Appendix A: Tables Showing Gibbs

Free Energy as a Function of Temperature

of Formation Reactions

Table A.1 Gibbs free energy of methane formation at differ-

ent temperatures (Adapted from David 2012)
C + 2H2 ! CH4
T (K) ΔG (kJ/mol)
298.15 50.53
300 50.381
400 41.827
500 32.525
600 22.69
700 12.476
800 1.993
900 8.677
1000 19,475
1100 30.358
1200 41.294
1300 52.258
1400 63.231
1500 74.2

Table A.2 Gibbs free energy of ethane formation at different

temperatures (Adapted from David 2012)
2C + 3H2 ! C2H6
T (K) ΔG (kJ/mol)
298.15 32.015
300 31.692
(continued)

© Springer International Publishing Switzerland 2017 177

J.L. Silveira (ed.), Sustainable Hydrogen Production Processes, Green Energy
and Technology, DOI 10.1007/978-3-319-41616-8
178 Appendix A: Tables Showing Gibbs Free Energy. . .

Table A.2 (continued)

2C + 3H2 ! C2H6
T (K) ΔG (kJ/mol)
400 13.473
500 5.912
600 26.086
700 46.8
800 67.887
900 89.231
1000 110.75
1100 132.385
1200 154.096
1300 175.85
1400 197.625
1500 219.404

Table A.3 Gibbs free energy of ethanol formation at different

temperatures (Adapted from David 2012)
2C + 3H2 + 1/2O2 ! C2H5OH
T (K) ΔG (kJ/mol)
298.15 167.874
300 167.458
400 144.216
500 119.82
600 94.672
700 69.023
800 43.038
900 16.825
1000 9.539
1100 36
1200 62.52
1300 89.07
1400 115.63
1500 142.185

Table A.4 Gibbs free energy of carbon dioxide formation at

different temperatures (Adapted from David 2012)
C + O2 ! CO2
T (K) ΔG (kJ/mol)
298.15 394.373
300 394.379
400 394.656
500 394.914
600 395.152
(continued)
Appendix A: Tables Showing Gibbs Free Energy. . . 179

Table A.4 (continued)

C + O2 ! CO2
T (K) ΔG (kJ/mol)
700 395.367
800 395.558
900 395.724
1000 395.865
1100 395.984
1200 396.081
1300 396.159
1400 396.219
1500 396.264

Table A.5 Gibbs free energy of carbon monoxide formation

at different temperatures (Adapted from David 2012)
C + 1/2O2 ! CO
T (K) ΔG (kJ/mol)
298.15 137.168
300 137.333
400 146.341
500 155.412
600 164.48
700 173.513
800 182.494
900 191.417
1000 200.281
1100 209.084
1200 217.829
1300 226.1518
1400 235.155
1500 243.7424

Table A.6 Gibbs free energy of water formation from carbon

at different temperatures (Adapted from David 2012)
H2 + 1/2O2 ! H2O
T (K) ΔG (kJ/mol)
298.15 228.582
300 228.5
400 223.9
500 219.05
600 214.008
700 208.814
800 203.501
(continued)
180 Appendix A: Tables Showing Gibbs Free Energy. . .

Table A.6 (continued)

H2 + 1/2O2 ! H2O
T (K) ΔG (kJ/mol)
900 198.091
1000 192.603
1100 187.052
1200 181.45
1300 175.807
Appendix B: Adaptation of Cardu
and Baica’s Methodology

As it is proposed by Cardu and Baica (1999), it is assumed that the ecological

efficiency has the following form:

ε ¼ ½c  φðη, indicador Þ  ψ ðindicador Þn

Constant “c” and the exponent “n” are going to be calculated by the boundary
conditions. The Pollutant Indicator is used to quantify the environmental impact of
a technology. Its unit is kgCO2(eq)/kgH2.
By following the concepts of the authors, it is proposed that φ(η, indicator) is as
follows:
ηsystem
φ¼

ηsystem þ indicator

where ηsystem is the efficiency of the hydrogen production system.

In order to reduce the range of values and approximate the efficiency

curves of
various technologies, the authors propose using function ψ indicator ) as
ψ ¼ lnðK  indicator Þ. As the logarithm transforms a high number into a lower
number, the distance between extreme points is attenuated. For example, ln
10 ¼ 2.3 and ln 100 ¼ 4.6. Therefore, an interval of [10–100] became [2.3–4.6].
In order to validate the equation, three boundary conditions are adopted, which
are different from those defined by Cardu and Baica and with the indicator in
kgCO2(eq)/kgH2:
Condition 1. If the indicator ¼ 0, ε ¼ 1 for any η.
Condition 2. If the indicator ¼ 50 kgCO2ðeqÞ =kgH2 , ε ¼ 0 for any η. This indi-
cator corresponds to the impact of Lignite (coal with high carbon content).

© Springer International Publishing Switzerland 2017 181

J.L. Silveira (ed.), Sustainable Hydrogen Production Processes, Green Energy
and Technology, DOI 10.1007/978-3-319-41616-8
182 Appendix B: Adaptation of Cardu and Baica’s Methodology

Condition 3. In this case, the hydroelectric power plant was adopted because
the ecological efficiency of this hydrogen production process has already
been previously calculated by Braga (2010), Siqueira and Silveira (2011),
which corresponds to 0.99. It is obtained the indicator ¼ 0.34 kgCO2(eq)/kgH2
and η ¼ 0:78 (value calculated for the hydrogen production process with
electricity from a hydroelectric power plant).
If:

ψ ¼ lnðK  indicator Þ

Thus, through condition 2 and formulation 1, it is obtained:

ψ ¼ lnð51  indicator Þ

consequently:
" #n
ηsystem
ε¼ c
  ln ð51  indicator Þ
ηsystem þ indicator

From condition 1, it is found that

1 ¼ ½c  ln ð51Þn
Then c ¼ 0.25
From condition 3, it is found that n ¼ 0.023 for ε ¼ 0:99n and the ecological
efficiency equation for hydrogen production process is written as:
" #0:023
ηsystem
ε ¼ 0:25 
  lnð51  indicator Þ
ηsystem þ indicator

where:
Indicator: [kgCO2(eq)/kgH2]

References

Braga LB (2010) Análise econômica do uso de célula a combustı́vel para acionamento de ônibus
urbano. Dissertation—Curso de Engenharia Mec^anica, Departamento de Energı́a, UNESP,
Guaratinguetá
Cardu M, Baica M (1999) Regarding a global methodology to estimate the energy-ecologic
efficiency of thermopower plants. Energy Convers Manage 40:71–87
David R (2012) CRC handbook of chemistry and physics, 87th edn. Internet version 2007
Siqueira RBP, Silveira JL (2011) Eficiência ecológica aplicada a uma PCH em funç~ao da operaç~ao
de um reservatório hipotético. PCH Notı́cias e SHP News 50:24–28
Index

A E
Algae growth, 104, 105
Annuity factor, 109–111
B steam reforming process, 129–134
Belo Monte hydroelectric power plant
project, 140
Biocrude, 154
Biogas, 77, 79, 82, 84–86, 88, 90, 92, 94, 95,
99–100, 106, 107, 111, 115, 124, 175, 176
ecological efficiency, 175
steam reforming process, 133–134, 136
Biological hydrogen production, 155
Biophotolysis, 155
Brazil, 104, 111
Brazil’s energy policy, 145, 147, 148, 171
Brazilian conditions, 145, 149, 152, 157,
162, 168, 171
C 89, 91, 92
Carbon cycle, 130, 131, 136
Carbon dioxide (CO2), 127, 128, 130–133,
135, 136, 159
Carbon monoxide, 151, 152, 154
Chemoheterotrophic species, 154
Closed reactors, 105
Coal gasification, 159, 165, 166, 168
Ecological efficiency
electrolysis, 134–135
hydrogen production from microalgae,
135–136
Economic analysis, 111–124
Economic indicators, 162–163
Economical comparison, 123–124
Electrolysis, 2, 128, 135, 136, 153
Electrolytic process, 116–120
electrolysis using hydroelectric power, 103
electrolysis using solar energy, 103
electrolyzer, 102
using wind power, 102
Electrolyzer, 101–103, 109, 110, 116, 124
Endothermic process, 87
Environmental analysis, 127, 128
Environmental indicators, 161–162
Eolic energy, 135
Equilibrium constant (K ), 2, 77, 78, 87,
Ethanol fuel car, 149
Ethanol industry, 146
F
Fossil fuels, 142, 147, 153, 154, 157, 159,
160, 162, 165, 166, 168, 169
Fuel cell program, 150

D
Degree of advancement (α), 2, 78, 87–94 G
Direct ethanol fuel cells (DEFC), 150 Gas emissions, 127
Dry reforming reactions, 99 Gasification, 154, 159

© Springer International Publishing Switzerland 2017 183

J.L. Silveira (ed.), Sustainable Hydrogen Production Processes, Green Energy
and Technology, DOI 10.1007/978-3-319-41616-8
184
GHG emissions. See Green house gas (GHG)
emissions
Gibbs free energy
reforming process and shift reaction,
82–86
change as function of temperature, 79–94
degree of advancement, 87–94
equilibrium Constant, 87
Gibbs free energy change (ΔGo), 77
Global sustainable development, 141
Global warming potential (GWP), 128
Green house gas (GHG) emissions, 143,
165, 167
Group of optimization of energy systems
(GOSE ), 170
H
H2 production process, 100
Hydraulic power, 165
Hydroelectric power, 103, 128
Hydroelectric power plants, 135, 136
Hydrogen, 1–3
production from algae, 104–106, 176
production from microalgae, 104
production process from algae,
121–124
storage and distribution, 155–156
Hydrogen cost, 109–124, 175
Hydrogen from biological processes
(biophotolysis) (HBP), 159
Hydrogen from coal gasification with
carbon capture (HCGCC), 159
Hydrogen from electrolysis powered by
renewable sources (HEPRS), 159
Hydrogen from the steam reforming of
ethanol (HSRE), 160
Hydrogen from the steam reforming of
natural gas (HSRNG), 160
Hydrogen production, 128, 134, 136
bacteria/algae, 165
biological processes, 154–155
in Brazil, 146–156
electrolysis, 153
fuel cells, 150, 152, 165
pipelines, 155
process, 166
pyrolysis/gasification, 154
steam reforming of ethanol, 152–153
steam reforming of natural gas, 151–152
technologies in Brazil, 139–147, 149–152,
154–163, 166, 168–171
Hydropower, 147
Index
I
Indicators
economic, 162–163
environmental, 161–162
social, 163
weighting of criteria/indicators, 164
Interest rate, 111–123
Internal combustion engines (ICE), 151, 168
Investment costs, 124
L
Laboratory for optimization of energy
systems (LOSE), 79, 111
Life cycle assessment (LCA), 128, 145
Lower heating value (LHV), 96–100
M
Maintenance cost, 109, 110, 124
Methane, 159
Microalgae, 135–136
Microwave plasma reforming, 101
Microwave plasma sources (MPSs), 101
Multi-criteria analysis (MCA), 139, 143–145,
156–158, 160, 161, 166, 168, 170, 171
N
Natural gas (NG), 77, 79, 82, 83, 85, 86, 88, 90,
91, 93–95, 97–99, 101, 106, 107, 111,
113, 114, 124, 160, 165, 175
steam reforming process, 131–132, 136
National Renewable Energy Laboratory
(NREL), 116
O
Organisation for Economic Co-operation and
Development (OECD), 148
Operation cost, 109, 110, 116, 124
Operation time, 111–113, 115–120, 122, 123
P
Payback period, 112, 114, 115, 117, 119,
120, 122
Performance matrix, 163
Photobiological process, 175
Photofermentation, 154
Photosynthesis process, 104
Photovoltaic
energy, 135
Index
power, 117–119, 128
power plants, 134
Physicochemical analysis, 77–79, 82, 94, 95
Plasma reforming, 100–101
Pollutant indicator, 128, 129, 135, 136
Potential to emit (PTE), 165
Proalcohol program, 149
Proton exchange membrane fuel cell
(PEMFC), 153
Pyrolysis, 154
R T
Renewable energy, 146–156
Renewable fuels, 147–150
Revamping power generation, 157
S steam reforming process, 94–95
S~ao Paulo, 158
Sensitivity analysis, 168
Shift reaction process, 77, 79, 84, 86,
87, 89, 91, 92, 95
Social indicators, 163
Solar energy, 103
Solar hydrogen energy system, 142
Solar power, 116
Solar spectrum, 104
Steam reforming process
biogas, 133–134, 136
ethanol, 152–153
natural gas, 131–132, 136, 151–152,
168, 169
Steam reforming processes
ecological efficiency, 129–134
ethanol, 129–131, 136
Stoichiometric equations, 129–133
185
Stoichiometry, 82, 94, 96–99
Sugar cane bagasse, 129–132, 136,
146, 147, 149, 154, 170
Sulphur dioxide (SO2), 127, 130–134
Sustainability
assessment, 161–163
indicators, 139, 141, 145, 146, 160,
161, 165
Sustainable fuel, 142, 156–158
Syngas, 154
Thermochemical process
Gibbs free energy (G), 79–94
physicochemical analysis, 77–78
plasma reforming, 100–101
steam reforming of biogas, 99–100
thermodynamic efficiency, 95–99
Thermodynamic
analysis, 2, 77–79, 82, 87, 89, 92, 94–97,
99–102, 104–107
efficiency, 77, 95–100, 102, 105–106,
135, 175
function, 77
W
Water electrolysis, 153
Water spillage, 135
Water-gas shift reaction, 152
Water-gas shift reactor, 129
Wind power, 102, 116–118, 128, 136
Wolfram Mathematica software, 89
World Commission on Environment and
Development, 156