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You are on page 1of 11

Assignment #3 Solution

1.

1.a.

Use the cyclic rule

_

P

T

_

v

_

v

P

_

T

_

T

v

_

P

= 1

Apply the denitions of and

_

v

T

_

P

= v

_

v

P

_

T

= v

Substitute in these expressions

_

P

T

_

v

=

_

P

v

_

T

_

v

T

_

P

=

_

v

v

_

=

= 15.9

bar

C

We can use this to nd T

T =

P

_

P

T

_

v

=

(121 bar 1 bar)

15.9

bar

C

= 7.5

C

1

1.b.

Rearrange the provided expression for C

P

C

P

C

v

= T

_

P

T

_

v

_

v

T

_

P

= T

_

P

v

_

T

_

v

T

_

2

P

= Tv

u =

_

C

v

dT

=

_

T

2

T

1

_

C

P

Tv

_

dT

= C

P

(T

2

T

1

)

v

2

2

(T

2

2

T

2

1

)

= 938

J

mol

432

J

mol

= 506

J

mol

where v =

MW

= 7.35 10

5 m

3

mol

. Use this value to nd h

h = u + (Pv)

= u +vP

= 1388

J

mol

Now, nd the change in entropy

ds =

_

s

T

_

v

dT +

_

s

v

_

T

dv

=

_

s

T

_

v

dT =

C

v

T

dT

s =

_

T

2

T

1

1

T

_

C

P

Tv

_

dT

= C

P

ln

_

T

2

T

1

_

v

2

T

= 1.70

J

mol K

2

1.c.

Perform an energy balance

u = Q = 506

J

mol

3

2.

Begin with the dierential for internal energy

du = C

v

dT +

_

u

v

_

T

dv

Thus

_

u

T

_

v

= C

v

_

u

T

_

P

= C

v

+

_

T

_

P

T

_

v

P

_ _

v

T

_

P

_

u

T

_

P

_

u

T

_

v

=

_

T

_

P

T

_

v

P

_ _

v

T

_

P

2.a.

For an ideal gas, P =

RT

v

.

T

_

P

T

_

v

P = T

_

R

v

_

RT

v

= 0

Therefore

_

u

T

_

P

_

u

T

_

v

= 0

2.b.

For a van der Waals gas

P =

RT

v b

a

v

2

Use this to nd that

_

P

T

_

v

=

R

v b

So that

T

_

P

T

_

v

P =

a

v

2

Also realize that

4

dP =

R

v b

dT

RT

(v b)

2

dv +

2a

v

3

dv

Rearrange this and solve for

_

v

T

_

P

_

v

T

_

P

=

R

(vb)

RT

(vb)

2

2a

v

3

=

_

T

(v b)

2a(v b)

Rv

3

_

1

Therefore

_

u

T

_

P

_

u

T

_

v

=

a

v

2

T

vb

2a(vb)

Rv

=

aRv(v b)

RTv

3

2a(v b)

2

5

3.

3.a.

Recall the following denitions

=

1

v

_

v

T

_

P

=

1

v

_

v

P

_

T

Use them to nd

=

_

v

T

_

P

_

v

P

_

T

=

_

v

T

_

P

_

P

v

_

T

Apply the cyclic rule

1 =

_

v

T

_

P

_

P

v

_

T

_

T

P

_

v

Thus,

=

_

P

T

_

v

3.b.

Write T = T(v, P) and write

dT =

_

T

v

_

P

dv +

_

T

P

_

v

dP (3.1)

We can also write

ds =

C

v

T

dT +

_

P

T

_

v

dv =

C

P

T

dT

_

v

T

_

P

dP

Rearrange this equation and solve for dT. Then, set it equal to Equation 3.1 and group

terms

_

T

v

_

P

dv +

_

T

P

_

v

dP =

T

C

P

C

v

_

P

T

_

v

dv +

T

C

P

C

v

_

v

T

_

P

dP

__

T

v

_

P

T

C

P

C

v

_

P

T

_

v

_

dv +

__

T

P

_

v

T

C

P

C

v

_

v

T

_

P

_

dP = 0

6

In order for this to be true, both terms in square brackets must be equal to zero. There-

fore, we can write

_

T

v

_

P

=

T

C

P

C

v

_

P

T

_

v

C

P

C

v

= T

_

P

T

_

v

_

v

T

_

P

= T

_

v

T

_

P

=

Tv

2

7

4.

Determine the ideal gas heat capacity from Table A.2.1

C

P

R

= 1.213 + 28.785 10

3

T 8.824 10

6

T

2

This process is isentropic, so construct a solution so that the sum of the entropy changes

for each step is equal to zero.

4.a.

Choose two steps as follows

Write the dierential of entropy

ds =

_

s

T

_

v

dT +

_

s

v

_

T

dv = 0

=

C

v

T

dT +

_

P

T

_

v

dv

For this system, use

P =

RT

v b

a

v

2

_

P

T

_

v

=

R

v b

to nd the entropy change for the rst step

8

s

1

=

_

ds

=

_

v

2

v

1

_

P

T

_

v

dv

=

_

v

2

v

1

R

v b

dv

= Rln

_

v

2

b

v

1

b

_

Because P

2

is low, we can assume that the gas at this state behaves as an ideal gas

s

1

= Rln

_

RT

2

P

2

b

v

1

b

_

Next, calculate s

1

s

2

=

_

T

2

T

1

C

v

T

dT = R

_

T

2

623.15 K

0.213 + 28.785 10

3

T 8.824 10

6

T

2

T

dT

Add both of the entropy changes and set them equal to zero

s = s

1

+ s

2

= 0

Substitute in the expressions from above and solve for T

2

= 448.3 K .

9

5.

Perform an energy balance to nd that u = 0. The gas is not ideal under the stated

conditions, so we must create a path that connects the initial to the nal state through

three steps into a region where we can assume the gas behaves as an ideal gas, as shown

below

First, nd u

1

u

1

=

_

v=

v

i

_

u

v

_

T

dv

=

_

v=

v

i

_

T

_

P

T

_

v

P

_

dv

For the van der Waals equation of state

_

P

T

_

v

=

R

v b

+

a

T

2

v

2

Plug this into the expression for u

1

u

1

=

_

v

i

=2.510

4

_

RT

v b

+

a

Tv

2

P

_

dv =

_

v

i

=2.510

4

2a

T

i

v

2

dv = 1120

J

mol

Perform a similar procedure for the third step

u

3

=

_

v

f

=510

4

_

RT

v b

+

a

Tv

2

P

_

dv =

_

v

f

=510

4

2a

T

f

v

2

dv =

168000

T

f

J

mol K

The molar volume is innite for step 2, so we can use the ideal gas heat capacity to nd

u

2

10

u

2

=

3

2

R(T

f

300 K)

Sum the internal energies

u = u

1

+ u

2

+ u

3

= 1120

J

mol

+

3

2

_

8.314

J

mol K

_

(T

f

300 K)

168000

T

f

= 0

Solve for T

f

= 262 K .

11

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