Q.Give two important characteristics of physisorption.
Concept understanding — Adsorption — Physisorption and Chemisorption
A solid surface attracts contacting gas or liquid species because atoms sitting right at the surface — unlike atoms buried in the bulk — have unsatisfied ('residual') valency, and this attraction happens strictly at the surface, which is what marks adsorption out as a surface phenomenon, distinct from absorption, where the absorbed substance spreads uniformly through the whole bulk of the absorbing material. The solid that does the attracting is the adsorbent; the substance attracted and held is the adsorbate; the surface of separation where the adsorbate's concentration builds up is the interface; and removing the adsorbed substance again is desorption. Where adsorption and absorption both occur together, the combined process is called sorption (M.C. Bain), and the specific case of gases taken up within a metal (e.g. hydrogen in palladium) is called occlusion (T. Graham).
Adsorption can occur at any interfacial surface — gas–solid, liquid–solid, liquid–liquid, solid–solid or gas–liquid — and is always spontaneous, so ΔG<0, reaching equilibrium exactly when ΔG=0. Because molecules moving from a free, disordered phase into an ordered adsorbed layer necessarily lose randomness, ΔS<0 for adsorption; since ΔG=ΔH−TΔS and −TΔS is therefore positive, ΔH must be sufficiently negative for ΔG to stay negative overall — so adsorption is always exothermic, a conclusion that follows directly from the entropy decrease. Adsorption is also characteristically fast, much faster than the comparatively slow, diffusion-limited process of absorption.
Based on the nature of the forces involved, adsorption splits into two kinds. Chemisorption holds the adsorbate by genuine chemical bonds, releases a large heat of adsorption (40–400 kJ/mole), is slow, highly specific to the particular adsorbent–adsorbate pair, involves real electron transfer, forms only a single monolayer, occurs only at fixed 'active centre' sites (so it depends on surface area), and needs appreciable activation energy to form an activated complex. With rising temperature it first increases (supplying the activation energy needed) and then decreases (desorption). Physisorption, by contrast, holds the adsorbate only by weak van der Waals forces, dipole–dipole interactions and dispersion forces, releases much less heat (of the order of 40 kJ/mole), is instantaneous and non-specific, involves no electron transfer, can build up a multilayer, occurs over the whole surface rather than fixed sites, needs essentially no activation energy, decreases monotonically as temperature rises, and — unlike chemisorption's amount, which pressure cannot increase much — genuinely increases in extent as pressure rises.
The extent of adsorption depends on four qualitative factors: the surface area of the adsorbent (higher area → more adsorbed, since adsorption is a surface effect); the nature of the adsorbate (easily-liquefiable gases like SO2, NH3, HCl, CO2, which have strong van der Waals attraction and high critical temperature, adsorb readily, while 'permanent' gases like H2, N2, O2, with low critical temperature, adsorb only slowly); temperature (chemisorption rises then falls, physisorption falls steadily); and pressure (chemisorption's rate rises with pressure but its total amount is capped by the fixed number of active sites, while physisorption's extent genuinely rises with pressure). These same trends show up directly in the adsorption isobar (x/m vs T at constant P): physisorption's isobar falls steadily, while chemisorption's isobar rises to a maximum (surface activation) and then falls (desorption as kinetic energy grows).
Physisorption is reversible and has a low heat of adsorption.
Two defining characteristics: it is held together only by weak van der Waals forces (so it is reversible and easily reversed by mild heating or reduced pressure), and its heat of adsorption is low, of the order of 40 kJ/mole.
Physisorption is reversible, and it has a low heat of adsorption (~40 kJ/mole), since it involves only weak van der Waals attraction rather than a genuine chemical bond.
Step 1. Physisorption is held together purely by weak physical forces — van der Waals attraction, dipole–dipole interaction, and dispersion forces — between adsorbent and adsorbate, rather than by any genuine chemical bond.
Step 2. Because these attractive forces are weak, physisorption is reversible: the adsorbate can be desorbed relatively easily, simply by mild heating or by reducing the pressure, without any lasting chemical change to either species.
Step 3. Also because the forces are weak, the heat released on physisorption (the heat of adsorption) is correspondingly low, typically of the order of 40 kJ/mole — much lower than the 40–400 kJ/mole released by chemisorption, where a real chemical bond forms.
Step 4. Two further characteristics worth noting: physisorption is non-specific (it can occur between almost any adsorbent–adsorbate pair, since van der Waals forces act universally) and it can build up a multilayer of adsorbate, since further layers can attach on top of the first via the same weak forces.
Two important characteristics of physisorption: it is reversible, and it has a low heat of adsorption (of the order of 40 kJ/mole) — both consequences of it being held together only by weak van der Waals-type forces rather than a chemical bond.
Recall the defining physical basis of physisorption (weak van der Waals-type forces, not a chemical bond) and derive its characteristics — reversibility and low heat of adsorption — directly from that weak-force basis.
Listing a chemisorption characteristic (e.g. high specificity, monolayer formation) by mistake instead of a genuine physisorption trait.
- CBSE 2024Set ANNUAL1 markQ.Define chemical adsorption.
›Reveal solutionSolution
Chemisorption binds adsorbate to adsorbent by real chemical bonds, unlike physisorption's weak van der Waals forces.
Adsorption is the accumulation of a substance (adsorbate) at the surface of another substance (adsorbent). It is of two types — physical adsorption (physisorption) and chemical adsorption (chemisorption).
Chemical adsorption (chemisorption): the adsorbate molecules are held to the adsorbent surface by strong chemical forces (covalent or ionic bonding), similar in strength to a true chemical bond.
Characteristics:
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Heat of adsorption is high, typically 80-240 kJ/mol (comparable to a chemical reaction).
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It is highly specific — occurs only between an adsorbate and adsorbent that can form a chemical bond.
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It generally requires activation energy, so it increases with temperature initially (unlike physisorption).
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It forms only a monolayer on the surface and is largely irreversible.
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Example: oxygen adsorbed on tungsten forms a layer of tungsten oxide (chemical bonding), and H2 chemisorbed on a Ni surface during catalytic hydrogenation.
✓Final answerChemisorption (chemical adsorption) is the adhesion of adsorbate molecules to an adsorbent surface via strong chemical bonds, with a high heat of adsorption (80-240 kJ/mol), high specificity, and (usually) monolayer, irreversible character.
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- CBSE 2022Set ANNUAL1 markMCQQ.In the equilibrium state adsorption process follows the condition(a) dH > 0(b) dH = T.dS(c) dH > T.dS(d) dH < T.dS OR The rate of adsorption increases in the solution of adsorbent when(a) the quantity of the adsorbent in the solution increases(b) the area of the surface of the adsorbent in the solution decreases(c) the temperature of the solution increases(d) the quantity of the adsorbent in the solution decreases
›Reveal solutionSolution
At equilibrium, the Gibbs free energy change for the adsorption process is zero, which forces ΔH=TΔS.
Reasoning: Adsorption is generally a spontaneous, exothermic process (ΔH<0) accompanied by a decrease in entropy (ΔS<0, since the adsorbate loses translational freedom on binding to the surface). The Gibbs free energy relation is:
ΔG=ΔH−TΔS
For the process to be spontaneous, ΔG<0 (requiring ∣ΔH∣>∣TΔS∣ in magnitude, since both terms are negative here). As adsorption proceeds, ΔS becomes progressively less negative in magnitude (or the system approaches a balance) until, at the equilibrium state (dynamic equilibrium between adsorption and desorption), ΔG=0. Setting ΔG=0 in the equation above gives:
0=ΔH−TΔS⟹ΔH=TΔS
✓Final answer(b) ΔH=TΔS — because at equilibrium ΔG=0 in ΔG=ΔH−TΔS.
- CBSE 2021Set TERM11 markMCQQ.The term "sorption" stands for :(a) absorption(b) adsorption(c) Both absorption and adsorption(d) None of these
›Reveal solutionSolution
Sorption is the general term used when it isn't clear (or both processes occur together) whether uptake is by absorption or adsorption.
Adsorption is a surface phenomenon — the substance gets concentrated only at the surface, not inside the bulk. Absorption is a bulk phenomenon — the substance is uniformly distributed throughout the bulk of the solid/liquid. When both processes occur simultaneously (e.g., water vapour taken up by anhydrous CaCl2 — partly adsorbed on the surface and partly absorbed into the bulk), the phenomenon is called sorption.
✓Final answerSorption stands for both absorption and adsorption (option c).
- CBSE 2019Set ANNUAL1 markMCQQ.The physical adsorption is due to(a) strong coulombic forces(b) Vander waals' forces(c) hydrogen bonding(d) covalent bond formation
›Reveal solutionSolution
Physisorption arises purely from weak van der Waals attractions between the adsorbate molecules and the adsorbent surface — option (b).
Physical adsorption does not involve any chemical bond formation; the adsorbate molecules are held to the adsorbent's surface only by weak, non-specific van der Waals forces (dispersion/dipole forces), similar to the forces responsible for the liquefaction of gases. Because these forces are weak, physisorption has a low enthalpy of adsorption (typically 20–40 kJ/mol), is readily reversible, and adsorbed molecules can build up in multiple layers. This is unlike chemisorption, which involves the formation of strong chemical bonds (ionic/covalent-type) between adsorbate and adsorbent.
✓Final answer(b) Van der Waals' forces — the weak, non-specific attractive forces responsible for physical adsorption.
- CBSE 2018Set ANNUAL1 markQ.Differentiate between chemisorption and physisorption.
›Reveal solutionSolution
The two types of adsorption differ in the strength/nature of the forces binding adsorbate to adsorbent.
Feature Physisorption Chemisorption Force involved Weak van der Waals forces Strong chemical bond (covalent-like) forces Enthalpy of adsorption Low (20–40 kJ/mol) High (80–240 kJ/mol) Specificity Not specific — occurs on any surface Highly specific — occurs only between suitable adsorbate–adsorbent pairs Reversibility Reversible Generally irreversible Layer formed Can form multimolecular layers Forms only a monomolecular layer Effect of temperature Decreases with rise in temperature First increases then decreases with temperature (needs activation energy) Activation energy Low/none needed Often needs significant activation energy Both phenomena occur at a surface (adsorbent) where adsorbate particles accumulate, but physisorption is essentially a physical, non-specific 'condensation'-like effect, while chemisorption involves actual electron sharing/transfer forming new chemical bonds.
✓Final answerChemisorption = strong chemical bonding, monolayer, mostly irreversible, specific. Physisorption = weak van der Waals forces, multilayer, reversible, non-specific.
- CBSE 2018Set ANNUAL1 markMCQQ.For chemisorption, which is wrong ?(a) it forms multimolecular layers on adsorbate(b) irreversible(c) surface compounds are formed(d) it requires activation energy
›Reveal solutionSolution
Chemisorption involves chemical bond formation between adsorbate and adsorbent, so it is confined to a single molecular layer, unlike physisorption which can form multiple layers.
Characteristics of chemisorption:
- It forms only a monomolecular layer on the adsorbent surface (never multimolecular) — statement (a) is therefore WRONG.
- It is generally irreversible because chemical bonds are formed between adsorbate and adsorbent — statement (b) is correct.
- Surface compounds are formed due to chemical interaction — statement (c) is correct.
- It requires activation energy (it is 'activated adsorption') — statement (d) is correct.
Multimolecular (multilayer) adsorption is instead a hallmark of physisorption (physical adsorption held together by weak van der Waals forces), not chemisorption.
✓Final answera) it forms multimolecular layers on adsorbate
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