CHAPTER 1 9 The First Law of Thermodynamics PROBLEMS AND SOLUTIONS 19-1. Suppose that a 10-kg mass of iron at 20°C is dropped from a height of 100 meters. What is the kinetic energy of the mass just before it hits the ground” What is its speed? What would be the final temperature of the massif al its kinetic energy at impact is transformed into intemal energy? Take the molar heat capacity of iron to be C, = 25.1 J-mol"!-K~! and the gravitational acceleration constant to be 9.80 m-s-*, Just before the mass hits the ground, all of the potential energy that the mass originally had will be converted into kinetic energy. So PE = mgh = (10 kg)(9.80 m-s*}(100 m) = 9.8 kJ = KE Since kinetic energy can be expressed as mu?/2, the speed of the mass just before hitting the ground is ( 1 f20-8KD) ay get m) ~(t0K | ~“™* For a solid, the difference between C, and C, is small, so we can write AU = (Equation 19.39). Thea y= 9.8kI on 1x 10° (SEB Es) e5.13-m00" Ky =22K 55.85 ‘The final temperature of the iron mass is then 22.2°C. ——— 19-2. Consider an ideal gas that ocoupies 2.50 dm? at a pressure of 3,00 bar. Ifthe gas is compressed {sothermally at a constant external pressure, P.,., $0 that the final volume is 0.500 dm*, calculate the smallest value P,, can have. Calculate the work involved using this value of P. Since the gas is ideal, we can write 0.500 da betereet ‘The smallest possible value of P,, P,, The work done in this case is (Equation 19.1) 8.3145 J-mol'-K7 0.083145 bar-dm?-mol--K w= —P,,AV = (-15.0 bar)(-2.0 dm) ( 585586 Chapter 19 19-3. A one-mole sample of CO,(g) occupies 2.00 dm? at a temperature of 300 K. If the gas is compressed isothermally at a constant external pressure, P.,.0 that the final volume is 0.750 dm’, calculate the smallest value P,, can have, assuming that CO, (g) satisfies the van der Waals equation of state under these conditions. Calculate the work involved using this value of P.,.. ‘The smallest value P.,, can have is P,, where P, is the final pressure of the gas, We can use the van der Waals equation (Equation 16.5) and the constants given in Table 16.3 to find P, (0.083145 dm®.bar-mol!-K~1)(300K) 3.6551 dmé-bar-mot? 0.750 dm®-mol’ = 0.042816 dm?-mol* ~~ (0.750 dm?-mol")* = 28.8 bar ‘The work involved is (Equation 19.1) w = —PAV = ~(28.8 x 10° Pa)(—1.25 x 10 m*) = 3.60 1d 19-4. Calculate the work involved when one mole of an ideal gas is compressed reversibly from 1,00 bar to 5.00 bar at a constant temperature of 300 K. Using the ideal gas equation, we find that nT PF and We can therefore write V,/¥V, = P,/P,.. Now we substitute into Equation 19.2 to find nRT _ va- [tay w f Pad / aa % P, Ss % Pe erin (32) narin( Ft) = ($1 mol)(8.315 J-mol“!.K~)(300 K) In0.2 = 4.01 KI 19-5. Calculate the work involved when one mole of an ideal gas is expanded reversibly from 20.0 dm? to 40.0 dm’ at @ constant temperature of 300 K. We can integrate Equation 19.2:o find the work involved: % =nRT ln (@) 1 mol)(8.315 J-mot K-")(00 K) In = -1.73 19-6. Calculate the minimum amount of work required to compress 5.00 moles of an ideal gas isothermally at 300 K from a volume of 100 dm? to 40.0 dm?The Fist Law of Thermodynamics 587 ‘We note that the minimum amount of work required is the amount of work needed to reversibly compress the gas, so we can write Equation 19.2 as =nRT In @) = ($8.00 mol (8.315 J-mol-K™!)(300 K) 1n0.400 = 11.4 15 19-7. Consider an ideal gas that occupies 2.25 L at 1.33 bar, Calculate the work required to compress the gas isothermally to a volume of 1.50 L at a constant pressure of 2.00 bar followed by another isothermal compression to 0.800 L at a constant pressure of 3.75 bar (Figure 19.4). Compare the result with the work of compressing the gas isothermally and reversibly from 2.25 L to 0.800 L. ‘We can iise Bquation 19.2 to describe the work involved with the compressions under different circumstances. a. Two-step process, each step at constant external pressure i. From (2.25, 1.33 bar) to (1.50 L, 2.00 bar), (2.00 bar)(1.50L — 2.25 1)(100 J-bar-* dm’ 507 ii, From (1.50L, 2.00 bar) to (0.800 L, 2.50 bar), == f nave ‘The total work involved in the two-step process is +413 J. b. Reversible process Because the gas is ideal, PV =n RT. We can then write —3.75 bar) (0.800 L — 1.50 L)(100 J-bar“! dm") = 263 J PY = (2.25 L)(1.33 bar) (100 J-bar“!.dm) = 299.25 J =n RT and use Equation 19.2 to find w: 0.800 ¥, -f Pav =—nRT in () 299.25) In GS) = 309) ‘The total work involved in the reversible process is +309 J. Note that the work involved in the reversible process is less than the work involved at constant external pressure, as is expected. 19-8. Show that for an isothermal reversible expansion from a molar volume V, to a final molar volume V,, the work is given by v; A w=-RTIn -saF (F54)- sha for the Redlich-Kwong equation. For the Redlich-Kwong equation, RT A prc Sasyesenieeseoney 16.7) VB TeV +B) st588 Chapter 19 ‘We can then use Equation 19.2 to find w. 19-9. Use the result of Problem 19-8 to calculate the work involved in the isothermal reversible expansion of one mole of CH, (g) from a volume of 1,00 dm?-mol~! to 5.00 dm*-mol™ at 300 K. (See Table 16.4 for the values of A and B.) From Table 16.4, A = 32.205 dm®-bar-mol”?-K'? and B = 0.029850 dm? mol”. Then, using the equation for w from the previous problem, ‘V,-B\) oA V,+2)¥, er), a For an ideal gas, 6 = 1/P, bat fora liquid, f is fairly constant over a moderate pressure range. If Bis constant, show that v Vis eter ® My where V, is the volume at a pressure P,. Use this result to show that the reversible isothermal work of compressing a liquid from a volume V, (at a pressure P,) to a volume V (at a pressure P) is given by viv =P Vy +oe (Pine 7 +1) ny YM = =P,Vile Fh) — 1} + B'V,{1 — [1 + BCP = Pe) 8) (You need to use the fact that [Inxzdx = xInx— x.) The fact that liquids are incompressible is reflected by f being small, so that B(P ~ P,) «1 for moderate pressures. Show that 4 BYP = PoP w= BPVg(P — Pa) + OC) V, = Pocps — Pa) +O) @) Calculate the work required to compress one mole of toluene reversibly and isothermally from 10 bar to 100 bar at 20°C. Take the value of 6 to be 8.95 x 10~* bar"? and the molar volume to be 0.106 L-mol~ at 20°C. ‘We begin with Equation 1 and integrate both sides, letting f be constant with respect to pressure. [-sae = f va BP — P,) =In (%) erBOHFD& TheFiattaw of Themodynnies 591 Now we wish to fd the reversible isothermal work of compressing a liquid from (P., V,) to (P, V), We know that 6w = —PaV (Equation 19.2), s0 we use the expression we found above for P towrite [- rin 2) its | av 1 (¥ = PAV +6" mn(Z)av bw= Integrating both sides of this equation gives —Pyv = ve" finvav—p foway = — PAV — V,) +8" [VInV—V—(VoIn V,— ¥y)] — BV — ¥y) In Ve =-P(V - Vy +81 (VinV—V—KIn¥,+¥~ Vin¥, + Vln) ry (YnX PLY = Ve) +8 «(Ee t) Substitution for V then yields the result wa —PiVaferr — 1] + A"V {1 [1 + CP ~ Pere} PCP — P,). Because ~B(P — P,) < which is Equation 3 in the text of the problem. Now let x = 1,2 < 1. We can now write Equation 3 as P.Y,(e* — 1) +B", (1—[1 + ACP — Pe} = A PAM(e* — 1) + BM — BI Vee" — VCP — Pade Now, recall from MathChapter I that if x is small, we can write e* as 1-+x-+24/2+ O(s') (Equation 1.2). Notice that to find w to O(6*), we must expand e* to O(2*), since one of the above terms multiplies e* by B~'. Expanding the above equation gives ge w= PV, [x + O)] +6 BTV, [i txt 5t 00)| -V,(P - P,) [1 +24 O()] = BP,Vo(P, — Py) + VP-P.) — Ber = Vol P = Py) + BVP — Py) + O18) BY,(P — Po)? = BPLVo(P — Py) + + 08) Vor pe = Teer py +08) Now, for one mole of toluene {to (A)], we use the parameters given in the problem to find (8.95 x 10~ bar™')(0.106 mol-L7")" ; [100 bary? — (10 bax)?] = 418 1 19-14” In the previous problem, you derived an expression for the reversible, isothermal work done ~Wwhen a liquid is compressed. Given that 6 is typically O(10~) bar, show that V/V, * 1 for pressures up to about 100 bar. This result, of course, reflects the fact that liquids are not very compressible. We can exploit this result by substituting dV = —Vd P from the defining equation of f into w = — J PdV and then treating V as a constant. Show that this approximation gives Equation 4 of Problem 19-13.592 Chapter 19 We are given that 8 ~ O(10~ bar“), and the largest pressure differential that can occur under the given conditions is on the order of O(10* bar). Then, using Equation 2 of Problem 19.13, we find HOB) = 6-000) = 9.999 ‘Therefore, V/V, © I for pressures ranging from 1 to 100 bar. Now dV = —BVdP, so ~ [ pav =r, f par Be fan as in Equation 4 of Problem 19.13. w OT ar), oH av\ _,,(aP\ _au\ fav), (au aH) _» ap) _ (av) (av) (20 Gr),-?° Gr), -" GR), (9,6), 0), Using the definitions of C, and C, (Equations 19.39 and 19.40), this expression becomes. av) _ (av) (av &--#(F),~(5r), (57), +6 aU av e-er=[°+(57),](5), “ av °F), Using the ideal gas equation to find P (8V/8T) p, we find that av (Fe) +y and PY =nRT (3), (19-28) Following Problem 19-27, show that op (*-Ge)]G), ‘We can write the total derivatives of P(V, T) and H(P, T) as (MathChapter H) ap ap a= (55). ave +(#), aT @ aH aH an=(#) ae+ (FF) aT o) ‘Substituting d P from Equation a into Equation b gives = (55),L(60),4”*Gr),<"|* Gor), <7 = (2), ($e), 4”* (2), Gr), + Ge) J”600 Chapter 19 We can also express H as a function of V and 7, in which case the total derivative dH is aH ‘aH (2) ave (FF) «r Because the coefficients of dV and dT in both expressions for dH are equal, we can write (sr), - (), Gr), (x), ~ Ge), Gr), * Gr), e Substituting U + PV for H into the left side of Equation ¢ gives al + PV] oH) (aP\ (aH ar y \aP),\ar),” \aT}, au av ap\' _ (aH) (ap), (aH Ge), ° (Ga), +"), = Ge), Gt), + @), Using the definitions of C, and C, (Equations 19.39 and 19.40, this expression becomes ap aH ‘aP ov+v(3r),= (Ge), (ir), + ‘aH ‘aP «-6=[¥- (35), (), aH and which is the desired result, 19-29, Starting with H = U + PY, show that (i), Interpret this result physically. Take the partial derivative of bot sides ofthis equation with especto 7 holding P constant, and substitute C,, for (0/87) ». H=U+PV oH aU av Gr),- (),+° (3), av)" _ au’ *(),-), ‘This expression tells us how the total energy of a constant-pressure system changes with respect to temperature, Recall that for a constant pressure process, dH = 8g. Then C, = (8q/8T). Because dU = 5g + bw. the work involved in the process must be — P(2V/3T) ». The equation above is equivalent to the statement (2) = (a ar), \ aT C,“The First Law of Thermodynamics 601 19-30. Given that (9U/3V), = 0 for an ideal gas, prove that (6H /@V), = 0 for an ideal gas. ‘Begin with Equation 19.35 and use the ideal gas law to write H=U+PV=U+nRT Now take the partial derivative of both sides with respect to volume (note that for an ideal gas, U is dependent only upon temperature) to find (54), Gr), +"), 19-31. Given that (8U/2V), = O for an ideal gas, prove that (8C,/8V), = 0 for an ideal gas, ‘We define C, as (U/8V), (Equation 19.39). Therefore, acy) _ #u__ a fav’ av), aver aT \av/, Since (9U/8V) = 0 for an ideal gas, (8C,/V), =0. 19-32, Show that C, — Cy = aR if (@H/9P), = 0, ass true for an ideal gas. From Problem 19.28, ‘aH aP =[v- (28) ](28) = e=[y- (Gr) 1G), where, as stated in the problem, (@H/3P), =0. Substituting P pression get (7), RT V-' into the above ‘aeRTV") _ c,-6,= v (SEE) at 19-33. Differentiate H = U + PV with respect to V at constant temperature to show that (QH/3V), = 0 for an ideal gas. (Notice that this problem has you prove the same thing as Problem 19.30 without assuming that (2U/AV), = 0 for an ideal gas.) We can use the ideal gas equation to write Equation 19.35 as H=U+PV =U 4nRT For an ideal gas, U is dependent only on temperature, and the product n RT is also dependent only on temperature. Therefore, H is a function only of temperature, and differentiating H at constant temperature will yield the result au ar a) ene (4) = (ar), +98 (@r),=° ()602 Chapter 19 19-34. Given the following data for sodium, plot A(T) — (0) against T for sodium: melt- ing point, 361 K; boiling point, 1156 K; A,,,H° = 2.60 kJ-mol"'; A,,,H® = 97.4 kJ-mol™'; (8) = 28.2 J-mol!-K"; C,() = 32.7 J-mol"!-K; C,(g) = 20.8 J-mol"'-K"! ‘We can use an extended form of Equation 19.46: f Ta ee Fr) - Fo = [ Ty(odT + Ay A+ f E,()dT + AgH + f C,@ar Notice the very large jump between the liquid and gaseous phases. t40F F(T) FI(O) 1 kom 200 600 1000 1400 TIK 19-35. The A,H* values for the following equations are 206 kI-mol~! 2Fe(s) + 30,(g) > Fe,O,(s) A.A? = 136 kI-mol"! 3 Fe(s) +2.0,(g) + Fe,0,(s) A.A" Use these data to calculate the value of A, Hf for the reaction described by 4 Fe,0,(8) + Fe(s) —> 3 Fe,0,(s) Set up the problem so thatthe summation of two reactions will give the desired reaction: 4{Fe,0,(8) > 2Fe(6) + 30,(@)]A,H = 4206) ks +313 Fe(s) +20,(g) > Fe,0,(9)] A,H = 3(-136) KI 4 Fe,0,(8) + Fe(s) 3 Fe,0,) AH =416KS 19-36, Given the following data, }AL()+45,@) > HF(@) 4,4? = -273.3 kI-mol H,(g)+40,(g) + HO) 4,H? = —285.8 KJ-mol™! ‘calculate the value of A, H for the reaction deseribed by 2F,(g) + 2,00) —> 4HF(g) +0,(g)“The Fist Law of Thermodynaeies 603 ‘Set up the problem so that the summation of two reactions will give the desired reaction 4[H,(g) + 1F,(g) > BF®) A,H = 4(-273.3) KI + 2[H,0() > Hy(g) + 30,(@)] A.W = 2(285.8) KI —521.6K0 2F,(g) +2H,0W) 4 HF) +0,(@)A,# 19-37. The standard molar heats of combustion of the isomers m-xylene and p-xylene are 4553.9 kJ-mo!~! and ~4556.8 kI-mol', respectively. Use these data, together with Hess's Law, to calculate the value of A, H® forthe reaction described by m-xylene —> p-xylene Because m-xylene and p-xylene are isomers, their combustion equations are stoichiometrically ‘equivalent, We can therefore write m-xylene > combustion products 4,H = —4553.9kI ++combustion products > p-xylene AH = $4556.81) ‘m-xylene—> p-xylene AH =42.91F 19-38. Given that A,H° = ~2826.7 KI for the combustion of 1.00 mol of fructose at 298.15 K, C,H,,0,(5) + 6 0,(g) —> 6CO,(¢) + 6,00 and the A, H? data in Table 19.2, calculate the value of A, H” for fructose at 298.15 K, We are given A, H” for the combustion of fructose in the statement of the problem. We use the values given in Table 19.2 for CO,(g), H,O(), and O,(@) A,H°[CO,(g)] = —393.509 kI-mol"! 4, H°{H,O(D)] = ~285.83 KI-mol~! 4,H°10,(8)] = 0 Now, by Hess's law, we write A,B = S78," Iproducts] — > A,H°[reactants] —2826.7 KI-mol™! = 6(—393.509 kJ-mol™!) + 6(—285.83 kI-mol™") — A, H°[fructose} A, H(fructose] = 1249.3 k-mol™ 19-39. Use the A,H° data in Table 19.2 to calculate the value of A, H” for the combustion reactions described by the equations: a. CH,OH() +3 0,(g) — CO,(g)+2H,00) b. NLH,(}) + O,(g) — N,(g) +2 H,O(1) ‘Compare the heat of combustion per gram of the fuels CH, OH(1) and N,H, (1).604 Chapter19 ‘We will need the following values from Table 19.2: A,H*ECOS)] A,H’IN,H, -393.509kJ-mol" A, H*[H,O@] = 285.83 KI-mol +50.6 kI-mol™ 4, H°ICH,OH()] = —239.1 kI-mol" a, Using Hess's law, Y4,H fproducts] — S° A,H° [reactants] = 2(—285.83 kJ) + (—393.5 kJ) ~ (—239.1 ks), 726.1kI_\ (1 mol e = & ee) (s 042 3) Pere ae A,H? =~ d,H° [products] — )~ A,H*[reactants] = 2(—285.83 kJ) — (+50.6 kJ) Erwan : = (22H) (tat) = asa b. Again, by Hess's law, More energy per gram is produced by combusting methanol. 19-40. Using Table 19.2, calculate the heat required to vaporize 1.00 mol of CCI, (I) at 298 K. CCI) > CCl) We can subtract A, H°{CCI,(1)] from A, H°(CCI,(g)] to find the heat required to vaporize CCl, AvogHl? = —102.9 KS + 135.44 KI = 32.5 KI 19-41. Using the A, H° data in Table 19.2, calculate the values of A, H for the following: a. CH(g) + H,00) — C,H,OH() b. CHL(g) +4CL(@) —+ CCL, + 4HCIg) In each case, state whether the reaction is endothermic or exothermic. a. Using Hess's law, A, H? = ~277.69 KI ~ (-285.83 b+ 52.28 KS) = ~44.14 Kd This reaction is exothermic. b. Again, by Hess's law, aH {(—92.31 KI) — 135.44 kJ — (—74.81 kJ) = 429.87 1S ‘This reaction is also exothermic. 19-42. Use the following data to calculate the value of A..." of water at 298 K and compare your answer to the one you obtain from Table 19.2: A.,,H® at 373 K = 40.7 kJ-mol™; E,() = 15.2 J-mol-K-; C,(g) = 33.6 J-mol-K“".“The First Law of Thermodynamics 605 We can create a figure similar to Figure 19.10 to illustrate this reaction: #00) ““=3"* How tan, LAH, 1,00) H,0() Now we use Hess's Law to determine the enthalpy of vaporization. Baggs x = AH, + MH, + Ay Hn x = (75 K)5.2 J-mol-K~) + (75 K)(33.6 J-mol|-K~) + 40.7 kI-mol"! = 43.8 k-mol Using Table 19.2, we find gl? = A¢HTHO(8)] ~ 4,1°H,00) =241.8 kI-mol™! + 285.83 kI-mol™! = 44.0 kI-mol™ ‘These values are fairly close. (Using values of C,, which include temperature-dependent terms may further improve the agreement.) {9AB_)Use the following data and the data in Table 19.2 calculate the standard eatin enthalpy of "re vatrgas reaction a 1273 K. Assume tha the gases behave ideally under these conditions Cs) + H,0(g) — CO(e) + H,(s) CHCO(I/R = 3.231 + (8.379 x 10 KY T — (9.86 x 10 KT? C3EH, (g)}/R = 3.496 + (1.006 x 10~ K""T + (2.42 x 1077 KT? C3{H,O@)Y/R = 652+ (1.156 x 10-7 KT + (1.42 x 1077 KR) T? CIC(S)]/R = —0.6366 + (7.049 x 10 KT ~ (5.20 x 10° KT? + (1.38 x 10° K>)7? ‘We can create a figure similar to Figure 19.10 to illustrate this reaction. ce +H) “2" cove) +He JAH, + AH, co+Ho@ “S* cow +H@ Now use Hess's Law to calculate the standard reaction enthalpy at 1273 K. To do the integrals, it is helpful to use a program like Excel or Mathematica (I used Mathematica), so that the tedium of adding and multiplying can be avoided. AH Kons = A, Hig + MH, + AH, (=110.5 kJ-mol™ + 241.8 kJ-mol~!) +R f , (CACO + C,LH,@I ~T,1H,0(81 ~ C,[C)]} a7 = 131.3 kI-mol™ + R[3725.01 K + 3649.92 K — 4542.43 K — 2151.29 K] 131.3 KJ-mol"! + 5.664 kI-mol” = 136.964 kI-mol"606 Chuo 19 19-44. The standard molar enthalpy of formation of CO,(g) at 298 K is 393.509 kI-mol™*. Use the following data to calculate the value of A,H° at 1000 K. Assume the gases behave ideally under these conditions. CpICO,(O/R = 2.593 + (7.661 x 10° KT — (4.78 x 10K) 7? + (1.16 x 10° K)7? CRLO,(@)I/R = 3.094 + (1.561 x 10° KT — (4.65 x 107 KT? = 0.6366 + (7.049 x 107 KT — (5.20 x 10-6 K-*)7* CHC + (1.38 x 10° KT? ‘We can create a figure similar to Figure 19.10 to illustrate this reaction. CS) + 0,18) Coys) AH, tan, co +0) “S* co. Now use Hess’s Law to calculate the standard reaction enthalpy at 1000 K: Hino = 4, Hing + OH, + AF, 393.509 kJ-mol! +R f ,, (CelC0,(8)1 ~E 10, - C {C91} 47 393.509 kI-mol"! + R [4047.167 K — 2732.278 K — 1419.433 K] 393.509 kI-mol"! — 0.869 kJ-mol~' = ~394.378 kJ-mot? (49-45) The value ofthe standard mola reaction enthalpy for CH, (g) +20,(g) — CO,(g) +2H,0(8) is 802.2 KI at 298 K. Using the heat-capacity data in Problems 19-43 and 19-44 in addition to C8ICH,(@)]/R = 2.099 + (7.272 x 10° K“YT + (1.34 x 10-7 KT? = (8.66 x 10" KT? to derive a general equation for the value of A,H® at any temperature between 300 K and 1500 K. Plot ,H° versus 7. Assume that the gases behave ideally under these conditions. We can create a figure similar to Figure 19.10 to illustrate this reaction. CH, +2018) “5 CO,(g) +2H,0%) YAH, NA CH) +20,2) ““2"* co,¢g) +28,01@)“The Fest Law of Thermodynamics 607 Now use Hess's Law: AH? = A, Hig + MH, + AH, = —802.2 kJ-mol™! r +R f {€,{CO,(@)] + 20 {H,0()1 - T ICH) ~2C 10,1} 47 = -202216.mot +f [.610~ (4.21 x10 K-)T] aT +e [-G.0 x 10° K)T? + 2.03 «10° KT] dT ass = —805.8 kJ-mol™! + (1.339 x 10°? KJ-mol KT (1.750 x 10° kS-mol"!-K™*)T? — (1.025 x 10°* kI-mol 4#(4.211 x 107? k-mot-K-7* -800 E 3-801 € = 802 & = aan 600 5000 1400 TIK Pee eee eee eee eee 19-46, Inall the calculations thus far, we have assumed the reaction takes place at constant temperature, so that any energy evolved as heat is absorbed by the surroundings. Suppose, however, that the reaction takes place under adiabatic conditions, so that all the energy released as heat stays within the system. In this case, the temperature of the system will increase, and the final temperature is called the adiabatic flame temperature. One relatively simple way to estimate this temperature is to suppose the reaction occurs atthe initial temperature of the reactants and then determine to ‘what temperature the products can be raised by the quantity A, 1°. Calculate the adiabatic flame temperature if one mole of CH,(g) is burned in two moles of O,(g) at an initial temperature of 298 K. Use the results ofthe previous problem. ‘We know from Problem 19-45 that 802.2 kJ-mol™ of energy is produced when one mole of methane is burned in two moles of oxygen at 298 K, Now we determine how much the temperature of the products, one mole of CO, and two moles of HO, can be raised by this energy: AH (products) = R f {E,(CO,(e)1 +26, 14,0} 27 802.2 kI-mol~! = f {C,[CO,(e)) +20 (H,0@))} 47 = ef [9.897 + (9.97 x 10°? K“) = (4.496 x 10° K)7? I $(1.160 x 10° KT] dT = 27.89 kI-mol! + (8.23 x 10? KF-mol1-K“)T + (4.15 x 10° KS -mol KT? = (1.25 « 107% kI-mol!-K“) 73 + (2.41 10°? kI-mol"!-K“)T*608 Chapter 19, We can solve this polynomial using Simpson’s rule or a numerical software package. Working in Mathematica, we find thatthe final temperature will be 4040 K. 19-47. Explain why the adiabatic flame temperature defined in the previous problem is also called the ‘maximum flame temperature. ‘The adiabatic flame temperature is the temperature of the system if all the energy released as heat stays within the system. Since we are considering an isolated system, the adiabatic flame ‘temperature is also the maximum temperature which the system can achieve, 19-48, How much energy as heat is required to raise the temperature of 2.00 moles of O,(g) from 298 K to 1273 Kat 1.00 bar? Take T[O4(@)I/R = 3.094 + (1.561 x 10-9 KT — (4.65 x 1077 KT? We can use Equation 19.44: i f a wn =@.00 man [2.0944 (1.561 x 107 KY (4.65 x 10-7 KAT] aT 64.795 k5-mol! —_—— 19-49, When one mole of an ideal gas is compressed adiabatically to one-half of its original volume, the temperature of the gas increases from 273 K to 433 K. Assuming that C, is independent of temperature, calculate the value of C, for this gas. Equation 19.20 gives an expression for the reversible adiabatic expansion ofan ideal gas Car = -tav Integrating both sides and substituting the temperatures given, we find that IF var -{F Aav ZnB -Rinp Ey nS = —RIn2 Gin = -Rh 1.50 19-50. Use the van der Waals equation to calculate the minimum work required to expand one mole. of CO,(g) isothermally from a volume of 0.100 dm® to a volume of 100 dm? at 273 K. Compare ‘your result with that which you calculate assuming ideal behavior.“The Fist Law of Thermodynamics 609 In Problem 19-10, we found that the work done by a van der Waals gas was Substituting a = 3.6551 dm.bar-mol™ and b = 0.042816 dmn!-mot the parameters in the statement of the problem gives from Table 16.3 and using 0.042816 dm?-mol~" — 0.042816 dm*-mol ] = ($169.5 dm*-bar-mol™! + 36.5 dm?-bar-mol™)(0.1 kJ-dm™-bar™")(1 mol) =13.3 KT 100 dm? -mol 0.100 dm?-mot 100 dm? mot~* — 0.100 dm’ -mol (106 dm®-mol) (0.100 dim®-mol™") = (0.083145 dm?-bar-mol™?-K™')(273 K) In +3.6551 dm*-bar-mol> For an ideal gas, w= f Pay =—nkT In (@) (156.80 dm? bar)(0.1 KI-bar™!) = —15.71I ‘The work needed to expand the van der Waals gas is greater than that needed for the ideal gas. 19-51. Show that the work involved in a reversible, adiabatic pressure change of one mole of an ideal gas is given by where 7, is the: For a reversible, adiabatic pressure change of an ideal gas, 4g = 0, so dU = dw. Since dU is defined as CydT, and so substituting gives610 Chapter 19 GBB In this problem, we will discuss a famous experiment called the Joule-Thomson experiment. Tn the first half of the 19th century, Joule tried to measure the temperature change when a gas is expanded into a vacuum. The experimental setup was not sensitive enough, however, and he found that there was no temperature change, within the limits of his erro. Soon afterward, Joule and Thomson devised a much more sensitive method for measuring the temperature change upon expansion. In their experiments (see Figure 19.11),a constant applied pressure P, causes a quantity of gas to flow slowly from one chamber to another through a porous plug of silk or cotton. If a volume, V,, of gas is pushed through the porous plug, the work done on the gas is P,V,. The pressure on the other side ofthe plug is maintained at P,, 50 if a volume V, enters the right-side chamber, then the net work is given by why Avy ‘The apparatus is constructed so that the entire process is adiabatic, so q = 0. Use the First Law of ‘Thermodynamics to show that Ut PM AHU+AY orthat AH = 0 for a Joule-Thomson expansion, Starting with a aH aps (GR) ar an=( show that : a aP), Interpret physically the derivative on the left side of this equati is called the. Joule-Thomson coefficient and is denoted by 44,,. In Problem 19-S4 you will show that it equals zero for an ideal gas. Nonzero values of (97/8 P),, directly reflect intermolecular interactions. ‘Most gases cool upon expansion [a postive value of (87/8 P),,} and a Joule-Thomson expansion is used to liquefy gases. iY wr YR—* 2— Yin Ye. FIGURE 19.11 [A schematic description ofthe Joul Thomson experiment. ‘The net work is w = P,V, — P,V,. Since q = 0,U 80. AY PM“The First Law of Theemodynarnics 611 ive of H asa Since AH = U, + P, function of P and 7 (U, + P,V,), AH = 0. Now we write the total deri an an dH= (3) ae+ (2 ar Using the definition of C,, we write this as aH dH= (3) aP+C,aT ‘The Joule-Thomson coefficient is a measure of the change of temperature of a gas with respect to the change in pressure in a Joule-Thomson expansion (or compression). 19-53) The Joule-Thomson coefficient (Problem 19-52) depends upon the temperature and pressure, ~ assuming an average constant value of 0.15 K-bat”! forN,(g), calculate the drop in temperature if N,(g) undergoes a drop in pressure of 200 bar. (0.15 K-bar~) (—200 bar) = 19-54. Show that the Joule-Thomson coefficient (Problem 19-52) can be written as om (i),--e 1G), Ge), ),] Show that (37/8 P),, = 0 for an ideal gas. From Problem 19-52, oe), z (3), + (2) | 21G).@),+CP),] For an ideal gas, U and PV depend only on temperature, 50 f4,, Since H=U+ PV, }9-55) Use the rigid rotator-harmonic oscillator model and the data in Table 18.2 to plot © (7) for Cote) from 300 K to 1000 K. Compare your reslt with the expression given in Problem 19-43612 Chapter 19 From Example 19-8, we know that for an ideal gas =C,4R 19.43) And from Chapter 18, we know that for a linear polyatomic ideal gas Gy _ 5, (On) goat (F) ~e,/t (18.41) ‘Therefore, since ©, (CO) = 3103 K, we wish to graph 1, (esx 2 pent 2 T — = = Experimental curve Rigid rotator Gre 400 600 800 1000 1200 1400 TIK 19-56. Use the rigid rotator-harmonic oscillator model and the data in Table 18.4 to plot C p(T) for CH,@) from 300 K to 1000 K. Compare your result with the expression given in Problem 19-45, Again, for an ideal ges Cy+R (19.43) ‘And from Chapter 18, we know that for a nonlinear polyatomic ideal gas. Gry) eal ) a Het Using the values given in the problem, we wish to graph e, ‘4170K\* 4 Rigen ( T ) d-e Tare 4320 K)” a( T ) mo KT‘The Fist Law of Thermodynamics 613 —— Experimental curve Rigid rotator Gir 400 600 800-1000, TIK PE eee 19-57. Why do you think the equations for the dependence of temperature on volume for a reversible adiabatic process (see Equation 19.22 end Example 19.6) depend upon whether the gas is a monatomic gas or 2 polyatomic gas? For an adiabatic process, no energy is transferred as heat, so the chenge in intemal energy is equal to the change in work, The internal energy of a monatomic gas (in the electronic ground state) is entirely in the translational degrees of freedom, which is directly related to the temperature of the «gas. If the volume of the system increases, work is done by the system, and so the internal energy of the system must decrease. The only way for it to do so is by decreasing the amount of energy in the translational degrees of freedom, which decreases the observed temperature of the gas. The internal energy of a polyatomic gas (in the electronic ground state) is in the rotational, vibrational, and translational degrees of freedom. These vibrational, rotational, and translational energy levels are not necessarily in equilibrium (see Problem 18-37). Ifthe volume of a polyatomic gas is increased, work is done by the system, as before, and the internal energy of the gas must again decrease. However, the gas can lose energy in the rotational or vibrational levels, which will not decrease the observed temperature of the gas. It can also lose energy in the translational levels, which will decrease the observed temperature of the gas, but the other available methods of decreasing the energy of the system will change the dependence of temperature on volume for a polyatomic gas from that observed for a monatomic gas.| MATHCHAPTER J The Multinominal Distribution and Stirling’s Approximation PROBLEMS AND SOLUTIONS JH1. Use Equation J.3 to write the expansion of (1 +), Use Equation J.4 to do the same thing. Using Equation J.3, we can write ata Lona it = 14 5x +102? + 10s + 5x4 +29 Equation 1.4 gives the same result. J-2. Use Equation J.6 to write out the expression for (x + y + 2)*, Compare your result to the one that you obtain by multiplying (x + y +z) by («+ +2). a dyet deep day tatty ee ‘We obtain the same result when we multiply (x+y +2) by (x+y +2). J-3. Use Equation J.6 to write out the expression for (x + y + z)*. Compare your result to the one that you obtain by multiplying (x + y + z)° from Problem J-2 by itself. Using Equation J.6, we can write suo @tyto= sa Len yea 4 A ae t5 in? maa ey + pom - ate A 4 og 4 ma? * Tsr0r Tose? + Tae” + Te 615616 MathChapter | Fl 2xy%2 + [aye? + yt +28 +4y2 +4 y's + 6y2? ‘We obtain the same result when we multiply (x + y +2)? by (x+y +2). J-4. How many permutations of the letters a, b, are there? 31=6 JAS. The coefficients of the expansion of (1+ x)* can be arranged in the following form: 1 4 6 4 1 ‘Do you see a pattern in going from one row to the next? The triangular arrangement here is called Pascal’s triangle. Each number in a row is the sum of the two numbers above it. J-6. In how many ways can a committee of three be chosen from nine people? =3xTx4= 84 J+7. Calculate the relative error for NV = 50 using the formula for Stirling's approximation given in Example J-3, and compare your result with that given in Table J.1 using Equation J.7. Take In Nt to be 148.47776 (CRC Handbook of Chemistry and Physics). InN! = NInN —N + In@xN)'* = 195.6012 — 50 + 2.87495 = 148.4761 ‘Compared to In N}, there is @ 1.12 x 10 relative error. This can be compared with the 0.0194 relative error obtained when using Equation 1.7 for In N!. J-8. Prove that xInx + Oasx + 0. im(x nx)i | j z | a ‘The Multinominal Distribution and Stirling's Approximation 617 ‘Since both numerator and denominator are undefined as x —> 0, we can apply I'HOpital’s rule: = ) =lim(-x) =0 x) Jimy(x In x) = Tim, ( eee J+9. Prove that the maximum value of W(N, N,) = N1/(N ~ N,)!N;! is given by N, ‘Treat N, as a continuous variable.) Let N, = x, with x being a continuous variable, Then 1 wo Wom! InN1 Inq = x)! —Inzt in nweng al ‘We are looking for the maximum value of W, so, at this value, (4W/dz) 0. Also, we know that Law _ dW) Wd dx |At the maximum value of W, then, d(In W)/dx = 0. We can express In W using Stirling's approximation (Equation J.7): InW = InN! —In(W ~ x)! —Inx! InN —N=((N —2)In(N —x) -(W 2] = (en ~ 9) ‘The derivative of In W is then ddnW) _),N=-x See eee Fee HOt ay thw x) Lins = InN =x) = Inx Setting (d(In W)/dx] = 0 gives 0 = In(N — x) In InN — x) Recall that N, = x, and that N, = N — N,. The maximum value of W then occurs when N, = N/2. esse J410. Prove that the maximum value of W(N,, Vj, ...« N,) in Equation 1.5 is given by N, =, =--=N,=N/r. Given:618 ‘MathChapter Take N, = N = N, — N, ~+++—N,_,, because 3D N, = N. Then we can use Stirling's approxi- mation (Equation J.7) to write In W as bnW = Wow == 3H, =a =winn—w-S'n,0N,— 1H, —(N —N,~ Ny = + —N,,)In(N ~ N= N= Now take the partial derivative of In W with respect to ,. We find that ainw a As in Problem J-9, we set d(in W)/dN, -IWN, +1 -14In(N —N,-N,----N,,)41-1 to find 0=-InN, —In(V —N, — InN, =I0N, NaN, We get a similar result for N, through N,_,, 50 N, = N, = +++ = N, and all are equal to N/r. JH11, Prove that ‘We know that (Equation J.3) w! wtyts Smwromr a = 1. we can write this as ceo Saw Wy lms Bi im Thus Savin mnt y= J+12. The quantity n! as we have defined it is defined only for positive integer values of n. Consider now the function of x defined by r@= [Pea w Integrate by parts (letting u = rey=e-vf “and dv = ede) to get tevtdt = (x — P(r 1) @‘The Malineminal Distribution and Siting’ Approximation 619 Now use Equation 2 to show that P(x) = (x — 1)! if x is a positive integer. Although Equation 2 provides us with a general function that is equal to (n — 1)! when x takes on integer values, itis, defined just as well for non-integer values. For example, show that (3/2), which in a sense is (3)!, is equal to x'/2, Equation | can also be used to explain why 0! = 1. Let x = 1 in Equation 1 to show that (1), which we can write as 0!, is equal to 1. The function ['(x) defined by Equation 1 is called the gamma function and was introduced by Baler to generalize the idea of a factorial to general values of 1. The gamma function arises in many problems in chemistry and physics. We can integrate P’ by parts, letting u andy Te = f eed tee = [mec — peat I =- of eed (I) Pe-1) Now if x is a positive integer, we can write P@)=@-)P@- == De-Hre-2 2 and write (3/2) a8 r@/2) f * eds f[ atetax We can let = 1 Qt Also, we can express (0) as