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Cyclohexane

C6H12 organic

Properties

StateLiquid
ColorColorless
SolubilityImmiscible with water (55 mg/L at 25°C); miscible with organic solvents
Melting Point6.5°C
Boiling Point80.7°C

About Cyclohexane

Cyclohexane is the molecule that conformational analysis was built on, and almost everything organic chemists know about three-dimensional shape preferences in saturated rings traces back to Hassel's and Barton's work on it (Nobel Prize, 1969). The chair conformation puts every C–C–C angle at the unstrained tetrahedral 111° and every C–H bond perfectly staggered, so there's no angle strain and essentially no torsional strain — which is why cyclohexane is far more stable than the planar hexagon a textbook drawing implies. The chair-flip interconverts axial and equatorial positions through a half-chair (about 45 kJ/mol barrier) and a twist-boat intermediate (about 23 kJ/mol above the chair), with the two chair forms in dynamic equilibrium at room temperature on the NMR timescale — at -90°C you can actually freeze the equilibrium out and see separate axial and equatorial signals. Substituent A-values (the energy preference for equatorial over axial) come directly from cyclohexane analysis: methyl 7.5 kJ/mol, isopropyl 9.2 kJ/mol, t-butyl about 21 kJ/mol — large enough that t-butyl essentially locks the ring conformation. Industrially, cyclohexane is overwhelmingly a feedstock for nylon: catalytic hydrogenation of benzene over Ni or Pt gives cyclohexane, which is then air-oxidized over a cobalt naphthenate catalyst to KA oil (cyclohexanone + cyclohexanol mixture), then HNO₃-oxidized to adipic acid HOOC–(CH₂)₄–COOH, the diacid for nylon-6,6. Roughly 90% of global cyclohexane goes into this chain, with the remainder going to cyclohexanone for caprolactam and nylon-6. As a solvent, cyclohexane is the conventional non-polar reference (¹H NMR singlet at 1.43 ppm) and is used as an internal standard in NMR work.

Where you'll encounter it

If you've ever drawn a chair on an organic chemistry exam and labeled axial-up and equatorial-out, the molecule was cyclohexane. In a research lab the colorless liquid often shows up as a non-polar recrystallization solvent (bp 80.7°C, easy to rotovap) or as a non-coordinating reference solvent for ¹H NMR at 1.43 ppm. The Bhopal disaster in 1984 traced back to a methyl isocyanate plant making intermediates for carbamate pesticides; nylon-6,6 plants making cyclohexanone via cyclohexane oxidation have had their own incidents (Flixborough, 1974), where 28 tonnes of leaking cyclohexane vapor exploded.

Common Uses

  • Catalytic feedstock for KA oil → adipic acid → nylon-6,6 (largest-volume use, ~90%)
  • Air-oxidation feedstock for cyclohexanone → caprolactam → nylon-6 polymer manufacture
  • Non-polar recrystallization solvent for moderately polar organic compounds with bp 80.7°C
  • Internal NMR reference and locking solvent (¹H singlet at 1.43 ppm) for non-polar samples
  • Conformational-analysis teaching molecule for axial/equatorial preferences and ring flip kinetics
  • Azeotrope partner with water (bp 69.5°C, 92% cyclohexane) for Dean–Stark dehydration setups
  • Calibration standard for differential scanning calorimetry (sharp 6.5°C melting transition)
  • Solvent for paint, ink, and adhesive formulations where pure aliphatic non-polar character is needed

Safety Information

GHS: H225 (highly flammable, flash point -20°C), H304 (aspiration hazard — fatal if swallowed and aspirated, the lung-toxicity mode for low-viscosity hydrocarbons), H315 (skin irritation), H336 (drowsiness/dizziness from CNS depression), H410 (very toxic to aquatic life). OSHA PEL 300 ppm (TWA), NIOSH REL 300 ppm, IDLH 1300 ppm. The fire hazard is significant — flash point -20°C means it's flammable at any normal lab temperature, and vapor density 2.9 (heavier than air) means leaks pool at floor level and travel to ignition sources. Use only in well-ventilated areas with no sparks or open flames; bond and ground containers when transferring. The Flixborough disaster (1974) was a cyclohexane vapor cloud explosion — 28 tonnes of escaped vapor from a temporary bypass pipe killed 28 people.

This safety summary is for educational reference only and may not be complete. It is not a substitute for Safety Data Sheets (SDS), medical advice, or professional chemical safety guidance. Always consult appropriate SDS and qualified professionals before handling chemicals.

Constituent Elements

Frequently Asked Questions

What is the molar mass of cyclohexane?
C₆H₁₂ is 84.159 g/mol — 6 × 12.011 + 12 × 1.008. Density at 20°C is 0.779 g/mL, so 1 mole occupies 108 mL of liquid. Useful for solvent measurements when you're using cyclohexane as an internal NMR standard or working out azeotrope ratios for Dean–Stark traps.
Why is cyclohexane in the chair and not flat?
A flat hexagon would force the C–C–C angles to 120° instead of the tetrahedral 109.5° preferred by sp³ carbon — 10° of angle strain at each vertex, plus eclipsing C–H bonds at every C–C edge giving torsional strain. The chair conformation puckers the ring so every angle is 111° (basically perfect) and every C–H bond is staggered with respect to its neighbor. Result: cyclohexane has zero strain and is the most stable saturated 6-ring possible — about 130 kJ/mol more stable per mole than the hypothetical flat form.
Why is cyclohexane the starting point for nylon?
The cleanest industrial route to adipic acid runs through cyclohexane: hydrogenate benzene → cyclohexane, air-oxidize over Co naphthenate at ~150°C → cyclohexanone + cyclohexanol (KA oil), then HNO₃ oxidation → adipic acid HOOC–(CH₂)₄–COOH. Adipic acid + hexamethylenediamine condense to nylon-6,6, the polymer in carpet, tire cord, and engineering plastics. Around 2.5 million tonnes of adipic acid get made this way per year, almost all from cyclohexane oxidation — which is also a major industrial source of N₂O emissions from the HNO₃ step, a known greenhouse-gas problem.