Extraction of Metals

A solid element or compound which occurs naturally in the Earth's crust is called a
mineral. A mineral which contains a high enough percentage of a metal for economic
extraction is called a metal ore. Economic extraction means that the cost of getting the
metal out of the ore is sufficiently less than the amount of money made by selling the
metal.

The most common metal ores are oxides and sulfides. Sulfides are the oldest ores,
formed in the Earth's history when there was a lot of sulfur from volcanic activity. Oxides
formed later when photosynthesis in plants released large amounts of oxygen into the
atmosphere.

Metal ore deposits are a finite resource (there are only a certain amount of them) and non-
renewable (once used, they are gone and will not be replaced).

Many metals are obtained today from recycling (melting and refining) scrap metals.
About half of the aluminium, copper, lead, steel and tin which are used in the UK come
from recycled scrap metal.

A metal above carbon in the reactivity series may be extracted from its ore by
electrolysis.

A metal below carbon in the reactivity series (zinc to silver) may be extracted from its ore
by heating with carbon. The metal is displaced from its non-metal anion by the more
reactive carbon. Carbon is used because it is readily available and cheap (coke or
charcoal are both carbon). The metal in the ore is said to be reduced by reaction with
carbon.

Hydrogen may be used to reduce metals which are lower than itself in the reactivity
series, but since it is more expensive than carbon it is only used on a large scale for the
extraction of tungsten, to avoid the formation of tungsten carbide.

Gold and platinum occur in the Earth as native metal, which means that they are found as
the element, not the compound, and so do not need to be reduced. Silver and copper may
also be found as native metal.

History.

Metals have been used by people for many thousands of years. Gold and silver, found as
native metal, were used both as jewellery and as a status symbol - nothing new there.
These metals were known in the Stone Age but gold and silver are too soft to be used as
tools.

The first really useful metal to be discovered was bronze - the Bronze Age. Bronze was
used extensively for tools and weapons in Asia and Africa from 4,500 B.C. (6,500 years
ago) and in Britain from 2,000 B.C. (4,000 years ago). News of the new material traveled
slowly in those days (no internet) and it took the Brits 2,500 years to get the message.

Bronze is not an element (like gold and silver) but an alloy (metal mixture) of copper and
tin. Ores of both copper and tin are easily reduced by heating with carbon. This would
have occurred accidentally as people lit wood fires in places where mixtures of tin ore
and copper ore existed. The hot burnt wood (carbon) would have reduced the ores to a
mixture of copper and tin metal, which is bronze

After the Bronze Age came the Iron Age. People discovered that a high temperature coal
fire could be used for the extraction of iron from iron ore. The extraction of iron today is
done in a blast furnace.

The Iron Age began in Asia and Africa in 1,100 B.C. and came to Britain in 500 B.C. In
many ways, we are still in the Iron Age - take a look around.

Metals above carbon in the reactivity series can only be extracted by electrolysis. The
discovery of electricity at the beginning of the nineteenth century allowed the extraction
of the more reactive metals. Aluminium has been extracted on a large scale since about
1870, 3,000 years after the discovery of iron and over 6,000 years after the discovery of
bronze.

For common metals in general, the more reactive a metal is, the harder it is to extract, and
the later it was discovered.

Extraction of Aluminium.

Aluminium ore is called bauxite. Bauxite contains aluminium oxide, water, iron oxide
and other impurities. The purified dry ore, called alumina, is aluminium oxide - Al2O3.

The alumina must be molten for electrolysis to work, since the ions are not free to move
in the solid state. Unfortunately, alumina has a high melting point (2040 °C) and it is not
practical to do electrolysis at such a high temperature.

In the middle of the nineteenth century it was found that alumina dissolved in cryolite.
Cryolite is sodium aluminium fluoride - Na 3AlF6. A solution of alumina in cryolite melts
at about 900 °C and electrolysis is done at about 950 °C.
The steel container is coated with carbon (graphite) and this is used as the negative
electrode (cathode).

Aluminium oxide (Al2O3) is an ionic compound. When it is melted the Al3+ and O2- ions
are free to move and conduct electricity. Electrolysis of the alumina/cryolite solution
gives aluminium at the cathode and oxygen at the anode.

4Al3+ + 12e- → 4Al (aluminium metal at the (-)cathode) reduction.

6O2- - 12e- 3O2 (oxygen gas at the (+)anode) oxidation.

Aluminium is more dense than the alumina/cryolite solution and so it falls to the bottom
of the cell where it can be tapped off as pure liquid metal.

The overall reaction is

aluminium oxide →aluminium + oxygen.

2Al2O3(l) → 4Al(l) + 3O2(g)

Oxygen is given off at the positive carbon anode. Carbon dioxide is also given off at the
carbon anode because hot oxygen reacts with the carbon anode to form carbon dioxide
gas.

carbon + oxygen → carbon dioxide.

C(s) + O2(g) → CO2(g)

The carbon anodes slowly disappear because each molecule of carbon dioxide which is
given off takes a little piece of carbon away with it. The carbon anodes need to be
replaced when they become too small.

Aluminium - Cost and Recycling.

Aluminium is the third most abundant element in the Earth's crust after oxygen and
silicon. It is the most abundant metal but it is more expensive to produce than iron
because of the cost of the large amounts of electricity which are needed for electrolysis -
About half of the aluminium used in the UK is recycled.

Extracting aluminium from recycled scrap requires only about 5% of the energy needed
to extract aluminium from its ore. Collecting scrap metal and transport to the metal
extraction plant add extra costs.

Aluminium - Resistance to Corrosion.

Corrosion is the name given to the process where a metal reacts with oxygen in the air to
form a metal oxide. Corrosion is the reverse of the process used to extract the metal. If
the metal is iron, corrosion is called rusting. In general, the more reactive a metal is the
more quickly it will corrode.

Aluminium is a reactive metal. It is above carbon in the reactivity series but is resistant to
corrosion because aluminium reacts with oxygen in the air and forms a thin layer of
aluminium oxide (Al2O3). The oxide layer covers the surface of the aluminium metal and
prevents any further reaction (corrosion) from happening. The thickness of the oxide
layer can be increased by anodising.

The oxide layer will react with an acid or alkali to form an aluminium salt + water. The
exposed aluminium metal will then itself react with acid or alkali to form the aluminium
salt + hydrogen. It is therefore best to avoid contact of aluminium cookware with citrus
fruits or vinegar (acids), or alkali cleaners such as caustic soda (sodium hydroxide).

Aluminium in food is a health hazard and has been associated with Alzheimer's disease.

Aluminium - Anodising.

The thickness of the oxide layer on the surface of aluminium metal can be increased by a
process called anodising. This gives the aluminium extra corrosion resistance.

The aluminium metal is first treated with sodium hydroxide solution which removes the
thin oxide layer on the surface. The clean aluminium metal is then used as the anode for
the electrolysis of dilute sulfuric acid. Oxygen gas which is given off at the anode reacts
with the surface of the aluminium and forms a thick oxide layer.

The half equation at the anode is

2Al(s) + 6OH-(aq) - 6e- → Al2O3(s) + 3H2O(l)

Hydrogen gas is given off at the cathode. The half equation at the cathode is

6H+(aq) + 6e- → 3H2(g)

Properties and Uses of Aluminium.

Properties.

Aluminium

1) is strong, malleable and has a low density.

2) is resistant to corrosion.

3) is a good conductor of heat and electricity.

4) can be polished to give a highly reflective surface.

Uses.

1) Low density and strength make it ideal for construction of aircraft, lightweight
vehicles, and ladders. An alloy of aluminium called duralumin is often used instead of
pure aluminium because of its improved properties.

2) Easy shaping and corrosion resistance make it a good material for drink cans and
roofing materials.

3) Corrosion resistance and low density leads to its use for greenhouses and window
frames.

4) Good conduction of heat leads to its use for boilers, cookers and cookware.

5) Good conduction of electricity leads to its use for overhead power cables hung from
pylons (low density gives it an advantage over copper).

6) High reflectivity makes it ideal for mirrors, reflectors and heat resistant clothing for
fire fighting.

Extraction of Iron.

Iron is extracted from its ore in the blast furnace.

The main iron ore is called haematite. Haematite is iron(III) oxide - Fe 2O3. The iron ore
contains impurities, mainly silica (silicon dioxide). Limestone (calcium carbonate) is
added to the iron ore which reacts with the silica to form molten calcium silicate in the
blast furnace. The calcium silicate (called slag) floats on the liquid iron.

Since iron is below carbon in the reactivity series, iron in the ore is reduced to iron metal
by heating with carbon (coke). It is actually carbon monoxide which does the reducing in
the blast furnace.
Extraction of Iron.

Chemistry of the blast furnace.

Hot air is blasted into the furnace causing coke (carbon) to burn rapidly and raise the
temperature to 2000 °C.

carbon + oxygen → carbon dioxide + heat.

C(s) + O2(g) → CO2(g)

The carbon dioxide then reacts with hot carbon to form carbon monoxide.

carbon dioxide + carbon → carbon monoxide.

CO2(g) + C(s) → 2CO(g)

Carbon monoxide then reduces iron in the ore to iron metal.

carbon monoxide + iron(III) oxide→ carbon dioxide + iron.

3CO(g) + Fe2O3(s) → 3CO2(g) + 2Fe(l)

The temperature where the reduction takes place is above 1500 °C.

Iron falls to the bottom of the furnace where the temperature is 2000 °C.

Iron is liquid at this temperature and is tapped off periodically.

Limestone is calcium carbonate (CaCO3) and it is added to the blast furnace to remove
the impurities in the iron ore. Calcium carbonate is decomposed by heat in the furnace to
give calcium oxide (quicklime) and carbon dioxide. This is called thermal decomposition

calcium carbonate →calcium oxide + carbon dioxide.

CaCO3(s) → CaO(s) + CO2(g)

The main impurity is silica (sand or rock) which is silicon dioxide. Silicon dioxide is
solid at the furnace temperature and the furnace would become blocked if it was not
removed. Silicon dioxide reacts with calcium oxide to form calcium silicate (called slag)
which is liquid in the furnace. Slag flows to the bottom of the furnace where it floats on
the liquid iron and is easily removed.

calcium oxide + silicon dioxide →calcium silicate.

CaO(s) + SiO2(s) → CaSiO3(l)

The slag (CaSiO3) is allowed to cool until it becomes a solid and is used for road
construction.

Manufacture of Iron.

Iron from the blast furnace contains about 5% carbon which comes from the coke in the
furnace. It is cast into moulds called pigs and the iron is called cast iron or pig iron.

Molten scrap iron and molten scrap steel are mixed with molten iron from the blast
furnace in a converter. This is the stage when scrap iron and steel are recycled. Carbon is
removed from the mixture by bubbling pure oxygen through it. The oxygen reacts with
the carbon to form carbon dioxide. Other non-metals in the mixture react with the oxygen
to form acidic oxides. Calcium carbonate is then added to remove the acidic oxides.
These reactions produce pure iron which is called wrought iron.

The large majority of iron from the blast furnace is made into steel for construction, steel
contains 0·1% to 1·5% carbon - see alloys.

Properties and Uses of Iron.

Iron is one of the three magnetic elements (the others are cobalt and nickel).

Cast iron is very brittle (it cracks easily) but it has a greater resistance to corrosion (see
rusting) than either pure iron or steel. Cast iron is used for manhole covers on roads and
pavements and as engine blocks for petrol and diesel engines.
Pure iron is called wrought iron. Wrought iron is malleable and is mainly used in
ornamental work for gates. Iron is also the catalyst in the Haber Process. The large
majority of iron from the blast furnace is made into steel.

Extraction of Copper.

Copper is sometimes found as native metal.

Copper ores include copper(II) oxide and copper(II) sulfide. Copper(II) oxide can be
reduced by reaction with carbon. Some copper ores may contain only small amounts of
copper.
These are called low grade ores and have less than 1% copper but they are still used
because copper is so valuable. Bioleaching and phytomining are increasingly used
to extract copper from low grade ores (see below).

The traditional method of extraction is to heat the copper sulfide. Copper(II) sulfide gives
copper and sulfur dioxide during thermal decomposition. Thermal decomposition means
that the compound breaks down into other substances when it is heated. Thermal
decomposition is an endothermic reaction.

copper(II) sulfide → copper + sulfur dioxide

CuS(s) → Cu(s) + SO2(g)

The impure copper which results is called blister copper. The disadvantage of this method
is that it uses a lot of energy. If sulfur dioxide escapes into the atmosphere it causes
pollution. The advantage is that it is fast.

Bioleaching.

Some bacteria can live by using the energy of the bond between sulfur and copper. This
separates the metal from the ore and is called bioleaching. It has the advantage that it is
very energy efficient typically using only 30% to 50 % of the traditional method.
It has the disadvantage that it is very slow.

Phytomining.

Some plants absorb metal compounds (including copper) when they grow. The plants can
then be burned and the metal is extracted from the ash. The process is called phytomining
and it can also be used to extract metals from contaminated land. Brassicas (the cabbage
family) can extract metals including cadmium, cobalt and nickel.

Copper can also be extracted by displacement from a copper salt solution using scrap
iron.
Pure copper (99·99%) is needed for good electrical conductivity. Pure copper is obtained
by electrolysis.

About half of the copper used each year in the UK is recycled.

Extraction of Copper - Purification.

When electricity is passed through the cell copper is dissolved at the anode by oxidation,
Cu2+ ions go into solution.

Cu(s) - 2e- → Cu2+(aq)

At the cathode, copper is deposited by reduction.

Cu2+(aq) + 2e- → Cu(s)

As copper ions move from the anode to the cathode the anode gets smaller as the cathode
gets bigger. This is a redox reaction.

The rate at which the copper ions enter the electrolyte from the anode is the same as the
rate at which the copper ions leave the electrolyte at the cathode. The concentration of the
copper(II) sulfate solution therefore remains unchanged

As copper is transferred from the anode to the cathode any soluble impurities in the
copper anode dissolve in the copper(II) sulfate and are removed later.

Insoluble impurities fall to the bottom of the cell and form a sludge. The sludge often
contains precious metals (silver and platinum) which are extracted and refined.
Properties and Uses of Copper.

Properties

1) Copper is an excellent conductor of electricity and heat.

2) Copper is soft, easily bent and shaped (malleable).

3) Copper is resistant to corrosion (very unreactive).

Uses

1) Copper is the main metal for electrical wiring (compare with aluminium).

2) Copper is malleable which makes it an ideal material for gas pipes and water pipes.
Copper is below hydrogen in the reactivity series and therefore it does not react with
water. Copper is the metal used for plumbing in houses. Lead was used for plumbing in
the past but has been replaced by copper because lead compounds in water are toxic. This
is an example of a new material replacing an older one because of the new material's
superior properties.

3) Copper is sometimes used for cookware (not common).

4) Copper is mixed with other metals to form alloys. Copper is mixed with zinc to make
brass and with tin to make bronze.

Extraction of Titanium.

The extraction of titanium uses the Kroll process. Titanium ore is called rutile. Rutile
contains titanium dioxide - TiO2. Titanium dioxide is converted into titanium chloride -
TiCl4.

Titanium is more reactive than carbon but it is not extracted by electrolysis because
titanium chloride is covalent and therefore does not conduct electricity. Titanium chloride
is a yellow liquid (melting point is -24 °C). It is unusual for a metal to form covalent
bonds.

Magnesium or sodium are used to reduce titanium chloride to titanium metal. This is an
example of a metal displacement reaction. The reaction is carried out in an argon
atmosphere to prevent magnesium or sodium from reacting with oxygen in the air.

magnesium + titanium chloride magnesium chloride + titanium.

2Mg(l) + TiCl4(l) → 2MgCl2(l) + Ti(s)

sodium + titanium chloride→sodium chloride + titanium.

4Na(l) + TiCl4(l) → 4NaCl(l) + Ti(s)

Magnesium and sodium, both expensive metals, are used up in the production of
titanium. Titanium is therefore more expensive than either magnesium or sodium and has
limited specialised uses.

Often an alloy is composed mainly of one metal (the parent metal) with small amounts of
other metals added. The other metals replace positions of the parent metal in the metal
structure, or sometimes fit into the spaces in the metal structure.

The red balls are the parent metal. The blue and yellow balls are other metals. The blue
lines represent free electrons. Compare this with the metal structure of a pure metal.

The other metals in the structure can change the properties of the alloy by preventing the
metal ions from sliding over each other. This can make the alloy tougher and stronger
than the parent metal.

Alloys - containing Aluminium.

The main alloy of aluminium is duralumin. Aluminium is also a constituent of titanium

alloys.

Duralumin is an alloy of aluminium (94%), copper (4%) and magnesium (1%). Small
quantities of manganese and silicon may also be present.Duralumin is a low density
alloy. It has a higher strength to weight ratio than pure aluminium. Duralumin is used for
aircraft construction. Aluminium can also be used to make smart alloys.

Alloys - containing Copper.

Copper alloys include brass, bronze, cupro-nickel and duralumin. Brass is an alloy of
copper (70%) and zinc (30%). Brass is harder and cheaper than copper and is used for
musical instruments, corrosion resistant screws, fixtures and ornamental objects.
Bronze is an alloy of copper (90%) and tin (10%). Bronze is hard, strong and corrosion
resistant. Bronze is used for castings (statues) and bearings.

Cupro-nickel is an alloy of copper (70 to 80%) and nickel (20 to 30%). Cupro-nickel is
easily shaped, resistant to corrosion and is used to make "silver" coins such as the 5, 10,
20 and 50p piece. "Silver" coins have not contained real silver since 1947.

Copper can also be used to make gold alloys and smart alloys. For duralumin see
aluminium alloys.

Alloys - containing Iron

The alloys of iron are steel, manganese steel, stainless steel and titanium steel.

Steel is a mixture of iron and carbon. The amount of carbon may range from 0·1% to
1·5% giving steels of different properties. The exact composition of the steel can be
monitored by atomic emission spectroscopy during production. Over half of the steel
used each year in the UK is recycled.

Low carbon steel (less than 0·25% carbon) is called mild steel. Mild steel is cheap, strong
and easily shaped. It is the main metal for construction and is used to make bridges,
buildings, ships and vehicles.

High carbon steel (more than 0·5% carbon) is stronger than mild steel but it is more
brittle. High carbon steel is used to make tools and cutters.

Steel has the disadvantage of needing a protective coating (for example paint) or it will
react with oxygen in the air and rust. Rusting is the reverse of the process in the blast
furnace - see rusting.

Manganese steel is an alloy of iron (84%), manganese (15%) and carbon (1%).
Manganese steel is extremely hard and is used for railway points and dredging
equipment.

Stainless steel is an alloy of iron (80%), chromium (15%), nickel (4%) and carbon (0·5 to
1%). Stainless steel is strong and hard, with a very high resistance to corrosion (due to
chromium). It is used for cookware, cutlery and industrial chemical plant.

Titanium steel may contain 0·5 to 2% titanium with varying amounts of other metals
including chromium, nickel and vanadium. Titanium steel is very hard and finds uses in
aircraft and armour plating.

Corrosion (rusting) of Iron and Steel.

Iron exposed to moist air will react with oxygen in the air to form iron oxide. This
oxidation process is called rusting.
iron + oxygen → iron(III) oxide.

4Fe(s) + 3O2(g) → 2Fe2O3(s)

Rusting requires both oxygen and water. Salt or acid will accelerate rusting.

Rusting may be prevented by:

1) coating the surface to prevent contact with air.

2) sacrificial protection of a more reactive metal.

Iron and steel are most commonly protected by painting (bridges, buildings, vehicles),
plastic coating (household equipment) and metal plating. Zinc plating is called
galvanizing (this is also sacrificial protection). Chromium plating is used for wheels and
(formerly) bumpers to give a highly polished protective surface.

The metal plating process (also called electroplating) uses electrolysis of a solution
containing ions of the plating metal. The anode is made from the pure plating metal. The
metal object which needs plating is used as the cathode.

Most metals can be plated. Common plating metals are gold, nickel and silver as well as
chromium and zinc referred to above.

Silver plating could be done in the cell below.

When electricity is passed through the cell silver is dissolved at the anode by oxidation.
Ag+ ions go into the silver nitrate solution.

Ag(s) - e-→ Ag+(aq)

Silver is deposited onto the surface of the object by reduction at the cathode.

Ag+(aq) + e- → Ag(s)
As silver ions move from the anode to the cathode the anode gets smaller as the object
becomes silver plated. This is a redox reaction.

The rate at which the silver ions enter the electrolyte from the anode is the same as the
rate at which the silver ions leave the electrolyte at the cathode. The concentration of the
silver nitrate solution therefore remains unchanged.

Corrosion (rusting) of Iron and Steel - Sacrificial Protection.

Sacrificial protection is used for ships, under water pipelines and oil rigs (for example in
the North Sea).

Blocks of a more reactive metal (for example magnesium or zinc) are attached to the
ship's hull or the under water pipe. The magnesium or zinc can also be connected to a
pipeline or oil rig by conducting cables.

Sacrificial protection is similar to a displacement reaction with the electrons traveling

from the more reactive metal to the steel either directly or through the conducting cable.
This reverses the oxidation process.

3Zn(s) → 3Zn2+(aq) + 6e- Zinc is oxidised as it dissolves.

2Fe3+(s) + 6e- → 2Fe(s)

Iron ions are reduced to iron atoms. Rusty steel is returned to iron metal.

The block of zinc or magnesium is sacrificed to keep the steel from rusting and must be
replaced before it all dissolves. This is less expensive than rebuilding the ship or
replacing the pipe or oil rig.

Alloys - containing Lead.

The main alloy of lead is solder. Solder is an alloy of lead (70%) and tin (30%).

Solder is a low melting point alloy and is stronger than lead or tin.

Solder is used for connections in electrical wiring and in plumbing.

Over half of the lead and tin used each year in the UK are recycled.

Alloys - containing Titanium.

Titanium is mixed with aluminium (5%), and vanadium (5%). Chromium and
molybdenum might also be present.
Titanium is expensive, and is only used where its special properties of low density,
hardness and resistance to corrosion can not be reproduced by cheaper materials.

Titanium alloys are used in special parts of aircraft and ship construction, nuclear
reactors, chemical plant and hip joint replacements. Titanium is being increasingly used
in smart alloys.

Titanium can be used in small amounts in steel.

Alloys - containing Gold.

Pure gold is very soft. Gold is mixed with silver and copper in different amounts to make
an alloy which is harder and stronger.

The percentage of gold in an alloy is measured in carats or fineness. 100% pure gold is 24
carats, 75% gold is 18 carats 50% gold is 12 carats and 37.5% gold is 9 carats. The
available percentage of gold in jewellery is different in different countries. In the UK you
can get 22 carat, 18 carat,14 carat and 9 carat gold jewellery but not 12 carat gold
jewellery.

Fineness is the amount of gold in parts per thousand so 100% pure gold has a fineness of
1000 75% gold has a fineness of 750 50% gold has a fineness of 500 and 37.5% gold has
a fineness of 375.

Rates of reaction

Collision theory says that a chemical reaction can only occur between particles when they
collide (hit each other). Particles may be atoms, ions or molecules.

There is a minimum amount of energy which colliding particles need in order to react
with each other. If the colliding particles have less than this minimum energy then they
just bounce off each other and no reaction occurs. This minimum energy is called the
activation energy.

The faster the particles are going, the more energy they have. Fast moving particles are
more likely to react when they collide. You can make particles move more quickly by
heating them up (raising the temperature).

Changing the Rate of a Reaction.

There are 5 ways to increase the rate of a chemical reaction. They are all understood in
terms of collision theory.

The rate of a chemical reaction may be increased by:

1) Raising the temperature.

 2) Increasing the concentration (in solution).

3) Increasing the pressure (in gases).

4) Increasing the surface area of a solid.

5) Use a catalyst.

The opposite of 1, 2, 3 and 4 will decrease the rate of a reaction. A catalyst (strictly
speaking) will change the rate of a reaction. A catalyst can make a reaction go faster or
slower. In practice a catalyst is mainly used to make a reaction go faster.

Measuring the Rate.

The rate of a reaction may be measured by following the loss of a reactant, or the
formation of a product.

Three of the reactions which may be studied to show how the rate can be changed are
shown below.

They are:

1) The reaction between calcium carbonate and dilute hydrochloric acid.

2) The reaction between sodium thiosulfate solution and hydrochloric acid.

3) The decomposition of hydrogen peroxide solution.

Measuring the rate of reaction.

1) The reaction between calcium carbonate and dilute hydrochloric acid.

HCl + calcium carbonate→calcium chloride + carbon dioxide + water.

HCl(aq) + CaCO3(s) → CaCl2(aq) + CO2(g) + H2O(l)

The rate of this reaction can be measured by following the rate at which carbon dioxide is
formed.

This can be done by conducting the reaction in an open flask on an electric balance
(weighing machine). As the carbon dioxide escapes to the air, the mass of the flask will
decrease. You can take a reading from the balance every 30 seconds, then plot a graph of
loss of mass against time.

The gradient of the plot (the steepness of the slope) shows the rate of the reaction (how
fast it is going).
 Measuring the Rate.

2) The reaction between sodium thiosulfate solution and dilute hydrochloric acid.

HCl + sodium thiosulfate→sodium chloride + sulfur dioxide + sulfur + water.

HCl(aq) + Na2S2O3(aq) → NaCl(aq) + SO2(g) + S(s) + H2O(l)

The solid sulfur (S(s)) formed in this reaction makes the colourless solution go cloudy.

The reaction is usually carried out in a flask placed on a piece of white paper which has a
black cross on it. At the beginning of the reaction, the cross can be seen easily. As the
flask becomes more and more cloudy the cross gets harder to see.

You can measure the time from the start of the reaction until the cross can no longer be
seen. This is a way of measuring the rate of formation of sulfur.

The reaction between magnesium and dilute acid can be followed in a similar way noting
the time taken for the magnesium to disappear.

Measuring the Rate.

3) The decomposition of hydrogen peroxide solution.

hydrogen peroxide → oxygen + water.

2H2O2(aq) → O2(g) + 2H2O(l)

The reaction is carried out in a closed flask which has a gas syringe connected to the top
of it.

The reaction is started by adding a catalyst to the hydrogen peroxide. The catalyst is
manganese (IV) oxide.

The volume of oxygen in the syringe increases as the reaction proceeds. The volume of
oxygen can be noted every 30 seconds, and a graph of volume against time can be
plotted. The gradient of the plot (the steepness of the slope) shows how fast the reaction
is going.

Raising the Temperature.

Raising the temperature has the same effect on all three reactions.
Raising the temperature makes the particles move faster. This means that the particles
collide more frequently with each other and the rate of the reaction increases.

Also, the faster the particles are traveling, the greater is the proportion of them which will
have the required activation energy for the reaction to occur.

As a general guide, raising the temperature of a reaction by 10 °C will double the rate of
a reaction. The gradient of the plot will be twice as steep.

Increasing the Concentration (in solution).

Increasing the concentration of a substance in solution means that there will be more
particles per dm3 of that substance.

The more particles that there are in the same volume the closer to each other the particles
will be. This means that the particles collide more frequently with each other and the rate
of the reaction increases.

In the reaction between sodium thiosulfate solution and dilute hydrochloric acid:

HCl + sodium thiosulfate → sodium chloride + sulfur dioxide + sulfur + water.

HCl(aq) + Na2S2O3(aq) → NaCl(aq) + SO2(g) + S(s) + H2O(l)

Solid sulfur (S(s)) is formed in the flask. Increasing the concentration of sodium
thiosulfate means that the solid sulfur will be produced more quickly and there will be
less time before the cross can no longer be seen

When making different concentrations of sodium thiosulfate take care to use the same
total volume of sodium thiosulfate plus hydrochloric acid for the comparison to be fair.

Increasing the Pressure (in gases).

Increasing the pressure of a reaction where the reactant is a gas is similar to increasing
the concentration of a reactant in a solution. The gas particles (usually molecules) will be
closer together when the pressure increases. This means that the particles collide more
frequently with each other and the rate of the reaction increases.

If the reaction is reversible, then increasing the pressure will favour the side of the
reaction which has the smaller volume (see the Haber process).

Increasing the Surface Area of a Solid.

A solid in a solution can only react when particles collide with the surface. The bigger the
area of the solid surface, the more particles can collide with it per second, and the faster
the reaction rate is.

You can increase the surface area of a solid by breaking it up into smaller pieces. A
powder has the largest surface area and will have the fastest reaction rate. This is why
catalysts are often used as powders.

In the reaction between calcium carbonate and dilute hydrochloric acid

HCl + calcium carbonate → calcium chloride + carbon dioxide + water.

HCl(aq) + CaCO3(s) → CaCl2(aq) + CO2(g) + H2O(l)

calcium carbonate may be used in the form of marble chips.

The reaction rates can be compared using large marble chips, and the same mass of small
marble chips. The reaction can be followed by plotting the loss of mass against time.

The reaction rate is faster (the slope is steeper) for the reaction with small marble chips
(greater surface area).
Note that the final loss of mass is the same for both reactions. This is because the same
mass of calcium carbonate (marble chips) will give the same mass of carbon dioxide
whether the chips are large or small. The smaller chips will just do it more quickly.

Fast Reactions - Fireworks.

Fireworks have chemical reactions which are fast and highly exothermic. The reaction is
started by putting in heat energy (you light the firework).

Catalysts - What is a Catalyst?

A catalyst is a substance that will change the rate of a reaction. A catalyst is often used to
make a reaction go faster.

The catalyst itself does not take part in the reaction as a reactant. It is not changed by the
reaction, it is not used up during the reaction. It is still there in the same form when the
reaction is complete.

A catalyst is usually a transition metal, a transition metal oxide (see uses of transition
metals) or an enzyme in living cells. An exception is aluminium oxide, used in the
cracking of hydrocarbons. A substance which works well as a catalyst for one reaction
might not work well as a catalyst for a different reaction.

How does a catalyst work?

A catalyst works by providing a convenient surface for the reaction to occur. The reacting
particles gather on the catalyst surface and:

1) collide more frequently with each other

2) more of the collisions result in a reaction between particles because the catalyst can
lower the activation energy for the reaction.

A catalyst is often used as a powder, so that it has a bigger surface area per gram.

Hydrogen peroxide is stable at room temperature. The presence of a catalyst may cause it
to decompose.

hydrogen peroxide → oxygen + water.

2H2O2(aq) → O2(g) + 2H2O(l)

The rate of the reaction can be followed by recording the volume of oxygen produced
(you must know a test for oxygen). The catalyst used is Manganese(IV) oxide - MnO 2(s)
Using more catalyst will show an increase in reaction rate. This is because more catalyst
will have a greater surface area for the reaction to take place.
The reaction can be performed using (the same amount) of different catalysts to compare
how well each catalyst works for the same reaction.

As you can see from the graph, Manganese(IV) oxide (MnO 2(s)) is the best catalyst. The
gradient of the plot is greater (steeper) than the other two. Copper(II) oxide (CuO(s)) is not
as good as manganese(IV) oxide but is better than zinc oxide (ZnO(s)).Without a catalyst,
hydrogen peroxide will not decompose.

Catalysts - Enzymes - Temperature and pH.

An enzyme is a protein molecule.

Enzymes are used by living cells as catalysts. Enzymes are very specific catalysts. This
means that one particular enzyme will act as a catalyst for one particular reaction but
nothing else.

An enzyme will work best at a particular temperature and pH, called its optimum
conditions. Enzymes usually work best in warm conditions (around 40 °C) unlike
chemical catalysts which often work best when they are very hot.

A graph of enzyme activity plotted against temperature is shown below. Enzyme activity
is a measure of how well an enzyme works as a catalyst.
Above 45 °C, the enzyme starts to be destroyed and stops working. In these conditions
the shape of the enzyme changes and it is said to denature.

A graph of enzyme activity against pH would have a similar shape but the peak (the
optimum conditions) would be at a different pH for different enzymes.

Pepsin in the stomach works best at pH = 2.

Amylase in the mouth works best at pH = 7.

Catalysts - Enzymes - Classifications and Uses.

In the process of digestion, enzymes are used to break down large food molecules into
smaller soluble molecules. Enzymes are classified according to the type of food they
digest. Enzymes are classified as carbohydrase, lipase or protease.

Carbohydrase - changes carbohydrate (starch) into sugars (glucose).

Lipase - changes fat (lipid) into fatty acids and glycerol (in biology the posh word for
"fat" is "lipid").

Protease - changes protein into amino acids.

Enzymes are used in:

1) making alcohol (yeast)

2) making yoghurt and cheese (bacteria).

3) biological detergents (lipase and protease).

4) making soft-centred chocolates

5) making baby food6) changing starch syrup into sugar syrup and glucose syrup into
fructose syrup.
7) Industrial Processes.

Catalysts - Enzymes.

Fermentation.

Yeast is a microorganism containing an enzyme which will convert a sugar (glucose)

solution into carbon dioxide and alcohol (ethanol).

The word equation for fermentation is:

glucose + yeast → carbon dioxide + ethanol.

Carbon dioxide gas bubbles out of the solution into the air leaving a mixture of ethanol
and water. Ethanol can be separated from the mixture by fractional distillation.
Fermentation must be carried out in the absence of air to make alcohol. If air is present,
ethanoic acid is made instead of alcohol.

Yeast is used in a batch process to make alcohol in beer and wine. An enzyme in yeast
acts on the natural sugar in malt (to make beer) and grapes (to make wine). When the
alcohol concentration reaches about 10%, the alcohol damages the yeast and fermentation
stops. In a batch process the reaction vessel must be emptied and cleaned and then
refilled with the new starting materials. A batch process takes more time and is more
expensive than a continuous process.

Different alcoholic drinks contain different amounts of alcohol. Some people drink
alcohol for enjoyment, some drink to excess and some people become addicted to
alcohol. The harmful effects (physical and social) of drinking excess alcohol are
widespread and reach all parts of society.

Ethanol can be made on a large scale for use as a fuel or solvent by the hydration of
ethene or the fermentation of sugar cane. Sugar cane is a renewable resource. Renewable
means that the resource can be replaced. For example more sugar cane can be grown.
Compare this with the use of fossil fuels (the source of ethene) which are a non-
renewable resource.

Yeast is used in the baking of bread. The carbon dioxide produced causes the bread to
rise and fills the bread full of bubbles. The alcohol evaporates during the baking process.

Yoghurt and Cheese.

Bacteria can be added to milk to make yoghurt. An enzyme in the bacteria reacts with
sugar in the milk (called lactose) and converts it into lactic acid. Lactic acid changes milk
proteins and forms the thicker yoghurt.
Cheese is made by adding an enzyme called rennet after bacteria have produced lactic
acid in milk. Rennet makes milk proteins turn solid and this is the basis for cheese.

Catalysts - Enzymes - Biological Detergents.

Biological detergents and washing powders use lipases and proteases to break down fat
and protein molecules from food stains which have remained on clothing. The fatty acids,
glycerol and amino acids which are produced are removed in the water during the
washing process.

The use of enzymes in detergents has the advantage that effective washing can be carried
out in warm water. Warm water is preferable to hot water because:

1) it is more energy efficient (you don't have to heat the water so much).

2) the dye in coloured clothing is less likely to wash out of the fabric.

3) clothes are more likely to stay the same shape (hot water causes some fabric to shrink).

Catalysts - Enzymes - Chocolates and Baby Food.

Enzymes are used to make some soft-centred chocolates.

An enzyme called invertase will convert a sugar called sucrose into smaller sugar
molecules called glucose and fructose. The breaking down of some sucrose molecules
causes the chocolate to become softer and sweeter (fructose is particularly sweet).

Proteases may be used in making baby food. Large protein molecules can be partly
broken down into amino acids. This process happens naturally during digestion. Using
enzymes to pre-digest the protein in food makes it easier for digestion by the baby.

Catalysts - Enzymes - Syrup and Slimming Food.

Syrup is the name given to a saturated sugar or starch solution.

Starch is a natural polymer made from sugars. The starch in starch syrup may come from
many sources. Corn starch and potato starch are common.

A carbohydrase can be used to convert starch syrup into sugar syrup. An enzyme called
isomerase can convert glucose in sugar syrup into fructose syrup.

Fructose is much sweeter than glucose. A small amount of fructose in a food can replace
a larger amount of glucose without losing the sweet taste. This is useful in preparing
slimming food since a small amount of fructose is less fattening than a larger amount of
glucose.
 Catalysts - Enzymes - Industrial Use in Manufacturing.

Enzymes are used in industry so that reactions can happen at everyday temperatures and
pressures. This allows savings in terms of energy and the cost of building and
maintaining expensive plant.

Sometimes a whole organism containing the enzyme is used (for example yeast or
bacteria). Conditions are chosen to stabilise the organism. This means keeping it alive
and active for long periods of time by providing it with all its living needs.

Sometimes the enzyme is extracted and immobilised. This means that the enzyme is
trapped in an unreactive carrier. Alginate beads are often used for this (alginate is a
carbohydrate which is extracted from seaweed).

Either of these methods allow the enzymes to be used many times in a continuous process
rather than a batch process.

Energy - Endothermic and Exothermic.

A chemical reaction always has a change in energy

In a reaction going from reactants to products, either :

1) Heat is given out - called Exothermic or

2) Heat is taken in - called Endothermic.

The large majority of reactions are exothermic, they give heat out.

Some physical processes are associated with a change in energy. Melting and boiling are
endothermic, Freezing and condensing are exothermic.

Breaking bonds (overcoming the force of attraction) requires energy, you have to put heat
in - it is endothermic. This is why melting and boiling are endothermic.

Making bonds gives out energy - it is exothermic. This is why freezing and condensing
are exothermic.

In a chemical reaction you need to put energy in to break bonds in the reactants, you get
energy out when new bonds are formed to make the products.

If you get out more energy than you have to put in, then overall the reaction is
exothermic. This is what normally occurs.

If you have to put in more energy than you get out, then the reaction is endothermic, but
except in rare circumstances, the reaction doesn't happen.
 Bond Energy Calculations.

In the reaction between hydrogen and chlorine,

hydrogen + chlorine → hydrogen chloride.

H2(g) + Cl2(g) → 2HCl(g)

The reactants are hydrogen and chlorine, the product is hydrogen chloride.

You must put energy in to break the bonds in the reactants, before energy is given out by
forming the bonds in the products.

The minimum amount of energy you need to put in to make the reaction happen is called
the activation energy.

When the bonds between the hydrogen and chlorine molecules (the reactants) have been
broken, then both hydrogen and chlorine exist as atoms.

When an atom of hydrogen and chlorine react with each other they form a new bond,
give energy out, and the product is hydrogen chloride.

The table below shows bond energies. Bond energies are given in kilo Joules (thousand
Joules) per mole of bonds.

Bond Bond Energy (in kJ per mole)

H—H 436
Cl—Cl 242
H—Cl 431

The bond energy is the amount of energy which

1) you must put in to break the bond, or

2) is given out when the bond is formed.

In the reaction between hydrogen and chlorine, the big numbers used to balance the
equation (1H2 + 1Cl2 → 2HCl) tell you how many moles there are of reactant and
product. You must break 1 mole of H—H bonds, and 1 mole of Cl—Cl bonds. The
amount of energy needed is:

436 + 242 kJ = 678 kJ.

When 2 moles of H—Cl bonds are formed, the amount of energy given out is

2 x 431 kJ = 862 kJ.

The difference between these two energies (reactants minus products) is the overall
amount of energy given out per mole of reactants.

678 - 862 kJ = -184 kJ.

The change in energy during a reaction is given the symbol ΔH. In the reaction between
hydrogen and chlorine,

∆H = -184 kJ per mole.

For an exothermic reaction, ΔH is negative.

Energy Level Diagrams.

The change in energy can be plotted against the progress of a reaction, as the reactants
turn into products.

Going from reactants to the top of the curve, you are going up the energy scale. Energy
(heat) is being put in to break bonds in the reactants.
At the top of the curve, the bonds in the reactants have been broken. The amount of
energy put in to break these bonds is called the activation energy.

The activation energy is the minimum amount of energy needed for the reaction to occur.
A catalyst may work by lowering the activation energy for a reaction.

Going from the top of the curve to the products, you are going down the energy scale.
Energy (heat) is given out as bonds form in the products.

The reactants are higher up the energy scale than are the products. The amount of energy
(heat) you need to put in (the activation energy) is less than the amount of energy (heat)
you get out. This is a typical exothermic reaction.

The difference in energy levels between the reactants and the products is given the
symbol ∆H (pronounced 'delta H'). This is the amount of heat given out (or taken in)
during the reaction.

For an exothermic reaction, ∆H is negative.

For an endothermic reaction, ∆H is positive.

Energy - Examples of Endothermic and Exothermic Reactions.

Most reactions are exothermic. Examples are:

1) Combustion of methane (natural gas).

2) Neutralisation.

3) Adding concentrated sulfuric acid to water is highly exothermic (gives out a lot of
heat).

4) Adding water to anhydrous copper (II) sulfate is exothermic. Anhydrous copper (II)
sulfate is white. Anhydrous is pronounced "an-high-drus" Anhydrous means "without
water".

Anhydrous copper (II) sulfate is copper (II) sulfate which is completely dry. When water
is added to it, it turns into the familiar hydrated blue crystals. Hydrated is pronounced
"high-dray-tid", it means 'with water'. This is used as a test for water.

If blue (hydrated) copper (II) sulfate crystals are heated, an endothermic reaction occurs,
they lose their water, turn white and become anhydrous copper (II) sulfate crystals again.
The reaction is reversible. Blue copper (II) sulfate crystals will also turn white in the
presence of concentrated sulfuric acid.

Few reactions are endothermic. Examples are:

1) Photosynthesis. Chlorophyll is a very clever catalyst, which allows plants to make
sugar from carbon dioxide in the air. The energy needed for the reaction comes from
sunlight.

2) Thermal Decomposition.

3) The reaction of ethanoic acid with sodium carbonate.

4) Dissolving some salts in water is an endothermic process. Potassium chloride and

ammonium nitrate both take in energy when they dissolve. If you put a thermometer in
the solution as they are dissolving, you will see that the temperature drops.

5) Melting, boiling and evaporation are all endothermic processes (not reactions).

Enthalpy of Reaction

The purpose of calorimetry is to use an instrument known as a calorimeter to determine

the enthalpy of a substance undergoing chemical change. In a calorimeter known as a
bomb calorimeter, it is the enthalpy of combustion that is measured. This is how the
caloric content of foods is determined. In both cases, since the heat absorbed or released
is proportional to the amount of reactant used, molar enthalpy = ∆H/n is a more
meaningful and characteristic quantity.

In a bomb calorimeter, the actual chamber holding the sample is known as a “bomb”.
After opening its lid, we place a weighed sample in a cup at the bottom of the bomb. It is
sealed, and through a valve, O2 is delivered, saturating the bomb to prepare it for ignition.
The bomb is then secured within a calorimeter bucket that is filled with water (the water
is the environment which will absorb the heat of combustion). A stirrer keeps the
temperature of the water evenly distributed. A thermometer allows us to measure the
initial temperature; the ignition wire connected to a high voltage source initiates the
explosion; heat is released, and we measure the maximum temperature attained.

Q = mc ∆T

m = mass of the water in the calorimeter in grams (because of c ‘s units; see below), or
the mass of whatever substance is acting as the environment. In reality we should assume
that the material part of the calorimeter also absorbs heat. But in this course, we usually
ignore that part.

c = specific heat of water or whatever is acting as the environment.

Note c is usually expressed in , so that Q is in Joules

∆T = Tf – Ti.

To get ∆H, remember:

∆H = - Q.

We convert J to kJ by /1000, and then

Molar enthalpy = ∆H/n. n = number of moles of reactant. So we convert the

carefully measured mass in to moles by dividing by molar
mass.

In molar heat of neutralization problems, n = CV, where

C = concentration in “M” = moles/L.

V = volume in litres.

In-Class Examples

1. 9.0 grams of charcoal (C) were completely consumed in a bomb calorimeter. If we

assume that the 2.0 L of water absorbed all of the heat released by the charcoal, and
if the temperature of the water increased from 20.25 to 56.04 oC, what is the molar
enthalpy of carbon?

Answer

Q = mc ∆T

= 2000g(4.19 J/(g C))(56.04-20.25)

= 299 920 J
∆H = - Q = - 299 920 J = -299.92 kJ

n = 9.0g / 12.01 g/mole = 0.7493 mole

∆H/n = -299.92 kJ/ 0.7493 mole = -400.27kJ/mole of C = - 4.0 X 102 kJ/mole( sig figs)

2. CS2, a very flammable liquid, has a molar enthalpy of -1028 kJ/mole. What
do you expect aluminum's final temperature to be if 1.0 kg of Al is initially at
20.0 C, and it absorbs all the heat from the following sample of CS2:

mass of CS2 before burning: 22.6 g

mass of CS2 after burning: 11.6 g

specific heat capacity of Al: 0.900 J/[g C]

Answer

mass = 22.6 - 11.6 = 11.0 g

11.0g/ 76g/mole = 0.1447 moles

n(∆H/n) = ∆H = 0.1447moles (-1028 kJ/mole) = -148.79 kJ = --148 790 J

Q = - ∆H = 148790 J

Q = mc ∆T

148790 J = 1000g(0.900)(Tf - 20)

Tf = 185.3 C = 1.9 X 102 0C

3. 300 mL of 0.2 M aqueous KOH neutralizes 150 mL of aqueous 0.2 M H2SO4.

We go from an average initial temperature of 22.3 oC to a maximum of 29.2
C. Calculate the molar heat(enthalpy) of neutralization of KOH.

2KOH + H2SO4  K2SO4 + 2 H2O

Answer

Q = mc ∆T

= (300 + 150 g)(4.19)(29.2-22.3)

=13009.95 J

∆H = - Q = - 13009.95 J = -13.01 kJ

n = CV = 0.2mole/L(0.300 L) = 0.06 moles

∆H/n = -13.10 kJ/0.06 moles = -217 kJ/mole of KOH = -2 X 102 kJ/mole of KOH

Very important: When plugging in V, make sure by looking at the stoichiometry

that you consider only the volume of the KOH (since they asked for its
enthalpy)that actually reacted. If they had used an excess of KOH like 600 ml,
this would have changed the value for m but not for V. How do you calculate the
amount in L of KOH that actually reacts with a given amount of acid?

(0.2 moles/L H2SO4) (0.150 L) (2 moles KOH/ 1 mole H2SO4)(L/0.2 moles KOH) = 0.300
L

Basically VB = volume of the base= [CAVA/CB] [nB/nA] where nB = moles of base or

VA = [CBVB/CA] [nA/nB]
4. Find the final temperature of the following mixture:

400. g of Cu initially at 99.0 oC

25 L of water initially at 10.0 oC

c for Cu = 0.39 J/[g C]

Answer

QH2O = - QCu ( because the heat lost by Cu will be gained by the water)

mH2OcH2O (Τf - TH2O) = -mCucCu (Τf - TCu); Note that they reach the same final temperature.

25000g (4.19)( Τf-10) = -400 ( 0.39)( Τf -99)

Τf = 10.1 C = 10. oC

The temperature change is insignificant (especially if we pay attention to significant

figures) because the amount of water is much greater than the amount of Cu, and
because water has a higher specific heat than Cu.