Chapter One

Supplemental Questions for Colin Baird's

ENVIRONMENTAL CHEMISTRY THIRD EDITION
by Dietmar Kennepohl

Problem 1-1

Argon makes up 0.93% of the air in the atmosphere. Assume atmospheric pressure
(temperature) is 1.0 atm (25°C) at sea level and and 0.0030 atm (−10°C) at 40 km (high
in the stratosphere).

a. Calculate the partial pressure of Ar (in atm) at each altitude.

b. Convert these partial pressures to units of ppmv.

c. Compare your values in Parts (a) and (b). What is the limitation of reporting relative
concentrations in ppmv as compared to partial pressures?

Problem 1-2

The Beer-Lambert Law describes the transmittance of light (T) as a function of extinction
coefficient (ε), path length (b), and concentration of molecules (c).

T = e−εbc
The extinction coefficient is directly related to light absorbance (A) and is an intrinsic
property of that compound. The Beer-Lambert Law may also be written as

A = εbc

The table below give the extinction coefficients for ozone as a function of wavelength in
the UV-B region of the spectrum.

ε (cm−1) λ (nm)
100 280
32 290
10 300
3 310
0.8 320

a. From the table, calculate the percent UV-B light transmitted to ground level as a
function of wavelength. Note that T=1.0 is equivalent ot 100% transmittance. [Hint:
Assume bc = 0.35 cm  the average thickness of pure ozone at ground level and
equivalent to 350 DU overhead ozone.]

b. If the concentration of ozone were decreased by 1%, how would transmittance of

UV-B vary at each wavelength shown in the table?

Problem 1-3

Describe how the variation of each of the following factors would affect the incidence of
skin cancer in a given population. State your reasoning.

a. light frequency (in range of 240-360 nm)

b. geography

c. time of day

Problem 1-4

The average bond enthalpies of C-F and C-Cl are 484 and 338 kJ mol−1, respectively.

a. Calculate the maximum wavelength of light required to break each of these bonds.

b. In each case, are photons available in the troposphere energetic enough to break that
carbon-haloghen bond through photodissociation?

c. Why do CFCs not photodissociate to an appreciable extent in the troposphere?

Problem 1-5

a. Explain the difference between an equilibrium system and a steady-state system.

b. What feature is common to both systems that might cause an observer to mistake one
for the other?

c. Many of the species like ozone that are observed in the stratosphere are part of what
type of system? Explain.

Problem 1-6

Consider the reaction

NO + O3 → NO2 + O2

which has a rate constant give by k = 1.8 × 10−12 e−1370/T cm3 molecules−1 s−1. Use the
following standard heats of formation.

Substance ∆H of (kJ mol−1)

NO 90.25
NO2 33.18
O3 142.7

a. What is the activation energy of this reaction?

b. What is the standard enthalpy of this reaction? Is it exothermic or endothermic?

c. Draw the potential energy profile of this reaction.

d. From the energy profile can you predict if the reverse reaction (below) will have a
larger or smaller rate constant?

NO2 + O2 → NO + O3

Problem 1-7

It has been suggested that to fix an "ozone hole" one could simply synthesize ozone and
then inject it into the stratosphere. Assuming that enough ozone could be made and
delivered to the stratosphere, explain why this proposal would not work.

Problem 1-8

At 25°C the reaction below has a rate constant of 1.8 × 10−14 cm3 molecules−1 s−1.

NO + O3 → NO2 + O2
Use the following thermodynamic data:

Substance ∆G of (kJ mol−1)

NO 86.55
NO2 51.31
O3 163.2

a. Calculate the standard free energy of this reaction. Is this reaction spontaneous?

b. Calculate the rate constant for the reverse reaction.

NO2 + O2 → NO + O3

Problem 1-9

a. What two physical properties of CFCs make them ideal for various commercial
applications, but also make them a long-term primary cause of ozone depletion?

b. Name at least three common commercial applications of CFC-type compounds.

Problem 1-10

The rate constant for the degradation of the CFC replacement compound HFC-134a
(CF3CH2F) by OH in the troposphere is given by k =
−12 −1750/T −1 −1
1.5 × 10 e 3
cm molecules s . The tropospheric concentration of OH and
CF3CH2 F are 8.1 × 105 and 6.3 × 108 molecules cm−3, respectively.

a. Calculate the rate constant of HFC-134a destruction at 4°C.

b. What is the rate of reaction of HFC-134a with OH in the troposphere at this

temperature?

c. G.D. Hayman at the National environmental Technology Centre, England, uses

relative rate constants to estimate lifetimes of these sorts of substances. Lifetimes (τ)
are calculated with respect to the lifetime of CH3CCl3 (6.6 y at 277K) using:

k[ OH + CH 3 CCl 3 ]
τ(x) = 6.6 y
k [OH + x]

Estimate the lifetime of HFC-134a (at 277K) if k[OH + CH3CCl3] is

6.68 × 10−15 cm3 molecules−1 s−1.

d. Under similar conditions HFCs like HFC-125 and HFC-143a have estimated lifetimes
of 36.4 and 54.1 y, respectively. However, HCFCs used for CFC replacement have
estimated lifetimes generally ranging from 2 to 7 y. If HFCs have such long lifetimes,
why are they being used to replace CFCs?
Problem 1-11

Despite the rapid phase-out of CFC use and production with the Montreal Protocol
(1987) and subsequent amendments in London, Copenhagen, Vienna and Montreal, the
stratosphere chlorine equivalent level is projected to start decreasing slowly only by
2005. (see Figure 2-21 textbook). Suggest reasons why this projection predicts both a lag
in response and the slow rate of decline of chlorine equivalent levels in the stratosphere.

Problem 1-12

The following data was collected for the destruction of O3 by H.

O3 + H → O2 + OH

Run [O3] [H] Initial Rate

(molecules cm−3 × 1012) (molecules cm−3 × 105) (molecules cm−3 s−1)
1 3.11 1.94 1.13 × 107
2 1.55 1.96 5.68 × 106
3 3.12 3.89 2.27 × 107

a. Write an expression for the rate law.

b. Calculate the rate constant for the reaction.

Problem 1-13

The rate constant in units of cm3 molecules−1 s−1 for the reaction of atomic oxygen with
ozone is given by 1.47 × 10−11 e−2218/T , where T is the Kelvin temperature.

a. Assume the reaction follows second order kinetics. Calculate the reaction rate in units
of molecules cm−3 s−1 at −30°C (a typical stratospheric temperature) given that
concentration of O and O3 are 4.6 × 107 and 3.3 × 1012 molecules cm−3 , respectively.

b. Assuming Arrhenius behaviour, calculate the activation energy of this reaction at

−30°C.

Problem 1-14

Given the table of temperature (T) and rate constants (k) below, determine the Arrhenius
factor (A) and activation energy (Ea) of the following mid-stratospheric reaction:

Run T(K) k(cm3 molecules−1 s−1)

1 220 3.7768 × 10−11
2 255 3.8919 × 10−11
3 290 3.9815 × 10−11

© 2005 by W.H. Freeman and Company