Heat capacity and thermodynamic functions of partially dehydrated cation-exchanged (Na+, Cs+, Cd2+, Li+, and NH4+) $\mathrm{RHO}$ zeolites

Neilsen, Grace; Dickson, Matthew S.; Rosen, Peter F.; Guo, Xin; Navrotsky, Alexandra; Woodfield, Brian F.

doi:10.1016/j.jct.2021.106620

Title: Heat capacity and thermodynamic functions of partially dehydrated cation-exchanged (Na⁺, Cs⁺, Cd²⁺, Li⁺, and NH₄⁺) $$\mathrm{RHO}$$ zeolites

Journal Article · 21 August 2021 · Journal of Chemical Thermodynamics

DOI: https://doi.org/10.1016/j.jct.2021.106620 · OSTI ID:1977290

Neilsen, Grace ^[1]; Dickson, Matthew S. ^[2]; Rosen, Peter F. ^[2]; Guo, Xin ^[3]; Navrotsky, Alexandra ^[3]; Woodfield, Brian F. ^[2]

Brigham Young University, Provo, UT (United States); OSTI
Brigham Young University, Provo, UT (United States)
Arizona State University, Tempe, AZ (United States)

Synthetic zeolites have a myriad of applications in industry due to their porous frameworks, potential to exhibit flexibility, and specific interactions with guest molecules. One topology of zeolites, RHO, is known to be flexible and have strong interactions with both H₂O and CO₂. Here we have performed heat capacity measurements on three partially dehydrated zeolite RHO samples containing extra-framework cations Na⁺ and Cs⁺, Cd²⁺ and Cs⁺, and Li⁺ and NH₄⁺ to understand the energetics of these materials. Based on fits of the heat capacity data, we report smooth thermodynamic functions of C_p,m, Δ^T₀S_m°, Δ^T₀H_m°, and Φ_m° for these samples. The standard S_m° at 298.15 K are 76.3 ± 0.8, 72.1 ± 0.8, and 68.8 ± 0.7 J∙K^-1∙mol^-1 for the Na,Cs RHO, Cd,Cs RHO, and Li,NH₄ RHO samples, respectively, and the standard H_m° at 298.15 K are 12.1 ± 0.1, 11.4 ± 0.1, and 11.4 ± 0.1 kJ∙mol^-1. Our measurements also show a transition in the heat capacity of Na,Cs RHO, the sample with the highest water content, between 180 and 300 K that is not clearly observed in the other two samples. We attribute this transition to labile water and cations in the framework. This movement could also be coupled with a temperature-induced lattice expansion. Future work will include heat capacity measurements on fully dehydrated and fully hydrated zeolite RHO in order to separate these two possible phenomena.

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Research Organization:: Brigham Young University, Provo, UT (United States); University of California, Davis, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0016446; SC0016573

OSTI ID:: 1977290

Journal Information:: Journal of Chemical Thermodynamics, Journal Name: Journal of Chemical Thermodynamics Journal Issue: C Vol. 164; ISSN 0021-9614

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Heat capacity and thermodynamic functions of partially dehydrated cation-exchanged (Na+, Cs+, Cd2+, Li+, and NH4+) $$\mathrm{RHO}$$ zeolites

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Title: Heat capacity and thermodynamic functions of partially dehydrated cation-exchanged (Na⁺, Cs⁺, Cd²⁺, Li⁺, and NH₄⁺) $$\mathrm{RHO}$$ zeolites