4 THERMODYNAMICS Introduction Thermodynamics is the branch of physics that deals with the concepts of heat and temperature, the inter conversion on heat and other forms of energy. It can explain phenomena as simple as water boiling in a vessel and also something as complex as the creation of a new star. Thermal Equilibrium + Heat is form of energy. Heat is something that is transferred from a substance at a higher temperature to that at a lower tem- perature. This transfer continue till the level of heat content in both the substance is the same. + Wecan say that when two objects are of the same temperature, they are in thermal equilibrium. + Two systems in thermal contact with each other are in thermal equilibrium if they do not transfer heat between each other. Zeroth Law of Thermodynamics + It is called the Zeroth law because it was proposed after the first and the second laws of thermodynamics were formulated. + “If two systems are each in thermal equilib- rium with a third system, they are also in thermal equilibrium with each other” a + a = B) — B c Schematic representation of Zeroth law of thermodynamics GREER svwopsis WEWEEEE: + System A, Band C are at the same tempera- ture + For example, when we use a thermometer to measure temperature of an object, we use the same principle. When the thermometer and the object are in thermal equilibrium, the thermometer indicate the temperature of the object. The science of measuring temperature is called Thermometry. Heat, Internal Energy and Work + Internal energy is defined as the energy associated with the random, disordered motion of the molecules of a system. It is total energy of all its atoms/molecules. + For ideal monoatomic gas, the internal energy is just the translation kinetic energy. of the atoms having a linear motion. + For poly atomic gas, we consider the rotational and vibrational kinetic energy in additional to their translational kinetic energy. + This internal energy of a by U. stem is denoted Thermodynamic system and Thermodynamic. Process Surrounding (Environment) Boundary A system, its boundary and environment A thermodynamic system is a collection on a group of objects that can form a unit which may have ability to exchange energy with its surroundings.MHT-CET « PHYSICS =o + Anything that is not a part of the system is its surrounding or its environment. + For example, water kept in a vessel is a system, the vessel is its surroundings. Above diagram shows this schematically. + An open system : If a system that freely allows exchange of energy and matter with its environment. + Aclosed system, does not allow the exchange of matter but allows a energy to be trans- ferred. + An isolated system is completely sealed (isolated from its environment). Matter as well as heat can not be exchanged with its environment, + Thermodynamic state of a system can be expressed in term of pressure (P), volume (V) and temperature (7). + A thermodynamic process : It is process in which the thermodynamic state of a system is changed. We can describe the state of a system by using pressure, volume and temperature as its variables. Heat (Q) Is the energy that is transferred (between the system and its environment) due toa temperature difference that exists between the two. When the heat energy is transferred to a system from its environment, it is positive. The system gains or absorbs energy. When the energy is transferred from the system to its surrounding, it is negative. The system loses (or release) energy. + The internal energy (U) of a system can be changed in two different ways, (i) By heating it. (ii) By doing work on it. + The first law of thermodynamics gives the mathematical relation between heat and work, Q=au+W a AU=Q-W Therefore, change in the internal energy (AU) of a system is the difference between the heat supplied to the system and the work done by the system on its surroundings. Thermodynaiey. 4 : w= Jy pav= pv ~ vp Pressure, volume, temperature, densit of a system are some of the vara that are used to describe a system, These measurable properties and are called st roscopic variables of a system, aed ma Intensive variable do not depend on t a of the system. © size Example : Pressure, temperature, density Extensive variable depend on the size ofthe system Example : Total mass (M), internal energy (W). A system is in thermodynamic equilibrium ig the following three conditions of equilibrium are satisfied simultaneously, these are 1. Mechanical equilibrium. 2. Chemical equilibrium. 3. Thermal equilibrium. 1. Mechanical equilibrium: When there are no unbalanced force within the system and between the system and its surrounding, the system is said to be in mechanical equilibrium. 2. Chemical equilibrium : A system is said to be in chemical equilibrium when these are no chemical reaction going on with in the system. 3. Thermal equilibrium : When the temperature of a system is uniform throughout and does not change with time, the system is said to be in thermal equilibrium. ‘The mathematical relation between the state variable is called the equation of state For ideal gas, the equation of state its pV = nRT where, n = number of mole of a 628, R = universal gas constant. tion of equation of ) is called the P- of the syste™ sents tho work ‘The graphical representat state of a system (of a gas) diagram or indicator diagram Area under the p-Veurve repre: done in this process.BVP.) vy ve ‘Atypical p-V diagram mamic process is a procedure by ‘thermodynamic process is @ p a the initial state of @ system changes Reversible Thermodynamic Process + Some process such as melting of ice, freezing of water, boiling of water, condensation of steam can be reversed, that means the initial state of the system can he restored. A reversible process is a charge that can be retraced in reverse (opposite) direction, An irreversible process is a change that can not be retraced in reverse direction. There is @ permanent loss of energy from the system due to friction or other dissipative forces. Limitations of the First Law of Thermodynamics 1. It does not tell us whether any particular rite nal tte. I passe throug # serie process can actually occur. The first law does f intermediate state. This series of not predict practical observation, 7 tate, when plotted on a p-V jntermediate state, 2. According to the first law, we could convert diagram ded apathy de not only on all (100%) of the heat available to us in to —_ nly 4 Work done by a system depends not 0 work. Similarly, all the work could be the linked and the final states, but also on, converted into heat practically this is not the intermediate states, i.e., on the paths ea along which the change takes place. + Heat transferred to a system also depends on the path, Se Description AW 1 | Isothermal Temperature A process remain same. MRT log, + + pV= constant P . A B Ieobaric Pressure remain | nR(@dT)=p(V;-v) | %b¢———+ Process constant, | i Lit ay Y Y Isochoric Volume remain Zero Process constant 2 AVEO LMHT-CET + PHYSICS Adiabatic Q= constant process = AQ=0 5. Cyclic Reverseible path ‘Area under the process p-V diagram 6. Free Uncontrolled change Zero expansion | @=0, W=0,AV=0 . ‘The Second Law of Thermodynamics State- ments (A) Kelvin Planck statement It is impossible to extract an amount of heat Qy from a hot reservoir and use it all to do work W. Some amount of heat Qc must be exhausted to a cold reservoir. This prohibits the possibility of a perfect heat engine. (B) Clausius statement “Itis not possible for heat to flow from a colder body to a warmer body without any work having been done to accomplish this flow”. Heat Engines + Practical machines that converts some heat into useful work. + Heat engines are devices that transform heat partly into work or mechanical energy. + Heat engines work by using cyclic processes and involve thermodynamic changes. Example : Automobile engine, steam engine, Every heat engine basically consists of three elements. (i) Hot reservoir called source. (ii) Cold reservoir called sink. (ii) A working substance called system, ‘Any heat engine works in following three basie steps. (i) The working substance absorbs heat (Qy) from a hot reservoir at higher tempera- ture (Ty). (ii) Part of the heat absorbed by the working substance is converts into work (W’). Gi) The remaining heat is transformed to a cold reservoir (Qc) at lower temperature (To). Efficiency of a Heat Engine Heat absorbed ae Qu n= Mu= 8 Efficiency of a heat engi t engine is th. . the heat absorbed that is converte of p-V diagram is a vi muapenes represents the