Calorimetric measurements have been carried out on specimens of natrolite, mesolite, and scolecite in order to assess the thermodynamic properties of a zeolite series having the same alumino-silicate framework. Low-temperature heat capacity and high-temperature enthalpy increments of natrolite and scolecite were measured by adiabatic and drop-calorimetric techniques. Standard enthalpies of formation at 298.15 K of all three zeolites were determined by solution calorimetry. Thermodynamic functions have been calculated for natrolite to 660 K and for scolecite to 470 K. The heat capacity and standard entropy at 298.15 K have been estimated for mesolite. The following values at T = 298.15 K and a pressure of 1 bar have been obtained:

ΔH°f(T)C°p(T)S°(T)-S°(0)ΔG°f(T)
kJ/molJ/(mol · K)J/(mol · K)kJ/mol
natrolite −5718.6±5.0 359.23±0.72 359.23±0.72 −5316.6+5.0 
mesolite −5947.1±5.4 371 ±2 363 ±2 −5513.2±5.4 
scolecite −6049.0±5.0 382.81 ±0.77 367.42±0.73 −5597.9±5.0 
ΔH°f(T)C°p(T)S°(T)-S°(0)ΔG°f(T)
kJ/molJ/(mol · K)J/(mol · K)kJ/mol
natrolite −5718.6±5.0 359.23±0.72 359.23±0.72 −5316.6+5.0 
mesolite −5947.1±5.4 371 ±2 363 ±2 −5513.2±5.4 
scolecite −6049.0±5.0 382.81 ±0.77 367.42±0.73 −5597.9±5.0 

With reference to zeolitic water, it is concluded that the entropy of water molecules in both natrolite and scolecite is similar to that in ice. A consideration of the X-ray results for the present specimen of natrolite leads to the conclusion that a contribution of about 9.2 J/(mol · K) to the standard entropy is made by the Al-Si disorder in the alumino-silicate framework. The new results allow calculations to be made by which the pressure and temperature effect can be deduced for such equilibria as:
natrolite + SiO2(aq)=2 analcime
and
natrolite + Ca2+(aq) + H2O = mesolite + 2Na+(aq).

Results are consistent with observed parageneses in natural occurrences.

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