12/02/2015 Pesticides

Pesticides

Crops must compete successfully for resources in order to survive and produce a

good yield.

If the competition is too fierce, the crop yield can be seriously affected; this can

cause huge problems for farmers, who depend upon the crop yield in order to maintain

a healthy income.

Pesticides can be used to alleviate some of the competition that may cause the

crop’s yield to decrease.

Herbicides kill other plants (weeds etc.) which may compete with the crop,

insecticides kill insects which eat the crop, and fungicides eradicate moulds which may

rot plants/seeds.

Pesticides are also used to control many disease carrying organisms, such as

mosquitoes, which are renowned for spreading the malarial parasite in the tropics.

The advantages of pesticides must be balanced with their disadvantages; many of

them are toxic and can be damaging to human health and the environment if they are

not used appropriately.

They may also kill other organisms other than those which they are intended to kill;

this can even be advantageous to the pest; the pesticide may eradicate the pest’s

natural predator.

Other problems include leaching (the pesticide dissolves into water and is

transported to the water supply, contaminating it) and assimilation through the food

chains (the pesticide in soil builds up through the food chains).

The perfect pesticide must be:

Specific to the target organism.

Kill at low dosages­ only small amounts need to be applied.

Unable to remain in the soil and travel into the water supply.

As with developing a new medicine (What’s in a Medicine), developing a new

pesticide can be an expensive and time consuming process.

Many highly active compounds have been developed which are effective at low

dosages; others have been designed which satisfy the smaller, specialised markets.

The process usually starts with the discovery of a new compound which works

effectively as a pesticide.

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Chemists will then systematically alter the structure of the compound and then test

it on various pests.

Hundreds of field trials will then be conducted on the substances chosen for

development.

The compound will be judged on its:

Ease of manufacture.

Persistence in soil and leaching losses in drainage water.

Cost and marketability.

Toxicity.

Comparison with other known compounds.

Patents, which may be owned by someone else.

DDT

Fat soluble molecules are usually the most effective pesticides; because they are

non­polar, they are able to dissolve in the fatty tissues of the pest and so reach the

sites of action rapidly.

However, their solubility in organic substances may cause them to accumulate and

become concentrated up the food chain; bio­accumulation.

DDT was discovered in Germany, 1939; it has prevented millions of deaths from

diseases such as Typhus and Malaria.

DDT is from the organochlorine insecticides.

It has several advantages, such as:

It is toxic to insects, but not to mammals. This is due to the presence of

specific enzymes in mammals (see below).

It is made in a one­stage synthesis from cheap raw material (low cost).

A specific enzyme found in mammals, catalyses the removal of HCl from DDT

forming the non­toxic product of DDE. DDT is a three­dimensionally shaped molecule

that fits into a specific receptor site, whereas DDE is a planar molecule that is unable

to fit into the receptor site:

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12/02/2015 Pesticides

Some insects have also developed the specific enzyme and are thus resistant to DDT.

DDT’s major disadvantage is that it is an extremely stable molecule and therefore

accumulates in the environment where they can remain for years.

It has been banned in many countries, but is still used in developing countries due

to its low cost.

Parathyroids

The flowers from plants such as chrysanthemums contain their

own pesticides; they have been used for centuries as natural

insecticides.

In the 1920’s and 1930’s, the structure of the natural

insecticides were worked out; for example, Pyrethrin 1:

Pyrethrins are ideal insecticides in that they are powerful and are harmless to

mammals under normal circumstances.

Unfortunately, the natural pyrethrins are unstable in light; they are of limited use in

agriculture due to their rapid breakdown.

However, we now have synthetic compounds related to pyrethrins; in 1977, Michael

Elliott synthesised permathrin, which was sufficiently stable to use in agriculture:

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Cypermathrin was then later developed from permathrin:

How they work

The pyrethroids work by binding to membrane proteins within the nerve cells of

insects.

Nerve cell membranes act as channels for the passage into and out of the cells; the

pyrethroids work by penetrating the nerve cell membrane, blocking open the sodium

channels; this leads to the massive disruption of the nervous system of insects.

Pyrethroids are much more soluble in fats than in water; they are therefore able to

rapidly reach the target cells within the insects.

The pyrethroids are harmless to mammals, as the ester linkage within them is

hydrolysed (by digestive enzymes) to polar products; these polar products are unable

to join to the protein membranes and so remain dissolved in aqueous solution.

Soil active pyrethroids

Even though the pyrethroids are able to kill certain insects which live in the soil, they

were found not to do so.

This was because the pyrethroids became irreversibly bounded to organic matter in

the soil, where it became rapidly broken down into inactive compounds.

Chemists at ICI developed pyrethroids with lower boiling points so that more of the

molecules would vaporise into the air spaces into the soil. The compound then enters

the pests via the air is respires.

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The new pyrethroids was named Tefluthrin and is currently marketed as “Force”:

Herbicides

As previously mentioned, herbicides increase the yield of a crop by destroying weeds

which may be competing with the crop for resources.

There are two different types of herbicide; total herbicides which destroy all green

material and selective herbicides which only destroy selected plant material.

Paraquat is total herbicide; it is inactive once it reaches the soil, as it is absorbed and

decomposed by soil material; therefore it only kills those plants whose leaves it comes

into contact with.

Each soil is only capable of holding a particular amount of paraquat; the strong

absorption capacity of the soil.

If a greater amount of paraquat is then added, it will be displaced into the soil water,

damaging growing plants.

Total herbicides are used to clear a large area of land before the crop is planted.

Selective herbicides are then used to kill the other plants that may be competing

with the desired crop.

Selective herbicides have been developed which only kill broad­leaved plants,

grasses, grassy weeds etc. The pesticide is selected to suit the type of crop being

grown.

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12/02/2015 Nitrogen Cycle

Nitrogen Cycle

Almost all of the nitrogen in the soil is present in complex organic molecules and so is not

available to plants.

However, various processes convert the unreactive atmospheric nitrogen and organic nitrogen

compounds into ammonium and nitrate ions which are available to plants.

The main processes are shown in the nitrogen cycle below:

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12/02/2015 Inorganic Fertilisers

Inorganic Fertilisers

Today, more than half of the world’s cereal production relies on inorganic fertilisers.

Without fertiliser it would be near impossible to feed the world’s population.

The raw materials used to produce inorganic fertilisers are water, air, natural gas,

phosphate rock, potash rock and sulphur.

There is a vast range of inorganic fertilisers; there are ammonium nitrate,

ammonium sulphate, ammonium phosphate, urea and potassium nitrate fertilisers.

At the core of fertiliser production is the synthesis of ammonia from nitrogen and

hydrogen in the Haber Process.

The Haber Process

In 1909, Fritz Haber successfully synthesised 100g of ammonia from nitrogen and

hydrogen.

Carl Bosch then scaled up his process and the first industrial plant opened in 1913,

producing thirty tonnes per day.

Modern ammonia plants work on the same principles as the original plants, but now

produce in excess of one thousand five hundred tonnes per day.

In the modern plants, the hydrogen is formed by reacting water with natural gas.

Purified nitrogen from the air is then mixed with the hydrogen; the mixture is

heated and passed over an iron catalyst forming ammonia:

3H2(g) + N2(g) 2NH3(g) H = ­92 kJ mol­1

The reaction is reversible; ammonia is being decomposed to form hydrogen and

nitrogen at the same time as it is being produced; the reaction will eventually reach

equilibrium.

The equilibrium mixture depends upon the temperature and pressure chosen for the

reaction.

As can be seen from the reaction above, four moles of gaseous reactants (hydrogen

and nitrogen) react to form two moles of gaseous product (ammonia). Using Le

Chatelier’s Principle, which states that “a system at equilibrium, when subjected to a

disturbance, responds in a way that tends to minimize the effect of the disturbance”,

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the maximum yield of ammonia can be obtained by subjecting the reaction to a high

pressure.

The forward direction of the reaction is exothermic, thus to obtain the maximum

yield, the temperature must be low.

However, high pressures are very expensive to achieve, and at low temperatures, the

rate of the reaction will be very slow. Therefore, those reaction conditions which give

the most economic production of ammonia are selected.

A temperature of between 400­600oC is selected; this is a compromise between the

yield and the rate of the reaction; it is better to get moderate yields of ammonia

rapidly than wait a long time for a higher yield.

A pressure of between 70­200 atm. is selected; to achieve greater pressures would

cost more money.

Ammonia, due to the hydrogen bonding that occurs between its molecules, has a

higher boiling point than nitrogen and hydrogen. Thus the ammonia can be liquefied

and tapped off from the mixture as it is produced; this results in a greater yield of

ammonia.

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12/02/2015 Reaction rates, temperature and catalysis

Reaction rates, temperature and catalysis

As learned in previous modules, the rate of a reaction is increased by using a catalyst

or increasing the temperature.

The effect of using a catalyst and increasing the temperature can be explained using

the collision theory.

The collision theory of reactions

The basic principle of the collision theory is that chemicals react when their particles

collide with a certain minimum energy.

Take the following reaction between nitrogen and hydrogen to produce ammonia:

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

The collision theory states that H 2 and N2 will react when they collide with enough

energy. The more frequently they collide, the faster the reaction.

If the pressure is increased, there will be more molecules of gas per unit volume;

this will mean that there will be a greater chance of a successful collision; therefore the

rate of the reaction is greater. This is one of the reasons why the Haber process uses

high pressures.

Increasing the temperature of the reaction gives the molecules more kinetic energy;

this means that they will be moving around faster and will therefore be more likely to

collide and successfully react. It is possible to calculate how much faster they move

around, for the speed of the molecules is proportional to the square root of the

temperature. So if the temperature of a reaction is increased 10K from 300K to 310K,

then the speed of the molecules will increase by a factor of ; however the

actual rate of the reaction doubles.

This is related to the other part of the collision theory, which states that the particles

must collide with a certain minimum energy (the activation energy).

Unless they collide with this minimum amount of energy, they simply bounce off one

another and remain unreacted: this happens to most of the molecules most of the

time: at 300K only 1 in 1011 collisions of H 2 and N2 is successful.

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The distribution of energies

At any given temperature, the kinetic energies of the molecules in a substance are

spread over a wide range of values; some will have very high kinetic energies and

others will have lower kinetic energies.

The distribution of kinetic energies can be shown in a Maxwell­Boltzmann

Distribution:

As the temperature increases, the molecules move at higher speeds and therefore

have higher kinetic energies.

The Maxwell­Boltzmann distribution below shows the effect of increasing the

temperature by 10 K:

There is still a spread of kinetic energies; however, at the greater temperature, a

greater proportion of the molecules have a higher energy.

The effect of temperature on the rate of the reaction can be seen if the activation

energy is added to the distribution:

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Only those molecules with energy greater than the activation energy are able to

react; this is represented by the areas beneath the graphs to the right of the activation

energy line.

As you can see, at the higher temperature, a greater proportion of the molecules

have energies above the activation energy; this means that more molecules will have

enough energy to react, so the reaction goes faster.

This can be summarised by saying that reactions go faster at higher

temperatures because a larger proportion of the molecules have the minimum

activation energy needed to react.

Increasing the temperature does not make much difference to the individual

molecule, but it does make a significant difference to the proportion of molecules with

enough energy to react.

Temperature and rate constants

The rate constant for a reaction is given by the expression:

rate = k [A]a[B]b

For many reactions, if the temperature of the reaction is increased by 10 K, the rate

of the reaction will roughly double.

Since the concentrations of the reactants are not changed, the equation above shows

that it must be the rate constant, k, that changes with temperature.

Catalysis

Catalysts work by providing an alternative reaction pathway for the breaking and

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remaking of bonds. The activation energy for this new pathway is often less than the

activation energy of the normal pathway.

There are two different kinds of catalyst: heterogeneous catalysts are in a different

state as the reactants, and homogenous catalysts are in the same state as the

reactants.

However the catalyst works, its effect is always the same. A catalyst lowers the

activation energy needed for a reaction to occur; the molecular energy distribution

remains the same, but as the activation energy is lower, a greater proportion of

molecules will be above that energy and will therefore be able to react successfully.

The heterogeneous catalyst in the Haber process is iron, it works as follows:

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This process increases the rate of the reaction, because:

Adhering to the catalyst surface uses electrons and so weakens the bonds in

the reactants; this lowers the activation energy.

There will be a greater concentration of reactants at the surface of the catalyst.

The orientation of the reactants is correct for the reaction.

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12/02/2015 Equilibria and Partial Pressures

Equilibria and Partial Pressures

The following reaction between hydrogen and iodine is reversible:

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

If it is left for long enough, it will eventually reach dynamic equilibrium; this is where

the forward and backward reactions are occurring at the same rate; therefore the

concentrations of the reagents do not change.

The equilibrium constant, Kc, is given by the following expression:

In the equilibrium mixture, it is assumed that each gas behaves independently of

the other gases present; the total pressure (P) of the mixture is therefore equal to the

sum of the partial pressures of the gases present:

Total Pressure P = PH2 + PI2 + PHI

The partial pressure of each gas is proportional to its concentration; it is therefore

possible to write an expression for the equilibrium constant in terms of partial

pressures of the gases:

Similarly, it is also possible to write an equilibrium an expression for the equilibrium

constant for the reaction between nitrogen and hydrogen to form ammonia:

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

It is much more convenient to write the expression for the equilibrium constant in

terms of the partial pressure of the gases.

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Units

Pressure can be measured in Newtons per square metre (N m­2); this can also be

referred to as pascals: 1 Pa = 1 N m­2.

However, atmospheres (atm) are generally the unit of pressure in equilibrium

expressions: 1 atm = 1.01 x 102 kPa.

Therefore the units for the equilibrium constant for the reaction between iodine and

hydrogen can be caluclated:

The units cancel out, so there are no units for the equilibrium constant for the

reaction between hydrogen and iodine.

The units for the nitrogen/hydrogen/ammonia equilibrium constant are:

As for Kc, the units for each Kp expression must be worked out.

Changing the Pressure

If the total pressure of a gas mixture at equilibrium is increased, then the reaction

will respond by reducing the pressure again (Le Chatelier’s principle).

The pressure exerted by a gas is dependent on the number of gas molecules

present; therefore the position of equilibrium will shift to the side with the fewest

number of gas molecules if the pressure is increased.

In the reaction between nitrogen and hydrogen to form ammonia, there are four

molecules of gas on the reactant side for every two molecules of gas on the product

side:

1N2(g) + 3H2(g) 2NH3(g)

Therefore, if the pressure is increased, the position of equilibrium will shift to the

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12/02/2015 Equilibria and Partial Pressures

right to oppose the change made to the conditions of the reaction.

For example, at 1 atm total pressure, the equilibrium % of ammonia is equal to

24%. From this the equilibrium constant can be determined:

The nitrogen and hydrogen react according to a 1:3 ratio, therefore the 99.76% is split

into a 1:3 ratio:

Converting these to partial pressures:

PN2 = 0.2494 * 1

PH2 = 0.7482 * 1

PN2 = 0.0024 * 1

Substituting these into the equilibrium expression gives:

The graph below shows the percentage of ammonia at equilibrium at different

pressures:

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12/02/2015 Equilibria and Partial Pressures

As the pressure increases, the percentage of ammonia at equilibrium also increases;

this is why high pressures are used in the Haber process.

The Kp is constant for each reaction providing the temperature does not change.

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12/02/2015 Partition Equilibria

Partition Equilibria

In addition to phase equilibria (between gaseous and liquid state), and chemical

equilibria, there is also an equilibrium that exists between solutes in different solvents.

Iodine is a Group VII liquid that dissolves in both inorganic and organic solvents,

such as potassium iodide and tetrachloromethane.

When iodine is dissolved in potassium iodide, the solution is brown in colour:

If this solution is then added to a separating funnel with CCl4, the iodine passes

between the two liquids until an equilibrium is established:

The layers could be run into separate containers and the concentration of iodine in

each solvent determined:

This can be written as an equilibrium constant:

The value for the equilibrium constant comes out at around 84. This particular kind

of equilibrium constant measures how a substance distributes (partitions) itself

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12/02/2015 Partition Equilibria

between two solvents. It is called a partition coefficient Kow.

The partition coefficient in the above example is determined by the fact that iodine is

a non­polar substance and therefore prefers to be dissolved in an organic substance.

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12/02/2015 Group V and Nitrogen

Group V and Nitrogen

Group V of the periodic table shares similar characteristics of the other groups of the

p­block; at the top of the groups are the non­metals (nitrogen and phosphorus) and at

the bottom of the group are the metalloids (antimony and bismuth).

Atoms of the Group V elements can form three covalent bonds by sharing the three

unpaired p­electrons.

This gives them compounds in which the Group V element has an oxidation state of

+3 or ­3.

The lone pair of electrons that each element has allows them to form dative bonds.

This enables them to form compounds in which their oxidation state is five.

Nitrogen and phosphorous are very important elements within group five; they are

constituent elements in living things; they are both essential for healthy plant growth.

Nitrogen

Nitrogen is the most abundant gas in our atmosphere; however it is extremely

unreactive.

This low reactivity arises due to the strong triple bond between nitrogen atoms in N2

molecules.

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12/02/2015 Group V and Nitrogen

In order for nitrogen to react, the triple bond between the nitrogen atoms must be

broken, or partially broken.

This requires large amounts of energy, thus the activation energy for reactions

involving nitrogen is very high.

During thunderstorms, the highly energetic lightening flash can provide enough

energy to form nitrogen oxides from atmospheric oxygen and nitrogen.

Once reacted, it can form many useful compounds, for example ammonia, nitrogen

oxides and nitrates.

Ammonia

Ammonia is an example of a nitrogen hydride.

The lone pair of electrons on the ammonia allows it to acts as a nucleophile (donating

a pair of electrons to a positively charged carbon atom), as a base (forming a dative

bond with an H + ion) and as a ligand.

Nitrogen Oxides

Nitrogen forms many different oxides, all of which are gaseous.

Some of the more important ones are:

Nitrogen monoxide (NO), a colourless gas which turns to brown NO2 in air. It is

produced in combustion processes, especially from internal combustion engines.

It is also formed in thunderstorms, and in the soil by denitrifying bacteria.

Nitrogen dioxide (NO2) is a brown gas; it is toxic and is also formed in

combustion processes and thunderstorms.

Dinitrogen oxide (N2O) is a colourless gas formed in the soil by denitrifying

bacteria.

Nitrates

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There are two types of nitrate ions in the nitrogen cycle: nitrate (III), NO2­, and

nitrate (V), NO3­.

Their names are distinguishable from one another by their oxidation states.

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12/02/2015 Bonding, Structure and Properties

Bonding, Structure and Properties

The bonding and structure of substances determine their properties.

Bonding is the way the atoms are held together.

The structure is the way the atoms are arranged relative to each other.

There are two major types of structure: giant and molecular.

Giant structures go on indefinitely, whereas molecular structures are made up of groups of

atoms.

Three main factors are important in deciding the properties of a substance:

1. The type of basic particles it contains. The substance could contain atoms, ions or

molecules. For example, if it contains ions (such as sodium chloride), then it will conduct

electricity when molten or dissolved in water. To be soluble in water, the substance must

contain either ions or polar molecules.

2. The way the basic particles are bonded together. The bonding may be ionic,

covalent, metallic or weak intermolecular forces. The stronger the bonds, the higher the

melting/boiling point and the hardness of the substance.

For example, silica, SiO2, has strong covalent bonds linking every atom to several others

forming a giant covalent structure. The atoms in silica are very hard to separate, and

therefore it is very hard and difficult to melt. Carbon dioxide on the other hand has strong

covalent bonds between the C and O atoms, but only weak intermolecular forces between

each CO2 molecule. The molecules are therefore easily separated and so CO2 has a low

melting/boiling point.

3. The way the particles are arranged relative to one another. The particles may be

arranged in 1­dimensional plains (such as in polymers), 2­dimensional sheets (like clays) or

in many different kind of 3­dimensional arrangements. Graphite is arranged in 2­

dimesnional sheets, and so its layers can move past each other (think of writing using a

graphite pencil). Diamond, on the other hand, has a giant 3­dimensional structure and is

the hardest natural substance.

The tables below summarises the different structures and their main properties:

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Structure and the periodic table

There is a trend in the structure of the elements as you move from left to right across a period

of the periodic table.

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The trends in the structures of the oxides and chlorides are closely linked to the trends in their

properties; for example the acid­base character of the oxides and the behaviour of the chlorides

in water.

Acid­base properties of oxides

It is evident from the following table, that the acid­base properties of the oxides are linked

with the structures of the oxides (previous table).

The general pattern is that oxides with giant ionic lattices are basic, whereas structures with

covalent structures are acidic.

The bonding in Al2O3 is both ionic and covalent in nature; aluminium oxide is thus amphoteric.

Behaviour of the chlorides in water

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12/02/2015 Bonding, Structure and Properties

The behaviour of the chlorides with water is also closely linked to their structure. The general

pattern is for chlorides with giant ionic lattices to simply dissolve in water (no chemical reaction),

whereas the chlorides with covalent molecular structures react, producing fumes of hydrogen

chloride and forming acidic solutions.

The covalent chlorides are hydrolysed in water:

AlCl3(s) + 3H2O(l) Al(OH)3(aq) + 3HCl(g)

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