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11 5

3.8

Calculate the changes in H and G/T when 1,3 butadiene, in the idealgas state, is heated at constant pressure from 300 to 1000 K. The heat capacity for 1,3 butadi- ene as an ideal gas is given by c p R = A + B( T 100 ) + C( T 100 )

2

(P3.8.1)

where T is in Kelvin, A = 0.290, B = 4.70476, and C = 0.15714. 3.9 One mole of nitrogen undergoes the following three-step cyclic process, which starts and ends at 5 bar and 5 liter: (a) Reversible expansion at constant isothermal compressibility to 10 liter, (b) Reversible compression at constant volume expansivity to 5 liter, (c) Irreversible isometric cooling to 5 bar. Determine the net work done and the net heat transferred over one cycle. Assume the ideal-gas equation is obeyed with cv = 5R/2. 3.10 (a) Ten moles of liquid water are initially at 20C and 1 bar. The water is to be compressed isothermally to 500 bar, with the compression done in such a way that the required work is minimized. Use the response functions for water from Table 3.2 to estimate the nal density, the amount of work required, and the direction and amount of any heat transferred. (b) Repeat (a) for ten moles of air, assuming air is an ideal gas with cv = 5R/2. 3.11 (a) Prove (3.3.30): the ratio of compressibilities is the ratio of heat capacities. (b) Evaluate this ratio for air and for water using data from Table 3.2. 3.12 Consider a pure ideal gas with constant heat capacity cv . For an arbitrary state (P1, v1), prove (a) that the slopes of the reversible adiabat and reversible isotherm through (P1, v1) are both negative, and (b) that, as v increases, P along the adiabat decreases faster than does P along the isotherm. 3.13 Heat capacities are functions of state and their response to changes in pressure or volume are related to the equation of state. Prove that C p = P

TN

2V T T2 PN

and

2 P C v = T T2 V TN

VN

11 6

FUNDAMENTAL RELATIONS

3.14 Pure water is to be compressed from 1 bar, 20C. (a) If the compression is done adiabatically to 100 bar, can the nal temperature be 30C? (b) If the compression is done adiabatically to 200 bar, what is the lowest possible nal temperature? 3.15 For a substance with constant cp, show that isobaric cooling and heating pro- cesses produce straight lines on a plot of s vs. ln T.

3.16 The sonic velocity w in a uid is a thermodynamic property related to the adia- batic compressibility by w = 1/(s )1/2, where is the mass density of the uid. (a) Show that w can also be written in terms of the isothermal compressibility 1 w = -----------------------------------------------------------T ( 1 ( TV v ) cp ) (P3.16.1 )

(b) Use data from Table 3.2 to compare the sonic velocity in air (used in deter- mining Mach numbers for speeds of aircraft) with that in water (used in detecting submarines and other underwater objects). (c) What are the magnitudes of the absolute and relative errors in the sonic velocity of air if we assume s = T at 1 bar and 25C? 3.17 Consider a binary mixture of 1 and 2 having molar volume v. Show that the par- tial molar volumes can be written in the form of Legendre transforms, v V 1 = v x2 x 2

TP

(P3.17.1 )

and

V2

v = vx 1 x TP 1

(P3.17.2 )

0.8306 g/cm 3. At these conditions, the partial molar volume of water is V 2 = 15.68 cm3/mole. (a) What is the value of V 1 , the partial molar volume for ethanol? (b) Estimate the mixture density when x1 is changed from 0.70 to 0.71 at xed T and P. (c) Do you expect V1

assumptions made. 3.19 At 20C and 1 bar a binary liquid mixture of 1 and 2 has the composition depen- dence of the partial molar volume of component 1 given by V1 = v pure 1+ Ax 2

2

(P3.19.1 )

where A is a constant. Find the analogous expression for V 2 . 3.20 Consider a binary mixture of components 1 and 2 at xed T and P. For such a mixture, show whether or not it is legitimate to represent a partial molar prop- erty as a linear function of composition. For example, show whether we may write the partial molar volume as V 1 = vpure x2 where A is a constant, independent of composition.

1

+A

(P3.20.1 )

3.21 (a) What information would enable you to integrate (3.5.7) to obtain S? (b) What information would enable you to integrate (3.5.13) to obtain S? 3.22 For a single-phase substance containing any number of components, show that Cv dT + V ( T dU i = 0

i v

P ) ( dT T dP )

N i

(P3.22.1 )

3.23 A stream of air (stream A) initially at 20C is to be heated to 60C by bringing it into contact with a second air stream (stream B) in a doubletube heat exchanger. Stream B enters the exchanger at 80C. Assume the exchanger is well-insulated and operates at constant P; also assume air obeys Pv = RT and has constant cp. (a) If the exchanger operates countercurrently and the mass ow rates of the two streams are the same, determine the outlet temperature of stream B. (b) If the exchanger operates co-currently and the mass ow rates are equal, determine the outlet temperature of stream B. (c) Schematically sketch, on the same diagram, your results from part (b) in the form of the temperature of each stream versus distance down the exchanger from inlet to outlet. Compare and discuss your results for (a) and (b); in par- ticular, whats the same and what differs in processes (a) and (b)? 3.24 Derive the expression for the shaft work wsh done by a reversible adiabatic com- pressor, assuming the uid is an ideal gas with constant heat capacities. Your result should take the form P out ---------= ---------------- 1 P in ( 1 ) RT in

( 1 )

wsh

(P3.24.1 )

where is the ratio of heat capacities (a measurable), = cp/cv . 3.25 A Joule-Thomson ( J-T) expansion occurs whenever a steadily owing uid passes through a conduit or device that is well-insulated and that involves no shaft work. (a) Because of friction, we expect a pressure drop across a J-T expansion; that is, Pout < Pin . Develop a thermodynamic argument to conrm this. (b) However, show thermodynamically that there is no constraint on the

relation between Tin and Tout : a uid may be heated or cooled by a JT expansion. (c) The J-T coefcient is dened by (T/P)h. Find an expression for this deriva- tive solely in terms of measurables. (d) Evaluate the J-T coefcient for an ideal gas. 3.26 Complete the derivation of (3.5.11) from (3.5.10) by showing that U N i TV N = Hi T v Vi (P3.26.1 )

j i

3.27 The forms of the fundamental equation contain ve conceptuals: U, S, H, A, and G. For these properties we can only obtain changes, such as U, or values relative to a prechosen reference state, such as U = Uref + U. As part of a process design project, you need to construct a table of these ve properties for a certain pure substance (like the steam tables). First, you select a reference state: a phase, a temperature Tref , and a pressure Pref . (a) Of the ve conceptuals, how many can be arbitrarily set to zero at the reference state? (b) Let n represent the number found in part (a); n 5. At the reference state, can any n of the ve conceptuals be set to zero? Or are there constraints on the identities of the n properties? 3.28 In modern steam tables, the reference state is usually taken to be the saturated liquid at its triple point (Tref = 273.16 K, Pref = 0.611 kPa); at this state the internal energy and entropy are set to zero: uref = sref = 0. An excerpt from such a table follows. P = 1 bar T(C) 100 400 h( J/g) 2676.2 3278.2 s ( J/g K) 7.3614 8.5435 P = 20 bar h( J/g) ... 3247.6 s ( J/g K) ... 7.1271

(a) For 1 g of steam heated isobarically at 1 bar from 100 to 400C, compute h, s, and g. (b) For 1 g of steam compressed isothermally from 1 to 20 bar at 400C, compute h, s, and g. (c) If, instead of the saturated liquid used above, the reference state is chosen to be superheated steam at Tref = 100C and Pref = 10 kPa, then the above table becomes the one below. For the same processes as in (a), use the following table to compute h, s, and g. P = 1 bar T(C) h( J/g) s ( J/g K) 3.9434 P = 20 bar h( J/g) s ( J/g K) ...

10 11.3 ... 0 40 590.7 5.1255 560.1 3.7091 0 (d) For the same processes as in (b), use this new table to compute h, s, and g. (e) Compare your results from (a) with those from (c) and compare your results from (b) with those from (d). Explain any differences.

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