CME4002

Hydrogen Economy
Professor K M Thomas
Lecture 1
 Hydrogen
• Fossil fuels are a pre-existing source
of energy.
• Hydrogen does not come as a pre-
existing source of energy
• It is a carrier. Hydrogen can be
made from both renewable and non-
renewable energy sources.
Why are we considering the possibility
of the hydrogen economy?
• We are close to, or at, peak oil
production
• Future decline in petroleum reserves
• Future high cost of petroleum
• Security of supply
• Climate change
• Environmental benefits
Drivers
The use of hydrogen energy for
transport applications will lead to
lower…
• use of fossil fuels
• CO2 emissions
• Climate change
• Pollution
and improved
• Energy security / diversity / flexibility
• New industries
Future Sustainable Hydrogen Energy Chain
J W Gosselink (2002). Int. J. Hydrogen Energy 27 1125-1129
 Current Hydrogen Use
• Hydrogen is widely used in industry
where safety issues and use can be
controlled. It is distributed in
pipelines over a limited area to
different chemical processes.
• The problems arise in the use of
hydrogen for transport applications
• Storage of hydrogen with a 300 mile
refuelling range is an unsolved problem
• Why?
fuel + [ O2(g) ]  [ CO2(g) ] + [ H2O(l) ] + energy

32.79
Calculation of Parameters in
Table
 Thermodynamic data (298 K)
HfH2O(l) = -285.8 kJ mol-1
HfH2O(g) = -241.8 kJ mol-1
HfCO2(g) = -393.5 kJ mol-1
HfCH4(g) = -74.6 kJ mol-1

HfO2(g) = HfH2(g) = HfC(s) = 0 kJ mol-1

 Enthalpy calculation
H2(g) + ½ O2(g)  H2O(l)
HrH2O(l)
Hf(products) – ’Hf(reactants)
HrH2O(l)= -285.8 – (0 + ½*0) kJ mol-1
HrH2O(l)= -285.8 kJ mol-1
Enthalpy for Reaction is negative
(exothermic)
Similarly C + O2  CO2
HrCO2(g) = -393.5 kJ mol-1
 Calculation for Hydrogen
Combustion
• Hydrogen
• 1 mole H2 = 2g gives 1 mole of H2O
• 1kg H2 = 500 moles
• Heat released = 500 x 285.8 x 103 J
= 142.9 x 106 J
= 142.9MJ/kg Fuel
 Methane
• Reaction CH4 + 2O2  CO2 + 2H2O
• Enthalpy of reaction
Hf -393.5 -2 x 285.8 –(-74.6) = -890.5
kJ exothermic – heat given out
1 mol CH4 = 12 + 4 = 16 g
• 1 kg = 1000/16 moles = 62.5 moles
• Heat released from 1 kg = 62.5 x 890.5
kJ = 55656 kJ
• = 55.656 MJ/kg
• 1 kg CH4 contains 750 g of carbon and 250
g of hydrogen
CO2 = 0.75 x (44/12) = 2.75 kg/kg Fuel
H20 = 0.25 x (18/2) = 2.25 kg/kg Fuel
Thermodynamic Calculations
• Use HfH2O (g) = -241.8 kJ mol-1
instead of
HfH2O (l) = -285.8 kJ mol-1
• H2(g) + ½ O2(g)  H2O(l)
HrH2O(l)= -241.8 kJ mol-1
• 1kg H2 = 500 moles
• Heat released = 500 x 241.8 x 103 J
= 120.9 x 106 J
= 120.9 MJ/kg Fuel
Lower heating values (LHVs) - per mass basis
LHVs – per liquid volume basis
 Calculations
• H2(g) + ½ O2(g)  H2O(l)
• Heat released = 142.9 MJ/kg Fuel
• Density H2(liquid) = 0.0708 kg L-3
• Heat released = 142.9 x 0.0708 =
• =10.12 MJL-1
• H2(g) + ½ O2(g)  H2O(l)
• Heat released = 120.9 x 0.0708
=8.56 MJL-1
 The Problems for Vehicles
• The low energy density of hydrogen
on a volume basis.
• The very low critical temperature of
hydrogen (33 K).
• Large tanks required and possibly
pressure control, cooling, insulation
etc
• Hydrogen has 3 x the energy of
petrol on a mass basis but only ¼ x
the energy on a volume basis
 How can we overcome these
Problems?
• Develop new storage methods. The
issues are size, weight, resistance to
impacts, safety, durability, materials
strength (high pressure cylinders),
insulation (for cryogenic temperatures)
etc
• Use of the more efficient fuel cell
technology. The issues are purity of
gas, efficiency, reliability, etc.
 Liquid H2 Storage volume
• Amount to be stored = 5-13 kg H2
Density = 0.0708 kg L-1
• Volume storage =
5/0.0708 = 64 L
13/0.0708 = 183.6 L
• If smaller cars are used for greater
efficiency these values are large even
with liquid hydrogen
 The grand H2 storage challenge
sustainable production of H2 → store / transport → energy

5 kg H2 gas (ambient)
~ 5 m diameter vessel

5 kg H2 liquid (triple point)

~ 0.5 m diameter vessel
Fundamentals
 Hydrogen Properties
• Hydrogen is a diatomic molecule (H2)
• Molecular weight = 2 g mol-1
• Critical temperature = 33 K (-240oC)
• Liquid density
0.0708 g cm-3 at 20 K
0.0708 kg L-1
70.8 kg m-3
Hydrogen Storage Technologies
 Different materials storage types

Physical storage
Molecular hydrogen (H2)

Chemical storage
Atomic / ionic / covalent hydrogen

Storage at low Storage in close to

temperatures and/or ambient conditions
high pressures

Fast and reversible Slow and

charging and irreversible charging
delivery and delivery

optimum ?
 Hydrogen Storage Problems
• Cylinders: Materials problems are an issue above
500 bar, can the cylinder be filled easily, quickly
and safely

• Liquid hydrogen: very low (< 240 K) temperature,

fuel evaporation, safety, can the tank be filled
safely by a member of the public – rocket fuel

• Materials Storage
Adsorption: Only works at cryogenic temperatures
Hydrides: High desorption temperatures
Chemical methods: regeneration of materials
Hydrogen storage where volume
is not an issue
The Ross Barlow Hydrogen Hybrid Canal Boat
Launched 21 September 2007
 Public Perception of Hydrogen
• Most people accept the argument for reducing CO 2
emissions; but few think that their own contribution
can make a difference; they hold government,
business and even other end-consumers primarily
responsible
• Regular motorists - especially those with families –
are reluctant to change behaviour than those
already ‘converted’ (to public transport, cycling, etc)
• Most people accept that hydrogen energy may have
a part in the sustainable energy future.
• Volume sustainable production and distribution of
hydrogen would enable current car use to continue if
shift to public transport unachievable.
• Slides will be put on Blackboard today