Q.Given the standard electrode potentials:
K+/K=−2.93 V, Ag+/Ag=0.80 V, Hg2+/Hg=0.79 V,
Mg2+/Mg=−2.37 V, Cr3+/Cr=−0.74 V
Arrange these metals in their increasing order of reducing power.
Concept understanding — Standard Electrode Potentials
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,
the ions of any metal whose couple sits above it (less negative / more positive) in
the table — Zn displaces Cu²⁺, Cu displaces Ag⁺, never the reverse.
Common Mistakes
- Flipping the sign when a half reaction is reversed and then double-counting. Use Ecell⊖=Ecathode⊖−Eanode⊖ with BOTH values as tabulated (reduction) potentials — the subtraction already handles the reversal.
- Multiplying E⊖ by stoichiometric coefficients. Potentials are intensive: doubling a half reaction does not double its E⊖.
- Reading "negative" as "impossible". A negative E⊖ only ranks the couple as a stronger reducing agent than H⁺/H₂ — zinc's −0.76 V is exactly why zinc is so good at reducing other ions.
Exam Relevance
Standard-potential questions are staples: pick the strongest oxidising/reducing agent
from given E⊖ values, decide whether a pair reacts (CBSE Class 11 Exercise
7.26; Exemplar Q2–Q4, Q16, Q34), order metals by reducing power, or justify a
displacement series. In Class 12 the same idea grows into full electrochemistry — the
Nernst equation extends E⊖ to non-standard concentrations, and cell EMF
connects to thermodynamics via ΔG=−nFE.
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).
- Large anode + small cathode → mild corrosion.
Why this holds: The current density on the anode is ia=Igalvanic/A1. For a fixed Igalvanic, smaller A1 gives higher ia, which accelerates corrosion.
6. The Driving Force: Potential Difference
The driving force for galvanic corrosion is the difference in open-circuit potentials:
ΔE=Ecorr,2−Ecorr,1
A larger ΔE generally leads to a larger Igalvanic, but the exact relationship depends on the polarization behavior (Tafel slopes) of both electrodes.
Why this holds: The mixed potential Emix is determined by the intersection of the anodic and cathodic polarization curves. A larger separation between the two curves shifts the intersection to a higher current.
Summary of Key Takeaways
| Concept | Formula | Why It Holds |
|---|---|---|
| Mixed potential | Ianode=Icathode | Charge conservation in a closed circuit |
| Galvanic current | A1ia(Emix)=A2ic(Emix) | Butler-Volmer kinetics + area balance |
| Corrosion rate | nFρIgalvanicM | Faraday's law of electrolysis |
| Area effect | Small anode → high ia | Current density inversely proportional to area |
| Driving force | ΔE=Ecorr,2−Ecorr,1 | Larger potential difference → larger current (generally) |
Exam tip: Always start with the mixed potential condition — it's the foundation. Then apply Faraday's law for the rate. Never forget the area ratio — it's the most common trick in exam problems.
Concept: Standard Electrode Potentials — A more negative reduction potential means the metal is a stronger reducing agent (it loses electrons more readily).
Reasoning:
- Reducing power is the ability to donate electrons. The more negative the standard reduction potential (E∘), the stronger the reducing agent.
- Arrange the given E∘ values from most negative to most positive: K+/K=−2.93 V (most negative → strongest reducing agent) Mg2+/Mg=−2.37 V Cr3+/Cr=−0.74 V Hg2+/Hg=0.79 V Ag+/Ag=0.80 V (most positive → weakest reducing agent)
- The increasing order of reducing power is the reverse of this list: weakest to strongest.
The increasing order of reducing power is: Ag<Hg<Cr<Mg<K.
Reducing power increases as the standard electrode potential becomes more negative. The order of increasing reducing power is: Ag < Hg < Cr < Mg < K.
The reducing power of a metal is its ability to lose electrons and get oxidised. In electrochemistry, this is directly linked to the standard electrode potential (E∘) of the metal/metal-ion half-cell.
A more negative E∘ means the metal is more easily oxidised — it is a stronger reducing agent. A more positive E∘ means the metal is harder to oxidise — it is a weaker reducing agent (and its ions are stronger oxidising agents).
So, to arrange metals in increasing order of reducing power, we need to go from the most positive E∘ (weakest reducing agent) to the most negative E∘ (strongest reducing agent).
Let's list the given potentials:
| Metal | E∘ (V) |
|---|---|
| Ag | +0.80 |
| Hg | +0.79 |
| Cr | -0.74 |
| Mg | -2.37 |
| K | -2.93 |
-
Identify the weakest reducing agent. The most positive potential is Ag+/Ag at +0.80 V. Silver is the least willing to lose electrons, so it has the least reducing power. It comes first.
-
Next comes mercury. Hg2+/Hg is +0.79 V, very close to silver but slightly less positive. So Hg is a slightly stronger reducing agent than Ag, but still much weaker than the others. It comes second.
-
Now we cross into negative potentials. Chromium has E∘=−0.74 V. This is significantly more negative than Ag or Hg, meaning Cr is a much stronger reducing agent. It comes third.
-
Magnesium follows. Mg2+/Mg at −2.37 V is more negative than Cr, so Mg is a stronger reducing agent than Cr. It comes fourth.
-
Potassium is the strongest. K+/K at −2.93 V is the most negative potential given. Potassium is the most powerful reducing agent in this list. It comes last.
A common mistake is to confuse reducing power with the tendency to get reduced. Remember: more negative E∘ = stronger reducing agent. If you accidentally arrange by increasing tendency to get reduced (i.e., by increasing E∘), you would get the exact opposite order.
You can think of the electrochemical series as a ladder: metals at the top (like Li, K, Ca) have very negative E∘ and are strong reducing agents. Metals at the bottom (like Au, Pt, Ag) have very positive E∘ and are weak reducing agents. Here, K is near the top, Ag is near the bottom.
The increasing order of reducing power is Ag < Hg < Cr < Mg < K.
Method: Using Standard Electrode Potentials to Compare Reducing Power
Method Name: The More Negative E∘, the Stronger the Reducing Agent
Concept (Why this works)
Reducing power means the ability to lose electrons (get oxidized).
A more negative standard reduction potential (E∘) means the metal is more difficult to reduce — which means it is easier to oxidize (i.e., it is a stronger reducing agent).
Steps
-
List the given E∘ values (all are reduction potentials):
- K+/K: −2.93 V
- Mg2+/Mg: −2.37 V
- Cr3+/Cr: −0.74 V
- Hg2+/Hg: +0.79 V
- Ag+/Ag: +0.80 V
-
Arrange in increasing order of E∘ (most negative → most positive):
- −2.93 V (K)
- −2.37 V (Mg)
- −0.74 V (Cr)
- +0.79 V (Hg)
- +0.80 V (Ag)
-
Apply the rule:
More negative E∘ = stronger reducing agent.
So increasing reducing power means going from weakest (most positive) to strongest (most negative).
-
Final order (increasing reducing power):
Ag < Hg < Cr < Mg < K
Key Result
Increasing reducing power:
Ag<Hg<Cr<Mg<K
Quick Check
- Ag (+0.80 V) is the weakest reducing agent — it prefers to stay as Ag+ rather than lose electrons.
- K (−2.93 V) is the strongest — it readily loses electrons to become K+.
Mistake 1: Confusing Reducing Power with Oxidising Power
The error:
Students often think: "Higher (more positive) electrode potential = stronger reducing agent."
This is wrong. Reducing power is the ability to lose electrons (get oxidised). A more negative E∘ means the metal is more eager to give away electrons.
How to avoid:
Remember the mnemonic:
More negative = more reactive (as a reducing agent).
- K+/K=−2.93 V -> very strong reducing agent
- Ag+/Ag=+0.80 V -> very weak reducing agent
Correct order (increasing reducing power):
Ag<Hg<Cr<Mg<K
Mistake 2: Forgetting the Sign Convention
The error:
Some students rank by absolute value (ignoring the negative sign), e.g., putting K and Mg in the middle.
How to avoid:
Always compare the actual signed values on a number line:
-3.0 V -2.0 V -1.0 V 0 V +1.0 V
K Mg Cr Hg Ag
(most negative = strongest reducing agent)
Increasing reducing power = from most positive to most negative E∘.
Mistake 3: Mixing Up the Order (Ascending vs Descending)
The error:
The question asks for increasing order of reducing power. Students often write the decreasing order (strongest first).
How to avoid:
- Increasing = weakest first -> strongest last
- Decreasing = strongest first -> weakest last
For this data:
- Increasing reducing power: Ag<Hg<Cr<Mg<K
- Decreasing reducing power: K>Mg>Cr>Hg>Ag
Mistake 4: Not Writing the Metal Symbols Correctly
The error:
Writing K+, Ag+ etc. instead of the metal (K, Ag). The question asks for metals, not ions.
How to avoid:
The reducing agent is the metal in its elemental form (M), not the ion (Mn+). Always list the neutral metal.
Final Correct Answer
Increasing order of reducing power:
Ag<Hg<Cr<Mg<K
Reasoning:
- Ag+/Ag=+0.80 V -> weakest reducing agent
- K+/K=−2.93 V -> strongest reducing agent
Quick Checklist to Avoid These Mistakes
| Mistake | Fix |
|---|---|
| Confusing reducing/oxidising power | More negative E∘ = stronger reducing agent |
| Ignoring negative signs | Plot on a number line |
| Reversing order | Read "increasing" carefully |
| Writing ions instead of metals | List only the neutral metal symbols |
Showing the 12 most recent of 16 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
To decide which is easier to oxidise, we look at the reverse reactions. The more negative the reduction potential, the easier it is to oxidise the reduced form. Here, water (or OH−) has a lower reduction potential (+1.23 V) than chlorine (+1.36 V). So water should be oxidised more readily — but only if concentrations are equal.
TipThe Nernst equation is the key: for the chlorine half-reaction, E=E∘−20.059logPCl2[Cl−]2. In very dilute NaCl, [Cl−] is extremely small, making logPCl2[Cl−]2 very negative, so E becomes much larger than +1.36 V. That means chlorine evolution becomes even harder (requires a more positive potential). Meanwhile, the oxygen evolution potential is nearly independent of [Cl−] (it depends on pH, which stays near neutral). So water oxidation wins decisively.
Result at anode: O2 gas is evolved. This matches option (C).
3. Eliminating the wrong options
- (A) H2 at anode: Hydrogen is produced at the cathode, not the anode. Anode is where oxidation occurs — hydrogen would need to be oxidised, but there’s no H2 present initially.
- (B) Na at cathode: As argued, water reduction outcompetes sodium ion reduction. Sodium metal is never formed in aqueous solution.
✓Final answerThe correct options are (C) and (D): O2 gas is evolved at the anode and H2 gas is evolved at the cathode.
- 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.
4. Gibbs energy.
ΔrGo=−nFEcello=−(2)(96500 C mol−1)(1.56 V)
ΔrGo=−301080 J mol−1=−301.080 kJ mol−1
The negative value confirms the reaction is spontaneous, consistent with the positive Ecello.
✓Final answerΔrGo=−301.080 kJ mol−1 — option (A).
- 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)
E(cell) = -0.44 + 0.76 = +0.32 V
The positive value confirms the reaction (Zn + Fe2+ -> Zn2+ + Fe) is spontaneous.
✓Final answer(B) 0.32 V.
- 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 Ecell=Eoxidation,anode+Ereduction,cathode, which is mathematically the same subtraction in disguise. Since the statement explicitly calls both 'reduction potentials' and says they are added, it is not correct as worded.
✓Final answerFalse.
- 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).
Ranking E° from most positive (weakest reducing agent) to most negative (strongest reducing agent):
Ag(+0.80 V)>Hg(+0.79 V)>Mg(−2.37 V)>K(−2.93 V)
So reducing power increases in the reverse order:
Ag<Hg<Mg<K
✓Final answerIncreasing order of reducing power: Ag < Hg < Mg < K (potassium is the strongest reducing agent, silver the weakest).
- 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.
- Predicting displacement reactions: a metal higher up in the reactivity order (more negative E°, i.e. a stronger reducing agent) can displace a metal lower in the series from a solution of its salt — e.g. Zn (more negative E°) displaces Cu from CuSO4 solution.
(Other valid applications include calculating standard cell EMF, and predicting the relative strength of oxidizing/reducing agents.)
✓Final answer- To predict the feasibility (spontaneity) of a given redox reaction;
- To predict which metal can displace another metal from a solution of its salt (relative reactivity of metals).
- 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.
-
Apply the principle of preferential discharge.
During electrolysis, the species with the higher (less negative) reduction potential gets reduced first. So water is reduced at the cathode, producing hydrogen gas and hydroxide ions, not sodium metal.
-
Check the options.
- (A) Oxidation of Cl− — this happens at the anode, not the cathode.
- (B) Reduction of Na+ — thermodynamically unfavourable compared to water.
- (C) Oxidation of H2O — oxidation occurs at the anode.
- (D) Reduction of H2O — this is exactly what happens.
TipA quick way to remember: In aqueous electrolysis, if the cation is from a highly reactive metal (Group 1 or 2, like Na, K, Mg, Ca), water is reduced instead. The metal ion stays in solution. This is why electrolysis of aqueous NaCl gives H2 at the cathode, not Na metal.
For competing reductions at the cathode:
The species with the higher (less negative) E∘ is reduced first.
✓Final answerThe correct option is (D) Reduction of H2O.
- 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− occurs at the zinc anode. The electrode at which reduction (gain of electrons) occurs is the cathode, the positive electrode.
✓Final answerOxidation occurs at the anode (negative electrode).
- 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
E-degree(cell) = E-degree(cathode) - E-degree(anode) = 0.34 V - (-0.25 V) = 0.59 V
Since this is positive, the cell reaction as written is spontaneous.
✓Final answer(b) +0.59 V.
- 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:
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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.
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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).
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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.
Watch outDon't confuse the sign convention. A positive Ecell∘ corresponds to a negative ΔG∘ because of the minus sign in the relationship. Students sometimes flip this, thinking "positive energy" means "positive ΔG," but thermodynamically, releasing energy means losing free energy (negative ΔG).
TipRemember the mnemonic: Spontaneous = Supplies energy. A spontaneous electrochemical reaction supplies electrical energy (positive voltage) to the external circuit, which means it's releasing Gibbs free energy (negative ΔG).
Checking the options:
- (A) positive ΔG, negative Ecell∘: non-spontaneous reaction
- (B) negative ΔG, negative Ecell∘: contradicts ΔG∘=−nFEcell∘
- (C) negative ΔG, positive Ecell∘: consistent with spontaneity ✓
- (D) positive ΔG, positive Ecell∘: contradicts the fundamental equation
✓Final answerThe correct option is (C): ΔG is negative and Ecell∘ is positive for a spontaneous reaction.
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- CBSE 2023Set 56/3/11 markMCQQ.Assertion (A): Electrolysis of aqueous solution of NaCl gives chlorine gas at anode instead of oxygen gas. Reason (R): Formation of oxygen gas at anode requires overpotential. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true.
›Reveal solutionSolution
In the electrolysis of aqueous NaCl, chlorine is produced at the anode instead of oxygen because the overpotential for oxygen evolution makes the actual potential needed for oxygen formation higher than that for chlorine, even though the standard potential for oxygen is lower. Both Assertion and Reason are true, and the Reason correctly explains the Assertion — so the answer is (A).
Why this question is about real-world electrochemistry
Standard electrode potentials tell you which reaction is thermodynamically favoured. But electrolysis happens under kinetic conditions. The key twist here: oxygen evolution at an inert anode (like platinum or graphite) has a large overpotential — an extra voltage needed to overcome the activation barrier. Chlorine evolution, on the other hand, has a much smaller overpotential. So the reaction that actually occurs at the anode is not the one with the lower standard potential, but the one that requires the lower actual voltage (standard potential + overpotential).
Let’s see the numbers.
1. What are the possible anode reactions?
In aqueous NaCl, the solution contains these ions:
Na+, Cl−, H+ (from water), and OH− (from water).
At the anode, oxidation happens. The two candidates are:
- Oxidation of chloride ions:
2Cl−→Cl2+2e−E∘=+1.36 V
- Oxidation of water (to oxygen):
2H2O→O2+4H++4e−E∘=+1.23 V
NoteStandard potentials are given as reduction potentials. For oxidation, we reverse the sign. But when comparing which oxidation is easier, we compare the actual potentials needed — the more negative the oxidation potential (or the lower the reduction potential), the easier it is to oxidise. Here, water oxidation has E∘=+1.23 V (reduction), so its oxidation potential is −1.23 V. Chloride oxidation has E∘=+1.36 V (reduction), so its oxidation potential is −1.36 V. Since −1.23>−1.36, water oxidation is thermodynamically easier — it should occur first.
So why doesn’t it?
2. The role of overpotential
Overpotential (η) is the extra voltage beyond the thermodynamic value required to drive a reaction at a noticeable rate. For oxygen evolution on common anode materials (Pt, graphite), η is substantial — typically around 0.4–0.6 V. For chlorine evolution on the same materials, η is very small (often <0.1 V).
So the actual potential needed for each reaction is:
- For oxygen:
Eactual(O2)=1.23 V+ηO2≈1.23+0.5=1.73 V
- For chlorine:
Eactual(Cl2)=1.36 V+ηCl2≈1.36+0.05=1.41 V
Now compare: chlorine requires a lower actual voltage (1.41 V) than oxygen (1.73 V). So chlorine is produced preferentially.
Watch outA common mistake is to compare only the standard potentials and conclude oxygen should form. That would be correct only if overpotentials were zero. In real electrolysis, overpotential flips the order.
3. Why the Reason is correct
The Reason states: “Formation of oxygen gas at anode requires overpotential.” This is true — and it is precisely this overpotential that makes oxygen evolution harder than chlorine evolution under these conditions. Without it, oxygen would be the product. So the Reason is the correct explanation for the Assertion.
TipOverpotential is why many electrolysis predictions based solely on E∘ fail. Always ask: “Is there a significant overpotential for one of the products?” For gases on inert electrodes, oxygen almost always has a high overpotential; hydrogen does too, but less so.
4. Evaluating the options
- (A) Both true, Reason explains Assertion — this matches our analysis.
- (B) Both true, but Reason does not explain — false, because overpotential is the very reason.
- (C) Assertion true, Reason false — false, Reason is true.
- (D) Assertion false — false, Assertion is true (chlorine is produced at the anode in practice).
✓Final answerThe correct option is (A) — Both Assertion and Reason are true, and the Reason correctly explains the Assertion.
- CBSE 2023Set ANNUAL1 markMCQQ.When concentration of Zn2+ and Cu2+ ions is unity (1 mol dm-3), then electrical potential of Daniell cell will be -(a) 0.00 V(b) 1.10 V(c) 1.35 V(d) 2.00 V
›Reveal solutionSolution
A Daniell cell is Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s); its EMF is the difference of the two standard reduction potentials, and at unit concentration this IS the standard cell potential.
The Daniell cell has the cell reaction Zn(s) + Cu2+(aq) -> Zn2+(aq) + Cu(s), with Zn as the anode (oxidation) and Cu as the cathode (reduction).
Standard reduction potentials: E-standard(Cu2+/Cu) = +0.34 V, E-standard(Zn2+/Zn) = -0.76 V.
E-cell-standard = E-cathode-standard - E-anode-standard = 0.34 - (-0.76) = 1.10 V.
Since both Zn2+ and Cu2+ are at unit concentration (1 mol dm^-3), the Nernst equation's log term is zero (log 1 = 0), so the actual cell potential equals the standard potential.
✓Final answer(b) 1.10 V.
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