Cryogenic heat capacity measurements and thermodynamic analysis of lithium aluminum layered double hydroxides (LDHs) with intercalated chloride

Abstract

This is the peer-reviewed, final accepted version for American Mineralogist, published by the Mineralogical Society of America.The published version is subject to change. Cite as Authors (Year) Title. American Mineralogist, in press.

Role of Anions in Stabilizing the [Zn–Al] Layered Double Hydroxides: A Thermodynamic Study

“…This explains the higher %RMS values for these fits compared to previous ones. 14 However, eq 4 provided satisfactory fits for all these samples. These fits of the heat capacity data were then used to calculate the thermodynamic functions C p,m , Δ T S m , Δ T H m , and Φ m .…”

“…Schottky anomalies can be used to fit the low-temperature heat capacity of other LDHs as well. Our groups have previously published a paper about [Li–Al–Cl] LDHs with a similar “leveling off” seen at low temperatures . In that paper, the heat capacity below 11 K was fit using C normalp , normalm = γ T + B 3 T 3 + B 5 T 5 + B 7 T 7 with γ being the parameter for the linear term obtained from the fitting procedure.…”

“…Our groups have previously published a paper about [Li−Al−Cl] LDHs with a similar "leveling off" seen at low temperatures. 14 In that paper, the heat capacity below 11 K was fit using…”

“…We then revisited the [Li−Al−Cl] LDH data and found that using eq 1 resulted in comparable or better fits for the three undoped LDH samples reported previously. 14 The parameters for these samples using eq 1 are given in Table S5.…”

“…16−19 A detailed description of S°c onfig has already been reported in the previous papers from our group. 11,14 S°c onfig decreases as water content increases as water molecules fill any vacancies in the interlayer and decrease the overall disorder in the interlayer. Accordingly, the S°c onfig values for these LDHs follow the inverse trend with the water content ([Zn−Al−…”