Problem 1.

Enthalpy
Given: Table of properties for two substances

Substance p (bar) T (K)  (kg/m3) u (kJ/kg)

A 1.00 300 1.20 0.00
A 20.0 300 24.0 0.50
A 20.0 1000 7.20 440

B 1.00 300 500 0.00

B 20.0 300 505 1.00
B 20.0 1000 490 800
Find: (a) enthalpy, h at each condition
(b) which substance likely to be gas
(c) can gas be considered calorically perfect
Assume: none
Analysis:
a) Enthalpy
By definition, h  u  p  . So for the first condition, we have
p 1.00bar 106 N m 2 J
hu  0 kJ kg   83.3 kJ kg
 1.20 kg m 3 1 bar Nm
Using a similar approach for the other conditions, we get
Substance p (bar) T (K)  (kg/m3) u (kJ/kg) h (kJ/kg)
A 1.00 300 1.20 0.00 83.3
A 20.0 300 24.0 0.50 83.8
A 20.0 500 14.0 110 253
A 20.0 1000 7.20 440 718

B 1.00 300 500 0.00 0.20

B 20.0 300 505 1.00 5.00
B 20.0 500 501 220 224
B 20.0 1000 490 800 804

b) Gas
For an ideal gas,   p RT ; so density should be roughly proportional to pressure for a gas.
Since density is nearly independent of pressure for substance B, it is unlikely to be a gas.
For substance A, the first two conditions show that the density is proportional to pressure
when the temperature is held constant. So substance A is likely to be a gas.

c) Calorically perfect
To be calorically perfect, we would expect a gas to have c v~constant or cp~constant. Since
we have a number of values for constant pressure, let’s look at cp=h/T|p. Approximating this
from our table of data,
h 253  83.8 kJ kg
e.g., c p    0.85 kJ kg K
T 500  300K

Substance p (bar) T (K) h (kJ/kg) h/T (kJ/kgK)

A 20.0 300 83.8 ---
A 20.0 500 253 0.85
A 20.0 1000 718 0.93

Therefore, cp increases by at least 10% from 300 to 1000 K. To be calorically perfect, c p

should be nearly constant.
Strictly speaking, this is NOT a calorically perfect gas…
BUT, is a 10% change significant? Answer – it depends. For example, for a given h, using
a calorically perfect assumption could produce a 10% error in calculating T
- in our case, 0.10(1000K-300K)=70K
This error in temperature may or may not be significant depending on the situation (like how
accurately you could measure temperature?).

Implications:
1) For a gas (substance A), enthalpy is mostly a function of temperature, not pressure.
2) For other substances (like B) where density is nearly constant (i.e., an incompressible
substance) with changes in pressure, enthalpy is a stronger function of pressure.
3) For high density substances (like B), enthalpies are much less than for for a low
density substance at the same internal energy.
4) Whether a substance can be considered calorically perfect depends on the size of the
error introduced relative to the “acceptable” error.

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Problem 2. Gas Storage
Given: 50.0 kg of N2 initially in closed, rigid T1= 5C=278K T2=45C=318K
container that eventually is heated to p1=65.0 bar V2=V1
conditions shown in figure. m=50.0 kg
Find: (a) V1min
(b) p2
(c) Estimate of V error due to ideal N2 N2
gas assumption
Assume: ideal gas for parts (a) and (b), at
equilibrium Q
Analysis:
a) Volume
We know our initial state because we know (p,T), so we can use a state equation to find other
state variables. In this case, use ideal gas state eqn. pV  mRT

mRT mR MW T 8314 Nm kmolK  105 N m 2 

V   50.0kg 278K  65.0bar   0.635 m3
p p 28.01kg kmol  bar 
and for use below   m V  50.0kg 0.635 m3  78.7 kg m3
b) p2
Since V=const. and the system is closed (m=const), we know density (or specific volume)
also does not change, so state 2 is also known (v2, T2). Therefore, we can again use a state
equation to find the other state variables.
m2 RT2  mR  p 
p2   T2   1 T2
V2  V   T1 
since (mR/V ) is a constant in this problem. So
 65.0bar 
p2   318K   74.4bar
 278K 
c) V1 error
First let’s define the fractional error
Videal  Vreal Videal
Verror   1
Vreal Vreal
We need some “real” gas EOS information about N2 at our conditions (278K, 65bar). There
are a number of possible options. We could find a new EOS for N2, or we could estimate the
compressibility using the generalized compressible chart to find Zpv/RT. Using the latter
approach,

Verror 
mRT p   1  1  1
mRT p Z Z
To find Z, we first need to find the critical temperature and pressure for N2.

-3-
From Appendix H of Black and Hartley or from the web, e.g.,
http://encyclopedia.airliquide.com, we get Tcrit=126K, pcrit=34 bar.
So we have for the reduced temperature and pressure:
278 K 65bar
Tr   2 .2 pr   1 .9
126 K 34 bar
Examining Figure E.3 of the text (or from many places on the web), we find Z0.98.
1
So Verror   1  0.02 or the ideal-gas-based volume will be a few % LARGER than the
0.98
necessary volume.
ALTERNATIVELY,
We can calculate the N2 specific volume (or density from an EOS like the Beattie-
Bridgeman EOS given in Table H.2 in the textbook – or using an online calculator like
http://www.peacesoftware.de/einigewerte/stickstoff_e.html. Using the latter, we find
  79.99 kg m3
which means our ideal gas density was 1.6% too low (or – again - our volume calculated
from the ideal gas EOS was about 2% too high).
Implications:
1) If our storage tank was a sphere, it would have a diameter of ~1 m. So it takes a pretty
big tank to hold 50 kg of a gas, even at high pressure.
2) Even though the gas is being stored at a pressure almost twice the critical pressure,
the fact that the temperature is well above the critical temperature means the gas is
still nearly ideal.

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Problem 3. Work & Energy Change
Given: 10.lbm of ideal gas with p1=2.0 atm p2=3 p1
MW=60.1,  =1.23 T1=140.F=600.R v2= v1
m1=10. lbm m2=m1
Find: (a) U12 (kJ)
(b) H12 (kJ)
(b) W12 p 2

Assume:  calorically perfect gas (since one value

of  given)
 no work but compression/expansion
work 1
 volume stays constant during the
ENTIRE process v
Analysis:
a) U12
Using the caloric equation of state of an ideal gas AND assuming cal. perfect

U12  mu12  m  cv dT  mcv T2  T1   m T  T 

T2 R MW
T1  1 2 1
We know everything in this equation except T2. To get the final temperature, we can use
the ideal gas eq’n of state since we know two intensive variables at state 2, i.e., p2 and v2
(actually we don’t know v2, but we know it is the same as v1 which we can get from a state
equation too).

p2 3p 3 p  RT 
T2  v2  1 v1  1  1   3T1 or T2  T1  3T1  T1  2T1
R R R  p1 
=0.033 BTU/lbmR
BTU lbm
1.986 60.1
So U 12  10.lbm lbmolR lbmol 2600.R   1730BTU
1.23  1
b) H12

H12  U12   pV 12  U12  mRT 12  U12  mRT12

 BTU 
So H12  1730BTU  10lbm  0.033 1200R  2120BTU
 lbm R 
or we could have gotten there even more simply for our TPG/CPG …
H12  mcp T2  T1   mcv T2  T1   U12  1.231730BTU   2120BTU

c) With the standard expression for compression/expansion work

-5-
 2
W12   pdV  0 since there is no change in volume in our assumed path. There could also
1
be other kinds of work being done, but we assumed there was none.

Implications:
1) In this case the internal energy increases without NET work being done to the system
– this suggests there must have been some heat transfer to raise the temperature
2) Note that if we had not had V stay constant
during the complete process (for example look at
the path shown in the figure), then there WOULD p 2
have been net compression work done to the gas
in the vessel. (In the example path shown, the
work done in the third part of the path to the gas
would be greater than the work done by the gas
as it expanded in the first part of the path.) 1
3) So if we had NOT assumed a fixed volume for
the whole path and NOT assumed that v
compression work was the only possible work,
then we could not have provided an answer for part c. Without knowing the process
involved in going from state 1 to state 2, you can’t figure out how much work was
required.

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Problem 4. Ideal Gases – U and H
T T2=1000. K
Given: Simple compressible substance, H2 or H2O p2=10.0 atm
undergoing change shown in figure.
Find: h12 and u12 for
(a) calor. perfect (with room T values) T1=350. K
(b) polynomial fits from D.11 p1=1.0 atm
(c) tables (D.4 and D.7)
Assume: Ideal gases
p
Analysis: We can use the following for thermally perfect gases:
h12   c p dT and (1)
u12   cv dT (2)

cv  c p  R  c p  R MW (3)

In addition, since h  u  pv or for a thermally perfect/ideal gas h  u  RT then

h2  h1  u2  u1   RT2  T1 
or
u12  h12 
R
T2  T1  (4)
MW

a) For calor. perfect assumption, specific heats are constants. So eq (1) gives:
h12  c p dT  c p T2  T1  and u12  cv T2  T1 

From Table D.9 cp,H2=14.31 kJ/kgK, cp,H2O =1.865 kJ/kgK,
cv,H2=10.19 kJ/kgK, cv,H2O =1.404 kJ/kgK
and T2  T1  =650K.

kJ kJ
So h12, H 2  9300 , h12, H 2O  1210
kg kg

Similarly from eq (2)

kJ kJ
u12, H 2  6620 , u12, H 2O  913
kg kg
b) From Table D.11, (T in Kelvin)
H2 H 2O
a 3.057 4.07
cp b 2.677  10 3  1.108  10 3
 a  bT  cT  dT  eT
2 3 4
with
R c  5.180  10 6 4.152  10 6
d 5.521  10 9  2.964  10 9
e  1.812  10 12 8.07  10 13

 Ra  bT  cT 
T2

From eq (1), h12  c p dT   dT 3  eT 4 dT
2
T1

1000
R  T2 T3 T4 T5
h12   aT  b  c  d  e 
MW  2 3 4 5  350

kJ kJ
So using the values from above h12, H 2  10340 , h12, H 2O  1350
kg kg

650 K  10340  4.124650

8.314 kJ kmolK kJ kJ
and from eq (4), u12, H 2  h12, H 2 
2.016 kg kmol kg kg

u12, H 2  7660 kJ kg

8.314 kJ kJ
Similarly u12, H 2O  1350  650.  1050
18.02 kg kg

h12, H 2  h1000K   h350K   14459  9945

kJ kJ
c) From Table D.4,  9510 and
kg kg
 h1000K   h350K   1993.0  6436.74  1350
kJ kJ
from Table D.7, h12, H 2O
kg kg

u12, H 2  10334  3502

kJ kJ
Similarly,  6830 and
kg kg Values given to the same
 1531.5  485.2  1050
kJ kJ ~number of significant figures as
and u12, H 2O in part (b)
kg kg

For H2O, these are essentially the same numbers obtained from the polynomial fits to cp
in part b, BUT NOT for the H2 results.
Implications:
1) The results for H2 using the table data are close (within ~2-3%) to the ones we
found using the simpler calorically perfect gas assumption (case a) meaning H2 is
close to being calorically perfect from 350-1000K.
2) HOWEVER for H2O, the change in the values are somewhat larger (~10-13%)
comparing the (room T) constant specific heat calculation to the more accurate table
data. Therefore, we can conclude that the calorically perfect assumption is less
valid for H2O from 350-1000K.
3) The polynomial fit data for the H2O specific heat provides essentially the same
answer as the table data, BUT the polynomial fit given for H 2 produces significantly
different results from the table data. This suggests the H 2 polynomial may be a poor
fit to its actual cp/R values.
For example, another source (NASA tables) suggests the following polynomial
values for H2’s cp/R:
a B c d e
3.337279 -4.94024710-05 4.99456810-07 -1.79566410-10 2.00255410-14
Problem 5. Liquid Methane – Compression and Heating
Given: 525 kg of liquid methane stored at 120 K
Find: (a) Volume of container for p=2.5 MPa
(b) V/V for p changed to 0.5 MPa (but same T=120K)
(c) T required for same V/V with p still 2.5 MPa
(d) H(5.0MPa,120K) - H(0.5MPa,120K) vs H(2.5MPa,125K) - H(2.5MPa,120K)
Assume: none
Analysis:
a) Volume

From the table, we know the methane density, therefore

m 525kg
V   1.27m 3
 120 K ,2.5MPa  412.42 kg m 3

b) Fractional Volume Change

We want to know
V 0.5MPa,120 K   V 2.5MPa,120 K  1  CH 4 0.5MPa,120 K 
 1
V 2.5MPa,120 K  1  CH 4 2.5MPa,120 K 

V 1 410.25
  1  0.0053
V 1 412.42

c) Required Temperature Change

To get the same fractional volume change, we need to find the temperature such that
CH 2.5MPa,T   CH 0.5MPa,120K   410.25 kg m3
4 4

We can use the 2ndtable given in this problem (properties for p=2.5MPa) and interpolate,
e.g., using a linear approximation between temperatures. From the table, we can see that
the temperature will be between 120 and 125K. Using the linear approximation:
 125K    120 K 
 T    120 K   T  120K 
125K  120 K
 T    120K 
or T  120K  5K
 125K    120K 
Inserting values from the table
410.25  412.42
T  120 K  5K  121.4 K
404.81  412.42
d) Enthalpy Changes

Since our tables give the specific internal energy, not the specific enthalpy, we can use the
general expression h  u  pv  u  p  . So for example

kJ 0.5 106 N m 2
hCH 4 0.5MPa,120K   28.599
kJ J kJ
 3
 28.599  1219  29.82
kg 410.25 kg m kg kg kg
Using a similar approach for the other specific enthalpy values, and with H=mh, we find

H CH 4 5MPa,120K   H CH 4 0.5MPa,120K   525kg35.99  29.82

kJ
 3.24MJ
kg

H CH 4 2.5MPa,125K   H CH 4 2.5MPa,120K   525kg50.20  32.53

kJ
 9.29MJ
kg

Implications:
1) Liquid methane under the conditions given can be well approximated as a nearly
incompressible substance. The volume or density change only increase by ~0.5%
as the pressure is raised from 5 bar to 25 bar.
2) Even though this liquid can be considered incompressible, that does not mean its
density can’t change. Just a 1 K change in the temperature causes the same
density to drops as much as a 5 pressure decrease at these conditions. The
density of an incompressible substance can change with temperature.
3) Similar to the findings for density, a large change in pressure produces a smaller
(but not negligible) change in a (nearly incompressible) liquid’s enthalpy compared
to a small change in temperature. This has implications if we were to want to pump
(i.e., compress) a liquid.
Problem 6. Water - Energy Change and Work
Given: Closed piston/cylinder (Vconst)
undergoing p=constant process and initial
conditions shown p2=p1
T2
Find: (a) T2 if V2=0.40 ft3
V2
(b) h2-h1 if V2=0.40 ft3
(c) h2-h1 if T2=600.F
(d) W 12 if T2=600.F m=0.50 lbm
T1=300. F
Assume: process slow enough to be quasi- p1=500. psia
equil.
Analysis:
a) T2 p
At state 2, we know
p2=p1=500.psia
and v2=V2/m=0.4 ft3/0.50lbm=0.8 ft3/lbm
2
we have from B.1E that at 500 psia 1 2
vf=0.01975 ft3/lbm and vg=0.92806 ft3/lbm. T

Since our specific volume is between these two

 saturated mixture v

So T  Tsat 500 psia   467F

b) h2-h1

To find h1, we need to find the initial state. Since T1  300F  Tsat 500 psia  , the initial
state is a compressed liquid. From Table B.4E,

h1  hH 2O 500 psia ,300 F   270.58 BTU lbm

To find h2, we can find the quality at state 2. From Table B.2E at 500 psia,

x2 
v2  v f

0.80  0.019749 ft 3 lbm
 0.859
3
v fg 0.90831 ft lbm

Then

h2  h f 500 psia   h fg x2  449.47 BTU lbm  755.50.859 BTU lbm  1098.5 BTU lbm

And h2  h1  1098.5  270.58 BTU lbm  828 BTU lbm

This process is shown on the p-v state diagram above.

c) h2-h1 for T2=600F

At our new state 2 (let’s call it 2), we now have p2=500.psia and T2=600.F.

Since T2'  Tsat 500 psia   467F , state 2 is a superheated vapor. From Table B.3E,

h2' 500 psia ,600F   1297.9 BTU lbm

and h2'  h1  1297.9  270.58 BTU lbm  1027 BTU lbm

This process is also shown on the p-v diagram above.

d) W12

To calculate the work in the expansion process 12 (with our quasi-equil. assumption)
we can use
2'
W12   pdV  p1 V2'  V1 
1
since pressure is constant during the whole process.

From Table B.4E, v1  vH2O 500 psia,300F   0.017415 ft lbm

3

From Table B.3E, v2'  vH2O 500 psia,600F   1.1580 ft lbm

3

So
W12'  pmv2'  v1 
lb f 144in 2 ft 3
 500. 2 0.50lbm 1.1580  0.017415
in ft 2 lbm
 52.8BTU  55.7kJ 
1BTU
 4.11 10 4 ftlb f  4.11  10 4 ftlb f
778 ftlb f

Implications:
1) Work is done BY the water as it expands from a liquid to a gas, and since most of
the volume change occurs as it evaporates (liquid to gas), that is where most of the
work is done
2) Comparing the work done in this process (52.8 BTU or 105.6 BTU/lbm) to the enthalpy
change (1027 BTU/lbm), we get the idea that the energy change in the process is MUCH
greater than the work done (this implies the process requires a lot of heat transfer into the
water, much more than the work done).