9.

3 - The Acidic Environment

Section #2
The Acidic Atmosphere
While we usually think of the air around us as neutral, the atmosphere naturally contains acidic oxides of carbon, nitrogen and sulfur. The concentrations of these acidic oxides have been increasing since the Industrial Revolution

The Acidic Atmosphere

Oxides are chemical compounds formed when an element reacts with oxygen. For example, when a metal such as magnesium is burnt in oxygen, the magnesium burns with a brilliant white flame to generate a white powder (magnesium oxide). 2Mg(s) + O2(g) g 2MgO(s)

When magnesium oxide is added to water containing universal indicator the indicator changes from green to blue-violet. This shows that magnesium oxide is a basic oxide. This reaction occurs because of the presence of water. The magnesium oxide dissolves in the water to generate magnesium hydroxide. The hydroxide ions that are released cause the colour change of the indicator. 2MgO(s) + H2O(l) g 2Mg(OH)2(aq)

The Acidic Atmosphere

Remember
The general equation for Neutralisation is Acid + Base g Salt + Water

The salt that is formed is an ionic compound that is named after their parent acid... with the metal ion of the base is named first, followed by the name of the anion of the parent acid.

The Acidic Atmosphere

Oxides - Acidic or Basic?

If we take an amount of an oxide, dissolve them in water, then the resulting solution may display acidic or basic properties. The general trend is 1. Metal Oxides usually form basic solutions.
remember that basic aqueous solutions are called Alkalis

2. Non-Metal Oxides usually form acidic solutions.

3. Several elements that are located on the boundary between the metals and the non-metals, form solutions that are both acid and basic in nature, and these are called Amphoteric oxides.
Amphoteric = able to react chemically as either an acid or a base

4. The Inert Gases do not form oxides!

The Acidic Atmosphere

In summary

Also there are some other trends to understand

1. The strength of the basicity of metallic oxides increases as you go down a group, hence BaO is a stronger basic oxide than MgO.

The Acidic Atmosphere

2. The strength of the acidity of non-metallic oxides decreases as you go down a group (examine the group 5 N, P, As, Sb, Bi note the change from acidic to basic oxides). 3. Generally, the higher the oxidation state of the metal or non-metal, the more amphoteric or acidic the oxide Cl2O7 is more acidic than Cl2O (in fact the effect of differing oxidation states on the acidity of oxides makes it difficult to discuss trends in acidity and basicity in the oxides of the elements of the periodic table).

Oxides & Pollution

Our atmosphere is a sink for many pollutants. Some of these pollutants are oxides. Volcanoes and geysers release many different gases into the atmosphere, including sulfur dioxide.

The Acidic Atmosphere

Carbon monoxide, carbon dioxide and sulfur dioxide are also formed during the combustion of organic matter during bushfires. Bacterial decomposition can also release sulfur dioxide into the environment. Lightning storms produce toxic nitrogen oxides as nitrogen and oxygen molecules react together. The activities of human beings result in the release of oxides into the atmosphere. Industries generate a variety of oxides such as carbon monoxide (CO), carbon dioxide (CO2), sulfur dioxide(SO2) and the oxides of nitrogen (NOX).

The Acidic Atmosphere

i. Carbon Oxides
The natural cellular respiratory processes of animals and plants produce carbon dioxide, which is ultimately released into the atmosphere. Green plants utilise the carbon dioxide for photosynthesis. Large amounts of carbon monoxide and carbon dioxide are also produced during bushfires, since the process of incomplete combustion produces carbon monoxide, whereas carbon dioxide is the product of complete combustion. The combustion of fossil fuels such as petrol, kerosene and diesel oil releases large amounts of the carbon oxides into the atmosphere. Coal-fired power plants also release vast amounts of carbon oxides into the atmosphere. The increasing levels of carbon dioxide in the atmosphere are often linked to global warming. Carbon monoxide does not build up over time in the atmosphere as it is rapidly removed by the action of soil organisms or by oxidation to carbon dioxide.

The Acidic Atmosphere

ii. Sulfur Oxides
The oxides of sulfur are generally irritating, poisonous gases.

These gases particularly affect people who suffer from respiratory problems such as asthma and emphysema.
About 50% of the sulfur dioxide that enters our atmosphere is derived from the oxidation of hydrogen sulfide (H2S) produced from bacterial decomposition. Many oxides of sulfur are also released into the atmosphere during volcanic eruptions. Sulfur dioxide is produced by the combustion of fuels such as coal and diesel oil. In Australia considerable quantities of coal are burnt to generate most of our electricity (~75%). Fossil fuels usually contain small quantities of sulfur minerals (e.g. FeS2) although the bituminous coal from eastern NSW is lower in sulfide minerals than coal from other locations.

The Acidic Atmosphere

These sulfide minerals in coal are oxidised during combustion, and sulfur dioxide is released.

4FeS2(s)

11O2(g)

2Fe2O3(s)

8SO2(g)

Metal smelters that convert sulfide minerals into metals are also a major source of sulfur dioxide pollution.

Example The smelting of chalcopyrite (CuFeS2) during the production of copper results in the release of sulfur dioxide. Towns near these smelters can suffer from sulfur dioxide pollution. + 5O2(g) + 2SiO2(s) g 2Cu(l) + 4SO2(g) + 2FeSiO3(l)

2CuFeS2(s)

In regions such as the lower Hunter, about 95% of SO2 emissions are associated with power and smelting industries.

The Acidic Atmosphere

Sulfur trioxide is produced mainly by oxidation of sulfur dioxide in the atmosphere. Oxygen and ozone are the oxidants involved in this oxidation process.

2SO2(g)
SO2(g) +

+
O3(g)

O2(g)
g

g
SO3(g)

2SO3(g)
+ O2(g)

iii. Nitrogen Oxides

Nitric oxide (NO) and nitrogen dioxide (NO2) are the most common atmospheric oxides of nitrogen found in urban air. In Sydney, about 86% of the total emissions of NOX comes from the engines of motor vehicles and other transport. The nitric oxide (a colourless gas) is formed when nitrogen and oxygen react at high temperatures. Nitric oxide is a neutral oxide. N2(g) + O2(g) g 2NO(g)

The Acidic Atmosphere

NO2 is a brown gas and is produced by oxidation of NO. The rate of NO2 formation depends on the concentration of NO in the air. Up to 10% of the total NOX in air is NO2. Nitrogen dioxide is an acidic oxide. 2NO(g) + O2(g) g 2NO2(g)

NOX is also derived from other sources, including industries, electrical power production and oil refining. NO2 is of concern as it causes damage to the respiratory system of humans as well as irritating the eyes.

Young children and older people are particularly susceptible.

Un-flued gas heaters and kerosene heaters also contribute to NO2 pollution of the air inside houses.

The Acidic Atmosphere Monitoring Atmospheric Pollution

During the industrial revolution of the 19th century, large amounts of coal were burnt to provide power for factories and their machines. Vast quantities of carbon dioxide and sulfur dioxide poured into the air. Iron smelters generated large volumes of sulfur dioxide as they produced the growing quantities of steel required for industry. The atmosphere of large industrialized cities in Europe and the USA became highly polluted with acidic gases. The increased use of motor vehicles in the 20th century (particularly after 1945) increased oil consumption. Emissions of sulfur dioxide doubled in the 25-year period following World War II.

The Acidic Atmosphere

Adding to this pollution burden on the atmosphere was the increasing production of nitrogen oxides in internal combustion engines. Following numerous deaths (about 4000) in London in 1952 due to heavy acidic smogs, pollution controls began to be introduced to clean up the air of these large cities. High levels of photochemical smog (produced by the action of sunlight on air containing moisture, ozone, hydrocarbons and NOX) in cities such as Los Angeles and Tokyo in the 1960s accelerated the push for emission controls on motor vehicles. In the 1970s the development of more sensitive gas analysis technologies allowed chemists to monitor the global increase in sulfur dioxide emissions due to the expansion of industries in Asia. In recent years the air quality has improved in most westernized countries. In Europe, the sulfur dioxide emissions dropped by about 45% in the 1990s.

The Acidic Atmosphere

In the same period, nitrogen dioxide emissions dropped by about 20%. However, due to increasing population and usage of motor vehicles, the levels of pollutants have stabilised rather than continuing to decrease.

The Environmental Protection Agency of NSW (EPA) monitors the levels of pollutant gases in the atmosphere in many regions across NSW.
The NSW Department of Environment and Conservation prepares quarterly reports on air quality.

The Acidic Atmosphere

This data confirms that the air quality in Sydney with respect to SO2 and NO2 is high when compared with NEPC standards. The data shows no discernible trends overall across the 5-year period. The air in Sydney compares favorably with that of much larger cities overseas. The large industrialised cities in China, the USA and Europe have much higher levels of atmospheric NO2 and SO2 than Sydneys.

The Acidic Atmosphere Reducing Atmospheric Pollution

In order to reduce emissions of sulfur dioxide and nitrogen oxides there are a number of options available...

i. Reduce the amount of coal being burnt

this can be achieved if people use appliances that are more energy-efficient; as individuals we can help by reducing our own personal use of electricity

ii. Use Coal with lower sulfur content

Power companies could switch to burning low-sulfur coal rather than high-sulfur Coal. They can also switch to natural gas, which produces very little sulfur dioxide on combustion

iii. Reduce the reliance of Fossil Fuels

The development of other forms of power production such as hydroelectricity and solar power, this reducing our need to burn fossil fuels.

The Acidic Atmosphere

iv. Recycling the gases
Techniques such as collecting the sulfur dioxide produced by smelting metal sulfides and the using it to make sulfuric acid (a very important industrial chemical) could be employed.

v. Flue Gas Scrubbing

The acidic gases are passed through a slurry of a base such as calcium oxide; would cause the sulfur dioxide to react with the calcium oxide to form solid calcium sulfite. Hence the gas is removed from the smoke that is released into the atmosphere.

vi. Catalytic Converters

Most modern cars are equipped with catalytic converters, which convert the nitrogen oxides back to nitrogen gas.

2NO(g)

2CO(g)

N2(g)

2CO2(g)

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Acid Rain
When all gases are removed from pure water, its pH is 7.0 (neutral) at 25C. However, natural water contains dissolved gases including carbon dioxide, which makes the water weakly acidic (pH 6.06.5) due to the presence of carbonic acid. CO2(g) + H2O(l) g H2CO3(aq)

When the atmosphere is polluted with acidic oxides such as sulfur dioxide and nitrogen dioxide, rainwater can become quite acidic (pH 4.05.0) due to the high solubility of these gases in water. Rain that has such a low pH is called Acid Rain. Acid rain with a pH of 3.6 has been recorded in many severely polluted industrialised areas in Europe and the USA.

The Acidic Atmosphere

When the oxides of sulfur and nitrogen dioxide dissolve in water they produce solutions of various acids.
Sulfur dioxide forms weak sulfurous acid (H2SO3) whereas sulfur trioxide produces strong sulfuric acid (H2SO4). SO2(g) SO3(g) + + H2O(l) H2O(l) g g H2SO3(aq) H2SO4(aq)

Sulfurous acid can be catalytically oxidised to produce sulfuric acid.

2H2SO3(aq)

O2(g)

2H2SO4(aq)

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Nitrogen dioxide produces weak nitrous acid (HNO2) and strong nitric acid (HNO3) when it dissolves in water.
2NO2(g) + H2O(l) g HNO2(aq) + HNO3(aq)

In the presence of water and oxygen the nitrous acid is catalytically oxidised to nitric acid.
2HNO2(aq) + O2(g) g 2HNO3(aq)

Effects of Acid Rain

When you visit the ancient cities of Europe you may observe that many marble statues and building facades are eroded. When the calcium carbonate of the marble (& limestone) is attacked by the sulfuric acid in acid rain, the surface of the marble is converted into insoluble calcium sulfate.

The Acidic Atmosphere

CaCO3(s) + H2SO4(aq) g CaSO4(s) + H2O(l) + CO2(g)

The wet calcium sulfate crystallises to form a porous and crumbly mineral called gypsum (calcium sulfate dihydrate). Over several centuries the soot from coal burning, as well as various dusts, have collected in the pores of the gypsum and turned the marble black.

The Acidic Atmosphere

Acidic rain can also attack metallic structures composed of iron and steel. The iron is oxidised by the hydrogen ions in the acid and becomes chemically weathered. Fe(s) + H2SO4(aq) g FeSO4(aq) + H2(g)

Acid rain has had a devastating effect on many northern hemisphere forests, especially the famous Black Forest in Germany that has been significantly damaged by acid rain.

Acid rain also affects the soil, and the acidified soils inhibit the growth of plant seedlings.
Basic minerals in the soil (such as dolomite and limestone) are attacked and dissolved by acidic water. Many types of sandstone have grains that are cemented together with calcite (calcium carbonate), and the acid rain will dissolve this cement and so cause significant chemical weathering and erosion.

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Equilibrium
The term Equilibrium is used in many science disciplines. For example, in physics if a hot coin is dropped into a cup of cold water, the water/coin system will reach thermal equilibrium when both water and coin are at the same temperature. Although the configuration (or large-scale properties) of a system in equilibrium do not change over time, the small-scale, microscopic configuration of the system is not static & unchanging. This is especially important in the study of chemistry since not all reactions proceed to completion. In many reactions, the final reaction mixture consists of both products and reactants

The Acidic Atmosphere

Consider the following, chemical reaction A + B g C + D

Molecules A & B react to form molecules C & D. the reactant molecules are totally converted in to the product molecules, the reaction has gone to completion (combustion of ethanol). However for many some reactions, once the molecules of C & D are formed, they can react together to produce the original molecules of A & B C + D g A + B

The overall reaction is often written as Forward Reaction A + B C + D The system is in Chemical Equilibrium.

Reverse Reaction

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Microscopically the configuration of the equilibrium system is not static, because forward and reverse reactions are always occurring.

However since the microscopic reactions are in balance the large-scale properties of the system appear constant (no colour change etc).

Example
Consider the following, equilibrium system N2O4(g) 2NO2(g)

Initially there would only be N2O4 molecules in the container.

N2O4

Concentration

Oxygen Nitrogen

NO2 Time

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Example
continued

Over time, the N2O4 reacts to make NO2 Concentration

N2O4 NO2 Time

Some of the NO2 molecules will recombine to create N2O4 and the system settles into an equilibrium.

Concentration

N2O4 NO2 Time

The Acidic Atmosphere Features of Equilibrium

All systems in chemical equilibrium exhibit the following characteristics Atoms, molecules or ions cannot leave or enter the system. Thus the reaction of calcium carbonate with hydrochloric acid in a beaker is not a closed system as the carbon dioxide escapes. The observable or measurable properties of the system are constant. These include colour, electrical conductivity, concentration and gas pressure.

i. The system is closed

ii. Constant Observable Properties

iii. Constant Equilibrium Concentrations

The concentrations of reactants and products are constant once equilibrium is achieved.

iv. Equal Reaction Rates

The rate of the forward reaction equals the rate of the reverse reaction.

The Acidic Atmosphere The Equilibrium Constant

Chemists use the Equilibrium Constant (Kc) as a mathematical tool to help them study systems in equilibrium.
Consider the following general equilibrium system aA + bB gC + dD

The equilibrium constant for this system is given by the formula

Kc =

[C] [D]

products reactants

[A]

a [B]b

The equilibrium constant allows us to predict the position of the equilibrium.

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Reactants aA + bB gC + dD Products

If the equilibrium constant (Kc) is very less than one then virtually no products are formed or no reaction occurs at all. less than one then the [reactants] are favoured reverse reaction is predominant little products are formed. equal to one then the [reactants] & [products] are about the same neither the reactants or products are favoured. greater than one then the [products] are favoured forward reaction is predominant little reactants remain. very greater than one then virtually no reactants remain or the reaction goes to completion.

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Example H2(g) + I2(g) 2HI(g)

The equilibrium constant for this reaction is given by Kc =

[HI]2
[H2] [I2]

The concentrations of each of the substances in the above reaction were analysed

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Example continued H2(g) + I2(g) 2HI(g)

For experiment I: Kc = [0.156]2 [0.0222] [0.0222]

Kc = 49.4 Repeating this calculation for the other experiments we get Exp II = 49.8, Exp III = 49.4, Exp IV = 49.5 average for all four experiments = 49.5. Hence in this equilibrium system the products are favored and there will be small amounts of the reactants remaining.
Note the variance between values is due to experimental error!!

The Acidic Atmosphere Le Chatelier's Principle

Since no chemical equilibrium system can remain completely undisturbed by the outside environment for a long period of time, humans began to investigate the effect of altering systems that were at chemical equilibrium. Le Chateliers principle governs disturbances to equilibrium systems If a chemical system at equilibrium is disturbed, the equilibrium moves in the direction that tends to reduce the disturbance.

This principle allows us to predict the effect of any change we wish to make to equilibrium systems.

The Acidic Atmosphere Factors that Effect Equilibrium

There are several external factors that can potentially effect a system in equilibrium. The most common being 1. The Addition / Removal of a reactant or product. 2. Changing the Volume of the system.

3. Changing the Temperature of the system.

4. The addition of a Catalyst.

The Acidic Atmosphere 1. Addition / Removal of a Reactant / Product

The equilibrium will shift to consume the added reactant/product, or to replace the removed reactant/product.

Example 3H2(g)

N2(g)

2NH3(g)

If N2 is added N2 must be consumed forward reaction favoured g more NH3 will be produced

If NH3 is removed NH3 must be replaced forward reaction favoured g more NH3 will be produced

Effect of change in concentration

The Acidic Atmosphere 2. Changing the Volume of the System

Changing the volume of a reaction system will only effect Gaseous reactants or products.

Remember from the preliminary course, the volume and pressure of a gas are inversely proportional
Va

1
P

h Volume i Pressure

i Volume h Pressure

Also remember from the preliminary course, 1 mole of any gas has the same volume if they are at the same temperature & pressure.
0C & 1atm = 22.71 Lmol-1

25C & 1atm = 24.79 Lmol-1

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So the effect of changing the volume (or pressure) of an equilibrium system that contains a gaseous material will depend upon the number of mole of gas reactants or products. The equilibrium will shift to ensure that the total number of mole of gases will be advantageous in the altered system.

Example 3H2(g) + N2(g) 2NH3(g)

2 mol gas products

4 mol gas reactants If i Volume h Pressure

#mol of gas will want to decrease g more NH3 will be produced

forward reaction favoured

If h Volume i Pressure

#mol of gas will want to increase g more H2 & N2 will be produced

reverse reaction favoured

Effect of change in pressure

The Acidic Atmosphere 2. Changing the Temperature of the System

Remember from the preliminary course, exothermic reactions give off heat and have a negative DH value 3H2(g) + N2(g) g 2NH3(g)
DH = -46.19 kJmol-1

If heat is given off then you can imagine heat as one of the products 3H2(g) + N2(g) g 2NH3(g) + HEAT

Likewise, endothermic reactions absorb heat and have a positive DH value

2NH3(g) g 3H2(g) + N2(g)
DH = +46.19 kJmol-1

If heat is absorbed then you can imagine heat as one of the reactants 2NH3(g) + HEAT g 3H2(g) + N2(g)

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So the effect of changing the temperature of an equilibrium system will depend upon exothermic/endothermic nature of the forward reaction.

Decreasing the temperature of an equilibrium favour the exothermic reaction direction.

Example 3H2(g) + N2(g) 2NH3(g) + HEAT DH = -46.19 kJmol-1

Negative DH
removed heat

Forward Reaction is Exothermic added heat

If temperature is increased

endothermic reaction is favoured g NH3 will be consumed

added heat

reverse reaction is enhanced

If temperature is decreased

removed heat

exothermic reaction is favoured

forward reaction is enhanced

g NH3 will be produced

Effect of changing temperature

For the N2O4/NO2 system, the forward reaction is endothermic. N2O4(g) + 57 kJ 2NO2(g) The forward reaction therefore absorbs heat and the reverse reaction releases heat.

The Acidic Atmosphere 4. The Addition of a Catalyst

Catalysts speed up reactions without being altered in the reaction. The addition of a catalyst will speed up the forward and reverse reaction rates, but will have no effect on the reactants or products of the reactions. So the composition of the equilibrium mixture is unchanged, the catalyst simply helps the reaction reach equilibrium faster.

Carbon Cycle

Aqueous CO2 Equilibrium

NB: solubility of gases increase as temperature decreases

Carbon Dioxide Water Equilibrium

The reaction between carbon dioxide and water CO2(g) + H2O(l) H2CO3(aq) is of great practical significance. The The The The removal of carbon dioxide from our bodies transport of carbon dioxide in photosynthesis removal of carbon dioxide from the atmosphere preparation of aerated drinks.

The reaction does not go to completion, rather it is an equilibrium reaction. CO2(g) + H2O(l) H2CO3(aq)

The Acidic Atmosphere Aqueous CO2 Equilibrium

Carbon dioxide is an acidic oxide, that dissolves in water CO2(g) g CO2(aq)

to produce a solution of carbonic acid (H2CO3) CO2(g) + H2O(l) g H2CO3(aq)

and the carbonic acid is in equilibrium with hydrogen ions and hydrogen carbonate ions H2CO2(aq) g H+(aq) + HCO3-(aq)

This dissolution of CO2 in water, overall is exothermic.

The Acidic Atmosphere

Carbonated soft drinks are manufactured by dissolving carbon dioxide in water under pressure (~400500kPa), hence the water in the soft drink is supersaturated in carbon dioxide.
If the bottle is sealed, high pressure in the space under the cap causes... CO2(g) g
favored

CO2(aq)

carbon dioxide is dissolved

CO2(g)

H2O(l)
favored

H2CO3(aq)

carbonic acid created

H2CO2(aq)

H+(aq)
favored

HCO3-(aq)

H+ is created increasing the acidity of the drink

Hence soft drink tastes sour because of their acidity (pH ~ 4).

The Acidic Atmosphere

When the cap of a soft-drink bottle is unscrewed, there is a rapid effervescence observed, and overtime the soft drink eventually goes flat and tastes less sour due to the reversal of these three equilibria.

The equilibrium of a soft drink can also be altered by changing its pH, and heating/cooling the drink.

The Acidic Atmosphere Calculating Gas Volumes

Gas volumes involved in chemical reactions can be calculated using very simple techniques.
mass
(g)

Molar Mass Molar Mass

Avogadros
Number

# species
(atoms, molecules, ions)

Avogadros
Number

# mol
Gas Constant Volume (L) Volume (L)

gas volume
(L)

Gas Constant

concentration
(molL-1)

only if in the gas state

only if an aqueous solution

The Acidic Atmosphere

Hence the volume of gases can be directly compared to the #mol of gas in a sample, using the following constants
1 mol of any gas at 100kPa and at 0C
(273.15 K) (298.15 K)

g 22.71 L g 24.79 L

at 25C Example

If 4.5g of Sodium Carbonate is reacted with excess Hydrochloric Acid, calculate the volume of CO2 gas that is produced (assume conditions to be 25C & 100kPa). 2HCl(aq) + Na2CO3(s) g 2NaCl(aq) + CO2(g) + H2O(l)

#mol Na2CO3 = 4.5 106 = 0.042mol

Na2CO3:CO2 g 1:1

#mol CO2 = 0.042mol

volume CO2 = 0.042 24.79 = 1.05L