| Cy TATISTICA ECHANICS M.Sc. (Physics) Classes ¢ B.S. Physics Program MAJEED 22-Urdu Bazar,[CHAPTER O11 THERMODYNAMICS 1 THERMODYNAMICS ; The branch of physics which deals with study of heat and its inter conversion with other form is called thermodynamics. SYSTEM © The part of universe which is under observation is called system. The thermodynamic system is mainly divided into three types. 1. Open system The system is called open system when it exchanges both energy and matter with surroundings. Air at low pressure enters and air at high pressure leay is exchange of matter and energy with Surroundings. i 2. Closed systent | j The system is called closed system when it can excl matter with surroundings. Gas enclosed in a cylinder expands \ piston outwards, The boundary of the system moves but mi constant, 3 3. Isolated system The system js called isolated system when it neither with surroundings. SURROUNDINGS / The part of universe which can affect system Is called BOUNDARY The envelope which boundary can be divided into two types. h separates system from surrourSTICAL MECHANICS (MSc. 2 go start , Le 1. Diathermic boundary — rekot} THERMODYNAMICS ‘The boundary which allows exchange of heat between system and sup), souat called diathermic boundary. nj ‘ PIRES jiabatic boundary . nus 2, Adiabatie boundary tow exchange of heat betwee inst LAW OF THERMODYNAMICS ried to the system The boundary which does nett ” 8Y8Heq ‘The change in internal energy is equal to the heat SUPT or enerBY: surroundings is called adiabatic boundary ay] work done by the system, Isa special form of aw of conservation ‘THERMODYNAMIC EQUILIBRIUM : and heat ich any two of three var PLANATION sical work ‘Any state of homogencous system! ire 1S Sa ia eas By a “The Joule’s work in 1840 established a relation ‘between mechanical nae jount of remains constant as Tong as the extemal conditions Tenens Wir aed is sag! ky Se ee eect ta beat Teva form of SBE: siced related thermodynamic equa. & sytem in emouy mutate Sechnical wok W is convened into heat Q then amount of heat produ following requirements 1] mzeMiechanicl worcas 1, Mechanical equilibrium 4: . For a system to be in mechanical equilibrium thers should Be 20 my us . io See nin he yeas of toeen ie oe eee see ee 38 joue's mechanical equivatent of heat. 2, Thermal equilibrium valuels 418 Veal, Thus 418 J of mechanical work can produce OTE ae ils and sider an ic is enclosed ii o jth non-coF Consider an ideal gas Josed in a cylinder _ noncontpcorbs Q ‘amount Fara ‘yntem tobe in thermal equilibrium there should be no femperature gi between the vas ‘of the system or between the system ‘and surroundings, ite, 3. Chemical equilibrium For a system to be in chemical equi system and also no movement of any chemical the other part of the system. GREE ED THERMAL EQUILIBRIUM ae ture of i jum, when temperature of var rit tious pag | ston. Only the bottom of the cylinder is conducting. Ass! Peat from heat reservoi rium there should be no reaction yg, 1 constituent from one part ofthe sy a ny Sy ‘The heat energy Q is used to increases the internal energy AU of the system and do some work W to move the piston against its weight. - : Q= aU+w This is mathematical form of first law of thermodynamics amount of heat energy. given to the system is equal to the sum o! energy of the system and work done by the system”. ‘The differential form of first law of thermodynamics is ‘A system is said to be in thermal equilib the system is. same, Heat transfer does not take places, fom the system Surroundings and vice versa when a system isin thermal equilibrium. ZEROTH LAW OF THERMODYNAMICS a It states that if two systems are separately in thermal equilibrium witha gy system, then they are in thermal equilibrium with each other also, Consider three thermodynamics systems A, B and C having temperatures yy ‘and can be stated as “the f increase in internal “0 Ty respectively. q Thermal equilibrium of system B with systems A gives dQ = dU+aW TeQo 0 vO) @) Work is defined as ‘Thermal equilibrium of system B with systems C gives M aW= Fxex al @ aot, Be ' aW = (@A)xdx Comparing eq(1) and eq(2) Q dW = P(A x dx) ae == ‘ oe ® It shows system A and system C are in thermal ‘eee Put eq(2) in eq(1) ‘equilibrium with each other. dQ = dU+PdV a _sp STATISHE = the Following points, ody to cold body a bo dy only. ‘Thies ‘i eng is ie pl iynamics could not &S LIMITATIONS «of heat from hot ‘The first law of thermod} «This aw permits the flow drveaity, the heat flows from hot body 1 in Tradicate the direction of beat HOW: «eerdoes not tel us the quant oF ene which will change from ong other form. form, ES 1ODYNAMICS jodynamics has di Ror thermodynamics, EES SECOND LAW OF THERM ‘The second law of therm KELVIN-PLANK STATEMENT ‘The Kelvin-Planck statement i ivr the second law of ther that ean absorb enerEY i perfect heat engine is impossit ferent statements. 5 also known as heat engine rodynamies and tells us that tis ee Po, statement is part devise a heat engine ble. ofan equivalent amoun CLAUSIUS STATEMENT i Itis impossible to construct a hot reserve without aid from extemal source. Perfect refrigerator is impossi le. in the form of heat as v a5 well as progyeetle refrigerator that transfers heat from a cold rse Voi 5 |cuAPTELOt! THERMODYNAMICS ystem ether ee toil entropy of 28 60ND Law an eras ae aaa process. It never decreases: ond law of thermodynamics ir wetcm ae ereesa ies nds ‘IRD LAW OF THERMODYNAMICS entropy o : - er = perfectly crystalline substance is zero at absol relation between entropy $ and thermodyns given as ‘Where k is Bol S = kLogw ee ee eat is taken av absolute zero. temperature, all the mol oy gmum energy. t means at T= OK 1 - ute zero temperature(0K), ty Wis amics probabilit -a) yy from the sy ecules posses em, entropy 3 some -Q2 Put eq(2) in eq(1) S = kLog(1) Consider temperature of a system i “ tee eee OK to T. The increase in as= sr-s, = fo Vy 48 = -g7-0 = [22 {T ty AS = Sr yee It is mathemati tee on ical form of third law of thermodynamics. It is also called N s also called Nernst PERSE ; 5 THERMODYNAMICAL VARIABLES The measurable macroscopic it e the state of a ‘ : uanties used to deseriby f The state of a gas enclosed in a contaii ribed by thermodynamics variables i tainer is descril i i such as mass, vol » Volume, pressure and temperature.Sop a INTENSIVE VARIAB) seated i The thermodynamics varia is inte variables are indey remain unchanged a ‘partition of th feystem. These VON : idependeny| aa no. of particles ium. SUPPOSE Syste Consider a homogencous cysteine em Pees di sft may pans. a macroscopic variable x" of to aid to bein 1 XS, asi pr oft sem even : Hensive vat fy 2X thy 8 ate are intensive variables, it ‘Temperature, pressure and surface tension EXTENSIVE VARIABLES . ‘The thermodynamics vari] whole of the system is equal 10 the S tensive variable when val isco the variables of cacy the tt % system. ae «equilibrium. SUPPOSE syste * nsder 2 homogeneous stem Hn OO m is diyg ‘many parts. If a macroscop!¢ variable “X” of Cea ia values X,, x, ied ‘each of these parts of the system respectively then "18 said to be extensive ers : ox, +h t%* as care examples of extensive variables, eis called € sum of the Entropy, volume internal ener me PROCESS which no net "iy as enclosed in an insulted eylinderprovigg ne a REVERSIBLE ADIABATIC. ‘Thermodynamic process in conditions is adiabatic process. Consider one mole of ideal 8 1 heat transfer occurs duet : 0 piston. First law of thermodynamics is au + dW aQ dQ = dt PdV aves the system in adiabatic proc 0 --() ess. -@ Heat neither enters nor le dQ ut eq(2) in eq(!) 0 = dU + PV ‘deal gas equation for one inole is PV = RT a. v A canrTeR oH) THERMO, 5 DYNAMICS ©9@) Put eq(4) oes ert Vv Change in intemay neay in terms of Cy for one mote fs U=CydT eee o Put €4(6) in (5) wer 7 O= cary ar c+ T Integrating on both sides Log,t +R, eT + Clog, V = LogeK Log,1 + Se=Cv, Et Loe, V = LogeK Log.t +(e. c, 7 Thee. V= LogeK. Log,.T + Using eq(4) in eq(7) (r ~ Log, V = LogeK Log, FY. 8, E+ Log, V"~! = LogeK L oePV'"!) = Logek Where R Loge K = C is constant, Log,PV' = RLogeK Using eq(4) Pvr=c RT: Roy = 7 c ty = Lf R e Ty" =» pe ee asses woRK . ‘The work done in’ ‘Feversible adiabatic process is. we few -fSa = cfv-rav * — bl 1 7a : =o (2 et) ey sew) y=1 v veel Since F\V! =P, V3 = Constant w = (Re case) yt woe (RYE pyre - Liem -Py) yt cae Since PV =RT (RT, - RT) sore) wT This is amount of work done in reversible adiabatic process. First law of thermodynamics is : Q dU +W oo: (2) Heat transfer Q in reversible adiabatic process is zero 0 du +W Ww -dU It shows when change. in internal energy decreases, then work, done by the (12) ne | Combing 1 ae) Fe system inereases which means expansion adiabatic process. When change in internal Te @ = (% q energy increases, because of work done on the system. It means compression Teh 2 ae adiabatic process. i ble adiabatic proces. id volume in reversil pressure an ‘This is for temperature,which remains constany enetsy fon : « Intemal enet® funtion id oF 82 is convert nai wre : LENTHALPY yar termosyrir high Pe aive is called throtting pg, The ential 1 cess it WHT ortho aerng poo THE POC ug or fi ‘fluid or gas by US 7 Pi>Ps n ° First law of thermody ug - wu td ag = u+rv Put eq) in ea@) as - dU - pdv 20 qds - dU = pdV r For isothermal process. Tis ‘constant. acrs) - aU = pdV - For isochoric process. 'V is constant SO dv=0 acts - U) 20 aq - TS) <0 dF <0 : 5 free energy OF Helmholtz’s function and defined ay F = U-TS amies increases the useful work obtai ture and volume. tainable Where F is called Helmholtz’ Helmholtz’s free energy in thermodyn: ‘fom closed thermodynamical system at constant tempera From eq(2) Tas - dQ > 0 Tas > 4Q Tas 2 dU+dW Tas -dU > dW aw s TéS-dU [Queteson menoenianes Integrating both sides: “8 Tow ¢ thas - tau Tow eae ue faw s TE, - 8) = W, - Uy OS ee ot 1) = (Us = 78) Helmholtz free energy in terms of P, V, T and S can be derived as F = U-TS ar = dU -acrs) dF = dU-(TdS+SaT) ar = dU-TdS- SAT aF = dU- dQ - SaT dF = dU-(U+Pav) - SaT dU-dU —PaVv - Sat oF = -PdV - SdT For isochoric process, dV = 0 dF = —P(0) — SaT dF = - SdT aE oF aT i For isothermal process, dT = 0 dF = —Pav - $0) oF = -Pdv -P= g-(2 dv ov),A Stee Se eatin aa fanemol2' fe energy, jn refrigerators 2s it jg vse instal appticng ; . free en ‘This is «ete Equation of S06 ve ce ener8Y OO : fice emeetsg0 sw encode dat. DUC 1 it gi ‘auto encoder iM artificially, predict pure Subsio” nelpful a Ing AUto-ERCOdET! sen ver) Mf BUCO otal cod Hetrot's fe em cts 9S wwondsreulation of IE Codes x ly, isk a to ts high precision alyze 50 PCS eh ara I proves Pel ces dv Peonsucted Ode ye subst eis an excellent 2nsly2eT Jf atoms/molecu veRNAL ENERGY Iarge MUPeE peratures above abso) My INTERNAL PNG composed OF 3 qion aa of kinetic energie fo nate of oe ney: Torte system. ey ato os 8 ‘ fo each atom/molecule psstaled internal Kinet ye ofthe SYStEM alSO Possess, ‘atoms/molecules in 2 sYSt each stom/mo ar interactions. The sum op In addition to Kinetic Oe ge interme he system. hy potential eneray die #0 IHR al potential em tential energies i called portal ener called ST es an ite™ tg Lire ols value of internal Energy of gy ae pod be ted that ee BS change in internal energy of jven state can be found nor 18 EQUI her state is required. fystem during its transition from on¢ SUT ange in internal energy of a system, The types of interaction can ban 3 Thal inetons Het AE or or done by th mad 4 Mechanical intration(doing Wor «Diffusion inteactions(Exchang® Of mater) law of thermodynamics is Fintavof bemadeamis is yy Tas = dU+PaV au = TaS-PdV Tntemal energy ofa system isa state function. The change in internal eneryq system depends upon only on its initial and final state when a system makes [CHAPTER 01] THERMODYNAMICS from one state to another state, It doe: js carried about, FOR ADIADATIC PROC! Firs law of thermodynamics is dQ = “Adiabatic process gives . aq Put eq@2) in eq(1) oo dw = ‘Thus work done by a system in enerey- )R ADIABATIC ISOCHORIC PROCESS FO) First law of thermodynanies is dQ = dQ = ‘Adiabatic process gives dQ = Isochoric process gives dv = Put eq(2) and eq(3) in eq(1) o= CHEMICAL POTENTIAL The chemical potential due to a change of the particle Chemical potential i ; amount of the species suc ne Pattial Such that all oth, 7 not depend upon the path along which the change du +aw “ay 0 -@) du +dw -du an adiabatic process causes decrease in internal dU +aw dU +Pav derivative of the : tespect to the ler species concentra free energy with© When bot femperature ah tempera jcles is eXPRSSS free eneney mperstu When 8 AE I © Thus Considk For small change in foe ¢ i2).. ~“ wnt, and the tae 11 cons cane 6 eld Sri he aril mtg resid POT Nola Gat nates and the nupy constant fal is the partigh ° of nel se Fel he Q eepatia molE FE nergy sential sy ib’s fee energy” g eof % ents My my nical cons yr ates oF 44 nu gp, Tt Be (oO) ae (2) (6 a ae, Pe S| dn, +- * (ams Jaron aG = (4 se of change of HPS foe eneray ith ope where |S is rt ig «woe (FI rgors ae constant when all other factors are cons! spo's free energy With re where ( a js rate of change of Gibb’s sey ee when ll tke factor are const (4 p's free energy With res + Where 2] jerateof change of eal 2, Jere . ena ther factors are constant ra &dT=0 of’moles of component I, W If pressure P and temperat v-o-(2). a a dy #3. 4G 3G én, dG dG én, (2 2) dn, + => do,+ Meee = Gant = yy d+ Hy dn + quar on THERMODYNAMICS = » where Gi is parti molar Gibb’s fe ar Gibb’s fee energy of component poverty a ene as spite alae 4 = Gs where Geis paral moar Gibbs free energy of component 2 ell is chemi and defined as = .(% Gi (a woof) rents. It can be generalized as »-&) ‘The chemical potential pj is a measure of how much free energy . energy of janges, if you ad or remove a number dn, panicles of the particle species { while feeping the numberof the ther particles(and T & P) constant. ve asider y amount of energy is added to a system when an additional particles dn ofa given type is added to it ‘The change in intemal energy dU is given as aU = dQ- dW+pdn dU = TaS- Pav +pdn Where N is actually a discrete values, so notation is slightly abusive am sey ightly abusive unless we get dU = T)- PO)+Hadn aU = pda (8, ‘The Gibb’s free energy is defined as G = U+PV-TS dG = dU+PdV + VdP -TdS -— Put eq(1) in eq(2) a dG = VdP-SdT+pdn ‘At constant temperature and pressure &G = V(0)-S@)+ dn dG = pan potential similarly for other compon the ®6) 1 energy per unit temperature tained from ordered moet ENTROPY sen’ er slecular disorder or Tandog Entropy is the m unavailable for doing ‘motion, the amount of entropy is ofa system. « the mol ENTROPY OF CANONICAL’ sYSTEM(PERFECT CAS ne cae having pressure P, volume, empe oteter oon moe of perc as having SSS FLOSS ad sent [A small amount of heat dQ is absorbed by the B85: thermodynamics 2S amount dU given by first law of ag = au+dW ay Increase in internal energy when temperature of gas changes by AT is given ag aU = CyaT +++---Q) Where Cy is molar heat capacity at constant volume. Put eq(2) in eg(!) dQ = CydT+dW TdS = CydT+PdV a,P a = C+ TeV --+=+-@) ‘Three different expressions for increase in entropy of the gas are possible, WAPTERLO1) THERMODYNAMICS ROPY IN‘TERMS OF VOLUME & TEMPERATURE ges from one state io second state. Assume ature Tor first state of gas and Pevety nee (c ENT Consider state of a gas chanj fare pressure, volume and temper pyVott pressure, volume and temperature for second state of gas. ‘The total change in entropy of gas is given as oe a ey fos eff elev Se ® Perfect gas equation for one mole is pv = RT me TV ut eq(5) in ea(4) ‘ Vat, p fav. dS = +R] — [aa [si = CylLoatl} + R|Logv|\? $,-§,= Cy(Log T; —Log T,) + R(Log V, —Log V,) T, Vv; AS ¢C t+ aa v Loge +R Logs? rT V; +G- a Ft (Cp-Cy) Lows IfM is molecular mass of gas, then change in entropy for one gram of gas is given as 1 fr as = 4c, toe = afi + 3 Logs + (C,—Cy) Logs ENTROPY IN TERMS OF PRESSURE The change in entropy of gas is given as AS’ = Cy Log Perfect gas equation for one mole is PY = RT—— pygo STATIONS ty ey r 2 ere es HAPTER O11 THERMODYNAMICS Ditereninex@entee ar | w . Vay © Rav Ve » Perfect gas equation for one mole is “4 pv = RT Pat eq(3) in ea) : aie. pav = RAT = . ee i TOW Pat a(S) in a Differentiate eq(2) on both sides i a pav+VaP = RAT gn = PAENAE as = R a eg) and (nea ae as = OLA Be w . as = av . : S= c +e Integrating both sides "ap as = al’ +e co 5 aT ane 3 v fos= 6, [ P-&) P w % 2 : as = Cy + Cop _¢c,-¢,))Los Pf as = CylLoeti ~ (CeCe I Integrating both sides as = Cp(Log T,-Loe%) (Cp-Cy) (Los Pa Log B,) |s- cl &, c \ aw T, BR ne = C, Log - (C,-Cy) Loe Ce een P, as = CylLog PR + “c,ttos iFM is molecular mas of gis then change in entropy For one Bram of pai AS = Cy(LogP,—LogR) + Cp(Log V,—Los given as . : AS = Cy Log™ + C, Log as = : x \y : If Mis molecular mass of gas, then change in éntropy for one gram o ENTROPY IN TERMS OF PRESSURE & VOLUME : 1 P, : as = Uc, rg +c, Loe . M % N The change in entropy of gas is given as at, Pay oe“a RMOI [CHAPTER 01] THERMODYNAMICS 23 Perfect gas equation for one mole is Pv = eo sreeee (2) Tee ‘ 1_ OR a Vee (3) Differentiate eq(2) on both sides PdV+VdP = RdT PdV + VdP dT = 7 meee (4) put eq(3) and eq(4) in eq(1) as = ¢, Pavevah, Ray PV v dv | dP dv dS = + SH ]4+R— IG e Vv av | oP av ds= oc fM%+2]4C,-cy (2-2 e-co8 ap dv dS = Cy—+C,— vp t Ory Integrating both sides B ae fes- of2+0,(/% 5 4? av 28 = GyLor + Gla vi AS = Cy (Log P, Log B}) + C, (Log V, —Log V,) - = Pe Vv, AS = Cy Log + vy v Logp + Cy Loe IfMis molecular mass of gas, then change in éntropy for one gram of gas is given as 1 P, AS = —{C, Loge 5; wa v Lose *¢; Log) pyichangelinjalreversible: ety ENTROPY CHANGE IN REVERSIBLE PROCESS Consider a Camot cycle as a reversible 01 rersibl . Poa ee ver i oe cess to measure the change in entropy.avs process( AB): “Change in entropy is given asi = a T IN Noted nor retesed By the system au ag 2, ADIABATIC EXPANSIO! ‘The heat Q is neither expansion process(BC)- Change inentopy 8 VERA. 5) | ISOTHERMAL COMPRESSION ee “The heat Q2 is rejected by the syster" compression process(CD). _ . Change in entropy is given as sink at temperature Ts during isothey -@) 4, ADIABATIC COMPRESSION The heat Q is neither absorbed nor ‘compression process(DA). sreleased by the system duririg adiabss Change in entropy is given as dS, = 0 ware), ‘entropy in Carnot reversible cycle is, we o-oo tO} For reversible process © Put eq(6) in eq(5) s2a-Q fee ds = 0 ‘Change in entropy in Carnot cyclic process or reversible process is zero. CAME ene one ees ENTROPY CHANGE IN IRREVERSIBLE PROCESS Consider a reversible Camot engine “R” operating between a source at temperature T, and a sink at temperature Ta. Efficiency of reversible Camot engine is nS th io ae TZ Consider an other irreversible heat engine “I” operating between sante source and sink. It extracts heat Q, from source and rejects heat Qs to sink. mR = Q ‘Sink (Ta) Efficiency of irreversible Carnot engine is pups[CHAPTER 01] THERMODYNAMICS 27 4) 7 ‘Second law of thermodynamics is Divide both sides by T Put eq(2) in eq(1) ais ais als ; aim ie aie ie ae 2|3 218 or = Where B= (F) is coefficient of increase of pressure at constant volume and (3) is molar specific heat of gas at constant volume. ‘The cooling takes place during adiabatic expansion because GT is negative. The temperature decreases during adiabatic expansion. Discuss adiabaticic ADIABATIC COMPRESSION < ‘The entropy remains constant when a gas is compressed adiabatically. Tt temperature of gas is affected during adiabatic compression due to increase in pressure. Maxwell's third thermodynamical relation is ‘ ERS It shows increase in AEiEee IN : : aba "ADIABATIC EXPANSIO Jnen a gas is expanded adiabaticaly, The enn tel je atabatic expansion due to inereas¢ in Volung (3) (3) perature aah Is . = Maxwell's first thermodynamical relation is Divide both sides by T (2),--@) Ym) (MV) a ‘ av), Shy tla), \tas),--B) a: f volume at constant ff increase © PRES constant pressure. a ‘) is coefticient 0 -1fB) ise Where « i a) 2) js molar specific heat of B8 a Where Cp ( oh, The heating takes temperature increases during 1g adiabatic compression because oT is Positive. 7, uring place du. compression. diabat mmc resis FREE ENERGY fa system can be express Q.15. Dis ‘MINIMIZATION OF The free energy 0 energy equation as ed mathematically using the Gib ‘g= H-TS o Whexé isthe Gibbs fee energy, His he enthalpy: Tis the temperature, and gi the entropy. The enthalpy represents the amount of disorder in the syst scales the contributions of H and S to the The Gibbs free energy equation shows is minimized when enthalpy and entropy are balance the internal energy of the system, the enttopy repre em, and the temperature 1S the important factor thy free energy of the system. that for a given temperature, the free ener .d, At equilibrium, the free energy ICHAPTEROM THERMODYNAMIeS a 29 ho aysec lot msininey, ac ny change i sonitooa wt teal towards this state of equilibrium. ela aati riateaes ‘The minimization of free energy is a fundamental principle i sa pt tech ae ‘The minimization of ean, acoaing chemical reasons, phase wanaona ed It provides a quantitative framework for understanding the behavior ‘and has practical applications in fields such as materials science, wide iological processes. cof complex systems, Chemistry, and biology. (ESA LAW OF EQUIPARTITION OF ENERGY ‘energy for any system in thermal equilibrium is equally distributed among The total all degrees of freedom aid energy associated with each degree of freedom is Her. pRoOF 7 : ature T using ‘Average translational kinetic energy of gas molecules at temper kinetic theory of gases is given as ° 1 Any? = 2 2 Where “m” is mass.of gas molecule, k is Boltzmann constant and V is root mean square speed of gas molecules defined as, -Q) KT Pavia V+ .aAVE a - ve Magnitude of velocity V having cor i sani ami of velocity V having mponents V,, Vy and V; along x-axis, y-axis an Vie vieviev? Put eq(2) ineq(l) dawtave 3 pms +Vy +V2) = Ser Gy Gas molecules have i _ Gas o random motion and i seen have no preference’to move in -@ Put eq(4) in eq(3) 1 pms +V3 V2) = Sera [CHAPTER OI THERMODYNAIAICS, y 7 MULTIPLE CHOICE QUESTIONS Law of thermodynamics that states energy can neither be created nor similarly o destroyed is (a) First Law (b) Second Law (©) Third Law (6) Lerath Law (2. Property of 4 substance measures its ability to transfer heat or conduct electricity is (@) Conductivity (by Specific Hear (©) Heat Capacity (a) Entropy 03. Law of thermodynamics that states entropy of 2 closed system will always increase over time js (a) First Law (b) Second Law (© Third La (a) Zeroth Law 04 STunit for heat is (a) Kelvin (b) Joule © Watt (4) Ampere 05 The maximum efficiency of a heat engine operating between two temperatures, Ty and Tp, in Kelvin s a-1 (b) @ 06 Entropy change of a reversible process is (a) Zero (b) Positive (©) Negative (4) Can be positive or negative 07 Specific héat of an ideal gas at constant volume is (a) Cy (b) Cy (c) Both are equal (d) Cannot be determined 08 The internal energy of an ideal gas at constant volume is iO] u= Zar (be) U=nRTier Be Similarly Savy “2 eS ae kn 3mvi * 2 2 a a 03 Iishows KE ass . ICHAPTER 01] THERMODYNAMICS Ma, MULTIPLE CHOICE QUESTIONS Law of thermodynamics that states energy can neither be ‘created nor destroyed is (@) First Law (6) Second Law (© Third Law @ = Zeroth Law Property of a substance measures its ability to transfer heat or conduct electricity is @ Conductivity (0) Specific Heat (©) Heat Capacity (@ Entropy Law of thermodynamics that states entropy of a closed system will always increase over time.is (@) First Law (b) Second Law (© Third Law @ = Zeroth Law ST unit for heat is, (@ Kelvin (b) Joule (© Watt (@ Ampere The maximum efficiency of a heat engine operating between two temperatures, Ty and T;, in Kelvin s @ (b) © "5 @ Entropy change of a reversible process is (=) Zero (b) Positive (@ Can be positive or negative (©) Negative Specific heat of an ideal gas at constant volume is @ Cy ) (© Both are equal * @)_ Cannot be determined The internal energy of an ideal gas at constant volume is. 3 @ U= Sarr (>) U=nRT © vad;syste srt a eg NY w W7e SY] so _ baa [CHAPTER 01] THERMODYNAMICS. | ete 18. Relationship between the te ‘ ta ‘ Sane ip 7 n the enthalpy and internal ener; = 2 ‘ hin Sy of substance k - (c) H=Ux PV 7 ‘ ey - 9, Change ii 3 Bee cea ere bene ible isothermal process is (@ AU=0 (@ au-w (b) AU= (d) AU=Q-W. y of a ; © Users mone {@)_ Cannot be deter, ogy ersible isothermal Docent \ Ere er eee = 5 - . Be Q ole Te [3 a a we EO : ey u | @ @ [10 ing between 69 femPeraty is [| & a 7 3 iG) ta EDs f o \ : (a) 5 "1 iw | @ | 9 | @ | 2 | o 7 t, ae @ 1-7 8% oxw i @ PeaRTIV Oris 1 pressure is inv 1 transfer at constant P! 15. Ten prose volves heat t4 ‘ay Adiabatic e sta (@_Isochoric 16. res nove ent rat 7 (@) Isothermal (b) Adiabatic (©) _Isobaric @ Isochoric isothermal process is J by an ideal gas in am 17, The reversible work dont (b) W=nRT La Wy a . %). @ Ww wru(] ( W=akT ua) (@ W=nkT uli i) 5rent occurring, It ig g yf of an eve ciple event and I Fepresents ee) of the likeli ‘an impo’ PROBABILITY isa mieasure comes tothe otal MBE OF OUpp Probability ferneen 0 and 1. Where 0 represen event “The ratio of the number 1 is called probability. Probability = “Tot it an event E has m(E) favorable out ‘denoted by P(E) is elven 95 ©) a PE) = “n(S) + of favorable ou! et anevent ner of lavorable outcomes Lmumbe of possible Outcomes Mathematically, icomes in a sample spay. then the probability of E EXAMPLE ' probability of getting a is &, as thet ing Consider a fair die is rolled. The favorable ostome (rolling a2) ou of sx possible outcomes (rolling a 1,2, 3,4, So, derstanding of the concepts of probability are; The tems helpfal ina beter un EXPERIMENT wh ral or an operation conducted to produce an outcome i called an experimey, SAMPLE SPACE ‘All the possible outcomes of an experiment together make @ sample space, . Fa ‘example, the sample space of tossing a coin is head and tail. [CHAPTER OU) PROBABILITY DISTRIBUTION FAVORAB) "A favorable outcome is t favorable outcome in the ip of a. coin se 9 he For example, when we roll «wo dice, X numbers on the two dice as 4are (1,3) 2.2) yea. and (3, 1). ‘TRIAL 1 denotes doing a random experiment. Atrial RANDOM EXPERIMENT van experiment that has a well- by EXPECTATION OF DISCRETE RANDOM VARIABLE die ome te long for probabilities are equal and calculated ig ae der X is disrete random vatiable whose distribution is given as P(asXpulation Standard deviation = XC oF Ae = 398 = ili ‘sample variance ample Standard devi , varian e = set: (10, Sica data is (10, 13, Calculation of mean ‘Sample Variance = sa FL, Ke Tample Size — 1 nat ge Baas (=X) = iation = pe = NS = V435 =66 ee and standard deviation for the following sample te mean eT 13, 14, 16, 18, 23; 25,29) , 14, 16, 18, 23, 25,29) Sum of all data values Mean = Total number of values ze jor 13-+14+16+18+23 +254 29 = 8 K = 185 Calculation of variance Data values | Mean | X-X =H M a) te (x-X) 10 185_[ -85 72.25 13 185 | 55 3025 4 185 | 45 20.25 16 185 | -25 625 18 18.5 =0.5 025 a Be 20.25 29 18.5 ; 42.25 ce 110.25 DXiK-XF = 302 Sample Variance = X=)? Sample Size — gg = 302 ~ 302 Sere a53 grouped data s soem [DISTRIBUTION age median, mode, Tang AN, “riance and standard deviation for he 4 cae Fe following sample ‘aata set: (Ty 1b Th ‘20, 15, 20, 28) sol. . First of all arrange dato values in ascending order- @, Mh 11, 15, 205 20, 28) Median : Sol. Middle value of data is called ‘median. ol. : ante SoL_Mean seated Median = 18 Mid point 7 = ‘ Mode a 40-45 x fe x-X | &-XF | wx “rhe value that appears most often in data is called mode- Value 11 appears oe XH? twice. Value 20 ‘appears twice. eas], \ 3aa39 Pies 3 | ims | 254] itt 292.41 a7, Mode | 11&20 Meas 23 Range 23 maT 6s} | ses fase | ma | 12321 ‘Biggest value minus smallest valu is called range of data. B33 sos 123.2) ‘Range = B-S =28-7=21 yo a30 Ba] nay 4 | ie |ase | sa | 2601 . Mean ems 404 _ Sumofall data values,” 2% ieeanfnieey 5 | mas | 254 ost Mean = “Total number of values a2e a. 4.05 = wt fe een K- Te M4 +15 +20420 +28 iS] tosis i Z 4761 : = 7 7 ae ne 5.22, X= 16 3 | es asa] 29 | 1641 | s300, Daa values | Mean | -X-X mE T 5 = a -x) Die Tae x x y =508 13 7 aD a = 2035.8 16 3 7 x a 2 Men = Xu Qo og N ie | -s 7 >. 15 eT : Variance = Of &-X)? 20 jance = ae = 2035.8 20 ‘6 2 16 Standard deviation = oo 28 6 2 16 = Wariance = 107.15 = 10.35 is i 144 : LK-X} = 308=F = SSIS = Tags 25.6.7. 13,95, 33, Sel. Median, Middle value of dats is called medi 1 Median = an, Middle values are (7 & 13) Sn The binomial dsoibusion isthe discrete probsbiliy distibation that gives g Poss ible results in an experiment, either success OF failure. This distribution js ajo inomial probability distribution. SO ally MEAN OF BINOMIAL DISTRIBUTION The binomial distribution for eny discrete random variable “X" is given as Pasi) = "Cpa Where p=q = 1. ‘Mean of binomial distibution is apy = Sir@=d = Y ax =D BX] = Liga ai ®? 3% GD pq = apy gt : OX] = 9P2 Gopi x =D! ER) = my, Capa 35 EpX] = np) E(x] = 5P IN F BINOMIAL DISTRIBUTIO omic vA Tretbution fr any discret random variable “X” is given as i or a Variance is given as : var(X} = EDC} - {ERS} ceeeee oO varx] = EDC] = ap Where E(X?] canbe calculated as BX!) = DF P=) ae alg grt ERC) = 2" a-p! a n(a-D! = DE x @-D! eS ee ee 2 ED «OD! EDC] = apy imc. tat Let rei-l, then i=rt1 Hist, then r=0 Gif, iEDX] = np{o EX] = ap{(o—De+ EP?) = (n-Dnp’ + oP Pate) inca ree va) = stp ap + *P Var{X] = mp. - 29 ae = np - P) fens oe o = Wax o= vipa PA The mean and standard deviation of 2 binomial a. Find the value of n and p. Hence find P( P(x=i) = P(c=0) = P(x=0) = rat distribution #8 3 ye mean of binomi ost 3 Success p2 faining at probability of bt pearl sol. : Mean = 9 3 vax) = P47 probability of X at most 3 ony? INI= Wie IE wie istribution are 4 P(xg3) = PCC=0) + PO { x= 0) | R53) = “Cy phgh* + ‘CPI Pxs3) =4C, af + “Cpa + C,pha’ + °C wean ‘(2+ 0) tc, (2 2 Hao beens P(x$3) = §C, 1¥ 5 (2) 1y | aye tale o(t)ere(Bfe's "cpg Ly P( bole (1 i. wes (x3) (3) {y+ °C+°C, + *c,} vel Of fe tartar s) (2 2) \oue-o * 146-1” 246-2)! 1 P(x<3) = at 4 6 2) to * saa * at cs 4 SKS! 6xSxa 31” 21a! and variance is > a vari 3 ni) + P(x=2) + POR=3) ori te pa? + Cee 3. calculate Pd fy-sO@ (F) + } 33 31MECHANICS wm. . op _sTATisTiCAL S, 1x53) =( freer +2 P(xs3) = (ye +6415 420) * (Je) r(xs3) = 325 = 2x2? PEERED on DISTRIBUTION discret ie Fa penne Lag pend = ao il @ w>0 > #50 a et . % it ME: ~ = POISSON DISTRIBUTION ‘of Poisson distribution is Ep} = Sipw=) = E(x] = e(é + ERX] = o(t 1 yaRIANCE raiance is given 8 ee ee vartx} = EXD) pie ‘where B{x(x-D) ean be calculated as prce-m) = Eid poe=i) Efx(x-D] = x 60 yp) i@-G-9! Efx(x-D] = 7 E[x(x-D] = oF a y= 2 Ew He a (40,1, 2502s Seth ee Par) Bete) = [oa ee @a! * G2! aa, | E[x(x-D] = we *e") Efx(x-D] = “iliaca Put o9(2) in eq(1) y= pai“) smosantt tH conn 21 MM RECTANGULAR DISTRIBUTION vaixl- OE Se vax} = TE n rectangular distribution "Se y mean and variance a = * ec : t ax Binomial approximation to Poisson distribution, = fx roext fa roode + fx POO tin oo & p+0 such that np = (87° Be = J : | tpt 1 ay 2 txd Se ira Limit(*C, ¢'@") = Gi ao = 0+ [S40 eal aot 5 ill be found i a P.1_ Find probability that at most $ dts fe me rasa bo tay on @-2) fuses, if experience shows that 2 percent of Si : eel = 3(b-a) en xp st BX = 5-4/2 |, ‘2(b-a) 1 P@ss) =? (b+ayo-a) = 14a) n= 200 ER) = “3b-a) 2 a 2 STRIBUT] P me VARIANCE OF UNIFORM RECTANGULAR pis ‘ jstribution because ni is givenas Apply Binomial sii Pe ne ecaUse nis Very large ‘Variance xy = pe) ~ (200) w= np=2 - 1 aby P(xss) = PS) + PA) + PO) ian 4 Varix] = EEX] ~ Gb) ep cl ets! ety > P(xs5) = 7 0 Where E[X?]can be calculated as ao a2 fe P(x <5) = 2 *) EX?) = : P(x)dx, ’ . . P(x <5) = BEX] = fx’ P(x)dx + fe P@dx + fx? P@dx P(xs5) = 0.785 PDX?) = o+fe (qy)uro CREE Sennen ee eon UNIFORM RECTANGULAR DISTRIBUTION AA discrete random variable X has uniform rectangular distribution on the inten [a, bj, if its probability distribution function is given as fe asxsb 0 Otherwisea Put eq(2) in eat) variX} vartX} * fia Foc’ dot te S var{X1 - dap is even 10N lled normal probabj 2 ns ~0 109" spution. The probability densi of distribution. faa Where ys and o are parameters : following two properties: f(x) 20 vs(for all) food =1 MEAN OF GAUSSIAN DISTRIBUTION : X is also called its ‘The expectation value of a random variable mean | : ‘The mean m can be written as meu given as 1 a pode peta laa i t = {x Bp = [xfer ! (; an VARIANCE OF GAUSSIAN DISTRIBUTION Variance is the ‘expectation of the squared deviation of a random variable. A deviation isthe diffezence between the observed value and mean value. Var[X] = E(x-m)*] Var[X] = E[(x-u)'] Jo») ( See Var[X]MBD_ STATISTICAL MECHANICS (M.Sc. & Bs so (x=V2o0+n) So dx= V20do Var(X] = Jee’) (aE ) (8 as) vary] = 22 foto do Apply even function property . Vartx) = la joe? «| Put o? =a s0 20do=da => do- 24 = 2 20 * We Var[X] = —=| a 2a F f) Ee) Var[X] ; Va Standard deviation is pee Spx] = WVarfX] SX] =o BELL CURVE Normal distrit . ace ee or Gaussian distribution is a probability distributi ‘occurrence than ui ae _— that data near the mean are coe ae ae ee The graphical form of the norm. aa 65. a on is the proper erm for 20 | van is zero and the standard de frical, but not all symmetric the normal distribution .fectly normal. tribution the mes .ymme' + Norma mal. or aly ocurng enone in finance, most PriciNB distributions ar -ANDARD NORMAL DISTRI tandard normal distribution end to approximate e not, however, Pe BUTION has p=0&O=1 GAUSSIAN ST! ‘The Gaussian st Under these conditions Medin “m” of normal distribution is — standard normal distribution becomes oon =O standard deviation SEX] of normal distribution is : sx] =o standard deviation S[X] for Gaussian standard normal distribution becomes sxx} = 1 ‘Var[X] of normal distribution is Var[X] = 3° \Var[X] for Gaussian standard normal distribution becomes Var[X] = 1 The probability density function of normal distribution is given as A ae: 6 0 ‘The probability density function of standard Gaussian normal distribution becomes ‘ 1 sop One Gc £00) The random variable omad® fandom variable X having standard normal distribution is called standa X-m[BD _ STATISTICAL MECHANICS MSC. & 8, yg $8 ty -NTRAL LIMIT THEOREM ee tes that the sampling distribution of the sample - cel ‘The central limit theorem st s the sample size gets larger — no matter wat ye™™*Stg mes from distribution X 5° t ns onsight side t Mg) = Mxla approaches a normal distribution as. ofthe population distibution. This fact holds especially true for sample sizes over 39, Consider X,, Xp» Xsy «Xe 18 @ random sample drawn from any distrbutio, te inean and variance o For lage “n” the sampling distribution of sample Wit i approaches to normal distribution(Gaussian distribution) with mean js =p an da g : [™ ( 1 J : i mgt) = [Mx : deviation ie. tary a Define a new random variable Za X ~ Any distribution (n,c*) | For n> pier : ae X ~ Normal dito, is i Now write moment generating function of Zas M,() = Ble"]* PROOF ‘Moment generating function of X is given as Mx() = Efe*] ‘Moment generating function of X is given as Mz() = Ele™] Where X is defined as a Put eq(3) in eq(2) (Att eKtas Mh) Apply concept of eq(4) M(t) = Efe 7 oe wet (Sih) ‘ MA) = @* [Mal=5/# Mg(t) = Bele 4 M,() = M,() = of EO Gee : » Taking Loge on both sides Since X,, X,, Xj, «.X; are independent so expectation vales can be written Log. M,) = — LogM,(t) = — eparately asA ICAL MECHANICS (M.Se. LogyMy cos Bi = nLog, My ( ome a A) Mx| sa GJn 20" i venta) * 2 ee 2a «A(2) i) = Be HOR s an(t) a toes a i) Py am ete nol EE oso (o) t wf a) atoems(=fg] oe t). wi (2) -@) viain(cg) “SEE omG Comparing eq(8) and eq(9) Log.M,(t) + Log.M;(t) ‘Taking limit on both sides as it Log.Mz(t) = > + 2 M(t) = > Limit M,(t) = ¢? Limit Z ~ N@, 1) This jormal distribution. Hence proved. This implies Xan _ z= NO, 1) In,CRAP ene Consider 2-identical boxes. The particle can fall into any of the 2 boxes ten ii la GERCSeIoe MACROSTATE AND MICROSTATE thrown into the boxes. The probability ofthe particle entering the box 1 or box 2 is. ‘The distribution of 2-distinguishable particles in 2-identical boxes is given as Macrostates | Microstates ‘Thermodynamical Probability Box 1 | Box2 | probability/frequency Frequency Farangemenis @, 0) ab ) 1 y (ies (0F 2). 0 ab 1 % (1) a b 2; 24 b a No. of distinct arrangements = 4 = 2° Distribution of 2-indistin, iguishable particles in 2-identical boxes is given as, ‘Macrostates [__Microstaies | Thermodynamical -| Probability + [Box 1 [| Box2 | probability/frequency 2,0) ee 0 1 2) 0 ee I GD ° ° 1 No. of distinct arrangements = (cHarren 02) 2 awivation of 3-diatinguishable pa ‘No. of distinet arrangements = 341 Miicrosates | Thermodynamical [ Macross ee) Box? | Probability frequency Box! | Box _sa ee 8 be a fone an [2 20 = e a |e a2 [|b | 3 es + Us (0, 3) 0 abe = ‘ ‘No. of distinct arrangements g=2 : Distribution of 3-indistinguishable particles in 2-identical boxes is given im \crostates Microstates ‘Thermodynamica! ee eee jility/frequency ‘requenc) Box | Box 2, | Probability/freat - eae Va GO 0 7 aaa ea» . 1 lao 4,2) 2 ry { hm @3) 0 2 7 a Distribution of 4-distinguishable particles in 2-identical boxes is given as Macrostates Microstates ‘Thermodynamical_ Probability Box1 | Box2 | Probability/frequency | __ Frequency Arrangements @0 | abed | 0 1 (eee bed a Gn | ed [oo 4 4 abd |e 16(1,3) 2,2) 4) Distribution of 4-indi Macrostates 4,9) BY PROBABILITY oe HRN rrigrosates corresponds, {0 a given macrostate is C ‘The 10. sear *W i ability a : . ee = ee corresponding, to macrostale a, 1) is 2[G@, EO a)] for no, of microstal jing to act ! oa of -gadistingushable particles in ae al boxes. i nodal probabil) sw iver a8 wi, D = reater than The no. of microstates corresponding to # macrostae AY be equal or F orotate: oC i 10. ee are mdistingulshoble patcles 9 be distributed in pee boxes, the sible macrostates are (Ms (0),(n—1, D482 2) = (n—1,1)---(™)- : : No. of microstates. = 2" =r, 1) is given as probability of macrostate (n al ri(n= Probability of most probable macrostate (3. 2) is given as a @2) a, 3) oe ol a A Consider a macrostate ( Bex oH 5) which is slightly differ from most probable 0,4) MACROSTATE The no. of arrangements one another is called macrostate of the system. MICROSTATE ‘The distinct arrangement Ae un. 3) romania en. i without distinguishi i of particles ofa system without distinguishing ty Probability of new probable macrostate ( x) is giv en as --@) of panicles ofa system called microstate of sie,za. mop STATISTICAL MECHANICS (M.S ck Bs, ae rou ex | PROBADILITY OISTRIE ‘Multiply an. ; ily and divide right hand side by [ y soe peri te +20 epd= # () Ba BE ) epg= Heme”) ppg» mean ™ ARIANCE OF porssON DISTRIBUTION ‘Variance is given a8 Vartxy = ELx@x-D} — m(m=!) ver ~ Beale ol e? _pyean be ealeulated 95 = Yi-y PED -@ where E(x Efx(x-D] » Sic E[x(x-D)] E[x(x-D] = ya i 1D G—HG-2! Aa xy G-2! Efx(x-D] = Elx(x-D] 0,1, 2 2s Spe} tm (243) - ton 2 yen se) onl) = Log,P, +2108,(2) a (E>) : Use Stirling formula (Log.n! =n Log, a ef ate m t08,($-») ae 3. nT . wor. f(s}oe (3) wen] -Gonhenldes) Ge} - Gah) Loge P; = Log,P, + Log, ( ') (FZ! E[x(x-D] E[x(x-D] = &* [ ee . @-ai* Ga” ata ie 2 [5 apt Hen] E[x(x-D] E[x(x-] = pi e™ [i on Ww E[x(x-D] = pw? e*e")" '§ (MSe, STATISTICAL MECHANICS ( ABS pp STATIS ' ( n i) r le by Jy? Multiply: and divide right hand side by [ (3) a rR Pat ©9(2) in eq(4) Pos Py Take Log. on both sides Log. Py = . 2 | Loge Py = LogP. +1 St] ~ toa,{%4,)) [2 7 2.P., 2. (3 og, 3tx ! Log, 2x ! . Log. Py = Lop p 5!) ~ Log, {2 . Be o8,P, *2Log,(2 og.(5-+x}! ~ Log, Use Stirling formula (Log.n! =n Log, n ~n) fol) Loe P=] _ (($+>)i0e (B05)- (2 . {(G-x).(2=[CHAPTER 02] PROBABILITY DISTRIBUTION e Log,P, + atog,(2)-n - ($+*)t08,(2+x) n n n n +[=+x| -]=- y | BL a (5+) - Goel) (G9) Log P. +nLog.{2) — [24x |Log.| 24x cr +atan(8) ~ (Sesion (a Loge Py = Loge Px = Consider term . n n x Log, nae) = Log.—|1+— ca(§ )) oe i) n n 2x : | > = Log. =+L 14] 0 weeeee 6 Loe,(3+x) 85 on, =) ) According to Taylor’s theorem : 2 ; Log,(Ity) = y- y + higher order terms Neglecting higher order terms y Log. (ity) = y> “> Using this expansion in eq(6) toe,(3+x) = pee an mel 2x wereee () *k2 "2° on 2\n Similarly n n 2x 1(2x) Log.|=-x | = Log.- - — - > ore | eer 8 a.(S-x) = 108.5 - 3 3(2] @) Put eq(7) and eq(8) in eq(5) Loe.r, aloe, (3 ‘Loge Px = ‘Pr 2 | apt 02] PROBAUIITY DISTR ic probability PCE) of sys 1B posse P(e) & Wall) CE) = ke Wal) : : ore ky is constant of proportionality and W3(E3) is amount of microstates ‘1 were hy is coms! se 2) of system is site probability P(E E Compo 2) = PCED * PES) 1. 1 on * smmost probable state and deg, , both sides isc tional deviation from 1 * define ‘Taking Loge 0% ; 5) W,(Ey Where fis call frac ms i % Loge P(E. Es) = Log, {kik WE) WED} . ae Lop, PE Log,k; +Log,k; Log, W\(E,) + Los, WHE) The graph tetweenfand 2 ical — tine on both sides with respect Ei- : B ove one 2 Log, WE.) oo en 2 Lop,P(Ey E,) = 00+ gee} + Ue ; from most ze a. a 2 jog qe + (tee 09) = = 2 {Log,W, = (Los. 5 : atone) 3, eM oe, * 26, e, a a yj ----- 8) ARAMETER . i 2 Log,P(E,, E:) = Zttes, mi} + gp (bon Mle © Two systems are said to be in thermal contact with each other, if they arg , t 1 ‘of exchange heat energy between them. sVeansh ‘ray For maximum P(E, E:) Consider 2systems(A& B) having volume Vi and V2as shown in fig, Thy BS of system A is E, and energy of system B is Ep at equilibrium state. Total cont ag 3, -Log,P(E,, E,) system q that probability of deviatio Pemneir ne Comparing eq(5) and eq(6) a a GE, a 2 fuog,w,} 0 = tessa) + ge lla wel E= +B : The probability of both systems at equilibrium state will be maximum. The probability of a system depends upon no. of microstates in a particular energy state. ‘Total energy of system is given as ___ The probability P(E) of system A possessing energy E) EsEith is given as R= E-E PE,) « Wi(E)) . : : PE) = ky Wi(E:) : GB) NBs kis constant of propronaiy and WiC) is amount of mine: 79 Msp 2" . on 2 Pr Put eq(8) inea(7) 2 (toe.M) ~ ay lLBM) a a oe Hoe. Wy , 1) put eq(3) in eat 2 (toe,¥,) * © (Log. ¥i) =. TON, * Wa) Ae sntopy "Sr" Forsystem A is : a ith eachother, the funtion 2 7 ge) eee 6 Thus for 2-systems to be in equilibrium Fly, ee called -parameter must be constant and ae “ Entropy “S2 sy= £0) 2) = Zoe, WE) . - « put eq(d) e965) and (6) i ah rem) + 0) Where Loge W is a number so dimensionless. fw, x W) : / ‘The dimensions of B are given as iterentate€g(7) with respect to Wie : 1O- = cee : Py, = WW, = PO) +O ae) ase % th respect to W2- “The dimensions of are given 38 kT L Energy ‘Comparing eq(9) and e9(10) L Be it Where k is Boltzmann constant and T is absolute temperature, The -paray 2-systems in equilibrium should be same. a Derivela relation between entropy & thermodynamicaliprobaty ENTROPY& THERMODYNAMIC PROBABILITY Entropy of a system is the measure of its molecular dis ison Thermodynamical probability is the amount of microstates in macrostate, Bote and thermodynamical probability ofa system become maximum at equilibrium, ® The entropy “S" is a function of thermodynamical probability “W" and givenay s= W) “a Consider 2-independent i endent systems A and B having entopies Sy and S> respect The entropy S of both systems when taken together is given as eg S= +S, -2) Assume that W; and W are the thermodynami it Assume : iynamical probabilities of systern A anda respectively. The composite thermodynamical probability i given as W= WxW, cz -@) pifferentiate €9(7) wit FW, Divide e9(8) and ea(9) rw, * W) We ww, = 0+) row x W) FCW, * Wa) W wy, Ww Ww, POW werow w, f°) 0%) = yr : Integrating on both sides with respect to W). from aw, Kay +O ms +G, £(W,) =k Log,W, + C, £(W,) =k Log,W, + Cy ‘These both relations can be generalized as £(W) = k Log,W+C S= k Log,W+C aaaapp STATISTICAL MECHANICS (MS. & 96 80 wel “At absolte zero terpersti absolute zero temPeES yop) +E o= 0c ceo areal) Put eq(11) in eq(10) g= kLog, ation between entropy and thermodynamical probability ‘This required rel cE SEES SR ETEES "ENSEMBLES : The collection of particles is called system. ‘The imaginary collection ofa cof macroscopically identical but essentially {independent systems is called cane ans that each of the syStemé cong Ie. ity ‘The term macroscopically identical me ensemble satisfies the same macroscopic conditions, ‘of particles ete. temperature and the total number Tee team essetaly independent means each of the SYSIEMS consti” ensemble are mutually non-interacting. The systems differ in microscopic con 4 parity, symmetry, quantum states ele ‘TYPES OF ENSEMBLES “There ae thre types of ensembles: * Micro-canonical ensemble. * Canonical ensemble. like ve at ike volume, energy, yy © Grand canonical Ensemble. MICRO-CANONICAL ENSEMBLE It is the collection of a larg Iris th ze number of cssentally independent. systems having ‘the Sane carp U, volume V aed tol number of sea mS of 8 rmicro-canonical a separate i i — yy rigid impermeable and insulated walls, such thatthe values of U,V False affected by the muta preseure of other ystems. This ensemble is shown inthe ILITY DISTRIBUTION a ‘AL ENSEMBLE snonical ensemble i of essentially independent systems having particles N. ‘ANONIC ‘The 68 sa collection eT, volume V and number of identical systems" of a canonical 4 by rigid, impermeable but mperatu individual sparated same the seme © 5° emusing Wal “The beat can be exchang ca each common {Emre because 1 ee Conducting. Thus canonical ‘exchange heat ‘energy but not particles. .ND (CANONICAL ENSEMBLE. : - itis the collection ofa IO"Be number of essentially independent systems hi qemperature T, volume V ‘and chemical potential H tenPeiviualsystems-of grand eanonic anamble te sped id permeable and aneteting walls. AS the separating walls are onguting and permeable, the ‘exchange of heat conf as well as particles Between the systems takes yas ha way that all the system arrive at plata temperature and chemical potential. ENSEMBLE AVERAGE Every statistical quantity has not an statin! quantity during motion is equal ‘Consider R(x) is a statistical quantity along the x-axis then the ensemble average of the red between’ the aving the same exact but an approximate value. The average of | to its ensemble average. and N(x) is the number of statistical quantity R is phase pints in phase space, ‘defined as JRCONGOdx . JNoods i POSITION SPACE Consider a static system having “n" il der aise baving particles distributed in a given vol pesto of pare can be detemined fon thes, ‘coordinates, 2) Tae kaoatge . dimensional space gives the complete information about such a system.ICS (MSc, ICAL MECHANICS (MSE & 9 Pr 7 oon} PROBAMITY DISTRIBUTION oe fffaraae [fendered . in which posto ‘The Jeimensional $928 es is particles is specified by 3 i No. of phase sp osition spa nent i fe : mes te al se sex cfias pac cells g¢pnip in momentum in val p& pedpis position space is given as ae oo) Tee (axdydz) f f J(@p.dp,dp.) ay = axdy . steve = . : «articles distributed in a give vo ge : MOMENTUM SPACE ping es ving ny aowr =“ ( Consider a dynamic system™ ess aitferen : na SS “The particles are in random motions" Pic " ny carl 1is votume occupied BY momentum. 5pé "A edimensional space in NHN Ng in where integral state of the particles of the system is 45°" ig ped 85 sate of Peetu coors ete ff fien.se, ao called momentum space. i. i a The volume of small volume cle 1= Sapte’ - $0 . momentum space is given as a4 ar = dp,dp,d. Og i dnt ? +dp'+ 3p'dp + 3pdp") ~ 3 7P PHASE SPACE space is called phe eee ip? - p’) omentum sPae& Phase 1 ++ 3ptap + 3pdp" ~ P The combination of positon s700° and rate of 2 particle is speciteg yo 1 = Snip +p'+ 30d? space is a 6-dimensional space in which & articles 6mnet Y ioe : Secerdinatst, See fara system of 2 PATICES Croan 4 x(dp'+ 3p'dp + 3pap") required o deseibe is behavior in phase SP i gual to th — The volume of small ‘volume element a een oe Pra, 1 Sap neglecting higher order terms volume element in position space and volume = : Coo [oop o de = (dxdydz) (dp. dP, Ps -@) pateq() in ea(5) SIZE OF PHASE SPACE CELL ‘dp, dp, dt oe * Volume of one phase space cell = (axdydz)(dP, ~ _ Volume of one phase space ell = (6x dp,) (dy dp,)(az dp,) CERIN GENE nee MEET} ‘Apply Uncertainty principle 7 QUANTUM STATE Volume of one phase space cell = (t) +) “The condition in which a physical system exists is called state of system. The state of y “13 athemmodynamie system is defied by its intemal energy(U), entropy(S) as well as a set of Site variables including temperature(T), pressute(P), volume(V) and number of moles(n). ‘Quantum state of a system is a mathematical entity that carries all information shout the system and when that quantity is plugged into Schrédinger wave equation or related quantum laws gives the time evolution of the state of the system. This mathematical entity provides a probability distribution for all outcomes of each possible ‘measurement on a system and called wave function of the system. Volume of one phase space cell = ‘The yolume of phase space is given as : Volume of phase space = ff f(éxéyd2) JJ fccn.ae, ar.) ells in phase space is. given as Total volume of phase space Volume of one phase space cell ‘Amount of phase space ¢ No. of phase space cellsSTATISTICAL MECHANICS (M.S ‘wave equation is a machine in which potential «, aie ast Theo olution of Schrddinger wave equation) system is input. The machines runs‘ ‘output is called quantum state of the system. Every electron in an atom quantum state ofthe cleetro in tom, Consider Is? energy state i Ithas two electrons. The quantum states ae (ont 0.m-a.mee),(s0 QUANTUM STATIONARY STATE ‘The states for which the probability density does not depend on tim, quantum stationary state. : the probability density is P= [yoo =v Owe - , = ‘The wave furiction is 6s.) = yooe ® Put eq(2) in eq(1) Wee’ ® yaye® ie vend Jue P= yv@e'v) : P= w(xy(x) This probability density does not depend upon time s stationary state. | ae Pea PES Seen aE SYSTEMS WITH VARIABLE NUMBER OF PARTICLES ma ot ares atch output suchas encrey of system, quantum numbers, Wave Funetgg Pe x hhas its own unique set of fou, umber((n, é,1m,,m,). This set of quantum numbers (0, ¢, mgym,) 5% i a haf) are 7a) “2 ong at £5 ‘alg quantuy ‘The mathematical treatment of systems with variable number of parti ath Cc ten particles is based on statistical mechanics and probability theory. The behavior of individual as cannot be predicted with certainty, but the overall behavior of the system can be described statistically. One common approach is based on the conce; i i n approach pt of ensembles, which are collections, systems that are identical in terms of their macroscopic properties (such -as coat tion funtion ‘The Fh variable numbei rem S34 * peter reaction rates respective ex and ota available rm in tert syst function is use yr example, coos of diferent 5 sn sere ies ea tet my atin negates, sige Se wee bay gn oi i a oe Tt ps ene pemen ftie ms eed to calculate averages of thermodynamic, variables, such as ‘mathematical methods such as differential to model systems with variable number of Iso Pe ations describe the time evolution of the a a Sponkareacion sytem, based on tet jchiometries. and stoichiometry systems with variable number of particles is Soy many different mathematical tools and ‘and problem. the mathematical treatment challenging area of research, ‘depending on the specific systemo 02 “04 os 07 green balls. Ifa b and 2 grece bats Ifa bat, vial got BME? “6 © 1 ‘0 oF “4 io a 2 © 0 OF i ting a sur 2 pability of getting # sum of Gy ice are rotted, what is the PPO ty Hove dice led wt @ uw 6 2 os we 2 ples. If two marb) en marl les A jar contains 4 red) 3 blue, ame 5 greting one Fed and one areas at random, what is the probability cep ty @ Os 6 2 oz og Which of the following statements Is tre for a normal distribution» 3 (@) Mean= Mode = Median 7 ‘Mean = Median, Mode may or may not be > fo we Median = Mode, Mean may or may not Pe eH to Median (d) None of the above . ‘es withi 14 oer Gstributton, what fraction of date Tes within one x) deviation of the mean? 0). 6.2% @ A.50% Deca © 95.4% Os © sabe normal disthbution has # wens of___amd.astandardieg) 18 oan : @ O1 @ 1,0 © Le @ 0,0 16 Ifa normal distribution has a mean of $0 and a standard deviation of, is the z-score for an observation of 60? 1 @ 2.00 (b) 1.50 © 0.50 (b) -2.00 jn @ ai sistribution, the mean and variance are equal (b) False J statements is true regarding the para meters of @ positive number. ‘any positive number. ers are always equal. “The mes “The varia ; ‘The mean and vari Both aand bare true. veage number of cars that pas the probability that ex 4, what is next hour? ice paramet o ance @ 1s through a particular intersection in if the aver actly 6 cars will pass through the - fone hour is Satersection in the i) 0.067 o 0.247 Mierostate is (a) A large-scale configuration ofa system (b)_ Asmal-seale configuration ofa system (@) Ameasure of the disorder of a system (6) A measure ofthe energy ofa system Macrostate is G@) A large-scale configuration of system ()_ Asmall-scale configuration of a system (©) Ameasure of the disorder of a system (6) Ameasure of the energy of a system ‘Example of a macrostate is (@ The position of each molecule in a gas (6) The temperature of a gas. (©) The number of atoms ina gas (@) The distribution of velocities of the molecules in a gas (b) The pressure of a gas (0.148 @ 0.406 Example of a microstate is (@) The volume ofa gas. () The position ofeach molecule ina gas (d) The total energy of the gas Relationship between microstates and macrostates is : (a) There is no relationship (©) Microstates are subsets of macrostates (©) Macrostates are subsets of microstates (@ — Microstates and macrostates are the same thingoD igh entrony Isobaric-isothermal ensemble a ; 17 Example of macresate wi * of ice GA sold block ofice : er ©) liquid don oe yon omer of 8 con, * eee @ ee te with » low em 26 : 18 Example ofa macrostate ices : (Gas eu : aistibut jonical ensemble (2) A gue ntne i concent mane comer OF acon, Choro eanonical ensemble (@)_Yeobarie-isthermalengemble _ © ote accounts for constant energy, Volume, and number of particles is Amid bectoti= Fae Canonical ensemble (&) Grand canonical ensemble ‘A solid block of ¥ i y is (a) ne |sobaric-isothermal ensemble 9 oe sofa macrostate with # igh enerBy ' ° Micro canonical ensemble (@)_sobarie-isothermal ensemb (@ A gas at oom temperature ag Ensemble accounts for constant pressure and ae Cee wi ture jical ens le ense ©) Agasata very low tempers sin one comer of a conta; (@) Canonical ensemble (4) tsobaric-isothermal ensembl (© A gas with all the particles concent” maine (© Micro canonical ensemble (@)__sobaric-isothermal ensemble @ _Agas ith uniform distribution of ESS 1) Ensemble used to study liquids and gases ina gravitational field is 20 Example ofa macrostate with low ener) 6 9 ee eoaical ce (@) A gas at room temperature (6) Grand canonical ensemble 5) Agasatavery low temperature (© Micro canonical ensemble . ly distributed throughout a conting, (@ Canonical ensemble in a gravitational field Ensemble used to study magnetic systems is (®) Grand canonical ensemble ® (©) A gas wit all the particles evea! (© A gas withall the parcles concentrated in one comer ofa cont (@) Canonical ensemble @ Micro canonical ensemble Example of a macrostate that can contain multiple microstates ig (©) Canonical ensemble with a magnetic feld 2 (@) The position of each molecule ina gas (b) The pressure of a pa, (@ The temperature or, | 31 Phase space is ry (@) - A space for conducting space exploration (©) The volume of a gas 22 Relation between entropy and thermodynamic probability is oe (@) Direct (b) A-space for conducting scientific research on the brain @ tosis (©) A:space for describing the motion of particles or systems (@ A space for virtual reality gaming © Non-existent ding the relation between entry m A point in phase space represent 23° Which statement is true rega (emodynanic probability? ys (@) Increase in entropy implies an increase in thermodynamic (@) The temy i probabj iperature of the system (©) Increase in entopy implies a decrease in thermodynamic probebifj. (© Momentum and pesition of the syste oo © Norelation exists between entropy and thermodynamic Probability 33. The significance of the phase space i Qh ee ee (0) Tropes he diane ee between two points is 1 two points, {ynamic probability decreases, then increases as entropy j Yin pee ea ©)" Itrepresents the difference in potential energy between the tw rey 0 points ag OQ, Thermos Concept ex i ae, cn the relation between entropy and thermody Probab oe © It represents the probability of the ste itionit Ot — ae . « ater : “ystem transitioning from one state to the ichhoff’s Law @ Boyle's Law si eaiicance Ipre 03]_STATISTICAL MECHANICS (cH! PIAS ee ox STICAL MECHANICS ; ; ; ay branch of physics that deals with interpretation of macroscopic behavior of a alled statistical mechanics. The system as a i ic properties is ¢ apten using i et rather an indvidal particles such a5 atoms or molecules wisical inechanics. Statistical mechanics works well for a system of large number of icles. ‘Statistical mechanics have two types. Classical statistical mechanics. © Quantum statistical mechanics. CLASSICAL STATISTICAL MECHANICS Classical statistical mechanics deals with the classical systems such as molecules of . Maxwell, Boltzmann, Gibbs etc. applied classical statistics to study the behavior of classical systems. The macroscopic variables such as pressure, temperature, volume, internal energy, entropy etc. were explained successfully by using classical statistics. Classical statistical mechanics is also called Maxwell-Boltzmann statistics. QUANTUM STATISTICAL MECHANICS The classical statistical mechanics failed to explain black body radiation, photoelectric effect, specific heat at low temperature etc, Bose, Einstein, Fermi and Dirac made use of quantum mechanics to explain these phenomena. The statistical mechanics based on quantum mechanics is called quantum statistical mechanics. The quantum statistical mechanics is further classified into two groups. Bose-Einstein statistics. « Fermi-Dirac statistics