### Related Formula
E_textcell = E_textcell^circ - fracRTnF ln Q$$E_{\text{cell}} = E_{\text{cell}}^{\circ} - \frac{RT}{nF} \ln Q$$
### Core Logic
Let us explicitly formulate the complete chemical oxidation-reduction equations :
Anode oxidation: mathrmMg_(s) rightarrow mathrmMg^2+_(aq) + 2e^-$\mathrm{Mg}_{(s)} \rightarrow \mathrm{Mg}^{2+}_{(aq)} + 2e^-$
Cathode reduction: 2mathrmAg^+_(aq) + 2e^- rightarrow 2mathrmAg_(s)$2\mathrm{Ag}^{+}_{(aq)} + 2e^- \rightarrow 2\mathrm{Ag}_{(s)}$
Net total equation :
mathrmMg_(s) + 2mathrmAg^+_(aq) rightleftharpoons mathrmMg^2+_(aq) + 2mathrmAg_(s)$$\mathrm{Mg}_{(s)} + 2\mathrm{Ag}^{+}_{(aq)} \rightleftharpoons \mathrm{Mg}^{2+}_{(aq)} + 2\mathrm{Ag}_{(s)}$$
Total transferred moles of electrons n = 2$n = 2$ .
Reaction quotient :
Q = frac[mathrmMg^2+][mathrmAg^+]^2$$Q = \frac{[\mathrm{Mg}^{2+}]}{[\mathrm{Ag}^{+}]^2}$$
Substituting into Nernst form :
E_textcell = E_textcell^circ - fracRT2F lnleft( frac[mathrmMg^2+][mathrmAg^+]^2 right)$$E_{\text{cell}} = E_{\text{cell}}^{\circ} - \frac{RT}{2F} \ln\left( \frac{[\mathrm{Mg}^{2+}]}{[\mathrm{Ag}^{+}]^2} \right)$$
Inverting the inside quotient changes the sign of the logarithm term from negative to positive:
E_textcell = E_textcell^circ + fracRT2F lnleft( frac[mathrmAg^+]^2[mathrmMg^2+] right)$$E_{\text{cell}} = E_{\text{cell}}^{\circ} + \frac{RT}{2F} \ln\left( \frac{[\mathrm{Ag}^{+}]^2}{[\mathrm{Mg}^{2+}]} \right)$$
### Pattern Recognition
A standard negative logarithmic quotient can always toggle into an addition configuration by inverting the products/reactants variables concentration ratio.
More Electrochemistry Previous-Year Questions
Q72jee_main_2026_21_jan_morningConductance of Electrolytic Solutions
The pH and conductance of a weak acid (HX) was found to be 5 and 4 times 10^-5$4 \times 10^{-5}$ S, respectively. The conductance was measured under standard condition using a cell where the electrode plates having a surface area of 1text cm^2$1\text{ cm}^2$ were at a distance of 15text cm$15\text{ cm}$ apart. The value of the limiting molar conductivity is ..... textS m^2text mol^-1$\text{S m}^2\text{ mol}^{-1}$. (nearest integer)
(Given: degree of dissociation of the weak acid (alpha) ll 1)$(\alpha) \ll 1)$
Numerical Answer.Answer: 6 to 6
Solution
### Related Formula
kappa = G times fraclA$$\kappa = G \times \frac{l}{A}$$Lambda_m = frackappa times 1000C$$\Lambda_m = \frac{\kappa \times 1000}{C}$$alpha = fracLambda_mLambda_m^infty$$\alpha = \frac{\Lambda_m}{\Lambda_m^{\infty}}$$[H^+] = Calpha$[H^+] = C\alpha$
### Core Logic
Given: pH = 5$pH = 5$, so [H^+] = 10^-5text M$[H^+] = 10^{-5}\text{ M}$.
Since [H^+] = C cdot alpha = C cdot fracLambda_mLambda_m^infty$[H^+] = C \cdot \alpha = C \cdot \frac{\Lambda_m}{\Lambda_m^{\infty}}$, we have 10^-5 = C cdot fracLambda_mLambda_m^infty$10^{-5} = C \cdot \frac{\Lambda_m}{\Lambda_m^{\infty}}$.
First, calculate conductivity (kappa$\kappa$):
Conductance G = 4 times 10^-5text S$G = 4 \times 10^{-5}\text{ S}$.
Cell constant G^* = fraclA = frac15text cm1text cm^2 = 15text cm^-1$G^* = \frac{l}{A} = \frac{15\text{ cm}}{1\text{ cm}^2} = 15\text{ cm}^{-1}$.
kappa = G cdot G^* = (4 times 10^-5) times 15 = 6 times 10^-4text S cm^-1$$\kappa = G \cdot G^* = (4 \times 10^{-5}) \times 15 = 6 \times 10^{-4}\text{ S cm}^{-1}$$
Molar conductivity (Lambda_m$\Lambda_m$):
Lambda_m = frackappa times 1000C = frac6 times 10^-4 times 1000C = frac0.6C$$\Lambda_m = \frac{\kappa \times 1000}{C} = \frac{6 \times 10^{-4} \times 1000}{C} = \frac{0.6}{C}$$
Substitute Lambda_m$\Lambda_m$ into the proton concentration formula:
[H^+] = 10^-5 = C cdot frac0.6 / CLambda_m^infty$$[H^+] = 10^{-5} = C \cdot \frac{0.6 / C}{\Lambda_m^{\infty}}$$10^-5 = frac0.6Lambda_m^infty$$10^{-5} = \frac{0.6}{\Lambda_m^{\infty}}$$Lambda_m^infty = frac0.610^-5 = 60000text S cm^2text mol^-1$$\Lambda_m^{\infty} = \frac{0.6}{10^{-5}} = 60000\text{ S cm}^2\text{ mol}^{-1}$$
Convert units to textS m^2text mol^-1$\text{S m}^2\text{ mol}^{-1}$:
Since 1text m^2 = 10^4text cm^2$1\text{ m}^2 = 10^4\text{ cm}^2$,
Lambda_m^infty = 60000 times 10^-4text S m^2text mol^-1 = 6text S m^2text mol^-1$$\Lambda_m^{\infty} = 60000 \times 10^{-4}\text{ S m}^2\text{ mol}^{-1} = 6\text{ S m}^2\text{ mol}^{-1}$$
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Electrochemistry
Class 11 Chemistry: Equilibrium
Q47jee_main_2025_02_april_eveningConductivity 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
Qjee_main_2025_02_april_morningNernst 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
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
Q34jee_main_2025_03_april_eveningFuel 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
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