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Energy efficiency of hydrogen as a fuel

Candidate code: ghp024

Word count: 3296

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Abstract

The research question; how does the concentration of the electrolyte (potassium sulfate) in
an electrolytic cell affect the amount of hydrogen produced, and how does that affect the
efficiency if we get the energy from the hydrogen by combusting it? was investigated by
comparing the amount of hydrogen produced during electrolysis of water using a Hoffman
Voltameter with graphite electrodes when different concentrations of potassium sulfate were
used as an electrolyte. The current and voltage were measured for each trial, so that the
energy used to produce the amounts of hydrogen could be compared to the literature value for
combustion of hydrogen to determine the energy efficiency in this process. A clear
correlation between an increase in the electrolyte concentration and an increase in the rate of
hydrogen production and energy efficiency could be concluded from the experiment. The
results are still of interest even if the energy from the hydrogen fuel is not from combustion
since there will always be an energy expenditure to produce the hydrogen, thus having an
impact on efficiency.

Word count: 174

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Table of contents

Introduction 4

Experimental 7
Table 1 9

Results 10
Table 2 10

Data Collection and analysis 11


Table 3 11
Current vs. concentration 12
Efficiency vs concentration 13
Hydrogen to oxygen ratio 14

Conclusion and Evaluation 14


Limitations 14

Bibliography 16

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Introduction
In recent years, use of hydrogen as an energy transmitter has been increasing as used as fuel
for cars with either a fuel cell or in a combustion engine, as it is said to be "zero-emission"
and environmentally friendly.1 What is not always considered is that the hydrogen has to be
produced in order to be combusted, and this production requires energy.
The two most common source for hydrogen is water, which has to be electrolyzed to separate
the hydrogen from the oxygen, and methane where the carbon atom has to be removed to
produce pure hydrogen, during which carbon dioxide is produced.2 This makes the hydrogen
production from methane less environmentally-friendly, but both of these processes requires
energy. The idea is that renewable power sources like wind and solar power plants can
produce hydrogen when there is surplus of energy in the grid, as they have to produce the
power when there is wind or sun, and this does not coincide with the need for electric power.
The hydrogen can be stored and used to produce electricity for cars or to the grid.3
When hydrogen is used as a fuel in an engine it is either by burning hydrogen in an internal
combustion engine to generate heat and move pistons, or by reacting hydrogen with oxygen
in a fuel cell to run electric motors.4 This essay will explore hydrogen efficiency under the
assumption that hydrogen is combusted when used as a fuel.

The common reaction for the combustion of hydrogen is 2H2(g) + O2(g) 2H2O(g). This is
an exothermic reaction as it releases energy to the surroundings and thus has a negative
enthalpy change. This experiment will attempt to determine how efficiently pure hydrogen
gas can be produced from water electrolysis, using different concentrations of potassium

1
https://www.theguardian.com/environment/2015/nov/04/the-future-is-here-mass-market-hydrogen-cars-take-to-
britains-roads

2
https://energy.gov/eere/fuelcells/hydrogen-production-natural-gas-reforming

3
https://en.wikipedia.org/wiki/Grid_energy_storage#Hydrogen

4
https://en.wikipedia.org/wiki/Hydrogen_vehicle

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sulfate as an electrolyte and graphite electrodes. How the concentration of potassium sulfate
affects the efficiency of hydrogen production will be evaluated, as well as the efficiency of
energy use in the hydrogen production itself. The hydrogen gas produced could later be
combusted and used as a fuel, and the energy transformations of this process will be
investigated.

How does the concentration of the electrolyte (potassium sulfate) in an electrolytic cell
affect the amount of hydrogen produced, and how does that affect the efficiency if we
get the energy from the hydrogen by combusting it? The energy produced by combusting
hydrogen will not be determined experimentally, but the literature value of 286 kJ mol1
for combustion will be used to determine the efficiency.5

The apparatus used in this experiment to carry out the electrolysis is a Hoffman Voltameter, a
glass apparatus containing of three vertical cylinders. Platinum electrodes are ideally to be
placed inside the bottom of the two outer cylinders, but as it was not possible to obtain
platinum electrodes, graphite electrodes were used instead. The electrodes was connected to
the positive and negative terminals of the power supply, so that when current is running
through Hoffman's voltameter, oxygen is formed at the positive electrode (anode) and
hydrogen is formed at the negative electrode (cathode), as each gas displaces water and
collects at the top of its designated cylinder.6

The ideal gas law states that the pressure of a gas (P) in Pascals multiplied with the volume of
the gas in cubic meters (V) equals the amount of gas in moles (n) multiplied with the ideal
gas constant (R), which equals 8.31 J K 1 mol1 multiplied with the temperature of the gas in
Kelvin (T).7 This gives the equation PV=nRT, that can be used to find the number of moles of
gas collected in the cylinders when carrying out an electrolysis, as the volume of hydrogen
can be measured and the number of moles of hydrogen can be found from this volume. The
energy (E) used to produce the hydrogen will be calculated by finding the power used

5
IB Chemistry data booklet, Table 13

6
https://en.wikipedia.org/wiki/Hofmann_voltameter

7
https://en.wikipedia.org/wiki/Ideal_gas_law

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(voltage (V) multiplied with current (I)) and by multiplying this with the time (t) the power
was applied. The energy will then be found by the formula E=VIt.8 This value will then be
compared to the literature value for energy of combustion of hydrogen to find the efficiency.

As the electrical conductivity of pure water as an electrolyte is very low, a great amount of
voltage would be required to produce a measurable amount of hydrogen. Therefore, a soluble
salt (potassium sulfate) was used as an electrolyte to increase the amount of mobile ions that
contribute to the movement of charge. While there exists mobile ions in pure water, these
only occur as water partially dissociates, but the dissociation is so small that there is a lack of
mobile ions to effectively conduct electricity. However, when potassium sulfate is used as an
electrolyte and is dissolved in water mobile potassium and sulfate ions of varying
concentrations are present, depending on the concentration of the electrolyte. This will
produce hydrogen at a faster rate than with the small amounts of hydroxide ions present when
pure water is used.

Aqueous potassium sulfate produces hydrogen and oxygen because water is more easily
oxidised than sulfate ions and water is more easily reduced than potassium.
In this electrolysis, the anode is the positive electrode and has a deficit of electrons, so
species in contact with the anode will be oxidised. The cathode is the negative electrode,
meaning it has a surplus of electrons and is were the reduction happens. In an electrolysis of
dilute potassium sulfate hydrogen is produced at the negative electrode.
The cathode reaction is 2H 2 O + 2e H 2 (g) + 2OH and the anode reaction is

2H 2 O O2 (g) + 4H + + 4e . By adding the anode and two times the cathode reaction, we

get the cell reaction: 6H 2 O H 2 (g) + O2 (g) + 4OH + 4H + . The positive hydrogen ions

will combine with the negative hydroxide to form water; 4OH + 4H + 4 H 2 O , so that
the overall reaction then becomes; 2H 2 O 2H 2 (g) + O2 (g) .9 Where the hydrogen is

produced, the solution becomes basic, and near this cathode the reduction half-reaction
occurs. Where the oxidation happens, at the anode, the solution becomes acidic. The

8
http://www.appropedia.org/Power_and_energy_basics#Energy_.3D_Power_x_Time

9
https://en.wikipedia.org/wiki/Electrolysis_of_water

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ion-electron equation for the hydrogen production process is 2H+ + 2e- H2. This indicates
that 2 moles of electrons are required for the production of 1 mole of hydrogen.10 Since water
is made of two molecules of hydrogen and one molecule of oxygen, and both oxygen and
hydrogen gas is diatomic and is made by two molecules, we would expect to get exactly a 1:2
ratio of oxygen to hydrogen gas from the water electrolysis, as we are simply splitting the
water molecules to hydrogen and oxygen gas.

The efficiency is found by multiplying the number of moles of hydrogen produced with the
literature value for energy released during hydrogen production divided by the energy used to
produce the hydrogen combusted.

Experimental
The equipment used in the experiment was a Hoffmann voltameter, a power source, graphite
electrodes, a voltmeter, a ammeter, an electronic balance, potassium sulfate solution, water, a
stopwatch, 25 cm3 graduated cylinder, a 50 cm3 , a 100 cm3 graduated cylinder, two 100
cm3 volumetric flasks and a 200 cm3 beaker.

Experimental setup

10
https://en.wikipedia.org/wiki/Electrolysis_of_water

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The Hoffman voltameter was connected to a power supply with an ammeter connected and a
voltmeter connected between the two electrodes.

Circuit diagram

When the original stock solution was made the solubility of potassium sulfate was consulted
to get the highest possible concentration. 80.001 grams of potassium sulfate was measured
with an electronic balance with an uncertainty of 0.001 grams, dissolved in a beaker and
transferred to a 500.00 cm3 volumetric flask with an uncertainty of 0.15 cm3 that was filled
up to the mark with water. The concentration made was
80.003 g 0.001 g
174.259 g mol1 (500.00 0.15)103 dm3
= 0.918 mol dm3 0.029 mol dm3 .

The potassium sulfate solutions were made by diluting 0.918 mol dm 3 0.029 mol dm3
stock solution of potassium sulfate with water. The concentrations were made by diluting
0.918 mol dm3 0.029 mol dm3 in 100%, 66%, 50%, 25%, 12.5%, and 0% ratios with
water.

In the first trial, pure stock solution was transferred to two 100.00 cm3 0.08 cm3 volumetric
flasks and filled up to the mark to make 200.00 cm3 0.16 cm3 of a
0.918 mol dm3 0.029 mol dm3 concentration.
In the second trial, 100.00 cm3 of stock solution was measured in a 10.000 cm3 0.05 cm3
graduated cylinder, and transferred and divided into two 100.00 cm3 0.08 cm3 volumetric

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flasks. Then 33.34 cm3 of stock solution was measured in a 50.00 cm3 0.05 cm3 graduated
cylinder and added evenly to the two 100.00 cm3 0.08 cm3 beakers, and the two volumetric
flasks was filled up to the mark with water. This made a 200.00 cm3 0.16 cm3 solution
with 133.34 cm3 0.10 cm3 of stock solution, with a concentration of
0.1334 dm3 0.00010 dm3 0.918mol dm 3 0.029 mol dm3
0.20000 dm3 0.00016 dm3
= 0.612 mol dm3 0.001 mol dm3 .

The following solutions were made in a similar matter, with the exception of the last trial
where a 200.00 cm3 beaker was filled with pure water. The concentrations that were made
are presented in the table below:

Table 1

Trial Measurements and calculation Concentration made

1 Pure stock-solution 0.918 mol dm3 0.029 mol dm3

2 0.1334 dm3 0.00010 dm3 0.918mol dm 3 0.029 mol dm3 0.612 mol dm3 0.002 mol dm3
0.200 dm3 0.00016 dm3

3 0.100 dm3 0.00005 dm3 0.918 mol dm 3 0.029 mol dm3 0.459 mol dm3 0.017 mol dm3
0.200 dm3 0.00016 dm3

4 0.050 dm3 0.00050 dm3 0.918 mol dm 3 0.029 mol dm3 0.230 mol dm3 0.001 mol dm3
0.200 dm3 0.00016 dm3

5 0.025 dm3 0.00030 dm3 0.918 mol dm 3 0.029 mol dm3 0.115 mol dm3 0.005 mol dm3
0.200 dm3 0.00016 dm3

6 Pure water 0.000 mol dm3 0.000 mol dm3

After the electrolyte solutions were made, the Hoffman voltameter was in each trial filled
with the solution from the volumetric flasks or beaker, filling it up the past the gas vessels to
make sure that there was no air bubbles left in the cylinders. The graphite electrodes was
mounted in the two outer cylinders. The power source was turned on, set to apply 10 V, and
the current and voltage was recorded. When the given time had passed, the time was
recorded. The amount of each gas collected in the vessels was recorded. The Hoffman

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Voltameter was then emptied and rinsed carefully, and dried before the next trial. The
temperature was measured using a digital thermometer with an uncertainty of 0.1 degrees
Celsius, and recorded. The electrodes was disconnected, and any carbon that had reacted
during the electrolysis was brushed of with a paper towel between each trial.

Results
All the data recorded from the experiment is presented in Table 2 below. Trial 6 has been
made its own separate row as this was a unique trial with different conditions from the rest,
as only pure water was used.

Table 2

Trial Concentration Duration of Current Measured Volume of Volume of


of K 2 SO4 (aq) ( electrolysis ( 0.005 voltage H 2 (g) produced O2 (g) produced
3 ( 2 s) A) (0.05 V) 3 3 3 3
mol dm ) ( 0.1 10 dm ) ( 0.1 10 dm )
Temperature
( 0.1 C)

1 0.918 1510 0.065 10.45 18.8 5.8


0.029 20.9

2 0.612 2700 0.060 10.35 28.8 4.0


0.002 20.9

3 0.459 1564 0.050 10.30 10.2 2.8


0.017 20.8

4 0.230 2153 0.050 10.30 8.2 2.2


0.001 20.8

5 0.115 2708 0.045 10.25 5.3 1.6


0.005 20.9

6 0 3320 0.030 10.25 2.2 0.6 21.0

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Data Collection and analysis
The moles of hydrogen produced, and the energy used to produce the hydrogen will be
compared with the energy of combustion of hydrogen to calculate the energy efficiency of
hydrogen production. The moles of hydrogen can be calculated by using the formula
PV
PV=nRT, and rearranging it to give n = RT
. If the data from Table 1 is used, for the first
3 3
101.3 kP a(18.8 0.1)10 dm
trial this becomes n = = (0.779 mol 0.004) 103 mol .
8.31 JK 1 mol1 (20.9+273.2) 0.1K

To find the energy used to produce the hydrogen, the formula E=VIt will be used. Using the
data from Table 2, this becomes E= 10.45 0.05 V 0.065 0.005 A 1510 2 s = (1.03
3
0.09) 10 J for the first trial. To find the efficiency the moles of hydrogen produced will be
multiplied with the energy of the literature value of 286 kJ mol1 for combustion of hydrogen
and divided by the energy used to produce the hydrogen.11 The efficiency in the first trial then
3 3 1
(0.779 0.004)10 mol286 10 J mol
becomes e = (1.030.09)103 J
= 0.217 0.019 . This calculation was done in

a similar manner for all trials. The results are presented in the table below:

Table 3

Number of moles of Energy used to produce


3
Trial hydrogen ( 10 mol ) hydrogen Efficiency
3
1 0.779 0.004 mol (1.03 0.09) 10 J 0.217 0.019
3
2 1.194 0.005 mol (1.68 0.15) 10 J 0.203 0.019
3
3 0.423 0.004 mol (0.80 0.09) 10 J 0.150 0.017
3
4 0.340 0.004 mol (1.10 0.12) 10 J 0.088 0.010
3
5 0.220 0.004 mol (1.24 0.15) 10 J 0.051 0.007

3
6 0.091 0.004 mol (1.01 0.17) 10 J 0.026 0.006

A higher current through the cell means more electrons is passing through it per second.
More electrons passing through per unit time (a higher current) means a faster rate of

11
IB Chemistry data booklet, Table 13

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reduction at the cathode and oxidation at the anode. This means a greater number of moles of
each gas will be produced per unit time. Using the data for current and concentration from
Table 2 to the following graph was plotted.

Current vs. concentration

It is clear from the data presented in Table 2, that there is an increase in current as the
concentration increases. Using linear regression the correlation coefficient becomes 0.921,
indicating a strong correlation between the variables. The variations of amperage depends on
the conductance of the electrodes and electrolyte and the power from the power source. Since
the electrodes and power supplied remains constant, we can deduce that a higher
concentration of the electrolyte is responsible for the increase in current.

We can then deduct that an increase in concentration will lead to a faster rate of hydrogen
production, as the current increases. By comparing the hydrogen produced per second (total
hydrogen produced in cm3 divided by the number of seconds) with the concentration of
dilute potassium sulfate, we can see the correlation between increased electrolyte
concentration and hydrogen production. The correlation between concentration and rate of
hydrogen production is shown in the graph below, made using the data for current and
concentration from Table 3.

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Hydrogen production vs. concentration

Using linear regression, the correlation constant is found to be 0.984, thus showing that there
is a strong linear correlation between the concentration and rate of hydrogen production. This
directly affects the efficiency of hydrogen production as seen in the following graph made by
using the efficiency and concentration data from Table 3.

Efficiency vs concentration

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Linear regression gives 0.970 as the correlation constant for the correlation between energy
efficiency and concentration. We can see that an increase in the electrolyte concentration
increases the energy efficiency, so a stronger concentration of electrolyte will be favoured to
produce the most available energy when hydrogen is combusted compared to the energy used
to produce the hydrogen.

Hydrogen to oxygen ratio


Water is made of two molecules of hydrogen and one molecule of oxygen. Both oxygen and
hydrogen gas is diatomic and is made by two molecules. Thus, we would expect to get
exactly a 1:2 ratio of oxygen to hydrogen gas from the water electrolysis, as the water
molecules are splitted to hydrogen and oxygen gas. Still, as we can see from Table 2, that a
lot more hydrogen was produced relative to the oxygen. This could be because the Hoffman
voltameter should use platinum electrodes, and as graphite electrodes was used instead, some
of the oxygen produced will have reacted with the carbon.

Conclusion and Evaluation


From the results of the experiment, it is clear that the concentration of the electrolyte
(potassium sulfate) in an electrolytic cell directly affects the amount of hydrogen produced,
and that an increased concentration in the electrolyte increases the efficiency if we get the
energy from the hydrogen by combusting it. The increase in electrolyte concentration
increases the amount of mobile ions that can take part in the redox-processes necessary to
produce hydrogen, and thus increases the rate of reaction, making the production more
energy efficient, under the assumption that it will later be combusted.

Limitations
A experimental limitation to my experiment is the the few trial and data points, as more data
points would have enabled me to ascertain better what the relationship between the data
points are in the various graphs. Also, since graphite electrodes was used, some of the
electrodes reacted with the oxygen and was oxidized. This only affects the amount of oxygen
produced, and as the hydrogen production was the focus of the investigation, the use of
graphite electrodes instead of platinum can be justified.

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Another limitation is how to what extent the results of this experiment can be applied to
hydrogen as a fuel in real life, as the majority of hydrogen cars use hydrogen in a fuel cell to
generate electricity for an electric motor, instead of combusting it an an engine. While most
hydrogen cars use fuel cells, there are still a few cars that use internal hydrogen combustion
engines, where the results from this experiment applies.12 Regardless of whether or not the
hydrogen is used in a fuel cell to produce the energy or directly combusted, the hydrogen still
has to be made, thus the energy required for the production of the hydrogen itself will still
play a role in the overall efficiency of using this fuel.

12
https://en.wikipedia.org/wiki/Hydrogen_internal_combustion_engine_vehicle

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