5.

IDEAL GASES AND MIXTURES

At temperatures that are very much in excess of the critical temperature of a fluid, and

also as its pressure is considerably lowered, the vapor of the fluid tends to obey Boyles law and
Charles law exactly
Boyles law At constant temperature the pressure of a fixed mass of gas and its volume
are connected by the law
Pv = constant
i.e.

pv= f(T) ..5.1

Charles law
a. At constant pressure v T for a fixed mass of gas
i.e.

v
(P)......... ......... 5.2
T

b. At constant volume pT for a fixed mass of mass.

P
(P)......... ......... 5.3
T
Gay-Lussac also arrived at Charles law independently
5.1

THE EQUATION OF STATE FOR THE PREFECT GAS

Now consider a fixed mass of gas obeying both Boyles and charles laws. Change its

state from p1, v1, T1 to P2, V2, T2 by passing through an intermediate state P2, Vx, T1.
By Boyles law
P1V1 = P2Vx at T1
Vx =

p1v1
(5.4)
p2

By Charles law

Vx V2

at p2
T1
T2

Vx

T1V2
(5.5)
T2

eqn 5.4 and 5.5

p1V1 T1V2

P2
T2

P2V2
= R where R is a constant for the particular gas.
T2

pv RT 5.6
Suitably selecting the intermediate state, eqn 5.6 can also be obtained from the
combination of any other two of equations 5.1, 5.2, and 5.3. Perfect (or ideal) gas may be defined
as one which obeys exactly the equation pv=RT, where R is a constant having a particular value
for each substance and is called the characteristic Gas constant.
This equation is known as the equation of state for a perfect gas

pv mRT 5.7
Where m is the mass of the gas
The unit of R is Nm/kgK or kJ/kgK.
The molecular weight of a =

mass of one molecule of the subs tan ce

1 / 32 (mass of one molecule of oxygen)

The mole is a quantity of a substance whose mass is numerically equal to its molecular
weight.
In SI units the mole is the kilogram-mole
1 kilogram-mole of a substance has mass equal to M kg
Where M is molecular weight of the substance.
Eq. 5.5 then becomes
Pv= n MRT -------(5.8)
Where n is the number of moles

Now, Avogadros hypothesis states that equal volume of different ideal gases at the same
pressure and temperature contain the same number of molecules. This means that at the same
temperature and pressure 1 mole of any local gas will occupy a fixed volume.
Experiment has shown that the volume of one mole, of any perfect gas at 1 bar and
273.15k is appropriately 22.71m3
Consider equal volumes of ideal gases a and b at the same pressure and temperature.
Pv = nMaRaT
and pV = nMbRbT since equal volumes of different ideal gases contain the same number
of moles.
MaRa = MbRb
So the product MR is a constant for all gases and is called the universal gas constant and
is denoted by Ro.
MR = Ro
The unit of Ro is Nm/Kgmole-K or KJ/kgmole-K from of 5.6

pV
nRo 5.9
T
PV 1x105 x 22.71
Ro

8314.3 Nm / kgmole K
nT
1x273.15
= 8.3143kJ/kgmole-K

5.2

Joules Law
Joule deduced experimentally that the change in internal energy of a gas is a function of

only the temperature change. The experiment, first performed by Gay-Lussac, had two copper

vessels A and B submerged in water (Fig. 5.1). Vessel A held air at 22atm while B, of the same
volume, was evacuated. The two vessels were connected with an initially closed value. The
system consisted of the insulated water container and the copper vessels. The contents of the
insulated system were in thermal equilibrium.
After the valve was opened and the gas had settled, the pressure was measured to be
1l atm. No water temperature change was observed and so Joule concluded that no change in air
temperature would have occurred.

dQ = 0 and dW = 0
since dQ = du + dW
du = 0.
The pressure of the air changed, the volume also changed and so
u
0 and
v T
u
0
p T

Consequently Joule concluded that internal energy of the gas was not a function of the
volume or pressure. It must be a function of temperature.
Since the mass of the water and container was very much larger than that of the air; a
small change in air temperature might go undetected in water temperature. The experiment could

not have been accurate enough to make deductions, it is now known that a real gas should exhibit
a small drop in temperature after a free expansion. Nevertheless, Joules deduction can now be
proved mathematically for the perfect gas. The proof is beyond the present scope of work.
What is now known as Joules law will be stated as follows:
The internal energy of a perfect gas is a function of only the temperature.
U= U(T)
Enthalpy of a Perfect Gas
Since Pv = F(T) for a perfect gas
and U = U(T), it follows that h(=u + pv) is a function of only temperature for a perfect gas.
h = h(T)
5.3

The Joule-Thomson Experiment

As a result of criticisms of the Joule experiment described above, Joule and Thomson

(later Lord Kelvin) carried out the porous plug experiment to obtain more accurate results.
The experiment consisted of a well-insulated pipe with a porous plug that offered
considerable resistance to flow so that there could be relatively large drop in pressure from p1 to
p2 (fig. 5.2).

Fig. 5.2
It had been shown earlier that applying SFEE and neglecting potential and kinetic energies
h1 = h2

Joule and Thomson found that for air T2 < T1 and for hydrogen T2 >T1 and so found out
that for real gases h and u are functions of temperature. However for all the conditions for which
real gas behaviours approaches that of the perfect gas, T2 = T1; i.e h1=h2
5.4

Specific Heat of Perfect Gases

For constant volume process,

h
Cv

T p
i.e. rate of change of enthalpy with temperature.
Since u and h are independent of p and v, the partial notation may be dropped for perfect
gases.

Cv
5.5

du
dh
and C p
dT
dT

Relation between Cv, Cp, and R for a Perfect Gas

h u pv u RT
dh
du

R
dT dT
C p Cv R 5.10

Molar Specific Heats:

and C v MC v

C p MC p
C v and C p are known as molar specific heats
C p C v R 5.11

Ratio of Specific Heats

CP C p

CV
Cv
R C p Cv
R
1 5.12
Cv

1
R
1 1/
5.13
Cp

Similarly
R
R 1
1 and

Cv
Cp

Units
du
Cv
KJ / kg K
dT
du

Cv M
KJ / kg mole K
dT

dh
Cp
KJ / kg K
dT
Mdh
C p
KJ / kg mole K
dT
5.6
Mean (on Average) Specific Heat for Gases
The mean specific heat for any process between T1 and Ti is defined by the relation

CV

T2

T1

Cv DT

T2 T1

U 2 U1
T2 T1

h2 h1
T2 T1

and
Cp
5.7

T2

T1

Cv DT

T2 T1

Properties of a Perfect Gas

For a perfect gas Cv and Cp are constant. For any change from state (1) i.e. p1, v1, T1 to
state (2) i.e. p2, v2, T2
U2-U1 = Cv (T2-T1) and h2-h1 = Cp (T2-T1)
Entropy of a Gas During a change from state, p1, v1, T1 to state p2, v2, T2
From the 1st law equation

dQ = du + dW
= du + pdv
From the definition of entropy
dQ = Tds
Tds du pdv --------5.14
Now h = u + pv
dh = du + pdv + vdp
du = dh-pdv vdp
Tds dh vdp ------- 5.15
The entropy of a perfect gas may be obtained by impetrating eq. 5.14 or eq. 5.15.
from eq. 5.14
Tds = du + pdv
dv
CvdT + RT
v
dT Rdv
ds = Cv

T
V
T
V
S1 S2 Cv1n 2 R1n 2
T1
V1
But

T2 P2V2

T1
P1V1

PV
V
S 2 S1 Cv 1n 2 2 R ln 2
P1V1
V1
P
V
V
Cv 1n 2 Cv 1n 2 R ln 2
V1
V1
P11
P
V
Cv 1n 2 Cv R 1n 2
V1
P11
P
V
Cv 1n 2 C p 1n 2
V1
P11
P
V
S 2 S1 Cv 1n 2 C p ln 2 .......... .5.16
P1
V1

5.8
a.

PROCESSES PERFORMED BY PERFECT GASES

Reversible Adiabatic (Isentropic) Process
If the change is isentropic
S2-S1 = 0
P
V
S 2 S1 Cv 1n 2 C p ln 2 0
P1
V1

P C
V
ln 2 p ln 2 0
P1 Cv
V1
P
V
ln 2 ln 2 0
P1
V1
P
ln 2
P1

V
ln 2

V1

P V
2 2
P1 V1
PV cons tan t 5.17

NOW P1V1 P2V2

1

RT2V2

P
1
P2

RT1V1
T1 V2

T2 V1

V1 P2

V2 P1

T V
1 2
T2 V1
b.

Constant volume Process

dQ = du + dw
dw = 0
dQ = du
=CvdT
Q = Cv (T2-T1) -----5.19

Also dQ = Tds = CvdT

dT
ds = Cv
T

5.18

 S 2 S1 Cv ln

c.

T2
5.20
T1

Constant Pressure Process

dQ = du + dw = cvdT + pdv
T2

V2

T1

V1

Q Cv dT Pdv
Cv T2 T1 p V2 V1

Cv R T2 T1 C p T2 T1

Q C p T2 T1 5.21
dQ Tds C p dT
ds C p

dT
T

T
S 2 S1 C p ln 2 5.22
T

Fig. 5.5
Since Cp > Cv change in entropy in the constant pressure process is greater than entropy change
at constant volume.
A - Constant volume process;
B constant Pressure Process;

Entropy change (s2)v s1

Entropy Change (s2)p S1

WORK DONE IN ADIABATIC PROCESS (PERFECT GAS)

a.
Non Flow Process
dQ = du + dw
= u2 u1 + w = 0
W= u1 u2 = cv (T1-T2)
W= cv (T1-T2) .5.23
R
Cv =
and pv RT
1
R p1v1 p2v2
W

1 R
R
1
p v p1v1

1 2 2
p v p1v1
W 2 2
5.24
1
b.
Steady Flow Process
Using SFEE we have
C2
C2
- h2 1 Z1 g Q Wx h 2 2 Z 2 g
2
2
Where Wx is external shaft work. Q = 0 for adiabatic process, if kinetic and potential energy
terms are negligible.
Wx h1 h2 C p T1 T2

R
1
R
T T
Wx
1 1 2
PV
T
R
Cp

Wx

p v

pv

2 2
1 2 1

p v p2v2
Wx
1 1 1

p v p1v1 5.25
Wx
1 2 2

The work done in a reversible adiabatic process may also be calculated by means of integration.

Work done W

v2

pdv

v1

v2

C V dv p1 v1
y

v2

v1

dv

v \1

v2

y
v1
p1v1
1 y
1 y
p1v1

v2 V1

1
1 r v
y

y 1

p1v1v1
1

p1v1v1
1

y 1

y 1

y 1

v1

y 1

1
1
y 1 y 1
v
v1
2

y 1

v1
1

p1v1 p2v1
1
v2
R T 1 T2
p v p2v2
W 11

5.26
1
1
POLYTROPIC PROCESS
When a gas undergoes a reversible process in which there is heat transfer, the process is called a
polytropic process. In this case pvn = c
pv
11
1

The p-v-T relations are similar to those reversible adiabatic process

n 1

p2 nn1
T2 v1

5.27
T1 v2
p1
Entropy Change
Using the expression for entropy
T
V
S 2 S1 Cv ln 2 R ln 2 and
T1
V1

Substituting
1
V2 T1 n 1

V1 T2

and

Cv

R
R
, Cp
1
1
T
T
R
R
ln 2
ln 2
1 T1 n 1 T1
1
1 T2

ln
1 n 1 T1

S 2 S1

S 2 S1

T
n
ln 2 5.28
1n 1 T1

S 2 S1

n n 1 ln P2
1n 1n P1

S 2 S1

P
n
ln 2 5.29
n 1 P1

Or

Or

n R n ln V2
V
n 1
1
n R V2
S 2 S1
ln 5.30
1
V1
S 2 S1

Heat and Work in Polytropic Processes

Non Flow Process
Using First Law Equation
R
T T
Q W U 2 U1 T2 T1
1 2 1
p v p1v1
2 2
1
p v p1v1
Q W 2 2
5.31
1
Steady Flow Process
Using SFEE

Q Wx h2 h1

c22
c2
Z 2 g 1 0 Z1g
2
2

Neglecting kinetic and potential energy termsd

Q Wx h2 h1 c p T2 T1

R
T T
1 2 1
R
P V PV

1 2 2 1 1
R
P V PV 5.32
Q Wx
1 2 2 1 1

Work Transfer in Polytropic Process (non flow)

n 1
v2
p1v1 v1
1
W pdv
n

1
v1
v1
p v p2v2
RT1 T2
W 11

5.33
n 1
n 1
Heat Transfer in Polytropic Process (non flow)

Q U 2 U1 W

RT2 T1
n 1
1
1
R T2 T1

1 n 1
Cv T2 T1

R T2 T1
1n 1

R T2 T1
n 1 1
n
Cv T2 T1
n 1
n
Q
Cv T2 T1 5.34
n 1
The Isothermal Process

Pv=constant. In this case n=1, but the substitution of n=1 in the equations for work and heat in
the general polytropic case is invalid.
v2
v
W pdv p1v1 p1v1 ln 2
v1
v1

p
W p1v1 ln 2
p2
p
RT1 ln 2 5,.35
p2
To find entropy
s2

v2

s1

v1

Q Tds u2 u1 pdv

But u = f(T). For isothermal process u2 u1 = 0

s2

v2

s1

v1

Tds

pds

p1v1 v2
ln
T1
v1

s2 s1
v
R ln 2
v1

v
s2 s1 R ln 2 5.36
v1
5.9
Mixtures of perfect Gases
Following two properties common for all ideal gas components overall.
Temperature = T2 = TA = TB TN
Overall volume = V = VA = VB ..
Since each component occupies V as if present alone (molecular volume negligible) for any
component.
Partial volume = V1 = Volume occupied by i when compressed to the overall pressure P.
Then V = V1 = (Amagat Leduc Law)
= mv = mA vA = mBvB = mivi
Partial pressure = pi = Pressure exerted when i occupies overall volume V.
Then P = p1
Since PAV = PAV (mAvA) = mARAT
RT
RT
P' A A A
P' B B etc
VA
VA

P Pi

RiT
Vi

v
mv
mv mAVA mBVB ........

mi
m
T mR
P i i mAv A mB RA ....... T / mv
v m

But V 1

mR
pv i i T
m
This is the form PV = RT for ideal gas
Mixture behaves as ideal gas, where
mR
Rmixture i i
m
Since V U i mu (mi vi )

H H i mh (mi hi )
S Si ms (mi si )
and

du Cv dT
dU mCv dT

dTmiCv )

Cv
And

Cp

miCvi
m

miC pi
m