Some thermodynamical terms

Some common terms, which are frequently used in the discussion of energetics need to be known. System 'A specified part of the universe which is under investigation is called the system'. The system is separated from the rest of the universe by a definite (real or imaginary) boundary. TYPES OF SYSTEMS Systems are of various types depending upon the exchange of mass and energy and the constituent between the system and the surroundings. Isolated system A system, which can neither exchange mass nor energy with surroundings, is called an isolated system. They are also called insulated systems. Hot coffee (in contact with its vapour) in a closed and insulated thermos is an example of isolated system. Since the vessel is closed, matter can neither enter nor leave the vessel. Moreover, as the vessel is well insulated, heat can neither leave the system nor enter from the surroundings. Closed system A system, which can exchange energy but not mass with the surroundings is called a closed system. For example, boiling water in a closed steel vessel is an example of a closed system. The energy can be gained or lost (through the steel walls) but not matter. Similarly, all reactions carried out in a closed container are examples of closed systems. Open system A system, which can exchange matter as well as energy with the surroundings is called an open system. All reactions carried out in open containers are examples of open systems. Evaporation of water in a beaker or hot coffee in a cup represents an open system. Here vapour of water or coffee (matter) can leave the system and escape into atmosphere. The heat energy required for this purpose is absorbed from the surroundings. All physical and chemical processes taking place in open in our daily life are open systems because they are continuously exchanging matter and energy with the surroundings. Homogeneous system A system is called homogeneous if physical properties and chemical composition are identical throughout the system. A pure gas or consistent mixture of gases e.g., an oxygen cylinder, or a pure liquid or solid in a container are examples of homogeneous systems. Heterogeneous system A system is said to be heterogeneous if it consists of parts separated by definite boundaries, each of which has different physical and chemical properties. A mixture of fertilizer granules (N P K) or ice with water are typical examples of this system. STATE OF A SYSTEM The condition of the system when its macroscopic properties have definite measurable values, is the state of a system. If any of the macroscopic properties of the system

changes such as its temperature, pressure etc., the state of the system is also said to change. To define the state of the system all its macroscopic properties need not be specified. State variable A measurable property required to describe the state of a system is called state variable. For example, temperature (T), pressure (P), volume (V) etc. are the state variables. For any system, a certain minimum number of variables are sufficient to define its state, as the other variables become automatically fixed. For instance, in a system consisting of an ideal gas, the state may be defined by only three variables such as temperature (T), pressure (P) and volume (V). The values of other variables such as amount of gas, density, etc. will be definite and can be easily calculated. State functions A property whose values depend on only the state of the system and not on the path by which the change from initial to final state is brought about is called state function. The change in the value of the state functions depends only upon the initial and final state the system. Some common state functions used in thermodynamics are, pressure, (P), volume (V), temperature (T), internal energy (E or U), enthalpy (H), entropy (S) free energy (G) etc. State properties State variables and functions may posses either extensive or intensive properties. Extensive properties are those, whose values depend on the quantity of matter contained in any system or size of the system. Typical properties are mass, volume, area, energy, number of moles, enthalpy, entropy etc. Intensive properties are those, which depend on the nature of the substance system but is independent of its amount / size in the system. Examples are density, viscosity, surface tension, temperature, pressure, boiling point etc. State processes Isothermal process is that in which the temperature of the system remains constant. Adiabatic process is where there is no exchange of heat between the system and the surrounding. Isobaric process is when the pressure on the system remains constant during any operation. Isochroic process is that in which the volume of the system does not change. Cyclic process is one when the system returns to its initial state after having undergone a series of change. Reversible process occurs when a process is carried out slowly so that the system and the surrounding are always in equilibrium. Irreversible process is that which is carried out rapidly so that the system does not return to its initial state. Surroundings The region outside the boundary of the system is termed as surrounding. The rest of the universe, which is not the part of the system, is separated by a real and imaginary boundary. The boundary sets the limits of the system.

For example, while studying the effects of adding acid to water in a beaker, the acid water mixture forms the system, the walls of the container is the boundary and the rest of the part that is around it is the surrounding. ENERGY TERMS IN THERMODYNAMICS Every system has a definite amount of energy. It can exchange energy (lose or gain) with the surroundings in a variety of ways. In chemical systems the two important modes of transference of energy between the system and the surroundings are heat and work. Heat (Q) Energy exchanged between the system and the surroundings when they are at different temperatures is commonly known as heat. If a system is at a higher temperature than the surroundings, then there is a flow of heat (or energy) from system to surroundings, causing a decline of the systems temperature and an increase in the surrounding temperature. These processes continue till the fall in temperature of the system and rise in temperature of the surroundings, become equal.

Fig: 5.1 - Heat exchange between system and surroundings Work (W) Work is another mode of transference of energy. Work is said to be done if the point of application of force undergoes displacement in the direction of the force. If the system loses energy, we say that the work is done by the system. Alternatively, if the system gains energy, we say that work is done on the system. For example, if a gas, enclosed in a cylinder with a piston, has a higher pressure than the surroundings, the piston will move upward until the pressure inside and outside become equal. The gas expands against a constant external pressure 'P' and its volume changes by an amount equal toDV. The energy transfer that takes in this case is called work. At this step the work is done by the system on the surroundings. This is given as: Work done by the system = PDV. Alternatively, if the system is at lower pressure, piston will be pushed down until the pressure of the system becomes equal to that of the surroundings. In this case work is done on the system by the surroundings. Obviously, if there is no change in volume, i.e., DV = 0, no work is done by the system, i.e. work = 0.

In addition to these two modes, radiant energy and electrical energy are also modes of transference of energy between the system and the surroundings. Units of heat and work The heat changes are measured in calories (cal), kilo calories (kcal), joules (J) or kilojoules (kJ). These are related as: 1 cal = 4.184J 1 kcal = 4.184kJ The S.I. unit of heat is joule or kilojoule Work is measured in terms of ergs or joules. I Joule = 107 ergs. 1calorie = 4.184 x 107 ergs The S.I. unit of work is joule. SIGN CONVENTIONS FOR HEAT AND WORK The signs of 'w' and 'q' are related to the internal energy change. When 'w' or 'q' is positive, it means that energy has been supplied to the system as work or as heat. The internal energy of the system in such a case increases. On the other hand, if 'w' or 'q' is negative, it means that energy has left the system as work or heat. The internal energy of the system decreases. The signs of 'q' and 'w' are: Heat absorbed by the system= q positive Heat evolved by the system= q negative Work done on the system= w positive Work done by the system= w negative Problem 1. Assuming ideal behaviour, calculate the work done when 1.6 mole of water evaporates at 373 K against the atmospheric pressure of 760 mm of Hg. Solution Volume of 1.6 mole of water at 373 K in gaseous state

Volume of 1 mol = 18 g of liquid water (density = 1 g ml-1) = 18 x 1.6 x 10-3L = 0.0288 L Now work done (W) = -P(V2 - V1) = -1(48.93 - 0.0288) = - 48.90 atm L = - 48.90 x 101.325 J = - 4954.8 J.

Exchange of energy between the system and surrounding

Exothermic reactions When chemical reactions take place, energy is either absorbed or evolved. A reaction is said to be exothermic, if heat is 'evolved'. The heat energy produced during the reactions

is indicated by writing + q or more precisely by giving the actual numerical value on the products side. In general, exothermic reactions may be represented as: In the exothermic reactions, the enthalpy of the products will be less than the enthalpy of the reactants so that the enthalpy change is negative as shown below: DH = Hp - Hr (since Hp <>r) DH = -ve Some examples of reactions evolving energy are given below:

Coal is burnt simply for the large amount of energy available during its combustion:

When water is added to quick lime (CaO) for preparing whitewash, a considerable amount of heat is produced during the reaction. The heat produced warms up the water.

When we add dilute hydrochloric acid to a test tube containing granulated zinc, hydrogen gas is evolved. The reaction is accompanied by evolution of heat. One mole of carbon reacts with one mole of oxygen to form one mole of carbon dioxide and 393.5 kJ of heat is evolved at constant temperature and constant pressure. The reaction may be expressed as:

or, Similarly,

Endothermic reactions Reactions that are accompanied by absorption of energy from the surroundings are called endothermic reactions. Since heat is added to the reactants in these chemical reactions, it is indicated by either putting +q or by writing the actual numerical value of heat on the reactants side. Alternatively, this may be written as, We know DH = the heat absorbed at constant temperature and constant pressure. Because of the absorption of heat, the enthalpy of the products will be more than the

enthalpy of the reactants. Consequently, DH will be positive (+ ve) for the endothermic reactions. DH = Hp - Hr since (Hp > Hr) DH = +ve For example:

When a small quantity of ammonium chloride (NH4Cl) is dissolved in water in a test tube, the tube becomes colder than before. During this chemical reaction heat is absorbed from the surroundings (test tube). When crystals of sodium thiosulphate (Na2S2O3.5H2O) commonly called hypo, are dissolved in water a cooling effect takes place. One mole of nitrogen reacts with one mole of oxygen to form two moles of nitric oxide. 180.5kJ of heat is absorbed at constant temperature and the reaction may be expressed as:

or, Similarly,

Fig: 5.2 - Enthalpy changes for exothermic and endothermic reactions Similarly, if we consider heat change at constant volume and temperature, DE is -ve for exothermic reactions and DE is +ve for endothermic reactions. Thus it may be concluded that: For exothermic reactions, DH or DE = -ve For endothermic reactions, DH or DE = +ve Problem 4. Calculate, Q, W, DE and DH for isothermal reversible expansion of one mole of ideal gas from initial pressure of 1 bar to 0.1 bar at a constant temperature of 273 K.

Solution For isothermal reversible expansion of ideal gas

q = -w = -(- 5227.16) = 5227.16 J DE = 0 DH = 0. OTHER ENERGY CHANGES IN CHEMICAL REACTIONS Energy changes in chemical reactions can also take place in forms other than heat, such as light, electricity, mechanical energy, etc. Some common examples are:

The burning of petrol or diesel in motor engines of cars, trucks, tractors or buses produces mechanical energy, which is used in running these vehicles.

Chemical reactions taking place in batteries produce electrical energy to run transistors radios, torches and watches, etc. For example, in a Daniel cell, the chemical reaction between zinc metal and copper sulphate solution is accompanied by electrical energy.

Photosynthesis In this process chlorophyll in green plants converts carbon dioxide and water into glucose and oxygen, energy is provided by the energy of sunlight,

This reaction is very important for the life of plants

Different types of thermodynamic process

Thermodynamic Process Whenever one or more of the properties of a system change, a change in the state of the systemoccurs. The path of the succession of states through which the system passes is called thethermodynamic process. One example of a thermodynamic process is increasing the temperatureof a fluid while maintaining a constant pressure. Another example is increasing the pressure ofa confined gas while maintaining a constant temperature. Thermodynamic processes will bediscussed in more detail in later chapters. Cyclic Process When a system in a given initial state goes through a number of different changes in state (goingthrough various processes) and finally returns to its initial values, the system has undergone acyclic process or cycle. Therefore, at the conclusion of a cycle, all the properties have the samevalue they had at the beginning. Steam (water) that circulates through a closed cooling loopundergoes a cycle.

Reversible Process A reversible process for a system is defined as a process that, once having taken place, can bereversed, and in so doing leaves no change in either the system or surroundings. In other wordsthe system and surroundings are returned to their original condition before the process took place.In reality, there are no truly reversible processes; however, for analysis purposes, one usesreversible to make the analysis simpler, and to determine maximum theoretical efficiencies.Therefore, the reversible process is an appropriate starting point on which to base engineeringstudy and calculation.Although the reversible process can be approximated, it can never be matched by real processes.One way to make real processes approximate reversible process is to carry out the process in aseries of small or infinitesimal steps. For example, heat transfer may be considered reversibleif it occurs due to a small temperature difference between the system and its surroundings. Forexample, transferring heat across a temperature difference of 0.00001 F "appears" to be more reversible than for transferring heat across a temperature difference of 100 F. Therefore, bycooling or heating the system in a number of infinitesamally small steps, we can approximate areversible process. Although not practical for real processes, this method is beneficial forthermodynamic studies since the rate at which processes occur is not important. Irreversible Process An irreversible process is a process that cannot return both the system and the surroundings totheir original conditions. That is, the system and the surroundings would not return to their

The first law of thermodynamics

We have seen that heat is just a form of energy. A system can be given energy either by supplying heat to it (by placing it in contact with a hotter object) or by doing mechanical work on it. Consider an ideal gas in a cylindrical container, fitted with a piston as shown in the figure given below. The piston is fixed in its position and the walls of the cylinder are kept at a temperature higher than that of the gas. The gas molecules strike the wall and rebound. The average kinetic energy of a molecule in the wall is greater than the average kinetic energy of a gas molecule. Thus, on collision, the gas molecules receive energy from the molecules of the wall. This increased kinetic energy is shared by other molecules of the gas, and in this way, the total internal energy of the gas increases.

Next, consider the same initial situation but now with the walls at the same temperature as the gas. When the piston is pushed slowly to compress the gas, the gas molecule collides with the piston coming towards it and the speed of the molecule increases on collision (assuming elastic collision, v2= v1 + 2u in the figure below). This way the internal energy of the molecules increases as the piston is pushed in.

We see that the total internal energy of the gas can increase either due to the temperature difference between the walls and the gas (heat transfer) or due to the motion of the piston (work done on the gas). In a general situation, both modes of energy transfer may happen together. As an example, consider a gas kept in a cylindrical can, fitted with a movable piston. If the can is kept on a heater, the hot bottom of the cylinder supplies heat to the gas. If the piston is pushed out to some distance, as the piston moves out, the gas does work and the gas loses that amount of energy. Thus, the gas gains energy as heat gets supplied to it and it loses energy as work is done by it. Suppose, in a process, an amount DQ of heat is given to the gas and an amount DW of work is done by it, the total energy of the gas must increase by (DQ - DW). As a result, the entire gas, together with its container, may start moving (systematic motion) or the internal energy (random motion of the molecules) of the gas may increase. If the energy does not appear as a systematic motion of the gas, then this net energy (DQ - DW) must go in the form of its internal energy. If we denote the change in internal energy as DU, we get Equation (1) is the statement of the first law of thermodynamics. In an ideal monatomic gas, the internal energy of the gas is simply translational kinetic energy of all its molecules. In general, the internal energy may get contributions from the vibrational kinetic energy of molecules, rotational kinetic energy of molecules as well as from the potential energy corresponding to the molecular forces. Equation (1) represents a statement of conservation of energy and is applicable to any system, however complicated it might be.

Sign convention of heat and work

SIGN CONVENTIONS FOR HEAT AND WORK The signs of 'w' and 'q' are related to the internal energy change. When 'w' or 'q' is positive, it means that energy has been supplied to the system as work or as heat. The internal energy of the system in such a case increases. On the other hand, if 'w' or 'q' is negative, it means that energy has left the system as work or heat. The internal energy of the system decreases. The signs of 'q' and 'w' are: Heat absorbed by the system= q positive Heat evolved by the system= q negative Work done on the system= w positive Work done by the system= w negative

Enthalpy, enthalpy change in chemical reactions

The change in internal energy gives the heat change accompanying a chemical reaction at constant volume. However, most of the chemical reactions carried out in laboratories, are open to normal atmospheric conditions. A chemical reaction in a laboratory may incur change in volume but the pressure remains constant i.e. atmospheric pressure. To study the heat changes for reactions at constant pressure and at constant temperature, a new term called enthalpy has been introduced. The enthalpy of a system may be defined as the sum of the internal energy and the product of its pressure and volume. It is denoted by the symbol H and is given by H = E + PV where, E = internal energy, P = pressure and V = the volume of the system. Enthalpy is also called heat content.Enthalpy-Change"> ENTHALPY CHANGE Every substance has a definite value of enthalpy in a particular state. Like internal energy, the absolute value of enthalpy cannot be measured. However, the change in enthalpy accompanying a process can be determined as the difference between the enthalpies of the products and the reactants, i.e., DH = Hproducts - Hreactants = Hp - Hr where, 'Hp' is the enthalpy of the products, 'Hr' is the enthalpy of the reactants and DH is the enthalpy change. If a reaction is carried out at constant temperature and pressure the heat exchanged (evolved or absorbed) by the system with the surroundings (i.e., heat change - DH) is equal to change in enthalpy. Origin of enthalpy change in a reaction We know that in chemical reactions, energy is required to break old bonds of the reactants. Energy is also released to form new bonds, which give the end products. The net energy change (released or absorbed) in a reaction will be equal to energy required to break all the bonds in reactants minus the energy released during the formation of bonds in the products.

If energy required is greater than energy released, the net result will be the absorption of energy and the reaction will be endothermic, i.e. DH = + ve. If energy released is greater than energy required, the net result is the release of energy and the reaction will be exothermic (DH = - ve). This can be illustrated by considering a chemical reaction between hydrogen gas and chlorine gas to form hydrochloric acid gas:

The energy required in breaking one mole of bonds in hydrogen and chlorine molecules are 437 and 244 kJ respectively.

It is observed that for the formation of one mole of HCl, 433 kJ of energy is released. Therefore, the energy released during the formation of 2 moles of HCl is 2 x 433 = 866 kJ.

Thus, Enthalpy change = (437+244) - (2 x 433) = -185 kJ DH = - 185kJ Therefore, 185 kJ of energy is released during the formation of 2 moles of gaseous HCl from one mole each of gaseous hydrogen and gaseous chlorine. The amount of heat exchanged with the surroundings for a reaction at constant pressure (DH) is different from that exchanged at constant volume (DE) and temperature. The energy changes for reactions at constant pressure, includes energy contributions due to expansion or contraction against atmospheric pressure i.e. the volume of the reacting system changes. If the volume increases, the system expands against the atmospheric pressure and energy is required for this expansion. Therefore, a part of energy will be used for the expansion. Thus the amount of heat exchanged at constant pressure (DH) would be less than the amount of heat exchanged at constant volume (DE). Alternatively, if the system contracts at constant pressure, work is done on the system and the system absorbs some energy from the surroundings. Therefore, the amount of heat exchanged at constant pressure is greater than that exchanged at constant volume.DH-and-DE"> Relationship between DH and DE Consider a reaction at constant pressure 'P'. Let HA be the enthalpy of the reactants and HB be the enthalpy of products so that change in enthalpy, DH may be DH = HB - HA But H = E + PV. Let EA and VA be the internal energy and volume of the reactants and EB and VB corresponding values for the products. Therefore, HA = EA + PVA and HB = EB + PVB DH = (EB + PVB) - (EA + PVA) or DH = (EB - EA) + P(VB - VA) or DH = E+ PDV where DE is the change in internal energy and DV is the change in volume of the system.

Hess's law of constant heat summation

HESS'S LAW OF CONSTANT HEAT SUMMATION G.H.Hess proposed a law regarding the heats or enthalpies of reaction in 1840 called the Hess's law. This law states that 'the heat change in a particular reaction is the same whether it takes place in one step or several steps'. For example, a reactant 'A' changes to a product 'B' in one step and the heat change during this process is DH. If the reaction is carried out in two steps where 'A' first changes to 'C' an intermediate stage and then 'C' changes to 'B' in the following step then

let the heat change during the formation of 'A' to 'C' beDH1 and that from 'C' to 'B' be DH2. From Hess's law the heat change for the reaction is given as: DH = DH1 + DH2

Fig: 5.4 - Illustration of Hess's law This means that the amount of heat evolved or absorbed in a chemical reaction depends only upon the energy of initial reactants and the final products. The heat change is independent of the path or the manner in which the change has taken place. The formation of carbon dioxide from carbon and oxygen can be illustrated as follows. Carbon can be converted into carbon dioxide in two ways. Firstly solid carbon combines with sufficient amount of oxygen to form CO2. The same reaction when carried in presence of lesser amount of oxygen gives carbon monoxide which then gets converted to CO2 in step two in the presence of oxygen.

DH = DH1 + DH2 Thus, one can conclude that thermochemical equations can be added, subtracted or multiplied like algebraic equations to obtain the desired equation. APPLICATION OF HESS'S LAW Hess's law has been useful in determining the heat changes of reactions, which cannot be measured directly with calorimeter. Some of its applications are: Applications and problems Determination of heat of formation Compounds whose heats of formation cannot be measured directly using calorimetric methods because they cannot be synthesised from their elements easily e.g. methane, carbon monoxide, benzene etc are determined using Hess's Law. For example, the heat of formation of carbon monoxide can be calculated from the heat of combustion data for carbon and carbon monoxide as shown above. Determination of heat of transition

The heats of transition of allotropic modification of compounds such as diamond to graphite, rhombic sulphur to monoclinic sulphur, yellow phosphorous to red phosphorous etc. can be determined using Hess's Law. For example, the heat of transition of diamond to graphite can be calculated from the heat of combustion data for diamond and graphite, which is -395.4 kJ and -393.5 kJ respectively. The thermochemical equations showing the combustion reaction of diamond and graphite are:

The conversion that is required is: This can be obtained by subtracting the second equation from the first one.

Determination of heat of hydration The heats of hydration of substances is calculated using Hess's law. For example the heats of hydration of copper sulphate can be calculated from the heats of solution of anhydrous and hydrated salts of copper. The heats of solution of CuSO4 and CuSO4.5H2O are -66.5 and -11.7 kJ mol-1. The corresponding thermochemical equations are:

The process of hydration can be expressed as:

According to Hesss law, DH1 = DH + DH2 DH = DH1 - DH2 = -66.5 11.7 = -78.2 kJ/mol Determination of heats of various reactions Hess's law is useful in calculating the enthalpies of many reactions whose direct measurement is difficult or impossible. Problems

19. Calculate the standard heat of formation of carbon disulphide (l). Given that the standard heats of combustion of carbon (s) sulphur (s) and carbon disulphide (l) are 393.3, -293.72 and -1108.76kJ mol-1respectively. Solution The given data can be written in thermochemical equation form as:

The required equation is: Multiplying equation (ii) by 2 and adding to equation (i) we get,

Subtracting equation (iii) from the above equation we have,

20. Calculate lattice energy for the change, Given that DHsubl. of Li = 160.67 kJ mol-1, DHDissociation of Cl2 = 244.34 kJ mol-1, DHionisation of Li(g) = 520.07 kJ mol-1, DHE.A of Cl(g) = - 365.26 kJ mol-1, DHof of LiCl(s) = - 401.66 kJ mol-1. Solution Considering the different changes that occur in the formation of solid lithium chloride based on the data given the lattice energy of the above can be constituted as:

or = - 839.31 kJ mol-1

Heat of neutralization, heat of solution, heat of combustion, heat of vapourization, heat of formation and bond energy
The calorimeter is kept open to the atmosphere in the determination of change in enthalpy of a reaction. The calorimeter is immersed in an insulated water bath fitted with stirrer and thermometer. The temperature of the bath is recorded in the beginning and after the end of the reaction and the change in temperature is calculated. Knowing the heat capacity of water bath and calorimeter and also the change in temperature the heat absorbed or evolved in the reaction is calculated. This gives the enthalpy change (DH) of the reaction. ENTHALPY OF COMBUSTION The enthalpy of combustion of a compound is the enthalpy change at normal pressure and at constant temperature accompanying complete combustion of one mole of the compound. It is denoted by DHc. Combustion here means the burning of the given compound to the highest oxides of the constituent elements in the presence of excess of oxygen. For example, the enthalpy of combustion of benzene at 298 K is the enthalpy change of the reaction.

Thus, DHcomb C6H6(l) = -3268kJmol-1.

Enthalpy of combustion is generally obtained experimentally. For cases, where it is not possible to measure it experimentally, it is estimated from the enthalpies of formation of the various compounds involved in the process. Problems 11. The heats of combustion of CH4 and C2H6 are -890.3 and -1559.7kJ mol-1 respectively. Which of the two has greater efficiency of fuel per gram? Solution The fuel efficiency can be predicted from the amount of heat evolved for every gram of fuel consumed. (i) The combustion of methane is as follows: DHc = 890.3 kJmol-1 Molar mass of CH4 = 16

(ii) The combustion of ethane is as follows:

DHc = 1559.7kJmol-1 Molar mass of C2H6 = 30

Thus, methane has greater fuel efficiency than ethane. 12. (a) A cylinder of gas supplied by a company is assumed to contain 14 kg of Butane. If a normal family requires 20,000 kJ of energy per day for cooking, how long will the cylinder last? (b) If the air supplied to the burner is insufficient, a portion of gas escapes without combustion. Assuming that 25% of the gas is wasted due to this inefficiency, how long will the cylinder last? (Heat of combustion of butane = 2658 kJ/mol). Solution (a) Molecular formula of butane = C4H10 Molecular mass of butane = 4 x 12 + 10 x 1 = 58 Heat of combustion of butane = 2658kJmol-1 1 mole of 58 g of butane on complete combustion give heat = 2658 kJ 14 x 103 g of butane on complete combustion gives heat =

The family needs 20,000 kJ of heat for cooking per day. 641586 kJ of heat will be used for cooking by a family in

The cylinder will last for 82 days

(b) 25 per cent of the gas is wasted due to inefficiency. This means that only 75% of butane is combusted. Therefore, the energy produced by 75% combustion of butane

13. The enthalpy change involved in the oxidation of glucose is - 2880 kJ mol-1. Twenty five percent of this energy is available for muscular work. If 100 kJ of muscular work is needed to walk one kilometer, what is the maximum distance that a person will be able to walk after eating 120 g of glucose. Solution DHcomb of Glucose (C6H12O6) = - 2880 kJ mol-1

14. Calculate the enthalpy change of combustion of cyclopropane at 298 K. The enthalpy of formation of CO2(g) , H2O(l) and propane(g) are -393.5, -285.8 and 20.42 kJmol-1 respectively. The enthalpy of isomerisation of cyclopropane to propene is -33.0 kJ mol-1. Solution The required DH is

The given equations are:

Multiply equation (i) and (ii) by 3 and add them. Now subtract equation (iii) and subsequently add equation (iv) from the resulting expression. DH = 3DH1 + 3DH2 - DH3 - DH4 = 3(- 393.5) + 3(- 285.8) - (20.42) + (-33.0) = - 2091.32 kJ. HEAT OR ENTHALPY OF NEUTRALISATION The reaction in which an acid and a base react to give a salt and water is called neutralization reaction. Neutralization reactions are exothermic in nature. The heat

change when one gram equivalent of an acid is completely neutralised by a base or vice versa in dilute solution, is called heat of neutralization. Examples of heat of neutralization are: Neutralization of HCl with NaOH Neutralization of CH3COOH with NaOH DH =-55.9 kJ It is important to note that the term gram equivalent is used in the definition of heat of neutralization. This is because neutralization involves 1 mole of H+ ions and 1 mole of OH- ions to form 1mole of water and 57.1 kJ of heat is liberated. Now, one gram equivalent of various acids on complete dissociation liberates one mole of H+ ions. But one mole of the acid may produce more than one mole of H+ ions in solution depending upon its basicity; for example 1mol of H2SO4 gives 2 mol of H+ ions and 1mol of H3PO4 gives 3 mol of H+ ions on complete dissociation. But 1gram equivalent of both (H2SO4 or H3PO4) produces only 1 mol of H+ions. Thus, it is more appropriate to use the term gram equivalent in the definition of enthalpy of neutralization. The average enthalpy of neutralization of any strong acid by a strong base is found to be - 57.7 kJ (- 13.7 kcal) irrespective of the nature of acid or the base. This suggests that the net chemical reaction in all neutralization reactions is the same, viz., This is because strong acids and strong bases are completely ionized in aqueous solutions. The aqueous solution of one gram equivalent of all strong acids contains the same number of H+ ions. Similarly, aqueous solution of one gram equivalent of all strong bases also contains same number of OH-. The neutralization reactions between strong acids and strong bases in aqueous solutions involve simply the combination of H+ ions (from an acid) and OH- ions (from a base) to form unionized water molecules. For example, in the reaction between hydrochloric acid and sodium hydroxide ion. The neutralization can be represented as:

DH = -57.1kJ Cancelling common ions: Neutralization of weak acids and weak bases The heat of neutralization of a weak acid or a weak base is less than -57.1 kJ and is also different for different weak acids or bases. For example for acetic acid the enthalpy of neutralization is -54.9 kJ. This can be explained as follows:

Acetic acid (CH3COOH) is a weak acid. Weak acids (or weak bases) are ionised to a small extent in solutions. So acetic acid is only partially ionised in solution. Since the neutralization involves a reaction between H+(from the acid) and OH- (from the base), hence acetic acid must be fully ionised as per the reaction, DH = +1.2 kJ The ionization reaction is endothermic reaction. So, during ionization of acetic acid a small amount of heat (1.2 kJ) is absorbed. As a result, the enthalpy of neutralization of acetic acid is 1.2 kJ less than that for a strong acid-strong base pair. Therefore, the aqueous solutions containing one gram equivalent of different weak acids do not contain 1 gm equivalent of H+ ions. Similarly, the aqueous solutions containing 1 gram equivalent of different weak bases do not contain 1 gram equivalent of OH- ions. The weak acids, weak bases therefore, have to be dissociated to give 1 gram equivalent of H+ or OH- ions but, neutralisation of weak acid and strong base (or a weak base and strong acid) not only involves the combination of H+ and OH- ions but also the dissociation of a weak acid (or a weak base). The dissociation process is accompanied by the absorption of energy. This energy is called the heat of dissociation. Therefore, the overall liberated energy is less than 57.1 kJ (i.e., 57.1 of dissociation of acid or base). The neutralization of acetic acid with sodium hydroxide can be explained as follows:

DH = -55.9kJ Thus, heat of neutralization of acetic acid and sodium hydroxide is -55.9 kJ, because 1.2 kJ of heat energy is used up in dissociating acetic acid. Similarly, heat of neutralization of ammonium hydroxide and hydrochloric acid is -51.5 kJ as 5.6 kJ is the heat of dissociation of NH4OH. Problems 15. 100 ml of 1N of an acid and 100 ml of 1N of a base are mixed at 298K. During the experiment, the temperature arose to 298.0067 K. Calculate the heat of neutralization. Solution Heat capacity of solution = Mass of solution x Specific heat capacity Total mass of solution = 100 + 100 = 200 ml Heat capacity of solution = 200 x 4.2 = 840 JK-1 Heat change in the reaction = Heat capacity x Rise in temperature = (840 JK-1) (298.0067 - 298)K = 840 x 0.0067 J = 5.63 J Now, one gram equivalent of acid = 1N HCl in 1000 ml

100 ml of 1N acid on neutralization gives heat = 5.63 J

= 56.3J Heat of neutralization = -56.3 J 16. Whenever an acid is neutralized by a base, the net reaction is: Calculate the heat evolved for the following experiments: (a) 0.60 mol of HNO3 solution is mixed with 0.30 mol of KOH solution. (b) 400 cm3 of 0.2 M H2SO4 is mixed with 600 cm3 of 0.1 M NaOH solution. Solution According to the reaction, When 1 mole of H+ ions and 1 mol of OH- ions are neutralized to form 1 mol of water, 57.1 kJ of energy is released. (a) Heat evolved on mixing 0.60 mol of HNO3 with 0.30 mol of KOH solution. Since HNO3 and KOH are strong acids and bases, O.60 mol of HNO3 0.60 mol of H+ ions 0.30 mol of KOH 0.30 mol of OH- ions In this case, out of 0.60 mol of H+ ions (from HNO3) only 0.30 mol will be neutralised (equal to OH- ions present) by the base. 0.3 mol of H+ ions of HNO3 will remain unreacted. The net reaction is: Now, heat evolved during the formation of 1 mol of H2O = 57.1kJ Heat evolved in the formation of 0.3 mol of H2O=57.1 x 0.3=17.13 kJ. DHsol)"> Enthalpy of solution (DHsol) When a solute is dissolved in a solvent a solution is formed. During dissolution of a solute in any solvent, a certain amount of heat is either absorbed or evolved. Such heat changes under constant pressure conditions are known as the enthalpy of solution. 'The change in enthalpy when one mole of a solute is dissolved in a specified quantity of a solvent at a given temperature is called enthalpy of solution'. To avoid the amount of solvent, heat of solution is usually defined for an infinite dilute solution. Thus, heat of solution at infinite dilution is the heat change when one mole of a substance is dissolved in such a large quantity of solvent so that further dilution does not give any further heat change. For example, dissolution of sodium chloride Here 'aq' represents aqueous meaning a large excess of water.

For substances, which dissolve with the absorption of heat (endothermic), the enthalpy of solution is positive while for the substances which dissolve by liberating heat (exothermic), the enthalpy of solution is negative. For example, when KCl is dissolved in water, heat is absorbed. Thus, the enthalpy of solution of KCl is positive. For a 200 times dilution (water : KCl = 200 : 1), the enthalpy change during the process, So, the enthalpy of solution of KCl at a dilution of 200 is 18.6 kJ mol-1. The dissolution of CaCl2(s) in water is an exothermic process. So, the enthalpy of solution of calcium chloride (CaCl2) is negative. At a dilution of 400, the enthalpy change for the reaction, So, the enthalpy of solution of CaCl2(s) at a dilution of 400 is -75.3 kJ mol-1. DHfus)"> Enthalpy of fusion (DHfus) The enthalpy of fusion of a substance is defined as 'the change in enthalpy when one mole of a solid substance is melted at its melting temperature'. For example, the enthalpy change of the reaction, is the enthalpy of fusion of ice. Enthalpy of fusion for some common substances are given below: Substance: Ethanol Oxygen Hydrogen sulphide Sodium chloride (C2H5OH) (O2) (H2S) (NaCl) Hfus kJmol-1: +4.8 +0.45 +2.0 +29 Melting point: 156 K 55 K 188 K 1074 K From the data given above, we see that the enthalpies of fusion for ionic substances are very high. This is due to strong Coulombic forces between the constituent ions in ionic solids. The solids such as O2and H2S, which are molecular solids, have low heats of fusion because the forces of attraction between their molecules are weak forces. Thus, the heats of fusion of substances give an idea of nature of solid and the magnitude of forces acting between the particles constituting the solids.vap)"> Enthalpy of Vapourisation (vap) 'The change in enthalpy when one mole of a liquid is converted into vapours at its boiling temperature is called enthalpy of vapourisation' (DHvap). Thus, the enthalpy change of the reaction is the enthalpy of vapourisation of water. The enthalpies of vapourisation for certain common liquids are: Substance Boiling point He(l) 4K H2(l) 20K O2(l) 90K HCl(l) 188K H2O(l) 373K NaCl(l) 1738 K

Hvap kJmol -1

0.1

0.9

6.7

16.2

40.6

170

From the data given above, we can say DHvap (ionic liquids) > DHvap (polar liquids) > DHvap (non-polar liquids) Thus, the DHvap depends upon the strength of intermolecular forces in any liquid. Problem 17. Determine the value of DH and DE for the reversible isothermal evaporation of 90.0 g of water at 100C. Assume that water vapours behave as ideal gas and heat of evaporation of water is 540 cal g -1. (R = 2 cal mol-1 K-1) Solution

Heat of evaporation of 1 g of water = 540 cal Heat of evaporation of 90 g of water = 540 x 90 = 48600 Cal. D H = 48600 Cal The evaporation of 5 mol of water is represented as Dn = (5 - 0) = 5 DH = DE + DnRT or DE = DH - DnRT = 48600 - (5) (2.0) (373) = 44870 cal DHsub)"> Enthalpy of Sublimation (DHsub) Sublimation is a process in which a solid substance directly changes into its vapours at any temperature below its melting point. Enthalpy of sublimation is defined as follows: The change in enthalpy when one mole of a solid substance is converted into its vapours without melting at a temperature below its melting point is called the enthalpy of sublimation. For example, when one mole of solid iodine is converted into its vapours at room temperature, heat equal to 62.4 kJ is absorbed. So, the enthalpy of sublimation of iodine is + 62.4 kJ mol-1, i.e., Compounds, which sublime on heating are camphor, dry ice, ammonium chloride etc. The heat of sublimation is related to heat of fusion and heat of vaporization as: DHsublimation = DHfusion + DHvaporization Problem 18. When 1 g of liquid naphthalene (C10H8) solidifies, 149 J of heat is evolved. Calculate the heat of fusion of naphthalene. Solution The molecular mass of naphthalene is C10H8, = 10 x 12 + 8 x 1 =128 Heat evolved when 1 g of naphthalene solidifies = 149 J

Heat evolved when 128 g of naphthalene solidifies = 149 x 128 = 19072 J For the fusion reaction, This reaction is the reverse of the above solidification reaction so that DHfusion = - DHsolidification DHfusion = 19072 J or = 19.072 kJ Enthalpy of hydration This is defined as the heat change (evolved or absorbed) when one mole of the anhydrous salt combines with the required number of moles of water to form the specific hydrated salt

Concept of equivalent mass

It is defined as the mass of an element/compound/ion which combines or displaces 1 part of hydrogen or 8 parts of oxygen or 35.5 parts of chlorine by mass.It is not always possible to apply this classic definition to determine equivalent weights of chemical entities. It is so because, we can not conceive of reactions involving chemical entities with three named reference of hydrogen, oxygen and chlorine. Generally, we are limited to determination of equivalent weights of elements and few compounds by using this definition of equivalent weight. A more workable definition is given as : Equivalent weight,E= Molecular weight Valence factor = MO x Clearly, determination of equivalent weight amounts to determining valence factor x. Here, we shall classify chemical entities and the techniques to determine x. or, Equivalent mass is equal to the molecular or atomic mass divided by the number of electrons involved in the reaction per molecule, atom or ion. For example in the reaction,

two electrons are needed to produce one molecule of hydrogen gas. So, 2 Faraday of electricity is needed to produce one mole of hydrogen gas. Hence,

For the reaction, per mole of copper atoms, 2 faradays are needed. So, the equivalent mass of copper is half of its atomic mass.

The equivalent mass of any species is not simply a property of the species, but depends upon the reaction in which it participates, i.e., one chemical species can have more than one value for its equivalent mass depending upon the reaction it participates. The equivalent mass of a substance is the quantity of material deposited or dissolved by 1 F (= 96500 C) of electricity.

Equivalent weight of elements, and compounds

Equivalent weight of an element In the case of an element, the equivalent weight is defined as : Equivalent weight,E= Atomic weight Valency = A x Note that atomic weight substitutes molecular weight and valency substitutes valence factor in the definition. Valencies of hydrogen, calcium and oxygen are 1,2 and 2 respectively. Hence, their equivalent weights are 1/1 =1, 40/2 = 20 and 16/2 = 8 respectively. Equivalent weight of an acid

The valence factor of an acid is equal to its basicity. The basicity of an acid is equal to furnishable hydrogen ion (proton) in its aqueous solution. Importantly, basicity is not same as the number of hydrogen atoms in acid molecule. Consider acetic acid (CH3COOH). It contains 4 hydrogen atoms in it, but only 1 furnishable hydrogen ion. As such, basicity of acetic acid is 1. With this background, we define equivalent weight of an acid as : Equivalent weight,E= Molecular weight of acid Basicity Basicity of sulphuric acid is 2. Hence, equivalent weight of sulphuric acid (H2SO4) is (2X1 + 32 + 4X16)/2 = 98/2 = 49. Similarly, basicity of oxalic acid is 2. Hence, equivalent weight of oxalic acid (H2C2O4 ) is (2X1 + 2X12 + 4X16)/2 = 90/2=45. Phosphorous based acids like phosphoric acid (H3PO4 ), phosphorous acid (H3PO3) and hypo-phosphorous acid (H3PO2) need special mention here to understand their basicity. The structures of three acids are shown here. From the structure, it appears that these compounds may furnish OH ions, but bond strengths between phosphorous and oxygen (P-O) and phosphorous and hydrogen (P-H) are stronger than between oxygen and hydrogen (O-H) in OH group. As such, these molecules release hydrogen ions from OH group and behave as acid. Clearly, basicities of phosphoric acid (H3PO4), phosphorous acid (H3PO3) and hypo-phosphorous acid (H3PO2) are 3, 2 and 1 respectively. Phosphorous based acids

Figure 1: Furnishable hydrogen ions of acids Equivalent weight of a base

The valence factor of a base is equal to its acidity. The acidity of a base is equal to furnishable hydroxyl ion (OH-) in its aqueous solution. With this background, we define equivalent weight of a base as : Equivalent weight,E= Molecular weight of base Acidity Acidity of KOH is 1, whereas acidity of Ca(OH)2 is 2. Hence, equivalent weight of KOH is (39 + 16 + 1)/1 = 56/1 = 56. Similarly, equivalent weight of Ca(OH)2 is {40 + 2X(16+1)}/2 = 74/2=37. Equivalent weight of a compound The valence factor of a compound depends on the manner a compound is involved in a reaction. The compounds of alkali metal salts and alkaline earth metal salts are, however, constant. These compounds are ionic and they dissociate in ionic components in aqueous solution. In this case, valence factor is equal to numbers of electronic charge on either cation or anion. Equivalent weight,E= Molecular weight of compound Numbers of electronic charge on cation or anion The numbers of electronic charge on cation of NaHCO3 is 1. Hence, equivalent weight of NaHCO3 is (23 + 1 + 12 + 3X16)/1 = 84. If we look at the defining ratio of equivalent weight of a compound (AB) formed of two radicals (say A and B), then we can rearrange the ratio as : Equivalent weight, E= Molecular weight of Radical A Numbers of electronic charge +

Molecular weight of Radical B Numbers of electronic charge Thus, Equivalent weight of AB=Equivalent weight of A+Equivalent weight of B Equivalent weight of an ion The valence factor of an ion is equal to numbers of electronic charge on the ion. Therefore, we define equivalent weight of an ion as : Equivalent weight,E= Molecular weight of ion Numbers of electronic charge The numbers of electronic charge on carbonate ion (CO32 ) is 2. Hence, equivalent weight of carbonate ion is (12 + 3X16)/1 = 60/2 = 30. Similarly, equivalent weight of aluminum ion (Al3+) is 27/3 = 9. Equivalent weight of an oxidizing or reducing agent In a redox reaction, one of the reacting entities is oxidizing agent (OA). The other entity is reducing agent (RA). The oxidizer is recipient of electrons, whereas reducer is releaser of electrons. The valence factor for either an oxidizing or reducing agent is equal to the numbers of electrons transferred from one entity to another. Equivalent weight,E= Molecular weight of compound Numbers of electrons transferred in redox reaction Alternatively, Equivalent weight,E= Molecular weight of compound Change in oxidation number in redox reaction

Potassium dichromate in acidic medium is a strong oxidizer. It means it gains electrons during redox reaction. Potassium dichromate in acidic solution results in : K2Cr2O7+14H++6e2K++2Cr3++7H2O Equivalent weight ofK2Cr2O7= 294.2 6 =49 Study of redox reaction is in itself an exclusive and extensive topic. We shall, therefore, discuss redox reaction separately

Gram equivalent weight

GRAM EQUIVALENT(GEQ) It is equal to mass in grams numerically equal to equivalent weight. If the mass of a chemical entity is g grams, then the given mass contains gram equivalents given by : Gram equivalent (geq)= g E This formula is widely used to express grams of substance in terms of gram equivalent and vice-versa. Relation between moles and gram equivalents (geq) Gram equivalents is given by : geq= g E Substituting for equivalent weight, we have :

geq= g E = xg MO Moles is given by : n= g MO Combining expressions, we have : geq=xn gram equivalent=valence factorXmoles GRAM EQUIVALENT CONCEPT Consider the example of formation of water : 2H2+O22H2O Here, 2 moles of hydrogen combines with 1 mole of oxygen to form 2 moles of water molecule. In terms of mass, 4 gm of hydrogen combines with 32 gm of oxygen to form 36 gm of water molecule. The relevant proportions involved with this equation are : Coefficients of balanced equation = 2:1:2 Molecules/moles = 2:1:2 Mass = 4:32:36 = 1:8:9 On the other hand, equivalent weights of hydrogen, oxygen and water are 1, 8 and 9. Clearly, proportion of mass in which chemical entities participate is exactly the proportion of equivalent weights! Note that mole concept depends on the coefficient of balanced chemical equation. On the other hand, the equivalent weight concept is independent of coefficient of balanced chemical equation. If we know that hydrogen and oxygen combines to form water molecule, then we can say straightway that entities are in the proportion of equivalent weights - without any reference to coefficients in the balanced chemical equation.

equivalent weight of hydrogenequivalent weight of oxygenequivalent weight of water Note that there is no mention of coefficients of balanced chemical equation in the equivalent weight relation. We should, however, understand that two techniques of analyzing chemical reactions are essentially equivalent. We need to consider coefficients involved in balanced chemical equation for applying mole concept. On the other hand, coefficients are not considered when using equivalent weight concept, but we need to know the corresponding valence factor of each entity. It is important to realize that above relation is not a relation connected by "equal to (=)" sign. Rather, they are connected by equivalent sign (). As such, we still need to apply unitary method to analyze the relation. Gram equivalent concept is a step head in this context. The gram equivalents of participating entities are same. For the case of formation of water, the proportion of mass of hydrogen, oxygen and water is 1 gm: 8 gm : 9 gm. Now, we know that the gram equivalents of entities are obtained by dividing mass by equivalent weight. Hence, gram equivalents of three entities are 1/1 = 1, 8/8=1 and 9/9 = 1. Thus, gram equivalents of participating entities are same. If gram equivalents of hydrogen is 2, then gram equivalents of oxygen and water will also be 2. As such : x gm equivalents of hydrogen=x gm equivalents of oxygen=x gm equivalents of water Significant aspect of this relation is that it is connected with equal to (=) sign and as such relieves us from applying unitary method altogether

Relation between equivalent weight, valency and atomic weight

Consider an element X of atomic weight A and valency n. Suppose the element X combines with hydrogen to give the compound hydride, XHn. X + nH ?XHn 1 atom of X combines with n atoms of hydrogen. 1 gram-atom of X combines with n gram-atoms of hydrogen. Atomic weight of X = A Atomic weight of hydrogen = 1.008 n 1.008g of hydrogen combines with = A gram of X A 1.008 grams of hydrogen combines with = ------------- 1.008 n 1.008 A = -----n By definition, this gives the equivalent weight of the element X.

Atomic weight Equivalent weight = ------------------Valency In the case of univalent elements, the atomic weight itself gives the equivalent weight. Elements having varying valency have different equivalent weight. Equivalent weight of copper in cuprous oxide Cu2O is 63.5. (here, valency of Cu is one). Equivalent weight of copper in cupricoxide, 63.5 CuO is ------ = 31.75 (here, valency of Cu is 2).