I developed this set of slides for my upper level nutrient management course.

1. What is Anhydrous Ammonia?
• “Dry” or pure ammonia – NH3
• Colorless gas at room
temperature and pressure
• Stored as a liquid under pressure
(nurse tanks rated for > 250 psi)
• When pressure is released, liquid
NH3 vaporizes forming an
invisible highly hydrophilic gas
with a very pungent odor
(detectable at ~ 25 ppm)
• Low levels of human exposure
can result in injury and higher
levels can result in death

2. Boiling point = -28F (-33.3 C)
Density = 681.9 kg/m3 at −33.3 C (liquid)
How does this compare with water?
What is a picometer (pm)?
atomic weight of N = 14 g/mol
molecular weight of NH3 = 17 g/mol
14/17 = 82.3% N

3. Does NH3 dissolve in water?
YES!!
NH3 is polar !
Solubility in water decreases with temperature
47% (0 C)
31% (25 C)
28% (50 C)

4. What does “most reduced” mean?
Nitrogen has many different oxidation states !
Species Name Oxidation State
NH3, NH4+ Ammonia, ammonium ion -3 Most reduced
N2H4 Hydrazine -2
NH2OH Hydroxylamine -1
N2 Nitrogen 0
N2O Nitrous oxide +1
NO Nitric oxide +2
HNO2, NO2- Nitrous acid, nitrite ion +3
NO2 Nitrogen dioxide +4
HNO3, NO3- Nitric acid, nitrate ion +5 Most oxidized

5. NH3 is an important component of the N cycle!
Soil NH3
Plant biomass

6. Human activities now
dominate global
cycling of reactive N
> 150 million metric tons of
NH3 synthesized in 2008

7. Ammonia is an important industrial chemical.
85%
Agrochemicals and Security: Security and Anhydrous Ammonia Anhyd-03

8. Industrial uses of NH3
Ammonium nitrate is used to make explosives as well as nitrous oxide
(laughing gas). Ammonium bicarbonate has applications in baking powder
formulations, in fire extinguishers and as a blowing agent in the
manufacture of polymers.
Ammonia is used in the production of hexamethylenediamine for nylon,
acrylonitrile for fibres and plastics, caprolactam for nylon, isocyanates for
polyurethanes, and hydrazine. It is used as a catalyst in phenol-
formaldehyde condensation and in urea-formaldehyde condensation to
make synthetic resins.
Ammonia is making a come-back as a refrigerant because it does not
contribute to ozone depletion and global warming when released to the
atmosphere. It is said to be an efficient refrigerant in food processing and
preservation as well as other refrigeration and air conditioning processes.
Other uses for ammonia include as a cleaning and bleaching agent, and a
household cleaner.

9. Why is NA the
only region
where NH3 is
used directly as
a fertilizer?

10. TWA = time weighted average, STEL = short-term exposure limit, IDLH = immediately dangerous to life/health
Ammonia Hazards
• Caustic (alkali) burns
• Frost bite
• Inhalation danger to
lining of mouth, throat
and lungs
• Does not support
respiration – suffocation
danger
• Especially dangerous to
eyes
TWA = 25 ppm
STEL = 35 ppm
IDHL = 500 ppm
Agrochemicals and Security: Security and Anhydrous Ammonia Anhyd-06

11. Exposure to > 5000 ppm normally results in death
Means of Exposure
• Hose – rupture, not bled
• Connection – faulty, worn,
improperly connected, freezing
• Valve – corroded, worn, or freezing
• Inhalation danger to lining of
mouth, throat and lungs • Tank rupture or pressure
• Does not support respiration relief (Never fill tank over 85%)
– suffocation danger
• Very dangerous to eyes
Agrochemicals and Security: Security and Anhydrous Ammonia Anhyd-07

12. Personal Protective Equipment
• Always use eye and
hand protection when
working with
anhydrous ammonia
• Use full-body
protection when
working with large
tanks
Agrochemicals and Security: Security and Anhydrous Ammonia Anhyd-08

13. Response
Water, water, water!
Carry a squirt bottle on
your person and in your
vehicle for immediate
first aid to eyes.
Have a water hose installed
near all storage tanks.
Know the location of
showers and eye wash
stations.
Agrochemicals and Security: Security and Anhydrous Ammonia Anhyd-09

15. Fritz Haber – a man with many faces

16. Laboratory
apparatus designed
by Fritz Haber in
1909 for producing
NH3 from H2 and
N2. The catalytic
process took place
in the large cylinder
on the left.

18. Part I
Discuss Sir William Crookes doomsday speech to the British Academy of Science in 1898. What was
he concerned about?
What happened in Germany 10 years after Crookes speech?
What is Dr. Vaclav Smil’s explanation for why China decided to increase its diplomatic relations with
the US during the Nixon administration?
Discuss the N budget on Bob Fry’s farm in Maryland. How much N is coming in and where is it going?
The end of part I includes some comments by Dr. James Galloway who is a leading investigator of the
ecological impacts of N pollution. Identify 4 problems that can occur when N leaks out of agricultural
systems into the surrounding environment.
Part 2
The phrase “paradox” of science is used midway through the second audio file about Fritz Haber.
What is meant by this phrase? Why is Haber considered a prime example of the “paradox of science”?
Briefly discuss Haber’s role in the weaponization of some of his scientific discoveries. Was he actively
involved? Why?
What happened to Haber’s first wife?
Why was Haber’s memorial service only attended by women?
Why was Zyklon B developed and how was it used during WWII?

19. If you want to learn more about Fritz Haber…

20. Founded in 1865, BASF is the world's largest chemical
company, ahead of Dow and DuPont, ~ 100,000 employees,
> $80 billion in sales in 2007.
Karl Bosch worked for BASF and designed the technology
for upscaling Haber’s method of NH3 production.
Nitrates and ammonia made up 59 percent of BASF sales in
1919.

21. Haber – Bosch process development
• Haber and Bosch tested > 6500 catalysts before
discovering the high activity of iron based
catalysts.
• Modern catalysts are still closely related to
original ones
• High pressure and temperature are needed
• At temperatures lower than 400C, the reaction
rate is very slow
→ minimum temperature required to reach the
equilibrium sufficiently fast
• Typical reaction conditions:
– 402C at inlet; 447 – 497C at outlet
– 100 – 250 bar

22. Catalysts lower the activation energy
required to react N2 with H2

23. Industrial N fixation is very energy intensive
> 700 GDF/ton NH3
Large
improvements
in energy
efficiency were
made during
the 20th
century.
~ 300 GDF/ton NH3
~ 185 GDF/ton NH3
130 GDF/ton NH3 Theoretical minimum
GDF = gal. diesel fuel
Diesel fuel is not actually equivalent
used to make NH3
Fig. 6.12 in Smil (2001)

24. Energy required to produce NH3
1 GJ = 6.8 gal. diesel

27. CH4 Haber-BoschN fixation
Industrial process
Where does
the hydrogen
come from??
http://4.bp.blogspot.com/_7RVwVtep2vE/SmrKGGhX4JI/AAAAAAAAAHI/iJUdqNU-ROg/s1600-h/haber2.gif

28. Can be used
to make urea

31. Recent

35. Nitrogen imported by the US

38. 23 facilities

39. Domestic NH3 Production in 2010
Ammonia was produced by 12 companies at 24 plants in
16 States in the United States during 2010; 4 additional
plants were idle for the entire year.
Sixty percent of total U.S. ammonia production capacity
was centered in Louisiana, Oklahoma, and Texas
because of their large reserves of natural gas, the
dominant domestic feedstock. In 2010, U.S. producers
operated at about 85% of their rated capacity.
http://minerals.usgs.gov/minerals/pubs/commodity/nitrogen/mcs-2011-nitro.pdf

40. http://minerals.usgs.gov/minerals/pubs/commodity/nitrogen/mcs-2011-nitro.pdf

41. http://minerals.usgs.gov/minerals/pubs/commodity/nitrogen/mcs-2011-nitro.pdf

42. CF Industries
*
* = IL terminal *
*
*
*

44. Ammonia Distribution Network
1005
Application
Manufacture
Distribution Storage Delivery
Agrochemicals and Security: Security and Anhydrous Ammonia Anhyd-04

45. Ammonia pipelines in the US
The pipelines are 8-10 inch diameter, constructed of plain carbon steel,
with a total length of approximately 3000 miles.

46. Ammonia pipelines
Three companies served 11 States with 5,090 kilometers (km) of pipelines and
4,800 km of river barge transport; rail and truck were used primarily for interstate
or local delivery.
NuStar Energy L.P. continues to operate the Gulf Central ammonia pipeline. The
3,200-km ammonia pipeline originated in the Louisiana Delta area, where it had
access to three marine terminals and three anhydrous ammonia plants on the
Mississippi River. The capacity of this pipeline was about 2 million metric tons per
year (Mt/yr) of ammonia, with a storage capacity of more than 1 Mt. In 2008,
about 1.5 Mt of ammonia was shipped through the Gulf Central ammonia
pipeline.
On June 1 2010, Magellan Midstream Partners, L.P. assumed operations of its
ammonia pipeline from a third-party pipeline company. The 1,750-km pipeline
system, which transported and distributed ammonia from production facilities in
Oklahoma and Texas to various distribution plants in the Midwest, had a delivery
capacity of about 820,000 t/yr. In 2008, 746,000 t of ammonia was shipped
through Magellan’s pipeline compared with 650,000 t in 2007.
http://minerals.usgs.gov/minerals/pubs/commodity/nitrogen/mcs-2011-nitro.pdf

48. Main concepts in the article
12 anhydrous terminals in Illinois
Most are supplied by barge or pipeline
Only one terminal is supplied by rail
The pipeline is currently at capacity
Terminals were built in the late 60s and early 70s.
Rail carriers have petitioned for indemnification
Retailers have expressed interest in receiving NH3 directly by rail
Fall applications are necessary

51. N fertilizer materials (tons) purchased in IL
Material fall06 spring07
MAP 11-52-0 6,955 4,017 10.5%
DAP 18-46-0 56,653 42,147
10-34-0* 766 1,567
28-0-0 19,173 127,447
UAN 22.5%
32-0-0 12,616 75,737
Urea 46-0-0 10,136 23,480 3.2%
AA 82-0-0 293,375 277,952
55 %
82.5-0-0 17,906 4830
98.8 % of material grade 1,043,307
94.6% of total N
* (10-30-0, 10-32-0, 10-34-0, 11-33-0, 11-37-0)

54. Shift toward greater use of urea and UAN in the Midwest

55. Reasons for the decline in use of AA
Concerns about human safety
Concerns about impacts on soil (little research evidence)
Rail companies are raising rates and limiting transport of NH3
Weather/soil conditions limit NH3 application window
UAN application is faster and more flexible
(1-2 thousand acre/day for UAN vs. a few hundred acres for NH3)
UAN can be applied with other crop inputs

56. What do farmers think about anhydrous?
Anyone
know this
guy?

57. Tom Oswald wrote:
It is our preferred source of N for a number of reasons. My Dad remembers
going to ammonia meetings back in the late 1950's-1960's and the optimums
discussed at those meetings are still the same though we stretch into fall
application as part of strip till and earlier corn planting than in years past.
1- N is at depth. In the sometimes dry western corn belt, this is a good thing.
In 2007, my sidedress liquid N plots were 20 bu/ac less than fall+ planter 20#.
Rain stopped right after sidedressing. and the corn suffered.
2- N is banded..... a good thing.... concentrated in less soil volume. Unlike
sprayed on 28% or broadcast urea which is a horizontal band.
3- Concentrated form of N, less gallons handled.
4- Some suggest ammonium form better for corn. (Charles Tai, Purdue,
1980's I think)
5 "Here" pipelines and tankers handle most of it.
6- Have my own toolbars and controllers (can be used for both liquid or
ammonia, strip or sidedress).
7- Manly way to farm (big tractors, lots of iron, dangerous)
8- Believe that compaction (runway construction etc) is mostly a myth. Tillage
is harder on the soil than ammonia.
9- liming behind ammonia not that much worse. Ammonium sulfate is worse I
believe. Talk to a soil chemist.

58. Cons:
1- Manly way to farm (big tractors, lots of iron, dangerous)
2- Theft
3- Environmentalists target ammonia tanks in their advertising
4- requires soil incorporation (tillage via knife)
5- control equipment is expensive
6- gassing can burn emerged crop if done improperly
In summary, we (Dad and I) like AA and hope to keep using it as the primary
N source on our farm. I think the benefits outweigh the negatives and
believe that our yields would be somewhat lower (on average over the
years) and our costs would be higher if we had to switch to urea or liquids.
We hope that the regulators and nitrogen production companies don't take it
away.
Tom
-----
Thomas E. Oswald
Oswald Family Farm
Cleghorn Iowa

59. Unusually high

60. http://www.ipm.iastate.edu/ipm/icm/node/181/print

61. Maximum soil temps
under bare soils at 4”
http://www.isws.illinois.edu/warm/
DOof I anhydrous
U NOT APPLY
application guidelines
are basedYOUR
WHEN on daily
maximumIS RED!
AREA temp at 4”
Fall N application south of
IL HWY 16
is never recommended
by the U of I

62. “If the industry is to
continue the practice of
fall N application, we
must police ourselves or
risk being regulated by
federal government
agencies and lose the
ability to apply fall
nitrogen.”

63. Being smart about the timing of anhydrous application can
pay large dividends!
Wait until soil temperatures at the 4-inch depth are below
50 degrees Fahrenheit.
The rate of nitrification is significantly reduced when soil
temperature is below 50 degrees F, but microbial activity
continues until temperatures are below freezing.
In order to minimize risk, don’t apply nitrogen before the third
week of October in central Illinois, or the second week in
northern Illinois, even if air temperatures are getting cooler.
In addition, do not use nitrogen or nitrogen with a nitrification
inhibitor if you live south of Illinois Route 16 or if soils are
prone to leaching.

64. Nitrification inhibitors are not 100% effective
and are only cost-effective in some situations
Sample Date
Dec. 8 Apr. 2 May 3
Application N-serve % NH4-N Remaining
No 39 19 3
Nov. 7 (>50°F)
Yes 63 28 17
No 40 33 7
Nov. 18 (<50°F)
Yes 67 58 26
http://www.ipm.iastate.edu/ipm/icm/2001/10-22-2001/why50.html

65. It is normally more efficient to apply N in the spring
even if a nitrification inhibitor is used
Spring w/o N serve
Fall with N serve
Fall without N serve

66. Impact of pH and N-serve on % nitrification
Inhibitor = N-Serve
w/o N serve
w/ N serve
% Nitrification
High ph inhibits nitrification as
Low ph can override N-serve
much or more than N-serve
Soil pH
http://soil.scijournals.org/cgi/content/full/68/2/545/FIG4

67. Soil pH should be considered an important
factor affecting the risks and benefits
associated with fall applications of anhydrous
ammonia under climatic conditions found in the
Corn Belt.
Relatively rapid nitrification in higher-pH soils increases
the potential for early season losses of fertilizer N by
leaching and denitrification of NO–3 before plants begin
rapid growth and uptake of N.
N-Serve is probably a waste of money on low pH soils!

68. So what do you think of the rule of thumb – 10 lbs of NH3-N per unit of CEC?
This may be one of the worst and misguided soil fertility concepts
that I have heard (OK, ranks up there). I am not going to do the CEC
math, but I think Joel has a decimal point or unit charge off
somewhere. What is missing from his explanation is the fact that
ammonia interacts with the soil organic matter and soil clays (beyond
negative charges). Soil moisture helps retain and limit ammonia
movement at injection time, but it is all of the soil properties that
result in a small retention zone. Take a look at Joe Touchton's
publications (and go way back in time to McIntosh and Frederick --
1950's) and you will see the small size of an ammonia retention
zone, even in "low" organic matter and "low" CEC soils. So, it is
much more than CEC alone that influences ammonia retention.

69. What rate is this in lbs/ac? 8.4 g N/m in Kahola siltloam
Izaurralde et al. (1987)

71. If uniformly distributed in a 2 million lb/ac plow layer,
1000 ppm N = 2000 lbs of N/ac
Soils can clearly retain a lot more N than 10 lbs * CEC!

72. In the retention zone, 33% of the CEC is saturated with NH4+

73. Many anhydrous ammonia applicators give uneven
applications, particularly applicators with older
manifolds.
Manifold outlets across from the intake usually put
out higher rates than outlets near the intake.
When an older manifold is used, the most important
management practice is to randomize the hoses. This
means that a row getting a low rate is more likely to
be next to a row getting a high rate, which will
minimize yield loss.

74. http://www.extension.iastate.edu/Publications/PM1875.pdf

76. How Equaply® Works
Accurate control of mixed gas and liquid phases is difficult to
achieve. Conventional application systems do an excellent
job of applying consistent amounts of anhydrous ammonia
over a field. But they don't provide equal flow to each injector
knife. Heat exchangers cool the ammonia below its boiling
point before entering a flow meter and control valve. With
only liquid present, the valve can exert near perfect control.
However, when the anhydrous goes through the control valve
it loses pressure and boils, creating a mixture of liquid and
gas. This mixture is difficult to be split evenly in a manifold.
So distribution among the knives is random and variable.
http://www.anh3.com/about%20anh3.html

80. http://www.bcsclients.com/email/jd/20080807/08/index.html

82. Shallow placement of anhydrous
Traditional thinking is that anhydrous ammonia must be placed 8 in. deep in
the soil. The 2510H High Speed Applicator places anhydrous at 4.5-in. depth,
which is quite a difference from traditional thinking.
John Deere has tested this placement across the Corn Belt in real-world field
applications and plot-size treatments. More than 10,000 acres of spring pre-
plant anhydrous ammonia application yielded no reports of seedling damage.
To further evaluate shallow placement, plot-scale studies were initiated with
three university cooperators that put the concept to the test by planting right
over the anhydrous application track seven days after application.
To avoid seedling damage with the 2510H, the same recommendations apply
as when using a conventional shank applicator:
* Allow a window of opportunity
* Apply to the rows at an angle
* Soil moisture conditions
http://salesmanual.deere.com/sales/salesmanual/en_NA/primary_tillage/2010/feature/nutrient_applicator/2510h_shallow_placement.html

83. Retention at a shallow depth
What about retention at a shallow depth? John Deere has gone to
great lengths to verify the anhydrous retention provided by a 2510H
is equal to that of a shank.
Three methods were used to measure retention.
The brick soil sampling method entailed extracting a brick of soil in
the injection zone 24 hours after application and send it off to a lab
for analysis. A side-by-side comparison of the 2510H with a
conventional shank revealed equal retention.
The other two methods were the litmus paper test and the chamber
technique to collect emissions.
All three methods revealed equal retention with a shank applicator.
http://salesmanual.deere.com/sales/salesmanual/en_NA/primary_tillage/2010/feature/nutrient_applicator/2510h_shallow_placement.html

85. http://www.youtube.com/watch?v=8xpBd1cI_6Y

86. http://nebraskafarmer.com/story.aspx/anhydrous/hookup/offers/no/hands/convenience/30914

87. http://www.youtube.com/watch?v=L4FsvwKT70g

88. Standard (24 steps) PitStop Pro (10 steps)
1) NH3 Application 1) NH3 Application
2) Tank goes empty 2) Tank goes empty
3) Operator moves tractor, applicator, and empty tank to end 3) Operator moves tractor, applicator, and empty tank to end of
of field or full tank location field or full tank location
4) Operator exits tractor 4) Operator presses Detach Hose button in cab
5) Operator outfits PPE while approaching rear of applicator 5) Operator presses Detach Hitch button in cab
6) Operator closes tank supply valve 6) Operator moves tractor/applicator to full tank
7) Operator closes supply hose valve 7) Operator backs applicator up for attachment to full tank
8) Operator opens bleeder on supply hose 8) After contacting full tank with implement hitch, operator
pulls forward to confirm attachment
9) Operator waits while NH3 bleeds out between tank shutoff 9) Operator presses “Attach Hose” button in cab
valve and supply hose shutoff valve
10) Operator removes supply hose from tank 10) Operator returns to location and begins to apply NH3
11) Operator climbs down from tank with supply hose and
places on rear of applicator
12) Operator pulls out drawbar pin
13) Operator returns to tractor cab
14) Operator removes PPE while walking to tractor
15) Operator moves tractor/applicator to full tank
16) Operator backs applicator up for attachment to full tank
17) Operator exits tractor and returns to rear of applicator to
attach drawbar of tank to applicator
18) Operator pulls out applicator adjustable rear hitch, lifts
tank drawbar and attaches with pin
19) Operator outfits with PPE
20) Operator places supply hose on tank then climbs up tank
21) Operator attaches NH3 supply hose to tank
22) Operator opens both supply hose valve and tank valve
23) Operator returns to tractor
24) Operator returns to location and begins to apply NH3
Green = tractor in motion

91. Does NH3 really have potential as a fuel?
• Ammonia (NH3) can be produced from any raw
energy source, including all fossil, renewable and
nuclear sources.
• Ammonia is cost competitive with gasoline as a
transportation fuel (need to check on this)
• Ammonia has extensive, worldwide transportation
and storage infrastructure already in place
• Ammonia is very environmentally friendly when used
as a transportation fuel and produces only N2 and
H20 at the tailpipe with low-cost emissions controls.
• Ammonia has been successfully demonstrated in SI
engines, CI engines, and fuel cells.