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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 1 of 23

GAS LAWS AND


EQUATIONS OF STATE

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
PT  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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 2 of 23

Process a – 2 : Constant Pressure Process Avogadro's Law:


“At a constant temperature and pressure, the volume of a
Va Ta Va gas is directly proportional to the number of moles of that gas.”
  Ta  T2
V2 T2 V2 Mathematically, this can be represented as:”

V  C n
Volume (V) = Constant (C) x Moles (n)

Avogadro's Interpretation of Joseph Guy-Lassac's Law:


The pressure and temperature of a gas, like the volume
and temperature, are directly proportional (assuming volume
remains constant). Mathematically, this is:
P
C
T

Explanation and Discussion:


Avogadro's Interpretation of Guy-Lussac's observations is
a law that creates a similar equation to Charles' Law. This lets
Equating the two equation of Ta, pressure and temperature be solved for with an unknown or
V P P1Va PaV2 constant volume. This completes the third part of the Combined
Ta  T2 a  T1 a   Gas Law. Avogadro's Hypothesis and Law describe the
V2 P1 T1 T2
relationship of moles of a gas to the volume of its container.
When pressure and temperature remain constant, there is a
but Va = V1 and Pa = P2,
direct relationship between the two. Experimentation has
P2 V2 P1 V1
 determined this to be about 22.4 L per each mole of a gas at
T2 T1
STP. Here is an example of this, note that the volume stays the
same but the mass varies:

Quasi-equilibrium process is a process when the


system is in equilibrium (e.g. mechanical, thermal, chemical)
at each point going from its initial to final state.

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. “

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 3 of 23

JOULE’S LAW molecules. This relationship is equal to the square-root of the


James Prescott Joule arranged two copper containers, inverse of the molecular masses of the two substances.
in a bath of water. The water was in an insulated vessel, so
that the whole apparatus could be considered as an isolated Diffusion - The rate at which two gases mix.
system, without thermal contact with outside bodies. One of Effusion - The rate at which a gas escapes through a
the containers held air at a pressure of 22 atm, and the pinhole into a vacuum.
other container was evacuated as nearly as possible. After
all parts had reached thermal equilibrium, the valve was Graham's Law of Diffusion
opened. The air rushed into the evacuated container, and The rate at which gases diffuse is inversely proportional to
the whole mass of air finally came to rest at a pressure of 11 the square root of their densities.
atm. Joule observed that there was no change in the 1
RDIFFUSION 
temperature of the water surrounding the containers, a 
simple observation that leads to an important deduction.
Since volumes of different gases contain the same
number of particles, the number of moles per liter at a given T
and P is constant. Therefore, the density of a gas is directly
proportional to its molar mass (MW).
1
RDIFFUSION 
MW

Graham's Law of Effusion


The rate of effusion of a gas is inversely proportional to
the square root of either the density or the molar mass of the
gas.
1
REFFUSION 

1
REFFUSION 
Now, from the simple energy equation MW
U  H  PV  . The pressure changed, the volume
changed, but the internal energy did not change. From this
observation Joule deduced that “the change of internal
energy of a perfect gas is a function of the temperature
change.”

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"

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 4 of 23

DALTON'S LAW OF PARTIAL PRESSURES V V i  V1  V2    Vi


The Dalton’s law of partial pressure states that “the
i

total pressure of the mixture is the sum of the pressures P  P1  P2    Pi


that each gas would exert if each of the components of
the mixture would occupy the whole container.” T  T1  T2    Ti

The ideal gas equation of state of the components of the


mixture can be written as

PVi  ni RT

dividing this equation by equation of state of the mixture

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

The ideal gas equation of state of the components of


Equation of state is a constitutive equation describing
the mixture can be written as
the state of matter under a given set of physical conditions. It
PiV  ni RT provides a mathematical relationship between two or more
state functions associated with matter, such as its temperature,
dividing this equation by equation of state of the mixture pressure, volume, or internal energy. Equations of state are
useful in describing the properties of fluids, mixtures of fluids,
PiV ni RT Pi ni
   solids, and even the interior of stars.
PV n RT P n
p1  f  p2 , p3 ,, pi 
Pi ni
yi  
P n where p1, p2, …, pi are the properties of the gas

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

Two special cases

(a) Incompressible fluid


  0
dV
 0 (no equation of state exist)
V
V is constant
(b)  and  are temperature and pressure
independent

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 5 of 23

IDEAL GAS EQUATION OF STATE PV  nT


(Perfect Gas)
By introducing a constant (universal gas constant, R ) to
The Ideal Gas Law was first written in 1834 by Emil
remove the proportionality symbol
Clapeyron. Ideal gas equation of state is simple function
that relates the dependence of pressure, volume, PV  n RT
temperature and mass at a state. It is sometimes defined as
the one that obeys the gas laws. Variations of Ideal Gas Equation of State
In terms of molecular theory, a perfect gas is one in
which P
V
 RT  Pv RT
 The molecules of the gas occupy negligible volume n
compared with the volume of the containing PV  n RT 
m
RT m
R
T
vessels MW MW
 The molecules move independently of one another but R
R
except when a collision occurs. A collision causes MW
an internal redistribution of energy between the
colliding molecules. PV  m RT
 Energy transfer into or out of the gas cause a m P 1 RT
   v 
change in molecular linear kinetic energy only; V RT  P
hence any net energy transfer result in a
proportional change in temperature. This means P   RT and Pv RT
that the specific heat capacity of a perfect gas is
constant and does not change with temperature Universal Gas Constant
and pressure. kJ ft  lb f
R  8.31451  1545
kgmol  K lbmol  R
The assumption of perfect gas behavior is usually a
good approximation for many real gases such as :
 Mono-atomic gases such as helium and argon NON-IDEAL GAS EQUATION OF STATE
 Diatomic gases such as nitrogen, oxygen and (Real Gas or Imperfect)
carbon dioxide
 Gas mixture such as air In actual gas the molecular collision are inelastic; at
high densities in particular there are intermolecular forces that
It is not such a good assumptions for vapors such as the simplified equations of state do not account for. There are
refrigerants and steam, whose properties are usually many gas equations of state that attempt to correct for the non-
obtained from property charts or tables. Perfect gas ideal behavior of gases. The disadvantages of all methods are
behavior is not a good assumptions for real gas if : that the equations are more complex and require the use of
 The gas is close to liquefaction, either highly experimental coefficients.
compressed and/or at low temperature, because
in this case, the molecules are close together.
 The gas is at very high temperature, because (a) Van der Waal’s Equation of State
dissociation and electron excitation may occur,
which involves energy other than linear kinetic A modification of the ideal gas law was proposed by
energy. Johannes D. Van der Waals in 1873 to take into account
molecular size and molecular interaction forces. It is usually
Combining all the ideal gas laws : referred to as the Van der Waals equation of state. This was
1 one of the first to perform markedly better than the ideal gas
P ; P T ; V T and V n
V law. In this landmark equation a is called the attraction
2
parameter ( a v accounts for intermolecular forces) and b
1
P 
1
T 
n V

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 6 of 23

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

Carbon monoxide (CO) 146.3 0.0394


Helium (He) 3.41 0.0234
The Redlich-Kwong equation is adequate for calculation of
Hydrogen (H2) 24.7 0.0265
gas phase properties when the ratio of the pressure to the
Methane (CH4) 228.5 0.0427
Nitrogen (N2) 136.1 0.0385 critical pressure is less than about one-half of the ratio of the
Oxygen (O2) 136.9 0.0315 temperature to the critical temperature.

The critical point has a unique temperature and pressure


known as the critical pressure and temperature. At pressures
(b) Beattie-Bridgeman Equation of State
higher than the critical pressure, the liquid could be heated from a
low temperature to a high temperature without a phase transition
R T 1 
P 2
v  B   A
2
occuring. At temperatures that are greater than the critical
v v temperature, the pressure may be increased to very high value,
and no liquefaction will occur.
where A  AO 1  a  ; B  BO 1  b 
 v  v The value of the constants a and b can be determined by
 c noting that the first and second derivatives of pressure with
vT3 respect to specific volume at the critical point are zero.
P 2P
CONSTANTS FOR THE BEATTIE-BRIDGEMAN EQUATION OF STATE 0 and 0
v TC v 2 T
C
SUBSTANCE AO a
Air 131.8441 0.01931
Argon (Ar) 130.7802 0.02328
Carbon dioxide (CO2) 507.2836 0.07132
Helium (He) 2.1886 0.05984
Hydrogen (H2) 20.0117 - 0.00506
Nitrogen (N2) 136.2315 0.02617
Oxygen (O2) 151.0857 0.02562

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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 7 of 23

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
vb v vb  
(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.

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 8 of 23

T and pressure P, The equation of state may be written for each


Reduced Temperature TR  gases as
TC
PVi  ni RT
v
Reduced Specific Volume vR 
vC
The volume fraction of the component of the mixture can
be obtain by dividing the volume occupied by the component i
A generalized chart of compressibility factors for
by the total volume occupied by all the components
reduced temperatures and pressures was developed by
Nelson and Obert. This may be used to find the properties
ni RT
of a gas if we know the critical properties. The reduced Vi ni
 P   yi
volume, V 'R , is defined as V n RT n
ZRT P
V V P TR
V 'R     Z
VC RTC RTC PR
PC PC Molecular Weight of the mixture
m m  m2    mi
MW   1
n n
MW1n1  MW2 n2   MWi ni
MW 
M I X T U R E OF N O N R E A C T I V E G A n
S n n n
MW  MW1 1  MW2 2    MWi i
n n n
IDEAL GAS MIXTURES
MW  MW1 y1  MW2 y2    MWi yi
The gases in a gas mixture are called “components of
the mixtures.” A given component i will heave a mass mi,
and the total mixture will have a mass m, where MW   MW y
i
i i

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

Enthalpy of the Mixture


The mole fraction of the gas i is defined as yi,
H  H1  H 2    H i  m1h1  m2 h2    mi hi
ni
yi  H  n1 h1  n2 h 2    ni h i
n

The ideal gas equation of state of the mixture is H  Hi


i  n hi
i i  m h
i
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,

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 9 of 23

m1C P1  m2 C P 2    mi C Pi If the components a and b are same gas, the entropy of


CP 
m mixing is zero.
C P  x1C P1  x2C P 2    xi C Pi
For Ideal Gas:

CP   xi CPi CV 
R ;
CP 
kR ; C
k  P & R  C P  CV
i k 1 k 1 CV

Internal Energy of the Mixture


U  U 1  U 2    U i  m1u1  m2 u 2    ui hi REAL GAS MIXTURES
U  n1 u1  n2 u 2    ni u i
Mixtures of real gases can be treated using any equation
of state. Empirical (experience-based) rules have been
U  U
i
i  n u
i
i i  m ui
i i developed to address such condition.

Dalton’s Law and Generalized Chart


mCV T  m1CV 1T1  m2CV 2T2    mi CViTi
Calculate reduced pressure according to
but T  T1  T2    Ti
m1CV 1  m2 CV 2    mi CVi Pi
CV  PR ,i 
m PC ,i
CV  x1CV 1  x2CV 2    xi CVi
PiV  Z i ni RT
CV   xi CVi
i
From Dalton’s law of partial pressure,

Change of Entropy and Entropy of Mixing and


P P i
i  P1  P2    Pi

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  nZ1 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

S  Sa  S b Amagat’s Law and Generalized Chart


Calculate reduced pressure according to
or
Pi
S a  S 2  S1 a  ma C Pa ln
T2 a P
 ma Ra ln 2 a PR ,i 
T1a P1a PC ,i
PiV  Z i ni RT
S b  S 2  S1 b  mb C Pb ln
T2b P
 mb Rb ln 2b
T1b P1b
S  S a  S b From Amagat’s law of additive volume,
(FOR DIFFERENT TEMPERATURE) V V
i
i  V1  V2    Vi

where:
P1  P2  ....  Pi V  Z1n1  Z 2 n2  ...  Z i ni RT
T2a = T2b mixture temperature PV1  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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 10 of 23

PV  Z1 y1  Z 2 y2  ...  Z i yi RT


The Kay’s rule assumes a linear critical curve between the
critical points for gases A and B.
PV  nZ mix RT

Kay’s Method
Kay's Rule uses psuedo-critical properties to calculate
psuedo-reduced quantities that are then used in the
generalized compressibility charts

The mixture compressibility factor, Zmix, is found from


the generalized compressibility factor chart using the system PSEUDO-CRITICAL CONSTANTS
temperature and pressure reduced using "pseudocritical
constants" given by: When answers are near the critical point for the mixture, we
PC   yi PC ,i cannot be certain that we are not dealing with a liquid vapor
p

i mixture
TC  yT
p
i C ,i
i

Generalized Compressibility Chart

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 11 of 23

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
1.5kg300K  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 25C, to the surface were the temperature is
m Final   m  42.6621kg 27C. 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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 12 of 23

Change of internal energy


H C 0.1573
U   H V  83BTU  58.65 BTU
k CP 0.2226

3.6 Determine the size of a spherical balloon required to lift a


payload of 1360 kg. The gas to be used is helium at 101.3 kPa
and 23°C. The surrounding air is 101.3 kPa and 10°C.
Solution :
P1g   h
kg  m
1000  9.8066 2 
m3  s   1kN 
P1g   5m   49.033 kPa
kg  m  1000N 
1 2
s N
P1  Patm  P1g  100  49.033kPa  149.033
Percentage Increase: V2  V1 V2
%I   1
V1 V1
mRT2
V2 P2 P1T2
%I  1   1
V1 mRT1 P2T1
P1
149.033kPa 300K  
%I    1 100 %  50.03 %
 100kPa 298K  

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  D3
6m PL 

1

1 

R P2V2  P1V1 P  AIR AIR
R T R He T He 
 778.16 ft  lb f 61360kg  
1
CP  83BTU  ft 2  1 1  kg  K 1
    D 
kN   0.287283 2.077296 kN  m K
 ,

1516.56  954 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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 13 of 23

PAIRV AIR PH 2VH 2 VUSED  1.983 ft 3


m PL  m AIR  m H 2  m PL  
R AIR T AIR RH 2TH 2
 1 1  3.9 A closed vessel A contains 3 ft3 of air at a pressure of 500
mPL  PV   
 R AIRTAIR RH 2TH 2  psia and a temperature of 120°F. This vessel connects with
vessels B, which contains an unknown volume of air at 15 psia
 14.7 lb 2 
 in  144in   2094.16 lb
2
P  29.6inHg and 50°F. After the valve separating the two vessels is opened,
  2  ft 2
 29.92inHg  1 ft  the resulting pressure and temperature are 200 psia and 70 °F,
 
respectively. What is the volume of the gas in vessel B?
D 3  30 ft 3
V    14,137 ft 3 Solution :
6 6
    lbm
 
lb f 1 1
m PL   2094.16 2  14137 ft 3 
  
 ft   53.34520 766.54530 ft  lb f
mPL  994.5 lbm

994.5 lbm  32.03 ft 2 


WPL
m g
 PL O   s 
gC lbm  ft
32.174 2
s  lb f
W PL  990 lb f

3.8 A drum 6 inches in diameter and 40 inches long


contained acetylene at 250 psia and 80°F. After some of the The mixture properties are
acetylene was used the pressure was 200 psia and the VM  VA  VB and mM  mA  mB
temperature was 70°F (a) what portion of the acetylene was
used, and (b) what volume would the used acetylene occupy PM VM PAV A PBVB PM V A  VB  PAV A PBVB
    
at 14.7 psia and 60°F. RTM RT A RTM TM TA TM
Solution : PM V A PM VB PAV A PBVB
  
Assuming that the tank is rigid, therefore, V1 = V2 TM TM TA TM
D 2  6in2  1 ft 3 
V h  40in   0.6545 ft 3
3 
P P  P P 
4 4 3
 12 in  VB  M  B   V A  A  M 
 M
T TM   A
T TM 
1
P  PM PB 
lb
2502
0.6545 ft 3   144in 2  P
VB  V A  A  M   
in  TA TM  TM TM 
m1 
ft  lb f  2   0.7352lbm
59.35 80  460R  ft 
lbm  R 1
 500 200  200 15 
VB  3 ft 3     
200 2 0.6545 ft 3 
lb
 120  460 70  460  70  460 50  460 
in  144in 2 
m2     0.5992lbm VB  4.1791 ft 3
ft  lb f 2
59.35 70  460R  ft 
lbm  R
3.10 The gravimetric analysis of dry air is approximately
mUSED  m1  m2  0.7352  0.5992  0.136lbm O2=23.1% and N2=76.9%. Calculate (a) the volumetric analysis
m  0.136 
(b) the gas constant, (c) the respective partial pressures, and
%mUSED  USED   100%  18.5% (d) the specific volume and density of the mixture when the
m1  0.7352 
mixture pressure and temperature are 14.7 psia and 60°F,
mUSED RTUSED respectively. (e) How many pounds of oxygen must be added
VUSED  to 5 lb air to produce a mixture which is 50% oxygen by
PUSED
volume?
 ft  lb f 
0.136lbm  59.35 60  460R Solution :
 lbm  R   ft 2 
VUSED   2

lb f  144in 
14.7 2 Mass MW n
in GAS % Grav. % Vol.
(lb) (lb/lbmol) (lbmol)

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 14 of 23

O2 0.231 1.155 32 0.03604 0.2082 mO 2 added  nO 2 added MWO 2


N2 0.769 3.845 28.0116 0.13731 0.7918
 lb 
SUM 1.00 5 lb - 0.17341 1.00 mO 2 added 0.101222lbmol 32   3.2391lbm
 lbmol 

(a) volumetric analysis


3.11 A rigid tank containing 3 lb of a gaseous mixture of
yO 2  20.814 and y N 2  79.186
nitrogen and carbon dioxide (each 50% by volume) at 40 psia
and 150°F receives 1 lb more of nitrogen with the temperature
(b) gas constant remaining at 150°F. For the resulting 4lb, determine (a) the
xi
R  R gravimetric and volume analyses, (b) the pressure and (c) the
MWi
i
molecular weight.
ft  lb f  0.231 0.769  lbmol
R  1545  , Solution :
lbmol  R  32 28.016 lb Since the tank is rigid, therefore V1 = V2 = V
ft  lb f
R  53.5611 MW1   MWi yi
lbm  R i

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 psia0.20814 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 psia0.79186 m1T1
P n V  V1  V2  R1
PN 2  11.64 psia P1
3lbm 150  460R  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  460R  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  0.0833lbmol0.50  0.04165 lbmol
 lbm  ft
n1CO2  n1 y1CO2  0.0833lbmol0.50  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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 15 of 23

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  2lbm  0.24723  90R  133.506 BTU
lbmol
n2CO2  n1CO2  0.04165lbmol  lbm R

n2  n2 N 2  n2CO2  0.077345 0.04165lbmol


n2  0.119lbmol 3.13 A rigid insulated tank is divided into two sections by a
membrane. One side contains 0.5 kg of nitrogen at 200 kPa
and 320°K, and the other side contains 1.0 kg of helium at 300
(a) the gravimetric and volume analyses,
kPa and 400 °K. The membrane is removed. Determine (a) the
m 2.1669 lbm
x2 N 2  1 N 2  100%  54.17 % mixture temperature and pressure; (b) the change of entropy
m2 4lbm
for the system; (c) the change of internal energy of the system.
m1CO 2 1.8331 lbm
x2CO 2   100%  45.83 % Solution :
m2 4lbm
n 0.077345
y2 N 2  2N 2  100%  65 %
n2 0.119
n2CO 2 0.04165
y 2CO 2   100%  35 %
n2 0.119

(b) the pressure of the 4 lb mixture


xi
R2  R 
MWi
ft  lb f
 0.5417 0.4583 lbmol
R2  1545  ,
lbmol  R  28.016 44.01  lbm xN 2 
0.5
 0.3333 and x He 
1
 0.6667
0.5  1 0.5  1
ft  lb f
R2  45.9621 xi  x x 
lbm  R R  R  R  N 2  He 
m 2T2
MWi  MWN 2 MWHe 
P2  R2
V2 kJ  0.3333 0.6667 kgmol
R  8.31451  ,
kgmol  R  28.016 4.003  kg
4lbm 150  460R  ft  lb f   1 ft 2 
P2   45.9621   kJ
13.63 ft 3
 lbm  R   144in 2  R  1.48364
kg  R
P2  57.14 psia
Volume of the mixture
(c) the molecular weight of the 4 lb mixture m N 2 RN 2TN 2 mHe RHeTHe
m 4lb lb V  VN 2  VHe  
MW2  2   33.61 PN 2 PHe
n2 0.119lbmol lbmol  0.50.2968320 1.02.077400 kg, K kN  m
V    , kN kg  k
 200 300
3.12 Four pounds of CO and 2 lb of CH4 at 90°F are in a 20 m2
V  3.0068m 3
ft3 rigid drum. Find the amount of heat needed to cause a
temperature rise of 100°F.
Solution : (a) the mixture temperature and pressure
Heat addition at constant volume process, therefore
internal energy given up by helium= internal energy absorbed by
C = CV,
nitrogen
T2  T1  90F  100F   190F
 U N 2  U He  U He  U N 2  0  U
T  T2  T1  90F  or R
mN 2CVN 2 T  TN 2   mHe CVHe T  THe   0
CV   CVi xi  CVCO xCO  CVCH 4 xVCH 4
i
mN 2CVN 2T  mN 2CVN 2TN 2  mHeCVHeT  mHeCVHeTHe  0
BTU  4  BTU  2  T mN 2CVN 2  mHe CVHe   mN 2CVN 2TN 2  mHe CVHeTHe   0
CV  0.1778    0.3861  
lbm  R  4  2  lbm  R  4  2  m N 2 CVN 2TN 2  mHe CVHeTHe
T 
CV  0.24723
BTU m N 2 CVN 2  mHe CVHe
lbm  R

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 16 of 23

0.50.7431320K   1.03.1189400K  For adiabatic system, Q = 0, no heat is rejected and added to


T
0.50.7431  1.03.1189 the system. Therefore from SFEE;
T  391.48 K Q  H  WSF  0
mRT 0.5  1.0kg 391.48K   kN  m  WSF   H   mC P T
P  1.48364 
V 3.0068m 3  kg  K 
C P   xi C Pi
i

P  289.75 kPa CP  1.03990.50  0.8440.30  0.91850.20


kJ
C P   0.95685
(b) the change of entropy for the system kg  K

nN 2 
mN 2

0.5kg
 0.0178kgmol R   xi Ri
MWN 2 28.016 kg i
kgmol R  0.29680.50  0.18890.30  0.25980.20
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  280K
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 sK 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 :

MIT-School of Mechanical Engineering 


THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 17 of 23

 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
sK

 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  0.4996328.016  13.9975kg
360
kJ
kg S He  6.351586
m He  2 sK
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  1.03990.12502  5.19540.87498
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

H N 2  H He  m N 2 C PN 2 T  T1N 2  Van der Waals Equation of State


m3  kg 
 mHe C PHe T  T1He  v
V

V
 vMW  0.40  28.01 
n m kg  kgmol 
mN 2C PN 2T  mN 2C PN 2T1N 2  mHe C PHeT MW
 mHe C PHeT1He  0 m3
v  11.204
kgmol
m N 2 C PN 2T1N 2  m He C PHeT1He
T RT a
m N 2 C PN 2  m He C PHe P 
vb
2

13.99751.0399560K   25.1954360K  v
T
500K  146.3 kPa  m2
6
13.99751.0399  25.1954
kJ
8.31451
kgmol  K kgmol
T  476.7 K or 203.7C 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  350kPa0.50  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  350kPa0.50  175 kPa Show that, at critical isotherm, (a) a  9 2
RvCTC ; (b)
8

b  13 vC

MIT-School of Mechanical Engineering 


THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 18 of 23

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  273K
kg  K
 RTC
2 3
2a RTC vC
 0 ; a  v
V

V V
 MW 
0.2m 3 
18.016
kg 

vC  b2 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  b3 TC vC 4 3vC  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 :
3vC  b 
3
2 vC  b 
2
3vC  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 : 8.3145725  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

dT  P  After a series of iteration, using numerical method to find v


d s  CV  dv
T  T  V (m3/kgmol) with initial trial based on the specific molecular
2 dT 2 dv
2 volume obtain from the ideal gas equation of state (8.29772
d s   ds  CV  R
1 T 1 1
vb m3/kgmol).
T v2  b m3
s 2  s 1  CV ln 2  R ln v  8.261624
T1 v1  b kgmol
 v2  b  to check
 T 
 s  CV  ln 2   R  ln 
 553.18782 8297.88098
 T1   v1  b  1000   0
8.2616242
8 . 261624 0.030455

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 19 of 23

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  273K  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  0.0663300lb  19.89lb
kN
10000.2m 3 
mC 4 H 10  xC 4 H 10 m  0.1747300lb  52.41lb
2
m m  0.4352 kg
 kN  m 
0.998 0.4615  725  273K mC 5 H 12  xC 5 H 12 m  0.7590300lb  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 x106 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
 r3

3 6.542568207x10  29
m 3
 PC   yi PC ,i  0.142  0.237.47  0.733.3
p

4
i
3
V  0.25 nm  14.7 psi 
PC  35.004atm   514.56 psi
p

 1atm 
TC   yiTC ,i  0.1665.8  0.2765.31  0.7845.64
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.

MIT-School of Mechanical Engineering 


THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 20 of 23

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  460R  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

(07) The increase of the enthalpy of an ideal gas is 134.3 BTU


Basis: 1 hour flow
when the pressure increases from 15 psia to 150 psia and the
Z mix n RT volume decreases from 16.84 to 2.63 cubic feet. Determine (a)
V 
P
the change of internal energy and (b) the final temperature of
 ft  lb f 
0.754.5181lbmol1545 515  460R the gas if the initial temperature is 83°F. ( a. 108.2 BTU, b.
 lbm  R 
V  388°F )
 lb  144in 2 
 600 2  
 in  ft 2 
(08) An empty, opened can is 30 cm high with a 10 cm
V  59.08 ft 3 diameter. The can, with the open end down, is pushed under
V 59.08 ft 3  1hr  water with a density of 1000 kg/m3. Find the water level in the
V     0.985CFM
t 1hr  60 min  can when the top of the can is 50 cm below the surface.
Thermal equilibrium exists at all times. (2.1cm)

(09) A 1 kg gaseous system in a piston-cylinder receives heat


EXERCISES at a constant pressure of 350 kPa. The internal energy
increases 200kJ, and temperature increases 70°K. If the work
(01) Carbon dioxide at 25°C and 101.3 kPa has a density of done is 100 kJ, determine (a) CP; (b) the change in volume. (
1.799 kg/m3. Determine (a) the gas constant; (b) the a. 4.286kJ/kg-K b. 0.286m3 )
molecular weight based on the gas constant.
(a.0.18896kJ/kg-K, b. 44 kg/kgmol ) (10) A spherical balloon measures 10 m in diameter and is
filled with helium at 101 kPa and 325 °K. The balloon is
(02) For a certain ideal gas R = 0.270 kJ/kg-K and k=1.25. surrounded by air at 101 kPa and 320 °K. Determine the lifting
Determine (a) CP (b) CV and (c) MW. ( a. 1.35, b.1.08, c. force. ( 4875.5 N )
30.79 )
(11) A hot air balloonist wishes to operate at an altitude were
(03) For a certain ideal gas, R=51.4ft-lbf/lbm–R and the pressure is 94kPa, temperature is 274 K, the balloon
k=1.384. (a) What are the values of CP and CV (b) What diameter is 10 m, the payload is 200kg. What temperature
mass of this gas would occupy a volume of 15m3 at 75psia must air in the balloon be, to achieve this? (400.5 K)
and 80°F? (c) If 30 BTU are transferred to this gas at
constant volume in (b), what are the resulting temperature (12) Helium is assumed to obey the Beattie-Bridgeman
and pressure? (a. 0.238, 0.172BTU/lb-R, b.5.84 lb, equation of state. Determine the pressure for a temperature of
c.109.9°F and 79.1 psia ) 500°C and a specific volume of 5.2 m3/kg. Compare with the
ideal gas equation of state. (309.0kPa, 308.8kPa)
(04) Ten pounds of an ideal gas with R = 50.8 ft-lbf/lbm–R
and k=1.18 are heated from 75°F to 200°F. What is (a) the (13) Given a pressure of 500 kPa and a temperature of 500°K
change of internal energy, (b) change of enthalpy, (c) for a carbon dioxide, compute the specific volume using the
change in flow work and (d) CP? (a. 453.3BTU, b.535BTU, Beattie-Bridgeman and ideal gas equation of state.
c. 84.7 BTU d. 13.02 BTU/lbmol-R)
(14) Two spheres, each 6 ft in diameter, are connected by a
(05) Calculate the change of (a) internal energy and (b) pipe in which there is a valve. Each sphere contains helium at a
enthalpy for 4 lb each of the following gases, when the temperature of 80 °F. With the valve closed, one sphere

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 21 of 23

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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 22 of 23

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)

(36) A gas mixture has components with the following mass


fraction: 50% carbon dioxide, 20% carbon monoxide and 30%
Helium. The mixture temperature and pressure are 50°C and
( Problems 30, 31 and 32 ) 150 kPa. Determine (a) the mole fractions; (b) the partial
pressure of each component; (c) the mixture gas constant. (
(30) The thermodynamic system shown in the figure is an a. 0.122, 0.076, 0.802; c.0.777 kJ/kg-K )
insulated rigid container divided internally with a partition.
Initially, side A contains 1 lb of nitrogen at 15 psia and (37) A gas mixture with molal analysis of 60% nitrogen and
100°F, and side B contains 2 lb of methane at 50 psia and 40% oxygen enters an adiabatic compressor at 1.5 kg/s,
300°F. If the partition is removed and the gases mix, 100kPa, and 290°K. The discharge pressure is 500 kPa and
determine (a) the pressure and temperature of the mixture, the discharge temperature is 500 °K. Determine (a) power; (b)
(b) the changes in internal energy and entropy for the entropy production. (-311.1kW, 0.128kW/K)
system AB.
(38) A mixture containing 50% He and 50% N2 on a mass
(31) In the figure shown, there is O2 in compartment A and basis enters a nozzle at 450 °K and 500 kPa with a velocity of
CO in B, each gas being at 50 psia and 150°F; VA=VB=3 ft3. 50 m/s. It expands adiabatically through the nozzle. The exit
The partition is removed and the gases mix. What is the velocity from the nozzle is 300 m/s. Determine the exit
change of entropy? ( +0.06295 BTU / R ) temperature and pressure.

(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

component determine the volumetric analysis and its partial P v  b  e RT v


 RT , where a and b are constants. Show
pressure. ( 0.94, 0.06; 141 kPa, 9 kPa ) that, at the critical isotherm is a  2 R TC vC and b  12 vC .

(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

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THERMODYNAMICS-I : Gas Laws and Equations of State chapter III - 23 of 23

(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

(46) Two kilogram of air occupies a volume of 0.05 m3 at a


(50) A rigid tank contains 1.5 kg of oxygen at 5000 kPa and
temperature of 318°C. The air expands isothermally until the
190°K. The temperature of the oxygen is lowered, and the
pressure is 1390 kPa. Using the van der Waals equation of
pressure becomes 4000 kPa. Determine the tank’s volume and
state determine; (a) the initial pressure; (b) the final; volume
the final temperature using (a) the ideal gas-equation of state;
(c) the work. ( 6885kPa, 0.244 m3, 563kJ )
(b) the compressibility chart; (c) the Redlich-Kwong equation of
state.

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