THERMODYNAMICS

Thermodynamics deals with the relationship between heat and work. Thermodynamics is the study of 3 E's Energy, Equilibrium and Entropy. Basic Definitions : System: It is a definite quantity of matter of fixed mass and identity bounded by a closed surface. All things other than the system is surroundings ( Both space and matter ). There are three types of systems. 1. Closed system - There is no mass transfer between the system and surroundings. But their is energy transfer. Eg. compression of a gas in a piston cylinder. 2. Open system - Both mass and energy transfer takes place. It is classified into steady and unsteady flows. 3. Isolated system - No mass and no energy transfer takes place. Eg. Properties: Properties are used to identify the state of the system and solely dependent upon the state of system and not upon how the state was reached. A quantity is a property if it has a exact differential. A quantity can be called a property of the system if the changes in the value between two equilibrium states of system is same. There are two types of properties. They are

Extensive state properties: Here the value of entire system is equal to sum of the values of the parts of the system. There are dependent upon the mass. E.g.. Total Volume, total energy Intensive state properties: The value of the entire system is not equal to the sum of the parts of the system. There properties are not dependent upon the mass. E.g.. Temperature, pressure, Density etc. Process: Whenever a system undergoes a change, process is said to have taken place. There are different types of process. They are

1. Reversible process: Is the one in which both the system and surroundings return to their original state. All real time process are irreversible. Process are irreversible due to turbulence, temperature gradient and Friction. In a reversible process there should be no viscous force or coulomb friction in the system 2. Cyclic Process: The end states are identical. The system undergoes a series of change and returns to original condition.

3. Quasi-static Process: The system departs from the equilibrium condition only infinitesimally. 4. Adiabatic Process : There is no heat flow between the system and surroundings. ( = 0 ) Work and Heat : Work is the energy in transition in which the energy flows from the system to the surroundings. Heat is the energy in transition which flows from one body to another body on account of the temperature difference between the two bodies. Both the Heat and work are Transient Phenomena, Boundary Phenomena and Path functions. Derivation for displacement work : Valid only for quasistatic process. Consider a cylinder of area 'a' and length of the piston is 'l'. The piston moves due to gas pressure. Between section 1 and 2, the value of pressure and volume is P and V. When the piston moves the force acting on the piston is F = pressure x area = P.a Work done = Force x distance moved = F.dl = P.a.dl We know that area x length = volume. Hence a.dl = v. Thus the above equation for work done becomes P.v. Thus when a piston moves from 1 to 2 the amount of work done is given by dw = Pdv Heat Reservoir : May be a source or sink which can absorb or reject any amount of heat, without it temperature being affected. Path and point functions : This is with reference to a system being taken from state 1 to 2. There may be any three quasi static process A, B, and C. Area below the curve gives the amount of work involved in each case. Thus the value of work depends upon the path and not on the end state of the process. Hence work ( and also heat ) are path functions. On the contrary thermodynamic property are point functions. These are definite values for a given state. The change in property is independent of the path and depends on only the initial and final states ( Exact differential )

Internal energy: A system undergoes a change of state in which both heat transfer and work transfer are involve. The net energy accumulated is stored in the system. The internal energy is just a form of energy like the potential energy of an object at some height above the earth, or the kinetic energy of an object in motion. In the same way that potential energy can be converted to kinetic energy while conserving the total energy of the system, the internal energy of a thermodynamic system can be converted to either kinetic or potential energy. Like potential energy, the internal energy can be stored in the system. Q - Heat to the system. W - Work from the system. ( Q - W ) is the net energy stored in the system. This ( Q - W ) is neither heat or work and is given the name, internal energy of system. Entropy: Entropy means transformation. It increases with the addition of heat and vice versa. Change in entropy can be defined. Over a small range the increase or decrease in entropy when multiplied with absolute temperature, gives the heat absorbed or heat rejected. For any reversible process, the change in Entropy of system and surroundings is Zero. Entropy is the index of unavailability of energy. Energy that goes down the sink is less available for any useful work. Entropy changes are accompanied by heat transfers. But may also take place with out the transfer of heat. In a reversible process, if the entropy of the system increases, then the entropy of surroundings decreases by a equal amount. Entropy is a property like T and V. Change in entropy of a system along two equilibrium states can be obtained by taking the system along any reversible path connecting the states, dividing the heat added at each pointing the point with the temperature and summing the quotients. Energy : It is the capacity to produce effect. There are two types of energy. They are stored energy ( E.g.. Potential energy, Kinetic energy and Internal energy ) and Transient energy ( Heat, work and electric energy ). Throttling : The fluid expands from high pressure to low pressure without doing any work. There is no change in KE and PE. Hence there is no heat transfer. Nozzles and Diffusers :

Nozzles increases the kinetic energy of flowing fluid by creating a pressure drop. But in diffusers, the pressure is increased and Kinetic energy is decreased. Carnot's Cycle: It is a reversible cycle in which the ideal gas receives heat at one temperature and rejects heat at another temperature. There are 2 isothermal and 2 reversible adiabatic process. Efficiency of carnots cycle is given by = W / Qa = ( Qa - Qr ) / Qa Enthalpy : Of a substance is defined as the sum of flow work and internal energy. h = u + pv. Graham's Law of Diffusion of Gas : It states that the rate of diffusion of a gas is inversely proportional to square root of density. Laws In Thermodynamics: Zeroth Law of Thermodynamics: If two bodies are in equilibrium with a third body, then the two bodies are in equilibrium with each other. This permits temperature measurement. First Law of Thermodynamics: This law deals with conservation of energy, which states that energy can neither be created not destroyed, but can be changed from one form to another. Whenever a system under goes a cyclic change the algebraic sum of work transfer is proportional to the algebraic sum of heat transfer. Work and heat are inter convertible. First law could be said as law of internal energy. However the drawback in this law is that it does not tell anything about direction of heat flow. Second Law of Thermodynamics: For an isolated system, only those processes can take place for which the entropy of the system increases or remains constant. In this there are two statements. Lord Kelvin and Max Planck's statement of the Second Law: It is impossible to construct a device operating in a cycle for the sole purpose of extracting

heat from a reservoir and changing it into an equal amount of work without rejecting a part of the heat. i.e. it is impossible to devise a machine that converts 100% of heat into work. i.e. The universe is cooling down. Clausius' statement of the Second Law: It is impossible to construct a device that operating in a cycle will produce no effect other than the transfer of heat from a cooler to a hotter body. The spontaneous flow of heat from a colder body to a hotter body is impossible. Second law could be called as law of entropy. Third Law of Thermodynamics: It introduces the concept of absolute entropy. It states that the total entropy of pure substances approaches 0o as the absolute temperature approaches 0o. ( It is impossible to reach the absolute zero of temperature in any physical process. ) Important Thermodynamic Process : The below mentioned process uses the concept of U = Q - W Process Isobaric Process Significance Pressure is Constant ( P = 0) Example Implications U is zero in a constant pressure process. For an ideal gas, constant pressure work is W = PdV = P V Heat that flows into the system causes the temperature to rise. Q = m Cp T = mR( T2 - T1 ) For an Ideal gas U is a function of the temperature, Hence U is zero since T = 0. Since U = 0 then W = Q. P1V1 = P2V2 = nRT, for an isothermal process. Work done W = PV ln( V2/V1 ) which is also the equation for Q. Pictorial Representation

Gas heated in a cylinder fitted with a movable frictionless piston. The pressure the atmosphere and the pressure due to the weight of the piston remains constant as the gas heats up and expands. Isothermal Temperature The gas in a cylinder is Process is constant compressed slowly enough that heat flows ( T = 0) out of the gas at the same rate at which is being done on the gas.

Isochoric process

Volume is constant ( V = 0)

Heating of a gas in a rigid, closed container.

No work is done on the gas because W = PdV = P ( 0 ) = 0. This implies that U = Q = m Cv T. V1 = V2 = nRT1/P1 = nRT2/P2, the ideal gas law for constant volume process.

Adiabatic process

No heat Compression of a Gas in flows into or an Insulated Cylinder. out of the system ( Q = 0) A heat engine in which the working fluid undergoes an adiabatic reversible cyclic process.

U = W ( Since Q = 0 ). Hence any temperature rise or fall is due to the work done or by the gas alone. W = (P1V1 - P2V2) / ( - 1) Any isentropic process is also adiabatic since U = dQ/T and Q = 0. However, not all adiabatic process are isentropic. For a reversible heat engine, not only the change in entropy of the working fluid must be zero but also U of the environment (heat reservoirs) must also be zero.

Isentropic Entropy is process constant ( S = 0)

Polytropic PVn is process constant

Compression or Expansion of a gas in a real system such as a Turbine.

n = 0 for Isobaric process since PV0= P = constant. n = 1 for Isothermal process since PV1 = PV = NKT = constant. n = 0 for Isovolumetric process and n = for Adiabatic process.

Specific Heat : It is the heat required to raise the temperature of unit mass of substance by one degree. There are two types, they are specific heat at constant volume ( Cv )and Specific heat at constant pressure ( Cp ). For air Cp = 0.24 and Cv = 0.171 The ratio of Cp / Cv = Gamma. and Cp - Cv = R / j Gas Laws :

There are 5 gas laws. All perfect gases obey all gas laws under all conditions of pressure and temperature. 1. Boyle's law : At constant temperature PV = C. The magnitude of C depends upon the volume of the gas. 2. Charles lay : At constant pressure V T. 3. Gay - Lussac law : At constant volume P T. 4. Joules law : Change of internal energy is directly proportional to the change in temperature. 5. Avagadro law : Equal volumes of all gases under the same pressure and temperature contain equal number of molecules. Ideal Gas Obeys the equation of state at all conditions of pressure and temperature. The gases cannot be liquefied or solidified Specific heat values are constant Real Gas Obeys the equation of state at all conditions of Pressure and temperature, except at the point where Pressure approaches absolute Zero. Can be solidified and liquefied. Not so, Varies with temperature and pressure.

Ideal gas equation : PV = mRT where P is in N / m2 V is in m3 T is in K Kg oK R is gas constant in Nm /

Following are the assumptions for a ideal gas

Molecules occupy a negligible volume fraction.

Long range forces of attraction between the particles are negligible. Assumptions of Kinetic Theory

Large number of molecules ~ their motion can be treated statistically.

Molecules are in continuous and rapid motion which is random, colliding with each other and the walls of the vessel very frequently, the collision being elastic. Pressure originates from the summation of large number of reacting forces as the molecules bounce off the walls. Combustion chamber :

Combustion Chambers convert the chemical energy stored in a liquid or gaseous fuel to an enthalpy increase in the gas passing through them. Usually, the gas is air, but it could be any gas with the proper components to react with the fuel. A combustion chamber requires one initial spark to begin the combustion of the fuel in the chamber. After that, the chamber will function as long as it has fresh fuel and gas. The fuel combusts, or burns, in the chamber. This combustion releases large amounts of energy to be absorbed by the gas. This increases the temperature and enthalpy of the gas. Last updated on ,