~ Fundamental Equations of

~

I

4.1

One mole of nitrogen is allowed to expand from 0.5 to 10 L. Calculate the change in entropy using (a) the ideal gas law and (b) the van der Waals equation. .SOLUTION
(a)
L\S = R In(V2 = (8.314 = 24.91 /VI) J K-I J K-I mol-l) mol-l In(10/0.5)

(b)

M

=

R

In[(V2

-b)/(VI -I

-b)]

= (8.314 J K

mol)

-I

In (0.5-

(

10-

0.039)

0.039)

]

= 25.55 J K-I mol-l

4.2
SOLUTION

Cp-cv ---

=TYa2/K=-T

(aY -- ) (ap )
2

aT The van der Waals equation

p

av

T in the following form:

can be written

~

11 9 mol-l.99 J K-l mol-l .3 Earlier we derived the expression for the entropy of an ideal gas as a function of T and P.237 x 10-3 K-l)(1000 bar) 0.237 x 10-3 K-l. SOLUTION dS = (dSld7)p = (Cpl7) = ( Cpl7) dT + (dSldP)TdP dTdT(dVld7)p aVdP dP 4. -~S=-Vaf). p where a is defined by equation 1..50 Chapter 4/Fundamental Equations of Thermodynamics j:']i a-l=v(~~ av Eliminating TV a-l=--V-b K is calculated =~p p with R !!.p = -78.4 What is the change in molar entropy of liquid benzeneat 25 °C when the pressureis raised from 1 to 1000 bar? The coefficient of thermal expansion a is 1. derive the expression for dS for any fluid.879 9 cm-3.879 9 cm-3 = -10.i l ir I " " ~ RV + ~ RV2 equation yields the van der Waals ~(V-b) RV2 from CaPay =-+ T RT (V-b)2 R 2a ii3 Cp- Cy = 2a~ l-RT V3 4.50 can be written as -(~\ =. Now that we have the Maxwell relations. and the molar mass is 78. SOLUTION Equation 4.pJ T ar =.11 9 mol-l (10-2 m cm-l)3 (1.36.Va.(~) t. the density is 0.

86 9 cm-3. SOLUTION -55. :E VRT ) -1 What is the difference between the molar heat capacity of iron at constant pressure and constant volume at 25 °C? Given: a = 35.Chapter 4/Fundamental Equations of Thermodynamics 51 4.86 17 mol-l . (a) To this degree of approxima!ion. and the density is 7.11 cm3 mol-l 90 cm-3 (102 cm m-l)3 = 7.11 x 10-6 m3 mol- Cp- Cv = a2TV/1( -(35. p=~- RT a v ~ RT -+2a (~) =3V T - "ii2 RV V3 (~) p = 2PV-RT CpCV= R( 1 --.11 x 10-6 m3 mol-l)(105 Pa barl) x 10-6 barl) In equation 1.1 -(0. (b) Calculate (dH/dP)T . 1( = 0.:.52 x 10-6 barl.847 V -7.52 = 0.7.5 Derive the expression for Cp -Cv for a gas with the following [p + (a/V2) ]v= SOLUTION RT equation of state. derive the expression for (dH/dP)Tfor a van der Waals gas.51 J K-l mol-l x 10-6 K-l)2(298 K)(7.27 we saw that the compressibility be written as factor of a van der Waals gas can where tenns in p2 and highe! are negligible.1 x 10-6 K-l.

and we calculated that the entropy of freezing water is -20.9 we calculated that the enthalpy of freezing water at -10 °C is -5619 J mol-l.52 Chapter 4/Fundamental Equations of Thermodynamics for CO2(g) in J barl 0.08314 mol-l mol- L bar K-l 1 I = 0.9 In Section 3.V)T (the internal pressure) for a gas following the virial equation with Z = 1 + B/V.01 L bar 1-1 = 1. SOLUTION --(dH/dP)T PV=RT+ mol-l at 298 K.251 -0. What is the Gibbs energy of freezing water at -10 °C? SOLUTION -- .8 Derive the expression for (dU/J!.640 L2 bar mol-2 and b = (a) = V- T(dV/d7)p (b-alR7)P v= RT/P + b -alRT = RIP + a/RT2 VRTIP -alRT (aVla7)p -(oHloP)T= = b -2a/RT (b) (diI/dP)T= 0. SOLUTION p= RT + BRT 'ii2 V (ap).04267 L mol-l.01 L bar or 0.04267 L mol-l - = -0.= ~ + ~ dT V ---2 V 112 v + !1I(aB)dT v fap (aUlaV)T='\dT ) V-P = ~(aB) -2 dT V V 4.01 L bar 1-1 = -25 I barl Since R = 8.54 J K -I mol-l at 10 °C.251 L mol-l L mol-l = 0.314 I K-l mol-l Therefore. 4. = 0. Given: a = 3.

54 J K-l mol-l) This is negative. SOLUTION f Using equation 4. In this case the increase in order due to the crystallization of part of the ice is more than compensated for by the increase in disorder of the system as a whole by the rise in temperature. If the water was at -10 °C in an isolated system.15 K)(. 4. but part of the water would freeze. (b) Obtain an expression for AG2 using the more accurate approximation that MI = MIl + (T. assuming MI is independent of temperature.62 dG2lT dGl/T d(i1G/7) = - f T2 (Llli/T2)dT TI i1Gl T1=-MI i1~ -r-z- ( 1 TI-f2 1 ) i1G2 = i1Gl T2/Tl + MI[l -(T2/Tl)] 4.20. What is the change in the molar Gibbs energy for liquid water when it is compressed to 1000 bar? SOLUTION . assuming a constant molar volume. the temperature would rise. To a first approximation the increase in molar Gibbs energy can be calculated using caG/ap)T = V.10 (a) Integrate the Gibbs-Helmholtzequation to obtain an expression for AG2 at temperature T2 in terms ofAGI at TI.11 When a liquid is compressed its Gibbs energy is increased.Chapter 4/Fundamental Equations of Thermodynamics 53 L\GO = I1HO -TL\So = -5619 = -213. as expected for a spontaneous process at constant T and P.TI)ACp where TI is an arbitrary reference temperature.9 J mol-l J mol-l -(263.

r 54 4.15 K) In 0.12 An ideal gas is allowed to expand reversibly and isothermally (25 °C) from a pressure of 1 bar to a pressureof 0. 4.U=q+W=O = -4993 J mol-l (b) (c) (d) M = Wmax= 4993 J mol-l --MI= ~u+ ~ (PV) = 0 (e) ~ . assuminghelium is an ideal gas.1 bar. (a) What is the change in mC!larGibbs energy? (b) What would be the change in molar Gibbs energy if the process occurred irreversibly? SOLUTION =-- ( oG ) (a) --voP T ---:!iI p = (8.1 l1G = RTln ~ = -5708 J mol-l ~G = -5708 J mol-l (b) because G is a state function and depends only on the initial state and the final state.SOLUTION - (a) h.314 J K-l mol-l)(298.14 (g) !15.13 energy of formation at 100 bar'! SOLUTION 4. .

9 J g-1)(92. the work on the toluene is w = -PIlV= -RT= -(8. SOLUTION (a) Assuming that toluene vapor is an ideal gas and that the volume of the liquid is negligible. 111 °C.15 K = -13.340- 3193 = 30.314 J K-l mol-l)(384 K) = -3193 J mol-l (b) (c) (d) qp = 11 if = (361. (d) L\U. (c) MI.147 J mol-l (e) (f) If the Gibbs energy varies with temperature according to GIT = a + blT + clt? How will the enthalpy . calculate (a) w per mole. FQr the v~rization Qf toluene. and entropy vary with temperature? Check that these three equatIons are COnsIstent. (e) L\G. dU= q + w = 33.I Chapter 4/Fundamental Equations of Thermodynamics 55 - (f) L\U=O -- ~G (g) ~S=illi- T = 0 -4933 J mol-l 373.340 J mol-l. and (f) L\S.. The heat of vaporization at this temperature is 361.340 J mol-l 9 mol-l) = 33. (b) q per mole.13 MI = 33.91 g-l. SOLUTION G = aT + b + c/T (~) dT = -S = a -c/T2 p S = -a + c/T2 [ -] a(G/7) aT p = -H/T2 = -b/T2 -2c/T3 H= b + 2c/T G = H -TS = aT + b + c/T .38 J K-l mol-l Toluene is vaporized at its boiling point.

the calculation uses the following reversible . The density of ice at -3 °C is 0. SOLUTION ~ -{18.56 4. 489 Pa) l' ~G4= o H20(g.2+1. isothermal path: the calculation uses the following reversible H2O(1.15 K. 270.15 K.0 J mol-l 4.965 x 10-5 m3 mol-l ~ -{18.15 K. 270. 270.9996 kg m-3 and its vapor pressure is 489 Pa.9 : -65. The heat capacities of water and ice in the vicinity of the freezing point are 75. 105 Pa) -1' 105 489 V1dP=-1.917 x 103 kg m-3. and its vapor pressure is 475 Pa.9Jmol-l 475 H2O(S. 105 Pa) H20(S.2 J mol-l ~G: ~Gl + ~G2 + ~G3 + ~G4 + ~G5 :-1. SOLUTION Since the actual process in irreversible. The density of supercooled water at -3 °C is 0.802 x 10-5 m3 mol-l Since the actual process is irreversible.7Jmol-l 105 It1G5=f VsdP=-1. respectively. isobaric path.9996 x 10-3 kg !!!01--1) x 103 kg m-3) = 1. The molar enthalpy of fusion of ice is 6000 J mol-l at 0 °C.18 Calculate the molar Gibbs energy of fusion when supercooled water at -3 °C freezes at constant T and P.15 K. 475 Pa) ~G3 = RTln (475/489) = -65.7+0-65.015 1 -(0.3 and 38 J K-l mol-l. 489 Pa) = H20(g. 270.015 x 10-3 kg mo-l-~ s(0.15 K. 475 Pa) H20(1. 270.15 K.917 x 103 kg m-3) = 1.17 Chapter 4/Fundamental Equations of Thermodynamics Calculate the change in molar Gibbs energy G when supercooled water at -3 °C freezes at constant T and P. 270.

A. 270. 270.56) = -63. U.15 ~fusH(270.is use~. 273.15)(. a real gas has a fugacity coefficient ~ of 2.15 = -6000 + (38 -75. 270.!.15 + ~fusCp In(270.u(real) = . SOLUTION aP RT2 .15 = 1. 1 bar) t H20(1.21.u(ideal) = Rnnf/J = (8.u° + Rnn(f/JP/PO) . To this degreeof approximation derive the expressionsfor G. 1 bar) -7 H20(S. what is the difference in the chemical potential of this real gas and an ideal gas? SOLUTION .15 K.3)( -3) = -5888 J mol-l ~fusS(270.15 K). and V.15 K) + J 273. H. .15 K.15 K) = -6000/273.15 K) separately and use L\fusG = L\fusH -270.7.T~fusS = -5888.15) ~fusCp dT = -21.00. we have to calculate L\fusH (270.72kJmol-l K)ln2 As shown in Example 4.u(real) -.15. 1 bar) -7 H20(S.uo + Rnn(P/PO) .314 J K-l mol-l)(298. At this pressure. 273.(270.15. S.Chapter 4/Fundamental Equations of Thermodynamics 57 H20(1.15 K) = ~fusH(273.15/273.15 L\fusS.6 J mol-l At 298.15 K and a particular pressure.56 J mol-l ~fusG = ~fusH. the fugacity of a van der Waals gas is given by a fairly simple expression if only the second virial-c~effic~en!.15 K) and L\fusS (270. 1 bar) To obtain L\fusG (270.u(ideal) = .

22 Show that if the compressibility factor is given by Z = 1 + BPIRT the fugacity is given byf=PeZ-l. calculate the fugacity of H2(g) at 100 bar at 298 K. IfZisnot very different from unity.4) that ( au/ay )T= a/\i2 V= ( aG ) RT a -=p+b-RT ap T 4.21 Using the relation derived in Example 4.9 bar 4. we can use the ideal gas law to obtain --U = Uo -(alV) Note that this agrees with the earlier result (Section 4. what is the fugacity of H2(g) at 50 bar and 298 K using its van der Waals constants? SOLUTION = exp(BPIR7) = exp(Z -I) .Since the second term is small.7. SOLUTION = 106..=Z so thatf= PZ. Using this approximation. eZ-l = 1 +(Z-l) +..

Chapter 4/Fundamental Equations of Thermodynamics 59 If z is not very different For H2(g) from unity.0891 1.194 1020.08314)(298) *4. The volume of solution containing 1000 g of H20 is given by 1020.0532 1.1 6 10 14 18 0. f = PZ.2 1031.6 cm3 Volume Containing Wt% 2 Molality 0. the molality is given by m(ZnCI2) = 20 x 1000/136. of ZnCl2 2 6 10 14 18 Density/g cm-3 SOLUTION 1.0.0335 f= (50 bar)(1.0167 g cm-3 -0 1 0 3.4 g 1.02476 L2 bar mol-2 = 1.28 9 mol-l) mol for 980 9 H20.1275 1.23 Calculate the partial molar volume of zinc chloride in I-molal ZnC12 solution using the following % by weight data.4683 0.1497 m 1000 9 of H2Q 1003.08314 L bar K-l mol-l 50 bar (0.14975 mol kg-l.0335) = 5.3 1045.17 bar ) 0. so that it contains 20 9 of ZnCl2 and 980 9 of H20.58 x 980 = 0. Since there are (20 g/136.610 .1665 Consider a kilogram of solution that is 2% by weight ZnCI2.2 1010.8152 1.0167 1.02661L mol-l . z = 1 + (b -a/R7) P/RT = 1 + ( 0. at 50 bar and 298 K.5 1.

.314 J K-l = -1239 L\mixS = -R(ylln J mol-l Yl + Y2 In Y2) = 4.15 K.60 Chapter 4/Fundamental Equations of Thermodynamics v m 0. How much work is required to separate these gases to produce a container of each at 1 bar and 298 K? SOLUTIQN The mixture can be separated by diffusion through a perfect semipermeable membrane. The highest partial pressure of each that can be reached is 1/2 bar.15 K)(0.mixSfor the fonnation of a quantity of air containing 1 mol of gas by mixing nitrogen and oxygen at 298. This yielded V= 999. this yields 30.25 A mole of gas A is mixed with a mole of gas B at 1 bar and 298 K.-l mol-l 4.1601 m + 4.2) = (8. Mathematica TMwas used to obtain a quadratic fit of the data.8 In 0.314)(298) In 2 = 3. 1 1 VdP = (2 mol) (RT/P)dP = (2 mol) RT In 2 w = (2 mol) 1/2 1/2 f f = 2(8. These gases then have to be compressed to 1 bar.06 cm3 4.mixG and /). SOLUTION L\mixG = RT(ylln Yl + Y2 In Y2) moI-l)(298. This yields 29.5 1 1.159 J K.4 kJ The actual process will require more work.706 + 21.8 + 0.5 2 The slope of this plot at m = 1 molar can be obtained by drawing a tangent at m = 1 and calculating its slope. Air may be taken to be 80% nitrogen and 20% oxygen by volume.4639)m. At m = 1 molal.3 cm3 mol-l.1601 + (2)(4.2In 0. and so this is the partial molar volume of ZnCl2. mol-l.24 Calculate /).4639 m2 so that the slope is 21.

Chapter 4/Fundamental Equations of Thermodynamics 61 4. H. the molar Gibbs energy is given by G=- Tln~ p where numerical constants Eave been omitted so that only the functional dependence on the natural ~~a!?:le!!. Derive the corresponding equations for S. is shown.26 In studying statistical mechanics we will find (see Table 16. of G..!hat is T and P.27 Statistical mechanics shows that for a monatomic ideal gas. the molar Gibbs energy is given by -5 = -2 T In T + T In p G . and Helmholtz energy can be calculated from the following Legendre transforms: ---5 p/2 A = G -PV = -2T In T + T In p -T = -T In p -T 4. SOLUTION The fundamental equation for G is --dG = -SdT+ VdP Since the molar entropy is given by and the molar volume is given by v= (~) ap =~ T The expressions for the molar enthalpy.. V. and A. internal energy. U.1) that for a monatomic ideal gas.

T and P. and n. ideal monatomic use the following A=G-PV If w.62 Chapter 4/Fundamental Equations of Thermodynamics where the numerical dependence information. SOLUTION Substitute the expressions for G and p into the Legendre transform to obtain -3 A = -2 T In T -T In V -T The fundarnental equation for the molar Helmholtz energy is --d4 = -SdTPdV Thus the molar entropy is given by s = -aT ( aA ) 5 3 -5 y = :2 + :2 In T + In V = :2 + In T3/2 V is given by and the molar volume P=-(~) av T =I v The values of the molar enthalpy and molar internal energy are given by the following H=A ---3 U=A Legendre transforms: 5 + TS+PV=:2T + TS=:2T Substituting V= TIP in these expressions yields the same equations obtained in the previous problem for these thermodynamic properties.-ewant to treat the thermodynamics lq~ing any information. and U for an ideal monatomic gas as a function of T and v. -Use the expression for A obtained in t~s way to calculate S. thermodynamics factors have been omitted so that only the functional If we ~ant to treat the losing any use on the natural variables. but we cannot differentiate this expression to obtain other thermodynamic properties unless the variables in the expression are the natural variables for the thermodynamic potential. H. to define the molar Helmholtz of an we Eave to gas at specified Legendre T and V without transform energy A. U. 4. V. is shown.28 We already know enough about the thennodynamics of a monatomic ideal gas to express \I. Show that these expressions agree with the expressions obtained in the preceding problem. and S in tenns of the natural variables of G. The moral is that we can change the variables in the expression for a thermodynamic property. namely T.ecified T and V without we cannot simply replace p with T/Vand -5 T G = -2 T In T + T In = even though this relatYon is correct. ~ . P. of an ideal monatomic gas at sE.

Chapter 4/Fundamental Equations of Thermodynamics 63 v = nRT/P The last equation is the Sackur-Tetrode equation.E.30 dS = (CvlT)dT+ (alK)dV -0.n ] } ] } ] } + nRTlr(~ In T) }J= (~) =RT(~-SO) +RTln [(L)5/2(~)] on T.0252 J K-l mol-l (as/ap)T = 0.n) of the ideal monatomic gas can be calculated by using the Legendre transform G = u + PV -TS The fundamental equation for G is dG = -SdT + VdP + .15K) and standard pressure PO(l bar).u are obtained by using the partial derivatives of G indicated by this fundamental equation. (aU/ap)T = ° 4. and.36 88.nR + nR{ ~ + In[ (~)5/2(~) = nR{~+ V= (~) gP In[ (~)5/2(~) = nRT/P T.udn Show that the correct expressions for S. The Gibbs energy G(T. 4.nRT{ ~ + In[ (~)5/2(~) S= -(~) oT P. V.n = -~nRT.2 J mol-l . (aH/p)T = V.P 2 1" Po Thus the correct expressions are obtained for S and Vand the equation for the chemical potential is consistent with }J = . where 5Y> is the molar entropy at the standard temperature YO(298.uo + RT In (PlPO). SOLUTION G = ~nRT+nRT.

14 J K-l mol-l.40 (a) 4993.1 kJ mol-l.51 4. G) 19.36 x 10-6 m3 mol-l -4731 I. (e) 19.34 kJ mol-l.52 !lvapG = -3.9 kJ mol-l 4.37 4.6 kJ mol-l. -11.39 4.6 kJ mol-l ~ .5 kJ mol-l.64 Chapter 4/Fundamental Equations of Thermodynamics 4. (d) -5229 J mol-l.45 4.88 I K-l L\vapS= 109. 19. (e) 22. (a) 6820 J mol-l 0.9 J K-l mol-l (d) 0 (b) 6072 J mol-l (a) -5229 J mol-l.690 J mol-l. (I) 19.14 J K-l mol-l 3100 J mol-l.754 kJ mol-l.754 kJ mol-l.46 4. 4991 J mol-l 33. (g) 0.16 J K-l mol-l 0.2033 x 10-3 m-3 kg-l (b) 19. (k) 0.3 J K-l mol-l LlvapH = 39. (h) 0. (d) -6.38 J K-l mol-l. (b) 3655 J mol-l 168. 73.41 4. 0 kJ mol-l (a) -6.49 0. (b) 5229 J mol-l. 15. (f) 0. (c) 0.50 4.44 4. -109. 3.0 J K-l mol-l. -37.42 4. (i) -5229 J mol-l. (b) 0.42 kJ mol-l (c) 75.47 4. -40.51 J K-l mol-l 0.97 J K-l mol-l. -13.43 4.14 J K-l mol-l. -34. (c) 0.38 4.52 J K-l mol-l.79 x 10-3 m3 kg-l (a) 0. O -2121 J mol-l ~G = RT In (P2IPI) + (b -aIR7)(P2 -PI) 4.

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