Potassium Nitrate has much higher thermal stability than calcium nitrate.
Group II nitrates become more thermally stable down the group. WHY?: the smaller metal ion has a higher charge density therefore a higher polarising power compared to the nitrate ion. The nitrate ions has a large, easily polarisable electron cloud. Calcium ion easily polarises the large anion, attracting the electrons, this distorts the shape of the anion, the lattice is easier to breakup, this encourages decomposition.
Group I nitrates have a higher thermal stability because the potassium ion is much larger than the calcium, therefore much less polarising.
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