Free Radicals Defined:
Free radicals are a byproduct of normal cell function. When cells create energy, they also produce unstable oxygen molecules. These molecules, called free radicals, have a free electron. This electron makes the molecule highly unstable. The free radical bonds to other molecules in the body – causing proteins and other essential molecules to not function as they should. Luckily, antioxidants can minimize free radical damage.
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Last week the US government announced that it believes it has successfully breached the fuel tank on a dead satellite, effectively destroying the toxic fuel stored on board: 1000 pounds of hydrazine. Hydrazine is a simple nitrogen compound, two NH2 groups joined by a NN single bond. How does such a simple compound power a rocket?
Hydrazine is a hypergolic propellant – one that ignites as soon as it comes into contact with an oxidant (something that will react with it to effectively strip away some electrons from the reactant and force the molecule to bond differently, the changes in the bonds between atoms are what release the energy). Hypergolic is apparently a term coined by the German rocket program from hyper (very) + ergon (Greek for work) + ol (from oleum, the Latin for oil). Hydrazine is that, a liquid (if not particularly oily one) that can be used to push satellites around in orbit – to do work.
Hydrazine is a solid in the satellite’s tanks, and once thawed can be catalytically and rapidly decomposed. Almost any metal will do, though iridium is the usual choice. The reactions produce lots of very hot gases, which you can direct through a thruster:
3 N2H4 → 4 NH3 + N2
N2H4 → N2 + 2 H2
NH3 + N2H4 → 3 N2 + 8 H2
A little thermochemistry can quickly tell you just how much energy you might produce from 1000 pounds of hydrazine. The overall reaction is:
5 N2H4 → 5 N2 + 10 H2
which releases 50,000 Joules of energy per mole of hydrazine. A mole of hydrazine weighs about 32 grams, so you get enough energy to make a cold cup of coffee hot from just over an ounce of hydrazine (do NOT try this at home!). If all the hydrazine in that satellite went up at once, it would release about 8 billion Joules (enough to keep the average US citizen in energy for more than a week).
The pinacol rearrangement is essentially a dehydration reaction of an alcohol, specifically a diol. The following is an example of a pinacol rearrangement in which the (R,R)-diol (TBDMS is tert-butyldimethylsilyl) was allowed to react with 2,2 dimethylpropane (2,2-DMP) in the presence of boron trifluoride etherate at room temperature. This particular reaction was done in order to attain the acetone derivative.
Interestingly, instead of retaining its chirality, the product of the pinacol arrangement actually resulted in a racemic mixture. Subsequent derivatives of this product eventually yield benzophenone (hydroxyphenstatin), which, biologically, is a potent antitumor and antimitotic agent. Accordingly, hydroxyphenstatin has also been proven to inhibit tubulin assembly.
Regulations controlling diesel exhaust become more exacting with each passing year. Accordingly, diesel fuel properties are constantly being analyzed in an attempt to further reduce fuel emissions. There are many options, most often refinement processes or improving the cetane number. Essentially, short and branched ethers (used in gasoline) have a good octane number but poor cetane number, while those ethers used in diesel are linear and have a comparatively long chain (ideally 9 or more carbons). Di-n pentyl ether (DNPE) has shown most effective in reducing emissions, and is also relatively simple to synthesize via the bimolecular dehydration of 1-pentanol on acid catalysts, as seen below.
However, the dehydration reaction results in quite a lot of byproducts, including other ethers. As such, a selective catalyst is required to favor production of DNPE by reducing the amount of alkenes. Increased selectivity can be accomplished via gel-type acidic resins at a reaction temperature of 150°C. The article I looked at analyzed the selectivity and reaction rate of the dehydration of 1-pentanol to DNPE using a gel-type resin at various temperatures and alcohol flow rates.
Almost everyone has seen a lightstick. A lightstick is a plastic tube with a glass vile inside it. When the tube is bent, the vial breaks allowing the chemicals to mix and react. The colorfully glowing sticks utilize a chemical process called chemiluminescence where energy is released in the form of light. The most common lightsticks use chemiluminescence with colored tubes to provide the desired color.
This process is not caused by heat and may not produce heat, but the speed of reaction is still dependence on environmental heat. The colder the environment, the slower the reaction and will glow longer.
Lightsticks have three parts. There are two chemicals that react to release energy which is converted to light. Usually, commercial lightsticks utilize the reaction between hydrogen peroxide and acetonitrile. When the glass vile is broken and the two chemicals are mixed, it will release enough energy to excite the electrons in the oxygen to cause the electrons to jump to a higher energy level and then fall back releasing light.
Specifically, the hydrogen peroxide oxidizes the acetonitril eventually forming excited oxygen. This decomposes and releases the energy as light as can be seen stepwise above.
More on chemiluminescence can be found here on “A Chemiluminescence Reaction between Hydrogen Peroxide and Acetonitrile and Its Applications.”
