### Core Logic
Limiting molar conductivity relies heavily on the charge and hydrodynamic radius of the hydrated ion. Let us verify the standard experimental limiting molar ionic conductivities (lambda^circ$\lambda^{\circ}$) at 298text K$298\text{ K}$:
* H^+: 349.8text S cm^2text mol^-1$H^{+}: 349.8\text{ S cm}^2\text{ mol}^{-1}$ (exhibits Grotthuss proton-hopping conduction mechanism)
* Ca^2+: 119.0text S cm^2text mol^-1$Ca^{2+}: 119.0\text{ S cm}^2\text{ mol}^{-1}$
* Mg^2+: 106.1text S cm^2text mol^-1$Mg^{2+}: 106.1\text{ S cm}^2\text{ mol}^{-1}$
* K^+: 73.5text S cm^2text mol^-1$K^{+}: 73.5\text{ S cm}^2\text{ mol}^{-1}$
* Na^+: 50.1text S cm^2text mol^-1$Na^{+}: 50.1\text{ S cm}^2\text{ mol}^{-1}$
### Step 1: Trend Layout
Arranging these values in descending order yields:
H^+ > Ca^2+ > Mg^2+ > K^+ > Na^+$H^{+} > Ca^{2+} > Mg^{2+} > K^{+} > Na^{+}$
### Pattern Recognition
Shortcut: H^+$H^{+}$ always has the absolute highest value due to its unique proton-hopping transport system. For metal ions, a higher ionic charge boosts conductivity (M^2+ > M^+$M^{2+} > M^{+}$), and within a group, a smaller hydrated radius (larger bare ion) increases mobility (K^+ > Na^+$K^{+} > Na^{+}$).
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Keywords:#Limiting molar conductivity values#Hydration radius ionic mobility#Electrochemistry electrolytes JEE Main 2025#JEE Main 2025 Morning Q45
More Electrochemistry Previous-Year Questions
Q472025Conductivity and Molar Conductivity
0.2\%$0.2\%$ (w/v) solution of mathrmNaOH$\mathrm{NaOH}$ is measured to have resistivity 870.0~mathrmmOmega~m$870.0~\mathrm{m\Omega~m}$. The molar conductivity of the solution will be times 10^2~mathrmmS~dm^2~mol^-1$\times 10^{2}~\mathrm{mS~dm^{2}~mol^{-1}}$. (Nearest integer)
Numerical Answer.Answer: 23 to 23
Solution
### Related Formula
kappa = frac1rho$\kappa = \frac{1}{\rho}$Lambda_m = frackappaM$\Lambda_m = \frac{\kappa}{M}$
### Core Logic
To compute the molar conductivity, we first calculate the molarity of the solution and the conductivity of the electrolyte from the given resistivity.
### Step 1: Calculate Molarity (M)
0.2\%$0.2\%$ (w/v) mathrmNaOH$\mathrm{NaOH}$ means 0.2~mathrmg$0.2~\mathrm{g}$ of mathrmNaOH$\mathrm{NaOH}$ is present in 100~mathrmmL$100~\mathrm{mL}$ of solution.
textMolar mass of NaOH = 23 + 16 + 1 = 40~mathrmg~mol^-1$\text{Molar mass of NaOH} = 23 + 16 + 1 = 40~\mathrm{g~mol^{-1}}$textMolarity M = fractextMass of solutetextMolar mass times frac1000V_mathrmmL = frac0.240 times frac1000100 = 0.05~mathrmmol~L^-1 = 0.05~mathrmmol~dm^-3$\text{Molarity } M = \frac{\text{Mass of solute}}{\text{Molar mass}} \times \frac{1000}{V_{\mathrm{mL}}} = \frac{0.2}{40} \times \frac{1000}{100} = 0.05~\mathrm{mol~L^{-1}} = 0.05~\mathrm{mol~dm^{-3}}$
### Step 2: Calculate Conductivity (kappa) in dm Units
Given resistivity rho = 870.0~mathrmmOmega~m = 870 times 10^-3~Omega~m = 0.87~Omega~m$\rho = 870.0~\mathrm{m\Omega~m} = 870 \times 10^{-3}~\Omega~m = 0.87~\Omega~m$.
Since 1~mathrmm = 10~mathrmdm$1~\mathrm{m} = 10~\mathrm{dm}$:
rho = 0.87~Omega times (10~mathrmdm) = 8.7~Omega~dm$\rho = 0.87~\Omega \times (10~\mathrm{dm}) = 8.7~\Omega~dm$
Now, conductivity kappa$\kappa$ is:
kappa = frac1rho = frac18.7~Omega^-1~dm^-1$\kappa = \frac{1}{\rho} = \frac{1}{8.7}~\Omega^{-1}~dm^{-1}$
### Step 3: Calculate Molar Conductivity (Lambda_m)
Lambda_m = frackappaM = fracfrac18.7~mathrmS~dm^-10.05~mathrmmol~dm^-3 = frac18.7 times 0.05 = frac10.435 approx 2.29885~mathrmS~dm^2~mol^-1$\Lambda_m = \frac{\kappa}{M} = \frac{\frac{1}{8.7}~\mathrm{S~dm^{-1}}}{0.05~\mathrm{mol~dm^{-3}}} = \frac{1}{8.7 \times 0.05} = \frac{1}{0.435} \approx 2.29885~\mathrm{S~dm^2~mol^{-1}}$
Converting mathrmS$\mathrm{S}$ to mathrmmS$\mathrm{mS}$ (1~mathrmS = 10^3~mathrmmS$1~\mathrm{S} = 10^3~\mathrm{mS}$):
Lambda_m = 2.29885 times 10^3~mathrmmS~dm^2~mol^-1 = 22.9885 times 10^2~mathrmmS~dm^2~mol^-1$\Lambda_m = 2.29885 \times 10^3~\mathrm{mS~dm^2~mol^{-1}} = 22.9885 \times 10^2~\mathrm{mS~dm^2~mol^{-1}}$
Rounding off to the nearest integer gives **23**.
### Pattern Recognition
Ensure careful handling of volumetric conversions. Since concentration is expressed in moles per liter (equivalent to mathrmdm^-3$\mathrm{dm^{-3}}$), expressing conductivity in terms of mathrmdm^-1$\mathrm{dm^{-1}}$ directly eliminates the need for arbitrary 1000$1000$ multiplication factors.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Q2025Nernst Equation and Salt Hydrolysis pH
Consider the following electrochemical cell at standard condition.
mathrmAu(s) vert mathrmQH_2, mathrmQ vert mathrmNH_4mathrmX (0.01 mathrmM) vert vert mathrmAg^+ (1 mathrmM) vert mathrmAg(s)$\mathrm{Au(s)} \vert \mathrm{QH}_2, \mathrm{Q} \vert \mathrm{NH}_4\mathrm{X} (0.01 \mathrm{M}) \vert \vert \mathrm{Ag}^+ (1 \mathrm{M}) \vert \mathrm{Ag(s)}$mathrmE_textcell = +0.4 mathrmV$\mathrm{E}_{\text{cell}} = +0.4 \mathrm{V}$
The couple mathrmQH_2 / mathrmQ$\mathrm{QH}_2 / \mathrm{Q}$ represents quinhydrone electrode, the half cell reaction is given below:
The diagram displays the balanced chemical equation for quinhydrone reduction, consuming two electrons and two protons to yield hydroquinone.left[ textGiven: E_Ag^+ / Ag^o = +0.8 mathrmV text and frac2.303 RTF = 0.06 mathrmV right]$\left[ \text{Given}: E_{Ag^+ / Ag}^o = +0.8 \mathrm{V} \text{ and } \frac{2.303 RT}{F} = 0.06 \mathrm{V} \right]$
The mathrmpK_b$\mathrm{pK_b}$ value of the ammonium halide salt (mathrmNH_4mathrmX)$(\mathrm{NH}_4\mathrm{X})$ used here is _____.
Numerical Answer.Answer: 6 to 6
Solution
### Related Formula
Nernst equation for the net combined redox cell expression:
E = E^circ - frac0.062logleft(frac[mathrmH^+]^2[mathrmAg^+]^2right)$E = E^\circ - \frac{0.06}{2}\log\left(\frac{[\mathrm{H}^+]^2}{[\mathrm{Ag}^+]^2}\right)$
Hydrolysis equation for a salt composed of a weak base and strong acid:
mathrmpH = 7 - frac12mathrmpK_b - frac12logmathrmC$\mathrm{pH} = 7 - \frac{1}{2}\mathrm{pK_b} - \frac{1}{2}\log\mathrm{C}$
### Core Logic
Let's compute the operational values line-by-row:
* Combined redox process: mathrmQH_2 + 2Ag^+ rightarrow Q + 2Ag + 2H^+$\mathrm{QH_2 + 2Ag^+ \rightarrow Q + 2Ag + 2H^+}$.
* Standard cell potential difference: E^circ_textcell = E^circ_mathrmAg^+/Ag - E^circ_mathrmQ/QH_2 = 0.8 - 0.7 = +0.1mathrm~V$E^\circ_{\text{cell}} = E^\circ_{\mathrm{Ag^+/Ag}} - E^\circ_{\mathrm{Q/QH_2}} = 0.8 - 0.7 = +0.1\mathrm{~V}$.
* Apply Nernst adjustments using known concentrations ([mathrmAg^+] = 1mathrm~M$[\mathrm{Ag}^+] = 1\mathrm{~M}$):
0.4 = 0.1 - 0.06 log [mathrmH^+]$0.4 = 0.1 - 0.06 \log [\mathrm{H}^+]$0.3 = 0.06 times mathrmpH implies mathrmpH = 5$0.3 = 0.06 \times \mathrm{pH} \implies \mathrm{pH} = 5$
### Step 1: Salt Hydrolysis Substitution
Substitute the determined mathrmpH$\mathrm{pH}$ along with salt molarity (C = 0.01mathrm~M = 10^-2mathrm~M$C = 0.01\mathrm{~M} = 10^{-2}\mathrm{~M}$) into the hydrolysis equation:
5 = 7 - frac12mathrmpK_b - frac12log(10^-2)$5 = 7 - \frac{1}{2}\mathrm{pK_b} - \frac{1}{2}\log(10^{-2})$5 = 7 - frac12mathrmpK_b - frac12(-2)$5 = 7 - \frac{1}{2}\mathrm{pK_b} - \frac{1}{2}(-2)$5 = 7 - frac12mathrmpK_b + 1$5 = 7 - \frac{1}{2}\mathrm{pK_b} + 1$5 = 8 - frac12mathrmpK_b implies frac12mathrmpK_b = 3 implies mathrmpK_b = 6$5 = 8 - \frac{1}{2}\mathrm{pK_b} \implies \frac{1}{2}\mathrm{pK_b} = 3 \implies \mathrm{pK_b} = 6$
### Pattern Recognition
Quinhydrone electrodes act as excellent pH indicators in electrochemical cells. Note that each change of 1 pH unit shifts the cell output potential by exactly 0.06mathrm~V$0.06\mathrm{~V}$ at standard ambient conditions.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Class 11 Chemistry: Equilibrium
Q262025Conductometric Titrations
40mathrm~mL$40\mathrm{~mL}$ of a mixture of mathrmCH_3mathrmCOOH$\mathrm{CH}_{3}\mathrm{COOH}$ and mathrmHCl$\mathrm{HCl}$ (aqueous solution) is titrated against 0.1mathrm~M~NaOH$0.1\mathrm{~M~NaOH}$ solution conductometrically. Which of the following statements is correct? Conductance vs Volume of NaOH added curve showing two equivalence points at 2.0 mL and 5.0 mL.
A. The concentration of mathrmCH_3mathrmCOOH$\mathrm{CH}_3\mathrm{COOH}$ in the original mixture is 0.005mathrm~M$0.005\mathrm{~M}$
B. The concentration of mathrmHCl$\mathrm{HCl}$ in the original mixture is 0.005mathrm~M$0.005\mathrm{~M}$
C.mathrmCH_3mathrmCOOH$\mathrm{CH}_3\mathrm{COOH}$ is neutralised first followed by neutralisation of mathrmHCl$\mathrm{HCl}$
D. Point 'C' indicates the complete neutralisation of mathrmHCl$\mathrm{HCl}$
Solution
### Related Formula
At the equivalence point during titration:
M_textacid V_textacid = M_textbase V_textbase$M_{\text{acid}} V_{\text{acid}} = M_{\text{base}} V_{\text{base}}$
### Core Logic
In a mixture of a strong acid (mathrmHCl$\mathrm{HCl}$) and a weak acid (mathrmCH_3mathrmCOOH$\mathrm{CH}_3\mathrm{COOH}$):
1. mathrmHCl$\mathrm{HCl}$ is a strong acid and is completely ionized. When mathrmNaOH$\mathrm{NaOH}$ is added, highly mobile mathrmH^+$\mathrm{H}^+$ ions are replaced by less mobile mathrmNa^+$\mathrm{Na}^+$ ions, causing a sharp drop in conductance (segment AB).
2. At point B (2.0mathrm~mL$2.0\mathrm{~mL}$), mathrmHCl$\mathrm{HCl}$ is completely neutralized.
3. Segment BC represents the neutralization of the weak acid mathrmCH_3mathrmCOOH$\mathrm{CH}_3\mathrm{COOH}$ to form highly conducting sodium acetate, causing a moderate rise in conductance up to point C (5.0mathrm~mL$5.0\mathrm{~mL}$).
4. Beyond point C, excess mathrmOH^-$\mathrm{OH}^-$ ions cause a rapid rise in conductance (segment CD).
### Step 1: Calculate concentration of mathrmHCl$\mathrm{HCl}$
Volume of mathrmNaOH$\mathrm{NaOH}$ used to neutralize mathrmHCl$\mathrm{HCl}$ is V_1 = 2.0mathrm~mL$V_1 = 2.0\mathrm{~mL}$:
M_mathrmHCl times 40mathrm~mL = 0.1mathrm~M times 2.0mathrm~mL$M_{\mathrm{HCl}} \times 40\mathrm{~mL} = 0.1\mathrm{~M} \times 2.0\mathrm{~mL}$M_mathrmHCl = frac0.240 = 0.005mathrm~M$M_{\mathrm{HCl}} = \frac{0.2}{40} = 0.005\mathrm{~M}$
### Step 2: Calculate concentration of mathrmCH_3mathrmCOOH$\mathrm{CH}_3\mathrm{COOH}$
Volume of mathrmNaOH$\mathrm{NaOH}$ used to neutralize mathrmCH_3mathrmCOOH$\mathrm{CH}_3\mathrm{COOH}$ is V_2 = 5.0mathrm~mL - 2.0mathrm~mL = 3.0mathrm~mL$V_2 = 5.0\mathrm{~mL} - 2.0\mathrm{~mL} = 3.0\mathrm{~mL}$:
M_mathrmCH_3mathrmCOOH times 40mathrm~mL = 0.1mathrm~M times 3.0mathrm~mL$M_{\mathrm{CH}_3\mathrm{COOH}} \times 40\mathrm{~mL} = 0.1\mathrm{~M} \times 3.0\mathrm{~mL}$M_mathrmCH_3mathrmCOOH = frac0.340 = 0.0075mathrm~M$M_{\mathrm{CH}_3\mathrm{COOH}} = \frac{0.3}{40} = 0.0075\mathrm{~M}$
### Pattern Recognition
Conductometric titration curves are analyzed sequentially: the strongest electrolyte is always neutralized first. A steep drop in conductance always signals the neutralization of a strong acid (mathrmH^+$\mathrm{H}^+$ depletion). A weak acid titration shows a gentle upward slope due to salt formation.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Class 11 Chemistry: Equilibrium
Q342025Fuel Cells and Standard Cell Potential
The standard cell potential left(E_mathrmcell^ominusright)$\left(E_{\mathrm{cell}}^{\ominus}\right)$ of a fuel cell based on the oxidation of methanol in air that has been used to power television relay station is measured as 1.21mathrm~V$1.21\mathrm{~V}$. The standard half cell reduction potential for mathrmO_2$\mathrm{O}_2$left(E_mathrmO_2/mathrmH_2mathrmO^circright)$\left(E_{\mathrm{O}_2/\mathrm{H}_2\mathrm{O}}^{\circ}\right)$ is 1.229mathrm~V$1.229\mathrm{~V}$. Choose the correct statement:
A. The standard half cell reduction potential for the reduction of mathrmCO_2$\mathrm{CO}_2$left(E_mathrmCO_2/mathrmCH_3mathrmOH^circright)$\left(E_{\mathrm{CO}_2/\mathrm{CH}_3\mathrm{OH}}^{\circ}\right)$ is 19mathrm~mV$19\mathrm{~mV}$
B. Oxygen is formed at the anode.
C. Reactants are fed at one go to each electrode.
D. Reduction of methanol takes place at the cathode.
Solution
### Related Formula
Standard cell EMF is related to standard reduction potentials:
E_mathrmcell^circ = E_mathrmcathode^circ - E_mathrmanode^circ$E_{\mathrm{cell}}^{\circ} = E_{\mathrm{cathode}}^{\circ} - E_{\mathrm{anode}}^{\circ}$
### Core Logic
In a methanol-oxygen fuel cell:
- Anode reaction (Oxidation): Methanol is oxidized to carbon dioxide:
mathrmCH_3mathrmOH + mathrmH_2mathrmO rightarrow mathrmCO_2 + 6mathrmH^+ + 6e^-$\mathrm{CH}_3\mathrm{OH} + \mathrm{H}_2\mathrm{O} \rightarrow \mathrm{CO}_2 + 6\mathrm{H}^+ + 6e^-$
- Cathode reaction (Reduction): Oxygen is reduced to water:
mathrmO_2 + 4mathrmH^+ + 4e^- rightarrow 2mathrmH_2mathrmO$\mathrm{O}_2 + 4\mathrm{H}^+ + 4e^- \rightarrow 2\mathrm{H}_2\mathrm{O}$
Hence, cathode is the oxygen electrode, and anode is the methanol electrode.
### Step 1: Calculate Standard Reduction Potential of Anode
Using the EMF equation:
1.21mathrm~V = 1.229mathrm~V - E_mathrmanode^circ$1.21\mathrm{~V} = 1.229\mathrm{~V} - E_{\mathrm{anode}}^{\circ}$E_mathrmanode^circ = 1.229 - 1.21 = 0.019mathrm~V = 19mathrm~mV$E_{\mathrm{anode}}^{\circ} = 1.229 - 1.21 = 0.019\mathrm{~V} = 19\mathrm{~mV}$
The standard half-cell reduction potential for the mathrmCO_2/mathrmCH_3mathrmOH$\mathrm{CO}_2/\mathrm{CH}_3\mathrm{OH}$ couple is 19mathrm~mV$19\mathrm{~mV}$, matching Option (1).
### Pattern Recognition
Fuel cells are galvanic cells where reactants (like fuels and oxidants) are fed continuously to the electrodes, not at one go. Oxidation always occurs at the anode (methanol) and reduction at the cathode (oxygen).
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Q352025Kohlrausch's Law
Given below are two statements:
Statement I: Mohr's salt is composed of only three types of ions-ferrous, ammonium and sulphate.
Statement II: If the molar conductance at infinite dilution of ferrous, ammonium and sulphate ions are mathbfx_1$\mathbf{x}_1$, mathbfx_2$\mathbf{x}_2$ and mathbfx_3$\mathbf{x}_3$mathrmS\ cm^2\ mathrmmol^-1$\mathrm{S\ cm}^2\ \mathrm{mol}^{-1}$, respectively then the molar conductance for Mohr's salt solution at infinite dilution would be given by mathbfx_1 + mathbfx_2 + 2mathbfx_3$\mathbf{x}_1 + \mathbf{x}_2 + 2\mathbf{x}_3$.
In the light of the given statements, choose the correct answer from the options given below:
A.textBoth Statement I and Statement II are false$\text{Both Statement I and Statement II are false}$
B.textStatement I is false but Statement II is true$\text{Statement I is false but Statement II is true}$
C.textStatement I is true but Statement II is false$\text{Statement I is true but Statement II is false}$
D.textBoth Statement I and Statement II are true$\text{Both Statement I and Statement II are true}$
Solution
### Related Formula
lambda_m^infty = nu_+ lambda_+^infty + nu_- lambda_-^infty$\lambda_m^{\infty} = \nu_+ \lambda_+^{\infty} + \nu_- \lambda_-^{\infty}$
### Core Logic
Statement I: Mohr's salt is a double salt with chemical formula:
mathrmFeSO_4 cdot (NH_4)_2SO_4 cdot 6H_2O$\mathrm{FeSO_4 \cdot (NH_4)_2SO_4 \cdot 6H_2O}$
When dissolved in water, it completely dissociates into three distinct ionic species:
mathrmFe^2+ text (ferrous), quad mathrmNH_4^+ text (ammonium), quad textand mathrmSO_4^2- text (sulphate)$\mathrm{Fe}^{2+} \text{ (ferrous)}, \quad \mathrm{NH}_4^+ \text{ (ammonium)}, \quad \text{and } \mathrm{SO}_4^{2-} \text{ (sulphate)}$
Thus, Statement I is true.
Statement II: According to Kohlrausch's law of independent migration of ions:
lambda_m^infty(textMohr's Salt) = 1 cdot lambda_m^infty(mathrmFe^2+) + 2 cdot lambda_m^infty(mathrmNH_4^+) + 2 cdot lambda_m^infty(mathrmSO_4^2-)$\lambda_m^{\infty}(\text{Mohr's Salt}) = 1 \cdot \lambda_m^{\infty}(\mathrm{Fe}^{2+}) + 2 \cdot \lambda_m^{\infty}(\mathrm{NH}_4^+) + 2 \cdot \lambda_m^{\infty}(\mathrm{SO}_4^{2-})$lambda_m^infty = x_1 + 2x_2 + 2x_3$\lambda_m^{\infty} = x_1 + 2x_2 + 2x_3$
Statement II claims the expression is x_1 + x_2 + 2x_3$x_1 + x_2 + 2x_3$ (missing the coefficient 2$2$ for ammonium). Thus, Statement II is false.
### Pattern Recognition
Kohlrausch's law matches stoichiometric coefficients directly to the ion quantities released. Mohr's salt formula contains (NH_4)_2$(NH_4)_2$, requiring a multiplier of 2$2$ for ammonium ion conductance.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Class 12 Chemistry: d- and f-Block Elements
More Electrochemistry Questions — jee_main_2025_03_april_morning
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