First Law of Thermodynamics Introduction The branch of chemistry, which deals with energy changes during various physical

processes and chemical reactions, is called chemical energetics. Important Thermodynamic Terms '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. Energy Changes in Chemical Reactions Every substance possesses a definite quantity of energy, under a given set of factors such as chemical nature of the substance, temperature and pressure. The total energy contained in a system or substance is called its internal energy or intrinsic energy. It is represented by the symbol 'E' or 'U'. Enthalpy 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. 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. 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. Laws of Thermodynamics - Zeroth Law The 'zeroth law' states that 'if two bodies (say A and B) are in thermal equilibrium with another body C, then the bodies A and B will also be in thermal equilibrium with each other'. This law is important as it helps in understanding the concept of temperature. First Law of Thermodynamics or Law of Conservation of Energy The total energy in the universe is present either as kinetic energy or as potential energy. For example, the water stored in a dam possesses potential energy by virtue of its height (position). When this water is allowed to fall, its potential energy gets converted into kinetic energy. Falling water can rotate the turbines and produces electricity, due to its kinetic energy. In other words, the total energy remains constant even when a body changes its position, because one form of energy may be converted into another. This leads to an important conclusion known as conservation of energy or the first law of thermodynamics. Heat Capacity Heat capacity gives a measure of the quantity of heat absorbed by a system. It is defined as the amount of heat required to rise the temperature of the system through 1oC. If the quantity of heat required is to raise the temperature of unit mass of the substance through 1oC then it the specific heat of the substance. Whereas when the whole mass of the substance is considered, it is the heat capacity. Thermochemical Reactions Chemical reactions involve energy changes. These changes can be represented in a standard way called the thermochemical equation. Heat or Enthalpy of Reaction The amount of heat evolved or absorbed in a reaction is known as heat of reaction. As the amount of heat evolved or absorbed at constant temperature and pressure is called enthalpy, the heat

changes for various reactions may also be called enthalpy changes. The heat change during a chemical reaction depends upon the amount of substance (number of moles) that has reacted. Thus, heat of reaction may be defined as 'the amount of heat evolved or absorbed in a reaction when the number of moles of reactants react completely to give the products as given by the balanced chemical equation'. Standard Enthalpy of Reaction As the heat of a reaction varies with temperature it is desirable to fix up a standard or a reference state. A substance is said to be in standard state when it is present in its most stable state at 298 K under a pressure of one atmosphere. Types of Heat (enthalpy) of Reactions The heat or enthalpy changes taking place during the chemical reactions are expressed in different ways depending upon the nature of the reaction. Measurement of Enthalpy of Reactions The heat changes in chemical reactions are measured with the help of calorimeters. Depending upon the requirements of experiments different types of calorimeters are used. In general, reactions taking place at constant volume and involving gases are carried out in a closed container with rigid walls that can withstand high pressures such as a bomb calorimeter. The body of the bomb calorimeter is made of heavy steel. The steel vessel is coated inside with gold or platinum to avoid oxidation of steel during the chemical reactions. The vessel is fitted with a tight screw cap. There are two electrodes R1 and R2, which are connected to each other through a platinum wire S, which remains dipped in a platinum cup just below it. Determination of Enthalpy Change 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. Laws of Thermochemistry A.L.Lavoisier and P.S.Laplace gave this law in 1780 which states that 'the enthalpy of a reaction is exactly equal but opposite in sign for the reverse reaction'. Bond Energy or Bond Enthalpy In chemical reactions the formation of a chemical bond is accompanied by the release of energy. Conversely energy has to be supplied for the breaking of a bond. Sources of Energy The Sun radiates energy in the form of heat and light. We utilize these forms of energy either directly or indirectly, after conversion into some other forms. Utilization of solar energy in various ways is as represented. Besides the primary role of the Sun's energy, it is now believed that elements have been formed from hydrogen by the process of nuclear fusion occurring in stars, similar to the sun. In that sense, everything that we see around us, including ourselves and the uranium we use as nuclear fuel, are products of the star-dust. Hence, stars in general and our sun in particular, are the ultimate source of energy. Calorific Value of Foods and Fuels Nutritional value of foods, and the usefulness of fuels is determined by the heat (energy) they produce on heating. The energy released by the combustion of foods or fuels is usually compared in terms of their combustion energy per gram. It is known as calorific value. It is defined as the amount of heat produced in calories (or joules) when one gram of a substance (food or fuel) is completely burnt. Conservation of Energy Sources Fossil fuels are the major source of energy on Earth. With the development of technology, the worlds consumption of the concentrated sources of energy like coal, petroleum and natural gas and uranium has

increased. Very slow physical and chemical processes spread over many thousand years form these fuels. It is estimated that the use of nonrenewable reserves of energy fuels at a faster rate than at which they are getting formed will deplete the fossil fuels within 30 - 40 years. Their fast depletion in such circumstances has come to be known as 'the energy crisis'. Pollution Due to the Burning of Fossil Fuels (Additional) Contamination of air with harmful toxic gases, smoke and particulate matter (e.g., dust etc.) is called air pollution. The substances that cause pollution are called pollutants. Combustion of fossil fuels is one of the main causes of pollution of the atmosphere in our cities and towns. Fossil fuels are mainly used in the generation of electricity (thermal power plants), and as fuel for transport.