The p-Block Elements (Group 13 & 14) • Topic 1 of 3

Group 13: Boron Family

The p-block occupies the right-hand side of the periodic table — Groups 13 to 18. In these elements the last electron enters a p-orbital, giving a general valence configuration of ns2np1-6. Because the p-block spans both metals (Al, Sn, Pb), metalloids (B, Si, Ge) and non-metals (C, N, O), it shows the widest variety of properties of any block. The chemistry of these elements is dominated by the gradual filling of p-orbitals and by the presence of completely filled inner d and f sub-shells in the heavier members.

Group 13 — the boron family — contains boron (B), aluminium (Al), gallium (Ga), indium (In) and thallium (Tl). Their valence configuration is ns2np1, so they have three valence electrons and a common oxidation state of +3. Boron is the only non-metal (a metalloid); the rest are typical metals whose metallic character increases down the group.

Going down the group the atomic radius increases, but not smoothly. Ga is actually slightly smaller than Al because the poor shielding by the intervening 3d electrons (the d-block contraction) lets the nucleus pull the outer electrons in more tightly. Ionisation enthalpy therefore decreases from B to Al but then behaves irregularly. A central feature is the growing stability of the +1 oxidation state on descending the group — the inert pair effect. For Tl the +1 state is actually more stable than +3, so Tl3+ is a strong oxidising agent. Aluminium is exclusively +3, gallium and indium show both, and thallium prefers +1.

Anomalous behaviour of boron. Boron differs sharply from the rest of the group because of its very small size, high ionisation enthalpy, high electronegativity and absence of d-orbitals in its valence shell. It is a hard, refractory non-metallic solid, forms only covalent compounds, and its maximum covalency is restricted to four (it cannot expand its octet, unlike Al which forms [AlF6]3-). Boron's compounds such as BF3 and BCl3 are electron-deficient Lewis acids. Boron resembles silicon (its diagonal neighbour) more than it resembles aluminium.

Important compounds. Borax, Na2B4O7·10H2O, is a white crystalline solid; in solution it is alkaline (it hydrolyses) and on strong heating gives a transparent borax bead of NaBO2 and B2O3, used to identify coloured metal ions. Orthoboric acid, H3BO3, is a weak monobasic Lewis acid (not a protonic acid): it accepts OH- rather than donating H+, forming [B(OH)4]-. It has a layered structure held by hydrogen bonds and feels soapy. Diborane, B2H6, is the simplest borane; it is electron-deficient and held together by two three-centre two-electron (3c-2e) ‘banana’ bonds in which two bridging hydrogens each bind to both boron atoms using only one electron pair for the three atoms.

Aluminium is the most abundant metal in the Earth's crust. It is strongly electropositive yet protected by a tough oxide film. It is amphoteric — it dissolves in both acids and alkalis: 2Al + 6HCl → 2AlCl3 + 3H2, and 2Al + 2NaOH + 6H2O → 2Na[Al(OH)4] + 3H2. Al2O3 and Al(OH)3 are likewise amphoteric. Aluminium is used in aircraft, electrical cables, packaging and in the thermite welding reaction (it reduces Fe2O3).

Diborane B2H6 structure with two three-centre two-electron banana bondsDiborane (B₂H₆): two 3c-2e bridge bondsBBHHbridging H (banana bonds)HHHH4 terminal B-H (normal 2c-2e) + 2 bridging B-H-B (3c-2e)
1
Worked Example
Write the general valence-shell electronic configuration of Group 13 elements and state their common oxidation state.
Solution
  1. Group 13 elements have three valence electrons.
  2. These occupy the ns and np sub-shells as ns2np1.
  3. Loss/sharing of all three gives the common oxidation state.

Answer: Configuration ns2np1; common oxidation state +3 (with +1 increasingly stable down the group).

2
Worked Example
Explain, with an equation, why aluminium is described as an amphoteric metal.
Solution
  1. An amphoteric metal reacts with both acids and bases.
  2. With acid: 2Al + 6HCl → 2AlCl3 + 3H2.
  3. With alkali: 2Al + 2NaOH + 6H2O → 2Na[Al(OH)4] + 3H2.

Answer: Because Al liberates H2 with both HCl and NaOH, it is amphoteric; Al2O3 and Al(OH)3 are likewise amphoteric.

3
Worked Example
Why is boron unable to form the [BF6]3- ion whereas aluminium readily forms [AlF6]3-?
Solution
  1. Maximum covalency is set by the number of available valence orbitals.
  2. Boron (2s2p) has only four valence orbitals, so its maximum covalency is 4.
  3. Aluminium has vacant 3d orbitals, so it can expand its octet to a covalency of 6.

Answer: Boron lacks d-orbitals (covalency limited to 4); aluminium has vacant 3d orbitals, allowing six-coordination in [AlF6]3-.

4
Worked Example
Orthoboric acid is a monobasic acid yet it does not donate a proton. Explain how it acts as an acid.
Solution
  1. H3BO3 does not ionise to give H+.
  2. The electron-deficient B accepts a lone pair from a hydroxide ion of water.
  3. B(OH)3 + 2H2O → [B(OH)4]- + H3O+.

Answer: It is a weak monobasic Lewis acid: it accepts OH- from water, releasing one H3O+, rather than donating its own protons.

5
Worked Example
Describe the bonding in diborane (B2H6) and state how many of each type of B-H bond it contains.
Solution
  1. Diborane has 12 valence electrons — too few for 8 normal 2c-2e bonds.
  2. Four terminal B-H bonds are ordinary 2-centre 2-electron bonds.
  3. Two bridging hydrogens form 3-centre 2-electron (banana) bonds, each spanning B-H-B with a single electron pair.

Answer: 4 terminal (2c-2e) B-H bonds and 2 bridging (3c-2e) B-H-B banana bonds; it is electron-deficient.

6
Worked Example
What happens when borax is heated strongly? Give the products and name the test it is used for.
Solution
  1. Borax first loses water of crystallisation and swells.
  2. On strong heating: Na2B4O7·10H2O → Na2B4O7 → 2NaBO2 + B2O3.
  3. B2O3 fuses to a transparent glassy bead.

Answer: It gives sodium metaborate and boric anhydride (NaBO2 + B2O3), a glassy bead used in the borax bead test to identify coloured metal ions.

Key Points

  • p-block (Groups 13-18) has valence configuration ns2np1-6; Group 13 (boron family) is ns2np1 with common oxidation state +3.
  • The +1 state grows more stable down the group (inert pair effect): Al only +3, Ga/In both, Tl mainly +1; Ga is smaller than Al due to poor 3d shielding.
  • Boron is anomalous — small, high IE, no d-orbitals, max covalency 4, forms only covalent electron-deficient Lewis acids (BF3, BCl3); resembles Si diagonally.
  • Key boron compounds: borax (alkaline, borax-bead test), orthoboric acid H3BO3 (weak monobasic Lewis acid), diborane B2H6 with two 3c-2e banana bonds.
  • Aluminium is amphoteric (reacts with both acids and alkalis liberating H2); used in thermite, alloys, cables and packaging.
Tap an option to check your answer0 / 4
Q1.The general valence-shell electronic configuration of Group 13 elements is:
Explanation: Group 13 elements have three valence electrons arranged as ns2np1.
Q2.Diborane (B2H6) contains:
Explanation: It has four terminal B-H bonds and two bridging B-H-B three-centre two-electron banana bonds.
Q3.Which oxidation state is most stable for thallium?
Explanation: Due to the inert pair effect, Tl+1 is more stable than Tl+3, which is a strong oxidising agent.
Q4.Orthoboric acid (H3BO3) behaves as a:
Explanation: It is a weak monobasic Lewis acid that accepts OH- from water to give [B(OH)4]- rather than donating protons.