3.10 In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial concentrations of A and B as given below: A/ mol L–1 0.20 0.20 0.40 B/ mol L–1 0.30 0.10 0.05 r0/mol L–1s–1 5.07 × 10–5 5.07 × 10–5 1.43 × 10–4 What is the order of the reaction with respect to A and B? 3.11 The following results have been obtained during the kinetic studies of the reaction: 2A + B ® C + D Experiment [A]/mol L–1 [B]/mol L–1 Initial rate of formation of D/mol L–1 min–1 I 0.1 0.1 6.0 × 10–3 II 0.3 0.2 7.2 × 10–2 III 0.3 0.4 2.88 × 10–1 IV 0.4 0.1 2.40 × 10–2 Determine the rate law and the rate constant for the reaction. 3.12 The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks in the following table: Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate/ mol L–1 min–1 I 0.1 0.1 2.0 × 10–2 II – 0.2 4.0 × 10–2 III 0.4 0.4 – IV – 0.2 2.0 × 10–2 3.13 Calculate the half-life of a first order reaction from their rate constants given below: (i) 200 s–1 (ii) 2 min–1 (iii) 4 years–1 3.14 The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had only 80% of the 14C found in a living tree. Estimate the age of the sample. 3.15 The experimental data for decomposition of N2O5 [2N2O5 ® 4NO2 + O2] in gas phase at 318K are given below: t/s 0 400 800 1200 1600 2000 2400 2800 3200 102 × [N2O5]/ 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35 mol L–1 (i) Plot [N2O5] against t. (ii) Find the half-life period for the reaction. (iii) Draw a graph between log[N2O5] and t. (iv) What is the rate law ? Chemistry 86 Reprint 2025-26 (v) Calculate the rate constant. (vi) Calculate the half-life period from k and compare it with (ii).

1.37 Vapour pressures of pure acetone and chloroform at 328 K are 741.8 mm Hg and 632.8 mm Hg respectively. Assuming that they form ideal solution over the entire range of composition, plot ptotal, pchloroform, and pacetone as a function of xacetone. The experimental data observed for different compositions of mixture is: 100 x xacetone 0 11.8 23.4 36.0 50.8 58.2 64.5 72.1 pacetone /mm Hg 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1 pchloroform /mm Hg 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7 Plot this data also on the same graph paper. Indicate whether it has positive deviation or negative deviation from the ideal solution. 1.38 Benzene and toluene form ideal solution over the entire range of composition. The vapour pressure of pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate the mole fraction of benzene in vapour phase if 80 g of benzene is mixed with 100 g of toluene. 1.39 The air is a mixture of a number of gases. The major components are oxygen and nitrogen with approximate proportion of 20% is to 79% by volume at 298 K. The water is in equilibrium with air at a pressure of 10 atm. At 298 K if the Henry’s law constants for oxygen and nitrogen at 298 K are 3.30 × 107 mm and 6.51 × 107 mm respectively, calculate the composition of these gases in water. 1.40 Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such that its osmotic pressure is 0.75 atm at 27° C. 1.41 Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 litre of water at 25° C, assuming that it is completely dissociated. Answers to Some Intext Questions 1.1 C6H6 = 15.28%, CCl4 = 84.72% 1.2 0.459, 0.541 1.3 0.024 M, 0.03 M 1.4 36.946 g 1.5 1.5 mol kg–1 , 1.45 mol L–1 0.0263 1.9 23.4 mm Hg 1.10 121.67 g 1.11 5.077 g 1.12 30.96 Pa Chemistry 30 Reprint 2025-26 UnitUnitUnitUnit Unit22 Objectives ElectrochemistryElectrochemistry After studying this Unit, you will be able to · describe an electrochemical cell Chemical reactions can be used to produce electrical energy, and differentiate between galvanic conversely, electrical energy can be used to carry out chemical and electrolytic cells; reactions that do not proceed spontaneously.· apply Nernst equation for calculating the emf of galvanic cell and define standard potential of Electrochemistry is the study of production of the cell; · derive relation between standard electricity from energy released during spontaneous potential of the cell, Gibbs energy chemical reactions and the use of electrical energy of cell reaction and its equilibrium to bring about non-spontaneous chemical constant; transformations. The subject is of importance both · define resistivity (r), conductivity for theoretical and practical considerations. A large (k) and molar conductivity (✆m) of number of metals, sodium hydroxide, chlorine, ionic solutions; fluorine and many other chemicals are produced by · differentiate between ionic electrochemical methods. Batteries and fuel cells (electrolytic) and electronic convert chemical energy into electrical energy and are conductivity; · describe the method for used on a large scale in various instruments and measurement of conductivity of devices. The reactions carried out electrochemically electrolytic solutions and can be energy efficient and less polluting. Therefore, calculation of their molar study of electrochemistry is important for creating new conductivity; technologies that are ecofriendly. The transmission of · justify the variation of sensory signals through cells to brain and vice versa conductivity and molar and communication between the cells are known to conductivity of solutions with have electrochemical origin. Electrochemistry, is change in their concentration and therefore, a very vast and interdisciplinary subject. In define m (molar conductivity at this Unit, we will cover only some of its important zero concentration or infinite elementary aspects. dilution); · enunciate Kohlrausch law and learn its applications; · understand quantitative aspects of electrolysis; · describe the construction of some primary and secondary batteries and fuel cells; · explain corrosion as an electrochemical process. Reprint 2025-26 2.12.12.12.12.1 ElectrochemicalElectrochemicalElectrochemicalElectrochemicalElectrochemical We had studied the construction and functioning of Daniell cell CellsCellsCellsCellsCells (Fig. 2.1). This cell converts the chemical energy liberated during the redox reaction Zn(s) + Cu2+(aq) ® Zn2+(aq) + Cu(s) (2.1) to electrical energy and has an electrical potential equal to 1.1 V when concentration of Zn2+ and Cu2+ ions is unity (1 mol dm–3)*. Such a device is called a galvanic or a voltaic cell. If an external opposite potential is applied in the galvanic cell [Fig. 2.2(a)] and increased slowly, we find that the reaction continues to take place till the opposing voltage reaches the value 1.1 V [Fig. 2.2(b)] when, the reaction stops altogether and no current flows through the cell. Any further increase in the external potential again starts the reaction but in the opposite direction [Fig. 2.2(c)]. It now functions as an electrolytic cell, a device for using electrical energy to carry non-spontaneous chemical reactions. Both types of cells are Fig. 2.1: Daniell cell having electrodes of zinc and quite important and we shall study some of copper dipping in the solutions of their their salient features in the following pages. respective salts. Eext < 1.1V Eext = 1.1V (a) (b) e current cathodeanode I=0 Zn salt Cu Zn Cu -ve bridge +ve When Eext = 1.1 V (i) No flow of electrons or current. (ii) No chemical ZnSO4 CuSO4 ZnSO4 CuSO4 reaction. When Eext < 1.1 V Eext >1.1 (i) Electrons flow from Zn rod to (c) Cu rod hence current flows from Cu to Zn. – When Eext > 1.1 V (ii) Zn dissolves at anode and e (i) Electrons flow copper deposits at cathode. Cathode Current Anode from Cu to Zn +ve –ve and current flows Zn Cu from Zn to Cu. Fig. 2.2 (ii) Zinc is deposited Functioning of Daniell at the zinc cell when external electrode and voltage Eext opposing the copper dissolves at cell potential is applied. copper electrode. *Strictly speaking activity should be used instead of concentration. It is directly proportional to concentration. In dilute solutions, it is equal to concentration. You will study more about it in higher classes. Chemistry 32 Reprint 2025-26 2.22.22.22.22.2 GalvanicGalvanicGalvanicGalvanicGalvanic CellsCellsCellsCellsCells As mentioned earlier a galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into electrical energy. In this device the Gibbs energy of the spontaneous redox reaction is converted into electrical work which may be used for running a motor or other electrical gadgets like heater, fan, geyser, etc. Daniell cell discussed earlier is one such cell in which the following redox reaction occurs. Zn(s) + Cu2+(aq) ® Zn2+ (aq) + Cu(s) This reaction is a combination of two half reactions whose addition gives the overall cell reaction: (i) Cu2+ + 2e– ® Cu(s) (reduction half reaction) (2.2) (ii) Zn(s) ® Zn2+ + 2e– (oxidation half reaction) (2.3) These reactions occur in two different portions of the Daniell cell. The reduction half reaction occurs on the copper electrode while the oxidation half reaction occurs on the zinc electrode. These two portions of the cell are also called half-cells or redox couples. The copper electrode may be called the reduction half cell and the zinc electrode, the oxidation half-cell. We can construct innumerable number of galvanic cells on the pattern of Daniell cell by taking combinations of different half-cells. Each half- cell consists of a metallic electrode dipped into an electrolyte. The two half-cells are connected by a metallic wire through a voltmeter and a switch externally. The electrolytes of the two half-cells are connected internally through a salt bridge as shown in Fig. 2.1. Sometimes, both the electrodes dip in the same electrolyte solution and in such cases we do not require a salt bridge. At each electrode-electrolyte interface there is a tendency of metal ions from the solution to deposit on the metal electrode trying to make it positively charged. At the same time, metal atoms of the electrode have a tendency to go into the solution as ions and leave behind the electrons at the electrode trying to make it negatively charged. At equilibrium, there is a separation of charges and depending on the tendencies of the two opposing reactions, the electrode may be positively or negatively charged with respect to the solution. A potential difference develops between the electrode and the electrolyte which is called electrode potential. When the concentrations of all the species involved in a half-cell is unity then the electrode potential is known as standard electrode potential. According to IUPAC convention, standard reduction potentials are now called standard electrode potentials. In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative potential with respect to the solution. The other half-cell in which reduction takes place is called cathode and it has a positive potential with respect to the solution. Thus, there exists a potential difference between the two electrodes and as soon as the switch is in the on position the electrons flow from negative electrode to positive electrode. The direction of current flow is opposite to that of electron flow. 33 Electrochemistry Reprint 2025-26 The potential difference between the two electrodes of a galvanic cell is called the cell potential and is measured in volts. The cell potential is the difference between the electrode potentials (reduction potentials) of the cathode and anode. It is called the cell electromotive force (emf) of the cell when no current is drawn through the cell. It is now an accepted convention that we keep the anode on the left and the cathode on the right while representing the galvanic cell. A galvanic cell is generally represented by putting a vertical line between metal and electrolyte solution and putting a double vertical line between the two electrolytes connected by a salt bridge. Under this convention the emf of the cell is positive and is given by the potential of the half- cell on the right hand side minus the potential of the half-cell on the left hand side i.e., Ecell = Eright – Eleft This is illustrated by the following example: Cell reaction: Cu(s) + 2Ag+(aq) ¾® Cu2+(aq) + 2 Ag(s) (2.4) Half-cell reactions: Cathode (reduction): 2Ag+(aq) + 2e– ® 2Ag(s) (2.5) Anode (oxidation): Cu(s) ® Cu2+(aq) + 2e– (2.6) It can be seen that the sum of (3.5) and (3.6) leads to overall reaction (2.4) in the cell and that silver electrode acts as a cathode and copper electrode acts as an anode. The cell can be represented as: Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s) and we have Ecell = Eright – Eleft = EAg+úAg – ECu2+úCu (2.7) 2.2.1 The potential of individual half-cell cannot be measured. We can Measurement measure only the difference between the two half-cell potentials that of Electrode gives the emf of the cell. If we arbitrarily choose the potential of one Potential electrode (half-cell) then that of the other can be determined with respect to this. According to convention, a half-cell called standard hydrogen electrode (Fig.3.3) represented by Pt(s)ú H2(g)ú H+(aq), is assigned a zero potential at all temperatures corresponding to the reaction 1 H+ (aq) + e– ® H2(g) 2 The standard hydrogen electrode consists of a platinum electrode coated with platinum black. The electrode is dipped in an acidic solution and pure hydrogen gas is bubbled through it. The concentration of both the reduced and oxidised forms of hydrogen is maintained at unity (Fig. 2.3). This implies that the pressure of hydrogen gas is one bar and the concentration of hydrogen ion in the Fig. 2.3: Standard Hydrogen Electrode (SHE). solution is one molar. Chemistry 34 Reprint 2025-26 At 298 K the emf of the cell, standard hydrogen electrode ççsecond half-cell constructed by taking standard hydrogen electrode as anode (reference half-cell) and the other half-cell as cathode, gives the reduction potential of the other half-cell. If the concentrations of the oxidised and the reduced forms of the species in the right hand half-cell are unity, then the cell potential is equal to standard electrode potential, Eo R of the given half-cell. Eo = EoR – Eo L As Eo L for standard hydrogen electrode is zero. Eo = Eo R – 0 = EoR The measured emf of the cell: Pt(s) ç H2(g, 1 bar) ç H + (aq, 1 M) çç Cu 2+ (aq, 1 M) ú Cu is 0.34 V and it is also the value for the standard electrode potential of the half-cell corresponding to the reaction: Cu2+ (aq, 1M) + 2 e – ® Cu(s) Similarly, the measured emf of the cell: Pt(s) ç H2(g, 1 bar) ç H+ (aq, 1 M) çç Zn2+ (aq, 1M) ç Zn is -0.76 V corresponding to the standard electrode potential of the half-cell reaction: Zn2+ (aq, 1 M) + 2e– ® Zn(s) The positive value of the standard electrode potential in the first case indicates that Cu2+ ions get reduced more easily than H+ ions. The reverse process cannot occur, that is, hydrogen ions cannot oxidise Cu (or alternatively we can say that hydrogen gas can reduce copper ion) under the standard conditions described above. Thus, Cu does not dissolve in HCl. In nitric acid it is oxidised by nitrate ion and not by hydrogen ion. The negative value of the standard electrode potential in the second case indicates that hydrogen ions can oxidise zinc (or zinc can reduce hydrogen ions). In view of this convention, the half reaction for the Daniell cell in Fig. 2.1 can be written as: Left electrode: Zn(s) ® Zn 2+ (aq, 1 M) + 2 e – Right electrode: Cu 2+ (aq, 1 M) + 2 e – ® Cu(s) The overall reaction of the cell is the sum of above two reactions and we obtain the equation: Zn(s) + Cu 2+ (aq) ® Zn2+ (aq) + Cu(s) emf of the cell = Eocell = Eo R – Eo L = 0.34V – (– 0.76)V = 1.10 V Sometimes metals like platinum or gold are used as inert electrodes. They do not participate in the reaction but provide their surface for oxidation or reduction reactions and for the conduction of electrons. For example, Pt is used in the following half-cells: Hydrogen electrode: Pt(s)|H2(g)| H+(aq) With half-cell reaction: H+ (aq)+ e– ® ½ H2(g) Bromine electrode: Pt(s)|Br2(aq)| Br–(aq) 35 Electrochemistry Reprint 2025-26 With half-cell reaction: ½ Br2(aq) + e– ® Br–(aq) The standard electrode potentials are very important and we can extract a lot of useful information from them. The values of standard electrode potentials for some selected half-cell reduction reactions are given in Table 2.1. If the standard electrode potential of an electrode is greater than zero then its reduced form is more stable compared to hydrogen gas. Similarly, if the standard electrode potential is negative then hydrogen gas is more stable than the reduced form of the species. It can be seen that the standard electrode potential for fluorine is the highest in the Table indicating that fluorine gas (F2) has the maximum tendency to get reduced to fluoride ions (F–) and therefore fluorine gas is the strongest oxidising agent and fluoride ion is the weakest reducing agent. Lithium has the lowest electrode potential indicating that lithium ion is the weakest oxidising agent while lithium metal is the most powerful reducing agent in an aqueous solution. It may be seen that as we go from top to bottom in Table 2.1 the standard electrode potential decreases and with this, decreases the oxidising power of the species on the left and increases the reducing power of the species on the right hand side of the reaction. Electrochemical cells are extensively used for determining the pH of solutions, solubility product, equilibrium constant and other thermodynamic properties and for potentiometric titrations. IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.1 How would you determine the standard electrode potential of the system Mg2+|Mg? 2.2 Can you store copper sulphate solutions in a zinc pot? 2.3 Consult the table of standard electrode potentials and suggest three substances that can oxidise ferrous ions under suitable conditions. 2.32.32.32.32.3 NernstNernstNernstNernstNernst We have assumed in the previous section that the concentration of all EquationEquationEquationEquationEquation the species involved in the electrode reaction is unity. This need not be always true. Nernst showed that for the electrode reaction: Mn+(aq) + ne–® M(s) the electrode potential at any concentration measured with respect to standard hydrogen electrode can be represented by: RT o [M] E = E ln ( M n + / M ) ( M n + / M ) – nF [M n+ ] but concentration of solid M is taken as unity and we have o RT 1 E = E (2.8) ( M n + / M ) ( M n + /M ) – nF ln [M n+ ] o E ( M n + / M ) has already been defined, R is gas constant (8.314 JK–1 mol–1), F is Faraday constant (96487 C mol–1), T is temperature in kelvin and [Mn+] is the concentration of the species, Mn+. Chemistry 36 Reprint 2025-26 Table 2.1: Standard Electrode Potentials at 298 K Ions are present as aqueous species and H2O as liquid; gases and solids are shown by g and s. Reaction (Oxidised form + ne– ® Reduced form) E o/V ® 2F– 2.87 F2(g) + 2e– Co3+ + e– ® Co2+ 1.81 H2O2 + 2H+ + 2e– ® 2H2O 1.78 MnO4– + 8H+ + 5e– ® Mn2+ + 4H2O 1.51 Au3+ + 3e– ® Au(s) 1.40 Cl2(g) + 2e– ® 2Cl– 1.36 Cr2O72– + 14H+ + 6e– ® 2Cr3+ + 7H2O 1.33 O2(g) + 4H+ + 4e– ® 2H2O 1.23 MnO2(s) + 4H+ + 2e– ® Mn2+ + 2H2O 1.23 Br2 + 2e– ® 2Br– 1.09 NO3– + 4H+ + 3e– ® NO(g) + 2H2O 0.97 2Hg2+ + 2e– ® Hg22+ 0.92 Ag+ + e– ® Ag(s) 0.80 agent agent Fe3+ + e– ® Fe2+ 0.77 O2(g) + 2H+ + 2e– ® H2O2 0.68 I2 + 2e– ® 2I– 0.54 oxidising reducing 0.52 of Cu+ + e– ® Cu(s) of Cu2+ + 2e– ® Cu(s) 0.34 AgCl(s) + e– ® Ag(s) + Cl– 0.22 strength AgBr(s) + e– ® Ag(s) + Br– strength 0.10 2H+ + 2e– ® H2(g) 0.00 Pb2+ + 2e– ® Pb(s) –0.13 Sn2+ + 2e– ® Sn(s) –0.14 Increasing Increasing Ni2+ + 2e– ® Ni(s) –0.25 Fe2+ + 2e– ® Fe(s) –0.44 Cr3+ + 3e– ® Cr(s) –0.74 Zn2+ + 2e– ® Zn(s) –0.76 2H2O + 2e– ® H2(g) + 2OH–(aq) –0.83 Al3+ + 3e– ® Al(s) –1.66 Mg2+ + 2e– ® Mg(s) –2.36 Na+ + e– ® Na(s) –2.71 Ca2+ + 2e– ® Ca(s) –2.87 K+ + e– ® K(s) –2.93 Li+ + e– ® Li(s) –3.05 1. A negative Eo means that the redox couple is a stronger reducing agent than the H+/H2 couple. 2. A positive Eo means that the redox couple is a weaker reducing agent than the H+/H2 couple. 37 Electrochemistry Reprint 2025-26 In Daniell cell, the electrode potential for any given concentration of Cu2+ and Zn2+ ions, we write For Cathode: E E o RT 1 (2.9)  Cu 2  /Cu  = (Cu 2 + /Cu ) – 2F ln   Cu 2   aq   For Anode: E E o RT 1 (2.10)  Zn 2  /Zn  = ( Zn 2 + / Zn ) – 2F ln   Zn 2   aq   E E 2  2  /Zn  The cell potential, E(cell) =  Cu /Cu  –  Zn o RT 1 E o RT 1 E = (Cu – ( Zn 2 + / Cu ) – 2 F ln 2 + / Zn ) + 2 F ln    Zn 2+ (aq)   Cu 2+ (aq) E o E o RT 1 1 – ln = (Cu 2 + / Cu ) – ( Zn 2 + / Zn ) – 2F ln    Cu 2+  aq    Zn 2+  aq   2  ] RT [ Zn o E(cell) = E ( cell ) – 2 F ln 2 + (2.11) [Cu ] It can be seen that E(cell) depends on the concentration of both Cu2+ and Zn2+ ions. It increases with increase in the concentration of Cu2+ ions and decrease in the concentration of Zn2+ ions. By converting the natural logarithm in Eq. (2.11) to the base 10 and substituting the values of R, F and T = 298 K, it reduces to 2 + ] 0 .059 [ Zn (2.12) 2 + ] E(cell) = E (ocell ) – 2 log [Cu We should use the same number of electrons (n) for both the electrodes and thus for the following cell Ni(s)ú Ni2+(aq) úú Ag+(aq)ú Ag The cell reaction is Ni(s) + 2Ag+(aq) ® Ni2+(aq) + 2Ag(s) The Nernst equation can be written as RT [Ni 2+ ] o + E(cell) = E ( cell ) – 2F ln [Ag ]2 and for a general electrochemical reaction of the type: a A + bB ne– cC + dD Nernst equation can be written as: RT E(cell) = E (ocell ) – nF 1nQ RT [C]c [D]d o (2.13) = E ( cell ) – nF ln [A] a [B]b Chemistry 38 Reprint 2025-26 Represent the cell in which the following reaction takes place ExampleExampleExampleExampleExample 2.12.12.12.12.1 Mg(s) + 2Ag+(0.0001M) ® Mg2+(0.130M) + 2Ag(s) Calculate its E(cell) if E (ocell ) = 3.17 V. The cell can be written as Mgú Mg2+(0.130M)úú Ag+(0.0001M)ú Ag SolutionSolutionSolutionSolutionSolution 2 + Mg RT o E = E ln (  cell  cell ) – 2F + 2 Ag 0 .059V 0.130 = 3.17 V – log 2 = 3.17 V – 0.21V = 2.96 V. 2 ( 0 . 0001) 2.3.1 Equilibrium If the circuit in Daniell cell (Fig. 2.1) is closed then we note that the reaction Constant Zn(s) + Cu2+(aq) ® Zn2+(aq) + Cu(s) (2.1) from Nernst takes place and as time passes, the concentration of Zn2+ keeps Equation on increasing while the concentration of Cu2+ keeps on decreasing. At the same time voltage of the cell as read on the voltmeter keeps on decreasing. After some time, we shall note that there is no change in the concentration of Cu2+ and Zn2+ ions and at the same time, voltmeter gives zero reading. This indicates that equilibrium has been attained. In this situation the Nernst equation may be written as: o 2.303 RT [Zn 2 + ] 2 + E(cell) = 0 = E ( cell ) – 2 F log [Cu ] o 2.303 RT [Zn 2  ] or E ( cell ) = log 2  2 F [Cu ] But at equilibrium, [ Zn 2 + ] = Kc for the reaction 2.1 [Cu2 + ] and at T = 298K the above equation can be written as o 0. 059 V o E ( cell ) = log KC = 1.1 V ( E ( cell ) = 1.1V) 2 (1.1V × 2) log KC =  37.288 0.059 V KC = 2 × 1037 at 298K. In general, o 2.303RT E ( cell ) = log KC (2.14) nF Thus, Eq. (2.14) gives a relationship between equilibrium constant of the reaction and standard potential of the cell in which that reaction takes place. Thus, equilibrium constants of the reaction, difficult to measure otherwise, can be calculated from the corresponding Eo value of the cell. 39 Electrochemistry Reprint 2025-26 ExampleExampleExampleExampleExample 2.22.22.22.22.2 Calculate the equilibrium constant of the reaction: Cu(s) + 2Ag+(aq) ® Cu2+(aq) + 2Ag(s) Eo( cell ) = 0.46 V o 0. 059 V SolutionSolutionSolutionSolutionSolution E ( cell ) = log KC = 0.46 V or 2 0 .46 V × 2 = 15.6 log KC = 0 .059 V KC = 3.92 × 1015 2.3.2 Electro- Electrical work done in one second is equal to electrical potential chemical multiplied by total charge passed. If we want to obtain maximum work Cell and from a galvanic cell then charge has to be passed reversibly. The Gibbs reversible work done by a galvanic cell is equal to decrease in its Gibbs Energy of energy and therefore, if the emf of the cell is E and nF is the amount the Reaction of charge passed and DrG is the Gibbs energy of the reaction, then DrG = – nFE(cell) (2.15) It may be remembered that E(cell) is an intensive parameter but DrG is an extensive thermodynamic property and the value depends on n. Thus, if we write the reaction Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s) (2.1) DrG = – 2FE(cell) but when we write the reaction 2 Zn (s) + 2 Cu2+(aq) ¾®2 Zn2+(aq) + 2Cu(s) DrG = – 4FE(cell) If the concentration of all the reacting species is unity, then E(cell) = E (ocell ) and we have DrGo = – nF E(cell)o (2.16) Thus, from the measurement of E (ocell ) we can obtain an important thermodynamic quantity, DrGo, standard Gibbs energy of the reaction. From the latter we can calculate equilibrium constant by the equation: DrGo = –RT ln K. ExampleExampleExampleExampleExample 2.32.32.32.32.3 The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s) SolutionSolutionSolutionSolutionSolution DrGo = – nF E(cell)o n in the above equation is 2, F = 96487 C mol–1 and E o( cell ) = 1.1 V Therefore, DrGo = – 2 × 1.1V × 96487 C mol–1 = – 21227 J mol–1 = – 212.27 kJ mol–1 Chemistry 40 Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.4 Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10. 2.5 Calculate the emf of the cell in which the following reaction takes place: Ni(s) + 2Ag+ (0.002 M) ® Ni2+ (0.160 M) + 2Ag(s) Given that Ecello = 1.05 V 2.6 The cell in which the following reaction occurs: E o = 0.236 V at 298 K. 2Fe 3 + ( aq ) + 2I − ( aq ) → 2Fe 2 + ( aq ) + I 2 ( s ) has cell Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction. 2.42.42.42.42.4 ConductanceConductanceConductanceConductanceConductance It is necessary to define a few terms before we consider the subject of ofofofofof ElectrolyticElectrolyticElectrolyticElectrolyticElectrolytic conductance of electricity through electrolytic solutions. The electrical resistance is represented by the symbol ‘R’ and it is measured in ohm (W) SolutionsSolutionsSolutionsSolutionsSolutions which in terms of SI base units is equal to (kg m2)/(S3 A2). It can be measured with the help of a Wheatstone bridge with which you are familiar from your study of physics. The electrical resistance of any object is directly proportional to its length, l, and inversely proportional to its area of cross section, A. That is, l l R µ or R = r (2.17) A A The constant of proportionality, r (Greek, rho), is called resistivity (specific resistance). Its SI units are ohm metre (W m) and quite often its submultiple, ohm centimetre (W cm) is also used. IUPAC recommends the use of the term resistivity over specific resistance and hence in the rest of the book we shall use the term resistivity. Physically, the resistivity for a substance is its resistance when it is one metre long and its area of cross section is one m2. It can be seen that: 1 W m = 100 W cm or 1 W cm = 0.01 W m The inverse of resistance, R, is called conductance, G, and we have the relation: 1 A A G = = = κ (2.18) R ρ l l The SI unit of conductance is siemens, represented by the symbol ‘S’ and is equal to ohm–1 (also known as mho) or W–1. The inverse of resistivity, called conductivity (specific conductance) is represented by the symbol, k (Greek, kappa). IUPAC has recommended the use of term conductivity over specific conductance and hence we shall use the term conductivity in the rest of the book. The SI units of conductivity are S m–1 but quite often, k is expressed in S cm–1. Conductivity of a material in S m–1 is its conductance when it is 1 m long and its area of cross section is 1 m2. It may be noted that 1 S cm–1 = 100 S m–1. 41 Electrochemistry Reprint 2025-26 Table 2.2: The values of Conductivity of some Selected Materials at 298.15 K Material Conductivity/ Material Conductivity/ S m–1 S m–1 Conductors Aqueous Solutions Sodium 2.1×103 Pure water 3.5×10–5 Copper 5.9×103 0.1 M HCl 3.91 Silver 6.2×103 0.01M KCl 0.14 Gold 4.5×103 0.01M NaCl 0.12 Iron 1.0×103 0.1 M HAc 0.047 Graphite 1.2×10 0.01M HAc 0.016 Insulators Semiconductors Glass 1.0×10–16 CuO 1×10–7 Teflon 1.0×10–18 Si 1.5×10–2 Ge 2.0 It can be seen from Table 2.2 that the magnitude of conductivity varies a great deal and depends on the nature of the material. It also depends on the temperature and pressure at which the measurements are made. Materials are classified into conductors, insulators and semiconductors depending on the magnitude of their conductivity. Metals and their alloys have very large conductivity and are known as conductors. Certain non-metals like carbon-black, graphite and some organic polymers* are also electronically conducting. Substances like glass, ceramics, etc., having very low conductivity are known as insulators. Substances like silicon, doped silicon and gallium arsenide having conductivity between conductors and insulators are called semiconductors and are important electronic materials. Certain materials called superconductors by definition have zero resistivity or infinite conductivity. Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were known to behave as superconductors, but nowadays a number of ceramic materials and mixed oxides are also known to show superconductivity at temperatures as high as 150 K. Electrical conductance through metals is called metallic or electronic conductance and is due to the movement of electrons. The electronic conductance depends on (i) the nature and structure of the metal (ii) the number of valence electrons per atom (iii) temperature (it decreases with increase of temperature). * Electronically conducting polymers – In 1977 MacDiarmid, Heeger and Shirakawa discovered that acetylene gas can be polymerised to produce a polymer, polyacetylene when exposed to vapours of iodine acquires metallic lustre and conductivity. Since then several organic conducting polymers have been made such as polyaniline, polypyrrole and polythiophene. These organic polymers which have properties like metals, being composed wholly of elements like carbon, hydrogen and occasionally nitrogen, oxygen or sulphur, are much lighter than normal metals and can be used for making light-weight batteries. Besides, they have the mechanical properties of polymers such as flexibility so that one can make electronic devices such as transistors that can bend like a sheet of plastic. For the discovery of conducting polymers, MacDiarmid, Heeger and Shirakawa were awarded the Nobel Prize in Chemistry for the year 2000. Chemistry 42 Reprint 2025-26 As the electrons enter at one end and go out through the other end, the composition of the metallic conductor remains unchanged. The mechanism of conductance through semiconductors is more complex. We already know that even very pure water has small amounts of hydrogen and hydroxyl ions (~10–7M) which lend it very low conductivity (3.5 × 10–5 S m–1). When electrolytes are dissolved in water, they furnish their own ions in the solution hence its conductivity also increases. The conductance of electricity by ions present in the solutions is called electrolytic or ionic conductance. The conductivity of electrolytic (ionic) solutions depends on: (i) the nature of the electrolyte added (ii) size of the ions produced and their solvation (iii) the nature of the solvent and its viscosity (iv) concentration of the electrolyte (v) temperature (it increases with the increase of temperature). Passage of direct current through ionic solution over a prolonged period can lead to change in its composition due to electrochemical reactions (Section 2.4.1). 2.4.1 Measurement We know that accurate measurement of an unknown resistance can be of the performed on a Wheatstone bridge. However, for measuring the resistance Conductivity of an ionic solution we face two problems. Firstly, passing direct current of Ionic (DC) changes the composition of the solution. Secondly, a solution cannot Solutions be connected to the bridge like a metallic wire or other solid conductor. The first difficulty is resolved by using an alternating current (AC) source of power. The second problem is solved by using a specially designed vessel called conductivity cell. It is available in several designs and two simple ones are shown in Fig. 2.4. Connecting Connecting wires wires Platinized Pt Fig. 2.4 electrodes Two different types of conductivity cells. Platinized Pt electrode Platinized Pt electrode Basically it consists of two platinum electrodes coated with platinum black (finely divided metallic Pt is deposited on the electrodes electrochemically). These have area of cross section equal to ‘A’ and are separated by distance ‘l’. Therefore, solution confined between these electrodes is a column of length l and area of cross section A. The resistance of such a column of solution is then given by the equation: l l R = r = (2.17) A A 43 Electrochemistry Reprint 2025-26 The quantity l/A is called cell constant denoted by the symbol, G*. It depends on the distance between the electrodes and their area of cross-section and has the dimension of length–1 and can be calculated if we know l and A. Measurement of l and A is not only inconvenient but also unreliable. The cell constant is usually determined by measuring the resistance of the cell containing a solution whose conductivity is already known. For this purpose, we generally use KCl solutions whose conductivity is known accurately at various concentrations (Table 2.3) and at different temperatures. The cell constant, G*, is then given by the equation: l G* = = R k (2.18) A Table 2.3: Conductivity and Molar conductivity of KCl solutions at 298.15K Concentration/Molarity Conductivity Molar Conductivity mol L–1 mol m–3 S cm–1 S m–1 S cm2mol–1 S m2 mol–1 1.000 1000 0.1113 11.13 111.3 111.3×10–4 0.100 100.0 0.0129 1.29 129.0 129.0×10–4 0.010 10.00 0.00141 0.141 141.0 141.0×10–4 Once the cell constant is determined, we can use it for measuring the resistance or conductivity of any solution. The set up for the measurement of the resistance is shown in Fig. 2.5. It consists of two resistances R3 and R4, a variable resistance R1 and the conductivity cell having the unknown resistance R2. The Wheatstone bridge is fed by an oscillator O (a source of a.c. power in the audio frequency range 550 to 5000 cycles per second). P is a suitable detector (a headphone or other electronic device) and the bridge is balanced when no current passes through the detector. Under these conditions: Fig. 2.5: Arrangement for measurement of R 1 R 4 resistance of a solution of an Unknown resistance R2 = (2.19) R 3 electrolyte. These days, inexpensive conductivity meters are available which can directly read the conductance or resistance of the solution in the conductivity cell. Once the cell constant and the resistance of the solution in the cell is determined, the conductivity of the solution is given by the equation: cell constant G*   (2.20) R R The conductivity of solutions of different electrolytes in the same solvent and at a given temperature differs due to charge and size of the Chemistry 44 Reprint 2025-26 ions in which they dissociate, the concentration of ions or ease with which the ions move under a potential gradient. It, therefore, becomes necessary to define a physically more meaningful quantity called molar conductivity denoted by the symbol Lm (Greek, lambda). It is related to the conductivity of the solution by the equation:  Molar conductivity = Lm = (2.21) c In the above equation, if k is expressed in S m–1 and the concentration, c in mol m–3 then the units of Lm are in S m2 mol–1. It may be noted that: 1 mol m–3 = 1000(L/m3) × molarity (mol/L), and hence  (S cm  1 ) Lm(S cm2 mol–1) =  3 1 1000 L m × molarity (mol L ) If we use S cm–1 as the units for k and mol cm–3, the units of concentration, then the units for Lm are S cm2 mol–1. It can be calculated by using the equation:  (S cm 1 ) × 1000 (cm 3 /L) Lm (S cm2 mol–1) = molarity (mol/L) Both type of units are used in literature and are related to each other by the equations: 1 S m2mol–1 = 104 S cm2mol–1 or 1 S cm2mol–1 = 10–4 S m2mol–1. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is ExampleExampleExampleExampleExample 2.42.42.42.42.4 100 W . If the resistance of the same cell when filled with 0.02 mol L–1 KCl solution is 520 W , calculate the conductivity and molar conductivity of 0.02 mol L–1 KCl solution. The conductivity of 0.1 mol L–1 KCl solution is 1.29 S/m. SolutionSolutionSolutionSolutionSolution The cell constant is given by the equation: Cell constant = G* = conductivity × resistance = 1.29 S/m × 100 W = 129 m–1 = 1.29 cm–1 Conductivity of 0.02 mol L–1 KCl solution = cell constant / resistance G * 129 m –1 = = = 0.248 S m–1 R 520  Concentration = 0.02 mol L–1 = 1000 × 0.02 mol m–3 = 20 mol m–3  Molar conductivity = m  c 248 × 10 –3 S m –1 = –3 = 124 × 10–4 S m2mol–1 20 mol m 1.29 cm –1 Alternatively, k = = 0.248 × 10–2 S cm–1 520  45 Electrochemistry Reprint 2025-26 and Lm = k × 1000 cm3 L–1 molarity–1 0.248×10 –2 S cm –1 ×1000 cm 3 L–1 = –1 0.02 mol L = 124 S cm2 mol–1 ExampleExampleExampleExampleExample 2.52.52.52.52.5 The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1 cm and length 50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity. SolutionSolutionSolutionSolutionSolution A = p r2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2 l = 50 cm = 0.5 m  l RA 5.55  10 3  0.785cm 2 R = or    = 87.135 W cm A l 50cm 1  1  Conductivity =  = =   S cm–1   87.135  = 0.01148 S cm–1  × 1000 Molar conductivity, m = cm3 L–1 c 0.01148 S cm –1 ×1000 cm 3 L–1 = –1 0.05 mol L = 229.6 S cm2 mol–1 If we want to calculate the values of different quantities in terms of ‘m’ instead of ‘cm’, RA = l 5.55 × 10 3  × 0.785×10 –4 m 2 = = 87.135 ×10–2 W m 0.5 m 1 100  =  m = 1.148 S m–1 = 87.135  1.148 S m –1 and m = = –3 = 229.6 × 10–4 S m2 mol–1. c 50 mol m 2.4.2 Variation of Both conductivity and molar conductivity change with the Conductivity concentration of the electrolyte. Conductivity always decreases with and Molar decrease in concentration both, for weak and strong electrolytes. Conductivity This can be explained by the fact that the number of ions per unit with volume that carry the current in a solution decreases on dilution. Concentration The conductivity of a solution at any given concentration is the conductance of one unit volume of solution kept between two Chemistry 46 Reprint 2025-26 platinum electrodes with unit area of cross section and at a distance of unit length. This is clear from the equation: A G = =  (both A and l are unity in their appropriate units in l m or cm) Molar conductivity of a solution at a given concentration is the conductance of the volume V of solution containing one mole of electrolyte kept between two electrodes with area of cross section A and distance of unit length. Therefore, κA Λm = =κ l Since l = 1 and A = V ( volume containing 1 mole of electrolyte) Lm = k V (2.22) Molar conductivity increases with decrease in concentration. This is because the total volume, V, of solution containing one mole of electrolyte also increases. It has been found that decrease in k on dilution of a solution is more than compensated by increase in its volume. Physically, it means that at a given concentration, Lm can be defined as the conductance of the electrolytic solution kept between the electrodes of a conductivity cell at unit distance but having area of cross section large enough to accommodate sufficient volume of solution that contains one mole of the electrolyte. When concentration approaches zero, the molar conductivity is known as limiting molar conductivity and is represented by theFig. 2.6: Molar conductivity versus c½ for acetic acid (weak electrolyte) and potassium symbol L°m . The variation in Lm with chloride (strong electrolyte) in aqueous concentration is different (Fig. 2.6) for solutions. strong and weak electrolytes. Strong Electrolytes For strong electrolytes, Lm increases slowly with dilution and can be represented by the equation: Lm = L°m – A c ½ (2.23) It can be seen that if we plot (Fig. 2.6) Lm against c1/2, we obtain a straight line with intercept equal to L°m and slope equal to ‘–A’. The value of the constant ‘A’ for a given solvent and temperature depends on the type of electrolyte i.e., the charges on the cation and anion produced on the dissociation of the electrolyte in the solution. Thus, NaCl, CaCl2, MgSO4 are known as 1-1, 2-1 and 2-2 electrolytes respectively. All electrolytes of a particular type have the same value for ‘A’. 47 Electrochemistry Reprint 2025-26 ExampleExampleExampleExampleExample 2.62.62.62.62.6 The molar conductivity of KCl solutions at different concentrations at 298 K are given below: c/mol L–1 Lm/S cm2 mol–1 0.000198 148.61 0.000309 148.29 0.000521 147.81 0.000989 147.09 Show that a plot between Lm and c1/2 is a straight line. Determine the values of L°m and A for KCl. SolutionSolutionSolutionSolutionSolution Taking the square root of concentration we obtain: c1/2/(mol L–1 )1/2 Lm/S cm2mol–1 0.01407 148.61 0.01758 148.29 0.02283 147.81 0.03145 147.09 A plot of Lm ( y-axis) and c1/2 (x-axis) is shown in (Fig. 3.7). It can be seen that it is nearly a straight line. From the intercept (c1/2 = 0), we find that L°m = 150.0 S cm2 mol–1 and A = – slope = 87.46 S cm2 mol–1/(mol/L–1)1/2. Fig. 2.7: Variation of Lm against c½. Chemistry 48 Reprint 2025-26 Kohlrausch examined L°m values for a number of strong electrolytes and observed certain regularities. He noted that the difference in L°m of the electrolytes NaX and KX for any X is nearly constant. For example at 298 K: m L°m (KCl) – L°m (NaCl) = L°m (KBr) – L° (NaBr) = L°m (KI) – L°m (NaI) ≃ 23.4 S cm2 mol–1 and similarly it was found that L°m (NaBr)– L°m (NaCl) = L°m (KBr) – L°m (KCl) ≃ 1.8 S cm2 mol–1 On the basis of the above observations he enunciated Kohlrausch law of independent migration of ions. The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the anion and cation of the electrolyte. Thus, – are limiting molar conductivity of the sodium and chlorideif l°Na+ and l°Cl ions respectively, then the limiting molar conductivity for sodium chloride is given by the equation: l° l° L°m – (2.24) (NaCl) = Na+ + Cl In general, if an electrolyte on dissociation gives n+ cations and n– anions then its limiting molar conductivity is given by: L°m = n+ l°+ + n– l°– (2.25) Here, l°+ and l°– are the limiting molar conductivities of the cation and anion respectively. The values of l° for some cations and anions at 298 K are given in Table 2.4. Table 2.4: Limiting Molar Conductivity for some Ions in Water at 298 K Ion l0/(S cm2mol–1) Ion l 0/(S cm2 mol–1) H+ 349.6 OH– 199.1 Na+ 50.1 Cl– 76.3 K+ 73.5 Br– 78.1 Ca2+ 119.0 CH3COO– 40.9 2 Mg2+ 106.0 SO4 160.0 Weak Electrolytes Weak electrolytes like acetic acid have lower degree of dissociation at higher concentrations and hence for such electrolytes, the change in Lm with dilution is due to increase in the degree of dissociation and consequently the number of ions in total volume of solution that contains 1 mol of electrolyte. In such cases Lm increases steeply (Fig. 2.6) on dilution, especially near lower concentrations. Therefore, L°m cannot be obtained by extrapolation of Lm to zero concentration. At infinite dilution (i.e., concentration c ® zero) electrolyte dissociates completely (a =1), but at such low concentration the conductivity of the solution is so low that it cannot be measured accurately. Therefore, L°m for weak electrolytes is obtained by using Kohlrausch law of independent migration of ions (Example 2.8). At any concentration c, if a is the degree of dissociation 49 Electrochemistry Reprint 2025-26 then it can be approximated to the ratio of molar conductivity Lm at the concentration c to limiting molar conductivity, L0m . Thus we have: m  = ° (2.26) m But we know that for a weak electrolyte like acetic acid (Class XI, Unit 7), c  2 cm2 c m2 K = = =   a 1   m m  m   m  (2.27) m 2 1     m  Applications of Kohlrausch law Using Kohlrausch law of independent migration of ions, it is possible to calculate L0m for any electrolyte from the lo of individual ions. Moreover, for weak electrolytes like acetic acid it is possible to determine the value of its dissociation constant once we know the L0m and Lm at a given concentration c. ExampleExampleExampleExampleExample 2.72.72.72.72.7 Calculate L0m for CaCl2 and MgSO4 from the data given in Table 3.4. SolutionSolutionSolutionSolutionSolution We know from Kohlrausch law that – = 119.0 S cm2 mol–1 + 2(76.3) S cm2 mol–1 m  CaCl 2  = Ca 2+  2 Cl = (119.0 + 152.6) S cm2 mol–1 = 271.6 S cm2 mol–1 2+  m  MgSO 4  = Mg  SO 2–4 = 106.0 S cm2 mol–1 + 160.0 S cm2 mol–1 = 266 S cm2 mol–1 . ExampleExampleExampleExampleExample 2.82.82.82.82.8 L0m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol–1 respectively. Calculate L0 for HAc.       +  Ac – H + Cl – Ac – Na + Cl – Na + SolutionSolutionSolutionSolutionSolution m  HAc  = H = m  HCl   m  NaAc   m  NaCl  = (425.9 + 91.0 – 126.4 ) S cm2 mol –1 = 390.5 S cm2 mol–1 . ExampleExampleExampleExampleExample 2.92.92.92.92.9 The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 S cm–1. Calculate its dissociation constant if L0m for acetic acid is 390.5 S cm2 mol–1.  4 . 95 10  5 Scm  1 1000cm 3 SolutionSolutionSolutionSolutionSolution m =  1  = 48.15 S cm3 mol–1 c 0 . 001028 mol L L m 48.15 Scm 2 mol 1 a =   2  1 = 0.1233 m 390.5 Scm mol c2 0 .001028molL–1  (0 .1233) 2 k = = 1.78 × 10–5 mol L–1  1   1  0 .1233 Chemistry 50 Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.7 Why does the conductivity of a solution decrease with dilution? 2.8 Suggest a way to determine the L°m value of water. 2.9 The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2 mol–1. Calculate its degree of dissociation and dissociation constant. Given l0(H+) = 349.6 S cm2 mol–1 and l0 (HCOO–) = 54.6 S cm2 mol–1. 2.52.52.52.52.5 ElectrolyticElectrolyticElectrolyticElectrolyticElectrolytic In an electrolytic cell external source of voltage is used to bring about a chemical reaction. The electrochemical processes are of great importance CellsCellsCellsCellsCells andandandandand in the laboratory and the chemical industry. One of the simplest electrolytic ElectrolysisElectrolysisElectrolysisElectrolysisElectrolysis cell consists of two copper strips dipping in an aqueous solution of copper sulphate. If a DC voltage is applied to the two electrodes, then Cu 2+ ions discharge at the cathode (negatively charged) and the following reaction takes place: Cu2+(aq) + 2e– ® Cu (s) (2.28) Copper metal is deposited on the cathode. At the anode, copper is converted into Cu2+ ions by the reaction: Cu(s) ® Cu2+(s) + 2e– (2.29) Thus copper is dissolved (oxidised) at anode and deposited (reduced) at cathode. This is the basis for an industrial process in which impure copper is converted into copper of high purity. The impure copper is made an anode that dissolves on passing current and pure copper is deposited at the cathode. Many metals like Na, Mg, Al, etc. are produced on large scale by electrochemical reduction of their respective cations where no suitable chemical reducing agents are available for this purpose. Sodium and magnesium metals are produced by the electrolysis of their fused chlorides and aluminium is produced by electrolysis of aluminium oxide in presence of cryolite. Quantitative Aspects of Electrolysis Michael Faraday was the first scientist who described the quantitative aspects of electrolysis. Now Faraday’s laws also flow from what has been discussed earlier. Faraday’s Laws of Electrolysis After his extensive investigations on electrolysis of solutions and melts of electrolytes, Faraday published his results during 1833-34 in the form of the following well known Faraday’s two laws of electrolysis: (i) First Law: The amount of chemical reaction which occurs at any electrode during electrolysis by a current is proportional to the quantity of electricity passed through the electrolyte (solution or melt). (ii) Second Law: The amounts of different substances liberated by the same quantity of electricity passing through the electrolytic solution are proportional to their chemical equivalent weights (Atomic Mass of Metal ÷ Number of electrons required to reduce the cation). 51 Electrochemistry Reprint 2025-26 There were no constant current sources available during Faraday’s times. The general practice was to put a coulometer (a standard electrolytic cell) for determining the quantity of electricity passed from the amount of metal (generally silver or copper) deposited or consumed. However, coulometers are now obsolete and we now have constant current (I) sources available and the quantity of electricity Q, passed is given by Q = It Q is in coloumbs when I is in ampere and t is in second. The amount of electricity (or charge) required for oxidation or reduction depends on the stoichiometry of the electrode reaction. For example, in the reaction: Ag +(aq) + e– ® Ag(s) (2.30) One mole of the electron is required for the reduction of one mole of silver ions. We know that charge on one electron is equal to 1.6021 × 10–19C. Therefore, the charge on one mole of electrons is equal to: NA × 1.6021 × 10–19 C = 6.02 × 1023 mol–1 × 1.6021 × 10–19 C = 96487 C mol–1 This quantity of electricity is called Faraday and is represented by the symbol F. For approximate calculations we use 1F ≃ 96500 C mol–1. For the electrode reactions: Mg2+(l) + 2e– ¾® Mg(s) (2.31) Al3+(l) + 3e– ¾® Al(s) (2.32) It is obvious that one mole of Mg2+ and Al3+ require 2 mol of electrons (2F) and 3 mol of electrons (3F) respectively. The charge passed through the electrolytic cell during electrolysis is equal to the product of current in amperes and time in seconds. In commercial production of metals, current as high as 50,000 amperes are used that amounts to about 0.518 F per second. ExampleExampleExampleExampleExample 2.102.102.102.102.10 A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the mass of copper deposited at the cathode? SolutionSolutionSolutionSolutionSolution t = 600 s charge = current × time = 1.5 A × 600 s = 900 C According to the reaction: Cu2+(aq) + 2e– = Cu(s) We require 2F or 2 × 96487 C to deposit 1 mol or 63 g of Cu. For 900 C, the mass of Cu deposited = (63 g mol–1 × 900 C)/(2 × 96487 C mol–1) = 0.2938 g. 2.5.1 Products of Products of electrolysis depend on the nature of material being Electrolysis electrolysed and the type of electrodes being used. If the electrode is inert (e.g., platinum or gold), it does not participate in the chemical reaction and acts only as source or sink for electrons. On the other hand, if the electrode is reactive, it participates in the electrode reaction. Thus, the products of electrolysis may be different for reactive and inert Chemistry 52 Reprint 2025-26 electrodes.The products of electrolysis depend on the different oxidising and reducing species present in the electrolytic cell and their standard electrode potentials. Moreover, some of the electrochemical processes although feasible, are so slow kinetically that at lower voltages these do not seem to take place and extra potential (called overpotential) has to be applied, which makes such process more difficult to occur. For example, if we use molten NaCl, the products of electrolysis are sodium metal and Cl2 gas. Here we have only one cation (Na+) which is reduced at the cathode (Na+ + e– ® Na) and one anion (Cl–) which is oxidised at the anode (Cl– ® ½Cl2 + e– ). During the electrolysis of aqueous sodium chloride solution, the products are NaOH, Cl2 and H2. In this case besides Na+ and Cl– ions we also have H+ and OH– ions along with the solvent molecules, H2O. At the cathode there is competition between the following reduction reactions: Na+ (aq) + e– ® Na (s) E (ocell ) = – 2.71 V H+ (aq) + e– ® ½ H2 (g) E (ocell ) = 0.00 V The reaction with higher value of Eo is preferred and therefore, the reaction at the cathode during electrolysis is: H+ (aq) + e– ® ½ H2 (g) (2.33) but H+ (aq) is produced by the dissociation of H2O, i.e., H2O (l ) ® H+ (aq) + OH– (aq) (2.34) Therefore, the net reaction at the cathode may be written as the sum of (2.33) and (2.34) and we have H2O (l ) + e– ® ½H2(g) + OH– (2.35) At the anode the following oxidation reactions are possible: Cl– (aq) ® ½ Cl2 (g) + e– E (ocell ) = 1.36 V (2.36) 2H2O (l ) ® O2 (g) + 4H+(aq) + 4e– E (ocell ) = 1.23 V (2.37) The reaction at anode with lower value of E o is preferred and therefore, water should get oxidised in preference to Cl– (aq). However, on account of overpotential of oxygen, reaction (2.36) is preferred. Thus, the net reactions may be summarised as: NaCl (aq) H 2 O → Na+ (aq) + Cl– (aq) Cathode: H2O(l ) + e– ® ½ H2(g) + OH– (aq) Anode: Cl– (aq) ® ½ Cl2(g) + e– Net reaction: NaCl(aq) + H2O(l) ® Na+(aq) + OH–(aq) + ½H2(g) + ½Cl2(g) The standard electrode potentials are replaced by electrode potentials given by Nernst equation (Eq. 2.8) to take into account the concentration effects. During the electrolysis of sulphuric acid, the following processes are possible at the anode: 2H2O(l) ® O2(g) + 4H+(aq) + 4e– E (ocell ) = +1.23 V (2.38) 53 Electrochemistry Reprint 2025-26 2SO42– (aq) ® S2O8 2– (aq) + 2e– E (ocell ) = 1.96 V (2.39) For dilute sulphuric acid, reaction (2.38) is preferred but at higher concentrations of H2SO4, reaction (2.39) is preferred. IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.10 If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would flow through the wire? 2.11 Suggest a list of metals that are extracted electrolytically. 2.12 Consider the reaction: Cr2O7 2– + 14H+ + 6e– ® 2Cr3+ + 7H2O What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2O7 2–? 2.62.62.62.62.6 BatteriesBatteriesBatteriesBatteriesBatteries Any battery (actually it may have one or more than one cell connected in series) or cell that we use as a source of electrical energy is basically a galvanic cell where the chemical energy of the redox reaction is converted into electrical energy. However, for a battery to be of practical use it should be reasonably light, compact and its voltage should not vary appreciably during its use. There are mainly two types of batteries. 2.6.1 Primary In the primary batteries, the reaction occurs only once and after use Batteries over a period of time battery becomes dead and cannot be reused again. The most familiar example of this type is the dry cell (known as Leclanche cell after its discoverer) which is used commonly in our transistors and clocks. The cell consists of a zinc container that also acts as anode and the cathode is a carbon (graphite) rod surrounded by powdered manganese dioxide and carbon (Fig.2.8). The space between the electrodes is filled by a moist paste of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2). The electrode reactions are complex, but they can be written approximately as follows : Anode: Zn(s) ¾® Zn2+ + 2e– Cathode: MnO2+ NH4 ++ e–¾® MnO(OH) + NH3 In the reaction at cathode, manganese is reduced from the + 4 oxidation state to the +3 state. Ammonia produced in the reaction forms a complex with Zn2+ to give [Zn (NH3)4]2+. The cell has a potential of nearly 1.5 V. Mercury cell, (Fig. 2.9) suitable for low current devices like hearing aids, watches, etc. consists of zinc – mercury amalgam as anode and a paste of HgO and carbon as the Fig. 2.8: A commercial dry cell cathode. The electrolyte is a paste of KOH and ZnO. The consists of a graphite electrode reactions for the cell are given below: (carbon) cathode in a Anode: Zn(Hg) + 2OH– ¾® ZnO(s) + H2O + 2e– zinc container; the latter Cathode: HgO + H2O + 2e– ¾® Hg(l) + 2OH– acts as the anode. Chemistry 54 Reprint 2025-26 The overall reaction is represented by Zn(Hg) + HgO(s) ¾® ZnO(s) + Hg(l) The cell potential is approximately 1.35 V and remains constant during its Fig. 2.9 life as the overall reaction does not Commonly used involve any ion in solution whose mercury cell. The concentration can change during its life reducing agent is time. zinc and the oxidising agent is mercury (II) oxide. 2.6.2 Secondary A secondary cell after use can be recharged by passing current Batteries through it in the opposite direction so that it can be used again. A good secondary cell can undergo a large number of discharging and charging cycles. The most important secondary cell is the lead storage battery (Fig. 2.10) commonly used in automobiles and invertors. It consists of a lead anode and a grid of lead packed with lead dioxide (PbO2 ) as cathode. A 38% solution of sulphuric acid is used as an electrolyte. The cell reactions when the battery is in use are given below: Anode: Pb(s) + SO42–(aq) ® PbSO4(s) + 2e– Cathode: PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– ® PbSO4 (s) + 2H2O (l) i.e., overall cell reaction consisting of cathode and anode reactions is: Pb(s) + PbO2(s) + 2H2SO4(aq) ® 2PbSO4(s) + 2H2O(l) On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is converted into Pb and PbO2, respectively. Fig. 2.10: The Lead storage battery. 55 Electrochemistry Reprint 2025-26 Another important secondary cell is the nickel-cadmium cell (Fig. 2.11) which has longer life than the lead storage cell but Fig. 2.11 more expensive to manufacture. A rechargeable We shall not go into details of nickel-cadmium cell working of the cell and the Positive plate in a jelly roll electrode reactions during arrangement and Separator charging and discharging. separated by a layer Negative plate The overall reaction during soaked in moist discharge is: sodium or potassium hydroxide. Cd (s) + 2Ni(OH)3 (s) ® CdO (s) + 2Ni(OH)2 (s) + H2O (l ) 2.72.72.72.72.7 FuelFuelFuelFuelFuel CellsCellsCellsCellsCells Production of electricity by thermal plants is not a very efficient method and is a major source of pollution. In such plants, the chemical energy (heat of combustion) of fossil fuels (coal, gas or oil) is first used for converting water into high pressure steam. This is then used to run a turbine to produce electricity. We know that a galvanic cell directly converts chemical energy into electricity and is highly efficient. It is now possible to make such cells in which reactants are fed continuously to the electrodes and products are removed continuously from the electrolyte compartment. Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane, methanol, etc. directly into electrical energy are called fuel cells. One of the most successful fuel cells uses the reaction of hydrogen with oxygen to form water (Fig. 2.12). The cell was used for providing electrical power in the Apollo space programme. The water vapours produced during the reaction were condensed and added to the drinking water supply for the astronauts. In the cell, hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated aqueous sodium hydroxide solution. Catalysts like finely divided platinum or palladium metal are incorporated into the electrodes for increasing the rate of electrode Fig. 2.12: Fuel cell using H2 and O2 produces electricity. reactions. The electrode reactions are given below: Cathode: O2(g) + 2H2O(l) + 4e–¾® 4OH–(aq) Anode: 2H2 (g) + 4OH–(aq) ¾® 4H2O(l) + 4e– Overall reaction being: 2H2(g) + O2(g) ¾® 2H2O(l ) The cell runs continuously as long as the reactants are supplied. Fuel cells produce electricity with an efficiency of about 70 % compared Chemistry 56 Reprint 2025-26 to thermal plants whose efficiency is about 40%. There has been tremendous progress in the development of new electrode materials, better catalysts and electrolytes for increasing the efficiency of fuel cells. These have been used in automobiles on an experimental basis. Fuel cells are pollution free and in view of their future importance, a variety of fuel cells have been fabricated and tried. 2.82.82.82.82.8 CorrosionCorrosionCorrosionCorrosionCorrosion Corrosion slowly coats the surfaces of metallic objects with oxides or other salts of the metal. The rusting of iron, tarnishing of silver, development of green coating on copper and bronze are some of the examples of corrosion. It causes enormous damage to buildings, bridges, ships and to all objects made of metals especially that of iron. We lose crores of rupees every year on account of corrosion. In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of oxides. Corrosion of iron (commonly known as rusting) occurs in presence of water and air. The chemistry of corrosion is quite complex but it may be considered Oxidation: Fe (s)® Fe2+ (aq) +2e– essentially as an electrochemical Reduction: O2 (g) + 4H+(aq) +4e– ® 2H2O(l) phenomenon. At a particular spot Atomospheric (Fig. 2.13) of an object made of iron,oxidation: 2Fe2+(aq) + 2H2O(l) + ½O2(g) ® Fe2O3(s) + 4H+(aq) oxidation takes place and that spot Fig. 2.13: Corrosion of iron in atmosphere behaves as anode and we can write the reaction E o Anode: 2 Fe (s) ¾® 2 Fe2+ + 4 e– (Fe 2+ /Fe) = – 0.44 V Electrons released at anodic spot move through the metal and go to another spot on the metal and reduce oxygen in the presence of H+ (which is believed to be available from H2CO3 formed due to dissolution of carbon dioxide from air into water. Hydrogen ion in water may also be available due to dissolution of other acidic oxides from the atmosphere). This spot behaves as cathode with the reaction E o =1.23 V Cathode: O2(g) + 4 H+(aq) + 4 e– ¾® 2 H2O (l) H + | O 2 | H 2 O The overall reaction being: 2Fe(s) + O2(g) + 4H+(aq) ¾® 2Fe2 +(aq) + 2 H2O (l) E o(cell) =1.67 V The ferrous ions are further oxidised by atmospheric oxygen to ferric ions which come out as rust in the form of hydrated ferric oxide (Fe2O3. x H2O) and with further production of hydrogen ions. Prevention of corrosion is of prime importance. It not only saves money but also helps in preventing accidents such as a bridge collapse or failure of a key component due to corrosion. One of the simplest methods of preventing corrosion is to prevent the surface of the metallic object to come in contact with atmosphere. This can be done by covering the surface with paint or by some chemicals (e.g. bisphenol). Another simple method is to cover the surface by other metals (Sn, Zn, etc.) that are inert or react to save the object. An electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn, etc.) which corrodes itself but saves the object. 57 Electrochemistry Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.13 Write the chemistry of recharging the lead storage battery, highlighting all the materials that are involved during recharging. 2.14 Suggest two materials other than hydrogen that can be used as fuels in fuel cells. 2.15 Explain how rusting of iron is envisaged as setting up of an electrochemical cell. TheTheTheTheThe HydrogenHydrogenHydrogenHydrogenHydrogen EconomyEconomyEconomyEconomyEconomy At present the main source of energy that is driving our economy is fossil fuels such as coal, oil and gas. As more people on the planet aspire to improve their standard of living, their energy requirement will increase. In fact, the per capita consumption of energy used is a measure of development. Of course, it is assumed that energy is used for productive purpose and not merely wasted. We are already aware that carbon dioxide produced by the combustion of fossil fuels is resulting in the ‘Greenhouse Effect’. This is leading to a rise in the temperature of the Earth’s surface, causing polar ice to melt and ocean levels to rise. This will flood low-lying areas along the coast and some island nations such as Maldives face total submergence. In order to avoid such a catastrope, we need to limit our use of carbonaceous fuels. Hydrogen provides an ideal alternative as its combustion results in water only. Hydrogen production must come from splitting water using solar energy. Therefore, hydrogen can be used as a renewable and non polluting source of energy. This is the vision of the Hydrogen Economy. Both the production of hydrogen by electrolysis of water and hydrogen combustion in a fuel cell will be important in the future. And both these technologies are based on electrochemical principles. SummarySummarySummarySummarySummary An electrochemical cell consists of two metallic electrodes dipping in electrolytic solution(s). Thus an important component of the electrochemical cell is the ionic conductor or electrolyte. Electrochemical cells are of two types. In galvanic cell, the chemical energy of a spontaneous redox reaction is converted into electrical work, whereas in an electrolytic cell, electrical energy is used to carry out a non- spontaneous redox reaction. The standard electrode potential for any electrode dipping in an appropriate solution is defined with respect to standard electrode potential of hydrogen electrode taken as zero. The standard potential of the cell can be obtained by taking the difference of the standard potentials of cathode and anode ( E (ocell ) = Eocathode – Eoanode). The standard potential of the cells are related to standard Gibbs energy (DrGo = –nF E (ocell ) ) and equilibrium constant (DrGo = – RT ln K) of the reaction taking place in the cell. Concentration dependence of the potentials of the electrodes and the cells are given by Nernst equation. The conductivity, k, of an electrolytic solution depends on the concentration of the electrolyte, nature of solvent and temperature. Molar conductivity, Lm, is defined by = k/c where c is the concentration. Conductivity decreases but molar conductivity increases with decrease in concentration. It increases slowly with decrease in concentration for strong electrolytes while the increase is very steep for weak electrolytes in very dilute solutions. Kohlrausch found that molar conductivity at infinite dilution, for an electrolyte is sum of the contribution of the Chemistry 58 Reprint 2025-26 molar conductivity of the ions in which it dissociates. It is known as law of independent migration of ions and has many applications. Ions conduct electricity through the solution but oxidation and reduction of the ions take place at the electrodes in an electrochemical cell. Batteries and fuel cells are very useful forms of galvanic cell. Corrosion of metals is essentially an electrochemical phenomenon. Electrochemical principles are relevant to the Hydrogen Economy. ExercisesExercisesExercisesExercisesExercises

6.4 LINEAR MOMENTUM OF A SYSTEM OF Eq. (6.15), this also means that when the PARTICLES total external force on the system is zero the velocity of the centre of mass remainsLet us recall that the linear momentum of a constant. (We assume throughout the particle is defined as discussion on systems of particles in this p = m v (6.12) chapter that the total mass of the system Let us also recall that Newton’s second law remains constant.) written in symbolic form for a single particle is Note that on account of the internal forces, dp i.e. the forces exerted by the particles on one F = (6.13) another, the individual particles may have dt Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 101 complicated trajectories. Yet, if the total external force acting on the system is zero, the centre of mass moves with a constant velocity, i.e., moves uniformly in a straight line like a free particle. The vector Eq. (6.18a) is equivalent to three scalar equations, Px = c1, Py = c2 and Pz = c3 (6.18 b) (a) (b) Here Px, Py and Pz are the components of the total linear momentum vector P along the x–, y– Fig. 6.14 (a) Trajectories of two stars, S1 (dotted line) and z–axes respectively; c1, c2 and c3 are and S2 (solid line) forming a binary constants. system with their centre of mass C in uniform motion. (b) The same binary system, with the centre of mass C at rest. move back to back with their centre of mass remaining at rest as shown in Fig.6.13 (b). In many problems on the system of particles, as in the above radioactive decay problem, it is convenient to work in the centre of mass frame rather than in the laboratory frame of reference. (a) (b) In astronomy, binary (double) stars is a common occurrence. If there are no external forces, the centre of mass of a double star Fig. 6.13 (a) A heavy nucleus radium (Ra) splits into moves like a free particle, as shown in Fig.6.14 a lighter nucleus radon (Rn) and an alpha (a). The trajectories of the two stars of equal particle (nucleus of helium atom). The CM mass are also shown in the figure; they look of the system is in uniform motion. complicated. If we go to the centre of mass (b) The same spliting of the heavy nucleus radium (Ra) with the centre of mass at frame, then we find that there the two stars rest. The two product particles fly back are moving in a circle, about the centre of to back. mass, which is at rest. Note that the position of the stars have to be diametrically opposite As an example, let us consider the to each other [Fig. 6.14(b)]. Thus in our frame radioactive decay of a moving unstable particle, of reference, the trajectories of the stars are a combination of (i) uniform motion in a straightlike the nucleus of radium. A radium nucleus line of the centre of mass and (ii) circulardisintegrates into a nucleus of radon and an orbits of the stars about the centre of mass.alpha particle. The forces leading to the decay As can be seen from the two examples,are internal to the system and the external separating the motion of different parts of aforces on the system are negligible. So the total system into motion of the centre of mass andlinear momentum of the system is the same motion about the centre of mass is a verybefore and after decay. The two particles useful technique that helps in understanding produced in the decay, the radon nucleus and the motion of the system. the alpha particle, move in different directions in such a way that their centre of mass moves 6.5 VECTOR PRODUCT OF TWO VECTORS along the same path along which the original decaying radium nucleus was moving We are already familiar with vectors and their [Fig. 6.13(a)]. use in physics. In chapter 5 (Work, Energy, Power) If we observe the decay from the frame of we defined the scalar product of two vectors. An reference in which the centre of mass is at rest, important physical quantity, work, is defined as the motion of the particles involved in the decay a scalar product of two vector quantities, force looks particularly simple; the product particles and displacement. Reprint 2025-26 102 PHYSICS We shall now define another product of two A simpler version of the right hand rule is vectors. This product is a vector. Two important the following : Open up your right hand palm quantities in the study of rotational motion, and curl the fingers pointing from a to b. Your namely, moment of a force and angular stretched thumb points in the direction of c. momentum, are defined as vector products. It should be remembered that there are two angles between any two vectors a and b . In Definition of Vector Product Fig. 6.15 (a) or (b) they correspond to θ(as shown) A vector product of two vectors a and b is a and (3600– θ). While applying either of the above vector c such that rules, the rotation should be taken through the (i) magnitude of c = c = ab sinθ where a and b smaller angle (<1800) between a and b. It is θ are magnitudes of a and b and θ is the here. angle between the two vectors. Because of the cross (×) used to denote the (ii) c is perpendicular to the plane containing vector product, it is also referred to as cross product. a and b. • Note that scalar product of two vectors is (iii) if we take a right handed screw with its head commutative as said earlier, a.b = b.a lying in the plane of a and b and the screw The vector product, however, is not perpendicular to this plane, and if we turn commutative, i.e. a × b ≠ b × a the head in the direction from a to b, then The magnitude of both a × b and b × a is the the tip of the screw advances in the direction same ( ab sin θ ); also, both of them are of c. This right handed screw rule is perpendicular to the plane of a and b. But the illustrated in Fig. 6.15a. rotation of the right-handed screw in case of Alternately, if one curls up the fingers of a × b is from a to b, whereas in case of b × a it right hand around a line perpendicular to the is from b to a. This means the two vectors are plane of the vectors a and b and if the fingers in opposite directions. We have are curled up in the direction from a to b, then a × b = − b × a the stretched thumb points in the direction of • Another interesting property of a vector c, as shown in Fig. 6.15b. product is its behaviour under reflection. Under reflection (i.e. on taking the plane mirror image) we have x →− x , y →−y and z →− z . As a result all the components of a vector change sign and thus a →−a , b →−b . What happens to a × b under reflection? a × b →−( a ) × ( − b ) = a × b Thus, a × b does not change sign under reflection. • Both scalar and vector products are distributive with respect to vector addition. Thus, a.( b + c ) = a.b + a.c a × ( b + c ) = a × b + a × c (a) (b) • We may write c = a × b in the component form. For this we first need to obtain some elementary cross products: Fig. 6.15 (a) Rule of the right handed screw for (i) a × a = 0 (0 is a null vector, i.e. a vector defining the direction of the vector with zero magnitude) product of two vectors. This follows since magnitude of a × a is (b) Rule of the right hand for defining the direction of the vector product. a 2 sin0° = 0 . Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 103 From this follow the results ˆ ˆ ˆ i j k (i) ˆi × ˆi = 0, ˆj × ˆj = 0, kˆ × kˆ = 0 a × b = 3 − 4 5 = 7 ˆi − ˆj − 5 kˆ (ii) ˆi × ˆj = kˆ − 2 1 − 3 Note that the magnitude of ˆi × ˆj is sin900 Note b × a = −7ˆi + ˆj + 5 kˆ ⊳ or 1, since ˆi and ˆj both have unit magnitude and the angle between them is 900. 6.6 ANGULAR VELOCITY AND ITS RELATION WITH LINEAR VELOCITY Thus, ˆi × ˆj is a unit vector. A unit vector In this section we shall study what is angular perpendicular to the plane of ˆi and ˆj and velocity and its role in rotational motion. We related to them by the right hand screw rule is have seen that every particle of a rotating body moves in a circle. The linear velocity of the ˆk . Hence, the above result. You may verify particle is related to the angular velocity. The similarly, relation between these two quantities involves ˆ j × kˆ = ˆi and kˆ × ˆi = ˆj a vector product which we learnt about in the last section. From the rule for commutation of the cross Let us go back to Fig. 6.4. As said above, inproduct, it follows: rotational motion of a rigid body about a fixed ˆ j × ˆi = − kˆ , kˆ × ˆj = − ˆi, ˆi × kˆ = − ˆj axis, every particle of the body moves in a circle, Note if ˆi, ˆj, kˆ occur cyclically in the above vector product relation, the vector product is positive. If ˆi, ˆj, kˆ do not occur in cyclic order, the vector product is negative. Now, a × b = (a x ˆi + a y ˆj + a z kˆ ) × (b x ˆi + b y ˆj + b z kˆ ) = a x b y kˆ − a x b z ˆj − a y b x kˆ + a y b z ˆi + a z b x ˆj − a z b y ˆi = (a y b z − a z b y )i + (a z b x − a x b z ) j + (a x b y − a y b x )k We have used the elementary cross products in obtaining the above relation. The expression for a × b can be put in a determinant form which is easy to remember. ˆ ˆ ˆ i j k a × b = a x a y a z b x b y b z u Example 6.4 Find the scalar and vector Fig. 6.16 Rotation about a fixed axis. (A particle (P) of the rigid body rotating about the fixed products of two vectors. a = (z-) axis moves in a circle with centre (C) and b = on the axis.) Answer which lies in a plane perpendicular to the axis a i b = (3ˆi − 4 ˆj + 5 kˆ )i( − 2ˆi + ˆj − 3 kˆ ) and has its centre on the axis. In Fig. 6.16 we redraw Fig. 6.4, showing a typical particle (at a = −6 − 4 − 15 point P) of the rigid body rotating about a fixed = −25 axis (taken as the z-axis). The particle describes Reprint 2025-26 104 PHYSICS a circle with a centre C on the axis. The radius and points out in the direction in which a right of the circle is r, the perpendicular distance of handed screw would advance, if the head of the the point P from the axis. We also show the screw is rotated with the body. (See Fig. 6.17a). linear velocity vector v of the particle at P. It is The magnitude of this vector is ω = d θ dt along the tangent at P to the circle. referred as above. Let P′ be the position of the particle after an interval of time ∆t (Fig. 6.16). The angle PCP′ describes the angular displacement ∆θ of the particle in time ∆t. The average angular velocity of the particle over the interval ∆t is ∆θ/∆t. As ∆t tends to zero (i.e. takes smaller and smaller values), the ratio ∆θ/∆t approaches a limit which is the instantaneous angular velocity dθ/dt of the particle at the position P. We denote the instantaneous angular velocity by ω (the Greek letter omega). We know from our study Fig. 6.17 (a) If the head of a right handed screw of circular motion that the magnitude of linear rotates with the body, the screw velocity v of a particle moving in a circle is advances in the direction of the angular related to the angular velocity of the particle ω velocity ω. If the sense (clockwise or by the simple relation υ = ωr , where r is the anticlockwise) of rotation of the body changes, so does the direction of ω.radius of the circle. We observe that at any given instant the relation v = ωr applies to all particles of the rigid body. Thus for a particle at a perpendicular distance ri from the fixed axis, the linear velocity at a given instant vi is given by v i = ωri (6.19) The index i runs from 1 to n, where n is the total number of particles of the body. For particles on the axis, r = 0 , and hence v = ω r = 0. Thus, particles on the axis are stationary. This verifies that the axis is fixed. Note that we use the same angular velocity ω for all the particles. We therefore, refer to ω as the angular velocity of the whole body. We have characterised pure translation of a body by all parts of the body having the same Fig. 6.17 (b) The angular velocity vector ω is directed velocity at any instant of time. Similarly, we along the fixed axis as shown. The linear may characterise pure rotation by all parts of velocity of the particle at P is v = ω × r. the body having the same angular velocity at It is perpendicular to both ωωωωω and r and any instant of time. Note that this is directed along the tangent to the circle described by the particle. characterisation of the rotation of a rigid body about a fixed axis is just another way of saying We shall now look at what the vector as in Sec. 6.1 that each particle of the body moves product ω × r corresponds to. Refer to Fig. in a circle, which lies in a plane perpendicular 6.17(b) which is a part of Fig. 6.16 reproduced to the axis and has the centre on the axis. to show the path of the particle P. The figure In our discussion so far the angular velocity shows the vector ω directed along the fixed (z–) appears to be a scalar. In fact, it is a vector. We axis and also the position vector r = OP of the shall not justify this fact, but we shall accept particle at P of the rigid body with respect to it. For rotation about a fixed axis, the angular the origin O. Note that the origin is chosen to velocity vector lies along the axis of rotation, be on the axis of rotation. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 105 Now ω × r = ω × OP = ω × (OC + CP) If the axis of rotation is fixed, the direction But ω × OC = 00000 as ωωωωω is along OC of ωωωωω and hence, that of α is fixed. In this case Hence ω × r = ω × CP the vector equation reduces to a scalar equation dω α = (6.22) The vector ω × CP is perpendicular to ω, i.e. dt to the z-axis and also to CP, the radius of the circle described by the particle at P. It is 6.7 TORQUE AND ANGULAR MOMENTUM therefore, along the tangent to the circle at P. In this section, we shall acquaint ourselves with Also, the magnitude of ω × CP is ω (CP) since two physical quantities (torque and angular ω and CP are perpendicular to each other. We momentum) which are defined as vector products shall denote CP by ⊥r and not by r, as we did of two vectors. These as we shall see, are earlier. especially important in the discussion of motion Thus, ω × r is a vector of magnitude ωr⊥ of systems of particles, particularly rigid bodies. and is along the tangent to the circle described by the particle at P. The linear velocity vector v 6.7.1 Moment of force (Torque) at P has the same magnitude and direction. We have learnt that the motion of a rigid body, Thus, in general, is a combination of rotation and v = ωωωωω × r (6.20) translation. If the body is fixed at a point or along In fact, the relation, Eq. (6.20), holds good a line, it has only rotational motion. We know even for rotation of a rigid body with one point that force is needed to change the translationalfixed, such as the rotation of the top [Fig. 6.6(a)]. In this case r represents the position vector of state of a body, i.e. to produce linear the particle with respect to the fixed point taken acceleration. We may then ask, what is the as the origin. analogue of force in the case of rotational We note that for rotation about a fixed motion? To look into the question in a concrete axis, the direction of the vector ω does not situation let us take the example of opening or change with time. Its magnitude may, closing of a door. A door is a rigid body which however, change from instant to instant. For can rotate about a fixed vertical axis passing the more general rotation, both the magnitude and the direction of ωωωωω may change through the hinges. What makes the door from instant to instant. rotate? It is clear that unless a force is applied the door does not rotate. But any force does not 6.6.1 Angular acceleration do the job. A force applied to the hinge line You may have noticed that we are developing cannot produce any rotation at all, whereas a the study of rotational motion along the lines force of given magnitude applied at right angles of the study of translational motion with which to the door at its outer edge is most effective in we are already familiar. Analogous to the kinetic producing rotation. It is not the force alone, but variables of linear displacement (s) and velocity how and where the force is applied is important (v) in translational motion, we have angular in rotational motion. displacement (θ) and angular velocity (ω) in The rotational analogue of force in linear rotational motion. It is then natural to define motion is moment of force. It is also referred to in rotational motion the concept of angular as torque or couple. (We shall use the words acceleration in analogy with linear acceleration moment of force and torque interchangeably.) defined as the time rate of change of velocity in We shall first define the moment of force for the translational motion. We define angular special case of a single particle. Later on we acceleration α as the time rate of change of shall extend the concept to systems of particles angular velocity. Thus, including rigid bodies. We shall also relate it to d ω a change in the state of rotational motion, i.e. is α = (6.21) dt angular acceleration of a rigid body. Reprint 2025-26 106 PHYSICS of the line of action of F from the origin and F⊥=( F sin θ) is the component of F in the direction perpendicular to r. Note that τ = 0 if r = 0, F = 0 or θ = 00 or 1800 . Thus, the moment of a force vanishes if either the magnitude of the force is zero, or if the line of action of the force passes through the origin. One may note that since r × F is a vector product, properties of a vector product of two vectors apply to it. If the direction of F is reversed, the direction of the moment of force is reversed. If directions of both r and F are reversed, the direction of the moment of force remains the same. 6.7.2 Angular momentum of a particle Just as the moment of a force is the rotational analogue of force in linear motion, the quantity angular momentum is the rotational analogue Fig. 6.18 τττττ ===== r × F, τττττ is perpendicular to the plane of linear momentum. We shall first define containing r and F, and its direction is angular momentum for the special case of a given by the right handed screw rule. single particle and look at its usefulness in the context of single particle motion. We shall then If a force acts on a single particle at a point extend the definition of angular momentum to P whose position with respect to the origin O is systems of particles including rigid bodies. given by the position vector r (Fig. 6.18), the Like moment of a force, angular momentum moment of the force acting on the particle with is also a vector product. It could also be referred respect to the origin O is defined as the vector to as moment of (linear) momentum. From this product term one could guess how angular momentum τ = r × F (6.23) is defined. The moment of force (or torque) is a vector Consider a particle of mass m and linear quantity. The symbol τττττ stands for the Greek momentum p at a position r relative to the origin letter tau. The magnitude of τττττ is O. The angular momentum l of the particle with τ = r F sinθ (6.24a) respect to the origin O is defined to be l = r × p (6.25a)where r is the magnitude of the position vector r, i.e. the length OP, F is the magnitude of force The magnitude of the angular momentum F and θ is the angle between r and F as vector is shown. l = r p sinθ (6.26a) Moment of force has dimensions M L2 T -2. where p is the magnitude of p and θ is the angle Its dimensions are the same as those of work between r and p. We may write or energy. It is, however, a very different physical l = r p⊥ or r ⊥ p (6.26b)quantity than work. Moment of a force is a vector, while work is a scalar. The SI unit of where r⊥ (= r sinθ) is the perpendicular distance moment of force is newton metre (N m). The of the directional line of p from the origin and magnitude of the moment of force may be p ⊥=( p sin θ) is the component of p in a directionwritten perpendicular to r. We expect the angular τ = (r sin θ)F = r⊥ F (6.24b) momentum to be zero (l = 0), if the linear or τ = r F sin θ = rF ⊥ (6.24c) momentum vanishes (p = 0), if the particle is at the origin (r = 0), or if the directional line of p where r⊥ = r sinθ is the perpendicular distance passes through the origin θ = 00 or 1800. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 107 The physical quantities, moment of a force and angular momentum, have an important An experiment with the bicycle rim relation between them. It is the rotational Take a analogue of the relation between force and linear bicycle rim momentum. For deriving the relation in the and extend context of a single particle, we differentiate its axle on l = r × p with respect to time, both sides. Tie two d l d = ( r × p ) s t r i n g s d t d t at both ends Applying the product rule for differentiation A and B, to the right hand side, as shown in the d d r d p ( r × p ) = × p + r × a d j o i n i n g d t d t d t figure. Hold Now, the velocity of the particle is v = dr/dt both the and p = m v Initially After s t r i n g s together in dr one hand such that the rim is vertical. If you Because of this × p = v × m v = 0, dt leave one string, the rim will tilt. Now keeping the rim in vertical position with both the stringsas the vector product of two parallel vectors in one hand, put the wheel in fast rotation vanishes. Further, since dp / dt = F, around the axle with the other hand. Then leave d p one string, say B, from your hand, and observe r × = r × F = t dt what happens. The rim keeps rotating in a vertical plane d and the plane of rotation turns around the string Hence ( r × p ) = τ A which you are holding. We say that the axis dt of rotation of the rim or equivalently or (6.27) its angular momentum precesses about the string A. Thus, the time rate of change of the angular The rotating rim gives rise to an angular momentum of a particle is equal to the torque momentum. Determine the direction of this acting on it. This is the rotational analogue of angular momentum. When you are holding the the equation F = dp/dt, which expresses rotating rim with string A, a torque is generated. (We leave it to you to find out how the torque isNewton’s second law for the translational motion generated and what its direction is.) The effect of a single particle. of the torque on the angular momentum is to make it precess around an axis perpendicular Torque and angular momentum for a system to both the angular momentum and the torque. of particles Verify all these statements. To get the total angular momentum of a system of particles about a given point we need to add vectorially the angular momenta of individual particles. Thus, for a system of n particles, particle has mass mi and velocity vi) We may write the total angular momentum of a system of particles as (6.25b) The angular momentum of the ith particle is given by li = ri × pi This is a generalisation of the definition of angular momentum (Eq. 6.25a) for a singlewhere ri is the position vector of the ith particle particle to a system of particles.with respect to a given origin and p = (mivi) is Using Eqs. (6.23) and (6.25b), we getthe linear momentum of the particle. (The Reprint 2025-26 108 PHYSICS d L d d l Note that like Eq.(6.17), Eq.(6.28b) holds = ( l ) = ∑ = ∑ τ (6.28a) good for any system of particles, whether it is a d t d t i d t i rigid body or its individual particles have all where τi is the torque acting on the ith particle; kinds of internal motion. τi = ri × Fi Conservation of angular momentum The force Fi on the ith particle is the vector ext If τext = 0, Eq. (6.28b) reduces to Fi sum of external forces acting on the particle d L = 0 and the internal forces iFint exerted on it by the dt other particles of the system. We may therefore or L = constant. (6.29a) separate the contribution of the external and Thus, if the total external torque on a system the internal forces to the total torque of particles is zero, then the total angular momentum of the system is conserved, i.e. τ = ∑ τ i = ∑ ri × Fi as remains constant. Eq. (6.29a) is equivalent to i i three scalar equations, τ = τext + τ int , Lx = K1, Ly = K2 and Lz = K3 (6.29 b) Here K1, K2 and K3 are constants; Lx, Ly and τ ext = ∑ri × Fi ext Lz are the components of the total angular where i momentum vector L along the x,y and z axes respectively. The statement that the total i × Fiint τ int = ∑r and angular momentum is conserved means that i each of these three components is conserved. We shall assume not only Newton’s third law Eq. (6.29a) is the rotational analogue of of motion, i.e. the forces between any two particles Eq. (6.18a), i.e. the conservation law of the total of the system are equal and opposite, but also that linear momentum for a system of particles. these forces are directed along the line joining the Like Eq. (6.18a), it has applications in many two particles. In this case the contribution of the practical situations. We shall look at a few of internal forces to the total torque on the system is the interesting applications later on in zero, since the torque resulting from each action- this chapter. reaction pair of forces is zero. We thus have, τint = 0 and therefore τ = τττext.ττ u Example 6.5 Find the torque of a force Since τ = ∑ τ i , it follows from Eq. (6.28a) + – about the origin. The force acts on a particle whose position vector is .that d L = τ ext (6.28 b) Answer Here r = ˆi − ˆj + kˆ d t and F = 7 ˆi + 3 ˆj − 5 kˆ . Thus, the time rate of the total angular We shall use the determinant rule to find themomentum of a system of particles about a τ = r × Fpoint (taken as the origin of our frame of torque reference) is equal to the sum of the external torques (i.e. the torques due to external forces) acting on the system taken about the same point. Eq. (6.28 b) is the generalisation of the single particle case of Eq. (6.23) to a system of particles. Note that when we have only one or ⊳ particle, there are no internal forces or torques. Eq.(6.28 b) is the rotational analogue of Example 6.6 Show that the angular u momentum about any point of a single d P = Fext (6.17) particle moving with constant velocity d t remains constant throughout the motion. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 109 Answer Let the particle with velocity v be at acceleration nor angular acceleration. This means point P at some instant t. We want to calculate (1) the total force, i.e. the vector sum of the the angular momentum of the particle about an forces, on the rigid body is zero; arbitrary point O. n F1 + F2 + ... + Fn = =∑i 1 Fi = 0 (6.30a) If the total force on the body is zero, then the total linear momentum of the body does not change with time. Eq. (6.30a) gives the condition for the translational equilibrium of the body. (2) The total torque, i.e. the vector sum of the torques on the rigid body is zero, n τ + τ i = 0 (6.30b) 1 2 + ... + τ n = =∑i 1 τ Fig 6.19 If the total torque on the rigid body is zero, The angular momentum is l = r × mv. Its the total angular momentum of the body does magnitude is mvr sinθ, where θ is the angle not change with time. Eq. (6.30 b) gives the between r and v as shown in Fig. 6.19. Although condition for the rotational equilibrium of the the particle changes position with time, the line body. of direction of v remains the same and hence One may raise a question, whether theOM = r sin θ. is a constant. rotational equilibrium condition [Eq. 6.30(b)] Further, the direction of l is perpendicular remains valid, if the origin with respect to whichto the plane of r and v. It is into the page of the the torques are taken is shifted. One can showfigure.This direction does not change with time. Thus, l remains the same in magnitude and that if the translational equilibrium condition direction and is therefore conserved. Is there [Eq. 6.30(a)] holds for a rigid body, then such a any external torque on the particle? ⊳ shift of origin does not matter, i.e. the rotational equilibrium condition is independent of the 6.8 EQUILIBRIUM OF A RIGID BODY location of the origin about which the torques are taken. Example 6.7 gives a proof of this result We are now going to concentrate on the motion in a special case of a couple, i.e. two forcesof rigid bodies rather than on the motion of acting on a rigid body in translationalgeneral systems of particles. equilibrium. The generalisation of this result to We shall recapitulate what effect the external forces have on a rigid body. (Henceforth n forces is left as an exercise. we shall omit the adjective ‘external’ because Eq. (6.30a) and Eq. (6.30b), both, are vector unless stated otherwise, we shall deal with only equations. They are equivalent to three scalar external forces and torques.) The forces change equations each. Eq. (6.30a) corresponds to the translational state of the motion of the rigid n n n body, i.e. they change its total linear =∑i 1 Fix = 0 , =∑i 1 Fiy = 0 and =∑i 1 Fiz = 0 (6.31a)momentum in accordance with Eq. (6.17). But this is not the only effect the forces have. The where Fix, Fiy and Fiz are respectively the x, y and total torque on the body may not vanish. Such z components of the forces Fi. Similarly, Eq. a torque changes the rotational state of motion (6.30b) is equivalent to three scalar equations of the rigid body, i.e. it changes the total angular n n 0momentum of the body in accordance with τix = 0 , τiy = and (6.31b) =∑i 1 =∑i 1 Eq. (6.28 b). where τix, τiy and τiz are respectively the x, y and A rigid body is said to be in mechanical z components of the torque τi .equilibrium, if both its linear momentum and Eq. (6.31a) and (6.31b) give six independentangular momentum are not changing with time, conditions to be satisfied for mechanicalor equivalently, the body has neither linear Reprint 2025-26 110 PHYSICS equilibrium of a rigid body. In a number of problems all the forces acting on the body are coplanar. Then we need only three conditions to be satisfied for mechanical equilibrium. Two of these conditions correspond to translational equilibrium; the sum of the components of the forces along any two perpendicular axes in the plane must be zero. The third condition corresponds to rotational equilibrium. The sum of the components of the torques along any axis Fig. 6.20 (b) perpendicular to the plane of the forces must be zero. The force at B in Fig. 6.20(a) is reversed in Fig. 6.20(b). Thus, we have the same rod with The conditions of equilibrium of a rigid body two forces of equal magnitude but acting inmay be compared with those for a particle, which opposite diretions applied perpendicular to the we considered in earlier chapters. Since rod, one at end A and the other at end B. Here consideration of rotational motion does not apply the moments of both the forces are equal, but to a particle, only the conditions for translational they are not opposite; they act in the same sense equilibrium (Eq. 6.30 a) apply to a particle. Thus, and cause anticlockwise rotation of the rod. The for equilibrium of a particle the vector sum of total force on the body is zero; so the body is in all the forces on it must be zero. Since all these translational equilibrium; but it is not in forces act on the single particle, they must be rotational equilibrium. Although the rod is not fixed in any way, it undergoes pure rotation (i.e.concurrent. Equilibrium under concurrent rotation without translation).forces was discussed in the earlier chapters. A pair of forces of equal magnitude but acting A body may be in partial equilibrium, i.e., it in opposite directions with different lines of may be in translational equilibrium and not in action is known as a couple or torque. A couple rotational equilibrium, or it may be in rotational produces rotation without translation. equilibrium and not in translational When we open the lid of a bottle by turning equilibrium. it, our fingers are applying a couple to the lid Consider a light (i.e. of negligible mass) rod [Fig. 6.21(a)]. Another known example is a compass needle in the earth’s magnetic field as(AB) as shown in Fig. 6.20(a). At the two ends (A shown in the Fig. 6.21(b). The earth’s magneticand B) of which two parallel forces, both equal field exerts equal forces on the north and southin magnitude and acting along same direction poles. The force on the North Pole is towards are applied perpendicular to the rod. the north, and the force on the South Pole is toward the south. Except when the needle points in the north-south direction; the two forces do not have the same line of action. Thus there is a couple acting on the needle due to the earth’s magnetic field. Fig. 6.20 (a) Let C be the midpoint of AB, CA = CB = a. the moment of the forces at A and B will both be equal in magnitude (aF ), but opposite in sense as shown. The net moment on the rod will be zero. The system will be in rotational equilibrium, but it will not be in translational fingers apply a couple to turnequilibrium; F ≠ 0 Fig. 6.21(a) Our ∑ the lid. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 111 length. This point is called the fulcrum. A see- saw on the children’s playground is a typical example of a lever. Two forces F1 and F2, parallel to each other and usually perpendicular to the lever, as shown here, act on the lever at distances d1 and d2 respectively from the fulcrum as shown in Fig. 6.23. Fig. 6.21(b) The Earth’s magnetic field exerts equal and opposite forces on the poles of a Fig. 6.23 compass needle. These two forces form a couple. The lever is a system in mechanical equilibrium. Let R be the reaction of the supportu Example 6.7 Show that moment of a at the fulcrum; R is directed opposite to the couple does not depend on the point about forces F1 and F2. For translational equilibrium, which you take the moments. R – F1 – F2 = 0 (i) Answer For considering rotational equilibrium we take the moments about the fulcrum; the sum of moments must be zero, d1F1 – d2F2 = 0 (ii) Normally the anticlockwise (clockwise) moments are taken to be positive (negative). Note R acts at the fulcrum itself and has zero moment about the fulcrum. Fig. 6.22 In the case of the lever force F1 is usually Consider a couple as shown in Fig. 6.22 some weight to be lifted. It is called the load and acting on a rigid body. The forces F and -F act its distance from the fulcrum d1 is called the respectively at points B and A. These points have load arm. Force F2 is the effort applied to lift the position vectors r1 and r2 with respect to origin load; distance d2 of the effort from the fulcrum O. Let us take the moments of the forces about is the effort arm. the origin. Eq. (ii) can be written as The moment of the couple = sum of the d1F1 = d2 F2 (6.32a) moments of the two forces making the couple or load arm × load = effort arm × effort = r1 × (–F) + r2 × F The above equation expresses the principle = r2 × F – r1 × F of moments for a lever. Incidentally the ratio = (r2–r1) × F F1/F2 is called the Mechanical Advantage (M.A.); But r1 + AB = r2, and hence AB = r2 – r1. F1 d 2 The moment of the couple, therefore, is M.A. = = (6.32b) F2 d1AB × F. Clearly this is independent of the origin, the If the effort arm d2 is larger than the load point about which we took the moments of the arm, the mechanical advantage is greater than forces. ⊳ one. Mechanical advantage greater than one means that a small effort can be used to lift a 6.8.1 Principle of moments large load. There are several examples of a lever An ideal lever is essentially a light (i.e. of around you besides the see-saw. The beam of a negligible mass) rod pivoted at a point along its balance is a lever. Try to find more such Reprint 2025-26 112 PHYSICS examples and identify the fulcrum, the effort and The CG of the cardboard is so located that effort arm, and the load and the load arm of the the total torque on it due to the forces m1g, m2g lever in each case. …. etc. is zero. You may easily show that the principle of If ri is the position vector of the ith particle moment holds even when the parallel forces F1 of an extended body with respect to its CG, then and F2 are not perpendicular, but act at some the torque about the CG, due to the force of angle, to the lever. gravity on the particle is τi = ri × mi g. The total gravitational torque about the CG is zero, i.e. 6.8.2 Centre of gravity i × m i g = 0 (6.33) τ g = ∑ τ i = ∑r Many of you may have the experience of We may therefore, define the CG of a body balancing your notebook on the tip of a finger. as that point where the total gravitational torque Figure 6.24 illustrates a similar experiment that on the body is zero. you can easily perform. Take an irregular- We notice that in Eq. (6.33), g is the same shaped cardboard having mass M and a narrow for all particles, and hence it comes out of the tipped object like a pencil. You can locate by trial summation. This gives, since g is non-zero, and error a point G on the cardboard where it ir = 0. Remember that the position vectorscan be balanced on the tip of the pencil. (The ∑mi cardboard remains horizontal in this position.) (ri) are taken with respect to the CG. Now, in This point of balance is the centre of gravity (CG) accordance with the reasoning given below of the cardboard. The tip of the pencil provides Eq. (6.4a) in Sec. 6.2, if the sum is zero, the origin a vertically upward force due to which the must be the centre of mass of the body. Thus, cardboard is in mechanical equilibrium. As the centre of gravity of the body coincides with shown in the Fig. 6.24, the reaction of the tip is the centre of mass in uniform gravity or gravity- equal and opposite to Mg and hence the cardboard is in translational equilibrium. It is also in rotational equilibrium; if it were not so, due to the unbalanced torque it would tilt and fall. There are torques on the card board due to the forces of gravity like m1g, m2g …. etc, acting on the individual particles that make up the cardboard. Fig. 6.25 Determining the centre of gravity of a body Fig. 6.24 Balancing a cardboard on the tip of a of irregular shape. The centre of gravity G pencil. The point of support, G, is the lies on the vertical AA1 through the point centre of gravity. of suspension of the body A. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 113 free space. We note that this is true because = 30 cm, PG = 5 cm, AK1= BK2 = 10 cm and K1G = the body being small, g does not K2G = 25 cm. Also, W= weight of the rod = 4.00 vary from one point of the body to the other. If kg and W 1= suspended load = 6.00 kg; the body is so extended that g varies from part R1 and R2 are the normal reactions of the to part of the body, then the centre of gravity support at the knife edges. and centre of mass will not coincide. Basically, For translational equilibrium of the rod, the two are different concepts. The centre of R1+R2 –W1 –W = 0 (i) mass has nothing to do with gravity. It depends Note W1 and W act vertically down and R1 only on the distribution of mass of the body. and R2 act vertically up. In Sec. 6.2 we found out the position of the For considering rotational equilibrium, we centre of mass of several regular, homogeneous take moments of the forces. A convenient point objects. Obviously the method used there gives to take moments about is G. The moments of us also the centre of gravity of these bodies, if R2 and W1 are anticlockwise (+ve), whereas the they are small enough. moment of R1 is clockwise (-ve). Figure 6.25 illustrates another way of For rotational equilibrium, determining the CG of an irregular shaped body –R1 (K1G) + W1 (PG) + R2 (K2G) = 0 (ii) like a cardboard. If you suspend the body from It is given that W = 4.00g N and W1 = 6.00g some point like A, the vertical line through A N, where g = acceleration due to gravity. We passes through the CG. We mark the vertical take g = 9.8 m/s2. AA1. We then suspend the body through other With numerical values inserted, from (i) points like B and C. The intersection of the R1 + R2 – 4.00g – 6.00g = 0 verticals gives the CG. Explain why the method or R1 + R2 = 10.00g N (iii) works. Since the body is small enough, the = 98.00 N method allows us to determine also its centre From (ii), – 0.25 R1 + 0.05 W1 + 0.25 R2 = 0 of mass. or R1 – R2 = 1.2g N = 11.76 N (iv) From (iii) and (iv), R1 = 54.88 N, u Example 6.8 A metal bar 70 cm long and R2 = 43.12 N 4.00 kg in mass supported on two knife- Thus the reactions of the support are about edges placed 10 cm from each end. A 6.00 55 N at K1 and 43 N at K2. ⊳ kg load is suspended at 30 cm from one end. Find the reactions at the knife-edges. u Example 6.9 A 3m long ladder weighing (Assume the bar to be of uniform cross 20 kg leans on a frictionless wall. Its feet section and homogeneous.) rest on the floor 1 m from the wall as shown in Fig.6.27. Find the reaction forces of the Answer wall and the floor. Answer Fig. 6.26 Figure 6.26 shows the rod AB, the positions of the knife edges K1 and K2 , the centre of gravity of the rod at G and the suspended load at P. Note the weight of the rod W acts at its centre of gravity G. The rod is uniform in cross section and homogeneous; hence G is at the centre of the rod; AB = 70 cm. AG = 35 cm, AP Fig. 6.27 Reprint 2025-26 114 PHYSICS The ladder AB is 3 m long, its foot A is at from the axis, the linear velocity is υi = ir ω. The distance AC = 1 m from the wall. From kinetic energy of motion of this particle is Pythagoras theorem, BC = 2 2 m. The forces 1 2 1 2 2 on the ladder are its weight W acting at its centre k i = m i υi = m i ri ω 2 2 of gravity D, reaction forces F1 and F2 of the wall where mi is the mass of the particle. The totaland the floor respectively. Force F1 is kinetic energy K of the body is then given byperpendicular to the wall, since the wall is the sum of the kinetic energies of individualfrictionless. Force F2 is resolved into two particles,components, the normal reaction N and the force of friction F. Note that F prevents the ladder n 1 n 2 2 from sliding away from the wall and is therefore K = ∑ k i = ∑ (m i ri ω ) i =1 2 i =1 directed toward the wall. For translational equilibrium, taking the Here n is the number of particles in the body. forces in the vertical direction, Note ωis the same for all particles. Hence, taking N – W = 0 (i) ω out of the sum, Taking the forces in the horizontal direction, n 1 2 2 i ri ) F – F1 = 0 (ii) K = 2 ω ( ∑i =1 m For rotational equilibrium, taking the We define a new parameter characterisingmoments of the forces about A, the rigid body, called the moment of inertia I , 2 2 F1 −(1/2) W = 0 (iii) given by Now W = 20 g = 20 × 9.8 N = 196.0 N n 2 I = ∑ m i ri (6.34)From (i) N = 196.0 N i =1 With this definition,From (iii) F1 = W 4 2 = 196.0/4 2 = 34.6 N 1 2 From (ii) F = F1 = 34.6 N K = Iω (6.35) 2 2 2 Note that the parameter I is independent of F2 = F + N = 199.0 N the magnitude of the angular velocity. It is a The force F2 makes an angle α with the characteristic of the rigid body and the axis horizontal, about which it rotates. −1 Compare Eq. (6.35) for the kinetic energy oftan α = N F = 4 2 , α = tan (4 2) ≈ 80 ⊳ a rotating body with the expression for the kinetic energy of a body in linear (translational)6.9 MOMENT OF INERTIA motion, We have already mentioned that we are 1 2developing the study of rotational motion parallel K = m υ 2to the study of translational motion with which Here, m is the mass of the body and v is itswe are familiar. We have yet to answer one major velocity. We have already noted the analogy question in this connection. What is the between angular velocity ω (in respect of analogue of mass in rotational motion? We shall rotational motion about a fixed axis) and linear attempt to answer this question in the present velocity v (in respect of linear motion). It is then section. To keep the discussion simple, we shall evident that the parameter, moment of inertia consider rotation about a fixed axis only. Let us I, is the desired rotational analogue of mass in try to get an expression for the kinetic energy of linear motion. In rotation (about a fixed axis), a rotating body. We know that for a body rotating the moment of inertia plays a similar role as about a fixed axis, each particle of the body moves mass does in linear motion. We now apply the definition Eq. (6.34), toin a circle with linear velocity given by Eq. (6.19). calculate the moment of inertia in two simple cases.(Refer to Fig. 6.16). For a particle at a distance Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 115 (a) Consider a thin ring of radius R and mass change in its rotational motion, it can be M, rotating in its own plane around its centre regarded as a measure of rotational inertia of with angular velocity ω. Each mass element the body; it is a measure of the way in which of the ring is at a distance R from the axis, different parts of the body are distributed at and moves with a speed Rω. The kinetic different distances from the axis. Unlike the energy is therefore, mass of a body, the moment of inertia is not a fixed quantity but depends on distribution of 1 2 1 2 2 K = M υ = MR ω mass about the axis of rotation, and the 2 2 orientation and position of the axis of rotation Comparing with Eq. (6.35) we get I = MR 2 with respect to the body as a whole. As a for the ring. measure of the way in which the mass of a rotating rigid body is distributed with respect to the axis of rotation, we can define a new parameter, the radius of gyration. It is related to the moment of inertia and the total mass of the body. Notice from the Table 6.1 that in all cases, we can write I = Mk2, where k has the dimension of length. For a rod, about the perpendicular axis at its midpoint, k 2 = L2 12, i.e. k = L 12 . Similarly, k = R/2 for the circular disc about its diameter. The length k is a geometric property of the body and axis of rotation. It is called the radius of Fig. 6.28 A light rod of length l with a pair of gyration. The radius of gyration of a body masses rotating about an axis through about an axis may be defined as the distance the centre of mass of the system and perpendicular to the rod. The total mass from the axis of a mass point whose mass is of the system is M. equal to the mass of the whole body and whose moment of inertia is equal to the moment of (b) Next, take a rigid rod of negligible mass of inertia of the body about the axis. length of length l with a pair of small masses, Thus, the moment of inertia of a rigid body rotating about an axis through the centre of depends on the mass of the body, its shape and mass perpendicular to the rod (Fig. 6.28). size; distribution of mass about the axis of Each mass M/2 is at a distance l/2 from rotation, and the position and orientation of the the axis. The moment of inertia of the masses axis of rotation. is therefore given by From the definition, Eq. (6.34), we can infer (M/2) (l/2)2 + (M/2)(l/2)2 that the dimensions of moments of inertia are Thus, for the pair of masses, rotating about ML2 and its SI units are kg m2. the axis through the centre of mass The property of this extremely important perpendicular to the rod 2 quantity I, as a measure of rotational inertia of I = Ml / 4 the body, has been put to a great practical use. Table 6.1 simply gives the moment of inertia of The machines, such as steam engine and thevarious familiar regular shaped bodies about automobile engine, etc., that produce rotationalspecific axes. (The derivations of these motion have a disc with a large moment ofexpressions are beyond the scope of this inertia, called a flywheel. Because of its largetextbook and you will study them in higher classes.) moment of inertia, the flywheel resists the As the mass of a body resists a change in its sudden increase or decrease of the speed of the state of linear motion, it is a measure of its inertia vehicle. It allows a gradual change in the speed in linear motion. Similarly, as the moment of and prevents jerky motions, thereby ensuring inertia about a given axis of rotation resists a a smooth ride for the passengers on the vehicle. Reprint 2025-26 116 PHYSICS Table 6.1 Moments of inertia of some regular shaped bodies about specific axes Z Body Axis Figure I (1) Thin circular Perpendicular to M R 2 ring, radius R plane, at centre (2) Thin circular Diameter M R2/2 ring, radius R (3) Thin rod, Perpendicular to M L2/12 length L rod, at mid point (4) Circular disc, Perpendicular to M R2/2 radius R disc at centre (5) Circular disc, Diameter M R2/4 radius R (6) Hollow cylinder, Axis of cylinder M R2 radius R (7) Solid cylinder, Axis of cylinder M R2/2 radius R (8) Solid sphere, Diameter 2 M R2/5 radius R 6.10 KINEMATICS OF ROTATIONAL MOTION translation. We wish to take this analogy further. ABOUT A FIXED AXIS In doing so we shall restrict the discussion only We have already indicated the analogy between to rotation about fixed axis. This case of motion rotational motion and translational motion. For involves only one degree of freedom, i.e., needs example, the angular velocity ω plays the same only one independent variable to describe the role in rotation as the linear velocity v in motion. This in translation corresponds to linear Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 117 motion. This section is limited only to kinematics. We shall turn to dynamics in later sections. We recall that for specifying the angular displacement of the rotating body we take any particle like P (Fig.6.29) of the body. Its angular displacement θ in the plane it moves is the angular displacement of the whole body; θ is measured from a fixed direction in the plane of motion of P, which we take to be the x′-axis, chosen parallel to the x-axis. Note, as shown, the axis of rotation is the z – axis and the plane of the motion of the particle is the x - y plane. Fig. 6.29 also shows θ0, the angular displacement at t = 0. We also recall that the angular velocity is the time rate of change of angular displacement, ω = dθ/dt. Note since the axis of rotation is fixed, there is no need to treat angular velocity as a Fig.6.29 Specifying the angular position of a rigid vector. Further, the angular acceleration, α = body. dω/dt. u Example 6.10 Obtain Eq. (6.36) from first The kinematical quantities in rotational principles. motion, angular displacement (θ), angular velocity (ω) and angular acceleration (α) Answer The angular acceleration is uniform, respectively are analogous to kinematic hence quantities in linear motion, displacement (x), dω velocity (v) and acceleration (a). We know the = α = constant (i) kinematical equations of linear motion with d t uniform (i.e. constant) acceleration: Integrating this equation, α dt + c v = v0 + at (a) ω = ∫ 1 2 x = x 0 + υ0t + at (b) = αt + c (as α is constant) 2 At t = 0, ω = ω0 (given) 2 2 υ = υ0 + 2ax (c) From (i) we get at t = 0, ω = c = ω0 Thus, ω = αt + ω0 as required. where x0 = initial displacement and v0= initial With the definition of ω = dθ/dt we may velocity. The word ‘initial’ refers to values of the integrate Eq. (6.36) to get Eq. (6.37). This quantities at t = 0 derivation and the derivation of Eq. (6.38) is left The corresponding kinematic equations for as an exercise. rotational motion with uniform angular acceleration are: u Example 6.11 The angular speed of a motor wheel is increased from 1200 rpm to ω= ω0 + αt (6.36) 3120 rpm in 16 seconds. (i) What is its angular acceleration, assuming the 1 2 θ = θ0 + ω0t + αt (6.37) acceleration to be uniform? (ii) How many 2 revolutions does the engine make during and ω2 = ω0 2 + 2α(θ– θ0 ) (6.38) this time? Answer where θ0= initial angular displacement of the (i) We shall use ω = ω0 + αt rotating body, and ω0 = initial angular velocity ω0 = initial angular speed in rad/s of the body. Reprint 2025-26 118 PHYSICS = 2π × angular speed in rev/s It is, however, necessary that these correspondences are established on sound 2π × angular speed in rev/min dynamical considerations. This is what we now = 60 s/min turn to. Before we begin, we note a simplification 2π × 1200 that arises in the case of rotational motion = rad/s 60 about a fixed axis. Since the axis is fixed, only those components of torques, which are along = 40π rad/s the direction of the fixed axis need to be Similarly ω = final angular speed in rad/s considered in our discussion. Only these 2π × 3120 components can cause the body to rotate about = rad/s the axis. A component of the torque 60 perpendicular to the axis of rotation will tend to = 2π × 52 rad/s turn the axis from its position. We specifically = 104 π rad/s assume that there will arise necessary forces of constraint to cancel the effect of the ∴Angular acceleration perpendicular components of the (external) torques, so that the fixed position of the axis ω − ω will be maintained. The perpendicular α = 0 = 4 π rad/s2 t components of the torques, therefore need not be taken into account. This means that for our The angular acceleration of the engine calculation of torques on a rigid body: = 4π rad/s2 (1) We need to consider only those forces that (ii) The angular displacement in time t is lie in planes perpendicular to the axis. given by Forces which are parallel to the axis will give torques perpendicular to the axis and need 1 2 θ = ω0 t + αt not be taken into account. 2 (2) We need to consider only those components 1 2 of the position vectors which are = (40π × 16 + × 4π × 16 ) rad 2 perpendicular to the axis. Components of position vectors along the axis will result in = (640π + 512π) rad torques perpendicular to the axis and need = 1152π rad not be taken into account. 1152π = 576 ⊳ Work done by a torqueNumber of revolutions = 2π