Detection of Hetero Element

Experiment-8
TO DETECT THE FOREIGN ELEMENTS PRESENT IN A GIVEN ORGANIC COMPOUNDS (N,S AND X)

Theory
The study of hydrocarbons and their derivatives are called organic compounds. Organic compounds besides carbon
and hydrogen contain other foreign elements like N, X, S, etc. Organic compounds form covalent bonds and do
not ionize as they are water insoluble. These foreign elements are detected by converting these organic compounds into water
soluble compounds.
The best method to convert these elements into water soluble compounds is Lassaign's test or sodium test which is one of the
golden methods that can easily be done in the laboratory. Once these organic compounds are converted into water soluble
components, the element present can be identified with the help of differentTM laboratory reagents.

Preparation of Na-extract
Take a small piece of Na metal kept in kerosene oil, dry between folds of scrap filter paper and insert in a fusion tube. Heat the
fusion tube on bunsen flame slowly, when sodium becomes a shining globule, add organic compound into the fusion tube. Heat
first slowly and then strongly. When the fusion tube becomes red hot, Plunge the fusion tube into the crucible containing half a
test-tube of distilled water. While plunging, cover the crucible with asbestos sheet. Now, crush the fusion tube with the
help of glass rod. Boil it for sometimes 10-15 minutes. Filter the solution. The filtrate is known as sodium- extract. Sodium extract
must be colorless transparent and alkaline. If not alkaline, add 1-2 drops of NaOH in the Na-extract.

Reaction Involved

1) Na + C + N→ NaCN

2) 2NaOH + FeSO,→ Fe(OH)2 + Na2SO4 3) Fe(OH)2+2NaCN →

Fe(CN), + NaOH

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4) Fe(CN)2 + 4NaCN → Na,(Fe(CN)6]
5) Na [Fe(CN)6] + 4FeCl → Fe4[Fe(CN)6]3 + 12 NaCl
Note: Since, the color of Prussian blue is masked by the color of FeCl3, the oxidation of FeCl can be replaced by
the use of dil. H,SO, as below:
Na+C+N→ NaCN

2NaOH + FeSO4 →→Fe(OH)2 + Na2SO4 Fe(OH)2+2NaCN → Fe(CN),

+NaOH Fe(CN)2 +4NaCN → Na[Fe(CN)6]
sodium ferrocyanide

3Na [Fe(CN)6] + 4FeCl → Fe,[Fe(CN)6] + 12NaCl

Ferric ferrocyanide
(Prussian blue)
To dissolve dirty green precipitate of ferrous hydroxide, conc. HCl must be added. Otherwise it masks the color of ferric
ferrocyanide.

Fe(OH)2 + 2HCl → FeCl2 + 2H2O

Test for sulphur
2 Na + S→ Na2S
Na2S + Na2 [Fe(CN),NO]
Sodium nitroprusside
→ Na [Fe(CN),NOS]
Sodium thionitroprusside
(Transient-violet)

Na,S+ (CH,COO), Pb CH3COOH PbS↓ + CH,COONa

2

Test for both Nitrogen and sulphur

Na + C+N+S→ NaCNS

Test for halogens

Na + X→ NaX
Black (lead sulphide)

Fe3+

→ Fe(CNS), (red)
blood red coloration

dil.HNO3
NaX + AgNO3
AgX↓ + NaNO3
boil

Halides ions are tested with AgNO, solution, as usual. But before adding AgNO3, the sodium extract is boiled with dil.
HNO3 to remove NaCN and NaS which are present in the solution, if nitrogen and sulphur are already present and if
these cyanide and sulphide
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are not removed before hand, it will give white ppt of AgCN and black ppt of Ag,S. When heated
with dil. HNO,, these are removed as HCN and HS gases as below:
1. AgNO, + NaCN→ AgCNĮ + NaNO3
White

2. AgNO3 + Na2S→ Ag2S↓ + NaNO3

(black)
HNO3 + NaCN
boil
HCN↑ + NaNO3
(dil.)

HNO3 + Na2S
boil
→

> H2S↑ + NaNO3

(dil.)

Confirmative test for Chloride

NaCl + AgNO, → AgCl + NaNO3 AgCl + NH2OH → [Ag(NH3)2]Cl + H2O

[Ag(NH,),]Cl + HNO, → AgCl + NHẠNO,
+ NaBr/Nal + AgNO,→ AgBr↓/AgI + NaNO3

Confirmative test for Bromide and Iodide KMnO4 + HCl →→ KCl + MnCl2 + H2O
+ Cl2 Cl2 + 2Br → Br2+ 2C1
-
2

Cl2+ 21 → 12+2C1
CHCI, + Br2→ CHCl3.Br2 yellow/brown bottom layer CHCl3 + I2 → CHCI.I2
pink/violet bottom layer
Observation

S.N.

1.
Experiment

Detection of Nitrogen
 Observation

2.

Take about 2ml sodium extract, add 1-2 | Prussian blue or greenish blue drops of NaOH and few drops of
freshly colouration
prepared FeSO. Boil the solution, cool
4°

and add 1-2 drops of FeCl solution.

Finally, add few drops of conc. HCI.

Detection of sulphur
i. Take about 1-2ml of sodium extract, Transient violet colouration
add few drops of freshly prepared
sodium nitro prusside solution.

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Inference

Presence of nitrogen

Presence of sulphur

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ii. Take about 1-2ml of sodium extract, Black precipitate forms
add few drops of acetic acid and then
Presence of sulphur
add few drops of lead acetate solution.

3.
Detection of both Nitrogen and Sulphur
together

Take about 1-2ml of sodium extract, Blood red colouration and add few drops of FeCl3.
Presence of both Nitrogen and Sulphur

4.
Detection Halogen
 1. White precipitate readily
Take about 1-2ml of sodium extract,
add few drops of dil. HNO,. Boil for
soluble in NH,OH and reappears on the addition
Presence of Chlorine

5-7 minutes. Cool and add 1-2 drops of AgNO, solution.

of dil. HNO3.
2.
Pale yellow ppt sparingly soluble in NH.OH.
Presence of
bromine

3. Yellow ppt insoluble in Presence of

NH2OH.
Iodine

Presence of
yellow or brown color.
bromine
Confirmative test for Bromine and 1. CCI, layer becomes
5.
Iodine

Take about 1-2ml of sodium extract,

add few drops of CCI4, KMnO4 solution 2. CCI, layer becomes violet Presence of
and 1-2 drops of dil. HCl. shake it well.
colour.
Iodine

Reaction Involved:

1. Na + C + N→ NaCN

2NaOH + FeSO →Fe(OH)2 + Na2SO4

4

Fe(OH)2+2NaCN→ Fe(CN)2 +NaOH

Fe(CN), +4NaCN→ Na [Fe(CN)6]
2

3Na[Fe(CN)6] + 4FeCl → Fe[Fe(CN)6] + 12NaCl

(Prussian blue)

2. Na2S + Na2[Fe(CN),NO] → Na,[Fe(CN),NOS] 3. Na2S + (CH,COO), Pb

CH,COOH PbS↓ + CH3COONa
-

4. NaCNS + FeCl3 → Fe(CNS), + NaCl

5. NaCl + AgNO,→ AgCl↓ + NaNO3
3

AgCl + NH2OH → [Ag(NH3)2]Cl + H2O [Ag(NH3)2]Cl + HNO3 → AgCl↓↓ +

NHNO,
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6. NaBr + AgNO, -> AgBr↓ + NaNO, 7. Nal + AgNO. --> Agl↓ + NaNO,
8. KMnO4 + HCl -> KCl + MnCl, + HO + Cl
Cl2 + 2Br → Br12 + 2CI
CHCI + Br→ CHCI,.Br, yellow/brown bottom layer 9. KMnO4 + HCl -> KCl + MnCl, +
H2O + Cl2
Cl2+ 21 → I, + 2CI
2

CHCI + I → CHCI,.I, pink/violet bottom layer

Result:
Hence the given sample E, contains ....... as heteroelement.
Conclusion:
Thus, Na extract of organic compound can be used to detect the heteroelement, present in it.

Precaution
1. Na-extract shold be concentrated.
2. Na-extract should be colorless and alkaline.
3. Na-extract should not be tested because it contains poisonous NaCN.

Viva-voce Questions
1. What do you mean by heteroelement?
2. Define Na-extract? Why is it prepared?
3. Why only Na-extract not Na, K, Ca and Mg extract is prepared?
4. Why is Na-extract always alkaline?
5. Na-extract must always be prepared with distilled water, why?
6. What is the formula of prussian blue?
7. Na-extract is boiled with HNO, in halogen test, why?
8. Why is freshly prepared FeSO4 added to Na-extract in nitrogen?
9. Do you know the forilla of sodium nitroprusside?
10. Can you calculate the O.N. of Fe in prussian blue?
11. In a special halogen test, brown layer and violet layer are formed, why?
12. The curdy white ppt readily dissolves in excess NH,OH in chlorine test, why?

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