Ozone and Smog

Ground level ozone is produced when hydrocarbons, nitrogen oxides, light, and oxygen are present. The
mixture of molecules present under these conditions is called smog, or photochemical smog. Many of the
component molecules are toxic to humans, other animals, and plants. Smog causes severe respiratory
problems in people. It is most common in cities during the summer months. Today we'll discuss the
chemistry behind ground level ozone formation.

Outline
• Nitrogen Oxides
• Ground Level Ozone
• Acids in the Atmosphere
• Homework

Nitrogen Oxides

Nitrogen is to the right of oxygen in the periodic table. Nitrogen is less electronegative than oxygen. All
N-O bonds are polar bonds with more electron density on the oxygen atom.

Nitrogen has 5 valence electrons and is in a row with a maximum valence number of 8. It typically
forms 3 bonds and has a lone pair (:NH3) or makes 4 bonds with a positive charge (NH4+).

Nitrogen is one of the few elements that readily forms strong multiple bonds. (Carbon is another.) There
is a very strong triple bond between nitrogen atoms in molecular nitrogen. The N=N bond energy of
azides is less than half the energy of a triple bond and N-N bonds are quite weak. Single N-O bonds are
considerably weaker than N-H bonds. A summary of N-X bond energies (in kJ/mol) is below.

Most of the nitrogen compounds in the atmosphere, apart from molecular nitrogen, are nitrogen oxides.
(a) N2O, or nitrous oxide, and some NO, or nitric oxide, are produced by bacteria in the soil and in the
oceans. Nitrous oxide is relatively unreactive in the troposphere and is the main source of nitric acid and
other nitrogen oxides in the stratosphere. We've seen that this is important in the chemistry related to
ozone destruction in the stratospheric ozone layer.

(b) Nitric oxide (NO) results from the combination of O2 and N2 in lightning strikes. It is a radical and so
is very reactive in the atmosphere. Reaction of NO with oxygen atom or ozone produces nitrogen dioxide.

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(c) Nitrogen dioxide (NO2) is a brown gas, responsible for the color of photochemical smog. It is a
radical and so is reactive in the atmosphere. Nitrogen dioxide is in equilibrium with its colorless dimer,
N2O4. Visible light can photolyze NO2 to NO and oxygen atom.

(d) Dinitrogen tetraoxide (N2O4) is a colorless gas with a very weak N-N bond and is in equilibrium
with NO2.

(e) Other neutral nitrogen oxides include N2O5 and N2O3.

(f) Nitrogen trioxide (NO3) is a radical with an unpaired electron on one of the oxygen atoms. Its
reactivity is similar to that of the hydroxy radical (HO).

The structures of NO2, N2O4, and N2O5 are below.

Nitrogen Dioxide Equilibrium at Low Temperature

Let's consider the dimerization reaction of nitrogen dioxide.

The activation barrier for the coupling of the two nitrogen-centered radicals is low so the forward reaction
is fast. All N-N bonds are weak and this one especially weak due to the repulsive effect of the formal
positive charge on each nitrogen atom. Because of this, activation barrier for the reverse reaction is also
low and the reverse reaction is fast.

Knowing the Gibbs free energy change for the reaction at 0 deg and 1 atmosphere pressure, we can
calculate an equilibrium constant and so the ratio of the two gases.

ΔG = - R T lnKeq -9.2 kJ/mol = -9.2 x 103 J/mol = - (8.31 J K-1 mol-1)(273.15 K) lnKeq

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 4.053 = lnKeq

e4.053 = Keq

57.6 = Keq = [N2O4]/[NO2][NO2]

There should be more N2O4 at this low temperature than NO2. In fact, for every molecule of NO2, there
will be nearly 7 molecules of N2O4.

Nitrogen Dioxide Equilibrium at High Temperature

Notice that the equation defining Gibbs free energy includes a term for enthalpy, ΔH, and a term for
entropy, ΔS.
ΔG0 = ΔH0 - TΔS0

The enthalpy term is the heat released or absorbed by the chemical reaction. We can explain the enthalpy
change by looking at the relative strength of the bonds made or broken. Usually, this term is large and
dominates the Gibbs free energy value.

In the nitrogen dioxide dimerization however, the enthalpy change is small because the bond being made
or broken is very weak. The entropy term becomes important. This is especially true at high temperature
because the entropy term includes temperature and becomes larger with temperature.

What is entropy? This is the disorder of the system. When we look at the nitrogen dioxide dimerization,
it is easy to see that the order increases (disorder or entropy decreases) in the forward direction. Two,
separated molecules are converted into one molecules.

OK, the value of ΔS will be negative because entropy decreases in the forward direction. At 100 deg C,
the entropy term is large enough to change the sign of ΔG. It is +8.4 kJ/mol at 100 deg. This changes the
equilibrium constant:

ΔG = - R T lnKeq +8.4 kJ/mol = 8.4 x 103 J/mol = - (8.31 J K-1 mol-1)(373.15 K) lnKeq

-2.7 = lnKeq

e-2.7 = K
eq

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 0.066 = Keq = [N2O4]/[NO2][NO2]

At this higher temperature, the monomer is favored over the dimer in the equilibrium. There will about 31
molecules of NO2 for every N2O4 at equilibrium.

Le Chatelier's Principle and Pressure Effects

When there is a change in concentration, temperature, volume, or partial pressure to a chemical
system at equilibrium, the equilibrium shifts to counteract the change and a new equilibrium is
established.

We can use this principle to predict what would happen with pressure changes to the NO2/N2O4
equilibrium.

We know from the ideal gas law (PV=nRT) that the pressure is proportional to the number of gas
molecules. When some NO2 molecules dimerize, the total number of molecules decreases.

Therefore, an increase in pressure should lead to a new equilibrium that favors N2O4 more over NO2.

A decrease in pressure should lead to a new equilibrium that favors NO2 over N2O4.

Ground Level Ozone Formation

Ground level ozone levels are highest in cities with high levels automobile traffic during daylight hours in
the summer. Why? We can explain this through chemical reactions of nitrogen oxides, oxygen, and
hydrocarbons.

Hydrocarbon Oxidation
Automobiles use hydrocarbons, gasoline or diesel, as fuel. The hydrocarbons are burning in the internal
combustion engines. Complete combustion of a hydrocarbon should produce only carbon dioxide and
water. Fro example:

C7H16 + O2 7 CO2 + 8 H2O

However, the fuels are not pure hydrocarbons. Nitrogen impurities burn with the fuel to form NO and
NO2.

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A significant amount of volatile hydrocarbons are released without combustion or with only partial
combustion. These can be oxidized by hydroxyl radical and oxygen to form alkylperoxy radicals. For
example:

Nitric Oxide and Alkylperoxy Radicals

Nitric oxide from the gasoline impurities can react with peroxy radicals to make nitrogen dioxide and
another radical.

Alcohols
The next step is the reaction of the new radical with more hydrocarbon. This generates a more stable
carbon molecule called an alcohol.

An alcohol is a hydrocarbon derivative with an oxygen atom between on of the C-H units. They are
named by substituting the final "e" from the hydrocarbon name with "ol".
• methane + ol = methanol
• ethane + ol = ethanol
• propane + ol = propanol
• butane + ol = butanol

Ozone Formation
The brown gas NO2 is photolyzed by visible light to make NO and oxygen atom. The oxygen atom can
combine with O2 to make ozone.

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The Catalytic Cycle
NO is converted to NO2, then reconverted to NO as ozone forms. The nitrogen oxide is not used up. We
can combine the reactions to make a catalytic cycle.

Acids in the Atmosphere

Acids release H+(aq) when dissolved in water. In water, we use pH, or -log[H+] to measure acidity. Many
acids are formed in the atmosphere through the oxidation and hydrolysis reactions.

Strong Acids in Water

Strong acids are those that completely dissociate in water: HCl, HBr, HI, H2SO4, HNO3, and HClO4.

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The concentration of solvated protons is equal to the moles of the acid added to each liter of water.
When 0.05 mol of HNO3 is added to 50 mL water:
[H+] = (0.05 mol)/(50 mL)(1 L/1000 mL) = 1.0 M

pH = -log(1.0) = -log(100) = 0

When 0.05 mol of H2SO4 is added to 10 L water:

[H+] = (0.05 mol)/(10 L) = 0.005 M = 5 x 10-3 = 100.70 x 10-3

pH = -log(10-2.3) = 2.3

Weak Acid Equilibrium

Nitrous acid is in equilibrium with a proton and its conjugate base, NO2-. Because the concentration of
water is constant, we can define a constant equal to the product of the concentration of water and the
equilibrium constant. This constant, the Ka is 10-3.29 for HNO2.

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We can use the Ka to determine the pH of a solution of nitrous acid. For example, let's determine the pH
of a solution made from 0.01 mole of HNO2 in 1.0 L of water.

Some of the acid will dissociate into H+ and NO2- but we don't know w=how much. We'll call the molar
concentration of solvated protons x so [H+] = x. This means that the concentration of NO2- must also be x
because they form in equal amounts by the dissociation of the acid. The concentration

It is always possible to solve for x by using the quadratic equation but most of the time we can solve it
using an approximation. If we assume that the extent of dissociation is small, then the equilibrium

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concentration of acid doesn't change very much from its original concentration. We can then use the
original acid concentration in the Ka expression.

The approximation is a good one in this case because we get the same pH value using it as we did from
the quadratic equation.

Weak Acids and Strong Acids

The acid dissociation constants of a selection of acids is in the tables. In the table are listed pKa values.

pKa = -log(Ka)

The very strong acids, those that are completely dissociated in water, are distinguished by examining their
acid dissociation equilibrium in non-aqueous solvents and the pKa for water is estimated. The equilibrium
constants for the weaker acids (pKa >0) are determined from pH measurements of solutions.

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