Assertion: EAg^+/Ag increases with increase in concentration of Ag^+ ions. Reason: EAg^+/Ag has a positive val

NCERT Exemplar · Q67

E_{Ag^+/Ag}

(i) Both assertion and reason are true and the reason is the correct explanation of assertion.

(ii) Both assertion and reason are true and the reason is not the correct explanation of assertion.

(iii) Assertion is true but the reason is false.

(iv) Both assertion and reason are false.

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Concept understanding — Cell Representation Nernst Equation

Cell Representation and the Nernst Equation: From Intuition to Precision

Imagine you have a Daniell cell — a zinc rod in zinc sulphate solution connected by a salt bridge to a copper rod in copper sulphate solution. You know it produces a voltage. But what happens if you dilute the copper sulphate solution? Or if you change the temperature? The voltage changes. The Nernst equation is the tool that tells you exactly how much it changes.

The Intuition First

A battery works because the two half-cells "want" to react — zinc wants to lose electrons, copper ions want to gain them. This "want" is measured as a tendency, or potential. But the strength of that tendency depends on how crowded the ions are.

Think of it like this: If you have a room full of people who all want to leave (like zinc ions wanting to form), the push to get out is stronger when the room is packed. If the room is nearly empty, the push is weaker. Similarly, for copper ions wanting to enter the metal (gain electrons), the pull is stronger when there are many copper ions around, and weaker when there are few.

The Nernst equation quantifies this: the actual cell potential depends on the concentrations (or activities) of the ions involved.

The Precise Statement

For a general cell reaction:

aA + bB \rightarrow cC + dD

The cell potential $E$ under non-standard conditions is given by:

E = E^\circ - \frac{RT}{nF} \ln Q

Where:

$E$ = cell potential under the given conditions (in volts)
$E^\circ$ = standard cell potential (when all reactants/products are at 1 M, 1 atm, 25°C)
$R$ = universal gas constant (8.314 J/mol·K)
$T$ = temperature in Kelvin
$n$ = number of moles of electrons transferred in the balanced half-reactions
$F$ = Faraday constant (96,485 C/mol)
$Q$ = reaction quotient = $\frac{[C]^c [D]^d}{[A]^a [B]^b}$ (using concentrations for dilute solutions)

At 25°C (298 K), the equation simplifies to a very practical form:

E = E^\circ - \frac{0.0591}{n} \log_{10} Q

The 0.0591 comes from $\frac{2.303RT}{F}$ at 298 K. Notice it uses $\log_{10}$ (common log), not natural log.

Cell Representation: How We Write It

In electrochemistry, we represent a cell with a shorthand notation. For the Daniell cell:

\text{Zn(s)} \mid \text{Zn}^{2+}(\text{aq}) \parallel \text{Cu}^{2+}(\text{aq}) \mid \text{Cu(s)}

The single vertical line $\mid$ represents a phase boundary (solid electrode | solution). The double line $\parallel$ represents the salt bridge.

The anode (oxidation) is written on the left, the cathode (reduction) on the right. Electrons flow from left to right in the external circuit.

Applying the Nernst Equation to a Cell Representation

For the Daniell cell, the half-reactions are:

Anode (oxidation): $\text{Zn(s)} \rightarrow \text{Zn}^{2+}(\text{aq}) + 2e^-$
Cathode (reduction): $\text{Cu}^{2+}(\text{aq}) + 2e^- \rightarrow \text{Cu(s)}$

Overall: $\text{Zn(s)} + \text{Cu}^{2+}(\text{aq}) \rightarrow \text{Zn}^{2+}(\text{aq}) + \text{Cu(s)}$

Here $n = 2$ (two electrons transferred). The reaction quotient is:

Q = \frac{[\text{Zn}^{2+}]}{[\text{Cu}^{2+}]}

So the Nernst equation becomes:

E = E^\circ - \frac{0.0591}{2} \log_{10} \frac{[\text{Zn}^{2+}]}{[\text{Cu}^{2+}]}

Note

Solids (Zn, Cu) do not appear in $Q$ because their concentrations are constant (activity = 1).

A Worked Example

Suppose you have a Daniell cell where $[\text{Zn}^{2+}] = 0.1$ M and $[\text{Cu}^{2+}] = 1.0$ M at 25°C. $E^\circ$ for the cell is 1.10 V.

$E = 1.10 - \frac{0.0591}{2} \log_{10} \frac{0.1}{1.0}$ …

Why this formula?

Cell Representation & the Nernst Equation: Why It Works

The Core Question

Why does a cell's voltage change when concentrations change? The Nernst equation answers this — but the reason lies in the link between chemical free energy and electrical work.

1. The Fundamental Link: Gibbs Free Energy & Cell Potential

A galvanic cell does electrical work. The maximum useful work a cell can do equals the change in Gibbs free energy ( $\Delta G$ ):

\Delta G = -nFE_{\text{cell}}

Where:

$n$ = moles of electrons transferred
$F$ = Faraday constant ( $96,485 \, \text{C mol}^{-1}$ )
$E_{\text{cell}}$ = cell potential (volts)

Why negative? A spontaneous reaction has $\Delta G < 0$ and $E_{\text{cell}} > 0$ — the negative sign makes this consistent.

2. The Chemical Side: $\Delta G$ Depends on Concentration

For a general redox reaction:

aA + bB \rightarrow cC + dD

The Gibbs free energy under non-standard conditions is:

\Delta G = \Delta G^\circ + RT \ln Q

Where $Q$ is the reaction quotient:

Q = \frac{[C]^c [D]^d}{[A]^a [B]^b}

Why this form? It comes from the relationship between chemical potential and concentration — the entropy of mixing drives concentration dependence.

3. Combining Both Sides: The Derivation

Set the electrical work equal to the chemical free energy change:

-nFE_{\text{cell}} = -nFE^\circ_{\text{cell}} + RT \ln Q

Divide both sides by $-nF$ :

E_{\text{cell}} = E^\circ_{\text{cell}} - \frac{RT}{nF} \ln Q

This is the Nernst equation.

4. The "Why" in Plain Terms

Concept	Physical Meaning
$E^\circ_{\text{cell}}$	Voltage when all species are at 1 M (standard state)
$-\frac{RT}{nF} \ln Q$	Correction factor — adjusts voltage for real concentrations
$Q$	Tells you how far the reaction is from equilibrium

Key insight: When $Q = K$ (equilibrium), $E_{\text{cell}} = 0$ — the battery is dead because no net reaction occurs.

5. The Common Form (log base 10)

At $25^\circ \text{C}$ ( $298 \, \text{K}$ ):

\frac{RT}{F} \ln 10 \approx 0.0592 \, \text{V}

So:

E_{\text{cell}} = E^\circ_{\text{cell}} - \frac{0.0592}{n} \log_{10} Q

Why convert to log? Exam convenience — most concentration values are powers of 10.

--- …

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The Nernst equation shows that $E_{Ag^+/Ag}$ depends on $\log[Ag^+]$ , so increasing $[Ag^+]$ raises the potential. The reason given — that $E^\circ$ is positive — is true but does not explain this change; it only describes the standard value. Hence assertion true, reason true but not the correct explanation.

The heart of this question is the Nernst equation for a metal/metal-ion electrode. For the half-cell reaction

Ag^+ + e^- \rightarrow Ag(s)

the electrode potential is not fixed — it varies with the concentration of $Ag^+$ ions in solution. The standard reduction potential $E^\circ_{Ag^+/Ag} = +0.80\ \text{V}$ is just the reference value when $[Ag^+] = 1\ \text{M}$ at 298 K.

The Nernst equation at 298 K gives:

E_{Ag^+/Ag} = E^\circ_{Ag^+/Ag} - \frac{0.059}{1} \log \frac{1}{[Ag^+]}

which simplifies to

E_{Ag^+/Ag} = E^\circ_{Ag^+/Ag} + 0.059 \log [Ag^+]

Since $\log [Ag^+]$ increases when $[Ag^+]$ increases, the whole expression $E_{Ag^+/Ag}$ increases. That is the direct, quantitative reason the assertion is true. …

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Here are the common mistakes students make on this assertion-reason question and how to avoid each.

Mistake 1: Confusing “increase in $E$ ” with “more positive $E$ ”

What students do wrong:

They think that because the standard reduction potential $E^\circ_{Ag^+/Ag} = +0.80\ \text{V}$ is positive, any increase in concentration will make $E$ even more positive — so they mark option (i) or (ii).

Why it’s wrong:

The Nernst equation for $Ag^+ + e^- \rightarrow Ag$ is:

E = E^\circ - \frac{0.059}{1} \log \frac{1}{[Ag^+]}

Simplifying:

E = E^\circ + 0.059 \log [Ag^+]

If $[Ag^+]$ increases, $\log [Ag^+]$ increases → $E$ increases (assertion is true).
But the reason says “ $E_{Ag^+/Ag}$ has a positive value” — this is a fact about $E^\circ$ , not an explanation of why $E$ changes with concentration.

How to avoid:

Always write the Nernst equation explicitly. The reason must directly cause the assertion. A positive $E^\circ$ does not explain the change in $E$ with concentration — the Nernst equation does.

Mistake 2: Thinking the reason is false

What students do wrong:

They see that $E^\circ$ is positive but think “ $E$ can become negative if $[Ag^+]$ is very low” — so they mark option (iii).

Why it’s wrong:

The reason says “ $E_{Ag^+/Ag}$ has a positive value” — this is true for the standard value ( $E^\circ = +0.80\ \text{V}$ ). The statement does not say “always positive under all conditions.” It is a true statement about the standard potential.

How to avoid:

Read the reason carefully. If it states a known standard value, it is true unless it says “under all conditions.” Here, it simply states a fact about $E^\circ$ .

Mistake 3: Choosing (i) — “reason is correct explanation”

What students do wrong:

They think: “Positive $E^\circ$ means the reaction is spontaneous, so increasing $[Ag^+]$ makes it even more spontaneous → $E$ increases.”

Why it’s wrong:

The reason (positive value) does not explain the change in $E$ with concentration. The change is governed by the log term in the Nernst equation, not by the sign of $E^\circ$ .

How to avoid: …

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Same / Similar Concept — real previous-year questions on the same or a closely similar concept, not this exact question.

Showing the 12 most recent of 13 on this concept.

CBSE 2026Set ANNUAL1 mark
$Q. What is the potential difference between the two electrodes of the galvanic cell called?$
›Reveal solutionSolution

The potential difference between the two electrodes of a galvanic cell (measured when no current is drawn) is called the electromotive force (EMF) or cell potential, $E_{\text{cell}}$ .

Concept. In a galvanic (voltaic) cell, the two half-cells are at different electrode potentials. The difference between the cathode and anode potentials is what pushes electrons through the external circuit:

$E_{\text{cell}} = E_{\text{cathode}} - E_{\text{anode}}$

…

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CBSE 2025Set ANNUAL1 mark
$Zn(s)+Cu^{2+}(aq) \rightarrow Zn^{2+}(aq)+Cu(s)$
›Reveal solutionSolution
An external potential exactly equal and opposite to the cell's own EMF brings the system to balance, so no net current flows in either direction — this is the basis of potentiometric EMF measurement.

The Daniell-type cell $Zn(s)|Zn^{2+}(aq)\|Cu^{2+}(aq)|Cu(s)$ spontaneously drives current in the galvanic direction (electrons flow from Zn anode to Cu cathode through the external circuit) with an EMF of 1.1 V under standard conditions.

If an external opposing potential is applied, it works against this spontaneous cell reaction:

If the external potential is less than 1.1 V, the cell's own EMF still dominates, and current continues to flow in the original (galvanic) direction, though at a reduced magnitude.

If the external potential is greater than 1.1 V, it overpowers the cell's own EMF, and current is forced to flow in the reverse direction (the cell now behaves as an electrolytic cell, being charged/driven backward). …
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CBSE 2025Set ANNUAL1 markMCQ
$Q. The correct statement in a cell of zinc and copper is$
(a) zinc acts as cathode and copper as anode
(b) zinc acts as anode and copper as cathode
(c) the standard reduction potential of zinc is more than that of copper
(d) the flow of electrons is from copper to zinc
›Reveal solutionSolution

Zinc has a lower (more negative) standard reduction potential than copper, so it is oxidized (anode) while copper is reduced (cathode).

In a Daniell-type zinc–copper cell, E°(Zn²⁺/Zn) = −0.76 V is lower than E°(Cu²⁺/Cu) = +0.34 V. The electrode with the lower (more negative) reduction potential is oxidized — zinc loses electrons and acts as the anode (Zn → Zn²⁺ + 2e⁻) — while the electrode with the higher reduction potential is reduced — copper gains electrons and acts as the cathode (Cu²⁺ + 2e⁻ → Cu). Electrons flow …

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CBSE 2024Set D1 markMCQ
$Q. The electromotive force of the cell Zn | ZnSO4 || CuSO4 | Cu is 1.1 volt. Its cathode is$
(a) Zn
(b) Cu
(c) ZnSO4
(d) CuSO4
›Reveal solutionSolution
Reduction happens at the cathode; Cu2+ is reduced to Cu, so Cu is the cathode.

In the Daniell cell Zn | ZnSO4 || CuSO4 | Cu:

Anode (oxidation, left): Zn -> Zn2+ + 2e-

Cathode (reduction, right): Cu2+ + 2e- -> Cu …
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CBSE 2024Set ANNUAL1 markMCQ
$Q. An electrochemical cell can behave like an electrolytic cell when _______.$
(a) Ecell = 0
(b) Ecell > Eext
(c) Eext > Ecell
(d) Ecell = Eext
›Reveal solutionSolution
A galvanic (electrochemical) cell starts behaving like an electrolytic cell when an external potential greater than the cell's own emf is applied against it, reversing the direction of current flow.

Consider a Daniell cell: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s), which normally works as a galvanic cell producing a cell potential Ecell, with electrons flowing from Zn (anode) to Cu (cathode) through the external circuit.

If an external opposing emf (Eext) is applied to this cell:

When Eext < Ecell, the cell continues to work as a galvanic cell, but the current decreases.

When Eext = Ecell, no current flows through the cell (this is used to measure the cell's emf accurately, e.g. using a potentiometer). …
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CBSE 2024Set ANNUAL1 mark
$Q. Write True/False: A hydrogen bridge is used to maintain continuity of ion flow in a Daniell cell.$
›Reveal solutionSolution

This statement is FALSE. A Daniell cell uses a salt bridge (e.g. containing KCl or KNO3 in agar-agar gel), not any "hydrogen bridge", to complete the internal circuit.

A Daniell cell consists of a Zn electrode dipped in ZnSO4 solution (anode) and a Cu electrode dipped in CuSO4 solution (cathode), connected externally by a wire and internally by a salt bridge. The salt bridge allows ions to migrate between the two half-cells, maintaining electrical neutrality in each compartment as the cell reaction proceeds, and completes the internal circuit …

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CBSE 2023Set 56/1/11 markMCQ
$Zn + 2Ag^+ \rightarrow Zn^{2+} + 2Ag$
›Reveal solutionSolution
By convention the anode (oxidation) is written on the left and the cathode (reduction) on the right. Zinc is oxidised and silver ions are reduced, so the cell is $Zn \mid Zn^{2+} \parallel Ag^+ \mid Ag$ — option (D).

A cell diagram is written anode (left) $\parallel$ cathode (right), with each half-cell running from the electrode metal outward and the double bar $\parallel$ marking the salt bridge.

For the reaction
$Zn + 2Ag^+ \rightarrow Zn^{2+} + 2Ag$

Zinc loses electrons: $Zn \rightarrow Zn^{2+} + 2e^-$ (oxidation, anode, left).

Silver ions gain electrons: $Ag^+ + e^- \rightarrow Ag$ (reduction, cathode, right).

Writing the anode as metal $\mid$ ion and the cathode as ion $\mid$ metal gives
$Zn \mid Zn^{2+} \parallel Ag^+ \mid Ag$
Checking the options: …
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CBSE 2022Set E1 markMCQ
$Q. The standard electrode potentials for the following reactions are given ( At 25°C ): Ag+(aq) + e- -> Ag(s), E° Ag+/Ag = +0.80 V ; Sn2+(aq) + 2e -> Sn(s), E° Sn2+/Sn = -0.14 V. The electromotive force (EMF) of the given cell Sn | Sn2+ (1M) || Ag+ (1M) | Ag is$
(a) 0.66 V
(b) 0.80 V
(c) 1.08 V
(d) 0.94 V
›Reveal solutionSolution
For Sn | Sn2+ || Ag+ | Ag, EMF = E°(Ag+/Ag) - E°(Sn2+/Sn) = 0.80 - (-0.14) = 0.94 V.

In the cell notation the left electrode is the anode (oxidation) and the right is the cathode (reduction):

Cathode (reduction): Ag+ + e- -> Ag, E° = +0.80 V

Anode (oxidation): Sn -> Sn2+ + 2e-, E°(Sn2+/Sn) = -0.14 V

E°cell = E°cathode - E°anode = (+0.80) - (-0.14) = +0.94 V.

…
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CBSE 2022Set ANNUAL1 markMCQ
$Q. Which one of the following statements is incorrect for a voltaic cell ?$
(a) It converts chemical energy to electrical energy.
(b) It uses electrical energy to carry out chemical changes.
(c) It is based on a redox reaction.
(d) It has $-\Delta G$ .
›Reveal solutionSolution
A voltaic cell produces electricity from a spontaneous redox reaction — it does not consume electrical energy, so statement (b) describes an electrolytic cell instead.

Checking each option against what a voltaic (galvanic) cell actually does:

(a) True — a voltaic cell converts chemical energy into electrical energy.

(b) False — this describes an electrolytic cell, which uses externally supplied electrical energy to force a non-spontaneous chemical change. A voltaic cell does the opposite. …
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CBSE 2022Set ANNUAL1 markMCQ
$Mg\,|\,Mg^{2+}\,||\,Cu^{2+}\,|\,Cu$
(a) $Mg$ as cathode
(b) $Cu$ as cathode
(c) $Cu$ is oxidizing agent
(d) None of the above
›Reveal solutionSolution
By IUPAC convention the electrode written on the LEFT of a cell is the anode and the one on the RIGHT is the cathode. Here Mg is the anode and Cu is the cathode. Option (B).

The cell is written as $Mg\,|\,Mg^{2+}\,||\,Cu^{2+}\,|\,Cu$ .

Convention: anode (negative, oxidation) is written on the left; cathode (positive, reduction) is written on the right.

The electrode reactions are:

Anode (Mg, oxidation): $Mg \rightarrow Mg^{2+} + 2e^-$

Cathode (Cu, reduction): $Cu^{2+} + 2e^- \rightarrow Cu$ …
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CBSE 2021Set A1 markMCQ
$Q. Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) is$
(a) Weston cell
(b) Daniel cell
(c) Calomel cell
(d) None of these
›Reveal solutionSolution
A zinc-copper galvanic cell with this notation is the Daniell cell.

The cell Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) is the Daniell cell, a galvanic (voltaic) cell.

At the anode (LHS): Zn(s) → Zn2+ + 2e- (oxidation).

At the cathode (RHS): Cu2+ + 2e- → Cu(s) (reduction). …
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CBSE 2018Set ANNUAL1 mark
$Q. What is salt bridge?$
›Reveal solutionSolution
The salt bridge completes the electrical circuit of a galvanic cell by letting ions migrate between the two half-cells (maintaining charge neutrality) while physically keeping the two electrolyte solutions from mixing.

A salt bridge is typically a U-shaped glass tube filled with a gel (agar-agar or gelatin) containing a concentrated solution of an inert electrolyte (one whose ions do not react with the cell's other ions and are not involved in the electrode reactions), commonly KCl, KNO $_3$ or NH $_4$ NO $_3$ . Its two functions:

It completes the internal electrical circuit of the cell, allowing ions to flow between the two half-cells, so that current continues to flow through the external circuit.

As oxidation at the anode generates excess positive ions and reduction at the cathode depletes positive ions (or vice-versa), the salt bridge's ions migrate to maintain electrical neutrality in both half-cell solutions (anions flow toward the anode compartment, cations toward the cathode compartment) — without this, charge would build up and stop the current flow almost immediately. …
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←Previous questionQ66 — Assertion: Current stops flowing when ECell = 0. Reason: Equilibrium o…→Next questionQ68 — Assertion: Copper sulphate can be stored in zinc vessel. Reason: Zinc …

Q.Assertion: $E_{Ag^+/Ag}$ increases with increase in concentration of $Ag^+$ ions.
Reason: $E_{Ag^+/Ag}$ has a positive value.

Concept understanding — Cell Representation Nernst Equation

Cell Representation and the Nernst Equation: From Intuition to Precision

The Intuition First

The Precise Statement

Cell Representation: How We Write It

Applying the Nernst Equation to a Cell Representation

A Worked Example

Why this formula?

Cell Representation & the Nernst Equation: Why It Works

The Core Question

1. The Fundamental Link: Gibbs Free Energy & Cell Potential

2. The Chemical Side: $\Delta G$ Depends on Concentration

3. Combining Both Sides: The Derivation

4. The "Why" in Plain Terms

5. The Common Form (log base 10)

Method: Nernst Equation Analysis for Electrode Potential

Mistake 1: Confusing “increase in $E$ ” with “more positive $E$ ”

Mistake 2: Thinking the reason is false

Mistake 3: Choosing (i) — “reason is correct explanation”

Q.Assertion: EAg+/AgE_{Ag^+/Ag}EAg+/Ag​ increases with increase in concentration of Ag+Ag^+Ag+ ions. Reason: EAg+/AgE_{Ag^+/Ag}EAg+/Ag​ has a positive value.

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Q.Assertion: $E_{Ag^+/Ag}$ increases with increase in concentration of $Ag^+$ ions.
Reason: $E_{Ag^+/Ag}$ has a positive value.

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