Cadmium is then determined by galvanic deposition, after addition of potassium hydroxide and potassium cyanide, or by evaporation of the solution

with sulfuric acid to obtain weighing cadmium sulfate. Zinc volumetrically determined by the method of ferrocyanide or gravimetrically as zinc oxide.

For the determination of impurities that may be present the following methods are recommended:

Is determined as tin oxide, obtained by treating 5 g of alloy, in a solution of 25% nitric acid.
Lead is determined as lead sulfate by the method 'lead acid'.

El hierro se determina volumtricamente con permanganato de potasio normalizado despus de la reduccin, en el reductor de Jones. The precipitating nickel dimethylglyoxime is determined.

2. Recovery, separation and refining of silver

2.1 Recovery. The silver can be in the form of salts or compounds of the metal or solutions, which may be acidic or

alkaline.When silver is dissolved in the form of chloride or sulfate, the most economical for its recovery, chemical, or, alternatively, electrochemistry. 2.1.1 From silver cyanide baths. Often spoken of disposing silver cyanide baths that are dangerous to handle. This advice is suitable mostly for small amounts. If the decision is made to store must be in good condition because cyanide can des ignite fumes harmful to health.Remember that, overall mind, silver residues often have little value and usually not worth retrieve, but can be mixed with sweepings, sinks, and other low-grade materials. Sometimes, to precipitate the silver, we propose the use of hydrochloric acid, but its incorporation into a cyanide solution is extremely dangerous due to the formation and release of very poisonous hydrogen cyanide. When you choose this method, the work must be done, necessarily, under the extractor
hood and taking every precaution.

2. 1. 1. 1 with zinc recovery. If zinc is recovered, there will be no dangerous reaction. To the solution to recover silver is added in an amount of zinc

powder, equivalent to about four times the amount of silver that is supposed to contain. Stir from time to time and, after a few days, to see if the zinc has displaced all the silver, removes a small sample solution and takes a test tube. A solution of the test tube, were added a few drops of concentrated solution of liver of
2

sulfur (potassium sulfide, K

S).

If the sample does not change and remains transparent appearance or acquires a slight whitish haze, is that there is no more money, whereas if, on the contrary, shows a color that can range from brown to black, is that the still segregates solution of silver sulfide, and in this case more zinc must be added in powder form. When it is found that there no longer remains dissolved silver, the solution is decanted and the Then the residue is etched with dilute sulfuric acid to remove zinc, and then washed again

residue washed with water. with hot water to remove the last traces of zinc sulfate and sulfuric acid. The solution was decanted and the bottom of the vessel, a residue with a high content of silver that was subsequently dissolved in dilute nitric acid (1:1).

Adding hydrochloric acid, or table salt, silver is precipitated in the form of 'curd' white silver The obtained silver chloride can be used for the preparation of novel silver baths or reduced to

chloride. metallic silver.

2.1.1.2 sodium hydroxide and aluminum. A old silver baths, is added about 2 grams of sodium hydroxide (caustic soda, NaOH), for every ounce of silver in the solution. However, if the silver content is less than 7 g / I, the amount of sodium hydroxide to be added should be at least 15 g / I. Is stirred with a wooden stick to dissolve sodium hydroxide and then added about 5 grams of aluminum per gram of silver recovered. The abundant foaming indicate that silver already has been completely precipitated, in the form of thick flakes. The treated solution was decanted to reduce its caustic action ca and, with the help of a wooden paddle, collect the silver clay, washed by filtering on a cloth, with plenty of hot water and dried in the same cloth.If all opera tions have been carried out correctly, the product obtained shall silver metal can be melted directly, as if it were filings. Caustic soda Beware! The hands should be protected with rubber gloves and eyes with proper eyewear. 2.1.1.3 Recovery electrolysis. Another good chance to recover dissolved silver in electroplating baths, is electrolysis, under the following conditions: Cubas Plastic, glass, ceramic, enamel, iron, etc.. ambient temperature (20 to 30 C). Anodes stainless steel or graphite. stainless steel cathodes, in sheets on which silver deposits. Voltage: 1 to 2 volts. Time until all the money has been separated, it is known because, although the ammeter continue to draw current step can be seen that no silver is deposited only shows gas or mud, which, once melted, provide no metallic silver. 2.1.2 photographic solutions. 2.1.2.1 Using hydrochloric acid and zinc. And the solution is stirred for acidularla, is commercial hydrochloric acid is added until, by introducing a strip of litmus paper therein, it clearly turns red.

 Then add zinc powder or filings. The hydrochloric acid dissolves the zinc drgeno hi detachment.A part of hydrogen pe follows flutes forming bubbles, while other "down" the silver compound. Beware of sparks or fire! The gas is explosive. This produces fine silver, gray clay-like, which is deposited in the bottom of the container. While depositing silver follow, are repeated additions of zinc and acid.

Once it has been reduced all the silver, the solution is filtered, the sediment is bo iled in hydrochloric acid to completely remove possible traces of zinc, washed several times with hot water, dried and melted. 2.1.2.2 sodium sulfide. Photographers separate the silver from fixing baths, as silver sulfide, black, the same product that causes the alteration of silver in contact with air. Preparing a concentrated solution of sodium sulfide to be added to the solution recovered. Immediately silver sulfide is formed. The operation continues until, by adding more sodium sulfide solution, there is no more silver sulfide. 2.2 Separation. Once the button or silver bullion, usually alloyed with other metals, it is necessary to remove impurities that may contain, in order to get a degree as high as possible. Depending on the circumstances, this operation is performed by cupellation, via electro - lytic or by chemical means.The choice of one procedure or another depending on the amount of silver to refine, continuity of production and the state of the material. 2.2.1 Separation of filings or shavings mixed silver and copper. If copper and silver are mixed, without being alloyed, for example, in the form of shavings or chips of each of the two metals can dissolve only the silver, attacking with the mixture of acids that are cited below: Concentrated sulfuric acid at 66 B 900 g in weight or 500 cc in volume. Concentrated nitric acid at 42 B 100 g in weight or 70 cc in volume. This solution works well at room temperature, but is more vigorous attack if heated. As used container glass, stoneware or porcelain.If not directly heatable, becomes water bath.

This method is good, for example, when to dissolve the silver plated objects, although it should be noted that in some cases it may also attack the base metal, so it is advisable to perform some preliminary experiments. 2.2.2 Separation of dissolving silver in nitric acid. Chemically pure silver can be prepared by dissolving silver trade or Coin, chemically pure nitric acid lowered to 60%. Nitric acid, chemically pure 6 parts 4 parts distilled water The operation can be accelerated by heating them in a bath of water at 40/60 C.

Silver Once dissolved, the solution is left at rest, any residual gold is siphoned, is added an equal volume of distilled water and filtered into another container. 2.2.2.1 Precipitation of silver, in the form of silver chloride, common salt. The dissolved silver in nitric acid, as well as any that may contain metals such as copper, zinc, nickel, etc. were converted into nitrates. If an alloy is formed only with silver and copper, the solution will consist of two metal nitrate (silver nitrate and copper nitrate). To separate the silver nitrate nitrates others, must be transformed into silver chloride, insoluble in nitric solutions. There are several ways to precipitate silver chloride, in this case we refer to the most common and inexpensive, common salt. For this, using a container of any kind (size depends on the size of the amount of silver that has to precipitate) is filled with water. Then it is added salt (sodium chloride, NaCl) and goes stirring until it reaches a point where they no longer can dissolve more salt. When no more salt is dissolved, the solution is said to be saturated. The hot solutions are prepared by dissolving more power than those made in cold, more quantity of salt dissolved or product in question, go However, when cooled back to release the dissolved amount of more differences temperature therefore should not be surprised if we prepare a saturated solution in hot tea, the store has left us, in any container and, when we need it, we note that at the bottom of the container appears a certain amount of undissolved salt.The solution remains valid, the only difference is that, with having less amount of dissolved salt that when hot, we will need a greater volume of solution to precipitate the same amount of silver chloride. The saturated solution of common salt to be added containing silver nitrate, with stirring.They shall forthwith, silver chloride is formed, with a white appearance similar to cream. Stirring is continued for some time, which depends on the amount of solution.If vigorous stirring, silver chloride coagulates and settles more quickly.

 Is allowed to stand, so that the chloride is deposited on the bottom of the container.If the solution does not contain copper, the upper liquid is clear and colorless, however, if it contains or is bluish green. Add a small amount of saline solution to clear liquid, to see if all the money is called precision chloride form.This operation is repeated as many times as necessary see until, finally, to add common salt solution, no silver chloride precipitates. Is allowed to stand and the acid is decanted.

When working with large amounts, before discarding the acid, filter it is advisable because frequently contains small amounts of silver gold tie them with a look-wave, which in this case remain in the filter. Then, the silver chloride is washed several times with hot running water.

After each washing operation, a small sample is taken and water is introduced into a test tube or in a small beaker is added a few drops of ammonia.If the water contains traces of copper nitrate, will turn blue. In this case, the re-washed chloride, stirred, allowed to settle, decant the water and the test is repeated. This operation is repeated as many times as necessary, until adding ammonia acquiring any blue hue. When no copper traces warn, will check the water test with litmus paper to determine its acidity.If the paper turns red, the water is still contains nitric acid, so it is advisable to continue the washing until a neutral pH value. For a sample of the color to show the strip of litmus paper to give a neutral pH, may be wet with distilled or tap water. After reaching a satisfactory result, the solution is allowed to stand for a few days for the chloride perch on the bottom of the container, preferably in the dark.Trans - elapsed period of sedimentation, the clear liquid is decanted and discarded.Silver chloride is stored in a stoneware container and lid to keep it clean, to collect an amount sufficient to justify dad later use, treatment or delivery to the refinery.Keep wet. 2.2.2.2 ammonium chloride. Some goldsmiths silversmiths silver chloride precipitated by adding ammonium chloride to the acidic solution. In this case the procedure is

the same manner as indicated for the salt.The results are exactly the same and table salt is cheaper. 2.2.2.3 Using hydrochloric acid. A hot nitrate solution, hydrochloric acid is added, stirring and without expelling excess nitric acid, until no precipitate silver chloride.If this operation is used in an excess of hydrochloric acid in hot and operated, lead, bismuth, tin, etc. was dissolved in the form of chlorides Let stand the silver chloride precipitate and decant the remaining liquid containing dissolved Silver chloride is washed several times with hot water by decantation desechndola.

chlorides.

Next, a small amount of aqua regia to digest substances still contain contaminants, boiled a few times with hydrochloric acid and, finally you with distilled water until neutral

reaction.This ar gntico chloride can be reduced to metallic silver by any of the processes outlined below.

2.2.2.3.1 Metallization of silver chloride with sulfuric acid and soft iron or zinc. If silver chloride is fused directly, without any preparation, it loses much of it will remain nonmetallized metal from the slag. For this reason, it is advisable to previously reduce silver chloride to silver metal. For this, one possibility is to prepare rar sulfuric acid solution 20%: 4 parts tap water Sulfuric acid 1 part Is passed to a evaporadera chloride or other wide-mouth container is added the same volume of water acidulated Then, add pieces of soft iron, which can be pins or any other disposable iron, oxide free.The white chloride, when in contact with iron, immediately begins to darken. * Is left to react for several days, stirring occasionally do when a glass rod in order that the iron in contact with most of the chloride.Rarse Procu must not interrupt the reaction, which can be observed through the gas evolution takes place by removing the dough. When there is no reaction appreciated, and it is presumed that the chloride is not completely reduced, must be added, as appropriate, further more metal or sulfuric acid. The reaction can be accelerated: increasing the concentration of acid, heating the solution and stirring continuously.

Upon completion of the reduction of silver chloride to metallic silver, white color chloride initially acquires a leaden uniform tone. At this point, to ensure the complete reduction to metallic silver chloride, more acid is added and stirring is continued for some time. Then the iron is separated, washed silver precipitated with dilute hydrochloric acid and then with distilled water to remove the soluble salts formed in the foregoing reactions (sulfate and zinc chloride or iron). A portion of the decanted liquid is boiled with a few drops of nitric acid to oxidize any trace of iron present and then checking the iron ammonium thiocyanate, NH4C N S. If it contains iron, appear red coloration. The silver powder, dry, low melting a layer of charcoal in a graphite crucible or clay, with borax, together with an equal volume of sodium carbonate in order to reduce the bit silver chloride, optionally , do not been reduced in the preceding operations.Then poured into an ingot mold to obtain an ingot, or molten metal is poured into the water and thus the fine silver is obtained, under the form of granules. The silver thus obtained is analyzed to ensure that it contains gold and has reached the required degree. If all operations have been made with due care, the money collected will provide a degree of about 998-999 milliseconds. It slightly improves the purity merging. The reduced silver with zinc or aluminum is not as pure as that achieved with iron, due to the difficulty of separating the last traces of contaminating metal salts.

2.2.2.3.2 Using hydrochloric acid and iron, zinc or aluminum. Another possibility is to use hydrochloric acid instead of sulfuric acid with iron, zinc or aluminum. The cycle of operations is the same as indicated in the previous case.

2.2.2.3.3 sodium hydroxide and sugar. Another way to reduce silver chloride to silver metal is: Then wash the silver chloride is added to tap water to cover.

Then prepare a saturated solution of sodium hydroxide (caustic soda, NaOH) and it is added to the silver chloride, stirring continuously until the color of the mix ture changes completely undetected black and white particles or lumps. Then prepare a saturated solution of raw sugar and it is added to the mixture of silver chloride and sodium hydroxide with constant stirring until completely metalized silver. The reaction may be accelerated to do calentan 40/60 C. Vacuum filtered, washed with hot water until the filtrate look crystal clear.

Then neutralized with a sulfuric acid solution 10% co vinegar or undiluted.Washed again, until the filtrate to give a pH 7 (neutral). Dry and melt, as if it were filings, adding borax and sodium carbonate.

Fig 24. Device for vacuum filtration. A) Funnel porcelain, with a flat, bored, B) solution to filter, C) filter paper, round unfolded, D) Area vacuum or suction, E) filtered solution, F) Vessel Safety; G ) A vacuum pump.

2.2.2.3.4 sodium carbonate and glucose. Another procedure involves adding the freshly precipitated silver chloride, purified and washed, five times its weight of a solution formed by: Sodium carbonate 1 part 3 parts tap water

* Then, the mixture is boiled for some time, with one part of glucose. The reduced silver powder being thin, greyish black, which is just washed with boiling water. * Melts into a fireclay crucible using as funfundente, a mixture consisting of: Crystallized anhydrous Borax 5% 10% 0.5% sodium nitrate If not available anhydrous borax, borax can be replaced by crystallized.

2.2.2.3.5 by electrolysis.

Fig 25. Electrolytic reduction of silver chloride 1) and clamping washer hangers, 2) water acidulated with hydrochloric acid, 3) Anode, wrought iron
cylinder, 4) cathode, fine silver, 5) silver chloride; 6) Cuba plastic or any material insulation; 7) porous porcelain cup.

Silver chloride washing can also be reduced by transferring it to a glass porous porcelain dipped in hydrochloric acid Drico for several days to soak and then wash your best.After long time is left immersed in distilled water clean, renewing it frequently. * The porous glass is introduced into the water contained in an outer container in which, as an anode, is immersed cast iron cylinder, then, add a little hydrochloric acid Drico to initiate action. The silver chloride content in the glass is immersed porous cathode pure silver or platinum.Anode and cathode are connected to a battery as electricity. The white chloride situated around the cathode, and immediately blackens in the course of a few days, the reduction is complete. It forms iron chloride diffuses into the inner container and contaminates the silver, but can be removed by washing. Once free of impurities, the silver powder is melted as described above. The anode of wrought iron anodes may be replaced by graphite, but its action is slower and the external liquid permeates chlorine gas tightly and must be renewed once or twice a day, however, in this case, the silver not contaminated with impurities. 2.2.2.3.5.1 Melt the silver chloride without reducing prior to silver metal, sodium hydroxide and sodium carbonate.

Although, as indicated above, it is always better to reduce the metallic silver chloride before melting, fusing can also be reduced directly with sodium hydroxide (caustic soda, NaOH) and sodium carbonate (Na 2 CO 3), for separating silver chlorine and it is collected in the slag. It is essential that can be checked for the formation of a thin layer of salts, completely smooth, and the crucible must be careful not to break or that the molten material leaves the same, causing the consequent loss of metal.In these cases, adding mamiento prevents spills cooking salt melt. After separating the layers of sodium hydroxide and chloride from melting, the metal ingot can be emptied in a form suitable for electrolytic refining. 2.2.2.3.5.2 With sodium carbonate. Another method often used for small quantities, is reduced by melting silver chloride with anhydrous sodium carbonate. The dry silver chloride is transferred to a fireclay crucible, large enough to be filled with: a layer of sodium carbonate in equal volume to the amount of chloride melt, silver chloride covered with a layer of sodium carbonate same as above. After entering these volumes, the pot should be free the upper third of it, so that the dough does not spill boiling. Given the considerable gas formation that takes place during fusion, it must be given a moderate temperature, until gas evolution ceased in the form of white smoke.Then the temperature is increased - ture until the melt acquires a regular appearance, the stirring rod with a hot iron, no noticeable resistance.The reduction is complete, mind about 30 minutes. At this time, the crucible may be removed from the furnace and pour the contents into a

suitable iron mold, where it is allowed to cool. Next, silver is released from the sodium chloride slag adhered thereto, and finally washed in hot

water. Sometimes, always referring to small amounts, the crucible is cooled, break, remove the button and it blows again normally, emptying into the mold. This method offers the advantage that the metal can be obtained quickly, but deteriorates the crucibles soda. The money thus obtained is practically pure and still can be improved slightly, vol watching to melt under a layer of powdered charcoal. 2.2.2.3.5.3 sodium carbonate and potassium nitrate. Another possibility of carrying out the reduction by dry, is intimately mixing: Silver chloride, purified and dried 5 parts Anhydrous sodium carbonate 2 parts Potassium nitrate 1 part The mixture is poured, slowly, to a preheated crucible red earth. The melt is repeatedly removed with a rod of graphite or refractory clay until it meets the metallic silver at the bottom, forming a button. Cool, breaks the crucible and separating the silver button.2.2.3 nitric solutions.

In many workshops where container has a nitric solutions are kept clean from gold filings, removing welds, etc. that contain silver. These solutions are discussed, like exact istering the resulting solutions to attack silver alloys with nitric acid, cited above in 2.2.2. 2.2.3.1 Preparation of silver nitrate silver based alloy / copper. The silver nitrate crystals also can be prepared starting from commercial or coin silver. The silver alloyed with copper, as indicated above, is dissolved in a solution of chemically pure nitric acid, diluted to 50 or 60% using distilled water. The silver nitrate solution is passed to a porcelain evaporadera and evaporated to dryness by heating in a sand bath. Once expelled water and oxide free, sediment remains a greenish compound to silver nitrate and decobre.Further heating and silver nitrate melts, the copper is in trans form black copper oxide. Cool, add a small amount of distilled water and stir the content.

Then filtered.The dissolved silver nitrate through the filter, while black cupric oxide, insoluble, is retained therein. Re-evaporate the filtrate until crystallisation, obtaining silver nitrate free copper.If the operation is repeated, it improves the purity of silver nitrate. 2.2.3.2 Separation from impure silver filings and other debris. Silver, as repeatedly stated, is dissolved in nitric acid, chemically pure, diluted to 50 or 60%. The dissolution of the silver is carried out in a porcelain sufficiently large. Small cuts are covered with dilute nitric acid, cold filings are incorporated in small amounts.That is, first the acid is poured to the porcelain dish and it is added slowly filing, thus avoiding the formation of foam, splashes and overheating - ment.The large cutouts, especially bars and badges, previously, melt and dissolves granallarse to go easily. The solution is performed slowly and after some time, the capsule cam sand bath and heated gradually, reaching the boiling point. If silver remain undissolved residues be incorporated fresh acid to the solution. The copper content in the alloy dissolves at the same tim e, blue coloring of the solution.If the filing contains hie rro, the solution shows a yellow, yellowish or greenish brown, however, no influence on the subsequent working process. If the metal is completely dissolved, the solution is filtered to remove impurities and proceeds as indicated in 2.2.2.1 and following.

2.2.4 Separation attacking silver precipitating with sulfuric acid and hydrochloric acid. The metal foil as thin as possible and is wound in a spiral or is chopped and dissolves in hot concentrated sulfuric acid. Once the silver dissolved, the solution was allowed to cool and taking every precaution (by mixing sulfuric acid with water is a strong reaction), the solution is diluted decantndola on a considerable amount of water and let stand, if have remained undissolved particles that settle.

 These particles are collected, which may possibly contain gold and platinum, and bind to the next batch to be treated. When the silver sulphate solution is clear perfectamante, hydrochloric acid is added in sufficient quantity to precipitate all the silver, in the form of silver chloride. Silver chloride is treated as indicated above. 2.2.5 Separation of silver by cementation. Encuarte silver can also be prepared as follows: Coins, cuts, broken parts, etc.. Are dissolved in nitric acid at a ratio of three parts half of acid and a metal. Obtained clear solution of silver nitrate in distilled water diluted to about 6 times its own volume and introduced into the same copper foil, on which the money will be deposited gradually, gray powder form while others remain dissolved cough extraneous metals.After some hours, silver coated copper completely, preventing contact of the metal with the solution. When this occurs, should be stirred occasionally.Some days you get the complete deposition of silver. To make sure the solution is sufficient to add a few drops of hydrochloric acid or a sodium chloride solution, which should not produce any clouding due to the formation of silver chloride.Otherwise, if there is clouding, it will continue to act as copper with silver nitrate until the addition of the reagent does not lead to any cloud. Verified these conditions, copper is removed, the silver is removed and overlying liquid is decanted. The money obtained was washed thoroughly with running water until the washings give a neutral pH value.

Adding ammonia should not give bluish and with the addition of potassium ferrocyanide red color should not appear. Then, the silver is melted and dried with the aid of some borax.

2.2.6 Separation of silver Encuartes. The encuarte silver is used for the quantitative analysis of gold alloys. Title has to be high and be completely free of gold and platinum. Encuarte called because silver is believed to dissolve in nitric acid must be alloyed with gold in proportions of at least 3 parts silver per 1 gold.The gold part corresponds to "quarter" from which is supposed origin of the name "encuarte '. Ideally, use electrolytically refined silver but if not available, you can replace it with one that can be prepared as follows: Dissolve a silver alloy either in nitric acid.

 Dilute with distilled water and allowed to stand for several days, for alighting all traces of gold, together with the insoluble compounds that can be formed of certain metals that may be alloyed with silver, for example, tin or antimony. When the liquid is perfectly clear, the solution is removed from the container that contains it, trying not to remove it, using an appropriate siphon device which is rare Procu not reach the bottom of the container.To the solution containing silver nitrate, diluted with enough water is added an excess of a solution containing either transparent Cl '(solution of hydrochloric acid, chlorides - ro sodium, etc.).As you know, the silver chloride precipitate insoluble form, which, after being some - days we rest, settle to the bottom of the container.This silver chloride is reduced to metal and which melts following any of the processes indicated previously. 2.2.7 Chemically pure silver. Used to headline the solutions used to conduct trials of silver alloys and therefore must be pure. One method which has given good results for the preparation of chemically pure silver is as follows: Having obtained the well washed silver chloride is dissolved in ammonia.

Allow to stand for several days to pellet all impurities in chloride.If necessary, the liquid, filtering, carefully decanted with a siphon. Reprecipitated silver chloride with hydrochloric acid, to which it is added, to fully neutralize the ammonia. It is left to stand for some days so that the chloride settle at the bottom of the container; excess liquid is decanted and the silver chloride is repeatedly washed with disti lled water by decantation until the wash water give a neutral pH value . Chloride, washed, distilled water is added and brought to boiling.While boiling, is added pieces of sodium or potassium hydroxide Sodium hydroxide (NaOH) of from 350 to 400 g / kg Potassium hydroxide (KOH) of 400-520 g / kg Thus silver oxide formed is reduced to metallic silver with any reducer.It is suitable glucose (grape sugar), which is sufficient commercially - pure mind.Also formalin may be used, liquid at a rate of 300 g / kg, in cold. This has the advantage of finely divided metallic silver, with very solu ble substances and which can be easily removed by repeated washings with distilled water. If, as a reducing glucose is used you need: For silver kilo 830 grams Per kilo 630 grams silver chloride

Before washing the silver powder is advisable to ensure that it contains no unreduced chloride.To test this, ammonia is treated with a small amount of reduced silver is filtered and acidified. If turbidity is seen that one entire track remains unreduced silver chloride, in that case, should add more glucose and boil. Reactions are slow and, therefore, it is necessary hot mix clar substances during a period of time long enough.You can check whether the money has been totally re duced when, stirring with a spatula, sandy note.

 After washed and dried, the silver is melted in a crucible new vo without flux, which empty into an ingot can be laminated to bring it to the desired thickness.Dadosamente cui operating in a single operation, chemically pure silver can be obtained.

2.2.8 Separation of alloys silver / platinum. If a silver bullion containing much and little platinum is etched with nitric acid, part of the solution will platinum. and If the platinum content is too low, will dissolve completely. If the platinum content is high, only partly dissolve, and remain in the residue silver.

In other words, alloys, silver / platinum, can not be separated with nitric acid.Moreover, it is also not easy to recover the platinum nitric acid solution. The procedure in these cases, the slugs attack some diluted sulfuric acid, about one part water to three of acid.(Decant the sulfuric acid on the water slowly, while stirring). This may have CERSE when the content of platinum does not exceed 25%. After the sulfuric acid has dissolved much material as possible, decant the acid into a container with water, leaving the residue in the beaker. The liquid container contains silver sulfate and such common me.Silver may recover as has been indicated in 2.2.4 do (Separation attacking silver precipitating with sulfuric acid and hydrochloric acid). The residue containing platinum and possibly silver somewhat the acid has completely dissolved. Gather all the residue, wash thoroughly and then attack with aqua regia. If, by mistake, dissolves a silver / platinum in nitric acid, nitrate and the amount of platinum is formed so warrants, add enough hydrochloric acid to precipitate any silver as silver chloride.Filter and treat the silver chloride as indicated in 2.2.2.3.1 et seq. The filtered solution containing platinum dissolved in aqua regia type with a percentage of nitric acid much larger than usual.Evaporate, as usual, to remove nitric acid and then precipitating the platinum with ammonium chloride, as always.

2.2.9 Separation of the alloy silver / gold When these two metals alloys containing less than 25% gold, are attacked by dilute nitric acid, silver and gold dissolves as a residue remains invariably retains a small amount of silver. If the amount of gold present in the alloy is higher than 25%, prior to separation, should be added more silver or copper to lower the percentage indicated. The filtered solution containing the silver, it is the same as indicated for the above cases.

2.2.10 Separation of alloys silver / palladium. The alloys of these metals are attacked with concentrated nitric acid and silver as well dissolve the palladium nitrate form. Silver can be precipitated as chloride dissolved in hydrochloric acid Palladium can be precipitated with dimethylglyoxime or other suitable precipitant.

2.2.11 Separation of silver alloys / lead.

In this case, it is usually more convenient and separate silver by cupellation. If the two metals are in solution as nitrates, the first lead is separated by evaporating the solution, with excess of sulfuric acid, which precipitates as lead sulfate. Filtering the silver chloride is precipitated and then adding hydrochloric acid.
2.2.12 Separation of alloys silver / zinc.

Were dissolved with dilute nitric acid is precipitated as silver chloride and filtered. If one wants to recover zinc, the filtrate is added an excess of ammonia and, therethrough, is passed a rapid stream of hydrogen sulfide to precipitate the zinc sulphide.
2.2.13 Separation of silver alloy / cadmium.

Silver is dissolved in dilute nitric acid, precipitated as chloride and separated by filtration. To recover the cadmium is added an excess solution of the filtrate naco master, and then an excess of potassium cyanide solution.Then cadmium is precipitated under the form of bright yellow sulfur, heating the solution and by passing a stream of co hydrogen sulfide through it.
2.2.14 Separation of silver alloy / tin.

When alloys of these two metals are attacked with nitric acid dissolves silver and tin metaestnnico acid becomes insoluble. Filter and hydrochloric acid is added to the filtrate. Ta silver is precipitated in the form of silver chloride. The tin content, usually, is calculated by the difference, but may be determined by weighing the insoluble residue, or a mixture can be melted, approximately equal parts sodium carbonate and

sodium nitrite in a nickel crucible, fusion filtered with dilute hydrochloric acid and water, and tin, in the solution is determined through usual iodometric method or otherwise.
Cupellation 02/02/15. For silver alloyed title is appropriate under cupellation. It uses a reverberatory furnace with a crucible called concave cup, whence comes the name cupellation.The oven interior is lined with loam, which is a porous sedimentary rock calcareous clay.Its clay content between 25 and 75%, the remainder being calcium carbonate. This material, on contact with air, offering a great resistance to decomposition and is capable of absorbing ber lead oxide is produced, on the molten mixture as a result of oxidation by the air stream that surrounds it. The cupellation is the oldest method known to separate the precious metals (gold, silver, platinum and other metals of the latter) of metals. In the first operations of separation of silver by this means, from which data are available, the ore is smelted in a porous container shallow ash fact bones and continuous tion is exposed to a stream of air , at elevated temperature.The metals are oxidized with lead and were absorbed in the porous cup, while silver remained in the surface. When oxidation is complete and has passed all the lead to litharge, first produced iridescent coloration after vivid light emanating from the molten silver, the 'silver lightning' right when it opens the oxide layer that floats on the molten metal.The occurrence of lightning indicates the end of the separation. Electrolytic Refining 2.3. A few years ago there were factories in gold and silver refining equipped wholly or partially own recoveries containing precious metals. With scientific and technological progress goldsmith's workshop has been transformed, mass production with the introduction of increasingly numerous machines and the requirement of having to continually increase the quality, have moved out of the refining business. In general, electrolytic methods are not used for small scale operations.

2.3.1 Special services and process control. Methods for refining silver electrolytic processes involve requiring special attention, so they are carried out by trained and separately from other chemical activities described above. 2.3.2 Concentration upon. Refinery operations are possible only in metals that previously have been chemically treated to separate more components of the alloy.Purification and concentration of metal, before refining, are essential to prevent, if possible, contamination of the electrolyte during refining. 2.3.3 Development of the process. The process begins with the treatment of the crude silver anode, contaminated with other noble metals or with the aid of a suitable electrolyte, provides a very pure metal deposited on the

cathode. The metals or contaminants that give retained inside the anode bag, as insoluble material, or dissolved in the electrolyte. These processes are expected never treated solutions or waste obtained, reaching be completely free of noble metals. 2.3.4 Electrolytic cells. Electrolytic refining is carried out in cells or plastic tile. 2.3.5 electrolyte. The electrolyte composition is: Silver metal form silver nitrate 50 to 60 g / l Nitric acid 1.5 g / l 2.3.5.1 Pollution. The impurities that dissolve the anode, especially copper accumulate in the electrolyte. When copper is present, from certain concentration, begins to deposit on the cathode, together with the silver. When this happens the electrolyte contaminated must be replaced with a new one. The silver contained in the contaminated electrolyte is recovered as described in 9.2.2.1 and following. 2.3.6 Current density. Usually about 2 amp / dm
2.

2.3.7 Voltage.

In the electrolysis, in silver nitrate solution, the anodes of copper / silver are treated with a tension of 1.5 to 3.5 volts. 2.3.8 Anodes. The impure silver anodes can be caused by sludge from the electrolysis of copper or silver be obtained from secondary old objects, coins, etc., must be of the highest possible degree, in the dor, usually 995 parts of silver and the remainder gold. Materials from the photographic field. For the opera - tion more economical refining the anode composition should be adjusted carefully.The anodes are suspended in the anode rods and dissolved in the electrolyte. 2.3.8.1 Packets for anodes. The anodes are enclosed in sacks or bags, made of a fabric resistant electrolyte do.Inside these sachets is re mud or mud taken from gold or platinum group metals, which are washed well and subsequently treated according to advise its com position.In the electrolytic refining of silver are obtained significant amounts of gold. If in the sludge are not present platinum group metals, after washings, simply boiled in sulfuric acid, rinsed and dried so that they melt and marketed. Cathodes 2.3.9. As cathodes can be used stainless steel sheets. Silver, in its purest form, is deposited on the cathode in the form of macroscopic dendritic crystals, half that increase, is getting closer to the opposite pole, to cause shorts.

Scrapers 2.3.9.1. To prevent short circuits using scrapers activated by a reciprocating motion parallel to the electrodes and slightly away from the cathode, thereby breaking twigs.

2.3.9.2 collection basket. The crystals falling in a basket located in the bottom of Cuba, where periodically extracted.

2. 3. {0}9 . {/0}{1}

{/1}{0}

{/0} 3 Agitation.

Necessary, but controlled. If the bath is stirred excessively violent mind, the mud is removed and can contaminate the cathode, if sufficiently stirred, the electrolyte around the cathod e is locally depleted and increase operating costs.

02.03.10 Casting. Silver crystals from the electrolytic cell, washed, dried in a rotary oven heated by a gas burner, and then melt and emptied as granules or bars ready to be marketed. Its title is usuall y somewhere around the 999 Mil chasms.

2.3.11 Production costs and results. If this method is carried out correctly provides a high purity metal, a convenient and cost relatively little fuming.

2.3.12 installation cost. The installation cost is high and the job needs to be controlled by very skilled personnel. As it is the case that costs the same monitor a small plant to a large, in the second case is, labor costs, per ounce refined, are low. Disadvantages 02/03/13. 2.3.13.1 The process is slow and requires significant amounts of dead material. The main drawback of electrolytic refining is the slowness and the fact that much precious metal is permanently dissolved in the electrolyte, anode and cathode scrap.

2.3.13.2 The material must have a bachelor refine as high as possible.

When compared with separation methods are carried out by means of acids (9.2 Separation), the difference being that the material should exhibit a degree refining of at least 980 mils. The need to have, as a starting point, an almost pure metal is currently, one of the reasons why the electrolytic methods generally are not adopted by jewelers or by dental laboratories. Thus, it is assumed that a jeweler who has any amount of scrap silver to refine successfully through an electrolytic process, accurate first raise considerably the title you either scrap melting adding a generous amount of fine silver or by a preliminary treatment with acids.All these means involve such high costs that nullify the advantages attributed to the electrolytic process.

2.3.13.2.1 Lower titers increase production costs and decrease the quality of the final product. Although it is also possible to start the operation with anode electrolytic refining lower title, this makes the operating costs increase significantly. A greater amount of impurities - pray on the anode corresponds faster contamination of the electrolyte, or the cathode.This can lead contamination or mechanical codeposition or the inclusion of small metal particles on the rough surface o f the cathode.

2.3.13.2.2 Some impurities hinder the progress of the process. Some impurities, if present in sufficient quantity, may even stop the process. For example, if silver electrolysis, the anode containing an excessive amount of gold, can reach sludge form a gold layer on the anode which interrupts below attack thereof.

This drawback can be alleviated by cutting mechanically the sludge which adheres to the anode. 2.4.2 residues.

2.4 Cells Moebius and Thum. The cell types used are two: Moebius and Thum, also known as Balbach-Thum, which is also used for other types of operations. 2.4.1 Main differences. The two cells are used basically for the same electrolytic process but its structure is quite different. In the method of Moebius, anodes and cathodes are hung vertically, the anodes are engaged in individual bags and each cell contains alternately anodes and cathodes number two.Thum In the process a single anode is used, placed in horizontal position, the cathode, also in hori zontal position, rests on the bottom of the cell. Moebius cell can only work with cast anodes, while Thum cell can dissolve the material regardless of the shape thereof. The cell produces a lot more junk Moebius anodic Thum cell.When the anodes are not emptied clean - can be cut in mind the level of the electrolyte surface, leaving a substantial portion thereof into the anode bag.This scrap anode, usually melted for recycling. The anodes have to be emptied of conical shape, suspended with the thickest part of the anode to the anode rod and, thus, the erosion occurs tively progressively from the bottom upwards, being the lowest possible amount of anode scrap.

Fig 26.Moebius cell.

1) c at ho de s. 2) Li nk a ge a no de, 3) to t h re e a nod e s a nod e b ag, 4) an ode s, 5) fi lt e ri n g a nd co ll ec ti ng dis h, 6) El ec t rol yt e, 7) Cub a f or el ec tr oly si s, 8) s lidi ng g uid e s lin k a ge c a t hodi c be a ri ng s fi t ted, 9 ) st ai nl es s s t eel c at ho de s, 1 0) Sup por t d evi c e for r e cip ro c a ti ng e ngi n e, 1 1) Sc r a tc h re s, 1 2) Li nk ag e c a t hod e, 1 3) M o to r.

2.5 Cell Moebius.

For the electrolytic separation of silver is often used mind preferred Moebius process.The Moebius cell is a small Cuba refining multiple, working vertically. The anodes and cathodes are hung on hangers. Although, at present, there have been significant improvements in this type of cells, the basics remain the same. 2.5.1 Cubas.

The cell dimensions 60x60x55 typically be between 61 and x73x55cm. These tanks, working at room temperature, can be manufactured from polyvinyl chloride or polypropylene. Each Cuba has three to five anodic bars, where the anodes are suspended in rows of three, corresponding TES suspended from hooks.The anodic bars are connected in parallel to the positive pole of a DC source. Each row of anodes have the anode bag corresponding to the entire row or separate bags are used for each anode. It has four to six cathode rods connected in parallel to the negative pole, so arranged that each anode it stand between two stainless steel cathodes.The cathode r ods, reciprocating motion feature. The speed of the reciprocating move-ment is usually about 25 swings per minute and a range of 5 to 10 cm. The cathodic surfaces undergo the action of a con tinuous brushed to loosen silver crystals that are deposited therein.The brushing is carried out by means of combs made of insulating material, subject to Cuba. This operation aims to prevent excessive growth of the crystal mass of silver deposited on the cathode to avoid coming into contact with the anode and cause a short circuit. Silver crystals emerging from the cathode plates, they fall through the solution will stop at a platform or filter basket, placed in the bottom of Cuba, covering the entire bottom surface. Once the daily work, the mechanical linkages ONLY rise above the tanks.The bottom of the platform is empty Cuba, collecting silver crystals that have been accumulated lando therein, which are washed and filtered. The obtained silver hereby called electro lytic silver and has a very high degree of purity, of from 999.5 to 999.8 milliseconds.The most common type impurity is copper. Repi the eiectrolisis tend still be achieved a degree of purity higher.

Figure 27.Separation of the three main parts of the cell Moebius 1)

The Cuba with the reciprocating engine, 2) filtration Shopping for silver refined, 3) Top with linkages, anodes, cathodes, etc..

2.5.2 Anodes.
Ingots are used as anodes from cas chemical separations, which typically have dimensions of 350x120x12 mm, with a bulge at the top to hang (See fig.28).Bags are introduced into suitable tissue in which picking will do all matter that is insoluble off. Although it is recommended that the title of the anodes is as high as possible, the alloy thereof may be up to 30% gold and copper 1 0%, in exceptional cases, the copper content can reach 20%.

They can also be alloys containing: 269 parts of gold, of silver 592, 112 copper, zinc and with some anti mony.Containing unusually ele - ford gold, he is very attached to the anode in the form of pasta and causes an increase in stress and a delay in the progress of the solution.For this reason, the gold crust formed by the solution must be removed mechanically. Anodes of the silver is dissolved and the impurities it contains, ie metals. When the submerged part of the anodes is completely dissolved, are replaced by new ones. To avoid having to merge the remaining portion, which was not dipped in the solution, leading to c ell Thum, here where dissolving bara.

9.5.2.1 Treatment of anode slimes.

The sludge from the filter bags are transferred to a boiling water Cuba, of adequate size to the amount of waste treated. Add a little sulfuric acid to dissolve the copper salts. Allow to settle and sifonea. The mud is transferred to a centrifuge Tolhurst, with filter, to finish washing with water and

drying, The dried sludge is taken to a cast iron boiler, gift boiled for about 3 hours, with sulfuric acid of 60 Be.This treatment removes much of the copper and silver mud, leaving a gritty appearance brown residue, which can contain about 950 parts gold. This sand, after thoroughly washed and dried and is ready to be melted. The first washing water of the crystals of silver and silver crystals and sludge, containing nitrates of copper and silver, filtered and treated to separate silver.

This wash water is also used to compensate for losses due to evaporation of electrolyte and trawls.The excess electrolyte meets old, discarded and two, for recovery. * The solution of sulfuric acid from washing the mud, the concentrated acid from the boiler and water from washing of golden sand, gather in a Cuba that serves as a sink for undergoing a process so special cement.Bringing the solution was precipitated into boiling and introducing the same copper foil. Gold and silver thus cemented periodically den is fun and refined.

Cathodes 2.5.3.

The cathodes can be stainless steel sheets or fine silver, with approximate dimensions of 300x500x1, 5 mm (Fig. 29). The silver is deposited on the cathode, in the form of discrete crystals, adherent, elongated. 2.5.4 Current Conditions. The cell operated with an anode current density of 1 Amp / dm 2, the cathode amounts to 2 Amp / dm 2. Sometimes it can get worked up to about 5.4 Amp / dm 2. When working with silver anodes of lead and selenium impurities not exceeded the 1.3 Amp / dm
2.

With respect to the bath voltage is uneven and varies between 1.5 and 2.7 volts. 2.5.5 electrolyte. Electrolyte is used as a solution of silver nitrate 1 to 5%, acidified with nitric acid to about 1%, which may contain about 60 grams of fine silver and copper metal 30 g per liter. When the process is used for separating gold containing 60 to 80 g / l silver nitrate and an equivalent amount of nitric acid. However, the concentration may vary depending on the composition of the anodes, the most common being from 20 to 30 g / l of silver and 5 to 10 g / l of nitric acid. 2.5.6 Maintenance. Daily, part of the electrolyte is removed from Cuba and replaced by fresh electrolyte to maintain impurities below tolerable limits and silver content increases when depleted. At least once a day, to determine the content of silver metal dissolved in the electrolyte. If the electrolyte becomes dark, it may be necessary to replace it. 2.5.6.1 dirty or depleted electrolytes. The electrolyte can be used in dirty cell Thum, until exhausted. The exhausted electrolyte must be diluted to twice its volume men with distilled water, and adding silver precipitate sodium chloride. 2.5.6.2 Preparation of a fresh electrolyte. For silver nitrate may proceed as indicated in "2.2.3.1 Preparation of silver nitrate silver based alloy / copper", although in this case, instead of from a silver alloy / copper, silver is better to use thin.However, it can also be noted that the process shown below:

Silver is dissolved in nitric acid and the silver nitrate solution is boiled to concentrate. Then reheated to boiling nitric acid, to evaporate. The vapor and nitric acid fumes are expelled work

down in a booth equipped with vapor extraction. The silver nitrate crystals are dissolved again in distilled water.The volume is adjusted to an

appropriate concentration and stored. Daily concentration is determined

Silver electrolyte and, if necessary, using the previously prepared solution to compensate. Through this process, trying the same silver twice, achieves a very high purity. 2.5.7 Advantages of the process relating to the Moebius process Thum. They are the following: The remote anode / cathode is very short, about 30 mm, which, together with the dissolution of both faces of the anodes, providing a high production yield per unit floor area and volume of electrolyte. No precise membrane anode muslin because not lying along the mud that accumulate. Requires labor cost very low, because the separation of the silver deposited at the cathode Reciprocating available that provides a more uniform deposit and a current efficiency of

takes place mechanically 98%, which is from 5 to 10% higher than that provided by the process of Thum. 2.5.8 Disadvantages. They are: To extract the silver crystals produced have to completely stop production. Mechanics and current conduction are complex, resulting in high installation costs and

maintenance.

Thum cell 2.6. 2.6.1 Cubas. This cell consists of one shallow Cuba, about 127 x 60.9 x 22.8 cm or also 122 x 35.5 x 17.7 cm. The Cuba is constructed of polypropylene or polyvinyl chloride.

2.6.2 The anode. Thum In the process, the anode is placed inside a weapon Zon lined with muslin and covered with a thick canvas bag.In turn, the frame is placed on a platform resting on the sides of the electrolytic cell. The anode frame covers approximately half of the cell, leaving the other half free. The silver anode dissolves passed through muslin and canvas that acts as a filter, keeping the mud.

Figure 30. Thum cell 1) piece of muslin covering glass rods used as a support for the anode, 2) stainless steel cathode;
3) Anode; 4) glass support bars.

2.6.3 The cathode. Cuba The bottom is covered with a sheet of stainless steel or graphite, which acts as cathode. Above the cathode is disposed a basket, like a shelf. The perforated bottom of the basket is covered with glass cloth,

without interrupting the deposition.Access to the cathode is facilitated by moving the basket from one side to another of the Cuba. This cell produces less scrap because the anodic material to be incor porating the same may be placed on top of the basket, while the remaining material is attacked. The deposit accumulated on the open end collected, washed and filtered. Before completely dissolve the anode, is placed above a new, complete dissolution is not to consolidate remnants.

The anode waste can be processed for the separation of the noble metals. In the case of process Thum, these sludges are collected every three days, removing the support covered with muslin, washing and filtering the washing water. The silver produced in cell Thum is revisited in the Moebius cell, which is what provides the final product. 2.6.4 The electrolyte. The electrolyte is composed of a neutral solution of silver nitrate and copper, 60 g / I of silver metal and 40 g / l of copper metal. 2.6.5 Current Conditions. Operating at a voltage between 3 and 3.5 volts. The cathode is connected to the power source (-), through contacts of stainless steel and copper bar, while the anode (metal placed in the basket ()), is connected to the copper bar and by a long silver solid metal block which serves as contact between the bar and the metallic scrap. The normal current density at the anode is 5.4 Amp / dm 2, the maximum current, per cell, is about 1 50 amp. 2.6.6 Advantages of the process. Thum process advantages are: Its mechanical simplicity and management, contribute to the costs of installation and maintenance are very low. Complete dissolution of the anodes, which may be of any size or weight, provided they fall within the scope of capacity and resistance of the anodic support. To collect the crystals of silver is not necessary to stop the work.

2. 6. 7 Disadvantages. They are: The anode dissolves on one side which causes comparatively output per unit of floor area and volume of electrolyte is low. Manual separation of the silver cathode which means labor costs. Absence or reciprocating movement within Cuba.

3. Precipitating and Reducers LA PLATA

Several reducing agents precipitate silver from their solutions to the metallic state.
3.1 organic precipitant.

Silver compounds are quickly reduced through tas certain organic substances such as sugar, tartrates, aldehydes, etc.For example, when a hot solution of silver nitrate was added a solution of sugar, we obtain a grayish white powder of metallic silver. Also many inorganic salts, which act as reducing agents, for example ferrous sulphate, silver precipitating solutions of their salts.
Precipitating metal 3.2.

The chemical attack or corrosion is basically an electronic process troqumico.The metal attacked behaves similarly as does an electrode in an electrolytic cell or battery. When a metal in contact with certain substances, corrosive or potentially creates a potential difference. Je volta value depends on each metal chemical system in particular compared with an electrode rndolo standardized in practice a hydrogen electrode.Each metal can be assigned a single value, known as standard electrode potential (E ). The values for some metals us shown in the following electrochemical series.

Table X

Electrochemical series
Metálico E Volts Metálico E Volts

Gold Platinum Iridium

+ 1,68 1:20 1/00

Ruthenium Copper Nickel Iron

0.45 0.34 - 0.23 - 0.41

Palladium + 0,83 Zinc Rhodium 0.80 Silver + 0,81 Aluminum Magnesium - 1.70 2.13 - 0.76

Osmium 0.70

Many metals are capable of reducing silver salts in solution.The fully precipitated silver nitrate solutions or sulfate, using copper, iron, zinc, magnesium, tin or lead. Silver precipitates in a crystalline state or foamed, depending on concentration and temperature of the solution. The reducing action of silver metal solutions, often provides advantages in the separation and determination of silver alloys, and also to reduce silver chloride to silver metal.

The more positive the value, the greater resistance offered by the metal to be attacked. Gold is found in the top of the list, followed by the other precious metals. This is due to their position in the series, so that these metals are called noble metals and have much resistance to corrosion.