Continuation. Previous part here: Death from a test tube (part 1)
I guess it's time to let it down first results.
The confrontation between armor and a projectile is a theme as eternal as the war itself. Chemical weapons are no exception. For two years of use (1914-1916), it has already evolved from practically harmless (as far as this term is generally applicable in this case) lacrimators
to murderous poisons [3]:
For clarity, they are summarized in the table.
LCt50 - relative toxicity of OM [5]
As you can see, all representatives of the first wave of OS were directed to the most affected human organs (lungs) and were not designed to meet with any serious means of protection. But the invention and widespread use of the gas mask made changes in the eternal confrontation between armor and a projectile. The howling countries again had to pay a visit to the laboratories, after which they appeared in the trenches arsenic and sulfur derivatives.
The filters of the first gas masks contained only impregnated activated carbon as an active body, which made them very effective against vapor and gaseous substances, but they were easily "pierced" by solid particles and aerosol droplets. Arsines and mustard gas became toxic substances of the second generation.
The French have proved here too that they are good chemists. On May 15, 1916, during an artillery bombardment, they used a mixture of phosgene with tin tetrachloride and arsenic trichloride (COCl2, SnCl4 and AsCl3), and on July 1 - a mixture of hydrocyanic acid with arsenic trichloride (HCN and AsCl3). Even I, a certified chemist, can hardly imagine that branch of hell on earth, which was formed after this artillery preparation. True, one nuance cannot be ignored: the use of hydrocyanic acid as an agent is completely unpromising, because, despite its fame as a note-taking killer, it is an extremely volatile and unstable substance. But at the same time, a serious panic arose - this acid was not delayed by any gas mask of that time. (In fairness, it must be said that the current gas masks do not cope with this task very well - a special box is needed.)
The Germans did not hesitate to answer for a long time. And it was much more crushing, for the arsines they used were much stronger and more specialized substances.
Diphenylchloroarsine and diphenylcyanarsine - and it was they - were not only much more deadly, but also because of the strong "penetrating action" were called "pests of gas masks." The arsine shells were marked with a "blue cross".
Arsines are solids. To spray them, it was required to significantly increase the explosive charge. So a chemical fragmentation projectile reappeared at the front, but already extremely powerful in its action. Diphenylchloroarsine was used by the Germans on July 10, 1917 in combination with phosgene and diphosgene. Since 1918, it was replaced by diphenylcyanarsine, but was still used both individually and mixed with a successor.
The Germans even developed a method of combined fire with "blue" and "green cross" shells. The shells of the "blue cross" hit the enemy with shrapnel and forced them to take off their gas masks, the shells of the "green cross" poisoned the soldiers who had taken off their masks. So a new tactic of chemical shooting was born, which received the beautiful name of "shooting with a multi-colored cross".
July 1917 turned out to be rich in German OV debuts. On the twelfth, under the same long-suffering Belgian Yprom, the Germans used a novelty that had not previously appeared on the fronts. On this day, 60 thousand shells containing 125 tons of yellowish oily liquid were fired at the positions of the Anglo-French troops. This is how the mustard gas was first used by Germany.
This OM was a novelty not only in the chemical sense - sulfur derivatives were not yet used in this capacity, but it also became the ancestor of a new class - skin blister agents, which, moreover, had a generally toxic effect. The properties of mustard gas to penetrate porous materials and cause severe injuries on contact with the skin made it necessary to have protective clothing and footwear in addition to a gas mask. The shells filled with mustard gas were marked with a "yellow cross".
Although mustard gas was intended to "bypass" gas masks, the British did not have them at all on that terrible night - an unforgivable carelessness, the consequences of which fade only against the background of its insignificance.
As is often the case, one tragedy follows another. Soon the British deployed reserves, this time in gas masks, but after a few hours they were also poisoned. Being very persistent on the ground, mustard gas poisoned the troops for several days, sent by the command to replace the defeated with a tenacity worthy of better use. The losses of the British were so great that the offensive in this sector had to be postponed for three weeks. According to the estimates of the German military, mustard shells were about 8 times more effective at destroying enemy personnel than their "green cross" shells.
Fortunately for the Allies, in July 1917, the German army did not yet have a large number of mustard shells or protective clothing that would allow an offensive in an area contaminated with mustard gas. However, as the German military industry increased the rate of production of mustard shells, the situation on the Western Front began to take on a far from being the best for the Allies. Sudden night attacks on British and French positions with yellow cross shells began to be repeated more and more often. The number of mustard gas poisoned among the Allied troops grew. In just three weeks (from July 14 to August 4 inclusive), the British lost 14,726 people from mustard gas alone (500 of them died). The new poisonous substance seriously interfered with the work of the British artillery, the Germans easily gained the upper hand in the counter-gun struggle. The areas designated for the concentration of troops were infected with mustard gas. The operational consequences of its use soon appeared. In August-September 1917, mustard gas made the 2nd French army's offensive near Verdun drown. French attacks on both banks of the Meuse were repelled by the Germans with yellow cross shells.
According to many German military authors of the 1920s, the Allies failed to carry out the planned breakthrough of the German front for the fall of 1917 precisely because of the widespread use of shells by the German army of “yellow” and “multi-colored” crosses. In December, the German army received new instructions for the use of various types of chemical projectiles. With the pedantry characteristic of the Germans, each type of chemical projectile was given a strictly defined tactical purpose and methods of use were indicated. The instructions will still do a very disservice to the German command itself. But that will happen later. In the meantime, the Germans were full of hope! They did not allow their army to be “ground” in 1917, Russia withdrew from the war, thanks to which the Germans achieved a small numerical superiority on the Western Front for the first time. Now they had to achieve victory over the allies before the American army became a real participant in the war.
The effectiveness of mustard gas became so great that it was used almost everywhere. It flowed through the streets of cities, filled meadows and hollows, poisoned rivers and lakes. Sites contaminated with mustard gas were marked in yellow on the maps of all armies (this marking of areas of terrain affected by OM of any type remained to this day). If chlorine became the horror of the First World War, then mustard gas can no doubt claim to be its calling card. Is it any wonder that the German command began to view chemical weapons as the main weight on the scales of the war, which they were going to use to tip the cup of victory to their side (does not resemble anything, eh?). German chemical plants produced over a thousand tons of mustard gas every month. In preparation for a major offensive in March 1918, German industry launched the production of a 150-mm chemical projectile. It differed from the previous samples by a strong charge of TNT in the nose of the projectile, separated from the mustard gas by an intermediate bottom, which made it possible to more efficiently spray the OM. In total, more than two million (!) Shells with different types of weapons were produced, which were used during Operation Michael in March 1918. The breakthrough of the front in the Leuven - Guzokur sector, the offensive on the Lys River in Flanders, the storming of Mount Kemmel, the battle on the Ain River, the offensive on Compiegne - all these successes, among other things, became possible thanks to the use of the “multi-colored cross”. At least such facts indicate the intensity of the use of OM.
On April 9th, the offensive zone underwent a hurricane of fire with a "multi-colored cross". The shelling of Armantier was so effective that mustard gas literally flooded its streets. The British left the poisoned city without a fight, but the Germans themselves were able to enter it only after two weeks. The losses of the British in this battle by the poisoned reached 7 thousand people.
In the offensive zone on Mount Kemmel, German artillery fired a large number of "blue cross" shells and, to a lesser extent, "green cross" shells. Behind enemy lines, a “yellow cross” was set up from Sherenberg to Kruststraaetskhuk. After the British and French, hurrying to rescue the garrison of Mount Kemmel, stumbled upon mustard-infested areas of the terrain, they stopped all attempts to help out the garrison. The losses of the British from April 20 to April 27 - about 8,500 poisoned people.
But the time for victories was running out for the Germans. More and more American reinforcements arrived at the front and joined the battle with enthusiasm. The Allies made extensive use of tanks and aircraft. And in the matter of chemical warfare itself, they took over a lot from the Germans. By 1918, the chemical discipline of their troops and the means of protection against toxic substances were already superior to those of Germany. The German monopoly on mustard gas was also undermined. The allies could not master the rather complex Mayer-Fischer synthesis, so they produced mustard gas using the simpler Nieman or Pope-Green method. Their mustard gas was of inferior quality, contained a large amount of sulfur, and was poorly stored, but who was going to store it for future use? Its production grew rapidly both in France and in England.
The Germans feared mustard gas no less than their opponents. The panic and horror caused by the use of mustard shells against the 2nd Bavarian Division by the French on July 13, 1918, caused a hasty withdrawal of the entire corps. On September 3, the British began using their own mustard shells at the front, with the same devastating effect. Played a cruel joke and German pedantry in the use of OV. The categorical requirement of the German instructions to use only shells with unstable poisonous substances for shelling the point of attack, and shells of the "yellow cross" to cover the flanks, led to the fact that the Allies, during the period of German chemical training in the distribution along the front and in depth of shells with persistent and low-resistance with poisonous substances, they found out exactly which areas were intended by the enemy for a breakthrough, as well as the estimated depth of development of each of the breakthroughs. Long-term artillery preparation provided the allied command with a clear outline of the German plan and excluded one of the main conditions for success - surprise. Accordingly, the measures taken by the Allies significantly reduced the subsequent successes of the grandiose chemical attacks of the Germans. Winning on an operational scale, the Germans did not achieve their strategic goals by any of their "big offensives" in 1918.
After the failure of the German offensive on the Marne, the Allies seized the initiative on the battlefield. Including in terms of the use of chemical weapons. What happened next is known to everyone …
But it would be a mistake to think that the history of "combat chemistry" ended there. As you know, something once applied will excite the minds of generals for a long time. And with the signing of peace treaties, the war, as a rule, does not end. It just goes into other forms. And places. Very little time passed, and a new generation of deadly substances came from the laboratories - organophosphorus OM.
After the end of the First World War, chemical weapons took a strong, and far from the last place in the arsenals of the warring countries. In the early 1930s, few doubted that a new clash between the leading powers would not be complete without the large-scale use of chemical weapons.
Following the results of the First World War, mustard gas, which bypasses the gas mask, became the leader among the poisonous substances. Therefore, research on the creation of new chemical weapons was carried out in the direction of improving the skin blister agents and the means of their use. In order to search for more toxic analogs of mustard gas, hundreds of structurally related compounds were synthesized in the period between the world wars, but none of them had an advantage over the "good old" mustard gas of the First World War in terms of the combination of properties. The disadvantages of individual agents were compensated for by the creation of formulations, that is, by obtaining mixtures of agents with different physicochemical and damaging properties.
The most "prominent" representatives of the interwar period of the development of lethal molecules include lewisite, a skin blister agent of the class of chlorinated arsines. In addition to the main action, it also affects the cardiovascular, nervous system, respiratory organs, and the gastrointestinal tract.
But no improvement in recipes or synthesis of new analogs of OM, tested on the battlefield during the First World War, did not go beyond the general level of knowledge of that time. Based on the anti-chemical guidelines of the 1930s, the methods of their use and means of protection were quite obvious.
In Germany, war chemistry research was banned by the Treaty of Versailles, and Allied inspectors closely monitored its implementation. Therefore, in German chemical laboratories, only chemical compounds designed to combat insects and weeds were studied - insecticides and herbicides. Among them was a group of compounds of phosphorus acid derivatives, which chemists have been studying for almost 100 years, at first without even knowing about the toxicity of some of them to humans. But in 1934, an employee of the German concern "IG-Farbenidustri" Gerhard Schroeder synthesized a new insecticide herd, which, when inhaled, turned out to be almost 10 times more toxic than phosgene, and can cause death of a person within a few minutes with symptoms of suffocation and convulsions, turning into paralysis …
As it turned out, the herd (in the designation system it received the GA marking) represented a fundamentally new class of military weapons with a nerve-paralytic effect. The second innovation was that the mechanism of action of the new OS was quite clear: blocking of nerve impulses with all the ensuing consequences. Another thing was also obvious: not the entire molecule as a whole or one of its atoms (as it was before) is responsible for its lethality, but a specific grouping that carries a quite definite chemical and biological effect.
The Germans have always been excellent chemists. The theoretical concepts obtained (albeit not as complete as we have at the present time) made it possible to conduct a purposeful search for new deadly substances. Right before the war, German chemists, under the leadership of Schroeder, synthesized sarin (GB, 1939) and, already during the war, soman (GD, 1944) and cyclosarin (GF). All four substances have received the general name "G-series". Germany has once again gained a qualitative advantage over its chemical opponents.
All three OM are transparent, water-like liquids; with slight heating, they evaporate easily. In their pure form, they practically do not have a smell (the herd has a faint pleasant smell of fruit), therefore, at high concentrations, easily created in the field, a lethal dose can quickly and imperceptibly accumulate inside the body.
They perfectly dissolve not only in water, but also in many organic solvents, have a durability of several hours to two days, and are quickly absorbed into porous surfaces (shoes, fabric) and leather. Even today, this combination of combat capabilities has a mesmerizing effect on the imaginations of generals and politicians. The fact that it was not necessary to apply new developments on the fields of a new world war is the greatest historical justice, because one can only guess how petty the past world carnage might seem if the compounds of the "element of thought" were used.
The fact that Germany was not given new weapons during the new war did not mean that work on them would not be continued. The captured stocks of FOV (and their account was in the thousands of tons) were carefully studied and recommended for use and modification. In the 50s, a new series of nerve agents appeared, which are ten times more toxic than other agents of the same action. They were labeled V-gases. Probably, every graduate of the Soviet school heard the abbreviation VX in the CWP lessons on the topic “Chemical weapons and protection against them”. This is perhaps the most toxic of artificially created substances, which, moreover, was also mass-produced by chemical plants on the planet. Chemically, it is called S-2-diisopropylaminoethyl or O-ethyl ester of methylthiophosphonic acid, but it would be more correctly called Concentrated Death. Only out of love for chemistry, I am placing a portrait of this deadly substance:
Even in the school course, they say that chemistry is an exact science. Maintaining this reputation, I propose to compare the toxicity values of these representatives of the new generation of killers (OVs are selected in an order approximately corresponding to the chronology of their use or appearance in arsenals):
Below is a diagram illustrating the change in the toxicity of the listed OM (the -lg (LCt50) value is plotted on the ordinate, as a characteristic of the degree of toxicity increase). Quite clearly, it can be seen that the period of "trial and error" ended quite quickly, and with the use of arsines and mustard gas, the search for effective agents was carried out in the direction of enhancing the damaging effect, which was especially clearly demonstrated by a series of FOVs.
In one of his monologues M. Zhvanetsky said: "Whatever you do with a person, he stubbornly crawls into the cemetery." One can argue about the awareness and desire of this process by each individual person, but there is no doubt that the politicians who dream of world domination and the generals who cherish these dreams are ready to send a good half of humanity there to achieve their goals. However, they, of course, do not see themselves in this part. But the poison does not care who to kill: enemy or ally, friend or foe. And having done her dirty work, she will not always strive to leave the battlefield. So in order not to fall under their own "gifts", like the British in WWI, a "brilliant" idea appeared: to equip ammunition not with ready-made agents, but only with its components, which, when mixed, can react relatively quickly with each other, forming a deadly cloud.
Chemical kinetics says that reactions will proceed most rapidly with the minimum amount of reactants. This is how binary OBs were born. Thus, the chemical munition is given the additional function of a chemical reactor.
This concept is not a supernova discovery. It was studied in the USA before and during WWII. But they began to actively deal with this issue only in the second half of the 50s. In the 1960s, US Air Force arsenals were replenished with VX-2 and GB-2 bombs. The two in the designation indicates the number of components, and the letter marking indicates the substance that appears as a result of mixing them. In addition, the components may include small amounts of catalyst and reaction activators.
But, as you know, you have to pay for everything. The convenience and safety of binary ammunition were purchased due to the smaller amount of OM compared to the same unitary ones: the place is “eaten up” by partitions and devices for mixing reagents (if necessary). In addition, being substances of an organic nature, they interact rather slowly and not completely (the practical reaction yield is about 70-80%). In total, this gives an approximate loss of efficiency of 30-35%, which should be compensated for by the high consumption of ammunition. All this, in the opinion of many military experts, speaks of the need for further improvement of binary weapons systems. Although, as it seems, much further, when, and so, in front of your feet is a bottomless grave …
Even such a relatively small excursion into the history of chemical weapons allows us to make a quite definite output.
Chemical weapons were invented and first used not by “eastern despots” such as Russia, but by the most “civilized countries” that are now bearers of the “highest standards of freedom, democracy and human rights” - Germany, France and the United Kingdom. Engaged in the chemical race, Russia did not seek to create new poisons, while its best sons spent their time and energy creating an effective gas mask, the design of which was shared with allies.
The Soviet power inherited everything that was stored in the warehouses of the Russian army: about 400 thousand chemical projectiles, tens of thousands of cylinders with special valves for gas launches of a chloro-phosgene mixture, thousands of flamethrowers of various types, millions of Zelinsky-Kummant gas masks. Also, this should include more than a dozen phosgene factories and workshops and first-class equipped laboratories for the gas mask business of the All-Russian Zemstvo Union.
The new government perfectly understood what kind of predators they would have to deal with, and least of all they wanted a repetition of the tragedy of May 31, 1915 near Bolimov, when the Russian troops were defenseless against the chemical attack of the Germans. Leading chemists of the country continued their work, but not so much to improve the weapons of destruction, but to create new means of protection against it. Already on November 13, 1918, by order of the Revolutionary Military Council of the Republic No. 220, the Chemical Service of the Red Army was created. At the same time, the All-Russian Soviet courses of military gas engineering were created, where military chemists were trained. We can say that the beginning of the glorious history of the Soviet (and now Russian) radiation, chemical and biological defense troops was laid precisely in those terrible and turbulent years.
In 1920, the courses were transformed into the Higher Military Chemical School. In 1928, a research organization in the field of chemical weapons and anti-chemical protection was created in Moscow - the Institute of Chemical Defense (in 1961 it was transferred to the city of Shikhany), and in May 1932 the Military Chemical Academy was formed to train specialists -chemists for the Red Army.
Over the twenty post-war years in the USSR, all the necessary weapon systems and means of destruction were created, which made it possible to hope for a worthy response to the enemy who risked using them. And in the post-war period, the chemical defense troops were ready to use all the forces and means available in their arsenal for an adequate response to any situation.
But … The fate of such a "promising" means of mass murder of people was paradoxical. Chemical weapons, as well as later atomic ones, were destined to turn from combat to psychological. And let it stay that way. I would like to believe that the descendants will take into account the experience of their predecessors and will not repeat their deadly mistakes.
As Mark Twain used to say, in any work of writing, the most difficult thing is to put the last point, since there is always something else that I would like to talk about. As I suspected from the outset, the topic turned out to be as vast as it is tragic. Therefore, I will allow myself to conclude my small chemical-historical review with a section called "Historical background or picture gallery of the murderers."
In this part, brief information will be given about the history of the discovery of all the participants in our study, who, if they were living people, could be safely ranked among the most dangerous mass murderers.
Chlorine … The first artificially created chlorine compound - hydrogen chloride - was obtained by Joseph Priestley in 1772. Elemental chlorine was obtained in 1774 by the Swedish chemist Karl Wilhelm Scheele, who described its release by the interaction of pyrolusite (manganese dioxide) with hydrochloric acid (a solution of hydrogen chloride in water) in his treatise on pyrolusite.
Bromine … It was opened in 1826 by a young teacher of the Montpellier college, Antoine Jerome Balard. Balar's discovery made his name known to the whole world, despite the fact that he was a very ordinary teacher and a rather mediocre chemist. One curiosity is connected with its discovery. A small amount of bromine was literally "held in his hands" by Justus Liebig, but he considered it one of the compounds of chlorine with iodine and abandoned research. Such disregard for science, however, did not prevent him from later sarcastically saying: "It was not Balar who discovered bromine, but Balar discovered bromine." Well, as they say, to each his own.
Hydrocyanic acid … It is widely represented in nature, it is found in some plants, coke oven gas, tobacco smoke (fortunately, in trace, non-toxic amounts). It was obtained in its pure form by the Swedish chemist Karl Wilhelm Scheele in 1782. It is believed that she became one of the factors that shortened the life of the great chemist and became the cause of severe poisoning and death. It was later investigated by Guiton de Morveau, who proposed a method for obtaining it in commercial quantities.
Chlorocyanogen … Received in 1915 by Joseph Louis Gay-Lussaac. He also received cyanogen, a gas that is the ancestor of both hydrocyanic acid and many other cyanide compounds.
Ethyl bromine (iodine) acetate … It was not possible to establish reliably who exactly was the first to receive these representatives of the glorious family of poisoners (or rather, tearguns). Most likely, they were the side children of the discovery in 1839 by Jean Baptiste Dumas of chlorine derivatives of acetic acid (from personal experience, I note - indeed, the stinker is still the same).
Chlorine (bromine) acetone … Both caustic stinkers (also personal experience, alas) are obtained in similar ways according to the Fritsch (first) or Stoll (second) method by the direct action of halogens on acetone. Obtained in the 1840s (no more precise date could be established).
Phosgene … Received by Humphrey Devi in 1812 when irradiated with ultraviolet light a mixture of carbon monoxide and chlorine, for which he received such an exalted name - "born of light."
Diphosgene … Synthesized by the French chemist Auguste-André-Thomas Caur in 1847 from phosphorus pentachloride and formic acid. In addition, he studied the composition of cacodyl (dimethylarsine), in 1854 he synthesized trimethylarsine and tetramethylarsonium, which played an important role in chemical warfare. However, the love of the French for arsenic is quite traditional, I would even say - fiery and tender.
Chloropicrin … Obtained by John Stenhouse in 1848 as a by-product in the study of picric acid by the action of bleach on the latter. He also gave it the name. As you can see, the starting materials are quite available (I already wrote about PC a little earlier), the technology is generally simpler (no heating-distillation-extractions), so this method was applied practically without any changes on an industrial scale.
Diphenylchloroarsine (DA) … Discovered by the German chemist Leonor Michaelis and the Frenchman La Costa in 1890.
Diphenylcyanarin (DC) … Analogue (DA), but discovered a little later - in 1918 by the Italians Sturniolo and Bellizoni. Both poisoners are almost analogs and became the ancestors of a whole family of organic substances based on organic compounds of arsenic (direct descendants of the Kaura arsines).
Mustard (HD) … This calling card of the First World War was first synthesized (ironically) by the Belgian-born Cesar Despres in 1822 in France and in 1860 independently of him and of each other by the Scottish physicist and chemist Frederic Guthrie and the former German pharmacist Albert Niemann. They all came, oddly enough, from the same set: sulfur and ethylene dichloride. It seems that the devil has taken care of the bulk deliveries in advance in the coming years …
The history of the discovery (praise heaven, not the use!) Of organophosphorus is described above. So there is no need to repeat.
Literature
1.https://xlegio.ru/throwing-machines/antiquity/greek-fire-archimedes-mirrors/.
2.https://supotnitskiy.ru/stat/stat72.htm.
3.https://supotnitskiy.ru/book/book5_prilogenie12.htm.
4. Z. Franke. Chemistry of toxic substances. In 2 volumes. Translation from it. Moscow: Chemistry, 1973.
5. Alexandrov V. N., Emelyanov V. I. Poisonous substances: Textbook. allowance. Moscow: Military Publishing, 1990.
6. De-Lazari A. N. Chemical weapons on the fronts of the world war 1914-1918 A brief historical sketch.
7. Antonov N. Chemical weapons at the turn of two centuries.
