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NCERT Solutions for Class 12 Chemistry Chapter 3 - Electrochemistry

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NCERT Class 12 Chemitry Chapter 3: Complete Resource for Electrochemistry

Ch 3 Chemistry Class 12 NCERT Book Solutions focuses on Electrochemistry and its implications in the real world. Some of the topics covered here are electrochemical cells, galvanic cells, and electrolytic cells.


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Class:

NCERT Solutions for Class 12

Subject:

Class 12 Chemistry

Chapter Name:

Chapter 3 - Electrochemistry

Content-Type:

Text, Videos, Images and PDF Format

Academic Year:

2023-24

Medium:

English and Hindi

Available Materials:

  • Chapter Wise

  • Exercise Wise

Other Materials

  • Important Questions

  • Revision Notes



The Nernst equation follows these topics for calculating emf and definition of the standard potential of a cell. Important terms like resistivity, conductivity and molar conductivity of the cell are explained briefly. Kohlrausch’s law and its applications are the next topics. Quantitative aspects of electrolysis and construction of primary and secondary batteries are presented next.


List of Subtopics from Class 12 Chemistry Chapter 3 Electrochemistry

  • Electrochemical Cells

  • Galvanic Cells

  • Measurement of Electrode Potential

  • Nernst Equation

  • Equilibrium Constant from Nernst Equation

  • Electrochemical Cell and Gibbs Energy of Reaction

  • The Conductance of Electrolytic Solutions

  • Measurement of the Conductivity of Ionic Solutions

  • Variation of Conductivity and Molar Conductivity with Concentration

  • Electrolytic Cells and Electrolysis

  • Products of Electrolysis

  • Batteries

  • Primary Batteries

  • Secondary Batteries

  • Fuel Cells

  • Corrosion


Electrochemistry Chapter at a Glance - Class 12 NCERT Solutions


  • Electrochemical Cells

It is device for converting chemical energy into electrical energy and vice versa


Types

(i) Galvanic Cells/Voltaic Cells:

Converts chemical energy into electrical energy

(ii) Electrolytic Cells:

Converts electrical energy into chemical energy.


  • Electrode Potential

The tendency of an element, when it is placed in contact with its own ions to either lose or gain electrons and in turn becomes positively or negatively charged.

  • Electrochemical Series

The half cell potential values are standard values and are represented as the standard reduction potential values as shown in the table at the end which is also called Electrochemical Series.

  • Cell potential or EMF of a cell

The difference between the electrode potentials of two half cells is called cell potential.

ECell = ERed, cathode – ERed, anode


  • Kohlrausch’s Law

It states that the limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the anion and cation of the electrolyte.


  • Application of Kohlrausch’s law

(i) Calculation of molar conductivities of weak electrolyte at infinite dilution

(ii) Determination of Degree of Dissociation of Weak Electrolytes

(iii) Determination of Dissociation Constant (K) of Weak Electrolyte


  • Batteries

Primary Batteries

Primary cells are those which can be used as long as the active materials are present. Once they get consumed, the cell will stop functioning and cannot be reused.

Example: Dry Cell or Leclanche cell and Mercury cell. 

Secondary Batteries

Secondary cells are those which can be recharged again and again for multiple uses. e.g. lead storage battery and Ni – Cd battery


  • Fuel Cell

It is designed to convert the energy of combustion of fuels like hydrogen, methane, methanol, etc. directly into electrical energy.


  • Corrosion

It involves a redox reaction and formation of an electrochemical cell on the surface of iron or any other metal. Rusting of iron can be avoided by painting it or by coating it with some other metals like Zinc. This process is known as Galvanisation.


Electrochemistry Formulas


Electrochemistry Formulas


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Mastering Class 12 Chemistry Chapter 3: Electrochemistry - Notes, Question and Answers and Tips for Success

Intext Questions

1. How would you determine the standard electrode potential of the system ${\text{M}}{{\text{g}}^{2 + }}{\text{|Mg}}?$

Ans. A cell with ${\text{Mg}}/{\text{MgS}}{{\text{O}}_4}(1{\text{M}})$ as one electrode and standard hydrogen electrode ${\text{Pt}},{\text{H}},(1\;{\text{atm}}){{\text{H}}^ + }(1{\text{M}})$ as the second electrode will be set up, and the emf of the cell will be measured along with the direction of deflection in the voltmeter. The direction of deflection indicates that ${{\text{e}}^ - }$ move from the magnesium electrode to the hydrogen electrode, implying that oxidation occurs on the magnesium electrode and reduction occurs on the hydrogen electrode. As a result, the cell can be represented in the following way:

$\mathrm{Mg}\left|\mathrm{Mg}^{2+}(1 \mathrm{M}) \| \mathrm{H}^{+}(1 \mathrm{M})\right| \mathrm{H}^{2},(1 \mathrm{~atm}) \mathrm{Pt}$

$E_{\text {cell }}^{o}=E_{H{+} \frac{1}{2}}^{o}-E^{o} \mathrm{Mg}^{2+} / \mathrm{Mg}$

$\text { put } E_{H+\frac{1}{2} H_{2}}^{o}=0$

$\therefore E_{\mathrm{Mg}^{2+} / \mathrm{Mg}}^{o}=-E^{o}{ }_{\text {cell }}$


2. Can you store copper sulphate solutions in a zinc pot?

Ans. ${\text{Cu}}$ is less reactive than ${\text{Zn}}$, so ${\text{Cu}}$ is easily shifted from ${\text{CuS}}{{\text{O}}_4}$solution in the following reaction: 

$\left. {{\text{Zn}}({\text{s}}) + {\text{CuS}}{{\text{O}}_4}({\text{aq}}) \to {\text{ZnSO}}{4_{({\text{q}}q}}} \right) + {\text{Cu}}({\text{s}})$

If we express it in relations of emf, it will be like: 

$\text { Ecell }^{\circ}=\mathrm{Ecu}^{2+} / \mathrm{Cu}^{\circ}-\mathrm{E}^{\circ} \mathrm{zn}^{2+} / \mathrm{Zn}$

$= 0.34\;{\text{V}} - ( - 0.76\;{\text{V}}) = 1.10\;{\text{V}}$

 As, The positive ${\text{E}}_{{\text{cell }}}^{\text{^\circ }}$value indicates the occurrence of spontaneous reactions. if ${\text{CuS}}{{\text{O}}_4}$ is stored in ${\text{Zn}}$ pot, ${\text{Zn}}$ will react will ${\text{Cu}}$ and originality of ${\text{CuS}}{{\text{O}}_4}$ will not be maintained.


3. Consult the table of standard electrode potentials and suggest three substances that can oxidize ferrous ions under suitable conditions.

Ans. In the process of oxidation of ${\text{F}}{{\text{e}}^{2 + }}$ to ${\text{F}}{{\text{e}}^{3 + }}$, i.e., ${\text{F}}{{\text{e}}^{2 + }} \to {\text{F}}{{\text{e}}^{3 + }} + {{\text{e}}^ - };$the reduction potential value is negative in nature i.e. ${{\text{E}}^{\text{o}}}\text{ox}=\text{ }\!\!~\!\!\text{ }-0.77\ \text{V}$. Only compounds with powerful oxidizing agents and positive reduction potentials larger than $0.77\;{\text{V}}$ may oxidize ${\text{F}}{{\text{e}}^{2 + }}$ to ${\text{F}}{{\text{e}}^{3 + }}$, resulting in a positive emf of the cell reaction. This is true for elements like halogens  ${\text{B}}{{\text{r}}_2},{\text{C}}{{\text{l}}_2}$ and ${{\text{F}}_2}$ in the series below ${\text{F}}{{\text{e}}^{3 + }}/{\text{F}}{{\text{e}}^{2 + }}$.


4. Calculate the potential of hydrogen electrode in contact with a solution whose ${\text{pH}}$ is 10.

Ans. For hydrogen electrode, ${{\text{H}}^ + } + {{\text{e}}^ - } \to 1/2{{\text{H}}_2}$

Given: ${\text{pH = 10}}$

Using Nernst equation,

$E_{H^{-} \frac{1}{2} H_{2}}=E_{H^{+} \frac{1}{2} H_{2}}^{o}-\frac{0.0591}{n} \log \frac{1}{\left[H^{+}\right]}$

$0 - \dfrac{{0.0591}}{1}\log \dfrac{1}{{{{10}^{ - 10}}}}$

${{\text{pH  =  10}}}$

${\text{  = -  0}}{\text{0519}} \times {\text{10}}$

$= 0.591{\text{V}}$

Hence, the potential of hydrogen electrode in contact with a solution whose ${\text{pH}}$ is 10 is $0.591\;{\text{V}}$.


5. Calculate the emf of the cell in which the following reaction takes place: ${\text{N}}{{\text{i}}_{({\text{a}})}} + 2{\text{A}}{{\text{g}}^ + }(0.002{\text{M}})$ $ \to {\text{N}}{{\text{i}}^{\text{i}}}^ + (0.160{\text{M}}) + 2{\text{A}}{{\text{g}}_{({\text{a}})}}$ Given that $=\text{E}{}^\circ (\text{coll})1.05\ \text{V}$.

Ans.Using Nernst equation,

${{\text{E}}_{{\text{cell}}}}{\text{ = E}}_{{\text{cell}}}^{\text{o}}{\text{ - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{n}}}{\text{log}}\dfrac{{\left[ {{\text{N}}{{\text{i}}^{{\text{2 + }}}}} \right]}}{{{{\left[ {{\text{A}}{{\text{g}}^{\text{ + }}}} \right]}^{\text{2}}}}}$

$= 1.05\;{\text{V}} - \dfrac{{0.0519}}{2}\log \dfrac{{0.160}}{{{{(0.002)}^2}}}$

$= 1.05 - \dfrac{{0.0591}}{2}\log \left( {\log 4 \times {{10}^4}} \right)$

$= 1.05 - \dfrac{{0.0591}}{2}(4.6021)$

$= 1.05 - 0.14\;{\text{V}} = 0.91\;{\text{V}}$

Therefore, the emf of the cell is $0.91\;{\text{V}}$. 


6.  $0.236\;{\text{V}}$ at $298\;{\text{K}}$. calculate the standard Gibbs energy and the equilibrium constant of the cell reaction.

Ans. $2{\text{F}}{{\text{e}}^3} + ({\text{zg}}) + 2{{\text{I}}^ - }({\text{zq}}) \to 2{\text{F}}{{\text{e}}^2} + ({\text{zg}}) + {{\text{I}}_2}(\;{\text{g}})$

For the given cell, the number of transacted electrons i.e. ${\text{n}} = 2$ 

Using the given formula;

$\Delta_{r} G^{o}=-F E^{o}{ }_{c e l l}$

$=-2 \times 96500 \times 0.236$

$=-45.55 \mathrm{~kJ} \mathrm{~mol}-1$

Also, $\Delta_{r} \mathrm{G}^{\circ}=-2.303 \mathrm{RT} \log \mathrm{KC}$

$\Rightarrow \log K_{c}=\frac{\Delta, G^{o}}{2.303 R T}=\frac{-45.55}{2.303\times 8.314 \times 10^{-3} \times 298}=7.983$

$\Rightarrow K_{c}=\operatorname{antilog}(7.983)$

$=9.616 \times 10^{7}$


7. Why does the conductivity of solution decrease with dilution?

Ans. The conductance of ions contained in a unit volume of solution is called conductivity. The number of ions per unit volume decreases with increase in dilution. As a result, the conductivity drops.


8. Suggest a way to determine the value $\Lambda {}^\circ $of water.

Ans. By using Kohlrausch's law for ${{\text{H}}_2}{\text{O}}$, we can calculate $\Lambda \text{m}{}^\circ$ 

The Kohlrausch Law says that when dissociation is complete at infinite dilution, each ion adds a definite amount to the electrolyte's equivalent conductance, regardless of the nature of the ion with which it is involved, and the value of equivalent conductance at infinite dilution for any electrolyte is the sum of contributions of its ionic species (cations and anions).

$\Lambda \text{m}{}^\circ \text{ }\!\!~\!\!\text{ }=\Lambda \text{m}{}^\circ (\text{Hcl})+\Lambda \text{m}{}^\circ (\text{NaOH})-\Lambda \text{m}{}^\circ (\text{NaCl})$

The  $\Lambda {}^\circ$ values of ${\text{HCl}},{\text{NaOH}}$ and ${\text{NaCl}}$ are known as they are strong electrolytes and dissociates completely.. By putting their values in the above equation, we can have value of  $\Lambda {\text{m}}^\circ $ for ${{\text{H}}_2}{\text{O}}$.


9. The molar conductivity of $0.025 \mathrm{~mol} \mathrm{~L}^{-1}$ methanoic acid is $46.1 \mathrm{~S} \mathrm{~cm}^{2} \mathrm{~mol}^{-1} .$ Calculate its degree of dissociation and dissociation constant Given $\lambda^{0}\left(H^{+}\right)=$ $349.6 \mathrm{~cm}^{2}$ and $\lambda^{\circ}\left(\mathrm{HCOO}^{-}\right)=54.6 \mathrm{~cm}^{2} \mathrm{~mol}^{-1}$

Ans. $\Lambda_{m}^{o}(H C O O H) \lambda^{\circ}\left(H^{+}\right)+\lambda^{\circ}(H C O O)^{-}$

$=349.6+54.6$

$=404.2 \mathrm{~S} \mathrm{~cm}^{2} \mathrm{~mol}^{-1}$

$\Lambda_{m}^{c}=46.1 \mathrm{~S} \mathrm{~cm}^{2} \mathrm{~mol}^{-1}$

$\therefore \alpha= \frac{\Lambda_{m}^{c}}{\Lambda_{m}^{c}}=\frac{46.1}{404.2}=0.114$


10. If a current of $0.5$ampere flows through a metallic wire for 2 hours, then how many electrons would flow through the wire?

Ans. As from the formula, 

$\mathrm{Q}=\mathrm{It}$

$=0.5 \times(2 \times 60 \times 60)=3600 \mathrm{C}$

$1 \mathrm{~F} \Rightarrow 96500 \mathrm{C} \Rightarrow 1 \mathrm{~mole} \text { of } \mathrm{e}^{-1} \mathrm{~s}$

$\therefore 6.02 \times 10^{23} \mathrm{e}^{-1} \mathrm{~s}$

$\therefore 3600 \mathrm{C}$ is equivalent to the flow of $\mathrm{e}^{-1} \mathrm{~s}$

$=\frac{6.02 \times 10^{23}}{96500} \times 3600=2.246 \times 10^{22} e^{-1} s$


11. Suggest a list of metals that are extracted electrolytically.

Ans. ${\text{Na}},{\text{Ca}},{\text{Mg}}$, and ${\text{Al}}$


12. Consider the reaction: ${\text{CrO}}_7^{2 - } + 14{{\text{H}}^ + } + 6{{\text{e}}^ - } \to 2{\text{C}}{{\text{r}}^{3 + }} + 7{{\text{H}}_2}{\text{O}}$. What is the quantity of electricity in coulombs needed to reduce $1\;{\text{mol}}$ of ${\text{C}}{{\text{r}}_2}{\text{O}}_7^{2 - }$

Ans. For the above reaction to take place, $1\;{\text{mol}}$ of ${\text{C}}{{\text{r}}_2}{\text{O}}_7^{2 - }$ will require $6\;{\text{F}}$ $ = 6 \times 96500 = 579000{\text{C}}$0f electricity.

Hence,$579000{\text{C}}$ of electricity are required for reduction of ${\text{C}}{{\text{r}}_2}{\text{O}}_7^{2 - }$ to ${\text{C}}{{\text{r}}^{3 + }}$


13. Write the chemistry of recharging the lead storage battery, highlighting all the materials that are involved during recharging.

Ans. A lead storage battery has a lead anode, a lead cathode with lead dioxide packed$\left( {{\text{Pb}}{{\text{O}}_2}} \right)$ in it, and a $38\% {{\text{H}}_2}{\text{S}}{{\text{O}}_4}$solution as the electrolyte. When the battery is in operation, the following reactions occur:

At Anode: ${\text{P}}{{\text{b}}_{(s)}} + {\text{SO}}_4^{2 - } \to {\text{PbS}}{{\text{O}}_{4(s)}} + 2{e^ - }$

At cathode:${\text{ Pb}}{{\text{O}}_{{\text{2(s)}}}}{\text{  +  S}}{{\text{O}}_{\text{4}}}{^{{\text{2 - }}}_{{\text{(ag)}}}}{\text{  +  4}}{{\text{H}}^{\text{ + }}}_{{\text{(aq)}}}{\text{  +  2}}{{\text{e}}^ - }\xrightarrow{{}}{\text{PbS}}{{\text{O}}_{{\text{4(s)}}}}{\text{ +  2}}{{\text{H}}_{\text{2}}}{{\text{O}}_{{\text{(l)}}}}$

Complete reaction: $P{b_{(s)}} + Pb{O_{2(s)}} + 2{H_2}S{O_{4(aq)}} \to 2PbS{O_{4(s)}} + 2{H_2}{O_{(l)}}$

The reverse process occurs when the battery is charged, in which ${\text{PbS}}{{\text{O}}_{\text{4}}}$ deposited on the electrodes is transformed back to ${\text{Pb}}$and ${\text{Pb}}{{\text{O}}_2}$, and ${{\text{H}}_2}{\text{S}}{{\text{O}}_4}$ is restored.


14. Suggest two materials other than hydrogen that can be used as fuels in fuel cells.

Ans. Methane and Methanol.


15. Explain how rusting of iron is envisaged as setting up of an electro chemical cell

Ans.The Water present on the surface of iron dissolves acidic oxides of air like ${\text{C}}{{\text{O}}_2},{\text{S}}{{\text{O}}_2}$ etc, to form acids which dissociate to give ${{\text{H}}^ + }$ ions:

${{\text{H}}_2}{\text{O}} + {\text{C}}{{\text{O}}_2} \to {{\text{H}}_2}{\text{C}}{{\text{O}}_3} \rightleftharpoons 2{{\text{H}}^ + } + {\text{CO}}_3^{2 - }$

In the presence of ${{\text{H}}^ + }$, iron${\text{F}}{{\text{e}}^{2 + }}$ releases ${{\text{e}}^{ - 1}}$ to form ${\text{F}}{{\text{e}}^{3 + }}$. Hence, this acts as anode:

${\text{F}}{{\text{e}}_{(s)}} \to {\text{F}}{{\text{e}}^{2 + }}_{({\text{aq}})} + 2{{\text{e}}^ - }$

The ${{\text{e}}^{ - 1}}$ lost then travel through the metal to reach place where these electrons are utilized by ${{\text{H}}^ + }$ ions and dissolved oxygen and reduction takes place. Thus acts as cathode:

${{\text{O}}_2}(\;{\text{g}}) + 4{{\text{H}}^ + }_{({\text{aq}})} + 4{{\text{e}}^ - } \to 2{{\text{H}}_2}{{\text{O}}_{({\text{g}})}}$

The overall reaction is:

$2{\text{F}}{{\text{e}}_{({\text{s}})}} + {{\text{O}}_2}_{(\;{\text{g}})} + 4{{\text{H}}^ + }_{({\text{aq}})} \to 2{\text{F}}{{\text{e}}^{2 + }}_{({\text{aq}})} + 2{{\text{H}}_2}{{\text{O}}_{({\text{l}})}}$

As a result, an electrochemical cell is established on the surface. The atmospheric oxygen oxidizes ferrous ions to ferric ions, which mix with water to produce hydrated ferric oxide., ${\text{F}}{{\text{e}}_2}{{\text{O}}_3}.{\text{X}}{{\text{H}}_2}{\text{O}}$ which is known as rust.


Ncert Exercises 

1. Arrange the following metals in the order in which they displace each other from the solution of their salts: ${\text{Al}},{\text{Cu}},{\text{Fe}},{\text{Mg}}$ and ${\text{Zn}}$

 Ans. ${\text{Mg}},{\text{Al}},{\text{Zn}},{\text{Fe}},{\text{Cu}},{\text{Ag}}$


2. Given the standard electrode potentials, ${{\text{K}}^ + }/{\text{K}} = 2.93\;{\text{V}},{\text{A}}{{\text{g}}^ + }/{\text{Ag}} = 0.80\;{\text{V}}$

${\text{H}}{{\text{g}}^{2 + }}/{\text{Hg}} = 0.79\;{\text{V}}$

${\text{M}}{{\text{g}}^{2 + }}/{\text{Mg}} =  - 2.73\;{\text{V}},{\text{C}}{{\text{l}}^{3 + }}/{\text{Cr}} = 0.74\;{\text{V}}$

Arrange these metals in their increasing order of reducing power.

Ans: The larger the oxidation potential, the easier it is to oxidize it, and hence the higher the reducing power. As a result, the reducing power of the elements will be in the following ascending sequence: ${\text{Ag}} < {\text{Hg}} < {\text{Cl}} < {\text{Mg}} < {\text{K}}$.


3. Depict the galvanic cell in which the reaction, $2\text{A}{{\text{g}}^{\text{ + }}}\ \left( \text{aq} \right)\ \xrightarrow{{}}\text{Z}{{\text{n}}^{\text{2 + }}}\left( \text{aq} \right)\text{ + 2Ag(s)}$takes place. Further show:

Ans.  The set-up will be similar to the one seen below.


Galvanic cell

(i) Which of the electrode is negatively charged?

Ans. The anode, or zinc electrode, will have a negative charge.

(ii) The carriers of the current in the cell.

Ans. In the external circuit, current will travel from silver to copper.

(iii) Individual reaction at each electrode.

Ans. At anode: ${\text{Zn}}\left( {({\text{n}}) \to {\text{Z}}{{\text{n}}^{2 + }}({\text{q}}) + 2{{\text{e}}^ - }} \right.$

At cathode: $2{\text{A}}{{\text{g}}^ + }_{({\text{zq}})} + 2{{\text{e}}^ - } \to 2{\text{A}}{{\text{g}}_{({\text{i}})}}$


4. Calculate the standard cell potentials of galvanic cell in which the following reactions take place

(i) $2 \mathrm{Cr}(\mathrm{s})+\mathrm{Cd}^{2+}_{(a q)} \rightarrow 2 \mathrm{Cr}^{3+}{ }_{(a q)}+3 \mathrm{Cd}_{(s)}$

(ii) $\mathrm{Fe}^{2+}_{(a q)}+\mathrm{Ag}_{(a q)}^{+} \rightarrow \mathrm{Fe}^{3+}_{(a q)}+\operatorname{Ag}(s)$

Calculate the $\Delta_{r} G^{o}$ and equilibrium constant of the reactions

Given

$E_{\mathrm{Cr}^{3}, \mathrm{Cr}}^{o}=-0.74 \mathrm{~V}$

$E_{\mathrm{Cr}^{2+}, \mathrm{Cd}}^{o}=-0.40 \mathrm{~V}$

$E_{\mathrm{Ag}^{+}}^{o} A g=0.80 \mathrm{~V}$

$E_{F e^{3},{ }_{F e^{2+}}}^{o}=0.77 \mathrm{~V}$

Ans: $E^{\circ} \text { cell }=E^{\circ} \text { cathode }-E^{\circ} \text { Anode }$

$=-0.40 \mathrm{~V}-(-0.74 \mathrm{~V})=+0.34 \mathrm{~V}$

$\Delta_{r} G^{o}=\mathrm{nFE}^{\circ} \text { cell }$

$=-6 \times 96500 \mathrm{C} \mathrm{mol}^{-1} \times 0.34 \mathrm{~V}$

$=196860 \mathrm{C} \mathrm{V} \mathrm{mol}^{-1}$

$=196860 \mathrm{~J} \mathrm{~mol}^{-1}$

$=-196.86 \mathrm{~kJ} \mathrm{~mol}^{-1}$

$-\Delta_{r} G^{\circ}=2.303 \mathrm{x} 8.314 \times 298 \log \mathrm{K}$

$196860=2.303 \times 8.314 \times 298 \log \mathrm{K}$

$\text { or } \log \mathrm{K}=34.5014$

$\mathrm{~K}=\text {Antilog} 34.5014=3.172 \times 10^{34}$

(ii) $\mathrm{E}^{\circ} \mathrm{cell}=+0.80 \mathrm{~V}-0.77 \mathrm{~V}=+0.03 \mathrm{~V}$

$\Delta_{r} G^{o}=\mathrm{nFE}^{\circ} \text { cell }$

$=-1 \times\left(96500 \mathrm{C} \mathrm{V} \mathrm{mol}^{-1}\right) \times(0.03 \mathrm{~V})$

$=-2.895 \mathrm{C} \mathrm{V} \mathrm{mol}^{-1}=-2895 \mathrm{~J} \mathrm{~mol}^{-1}$

$=2.895 \mathrm{~kJ} \mathrm{~mol}^{-1}$

$\Delta_{r} G^{o}=2.303 \mathrm{RT} \log \mathrm{K}$

$-2895=-2.303 \times 8.314 \times 298 \times \log \mathrm{K}$

or $\log \mathrm{K}=0.5074$

or $\mathrm{K}=\operatorname{Antilog}(0.5074)=3.22$


5. Write the Nernst equation and emf of the following cells at $298\;{\text{K}}$

(i) $\mathrm{Mg}_{(s)} \mid \mathrm{Mg}^{2+}(0.001 \mathrm{M}) \| \mathrm{Cu}^{2+}(0.0001 \mathrm{M}) \mathrm{Cu}_{(\mathrm{s})}$

(ii) $\text{F}{{\text{e}}_{(s)}}\mid \text{F}{{\text{e}}^{2+}}(0.001\text{M})\|{{\text{H}}^{+}}(1\text{M}){{\text{H}}_{2}}(~\text{g})(1\,\text{bar)P}{{\text{t}}_{(\text{S})}}$

(iii) $\text{S}{{\text{n}}_{(\text{s})}}\left| \text{S}{{\text{n}}^{2+}}(0.050\text{M})\|{{\text{H}}^{+}}(0.020\text{M}) \right|{{\text{H}}_{2}}(~\text{g})(1\,\text{bar)P}{{\text{t}}_{\text{(S)}}}$

(iv) $\text{P}{{\text{t}}_{(\text{s})}}\left| \text{B}{{\text{r}}_{2(\text{I})}} \right|\text{Br}-(0.010\text{M})\|\text{H}+(0.030\text{M}){{\text{H}}_{2(~\text{g})}}(1\,\text{bar)P}{{\text{t}}_{(\text{S})}}$

Given ${\text{E}}^\circ {\text{CellM}}{{\text{g}}^{2 + }},{\text{Mg}} = - 2.37\;{\text{V}}$,

\[{\text{E}}^\circ {\text{c}}{{\text{u}}^{2 + }},{\text{Cu}} = + 0.34\;{\text{V}},{\text{E}}^\circ {\text{F}}{{\text{e}}^{2 + }}{\text{Fe}} = - 0.44\;{\text{V}}\]

${\text{E}}^\circ {\text{S}}{{\text{n}}^{2 + }}/{\text{Sn}} = - 0.14\;{\text{V}}$

\[{\text{E}}^\circ 1/2{\text{B}}{{\text{r}}_2}/{\text{B}}{{\text{r}}^ - } = + 1.08\;{\text{V}}\]

(i) 

Ans. Cell reaction:

${\text{Mg}} + {\text{C}}{{\text{u}}^{2 + }} \to {\text{M}}{{\text{g}}^{2 + }} + {\text{Cu}}({\text{n}} = 2)$

Applying Nernst equation:

${{\text{E}}_{{\text{cell }}}}{\text{ = E}}_{{\text{Cell }}}^{\text{^\circ }}{\text{ - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{\left[ {{\text{M}}{{\text{g}}^{{\text{2 + }}}}} \right]}}{{\left[ {{\text{C}}{{\text{u}}^{{\text{2 + }}}}} \right]}}$

${{\text{E}}_{{\text{cell }}}}{\text{ = 0}}{\text{.34 - ( - 2}}{\text{.37) - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{{\text{1}}{{\text{0}}^{{\text{ - 3}}}}}}{{{\text{1}}{{\text{0}}^{{\text{ - 4}}}}}}$

$= 2.71 - 0.02955 = 2.68\;{\text{V}}$

(ii) 

Ans. Cell reaction:

${\text{Fe}} + 2{{\text{H}}^ + } \to {\text{F}}{{\text{e}}^{2 + }} + {{\text{H}}_2}({\text{n}} = 2)$

Applying Nernst equation  

${{\text{E}}_{{\text{cell }}}}{\text{ = E}}_{{\text{cell }}}^{\text{o}}{\text{ - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{\left[ {{\text{F}}{{\text{e}}^{{\text{2 + }}}}} \right]}}{{{{\left[ {{{\text{H}}^{\text{ + }}}} \right]}^{\text{2}}}}}$

${{\text{E}}_{{\text{cell }}}}{\text{ = 0 - ( - 0}}{\text{.44) - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{{\text{1}}{{\text{0}}^{{\text{ - 3}}}}}}{{{{{\text{(1)}}}^{\text{2}}}}}$

$= 0.44 - \dfrac{{0.0591}}{2} \times ( - 3)$

$= 0.44 + 0.0887 = 0.5287\;{\text{V}}$

(iii) 

Ans. Cell reaction:

${\text{Sn}} + 2{{\text{H}}^ + } \to {\text{S}}{{\text{n}}^{2 + }} + {{\text{H}}_2}({\text{n}} = 2)$

Applying Nernst equation:

${{\text{E}}_{{\text{cell}}}}{\text{ = E}}_{{\text{cell}}}^{\text{^\circ }}{\text{ - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{\left[ {{\text{s}}{{\text{n}}^{{\text{2 + }}}}} \right]}}{{{{\left[ {{{\text{H}}^{\text{ + }}}} \right]}^{\text{2}}}}}$

${{\text{E}}_{{\text{cell}}}}{\text{ = E}}_{{\text{cell}}}^{\text{^\circ }}{\text{ - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{{\text{0}}{\text{.05}}}}{{{{{\text{(0}}{\text{.02)}}}^{\text{2}}}}}$

$= 0 - ( - 0.14) - \dfrac{{0.0591}}{2}\log \dfrac{{0.05}}{{{{(0.02)}^2}}}$

$= 0.14 - \dfrac{{0.0591}}{2}\log 125$

$= 0.14 - \dfrac{{0.0591}}{2}(2.0969) = 0.078\;{\text{V}}$

(iv)

Ans. Cell reaction:

$2{\text{Br}} + 2{{\text{H}}^ + } \to {\text{B}}{{\text{r}}_2} + {{\text{H}}_2}({\text{n}} = 2)$

Applying Nernst equation:

${{\text{E}}_{{\text{cell}}}}{\text{ = E}}_{{\text{cell}}}^{\text{^\circ }}{\text{ - }}\dfrac{{{\text{0}}{\text{.0591}}}}{{\text{2}}}{\text{log}}\dfrac{{\text{1}}}{{{{\left[ {{\text{B}}{{\text{r}}^{\text{ - }}}} \right]}^{\text{2}}}{{\left[ {{{\text{H}}^{\text{ + }}}} \right]}^{\text{2}}}}}$

$= (0 - 1.08) - \dfrac{{0.0591}}{2}\log \dfrac{1}{{{{(0.01)}^2}{{(0.03)}^2}}}$

$=  - 1.08 - \dfrac{{0.0591}}{2}\log \left( {1.111 \times {{10}^7}} \right)$

$=  - 1.08 - \dfrac{{0.0591}}{2}(7.0457)$

$=  - 1.08 - 0.208 =  - 1.288\;{\text{V}}$

As a result, oxidation will take place at the hydrogen electrode, whereas reduction will take place at the ${\text{B}}{{\text{r}}_2}$ electrode.


6. In the button cells widely used in watches and other devices the following reaction takes places:

Determine $\Delta \text{rG}{}^\circ $ and $\text{E}{}^\circ $ for the reaction.

Given \[\text{Zn}\to \text{Z}{{\text{n}}^{2+}}+2{{\text{e}}^{-}},\text{E}{}^\circ =0.76\ \text{V}\]

\[\text{A}{{\text{g}}_{2}}\text{O}+{{\text{H}}_{2}}\text{O}+2{{\text{e}}^{-}}\to 2\text{Ag}+2\text{O}{{\text{H}}^{-}},\text{E}{}^\circ =0.344\text{v}\]

Ans. In the given reaction, ${\text{Zn}}$is getting oxidized and ${\text{A}}{{\text{g}}_2}{\text{O}}$ is being reduced.

$\text{E}{}^\circ \text{cell}$$= 0.344 + 0.76 = 1.104\;{\text{V}}$

$\Delta \text{G}{}^\circ =\text{nFE}{}^\circ \text{cell}=\text{ }\!\!~\!\!\text{ }-2\times 96500\times 1.104\ \text{J}$

$\Delta \text{G}{}^\circ $$=  - 2.13 \times {10^5}\;{\text{J}}$


7. Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation with concentration.

Ans. The conductivity of a solution is defined as the conductance of a solution with a length of 1${\text{cm}}$and a cross-sectional area of 1 s${\text{cm}}$. 

When the electrodes are one cm apart and the area of cross-section of the electrodes is large enough that the entire solution is contained between them, the molar conductivity of a solution at a dilution$({\text{V}})$ is the conductance of all the ions produced from one mole of the electrolyte dissolved in the solution${\text{Vc}}{{\text{m}}^3}$. ${\Lambda _m}$ is the most common symbol for conductivity.

The conductivity of a solution (for both strong and weak electrolytes) diminishes as the concentration of the electrolyte drops, i.e. as dilution occurs. This is owing to the fact that when the solution is diluted, the number of ions per unit volume of the solution decreases.

On dilution, the molar conductivity of a solution increases as with decrease in concentration of the electrolyte. This is owing to the fact that when the solution is diluted, the number of ions per unit volume of the solution decreases. The molar conductivity of a solution increases as the electrolyte content drops. This is because dilution increases both the quantity of ions and their mobility. The molar conductivity is known as limiting molar conductivity as the concentration approaches zero.


8. The conductivity of $0.20{\text{M}}$ solution of ${\text{KCl}}$ at $298\;{\text{K}}$ is $0.0248\;{\text{S}}\;{\text{c}}{{\text{m}}^{ - 1}}.$ Calculate its molar conductivity.

Ans. ${\Lambda _{\text{m}}}{\text{ = }}\;\dfrac{{{\text{k}} \times {\text{1000}}}}{{{\text{ Molanity }}}}{\text{ = }}\;\dfrac{{{\text{0}}.{\text{2485}}\;{\text{c}}{{\text{m}}^{\:{\text{ - }}\:{\text{1}}}} \times {\text{1000}}\;{\text{c}}{{\text{m}}^{\text{3}}}{{\text{L}}^{\:{\text{ - }}\:{\text{1}}}}}}{{{\text{0}}{\text{.20mo}}{{\text{L}}^{\:{\text{ - }}\:{\text{1}}}}}} = 124\;{\text{Sc}}{{\text{m}}^2}{\text{mo}}{{\text{l}}^{ - 1}}$


9. The resistance of a conductivity cell containing $0.001{\text{MKCl}}$ solution at $298\;{\text{K}}$ is $1500\Omega $. What is the cell constant if conductivity of $0.001{\text{MKCl}}$ solution at $298\;{\text{K}}$ is $0.146 \times {10^{ - 3}}\;{\text{S}}\;{\text{c}}{{\text{m}}^{ - 1}}?$

Ans. From the following relation:

$\;\;{\text{Cell constant}} = \dfrac{{{\text{ Conductivity }}}}{{{\text{ Conductance }}}} = {\text{ Conductivity }} \times {\text{Resistance}}\;\;$

 $= 0.146 \times{10^{ - 3}}\;{\text{S}}\;{\text{c}}{{\text{m}}^{ - 1}} \times 1500\Omega$

$=0.218\;{\text{c}}{{\text{m}}^{ - 1}}$

 

10. The conductivity of ${\text{NaCl}}$ at $298\;{\text{K}}$ has been determined at different concentrations and the results are given below:

${\text{concentration/M}}$

${\text{0}}{\text{.001}}$

${\text{0}}{\text{.010}}$

${\text{0}}{\text{.020}}$

${\text{0}}{\text{.050}}$

${\text{0}}{\text{.100}}$

${\text{1}}{{\text{0}}^2} \times {\text{ K/S }}{{\text{m}}^{ - 1}}$

${\text{1}}{\text{.237}}$

${\text{11}}{\text{.85}}$

${\text{23}}{\text{.15}}$

${\text{55}}{\text{.53}}$

${\text{106}}{\text{.74}}$


for all concentrations and draw a plot between ${\Lambda _{\text{m}}}$ and ${{\text{C}}^{1/2}}$

Find the value of ${{\Lambda }_{\text{m}}}{}^\circ$

Ans.

Using the following unit conversion factor, $\dfrac{{1S\;{\text{c}}{{\text{m}}^{ - 1}}}}{{100{\text{S}}{{\text{m}}^{ - 1}}}} = 1$

Concentration (M)

${\text{K}}\left( {{\text{S}}{{\text{m}}^{ - 1}}} \right)$

${\text{K}}\left( {{\text{Sc}}{{\text{m}}^{ - 1}}} \right)$

${\Lambda _m} = \dfrac{{1000 \times k}}{{{\text{ Molanity }}}}\left( {{\text{Sc}}{{\text{m}}^2}\;{\text{mo}}{{\text{l}}^{ - 1}}} \right)$

${{\text{C}}^{1/2}}\left( {{{\text{M}}^{1/2}}} \right)$

${10^{ - 3}}$

$1.237 \times {10^{ - 2}}$

$1.237 \times {10^{ - 4}}$

$\dfrac{{1000 \times 1.237 \times {{10}^{ - 4}}}}{{{{10}^{ - 3}}}} = 123.7$

$0.0316$

${10^{ - 2}}$

$11.85 \times {10^{ - 2}}$

$11.85 \times {10^{ - 4}}$

$\dfrac{{1000 \times 11.85 \times {{10}^{ - 4}}}}{{{{10}^{ - 2}}}} = 1118.5$

$0.100$

$2 \times {10^{ - 2}}$

$23.15 \times {10^{ - 2}}$

$23.15 \times {10^{ - 4}}$

$\dfrac{{1000 \times 23.15 \times {{10}^{ - 4}}}}{{2 \times {{10}^{ - 2}}}} = 115.8$

$0.141$

$5 \times {10^{ - 2}}$

$55.53 \times {10^{ - 2}}$

$55.53 \times {10^{ - 4}}$

$\dfrac{{1000 \times 55.53 \times {{10}^{ - 4}}}}{{5 \times {{10}^{ - 2}}}} = 111.1$

$0.224$

${10^{ - 1}}$

$106.74 \times {10^{ - 2}}$

$106.74 \times {10^{ - 4}}$

$\dfrac{{1000 \times 106.74 \times {{10}^{ - 4}}}}{{{{10}^{ - 1}}}} = 106.7$

$0.316$


Graph molar concentration vs. concentration

$\Lambda {}^\circ \text{cm}=$ Intercept of $\Lambda {\text{m}}$axis $= 124.0\;{\text{S}}\;{\text{c}}{{\text{m}}^2}\;{\text{mo}}{{\text{l}}^{ - 1}}$, Extrapolation to zero concentration yields this result.

 

11. Conductivity of $0.00241{\text{M}}$ acetic acid is $7.896 \times {10^{ - 5}}{\text{Sc}}{{\text{m}}^{ - 1}}.$ Calculate its. Calculate its molar conductivity. If $\Lambda {}^\circ \text{m}$ for acetic acid is $390.5\;{\text{S}}\;{\text{c}}{{\text{m}}^2}\;{\text{mo}}{{\text{l}}^{ - 1}}$, what is its dissociation constant?

Ans. $\Lambda _{\text{m}}^{\text{c}}{\text{ = }}\dfrac{{\kappa \times {\text{1000}}}}{{{\text{ Molarity }}}}$

$=\frac{(7.896\times10^{-5}Scm^{-1}\times1000cm^{3}L^{-1})}{0.241\times mol L^{-1}}=32.76 S cm^{2}mol^{-1}$

\[\alpha  = \dfrac{{\Lambda _m^c}}{{\Lambda m^\circ }} = \dfrac{{32.76}}{{390.5}} = 8.4 \times {10^{ - 2}}\]

${k_a} = \dfrac{{C{\alpha ^2}}}{{1 - \alpha }} = \dfrac{{0.24 \times {{\left( {8.4 \times {{10}^{{\text{ }} - 2}}} \right)}^2}}}{{1 - 0.084}} = 1.86 \times {10^{{\text{ }} - 5}}$


12. How much charge is required for the following reductions:

  1. $\mathbf{1\;{\text{mol}}}$of $\mathbf{{\text{A}}{{\text{l}}^{3 + }}}$ to $\mathbf{{\text{Al}}}$ ?

 Ans. Aluminum ion have to lose three electrons to be in aluminum elemental state and the reaction is ${\text{A}}{{\text{l}}^{3 + }} + 3{\text{e}} \to {\text{Al}}$. The amount of charge needed for reduction of $1\;{\text{mol}}$ will be: ${\text{A}}{{\text{l}}^{3 + }} = 3\;{\text{F}} = 3 \times 96500{\text{C}} = 289500{\text{C}}$.

  1. $\mathbf{1\;{\text{mol}}}$ of $\mathbf{{\text{C}}{{\text{u}}^{2 + }}}$ to $\mathbf{{\text{Cu}}?}$

Ans. cupric ion needs to lose two electrons to be in copper (0) state. The electrode reaction occurring is as follows: ${\text{C}}{{\text{u}}^{2 + }} + 2{{\text{e}}^ - } \to {\text{Cu}}$

The amount of charge required for conversion of $1\;{\text{mol}}$ of ${\text{C}}{{\text{u}}^{2 + }} = 2\;{\text{F}} = 2 \times 96500 = 193000{\text{C}}$.

  1. $\mathbf{1\;{\text{mol}}}$ of $\mathbf{{\text{Mn}}{{\text{O}}^4}}$ to $\mathbf{{\text{M}}{{\text{n}}^{2 + }}}$ 

Ans. in the compound ${\text{Mn}}{{\text{O}}^4}$, manganese is in +7 oxidation state; which is reduced to +2 oxidation state with the release of five electrons.

${\text{Mn}}{{\text{O}}_4} \to {\text{M}}{{\text{n}}^{2 + }}$ i.e. ${\text{M}}{{\text{n}}^{7 + }} + 5{{\text{e}}^ - } \to {\text{M}}{{\text{n}}^{2 + }}$

The Quantity of charge needed for reduction of  $1\;{\text{mol}}$ of ${\text{Mn}}{{\text{O}}^4}$ to ${\text{M}}{{\text{n}}^{2 + }}$ $ = 5\;{\text{F}} = 5 \times 96500{\text{C}} = 4825000{\text{C}}$.


13. How much electricity in terms of Faraday is required to produce.

  1. $\mathbf{20.0\;{\text{g}}}$ of $\mathbf{{\text{Ca}}}$ a from molten $\mathbf{{\text{CaC}}{{\text{l}}_2}}$ ?

Ans. ${\text{C}}{{\text{a}}^{2 + }} + 2{{\text{e}}^ - } \to {\text{Ca}}$

As There are two electrons transacted in the above reaction, therefore ${\text{1 mol}}$ of ${\text{Ca}}$or $40\;{\text{g}}$ of ${\text{Ca}}$will require $ = 2\;{\text{F}}$ electricity and $20\;{\text{g}}$ of ${\text{Ca}}$will require $ = 1\;{\text{F}}$ of electricity.

  1. $\mathbf{40.0\;{\text{g}}}$ of $\mathbf{{\text{Al}}}$ from molten $\mathbf{{\text{A}}{{\text{l}}_2}{{\text{O}}_3}}$ ?

Ans. ${\text{A}}{{\text{l}}^{3 + }} + 3{{\text{e}}^ - } \to {\text{Al}}$

As the number of electrons transacted in the above reduction of aluminum ion is three,

Therefore,  ${\text{1 mol}}$of ${\text{Al}}$ or $27\;{\text{g}}$ of ${\text{Al}}$ will require = $3\;{\text{F}}$ electricity

And,

$40\;{\text{g}}$ of ${\text{Al}}$ will require electricity

${\text{ = }}\dfrac{{\text{3}}}{{{\text{27}}}}{{ \times 40 = 4}}{\text{.44F}}$ of electricity.


14. How much electricity is required in coulomb for the oxidation of

  1. $\mathbf{1\;{\text{mol}}}$ of $\mathbf{{{\text{H}}_2}{\text{O}}$ to ${{\text{O}}_2}}$

Ans. The oxidation of water occurs in the following way:

${{\text{H}}_{\text{2}}}{\text{O}}\xrightarrow{{}}{{\text{H}}_{\text{2}}}{\text{ + }}\dfrac{{\text{1}}}{{\text{2}}}{{\text{O}}_{\text{2}}}$

Or

${{\text{O}}^{{\text{2 - }}}}\xrightarrow{{}}\dfrac{{\text{1}}}{{\text{2}}}{{\text{O}}_{\text{2}}}{\text{ + 2}}{{\text{e}}^{\text{ - }}}$

The number of electrons transacting are two. Therefore the amount of electricity needed $ = 2\;{\text{F}} = 2 \times 96500{\text{C}} = 193000{\text{C}}$

  1. $\mathbf{1\;{\text{mol}}}$ of $\mathbf{{\text{FeO}}}$ to $\mathbf{{\text{F}}{{\text{e}}_2}{{\text{O}}_3}}$

Ans. The oxidation reaction of ${\text{FeO}}$ takes place in the following manner:

${\text{FeO}} + \dfrac{1}{2}{{\text{O}}_2} \to \dfrac{1}{2}\;{\text{F}}{{\text{e}}_2}{{\text{O}}_3}$

Or

${\text{F}}{{\text{e}}^{2 + }} \to {\text{F}}{{\text{e}}^{3 + }} + {{\text{e}}^ - }$

The electron transfer is of one electron unit, therefore the Quantity of electricity essential $ = 1\;{\text{F}} = 96500{\text{C}}$


15. A solution of $\mathbf{{\text{Ni}}{\left( {{\text{N}}{{\text{O}}_3}} \right)_2}}$ is electrolyzed between platinum electrodes using a current of 5 amperes for 20 minutes. What mass of Ni is deposited at the cathode?

Ans. firstly, we will find charge in coulombs using the formula: ${\text{Q  =  It}}$

Amount of electricity passed${\text{(Q)}}$ $ = (5\;{\text{A}}) \times (20 \times 60{\text{sec}}) = 6000{\text{C}}$

The reduction of nickel occurs in the following way:

${\text{N}}{{\text{i}}^{2 + }} + 2{{\text{e}}^{\text{ - }}}{\text{ }}\xrightarrow{{}}{\text{Ni}}$

Therefore, $2\;{\text{F}}$or $2 \times 96500{\text{C}}$is the amount of charge deposit for \[{\text{1 mol}}\] of ${\text{Ni}} = 58.7\;{\text{g}}$

Now,

The $6000{\text{C}}$ of charge will deposit $ = \dfrac{{58.7 \times 6000}}{{2 \times 96500}} = 1.825\;{\text{g}}$ of ${\text{Ni}}$


16. Three electrolytic cells, $\mathbf{{\text{A}},{\text{B}},{\text{C}}}$ containing solutions of $\mathbf{{\text{ZnS}}{{\text{O}}_4},{\text{AgN}}{{\text{O}}_3}}$ and $\mathbf{{\text{CuS}}{{\text{O}}_4}}$, respectively are connected in series. A steady current of 1.5amperes was passed through them until $\mathbf{45\;{\text{g}}}$ of silver deposited at the cathode of cell B. How long did the current flow? What mass of copper and zinc were deposited?

Ans. Given: ${\text{I = 1}}{{.5\;A,\;W = 1}}{{.5\;g}}$ of ${\text{Ag t}} = ?,{\text{E}} = 108,{\text{n}} = 1$

Applying Faraday's first law of electrolysis,

${\text{W}} = {\text{ZIt}}$ 

Or

 ${\text{W = }}\dfrac{{\text{E}}}{{{\text{nF}}}}{\text{It}}$ 

By substituting the values provided in the about formula,${\text{t}}$can be calculated;

 ${\text{t = }}\dfrac{{{\text{1}}{{.45 \times 96500}}}}{{{\text{1}}{{.5 \times 108}}}}{\text{ = 863}}{\text{.73}}$ seconds.

Now for ${\text{Cu}},{{\text{W}}_{\text{1}}} = 1.45\;{\text{g(given)}}$ of ${\text{Ag}}{{\text{E}}_1} = 108,\;{{\text{W}}_2} = ?$

${{\text{E}}_2} = 31.75$

Applying Faraday's ${2^{{\text{nd }}}}$ law of electrolysis

 $\dfrac{{{{\text{W}}_{\text{1}}}}}{{{{\text{W}}_{\text{2}}}}}{\text{ = }}\dfrac{{{{\text{E}}_{\text{1}}}}}{{{{\text{E}}_{\text{2}}}}}$

$\dfrac{{{\text{1}}{\text{.45}}}}{{{{\text{W}}_{\text{2}}}}}{\text{ = }}\dfrac{{{\text{108}}}}{{{\text{31}}{\text{.75}}}}{{\;\;}}$

${{\text{W}}_{\text{2}}}{\text{  =  }}\dfrac{{{\text{1}}.{\text{45}} \times {\text{31}}{\text{.75}}}}{{{\text{108}}}}$

Copper deposited $ = 0.426\;{\text{g}}$ of ${\text{Cu}}$

likewise, 

for ${\text{Zn}},{{\text{W}}_1} = 1.45\;{\text{g}}$ of ${\text{Ag}},{{\text{E}}_1} = 108$,

${\text{W}}2 = ?{\text{E}}2 = 32.65$

Using formula, $\dfrac{{{{\text{W}}_{\text{1}}}}}{{{{\text{W}}_{\text{2}}}}}{\text{ = }}\dfrac{{{{\text{E}}_{\text{1}}}}}{{{{\text{E}}_{\text{2}}}}}$

$\dfrac{{{\text{1}}{\text{.45}}}}{{{{\text{W}}_{\text{2}}}}}{\text{ = }}\dfrac{{{\text{108}}}}{{{\text{32}}{\text{.65}}}}$

${{\text{W}}_{\text{2}}}{\text{ = }}\dfrac{{{\text{1}}{{.45 \times 32}}{\text{.65}}}}{{{\text{108}}}}{\text{ = 0}}{\text{.438}}$ of ${\text{Zn}}$

Zinc deposited by \[{\text{1295}}{\text{.6g C}}\] is 0.438 g.


17. Predict if the reaction between the following is feasible:

Given standard electrode potentials:

$\mathbf{E_{1 / 2, I_{2}, I^{-}}^{o}=+0.451 V}$

$\mathbf{E_{C u^{2+}, C u}^{o}=+0.34 V}$

$\mathbf{E_{1 / 2 B r_{2}, B r^{-}}^{o}=+1.09 V}$

$\mathbf{E_{A g^{+}, A g}^{o}=+0.80 V, E_{F e^{3+}, F e^{2+}}^{o}=+0.77 V}$

  1. $\mathrm{Fe}^{3+} \text { (aq) and } \mathrm{I}^{-} \text {(aq) }$

Ans: The reaction is feasible if the emf of the cell reaction is positive.

$\text { (i) } F e^{3+}(a q)+I_{(a q)}^{-} \rightarrow F e^{2+}(a q)+\frac{1}{2} I^{2}(g)$

$\text { i.e., } P t / I^{2} / I^{-}(a q) \| F e^{3+}(a q)\left|F e^{2+}(a q)\right| P t$

$\therefore E_{c e l l}^{o}=E_{F e^{3+} \cdot F e^{2+}}-E^{o}_{1 / 2 I_{2}, f^{2}}$

$=0.77-0.54=0.23 V \text { (Feasibles)}$

  1. $\mathbf{2 \mathrm{Ag}^{+}{ }_{(a q)}+C u_{(s)} \rightarrow 2 \mathrm{Ag}_{(s)}+\mathrm{Cu}^{2+}_{(a q)}}$

Ans: $2 \mathrm{Ag}^{+}{ }_{(a q)}+C u_{(s)} \rightarrow 2 \mathrm{Ag}_{(s)}+\mathrm{Cu}^{2+}_{(a q)}$

$\text { i.e., } \mathrm{Cu}\left|\mathrm{Cu}^{2+}{(a q)} \| \mathrm{Ag}_{(a q)}^{+}\right| \mathrm{Ag}$

$\therefore E_{c e l l}^{o}=E^{o}{ }_{A g^{+A g}}-E_{C u}^{o}, Cu$

$=0.80-0.34=0.46 V \text { (Feasible) }$

  1. $\mathbf{\mathrm{Fe}^{3+}{(a q)}+\mathrm{Br}_{(a q)}^{-} \rightarrow \mathrm{Fe}^{2+}{ }_{(a q)}+\frac{1}{2} \mathrm{Br}_{2(\mathrm{~g})}}$

Ans: $\mathrm{Fe}^{3+}{(a q)}+\mathrm{Br}_{(a q)}^{-} \rightarrow \mathrm{Fe}^{2+}{ }_{(a q)}+\frac{1}{2} \mathrm{Br}_{2(\mathrm{~g})}$

$E_{c e l l}^{o}=0.77-1.09=-0.32 v(\text { Not feasible })$

  1. $A g_{(s)}+F e^{3+}_{(a q)} \rightarrow A g^{+}_{(a q)}+F e^{2+}(a q)$

Ans: $A g_{(s)}+F e^{3+}_{(a q)} \rightarrow A g^{+}_{(a q)}+F e^{2+}(a q)$

$E_{c e l l}^{o}=0.77-0.80=-0.03 v(\text { not feasible })$

  1. $\frac{1}{2} B r_{2(g)}+F e^{2+}(a q) \rightarrow B r_{(a q)}^{-} F e^{3+}(a q)$

Ans: $\frac{1}{2} B r_{2(g)}+F e^{2+}(a q) \rightarrow B r_{(a q)}^{-} F e^{3+}(a q)$

$E_{c e l l}^{o}=1.09-0.77=0.32 V(\text { Feasible })$


18. Predict the products of electrolysis of the following:

  1. An aqueous solution of \[{\text{AgN}}{{\text{O}}_{\text{3}}}\] with silver electrodes.

Ans. ${\text{AgN}}{{\text{O}}_{\text{3}}}{\text{(s) }}\xrightarrow{{}}{\text{ A}}{{\text{g}}^{\text{ + }}}{\text{(aq)  +  N}}{{\text{O}}_{\text{3}}}^{\text{ - }}{\text{(aq)}}$

${{\text{H}}_{\text{2}}}{\text{O}}\overset {} \leftrightarrows {\text{ }}{{\text{H}}^{\text{ + }}}{\text{  +  O}}{{\text{H}}^{\text{ - }}}$

At cathode: The discharge potential of ${\text{A}}{{\text{g}}^ + }$ ions is lower than that of ${{\text{H}}^ + }$ions. As a result, Ag ions will be deposited as ${\text{Ag}}$rather than ${{\text{H}}^ + }$ ions.

At anode: When the ${\text{Ag}}$ anode is attacked by ${\text{N}}{{\text{O}}_{\text{3}}}^-$ ions, the ${\text{Ag}}$ dissolves and forms ions in the solution.

${\text{Ag(s)}}\xrightarrow{{}}{\text{A}}{{\text{g}}^{\text{ + }}}{\text{(aq)  +  }}{{\text{e}}^{\text{ - }}}$

  1. An aqueous solution of \[{\text{AgN}}{{\text{O}}_{\text{3}}}\]  with platinum electrodes.

Ans. At cathode: The discharge potential of ${\text{A}}{{\text{g}}^ + }$ ions is lower than that of ${{\text{H}}^ + }$ions. As a result, Ag ions will be deposited as ${\text{Ag}}$rather than ${{\text{H}}^ + }$ ions.

At anode: Because the anode is not attackable, ${\text{OH}}$ions have a lower discharge potential than${\text{N}}{{\text{O}}_{\text{3}}}^ - $ions. As a result, ${\text{OH}}$ will be evacuated first, followed by ${\text{N}}{{\text{O}}_{\text{3}}}^ - $ions, which will disintegrate and release ${{\text{O}}_2}$.

${\text{OH}}_{}^ -  \to {\text{OH}} + {{\text{e}}^ - }$

$4{\text{OH}} \to 2{{\text{H}}_2}{{\text{O}}_{(1)}} + {{\text{O}}_{2(g)}}$

  1.  A dilute solution of \[{{\text{H}}_{\text{2}}}{\text{S}}{{\text{O}}_{\text{4}}}\] with platinum electrodes.

Ans. ${{\text{H}}_2}{\text{S}}{{\text{O}}_4} \to 2{{\text{H}}^{\text{ + }}} + {\text{S}}{{\text{O}}_4}^{2 - }$

${{\text{H}}_2}{\text{O}} \rightleftharpoons {\text{H  +  O}}{{\text{H}}^ - }$

At cathode: ${{\text{H}}^ + } + {{\text{e}}^ - } \to {\text{H}}$

${\text{H}} + {\text{H}} \to {{\text{H}}_{2(\;{\text{g}})}}$

At anode: ${\text{O}}{{\text{H}}^ - } \to {\text{OH}} + {{\text{e}}^ - }$

$4{\text{OH}} \to 2{{\text{H}}_2}{\text{O}} + {{\text{O}}_{2(g)}}$

Therefore, Hydrogen gas is released at the cathode and ${{\text{O}}_2}$ gas at the anode.

  1. An aqueous solution of \[{\text{CuC}}{{\text{l}}_{\text{2}}}\] with platinum electrodes.

Ans. ${\text{CuC}}{{\text{l}}_{\text{2}}} \to {\text{C}}{{\text{u}}^{2 + }} + 2{\text{Cl}}_{}^ - $

${{\text{H}}_2}{\text{O}} \rightleftharpoons {\text{H  +  O}}{{\text{H}}^ - }$

At cathode:${\text{C}}{{\text{u}}^{2 + }}$ ions will be reduced more than ${{\text{H}}^ + }$ ions, resulting in copper deposition at the cathode. 

${\text{C}}{{\text{u}}^{2 + }} + 2{{\text{e}}^ - } \to {\text{Cu}}$

At anode: \[{\text{C}}{{\text{l}}^{\text{ - }}}\]ions will be released first, followed by ${\text{O}}{{\text{H}}^{\text{ - }}}$ ions that will stay in solution. ${\text{C}}{{\text{l}}^{\text{ - }}} \to {\text{Cl}} + {{\text{e}}^ - }$

${\text{Cl}} + {\text{Cl}} \to {\text{C}}{{\text{l}}_{2(\;{\text{g}})}}$

Hence, copper will get set down on the cathode and ${\text{C}}{{\text{l}}_2}$ gas will be liberated at the anode.


Important Points Covered in Class 12 Chemistry Chapter 3 - Electrochemistry

  1. The field of chemistry that deals with the link between electrical and chemical energy, as well as the interconversion of one form into another, is known as electrochemistry.

  2. Two metallic electrodes submerged in electrolytic solutions make up an electrochemical cell. There are two sorts of cells:

  1. Electrolytic cells

  2. Galvanic cells are two types of cells.

  1. Two half cells make up a galvanic cell. An electrolytic solution and a metallic electrode are contained in each half cell. The anode is the electrode where oxidation takes place, and the cathode is the electrode where reduction takes place. A permeable pot or a salt bridge is used to divide the half-cells from one another.

  2. The presence of a potential difference between two electrodes is indicated by the passage of current from one to the other. The electromotive force is the difference in potential that causes current to flow from the electrode with a higher negative potential (emf).

  3. Emf (volts) x Quantity of electricity Equals Electrical energy (coulombs)

  4. SHE's potential is set to a value of zero at random. E° = 0 volts It is used to measure the standard electrode potentials as a reference electrode.

  5. The electrochemical series is created when the components are ordered in order of their standard electrode potentials.


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Electrochemistry Class 12 NCERT Solutions

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NCERT Solutions for Class 12 Chemistry PDF Download

NCERT Solutions Class 12 Chemistry - Related Links

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Chapter 3 Chemistry Class 12 Questions are Based on the Following Topics:

  • Standard electrical potential.

  • Calculating the emf of the cell.

  • Calculating the Gibbs energy.

  • Sums on Kohlrausch’s Law.

  • Sums on molar conductivity.

  • Conceptual long answer type questions.

  • Setting up various cells.


Students finding Electrochemistry difficult should check out the Chemistry Class 12 NCERT solutions Chapter 3.


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  • Vedantu's NCERT Chemistry Solutions provide comprehensive and well-researched materials with precise and easily understandable answers to the exercise questions in the NCERT Textbook.

  • These solutions are developed by expert faculty members at Vedantu, adhering to the latest CBSE Term 1 and Term 2 syllabus and guidelines for the academic year 2021-22.

  • Apart from preparing students for their board exams, these solutions also equip them for various competitive exams, as NCERT books are highly recommended study materials for such exams.

  • The study materials, including the required PDFs, can be downloaded free of cost, providing convenient access to students.


Conclusion

Vedantu's Electrochemistry Class 12 NCERT solutions for CBSE Chemistry Chapter 3 provide a comprehensive and effective resource for students studying this topic. The solutions cover all the important concepts and exercises outlined in the NCERT textbook, ensuring that students have a clear understanding of electrochemistry. Vedantu's solutions are well-structured and easy to follow, making it easier for students to grasp complex concepts and solve problems. The explanations are detailed and thorough, addressing common difficulties and providing step-by-step solutions. With Vedantu's Electrochemistry Class 12 NCERT solutions, students can enhance their understanding of electrochemistry and improve their performance in examinations. Overall, Vedantu's solutions are a valuable tool for Class 12 Chemistry students.

FAQs on NCERT Solutions for Class 12 Chemistry Chapter 3 - Electrochemistry

1. What is Electrochemistry all About?

Electrochemistry deals with the relationship between Chemistry and electricity. It focuses on how electricity can be produced from chemical changes and how chemical changes, in turn, produce electricity. It discusses how reactions can take place in a battery between a cathode and an anode with electrolyte in between them.


Electrochemical reactions are that branch of study where any chemical reaction such as in a battery produces an electric current or where the application of electricity produces a chemical reaction. Ch 3 Chemistry Class 12 can be quite challenging for most students.


Students having difficulty with this chapter can refer to Electrochemistry Class 12 NCERT Solutions.

2. How to Prepare for Electrochemistry?

As a common denominator of preparation, just studying the chapter at least three times will suffice. Students can then make notes on the chapter and tackle the exercises. Ch 3 Chemistry Class 12 is quite a tough chapter so students can make use of Electrochemistry Class 12 solutions.


After studying the chapters students can begin their preparation on past year papers and sample papers. These will help students to gain confidence and experience in solving these types of problems.


Another trick of preparing for Electrochemistry is that students should clearly understand when electrical changes give rise to chemical changes and when chemical changes give rise to electrical changes.

3. Where can I Find Solutions to Class 12 Chapter 3 Electrochemistry?

Students can find ElectroChemistry Class 12 solutions on Vedantu's website. The solutions are presented in a light, clear, and straightforward way. They are easily downloadable in pdf format and they are free of cost. Whenever students have any difficulty with their understanding they can refer to the solutions provided.


Chapter 3 Chemistry Class 12 is not an easy chapter. Students struggle to understand concepts of anode, cathode and electrolyte. They get confused with these topics. Also, conductivity and resistivity are difficult concepts to explain. Students should know that perseverance is the only key to cracking Electrochemistry.

4. What is Molar conductivity according to Chapter 3 of Class 12 Chemistry?

Molar conductivity can be defined as the conducting power of all the ions. It is formed by dissolving one mole of electrolyte in the solution. Molar conductivity is not constant. The efficiency of a given electrolyte in conducting electricity in a solution is known by molar conductivity.

5. What is Kohlrausch’s Law? Explain?

An equivalent conductivity of an electrolyte at an infinite solution is equal to the sum of conductances of anions and cations. This is called Kohlrausch's law. Students can refer to NCERT Solutions to learn the definitions, which are given in a simple and understanding way. Kohlrausch's law of migration of ions helps in calculating any electrolyte of λ o. But for the weak electrolytes, the value can be determined if we know Ëm ° and Λm at C, which is a given concentration.

6. What is electrical potential? How can you define the magnitude of the electrical potential?

The amount of work required to move a unit charge from a reference point to a particular point against the electric field is known as electrical potential. The magnitude of the electrical potential depends on the amount of work done in moving an object from one point to another against the electric field. Whenever there is a movement of the object against the electric field there is a gain of some energy. This is known as electrical potential energy.

7. What is Gibbs free energy?

Gibbs free energy is the quantity used to measure the amount of work done in a thermodynamic system when temperature and pressure are constant. There are many problems in this chapter. Students have to be thorough with the formula to solve the problems. You can also refer to NCERT Solutions and practice formula-based problems to get a proper concept of the topic. Gibbs Law is also a reduced chemical potential when it attains equilibrium. This is also known as free enthalpy and also it serves as an impulsiveness measure with content variables of temperature and pressure.

8. What is Electronic Conductance?

Electrical conductance through metals is called metallic or electronic conductance that is due to the movement of electrons, which depends on the nature of the structure of the metal, the number of valence electrons per atom and temperature(decrease or increase in temperature). As the electrons enter at one end and go out through the other end, the composition of the metallic conductor remains unchanged.