Heat capacity and thermodynamic functions of transition metal ion (Cu²⁺, Fe²⁺, Mn²⁺) exchanged, partially dehydrated zeolite A (LTA)

We have measured the heat capacity from 1.8 to 300 K of partially dehydrated zeolite A (LTA), fully exchanged with Cu²⁺, Fe²⁺, and Mn²⁺ ions. The samples have a broad excess heat capacity contribution centered around 4 K, which we attribute to local electric fields splitting the magnetic moments of the cations. The excess heat capacity is modelled using a sum of several Schottky anomalies. From these models, we conclude that the cations in the Cu²⁺ zeolite reside in at least four distinct coordination environments, and that some of the coordination environments in all three zeolites are highly asymmetric. We also report theoretical fits of the heat capacity data, and values of the standard thermodynamic functions C_P,_m, Δ_0K^TS_m°, Δ_0K^TH_m°, and Φ_m° at smooth temperatures. The standard molar entropies at 298.15 K are 71.8 J·K⁻¹·mol⁻¹ for Cu-zeolite A (Cu_0.22Al_0.49Si_0.51O₂⋅1.04 H₂O), 71.1 J·K⁻¹·mol⁻¹ for Fe-zeolite A (Na_0.01Fe_0.23Al_0.50Si_0.51O₂⋅0.77 H₂O), and 66.0 J·K⁻¹·mol⁻¹ for Mn-zeolite A (Mn_0.26Al_0.49Si_0.50O₂⋅0.53 H₂O).