IDEAL & REAL GASES

Plotting the variables P, V, T for an ideal gas on three mutually

perpendicular axes, the three dimensional entity generated is
called P-V-T surface and can be used for studying the
THERMODYNAMIC PROPERTIES.
SPECIFIC HEATS OF AN IDEAL GAS
Cavg= Q/n∆T =q /∆T
c = lim∆T⇾O q/∆T = ∆q/∆T
McpdT = mcvdT+pdv
Mc p(T 2-T1 )+mR(T2 –T1)
Cp = C v + R
ϒ – 1 = R/Cv
Cp = ϒR/ ϒ -1
Cv = (dq/dT)v = dU/dT
CP = ( dq/dT)P =dh/dT
Specific heats
The specific heats at constant volume and at constant
pressure may be found on either mass or molar basis
since internal energy and enthalpy are functions of
temperature only.
mmum =maua + mb ub + mc uc + …
Since Um =cv dT
mmcvdT =( ma cva + mb cvb + …)dT
cvm =yb cva + yb cvb + …=∑ yi cvi
Similarly cvm =xa cvb + …=∑ xi cvi
The specific heat at constant pressure can be obtained
using mm hm =ma ha + mb hb + … since h = cp dT
mm cpm dT =(ma cpa + mb cpb ) dT
cpm = ya cpa + yb cpb + ….=∑i=1 yi cpi
Similarly cpm=xa cpa + xb cpb+ …. =∑i=1 xi cpi
 PROPERTIES OF GAS MIXTURES

INTERNAL ENERGY
On the basis of Gibbs Dalton law the internal energy
of a mixture is given as following which is known as
Gibbs theorem
V m = Va + Vb + …
M m Vm = m a Va + m b Vb + …
Nm Vm = na Va + nb Vb + ..
Vm = xa Va + x b Vb + xc Vc + …
Vm = ya Va+ yb Vb + yc Vc+ …
(Total internal energy = sum of the internal energy of
individual constituents)
U=∑yiVi = ∑ xi Vi = ∑ mi Vi ⁄ ∑mi = ∑ ni Vi ⁄ ∑ ni
Enthalpy
The enthalpy of mixture of ideal gases is simply
the sum of enthalpies of individual chemical
constituents.
Hm = Ha + Ha +Hc + … mm
hm = m a ha + m b hb + …
hm = ya ha + yb hb +…
hm = ya ha + yb hb + …. ∑i=1 yi hi Also
nm hm = na ha + nb hb + …
hm = xa ha + xb hb + …∑i=1 xi hi
Entropy
Sm = S a + S b + …
Mm Sm = ma Sa+ mb Sb + mc Sc + …
Sm = ya Sa + yb Sb + yc Sc + …=∑i=1 yi Si
Also nm Sm = na Sa + nb Sb + nc Sc + …
Sm = xa Sa + xb Sb + xc Sc + ….∑i=1 xi Si
Entropy change of a perfect gas a function of temperature and
pressure is expressed as
dS = cpdT/T
ma [cpa dT/T – Ra dpa/Pa ] + mb [ cpb dT/T - R dpb/Pb ] + ….
S2 – S1 = ma [ cpa In T2/T1 - Ra In Pa2/P a1 ] + m b [ cpb In T2/T1 - Rb
In Pb2/Pb1 ]
Similarly on molar basis
(S2 – S1 ) = ma ( cpa In T2/T1 - Ra In Pa2/Pa1 ) + mb( cpb In T2/T1 -
Rb In Pb2/Pb1 )
Entropy change due to mixing
dS = ∑ yi (dSi)>= 0
∆S = -( ma Ra In Pa/ P + mb Rb In Pb/p + ..)
= - ∑ mi Ri In Pi2/ Pi1
∆S = - ∑ yi Ri In Pi2/Pi1
 IDEAL & REAL GAS BEHAVIOR

Equation of state: P= (RT/V) P⇾0

BOYLES LAW :V∝1/P
PV=C
CHARLES LAW: V∝T
V/T= C When pressure is constant
Similarly
P∝T
P/T= C when volume is constant
CHARACTERSITIC EQUATION OF GAS
PV/T = CONSTANT= R
Where R is called characteristic gas constant.
AVAGADRO’S HYPOTHESIS:6.023*1026
1Kg mole of all gases at norma pressure and temp have 22.4m3
UNIVERSAL GAS CONSTANT
PV=mRT
PV=n T

=8.314 kJ/kgmol.K

FREE EXPANSION: The process is irreversible and adiabatic,

W=0,Q=0 at the same time U=0 hence this process is constant
enthalpy process but not as adiabatic and isothermal process.
Thus isothermal or adiabatic process can be reversible but
FREE EXPANSION is irreversible.
GAS PROCESS AND ENERGY INTERACTION
 REAL GAS BEHAVIOR:

EQUATION OF STATE FOR A REAL GAS

PV= a+b/V +c/V2

VANDERWALL’S EQUATION OF STATE:

(P+a/V2 )(V-b)= RT
At critical state
PC =[RTC / (VC -b)] – a/VC2
Differentiate Twice the above equation w.r.t. to Volume at
temperature constant we have
b= VC /3
a= 27RTcb/8
PC= a/27b2
VANDERWALL’S REAL GAS
LAW OF CORRESPONDING STATES:
P R = P/PC , V R = V/VC , T R = T/TC

COMPRESSIBILITY CHARTS
PV/RT=Z
Z=V/ (RT/P)
LtP⇾0 Z=1
Z<1 WILL BE MORE COMPRESSIBLE THAN A PERFECT
GAS
V R = V/VC =(ZRT/P) / Z CRT C/PC
Z/ZC = TR /PR
f(TR ‘PR ‘Z/ZC )=a
ZC =3/8
WHILE FROM THE CHART ZC =0.25
vanderwall’s equation gives much error at low pressures if the gas
has different zc values
VARIABLE SPECIFIC HEATS
CP = a+bT+cT2 +dT3
 PROPERTIES OF GAS MIXTURES
MASS OF THE MIXTURE
mm = ma + mb + mc
MASS FRACTION
Ya = m a / m b
Ya + Yb + Yc +…..= 1
Number of Moles = Mass of the gas / Molecular
Weight
na + nb + nc +…..= nm
MOLE FRACTION
xa=na/nm

xa + xb + xc +…..= xm
AVERAGE MOLECULAR WEIGHT OF THE MIXTURE
M=nm
nmm m = na m a + nb m b + ncm c +…..
m m = xa m a + xb m b + xc m c +…..
xa = na /nm

GIBB’S DALTON LAW OF PARTIAL PRESSURES

P =Pa +Pb + PC +Pd +………….
(Pa +Pb + PC +Pd +……..)V = (na + nb + nc +…..) T
Pa /P = na /nm = xa
Pa = xaP
Similarly
Va /V = na /nm = xa Therefore Va = xaV
GAS CONSTANT OF THE MIXTURE
PV= mRT
PaV= m aR aT
PbV= m bR bT
PcV= m cR cT
(Pa +Pb + PC )V= (m aR a + m bR b+ m cR c )T
PV= (m aR a + m bR b+ m cR c )T
Compare this with equation PV=mRT
mR= (m aR a + m bR b+ m cR c +…….)
R= (ma /m )R a + (mb /m )R b +…….)
R= ya R a + yb R b + yc R c +…………
Molecular weight of the mixture
m mRm= (m aR a + m bR b+ m cR c +…….)

mm R0 /Mm =m a R0 /Ma + m b R0 /Mb + m c R0 /Mc +…….)

1/ Mm = Ya / Ma + Yb / Mb + Yc / Mc +………

Mm = 1/ [Ya / Ma ] + 1/ [Yb / Mb ] + 1/ [Yc / Mc ] +…..

Determine the pressure of 5 kg carbon dixoide contained
in a vessel of 2 m3 capacity at 27º C,
considering it as
(i) perfect gas
(ii) real gas.
2) In 5 kg mixture of gases at 1.013 bar and 300 K the various
constituent gases are as follows,80% N2, 18% O2, 2%
CO2.Determine the specific heat at constant pressure, gas
constant for the constituents and mixture and also molar mass
of mixture taking ã = 1.4 for N2 and O2 and ã = 1.3 for CO2.
Universal gas constant = 8314 J/kg K.
3) A gas mixture comprises of 18%O2, 75% N2 and 7%CO2 by volume at
0.5 MPa and 107ºC. For 5kg mass of mixture carry out gravimetric
analysis and determine the partial pressure of gases in mixture.
9) 0.1m3 of hydrogen initially at 1.2 MPa, 200°C undergoes a reversible
isothermal expansion to 0.1 MPa. Find (a) the work done during the
process, (b) the heat transferred, and (c) the entropy change of the gas
8) A closed adiabatic cylinder of volume 1 m3 is divided by a
partition into two compartments 1 and 2. Compartment 1 has a
volume of 0.6 m3 and contains methane at 0.4 MPa, 40°C, while
compartment 2 has a volume of 0.4 m3 and contains propane at
0.4 MPa, 40°C. The partition is removed and the gases are
allowed to mix.(a) When the equilibrium state is reached, find
the entropy change of the universe.
(b) What are the molecular weight and the specific heat ratio of
the mixture?The mixture is now compressed reversibly and
adiabatically to 1.2 MPa. Compute(c) the final temperature of
the mixture,(d) The work required per unit mass, and (e) The
specific entropy change for each gas. Take p c of methane and
propane as 35.72 and 74.56 kJ/kg mol K respectively.
10) A vessel is divided into three compartments (a), (b), and (c)
by two partitions. Part (a) contains oxygen and has a volume of
0.1 m3 , (b) has a volume of 0.2 m3 and contains nitrogen, while
(c) is 0.05 m3 and holds CO2 . All three parts are at a pressure of
2 bar and a temperature of 13°C. When the partitions are
removed and the gases mix, determine the change of entropy of
each constituent, the final pressure in the vessel and the partial
pressure of each gas. The vessel may be taken as being
completely isolated from its surroundings.

T=276K