Tag Archives: chemistry

Most flushable wipes aren’t flushable.

I’m a chemical engineer running for Oakland county water resources commissioner, and as the main job of the office is sewage, and as I’ve already written on the chemistry, I thought I might write about an aspect of the engineering. Specifically about toilet paper. Toilet paper is a remarkable product: it’s paper, compact and low in cost; strong enough to clean you, smooth on your bum, and beyond that, it will disintegrate in turbulent water so it doesn’t clog pipes. The trick to TP’s dry strength and wet-weakness, is that the paper pulp, wood cellulose, is pounded very thin, yet cast fluffy. For extra softness, the paper is typically coated with aloe or similar. Sorry to say, the same recipe does not work for wet-wipes, paper towels or kleenex (facial tissues); all of these products must have wet-strength, and this can cause problems with sewer clogs.

Patent 117355 for perforated toilet paper claimed it as an improved wrapping paper.

Patent 117,355 for perforated toilet paper on a roll. It’s claimed as an improved wrapping paper.

Before there was toilet paper, the world was a much sadder, and smellier place. Much of the world used sticks, stones, leaves, or corn cobs, and none of these did a particularly thorough job. Besides, none of these is particularly smooth, or particularly disposable, nor did it fall apart — not that most folks had indoor plumbing. Some rich Romans had plumbing, and these cleaned themselves with a small sponge on the end of a stick. They dipped the sponge ned in water for each use. It was disgusting, but didn’t clog the pipes. I’ve seen this in use on a trip to Turkey 25 years ago — not in actual use, but next to the commode.

The first reasonably modern toilet was invented in 1775 by Alexander Cummings, and by 1852 the first public flush toilets were available. The design looked pretty much like it looks today and the cost was 1¢. You got a towel and a shoe-shine too for that penny, but there was no toilet paper as such. Presumably one used a Roman sponge or some ordinary, standard paper. A popular wipe, back int he day  was the Sears-Roebuck catalog. It came free to most homes, and included a convenient hole in the corner allowing one to hang it in and outhouse or near the commode. It was rough on the bum, and didn’t fall apart. My guess is that it clogged the pipes too, for those who used it with flush toilets. The first toilet-specific paper wasn’t invented till 1859. Joseph Gayetty, an American, patented a product from pulverized hemp, a relatively soft fiber, softened further with aloe. The paper softer than standard, and had less tendency to clog pipes.

Toilet paper has to be soft

Toilet paper is either touted to be soft or strong; Modern Charmin touts wet strength, while Cottonelle touts completeness of wipe: ‘go commando.” 

The next great innovation was to make toilet paper as a perforated product on a roll. These novelties appear as US Patent #117,355 awarded to Seth Wheeler of Albany, NY 25 July 1871 (Wheeler also invented the classic roll toilet paper dispenser). Much of the sales pitch was that a cleaner bum would prevent the spread of cholera, typhoid, and other plagues and that is a legitimate claim. As the  market expanded, advertising followed. Some early brands of paper touted their softness, others their strength. Facial tissues, e.g. Kleenex, were sold specifically as a soft TP-like product that does not fall apart when wet. Sorry to say, this tends to go along with clogged toilets; do not flush more than one kleenex down at a flush. Kleenex is made with the same short fibers and aloe as toilet paper, but it contains binders (glue) to give it wet-strength. My guess is that Charmin is made the same way and that it isn’t great on your plumbing.

Paper towels and most baby wipes are worse to flush than Kleenex. They are made with lots of binder and they really don’t fall apart in water. Paper towels should never be flushed, and neither should most baby wipes, even brands that claim to be ‘flushable.” When flushed, these items tend to soak up fat and become fat bergs – the bane of sewer workers everywhere. There is a class action law suit against flushable wipe companies, and New York City is pursuing legislation to prevent them from claiming to be flushable. Still, as with everything, there are better and worse moist-wipe options. “Cottonelle” brand by Kleenex, and Scott flushable wipes will eventually (In a day or less) dissolve in water. These products are made with binders like kleenex, but the binder glue is a type that dissolves in any significant amount of water. As a result, these brands fall apart when flushed. For now, these are the only flushable brands I’d recommend flushing, and even then I suggest you only flush one at a time. In tests by Consumer Reports, other brands, e.g. Charmin and Equate flushable wipes do not dissolve. These manufacturers either have not quite figured out how to make dissolvable binders, or they can’t get around Kleenex’s patents.

Robert Buxbaum. October 10, 2016. If you live in Oakland county, MI vote for me for water commissioner. Here’s my web-site with other useful essays. I should mention Thomas Crapper, too. He invented the push-button flush and made some innovations in the water cistern, and he manufactured high-end commodes for Parliament and the royal family, but he’s irrelevant to the story here.

The chemistry of sewage treatment

The first thing to know about sewage is that it’s mostly water and only about 250 ppm solids. That is, if you boiled down a pot of sewage, only about 1/40 of 1% of it would remain as solids at the bottom of the pot. There would be some dried poop, some bits of lint and soap, the remains of potato peelings… Mostly, the sewage is water, and mostly it would have boiled away. The second thing to know, is that the solids, the bio-solids, are a lot like soil but better: more valuable, brown gold if used right. While our county mostly burns and landfills the solids remnant of our treated sewage, the wiser choice would be to convert it to fertilizer. Here is a comparison between the composition of soil and bio-solids.

The composition of soil and the composition of bio-solid waste. biosolids are like soil, just better.

The composition of soil and the composition of bio-solid waste. biosolids are like soil, just better.

Most of Oakland’s sewage goes to Detroit where they mostly dry and burn it, and land fill the rest. These processes are expensive and engineering- problematic. It takes a lot of energy to dry these solids to the point where they burn (they’re like really wet wood), and even then they don’t burn nicely. As shown above, the biosolids contain lots of sulfur and that makes combustion smelly. They also contain nitrate, and that makes combustion dangerous. It’s sort of like burning natural gun powder.

The preferred solution is partial combustion (oxidation) at room temperature by bacteria followed by conversion to fertilizer. In Detroit we do this first stage of treatment, the slow partial combustion by bacteria. Consider glucose, a typical carbohydrate,

-HCOH- + O–> CO+ H2O.    ∆G°= -114.6 kcal/mol.

The value of ∆G°, is relevant as a determinate of whether the reaction will proceed. A negative value of ∆G°, as above, indicates that the reaction can progress substantially to completion at standard conditions of 25°C and 1 atm pressure. In a sewage plant, many different carbohydrates are treated by many different bacteria (amoebae, paramnesia, and lactobacilli), and the temperature is slightly cooler than room, about 10-15°C, but this value of ∆G° suggests that near total biological oxidation is possible.

The Detroit plant, like most others, do this biological oxidation treatment using either large stirred tanks, of million gallon volume or so, or in flow reactors with a large fraction of cellular-material returning as recycle. Recycle is needed also in the stirred tank process because of the low solid content. The reaction is approximately first order in oxygen, carbohydrate, and bacteria. Thus a 50% cell recycle more or less doubles the speed of the reaction. Air is typically bubbled through the reactor to provide the oxygen, but in Detroit, pure oxygen is used. About half the organic carbon is oxidized and the remainder is sent to a settling pond. The decant (top) water is sent for “polishing” and dumped in the river, while the goop (the bottom) is currently dried for burning or carted off for landfill. The Holly, MI sewage plant uses a heterogeneous reactors for the oxidation: a trickle bed followed by a rotating disk contractor. These have higher bio-content and thus lower area demands and separation costs, but there is a somewhat higher capital cost.

A major component of bio-solids is nitrogen. Much of this in enters the form of urea, NH2-CO-NH2. In an oxidizing environment, bacteria turns the urea and other nitrogen compounds into nitrate. Consider the reaction the presence of washing soda, Na2CO3. The urea is turned into nitrate, a product suitable for gun powder manufacture. The value of ∆G° is negative, and the reaction is highly favorable.

NH2-CO-NH2 + Na2CO3 + 4 O2 –> 2 Na(NO3) + 2 CO2 + 2 H2O.     ∆G° = -177.5 kcal/mol

The mixture of nitrates and dry bio-solids is highly flammable, and there was recently a fire in the Detroit biosolids dryer. If we wished to make fertilizer, we’d probably want to replace the drier with a further stage of bio-treatment. In Wisconsin, and on a smaller scale in Oakland MI, biosolids are treated by higher temperature (thermophilic) bacteria in the absence of air, that is anaerobically. Anaerobic digestion produces hydrogen and methane, and produces highly useful forms of organic carbon.

2 (-HCOH-) –> COCH4        ∆G° = -33.7 Kcal/mol

3 (-HCOH-) + H2O –> -CH2COOH + CO2 +  2 1/2 H2        ∆G° = -21.9 kcal/mol

In a well-designed plant, the methane is recovered to provide heat to the plant, and sometimes to generate power. In Wisconsin, enough methane is produced to cook the fertilizer to sterilization. The product is called “Milorganite” as much of it comes from Milwaukee and much of the nitrate is bound to organics.

Egg-shaped, anaerobic biosolid digestors.

Egg-shaped, anaerobic biosolid digestors, Singapore.

The hydrogen could be recovered too, but typically reacts further within the anaerobic digester. Typically it will reduce the iron oxide in the biosolids from the brown, ferric form, Fe2O3, to black FeO.  In a reducing atmosphere,

Fe2O3 + H2 –> 2 FeO + H2O.

Fe2O3 is the reason leaves turn brown in the fall and is the reason that most poop is brown. FeO is the reason that composted soil is typically black. You’ll notice that swamps are filled with black goo, that’s because of a lack of oxygen at the bottom. Sulphate and phosphorous can be bound to ferrous iron and this is good for fertilizer. Generally you want the reduction reactions to go no further.

Weir dam on the river dour. Used to manage floods, increase residence time, and oxygenate the flow.

Weir dam on the river Dour in Scotland. Dams of this type increase residence time, and oxygenate the flow. They’re good for fish, pollution, and flooding.

When allowed to continue, the hydrogen produced by anaerobic digestion begins to reduce sulfate to H2S.

NaSO4 + 4.5 H2 –>  NaOH + 3H2O + H2S.

I’m running for Oakland county, MI water commissioner, and one of my aims is to stop wasting our biosolids. Oakland produces nearly 1000,000 pounds of dry biosolids per day. This is either a blessing or a curse depending on how we use it.

Another issue, Oakland county dumps unpasteurized, smelly black goo into Lake St. Clair every other week, whenever it rains more than one inch. I’d like to stop this by separating the storm and “sanitary” sewage. There is a capital cost, but it can save money because we’d no longer have to pay to treat our rainwater at the Detroit sewage plant. To clean the storm runoff, I’d use mini wetlands and weir dams to increase residence time and provide oxygen. Done right, it would look beautiful and would avoid the flash floods. It should also bring natural fish back to the Clinton River.

Robert Buxbaum, May 24 – Sept. 15, 2016 Thermodynamics plays a big role in my posts. You can show that, when the global ∆G is negative, there is an increase in the entropy of the universe.

How to help Flint and avoid lead here.

As most folks know, Flint has a lead-poisoning problem that seems to have begun in April, 2014 when the city switched its water supply from Detroit-supplied, Lake Huron water to their own plant pulling water from the Flint River. Here are some thoughts on how to help the affected population, and how to avoid a repeat in Oakland county, where I’m running for water commissioner. First observation, it is not enough to make sure that source water does not contain lead. The people who decided on the switch had found that the Flint river water had no significant lead or other obvious toxins. A key problem, it seems: the river water did not contain anticorrosion phosphates, and none, it seems, were added by the Flint water folks. After the switch, citizens started seeing disgusting, brown water come from their taps, and citizens with lead pipes or solder were poisoned with ppb-levels of lead.

Flint water, Sept 2015, before switching back to Lake Huron.

Flint water after 5 hours of flushing, Sept 2015, before switching back to Lake Huron.

The city switched back to Detroit-supplied, Lake Huron water in October, 2015, and they started adding triple doses of phosphates to the water in December. As a result, Flint tap-water is now back within EPA standards, but it’s still likely unsafe, see here for more details.

There has been a fair amount of finger-pointing. At Detroit for raising the price of water so Flint had to switch, at workers for ignoring the early signs of lead, at other employees for not adding the additive, and at “the system” for not caring, or providing Flint with decent infrastructure. I suspect that a lot of the problem is ignorance in the water commission. We elect our water commissioners, and folks seem to pick them the same way we pick presidents: for a nice smile, a great handshake, and an ability to remember names. That, anyway, seems to be the way that Oakland got its current water commissioner. When you pick your commissioner that way, it’s no surprise that he (or she) isn’t particularly sensitive to corrosion, an invisible chemical phenomenon that few people understand.

Flint river water contains corrosive chloride. Contributing to the corrosion problem, I’m going to guess that Flint River water also contains an industrial chelating chemical used in plating, EDTA in 10s of ppb concentrations. EDTA isn’t poisonous at these concentrations, but it’s the most commonly used antidote for lead poisoning and commonly used in industry. At these concentrations, EDTA extracts lead and other metals from people and I’m going to guess that this same chemical, or something very similar, contributed to the process that extracted lead and iron oxide from the pipes. With EDTA in the water, no amount of phosphate would avoid or solve the lead poisoning problem.

Detroit ex-mayor Kwame Kilpatrick has claimed that both Flint water and Detroit water were known to be poisoned even a decade before the switch. I find these claims believable given the high levels of lead in kids blood even before the switch. Also, I note that there are areas of Detroit where the blood-lead levels are higher than Flint. Flint did not test at the taps in a scientifically acceptable way during the first days of the poisoning, and neither, I suspect, do many of our MI cities today. My first suggestion therefore is to test correctly, both at the pipes and at the taps; lead pipes are most-often found in the last few feet before the tap. In particular, we should test at all schools and other places where the state has direct authorization to fix the problem. A MI senate bill has been proposed to this effect, but I’m not sure where it stands in the MI house. It seems there are movements to add lots of ‘riders’ and that’s usually a bad sign.

Another thought is that citizens should be encouraged to test their private taps and helped to fix them. The state can’t come in and test or rip out your private pipes, even if they suspect lead, but the private owner has that authorization. The state could condemn a private property where they believe the water is bad, but I doubt they could evict the residents. It’s a democratic republic, as I understand; you have the right to be deadly stupid. But I’ll take my own suggestion to encourage you: If you think your water has lead, take a sample and call (517) 335-8184. Do it.

Another suggestion, perhaps the easiest and most important, is to provide an antidote. The main antidotes for lead are chelating compounds, and we’re already providing bottles of imported water. Why not provide some of the water with compounds that help extract lead from people. And here I have an interesting thought. Assuming I am right that Flint River water had enough EDTA to cause/ worsen the problem, the cheapest/ best antidote might be Flint River water. You’d want to draw the water with plastic pipes and chlorinate it to rid it of bugs, but if there is EDTA it will help the poisoned. EDTA is a known lead-poisoning antidote. Another antidote is Succinct acid, something sold by REB Research, my company. There are other antidotes too, but wouldn’t it be cool if Flint river water worked?

Robert E. Buxbaum, January 19-31, 2016. I hope this helps. We’d have to check Flint River water for levels of EDTA, but I suspect we’d find it at 50 ppb, or so, a biologically significant concentration. If you think Oakland should have an engineer in charge of the water, elect Buxbaum for water commissioner.

Why are glaciers blue

i recently returned from a cruse trip to Alaska and, as is typical for such, a highlight of the trip was a visit to Alaska’s glaciers, in our case Hubbard Glacier, Glacier bay, and Mendenhall Glacier. All were blue — bright blue, as were the small icebergs that broke off. Glacier blocks only 2 feet across were bright blue like the glaciers themselves.

Hubbard Glacier, Alaska. Note how blue the ice is

Hubbard Glacier, Alaska. My photo. Note how blue the ice is

What made this interesting/ surprising is that I’ve seen ice sculptures that are 5 foot thick or more, and they are not significantly blue. They have a very slight tinge, but are generally more colorless than glass to my ability to tell. I asked the park rangers why the glaciers were blue, but was given no satisfactory answer. The claim was that glacier ice contained small air bubbles that scattered light the same way that air did. Another park ranger claimed that water is blue by nature, so of course the glaciers were too. The “proof” to this was that the sea was blue. Neither of these seem quite true to me, though there seamed some grains of truth. Sea water, I notice, is sort of blue, but isn’t this shade of blue, certainly not in areas that I’ve lived. Instead, sea water is a rather grayish similar to mud and sea-weeds that I’d expect to find on the sea floor. What’s more, if you look through the relatively clear water of a swimming-pool water to the white-tile bottom, you see only a slight shade of blue-green, even at the 9 foot depth where the light you see has passed through 18 feet of water. This is far more water than an iceberg thickness, and the color is nowhere near as pure blue and the intensity nowhere near as strong.

Plymouth, MI Ice sculpture -- the ice is fairly clear, like swimming pool water

Plymouth, MI Ice sculpture — the ice is fairly clear, like swimming pool water

As for the bubble explanation, it doesn’t seem quite right, either. The bubble size would be non-uniform, with many quite large resulting in a mix of scattered colors — an off white– something seen with the sky of mars. Our earth sky is a purer blue, but this is not because of scattering off of ice-crystals, dust or any other small particles, but rather scattering off the air molecules themselves. The clear blue of glaciers, and of overturned icebergs, suggests (to me) a single-size scattering entity, larger than air molecules, but much smaller than the wavelength of visible light. My preferred entity would be a new compound, a clathrate structure compound, that would be formed from air and ice at high pressures.

An overturned ice-burg is remarkably blue: far bluer than an Ice sculpture. I claim clathrates are the reason.

An overturned ice-burg is remarkably blue: far bluer than an Ice sculpture. I claim clathrates are the reason.

Sea-water forms clathrate compounds with natural gas at high pressures found at great depth. My thought is that similar compounds form between ice and one or more components of air (nitrogen, oxygen, or perhaps argon). Though no compounds of this sort have been quite identified, all these gases are reasonably soluble in water so that suggestion isn’t entirely implausible. The clathrates would be spheres, bigger than air molecules and thus should have more scattering power than the original molecules. An uneven distribution would explain the observation that the blue of glaciers is not uniform, but instead has deeper and lighter blue edges and stripes. Perhaps some parts of the glacier were formed at higher pressures one could expect that these would form more clathrate compounds, and thus more blue. One sees the most intense blue in overturned icebergs — the parts that were under the most pressure.

Robert Buxbaum, October 12, 2015. By the way, some of Alaska’s glaciers are growing and others shrinking. The rangers claimed this was the bad effect of global warming: that the shrinking glaciers should be growing and the growing ones shrinking. They also worried that despite Alaska temperatures reaching 40° below reasonably regularly, it was too warm (for whom?). The lowest recorded temperature in Fairbanks was -66°F in 1961.

Much of the chemistry you learned is wrong

When you were in school, you probably learned that understanding chemistry involved understanding the bonds between atoms. That all the things of the world were made of molecules, and that these molecules were fixed proportion combinations of the chemical elements held together by one of the 2 or 3 types of electron-sharing bonds. You were taught that water was H2O, that table salt was NaCl, that glass was SIO2, and rust was Fe2O3, and perhaps that the bonds involved an electron transferring between an electron-giver: H, Na, Si, or Fe… to an electron receiver: O or Cl above.

Sorry to say, none of that is true. These are fictions perpetrated by well-meaning, and sometime ignorant teachers. All of the materials mentioned above are grand polymers. Any of them can have extra or fewer atoms of any species, and as a result the stoichiometry isn’t quite fixed. They are not molecules at all in the sense you knew them. Also, ionic bonds hardly exist. Not in any chemical you’re familiar with. There are no common electron compounds. The world works, almost entirely on covalent, shared bonds. If bonds were ionic you could separate most materials by direct electrolysis of the pure compound, but you can not. You can not, for example, make iron by electrolysis of rust, nor can you make silicon by electrolysis of pure SiO2, or titanium by electrolysis of pure TiO. If you could, you’d make a lot of money and titanium would be very cheap. On the other hand, the fact that stoichiometry is rarely fixed allows you to make many useful devices, e.g. solid oxide fuel cells — things that should not work based on the chemistry you were taught.

Iron -zinc forms compounds, but they don't have fixed stoichiometry. As an example the compound at 60 atom % Zn is, I guess Zn3Fe2, but the composition varies quite a bit from there.

Iron -zinc forms compounds, but they don’t have fixed stoichiometry. As an example the compound at 68-80 atom% Zn is, I guess Zn7Fe3 with many substituted atoms, especially at temperatures near 665°C.

Because most bonds are covalent many compounds form that you would not expect. Most metal pairs form compounds with unusual stoicheometric composition. Here, for example, is the phase diagram for zinc and Iron –the materials behind galvanized sheet metal: iron that does not rust readily. The delta phase has a composition between 85 and 92 atom% Zn (8 and 15 a% iron): Perhaps the main compound is Zn5Fe2, not the sort of compound you’d expect, and it has a very variable compositions.

You may now ask why your teachers didn’t tell you this sort of stuff, but instead told you a pack of lies and half-truths. In part it’s because we don’t quite understand this ourselves. We don’t like to admit that. And besides, the lies serve a useful purpose: it gives us something to test you on. That is, a way to tell if you are a good student. The good students are those who memorize well and spit our lies back without asking too many questions of the wrong sort. We give students who do this good grades. I’m going to guess you were a good student (congratulations, so was I). The dullards got confused by our explanations. They asked too many questions, and asked, “can you explain that again? Or why? We get mad at these dullards and give them low grades. Eventually, the dullards feel bad enough about themselves to allow themselves to be ruled by us. We graduates who are confident in our ignorance rule the world, but inventions come from the dullards who don’t feel bad about their ignorance. They survive despite our best efforts. A few more of these folks survive in the west, and especially in America, than survive elsewhere. If you’re one, be happy you live here. In most countries you’d be beheaded.

Back to chemistry. It’s very difficult to know where to start to un-teach someone. Lets start with EMF and ionic bonds. While it is generally easier to remove an electron from a free metal atom than from a free non-metal atom, e.g. from a sodium atom instead of oxygen, removing an electron is always energetically unfavored, for all atoms. Similarly, while oxygen takes an extra electron easier than iron would, adding an electron is energetically unfavored. The figure below shows the classic ion bond, left, and two electron sharing options (center right) One is a bonding option the other anti-bonding. Nature prefers this to electron sharing to ionic bonds, even with blatantly ionic elements like sodium and chlorine.

Bond options in NaCl. Note that covalent is the stronger bond option though it requires less ionization.

Bond options in NaCl. Note that covalent is the stronger bond option though it requires less ionization.

There is a very small degree of ionic bonding in NaCl (left picture), but in virtually every case, covalent bonds (center) are easier to form and stronger when formed. And then there is the key anti-bonding state (right picture). The anti bond is hardly ever mentioned in high school or college chemistry, but it is critical — it’s this bond that keeps all mater from shrinking into nothingness.

I’ve discussed hydrogen bonds before. I find them fascinating since they make water wet and make life possible. I’d mentioned that they are just like regular bonds except that the quantum hydrogen atom (proton) plays the role that the electron plays. I now have to add that this is not a transfer, but a covalent spot. The H atom (proton) divides up like the electron did in the NaCl above. Thus, two water molecules are attracted by having partial bits of a proton half-way between the two oxygen atoms. The proton does not stay put at the center, there, but bobs between them as a quantum cloud. I should also mention that the hydrogen bond has an anti-bond state just like the electron above. We were never “taught” the hydrogen bond in high school or college — fortunately — that’s how I came to understand them. My professors, at Princeton saw hydrogen atoms as solid. It was their ignorance that allowed me to discover new things and get a PhD. One must be thankful for the folly of others: without it, no talented person could succeed.

And now I get to really weird bonds: entropy bonds. Have you ever noticed that meat gets softer when its aged in the freezer? That’s because most of the chemicals of life are held together by a sort of anti-bond called entropy, or randomness. The molecules in meat are unstable energetically, but actually increase the entropy of the water around them by their formation. When you lower the temperature you case the inherent instability of the bonds to cause them to let go. Unfortunately, this happens only slowly at low temperatures so you’ve got to age meat to tenderize it.

A nice thing about the entropy bond is that it is not particularly specific. A consequence of this is that all protein bonds are more-or-less the same strength. This allows proteins to form in a wide variety of compositions, but also means that deuterium oxide (heavy water) is toxic — it has a different entropic profile than regular water.

Robert Buxbaum, March 19, 2015. Unlearning false facts one lie at a time.

Toxic electrochemistry and biology at home

A few weeks back, I decided to do something about the low quality of experiments in modern chemistry and science sets; I posted to this blog some interesting science experiments, and some more-interesting experiments that could be done at home using the toxic (poisonous dangerous) chemicals available under the sink or on the hardware store. Here are some more. As previously, the chemicals are toxic and dangerous but available. As previously, these experiments should be done only with parental (adult) supervision. Some of these next experiments involve some math, as key aspect of science; others involve some new equipment as well as the stuff you used previously. To do them all, you will want a stop watch, a volt-amp meter, and a small transformer, available at RadioShack; you’ll also want some test tubes or similar, clear cigar tubes, wire and baking soda; for the coating experiment you’ll want copper drain clear, or copper containing fertilizer and some washers available at the hardware store; for metal casting experiment you’ll need a tin can, pliers, a gas stove and some pennies, plus a mold, some sand, good shoes, and a floor cover; and for the biology experiment you will need several 9 V batteries, and you will have to get a frog and kill it. You can skip any of these experiments, if you like and do the others. If you have not done the previous experiments, look them over or do them now.

1) The first experiments aim to add some numerical observations to our previous studies of electrolysis. Here is where you will see why we think that molecules like water are made of fixed compositions of atoms. Lets redo the water electrolysis experiment now with an Ammeter in line between the battery and one of the electrodes. With the ammeter connected, put both electrodes deep into a solution of water with a little lye, and then (while watching the ammeter) lift one electrode half out, place it back, and lift the other. You will find, I think, that one of the other electrode is the limiting electrode, and that the amperage goes to 1/2 its previous value when this electrode is half lifted. Lifting the other electrode changes neither the amperage or the amount of bubbles, but lifting this limiting electrode changes both the amount of bubbles and the amperage. If you watch closely, though, you’ll see it changes the amount of bubbles at both electrodes in proportion, and that the amount of bubbles is in promotion to the amperage. If you collect the two gasses simultaneously, you’ll see that the volume of gas collected is always in a ratio of 2 to 1. For other electrolysis (H2 and Cl2) it will be 1 to1; it’s always a ratio of small numbers. See diagram below on how to make and collect oxygen and hydrogen simultaneously by electrolyzing water with lye or baking soda as electrolyte. With lye or baking soda, you’ll find that there is always twice as much hydrogen produced as oxygen — exactly.

You can also do electrolysis with table salt or muriatic acid as an electrolyte, but for this you’ll need carbon or platinum electrodes. If you do it right, you’ll get hydrogen and chlorine, a green gas that smells bad. If you don’t do this right, using a wire instead of a carbon or platinum electrode, you’ll still get hydrogen, but no chlorine. Instead of chlorine, you’ll corrode the wire on that end, making e.g. copper chloride. With a carbon electrode and any chloride compound as the electrolyte, you’ll produce chlorine; without a chloride electrolyte, you will not produce chlorine at any voltage, or with any electrode. And if you make chlorine and check the volumes, you’ll find you always make one volume of chlorine for every volume of hydrogen. We imagine from this that the compounds are made of fixed atoms that transfer electrons in fixed whole numbers per molecule. You always make two volumes of hydrogen for every volume of oxygen because (we think) making oxygen requires twice as many electrons as making hydrogen.

At home electrolysis experiment

At home electrolysis experiment

We get the same volume of chlorine as hydrogen because making chlorine and hydrogen requires the same amount of electrons to be transferred. These are the sort of experiments that caused people to believe in atoms and molecules as the fundamental unchanging components of matter. Different solutes, voltages, and electrodes will affect how fast you make hydrogen and oxygen, as will the amount of dissolved solute, but the gas produced are always the same, and the ratio of volumes is always proportional to the amperage in a fixed ratio of small whole numbers.

As always, don’t let significant quantities of use hydrogen and oxygen or pure hydrogen and chlorine mix in a closed space. Hydrogen and oxygen is quite explosive brown’s gas; hydrogen and chlorine are reactive as well. When working with chlorine it is best to work outside or near an open window: chlorine is a poison gas.

You may also want to try this with non-electrolytes, pure water or water with sugar or alcohol dissolved. You will find there is hardly any amperage or gas with these, but the small amount of gas produced will retain the same ratio. For college level folks, here is some physics/math relating to the minimum voltage and relating to the quantities you should expect at any amperage.

2) Now let’s try electro-plating metals. Using the right solutes, metals can be made to coat your electrodes the same way that bubbles of gas coated your electrodes in the experiments above. The key is to find the right chemical, and as a start let me suggest the copper sulphate sold in hardware stores to stop root growth. As an alternative copper sulphate is often sold as part of a fertilizer solution like “Miracle grow.” Look for copper on the label, or for a blue color fertilizer. Make a solution of copper using enough copper so that the solution is recognizably green, Use two steel washers as electrodes (that is connect the wires from your battery to the washers) and put them in the solution. You will find that one side turns red, as it is coated with copper. Depending on what else your copper solution contained, bubbles may appear at the other washer, or the other washer will corrode. 

You are now ready to take this to a higher level — silver coating. take a piece of silver plated material that you want to coat, and clean it nicely with soap and water. Connect it to the electrode where you previously coated copper. Now clean out the solution carefully. Buy some silver nitrate from a drug store, and dissolve a few grams (1/8 tsp for a start) in pure water; place the silverware and the same electrodes as before, connected to the battery. For a nicer coat use a 1 1/2 volt lantern battery; the 6 V battery will work too, but the silver won’t look as nice. With silver nitrate, you’ll notice that one electrode produces gas (oxygen) and the other turns silvery. Now disconnect the silvery electrode. You can use this method to silver coat a ring, fork, or cup — anything you want to have silver coated. This process is called electroplating. As with hydrogen production, there is a proportional relationship between the time, the amperage and the amount of metal you deposit — until all the silver nitrate in solution is used up.

As a yet-more complex version, you can also electroplate without using a battery. This was my Simple electroplating (presented previously). Consider this only after you understand most everything else I’ve done. When I saw this the first time in high school I was confused.

3) Casting metal objects using melted pennies, heat from a gas stove, and sand or plaster as a cast. This is pretty easy, but sort of dangerous — you need parents help, if only as a watcher. This is a version of an experiment I did as a kid.  I did metal casting using lead that some plumbers had left over. I melted it in a tin can on our gas stove and cast “quarters” in a plaster mold. Plumbers no longer use lead, but modern pennies are mostly zinc, and will melt about as well as my lead did. They are also much safer.

As a preparation for this experiment, get a bucket full of sand. This is where you’ll put your metal when you’re done. Now get some pennies (1970 or later), a pair of pliers, and an empty clean tin can, and a gas stove. If you like you can make a plaster mold of some small object: a ring, a 50 piece — anything you might want to cast from your pennies. With parents’ help, light your gas stove, put 5-8 pennies in the empty tin can, and hold the can over the lit gas burner using your pliers. Turn the gas to high. In a few minutes the bottom of the can will burn and become red-hot. About this point, the pennies will soften and melt into a silvery puddle. By tilting the can, you can stir the metal around (don’t get it on you!). When it looks completely melted you can pour the molten pennies into your sand bucket (carefully), or over your plaster mold (carefully). If you use a mold, you’ll get a zinc copy of whatever your mold was: jewelry, coins, etc. If you work at it, you’ll learn to make fancier and fancier casts. Adult help is welcome to avoid accidents. Once the metal solidifies, you can help cool it faster by dripping water on it from a faucet. Don’t touch it while it’s hot!

A plaster mold can be made by putting a 50¢ piece at the bottom of a paper cup, pouring plaster over the coin, and waiting for it to dry. Tear off the cup, turn the plaster over and pull out the coin; you’ve got a one-sided mold, good enough to make a one-sided coin. If you enjoy this, you can learn more about casting on Wikipedia; it’s an endeavor that only costs 4 or 5 cents per try. As a safety note: wear solid leather shoes and cover the floor near the stove with a board. If you drop the metal on the floor you’ll have a permanent burn mark on the floor and your mother will not be happy. If you drop hot metal on your you’ll have a permanent injury, and you won’t be happy. Older pennies are made of copper and will not melt. Here’s a video of someone pouring a lot of metal into an ant-hill (kills lots of ants, makes a mold of the hill).

It's often helpful to ask yourself, "what would Dr. Frankenstein do?"

It’s nice to have assistants, friends and adult help in the laboratory when you do science. Even without the castle, it’s what Dr. Frankenstein did.

4) Bringing a dead frog back to life (sort of). Make a high voltage battery of 45 to 90 V battery by attaching 5-10, 9V batteries in a daisy chain they will snap together. If you touch both exposed contacts you’ll give yourself a wicked shock. If you touch the electrodes to a newly killed frog, the frog legs will kick. This is sort of groovy. It was the inspiration for Dr. Frankenstein (at right), who then decides he could bring a person back from the dead with “more power.” Frankenstein’s monster is brought back to life this way, but ends up killing the good doctor. Shocks are sometimes helpful reanimating people stricken by heat attacks, and many buildings have shockers for this purpose. But don’t try to bring back the long-dead. By all accounts, the results are less-than pleasing. Try dissecting the rest of the frog and guess what each part is (a world book encyclopedia helps). As I recall, the heart keeps going for a while after it’s out of the frog — spooky.

5) Another version of this shocker is made with a small transformer (1″ square, say, radioshack) and a small battery (1.5-6V). Don’t use the 90V battery, you’ll kill someone. As a first version of this shocker, strip 1″ of  insulation off of the ends of some wire 12″ long say, and attach one end to two paired wires of the transformer (there will usually be a diagram in the box). If the transformer already has some wires coming out, all you have to do is strip more insulation off the ends so 1″ is un-inuslated. Take two paired ends in your hand, holding onto the uninsulated part and touch both to the battery for a second or two. Then disconnect them while holding the bare wires; you’ll get a shock. As a nastier version, get a friend to hope the opposite pair of wires on the uninsulated parts, while you hold the insulated parts of your two. Touch your two to the battery and disconnect while holding the insulation, you will see a nice spark, and your friend will get a nice shock. Play with it; different arrangements give more sparks or bigger shocks. Another thing you can do: put your experiment near a radio or TV. The transformer sparks will interfere with most nearby electronics; you can really mess up a computer this way, so keep it far from your computer. This is how wireless radio worked long ago, and how modern warfare will probably go. The atom bomb was detonated with a spark like this.

If you want to do more advanced science, it’s a good idea to learn math. This is important for statistics, for engineering, for quantum mechanics, and can even help for music. Get a few good high school or college books and read them cover to cover. An approach to science is to try to make something cool, that sort-of works, and then try to improve it. You then decide what a better version would work like,  modify your original semi-randomly and see if you’re going in the right direction. Don’t redesign with only one approach –it may not work. Read whatever you can, but don’t believe all you read. Often books are misleading, or wrong, and blogs are worse (I ought to know). When you find mistakes, note them in the margin, and try to explain them. You may find you were right, or that the book was right, but it’s a learning experience. If you like you can write the author and inform him/her of the errors. I find mailed letters are more respectful than e-mails — it shows you put in more effort.

Robert Buxbaum, February 20, 2014. Here’s the difference between metals and non-metals, and a periodic table cup that I made, and sell. And here’s a difference between science and religion – reproducibility.

Toxic chemistry you can do at home

I got my start on science working with a 7 chemical, chemistry set that my sister got me when I was 7 years old (thanks Beverly). The chemicals would never be sold by a US company today — too much liability. What if your child poisons himself/herself or someone else, or is allergic, or someone chokes on the caps (anything the size of a nut has to be labeled as a hazard). Many of the experiments were called magic, and they were, in the sense that, if you did them 200 years earlier, you’d be burnt as a witch. There were dramatic color changes (phenolphthalein plus base, Prussian Blue) a time-delay experiment involving cobalt, and even an experiment that (as I recall) burst into fire on its own (glycerine plus granulated potassium permanganate).

Better evil through science. If you get good at this, the military may have use of your services.

“Better the evil you know.” If you get good at this, the military may have use of your services. Yes, the American military does science.

Science kits nowadays don’t do anything magically cool like that, and they don’t really teach chemistry, either, I think. Doing magical things requires chemicals that are reasonably reactive, and that means corrosive and/or toxic. Current kits use only food products like corn-starch or baking soda, and the best you can do with these is to make goo and/ or bubbles. No one would be burnt at the stake for this, even 300 years ago. I suppose one could design a program that used these materials to teach something about flow, or nucleation, but that would require math, and the kit producers fear that any math will turn off kids and stop their parents from spending money. There is also the issue of motivation. Much of historical chemistry was driven by greed and war; these are issues that still motivate kids, but that modern set-makers would like to ignore. Instead, current kits are supposed to be exciting in a cooperative way (whatever that means), because the kit-maker says so. They are not. I went through every experiment in my first kit in the first day, and got things right within the first week — showing off to whoever would watch. Modern kits don’t motivate this sort of use; I doubt most get half-used in a lifetime.

There are some foreign-made chemistry sets still that are pretty good. Here is a link to a decent mid-range one from England. But it’s sort of pricy, and already somewhat dumbed down. Instead, here are some cheaper, more dangerous, American options: 5 experiments you can do (kids and parents together, please) using toxic household chemicals found in our US hardware stores. These are NOT the safest experiments, just cheap ones that are interesting. I’ll also try to give some math and explanations — so you’ll understand what’s happening on a deeper level — and I’ll give some financial motivation — some commercial value.

1) Crystal Drano + aluminum. Crystal Drano is available in the hardware store. It’s mostly lye, sodium hydroxide, one of the strongest bases known to man. It’s a toxic (highly poisonous) chemical used to dissolve hair and fat in a drain. It will also dissolve some metals and it will dissolve you if you get it on yourself (if you do get it on yourself, wash it off fast with lots of water). Drano also contains ammonium nitrate (an explosive) and bits of aluminum. For the most part, the aluminum is there so that the Drano will get hot in the clogged drain (heat helps it dissolve the clog faster). I’ll explain the ammonium nitrate later. For this experiment, you’re going to want to work outside, on a dinner plate on the street. You’ll use additional aluminum (aluminum foil), and you’ll get more heat and fun gases. Fold up a 1 foot square of aluminum foil to 6″ x 4″ say, and put it on the plate (outside). Put an indent in the middle of the foil making a sort of small cup — one that can stand. Into this indent, put a tablespoon or two of water plus a teaspoon of Drano. Wait about 5 minutes, and you will see that the Drano starts smoking and the aluminum foils starts to dissolve. The plate will start to get hot and you will begin to notice a bad smell (ammonia). The aluminum foil will turn black and will continue to dissolve till there is a hole in the middle of the indent. Draino

The main reaction is 2 Al + 3 H2O –> Al2O3 + H2; that is, aluminum plus water gives you aluminum oxide (alumina), and hydrogen. The sodium hydroxide (lye) in the Drano is a catalyst in this reaction, something that is not consumed in this reaction but makes it happen faster than otherwise. The hydrogen you produce here is explosive and valuable (I explain below). But there is another reaction going on too, the one that makes the bad smell. When ammonium nitrate is heated in the presence of sodium hydroxide, it reacts to make ammonia and sodium nitrate. The reaction formula is: NH4-NO3 + NaOH –> NH3 + NaNO3 + H2O. The ammonia produced gives off a smell, something that is important for safety — the smell is a warning — and (I think) helps keep the aluminum gunk from clogging the drain by reacting with the aluminum oxide to form aluminum amine hydroxide Al2O3(NH3)2. It’s a fun experiment to watch, but you can do more if you like. The hydrogen and ammonia are flammable and is useful for other experiments (below). If you collect these gases, you can can make explosions or fill a balloon that will float. Currently the US military, and several manufacturers in Asia are considering using the hydrogen created this way to power motorcycles by way of a fuel cell. There is also the Hindenburg, a zeppelin that went around the world in the 1930s. It was kept aloft by hydrogen. The ammonia you make has value too, though toxic; if bubbled into water, it makes ammonium hydroxide NH3 + H2O –> NH4OH. This is a common cleaning liquid. Just to remind you: you’re supposed to do these experiments outside to dissipate the toxic gases and to avoid an explosion in your house. A parent will come in handy if you get this stuff on your hand or in your eye.

Next experiment: check that iron does not dissolve in Drano, but it does in acid (that’s experiment 5; done with Muriatic acid from the hardware store). Try also copper, and solder (mostly tin, these days). Metals that dissolve well in Drano are near the right of the periodic table, like aluminum. Aluminum is nearly a non-metal, and thus can be expected to have an oxide that reacts with hydroxide. Iron and steel have oxides that are bases themselves, and thus don’t react with lye. This is important as otherwise Drano would destroy your iron drain, not only the hair in it. It’s somewhat hard on copper though, so beware if you’ve a copper drain.

Thought problem: based on the formulas above figure out the right mix of aluminum, NaOH, water and Ammonium nitrate. Answer: note that, for every two atoms of aluminum you dissolve, you’ll need three molecules of water (for the three O atoms), plus at least two molecules of ammonium nitrate (to provide the two NH2 (amine) groups above. You’ll also want at least 2 molecules of NaOH to have enough Na to react with the nitrate groups of the ammonium nitrate. As a first guess, assume that all atoms are the same size. A better way to do this involves molecular weights (formula weights), read a chemistry book, or look on the internet.

Four more experiments can be seen here. This post was getting to be over-long.As with this experiment, wear gloves and eye protection; don’t drink the chemicals, and if you get any chemicals on you, wash them off quick.

Here are a few more experiments in electrochemistry and biology, perhaps I’ll add more. In the meantime, if you or your child are interested in science, I’d suggest you read science books by Mr Wizard, or Isaac Asimov, and that you learn math. Another thought, take out a high school chemistry text-book at the library — preferably an old one with experiments..

Robert Buxbaum, December 29, 2013. If you are interested in weather flow, by the way, here is a bit on why tornadoes and hurricanes lift stuff up, and on how/ why they form. 

chemistry and dentistry joke

What do you get when you dissolve all your rear teeth in water.

 

 

An eight molar solution.

 

Is funny because ….. most adults have eight molars (four on the bottom, four on the top); and there is a measure of solution concentration called molarity; an eight molar solution is one that contains 8 formula weights of solute per liter of solution.

For a chemistry joke about dissolving bears, go here; for a chemist v chemical engineer joke, here; for my latest quantum joke, here; and for an architecture joke, here. On a more serious note, if you’d like to see how we do simple electroplating, see the previous post.

 

R.E.Buxbaum, July 24, 2013

Simple electroplating of noble metals

Electro-coating gold onto a Pd tube by dissolving an iron wire.

Electro-coating gold onto at Pd-coated tube by dissolving an iron wire at REB Research.

Here’s a simple trick for electroplating noble metals: gold, silver, copper, platinum. I learned this trick at Brooklyn Technical High School some years ago, and I still use it at REB Research as part of our process to make hydrogen permeation barriers, and sulfur tolerant permeation membranes.  It’s best used to coat reasonably inactive, small objects,  e.g. to coat copper on a nickel or silver on a penny for a science fair.

As a first step, you make a dilute acidic solution of the desired noble metal. Dissolve a gram or so of copper sulphate, silver nitrate, or gold chloride per 250 ml of water. Make sure the solution is acidic using pH paper, add acid if needed aiming for a pH of 3 to 4. Place some solution into a test tube or beaker of a size that will hold the object you want to coat. As a next step, attach an iron or steel wire to the object, I typically use bailing wire from the hardware store wrapped several times about the top of the object, and run the length of the object; see figure. Place the object into your solution and wait for 5 to 30 minutes. Coating works without the need for any other electric source or any current control.

The iron wire creates the electricity used in electroplating the noble metal. Iron has a higher electro-motive potential than hydrogen and hydrogen has a higher potential than the noble metals. In acid solution, the iron wire dissolves but (it’s hoped) the substrate does not. Each iron atom gives up two electrons, becoming Fe++. Some of these electrons go on to reduce hydrogen ions making H2 (2H+ 2e –> H2), but most should go to reduce the noble metal ions in the solution to form a coat of metallic gold, silver, or copper on both the wire and the object. See an example of how I do calculations regarding voltage, electron number, and Gibbs free energy.

Transferring electrons requires you have good electrical contact between the wire and the object. Most of the noble metal coats the object, not the wire since the object is bigger, typically. Thanks to my teachers at Brooklyn Technical High School for teaching me. For a uniform coat, it helps to run the wire down parallel to the entire length of tube; I think this is a capacitance, field effect. For a larger object, you may want several wires if you are plating a larger object. For a thicker coat, I found you are best off making many thin coats and heating them. This reduces tension forces in the coat, I think.

The picture shows a step in the process we use making our sulfur-resistant hydrogen permeation membranes (buy them here), used, e.g. to concentrate impurities in a hydrogen stream for improved gas chromatography. The next step is to dissolve the gold or copper into the palladium.

Go here for a great periodic table cup from REB Research, or for the rest of our REB Research products. I occasionally make silver-coated pennies for schoolchildren, but otherwise use this technology only for in-house production.

R.E. Buxbaum, July 20, 2013.

Chemist v Chemical Engineer joke

What’s the difference between a chemist and a chemical engineer?

 

How much they make.

 

I made up this joke up as there were no other chemical engineer jokes I knew. It’s an OK double entente that’s pretty true — both in terms of product produced and the amount of salary (there’s probably a cause-and-effect relation here). Typical of these puns, this joke ignores the internal differences in methodologies and background (see my post, How is Chemical engineering?). If you like, here’s another engineering joke,  a chemistry joke, and a dwarf joke.

R.E. Buxbaum –  June 28, 2013.