Discovery of Nitrogen :
The study of the atmosphere led to the discovery of nitrogen. Although it is associated with the name of a certain scientist and a certain date, this certainly is misleading. It is rather difficult to separate the history of nitrogen discovery from the mainstream of pneumatic chemistry; one can only think of a more or less logical sequence of events.
Very early in history man came across nitrogen compounds, for instance, saltpeter and nitric acid, frequently observing liberation of brown vapours of nitrogen dioxide. Obviously, it would be impossible to discover nitrogen by decomposing its inorganic compounds. Tasteless, colourless, odorless, and chemically rather inactive, nitrogen would have remained unnoticed.
Therefore, it is not easy to decide where to begin the story of the discovery of nitrogen. Although our choice may seem subjective, we start with 1767 when H. Cavendish and J. Priestley, another outstanding English physicist, chemist, and philosopher, set out to study the action of electric discharges on various gases. There were only few such gases at that time: ordinary air, fixed air, and inflammable air. Although the experiments did not produce definite results, it was shown later that electric discharge in humid air yields nitric acid. Later this fact proved to be useful for the analysis of the earth’s atmosphere.
In 1777 H. Cavendish reported in a private letter to J. Priestley that he had succeeded in preparing a new variety of air named by him asphyxiating or mephitic air. Cavendish repeatedly passed atmospheric air over red–hot coal. The resulting fixed air was absorbed with alkali. The residue was mephitic gas. Cavendish did not study it thoroughly and only reported the fact to Priestley. Cavendish returned to the study of mephitic air much later, did a large work but the credit for the discovery had already gone to another scientist.
When Priestley received the letter from Cavendish he was busy with important experiments and read it without due attention. Priestley burned various inflammable compounds in a given volume of air and calcinated metals; the fixed air formed during these processes was removed with the aid of limewater. The main thing which he noticed was that the volume of air decreased considerably. A reader will prompt that as a result of metal calcination or combustion of compounds the oxygen present in the apparatus was bonded and nitrogen remained. Priestley, however, had no idea about the existence of such a gas as oxygen (two years later, however, he became one of its discoverers) and, to explain the observed phenomenon, he turned to phlogiston. Priestley believed that the result of metal calcination was due exclusively to the action of phlogiston. The remaining air is saturated with phlogiston and, consequently, it can be named “phlogisticated” air; it sustains neither respiration nor combustion.
Thus, Priestley was in possession of a gas which subsequently became known as nitrogen. But this extremely important result was treated by him as something of secondary importance. The existence of “phlogisticated” air was for Priestley evidence of the fact that phlogiston did play a role in natural processes. This story shows once more how the erroneous phlogistic theory hampered the discovery of elemental gases.
So, neither Cavendish nor Priestley could understand the real nature of the new gas. The understanding came later when oxygen appeared on the scene of chemistry. The English physician D. Rutherford, the pupil of J. Black, who is considered to be the discoverer of nitrogen, did, in principle, nothing new compared with his famous colleagues. In September 1772, Rutherford published a magisterial thesis On the So–called fixed and Mephitic Air in which he described the properties of nitrogen. This gas, according to Rutherford, was absorbed neither by limewater nor by alkali and was unsuitable for respiration; he named it “corrupted” air.
Not properly discovered or understood as a gaseous chemical element, nitrogen in the seventies of the 18th century had three names which confused still more the fuzzy chemical concept muddled by the persisting influence of the phlogistic theory. Phlogisticated, mephitic, or corrupted air was yet receive its final name.
This name was proposed in 1787 by A. Lavoisier and other French scientists who developed the principles of as new chemical nomenclature. They derived the word “azote” from the Greek negative prefix “a” and the word “zoe” meaning “life”. Lifeless, not supporting respiration and combustion, that was how the chemists saw the main property of nitrogen. Later this view turned out to be erroneous: nitrogen is vitally important for plants. The name “azote”, however, remained. The symbol of the element, N, originates from the Latin nitrogenium which means “saltpeter–forming”.Cavendish studied the properties of nitrogen in detail. He was one of the first scientists to believe that phlogisticated air is a component of ordinary air. One day, in the course of his experiments Cavendish questioned the homogeneity of phlogisticated air. He passed an electric spark through its mixture with oxygen transforming the whole into nitrogen oxides which were removed from the reaction zone. But every time a small fraction of the phlogisticated air (nitrogen) remained unchanged and did not react with oxygen. It was a very small fraction, a slightly noticeable gas bubble–only 1/125 of all nitrogen taken for the phenomenon observed in 1785. The answer was found only over one hundred years later. You will read about it in chapter 9 devoted to inert gases.