Chapter 10 - Section B - Non-Numerical Solutions

10.5 For a binary system, the next equation following Eq. (10.2) shows that P is linear in x1 . Thus no maximum or minimum can exist in this relation. Since such an extremum is required for the existence of an azeotrope, no azeotrope is possible. 10.6 (a) Because benzene and toluene are chemically similar and the pressure is only 1(atm), this system can be modeled by Raoults law to a good approximation. (b) Although n-hexane and n-heptane are chemically similar, a pressure of 25 bar is too high for modeling this system by Raoults law. (c) At 200 K, hydrogen is supercritical, and modeling the hydrogen/propane system at this temperature by Raoults law is out of the question, because no value of P sat for hydrogen is known. (d) Because isooctane and n-octane are chemically similar and at a temperature (373.15 K) close to their normal boiling points, this system can be modeled by Raoults law to a good approximation. (e) Water and n-decane are much too dissimilar to be modeled by Raoults law, and are in fact only slightly soluble in one another at 300 K. 10.12 For a total volume V t of an ideal gas, P V t = n RT . Multiply both sides by yi , the mole fraction of species i in the mixture: yi P V t = n i RT or pi V t = mi RT Mi

where m i is the mass of species i, Mi is its molar mass, and pi is its partial pressure, dened as pi yi P. Solve for m i : Mi pi V t mi = RT Applied to moist air, considered a binary mixture of air and water vapor, this gives:

m H2 O =

MH2 O pH2 O V t RT

and

m air =

Mair pair V t RT

(a) By denition, h

m H2 O m air

or

h=

MH2 O pH2 O Mair pair

Since the partial pressures must sum to the total pressure, pair = P pH2 O ; whence,

h=

p H2 O MH2 O Mair P pH2 O

(b) If air is in equilibrium with liquid water, then the partial pressure of water vapor in the air equals the vapor pressure of the water, and the preceding equation becomes:

h sat =

PHsat MH2 O 2O Mair P PHsat 2O

676

(c) Percentage humidity and relative humidity are dened as follows: h pc

pH2 O P PHsat h 2O (100) sat = sat PH2 O P pH2 O h

and

h rel

p H2 O (100) PHsat 2O

Combining these two denitions to eliminate pH2 O gives:

h pc = h rel

P PHsat (h rel /100) 2O

P PHsat 2O

10.14 Because the vapor space above the liquid phase is nearly pure gas, Eq. (10.4) becomes P = xi Hi . For the same mole fraction of gas dissolved in the liquid phase, P is then proportional to Hi . Values given in Table 10.1 indicate that were air used rather than CO2 , P would be about 44 times greater, much too high a pressure to be practical. 10.15 Because Henrys constant for helium is very high, very little of this gas dissolves in the blood streams of divers at approximately atmospheric pressure. 10.21 By Eq. (10.5) and the given equations for ln 1 and ln 2 ,
2 y1 P = x1 exp(Ax2 )P1sat

and

2 y2 P = x2 exp(Ax1 )P2sat

These equations sum to give:

2 2 P = x1 exp(Ax2 )P1sat + x2 exp(Ax1 )P2sat

Dividing the equation for y1 P by the preceding equation yields: y1 =

2 x1 exp(Ax2 )P1sat 2 2 x1 exp(Ax2 )P1sat + x2 exp(Ax1 )P2sat

For x1 = x2 this equation obviously reduces to:

P=

P1sat P1sat + P2sat

10.23 A little reection should convince anyone that there is no other way that BOTH the liquid-phase and vapor-phase mole fractions can sum to unity. 10.24 By the denition of a K -value, y1 = K 1 x1 and y2 = K 2 x2 . Moreover, y1 + y2 = 1. These equations combine to yield: K 1 x1 + K 2 x2 = 1 Solve for x1 : or K 1 x1 + K 2 (1 x1 ) = 1

x1 =

1 K2 K1 K2

Substitute for x1 in the equation y1 = K 1 x1 :

y1 =

K 1 (1 K 2 ) K1 K2

677

Note that when two phases exist both x1 and y1 are independent of z 1 . By a material balance on the basis of 1 mole of feed, x1 L + y1 V = z 1 or x1 (1 V) + y1 V = z 1

Substitute for both x1 and y1 by the equations derived above:

K 1 (1 K 2 ) 1 K2 V = z1 (1 V) + K1 K2 K1 K2

Solve this equation for V:

V=

z 1 (K 1 K 2 ) (1 K 2 ) (K 1 1)(1 K 2 )

Note that the relative amounts of liquid and vapor phases do depend on z 1 . 10.35 Molality Mi =

xi ni = x s Ms ms

where subscript s denotes the solvent and Ms is the molar mass of the solvent. The given equation may therefore be written: xi = ki yi P x s Ms

or

xi

1 x s Ms k i

= yi P

Comparison with Eq. (10.4) shows that Hi = 1 x s Ms k i

or for xi 0

Hi =

1 Ms k i

For water, Ms = 18.015 g mol1 Thus,

or

0.018015 kg mol1 .

Hi =

1 = 1633 bar (0.018015)(0.034)

This is in comparison with the value of 1670 bar in Table 10.1.

678