Rate processes in cycling a reversible gas‐solid reaction

Stanish, M. A.; Perlmutter, David D.

doi:10.1002/aic.690300110

Cited by 27 publications

(9 citation statements)

References 11 publications

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“…It is a single step reaction leading to a simple kinetic mechanism. The only stable states of hydration reported in literature [5,24,30,31] and experimentally observed in the present work are the anhydrate and sesquihydrates forms.…”

Section: Potassium Carbonatesupporting

confidence: 44%

Characterization of potassium carbonate salt hydrate for thermochemical energy storage in buildings

Gaeini

shaik

Rindt

2019

Energy and Buildings

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Section: Potassium Carbonatesupporting

confidence: 44%

Characterization of potassium carbonate salt hydrate for thermochemical energy storage in buildings

Gaeini

shaik

Rindt

2019

Energy and Buildings

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“…In the range 1 < (P/Pe,) < 2, the model correctly predicts that the rate function is convex to the reduced-pressure axis. However, for (PIP,) > 2, the model predicts that the relative rate should asymptotically approach RAR = 3.67, whereas experiment shows that the rate of rehydration becomes proportional to pressure for (P/P,) > 3 (Stanish and Perlmutter, 1984).…”

Section: Rehydration Ratesmentioning

confidence: 92%

“…19 for rehydration may be rewritten in the form: suggesting the linearity test used on the coordinates of Figure 4(a). The data points on this figure are from the previous report of Stanish and Perlmutter (1984). The slope and intercept of the straight line yield 2' ' = 1.91 X 107K3 and [In kb -1/2 In T -€;/kT] = 1.30.…”

Section: Rehydration Ratesmentioning

confidence: 93%

“…Characteristic rehydration-dehydration cycling behavior is presented in Figure 5, taken from the data reported by Stanish and Perlmutter (1984) for KzC03, showing that both the forward and reverse reactions are accelerated by cycling. The primary effect occurs after the first cycle; iri addition, the induction and acceleration periods observed in the first-cycle dehydration and rehydration are eliminated in the second and later cycles.…”

Section: Role Of Solld-phase Propertiesmentioning

confidence: 99%

“…The behavior shown in Figure 5 thus suggests that cycling influences the reactivity of the solid phase itself, as indicated by the relative rate of nucleation. In drawing this irifcrerrce it should be noted that diffusional effect5 are insufficient to alone account for the rate changes produced by cycling (Stanish and Perlmutter, 1984) and cannot account for the elimination of the induction periods.…”

Section: Role Of Solld-phase Propertiesmentioning

confidence: 99%

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Kinetics of hydration‐dehydration reactions considered as solid transformations

Stanish¹,

Perlmutter²

1984

AIChE Journal

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A mechanism is proposed for the dehydration-rehydration process in solid inorganic salts, and model rate equations are derived and applied to the observed behavior of potassium carbonate. Quantitative expressions for the effect of pressure on the reaction rates are derived using basic principles from nucleation and heterogeneous phase transformation theory. Model equation predictions agree with experimental dehydration and rehydration rate data at all but extreme pressures. The basic rate equation is also used to interpret the data of Eckhardt and Flanagan (1964) for the effect of pressure on the dehydration of manganous formate dihydrate. The mechanism on which the model equations are based is also consistent with the observed effects of cycling and of high temperature pretreatment on the KzC03 rehydration rate. SCOPEA new mechanistic interpretation is offered for the analysis of the kinetics of gas-solid reactions and applied in detail to the reversible dehydration and rehydration of solid inorganic salts. These processes are considered as solid-solid transformations, and an expression is derived for the intrinsic rate of reaction in terms of the velocity of the movement of the boundary separating the reactant and product phases. The rate dependence on pressure and temperature predicted by the model equations is compared to those observed for both dehydration and rehydration in experiments with potassium carbonate hydrate and to that reported in the literature for the dehydration of manganous formate dihydrate. In addition, the effects of cycling and of high-temperature pretreatment on the reaction rates of KzCO3 are presented, and the ability of the proposed mechanism to account for these effects is discussed.A new mechanistic rate model has been formulated for reversible gas-solid reactions and applied to interpret the dehydration and rehydration kinetics of salt hydrates. Quantitative rate expressions predicting the effects of pressure and temperature were derived using basic principles from nucleation and heterogeneous phase transformation theories. The dehydration model rate equation provides accurate quantitative predictions for the velocity of movement of the KzCOs*3/2HzO dehydration interface at all three temperatures studied. The dehydration equation also provided a close correlation with data from the literature for the dehydration of manganous formate dihydrate.A comparison of the rehydration model equation with experimental KzC03 particle rehydration rates revealed good agreement of the model with the experimental data for reduced pressures within the range 1 < (Pes/P) < 2. At higher rehydration pressure, the reaction rates are not controlled by the transformation process at the reaction interface and the model equations are not applicable. Within the range of moderate pressures both above and below the equilibrium pressure, the model effectively describes the rapid decline of both dehydration and rehydration rates as the equilibrium pressure is approached.The model equations imply that reaction ra...

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Particle Size Optimization of Thermochemical Salt Hydrates for High Energy Density Thermal Storage

Martin

Lilley

Prasher

et al. 2023

Energy & Environ Materials

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Thermal energy storage (TES) solutions offer opportunities to reduce energy consumption, greenhouse gas emissions, and cost. Specifically, they can help reduce the peak load and address the intermittency of renewable energy sources by time shifting the load, which are critical toward zero energy buildings. Thermochemical materials (TCMs) as a class of TES undergo a solid–gas reversible chemical reaction with water vapor to store and release energy with high storage capacities (600 kWh m−3) and negligible self‐discharge that makes them uniquely suited as compact, stand‐alone units for daily or seasonal storage. However, TCMs suffer from instabilities at the material (salt particles) and reactor level (packed beds of salt), resulting in poor multi‐cycle efficiency and high‐levelized cost of storage. In this study, a model is developed to predict the pulverization limit or Rcrit of various salt hydrates during thermal cycling. This is critical as it provides design rules to make mechanically stable TCM composites as well as enables the use of more energy‐efficient manufacturing process (solid‐state mixing) to make the composites. The model is experimentally validated on multiple TCM salt hydrates with different water content, and effect of Rcrit on hydration and dehydration kinetics is also investigated.

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Rate processes in cycling a reversible gas‐solid reaction

Cited by 27 publications

References 11 publications

Characterization of potassium carbonate salt hydrate for thermochemical energy storage in buildings

Characterization of potassium carbonate salt hydrate for thermochemical energy storage in buildings

Kinetics of hydration‐dehydration reactions considered as solid transformations

Particle Size Optimization of Thermochemical Salt Hydrates for High Energy Density Thermal Storage

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