Q.For testing halogens in an organic compound with AgNO3 solution, sodium extract (Lassaigne's test) is acidified with dilute HNO3. What will happen if a student acidifies the extract with dilute H2SO4 in place of dilute HNO3?
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Lassaigne Test Principle
The Lassaigne Test: Why We Fuse Sodium with the Sample
Imagine you have an organic compound — say, a drug, a pesticide, or a dye — and you need to find out if it contains nitrogen, sulfur, or a halogen (chlorine, bromine, iodine). You cannot simply test the original compound directly because these elements are covalently bonded inside the molecule. They are "hidden" — not present as free ions.
The Lassaigne test solves this by breaking the covalent bonds and converting these elements into water-soluble ionic salts. That is the entire point: turn invisible atoms into detectable ions.
The Intuition
Think of the organic molecule as a locked safe. Inside the safe are the atoms you want to detect (N, S, X). The safe is the covalent framework. To get the atoms out, you need to smash the safe open. Sodium metal is the sledgehammer.
When you heat the organic compound with a piece of sodium metal, the sodium reacts violently. It rips apart the carbon‑carbon and carbon‑heteroatom bonds. In the process, the sodium itself gets oxidised (loses an electron) and the atoms from the compound get reduced (gain electrons). The result is a set of simple, stable, ionic compounds:
- Nitrogen (from the compound) combines with sodium and carbon to form sodium cyanide (NaCN).
- Sulfur forms sodium sulfide (Na2S).
- Halogens form sodium halides (NaX, where X = Cl, Br, I).
These are all water‑soluble. Once you dissolve the fused mass in water, you have a solution containing CN−, S2−, and X− ions — ready for standard qualitative tests.
If both nitrogen and sulfur are present in the same compound, they can also form sodium thiocyanate (NaSCN) during fusion. This is important because it can interfere with the test for sulfur — more on that later.
The Precise Statement
Lassaigne’s test (or sodium fusion test): A small piece of dry sodium metal is heated with a sample of the organic compound in a fusion tube until the tube is red hot. The fused mass is then extracted with distilled water, boiled, cooled, and filtered. The filtrate (called the Lassaigne’s extract) is used to test for the presence of nitrogen, sulfur, and halogens.
The chemical principle is:
Organic compound (containing N, S, X)+Na (excess)ΔNaCN+Na2S+NaX+residue
Why This Works (and What Can Go Wrong)
For nitrogen: The cyanide ion (CN−) is detected by adding ferrous sulfate and ferric chloride — a deep blue precipitate of Prussian blue (Fe4[Fe(CN)6]3) confirms nitrogen.
For sulfur: The sulfide ion (S2−) gives a purple/violet colour with sodium nitroprusside (Na2[Fe(CN)5NO]). Alternatively, it forms a black precipitate of lead sulfide (PbS) with lead acetate.
For halogens: The halide ion (X−) is detected by acidifying the extract with nitric acid and adding silver nitrate — a curdy white precipitate (AgCl), pale yellow (AgBr), or yellow (AgI) indicates the halogen. …
Concept: Lassaigne's test for halogens — why HNO₃, not H₂SO₄.
The sodium fusion extract contains halide ions (XX−). Adding silver nitrate should
precipitate the silver halide (AgX) — white AgCl, pale-yellow AgBr,
yellow AgI. The extract is first acidified to destroy interfering CNX− and
SX2− (as volatile HCN and H₂S), and the acid used must not itself give a
precipitate with AgX+.
If dilute H₂SO₄ is used instead of dilute HNO₃, the sulphate ions it introduces react
with the silver nitrate to give a white precipitate of silver sulphate:
2AgNOX3+HX2SOX4AgX2SOX4↓+2HNOX3
Silver sulphate is only sparingly soluble, so this white precipitate forms whether or not …
Acidifying the sodium extract with dilute H2SO4 instead of dilute HNO3 will produce a white precipitate of Ag2SO4 that interferes with the halide test, making it impossible to confirm the presence of halogens reliably.
Why We Acidify in Lassaigne's Test
When an organic compound containing halogens is fused with sodium metal, the halogen converts to sodium halide (NaX, where X=Cl,Br,I) in the aqueous extract. To detect these halides, we add AgNO3, which precipitates them as silver halides:
NaX+AgNO3→AgX↓+NaNO3
The precipitate colour tells us which halogen is present: AgCl is white, AgBr is pale yellow, and AgI is yellow.
But the sodium extract is alkaline (from excess sodium and the formation of NaOH, Na2CO3, NaCN, etc.). If we add AgNO3 directly to this alkaline solution, silver hydroxide and silver oxide precipitate:
AgNO3+NaOH→AgOH↓+NaNO3
2AgOH→Ag2O↓+H2O
These brown/black precipitates mask the halide test. So we acidify first to neutralise the alkalinity.
Why Nitric Acid, Not Sulphuric Acid?
The choice of acid matters because we need one that does not itself interfere with the silver ion.
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With dilute HNO3: Nitric acid neutralises the alkaline impurities (NaOH, Na2CO3, NaCN, Na2S) without forming any precipitate with Ag+. The nitrate ion (NO3−) does not precipitate silver, so the only precipitate that forms is from the halide ions—exactly what we want to observe.
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With dilute H2SO4: Sulphuric acid also neutralises the alkaline species, but it introduces sulphate ions (SO42−) into the solution. When AgNO3 is added, these sulphate ions react:
2AgNO3+H2SO4→Ag2SO4↓+2HNO3 …
- TG EAPCET 2025Set eng-2025-05-02-FN1 markMCQQ.Identify the reaction, which is not related to extraction of copper (A) 2Cu2S+3O2→2Cu2O+2SO2 (B) 2FeS+3O2→2FeO+2SO2 (C) FeO+SiO2→FeSiO3 (D) SiO2+CaO→CaSiO3
›Reveal solutionSolution
The question asks which reaction is not part of copper extraction. The correct answer is (D), because CaO and SiO₂ are used in iron extraction (slag formation), not in copper smelting.
The key concept here is metallurgical extraction sequences. Each metal has a specific set of chemical reactions used to purify it from its ore. Copper extraction from chalcopyrite or copper glance involves roasting, smelting, and converting — but never uses calcium oxide. The reactions in (A), (B), and (C) are all directly part of the copper extraction process, while (D) is a slag-forming reaction from the iron extraction process.
Let’s go through each option step by step.
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Option (A):
2Cu2S+3O2→2Cu2O+2SO2
This is the roasting of copper(I) sulfide (from ores like chalcocite). It converts sulfide to oxide and removes sulfur as SO₂. This is a core step in copper extraction.
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Option (B):
2FeS+3O2→2FeO+2SO2
Copper ores often contain iron sulfides (e.g., chalcopyrite CuFeS₂). During roasting, iron sulfide is oxidized to iron(II) oxide. This is essential to later remove iron as slag. So this reaction is part of copper extraction.
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Option (C):
FeO+SiO2→FeSiO3
In copper smelting, silica (SiO₂) is added as a flux to combine with FeO, forming iron silicate slag (FeSiO₃). This removes iron impurities from the molten copper. So this reaction is part of copper extraction.
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Option (D):
SiO2+CaO→CaSiO3 …
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- TG EAPCET 2025Set eng-2025-05-04-AN1 markMCQQ.Which of the following gives more number of oxides on reacting with HCl? (A) Na2CO3 (B) NaNO2 (C) Na2SO3 (D) NaHCO3
›Reveal solutionSolution
The key is that HCl reacts with these sodium salts to produce gases (oxides) like CO₂, NO₂, and SO₂; NaNO₂ gives the most oxides because it can produce both NO and NO₂ depending on conditions, while the others yield only one oxide each.
The question asks which compound, when reacted with HCl, produces the most number of different oxides (as gases). We need to consider the products of each reaction, focusing on the gaseous oxides formed.
Concept & Intuition:
When a salt of a weak acid reacts with a strong acid like HCl, the weak acid is displaced. If the weak acid is unstable, it decomposes into an oxide (often a gas) and water. The "number of oxides" here means the distinct chemical species that are oxides (e.g., CO₂, SO₂, NO₂). Some reactions may yield more than one oxide if the salt contains an element that can exist in multiple oxidation states in its gaseous products.
Step-by-step reasoning:
- Reaction of Na₂CO₃ with HCl Sodium carbonate reacts with HCl to give carbonic acid, which immediately decomposes:
Na2CO3+2HCl→2NaCl+H2O+CO2↑
Only one oxide is produced: CO₂.
- Reaction of NaNO₂ with HCl
Sodium nitrite reacts with HCl to form nitrous acid (HNO₂), which is unstable and decomposes in multiple ways:
- Primary decomposition:
2HNO2→NO↑+NO2↑+H2O
This yields **two oxides**: NO (nitric oxide) and NO₂ (nitrogen dioxide).- Additionally, in the presence of excess HCl, some NO₂ can further react, but the key point is that at least two distinct nitrogen oxides are formed directly from the decomposition. Thus, NaNO₂ gives two different oxides.
- Reaction of Na₂SO₃ with HCl Sodium sulfite reacts with HCl to give sulfurous acid, which decomposes: Na2SO3+2HCl→2NaCl+H2O+SO2↑ …
- TG EAPCET 2025Set ap-2025-04-29-FN1 markMCQQ.Which of the following sets are correctly matched? I. NaHCO3 – used in fire extinguisher II. Na2CO3 – water softening III. NaOH – purification of bauxite The correct option is (A) I, II only (B) II, III only (C) I, III only (D) I, II, III
›Reveal solutionSolution
All three statements — NaHCO₃ in fire extinguishers, Na₂CO₃ in water softening, and NaOH in bauxite purification — are correct. The answer is (D).
The question tests your knowledge of the everyday uses of three important sodium compounds. Each of these uses is a direct consequence of the compound’s chemical properties — not something to memorise blindly, but something to connect to the chemistry you already know.
Let’s examine each statement one by one.
- NaHCO₃ – used in fire extinguisher Sodium bicarbonate decomposes on heating to give CO₂ gas:
2NaHCO3ΔNa2CO3+H2O+CO2
The CO₂ produced is heavier than air and smothers the fire by cutting off the oxygen supply. This is the principle behind soda-acid fire extinguishers. Statement I is correct.
- Na₂CO₃ – water softening Hard water contains Ca²⁺ and Mg²⁺ ions. Sodium carbonate (washing soda) precipitates these as insoluble carbonates:
Ca2++CO32−→CaCO3↓
Mg2++CO32−→MgCO3↓
This removes the hardness permanently. Statement II is correct.
- NaOH – purification of bauxite …
- TG EAPCET 2024Set eng-2024-05-09-FN1 markMCQQ.Which of the following when subjected to thermal decomposition will liberate dinitrogen?(i) sodium nitrate(ii) ammonium dichromate(iii) barium azide (A) i, ii only (B) ii, iii only (C) i, iii only (D) i, ii, iii
›Reveal solutionSolution
The key is to recall the thermal decomposition products of each compound: only ammonium dichromate and barium azide liberate dinitrogen gas, while sodium nitrate gives nitrogen dioxide and oxygen. The correct option is (B).
Concept and Intuition
Thermal decomposition reactions often produce gases, and the identity of those gases depends on the stability of the anion and the metal’s reactivity. For dinitrogen (N₂) to be released, the compound must contain nitrogen in a form that can pair up into N≡N bonds upon heating. Nitrates (NO₃⁻) tend to decompose to oxygen and nitrogen dioxide (or nitrites), not N₂. Azides (N₃⁻) are famous for yielding N₂ because the azide ion is inherently unstable. Ammonium dichromate is a special case: the ammonium ion (NH₄⁺) acts as a reducing agent, and the dichromate (Cr₂O₇²⁻) oxidizes it, producing N₂, water, and chromium(III) oxide. So we check each compound’s decomposition pathway.
Step-by-step reasoning
- Sodium nitrate (NaNO₃)
- Sodium is a highly reactive metal (Group 1). On heating, sodium nitrate decomposes to sodium nitrite and oxygen:
2NaNO3Δ2NaNO2+O2
- No nitrogen-containing gas is produced; the nitrogen remains in the nitrite ion. Thus, no dinitrogen is liberated.
- Ammonium dichromate ((NH₄)₂Cr₂O₇)
- This is a classic “volcano” reaction. The ammonium ion (oxidation state –3) is a strong reducing agent, and dichromate (Cr⁺⁶) is a strong oxidizer. Upon heating, they undergo an internal redox reaction:
(NH4)2Cr2O7ΔCr2O3+4H2O+N2
- The nitrogen in NH₄⁺ is oxidized from –3 to 0 (N₂), while chromium is reduced from +6 to +3. Dinitrogen gas is clearly liberated.
- Barium azide (Ba(N₃)₂) …
- Sodium nitrate (NaNO₃)
- TG EAPCET 2024Set ap-2024-05-07-AN1 markMCQQ.The number of products formed by thermal decomposition of lithium nitrate, sodium nitrate respectively are (A) 2,3 (B) 2,2 (C) 3,3 (D) 3,2
›Reveal solutionSolution
The thermal decomposition of lithium nitrate yields 3 products (Li₂O, NO₂, O₂), while sodium nitrate yields 2 products (NaNO₂, O₂). The correct option is (D).
The key to this question lies in understanding how the alkali metal nitrates behave differently on heating. Lithium, being the smallest alkali metal, has a significantly different chemistry from its heavier cousins — it behaves more like magnesium in many ways. Sodium, potassium, rubidium, and caesium follow a different decomposition pattern.
When you heat a nitrate, the central nitrogen atom is already in its +5 oxidation state. The question is: does the metal cation force the nitrate to break down all the way to the oxide, or can it stop at the nitrite stage? That depends on the polarising power of the cation.
Lithium ion is tiny and highly polarising — it pulls electron density so strongly that the nitrate ion cannot hold together. It decomposes completely, giving lithium oxide, nitrogen dioxide, and oxygen. Sodium ion is larger and less polarising; its nitrate merely loses one oxygen atom to form the nitrite, releasing only oxygen gas.
Let’s work through each case.
- Lithium nitrate decomposition Lithium nitrate (LiNO3) on strong heating gives:
2LiNO3ΔLi2O+2NO2+21O2
Count the products: lithium oxide (Li2O), nitrogen dioxide (NO2), and oxygen (O2) — that’s three distinct products.
Watch outA common mistake is to think lithium nitrate gives lithium nitrite like sodium does. It does not — lithium nitrite is unstable at the decomposition temperature and further breaks down. Always check the position of the metal in the periodic table.
- Sodium nitrate decomposition Sodium nitrate (NaNO3) on heating gives:
2NaNO3Δ2NaNO2+O2
The products are sodium nitrite (NaNO2) and oxygen (O2) — that’s two distinct products. …
- TG EAPCET 2022Set eng-2022-07-19-FN1 markMCQQ.A nitrogen oxide that forms "in situ" when dilute FeSO4 is treated with aqueous solution of nitrate ion and then careful addition of conc. H2SO4 along the sides of test tube, is (A) NO2 (B) NO (C) N2O (D) N2O3
›Reveal solutionSolution
The brown ring test for nitrate relies on the formation of the nitrosyl complex [Fe(HX2O)X5(NO)]X2+; the nitrogen oxide formed in situ is NO (nitric oxide), which coordinates to Fe(II) to give the characteristic brown ring. The correct option is (B).
The question describes the classic brown ring test for nitrate ions — a staple in qualitative inorganic analysis. When dilute ferrous sulphate is added to a solution containing nitrate, and then concentrated sulphuric acid is carefully poured down the side of the test tube, a brown ring appears at the junction of the two liquids. That ring is not a simple oxide of nitrogen floating around; it is a coordination complex. But the oxide that forms first, right there in the solution, is what we need to identify.
The key insight: the nitrate ion (NOX3X−) is a poor oxidising agent in dilute acid, but concentrated sulphuric acid provides a strongly acidic medium that reduces nitrate to nitric oxide (NO). The Fe(II) ions reduce the nitrate, and in the process get oxidised to Fe(III) — but the NO that is produced immediately binds to excess Fe(II) to form a stable, coloured complex.
Let’s walk through the chemistry step by step.
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The role of concentrated sulphuric acid.
Conc. HX2SOX4 is added carefully so it forms a separate layer below the aqueous mixture. It does two things: it provides a high concentration of HX+ ions, and it dehydrates the medium, making the reduction of nitrate possible. Without this strong acid, the reaction is too slow to be observed.
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Reduction of nitrate to nitric oxide.
In the strongly acidic environment, the nitrate ion is reduced by ferrous ions:
NOX3X−+3FeX2++4HX+NO+3FeX3++2HX2O
The product is nitric oxide (NO), a neutral gas. This is the oxide that forms "in situ" — right there in the test tube, not added from outside.
- Formation of the brown ring complex. The freshly formed NO is not free for long. It coordinates with excess FeX2+ ions (which are present in the dilute FeSO4 solution) to form the brown-coloured nitrosyl complex: [Fe(HX2O)X6]X2++NO[Fe(HX2O)X5(NO)]X2++HX2O …
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- TG EAPCET 2021Set ap-2021-08-09-AN1 markMCQQ.The mixture of three parts of concentrated HCl and one part of concentrated HNO3 is reacted with gold metal. The main products of reaction are (A) AuCl4−+NO2 (B) AuCl4−+NO (C) AuCl3O+NO (D) AuClO+NO2
›Reveal solutionSolution
Aqua regia (3:1 HCl:HNO₃) dissolves gold by forming the stable tetrachloroaurate(III) complex, AuCl4−, while nitric acid is reduced to nitrosyl chloride or nitrogen monoxide; the main products are AuCl4− and NO.
Concept & Intuition
Gold is a “noble” metal — it resists oxidation by either HCl or HNO₃ alone. But when you mix them in a 3:1 ratio (aqua regia), you get a powerful one-two punch:
- HNO₃ oxidizes gold to Au³⁺.
- HCl provides Cl⁻ ions that immediately complex with Au³⁺ to form the very stable AuCl4− ion, pulling the equilibrium forward. Meanwhile, the HNO₃ is reduced. In concentrated acid, the typical reduction product is NO (not NO₂, which forms in dilute conditions). The reaction also produces water and sometimes traces of nitrosyl chloride (NOCl), but the net ionic equation gives NO as the main gaseous product.
Let’s walk through the reasoning step by step.
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Identify the oxidizing and complexing agents
- HNO₃ is the oxidizer: it takes electrons from Au.
- HCl supplies Cl⁻, which binds Au³⁺ tightly as AuCl4− (stability constant ~10²⁵). This lowers the effective concentration of Au³⁺, making the oxidation thermodynamically favorable.
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Write the half-reactions
- Oxidation: Au(s)→Au3++3e−
- Reduction of nitrate in concentrated acid: NO3−+4H++3e−→NO+2H2O (This is the standard reduction in strong acid; NO₂ forms only when HNO₃ is dilute or heated.)
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Combine and add chloride
- Balance electrons: multiply the gold oxidation by 1 and the nitrate reduction by 1 (both involve 3 electrons).
- Net ionic (before complexation): Au+NO3−+4H+→Au3++NO+2H2O
- Now add Cl⁻: Au³⁺ immediately forms AuCl4−: Au3++4Cl−→AuCl4−
- Overall: Au+NO3−+4H++4Cl−→AuCl4−+NO+2H2O
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Check the options …
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