Pa aod DEFINITION OF THERMODYNAMICS Thermodynamics may he defined as follows: ‘Themodysamis is an axiomatic science which deals with the relations among, heat, work and properties of system which are in eguiibrim. It Aescrbes sate and changes in sate of physical systems. or Thermodynamics isthe science ofthe regularities governing processes of energy conversion, Or Thermodynamics isthe science that deals with the intersection between energy and. material systems ‘Thermodynamics, basically entils four laws or axioms known as Zeroh, Fist, Second and Thit law of thermodynamics 1. The Fist law throws light on concept of internal enerey: 2. The. Zeroth law deals with ermal esulibrum and establishes a concept of ‘The Second law indicates the limit of converting heat into work and introduces the principle of increase the trop. 4. The Third aw defines the absolute zero of entropy. These laws are based on experimental observations and have no mathematical proof Like, all physical laws, these laws are based on Iogieal reasoning ‘THERMODYNAMIC SYSTEMS (Gystem, Boundary and Surroundings) System, A system is finite quantity of matter or prescribed region of space Boundary. The actual or hypothetical envelope enclosing. the system is the boundary of the system. The boundary may be fixed or it may move, a8 and when a system containing a gas i ‘compressed or expanded. The boundary miy be real or imaginary It isnot dfiul to envisage a real boundary but an example of imaginary boundary would be one dravn around a system consisting of the fresh mixture about to enter the cylinder of an LC. engine together with the ) remnants of the alter the | exhaust process | During the analysis of the systems all the mass and energy exchanges with the surrounding are «evaluated at he boundary ‘Based on the mass and energy trans | ‘and surrounding, the systert can be further classified as 1. Closed system 2. Isolated sytem 3. Opensystom 1, Closed syste A system without mass transfer across. its boundaries is called a closed system. Such systems have ony the energy transfer inthe form of heat and work wih its surroundings aeross the system boundary, For example, consider a _piston-ylinder arrangement of an engine s shown in Fig It can be noted thatthe boundary ofthe system moves in this system with the movement of the piston sand transfer of energy like heat and work takes place a its boundary2 Teolated system: 1 there is no mass and energy transfer between the system and its surroundings, a system is said to be an isolated system. Therefor, by definition the universe isan isolated system Other examples of an isolated system ace the perfectly insulated containers like thermos sk 3. Opensystem: = colt, MACROSCOPIC AND MICROSCOPIC POINTS OF VIEW ‘Thermodynamic studies ae undertaken by the following two different appeoaches: 1. Macroscopic approach — (Macro mean big or total) 2._ Microscopie approach — (Micro means small) ‘Simo, | Macroscopic Microscopic approach approsch Tin this approach a The approach | certain quantity of | considers that the satter is| system is made considered without | up of very large faking into account| numberof the ‘events | discrete particles occuring at known as ‘molecular love In| molocules. These other words this | molooules have spproach to) different tGermodynemies is | velocities and concemed with | energies. The gross or overall | values of these behavior. This is| energies are Known a classical | constantly thermodynamics. | changing with time. This approach ‘thermodynamics ‘which is concerned edly with the truce of the rater is known statistical thermodynamics The analysis of | The behavior of macroscopic | tho system is system requres| found by using simple statistical mathematical | methods a¢. the formulae. umher of ‘moleculesis very larg. So advanced Statistical and ‘mathematical rethods are needed 10 explain the changes in the The values of the | The properties properties. of the | ike velocity, system are their] momentum, average values. For| impulses, kinetic texampl, considera | eneray, Forse of sample of gasina| impact et. closed container. | which desetibe “The pressure ofthe | the molecules ais is the average | cannot be es vale of the pressure exerted by millions of individual, molecules. Similarly the temperature of this wi he avenge translational kinetic ‘energies of millions of individual molecules. These properties ike pressure and Temperature ean be measured very ccasly. The changes in properties can be felt by our senses. measured by instruments. Our senses cannot feel them, Tn onder to deseribe system only afew Targe namber of variables are needed iGproperies are |descibe a needed. system, So the approach is complicated. Note: Although the macroseapie approach seems to be diferent from microscopic one, there exists relation between them, Henee when both the methods ar sive thes plied to particular syste, they esl. PURE-SUB ‘A pure substance is one that has a homogenous ‘and invariable chemical composition ever: though there isa change of phase. In other words, itis a system which is (a) homogeneous composition, (6) homogeneous in chemical aggregation Examples: Liguid, water, mixture of liquid water and stam, mikture of ee and water. Tae mixture of liquid it and gaseous air is not a pure substance THERMODYNAMIC EQUILIBRIUM, A system isin thermodynamic equilibrium if the temperature and pressure at all pints as same: there should be no velocity gradient; the chemical ccquilibrium is also necessary. System under femperature and pressure equilibrium but not ‘under chemical equilibrium are sometime said to be in metastable equilibrium conditions. is only under thermodynamic equilibrium condition that the properties ofa system ean be fixed ‘Thus for attaining a state of thermodynamic equilibrium the following three (pes of ulibrium states must be achieved: STATE AND PROPERTY: ‘Any thermodynamic system can be identified at ‘any time by cerain observable measurable characteristics Tike pressure, volume, temperature, mass, density, iis physical composition ete Te identification ofthe system by observable or measurable characteristics is called the state of the system, These thermodynamic co-onlnates representing a system are called property of the system, Important aspeets ofthe thermodynamie property 1. It helps to distinguish one system fom, another 2. represents unique value when the system fs aa paricolar state 3. Ttis independent of the path followed by the system inorder to attain required state, 4. Wis an exact diferenial eg. if T is the thermodynamics. property with dT representing differential change, then the integration of aT between initial stats 1 and final state 2 ofthe system will have the value sven bythe equation. jaren-1 Classification of Properties Properties may be classified in two categories as fallow: 1 Intensive property: “The properties which are independent of the mass ‘of the system ae called properties e.g pressure, temperature, viscosity, ete. For example, considera room where the pressure isp. If the room is divided into numberof pars, still we find thatthe pressure at any point is same snd it is equal t exginal pressure p though the ‘mass in each part has changed [shows tat the intensive property as a definite value and it is independent mass, therefore, it represents the point finetion, 2. Extensive property: The property ofthe system which depends upon the size and mass of the system is called an ‘extensive propery, eg length, volume, all forms “of energies and entopy, Te should be noted thatthe ratio of to extensive properties of the homogeneous (ingle phase) system represents the specific extensive property. For example, mass per unit volume, called density, represents asprific extensive propery. Therefore the ratio of an extensive property to sass i called the specific value ofthat property. Hence, all specific. properties are intensive propertiesjs "Note: In this book, the extensve propery will be represented by capital letters and their specifi values will be represented by small letes, 3. Check fora thermodynamie property: A given function aZ = Mx + Ndy would be a thermodynamic propery iis differential is ex eit Example: Discuss whether (p dV + V dp) represent the system properties 0 not Solution: Basically we are required to determine whether the given differeail i an exact differential or A differential is considered to be exact if the integeation between two end states can be cami cout without requiring any information on the variation of variables, Inthe above problem, p-dV+Vdp=dip-V)=p-V Since the integration of pV is oblained without requiring any information as to how p ai V are related, it represents an exact differential, henes the given difereatial represents a propery. Example Discuss whether the following quantities represent the property ofthe system or not @ pay © Veep Solution: @ pa Since the integration of | p - €V can only be determined if the relationship. between the variation of p with respeet 19 Vis known, therefore (p - dV) is not an exact differential, Doence itis not the propery of the system. PROCESS A process occurs when the system undergoes a change ina state or an energy transfer ata steady stale process may be non-flow in which a fixed mass within the defined boundary is undergcing ‘change of state. Example: A substance whichis being heated in a closed eylinder undergoes = nomflow process (Fig._). Closed systems undergo nen-flow process. A process may be & ‘How process in which mass is entering and Jeaving though the Boundary of an open system, Ins steady flow proces (Fig.) mass is erssing the boundary ftom surroundings a entry, and an sual mass is crossing the boundary at th exit 0 ‘hat the foal mass ofthe system remains constant, Iman open system iti necessary to tae account of the work delivered from the surroundings to the system at enry to cause the mass to enter, and also of the work delivered from the system at surroundings to cause the mass to leave, a5 well 5 any heat or work erasing the boundary of the cveLe [Any process or series of processes wihose end states are identical ig tenmed a cycle, The processes through which the system bas passed can be shown on a sate diagram, but a complete section of the path requires in addition a statement of the eat and. work crossing the boundary of the system. Fig. shows such a yee in which asystem commencing st condition 1" changes in pressure and volume through a path 123 snd returns to its iil contin “1 POINT FUNCTION When two properties locate a point on the graph (Co-ordinate axes) then properties are called as point funtion, Examples. Pressure, temperature, volume ete jar-r, , (an exact differentia, PATH FUNCTION There are certuin quantities which cannot be located ona graph by apoint but are given bythe‘twa oF 80, on that graph. In that ease, the area on the graph, pectalning tothe particular proces, i 1 function of the path of the process. Such «quantities are called path functions. Examples. Heat, work et. Heat and work are inexaet ferent change cannot be written as difference hetwe their end states. ‘QUASI-STATIC PROCESS: A. quasi-static process is defined as a process in which the properties of the system depart infinitesimally (extremely small) from the ‘hermodynamie equilibrium path IE the properties of the system have finite | departures trom thermodynamic equilivium path the proces is sad tbe non-quassttic. ‘To understand the above concept let us consider a fitionlesspiston-cylinder arrangement having fs at state I defined by (pi, Vis T»). The system, {sin thermodynamic equlitsium due to external ‘weight W as shown in fig, and itis isolated If the weight is removed, there would be large (nite) unbalanced pressure forces between the system and surroundings. Duet this the gas will suddenly expand and the piston will move up til ithits the stop provided in the eylinder The system will each to new equilibrium state-2 defined by (pr, Var Ta). However, the intermediate states of the system cannot be defined. since it has passed through non qulibrum states. Th proces is said to be nom ‘quasistatic or iereversible and itis represented by the dotted curve fig,_in which state-1 and sate 2 represent only the intial and final stats. "Now, consider the above ease in Which the weight Wismade up of infinitesimal amount of weighs Tle made up of very large number of small ‘Weights dW each so that EdW = W., If weight dW is removed in succession gradually from the top of piston, dhe ga will expand slowly snd it would pass through large number of ‘thermodynamic equilibrium stats tl the system again reaches tosate-2, Such pot isepeesented infg We find inthis case that the departure of each state of the system from thermodynamic ‘silibrum stat is infinitesimally small andthe Jocus of sich thermodynamic equilibrium states is represented by process path by slid ins. Such a process is said to be quasistatic or reversible proces ‘Therefore, we conclude that a quasistatic process is the succession of thermodynamic equilibrium states while in ease of non-quasstate process the fend slates only represent the thermodynamic equilibrium states Although in practice most ofthe process are non quasitatic, however, the concept of quasistatic process. is very useful for the analysis of thermodynamic problems. Many processes are sharacerized by the fact that either some of the wperties ofthe system remain constant or itis Characterized by the nature of energy transfer cross its boundaries Conditions for reversible process are: 1. There is no fietion, 2. Heat transfer is though infinitely Temperature difference. There ate 0 spontaneous changes in the system. 3. All processes in nature are ineversible ‘eg, expansion or compression of gas with fluid section in engines, turbines, ‘compressors ete, flow through rsticted vale, steching of wire magnetic effets‘THE THERMOMETER = AND ‘THERMOMETRIC PROPERTY Introduction ‘The zeroth law of thermodynamics provides the basis for measurement of temperate, It enables sto compare temperatures of two bodies "I and “2 withthe help ofa thitd body °° and say that, the temperature of “I" is the same as. the temperature 2” without aetually bringing 1" are “2 imthermal contact. In practice, hody “3 in the zeroth law is called the thermometer. Is brought ito thermal equilibrium with set of standard temperature ofa body 2", and is ths calibrate. Later, when any other Body <1" is brought in thermal communication with the thermometes, we say thatthe body “I” has attained equality of temperature with the thermometer, and ence with body “2. This way, the body “1” has the temperature of body °2" given for exampleby, say the height of mercury column in the thermometer a “The height of mercury column ina thermometer, therefore, becomes thermometie property. ‘There are other methods of tempersture measurement uilize various other properties of materials, that are functions of temperature, as thermometrie properties, Six different kinds of themometers, and the hnames of the corresponding thermometic ‘properties employed are given below: | ‘Themmometer | Thamometie Proper T, Constant volumes | Pressure (p) 2. Constant presare | Volume V) gas 5. Aleohol oF Teng) mereury-inlass 4, Fletricresswice | Resistance (R) 3. Thermocouple | Elecromotive forse we © Radiation tensiy OF ation pyrometer) Gerd) ENERGY, WORK AND HEAT fa general term embracing energy in transition and stored energy, The stored energy of ‘substance may be in the forms of mechanical energy and intemal energy (other forms of stored energy may be ehemical energy and electrical energy). Part of the stored energy may take the fom of ter ten ery (ih is he energy due to eight above a chosen Gatun ino ints nergy dt veo. The balance part ofthe energy is known as internal ‘energy. Ina noa-flow process usualy there is no change of potential or kietic energy and hence cchange of mechanical energy will not enter the caleulatoas. In flow process, however, there ‘may be changes in both potential and kinetic enecgy and these must be taken into account while considering the changes of stored energy. Heat and work are the forms of exergy in transition, These are the only foes in which ‘energy can cross the boundaries of a system. "Neither heat nor work can exist as stored energy. Work ‘Work is said wo be done when a force moves throug «distance. Ifa part ofthe boundary of @ system undergoes & displacement under the setion of a pressure, the work dane W is the product of the force (pressure * area), and the fistance it moves in the direction ofthe force. Fig. illuseates this with the conventional piston and cylinder arrangement, the heavy line efining the boundary of the system. Fig. ilustrates another way in which work might Be applied to system. force is exerted by the puddle as it changes the momentum ofthe Nuid, and since this force moves during rotation ofthe dle work is done. Work is a transient quantity which only appears ‘atthe boundary while change of state i aking in system, Work is ‘something’ sal the boundary when a sysem‘thangs its state die othe movement of apart of the boundary under the action of fore, Siga convention ‘© the work is dane by the system on the surroundings, e.g. when a fluid expands pushing « piston outwards, the work is sald tobe positive. i.e, Work output ofthe system = +W ‘+I the work is dane onthe system by the surroundings, eg, when force isapplied to 4 rotating handle, or 0 & piston to compress Muid, the work is said tbe negative ie, Work input to system = -W Heat Heat (denoted by the symbol Q), may be, defined in an analogous way to work as follows: “Heat is ‘something’ which appears at the ‘boundary when a system changes its sate due 19 a difference in temperature between the system and its suroundings” Heat, lke work, ia tfansent quantity which only ‘appears tthe boundary while @ change i aking place within the system Te is appacent that either BW or AQ are exact differentials and therefore any integration of the Clement quantities of work of heat whick appear ‘during a change from state | to state 2 must be ‘writen as jor- or Wh(or W), and J90=0., 0 0,(0r0) Sign convection: Hf the heat flows into a system fom the surroundings, the quantity is sad 10 be positive and, conversely, iP hea! flows from the system to the surroundings itis said to be negative nother word ‘Heat received bythe system = +Q + Heat rjected or given up by the eystem = Q REVERSIBLE WORK Let us consider an ideal fiietionless uid contained in aeylinder above a piston as shovm in fig. Assume that the pressure and emperatce ofthe Md ae uniform ad that thee {so ition between the piston and the cylinder walls Let A= Cross-sectional area ofthe piston P= Pressure ofthe Muid at any instant, ( ~ ep) A= Resting force exerted by the surroundings of te piston, and = the distance moved by the piston under the section ofthe force exerted, Ten work doneby the Mui onthe pistons given by force times the distance moved. ie, Work done bythe fvid pa) xdl= pa (where dV ~ a smal increase in volume) (Or considering unit mass Werk done = pv (shore v= specie volume) This is only true wien (a) the process is frictionless and (b) the difference in pressure between the uid and its. surroundings daring. the process is infinitely’ small. Hence when the reversible process takes place between state | and stte 2, wwe have Work done by th nit mase of Bud f a ‘When a did undergoes a reversible process series of state points can be joined up to form a Tine on a diagram of properies. The work done by the Muid duting any reversible process is therefore given by the area under the line of process plotted on ap- diagram (fig. ite, Work done = Shaded aren on ig =r When p can be expressed in terms of v then the integra, =f pa canbe ved ZaROTH LAY OF THERMODYNAMICS two bodies and 8 are individually in thermal ‘uilibeium witha tied body C, these ewo bodies, ‘A and B will also be in thermal equiibeium with each other ‘Above statement is known as zeroth law of thermodynamics‘This Statement is represented schematically in Wa © ‘Since body Aisin thermal equilibrium with body therefore, they are at equality of temperature T cach, Similarly, the body B being in thermal equilibrium with body C, the temperature of ody wil also be T 1h follows that body A and B are both at temperature T, hence they are also in thecmal cquilbsium, Te science of measurement of temperature is called thermometer. tis based on the concept of zeroth law of theemodyeamics. It can be explained as follows The body ‘C° can be wsed as a thermometer to measure the temperature of the bodies, ‘Altemately, if body “C’ is used to measure the temperature of body A and Bit wll only show the ‘equality of temperature, of in other words the thermometer "C” indicates it own trmporature ‘which s bing in thermal equilibrium with bogies And B. However, the problem remains to relate the temperatures which might be read on diferent thermometers or on the other measuring devices a diseussed below: (@)Real gas: The behavior of ll gases at high pressures and at lows temperatures is different. All hese gases are called real gases eg air, oxygen, hydrogen ete () Ideal or perfect The experimental results have shown that all eat ases tend wo behave similarly at very low pressures (asthe pressive approaches to zero) and thigh temperatures where the volume "approaches t infinity Ie follows tht the behavior of ll eases would be ideal atthe state of zero pressure and volume approaches to infinity. Sueh state ofthe gasses iscalled ideal state Therefore, the behavior of ral gases atthe ideal state is called ideal or perfect gas. Henee, we define an ideal gus “which would ‘have in an ideal manser at all pressures and temperatures, Sch a gas wil follow al gs laws and characteristic was equation”. deal Gas Laws: Behavior of ideal gases based on experimental results are governed by following laws known a ideal gas las: 1. Boye's law 2 Chark's law 3. Gay — Lassa law 4. Meal or characteristic gas equation 5. Avogadro's law Boyle's Lav: This law was Formulated by Robert Boyle Statement: Boyle's law states tht the absolute pressure of iven mass of an ideal gas. is. inversely proportional to its volume, ithe temperature of the gas is kept constant. 1 i. par} i T= constant) of pV =C (constant) Consider a gas at point 1 at pus which undergoes a change of state 2 at pV while temperature Is Kept constant. Such & process is shown in fig. It is knows as Isothermal proces. ‘According to Boyle's la prVi= pa: Ve= Constant ‘The curve on (p ~ V) dingram represents relangular hyperbola. For this reasons, an isothermal process is also called as hyperbolic process ineate of gases onlyis posible to change the state 1 to state 2 by infinite numberof paths lke a, b ore. However, for given mass *n ofthe gas, the state? can be This law was formulated by Jacques A.C achieved Charles, follows sm state 1 by following the paths as Statement: 1 states thatthe volume of a given mass of an ideal gas is directly proportional to its absolute temperature if the pressite of the gas is kept (@) Known path state 1 to state “dat constant volume. It follows Gay Tsste lave | | Charle's Law: | | | Poe (b) Followed by path from state “A 10 ie Var (p= Constant) state 2 at constant presse It follows ee ony Charie's law. For pu (l~ @), r solving Gay Lassacs Equation Betwecn ay two sates 1 and2, | wehwe Constant (if p= constant) Gay Lussae Law Fer tty Gy Laas torpah(42 epg Che's Bg Suumtiecoae peas eteghenms | RNa seer Coe) " Pacem panen 3 Zh r Or, Between any two states Land 2, D x, «tn 2. constant (if p= constant maa h Bing ioe ad wee, aur {Weal Gas Equation or Equation of State: n= Foran ideal gas, the equation or state represents her the relationship between pressure, volume and | Or, ak temperature. i On, it follows that for any fixed mass of gas (mn), Consider 9 gas whose original sate is at pr, Vi, | the change of state Ty represented by state 10n (p ~ V) diagrams as | shown in fig. and lt is final properties be ps, P¥ _ coosnt | Va, Te represented by state 2 ssLet, v= specific volume of gas Le. volume for 1 kgof xs implies, V=m-y Equation for nit mass of gas can be writen P* _ R(Constant) P= R{ Const) where, R ical chanetersi as consti since, »=/ from Eqution _ and abetting the value of vin Equation_, we get, or pV mT Equation is known as characteristic: gas ceqution fran ideal gas Units in Gas Equation: Letpin %-V inn, minkg, Tin K. From equation __ weave, (5) v(m?) =m(hg)-®-(K) J s 2m oy UnisotRin Bor ek Remember, R for ais, R297 eK or, R represents the magnitude of work that can be done by 1 ky of yas when subjected to I degree ‘change in temperature, Avogadro's Law ‘Statement: ‘Avogacto's law states that equal volume of different ideal gases at the same pressure and temperature contain the same number of molecules Since the molecular weight (M) refers fo relative ‘mass of individual molecules, it follows that the different ideal gnses atthe same pressure and temperature having. equal volumes contain the same number of moleules, Thetefare, ‘Number of moles (2) Total mass ( ‘Molecular weight (34) =a-M ese ccc Universal Gas Constant: Substituting the value of m from equation in ‘gas equation _, we Bet, peV=n-MRT | pea ‘where, Molar volume, (total volume) ~ Grumber of moles) pevieMR-T According to Avogadro's law equal volumes have the same momber molecules at equal pressure ad temperature, it implies that: Mf sconstnt (8°) pe T ° js called universal gas constant. It is equal to product of molecular weight, M and characteristic ns constant Since, pV =mRT piven MRT brp.V= aR") ond, m=n-M ¥ MR where, =v" and RE Value of R° as determined by experimental results is given as ee =s3143_Nm since, R= therefore, the value of wf characteristic gas constant canbe determined any ‘gs with the help ofthis equation. Heat: Heat isthe form of energy which is transfered without tansfer of mass, from one body to smother body (or botwoon system and surroundings) from higher temperature to lower temperature by virtue of temperature diference between two bodies. tis generally abbreviated as ‘Heat i the energy in transition because it exists only when the temperature difference exists between the system and its surroundings and ‘when it ersses the bournares ofthe sytem, The teansfer of heat energy from or to the system changes its slate, Th uni ot heat energy is kl‘Also, the taser of Heat into feequently referred as heat dition and the | transfer of heat from the systom as heat rejection ISX It should he noted that heat is never contained in ‘body. In practice, we usually refer to sensible and latent form of intemal energy as eat or heat content ofthe body. ‘Thenmodynamiclly, we refer these quantities or ‘energies as thermal energy of the system, while the heat i¢ tansfer of thermal energy due 10 terperature difference which changes the sate of the system, ‘Amount of heat transfer between the system and surroundings betwen the sates I to 2is denoted Qe-2 0rsQeorjustQ It represents an extensive property. Magnitude of heat transfer depends onthe path it follows between the given end states and not on For example, refering to fig, the amount of Ioeat iransfer for paths, bande wil be different. Therefore, heat is said tobe a path function. Tis sn inexact diferent Sometimes it is desirable to know the rate of heat, transfer instead of total heat transfer over given time interval {A process in which no heat erosses the boundary ‘ofthe system scaled an adiabatic proces, ‘A wall which is impermeable othe flow of heat isanadiabatie wal, whereas a well which permits the flow of heat is called diathermicordindiabatic wall Fy Lorsimply @. Important note + [40Q=0,-Q, being ma inexact differential Notation dor 8 of are we hy various authors to represent that d°Q ig an ine dient Rate, | Heat transfer rate It is defined asthe amount of heat transfered per unit time. It is denoted as Q. Its units are Kis or kW. Therefore, 9-foa(u) ‘Also, eat transir unit mss qs even a a-2(uyie) Sign convention: Heat transfer tothe system fiom surroundings is considered positive and heat transfe from the system to suroundings as negative Work Analogous to heat, work is also a transient form of energy which is observed when it crosses the houndaries of the system without transfer of Definition of work from mechanics: Inmechanies if force "F causes displacement, "aS" in the direction of force, i is said to have ne the work equal to (F.48). If the object moves fom point 1 to 2, the total work done is jew-fr-as External and Internal wo Work may be an exter wore oF an intra work In ower to diferente teen thes wo typ af works et us considera system whose soe effect exten the stem st exert a force 08 the sunoundings. This wok sclled sn exter work Tnmother case the work may be done by the force of ene part of the system (intemal fore) on to mother part ofthe same system, it ssa that it has done a internal work| Tn macroscopic study, we ate only concerned With extemal work, therefore, in the further text the “work”, unless or otherwise indicated, will mean the exteral work. ‘Thermodynamic definition of work: In thermodynamics, the concept of work is necessarily associated with a process which ean be indicated and specified with the sate of the system defined by its properties Since the external force on a system ean do the work only when it causes the displacement the boundaries ofthe system, the definition of work five from the concept mechanies now be related thermodyzamically as follows: ‘Work is done by ofan to the system ifthe sole effect on the things external to the sytem could be equivalent to rising or lowering a weight in the suroundings" shouldbe noted that ou definition of work does not imply that a force has sctually applied through a distance so as t0 raise or 10 lower 8 weight rather, itonly specifies that the sole effect, ofthe system could have been equivalent it Fow illustrations would be helpfal to understand {his definition of work Consider a storage batiery as a system which is ‘connected to a resistor with boundaties ‘A’ a eator gets warmer. Now the question arises, “does the work erosses the boundary of the system?” ‘According tothe definition of work as given from mechanics point of view, the answer would be 'No'. But, fom thermodynamic definition of work, the answer would be "Yes". This could be explained as follows Replace the resistor by an electrical motor, fectonless pulley and weight arrangement 3s shown in fig. _ with the same boundaries ‘The electrical energy is now supplied to the motor ‘which in tun ulizes this energy to raise a weight trough a distance °Z'. Hence, the sole effect extemal tothe system is of raising weigh Le the work has been done by the sytem extemal to it and eroses its boundaries, Further suppose we draw the boundary-B such that the new system eoasist of battery and resistor as shown in fig. and comespondingly the bratery, motor, pulley and weight arrangement shown ini, Aguin we ask, “does the work crosses the ‘boundary ofthe system”? We find with these new ‘boundaries ofthe system, all changes are taking places within the boundary of the system, therefore, in this case on work crosses the boundary of system. Wercalizethatone part of the system does a work fon fo the other part ofthe same system and we recognize this work as internal work. In other words it represents the fat that work i identified only asi rosses the boundaries ofthe system inthe form of energy, hence, the work is 4 transient phenomenon ie. the work is the ‘energy in ans, Limitations of f p-dy work: ‘Therefore the equation for work, W ~ J prdV is valid under the following conditions (System is closed (i) Process. quasistatic i reversible i)Work done for a process can only. be fectonless and connie eer | eeepath is known isknown, (Gv) The properties have a unique val during the process a all points on process pa, (©) Bfteets due to gravity, magnetism, elect etc, are neglected. (way There are no viscous effets in the system. ‘variation of pin tenn 50 FV Work isa Path Function Consider two. states I and 2 of a system represented by is properties. The slate2 could be ‘obiained from state 1 with the help of vatious ‘quasistatic processes, such as along the path or path Bas shown in fig, Similarities Between Heat and Work: Similarities between heat and work from the above discussions are summarized below: (© Bot heat and work exist i transit and these are never possessed or contained in a system, Both heat and work refer to boundary ‘Phenomena ie. both represent the transfer of ‘energy across the boundary ofthe system. (GapBott heat and work are path functions and do ‘not represent the propery of the system. Both are inexact differentials, Differences Between Hear and Wor “The differences between heat and work are: (Heat ean only be tansferred when thee is difference of temperature between the system and suroundings, while the work transfer can take place even without the change in temperature between the system and surroundings. Gi) In a constant volume process through the clisplacement work cannet take place, Dowever, hea canbe transfered (pln case of work transfer, its sole effect could ‘be raising or lowering 2 weight in the surrounding but in ease of eat transfer other efets ae also observed, ‘Specific Heats The specific heat ofa solid o lguid is usually defined asthe teat required fo raise unit mass through one-dogree temperature tse. For small quantities, we have “dO med? where m ~~ = mass © = specific het, and T= teraperatuce rise For a gas there are an infinite number ways in which heat may be added between any to temperatures, and hence gas could have an infinite numberof specific heats. However, only to specific heats for gases are defined, ‘Specific heat at constant volume, and. Specific heat at constan pressure, ep. Weave dQ ~ me, dT For a reversible non flow and dQ = mes aT For a reversible non-flow ‘Processes at constant volume ‘The value of cp and oy, for a perfect gas, are constant for anyone gas at all pressures’ and tempts, Hens, ineprainge_ ad, Flow of heat in a reversible constant pressure process cy (3-1) Flow of heat in a reversible constant volume process = me (3-1) Jn case of real gases, cp and we vary with temperature, but a suitable average value may be ‘used for most practical purpose. JJoule’s Law Toul’ law states a follows “Te Internal energy ofa perfect gas isa function ofthe absolute temperature only.” ie, w=) ‘To evaluate this function let kg ofa perfect gas be heated at constant volume. ‘According to non-flow energy’ equation, ao dW N=, sine volume remains constant dQ = du ‘At constant volume fora perfect gas, rom eqn. for kg dQ =odT dO=du= eal and integrating ‘u~ eoT + K, Kbeing constant cry‘Acconing to Joules law u = 7), which means ‘that internal energy varies linearly with absolute temperature. Intemal energy ean be made zero at any arbitrary reference temperature. For a perfect gas it can be assumed that u = 0 when T ~ 0, hence constant K is 270, ile, Internal energy, = eT fora pert gas fr Formassm, ofa perfect gas Intemal energy, U~ mes Fora perfect gu, in any process been sates 1 and2, we have from eqn, Gain in internal enerey, U;-U;=me, (12-7) qn. gives the gins of intemal eneray for 8 elect gus between two states Tor any process, ‘eversibieor ineversible Relationship between Two Specific Heats Consider perfect gas being heated at constant pressure fiom Ty to, ‘According to non-ow equation, Q= (UU) + Also fora perfest gs, UU; Q In. constant pressure process the work done by the fui, 25 (TT) me (TT) W w ‘p(V2— Vi) mR (T2-Ti) P=, Y= mk, a (on subttuing Q = me, (12-11) + mR (Ti) =m (ey +R) (Ts = TH), in this case, ‘But fora constant pressure process, Q = me (2-1) By exquatng the two expressions, we have 1 (+ RY (Tz) = my (TT) ent Roe or an o=k Dividing both sides by es, we got yl (Where y= ee) Similarly, dividing both sides by y, we get IN"? (rts |» unis the vas of is unity, Enthalpy One of the fundamental qunties which occur invariably in thermodynamic is the sum of internal enery (u) and pressure volume product (8). This sum i called Enthalpy (h), ie, hewepe ‘The enthalpy ofa Muidis the property ofthe Mid, since it consits ofthe sum ofa property and the ‘product of the 190 properties Since enthalpy isa property like internal energy, pressure, specific ‘lume and temperature, it ean be introdced ito any problema whether the process is a flow of a nor-flow process, ‘The toal enthalpy of mass, m, ofa Hid ean be H= U+ pV, where Hf = mh. Fora perfect gs, Referring equation —_ =n (4R)T mar be ero Rl ie hk "=or ad oH it (Note tha, since it has been assumed thatu= Oat T=0, then h= Ost T=0). Ratio of Specific Heats ‘The rato of specific heat at constant pressure to the sposfic heat at constant volume is given the symbol y (gamma). ie ee &Since cp “ey FR, itis clear that cp must be greater than ey for any perfet gas. Tt follows, therefore thatthe ratio, “t= y is always grate than unity, First Law of Thermodynamics Application of First Law of Thermodynamics 1s Applied t0 Closed System or Non Flow Processes Following. processes will be considered as applied to a closed system: ‘Constant volume process, V=C. ‘Constant pressure process, p= C. Constant temperature of isothermal process, Corp V= Constant, Hyperbolic process (p- V= V). Reversible adiabatic process, p-V'= C. Polytropie process,p -V"=C. The application of I law of thermodynamics is now'being discussed for the above processes with working substance as an ideal gs. Constant Volume Process (Closed System or Non-flow Process) Consider a pston-cylinder arrangement having an ideal gas of masse" at present temperate ‘and vecupies a volume Vi as shown in fig, If the gas is heated, its pressure and temperature ‘would rise and the gas will expand the to carry ‘out constant volume process itis necessary that the additonal weights ae kept piston in order to ‘equalize the increase in pressure due to heating. et the final pressure, volume ad temperature be (2.2, Since itis constant volume process, va=Vi (@) Werk done: WeIpdv Since, dV = 0; (sing a constant volume process). eee w=0 () Heat supplied d0=mc,-at (for infinitesimal proces) Q=mC(h-T) (for proces between state It (c)Application of 1" law of hemodynamics: Q=WiUn-U) (eT) =0+U2—Uy, ive, Change in internal energy, AU =m, (27) For infinitesimal process, aU =mCy a ‘on unit mass basis, du" Cyd i Specific heat, |C, In equation _, T is « propeny of the system, therefore, iniemal energy isa property and it is ‘the function of temperature lone Ie follows that: AU =m Cy dT will be applicable to any process though this expression has been defined With the help of constant volume process, Constant Pressure Process: Gass trapped in a piston eyliner erangement at state I (ps, vin T) and heat energy is supplied to the system keeping the pressure constant with the help of dead weight W as shown in ig Let the final stat 2 be represented by (po, V> 2 The process is shown on (pV) diagram ‘Since iis constant pressure process, Poconstant ip" pr" pr (@ Workdone:reese PUY) =(e.~ 2K) (since p= p= m) =me(7,-1)) (nse pV = mT) (©) Hest supplied By deinton, F0=mC,d Q «mc, far=m-c,(,-%) (©)Application of 1* Law of thermodynamics: O HW +AU =W4(U,-U,) Note: (U2—Ui) is alvays mC, (Tz 7) whatever law of process may by being the property af system, mC, (hy—T))= aR (T}~T))* mes (ToT) Equation _ is called Meyers equation Again, Q [=w+(:-Uy Q = G:Ve-pVi)+ User Q = Ur+p: V9 — (s+ piv) Q HHH. ince, =U + pv) Heat tansfered in a constant pressure process is also eal to change i called the gus, Constant Temperature or Isothermal Process: Since the gas is assumed to be an ideal gas at constant temperature it will follows the Boyle's Taw given by equation, p-V=C (aconstant) o Process is represented on (p ~ V) diagram in fig.__ when the gas undergoes an isothermal process from state I to state 2. (@ — Workdone: w four =[Sar 7] [rns But, pv=C piVi=peV2 «Ci [rom proces equation) y W = pTiog. ma Equation i), nom W =mRT tog, Pb (©) Change in intemal energy: mC (TT), Ty being constant temperature process au=0 (©) Heat transfer: From 1" law, Q= W-+ A; But AU =0, But, Te 2 Wa pile .f-av=0] Iyperbolie Process: ‘The plot of rectangular hyperbola is represented by the Equation pV» constant. Since the law ofan isothermal proces is also p-Y =C, it follows that in ease of gases the hyperbole and isothermal procesesre the same Therefore the equations derived for work, heat ‘and change in intemal energy for an isothermal process earlier are also applicable to hyperbolic processes, ‘An adiabatic process is one in which there is no heat exchange berwoon the system and its surroundings, ie dQ=0, o O=0 To prove that the law of reversible adiabatic process is p= where, ¥ =C,/C. Proof‘Consider an infinitesimal reversible adiabatic process. Appling 1” lw of thermodynamic dQ=aW +d Since it is adiabatic process, d'Q=0, dW = p-d¥ and dU =mC,-dT Substituting values of 0, dW and dU in equation __we get, 0 pa +mCrat From equation of state, pV =m R dT ar Pa Vib mk ‘Substituting the value of dT in equation _we get ped Vs 0 =p-dv smcy| PAY eb ’ UO ar 0 = pay 2(p.d¥ +¥ap) ped «(ped¥ sap) From Meyer's equation we have Cy ~ Cy = R a pal aC Gun c/R=Ylr-1) Sbstng vale of CR in equation we | 0 =p-d¥ +{Y(y-1)\[(- +¥ -dp)) yo prdl ~ ped + ped +V dp ° yep +V-dp=0 Dividing the above expression by (p-V), we get, “(VN + dplp=0 Integrating above equation we have, dV pdb Tee! ‘log, ¥ +108, p= log, C ‘where lop.C is a constant of integration. og, p-¥" =log, C Taking antilog pv=c Therefore, the reversible adiabatic process [p-¥7=C], where scaled the index of reversible process and y= CC follows the law]p-7™ (0) Work done: Refer fig w =fo-a Law of process isp 77 = (@)Application Taw of thermodynamics: Q=W+Gh-U) Since itis an adiabatic process, Q= 0 0 = Wean-U9 Wo =Ui-U = ey (1-1) [esU) Us mC, 2-7) Wo) Ui Us=mey ri) Equation __ shows thatthe work done by the system during an adiabatic process isthe expense af intemal energy i.e. during an_ expansion process the internal energy of the system decreases Polytropie Process ‘The reversible adiabatic process deserbed above ray be extended to describe » gas process in ‘which the heat transfer Between the system and surroundings takes place, ‘The process equation canbe represented a: 7‘Various processes discussed above represent ie VRC, ie pe, snd The constant volume, constant pressure, isothermal or hyperbolic (for geses only) and reversible adiabatic processes are shown in fig The value of y is approximately 1.4 for perfect lstomie gases like Nz, Ho, On, CO> ee. ‘The value of ‘x’ may be greater than or les than + for palytopic proses, The deviation even in eas of perfet gases occurs due to the internal heat generated the fretion violating the reversible adiabatic concept hence, the polytopie process is evolve. (®) —_Workdone: Replacing y by m for polytopie proces, the work cation can be written as () Change in internal energy AU=Ur-Ui=m, (T2-T) (Application of 1 law of thermodynamics: G-D=R R (r=) Substituting the value of et, = (r=) o -na 28 ome (Zr, n) Letus define Polytope specific eat Ca then the teat transfer during 2 po¥trepic process between the change of sate from | 2 is given by, Q=m-Ca(-T) Comparing equstion and _we get (2) Get Polytropie specific heat, C (© Heat transfer during plytropie process in tens of work Again fom 1 law, ° =i AEB) ne 1) 1) | «wou deo pyophis process (0-0) econ ca (0) To combo of plywole ew ane seer GeeDuring a polytropic process the ratio of temperatures can be determined in terms of pressures and volumes. ‘The index of process can be determined by combining the polyizopic la and equal sate Consider a polytropie process betwoon state-1 stato2 defined by property (pi, Vi, Ti) an (Pa Va,13) Which follows the plytropie law pV" = DM =P Also aplyng the chasse ges euton a pei = mR, PeV: = mRTs | Dividing Equation _ by Equation, we get, ») ta) f equation lal Also, from equation, J 7a) ti o ibe 7 Ye) Combining equation and Ratio of absofute temperatures | (Ratio of pressure) ®-P* = (Ratio of inverse volume) *-»