ChE 381Chemical Engineering Thermodynamics

Fall 2009
MWF 9:00am 9:50am
1126 Sweeney Hall
(100 Points total)

Mid-Term Exam #1

NAME: Solution by Eric Cochran

By writing my name I certify that I have abided by all
academic honesty policies.

This exam is closed book, closed course material

You may use a calculator.
Write your answers to be graded on the paper provided. Additional scratch paper is available
if needed.
If you wish for your work on scratch paper to be graded, add your initials to the page, and
insert it next to the problem it belongs to.

Show all of your work for full credit!

1
 Problem 1

Problem 1 (10 Points) For a process in which the pressure is not kept
constant, but P n = Pnt , can we write
Z
Q= CP dT

? Explain.

SOLUTION: Problem 1
No, Q is a path function that most certainly depends on how the final state is reached. For example,
consider the two following combinations of isochoric and isobaric paths. Assume constant CV / CP for
simplicity.

TA = 2T1 , PB , V1
PB = 2P1
(V)PA V1 (2P1 )
Q = CP T = CP R
= CP R
= 2CP T1

(P)V2
(P)V1 Q = CV T = CV R
=
Q = CV T = CV R
= CV T1 (P1 )(2V1 )
CV R
= 2CV T1

T1 , P1 , V1
P1 T2 , P1 , V2
P

(P)V2
Q = CV T = CV =
(P)V R
Q = CV T = CV R 1 = 12 CV T1 P
( 21 )(2V1 )
CV R
= CV T1

P
(V)PB V1 ( 21 ) 1
Q = CP T = CP R
= CP R
= C T
2 P 1
P1
PA = 2

V1 V2 = 2V1
V

CP dT = CP T = CP PV
R
For the entire state change R
= CP T1 .
For path A,
QA = CV T1 + 2CP T1 2CV T1 = (CP + R)T1

For path B,
1 1 R
QB = CV T1 + CP T1 + CV T1 = (CP )T1
2 2 2

2 of 7
 Problem 2

Problem 2 (20 Points) Reduce the energy balance for each of the fol-
lowing processes and systems to the simplest
possible form. Specify the system/control vol-
ume. State and justify any assumptions.

2a Steam flowing at steady state through a throttling valve.

Throttling valves typically operate isenthalpically (from homework problem 4.3)

Control volume: The throttling valve.
Potential energy (assume horizontal or small elevation change).
Kinetic energy (even though it will contribute slightly, we have seen the contribution
is usually small compared to other terms even when the velocity change is signifi-
Neglect:
cant)
Time derivatives (steady state, given)
Shaft work (the device requires no work to operate and drives no external devices)
Open system energy balance:
d(mU)c
dt
= (mH) mEP mEK + Q + Ws
| {z }
senthpc

This leaves
Q = 0

2b A tennis ball, bounced from shoulder height until it comes to rest on the
ground.

Closed system: The tennis ball.

Kinetic energy (assume the ball begins and ends at rest).
Work (assume the volume of the ball remains constant and assume that the ball
transfers 0 energy to the ground. Neglect friction from air resistance. You could also
Neglect:
argue that for accuracy you should keep this term but it will be small)
Heat (heat is the flux of energy due to a temperature difference. Assume T differ-
ences are so small that heat is negligible.)
Closed system energy balance:
Ut + EP + mEK = Q + W

This leaves
CV T = mgz

3 of 7
 Problem 2

2c A heated, lidless saucepan of boiling water.

Control volume: The water in the kettle. The system is not at steady state since the kettle is
uncovered and liquid water is continuously being converted to steam. The temperature however is
constant.
Potential energy.
Neglect: Kinetic energy (steam rising from the water slowly enough that this is really small)
Shaft work (the device requires no work to operate and drives no external devices)
Open system energy balance:

d(mU)c
= (mH) mEP mEK + Ws + Q
dt

This leaves
dmc
Uc = mHstem + Q
dt

2d A piece of hot steel immersed into a bucket of cold water.

System (option 1): The steel

Kinetic energy (assume the steel begins and ends at rest).
Neglect:
Work (neglect volume changes in the steel/water)
Closed system energy balance:
Ut + EP + mEK = Q + W

This leaves
CV T = Q

System (option 2): The steel and the water

Kinetic energy (assume the steel begins and ends at rest).
Work (neglect volume changes in the steel/water)
Neglect:
Heat (assume the bucket is well-insulated, so only heat transfer is within the system
boundary)
Closed system energy balance:

Ut = Utstee + Utter = EP mEK + Q + W

This leaves
(mCV T)stee + (mCV T)ter = 0

4 of 7
 Problem 3

Problem 3 (20 Points)

J
A balloon is inflated with a gas to 2 L and 11.5 bar at 300 K and suddenly explodes (CP = 29.1 mol K ).
Write the equation for the total work if the final temperature of the gas 221 K. (You do not need to
reach a numerical answer). State your assumptions.
Is the process reversible and why/why not?
SOLUTION: Problem 3
The process of the balloon exploding is a sudden process and one could argue based on that obser-
vation alone that it is irreversible.
Take the air in the balloon as a closed system. Then

Ut = Q + W

One assumption that may be made is that since the process is occurring so quickly, that even though
the gas ends up at a lower temperature than the surroundings that the amount of time elapsed is too
small for heat to be an important contribution. Thus this process can be modeled as an irreversible
adiabatic expansion, with Q = 0. (And the return of the released gas to room temperature could
subsequently be modeled as an isobaric expansion, for which there would be an additional work
term). So

P1 V1
W = Ut = nCV T = CV T
RT1

Another, more formal way to check if the process is irreversible is to consider SG , assuming the
balloon exploded at atmospheric pressure:

Q
T2 P2 J
SG = S Tsrr
= CP ln R ln = 11.4 >0
T1 P1 mol K

SG > 0 so the process is irreversible.

5 of 7
 Problem 4

Problem 4 (20 Points) For each of the following schemes indicate if

the process is possible or not and why.

(a)
TH SOLUTION: 4a
QH Not possible, heat transfer from a cold reservoir to a hot one is only
possible with the input of work:

W |QH | |QC |
Process S = <0
TH TC

Wde = H
|{z} Tsrr |{z}
S > 0
At most zero if work is <0
n o
QC exiting the process

TC So the work term must be positive

(b)
TH
QH

SOLUTION: 4b
W Possible, work can be converted completely into heat (Joules Experi-
Process
ments), and heat transfer from a hot reservoir to a cold one always
increases entropy.

QC
TC

(c)
TH
QH
SOLUTION: 4c
W Possible, for the same reason as above. Example: Rubbing a file on a
Process piece of metal resting on a block of ice. The rubbing (work) raises the
internal energy of the metal, which induces heat to flow to both a cold
reservoir (the ice) and a hot one (the air).
QC
TC

(d)
TH
QH

W
SOLUTION: 4d
Process Not possible, heat cannot be converted completely into work (Statement
1 of the second law).

QC
TC

6 of 7
 Problem 5

Problem 5 (30 Points)

Naphthalene (C10 H8 ) is catalytically converted with N2 (g) and H2 O(g) into HCN(g) and N2 O(g) at room
temperature. How much heat is required/released per mole of naphthalene? The combustion of 1
mole naphthalene releases 5157 kJ.
Standard Heats of Formation
kJ
Species H298 , mol
H2 O(g) -242
CO2 (g) -394
HCN(g) 135
N2 O(g) 33.2
C10 H8 (s) ?

First, write out the reaction and balance the stoichiometry:

C10 H8 + H2 O + N2 10 HCN + N2 O

The reaction is at room temperature, about 298K so we can neglect any heat capacity integrals.

T = 298 K T = 298 K
nC10 H8 = 1mol nHCN = 10mol
nH2 O = 1mol nN2 O = 1mol
nN2 = 1mol

H = Q

The above diagram indicates that

Q = 10H298,HCN + H298,N H298,C H298,H H298,N

2O 10 H8 2O 2

We are not given H298,C , but that the combustion of 1 mole C10 H8 releases 5157 kJ:
10 H8

C10 H8 + 12 O2 10 CO2 + 4 H2 O

T = 298 K T = 298 K
nC10 H8 = 1mol nCO2 = 10mol
nO2 = 12mol nH2 O = 4mol

H = Q

The above diagram indicates that

H = Q = 10H298,CO + 4H298,H H298,C 12H298,O = 5157kJ
2 2O 10 H8 2

kJ
Solving for H298,C : H298,C = 5157 + 10H298,CO + 4H298,H = 249 mol
10 H8 10 H8 2 2O

Finally, Q = 10H298,HCN + H298,N H298,C H298,H = 1376.2 kJ required

2O 10 H8 2O

7 of 7