Mathematics for Chemists – Year 1
Calculus Michaelmas 2023
Problem Class: Christmas Crackers
1. (Prelim 2014 Q1) The vectors a, b and c are defined by
a = i − 2j − 2k ,
b = 2i + j + k ,
c = 3i + j + k ,
where i, j and k are unit vectors along the x, y and z directions, respectively. Find a unit vector perpendicular
to a and b, and then determine the angle between this unit vector and c.
2. The vectors a and b are of the same length, but point in different directions. Show that a + b is orthogonal
to a − b.
3. Determine the following limits
2x − 1
3x + 2 arctan x
(a) lim . (b) lim . (c) lim .
x→∞ 4x − 1 x→∞ x x→0 x
√
4. Form first principles, differentiate f (x) = x.
5. (Prelim 2001 Q1)
∂2u dy
(a) If u = cos(xy) determine . (b) If xy = sin(x + y) determine .
∂x∂y dx
dz √
6. By using an appropriate chain rule, find if z = sin(3x + 4y) in which x = 1 + t2 and y = 3t − 1.
dt
2 ∂y ∂z
7. If xyz = xz sin(xy) + exp(xyz) determine and .
∂z x ∂y x
∂f ∂f
8. Use a chain rule to evaluate and if
∂r θ ∂θ r
f (x, y) = x3 − xy + y 3 ,
in which x = r cos θ and y = r sin θ. Verify your answer by direct substitution.
9. (Prelim 2007 Q12(a) - modified) Given constants a and b, show that if
z = z(x, y) = (x + y) f g(x, y) where g(x, y) = ax + by ,
then !
∂z ∂z
b −a (x + y) = (b − a)z .
∂x y ∂y x
10. (Prelim 1997) Find and classify the stationary points of
1
x2 + y 2 + x2 y − 13 y 3 .
f (x, y) = 2
11. (Prelim 2002 Q5) Expand (i) sin2 x and (ii) cos2 x as power series in x up to and including terms in x6 .
12. (Prelim 2005 Q3) Evaluate
1
e−x − ex
Z
dx .
−1 e−x + ex
13. (Prelim 2007 Q11)
(b) Evaluate
Z 1
1
dx .
0 x2 + 2x + 3
Dr Rob Penfold 1
(c) Show that Z a Z a
f (x) dx = f (a − x) dx ,
0 0
and hence, or otherwise, evaluate Z π
x sin x
dx .
0 1 + cos2 x
14. (Prelim Resit 1998) By appropriate substitutions, show that
Z ∞ Z 1
dz dx π
√ = √ = .
0
2z
e −1 0 1−x 2 2
15. (a) The Lennard-Jones potential function is often used to simply quantify the interactions between atoms and
molecules. The function is
σ 12 σ 6
V (r) = 4ε − ,
r r
where r is the separation between the interacting particles. The constants ε and σ are positive.
(i) Based on the physical interpretation, state an appropriate domain for the function V (r).
(ii) Find r0 such that V r0 = 0.
(iii) Show that V (r) has a single stationary point re within its domain.
d2 V
(iv) By calculating , classify re as a local maximum, a local minimum or neither.
dr2
(v) Find limr→∞ V (r), and discuss the behaviour of V as r → 0+ .
(vi) By considering all the previous results, sketch the graph of V (r) showing clearly all the relevant
information (intercepts, turning points, asymptotic behaviour).
(vii) State the image set of the function V (r).
(viii) Expand V (r) in a Taylor polynomial of degree 2 about the point r = re = 21/6 σ.
(ix) Hence, sketch the graph of this Taylor polynomial together with the graph of V (r) carefully showing
how these are related.
(b) The van der Waals equation of state can be written as
a
p + 2 (V − b) − RT = 0 ,
V
where R is the gas constant. The constants a and b are positive.
(i) By differentiating implicitly, show that
∂2p
∂p 2a RT 2RT 6a
= 3− and = − 4 .
∂V T V (V − b)2 ∂V 2 (V − b)3 V
(ii) The critical point of the equation of state is defined by simultaneous solutions of the equations
∂2p
∂p
= 0 and =0 .
∂V T ∂V 2
Find the critical values Vc , pc and Tc of the thermodynamic variables for the van der Waals equation
in terms of the constants a, b and R.
(iii) The compressibility factor Z of a fluid is defined by
pV
Z= .
RT
Calculate the critical point compressibility factor Zc for the van der Waals fluid.
Compare this result with Zc for a fluid of argon atoms where
Vc = 0.077 dm3 mol−1 , pc = 49 atm , Tc = 150.7 K .
(iv) The constant a is defined by Z ∞
a = −2π r2 V (r) dr ,
r0
16
3
where r0 satisfies V r0 = 0. For the Lennard-Jones potential, show that a = 9 πεσ
Dr Rob Penfold 2
(v) The van der Waals constant b measures the volume that a rigid spherical particle excludes from its
neighbours. By referring to the diagram below, explain why b = 23 πσ 3 .
σ
(vi) Suggest how the measured critical point data for a real fluid might be used to estimate the constants
ε and σ of the Lennard-Jones interaction potential.
16. A nefarious casino owner wishes to construct a loaded die. He wants the average die roll to be 3. (A fair die
has an average roll of 21/6.) There are various ways to achieve this: for example, he could make the die always
land on 3, or he could make it land only on 2 and 4 with equal probabilities. However, if he chose either of
these, it would be far too obvious that the die was loaded.
After reading some scientific papers, he decides to assign probabilities to the die rolls by maximising the entropy
of the probability distribution. If pi is the probability that the die lands on face i, the entropy of the distribution
is
6
X
S p1 , . . . , p 6 = − pi ln pi .
i=1
The probabilities must satisfy
6
X
pi = 1 ,
i=1
and he wants the average (or ‘expected’) die roll, hii, to be fixed at 3.
(a) Write down an expression for hii, in terms of the probabilities pi and the numbers i. Write it in the form
of a sum.
1
(b) Check that your answer to (a) gives the known result in the case of a fair die (where pi = 6 for all i).
P6
(c) Taking i=1 pi = 1 and hii = 3 as constraints, show that S is maximised if
− ln pi + 1 − λ − βi = 0 , for i = 1, . . . , 6 (1)
6
X
pi − 1 = 0 , (2)
i=1
6
X
ipi − 3 = 0 , (3)
i=1
where λ and β denote two Lagrange multipliers.
(d) By solving (1) for pi and then using (2), eliminate λ to show that
6
e−βi X
pi = where Q= e−βi .
Q i=1
Using (3) to eliminate β is difficult to do without a computer. It turns out that β ' 0.175 and the probabilities
look like:
Dr Rob Penfold 3
β=0.174629
pi
1.0
0.8
0.6
0.4
0.2
i
0 1 2 3 4 5 6
If the casino owner wanted the die to have an average roll of 2 (i.e. even more biased), then he would need
β ' 0.630 and the distribution would look like:
β=0.629571
pi
1.0
0.8
0.6
0.4
0.2
i
0 1 2 3 4 5 6
Notice how the probabilities decay exponentially as i increases. You will do a very similar calculation next year
in your Statistical Mechanics course.
Dr Rob Penfold 4
