Objectives

• Outline the steps involved in industrial

production of hydrogen peroxide
• Comprehend pertinent chemical
reactions involved in the
production of hydrogen peroxide
 Scope of Discussion

 Inorganic Peroxy-compounds
 Hydrogen Peroxide
 Peroxymonosulfuric Acid
 Sodium Peroxide
 Inorganic Peroxy-compounds
Inorganic chemistry describes
the properties and behaviors of all
elements and their compounds
EXCEPT for the majority of the carbon
compounds.
The term organic was coined to the
fact that it was previously believed
that organic compounds only occur
in living organisms, and inorganic
compounds were thought to be
present in minerals and other non-
living matter. However, Friedrich
Wohler synthesized urea from
ammonium cyanate.
 Inorganic Peroxy-compounds

A peroxide or peroxy
compound is a chemical
compound characterized by two
linked oxygen atoms. The most
widely used peroxy compound is
hydrogen peroxide. All the alkali
metals and alkali earth metals
can form peroxides, and sodium
peroxide (Na2O2) is the most
important in an industrial sense.
 Peroxygens
Where are they found?
Commonly used for sterilisation, particularly of surgical tools
and surfaces, and antisepsis.

How do they work?

Peroxygen compounds have a broad spectrum of activity,
effective against bacteria, fungi, and viruses. They work by reacting
with proteins and enzymes, and making cell walls more permeable.
 Peroxygens
Advantages:
The breakdown products of peroxygen compounds are
environmentally-friendly: for hydrogen peroxide, water and oxygen are
produced, whilst peracetic acid creates oxygen and acetic acid as
decomposition products.
Disadvantages:
Their instability does mean that stabilisers sometimes need to be
added to solutions. More so, their effectiveness wanes at low
concentrations.
 Hydrogen Peroxide
Hydrogen Peroxide (H2O2) is a colorless
(blue in thick layers), odorless liquid at room
temperature. It is the simplest peroxide and is
commercially available in aqueous solution over
a wide concentration range.
Because of its strong oxidizing properties
and that it leaves no residue, it is used as a
* It was first produced from the
powerful bleaching agent in paper production reaction of barium peroxide (BaO2)
and can also be used as disinfectant and oxidizer and sulfuric acid (H2SO4) for use as
an antiseptic.
 Hydrogen Peroxide
History
1799
oAlexander von Humboldt synthesized
one of the first synthetic peroxides,
barium peroxide (BaO2) as a by-product.

Alexander von Humboldt Barium Peroxide (BaO2)

 Hydrogen Peroxide
History
1818
oIt was first identified and isolated in 1818 by Louis
Jacques Thénard and was initially described as
“oxidized water”
oThénard's process was used from the end of the
19th century until the middle of the 20th century.
Louis Jacques Thénard
 Hydrogen Peroxide
Chemical formula: H2O2
Molar mass: 34.0147 g/mol
Physical State: Liquid
Appearance: Colorless
Taste: Bitter
Melting point: -0.43 °C
Boiling point: 150.2 °C
Solubility in water: Miscible * Hydrogen peroxide is unstable
Main hazards: Strong oxidizer and decomposes readily
 Hydrogen Peroxide
USES
At low concentrations (3-9%):
• Bleaching Agent
• Antiseptic and Disinfectant
At high concentrations (40%):
• Oxidizing Agent
• Oxidizer in rocket motors for
small rockets
Industry Application
Pulp and paper Bleaching wood pulp
Mining Detoxification of cyanide
tailings
Textile bleaching Bleaching of cotton fabrics
Wool scouring Bleaching of wool
Waste water treatment Measuring dissolved oxygen;
destroying soluble cyanides,
sulfides, and phenols
Packaging Aseptic packaging of milk and
fruit juice
 Hydrogen Peroxide
Manufacture
Electrolytic (Inorganic) method:
• Electrochemical formation of peroxydisulfuric acid (H2S2O8)
or peroxydisulfates (S2O82−)

Organic method:
• Anthraquinone process
• Oxidation of propane or propane derivative (isopropyl
alcohol)
 Hydrogen Peroxide
Electrolytic (Inorganic) method:

1. Formation of peroxydisulfate intermediates

2. Hydrolysis
3. Distillation
 Hydrogen Peroxide
First step

• Ammonium bisulfate (NH4)HSO4 or Sulfuric acid (H2SO4) may be used as

the starting material (electrolyte).
Disadvantages
H2SO4 electrolyte has low current efficiency (70-75%)
(NH4)HSO4 electrolyte causes crystallization problems and blocks the cell
 Hydrogen Peroxide
First step

• The electrolyte is fed into an electrolysis tank at

35°C
• Conversion takes place in the anode
• Product: Peroxydisulfate or persulfate (S2O82−)

Electrolysis tank
 Hydrogen Peroxide
Second step

• Hydrolysis of the persulfate (with steam) in an evaporator at 60 to

100°C
• Product: Dilute aqueous H2O2 solution
 Hydrogen Peroxide
Third step
• Dilute aqueous H2O2 solution is distilled in a distillation column
• Product: 30% w/w H2O2
• The cathode liquor (after purification) and bisulfate from the
evaporator are recycled back to the cells
Disadvantages of the process
The electrolytic process requires that the electrolyte be continuously
purified and also has very high capital and power requirements
 Hydrogen Peroxide
Hydrogenation
Anthraquinone Process:

1. Hydrogenation
Filtration
2. Filtration Oxidation
3. Oxidation
4. Extraction
Extraction
 Hydrogen Peroxide
Hydrogenation

Anthraquinone 2 - alkylanthraquinol
• Anthraquinone is hydrogenated to 2 - alkylanthraquinol using H2 gas and
Raney nickel, nickel, palladium or platinum as catalyst
• *Raney nickel is easily deactivated by dissolved oxygens or hydrogen
peroxide, and is pyrophoric
• Usage of small amounts of palladium along with alumina as support is used
instead
 Hydrogen Peroxide
Hydrogenation

Anthraquinone 2 - alkylanthraquinol

• Hydrogenation stage is carefully controlled to avoid over-

hydrogenation of the anthraquinone rings
• Operating conditions are 45°C and 1-3 atm
• Equipment: Hydrogenator
 Hydrogen Peroxide
Filtration

• The working solution that now contains 2 – alkylanthraquinol is then

filtered to remove any trace levels of catalyst
• Failure to remove the catalyst will result in decomposition of hydrogen
peroxide in later stages of manufacturing, reducing yields and causing
potential hazards
• The recovered catalyst is recycled back to the hydrogenator
 Hydrogen Peroxide
Oxidation

2 - alkylanthraquinol Anthraquinone

• The solution is oxidized by blowing air through it

• No catalyst is used
• Often referred to as auto-oxidation
• Product: Anthraquinone solution containing 0.5 to 1%
w/w H2O2 Oxidizer
 Hydrogen Peroxide
Extraction
• Solution is put into a liquid-liquid extraction
column where demineralized water is added
• H2O2-Water solution flows down the column
while the quinone solution is pumped up the
column and recycled back to the
hydrogenator
• Operating conditions are 25 to 40°C and the
product is aqueous solution containing 40%
H2O2
 Hydrogen Peroxide
Oxidation of propane or isopropyl alcohol
• The side products are a variety of
oxygenated organic species:
propylene, methane, and ethylene
• 15-17% w/w H2O2 can be obtained
• This can be conducted either in the
liquid phase or in the vapor phase.
• 25-30% w/w H2O2 can be obtained
• Distillation of acetone and
unreacted alcohol will produce
concentrated H2O2
 Peroxymonosulfuric Acid
Peroxymonosulfuric acid (H2SO5) was
first described in 1898 by Heinrich Caro,
after whom it is named. Caro's acid is one of
the strongest oxidants known (E0 = +2.51 V)
and is highly explosive.
IUPAC name:
(Dioxidanido)hydroxidodioxidosulfur
Other names:
Peroxysulfuric acid
Persulfuric acid
 Peroxymonosulfuric Acid
Chemical formula: H2SO5
Molar mass: 114.078 g/mol
Appearance: White crystals
Density: 2.239 g/cm3
(solutions) 1.7 – 1.8 g/cm3
Melting point: 45 °C
Boiling point: Decomposes
Solubility in water: Miscible
*Reacts violently with many organic solvents
Coordination geometry: Tetrahedral at S
Main hazards: Strong oxidizer
 Peroxydisulfuric Acid
H2SO5 is sometimes confused with
H2S2O8. Peroxydisulfuric acid is a sulfur
oxoacid, also called as Marshall's acid. Its
salts, commonly known as persulfates, are
industrially important as powerful oxidizing
agents. The acid is prepared by the reaction of
chlorosulfuric acid with hydrogen
peroxide:
2ClSO2OH + H2O2 → H2S2O8 + 2 HCl
 Peroxydisulfuric Acid
The acid is prepared by the reaction of chlorosulfuric acid with hydrogen peroxide:

2ClSO2O + O2 → S2O8 + 2 Cl
 Peroxymonosulfuric Acid
Synthesis and production
The laboratory scale preparation of Caro's acid:
1. Combination of chlorosulfuric acid and hydrogen peroxide
H2O2 + ClSO2OH ⇌ H2SO5 + HCl
Advantage: Pure Caro’s acid (94-97%) can be obtained.
Impurities: H2S2O8 and traces of Cl
 Further purification by partial remelting. The yield is 50-70%.
Disadvantage: Unstable acid which rapidly degrades and become
diluted.
 Peroxymonosulfuric Acid
Synthesis and production
1. Combination of chlorosulfuric acid and hydrogen peroxide

O2 + ClSO2O ⇌ SO5 + Cl
 Peroxymonosulfuric Acid
Synthesis and production
1. Combination of chlorosulfuric acid and hydrogen peroxide

HCl gas Aspirator vacuum

removed

Pure, cooled
~ Anhydrous H2O2 Mixture
slowly added ClSO2OH

gradually warmed
 Peroxymonosulfuric Acid
Synthesis and production
1. Combination of chlorosulfuric acid and hydrogen peroxide

Crystals

Rapid suction 12 HCl-free

Well-sealed flask
filtration hrs mixture
Fritted Glass Disk crystallized
*cooling bath
Mother Liquor
 Peroxymonosulfuric Acid
Synthesis and production
2. Addition of H2O2 to concentrated sulfuric acid
• contained in a inert container (glass)
Heat of dilution of the sulfuric acid causes strong heating.
• surrounded by an ice bath for temperature control
Advantage: Caro's acid can be stored under refrigeration for
several days
Disadvantage: Caustic aerosol release into the air that can damage
skin and clothing
Peroxymonosulfuric Acid
Synthesis and production
Large scale production
of Caro's acid is usually done
on site, due to its instability.
According to the patent by
Dilber, Caro's acid is produced
by reacting sulfuric acid (>
85%) and hydrogen peroxide (>
50%)*.
H2O2 + H2SO4 ⇌ H2SO5 + H2O
 Peroxymonosulfuric Acid`
Addition of H2O2 to concentrated sulfuric acid*

O2 + SO4 ⇌ SO5 + O
 Peroxymonosulfuric Acid
Uses in industry
• variety of disinfectant and cleaning applications
o swimming pool treatment
o denture cleaning
o industrial organic syntheses (oxidation of ketones to lactones or
esters)
o oxidizing acidic leaching solution for the extraction of uranium
from ore
 Sodium Peroxide
• Sodium Peroxide (Na2O2) is a yellow-
white to yellow granular solid and is the
most important peroxide in an industrial
scale. Pure Na2O2 is a colorless powder.
The yellow tinge is due to an impurity,
the sodium superoxide (NaO2+).
• Decomposition of Na2O2 occurs with the
release of O2 upon heating above 300
°C.
 Sodium Peroxide
Chemical formula: Na2O2
Molar mass: 77.978 g/mol
Physical state: Solid powder
Appearance: White to Yellowish
Melting Point: 460 C (decomposes)
Boiling point: 657 C (decomposes)
Solubility: soluble in hot > cold water, in acid; insoluble in base
*reacts with methanol
Main hazard/s: highly reactive with water; strong oxidizer
 Sodium Peroxide
Manufacture
produced industrially by burning sodium in air
2 Na + O2  Na2O2
o aluminum vessels are used to prevent decomposition of sodium
peroxide, which happens in temperatures above 400 °C; a current of
dry air (free of CO2) is passed over it
2 Na2O2  2 Na2O + O2 (decomposition of Na2O2)
oIn the beginning of the process, Na2O is produced before coming in
contact with oxygen-rich air and eventually producing Na2O2 (at 350
°C)
 Sodium Peroxide
Manufacture
produced industrially by burning sodium in air
2 Na + O2  Na2O2
o in a rotating drum, heated to 150 – 200 °C, sodium is primarily
oxidized to Na2O; further heating (at 350 °C) yields the peroxide
o in the presence of O2 at 30 MPa and 500 °C, Na2O2 (diamagnetic) is
converted to sodium superoxide (NaO2, paramagnetic)
Na2O2 + O2  2 NaO2
 Sodium Peroxide
Manufacture
Hydrogen peroxide & sodium hydroxide are produced by the
hydrolysis of Na2O2
Na2O2 + 2 H2O  2 NaOH + H2O2
The reaction is accompanied by the release of heat and by the partial
decomposition of H2O2 to H2O and O2 due to the basic solution
(NaOH).
 Sodium Peroxide
Uses
obleaching agent for wood pulp in production of paper and textiles
osolid substitute for hydrogen peroxide
ostrong oxidizing agent
ostarting material for the production of other peroxo compounds
omedicine (germicide, antiseptic, and disinfectant)
odiving equipment
Na2O2 + CO2  Na2CO3 + ½ O2
References
• http://www.essentialchemicalindustry.org/chemicals/hydrogen-
peroxide.html
• https://encyclopedia.thefreedictionary.com/Peroxydisulfuric+acid
• https://encyclopedia.thefreedictionary.com/Peroxymonosulfuric+acid
• https://www.youtube.com/watch?v=rq2U7ma15b0
• http://www.sciencemadness.org/smwiki/index.php/Peroxymonosulfu
ric_acid#Preparation
• US Patent No. 6368570
• Sodium Peroxide (n.d.). Retrieved from:
https://encyclopedia2.thefreedictionary.com/sodium+peroxide
• Holleman, A.F., Wiberg, E., et al. Inorganic Chemistry (2001). Academic
Press.
• Chemical Data Sheet: Sodium Peroxide (n.d.). Retrieved from:
https://cameochemicals.noaa.gov/chemical/1516
Hydrogen Peroxide