The author would like to devote this study to one known substance. The substance that gave the world Marilyn Monroe and white threads, antiseptics and foaming agents, epoxy glue and a reagent for the determination of blood, and even used by aquarists to refresh the water and clean the aquarium. We are talking about hydrogen peroxide, more precisely, about one aspect of its use - about its military career.
But before proceeding with the main part, the author would like to clarify two points. The first is the title of the article. There were many options, but in the end it was decided to use the title of one of the publications written by the engineer-captain of the second rank L. S. Shapiro, as the most clearly meeting not only the content, but also the circumstances accompanying the introduction of hydrogen peroxide into military practice.
Second, why was the author interested in this particular substance? Or rather, how exactly did it interest him? Oddly enough, its completely paradoxical fate in the military field. The thing is that hydrogen peroxide has a whole set of qualities that, it would seem, promised him a brilliant military career. And on the other hand, all these qualities turned out to be completely inapplicable for using it as a military supply. Well, it's not like calling it completely unusable - on the contrary, it was used, and quite widely. But on the other hand, nothing extraordinary came out of these attempts: hydrogen peroxide cannot boast such an impressive track record as nitrates or hydrocarbons. It turned out to be to blame for everything … However, let's not rush. Let's just look at some of the most interesting and dramatic moments in the military history of peroxide, and each of the readers will draw their own conclusions. And since each story has its own beginning, we will get acquainted with the circumstances of the birth of the hero of the story.
Opening of Professor Tenar …
Outside the window was a clear, frosty December day in 1818. A group of chemistry students from the Ecole Polytechnique Paris hastily filled the auditorium. There were no people who wanted to miss the lecture of the famous professor of the school and the famous Sorbonne (University of Paris) Jean Louis Thénard: each of his classes was an unusual and exciting journey into the world of amazing science. And so, opening the door, the professor entered the auditorium with a light springy gait (a tribute to the Gascon ancestors).
Out of habit, nodding to the audience, he quickly walked over to the long demonstration table and said something to the drug to old man Lesho. Then, rising to the pulpit, looked around the students and began quietly:
“When a sailor shouts“Earth!”From the front mast of a frigate and the captain first sees an unknown shore through a telescope, this is a great moment in the life of a navigator. But isn't the moment when a chemist first discovers particles of a new, hitherto unknown substance at the bottom of the flask, is not just as great?
Thenar left the lectern and walked over to the demonstration table, on which Leshaux had already managed to put a simple device.
“Chemistry loves simplicity,” Tenar continued. - Remember this, gentlemen. There are only two glass vessels, an outer and an inner one. There is snow in between: the new substance prefers to appear at low temperatures. Diluted 6% sulfuric acid is poured into the inner vessel. Now it is almost as cold as the snow. What happens if I drop a pinch of barium oxide into the acid? Sulfuric acid and barium oxide will give harmless water and a white precipitate - barium sulfate. Everyone knows that.
H2SO4 + BaO = BaSO4 + H2O
“But now I’ll ask your attention! We are approaching unknown shores, and now the shout of "Earth!" Will be heard from the front mast. I throw in the acid not oxide, but barium peroxide - a substance that is obtained when barium is burned in an excess of oxygen.
The audience was so quiet that the heavy breathing of Lesho's cold was clearly heard. Thenar, gently stirring the acid with a glass rod, slowly, grain by grain, poured barium peroxide into the vessel.
“We'll filter the sediment, ordinary barium sulfate,” said the professor, pouring water from the inner vessel into a flask.
H2SO4 + BaO2 = BaSO4 + H2O2
- This substance looks like water, doesn't it? But this is strange water! I throw a piece of ordinary rust into it (Lesho, a splinter!), And watch how the barely smoldering light flares up. Water that keeps burning!
- This is special water. It contains twice as much oxygen as usual. Water is hydrogen oxide, and this liquid is hydrogen peroxide. But I like another name - "oxidized water". And by right as a pioneer, I prefer this name.
- When a navigator discovers an unknown land, he already knows: someday cities will grow on it, roads will be laid. We chemists can never be sure of the fate of our discoveries. What's next for a new substance in a century? Perhaps the same widespread use as sulfuric or hydrochloric acid. Or maybe complete oblivion - as unnecessary …
The audience clamored.
But Tenar continued:
- And yet I am confident in the great future of "oxidized water", because it contains a large amount of "life-giving air" - oxygen. And most importantly, it stands out very easily from such water. This alone instills confidence in the future of "oxidized water". Agriculture and handicrafts, medicine and manufacture, and I don't even know yet where "oxidized water" will be used! What still fits in the flask today can burst into every house with power tomorrow.
Professor Tenar slowly left the lectern.
A naive Parisian dreamer … A convinced humanist, Thénard always believed that science should bring benefits to mankind, making life easier and making it easier and happier. Even constantly having before his eyes examples of a directly opposite nature, he firmly believed in a great and peaceful future of his discovery. Sometimes you start to believe in the fairness of the statement “Happiness is in ignorance” …
However, the start of the hydrogen peroxide career was quite peaceful. She worked regularly in textile factories, bleaching threads and linen; in laboratories, oxidizing organic molecules and helping to obtain new substances that do not exist in nature; began to master the medical wards, confidently establishing herself as a local antiseptic.
But some negative aspects soon became clear, one of which turned out to be low stability: it could exist only in solutions of relatively low concentration. And as usual, since concentration does not suit you, it must be increased. And that's how it began …
… and the find of engineer Walter
The year 1934 in European history was marked by quite a few events. Some of them excited hundreds of thousands of people, others passed quietly and unnoticed. The first, of course, can be attributed to the appearance in Germany of the term "Aryan science". As for the second, it was the sudden disappearance from the open press of all references to hydrogen peroxide. The reasons for this strange loss became clear only after the crushing defeat of the "millennial Reich".
It all started with an idea that came to the head of Helmut Walter, the owner of a small factory in Kiel for the production of precision instruments, research equipment and reagents for German institutes. He was a capable, erudite man and, importantly, enterprising. He noticed that concentrated hydrogen peroxide can persist for quite a long time in the presence of even small amounts of stabilizing substances, such as, for example, phosphoric acid or its salts. Uric acid proved to be a particularly effective stabilizer: 1 g of uric acid was sufficient to stabilize 30 liters of highly concentrated peroxide. But the introduction of other substances, decomposition catalysts, leads to a violent decomposition of the substance with the release of a large amount of oxygen. Thus, the tempting prospect of regulating the degradation process with fairly inexpensive and simple chemicals has emerged.
In itself, all this was known for a long time, but, besides this, Walter drew attention to the other side of the process. The decomposition of peroxide
2 H2O2 = 2 H2O + O2
the process is exothermic and is accompanied by the release of a rather significant amount of energy - about 197 kJ of heat. This is a lot, so much that it is enough to bring to a boil two and a half times more water than is formed during the decomposition of peroxide. Unsurprisingly, the entire mass instantly turned into a cloud of superheated gas. But this is a ready-made steam-gas - the working fluid of the turbines. If this superheated mixture is directed to the blades, then we get an engine that can work anywhere, even where there is a chronic lack of air. For example, in a submarine …
Keel was an outpost of German submarine construction, and the idea of a hydrogen peroxide submarine engine captured Walter. It attracted with its novelty, and besides, the engineer Walter was far from unmercenary. He understood perfectly well that under the conditions of a fascist dictatorship, the shortest path to prosperity was to work for the military departments.
Already in 1933, Walter independently undertook a study of the energy potential of H2O2 solutions. He made a graph of the dependence of the main thermophysical characteristics on the concentration of the solution. And that's what I found out.
Solutions containing 40-65% H2O2, decomposing, noticeably heat up, but not enough to form a high-pressure gas. When decomposing more concentrated solutions, much more heat is released: all the water evaporates without residue, and the residual energy is completely spent on heating the steam-gas. And what is also very important; each concentration corresponded to a strictly defined amount of heat released. And a strictly defined amount of oxygen. And finally, the third - even stabilized hydrogen peroxide decomposes almost instantly under the action of potassium permanganates KMnO4 or calcium Ca (MnO4) 2.
Walter managed to see a completely new field of application of the substance, known for over a hundred years. And he studied this substance from the point of view of the intended use. When he brought his considerations to the highest military circles, an immediate order was received: to classify everything that is somehow connected with hydrogen peroxide. From now on, technical documentation and correspondence featured "aurol", "oxylin", "fuel T", but not the well-known hydrogen peroxide.
Schematic diagram of a steam-gas turbine plant operating on a "cold" cycle: 1 - propeller; 2 - reducer; 3 - turbine; 4 - separator; 5 - decomposition chamber; 6 - control valve; 7- electric pump of peroxide solution; 8 - elastic containers of peroxide solution; 9 - non-return valve for overboard removal of peroxide decomposition products.
In 1936, Walter presented the first installation to the submarine fleet management, which worked on the indicated principle, which, despite the rather high temperature, was called "cold". The compact and lightweight turbine developed 4000 hp at the stand, fully meeting the designer's expectations.
The products of the decomposition reaction of a highly concentrated solution of hydrogen peroxide were fed into a turbine, which rotated a propeller through a reduction gearbox, and then were discharged overboard.
Despite the obvious simplicity of such a solution, there were accompanying problems (and how can we do without them!). For example, it was found that dust, rust, alkalis and other impurities are also catalysts and dramatically (and much worse - unpredictably) accelerate the decomposition of peroxide, thereby creating an explosion hazard. Therefore, elastic containers made of synthetic material were used to store the peroxide solution. It was planned to place such containers outside a solid body, which made it possible to efficiently use the free volumes of the interbody space and, in addition, create a backwater of the peroxide solution in front of the unit pump due to the seawater pressure.
But the other problem turned out to be much more complicated. The oxygen contained in the exhaust gas is rather poorly soluble in water, and betrayed the location of the boat, leaving a trail of bubbles on the surface. And this despite the fact that "useless" gas is a vital substance for a ship designed to stay at depth for as long as possible.
The idea of using oxygen as a source of fuel oxidation was so obvious that Walter started a parallel design of a hot cycle engine. In this variant, organic fuel was supplied to the decomposition chamber, which was burned in previously unused oxygen. The power of the installation increased sharply and, in addition, the trace decreased, since the combustion product - carbon dioxide - dissolves much better than oxygen in water.
Walter was aware of the shortcomings of the "cold" process, but put up with them, since he understood that in a constructive sense, such a power plant would be incomparably simpler than with a "hot" cycle, which means that you can build a boat much faster and demonstrate its advantages …
In 1937, Walter reported the results of his experiments to the leadership of the German Navy and assured everyone of the possibility of creating submarines with steam-gas turbine installations with an unprecedented submerged speed of more than 20 knots. As a result of the meeting, it was decided to create an experimental submarine. In the process of its design, issues related not only to the use of an unusual power plant were solved.
So, the design speed of the underwater course made the previously used hull contours unacceptable. Here the sailors were helped by aircraft manufacturers: several models of the hull were tested in a wind tunnel. In addition, to improve controllability, we used double rudders modeled on the rudders of the Junkers-52 aircraft.
In 1938, the world's first experimental submarine with a hydrogen peroxide power plant with a displacement of 80 tons, designated V-80, was laid down in Kiel. Tests carried out in 1940 literally stunned - a relatively simple and light turbine with a capacity of 2000 hp. allowed the submarine to develop a speed of 28.1 knots under water! True, such an unprecedented speed had to be paid for with an insignificant cruising range: the reserves of hydrogen peroxide were enough for one and a half to two hours.
For Germany during the Second World War, submarines were a strategic weapon, since only with their help it was possible to inflict tangible damage on the economy of England. Therefore, already in 1941, the development began, and then the construction of the V-300 submarine with a steam-gas turbine operating on a "hot" cycle.
Schematic diagram of a steam-gas turbine plant operating on a "hot" cycle: 1 - propeller; 2 - reducer; 3 - turbine; 4 - rowing electric motor; 5 - separator; 6 - combustion chamber; 7 - ignition device; 8 - valve of the ignition pipeline; 9 - decomposition chamber; 10 - valve for switching on injectors; 11 - three-component switch; 12 - four-component regulator; 13 - pump for hydrogen peroxide solution; 14 - fuel pump; 15 - water pump; 16 - condensate cooler; 17 - condensate pump; 18 - mixing condenser; 19 - gas collector; 20 - carbon dioxide compressor
The V-300 boat (or U-791 - she received such a letter-digital designation) had two propulsion systems (more precisely, three): a Walter gas turbine, a diesel engine and electric motors. Such an unusual hybrid appeared as a result of the understanding that the turbine is, in fact, an afterburner engine. The high consumption of fuel components made it simply uneconomical for making long “idle” crossings or quietly “sneaking up” on enemy ships. But she was simply indispensable for quickly leaving the position of attack, changing the place of attack or other situations when it "smelled fried."
U-791 was never completed, but immediately laid four experimental combat submarines of two series - Wa-201 (Wa - Walter) and Wk-202 (Wk - Walter Krupp) of various shipbuilding firms. In terms of their power plants, they were identical, but differed in aft plumage and some elements of the cabin and hull contours. In 1943, their tests began, which were difficult, but by the end of 1944. all major technical problems were over. In particular, the U-792 (Wa-201 series) was tested for its full cruising range, when, having a supply of hydrogen peroxide of 40 tons, it went under the afterburner for almost four and a half hours and maintained a speed of 19.5 knots for four hours.
These figures so amazed the leadership of the Kriegsmarine that, without waiting for the end of the tests of experimental submarines, in January 1943 the industry was given an order for the construction of 12 ships of two series - XVIIB and XVIIG at once. With a displacement of 236/259 tons, they had a diesel-electric unit with a capacity of 210/77 hp, which made it possible to move at a speed of 9/5 knots. In case of combat necessity, two PGTUs with a total capacity of 5000 hp were switched on, which made it possible to develop an underwater speed of 26 knots.
The figure schematically, schematically, without observing the scale, shows the device of a submarine with a PGTU (one of two such installations is shown). Some designations: 5 - combustion chamber; 6 - ignition device; 11 - peroxide decomposition chamber; 16 - three-component pump; 17 - fuel pump; 18 - water pump (based on materials from
In short, the work of PSTU looks like this [10]. A triple-action pump was used to supply diesel fuel, hydrogen peroxide and pure water through a 4-position regulator for supplying the mixture to the combustion chamber; when the pump is running at 24000 rpm. the mixture supply reached the following volumes: fuel - 1, 845 cubic meters / hour, hydrogen peroxide - 9, 5 cubic meters / hour, water - 15, 85 cubic meters / hour. The dosing of these three components of the mixture was carried out using a 4-position regulator of the mixture supply in a weight ratio of 1: 9: 10, which also regulated the fourth component - seawater, which compensates for the difference in the weight of hydrogen peroxide and water in the control chambers. The control elements of the 4-position regulator were driven by a 0.5 hp electric motor. and provided the required flow rate of the mixture.
After the 4-position regulator, hydrogen peroxide entered the catalytic decomposition chamber through holes in the lid of this device; on the sieve of which there was a catalyst - ceramic cubes or tubular granules about 1 cm long, impregnated with a solution of calcium permanganate. The steam-gas was heated to a temperature of 485 degrees Celsius; 1 kg of catalyst elements passed up to 720 kg of hydrogen peroxide per hour at a pressure of 30 atmospheres.
After the decomposition chamber, it entered a high-pressure combustion chamber made of strong hardened steel. Six nozzles served as inlet channels, the side holes of which served for the passage of steam and gas, and the central one for fuel. The temperature in the upper part of the chamber reached 2000 degrees Celsius, and in the lower part of the chamber it dropped to 550-600 degrees due to the injection of pure water into the combustion chamber. The resulting gases were supplied to the turbine, after which the spent steam-gas mixture entered the condenser installed on the turbine housing. With the help of a water cooling system, the temperature of the mixture at the outlet dropped to 95 degrees Celsius, the condensate was collected in the condensate tank and, with the help of a condensate extraction pump, entered the seawater refrigerators, which used running seawater for cooling when the boat was moving in a submerged position. As a result of passing through the refrigerators, the temperature of the resulting water decreased from 95 to 35 degrees Celsius, and it returned through the pipeline as clean water for the combustion chamber. The remains of the steam-gas mixture in the form of carbon dioxide and steam under a pressure of 6 atmospheres were taken from the condensate tank by a gas separator and removed overboard. Carbon dioxide dissolved relatively quickly in seawater without leaving a noticeable trace on the surface of the water.
As you can see, even in such a popular presentation, PSTU does not look like a simple device, which required the involvement of highly qualified engineers and workers for its construction. The construction of submarines from PSTU was carried out in an atmosphere of absolute secrecy. A strictly limited circle of persons was allowed on the ships according to the lists agreed upon in the higher authorities of the Wehrmacht. At the checkpoints there were gendarmes disguised as firemen … At the same time, production capacities were increased. If in 1939 Germany produced 6,800 tons of hydrogen peroxide (in terms of 80% solution), then in 1944 - already 24,000 tons, and additional capacities were built for 90,000 tons per year.
Still not having full-fledged combat submarines from PSTU, not having experience in their combat use, Grand Admiral Doenitz broadcast:
The day will come when I will declare another submarine war on Churchill. The submarine fleet was not broken by the 1943 strikes. He is stronger than before. 1944 will be a difficult year, but a year that will bring great success.
Doenitz was echoed by state radio commentator Fritsche. He was even more outspoken, promising the nation "an all-out submarine war involving completely new submarines, against which the enemy will be helpless."
I wonder if Karl Doenitz remembered these loud promises during those 10 years that he had to while away in Spandau prison by the verdict of the Nuremberg Tribunal?
The final of these promising submarines turned out to be deplorable: for all the time, only 5 (according to other sources - 11) boats were built from Walter PSTU, of which only three were tested and were enrolled in the fleet's combat strength. Without a crew, not making a single combat exit, they were flooded after the surrender of Germany. Two of them, dumped in a shallow area in the British zone of occupation, were later raised and transported: U-1406 to the United States, and U-1407 to the UK. There, experts carefully studied these submarines, and the British even conducted field tests.
Nazi legacy in England …
Walter's boats shipped to England were not scrapped. On the contrary, the bitter experience of both past world wars at sea instilled in the British the conviction of the unconditional priority of anti-submarine forces. Among others, the Admiralty considered the issue of creating a special anti-submarine submarine. It was supposed to deploy them on the approaches to enemy bases, where they were supposed to attack enemy submarines going out to sea. But for this, the anti-submarine submarines themselves had to possess two important qualities: the ability to covertly stay under the enemy's nose for a long time and at least for a short time develop high speeds for a quick approach to the enemy and his sudden attack. And the Germans presented them with a good start: RPD and a gas turbine. The greatest attention was focused on the Perm State Technical University, as a completely autonomous system, which, moreover, provided truly fantastic underwater speeds for that time.
The German U-1407 was escorted to England by the German crew, who were warned of the death penalty in case of any sabotage. Helmut Walter was also taken there. The restored U-1407 was enlisted in the Navy under the name "Meteorite". She served until 1949, after which she was withdrawn from the fleet and dismantled for metal in 1950.
Later, in 1954-55. the British built two similar experimental submarines "Explorer" and "Excalibur" of their own design. However, the changes concerned only the external appearance and internal layout, as for the PSTU, it remained practically in its original form.
Both boats never became the progenitors of something new in the English navy. The only achievement is the 25 submerged knots obtained during the tests of the Explorer, which gave the British an excuse to trumpet the whole world about their priority for this world record. The price of this record was also a record one: constant failures, problems, fires, explosions led to the fact that they spent most of their time in docks and workshops in repair than in campaigns and trials. And this is not counting the purely financial side: one running hour of the "Explorer" cost 5,000 pounds, which at the rate of that time is equal to 12, 5 kg of gold. They were expelled from the fleet in 1962 ("Explorer") and in 1965 ("Excalibur") with the murderous characteristic of one of the British submariners: "The best thing that can be done with hydrogen peroxide is to interest potential opponents in it!"
… and in the USSR]
The Soviet Union, unlike the allies, did not get the XXVI boats, just as they did not get the technical documentation for these developments: the “allies” remained true to themselves, once again hiding a tidbit. But there was information, and quite extensive information, about these failed novelties of Hitler in the USSR. Since Russian and Soviet chemists have always been at the forefront of world chemical science, the decision to study the capabilities of such an interesting engine on a purely chemical basis was made quickly. The intelligence agencies managed to find and assemble a group of German specialists who had previously worked in this area and expressed a desire to continue them on the former enemy. In particular, such a desire was expressed by one of Helmut Walter's deputies, a certain Franz Statecki. Statecki and a group of "technical intelligence" for the export of military technology from Germany under the leadership of Admiral L. A. Korshunov, found in Germany the firm "Bruner-Kanis-Raider", which was an associate in the manufacture of Walter turbine units.
To copy a German submarine with Walter's power plant, first in Germany and then in the USSR under the leadership of A. A. Antipin's "Bureau of Antipin" was created, an organization from which, through the efforts of the chief designer of submarines (Captain I rank AA Antipin), LPMB "Rubin" and SPMB "Malakhit" were formed.
The task of the bureau was to study and reproduce the achievements of the Germans in new submarines (diesel, electric, steam and gas turbine), but the main task was to repeat the speeds of German submarines with the Walter cycle.
As a result of the work carried out, it was possible to completely restore the documentation, manufacture (partly from German, partly from newly manufactured units) and test the steam-gas turbine installation of German boats of the XXVI series.
After that, it was decided to build a Soviet submarine with a Walter engine. The theme of the development of submarines from Walter PSTU was named Project 617.
Alexander Tyklin, describing the biography of Antipin, wrote:
“… It was the first submarine in the USSR to overstep the 18-knot value of the underwater speed: within 6 hours, its underwater speed was more than 20 knots! The hull provided a doubling of the immersion depth, that is, to a depth of 200 meters. But the main advantage of the new submarine was its power plant, which was an amazing innovation at that time. And it was no coincidence that this boat was visited by academicians I. V. Kurchatov and A. P. Aleksandrov - preparing for the creation of nuclear submarines, they could not help but get acquainted with the first submarine in the USSR, which had a turbine installation. Subsequently, many design solutions were borrowed in the development of nuclear power plants …"
When designing the S-99 (this number was given to this boat), both Soviet and foreign experience in creating single engines was taken into account. The pre-sketch project was completed at the end of 1947. The boat had 6 compartments, the turbine was in a sealed and uninhabited 5th compartment, the control panel of the PSTU, a diesel generator and auxiliary mechanisms were mounted in the 4th, which also had special windows for observing the turbine. The fuel was 103 tons of hydrogen peroxide, diesel fuel - 88.5 tons and special fuel for the turbine - 13.9 tons. All components were in special bags and tanks outside the robust housing. A novelty, in contrast to German and British developments, was the use of manganese oxide MnO2 as a catalyst, not potassium (calcium) permanganate. Being a solid substance, it was easily applied to gratings and meshes, did not get lost in the process of work, took up much less space than solutions and did not decompose over time. In all other respects, PSTU was a copy of Walter's engine.
The S-99 was considered experimental from the very beginning. On it, the solution of issues related to high underwater speed was practiced: the shape of the hull, controllability, stability of movement. The data accumulated during its operation made it possible to rationally design the first generation nuclear-powered ships.
In 1956 - 1958, project 643 large boats were designed with a surface displacement of 1865 tons and already with two PGTUs, which were supposed to provide the boat with an underwater speed of 22 knots. However, in connection with the creation of a draft design of the first Soviet submarines with nuclear power plants, the project was closed. But the studies of the PSTU S-99 boats did not stop, but were transferred to the mainstream of considering the possibility of using the Walter engine in the giant T-15 torpedo with an atomic charge, proposed by Sakharov for the destruction of US naval bases and ports. The T-15 was supposed to have a length of 24 meters, an underwater range of up to 40-50 miles, and carry a thermonuclear warhead capable of causing an artificial tsunami to destroy coastal cities in the United States. Fortunately, this project was also abandoned.
The danger of hydrogen peroxide did not fail to affect the Soviet Navy. On May 17, 1959, an accident occurred on it - an explosion in the engine room. The boat miraculously did not die, but its restoration was considered inappropriate. The boat was handed over for scrap.
In the future, PSTU did not become widespread in submarine shipbuilding, either in the USSR or abroad. The advances in nuclear power have made it possible to more successfully solve the problem of powerful submarine engines that do not require oxygen.
