PREFACE ‘This manval contains solutions to Exercise Problems presented atthe end of cach chapter in Thermodynamic Loop Applications in Materials Systems ‘Volume One). Aithough answers are given in this book, the specific methods used to derive those answers are presented in this manual. Data not provided in a problem statement can be found in the book appendices. Due to the difficulty in reading graphs or variations in the computational path used to obiain an answer, the reader may obtain slightly different numerical values (not regarded as incorrect) than those given. Likewise, certain assump- tions made by the reader may yield somewhat more significant differences than those obtained using assumptions made inthis manual. Again, such differences are not regarded as errors as long as the assumptions used can be justified. ‘Throughout the book, an attempt is made to avoid this difficulty by making plausible engineering assumptions wherever possible. As will be noted, data limitations are often the reason that thermodynamics cannot be applied in a sziven situation, ‘The authors have used great care to eliminate computational errors, How- ever, if any are found, we would be grateful to readers for information about such errors including misprints in both the book and the solutions manual. DONALD L. JOHNSON GLENN B. STRACHER (CHAPTER 1 Chapter 1 {1.1] Calculate the coefficient of thermal expansion, @, at 273 K for an ideal es. Solution (3) RT a3 ( vei ver), ? a) Lk a)» P 278 = 3.66%103K4 [1.2] Consider the reversible expansion process represented by the straight line 1-2 in the figure below:The working substance is 1 mole of an ideal 408. P, = 1 atm, P, = 2 atm, V = 2V, and T; = 300 K. Find W for theTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution 2 a 2M w= [rar Act raat = PDEA 4 104,617) = 36,926 cm?- aum, = 36,926 x 0.0242 x 4.184 = 3739 Ymol 24,617 m*/mol 300K [1.3] The generalized expression av) (ar c,-¢,=1( 2) (= a (E)(), ‘can be used to calculate C, ~C, for any substance. Show that C, ~C, = R for an ideal gas. Solution PV=RT wheren=1 -BT_(a¥) 8 vero) [1.4] An ideal gas undergoes an isobaric change from an initial State 1:(P Vy’) 0 a final State 2:(P ,V9'T,). Prove Va V; -T). CHAPTER 1 Solution and PV; = nT, 1RT, = ep [1.5] Show thatthe total work performed during the reversible isothermal expansion or compression of an ideal gas from a volume V,’to Va"is given by the equivalent expressions W’= nRT In(V21V,") and W’= RT In(P /P,) W’ = ART INR, /B). [1.6] The reading on a pressure gauge relative to vacuum has to be added to atmospheric pressure in order to determine absolute pressure, ie.,abso- lute pressure = gauge pressure + atmospheric pressure. (@) Calculate the work done by 10 moles of an ideal gas expanding re- versibly from 58.784 to 14.696 psig (Iby/in® gauge) in a piston-cyl- inder arrangement at a constant temperature of 125°F. Perform the calculation without using numerical gas volumes at absolute pres sure. Express the answer in joules. (b) Calculate the volume occupied by 10 moles ofan ideal gas at 14.696 and 58.784 psig at a temperature of 125°F. (© Using the gas volumes obtained in (b), calculate the work done by 10 moles of an ideal gas expanding reversibly at a constant tem- perature of 125°F. Express the answer in joules. How does the an- swer compare to the one in (a)? Why are they the same or different?THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution 2 Vy Ege = PDEA + 104,617) = 36,926 cm?- aum, = 36,926 x 0.0242 x 4.184 = 3739 Ymol 24,617 m*/mol 300K [1.3] The generalized expression av) (ar ¢,-6, =") (= oo) ‘can be used to calculate C,~C, for any substance. Show that C, ~C, = R for an ideal gas. Solution PV=RT wheren=1 -BT_(a¥) 8 ver =F) [1.4] An ideal gas undergoes an isobaric change from an initial State 1:(P Vy’) 0 a final State 2:(P ,V9‘T,). Prove Va Vj -T). CHAPTER 1 Solution and PVs = nT, nT, = ya [1.5] Show thatthe total work performed during the reversible isothermal expansion or compression of an ideal gas from a volume V,’to Va"is given by the equivalent expressions W’= nRT In(V2V,’) and W’= ART In( PP, ‘Solution “5 = frw ART In V/V) nT /P, RTP, W’ = ART INR /B). or YEIM= HRI, [1.6] The reading on a pressure gauge relative to vacuum has to be added to atmospheric pressure in order to determine absolute pressure, ie.,abso- lute pressure = gauge pressure + atmospheric pressure. (@) Calculate the work done by 10 moles of an ideal gas expanding re- versibly from 58.784 to 14.696 psig (Iby/in® gauge) in a piston-cyl- inder arrangement at a constant temperature of 125°R, Perform the calculation without using numerical gas volumes at absolute pros sure. Express the answer in joules. (b) Calculate the volume occupied by 10 moles ofan ideal gas at 14.696 and 58.784 psig at a temperature of 125°F. (© Using the gas volumes obtained in (b), calculate the work done by 10 moles of an ideal gas expanding reversibly at a constant tem- perature of 125°F, Express the answer in joules. How does the an- swer compare to the one in (a)? Why are they the same or different?THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. Solution (@) Absolute gas pressures can be calculated from Paoa = Pynge + Pao Ig P, =14.696 psig + 14.696 psi = P, = 29.3925 , = 58,784 psig + 14.696 pai =P, = 73.48 PL ‘The work done by the gas is given by w= [rar ‘Since the calculation is to be done without using numerical gas volumes at absolute pressures, an expression for dV” must be derived. Pv" RT dV’ =-nRIP-*4P Substituting for dV” in the work integral, Pe we J Ponte? A Converting 125°F to K, °C = 5/9(°F — 32) and K = °C + 273.16° =» K = 5/9(125°F ~ 32) + 273.16° wee eae snes, pmol MAS sas01 Wo 10 maf S242 ats 2222) w= a1 (b) From the solution to (a), Paroge= 14.696 psig, Pase= 29.392. Ibyfin? and Page = 58.784 psig, Pate 73.48 Ibi? From the ideal gas law, PV’ = nRT =V"=nRTP. CHAPTER 1 ‘Thus, (omer(aa144. 22 \o0489%0) LK, - aoanBy (SAO) 3 1 Be Visepe = 0.133 m3 Views oman(s3144 2% \a2485%) ae tin i BABS aaten Vigo = 0053 m2 (©) The work done by the gas is given by we fra. ‘Since the calculation is to be done using numerical gas volumes at absolute pressure, an expression for P must be derived. = nRT=5P = nRTIV’. ‘Substituting for P in the work integral, -am [8 anou() : W's 24,7501. This is the same answer as in part (a) because the path ‘between identical initial and final states is the same. [1.7] Calculate the work done when the hydrostatic pressure on a cube of Cu measuring 2.cm on an edge is increased reversibly and isothermally at 0°C from 1 to 100 atm, Assume a negligible change in V over the pres- sure interval.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS em? , 63.54 gm Sem? “896 gm mol = 0.027 })mol, [1.8] Calculate the work done on the surroundings when one mole of liquid ‘potassium expands to vapor reversibly and isothermally at 1000 K and. (0.753 bar in a piston — cylinder arrangement. Solution worfw 0.783 bar(2592--1.493) Ee 8314, 39.108 kg 83.1441 bar ~ kg mol 27 kg mol. {1.9} Calculate the work done (internal compression) when a 350 lb mass of low carbon steel transforms from 7(austenits) wo c (ferrite) during an air ‘quench. Given that ¥,” = 0.0486 nm? and 2V7; = 0.0493 nm?, the basis, for these volumes is 4 atoms of iron (one unit cell of 7 or two unit cells, of a {Van Vlack, 1985, p. 76). CHAPTER 1 Solution W'=P| dv’ where P = 1 bar, Vj= 0.0486 nm; Vz = 0.0493 nm? nm? 33144 =1 bar(0.0493 a a 0.0886) ma sex ae eer 453.6 grillby _ 39 ‘gm-mol 35.85 em/(gm-mol) {1.10} Calculate the isobaric temperature change necessary to produce a molar volume change of 0.02 cm*/mol in a pyrope gamet, MgsAl,Si;O1a, crys- tal. Assume CV; js, aax i8 Constant over the temperature interval. 0.02 em?/mol r= T9810 em'fmot) SK ‘where Vite 298% = 113.18, OV pe, 2 = 2.98 X 10°, [1.11] Calculate the molar volume of the pyroxenoid wollastonite, CaSiO, at a pressure of 200 bar and temperature of 298 K. Assume fy, 2nx 8 constant over the pressure interval. Te initial pressure is 1 bar.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ‘av OP Jy Jr =- tinh = Ph? Yyaveav =39.93 em"/mol ~3.6x10-° — bar =2993 enna -2.6x10° 200-0 = 39.93 -0.01 = 39.92 cm* /mol 9.93, BV, on = 3.6 10S [1.12] Express (dP/4M)y in terms of the volume thermal expansion (a) and ‘isothermal compressibility (B) coefficients of a mineral. Assume Aarand ‘AB are negligible for small changes in P and T. where Vi 294 [1.13] Calculate the pressure on a crystal of spinel, MgAl,0,, heated iso- chorically from 273 to 308 K. The pressure at 273 K is I bar. Assume negligible changes in a and f over the P-T interval. The volume re- ‘mains constant because of external constraint. Soluion 5 avn ( 4 2 v= ser) wv -(F) es (F) ar Talat): 9" i (CHAPTER 1 oa tie Rearranging and substituting where @V; 295 = 1.03 x 10 cm3/(mol-K), BV 299= 1.9 x 10% cm?/(mok-bar) 1.03% 10° cm?/(mol-K) =1 e B+ T 9 a0 em'Z(mol-bar) OS 77% = 14 542,12 = S43bar. [1.14] A beam in a truss bridge is subject to uniaxial tension and compression (9) in such a manner that the beam undergoes infinitesimal changes from one thermodynamic equilibrium state (T,,0,) to another (T,0;). ‘The total differential of the dependent variable e involves two param- ‘eters known from experiments to be nearly constant for small tempera- ture changes. These parameters are the coefficient of linear thermal ex- pansion a: and Young's Modulus £. Mathematical definitions and addi- tional experimental properties are as follows: a= () + vis nearly independent of o t+ (22), i (@) Write an equation of state for the beam as a functional relationship. (b) Express the exact differential of ein terms of ceand E. (©) Show that if eis constant, (20107) <= —0E. Solution (a)Since e is the dependent variable and T and care independent variables, de r, (2 09 ae= (36) ao ( 32) ueTHeRVCOMANIC LOOP APUCATONS NMITERALS rE and substituting from the problem statement, ' de ait +(e oar (2) (©de=0 1 onear()a aar(De [1.15] Beginning with the expression P = f(V.T) (@) Express the total differential of P in terms of partial derivatives and ‘name the partial differentials. (b) Use the condition of exactness to demonstrate that dP is an exact differential. ‘Solution (@) Applying the chain rule to P = f(V.T) ¥ Expressions 1_& 2 are the “partial differer (b) If dP is an exact differential, the condition for exactness must hold true. Applying the condition to ‘ap oP. n= (35) ars (F) ar HG]: sl) -aaecae CHAPTER 1 11.16] Uniaxial tensile first cycle stress-strain loops for the magnesium alloy Dowmetal A-T4 are illustrated below. Small partial cycles beginning at the lower end of each loop are on a constant slope of modulus = 6.5 x 10* ksi since the frst part of each loop side isa line parallel tothe origi- nal modulus line. For each such partial cycle, assume total elastic return ‘upon the removal of stress. Compute the total work performed in ft -Iby ‘when a 10.0 in. long Dowmetal A-T4 cylinder of radius 2.50 in. under- {goes the partial cycles for loops 1 and 2 shown, (@) Loop 1: 6; = 1ksi, 6) = 5 ksi. (0) Loop 2: €, = 2000 pin/in, €, = 2500 pin/in. 7005 7060 008 000 308 errant Firat cycle uniaxial tensile stress-strain curves for Dowmetal A-T4 magnesium alloy. Loops 1 and 2 are labeled. MII = microinches/inch, (Prom M.H. Polzin, 1951, Fig. 9 with modifications. Reprinted by permission ofthe Society for Experimental Mechan- ies, Inc. Bethel, CT.) Solution (a) Given 0; = 1 ksi, 0 = 5 ksi, B= 6.5 x 10 Ibyin? W, =~] ode (work per unit volume) thus -¥ fate sme roi consTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEM 1 ~m(2.50 in)*(10 in) ff By -( By 18) eae 1a) “UO in) fain 4) +01) {(2500% 10-)* -(2000x 10) 34) = 2119.7 ft-Iby ‘The work is negative, hence work is done on the cylinder. 12