Thursday, March 19, 2009

Health and Environment Effects of Hydrogen

Effects of exposure to hydrogen: Fire: Extremely flammable. Many reactions may cause fire or explosion.Explosion: Gas/air mixtures are explosive. Routes of exposure: The substance can be absorbed into the body by inhalation. Inhalation: High concentrations of this gas can cause an oxygen-deficient environment. Individuals breathing such an atmosphere may experience symptoms which include headaches, ringing in ears, dizziness, drowsiness, unconsciousness, nausea, vomiting and depression of all the senses. The skin of a victim may have a blue color. Under some circumstances, death may occur. Hydrogen is not expected to cause mutagenicity, embryotoxicity, teratogenicity or reproductive toxicity. Pre-existing respiratory conditions may be aggravated by overexposure to hydrogen. Inhalation risk: On loss of containment, a harmful concentration of this gas in the air will be reached very quickly.

Physical dangers: The gas mixes well with air, explosive mixtures are easily formed. The gas is lighter than air.

Chemical dangers: Heating may cause violent combustion or explosion. Reacts violently with air, oxygen, halogens and strong oxidants causing fire and explosion hazard. Metal catalysts, such as platinum andnickel, greatly enhance these reactions.

High concentrations in the air cause a deficiency of oxygen with the risk of unconsciousness or death. Check oxygen content before entering area. No odor warning if toxic concentrations are present. Measure hydrogen concentrations with suitable gas detector (a normal flammable gas detector is not suited for the purpose).

First aid: Fire: Shut off supply; if not possible and no risk to surroundings, let the fire burn itself out; in other cases extinguish with water spray, powder, carbon dioxide. Explosion: In case of fire: keep cylinder cool by spraying with water. Combat fire from a sheltered position. Inhalation: Fresh air, rest. Artificial respiration may be needed. Refer for medical attention. Skin: Refer for medical attention.


Hydrogen in the environment: Hydrogen forms 0.15 % of the earth's crust, it is the major constituent of water. 0.5 ppm of hydrogen H2 and varial proportions as water vapour are present in the atmosphere. Hydrogen is also a majosr component of biomass, consituing the 14% by weight.

Environmental stability: hydrogen occurs naturally in the atmosphere. The gas will be dissipated rapidly in well-ventilated areas.

Effect on plants or animals: Any effect on animals would be related to oxygen deficient environments. No adverse effect is anticipated to occur to plant life, except for frost produced in the presence of rapidly expanding gases.

Effect on aquatic life: No evidence is currently available on the effect of hydrogen on aquatic life.


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Hydrogen

  • Name: Hydrogen 
  • Symbol: H 
  • Atomic Number: 1 
  • Atomic Mass: 1.00794 amu 
  • Melting Point: -259.14 °C (14.009985 K, -434.45203 °F) 
  • Boiling Point: -252.87 °C (20.280005 K, -423.166 °F) 
  • Number of Protons/Electrons: 1 
  • Number of Neutrons: 0 
  • Classification: Non-metal 
  • Crystal Structure: Hexagonal 
  • Density @ 293 K: 0.08988 g/cm3 
  • Color: colorless

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HYDROGEN USE IN VEHICLES

Today, there are an estimated 400 to 500 hydrogen-fueled vehicles in the U.S., mostly in California. Most of these vehicles are buses and automobiles powered by electric motors. They store hydrogen gas or liquid on board and convert the hydrogen into electricity for the motor using a fuel cell. Only a few of these vehicles burn the hydrogen directly (producing almost no pollution). The present cost of fuel cell vehicles greatly exceeds that of conventional vehicles in large part due to the expense of producing fuel cells.

Hydrogen vehicles are starting to move from the laboratory to the road. One California family has recently leased a hydrogen car for personal use. The U.S. postal service, a package delivery company, a few Florida Park rangers, and a few private utility companies are also using hydrogen vehicles. It will probably be at least 10 years, though, before you can walk into your local car dealer and drive away in an affordable hydrogen-powered car. 

Even then, you will need a place to refuel your hydrogen car. Currently, there are 63 hydrogen refueling stations nationwide, about half of which are located in California. This is the so-called “chicken and egg” problem that hydrogen developers are working hard to solve. Namely: who will buy hydrogen cars if there are no refueling stations? And who will pay to build a refueling station if there are no cars and customers? 

One possible solution is to eliminate refueling stations entirely. Automobile manufacturers have already designed a refrigerator-sized hydrogen generator for your garage that works off electricity.  Consumers would simply refill their cars with hydrogen each night while it is parked.

Hydrogen has great potential as an environmentally clean energy fuel and as a way to reduce reliance on imported energy sources. Before hydrogen can play a bigger energy role and become a widely used alternative to gasoline, many new facilities and systems must be built. We will need facilities to make hydrogen, store it, and move it. We will need economical fuel cells. And consumers will need the technology and the education to safely use it.

Last Reviewed: October 2008 
Sources: Energy Information Administration, The Impact of Increased Use of Hydrogen on Petroleum Consumption and Carbon Dioxide Emissions, August 2008.
Energy Information Administration, Alternatives to Traditional Transportation Fuels 2006, May 2008.
The National Energy Education Development Project, Intermediate Energy Infobook, 2005.

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How Hydrogen Made and Uses of Hdrogen

HOW IS HYDROGEN MADE?

Since hydrogen doesn't exist on earth as a gas, we must separate it from other elements. We can separate hydrogen atoms from water, biomass, or natural gas molecules. The two most common methods for producing hydrogen are steam reforming and electrolysis (water splitting). Scientists have even discovered that some algae and bacteria give off hydrogen.

  • Steam reforming is currently the least expensive method of producing hydrogen and accounts for about 95 percent of the hydrogen produced in the United States. It is used in industries to separate hydrogen atoms from carbon atoms in methane(CH4). Because methane is a fossil fuel, the process of steam reforming results in greenhouse gasemissions that are linked with global warming.

  • Electrolysis is a process that splits hydrogen from water. It results in no emissions but it is currently a very expensive process. New technologies are being developed all the time.

Hydrogen can be produced at large central facilities or at small plants for local use. Every region of the country (and the world) has some resource that can be used to make hydrogen. Its flexibility is one of its main advantages


USES OF HYDROGEN

About 9 million metric tonnes of hydrogen are produced in the United States today, enough to power 20-30 million cars or 5-8 million homes. Nearly all of this hydrogen is used by industry in refining, treating metals, and processing foods. Most of this hydrogen is produced in just three states: California, Louisiana, and Texas.

The National Aeronautics and Space Administration (NASA) is the primary user of hydrogen as an energy fuel; it has used hydrogen for years in the space program. Liquid hydrogen fuel lifts the space shuttle into orbit. Hydrogen batteries—called fuel cells—power the shuttle’s electrical systems. The only by-product is pure water, which the crew uses as drinking water.

Hydrogen Fuel CellHydrogen fuel cells (batteries) make electricity. They are very efficient, but expensive to build. Small fuel cells can power electric cars. Large fuel cells can provide electricity in out of the way places with no power lines.

Because of the high cost to build fuel cells, large hydrogen power plants won't be built for a while. However, fuel cells are being used in some places as a source of emergency power to hospitals and to wilderness locations. Portable fuel cells are being sold to provide longer power for laptop computers, cell phones, and military applications.

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HYDROGEN - AN ENERGY CARRIER

Energy carriers move energy in a usable form from one place to another. Electricity is the most well-known energy carrier. We use electricity to move the energy in coal, uranium, and other energy sources from power plants to homes and businesses. We also use electricity to move the energy in flowing water from hydropower dams to consumers. It is much easier to use electricity than the energy sources themselves.

Like electricity, hydrogen is an energy carrier and must be produced from another substance. Hydrogen is not widely used today but it has great potential as an energy carrier in the future. Hydrogen can be produced from a variety of resources (water, fossil fuels, biomass) and is a byproduct of other chemical processes. Unlike electricity, large quantities of hydrogen can be easily stored to be used in the future. Hydrogen can also be used in places where it’s hard to use electricity. Hydrogen can store the energy until it’s needed and can be moved to where it’s needed.


Last Reviewed: October 2008 
Sources: Energy Information Administration, The Impact of Increased Use of Hydrogen on Petroleum Consumption and Carbon Dioxide Emissions, August 2008.
Energy Information Administration, Alternatives to Traditional Transportation Fuels 2006, May 2008.
The National Energy Education Development Project, Intermediate Energy Infobook, 2005.


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What is Hydrogen

Hydrogen is the simplest element known to man. Each atom of hydrogen has only one proton. It is also the most plentiful gas in the universe. Stars are made primarily of hydrogen.

The sun is basically a giant ball of hydrogen and helium gases. In the sun's core, hydrogen atoms combine to form helium atoms. This process—called fusion—gives off radiant energy.

This radiant energy sustains life on earth. It gives us light and makes plants grow. It makes the wind blow and rain fall. It is stored as chemical energy in fossil fuels. Most of the energy we use today came from the sun's radiant energy.

Hydrogen gas is lighter than air and, as a result, it rises in the atmosphere. This is why hydrogen as a gas (H2) is not found by itself on earth. It is found only incompound form with other elements. Hydrogen combined with oxygen, is water (H2O). Hydrogen combined with carbon, forms different compounds such as methane (CH4), coal, and petroleum. Hydrogen is also found in all growing things—biomass. It is also an abundant element in the earth's crust.

Hydrogen has the highest energy content of any common fuel by weight(about three times more than gasoline), but the lowest energy content by volume (about four times less than gasoline). It is the lightest element, and it is a gas at normal temperature and pressure.

Last Reviewed: October 2008 
Sources: Energy Information Administration, The Impact of Increased Use of Hydrogen on Petroleum Consumption and Carbon Dioxide Emissions, August 2008.
Energy Information Administration, Alternatives to Traditional Transportation Fuels 2006, May 2008.
The National Energy Education Development Project, Intermediate Energy Infobook, 2005.


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Friday, March 13, 2009

Chemical Bonding - An Introduction

Chemical Bonding.

These notes are based (loosely) on my series of lectures given in the Introductory Chemistry module (Biology, Environmental Science degree) and in the first year inorganic unit of the Higher National Certificate course at the North East Wales Institute, Wrexham. These notes should be seen as supplementary to those lectures and not as replacing them ! These notes are designed to give a quick guide to bonding - there is a lot more to this subject than is covered here and I would love it if these brief notes encouraged you to study the subject further but, hey, life is short, so if these help you then great. If you find them useful or have any comments to make then please e-mail me. You might also want to take a look at the more advanced material available here - links at the end of these notes.

Why are chemical bonds formed ?

Chemical bonds form to lower the energy of the system, the components of the system become more stable through the formation of bonds. Everything wants to be more stable - its easy to lie down than stand up, bonding is Nature's way of allowing the elements to lie down.

There are several types of chemical bond. Initially we will concern ourselves with three basic types, ionic bonding, which involves the transfer of electron(s), covalent bonding, which involves sharing of electrons and metallic bonding, which in some ways can be considered as a combination of both.

If we examine the periodic table, we find that the elements in Group VIII (or 18), helium, neon, argon and so on, are particularly stable, so much so that they were once labeled the "inert gases". We now know that these elements are not inert, indeed xenon forms a range of compounds, but, nevertheless, they are very stable (although now we refer to these elements as the noble gases). This stability is the result of their electronic configuration, they have a full valence shell of electrons (ns2, np6) and this imparts stability. G. N. Lewis (1916) suggested that bonds (covalent) formed to enable elements to attain this "noble gas configuration". We can extend this idea to ionic compounds, in a compound such as sodium chloride, one element loses electron(s) to gain this stable electronic configuration whilst the other gains electron(s) to achieve the same result.

We can see that in each case, sharing or transfer of electrons, results in a more stable system.

So can we predict the type of bonds which will form between different elements in the periodic table ? The answer is yes (usually). The elements to the left of the periodic table (Groups I and II) can achieve the noble gas electronic configuration by losing electron(s). Ionization enthalpies show that lose of these is relatively easy (ionization enthalpies are fairly low for the elements in these groups). These elements are termed "electropositive". The opposite is true of the elements to the right of the periodic table. Elements in groups VII and VIII (17, 18) can most easily attain the noble gas configuration by gaining electron(s). These are the electronegative elements. (A measure of their ability to accept electrons can be seen in the electron affinity values for these elements).

This information allows us to predict that compounds formed by the combination of an electropositive element with an electronegative element will involve the transfer of electron(s) from the electropositive element to the electronegative element and hence ionic bonding will occur. The degree of ionic bonding will depend upon how extreme the differences are (in terms of electropositive / electronegative character) between the particular elements. Electropositive character increases down the group whilst electronegative character increases up a group. Combination of the most highly electropositive elements (e.g. Cs, Fr) with the most electronegative element (F) will result in the "most ionic" compounds, other combinations (such as Li with Br) will be much less ionic. In other words, transfer of electron(s) is never total, for example CsF is approximately 97% ionic, there is always some degree of covalency (however small).

When we get combination between two electronegative elements, the result is a sharing of electrons and so covalent bonds form. This is best illustrated by the combination of two atoms of the same element (a homonuclear diatomic). Combination of two fluorine atoms to produce F2, for example is achieved by sharing electrons, each fluorine atom donating one electron to form a two electron (two centre, two atoms) bond. The covalent bond is formed by overlap (or combination) of atomic orbitals of each element to form a molecular orbital. The formation of molecular orbitals lies at the heart of Molecular Orbital Theory and is the subject of another set of notes. In simplistic terms, we can visualise the sharing of two electrons between atoms as forming a single bond between the two atoms, joining them together. If the atoms share two electrons each (i.e. 4 in total) we have a double bond which will be stronger (and shorter) than a single bond. Likewise, sharing six electrons gives us a triple bond.

For combination of two electropositive elements we have metallic bonding. Perhaps the best way to model this is with "band theory" but that is the basis of other notes (when they are written). For now, we can simply visualise this as each metal donating electron(s) to a common "sea" of electrons which are shared by all the ions within the solid.

Properties of compounds.

We can make some general statements about the properties of compounds based on the bonding present. These are general statements and so you will find exceptions to these descriptions but they should prove useful for a basic understanding of the chemistry involved.

Ionic Compounds

Ionic compounds are generally solids at room temperature and have high melting and boiling points. They are hard but brittle solids and are poor conductors of electricity in the solid state (good conductors when molten or in solution). To explain these properties we must examine the nature of the bonding in these compound. Ionic bonds are "strong" and omnidirectional (i.e. the ions are attracted to ions of opposite charge in all directions). The ions are (to an extent) fixed in their position within the crystal lattice and have difficulty moving from these positions, being held in position by their attraction to the surrounding ions. If the ions are moved (say through physical force) this attraction is broken and alignment of like charges can occur resulting in repulsion - hence the solid is brittle. The observation that electrical conduction (however low) does occur is caused by defects in the crystal structure and this subject forms part of another series of my lectures (catch them if you can !). In solution (or when molten) the ions are able to move more easily and hence conduction (through the movement of these ions) is possible. As a side note, there are compounds which are essentially ionic which do conduct electricity rather well. These are called solid electrolytes, this is a rather speciallised area and I don't want to confuse you by spending time on this subject - if you are interested look up "silver iodide" or "ß-alumina" in a solid state chemistry text book.

Covalent Compounds

In general, covalent compounds have the property of being boring at least in terms of their physical properties. They represent most of that branch of chemistry known as organic chemistry, which perhaps explains a lot. I’m joking, organic chemistry is very interesting, especially if you are an organic chemist (I am not!). Covalent compounds are not boring. Maybe a little dull, but definitely not boring. What can we say about covalent compounds ? In general they are gases or liquids at room temperature.

That about says it.
Okay, one or two are solids because of extended 3 dimensional networks (diamond for example) but most are not solids (and in any case, most of these interesting ones belong in inorganic chemistry!). I suppose there’s some interest in polar covalent compounds (polar means a little ionic) but really that’s about it as far as properties go. There is some interesting chemistry of covalent compounds (I suppose) and we will look at that later but for now if you want to find out more about the properties then look elsewhere (ask an organic chemist - they are instantly recognisable).

Metals

Metals are much more interesting. They are generally solids at room temperature. They conduct electricity and heat well and are malleable. They have high tensile strength and are usually hard. To explain these properties we must examine the bonding present. We can visualise the bonding in terms of the valence electrons of the atoms being shared throughout the metal structure. The model that tends to be applied is Band Theory but for now we can imagine the metal ions held together by this "sea" of electrons. This allows the metal to be bent and distorted without the structure breaking. These electrons are also relatively free to move and this explains the high electrical conductivity of metals.

Other types of bonding

We have looked briefly at the three major types of bonding but there are other, in many ways, just as important types of bonding.

Dative (Covalent) Bonding

If a atom has a lone (non-bonding) pair of electrons, this can be donated to form a dative covalent bond (provided the receiving atom can accept them). Atoms (or molecules) which have such lone pairs are called Lewis Bases, atoms (or molecules) which can accept such lone pairs are Lewis Acids. For example ammonia, NH3. The nitrogen has a lone pair of electrons, we can represent this as :NH3, ammonia is a Lewis Base. Boron trifluoride, on the other hand is a Lewis Acid, the boron has a vacant p orbital (there are six valence shell electrons around the boron, two short of the "stable octet"). The boron can accept the lone pair of electrons from the nitrogen and we get the adduct F3B-NH3. (Strange word that adduct - wonder what it means? Why not look it up?)

Polar Bonds

I have already suggested that our models for covalent and ionic bonds are idealised and that in reality we have bonds which are intermediate between these two types. If we take HCl for example, we might suppose that there is a covalent bond between the hydrogen and the chlorine. In fact the chlorine atom is more electronegative than the hydrogen atom and so attracts more of the electron density than does the hydrogen. The upshot of this is that the chlorine becomes slightly negative (i.e. has more than an equal share of the electrons) and the hydrogen becomes slightly positive (i.e. has less than an equal share). The bond becomes slightly "ionic" in nature and the molecule becomes polar (one end is slightly negative, the other slightly positive). It is fairly simple to decide whether or not a diatomic (two atom) molecule is polar, all we need do is judge whether or not there is a significant difference in the electronegativities of the two elements present. When we get multi-atom molecules the situation is a little more complex and we have to take into account how the atoms are arranged. Carbon tetrachloride (CCl4) for example, each C-Cl bond is polar since the chlorine is more electronegative than the carbon, but the chlorine atoms are arranged symmetrically about the carbon (tetrahedrally arranged) and so overall the molecule is non-polar. Before we can predict whether or not such a molecule is polar we have to know, or be able to predict, the shape of the molecule and this topic forms another series of notes.

The effect of molecule polarity upon the physical properties of a substance can be quite startling. What do you think might happen between different molecules of a substance when that molecule is polar ? The answer lies in the attraction between non-like (opposite) charges. Opposite charges will attract one another and so in polar substance molecules will associate with one another, this is called dipole-dipole interaction. What effect do you think this will have on, say, boiling point ?

Hydrogen bonding

One very important example of dipole-dipole interaction has been given its own name, hydrogen bonding. An every day example of this is in water. The oxygen - hydrogen bond is polar, oxygen being the more electronegative element. The molecule is therefore polar (the molecule is not linear but has a bent, V, shape). This is extenuated by the two lone pairs of electrons on the oxygen atom. One end of the molecule is partially negative whilst the two hydrogen atoms become partially positive. The molecules of water are attracted to one another, with the slightly positive hydrogens attracted to the negative "ends" (the oxygens) of other water molecules. This intermolecular attraction is termed "hydrogen bonding", and acts almost like a glue holding the molecules of water together. In the case of water the effect on the physical properties of water are quite astounding, the boiling point of water, for example, is very much greater than would be the case if such bonding did not exist. This fact alone should make the human race (and the rest of life) grateful for hydrogen bonding since water would otherwise be a gas at room temperature. Can you think of another physical property which would be strongly influenced by this "glue"?

Other forces of attraction.

It is possible to liquefy the elements known as the noble gases. Maybe you don’t find this surprising, cool anything and it will liquefy. But what holds the atoms of these elements together ? There must be some form of attraction.

Imagine an atom. The atom is not a static thing, electron density fluctuates around that atom. At some point in time it is possible that the electron density on one side of the atom is greater than on the other side. We have an instantaneous dipole. If the mixture is sufficiently cold (the atoms are not moving quickly) then an adjacent atom will experience this dipole and will itself establish a dipole in response. We now have an attraction between the atoms (instantaneous dipole - induced dipole interaction). Such attraction is not strong, rather it is very weak, but nevertheless it exists.

Intermolecular forces of attraction, those not involving ions, are generally referred to as van der Waal’s forces.



Dr Clive Buckley
Updated 09 December 1999

School of Education and Humanities
Faculty of Science & Technology
Athrofa Addysg Uwch Gogledd Ddwyrain Cymru
North East Wales Institute of Higher Education
Wrexham, NORTH WALES

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PFR (Plug Flow Reactor)

In a PFR, one or more fluid reagents are pumped through a pipe or tube. The chemical reaction proceeds as the reagents travel through the PFR. In this type of reactor, the changing reaction rate creates a gradient with respect to distance traversed; at the inlet to the PFR the rate is very high, but as the concentrations of the reagents decrease and the concentration of the product(s) increases the reaction rate slows. Some important aspects of the PFR:
  • All calculations performed with PFRs assume no upstream or downstream mixing, as implied by the term "plug flow".
  • Reagents may be introduced into the PFR at locations in the reactor other than the inlet. In this way, a higher efficiency may be obtained, or the size and cost of the PFR may be reduced.
  • A PFR typically has a higher efficiency than a CSTR of the same volume. That is, given the same space-time, a reaction will proceed to a higher percentage completion in a PFR than in a CSTR.
For most chemical reactions, it is impossible for the reaction to proceed to 100% completion. The rate of reaction decreases as the percent completion increases until the point where the system reaches dynamic equilibrium (no net reaction, or change in chemical species occurs). The equilibrium point for most systems is less than 100% complete. For this reason a separation process, such as distillation, often follows a chemical reactor in order to separate any remaining reagents or byproducts from the desired product. These reagents may sometimes be reused at the beginning of the process, such as in the Haber process.

Continuous oscillatory baffled reactor (COBR) is a tubular plug flow reactor. The mixing in COBR is achieved by the combination of fluid oscillation and orifice baffles, allowing plug flow to be achieved under laminar flow conditions with the net flow Reynolds number just about 100.

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CSTR (Continuous Stirred-Tank Reactor)

In a CSTR, one or more fluid reagents are introduced into a tank reactor equipped with an impeller while the reactor effluentis removed. The impeller stirs the reagents to ensure proper mixing. Simply dividing the volume of the tank by the averagevolumetric flow rate through the tank gives the residence time, or the average amount of time a discrete quantity of reagent spends inside the tank. Using chemical kinetics, the reaction's expected percent completion can be calculated. Some important aspects of the CSTR:

  • At steady-state, the flow rate in must equal the mass flow rate out, otherwise the tank will overflow or go empty (transient state). While the reactor is in a transient state the model equation must be derived from the differential mass and energy balances.
  • The reaction proceeds at the reaction rate associated with the final (output) concentration.
  • Often, it is economically beneficial to operate several CSTRs in series. This allows, for example, the first CSTR to operate at a higher reagent concentration and therefore a higher reaction rate. In these cases, the sizes of the reactors may be varied in order to minimize the total capital investment required to implement the process.
  • It can be seen that an infinite number of infinitely small CSTRs operating in series would be equivalent to a PFR.

The behavior of a CSTR is often approximated or modeled by that of a Continuous Ideally Stirred-Tank Reactor (CISTR). All calculations performed with CISTRs assume perfect mixing. If the residence time is 5-10 times the mixing time, this approximation is valid for engineering purposes. The CISTR model is often used to simplify engineering calculations and can be used to describe research reactors. In practice it can only be approached, in particular in industrial size reactors.

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