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SULPHURIC ACID / SULFURIC ACID
Sulphuric acid or sulfuric acid is a highly corrosive, strong mineral acid. It has a molecular formulae of
H2SO4 (2 hydrogen atoms,1 sulfur atom and 4 oxygen atoms) and mostly colorless (other variants
include pale yellow & dark brown). It has the molar mass of 98.079g/mol. No matter how concentrated it
is, it is still soluble in water.
The chemical structure of sulfuric acid is as below:
As sulphuric acid is a kind of diprotic acid too, it also chows different properties depending on its
concentration. As it has a strong acidic nature, it is god darn corrosive and is able to corrode metals, living
tissue and even stable substances like sand and rock. And if the concentration of sulphuric acid is high, it
will gain the properties of strong dehydration and oxidization and it will also be more dangerous. This is
because it will not only cause chemical burns (via hydrolysis) but will also cause secondary thermal burns
(via dehydration). The increase in concentration will also cause sulphuric acid to become more
hygroscopic, making it easier for it to absorb water vapour from the air.
A little bit of history
The old name for sulphuric acid was oil of vitriol. (vitriol usually refers compounds of sulphur in ancient
times). Ancient doctors in the east and west have long ago tried to use the oil of vitriol for medical use.
The name oil of vitriol was coined by European alchemist because they prepared it by roasting green
vitriol :iron (II) sulphate on an iron retort. Earlier recipes on the way to produce sulphuric acid as found in
the Compositum de Compositis and Summa Perfectionis both involve the distillation of alum, but the
recipe stated there was not quite right and was misinterpreted.
17th century chemist Johann Glauber successfully prepared sulphuric acid through burning sulphur
together with saltpeter (a.k.a. potassium nitrate, KNO3) in the presence of steam. The decomposition on
saltpeter oxidized the sulphur to turn into SO3 and after adding water, it had a reaction and therefore
produce sulphuric acid. Joshua Ward began using this method to mass produce sulphuric acid in 1736.
Sulphuric acid was produced in glass bottles several pounds at a time.
Later in 1746 ,John Roeback adapted this method to produce sulphuric acid using lead-lined chambers
(stronger & less expensive) that produced more than the previously used glass containers. This process
enabled sulphuric acid to be industrailized affectively. Moreover , this process managed to produce
sulphuric acid approaching the concentration of 65%.This method, the lead chamber process or chamber
process remain the standard way to produce supluric acid for the next 200 years. Refinements to the
lead chamber process by Joseph L. Gay-Lussac and John Glover improved the concentration of sulphuric
produced by this process to 78%.
However, the manufacture of some dyes and other chemical processes require a more concentrated
product. Throughout the 18th century, highly concentrated sulphuric acid could only be made through the
process of dry distilling minerals, a similar technique used in the original alchemical processes. But, this
process was costly and prevented a large scale production of concentrated sulphuric acid. Pyrite (iron
disulphate,FeS2) was heated in air to obtain iron(II) sulphate (FeSO4), which was oxidized through further
heating in air to form iron(III) sulphate ,Fe(SO4)3. When iron (III) sulphate was heated to 480C, it
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decomposes into iron(II) sulphate and sulphur trioxide. The concentration of sulphuric acid produced will
be inversely proportional to the amount of water that was passed through.
The contact process, a far more economical process for producing sulphur trioxide and sulphuric acid of a
variety of concentrations and also pure sulphuric acid was patented in 1831 by Peregrine Phillips and this
process has since become the main method to produce sulphuric acid today.
Physical properties of sulphuric acid
There are many different concentrations of sulphuric acid, there are:
a) 10% concentration: Dilute sulphuric acid, with the density of 1.07kg/L and a concentration of
approximately 1mol/L.
b) 29-32% concentration: Used as electrolytes in leadacid batteries. The battry acid. Has the
density of 1.23-1.28kg/L and the concentration of 4.2-5 mol/L.
c) 62-70% concentration: Produced during the chamber process, called chamber acid.
Also used as fertilizer. Has the concentration of 1.52-1.60kg/L and
concentration of 9.6-11.5mol/L.
d) 78-80% concentration: Can be obtained from the bottom of the Glover tower during the
lead chamber process. The acids are tower acid and Glover acid.
Has the density of 1.70-1.73kg/L and a concentration of 13.5-14mol/L.
e) 98% concentration: Known as concentrated sulphuric acid. Has the density of 1.83kg/L and
the concentration of 18mol/L.
Besides that, in a pure state, sulphuric acid (L) has a density 1.84g/cm3 and a molar mass of
98.079g/mol. The melting point of the sulphuric acid is 10C and the boiling point of 337C, but when the
acid gets heated above 300C, the sulphuric acid shall decompose slowly. Pure sulphuric acid has a
vapour pressure of
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Anhydrous (no water) H2SO4 is a very polar liquid, having a dielectric constant of around 100 this makes it
have a high electrical conductivity, caused by a process known as autoprotonlysis (dissociation
through protonating itself).
Chemical properties of sulphuric acid
Sulphuric acid has hydration properties. Sulphuric acid is highly exothermic (releases heat when
undergoing a process) because of its hydration reaction. As the reaction that occurs is in an equilibrium
that favours the rapid protonation (adding of proton, a process of molecule autoionization), sulphuric acid
is added into the water during dilution of sulphuric acid rather than adding water into sulphuric acid as this
ensures sulphuric acid is the limiting agent. This reaction forms hydronium ions.
H2SO4 + H2O H3O+ (hydronium ions) + HSO4
(bisulphate anion)
The product formed has an acid dissociation constant of 2.4106 [a strong acid]
HSO4
+ H2O H3O+
(hydronium ions) + SO42-
(sulphate anion)
The product formed has an acid dissociation constant of 1.0102 [acid has become weaker]
The hydration property of sulphuric acid is significantly strong since it is thermodynamically favourable
and has strong affinity of water. It can remove water (H2O) from other compounds such as carbohydrates,
thus producing heat, steam, carbon and a more diluted acid with increased amounts of hydronium and
bisulphate ions.
The following demonstrates the hydration property of sulphuric acid when reacted with sugar:
Table sugar (sucrose) is mixed with sulphuric acid. The white sucrose changes from white to
black (formation of carbon).The carbon would smell like caramel due to the heat produces. The
following chemical reaction happens:
Sucrose (C12H22O11)+sulphuric acid (H2SO4) Black foam(12 C)+ Steam(11 H2O)+ acid/water mix
The reaction of copper (II) sulphate with sulphuric acid changes the blue copper (II) sulphate
crystals into white power as water is dehydrated. The following reaction happens:
Blue crystal (CuSO45H2O ) + sulphuric acid (H2SO4) white powder (CuSO4) + Water (5 H2O)
Similarly, mixing starch into concentrated sulphuric acid will react and produce carbonand water as
absorbed by the sulphuric acid (which becomes slightly diluted). The effect of this can be seen when
concentrated sulphuric acid is spilled on paper which (composed ofcellulose). The cellulose reacts and
becomes burnt , the carbon appears much as soot would in a fire. Although less dramatic, the action ofthe acid on cotton, even in diluted form, will destroy the fabric.
As sulphuric acid is obviously an acid, it will react with most bases and will produce its corresponding
sulphate. A notable example is the preparation of blue copper salt copper (II) sulphate can be prepared
through a reaction between copper (II) oxide with sulphuric acid. Copper (II) sulphate is commonly used
for electroplating and as a fungicide. The following is the chemical equation:
Copper (II) oxide [CuO](s) + Sulphuric acid [H2SO4](aq) copper(II) sulphate[CuSO4](aq) +water [H2O](l)
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Also, the displacement of weaker acids from their salts can be done by using sulphuric acid. An example
of this process is the displacement of acetic acid when sulphuric acid reacts with sodium acetate. The
process also produces sodium bisulphate.
Sulphuric acid (H2SO4) + Sodium acetate (CH3COONa) Sodium bisulphate (NaHSO4)+ Acetic acid (CH3COOH)
Similarly, the reaction between sulphuric acid and potassium nitrate and displace nitric acid and
potassium bisulphate precipitate. When sulphuric acid combines with nitric acid, sulphuric acid acts as
both acid and dehydration agent, forming the nitronium ion (NO2+) which is important in nitration reactions
involving electrophilic aromatic substitution (an atom in a hydrocarbon with alternating double/single
bonds between carbon atoms forming rings which has been replaced by an electron lover -a
regent/substance that is attracted to electrons-). This type of reaction involves the protonation of oxygen
atoms.
When sulphuric acid reacts with superacids (acids with acidity greater than 100% sulphuric acid),
sulphuric acid would act as a base and would be protonated, forming an [H3SO4]+ ion.
Dilute sulphuric acid reacts with metals through a single displacement reaction, producing hydrogen gas
and salts (metal sulphates). It is especially reactive with reactive metals from the reactivity series, above
copper (iron,aluminium, zinc,manganese,magnesium,nickel).
Iron [Fe](s) + Sulphuric acid [H2SO4](aq) Hydrogen gas [H2](g) + Iron sulphate [FeSO4](aq)
Since concentrated sulphuric acid is a strong oxidising agent, it does not react with metals the same way
other acids react. Its strong oxidising agent makes sulphuric acid evolves into water, sulphur dioxide &
SO42- ions instead of hydrogen and salts.
2 molecules of H2SO4 + accepts 2 electrons (2e-) (Sulphur dioxide)SO2 + 2 molecule of water(H2O) + sulphate ion (SO42-)
Concentrated sulphuric acid is also capable of oxidising non-active metals like tin & copper, depending on
temperature. Lead & tungsten are however resistant to sulphuric acid.
Copper (Cu) + 2 molecules of sulphuric acid (H2SO4 )
Sulphur dioxide (SO2)+ 2 molecules of water (H2O) + sulphate ion (SO42-)+ copper ion (Cu2+)
High temperature sulphuric acid is also able to react and oxidise non-metals like carbon & sulphur.
-Carbon (C) + 2 molecules of sulphuric acid (H2SO4)
Carbon dioxide (CO2)+ 2 molecules of sulphur dioxide (SO2)+ 2 molecules of water (H2O)
-Sulphur (S) + 2 molecules of sulphuric acid (H2SO4)
3 molecules of sulphur dioxide (SO2)+ 2 molecules of water (H2O)
Reaction with sodium chloride:
- Sodium chloride (NaCl) + Sulphuric acid (H2SO4)
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Sodium bisulphate (NaHSO4)+Hydrogen chloride gas (HCl)
The manufacturing of sulphuric acid
a) The lead chamber process
The first known method to mass produce sulphuric acid efficiently was conceived by Englishman John
Roebuck in 1746. As stated before, sulphuric acid was produced by using lead-lined chambers that were
more stronger and more economical than glass chambers that was used previously. Several refinements
were done in this process to produce a variety of concentration of sulphuric acid. Since sulphuric acid was
extremely exothermic, the lead chambers was designed in a way to dissipate heat formed during the
reactions.This process was used for almost 2 centuries until it got replaced by the contact process.
Type 1
The original process was highly similar to the methods used by Johann Gaubler. Sulphur and saltpeter
(potassium nitrate) was ignited in a room lined with lead foil. Saltpeter (potassium nitrate) acts as a
oxidising agent that oxidises sulphur to become sulphur trioxide. Based on the following reaction:
6 molecules of potassium nitrate [KNO3](s) + 7 molecules of sulphur [S](s)
3 molecules of potassium sulphite (K2S) + 6 molecules of nitrogen monoxide [NO](g) + 4 molecules of sulphur trioxide [SO3](g)
The room itself would have a floor covered with water and the sulphur trioxide would react with the water,
thus producing sulphuric acid. Based on the following equation:
Sulphur trioxide[SO3](g) + Water [H2O](l) Sulphuric acid [H2SO4](aq)
However, this process was a batch process (1 time use) and it would result in the permenant consumption
of saltpeter (potassium nitrate).
Early plants used very large lead-lined wooden rectangular chambers (Faulding box chambers) that were
cooled by ambient air. The internal lead sheathing served to contain the corrosive sulphuric acid and to
render the wooden chambers waterproof.
Type 2
Later Joseph Gay-Lussac and John Glover both refined the original process in 1835. Both of them had
found a way to recover the nitrogen from the nitrogen monoxide that was produce during the reaction.
The recycling of nitrogen through this process sharply reduced the dependence on expensive saltpeter
(potassium nitrate) as a source for nitrogen and reduce the nitrogen monoxide emission. The equation of
this process is shown below:
*4 molecules of nitrogen monoxide [NO](g) + Oxygen gas [O2](g) + 2 molecules of water [H2O](l)
4 molecules of nitrous acid [HNO2](l)
*4 molecules of nitrous acid [HNO2](l) + 2 molecules of sulphur dioxide [SO2](g)
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2 molecules of sulphuric acid [H2SO4](aq) + 4 molecules of nitrogen dioxide [NO](g)
Both of them also refined the whole process by replacing the traditional rectangular chambers into
stoneware packed masonry cylinders. Also they successfully managed to make a process that produced
a specific concentration of sulphuric acid. This led to the making of the classical lead chamber process.
The classical lead chamber process consisted of 3 main components:
a) The Glover tower
b) The lead chambers
c) The Gay-Lussac Tower
The following is the process:
1) Hot sulphur dioxide gas enters the bottom of the Glover tower.
2) The sulphur dioxide gas will be washed with nitrous vitriol [a solution consisting of sulphuric acid with
recycled nitrogen monoxide (NO) and dissolved nitrogen dioxide (NO2)] and mixed with nitric oxide and
nitrogen dioxide gas.
3) Sulphuric acid with a concentration of 62%-68% (chamber acid) is achieved when the hot gases
evaporates water from the sulphuric acid.
4) Some of the sulphur dioxide are oxidized to become sulphur trioxide and dissolves in the acid wash
to form tower acid (sulphuric acid with concentration of 78% to 80%) .
5) Denitration occurs. The nitrogen monoxide from the acid wash is stripped back into gaseous state
in the Glover tower and is carried out to enter the lead chamber.(?)
6) A mixture of gases (including nitrogen monoxide, sulphur dioxide & trioxide, nitrogen, water & steam)
enter the lead chamber where these substances reacts with more water. The chamber is a large, box-
liked room that is enclosed in a form of a truncated cone.
7) Here, sulphuric acid is formed through numerous complicated reactions: It condenses on the walls of
the chamber and is collected at the floor of the chamber. The number of chambers used is usually
between 3-12. Sulphuric acid with a concentration of 62%-68% (chamber/fertilizer acid) is produced
and drawn out from the chambers.
8) The following reactions occur in the lead chamber chronologically:
a) Nitrogen monoxide (NO) + oxygen gas (O2) Nitrogen dioxide (NO2)
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b) Nitrogen dioxide (NO2) + Nitrogen monoxide (NO) + water (H2O)
2 molecules of nitrous acid (HNO2)
c) Sulphur dioxide (SO2) + Water (H2O) Sulphurous acid (H2SO3)
d) Sulphurous acid (H2SO3) Bisulphite ion (HSO3-
) + Hydrogen ion (H
+
)
e) Nitronium ion (NO+) + Bisulphite ion (HSO3-) NOSO3
- + Hydrogen ion (H+)
f) Nitronium ion (NO+) + NOSO3-
2 molecules of nitrogen monoxide (NO) + sulphur trioxide (SO3)
g) 2 molecules of nitrous acid (HNO2) + 2 hydrogen ions (H+)
2 molecules of nitrogen monoxide (NO) + 2 molecules of water (H2O)
h) Sulphur trioxide (SO3) + water (H2O) sulphuric acid (H2SO4)
--------------------------------------------------------Overall reaction------------------------------------------------------
Sulphur dioxide (SO2) + oxygen gas (O2) + water (H2O) Sulphuric acid (H2SO4)
------------------------------------------------------------------------------------------------------------------------------------------
There is also another variant to this process:
a) 2 molecules of nitrogen dioxide (NO2) + water (H2O) Nitrous acid (HNO2) + Nitric acid (HNO3)
b) Sulphur dioxide [SO2] (l) + Nitric acid (HNO3) Nitrosylsulfuric acid (NOHSO4)
c) Nitrosylsulfuric acid (NOHSO4) + Nitrous acid (HNO2)
Sulphuric acid (H2SO4) + Nitrogen dioxide (NO2) + Nitrogen monoxide (NO)
d) Sodium dioxide [SO2] (l) + 2 molecules of nitrous acid (HNO2)
Sulphuric acid (H2SO4) + 2 molecules of nitrogen monoxide (NO)
------------------------------------------------------------Overall reaction---------------------------------------------------
2 molecules of sulphur dioxide (SO2) + 2 molecules of water (H2O) + Oxygen gas (O2)
2 molecules of sulphuric acid (H2SO4)
------------------------------------------------------------------------------------------------------------------------------------
9) Finally, after the gases pass through the lead chambers, they go through the last component, the
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Gay-Lussac tower. Here, the gases shall be washed & cooled by the Glover/tower acid (that is drawn
from the cooled acid stream.)
10) The nitrogenous oxides and the unreacted sulphur dioxide dissolve in sulphur dioxide to form the
nitrous vitriol that will be used in the Glover tower. The waste gases exiting the Gay-Lussac tower
discharged into the atmosphere.
11) The process shall repeat itself again and again continuously. The losses in nitrogen is compensated
with nitric acid which is added into the Glover tower that was formed through the catalytic oxidation
of ammonia.
Sulphur dioxide can be produced by burning sulphur or roasting pyritic ore (Iron pyrite) with presence of
oxygen. The equation for generation of sulphur dioxide is as follows.
- S8 + 8 oxygen gas (O2) 8 sulphur dioxide molecules (SO2)
- 4 molecules of iron pyrite (FeS2) + 11 molecules of oxygen gas (O2)
2 molecules of iron (III) oxide (Fe2O3) + 8 Molecules of sodium dioxide (SO2)
Nitrogen dioxides can be produced decomposition ofnitre in the presence of sulphuric acid or hydrolysis
ofnitrosylsulphuric acid:
- 2 molecules of nitre (NaNO3) + sulphuric acid (H2SO4)
Sodium sulphate (Na2SO4)+ water (H2O) + nitrogen monoxide (NO) + nitrogen dioxide (NO2) + oxygen gas (O2)
- 2 molecules of nitrosylsulphuric acid (NOHSO4) + water (H2O)
2 molecules of sulphuric acid (H2SO4) + nitrogen monoxide (NO) + nitrogen dioxide (NO2)
Since nitrogen oxides serve as a catalyst, they are absorbed and regenerated during the process.
b) The contact process
The contact process is the most commonly used process to produce sulphuric acid today. Patented in
1831 by Englishman Peregrine Phillips, the contact process was found to be much more economical and
efficient in producing concentrated sulphuric acid than the lead chamber process. This process involves
the use of the catalyst Vanadium oxide (V2O5).
Platinum is actually a more efficient than Vanadium oxide but since platinum is especially vulnerable tocatalyst poisoning when exposed to arsenic impurities in the sulphur feedstock, also Vanadium oxide is
much more cheaper than platinum. This makes Vanadium oxide a better choice of catalyst rather than
platinum. Also the catalyst process gives a greater purity of sulphuric acid up to 100%.
Process
Stage 1
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Sulphuric acid is produced through the combustion of sulphur in air or the combustion of pyrite to produce
sulphur dioxide.
* S8 + 8 oxygen gas (O2) 8 sulphur dioxide molecules (SO2)
* 4 molecules of iron pyrite (FeS2) + 11 molecules of oxygen gas (O2)
2 molecules of iron (III) oxide (Fe2O3) + 8 Molecules of sodium dioxide (SO2)
Stage 2
This stage is the purification process which is where sulphur dioxide is purified to avoid catalyst poisoning
from occurring during the catalyst stage. The purification unit consists of 6 processes. Note that oxygen
has also entered.
First, the sulphur dioxide gas enters the dust chamber to have the dust particles in it removed.
Then, the sulphur dioxide gas flows to the cooler where it is cooled.
Afterwards, it enters the scrubber chamber to be washed.
After that, sulphur dioxide shall enter the drier where water vapour in the sulphur dioxide is removed to
prevent the water vapour from reacting with the sulphur trioxide later on.
Finally, sulphur dioxide enters the arsenic purifier where its arsenic impurities shall be removed to prevent
catalyst poisoning from occurring that will make the catalyst become ineffective.
During the purification process, sulphuric acid can also be formed. The sulphuric acid shall be directly
sent to the absorption tower to assist in the production of oleum.
The gases are sent into the testing box to ensure their purification. The impure sulphur dioxide shall be
sent to the dust chamber again to be reprocessed while the pure sulphur dioxide gas will be sent to the
catalyst chamber for it to undergo catalystization.
Stage 3
This is the most important process in the contact process because this is where the catalyst Vanadium
oxide reacts with oxygen gas and sulphur dioxide to produce sulphur trioxide. But, for the reaction to
occur, some requirements are needed. There requirements can be determined through the application of
Le Chatelier's Principle. There requirements are:
a) Sulphur dioxide & oxygen gas both must have volumes with the ratio of 1:1
b) A high temperature between 450C - 550C is required. (Thats why gas is heated beforehand)
c) The medium standard atmospheric (atm) of 1 (pressure of 101,325 pascals)
d) The presence of Vanadium oxide catalyst (V2O5)
All of there requirements is to ensure 96% to 98% of the sulphur dioxide is converted into sulphur trioxide.
The reasons of these requirements shall be explained later on below.
The following shows what happens during the reaction:
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2 molecules of sulphur dioxide [SO2] (g) +Oxygen gas [O2] (g) 2 molecules of sulphur trioxide [SO3](g)
The reaction has a total thermodynamic system energy of -197 kJ mol1.
The following shows the mechanism of catalyst reaction that happens in the process.
a) Oxidation of SO2 into SO3 by V5+
. This is what mainly happens:
2 molecules of sulphur dioxide (SO2) + 4 vanadium ions (V5+) + 2 oxygen ions (O2-)
2 molecules of sulphur trioxide (SO3) + 4 vanadium ions (V4+)
b) Oxidation of V4+ back into V5+ by oxygen. This is where the catalyst regenerates back into its original
form as shown below:
4 vanadium ions (V4+)+ oxygen gas (O2) 4 vanadium ions (V5+) + 2 oxygen ions (O2-)
Stage 4
Even though directly dissolving sulphur trioxide into water would enable us to obtain sulphuric acid as
shown:
Sulphur trioxide (SO3) + water (H2O) Sulphuric acid (H2SO4)
BUT, since sulphur trioxide itself is exothermic, the addition of water might trigger its hydration property
and turn it into gaseous sulphur dioxide in the form of foggy aerosol that is highly uncontrollable and will
not bring any good for production as it becomes harder to contain. The gas itself is also corrosive and
difficult to condense, making it a threatening pollutant.
In order to avoid any of that from happening, after sulphur trioxide is produced in the catalization
chamber, it is sent into the absorption tower where the deposited concentrated sulphuric acid is waiting.These event occur in the absorption tower:
Sulphuric acid (H2SO4)(l) + Sulphur trioxide (SO3)(g) Oleum (H2S2O7)(l)
The reason why oleum is produced is because it is more stable than sulphuric acid and not as exothermic
as sulphuric acid. The oleum will be collected in a chamber where water shall be placed into it. The
following reaction happens:
Oleum [H2S2O](l) + Water [H2O](l) 2 molecules of sulphuric acid [H2SO4](l)
Through this reaction, the producer shall get a profit of x2 since 2 molecules of sulphuric acid is produced
rather than 1 molecule. The sulphuric acid made is concentrated (98%) and shall finally undergo the
process of bottling in the factories to be sent for commercial use.
Le Chateliers principal (The law of equilibrium)
This principal is defined as:
If a chemical system at equilibrium experiences a change in concentration, temperature, volume, or
partial pressure, then the equilibrium shifts to counteract the imposed change and a new equilibrium is
established.Any change in status quoprompts an opposing reaction in the responding system.
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This principal is used to predict chemical equilibrium in a chemical equation and in applies to reactions in
a state of dynamic equilibrium. It also explains how catalysts have no effect in on the position of
equilibrium. How does this work during the contact process?
2 molecules of sulphur dioxide [SO2] (g) +Oxygen gas [O2] (g) 2 molecules of sulphur trioxide [SO3](g)
a) The proportions of sulphur dioxide and oxygen
Why must it have an equal proportion in volume?
Since Avogadros Law states that gases at an equal volume at a same pressure contain the equal number
of particles, this would mean the reaction takes place in a ratio of 1 sulphur dioxide molecule to 1 oxygen
molecule. There is however an excess of sulphur dioxide gas relative to oxygen gas as demanded by the
equilibrium equation.
But according to Le Chateliers Principle, by increasing the concentration of oxygen gas in the mixture,
the position of equilibrium shall shift to the right. Since oxygen is easily obtained in our atmosphere, it is
very simple and cheap way to increase the conversion and yield of sulphur trioxide.
Through Le Chatelies Principle, through increasing the proportion of oxygen gas in the equation is
possible and can virtually turn every molecule of sulphur dioxide into sulphur trioxide since there is more
oxygen gas than sulphur dioxide, but there is a major drawback. Increasing the proportion and assuredly
increase the conversion of sulphur dioxide into sulphur trioxide but at the same time the amount of
sulphur trioxide produce will be reduced because too much oxygen would cause the excess oxygen to
have nothing to react with. So, in conclusion, the volume ratio of 1:1 is the most suitable in obtaining the
best overall yield.
b) The suitable temperature needed for the reaction to occur?
Why must the temperature have to be suitable?
According to Le Charteliers principal, the forward reaction (production of sulphur trioxide) is favoured
when the temperature is lowered. The system shall respond by tilting the position of equilibrium to the
right to counter react this, thus, producing more heat in the process ( H< -196 kg/mole). By shifting
the position of equilibrium as far as possible to the right, the maximum amount of sulphur
trioxide would be produced. But, the temperature of 450C to 550C isnt a low temperature,
why use such a high temperature as low?
As the temperature goes lower, yes you will produce more sulphur trioxide. But, this will makethe reaction to produce sulphur trioxide take a very, very, very, VERY long time. This is a major
loss for manufactures since they want to make sulphur trioxide in a suitable amount of time
since consumers have no time to wait for so long (it would take several years).
The gases need to reach equilibrium within a short period of time so that they would be able to
be in contact with the catalyst in the reactor. That is why the temperature of 450C - 550C is
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used as a compromise temperature as it produces a fair amount of sulphur trioxide in the
equilibrium mixture in a short amount of time.
Increasing the temperature however is totally not an option because instead of producing
sulphur trioxide, you would be getting back sulphur dioxide and oxygen gas because the point of
equilibrium tilts to the left. After forming sulphur trioxide, the temperature will cause the sulphur
trioxide to absorb heat and make it change back into more sulphur dioxide and more oxygen
gas. No manufacturer wants that to happen right? Because that would be quite silly.
c) The suitable pressure needed
Why is the pressure of 1atm needed in this reaction?
It should be noted beforehand that based on the reaction above, there are 3 molecules on the
left and 2 molecules on the right.
According to Le Charteliers Principal, as the pressure increases, the equilibrium system shall
respond by favouring the reaction that produces lesser molecules. As seen in the reactionabove, more sulphur trioxide can be produced as the pressure increases. Not only that, the rate
of reaction also increases.
But, the reaction above is done at a pressure close to the atmospheric pressure. (1 atm =
101.325 kPa)
Even though at relatively lower pressure, we are still able to conversion 99% from sulphur
dioxide and oxygen to sulphur trioxide. Due to economical restraints, increasing the pressure is
irrelevant and such insignificant change of 1% is not needed and manufactures can save more
money. Thus, the reaction above takes place at a pressure close to 1 atm.
If you decrease the pressure though, the point of equilibrium shall tilt to the left, thus producing more
sulphur dioxide and oxygen gas which is not what the manufacturer wants.
*Please note that if the reactant and product have the same amount of molecules, the equilibrium of
pressure shall NOT apply.
The reason why the presence of catalyst (vanadium oxide) is needed
Catalysts do not affect the position of equilibrium in an equation or increase the production of products, it
only speeds up the reaction (like enzymes in our bodies)
The absence of catalysts would make the reaction so slow until the point there is virtually no reaction
happening. That is catalysts are needed to ensure the reaction is fast enough so that the dynamicequilibrium (changing to obtain equilibrium) can be set up so that the products can be produced faster in
the reactor.
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c) The wet sulphuric acid (WSA) process
The most modern process to date. Patented by Danish company Haldor Topse in 1980, this process
was found by the founder of the company, Haldor Topse. This process involves the extraction of sulphur
dioxide from sulphur compounds to be made into sulphur trioxide. After that, sulphur trioxide is directly
placed into water to produce sulphuric acid mist and energy (measured by kg/mole). Special counter
measures are taken to prevent the gases from escaping. Lastly, the acid mist is cooled back into liquid
state to be bottled. The whole process is found to be more environmental friendly due to it has a low
sulphur dioxide emission and the thermal energy and molecular energy involved in the process is
conserved and the energy could be used to make the process go on. This process can remove 95%-99%
of the sulphur content in sulphur compounds and is able to produce sulphuric acid with a maximum
concentration of 99.6%. Catalysts are also involved in the process (Vanadium oxide, V2O5 or Topsoe VK
Series). Due to my lack of understanding, I am unable to give an accurate description on the processes
that happens in the wet sulphuric acid process, though it is highly similar to the contact process.
Features of the Wet Sulphuric Acid (WSA) process
95% - 99% recovery of sulphur from a sulphur compound.
Produces clean and concentrated sulphuric acid of commercial quality.
Heat produced during the reactions of the substances can be recovered 100% as superheated
and saturated steam and can be reused. Making the process autothermic.
Very low consumption of cooling water & no consumption of process water.
Minimal to none consumptions of chemicals (except for the optional DeNOx)
Optional DeNOx for gases with high content of Ammonia (NH3) & hydrogen cyanide (HCN)
Wide range turnout
Process of Wet Sulphuric Acid (WSA) process
Let us use hydrogen sulphide (H2S) as an example of sulphur feed gas.
First, hydrogen sulphide is combusted under high temperatures (with oxygen of course!). This would
make the following reaction happen:
Hydrogen Sulphite (H2S)+3/2 Oxygen Gas (O2) Sulphur dioxide (SO2)+ Water (H2O) +518kJ/mole
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H= -518kJ/mole
Then the processed gas shall move to the SO2 reactor, where it shall be oxidised by oxygen. The
chemical reaction below happens:
Sulphur dioxide (SO2) +1/2 Oxygen gas (O2) Sulphur trioxide (SO3) +99kJ/mole
H= -99kJ/mole
After that the processed gas enters the SO2 converter where it is hydrated as follows:
Sulphur trioxide (SO3) + Water (H2O) Sulphuric acid (H2SO4) [g] + 101kJ/mole
H= -101kJ/mole
Finally, the processed sulphuric acid gas now enters the WSA condenser where it is condensed into
liquid:
Sulphuric acid (H2S04) [g] + 0.17molecules of steam (H2O) [g] Sulphuric acid (H2SO4)[l] + 69kJ/mole
H= -69kJ/mole
*If the feed gas contains high amounts of ammonia, hydrogen cyanide or other nitrogen compunds,
nitrogenous oxides shall be formed. It may be necessary to remove the nitrogenous compounds, and this
can be done by adding ammonia in relative to the nitrogenous compounds and this reduces the
nitrogenous compounds into nitrogen gas and water. This is shown by the following:
Nitrogenous compound (NO) + Ammonia (NH3) +1/4 molecules of oxygen gas (O2)
Nitrogen gas (N2) +3/2 molecules of water (H2O) + 410kJ/mole
H= -410kJ/mole
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d) Methods to produce sulphuric acid manually
The following methods are all hazardous and dangerous in nature. When attempting to produce sulphur
acid, please be cautious when doing so. The following processes does not require a catalyst because
catalysts are expensive and home chemist cant purchase it.
I) Combustion of sulphur
In the laboratory, sulphuric acid can be produced by combusting sulphur in air to produce sulphur dioxide.After that the gas is dissolved in hydrogen peroxide to produce sulphuric acid. The whole process occurs
in a gas jar. The gas jar must be covered at all times.
Sulphur (S) + Oxygen gas (O2) Sulphur dioxide (SO2)
Sulphur dioxide (SO2) + Hydrogen peroxide (H2O2) Sulphuric acid (H2SO4)
The method to conduct this process is illustrated below
II) The metabisulphite/oxidizer method
The procedure in conducting this process is highly dangerous because of the involvement of toxic gases
and highly corrosive acids. All apparatus used must be ensured to be made from glass to withstand the
acids. This process has reaction similarities with the lead chamber process.
Potassium metabisulphate or sodium metabisulphite both can be used in this experiment. It is relatively
easy to obtain metabisulphates because they can be found in home brewers and used in homemade
dyeing.
To make sulphuric acid, first we must make a reaction that generates sulphur dioxide.50mg of
metabosulphate and a stir bar is placed at the bottom of the flask before adding 50ml of water. A pressure
equalizer dripping funnel is placed on to the flask. 50 ml of hydrochloric acid (with a concentration of
approx.12 molar) is then added into the funnel. Connect the flask with a gas adapter that has a glass tube
at the end. Prepare a beaker and measuring cylinder that has almost the same height and place the
measuring cylinder into the beaker and the place the glass tube end into the measuring cylinder.
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Next, fill the measuring cylinder with 25 ml of concentrated/pure nitric acid (a good oxidizer and indicator).
The beaker is then filled with ice (make sure the ice does not overlap the measuring cylinder containing
nitric acid) to conduct an ice bath.
Now, carefully open the dripping funnel to let the hydrochloric acid out drop by drop. Make sure to turn on
the stir bar to ensure the reaction that occurs is properly done. This would produce sulphur dioxide and
the gas would be transported into the measuring cylinder. Do not mix too fast to ensure the nitric aciddoes not splutter out. Stage 1 is complete.
As sulphur dioxide reacts with nitric acid, copious amount of nitrogen dioxide would be obtained (Which
shall act as a catalyst)*Note that sulphur dioxide is still being produced. The nitric acid which is originally
red brown shall gradually change its colour, slowly turning yellow-green before finally turning transparent.
When the nitric acid turns completely transparent, this indicates that all the nitric acid has been converted
into sulphuric acid. Stage 2 is complete.
To obtain a desirable concentration of sulphuric acid, the measuring cylinder is taken out and warmed
back to room temperature. As it warms, the excess sulphur dioxide present in the sulphuric acid will
bubble out into the atmosphere. After that, boil the sulphuric acid to get the concentration you want and
also remove the remaining sulphur dioxide. As the heating continues and its concentration rises, sulphuricacid fumes can be seen coming out. (indicates sulphuric acid has reached 70% concentration). To get a
near pure concentration of above 95%, the sulphuric acid would need to be heated up to the temperature
of 300 C. After cooling the acid to room temperature, you have now obtained sulphuric acid!
Below shows the chemical reactions that happen during the process:
Below shows an illustration of the process being carried out:
III) Copper Sulphate Electrochemical Method
As stated here, the process here involved electrolysis, a part of electrochemistry. Copper sulphate
consists of copper and sulphur. The process here makes it evident that breaking down copper sulphate
can produce the products: copper and sulphuric acid.
First we shall need carbon electrodes (can be obtained from batteries) or preferably a platinum electrode
(platinum coated is fine) . Attach and tape in a wire to the top of the electrode so it can be connected to
the power source. Now, we shall need a solution of sulphate (best if concentrated). Then place a copper
electrode into the solution and attach it to the negative terminal of the power supply. The platinum
electrode is connected to the positive terminal of the battery and is suspended mid air. The carbon
electrode acts as the anode and the platinum electrode acts as the cathode. The setup is now completed.
Now, the power source is turned on. A adjustable power source is preffered so the current can be
adjusted to find a current level that minimizes the corrosion of the anode (platinum is very hard to corrode,
so there is no worry, but this action must be done if electrodes from the electrochemical series is used.An
eroded would make the solution impure and the solution has to be filtered). The time taken for the copper
in the copper sulphate the convert back into copper depends on the:
Current applied
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Efficiency of the electrical charge (coulomb)
Number of moles in copper sulphate solution
The reaction would take some time. It is observed that the blue copper ions are being electrolysed out of
the copper sulphate solution and is attracted to the negative copper cathode. A spongy looking lump of
copper is seen forming around the copper cathode. At this time, the solution shall gradually become
lighter as the copper sulphate solution is gradually converted into sulphuric acid. The electrodes used in
this process is the best one you can use because the usage certain kinds of electrodes would not
produce sulphuric after the electrolysis process.
Finally, after the electrolysis process is complete, it is observed that the solution is totally clear and
transparent and a lump of copper is available inside. This clear solution is diluted sulphuric acid. Filter off
the copper and boil the dilute sulphuric acid to increase the concentration of the sulphuric acid. As stated
in the statement in the experiment above, sulphuric acid with 95% concentration can be obtained after
being heated up until 300C. This process is remarkably easier than the metabisulphide process above.
Below shows the chemical reactions that occur during the process:
Below shows the illustrated of the setup of the apparatus:
Uses of sulphuric acid
Manufacturing of fertilizers
The following fertilizers can be produced through the involvement of sulphuric acid:
a) Calcium dihydrogen phosphate
It is sometimes referred as monocalcium phospahte. Since plants need phosphorus for the health of their
roots, this compound is beneficial to plants. When together with calcium sulphate, theyre called
superphosphate. Superphosphates are made through the reaction between powdered phosphate rock
and sulphuric acid. The reaction is shown below:
Tricalcium phosphate [Ca3(PO4)2](s) + 2 molecules of sulphuric acid [H2SO4](l)
2 molecules of calcium sulphate [CaSO4](l) + Calcium dihydrogen phosphate [Ca(H2PO4)2](l)
b) Potassium sulphate
A kind of fertilizer that does not contain chloride, which is why it is used in tobacco corps. Sensitive corps
need potassium sulphate for optimal growth if the soil has accumulated chloride from irrigated water.
Potassium sulphate can be manufactured through the reaction between potassium chloride and sulphuric
acid as according to the Leblanc process. The following reaction occurs:
2 molecules of potassium chloride (KCl) + Sulphuric acid (H2SO4)
2 molecules of hydrochloric acid (HCl) + Potassium sulphate (K2SO4)
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c) Ammonium sulphate
It is an inorganic salt used commonly for fertilizing alkaline soil. However, its function is the opposite of
alum. It lowers the pH balance of alkaline soil for in to become neutral. Not only that, it also provides
nitrogen which are good for the leaf growth. However, the disadvantage of this fertilizer is that the nitrogen
content relative to the ammonium nitrite is low, somehow making it expensive to transport.
Ammonium sulphate can be produced through the reaction between ammonia gas (by product of coke-
oven) with sulphuric acid. Fine droplets of sulphuric acid is sprayed into a chamber filled with ammonia
gas. Since the reaction is exothermic, all the water is evaporated and the products are in the form of
powdery salt. The following reaction occurs:
2 molecules of ammonia gas (NH3) + Sulphuric acid (H2SO4) Ammonium sulphate [(NH4)2SO4]
d) Aluminium sulphate
As a fertilizer, aluminium sulphate has the same function as ammonium sulphate: reducing the pH value
of soil. It hydrolyses to form aluminium hydroxide precipitate and dilute sulphuric acid. Because of this,
the fertilizer is used by gardeners to produce flowers with a variety of colours. Eg: The flower of
hydrangea macrophylla changes colour according to the pH value of the soil.
Aluminium sulphate can be produce through the reaction between aluminium hydroxide and sulphuric
acid as shown below:
2 molecules of aluminium hydroxide [Al(OH)3] + 3 molecules of hydrochloric acid (H2SO4)
Aluminium sulphate [Al2(SO4)3]6 molecules of water [H2O]
Catalyst
Sulphuric acid is used as an acid catalyst to convert cyclohexanone oxime into caprolactam that is usend
foe the making of nylon. It is also used in the Mannheim process that produces hydrogen chloride andsodium sulphate (salt cake)
Electrolyte
Sulphuric acid is used as an electrolyte in car batteries (lead-acid accumulators) where it acts as a
medium between the anode (Lead) and the cathode (Lead dioxide). The reaction itself produces lead (II)
sulphate and water. The molecular weight that is obtain is 642.6 which produces 2 faraday of charge.
Simply saying, energy is produced due to some factors.
The electrochemical chemistry that happens in the lead-acid accumulator is as follows:
At the anode:
Pb+SO42-PbSO4+2e-
At the cathode:
PbO2+4H++DO42-+2e- PbSO4 +2H2O
Overall:
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Pb+PbO2+4H++2SO42- 2PbSO4 + 2H2O
Manufacturing of white pigment in certain paints
This white pigment, barium sulphide is an inorganic compound. It appears as a white and odourless
crystallite substance. It is used to produce a paint called blanc fixe (permanent white) after being
combined with titanium white pigment (titanium oxide). It is also used in coating certain photographicpapers white.
Sulphuric acid here is used for producing pure barium sulphate. The chemical equation that happens is
seen below:
Barium sulphide (BaS )+ Sulphuric acid (H2SO4)
Barium Sulphate (BaSO4) + Hydrogen sulphide (H2S)
Drain cleaners
Sulphuric acid is widely used in producing acidic drain cleaners. The strong dehydrating property present
in sulphuric acid makes it a perfect substance in removing grease, hair tissue papers (dehydrates into
carbon) in the drain. Through hydrolysis, it also can remove fats and proteins. Because the reaction
between sulphuric acid and water is vigorous, that is why these kinds of cleaners should be added
carefully and slowly into drains to clean them.
The following processes (acid hydrolysis) happen:
Proteins or amides + H2O+ Acid NH4+ + RCOOH
Ester or fats + H20 + Acid RCO2H + R'OH
Negative effects caused by sulphur
The pollution of the environment caused by sulphur elements is mainly caused by sulphur dioxide, a
molecular compound thats formed through the covalent bonding between sulphur and oxygen. The main
sources of sulphur dioxide include emission from combustion of fossil fuels and waste gases from
factories. Sulphur dioxide is also made naturally. Natural sources of sulphur dioxide include volcanoes,
decaying matter, solar action on sea water and oxidation of dimethyl sulphide emitted from the ocean.
Decaying matter emits hydrogen sulphite that would be oxidised into sulphur dioxide within hours.
Sulphur dioxide is a kind of gas that is colourless and non-flammable, yet its odour is pungent, sharp
strong irritating and also might cause choking. Sulphur dioxide also dissolves in water and this would
change the pH value of water.
On average, sulphur dioxide exist in a concentration ranging from 0.03 to o.3g/m
3
. This number isobviously higher in urban and industrialized areas. The concentrations of sulphur dioxide ranges from
place to place.
Oxidation of sulphur dioxide (aka how acid rain happens) can occur in the atmosphere in the gas phase
and aqueous phase (raindrops) homogeneously and heterogeneously on the surface of the particles of all
3 states of water. The rate of oxidation of sulphur dioxide is affected by photochemistry and temperature.
The rate of sulphur dioxide oxidation is especially high on warm and hot weathers. The oxidation process
is determined by the humidity and concentration and composition of the atmosphere.
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Homogeneous gas phase of sulphur dioxide involves 3 mechanisms:
a) Oxidation by photochemically generated reactive substances.
b) Oxidation by thermally generated reactive substances.
c) Direct photooxidation of the exited sulphur dioxide molecules.
The most important photochemical oxidation reaction is the reaction of sulphur dioxide with hydroxyl
radical (OH).
SO2 + OH (+ X) HSO3
The x molecule represents nitrogen dioxide, oxygen gas or water molecules present in air that functions
to transport excess energy away from the reaction. The HSO3 is eventually involved in the formation of
sulphuric acid aerosol.
HSO3 + O2 SO3 + H2O
SO3 + H2O H2SO4
The sulphur dioxide that is present in clouds are removed through a process called washout, basically
where sulphur is deposited from the clouds during rain, forming acid rain. This process involves the
formation of sulphur particles, coagulation and diffusional uptake. Whereas, the rainout process involes
the interception of sulphur dioxide molecules during raining, the sulphur dioxide thus diffuses into the
raindrops, also forming acid rain. Washout and rainout are general processes that occur during wet
deposition. Dry deposition is affected by:
Type of precipitate
Intensity of sulphur dioxide
Duration and frequency of rainfall
Amounts of sulphur dioxide relative to sulphate in air
Size distribution of sulphate particles
The direct collection of gaseous and particulate sulphur dioxide on land or water is called dry deposition.
This process removes sulphur from the atmosphere. Dry deposition of sulphur particles can occur:
Directly onto plants
Gravitational settling
Physical/chemical capture of sulphur dioxide particles by moist surfaces.
Sulphur dioxide usually resides in the atmosphere for 1-5 days,where it shall be deposited occationally
through rainfall.
Sulphur dioxide is proven to be harmful to the ecosystem and the environment. For example, exposure to
sulphur dioxide by animals or lifestocks shall lead them to suffer from broichiel constriction and the
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narrowing of the breathing airways. Chronic exposure to sulphur dioxide would result in the swelling of the
mucosal tissues and also aggravate pulmonary diseases.
http://environment.gov.ab.ca/info/library/6615.pdf
http://www.hpa.org.uk/webc/HPAwebFile/HPAweb_C/1287148063808
Ammonia/ azane
http://en.wikipedia.org/wiki/Ammonia
http://en.wikipedia.org/wiki/History_of_the_Haber_process
http://en.wikipedia.org/wiki/Haber-Bosch_process
http://www.chemguide.co.uk/physical/equilibria/haber.html
http://www.kentchemistry.com/links/Kinetics/Haber.htm
http://haberchemistry.tripod.com/
http://chemwiki.ucdavis.edu/Physical_Chemistry/Chemical_Equilibrium/Case_Studies
/Haber_Process
Glass and ceramics
https://en.wikipedia.org/wiki/Silica
https://en.wikipedia.org/wiki/Glass
https://en.wikipedia.org/wiki/History_of_glass
https://en.wikipedia.org/wiki/Glass_production
https://en.wikipedia.org/wiki/Float_glass
https://en.wikipedia.org/wiki/List_of_physical_properties_of_glass
https://en.wikipedia.org/wiki/Fused_silica
https://en.wikipedia.org/wiki/Borosilicate_glass
https://en.wikipedia.org/wiki/Soda-lime_glass
https://en.wikipedia.org/wiki/Lead_glass
http://environment.gov.ab.ca/info/library/6615.pdfhttp://www.hpa.org.uk/webc/HPAwebFile/HPAweb_C/1287148063808http://en.wikipedia.org/wiki/Ammoniahttp://en.wikipedia.org/wiki/History_of_the_Haber_processhttp://en.wikipedia.org/wiki/Haber-Bosch_processhttp://www.chemguide.co.uk/physical/equilibria/haber.htmlhttp://www.kentchemistry.com/links/Kinetics/Haber.htmhttp://haberchemistry.tripod.com/http://chemwiki.ucdavis.edu/Physical_Chemistry/Chemical_Equilibrium/Case_Studies/Haber_Processhttp://chemwiki.ucdavis.edu/Physical_Chemistry/Chemical_Equilibrium/Case_Studies/Haber_Processhttps://en.wikipedia.org/wiki/Silicahttps://en.wikipedia.org/wiki/Glasshttps://en.wikipedia.org/wiki/History_of_glasshttps://en.wikipedia.org/wiki/Glass_productionhttps://en.wikipedia.org/wiki/Float_glasshttps://en.wikipedia.org/wiki/List_of_physical_properties_of_glasshttps://en.wikipedia.org/wiki/Fused_silicahttps://en.wikipedia.org/wiki/Borosilicate_glasshttps://en.wikipedia.org/wiki/Soda-lime_glasshttps://en.wikipedia.org/wiki/Lead_glasshttp://environment.gov.ab.ca/info/library/6615.pdfhttp://www.hpa.org.uk/webc/HPAwebFile/HPAweb_C/1287148063808http://en.wikipedia.org/wiki/Ammoniahttp://en.wikipedia.org/wiki/History_of_the_Haber_processhttp://en.wikipedia.org/wiki/Haber-Bosch_processhttp://www.chemguide.co.uk/physical/equilibria/haber.htmlhttp://www.kentchemistry.com/links/Kinetics/Haber.htmhttp://haberchemistry.tripod.com/http://chemwiki.ucdavis.edu/Physical_Chemistry/Chemical_Equilibrium/Case_Studies/Haber_Processhttp://chemwiki.ucdavis.edu/Physical_Chemistry/Chemical_Equilibrium/Case_Studies/Haber_Processhttps://en.wikipedia.org/wiki/Silicahttps://en.wikipedia.org/wiki/Glasshttps://en.wikipedia.org/wiki/History_of_glasshttps://en.wikipedia.org/wiki/Glass_productionhttps://en.wikipedia.org/wiki/Float_glasshttps://en.wikipedia.org/wiki/List_of_physical_properties_of_glasshttps://en.wikipedia.org/wiki/Fused_silicahttps://en.wikipedia.org/wiki/Borosilicate_glasshttps://en.wikipedia.org/wiki/Soda-lime_glasshttps://en.wikipedia.org/wiki/Lead_glass7/27/2019 chm flio HAHA FAIL
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http://en.wikipedia.org/wiki/Transparent_conducting_film
https://en.wikipedia.org/wiki/Photochromic_lens
http://en.wikipedia.org/wiki/Ceramic
http://en.wikipedia.org/wiki/Superconductivity
Sulfur dioxide is introduced with steam and oxides of nitrogeninto large chambers lined withsheet leadwhere the gases are sprayed down with water and chamber acid. The sulfur dioxide and
nitrogen dioxide dissolve and over a period of approximately 30 minutes the sulfur dioxide is oxidized to
sulfuric acid. The presence of nitrogen dioxide is necessary for the reaction to proceed. The process is
highly exothermic, and a major consideration of the design of the chambers was to provide a way to
dissipate the heat formed in the reactions.
Early plants used very large lead-lined wooden rectangular chambers (Faulding box chambers) that were
cooled by ambient air. The internal lead sheathing served to contain the corrosive sulfuric acid and to
render the wooden chambers waterproof. Around the turn of the nineteenth century, such plants required
about half a cubic meter of volume to process the sulfur dioxide equivalent of a kilogram of burned sulfur.
In the mid 19th century, French chemist Gay-Lussacredesigned the chambers as stoneware packed
masonry cylinders. In the 20th century, plants using Mills-Packard chambers supplanted the earlierdesigns. These chambers were tall tapered cylinders that were externally cooled by water flowing down
the outside surface of the chamber.
Sulfur dioxide for the process was provided by burningelemental sulfuror by theroastingofsulfur
containing metal oresin a stream of air in a furnace. During the early period of manufacture, nitrogen
oxides were produced by the decomposition ofniterat high temperature in the presence of acid, but this
process was gradually supplanted by the air oxidation ofammoniato nitric oxide in the presence of a
catalyst. The recovery and reuse of oxides of nitrogen was an important economic consideration in the
operation of a chamber process plant.
In the reaction chambers,nitric oxidereacts with oxygen to produce nitrogen dioxide. Liquid from the
bottom of the chambers is diluted and pumped to the top of the chamber and sprayed downwards in afine mist. Sulfur dioxide and nitrogen dioxide are absorbed in the liquid and react to form sulfuric acid and
nitric oxide. The liberated nitric oxide is sparingly soluble in water and returns to the gas in the chamber
where it reacts with oxygen in the air to reform nitrogen dioxide. Some percentage of the nitrogen oxides
are sequestered in the reaction liquor asnitrosylsulfuric acidand as nitric acid, so fresh nitric oxide must
be added as the process proceeds. Later versions of chamber plants included a high temperature Glover
tower to recover the nitrogen oxides from the chamber liquor, while concentrating the chamber acid to as
much as 78% H2SO4. Exhaust gases from the chambers are scrubbed by passing into a tower through
http://en.wikipedia.org/wiki/Transparent_conducting_filmhttps://en.wikipedia.org/wiki/Photochromic_lenshttp://en.wikipedia.org/wiki/Ceramichttp://en.wikipedia.org/wiki/Superconductivityhttp://en.wikipedia.org/wiki/Sulfur_dioxidehttp://en.wikipedia.org/wiki/Nitrogen_oxidehttp://en.wikipedia.org/wiki/Leadhttp://en.wikipedia.org/wiki/Leadhttp://en.wikipedia.org/wiki/Joseph_Louis_Gay-Lussachttp://en.wikipedia.org/wiki/Sulfurhttp://en.wikipedia.org/wiki/Sulfurhttp://en.wikipedia.org/wiki/Roasting_(metallurgy)http://en.wikipedia.org/wiki/Roasting_(metallurgy)http://en.wikipedia.org/wiki/Sulfide_mineralhttp://en.wikipedia.org/wiki/Sulfide_mineralhttp://en.wikipedia.org/wiki/Nitrogen_oxidehttp://en.wikipedia.org/wiki/Nitrogen_oxidehttp://en.wikipedia.org/wiki/Nitrehttp://en.wikipedia.org/wiki/Ammoniahttp://en.wikipedia.org/wiki/Ammoniahttp://en.wikipedia.org/wiki/Nitric_oxidehttp://en.wikipedia.org/wiki/Nitric_oxidehttp://en.wikipedia.org/wiki/Nitric_oxidehttp://en.wikipedia.org/wiki/Nitric_oxidehttp://en.wikipedia.org/wiki/Nitrogen_dioxidehttp://en.wikipedia.org/wiki/Nitrogen_dioxidehttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Transparent_conducting_filmhttps://en.wikipedia.org/wiki/Photochromic_lenshttp://en.wikipedia.org/wiki/Ceramichttp://en.wikipedia.org/wiki/Superconductivityhttp://en.wikipedia.org/wiki/Sulfur_dioxidehttp://en.wikipedia.org/wiki/Nitrogen_oxidehttp://en.wikipedia.org/wiki/Leadhttp://en.wikipedia.org/wiki/Joseph_Louis_Gay-Lussachttp://en.wikipedia.org/wiki/Sulfurhttp://en.wikipedia.org/wiki/Roasting_(metallurgy)http://en.wikipedia.org/wiki/Sulfide_mineralhttp://en.wikipedia.org/wiki/Sulfide_mineralhttp://en.wikipedia.org/wiki/Nitrogen_oxidehttp://en.wikipedia.org/wiki/Nitrogen_oxidehttp://en.wikipedia.org/wiki/Nitrehttp://en.wikipedia.org/wiki/Ammoniahttp://en.wikipedia.org/wiki/Nitric_oxidehttp://en.wikipedia.org/wiki/Nitric_oxidehttp://en.wikipedia.org/wiki/Nitrogen_dioxidehttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acid7/27/2019 chm flio HAHA FAIL
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which some of the Glover acid flows over broken tile. Nitrogen oxides are absorbed to form nitrosylsulfuric
acid which is then returned to the Glover tower to reclaim the oxides of nitrogen.
Sulfuric acid produced in the reaction chambers is limited to about 35% concentration. At higher
concentrations,nitrosylsulfuric acidprecipitates on the lead walls aschamber crystalsand is no longer
able to catalyzethe oxidation reactions.
Acid-base properties [edit]
As an acid, sulfuric acid reacts with most bases to give the corresponding sulfate. For
example, the blue coppersalt copper(II) sulfate, commonly used forelectroplatingand asa fungicide, is prepared by the reaction ofcopper(II) oxide with sulfuric acid:
CuO (s) + H2SO4 (aq) CuSO4 (aq) + H2O (l)
Sulfuric acid can also be used to displace weaker acids from their salts. Reaction
with sodium acetate, for example, displaces acetic acid, CH3COOH, and
formssodium bisulfate:
H2SO4 + CH3COONa NaHSO4 + CH3COOH
Similarly, reacting sulfuric acid with potassium nitrate can be used to
producenitric acid and a precipitate ofpotassium bisulfate. When combined
with nitric acid, sulfuric acid acts both as an acid and a dehydrating agent,
forming the nitronium ion NO+
2, which is important in nitration reactions involvingelectrophilic aromatic
substitution. This type of reaction, where protonation occurs on
anoxygenatom, is important in many organic chemistryreactions, such
as Fischer esterificationand dehydration of alcohols.
http://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Catalysishttp://en.wikipedia.org/wiki/Catalysishttp://en.wikipedia.org/w/index.php?title=Sulfuric_acid&action=edit§ion=7http://en.wikipedia.org/wiki/Base_(chemistry)http://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Copper(II)_sulfatehttp://en.wikipedia.org/wiki/Electroplatinghttp://en.wikipedia.org/wiki/Electroplatinghttp://en.wikipedia.org/wiki/Fungicidehttp://en.wikipedia.org/wiki/Copper(II)_oxidehttp://en.wikipedia.org/wiki/Sodium_acetatehttp://en.wikipedia.org/wiki/Sodium_acetatehttp://en.wikipedia.org/wiki/Acetic_acidhttp://en.wikipedia.org/wiki/Sodium_bisulfatehttp://en.wikipedia.org/wiki/Sodium_bisulfatehttp://en.wikipedia.org/wiki/Sodium_bisulfatehttp://en.wikipedia.org/wiki/Potassium_nitratehttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Potassium_bisulfatehttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Nitronium_ionhttp://en.wikipedia.org/wiki/Nitrationhttp://en.wikipedia.org/wiki/Electrophilic_aromatic_substitutionhttp://en.wikipedia.org/wiki/Electrophilic_aromatic_substitutionhttp://en.wikipedia.org/wiki/Electrophilic_aromatic_substitutionhttp://en.wikipedia.org/wiki/Oxygenhttp://en.wikipedia.org/wiki/Oxygenhttp://en.wikipedia.org/wiki/Oxygenhttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Fischer_esterificationhttp://en.wikipedia.org/wiki/Fischer_esterificationhttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Nitrosylsulfuric_acidhttp://en.wikipedia.org/wiki/Catalysishttp://en.wikipedia.org/w/index.php?title=Sulfuric_acid&action=edit§ion=7http://en.wikipedia.org/wiki/Base_(chemistry)http://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Copper(II)_sulfatehttp://en.wikipedia.org/wiki/Electroplatinghttp://en.wikipedia.org/wiki/Fungicidehttp://en.wikipedia.org/wiki/Copper(II)_oxidehttp://en.wikipedia.org/wiki/Sodium_acetatehttp://en.wikipedia.org/wiki/Acetic_acidhttp://en.wikipedia.org/wiki/Sodium_bisulfatehttp://en.wikipedia.org/wiki/Potassium_nitratehttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Potassium_bisulfatehttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Nitronium_ionhttp://en.wikipedia.org/wiki/Nitrationhttp://en.wikipedia.org/wiki/Electrophilic_aromatic_substitutionhttp://en.wikipedia.org/wiki/Electrophilic_aromatic_substitutionhttp://en.wikipedia.org/wiki/Oxygenhttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Fischer_esterification7/27/2019 chm flio HAHA FAIL
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Solid state structure of the [D3SO4]+ ion present in [D3SO4]
+[SbF6]-, synthesized by
using DF in place of HF. (see text)
When allowed to react withsuperacids, sulfuric acid can act as a base and be
protonated, forming the [H3SO4]+ion. Salt of [H3SO4]
+ have been prepared using
the following reaction in liquid HF:
((CH3)3SiO)2SO2 + 3 HF + SbF5 [H3SO4]+[SbF6]
- + 2 (CH3)3SiF
The above reaction is thermodynamically favored due to the high bond
enthalpyof the SiF bond in the side product. Protonation using
simply HF/SbF5, however, have met with failure, as pure sulfuric acid
undergoes self-ionizationto give [H3O]+ ions, which prevents the
conversion of H2SO4 to [H3SO4]+ by the HF/SbF5 system:
[16]
2 H2SO4 [H3O]+ + [HS2O7]
-
Reactions with metals and strong oxidizing
property [edit]Dilute sulfuric acid reacts with metals via a single displacement
reaction as with other typicalacids, producinghydrogengas
andsalts (the metal sulfate). It attacks reactive metals (metals at
positions abovecopperin thereactivity series) such
asiron,aluminium,zinc,manganese,magnesiumand nickel.
Fe (s) + H2SO4 (aq) H2 (g) + FeSO4 (aq)
However, concentrated sulfuric acid is a strong oxidizing
agent[17] and does not react with metals in the same way as other
typicalacids. Sulfur dioxide,waterand SO42- ions are evolved
instead of the hydrogenandsalts.
2 H2SO4 + 2 e- SO2 + 2 H2O + SO4
2-
It can oxidize non-active metals such as tin and copper,
depending upon the temperature of it like thenitric acid.
Cu + 2 H2SO4 SO2 + 2 H2O + SO42- + Cu2+
http://en.wikipedia.org/wiki/Deuteriumhttp://en.wikipedia.org/wiki/Superacidhttp://en.wikipedia.org/wiki/Superacidhttp://en.wikipedia.org/wiki/Hydrogen_fluoridehttp://en.wikipedia.org/wiki/Bond_enthalpyhttp://en.wikipedia.org/wiki/Bond_enthalpyhttp://en.wikipedia.org/wiki/Bond_enthalpyhttp://en.wikipedia.org/wiki/Fluoroantimonic_acidhttp://en.wikipedia.org/wiki/Fluoroantimonic_acidhttp://en.wikipedia.org/wiki/Molecular_autoionizationhttp://en.wikipedia.org/wiki/Molecular_autoionizationhttp://en.wikipedia.org/wiki/Sulfuric_acid#cite_note-InorgChem-16http://en.wikipedia.org/w/index.php?title=Sulfuric_acid&action=edit§ion=8http://en.wikipedia.org/wiki/Acidhttp://en.wikipedia.org/wiki/Acidhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Salthttp://en.wikipedia.org/wiki/Salthttp://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Reactivity_serieshttp://en.wikipedia.org/wiki/Ironhttp://en.wikipedia.org/wiki/Ironhttp://en.wikipedia.org/wiki/Ironhttp://en.wikipedia.org/wiki/Aluminiumhttp://en.wikipedia.org/wiki/Zinchttp://en.wikipedia.org/wiki/Zinchttp://en.wikipedia.org/wiki/Zinchttp://en.wikipedia.org/wiki/Manganesehttp://en.wikipedia.org/wiki/Manganesehttp://en.wikipedia.org/wiki/Magnesiumhttp://en.wikipedia.org/wiki/Magnesiumhttp://en.wikipedia.org/wiki/Magnesiumhttp://en.wikipedia.org/wiki/Nickelhttp://en.wikipedia.org/wiki/Oxidizing_agenthttp://en.wikipedia.org/wiki/Oxidizing_agenthttp://en.wikipedia.org/wiki/Oxidizing_agenthttp://en.wikipedia.org/wiki/Oxidizing_agenthttp://en.wikipedia.org/wiki/Sulfuric_acid#cite_note-OA-17http://en.wikipedia.org/wiki/Sulfuric_acid#cite_note-OA-17http://en.wikipedia.org/wiki/Acidhttp://en.wikipedia.org/wiki/Acidhttp://en.wikipedia.org/wiki/Sulfur_dioxidehttp://en.wikipedia.org/wiki/Waterhttp://en.wikipedia.org/wiki/Waterhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Salthttp://en.wikipedia.org/wiki/Salthttp://en.wikipedia.org/wiki/Tinhttp://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Nitric_acidhttp://en.wikipedia.org/wiki/Deuteriumhttp://en.wikipedia.org/wiki/Superacidhttp://en.wikipedia.org/wiki/Hydrogen_fluoridehttp://en.wikipedia.org/wiki/Bond_enthalpyhttp://en.wikipedia.org/wiki/Bond_enthalpyhttp://en.wikipedia.org/wiki/Fluoroantimonic_acidhttp://en.wikipedia.org/wiki/Molecular_autoionizationhttp://en.wikipedia.org/wiki/Sulfuric_acid#cite_note-InorgChem-16http://en.wikipedia.org/w/index.php?title=Sulfuric_acid&action=edit§ion=8http://en.wikipedia.org/wiki/Acidhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Salthttp://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Reactivity_serieshttp://en.wikipedia.org/wiki/Ironhttp://en.wikipedia.org/wiki/Aluminiumhttp://en.wikipedia.org/wiki/Zinchttp://en.wikipedia.org/wiki/Manganesehttp://en.wikipedia.org/wiki/Magnesiumhttp://en.wikipedia.org/wiki/Nickelhttp://en.wikipedia.org/wiki/Oxidizing_agenthttp://en.wikipedia.org/wiki/Oxidizing_agenthttp://en.wikipedia.org/wiki/Sulfuric_acid#cite_note-OA-17http://en.wikipedia.org/wiki/Acidhttp://en.wikipedia.org/wiki/Sulfur_dioxidehttp://en.wikipedia.org/wiki/Waterhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Salthttp://en.wikipedia.org/wiki/Tinhttp://en.wikipedia.org/wiki/Copperhttp://en.wikipedia.org/wiki/Nitric_acid7/27/2019 chm flio HAHA FAIL
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Lead and tungsten, however, are resistant to sulfuric
acid.
Reactions with non-metals [edit]
Hot concentrated sulfuric acid oxidizes non-metals such
as carbon andsulfur.
C + 2 H2SO4 CO2 + 2 SO2 + 2 H2O
S + 2 H2SO4 3 SO2 + 2 H2O
Reaction with sodiumchloride [edit]
It reacts with sodium chloride, and
gives hydrogen chloridegasandsodium
bisulfate:
NaCl + H2SO4 NaHSO4 + HCl
Electrophilic aromaticsubstitution [edit]
Benzene undergoes electrophilic aromatic
substitution with sulfuric acid to give the
corresponding sulfonic acids:[18]
Although nearly 99% sulfuric acid can be made, the subsequent loss ofSO3 at the boiling point
brings the concentration to 98.3% acid. The 98% grade is more stable in storage, and is the
usual form of what is described as "concentrated sulfuric acid." Other concentrations are used
for different purposes. Some common concentrations are:[9][10]
"Chamber acid" and "tower acid" were the two concentrations of sulfuric acid produced by
the lead chamber process, chamber acid being the acid produced in lead chamber itself (
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2H2SO4 H3SO4+ + HSO4
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