(a) (i) Calculate the electrode potential of a half-cell for zinc electrode dipping in 0.01 M ZnSO₄ solution a

Question

Q. (a)

(i) Calculate the electrode potential of a half-cell for zinc electrode dipping in

0.01

ZnSO_4

solution at

25^\circ

C. Given :

E^\circ_{Zn^{2+}/Zn} = -0.76

V [

\log 10 = 1

]

(ii) Write anode, cathode and overall reaction involved in dry cell.

(iii) Equilibrium constant (

K_c

) is related to

E^\circ_{cell}

, but not to

E_{cell}

. Why ?

(OR)

(b)

(i) The conductivity of

0.001

M solution of acetic acid is

3.905 \times 10^{-5}

S cm

^{-1}

. Calculate its molar conductivity and degree of dissociation (

\alpha

). Given :

\lambda^\circ_{CH_3COO^-} = 40.9

S cm

^2

mol

^{-1}

\lambda^\circ_{H^+} = 349.6

S cm

^2

mol

^{-1}

(ii) Give reasons for the following : (I) Why does a mercury cell deliver a constant voltage for its entire life ? (II) Why is it necessary to use salt bridge in a galvanic cell ?

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Part (a)Concept understanding — Nernst Equation

The Nernst Equation: Why Batteries Don't Always Give Their Rated Voltage

Imagine you have a fresh AA battery. It says 1.5 V on the side. But if you measure it with a voltmeter, you might get 1.58 V when it's new, and 1.2 V when it's almost dead. Why does the voltage change? The Nernst equation is the tool that tells you exactly why.

The Core Idea: Concentration Drives Voltage

Every electrochemical cell works because of a chemical reaction that wants to happen. But here's the key: how badly the reaction wants to happen depends on how much of each chemical is present.

Think of it like a slope. A steep hill gives you more energy when you roll down. A shallow hill gives you less. In a battery, the "hill" is the difference in concentration (or more precisely, activity) of ions between the two electrodes. When the battery is fresh, the hill is steep — lots of reactants, few products. As the battery runs, reactants get used up, products build up, the hill flattens, and the voltage drops.

The Nernst equation is the mathematical formula that calculates the exact voltage for any given set of concentrations.

The Precise Statement

For a general electrochemical reaction:

aA + bB \rightarrow cC + dD

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

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

Where:

$E$ = cell potential under the given conditions (what you actually measure)
$E^\circ$ = standard cell potential (the voltage when all reactants and products are at 1 M concentration, 1 atm pressure, 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 reaction
$F$ = Faraday constant (96,485 C/mol)
$Q$ = reaction quotient = $\frac{[C]^c [D]^d}{[A]^a [B]^b}$ (using concentrations for now)

At 25°C (298 K), the constants combine into a simpler form:

E = E^\circ - \frac{0.0592}{n} \log_{10} Q

Note

The 0.0592 comes from $\frac{2.303RT}{F}$ at 298 K. The 2.303 converts natural log to base-10 log, which is more convenient for calculations.

What It Actually Means

The equation has three parts:

$E^\circ$ — the "ideal" voltage when everything is at standard conditions. This is what you'd get in a textbook table.
$\frac{RT}{nF}$ — a scaling factor. It tells you how sensitive the voltage is to concentration changes. More electrons transferred ( $n$ ) means less sensitivity.
$\ln Q$ — the "concentration penalty". When $Q$ is small (lots of reactants, few products), $\ln Q$ is negative, so $E$ is higher than $E^\circ$ . When $Q$ is large (products building up), $\ln Q$ is positive, so $E$ drops below $E^\circ$ .

A Concrete Example

Consider the Daniell cell: $\text{Zn} | \text{Zn}^{2+} || \text{Cu}^{2+} | \text{Cu}$

The reaction is: $\text{Zn} + \text{Cu}^{2+} \rightarrow \text{Zn}^{2+} + \text{Cu}$

$E^\circ = 1.10 \text{ V}$ , $n = 2$

If $[\text{Cu}^{2+}] = 0.1 \text{ M}$ and $[\text{Zn}^{2+}] = 1.0 \text{ M}$ :

Q = \frac{[\text{Zn}^{2+}]}{[\text{Cu}^{2+}]} = \frac{1.0}{0.1} = 10

$E = 1.10 - \frac{0.0592}{2} \log_{10}(10) = 1.10 - 0.0296 \times 1 = 1.07 \text{ V}$ …

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): Nernst gives $E = -0.819$ V; dry-cell reactions stated; $K_c$ relates only to the constant $E^\circ_{cell}$ (since $E_{cell}$ varies with concentration and is 0 at equilibrium).

Part (b): acetic acid $\Lambda_m = 39.05$ , $\Lambda_m^\circ = 390.5$ , $\alpha = 0.1$ ; mercury cell holds constant voltage (solids/pure liquids); salt bridge maintains neutrality.

Part (a)

(i) Electrode potential of the Zn half-cell

For $Zn^{2+} + 2e^- \rightarrow Zn(s)$ at 25 °C:

E = E^\circ - \frac{0.059}{n}\log\frac{1}{[Zn^{2+}]}

With $n=2$ , $E^\circ=-0.76$ V, $[Zn^{2+}]=0.01$ M:

E = -0.76 - \frac{0.059}{2}\log\frac{1}{0.01} = -0.76 - \frac{0.059}{2}(2) = -0.76 - 0.059 = -0.819\ \text{V}

(ii) Dry cell (Leclanché) reactions

Anode: $Zn \rightarrow Zn^{2+} + 2e^-$
Cathode: $2MnO_2 + 2NH_4^+ + 2e^- \rightarrow Mn_2O_3 + 2NH_3 + H_2O$
Overall: $Zn + 2MnO_2 + 2NH_4^+ \rightarrow Zn^{2+} + Mn_2O_3 + 2NH_3 + H_2O$

(iii) Why $K_c$ relates to $E^\circ_{cell}$ , not $E_{cell}$

Nernst: $E_{cell} = E^\circ_{cell} - \frac{0.059}{n}\log Q$ . At equilibrium $Q=K_c$ and $E_{cell}=0$ , so

$E^\circ_{cell} = \frac{0.059}{n}\log K_c \quad(\Delta G^\circ = -nFE^\circ_{cell} = -RT\ln K_c).$ …

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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 41 on this concept.

CBSE 2025Set 56/4/11 markMCQ
$2Cu^{+} (aq) + Zn (s) \rightarrow 2Cu (s) + Zn^{2+} (aq)$
›Reveal solutionSolution
The cell voltage depends on the reaction quotient via the Nernst equation. As the reaction proceeds, $[Zn^{2+}]$ increases and $[Cu^+]$ decreases, so the voltage decreases. The correct option is (B).

The Nernst equation tells us that the actual voltage of an electrochemical cell under non-standard conditions is:
$E_{\text{cell}} = E^\circ_{\text{cell}} - \frac{0.059}{n} \log Q$
where $Q$ is the reaction quotient. For the given reaction:
$2Cu^+ (aq) + Zn (s) \rightarrow 2Cu (s) + Zn^{2+} (aq)$
the reaction quotient is:
$Q = \frac{[Zn^{2+}]}{[Cu^+]^2}$
(Remember: pure solids like Zn and Cu have activity = 1, so they don’t appear in $Q$ .)

The number of electrons transferred, $n$ , is 2 (each Cu⁺ gains one electron, and two Cu⁺ ions are reduced; Zn loses two electrons).

So the Nernst equation becomes:
$E_{\text{cell}} = 1.28 - \frac{0.059}{2} \log \frac{[Zn^{2+}]}{[Cu^+]^2}$
Now, as the reaction progresses:

$[Zn^{2+}]$ increases — Zn metal is oxidised to Zn²⁺, so its concentration in solution rises.

$[Cu^+]$ decreases — Cu⁺ ions are reduced to Cu metal, so their concentration falls.

Both changes make the fraction $\frac{[Zn^{2+}]}{[Cu^+]^2}$ larger.

A larger $Q$ means $\log Q$ is larger (more positive).

Since we subtract this term, $E_{\text{cell}}$ decreases.

Watch out

A common mistake is to think that because $[Zn^{2+}]$ appears in the numerator, the voltage might increase. But the Nernst equation has a minus sign in front of the log term — so anything that increases $Q$ actually lowers the voltage. …
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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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CBSE 2025Set ANNUAL1 markMCQ
$Q. Equivalent conductances of sodium acetate, sodium chloride and hydrochloric acid at infinite dilution are 224, 38.2, 203 ohm^-1 cm^2 eqv^-1 respectively at 298K. So the (lambda)0 CH3COOH is:$
(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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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
$Q. The formula used to calculate molar conductivity of an electrolyte is _____.$
(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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CBSE 2024Set A11 markMCQ
$Q. When the concentration of electrolytic solution approaches zero, the resulting molar conductivity is known as ;$
(a) specific conductance
(b) resistivity
(c) conductivity
(d) limiting molar conductivity
›Reveal solutionSolution

Molar conductivity at zero concentration (infinite dilution) is called the limiting molar conductivity — option (d).

Molar conductivity $\Lambda_m$ increases as an electrolytic solution is diluted, because more of the electrolyte is present as free, effectively conducting ions. As the concentration approaches zero (infinite dilution), $\Lambda_m$ reaches a limiting maximum value denoted $\Lambda_m^\circ$ , the **limiting molar co …
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CBSE 2024Set B1 mark
$Q. Answer in one word/sentence: Write the unit of Equivalence conductivity.$
›Reveal solutionSolution

Equivalent conductivity is conductivity per gram-equivalent of electrolyte per unit volume, giving units of S cm^2 eq^-1.

Equivalent conductivity, $\Lambda_{eq}$ , is defined as $\Lambda_{eq} = \kappa \times V$ , where $\kappa$ (specific conductivity) has units of S cm^-1 (ohm^-1 cm^-1) and V is the volume in cm^3 containing one gram-equivalent of …

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CBSE 2024Set ANNUAL1 mark
$Q. In an electrochemical cell the free energy change is related to EMF of the cell as ______.$
›Reveal solutionSolution

The free energy change of a cell reaction is related to its EMF by Delta G = -nFE, which is the thermodynamic basis for the Nernst equation.

The electrical work done by a galvanic cell is equal to the product of the total charge passed and the EMF of the cell. The total charge passed when n moles of electrons flow is nF (F = Faraday constant = 96500 C/mol).

Maximum electrical work obtainable = nFE (E = EMF of the cell)

This maximum work done by the system equals the decrease in Gibbs free energy of the system, so:

Delta G = -nFE

…

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Q.(a)

Part (a)

(i) Electrode potential of the Zn half-cell

(ii) Dry cell (Leclanché) reactions

(iii) Why KcK_cKc​ relates to Ecell∘E^\circ_{cell}Ecell∘​, not EcellE_{cell}Ecell​

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(iii) Why $K_c$ relates to $E^\circ_{cell}$ , not $E_{cell}$

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