Chemistry · Classification of Elements and Periodicity

Atomic Radius & Ionic Radius

Atomic and ionic size is the first periodic property NCERT develops in §3.7.1, and it underpins almost every later trend — ionisation enthalpy, electron gain enthalpy and electronegativity all track back to how far the valence electrons sit from the nucleus. This note builds the idea from the operational definitions of covalent, metallic and van der Waals radius, through the across-period contraction and down-group expansion, to the rule that orders cations, anions and isoelectronic species. For NEET, ordering questions on radii and isoelectronic series are a near-annual fixture, so the reasoning here is worth holding as a reflex rather than a recalled fact.

Why atomic size is hard to define

Measuring the size of an atom is not like measuring the radius of a ball. An atom is exceedingly small — roughly $1.2\ \text{Å}$ ($1.2 \times 10^{-10}\ \text{m}$) in radius — and, more fundamentally, the electron cloud surrounding the nucleus has no sharp boundary at which we can say the atom ends. NCERT is explicit on this point: there is no practical way to measure the size of an isolated atom directly. What chemists do instead is estimate the size from the distance between atoms in the combined state, then assign each atom a share of that distance.

Because the estimate depends on how the atoms are bound — by a covalent bond, packed in a metal, or merely touching as neighbouring molecules — three operational radii arise: the covalent radius, the metallic radius and the van der Waals radius. They are not interchangeable, and a NEET stem that quotes a value usually implies one specific kind. The first task, then, is to keep the three definitions distinct.

Covalent, metallic and van der Waals radius

The covalent radius is obtained from a non-metallic element by measuring the bond length between two like atoms joined by a single covalent bond and taking half of it. In the chlorine molecule $\ce{Cl2}$ the internuclear distance is $198\ \text{pm}$, so the covalent radius of chlorine is $99\ \text{pm}$. The metallic radius is defined the same way for a metal: it is half the internuclear distance between adjacent atoms in the metallic crystal. In solid copper the nearest neighbours are $256\ \text{pm}$ apart, giving a metallic radius of $128\ \text{pm}$.

NCERT, for simplicity, uses the single term atomic radius to mean the covalent radius for non-metals and the metallic radius for metals. The van der Waals radius is different in kind: it is half the distance between the nuclei of two non-bonded atoms of adjacent molecules in close contact. Because non-bonded atoms cannot approach as closely as bonded ones, the van der Waals radius is the largest of the three for a given element. Atomic radii of all kinds are measured by X-ray or other spectroscopic methods.

Figure 1

Covalent radius from a bond length — chlorine as the worked case.

Cl Cl internuclear distance = 198 pm r = 99 pm

Half the bond distance in $\ce{Cl2}$ is taken as the atomic (covalent) radius of chlorine. The same halving applied to the $256\ \text{pm}$ separation in copper metal gives a metallic radius of $128\ \text{pm}$.

Type of radiusHow it is measuredApplies toNCERT example
Covalent radiusHalf the single-bond internuclear distance between two like atomsNon-metalsCl₂: 198 → 99 pm
Metallic radiusHalf the internuclear distance between adjacent atoms in a metal crystalMetalsCu: 256 → 128 pm
van der Waals radiusHalf the distance between non-bonded atoms of neighbouring molecules in contactNoble gases; non-bonded contactsLargest of the three
NEET Trap

Do not compare a noble gas using a covalent radius.

Noble gases are monoatomic and form no normal covalent bonds, so no covalent radius can be defined for them. NCERT notes that their non-bonded radii are very large, and they must be compared with the van der Waals radii of other elements — never with covalent radii. A stem that lists a "very large" radius for argon or neon is using the van der Waals scale.

For noble gases, size is a van der Waals radius — always larger than the covalent radius of a neighbouring element.

Two trends emerge clearly from the tabulated radii. Across a period, atomic size generally decreases. Moving from lithium to fluorine in the second period, the outer electrons all occupy the same valence shell, but the nuclear charge rises with each successive element. The growing positive charge draws the valence electrons inward, so the atom contracts steadily from left to right. NIOS states the same rule plainly: the first member of each period — the group 1 atom — is the largest in its row, and size falls as we move rightward.

Down a group, atomic size increases. Descending group 1 from lithium to caesium, or group 17 from fluorine to iodine, the principal quantum number $n$ increases at each step and a new electron shell is added. The valence electrons lie progressively farther from the nucleus, and the filled inner shells shield them from the nuclear pull, so the radius grows regularly with atomic number. This is why a 2025 NEET option testing "the atomic radius of Cs is greater than that of Li and Rb" is correct on the down-group rule.

Figure 2

The two directions of the trend on a periodic-table grid.

period → radius DECREASES group ↓ radius INCREASES

The largest atoms cluster at the bottom-left (low nuclear charge, high $n$); the smallest at the top-right (high nuclear charge, same shell). The largest atom of any period is its group 1 member.

DirectionWhat changesWhyEffect on radius
Left → right (period)Nuclear charge rises; same valence shellEffective nuclear charge increases, pulling electrons inDecreases
Top → bottom (group)New shell added; $n$ increasesValence electrons farther out; inner shells shield the nucleusIncreases

Effective nuclear charge and shielding

Both trends are governed by one concept: the effective nuclear charge ($Z_{\text{eff}}$) — the net positive charge a valence electron actually experiences after the inner electrons partially screen the full nuclear charge. Across a period, each added proton is only weakly offset by an electron entering the same shell, so $Z_{\text{eff}}$ rises and the atom contracts. Down a group, the addition of a complete inner shell sharply increases the shielding, so $Z_{\text{eff}}$ on the outermost electrons grows only slowly while $n$ jumps, and the radius expands.

This single lens also explains the few irregularities NEET likes to probe. In group 13, the order is $\ce{B} < \ce{Ga} < \ce{Al} < \ce{In} < \ce{Tl}$ — gallium is slightly smaller than aluminium because the newly filled $3d$ electrons in Ga shield poorly, letting $Z_{\text{eff}}$ rise enough to contract the atom below Al. The same poor $d$-shielding logic recurs throughout the p-block.

Build the chain

A smaller radius means valence electrons are held more tightly — the direct cause of higher ionisation enthalpy across a period. Read size and energy together.

Ionic radius: cations and anions

When an atom loses or gains electrons it becomes an ion, and its radius changes in a direction that follows directly from the electron count. Ionic radii are estimated from the distances between cations and anions in ionic crystals, and in general they follow the same period and group trends as atomic radii.

A cation is always smaller than its parent atom. Removing electrons leaves the nuclear charge unchanged but reduces the number of electrons, so each remaining electron feels a stronger net pull and the cloud contracts; frequently an entire outer shell is removed. NCERT's figures make the magnitude clear: the sodium atom has a radius of $186\ \text{pm}$, but the sodium ion $\ce{Na+}$ is only $95\ \text{pm}$. An anion is always larger than its parent atom. Adding electrons increases electron–electron repulsion and lowers the effective nuclear charge per electron, so the cloud swells: the fluorine atom is $64\ \text{pm}$, while the fluoride ion $\ce{F-}$ is $136\ \text{pm}$.

Figure 3

Cation shrinks, anion expands — the same nucleus, a different electron count.

Na 186 pm Na⁺ 95 pm F 64 pm F⁻ 136 pm

Losing an electron contracts sodium to roughly half its radius; gaining one expands fluorine to more than double. The nucleus is the same in each pair — only the electron count and the resulting repulsion change.

Isoelectronic species and their ordering

Atoms and ions that contain the same number of electrons are called isoelectronic species. NCERT's standard example is the ten-electron set $\ce{O^2-, F-, Na+, Mg^2+}$, to which $\ce{Ne}$, $\ce{N^3-}$ and $\ce{Al^3+}$ also belong. Since every member carries the identical electron cloud, the only thing distinguishing their sizes is the nuclear charge holding that cloud.

The rule is therefore sharp: among isoelectronic species, the greater the nuclear charge (number of protons), the smaller the radius. A cation with a larger positive charge pulls the fixed cloud in tightest; an anion with a larger negative charge has the fewest protons relative to its electrons, so net repulsion outweighs nuclear attraction and the species expands. Ordering by increasing atomic number gives decreasing size in lockstep.

Species (10 electrons)Protons (Z)Net chargeRelative size
$\ce{N^3-}$73−Largest
$\ce{O^2-}$82−
$\ce{F-}$91−
$\ce{Ne}$100middle
$\ce{Na+}$111+
$\ce{Mg^2+}$122+
$\ce{Al^3+}$133+Smallest
NEET Trap

Two different rules — keep them apart.

Confusing the cation/anion rule with the isoelectronic rule is the single most common error here. For a parent atom versus its own ions, the comparison is by electron count: cation < atom < anion. For an isoelectronic set, the electron count is fixed and the comparison is by nuclear charge: more protons means smaller. Always check first whether you are comparing one element's species or many species with equal electrons.

Same element, different electrons → use charge sign. Same electrons, different elements → use proton count: more Z, smaller size.

Worked ordering example

The reasoning becomes mechanical once the right rule is selected. The two NCERT-style problems below combine both ideas, exactly as NEET stems do.

Worked example

Arrange the following in increasing order of size: $\ce{Mg, Mg^2+, Al, Al^3+}$.

Step 1. Mg and Al are neutral atoms in the same period; atomic radius decreases left to right, so $\ce{Al} < \ce{Mg}$.

Step 2. Each cation is smaller than its parent atom: $\ce{Mg^2+} < \ce{Mg}$ and $\ce{Al^3+} < \ce{Al}$.

Step 3. $\ce{Mg^2+}$ and $\ce{Al^3+}$ are isoelectronic (10 electrons each); the larger nuclear charge of $\ce{Al^3+}$ (Z = 13) makes it smaller than $\ce{Mg^2+}$ (Z = 12).

Result: $\ce{Al^3+} < \ce{Mg^2+} < \ce{Al} < \ce{Mg}$. The largest species is $\ce{Mg}$; the smallest is $\ce{Al^3+}$.

Worked example

Order the ions $\ce{Al^3+, Mg^2+, Na+, F-}$ by increasing ionic size.

Step 1. Check electrons: each ion has 10 electrons, so this is an isoelectronic set — order by nuclear charge alone.

Step 2. Proton counts are Al = 13, Mg = 12, Na = 11, F = 9. More protons pull the fixed cloud tighter, so size rises as Z falls.

Result: $\ce{Al^3+} < \ce{Mg^2+} < \ce{Na+} < \ce{F-}$ — precisely the NEET 2016 answer key for increasing ionic size.

Quick Recap

Atomic & ionic radius in one screen

  • Atomic radius is estimated from bonded distances: covalent radius (half a single-bond length, e.g. $\ce{Cl2}$ → 99 pm), metallic radius (half the crystal separation, e.g. Cu → 128 pm), and van der Waals radius (non-bonded, largest, used for noble gases).
  • Across a period, radius decreases as effective nuclear charge rises; down a group it increases as new shells are added and shielding grows.
  • A cation is smaller than its parent atom ($\ce{Na+}$ 95 pm vs Na 186 pm); an anion is larger ($\ce{F-}$ 136 pm vs F 64 pm).
  • Isoelectronic species share the same electron count, so size is set by nuclear charge: $\ce{N^3- > O^2- > F- > Ne > Na+ > Mg^2+ > Al^3+}$.
  • Watch group 13: $\ce{B < Ga < Al < In < Tl}$ — Ga dips below Al because poor $3d$ shielding raises $Z_{\text{eff}}$.

NEET PYQ Snapshot — Atomic Radius & Ionic Radius

Radius ordering and isoelectronic comparisons are a recurring theme — these are verbatim from official NEET papers.

NEET 2023 · Q.62

The element expected to form the largest ion to achieve the nearest noble gas configuration is —

  • (1) Na
  • (2) O
  • (3) F
  • (4) N
Answer: (4) N

To reach the neon configuration, N gains 3 electrons to form $\ce{N^3-}$. For isoelectronic species, as the negative charge on the anion increases the ionic size increases, so $\ce{N^3-}$ is the largest of the resulting ions.

NEET 2018 · Q.66

The correct order of atomic radii in group 13 elements is —

  • (1) B < Al < In < Ga < Tl
  • (2) B < Al < Ga < In < Tl
  • (3) B < Ga < Al < Tl < In
  • (4) B < Ga < Al < In < Tl
Answer: (4)

Ga is slightly smaller than Al because the poorly shielding $3d$ electrons let the effective nuclear charge rise, so atomic size runs $\ce{B < Ga < Al < In < Tl}$ — a deliberate break from the simple down-group rule.

NEET 2016 · Q.23

In which option does the order NOT agree with the indicated property? (radius-relevant options shown)

  • (3) Li < Na < K < Rb (increasing metallic radius)
  • (4) $\ce{Al^3+ < Mg^2+ < Na+ < F-}$ (increasing ionic size)
Answer: options (3) and (4) are correct as stated

Metallic radius increases down group 1, so $\ce{Li < Na < K < Rb}$ holds. The four ions are isoelectronic (10 e⁻); increasing size follows decreasing nuclear charge, so $\ce{Al^3+ < Mg^2+ < Na+ < F-}$ is correct. Both confirm the size rules of this note.

NEET 2025 · Q.69

Which statements are true? (radius/isoelectronic statements shown) C. Ar, K⁺, Cl⁻, Ca²⁺ and S²⁻ are all isoelectronic species. E. The atomic radius of Cs is greater than that of Li and Rb.

  • Correct combination among the options: C and E only
Answer: (3) C and E only

$\ce{Ar, K+, Cl-, Ca^2+, S^2-}$ each have 18 electrons, so statement C is a valid isoelectronic set. Atomic radius increases down group 1, so Cs (262 pm) exceeds both Rb (244 pm) and Li (152 pm), making E true.

FAQs — Atomic Radius & Ionic Radius

The size-comparison questions students most often get wrong, answered against the NCERT rules.

Why does atomic radius decrease across a period but increase down a group?

Across a period the outer electrons stay in the same valence shell while the nuclear charge rises with atomic number, so the effective nuclear charge experienced by the valence electrons increases and pulls them closer, shrinking the atom. Down a group the principal quantum number increases, a new electron shell is added at each step, and the filled inner shells shield the outer electrons from the nucleus, so the valence electrons lie farther out and the atom grows larger.

Why is a cation smaller than its parent atom and an anion larger?

A cation forms by losing one or more electrons while the nuclear charge stays the same, so the remaining electrons feel a stronger pull and the ion contracts; often an entire outer shell is lost. An anion forms by gaining electrons, which increases electron-electron repulsion and lowers the effective nuclear charge per electron, so the electron cloud expands and the ion is larger than the neutral atom. For example, the fluoride ion (136 pm) is far larger than the fluorine atom (64 pm), while the sodium ion (95 pm) is much smaller than the sodium atom (186 pm).

How do you order isoelectronic species by size?

Isoelectronic species have the same number of electrons but different nuclear charges, so size depends only on nuclear charge: the more protons, the tighter the pull on the fixed electron cloud and the smaller the species. Arrange them by increasing number of protons (atomic number) and the radius falls in that direction. For the 10-electron set, size decreases as N3- > O2- > F- > Ne > Na+ > Mg2+ > Al3+, which is the order of increasing nuclear charge.

What is the difference between covalent, metallic and van der Waals radius?

The covalent radius is half the internuclear distance between two like atoms joined by a single covalent bond; for chlorine the Cl-Cl distance is 198 pm, so the covalent radius is 99 pm. The metallic radius is half the distance between adjacent atoms in a metallic crystal; in copper the nearest neighbours are 256 pm apart, giving a metallic radius of 128 pm. The van der Waals radius is half the distance between the nuclei of two non-bonded atoms of neighbouring molecules in close contact; it is the largest of the three and is used for noble gases, which form no normal bonds.

Why is the van der Waals radius used for noble gases instead of the covalent radius?

Noble gases are monoatomic and do not normally form covalent bonds, so a bonded covalent radius cannot be defined for them. Their size is therefore measured from the distance between non-bonded atoms in close contact, which gives a van der Waals radius. Because non-bonded atoms approach less closely than bonded ones, van der Waals radii are large, so noble-gas radii should be compared with the van der Waals radii of other elements rather than with their covalent radii.

Is the increase in atomic radius down group 13 perfectly regular?

No. The general rule is that size increases down a group, but group 13 shows an irregularity at gallium: the correct order is B < Ga < Al < In < Tl, with Ga slightly smaller than Al. The newly filled 3d electrons in Ga shield the nucleus poorly, so the effective nuclear charge felt by the outer electrons rises and gallium contracts to a size just below aluminium. This is why blindly applying down-the-group reasoning to group 13 can give the wrong answer in NEET ordering questions.