8.
2 Industrial Gases
Industrial Gases
 
Industrial gases perform varied and essential functions in
our economy.  Some are raw materials for the manufacture
of other chemicals.  This is particularly true of oxygen,
nitrogen, and hydrogen.  Nitrogen preserves the flavor of
packaged foods by reducing chemical action leading to
rancidity of canned fats.  Some gases are essential
medicaments, like oxygen and helium.  However, many of
these gases their liquids,  and their solids have a common
application in creating cold, by absorbing heat upon
evaporized by performing work, or by melting.  In past
decades,  the outstanding examples of this have been liquid
carbon dioxide and dry ice.  On the other hand, with the
modern expansion of industry, a new division of engineering
has risen called cryogenics. This widely embracing term
pertains to the production and use of extreme cold at
temperatures below -100 deg centigrade.  The term has
been applied very extensively during the last decade and is
exemplified by the use of liquid hydrogen, oxygen and
fluorine in missiles for military and space projects. New
cryogenic techniques have been worked out, reducing the
cost of liquefaction, and improving and simplifying the
equipment used for storage, handling and shipment of very
cold liquids and gases.  The economic advantage of using
cryogenic liquids is apparent when it is realized that a
cylinder weighing 113 kg contains 169 kg of liquid oxygen
(equivalent to 126 cubic meters of gaseous oxygen at
normal temperature and pressure).  Eighteen small cylinders
of of gaseous oxygen contain a total of 166 kg of oxygen
gas at a pressure of 15  MPa, but they weigh 1090 kg.  frostbite.
Cryogenic liquids are stored and shipped in tanks or large
tank cars built on the multiple-walled vacuum bottle (Dewar)
principle.  The value of cryogenic gases, oxygen, nitrogen,
argon, helium, and hydrogen (merchant only) , amounted to
$1250 million in 1980.  Of the total, oxygen accounted for
$500 million, nitrogen $450 million, and hydrogen $110
million.  These cryogenic, or supercold, cause fundamental
changes in properties of materials.  Cryogenics is being
applied to rocket propulsion, infrared photooptics and
electronic data processing, with newer applications in
magnetics and high-vacuum pumping.  The major
application of cryogenics to the chemical field is in the
manufacture of nitrogen for ammonia production, and in
metallurgy , where the use of oxygen hastens (by 25 % or
more) the production pf steel in open hearth furnaces,
converters and even blast furnaces for pig iron. 
Carbon dioxide
Carbon dioxide in liquid and solid forms has been known for
over a century.  Although Thilolier produced solid carbon
dioxide in 1835 from the liquid material, it was not until
1924 that  the solid product gained industrial importance
through its first and still most important use for
refrigaration.  The production of merchant carbon dioxide in
1981 was about 3.6 x 106 tons  total for the gaseous, liquid
and solid forms.
 
Industrial gases are gaseous at room temperature and
pressure and used in various industries. These industries
include chemicals, power, medicine, electronics, aerospace,
and even food. As useful as these gases are, they may be
flammable and come with other dangers.
Hydrogen (H2)
Hydrogen is the most common element in the universe, but
it takes a lot of processing to extract and contain pure
hydrogen. This gas can be liquefied, compressed, or mixed
with other gases for various uses. Hydrogen fuels space
rockets, helps the steel welding process, powers alternative
energy cars, refines crude oil, aids in the production of
common household chemicals, and more.
The main danger of hydrogen is its explosiveness. When
exposed to oxygen, even a regular static shock can set
hydrogen on fire. On the opposite end of the spectrum,
liquid hydrogen is extremely cold and can cause severe
 
Acetylene (C2H2)
Acetylene is most notably used to weld materials at very
high temperatures–too high for most industrial gases to
achieve. It’s also used in the chemicals industry to synthesize
substances like Vitamin A and some plastics.
Like hydrogen, acetylene is highly flammable and explosive.
Acetylene can also form explosive compounds when
combined with metals like brass and silver. A portable gas
leak detector can tell you if there is too much acetylene in
your work environment.
Oxygen (O2)
Oxygen is manufactured in compressed, liquid, and mixed
forms. It’s most commonly known as the main gas necessary
to sustain human life. Thus, oxygen tanks help people with
many medical conditions that interfere with breathing.
Other uses of industrial oxygen include launching rockets,
laser cutting, oxidizing chemicals, cleaner combustion,
fermentation, food preservation, and wastewater treatment.

Oxygen itself is not flammable. However, an overabundance

of oxygen can help other materials catch fire, even materials
that are flame-retardant in normal air. People on oxygen
support must stay away from heat sources and never smoke
near their oxygen tank.

Methane (CH4)

Methane comes from fermenting organic matter and is a

major component in natural gas. It’s most commonly used
to produce energy for homes and industries. This substance
is also used in plastics, fertilizers, and more. Methane can
help produce other industrial gases.

Methane is explosive and a major greenhouse gas. High

levels of methane in an enclosed space can cause
asphyxiation.

These and other industrial gases benefit industries in

enormous ways that outweigh the risks as long as you use
adequate safety measures. Always store gases properly and
use a portable multi gas detector to detect gas leaks before
they become hazardous.
8.3 Industrial Acids-2
Sulfuric acid is the largest-volume industrial chemical
produced in the world (200 million tons per year).
Concentrated sulfuric acid (93-98 %) is used in the
Manufacturing Process of Industrial Acid
manufacture of fertilizers, explosives, dyes, and petroleum
Acids may be identified as either strong or weak acids based products.
on how completely they dissociate into their ions in water. A
 
strong acid, such as hydrochloric acid, completely
dissociates into its ions in water. A weak acid only partly Mining and Manufacture of Sulfur
dissociates into its ions, so the solution contains water, ions,
 Elemental sulfur ores were mined manually
and the acid (e.g., acetic acid).
 The sulfur in these ores was then concentrated by
 
burning part of the sulfur piles to melt the
These are examples of types of acids and specific acids: remainder, drawing off the liquid, and casting it into
molds
 Arrhenius acid
- Hydrochloric acid  

    - Nitric acid Schematic diagram of Frasch Process

    - Sulfuric acid

  
    - Acetic acid
 
 Lewis acid
- Borane (BH3) Claus Process
- Aluminum Chloride (AlCl3)
- Iron (III) Bromide (FeBr3)
  
 Hydrofluoric acid
 
 Stomach acid (which contains hydrochloric acid)
The acid feed (191,000 std m3/day, 38°C) is composed of
 Vinegar (which contains acetic acid) 75.1% H2S, 24.7% CO2, and 0.2%
hydrocarbons. (Monsanto Enviro-Chem.)
 Citric acid (found in citrus fruits)
Location Temperature, C° Location Temperature, C°
 

Tannic Acid is quite a colossal molecule, relatively speaking. 1 1049 6 166

Its molecular formula is a substantial C72H52O46 with a
2 379 7 208
molecular mass of 1701 grams/mole. And even so, it has a
considerable appearance, turning pond water murky and 3 149 8 224
brownish giving a sense of eerie cloudiness.
4 258 9 133
Sulfur and Sulfuric Acid
5 332 10 538
Sulfur is one of the most important and basic material in the
Claus-type sulfur recovery unit of the Okotoks plant
chemical process industries. It exists in nature both in the
free state and combined in ores such as pyrite(FeS2),  
sphalerite (ZnS), and chalcopyrite (CuFeS2). It is also an
important constituent of petroleum and natural gas (as Sulfuric Acid
H2S). The largest application of sulfur is in the manufacture  It is the agent for sulfate formation and for
of sulfuric acid. sulfonation, but more frequently it is used because
 it is a rather strong and cheaply priced inorganic of metals like zinc or lead. If so this stage can be
acid. skipped.

 It is employed in the manufacture of fertilizers,  

leather, and tin plate, in the refining of petroleum,
2. The converter
and in the dyeing of fabrics.
 The converter contains trays or layers of porous
 
pellets of a catalyst, vanadium (V) oxide (V2O5).
Hydrates of Sulfuric Acid The sulphur dioxide reacts with more air to form
sulphur trioxide.  This reaction is reversible and
Melting Specific reaches an equilibrium.  It is also an exothermic
Formula
Point, °C Gravity reaction and the temperature will rise to over
600oC. The mixture is continuously cooled to
Sulfuric acid
H2SO7 35 1.9^20° 400oC between each tray.
fuming

100% H2SO4 10.37 1.834^18°/4 SO2(g) + ½O2(g)  <---> SO3(g)

Monohydrat  As the temperature rises the equilibrium shifts to

H2SO4-H20 8.48 1.842^15°/4
e the left (not forming SO3). To counter this the
gases are allowed to cool slightly before they pass
H2SO4- over the next layer of catalyst, by carefully
Dihydrate -38.57 1.650^0°/4
2H2O controlling the process almost all sulphur dioxide is
converted to sulphur trioxide.
 

Production of Sulfuric Acid

  
Sulfuric acid is made in several stages from SO2, obtained
 
from the oxidation of sulphur or collection of SO2 from the
smelting of sulfide ores such as copper, zinc or lead. This 3. The absorption tower
second collection of SO2 is very attractive as it is utilising the
 Sulphur trioxide will dissolve in water to form our
by-products of other processes and reduces emissions and
final goal of sulfuric acid. However it is violently
waste.
exothermic and usually results in a mist of sulfuric
SO2(g) ---> SO3(g) ---> H2SO4(aq) acid droplets that are very difficult to control.

   In practice the sulphur trioxide dissolves almost

completely and is bubbled through concentrated
Three main steps:
sulfuric acid (that contains relatively little water) to
1.Furnace or Burner (Only necessary if raw sulfur is used) form 98% sulfuric acid, known as Oleum (H2S2O7)

 Air is cleaned by electrostatic precipitation, dried a)SO3(g) + H2SO4(l)  ---> H2S2O7(l)

then heated to approx. 600oC.
b)H2S2O7(l) + H2O(l)  ---> H2SO4(l)
 Pure (liquid) sulphur is sprayed under pressure into
 
the furnace, reacting with the oxygen in the air. The
product is sulphur dioxide Waste products

S(l) + O2(g) --->SO2(g) Most of the “waste” heat is recovered  and used to heat
water, in this way much of the energy can be reused.
 Alternative sources of sulphur dioxide are also
Because of this many sulfuric acid plants are co-located with
used, either extracted from natural gas (some
other industrial processes.
deposits contain a lot of hydrogen sulphide) or
from the roasting of sulphide ores in the extraction
Great care needs to be taken with the waste gases that are 2NaCl   +  H2SO4 ------------------>Na2SO4      +    2HCl
formed.  There will be small amounts of sulphur dioxide,
 
sulphur trioxide, sulfuric acid and possibly particle sulphur,
all of which must be removed to prevent environmental  
damage. There is a double absorption method that can be
used to prevent SO2 emissions. After a first round of
processing through the  converter, any SO2 that was not
converted into SO3, can be collected and passed back
through. SO2 that is released into the atmosphere can
cause acid rain and respiratory irritants.

The Contact Process

Hydrochloric or Muriatic Acid

Hydrogen Chloride is a gas at ordinary temperature and

pressure. Aqueous solutions of it are known as hydrochloric
acid or, if the HCl in solution is of the commercial grade, as
muriatic acid.

Manufacture of HCl

 A by-product of chlorination of both aromatic and

aliphatic hydrocarbons
(C6H6 + Cl2 ----------> C6H5Cl + HCl)

 Reacting salt and sulfuric acid

 Combustion of hydrogen and chlorine

 Hargreaves-type operations :
(4NaCl + 2SO2 + O2 + 2H2O -------->2Na2SO4 +
4HCl)

Preparation of HCl in Laboratory

By synthesis,

   H2     +    Cl -----------------> HCl

Salt  +   Acid                Other Salt    +   Other Acid

                                     >200°C