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Introduction To Physical Chemistry Lecture 3
Introduction To Physical Chemistry Lecture 3
We know, however, that at sufficiently high tempera- variables. In other words, two gases at the same reduced
tures, the van der Waals equation behaves similarly to temperature and volume will have the same reduced pres-
the ideal gas equation, for which no phase transitions are sure.
possible. Intuitively, the motivation for this hypothesis is that
The transition from the low temperature behavior of two gases with the same set of reduced variables have
the van der Waals equation to the high temperature be- an equal level of deviation from ideal gas behavior. The
havior must therefore occur by the steady disappearance idea is that the values of the critical constants set up
of the van der Waals loops as the temperature increases. natural “length” scales characterizing the behavior of the
This means that V̄min and V̄max should converge as T gas. Rescaling the parameters associated with the gas in
approaches Tc . Finally, at Tc , V̄min = V̄max , so that this terms of these natural length scales gives a set of dimen-
point is neither a local minimum or maximum, but rather sionless parameters that effectively hides these “length”
a point where both dP/dV̄ and d2 P/dV̄ 2 vanish. scales. Therefore, it is not unreasonable to assume that
Differentiating the van der Waals equation of state real gases may exhibit universal behavior when expressed
twice, we obtain, in terms of the reduced variables.
In reality, the law of corresponding states only works
dP RT 2a for gases composed of spherical, non-polar molecules.
=− + 3
dV̄ (V̄ − b)2 V̄ For non-spherical or polar molecules, the principle fails,
d2 P 2RT 6a sometimes badly.
2
= 3
− 4 (14)
dV̄ (V̄ − b) V̄
Setting both derivatives equal to 0 and solving, we ob- V. AN ALTERNATE DERIVATION OF THE
tain, V̄ = 3b, T = 8a/(27bR), and P = a/(27b2 ), and VAN DER WAALS EQUATION
so,
We conclude this lecture by providing a plausible, al-
V̄c = 3b ternative derivation to the van der Waals equation of
8a state. The idea is as follows: Because of intermolecular
Tc =
27bR interactions, the individual gas particles, denoted A, may
a form transient pairwise associations with one another, so
Pc = (15)
27b2 that the gas may be regarded as a chemically reacting
Of course, different equations of state will yield differ- system with the pair of chemical reactions,
ent values for the critical constants. A + A → A2
In concluding this subsection, we should point out that
A2 → A + A (16)
the van der Waals equation gives a value of 3/8 = 0.375
for the critical compression factor, defined by Zc = where the first reaction has a second-order rate constant
pc Vc /(RTc ). This value turns out to be somewhat larger of kf , and the second reaction has a first-order rate con-
than what is measured for a variety of real gases. Never- stant of kr . We then have,
theless, it turns out that Zc is fairly constant at around
0.3 for many gases. This certainly suggests that the van d[A]
= −kf [A]2 + 2kr [A2 ]
der Waals equation captures key physical properties as- dt
sociated with real gases. d[A2 ] 1
= kf [A]2 − kr [A2 ] (17)
dt 2
G. The law of corresponding states At steady-state, we have kf [A]2 = 2kr [A2 ], so that
2[A2 ]/[A]2 = K ≡ kf /kr .
The law of corresponding states is a misnomer, in that Now, the total concentration of gas particles A is given
it is not a derivable law, but rather an educated guess, by [A] + 2[A2 ]. By conservation of mass, this quantity is
backed by experiment, that approximates the behavior a constant, given by [A]0 . We therefore have that,
of real gases. [A]0 − [A]
The idea is as follows: Different gases will generally =K (18)
[A]2
have different values of Tc , Pc , and V̄c . This follows from
the different characteristic particle sizes and strength of Now, define x = [A]0 − [A], so that [A] = [A]0 − x. Then,
the interparticle interactions. However, for a given gas, x is the solution to the quadratic,
we can define reduced variables as follows: At a temper-
ature T , define Tr = T /Tc . The reduced variables Pr and 0 = x2 − (2[A]0 + 1/K)x + [A]20 (19)
V̄r are defined similarly.
The law of corresponding states then argues that there so that,
is a universal equation of state for real gases when the 1 p
equation of state is expressed in terms of the reduced x = [A]0 + (1 − 1 + 4K[A]0 ) (20)
2K
5
where the alternative solution is not realistic since it gives Therefore, intermolecular interactions have reduced
x > [A]0 . the effective molar concentration [A]0 = n/V of gas par-
Now, we are ultimately considering a gas with weak ticles by an amount (K/2)(n/V )2 .
intermolecular interactions. Therefore, the steady-state
concentration of particle-pairs A2 should be small, which
means that K is small. This allows us to Taylor-expand
Applying the ideal gas law using this reduced molar
the square root term out to second-order in K, giving,
concentration, we obtain,
p
1 + 4K[A]0 ≈ 1 + 2K[A]0 − 2K 2 [A]20 (21)
so that,
x ≈ K[A]20 (22)