Sulfuric Acid Train Derailed

A locomotive and all 26 carriages containing sulfuric acid derailed in north Queensland on Sunday 27^th December 2015.
The 800,000 L of sulfuric acid was bought by Incitec Pivot Limited (IPL) to be used in the production of ammonium phosphate fertiliser at its plant at Phosphate Hill (south of Mount Isa).

Glencore Plc has an agreement with Incitec Pivot Ltd to provide sulfur dioxide from the copper smelter to the Mount Isa acid plant. Sulfuric acid is produced by collecting and cleaning sulfur dioxide before converting it, first to sulfur trioxide, and then to sulfuric acid. The acid plant has the capacity to take up to 80% of the sulfur dioxide emissions from the copper smelter, significantly reducing the emissions of sulfur dioxide into the atmosphere. The sulfuric acid is then taken by train to Phosphate Hill, more than 100 km away.

Phosphate Hill combines a large open-cut phosphate mine with a plant for the production of fertiliser. The proved reserve is 29 Mt at 24.6% P₂O₅. The phosphate ore is first crushed and washed before being dissolved in sulfuric acid to produce phosphoric acid. Gypsum, CaSO₄.2H₂O, a by-product of the process, is stockpiled. The phosphoric acid is converted into ammonium phosphate fertiliser using ammonia gas:
 NH₃ + H₃PO₄ → NH₄H₂PO₄ (known as MAP)
2NH₃ + H₃PO₄ → (NH₄)₂HPO₄ (known as DAP)
The ammonium phosphate is then sent by train to the port at Townsville about 900 km away for shipment.

Wet weather hampered access to the disaster site for several days, but testing of the waters 8 km downstream in Horse Creek revealed changes in acidity. Locally sourced limestone is being used to treat the water.

References:
http://statements.qld.gov.au/Statement/2015/12/31/environmental-testing-continues-around-train-derailment-near-julia-creek
 http://www.abc.net.au/news/2015-12-30/fear-sulphuric-acid-leaked-train-derailed-waterway-julia-creek/7060070

Further Reading
 Copper Smelting
 Electrorefining
 Sulfuric Acid Production
Density Calculations
Percentage Composition 
 Intermolecular Forces
pH Scale 
pH Calculations for Acids  
Neutralisation

Suggested Study Questions:

1. Convert 800 000 L of sulfuric to a volume in:
   • megalitires (ML)
   • kilolitres (KL)
   • millilitres (mL)
2.  Assume the density of this sulfuric acid is 1.84 g mL^-1. What is the mass of 800,000 L of sulfuric acid?
3. Assuming all the sulfuric acid was distributed equally between the 26 carriages, what volume of sulfuric acid was contained in each carriage?
4. Write the chemical formula for each of the following:
• sulfur dioxide
• sulfur trioxide
• sulfuric acid
• sulfurous acid
5.  Convert 29 Mt of phosphate ore to a mass in
   • tonnes (t)
   • kilotonnes (kt)
   • kilograms (kg)
   • grams (g)
6.   A phosphate ore contains 24.6% P₂O₅
   • What mass of P₂O₅ is present in 1 tonne of the ore?
   • What mass of the element phosphorus is present?
   • What mass of the element oxygen is present?
7.  Give the systematic IUPAC name for each of the following:
   • NH₄H₂PO₄
   • (NH₄)₂HPO₄
8. Calculate the percentage by mass of nitrogen in
   • NH₄H₂PO₄
   • (NH₄)₂HPO₄
9. In situations in which too much nitrogen in the fertiliser can adversely affect germination, which phosphate, MAP or DAP, should be used? Explain your answer. 
10. Hygroscopy is the ability of a substance to  attract and hold water molcules from the surrounding environment. Which phosphate, MAP or DAP, would you expect to be more hygroscopic? Explain your answer.
11. Sulfuric acid from the derailed carriages is believed to be leaking into the water of Horse Creek. Do you expect the pH of the creek to be rising or falling? Explain your answer.
12. If the pH of the creek water was 3.0, calculate the concentration of hydrogen ions in the creek water.
13. Explain what the term neutralisation means.
14. Assuming limestone is composed of calcium carbonate only, write a balanced chemical equation for the reaction between sulfuric acid and limestone.
15. Would you describe the chemical reaction described by the equation in question 14 as a neutralisation reaction? Explain your answer.
16. In the laboratory you could use sodium hydroxide to neutralise sulfuric acid. Why isn't sodium hydroxide used to neutralise the sulfuric acid at the train derailment site?

 

Green Hair

Imagine you are living in a small town in Sweden.
You go to bed one night, naturally blonde.
When you wake up in the morning and look in the mirror your blonde hair has turned green!
Not only that, but your naturally blonde neighbour also has green hair!

This actually did happen in 2011, and, no doubt, caused a certain amount of distress.

Where would you begin in order solve the "green hair" mystery?
What could turn hair green?

Blonde hair often turns green after swimming in chlorinated pool water.
Copper, used in compounds to reduce algae growth in water, can be present in concentrations of about 0.5 ppm in pool water. When bleach (often sold as "liquid chlorine") is added to the pool water it oxidizes the copper resulting in a pretty green colour, and the oxidized copper binds to the proteins in the hair.
If you happen to have copper pipes in your bathroom, you've probably seen "green stains" on the pipes where the copper has been oxidized.

So, back to the story in Sweden.
Samples of drinking water were taken from a number of homes in order to measure the amount of copper present but the concentration of copper in the water did not exceed the recommended guidelines (that is, the copper ion concentration was less than 1 ppm).

However, in new houses, when hot water was left overnight and tested the next morning, the concentration of copper in the water increased dramatically. On further investigation it was discovered that the hot water pipes in new houses lacked the coating that the pipes in older houses had. So, overnight, when the water in the pipes was still and not being continuously "flushed" through the pipes, copper particles were being added to the water.

For solving the "Swedish Green Hair Mystery" Johan Pettersson was rewarded with a 2012 Ig Nobel Prize for Chemistry.


References:
http://www.thelocal.se/37994/20111217/
http://www.improbable.com/ig/winners/#ig2012

Further Reading 
http://www.ausetute.com.au/waterana.html 
http://www.ausetute.com.au/aas.html 
http://www.ausetute.com.au/partspm.html 
http://www.ausetute.com.au/concsols.html 
http://www.ausetute.com.au/weightpc.html 
http://www.ausetute.com.au/corrosion.html 

Suggested Study Questions:

1. Describe 2 methods you could use to detect the presence of copper ions in water.
2. Describe the process by which Atomic Absorption Sepctroscopy (AAS) could be used to measure the concentration of copper ions in a water sample.
3. Describe a way that you could prevent copper from entering the water in the copper water pipes in this Swedish town.
4. Copper is often present in soils at a concentration of around 50 ppm. What mass of copper would be present in 0.5 tonne of soil?
5. A particular pool contains 40,000 L of water. If the pool water contains 0.5 ppm copper ions, what is the concentration of copper ions in mol L^-1 ?
6. Chocolate can contain 10 mg/kg  copper. What mass of copper is present in a 250 g bar of chocolate?
7. Doses of copper that exceed 50 mg/kg of body mass can be lethal. Calculate the mass of copper that would be the lethal limit for an 80 kg adult.
8. What advice could you give the inhabitants of this Swedish town in order for them to avoid having green hair?

Atom Transfer Radical Polymerization

Atom transfer radical polymerization (ATRP) is a way of forming carbon-carbon bonds in a controlled piece-by-piece fashion using a transition metal catalyst. ATRP is used to make polystyrene, poly(methyl methacrylate) and polyacrylamide.

The ATRP process relies on paired reduction-oxidation (redox) reactions between two species of copper:

• the activator, Cu⁺
  
• the deactivator, Cu²⁺
  

where the two catalysts exchange electrons back and forth.
Occasionally, one of the exchanges will spontaneously stop, called a radical termination, resulting in the accumulation of Cu²⁺. To keep the polymerization going, chemists must re-balance the system by compensating for the excess Cu²⁺. Simply adding more Cu⁺ to the system produces materials with high, sometimes toxic, levels of copper, up to 5,000 ppm. Such levels of copper are hard to remove using current industrial equipment. It has been found that reducing agents like sugars or vitamin C are highly effective in reducing the amount of copper catalyst used in ATRP reactions.

In a new study, Carnegie Mellon University chemists have found that they can use electricity from a battery to drive these ATRP reactions. Adding electricity capitalized on the redox reaction by moderating the transfer of electrons. This allowed them to compensate for the radical terminations and reduce the amount of copper needed to run ATRP. As a result the amount of copper in the system was reduced to 50 ppm, a 100-fold decrease.

Reference
Andrew J. D. Magenau, . Nicholas C. Strandwitz, . Armando Gennaro and Krzysztof Matyjaszewski. Electrochemically Mediated Atom Transfer Radical Polymerization. Science, 1 April 2011: Vol. 332 no. 6025 pp. 81-84 DOI: 10.1126/science.1202357

Further Reading:
Parts per Million (ppm)
Polymers and Polymerization
Oxidation and Reduction
Le Chatelier's Principle

Study Questions:

1. If 1kg of polystyrene contained 5000 ppm copper, what mass of copper would be present?
2. If 1kg of polyacrylamide contained 50 ppm copper, what mass of copper would be present?
   
3. Name the monomer that is used to produce each of the following polymers:
   
   • polystyrene
   • poly(methyl methacrylate)
   • polyacrylamide
4. Provide the structural formula for each of the monomers in question 1.
5. Draw the structure for each of the polymers listed in question 1.
6. In the reaction:
   Cu⁺ Cu²⁺ + e
   which species is
   • being oxidized?
   • being reduced?
   • the oxidant?
   • the reductant?
7. What is meant by each of the following terms:
   • oxidation
   • reduction
   • redox
     
   
   
8. Explain the statement "Adding electricity capitalized on the redox reaction by moderating the transfer of electrons. "
9. In the article, it is suggested that adding Cu⁺ or using electricity can moderate the transfer of electrons. Suggest another way that this might be accomplished.