Introduction to Thermodynamic The field of science dealing with energy in the form of heat and work and their

conversion into each other and the effect of energy transfer on the properties of systems is called Thermodynamics. The study of thermo dynamics began with mans desire to convert heat into mechanical work and to produce desired changes in a system by means of exchange of heat or work in the most economical way. Macroscopic and Microscopic Analysis The description of a system using a few measurable properties is known as Macroscopic analysis of the system. If the analysis is made on the basis of the behaviour of individual atoms and molecules of a substance under investigation, then the analysis is said to be microscopic behaviour of systems and helps to reinforce the conclusions of macroscopic studies. System and Surroundings A thermodynamic system is defined as a region in space or a quantity of matter upon which attention is focussed for the study of work and heat transfer and conversion. Everything outside the system which has direct bearing on its behaviour is known as surroundings. The system is separated from the surroundings by the system boundary. The boundary may be real or hypotentical. mass and energy transfer take place between the system and surroundings through the boundary of the system. Closed system An example of a colosed system is piston in a cylinder. The mass of the closed system remains constant and only energy can flow through the boundary in or out of a closed system. The volume of a closed system need not be constant and it changes due to the movement of the piston in the cylinder. Work transfer between system and surroundings takes place due to the movement of the boundary of the system considered. Closed system concept is very often used in thermodynamic analysis. Open system Mass transfer also takes place through the boundary in addition to the work and heat transfer in case of open systems. The boundary of the open system is known as control volume. The boundary during the transfer of mass and energy may change or may not change. State Each unique condition of a system is called a state. The state of a system can be represented by a point on a diagram whose co-ordinates are properties. This is possible as any two independent properties define the state of a system. When the

system undergoes a change from one thermodynamic equilibrium state to another equilibrium state due to heat or work transfer, the new state is represented by another point on the property diagram. Thermodynamic/Thermal Equilibrium A system is said to be in thermal equilibrium when the temperature at all points in the system is same. A system is said to be in mechanical equilibrium when the pressure at all points in the system is same. The properties, pressure and temperature do not change with respect to time if the system is isolated and is in equilibrium condition. Thermal equilibrium denotes only uniformity of temperature. Mechanical equilibrium denotes only uniformity of pressure. Chemical equilibrium denotes absence of chemical reaction. But thermodynamic equilibrium includes all types of equilibrium. PROCESS AND CYCLE Process. A process is said to occur when the system undergoes a change in state. The state points from the initial to final can be marked on a property diagram if the properties at all states are known. Cycle. If a number of processes in sequence bring back the system to its original state, the system is said to execute a cycle. Work. The work performed by a thermodynamic system that undergoes a volume change from V1 to V2 is Geometrically, the work done by a system is the area under the P versus V curve. The work depends on the path between the initial and final states. Internal Energy In the macroscopic approach of thermodynamics, there is no need to specify the physical nature of the internal energy. The experimental results are sufficient proof that such a function exists. However, it is worth noting that the internal energy is the sum of all possible kinds of energy stored in the system-mechanical, electrical, magnetic, chemical, nuclear, and so on. It does not include the kinetic and potential energies associated with the random motion of particles form a part of the internal energy called thermal energy. First law of Thermodynamics This law based onJoules experiment states that if a system executes a cycle transferring work and heat through its boundary, then the net work transfer is equivalent to the net heat transfer The first law of thermodynamics cannot be proved mathematically but experimental evidences have repeatedly confirmed its validity. Also, no phenomenon has been

shown to contradict it and therfore it is accepted as a law of nature. No restriction was imposed which limited the application of first law to reversible energy transformations. hence the first law of thermodynamics applies to reversible as well as to irreversible transformations. When a system executes a process, the change in stored energy of the system is numerically equal to the net heat interactions minus the net work interaction during the process. Where is the change in internal energy during the process. In general, the addition of heat to a system results in a rise in temperature of the system and external work is performed due to increase in volume of the system. The rise in temperature is an indication of increase of internal energy. Heat added to the system will be considered as positive and the heat removed or rejected, from the system, as negative. First law does not merely define the internal energy but it states that the internal energy is a quantity different in kind from heat and work. Internal energy being a property can be increased or decreased by the change of state of a system. The internal energy of a closed system remains unchanged if the system is isolated from its surroundings. APPLICATION OF FIRST LAW Constant Volume Process. In this process volume remain constant during the Heat addition. During the process Work done ; where Cv is the molar specific heat at constant volume. Constnat Pressure Process. The workdone W = P (V2 V1) = nR (T2 T1) If the change in temperature is , the heat absorbed Q = Where CP is the molar specific heat at constant pressure. Applying first law At constant pressure constant temperature process. In an isothermal process, PV = constant ; Adiabatic Process. In an adiabatic process, the system does not exchange heat with its surroundings; that is Q=0. This may be accomplished in two ways. First, the system can be enclosed in a thermally insulated container. Second, the process could occur so quickly that there is not enough time for an appreciable quantity of heat to be exchanged with the surroundings. For example, the rapid compression stroke in a

diesel engine is approximately adiabatic. The first law for an adiabatic process takes the form . constant ; Second Law of thermodynamics The ffirst law of thermodynamics states the equivalence of different forms of energy and makes no distinction between the forms of energy. If one form of energy disappears (say work), it appears in another form in equal amount and that means energy is neither creasted nor destroyed. First law is silent about the possibility or otherwise of any energy conversion. If a closed system executes a cycle, then As per the above equation the first law merely states that the work transfer during the cycle is equal to the heat transfer and does not place any restriction on the direction of heat and work transfer. According to this law, it is assumed that the energy transfer can take place is either direction. It does not specify the direction of the energy transfer. The second law states whether it is possible for energy transfer to proceed along a particular direction or not. Many day-today experiences indicate that the transfer process can proceed along one direction but reverse is impossible. Example : A hot cup of tea cools by virtue of heat transfer to the cooler surrounding but once it is cooled, it can never be heated by addition of heat from the cooler surroundings. As per the Joules experiment, it has been found that when the free expansion takes place with a gas, there is no change in temperature, but the volume increases and pressure decreases without doing any work. If the above process has to take place in opposite direction, then the gas at low pressure should rush back through the value and compress itself to its original process. It is found in practice that such process is impossible. In the above example, it is obvious that the energy transfer or the process can proceed along a particular direction while it is impossible in the opposite direction even if the first law is satisfied. It is obvious that the first law of thermodynamics is not sufficient to predict whether a system will or will not undergo a particular change, as no restriction has been imposed on the possibility of conservation of energy from one form to another by the first law of thermodynamics. The first law of thermodynamics is a necessary but not sufficient condition for a process to take place. Reversible and Irreversible process

It is logical to investigate the maximum possible efficiency that a heat engine can have if it cannot have 100% efficiency. The concept of a reversible process helps us to determine this. A reversible process can be defined as that process which can be performed in the reverse direction restoring the system to its original state 1 and the surroundings back to its initial condition as at the beginning of the process. That is, at the end of the reversal of a reversible process, the system and the surroundings are unaffected. In other words, it can be stated that it will be impossible to know whether the process has been performed or not if reversibility is achieved. A process that does not meet these requirements is irreversible. The conditions to be fulfilled by a reversible process : (1) The energy transfer as heat and work during the forward process should be identically equal to the energy transfer as heat and work during the reversal of the process. (2) The process should not involve friction of any kind (fluid friction or mechanical friction) (3) Heat transfer should not take place with finite temperature difference. (4) There should not be mixing of the fluids. (5) There should be no free or unrestricted expansion. (6) The process must proceed in a series of equilibrium states. Few examples of reversible processes : (1) Frictionless adiabatic expansion or compression. (2) Frictionless isothermal expansion or compression. (3) Condensation and boiling of liquids The processes which occur naturally or which are performed in engines are mostly irreversible. Few of such commonly known processes : (1) Process of combustion. (2) Heat flow from a higher temperature to lower temperature. (3) Flow of electric current through a register. (4) Mixing of two fluids. (5) All processes involving friction. Heat Engines A heat engine is a device that converts heat into mechanical work. Examples include steam engines, gasoline engines, and diesel engines. In each cycle the engine absorbs heat Q1 from the hot reservoir. Some of this heat is used to do work, W, and the remaining heat, Q2, is discharged to the cold reservoir. The net work done by the engine in a cyclic process is equal to the net heat influx :

The thermal efficiency of a heat engine is defined as the work output divided by the heat inpur (Woutput/Qinput):

The engine would be 100% efficient only if . In this case, all the heat input would be converted into work. However, this is not possible, and the efficiency of even an ideal engine is less than 100%. A gasoline engine has an efficiency of about 20%, whereas for a diesel engine it is about 30%. The Kelvin-Planck Statement of the Second Law It is impossible for a heat engine that operates in a cycle to convert its heat input completely into work. The Clausius Statement of the Second Law It is impossible for a cyclical device to transfer heat continuously from a cold body to a hot body without the input of work or other effect on the environment. Carnot Cycle The following assumptions are made in the operation of Carnot cycle. (1) The piston moving in a cylinder does not encounter any friction during motion. (2) The walls of piston and cylinders are considered as perfect heat insulators. (3) The cylinder head of the cylinder is so arranged that it can be a perfect heat conductor or perfect heat insulator as required (interchangeable cylinder head). (4) The transfer of heat does not affect the temperature of the source or sink. Process ab isothermal expansion, Process bc : adiabatic expansion, Process cd : isothermal compression and Process da : adiabatic compression. Efficiency of the Carnot Cycle In carnot engine The efficiency of a Carnot heat engine is . The Carnot efficiency depends only on the Kelvin temperatures of the reservoirs. The efficiency is always less than 100%, unless T2 = 0. Carnots Theorem (i) All reversible engines operating between two given reservoirs have the same efficiency. (ii) No cyclical heat engine has a greater efficiency than a reversible engine operating between the same two temperatures. Clasius Theorem and Clausius Inequality

The Clausius theorem which states that whenever a system is taken through a reversible cycle, the cycle integral of dQ/T around the reversible cycle vanishes. We know that this is the characteristic of a property and hence (dQ/T)R is a property of the system known as entropy. Clausius Inequality : If the cycle is irreversible the above integral . Third law of Thermodynamics The third law states that it is impossible to attain absolute zero within infinite number of reversible engines in series developing work reveiving energy from the source at a particular temperature.