Hydrogen: The Future of Energy?

Omar Garcia-Navarro

MAE 219: Thermodynamics

Professor Hendrick H. Delcham

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 According to a recent study, Americans use 30% of the world's oil supply but only 2% of

that comes from American soil. In addition to this alarming fact, the United States was one of

the top five countries responsible for the most carbon dioxide emissions in 2004, along with

China and Taiwan, Russia, India and Japan. There was a time when the earth was well-equipped

to eliminate air pollution, like carbon dioxide thanks to processes like the water cycle and

photosynthesis. The earth’s oceans also helped to absorb some of the excess carbon dioxide in

the atmosphere. Natural systems were able to purify small amounts of air pollution. But, due to

the industrialization of society and more recently deforestation, the earth can no longer eliminate

air pollution, like carbon dioxide as fast as we humans create it. Due to the heat-retaining nature

of carbon dioxide, the temperature of the oceans is rising. At a higher temperature, they are

unable to hold excess carbon dioxide. Then, the carbon dioxide holds the infrared radiation we

get from the sun. This prevents the earth from completely cooling at night. The temperature of

the earth is slowly increasing, a few degrees each year, resulting in drastic consequences, such as

the melting of the ice caps, habitat destruction, and more extreme weather patterns. This is what

is generally referred to as global warming.

The fact that we are demanding more from earth is causing the ecosystem to fail.

Manifestations of global warming such as hurricanes, floods and animal deaths are being seen in

places where they have never happened before. The equilibrium between the human kind and

the ecosystem has broken its bonds and the thermal equilibrium between them has been

disturbed. The consumption of fossil fuels is one of the main reasons that we are placing so

much demand on our earth’s fragile ecosystem. We are demanding more and more from the

earth by constantly harvesting fossil fuels, like petroleum. Just the process of removing the oil

from the earth causes harm to the environment.

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 The methods and the chemicals used to drill and process oil requires a large amount of

energy that is transformed into work, work that is used to make large machines perform a series

of operations such as digging or extracting of the oil. Furthermore, during the production of new

products some of the energy is lost and released into the atmosphere in the form of vapor. The

vapor causes a disruption of the ecosystem’s temperature due to the heat applied on the system

by the machines. The heat absorbed by the atmosphere affects the internal state of equilibrium

of earth due to the change in temperature between the bodies within the ecosystem. Based on the

zeroth law of thermodynamics, we can determine that the internal equilibrium is disrupted when

an increase in temperature exist in one of the bodies in the system. If the same process is

repeated over and over, a big quantity of energy is lost into the atmosphere and there is nothing

that can be done to gain it back. During the production of work on a system, some of the energy

is always lost, but we can aid the environment to get back to an internal state of equilibrium by

conserving energy. In addition, the chemicals released in to the atmosphere in the form of vapor

also create other pollutants that can cause acid rain, smog, and fouled waterways.

The combustion of gas as a fuel leads to one of the most damaging forms of air pollution,

carbon dioxide. Carbon dioxide is released into the atmosphere through the burning of fossil

fuels. Carbon based fuels and the combination of oxygen produces carbon dioxide, water and

energy. This is an example of the first law of thermodynamics, which states the change in

internal energy is equal to the amount of energy added through heat minus the amount lost by

doing work on the environment. For instance, in the case of one alternative fuel, methane, it

undergoes a chemical reaction when heat is applied to it between the gas and the oxygen in the

air. As a result, we obtain the desired energy that is used as work to power machines. We can see

this in the following equation: CH4[g] + 2 O2[g] -> CO2[g] + 2 H2O[g] + energy. One

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molecule of methane combined with two oxygen molecules react to form a carbon dioxide

molecule, and two water molecules usually given off as water vapor during the reaction and

energy. Water causes little impact on the environment, but the extra carbon dioxide is very

damaging. Of all the fossil fuels, natural gas burns the cleanest. When it is combusted, the main

waste products are carbon dioxide and water. The others, like petroleum or coal, are much more

complex on a chemical level and release more harmful byproducts when they are burned.

Taking that same principle, scientists have developed the use of hydrogen as a fuel

source, through both modified combustion engines and hydrogen fuel cells. When this energy is

used to power machines, such as automobiles, the only waste product is water. Vehicles have

been created that use hydrogen as a main fuel source to generate power, power that is

transformed into work and make the vehicle to run. The principle behind hydrogen cars lays in

converting the chemical energy of hydrogen to mechanical energy, through either a modified

combustion engine or electrochemical conversion in a fuel cell. The combustion process occurs

when hydrogen is burned in engines just like in gasoline based cars. The fuel-cell conversion,

the hydrogen reacts with oxygen to produce water and electricity, the latter of which is used to

power an electric traction motor.

Hydrogen is one of the simplest, most abundant elements in the universe, accounting for

nearly 75% of the universe’s elemental mass. It is made of only one proton, one electron, and

with an atomic weight of nearly 1. Due to its light weight but great energy potential, its

capability for energy is much higher than any other energy source. However, it is a large

element and takes up lots of space, therefore giving it the lowest energy content by volume.

Hydrogen does not occur naturally on the earth as an isolated element. It is found exclusively in

compound form. It is also important to note that hydrogen is not an energy source, but an energy

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carrier, meaning that it can be used to produce mechanical work. Therefore, to harvest its power

as an energy source, it must be made, either from methane or methanol, through a process called

fossil fuel reforming or from water through a process called electrolysis.

Currently, fossil fuel reforming is the most common method used to produce hydrogen.

Typically, the two gases that are reformed are

natural gas and less commonly, methanol.

Steam methane reforming, which is the name

of the process applied to natural gas to extract

hydrogen, accounts for 95% of the hydrogen

production in the United States. To extract

hydrogen from natural gas, heat is applied to

water to create very hot steam, 750◦ to 800◦ C. Steam Methane Reforming Process

The steam then reacts with the methane, making a synthetic gas, called syngas, which is

composed of mostly hydrogen and carbon monoxide. That chemical formula looks like this: CH4

+ H2O => CO + 3H2; methane reacts with water to create carbon monoxide and three hydrogen

molecules. Then a catalyst is applied to the carbon monoxide and the water vapor, forming

hydrogen and carbon dioxide, represented with this chemical equation: H2O + CO => CO2 + H2.

This is known as the water gas shift.

This process is one of the most efficient in the United States when compared with other

energy production processes, 65% to 75% efficient. Natural gas is also a convenient, readily

available resource in both the US and Canada. Unfortunately, this process is not without its

problems. The hydrogen produced through steam methane reforming is not totally pure; it

contains trace elements of hydrogen sulfide, carbon dioxide, and carbon monoxide. It needs to

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be purified before use in fuel cells, as any impurities in the fuel cell with make it less efficient.

This process is also not very efficient, as twice as much CO2 waste is produced than actual usable

hydrogen. This is the very form of pollution that experts are trying to avoid, as it is the main

cause in the rising overall temperature of the earth. Although the fuel cells are completely clean,

producing the hydrogen needed to fuel them is a very polluting process. Scientists are trying a

process called CO2 sequestration, where CO2 is concentrated collected and then held is some

other environment. Unfortunately, these technologies are too new to be widespread, and their

overall effectiveness has not been proven.

Another less common procedure

used to extract hydrogen from its

compound form is to use a process

called electrolysis, which is process

where an electrical current it passed

through a liquid ionic substance to

separate materials. Typically,

electrolysis is processed used by the

Electrolysis of Water mining industry to extract metals from

their ores or to metal-plate objects. However, in the case of hydrogen production, an electrical

current is passed through water, which results in the molecular gaseous elements of oxygen and

water. This process does not emit any greenhouse gases; however, it is rarely used as hydrogen

is more economically extracted through steam reforming. Electrolysis of pure water is a very

inefficient process, due to the need of overpotential, or the half-reaction’s difference between the

reduction potential and the actual event. Salt water is a much more electrically conductive

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substance, as compared with fresh water. Through the addition of salt or another electrolyte, the

process becomes much more efficient. The electrolyte breaks up into cations and anions, flow

directly to their respective locations and prevent the build-up of excessive positively charged

hydrogen ions, allowing of a continuous flow of electricity.

To supply an electrical flow, two metal plates, usually make from platinum or stainless

steel are put into the water, one which is positively charged called the anode and one which is

negatively charged called the cathode. Then, an electrical current is released, and the hydrogen,

as it is positively charged, travels and collects at the cathode. At the cathode, a chemical

reduction process takes place, the hydrogen cations combine with the negatively charged

electrons from the electrical current coming from the cathode. This combination creates the all

important hydrogen gas, which is collected to be used as fuel source. This process is represented

by the following equation: 2H+(aq) + 2e− → H2(g). Simultaneously, at the anode, oxidation

occurs as it attracts negatively-charged oxygen from the water molecules. This reaction is shown

in the equation 2H2O(l) → O2(g) + 4H+(aq) + 4e−. Two times more hydrogen are generated than

oxygen when the system is perfect.

Thermodynamically speaking, water electrolysis is a very inefficient system in terms of

energy used to decompose the water into hydrogen and oxygen. This process consumes much

more energy than the resulting hydrogen obtained. The table below shows the property changes

when one mole of water is decomposed into its basic elements of hydrogen and oxygen.

Quantity H2O H2 0.5 O2 Change

Enthalpy -285.83 kJ 0 0 ΔH = 285.83 kJ
Entropy 69.91 J/K 130.68 J/K 0.5 x 205.14 J/K TΔS = 48.7 kJ

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Breaking the water molecule into its elemental compounds uses energy not only to lead to

decomposition of water but also to expand the resulting gases. The formula for the system work

(assumed at 298K and one atmosphere pressure) is W = PΔV = (101.3 x 103 Pa)(1.5 moles)(22.4

x 10-3 m3/mol)(298K/273K) = 3715 J. Since the enthalpy H= U+PV, the change in internal

energy U is then ΔU = ΔH - PΔV = 285.83 kJ - 3.72 kJ = 282.1 kJ. In other words the difference

in enthalpy is understood to be the required energy to accomplish the process of electrolysis.

The change in Gibbs free energy is the amount of electrical energy necessary from the battery

and is represented by ΔG = ΔH - TΔS = 285.83 kJ - 48.7 kJ = 237.1 kJ. Entropy speeds up the

decomposition process of water and accounts for the rest of the energy needed to complete the

process. It comes from the environment in the form of temperature change, as this increases the

entropy in the system.

When the collected hydrogen is used as an energy carrier in a hydrogen fuel cell, it is the

opposite process of water electrolysis. Hydrogen and oxygen are combined producing a

chemical reaction to provide electrical energy. Fuel cells are more efficient than burning

hydrogen as fuel in altered combustion engines, as no heat is necessary to convert the hydrogen

and oxygen combination into energy. Since an automobile powered by a fuel cell does not

require heat, nearly all of the energy produced in the cell can be used to power the vehicle and it

is more efficient. It differs from a traditional combustion engine in that the all the energy created

can be used to do work. In a regular combustion engine, some of the heat is lost, as explained by

the second law of thermodynamics.

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 The fuel cell is made up of two field

flow plates, two electrodes (an anode and a

cathode) and two thin platinum-based catalysts.

The two sides of the fuel cell are separated by a

plastic membrane. Hydrogen is fed into one

side of the cell and oxygen is taken into the

other side. The two gases flow through the

plates into the platinum catalyst. The catalysts

split the hydrogen molecules into protons and

electons. The membrane allows the protons to

pass through, but the electrons cannot. The negatively charged electrons travel through an

external circuit. In doing this create electricity that can be used to power a vehicle, for example.

On the oxygen side of the cell, the protons and the electrons react with oxygen in the air, thanks

to the other catalyst. This generates water, the fuel cell’s only by-product and heat.

In a reverse process of water electrolysis, one mole of hydrogen is combined with a half-

mole of oxygen gas forming a mole of water. The table below shows the thermodynamic

potentials of this process at 298K.

Quantity H2 0.5 O2 H2O Change

Enthalpy 0 0 -285.83 kJ ΔH = -285.83 kJ
Entropy 130.68 J/K 0.5 x 205.14 J/K 69.91 J/K TΔS = -48.7 kJ
The formula for system work is W = PΔV = (101.3 x 103 Pa)(1.5 moles)(-22.4 x 10-3 m3/mol)

(298K/273K) = -3715 J. The energy in this system comes from the combination of the atoms

and the decreased volume of the gases, as shown in the change in enthalpy. When considering

the enthalpy of the system, the change in internal energy U is ΔU = ΔH - PΔV = -285.83 kJ -

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3.72 kJ = -282.1 kJ. The entropy in the system decreases by 48.7 kJ because there are fewer

water molecules than hydrogen and oxygen molecules combining. The extra entropy is released

into the environment as heat. The amount of energy per mole of hydrogen is the change in Gibbs

free energy, show in this equation: ΔG = ΔH - TΔS = -285.83 kJ + 48.7 kJ = -237.1 kJ. Fuel

energy is converted to electrical energy at 83% efficiency in this ideal system.

The problem of climate change and global warming is not going away on its own. The

solution to this problem depends on every citizen taking responsibility for the amount of energy

they consume and the consumption of products generated from the derivatives of raw products.

Driving less will reduce the amount of CO2 released into the atmosphere and keeping the tire

pressure of our car’s tires at the recommended level can increase the fuel efficiency of our cars.

By taking action we will reduce the amount of CO2 released into the atmosphere. It is necessary

to educate young generations about ways to protect our surroundings to help it return to its

normal equilibrium stage. There are more and more technological advances that can help us set

our minds right and realize the importance of saving energy. Citizens can use more public

transportation which will lead to less consumption of oil and less carbon monoxide and carbon

dioxide production.

In addition, the government also has a responsibility to develop new technologies for

alternative fuels. Using bio diesel or ethanol are good options. Hydrogen is an alternative fuel

source that was pursued and funded by the Bush administration in 2003. There is currently a

government project in place called the Hydrogen Fuel Initiative, whose goal is to make fuel cell

technology for automobiles cost-effective and practical by 2020.

Another more cost-effective option for hydrogen as an energy carrier is using it in altered

combustion engines in place of gasoline. Engines would have to be adjusted to change ignition

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timing, some type of fluid would need to be used in place of oil to lubricate the cylinders, and

scientists would need to develop a safer more space-efficient way to store liquid hydrogen. The

main problem with using altered combustion engines is that hydrogen in its liquid form can be

highly volatile and takes up much more space than gasoline. Gas stations cannot be easily

changed to hydrogen filling stations.

The bottom line is that climate change is a global problem that we are facing and it needs

to be addressed. If not, life as we know it now will be drastically different within 50 years.

Using alternative fuel sources is one of the most effective ways to make serious changes in our

worlds. Hydrogen as a fuel source is one option, but it may not be the best because of its cost,

the energy consumed in making hydrogen and the fact that making hydrogen contributes to more

greenhouse gases. The government has a responsibility to also pursue other fuel sources.

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2006_A_10000000000000049032

http://www.hi2h2.com/

http://www.weltemp.eu/

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