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APRIL 2016

Chemistry in “The Martian” and for a

mission to Mars
DAVID CASH PHD, MOHAWK COLLEGE (RETIRED), HAMILTON ON

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Introduction
“The Martian”1 is the title of both an excellent novel by Andy Weir and of an enjoyable motion picture
based on that novel. The Wikipedia article summarizes the publishing history and the plot. Chemistry,
specifically the synthesis of water from hydrazine, is very important to the story of “The Martian”.
Even without the plight of a marooned astronaut, chemistry is essential to the survival of humans on
long space flights where carbon dioxide must be recycled into oxygen. It will also be needed to produce
the chemicals needed for an ascent from the surface of Mars.
 CHEM13 NEWS MAGAZINE

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On-line quote, purporting to be from Andy Weir:2

“The most challenging parts of the book for me were things related to chemistry. I’m pretty good at
physics and orbital dynamics, but I’m weak on chemistry, so I had to work hard to get it right.”

Ascent from the surface of Mars

A Mars atmospheric entry1 and descent to the surface of Mars requires atmospheric braking,
parachutes and some low-thrust retro-propulsion for a soft, controlled set-down. An ascent from the
surface of Mars1 requires the greater thrust of a chemical combustion rocket, despite the lower gravity
(g = 3.71 m/s2) relative to that on Earth. The mass of chemicals required for an ascent will be
extremely costly and difficult to supply from the surface of the Earth. Zubrin3 and others in 1991
suggested that the ascent vehicle should use liquid methane1 as the fuel and liquid oxygen1 as the
oxidizer, both chemicals synthesized in situ on the surface of Mars from Martian carbon dioxide and
liquid hydrogen from Earth. The atmosphere of Mars1 is 96% carbon dioxide with an atmospheric
pressure of 600 Pa. Thrust is produced by the combustion reaction shown.

CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆H = -890.3 kJ

Chemical fuel factory (1)

In Zubrin’s scenario, an ascent vehicle sent to Mars would be equipped with a chemical fuel factory
and low-mass cryogenic liquid hydrogen as the only chemical sent from the Earth. The fuel factory is
left behind on the surface when the ascent vehicle departs. The Wikipedia article titled Sabatier
reaction1 covers the chemistry of theCHEM13
synthesis NEWS MAGAZINE
of methane from carbon dioxide. The product water is
electrolyzed to form the required oxygen.
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CO2(g) + 4 H2(g) → CH4(g) + 2 H2O(g) ∆H =MENU
-165.0 kJ

2 H2O(l) → 2 H2(g) + O2(g) ∆H = 571.6 kJ

Step 1. Collect Martian air. Purify the carbon dioxide by filtration, liquefaction and distillation.3

Step 2. Carry out the Sabatier reaction (known since 1910s). The catalyst is the platinum group metal
ruthenium1 supported on alumina. Some initial energy/heat is required to start the reaction. Separate
the products. Cryogenically liquefy and store the methane fuel.

Step 3. Electrolysis of water1 by polymer electrolyte membrane electrolysis.1 Solid-state electrolysis

cells were developed for industrial production of hydrogen from water. They are extremely rugged and
are utilized in nuclear submarines and on the International Space Station (ISS). The anode catalyst
is iridium1 and the cathode catalyst is platinum.1 Separate the products. Cryogenically liquefy and
store the oxygen. Reuse the hydrogen in Step 2.

In “The Martian”, the Mars Ascent Vehicle (MAV) is soft-landed several years before the human
mission arrives. A radioisotope thermoelectric generator1 (Pu-238) power source provides 1500 W of
heat and 100 W of electrical power for the fuel factory computer, electronics, fans, pumps,
compressors, heaters, Sabatier reactor, electrolysis cell and refrigerator units. The liquid methane and
liquid oxygen for the ascent must be ready before the human mission lands.

Note: This chemistry produces equimolar amounts of methane and oxygen. The mass ratio is 32 g
O2 to 16 g CH4, or 2:1. As Zubrin points out (ref. 3, page 15), burning this fuel mixture produces
maximum thrust when the fuel ratio is 3.5:1 by mass. Extra oxygen is required, preferably made
without hydrogen.

Chemical fuel factory (2)

Because of the importance of producing oxygen on Mars without the need for other chemicals,
NASA1 has commissioned a group at MIT1 to produce a Mars Oxygen In-situ resource utilization
Experiment (MOXIE4) cell for a Mars mission in 2020. The MOXIE cell is a fuel cell running in
reverse as an electrolysis cell,5 producing oxygen on Mars from the Martian carbon dioxide. The cell
electrolyte is solid scandia-stabilized zirconia, through which oxide ions migrate from the cathode to
the anode. This cell requires no other chemicals to produce some of the oxygen needed as the oxidizer
for an ascent from the surface of Mars, and oxygen for future use by astronauts on Mars.

Cathode half equation: CO2 + 2 e1- → CO + O2-

Anode half equation: 2 O2- → O2 + 4 e1-

Oxygenator
The novel refers to an oxygenator in the habitat. It is simply a black box that converts carbon dioxide
to oxygen. This may be the same chemistry that is happening in the MAV fuel factory. On board the
ISS, the Sabatier reaction and electrolysis of water are used to recycle carbon dioxide exhaled by the
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astronauts to oxygen. It has been suggested NEWS
that MAGAZINE
the methane produced could be pyrolysed to recover
and recycle the hydrogen so that less hydrogen is needed.

Hydrazine thruster chemistry MENU

In the story of “The Martian”, the Mars Descent Vehicle (MDV) in which
the astronauts arrive uses hydrazine1 thruster(s) to maneuver and soft-
land. Hydrazine thrusters are a type of monopropellant thruster that have
been in use for spacecraft for many years. The Wikipedia article hydrazine
summarizes the chemistry. Hydrazine is passed over the platinum-group
metal iridium as catalyst, breaking down into nitrogen and hydrogen. The
overall reaction is exothermic, producing thrust.

3 N2H4(l) → 4 NH3(g) + N2(g)

N2H4(l) → N2(g) + 2 H2(g)

4 NH3(g) + N2H4(l) → 3 N2(g) + 8 H2(g)

Overall: 5 N2H4(l) → 5 N2(g) + 10 H2(g) ∆H = -253 kJ

Water from hydrazine

Watney can live in the habitat module but needs more food calories if he is to survive four plus years
until the next scheduled mission to Mars. He decides to grow potato plants for food. Amongst the
many things Watney needs to grow his potato plants is a lot of water. In the novel, Weir postulates that
there was almost 300 L of hydrazine leftover from the landing in six tanks in the MDV. Watney brings
the tanks into the habitat. In the film, Watney is shown pumping the hydrazine into a tank for this
transfer. Watney then synthesizes water from hydrazine and oxygen in his habitat. He constructs a
reaction chamber to lead the product gases from decomposing the hydrazine into nitrogen and
hydrogen up through a collecting hood into a polymer tube obtained from an EVA suit. He ignites a
wood splinter cut from Martinez’ crucifix, and burns the product hydrogen gas at the exit of the tube,
producing water:

2 H2(g) + O2(g) → 2 H2O(l) ∆H = -571.6 kJ

This procedure showing the flame is simulated in the film. In the novel, he realizes this reaction would
use up all of his available habitat oxygen, so he powers up the MAV fuel plant to collect and purify
Martian carbon dioxide and compress it into a liquid. He releases this liquid into the habitat, where
the habitat oxygenator turns it into liquid oxygen and stores it. This is left out of the film. Both
hydrazine and ammonia are highly toxic. Watney carries out the drop-wise decomposition of
hydrazine and the burning of the hydrogen produced in his habitat module, while wearing a self-
contained breathing apparatus and multiple layers of clothing as protection.

In the novel, after preparing the first batch of water, he realizes that he has made less water than he
had predicted for the theoretical yield from the amount of hydrazine he has reacted. The burning of
hydrogen gas has been incomplete and a check using a rover cabin gas analyser shows that the habitat
atmosphere is 64% hydrogen gas! He knows he must remove the hydrogen gas from the atmosphere.
He moves his potato plants to a heated rover, reduces the habitat temperature to put his soil bacteria
into hibernation, and greatly reducesCHEM13 NEWS
the oxygen MAGAZINE
level in the habitat. Then, wearing a breathing
apparatus and protective clothing, he releases bursts of oxygen from a tank, while using a spark to
burn the hydrogen. None of this is in the film. MENU

In the novel, during the removal of the hydrogen gas, a minor explosion occurs. This he attributes to
the excess oxygen he has exhaled while breathing. This oxygen has been released from his breathing
apparatus and entered the habitat atmosphere. He exclaims, “I forgot to account for oxygen exhaled in
my breathing”. This dialog made it into the film, but makes no sense without the context.

Sucrose – liquid oxygen pipe bomb

The Hermes shuttle is on a one-shot near-approach path around Mars to rescue Watney, who has
ascended from the surface in a modified MAV. The crew need to reduce their velocity relative to
Watney, and have run out of thruster fuel. They devise a plan to align the long axis of the Hermes
along the line of flight, and then blow out the docking-hatch outer door with a bomb. They place just
enough atmosphere in the central compartments to blow out through the open hatches and provide
the needed retro-thrust.

Mission chemist Vogel makes a pipe bomb, using sucrose1 and liquid oxygen (see Question 4). The
novel points out that the complete combustion of 1 kg of sucrose will produce 16.7 MJ of energy, and
claims this is equivalent to 8 sticks of dynamite1 (5 MJ/kg). The amount of sucrose used is not stated,
just that “he measured the amount carefully” in the Hermes lab, and placed it along with the required
liquid oxygen in a “thick-walled glass beaker with a screw-on cap”. In the film, Vogel is shown adding
what seems to be perhaps a few hundred grams of sucrose, then an unmeasured amount of liquid
oxygen, to what seems to be either a Dewar1 flask or a hot/cold beverage flask with a screw cap closure.

Points of interest
Film vs Novel
Understandably, the film cuts out much of the novel’s chemistry, leaving the flames and the
explosions, and just enough chemistry to make sense of the story line.

Safety
In the novel, Watney employs admirable chemical safety precautions. In the film, Watney reacts
hydrazine without any safety precautions at all until after he has had an explosion!

Stoichiometry
There are incorrect statements in the novel about the volumes of liquid products. Weir mistakenly
takes liquid volumes as if they were mole quantities. Referring to the chemical equations below he
makes the erroneous statements: “..from 300 L of liquid hydrazine I can make 600 L of liquid
water...”; “..I need 300 L of liquid oxygen to make the 600 L of liquid water...”; and “..I need 250 L of
liquid carbon dioxide to make 250 L of liquid oxygen. (see Question 1).

N2H4 → N2 + 2 H2 2 H2 + O2 → 2 H2O
CO2 + ? → O2 + ?

Making Oxygen
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Watney needs the MAV fuel factory to NEWS
make a lot MAGAZINE
of liquid carbon dioxide in a short time, which the
habitat oxygenator will turn into oxygen. Could a fuel factory designed to run for several years at 100
watts be able to run faster? Would it have been designed
MENU to produce and store liquid carbon dioxide in
bulk? Would the habitat oxygenator have the capacity to convert it to oxygen at the required rate?
What if the oxygenator requires hydrogen to operate?

Sucrose Bomb
How does one measure the amount of sucrose in low g or varying g conditions? Sucrose is not a high
explosive (explosive material1), so even if a suspension of sucrose in liquid oxygen can be ignited, it
cannot detonate and produce a shock wave. Would it explode and if so, would it blow out the airlock
door?

Question for students

1. Watney starts with 300 L of liquid hydrazine (density 1.02 kg/L).Answer in L volume units to 3
significant figures (SF).

a. How much liquid water (density 1.00 kg/L) can he make? (344 L)

b. How much liquid oxygen (density 1.14 kg/L) will be used up? (268 L)

c. How much liquid carbon dioxide (density 1.10 kg/L) is required to make the oxygen? (383 L)

2. Watney finds that unreacted hydrogen gas equivalent to a 60 L shortfall of water makes up 64%
of the habitat atmosphere by volume. If the habitat atmosphere is at 100 kPa pressure and 21
ºC, what is its volume?Answer in m3 units to 2 SF. (52 m3)

3. The overall unbalanced reaction of the MOXIE electrolysis cell is: CO2 → CO + O2

a. Balance this equation. How many moles of electrons pass through the cell per mole of oxygen
produced? (4)

b. How many faradays (see Faraday constant1) of charge must be driven through the cell to
produce 1 kg of oxygen? Convert this value to coulombs. Answer to 3 SF.
(125 F; 1.21 x 107 C)

c. This cell reaction is not suitable for recycling carbon dioxide to oxygen on long space flights.
Explain.

4. What volume of liquid oxygen in L units is required to completely combust with 1 kg of sucrose?
Answer in L units to 2 SF. (0.98 L)C12H22O11 + 12 O2 → 12 CO2 + 11 H2O

References

1. www.wikipedia.org for: The Martian; Mars atmospheric entry; Mars; methane; oxygen;
atmosphere of Mars; Sabatier reaction; radioisotope thermoelectric generator; ruthenium;
 electrolysis of water; polymer electrolyte membrane electrolysis; iridium; platinum; hydrazine;
NASA; MIT; sucrose; dynamite; Dewar flask; explosive material; Faraday constant.

2. Andy Weir on
CHEM13 NEWS MAGAZINE
Reddit: https://www.reddit.com/r/sciencefiction/comments/1wwjol/i_am_andy_weir_author_

3. Robert Zubrin is the president of the Mars Society (marssociety.org). The 1991 article is reached
by a link from the Mars Society web pages.MENU

4. NASA MOXIE cell: http://news.mit.edu/2014/going-red-planet.

5. MOXIE Electrolysis Cell: http://ssed.gsfc.nasa.gov/IPM/PDF/1134.pdf.

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