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Neutral FeCl3 Test: Detection of Phenols & Enols | Chemca

Neutral FeCl3 Test: Detection of Phenols & Enols | Chemca
Organic Chemistry

Neutral Ferric Chloride Test: Detection of Phenols

By Chemca Editorial Team Last Updated: January 2026 7 min read

The Neutral Ferric Chloride Test is the characteristic qualitative test for Phenols and compounds containing the Enol group ($=C(OH)-$). It relies on the formation of a colored coordination complex between the iron(III) ion and the phenolic/enolic oxygen.

1. Preparation of "Neutral" FeCl3

Ferric Chloride ($FeCl_3$) solution is acidic due to hydrolysis ($FeCl_3 + 3H_2O \rightleftharpoons Fe(OH)_3 + 3HCl$). The free HCl can interfere with the test or protonate the phenol.

How to Neutralize?

Ammonium Hydroxide ($NH_4OH$) is added dropwise to the $FeCl_3$ solution until a reddish-brown precipitate of ferric hydroxide just starts to appear. The solution is then filtered. The clear filtrate is Neutral $FeCl_3$.

2. General Reaction & Mechanism

Phenols react with neutral ferric chloride to form a water-soluble violet-colored complex.

$$ 6 C_6H_5OH + FeCl_3 \longrightarrow \underbrace{[Fe(OC_6H_5)_6]^{3-}}_{\text{Violet Complex}} + 3H^+ + 3HCl $$

Key Concept: The reaction is a ligand exchange where the phenol molecules (acting as ligands) replace the water/chloride ligands around the central Iron(III) ion. The colour arises from Ligand-to-Metal Charge Transfer (LMCT).

3. Color Variations (Diagnostic)

The specific color observed depends on the structure of the phenol or enol.

Compound Observed Color
Phenol, o-Cresol, Resorcinol Violet / Blue
Catechol (1,2-Benzenediol) Green
p-Cresol, Hydroquinone Transient Blue / Green (quickly oxidizes to quinhydrone)
$\alpha$-Naphthol Pink / Red
$\beta$-Naphthol Green
Salicylic Acid Violet

4. Test for Enols

Compounds containing a stable enol form (like $\beta$-keto esters) also give a positive test.

Example: Ethyl Acetoacetate

Ethyl Acetoacetate exists in equilibrium between keto and enol forms. The enol form coordinates with $Fe^{3+}$ to give a Reddish-Violet color.

$$ CH_3-C(OH)=CH-COOEt + FeCl_3 \rightarrow \text{Violet Complex} $$

5. Test for Acetate/Formate Salts

While principally for phenols, neutral $FeCl_3$ reacts with neutral solutions of Acetate or Formate ions to give a Blood Red coloration.

$$ 3CH_3COO^- + Fe^{3+} \rightarrow (CH_3COO)_3Fe \text{ (Red Solution)} $$

Upon boiling, this red solution forms a reddish-brown precipitate of Basic Ferric Acetate.

6. Limitations

  • Aliphatic Alcohols: Do not react (Color remains yellow/orange).
  • Sterically Hindered Phenols: (e.g., 2,4,6-tritert-butylphenol) may fail to form the complex.
  • Some Acids: Picric Acid does not give the typical violet color. Meta and Para-nitrophenols may not give a distinct color change.

FeCl3 Test Quiz

Test your concepts on Phenol identification. 10 MCQs with explanations.

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