1 1.

0 INTRODUCTION AND APPLICATIONS OF THERMODYNAMICS

INTRODUCTION Thermodynamics is the study of the flow of heat into or out of a system, as the system undergoes a physiacal or chemical transformation. (dynamics). It deals thus with the energy interactions in physical systems. Classical thermodynamics can be stated in four laws called the zeroth, first, second, and third laws respectively. The laws of thermodynamics are empirical, i.e., they are deduced from experience, and supported by a large body of experimental evidence. Metallurgical Thermodynamics is thermodynamics applied to Metallurgy. 1.1 APPLICATIONS OF THERMODYNAMICS a) It tells whether a particular physical or chemical change can occur under a given set of conditions of temperature, pressure and concentration. b) It also helps how far a physical or chemical change can proceed until equilibrium conditions are established APPLICATIONS IN METALLURGY a) In the construction of phase diagrams b) To understand various chemical reactions and to predict the correct reducing agent in ferrous and non ferrous extractive metallurgy c) To understand various phase transformations in the heat treatment process d) To understand interactions of various alloying elements in alloys. 1.2 GAS LAWS

The laws which describe the behavior of a gas are known as gas laws. Which are as follows: 1) Boyles Law : Boyles Law states that , if the temperature remains constant , the volume of a given mass of a gas varies inversely as the pressure to which it is subjected that is 1 V P Or P V = K (constant) 2) Charles Law : It states that, if the pressure remains constant , the volume of a given mass of a gas varies directly as its absolute temperature. That is V T, when P is constant

1.3

Daltons law of partial pressures Dalton's law of partial pressures states that the total pressure exerted by a gaseous mixture is equal to the sum of the partial pressures of each individual component in a gas mixture Mathematically, P total = P1 + P2 +..+Pn

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STATEMENT AND DERIVATION OF IDEAL GAS EQUATION The statement of Ideal gas equation is P V = n R T Where P---pressure V---Volume n---no.of moles of ideal gas R--- Universal gas constant T--- Absolute Temperature of ideal gas.

2 Derivation of Ideal gas equation According to Boyles Law V

1 P

At Constant T and m According to Charles Law is V T at constant P and m Combining the above two laws we can write V

T P

Or PV T = K

Where K is a constant whose value can be found as follows P0V0 T0 = K

Where P0 is 1 atm pressure V0 is 22.4 lit T0 is 2730K If the above values are substituted in the above equation we get K =0 .0821 lit-atm Now K is known as universal gas constant and is represented by R Therefore now the ideal gas law takes the following form PV = RT

For n moles of ideal gas the equation then becomes PV 1.5 = nRT

PERFECT AND REAL GAS

An ideal gas or perfect gas is a hypothetical gas consisting of identical particles of zero volume, with no intermolecular forces. Additionally, the constituent atoms or molecules undergo perfectly elastic collisions with the walls of the container. Ideal gases follow the Boyles Law and Charles Law at all temperatures and pressures Real gases do not exhibit these exact properties, although the approximation is often good enough to describe real gases. Real gases behave as ideal gases only at at high temperatures and low pressure. 1.6 SYSTEM SURROUNDING & BOUNDARY WITH EXAMPLES

System: A System is that part of the universe which is under thermodynamic study. Surroundings: Everything external to the system is called surroundings. Boundary: The real or imaginary surface separating the system from the surroundings is called the boundary.

In experimental work, a specific amount of one or more substances constitutes the system. Thus 1 mole of oxygen confined in a cylinder fitted with a piston is a thermodynamic system. The cylinder and the piston and all other objects outside the cylinder form the surroundings. Here the boundary between thy system (oxygen) and the surroundings (cylinder and piston) is clearly defined. TYPES OF SYSTEMS 1.7 Homogeneous and heterogeneous systems

When a system is uniform throughout, it is called a Homogeneous system. Examples are: a pure single solid, liquid or gas, mixture of gases and true solution of a solid ion a liquid. In metallurgy, Austenite (FCC solid solution of carbon in iron), ferrite (BCC solid solution of carbon in iron), Cu-Ni alloys, etc are some of the examples of homogeneous systems. A Homogeneous system is made of one phase only. A heterogeneous, system is one, which consists of two or more phases. In other words it is not uniform through out. Examples of heterogeneous, systems are: Ice in contact with water, ice in contact with vapour, etc. Here ice water and vapour constitute separate phases. In metallurgy, Fe-0.4%C, Al-12%Si, Grey cast iron etc. are some of the examples of heterogeneous, systems. Differences between Homogeneous and Heterogeneous Systems Homogeneous System 1) Composition is Uniform 2) Consists of Single Phase 3) Example: Solutions, Cu-Ni Alloys 1.8 Heterogeneous System 1) Composition is not Uniform 2) Consists of more than one Phases 3) Example: Mixtures, Grey Cast Iron

Isolated system, Closed system, Open system and Adiabatic system

Basing on the criterion that whether or not the energy or mass transfer takes place through the boundary of the system systems are of three types they are 1) Isolated system: An Isolated system is one that can transfer neither matter nor energy to and from its surroundings Let us consider a system 100 ml of water in contact with its vapour in a closed vessel, which is insulated. Since the vessel is sealed, no water vapour (matter) can escape from it. Also because the vessel is insulated no heat (energy) can be exchanged with the surroundings. A substance say hot coffee contained in a thermos flask is another example of an isolated system.

2) Closed system: A closed system is one which cannot transfer matter but can transfer energy in the form of heat, work and radiation to and from its surroundings. Here the boundary is sealed but not insulated. A specific quantity of hot water contained in a sealed tube is an example of a closed system. While no water vapour can escape from this system, it can transfer heat through the walls of the tube to the surroundings. A gas contained in a cylinder fitted with a piston constitutes a closed system. As the piston is raised the gas expands and transfers heat (energy) in the form of work to the surroundings.

3) Open System: An Open System is one, which can transfer both energy and matter to and from its surroundings. Hot water contained in a beaker placed on laboratory table is an open system. The water vapour (matter) and also heat (energy) is transferred to the surroundings through the imaginary boundary. 4) Adiabatic System: The system, in which no thermal energy passes into or out of the system, is said to be Adiabatic System. THERMODYNAMIC PROPERTIES Thermodynamic properties are the thermodynamic coordinates, which fixes up the state of the system. Examples are: Pressure, Volume, Temperature and Mass. TYPES OF PROPERTIES 1.9 Intensive, Extensive, State and Path Properties The macroscopic or bulk properties of a system (volume, pressure, mass etc) basing on whether or not they can depend on mass can be divided into two classes a) Intensive Properties b) Extensive Properties A property, which does not depend on the quantity of matter present in the system, is known as Intensive property. Examples: Pressure, Temperature, density and Concentration etc. A property that does depend on the quantity of matter present in the system is known as Extensive property. Examples: Volume, No. Of moles, free energy, entropy etc.

5 Basing on the criterion whether or not the properties depend on the path followed by the system they are two types a) State properties b) Path properties State properties are those, which do not depend on the path followed by the system but depend only on the initial and final states of the system. Examples: Internal energy, Free energy, Entropy, Pressure, Volume, Temperature, Enthalpy etc. Path properties are those, which do depend on the path followed by the system. Examples: Work done, Heat etc. By definition the Extensive Properties are additive while intensive properties are not. 1.10 STATE OF A SYSTEM AND EQUATION OF STATE

State: A Thermodynamic system is said to be in certain state when all its properties are fixed. The fundamental properties, which determine the state of a system, are pressure (P), temperature (T), volume (V) and composition. Since a change in the magnitude of such properties alters the state of the system, these are referred to as state variables or thermodynamic parameters. State Equation: An algebraic relation ship between state variables is called the equation of State. Example: For one mole of an Ideal gas the state equation is given as PV=nRT Where P is pressure, V is Volume, n is No. of moles, R is Universal gas constant and T is Temperature 1.11 EQUILIBRIUM STATE AND THE CRITERIA FOR EQUILIBRIUM Equilibrium State A System in which the state variables have constant values through out the system is said to be in a state of thermodynamic equilibrium. Example: Suppose we have a gas confined in a cylinder that has a friction less piston. If the piston is stationary, giving the values of pressure and volume can specify the state of the gas. The system is then in a state of equilibrium.

Non-Equilibrium State A System in which the state variables have different values in different parts of the system is said to be in a non-equilibrium state. If the gas contained in a cylinder is compressed very rapidly by moving down the piston, it pass through states in which pressure and temperature cannot be specified, since these properties change through out the gas. The gas near the piston is compressed and heated and that at the far end of the cylinder is not. The gas then would be said to be in nonequilibrium state. Thermodynamics is concerned only with equilibrium states.

The Criteria for Equilibrium: For the establishment of thermodynamic equilibrium the system should be in the following equilibria. 1) The temperature of the system must be uniform through out the system (Thermal equilibrium). 2) The mechanical properties must be uniform through out the system (Mechanical Equilibrium). 3) The Chemical composition of the system must be uniform through out the system (Chemical equilibrium). THERMODYNAMIC PROCESSES When a thermodynamic system changes from one state to another, the operation is called a process. These processes involve the change of properties such as changes in temperature, pressure and volume etc. 1.12 Types of thermodynamic processes

1) Isothermal Process: Those Processes in which the temperature remains constant are termed Isothermal Processes. For an Isothermal Process dT = 0 (dT means difference or change in T)

2) Adiabatic Process: Those Processes in which no heat can flow into or out of the system, are called Adiabatic Processes. For an Adiabatic Process Q = 0 (Q means difference or change in Q)

3) Isobaric Process: Those Processes in which the pressure remains constant are termed Isobaric Processes. For an Isobaric Process dP = 0 (dP means difference or change in P)

4) Isochoric Process: Those Processes in which the volume remains constant are termed Isochoric Processes. For an Isochoric Process dV = 0 1.13 (dV means difference or change in V)

REVERSIBLE AND IRREVERSIBLE PROCESSES

Reversible Process: A Thermodynamic reversible Process is one that takes place infintesimally slowly and its direction at any point can be reversed by an infintesimal change in the state of the system. In fact, a reversible process is considered to proceed from the initial state to the final state through an infinite series of infinitesimally small stages. At the initial, final and all intermediate stages, the system is in equilibrium state. This is so because an infintesimal change in the state of the system at each intermediate step is negligible. Irreversible Process: When a process goes from the initial to final state in a single step and cannot be carried in the reverse order, it is said to be an irreversible process. Here the system is in equilibrium state in the beginning and at the end, but not at points in between. Example:

7 Consider a certain quantity of gas contained in a cylinder having a weightless and friction less piston. The expansion of the gas can be carried by two methods illustrated below.

Let the pressure applied to the piston be P and this is equal to the internal pressure of the gas. Since the external and internal pressures are exactly counter balanced, the piston remains stationary and there is no change in volume of the gas. Now suppose the pressure on the piston is decreased by an infintesimal amount dP. Thus the external pressure on the piston is being P-dP, the piston moves up and the gas will expand by an infintesimally small amount. The gas will therefore, be expanded infinitely slowly that is by a thermodynamically reversible process. At all stages in the expansion of the gas, dP being negligibly small, the gas is maintained in a state of equilibrium through out, If at any point of the process, the pressure is increased by dP, the gas would contract reversibly (fig. a). On the other hand, the expansion is irreversible (fig. b) if the pressure on the piston is decreased suddenly. It moves upward rapidly in a single operation. The gas is in equilibrium state in the initial and final stages only. The expansion of the gas, in this case takes place in an irreversible manner. Differences between Reversible and Irreversible Processes Reversible Process 1) Takes place infintesimally slowly 2) These are idealized and true in principle only 3) System is at equilibrium at all stages of the process 4) Work done is maximum Irreversible Process 1) Takes place with finite speed 2) All actual processes which occur are Irreversible 3) System is at equilibrium only at the initial and final stages of the process 4) Work done is less than that of reversible process 5) Efficiency of reversible process is 5) Efficiency is less maximum

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HEAT AND WORK

When a change in the state of a system occurs, energy is transferred to or from the surroundings. This energy may be transferred as heat or mechanical work. Heat: Heat is defined as the energy in transit Work: Mechanical work is defined as forceXdistance. Units of Heat: In S.I units heat is measured in joules. Units of Work: In S.I units Work is measured in joules. Sign Convention of Heat: The symbol of Heat is Q. If the heat flows from the surroundings into the system to raise the energy of the system; it is taken to be positive,

8 +Q. If heat flows from the system into the surroundings, lowering the energy of the system, it is taken to be negative, -Q. Sign Convention of Work: The symbol of Work is W. If the Work is done by the system then work is taken as positive +W. On the other hand if work is done on the system it is taken as negative, -W. 1.15 PRESSURE-VOLUME WORK

In physics mechanical work is defined as force multiplied by the distance through which the force acts. In thermodynamics the only type of work generally considered is the work done in expansion (or compression) of a gas. This is known as Pressure Volume Work or PV work or Expansion work. Derivation of equation for work of expansion Consider a gas contained in a cylinder fitted with a friction less piston. The constant pressure acting is P. If the gas expands at constant pressure, the piston moves through a distance let this distance is l. Then work = forceXdistance W = fxl But f = PxA (here A=area of cross section of the piston) There fore W = PxAxl = Pxl (here l = change in volume) There fore Work = Pressure X change in Volume

l Gas at constant pressure

1.16 COMPLETE PROPERTIES

EXACT

DIFFERENTIAL

OF

THERMODYNAMIC

If value of a thermodynamic property is independent of the path followed by the system then that property is called exact differential Mathematically, if Z is a thermodynamic property and is a function of two other thermodynamic properties x and y then Z is said to be a complete differential if the following changes in Z are equal Z x Z y Z y Z x

dZI

dx dy

+ +

dy dx

dZII = Then

dZI = dZII

Or the condition for Complete or Exact differential is 2Z xy = 2Z yx