TUTORIAL PROBLEMS PHYSICAL CHEMISTRY 2

COLLISION THEORY AND TRANSPORT PHENOMENA

(TD-1) BASIC COLLISION THEORY

(a) Calculate the average number of collisions per second for a nitrogen molecule in a gas of pure
nitrogen at equilibrium at 1.000 bar and 300 K.

(b) The experimentally determined pre-exponential factor for the dimerization reaction of methyl
radicals is 2.4 ⋅ 1010 L ⋅ mol−1 ⋅ s−1.

(b.1) Show, by starting from the collision frequency, zAB, that the maximum second-order rate
constant for a bimolecular reaction A + B → P is given by:

k 2,max = σAB v̄rel NAv

(b.2) Show that the Arrhenius prefactor A can be identified as the maximum rate of reaction if the
activation energy is zero.

(b.3) Explain what the steric factor of a reaction reveals, and calculate the reactive collision cross
section and the steric factor for this dimerization reaction of methyl radicals, given that the C-H
bond length is equal to 154 pm and that the temperature is 298 K.

PC2-TP-TD-1
(c) Nitrogen dioxide reacts in the gas phase in an elementary bimolecular reaction step:

NO2 + NO2 → NO + NO + O2.

The temperature dependence of the second-order reaction rate constant for the rate law
d[P ]/dt = kr[NO2]2 is given in Table TP-TD-1.1. Calculate the reactive collision cross section and
the steric factor for the reaction, based on the non-reactive collision cross section of NO2 with NO2
of 0.60 nm2.

Table TP-TD-1.1: bimolecular reaction rate as a function of temperature.

T (K ) 600 700 800 1,000

kr ( cm3 ⋅ mol−1 ⋅ s−1) 4.6 10 2 9.7 103 1.3 10 5 3.1 106

(d) Calculate the mean free path of nitrogen molecules in a gas of pure nitrogen at equilibrium at
1.000 bar and 300 K. Explain what the mean free path is in words.

(e) At which temperature is the mean free path of nitrogen molecules in a gas of pure nitrogen at
thermal equilibrium and pressure of 1.00 ⋅ 10−6 bar equal to 10 cm?

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(TD-2) EFFUSION

(a) A solid surface with dimensions 2.5 mm by 3.0 mm is in contact with Argon gas at a pressure of
90 Pa and a temperature of 500 K. Calculate the number of collisions of Ar atoms with the surface
during 15 s.

(b) A circular hole of diameter 2.50 mm is punched in an effusion oven. The solid in the effusion
oven has a molecular mass of 260 g ⋅ mol−1 and a vapor pressure of 0.835 Pa at 400 K. Calculate
the mass lost from the effusion oven during a time interval of 2.00 hours.

(c) A circular hole of diameter 2.50 mm is punched in an effusion oven. The solid in the effusion
oven is naphthalene (C10 H8), which has a molecular mass of 128 g ⋅ mol−1 and is kept at a constant
temperature of 350 K. The mass lost from the effusion oven during a time interval of 2.00 hours
was 0.072 kg. Calculate the vapor pressure of solid naphthalene at 350 K.

PC2-TP-TD-3
(TD-3) STAYING ALIVE…

A space vessel with internal volume of 3.0 m3 is hit by debris, resulting in a circular hole in the
vessel's hull with a radius of 0.10 mm. Calculate the time it takes for the pressure of oxygen gas to
drop from 80 kPa to 70 kPa at a constant temperature of 298 K.

HINTS: you need to find an expression for the number of molecules of oxygen that leave the vessel
per unit time. You will find that this number depends on the number of oxygen molecules present.
Set up a differential equation for this problem (either in the number of oxygen molecules or first
convert to oxygen pressure). Solve the differential equation and calculate the required time.

PC2-TP-TD-4
(TD-4) THERMODYNAMIC FORCE

Consider the following situation: two containers with equal volume (1.00 m3) are filled with CO2
gas at a temperature of 300 K, and they are connected by a small tube containing a valve, that is
originally closed. The width of the valve, Δx, is 3.00 mm. When opened, the cross sectional area of
the open connection in the valve is 1.00 mm2. Initially, the pressure in one the containers (left) is
0.500 bar and the pressure in the other container (right) is 1.500 bar. The gas may be considered to
behave as a perfect gas.

(a) Show that the so-called thermodynamic force (in N per particle) on the molecules across the
valve, i.e. over the width of the valve, Δx, can be written as:
kBT ΔP
Fth ≈ − ×
P Δx
P(x) + P(x + Δx)
Here, P = is the average pressure across the opening.
2

(b) Calculate the thermodynamic force across the given valve.

(c) The mobility u of the molecules in a gas or liquid is defined as the drift speed acquired per unit
applied force: s = u ⋅ F. Here, the applied force is the thermodynamic force (other forces are
absent, small, or irrelevant, for example the gravitational force). The valve is equipped with a flow
meter. This can be a small turbine that starts rotating due to the difference in force exerted by
moving particles, or the average flow speed of particles can be measured directly using a thermal
mass flow meter. Some time after opening the valve, the measured drift (or flow) speed reaches a
steady value if the pressure difference between the compartments remains the same, which is the
case if the mass flow through opening is small compared to the masses present in the containers.

Calculate the mobility of CO2 if the flow speed is measured to be 3.62 × 10−3 m ⋅ s−1.

PC2-TP-TD-5
(d) Argue that the flux at steady state can be written as the flow (or drift) speed s and the
N
concentration or number density as J = s .
V

(e) The diffusion coefficient D is defined as the coefficient of proportionality of the flux to the
negative gradient of the number density (or concentration, depending on the definition of the flux as
d(N/V )
particle or molar flux), i.e. Jx = − D . Show that D = u kBT, and calculate the diffusion
dx
coefficient of CO2 at 300 K and 1 bar pressure.

PC2-TP-TD-6
(TD-5) DIFFUSION

{ 4Dt }
1 x2
c(x, t) = exp − is a solution to Fick's second law.
4π Dt

c(x, t) is the concentration of some compound at position x and at time t. D is the diffusion constant
or diffusion coefficient of the compound.

(a) An interesting feature of this solution is that the mean-squared displacement as a function of
time, is the same as for the random walk (see Brightspace for presentation on the random walk).
Show that for the solution given , the mean-squared displacement as a function of time, i.e.

⟨x (t) ⟩ is given by 2Dt.

(b) How long does it take a CO2 molecule in water to travel 100 meters in one direction in the RMS

sense ( ⟨x 2⟩ , for example from the surface of the ocean to the bottom)? Given is the diffusion

constant of CO2: DCO2 = 2 × 10−9 m2 ⋅ s−1.

(c) How long does it take a CO2 molecule in water to travel 10 μm in three dimensions in the RMS
sense (for example from center of a biological cell to its surface)?

(d) How long does it take a protein molecule with a diffusion coefficient D = 1 × 10−6 cm2 ⋅ s−1 to
travel a distance of 10 μm in the RMS sense in three dimensions (for example from the center of a
biological cell to its outer membrane)?

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(TD-6) SPECIFIC SOLUTIONS TO THE DIFFUSION EQUATION, PART I

A quantity of drug molecules is present in a tablet whose walls are positioned at x = 0 and x = h.
The drug molecules diffuse through both walls at constant rate R. We will consider transport in one
direction only. The diffusion equation is therefore given as:

d 2 c(x)
D =R
d x2

(a) Solve the diffusion equation and find the concentration c(x) between the walls of the tablet,
applying the boundary conditions c(0) = 0 and c(h) = 0; i.e, the drug molecules react as soon as
R 2 Rh
they leave the tablet. (Answer: c(x) = x − x).
2D 2D

(b) Calculate the flux of the drug molecules out of the tablet, i.e. at the walls of the tablet.

PC2-TP-TD-8
(TD-7) SPECIFIC SOLUTIONS TO THE DIFFUSION EQUATION, PART II

Fick's second law of diffusion for spherical symmetric systems under steady state conditions (for
example for the concentration c(r) of particles at a distance r from the center of a sphere with
radius R*) is given by:
d 2 c(r) 2 dc(r)
+ =0
dr 2 r dr

(a) Show that the flux of particles that arrive at the surface of a sphere with radius R*, is given by:
c
J = D bulk
R*

cbulk is the concentration of the particles in the bulk of the solution, i.e. at large distance from the
surface of the sphere; at R* the concentration is 0; this condition implements the idea that when a
particle arrives at the surface of the sphere it ceases to exist as such (it forms an intermediate).

(b) Use the results at (a) to show that the diffusion-controlled reaction rate constant for the reaction
between particles A and B with two different hydrodynamic radii aA and aB, respectively, is given
by:
kd = 4π (DA + DB )(aA + aB )NAv

Here, the effective diffusion coefficient for the motion of A and B with respect to each other is
approximated by the sum of the diffusion coefficients, and the distance at which A and B react is
taken as the sum of their hydrodynamic radii.

(c) Show that kd = 8RT /3η if both the hydrodynamic radii and the diffusion coefficients of
molecules A and B are the same.

(d) Calculate the diffusion-controlled reaction rate constant for the dimerisation of two identical,
spherical molecules in water (η = 0.01 poise) at 300 K.

PC2-TP-TD-9
(e) Calculate the hydrodynamic radius of haemoglobin in aqueous solution from its diffusion
coefficient (D = 6.9 × 10−7 cm2 ⋅ s−1), under the assumption haemoglobin is a spherical molecule.
Use a temperature of 298 K. You will need to find the viscosity of water yourself.

(f) Calculate the number of protein molecules that reach the wall of a biological cell per unit of time
in the diffusion-controlled limit, the proteins originating from a solution at a bulk concentration of 1
μM. Model the biological cell as a sphere with radius R = 10 μ m and solve the diffusion equation
as a function of the distance from the center of the biological cell. For the protein, use the diffusion
coefficient D = 6.9 × 10−7 cm2 ⋅ s−1.

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(TD-E1) MOLECULAR INFORMATION FROM MEASUREMENT OF DIFFUSION
COEFFICIENT

Enderlein et al. (Chem. Phys. Chem. 8, 433) determined the diffusion coefficient (D) at 25 ∘C of
the molecule Atto655 in aqueous solution as a function of its viscosity (η). The viscosity of the
solution was varied by changing the concentration of guanidinium chloride. Figure TP-TD-E1.1
shows how the measured diffusion coefficient depends on 1/η. The drawn line is the best linear fit
to the set of measurements.

Figure TP-TD-E1.1: Experimental data for diffusion coefficient of Atto655 in water.

(a) Determine the slope of the drawn line from the graph. Do not forget the units!

(b) What is the meaning of the slope in the context of the Stokes-Einstein relation for the diffusion
coefficient, and which property of the molecule can be calculated from the slope of the graph?

(c) Calculate the property of Atto655 that can be obtained from the slope of the graph.

PC2-TP-TD-11
(TD-E2) TRANSPORT OF ENERGY
The walls of a section of double glass are 5.0 cm apart. The space between the walls is filled with
Ar gas, which may be taken to behave as a perfect gas. You may also assume that the average
pressure in the space between the walls is 1 atm.

(a) Estimate by a reasonable calculation the rate of the heat transport per unit area of the double
glass through the double glass section from the inside, where the temperature is 298 K, to the
outside, where the temperature is 273 K. You may assume that the temperature gradient over the
double glass section is constant. Discuss the simplifications you made to give a reasonable estimate
of the rate of heat transport per unit area.

HINTS: What other name can you give to the rate of the heat transport per unit area? What
transport law(s) should you invoke here? Use collision theory to get the appropriate transport
coefficient for Argon.

(b) If a room has double glazed windows as described, and the temperature inside the room is to be
maintained at 298 K, calculate the power required by a heating apparatus in the room to supply the
heat lost to the outside, given that the area of the double glass section is 4.0 m2.

(TD-E3) A SOLUTION TO THE DIFFUSION EQUATION

{ 4Dt }
1 x2
State Fick's second law, and show by calculation that c(x, t) = exp − is a
4π Dt

solution to Fick's second law. What is another name for Fick's second law?

PC2-TP-TD-12