Qualitative Analysis of Elements in Organic Compounds

A. Carbon and Hydrogen

 Combustion:

C 12 H 22 O 11 + 48CuO →12 C O 2 ↑+11 H 2 O+ 24 C u2 O

Sugar black powder moisture dark red/brown

(white crystals) formed solid

H 2 O (moisture) formed N

At the other end of delivery tube:

C O2 ↑+ Ca ( OH )2 →CaC O3 ↓+ H 2 O
Lime water white
precipitate

CaC O3 ↓ ¿white precipitate) formed C

B. Test for Oxygen

 Ferrox paper: absorbed with SC N and Fe3 +¿¿ions

−¿ ¿

 Fe3 +¿¿ forms blood red complex with SC N

−¿ ¿
2+¿ (aq )¿
−¿( aq)→ Fe( SCN ) ¿

Fe3 +¿ (aq )+SC N ¿

blood red complex

 Oxygen in the compound forms a deep red to purple complex with Fe ( SCN )2+ ¿¿
2+ ¿¿

( SCN )2 +¿ Fe−−O −−Fe ( SCN ) ¿

C. Sodium Fusion

 Na metal and an organic compound melt together (fusion) during heating

 They undergo a redox reaction in which Na is oxidised and hetero elements
are reduced
R= alkyl group RX , R3 N , R 2Na
S→ NaX , NaCN , Na2 S
heat
 Ions of X, N, and S are dissolved and tested

D. Test for N, S, X

 Lassaigne’s test (presence of N):

2 NaCN + FeS O 4 → Fe(CN )2 + Na2 S O 4
Fe(CN )2+ 4 NaCN → N a4 Fe(CN )6
Na4 Fe(CN )6+ 4 Fe Cl3 → F e 4 [ Fe ( CN )6 ]3
Prussian blue ppt
(bluish green)
  Test for Sulfur (S):
N a2 S + Pb ( CH 3 COO )2 → PbS ↓+ 2 Na CH 3 COO
Black ppt
 Test for Halogens (X) (Silver Nitrate Test):
+ ¿ ( aq ) ¿

Ag+¿ ( aq)+ NaX → AgX ↓ +N a ¿

Cl white ppt
Br, I yellow ppt
- Yellow ppt indicates presence of Br or I but may not imply the absence
ofCl
- White ppt of AgCl may be obscured by the intense yellow color of AgBr or
AgI
- For better differentiation among halogens:
1. Acidify fusion filtrate with 3N H2SO4, boil, cool
2. Add carbon tetrachloride CCl4
3. Add few drops of NaClO (laundry bleach), shake
a. If the CCl4 layer remains colorless Cl
b. If the CCl4 layer is brown Br
c. If the CCl4 layer is violet I

Qualitative Analysis of Organic Functional Groups

A. Test for Hydrocarbons (Unsaturated)

 Baeyer’s Test for Multiple Bonds KMnO4 Sol.

- Uses dilute alkaline KMnO4 to Oxidize the C-C double or triple bond

- >1 drop of reagent to give purple color unsaturation or easily

oxidized
functional group is present
- Positive Test: brown suspension of MnO2
- Cyclohexane ( - ) Cyclohexene/Linoleic Acid ( - ) Bromobenzene ( + )
 Ignition Test for High Degrees of Unsaturation
- Unsaturated bonds form luminous flame and sooty deposits
 15
C6 H6+ → 6 C O 2 +3 H 2 O(+C ( s) )
2O 2
- Positive Test: sooty yellow flame (aromatic, unsaturated)
- Negative Test: luminous flame/not sooty/less yellow (aliphatic, saturated)
- Benzophenone ( - ) Cyclohexane ( + )

B. Alcohols by Jones Oxidation

 Jones Reagent
- Consists of chromium trioxide CrO3 and sulphuric acid dissolved in a
mixture of acetone and water. As an alternative, potassium dichromate
can be used in place of chromium trioxide

- Positive Test: Green color within 15 sec of addition with reagent

- Negative Test: Remain orange
- 1-butanol > 2-butanol >>> t-butylaic

C. Aldehydes and Ketones

- Formaldehyde has a sharp, somewhat unpleasant odor

- Aromatic Aldehydes have very pleasant “flavour”
- Benzaldehyde has the characteristic odor of almonds

 2,4-Dinitrophenylhydrazine/DNPH Test (General Test for Carbonyl

Compounds)
- General test for aldehydes and ketones

- Positive Test: yellow, orange, yellow-orange, reddish-orange precipitate

- Formaldehyde ( + ) Benzaldehyde ( + ) Acetone ( + )

 Tollen’s Test (General Test for Aldehydes)

- General test for aldehydes
- Oxidation reaction in which aldehydes reacts with ammoniacal silver nitrate to
yield a ppt of silver metal, which appears as a mirror
- Positive Test: Silver metal like a mirror
- Formaldehyde ( + ) Benzaldehyde ( + ) Acetone ( - )
O H¿
A g2 O+ 4 N H 3+ H 2 O →2 Ag ( N H 3 )+¿+2
2

 Fehling’s Test (General Test for Aliphatic Aldehydes)

- General test for aliphatic aldehydes
- Oxidation reaction
- Fehling’s A sol. → CuSO 4
- Fehling’s B sol. → NaOH + potasium tartate (Rochelle Sal t)
- Positive Test: Red C u2 O precipitates
- Formaldehyde ( + ) Benzaldehyde ( - ) Acetone ( - )

D. Carboxylic Acids

 Sodium Bicarbonate Test for Carboxylic Acids

- Evolution of carbon dioxide
- Positive Test: Bubbles presence of CO2