1 Sulfur and Nitrogen Introduction The reactivity of nitrogen is relatively low because of its _____________.

The nitrogen molecule, N2, has a __________ bond between the two nitrogen atoms.

dot and-cross diagram of nitrogen This is a very __________ bond with a bond energy of +944 kJ mol-1. If nitrogen and oxygen are sparked together, nitrogen monoxide is formed.

Similarly, magnesium nitride is formed when magnesium is burnt in nitrogen. The activation energy is going to be _____________, because of the need to break the very strong nitrogen-nitrogen bond. Nitrogen molecules are _______________. Therefore, they aren't so attractive to nucleophiles or electrophiles.

Chemical Bonding in Ammonia Ammonia has an active _____________ pair on the nitrogen which accepts a hydrogen ion to form an ammonium ion. A ________________ bond is formed between the nitrogen and the incoming hydrogen ion. Ammonia is a Bronsted-Lowry base. For example, ammonia reacts with hydrogen chloride gas:

Ammonia

hydrogen choride

ammonium chloride

2 When ammonia reacts with water.

Ammonia

water

ammonium ion

hydroxide ion

Ammonium ion has ____________________ shape like methane

Reactions of ammonia Ammonia is only a _____________ base and ammonium salts react readily with bases to produce ammonia gas. For example:

When ammonium salt is warmed with sodium hydroxide solution, __________________ gas is pungent and it turns red litmus paper blue. The ionic equation for this reaction is:

Ammonium salts such as ammonium sulphate or ammonium nitrate are commonly used as ____________________. However, farmer wouldn't treat a field with an ammonium compound at the same time as using an alkali (a soluble base) like lime. The ammonium salt will react with the base to give off ammonia which will escape into the atmosphere as a gas, and so not be available to the plants.

Uses of ammonia

To make fertilisers, such as ammonium sulphate, ammonium nitrate or ammonium phosphate, or urea - CO(NH2)2. Some ammonia is also injected directly into the soil to act as a fertiliser. Ammonia is used to make ___________________ acid.

Uses of nitric acid

To make fertilisers such as ammonium nitrate. This is the major use of the nitric acid. To make explosives such as TNT (and many others). In the manufacture of dyes, drugs, polymers (etc).

Overuse of nitrate fertilisers

3 All nitrates are _________________________ in water, and so are all ammonium salts. That means that any fertiliser not used by the growing crop will dissolve in rainwater and eventually find its way into streams, rivers and lakes. This will fertilise the growth of water plants and algae which can choke the surface of the water, cutting off light to other plants underneath. When this excess growth dies and decomposes, the process can use up all the oxygen in the water. Loss of dissolved oxygen will cause fish to die. This process of excess growth leading to the destruction of life in the water is known as __________________________.

Role of Catalytic Converter (removal of nitrogen monoxide) In a petrol (gasoline) engine, a spark is passed through a mixture of petrol vapour and air to ignite the petrol. But it also causes some of the oxygen and nitrogen in the air to combine:

If this escapes into the atmosphere, it causes problems (see below), but it can be removed using a catalytic converter. A catalytic converter uses expensive metals like ______________________ coated on to a _________________structure to give a high surface area. The platinum catalyses various reactions which help to get rid of pollutants from the exhaust gases. In this case, it converts harmful carbon monoxide and nitrogen monoxide into __________________ and ____________________________.

Because all nitrates are soluble, removing them from water intended for drinking can be expensive. High levels of nitrates in drinking water can cause a disease in young babies called "__________________ syndrome" - so-called because the nitrates interfere with the way oxygen is carried in the blood. Unoxygenated blood has a bluish colour.

Acid Rain Nitrogen monoxide and nitrogen dioxides are pollutants that play their role in the formation of acid rain. Nitrogen monoxide reacts with oxygen in the atmosphere to form nitrogen dioxide.

Catalytic oxidation of SO2 to SO3 The main cause of acid rain is __________________________. It is _________________ to give sulphur trioxide which reacts with rain water to give very dilute sulphuric acid.

Nitrogen dioxide acts as a ______________________ in the conversion of sulphur dioxide into sulphur trioxide. The nitrogen dioxide first oxidises sulphur dioxide to sulphur trioxide. In the process, the nitrogen dioxide is reduced to ________________________.

Now the nitrogen monoxide is converted back to nitrogen dioxide again by reaction with oxygen.

So, the nitrogen dioxide is _________________________ at the end of the reaction. Nitrogen dioxide is contributing to the formation of ______________________ smog. It has a role in the formation of ___________________, and of chemicals called peroxyacetylnitrates (PAN). Ozone in smog is dangerous to health and so are peroxyacetylnitrates(PAN). These last substances are formed by complex reactions involving nitrogen dioxide, unburnt hydrocarbons present in exhaust gases, and oxygen from the air.

Formation of atmospheric sulphur dioxide Fossil fuels like coal and oil all contain __________________ compounds, and when the coal or the oil product (petrol or diesel or whatever) are burned, _________________________ is produced. This leads to acid rain. Burning coal in power stations was a major source of sulfur dioxide, but there are ways of removing this from the flue gases, known as "flue gas _______________________". The best of these methods allow the sulfur dioxide to be recovered and then converted into sulfuric acid. Sulfur compounds in petrol (gasoline) or diesel oil were also an important source of sulfur dioxide pollution. Nowadays, these sulfur compounds can be removed at the refinery to produce low-sulfur fuels.

The role of sulphur dioxide The role of sulphur dioxide includes:

its formation during the combustion of fossil fuels. the oxidation of sulphur dioxide to sulphur trioxide catalysed by nitrogen dioxide. the reaction of the sulphur trioxide with water to produce very dilute sulphuric acid.

The consequences of acid rain The consequences of acid rain include:

the corrosion of limestone buildings as the calcium carbonate reacts with the acid. the corrosion of ironwork as the iron reacts with the acid. the acidification of lakes and rivers leading to the death of aquatic life. This is complicated by the fact that a fall in pH dissolves aluminium ions from the soil. Aluminium ions are toxic to fish. damage to trees. This again is partly the result of aluminium ions being toxic to plants.

Contact Process The Contact Process:

makes sulphur dioxide; convers the sulphur dioxide into sulphur trioxide (the reversible reaction at the heart of the process); converts the sulphur trioxide into concentrated sulphuric acid.

Making the sulphur dioxide This can either be made by burning sulphur in an excess of air:

. . . or by heating sulphide ores like pyrite in an excess of air:

In either case, an excess of air is used so that the sulphur dioxide produced is already mixed with oxygen for the next stage. 1. Converting the sulphur dioxide into sulphur trioxide This is a reversible reaction, and the formation of the sulphur trioxide is exothermic.

A flow scheme for this part of the process looks like this: Sulfur dioxide + oxygen(from air) in the ratio 1:1 by volume 400 -450 oC ;1-2 atm ; V2O5 catalyst Sulfur trioxide

2. Converting the sulphur trioxide into sulphuric acid This can't be done by simply adding water to the sulphur trioxide - the reaction is so uncontrollable that it creates a fog of sulphuric acid. Instead, the sulphur trioxide is first dissolved in _____________________sulphuric acid:

The product is known as fuming sulphuric acid or ___________________. This can then be reacted safely with __________________ to produce concentrated sulphuric acid - twice as much as you originally used to make the fuming sulphuric acid.

Explaining the conditions The proportions of sulphur dioxide and oxygen The mixture of sulphur dioxide and oxygen going into the reactor is in ____________l proportions by volume. Avogadro's Law says that equal volumes of gases at the same temperature and pressure contain equal numbers of molecules. That means that the gases are going into the reactor in the ratio of 1 molecule of sulphur dioxide to 1 of oxygen. That is an excess of oxygen relative to the proportions demanded by the equation.

According to Le Chatelier's Principle, Increasing the concentration of oxygen in the mixture causes the position of equilibrium to shift towards the _____________. Since the oxygen comes from the air, this is a very cheap way of increasing the conversion of sulphur dioxide into sulphur trioxide.

7 By increasing the proportion of oxygen you can increase the percentage of the sulphur dioxide converted, but at the same time decrease the total amount of sulphur trioxide made each day. The 1 : 1 mixture turns out to give you the best possible overall yield of sulphur trioxide.

The temperature 1.Equilibrium considerations You need to shift the position of the equilibrium as far as possible to the ________________ in order to produce the maximum possible amount of sulphur trioxide in the equilibrium mixture. The forward reaction (the production of sulphur trioxide) is exothermic.

According to Le Chatelier's Principle, this will be favoured if you lower the temperature. The system will respond by moving the position of equilibrium to counteract this - in other words by producing more heat. In order to get as much sulphur trioxide as possible in the equilibrium mixture, you need as low a temperature as possible. However, 400 - 450C isn't a low temperature!

2. Rate considerations The lower the temperature you use, the _________________ the reaction becomes. A manufacturer is trying to produce as much sulphur trioxide as possible per day. You need the gases to reach equilibrium within the very short time that they will be in contact with the catalyst in the reactor.

3. The compromise 400 - 450C is a compromise temperature producing a fairly high proportion of sulphur trioxide in the equilibrium mixture, but in a very short time.

The pressure 1. Equilibrium considerations

Notice that there are 3 molecules on the left-hand side of the equation, but only 2 on the right. According to Le Chatelier's Principle, if you increase the pressure the system will respond by favouring the reaction which produces _________________ molecules. That will cause the pressure to fall again. In order to get as much sulphur trioxide as possible in the equilibrium mixture, you need as high a pressure as possible. High pressures also increase the rate of the reaction. However, the reaction is done at pressures close to atmospheric pressure!

8 2. Economic considerations Even at these relatively low pressures, there is a 99.5% conversion of sulphur dioxide into sulphur trioxide. The very small improvement that you could achieve by increasing the pressure isn't worth the expense of producing those high pressures.

The catalyst 1. Equilibrium considerations The catalyst has _________ effect whatsoever on the position of the equilibrium. Adding a catalyst doesn't produce any greater percentage of sulphur trioxide in the equilibrium mixture. Its only function is to speed up the reaction. 2. Rate considerations In the absence of a catalyst the reaction is so slow that virtually no reaction happens in any sensible time. The catalyst ensures that the reaction is fast enough for a dynamic equilibrium to be set up within the very short time that the gases are actually in the reactor.

Sulphuric acid The list below is based on examples such as

Production of fertilisers such as ammonium sulphate. Lead-acid batteries (for example, car batteries). Metal pickling. This is treatment of a metal with a dilute acid (which may be sulphuric acid or hydrochloric acid, depending on the metal being treated). This removes any layers of oxide (or similar impurities) from the surface of the metal. Manufacture of detergents.

Sulphur dioxide Sulphur dioxide is used as a __________________ in, for example, wine and dried fruit and vegetables. It has two functions. It is a ___________________ agent and so slows oxidation of the wine or dried fruit by oxygen in the air. And it also kills bacteria.