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Alexandra Barbera

SCH 106 01: Foundations of Chemistry

December 3, 2015

Dr. Moerdyk

Haber Bosch Process

There are things in this world that have the potential to help people as well as to kill

people. The Haber Bosch process is one of these things. Research for ammonia synthesis had

gone on long before Haber and Bosh had any results, but it was not until World War I that the

tensions rose and the work was finally completed. A blockade put on Germany froze the

countrys nitrates supply (Kiefer). Nitrates from Chile were used not only for explosives but

aided in the production of food. Once the supply was cut off, Germany rushed to find an

alternate source. Fritz Haber and Carl Bosch came together in their work and made the Haber

Bosch Process a success. The Haber Bosch Process combined hydrogen and nitrogen to form

ammonia. This process had a rough beginning due to the difficulty of the actual process. This

process had to overcome forces such as reactivity, thermodynamics, entropy, enthalpy, and all

the while keeping the production cost low enough to produce a profit.

The combination of nitrogen and hydrogen forms an equilibrium reaction to ammonia.

The hydrogen for this reaction was originally obtained through electrolysis of water, but recently

new ways of obtaining hydrogen were implemented, such as the steaming of methane gas (Bosch

198 & Helmenstine). Nitrogen is pulled from the air when the oxygen is burned (Bosch 198).

The combination of these gasses seems like a simple reaction, but many complications arise. One

of these complications is enthalpy. Enthalpy is defined as the amount of energy needed to break

the bond between a pair of atoms in a gaseous molecule (Bond Breaking and Bond Making in
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Chemical Reactions). In triple and double bonds, more energy is required than a single bond. For

a strong triple bond, such as N2, to be broken, energy is required to overcome such bonds. The

breaking of hydrogen bonds in H2, still requires energy, but far less than nitrogen due to its

single bond properties (Haber 330). The addition of a catalyst has the potential to lower the

activation energy by assisting with the breaking of bonds (Masterson 393). With enough energy

and the right conditions, the equilibrium equation between hydrogen, nitrogen, and ammonia can

be formed.

N2 (g) + 3 H2 (g) 2 NH3 (g) (H = -92.4 kJmol-1)

This reaction suggests that the overall reaction is exothermic, which is associated with

bond making reactions (Bond Breaking and Bond Making in Chemical Reactions).

Thermodynamically, the reaction favors the products while at room temperature and pressure,

but the reaction does not produce significant amounts of ammonia due to the stability of the

reactants (Helmenstine). Increases in temperature favors endothermic reactions while disfavoring

exothermic reactions (Masterson 390). Because the reaction is exothermic, or gives off heat, the

addition of excess heat into the system, or increase in the temperature, pushes the reaction to the

left (Helmenstine). The reaction then favors the reactants more and disfavors the synthesis of

ammonia. In order to favor the products, the reaction must take place at lower temperatures. If

the temperature is too low this poses a question on the rate. Higher temperatures influence a

faster rate while with lower temperatures, the rate is much slower (Clark). Having extremely

slow rates would not be efficient, and would not produce enough ammonia in an appropriate time

for manufactures (Clark). To settle a compromise between rates and temperatures, the Haber

Bosch reaction is set between 400 to 450 C to produce an estimated 15% product yield (Clark).
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These complications and low product yield values slowly begin to settle as we look into

Le Chateliers Principle. Le Chatleiers Principle states that when a system is disturbed, the

system will shift to counteract the change (Hillert). This means that an increase in pressure

would push the reaction towards the side with the least amount of moles (Hillert). Pressure helps

to shift the equilibrium reaction of nitrogen and hydrogen to favor the formation of ammonia due

to the reactant moles to product moles ratio. This ratio of reactants to products is 3 to 2. When

pressure is added to the Haber Bosch system, the equilibrium shifts to the products (Clark). The

added pressure would help produce more ammonia, but the production costs of operating

extremely high pressure systems is extremely high (Clark). To compromise this pressure

situation, the process runs around 200 to 300 atm. This is a high enough pressure to influence the

formation of ammonia while still keeping the production prices at a manageable amount (Clark).

Le Chateliers Principle also means that an increase in the reactants will push the reaction

to the right as well as the decrease in products would push the reactions to the right (Le

Chatleiers Principle). This suggests that if the resulting ammonia is removed from the system,

the system would no longer be in equilibrium and the system would continue to form products

until the equilibrium value is reached. This idea is achieved though a heating and cooling cycle

the system undergoes (Clark). Ammonia is easily liquefied under pressure as long as the

temperature is not too high (Clark). To liquefy the ammonia, the system is cooled, and the

ammonia is drained out (Clark). The reaction only yields about 15% ammonia each time

(Helmenstine). The gases are then recycled, passed over catalyst beds and cooled until about

97% of hydrogen and nitrogen is converted to ammonia (Helmenstine).

Catalysts are substances, either homogeneous or heterogeneous, that are not used up in a

reaction but helps to lower the activation energy. In order to keep the equilibrium reaction at
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manageable temperatures and pressures, as well as a low enough activation energy for the

reaction to proceed, a catalyst must be present in the system. Haber originally chose catalysts,

osmium and uranium, but they were quickly replaced with cheaper or better alternatives

(Helmenstine). Osmium volatilizes when in contact with air, and the worlds supply of osmium

is extremely low for industrialized processes (Bosch 198). Uranium was extremely expensive

and is extremely sensitive to oxygen and water which made the need for better and cheaper

alternatives grow in order to send the process to an industrial level (Bosch 198). An iron-based

catalyst that included potassium oxide (K2O) and aluminum oxide (Al2O3), was used to help

break bonds and lower the activation energy (May). Today, two different catalysts are used in

the reaction. The other, slightly newer catalyst involves ruthenium (Ru) divided evenly over a

graphite surface (Masterson 393).

The ability for the Haber Bosch reaction to proceed towards products, ammonia, also

depends on entropy. Entropy is defined as the measure of disorder or randomness of a system

(Masterson 393). Entropy is higher in gas than in liquids and solids and the value increases as

temperature increases (Masterson 499). This means that gases and substances at higher

temperatures possess a greater degree of entropy because their particles are spread further apart

as well as moving faster. The entropy of a reaction increases as the number of moles increases

(Masterson 502). This means that because the number of moles decreased in the Haber Bosch

process, the entropy also decreased.

The Second Law of Thermodynamics determines if a reaction is a spontaneous process or

not (Masterson 503) The law states that taking into consideration both the system and the

surroundings, a net increase in the entropy signifies that the process is spontaneous (Masterson
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503). The Gibbs free energy equation, also known as the Gibbs-Helmholtz equation, determines

if the reaction is spontaneous or not (504). This equation is:

G = H - TS

This equation suggests that if the G, portion of the total energy change that is available, is

positive, the reaction is spontaneous and proceeds to the products, and that if G is negative, the

reverse reaction is spontaneous and proceeds to the reactants. If G were to equal zero, the

system is at equilibrium. This also states that if the reaction is exothermic (-H), then the

reaction is also spontaneous. If the entropy change is positive, then - TS will make a negative

contribution to the G (Masterson 504). This equation then suggests that the temperature alone

determines if the reaction is spontaneous or not and will result in the reaction either going

forward or backwards towards reactants.

The reaction was not always easy, and took many years to obtain a process that was

practical for industrialized use and production. In 1900, Henri Le Chatalier presented that

ammonia could be formed through the presence of a catalyst, but lost interest in the experiment

when an explosion destroyed the apparatus (Kiefer). This intrigued Haber and he began his own

investigation. His initial experiments were small scale and yielded small amounts of ammonia

(Kiefer). Around the same time, German chemist Walther Nernest investigated the equilibrium at

pressures and temperatures that were not practical for industrialized use (Kiefer). Their work had

conflicting results, but Haber persisted on repeating his experiment, and his more favorable data

proved to be correct (Kiefer). Within his lab, and with the help of English student Robert Le

Rossignol, Haber was able to produce adequate amounts of ammonia at pressures around 200

atm and temperatures around 500-600 C (Kiefer). They then would run the combined gases over
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a catalyst, osmium and uranium, to produce ammonia. This process was successful and Haber

eventually patented his process (Kiefer).

Not long after Haber had published his efforts, an engineer from a German chemical firm,

Badische Anilin- und Soda Fabrik, by the name of Karl Bosch saw the process and bought the

patens from Haber (Kiefer). Bosch translated the process into a large scale process by designing

vessels out of steel that could properly withstand the high pressures. Alwin Mittasch, an expert

on catalysis at BASF, developed an iron catalyst that was ultimately cheaper than the catalysts

used by Haber (Kiefer). The first ammonia plant opened in Oppau in 1913 (Kiefer).

During World War I, the British navy enabled a blockade on Germany. This blockade

blocked the supply of nitrates into Germany, and without any nitrates, Germany would suffer.

The Germans used their new Haber Bosch process to form ammonia that was then converted into

nitric acid and nitrates (Zmaczynski). The nitrates and nitric acid allowed for the production of

explosives and fertilizers that allowed Germany to keep their people fed while participating in

the war. The British and Americans tried to produce ammonia using the process, but were

unsuccessful due to the patents, and the lack of knowledge in building high pressure facilities

(Zmaczynski). It was not until the 1920s until the first Haber Bosch ammonia plants were built

in the United States and Europe, outside of Germany (Zmaczynski).

Ammonia in fertilizer quickly made it the second most important chemical in the United

States (Zmaczynski). Due to the population growth, the use of fertilizers today is over 400%

greater than compared to the use in 1940 (Zmaczynski). Soil does not lose its fixed nitrogen

under natural conditions, but when plants are harvested, some of the nitrogen is lost in the plant

matter and not returned to the soil (Haber 327). This creates the need to replenish the soil of

nitrogen through fertilizers to enable future plants to grow to feed the people of earth
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(Haber327). Haber himself did not produce ammonia on a large scale, but with the help of Karl

Bosch, the process is responsible for the worlds large population (Galloway). Before the

discovery of man mane ammonia, all ammonia used was made by bacteria. From the first real

ammonia plant in 1913 till today, the Haber Bosch process is responsible for supporting food

production for 50% of the world (Galloway). About 40% of the worlds production of protein

can be traced to nitrogen fixation and the Haber Bosch process (Razon). This shows that without

the Haber Bosch process, the availability of foods would be much lower as compared to food

availability now. Without the Haber Bosch process, almost two fifths of the worlds population

would be nonexistent (Smil 415). Global output of ammonia is about 130 million tons a year and

of which 80% goes towards fertilizers (Smil 415). This great influence is not only noticeable in

agricultural statistics but in also world statistics. Ammonia proposed the idea and application of a

non-carbon emitting alternative fuel (Razon). In 2009, 1.2% of the global energy consumption

was provided by the fuel provided by ammonia formed from the Haber Bosch process (Razon).

This processs importance will continue to grow as the population grows due to the growing

need for more food. The importance of alternate ways for fuel as well as food production has the

potential to become a major part of the global economy in future years.

Ammonia is a chemical that has many uses. Approximately 80% of the ammonia

produced is used in agricultural industries and applied to fields for plant growth (Uses of

Ammonia). Ammonia can also be used as an anti-fungal agent on certain fruits to protect them

from disease as well as acting as a preservative for high-moisture corn storage (Uses of

Ammonia). Ammonia has the potential to manufacture nitric acid, soda ash and dyes along with

the production of some pharmaceutical such as sulfa drugs, cosmetics, and vitamins (Uses of

Ammonia). The developing agent in photochemical processes, various printing and the diazo
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duplication process, is ammonia (Uses of Ammonia). This chemical is widely used as refrigerant,

as well as a source of nitrogen needed for yeast in cooking, a source of hydrogen for hydrogen

fuel cell, a leather curing agent as well as household and commercial cleaners (Uses of

Ammonia).

Almost any discovery can have its good or bad side, but it all depends on what that

chemical or discovery is used for. The synthesis of ammonia was initially good and bad. Other

discoveries had the intention to be good, but was later used for destructive purposes. The

ammonia provided the world with the opportunity to expand and feed the mouths of the growing

population; however, it did provide Germany more power to produce explosives used to bomb

civilians. This example shows that not all chemical is constructive or destructive since it is both

of these. Other scientific discoveries have the same situation. Another one of these examples

stems from the Haber Bosch process when Fritz Haber produced Zyklon B that was originally an

insecticide that was later responsible for 1.2 million peoples death (10 Useful Inventions that

went Bad). Another example is the chemical made by Arthur Galston, Agent Orange, that would

speed the growth of soybeans in low concentrations that was sprayed on Vietnam causing

numerous deaths and birth defects (10 Useful Inventions that went Bad). TNT was also

discovered to be used as a yellow dye, but eventually became better known and used as an

explosive (10 Useful Inventions that went Bad). All inventions have a vision for what it should

be used for and peoples opinion if that use is good or bad may vary on each individuals

perspective.

The Haber Bosch process is the synthesis of ammonia from hydrogen and

nitrogen. This process entails the consideration of aspects oh chemistry, such as the bond

strength of the atoms involved, the enthalpy, entropy, thermodynamics as well ad the Gibbs free
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energy concept. Together Fritz Haber and Karl Bosch industrialized one of the most important

processes dealing with the production of the worlds food supply and aiding in Germanys fight

during World War I. This process was a huge step forward for population growth and contributed

to various other discoveries and uses for ammonia. The combination of hydrogen nitrogen,

accurate values of pressure and temperature, and a catalyst form a versatile compound, ammonia,

that is used for feeding world populations, bombs in World War I, the manufacture of other

substances, refrigerant, cleaners and many other aspects of life on Earth.

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Works Cited

"10 Useful Inventions That Went Bad - Listverse." Listverse. Listverse, 18 July 2009. Web. 03

Dec. 2015.

"Ammonia and the Haber Process." BBC News. BBC, 2014. Web. 02 Dec. 2015.

"Bond Breaking and Bond Making in Chemical Reactions." Avogadro. N.p., n.d. Web. 01 Dec.

2015.

Bosch, Carl. "The Development of the Chemical High Pressure Method During the

Establishment of the New Ammonia Industry." Nobel Lecture. 21 May 1932. Nobel

Prize. Web. 1 Dec. 2015.

Clark, Jim. "The Haber Process for the Manufacture of Ammonia." Chem Guide. N.p., 2013.

Web. 30 Nov. 2015.

Galloway, James N., Allison M. Leach, Albert Bleeker, and Jan Willem Erisman. "A

Chronology of Human Understanding of the Nitrogen Cycle." The Royal Society

Publishing, 17 May 2013. Web. 11 Nov. 2015.

Haber, Fritz. "The Synthesis of Ammonia from Its Elements." Nobel Lecture. 2 June 1920.

Nobel Prize. Web. 28 Nov. 2015.

Hillert, M. "Le Chateliers PrincipleRestated and Illustrated with Phase Diagrams." Journal of

Phase Equilibria JPE (1995): 403-10. Print.

Kiefer, David M. "Chemistry Chronicles." Chemistry Chronicles. American Chemical Society,

Sept. 2001. Web. 14 Oct. 2015.

Masterson, William L., Cecile N. Hurley, and Edward J. Neth. "Gaseous Chemical Equilibrium,

and Spontaneity of Reaction." Chemistry: Principles and Reactions. 7th ed. Belmont:

Brooks/Cole, 2012. 390-525. Print.

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May, Paul. "The Haber Process." The Haber Process. N.p., 1999. Web. 02 Dec. 2015.

Razon, Luis. "Is Nitrogen Fixation (Once Again) 'Vital To The Progress Of Civilized

Humanity'?." Clean Technologies & Environmental Policy 17.2 (2015): 301-307.

GreenFILE. Web. 2 Dec. 2015.

Smil, Vaclav. "Detonator Of The Population Explosion." Nature 400.6743 (1999): 415.

Academic Search Elite. Web. 14 Oct. 2015.

"Uses of Ammonia." Uses of Ammonia. R M Technologies, 2003. Web. 02 Dec. 2015.

Zmaczynski, Raymond. "Zmaczynski - Haber Process." Princeton University. Princeton

University, n.d. Web. 14 Oct. 2015.