Taking a break from studying thermodynamics: Mme. Curie measuring picoamp leakage currents

Having read biographies of the Curies, Marie Curie’s doctoral thesis, and a number of scholarly articles about the radium phenomenon, I have come to the conclusion that the Marie Curie legend in popular culture tends to sideline her scientific achievements, focusing more on her imagined saintliness and perceived role as bringer of medical marvels than on her pioneering work as a physical chemist, in which her husband Pierre (above left) played an important facilitating role.

To my mind, the popular press of her day was largely responsible for the misconstruction of the Marie Curie legend, filling the public’s mind with the discovery of a miracle cure for cancer brought about by what it portrayed as an angelic young foreign-born mother slaving away in a dark shed in Paris for no wages.

The media frenzy around radium had consequences. Once radium production was established on a commercial scale, ignorant and unscrupulous marketers quickly morphed the Curies’ discovery of an element that glowed in the dark into revitalizing radium baths, radium drinking water, radium chocolate, radium toothpaste, radium cigarettes and even radium suppositories for restoring male potency while eradicating hemorrhoids:

Also splendid for piles and rectal sores. Try them and see what good results you get!

The dreadful damage these products must have caused doesn’t bear thinking about. Sadly, the Curies themselves seemed carried along similarly radium-dazzled tracks. They failed to connect Pierre’s rapidly deteriorating health with exposure to radioactive emissions, while stoically accepting the painful damage to Marie’s hands as a price worth paying for the greater good they somehow imagined radium to represent.

Irène Curie points to her mother’s radiation-damaged hands

The sensationalist aspects of the Curie legend, while an education in themselves, are however not the subject of this post. Physics and chemistry are the subjects here. When you look at Marie Curie as a physical chemist, and examine her contributions to the science of natural radioactivity, it is clear how crucial a role was played by the miracle machine designed and developed by Pierre Curie.

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The Curie quartz electrometer apparatus

The above diagram is taken from Méthodes de Mesure employées en Radioactivité published in Paris in 1911 by Albert Laborde, a graduate engineer who became Pierre Curie’s assistant in 1902. It shows the quartz electrometer apparatus developed by Pierre Curie and his brother Jacques for the precise measurement of very weak currents (of the order of tenths of picoamperes) following their discovery of piezoelectricity in 1880. It was this discovery that prompted the brothers Curie to build a calibrated electrostatic charge generator using a thin quartz lamella (center) to compensate and thus measure the leakage current from a charged capacitor (left) using a quadrant electrometer (right).

This apparatus was later adapted by Pierre Curie to allow accurate quantification of the tiny leakage currents produced in an ionization chamber by samples of radioactive material.

This is the experimental set-up that Marie Curie can be seen using in the header photograph, which dates from 1898.

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Amazing coincidences

When you consider the train of coincidences that led to Marie Curie’s choice of subject for her doctorate (Recherches sur les substances radioactives) it is nothing short of amazing. At the time she was looking around for suitable topic, five years after having journeyed from Poland to Paris to enroll as a Sorbonne student, Henri Becquerel had just accidentally discovered mysterious rays emanating from uranium which had the property of weakly ionizing air. This was in 1896. Just a year previously, Marie had married Pierre Curie who happened to possess the one instrument capable of accurately measuring small ionization currents, following his discovery of piezoelectricity sixteen years earlier.

Because uranic rays were a new phenomenon, Marie was saved the task of first researching the topic which otherwise would have entailed reading a lot of academic papers in unfamiliar French. This saving of time and effort attracted her to choose to study Becquerel’s uranic rays, something she admitted in later life. Furthermore she had no competition since Becquerel had shown little interest in pursuing his original finding – the big news at the time was X rays, discovered by Wilhelm Röntgen in 1895. No fewer than 1044 papers on X rays were published in 1896, when Becquerel first announced his discovery. Not surprisingly, nobody took any notice. Marie Curie had the field to herself.

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The weight, the watch and the light spot

This magnified portion of the header image shows Marie Curie as she sits at the quartz electrometer apparatus. Her right hand can be seen holding an analytical balance weight in a controlled manner while in her left hand the edge of a stopwatch can be seen. Her eyes are looking fixedly at a horizontal measuring scale above a light source (square hole) mounted on a wooden pedestal.

The light source is shining a beam onto the mirror of a quadrant electrometer out of view to the left. The light spot is reflected onto the horizontal scale (cf. diagram above) and Marie is endeavoring to keep the light spot stationary. She does this by gradually releasing the weight which is attached to the quartz lamella, thereby generating charge to compensate the ionization current produced by the radioactive sample in the ionization chamber also out of view to the left. The entire process of weight release is timed by a stopwatch. Once the weight is fully released the watch is stopped. The weight generates a specific amount of charge Q* on the quartz lamella during the measured time T. Hence Q/T is equal to the ionization current, which is directly proportional to the intensity of the ionizing radiation emitted by the sample, or to use the term Marie Curie coined, its radioactivity.

*The amount of charge Q is calculated from Q = W × K × L/B where W is the applied weight, K is the quartz specific constant, L is the lamella length and B is the lamella thickness.

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On Thursday 25th June 1903, at La Faculté des Sciences de Paris, Marie Curie presented her doctoral thesis to the examination committee, two of whose members were later to become Nobel laureates. The committee was impressed; in fact it expressed the view that her findings represented the greatest scientific contribution ever made in a doctoral thesis.

At the outset, Curie coined a new term – radioactivity – to describe the ionizing radiation emitted by the uranium compounds studied by Henri Becquerel. She announced her discovery that the element thorium also displays radioactivity. And she presented a method, using the quartz electrometer apparatus developed by Jacques and Pierre Curie, by which the intensity of radioactive emissions could be precisely quantified and expressed as ionization currents. This was a game-changing advance on the essentially qualitative methods that had been used hitherto e.g. electroscopes and photographic plates.

As one would expect, Curie began her experimental work with a systematic study of uranium and its compounds, measuring and tabulating their ionization currents. There was a considerable range from the largest to the smallest currents, and within the limits of experimental error it was evident that the ionization currents were proportional to the amounts of uranium present in the sample. The same was true for thorium.

From the chemist’s perspective this was a puzzling result. The properties of chemical compounds of the same element generally depend on what it is compounded with and the arrangement of atoms in the molecule. Yet here was a very different finding – the radioactivity Curie measured was independent of compounding or molecular structure.

Curie drew the conclusion that radioactivity was a property of the atom – une propriété atomique she called it. She wasn’t referring to the uranium atom or the thorium atom, but to the atom as a generalized material unit with an implied interior from which radioactive emissions issued. That is a profound conception, with which Marie Curie made a significant contribution to the advancement of physics.

And at this point in her thesis she hadn’t even mentioned radium.

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New elements

For the next part of her thesis, Marie Curie turned her attention to the study of uranium-containing minerals, one of which was the mineral pictured above. Today we call it uraninite but in Curie’s day it was called pitchblende. The sample she obtained was from a uranium mine near the town of Joachimsthal in Austria, now Jáchymov in the Czech Republic. She measured its ionization current and found it to be considerably higher than its uranium content warranted. If her radioactivity hypothesis was correct, there was only one explanation: pitchblende contained atoms that emitted much more intense radiation than uranium atoms, which meant that another radioactive substance must be present in the ore. Curie now had the task of finding it, and was joined in this quest by her husband Pierre and the chemist Gustave Bémont.

The quartz electrometer demonstrated its value yet again, since the various fractions derived from the pitchblende sample during chemical analysis could be tested for radioactivity. In this way, the radioactivity was followed to two fractions: one containing the post-transition metal bismuth* and another containing the alkaline earth metal element barium. The Curies announced their findings in July 1898, stating their belief that these fractions contained two previously unknown metal elements, and suggesting that if the existence of these metals were confirmed, the bismuth-like element should be called polonium and the barium-like element radium.

*unknown to the Curies, the uranium decay series actually produces two radioisotopes of bismuth along with the isotopes of polonium, so the presence of radioactivity in this fraction did not solely indicate the presence of a new element.

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The shed

The fabled shed where Marie Curie labored for four years, chemically processing tons of pitchblende to produce a tiny spoonful of radium.

The heroic work which made Marie Curie a legend took place in a shed at the back of a Grande École* in Rue Vauquelin. In order to produce sufficient quantities to isolate the new elements and determine their atomic weights, tons of pitchblende were needed. This was because the maximum amounts of radium and polonium that can coexist in secular equilibrium with uranium are in the ratios of their respective half lives. This fact and the limited human resources available rendered any attempt to isolate polonium impossible, and the situation with radium was not much better. At best, a quantity of uranium ore containing 3 metric tons of elemental uranium is needed to extract 1 gram of radium at a yield of 100%. In the primitive conditions of the shed, obtaining a gram of radium meant processing 8 or 9 tons of uranium ore. One can only wonder at how Marie Curie found the physical and mental strength for such an arduous task.

*At the time, it was called École supérieure de physique et de chimie industrielles de la ville de Paris. Today it is called ESCPI Paris.

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Did she deserve two Nobel Prizes?

Marie Curie was awarded a quarter of the Nobel Prize for Physics in 1903 for her work on radioactivity. In 1911 she was the sole recipient of the Nobel Prize for Chemistry, awarded for the discovery of radium and polonium.

There can be no doubt about her credentials for the 1903 award, but some biographers have questioned whether the 1911 Prize was deserved, claiming that the discoveries of radium and polonium were part of the reason for the first prize.

As described in this post, the experimental evidence which Marie Curie set forth to reason that radioactivity is an atomic property was based solely on her experiments with uranium and thorium. Neither radium nor polonium had anything to do with it. On these grounds the claims of those biographers can be rejected.

Which leaves the question of under what circumstances the discovery of a new element qualifies for a Nobel Prize in chemistry. Clearly the discovery of a naturally radioactive element is not sufficient, otherwise Marguerite Perey – who worked as Marie Curie’s lab assistant and discovered francium in 1939 – would have qualified. Other aspects of the discovery need to be taken into account, and in 1911 there were many such aspects to Marie Curie’s discovery of radium and polonium, and the isolation of radium.

Reading the award citation, what comes across to me – albeit between the lines – is a recognition of the monumental personal effort and dedication involved in the discovery and characterization of these remarkable elements that led to the modern science of nuclear physics.

The miracle machine

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P Mander June 2017

  1. FlowCoef says:

    Something else totally unrelated came from Joachimsthal: the word “thaler” and, from thence, “dollar”. A powerful substance of a different sort.

    I will see what other radio active crimes against credulity I can turn up going through my backfiles.

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