Diagonal Relationship: Why Lithium Acts Like Magnesium
You know the periodic table as rows and columns. Elements in the same group share similar valence electron configurations, so they behave alike. Sodium and potassium are both reactive metals that form +1 ions. That much is straightforward.
But here is the surprise: lithium, the first element of Group 1, is far more similar to magnesium (Group 2) than it is to its own group-mate sodium. Drop a piece of lithium into water — it fizzes slowly. Drop sodium — it races across the surface, sometimes catching fire. Lithium's behaviour is closer to magnesium's: both react slowly with water, both form nitrides when heated in nitrogen, both give carbonates that decompose on heating.
This unexpected kinship is the diagonal relationship.
The Intuition: A Balancing Act
Imagine two properties that pull in opposite directions as you move across the periodic table.
Going down a group: Atomic size increases, so the charge-to-size ratio (often called ionic potential, ϕ=radiuscharge) decreases. The element becomes more metallic, more reactive.
Going right across a period: Atomic size decreases, and charge increases, so the charge-to-size ratio increases. The element becomes less metallic, more covalent in its bonding.
Now move diagonally: one step down and one step right. The increase in size (down) is roughly compensated by the increase in charge (right). The charge-to-size ratio stays nearly the same.
Note
Charge-to-size ratio ϕ=rZ (for ions) or rZeff (for atoms) is the key. Two elements with similar ϕ values will polarise nearby electrons to a similar extent, leading to similar chemical behaviour.
Lithium (Li+, radius ~76 pm) and magnesium (Mg2+, radius ~72 pm) have almost identical charge-to-size ratios. So does beryllium (Be2+, ~31 pm) and aluminium (Al3+, ~53 pm). The numbers are not exactly equal, but they are close enough to produce striking parallels.
The Precise Statement
Important
Diagonal relationship: The first element of a group in the s- and p-blocks shows a marked similarity in properties with the second element of the next group — the element diagonally below and to the right.
The most important pairs are:
Pair
Groups
Li – Mg
1 and 2
Be – Al
2 and 13
B – Si
13 and 14
(You may also see C–P mentioned, but the similarity is weaker and rarely tested.)
Concrete Similarities: Li and Mg
Let's make this real with exam-relevant examples.
1. Reaction with nitrogen. Both lithium and magnesium burn in nitrogen to form nitrides.
6Li+N2→2Li3N
3Mg+N2→Mg3N2
Sodium and potassium do not form stable nitrides.
2. Carbonate decomposition. Lithium carbonate and magnesium carbonate both decompose on heating to the oxide and CO2.
Li2CO3ΔLi2O+CO2
MgCO3ΔMgO+CO2
Other alkali metal carbonates (Na2CO3, K2CO3) are thermally stable — they do not decompose even at red heat.
3. Solubility of fluorides and phosphates. LiF and MgF2 are both sparingly soluble in water. Li3PO4 and Mg3(PO4)2 are also insoluble. The corresponding sodium and potassium salts are freely soluble.
4. Hydroxide behaviour. LiOH is a weaker base than NaOH or KOH. Mg(OH)2 is a weak base too. Both are less soluble than the heavier alkali hydroxides.
5. Formation of organometallics. Both lithium and magnesium form alkyl and aryl compounds (organolithium reagents and Grignard reagents) that are used extensively in organic synthesis.
Be–Al Similarities
Beryllium and aluminium are another classic pair.
Both are amphoteric — their oxides and hydroxides dissolve in both acids and bases.
Both form covalent compounds (BeCl2 is covalent, AlCl3 is covalent in the anhydrous state).
Both give carbides that produce methane on hydrolysis: Be2C + 4H2O → 2Be(OH)2 + CH4; Al4C3 + 12H2O → 4Al(OH)3 + 3CH4.
Both are rendered passive by concentrated nitric acid. …
Same paired similarities as WBA5: covalent bridged chlorides, amphoteric hydroxides, complex-ion formation, methane-forming carbides, and passivation by nitric acid, driven by comparable charge density. …
Step 1. Although Be²⁺ (r = 0.45 Å) and Al³⁺ (r = 0.54 Å) are not extremely close in size, their charge per unit area (charge density) is much closer (Be²⁺ = 2.36, Al³⁺ = 2.50), and both elements share the same electronegativity (1.5) -- this similar charge density underlies the parallel chemistry below.
Step 2. Chlorides: BeCl₂ forms a chloride-bridged dimeric structure (and also a polymeric chain), just like AlCl₃'s dimer Al₂Cl₆; both are soluble in organic solvents and behave as strong Lewis acids.
Step 3. Hydroxides: Be(OH)₂ dissolves in excess alkali to give the beryllate ion, [Be(OH)₄]²⁻ (plus H₂), exactly as Al(OH)₃ dissolves to give the aluminate ion, [Al(OH)₄]⁻ -- both hydroxides are amphoteric.
Step 4. Complex formation: both cations show a strong tendency to form complex ions, e.g. BeF₄²⁻ and AlF₆³⁻.
Step 5. Carbides: beryllium carbide (Be₂C), like aluminium carbide (Al₄C₃), evolves methane (not acetylene) on hydrolysis with water. …
Recall each of the paired similarities listed for Be and Al (Table 5.12), grounding each one in the shared charge-density reasoning that underlies the diagonal re …
Treating this as a different question from Q5/Q30 and inventing new, unsupported similarities instead of the documented set -- the book genuinely repeats this ex …