INDIAN NATIONAL CHEMISTRY OLYMPIAD With SOLVED PAPERS NSEC & INChO 2014-2017First & Foremost Since the year 1999 when India started participating in the Chemistry Olympiads, the interest of the school students in the country has tremendously increased in this international jamboree in chemistry. Now, we find a number of really talented students in almost all the prestigious schools in India who are excited about this mega event and sincerely desire to participate in it, win a handful of medals and make the country proud. We just need to educate them about the competition, and provide them the relevant study material. The Chemistry Olympiad tests the participant's level of understanding and interest in chemistry and an outstanding ability to relate chemical facts with one another as well as the practical world. It requires the complete grasp of both theoretical and experimental chemistry at the level of senior secondary with an ability to think at the higher levels. The syllabus of the Olympiad encompasses several areas of chemistry organic, inorganic, physical, analytical chemistry, biochemistry and spectroscopy. ‘This book has been written, keeping in mind, the orientation required on the parts of students to face the Olympiads at international, national or regional level. The design of the book is such as to give the student an insight into both theoretical and experimental chemistry. Itishoped, this book will charge you up for the Olympiad juggernaut. Ihave tried my best to keep this book error-free. However, if there any error is left, I request the readers to bring forward to my notice. Suggestions for the further improvement ofthe bookare welcome, With best wishes Dr. Praveen KumarCONTENTS 1, Atomic Structure Chemical Equilibrium 3. Chemical Kinetics and Radioactivity 4, Chemical Energetics and Chemical Thermodynamics 5. Gaseous State 6. Redox Reactions and Electrochemistry 7. Solutions 8. Biomolecules 9. Organic Chemistry I 10. Organic Chemistry IL © NSEC & INChO Solved Papers 2014-2015 © NSEC & INChO Solved Papers 2015-2016 © NSEC & INChO Solved Papers 2016-2017 1-30 31-71 72-110 111-120 121-128 129-143 144-164, 165-203 204-241 242-316 1-34 1-42 1-44Introduction CHEMISTRY OLYMPIADS ABOUT THE EXAM & HOW TO SUCCEED IN IT? Indian National Chemistry Olympiad India is relatively new to the forum of Chemistry Olympiad. It participated for the first time in the competition in 1999 at Bangkok in Thailand. In 2001, India hosted the Chemistry (Olympiads and received ample of support and encouragement from all the participant countries Stages ‘Stage I National Standard Examination in Chemistry (NSEC) Homi Bhabha Centre for Science Education (HBCSE) is responsible for dealing with all activities related to Science and Mathematics Olympiads in India. The Indian Association of Chemistry Teachers conducts the theory part of the Indian National Chemistry Olympiad. This examination is called National Standard Examination in Chemistry in which students of class “X_ and XII participate, itis held in November of the year before the Indian National Chemistry Olympiad is held. Stage II Indian National Chemistry Olympiad (INChO) Based on performance in NSEC, the top 300 students in order of merit qualify to appear for the second Stage of the Olympiad program (INChO). In case there is a tie atthe last position, all students with the same marks qualify for INChO. {ll students who qualify to appear for INChO get a certificate of merit from IAPT. (Indian [Association of Physics Teachers) INChO is organised by HBCSE at about 15 centres in the country. Stage III Orientation Cum Selection Camp (OCSC) in Chemistry (On the basis of performance in INChO, the top 35 students in the merit list are selected for Stage III Orientation Cum Selection Camp (OCSC) in chemistry. In the event, there is a tie at the last position all students with the same marks at this last position will qualify for OCSC. There is no other criterion or provision for selection to OCSC. ‘OCSC in chemistry is organised by HBCSE sometime in April to June for 2-3 weeks.‘The camps include several theoretical and experimental tests. Orientation is provided to students especially in experiments, The camps conclude with a valedictory function where distinguished scientists are invited to speak to the students. ‘The merit list of OCSC is prepared on the basis of the combined theoretical and experimental score aggregated over all the tests in the camp, with 60% weightage for theory and 40% ‘weightage for experiment, Performance in previous stages (NSEC and INChO) will not be a consideration for the merit list and awards of the OCSC. ‘The top 4 in the OCSC chemistry merit list are declared to be special merit awardees. These special merit awardees are given Rs.5,000/- each in the form of books and cash. In addition there are special prizes to recognise meritorious performance in theory and experiments, ‘The 4 special merit awardees in chemistry selected at the end of the OCSC constitute the 4 ‘member student team for the International Chemistry Olympiad (IChO), provided they satisfy required criteria such as age limit, holding valid Indian passport, medical fitness, parental consent, etc. Stage IV Pre-departure Training (PDT) Camp for IChO The selected 4 member Indian team undergoes a rigorous training programme at HBCSE in theory and experiments, Special laboratories have been developed at HBCSE for the purpose of experimental training. Resource persons from HBCSE and different institutions across the country train the students, The duration of training is subject to IChO regulations, Stage V Participation in International Chemistry Olympiad (IChO) ‘The 4-member student team, 2 teacher leaders and 1 scientific observer constitute the delegation to represent India at the International Chemistry Olympiad (IChO). Career Prospects Participation in Indian National Chemistry Olympiad, becauseitisbased on merit isheldin esteemby the students parentsandteachersalike.tisa well publicisedaffairandisitsprogressis watched theenireIndian community jstparticipatinginthetraining camp ofthe Olympiad ensures openingat thetop institutions in India taddsto the candidates'curriculum vitae and opens for them new vistas ofopportunities. ‘The contest provides the students a chance to interact with the budding talent from other regions and interact with like minded people and exchange ideas. I gives impetus to their éreatve faculty and they are abe to explore new dimensions of learning Chemistry, Month and Frequency of Examination Indian National Chemistry Olympiad is conducted in Januar every year. The students are selected on the basis of NSEC.Craze of Examination Bio-Chemistry is a branch of Chemistry which has been attracting wide scale interest and features prominently in this examination, Most of the questions are asked on this topic. Its, application in the field of Medical Sciences is worth a mention. Participation in Chemistry Olympiad at national level is a position of distinction and is viewed with reverence by the parents, students, teachers and society at large. Since this is not a regular examination, the questions that feature are different and more difficult. It requires exercise of higher mental faculty to tackle the questions asked in this examination. However, itis a much awaited event and the students look forward to participating in them. General Eligibility ‘The candidates participating in this examination must be below 20 years of age and must be students of Class XI or Class XII. The candidates must be students who are enrolled in a school recognised by the government. ‘The contest is not open to students of colleges and universities. Course and Number of Papers ‘Though the entire course of pre-university level Chemistry features in it but there are no set boundaries. The problems are complex and require high degree of knowledge in subject. The following topics are most important part of Chemistry and questions from them feature regularly in the Olympiads, “Atomic Structure, Chemical Equilibria, Chemical Kinetics, Solutions, Bio-molecules, Boron Family, General Organic Chemistry. Skill Set Required ‘The Olympiads require quick thinking and efficient management of time. Speed with accuracy is the skill which is required most in the examination. The data has to be interpreted accurately and presented in a clear manner, leaving no room for ambiguity in practical examination. The candidates must be well versed with the fundamentals of Chemistry because unless the fundamentals are strong, it would be difficult to clear all the rounds and reach the International Chemistry Olympiads. The candidates must have systematic approach to solve the problem. ‘There must be a unity of purpose and all efforts should be directed towards achieving the goal. ‘The candidates must be well acquainted with the latest research in the field. Difficulty Level ‘The difficulty level of Indian National Chemistry Olympiad is high. The questions asked are unconventional and require practical as well as theoretical knowledge of the subject. The candidates must have a esearch oriented mind and ability to decipher the intricate details insubject. They must comprehend the data and provide the solution to the problem in the perfect way, The course is vast and covers the entire Class XI and Class XI, the difficulty increases due to this factor. The candidates face a tough challenge of providing perfect solution by demonstrating authority on the practical aspect of the subject as wel. Previous Years’ Trend Analysis In the national Olympiad the questions asked are of objective type but they require knowledge tobe on tip of the pen without which it would be difficult to be answered. There are questions from 20 questions from Organic Chemistry and 15 questions are from Inorganic Chemistry. ‘There are 15 more questions from other areas of Chemistry. How to Prepare for the Subject in Stipulated Time Since this is not a conventional examination, itis difficult to device a strategy for the preparation. However, regularly going through the syllabus and finding new methods of solving the problems in books isa good way of preparing forthe examination. One way is, to keep reading material on the most recent research in the field which will be conducive in giving exposure to the right kind of questions which feature in the examination. Apart from this, the books available in the market which aid the preparation. Arihant books are the best for helping in the preparation. General Mental set up for Succeeding in the Examination “The candidates, to participate in this examination, must have the power of concentration and hhave the ability to sustain stamina for working over a longer duration of time. Since the work involves exercise of mental faculty its essential thatthe candidates remain free of stress and inclined only to think in the direction of doing well in the examination. The candidates must possess self-confidence and be totally involved in the task of preparing for the examination, ‘They must have ability to think creatively and must be familiar with all the basic concepts of Chemistry. How This Book is Useful for you “This book on the Chemistry Olympiads is an invaluable source of knowledge for the students ‘who are attempting to take the Chemistry Olympiads. The book carries sophisticated and "unconventional problems which are along the lines of the real problems which feature in the Olympiads. Complete solutions to the practical and theoretical problems are given in the book. This book throws up examples before the students as to how to approach the Olympiads, With this book, in hand, the students are never short of practice,Unit 6 Redox Reactions and Electrochemistry Redox Reactions ‘The reactions in which the oxidation and reduction accur simultaneously are known as redox reactions or electron transformation reactions. (Oxidation reaction can be defined as follows + Loss of hydrogen + Gain of oxygen + Loss of electron Itis the process of de-lectronation during which oxidation number increases, Reduction reaction can be defined as follows + Gain of hydrogen, + Loss of oxygen + Gain of electron Itis the process of electronation during which oxidation number decreases. Oxidizing agent or oxidant Itis the substance which undergoes reduction and oxidizes other substance. It gains electrons and its oxidation number decreases. Reducing agent or reductant Itis the substance which undergoes oxidation and reduces other substance. It shows loss of electron during the process and electrons and its oxidation number increases, All the metals are reducing agents, Types of Redox Reactions The redox reactions are of three types (i) Intermolecular redox reactions ‘Those reactions in which oxidation and reduction take place separately in two compounds.130 Indian National Chemistry Olympiag (ii) Intramolecular redox reactions ‘Those reactions in which oxidation and reduction take place in single compound. For example 2KC10, —> 2KC1+30, (iii) Disproportionation reactions Those reactions in which oxidation and reduction of same element in a compound take place, For example sip, — 040, (iv) Direct redox reaction ‘The redox reactions in which oxidation and reduction both are carried out inthe same vessels called ‘direct redox reaction, In this case energy is liberated inthe form of heat energy. () Indirect redox reaction ‘The redox reactions in which oxidation and reduction both are carried out in different vessels is called {indirect redox reaction. In this case energy is liberated in the form of electrical energy. (vi) Oxidation number {Itcan be defined as the charge in which an atom appears to have when present in the given compound or it represents the extent of oxidation or reduction of an element when it changes from free state to that ‘compound. Oxidation state of an atom is defined as oxidation number per atom, Rules for Assigning Oxidation Numbers (© Sum of oxidation numbers of al atoms present in @ neutral compound is equal to zero, Gi) Sum of oxidation numbers of all atoms present in anion is equal to charge onthe on. (i) The oxidation number ofan stom in elementary state is zero. (i) The oxidation number of a monatomic ion is equal to charge oni, (9) The oxidation number of oxygen in most ofthe compounds is -2. But in peroxides its -1 and in Of, itis +2. (vi) The oxidation number of hydrogen is +1 in most of the compounds. But in active metal hydrides (aydrides of group 1 and 2) itis ~ (vii The oxidation number of alkali metals in all the compounds is +1, (vii The oxidation number of alkaline metals in all the compounds is +2, (Gx) The oxidation number of fuorine in all the compounds is 1. () The oxidation number of all halogens is -1 except when the other atom present in the compounds oxygen. (i) The oxidation number of metas in carbonyls and amalgams is zero Evaluation of Oxidation Numbers of Some Typical Compounds () Oxidation state o Fe in e088 (i) Oxidation state of Cr in Cr,0; is +6, (Because it has 5 oxygen atoms linked by peroxide linkage while fone oxygen ins normal Onidation sit), Lt be the nation state of neaRedox Reactions and Electrochemistry 131 X02) We D0 6 ii) H.S0, (or permonosulphuric acid) and H,S,0, have one peroxide linkage each. Calculation of oxidation number of atoms of compounds with covalent and coordinate bonds (i) While calculating oxidation number of covalently bonded atoms + +1 oxidation number is assigned to less electronegative atom. + -1 oxidation number is assigned to more electronegative atom. For example Oxidation number of carbon in HC: Let xbe the oxidation state of C in HCN 8 1x4 Gx) x=+2 () While calculating oxidation number of atoms bonded by coordinate bonds. + In case donor atom is more electronegative than acceptor atom then neglect contribution by the coordinate bond is neglected. + Incase when donor atom is less electronegative than acceptor atom oxidation number of donor atom is +2 and that of acceptor atom is - 2. 9, Oxidation number of carbonin HC=N Let xbe the oxidation state of C in HC: : +144 x20 x=2 4, Oxidation number of carbon in H=NC Let xe the oxidation state of Cin H=2NC ~ 14 (1x-3)4x=0 ( Coordinate bond is neglected as electronegativity of nitrogen atom is more than that of carbon) Some Special Examples for Determining Oxidation Numbers @ Ca0C1, (bleaching powder) has two chlorine atoms and both of them are in different oxidation states because bleaching powder exists as Ca** OCI” and CI”. ‘In Ca(OCI)C1 oxidation number of one chlorine is -1 and of other chlorine is +1. (G) FeO, has structure, FeO. Fe,0; (Oxidation state of one Fe is +2 and that of other two is +3 (ii) NH.NO, has structure; NHj + NO; For NH;, oxidation state of nitrogen; x + 4x — For NO; , oxidation state of nitrogen; x + 2x -2 xa3 foxe45 Electrochemistry IIs the study of relationship between chemical energy and electrical energy, their production during redox reaction and how these two forms of energy are converted into one another.132 Indian National Chemistry Olympiag ‘Conductors and insulators ‘The substances which allow electricity to pass through them are called conductors and those which do not allow electricity to pass through them are called insulators. Electrolytes and non-electrolytes Aqueous solution of some compounds allow electricity to pass through them and decompose when electricity is passed into them, such solutions are called electrolytes. The aqueous solution of certain compounds does not allow electricity to pass through them and they are called nomrelectrolytes, Conductance ‘The conductance is of two types Electronic conductance and electrolytic conductance. {i Electronic conductance + Ttis caused due to flow of electrons. + During electronic conductance substance does not decompose. + Tt decreases the temperature, (ii) Electrolytic conductance + It is caused due to flow of ions. «+ During electronic conductance substance decomposes. « Itincreases the temperature, Electrochemical Cell or Galvanic Cell or Voltaic Cell {i Itis the device to carry out indirect redox reactions. (a In this cell chemical energy changes to electrical energy. (ii) The electrochemical cell has two half cells (cathode and anode). Each half cell has an electrode dipped in an electrolyte. The half cells are connected by sat bridge. The sat bridge is filled with the Solution of strong electrolyte along with agar agar. The salt bridge helps in completing internal ‘ireuit of cell it maintains electrical neutrality between two cells and provides path for mobility of ‘Gharges, Current drops to zero when salt bridge when salt bridge is pulled out. iv) The cathode or reduction half cell is electron deficient and is positively charged. It acquires positive ‘Gharge because t attracts electrons from external circuit. When two or more ions compete at cathode for discharge then cation with higher reduction potential is discharged at cathode. {) The anode or oxidation half cell's electron rich and is negatively charged, It acquires negative charge due to liberation of electrons. When two or more ions compete at anode for discharge then anion ‘with higher oxidation potential is Uberated at anode. (vy Electrochemical cell i represented as follows ‘Anode/Anodie electrolyte Cathode/Cathodie electrolyte Celt reaction : zn+Cu® —+ zn +Cu (ii) In electrochemical cell low of electrons is from anode to cathode and flow of currents fro cathode to anode. (vit) Daniell cell is an electrochemical cell having zinc electrode dipped in zine sulphate solution (Anot®) (ad nd copper electrode dipped in copper sulphate solution (Cathode). Cell reaction in Daniell cell Zn +CuS0, —> ZnS0, +Cu‘Redox Reactions and Electrochemistry 133 Reaction at anode (Oxidation half reaction) Zn -2e” —+ Zn’* Reaction at cathode (Reduction half reaction) Cu2* + 2e7 —+ Cu Electrode Potential Itis tendency of an electrode to gain or lose electron when in contact with its own ions. Itis of two types. Reduction potential thas tendency to accept electrons, Oxidation potential Ithas tendency to lose electrons, Note (i) The numerical value of oxidation and reduction potential of an electrode are same but are ‘opposite in sign Eng =~ Eos and Bos When electrode potential is measured at 298 K (or 25°C), | atm pressure and I M concentration tis called standard electrode potential. (i) Negative value of standard reduction potential means that oxidation takes place on this electrode with respect to standard hydrogen electrode, EMF (E) It is the potential difference between two electrodes of a cell when no current is flowing in the circuit. Feu = Ec ~ Eq (where, Eg and Ey both values are substituted in terms of reduction potential) ‘Standard emf of the cell is calculated as follows Etay = Eg. ~ Ej (where, Fz 1s the standard reduction potential of cathode and £% is the standard ‘oxidation potential of anode) red = ~ Ere Electrochemical Series tis the arrangement of elements in the decreasing order oftheir standard reduction potentials. It helps in comparing reactivity of metals and to know if H, will be displaced by metal from acid or not. Applications of Electrochemical Series + Ithelps in predicting and comparing the reactivity of the elements. + Itpredicts if the metal wil displace hydrogen by metal from acid or not. + Itpredicts the feasibility of the reaction. If emf of cell is positive the reaction is feasible, + Ithelps in predicting the relative strengths of oxidizing and reducing agent or ease of oxidation and. reduction, Greater the value of E°more will be its tendency to be reduced, hence strong oxidizing agent. + Lower the value of reduction potential of an element greater wil be its reducing power. + Compounds having highly electronegative element in highest oxidation state behave as strong oxidizing agent, e.g, KCIO, 1s a strong oxidising agent because chlorine is in its highest oxidation state in this compound. + The oxide in which element Is in its highest oxidation state can't act as reducing agent. + Greater the reduction potential; stronger is the oxidizing agent.134 indian National Chemistry Olympiag Nernst Equation The Nemst equation gives the relationship between electrode potential and ionic concentration of electrolyte solution () Representation of Nernst equation for an electrode (reduction) For the electrode reaction Mt ne” —> MO) : DOOR yall pe Feng + Fae ni “Fame pata* pe BEM = Bee) where, n= number of electrons in electrode reaction, (ii) Representation of Nernst equation for cell For the cell reaction 591 log M™*] A+ bB —> eC + aD actant|_ p+ , 0.0591 9 ¢athodic electrolyte "| product |= "=" ‘anodic electrolyte n 7m Remember Greater the value of | Sathodic electrolyte | oy emf o! I. (0 Greater the vu of SREB IECUOHTE] more ibe ext o the cel Free energy change (4G) and emf (of cell At equilibrium Fy = 0 “8G = nF -AG"= NE (where, AG*is the standard free energy) (8) EME (® of cell and equilibrium constant (K.) NEE? __nFE® 10 ae ie 8 Ke =F 303RT ~ 0.0591 Electrolysis Iris the process of decomposition (a chemical reaction) of an electrolyte by passage of electric curent through molten or aqueous state. It is carried out in electrolytic cell. Electrolytic Cell "In an electrolytic cell electrical energy is converted into chemical energy. 1 Hhe’anode of electrolytic cell is negatively charged and cathode is positively charged. {Tons are discharged at both the electrodes. 1 Biche poeta minimum vlog equied for charg of on. The oder of aschare poets Of some ions is as follows : i) SO m=2QnzitRedox Reactions and Electrochemistry 135 where, m= mass of substance in grams, Q= amount of electricity passed Z = electrochemical equivalent xQ Amount of substance deposition = + Electrochemical equivalent is the weight of ion deposited by passing 1 A current for 1 s. + Unit of charge is Faraday and 1 F = 96500 C + Electrochemical equival cer lect quivalent (2) = St + Q=nxF (where, Q= charge, n = number of electrons, F = 96500 C mol + Amount of substance deposited = °4.™t*Q ‘96500 + 1 Faraday is charge carried by 1 mole of electrons + 1 mole of electrons can reduce | mole of monovalent cation or 1/2 mole of divalent cation or 1/3 ‘mole of trivalent cation. i Second Law of Electrolysis IK states that when same quantity of electricity is passed in solutions of different electrolytes, the amount of different ions deposited on electrodes is proportional to their equivalent weights. Weight of substance (1) equivalent weightof () 4.. 1 _ EL ‘weight of substance (2) “equivalent weight of (2) °" ws” Fy Ohm’s Law It relates potential difference, current and resistance. where, (= current, E Resistance (R) + Ttis defined as opposition to flow of electrons. Ret T ‘Its unit is ohm. Conductance (C) + Itis defined as the ease of flow of electrons and is reciprocal of resistance. 1 mho R + Its unit is mho. The SI unit of conductance is Siemens. Specific Resistance or Resistivity (p) + Its defined as resistance of conductor of length 1 cm and area of cross section 1 ¢m?, +p =44 (where,a = area of cross section of conductor and I = length of conductor) + Mts units ohm em136 Indian National Chemistry Olympiad Specific Conductivity or Conductivity (x) + Tis defined as reciprocal of specific resistance f Ts cul iret aed a celleontan) + Its unit is ohm“ cmt and its St unit is Sm“! R_observed resistance _ specific conductance a” 5 ~ specific resistance ~ observed conductance Cell constant Equivalent Conductivity (Coq) It is defined as conducting power of all ions produced by dissolving 1 gram equivalent of electrolyte in V ‘em? of solution. 1000 _x «1000 Gq” normality Where, aq = concentration of solution in gram equivalent /itre Its units is Sm? eq”! or ohm"! m? eq”, eg 2 xV = Molar Conductivity An) Itis defined as conduction power of all ions produced by dissolving 1 mole of electrolyte in Vem? of solution +1000 1000 xv. nexy- Seu a G ‘molarity ‘where, Cy, =molar concentration of solution Its unit is Sm? eq orohm~' m? eq Variation of molar conductivity with concentration ‘Molar and equivalent conductance of solution depends on nature of electrolyte, temperature and concentration of solution. (o For strong electrolytes the variation is given by Huckel Onsager equation, ‘hn = Nin - VE where, b = constant (depends on nature of solvent and temperature) ‘A, = molar conductance at infinite dilution ‘The conductance of strong electrelyte increases with dilution due to decrease in interioni attractions with dilation. (i) For weak electrolytes conductance increases with dilution due to increase in dissociation 0a lution. The magmitade of increase in conductance of weak electrolyte is much larger a compared to that of strong electrolytes Calculation of Molar Conductance of Electrolytes at Infinite Dilution A‘, ( For strong electrolytes itis calculated by extrapolation of graph of Ay, vs concentration to 7210: a) For weak electrolytes, ts not possible to find it by extrapolation of graph of Ay vs concentration ‘zero, So, itis determined by using Kohlrausch’s law,‘Redox Reactions and Electrochemistry 137 Kohlrausch’s Law It states that equivalent conductivity of an electrolyte at infinite dilution is the sum of equivalent conductivities of cations and anions, Ngee kh For electrolyte of A,B, type molar conductivity is calculated as fllows Kn = XFim (AP) + YG BY Applications of Kohlrausch’s Law (0 The Kohirausch's law is used to determine the molar conductivity of weak electrolytes a infinite (=) dlution. Aceti acid i a weak electrolyte and its molar conductivity i calculated as Follows Ngoon = Nx goo + Af = Nact (Gi) The Kohlrausch’s law is used to calculate the degree of dissociation (2) ‘qx _Molarconductivity at given diution inolar conductivity t infinite ution (li) The Kohlrausch’s law is used to calculate solubility of sparingly soluble salt. The solution of sparingly salt becomes saturated at infinite dilution, then Aw = Ay +1000 Solubility (moles/L) = Different Types of Cells (@) Primary cells are those cells which cannot be recharged. For example, Leclanche cell dy cell, mercury cll (©) Secondary cells are those cells which canbe recharged For example lead storage battery, NC cell. (@ Fuel cells are those cells which have continuous supply of fuel (eactant-The combustion of fuel directly forms electrical energy. For example, Hy ~O; fuel cell. 3G | aE ‘Thermodynamic efficiency of fuel ell q)= = opp Some Typical Examples of Cells (2) Lead-storage battery consists of anode made of lead and cathode made of lead oxide. Reaction occurting during discharge of cell At anode Pb +50 —> PbSO, + 2e At cathode PbO, +503 +2e7 —> PbSO, + 21,0 Cell reaction —_Pb + PbO, + 2H,SO, —+ 2PbSO, + 2H,0 Recharge reaction is reverse of cell reaction Discharin Pb PbO; + 211504 Taran, 2PS0, + 21,0138 Indian National Chemistry Olympiad (b) Dry cell In dry cell anode is made of zinc and cathode is made of graphite. Electrolyte touching anode is moist paste of NHCland ZnCl, Electrolyte touching cathode is the mixture of MnO, + C: Its life is not long because NH,Cl corrodes zinc container even when the cell § notin use (©) Concentration cell Te consists of two solutions of the same electrolyte having diferent concentrations separated by sl bridge with electrodes ofthe same material dipped in them. ‘n/t N20 y/20 2058 og er, c>) (d) Battery {trefers to two or more electrochemical cells connected in series to generate electricity. Corrosion It is deterioration (wasteful conversion) of metal into compounds by attack of water and atmospheric gases. Corrosion of iron is called rusting. Chemically rust is hydrated ferric oxide (Fe,0, -xH,0). on does not rust in vacuum. Chemical Reactions Involved in The Process of Rusting Pure iron acts as cathode and impurities act as anode. Water present on surface of iron reacts with carbon dioxide present in air to form carbonic acid. H0+CO, —+ HCO, HCO, — 2H CoP At cathode Fe —+ 2Fe®* + 20° are + 0, + 4H,O —+ Fe,0, + 8H" tamed mite * “BP > Fey Ot At anode wee aH 4H +0; —> 28,0 Factors Affecting the Rate of Rusting Impurities in the form of other metals present in iron, mots resence of electrolyte increase the rate of rusting. ture (HO) and ps f electrolyte Prevention of Rusting Rusting of iron can be prevented by the following methods. ) Barrier protection It involves covering the iron surface by paint. (G) Sacrificial protection It involves coating the tron surface by tin, (is) Galvanization_ In this process iron surface is coated with zineLet us Practice Level I (Objective Questions) 1, Which of the following is not a_ strong electrolyte? [NSEC 2000}, (@) Fused Nac () Acetic acid (6) Dilute perchloric acid (@) Aqueous NaOH solution 2. The increase in the equivalent conductance of asalt solution. On dilution itis due to increase in [NSEC 2000) (@) attraction between fon, (6) decrease of ionization of salt. ©) molecular attraction. (@) association of the salt. 3. When 965000 C of electricity are passed ‘through nickel sulphate solution, the amount of nickel deposited will be [NSEC 2000] @ 1.0 mol (©) 0.5 mol (0 0.1 mol (@) 20 mol 4, When a piece of copper wire is immersed in a silver nitrate solution, the colour of solution ‘tums blue due to {NSEC 2000) (a) oxidation of silver, (b) reduction of copper. (©) oxidation of copper. {@) formation of soluble complex. 5. In the following reaction, 50, +2H,S —> 3S +2H,0 [NSEC 2000] (a) sulphur is oxidized and reduced, (©) sulphur is oxidized and hydrogen is reduced, (© sulphur’ is reduced and there is no oxidation. (@) hydrogen is oxidized and sulphur is reduced. 6. The oxidation number of Mn in (MnO, is INse¢ 2001) @7 (0) +7 #2 @-2 7, The reduction potentials of Zn, Cu, Fe and Ag are in the order [NSEC 2001) (a) 2n,Cu, Fe, Ag (b) Cu, Ag, Fe, Zn (©) Ag,Cu, Fe, Zn (d) Fe, Zn, Cu, Ag 10. a 2. 13, Ma 15, 3. "The standard reduction potentials of Cu’* /Cu and Cu*/Cu are 0339 V and 0.518 V respectively. The standard electrode potential of Cu’ /Cu half cell is INSEc 2001] (a) -0.179V. (b) 0.827 (©) O.184V (a) 0.490 V 1. The cell potential (B and free energy change ‘electrochemical INSEC 2001), ©) AG=nFE (4G) accompanying reaction are related by (@) AG=nF log G (©) -8G = nFE (@) -AG=nF log E ‘The units of conductivity are {NSEC 2001] (@) Siemen-'cm"—(b) Siemen cm (© Siemen-em™ —_(@) iemen .em® mol ‘The calomel electrode used as reference ‘electrode contain INSEC 2001], (@) PbO, PSO, mixture (0) HCl, (© Hg Ch, (@) ZnCl, KClis used in salt bridge because [NSEC 2001) (a) it forms good jelly with agar-agar. (b) itis strong electrolyte. (©) itis good conductor of electric current. (@) the transference number of K" and Cl. {ons are almost equal, During the electrolyses of fused NaCl the reaction occurring at anode is [NSEC 2001] (@) reduction of Na*, (0) oxidation of Cr (6) oxidation of Na‘ (@) reduction of Cr . On electrolysis, one mole of chromium ions will be deposited by INSEC 2001] (@) three moles of electrons. (©) two moles of electrons. (©) one mole of electrons, (@) stx moles of electrons, ‘The quantity of electricity which deposits 1.08 g of silver from AgNO, solution is [NSEC 2002] an140 16, 17. 18, 19. 20. 21. 22. (a) 96500 ¢ @) 9650 (© 965 ¢ (@) 965 ‘The standard reduction potentials at 298 K for the half reactions are INSEC 2002] Zn**(ag)+ 20° —s Znis} -0.762V CP ag) + 3e” — Cx6s); 740 V 2H laq)+ 22° —> Hy@h 0.008 V Fe™ (ag)+ e” —» Fe (aq); 0.770 INSEC 2002] (a) Zm(s) ©) Cris) (© H.@) (@) Feiaq) The reaction occurring at cathode during electrolysis is INSEG 2002] (@) oxidation () reduction’ (©) decomposition _(d) hydrolysis The molar conductivities of H*, Lit, Na* in aqueous solutions at infinite dilution are in the order [NSEC 2003.04] (@) Ht >Lit > Nat (b) HY Na > Li" (a) Nat > HT> Li? Fe® +207 —» Fe Oy a ‘The standard potential (in volt) corresponding, to the reaction () and (i) are £, and £, respectively. The value (in volt) of ‘standard, potential corresponding to the reaction Fe +3e” —+ Feis NSEC 2003-04] 8+) 3 Gh) 3 ‘The quantity of electricity required to reduce 0.05 mol of MnO; to Mn** in acidic medium Fe +e" —» Fe © @ @A+E ) 2 could be [NSEC 2003-04) (a) 0.01F () 0.05 F (©) O15 F @) 025F ‘The standard reduction potentials of Cu*, zn** Sn and Ag” are 0.34 V, -0.76V, -0.14V and 0.80 V respectively. The storage that is possible without reaction fs for NSEC 2003-08) (a) CuSO, solution in zinc vessel. (b) AgNO, solution in zine vessel, (¢) AgNO, solution in tin vessel, (@) CuSO, solution in silver vessel ‘A certain current passed through CuSO, ‘solution for 100 s deposits 0.3175 g of copper. ‘The current passed (in A) is (NSEC 2004-05} 23. 24, 25, 26. 27, 28. 29, Indian National Chemistry Olympiag (@ 4.83, ©) 965, (© 0.963 (@) 0.483, ‘The salt that can be used in salt bridge of an electrochemical cel is [NSE 200645 (a) FeCh &) Age {0 CHCOONa ——_() KNO, ‘The metal that cannot be displaced fro aqueous solution by zincis [NSEC 2004.05 (@) Cu (©) Ag Al (@ tig In an alkaline energy cell the overall cell reaction is as follows, 2n(3) + 2Mn0,(@)+ 2H,0@) —> Zn(0FD46s) + 2Mn0(0H) Which of the following reaction is taking place at cathode? INSEC 2005-05) (@) 2Nn0,(5)+ 2H,0 + 20° —> Zn10F,65) + 2MnO(OHKS) (©) 2Mn04(5)+ 21,0 + 2° —> 2MnOKOHKS) + 201 aq) (© Za\s) +201 faq) —> 2n40HD,(9)+ 2e° (@) 2n(0H), + 2c” —> 2ns)+ 201 (aq) ‘The mass of copper, in grams, deposited during the passage of 2.5 A current through a ‘Cu sulphate solution for 1 hr is INSEC 2006-071 (a) 5.96 ©) 238 (©) 2.98 (a) 59.6 ‘The standard reduction potentials _ of Fe® /Fe* and Cu?*/Cu electrodes are -014 and 0.34 V respectively. The following reaction would occur [NSEC 2006-07] (a) copper will reduce Fe®* ions. (©) iron will reduce Cu®* ions, (6) iron with oxidise copper metal. (@) Cu® ions will reduce Fe* Jn thiosulphuric acid H,S,0,, the oxidation states of sulphur atoms are {NSEC 2006071 (@) 44,401 ©) O.4V (©) #1, 4 @ -I, v1 If the equilibrium constant of the aisproportionation reaction. Hg}! > Hg? + Hg? at 298 K is 0.795, the standard emf of the reaction Is nsec 2006-071 (a) -0.036 () -0.212V (©) 0.125 V (@ o.110VRedox Reactions and Electrochemistry 141 Level II (Subjective Questions) 1.A.Chiufen, the old mining town located within the his in the northeast Taiwan, isa place where you can really experience Tajwan's historical legacy. It was the site of one of the largest gold mines in Asia. Accordingly, Chiufen is often referred to as the Gold Capital of Asia. The compound KCN is ‘vaditionally used to extract gold from ore. Gold dissolves in cyanide (CN) solutions in the presence of air to form AU(CN);, which is stable in aqueous solution. 4AuGS)+ 8CN“lag)+ O,(9)+ 2H,0() = 4AUiCN);(ag) + 40H-(aq) (@) Draw a structure for Au(CN}; showing the spatial arrangements of the atoms. (©) How many grams of KCN are needed to extract 20 g of gold from ore? Show your work. Aquaregia, 3: 1 mixture (by volume) of concentrated hydrochloric acid and nitric acid, was developed by the alchemists as a means to “dissolve” gold. The process is actually a redox reaction with the following simplified chemical equation : AU(S)-+ NO§(aq)+CI-(aq) =* AuCl; (aq) + NO3(@) (¢) Write down the half reactions, and use them to obtain abbalanced redox reaction for this process. (4) What are the oxidizing and reducing agents for three process ? Gold is too noble to react with nitric acid. However, gold does react with aquaregia because the ‘complex ion AuCI; forms. Consider the following half-reactions : ‘Au? (aq)+ 32" —+ Au(s) Fr=+150V AUCI;(ag)+ Se” —» Au(s)+ 4C1(aa) = + 1.00 ‘An electrochemical cell can be formed from these two redox couples. {c) Calculate the formation constant for AUCI, at 25°C Clg} / [Aw tC (© The function of HCLis to provide. What isthe purpose of the CI” for the above reaction? Select ‘your answer from the following choices () CI is an oxidizing agent. {id CI-isa reducing agent. (ii) Cris complexing agent. (iv) Cis acatalyst. B. The synthesis and characterization of gold nanoparticles is currently an active research area. The Brust Schiffrin method for the synthesis of gold nanoparticle (AUNP) allows the facile preparation of thermally stable and alrstable AuNPs of reduced polydispersity with a controlled size diatrbetion ranging in dlameter between 1.5 and 5.2 nm. The preparative procedure is briefly deserbed og follows. An aqueous solution of HAUCl, is mixed with toluene solution of tetra-n-octylammoctics ‘bromide. The solution s mixed with dodecanethioland is treated with an excess of NaS, Formation othe AUNPs is evidenced by the immediate, pronounced darkening of the toluene phase. After 217 the toluene solvent is removed with arotary evaporator and the resulting solid washed on a frit wit ehanol and hexane to remove excess thiol. These AUNPS can be repeatedly isolated and reciscolng in common organte solvent without reversible aggregation or decomposition. (@) Is the methodology for this fabrication referred to a top-down or bottom-up approach? Select your answer from the following choices. () Top-down approach, which entalls reducing the size of the smallest structures to the nanoscale. (i) Bottom-up approach, which involves manipulating individual atoms and molecules (©) The trimethybnoctylammonium bromide can also be used as a phase-transfer reagent. It can cary AuCI, ffom an aqueous phase to an organie phase. Which property ‘does {rimethy!-roctylammonium bromide possess to function as an efficient phase- transfer reagent? Select your answer from the following choices 0 One side of the molecule is electropositve, the other side s electronegative, (i) One side ofthe molecule is hydrophilic, the other side is hydrophobic,142 Indian National Chemistry Olympiag (ii) One side of the molecule is acidic, the other side is basic. (©) Whats the function of NaBH, in this preparation? Select your answer from the following choices, () Reducing agent, i) Oxidizing agent (ii) Neutralization agent Gv) Complexing agent (@) Ifthe average diameter of a gold nanoparticle is 3 nm, what is the estimated number of Au atoms. in each nanoparticle (the atomic radius of Au is 0.144 nm). Select your answer from the following choices and show your work. wi wo ui) 10" avy 1 (6) Whatis the estimated percentage of Auatoms on the surface of a nanoparticle? Select your answer from the following choices and show your work. (i) 20-30% (Gi) 40-50% (iii) 60-70% {iv) 80-90% GAT [aa [HAS [aaa [aa [aa [amr [RO [a [ae [as | ToulomaReed | 2 | 4[4t2t[et?12t2l21elsle Answers with Solutions Level 1 Lo 2% «20 40k M8 20 00 LO Be 2h we Ie IEA 170 1819) 230) 2602) Level II 1. (a) [N=C— Au—C=NyJ- Calculation The structure of Au(CNJ is linear. “Au?*(aq)+ 3° —+Au(s) (b) 13.024 ¢ ‘Au(s)+ 4CI-(aa)—+ Aut Calculation: “Aus BKCN+ 0; + 2H,0 = AKAWCN), + 4KOH 20g +197 g/mol » 0.10 mol (Au) 0.10 mol x (8/4) x 65.12 g/mol= 13.024 g (KCN) Au(s)+ Au?*(aq)+ 4ci-(aq) —> ‘AuCl,"(aq) (© Oxidation Au(s)+ 4CI-(ag) —> AuCl;(aq) + 3e~ osov + Aut) Reduction +e 3NO5(ag)+ 6H" (aq)+ 3e°—+ 3NO,(@) E= E°—(0.059/n)log Q at equilibrium, Q= K, + 3H,00) ‘Au(s)+3NO;(aq) + 6H" (aq) + 4CI(aq) = AuCl;(aq) + 3NO,(@)+ 3H,0(1) (@) Oxidizing agent : HNO, or nitric acid Reducing agent : Au (@) K = 10° = 2.6 x10 uC] / (Au? Yer .059) /n log K, 050= (0.59/3) log K, K = 104? - 2.6x 10 G+ aG,°=4G"Redox Reactions and Electrochemistry CnFE,*) + CnFE,*)=—RT Ink E°=(RT/nF)in K = (0.059/n)log K (He Answer for multiple choice question :() (Answer for multiple choice question :() (ii) Answer for multiple choice question :(b) (Gi) Answer for multiple choice question :@) 6) Anawer For small chnice gestion) x calculation xm Rass xen 4 exam Mee Sams 3 ‘tune (25.1000 na J daa (0) Answer for multiple choice questions ‘by 40-50% calculation Method 1 $ eran Scns Panne =a Naw Surface area ofa gold nanoparticle Sranrs = 48s 143 Spunps = 4 ra, NEP N= Sunes = NIE PAN Nyy =ANE Nya =1000 P= 40% Method 2 wy Vases ~ Vises Yas YY P62 Ma 100% Yaw CS asAF— 02.128 = OSA O24. 100% 47KRedox Reactions JEEMainmesroxe Caton Naber aula sae Econ Bec c egos 1 Sasa dtc agent 1 SSR sink Recto 7.1 Oxidation Number ‘Thereal or imaginary charge which an atom appears to have in its combined state, is called oxidation state or oxidation numberof that atom. ‘The oxidation number (or oxidation state) of an element in a compound is determined as the number of electrons that have passed from one atom of a fgven element to other atom (positive oxidation) or to one atom of a given element from other atom (negative oxidation) We can also say that, oxidation, ‘state is the oxidation number per atom. Rules for Assigning Oxidation Number The oxdaton number ofan element or atom canbe calculated ath the help offallwing rules 1. The oxidation number of an atom in is free or elemental state is 2er0, eg, oxidation numberof Hin Hy, S in Sy, in R, 0 inO, oF, is zero (Oxidation numberof fluorine i alays 1 i all ofits compounds. ‘3. Oxidation number of oxygen is always -2 in all of its compounds except peroxides, superenides and oxygen fuarides In peroxides ts oxidation number {is -1, n superondes, its oidation number is -} while in OF its oxidation number is-02 4. The oxidation number of hydrogen in metallic hydriee s-1 while in rest ofthe ‘compounds thas +1 exidation number. 5. The oxidation numberof anion is equa tothe electrical charge present oni 6. For complex fons, the algebralc sum of oxidation numbers ofall the atoms is equal othe net charge on the fon. 1 Incase of neutral molecules, the algebraic sum of the oxidation numbers ofall the atoms present inthe molecule is zero, The reaction which involves ‘oxidation and reduction as its two hhalf-reactions is called redox reaction, Normally its found thot ‘oxidation and reduction reactions ‘are complementary t0 each other ‘ond occur simultaneously. Their simultaneous occurrence is seen it the form of redox reactionRedox Reactions 269 (wherever thee is doubs, the more electronegative atom takes the lower oxidation number) ‘The most common oxidation siates of representative elements are tabulated below Table 41 Common Oxidation States of Representative Elements ‘Common oxidation snes excep sero neo stat 1s) | anagiay | 42 ranquay | sa01 san vay | 44.45.42, 44,-1, on) He9a sted N-+shows a posstiecridason tales tom +510 Sincusng = Sint 4 tn cna) 46464202 srg | aras3.tte noo grup) | 200 {Caution Point Tansiton ements eit lugenunbe cf oaten snes he binant el) elec ao besides rs hte : Hot Spot 1> FINDING Oxidation State Finding oxidation state isan important topic of his chapter and easest.also as by just remembering afew rules, you can find the oxidation state ofthe desired element. ‘Theverous steps used to find out the oxidation stteare ‘(CAO wos, Step I Assign oxidation state of all other elements except the one, i Hy$20y (vill) KANSO,)-12H,0 stnton ste wh has tobe fred (Ue te es oF nberPFEE) NaHLEO, {Sing ena sates of wens) cM HDs, WE tte ouation number oP ex Wing he oxiaon number he to fnd the exidaton tate of Mn. ral Ive to Fr the ‘each tom above ts spmbol we get a BGs iid : compo hun th oxiaton ube ofall he ep Te sic sm ef odson sso a he cemensofs Serre neural molecule Is zero. incase of on it equal to charge Teds rede eedeD | orien i 10, | tie xe Cal4=0 ‘Hence, the oxidation number of P in NaH,PO, is + 5. | vre-* a {i NaHS, 1 aos Lette ordaton umber of be x | Thos he oxidation sate oF Me +7. SHS, | Nedenenecete Sample Problem 1 Asien oxen mumber 10 the be teae Underlined element in each ofthe fllowing species. (NCERT, ()NaH,EO« Nats, 46 in P,Or Gamat Hence the endation number ofS in NaHS, is +6270 JEE Main Chemistry 0 HP, Lette oxidation number af in HPO; Be HBS, see v 920847 Hence the ondation numberof in HyP,O; 1+ 5 tw» ao? {eth onan ter nin iO Be Mode eeseaerd bChageon halon b-2 ftratoneve a0, {athe oxaton nb fb ad, (Caisan alain cart mets onto ter 23 Wea aea0 aecterset ence, xan ber of On = wo naar Lethe oxidation number ofB be Fractional Oxidation States ‘Fractional oxidation states are often used to represent the ‘average oxidation states of several atoms (pa structure For example. in KO, the superoxide ion hasa charge of -1 ‘Givided among two equivalent atoms, o each oxygen ‘assigned an oxidation state of -1/2. This fon is described ‘asa resonance hybrid of two Lewis structures and each ‘rygen has oxidation tate in onestructure and ~1 in the other. For the cyclopentadienylion G85, the oxidation state of fs (1)+ C1/S)=-6/5 The -1. occurs because each C is Donded to one less electronegative H, and the ~1/3 because the total onic charge is divided among five equivalent Exceptional Cases of Oxidation States 1. Oxldation Sate of Sulphur in Na 5.06 Letus see the suture of 2,805 erate a Lion ia HABFTg dn Nab, H eis as atid fn, 0 oxidation umber is-9 len eat ate =0 Tran 4e0orx=+3 Hence he oxidation number of Io NeBHy i+ 3. wate ee conan oe aad mento soc een eer SHO caer erdesranerd nso 108 RU GOAT nee 1G 34 Bee 8D + 12E IED —O 4420-16 12 or x=46 2 Nate 1,0 neta melee treo sum of xdation ruber ot atone nkDie m0 Fence osdaton numberof S MKAKSO,),-12H,O% + 6 rom the structure clear tha he sulphur atoms Scum as donor somo have + oxidation number {Cech On the other hand he eulphur atom involved {a pure covalent bond formation has zero oxidation umber. 2. Oxidation State of Fe in Fe,Dy mo FO 9 x-20 nae? TM Fey —9 2-6-0 xa03 Ta Fay 4 3-8 O.x=+ 8/Mractional Here, in FeO, oxidation number isthe avereee ef those in 0 and Fey FeO + FeO, = Fey ‘Average oxidation numberof in 0,222 209). 48 cmiaié 3. Oxidation State of chromium in Cro, CO, be# butterfly structure having two peroxo bonds as i Pobec Grr ose tas onan sae tx he tin sate of crm be? esdeay taieo4 Oxidation state ofS in H,50, and W505 Jn ,50,(Caros acid) one peroxide linkages present. no ST ; ‘Thus, the oxidation numberof Se obtained as 2x fells x4 3% (2)s 2xCa)-0 (ir) or) Goro} for oo} 2ex-G-2-00r x= 468 ‘Similarly, n 5,0, the oxidation number ofS is 6. 5. Oxidation State of Clin Ca0Cl, In CaOCt; bleaching powder) or Cx(OC Cl, the wo Cl atoms are in diferent ‘oxidation states. The exidaton state of Cris 1 and that present in OCT is +1 6. Oxidation Number of Sulphur in (CH,),S0 (dimethyl sulphoxide) Here, oxidation number of O=-2 ‘oxidation number of each CH, group is + L 4 +2¢x-2-00rx=0 ‘Thus, sulphurlies n zero oxidation state Oxidation Number of Sulphur in hypo, Na,S,0, Let ‘he average oxidation number of sulphur be x $242 2 ‘Structure of hypo may be drawn as 9 metptd asf 3 Her the two eulphur atoms have diferent oxidation {0 Oxidation numberof donor supur atom is + 5 ves up four electrons in coordination and one ‘ecto in covalent bond formation with oxen. (9 sulphur, bonded wth Na es In state since one eecton of Na les towards the sulphut Eleatons of §-S bond are equally shared ‘beeen two sulphur atoms Thus, +5 and ~Lare o oxldation states ofthe two sulphur aoms Sample Problem 2 Oxidation state of nivogen in tydarate act a3 w-2 ww an Interpret Hydazoic acid ist mm ake100 Redox Reactions 271 xe-1/3 Ordon nuber of irogen is -113 Oxidation State in Covalent Compounds We should take into consideration the following fundamental aspects of bonding while counting the ‘oxidation state of covalently bonded molecules. 1. Single covalent bond contributes one unit for ‘oxidation number. 2. Negative oxidation number is assigned to more electronegative ator and postive oxidation number toless electronegative atom. 5. Coordinate bond is represented by an arrow from donor atom to acceptor atom, 4 8 aihor —* acfioe 1fdonostom sles electronegative and aceeporis more, then + ous given wo donor and 2 at legen 10 scree But it should be noted that if the donor is more Cleeronegnive than the acceptor, then conmbton of Coordinate bond for bath tome regarding oxidation sate Snegleud.eg, (Oxidation state of Wand Cin HCN can stea-3e0 a2 Catton in» 2st andniogen isin Each Sond centbster "tse moe eleroncete (i ouastion state of and CintING Hac Onidaon sate oer 1 Onan tate of mitogen = Ea} 2) valent bond wth hyogen contbutes (1) and covlnt bond wath eatbon ones and re ‘sto conttbudon of cotdnate bond, Let ihe Oslton ste of carbon be: pemieerieery Ui) repo lonidton sation sto be determined) Goer 20 s+2/0942200/04 W) Mii (Ordaton ste ef ltogen bir mest a des deo xe-2272 JEE Main Chemistry Stock Notations ‘While naming the ion or compound, itis desirable to put ‘oxidation number per atom (‘oxidation state) in Roman figures within brackets (anion end with ate Table 7.2) Such representation is called Stock notation given by German chemist Alfred Stock For example, nitrogen forms five oxides, te, NO, NO.NO,, NO, and NO; having the oxidation number +4424 44 and +5 respectively. therefore, according to Stock notation, they are represented 28 (00, N60, (WO, NIVI0, and N, (V0 respectively. Note He, is als called cla an ean ine compound whle Hays lio cle coos subimae ards a colent compound and patona.Anite of his wht fen eg, ‘Table 72 Naming the Acid and its tone Semone Feria | Aids | Ferma Bens) from | Heo Baten Joma | sexo, ems) a Bema) orice | Ho, Chromate Joremeen | Kc, sate here Hi, ‘tt twos | Ho, Proto) rosters | 470, supra sirums | 430, soprte umee | Hs0, Pecsetsipnae ()|s0% —Peray | MSO, ni [sulphur ‘Sample Problem 3. Write the formulae forthe following compounds. (@ Mercury chloride li Tin) oxide (6) Hen sulphate (in Nick sulphate (9 Thallium (sulphate (09 Chromium exe wceRN, Interpret. While writing the formula ofa compound oxidation {at (valency of cation s writen asthe subscript of anion and ‘alency of anion is writen asthe subscript of etion Valency of cherie (Cr), sulphate SO") and oxide (O) are <1)=2 and =2 respectively, valences of meals are sven In chee b Hence, the formula fhe given compounds i as @Heac — NIMS, GSU Oy (THOS, (Fe, AINEOY, WICH, HN, Difference Between Valency and Oxidation Number These vo terms have diferent meanings as explained above in the Table 73 ‘Table 7.3 Difference Between Oxidation Number ‘and Valency ‘SNo]__Oadation number + | Ovcaton nurber is the resi Charge ft on he ‘Som when oer atoms ae removed as ons. vary This te corbnng Sanaa olan comes, kas Cefn ae fhe rmbt 2 bom ortwee the nate Cate wth wicn an asm can never be 28. 8 aways posine.| 2 | neanteze. eg. axon umber of © in OH,8% 3. | reer tothe charge, wticn canbe posite omega, 20, iC the oxidation umber of Gute + Zandt | CuCl. ait and hat of Che 3. 4. | tan nave ocsna! value, | tis aksnys a who's namee. eg. ondatonrumber of S| snce atoms ans nk S015 + 52 combine fn single woe numbers. tie ted oot compounds, eg. te vamng of Cea nat compeunds, suchas CHC, CSCO, a8 ones, Wis only a prrbor and 6 5. | osdaion number of an foment can be dierent fiterer compcunds, 0g. ‘oxctien number of Cn Oh Cte Cry CO, and Chis, ae 4-3-2 ot and. 2 respec, Applications of Oxidation Number Oridation momber helps in comparing acidy and basicity of different substances, Moreover, these also help sn naming compounds Samant opplenons wedecrbed teow (Adie Character Gre he elon arbor of he dens te esta pune nad arse cconiraneaaed phosphorus Thus, acid strength increases as, who ensyenta | na 2KOH +1, (Oxidation of potasium todd) 2K,)nO, +l, —+ 2KCL + 2KMnOg (Oxidation of poassiu manganate) 2kU+ Cl, —s 2KCI +h (oxidation of potassium iodide) Reduction i just the reverse of oxidation, It is @ process Which involves (Removal ofaxygen eg, CuO+C —s Cu +C0 (Reduction of cupec oxide) HP+ © —+CO +H, (Reduction of water) sem coe Sate274 JEE Main Chemistry FeQ,+4tl; —» 3Fe +48,0 (Reduction of magnetic oxide Le, iron oxide] (i) Addition of hydrogen eg, +t, —+ 2H. Reduction of chlorine) Set, — HS eduction of sulphur) Cali +H, — Gly (eduction of ethene) (i) Removal ofan electronegative clement ¢, 2HgCl, + SnCl, —+ Hil, + Sy (Reduction of mere chloride) FeCl, +1, —+ 2FeCl, +2Ck (Reduction offers chord) 2Fecl, +1 —s 2FeCl, +2HC1 +8 {Reduction of fese chords) {u) Addition ofan electropositve element ech, +g —> Heel, ‘Reduction of mercuk chloride) uch, 1Cu —» Cust, (Reduction of cup chloride) Modern Concept According to the modem concept Iss of electrons fe, increase in the oxidation number) scaled exldaion Wille gain of electrons (Le, decrease In the oxidation ‘number is called reduction, on | Ring cxidation i lss | reduction i gain ce, The equation shows a simple redox reaction which an obviously be deseribedin terms of oxygen wanstr uO + Mg —+ Cu+ MgO Copper It) oxide and magnesium oxide are both tonic. ‘The metals cbviousl are not. lfyou rewrite his as anionic equation, becomes edlcion by gin of eleetons ‘Ca? + Mg —> Cut Mgt oxidavon by loss of electrons 7.3 Oxidising and Reducing Agent Asubetance which undergoes oxidation acts as reducing. ‘agent and the other one which undergoes reduction acts as oxidlsing agent. nother words Incase of reducing agent i) loses one or more electrons (i) undergoes oxidation Gi) oxidation number of atom increases ‘Table 7.4 Some Important Reducing Agent fective cxtaon ruber i nan aon Reducing agent ee_| exc a von a sts (ace) | et” —+ Fo™ 1 Tm) sats (ec) | Su —> Sot? 2 hanedeates ci) | C,0% —* CO 1 siphtos cig) | SOF —+ SOF 2 Hyogensupnice | sé 9S 2 iodide atu acid) fF 1 fees conc) | or at 2 Meas 29.20 zn — 2 2 toe HoH 1 [Amoxidising agent i gains one or more electrons (i) undergoes reduction {i oxidation numberof atom decreases Me.,Cu,F).1,H,C.KI_are reducing agents, while On chy HO, FeCl, CuCl, Fes0,, CuO, ee, are oxidising agents In the above examples, Some other examples are fabulated below. ‘Table 7.5 Some Important Oxidising Agent Decrease Onicising agent Etictve change | Ober or ‘mom vavrO, macs wouien | nO; —> wer 5 feve0, maka souten | uno, —s woe] 3 60; hacideouten | cL —> a bie HNO, No —+ No a Conanated HNO, | NO} —+ NO 1 ConcanttedH.s0, | SOF —s 80 2 MergaresoW)cxise | Mad —+ rt 2 Ctene Op or 1 nee 9 oo or 2 180, nate oo 1% 5 WO necrcenaesacis | 10 — 6 Equivalent Mass of Oxidant/Reductant Equivalent mass of oxidant/reductant is calculated by dividing their molecular mass by number of electrons taking part in the reaction, Le, Equivalent mass of oxidising/reducing agent “= Mol. mass of oxidising/ reducing agent ito. of electrons taking part in the reactionHot Spot 2> Generally question based on oxidant, reductant, oxidised and reduced species has been seen in previous year JEE Main (AIEEE) examination papers so itis an important topic for this examination. The level of questions is ‘generally ens Steps hed to find ot these espns ‘tp thei tte pe. te un Wedd 8 Sip soit ottoman Tangeta oie ma besa deeangop eS eaoe urn outer sre Sheet cd artes tented bated ne pe Supt Fol he sonfeese oon se of wn snip Tb gece bree sede og ‘oo ep. meson con ten ste af OG Kani ton Oe auc vraag ede uns Sample Problem @ In the following reaction which species sovidied? K{AGICNIg] + Zn—> 28 + KalZAICNl @ ACN T (0) ZaieNd ane (Zn FINDING Oxidising and | Reducing Agent | Incerpret a In this econ endton site of Zn increasing | freon 92, Ths teed In hs eatin. | Sample Problem § dently the covect statement (in| ieaton tothe flowing recto. INCERT empl | ‘Zn + 2HClL—> ZnCl, + Hy { (a ins acting at nod | 8) Chloe sacking asa redone i CG tyope fon actng san onda | (@ Zhe acing 5 a reductart | Interpret (c,d) | Reducion | | fyi aie +f | Orson i tn the shove reaction 2 is oie d and H* is reduced 30 Zn acts a6 | ‘decgoretendhydmpentonorNG]soslng gent ronan. | ‘ 7.4 Redox Reactions ‘hse easton inv oxtaton a wells ecto 35 1 al acon yor word thse eats whch andafon end Tels proces oc Shuarcousy re ced edo eacione ibd dll — wd, thc, tn» Deda sates ore ble S0 PDN oti nate 80) aso a ong get Orkin Cty an sl get rece 0 Thos + acl —~ Ta, + Ch+2io oniome ia Onkineses by perme Sample Problem 6 hich ofthe folowing reactions are edo reactions? incext (0) CuOs + Hyg) —+ Cu9+ 018) MDFe,049 + 3COW) — 2Fak)+ 3CO4®) i $BCYQ) + SLAM) —> 203400 + 3LICKD + 3ALChIO W2K9 + lg) 9 2K (ANHa)+ 50g) —+ 4NOW) + 6H,OK) (a) and (1, Mand ih mand (Atothee Interpret (1) Redox eactons ate those reactions in which one reactant oxtsed wile the other i reduced. 50, it find the Cndation state of each elemento find the substance undergoing nation reduction and then tls redox reaction or nt? 0 Cu010 + Hig — Cua + H,018) Assign oxidation numbers ofeach tom above fs symbol Gd Fis) — Cao she (Oxidation numberof Cuin CuO is+ 2 Rdecresses om + 2tozera InCu. Wile oxidation nurber of hydogeninereases fom in) 10 +1 in HO). Ths shows that CuO is reduced to Cu bu Hy i ‘oxidled 10 H,O. Hence, tan example of ex reaction, Lid FeOy0 +38 Gg) —> 2Fei + SCS)276 JEE Main Chemistry Oxidation number of Fe decreases fom +3 tin Fe) 10 2270 Fel and oxidation numberof increases from+ 2 in CO)10 ‘+4 Gr CO,). This shows that FeO, I reduced to Fe and CO is ‘oxidised 19 CO, Hence, iti a redo reaction, in Aq) + UAT) 28 fn sida Ao (Oxidation numberof 8 deceates from + 3 mB) t0—3 Gn BH) and oxidation number of H increases from ~1(n LAI) to #1 Gin BT shows that BC is rduced to BAM, and LAIN, is oxidised, Hence, ita redox reaction. o 2k + Fig) > 28 Fa ‘Oxidation number of Kinceases rom zero fin) t0 #1 (nF and ‘oxidation numberof F reduces kom zr (in) © ~1(n KF This Shows that Ks oxidised and Fs reduced. Hence, its a redox reaction, ANF Sug) —r ANS 67S Cnidation number of increas fom ~3 GaNH) to +2 (in NO} Sd oxidation number of © decrests lem 2er (ia O;) 19 ~2 (G@NO and H,0). Ths shows that NH 1 oxidised and O, reduced. Hence it sa redox eacton. ‘Types of Redox Reactions Redox reactions are divided int tz0 main types (a) Intermolecular Redox Reactions Im such redox reactions, molecule of one reactant is conidised whereas molecule of other reactant is reduced ee, NOJsH:S+Hg04 HY —e Nig + S03 ondied Reduced (0) Intramolecular Redox Reactions Xone atom ofa molecule is oxidised and other atom of same molecule is reduced then the feaction is called intmmolecular redox reaction NHNO, + ¥,0 + 21,0 ‘There are wo ypes of nltogen, one in NH; fon oxidation number=-d and the oer in NO; (oxidation number '=+9,On decomposiian, 8.0 (osdation number = + 01s formed Thus, Nis oxidised to NO and NO; reduced No. since, both the elements aren the same intial substance, reactions of this kind are known a¢ Intramolecular xiation-reducton or redox reactions. Inanothe example, Poh -* Pc, +c, tt ttt omen ano Phosphorus (V) of PCl, is thus reduced to POU!) of PC, Cli-H) is oxidised 0 Ch). ‘Thus, it's an intramolecular redox reaction. (©) Disproportionation Reactions tnsuch reactions, compounds ae simultaneously formed that contain a given elementin a more oxiised and more reduced state han the ti] one The inal substance Geplaye functions ofboth an oxidising and a reducing gent Such reactions are posible ifthe relevant element iS in an Intermediate oxidation state in the intial compound: Inthe following disproporionaion reaction 41,00, —> 3H,PO,+ PH Onidaton number of P_ (in POs) is +3 which isthe intermediate of +5 (in HyPO,) and ~3 (in PA), Such Substances have oxidation-redution duality. ‘he reaction between chlorine and cold dilute sodium hydroxide solution is Gi, +201" —+ c+ clo" +#,0 Obviously the chlorine has changed oxidation state because thas ended up in compounds starting from the original element Checkingall the oxidation states shows ch #208" —+ Gr +l" + 0 S 4h 4 4b 4a ‘he chlorine i the only thing to have changed oxidation state. One atom has been reduced because its oxidation sate has fallen, The otherhas been oxidised. This isa good example ofdisproporionation reaction. Thus, a dlproportionation reaction is one in which @ single substance (element) s both oxidized and reduced. Other examples of disproportonation reaction (eutoxdation-autoreduction) ae 0 aout PHBMPOMIONEES oy Reduction ‘Oxidation (i) 2HcHO +H" — cHoH + HOO" Reducuon ‘Onda Clos —s scl; + cr ‘Guidaton (reer (w)aminog + 2840 — nino, + 2xnoz a)CHO 14,08 Reduction 4 bo sor — | C00" Joxidation 2840, — 20+ 0, Semple Problem 7 Find the ciproportinaton rection among the lowing 18) Tes}+ NO}(Ga) —¥ TEO,6)+ NOI) 18 H04(00)+ Fe" aa) —+ Fe a0) + 00 (6 Mila + NOSlaa) —+ Ma) + NO) (dh) Mr?*(aqh —> MnO,isi + Mn?*(aq) Interpret 8) Tet) +NOF aa) — Teo, N0K) Oxidation Redcion Te) — Teo,8 NO} fq) —+ Nos) © HOso9) +Fe* a) — Fer aed +4400 Oxidation Fe" (ag) —» Feng) Reduction H,0,(a9) —> H,0 (© Ovation Mois) —+ Ma (ag) Reducion _NO}laq) —> NOx) (@ Ovidation —MaP"iag) —> MnOgis Reduction Ma"(aq) —> Mona) In tis reaction, Mn hasbeen oxidised to MnO. as wells reduced toMn®(a).Thus, tsa dsproportonation reaction. quvalent weight of the element of compound in dlsproporonation reaction Equivalent weight is the sumf the equivalent weights n oxidation and rection reaction, (04/7, » Mn), where M isthe molecaar ‘mas ofthe compound and n, and mare the numberof fleerons in oxidation and reduction reactions, respecively eg, the equivalent weight of Fy In the Phy + SHPO 12e"+%—=4PI4 —_(edveton) tx 0 tee 12-0 pani (oxidation) By 9 AtiPOR + de dino 84 d= 1628 dened MM) (six Gi) Eq.wt 14) ea133 Redox Reactions 277 ‘Sample Problem 8 Forthe reaction, 38x, +6OH? —> +808 «34,0 280 cn 3B, + 28607 +106" «=10) (reduction) (oxidation) 2420 2-12 ==2—924=10 Me came Conproportionation Reaction ‘This reaction is the reverse of disproportionation reaction. For example, Be* and 8:05 in acidic medium undergoes oxidation and reduction respectively o give By, 2B — By +20"]x5 12H +100" +2607 —+ Be + 6HLO de 12 2 TOR +2610} + 121° —+6B, + OHO or SB" +BrO$ +6 — 93h + 31,0 2 ano Cheek Point 2 1, Ils mo possbe waxes HN, Exp it 2, HS acts ony a reducing agent wile SO can act beth as 2 reducing agent ord an aiding agent, xpi, why? 8 Wy conroprionation reactons ae called the revese of epropornation ection? 4. NaCi+ 81) — Hato, Tic sore ection sa Yd reaction apn, win? 7.5 Molecular and lonic Equations When the reactants and products have been written in molecular forms, the equation is termed as molecular ‘equation eg, Consider the reaction between solutions of ferric chloride and stannous chloride. When they are mixed, ferous chloride and stannic chloride are formed. The cliemical change can be represented by the fllowing equation, 2FeCl, + SnCl, —+ 2ech, + SnCl,278 JEE Main Chemistry ‘Since, the reactants and products involved in the chemical change are lonic compounds, these will be present in the form of fons inthe solution. So, the above Chemical change can also be writen in the following Fe + Cl + Su ¥2cr —> aR + act-+ Sut + 4c or R= « Sot —> aR + Su ‘The ferric fons combine with stannous ions to form ferrous ions and stannic ions. This is an lone equation for the above chemical change. ‘The fons which do not undergo any electronic change during a chemical change are termed as spectator ions. ‘The spectator ons are not included in the final balanced equations. The rules to be followed for wrting (onic equations are (@ all soluble tonic compounds involved ina chemical ‘change ae expressed in ionic symbols wile covalent ‘substances are writen in moleculr form Le, #0,Ny TNO» NOSO4C0,00y et are expressed in molecular form. (i) Highly insoluble ionic compound is expressed in molecular form. (Gi The ons which are common and equal in number on both sides, te, spectator fons are cancelled, () Besides the stoma, the tonic charges must also be balanced on both thesides Sample Problem 9 Choose the correct onic form of the following equation. KC, + 7H,50,+ 6FeSO, —> 3Fey5O4h + Ce{SOW), 4 7H,0+ K,S0, (a) C05 + 7H + oFe* —s ore + 267" + 7H,0 () CrOF + 14H" + re —s Fe + 260+ 7H0 (CHO! + 7H+ of + 1950 —>6Fe + 13805 £2CP*4 74,0 (08407 +240 + 14H + 6Fe* > 6Fe™ + 13807 2c 2K Interpret (inthis equation except 0, ionicin nature Representing these compounds noni fers. 2K" + CHOP 4 14H + 730% + 6Fe" + 650 —> 6Fe" + 980%" + 200" 4 380} + 2K" + SOF + 7H 2K° ont and13SOF one are common on both sides, 50 these are ‘aralled. The desired onc equation reduces, CHO} + MH + Ge —4 Fe 4202" + 7H)0. ‘otal charges are equal on both ses; ths, the balanced onic uaton nthe sare as above Sample Problem 10. Write the following ionicequationin the molecular form the reactants are chlorides. ae + Sn" —9 2Fo! + Sat aFech + SnCl, — Foch + SC (eyre™ + Sat 4 Cr —> Fo + Sn** Cr {Qe + 50C —> 2FeCh + SHC, (e)aFecl, + SnCl—> 2FeCh, + SoC, Inerpret For wing the reac in molec fs IeRSre sin of core ons rae. Spor gece sap 2 « ech + Sh Satya ions ae aed oe RS to neta the hee aon A+ Sot ach or bakes ‘Thus the balanced molecular equation is FeCl, + Sich —+ FeCl + Sry 7.6 Balancing of Redox Reactions ‘The redox reactions can be balanced through 1. Ton-electron method 2, Oxidation number method 1, lon-Electron Method ‘Theion-electron method for balancing redox reactions ‘was given by Jette and Lamev in 1927. ‘The method involves the following steps Step Write the redox reaction in ionic form, Step U1 Split the redox reaction into its two hall reactions, 0, the oxidation-half and the reduction half, ‘Step Il Balance atoms of each half-reaction by using simple multiples (not applicable for hydrogen and oxygen) ‘Step V For balancing Hand ©. () Use simple multiples f possible. (i) For acidie and neutral solutions add water molecules to the side deficient in oxygen and HT tothe side deficient in hydrogen. (i) tm case ofatkatine solution foreach excess of ‘oxygen add one water molecule to the same side and wo OH tons on the other side ‘hydrogen is stl unbalanced add one Of io {or each excess of hydrogen an the same side land one water melecule o the other sidestep Addelectrons tothe side deficientin electrons, so ‘as to equalise the charge on both the sides. ‘step VI. Multiply one or both the half-reactions by @ suitable number so that the numbers. of electrons become equal in both the equations ‘sep vt da the two balance half reactions and cancel any term common to both the sides. in the reaction, Cut HNO; —+ CullNO,), + NO+ H,0 Stepwise approach is ‘Sept tonic equation. Cus I+ NOS — cuts Now 140 Step Mand 1 Spliting of lonic reaction into two halfreactions. cu Qeidatonhall, G26 nos Reduction ay StepI Adding 1,0 and H" to the side deficient in oxygen and hydrogen respectively (according to simple multiple approach) cu Leidatonhalt, gz, NO; +44" —+ NO+214,0 ‘Step Vand VI Adding electrons to the side deficient in electrons {cu 2sdation bal, Ing + nt sae~ BMDP, No.4 2H,0he2 For balancing electrons, oxldaton-alf reaction {sto be multiplied by 9 andthe reducion-half reaction ito be mulipied by 2 Hence we ge 3Cu —> SCu* + Ge"; 2NO5 + BH + Ge" —s 2NOs 4140 ‘Step VII Adding both the half-reactions ‘3Cus 2NO; + BHT —+ 3Cu? + 2NO+ 4,0 Converting the complete reaction into molecular form (wile doing go ore add NO; both the sides), we get 3eu+ 2NO; + BH + NOG —> SCAF* + 2NO 4+ 8NO; + 48,0 oF SCu+ SHINO, —+ SCu{NO,), + 2NO + 41,0 cut +203 Redox Reactions 279 2. Oxidation Number Method “his method i based upon the fact that total increase in oxidation number must be equal to total decrease in oxidation number. The stepwise approach s Step Wirite the skeleton equation Uf not given) representing the chemical change Step It Assign oxidation number to the atoms in the equation and find out which atoms are undergoing oxidation and reduction. Write separate equations for the atoms undergoing oxidation and reduction. ‘Step I nd the change tn oxidation number in each equation, Make the change equal in both the equations by muliplying with suitable integers. ‘Add both the equations. Step 1v Complete the balancing. First balance those substance which undergone change n oxidation number and then other atoms except and 0. lastly balance Hand O by puting HO molecules ‘whenever needed. eg, balance the equation, (Cu+ HINO, —+ CulNO,) + NO, +40 Stepwise approach Step land irng oxidation numbers of ll he atoms — CusthG, — Quito, «NG 1d chang neiaie number hcwmby sono, Gi maess5 Gpio,), HNo, P75 Ho, thus, In case of Cu, oxidation number is increased by 2 units while in the case of nitrogen, oxidation number is decreased by 1 unit. Step To make increase and decrease equal, the lower equation is to be multiplied by 2. Thus, the equation will be, Cu + 2HINO, —> CulNO,), *2NO, +10 StepIV Balancingnitrateions, Hand gave theresultas, (Cu +AHINO; —+ CulNO,) + 2NO, + 244,0280 JEE Main Chemistry ibe ream ‘ick oe a Battneduny by erkcen ated doula none Patil aed tye sang aoe and eg = ro eas ofan) —+ me spore Interpret Ri + OFF) —= Pads HPO;Ce Since fecha tl con ta Bae » sawcrtemmaiiy —4 Bas falince oxidation number by adding elections, Pd 12° —> APH) iy Balance charg by adding OH ons, Puld +1267 —> 4PHg) + 120H a9). Balance 0’ atoms by adding HO 1240+ Bl + 126° —> PHI) + 2OKTag 0) Osiaton halt reaction Pals) —> HPO;(20) oo Balance Pstoms, Fata > a4PO;ta0) si Balance oidation number by adding electrons, Paid —> AH,POGlag)+ 46° tin Balance charge by adding OFF fons si BOF (aq) —+ 4H,PO;(20) + 46° (Oxygen and hydiogen are balanced auzomaticaly First multpy Ea (i by 3t equalie numberof electrons gin and ocean i109, Thus, we Re, Anis + 12OH"(aq) + 12,00) —+APHlg) + 12H,PO;t00) or yl) + 30H (a9) + 3H,OM) —> PHLLg) + 3H,PO;lad By oxidation umber method Rw + owe —- Bio +HiPOaa) [aera Pa Inabalanced chemical reaction essa electon So, multiply HPO; by 3 and we get Pls + OFF faq) —+ PH4(g) + 34,POF -Mulply OF” by 3t balance the charge Py + 301 (aq) —> Prhig) + 3H,PO5(a0) Balance H by adding 3H,0to LHS Pus + 3H,O1 + 30H (an) —> PHLig) + 3H,PO;Laq) Ins eatin Pact both an ong agent as wel a9 reducing agent, arr sain ofelectonsWORKED OUT ‘Example 1 Inte eacton, HO, +NA,C0 —> N20, + CO, + H,0 tte substance undergoing oxidation is HO, 10) NascO, 0 Na, (8 None of hese Solution arid, +8;63, —n,3, + 28s 33 tire sation soe ofl telomere an a Sea deta eaten oredccon pees Rane cf te crn changes oon robe, Example 2-10 thefllowing reaction, 4° 4 3KOH + 3H,O —> 3KHPO, + PH, (a) Pisonlyexdied (bP only reduced {e) Pisbot oxidised a well as reduced (Nove ofthe above inti Solution (c) 4? + 3KOH + 34,0 —s 3KH,PO + Pry 3 unt decreases Hence, Pb oxidized 38 well 35 reduced. Example 3 Which fe llowing iota do ecton? in cay "9 0's CO, 1h as 40 Meow 92 fennel, — ech 180,624, — Ho Solution a) in edox reactions, oxdation and reduction aes lac simultaneously. Ges, — GB + Co, Since, in this reaction, there fo change inthe oxidation state of tlements, ie, tere sno oxidation of reduction in his reaction. Thus, tis not a redox reaction. (Al ether given reactions vol the change in oxidation sate, fe, oxidation and redtion) Example 4 The equivalent weight of $0, inthe following NiiCh; #380) 1350, —+ 9Na350, + C80uh + HO % o® (a98 é 98 o® Examples Solution (5) n this action, 6 moles of lecton are involved witht male of 50, So, H,S0, acts ete as acidic medium. Ge + CHOP + Cr" 6 (eduction) paiae-2 26 SO; SOF + 2613026) So, eqivalent weight of H,S0, Example For the redox reaction, MnO; + C,OF +H —+ Mai + CO, + HO CConect soichiometne coefficlents of MnO%, GO and H* are a) 2,165 6) 2.5.18 (© 16.5.2 (8 5,16,2 Solution.) the ‘allowing tps ae ive to tance this “G Slt theqution nto onion and reducion hall: eactions ‘MoOg Ma, Gor — co, (Baan the str ober han © and H Ny — ht cor — 2c0, (Ad ie ect in Oa ot ede MoO; + aH —s Me + 44,0; cot — 200, (Balance the charge by adng electrons. MnO; + H+ Se — Mn 4 44,0 Gok — 200, +28" (0) Equa he numb of lcs a then ald bh the enue Iso; + aH" + Se” — Mn + 4H,0)%2 [0h —s 200, + 26 1x5 Ban; 16H 95C,OF —> avn?” + 1060, +80 “Thus, the coefficients ofhn0;,C,OF and H” ae respectively 2, Sand 16Start Practice JEE Main Round I (Topically Divided Problems) Oxidation State 41, Oxidation number ofS in SOF +s +3 oe (nz 2. Oxidation numberof nitrogen is high @) at MO, (eyNon (8, 3. In which of tho following compounds, an element ‘exhibits two different oxidation states? INCERT temp) (a) w,0H mmm, (Oma One 4, The oxidation number of oxygen in OF 8 mez =z ort @-1 5. The oxidation number of Crin CrO, is @s3 O45 +e HO 6. The oxidation states of iodine in HIO, H.lO, and B10, are respectively (tieae? O77 43 (oanste7 @ 47.0543 7. In which ofthe following compounds, the oxidation ‘numberof iodine i factional? On Om Om 8. The oxidation numberof an element in ¢ compound {is evaluated on the basis of certain rules. Which of ‘the following rules isnot correc in this respect? INCERT Exemplar (2) The ondation numberof hydrogen ie always +1. (©) The algebraic sum of ll the oxidation numbers in & compound is ero, (6) An element in the fee or the uncombined state beats oxidation numer ere. (Gn ts compounds, the oxdaon numberof 9. The oxidation number of chromium in potassium dichromate is @ez wre ose +8 10. Im the conversion of By to BrO5, the oxidation number of Br changes from [a) za to 5 () +1045, (9 ze10t0-3 (a) +2t045 11. In permonosulphurle acid (F,S0,), the oxidation numberof sulphur is ‘+8 +4 (+5 (re 12. The oxidation number of N and Cl in NOCIO, respectively are (@)e2end+7 () +3and.07 (-Band-+5 (@) +20nd-7 13. The largest oxidation number exhibited by an clement depends on its outer electronic configuration, With which of the following outer lectronie configurations the element will exhibit largest oxidation number? INCERT emp (ad ast 304? (93a ast (a) 3d? aa? 14, Find the oxidation state of C, and G inthe fllowing ‘compound. CH,CH,OH nese @o2 20 (@-2-2 @-24 435. Oxidation state of CinGH,COOH Ss cea (@o or (2 @3 16, Theoxidation stato of wo sulphur atoms in1,8,05 8 (8 wre (ose @-«117. When K,C0; is converted into K,Cr0,, the change ‘mexidation numberof ehromium's ao OS 7 HD Redox Reactions 18, Which of the following is the best deserption ofthe ‘behaviour of bromine inthe reaction given below? H,0+By —> HOBr+ HBr (a) Proton aeeptr only (@) Both oridised and reduced (6 Oxiised onty (@ Reduced only 19, Which ofthe following not anintermolecular redox reaction? (2) MgC0, —> Mgo+ co, H+ a, — 2H (K+ —> Kos (1/2, (8) Minbs, —> Mindy + (1/2)B 20, Which conversion isan oxidation? (sit — so yeu + cw ors orn 24, In the reaction, Cl, + 6NaOH —> NaClO, + SNaCl+ 3H0 the element which loses as well a gins electrons is (Na wo a (€) None of these 22. OF the following reastions, only one is a redox reaction Identify this reaction. (e) ato + ttt —> cade + 2,0 (0) 25,0 + 2n40 —> 2s + 4” (oBacy + Mga, —> Bas0, + NGO, (@)cu,5+ 2fe0 —> 200+ 2Fe+ SO 23, Whive phosphorus reacts with caustic soda, the Droducts are PH and Nall,PO,, Tis reaction is an ‘example of (2) oxidation (0) reduction (© elsproportionation (4) neutralisation 24, Which of the following is the strongest reducing gent in aqueous media? Ow OM OL 25, Inthe reaction, 2FeCly+ HS —y 2FeCl, + 2HCL+S (6) ed ais an edsng agent (@) Both HS and Fey, ae ended (6) Fed, i onde wile Hy i reduced (OS tes a an oidsing agent wa Redox Reactions 283 26. Which othe following isthe strongestoridising agent? @k Or oe Om 27. In the reaction, SO, + 21,8 — 38 + 2H,0 the substance that exiises is ous (3 ws uo 28, Which of the following acs as an oxidising agent? ‘aN, wo, (ore, (@ al of the above 29. Identify disproportionation reaction {NCERT Exemplir (a), + 20 —> +2440 (ca + 40, > ch + HCL (2% + 209 —> 2+ OR +0 (@)2N0, «2087 —> nog +0; + #0 30. MnO{- undergoes disproportionation reaction in acidié medium bat Mn, does not because INCERT Exempla (o) In Moo, Mn isin imermediae oxidation state (8) In Moo, Mn isin owes oidation tte (© tn ing, Mn isin intermediate oxidation state (@) None of he stove 34, Which ofthe following (1,50 with Neo (@)matmosphee 0, from 0, by lightening (©) Wiuogen oxides fom aitiogen and oxygen ghtening ore (@ Brapoation oF ,0 32, The reaction, (Che) + 20H-(a0) —> CIO" (ag) + C1-Cagh + HyOKD) represents the process of bleaching. Identify and ‘name the species that bleaches the substances dust its oxidising action. redox reaction? INERT emp oa wo oor (oo 33. Whenever a reaction between an oxidising agent and reducing agent scarred oat ne ncn compend of we nation ate fred ne ‘cit apts ee (campo fh oton state om ‘the oxidising agent is in excess foe (oan ela) (8 one te co284 JEE Main Chemistry Balancing of Redox Reactions 34, The coefficients of F105 and H* in the redox T+10;+H" —+h+H,0 in the reaction, Dalanced form respectively are (sis Iss ELS (8) 561 35, In the equation NO? +H,0 —+ NO$ +2H° +ne stands for @r M2 3 ws 36. The value ofm in ‘MnO; +8H" + ne” —+ Ma?* + 4H,0i8 os Ms 2 ws 37. @KyCq0; + BKCI + cH,S0, —> "=CrO,Cl, + yKHSO, + 21,0 ‘The above equation balances when (a) a=2,b=4,e~6and 138, In the reaction, 8Al +3Fe,0, —+ 44103 +5Fe the Timber of electrons transferred from the redutant to the oxidant is (as ms ew (a) 24 39. The value of Win the craton TRO MH + aBo* + 20" + Fo 470 wibe a2 @)3 we @? ‘40. Tae Ma* ion is unstable in solution and undergoes disproportionation to give Mn**,MnO, and H'ton. ‘The balanced ionie equation for the reaction is Ince, (a) Ma? +210 —> Mn?™ + 5H” + nO, (oy 2m?" + 1,0 —> Mn + 211" + Mn, (o)2Mn?* +280 > Ma" + MnO, + 4H (@) None ofthe above Round IL (Mixed Bag) Only One Correct Option 4, What are the oxidation numbersofthe three Tstoms, inkl? tween, (@)0,0,-1 @)-19, 1 0-30 @ 2. Which ofthe following acts as an oxidising as well as reducing agent? (a) 0 emo, (o matt, (@ m0, 3. During a redox titration involving a solution containing Fe" ions against MnO; in the presence of ‘excess of H" ions, the number of electrons that gets transferred ae mS sR 4, Whon sulphur dioxide is passed in an acidified K,Cx0; solution, the oxidation state of sulphur is from (sto Q)st0z 5. In the following reaction, M+ a0; —+ MO; ema! «20, (ss Méws one mole of nO; oxtdses 2.6 moles of M** then. the value of xs OF 03 ew? 6. SKCIO, + 31,80, —s SKHSO, + HCIO, + 2010, +H Equivalent weight of C104 is " ” o£ mt clas 7. ‘The equivalent weight of ENO, (anolecular weight = 63) in the following reaction is 30a SHINO, —+ 3CuCNOsh +2NO + 4,0 yt a 8 e oF oF 08 wf 8. Amole of NH, loses 10 moles of electron to form new compound Y. Assuming that all the nitrge® appears in the new compound, what is the oxidator state of nitrogen in ¥? (There 18 no change inthe oxidation number of hydrogen.) O12 32 G5 9. Which of the following reactions donot involve oxidation reduction? L.2Rb +2H,0 —+ 2RLOH +H, IL2Cul —+ 2Cul+ 1, ULNH,Br +KOH —> KBr +NH, +1,0 IV. 4KCN +Fe(CN), —+ Kyl FACN 4] jin @Lm formw @mw10. a. 1. 2B, 14. 15, 16. uw. In which ofthe flowing pairs is there the greatest, Aiference inthe oxidation ‘numbers ofthe {nelned elements? (0) 0, sna, (@xpaano (2) $0, ana, ere ammonium sulphste and potassium Dermanginat are used an ordsing agen in ade Inedium for the oxidation of fereus ammonia rlphate to ferse sulphate The ratio of aumber of ‘oles of ceric ammonium sulphate required per ‘ol of ferrous ammonium eulphate to the umber Of moles of KMnO, required per mole of Terous ‘montium eulphate, a @)50 @) 02 (os @20 Oxidation states of X,¥,2 are +245 and -2 respectively. Formula ofthe compound formed by thete wil be @) 4, (b) HZ, om, wan In which of the following reactions hydrogen is scting os on oicaing agent? (@) Wht form LH () Wh to give HE Gmthstosiven,s (a) None of these (0), andR0, ‘The number of peroxide bonds in persenate ion [%00,)*"is| ao we 3 1 Oxidation states of the metal in the minorals Jhacmatite and magnetite, respectively, are (@) IL Hin haematite and I in magnetite (0), in haematite and It in magnetite (©)Min haematite and 1, Hin magnetite (@) Win haematite and 1, in magnetite Ma can be converted into Mn" by reacting with 50, ory (Ro, (sn, While eulphur dioxide and hydrogen peroxide ean act as oxidising as well as reducing agents in their reactions, ozone and nitric acid act oaly as oxidants. ‘This is beenuse 1ncenr) (2) in $0, andi, $ and Oarein their lowest oxidation Hate (@) in 0, and HWO,,€and 0 are in their highest dation state (ind, andi, w and Oarein theirlowest oxidation (2) Both (a) and Redox Reactions 285 18, Thiosulphate reacts diferently with tedine and ‘bromine in the reactions given below INERT taemplar, NCERT 28,0 +1, + 8,03 + 2r- 80% + 2Bq + 6H,O—> 280° + 4B" 4108" ‘Which of the fllowing statements justifies the above dual behaviour of thioeulphata? (a) Bromine ea stronger oxidant than iodine (@) Bromine ea weaker oxidant than iodine (c)Thioslghate undergoes oxidation by bromine and reduction by iodine in these reactions (@) Bromine undergoes oxidation and fdine undergoes reduction in these reactions 19, Which of tho following statements is not correct? (a) The oxidation number ofS in (NE), 5,0, is +8 (@) Te oxidation number of Os in 05, 18+ & (6) The oxidation numberof S in 50, i +8 (@) Tee oxidation number of 0 in KO, is -1/2 More than One Correct Option 20. Wich ofthe following reactions should be balanced indus median? Co) + a — oy +0, (0) CH(OH), +, —> Cr(OH), + 21° (HN, Fe 51 1, (Oa, +F* 50, +e" 24, Which of he folowing statements var errs? Inthe reaction 20uP +yCn0% —9 ca +1PO,+ Cet (0) Gwin? is ovtied tou wheeas Pin Cie sto ended tore (2) 6u in cuit oxi to Ca whereas Pin Cas is reduced 020, (tm the converion of CaP to cu and HP, 11 ectronsare involved (a) Te wae of xis 6 22, Which of the following statements about the flowing reaction is are wrong? 20.40)+ Crys) —> 6CU)+ SOX) (2 Bott and cae reduced (0 only cus reduced (04S the exdane, (8) only Cu redaced286 JEE Main Chemistry 23, Which ofthe fllowing hav/have been arranged in ter of decreasing esssatio stat of eulpbur? TO)ESO, > H9,5.0 > 835.0 > Se () SO > so" > St > HS, (R80, ~ 1,50» te = BS (€) 0, >, > 1S > HS05 24, Which of the following statemente(s) ilar not true bout the following decomposition reaction? 2KCIO —+ 2KCI+ 30, INCTET empl) (a) tassios undergoing oidation {8 Closine i undergoing oxidation (6) Oxygen is reduced {ah one of the species are undergoing oxidation or redaction Assertion and Reason Directions (0. Nos. 251027) Eachofthne uetions contains eo ets: Staten Aserton and Sate Ren). Each of these yustons alc as our tomate es, ny one ofc he tort ensue. You hi Io sl one of he es (a) (2 (0 08 ‘The oxidation number ofX te -2, and neither X nor water is {nvolved inthe redo process. 28. The element(s) undergoing oxidation is/are @a Oe or (@) Bor Forboth 29. The possible oxidation states of B and ¥ in BY are respectively (@en-1 ) 22-2 (943.3 (0) All of these 30, Ifthe above reaction is balanced with smallest whole umber coefficients, the sum of the stoichiometric tvefficients ofall the compounds is @s me 7 ws Directions (Q.Nos.31:034) Redox equations are balanoxd ‘ther by ion electron methed or by oxidation number method. WT to the correct form of the balanced The ton electron method has fo advantages, © ‘Se chemists prefer to use the soa electron method for redox ection carried out in dite aqucous solution, where free Both metheds fons have more oles independent existence. trio (2) Statement lis trie, Statement Iis true; Statement isa correct explanation fo Statement I (@) Statesnent is tre, Statement Is true; Statement Tis not a correct explanation for Statement 1 (6 Statement lis tre; Statement Ils alse. (a) Statement is alse; Statement Ili ime 25, Statemest | Among halogens fluorine 1s the best oxidant Statement ll Fluorine is the most electronegative atom. INCERT Exempla 26, Statement | In the reaction between potassium ‘permanganate and potassium iodide, permanganate fons actas oxidising agent. ‘Statement il Oxidation state of manganese changes from +2 0-47 during the reaction, INCERT Cxenpar] 27. Statomest The decomposition of hydrogen peroxide to form water and oxygen is an example of isproportionation reaction. ‘Statomeat The oxygen of peroxide isin -1 oxidation state and itis converted ta zero oxidation state nO fand ~Zoxidation state in HO. (NCERT Cempla] Comprehension Based Questions Directions 1. Nos. 28 t 30) Cons ‘unbalanced redox reaction HO +AX +BY —+ HAs OY #X:B the following ‘The enidaton sate method for redox reactions is mostly used fortolid chemical or for reactions in concentrated acid media. 31. For the reaction K,(Fe(CN),] —> Fe + CO, ~NOF the mfactor is @a on 5 @ @a 32, For the reaction, FeS, —+ Fe" +S, the n-fnctor ss at on ow oa 33, Forthe reaction, By +2NaOH —> NaBrO, + NaBr+ H,0 henner is en os oa we 3 34, For the reaction, As) —+ Ast + SOF the mfnetor i an ws wo weRedox Reactions 287 Previous Years’ Questions | 35, What products are expected ftom the Aisproportionation reaction of hypochlorous acid? TAKE 2051 (ayn, ana.a,0 () HoD,ana Ha0, (@ atandao (@ Hoare Han, 36, Which ofthe following chemical reactions depicts the oxidising behaviour of H,S0,? {AEE 2061 () 28 + H,50, —9 1, +90, «280 (Ca(OH, + H,5q —> 50, + 24,0 (O)NaCl+H90, —> NaHS, FEL (@)2P01, + 1,50, —+ 2F00, + H+ 90,0, 137. Thooxidation state of chromium in the final product farmed by the reaction between KI and acidified 38, Oxidation number of Cl in CaOCl, (bleaching powder) is (atee 2008 (@) sao, since it contains () since i eantains cr (0) since it contains 00" (@) +1and =, since it contains O™ and or 39, MnO; is good oxidising agent in different medium hangings ent tng Mat 4 Mn0, —+ MnO, (Changes in oxidation number respectively are Tateee 2002) 13.45 5.43.2 sass Meeas 40. Which the fllowing isa redox reaction? tates 2002 (1m +1000, —+ mao, + Ka potassium dichromate solutions 1ANEEZI85) ) ca, + ata —> cack 560, (oes as (9.GOH), + HA —s cat « MH, 210 (ore ws {)2R{Ag{ON,) 2a —s 2Ag + K20(C] Answers und | | 1@ 2% 3 4@ 50 66 26 B8@ 90 mw | £6 2m nO wo BO BO 2 BO Be DO | HO 26O 2O *O BO BOY RO BH BO De 2O 20 26 44 5H HO 7H BH BO MO Round i 1@ 2@ 30 40 §® 608 7M B80 30 wm ie 20 2@ xo 89 2O 7H BO ME 2—d Aland aed alec) wierd 6) 2%) WO 2) mW) se) LO ae ae 4H BO TO BH BO HOthe Guidance The su of oxidation sates ofall elements in anion is equal tocharge ont Let the oxidation state ofS in SOF = * HHO xM=-2 oF x= 46 2. nt ‘Oxidation umber of ‘oxidation umber ofN = 3 Hence, in N,0, the oxidation number of itogen Is highest InN, 3. Ne4NO,isacually NHj ard. In 'N is—3and in NO; onidaton sate of Nis +5 4. OB x 2-02 002 CttioyrnerofO= 2 5. Dog] tetsu ema g having an oxidation number of -1 and ane double bor in tahich oxidation numberof O52 Therefore, xt Ait) rat =O : aa46 6, The oxidation sate of iodine inHIO, is +788 Text 2-0 “The onidation state of fdine in Os +785 Peves 147 “The oxidation state ffdine in FIO, is +735 Sx 6-200 aes? 7. Oxidation umber oiodie inthe given species sas follows 43 9. Let the oxidation numberof Cr be 5 FOrKCHO; “baat res 2-0 aeaeia=0 ast x6 410, Bromine has zero oxidation sate because iis in fee sae, Br, —+ 8105 Letthe oxidation number ofr in BrO} sx. sa C23o-1 a4 62-1 xet6-1 +5 So oxidation number changes from 00+ 5. 114, Permanosulphuric acid (H:S0,) has two oxygen atoms in erode linkage, hence, ads x4 2-04.32) 24x-2-600 wat 12, Oxdasion numberof InNO* Is ten) e(-2=41 x43 (Oxidation number of Cin CIO; is (00) 6436-1 a7 13, Mavimum onidation state for dblock elements 1-1 unpaired de” se™ For 42? configuration, Maximum oxidation umber =5 + 2-7 14, CH.CHOH EHS dxs6(u941e21=0 ° wed Thereore, the average oxidation pumber of C52 Let us consider the structure of CH,CH,OH i mgepion (Oxidation numberof atom VG M42 D+ xe 1 eN=O [Gator i tached to one CH, group (oxidation numbet 12+ 1, tWoH atoms and one —H group (Ox 09. —U)x2 ‘Oxidation numberof C,atom=3 (+1) 4c 11-1) =0 {cy tom is atached to thee Hatoms and one —CHOH ‘woup (Ox 90.=-0) ye? 15, HCOOH 20 4026-220 nests 16, The chemical sructureofH.S,0, isa follows orx=0 2a(et) +254 60(-2) 4 2 (-1)=0 “$242e-12-2=0 Dee? a=46 11D. Lethe oxidation tte of Crim K CHO; (ovens 244 (2257) Let the oxidton sat of CrinKsCrOy = HUD 2H4)20 2418-0 16 ‘Change In oxidation state of Crs zero when it changes om3C20,; t0K:C!Oy 18. Iisa dspropotionation reaction. 19. Intermolecular edox reaction and redox rections are sare, 20. Loss of an electron or increase in oxdation numb is ‘oxidation process. Woe 21. Wis 2 dispoportonation reaction, s0 Cl undergoes both oxtation and eduction onion 22. Gui3 +283 —+ 2u+2Fe+ 30 ag In this reaction Cu and Fe undergo reduction while sulphur Undergoes oxidation, Hence, this sa redox reaction. 23. In this reaction phosphorus is simultaneously osaised and reduced. is adisproporionation reaction Bo 3NQOH+ 34,0 —s aNaitO, + Phy Redox Reactions 289 26, tn an aqucous medium, L is the strongest reducing aget, Since the high negative enthalpy of hyeston compenester wn, 25. +Fd" —+ Fo" tcton Tero oC 2 5 noid ae. 26. Reduction ental ores, >C 85> So,hysthe eons oiing ae. Oworaver ar reatendeey opted dito thigh cewenegatve ature) 28. Altes sana can cet scons ad cin decease aaron aoe a onan mn ae tile, —+ Ho, orto ch er ia, fo, ttn 25. Hows 20% —> 80; NOs + HO LL pextwction —P Sciatic ene element ie, Wisreucedas wales ntsc sot a dupeponionaon econ, 30, mvt he endatonrunber ot +6. Reaninenie it nation number f° or decrse ts onaon umber tb + 4,+3,4 2,0). Henee, it undergoes ‘Sepropotontion reaction is side medium, cepacia Indtno, Mn is ins highest oxidation state, Le, +7. Kean cnly decrease its oxidation number. Hence, it cannot ‘undergo disproporionation reaction, 34, a.Newwalsaton b. Iisthe change ofan element in ne form fxidation stale =0) 10 another form. € Redox reacton{ hs + ©: —+ 8G) 1. Physical change 32, Cig) + 264 “taq) —s GO-taq) + Crea + HOW ln this reaction, oxidation number of Cl increases fom 0 (inCh)t0 1 in C1O") 35 well as decreases from On C101 linCh).S,itactsasboth redacing agentas well as oxidising gent. Ths isan example of dspropoionation reaction. I thisreacion, CIO" species bleaches the substances due tits ‘xidisingacton In hypechlrte on{CIO", Clean decrease lsexidation eurber fom +1 100 oF =U]290 JEE Main Chemistry 133. Both the statements are core. Ths can be proved by folowing example ea reducing apent ard Chia onising agent aPa, 0 Pe (aescie) eee . Lomer oxidation state of P cakaassocys —> 4B taal” ar oneinsatetF Therefore, when Pe (educing agent tn exes PC) i qormed i which ondsion ste of Pi +3 and HCl Coding ap sce PC, formed which onion sane of Pie a6.rs Tor ent rhe ho ar tte es 5 woe +2707 9's Ai (manga and Gh we 100-2105 —> 6h Tebalnce Oso, a886HO melecioson RMS and 12H" oats, ben Tor 920; +124" —> 6 +6440 or ST+105 Ge" — 3, +3140 35. NOR + HO —+ NOB + 2H® 426" lance charge on bth sides 36. MnO; +H 653M + AHO 37. gh(20) + bRCL gH, —> BEE. Oe YA8 4 FO M90 431-0 ore Therlore, the average oxidation numberof 16 =: 1s wrong becave onidation number cant be factional. Let {conider the structure fy Ku=1<-0 tis suture, a coordinate bond is formed teweenly molecule andon. Henee the oxidation number ofthe ators nl a0, 0 in) and 1 vespecvely 2. NaNO, Godium rit) sce oth a oxising ab wel 5 reducing agent beau nN ator in Sexton sate (irtermediateoxdation sate Oxidising oper 2NINO, + 241+ 2H,$0, —+ Na,S0,+KS0, TINO 2H,0+ 4 Reducing property 110;+ NaNO, —+ NaNO, +H,0 38. BAI —p BAP" + 246° fel + 24e —> Fe 39. COP +14H" 4nFe!* —» 20°" + Fe + 7H, COP +14 +66" > 20P* +7H,0 (reduction Fe 9 Fe +e (oxidation) i a (i mail by © Gheth > GFE + 6 “Thus, blanced equations COP +14H" + 6Fe™ —+ 207" + 6Fe* 7H, Hence, the value of 6 “The skeletal equations, ‘Me?*iagh —» Mn*(aq) + MnO zs + Haq) (Oxidation half reaction san (aq) + Wins» 0 Balance charge by adding 4H* to RHS and then balance O toms by ading 4,00 LHS Ma? *(aq)+ 24010 —+ MnO, 6)+ + AH (ag) 8y dang) and i we ge 2M") +2400 —+ Mn +Mn049 + 4429) “This tepresents the final balanced redox reacon \dsproporionaton react). “i 3. MnO] + 8H" +52” —> Mini 44140 Wo" 5 Fe eps. OO Sa > wn Se Fie electrons ges wansfered. 4, Acide KC}, solution oxides SO, into CriSO4y 380, +610, + 1350, —+ K,504+ CYS. +H,0 Hence, oxidation tate of sulphur changes fom + 4t0 +6 xaiton ‘Cage in oidation ie 5. ste « ato; —s fds sun oto, Chap notion tees xe25 aeS-2036. Dispropertination reaction, ClO? —> ClO? +2 =2) oxidation) auivaent weight 7. nhs case ony 2 moles of NO$ undergo reduction 36+ NOS —+ NOW 3) redcton) vas ye? ‘6 moles ofHINO, ae not changing so NOP ate aed in the action to ge 3 moles of CutNO2), 63 ivaent weight as M9 SM teu tame MAS BLN, > 2¥ 4100" 2444-0 2y=2 9.1, Rb een Hore — Bi Sry pecion Vee on aon Meer > Gy Reto 2P 26 (Oxon Views ims fi, + nt, fo chngln ston bet ae) en W. Ne carein te dato ber ferro" OP Into eacanan pes ee, texan. 10. nope anove~a Die ntti f= 0 (1a eee in oon ste of? 260) | Nou=rndnonen, Orne in onan st wso,nenatsoyire Diener moto se of= 2 Fo co ye ve" SFel* + MnOy + 8H* —+ sei* + Mn" + 4H,0 Moles ceric ammonium subhale, 1.5.9 “Moles of potas permanganate "173 1 Redox Reactions 291 12. The oxidation sate of X, ¥ and Z are 42,45 and -2 respectively Um kYZq202454+6-220 tin xizy=24 542+ 6-2 W.inaye2+ 5.240 Wain XidqnB02 45+ D0 Hence, the formula of the compound is X52. 13. ie4, — ail (Oxidation numberof hydrogen is decreasing {rm 0 0 1 SoH acting ae oxidising agent in this acon, 14, Nomen td ineO4” Seu “OF soNemo 0 15 rete FO which xan nomber oo Mgpete is FOO, which 6 inc 9 ned one (F20:Fe40) hence ton ispresent ia beth iand I exidation 16. 20Cl, + 5Pb0, + 6HNOS —> 24ND, + 2POCl, + SPBINO,),+ 24,0 417, anctsrany ats lomest oxidation tate, can behave only as reducant while In Is highest oxidation state can behave ‘only as oxidant nitetredite oxidation states, elements ‘an behave as oxidant as wel reduc 1 1950, 5 isin + 4 oxidation sate can have minimum ‘oxidation number ~2 and maximum oxidation number +6. Therelore, Sin SO, caneither decrease or increas ‘oxidation number, So, SO; ean act bth a oxiising 36 ‘welasredicing age IoH,0,, Os in1 oxidation sate. ean have minim oxidation number ~2 and maximum oxidation number zero (+1 and +2 also possible in Ojf, and OF, respectively). Therefore, ("in H,O, can either dacreace or nceae its oxidation number. So, H,0,can at both 3¢ oxidising a wel reducing agent, {8 19 O,, 0 isin 2er oxidation sae. cannot increase ‘oxidation number, can only decrease is oxidation umber fom zero to 1 or 2.50, oxerecan actonly a6 ‘9 otnng agent. Gyn HNO, the oxdation number of N is +5. 8 ie ‘maximum So, NinFNO cancel decreas ts oxidation number. o, i can act san oxidising sent oly 25,0 Faq + fas —s 8, 62t00) + 2F10@) araas aby ean cs Boma +4 aq) +108 Ga)292 JEE Main Chemistry Bromine being sronger oxidising agent thant, oxdises Sof S,0F to SOF whereas, oxiiesitcnly ito $,07 fn, 19. anito,sor Oxidation sate of = +6 (Since 8,0 has one peroxide bond) (6) Oxidation sate of O49 (©) Onidation sate of inH.SO, = +6 eit has one peroxide bond) (@K"OF oxidation tate of O=-1/2 20. In ialMnc® —+ MnO, occurs only in basic medium In) CxOH,—» CHOY, occurs only in basic medium, {Gand (@) occurs only in sce medium 24, 44,04 Carbs acu 414p0, +1e + SHI x6 Ge SHH? 6 COP —+ 20°" 4 HOH 1wO +64 PO, + 22c1% «53140 22, In CuO and Cu the ondation sate of Cis + So theyre reduced to Cu"(Cu" +e —> CP 23, HS:0/242« Na,O,:2 44122059 1°25 ign tt, NaSi0p:2 624-620-042, [Ondsionsatets Syi8e-0-9x=0 {@ 1180, (Perxo linkage) Oxidation state of5= +6 1450,:2+4-¢ Oxidation state of 44 'sC:1-2=0 Oxidation state oS 5:2 + x=0 Oxidation sat of = -2 Fass re a 24, 2K G6, —+ 2436, idan 25, rine being mst eeconegaive emer te Bost net 26, 1041+ 20804 +850,—+ 24850, +6650, +Ho+5% Oxidation ¥ a7. apd 9 2G obs election’ “Thus, the above reaction isan example of alspropontionaton reaction 2B. Oxidation sate of X=-2-2 AX Oxidation sate of 0-2 OF Oxidation sate of =-2, 9 8 B Ris eyeno — > HAs O¥+ OB ea A® —> AP (eduction) BY —+ Bt +¥* toxidation) “Therefore, 8 or Vor both might have been oxiised 29. in BY the oxidation sate of B+ Oridton sate of ¥<+2 Pawndation ate of Bis stand that of Ys then bok ‘willbe oxide. te onidton sae of i +2and that of Yis-2 hen bo ‘wl ees tthe oxidation ate of Be +2and that of 53, hen bo willbe oxiied 30, A +H 4360 > HAL? BY +10 —» 6H + OY 2H +e" 28" +BY +H —» 2HAs Bt «OY or 2ACBY+HO —s A+ BX + OF Petet e aeted Tesumefal ie coun 8. 31. Ee] ovations arene Fe 5 Fee GCM? —+ 60, 126° GNP —+ 6NOP + 486" Onsidation mbes ane) FEGUI™ —> Fe + 6C0, + 6NOF + 32. Fo" 5 Fe ge Toute'=1t S$—+ 250, + 10° dea 33. By > 28:07 +100 dee De-t26-226 +8 —> 26155 > 2eOF + 8 valent weight of, = 218.2 Seana one Bh. Ady 280 4 Sh OF + 2 deeb Se 28en 35. HOC —+ 2HC1+ HCIO, lator =28 36. 2+ 80, —> Ta Sone ano HiS0, Reduced 9 —+ $0, oni een 37. CLOF 4 14H 46r > 20°* + 74,0431, CLOF is reduced to CP". Thus final state of Cs 3. Redox Reactions 293 38, C40¢1,e writen taialy as CAOCHCL (cr —+ clas +1oxidstion state (cr —+ Cihas—toxidaton sate iho; > Mat chee $ + thor canes + thoyehaee3 Zea anet 40. (9 NaCl Bids — Wind, + KEL wEce.+2t —+ Edi+teds (ad, aNd —s Gees ais 248 Inll hee cases during reaction, there is no change in Cudation tate of on or moleccle or constivent tom, ‘hese are simply fone reactions (4) 2KIAGICNIA1+ Zn —> 2AR + K2niCN) Ast —> Ag main of reduction Zn —+ Zn loss of oxidation.3 | Electrochemistry JEEMainsnestove + Electric and Motalle Conduction * Conductance in Electric Solutions + Electrochemical Cells * Danell Cet + Electrodes and Their Types * Battery 3.1 Electrolytic and Metallic Conduction ‘The substances which allow the passage of electric curent through them are called conductors, eg, metal such as Cu, Ag Sn ee. On the other hand, the substances which do not allow such passage through them aze called Insulators, eg, rubber, wood, said ete The conductors are of two types on the basis of thelr physical tate (a) Metallic Conductors ‘These are the metalic substances wich allow electricity to pase through, them without undergoing any chemical change. Most of them are solids. Pree clectrons and holes (positive charges) are responsible for the condition of such conductors. The conduction due to metalic conductors is called ‘electronic conductivity. It depends upon i) nature and structure of metal (i) numberof valence electons per ator (i) density of meta {) temperature inverse relation) Cs, Hg and Ga are metalic conductors but are liquids at room temperature, (b) Electrolytes or Electrolytic Conductors ‘These are the substances which allow the electelcty to pass through them in their molten states or in the form of their aqueous solutions. These undergo chemical decomposition when electricity passthrough ther. In real sense an electrolyte can be defined as a substance which dissociate into its fons when dissolved in apolar solvent like water. + Ful Ces + Blecrode Potential Electrochemical Series Electrochemistry is the branch of ‘chemistry which deals with inter-conversion of chemical energies and electrical energies. The chemical chonges invelving flow of electric current are ‘referred as eleetrochemical changes.746 JEE Main Chemistry ‘The conduction of eleciricty because of ions is called electrolytic conduction. The conductivity of electalyic solutions depends upon, (@ nature ofelecoite ly eizeofons produced and thee solvation faydration) (i) nature of solvent and its viscosity {) concentration ofthe electrolytes (0) temperature direct relation) ‘Acids, bases and their salts all are the examples of clectolyies, An electrolyte can be strong or weak. The strength of electrolyte depends upon its ability 10 dissociate. Strong electrolytes (eg, NaCl, HCl, KC, NaOH, HNO,,H,S0, te) have the ability to dissociate completly ‘or alma: completely while weak electrolytes (eg, H,COs, (CH,COOH, 27], HgCl, etc)on the otherhand are very ess cissociated ag compated to former one. ‘Table 3.1 Distinction between Metallic and Electrolytic Conduction ‘EN Mate conducion | Eecwoiic conduction 7. | Etc cures tows wy he | Beane cust tons By he frovwrerttaecrere” | moverenctios 2, | No chor! change tts | ndtn or eucton oon le ron wes | Crouse eee |i cow, not oko te | ewonos tans ctiraterh tecieaeymats” "| felametors 4 | peistance ceases win | Restance coseaee wth ceeeechemgorcut. | meee otters, «| Faraaylanicnct tones. | Fredy iwi flowed 3.2 Conductance in Electrolytic Solutions ‘The power of an electrolyte to conduct electric current is Called conductance or conductivity Just like metallic ‘conductors, electrolytic solutions also obey Ohm's lave, ‘hich siates,“The current lowing through a conductors ‘irecily proportional to the potential difference across it~ lev where, = current in ampere = potential diferencein volt v 1e¥ or Vere wars, Re proportonaty constant aed restsans of TA aly, resnce i the obsucton ah con aga conductor and is expres inom The conductance and re sonipte, jtance have reciprocal 1 cad ‘Thus, the unit of conductance is ohm“ or mbo and is enoted by 0°! In Slayster, its unt is stemen (S ‘The resistance of a conductor, is directly proportional to the length () and inversely proportional to the area of cross-section fa) ofthat conductor fe el and Red te rel vow pops const calepeti emt tliny. Mfl1cm anda =1cm?,then =p. conductor of 1 em length and having a cross-sectional area of 1 cm?. The unit of specific resistance is ohm-cm. Tete nknown ascent end expesed a he seco of ec restnce ead specie conductance, ie, the conductance of a solution of 1 em length and having 1 cm? area of cross-section. It is denoted by «(tappe). : where, C and & are conductance and resistance respectively Units ofspeciic conductance are ohm’ em“Yor mho can“? for stemens m* (in St system) QUPAC has recommended the use of term conductivity over specific conductance) ‘The measurement of resistance of ray be done with the help of a ‘Wheatstone bridge. ‘an electrolytic solution ‘conductivity cell in 2Fig. 3.1 Arango for mesuremen sfessanceot sient Teenie When nl pont ischained = 8 AOR Uno este, =A Knowing the values of, and R, R, can be calculated ‘Nowadays, inexpensive conductity meters are avallable ‘which can directly read the conductance or resistance of the solution in the conductivity cel. Gumectna Comes from Frac ie 22 Toten types fonda conduct cl ene anu decade nf usc and sr ote te 4 sana! Te fomuln ee eu/atra condo eal cone wir. cntnted For a cell itis determined by measuring the resistance of, the cell containing a solution whose conductivity is already known. The Wheatstone brige here is fed by an ‘AC source and, not by the DC source which may changes the composition of solution taken. Caution Point. Forsccuateresus he slurs sets be prepared (Raspecly parted wat, conan ofwhen evan eal Thal ‘Sealed conduct wa Electrochemistry 747 Sample Problem 1. the resistance ofa conductiviy cell ontaning0:001 M KCI solution at 298 Ki51 500.0. Whats the cell constant fconductityof 0.001 M KCL solution at 298 Kis 0.146.107 Sen? ween, @) 0.219e0" (t) 0.187 ont (0325 en" |e) 0.018 en? Interpret a) R=1500.0;«=0.146 x10” S en Cal conan =R xx =(1500 0) «(0.146 «10 Sem) =0.219 on"? Sample Problem 2 When acetain conductivity cell was filled with 0.020 M KCI which has a specific conductivity 0.27600", it had a resistance of 82.400 at 25°C. With 0.0025 M K,S0y, has a resitance of 3260 0. The conductivity of K80, solution is (a) 228 aor 054 (@ 0005 constant Interpret. 6) Call constant = xR 2760%82.4 = 2281" Specie conductance of S04 e904 = Molar Conductivity The conducting power of all the ions, produced Asclong terol ofan eeepc in slesoe eh ‘molar conductivity of that olution lis denotetby ora andi elated to specifi conductance) 38 ve=1000 M ‘concentration n mol/L, Le, molarity of he solution 1s units are ohmYem malt or mho em? mat Sem? met Ay OF w= where, Sample Problem 3. the conductivity of 0.20 M solution (OF KCI at 298 Kis 0.0248 Semis malar conductivity i ince, (a) 1.2400 mot en? (@ 1249" of en? (0) 124 S mor en? (8.01245 mot" ont 0248 «1000 020 2124 Smot on?748) JEE Main’ Chemistry Sample Problem 4 The electrical ressiance of a column (00.05 MNaOH solution of diameter tem and length 50. is 53510 ohm Caleult te molarcondetviy. wee 1148S ntmor! (2296 Sen?mol* {34895 cm!mol! (17535 en2m Interpret 5) Areata =n -2.143( 25% -o785 en? 1=500n atl og pf 555110 obmx0785 cn? aT ‘50cm 227335 08mm CCondectvity barcode) = 2 oe (201148 $e 21000 en? Et ~00smale* 2296S em? mol" Equivalent Conductivity The conducting power of all the Jons produced by isolving 1 equivalent of an electolyte in soluton is Called fs equivatent conductivity is denoted by eg OF tis elated to specific conductance 35 11000 Cu WY where, Gq ~ concentration of olution in equivalent per fie fe, normality) ris units re ohm rm? (equiv?) or mo em quit). or Ssem?(g-equiv”) ag OF Ae Gample Problem The resitance of a decinormal Solution of «salt occupying 2 volume between two platinum eco 1.80 em apart and’ 4crn? in area was found to be 50 ohm, The equivalent conductance ofthe solution is 667 (578 (a) 655 (0 0567 Interpret by Given,c = constant «= 82NCe 1.00 Cet cos saree 180 Normality 0.1 N 1000 conductance col consant ‘a= conceit formal 1090002 1 Or 6,66 Sen? eauivaent Effect of Nature of Electrolyte over ‘Conductivity he conductivity of an nature. of electrolyte. 35 ace eno Semi Sicp Sogn Sales a hn me in their solutions resulting t0 higher conductivity. Se band, dissociate less, meant Variation of Conducti (or Concentration) yor both weak and strong electrolytes, the electrolyte Conductance as well az the equivalent conductivity (Na) fd molar conduct (q) increase with dilution This is because the tial volume V of a solution containing t § equivalent or 1 mole of electrolyte also increases. It may be noted that decrease in on dilution of a solution i tote than that compensated by increase in its volume ‘conductivity (or speci conductivity, x always decreases ‘wth diuien, both for weak and strong electrolytes. This de tothe fact that the total numberof fons in the solution inreases on cluton but the numberof ons pet nit volume that camry the curent in the solution decreases on dilution. eee ty with Dilution (a) For Strong Electrolytes “The hug OF yf Stong electrolyte increases slowly with dilution and can be representec pre tuckel One ae “presented by Debye Huckel-Onsager ey Neg ENE OF Hig = Aig EVE Kin = Win ~ BNE OF Ney = Noy — BYE Ma plot of Ag OF Au agalnst VE is plated (a shown in figure) astaightline with intercept equal to ag or Afgan aus oat Cetin |at lower concentration, but isnot linea for higher concentration Te vl of fon the iype of electrolytes, Lo, the charges one eaton fand anion produced durin and anion Produced during the dissociation of the‘therefore, electrolytes ofa particular type have the same value ofb eg, CaSO, and 3-2 ype) have the same valu !MgS0« (2-2 ype) have the ‘Moreover, the curve obtained for a strong electrolyte shows that there is a small increase in A, OF Aq with dilution. This is because a strong electrolyte is completely Tonized in solution and so the number of ions remains almost constant. Athigher concentration, the greater inter-ione interaction decreases the movement of the tons and therefore, conductance decreases with increasing concentration, (On dilution, the fons are far apart, and therefore {nterionie attraction decreases and hence, conductance Increases and approaches a maximum limiting value at infinite dilution, 11 is also observed that the plot fora strong electrolyte becomes linear near high dilution and can be Electrochemistry 749 extrapolated to zero concentration to get the value of fF ‘N-(Conductivity at infinite dilution). (b) For Weak Electrolytes The conductance of weak electolyes is less than that of strong electrolytes at the same concentation since weak ecrlyes are not completely ionized. Moreover, the care for weakelecvlytes shows that there avery large Increase inthe conductance wth dion near the indinte lution suce on udon the degree of ionization increases Thus an increase in conductance with dluion is doctotheincreasein thenumber of onsin the solution However, it does not each & limiting value Foca weak electrolyte, Ay oF Ae increases sharply near high ciution. Hence, an extrapolation at fine dition 4s not possible. Experimentally, it also not posible to determine the A oF Ay value for a weak electrolyte because although the foizaton is complete but the numberof ions per unit volume is s0 low that the conductivity cannot be measured accurately. ‘his problem was solved by Kohsusch who gave a law ‘known as Kohlrausch law of independent migration ofHot Spot 1> ype and their level vary from easy to dificult. reer KOHLRAUSCH's Law Benen? Baan ~ Mec 18 sa very important topic for JEE Main examination. The question based on this ope are generally numerical | Accing to Kehlrauseh law, th mol cordtity of an lect tte in thea lr candy tna Drodacety he eet fit dston oth wor wean Say tht the sumaf molar conductivity of cation and ation at lannie diutionis called molar conductivity of electrlyte, oi ny andy rete mor conduct elon ond shoe Innit ton then her nad ac the of alos a arionsrespecey (Themen et rumter of one with lr conduc a por ion ced molar lone conductance ot pant nl In tems of eutaletcondchtes Koons’ aw i tied 9, equivalent conductivity ofan electrolyte at inte lution isthe sum af two values one depending upen the ‘ation and other on anion ey yk ere. ae iting egal oro condo ton and anion nape. ‘Some impart oppo o Kabah ewa as flows (a) Calculation of Aj, oF Ang ‘TH law is help in cletion of mol comfucance a infite tution for weak eleciotes. Suppose, we hve to eat the Tinting conductance fr CHCOOH ‘Then, according 0 Keble’ aw 0 Manca = Mean) * Hie “Tis equation can be obtained by the browledge of olsr Conductance at infte ution for some strong scabs, i, ‘ 8) Hnycooras * Meyconrs * Moar ise Fe Mer 9) ‘Te sbove Eg) an Be ete By aig Bs (an (Hand ‘acting 30 fom te, Les ico0n = Woo + Hy ~ Har Sample Problem 6%, fr NaCl, HCI, and Nahe ave 1264, 425.9, and91.0 Sem? mol” respectively Calculate A (Sem? mot" or He ween @) 3905) 1803) 4202 3505 Interpret) Mone: (425.9 +91.0 1264) Sem mot 1=3905 Sem mot ‘Sample Problem 7 0.1 M H;S0, is diluted to 0.01 M $0, Hence, ts molar conductance wil be je ® 55 (@) 10000 mes (3) 10 mes (6) 100:imes 11000 Interpret) in Bah Me ing Hoh 001 inate” 0 Ge 0.151 (Ag =10 x14, (0) Calculation of a For casing dee of doction, a of weak tot, he Formula used 15 ae here, a = degre of dissociation ME = malar conductance at any concentration molar conductance at fie dation (©) Calculation of k, "hep detemination of the lotion constant of weak lett, as we can ees w om | | ‘Sample Problem 8 The molar conductivi Ta mata acd 8461 Son me he | (Given, 2204) =349.65 em? mot-* BHCOO™) =54.65 cm? mol” @ 209%10+ (1.87 «10 (e367 «10+ © 420%10°+e = 46+ 349.6) 5 cn? mot! = 408.2 em? mor" Ki (46:1 Sem?! Ay 4042) en? mot?” O14? Sep It Calculation of dsocation constant Keacoom = Nraicoor HCOOHtea) “E HCOO tag) + Hag) isan ° Feullbiumeare. C=) Ge Ge (HCOOH) Diociation constant, K, = HCOOH") THCOOHT ~ Cd 025 mol Lx (0.114) a-o1@) -8.209%10" mo (0886) =267%10-4 mol? Placing values, (a) Determination of the Solubility of a Sparingly Soluble Salt Wasatisveryles soluble nthe gv sven ts molar or gate ‘conduct at some concentration toler ants mo ore ‘onduetniy stint diston Thuy fy = Ay ani y= Ay 1000 $ (5 = stain mal) oe 11000 4, x 100 Win yy 2 2 (5 = sain cate oF Kean be computed using Kohirausch' an ‘Ths, 5 con be omputed and canbe wed to cleat the laity [oducts For amie for AB, HS ml "the slay, then Ky ary? ‘Tous, tim Ay = A ‘Sample Problem 9 For a saturated solution of Ag at 250/Cspec conducance 8341x10" oben and that of water used for preparing the slain was {160% 10" ohm "cm The solubility product of ARC fs {Az (AgCh= 1303 ohm en equiv} (a) 13110" 174010 (a 172s10 361007 Interpret) ForAgCl molaty = normaly ‘Actual specie conductance = ipecifc conductance of ARC specie conductance of wate) Electrochemistry 751 Bat 1.460) 10 1.81510" ohm en For saturated solution of sparingly lubes, ‘Aag= Aeyand solubility =concentation 1000 specific conducance olay 10005 1.8110" 5 000% 1.81 10° 138 a 1a1aK AGC = Ag(29)+ CTIaq) Kye grr) =3* =aa110"7 72410" moP sss: Sol mol Sample Problem 10 Equivalene conductance of aC, HS0, and HCI are i, % and ay Sem? equiv at infinite luo, specie conductance of saturated BaS0, solution i Sem" ten Ky of B50, is 10y wy 08 Tat) Renae oY ay Won DF wy? Interpret (6 Ausoy = Mews, + Asoy —2 «ye, eat, aa 10 xy Men Ta) FerBS0,, Transport Number ‘Transport number or transference number is defined as the fraction ofthe current carted by an ion. ‘current carried Total current carried ‘Transport no of ction + Tansport no. of anion = 1 ‘Transport number752 JEE Main Chemistry Conductometric Titration ‘The measurement of conductance of resulting solution from an acid and base titration 18 used to calculate equivalence point if there is a regular change in the Conductance and sharp change at equivalence point. For various titrations, conductomeric curves are as follows Crs [poo Wun (op For arog ce vation base | i-< Enspore ue Mie (1 For mare of weak ad rong (orForweskackdveweakhase SoH ve stong bese e-33 Tntoncines Check Point 1 1, Soi NaCl does not conduct eecy tt an aaueos Solution of Naor mon NaCl conducts eer, Epi. 2. AE aint ivton, every fon. males an incependert rrton tthe al conduit of stir wy? [Hints because of ote aac] 3, Spe conductivity decease whe equiolent conductivity insets with dition li 4. Why sit neces to se AC curet for the measnenent of De conc ofthe sluton?| {5 Minit ut the conductance of weak 5 Wel 8 3t003 flees resame wey? 6. NOC te conducts weaker ardat 100, the conduct af he same eecle &Fd the coreet ‘eta between ad and ao giveth pope son 7, For weak ekeaes, ton increases emivence fendsctance very soy i higher coeetvatin rar tt Sepa seed wscancenton spaces oem? 3.3 Electrochemical Cells Htecmochemicd ola ome te eye, cca, 2 energy a chemical energy inerconverion of rial ceiver oft ba Pes ‘)aeorbcall Jn which (i) Galvanic cell Electrolytic Cell tian eleetlyic cella chemical renton i cared ou ih the hep of an extemal source of elec Terr, in an elecrolyc cel, clerical enrey Therefore chemical energy. Here a non-spontancous er ee

cht ‘Aveathode 2Nat+2e" —+ 2Nall) ‘Thus Cl, and Naare the products of electrolysis of molten NaCl Preferential Discharge Theory According to this theory if more than one type of tons are tracted towards a particular electrode then the one Gischarged ig the lon which requires least energy, The poteial at which the ion sdischanged or deposited onthe appropriate electrode is termed as the discharge. oF deposition potenal. The values of discharge potential are diferent for diferent ions. For example, the discharge potential of" ions is lower than Na ions when plan ‘ormos ofthe other metals are used as cathodes, Siralay dlschargepotental of Cons i ewer than that of OF: Jons This can be explained by some examples even Electrolysis of Aqueous NaCl In case of aqueous NaCl, 0 i alo i Nas and eres NaC HO i also present along wi aaa Cheloms Om Passing electelty, the following Atanode 2cH-aa) —+ Clie) + 26% ae 28,00) —+ 0.6) + at ag) ges Beoca23¥ X the colution of NaCl is concentrated, ly is the main produ However i i quite dae he se Ine fy Thins becneo a ne PE!(From experiments it was found thatthe applied voltage required is always higher than that calculated from the standard oxidation and reduction potentials. The ‘ditional voliage required is called the overvoltage). Avcathod 2Nar +26 5 Na Bre-2niy 2H0+2e + H,+201r Be2-0B3v ‘Similar to above, in case of dilute NaCl sclution, here also, ‘the product is instead of Na due to overvalloge However if cathode is made up of mercury, Nag isthe ‘main productas Na issoluble in Hg and the overpotentil of hydrogen is higher on mercury. In such ease, on, Ihydrolysis NaOH is obtained as main product. 2NaHig-+ 20,0 —> 2NaOH + 28g + Hy Caution Point ident sede acatads Ne as have oer Sich tet ane Hectrolysis of Aqueous CusO , Solution () wits ner electrodes ike Ft Atanode 2s0F'bq) —+ 50Fag)+2e;r=190 2H,O1) —+ Ox(g)+ aH « dese =123V Atcathode 2H) +26 —+ Hy 201"; B=-083V eu ag) + = —+ 205, B= +0337 ‘thus the main products of lecrobysis of aqueous (ue) solution of C80, are Gu and Os ‘his reaction fllows the principle of electrolysis and due to electrolysis, the blue colour of the CuSO, solution sadualy fades (G}with copper eectrodes Atanode ls) + cuP(ag)+ 263 0337 V ‘Aeathode cu (ag)+2e° —+ Cubsk a+ 0337¥ Fortis process ony avery light volage i requied. The Cancetaonof he slo ein unchangeTh takes the. bass of puricaion of metal called dleceorening Inia, this whole process involves the uanserene of copper tem anode cathode ‘Sample Problem 144 dilste aqueous solution of HS, it electrolysed using teletrodes. Te products athe anode and cathode are hea (@) O,ty (6) SOF,Na ) OnNa Electrochemistry 753. Interpret 2) When alte aqueous solution of HSO, ie subjected to electrolysis following reaction take place at shod andanode ‘Atanode 2H —+ 0, + aH + 4 20F —> $,0F 626 Ateathode at 62 > Hy “Thus, Oy aH, ae the main products Caution Point ten an aquous stron ofa st is elctaoed # ‘nal hs vn itn ptt estan “089 V0 cd a ‘Cxtodeibaatngh(g honing behindmetaon ite satson On the ote har ann lee spt, HO ended a arose ‘oaing 0.) Faraday’s Laws of Electrolysis Faraday was the frst scientist who described the quantiative aspect of electrolysis. He gave two laws of electrolysis, which in their modern combined version may, be stated as "Theamount of electricity or charge) required for oxidation or reduction depends upon stoichiometry of. the electrode reaction”. However, their previous forms wwasas follows Faraday's fist law states, ‘mass of any substance eposited or liberated at any electrode is directly proportional tothe quantity of electricity passed” Le, 2 proportionality constant, also called electrochemical equivalent ‘his electrochemical equivalent is defined as the mass of ‘substance deposited when 1 C electricity is passed through a solution. Itcan be calculated as 7 = Sdulvalent weight of substance ‘96500 Here, 96500 is called Faraday’s constant. its basicaly the charge on 1 mole of electrons. ts exact value is 96487 and with appreximation we take it 96500, Sample Problem 412. ita curent of 0.4 flows though 2 ‘metallic wite for 2 h. then how many electrons would flow {dnough the wiret ‘seta (a) 6022 «10 () 1202 10 (9 2.246107 (@) 30210 Interpret Quant of charge (2) passed = Current «Tine (0.501% (2% 603609 1600) A4= 3600 C754 JEE Main Chemistry "Number f electrons flowing though he wie on pasing charge of ‘one Faradsy (96500 C= 6.022% 10 "Number of electrons flowing ough the wire on passing a charge 213600 102210" «136000 (965006) 246.107 Number of elacrons= 2266 210 ‘Sample Problem 13 10800 C of elecrcty on passing ‘rough the elecolyte solution deposited 2.977 gof meta with ‘atomic mass 106 8 mol" The charge on the metal cation is +2 Mes aes at nearpret (9 £=126500 2977296500 Tat 70800 = 266g equ" 66 Faraday’s second law states, “When same quantity of ‘lecticiy i passed through solutions of dillerent tlectoytes connected in teres the weight of subsiance produced atthe electaces is directly proportional to their equivalent weights" Le, ‘yn of Cu deposited. wt of x Wicof Ag deposited” Eq wt. of Ag ‘The above forrula can be given when CuSO, and AgNO, {oliatons ate connected in geies and same quantity of tlectricty is passed through ther Now suppose for electrode reactions, ‘Mg()+ 22" —» Mas) ‘AD*(()+3e° —> All) the requirement of electrons is 2 moles and 3 moles respectively for completion, te, 2 Faraday and 3 Faraday. Similarly forthe electrode reaction, Ag'tigh © —> AR) only 1 mole (1) of electricity is requited for completion. ‘Thus, the requirements of electricity (or charge) is ‘lectiode reaction orfented and varies with the change in ‘lectrode reactions, Sample Problem 44_ Ioan aqueous slain AgNO and C80, are connected In series IF AK deposited a cathode is 1.08 gthen Cu deposited fs 1.053262 1 O18E Interpret id fa, ofAs 1.08 0, oe "a3 635x108 7 108 (@ 026 1 03176 9. 01CU Wess! 031758 Current Efficiency Sometimes the ammeter shows mechanical ft this 892, * actual eurent_100 ‘5 Curent efficlency = Zrmeter current false current due to Thickness of Coated Layer Let the dimensions of metal sheet to be coated = (ecmxb om ‘Thickness of coated layer =com™ ‘Volume of coated layer = (a xb xc) er? Mass ofthe deposited substance = volume «density 7 G@xbuclxde Dats laxbxelxd= ‘96500 Using above relation we may calcualte the thickness of coated layer. tnagalvanic cel. some spontaneous redox reaction rakes place producing lectie cuerent. Therefore, in galvanic Eel chemical energy ls converted into electrical ener. ‘tn example of galvanic cell i Daniell cell. Jn this cel Ateathode Cx ag) +22" —+ Ca (Reduction) ‘tanode nls) —+ zn?*laq)+ 26" (Oxidation) Overatt cu + 216) —+ Cus zn™*teg) ‘he change chemical enero letra nergy causes lowering tree enerw, which appears as ene Taser =i Ey some Fe4 dul twingscnde tts set eran In galvanic cel, chemical reactions takes place in two compartment cath of whic continsasuable lect and leceasaen eat mt‘The solution in two compartments is connected though an inverted U shaped tube containing a mixture of agaragar ely and an electrolyte lke KCN of KNO or NI4NO, (inert electrolyte) et. This Utube connecting the two compartment is called salt bridge The sgnifcance of salt bridge includes 1.1 connects the solution of two halfeells, thus completes thecal ert. 2 te prevents transference or diffusion of the solutions for one hal-cel io other 5.1 helps in keeping the solution in two half-cells electrically neural, te, it provides negative ions 19 anodic hal-cel, hs preventing the eccumulaton of ‘exta positive charge ip the solution and around ‘anode wich normally hinders the flow of electons from anode. Silay in cathodic half-cel, pomdes Positive ions to prevent the accumulation of extra egative ions in this hall 4 It prevents liquid Aiguid junction potential, (e, she Potential diflerence which arises between to Solutions when these are in contact with each olner ue to diferent movement of ions Characteristics of electrolyte used a salt bridge are 1. The electrolyte should be inert and should not reat ‘chemically with the electrclytof ether ofthe two alf cela 2 The cation as well as anion ofthe electrolyte should have same ionic mobility and almost same transport ‘number, vz, KCI KNO, NH.O ee: ‘Thesal bridge can be replaced by a porous partion ikea paper strip, clay porous pot, unglazed porcelain or asbestos fibre which allows the migration of ons without allowing the solutions to intermix, ‘The clectrochemical cells may be. reversible or Irreversible. cells considered as reversible f (@ The chemical reaction of cell stops when an exactly ‘equal opposing ems applied (i) the chemical reaction of the cell reversed and. Current fons in opposite direction when opposing emf sighily greater than that ofthe cel. [Any other cell which does not obey above two conditions ie called Irreversible cell, eg, 2 cell ‘consisting of 2n and Cu electrodes dipped in #,$0, is irreversible Difference between Electrolytic and Electrochemical Cells The main points of difference between these two cells are 1. The device in which elecrolysis (chemical reaction involving oxidation and reduction) is caried out by Electrochemistry 755 using eecrcty or m which conversion of electrical fenergy into chemical energy is done is called lecuolyuc cell while galvanle or voltale cell is a evice in which redox reaction is used t0 convert chemical energy to electrical energy. In ‘electrolyte cell, ancde is postive electrode, while cathode is negative electode. On the other hand, in ‘alvaniceelP anode is negative electrode and cathode In postive electrode Caution Point te cle andes alas the sit of exon srdestade ee econ 43.In electrolyte cell, ons are discharged at both the slectrdes, while in galvanic cll ns are discharged only at eathode, 44: In electrolytic cell, oth the electrodes are fited in ‘same compartment, while in galvanic cell both the electrodes are fied in different compartments. Arete Cates Anode Cathode {a} Seciyiccot—_ () Vaateo gave cet (emis saptec toca) ante preted coh S.esides salt bridge in both the cells, both the electtdes are connected extemally with the help ofa Wire connected through a volumeter. Flow of curent tnd electrons occur through tis wire 3.4 Daniell Cell ‘Among the galvanic cells when cells designed in such a manner to make the use of spontaneous reaction between Zn and Cu ions to produce an electric current, the cel i called Daniel cel, { Daniell ce the anode is made up of zn rod and dipped in a solution of 2n$0, (electrolyte). Similarly, the cathode is made up of Cu red and dipped in the solution of Cus0,756 JEE Main Chemistry WEES eae, "8 fone when ee ane ‘when the Zn and Gu electrodes are joined by a wie, the following observations are noted: 1. there is dow of electric currentin the extemal cireut ffom Gu electrode tn electrode, (electrode ve electrode 2. The Zn red loses tsmass while Curd gain its mass, 53 The concentration of 2n80, solution increases while {hat of CuSO, solution decreases 44 The solutions in both the eomparments remain ‘lecrcally neutral Acwally 2n metal is oxidised at Zn electrode and the ‘leetron released travel through the extemal ccuitto Cu lectrode where they are used in the reduction of Cu* {ons tnto metallic Cu which s deposited on the electrode ‘Thus, the overall redox reaction i, ‘Znle) + Cut fag) —> Zn**aq)+ Cus) |As you know that voltaic or galvanic cell consists of two, faves as halfcells. The half-cell in which oxidation occurs is called oxidation halfcell, while in. which ‘eduction occurs is called reduction hale, 2n —» 2n#*+ 26 (oxidation hale) cuts ne — co (eduction halcell) Representation of a Galvanic Cell ‘the following conventions are used In representing an lecrochemial oF Galvani cell tation contains anodic hal onthe let vpealc half on the right and side. ‘cell's represented by witing nd then the electrolyte ‘The cell epresen yhand side and cal 2-the aoa de of he ct ‘metal or slid phase first a infact cation of electrolsteh | ‘The cathodic side, on the other hand, represented by Tune the elecrlyte Sst anion) and then the metal ‘or solid phase “4 Metal and cain are separated by semicolon) orby vertical line (- ‘5 The concentration of electrolyte i also written within brackets afer the cation ‘ésalt bridge which separates wo hall-cells i represented by two vertical lines. ‘Thus, a complete cell can be represented as, ‘ni znt* ( M)HGu* (1 MC Caution Point He temy ao booted ht ace can bo writen by SSrargig each of he par Le, lettoght,snode-cathod, oor cus sagt poste an aphbetical re. Sample Preblem 15 The cell action of galvanic cell ‘Cus | Cua) | Hah | Hat is (0 Hg + ca? —+ Hg + co (Hg 4 Cu > Cut + Ht (9 Cus He —> Cutty (Cus He” —> cu + Hg Interpret (2) From the cel iti cear that ‘Anode half action is cu a s26 Cathode hateeaction He +26 + Hen ‘On adding Eo. (0 and Gwe net Cas He —s cu 4 TWisiteceleaciontreahanccet 3.5 Electrodes and Their Types Hlectodeis thé material which conducts electricity inthe cell due to movement of electrons it may Be take form like wire, rod, sheet, etc. ae Blectrodes may be classed further as 1. Inert and Attackable Electrode The electode which only conducts electricity ia called Inert elecwode andthe electrode which poriereay ca reaction alo scaled atachable lecuade Pen2, Anode and Cathode Anode is the electrode at which oxidation occurs and cathode is the electrode at which reduction takes place 3. Positive and Negative Electrode tn pani cell, the eect at which reucton ours {athode is postive elecroge whl the elecoode ot hick tidaton orcs anode ogni elecrode Honea it ‘he deculyceall heclecuode at whch caton des keane) isnegatve electode wine te eecbode at eh tions dcharpesaned) e pote eacuode 4, Reversible and Irreversible Electrodes ‘The electrode at which reduction as wells oxidation may take place is called reversible electrode while in treversible electrodes, reaction occurs only. in one direction. Some of the example of reversible electrodes areas follows (a) Metal-metal Salt Electrode When any metal is immersed in its salt solution, metal atoms have tendency tormove in he solution a metal fon (direction ofincrease in entropy) wine the metal ons from Solution have tendency to get deposited at the metal surface [direction of decrease in enthalpy). Mls) = Mag) + ne (b) Metal Insoluble Metal Salt Electrode In such electrode, normally the metal surface is coated ‘ith some ofits insoluble salt and the sytem is immersed in the aqueous solution of some salt having common anion.e4, ‘Ag AgCI| Chelectrode Ag() + C-laq) <=> Agcls) +e Calomel electrode 2Hg0) +2CIlag) <= HesClls) +26" (c) Gas Electrodes ‘Any asin contact with the solution of ts coresponding ton tap serves es electrode, In this case, Pee te normaly used to conduct elecscy. eg. Hydrogen electrode H,{g) = 2H" aq) + 2° Oxgen electrode 40H (aq) <> 0,(@)+ 24,00) + 46" (d) Redox Electrode ‘These are the electrodes in which the elelytic solution Consina the same element in to diferent ondation States and coments conducted by immersing Pie in the solution. Fe ag) = Fe") se sn?" aq) <= Si (aq) +26 Electrochemistry 757 3.6 Electrode Potential ‘When a metalic electrode is dipped in is salt solution, a Poleiil diference is developed between the elecirode and its salt solution. The reason for the development of such a potential difference is exchange of electrons benween the atoms of electrode and cations in is sat solution. Such a potential diference is called elecrode ppotental Thus, we can say that the electrode potential is the measure ofthe tendency of an electrolyte to gain or lose electrons in a half cell ‘he elecrode potential can be of wo types (0) Oxidation potentiat The tendency of an electrode to lose electrans orto ge oxide is called ts oxication potential Eee. Mle) MPa ne Inf) Zn™ + 26 H,lg) 2H 626 Nae) = Nat oe Such an electrodes negatively charged with respectta Issaltsolution (8) Reduction potential The tendency ofan electrode to ‘gin electrons, ie to get reduced scaled reduction Potential Eee, ‘BP*(ag)+ ne = Mb) GP +26 = Cus) Such an lectrode ie postively charged wih respectio tssaitsoluton Boat * Em The half cel actions are always writen as reduction half reactions and thelr potential are represented as reduction potential, The electrode potential depends upon 1) Nature of metal and its ons, (i) Concentration offons in the solution, (i) Temperature, Standard Electrode Potential ‘The potential difference developed between metal electrode and solution ofits ions of unit molarity (tM) at 1 atm pressure and 25°C (298 K) is called standard electrode potential. The standard electrode potential 1 by E*.eg, The potential ofthe galvanic eel, (0H (g 4 atm) 1H (1 mol) t1zn™*44 mol 1126) ‘298, called the standard electrode potential of ine electrode. This denoted by E , Eh py2 OTE V758 JEE Main Chemistry ‘Thus, the standord electrode potential of an electrode describes the electrons accepiing tendency of the electrode relative to that ofa standord hydrogen elecrode, under slandad condone 08am pressure and 1 mol concentration Measurement of Electrode Potential ‘The measurement of absolute value of electrode potential ‘snot possible fora single elecitode. Only the difierence of potentials between two elecirodes can be measured experimentally is due tothe reason that oxidation or reduction cannot occur alone (le, oxidation and reduction occur simultaneously For indirect ‘measurement of potential of an electrode, we couple the electrode with another electrode whose potenial Jknovn, This elecrade is called reference electrode, The emf of resulting cell is measured experimentally. Now, a8 we know the emf as well as the potential of reference electrode, the potential of other electrode is determined. ‘Some important reference electrode are as follows Normal Hydrogen Electrode (NHE) Hydrogen electrode isthe primary reference elactrode ast fs used normally 10 know the electrode potential of 2 hhallcell of galvanic cel. The reason for such a usage i. that can act as a cathode as well as an anode with respect to other electrode, due to following reactions Halg) —> 2H" +26 an 25 1 the elecuode potential of NHE is ten as reo 1s represented as ei (uo hydrogen electrode is constructed by bubbling ges Seren pressure over planed planum sheet tremersedin 1 MHC soon Standard Hydrogen Electrode (SHE) Abydrogen electrode in which the pressure of Hy gas is ee ‘maintained at 1 atm ile and the Concentration of HY fons in the solution is TM, is called standard _ hydrogen flecirode. The emt of ‘HEIs takenas.000 V atall temperatures, Fn chicos ci eae ‘Snelainom ob 27 Sanaa yoga erode 6) erotcoentrt cnet dat Caution Point nose errant Calomel Electrode isan another generally ted reference elerode tor tt comes in the Category al secondary felerence electrode Gemary reference Sccede is ‘sandard Syren lerode but {raiment to prepare ar mantinitheeecrode Seis of gat he fewtom, over which 8 sat mercury and mercurous {abe Thetube filled wit Sls cealed plain ‘tipo felecrode dep Cn thebosisofconcentationofKCh the calomel electrode named fen, egs HRC) solution is saturated, Seco scaled SC aturated calomel electode. Simla. cl slution is LN, the electrode called NCE inarmal calomel electrode) and DNCE_(ecinonmal Cafomeleecttogel for O41 solution of KCL The reducion potentials of calomel electodes on Hydrogen seal at 298 Kare forsaturated Kel ~ 02418 V for LOWKCl - 02800 for04 NKCI ~ 03998 V re 28 Galomel secre Jnlorde is placed in 2 fh Cl olution over the paste and ite is used for electrical contact, ends upon KC! solution, Silver-silver Chloride Electrode Besides hydrogen and calomel electrodes silversilver chloride electrode is another widely used secondary reference electrode. Caution Point goo ote wide atinedeny tte stir tomer rp voeen electrode, ie, where reduction accurs. Pea preeet Various Types of Half-Cells Vacious type of haltcells have been used, some a2 reference balfceli, to. make complee cel wih spontaneous reaction in. forward. Uscetion, These halele alongwith halteel eee summarised inable32 “SasHons have beenElectrochemistry 759. ‘Table 3.2 Various Types of Halt-Cels eo] ee Baro aa sen a1 [rnwatiow 1 Jeaeennateat Tr aa) Riel — rane TFT fn frei) | cre) Ioren — Lose mee 2 |eatnatainnnatet to ase) is) — Atay ver er |aotion tno sak ts fo) ee) gO) = 1 cron 3 [aatouaisar lag acticin fag crac) —> Agu. ae fates pee, 16m buns sn —anmyiwe | ET fren 5, |Metakenetal oxide |g, Hg0 | OFF + 20H (aa) —sHGO(s)+ HO) + 26" | _1_ JOH ion arate |ra.Ha0 onrn) ns 20% ua) —sg009 ar 6, |Oxidationreduction — |p | Fe’ Fe |Fe**(aq) —> Fe (aq)+ e [ret ret os LeaniFe™ on) feta) + Fe) ie 7 Jeeyrcuy |e ne60, 202) octane ana 2e™ 3 foor senewnat ent OF 7 8. Josirytenera.cat_ |p curve | Ha O-Q=~ wr | | be 1h is an important topic for JE Main examination point of view. The level of question is easy and a small practice ‘make you able to sotve problems of this topic. ty Gecrochemia cll the elecroes ferent ales have ‘ieent reduction potential. Ae a result of His fleet flow of Sleenors seen rom the eecode wih Neher cendeny 10 lose {ectons to ther ectode. Tis fence in eltrote poten of. ‘ectodes scaled electromotive force o ell potential of » {lL Tis the ving fre for al el actions “Wie know that reduction aca at cathode an eiation ocr 2 node, here EMF = reduction potent of Sathose coy EMF = ondation potential of ade = reduction potenti of anode {+ tedoction potent featoe “Toon, emf of 9 cll may ato be defined 5 the potenti derence Teoreen to electods when eterna eglabe caret salowed {0 ow inthe cet Het Spot > EMF of Cell 1 the owo taf ces ae séectedtbtanly for the purpose of | 0) Reduction poten! Is taken sanded ‘Potente I electode potent gen (nd rating mentored | ‘hth it exdation or redotion), i taken 36 The reduction | poten by dest760 JEE Main Chemistry Sample Problem 18 forthe given reaction, aCe! + Co—» 200" + Co* fe -0.28 V, what isthe value of Interpret (8) Ex Eley if 1.89 Ve Eegeyey ee Feereoe? 19--4-0.281+ ww 378v wey wo osey @ anv Farge ao ON EY ‘Table 3.3 Difference between Potential Difference and EME Potential itorenco 1. [hie he aternce between Ieeecroce potentials othe tho ode under” any Soren _ a TCs te patwrtal oiteerce becom tea lstoces ot owing athe csi aan ‘pen eeu. 1 te maunum votape ‘blaine om De et 2 | ne tess man te maxmum ‘estage obzanable fom Pe ‘Come, EMF ofthe cl 3. | ns measue ty a emple|t is ensued by ‘eleven Fotenomeare meted oy > at ne EMF cont by Te potontonetceouee sa Sndoppasteto matt be call fd tere et rt owing in Seat. Wennet te" measured by velmelt ‘i awe cent tis respon forte ow of ‘Send Curent te creat 4 | not responsi fr te fow of sandy euent De Check Point 2 1. Wow ite ie bina. Ns] be alee ent oer inctnt Ecmp) 12 Metatie sodium cant be obtained ty decrolsng on {ures ston of NC. Why? | brureagurous selon of NOH, HO, an 0, erate ‘thesove prods st the ceeds dr eecrohss Exit ‘re el potential ofa pontaneus reaction ways postive fa wih approprate rasan. 2 ganic has elec potent of 11 fan oppesing ‘poker sapped to tise wat wi happen othe el veaton and cen ling tough the ce? INCERT Exemplar a8 3.7 Electrochemical Series ‘The arrangement of metals in decreasing order of Tendency 1o lose electrons is called electrochemical series itis the sees in which the elements are arranged on the basis of the values of their standard reduction poeta Table Standard letrode Potentials 25°C se ecrochemica Sect aa cnacegoson | asap u wee Su a 7 war ok “ees K peared “ear a ears can elmer] |e mw G2 8] eee ow [BLE 5 18 o AER) oe sar ms [BIDE “on co B28] chs w or 18/3 8 -o78 fe BELB| vor ca ore (B[ 22 -ou co BBE] ca +00 — 0a |? gf -om : W is near £ Hen Hifi| seta So [El poo HEE oe ets c co var ts [E/E Sse to om ‘ ves ® came 4 ns - +150 ip 28g ot we ny dat he een womb caer Characteristics of Electrochemical Series Following characteristics ofelectroche Follox ofelectrochemical series canb 1. The negative sign of SRP(standard rede a) indicates that the el 3 romed with indctes that the electode when joined wih SHE(standard hydrogen electrode) behaves as anode, ce, ‘widation occurs a tat electrode. Similar, postive Sign of SRP suggests behaviour of electrode as eathode ‘when joined with SHE 2. The above findings suggest that elements which are better reducing agents than hydrogen get their place ‘above hydrogen in this series (such elements have regauve value of SRP) while elements which are beter cwidsing agents than hydrogen ge their place beowe the hydrogen in this Series (such elements have () ve value of thet S80) _ Hot Spot 3>- Electrochemistry 761 3. Blements which get oxidised easly are ood reducing agents metals) and elements which get reduced easly are good oxidising agents fnon-metals) 4 Ameial wit lower SRP can have the ability to displace fetal with higher SRP fom thei solutions Secondly, the rectory of metals decrease from op to bottom it ‘lecrochemical series, e, metals higher in the eres Sre more ecive than metals ving lower inthe series ‘The elements which are placed above hydrogen in ecttocherieal series, have the ablliy t0 displace fiydrogen from ry prove solution (any solution containing") NERNST Equation 18s the most important topic ofthe chapter for JEE Main examination. The questions asked were generally | numerically type. The level of question is easy to average. A retionhip Between elctode potential and corcentaton of ‘alton I alle Nernst equation. For a general redoction hal resco, Le, MP*tag) + ne > M8) “Ths equaton con Be gen 25 ry, =a a Eh Far = Paes et 230387 jy MD Ra Ee Re seg, 10 «290319 10) Ey uy = toe poe E Pra = Sanda eco potent "t= ga constant T= temperature Fo Feacy constant ‘n= mumber of eeeons ane rng trode con [a (ag = concentration o ns ts = concentration of meal ‘ince, the cncetaton of soi has Is taken 25 unity the Nest ‘quan all become Bem eas i Fora peel redo rection eons wm 6 the decode potentials for to haces ae gen 2, Fue nn = Fier an Im iain ha col eaetion, Hu" incase Ea dees, (ar tempertre nea coatant (MO Ey CR (Oi ieeases, Ey ieee (a tempera ince at ortant MBq eases We nota, he el potent i at = Baer n ~ Gy ney Ea = Eats Eee Weal eon OT gg Ila nF 8 Taal ‘Win both he hall, the numberof tons ae not sme, 220387 IM" (ag)h ey EIT Fan Re Te Tal aya!762 JEE Main Chemistry here and y = stokomet coeicent of Mand Min balanced cquaton. ‘Now ifthe values of ® Tard F Le, 8.314 JK" mol for, 290 for Tad 96500 for Far subnlitte in Neat cquation we gt, 2.0591 5 IM""(sll Ba a ea Sample Problem 17 calculate the emf of th cell in Which the following reaction takes place Nil + 2-Ag"(@.002 M)—+ Ni (0.160 Ml 2A Given that Ey = 1.05 iNcern, @osty won @osv (0023 Interpret 0) From thegiven cel action and Nemstequston, 0591 jog INP ait 0.0591 jg 0.160) = 105y=2252! 105v-203" og BS = 105-299! fog 4x10 0591 2105-222) 40000 = 105-044-0917 faa 81V Sample Problem 18 ‘lcrodeptnil omelet Sar according to eatin et 2.053 og 1 The graph off, ime 9 gy OR Fag slog Me™) ‘eo \ va veo) ; ; “/ “3 ‘ego Interpret) Thegivencqaton isfy =mx+ cre which iseqution of svg line. So, 0h OF jy ¥H0B ME" 10 0.059, 7 Is astaght tne wth slope 2252 and intercept ay Determination of the pH of a solution ‘sg a sutble reference hac Ho the unknown saan cin be determined 1) (Ng. Ho ua (tt 9 HEPC 9 Ps 000 Bhatt lg) —> 20) + & iS hls ae cys) #26" a2) + 207180 nes THe) Tg <> aN) + 2G + 20° Fey 02876 = tertor? “WF (since (C71 = 14 sg fg 8 ng HP «+ 005010 Bat ~[Eemee + Bie) ‘0.0581 fa ~ Bors ‘0581 In this cae reference hall clomel electrode. pHs Semple Problem 19 Calculate the potential of hychogen electrode in contact witha solution whose pH is 10. NCEE ‘a 00581 V 6) -o.0591 @ osstv ( ~oso1v Incerpret 9 fortonenelecioe H+ IH -Appring Nest equation, Sea" na 22 205%, 7 PGE Uo 10; 610° =0 2052, Galego 0381 Foe many #05910 Nernst Equation for Concentration Cells ‘The cell hot te eed ofthe sme pe Bute ceevahte Sahiion have diferent conterneton ee ‘oncenation els ae all (a) When Electrode is Rev to Cation co le with Respect Bn 122° (CN BPG | 26damole BEDS 2e Pea Meatode —_2MG)+ 2° — m= -a75V BEG) —> ae) P= omV ag Fag tag = 2 og "eG 0.0591 yg ° Ban 0 208g = 0058 & Fg Bg ‘Thus. for thi reaction tobe spontancaus, Cy > Ce (b) When Electrode is Reversible with Respect to Anion Fc Lee er we) For such cates, el ection spontaneous in foreard reactin, if OG. {c) When Electrodes at Different Concentration are Dipped into Same Electrolytes apg ric 0g) “Two haces are Joined by two strides since they fave common scrote. Mtamede WO) —> 24 meatal as e2e > Wa) Neeson HG) IAT Ba 000 050% 55 A. 0098 yy B Ba Cel restion 6 foward dtecion, if By) > PRS ‘Sample Problem 20. The emf of the following cel is 0.086 v, ae [Ag | ABNO, (0.0093 | ANNO (| AB. The value ofa on 020s ‘oon (0389 to 0266 Hog Interpret, (a) £=202tog le855055 0086 _ jy _* oias9 "F095 9008 Electrochemistry 763 Equilibrium Constant from Nernst Equation Fora gener!electocheric reacon mr bB > 604 0D the Nest egstn cn be wen =, at, FLOP Fan Fee oe arte warier / an Fan* oe (cror cceliriom Eye = 7 terior _ = (are “Tus, Nest equation my ako Be used to cake the equim tnt fora cel reaction through the fem Pg 2223! og, whee Ke quiron constant Sample Problem 21 Calculate the equiliirium constant INceRT ofthe reaction (Cu9 + 2A8%(ag) —r CuLag)+ 28K) EB oo 4nt0” eee Gano” (a 136010" Incerpret «| 25M og, oso lon Vos, ‘aosey 5 Aloe 3:=3.98 «10% Cano] Mecha] He (Cr saturstee) | Hg,C15 |g, ‘Whar isthe concenvation of Cin saturated solution? @ 1025M Wh) A84M 275M) 428M Interpret) Hace reaction is Hg,Cly+ 26° —> 24g + 2CF aura) Kat For saturated Cr solution, =0:244V and fr stated “al cl, F-03270 E log cr? 0244=0270- 008 eg tg er1- £28 - 04098 ford=2.75404 ose 2764 = JEE Main Chemistry Relationship between Cell Potential and Gibbs Energy Change (SG) ‘an decechem e,masin wok one (0) en by 20 = wher, = Fara’ comtant = numer of makes af econ wansened A. gaan el does lect work By wanfering esl charge fhvough an extemal crc When sal amount of camer ean from the cl then 86 Whe (9 140 oF stem paste then he proces oul be posse ‘ly he soreanding do ea work onthe te oI Sets (0 taco the ate epee teste dos ete wor ‘nthe sound fs mgeNae cs For a vote ce, the ‘eth s done onthe suoundings, hs gen «neath Sn 0M = Ea nd the stand fce energy L8G"T' hen bys 20 == FE ‘Sample Problem 23. The standardelecvode potential for Daniell cell 1.1 V. Calculate the standard Cabs enersy for the reaction cea Zaia + CoMaq) —> Za tag) + Cust ) 21241 mot" (@) 21241 mot (21224) mot" (@) 2122 ma Interpret (©) a,6° =-nFF% inthe above equation fF =96407 Cine and Ey =1.1¥, 130° =-2 96487 Col 1.1¥ 21227 wot =-2122714mor" Relation Between Cell Potential (E,,), Free Energy (AG*) and K ‘The relaon between ell ote (ys fee every (46*) and qatar constant) ghen Bi. AG" =~ 2303RT og K- 2302 FT 9g, as AGP e ny and Br = ge 18 Ke 1 moles of decors Wa pcs to which you apply 0 ae fered in the where 9 the number of a be Trlanced equation forthe equation indard Potentials of Relation Between Star Se eaen Half-cells Containing a Metal it Oxidation State iF to hifeactions Raving potentials 6° and & ae combined to tice thd Htfreeton having 2 potential 5° then Ise = AG + 46" na or = nF =~ nBt= mbt + mB = ES o ge ‘Sample Problem 24 1f for the halF-cell reactions, & ‘ales ae given Ghee 9 Git a0 Gh HI Cy = 034V Calelste ofthe hall action, Gr te 5 Ge @ sos ) -053¥ @ -080v (@ 020 Interpret (a) Cu" +o + cut, Fn0.15V a Cur 5 Cu +o = =0.15 Vn 1 ® Gu s2° 5 cu, =024V,0,=2 From Eg.) an i) atte Sw 15)+ 24034) stony Variation of EMF (E,.i) with Temperature Using ibe. Helmholtz equation, the temperature coefficient ofthe EMF ofthe cell is writen as: woman [Se] fat constant pressure) 1) (aince a6 =—nFE) ti)-Entalpy change from Ea. () AH = nF gg + NET “), as =r ()] nay change canbe determined by comparing a 0 with a6 = aH =, lag) ao), as [gi ¢0Peaa] -=(%a)_ at 3.8 Battery A cell or a battery (arrangement of 1 oF more cell connected in series) is basically a galvanic cll and used ‘where the chemical energy of redox reaction is converted into lecical nen. ‘an electrochemical cell tobe used asa commercial cell ‘must full the fellowing two reqlterents 1.1 should-have the compactness, lighmess, and rogues for porabiy. 2. is voltage should not drop much during use. drop ‘n voltage should be nelle over the smal ner fume during which ts being puto we Different applications require batteries with diferent properties The battery required to start car, for example, ‘ust becapable of deliveringa lage electrical curentfor a short me period. The battery that powers a hear pacemaker on the other hand, must be vey small and Capable of delivering a smal but steady current over an extended sme period. The batteries are of two types basically Primary Batteries ‘The primary batteries are those in which the cll reaction ‘occurs only once and the battery becomes dead after use ‘over period of time and cannot be reused again, eg, dry calls like Leclanche cell, mercury cell ec. (@) Leclanche Cell ‘The electrode reaction for Leclanche cells Anode Znis) —> Zn? +20 Cathode MnO: + NE +e” —+ Mno(oHt) + nit, Electrochemistry 765 ‘ase Teed) Saclack stctyate 28 conch) A commer dy cllcomalane eae ton cata secon theta ontheonede "Nt formed in the reaction at cathode combines with Zn to form the complex like [2n(NH)J". The cell has a potential of nearly 15 V. (b) Mercury Celt 1tshows following electrode reactions Anode ‘Zn{tig) + 20H” —+ ZnOls) + H0+2e~ Cathode Hg0+ H,0+ 26° —+ Hig) + 2017 ‘With the overall reaction, 2nlHig) + HgOle) —+ 22046) + Hg) "340 Mercy ce Hee he reac aents ie ante ‘cee oem tery Bene The cell potential is approximately 135 V and remains constant throughout it life since overall reaction does not Inve anyon, he eoncentaon ef ick cos cha during its life-time. ie ad Secondary Batteries A secondary batery can be recharge by curren throught oppestedrcaon so bat abe eone (@) Lead Storage Battery ‘he mos important secondary cells lead slorage bate, commonly aredin astomobiesand invertors 812 lead sore ney ores accamlatr prey coo ical cach producing 2V. Her 9 oon of S04 8 used as electrolyte, iste)766 JEE Main Chemistry e213 Lendstore tate ‘The overall reaction for lead stroage battery during discharging Le, when cell is in the use) is, his} + PbO,5) + 21,80,laq)—> 2FDSO446)+ 24,00) Reverse reaction occurs when cells charged, PSO, +26" —> PLS) + SOF (aq) P8045) + 21,0 —+ PbOs(s)+ SOF ag) + 4H" (aq) + 26° “FESO,G)+ 210 —> PUG) FbO,G) + 21,50, (b) Nickel Cadmium Battery Another important secondary battery is Ni-Cd battery with longer lfe but more expensive. Sepa ‘ate la F232 Ancl camnmbster strut sey ted inmetsodum “The overall reaction for NCA batery is, Cle} + 2Ni(OH}, (6) —+ CadOfs)+ 2NNON,)+ HON) 3.9 Fuel Cells ‘Galvanic cells which use energy of combustion of fuels ke My CR, CILOH, ete, asthe source to produce electrical ‘energy are called fel ellOne ofthe most successful fuel Celis use reaction of i; and O; in gaseous state to form a a ste dose 1 aa Tie 34 M0 Fue ‘The electrode reactions forthe cell are cathode 0,(g)+ 24,09) + 4e” —+ 4HO"@a) Anode 245 (g) + 401 (aq) —> 4H01) + 46° ‘with overall reaction being 2H,(g)+ 0x12) —> 214,08) Advantages of Fuel Cell 1. Due 16 continuous supply of eases, such cell never becomes dead. 2 Usual operated at 20-140°C 4. high eficleney than other power plans (703) 4 Pollan re. Caution Point Theory erosion) ya 8G mote Disadvantages of Fuel Cell 1. Rectolgte causes corosion, 2 Diet to make contact between gaseous fuel, the liquid elecwlye and te sod crake : 3. ih costo eatalst, ‘Gaseous fuels are dificult to handle at low tempertureand high pressure, © handle. at Check Point 3 4 he ston of AgNO, tums tue when a copper rod immersed init Epi, wy? 2 Wonern cy io exis npn ie 20 sn eons. 9. ye 2 rin ont 4 Ue st oe mea he See has a constant ct pte INERT FerWORKED OUT Example 1. the equivalent conductance of silver nivate solution at 250°C for an infinite dlution was found to be 133.3 ohm”? equiv". The transport numberof Ag ons in very dilute solution of AgNO, is 0464, Calculate the ‘equivalent conductance of NO; (ncn? equit-hatinfnite allan, a) 619 m3 & 1952 ona Solution (o) »°(A8")=transpornumberot Ag’ Ag*(O.1M) +e Cathe ection Aa code +e = Aascaoe) Callrencion _AeP eathode) = AgPO.IM Se, ABNO, i Examples (ake0 059 +006) legiAe?,=10g 0.09 ~10 = og 2 log 100)-10 -09-2-10=-11.4 gL = Antilog 11.9 = Antilog 129) =0.79 «10° 0.810"! Since, Kris 60% dstcited, Ko (As 181 08 x10 10.5 =0.48 «1077? Solubility 5) = fy = JOB =10° 0.5928 «10 20.710 M=7 107M Example 3 How many slecvons per second do pass through a cross section ofa copper wire carving 1™* At ta 555 6/5 0) 62ers 250% (@ 3e%s Solution 10° 4-10" crs ‘Charge on one elecvon= 1.603» 10° Cer Rae-— 10" Teaco sear Example 4 Arrange the following oxicising agents in oder of increasing stength under standerd state condions Given, COP + 14H + 6 + Gee 4 THO; ataBV Bf +26” —+ 20th G=106v Feiagh se” + Feagh g-07v (9 Fe" < By < CAOF ay < Fe €C40F (Fe FeCaa) + Aa) org. fe"1___ 020 «jpeg Fe" TAs") 0.1000) gent oti, Fanti 222 og Example 9. the EME ofthe cll, ‘Cd CCI, olution (tat | ACK | Ag 15 0675 at 25°C. The temperature coefficient of the cells 65x10" V degree”. Find the change in heat content Himol™ and entropy Wdeg") for the elecvochemical ‘action that occurs wien 1 Fo electricity s drawn fore omen sme are Zaman Sean vasa Solution 1 6us= 0673 Catron fot en Leas Letter Cato actan MON > pata chan cotrcn Fao Asc ws hay Fag cP Teworaie cotta ), som (2) , tat) 31596800 «166.5 «10-4 $6279 V deg”oH, (28 en (2) wT), 067s v= + 298(-65 x10) aH 196500 AH» ~83829.55 )=—83.83kImor* Example 10. 4: 25°C the ree energy of formation of 4,000 {s-$6,700 cal mot. The free energy of fonizaton of water to H® and BH is 19050 cal mot What i the everstble EMF of the fllowing coll at 25°C? Ht) otra |H° BH, 0,69, tau 0625 v ( 0305 @ os3av (@ 0.405 v Solution 1 Gives: Hin + tou = Hon 0 HO = He + OH 6700 calmer", AG, =19050 cal mot! i Cell reaction Hy eH ne Joyenos2e ea 28H Wyakojen w= at +268 iy 9 by 2nd tng me ys 0,¢H0 we 2 +384 sc + 286 56700 + 219050 19600 calmor* -==18600 «4.2 mor eats 4t84)=4.2)) 078120 Jmor ac=-nFFa =78120 Jmol" =-2 «96500 C xEat Fg) 70.405 V. Electrochemistry 769 Example 11. The EMF ofthe cel, Pricet*@o%), Ce*A0%)| Normal calomel elecvode is 1.468 Vat 25°C. Find the value of equilrium constant of the 262" e2H® —s 2cet +H, The electrode potential of the normal calomel electrode is $028. () 23810" 16700 (6) 1.08 108 (@ 3.2400" Solution (6) E.=E-~£,=1464V 059 Fageyete “EBs jeon 2 bog oe) (] 2, - 2058 gg 10 fats jce" (OB gg, Fou EateEt eg stata [fe oases] : 144 -02- (ju - 08512) Foss jeoe 128 Now 262424 cH oH, fa ua =0 2S ek aod 22" 4 2c 42 (Ontaion meahole 426 Hh econ) Callrsacton 260" + 2H —s 2Ce! + Hy =F ~ats = Fanaa eo) wo-12y01.24 loak=4203 > K=1.00«10!Start Practice JEE Main Round 1 (topically Divided Problems) Conduction and Electrolytic Conductance 1, Elostrolytes when diseolved in water distocates into fons bees (a) they are unstable (b) the water dissolves it (o) the force of repulsion increases (@) the force of electrostatic attraction ae broken down by water 2. The conductivity of strong electrolyte (2) incest on dilation slightly (@) decreases on ation (e) doesnot change with ation (@) depende upon density of electrolyte itslt 3. Which of the statements about solutions of electrolytes ia not coroct? INCEET Exemplar (a) Conductivity of soltion depends upon sie of fons (by Conductivity depends upon viscosity of solution {6) Conductivity doesnot depend upon solvation of ons present in solution (@ Conductivity fslation inereses with toy ‘4. The conductivity of a 0.01 N solution is found to be 0.005 chm’ cm”. The equivalent conductivity ofthe solution will be (a) 5% 20° obi en? equ"? (0) 5.00% 10° oh ent (6) 500 ohm em equir™® (8) 0.5 ohm em? equiv 5. Tho equivalont conductivity ofa solution containing 264 g of CuSO, por L te 9100" em* eq”. Ite conductivity would be (0) 295107 0 em @) 1810707 cw (9 24010 0 ow (@) 36210707 or 6. Conductivity (anit Stemen) is directly proportional to the area of veosel and the concentration of the faluton in it and is inversely proportional to the Tength ofthe vessel. Then, the units ofthe constantof proportionality is (@) $m mot () St mt mot® (9) Sm mol (4) Sm mot 7. The cll constant ofa conduetivity cell INCE amp (a) changes with change of electrolyte (©) changes with change of concentration of electiciyte (e) changes with temperature of electrolyte (@) remains constant fora cell, ‘The specific conductance of 0.1 N KCI solution at 23°C is 0.012 The resistance of cell ‘containing the solution atthe same temperature was {ound to be 56 che. The cell constant wil be (@) 066 em 0) Lzem* (6) 018 ew (© 166 en 9. Anoeu om 18 equal to... IN CERT Exerple (2) Aye + Saga.a)~ Aare) 0) Suomen + Aan ~ Ac) (9 Seomicy + Nau) = Sac) (©) Sagas * Saou ~ Axpacy 410, Given the limiting molar conductivity a8 HC) = 425.90" em? mol! (NAC ~ 126.40") om? mot? 185 (CH,COON) = 910 em? mot“! ‘The molar conductivity, at infinite dilution, of acetic acid (in em! mol) wil bo (@) 4a () 3505 (© 205 (@) 5169414, The limiting molar conductivities A° for NaCl, KBr and KCI are 126, 162 and 150 8 cm? mol? reopectively. The A°for NaBr is (@) 128m mot () 248 Sen? mot? (9 328Scm? mat (4) 348 Sen? met"? 12, Theresistance ofa conductivity cll filled with 0.1M. KCl solution is 1000.12 ofthe same call whea filled ‘with 0.02 MKC! solution 962001, calculate the molar conductivity of 0.02 M KCI solution Theconductvity of 0.1 MCL solution ig 1.29 8 mt iNceeh (2) 1265 mF mot) 12651078 Sa? mak® (0) 12620" Sm mot (@) 1265107 § mf mot* 13. Conductivity of 0.00241 M. aad is 1806%10° Sem". If Ay for acetic eed is 800.58 em® mel, what isis dlssocation constant? INC ( 260%107 mal (©) 3.98% 10° moti-t acetic (@) 2.85% 10° motto? (6) 84x10" mot Hectrolysis 16. During lectsotyte, the spaces dacharged at cathode are ‘e) anion (2) caton (©) ions {@) AM thee 415, Electrolysis involves oxidation and. reduction respectively (@) snode and cathode —() cathode and anode (6) at both the electrodes() None ofthese 16. In the electrolysis of aqueous sodium chloride solution which of the half cell reaction will occur at ‘anode? INCERT Exp (2) Nat (ag) + = —> Mal Ely =-2.1¥ (©) 28,00) —> 0,9) + 440 (oa) +40"; Ea =223 Faq =0000 wtegee — naar (eH) — Ponta re Fy =1360 17. During the electrolysis of fused NaCl, which reaction oveurs at anode? (a) Chloride ions are oxidied {() Sodium fons are oxidised (6) Chloride ions are reduced (6) Sodium ions are reduced 18. Use of electrolysis is (2) eloctrorefining {Both (2) and (2) (0) electroplating (@) None ofthese Electrochemistry 771 19, Forwhichofthe following highest changes required? (NCERT (@) A male of aD tol () mate of "to Cu (6) Amol of Ha, to Hx* (@) Sane for alt 20. The quantity ofcharge required tocbtain one mole of aluminium from AO ie INCERT Exempla] @iF oF (oF 2 24, The number of Faraday’s needed to reduce 4 pequivalente of Ca to Cu metal will be ot @?2 os es 22. During the electrolysis of an cletrolyte, tho number of ions produced is directly propertonal to the (@) tine consumed (0) mass of elections (quantity of electricity passed (@) electrochemical equivalent of electrolytes 23, The number of coulombs required to reduce 128 g of nitrebenzane to aniline, (@) 98800.¢ (@) 95700 () 57906 (@) 57900.¢ 26, On passing 3A of eleteety for 50 min, 1.8 g metal ‘eposits. The equivalent mass of metal is G93 (0) 193 ma @ 99 25. A solution of NWNO,), is electrolysed between platinum electrodes sing a current of 8A for 20 min. What mass of Ni is doposited at the cathode? (Atomic mass of Ni ~ 58.7) Incexn, (@) 5475 ©) 1828 (3876 @ 225 26. When 9.65 © of electricity is passed through « solution of silver nitrate (atomle weight of Ag = 107.87 taking as 108), the amount of iver deposited (a) samy 2089 (0 15809 (@ 2085 27, An electric current is passed through silver nitrate ‘solution using silver electrodes, 10.79 g of silver was found to be depesited on the cathode. Ifthe same amount of electricity Is passed through copper sulphate solution using copper electrodes, the weight ‘ofcopper deposited on the cathode is @iss 239 329 @ 64g772 SEE Main Chemistry Galvanic Cell and the Nernst’s Equation 28. Which of the fillowing statements So correct? Galvante cel converta (a) chemical eneray ito ec energy (2) eect energy into chemical enegy (0) tal Romitselenertal statete he conbind state (2) eecucyte int individual ions 29, Ina galvanic ell, the electrons fw trom (a) anode to eatode rough the extemal cect (0) anode to cathode tough the slstien {c) cathode to anode rough the extemal cst (2) cathode to anode Cough the sation ‘30, What ows inthe internal circuit of galvanie ell? (2) fons (@) eeuors (0 meetacty (@) mons 31, Which col wil measure standard electrode potential cfeapper electrode? INCE fre (2) G9) mo. 0-ba9 (00.199 100149 168 (0). bmg 119 (og. fa (6) FC) (0.300 26189 0 (Po [Hg Xba [Hag 01M) 000g, M00 32, The standard potential at 25°C for the following halfreactions are given against them Bat +e" —s Zn; B= 0.762 Mg?" +267 —> Mg, BY=-2.TV ‘When sine dust is added tothe solution of MgC! (@) 200, is Fomed () Mas precipitated (6) In disves in the solution (@) to raetion takes place 33, Arrange the following metals in the order in which ‘hey dinplace each other from the solution of their alte, Al, Cu, Fe, Mg and Zn (cern (@) Mg>tZn > Al Fe> ub) Mg>Fe> Al>Zn >O (0) Mop Al>2n > Fe> Ou (8) Mg> Al>Fe>7n >O2 bridge is removed from the tw half ells, the 34. 18 voltage (@) drop 220 (©) does not change {6 increxe graually (@) inceaes rpiy 35. An cletrochemiesl cell can behave like an. tlectolytic ell when INERT emp] (2) Eo =0 (©) Fea >Eo (0 Fr Fea @ few the correct order sin wen below find out 36. Using the data gi ee, ‘of reducing tendency 93 V: BB yer “136V SIV; BBsege2-078V (0) cP cor Age Cl {8-21.20 kd, the standard emf of cl (@) 02390 (6) 02200 (@ 03200 (@) -010¥ 54. What will be the emf for the PEL TQ(A)1 HP (og IIH 22) Pe? ven ell o) Fag, Bt Fog Be to Fen et 0) Fes, (Bog Fron (@) ose of these Batteries 55, When alead storage battery is charge, it ace as (@apimryete = (0) agate et (6) aconcetation cel (@) an eects eat 56, While charging the lead stroage battery Nett emp (2) Fo, anode ie edced to Po ii (8) Piso, cathode ie edaced to Po {6 P0, cathode is oie to Ps (@) P60, anode ioe to P80, 57. On the basis of electrochemical theory of aqueous torreon, the reaction oeurrng atthe cathode (0) 5) i (a)s4e" > 20) (Hyg) + 20479) —+ an) +2 (0 Fa) — Reg see (8) Fea) — Hegre774 SEE Main Chemistry 58. Which of the following statements is true for fuel cals? (@) They are more efficent (@) They ate fee fom polition () They run il reactants ae active (@) All of the above ‘59. Which of the following reactions ie used to make a fue ell? (2) 28a) + (0) —> 24400) oy a4 90) 22D . (5) + 21,80,(¢¢) —> (3) (P(e) + POG) + 2 Shap (cay + 285(0%) (2) —> OK) + ANHCOHD, +20) 60. When an acid cell s charged, then (4) voltage of cell increases (@) resistance of cel inreases (6) electolyte of call dates (@) Wone of the above Round UI (Mixed Bae) A. hey of 0.10N solution of Cal, ig 100.0 Sem eq” at 298 K.G* ofthe cell =0.25em™. How much current will flow when the potential difference between the mora (oa 2. The resistance of a solution A is 600 and that of solution B is 1000. Both the solutions are taken in ‘volumes ef olution fand Bare mixed, what 1s the resistance of the Imixture using the came cell? (Assume there is no change or increase inthe a of A and B on mixing) (@ 4a e670 wa (@ 780 3. Conductivity of saturated solution of Cox(Fe(CNy) {is 20x10 Sem”. The conductivity water used to prepare the solution has conductivity 80x 10-7 Sem If the ionic molar conductivities of Co and[ FCN) J" are 80.0and 440.0Sem? mol”, reopectvely, calenlate the solubility product (Kp) of GoylFe(CNigh assuming 100% ionization of” the complex, (@) 8x10 (@) 3210 (2x10 32x10 4, ‘The electrical conductivity of solution serves as a ‘means of determining the end point ina chemical ‘eaction, involved in the titratce of acid, bases, or precipitation. Which of the following conductemetric {trations represent the curve of HCl ve NH OH? -eaxie = Volume of alkali added yeaxie = Conductivity ea ae Py Ea ola mina we seater net oe (2) Hor, (B) OH —(€) Op Ma (4) 0, SO ve we to mete ate (a) 1.0dm? (b) 564m? («) 11.2dm? (a) 22.4 dm? tone Ti hcn — wap ttt Sate (a) Pt/H,(g) KC\éel) || AgCl(s) | Ag (©) Pt/H,(9) HCUsol) || AgNO,(sol) | Ag (c) PL/HA(g) HCIGsol) |] AgCt(s) | Ag (€) Ag/AgC\(s) KCUsol) || AGNO, | Ag Seetaccetiaz et (a) y will oxidise x and not 2 e9. A solution eating ome mole per ire of each ‘Cu(NOs)p, AgNOs, Hea(NOs)y and Mg(NO,), is being localised by using inert elecredes. The van of Standard slctrode potentials tn volt (eds tentials are Ag/ AS” = 908,212" = 0.1, Cul Cu = 40.34, Mg /Mg” =-2.37. With Ineressing voltage, the sequence of dapeiion ef sietalson the enthode wil be (2) AB H.C) On Hg ag (0) A833, 00,Mg——() M50 HA 10, Anlactrocheria cll ist up as floms Pula, Laem) (01M Het fo a Vict amet Enfef tis ll wil ot bo eo because (athe Hof 01 Hc ané 04 Macias at the acid () acids used in two compartments ae diferent (6) emfofa cel depends onthe molatie of aie used (@) the temperature is constant 11, On passing 1 F of eletrcity through the electrolytic calls containing Ag", Ni and CP sons solution, the posted Ag (at. wt. = 108), Ni (at. wt. = 68) and Cr (ot wt #59 18 ON OG (@) 108g 2955 735 ©) 108 5955 5208 (6 108g 1085 108g (@ 1085 11759 1669 12. Which of the following wil form a cell with the highest voltage? (@) 0.1 Mag’, 2 Mc (6 1magh, 1 Moo ( 2m as" 2Mc (@ 2M As" 02 Meo 13, ‘The Bdison storage col is represented a eis), FeOts) KOH (aq) INiO3(0 IN) ‘ae hal eationa are a (oe HyOD +24" —¥ 2NIO()+ 2080; ane (Be =+0.40V 6) + HyOKD + Be” > Fel) +200 Ota eH Be=-0.87V J the incorrect statement crag the ese wh reef cnetton of Fa (fan dees with nee in concration oir oru-12 (oFsainrenses ih inaeiin concentration Electrochemistry 775 16, 1.05 g of lead ore containing impurity of Ag was dissolved in INO, andthe volume was mede350 aL. ‘An Ag electrode was dipped in the solution. -PUH,) IT (LM LAS" LAR. ‘The Bay §# 0.508 V at 208 K.The por cont of Agin the ores (By .,, -080¥) (@ 03% & cosen (9 0.060% (@ 03% 15, Given, standard electrode potentials Felten 4 Fe, B Fe +3e > Fe, EY ‘The standard electrode potential E*) for Bete — Felis ( som @ -omny. () soatry (@ -oaa7v 16. The of the call, emt Zn | Zn** (0.01 M) || Fo(0.001 M0) | Feat 298 Kis (os ox 117, Consider the following dsproportionation reaction, 2C10; <= C10; + C10 Ifthe initial concentration of perchlorate ion i 0.1 M. what It would be at equilbrivm at 298 K? Fze995"226V tl Begs; "08 VI @)O1M (006M (997M (a) 019% 18, The standard emf for, the given ll reastion, En Cu —> Cu + Zn! is 110 V at 25°C. The ‘emf for the cell reaction, when 0.1 M Gu?" and 0.1 Bt ‘nt solutions are used, at 25°C, is (@) 1200 @ - L107 (0 220 (@ -2200 19, By how much is the oxidising power of CaO} /Ce* couple decreased if the" concentration is decreased from 1M to 10" Mat 25°C? (a) 0207 (0) 0414 (6 a001v (@ o2srv 20. The emf of a Danill call at 298 K is By 2a | Za80,|I CuSO; | Cu. When the concentration of (oom) com ZnSO, is 1.0 M and that of CuSO, is 0.01 M, the erat changed to Ey. What is tho relationship between Ey and E,? ie EPR ORse (@ R=0-8,776 SEE Main Chemistry 21. Cu" fonts not stable in aqueous solution because of Aisproportionation reaction. £° value for ‘isproportionstion of Cu is (ven, Bgysejoye = O15: =024 VD (0) +0380 @)-038¥ (9 s009¥ (0405 22. Consider the following reaction 2Ag* + CoHiOy + HO—+ 2g) + C01 + 24° ‘When ammonia in added tothe solution, pH is ralsed to 11 Which alf-cell reaction i affected by pH and bby how much? Ags > A Fxg =08V HigOy + HO —+ GathOs + 2H + 22% Eng =-008V. Ag(NT)} + e° —+ Aghs) + 2NHy; Big = 0397 V (@) Edu, wil increase by factor of 0.65 from Eas (©) Fe, wll decrease by a factor of 0.85 fom Fass (6) Bg, wil increase by a factor of 0.65 from Fi (@) Eg. wil decrease by a factor of 0.65 from Ea 23, EMF of which of the following cells at 208 Kis highest? Neer Give, Ehygteyy"-287¥5 Eigse) 10s Eigening OMY: Figgas OUY Biyaagrney 22 08¥- (0) Mate me" (o.com ca(.0032060) (@) Fe(ofFe*(o.0n¥ (AH) Hs) BATFE (Sas sn?*(0.950M) [0.020 %) (0) (base) (@ MEIER CIDE (0.01 H 1 ONBEENLD) (ab fs) 24, Using the flowing data, forthe electrode potentials {alate 46° in kl, for the indicated reaction. 15Ce**(aq) + Mn?*(ag) + AHO —+ 5C"(00) “+ Mn0y(0a)+ 81(a0) MnOzlog)+ 8H"(o0) +5” —+ Ma*(ag)+ 41,010 BeaelsiV rev coltag) 4 > CoPagh E* o (a) 626 s (3156 @ 965 25. The valon of Ku ca the standard half-eaction ee iSp PH and -08277 V forthe balf reaction 0-2" —> He +20H" Kei it @) 91-30 sane" (9 236030 (@ 555410" 1, Calculate reduction potential at 26. Banu the Ce/Ca couples. Ky of pH=14 for the,,| CuOrn, = 10-10 (a) 0220 0220 foouy (6) 044 27. The reversible reduction potential of pure mate it presrare. If the Tyas V under 100 atm Hy Fedocion ip cosidered to be 2 + pH of pare water is > 7 oe (a 635 More than One Correct Option 28. Molar conductivity of ionic solution depends on ~ INCERT fare 2 —>+ Ba, (0) tempeatase (0) distance between electrodes (0 concentration of electrolytes in soto (@) safoce area of electrodes 29, What wl happen during the electrolysis of aqusous tolution of C450, inthe presence of Cu electrode? (Neat erent (2) Copper wit depot at cathode (2) copper il dvolve at anode (© oxygen wb elesed at anode (@) copper wt epost at anode 30. F2q =1.1V for Daniell cell. Which ofthe following expressions are correct description of sate of cjulibeum in this al? INERT Ere (rar (0 ook = SE (8) tog K-22 31. How can the exidation Sao potential of a hydrogen (@) Inceasing the py, (0) Increasing the (8) (6) Decreasing the Pa, (@) Decreasing the pOH ofthe setation32, Which ofthe filling conditions wil jneroase the oltoge of tho cell represented by the felling union? Tals) + Cu(0q) —> Zang) + Cus) (0) Decrense in emperatare () tnceae in pressure (6) Decrease in the concentation of 2a ons (@) tneease in the concentration of Coq ons Assertion and Reason Directions (@.Nos 831037) Eschofte ution consis to» seers Statement Asseron) aed Statement Reser), Echo ‘hse queso sobs four leat chen lyon hc ie arcane Yotaeto secone et (@) Statement is true Statement Is tue, Sateen tsa cone explanation for Statement (t) Statement Tis tre Ststement Its tue Statement Is pots correc explanation for Statement (6) Statement Ii true Statement 1s ase. (@) Statement fale Statement is tru. 33, Statament 1 Mercury cell docs not. give steady potential Statement In the cell reaction, ions are not involved sn solution. INCERE empl 14, Sutemest | On increasing dilution, the specie conductance keep on sereasing Statement 1 On screaing_llaion, degree. of Tonisaton of weak electrolyte increas and molality of ons aso increases. Sitemet 1 Ege ing concentration of Ag” fons. etl Ey, pasa pone val. Satara Face mee cen te 35. increases with ineroase in 36, Statement | If an aqueous solution of NaCl is flectrolysed using inert electrodes, chlorine produced atthe anode, and Hy gas is produced at the tathode, Suatement M1 Electrolyois of aqueous solutions Stntaining metal fon that aa weaker oxidising agent than "Ca, ll produce H gas at cathode 37, Statemont! Baa should have a postive value for the cea to function. Statoment ll Eratate 0: 06 <0 @EnccaGso (Bay 0286 <0 39, If the 0.05 molar solution of M® is replaced by a (0.0025 molar M® soltion then the magnitude of the call potential would be (@) 35a © uoav ©) 70nv (@) 790av Directions (@. Nee. 40 t9 42) A fusl cell is continuously supplied with an ordant anda redictant ao that itean deliver Surreal indefitely. Fuel cll offer the possbiity of Schering high thermodynamie elicleney inthe conversion of Gibbs energy int mechanieal work. Internal combucion eine bent overt ony he tin othe hat £ cambunion ino mechanical woot Wile ge Shemodynami eieny ofthe fale gen by n= 2 re Ath Gi eee hangs forthe el ato sn [ni thenthiy change fib cl reason, Tyla FO) > Ha Bnav 40, For 9 hydrogen-onygen fuel cell if HPO, 1) --285 k/mal then what will be ite ‘thermodynamic efficiency under "standard conditions? “@) 0 () 048 (0a (@ 059 44. 1f500 mLoftl, gas at STP is fed inte and igconsumed ‘by the fuel eel im 10 min then whats the eurrent output of the fuel cet? 2 ow ws es 42. Tho advantage of using ful cal ina mator ear could be (a) low inka cost (6) Ughe weight (b)elssioness operation (4) reedom from refueling778 SEE Main Chemistry 43. 45. 46. 41. 48. Previous Years’ Questions ‘The standard reduction potentials for Za!*/2n, Ni IN and Fe /Pe are ~ 076, ~ 0.23 and ~ 0.44 V respectively. The reaction X+¥2 —> X® + willbe spontaneous when (ave 2015 (@X=MLY =F) X=NLY=2n (X-Feyamn — (@) Kam 7=m ‘The reduction potential of hydrogen halfcll will be negative if (aes 2011 (@) tg) 2am anda} = 20 (©) pti) ~ tat and] - 2.0 (6 alt) =2 etm andi") 2.00 (2 ft =2 am and] «20 Resistance of 0.2 M sultion of an electrolyte is 600 ‘Thespelicconductance of the slain is 1380" If resistance of the OAM solution of the same leerolyte 1s 2800, its molar conductivity is aes 2011 (262508 mt mot () 6.2510 Si mat (91625410 Smt mol (0) 625 Sf mot “The Gibbs energy forthe decomposition of ALO, at S00 sas flows FAO 5 Al + 03: 4,0 966 ki mot "The potential difference needed for electrolytic east NEE 2010) @) 307 @ Sov Given, BY, =-O72V.B 3 2p, 2-042. ‘The potential forthe call Gr| CP* (GAN) || Fe (0.07M) | Fess (ese 20081 (@) 0267 0300 (9-039 (@-026¥ ‘The equivalent conductances of two strong clectrolytes at infinite dilution in H,O (where fons nove freely through a solution) at 25°C are given blow Rengcoox = 91.0 Sem? equiv ‘Aor = 426.2 Sem? fequiv ‘What additional information/auantty one needs to caleulate A°of an aqueous solution of acatic acid? (ae 20071 (@ Arona ( Av ofcH,c008 49. 51. 53. (c) The tinting equivalent conductance of" 'y-) (@) A° of enloroacetic ack (ICH,EOOH) ‘The ell, | Zn2* (1M) 11 Cu (1M) | Cu be complete (B%qq= 110), was allowed ty ireiareea at 208 Kc The relative concentration of a weut( 20} eee (253) ave 2007) 73 (a) anttog (26.08) ; (@) 9.65% 10 (0? ‘The molar conductivities A" infinite dilution in water at 20°C are 91.0 and {26.2 Scm*/mol respectively. To caleulate A"yoye, the additional value required is 1 2006) @) Arno ©) A%ea (0) Asst (@) Atwo Given the data at 25°C, Agel —> Aste te se iat inthe val fog Ha fr A? 2an0 7 -0asov) vers oy -ais 802 Oona (0 tes cre |W [es [aoa] Calcite Sug sing appropiate lr conductances of the electrolytes listed above at ‘infinite dilution in H,0 at 25°C. ange 205) (@ 275 (b) 390.7 (95827 (@ sire Alumina onide may be electriyed at 100°C to femish aluminiam tal (atomic mane 27 1 Faraday 86500€) The cathode eacuon Alm 436° —s al? To prepare ‘led ealdrgeee| miam m (0) 540010 Co eecety (0 549010 Cotdeetiy (011.801 cet ateceey (@) 5.49% 107 C of electricity54. In a bydrogen-oxygen fucl cll, combustion of Inydrogen cecurs to (atte 2005 (@) generate heat (©) create potentisl diference between the two letodes (©) produce high purity water (@) remove adsorbed oxygen from electrode cufaces 55. The Bija.jyys value for Cr, Mn, Fe and Co are OAL, 41.57, 0.77 and + 1.97 V respectively, For ‘which one of these metals the change in oxidation Electrochemistry 779 ‘56. In a cll that utilises the reaction ‘o(s)+ 2H (ag) —> Zn*(aq)+ Hat) addition of H,S0, to cathode compartment will WEE 2004 (a) lower the and shift equim to the let (©) lower the & and shift the equilibrium tothe raht (e) increase the # and shift the equium tote ight (@) increase the and shift the eqilrum to the et 57, Standard reduction electrode potentials of three tmetals A,B and C are + 05V,-30V and ~12V ‘ate from+2to +3 iseaiest? ‘dutty Fespecuvely. The reducing power ofthese metals are Or ae (@) B>c>A wae a oi (casa (0) A>co8 | Answers Round 1 2 20 326 40 s@ 80 7 2a 20 2o BO 2O B® 4H BO BH 2H BO BO we 20 20 BO UH) BH 2H ZO BO BO WO BO 2G BRO ¥*G BO RH TO BH BO 2O 26 20 £0 4G 60 £0 79 #6 8 BO) 6 20 BO MA SO SO) Te SH SLA) Coe Round tt L@ 2 20 40 6 76 B® 90) s0.0) 2G 20 BO we %@ 70 2 2) 2.0) | 2@ 2@ 2@ 2 2 2.0) meas 2d he | neo Reo BO KO BO 1G BO BO MO | 26 20 #0 «oe 20 79 &@ BO Se | 26 2m Bo se BO oe) the Guidance 3. Conducvy lo depends ypn he slain ons eee 1000 4 Na aemali 095100 59 ah en ex hey + en? ea? (P54 een ovate gsriciaas *) =29 1072" en" R= 0.012455 = 0.6 em! 9. From Kobus’ ow, Haren Aronian? Arawors Bact 10. Sum of mol conductivity of resetan’s = sum of molar ‘ondtvity of produes Theretore, forthe reaction CCHCOOH + NaCI —+ CHCOONA + Het780 JEE Main Chemistry 18, CH{COOH = 18,CH,COONa + ABHCI- AyNaCl =914 4259-1264 390.5." om? ma * 11.126 Sen mol YAfuo. (052 Sen? mot) Aas = AG + My wo Get Ae ® (50S? mot) ig AE A 9 Bytes + 6-0 Man Ba +R tes 152-150 128 Sem? mor 12, celcontn.C*= Conuciiyaiace wia9ser's1000 Sage «ta3en onus f 002 Kon = CConcentation =0.02 M1000 »0.02 mole? = 20min? 0.248 5 20 maim 2410-4 Sr? mor Molar conductivity 13, Calculation of mola conductivity) 1 =7.096010" Sen 1.00281 ¢=0.00241mal rl 0024 a 241.007 nol crv “atx 10°F mol eh 2.765? mol Calculation of degree of dissociation of HCOOH a) A 0276 S.n? mar 1, "Q805Ser™ mor = 0.088= 6.4% 10°? Calculation of isocation constant) jxfHCOOLIM] _CaxCa _ Ca! =" [CHCOOH) ~ Gta) “=a 0.00241 mol) 0.086)" = 0.088) = 00900185 mot = 1.953107 mol of oxidation, Thus, the reaction lecton releases OCC Spore veaily 3 Compared 16, Ana i atays the tieteeutaion oc Se. Moreorers0 Bonded va 17. During the sects of sed Pie at anode ard is proces 19.00 t mol of AP 8) : ‘code acon Aa + 36 Mea? * Smt read for ection o 1 molec Sp.c= 209500 C 2,896 «10 C acl, chloride ons ae s called oxidation. Ake ‘Quant of chase ABTS Faraday = 3 1965 i) tol a? to Cu Becrode reaction Cui) + 26 —+ Cust ity of charge required reducing 1 meseCu™0 SETS Frotsoo c= 193000 ¢~ 1.23% 10°C (i 1 moto; to Ma?* Electrode rection: May + Se —> Mn Quant of charge equred for reducing 1 mole MO; tM" = 5 F= 5x 96500 482500 C= 4.825% 105 21, Number of equivalent = numberof faraday ass agar 22. according © Faraday law, number of ions produced ‘uary of lect passed 23. GINO, + 6H +62” —s GHyNH, + 24,0 Cstel(=128 leobezene rere eles of 96500 Ccharge 123 gniuobenzene wll require charge 696500 «123 a 639650 «579000 Exit £3 50060 36500 "96500 96500 x _ 96500%1.8 3450 x60 "355060 Beta tt pe ws <2 incs Chena eq te mse ec Ni(NOs) 4aq)+ 2H? + 26", > eee sg Me our dusrindsenn ett ane‘Charge required to depos 1 mote niche =2F=2 «965000 = 1.99. 10°C Molar mass of nickel = 58.75 mat! 1.934 10°Cof charge produces nickel = 58.75 000 C of charge preduces nickel = {28.7812 (6000 0 (199% 1050) = 18258 fgXQ _108%9.65, ng = fis 108% 107 26 ag a = OBS «1.065 107? 5 10.8. 27. Number of equivalents of ver formad number of equivalents of copper formed In AgNO, Ag isin +1 oxidation tte. InCuS04,Cu is in +2 oxidation sate, 34. Pus Haig, Than | Hag 1M] Cu(ag, 190 | Co ‘wile use to measure standard electrode potential of copper lectrode 32. Zn + MgCl, —+ no veaction “This ype of eacton does not occur because Mite =— 237 V,while ni = 0.76 33. Mg>Al>Z0>Fe> Cu Ihmeanethatevery metal on the ft siecan displace the next ‘one rom it salt solution. 34, When the salt bide removed potential opto er 35. When ye > Ezy the cell behaves ke an lett cell, 36. More negative of less postive is the value of reduction potential stongrsthe reducing age “Thus, he onder of ecg tendency 88h 2H sto, m0 ane! 2 +h0,426 —9 440 stone? Solutions. Hence, ther individual COM + 248 TAT feo") ta nS] Th ate cer genes ag 13. £20.87 +040 Cell reaction Fe + NO) —+ FeO + 2N'O jg fmaingurlfected from he concentation af FeO. av 14, Calleation :EHyig)+ Ag") se Asta + HAM £6205 ag HED 0503-080 905% gg) xo94a 10M Number of moles of Ag" in 380 mk 9.43 110° 5350 a 1052380 5.300 3 x10°* x108#3.5610" Mas of Ag recipe ot Ag inte = 22820 909 =oon9% 15, We know tha, AC =—nre* Fe 426 + Fe AG*=-24F x 0.490 i= 0.8805 o Fe"s3e + fe AG 2-3 ¥F xt 0.036)~ 0,100 F 9 (On subtracting Eas: fom i, we get Fee os Fe 86"= 0.108 F- 0800 Fa 072F forthe eacion «= AS" = (607727 TF omy 16, For the pven cell ection i Za + Fe —s zn + Fe 2.0591 59 G =e 205 og Sr ae 0.0591)... log Bae784 JEE Main Chemistry = 0.2905 + 20921 oxv so va "F197 LOD 0322 ‘0.0591 k,=10088 417. Oxiatonhltcell lo; + 0005+ 26" Reduction hee 105 +26" —+ C105: ox ‘0.0295 tog k. = Foy= 033-03 or 0.032228 ogk or 2010; <= ClO; + Clo; Behe RD 18, = 140v 19. Haat econ is : GqOP + HY + 60° — 9 2074 74,0 E Fy we op ce» —Feych 2.0591 ,, {cP 8 NGO 0.0591 6 log 1079" =-0414 0.0591, 0.07, , 00591, ~ 9.9591 og 091 a, + 295 fot ‘24. The required reaction (Cu + Cu—> 2Cu") can be obtained by using he following reactions ea ce + O, Boge TONS ll =034V a cu ez CH Fcc Matipying Ea. by 2, we set acu +26 9 200", AGy=-nfb 2-2 KF x05 iy coh +20 — Cu AG, <-nFE =-2xF 034 i subtract he from Ea i cul cu —> 200" (3G, nF =F XE aio, 8G 8G)~8C2 : offen (2 x019-C2F 1030 2-038 Tse te value forthe reaction cu + Cu —> 200" ‘rhe given eacton is just reverse oft | 1 Ea fr given reacion= + 0:38 ¥ | 22. Asammonia is aded the concentration of" decesssthas ‘uiton penta increases by 0.65 23.) Cetlequation: Mal) + Co?(ag) —+ Mea) + Cus 1.0591 MET 2 cur 0591 jg f107] (237-2224 1034-23-22" oo 2 2:71-0.02955= 2.68 EMF = 2.68 Gi Cell equation: Fe(s + 2H"(aq) > Fetaq)+ He) o=0 0591 jag (fe) erst equation : Eau =a lon ED _ aT, ft ttc = 0-0 40)-225% ngO! Nevnst equation: Ee EF ofthe cll =| 10° oF 044-2591 -9 +044 0.0887 05287 40.53 iMF=053V id Com equation: Saga + 2Hiaq) —s SoPaa) + He) wed 0.0591 9180") 2 Nemst equation : Fag = Ey EMF of the cal, = =0.10)-285 pg 25, | ooElectrochemistry 785 014-2251. 2097) OF +2 — 0.0591),4 1 =0.14- 0.0620 = Fa rcu Ey ey eo. 0.14~0.0620 = 0.08v or eee a eR Epezeey, 0.0591 reciept aes 34-2959 og 0% (0) Cell equation: 287-0) + 2H" (aq) —+ Br + Ha) z 00591219 =a 0.9591, 4 ‘Nemst equition : Eg =F pt pe 2 aE 2. 0.0597 1 we 1081-2859 gg 2 oa onr tothe 222 og 591 ™ 2 iF 1.08- Wogtt.111 « 107), 0.0591, we 0413 00 + Sos? 108-2259 e045 2 a 0.413 = -0.0591 log (HI, [since, ~log [H"]= pH] =-1.90- 0208-1288 =0059%9H owro1280 oa 6; Oxidation will occur at hydrogen electrode and reduction aa) by lecrse! 28. Nola conduciviy depends upon the concentration of Ths, ets it for Mu cl ‘Sec ion and seperti 26. i~Fixe) Ki" 161-151-0207 29, When aqua lution of C3804 i lected by wing Teen ceooe econ, copper vl cv om anode re gt Sond texted 7-3%56500%0.10) ae 30. Nerteatonis ‘cogs 23037 25, Wecan wre call reaction tale" and OH” on RAS Tg, Hie) —> 2Hag)+26° 2000 evi, 2H,0 426" —+ Hal) + 201F (aq) 208277 £8 ae 2.0K 2H,0 — 280 62047 n=2 Fy =-08277 ORT og, Qa HOHE =e 2200 og, = — it sor, beet or 2059 tog, QeHr OH “Korn Fa =0.00 Vivid BA, -ioak cag 25 og K orlog ke 21.1 z= 31, In the given case, 6.059 9009 og BEL IncreasetH Jr decree yt decree Ey 32. Egy Eoa~ SE in 2). Decrease in Zn or increase in ary 1 (cu) erase Ee kK, -101210" 26.pHt=14 » pOH=OOH}=1M [CP HOH? = Kp 1.0 0 [co }=10-? w 33. Since, ions ave not ovelved in soliton incase of mercury cal is potential steady786 JEE Main Chemistry 34, The speciic conductivity decreases wile equivalent and molar condoctivites increase with ditsion, 35. Eng Foren has postive value. 0.039145 1 Ene 2059N og 1 1 iRgFi F* + 0.05106 A8"T Ths Ege ag creases wih increase inthe concentaton of Ane fons 36. Nametal isnot produced atthe cathode instead iformed) because water contains HO" fons or H lors which are stronger oxidising agen than Na", and are therefore mee esl reduced 37. For a cellt function, Eau = v8 Feat Fest Eaade se, Fake 38. mia eAaN0 —> NEOSI0 61K) 24-0 Gorconantatin cl 30387 |, IMP loosaa tog Shoes F Slane 30387 og 107 » 230287 fg 5 10°) 10 mV and AG <0 forthe feastility of Hence Ec "Eo the reaction 39. substng the vale ofy =70 mV in fq. (in 38, we 2.303R7 ose, F set the value of. So, Fan ty~ 222g 0025 al 20578 tog st +og 10"*ilog 5 = 0.71 -005380 07-4) =-00538x-26 120.1398 V =0.140 V =140 mv 40. AG =n af 296500 »1.2286 =-237.1584 1) / mol sen 22371584 So, thermedynamicefciency = 24 41. seomt ott 2 = 58th = 0.05 mol = 00596500 4025 C ae slo csren= 4225 8.04 so, eee cue 2 42.Fo the emisontass operation, the fe al i ed in he moore 43, cll eacion s spontaneous 46° <0 Sine, sore nF Ths, Fea ayes 3 rar ey ® xen Yore Nis Fe® —+ NPP + Fe Etyyee 40.23 igege OMY ba ea Ener * Eee -o2v Feu CJ X=Ni, Y=Zn Nis za oN 4 Zn Expy “023 V Fy aa” -0.26V Fea - 0.53 V Fea <0 * X=Fe, Y=Zn Fes tes 2n @ ‘Thus, this reaction is spontaneous,‘44, Reduction hydrogen half is HE sD | Pu) scl reactions 7 2 ag) +27 — He reaction quotient Q= py [HP n= 2 b= fig 222 og a oss, pee Bu [Wenn |e @) tam | zom | cas | ve @} ram | rom | 10 0 fo 2am | rom | 20 | oe wo 2am | 20m | os | ve {jy 0.00 V for standard hydrogen eecrade HQ > then Eg 45. Specie conductance = conductance x cll constant Lan 25 a atin Coll constant =15 «50 0°" s65m" 165/100) en"* Molar conductivity "oa “360 “i00 25S.em? mol” 6.25 «10 Sm? ol" no, 2 Salo 8G = + 9661) mot" 966.10" mot™ AG =—0FEew 966 x10? = 4 96500 Et Fin 25V 47. ce| Co" (0.1 M0 II Fe* (001 NO [Fe ‘Oxidation hal cell Crs CP" 4362 Reduction alfcell Fe 4 2 Feed Net cal action 2¢r + 3 9 20" 43Fe; 06 Electrochemistry 787 fat OP 0.30-2258%)oq 10.1 6 Foon 0.0501). 10° 2.059 1j95 10% 60 =030-' 2.0591 510% 2030-225 ogo 030-295""iog & (48, Wenow fom Kolrausch’s aw ot 02606V Magoo = Necoons + Ma ~ Mr 49. Calis completely discharged, € means eaulibium gets sstablshed aus =O Zajzn¥ (1 M0 |] CoP" (18 | Co Cell reaction 2a + Cu oh Zn" + Cu a to) K Wietnon Eng 2821 or 11002238og aD ansilog 220 seam] BOs = antag 373 50. Acowdingt Kohatach’s aw (a0Ae = CHYC—O'NT Moyeoos= Manco +e 0 Mencoone =Mancoor + aut i “Thus on adding Eas (0 and Gi) Hye and sulurctd we can cbtained the value of Aone Thus, ‘aelonal value requied Mac 5A, Aga ee” Agta srs Aa —> Ag se Aah A ey Pes 208 ay788 JEE Main 0952 tog ky = 2952, 52, Reon = Kons + Nca~ Mag = 91.0 + 4262~ 1265=3907 53.AP 36" Al weg here, w= amount of metal = 5.121 =5:12%10 g ecrochemical equivalent _evalet weight 36500 ‘lecrors = 96500 “596500 a, ‘T9650 5.12% 10? «396500 @ " c 5.49 107 C 54, Any cel ke fuel cell, works when poten ference is ‘developed. 55, ae . 512010 = Q oa pe nate 2H NSTY Eppegee O77 Fetegat 2 1I7V indicates beter reducing agent, More negitive value of Eg dation of Cr t0 CP” Is the thus enly oxidised, Thus, ox 56.20) + 2H" —+ Zn¥(aq)+ Hite) zn") oF Reaction quotient, Q spring cei Zn | Zn**(C) || HE (ag) | PUD) 2039 gk woe nd a 0591 14404 isaded to cathodic compartment, towards reactant sid, then Q decrease (due to increase nF) Hence, equiliiun is diplaced towards fone placed towards right and Eat 57. More negative value of €* mea S28 patie value of £* means higher reducing power. Boo