Q.Given that ΔH = 0 for mixing of two gases. Explain whether the diffusion of these gases into each other in a closed container is a spontaneous process or not?
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Entropy Change Prediction
Entropy Change Prediction
Imagine you have a box of marbles — all neatly arranged, reds on one side, blues on the other. Now shake the box. What happens? The colours mix. They never spontaneously unmix. That tendency — for things to go from ordered to disordered — is what entropy measures. Entropy is a measure of disorder or randomness in a system.
When you predict an entropy change, you're asking: Will this process make the system more disordered or less disordered? And by how much?
The Core Intuition
Entropy change (ΔS) is positive when disorder increases, negative when disorder decreases. Three things drive this:
- Volume change — More space means more positions for particles → more disorder. A gas expanding into vacuum has ΔS>0.
- Temperature change — Higher temperature means particles move faster, explore more states → more disorder. Heating something increases entropy.
- Phase change — Solid → liquid → gas is a ladder of increasing disorder. Melting ice increases entropy; freezing water decreases it.
Entropy always increases for spontaneous processes in an isolated system (Second Law of Thermodynamics). But for a non-isolated system, entropy can decrease locally — as long as the surroundings' entropy increases enough to compensate.
The Precise Statement
For a reversible process at constant temperature, the entropy change is:
ΔS=TQrev
where Qrev is the heat transferred reversibly, and T is the absolute temperature (in Kelvin).
For an irreversible process (which is what actually happens), you calculate ΔS by imagining a reversible path between the same initial and final states — because entropy is a state function. It depends only on where you start and end, not how you get there.
ΔS=∫TdQrev
For common cases, you use these:
| Process | Formula | Sign intuition |
|---|---|---|
| Isothermal expansion/compression (ideal gas) | ΔS=nRlnV1V2 | Expanding → more volume → ΔS>0 |
| Heating/cooling (constant pressure) | ΔS=nCplnT1T2 | Heating → higher T → ΔS>0 |
| Phase change (melting, boiling) | ΔS=TphaseΔHphase | Melting/boiling → more disorder → ΔS>0 |
How to Predict Without Calculation
You don't always need numbers. Ask these questions in order:
- Is there a phase change? Solid → liquid or liquid → gas always increases entropy. Reverse decreases it.
- Is the number of gas molecules changing? In a reaction, more gas molecules means more disorder. 2H2+O2→2H2O (gas → liquid) has ΔS<0 because 3 gas molecules become 2 liquid molecules.
- Is temperature increasing or decreasing? Higher temperature → higher entropy.
- Is volume increasing? More space → more entropy. …
Concept: Gibbs free energy change (ΔG) determines spontaneity at constant temperature and pressure. For any process, ΔG=ΔH−TΔS.
Reasoning:
- For mixing of two ideal gases, ΔH=0 (no heat exchange, as intermolecular forces are negligible).
- Mixing increases disorder — the gases spread to occupy the full volume, so entropy increases: ΔS>0. …
For an ideal gas mixture, ΔH=0 but the process is spontaneous because the entropy increases (ΔS>0), making ΔG=−TΔS<0 — the second law of thermodynamics drives mixing even without any heat change.
The key insight here is that spontaneity is not decided by enthalpy change alone. Many students instinctively think "no heat change means no driving force" — but that's a trap. The real master of spontaneity is Gibbs free energy: ΔG=ΔH−TΔS. When ΔH=0, the sign of ΔG depends entirely on entropy.
For two gases diffusing into each other, the process is fundamentally about disorder. Before mixing, each gas is confined to its own volume — the molecules of gas A are segregated from those of gas B. After mixing, both gases occupy the entire container, intermingling freely. This is a classic example of increased randomness.
- Entropy change is the driver. For an ideal gas mixture at constant temperature and pressure, the entropy of mixing is always positive. The formula for two gases is:
ΔSmix=−nR(xAlnxA+xBlnxB)
where xA and xB are mole fractions. Since xA and xB are less than 1, their logarithms are negative, making the sum inside negative — and the negative sign outside gives a positive ΔS.
- Apply the Gibbs free energy criterion. With ΔH=0:
ΔG=ΔH−TΔS=0−TΔS=−TΔS
Since ΔS>0, we get ΔG<0. A negative ΔG is the thermodynamic condition for a spontaneous process at constant temperature and pressure.
- Physical intuition. Imagine a box divided by a removable partition, with nitrogen on one side and oxygen on the other. When you remove the partition, the gases spontaneously mix — you don't need to push them. This happens because the mixed state has more possible arrangements of molecules (microstates) than the separated state. Nature always moves toward higher probability, which is higher entropy. …
- KCET 2025Set D-41 markMCQQ.Match List-I with List-II and select the correct option:(A) a-iii, b-iv, c-i, d-ii (B) a-i, b-iv, c-iii, d-ii (C) a-ii, b-iii, c-iv, d-i (D) a-iv, b-iii, c-ii, d-i
List-I (Molecule / ion) List-II (Bond order) a. NO i. 1.5 b. CO ii. 2.0 c. O2− iii. 2.5 d. O2 iv. 3.0 ›Reveal solutionSolution
Count valence electrons, fill the molecular orbitals, and apply B.O.=21(Nb−Na) to each species.
Step 1 — The tool: molecular orbital bond order
Bond order=21(Nb−Na)
where Nb = electrons in bonding MOs and Na = electrons in antibonding MOs. For these second-row diatomics the filling order (for ≥14 electrons, i.e. O2 and beyond) is
σ1s, σ∗1s, σ2s, σ∗2s, σ2pz, (π2px=π2py), (π∗2px=π∗2py), σ∗2pz
Step 2 — Work out each species
(1) NO — total electrons =7+8=15
Up to N2-like filling we get Nb=10, Na=5 (one lone electron sits in a π∗ orbital — which is why NO is paramagnetic and readily loses that antibonding electron to form NO+):
B.O.=21(10−5)=2.5→(iii)
(2) CO — total electrons =6+8=14 (isoelectronic with N2)
Nb=10,Na=4
B.O.=21(10−4)=3.0→(iv)
A triple bond — consistent with CO's very high bond dissociation enthalpy.
(3) O2− (superoxide) — total electrons =16+1=17
The extra electron goes into an antibonding π∗ orbital, so Nb=10, Na=7:
B.O.=21(10−7)=1.5→(i) …
- KCET 2025Set D-41 markMCQQ.The equilibrium constant at 298K for the reaction A+BC+D is 100. If the initial concentrations of all the four species were 1M each, then equilibrium concentration of D (in mol L−1) will be (A) 0.182 (B) 1.818 (C) 1.182 (D) 0.818
›Reveal solutionSolution
Set up an ICE table with an unknown shift x, take the square root of K=100 to get a linear equation, solve x=9/11=0.818, and add it to D's initial 1 M.
Step 1 — Decide the direction of the shift.
Initially all four species are 1M, so
Q=[A][B][C][D]=1×11×1=1
Since Q=1<K=100, the reaction proceeds forward (left → right) to reach equilibrium.
Step 2 — ICE table. Let x mol L−1 of A react.
A B C D Initial 1 1 1 1 Change −x −x +x +x Equilibrium 1−x 1−x 1+x 1+x Step 3 — Apply the equilibrium constant.
K=[A][B][C][D]=(1−x)2(1+x)2=100
Step 4 — Take the (positive) square root.
1−x1+x=10
1+x=10−10x⇒11x=9⇒x=119=0.818 …
- KCET 2025Set D-41 markMCQQ.The correct statement/s about Galvanic cell is/are(a) Current flows from cathode to anode(b) Anode is positive terminal(c) If Ecell<0, then it is spontaneous reaction(d) Cathode is positive terminal (A) a and b only (B) a, b and c (C) a and d only (D) b only
›Reveal solutionSolution
Check each statement against two facts: in a galvanic cell the anode is negative and the cathode positive, and spontaneity requires Ecell>0 (since ΔG=−nFEcell).
Step 1 — Establish the ground rules for a galvanic cell.
A galvanic (voltaic) cell converts the energy of a spontaneous redox reaction into electrical energy.
- At the anode, oxidation occurs: M→Mn++ne−. Electrons are produced here and pile up, so the anode becomes the NEGATIVE terminal.
- At the cathode, reduction occurs: Mn++ne−→M. Electrons are consumed here, so the cathode is electron-deficient — the POSITIVE terminal.
- Electrons therefore flow through the external wire from anode → cathode.
- Conventional current is defined opposite to electron flow, so in the external circuit it flows cathode → anode.
(Note the contrast with an electrolytic cell, where an external supply forces the reaction and the anode is positive — this sign flip is the classic trap in this question.)
Step 2 — Evaluate each statement.
- Current flows from cathode to anode. ✓ CORRECT. Electrons go anode → cathode externally; conventional current, being opposite, goes cathode → anode in the external circuit. This is precisely what makes the cathode the + terminal that current "comes out of".
- Anode is positive terminal. ✗ WRONG. In a galvanic cell the anode is the site of oxidation, accumulates electrons and is the negative terminal. (Only in an electrolytic cell is the anode positive.)
(c) If Ecell<0, then it is spontaneous reaction. ✗ WRONG. Gibbs energy and cell potential are linked by
A reaction is spontaneous only when ΔG<0, which requires …
ΔG=−nFEcell
- KCET 2023Set D-21 markMCQQ.For a reaction, the value of rate constant at 300 K is 6.0×105 s−1. The value of Arrhenius factor A at infinitely high temperature is: (A) 6×105×e−Ea/300R (B) e−Ea/300R (C) 3006×105 (D) 6×105
›Reveal solutionSolution
As T→∞ the Arrhenius exponential tends to 1, so the rate constant tends to the pre-exponential factor A itself — no exponential term can survive in the answer.
1. The Arrhenius equation
k=Ae−Ea/RT
Here A is the Arrhenius (frequency / pre-exponential) factor — physically, the collision frequency with correct orientation — and e−Ea/RT is the fraction of collisions that carry at least the activation energy.
2. The infinite-temperature limit
limT→∞RTEa=0⟹limT→∞e−Ea/RT=e0=1
Therefore
T→∞limk=A
Interpretation: at infinitely high temperature every collision is energetic enough to cross the barrier, so the energy barrier stops mattering and the rate constant saturates at the collision frequency A. This is why A is often described as "the rate constant at infinite temperature".
3. Reading the numerical answer
The question quotes the value 6.0×105 s−1 and asks for A in that limit. Since k→A with the exponential factor equal to unity, the required value is simply
A=6×105 s−1 …
- COMEDK 2022Set 20221 markMCQQ.In which of the following changes, entropy decreases? (A) Rusting of iron (B) Melting of ice (C) Vaporisation of camphor (D) Crystallisation of sucrose from solution
›Reveal solutionSolution
The process asked for is the one where the system becomes more ordered, i.e. crystallisation of sucrose from solution (the standard textbook example of an entropy decrease).
Concept: Entropy increases with disorder/randomness; solid < liquid < gas, and dissolved/dispersed states have higher entropy than ordered solids.
(A) Rusting of iron: 4Fe(s) + 3O2(g) -> 2Fe2O3(s). Gas is consumed, so entropy DECREASES too - but this is a chemical change usually cited for its enthalpy; still, gas -> solid does lower S.
(B) Melting of ice: solid -> liquid, entropy INCREASES.
(C) Vaporisation of camphor: solid -> gas (sublimation), entropy INCREASES greatly. …
- KCET 2020Set A-11 markMCQQ.In which of the following cases a chemical reaction is possible ? (A) gold ornaments are washed with dil HCl (B) ZnSO4(aq) is placed in a copper vessel (C) AgNO3 solution is stirred with a copper spoon. (D) Conc. HNO3 is stored in a platinum vessel.
›Reveal solutionSolution
A chemical reaction is possible only when a more reactive metal displaces a less reactive metal from its salt solution. Here, copper displaces silver from AgNO3, so option (C) is correct.
The entire question hinges on the reactivity series of metals — a list that ranks metals from most reactive (like potassium) to least reactive (like gold and platinum). A chemical reaction occurs in a displacement scenario only if the metal doing the displacing is above the metal being displaced in this series. If the metal is below, no reaction happens.
Let’s examine each case one by one.
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Option (A): Gold ornaments washed with dilute HCl
Gold is one of the least reactive metals — it lies far below hydrogen in the reactivity series. Dilute HCl can only react with metals that are above hydrogen (like zinc, iron, magnesium), because those metals can displace hydrogen from the acid. Gold cannot. So no reaction occurs.
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Option (B): ZnSO4(aq) placed in a copper vessel
Here, the vessel is made of copper, and the solution contains zinc sulfate. For a reaction to happen, copper would have to displace zinc from its sulfate. But copper is less reactive than zinc (zinc is above copper in the series). A less reactive metal cannot displace a more reactive one. So no reaction.
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Option (C): AgNO3 solution stirred with a copper spoon
Copper is more reactive than silver (copper is above silver in the reactivity series). So copper can displace silver from silver nitrate:
Cu+2AgNO3→Cu(NO3)2+2Ag
You would see a greyish-black deposit of silver on the copper spoon, and the solution turns blue due to copper(II) nitrate. This reaction is possible.
- Option (D): Conc. HNO3 stored in a platinum vessel …
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- KCET 2019Set A-11 markMCQQ.The reaction in which ΔH>ΔU is (A) N2(g)+O2(g)⟶2NO(g) (B) N2(g)+3H2(g)⟶2NH3(g) (C) CaCO3(s)⟶CaO(s)+CO2(g) (D) CH4(g)+2O2(g)⟶CO2(g)+2H2O(l)
›Reveal solutionSolution
The key is the relation ΔH=ΔU+ΔngRT. For ΔH>ΔU, we need Δng>0 (increase in moles of gas). Only reaction (C) has Δng=+1, so the answer is (C).
The relationship between enthalpy change (ΔH) and internal energy change (ΔU) for a reaction is given by:
ΔH=ΔU+ΔngRT
where Δng is the change in the number of moles of gaseous substances (products minus reactants). This comes from the definition H=U+PV, and for ideal gases PV=nRT, so at constant temperature the PV term changes only when the number of gas moles changes.
For ΔH>ΔU, we need Δng>0 — the reaction must produce more gas moles than it consumes. Let’s check each option.
-
Option (A): N2(g)+O2(g)⟶2NO(g)
- Reactant gas moles: 1+1=2
- Product gas moles: 2
- Δng=2−2=0
- So ΔH=ΔU. Not greater.
-
Option (B): N2(g)+3H2(g)⟶2NH3(g)
- Reactant gas moles: 1+3=4
- Product gas moles: 2
- Δng=2−4=−2
- So ΔH<ΔU. Not greater.
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Option (C): CaCO3(s)⟶CaO(s)+CO2(g)
- Reactant gas moles: 0 (both solids)
- Product gas moles: 1 (only CO2 is a gas)
- Δng=1−0=+1
- So ΔH=ΔU+RT, meaning ΔH>ΔU. This fits.
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Option (D): CH4(g)+2O2(g)⟶CO2(g)+2H2O(l) …
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- KCET 2019Set A-11 markMCQQ.Which of the following is a network crystalline solid ? (A) I2 (B) NaCl (C) AlN (D) Ice
›Reveal solutionSolution
A network crystalline solid is one where atoms are bonded in a continuous 3D covalent network. Among the options, AlN fits this description, while the others are molecular or ionic solids. The correct answer is (C) AlN.
The key to this question lies in understanding the classification of crystalline solids based on the type of bonding and structural units. Network crystalline solids (also called covalent network solids) are held together by a continuous framework of covalent bonds extending throughout the crystal. This gives them very high melting points and extreme hardness. In contrast, molecular solids (like iodine or ice) have discrete molecules held by weak intermolecular forces, and ionic solids (like NaCl) consist of ions held by electrostatic attraction.
Let’s examine each option:
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Option (A): I2 (Iodine)
Iodine forms diatomic molecules held together in the solid state by weak van der Waals forces. These are discrete I2 units, not a continuous covalent network. It is a molecular solid, not a network solid.
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Option (B): NaCl (Sodium chloride)
NaCl is the classic example of an ionic solid. It consists of Na+ and Cl− ions arranged in a lattice, held by ionic bonds. While the structure is extended, the bonding is electrostatic, not covalent. So it is not a network covalent solid.
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Option (C): AlN (Aluminium nitride)
AlN is a compound where each Al atom is covalently bonded to four N atoms in a tetrahedral arrangement, and each N is similarly bonded to four Al atoms. This forms a three-dimensional network of covalent bonds, analogous to diamond or silicon carbide. It is a network covalent solid with a high melting point (over 2000°C) and great hardness. This matches the definition perfectly.
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Option (D): Ice (Solid H2O) …
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