THERMODYNAMICS

Thermodynamics is the science of the conversion of energy, in terms of heat and work and their mutual relationship along with properties of the system.

MACROSCOPIC AND MICROSCOPIC APPROACH There are two point of views to study a thermodynamics problem from which the behavior of matter can be studied. They are known as macroscopic approach and microscopic approach. In the macroscopic approach, we study the gross or time averaged effects of the particles which may be observable and measurable by instruments. The macroscopic approach is used in Classical Thermodynamics which is the subject matter of the text. In this point of view we deal with volumes that are considerably large compared to molecular dimensions. It is not concerned with the behaviour of individual molecules. Therefore, it treats the matter as continuous, or the whole of this as a Continuum. For example, when a container contains gas, the gas exerts pressure on the walls of its container. The pressure results from the change in momentum of the gas molecules as they collide against the wall of the container. In this approach, it is not concerned with the collisions of the molecules, but with the time averaged value of force exerted on the unit area of the surface of the container, which can be measured by a pressure gauge. In microscopic approach, we make an attempt to analyze system by considering it as comprising of discrete particles which are its atoms and molecules. It is difficult to adopt it in practice. The modified microscopic approach is employed to simplify this problem in which we deal with average value for all particles under consideration making use of the theory of probability. This modified approach is employed in statistical thermodynamics and kinetic theory of gases. It is particularly helpful, when dealing with the system in which the mean free path of the molecules is large compared with the dimension of the system such as in high vacuum technology.

What is meant by thermodynamic system? How do you classify it? THERMODYNAMIC SYSTEM Thermodynamic system is defined as the specified portion of universe which is under thermodynamic consideration or thermodynamic studies. It may be classified into three types. a) Open system b) Closed system c) Isolated system CLOSED SYSTEM When a system has only heat and work transfer, but there is no mass transfer, it is called as closed system. Example: Piston and cylinder arrangement, Thermal power plant. OPEN SYSTEM When a system has both mass and energy transfer it is called as open system. Example: Air Compressor, Gas turbine power plant. ISOLATED SYSTEM The system in which neither mass nor energy transfer takes place is called isolated system. Isolated system is not affected by surroundings. There is no heat; work and mass transfer take place. In this system total energy remains constant. Example: Entire Universe thermo-flask.

What is meant by surroundings? SOURROUNDING Any other matter out side the system boundary is called as surroundings. What is boundary? BOUNDARY System and surroundings are separated by an imaginary line is called boundary. Boundary may be fixed or movable. It may be real or imaginary.

Thermodynamic property Thermodynamic property is an observable characteristic of the system. Thermodynamic property is any characteristic of a substance which is used to identify the state of the system and can be measured, when the system remains in an equilibrium state. Thermodynamic property can be classified into two types. Intensive or Intrinsic and Extensive and Extrinsic property. Define Intensive and Extensive properties. Intensive properties. The properties which are independent on the mass of the system is called intensive properties. e.g., Pressure, Temperature, Specific Volume etc., Extensive properties The properties which are dependent on the mass of the system is called extensive properties. e.g., total energy, Total volume, weight etc. Differentiate Intensive and Extensive properties Intensive Properties 1. Independent on the mass of the system 2. If we consider part of the system these properties remain same. e.g. pressure, Temperature specific volume etc., 3. Extensive property/mass is known as intensive property Extensive Properties Dependent on the mass of the system. If we consider part of the system it will have a lesser value. e.g., Total energy, Total volume, weight etc., --

State of the system

State of the system is condition of the system as identified by the some fundamental measurable quantities like pressure, volume, temperature and density, etc Initial state (P1,V1,T1) Final state ( P2,V2,T2)

Define Point and Path function with examples? Point function The quantity which is independent on the process or path followed by the system is known as point functions. Example: Pressure, volume, temperature, etc., Path function The quantities which are dependent on the process or path followed by the system is known as path functions. Example: Heat transfer, work transfer. ----------------------------------------------------------------------------------------------------------CYCLE When a process is performed in such a way that the final state is identical with the initial state, it is called a thermodynamic cycle Closed and open cycle In a closed cycle, the same working substance will recirculate again and again. In a open cycle, the same working substance will be exhausted to the surroundings after expansion. ----------------------------------------------------------------------------------------------------------PROCESS A process may be as the path or operation by which system changes from one state to another. In other words, when the system changes its state from one state to another, it undergoes a process. A process involves the change of state variables. ----------------------------------------------------------------------------------------------------------CYCLIC PROCESS OR THERMODYNAMIC CYCLE When a process or processes are performed on a system in such a way that the initial and the final states will be same, then the process is called thermodynamic cycle or cyclic process. In figure 1.6 1-A-2 and 2-B-1 are two simple processes whereas 1A-2-B-1 is a cyclic process, whose final and initial states are the same.

THERMODYNAMIC EQUILIBRIUM A system is said to be in thermodynamic equilibrium, when no change in any one of the properties do occur. A system will be in a state of thermodynamic equilibrium, if it satisfies the following three requirements of equilibrium (a) Mechanical equilibrium, (b) Chemical equilibrium (c) Thermal equilibrium. Mechanical Equilibrium The system is said to be in mechanical equilibrium, when there is no unbalanced force within the system. Chemical Equilibrium The system is said to be in chemical equilibrium, if there is no chemical reaction and no transfer of matter from one part of the system to another. Thermal Equilibrium Thermal equilibrium means temperature at all the points of the system remains constant. When two bodies having different temperature are brought in contact with each other, after some time both attains same temperature. When this state of the temperature is attained then the bodies is said to be in thermal equilibrium.

What is Quasi-static process? State its significance in thermodynamics Quasi static process:

A Quasi-static process is defined as the process in which the property of system departs infinitesimally from the thermodynamic equilibrium path
Quasi-static process is a process carried out in such a way that at every instant, the deviation of the state from the thermodynamic equilibrium is very infinitesimally small. Every state passing through the system will be closely approximately succession of equilibrium states. The locus of all these points passed through the system is a quasi-static process. A quasis-static process can be viewed as a sufficient slow process that allow the system to adjust itself internally so that the properties in one part of the system do not change faster than those at the other parts.

A Quasi-static process is shown in the figure AB is a quasistatic process and at the successive stated (shown by the point 1, 2, 3 etc), the system is very near of thermodynamic equilibrium. Only quasi-static process can be represented on the thermodynamic plane.

Example: Very slow compression of the gas enclosed in a cylinder. Significance of Quasi static process Engineers are interested in quasi-static process for two reasons Easy to analyze.

Work producing devices delivers the most of work, when they operate on quasi-static process. Therefore the Quasi-static process serves as a standard to which the actual process is compared. What is meant by thermodynamic work? 1. THERMODYNAMIC WORK It is the work done by the system when the energy transferred across the boundary of the system. It is mainly due to intensive property difference between the system and surroundings. SIGN CONVENTION Work done on system = - ve. Ex: Compression Work done by the system = +ve Ex: Expansion 2. HEAT Heat is the energy crossing the boundary due to the temperature difference between the system and surroundings. It is mainly due to intensive property difference between system and surrounding. Unit ; N-m or Joule. SIGN CONVENTION Heat rejected by system = - ve. Heat added to the system = +ve

3. TEMPERATURE
It is a thermodynamic property which shows the degree of hotness or heat intensity of the body. It is measured with the thermometer, thermocouple and radiation pyrometer. It is expressed in degree centigrade or Kelvin.

4. ENTHALPY Enthalpy is defined as sum of internal energy and product of pressure volume. H = U + PV

REVERSIBLE AND IRREVERSIBLE PROCESS Reversible Process

Reversible process is a process carried out in such a way that at every instant, the system deviation is only infinitesimal from the thermodynamic state, and also which can be reversed in direction and the system retraces the same equilibrium states. Thus in reversible process, the interactions between the system and the surroundings are equal and opposite in direction. The Quasi-static or Quasiequilibrium process is also known as reversible process. In reversible process the work done could be written in the form W = pd When there is a change in system boundaries.

Two important conditions for the reversible process to occur. a) Firstly, the process should occur in infinitesimally small time and b) secondly all the initial and final state of the system should be in equilibrium with each other. Example : Frictionless relative motion. Frictionless adiabatic expansion or compression of gas. Isothermal expansion or compression. Extension and compression of spring.

Irreversible Process
A process is said to be irreversible, while initial and final states both being in equilibrium, when reversed, the system and the surroundings do not come to the original initial state and a trace of history of the forward process is left. In actual practice, most of the processes are irreversible, due to turbulence in the system, temperature gradients in the system and due to friction. A process will be irreversible if the system passes through the non equilibrium states. In Irreversible process, the network output is less than pd and is given by Wnet = pd - Wdissipated.

Examples: Relative motion with friction. Combustion of air fuel. Throttling Heat transfer finite temp difference.

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Reversible process
The process in which the system and surroundings can be restored to the initial state from the final state without producing any changes in the thermodynamics properties of the universe is called as the reversible process. It is an ideal process. It passes through a series of series of equilibrium states. During reversible process all the changes in state occurred in the system are in thermodynamic equilibrium with each other. The reversible process can be reversed completely and there is no trace left to show that the system had undergone thermodynamic change. For the system to undergo reversible change, it should occur infinitely slowly due to infinitesimal gradient. The phenomenon of undergoing reversible change is also called as reversibility. In actual practice the reversible process never occurs, thus it is an ideal or hypothetical process.

Irreversible process
The process in which the system and surroundings can not be restored to the initial state from the final state without producing any changes in the thermodynamics properties of the universe is called as the reversible process.

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All process occurring in nature is irreversible process. The irreversible process is such that change is spontaneous. During irreversible process the various states of the system on the path of change from initial state to final state are not in equilibrium with each other. In the irreversible process the initial state of the system and surroundings cannot be restored from the final state.

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During the irreversible process the entropy of the system increases decisively and it cannot be reduced back to its initial value. The phenomenon of system undergoing irreversible process is called as irreversibility The irreversible process is also called as natural process because all the processes occurring in the nature are irreversible processes.

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Example: Frictionless relative motion. Frictionless adiabatic expansion or compression of gas. Isothermal expansion or compression. For reversible process W = p. dv In reversible process the interaction between the system and surrounding are equal and opposite in directions.

Example: Relative motion with friction. Combustion of air fuel. Throttling Heat transfer finite temp difference. For irreversible process W = pdv W dissipated In irreversible process the interaction between the system and surrounding are not equal.

Explain Zeroth Law of thermodynamics? Zeroth Law of thermodynamics

If two states are each in thermal equilibrium with the third system, then the two system are also said to be in thermal equilibrium with each other.

Take three bodies namely A, B and C. suppose A and C are in thermal equilibrium with each other. Similarly B and C are in thermal equilibrium. Then According to Zeroth law, A and B are also in thermal equilibrium. 11

Significance of ZEROTH LAW OF THERMODYNAMICS

This Law allows, among other things, the creation and calibration of thermometers. It serves basis for the validity of temperature measurement.

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