Discuss the chemistry of Lassaigne's test.
Lassaigne's test: This test is used to detect the presence of nitrogen, sulphur, halogens, and phosphorous in an organic compound. These elements are present in covalent form in an organic compound. These are converted into the ionic form by fusing the compound with sodium metal.
The cyanide, sulphide, and halide of sodium formed are extracted from the fused mass by boiling it in distilled water. The extract so obtained is called Lassaigne's extract. This Lassaigne's extract is then tested for the presence of nitrogen, sulphur, halogens, and phosphorous.
(a) Test for nitrogen
Lassaignes's extract + Ferrous Sulphate
⬇ Conc. sulphuric acid
Prussian blue colour
(Ferriferro cyanide)
Chemistry of the test
In the Lassaigne's test for nitrogen in an organic compound, the sodium fusion extract is boiled with iron (II) sulphate and then acidified with sulphuric acid. In this process, sodium cyanide first reacts with iron (II) sulphate and forms sodium hexacyanoferrate (II). Then, on heating with sulphuric acid, some iron (II) gets oxidised to form iron (III) hexacyanoferrate (II), which is Prussian blue in colour. The chemical equations involved in the reaction can be represented as
6CN- + Fe2+ → [Fe(CN)6]4-
3[Fe(CN)6]4- + 4Fe3+ → Fe4[Fe(CN)6]3
Prussian blue colour
(b) Test for sulphur
(i) Lassaignes's extract + Lead acetate → Black precipitate
Chemistry of the test
In the Lassaigne's test for sulphur in an organic compound, the sodium fusion extract is acidified with acetic acid and then lead acetate is added to it. The precipitation of lead sulphide, which is black in colour, indicates the presence of sulphur in the compound.
S2- + Pb2+ → PbS
(Black)
(ii) Lassaignes's extract + Sodium nitroprusside → Violet colour
Chemistry of the test
The sodium fusion extract is treated with sodium nitroprusside. Appearance of violet colour also indicates the presence of sulphur in the compound.
S2- + [Fe(CN)5 NO]2- → [Fe(CN)5NOS]-4
(Violet)
If in an organic compound, both nitrogen and sulphur are present, then instead of NaCN, formation of NaSCN takes place.
Na + C + N + S → NaSCN
This NaSCN (sodium thiocyanate) gives a blood red colour. Prussian colour is not formed due to the absence of free cyanide ions.
Fe3+ + SCN → [Fe(SCN)]2+
(Blood Red)
(c) Test for halogens
Chemistry of the test
In the Lassaigne's test for halogens in an organic compound, the sodium fusion extract is acidified with nitric acid and then treated with silver nitrate.
X- + Ag+ → AgX
(X = Cl,Br,I)
If nitrogen and sulphur both are present in the organic compound, then the Lassaigne's extract is boiled to expel nitrogen and sulphur, which would otherwise interfere in the test for halogens.
What are hybridisation states of each carbon atom in the following compounds ?
(i) CH2=C=O,
(ii) CH3CH=CH2,
(iii) (CH3)2CO,
(iv) CH2=CHCN,
(v) C6H6
Explain the terms Inductive and Electromeric effects. Which electron displacement effect explains the following correct orders of acidity of the carboxylic acids?
(a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(b) CH3CH2COOH > (CH3)2CHCOOH > (CH3)3C.COOH
Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethyl butanal, Heptan-4- one.
Give condensed and bond line structural formulas and identify the functional group(s) present, if any, for :
(a) 2,2,4-Trimethylpentane
(b) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(c) Hexanedial
Indicate the σ and π bonds in the following molecules :
(i) C6H6,
(ii) C6H12,
(iii) CH2Cl2,
(iv) CH2=C=CH2,
(v) CH3NO2,
(vi) HCONHCH3
Identify the reagents shown in bold in the following equations as nucleophiles or electrophiles:
(a) CH3COOH + HO- → CH3COO- + H2O
(b) CH3COCH3 + C-N → (CH3)2 C (CN) (OH)
(c) C6H5 + CH3C+O → C6H5COCH3
For the following bond cleavages, use curved-arrows to show the electron flow and classify each as homolysis or heterolysis. Identify reactive intermediate produced as free radical, carbocation and carbanion.
Which of the following represents the correct IUPAC name for the compounds concerned?
(a) 2,2-Dimethylpentane or 2-Dimethylpentane
(b) 2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane
(c) 2-Chloro-4-methylpentane or 4-Chloro-2-methylpentane
(d) But-3-yn-1-ol or But-4-ol-1-yne
Draw the resonance structures for the following compounds. Show the electron shift using curved-arrow notation.
(a) C6H5OH
(b) C6H5NO2
(c) CH3CH=CHCHO
(d) C6H5–CHO
(e) C6 H5 - C+H2
(f) CH3CH = CHC+H2
Which of the following carbocation is most stable ?
How do you account for the formation of ethane during chlorination of methane?
What will be the minimum pressure required to compress 500 dm3 of air at 1 bar to 200 dm3 at 30°C?
What are the common physical and chemical features of alkali metals?
Calculate the molecular mass of the following:
(i) H2O
(ii) CO2
(iii) CH4
Assign oxidation number to the underlined elements in each of the following species:
(a) NaH2PO4
(b) NaHSO4
(c) H4P2O7
(d) K2MnO4
(e) CaO2
(f) NaBH4
(g) H2S2O7
(h) KAl(SO4)2.12 H2O
What is the basic theme of organisation in the periodic table?
Explain the formation of a chemical bond.
Choose the correct answer. A thermodynamic state function is a quantity
(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only.
A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature. The volume of the container is suddenly increased.
a) What is the initial effect of the change on vapour pressure?
b) How do rates of evaporation and condensation change initially?
c) What happens when equilibrium is restored finally and what will be the final vapour pressure?
Justify the position of hydrogen in the periodic table on the basis of its electronic configuration.
Write balanced equations for reactions between
(a) Na2O2and water
(b) KO2 and water
(c) Na2O and CO2
What happens when
(i) magnesium is burnt in air
(ii) quick lime is heated with silica
(iii) chlorine reacts with slaked lime
(iv) calcium nitrate is heated ?
The concentration of hydrogen ion in a sample of soft drink is 3.8 × 10–3 M. what is its pH?
Why does the following reaction occur ?
XeO4– 6(aq) + 2F – (aq) + 6H + (aq) → XeO3(g) + F2(g) + 3H2O(l)
What conclusion about the compound Na4XeO6 (of which XeO4– 6 is a part) can be drawn from the reaction.
How will you convert benzene into
(i) p - nitrobromobenzene
(ii) m - nitrochlorobenzene
(iii) p - nitrotoluene
(iv) acetophenone?
In a process, 701 J of heat is absorbed by a system and 394 J ofwork is done by the system. What is the change in internal energy for the process?
Whenever a reaction between an oxidising agent and a reducing agent is carried out, a compound of lower oxidation state is formed if the reducing agent is in excess and a compound of higher oxidation state is formed if the oxidising agent is in excess. Justify this statement giving three illustrations.
The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are, –890.3 kJ mol–1 , –393.5 kJ mol–1, and –285.8 kJ mol–1 respectively. Enthalpy of formation of CH4(g) will be
(i) –74.8 kJ mol–1
(ii) –52.27 kJ mol–1
(iii) +74.8 kJ mol–1
(iv) +52.26 kJ mol–1
Which of the alkali metal is having least melting point?
(a) Na (b) K (c) Rb (d) Cs
What is meant by the conjugate acid-base pair? Find the conjugate acid/base for the following species:
HNO2, CN– , HClO4, F –, OH–, CO2–3 and S-