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Problems

Part 1: Gas Region


a) The three graphs shown below are pvT plots obtained from a pure gas, that shows qualitative
behaviour of an ideal gas. Derive the ideal gas law from these plots. If you do the derivation
correctly, you will obtain a proportionality constant called the gas constant (R). Could you
determine the value of R, if the volume of 1 mole of an ideal gas is 22.4 L at a temperature of
0C and a pressure of 1 atm? Show the region in pvT diagram A and be where ideal gas law
is valid and where it is not.

1
We can see from the plots that V , V T and we already know that the number of
p
moles is proportional to the volume of a gas, so V n .

nT
We can utilise all these correlations together in order to make V= .
p
However, the unots are not of equal value for both sides of the equation, so we have to use a
constant, which in this case is also called the gas constant (R). When the gas constant is used,
nT
the equation will become V =R .
p
To find R when V =22.4 L , n=1mol , T =0 =273 K , and P=1 atm
vp 22.4 L 1 atm Latm
R= = =0.082
nT 1 mol 273 K molK
Diagram A
In both Diagram B
diagrams, the area which has been shaded blue signifies that ideal gas
law is not valid, while the area shaded red signifies that ideal gas law is valid. The reason why
the area shaded blue shows that ideal gas low isnt valid is due to its conditions; which is of
low temperature and low pressure. However, the optimal condition for an ideal gas is high
temperature and low pressure, which is the area shaded red. The red shaded area doesnt
spread into the area higher than the critical pressure, due to the phenomenon when a fluid
exceeds its critial pressure and temperature, where they become a supercritical fluid and is
almost indistinguishable from both a liquid and gas. Furthermore, a supercritical fluid needs
high pressure and temperature, which is not the optimal temperature for an ideal gas to exist.

b) Zetta learned that gases do not behave ideally at high pressures or low temperatures, as their
compressibility factor (Z) values are not unity (Z1). He obtained the following Z-chart of a
gas:

Give the definition of Z. Based on the Z-chart given,


explain how temperature and pressure affect
the value of Z.

Z, also known as the compressibility factor, is the ratio of molar volume of a gas to the molar
volume of an ideal gas at the same temperature and pressure. For reference, an ideal gas has a
compressibility factor of 1, so the further away a gas Z value to 1, the higher the deviation of
that gas in comparison to an ideal gas.

Based on the chart, the temperature is inversely proportional to the value of Z, while pressure
is directly proportional to Z. This is proven correct when we look at the equation for Z, which
pv
is Z= , where all the correlations that have been mentioned earlier checks out.
RT
c) Choose the condition most favorable to achieve ideal-gas state: (1) low T, low p; (2) low T,
high p; (3) high T, low p; or (4) high T, high p? Explain why your answer is correct.

The most favorable condition is (3) high T, low P. Ideal gas law assumes that gases occupy no
volume on their own, which means that the volume the gas particle occupies is so small
compared to the actual volume of the container that we can consider it to be 0. At low
pressure, which will induce larger volume, this is precisely what happens.

Secondly, ideal gas law assumes that there are no intermolecular interactions between the gas
molecules. At high temperatures, the kinetic energy given by the high amount of heat is so
large compared to the existing intermolecular forces among the gas molecules that we can
assume that there is not intermolecular force at all.

d) Susi found the following chart that gives Z as a function of reduced temperature (T r) and
reduced pressure (Pr). The interesting feature of the chart is that Z values for many gases are
similar when you compare them at the same Tr and Pr. This is called the two-parameter
generalised correlation. This concept emphasised the importance of the critical point. First,
define the critical point shown in the pvT diagram A and B using your own word. Second,
explain what you see in the graph!

In the pvT diagram A and B, we can see that the critical point shows the highest point where a
liquid-vapor equilibrium of a pure substance can exist. At this point, both the liquid and vapor
phase of the pure substance has the same density, so it is almost impossible to distinguish one
from another.

In the graph above, we can see a representation of the values of Z as a function of reduced
pressure (Pr) and reduced temperature (Tr). We observe that, even for different substances,
when Z is measured as a function of Pr and Tr, the deviation from an ideal gas is almost the
same and they all have a similar compressibility factor. This is due to T r and Pr being a ratio of
a substances actual temperature and pressure to its critical temperature and pressure.

P T
P r= T r=
Pc Tc

Furthermore, the reduced temperature and pressure has the same correlation with the Z value
as it is with temperature and pressure respectively. This further supports the theory that the
optimal condition for an ideal gas is at high temperature and low pressure.
e) Explain the difference between the two-parameter generalised correlation and the three-
parameter generalised correlation given in the Smith and van Ness book. Explain how Pitzer
defines the acentric factor ().

In the two-parameter generalised correlation, Z is shown as a function of Tr and Pr for


different pure substances. This results in a graph where the Z values of those different pure
substances are similar, but not completely exact. This means that the Z value of one substance
at the same Tr and Pr might slightly differ to another.

In the three-parameter generalised correlation, we have another parameter to add to the ones
already used, which is the acentric value (). In this correlation, when 2 different pure
substance which has the same acentric value is kept at the same Tr and Pr, they will have the
exact same value of Z and will deviate from an ideal gas state to the exact same degree.

The acentric value itself, as defined by Pitzer, is the difference between the characteristic of a
simple fluid to the more complex fluids that we use when depicted in a graph in reference to
its vaport pressure.

Tr
1/

d
d log Psat
r

sat
The equation above utilises the reduced vapor pressure ( Pr and the reduced
sat
temperature (Tr) of a pure substance to get the slope (S) when Pr vs. 1/ T r is drawn
graphically drawn. If the two-parameter generalised correlation will give the same value of Z
for every pure substance at the same Tr and Pr, then S would be the same for all substance.
However, this is not the case. Pitzer observed that, for simple fluids (Ar, Kr, Xe), the line
sat sat
when Pr vs. 1/ T r is plotted graphically will pass the same point at Pr =1.0
and T r=0.7 . This means that we can relate the vapor pressure of other, more complex
fluid at T r=0.7 to that of simple fluids to obtain the acentric factor. When written as an
equation, this will become:

=1.0log ( Psat
r )T =0.7r

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