Picric acid
Picric acid, systematically named 2,4,6-trinitrophenol, is an organic compound with the molecular formula C₆H₃N₃O₇, appearing as odorless, pale yellow crystals that exhibit strong acidity and explosive properties due to the presence of three nitro groups attached to a phenolic ring.[1][2] It is produced industrially via the nitration of phenol using a mixture of nitric and sulfuric acids, a process that yields the highly nitrated product valued for its chemical reactivity.[3] Historically, picric acid served as a vital high explosive in military applications, notably in French shells during World War I under the trade name mélinite, where its power surpassed that of black powder but was tempered by its sensitivity to impact and friction.[4] Prior to its explosive prominence, it found use as a yellow dye for silk and wool, an antiseptic in wound dressings during the 19th century, and even in early photographic processes, though these applications diminished with safer alternatives.[5] Its defining hazards stem from extreme sensitivity when dry, forming shock-sensitive picrate salts with metals that can detonate spontaneously, alongside acute toxicity causing liver and kidney damage upon ingestion, inhalation, or skin absorption, rendering it a restricted substance requiring perpetual moistening for safe storage.[6][2] Despite these risks, its legacy endures in specialized analytical chemistry, such as protein precipitation in Kjeldahl nitrogen determination, underscoring a balance between utility and peril in nitroaromatic compounds.[4]Chemical Identity and Properties
Molecular Structure and Formula
Picric acid has the molecular formula C₆H₃N₃O₇ and the IUPAC name 2,4,6-trinitrophenol.[1] Its structure consists of a benzene ring with a hydroxyl group attached to carbon 1 and nitro groups (-NO₂) substituted at the ortho and para positions (carbons 2, 4, and 6).[1] [7]
The three nitro groups exert strong electron-withdrawing inductive and resonance effects, which delocalize the negative charge in the conjugate base, enhancing acidity far beyond that of phenol (pKₐ ≈ 10).[1] Picric acid's pKₐ is 0.42, classifying it as a strong organic acid due to this stabilization of the phenolate ion.[1] These substituents also contribute to its high reactivity in electrophilic and oxidative processes by activating the ring toward certain reactions while deactivating it overall.[1]
Physical Characteristics
Picric acid is an odorless, pale yellow crystalline solid at standard conditions.[1][8] It exhibits a melting point of 122–123 °C, transitioning to a liquid phase without boiling under normal pressures, as it decomposes at approximately 300 °C.[8][2] The compound has a density of 1.76 g/cm³ for the solid form.[1][9] Its solubility in water is moderate, at about 12–14 g/L at 20 °C, while it shows high solubility in organic solvents such as ethanol (>100 g/L) and diethyl ether.[10][8] In wetted form, typically with 10–30% water content, it presents as a yellow paste or slurry, altering its handling characteristics due to the incorporated liquid phase.[1]| Property | Value |
|---|---|
| Appearance | Pale yellow crystals |
| Odor | None |
| Melting point | 122–123 °C |
| Density (solid) | 1.76 g/cm³ |
| Solubility in water (20 °C) | ~12 g/L |
| Solubility in ethanol | Highly soluble (>100 g/L) |