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Assignment #5 Solution

1.

1.a.

Add the Raoults Law expressions for both species

x

1

P

sat

1

(T) + x

2

P

sat

2

(T) = (y

1

+ y

2

)P

x

1

P

sat

1

(T) + (1 x

1

)P

sat

2

(T) = P

(1.1)

The Antoine equation allows us to express P

sat

1

and P

sat

2

in terms of T

P

sat

1

= exp

_

A

1

B

1

T + C

1

_

P

sat

2

= exp

_

A

2

B

2

T + C

2

_ (1.2)

where the constants A

i

, B

i

, and C

i

are material properties. Plug Eqns. 1.2 into Eqn.

1.1 to obtain one function in terms of one unknown (T). Solve the equation to nd

T = 382 K . Then, use this value to nd x

1

= 0.173 from Eqn. 1.1.

1.b.

In this part, we have T and can solve directly for the saturation pressures. Use this

information and Eqn. 1.1 to nd x

1

= 0.433 . Then, use the Raoults Law expression

for one of the components to nd y

1

= 0.650 .

1

2.

2.a.

Add the Raoults Law expressions for both species

x

1

1

P

sat

1

+ x

2

2

P

sat

2

= (y

1

+ y

2

)P

x

1

1

P

sat

1

+ (1 x

1

)

2

P

sat

2

= P

x

1

exp{0.85(1 x

1

)

2

}P

sat

1

+ (1 x

1

) exp{0.85(x

1

)

2

}P

sat

2

= P

(2.1)

The nal line is a single equation with one unknown (P). Plug in all of the known values

to nd P = 47.2 kPa . Then, rearrange Raoults Law for one of the components to nd

y

1

y

1

=

x

1

exp{0.85(1 x

1

)

2

}P

sat

1

P

= 0.182

2.b.

Rearrange Raoults Law for the rst component

P =

x

1

exp{0.85(1 x

1

)

2

}P

sat

1

y

1

(2.2)

Set this expression equal to Eqn. 2.1

x

1

exp{0.85(1 x

1

)

2

}P

sat

1

y

1

= x

1

exp{0.85(1 x

1

)

2

}P

sat

1

+ (1 x

1

) exp{0.85(x

1

)

2

}P

sat

2

Here, the only unknown is x

1

. Solve this equation to nd x

1

= 0.011 . Then, plug x

1

into Eqn. 2.2 to nd P = 40.4 kPa .

2.c.

At the azeotrope, x

1

= y

1

. Therefore, we can rewrite Raoults Law as P =

1

P

sat

1

. Set

this equation equal to Eqn. 2.1

2

P =

1

P

sat

1

= x

1

1

P

sat

1

+ (1 x

1

)

2

P

sat

2

(1 x

1

)

1

P

sat

1

= (1 x

1

)

2

P

sat

2

P

sat

1

P

sat

2

=

2

1

=

exp{0.85(x

1

)

2

}

exp{0.85(x

2

)

2

}

= exp{0.85[x

2

1

(1 x

1

)

2

]}

ln

_

P

sat

1

P

sat

2

_

= 0.85[x

2

1

(1 2x

1

+ x

2

1

)]

= 0.85[2x

1

1]

x

1

=

1

2

_

1

0.85

ln

_

P

sat

1

P

sat

2

_

+ 1

_

Plug in the known values of the saturation pressures to nd x

1

= y

1

= 0.900 .

3

3.

Make two assumptions:

1. At 1500 K, silver acts as an ideal gas

2. The molar volume of the vapor molar volume of the liquid

With these two assumptions, we can write

dP

sat

P

sat

=

h

vap

dT

RT

2

Rearrange this expression

dP

sat

dT

=

h

vap

P

sat

RT

2

(3.1)

Dierentiate the expression for P given in the problem statement

dP

sat

dT

=

_

14260

T

2

0.458

T

_

exp

_

14260

T

0.438 ln(T) + 12.23

_

=

_

14260

T

2

0.458

T

_

P

sat

Set this expression equal to Eqn. 3.1

_

14260

T

2

0.458

T

_

=

h

vap

RT

2

Finally, solve for h

vap

h

vap

= R(14260 0.458T)

= 112.8

kJ

mol

4

4.

From Problem 6.13, we know that

_

g

T

_

Sr(s)

=

_

g

T

_

Sr(l)

and

_

(g/T)

T

_

P

=

h

T

2

(4.1)

Since h =

_

C

p

dT, we can nd the enthalpies of the liquid and solid phases as functions

of temperature

h

l

(T) = 49179 +

_

T

1500 K

35.146dT = 35.146T 3540

h

s

(T) = 20285 +

_

T

900 K

37656dT = 37.656T 16305.4

Next, calculate reference

_

g

T

_

values for both phases. Use the values provided in the

problem statement to calculate g = h Ts. Then, divide by T to nd

_

g

l

T

_

ref

= 83.85

J

mol K

_

g

s

T

_

ref

= 68.68

J

mol K

Now we can write a general expression for

_

g

T

_

using Eqn. 4.1

_

d

_

g

T

_

=

_ _

(g/T)

T

_

P

dT =

_

h

T

2

dT

Substitute in the expressions we obtained for enthalpies and the reference

_

g

T

_

values to

nd

_

g

l

/T

83.85

d

_

g

T

_

=

_

T

1500 K

_

35.146T 3540

T

2

_

dT

_

g

l

T

_

= 35.145 ln T

3540

T

+ 176.04

_

g

s

/T

68.68

d

_

g

T

_

=

_

T

900 K

_

37.656T 16305.4

T

2

_

dT

_

g

s

T

_

= 37.646 ln T

16305.4

T

+ 205.5

5

Now, set

_

g

s

T

_

=

_

g

l

T

_

and solve for T to nd

T

melt

= 1060 K

Use the following denition to nd the enthalpy of melting

h

fus

= h

s

(T

melt

) h

l

(T

melt

)

= 26.30

kJ

mol

33.71

kJ

mol

= 7.41

kJ

mol

6

5.

5.a.

The range of pressures is from the bubble point to the dew point. First, nd the bubble

point pressure. At this point, x

1

= z

1

= 0.65

P(x

1

, x

2

) = x

1

1

(x

1

, x

2

)P

sat

1

+ x

2

2

(x

1

, x

2

)P

sat

2

P

bubble

= 0.65 exp[0.67(1 0.65)

2

](32.27 kPa) + (1 0.65) exp[0.67(0.65)

2

](73.14 kPa)

= 56.75 kPa

At the dew point, y

1

= z

1

= 0.65. Write two equations to nd the two unknowns P

dew

and x

i

P

dew

=

x

1

y

1

1

P

sat

1

P

dew

= x

1

1

P

sat

1

+ x

2

2

P

sat

2

Guess and check or use Excel to force these two equations to have the same output value

of P

dew

= 43.86 kPa. Thus, the pressure range is [43.86 kPa, 56.75 kPa] .

5.b.

Perform a BUBL P calculation

P = 0.7 exp[0.67(10.7)

2

](32.27 kPa)+(10.7) exp[0.67(0.7)

2

](73.14 kPa) = 54.46 kPa

5.c.

First, nd y

1

y

1

=

x

1

1

P

sat

1

P

= 0.441

Then, nd the vapor composition

=

z

1

x

1

y

1

x

1

= 0.193

7

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