La presente cronologia evidenzia come l’invenzione del barometro da parte di Torricelli e la relativa rivoluzionaria intuizione abbiano portato alla scoperta della Legge di Boyle, formula fondamentale della chimica fisica

1643

In Italia, Evangelista Torricelli inventa il barometro che, etimologicamente, significa “misura del peso”. È il primo ad affermare che l’atmosfera ha un peso e che tale peso controbilancia esattamente il peso della colonna di mercurio nel tubo barometrico. In una lettera a un collega, scrive la famosa frase:

“Noi viviamo sommersi nel fondo d’un pelago d’aria”.

Basandosi su tale affermazione, prevede che l’altezza del mercurio all’interno del tubo sarebbe risultata inferiore a un’altitudine superiore, poiché il peso dell’aria che agisce su di esso sarebbe stato inferiore.

1644

La notizia dell’invenzione di Torricelli, e del pensiero rivoluzionario che l’ha accompagnata, arriva in Francia. Blaise Pascal, talentuoso matematico e fisico allora solo 21enne, esegue una verifica della previsione di Torricelli misurando l’altezza del barometro ai piedi e in vetta al vulcano Puy de Dôme, alto 1465 metri, situato nella zona centro-meridionale della Francia.

La misura di 23 unità in vetta e di 26 unità ai piedi del vulcano confermano la previsione di Torricelli e forniscono convincenti prove a favore della teoria che l’atmosfera abbia un peso, esercitando una pressione che controbilancia il peso del mercurio nel tubo barometrico.

1647

Torricelli muore a Firenze, probabilmente di tifo, alla giovane età di 39 anni. Viene sepolto nella Basilica di San Lorenzo nel cui chiostro si trova una lapide commemorativa che lo ricorda.

1653

Il barometro di Torricelli viene discusso in Inghilterra nei centri scientifici di Londra, Oxford e Cambridge. Henry Power, uno studente di Cambridge, verifica l’osservazione di Pascal e inizia a studiare le caratteristiche di espansione e compressione dell’aria.

1661


Photo acknowledgement: Lee Pilkington

Nell’aprile del 1661, Henry Power e l’aristocratico inglese Richard Towneley conducono un esperimento a Pendle Hill, nel nord dell’Inghilterra. Dopo aver introdotto una quantità d’aria sopra al mercurio in un tubo torricelliano ne misurano il volume; utilizzando quindi il tubo come barometro, misurano la pressione dell’aria. Salgono poi sulla collina, alta 557 metri, e sulla vetta, ripetono le misurazioni di volume e pressione. Come previsto, si verifica una diminuzione della pressione, accompagnata da un corrispondente aumento del volume dell’aria nel tubo.

Tale esperimento permette loro di dedurre una semplice relazione numerica tra la pressione e il volume dell’aria nel tubo

dove p1 e v1 rappresentano le misurazioni della pressione e del volume dell’aria nel tubo ai piedi della collina e p2 e v2 le corrispondenti misurazioni in vetta. Tale formula, caposaldo della chimica fisica, viene comunicata e pubblicata in Inghilterra nel 1662 dal filosofo naturalista anglo-irlandese Robert Boyle e diventa nota come la Legge di Boyle.

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P Mander maggio 2022

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I have always had a fondness for classical experiments that revealed fundamental things about the particulate nature of our world. Examples that spring to mind include JJ Thomson’s cathode ray tube experiment (1897), Robert Millikan’s oil drop experiment (1909), and CTR Wilson’s cloud chamber (1912). The particles of interest in these cases were subatomic, but during this era of discovery there was another pioneering experiment that focused on molecules and their chemical reactivity. The insight this experiment provided was important, but the curious fact is that relatively few people have ever heard of it.

So to resurrect this largely forgotten piece of scientific history, CarnotCycle here tells the story of the Ozone Experiment conducted by the Hon. Robert John Strutt FRS at Imperial College of Science, South Kensington, London in 1912.

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The experimenter

NPG x122578; Lord Robert John Rayleigh, 4th Baron Rayleigh by Bassano

RJ Strutt (1875-1947) photographed in 1923

The Honorable Robert John Strutt, 4th Baron Rayleigh, might be an unfamiliar name to some of you. But you will undoubtedly have heard of his father, Lord Rayleigh of Rayleigh scattering fame. Where his father led, Robert John followed: first as a research student at the Cavendish Laboratory in Cambridge where his father had been Cavendish professor, and then at Imperial College of Science in South Kensington, London where he followed up his father’s eponymous work on light scattering.

But Robert John did some interesting work of his own. For one thing, he was the first to prove the existence of ozone in the upper atmosphere, and for another he studied the effect of electrical discharges in gases. Interestingly it was a combination of these two things – ozone produced in an electrical discharge tube – that formed the basis of Strutt’s groundbreaking 1912 experiment.

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The experiment

str03

Here is the apparatus that Strutt employed in his experiment. As the arrows indicate, air enters from the right via stopcock a, where the pressure is significantly reduced by the action of the air pump at left. Low-pressure air then passes through the discharge tube b, where ozone is formed from oxygen according to the reaction

The air, containing ozone at a few percent, enters chamber c where it encounters a silver gauze partition d, mounted between two mica discs e in each of which there is a hole 2 millimeters in diameter. A sealed-in glass funnel g supports the mica discs as shown. As the air passes the gauze, ozone reacts with the silver in what is thought to be an alternating cycle of oxidation and reduction which destroys the ozone while constantly refreshing the silver

The chambers on either side of the gauze partition are connected by tubes f, either of which could be put into communication with a McLeod pressure gauge. The rate of air intake was measured by drawing in air at atmospheric pressure from a graduated vessel standing over water. From this data, combined with the McLeod pressure gauge measurements, the volume v of the low-pressure air stream passing the gauze per second could be calculated.

So to recap, in Strutt’s steady-state experiment, air passes through the apparatus at a constant rate as ozone is generated in the discharge tube and destroyed by the silver gauze. The question then arises – What proportion of the ozone is destroyed as it passes the gauze?

This brings us to the luminous aspect of the ozone experiment, which enabled Strutt to provide an answer.

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The green glow

The conversion of oxygen into its allotrope ozone was not the only reaction taking place in the discharge tube of Strutt’s apparatus. There was also a reaction between nitrogen and oxygen – known to occur in lightning strikes – which produces nitrogen(II) oxide

Now it just so happens that nitrogen(II) oxide and ozone react in the gas phase to produce activated nitrogen(IV) dioxide, which exhibits chemiluminescence in the form of a green glow as it returns to its ground state

This was a crucial factor in Strutt’s experiment. The air flowing into the chamber c was glowing green due to the above reactions taking place in the gas phase. But as the flow passed the silver gauze, ozone molecules were destroyed with the result that the green glow was weaker in the left-hand chamber compared with the right-hand chamber.

By adjusting the rate of air flow through the apparatus, Strutt could engineer a steady state in which the green glow was just extinguished by the silver gauze – in other words he could find the flow rate at which all of the ozone molecules were destroyed by the silver/silver oxide of the gauze partition.

[To allay doubts, Strutt introduced ozone gas downstream of the gauze where the green glow had been extinguished. The glow was restored.]

Strutt was now in a position to interpret the experiment from a new and pioneering perspective – his 1912 paper was one of the very first to consider a chemical reaction in the context of molecular statistics.

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The analysis

In terms of chemical process, Strutt’s steady-state experiment was unremarkable. Air flowed through the apparatus and the ozone generated in the discharge tube was destroyed by the silver gauze. The novel feature was in the analysis, where Strutt applied both classical physics and the kinetic theory of gases to calculate the ratio of the mass of ozone impinging upon the silver gauze in a second to the mass passing the gauze in a second.

As mentioned above, Strutt could compute the volume v of the stream passing through the apparatus in a second, so the mass of ozone passing the gauze in a second was simply ρv, where ρ is the density of ozone in the stream as it arrives at the gauze.

In his paper, Strutt states a formula for calculating the mass of ozone impinging upon the silver surface in a second

without showing the steps by which he reached it. These steps are salient to the analysis, so I include the following elucidation due to CN Hinshelwood* in which urms is the root mean square velocity (i.e. the average velocity, with units taken to be cm/s) of the gas molecules:

Suppose we have a solid surface of unit area exposed to the bombardment of gas molecules. Approximately one-sixth of the total number of molecules may be regarded as moving in the direction of the surface with the average velocity. In one second all those within distance urms could reach and strike the surface, unless turned back by a collision with another molecule, but for every one so turned back, another, originally leaving the surface, is sent back to it. Thus the number of molecules striking the surface in a second is equal to one-sixth of the number contained in a prism of unit base and height urms. This number is 1/6.n’.urms,, n’ being the number of molecules in 1 cm^3. Thus the mass of gas impinging upon the surface per second is

A more precise investigation allowing for the unequal speeds of different molecules shows that the factor 1/6 should really be

We therefore arrive at the result that the mass of gas striking an area A in one second is

*CN Hinshelwood, The Kinetics of Chemical Change in Gaseous Systems, 2nd Ed. (1929), Clarendon Press

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The ratio

Strutt takes the above formula for the mass of ozone impinging on the gauze per second and divides it by the formula for the mass of ozone passing the gauze per second, ρv. This operation cancels out the unknown value of ρ, giving

The values of v (200 cm3s-1) and A (0.0369 cm2) were obtained by Strutt using direct measurements, while urms for ozone molecules is simply stated without mentioning that it is necessarily computed from the fundamental kinetic equation

If n is Avogadro’s number, v is the molar volume and pv = RT, whence

where M is the molar mass. The urms figure Strutt gives for ozone is 3.75 × 104; typically for the time he neglects to state the units which are presumed to be cm/s. This velocity seems a little low, implying a temperature of 270.6K for the air flow in his apparatus. But then again, the pressure dropped significantly at the stopcock so in all likelihood there would have been some Joule-Thomson cooling.

Inserting the values for A, v and urms in the ratio expression gives

Since we can interpret mass in terms of the number of ozone molecules, the ratio expresses the number of collisions to the number of molecules passing, or the average number of times each ozone molecule must strike the silver surface before it passes.

As the experiment is arranged so that no ozone molecules pass the silver gauze, the ratio must represent the average number of collisions that an ozone molecule makes with the silver surface before it is destroyed.

The 1.6 ratio reveals the astonishing fact that practically every ozone molecule which strikes the silver (oxide) surface is destroyed. To a chemical engineer that is a hugely important piece of information, which amply illustrates the value of applying kinetic theory to chemical reactivity.

The application of analogous calculations to the passage of gas streams over solid catalysts in industrial processes is obvious. All of which makes it even more curious that Robert John Strutt’s apparatus, and the pioneering work he did with it, is not better known.

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Further reading

Hon. RJ Strutt, The Molecular Statistics of some Chemical Actions (1912)
The principal source for this blog post.
http://rspa.royalsocietypublishing.org/content/royprsa/87/596/302.full.pdf

CTR Wilson, On an expansion apparatus for making visible the tracks of ionizing particles in gases and some results obtained by its use (1912)
The Cloud Chamber – a truly historic piece of apparatus and one of my favorites. This paper was published in September 1912, just a month before Strutt’s paper.
http://rspa.royalsocietypublishing.org/content/royprsa/87/595/277.full.pdf

P Mander August 2016

Carbon dioxide – aka CO2 – has a lousy reputation in today’s world. Most of us regard it as a significant greenhouse gas contributor to atmospheric heating and all the bad climate stuff that comes with it: heat domes, wildfires, droughts, flash floods, mudslides, loss of land, loss of property, loss of life. The best available science warns us not to keep adding more CO2 to what’s already up in the air, so it’s understandable that our basic instinct is to capture it before emission, pump it into caverns underground, and leave it there.

Carbon Capture and Sequestration (CCS) is already being implemented in subterranean spaces such as depleted oilfields. The CO2 is captured from power stations and industrial facilities such as cement works, and either directly piped or shipped to the disposal point.

As a business model it is capital intensive and relies on the costs of sequestration being sufficiently lower than the costs of emission to make the undertaking economically viable. Also CCS intrinsically demonstrates a preference for permanent disposal over carbon re-utilization and implicit in that choice is a value assessment of the carbon contained in CO2.

Such an assessment is not easily made without familiarity with carbon’s capacity to form bonds with itself and other atoms, a knowledge of what that means in terms of carbon’s oxidation state range, and an understanding of how that range makes carbon a suitable vehicle for energy storage and release, as well as feedstock for a broad spectrum of industrially useful molecules.

It is asking a lot of those educated in political science rather than physical science to make reasoned judgements on the desirability of permanent disposal or carbon re-utilization. And it is rare indeed for heads of government to have skills in both disciplines, although it has been known.

Fortunately however, state-backed investments in CCS need not carry the risk of being the wrong choice long term because it has been shown possible to re-utilize sequestered CO2. Here’s how.

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The Sabatier-Senderens reaction

In 1897, two French chemists discovered that carbon dioxide could be reduced by hydrogen over a nickel catalyst at elevated temperature and pressure to form methane and water vapor. This is the same carbon transformation that occurs in the Carbon Cycle via photosynthesis and the gradual degradation of biomass to coal, oil and natural gas – a process that takes Nature millions of years to accomplish. Sabatier and Senderens found a way to do it in real time.

Now consider the conditions in the underground caverns where carbon dioxide gas is sequestered. The temperature is elevated and so is the pressure. And in the pores of the geological formations holding the gas there are microbes capable of catalyzing the Sabatier-Senderens reaction. All it needs is to add hydrogen, which can be produced electrolytically from water using solar or wind.

To get technical for a moment, it is instructive to apply Hess’s Law (G.H. Hess, 1840) to the electrolysis of water and the Sabatier-Senderens reaction

In effect the energy released by the combustion of hydrogen is being used to reverse the combustion of methane, the energy being stored in the stable C-H bonds of the methane molecule. Note that the oxygen is formed above ground during electrolysis and is either stored for commercial use or vented to the atmosphere.

The pressurized subterranean gas can be piped up and passed through a separator where methane is extracted and carbon dioxide and hydrogen are returned underground to continue the reaction. Now if the sequestered CO2 was captured before emission, it would defeat the object to use the methane in the energy supply infrastructure since combustion would simply release CO2 to the atmosphere. So what can be done with this methane? The next section supplies the answer.

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Tri-Reforming Methane

ccu03

An LNG tanker

Methane (CH4) has certain characteristics which make it attractive as an energy carrier. It is not difficult to liquefy at 1 atmosphere pressure, it is energy dense and relatively efficient to transport as LNG (Liquid Natural Gas). So it is a practical proposition for methane gas produced in underground caverns to be transported to plants where CO2 capture is taking place.

Again to get technical for a moment, we notice that the oxidation states of carbon in the two molecules are at opposite ends of the scale. Methane has the most reduced form of carbon (-4) while carbon dioxide has the most oxidized form of carbon (+4). A redox reaction between the two looks possible and indeed is possible, albeit at elevated temperatures:

This catalyzed process, by which two greenhouse gases are converted into two non-greenhouse gases, is called dry reforming of methane (DRM) and was first introduced by Franz Fischer and Hans Tropsch in Germany in the 1920s. The 1:1 mixture of carbon monoxide and hydrogen is called syngas (synthesis gas), a key intermediate in the production of industrially useful molecules.

Germany’s dynamic duo: Franz Fischer and Hans Tropsch

Because of the high process temperature, DRM also results in thermal decomposition of both methane and carbon dioxide and the deactivating deposition of carbon on the catalyst. This problem can however be mitigated in a very neat way by combining DRM with another methane reforming process, namely steam reforming (SRM). This not only re-utilizes the deposited carbon but also adds another syngas product with a 3:1 ratio:

All these reactions are endothermic (requiring heat). This heat can be supplied by adding oxygen to the reactant stream, which allows partial oxidation of methane (POM) and catalytic combustion of methane (CCM) to take place, both of which are exothermic reactions (producing heat):

Putting three reforming agents – carbon dioxide, water and oxygen – together in the reactant stream with methane feedstock creates a sufficiently energy-efficient overall process known as Tri-reforming.

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Bringing it all together

We have seen that the decision to avoid CO2 emissions to the atmosphere by employing capital intensive Carbon Capture and Sequestration (CCS) in subterranean locations such as depleted oilfields does not preclude the subsequent or concurrent addition of hydrogen to facilitate a gas phase redox reaction in which carbon dioxide is converted into energy-rich methane.

Methane feedstock can efficiently be transported to plants where CO2 capture is taking place and fed into a tri-reforming reactor together with carbon dioxide, oxygen and steam to create commercially valuable syngas and obtain a return on CCS investment through the production of industrially useful carbon-containing molecules that do not pose a greenhouse gas risk.

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Suggested further reading

A mini-review on CO2 reforming of methane
Published in June 2018 this is a useful and easily readable grounder covering the thermodynamic, kinetic, catalysis and commercial aspects of the subject.

Tri-reforming: a new process for reducing CO2 emissions
A bedrock paper (January 2001) from the legendary Chunshan Song at Penn State.

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P Mander February 2022

As a follow-up to my 2018 Smart Temperature and Humidity Gauge here is a new and improved wireless version. A smartphone screen replaces the previous LCD display, allowing the data to be read remotely from the device location. The four displayed parameters are the same, but the previous Absolute Humidity formula with its -30°C to +35°C range has been replaced with a new formula (Mander 2020) with an extended temperature range.

The WiFi-enabled microcontroller can be programmed to operate in Station mode, Access Point mode or both modes simultaneously so you can use the device at home, at work, on the beach, wherever you want to know the values of the parameters which determine your comfort.

The original Smart Gauge prototype with attached LCD display

The wireless function also enables you to read temperatures inside a closed compartment such as a fridge. By following the readings on your smartphone (I set mine to refresh every 20 secs) you can see what the upper and lower thermostat settings are. For example the air in the 4°C compartment of our fridge cycles between 2.9°C and 7.5°C. I was surprised by this to begin with, but then realized that things stored in fridges generally have significantly larger heat capacities than air so their temperatures will fluctuate over narrower ranges.

A sensor mounted on jumper leads is ideal for testing condenser coil ventilation on a fridge, with the sensor placed directly in the airflow of the lower inlet and upper outlet.

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Hardware

The CarnotCycleAIR Smart Gauge is built around an Arduino IDE compatible Sparkfun ESP8266 Thing Dev microcontroller featuring an integrated FTDI USB-to-Serial chip for easy programming. A 2-pin JST connector has been soldered to the footprint alongside the micro-USB port and the board is powered by a rechargeable 3.7V lithium polymer flat pouch battery which fits neatly underneath the standard 400 tie-point breadboard. The system is designed to work with DHT sensors such as the DHT22 with a temperature range of -40°C to +80°C and relative humidity range of 0-100%, or the DHT11 with a temperature range of 0°C to +50°C and relative humidity range of 20-90%. These are available mounted on 3-pin breakout boards which feature built-in pull-up resistors. Both sensors are designed to function on the 3.3V supplied by the board, enabling the signal output to be connected directly to one of the board’s I/O pins without the need for a logic level converter [the ESP8266’s I/O pins do not easily tolerate voltages higher than 3.3V. Using 5V will blow it up].

Note: Comparing temperature readings in ambient conditions with an accurate glass thermometer has shown that when the sensors are plugged directly into the breadboard they record a temperature approx. 1°C higher than the true temperature, which in turn affects the accuracy of the computed absolute humidity and dewpoint. The cause appears to be Joule heating in the breadboard circuitry. Using jumper leads to distance the sensor from the board solves the problem.

The DHT22 sensor works happily down to –40°C, as does the new absolute humidity formula.

When used in Station mode the range is determined largely by the router. In Access Point mode where the device and smartphone communicate directly with each other, the default PCB trace antenna was found to work really well with an obstacle-free range of at least 35 meters (115 feet).

A Sparkfun LiPo Charger Basic, an incredibly tiny device just 3 cm long with a JST connector at one end and a micro-USB connector at the other, was used to recharge the battery. Charging time was about 4 hours.

The Sparkfun LiPo Charger Basic

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Circuitry

The circuitry for CarnotCycleAIR Smart Gauge couldn’t be simpler.

The ESP8266 (with header pins) is placed along the center of the breadboard and 3.3V is supplied to the power bus from the left header (3V3, GND). The DHT sensor is powered from this bus and the signal is routed to a suitable pin. I used pin 12 on the right header. That’s all there is to it.

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Coding

CarnotCycleAIR Smart Gauge is a further development of an ESP8266 project – “ESP8266 NodeMCU Access Point (AP) for Web Server” – published online by Random Nerd Tutorials which displays temperature and relative humidity on a smartphone with the ESP8266 set up as an Access Point. Code for both the Station-only version and Station and Access Point version using Arduino IDE can be copied from these mouse-over links:

Station-mode Temperature Humidity App for Smartphones

Dual-mode Temperature Humidity App for Smartphones

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© P Mander December 2021

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