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 Raoult’s 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 Raoult’s law.
(c) At 200 K, hydrogen is supercritical, and modeling the hydrogen/propane system at this tempera-
ture by Raoult’s 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 Raoult’s law to a good approximation.
(e) Water and n-decane are much too dissimilar to be modeled by Raoult’s 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:
mi
yi P V t = n i RT or pi V t = RT
Mi

where m i is the mass of species i, Mi is its molar mass, and pi is its partial pressure, defined 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:

MH2 O pH2 O V t Mair pair V t

m H2 O = and m air =
RT RT
(a) By definition,
m H2 O MH2 O pH2 O
h≡ or h=
m air Mair pair
Since the partial pressures must sum to the total pressure, pair = P − pH2 O ; whence,

MH2 O p H2 O
h=
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:

MH2 O PHsat
2O
h sat =
Mair P − PHsat
2O

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 (c) Percentage humidity and relative humidity are defined as follows:

h pH2 O P − PHsat
2O
pH2 O
h pc ≡ sat = sat (100) and h rel ≡ (100)
h PH2 O P − pH2 O PHsat
2O

Combining these two definitions to eliminate pH2 O gives:

P − PHsat
2O
h pc = h rel
P − PHsat
2O
(h rel /100)

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 Henry’s 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 γ1 and ln γ2 ,

y1 P = x1 exp(Ax22 )P1sat and y2 P = x2 exp(Ax12 )P2sat

These equations sum to give:

P = x1 exp(Ax22 )P1sat + x2 exp(Ax12 )P2sat

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

x1 exp(Ax22 )P1sat
y1 =
x1 exp(Ax22 )P1sat + x2 exp(Ax12 )P2sat
For x1 = x2 this equation obviously reduces to:

P1sat
P=
P1sat + P2sat

10.23 A little reflection 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 definition 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 or K 1 x1 + K 2 (1 − x1 ) = 1

1 − K2
Solve for x1 : x1 =
K1 − K2

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

K 1 (1 − K 2 )
y1 =
K1 − K2

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 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:

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

z 1 (K 1 − K 2 ) − (1 − K 2 )
Solve this equation for V: V=
(K 1 − 1)(1 − K 2 )

Note that the relative amounts of liquid and vapor phases do depend on z 1 .
ni xi
10.35 Molality ≡ Mi = =
ms x s Ms

where subscript s denotes the solvent and Ms is the molar mass of the solvent. The given equation
may therefore be written:


xi 1
= ki yi P or xi = yi P
x s Ms x s Ms k i

Comparison with Eq. (10.4) shows that

1 1
Hi = or for xi → 0 Hi =
x s Ms k i Ms k i

For water, Ms = 18.015 g mol−1 or 0.018015 kg mol−1 .

1
Thus, Hi = = 1633 bar
(0.018015)(0.034)

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

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