3.1 Given: N2 is at an initial state at 800 K and 8 atm and final state at 400 K and 1 atm.

It behaves
as an ideal gas.
Find: a.) Calculate the densities (kg /m3) at both states, b.) Using the JANAF table for N2, calculate
h2-h1, u2-u1 , s2-s1 and c.) Select a suitable average value for Cp and then calculate the quantities
in (b) using the assumption of constant specific heats, d.) use the polynominal representation for
Cp and find h2-h1, s2-s1, and e.) which method is most accurate and determine errors of the other
methods
Solution: For N2 the molecular weight (see Table A-2) is MN2 = 28.01 kg/kmole, treat as IG
kg kN
kg kN 28.01 101 2
808 2 kg kmole m kg
a 28.01 3.4027 3 2, IG 0.8507
1, IG
kmole m kN m m3
kN m
m 8.314 300 K
8.314 800 K kmole K
kmole K
b.) Using Table A-6 for N2 in Wark
T (K) h (kJ/kmole) u (kJ/kmole) so (kJ/kmole-K)
1 800 23,714 17,061 220.907
2 400 11,640 8,314 200.071
h = h2 h1 = (11,640- 23,714) kJ/kmole/28.01 kg/kmole = -431.06 kJ/kg
u = u2 u1 = (8,314- 17,061) kJ/kmole/28.01 kg/kmole = -312.28 kJ/kg
s = s2 s1 = so2 so1 Ru/M*ln(P2/P1) = {200.071- 220.907-8.314*ln (1/8)}/28.01= -0.127 kJ/kg-K
c From Table A-4-1 for N2: Cp(T= 800 K) = 1.121 kJ/kg-K and Cp(T= 400 K) = 1.044 kJ/kg-K
Cp,avg = (1.121 + 1.044)/2 = 1.0825 kJ/kg-K Cv,avg = Cp,avg Ru/M = 0.7857 kJ/kg-K
kJ
h h2 h1 C p , avg T2 T1 1.0825 400 800K -433.00 kJ/kg
kg K
kJ
u u 2 u1 Cv , avg T2 T1 0.7857 400 800 K -314.27 kJ/kg
kg K
400 1 -0.133 kJ/kg-K
s s 2 s1 C p,avg lnT2 T1 R gas lnP2 P1 1.0825 * ln 8.314 / 28.01 * ln
800 8
d Polynomial Table A-4_3 in Wark for a= 3.675, b=-1.208e-3, c=2.324e-6, d=-0.632e-9, e=-0.226e-12
T2 b 2 T2 c 3 T2 d 4 T2 e 5 T2
h h2 h1 Ru aT T T T T T
1
2 T1 3 T1 4 T1 5 T1
b
2
3
c
d
4

e

h Ru aT2 T1 T22 T12 T23 T13 T24 T14 T25 T15 12,072.85
5
kJ
kmol

T2
Cp P T2 2 T T2
P2
dT Ru ln 2 Ru a ln T T2 bT T2 T 2
c d e
s T3 T4 Ru ln
T T

T1
T P1
1 1
2 T1 3 T1 4
T1 P1
T c
d
e
P

s Ru a ln 2 bT2 T1 T22 T12 T23 T13 T24 T14 Ru ln 2 3.545
kJ
kmol K
T1 2 3 4 P1
h
h = -431.02 kJ/kg s s = -0.127 kJ/kg-K
M M
e Most accurate method is part b (JANAF tables) %error = (method best)/best*100
% error h for method c = 0.45%, % error s for method c = 5.1%
% error h for method d = -0.01%, % error s for method d = -0.08%
1
3.2 Given: Atomic nitrogen (N)
Find: Using the approach described in Ex. 5-3 of your course notes calculate the specific heat
for oxygen. Find a 4th order polynominal to Cp/Ru

Solution: For N use table 1600 of the NIST-JANAF tables for energy levels, ei, and the
degeneracies, gi

Section 6.1.1 of Monograph 9 (pp. 17-18) give the following equations for the contribution to
the molar specific heat due to translational and the electronic energy modes of an ideal
monotonic gas:

Translation energy mode: C o

p tr 5 2 Ru 5 2 8.3144 kmolekJ K 20.786 kmolekJ K
Electronic energy mode: C p 2 d ln Q d ln Q where Q g exp c2 i
o 2
T 2T i
Ru dT 2 dT i T
e

evaluating the first and second derivative of ln(Q) gives

c2 i
i gi exp
d ln Q c2
2 i T
dT T c
gi exp 2 i
i T
2
and c 2 i c2 i c 2 i
i g i exp 2 i g i exp i g i exp T
2

d 2 ln Q 2c2 T 2 i
c T c2
2
i
i
dT 2
T3 c T4 c T4 c 2 i
2
g i exp 2 i g i exp 2 i
T T g i exp T
i i i
2
c2 i c2 i
i gi exp i g i exp T
2
Thus C o
p c2 T c2
2
i
22 i
Ru T c 2
c2 i
2
e gi exp 2 i T
T g i exp T
i
i

Table 1600 gives the 5 lowest electronic energy levels. Thus we need to perform sums at EACH
temperature. For example,

c2 i c c c c c
g i exp g1 exp 2 1 g 2 exp 2 2 g 3 exp 2 3 g 4 exp 2 4 g 5 exp 2 5
i T T T T T T
c c c c c c
i g i exp 2 i 1 g1 exp 2 1 2 g 2 exp 2 2 3 g 3 exp 2 3 4 g 4 exp 2 4 5 g 5 exp 2 5
i T T T T T T

c2 i c 2 c 2 c 2 c 2 c
i gi exp 1 g1 exp 2 1 2 g 2 exp 2 2 3 g3 exp 2 3 4 g 4 exp 2 4 5 g5 exp 2 5
2 2
i T T T T T T

Using Excel to evaluate the sums at each temperature gives:

2
Nitrogen N 1600
c2(cmK) 1.438786 Ru(kJ/kmole 8.3144
e_i(cm^1) g_i
1 0.00 4
2 19224.46 6
3 19233.18 4
4 28838.92 2
5 28839.31 4
6
T Q sum(e_i*Q_i) sum(e_i^2*Q_ Cp,elec/Ru Cp,elec Cp,trans Cp,total Cp,total/Ru
100 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786
200 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786
250 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786
298.15 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786
300 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
350 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
400 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
500 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
600 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
700 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
800 4.0000 0.0000 0.0000 0.0000 0.0000 20.786 20.786 2.5000
900 4.0000 0.0000 0.0002 0.0000 0.0000 20.786 20.786 2.5000
1000 4.0000 0.0000 0.0036 0.0000 0.0000 20.786 20.786 2.5000
1500 4.0000 0.0019 36.1507 0.0000 0.0001 20.786 20.786 2.5000
2000 4.0000 0.1892 3639.92 0.0005 0.0039 20.786 20.790 2.5005
2500 4.0002 3.0171 58116.05 0.0048 0.0400 20.786 20.826 2.5048
3000 4.0010 19.1824 370475.13 0.0213 0.1770 20.786 20.963 2.5213
3500 4.0037 72.2123 1400303.48 0.0590 0.4910 20.786 21.277 2.5590
4000 4.0101 196.0659 3821922.26 0.1230 1.0227 20.786 21.809 2.6230
4500 4.0220 428.27 8399348.72 0.2123 1.7654 20.786 22.551 2.7123
5000 4.0410 803.37 15860962.53 0.3217 2.6750 20.786 23.461 2.8217
5500 4.0686 1348.86 26815840.00 0.4435 3.6876 20.786 24.474 2.9435
6000 4.1054 2083.66 41714568.78 0.5695 4.7348 20.786 25.521 3.0695

a = 2.481
b = 6.781 e-5
c = -6.338 e-8
d= 1.887 e-11
e = -1.241 e-15

3
3.3 Given: Consider a 5 1iter copper container with mass of 3 kg that contains gaseous regrigerant
134a at 500 kPa. The tank and R-134a are initially at equilibrium at 300 K. The tank and R-134a
are then heated to a new equilibrium temperature of 350 K.
Find: a.) change in internal energy for R-134a only, for tank only and for R-134a & tank
composite system, and b.) initial internal energy of R-134a and initial internal energy of
tank assuming constant specific heats and Tref = 0 K
Solution:
Assume pressures are absolute
Assume R-134a behaves as an ideal gas
Assume specific heats are constant over temperature range of process

a.) PR-134a,1 = 500 kPa, TR-134a,1 = TT,1 = 300 K , TR-134a,2 = TT,2 = 350 K, mT = 3 kg, VR-134a =
.005 m3
kN
500 .005 m 3
PR134a ,1VR134a m 2
mR134a 0.10227 kg
RR134aTR134a ,1 kN m
0.0815 300 K
kg K
Specific heats at 25 C and 27 C (~ the initial temperature - 300 K)

R-134a (Table A-1): Cv = 0.76 kJ/kg-K, copper (Table A-3-B), Cp = 0.386 kJ/kg-K ~ Cv (solid!)

UR-134a = mR-134a Cv,R-134a (TR-134a,2 TR-134a,1)

= 0.10227 kg 0.76 kJ/kg-K (350 300) K = 3.886 kJ

UT = mTCv,T(TT,2 TT,1) = 3 kg 0.386 kJ/kg-K (350 300) K = 57.9 kJ

UT+R134aU R134a + UT = 3.886 + 57.9 = 61.786 kJ

UT is much larger than UR134a due primarily to the large difference in mass
T
b.) for incompressible solid or liquid and ideal gases: u T C T dT
v
Tref

Note: if there are phase changes (freezing, melting, evaporation, condensation), this integral has
to be evaluated in a piecewise fashion were latent heats are considered. If Tref = 0 K all material
will be solids - we are ignoring this here, just to practice using this equation.

Assuming constant specific heats: u T C v T Tref

Selecting Tref = 0 K gives u T C v T
Using Tref = 0 K initial internal energies for the R134s and tank are:
u R134a,1 = Cv, R134a T R134a,1 = 0.76 kJ/kg-K300 K = 228.0 kJ/kg
U R134a,1 = m R134a u R134a,1 = 0.10227 kg 228.0 kJ/kg = 23.317 kJ
uT,1 = Cv,TTT,1 = 0.386 kJ/kg-K300 K = 115.8 kJ/kg
UT,1 = mT uT,1 = 3 kg 115.8 kJ/kg = 347.4 kJ