(a) (i) For a galvanic cell, the following half reactions are given. Decide, which will remain as reduction re

Question

Q. (a)

(i) For a galvanic cell, the following half reactions are given. Decide, which will remain as reduction reaction and which will be reversed to become an oxidation reaction. Give reason for your answer. (I)

Cr^{3+} + 3e^{-} \rightarrow Cr(s)

;

E^{\circ} = -0\cdot74

V (II)

Fe^{2+} + 2e^{-} \rightarrow Fe(s)

;

E^{\circ} = -0\cdot44

(ii) Represent the cell in which the following reaction takes place :

Mg(s) + 2Ag^{+} (0\cdot001\ M) \rightarrow Mg^{2+} (0\cdot100\ M) + 2Ag(s)

Calculate

E_{cell}

E^{\circ}_{cell} = 3\cdot17

V. (log 10 = 1)

(OR)

(b)

(i) State Kohlrausch's law. Give any two applications of it.

(ii)

\Lambda^{\circ}_{m}\,NH_4Cl

\Lambda^{\circ}_{m}\,NaOH

and

\Lambda^{\circ}_{m}\,NaCl

are 129·8, 217·4 and 108·9 S cm

^2

mol

^{-1}

respectively. Molar conductivity of

1 \times 10^{-2}

M solution of

NH_4OH

is 9·33 S cm

^2

mol

^{-1}

. Calculate the degree of dissociation (

\alpha

) of

NH_4OH

solution at this concentration.

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Part (a)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.

--- …

Part (b)Concept understanding — Molar Conductivity

From Resistance to Conductance: Flipping the Idea

You already know resistance ( $R$ ) — it tells you how much a material opposes the flow of current. A high resistance means the wire fights the current; a low resistance means it lets current through easily.

Now flip that thought. Instead of asking "how much does it resist?", ask "how easily does it let current flow?" That's exactly what conductance measures.

Note

Conductance ( $G$ ) is the reciprocal of resistance:

$G = \frac{1}{R}$

Unit: siemens (S) — named after Werner von Siemens. 1 S = 1 A/V (ampere per volt).

If a wire has $R = 10\ \Omega$ , its conductance is $G = 0.1\ \text{S}$ . If $R = 0.5\ \Omega$ , $G = 2\ \text{S}$ — it conducts twice as well.

Ohm's Law in Conductance Form

You know $V = IR$ . Rearranging:

I = \frac{V}{R} = G V

So current = conductance × voltage. A high-conductance material draws a large current for the same voltage — it's a "good conductor."

Now, Conductivity: The Material's Intrinsic Property

Resistance depends on two things: the material itself (its "resistivity" $\rho$ ) and the geometry (length $L$ , cross-sectional area $A$ ):

R = \rho \frac{L}{A}

Conductance also depends on geometry. A thicker wire (larger $A$ ) or a shorter wire (smaller $L$ ) has higher conductance. To isolate the material's inherent ability to conduct, we define conductivity ( $\sigma$ ):

\sigma = \frac{1}{\rho}

Conductivity is the reciprocal of resistivity. It tells you how well the material itself conducts, independent of shape and size.

Unit: siemens per metre (S/m).
High $\sigma$ → good conductor (copper: $\approx 5.8 \times 10^7\ \text{S/m}$ ).
Low $\sigma$ → poor conductor / insulator (glass: $\approx 10^{-12}\ \text{S/m}$ ).

Watch out

Don't confuse conductance (property of a specific object, depends on geometry) with conductivity (property of the material, independent of geometry). A short thick copper wire has high conductance; a long thin copper wire has lower conductance — but both have the same conductivity.

The Big Picture in One Table

Quantity	Symbol	Definition	Depends on	Unit
Resistance	$R$	$V/I$	Material + geometry	$\Omega$
Resistivity	$\rho$	$R A / L$	Material only	$\Omega \cdot \text{m}$
Conductance	$G$	$1/R$	Material + geometry	S
Conductivity	$\sigma$	$1/\rho$	Material only	S/m

Intuitive Analogy

Think of a water pipe:

Resistance = how hard it is to push water through (narrow, long pipe).
Conductance = how easily water flows (wide, short pipe). …

Why this formula?

Conductance and Conductivity: Why the Formulas Hold

Let's build this from first principles — understanding the why before the what.

1. The Core Idea: How Easily Does Current Flow?

Think of a conductor (like a copper wire). When you apply a voltage across it, electrons drift through the material. Two questions arise:

How much current flows for a given voltage? → This is conductance ( $G$ ).
How well does the material itself allow current? → This is conductivity ( $\sigma$ ).

The key distinction: Conductance depends on the size and shape of the object. Conductivity is an intrinsic property of the material.

2. Ohm's Law in Terms of Conductance

You know Ohm's law:

V = IR

But we can rewrite it as:

I = \frac{V}{R}

Define conductance $G$ as the reciprocal of resistance:

G = \frac{1}{R}

So:

I = G V

Why this makes sense:

A larger $G$ means more current for the same voltage — the conductor "conducts" better.
$G$ has units of siemens (S) = $\text{A/V}$ .

3. From Resistance to Conductivity: The Geometry Factor

Resistance of a uniform conductor depends on:

Length $L$ (longer → more resistance)
Cross-sectional area $A$ (thicker → less resistance)
Material property $\rho$ (resistivity)

The formula:

R = \rho \frac{L}{A}

Now, conductivity $\sigma$ is the reciprocal of resistivity:

\sigma = \frac{1}{\rho}

So:

R = \frac{1}{\sigma} \cdot \frac{L}{A}

Why this form?

If you double the length, electrons have to travel twice as far, colliding more → resistance doubles.
If you double the area, there's twice as many "lanes" for electrons → resistance halves.

4. The Key Formula: Conductance in Terms of Conductivity

Since $G = 1/R$ , we get:

G = \sigma \frac{A}{L}

This is the central relationship. Let's see why it holds:

$\sigma$ tells you how well the material conducts (intrinsic).
$A/L$ tells you how the geometry amplifies or reduces that.

Intuition:

A fat, short wire ( $A$ large, $L$ small) has high conductance.
A thin, long wire ( $A$ small, $L$ large) has low conductance.
A material with high $\sigma$ (like copper) gives higher $G$ than one with low $\sigma$ (like iron), for the same shape.

5. Microscopic Derivation (Why $\sigma$ Exists)

At the microscopic level, conductivity arises from electron motion:

\sigma = n e \mu

Where:

$n$ = number of free electrons per unit volume
$e$ = electron charge …

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Part (a): Higher- $E^\circ$ $Fe^{2+}/Fe$ stays reduction (cathode); $Cr^{3+}/Cr$ reverses to oxidation. Cell $Mg|Mg^{2+}||Ag^+|Ag$ , $E_{cell}=3.17-\frac{0.0591}{2}(5)=3.02$ V.

Part (b): Kohlrausch's law of independent ion migration; $\Lambda^\circ_m(NH_4OH)=129.8+217.4-108.9=238.3$ , so $\alpha=9.33/238.3=0.039$ .

Part (a)

(i) In a galvanic cell the half-reaction with the more positive (higher) standard reduction potential occurs as reduction at the cathode; the other is reversed to oxidation at the anode.

Comparing $E^\circ$ : $Fe^{2+}/Fe = -0.44$ V $>$ $Cr^{3+}/Cr = -0.74$ V.

$Fe^{2+}+2e^-\rightarrow Fe$ remains a reduction (cathode) because its $E^\circ$ is higher.
$Cr^{3+}/Cr$ is reversed to oxidation (anode): $Cr(s)\rightarrow Cr^{3+}+3e^-$ .

(ii) For $Mg(s)+2Ag^{+}\rightarrow Mg^{2+}+2Ag(s)$ , Mg is oxidised (anode, left) and Ag $^+$ reduced (cathode, right):

Mg\,|\,Mg^{2+}(0.100\ M)\,||\,Ag^{+}(0.001\ M)\,|\,Ag

Applying the Nernst equation ( $n=2$ ):

E_{cell}=E^\circ_{cell}-\frac{0.0591}{n}\log\frac{[Mg^{2+}]}{[Ag^{+}]^2}

$Q=\frac{0.100}{(0.001)^2}=\frac{0.100}{1\times10^{-6}}=1\times10^{5}, \qquad \log Q = 5$ …

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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 46 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 2026Set ANNUAL1 markMCQ
$Q. Consider the following statements about a reaction at equilibrium: A(g) + B(g) \leftrightarrow C(g). Statement I: Adding an inert gas at constant volume will shift the equilibrium to the right. Statement II: A catalyst changes the position of equilibrium.$
(a) i) Both statement I and II are correct
(b) ii) Both statement I and II are incorrect
(c) iii) Statement I is correct and statement II is incorrect
(d) iv) Statement I is incorrect and statement II is correct
›Reveal solutionSolution
[!TLDR]

ii) Both statement I and II are incorrect

Why

Adding an inert gas at constant volume does not change partial pressures/concentrations of reacting species, so it does not shift equilibrium (Statement I false). A catalyst speeds up attainment of equilibrium equally in …
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CBSE 2025Set ANNUAL1 mark
$Q. What is the SI unit of molar conductivity?$
›Reveal solutionSolution

Molar conductivity's SI unit is S m² mol⁻¹.

Molar conductivity $\Lambda_m = \dfrac{\kappa}{C}$ , where $\kappa$ (conductivity) has SI unit $S\,m^{-1}$ and concentration $C$ has SI unit $mol\,m^{-3}$ .

$\Lambda_m = \dfrac{S\,m^{-1}}{mol\,m^{-3}} = S\,m^2\,mol^{-1}$

…

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CBSE 2025Set ANNUAL1 mark
$Q. Define the following — Limiting molar conductivity$
›Reveal solutionSolution

Limiting molar conductivity is molar conductivity extrapolated to zero concentration.

Limiting molar conductivity ( $\Lambda_m^0$ or $\Lambda_m^\infty$ ) is the molar conductivity of an electrolyte solution when the concentration approaches zero (i.e. at infinite dilution). At infinite dilution, dissociation of the electrolyte is essentially complete and inter-ionic attractions vanish, so each ion conducts independently and to its maximum extent. For strong electrolytes, $\Lambda_m^0$ is obtained by extrapolating the $\Lambda_m$ …

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$Q. Equivalent conductances of sodium acetate, sodium chloride and hydrochloric acid at infinite dilution are 224, 38.2, 203 ohm^-1 cm^2 eqv^-1 respectively at 298K. So the (lambda)0 CH3COOH is:$
(a) 288.5 ohm^-1 cm^2 eqv.^-1
(b) 288.8 ohm^-1 cm^2 eqv.^-1
(c) 388.8 ohm^-1 cm^2 eqv.^-1
(d) 59.2 ohm^-1 cm^2 eqv.^-1
›Reveal solutionSolution

λ0(CH3COOH) = λ0(CH3COONa) + λ0(HCl) − λ0(NaCl) = 224 + 203 − 38.2 = 388.8 ohm^-1 cm^2 eqv^-1.

CH3COOH is a weak electrolyte, so its limiting equivalent conductance cannot be found by direct extrapolation. Instead, Kohlrausch's law of independent migration of ions lets us combine the limiting conductances of related strong electrolytes.

We want λ0(CH3COO-) + λ0(H+). Note that:

λ0(CH3COONa) = λ0(CH3COO-) + λ0(Na+) = 224

λ0(HCl) = λ0(H+) + λ0(Cl-) = 203

λ0(NaCl) = λ0(Na+) + λ0(Cl-) = 38.2

…

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CBSE 2025Set ANNUAL1 mark
$Q. Fill in the blank: Molar conductivity ________ with decrease in concentration.$
›Reveal solutionSolution
Molar conductivity increases as concentration decreases (i.e., on dilution), reaching a maximum limiting value at infinite dilution.

Molar conductivity is given by:

Λm = κ x 1000 / M

As a solution is diluted (concentration M decreases):

For weak electrolytes: the degree of dissociation increases sharply with dilution, so more ions are produced per mole, increasing Λm markedly. …
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CBSE 2025Set ANNUAL1 markMCQ
$Q. The unit of molar conductivity is$
(a) S cm^-2 mol^-1
(b) S cm^2 mol^-1
(c) S^-1 cm^2 mol^-1
(d) S cm^2 mol
›Reveal solutionSolution

Molar conductivity relates conductivity (S/cm) to concentration (mol/cm^3), giving the composite unit S cm^2 mol^-1.

Molar conductivity is defined as:

$\Lambda_m = \dfrac{\kappa \times 1000}{C}$

where $\kappa$ (specific conductivity) has units S cm^-1 and $C$ (concentration) has units mol L^-1 (mol per 1000 cm^3).

…

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$Zn(s)+Cu^{2+}(aq) \rightarrow Zn^{2+}(aq)+Cu(s)$
›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
$L^{-1}$
(a) 12.9 S cm $^2$ mol $^{-1}$
(b) 1.29 S cm $^2$ mol $^{-1}$
(c) 0.0129 S cm $^2$ mol $^{-1}$
(d) 129 S cm $^2$ mol $^{-1}$
›Reveal solutionSolution

Converting conductivity (per cm) into molar conductivity requires dividing by the molar concentration expressed per cm³, giving a factor of 1000 in the standard formula.

Molar conductivity is related to the specific conductivity (electrolytic conductivity, $\kappa$ ) and molar concentration $C$ (in $mol\,L^{-1}$ ) by:

$\Lambda_m = \frac{\kappa \times 1000}{C}$

…

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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 2025Set ANNUAL1 markMCQ
$Q. The formula used to calculate molar conductivity of an electrolyte is _____.$
(a) $\Lambda=\dfrac{1000c}{k}$
(b) $c=\dfrac{1000\Lambda}{k}$
(c) $\Lambda=\dfrac{1000k}{c}$
(d) $k=\dfrac{1000}{\Lambda c}$
›Reveal solutionSolution

$\Lambda_m = \dfrac{1000\,\kappa}{c}$ .

Molar conductivity ( $\Lambda_m$ ) relates to specific conductivity ( $\kappa$ ) and molar concentration $c$ (in $mol\,dm^{-3}$ ) by:

$\Lambda_m = \dfrac{\kappa \times 1000}{c}$

…

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CBSE 2025Set ANNUAL1 mark
$Q. What is the SI unit of molar conductivity? OR Write the relation between specific conductivity and molar conductivity.$
›Reveal solutionSolution

Molar conductivity's SI unit follows from $\Lambda_m = \kappa/C$ : siemens metre-squared per mole.

Molar conductivity is defined as $\Lambda_m = \dfrac{\kappa}{C}$ , where $\kappa$ (specific/electrical conductivity) has SI unit $S\,m^{-1}$ and $C$ (molar concentration) has SI unit $mol\,m^{-3}$ . Dividing, the SI unit of $\Lambda_m$ works out to

$\frac{S\,m^{-1}}{mol\,m^{-3}} = S\,m^2\,mol^{-1}.$

(In practical lab work, where $\kappa$ is often expressed in $S\,cm^{-1}$ and $C$ in $mol\,L^{-1}$ , the commonly used relation is $\Lambda_m = \dfrac{1000\,\kappa}{C}$ , giving the c.g.s.-style unit $S\,cm^2\,mol^{-1}$ .)

…

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Q.(a)

Part (a)

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