Using the graphs provided, you should have gained an appreciation
for the different subtle variations in the pressure- volume
relationship. In the context of the question, both $n$ and $T$ can
be considered constants within the $PV = nRT$ equation. It may help
to express the relationship as $P = \frac{nRT}{V}$.
The first of the given graphs displays an inverse relationship
between the two variables. Considering the form $P =
\frac{nRT}{V}$, this can be seen to be a plot of pressure compared
to volume. The y axis given ranges from 0 to 50 units. This is
likely to be the volume as pressure is usually given in units of
pascals (1 Nm$^{-2}$). So we can say that the form of the graphical
plot is something like $V = \frac{nRT}{P}$ where P is probably
given in kPa as the value of atmospheric 1 bar pressure is 10^5
pascals. The volume could be is units of dm$^3$. This is working on
an assumption that if we use quantities of 1 mole and 25$^o$C (298
K) we can calculate that an appropriate volume at a pressure of 200
kPa would be:
Graphically, a value of around 10 units is seen and we can see that
by scaling up by 1000, the value we have calculated is in the same
approximate range as that on the graph. So units of dm$^3$ are
appropriate.The value of nRT in this case is $0.01 \times 200,000$
= 2000 J = 2 kJ.
The second graph is a linear relationship of proportional increase.
If we consider a modification of the above reciprocal plot, a plot
of P vs 1/V or V vs 1/P are possible valid forms. If we consider a
comparison between the first and second graph, the values on the x
axis on the second graph correspond readily to the values on the y
axis for the second graph. We can see that if we read off the first
graph for a volume of 10 dm$^3$, the equivalent value of 1/P is
$\frac{1}{200} = 0.005$ which is the same as the equivalent value
on the second graph. This again maps for other possibilities. Units
of the y axis in this case are by inference kPa$^{-1}$. The value
of nRT putting in place these assumptions is again, 2kJ.
The third graph represents a situation where changing the value of
the variable on the x axis does not change the value on the y axis.
We already know that the value of nRT is fixed due to the fact that
we are dealing with a situation where we have a constant number of
moles and a constant temperature. As the axes must be in terms of
the variables P and V, the y axis must be PV. The x axis can be
either pressure or volume in sensible units. We can see again there
is a similarity with the x axis of the first graph meaning the x
axis is likely to be the variable P plotted in kPa for the reasons
stated before. The value of nRT can be simply read off the graph to
be 2250 J = 2.25 kJ.
The value of nRT is proportional to the internal energy of the
ideal gas with modest changes in volume and has units of energy. It
is clear that changes in pressure are compensated for by changes in
volume to ensure that the nRT value of the ideal gas is kept
constant.
Note that the values of units and assignment of axes is merely one
of many possible solutions. As long as there is a step by step
logical process behind your answer then other assignments of axes
and possible units may be equally valid.
The next part of the question is more open to investigation by a
variety of means including the use of spreadsheets. An outline of
some form of solution is given below.
Kinetic theory equation, PV =
$\frac{1}{3}mN\bar{c^2}$
This equation can be rewritten as P = $\frac{mN}{3V}\bar{c^2}$ and
where m is the momentum that a certain particle possesses, N is the
number of particles and $\bar{c^2}$ is the mean square velocity of
a molecule (resolved in all component directions).
The inverse relationship may be generated by plotting P against
$\frac{1}{\bar{c}}$ but clearly the gradient of the limbs of the
graph and the transition is different from a $\frac{1}{\bar{c^2}}$
which can be seen easily using a spreadsheet or considering the
change in P with variations in $\bar{c}$. Again if we plot P
against $\bar{c^2}$ we obtain a linear relationship similar to
graph 2. If we plot $\frac{P}{\bar{c}}$ against $\bar{c}$ a linear
relationship is also observed. The constant term is clearly
$\frac{P}{\bar{c^2}}$ and a graph qualitatively the same as the
third may be obtained by plotting this against P or
${\bar{c^2}}$.
Plotting P against $\bar{c}$ gives a squared relationship. Plotting
P against $\frac{1}{\bar{c}}$, as we have already considered, gives
an interesting variation to the first graph.
You might like to consider the appropriate units to use for your
axes given your choice of constants.
Van der Waals equations, $(P +
aV_m^{-2})(V_m - b) = RT$
In this case all terms are constant apart from the terms $P$ and
$V_m$, corresponding to pressure and volume. Expansion and
rearrangement of this equation gives:
The quadratic numerator in terms of $V_m$ is the numerator and a
cubic equation in $V_m$ the denominator in the LHS fraction. Thus
broadly speaking a plot of P against $V_m$ yields a relationship
similar to that in graph 1, as this again a type of reciprocal
relationship. Plots of P against $V_m^2$ and P against $V_m^3$
would also yield a plot that looks similar to the first. There are
many other plots that can yield this approximate relationship
including that of \frac{1}{V} against \frac{1}{P}.
How many can you find? Using a
spreadsheet or analytical methods, can you describe what the
differences are between each of these reciprocal
plots?
Consider the case when a and b are 0. If we then plot P against
$\frac{1}{V_m}$ a straight line relationship can be produced. This
is clear after viewing the algebraic form above as you generate a
$PV_m = RT$ type relationship.Plotting $(P + V_m^{-2})(V_m)$
against P yields a relationship that is close to a straight line.
If we also consider that our constant term is RT, then we can
effectively plot a relationship (P + V_m^2)(V_m - 1), where both
a=1 and b=1 (for simplicity), against either V_m or P to yield a
plot similar to the third graph.
An interesting plot is that of P against $\frac{1}{V_m^2}$ and
$\frac{1}{V_m^3}$which gives a graph with a diminishing gradient
over time. Plotting these two relationships on the same graph and
observing the difference between these trends would be an
interesting comparative exercise. A plot of P against
$\frac{1}{V_m}$ also gives a trend with an increasing gradient over
time.The form of this is again dependent on the values of your
constants.
Experiment what happens on
variation of these values, for example when they are very large and
when they become increasingly close to zero.
There are many other examples of plots and the aim of this task is
to find as many interesting alternatives as possible.
Show without recourse to any calculating aid that 7^{1/2} + 7^{1/3}
+ 7^{1/4} < 7 and 4^{1/2} + 4^{1/3} + 4^{1/4} > 4 . Sketch
the graph of f(x) = x^{1/2} + x^{1/3} + x^{1/4} -x