Tuesday 30 April 2019


Early Chemical Science

 1660-The royal Society was established in London for improvement of natural  knowledge.

1661-Robert Boyle defined element, acid and base concept.

1666-French Academy of Science started from Paris.the ore processing was studied  here.

 

Birth of chemistry

Demons in the ore: 1742-1751

 Miners in the Harz mountains have often been frustrated by a substance which appears to be copper ore but which, when heated, yields none of the expected metal. Even worse, it emits noxious fumes. In about 1735 Georg Brandt is able to show in his Swedish laboratory that the  previously unknown substance was Cobalt. It has been identified, and Brandt gives its name to the new substance - as cobalt

 A similar demon is blamed by miners in Saxony for another ore which yields a brittle substance instead of copper. The impurity in ore of this type is analyzed in Sweden in 1751 by Axel Cronstedt. He identifies its components as arsenic and a previously unknown hard white metal, quite distinct from copper. He honours the new substance and calls it nickel.

1754-Joseph Black heated lime-stone and produced his fixed air.

Joseph Black and fixed air: 1754-1756

Black has observed that if he heats chalk (calcium carbonate), he gets quicklime (calcium oxide) and a gas, the presence of which he can identify by its weight. Unwilling as yet to speculate on its identity, he calls it fixed air - because it exists in solid form until released.

The classic experiments of Joseph Black on magnesia alba (basic magnesium carbonate) in the 1750s; by extensive and careful use of the chemical balance, showed that an air with specific properties could combine with solid substances like quicklime and could be recovered from them.

1766-Henry Cevendish discovered inflamable gas, the hydrogen.

1773-Sheele isolated oxygen using silver carbonate.

1774-Priestly discovered Oxygen by heating HgO.

 

Priestley and oxygen: 1774

 In August 1774 Priestley directs his lens at some mercury oxide. He discovers that it gives off a colourless gas in which a candle burns with an unusually brilliant light.

 In October 1774, visiting Paris with his noble patron, he describes his discovery to a gathering of French scientists. Among them is Lavoisier, who develops Priestley's experiments in his own laboratory and realizes that he has the evidence to disprove the phlogiston theory.

1775-Micro-Organisms observed using Microscope.

 

Lavoisier: 1777-1794

 Although Antoine Laurent Lavoisier has no single glamorous discovery to add lustre to his name (such as identifying oxygen), he is regarded as the father of modern chemistry. The reason is that during the last two decades of the 18th century he interprets the findings of his colleagues with more scientific clarity than they have mustered, and creates the rational framework within which chemistry can develop.

 Lavoisier is most noted for his discovery of the role oxygen plays in combustion. He recognized and named oxygen (1778)

and hydrogen (1783) and opposed the phlogiston theory. Lavoisier helped construct the metric system, wrote the first

extensive list of elements, and helped to reform chemical nomenclature.

1778-Lavoisier named the elements, hydrogen Oxygen and Nitrogen. He announced that air is composed of two gases, oxygen and nitrogen.

He explained the combustion.He concluded that during calcination,metals absorb oxygen and incrase their weight.

He was able to show that Priestley's gas is involved in chemical reactions in the processes of burning and rusting, and that it is transformed in both burning and breathing into the 'fixed air' discovered by Joseph Black. His researches with phosphorus and sulphur cause him to believe that the new gas is invariably a component of acids. He therefore gives it in 1777 the name oxygen ( 'acid maker'). On a similar principle Lavoisier coins the word hydrogen ('water maker') for the very light gas isolated by Cavendish.

 With these two names chemistry takes a clear and decisive step into the modern era. It is an advance which Lavoisier soon consolidates.

1781-Cavendish synthesized water by burning Hydrogen in Oxygen.

Cavendish mixes hydrogen and oxygen, in the proportion 2:1, in a glass globe through which he passes an electric spark. The resulting chemical reaction leaves him with water, which stands revealed as a compound (H2O).

1782-Lavoisier established the law of conservation of mass.

He said,”In a chemical  change nothing is lost and nothig is created and everything is transformed.”  He was considered the father of modern chemistry.

1789-For the first time,He Made a list of 23 known elements. He wrote the elementary treatise of chemistry. This text clarified the concept of element as a substance that could not be broken down by any known method of chemical analysis.

 1793-Alessandro Volta, an Italian Physicist and chemist, discovered the Principle of primary battery.

In 1800, Volta invented the voltaic pile, an early electric battery, which produced a steady electric current.Volta had determined that the most effective pair  of dissimilar metals to produce electricity was zinc and copper. Volta's method of stacking round plates of copper and zinc separated by disks of cardboard moistened

with salt solution was termed a voltaic pile. 

 

Volta's invention built on Luigi Galvani's 1780s discovery of how a circuit of two metals and a frog's leg can cause the frog's leg to respond. Volta demonstrated in 1794 that when two metals and brine-soaked cloth or cardboard are arranged in a circuit they produce an electric current. In 1800, Volta stacked several pairs of alternating copper (or silver) and zinc discs (electrodes) separated by cloth or cardboard soaked in brine (electrolyte) to increase the electrolyte conductivity. When the top and bottom contacts were connected by a wire, an electric current flowed through the voltaic pile and the connecting wire.

Thus, Volta is considered to be the founder of the discipline of electrochemistry. A Galvanic cell (or voltaic cell) is an electrochemical cell that derives electrical energy from spontaneous redox reaction taking place within the cell. It generally consists of two different metals connected by a salt bridge, or individual half-cells separated by a porous membrane.

 A voltaic cell is an electro-chemical cell that uses a chemical reaction to produce electrical energy. The important parts of a voltaic cell: The anode is an electrode where oxidation

occurs. The cathode is an electrode where reduction occurs.

 In redox reactions, electrons are transferred from one species to another. If the reaction is spontaneous, energy is released, which can then be used to do useful work. To harness this energy, the reaction must be split into two separate half reactions: the oxidation and reduction reactions. The reactants are put into two different containers and a wire is used to drive the electrons  from one side to the other. In doing so, a Voltaic/ Galvanic Cell is created.

1794-Lavoisier was executed in French revolution.

1803-The law of multiple proportion by Dalton.The law of multiple proportions is one of the basic laws of stoichiometry used to

establish the atomic theory.1803-Dalton's atomic theory.

In 1803, an English meteorologist began to speculate on the phenomenon of water vapor. John Dalton (1766-1844) was aware that water vapor is part of the atmosphere, but experiments showed that water vapor would not form in certain other gases. He speculated that this had something to do with the number of particles present in those gases. Perhaps there was no room in those gases for particles of water vapor to penetrate. There were either more particles in the “heavier” gases or those particles were larger. Using his own data and the Law of Definite Proportions, he determined the relative masses of particles for six of the known elements: hydrogen (the lightest and assigned a mass of 1), oxygen, nitrogen, carbon, sulfur and phosphorous. Dalton explained his findings by stating the principles of the first atomic theory of matter.

 

Elements are composed of extremely small particles called atoms.

Atoms of the same element are identical in size, mass and other properties. Atoms of different elements have different properties.

Atoms cannot be created, subdivided or destroyed.

Atoms of different elements combine in simple whole number ratios to form chemical compounds.

In chemical reactions atoms are combined, separated or rearranged to form new compounds

 

Dalton  proposed a modern atomic theory in 1803 which stated that all matter was composed of small indivisible particles termed atoms, atoms of a given element possess  unique characteristics and weight, and three types of atoms exist: simple (elements), compound (simple molecules), and complex (complex molecules).

1804-French chemist Joseph Proust proposed the law of definite proportions, which states that elements always combine in small, whole number ratios to form compounds, based on several experiments conducted between 1797 and 1804.

 In chemistry, the law of definite proportion, sometimes called Proust's law or the law of definite composition, or law of constant composition states that a given chemical compound always contains its component elements in fixed ratio (by mass) and does not depend on its source and method of preparation.

 1808- Law of combining volumes by Gay-Lussac. Gay-Lussac announced what was probably his single greatest achievement: from his own

and others' experiments he deduced that gases at constant temperature and pressure; 

combine in simple numerical proportions by volume, and the resulting product or  products—if gases—also bear a simple proportion by volume to the volumes of the reactants. In other words, gases under equal conditions of temperature and pressure react with one another in volume ratios of small whole numbers. This conclusion subsequently became known as "Gay-Lussac's law" or the "Law of Combining Volumes".

 1811-Avogadro's law which states that equal volumes of different gases at the same temperature and pressure must contain the same number of particles. 

Amedeo Avogadro (1776-1856), hypothesized that equal volumes of gases at the same temperature and pressure contain equal numbers of molecules, from which it followed that relative molecular weights of any two gases are the same as the ratio of the densities of the two gases under the same conditions of temperature and pressure.

 

1812-using Volta's battery, Humphry Davy isolated new elements like,potassium,Sodium,Magnesium, Calcium,Strontium, Barium,and Boron. He went on to electrolyse molten salts and discovered several new metals, including sodium and potassium, highly reactive elements known as the alkali metals. During the first half of 1808, Davy conducted a series of further electrolysis experiments on  alkaline earths including lime, magnesia, strontites and barytes.

1814-On 30 June 1808 Davy reported to the Royal Society that he had successfully isolated four new metals which he named barium, calcium, strontium and magnesium. The observations gathered from these experiments also led to Davy isolating boron in 1809

1817-Jacob Berzelius was a Swedish Chemist.

Berzelius, [disciple of Dalton], named the elements and used symbols to represent elements in a chemical formula.He also calculated atomic weights of diferent elements.

Berzelius began his career as a physician but his researches in physical chemistry were of lasting significance in the development of the subject. He is especially noted for his determination of atomic weights; his experiments led to a more complete depiction of the principles of stoichiometry, or the field of chemical combining proportions. In 1803 Berzelius demonstrated the power of an electrochemical cell to decompose chemicals into pairs of electrically opposite constituents.

Berzelius's work with atomic weights and his theory of electrochemical dualism led to his development of a modern system of chemical formula notation that could portray the composition of any compound both qualitatively (by showing its electrochemically opposing ingredients) and quantitatively (by showing the proportions in which the ingredients were united). His system abbreviated the Latin names of the elements with one or two letters and applied subscripts to designate the number of atoms of each element present in both the acidic and basic ingredients

1834-Michael Faraday

Faraday discovered that when electricity is passed through ionic solutions, the amount of

chemical change produced was proportional to the quantity of electricity passed through it.

Electrochemistry, branch of chemistry concerned with the relation between electricity

and chemical change. Many spontaneously occurring chemical reactions liberate electrical energy, and some of these reactions are used in batteries and fuel cells to produce electric power. Conversely, electric current can be utilized to bring about many chemical reactions that do not occur spontaneously. In the process called electrolysis, electrical energy is converted directly into chemical energy, which is stored in the products of the reaction. This process is applied in refining metals, in electroplating, and in producing hydrogen and oxygen from water.

 

An electrolytic cell is an electrochemical cell that drives a non-spontaneous redox reaction through the application of electrical energy. They are often used to decompose chemical compounds, in a process called electrolysis—the Greek word lysis means to break up.

 

An electrolytic cell has three component parts: an electrolyte and two electrodes (a cathode and an anode). The electrolyte is usually a solution of water or other solvents in which ions are dissolved.

 

Faraday's law stating that the amount of any substance deposited or liberated during electrolysis is proportional to the quantity of electric charge passed and to the equivalent weight of the substance.” 

Faraday's First Law of Electrolysis. The mass of the substance (m) deposited or liberated at any electrode is directly proportional to the quantity of electricity or charge (Q) passed.

Faraday further observed that 1 Faraday (96,485C) of charge liberates 1 gram equivalent of the substance at the electrodes.

Faraday’s First Law of Electrolysis states that the chemical deposition due to the flow of current through an electrolyte is directly proportional to the quantity of  electricity (coulombs) passed through it.

 

Faraday’s First Law of Electrolysis states that the chemical deposition due to the flow of current through an electrolyte is directly proportional to the quantity of electricity (coulombs) passed through it.
i.e. mass of chemical deposition:

Where, Z is a constant of proportionality and is known as electro-chemical equivalent of the substance.

 Faraday’s second law of electrolysis states that, when the same quantity of electricity is passed through several electrolytes, the mass of the substances deposited are proportional to their respective chemical equivalent or equivalent weight.

Chemical Equivalent or Equivalent Weight

The chemical equivalent or equivalent weight of a substance can be determined by Faraday’s laws of electrolysis, and it is defined as the weight of that subtenancy which will combine with or displace the unit weight of hydrogen.
The chemical equivalent of hydrogen is, thus, unity. Since valency of a substance is equal to the number of hydrogen atoms, which it can replace or with which it can combine, the chemical equivalent of a substance, therefore may be defined as the ratio of its atomic weight to its valency.

 1841-chemical society was founded in England.

in1841-The Chemical Society was formed  (then named the Chemical Society of London) by 77 scientists as a result of increased interest in scientific matters. Chemist Robert Warington was the driving force behind its creation. Chemical Society of London is a "fruitful amalgamation of the technological and academic chemist".

1845-the Royal cillage of chemistry was founded.

1851-The Royal School of Mines was established in london

 

1852-concept of valency by Edward Frankland.

Research beginning about 1850 led him to the idea that an atom of an element can combine only with a certain limited number of atoms of other elements. He thus established a theory of valency (1852), which became the basis of modern structural chemistry.

In 1866 he published an influential textbook, Lecture Notes, in which he adopted Crum Brown’s graphic (structural) formulas and argued (against Kekulé) that elements could exhibit more than one valence below a fixed upper maximum. 

 From 1863 to 1870 he and Baldwin Duppa exploited zinc ethyl and other organic reagents, including ethyl acetate, in the synthesis of ethers, dicarboxylic acids, unsaturated monocarboxylic acids, and hydroxy acids. This meticulous work revealed clearly the structure and relationship of these compounds, and of course its methodology had great bearing on the growth of the chemical industry.

Reagents are "substances or compounds that are added to a system in order to bring about a chemical reaction or are added to see if a reaction occurs. 

 1860-world's first chemical conference held in Europe [Karlsruhe Congress] by Kekule.140 delegates prticipated in it. The young syberian Mendeleyev was also present in the meet.

 An important long-term result of the Karlsruhe Congress was the adoption of the now-familiar atomic weights.

Prior to the Karlsruhe meeting, and going back to Dalton'swork

in 1803, several systems of atomic weights were in use.In

one case, a value of 1 was adopted as the weight of hydrogen (the

base unit), with 6 for carbon and 8 for oxygen. As long as there were

uncertainties over atomic weights then the compositions of many

compounds remained in doubt. Following the Karlsruhe meeting, values

of about 1 for hydrogen, 12 for carbon, 16 for oxygen, and so forth

were adopted. This was based on a recognition that certain elements, such as hydrogen, nitrogen, and oxygen, were composed of diatomic

molecules and not individual atoms.

 

Rocke says. “If you believed Avogadro’s theory, then you could get the correct molecular formula for molecules, as well as the correct atomic weights, which was the groundwork required to construct the periodic table,“ he says.

 When the 1860 conference began, chemistry was in a total state of disarray.

Participants broke into groups to discuss contentious issues, such as stoichiometry or representation of molecular formulas, and then they would return to the plenary hall to share their deliberations, Podlech says. However, sometimes a group’s consensus was undermined by the presenter’s personal opinions

 In fact, the conference was mostly dominated by voices from the old guard—so much so that the organizers began to fear their efforts were in vain and that the conference was going to be a complete failure. But just before the meeting’s close, a relatively unknown Italian chemist named Stanislao Cannizzaro gave a long, impassioned, and eloquent lecture that argued for Avogadro’s perspective on molecules. After Cannizzaro’s lecture, one of his friends handed out a paper that effectively reiterated his speech and that several important delegates read on their trips home.

It was as though the scales fell from my eyes; doubt vanished, and it was replaced by a feeling of peaceful certainty,“ wrote Meyer, who would later go on to construct a correct periodic table around the same time as Mendeleev put his together. Mendeleev wrote that the meeting “produced such a remarkable effect on the history of our science that I consider it a duty ... to describe all the sessions ... and the results.“

 But Cannizzaro’s plea needed some time to sink in, and it took about a decade before scientists hashed out the correct molecular weights that enabled the periodic table to emerge. “On that last day in Karlsruhe, there were no cheers, no sudden enlightenment, no ovation,” Rocke notes. “The assembled chemists simply quietly filed out of the hall and went home.

 The Karlsruhe meeting was the first international meeting of chemists and that it led to the eventual founding of the International Union of Pure and Applied Chemistry (IUPAC).

Later, German chemist Lothar Meyer, and the Russian chemist Dmitri Mendeleev, who had  both been in attendance at Karlsruhe, constructed element arrangements using the Cannizzaro numbers - on tables: with the elements arranged in rows and columns - for schoolbooks. 

 1869-Mendeleyev constructed the periodic table of elements, based on inceasing  atomic weights of elements.

1898-discovery of Nobel gases by Willium Ramsay.

 


Sunday 21 April 2019



Uranium ore processing

Leaching:

Roasted uranium ores are leached of their uranium values by both acidic and alkaline aqueous solutions. For the successful operation of all leaching systems, uranium must either be initially present in the more stable hexavalent state or be oxidized to that state in the leaching process.
Acid leaching is commonly performed by agitating an ore-leach mixture for 4 to as long as 48 hours at ambient temperature. Except in special circumstances, sulfuric acid is the leachant used; it is supplied in amounts sufficient to obtain a final leach liquor at about pH 1.5. Sulfuric acid leaching circuits commonly employ either manganese dioxide or chlorate ion to oxidize the tetravalent uranium ion (U4+) to the hexavalent uranyl ion (UO22+). Typically, about 5 kilograms (11 pounds) of manganese dioxide or 1.5 kilograms of sodium chlorate per ton suffice to oxidize tetravalent uranium. In any case, the oxidized uranium reacts with the sulfuric acid to form a uranyl sulfate complex anion, [UO2(SO4)3]4-.
Uranium ores that contain significant amounts of basic minerals such as calcite or dolomite are leached with 0.5 to 1 molar sodium carbonate solutions. Although a variety of reagents has been studied and tested, oxygen is the uranium oxidant of choice. Typically, candidate ores are leached in air at atmospheric pressure and at 75° to 80° C (167° to 175° F) for periods that vary with the particular ore. The alkaline leachant reacts with uranium to form a readily soluble uranyl carbonate complex ion, [UO2(CO3)3]4-.
Prior to further processing, solutions resulting from either acidic or carbonate leaching must be clarified. Large-scale separation of clays and other ore slimes is accomplished through the use of effective flocculants, including polyacrylamides, guar gum, and animal glue.

Treatment of uranium leachates

The complex ions [UO2(CO3)3]4- and [UO2(SO4)3]4- can be sorbed from their respective leach solutions by ion-exchange resins. These special resins—characterized by their sorption and elution kinetics, particle size, stability, and hydraulic properties—can be used in a variety of processing equipment—e.g., fixed-bed, moving-bed, basket resin-in-pulp, and continuous resin-in-pulp. Conventionally, sodium and ammonium chloride or nitrate solutions are then used to elute the sorbed uranium from the exchange resins.
Uranium can also be removed from acidic ore leach-liquors through solvent extraction. In industrial methods, alkyl phosphoric acids—e.g., di(2-ethylhexyl) phosphoric acid—and secondary and tertiary alkyl amines are the usual solvents. As a general rule, solvent extraction is preferred over ion-exchange methods for acidic leachates containing more than one gram of uranium per litre. Solvent extraction is not useful for recovery of uranium from carbonate leach liquors, however.

Precipitation of yellow cake:

Prior to final purification, uranium present in acidic solutions produced by the ion-exchange or solvent-extraction processes described above, as well as uranium dissolved in carbonate ore leach solutions, is typically precipitated as a polyuranate. From acidic solutions, uranium is precipitated by addition of neutralizers such as sodium hydroxide, magnesia, or (most commonly) aqueous ammonia. Uranium is usually precipitated as ammonium diuranate, (NH4)2U2O7. From alkaline solutions, uranium is most often precipitated by addition of sodium hydroxide, producing an insoluble sodium diuranate, Na2U2O7. It can also be precipitated by acidification (to remove carbon dioxide) and then neutralization (to remove the uranium) or by reduction to less soluble tetravalent uranium. In all cases, the final uranium precipitate, commonly referred to as yellow cake, is dried. In some cases—e.g., with ammonium diuranate—the yellow cake is ignited, driving off the ammonia and oxidizing the uranium to produce uranium trioxide (UO3) or the more complex triuranium octoxide (U3O8). In all cases, the final product is shipped to a central uranium-purification facility.


Abundance:

Uranium is more plentiful than antimony, tin, cadmium, mercury, or silver, and it is about as abundant as arsenic or molybdenum.Uranium is found in hundreds of minerals, including uraninite (the most common uranium ore), carnotite, autunite, uranophane, torbernite, and coffinite.

The discovery of the element is credited to the German chemist Martin Heinrich Klaproth. While he was working in his experimental laboratory in Berlin in 1789, Klaproth was able to precipitate a yellow compound (likely sodium diuranate) by dissolving pitchblende in nitric acid and neutralizing the solution with sodium hydroxide.[27] Klaproth assumed the yellow substance was the oxide of a yet-undiscovered element and heated it with charcoal to obtain a black powder, which he thought was the newly discovered metal itself (in fact, that powder was an oxide of uranium).He named the newly discovered element after the planet Uranus.

Worldwide production of U3O8 (yellowcake) in 2013 amounted to 70,015 tonnes, of which 22,451 t (32%) was mined in Kazakhstan. Other important uranium mining countries are Canada (9,331 t), Australia (6,350 t), Niger (4,518 t), Namibia(4,323 t) and Russia (3,135 t).

Mining:
Uranium ore is mined in several ways: by open pit, underground, in-situ leaching, and borehole mining (see uranium mining).Low-grade uranium ore mined typically contains 0.01 to 0.25% uranium oxides. Extensive measures must be employed to extract the metal from its ore.High-grade ores found in Athabasca Basin deposits in Saskatchewan, Canada can contain up to 23% uranium oxides on average.Uranium ore is crushed and rendered into a fine powder and then leached with either an acid or alkali. The leachate is subjected to one of several sequences of precipitation, solvent extraction, and ion exchange. The resulting mixture, called yellowcake, contains at least 75% uranium oxides U3O8. Yellowcake is then calcined to remove impurities from the milling process before refining and conversion.

The most common forms of uranium oxide are triuranium octoxide (U3O8) and UO2.Both oxide forms are solids that have low solubility in water and are relatively stable over a wide range of environmental conditions. Triuranium octoxide is (depending on conditions) the most stable compound of uranium and is the form most commonly found in nature. Uranium dioxide is the form in which uranium is most commonly used as a nuclear reactor fuel.At ambient temperatures, UO2 will gradually convert to U3O8. Because of their stability, uranium oxides are generally considered the preferred chemical form for storage or disposal.

Enrichment:

In nature, uranium is found as uranium-238 (99.2742%) and uranium-235 (0.7204%). Isotope separation concentrates (enriches) the fissionable uranium-235 for nuclear weapons and most nuclear power plants, except for gas cooled reactors and pressurised heavy water reactors. Most neutrons released by a fissioning atom of uranium-235 must impact other uranium-235 atoms to sustain the nuclear chain reaction. The concentration and amount of uranium-235 needed to achieve this is called a 'critical mass'.
To be considered 'enriched', the uranium-235 fraction should be between 3% and 5%.This process produces huge quantities of uranium that is depleted of uranium-235 and with a correspondingly increased fraction of uranium-238, called depleted uranium or 'DU'. To be considered 'depleted', the uranium-235 isotope concentration should be no more than 0.3%.
At room temperatures, UF6 has a high vapor pressure, making it useful in the gaseous diffusion process to separate the rare uranium-235 from the common uranium-238 isotope. This compound can be prepared from uranium dioxide and uranium hydride by the following process:
UO2 + 4 HF → UF4 + 2 H2O (500 °C, endothermic)
UF4 + F2 → UF6 (350 °C, endothermic)
The resulting UF6, a white solid, is highly reactive (by fluorination), easily sublimes (emitting a vapor that behaves as a nearly ideal gas), and is the most volatile compound of uranium known to exist.