Group 2

The thermal stability 热稳定性 of the Group 2 nitrates 硝酸盐 and carbonates 碳酸盐 increases down the group. Here is the reason, in terms of how the ions affect each other.

A small cation 阳离子 with a small ionic radius 离子半径 has a high charge density. It pulls on the electrons of the nearby anion and distorts its shape — this is polarisation 极化. Distorting the large anion 阴离子 (the carbonate or nitrate ion) weakens a bond inside it, so the compound breaks down more easily.

Going down the group, the cation gets larger. Its charge density drops, so it polarises the anion less. The anion is less distorted, so the compound is harder to break down — it is more thermally stable and needs a higher temperature to decompose.

Worked example. Down Group 2 the hydroxides become more soluble while the sulfates become less soluble. Explain why the two trends run in opposite directions. Solubility is a contest between the lattice energy holding the solid together and the hydration energy rewarding the ions for dissolving. Both get less exothermic as the cation grows, so whichever falls faster decides the trend. With the small hydroxide ion, the lattice energy depends strongly on the cation's size, so it falls faster than the hydration energy: the lattice gets relatively easier to break and solubility rises. With the large sulfate ion, the lattice energy is already dominated by that big anion and barely changes down the group, while the cation's hydration energy still falls - so solubility falls. Name both energies and say which one falls faster; simply restating the trends earns no explanation marks.

When an ionic solid dissolves, two energy changes compete. The enthalpy change of solution 溶解焓变 is the sum of them:

• you must first pull the lattice apart (this needs the lattice energy 晶格能).
• then water surrounds the ions (this releases the enthalpy change of hydration 水合焓变).

If the energy released on hydration roughly matches (or beats) the energy needed to break the lattice, the solid dissolves easily.

Going down the group, both the lattice energy and the hydration enthalpy get smaller (less negative), because the cation is larger. But they shrink at different rates, and this explains the opposite trends:

• Thermal stability of carbonates and nitrates increases down the group — larger cations polarise the anion less.
• Give the decomposition products: carbonates → oxide + $\text{CO}_2$; nitrates → oxide + $\text{NO}_2$ + $\text{O}_2$ (brown gas).
• Hydroxides get more soluble and sulfates less soluble down the group.
• Explain trends with cation charge density (polarising power), not just size.