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Real Gases - Vanderwall Equation

This document discusses real gas behavior compared to ideal gases. It introduces molecular interactions, compression factors, and the van der Waals equation of state which accounts for attractive and repulsive molecular forces. The van der Waals equation includes parameters a and b that relate to molecular size and attractions. Critical constants like the critical temperature are also defined, above which gases cannot be liquefied. Real gas behavior is represented using virial equations, compression isotherms, and the principle of corresponding states using reduced variables.

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129 views6 pages

Real Gases - Vanderwall Equation

This document discusses real gas behavior compared to ideal gases. It introduces molecular interactions, compression factors, and the van der Waals equation of state which accounts for attractive and repulsive molecular forces. The van der Waals equation includes parameters a and b that relate to molecular size and attractions. Critical constants like the critical temperature are also defined, above which gases cannot be liquefied. Real gas behavior is represented using virial equations, compression isotherms, and the principle of corresponding states using reduced variables.

Uploaded by

Viejay
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Real Gases

Molecular Interactions

Molecular Interactions
Compression factor
Virial coefficients
Condensation
Critical Constants

Repulsive forces:
assist expansion of gas

van der Waals Equations


Attractive forces:
assist compression of gas

Corresponding States

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 1

Prof. Mueller

Compression Factor

Chemistry 451 - Fall 2003

Lecture 3 - 2

Important Question
How do we go about representing this real (i.e.
non-ideal) behavior in a logical manner ?

The compression factor of a gas can be defined


as:
where Vm is the molar volume, V/n.
Ideal gas:

Empirical Models

Intermediate Pressure:

Semi-empirical Models
High Pressure:

Theoretical Models
Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 3

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 4

Virial Coefficients

Virial Coefficients

For a real gas with large molar volumes and higher temperatures,
the isotherms are almost identical to those of an ideal gas.
However, there are some small differences which suggest that the
perfect gas law is only the first term in a power series:

Rewriting in terms of compression factor, Z:

These are the virial equations of state, where coefficients B and C


have to be evaluated at each temperature!
p = 0:
p increases:
p higher:

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 5

Prof. Mueller

Virial Coefficients for Methane

(oC)

pVm = RT (1+ Bp + C p + Dp

10-3

0
25
50
100
150
200
250
300
350
Prof. Mueller

B (x

D (x 10-9 bar-3)

-2.349
-1.727
-1.274
-0.677
-0.324
-0.106
+0.0345
+0.125
+0.186

bar-1)

C (x

10-6

bar-2)

-0.877
+0.438
+1.353
+1.447
+1.219
+0.967
+0.749
+0.583
+0.461
Chemistry 451 - Fall 2003

Lecture 3 - 6

Boyle Temperature
Perfect gas: dZ/dp = 0 (since Z = 1), but
in a real gas

Virial coefficients for methane up to about 400 bar, 350oC


2

Chemistry 451 - Fall 2003

29
17
7.9
4.1
2.0
0.99
0.56
0.31
0.16

At low T: initial dZ/dp < 0, B is negative


At high T: initial dZ/dp > 0, B is positive
(Correspond to the first order B
coefficients at these temperatures)
The temperature at which the initial slope
is zero is the Boyle Temperature, TB,
where B = 0 (real gas corresponds to an
ideal gas)
Lecture 3 - 7

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 8

A Compression/Condensation Experiment

CO2 Compression and Condensation


A: p rises, in accordance with Boyles law
B: deviations from ideal gas behavior
CDE: piston moves without any pressure increase
at all - non-ideal behavior
This line: vapor pressure (liq-gas equilibrium)

Increase p

A liquid appears, just to the left of C, amount of


liquid increases moving from C to D to E
Pressure does not increase, since the gas is
beginning to condense.
E: sample is almost entirely liquid
Even a small volume reduction (E to F) requires an
immense increase in applied pressure from the
piston

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 9

Prof. Mueller

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 11

Lecture 3 - 10

van der Waals

Critical Behavior: The 31.04oC Isotherm for CO2


If compression takes place at the so-called
critical temperature, Tc, the surface
separating the gas and liquid phase does
not appear, and the horizontal parts of the
isotherm merge at the critical point. A
liquid phase does not form above the
critical temperature.
The critical temperature, molar volume, and
pressure, Tc, Vc and pc, are called the
critical constants, which are unique to
each substance.
Certain substances have a very dense phase
which can fill an entire volume at T > Tc,
and these are referred to as supercritical
fluids.

Chemistry 451 - Fall 2003

Johannes Diderik van der Waals (1837-1923), a Dutch physicist,


won the 1910 Nobel Prize in Physics for his work on the equation
of state for gases and liquids.

His formulation is a semi-empirical model, which means it is based


upon experimental observations, combined with a rigorous
thermodynamic treatment.
Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 12

van der Waals

van der Waals Equation


The van der Waals equation is written as

where a and b are van der Waals coefficients,


specific to each gas.
Term a is adjusted to represent the attractive forces of
the molecules, without giving any specific physical
origin to these forces;
V - nb, not V, now represents the volume in which
molecules can move.
Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 13

Justifying the van der Waals Equation


The coefficients a and b are adjusted to model certain features of the gas
behavior, and are dependent upon the attractive and repulsive forces
between molecules in the gas.

The frequency and forces of the collisions are both reduced by attractive
forces, by a strength proportional to n/V (molar concentration); thus,
pressure is reduced as the square of this concentration, and this
contribution is written as:

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 14

Reliability of the van der Waals Equation


It is unrealistic to expect that such a simple equation
will be a perfect equation of state for all gaseous
substances.
- van der Waals equation:

- virial equation:
The parameters a and b should not be assigned specific molecular
properties, but rather, serve as coefficients which help to accurately model
gas behavior, and can be assigned specifically to each type of gas.
Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 15

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 16

Reliability of the van der Waals Equation


Compare these calculated isotherms with the experimental
isotherms of CO2: the most notable anomaly are the so-called van
der Waals loops, where the isotherms drop suddenly below Tc
(they suggest increase p results in increased V) - they can be fixed
by a Maxwell construction (see text) - and the vdW coefficients
are found by comparison of experimental and theoretical curves.

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 17

Summary of the van der Waals Equation


(3) Critical constants are related to the van der Waals coefficients:
- at the flat inflection, the 1st and 2nd derivatives are zero !

Solve using some algebra and find critical constants:

Prof. Mueller

Chemistry 451 - Fall 2003

Summary of the van der Waals Equation

(1)

Perfect gas isotherms are obtained at high temperatures and large


molar volumes:

(2)

Liquids and gases exist when cohesive and dispersive forces are
balanced:

(3)

Critical constants are related to the van der Waals coefficients:

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 18

Principle of Corresponding States


In many areas of science it is useful to compare a
fundamental property of different objects on a relative
scale for purposes of comparison.
For different gases, we use reduced variables:

The observation that real gases at the same V and T


exert the same reduced pressure is the principle of
corresponding states.

Lecture 3 - 19

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 20

Principle of Corresponding States


value of Tr

Prof. Mueller

Chemistry 451 - Fall 2003

Lecture 3 - 21

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