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.
Density of a gas is found to be 5.46 g/dm3 at 27 °C at 2 bar pressure. What will be its density at STP?
Enthalpy of combustion of carbon to CO2 is -393.5 kJ mol-1. Calculate the heat released upon formation of 35.2 g of CO2 from carbon and dioxygen gas.
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-
Depict the galvanic cell in which the reaction Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s) takes place, further show:
(i) which of the electrode is negatively charged,
(ii) the carriers of the current in the cell, and
(iii) individual reaction at each electrode.
What is meant by 'demineralised' water and how can it be obtained?
The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 × 105 ms–1. If the hockey ball of mass 0.1 kg is moving with this velocity, calculate the wavelength associated with this velocity.
Among the following pairs of orbitals which orbital will experience the larger effective nuclear charge?
(i) 2s and 3s,
(ii) 4d and 4f,
(iii) 3d and 3p
Calculate the amount of carbon dioxide that could be produced when
(i) 1 mole of carbon is burnt in air.
(ii) 1 mole of carbon is burnt in 16 g of dioxygen.
(iii) 2 moles of carbon are burnt in 16 g of dioxygen.
34.05 mL of phosphorus vapour weighs 0.0625 g at 546 °C and 0.1 bar pressure. What is the molar mass of phosphorus?
Calculate the standard enthalpy of formation of CH3OH(l) from the following data:
CH3OH (l) + 3/2 O2(g) → CO2(g) + 2H2O(l) ; ΔrH0 = –726 kJ mol–1
C(g) + O2(g) → CO2(g) ; ΔcH0 = –393 kJ mol–1
H2(g) + 1/2 O2(g) → H2O(l) ; ΔfH0 = –286 kJ mol–1.