Compressibility factor- a measure of deviation from ideal gas behavior

“Gases deviates from ideal gas behavior significantly at states near the saturation region and the critical point.
This deviation from ideal gas behavior at a given temperature and pressure can accurately be accounted for my
introducing of a correction factor called compressibility factor ‘Z’

Pv = ZRT

Pv V actual
Z¿ It can also be expressed as Z =
RT V ideal

Z =1for ideal gas

“Farther away Z is form unity, the more the gas deviates from ideal gas behavior”

P T
P R= T R=
P cr T cr

P R → reduced pressure, T R → reduced temperature,

Pcr → critical pressure, T cr → critical temperature,

“The Z factor all gases approximately the same at the same reduced pressure and temperature.” This is called the
principle of corresponding states. The gases seem to obey the principle of corresponding states reasonably well. By
curve-fitting all the data, we obtain generalized compressibility chart that can be used for all gases.

At very low pressures all the gases approach ideal gas behavior (regardless of their temperature)

Observations from the compressibility chart:

1. At very low pressures ( P R ≪ 1) the gas behave as an ideal gas regardless of temperature.
2. At high temperatures (T R >2 ) ideal- gas behavior can be assumed with good accuracy regardless of pressure
(except when P R ≫1)
3. The deviation of a gas from ideal gas behavior is greatest in the vicinity of the critical point.

Pseudo- reduced specific volume, V R

V actual
v R=
RT cr /P cr

v R is defined differently from P R and T R . It is related to T cr and Pcr instead of v cr. Lines of constant v r are aiso
added to the compressibility charts and this enables one to determine T and P without having to resort to time
consuming iterations.

Other equation of state:

It is the desirable to have equations of state that represent the PVT behavior of substances accurately over
alarge region with no limitations. There are some equations namely.
[2 constant]vander waals berthelet redlich-kwang, [5 constant]Beattie-bridgemann, [8 constant] Benedict-webb-
rubin, [16 constant] Strobridge, [depend on no of terms] Virial. “several equations of state been proposed throughout
history”

Vander waals equation of state:

This is one of the earliest equation proposed in 1873,and it has two constants that are determined from the
behavior of a substance at the critical point.

( p+a /v 2) ( v −b ) =RT

Vander waals included two effects that are not considered in the ideal gas equation of state. The inter
molecular attractoion forces and the volume occupied by the molecules themselves.

a
→Inter molecular forces.
v2

b→accounts for the volume occupied by gas molecules.

Theconstants a and b can be determined for any substance from the critical point data alone.

27 R 2 T 2cr R T cr
a¿ & b=
64 Pcr 8 Pcr

Properties of mixtures of gases-Dalton’s law of partial pressure:

Let us imagine a homogenious mixture of inert gases at a temperatures T,a pressure P and a volume V. Let
us suppose there are n1 molecules of gas A1, and n2 moles of gas A2…and up ton c moles of gas Ac . Since there is
no chemical reaction.the mixture is in a state of equilibrium with the equation of state.

Pv =( n 1+ n2+ n3 +…+n c ) RT

Where Ŕ =8.3143 KJ/kg mol k

n1 Ŕ T n2 ŔT n Ŕ T
P= + + ∙∙ ∙∙ ∙ ∙∙ ∙+ c
V V V

nk Ŕ T
The expression represents the pressure that the k t h gas would exert if it occupied the volume V alone at
V
temperature T. this is called the partial pressure of the k t h gas and is denoted by Pk .Thus

n1 Ŕ V n Ŕ T n Ŕ T
P 1= , P2 = 2 ∙ ∙∙ ∙∙ ∙ ∙ Pc = c
V V V

Now P= P1 +¿ P2 + P3 +∙ ∙∙ ∙ ∙∙ ∙∙ ∙+ Pc

T h is is knownas Dalton ’ s low of ∂ pressure , w h ic h states t h at t h e total pressure of a mixture of ideal gasesis equ

Ŕ T
Also v = (n1 +n 1+ n3+ ∙∙ ∙∙ ∙ ∙∙ ∙∙ ∙ ∙∙+n c ¿
P
 Ŕ T N m =nk mole contained ∈a gas mixture .
v = ∑ nk
P

The partial pressure of k t h gas is

Ŕ T
Pk =nk →(1)
V
Substitute the value of V in (1)

n k Ŕ T n
Pk = = k .P
∑ nk Ŕ T ∑ nk
P

∑ nk =n 1+ n2+ n3 +∙∙ ∙ ∙∙ ∙∙ ∙ ∙∙+n c →Total no of moles in s gas

Ni n
=mole fraction= k = y i
Nm ∑ nk
Thus for each gas from (1-m)

n1 n2 nc
y 1= ; y 2= ; yc=
∑ nk ∑ nk ∑ nk
∴ y 1+ y 2 +∙ ∙∙ ∙ ∙∙ ∙∙ ∙+ y c =1 →(A )

From Pk equation

P 1= y 1 P

P 2= y 2 P

Pc = y c P

Pk = y k P

In a mixture of gases, if all but one mole fraction is determined, the last can be calculated from the above equation
(A)

In the terms of mass

P1 V =m1 R1 T

P2 V =m2 R2 T

Pc V =mc R c T

Using Dolton’s low

 PV = (m 1 R1 +m 2 R 2+ ∙∙ ∙∙ ∙ ∙∙ ∙∙+ mc R c ¿ T

Where P= P1 + P2+ ∙∙ ∙∙ ∙ ∙∙ ∙∙+ P c

Assume Rm is the gas constant of the mixture then

m1 R1 +m2 R2 +∙ ∙∙ ∙ ∙∙ ∙∙ ∙∙+ m c Rc
Pv =
m1 +m2 +∙∙ ∙ ∙∙ ∙∙+m c

Total mass of gas mixture m m is

m m=m1 +m 2 +∙∙ ∙ ∙∙ ∙∙ ∙ ∙∙+m c

If μ denotes the equivalent molecular weight of the mixture having n total number of moles.

n μ=n1 μ1 +n 2 μ2 +∙ ∙∙ ∙∙ ∙ ∙∙ ∙∙ ∙+nc μ c

n1 n2 nc
μ= μ 1+ μ 2+∙ ∙ ∙∙ ∙∙ ∙∙ ∙+ μc
n n n

μ= y 1 μ1 + y 2 μ 2+∙ ∙∙ ∙ ∙∙ ∙∙ ∙ ∙+ y c μc

A quantity called the partial volume of a component of a mixture is the volume that the component alone would
occupy at the pressure & temperature of the mixture.

PV 1=m1 R1 T , PV 2=m 2 R2 T , PV c =mc Rc T

P(V ¿ ¿ 1+V 2 +∙∙ ∙ ∙∙ ∙∙ ∙ ∙∙+V c )=( m 2 R 2+ m1 R1 +∙∙ ∙ ∙∙ ∙∙+ mn Rn ) T ¿

Here V = V 1 +V 2 +∙∙ ∙ ∙∙ ∙∙+V c

The total volume (V) is the sum of the partial volumes (V 1 ,V 2 , V c ¿

The specific volume of the mixture, v is given by

V V
v= =
m m1 +m 2 +m 3 +∙∙ ∙ ∙∙ ∙+m c

1 m 1+ m2 +∙ ∙∙ ∙∙ ∙ ∙∙+m c m1 m 2 mc
= = + +∙ ∙ ∙∙ ∙∙+
v V V V V

1 1 1 1
= + +∙∙ ∙ ∙∙ ∙∙ ∙+
v v1 v2 vc

v1 , v 2 , v 3 denote the specific volume occupied by each components.

V m3 1 kg
v= = so =ρ=density 3
m kg v m ( )
There fore the density of the mixture.

ρ=ρ1+ ρ2+ ρ3 +∙∙ ∙∙ ∙ ∙∙+ ρ c