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This chapter discussed the different gas laws and equations of state used to model ideal or real gas behaviors and properties, either
acting as a pure gas or as a mixture. For instance, air at atmospheric pressure is a mixture of gases, though it is often, modeled as one
substance.
IDEAL GAS LAWS increased with the temperature. Charles's Law states “that the
volume of a given amount of dry ideal gas is directly
BOYLE’S LAW proportional to the absolute temperature provided the
Boyle's Law was perhaps the first expression of an amount of gas and the pressure remain fixed.” When we
equation of state. In 1662 Robert Boyle, an Irishman, plot the Volume of a gas against the Kelvin temperature it forms
performed a series of experiments employing a J-shaped a straight line. In mathematical statement,
glass tube, which was sealed on one end. Mercury was V
V T V aT a
added to the tube, trapping a fixed quantity of air in the T
short, sealed end of the tube. Then the volume of gas was V2 T2
carefully measured as additional mercury was added to the V1 T1
tube. The pressure of the gas could be determined by the
difference between the mercury level in the short end of the
tube and that in the long, open end. Through these GAY LUSSAC’S LAW
experiments, Boyle noted “that at constant temperature, In 1801 Joseph L. Gay Lussac investigated the
the gas volume varied inversely with the absolute relationship between the pressure of a gas and its temperature.
pressure.” In mathematical form, this can be stated as: He published similar results of experiments as that of Charles,
1 a indicating a linear relationship between volume and
V V a PV
P P temperature. The Gay Lussac’s Law states that “at constant
P1V1 P2V2 volume, the pressure of a gas sample is directly
proportional to the absolute temperature.” The
Where a is proportionality constant.. For two sets of mathematical statement is as follows:
conditions the following is a math statement of Boyles Law
is: P
PT P aT a
P2 V1 T
P1 V2 P2 T2
P1 T1
The above relationship has also been attributed to
Edme Mariotte and is sometimes referred to as Mariotte's
law. However, Mariotte's work was not published until 1676. COMBINED GAS LAW
Consider a quasi-equilibrium process from state 1 to state
2, this can be replaced by two processes consist of constant
CHARLES’ LAW volume (state 1 - a) and constant pressure (state a - 2).
In 1787 the French physist Jacques A. Charles (1746-
1823) found that oxygen, nitrogen, hydrogen, carbon Process 1 – a : Constant Volume Process
dioxide, and air expand to the same extent over the same Pa Ta
P
Ta T1 a
80 degree interval. He noted that the volume of a gas P1 T1 P1
V C n
Volume (V) = Constant (C) x Moles (n)
AVOGADRO’S LAW
During the first half of the nineteenth century, Lorenzo
Romano Amedeo Carlo Avogadro, count of Quaregna and
Cerreto, made major contributions towards elucidating
reaction stoichiometry and explaining why compounds
For instance, one liter of any ideal gas at a temperature of
reacted in certain well-defined integer ratios. These studies
0°C and a pressure of 101.3 kPa, contains 2.688x1022
led Avogadro to address the question of how the amount of
molecules. It has been experimentally determined that the
gas affect the volume of the gas and how best to think about
number of atoms in this quantity of 12C is 6.0221 x 1023. This
the amount of a gas. Experimentally, the easiest way to
number is called Avogadro's number.
quantify the amount of gas is as a mass. Avogadro played
an important role in establishing the existence of atoms. The
As one liter of gas, at STP, contains 2.688 x 1022
number of molecules in a mole is named after him.
molecules (or atoms in the case of a mono atomic gas), it
follows that a mole of gas (6.0221 x 1023 molecules) occupies a
Avogadro's Hypothesis:
volume of 22.4 liter at STP.
“Two equal volumes of gas, at the same temperature
and pressure, contain the same number of molecules. “
u f T
( for ideal gas equation of state )
GRAHAM’S LAW The time required for 25-mL samples of different gasses
As we stated earlier, the shape of a gas is determined to diffuse through a pinhole into a vacuum.
entirely by the container in which the gas is held. R1 MW2 2
Sometimes, however, the container may have small holes, R2 MW1 1
or leaks. Molecules will flow out of these leaks, in a process
where:
called effusion. Because massive molecules travel slower
r1=rate of effusion in molecules per unit time of gas "1"
than lighter molecules, the rate of effusion is specific to each
r2=rate of effusion in molecules per unit time of gas "2"
particular gas. Thomas Graham introduced the relationship
u1=molecular mass of gas "1"
between rates of effusion and diffusion for two different
u2=molecular mass of gas "2"
PVi ni RT
PVi ni RT Vi ni
PV n RT V n
P P
i
i P1 P2 Pi
Vi ni
yi
V n
V V1 V2 Vi
T T1 T2 Ti
EQUATIONS OF STATE
AMAGAT 'S LAW OF ADDITIVE VOLUMES The most general equation of state can be expressed as
The Amagat’s law of partial volume of an ideal gas in
the mixture states that “the total volume of the mixture of V V
dV dT dP
gases is equal to the sum of the individual volumes that T P P T
would be occupied by each component at the mixture dV
dT dP
temperature and pressure.” V
the repulsion parameter or the effective molecular (c) Redlich - Kwong Equation of State
volume (finite volume occupied by the gas molecules).
Introduced in 1949 the Redlich-Kwong equation of
RT a state was a considerable improvement over other equations of
P the time. It is still of interest primarily due to its relatively simple
v b v2
form. While superior to the van der Waals equation of state, it
performs poorly with respect to the liquid phase and thus
VAN DER WAALS CONSTANTS cannot be used for accurately calculating vapor-liquid equilibria.
a Although, it can be used in conjunction with separate liquid-
b
SUBSTANCE [ (kPa-m6) /
[ m3 / kgmol ] phase correlations for this purpose.
(kgmol2) ]
Air 135.8 0.0364
RT a
Ammonia (NH3) 423.3 0.0373 P 1
Carbon dioxide (CO2) 364.3 0.0427 v b T v v b
2
SUBSTANCE BO b 10 -4 c
Air 0.04611 - 0.001101 4.34
Argon (Ar) 0.03931 0.0 5.99
Carbon dioxide (CO2) 0.10476 0.07235 66.00
Helium (He) 0.01400 0.0 0.0040
Hydrogen (H2) 0.02096 - 0.04359 0.0504
Nitrogen (N2) 0.05046 - 0.00691 4.20
Oxygen (O2) 0.04624 0.004208 4.80
When these derivatives are taken, we find (f) Berthelot equation of state
2 5
R TC 2 R TC
a 0.42748 and b 0.08664
PC PC RT a
P
v b T v2
This same approach can be applied to the van der
Waals equation. When the partial derivatives are taken, the
following equations for constants results: (g) Benedict-Webb-Rubin BWRS) Equation of State
2
27 R 2 TC R TC
a and b
64 PC 8 PC
C0
B0 RT A0
P
RT
T 2 bBWR RT a BWR
2 3
v v v
(d) Soave Equation of State
a BWR c 2
3 1 2 e v
RT a 6
v T2 v
P v
vb v vb
(h) Virial Equation of State
(e) Peng-Robinson Equation of State
Although usually not the most convenient equation of
RT a state, the Virial Equation is important because it can be derived
P 2 directly from statistical mechanics. If appropriate assumptions
v b v 2bv b 2
are made about the mathematical form of intermolecular forces,
theoretical expressions can be developed for each of the
where: ω is the acentric factor for the species
2 2
coefficients. In this case B corresponds to interactions between
0.45724 R TC ; 0.07780R TC pairs of molecules, C to triplets, and so on.
a b
B T C T D T
PC PC
P v R T 1 2 3
1 0.37464 1.54226 0.26992 2 1 Tr 0.5
2
v v v
T
Tr
TC
The Peng-Robinson Equation was developed in 1976 in (i) Using Compressibility Factor
order to satisfy the following goals:
The parameters should be expressible in terms of Pv Z RT
the critical properties and the acentric factor.
The model should provide reasonable accuracy near
where Z is the compressibility factor
the critical point, particularly for calculations of the
Compressibility factor and liquid density.
The form of the equation of state using the
The mixing rules should not employ more than a
compressibility factor is simple. At this point the only difficulty
single binary interaction parameter, which should be
independent of temperature pressure and lies in acquiring charts for all gases. Fortunately, this task may
composition. be reduced to that of developing only one chart.
The equation should be applicable to all calculations
of all fluid properties in natural gas processes. This is accomplished using reduced equations of state.
The critical pressure, critical temperature and critical specific
volume are unique for each gas. The reduced coordinates are
For the most part the Peng-Robinson Equation exhibits
performance similar to the Soave equation, although it is P
Reduced Pressure PR
generally superior in predicting the liquid densities of many PC
materials, especially nonpolar ones.
m m1 m2 mi
m mi Gas Constant of the Mixture
i m1 m m
2 i
The mass fraction of the gas i is defined as xi, R n MW1 MW2 MWi
R R R
mi MW m m
xi
m x x x
R R 1 2 i
MW 1 MW 2 MW i
The total number of moles of the mixture is the sum of R R1 x1 R2 x2 Ri xi
all the number of moles of each component.
n n1 n2 ni xi
R R R x
n ni
i i
i MWi i
i
described as
PV n RT
mCPT m1CP1T1 m2CP 2T2 mi CPiTi
but T T1 T2 Ti
Let us consider that we have the components of a gas
mixture separated and existing at the same temperature T,
CP xi CPi CV
R ;
CP
kR ; C
k P & R C P CV
i k 1 k 1 CV
When two gases are mixed together, there will be an P1 P2 .... Pi V Z1n1 Z 2 n2 ... Z i ni RT
increase in entropy. This is called the entropy of mixing.
P1 P2 .... Pi V n Z1 n1 Z 2 n2 ... Z i ni RT
n n n
S S 2 S 1 n R ln
P2
P1 P1 P2 .... Pi V nZ1 y1 Z 2 y2 ... Z i yi RT
(FOR CONSTANT TEMPERATURE)
PV nZ mix RT
S a S 2 S 1
a
P
na R ln a na R ln y a
P where: Z mix yi Z i
S b S 2 S 1
b
P
nb R ln b nb R ln yb
P
i
where:
P1 P2 .... Pi V Z1n1 Z 2 n2 ... Z i ni RT
T2a = T2b mixture temperature PV1 V2 .... Vi Z1n1 Z 2 n2 ... Z i ni RT
P2 = P2a + P2b P2 is the mixture pressure
n n n
PV n Z1 1 Z 2 2 ... Z i i RT
n n n
Kay’s Method
Kay's Rule uses psuedo-critical properties to calculate
psuedo-reduced quantities that are then used in the
generalized compressibility charts
i mixture
TC yT
p
i C ,i
i
CRITICAL CONSTANTS
Molecular Weight (MW) Critical Temperature Critical Pressure Volume
SUBSTANCE
[kg / kgmol ] [K] [MPa ] [ m3 / kgmol ]
Air 28.97 133 3.76 0.0828
Ammonia (NH3) 17.03 405.5 11.28 0.0724
Argon (Ar) 39.948 151 4.86 0.0749
Carbon dioxide (CO2) 44.01 304.2 7.39 0.0943
Carbon monoxide (CO) 28.011 133 3.50 0.0930
Ethane (C2H6) 30.07 305.5 4.88 0.1480
Ethylene (C2H4) 28.054 282.4 5.12 0.1242
Helium (He) 4.00 38.4 1.66 -
Hydrogen (H2) 2.016 33.3 1.30 0.649
Methane (CH4) 16.043 191.1 4.64 0.0993
Methyl Alcodol (CH3OH) 32.0042 513.2 7.95 0.1180
Nitrogen (N2) 28.013 126.2 3.39 0.0899
Oxygen (O2) 32.0 154.8 5.08 0.0780
Propane (C3H8) 44.097 370 4.26 0.1998
Water (H2O) 18.015 647.3 22.09 0.568
SAMPLE PROBLEMS kN m
45.6621kg 0.1172 315K
3.1 An unknown diatomic gas has a mass of 1.5 kg and kg K
PInitial 337.15 kPa
occupies 2.5 m3 while at a temperature of 300°K and a 5m 3
pressure of 200 kPa. Determine the ideal-gas constant,
molecular weight, and the specific heat of the gas. (k=1.4 for 3.3 The density of the ideal gas is doubled were its
diatomic gas) temperature remains constant, determine (a) the ratio of
Solution : P1 / P2 (b) if P1g = 20 inHgvacuum, find the gage pressure at
Ideal gas constant: state 2.
Solution:
200
kN
2.5m3
R
PV
m 2
1.1111
kJ (a) P1/P2
1.5kg300K kg K
mT
P RT
Molecular Weight:
P1 1 R T1 1 1
kJ 1
R
8.31451
kgmol K kg P2 2 R T2 2 2 1 2
MW 7.483059
R kJ kgmol
1.1111
kg K (b) P2 gage P1 Patm P1g
Specific heat of diatomic gas: k 1.4
P1 29.92inHg 20inHg 9.92inHg
1.111 kJ
CV 2.7778 P1 1 9.92inHg
1 .4 1 kg K P2 19.84 inHg
P2 2 P2
C P kCV 2.7778 1.4
kJ
3.8889
kg K P2 19.84 inHg Patm P2 g
P2 g P2 Patm 19.84 inHg 29.92 inHg
3.2 A 5 m3 tank contains chlorine at 300kPa and 300°K
after 3 kg of chlorine has been used. Determine the original P2 g 10.08 inHg 10.08 inHgVACUUM
mass and pressure if the original temperature was 315°K.
Solution : 3.4 Air bubbles rises from the bottom of the well were the
PV
kN
300 2 5m 3 temperature is 25C, to the surface were the temperature is
m Final m 42.6621kg 27C. Find the percentage increase in the volume of the
kN m
RT
0.1172 300K bubble if the depth of the well is 5 meter and the barometer
kg K
m Initial m Final mUsed 45.6621kg reading is 100 kPa.
Solution:
m RT
PInitial Initial Initial
V INITIAL
3.5 An unknown gas at P1=95 psia and V1=4 ft3 undergoes THe 23 273 296K and TAIR 10 273 283K
a process to P2=15 psia and V2=16.56 ft3, during which the F upward F downward
enthalpy decreases 83 BTU; CV = 0.1573 BTU/lb-R. m AIR g o mPL g o mHe g o
Determine (a) CP (b) R, and (c) ΔU. W AIR WPL WHe
gc gc gc
Solution: PAIRV AIR PHeVHe
m AIR mHe mPL mPL
R AIRTAIR RHeTHe
R C P CV CP C
R C P CV 1 V D 3
R R R R R VHe VAIR and PAIR P He
6
H U PV mC P T CP mT2 mT1
D 3 P 1 1
PV PV C mPL
H C P 2 2 1 1 P P2V2 P1V1 6 RAIRTAIR RHeTHe
R R R
1
CP
H D3
6m PL
1
1
R P2V2 P1V1 P AIR AIR
R T R He T He
778.16 ft lb f 61360kg
1
CP 83BTU ft 2 1 1 kg K 1
D
kN 0.287283 2.077296 kN m K
,
1516.56 954 2 , ft 3 144in
2
R lb 1BTU 3
101.3 2
in m
CP D 13.4m
3.40823
R
CP C 0.1573 3.7 A balloon, considered spherical is 30 ft in diameter. The
1 V 3.40823 1
R R R surrounding air is at 60°F and the barometer reads 29.60 inHg.
BTU 778.16 ft lb f ft lb f What load may the balloon lift if it is filled with hydrogen at 70°F
R 0.06532 50.83
lbm R 1BTU
lb m R and atmospheric pressure if the observe average local gravity
BTU is 32.03 ft/s2?
CP 3.40823R 3.40823 0.06532
lbm R Solution :
BTU
C P 0.2226
lbm R From previous problem
MW1 28.016lb
lbmol
0.50 44.01lb lbmol 0.50
(c) partial pressures MW1 36.013lb
lbmol
PO 2 nO 2
PO 2 P yO 2 14.7 psia0.20814 R 1545 ft lb f
P n R1 42.9012
MW1 36.013 lbm R
PO 2 3.06 psia
PN 2 n N 2
PN 2 P y N 2 14.7 psia0.79186 m1T1
P n V V1 V2 R1
PN 2 11.64 psia P1
3lbm 150 460R ft lb f
V 42.9012 13.63 ft 3
2
(d) specific volume and density of the mixture lb f 144in lbm R
40 2
60 460R 53.5611 ft lb f ft 2
2
T in ft
v R
lb lbm R 144in 2
14.7 f 2
P
in
1
Total number of mols of 3 lb mixture
ft 3 ft 3 lb
v 13.1575 and v 1
13.1575 0.076 m3 n1
m1
3lb
0.0833 lbmol
lbm lbm ft MW1 36.013lb
1 lbmol
ft 3 lb
v 1 13.1575 0.076 m3 n1N 2 n1 y1N 2 0.0833lbmol0.50 0.04165 lbmol
lbm ft
n1CO2 n1 y1CO2 0.0833lbmol0.50 0.04165 lbmol
(e) oxygen added to produce a mixture which is 50% oxygen
by volume? Masses of components of the 3 lb mixture
m1N 2 n1N 2 MWN 2 0.04165 lbmol 28.016lb
lbmol
If oxygen is 50% by volume therefore nitrogen is also 50% m1N 2 1.1669 lbm
nN 2 new nN 2 0.137316lbmol since no addition and
, m1CO 2 n1CO 2 MWCO 2 0.04165 lbmol 44.01lb lbmol
rejection of nitrogen.
m1CO2 1.8331lbm
n 0.137316
y N 2 new N 2 new 0.50
nnew nnew
Masses of the components of the 4 lb mixture
nnew 0.274632lbmol
m2 N 2 m1N 2 maddedN 2 1.1669 lbm 1lbm
nO 2 new nnew nN 2 new 0.137316lbmol
m2 N 2 2.1669lbm
nO 2 new nO 2 nO 2 added m2CO2 m1CO2 1.8331lbm
nO 2 added nO 2 new nO 2 0.137316 0.036094
nO 2 added 0.101222lbmol
Total number of mols of 3 lb mixture
m2 N 2 2.1669lb U U 2 U 1 m CV T
n2 N 2 0.077345lbmol
MWN 2 28.016 lb
BTU
U 4 2lbm 0.24723 90R 133.506 BTU
lbmol
n2CO2 n1CO2 0.04165lbmol lbm R
nN 2
mN 2
0.5kg
0.0178kgmol R xi Ri
MWN 2 28.016 kg i
kgmol R 0.29680.50 0.18890.30 0.25980.20
mHe 1.0kg kJ
n He 0.2498kgmol R 0.25703
MWHe 4.003kg kg K
kgmol
n2 n N 2 n He 0.0178kgmol 0.2498kgmol
(a) power required
n2 0.2676kgmol kg kJ
WSF 2 0.95685 450 280K
P2 N 2 n N 2
n
P2 N 2 P2 N 2 289.75kPa
0.0178
s kg K
P2 n2 n2 0.2676 kg
P2 N 2 19.2734kPa WSF 325.329 or kW
s
P2 He n He n He 0.2498
P2 He P2 289.75kPa
P2 n2 n2 0.2676 (b) entropy production
P2 He 270.4766kPa T P
S m C P ln 2 R ln 2
T P T1 P1
S N 2 m N 2 C PN 2 ln 2 N 2 RN 2 ln 2 N 2
T1N 2 P1N 2 kg 450 500 kJ
S 2 0.95685ln 0.25703ln ,
391.48 19.2734 s 280 100 kg K
S N 2 0.5 kg 1.0399ln 0.2968ln
320 200 kJ kW
S 0.08062 or
S N 2 0.45202
kJ sK K
K
T P 3.15 Two kilogram per second of helium flows steadily into an
S He mHe C PHe ln 2 He RHe ln 2 He
T1He P1He adiabatic mixing chamber at 87°C and 400 kPa and mixes with
391.48 270.4766 nitrogen entering at 287°C and 400 kPa. The mixture leaves at
S He 1.0 kg 5.1954ln 2.077 ln
400 300 350 kPa with a molal analysis of 50%, He and %50, N2.
kJ Determine (a) the temperature of the mixture leaving the
S He 0.10331
K chamber; (b) the rate of entropy production.
Solution :
kJ
S S N 2 S He 0.45202 0.10331 0.55533
K Since helium and nitrogen are both 50% by volume, therefore
1
kg kg
n N 2 nHe mHe MWHe 2
1
4.003
(c) the change of internal energy of the system s kgmol
U U He U N 2 0 0.49963kgmol
n N 2 nHe
s
(14) An adiabatic compressor receives 2 kg/s of a gas
mixture and compresses it from 280°K and 100 kPa to
450°K and 500 kPa. The mixture’s mass fractions are 50%
N2, 30% CO2 and 20% O2. Determine (a) the power
required; (b) the entropy production.
Solution :
T P
S N 2 mN 2 C PN 2 ln 2 N 2 RN 2 ln 2 N 2
T1N 2 P1N 2
kg 476.7 175
S N 2 13.9975 1.0399ln 0.2968ln
s 560 400
kJ
S N 2 1.090166
sK
T P
S He mHe C PHe ln 2 He RHe ln 2 He
T1He P1He
476.7 175
mass of the components S He 2 kg 5.1954ln 2.077 ln
400
mN 2 nN 2 MWN 2 0.4996328.016 13.9975kg
360
kJ
kg S He 6.351586
m He 2 sK
s S S N 2 S He 1.090166 6.351586
kW
Gravimetric analysis S 7.44175
K
m 2
x He He 0.12502
m 2 13.9975 3.16 Given that a carbon monoxide gas has a temperature of
m 13.9975
xN 2 N 2 0.87498 500°K and a specific volume of 0.40 m3/kg, determine the
m 2 13.9975
pressure using the van der Waals equation of state and the
CP xi CPi 1.03990.12502 5.19540.87498
i
ideal gas equation of state.
kJ Solution :
C P 4.67588
kg K
Ideal Gas Equation of State
(a) Temperature of the mixture leaving the chamber For kN m
0.2968 500K
steady flow adiabatic system that does not require or RT kg K
P 371kPa
produce work, Q = WSF = 0 v m3
0.40
Q H WSF H H N 2 H He 0 kg
13.99751.0399560K 25.1954360K v
T
500K 146.3 kPa m2
6
13.99751.0399 25.1954
kJ
8.31451
kgmol K kgmol
T 476.7 K or 203.7C P
m3 m6
11.204 0.0394 11.2042
kgmol kgmol2
(b) rate of entropy production P 371.194 kPa
P2 N 2 n N 2
yN 2 P2 N 2 y N 2 P2
P2 n
P2 N 2 350kPa0.50 175 kPa 3.17 Berthelot proposed an equation of state for a fluid in the
P2 He nHe form P a v b RT where a and b are constants.
y He P2 He y He P2
P2 n T v 2
P2 N 2 350kPa0.50 175 kPa Show that, at critical isotherm, (a) a 9 2
RvCTC ; (b)
8
b 13 vC
Solution : (19) A 0.2 m3 tank contains steam at 725°C and 1000 kPa.
a Determine the mass in the tank using (a) the ideal gas-law; (b)
v b RT
RT a
P P 2
T v 2 v b T v the van der Waals equation of state; (c) the generalized
compressibility chart.
At critical isotherm
Solution :
P 2P
0 and 0 (a) the ideal gas-law
v TC v 2 T
C
PV
1000
kN
0.2m 3
P RT 2a m m2 0.43424kg
0 kN m
v TC v b 2 T v 3 RT
0.4615 725 273K
kg K
RTC
2 3
2a RTC vC
0 ; a v
V
V V
MW
0.2m 3
18.016
kg
vC b2 TC vC 3 2 vC b kgmol
2
n m m 0.43424kg
MW
2P 2 RT 6a m3 (to be used as initial trial to VWES)
0 v 8.29772
v 2 T
C
v b 3
T v4 kgmol
2 4
2 RTC 6a RTC vC
0 a (b) the van der Waals equation of state (VWES),
vC b3 TC vC 4 3vC b
3
RT a
P 2
v b v
Combining the two equations of constant a
2 4 2 3
RTC vC RTC vC vC 1
a Determination of the constants a and b :
3vC b
3
2 vC b
2
3vC b 2
2
kN m
v 27 8.31451 647.3K
2
2 vC 3 vC 3 b b c 2 2
kgmol K
3 a
27 R TC
2 3 2 3 2 3 64 PC kN
RTC vC RTC vC RTC vC 64 22090 2
a
2 vC b
2 2 2 m
v 2v
2 vC C 2 C kN m 4 m 2 kPa m 6
3 3 a 553.18782 2
, 2 or
2 3 2
kgmol m kgmol2
RTC vC 9 R vC TC
a a kN m
8vC
2
8 8.31451` 647.3K
R TC kgmol K
9 b
8 PC kN
8 22090 2
m
3.18 Derive an expression for the change of entropy of a m3
gas using the van der Waals equation of state. b 0.030455
kgmol
Solution : 8.3145725 273 553.18782
dT P 1000
v 0.030455
2
d s CV dv v
T T V
553.18782 8297.88098
1000 0
RT a P R 2
v 0.030455
P T v b
v
v b v2 V
V V
v MW m MW
m v 3.21 Three hundred pounds of a mixture of 10 mol% propane,
0.2m 3 kg 20% n-butane, and 70% n-pentane is completely vaporized in a
m 18.016 0.43614kg
m3 kgmol pipe still in one hour. At the outlet, the temperature and
8.261624
kgmol pressure are 515 F and 600 psia. What is the volumetric flow
(c) the generalized compressibility chart. rate in cfm at the outlet conditions?
Computing for reduced pressure and temperature Solution:
P 1000 kPa
PR 0.04527 Basis: 100 moles mixture
PC 22090kPA
n m %n %m
TR
T
725 273K 1.54179 Gas
(mol)
MW
(lb) yi xi
TC 647.3K
Propane 10 44 440 10 6.63
Butane 20 58 1160 20 17.47
From compressibility chart using reduced pressure and Pentatane 70 72 5040 70 75.90
volume, Z = 0.998 (approximation) 100 6640 100 100
PV
Pv ZRT PV ZmRT m
Z RT Given mass: m=300 lbs mixture
mC 3 H 8 xC 3 H 8 m 0.0663300lb 19.89lb
kN
10000.2m 3
mC 4 H 10 xC 4 H 10 m 0.1747300lb 52.41lb
2
m m 0.4352 kg
kN m
0.998 0.4615 725 273K mC 5 H 12 xC 5 H 12 m 0.7590300lb 227.70lb
kg K
To re-check all the answer, using steam table (superheated number of mols
condition), the specific volume at T=725°C and mC 3 H 8 19.89lb
nC 3 H 8 0.4520lbmol
MWC 3 H 8 44 lb
lbmol
P=1000kPa is v = 0.45945 m3/kg.
m 52.41lb
V 0.2m3 nC 4 H 10 C 4 H 10 0.9036lbmol
m 0.4353kg MWC 4 H 10 58lb
v m3 lbmol
0.45945
kg mC 5 H 12 227.70lb
nC 5 H 12 3.1625lbmol
MWC 5 H 12 72lb
lbmol
3.20 The constant b in the van der Waals equation of state
n 0.4520 0.9036 3.1625 4.5181lbmol
is an indication of molecular volume, it could be used to
estimate the radius of an atom or molecule, modeled as a
sphere. Fishbane et al. give the value of b for nitrogen gas The physical properties of the gas are:
as 39.4 x 10-6 m3/mol. Estimate the radius of nitrogen
molecules. Propane Butane Pentane
Solution : Tc 369.9 K 425.17 K 469.8 K
3 665.8 R 765.31 R 845.64 R
39.4 x106 m
b kgmol
V Pc 42.0 atm 37.47 atm 33.3 atm
N A 6.0221x1023 molecule
kgmol
29
V 6.542568207x10 m 3
Applying Kay's Rule:
V
4 r 3
r3
3 6.542568207x10 29
m 3
PC yi PC ,i 0.142 0.237.47 0.733.3
p
4
i
3
V 0.25 nm 14.7 psi
PC 35.004atm 514.56 psi
p
1atm
TC yiTC ,i 0.1665.8 0.2765.31 0.7845.64
p
In the periodic table is found an atomic radius of 0.075 nm for
i
nitrogen, so the above estimate for a nitrogen molecule is
TC 811.57R
p
plausible.
Solving for the reduced pressure and temperature temperature changes from 80°F to 200°F. The gases are
hydrogen and air. ( a. 82.3, 115.2 BTU )
P 600 psi
PR 1.166
p
PC
p
514.56 psi (06) The decrease in internal energy of 3 lb of an ideal gas is
T 515 460R 1.2014 225 BTU when the pressure decreases from 100 psia to 20
TR
p
p
811.57R psia and the volume increases from 1.5 to 4.5 ft3; CV=0.25
TC
BTU/lb-R. Determine (a) the change of enthalpy and (b)
From the generalized compressibility factor chart,
temperatures at the initial and final state.
Zmix = 0.76
contains 2.5 lb and the other 1.25 lb of helium. After the (21) An adiabatic tank has an internal partition that separates
valve has been open long enough for equilibrium to obtain, two gases. On one side of the partition is air – 1.5 kg at 500
what is the common pressure in the in the sphere if there is kPa and 350°K; on the other side is ammonia – 3.0 kg at
no loss or gain of energy? ( 24 psia ) 200kPa and 500°K. Imagine now that the partition is free to
move and allows the conduction of heat from one side to other.
(15) A system consists of two vessels A and B with a Determine the final temperature and pressure of each gas,
connecting valve. The vessel A contains 15 cubic feet of assuming that the ideal gas laws, constant specific heats, may
nitrogen at 220 psia and 110°F. Vessel B contains 2 lb of be used. (472.5°K, 225.96kPa )
nitrogen at 80 psia and 60 °F. After the valve separating the
two vessels is opened, the resulting equilibrium temperature (22) Air expands in a piston-cylinder from 200 kPa, 0.2 m3, and
becomes 90°F. What is the final pressure of the mixture? ( 300°K to a final state of 0.4 m3 and 400°K. The pressure varies
180.5 psia ) linearly with volume during the process. Determine the work
and the heat transfer. (27.73kJ, 61.1kJ )
(16) (a) A sphere, 6 ft in diameter, contains oxygen at 300
psia and 80°F. How many drums 6 inches in diameter and 2 (23) One pound of air and unknown mass of CO2 occupy a 3
ft long, which are initially devoid of any gas, can be filled to a cubic feet tank at 300 psia. If the partial pressure of the carbon
pressure of 50 psia and 65°F? Assume that the temperature dioxide is 50 psia (ideal gas), determine its mass. ( 0.304 lb )
of the oxygen left in the sphere remains at 80°F. (b) The
same as (a) except that the drums initially contains O2 at 20 (24) One mol of a gaseous mixture has the following
psia and 65°F. ( a. 1400, b. 2337 ) gravimetric analysis: O2 = 32%, CO2 = 44%, N2 = 24%. (a)
Find the molecular weight of the mixture, (b) the mass
(17) Air is pumped into a 10 ft 3 tank until the pressure is constituent, (c) the mols of each constituents in the mixture,
135 psig. When the pump is stopped, the temperature is and (d) the gas constant of the mixture. (a. 35lb/lbmol,
200°F. What mass is in the tank? What is its density? (b) If b.11.2lb for oxygen, c. 0.35 mol of oxygen, d. 44.1 )
the air is allowed to cool to 70 °F, what is the pressure of
the cooled air, and its density? (a.6.13lb, 0.613lb/ft3; (25) Four pounds of oxygen are mixed with 6 lb of unknown
b.120.2psia ) gas. The resulting mixture occupies a volume of 42 cubic feet
at 40 psia and 150 °F. Determine (a) R and MW of the
(18) A certain gas at 15 in. Hg and 90°F occupies 10 ft3 (a) unknown gas constituents, (b) the volumetric analysis, and (c)
If the state is changed until the volume is 30 ft3 and the the partial pressures. (a.R=33.75 b. 48.8% oxygen c. 19.52
temperature is 540°F, determine the final pressure (b) If the psia oxygen)
state is changed until the initial pressure is trebled and the
temperature increased to 400°F. Determine the final (26) A 10 ft3 drum contains a gaseous mixture at 100 psia and
volume. ( a. 0.446 psia, b. 5.21ft3 ) 100°F whose volumetric composition is 30% O2 and 70% CH4.
How many pounds of mixture must be bled and what mass of
(19) A rigid tank, 4.0 m3 tank, contains 40 kgmol of an ideal O2 added in order to produce at the original pressure and
gas at 50°C with a molecular weight of 25 kg/kgmol. (a) temperature a mixture whose new volumetric composition is
Determine the gas pressure (b) Heat transfer occurs, and 70% O2 and 30% CH4? (bleed 1.983 lb, add 3.045 lb O2 )
the temperature decreases to 20°C. What is the pressure?
(26,868 kPa, b. 24,373kPa) (27) Five mols of gaseous mixture are comprised of 1.5
mols of nitrogen, 2.75 mols of oxygen, and 0.75 mol of
(20) A typical adult breathes 0.5 liters of air with each carbon dioxide. Find (a) the volumetric analysis, (b) the
breath and has 25 breaths per minute. At 101.3 kPa and mass of the mixture, and (c) the equivalent molecular
22°C, determine the mass of air per hour entering a weight of the mixture. (a. 30% N2, b. 163 lb, c. 32.6
person’s lungs. This person now is skiing on a mountain lb/lbmol)
where air is -10°C and the pressure is 89 kPa. How many
breaths per minute are required if the mass of air per hour (28) A gaseous mixture has the following composition by
entering the lungs is to be constant? ( 25.37 br/hr ) volume: 20% N2, 30% CO2 and 50% CH4. Determine (a) the
gravimetric analysis (b) the molecular weight of the mixture, (c)
gas constant of the mixture, (d) the specific heat at constant
pressure for the mixture, and (e) the partial pressure of N2 if of entropy. (a. 84.01%, 2.83%, 13.16% by mass b.48.8,
that of the CH4 is 9 psia? (b.26.8lb/lbmol, e. 3.6 psia ) 31.66, c.35.9 psia, 97°F, d. 29.8 psia O2 e.0.0867 BTU/R)
(29) A mixture of two gases O2 and N2 occupies a given (34) A gaseous mixture of propane, nitrogen, and hydrogen
volume at 30 psia and 200°F. If the partial pressure of O2 is has partial pressures of 83 kPa, 102 kPa, and 55 kPa,
twice that of the N2, find (a) the volumetric and gravimetric respectively. Determine (a) the volumetric analysis (b)
analysis, (b) gas constant of the mixture, (c) density of the gravimetric analysis. ( 0.346, 0.425, 0.229; 0.552, 0.431,
mixture, and (d) the final pressure and temperature if 80 0.017 )
BTU/lb of heat absorbed with no change in volume. (a.
66.7%, 69.6%; b. 50.3, c. 0.1301 lb/ft3 d.1149°R, 52.2psia (35) Ethylene is stored in 5.6 liter spherical vessel at 260°C
) and 2750 kPa. To protect against explosion, the vessel is
enclosed in another spherical vessel with volume of 56 liters
and filled with nitrogen at 260°C and 10.1Mpa. The entire
assembly is maintained at 260°C in a furnace. The inner vessel
raptures. Determine (a) the final pressure; (b) the entropy
change. (9365 kPa, 0.1671kJ/K)
(32) Equal masses of hydrogen and oxygen are mixed. The (39) The Dieterici equation of state is
mixture is maintained at 150 kPa and 25°C. For each a
(33) Compartment A in figure contains 2 lb of O2 at 50 psia (40) Derive an expression for the change of internal energy
and 100°; B contains 5 ft3 of gaseous mixture with a and entropy of a gas using the van der Waals equation of state.
volumetric composition of 12 % CO2 and 88 % N2 at 14.7
psia and 80°F. The partition is removed and the gases mix. (41) A 0.2 m3 tank contains steam at 725°C and 1000 kPa..
For equilibrium condition, find (a) the volumetric and Determine the mass in the tank using (a) the ideal gas law; (b)
gravimetric analyses, (b) mixture gas constant and the van der Waals equation of state; (c) the generalized
molecular weight, (c) mixture pressure and temperature (d) compressibility chart.
the partial pressure of each constituent, and (e) the change
(42) What does the van der Waals equation of state (47) One of the following expressions for the change of
predicts for the compressibility factor at the critical points. pressure will yield an equation of state. Determine the equation
(0.375 ) of state.
2 v b v b dT 2
dP dv
(43) Compute the coefficient of thermal expansion for RT RT2
methane at 32° and 1400°kPa using (a) the ideal gas RT R
dP dv dT
equation of state; (b) the van der Waals equation of state. v b 2 v b
The coefficient of thermal expansion is expressed as
1 V . ( 0.00328 / K ; 0.0035 / K ) (48) Given that x = x(y,v), y = y(z,v) and z = z(x,v), show
.
V T P
that x y z 1 .
y z
v v x v
(44) Determine the difference between CP and CV for a gas
(49) Two kgmol of air at 400°K is contained in a 0.5m3 piston-
that obeys the (a) ideal-gas equation of state; (b) the van
cylinder. A change of state occurs, and finally pressure is
der Waals equation of state.
15MPa and the final temperature is 350°K, Determine the initial
pressure and the final specific volume, using the ideal gas law
(45) What would be the critical parameters for a gas
and van der Waals equation of state. ( P. 13.3 MPa, 13.4
obeying the ideal-gas equation of state?
MPa; v. 0.194, 0.25 m /kgmol )
3