MASTERING ORGANIC CHEMISTRY

By-- S.K.SINHA

PRACTICAL ORGANICCHEMISTRY
1. Test of unsaturation
(a)
addition of H2,
(b)

(c)

1 1 mole H2
addition of Br2 \ CCl4 or Brominewater
*Phenolic compounds gives light yellow ppt with Br2 water.
*Aromatic amines gives ppt with Br2/H2O
Bayers Reagent discharge the colour of dil, cold, alkaline KMnO4 to pink or brown.

Terminal alkynes gives red/brown ppt with Cu2Cl2/NH4OH dueto Copperalkylide.

(e)
Terminal alkynegives whiteppt with tollens reagent 3 Silver alkylide.
(f)
undergoesozonolysis.
2. Test of OHgroup
(i)
evolves H2 gas with Na metal.
(ii)
gives red soln. with ceric ammoniam nitrate.
(iii)
gives ester with acetic anhydrides, acid chloride, acids.
(iv)
gives halides with PCl5, PX3, anhy. ZnCl2 / conc. HCl or SOCl2.
(v)
lucas test (anhy. ZnCl2 / Conc. HCl)
(d)

(vi)

3 Formation of turbidity immediate

2 Formation of turbidity within 5 minutes.
1 No turbidity appears
Victor Mayer Test
(i) P/I2/
(a) Red soln. nitrolic acid salt 10
(ii) AgNO2.
Alcohol
(iii) NaNO2 / conc. H2SO4

(vii)

(iv) OH
with Cu/300C

(b) blue soln. of Pseudonitrol 20

(c) No colour 3 alcohol

(a) 1 Alcohol aldehyde
(b) 2 Alcohol Ketone
(c) 3 Alcohol alkene

(3) Test of Phenolic group

(a)
soluble in NaOH Insolublein NaHCO3 (Picric acid is only alcohol solublein NaHCO3)
(b)
Phenol gives red colour with alc. FeCl3
(c)
Phenols undergoes acetylation & Methylation.
(4) Test of ether linkage
(a)
Ethers insoluble in H2O.
(b)
with HI gives alcohol and alkyl Iodide
(c)
with excess HI only alkyl Iodide
(5) Test of Carbonyl groups
(a)
Phenyl hydrazine &HCl brown crystallinecompound of phenyl hydrazone.
(b)
2,4 DNPH (Bradys reagent) Red ppt (c)
NH2OH/H+ Oxime
(d)
Reduced to alkanes by
(i)Wolff = Kishner reduction NH2NH2/KOH
(ii)Clemeneson reduction Zn(Hg)/HCl
aldehydes only
Red ppt with Fehling soln. Cu2O.`
(b)
Red ppt with Benedicts soln. Cu2O
Silver mirror (Ag) with Tollens Reagent. (d)
Pink colour with Schiffs reagent.
Aldol condensation Aldehydes with Hydrogen with dil base NaOH
Cannizzaro Reaction aldehydes without no hydrogen with conc. NaOH/KOH.
Ketones
Winered colour with sod. nitroprusside
aliphatic methyl ketones gives ppt with NaHSO3.
(c)
On Reduction gives 2 alcohol.
8. Test of corboxylic acid
(a)
With NaHCO3 effervescenceof CO2 (b)
PCl5, PCl3, SOCl2 acid chloride
6. Test of
(a)
(c)
(e)
(f)
7. Test of
(a)
(b)

(c)

Amides with NH3/

(e)

HCOOH also gives oxidation with

(i) Tollens Reagent
(ii) Fehling solution

9. Test for dibasic acid

(a)
Oxalic acid .

CO +CO2 +H2O

B-7. J AWAHAR NAGAR.Main Road ,Kota.

(d)

(b)

Acetic acid gives blood red colour with FeCl3

(iii) HgCl2

(iv) Br2

Malonic acid CH3COOH + CO2

Ph-0744-2422383 .Mo-93149-05055

Test for elements

It is a general test for the detection of halogens, nitrogen and sulphur in an
organic compound. These elements are covalently bonded to the organic
compounds. In order to detect them, these have to be converted into their
ionic forms. This is done by fusing the organic compound with sodium metal.
The ionic compounds formed during the fusion are extracted in aqueous
solution and can be detected by simple chemical tests. The extract is called
sodium fusion extract or Lassaigne's extract.
Test for Halogen:
Halogens present in an organic compound forms sodium halide on fusion with
sodium metal. Sodium halide extracted with water can be easily identified by
adding silver nitrate solution after acidifying with dil. HNO3.
If chlorine is present, a white curdy precipitate soluble in ammonium
hydroxide solution is formed.
Na + Cl NaCl
NaCl + AgNO3 AgCl + NaNO3
If bromine is present, an yellowish white precipitate sparingly soluble in
ammonium hydroxide solution is formed.
Na + Br NaBr
NaBr + AgNO3 AgBr + NaNO3
If iodine is present, an yellow precipitate insoluble in ammonium hydroxide
solution is formed.
Na + I NaI
NaI + AgNO3 AgI + NaNO3
Test for Nitrogen:
The carbon and nitrogen present in the organic compound on fusion with
sodium metal gives sodium cyanide (NaCN) soluble in water. This is
converted in to sodium ferrocyanide by the addition of sufficient quantity of
ferrous sulphate. Ferric ions generated during the process react with
ferrocyanide to form prussian blue precipitate of ferric ferrocyanide.
Na + C + N NaCN
6NaCN + FeSO4 Na4[Fe(CN)6] + Na2SO4

Sodium
ferrocyanide
Na4[Fe(CN)6] + Fe3+ Fe4[Fe(CN)6]3
Ferric ferrocyanide
Test for Sulphur:
If sulphur is present in the organic compound, sodium fusion will convert it
into sodium sulphide. Sulphide ions are readily identified using sodium
nitroprusside.
Na + S Na2S
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS]
Sodium nitroprusside

violet colour

Test for both Nitrogen and Sulphur:

If both nitrogen and sulphur are present in an organic compound, sodium
fusion will convert it into sodium thiocyanate which then react with Fe 3+ to
form blood colour complex [Fe(SCN)]2+
Na + C + N + S NaSCN
Fe3+ + 2Na [Fe(SCN)]2+
Note: If the Lassaigne's extract containing excess of sodium metal, sodium
cyanide and sulphides are formed instead of sodium thiocyanate.
NaSCN + 2Na NaCN + Na2S
Here in this type of cases, both sulphur and nitrogen are to be identified in
separate tests.