A SUMMARY OF THERMODYNAMIC FUNDAMENTALS

Thermodynamics - the science that is concerned with energy, particularly energy in !ransi!" in the forms of hea! and #or$, and those %ro%er!ies of sys!ems that are related to .energy Energy the ability to do work. A&& energy .is relative' Energy-in-transit is not relative :Three $inds o( energy ,potential - energy due to relative position 1) ,kinetic - energy due to relative velocity !) internal - the sum of all potential and ") kinetic energies of constituent parts #atoms, .molecules, etc.$ of a system :"T#o $inds o( energy in !ransi! heat energy transferred between system and 1) surroundings because of a temperature difference, .or gradient work - energy transferred between system and !) surroundings because of a pressure difference, or .gradient Thermodynamic Sys!em %ust &the thing' that we are talking about( Everything else is called the s)rro)ndings. )he sum of the system and the .surroundings is the universe :Three $inds o( sys!ems closed system a fi*ed +uantity of material, 1) energy can cross the system boundaries but mass .can not open system a particular region of space, !) both mass and energy may cross the system .boundaries isolated system not an important concept) ") neither energy nor mass may cross the system .boundaries -n elementary thermodynamics all systems consist only of atoms and molecules where the net electric charge of the system is .ero. -n

addition, all electrical and magnetic and surface .forces are generally neglected Thermodynamic Ma!eria&s - /ystems composed of .atoms and molecules are called ma!eria&s :T#o $inds o( ma!eria&s pure materials - composed of only one 1) molecular species, and mi*tures - composed of two or more molecular !) .species ideal mi*tures - mi*tures where the volume and enthalpy of the mi*ture are simply the sums of the volumes and enthalpies of the pure components at the temperature and pressure of the mi*ture. Elementary thermodynamics deals only with ideal mi*tures. 0dvanced thermodynamics is concerned with non-ideal mi*tures, in phase .e+uilibrium and reaction e+uilibrium +Fo)r *asic conce%!s o( ma!eria&s ,)an!i!y 1) a) mass or weight in a known gravitational) field b) number of ob%ects one gram mole 1 2.3!4) * 135!" ob%ects mean-molar-mass molecular weight or atomic weight) is the mass of one mole of a particular collection of ob%ects, and is the constant which allow conversion between these two measures of .+uantity Com%osi!ion of a mi*ture !) a) fraction - +uantity of a particular) .species per unit +uantity of the mi*ture b) concentration - +uantity of a particular) .species per unit volume of the mi*ture -hase - a homogeneous +uantity of material, ") characteri.ed throughout by a single set of .thermodynamic properties a) solids - materials which are capable of) .resisting shear stresses b) fluids - materials which e*hibit) .continuous deformation under shear stress

c) li+uids - fluids which can conform to) their containers without occupying them .completely d) gases - fluids which conform to and) .completely occupy their containers e) vapors - gases at temperatures less) .than their critical temperature +uality - ratio of +uantity of vapor to the total +uantity of material #vapor 6 li+uid$ or #vapor 6 .solid$ in a system S!a!e - defined by the %ro%er!ies of a 7) .material a) subcooled li+uid or compressed li+uid) -) a li+uid at a temperature below its saturation temperature or at a pressure above its saturation .pressure b) superheated vapor - a vapor at a) temperature above its saturation temperature or .at a pressure below its saturation pressure c) saturated - if two or more phases e*ist) within a system at e.)i&i*ri)m, the system is said to be saturated and all phases present are saturated. -n particular, if vapor and li+uid phases are both present within a system, the vapor is said to be sa!)ra!ed /a%or and the li+uid is said to be sa!)ra!ed &i.)id. /imilarly, if two li+uid phases e*ist within a system at e+uilibrium, both li+uid .phases are saturated saturation pressure or vapor pressure) - the pressure at which a phase change will take place .at a given temperature saturation temperature - the temperature at which a phase change will take place at a given .pressure critical point - that state of a saturated system where the li+uid and vapor phases become indistinguishable. )he properties of a material at its critical point are the same for both vapor .and li+uid phases e+uilibrium - the condition of a system in which no net change in the properties of the system occur with time. 0 closed system is usually .implied

steady state - no accumulations of matter or$ energy occur within the system. 0n open system #.is implied

Thermodynamic -ro%er!ies - any +uantity that depends only on the state of a material and is independent of the process by which a material .arrives at a given state 8roperties of a /ystem - the average or homogeneous properties of a system at .e+uilibrium :T#o $inds o( %ro%er!ies intensive - independent of the +uantity of 1) material #), 8, 9p and 9v$, and all specific and .molar properties e*tensive - directly proportional to the !) .#.+uantity of material #:, /, ;, <, etc 8seudointensive properties - e*tensive properties e*pressed per unit +uantity of material #v, s, u, .#.h, etc :T#o $inds o( %se)doin!ensi/e %ro%er!ies specific properties - e*pressed on a unit 1) mass basis, and molar properties - e*pressed on a unit mole !) .basis +Fi/e *asic !hermodynamic %ro%er!ies temperature #)$ thermal potential) - a 1) measure of the relative hotness or coldness of a .material pressure #8$ mechanical potential) - the !) normal perpendicular) component of force per .unit area volume #:$ mechanical displacement) - the ") .+uantity of space possessed by a material entropy #/$ thermal displacement) - the 7) .+uantity of disorder possessed by a material internal energy #;$ - the energy of a 4) material which is due to the kinetic and potential energies of its constituent parts . atoms and molecules, usually :T#o secondary !hermodynamic %ro%er!ies enthalpy #<$ - internal energy plus the 1) .pressure-volume product heat capacity #9p or 9v$ specific heat) - !) the amount of energy re+uired to increase the temperature of one unit +uantity of material by .one degree, under specific conditions

a) constant pressure 9p 1 dh=d)) b) constant volume 9v 1 du=d)) ;nlike gases, li+uids and solids are nearly incompressible, and it is almost impossible to change their temperature while holding their volumes constant. )he specific heats of li+uids and solids almost always imply their constant pressure heat capacity usually on a unit mass basis), so that, in general, for li+uids and .solids we used 9p 0i**s -hase R)&e: F 1 2 3 Ns N% F - degrees of freedom of the system 1 the number ,of independent intensive thermodynamic variables properties or compositions) which must be specified to fi* the intensive state ,of the system Ns - number of molecular species within the system, and .N% - the number of phases within the system )he thermodynamic variables specified as degrees of freedom are normally temperature, pressure and compositions mole fractions) of the phases. >ote that only #>s - 1$ compositions of each phase are independent. )o fi* the extensive state of the system, an additional extensive variable must be specified . i.e. total moles of the system

Thermodynamic -rocesses and Cyc&es .process - any succession of events chemical process - a chemical or physical operation, or series of operations, which .transforms raw materials into products thermodynamic process - the path of succession of states through which the system passes in moving .from an initial state to a final state polytropic process - a thermodynamic process for which #8:n$ is constant. )hese processes are usually associated only to systems for which the .ideal gas assumption holds :Fo)r s%ecia& %o&y!ro%ic %rocesses isobaric - - - - - - - constant 1) #pressure #n 1 3 isothermal - - - - - - constant !) #temperature#n 1 1 isentropic - - - - - - constant ") # entropy #n 1 gamma, 9p=9v isochoric isometric) - constant 7) #volume #n 1 infinity :T#o o!her im%or!an! %rocesses .adiabatic - no heat transfer 1) isenthalpic - constant enthalpy. )his is the !) .same as isothermal for an ideal gas system reversible process an idealized process in which the deviation from thermodynamic e+uilibrium is infinitesimal at any particular instant during the process. 0ll of the states through which a system passes during a reversible process may be considered to be e+uilibrium states. )his is an idealizedsituation that would re+uire infinite time and=or e+uipment si.e to be reali.ed. )he concept of a reversible process serves to set a ma*imum for the efficiency of a given process. >ote that an isentropic process is an adiabaticreversible process, so that .real isentropic processes are not possible thermodynamic cycle - a process for which the .final and initial states are the same :Fo)r common idealized" !hermodynamic cyc&es

9arnot cycle

- isothermal and isentropic 1) compressions followed by isothermal and isentropic .e*pansions ?ankine cycle - isobaric and isentropic !) compressions followed by isobaric and isentropic .e*pansions @tto cycle - isentropic and ") isochoric compressions followed by isentropic and .isochoric e*pansions Aiesel cycle - isentropic compression 7) ,followed by isobaric isentropic and isochoric e*pansions

Thermodynamic Da!a -resen!a!ion Aata, such as properties of pure materials, is generally ac+uired by e*perimentation and can be :presented in three fundamentally different forms #Ta*&es #i.e. the steam tables 1) #0ra%hs #i.e. a )-s or 8-h diagrams !) #E.)a!ions #i.e. the ideal gas e+uation ") Each of these forms of presentation has .advantages and disadvantages )ables are precise but discontinuous, so that 1) interpolation is often re+uired. -n addition, they can be bulky and can be difficult to use when implicit variables are specified. )hey also can re+uire large amounts of data storage when .used with computer programs Braphs are continuous in their e*plicit !) variables but suffer loss of precision when they are of convenient si.e. -n addition, they are discontinuous for implicit variables, so that imprecise visual interpolation is often re+uired. )hey also suffer in readability as the number of implicit variables displayed increases above three or four. 0lthough they can give an e*cellent overall CfeelC for the data, they are .virtually useless for computer purposes E+uations are in many ways the best form of ") presentation for data. )hey allow mathematical manipulation, are easy to use with computer programs, and are as precise as the data used to generate their constants. <owever, e+uations that accurately represent significantly large ranges of data can be very comple* and usually employ a number of constant terms. 9omple* e+uations are usually difficult to solve for their implicit variables and often re+uire trial and error procedures in their use. )hey are most .suited for use in computer programs

Thermodynamic La#s 0 physical law is a simple statement of an observable physical phenomenon that has no underlying, more-basic reason for being e*cept that the most accurate observations have always .proved it to be true La#s o( Thermodynamics 4ero!h: )wo bodies in thermal e+uilibrium with a third body are in thermal e+uilibrium with each other. )his DEawD simply states that .GFthermometers work Firs!: 0 /imple /tatement: <eat and work are both forms of energy in transit, and energy is always conserved. or 0 9lassical /tatement: Auring any cyclic process on a closed system the cyclic integral of heat is always e+ual to the cyclic integral of .work Second: /imple /tatement H1: /pontaneous flu*es always take place down their corresponding potential gradients. or /imple /tatement H!: <eat and work are both forms of energy in transit, but they are not +ualitatively e+ual forms of energy because work can always be converted entirely into heat, but heat can never be converted entirely into work. or Ielvin-8lank /tatement: -t is impossible to construct a device which operates in a cycle and produces no effect other than the raising of a weight and the e*change of heat with a single reservoir. or 9lausius /tatement: -t is impossible to construct a device which operates in a cycle and produces no effect other than the transfer of .heat from a cooler body to a hotter body 0lbert Einstein considered the /econd Eaw of .)hermodynamics to be the on&y real physical law Third: )he absolute entropy of a pure, crystalline material at a temperature of absolute .ero is .ero. )his DEawD is the second half of .the definition of entropy O!her La#s o( Im%or!ance in Thermodynamics

9onservation of Jatter: Jatter can be neither created nor destroyed but only changed from one form to another. >ote that 0lbert Einstein showed that matter could be FdestroyedG by .converting it into energy KouleLs DEawD: )he internal energy of an ideal .gas is a function of temperature only 0vagadroLs DEawD: E+ual volumes of different ideal gases at the same temperature and pressure .contain the same number of molecules