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Chemistryp-Block Elements
Which of the following statements about halogens are correct?
A. Fluorine is the most electronegative element in the periodic table.
B. Chlorine is a stronger oxidising agent than fluorine.
C. Iodine is a solid at room temperature.
D. The bond dissociation enthalpy of F₂ is lower than Cl₂.
Options
1
A and B only
2
A, C and D only
3
B and C only
4
A, B, C and D
Correct Answer
Option 2 : A, C and D only
Solution — Each Statement
A

Statement A — TRUE ✓

Fluorine (F, electronegativity = 4.0 on Pauling scale) is the most electronegative element in the entire periodic table. This makes F the strongest oxidising agent among halogens and explains many of its unique properties.

B

Statement B — FALSE ✗

Fluorine is a stronger oxidising agent than chlorine — NOT the other way around. Oxidising power of halogens decreases down the group: F₂ > Cl₂ > Br₂ > I₂. F₂ can oxidise water, Cl₂ cannot oxidise F⁻. Statement B is wrong.

C

Statement C — TRUE ✓

Physical states at room temperature: F₂ = pale yellow gas, Cl₂ = yellow-green gas, Br₂ = reddish-brown liquid, I₂ = shiny grey-black solid. Iodine is indeed a solid at room temperature (25°C). It sublimes directly from solid to purple vapour when heated.

D

Statement D — TRUE ✓

Bond dissociation energy: F₂ = 158 kJ/mol, Cl₂ = 242 kJ/mol. F₂ has LOWER bond dissociation enthalpy than Cl₂ — unusual because normally bond energy decreases as atoms get larger. F₂ is weak because lone pair–lone pair repulsion is severe between small F atoms bonded together.

Theory: p-Block Elements — Halogens (Group 17)
1. General Characteristics of Halogens

Halogens (Group 17: F, Cl, Br, I, At) are the most reactive non-metals. They have 7 valence electrons (ns²np⁵) and need one more electron to complete their octet — making them powerful oxidising agents. Down the group, reactivity decreases as electronegativity decreases and atomic size increases. All halogens exist as diatomic molecules (X₂) in their elemental form.

📌 F₂: pale yellow gas, bp = −188°C, most reactive halogen

📌 Cl₂: yellow-green gas, bp = −34°C, pungent smell, used in water treatment

📌 Br₂: reddish-brown liquid, bp = 59°C, dense toxic vapour

📌 I₂: shiny grey-black solid, bp = 184°C, sublimes (purple vapour)

📌 At (astatine): radioactive, very short half-life, not practically available

2. Anomalous Properties of Fluorine

Fluorine shows several anomalous properties compared to other halogens due to its small size, highest electronegativity, and absence of d-orbitals. Key anomalies:

📌 F₂ has lower bond dissociation energy (158 kJ/mol) than Cl₂ (242 kJ/mol) — due to lone pair repulsion in small F atoms

📌 F shows only −1 oxidation state (no d-orbitals, cannot expand octet)

📌 Other halogens show −1, +1, +3, +5, +7 oxidation states

📌 HF is a weak acid (extensive H-bonding), HCl/HBr/HI are strong acids

📌 F₂ reacts with water to give OF₂ (fluorine displaces oxygen): 2F₂ + 2H₂O → O₂ + 4HF. Actually: F₂ + H₂O → HF + HOF

📌 F cannot be made by electrolysis of aqueous solution (oxidises water) — made by electrolysis of molten KHF₂

3. Oxidising Power of Halogens

Oxidising power follows the trend F₂ > Cl₂ > Br₂ > I₂, determined by the reduction potential (E°). F₂ has the highest reduction potential (E° = +2.87 V) — it can oxidise all other halide ions. Cl₂ can displace Br⁻ and I⁻ but not F⁻. Br₂ can displace I⁻ but not Cl⁻ or F⁻. I₂ cannot displace any other halide ion from solution. This is the basis of the "halogen displacement reactions" used in analytical chemistry.

4. Hydrogen Halides — Acid Strength and Thermal Stability

📌 Acid strength in aqueous solution: HF < HCl < HBr < HI

📌 HF is weak acid (Ka ≈ 6.8×10⁻⁴) — extensive H-bonding, strong H-F bond

📌 HI is strongest acid — weakest H-I bond, easiest to donate H⁺

📌 Thermal stability: HF > HCl > HBr > HI (bond strength decreases)

📌 HI decomposes at 300°C; HF is stable even at 1000°C

📌 Reducing power: HF < HCl < HBr < HI (HI is a good reducing agent)

5. Oxoacids of Halogens

Chlorine forms a series of oxoacids: HOCl (hypochlorous acid, +1), HOClO (chlorous acid, +3), HOClO₂ (chloric acid, +5), HOClO₃ (perchloric acid, +7). Acid strength increases with oxidation state of Cl: HClO₄ > HClO₃ > HClO₂ > HClO. More oxygen atoms pull more electron density from H-O bond, making H⁺ easier to release. HClO₄ (perchloric acid) is one of the strongest acids known. Fluorine forms no oxoacids (cannot show positive oxidation state — most electronegative).

6. Interhalogen Compounds

Interhalogens are compounds formed between two different halogens: XY, XY₃, XY₅, XY₇. Examples: ClF, BrF₃, IF₅, IF₇. The central halogen (larger) is the one with positive formal charge; fluorine always acts as the smaller terminal halogen (most electronegative). Properties are intermediate between parent halogens. ClF is used as fluorinating agent. IF₇ is the most complex known interhalogen. All are reactive and used as fluorinating/chlorinating agents in industry.

7. Noble Gases (Group 18)

Noble gases (He, Ne, Ar, Kr, Xe, Rn) have completely filled outer shells (ns²np⁶, except He which is 1s²). Traditionally considered inert — until Bartlett (1962) prepared XePtF₆, the first noble gas compound. Xenon forms XeF₂, XeF₄, XeF₆, XeO₃, XeO₄. Radon is radioactive. Noble gases have the highest ionisation enthalpies in their periods. Uses: He in balloons, He-O₂ for deep sea diving, Ne in signs, Ar in light bulbs, Kr in photography flashes, Xe in high-intensity lamps.

8. Trends in Group 17

📌 Atomic radius: increases F < Cl < Br < I

📌 Electronegativity: decreases F > Cl > Br > I

📌 Electron affinity: Cl > F > Br > I (F anomalously low — small size, high repulsion)

📌 Ionisation enthalpy: decreases down group

📌 Melting and boiling points: increase (F → I) due to stronger van der Waals forces with larger molecules

📌 Oxidising power: decreases F > Cl > Br > I

📌 Reducing power of halide ions: increases F⁻ < Cl⁻ < Br⁻ < I⁻

Frequently Asked Questions
1. Why does F₂ have lower bond energy than Cl₂?
F atoms are very small. When two F atoms bond, their lone pairs are very close together and repel each other strongly (F has 3 lone pairs on each atom). This lone pair–lone pair repulsion weakens the F–F bond. Cl atoms are larger — lone pairs are farther apart, less repulsion, stronger bond. F–F = 158 kJ/mol vs Cl–Cl = 242 kJ/mol.
2. Why can't fluorine show positive oxidation states?
Fluorine has no d-orbitals in its valence shell (2s²2p⁵ — only n=2 orbitals). To show positive oxidation states, an element needs to expand its valence shell using d-orbitals (e.g., Cl in ClF₅ uses 3d orbitals). Since F has no available d-orbitals, it cannot expand its octet and can only show −1 oxidation state (or 0 in F₂). It is also the most electronegative element, so it never gives electrons to another atom.
3. Why is HF a weak acid while HCl is strong?
H–F bond is very strong (567 kJ/mol vs H–Cl = 432 kJ/mol), making it hard to donate H⁺. Also, HF forms strong hydrogen bonds in water — HF molecules associate rather than dissociate fully. In dilute solution, HF partially dissociates. HCl has a weaker bond and no significant H-bonding — dissociates completely. Acid strength: HF < HCl < HBr < HI (bond strength decreases down group).
4. How is Cl₂ prepared industrially?
Chlor-alkali process: electrolysis of brine (NaCl solution). At cathode: 2H₂O + 2e⁻ → H₂ + 2OH⁻. At anode (graphite): 2Cl⁻ → Cl₂ + 2e⁻. Overall: 2NaCl + 2H₂O → Cl₂ + H₂ + 2NaOH. Products: Cl₂ (for PVC, pesticides, disinfectants), H₂ (fuel cells), NaOH (soap, paper, textiles). This is the Chlor-alkali industry — one of the largest chemical industries.
5. Why is iodine a solid at room temperature?
I₂ molecules (very large, highly polarisable) have strong London dispersion forces (van der Waals). As molecular size and surface area increase (F₂ → I₂), these intermolecular forces strengthen, requiring more energy to separate molecules → higher melting and boiling points. F₂ (very small) has very weak van der Waals → gas. I₂ (very large) has strong van der Waals → solid.
6. What is the bleaching action of Cl₂?
Cl₂ + H₂O → HCl + HOCl. HOCl (hypochlorous acid) decomposes: HOCl → HCl + [O] (nascent oxygen). This nascent oxygen oxidises the colouring matter (destroys the chromophore group), causing bleaching. Cl₂ bleaching is permanent (chemical oxidation). SO₂ bleaching is temporary (reduction). Cl₂ is used to bleach cotton, paper pulp, and is used in water purification to kill bacteria.
7. What is the first noble gas compound prepared?
Neil Bartlett prepared XePtF₆ in 1962, the first noble gas compound. He reasoned that O₂⁺PtF₆⁻ had been prepared (ionisation energy of O₂ = 1175 kJ/mol), and since Xe has a similar first ionisation energy (1170 kJ/mol), Xe should also form XePtF₆. This discovery overturned the belief that noble gases were completely inert and opened a new field of chemistry.
8. Why is perchloric acid (HClO₄) such a strong acid?
HClO₄ has four oxygen atoms around Cl (+7 oxidation state). The three non-OH oxygens withdraw electron density from Cl, which pulls electron density from the O in O–H, weakening it and making H⁺ very easy to release. More electronegative atoms/groups around the central atom → stronger acid. HClO₄ is one of the strongest known acids. Acid strength: HClO < HClO₂ < HClO₃ < HClO₄.
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