11.6 SPECIFIC HEAT CAPACITY average energy of 2 × ½ kBT = kBT. In three dimensions, the average energy is 3 kBT.Suppose an amount of heat ∆Q supplied to a For a mole of a solid, the total energy is substance changes its temperature from T to T + ∆T. We define heat capacity of a substance U = 3 kBT × NA = 3 RT (∵kBT × NA = R) (see Chapter 10) to be Now, at constant pressure, ∆Q = ∆U + P ∆V ≅ ∆ Q ∆U, since for a solid ∆V is negligible. Therefore, S = (11.4) ∆ T ∆ Q ∆U C = = = 3 R (11.7) We expect ∆Q and, therefore, heat capacity S ∆ T ∆ T to be proportional to the mass of the substance. Table 11.1 Specific and molar heat capacities Further, it could also depend on the of some solids at room temperature, i.e., a different amount of heat may temperature and atmospheric be needed for a unit rise in temperature at pressure different temperatures. To define a constant –v Speci"c heat Molar speci"c characteristic of the substance and Substance –1 –1 –1 –1 (J kg K ) heat (J mol K ) independent of its amount, we divide S by the mass of the substance m in kg : S  1  ∆Q s = (11.5) m =  m  ∆T s is known as the specific heat capacity of the substance. It depends on the nature of the As Table 11.1 shows, the experimentally substance and its temperature. The unit of measured values which generally agrees withspecific heat capacity is J kg–1 K–1. Reprint 2025-26 232 PHYSICS predicted value 3R at ordinary temperatures. ideal gas, we have a simple relation. (Carbon is an exception.) The agreement is known to break down at low temperatures. Cp – Cv = R (11.8) Specific heat capacity of water where Cp and Cv are molar specific heat capacities of an ideal gas at constant pressure The old unit of heat was calorie. One calorie and volume respectively and R is the universal was earlier defined to be the amount of heat gas constant. To prove the relation, we begin required to raise the temperature of 1g of water with Eq. (11.3) for 1 mole of the gas : by 1°C. With more precise measurements, it was found that the specific heat of water varies ∆Q = ∆U + P ∆V slightly with temperature. Figure 11.5 shows If ∆Q is absorbed at constant volume, ∆V = 0this variation in the temperature range 0 to 100 °C.  ∆Q   ∆ U   ∆ U  (11.9) C v =  ∆T  v =  ∆T  v =  ∆T  where the subscript v is dropped in the last step, since U of an ideal gas depends only on temperature. (The subscript denotes the quantity kept fixed.) If, on the other hand, ∆Q is absorbed at constant pressure,  ∆ Q   ∆ U   ∆V  (11.10) C p =  ∆T  p =  ∆T  p + P  ∆ T  p The subscript p can be dropped from the Fig. 11.5 Variation of specific heat capacity of first term since U of an ideal gas depends only water with temperature. on T. Now, for a mole of an ideal gas For a precise definition of calorie, it was, PV = RTtherefore, necessary to specify the unit temperature interval. One calorie is defined which gives to be the amount of heat required to raise the temperature of 1g of water from 14.5 °C to  ∆ V  P = R (11.11)15.5 °C. Since heat is just a form of energy,  ∆ T  p it is preferable to use the unit joule, J. In SI units, the specific heat capacity of water Equations (11.9) to (11.11) give the desired is 4186 J kg–1 K–1 i.e. 4.186 J g–1 K–1. The so relation, Eq. (11.8). called mechanical equivalent of heat defined 11.7THERMODYNAMIC STATE VARIABLES as the amount of work needed to produce AND EQUATION OF STATE 1 cal of heat is in fact just a conversion factor between two different units of energy : calorie Every equilibrium state of a thermodynamic to joule. Since in SI units, we use the unit joule system is completely described by specific for heat, work or any other form of energy, the values of some macroscopic variables, also term mechanical equivalent is now called state variables. For example, an superfluous and need not be used. equilibrium state of a gas is completely As already remarked, the specific heat specified by the values of pressure, volume, capacity depends on the process or the temperature, and mass (and composition if conditions under which heat capacity transfer there is a mixture of gases). A thermodynamic takes place. For gases, for example, we can system is not always in equilibrium. For example, define two specific heats : specific heat a gas allowed to expand freely against vacuum capacity at constant volume and specific is not an equilibrium state [Fig. 11.6(a)]. During heat capacity at constant pressure. For an the rapid expansion, pressure of the gas may Reprint 2025-26 THERMODYNAMICS 233 not be uniform throughout. Similarly, a mixture temperature do not. To decide which variable is of gases undergoing an explosive chemical extensive and which intensive, think of a reaction (e.g. a mixture of petrol vapour and relevant system in equilibrium, and imagine that air when ignited by a spark) is not an it is divided into two equal parts. The variables that remain unchanged for each part areequilibrium state; again its temperature and intensive. The variables whose values get halvedpressure are not uniform [Fig. 11.6(b)]. in each part are extensive. It is easily seen, forEventually, the gas attains a uniform example, that internal energy U, volume V, total temperature and pressure and comes to mass M are extensive variables. Pressure P, thermal and mechanical equilibrium with its temperature T, and density ρ are intensive surroundings. variables. It is a good practice to check the consistency of thermodynamic equations using this classification of variables. For example, in the equation ∆Q = ∆U + P ∆V quantities on both sides are extensive*. (The product of an intensive variable like P and an extensive quantity ∆V is extensive.) 11.8 THERMODYNAMIC PROCESSES 11.8.1 Quasi-static process Consider a gas in thermal and mechanical equilibrium with its surroundings. The pressure of the gas in that case equals the external Fig. 11.6 (a) The partition in the box is suddenly pressure and its temperature is the same as removed leading to free expansion of the that of its surroundings. Suppose that the gas. (b) A mixture of gases undergoing an external pressure is suddenly reduced (say by explosive chemical reaction. In both lifting the weight on the movable piston in the situations, the gas is not in equilibrium and container). The piston will accelerate outward. cannot be described by state variables. During the process, the gas passes through In short, thermodynamic state variables states that are not equilibrium states. The non- describe equilibrium states of systems. The equilibrium states do not have well-defined various state variables are not necessarily pressure and temperature. In the same way, if independent. The connection between the state a finite temperature difference exists between variables is called the equation of state. For the gas and its surroundings, there will be a example, for an ideal gas, the equation of state rapid exchange of heat during which the gas is the ideal gas relation will pass through non-equilibrium states. In due course, the gas will settle to an equilibrium P V = µ R T state with well-defined temperature and For a fixed amount of the gas i.e. given µ, there pressure equal to those of the surroundings. The are thus, only two independent variables, say P free expansion of a gas in vacuum and a mixture and V or T and V. The pressure-volume curve of gases undergoing an explosive chemical for a fixed temperature is called an isotherm. reaction, mentioned in section 11.7 are also Real gases may have more complicated examples where the system goes through non- equations of state. equilibrium states. The thermodynamic state variables are of two Non-equilibrium states of a system are difficult kinds: extensive and intensive. Extensive to deal with. It is, therefore, convenient to variables indicate the ‘size’ of the system. imagine an idealised process in which at every Intensive variables such as pressure and stage the system is an equilibrium state. Such a * As emphasised earlier, Q is not a state variable. However, ∆Q is clearly proportional to the total mass of system and hence is extensive. Reprint 2025-26 234 PHYSICS process is, in principle, infinitely slow, hence the A process in which the temperature of the name quasi-static (meaning nearly static). The system is kept fixed throughout is called an system changes its variables (P, T, V ) so slowly isothermal process. The expansion of a gas in that it remains in thermal and mechanical a metallic cylinder placed in a large reservoir of equilibrium with its surroundings throughout. fixed temperature is an example of an isothermal In a quasi-static process, at every stage, the process. (Heat transferred from the reservoir to difference in the pressure of the system and the the system does not materially affect the external pressure is infinitesimally small. The temperature of the reservoir, because of its very large heat capacity.) In isobaric processes thesame is true of the temperature difference pressure is constant while in isochoricbetween the system and its surroundings processes the volume is constant. Finally, if the(Fig.11.7). To take a gas from the state (P, T ) to another state (P ′, T ′ ) via a quasi-static process, system is insulated from the surroundings and no heat flows between the system and thewe change the external pressure by a very small surroundings, the process is adiabatic. The amount, allow the system to equalise its pressure definitions of these special processes are with that of the surroundings and continue the summarised in Table. 11.2 process infinitely slowly until the system achieves the pressure P ′. Similarly, to change Table 11.2 Some special thermodynamic the temperature, we introduce an infinitesimal processes temperature difference between the system and the surrounding reservoirs and by choosing reservoirs of progressively different temperatures T to T ′, the system achieves the temperature T ′. We now consider these processes in some detail : 11.8.2 Isothermal process For an isothermal process (T fixed), the ideal gas equation gives PV = constant i.e., pressure of a given mass of gas varies inversely as its volume. This is nothing but Boyle’s Law. Suppose an ideal gas goes isothermally (at temperature T ) from its initial state (P1, V1) to Fig. 11.7 In a quasi-static process, the temperature the final state (P2, V 2). At any intermediate stage of the surrounding reservoir and the with pressure P and volume change from V to external pressure differ only infinitesimally V + ∆V (∆V small) from the temperature and pressure of the system. ∆W = P ∆ V A quasi-static process is obviously a Taking (∆V → 0) and summing the quantity hypothetical construct. In practice, processes ∆W over the entire process, that are sufficiently slow and do not involve V2 accelerated motion of the piston, large W = ∫ P d V temperature gradient, etc., are reasonably V1 approximation to an ideal quasi-static process. V2 d V V2We shall from now on deal with quasi-static = µ RT = µRT In ∫ (11.12) Vprocesses only, except when stated otherwise. V1 V 1 Reprint 2025-26 THERMODYNAMICS 235 where in the second step we have made use of We can calculate, as before, the work done in the ideal gas equation PV = µ RT and taken the an adiabatic change of an ideal gas from the constants out of the integral. For an ideal gas, state (P1, V1, T1) to the state (P2, V2, T2). internal energy depends only on temperature. V 2Thus, there is no change in the internal energy W = ∫ P d Vof an ideal gas in an isothermal process. The V1First Law of Thermodynamics then implies that heat supplied to the gas equals the work done by the gas : Q = W. Note from Eq. (11.12) that for V2 > V1, W > 0; and for V2 < V1, W < 0. That is, in an isothermal expansion, the gas absorbs heat and does work while in an isothermal (11.15) compression, work is done on the gas by the environment and heat is released. From Eq. (11.14), the constant is P1V1γ or P2V2γ 11.8.3 Adiabatic process γ  γ  P2 V 2 P1V 1In an adiabatic process, the system is insulated W = 1 − 1   −1 γ γ − from the surroundings and heat absorbed or 1 − γ  V2 V1  released is zero. From Eq. (11.1), we see that work done by the gas results in decrease in its 1 µR(T1 − T2 ) = [ P2 V2 − P1V1 ] = (11.16)internal energy (and hence its temperature for 1 − γ γ − 1 an ideal gas). We quote without proof (the result that you will learn in higher courses) that for As expected, if work is done by the gas in an an adiabatic process of an ideal gas. adiabatic process (W > 0), from Eq. (11.16), P V γ = const (11.13) T2 < T1. On the other hand, if work is done on the gas (W < 0), we get T2 > T1 i.e., thewhere γ is the ratio of specific heats (ordinary temperature of the gas rises. or molar) at constant pressure and at constant volume. 11.8.4 Isochoric process Cp In an isochoric process, V is constant. No work γ = Cv is done on or by the gas. From Eq. (11.1), the heat absorbed by the gas goes entirely to change Thus if an ideal gas undergoes a change in its internal energy and its temperature. The its state adiabatically from (P1, V1) to (P2, V2) : change in temperature for a given amount of γ = P2 V2γ (11.14) heat is determined by the specific heat of the P1 V1 gas at constant volume. Figure11.8 shows the P-V curves of an ideal gas for two adiabatic processes connecting two 11.8.5 Isobaric process isotherms. In an isobaric process, P is fixed. Work done by the gas is W = P (V2 – V1) = µ R (T2 – T1) (11.17) Since temperature changes, so does internal energy. The heat absorbed goes partly to increase internal energy and partly to do work. The change in temperature for a given amount of heat is determined by the specific heat of the gas at constant pressure. 11.8.6 Cyclic process In a cyclic process, the system returns to its initial state. Since internal energy is a stateFig. 11.8 P-V curves for isothermal and adiabatic variable, ∆U = 0 for a cyclic process. From processes of an ideal gas. Reprint 2025-26 236 PHYSICS Eq. (11.1), the total heat absorbed equals the 11.10 REVERSIBLE AND IRREVERSIBLE work done by the system. PROCESSES Imagine some process in which a thermodynamic11.9 SECOND LAW OF THERMODYNAMICS system goes from an initial state i to a final state The First Law of Thermodynamics is the f. During the process the system absorbs heat Q principle of conservation of energy. Common from the surroundings and performs work W on experience shows that there are many it. Can we reverse this process and bring both conceivable processes that are perfectly the system and surroundings to their initial allowed by the First Law and yet are never states with no other effect anywhere ? Experience observed. For example, nobody has ever seen suggests that for most processes in nature this a book lying on a table jumping to a height by is not possible. The spontaneous processes ofitself. But such a thing would be possible if nature are irreversible. Several examples can bethe principle of conservation of energy were cited. The base of a vessel on an oven is hotterthe only restriction. The table could cool than its other parts. When the vessel is removed,spontaneously, converting some of its internal heat is transferred from the base to the otherenergy into an equal amount of mechanical parts, bringing the vessel to a uniformenergy of the book, which would then hop to a height with potential energy equal to the temperature (which in due course cools to the mechanical energy it acquired. But this never temperature of the surroundings). The process happens. Clearly, some additional basic cannot be reversed; a part of the vessel will not principle of nature forbids the above, even get cooler spontaneously and warm up the base. though it satisfies the energy conservation It will violate the Second Law of Thermodynamics, principle. This principle, which disallows if it did. The free expansion of a gas is irreversible. many phenomena consistent with the First The combustion reaction of a mixture of petrol Law of Thermodynamics is known as the and air ignited by a spark cannot be reversed. Second Law of Thermodynamics. Cooking gas leaking from a gas cylinder in the The Second Law of Thermodynamics gives kitchen diffuses to the entire room. The diffusion a fundamental limitation to the efficiency of a process will not spontaneously reverse and bring heat engine and the co-efficient of the gas back to the cylinder. The stirring of a performance of a refrigerator. In simple terms, liquid in thermal contact with a reservoir will it says that efficiency of a heat engine can convert the work done into heat, increasing the never be unity. For a refrigerator, the Second internal energy of the reservoir. The process Law says that the co-efficient of performance cannot be reversed exactly; otherwise it would can never be infinite. The following two amount to conversion of heat entirely into work, statements, one due to Kelvin and Planck violating the Second Law of Thermodynamics. denying the possibility of a perfect heat engine, Irreversibility is a rule rather an exception and another due to Clausius denying the in nature. possibility of a perfect refrigerator or heat Irreversibility arises mainly from two causes: pump, are a concise summary of these one, many processes (like a free expansion, or observations. an explosive chemical reaction) take the system Kelvin-Planck statement to non-equilibrium states; two, most processes No process is possible whose sole result is the involve friction, viscosity and other dissipative absorption of heat from a reservoir and the effects (e.g., a moving body coming to a stop and complete conversion of the heat into work. losing its mechanical energy as heat to the floor and the body; a rotating blade in a liquid coming Clausius statement to a stop due to viscosity and losing its No process is possible whose sole result is the mechanical energy with corresponding gain in transfer of heat from a colder object to a the internal energy of the liquid). Since hotter object. dissipative effects are present everywhere and It can be proved that the two statements can be minimised but not fully eliminated, most above are completely equivalent. processes that we deal with are irreversible. Reprint 2025-26 THERMODYNAMICS 237 A thermodynamic process (state i → state f ) in a reversible heat engine operating between is reversible if the process can be turned back two temperatures, heat should be absorbed such that both the system and the surroundings (from the hot reservoir) isothermally and return to their original states, with no other released (to the cold reservoir) isothermally. We change anywhere else in the universe. From the thus have identified two steps of the reversible preceding discussion, a reversible process is an heat engine : isothermal process at temperature idealised notion. A process is reversible only if T1 absorbing heat Q1 from the hot reservoir, and another isothermal process at temperature T2it is quasi-static (system in equilibrium with the releasing heat Q2 to the cold reservoir. Tosurroundings at every stage) and there are no complete a cycle, we need to take the systemdissipative effects. For example, a quasi-static from temperature T1 to T2 and then back fromisothermal expansion of an ideal gas in a temperature T2 to T1. Which processes shouldcylinder fitted with a frictionless movable piston we employ for this purpose that are reversible?is a reversible process. A little reflection shows that we can only adopt Why is reversibility such a basic concept in reversible adiabatic processes for these thermodynamics ? As we have seen, one of the purposes, which involve no heat flow from any concerns of thermodynamics is the efficiency reservoir. If we employ any other process that is with which heat can be converted into work. not adiabatic, say an isochoric process, to take The Second Law of Thermodynamics rules out the system from one temperature to another, we the possibility of a perfect heat engine with 100% shall need a series of reservoirs in the efficiency. But what is the highest efficiency temperature range T2 to T1 to ensure that at each possible for a heat engine working between two stage the process is quasi-static. (Remember reservoirs at temperatures T1 and T2? It turns again that for a process to be quasi-static and out that a heat engine based on idealised reversible, there should be no finite temperature reversible processes achieves the highest difference between the system and the reservoir.) efficiency possible. All other engines involving But we are considering a reversible engine that irreversibility in any way (as would be the case operates between only two temperatures. Thus for practical engines) have lower than this adiabatic processes must bring about the limiting efficiency. temperature change in the system from T1 to T2 and T2 to T1 in this engine.11.11 CARNOT ENGINE Suppose we have a hot reservoir at temperature T1 and a cold reservoir at temperature T2. What is the maximum efficiency possible for a heat engine operating between the two reservoirs and what cycle of processes should be adopted to achieve the maximum efficiency ? Sadi Carnot, a French engineer, first considered this question in 1824. Interestingly, Carnot arrived at the correct answer, even though the basic concepts of heat and thermodynamics had yet to be firmly established. We expect the ideal engine operating between two temperatures to be a reversible engine. Irreversibility is associated with dissipative Fig. 11.9 Carnot cycle for a heat engine with an effects, as remarked in the preceding section, ideal gas as the working substance. and lowers efficiency. A process is reversible if it is quasi-static and non-dissipative. We have A reversible heat engine operating between seen that a process is not quasi-static if it two temperatures is called a Carnot engine. We involves finite temperature difference between have just argued that such an engine must have the system and the reservoir. This implies that the following sequence of steps constituting one Reprint 2025-26 238 PHYSICS cycle, called the Carnot cycle, shown in Fig. 11.9. We have taken the working substance In  V 3  of the Carnot engine to be an ideal gas. T2   V4  = 1 −  T1   V2  (11.23)(a) Step 1 → 2 Isothermal expansion of the gas In  V1  taking its state from (P1, V1, T1) to (P2, V2, T1). Now since step 2 → 3 is an adiabatic process, The heat absorbed by the gas (Q1) from the γ −1 γ −1 reservoir at temperature T1 is given by T1 V 2 = T2 V3 Eq. (11.12). This is also the work done (W1 → 2) by the gas on the environment. 1 /( γ −1 ) V2  T2   V2  i.e. = (11.24) 3  T1  W1 → 2 = Q1 = µ R T1 ln  V1  (11.18) V (b) Step 2 → 3 Adiabatic expansion of the gas Similarly, since step 4 → 1 is an adiabatic from (P2, V2, T1) to (P3, V3, T2) process Work done by the gas, using γ −1 γ −1 Eq. (11.16), is T2 V 4 = T1 V1 µR ( T1 − T2 ) 1 /γ −1 W2 →=3 (11.19) V1  T2  γ − 1 i.e. = (11.25) V4  T1  (c) Step 3 → 4 Isothermal compression of the gas from (P3, V3, T2) to (P4, V4, T2). From Eqs. (11.24) and (11.25), 2 Heat released (Q2) by the gas to the reservoir V3 = V (11.26) at temperature T2 is given by Eq. (11.12). This V4 V1 is also the work done (W3 → 4) on the gas by the environment. Using Eq. (11.26) in Eq. (11.23), we get  V 3  2 W 3 → 4 = Q2 = µRT2 ln η = 1 −T (Carnot engine) (11.27)  V 4  (11.20) T1 (d) Step 4 → 1 Adiabatic compression of the gas from (P4, V4, T2) to (P1,V1, T1). We have already seen that a Carnot engine is a reversible engine. Indeed it is the only Work done on the gas, [using Eq.(11.16), is reversible engine possible that works between two reservoirs at different temperatures. Each  T1 − T2  W4 → 1 = µR (11.21) step of the Carnot cycle given in Fig. 11.9 can  γ -1  be reversed. This will amount to taking heat Q2 from the cold reservoir at T2, doing work W on From Eqs. (11.18) to (11.21) total work done by the gas in one complete cycle is the system, and transferring heat Q1 to the hot reservoir. This will be a reversible refrigerator. W = W1 → 2 + W2 → 3 – W3 → 4 – W4 → 1 We next establish the important result  V2   V3  (sometimes called Carnot’s theorem) that = µ RT1 ln  V1  – µ RT2 ln  V4  (11.22) (a) working between two given temperatures T1 and T2 of the hot and cold reservoirs respectively, The efficiency η of the Carnot engine is no engine can have efficiency more than that of the Carnot engine and (b) the efficiency of the W Q 2 η = = 1 − Carnot engine is independent of the nature of Q1 Q1 the working substance. Reprint 2025-26 THERMODYNAMICS 239 To prove the result (a), imagine a reversible reservoir and delivers the same amount of work (Carnot) engine R and an irreversible engine I in one cycle, without any change in the source working between the same source (hot reservoir) or anywhere else. This is clearly against the and sink (cold reservoir). Let us couple the Kelvin-Planck statement of the Second Law of engines, I and R, in such a way so that I acts Thermodynamics. Hence the assertion ηI > ηR like a heat engine and R acts as a refrigerator. is wrong. No engine can have efficiency greater Let I absorb heat Q1 from the source, deliver than that of the Carnot engine. A similar work W ′ and release the heat Q1- W′ to the sink. argument can be constructed to show that a We arrange so that R returns the same heat Q1 reversible engine with one particular substance to the source, taking heat Q2 from the sink and cannot be more efficient than the one using requiring work W = Q1 – Q2 to be done on it. another substance. The maximum efficiency of Now suppose ηR < ηI i.e. if R were to act a Carnot engine given by Eq. (11.27) is as an engine it would give less work output independent of the nature of the system performing the Carnot cycle of operations. Thus we are justified in using an ideal gas as a system in the calculation of efficiency η of a Carnot engine. The ideal gas has a simple equation of I state, which allows us to readily calculate η, but the final result for η, [Eq. (11.27)], is true for any Carnot engine. R This final remark shows that in a Carnot cycle, Q1 T1 = W (11.28) T2 Q 2 is a universal relation independent of the natureFig. 11.10 An irreversible engine (I) coupled to a reversible refrigerator (R). If W ′ > W, this of the system. Here Q1 and Q2 are respectively, would amount to extraction of heat the heat absorbed and released isothermally W′ – W from the sink and its full (from the hot and to the cold reservoirs) in a conversion to work, in contradiction with Carnot engine. Equation (11.28), can, therefore, the Second Law of Thermodynamics. be used as a relation to define a truly universal thermodynamic temperature scale that is than that of I i.e. W < W ′ for a given Q1. With R independent of any particular properties of the acting like a refrigerator, this would mean system used in the Carnot cycle. Of course, for Q2 = Q1 – W > Q1 – W ′. Thus, on the whole, an ideal gas as a working substance, this the coupled I-R system extracts heat universal temperature is the same as the ideal (Q1 – W) – (Q1 – W ′) = (W ′ – W ) from the cold gas temperature introduced in section 11.9. SUMMARY 1. The zeroth law of thermodynamics states that ‘two systems in thermal equilibrium with a third system separately are in thermal equilibrium with each other’. The Zeroth Law leads to the concept of temperature. 2. Internal energy of a system is the sum of kinetic energies and potential energies of the molecular constituents of the system. It does not include the over-all kinetic energy of the system. Heat and work are two modes of energy transfer to the system. Heat is the energy transfer arising due to temperature difference between the system and the surroundings. Work is energy transfer brought about by other means, such as moving the piston of a cylinder containing the gas, by raising or lowering some weight connected to it. Reprint 2025-26 240 PHYSICS 3. The first law of thermodynamics is the general law of conservation of energy applied to any system in which energy transfer from or to the surroundings (through heat and work) is taken into account. It states that ∆Q = ∆U + ∆W where ∆Q is the heat supplied to the system, ∆W is the work done by the system and ∆U is the change in internal energy of the system. 4. The specific heat capacity of a substance is defined by 1 ∆Q s = m ∆T where m is the mass of the substance and ∆Q is the heat required to change its temperature by ∆T. The molar specific heat capacity of a substance is defined by 1 ∆ Q C = µ ∆T where µ is the number of moles of the substance. For a solid, the law of equipartition of energy gives C = 3 R which generally agrees with experiment at ordinary temperatures. Calorie is the old unit of heat. 1 calorie is the amount of heat required to raise the temperature of 1 g of water from 14.5 °C to 15.5 °C. 1 cal = 4.186 J. 5. For an ideal gas, the molar specific heat capacities at constant pressure and volume satisfy the relation Cp – Cv = R where R is the universal gas constant. 6. Equilibrium states of a thermodynamic system are described by state variables. The value of a state variable depends only on the particular state, not on the path used to arrive at that state. Examples of state variables are pressure (P ), volume (V ), temperature (T ), and mass (m ). Heat and work are not state variables. An Equation of State (like the ideal gas equation PV = µ RT ) is a relation connecting different state variables. 7. A quasi-static process is an infinitely slow process such that the system remains in thermal and mechanical equilibrium with the surroundings throughout. In a quasi-static process, the pressure and temperature of the environment can differ from those of the system only infinitesimally. 8. In an isothermal expansion of an ideal gas from volume V1 to V2 at temperature T the heat absorbed (Q) equals the work done (W ) by the gas, each given by  V 2   Q = W = µ R T ln   V1  9. In an adiabatic process of an ideal gas γ PV = constant C p where γ = C v Work done by an ideal gas in an adiabatic change of state from (P1, V1, T1) to (P2, V2, T2) is µR ( T1 − T2 ) W = γ – 1 Reprint 2025-26 THERMODYNAMICS 241 10. The second law of thermodynamics disallows some processes consistent with the First Law of Thermodynamics. It states Kelvin-Planck statement No process is possible whose sole result is the absorption of heat from a reservoir and complete conversion of the heat into work. Clausius statement No process is possible whose sole result is the transfer of heat from a colder object to a hotter object. Put simply, the Second Law implies that no heat engine can have efficiency η equal to 1 or no refrigerator can have co-efficient of performance α equal to infinity. 11. A process is reversible if it can be reversed such that both the system and the surroundings return to their original states, with no other change anywhere else in the universe. Spontaneous processes of nature are irreversible. The idealised reversible process is a quasi-static process with no dissipative factors such as friction, viscosity, etc. 12. Carnot engine is a reversible engine operating between two temperatures T1 (source) and T2 (sink). The Carnot cycle consists of two isothermal processes connected by two adiabatic processes. The efficiency of a Carnot engine is given by T 2 η= 1 − (Carnot engine) T1 No engine operating between two temperatures can have efficiency greater than that of the Carnot engine. 13. If Q > 0, heat is added to the system If Q < 0, heat is removed to the system If W > 0, Work is done by the system If W < 0, Work is done on the system Quantity Symbol Dimensions Unit Remark Co-efficienty of volume αv [K–1] K–1 αv = 3 α1 expansion Heat supplied to a system ∆Q [ML2 T–2] J Q is not a state variable Specific heat capacity s [L2 T–2 K–1] J kg–1 K–1 dt Thermal Conductivity K [MLT–3 K–1] J s–1 K–1 H = – KA dx POINTS TO PONDER 1. Temperature of a body is related to its average internal energy, not to the kinetic energy of motion of its centre of mass. A bullet fired from a gun is not at a higher temperature because of its high speed. 2. Equilibrium in thermodynamics refers to the situation when macroscopic variables describing the thermodynamic state of a system do not depend on time. Equilibrium of a system in mechanics means the net external force and torque on the system are zero. Reprint 2025-26 242 PHYSICS 3. In a state of thermodynamic equilibrium, the microscopic constituents of a system are not in equilibrium (in the sense of mechanics). 4. Heat capacity, in general, depends on the process the system goes through when heat is supplied. 5. In isothermal quasi-static processes, heat is absorbed or given out by the system even though at every stage the gas has the same temperature as that of the surrounding reservoir. This is possible because of the infinitesimal difference in temperature between the system and the reservoir. EXERCISES 11.1 A geyser heats water flowing at the rate of 3.0 litres per minute from 27 °C to 77 °C. If the geyser operates on a gas burner, what is the rate of consumption of the fuel if its heat of combustion is 4.0 × 104 J/g ? 11.2 What amount of heat must be supplied to 2.0 × 10–2 kg of nitrogen (at room temperature) to raise its temperature by 45 °C at constant pressure ? (Molecular mass of N2 = 28; R = 8.3 J mol–1 K–1.) 11.3 Explain why (a) Two bodies at different temperatures T1 and T2 if brought in thermal contact do not necessarily settle to the mean temperature (T1 + T2 )/2. (b) The coolant in a chemical or a nuclear plant (i.e., the liquid used to prevent the different parts of a plant from getting too hot) should have high specific heat. (c) Air pressure in a car tyre increases during driving. (d) The climate of a harbour town is more temperate than that of a town in a desert at the same latitude. 11.4 A cylinder with a movable piston contains 3 moles of hydrogen at standard temperature and pressure. The walls of the cylinder are made of a heat insulator, and the piston is insulated by having a pile of sand on it. By what factor does the pressure of the gas increase if the gas is compressed to half its original volume ? 11.5 In changing the state of a gas adiabatically from an equilibrium state A to another equilibrium state B, an amount of work equal to 22.3 J is done on the system. If the gas is taken from state A to B via a process in which the net heat absorbed by the system is 9.35 cal, how much is the net work done by the system in the latter case ? (Take 1 cal = 4.19 J) 11.6 Two cylinders A and B of equal capacity are connected to each other via a stopcock. A contains a gas at standard temperature and pressure. B is completely evacuated. The entire system is thermally insulated. The stopcock is suddenly opened. Answer the following : (a) What is the final pressure of the gas in A and B ? (b) What is the change in internal energy of the gas ? (c) What is the change in the temperature of the gas ? (d) Do the intermediate states of the system (before settling to the final equilibrium state) lie on its P-V-T surface ? 11.7 An electric heater supplies heat to a system at a rate of 100W. If system performs work at a rate of 75 joules per second. At what rate is the internal energy increasing? Reprint 2025-26 THERMODYNAMICS 243 11.8 A thermodynamic system is taken from an original state to an intermediate state by the linear process shown in Fig. (11.13) Fig. 11.11 Its volume is then reduced to the original value from E to F by an isobaric process. Calculate the total work done by the gas from D to E to F Reprint 2025-26 CHAPTER TWELVE KINETIC THEORY 12.1 INTRODUCTION Boyle discovered the law named after him in 1661. Boyle, Newton and several others tried to explain the behaviour of 12.1 Introduction gases by considering that gases are made up of tiny atomic 12.2 Molecular nature of matter particles. The actual atomic theory got established more than 12.3 Behaviour of gases 150 years later. Kinetic theory explains the behaviour of gases 12.4 Kinetic theory of an ideal gas based on the idea that the gas consists of rapidly moving 12.5 Law of equipartition of energy atoms or molecules. This is possible as the inter-atomic forces, 12.6 Specific heat capacity which are short range forces that are important for solids and liquids, can be neglected for gases. The kinetic theory12.7 Mean free path was developed in the nineteenth century by Maxwell, Summary Boltzmann and others. It has been remarkably successful. It Points to ponder gives a molecular interpretation of pressure and temperature Exercises of a gas, and is consistent with gas laws and Avogadro’s hypothesis. It correctly explains specific heat capacities of many gases. It also relates measurable properties of gases such as viscosity, conduction and diffusion with molecular parameters, yielding estimates of molecular sizes and masses. This chapter gives an introduction to kinetic theory. 12.2 MOLECULAR NATURE OF MATTER Richard Feynman, one of the great physicists of 20th century considers the discovery that “Matter is made up of atoms” to be a very significant one. Humanity may suffer annihilation (due to nuclear catastrophe) or extinction (due to environmental disasters) if we do not act wisely. If that happens, and all of scientific knowledge were to be destroyed then Feynman would like the ‘Atomic Hypothesis’ to be communicated to the next generation of creatures in the universe. Atomic Hypothesis: All things are made of atoms - little particles that move around in perpetual motion, attracting each other when they are a little distance apart, but repelling upon being squeezed into one another. Speculation that matter may not be continuous, existed in many places and cultures. Kanada in India and Democritus Reprint 2025-26 KINETIC THEORY 245 Atomic Hypothesis in Ancient India and Greece Though John Dalton is credited with the introduction of atomic viewpoint in modern science, scholars in ancient India and Greece conjectured long before the existence of atoms and molecules. In the Vaiseshika school of thought in India founded by Kanada (Sixth century B.C.) the atomic picture was developed in considerable detail. Atoms were thought to be eternal, indivisible, infinitesimal and ultimate parts of matter. It was argued that if matter could be subdivided without an end, there would be no difference between a mustard seed and the Meru mountain. The four kinds of atoms (Paramanu — Sanskrit word for the smallest particle) postulated were Bhoomi (Earth), Ap (water), Tejas (fire) and Vayu (air) that have characteristic mass and other attributes, were propounded. Akasa (space) was thought to have no atomic structure and was continuous and inert. Atoms combine to form different molecules (e.g. two atoms combine to form a diatomic molecule dvyanuka, three atoms form a tryanuka or a triatomic molecule), their properties depending upon the nature and ratio of the constituent atoms. The size of the atoms was also estimated, by conjecture or by methods that are not known to us. The estimates vary. In Lalitavistara, a famous biography of the Buddha written mainly in the second century B.C., the estimate is close to the modern estimate of atomic size, of the order of 10 –10 m. In ancient Greece, Democritus (Fourth century B.C.) is best known for his atomic hypothesis. The word ‘atom’ means ‘indivisible’ in Greek. According to him, atoms differ from each other physically, in shape, size and other properties and this resulted in the different properties of the substances formed by their combination. The atoms of water were smooth and round and unable to ‘hook’ on to each other, which is why liquid /water flows easily. The atoms of earth were rough and jagged, so they held together to form hard substances. The atoms of fire were thorny which is why it caused painful burns. These fascinating ideas, despite their ingenuity, could not evolve much further, perhaps because they were intuitive conjectures and speculations not tested and modified by quantitative experiments - the hallmark of modern science. in Greece had suggested that matter may consist of matter. The theory is now well accepted by of indivisible constituents. The scientific ‘Atomic scientists. However even at the end of the Theory’ is usually credited to John Dalton. He nineteenth century there were famous scientists proposed the atomic theory to explain the laws who did not believe in atomic theory ! of definite and multiple proportions obeyed by From many observations, in recent times we elements when they combine into compounds. now know that molecules (made up of one or The first law says that any given compound has, more atoms) constitute matter. Electron a fixed proportion by mass of its constituents. microscopes and scanning tunnelling The second law says that when two elements microscopes enable us to even see them. The form more than one compound, for a fixed mass size of an atom is about an angstrom (10 -10 m). of one element, the masses of the other elements In solids, which are tightly packed, atoms are are in ratio of small integers. spaced about a few angstroms (2 Å) apart. In To explain the laws Dalton suggested, about liquids the separation between atoms is also 200 years ago, that the smallest constituents about the same. In liquids the atoms are not of an element are atoms. Atoms of one element as rigidly fixed as in solids, and can move are identical but differ from those of other around. This enables a liquid to flow. In gases elements. A small number of atoms of each the interatomic distances are in tens of element combine to form a molecule of the angstroms. The average distance a molecule compound. Gay Lussac’s law, also given in early can travel without colliding is called the mean 19th century, states: When gases combine free path. The mean free path, in gases, is of chemically to yield another gas, their volumes the order of thousands of angstroms. The atoms are in the ratios of small integers. Avogadro’s are much freer in gases and can travel long law (or hypothesis) says: Equal volumes of all distances without colliding. If they are not gases at equal temperature and pressure have enclosed, gases disperse away. In solids and the same number of molecules. Avogadro’s law, liquids the closeness makes the interatomic force when combined with Dalton’s theory explains important. The force has a long range attraction Gay Lussac’s law. Since the elements are often and a short range repulsion. The atoms attract in the form of molecules, Dalton’s atomic theory when they are at a few angstroms but repel when can also be referred to as the molecular theory they come closer. The static appearance of a gas Reprint 2025-26 246 PHYSICS is misleading. The gas is full of activity and the is 6.02 × 1023. This is known as Avogadro number equilibrium is a dynamic one. In dynamic and is denoted by NA. The mass of 22.4 litres of equilibrium, molecules collide and change their any gas is equal to its molecular weight in grams speeds during the collision. Only the average at S.T.P (standard temperature 273 K and properties are constant. pressure 1 atm). This amount of substance is Atomic theory is not the end of our quest, but called a mole (see Chapter 1 for a more precise the beginning. We now know that atoms are not definition). Avogadro had guessed the equality of indivisible or elementary. They consist of a numbers in equal volumes of gas at a fixed nucleus and electrons. The nucleus itself is made temperature and pressure from chemical up of protons and neutrons. The protons and reactions. Kinetic theory justifies this hypothesis. neutrons are again made up of quarks. Even The perfect gas equation can be written as quarks may not be the end of the story. There PV = µ RT (12.3)may be string like elementary entities. Nature always has surprises for us, but the search for where µ is the number of moles and R = NA truth is often enjoyable and the discoveries kB is a universal constant. The temperature T is absolute temperature. Choosing kelvin scale forbeautiful. In this chapter, we shall limit ourselves absolute temperature, R = 8.314 J mol–1K–1.to understanding the behaviour of gases (and a Herelittle bit of solids), as a collection of moving molecules in incessant motion. M N µ = = (12.4) M 0 N A

1.35 Henry’s law constant for the molality of methane in benzene at 298 K is 4.27 × 105 mm Hg. Calculate the solubility of methane in benzene at 298 K under 760 mm Hg.

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