GROUP 2

REAL GASES

Doan Huong Giang 20221792

Nguyen Thanh Hai 20221793
GV: Nguyen Ngoc Mai
1. What is real gases (non-ideal gases)?
 Definition:
Real gases are nonideal gases whose molecules occupy
space and have interactions; consequently, they do not adhere to
the ideal gas law.

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Real gases behavior:
Real gases exhibit ideal behavior when:
- Temperature is high (particles have enough energy to
overcome any attractions ).
- Pressure is low ( particles are so far apart their individual
volume is insignificant).

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- However, we know that in real life, gases are made up of atoms
and molecules that actually take up some finite volume, and we
also know that atoms and molecules interact with each other
through intermolecular forces.
- A real gas deviates most from an ideal gas at low temperatures
and high pressures.

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• Plots of PV/nRT versus P at 273 K for several common
gases:

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• A plot of PV/nRT versus P for nitrogen gas at three
temperatures

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2. Critical temperature and pressure
 Definition:
The highest temperature at which a species can coexist in
two phases (liquid and vapor) is the critical temperature of that
species,Tc, and the corresponding pressure is the critical
pressure Pc.
A substance at Tcand Pc is said to be at critical state.

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• The critical temperatures and pressures of some substances are
listed below:

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• Example:
Suppose a quantity of water is kept in a closed piston-fitted
cylinder.
The cylinder is first set to a specified value with
the cylinder pressure low enough for all the water to be vapor, then
water is compressed at constant temperature by lowering the piston
until a drop of liquid water appears(until condensation occurs).

The pressure at which condensation begins and the densities of

the vapor and of the liquid at that point are noted, and
the experiment is then repeated at several progressively higher
temperature.
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• The following results might be obtained :

• For water, Tc=374,15°C, Pc=218.3 atm.

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 Difference between gas and vapor
- A vapor is a gaseous species below its critical temperature.
- A gas is a species above its critical temperature at a pressure
low enough for the species to be more like a vapor than a liquid.
- Substances at temperature above and pressure above are
referred to as superficial fluid.
Question: The critical temperature and pressure of isopropanol
(isopropyl alcohol) are Tc = 508.8 K and Pc = 53.0 atm.
Isopropanol is in a gaseous state at T 400 K and P 1 atm. Would it
be classified as a vapor or a gas?

Vapor

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Reduced variables
Reduced variables are corrected or normalized ,conditions of
temperature, pressure or volume, normalized by their respective
critical conditions, as follow:

Tr=
Pr=
Vr =

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3. Equations of states for non-ideal gases
 What is equations of states?
An equation of state is a thermodynamic equation relating
state variables, which describe the state of matter under a given
set of physical conditions, such as pressure, volume, temperature,
or internal energy.
The simplest example of an equation of state is the ideal gas
law itself.
PV = nRT

P: pressure (Pa)
V: volume ( m3)
n: number of moles of gas (moles)
R: ideal gas constant (8.314 J/(mol·K) = 1.989
≈ 2 cal/(mol·K), or 0.0821 L⋅atm
/(mol⋅K)
T: absolute temperature (K)
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v Advantages and disadvantages of equations of states
Advantages:
1.Values of p-V-T can be predicted with reasonable errors in
regions where no data exists.
2.Only a few values of coefficients are needed in the equation
to be able to predict gas properties versus collecting large
amount of data by experiment.
3.The equations can be manipulated on a computer whereas
graphics methods cannot.
Disadvantages:
1. The form of an equation is hard to change to fit new data.
2. Inconsistencies may exist between equations for p-V-T and
equations for other physical properties.
3. Usually the equation is quite complicated and may not be
easy to solve for p, V or T because of its nonlinearity.

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 Cubic equations of state
1. Van der waals equation

a: signifies the intermolecular forces of attraction between the

molecules

b: signifies the volume of gas per mole occupied.

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• Each gas has its own a and b:

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Take a sample of gas:

4.25L P=?
3.46 mol CO2
229 °C
Ideal gas law: P=nRT/V=
(3.46mol)(0.0821Latm/molK)(502°K)/4.25L
= 33.5atm
Van der waals equation:
P=nRT/(V-nb) - an2/V2
(3.46mol)(0.0821Latm/molK)(502°K) - (3.59L2atm/mol2)(3.46mol)2 =
32.4atm​
4.25L-(3.46mol)(0.0427L/mol) (4.25L)2
( a=3.59 L2atm/mol2 b=0.0427L/mol)
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 4.25L
3.46 mol CO2
229 °C

Ideal gas law Van der waals

equation
33.5atm (good estimate) 32.4atm (more
accurate)

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• Exercise:
A cylinder 0.150 m3 in volume containing 22.7 kg of propane
(C3H8 ) stands in the hot sun. A pressure gauge shows that the
pressure is 4790 kPa gauge. Using the Van der Waals equation of
state, determine the temperature of the propane in the cylinder.

a = 9.24 x 106 atm (cm3/gmol)2

b= 90.7 cm3/gmol

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• Solution:
Given the following values:
n = 22.7 kg (1/44) = 0.516 kmol = 516 gmol
V = 0.150 m3 = 0.150 x 106 cm3
P = 4790 kPa + 101 kPa = 4891 kPa = 48.3 atm abs
R = 82.06 (atm)(cm3)/(gmol)(K
P + (=nRT
[48.3 + ][0.150x106- 516(90.7)]=516(82.06)T
T= 384K

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• The SRK equation of state is
P=
where the parameters a, b, and α are empirical functions of the
critical temperature and pressure (and from Table B.1), the Pitzer
acentric factor (ω from Table 5.3-1), and the system temperature.
The following correlations are used to estimate these three
parameters:
a = 0.42747 (5.3-9)
b = 0.08664
(5.3-10)
m = 0.48508 +1.55171 – 0.1561 (5.3-
11)
= T/ (5.3-
12)
= (5.3-13)

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Example

• A gas cylinder with a volume of 2.50 contains 1.00 kmol of

carbon dioxide at T = 300K. Use the SRK equation of state to
estimate the gas pressure in atm.

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Solution

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THE COMPRESSIBILITY-FACTOR EQUATION OF
STATE
• The compressibility factor of a gaseous species is defined as the
ratio
ɀ ==

ɀ=1 : = id P =RT (ideal)

ɀ<1 : id P <RT (attraction)
ɀ>1 : id P >RT(finite volume)
The extent to which ɀ differs from 1 is a measure of the extent to
which the gas is behaving nonideally. Equation above may be
rearranged to form the compressibility-factor equation of state,
= ɀRT
or since = V/n for a fixed quantity of gas and V/ṅ
̇ for a flowing
stream,
PV = ɀnRT
PV˙= ɀṅRT
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Compressibility factor ɀ for nitrogen:

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FIGURE 5.4-1

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FIGURE 5.4-2 Generalized compressibility chart, low pressures.
(Based on Footnote 7.)
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FIGURE 5.4-3 Generalized compressibility chart, medium
pressures. (Based on Footnote 7.)
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FIGURE 5.4-4 Generalized compressibility chart, high pressures.
(Based on Footnote 7.)
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• Figures 5.4-2 through 5.4-4 are expansions of various regions of
Figure 5.4-1. The parameter is introduced in these figures to
eliminate the need for trial-and-error calculations in problems
where either temperature or pressure is unknown. This
parameter is defined in terms of the ideal critical as
= = =

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The procedure for using the generalized
compressibility chart for PVT calculations is as follows:
• 1. Determine the critical temperature,, and critical pressure,, of
the species either by looking it up [e.g., in Table B.1 or with the
APEx functions Tcrit(“Species”) and Pcrit(“Species”)] or using an
estimation procedure such as those illustrated by Poling et al.
(see Footnote 1) or described on pp. 2-468 through 2-471 of
Perry’s Chemical Engineers’ Handbook (see Footnote 2).
• 2. If the gas is either hydrogen or helium, determine adjusted
critical constants from the empirical formulas
= 8K
= 8 atm
These equations are known as Newton’s corrections

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• 3. Calculate reduced values of the two known variables
(temperature and pressure, temperature and volume, or
pressure and volume) using the definitions
=
=
=
Perform whatever unit conversions may be necessary to make the
calculated reduced variables dimensionless. If the gas is H2 or He,
substitute for Tc and Pc the adjusted values of these quantities
calculated in Step 2. All temperatures and pressures used in
these calculations must be absolute.

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• 4. Use the compressibility charts to determine the
compressibility factor, and then solve for the unknown variable
from the compressibility-factor equation of state (Equation 5.4-
2).
The compressibility-factor equation of state used in conjunction
with the generalized compressibility chart is not generally as
accurate as a multiple-constant equation of state for PVT
calculations under highly nonideal conditions. Furthermore, it
lacks precision and cannot readily be adapted to computer
calculations. Its advantages include relative computational
simplicity and (as will be shown) adaptability to multicomponent
gas mixtures.

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• Example:
One hundred gram-moles of nitrogen is contained in a 5.00-liter
vessel at -20.6°C. Estimate the pressure in the cylinder.

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• Quiz:
1. A gas starts to deviate from what the ideal gas law predicts
when ___

a. the particles are dispersed

b. the particles are crowded

c. under low pressure

d. at high temperatures

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2. Van der Waal's correction to the volume term of the ideal gas
law accounted for ____

a. the interactions between molecules

b. the thickness of the container walls

c. the electron clouds of particles

d. the space that the particles themselves take up

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3.Which of the following is the correct equation for the ɀ factor?

a. PV = nRT

b. ɀ = PV/nRT

c. ɀ = nRT/PV

d. E = mc2

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4.

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THANK
YOU !

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