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Carbon Tetrachloride

CCl4 organic

Properties

StateLiquid
ColorColorless
SolubilityPractically insoluble in water (0.8 g/L at 20°C); miscible with organic solvents
Melting Point-22.9°C
Boiling Point76.7°C

About Carbon Tetrachloride

Carbon tetrachloride is the canonical example of how molecular symmetry can erase the macroscopic dipole of a molecule built from polar bonds. Each C–Cl bond carries a dipole of about 1.46 D, but the four bonds point to the corners of a perfect tetrahedron and the vector sum is exactly zero. The molecule belongs to the Td point group — the same symmetry as methane — which is why CCl4 is the textbook teaching molecule for tetrahedral geometry and the cancellation of bond dipoles. The practical consequence is a colorless liquid that dissolves fats, oils, greases, sulfur, iodine, and bromine handsomely while being immiscible with water, and that has no C–H bonds whatsoever. That last point is what kept it on the IR spectroscopy bench long after its other uses were banned: CCl4 has no fundamental absorptions in the C–H stretching region (2800 to 3000 cm⁻¹), the C–H bending region near 1450 cm⁻¹, or the C–H out-of-plane bands below 1000 cm⁻¹, so it is a clean window for IR work on hydrocarbons. From the 1920s through the 1970s, CCl4 was the dominant dry-cleaning solvent, the propellant in handheld 'Pyrene' fire extinguishers (which produced phosgene when sprayed on hot fires — a worse outcome than the original fire), and the first-generation refrigerant before CFCs. The Montreal Protocol classified it as an ozone-depleting substance with an ODP of 1.1 (more destructive per kilogram than CFC-11), and production for emissive uses was phased out globally by 2010. It also causes hepatic centrilobular necrosis through CYP2E1-mediated cleavage to the trichloromethyl radical (•CCl3), which initiates lipid peroxidation in hepatocytes — the textbook mechanism of free-radical liver injury, taught in every pharmacology course as the example of a CYP-bioactivated hepatotoxin.

Where you'll encounter it

If you have ever picked up a 1970s textbook and seen a beautifully clean IR spectrum of an alkane in CCl4, you are looking at the last gasp of carbon tet's most defensible use. Today the molecule shows up in the lab as the carbon source in the Appel reaction (PPh3 + CCl4 + ROH → RCl + Ph3PO + CHCl3) for converting alcohols to alkyl chlorides under mild conditions, and as a chlorinating agent in the Hunsdiecker reaction. Older fire-extinguisher cylinders labeled 'Pyrene' or 'Carbon Tet' still turn up at estate sales and need to be disposed of as hazardous waste rather than discharged. In a teaching lab the molecule is now a chalkboard exercise on Td symmetry rather than a bottle on the shelf — its acquisition is restricted in most jurisdictions to laboratory-quantity research use under Montreal Protocol rules.

Common Uses

  • Solvent for IR spectroscopy in the C–H stretching window (no interfering C–H bands)
  • Carbon source in the Appel reaction (PPh3 / CCl4) for converting alcohols to alkyl chlorides
  • Chlorinating agent in the Hunsdiecker decarboxylation
  • Teaching example of Td symmetry and bond-dipole cancellation
  • Historical dry-cleaning, fire-extinguishing, and refrigerant uses (phased out under the Montreal Protocol)

Safety Information

Severe hepatotoxin via CYP2E1-mediated formation of the •CCl3 radical, which initiates lipid peroxidation and causes centrilobular necrosis — the textbook mechanism of CYP-bioactivated liver injury. IARC Group 2B (possibly carcinogenic to humans). GHS: H301 (toxic if swallowed), H311 (toxic in skin contact), H331 (toxic if inhaled), H351 (suspected carcinogen), H372 (organ damage from repeated exposure), H420 (ozone layer damage). OSHA PEL 10 ppm (8-hour TWA), 25 ppm ceiling; ACGIH TLV 5 ppm. Production restricted under the Montreal Protocol with ODP 1.1. Decomposes on hot surfaces or in fires to phosgene — historically the lethal failure mode of Pyrene-style fire extinguishers. Handle in a hood with nitrile gloves and dispose as halogenated waste.

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 carbon tetrachloride?
CCl4 is 153.823 g/mol: carbon at 12.011 and four chlorines at 4 × 35.453 = 141.812. Density of the liquid is 1.59 g/mL at 25 °C — heavier than water, which is why historic 'carbon tet' fire extinguishers worked by smothering the fire with a denser-than-air vapor cloud, and why CCl4 forms the lower phase when shaken with water in a separatory funnel.
Why is carbon tetrachloride nonpolar despite having polar bonds?
Each C–Cl bond is polar — chlorine is more electronegative than carbon, so the bond dipole points toward chlorine at about 1.46 D. But the four bonds in CCl4 point to the corners of a regular tetrahedron, and the vector sum of four equal dipoles arranged that way is exactly zero. The molecule belongs to the Td point group (same symmetry as methane), which guarantees no net dipole. CCl4 is the standard textbook example for this cancellation-by-symmetry argument.
Why was carbon tetrachloride banned?
Two compounding reasons. First, ozone depletion: CCl4 has an atmospheric ODP of 1.1, slightly worse than CFC-11, because UV photolysis in the stratosphere releases chlorine radicals that catalytically destroy ozone in chain cycles. The Montreal Protocol (1987) phased out emissive production globally, with full restrictions by 2010. Second, hepatotoxicity: CYP2E1 in liver microsomes cleaves CCl4 to •CCl3, which abstracts allylic hydrogens from membrane lipids and starts a peroxidation cascade — centrilobular necrosis follows even at modest exposures. The combination of stratospheric and liver damage made the regulatory case overwhelming.