Q.(a)
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Standard Electrode Potentials: A Number for "How Badly It Wants Electrons"
Dip a zinc rod into a zinc-salt solution and a tiny tug-of-war begins at the surface:
metal atoms tend to dissolve as ions (leaving electrons behind on the rod) while ions
from the solution tend to deposit as metal (consuming electrons). The rod ends up with
a characteristic electrical potential relative to the solution — the electrode potential. It is a direct measure of the tendency of that redox couple to gain or
lose electrons.
The Core Idea
Different couples pull electrons with very different strengths. Copper's ion grabs
them readily; zinc's barely wants them. Put a number on each couple and you can
predict, before mixing anything, who will oxidise whom.
Two conventions make the numbers comparable:
- Standard conditions. Every species at unit concentration (1 M), any gas at 1 atm, temperature 298 K. The potential measured then is the standard electrode potential, written E⊖.
- A common zero. Potentials can only be measured as differences, so one electrode is defined as the reference: the standard hydrogen electrode (SHE), 2H++2e−→H2, is fixed at exactly 0.00 V. Every E⊖ is the voltage of a couple measured against it.
By convention the values are tabulated for the reduction direction:
Oxidised form+ne−→Reduced formE⊖ (in volts, at 298 K)
Reading the Table
The standard-potential table (Table 7.1 in the Class 11 chapter) runs from
F2/F− at +2.87 V down to Li+/Li at −3.05 V.
Two rules unlock it:
- More positive E⊖ → stronger oxidising agent (the oxidised form is hungrier for electrons). F₂ tops the table; that is why fluorine oxidises almost everything.
- More negative E⊖ → stronger reducing agent (the reduced form gives electrons up most easily). Li, K, Ca, Na at the bottom are the great electron donors. A negative E⊖ means the couple is a stronger reducing agent than the H⁺/H₂ couple; a positive one, weaker.
Predicting Whether a Reaction Goes
For any proposed redox reaction, the species being reduced acts as the cathode couple
and the species being oxidised as the anode couple:
Ecell⊖=Ecathode⊖−Eanode⊖
A positive Ecell⊖ means the reaction is feasible
(spontaneous) under standard conditions; a negative one means the reverse reaction
is the spontaneous direction.
Worked feel: can Fe³⁺ oxidise iodide? E⊖(Fe3+/Fe2+)=+0.77 V is above E⊖(I2/I−)=+0.54 V, so
Ecell⊖=+0.23 V — yes. Can silver metal reduce Fe³⁺?
0.77−0.80=−0.03 V — no.
This is also the logic of the activity series: a metal displaces, from solution, …
Why this formula?
Galvanic Corrosion: Why the Key Formulas Hold
Galvanic corrosion occurs when two dissimilar metals are electrically connected in the presence of an electrolyte. The key formula that governs this is the mixed potential theory, which leads to the galvanic current and corrosion rate expressions.
Let's build the reasoning step-by-step.
1. The Core Idea: Two Electrodes, One Circuit
When metals M₁ (more active, e.g., zinc) and M₂ (more noble, e.g., copper) are connected:
- M₁ acts as the anode — it oxidizes (corrodes):
M1→M1n++ne−
- M₂ acts as the cathode — it reduces something (e.g., oxygen or H⁺):
O2+2H2O+4e−→4OH−(in neutral/alkaline)
or
2H++2e−→H2(in acidic)
The two metals are electrically connected (via a wire or direct contact), and the electrolyte completes the circuit. Electrons flow from M₁ to M₂.
2. The Mixed Potential: Why It Exists
Each metal, when alone in the electrolyte, has its own open-circuit potential (OCP) — the equilibrium potential for its half-reaction. For M₁, it's Ecorr,1; for M₂, it's Ecorr,2.
When connected, the system cannot stay at two different potentials. The entire metal couple must reach a single potential — the mixed potential Emix.
- Emix lies between Ecorr,1 and Ecorr,2.
- At Emix, the total anodic current from M₁ equals the total cathodic current from M₂ (charge conservation):
Ianode=Icathode
This is the fundamental equation of galvanic corrosion.
3. Deriving the Galvanic Current
Assume each electrode follows Butler-Volmer kinetics (for activation-controlled reactions). For the anode (M₁), the anodic current density ia at potential E is:
ia=i0,1exp(RTαaF(E−E0,1))
For the cathode (M₂), the cathodic current density ic is:
ic=i0,2exp(−RTαcF(E−E0,2))
Where:
- i0,1,i0,2 = exchange current densities
- αa,αc = transfer coefficients (typically ~0.5)
- F = Faraday constant
- R = gas constant
- T = temperature
- E0,1,E0,2 = standard reduction potentials
At the mixed potential Emix:
Igalvanic=A1⋅ia(Emix)=A2⋅ic(Emix)
Where A1 and A2 are the surface areas of the anode and cathode.
Why this holds: The net current from the anode must exactly balance the net current consumed at the cathode — otherwise, charge would accumulate, which is impossible in a steady-state circuit.
4. The Corrosion Rate Formula
The corrosion rate (mass loss per time) of the anode is given by Faraday's law:
Corrosion rate=n⋅F⋅ρIgalvanic⋅M
Where:
- M = molar mass of the anode metal
- n = number of electrons transferred per atom
- ρ = density of the metal
- F = Faraday constant (96,485 C/mol)
Why this holds: Each mole of metal oxidized releases n moles of electrons. The total charge passed Q=Igalvanic⋅t corresponds to moles of metal lost:
moles lost=nFQ=nFIgalvanic⋅t
Multiply by M/ρ to get volume or thickness loss.
5. The Area Effect: Why It Matters
From the mixed potential equation:
A1⋅ia(Emix)=A2⋅ic(Emix)
If the cathode area A2 is large relative to the anode area A1, then ia(Emix) must be large to balance the current. This means:
- Small anode + large cathode → severe galvanic corrosion (high current density on the anode). …
Part (b)Concept understanding — Disproportionation Reaction
Disproportionation Reactions: The Self-Oxidation-Reduction
The Intuition
Imagine you have a group of friends who are all equally wealthy — each has exactly ₹100. Now suppose one friend decides to give ₹50 to another. After this transaction, one friend has ₹50 (lost money), another has ₹150 (gained money), and the rest are unchanged. Notice something: the same action — transferring money — made one person poorer and another richer.
A disproportionation reaction works on a similar principle, but with electrons instead of money. One atom of an element simultaneously gets oxidised (loses electrons) and reduced (gains electrons). The same element ends up in two different oxidation states — one higher, one lower — starting from a single intermediate oxidation state.
The word "disproportionation" literally means "breaking apart into unequal parts." The original state splits into two different states.
The Precise Definition
A disproportionation reaction is a redox reaction in which a single substance (element or compound) in an intermediate oxidation state is simultaneously oxidised and reduced, producing two different products — one with a higher oxidation state and one with a lower oxidation state.
The general form looks like this:
Element in intermediate state⟶Higher oxidation state+Lower oxidation state
The Key Condition
For disproportionation to occur, the element must be in an intermediate oxidation state — meaning it can both increase and decrease its oxidation number. If the element is already in its highest possible oxidation state, it can only be reduced. If it's in its lowest, it can only be oxidised. No disproportionation possible.
Disproportionation requires the element to have at least three accessible oxidation states: one lower, one intermediate (the starting point), and one higher.
Classic Example: Hydrogen Peroxide
Hydrogen peroxide (H2O2) is the textbook example. Oxygen in H2O2 has an oxidation state of -1. This is intermediate — oxygen can go to 0 (in O2) or to -2 (in H2O).
When H2O2 decomposes:
2H2O2⟶2H2O+O2
Let's track the oxygen:
- In H2O2: oxidation state = -1
- In H2O: oxidation state = -2 (reduction — gained an electron)
- In O2: oxidation state = 0 (oxidation — lost an electron)
The same oxygen atoms (from the same molecule) undergo both oxidation and reduction. That's disproportionation.
Another Common Example: Copper(I) in Solution
Copper(I) ion (Cu+) is unstable in aqueous solution and disproportionates:
2Cu+⟶Cu+Cu2+
- Cu+ (oxidation state +1) is the intermediate
- Cu (oxidation state 0) is the reduced product
- Cu2+ (oxidation state +2) is the oxidised product
A common mistake is to think that a single atom does both oxidation and reduction. In reality, two atoms of the same element are involved — one gets oxidised, the other gets reduced. The reaction requires at least two formula units of the starting substance.
How to Identify a Disproportionation Reaction
- Look for a single reactant that contains an element in an intermediate oxidation state.
- Check the products — the same element must appear in two different oxidation states (one higher, one lower than the starting state). …
Why this formula?
Disproportionation Reaction — Understanding the Why
A disproportionation reaction is a redox reaction where the same element in one oxidation state simultaneously undergoes oxidation (increase in oxidation number) and reduction (decrease in oxidation number).
The key formula that governs whether such a reaction is spontaneous is based on the standard electrode potentials (E∘) of the two half-reactions.
The Core Idea: Why Does Disproportionation Happen?
For an element in an intermediate oxidation state, it can be both oxidised and reduced.
Whether this happens spontaneously depends on the relative ease of these two processes.
Consider an element X in oxidation state +n:
-
Oxidation half-reaction:
X+n→X+(n+1)+e−
(loss of electron, oxidation number increases)
-
Reduction half-reaction:
X+n+e−→X+(n−1)
(gain of electron, oxidation number decreases)
The overall disproportionation reaction is:
2X+n→X+(n+1)+X+(n−1)
The Key Formula: Spontaneity Condition
For a disproportionation reaction to be spontaneous (under standard conditions), the overall cell potential Ecell∘ must be positive.
Derivation:
-
Identify the two half-reactions and their standard reduction potentials (E∘):
-
Reduction half-reaction (the one that gains electrons):
X+n+e−→X+(n−1)
Let its standard reduction potential be Ered∘.
-
Oxidation half-reaction (the one that loses electrons):
X+n→X+(n+1)+e−
This is the reverse of a reduction. So its standard oxidation potential is −Eox∘, where Eox∘ is the standard reduction potential for:
X+(n+1)+e−→X+n
-
-
Overall cell potential is:
Ecell∘=Ereduction half-cell∘−Eoxidation half-cell∘
But careful: The oxidation half-cell is the reverse of a reduction. So we write:
Ecell∘=Ered∘−Eox∘
where:
- Ered∘ = standard reduction potential for X+n→X+(n−1)
- Eox∘ = standard reduction potential for X+(n+1)→X+n
- Spontaneity condition:
Ecell∘>0⇒Ered∘>Eox∘
In words: Disproportionation is spontaneous if the reduction potential for the lower oxidation state is greater than that for the higher oxidation state.
Why This Makes Sense — A Conceptual Explanation
- Ered∘ tells you how easily X+n gets reduced to X+(n−1). …
Part (a)
(i)(I) The trend is irregular because EM2+/M∘ depends on the sum of sublimation, ionisation (IE1+IE2) and hydration enthalpies, which vary irregularly across the series (plus extra stability of half-filled/filled d-configurations). (II) ECu2+/Cu∘ is exceptionally positive (+0.34 V) because the high (IE1+IE2) of Cu is not offset by its atomisation/hydration enthalpies, so Cu2+ is readily reduced to Cu. (III) EMn2+/Mn∘ is highly negative (−1.18 V) because Mn2+ (3d5, half-filled) is very stable, making its formation from Mn easy / reduction to Mn hard. …
Part (a): the EM2+/M∘ trend is irregular (sublimation+ionisation+hydration enthalpies); Cu is exceptionally positive, Mn highly negative (stable half-filled Mn2+); KMnO4 oxidises I− to I2 (acidic) or IO3− (alkaline).
Part (b): Ce shows +4, Eu +2; transition metals catalyse via variable states/vacant d-orbitals; Cr melts higher than Mn; acidified KMnO4 decomposes (4MnO4−+4H+→4MnO2+3O2+2H2O) — an auto-oxidation.
Part (a)
(i) Interpreting the EM2+/M∘ values
EM2+/M∘ is governed by ΔHsub+(IE1+IE2)+ΔHhyd, none of which vary smoothly.
- (I) Irregular trend: the three enthalpies vary irregularly, and extra stability of half-filled (Mn2+ d5) or the special hydration/ionisation of Cu2+ distort the values (V and Mn both −1.18, Cr −0.91, Cu +0.34).
- (II) Cu2+/Cu exceptionally positive (+0.34 V): the very high (IE1+IE2) of copper is not compensated by its enthalpy of atomisation and hydration, so Cu2+ is readily reduced to Cu (Cu is a poor reducing metal — it does not liberate H2 from acids).
- (III) Mn2+/Mn highly negative (−1.18 V): Mn2+ has a stable half-filled 3d5 configuration; it forms easily from Mn and resists reduction back to Mn, giving a strongly negative potential.
(ii) Oxidising action of KMnO4 with I−
- Acidic medium (MnO4−→Mn2+, I−→I2):
2MnO4−+16H++10I−→2Mn2++8H2O+5I2
- Alkaline medium (MnO4−→MnO2, I−→IO3−): …
Showing the 12 most recent of 22 on this concept.
- CBSE 2026Set 56/3/11 markMCQQ.On electrolysis of very dilute aqueous solution of NaCl using platinum electrodes : (A) H2 gas is evolved at anode. (B) Na is produced at cathode. (C) O2 gas is evolved at anode. (D) H2 gas is evolved at cathode.
›Reveal solutionSolution
In very dilute aqueous NaCl with inert Pt electrodes, water’s reduction to H2 at the cathode and water’s oxidation to O2 at the anode outcompete the NaCl reactions. So H2 is produced at the cathode and O2 at the anode — making option (C) and (D) correct.
Why standard electrode potentials decide the outcome
Electrolysis is a battle of competing half-reactions. At each electrode, the species that is easier to oxidise (at the anode) or easier to reduce (at the cathode) will react first. “Easier” means having a more positive reduction potential for reduction, or a more negative reduction potential for oxidation (equivalently, a more positive oxidation potential).
For a very dilute aqueous solution of NaCl, the possible species are:
- Cathode (reduction): Na+ ions and H2O molecules.
- Anode (oxidation): Cl− ions and H2O molecules.
We compare their standard reduction potentials (at 298 K, 1 M concentration, 1 atm pressure). But remember: concentration matters. In very dilute NaCl, [Cl−] is tiny, which shifts the actual potential of the chlorine half-reaction significantly.
Step-by-step reasoning
1. What happens at the cathode?
Two reduction half-reactions compete:
Na++e−2H2O+2e−→Na(s)E∘=−2.71 V→H2(g)+2OH−E∘=−0.83 V
The reduction of water to hydrogen gas has a much less negative (i.e., more positive) standard potential. Even though the actual potential for water reduction depends slightly on pH (here neutral to slightly basic), it remains far above −2.71 V. So water is reduced preferentially.
Watch outA common mistake is to think that because Na+ is present, sodium metal will plate out. But sodium’s reduction potential is so negative that water (even in neutral solution) is reduced first. Sodium metal would instantly react with water anyway — it’s never produced in aqueous electrolysis.
Result at cathode: H2 gas is evolved. This matches option (D).
2. What happens at the anode?
Two oxidation half-reactions compete (written as reductions for comparison):
Cl2(g)+2e−O2(g)+4H++4e−→2Cl−E∘=+1.36 V→2H2OE∘=+1.23 V …
- CBSE 2026Set 56/2/11 markMCQQ.Consider the following reaction : Zn(s)+Ag2O(s)+H2O(l)→Zn2+(aq)+2Ag(s)+2OH−(aq) Given : EAg+/Ago=0.80 V, EZn2+/Zno=−0.76 V, 1F=96500 C mol−1 ΔrGo for the above reaction is : (A) −301.080 kJ mol−1 (B) +310.080 kJ mol−1 (C) −326.070 kJ mol−1 (D) −375.060 kJ mol−1
›Reveal solutionSolution
Zinc is oxidised and silver is reduced, giving Ecello=0.80−(−0.76)=1.56 V with n=2. Then ΔrGo=−nFEcello=−301.080 kJ mol−1, which is option (A).
The standard Gibbs energy of a cell reaction is linked to its standard cell potential by
ΔrGo=−nFEcello
so we first find Ecello, then n, and finally ΔrGo.
1. Identify the electrodes. Zinc is oxidised (anode) and silver is reduced (cathode):
Anode:Zn→Zn2++2e−
Cathode:Ag2O+H2O+2e−→2Ag+2OH−
2. Standard cell potential. Using the given reduction potentials,
Ecello=Ecathodeo−Eanodeo=0.80−(−0.76)=1.56 V
3. Electrons transferred. Each half-reaction involves 2 electrons, so n=2. …
- CBSE 2026Set ANNUAL1 markMCQQ.In the following reaction 4P + 3KOH + 3H2O -> 3KH2PO2 + PH3, which statement is correct?(a) 'P' is oxidised only(b) 'P' is reduced only(c) 'P' is oxidised as well as reduced(d) 'P' is neither oxidised nor reduced
›Reveal solutionSolution
When the same element, starting from a single oxidation state, ends up in both a higher and a lower oxidation state among the products, that is a disproportionation reaction.
Reaction: 4P + 3KOH + 3H2O -> 3KH2PO2 + PH3
Oxidation state of P in elemental phosphorus (P4, written here as P): 0 (element in its standard state).
Oxidation state of P in KH2PO2 (potassium hypophosphite): Using K = +1, H = +1 (bonded to O, standard H), O = -2:
(+1) + 2(+1 for the two H bonded to O) ... more directly: for the hypophosphite ion H2PO2-, charge = -1. With 2 H at +1 and 2 O at -2: 2(+1) + x + 2(-2) = -1 => 2 + x - 4 = -1 => x = +1.
So P is +1 in KH2PO2 -- this is an INCREASE from 0, i.e. P is OXIDISED here.
Oxidation state of P in PH3: H bonded to P (a less electronegative element than H here, since P and H have similar/P slightly higher electronegativity by the modified scale used for this compound) is taken as -1 in this hydride convention: x + 3(-1) = 0 => x = +3?
…
- CBSE 2026Set ANNUAL1 markMCQQ.In the disproportionation reaction 2 Cu⁺ (aq) ⇌ Cu (s) + Cu²⁺ (aq), the cuprous ion, Cu⁺(a) undergoes reduction only(b) undergoes both reduction and oxidation(c) undergoes oxidation only(d) does not undergo redox
›Reveal solutionSolution
Disproportionation means the same species is simultaneously oxidised and reduced; here half the Cu⁺ goes to Cu (reduction) and half to Cu²⁺ (oxidation) — option (B).
Disproportionation is a redox reaction in which an element in one intermediate oxidation state is simultaneously oxidised and reduced.
Track the oxidation number of copper in 2Cu+→Cu+Cu2+:
- One Cu+ (oxidation state +1) → Cu (oxidation state 0): gain of electron = reduction. …
- CBSE 2025Set D1 markMCQQ.The electromotive force of the following cell is: Zn | Zn2+ (1M) || Fe2+ (1M) | Fe, given E°Zn2+|Zn = -0.76 V, E°Fe2+|Fe = -0.44 V(a) 1.2 V(b) 0.32 V(c) -1.2 V(d) -0.32 V
›Reveal solutionSolution
E(cell) = E(cathode) - E(anode) = -0.44 - (-0.76) = +0.32 V.
In the cell notation Zn | Zn2+ || Fe2+ | Fe, zinc is the anode (oxidation, written left) and iron is the cathode (reduction, written right). The standard cell EMF is:
E(cell) = E(cathode) - E(anode)
E(cell) = E(Fe2+/Fe) - E(Zn2+/Zn)
E(cell) = (-0.44) - (-0.76) …
- CBSE 2025Set A1 markQ.Write True or False: The cell potential is the addition of the electrode potentials (reduction potentials) of the cathode and anode.
›Reveal solutionSolution
Cell potential is obtained by subtracting the anode's reduction potential from the cathode's, not by adding the two reduction potentials.
The standard cell potential is defined as:
Ecell∘=Ecathode(reduction)∘−Eanode(reduction)∘
If both electrode potentials are taken as reduction potentials (as the statement specifies), the correct operation is a subtraction (cathode minus anode), not an addition. The 'addition' phrasing is only valid if the anode's contribution is expressed as an oxidation potential (= −reduction potential): then …
- CBSE 2025Set ANNUAL1 markQ.Answer in one word/sentence: Given the standard electrode potentials, arrange these metals in their increasing order of reducting power: K+/K = -2.93 V, Ag+/Ag = 0.80 V, Hg2+/Hg = 0.79 V, Mg2+/Mg = -2.37 V.
›Reveal solutionSolution
Reducing power increases as the standard electrode (reduction) potential becomes more negative, so we simply rank the four E° values from most positive to most negative.
Given standard reduction potentials:
K+/K=−2.93 V,Mg2+/Mg=−2.37 V,Hg2+/Hg=+0.79 V,Ag+/Ag=+0.80 V
A more negative (or less positive) standard reduction potential means the metal has a greater tendency to lose electrons (be oxidised) — i.e. it is a stronger reducing agent. Conversely, a metal with a highly positive reduction potential prefers to stay reduced (gain electrons), making it a poor reducing agent (like Ag, a "noble" metal).
…
- CBSE 2025Set ANNUAL1 markQ.Write two applications of electrochemical series.
›Reveal solutionSolution
Electrochemical series: predicts reaction feasibility and metal-displacement reactivity.
The electrochemical series arranges elements/ions in order of their standard reduction potentials (E°). Two common applications:
- Predicting feasibility of a redox reaction: a reaction is spontaneous if the species with the higher (more positive) reduction potential is reduced while the species with the lower (more negative) reduction potential is oxidized, i.e. E°cell=E°cathode−E°anode>0. …
- CBSE 2024Set 56/3/11 markMCQQ.During the electrolysis of aqueous NaCl, the cathodic reaction is : (A) Oxidation of Cl− ion (B) Reduction of Na+ ion (C) Oxidation of H2O (D) Reduction of H2O
›Reveal solutionSolution
In aqueous NaCl electrolysis, the cathode is where reduction occurs. The competing reductions are Na+ and H2O; water has a much less negative reduction potential, so it is reduced instead of sodium. The correct answer is (D) Reduction of H2O.
The key to this question lies in understanding Standard Electrode Potentials — the numerical measure of a species’ tendency to gain electrons (be reduced). In electrolysis, the cathode is the negative electrode where reduction happens. When you have an aqueous solution, you must consider all possible reducible species, not just the obvious cation from the salt.
For aqueous NaCl, the solution contains:
- Na+ ions (from the salt)
- H2O molecules (the solvent)
- Cl− ions (from the salt — but these are oxidised at the anode, not reduced at the cathode)
At the cathode, two reduction reactions compete:
-
Reduction of Na+:
Na++e−→Na(s)
Standard reduction potential: E∘=−2.71 V
-
Reduction of water:
2H2O+2e−→H2(g)+2OH−
Standard reduction potential: E∘=−0.83 V
Watch outA common mistake is to assume that because Na+ is the cation, it must be reduced at the cathode. But the more positive (or less negative) the reduction potential, the easier the reduction. Here, water’s potential (−0.83 V) is far less negative than sodium’s (−2.71 V), meaning water is much more readily reduced.
Now, let’s work through the reasoning step by step.
-
Identify the cathode process.
The cathode is the electrode where reduction occurs — gain of electrons. So we look for which species can accept electrons.
-
List all reducible species in the solution.
In aqueous NaCl: Na+ ions and H2O molecules. (The Cl− ions are already in their lowest oxidation state for a halide; they cannot be reduced further under these conditions — they are oxidised at the anode.)
-
Compare their reduction potentials.
- Na++e−→Na: E∘=−2.71 V
- 2H2O+2e−→H2+2OH−: E∘=−0.83 V
The more positive (or less negative) the potential, the stronger the oxidising agent — i.e., the more likely it is to be reduced. Since −0.83>−2.71, water is a much stronger oxidising agent than Na+ in this system. …
- CBSE 2024Set ANNUAL1 markQ.In which electrode of a Galvanic cell, oxidation reaction takes place?
›Reveal solutionSolution
The anode of a galvanic cell is where oxidation (electron loss) occurs.
A Galvanic (voltaic) cell converts the chemical energy of a spontaneous redox reaction into electrical energy, splitting the reaction into two half-cells. The electrode at which oxidation (loss of electrons) takes place is called the anode; in a galvanic cell this is the negative electrode. For example, in the Daniell cell, Zn(s)→Zn2+(aq)+2e− o …
- CBSE 2024Set ANNUAL1 markMCQQ.Emf of a cell with Nickel and Copper electrode will be (Given E0 Ni+2/Ni = -0.25 V, E0 Cu2+/Cu = +0.34 V)(a) -0.59 V(b) +0.59 V(c) +0.09 V(d) -0.09 V
›Reveal solutionSolution
The electrode with the higher (more positive) standard reduction potential acts as the cathode; the cell EMF is Ecathode - Eanode.
Given: E-degree(Ni2+/Ni) = -0.25 V, E-degree(Cu2+/Cu) = +0.34 V.
Since Cu2+/Cu has the higher reduction potential, copper is reduced (cathode) and nickel is oxidised (anode):
Anode (oxidation): Ni -> Ni2+ + 2e-
Cathode (reduction): Cu2+ + 2e- -> Cu
…
- CBSE 2023Set 56/1/11 markMCQQ.ΔG and Ecell∘ for a spontaneous reaction will be : (A) positive, negative (B) negative, negative (C) negative, positive (D) positive, positive
›Reveal solutionSolution
A spontaneous reaction releases free energy (ΔG<0) and generates a positive cell potential (Ecell∘>0); the answer is (C).
The connection between thermodynamics and electrochemistry rests on a beautiful relationship: the Gibbs free energy change tells us whether a reaction will proceed on its own, while the standard cell potential measures the driving force behind electron flow. For a reaction to be spontaneous, it must release free energy to do useful work—including pushing electrons through a circuit.
The fundamental bridge between these quantities is:
ΔG∘=−nFEcell∘
where n is the number of moles of electrons transferred, F is Faraday's constant (96,485C/mol), and Ecell∘ is the standard cell potential.
The negative sign in this equation is the key. It tells us that a positive cell potential (electrons flowing spontaneously from anode to cathode, releasing energy) corresponds to a negative Gibbs free energy change (energy released, reaction spontaneous). Think of it this way: when a battery drives current through a device, it's doing work on the surroundings, which means the battery's chemical reaction is losing free energy—hence ΔG<0.
Now let's apply this to the question:
-
What does spontaneity require thermodynamically?
A spontaneous process proceeds without external intervention and releases free energy. The criterion is ΔG<0 (negative). This is the defining condition—if ΔG were positive, we'd need to supply energy to make the reaction go.
-
What does the equation tell us about Ecell∘?
Rearranging: Ecell∘=−nFΔG∘. Since n and F are always positive, and we've established that ΔG∘<0 for a spontaneous reaction, the negative sign in front flips the inequality: Ecell∘>0 (positive).
-
Physical interpretation
A positive standard cell potential means the cathode (reduction site) has a higher reduction potential than the anode (oxidation site). Electrons naturally flow "downhill" in potential, from lower to higher reduction potential, generating voltage. This is exactly what happens in a galvanic (voltaic) cell—the spontaneous reaction produces electrical energy. …
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