Gas-phase Hydrogen Research Articles

Synergic effects of temperature and pressure on the hydrogen diffusion and dissolution behaviour of X80 pipeline steel

Gas-phase hydrogen permeation experiments were conducted on X80 steel at temperatures from −15℃ to 60℃ and hydrogen pressures of 1, 4, 8 MPa. Hydrogen trap densities were determined, and a method for calculating nonlinear hydrogen concentration distribution was established and verified. Results reveal different temperature dependencies for hydrogen concentrations at varying pressures. At 4 and 8 MPa, the hydrogen concentration increases with temperature, whereas at 1 MPa, it initially decreases before increasing. Additionally, the influences of hydrogen pressure, hydrogen trap binding energy, and hydrogen trap density on this trend are discussed.

Numerical Investigation of the Flow Structure of Cryogenic Hydrogen in Corrugated Metal Flexhoses Due to Fluid Structure Interactions

Abstract In this paper, details of flow field characteristics and pressure drop of cryogenic hydrogen in corrugated metal flexhoses will be numerically evaluated using multiphase flow physics coupled with fluid structure interactions. Multiphase flow regime is often influenced by concentration ratio, shape factor, and orientation of the piping. Corrugated metal flexhoses are commonly used as part of cryogenic commodity transportation for their ability to operate in a large range of temperatures and pressures with a high degree of geometric flexibility. These sharp changes in the geometry of the flexhose convolutions are one of the leading factors of liquid and gas phase entrainment which can significantly reduce the efficiency of piping systems and fuel delivery systems to the engine components. The entrained gas phase hydrogen can eventually propagate in successive convolutes leading into the permanent entrapment of the gas phase hydrogen in the corrugations. The volume fraction up to 5% gas phase with various convolute heights and pitch will be evaluated, with a hose length to diameter ratio (L/D) range between 20 to 60 and a Reynolds number range between 5,000 to 350,000 based on the hose hydraulic diameter. The findings of the study contribute to a better understanding of multiphase flow physics of hydrogen in corrugated metal flexhoses.

Towards detailed combustor wall kinetics: An experimental and kinetic modeling study of hydrogen oxidation on Inconel

Gas-phase hydrogen combustion is ubiquitous in industrial processes, and the associated surface kinetics on heat-resistant alloys plays a crucial role in designing efficient low-carbon technologies. We conducted new temperature programmed reduction experiments to determine the reducibility of materials following an oxidation cycle. These experiments were modeled using a thermoconsistent multi-site microkinetic model for H2 heterogeneous oxidation on Inconels, which was validated against literature experiments. This competitive adsorption model considers iron bulk content, hydrogen spillover and subsurface oxygen migration on hydrogen surface oxidation kinetics. New X-ray diffraction experiments confirmed the postulated crystallographic structures in the Inconel samples, suggesting their presence on the surface scale. The phenomenological model was coupled with several state-of-the-art gas-phase oxidation mechanisms to assess gas/surface reactions interaction as a function of material and temperature. The results reveal a complex interaction in which surface removes H radicals from the gas-phase, while the Bradford (H2+OH) reaction converts OH into H2O, promoting water adsorption on Inconel. This interaction was found to give rise to gas-phase thermokinetic oscillations. The model predicts a non-monotonous effect of reactor area-to-volume ratio on reactivity and emphasizes the impact of Inconel composition on product selectivity. Overall, the multi-site model provides new insight into the contrasting reactivities among active sites, bridging the gap between material science and heterogeneous combustion modeling.

Natural hydrogen: sources, systems and exploration plays

Several sources of natural hydrogen are known or postulated but the process of serpentinization, the action of water on ultramafic rocks, is shown to be the most effective. Studies indicate that the rates and volumes generated by high-temperature serpentinization, (i.e. in the temperature range of 200–320°C), could feed a focused hydrogen system potentially capable of sealing and trapping gas-phase hydrogen in commercially-sized accumulations. Natural hydrogen is generated by serpentinization wherever ultramafic rocks can be penetrated by aqueous fluids. This includes diverse geotectonic settings ranging from divergent and convergent plate margins to intra-plate orogenic belts and Precambrian cratons. The ‘hydrogen system’ describes the generation, migration and sealing/trapping of hydrogen. There are two parts to the ‘generic hydrogen system’: the ‘source-generation sub-system’ requires an ultramafic protolith, usually in basement, and a supply of water penetrating basement rocks. In the ‘migration-retention sub-system’ migration, sealing and entrapment of gas-phase hydrogen behaves the same as for hydrocarbon gases. The hydrogen system by serpentinization is used to develop play models to guide exploration in the accessible and exploitable geotectonic settings of continental cratons, ophiolites and convergent margins. Thematic collection: This article is part of the Hydrogen as a future energy source collection available at: https://www.lyellcollection.org/topic/collections/hydrogen

Microbial hydrogen sinks in the sand-bentonite backfill material for the deep geological disposal of radioactive waste.

The activity of subsurface microorganisms can be harnessed for engineering projects. For instance, the Swiss radioactive waste repository design can take advantage of indigenous microorganisms to tackle the issue of a hydrogen gas (H2) phase pressure build-up. After repository closure, it is expected that anoxic steel corrosion of waste canisters will lead to an H2 accumulation. This occurrence should be avoided to preclude damage to the structural integrity of the host rock. In the Swiss design, the repository access galleries will be back-filled, and the choice of this material provides an opportunity to select conditions for the microbially-mediated removal of excess gas. Here, we investigate the microbial sinks for H2. Four reactors containing an 80/20 (w/w) mixture of quartz sand and Wyoming bentonite were supplied with natural sulfate-rich Opalinus Clay rock porewater and with pure H2 gas for up to 108 days. Within 14 days, a decrease in the sulfate concentration was observed, indicating the activity of the sulfate-reducing bacteria detected in the reactor, e.g., from Desulfocurvibacter genus. Additionally, starting at day 28, methane was detected in the gas phase, suggesting the activity of methanogens present in the solid phase, such as the Methanosarcina genus. This work evidences the development, under in-situ relevant conditions, of a backfill microbiome capable of consuming H2 and demonstrates its potential to contribute positively to the long-term safety of a radioactive waste repository.

In situ cell for grazing-incidence x-ray diffraction on thin films in thermal catalysis.

A cell for synchrotron-based grazing-incidence x-ray diffraction at ambient pressures and moderate temperatures in a controlled gas atmosphere is presented. The cell is suited for the in situ study of thin film samples under catalytically relevant conditions. To some extent, in addition to diffraction, the cell can be simultaneously applied for x-ray reflectometry and fluorescence studies. Different domes enclosing the sample have been studied and selected to ensure minimum contribution to the diffraction patterns. The applicability of the cell is demonstrated using synchrotron radiation by monitoring structural changes of a 3nm Pd thin film upon interaction with gas-phase hydrogen and during acetylene semihydrogenation at 150 °C. The cell allows investigation of very thin films under catalytically relevant conditions.

Polymer Waveguide Sensor Based on Evanescent Bragg Grating for Lab-on-a-Chip Applications.

In this work, an evanescent Bragg grating sensor inscribed in a few-mode planar polymer waveguide was integrated into microchannel structures and characterized by various chemical applications. The planar waveguide and the microchannels consisted of epoxide-based polymers. The Bragg grating structure was postprocessed by using point-by-point direct inscription technology. By monitoring the central wavelength shift of the reflected Bragg signal, the sensor showed a temperature sensitivity of -47.75 pm/K. Moreover, the functionality of the evanescent field-based measurements is demonstrated with two application examples: the refractive index sensing of different aqueous solutions and gas-phase hydrogen concentration detection. For the latter application, the sensor was additionally coated with a functional layer based on palladium nanoparticles. During the refractive index sensing measurement, the sensor achieved a sensitivity of 6.5 nm/RIU from air to 99.9% pure isopropyl alcohol. For the gas-phase hydrogen detection, the coated sensor achieved a reproducible concentration detection up to 4 vol% hydrogen. According to the reported experimental results, the integrated Bragg-grating-based waveguide sensor demonstrates high potential for applications based on the lab-on-a-chip concept.

Kinetic study of the CN + C2H6 hydrogen abstraction reaction based on an analytical potential energy surface.

The temperature dependence of the thermal rate constants and kinetic isotope effects (KIE) of the CN + C2H6 gas-phase hydrogen abstraction reaction was theoretically determined within the 25-1000 K temperature range, i.e., from very low- to high-temperature regimes. Based on a recently developed full-dimensional analytical potential energy surface fitted to highly accurate explicitly correlated ab initio calculations, three different kinetic theories were used: canonical variational transition state theory (CVT), quasiclassical trajectory theory (QCT), and ring polymer molecular dynamics (RPMD) method for the computation of rate constants. We found that the thermal rate constants obtained with the three theories show a V-shaped temperature dependence, with a pronounced minimum near 200 K, qualitatively reproducing the experimental measurements. Among the three methods used in this work, the QCT and RPMD methods have the best agreement with the experiment at low and high temperatures, respectively, while the CVT model shows the largest discrepancies. The significant increase in the rate constant at very low temperatures in this very exothermic and practically barrierless reaction could be attributed to the large value of the impact parameter, possibly ruling out the role of the tunneling effect and the intermediate complexes in the entrance channel. The theoretical H/D KIE depicted a "normal" behaviour, i.e., values greater than unity, emulating the experimental measurements and improving previous theoretical results. Finally, the discrepancies between theory and experiments were analysed as a function of several factors, such as limitations of the kinetics theories and the potential energy surface, as well as the uncertainties in the experimental measurements.

Reaction modelling of hydrogen evolution on nickel phosphide catalysts: density functional investigation.

Nickel phosphides (NixPy), particularly Ni2P, are promising catalysts for the acidic hydrogen evolution reaction (HER). Using density functional theory (DFT), we model HER at the potential of zero charge (PZC), incorporating solvation effects via an explicit water cluster and implicit surrounding solvent. Comparing the Volmer, Tafel, and Heyrovsky steps under saturated hydrogen coverage on Ni2P(0001) terminations, we find that the Ni3P2 (pristine) surface termination prefers the Volmer-Volmer-Tafel (VVT) pathway with activation energy (Ea) of 0.57 eV. Conversely, the Ni3P2 + 4P (reconstructed) surface favors the Volmer-Heyrovsky (VH) pathway with Ea = 0.60 eV. For the pristine surface termination, the differential gas-phase hydrogen adsorption free energies (ΔGdiff) correlate with the Volmer and Tafel step reaction energies, and a linear Bell-Evans-Polanyi relationship for the calculated activation and reaction energies validates the usefulness of the ΔGdiff descriptor for the Volmer step under PZC conditions. Nickel atoms play a crucial role in H2 production on both pristine and reconstructed surfaces, suggesting that modifications of the Ni sites can be used for catalyst design. Our findings highlight the importance of considering surface reconstruction and solvation effects on the HER catalytic performance.

Research progress on corrosion and hydrogen embrittlement in hydrogen–natural gas pipeline transportation

Hydrogen, clean, efficient and zero-carbon, is seen as a most promising energy source. The use of existing gas pipelines for hydrogen–natural gas transportation is considered to be an effective way to achieve long-distance, large-scale, efficient, and economical hydrogen transportation. However, the pipelines for hydrogen–natural gas transportation contain lots of impurities (e.g., CH4, high-pressure H2, H2S and CO2) and free water, which will inevitably lead to corrosion and hydrogen embrittlement. This paper presents a systematic review of research and an outlook for corrosion and hydrogen embrittlement in hydrogen–natural gas pipeline transportation. The results show that gas-phase hydrogen charging is suitable for hydrogen–natural gas transportation, but this technique lacks technical standards. By contrast, the liquid-phase hydrogen charging technique is more mature but has large deviation from the engineering reality. In the hydrogen–natural gas transportation pipelines, corrosion and hydrogen embrittlement are synergetic and competitive, but the failure mechanism and change law when corrosion and hydrogen embrittlement coexist remain unclear, which need to be further clarified by experiments. The failure mechanism is believed to be mainly sensitive to three key factors, i.e., the H2S/CO2 partial pressure ratio, the hydrogen blending ratio, and material strength. The increase of the three factors will make the pipeline materials more corrosive and more sensitive to hydrogen embrittlement. The research findings can be used as a reference for research and development of long-distance hydrogen–natural gas transportation technology and will drive the high-quality development of the hydrogen–natural gas blending industry.

Cold atomic gas identified by H I self-absorption

Context. Stars form in the dense interiors of molecular clouds. The dynamics and physical properties of the atomic interstellar medium (ISM) set the conditions under which molecular clouds and eventually stars form. It is, therefore, critical to investigate the relationship between the atomic and molecular gas phase to understand the global star formation process. Aims. Using the high angular resolution data from The H I/OH/Recombination (THOR) line survey of the Milky Way, we aim to constrain the kinematic and physical properties of the cold atomic hydrogen gas phase toward the inner Galactic plane. Methods. H I self-absorption (HISA) has proven to be a viable method to detect cold atomic hydrogen clouds in the Galactic plane. With the help of a newly developed self-absorption extraction routine (astroSABER), we built upon previous case studies to identify H I self-absorption toward a sample of giant molecular filaments (GMFs). Results. We find the cold atomic gas to be spatially correlated with the molecular gas on a global scale. The column densities of the cold atomic gas traced by HISA are usually on the order of 1020 cm−2 whereas those of molecular hydrogen traced by 13CO are at least an order of magnitude higher. The HISA column densities are attributed to a cold gas component that accounts for a fraction of ~5% of the total atomic gas budget within the clouds. The HISA column density distributions show pronounced log-normal shapes that are broader than those traced by H I emission. The cold atomic gas is found to be moderately supersonic with Mach numbers of approximately a few. In contrast, highly supersonic dynamics drive the molecular gas within most filaments. Conclusions. While H I self-absorption is likely to trace just a small fraction of the total cold neutral medium within a cloud, probing the cold atomic ISM by the means of self-absorption significantly improves our understanding of the dynamical and physical interaction between the atomic and molecular gas phase during cloud formation.

Neural network-based performance assessment of one- and two-liquid phase biotrickling filters for the removal of a waste-gas mixture containing methanol, α-pinene, and hydrogen sulfide

The performance of one- and two-liquid phase biotrickling filters (OLP/TLP-BTFs) treating a mixture of gas-phase methanol (M), α-pinene (P), and hydrogen sulfide (H) was assessed using artificial neural network (ANN) modeling. The best ANN models with the topologies 3-9-3 and 3-10-3 demonstrated an exceptional capacity for predicting the performance of O/TLP-BTFs, with R2 > 99%. The analysis of causal index (CI) values for the model of OLP-BTF revealed a negative impact of M on P removal (CI = -2.367), a positive influence of P and H on M removal (CI = +7.536 and CI = +3.931) and a negative effect of H on P removal (CI = -1.640). The addition of silicone oil in TLP-BTF reduced the negative impact of M and H on P degradation (CI = -1.261 and CI = -1.310, respectively) compared to the OLP-BTF. These findings suggested that silicone oil had the potential to improve P availability to the biofilm by increasing the concentration gradient of P between the air/gas and aqueous phases. Multi-objective particle swarm optimization (MOPSO) suggested an optimum operational condition, i.e. inlet M, P, and H concentrations of 1.0, 1.1, and 0.3 g m−3, respectively, with elimination capacities (ECs) of 172.1, 26.5, and 0.025 g m−3 h−1 for OLP-BTF. Likewise, one of the optimum operational conditions for TLP-BTF is achievable at inlet concentrations of 4.9, 1.7, and 0.8 g m−3, leading to the optimum ECs of 299.7, 52.9, and 0.072 g m−3 h−1 for M, P, and H, respectively. These results provide important insights into the treatment of complex waste gas mixtures, addressing the interactions between the pollutant removal characteristics in OLP/TLP-BTFs and providing novel approaches in the field of biological waste gas treatment.

Impedance of a tubular electrochemical cell with BZCY electrolyte and Ni-BZCY cermet electrodes for proton ceramic membrane reactors

In this work, impedance spectroscopy has been employed to explore the electrochemical behaviour of a 15 cm2 complete tubular cell with BaZr0.8Ce0.1Y0.1O3-δ (BZCY) electrolyte and two asymmetric Ni-BCZY cermet electrodes for hydrogen separation. Analyses of impedance spectra at different temperatures and gas compositions reveal that the thick inner electrode contributes most to the total polarisation resistance (Rp). For Rp there are four contributions with well-separated time constants of which gas phase hydrogen diffusion within the porous Ni-BZCY anode is predominant. The other three can be ascribed to proton migration through the space charge layer of the BZCY electrolyte adjacent to the Ni electrode, hydrogen redox charge transfer reactions, and hydrogen diffusion within Ni bulk. The present study guides the way to parameterise and, on this basis, optimise electrodes for scalable proton ceramic electrochemical cells.

Corrosion of X80 steel in the co-existence of sulfate reducing bacteria and permeating hydrogen

PurposeThis study aims to shed light on the corrosion behavior of X80 steel when sulfate-reducing bacteria (SRB) and permeating hydrogen interact.Design/methodology/approachIn this study, electrochemical tests were conducted between 25 and 55 °C, and the surface morphology of the specimen was observed using scanning electron microscopy and three-dimensional photos. The composition of the oxide film was characterized by X-ray photoelectron spectroscopy (XPS).FindingsUnder the condition of 6 MPa simulated natural gas (15% H2), the content of S-containing compounds (FeS and FeSO4) in the corrosion products on the surface of the specimen decreases from 60.8% to 54.4%. This finding indicates that hydrogen permeation inhibits the metabolic processes of SRB in this environment. By comparing the hydrogen-uncharged specimen, it was found that under the condition of 6 MPa simulated natural gas (15% H2) hydrogen charging, the uniform corrosion on the X80 surface was weakened, and the protection of the oxide film on the specimen surface in this environment was better than that without hydrogen charging.Originality/valueTo the best of the authors’ knowledge, most of these existing studies have focused on the effect of hydrogen on the mechanical properties of materials and very little is known about corrosion behavior in the hydrogen environment. In this study, a self-designed small gas phase hydrogen charging device was used to study the X80 surface corrosion behavior in the environment of the H2-doped natural gas pipeline.

Thermochemistry and Kinetics of the OH- and Cl-Initiated Degradation Pathways of the HCFC-132b Atmospheric Pollutant

The gas-phase hydrogen abstraction reaction of 1,2-dichloro-1,1-difluoroethane (CH2ClCClF2) with OH and Cl radicals is theoretically investigated by employing density functional theory methods combined with coupled-cluster-based composite schemes. The mechanism and kinetics of the degradation entrance channels of CH2ClCClF2, recently detected with increasing concentration in the atmosphere, is elucidated by using cost-effective ab initio triple-slash dual-level direct dynamics, jChS//B2PLYP-D3(BJ)/jun-cc-pV(T+d)Z///M06-2X-D3/jun-cc-pV(T+d)Z. Thermal rate constants are calculated over the temperature range of 200–1000 K by adopting both canonical- (CVT) and microcanonical (μVT)-variational transition state theory also including the microcanonically optimized multidimensional tunneling transmission coefficient (μOMT). The theoretical rate coefficient for the H-abstraction reaction initiated by the OH radical is computed to be kOHCVT/μOMT = 1.72 × 10–14 cm3 molecule–1 s–1 and kOHμVT/μOMT = 1.57 × 10–14 cm3 molecule–1 s–1 at 298 K, in excellent agreement with the available experimental data. The rate constant for the H-abstraction reaction by the Cl atom, here obtained for the first time, is predicted to be kClCVT/μOMT = 5.96 × 10–14 cm3 molecule–1 s–1 and kClμVT/μOMT = 5.65 × 10–14 cm3 molecule–1 s–1 at 298.15 K, thus showing increased efficiency with respect to the OH-prompted reaction.

Primary N2-He gas field formation in intracratonic sedimentary basins.

Helium, nitrogen and hydrogen are continually generated within the deep continental crust1-9. Conceptual degassing models for quiescent continental crust are dominated by an assumption that these gases are dissolved in water, and that vertical transport in shallower sedimentary systems is by diffusion within water-filled pore space (for example, refs. 7,8). Gas-phase exsolution is crucial for concentrating helium and forming a societal resource. Here we show that crustal nitrogen from the crystalline basementalone-degassing at a steady state in proportion to crustal helium-4 generation-can reach sufficient concentrations at the base of some sedimentary basins to form a free gas phase. Using a gas diffusion model coupled with sedimentary basin evolution, we demonstrate, using a classic intracratonic sedimentary basin (Williston Basin, North America), that crustal nitrogen reaches saturation and forms a gas phase; in this basin, as early as about 140 million years ago. Helium partitions into this gas phase. This gas formation mechanism accounts for the observed primary nitrogen-helium gas discovered in the basal sedimentary lithology of this and other basins, predicts co-occurrence of crustal gas-phase hydrogen, and reduces the flux of helium into overlying strata by about 30 per cent because of phase solubility buffering. Identification of this gas phase formation mechanism provides a quantitative insight to assess the helium and hydrogen resource potential in similar intracontinental sedimentary basins found worldwide.

Comparison of Designs of Hydrogen Isotope Separation Columns by Numerical Modeling

Mixtures of gas-phase hydrogen isotopologues (diatomic combinations of protium, deuterium, and tritium) can be separated using columns containing a solid such as palladium that reversibly absorbs hydrogen. A temperature-swing process can transport hydrogen into or out of a column by inducing temperature-dependent absorption or desorption reactions. We consider two designs: a thermal cycling absorption process, which moves hydrogen back and forth between two columns, and a simulated moving bed (SMB), where columns are in a circular arrangement. We present a numerical mass and heat transport model of absorption columns for hydrogen isotope separation. It includes a detailed treatment of the absorption–desorption reaction for palladium. By comparing the isotope concentrations within the columns as a function of position and time, we observe that SMB can lead to sharper separations for a given number of thermal cycles by avoiding the remixing of isotopes.

Constructing Collective Variables Using Invariant Learned Representations.

On the time scales accessible to atomistic numerical modeling, chemical reactions are considered rare events. Therefore, the atomistic simulations are commonly biased along a low-dimensional representation of a chemical reaction in an atomic structure space, i.e., along the collective variables. However, suitable collective variables are often complicated to guess a priori. We propose a novel method of collective variable discovery based on dimensionality reduction of the atomic representation vectors. These linear-scaling and invariant representations can be either fixed (untrained) or learned by supervised training of the end-to-end machine learning potential. The learned representations are expected to reflect not only the structural but also the energetic features of the system that are transferable to all of the reactive transformation covered by the machine learning potential. We demonstrate our approach on four high-barrier reactions ranging from a simple gas-phase hydrogen jump reaction to complex reactions in periodic models of industrially relevant heterogeneous catalysts. High data efficiency, automatized feature extraction, favorable scaling, and retention of inherent invariances are all properties that are expected to enable fast and largely automatic construction of suitable collective variables even in highly complex reactive scenarios such as reactive/catalytic transformations at solid-liquid interfaces.

Studies on In-situ regeneration of cold trap of a Bench-Top sodium loop

A cold trap (CT) is one of the crucial modules of the sodium coolant circuit of a sodium-cooled fast reactor as it controls hydrogen, oxygen and other impurities in liquid sodium within the threshold levels in dynamic mode. The major impurities are crystallized as NaH and Na2O in CT and get loaded during its continuous service. The CT at the secondary sodium circuit needs regeneration at regular intervals of time. In-situ regeneration of the CT during the reactor operation would be cost-effective while generating power. A bench-top sodium loop was employed to carry out the present study. The regeneration of CT was carried out by adopting a thermo-vacuum process in which the NaH decomposed into sodium and hydrogen. During the regeneration process, hydrogen release behavior as a function of time with varying temperature and cover gas pressure was investigated by deploying in-house developed online hydrogen sensors. An electrochemical hydrogen meter (ECHM) to measure hydrogen in liquid sodium in the ppb range, a semiconducting metal oxide-based hydrogen sensor (SMOHS) and a polymer electrolyte membrane-based hydrogen sensor (PEMHS) to measure hydrogen in the argon cover gas were used. Simultaneous measurement of hydrogen in both liquid sodium and cover gas phase played a central role in analyzing the hydrogen distribution phenomenon. The quantity of total hydrogen evolved and decomposed NaH was determined after the successful regeneration of the cold trap.

Ion-neutral clustering alters gas-phase hydrogen-deuterium exchange rates.

The rates and mechanisms of chemical reactions that occur at a phase boundary often differ considerably from chemical behavior in bulk solution, but remain difficult to quantify. Ion-neutral interactions are one such class of chemical reactions whose behavior during the nascent stages of solvation differs from bulk solution while occupying critical roles in aerosol formation, atmospheric chemistry, and gas-phase ion separations. Through a gas-phase ion separation technique utilizing a counter-current flow of deuterated vapor, we quantify the degree of hydrogen-deuterium exchange (HDX) and ion-neutral clustering on a series of model chemical systems (i.e. amino acids). By simultaneously quantifying the degree of vapor association and HDX, the effects of cluster formation on reaction kinetics are realized. These results imply that cluster formation cannot be ignored when modeling complex nucleation processes and biopolymer structural dynamics.