Chromyl Chloride Test

What is Chromyl Chloride Test?

Chromyl chloride test is a qualitative analysis test used for the conformation for Cl ions. Let’s take an example to further get a clearer understanding of the test. A sample of chlorine-containing salt is heated with potassium chromate (K­2Cr2O7) and concentrated sulfuric acid (H2SO4). If chloride is present, chromyl chloride is formed and red fumes are given out. Chromyl chloride test reaction is given as;

K2Cr2O7 +4NaCl+6H­2SO4 → 2CrO2Cl2 +2KHSO4 + 4NaHSO4 + 3H2O

However, for salts such as chlorides of mercury and silver chromyl chloride test is applicable. This is because the chlorides of mercury and silver are covalent and they do not generate Clions. The chromyl chloride test is applicable only for compounds having ­Cl ionic bonds. In essence, the chromyl chloride test is carried out if we suspect a sample having chloride or mainly for detecting the presence of Cl ions of ionic compounds.

Also Read: Qualitative Analysis of Organic Compounds

Chromyl Chloride and Its Properties

Chromyl chloride is a chemical compound and its chemical formula is given as CrO2Cl2. They are dark red blood colour liquid where the molecules of chromyl chloride are tetrahedral in shape. They are also mostly chromium (IV) derivatives (CrO4)2+.

Chemical Property

  • It is often used as an oxidizing agent. The chromyl chloride can be used for the oxidation of toluene to Benzaldehyde. This reaction is followed by two steps:

1. On reacting chromyl chloride with benzene a chromyl compound is formed.

C6H5CH3 + 2CrO2Cl2 → C6H5CH(CrO2Cl2)2

2. This chromyl compound is hydrolyzed with water to give the Benzaldehyde.

C6H5CH(CrO2Cl2)2 +2H2O → C6H5CH=O + CrO3 + 4HCl

This reaction is known as Etard’s Reaction and the chromyl chloride that is used here is a mild oxidizing agent which is excellent in making aldehydes.

  • Chromyl chloride can react with water to form chromic acid and hydrochloric acid. This reaction is exothermic.

CrO2Cl2 + 2H2O → H2CrO4 +2 HCl.

Physical Property

Chromyl chloride is a deep red viscous liquid, which fumes in the air. It reacts with water, alcohols, and is soluble in chlorinated carbons and carboxylic acids.

Chromyl Chloride Test Mechanism

The mechanism of chromyl chloride test is simple. On reacting potassium dichromate with sulphuric acid, chromate trioxide (oxidation state = +6) is formed. The colour of chromate trioxide (CrO3) varies from dark red to brown colour.

K2Cr2O7 + H­2SO4 → CrO3 + H2O

Now salt-containing chloride (NaCl) is reacted with sulphuric acid that gives sodium bisulphate (NaHSO­4) and hydrochloric acid (HCl) is also formed.

NaCl +H2SO4 → NaHSO­4 +HCl

In the next step, chromate trioxide is reacted with hydrochloric acid, which produces chromyl chloride (CrO2Cl2 ) which gives out red fumes.

CrO3 + HCl → CrO2Cl2

Confirmation for Chromyl Chloride Test

Now for the conformation of chromyl chloride, the red vapour needs to dissolves in a solution of sodium hydroxide (NaOH). The solution turns yellow (due to Na2CrO4).

CrO2Cl2 + NaOH → Na2CrO4 + NaCl +H2O

Reacting this solution further with the lead acetate and diluted acetic acid (CH3COOH) produces the yellow precipitate.

CrO42- + Pb(CH3COO)2 → PbCrO4 +CH3COONa

PbCrO4 is the yellow precipitate of chloride and hence the test is accurate.


Requirements: Orginal salt, powdered potassium dichromate, conc. Sulphuric acid, sodium hydroxide, dilute acetic acid, lead acetate, test tube, test holder, spatula, glass rod, dropper, bunsen burner.


  • A small quantity of salt is taken in the test tube. To this add a small amount of powdered potassium dichromate using a spatula. Mix it with a glass rod.
  • Add a small amount of concentrated sulphuric acid to the test tube dropper.
  • Heat the test tube over the bunsen burner and hold the test tube using the holder.
  • Red fumes should be given out indicating the formation of chromyl chloride.
  • This red fume should be collected using another test tube.
  • Next, add a small volume of sodium hydroxide to test tube filled with red fumes using a dropper.
  • Chromyl chloride reacts with the sodium hydroxide to form the yellow solution of sodium chromate.
  • Add a small amount of dilute acetic acid and the lead acetate using another dropper.
  • They react to form a yellow precipitate.

Precautions: Chromyl chloride is extremely corrosive and will fume in contact with air, releasing a mist of hydrochloric and chromic acids. Proper protection must be worn when handling the compound. As it is a Cr (VI) compound, it is also carcinogenic. Chromyl chlorides are usually sored in glass containers.

To dispose of the chromyl chloride, safely neutralize chromyl chloride, add child solvents like glacial acetic acid or chloroforms to the compound and stir the suspension/solution. Slowly add a reducing agent like ascorbic acid, until the colour changes from red/orange to green. Avoid adding the aqueous solutions, especially if you’re using glacial acetic acid as solvent, as the neutralization will generate heat.

Alternate Test for Chlorides

Prepare the soda extract of given salt, this method is feasible for heavy metal chlorides too. They produce NaCl even for the covalent chlorides. Sometimes we have to do this in the melt due to the insoluble chlorides. Then dilute this extract using the water and filter it. Then add AgNO3 (silver nitrate) to the solution, which produces a white precipitate AgCl. To confirm the chloride add sodium arsenite (Na3AsO3) to the solution and shake it well a yellow precipitate is formed, thus the presence of chloride is confirmed.