaos used in many of our pictures of chemical reaction dynamics. Out-of-time-order correlators (OTOCs) provide a quantum analog to the Lyapunov exponents that characterize classical chaotic motion. Maldacena, Shenker, and Stanford have suggested a fundamental quantum bound for the rate of information scrambling, which resembles a limit suggested by Herzfeld for chemical reaction rates. Here, we use OTOCs to study model reactions based on a double-well reaction coordinate coupled to anharmonic oscillators or to a continuum oscillator bath. Upon cooling, as one enters the tunneling regime where the reaction rate does not strongly depend on temperature, the quantum Lyapunov exponent can approach the scrambling bound and the effective reaction rate obtained from a population correlation function can approach the Herzfeld limit on reaction rates: Tunneling increases scrambling by expanding the state space available to the system. The coupling of a dissipative continuum bath to the reaction coordinate reduces the scrambling rate obtained from the early-time OTOC, thus making the scrambling bound harder to reach, in the same way that friction is known to lower the temperature at which thermally activated barrier crossing goes over to the low-temperature activationless tunneling regime. Thus, chemical reactions entering the tunneling regime can be information scramblers as powerful as the black holes to which the quantum Lyapunov exponent bound has usually been applied.