an autodidact meets a dilettante…

‘Rise above yourself and grasp the world’ Archimedes – attribution

Posts Tagged ‘hydrogen

a little about the chemistry of water and its presence on Earth

leave a comment »

So I now know, following my previous post, a little more than I did about how water’s formed from molecular hydrogen and oxygen – you have to break the molecular bonds and create new ones for H2O, and that requires activation energy, I think. But I need to explore all of this further, and I want to do so in the context of a fascinating question, which I’m hoping is related – why is there so much water on Earth’s surface?

When Earth was first formed, from planetesimals energetically colliding together, generating lots of heat (which may have helped with the creation of H2O, but not in liquid form??) there just doesn’t seem to have been a place for water, which would’ve evaporated into space, wouldn’t it? Presumably the still-forming, virtually molten Earth had no atmosphere. 

The most common theory put out for Earth’s water is bombardment in the early days by meteors of a certain type, carbonaceous chondrites. These meteors were formed further out from the sun, where water would have frozen. Carbonaceous chondrites are known to contain the same ratio of heavy water to ‘normal’ water as we find on Earth. Heavy water is formed with deuterium, an isotope of hydrogen containing a neutron as well as the usual proton. Obviously there had to have been plenty of these collisions over a long period to create our oceans. Comets have been largely ruled out because, of the comets we’ve examined, the deuterium/hydrogen ratio is about double that of the chondrites, though some have argued that those comets may be atypical. Also there’s some evidence that the D/H ratio of terrestrial water has changed over time.

So there are still plenty of unknowns about the history of Earth’s water. Some argue that volcanism, along with other internal sources, was wholly or partly responsible – water vapour is one of the gases produced in eruptions, which then condensed and fell as rain. Investigation of moon rocks has revealed a D/H ratio similar to that of chondrites, and also that of Earth (yes, there’s H2O on the moon, in various forms). This suggests that, since it has become clear that the Moon and Earth are of a piece, water has been there on both from the earliest times. Water ice detected in the asteroid belt and elsewhere in the solar system provides further evidence of the abundance of this hardy little molecule, which enriches the hypotheses of researchers. 

But I’m still mystified by how water is formed from molecular, or diatomic, hydrogen and oxygen. It occurs to me, thanks to Salman Khan, that having a look at the structural formulae of these molecules, as well as investigating ‘activation energy’, might help. I’ve filched the ‘Lewis structure’ of water from Wikipedia.

It shows that hydrogen atoms are joined to oxygen by a single bond, the sharing of a pair of electrons. They’re called polar covalent bonds, as described in my last post on the topic. H2 also binds the two hydrogen atoms with a single covalent bond, while O2 is bound in a double covalent bond. (If you’re looking for a really comprehensive breakdown of the electrochemical structure of water, I recommend this site).

So, to produce water, you need enough activation energy to break the bonds of H2 and O2 and create the bonds that form H2O. Interestingly, I’m currently reading The Emerald Planet, which gives an example of the kind of activation energy required. The Tunguska event, an asteroid visitation in the Siberian tundra in 1908, was energetic enough to rip apart the bonds of molecular nitrogen and oxygen in the surrounding atmosphere, leaving atomic nitrogen and oxygen to bond into nitric oxide. But let’s have a closer look at activation energy. 

So, according to Wikipedia:

In chemistry and physics, activation energy is the energy which must be available to a chemical or nuclear system with potential reactants to result in: a chemical reaction, nuclear reaction, or various other physical phenomena.

This stuff gets complicated and mathematical very quickly, but activation energy (Ea) is measured in either joules (or kilojoules) per mole or kilocalories per mole. A mole, as I’ve learned from Khan, is the number of atoms there are in 12g of carbon-12. So what? Well, that’s just a way of translating atomic mass units (amu) to grams (one gram equals one mole of amu). 

The point is though that we can measure the activation energy, which, in the case of molecular reactions, is going to be more than the measurable change between the initial and final conditions. Activation energy destabilises the molecules, bringing about a transition state in which usually stable bonds break down, freeing the molecules to create new bonds – something that is happening throughout our bodies at every moment. When molecular oxygen is combined with molecular hydrogen in a confined space, all that’s required is the heat from a lit match to start things off. This absorption of energy is called an endothermic reaction. Molecules near the fire break down into atoms, which recombine into water molecules, a reaction which releases a lot of energy, creating a chain of reactions until all the molecules are similarly recombined. From this you can imagine how water could have been created in abundance during the fiery early period of our solar system’s evolution. 

I’ll end with more on the structure of water, for my education. 

As a liquid, water has a structure in which the H-O-H angle is about 106°. It’s a polarised molecule, with the negative charge on the oxygen being around 70% of an electron’s negative charge, which is neutralised by a corresponding positive charge shared by the two hydrogen atoms. These values can change according to energy levels and environment. As opposite charges attract, different water molecules attract each other when their H atoms are oriented to other O atoms. The British Chemistry professor Martin Chaplin puts it better than I could:

This attraction is particularly strong when the O-H bond from one water molecule points directly at a nearby oxygen atom in another water molecule, that is, when the three atoms O-H O are in a straight line. This is called ‘hydrogen bonding’ as the hydrogen atoms appear to hold on to both O atoms. This attraction between neighboring water molecules, together with the high-density of molecules due to their small size, produces a great cohesive effect within liquid water that is responsible for water’s liquid nature at ambient temperatures.

We’re all very grateful for that nature. 

Written by stewart henderson

September 24, 2018 at 10:32 am

Posted in chemistry, science, water

Tagged with , , ,

exploring oxygen

leave a comment »


I’d much prefer choccy cigars

 

I’ve been reading David Beerling’s fascinating but demanding book The Emerald Planet, essentially a history of plants, and their contribution to our current life-sustaining atmosphere, and it has inspired me to get a handle on atmospheric oxygen in general and the properties of this rather important diatomic molecule. Demanding because, as always, basic science doesn’t come naturally to me so I have to explain it to myself in great detail to really pin it down, and then I forget. For example, I don’t have any understanding of oxidation right now, though I’ve read about it, and probably written about it, and more or less understood it, many times. Things fall apart, and then we fall apart…

Okay, let me pull myself together. Oxygen is a highly reactive gas, combining with other elements readily in a number of ways. A bushfire is an example of oxidation, in which free oxygen is ‘consumed’ rapidly, reacting with carbon in the dry wood to produce carbon dioxide, among other gases. This is also called combustion. Rust is a slower form of oxidation, in which iron reacts with oxygen to form iron oxide. So I think that’s basically what oxidation is, the trapping of ‘free’ oxygen into other gases or compounds, think carbon monoxide, sulphur dioxide, hydrogen peroxide, etc etc. Not to mention its reaction with hydrogen to form water, that stuff that makes up more than half our bodily mass. 

Well, I’m wrong. Oxidation doesn’t have to involve oxygen at all. Which I think is criminally confusing. Yes, fire and rust are examples of oxidation reactions, but so is a reaction between hydrogen and fluorine gas to produce hydrofluoric acid (it’s actually a redox reaction – hydrogen is being oxidised and fluorine is being reduced). According to this presumably reliable definition, ‘oxidation is the loss of electrons during a reaction by a molecule, atom or ion’. Reduction is the opposite. The reason it’s called oxidation is historical – oxygen, the gas that Priestley and Lavoisier famously argued over, was the first gas known to engage in this sort of  behaviour. Basically, oxygen oxidises other elements, getting them to hand over their electrons – it’s an electron thief. 

Oxygen has six valence electrons, so needs another two to feel ‘complete’. It’s diatomic in nature, existing around us as O2. I’m not sure how that works – if each individual atom wants two electrons, to make eight electrons in its outer shell for stability, why would it join with another oxygen to complete this outer shell, and then some? That makes for another four electrons. Are they now valence electrons? Apparently not, in this stable diatomic form. Here’s an expert’s attempt to explain this, from Quora

For oxygen to have a full outer shell it must have 8 electrons in it. But it only has 6 electrons in its valence shell. Each oxygen atom is actively seeking to get more electrons to complete its valence shell. If no other atoms except oxygen atoms are available, each oxygen atom will try to wrestle extra valence electrons from another oxygen atom. So if one oxygen atom merges with another, they “share” electrons, giving both a full outer shell and ultimately being virtually unreactive.

For a while this didn’t make sense to me, mathematically. Atomic oxygen has eight electrons around one nucleus. Six in the outer, ‘valence’ shell. Molecular oxygen has 16 electrons around two nuclei. What’s the configuration to make it stable? Presumably both nuclei still have 2 electrons configured in their first shells, that makes 12 electrons to make for a stable configuration, which doesn’t seem to work out. Did it have something to do with ‘sharing’? Are the shells configured now around both nuclei instead of separately around each nucleus? What was I missing here? Another expert on the same website writes this:

[The two oxygen atoms combine to] create dioxygen, a molecule (O2) in which both oxygen atoms have 8 valence electrons, so they are happy (the molecule is stable).

But what about the extra electrons? It seems I’d have to give up on understanding and take the experts’ word, and I hate that. However, the Khan academy has come to the rescue. In video 14 of his chemistry series, Khan explains that the two atoms share two pairs of electrons, so yes, sharing was the key.  So each atom can ‘kind of pretend’, in Khan’s words, that they have eight valence electrons. And this is a covalent bond, unlike an ionic bond which combines metals with non-metals, such as sodium and chloride. 

Anyway, moving on. One of the most important features of oxygen, as mentioned, is its role in water – which is about 89% oxygen by weight. But how do these two elements – diatomic molecules as we find them in our environment – actually come together to form such a very different substance?

Well. According to this video, when H2 and O2, and presumably other molecules, are formed

electrons lose energy to form the new orbitals, the energy gets away as a photon, and then the new orbitals are stuck that way, they can’t undo themselves until the missing energy comes back.

This set me on my heels when I heard it, I’d never heard anything like it before, possibly because photon stuff tends to belong to physics rather than chemistry, though photosynthesis rather undoes that argument…

So, sticking with this video (from Brigham Young University Physics Department), to create water from H2 and O2 you need to give them back some of that lost energy, in the form of ‘activation energy’, e.g by ‘striking a match’. The video turns out to be kind of funny/scary, and it again involves photons. After the explosion, water vapour was found condensing on the inside of the glass through which hydrogen was pumped and ignited…

Certainly the demonstration was memorable (and there are a few of these explosive vids online), but I think I need more theory. Hopefully I’ll get back to it, but it seems to have much to do with the strong covalent bonds that form, for example, molecular hydrogen. It requires a lot of energy to break them. 

Once formed, water is very stable because the oxygen’s six valence electrons get two extras, one from each of the hydrogens, while the hydrogens get an extra electron each. The atoms are stuck together in a type of bonding called polar covalent. Oxygen is more electronegative than hydrogen, meaning it attracts electrons more strongly – the negative charge is polarised at the oxygen, giving that part of the molecule a partial negative charge, with a proportional positive charge at the hydrogens. I might explore the effects of this polarity in another post.

The percentage of oxygen in our atmosphere seems stable at 21% – that’s to say, it appears to be the same now as when I was born, but that’s not a lot of time, geologically. The issue of oxygen levels in our atmosphere over geological time is complex and contested, but the usual story is that something happened with the prokaryotic life forms that had evolved in the oceans billions of years ago, some kind of mutation which enabled a bacterial species to capture and harness solar energy. This green mutation, cyanobacteria, gave off gaseous oxygen as a waste product – a disaster for other life forms due to its highly reactive nature. The photosynthesising cyanobacteria, however, multiplied rapidly, oxygenising the ocean. Oxygen reacted with the ocean’s iron, creating layers of rust (iron oxide) on the ocean floor, later visible on land through tectonic forces over the eons. Gradually over time, other organisms evolved that were adapted to the new oxygen-rich atmosphere. It became an energy source, which in turn produced its own waste product, carbon dioxide. This created a near-perfect cycle, as cyanobacteria required CO2 as well as water and sunlight to produce oxygen (and sugar). Other photosynthesising water-based and land-based life forms, plants in particular, emerged. In fact, these life forms had harnessed cyanobacteria as chloroplasts, a process known as endosymbiosis. 

I’ll end this bitsy post with the apparent fact, according to this Inverse article, that our oxygen levels are actually falling, and have been for near a million years, and that’s leaving aside the far greater effects due to human activity (fossil fuel burning consumes oxygen and releases CO2). Of course oxygen is very vastly more abundant in the atmosphere than CO2, and the change is minuscule on the overall scale of things (unlike the change we’re making to CO2 levels). It will make much more of a difference in the oceans however, where the lack of dissolved oxygen is creating dead zones. The article explains:

 The primary contributor to these apocalyptic scenes is fertilizer runoff from agriculture, which causes algal blooms, providing a great feast for bacteria that consume oxygen. The abundance of these bacteria cause O2 levels to plummet, and if they go low enough, organisms that need it to survive swim away or die.

Just another of the threats to sea-life caused by humans. 

Written by stewart henderson

September 16, 2018 at 4:20 pm

Posted in environment, science

Tagged with , ,

the continuing story of South Australia’s energy solutions

leave a comment »

In a very smart pre-election move, our state Premier Jay Weatherill has announced that there’s a trial under way to install Tesla batteries with solar panels on over 1,000 SA Housing Trust homes. The ultimate, rather ambitious aim, is to roll this out to 50,000 SA homes, thus creating a 250MW power plant, in essence. And not to be outdone, the opposition has engaged in a bit of commendable me-tooism, with a similar plan, actually announced last October. This in spite of the conservative Feds deriding SA labor’s ‘reckless experiments’ in renewables.

Initially the plan would be offered to public housing properties – which interests me, as a person who’s just left a solarised housing association property for one without solar. I’m in community housing, a subset of public housing. Such a ‘virtual’ power plant will, I think, make consumers more aware of energy resources and consumption. It’s a bit like owning your own bit of land instead of renting it. And it will also bring down electricity prices for those consumers.

This is a really important and exciting development, adding to and in many ways eclipsing other recently announced developments in SA, as written about previously. It will be, for a time at least, the world’s biggest virtual power plant, lending further stability to the grid. It’s also a welcome break for public housing tenants, among the most affected by rising power bills (though we’ll have to wait and see if prices do actually come down as a result of all this activity).

And the announcements and plans keep coming, with another big battery – our fourth – to be constructed in the mid-north, near Snowtown. The 21MW/26MWh battery will be built alongside a 44MW solar farm in the area (next to the big wind farm).

 

South Australia’s wind farms

Now, as someone not hugely well-versed in the renewable energy field and the energy market in general, I rely on various websites, journalists and pundits to keep me honest, and to help me make sense of weird websites such as this one, the apparent aim of which is to reveal all climate scientists as delusionary or fraudsters and all renewable energy as damaging or wasteful. Should they (these websites) be tackled or ignored? As a person concerned about the best use of energy, I think probably the latter. Anyway, one journalist always worth following is Giles Parkinson, who writes for Renew Economy, inter alia. In this article, Parkinson focuses on FCAS (frequency control and ancillary services), a set of network services overseen by AEMO, the Australian Energy Market Operator. According to Parkinson and other experts, the provision of these services has been a massive revenue source for an Australian ‘gas cartel’, which has been rorting the system at the expense of consumers, to the tune of many thousands of dollars. Enter the big Tesla battery , officially known as the Hornsdale Power Reserve (HPR), and the situation has changed drastically, to the benefit of all:

Rather than jumping up to prices of around $11,500 and $14,000/MW, the bidding of the Tesla big battery – and, in a major new development, the adjoining Hornsdale wind farm – helped (after an initial spike) to keep them at around $270/MW.

This saved several million dollars in FCAS charges (which are paid by other generators and big energy users) in a single day.

And that’s not the only impact. According to state government’s advisor, Frontier Economics, the average price of FCAS fell by around 75 per cent in December from the same month the previous year. Market players are delighted, and consumers should be too, because they will ultimately benefit. (Parkinson)

As experts are pointing out, the HPR is largely misconceived as an emergency stop-gap supplier for the whole state. It has other, more significant uses, which are proving invaluable. Its effect on FCAS, for example, and its ultra-ultra-quick responses to outages at major coal-fired generators outside of the state, and ‘its smoothing of wind output and trading in the wholesale market’. The key to its success, apparently, is its speed of effect – the ability to switch on or off in an instant.

Parkinson’s latest article is about another SA govt announcement – Australia’s first renewable-hydrogen electrolyser plant at Port Lincoln.

I’ve no idea what that means, but I’m about to find out – a little bit. I do know that once-hyped hydrogen hasn’t been receiving so much support lately as a fuel – though I don’t even understand how it works as a fuel. Anyway, this plant will be ten times bigger than one planned for the ACT as part of its push to have its electricity provided entirely by renewables. It’s called ‘green hydrogen’, and the set-up will include a 10MW hydrogen-fired gas turbine (the world’s largest) driven by local solar and wind power, and a 5MW hydrogen fuel cell. Parkinson doesn’t describe the underlying technology, so I’ll have a go.

It’s all about electrolysis, the production of hydrogen from H2O by the introduction of an electric current. Much of what follows comes from a 2015 puff piece of sorts from the German company Siemens. It argues, like many, that there’s no universal solution for electrical storage, and, like maybe not so many, that large-scale storage can only be addressed by pumped hydro, compressed air (CAES) and chemical storage media such as hydrogen and methane. Then it proceeds to pour cold water on hydro – ‘the potential to extend its current capacity is very limited’ – and on CAES ‘ – ‘has limitations on operational flexibility and capacity. I know nothing about CAES, but they’re probably right about hydro. Here’s their illustration of the process they have in mind, from generation to application.

Clearly the author of this document is being highly optimistic about the role of hydrogen in end-use applications. Don’t see too many hydrogen cars in the offing, though the Port Lincoln facility, it’s hoped, will produce hydrogen ‘that can be used to power fuel cell vehicles, make ammonia, generate electricity in a turbine or fuel cell, supply industry, or to export around the world’.

So how does electrolysis (of water) actually work? The answer, of course, is this:

2 H2O(l) → 2 H2(g) + O2(g); E0 = +1.229 V

Need I say more? On the right of the equation, E0 = +1.229 V, which basically means it takes 1.23 volts to split water. As shown above, Siemens is using PEM (Proton Exchange Membrane, or Polymer Electrolyte Membrane) electrolysis, though alkaline water electrolysis is another effective method. Not sure which which method is being used here.

In any case, it seems to be an approved and robust technology, and it will add to the variety of ‘disruptive’ and innovative plans and processes that are creating more regionalised networks throughout the state. And it gives us all incentives to learn more about how energy can be produced, stored and utilised.

Written by stewart henderson

February 14, 2018 at 4:50 pm