Q.Match the items given in Column I with the type of solutions given in Column II.
Column I:
Column II:
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Types Of Solutions
Types of Solutions: From Everyday Life to Chemistry
You already know what a solution is — sugar dissolved in water, salt in water, even the air you breathe. But not all solutions behave the same way. Some dissolve easily, some refuse to dissolve beyond a point, and some can hold more solute than they normally should. That difference is what we classify as types of solutions based on how much solute is dissolved.
The Intuition: A Cup of Tea
Imagine making a cup of tea. You add one spoon of sugar — it dissolves completely. You add a second spoon — still dissolves. A third spoon — maybe it dissolves, maybe it doesn't. At some point, no matter how much you stir, the sugar just sits at the bottom.
That moment — when no more sugar dissolves — is the saturation point. Before that, you have an unsaturated solution. At that exact point, you have a saturated solution. And if you carefully heat the tea, dissolve more sugar, then cool it down without disturbing it — you might get a supersaturated solution, where more sugar stays dissolved than should be possible at that temperature.
That's the entire idea. Three types, defined by how much solute is dissolved relative to the maximum possible.
The Precise Statement
A solution is a homogeneous mixture of a solute (the substance being dissolved) and a solvent (the substance doing the dissolving). Based on the amount of solute dissolved relative to its solubility at a given temperature, solutions are classified into three types:
Types of Solutions (by saturation)
- Unsaturated solution — contains less solute than the maximum that can be dissolved at that temperature.
- Saturated solution — contains exactly the maximum amount of solute that can be dissolved at that temperature.
- Supersaturated solution — contains more solute than the maximum normally possible at that temperature (a metastable state).
Breaking Down Each Type
Unsaturated solution — the most common type. You can still add more solute and it will dissolve. The concentration is below the solubility limit. If you have a glass of water at room temperature and add a pinch of salt, you get an unsaturated solution. Add more salt — still unsaturated, until you hit the limit.
Saturated solution — the solute and undissolved solute are in dynamic equilibrium. At the molecular level, the rate at which solute particles dissolve equals the rate at which they crystallize out. No net change. If you keep adding salt to water and it stops dissolving, the liquid above the undissolved salt is a saturated solution. The concentration is fixed at the solubility value for that temperature.
A common mistake: thinking a saturated solution is always "thick" or "concentrated." Not true. Saturation depends on the solute's solubility. Lead(II) chloride saturates at about 0.45 g per 100 mL water — that's a very dilute saturated solution. Saturation ≠ high concentration.
Supersaturated solution — this is a tricky one. You create it by heating the solvent, dissolving more solute than normally possible, then carefully cooling it. The excess solute stays dissolved because there's no nucleation site (no scratch, no dust particle) to trigger crystallization. It's unstable — the slightest disturbance (a dust speck, a scratch on the glass, even a sudden jolt) causes the excess solute to crystallize out instantly. …
Why this formula?
Types of Solutions: Why the Key Formulae Hold
Understanding why the formulae work is essential for Indian exams (JEE, NEET, CBSE). Let's break down the reasoning behind the most important relationships.
1. The Basic Classification: What Makes a Solution?
A solution is a homogeneous mixture of two or more substances. The key idea is intermolecular forces between solute and solvent particles.
- Ideal Solution: Solute-solvent interactions are identical to solute-solute and solvent-solvent interactions. Why? No net energy change on mixing — the molecules "fit" perfectly.
- Non-Ideal Solution: Interactions differ, leading to deviation from Raoult's law.
2. Raoult's Law: The Foundation
Formula:
Psolution=xsolvent⋅Psolvent0
Why does this hold?
Imagine a pure solvent surface. The vapour pressure P0 comes from molecules escaping the liquid. When you add a non-volatile solute, solute molecules occupy some surface area, blocking solvent molecules from escaping.
- The fraction of surface available to solvent = mole fraction of solvent (xsolvent).
- Therefore, the rate of escape (vapour pressure) is proportional to that fraction:
Psolution∝xsolvent
- At the limit xsolvent=1, Psolution=P0, so the constant is P0.
Key insight: Raoult's law is a surface-area argument, not a volume argument.
3. Relative Lowering of Vapour Pressure
Formula:
P0P0−P=xsolute
Derivation in one line:
From Raoult's law:
P=xsolvent⋅P0
Since xsolvent+xsolute=1,
P=(1−xsolute)P0
⇒P0−P=xsolute⋅P0
⇒P0P0−P=xsolute
Why is this useful?
It depends only on the mole fraction of solute, not on its identity — making it a colligative property.
4. Elevation of Boiling Point
Formula:
ΔTb=Kb⋅m
Why does boiling point rise?
- Boiling occurs when vapour pressure = atmospheric pressure.
- Adding a non-volatile solute lowers vapour pressure (Raoult's law).
- To reach atmospheric pressure again, you must raise the temperature.
- The shift ΔTb is proportional to the molality m (moles of solute per kg of solvent), because:
- More solute → greater vapour pressure lowering → more temperature needed.
- Kb (ebullioscopic constant) is a property of the solvent only.
5. Depression of Freezing Point
Formula:
ΔTf=Kf⋅m
Why does freezing point drop?
- At the freezing point, solid and liquid solvent are in equilibrium.
- Adding solute disrupts this equilibrium — solute molecules interfere with the orderly crystal formation of the solvent.
- To re-establish equilibrium, you must lower the temperature.
- Again, ΔTf∝m, and Kf depends only on the solvent.
Common exam trap: Both ΔTb and ΔTf are colligative — they depend on number of solute particles, not their nature.
6. Osmotic Pressure
Formula:
Π=i⋅C⋅R⋅T
Why does this hold?
- Osmosis is the net movement of solvent from low solute concentration to high solute concentration across a semipermeable membrane.
- The solvent moves to dilute the higher concentration — this is a entropy-driven process (mixing increases disorder). …
Concept: Types Of Solutions — based on the physical state of solute and solvent.
Reasoning:
- Soda water: carbon dioxide gas dissolved in water → gas in liquid → (e).
- Sugar solution: solid sugar dissolved in water → solid in liquid → (c).
- German silver: an alloy of copper, zinc, and nickel → solid in solid → (d).
- Air: a mixture of gases (oxygen, nitrogen, etc.) → gas in gas → (b). …
The key idea is to classify each mixture by the physical state of its solute and solvent. The correct matches are: (i)→(e), (ii)→(c), (iii)→(d), (iv)→(b), (v)→(a).
Concept and Intuition
A solution is a homogeneous mixture of two or more substances. The substance present in the larger amount is called the solvent, and the substance present in the smaller amount is called the solute. The type of solution is described by the phrase "a solution of [solute state] in [solvent state]".
To classify correctly, you must identify which component is the solute (the one being dissolved) and which is the solvent (the one doing the dissolving). The physical state of each at room temperature (or the given conditions) determines the classification.
A common mistake is to reverse the solute and solvent. For example, in "soda water", water is the solvent (liquid) and carbon dioxide is the solute (gas). The correct classification is "a solution of gas in liquid", not "a solution of liquid in gas".
Step-by-Step Matching
1. (i) Soda water
Soda water is carbon dioxide gas dissolved in water. The solvent is water (liquid), and the solute is carbon dioxide (gas).
→ This is a solution of gas in liquid.
Match: (i) → (e)
2. (ii) Sugar solution
Sugar solution is sugar (solid) dissolved in water (liquid). The solvent is water (liquid), and the solute is sugar (solid).
→ This is a solution of solid in liquid.
Match: (ii) → (c)
3. (iii) German silver
German silver is an alloy of copper, zinc, and nickel. Alloys are solid solutions where one metal is dissolved in another. Here, all components are solids.
→ This is a solution of solid in solid.
Match: (iii) → (d)
4. (iv) Air …
Method: Solute–Solvent Classification Based on Physical States
This method uses the physical states (solid, liquid, gas) of the solute and solvent to classify each solution.
Steps
-
Identify the solute and solvent in each mixture.
- The solvent is the component present in larger amount (or the one that dissolves the other).
- The solute is the component present in smaller amount (the one that gets dissolved).
-
Determine the physical state (solid, liquid, or gas) of both solute and solvent at room temperature.
-
Match the pair to the correct type from Column II using the pattern:
- Solution of gas in liquid → gas solute, liquid solvent
- Solution of gas in solid → gas solute, solid solvent
- Solution of solid in liquid → solid solute, liquid solvent
- Solution of solid in solid → solid solute, solid solvent
- Solution of gas in gas → gas solute, gas solvent
- Solution of liquid in solid → liquid solute, solid solvent
Applying the Steps
| Column I Item | Solute | Solvent | Type (Column II) |
|---------------|--------|---------|------------------| …
Here’s a breakdown of the common mistakes students make when matching types of solutions, along with how to avoid each.
Mistake 1: Confusing the solute and solvent in alloys (German silver)
What students do wrong:
Students often think German silver is a solution of solid in liquid (because it’s a metal alloy) or misidentify it as a solution of liquid in solid.
Why it happens:
They forget that an alloy is a solid-solid solution — both components are solids at room temperature.
How to avoid:
- Remember: Alloys = solid in solid.
- German silver is an alloy of copper, zinc, and nickel — all solids.
- So the correct match is (iii) → (d).
Mistake 2: Thinking “soda water” is a solution of liquid in liquid
What students do wrong:
They see “water” and assume it’s a liquid-liquid solution, ignoring the dissolved gas.
Why it happens:
They focus on the solvent (water) and forget the solute (carbon dioxide gas).
How to avoid:
- Identify the solute first: In soda water, CO₂ gas is dissolved in water.
- So it’s gas in liquid → match (i) → (e).
- Tip: If a drink fizzes, it contains dissolved gas.
Mistake 3: Misclassifying “air” as a solution of gas in liquid or solid
What students do wrong:
They sometimes match air with “gas in solid” or “gas in liquid” because they think of dust or moisture.
Why it happens:
They overcomplicate — air is primarily a mixture of gases (N₂, O₂, etc.) with no liquid or solid phase dominating.
How to avoid:
- Air is a homogeneous mixture of gases → gas in gas.
- Match (iv) → (b).
- Ignore trace impurities unless the question specifies them.
Mistake 4: Confusing “hydrogen gas in palladium” with a gas-gas solution
What students do wrong:
They see “hydrogen gas” and “palladium” and think both are gases, or they match it with “gas in liquid”.
Why it happens:
They don’t know that palladium is a solid metal that can absorb hydrogen gas.
How to avoid:
- Learn this classic example: Hydrogen in palladium is a gas in solid solution.
- Match (v) → (a).
- Remember: Palladium is a solid, so the solute (H₂ gas) is trapped in the solid lattice.
Mistake 5: Matching “sugar solution” with gas in liquid or solid in solid
What students do wrong: …
- COMEDK 2026Set 2026-A1 markMCQQ.The system that forms maximum boiling azeotrope is: (A) Benzene-toluene (B) Carbon-di-sulphide-acetone (C) Ethyl alcohol-water (D) Acetone-chloroform
›Reveal solutionSolution
A maximum‑boiling azeotrope forms when the solution’s vapour pressure is lower than Raoult’s law predicts (negative deviation), so the boiling point is higher than either pure component. Among the given pairs, only acetone‑chloroform shows strong negative deviation due to hydrogen bonding, making (D) the correct answer.
Concept and Intuition
An azeotrope is a mixture that boils at a constant composition because the vapour has the same composition as the liquid. For a maximum‑boiling azeotrope, the boiling point of the mixture is higher than that of either pure component. This happens when the intermolecular attractions between the two different molecules are stronger than those in the pure liquids — a situation called negative deviation from Raoult’s law. The stronger cross‑attractions make it harder for molecules to escape into the vapour, lowering the vapour pressure and raising the boiling point.
The key is to identify which pair forms such strong cross‑interactions. Let’s examine each option.
Step‑by‑Step Reasoning
-
Option (A): Benzene‑toluene
Benzene and toluene are both non‑polar hydrocarbons with similar structures. Their intermolecular forces (dispersion forces) are nearly identical, so the mixture behaves almost ideally — no significant deviation from Raoult’s law. No azeotrope forms; the boiling point lies between those of the pure components.
→ Not a maximum‑boiling azeotrope.
-
Option (B): Carbon disulphide‑acetone
Carbon disulphide (CS2) is non‑polar, while acetone (CH3COCH3) is polar. Mixing them disrupts the dipole‑dipole interactions in acetone, making it easier for molecules to escape. This gives a positive deviation from Raoult’s law (higher vapour pressure, lower boiling point). Such systems form minimum‑boiling azeotropes, not maximum‑boiling ones.
→ Incorrect.
-
Option (C): Ethyl alcohol‑water
Ethanol and water both form strong hydrogen bonds. However, when mixed, the hydrogen‑bond network in each pure liquid is partially broken, and the cross‑hydrogen bonds (ethanol‑water) are weaker than the sum of the pure‑liquid interactions. This leads to a positive deviation (higher vapour pressure, lower boiling point). Ethanol‑water indeed forms a minimum‑boiling azeotrope (boiling point ~78.2 °C, lower than both pure ethanol and water).
→ Incorrect.
-
Option (D): Acetone‑chloroform
Acetone (CH3COCH3) has a carbonyl oxygen with lone pairs; chloroform (CHCl3) has a hydrogen attached to three electronegative chlorines. The hydrogen in chloroform is sufficiently acidic to form a hydrogen bond with the oxygen of acetone:
CHCl3⋯O=C(CH3)2 …
-
- COMEDK 2026Set 2026-A1 markMCQQ.When 1 mole of benzene is mixed with 1 mole of toluene, the vapours will contain (A) Higher percentage of benzene (B) Equal mass of benzene and toluene since it is an ideal solution (C) Higher percentage of toluene (D) Equal number of moles of benzene and toluene since it is an ideal solution
›Reveal solutionSolution
In an ideal solution of benzene and toluene, the more volatile component (benzene) enriches the vapour phase, so the vapour contains a higher percentage of benzene. The correct option is (A).
Concept & Intuition
Benzene and toluene form an ideal solution (Raoult’s law holds). At a given temperature, benzene has a higher vapour pressure than toluene — it is more volatile. When a liquid mixture evaporates, the vapour is richer in the more volatile component. This is the key idea behind distillation: the vapour composition differs from the liquid composition. Here, with equal moles in the liquid, the vapour will not be 50:50; it will be skewed toward benzene.
Step-by-step reasoning
-
Identify the vapour pressures
At 25 °C, pure benzene has vapour pressure PB0≈95.1 mm Hg, and pure toluene has PT0≈28.4 mm Hg. (Exact values depend on temperature, but the key is PB0>PT0.)
-
Apply Raoult’s law for the liquid mixture
For 1 mole each, mole fractions in the liquid are xB=0.5 and xT=0.5.
Partial pressures above the liquid:
PB=xBPB0=0.5×95.1=47.55 mm Hg
PT=xTPT0=0.5×28.4=14.2 mm Hg
- Find the vapour composition The total pressure Ptotal=PB+PT=61.75 mm Hg. Mole fraction of benzene in the vapour (yB) is given by Dalton’s law:
yB=PtotalPB=61.7547.55≈0.77
So the vapour is about 77 % benzene and 23 % toluene. …
-
- COMEDK 2025Set 2025-E1 markMCQQ.At 300 K the vapour pressure of an ideal solution containing 1.0 mole each of volatile liquids X and Y is 1000 mm . Keeping the temperature constant, when 2.0 moles of liquid X is added to the solution, its vapour pressure increases by 200 mm . Calculate the vapour pressure of X and Y in their pure state (A) PX0=1400PY0=600 (B) PX0=1700PY0=400 (C) PX0=1200PY0=480 (D) PX0=1000PY0=500
›Reveal solutionSolution
Using Raoult’s law for an ideal solution, we set up two equations from the two given conditions (initial and after adding more X) and solve for the pure vapour pressures. The result is PX0=1200 mm and PY0=600 mm, which corresponds to option (A).
Concept & Intuition
Raoult’s law states that for an ideal solution, the partial vapour pressure of each component equals its mole fraction times its pure vapour pressure. The total vapour pressure is the sum of these partial pressures. Here we have two different compositions (before and after adding extra X), each giving a total pressure. That gives two linear equations in the two unknowns PX0 and PY0. Solving them is straightforward — no tricks, just careful algebra.
Step-by-step solution
- Initial condition Moles of X = 1, moles of Y = 1 → total moles = 2. Mole fractions:
xX=21,xY=21
Total vapour pressure Ptotal=1000 mm.
By Raoult’s law:
Ptotal=xXPX0+xYPY0=21PX0+21PY0
Multiply by 2:
PX0+PY0=2000(Equation 1)
- After adding 2.0 moles of X New moles: X = 1 + 2 = 3, Y = 1 (unchanged) → total moles = 4. New mole fractions:
xX′=43,xY′=41
Vapour pressure increases by 200 mm, so new total pressure = 1000+200=1200 mm.
Raoult’s law gives:
1200=43PX0+41PY0
Multiply by 4:
4800=3PX0+PY0(Equation 2) …
- COMEDK 2025Set 2025-M1 markMCQQ.Two volatile liquids X and Y form an ideal solution at 298 K and have vapour pressures equal to 100 mm and 200 mm of Hg respectively in their pure state. The mole fraction of X in the solution is 0.4 and the mole fraction of Y in the vapour phase is a/20. Calculate the value of a. (A) 25 (B) 15 (C) 10 (D) 5
›Reveal solutionSolution
Using Raoult’s law for an ideal solution and Dalton’s law for the vapour phase, the mole fraction of Y in the vapour is found to be 0.75, which equals a/20; solving gives a=15.
Concept & Intuition
For an ideal solution of two volatile liquids, the vapour above the solution is not simply the same composition as the liquid. Instead, the more volatile component (higher pure vapour pressure) enriches the vapour. Raoult’s law gives the partial pressure of each component in the vapour:
PX=xXPX∘,PY=xYPY∘
where x is the mole fraction in the liquid and P∘ is the pure vapour pressure. Dalton’s law then tells us the total pressure is the sum of partial pressures, and the mole fraction of a component in the vapour is its partial pressure divided by the total pressure. So we can compute the vapour composition directly from the liquid composition and pure vapour pressures.
Step-by-step solution
-
Identify given data
- Pure vapour pressures: PX∘=100 mm Hg, PY∘=200 mm Hg
- Mole fraction of X in the liquid: xX=0.4
- Since it’s a binary solution, xY=1−xX=0.6
- Mole fraction of Y in the vapour is given as 20a.
-
Apply Raoult’s law to find partial pressures
PX=xXPX∘=0.4×100=40 mm Hg
PY=xYPY∘=0.6×200=120 mm Hg
- Find total vapour pressure
Ptotal=PX+PY=40+120=160 mm Hg
- Compute mole fraction of Y in the vapour …
-
- COMEDK 2025Set 2025-M1 markMCQQ.A non-volatile solute A weighing 60 g when dissolved in 212 g of the solvent Xylene reduces its vapour pressure to 60%. What is the Molar mass of A in g/mol ? [MM of xylene =106 g/mol ] (A) 56 (B) 126 (C) 60 (D) 45
›Reveal solutionSolution
The key idea is that the relative lowering of vapour pressure equals the mole fraction of the solute. Using the given 60% reduction, we set up the mole fraction equation and solve for the molar mass of A, obtaining 60 g/mol.
Concept & Intuition
When a non-volatile solute is dissolved in a solvent, the vapour pressure of the solution is lower than that of the pure solvent. Raoult’s law tells us that the relative lowering of vapour pressure is exactly equal to the mole fraction of the solute. Here, the vapour pressure is reduced to 60% of its original value — meaning the lowering is 40% of the original. That fraction directly gives the mole fraction of solute, and from there we can find its molar mass.
Step-by-step solution
- Interpret the vapour pressure reduction Let P0 be the vapour pressure of pure xylene. The problem says the vapour pressure is reduced to 60% of P0. So the new vapour pressure P=0.60P0. The lowering of vapour pressure is:
ΔP=P0−P=P0−0.60P0=0.40P0
Hence the relative lowering is:
P0ΔP=0.40
- Apply Raoult’s law for a non-volatile solute For a dilute solution of a non-volatile solute, Raoult’s law states:
P0ΔP=xsolute
where xsolute is the mole fraction of the solute. Therefore:
xsolute=0.40
-
Express mole fraction in terms of masses and molar masses
Let MA be the molar mass of solute A (in g/mol).
Mass of solute = 60 g → moles of solute = MA60.
Mass of solvent (xylene) = 212 g, molar mass of xylene = 106 g/mol → moles of solvent = 106212=2.00 mol.
The mole fraction of solute is:
xsolute=moles of solute+moles of solventmoles of solute=MA60+2.0060/MA
- Set up the equation and solve …
- COMEDK 2024Set 2024-A1 markMCQQ.The system that forms minimum boiling azeotrope is : (A) Phenol-Aniline (B) Ethyl alcohol - Water (C) Acetone-Chloroform (D) Nitric Acid - Water
›Reveal solutionSolution
A minimum-boiling azeotrope arises from a positive deviation from Raoult's law. Ethanol–water is the textbook example; phenol–aniline, acetone–chloroform and nitric acid–water all show negative deviations and form maximum-boiling azeotropes.
Minimum-boiling azeotropes form in solutions showing positive deviation (weaker A–B interactions than A–A/B–B, higher vapour pressure, lower boiling point).
- (A) Phenol–aniline: strong O–H···N hydrogen bonding between components → negative deviation → maximum-boiling. …
- COMEDK 2023Set 2023-M1 markMCQQ.Which of the following shows negative deviation from Raoult's law? (A) Benzene-acetone (B) Benzene-chloroform (C) Benzene-ethanol (D) Benzene-carbon tetrachloride
›Reveal solutionSolution
Negative deviation occurs when the new A–B interactions are stronger than the average of A–A and B–B interactions. Among the pairs listed, benzene–chloroform develops extra attraction (weak C–H···π interaction), lowering vapour pressure — a negative deviation.
Negative deviation from Raoult's law ⇒ observed vapour pressure lower than ideal, arising when solute–solvent attractions exceed solvent–solvent and solute–solute attractions.
Evaluating the mixtures:
- Benzene–acetone: breaks acetone's dipole interactions; weaker new forces ⇒ positive deviation. …
- COMEDK 2022Set 20221 markMCQQ.Which among the following forms minimum boiling azeotropes?(i) Heptane + Octane(ii) Water + Nitric acid(iii) Ethanol + Water(iv) Acetone + Carbon dioxide (A) (i), (ii),(iv) (B) (i),(ii) only (C) (i), (iii),(iv) (D)(iv) only
›Reveal solutionSolution
So the genuine minimum-boiling pairs are (iii) and (iv). Option (ii) is definitely excluded (it is maximum boiling), which rules out options (A) and (B). Option (D) omits ethanol + water, the canonical minimum-boiling azeotrope. The only option containing both (iii) and (iv) is (C).
Concept: Azeotropes. A minimum-boiling azeotrope is formed by solutions showing a LARGE POSITIVE deviation from Raoult's law; a maximum-boiling azeotrope by solutions showing a large negative deviation.
- Heptane + octane: chemically very similar, near-ideal solution - strictly no azeotrope at all.
- Water + nitric acid: strong H-bonding/interaction -> negative deviation -> MAXIMUM boiling azeotrope (not minimum).
- Ethanol + water: the textbook example of a positive deviation -> MINIMUM boiling azeotrope (95% ethanol, 351.1 K). YES. …
- COMEDK 2021Set 20211 markMCQQ.Which of the following is correct mixture of azeotrope? (A) Chlorobenzene + bromobenzene (B) C2H5Br + C2H5Cl (C) C6H14 + C7H16 (D) CCl4 + CHCl3
›Reveal solutionSolution
- Chlorobenzene + bromobenzene: nearly ideal (very similar structures) - no azeotrope - C2H5Br + C2H5Cl: nearly ideal - no azeotrope - n-hexane + n-heptane: classic ideal solution - no azeotrope - CCl4 + CHCl3: shows a measurable (positive) deviation from Raoult's law because CHCl3-CHCl3 / CCl4-CCl4 interactions differ from the mixed ones; this pair is the non-ideal one and forms an azeotropic mixture.
Concept: Azeotropes form only from NON-IDEAL solutions (those showing appreciable positive or negative deviation from Raoult's law). Ideal solutions never form azeotropes.
- Chlorobenzene + bromobenzene: nearly ideal (very similar structures) - no azeotrope
- C2H5Br + C2H5Cl: nearly ideal - no azeotrope …
- KCET 2019Set A-11 markMCQQ.Solution 'A' contains acetone dissolved in chloroform and solution 'B' contains acetone dissolved in carbon disulphide. The type of deviations from Raoult's law shown by solutions A and B, respectively are (A) positive and positive (B) negative and negative (C) positive and negative (D) negative and positive
›Reveal solutionSolution
Compare the A–B interaction with the A–A and B–B interactions: stronger A–B ⇒ negative deviation (acetone/chloroform), weaker A–B ⇒ positive deviation (acetone/CS2).
Step 1 — The rule behind Raoult's-law deviations.
For a solution of A and B, let A−B be the new solute–solvent interaction and A−A, B−B the interactions in the pure liquids.
Comparison Escaping tendency Vapour pressure Deviation ΔmixH, ΔmixV A−B stronger decreases p<pRaoult Negative <0 (exothermic), <0 A−B weaker increases p>pRaoult Positive >0 (endothermic), >0 Step 2 — Solution A: acetone + chloroform.
Chloroform's C–H bond is strongly polarised by its three electronegative chlorine atoms, so its hydrogen is acidic enough to form a genuine hydrogen bond with the lone pair on the carbonyl oxygen of acetone:
ClX3C−H ⋯O=C(CHX3)X2
This A−B attraction is stronger than the dipole–dipole forces present in either pure liquid. The molecules are therefore held back from the vapour phase, the total vapour pressure falls below the Raoult prediction ⇒ negative deviation (this pair also forms a maximum-boiling azeotrope).
Step 3 — Solution B: acetone + carbon disulphide. …
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