Verdigris is little used as a pigment, but is important to the colour maker, because copper colours are made from it. In wine-growing countries it is made from the marc at small expense and without much labour.

In commerce several kinds of verdigris are distinguished; they differ in physical and chemical properties. All verdigris consists of copper acetate, either alone or combined with varying quantities of copper hydroxide.

Blue Verdigris is made in large quantities in France and is commonly known as French verdigris (vert de gris naturel). It has the following formula:—

Cu(OH)(C₂H₃O₂).2½H₂O.

The process adopted in southern France, especially in the neighbourhood of Montpellier, is as follows: copper plates are placed in layers in heaps of the freshly pressed grape residues, which always contain a certain quantity of must even when the most powerful presses are used. The process is conducted either in large heaps or in pots; in the first case care must be taken that the heaps are in a room whose temperature does not lie below 15° C. It is important to maintain this temperature, because the formation of acetic acid takes place with sufficient rapidity only at temperatures not below 12° to 15° C. Too high a rise of temperature in the heaps must also be avoided or a considerable quantity of acetic acid will be volatilised. The heaps should therefore not be made too large, otherwise the temperature cannot be kept within the proper limits.

The residues contain a considerable quantity of sugar, which can be transformed by fermentation into alcohol. If air has free access, the alcohol is at once oxidised to acetic acid, which is recognised by the acid smell given off. In order to make possible the entry of air into the interior of the heaps, rectangular wooden bars are introduced in piling up the heaps. These are carefully withdrawn when the heap is finished, so that it is traversed by passages through which air can enter. By the simultaneous action of air and acetic acid copper acetate is formed, and since copper is always in excess, the acetate produced is a basic salt. In consequence of the chemical processes, the temperature of the heap rises to 35° to 40° C.; it is endeavoured to attain this temperature by artificial heat. It has already been stated that too great a rise of temperature is accompanied by a considerable evaporation of acetic acid. The process is then finished in a short time, but the loss of acetic acid is remarkable. When the temperature is so regulated that it varies between 25° and 30° C. the process takes a normal course—four to five days may be regarded as its duration.

The grape residues are effective on account of the sugar, which is transformed into alcohol and then into acetic acid. Residues which have been extracted with water after pressing should not be used in the manufacture of verdigris; they contain but little sugar and hence undergo a very feeble acetic fermentation. When such residues are used the verdigris is often accompanied by black spots of copper sulphide upon the plates; this is due to incipient decomposition of the residues.

As a practical test for the termination of the process a strip of copper is plunged into the heap and left for some hours. It should be covered by a uniform coating of verdigris; if it is covered with small drops that is a sign that the process is not completed and the heaps must be left some time longer. The course of the process can be simply and safely followed by means of a thermometer. This is placed in a perforated copper tube and plunged into the interior of the heap. A continuous rise of temperature indicates a steady increase of chemical action; the temperature of the room is regulated in accordance. When the temperature in the interior of the mass begins to fall the process is nearing the end. More heat is now supplied to assist the chemical action. The process is at an end when, in spite of external heat, the temperature of the heap decreases and approaches the temperature of the air of the room.

Verdigris can also be made by placing sheet copper and grape residues in layers in pots, which are deposited in a room of fairly uniform temperature, such as a cellar. This method has the advantage that the formation of the verdigris is finished in a shorter time, which is more than counterbalanced by the labour and expense of filling the pots.

The copper plates, when removed from the heaps or pots, are covered by a crust of thin needle-shaped crystals of a bright green colour. They are shaken to free them from the adhering grape skins and seeds, and then treated with weak vinegar, in which they are dipped; they are then left standing on edge for several days. This treatment with vinegar has the object of converting the neutral salt formed on the plates into basic salt. The dipping into vinegar and exposure to air are repeated six to eight times, when the originally pure green crust on the plates is gradually changed into bluish-green verdigris. These processes are continued until the plates are covered uniformly by a layer of verdigris about 5 centimetres thick. The crust is then scraped off by copper knives and stirred with water to a paste, which is pressed in leather bags in rectangular moulds. The lumps are then slowly dried in the air.

Plates which have been once used give a larger quantity of verdigris in a second operation, which is to be ascribed to the fact that they possess a larger surface than unused plates. New plates are made more susceptible to the further action of the acid by dipping in strong vinegar, by which they become covered with a layer of copper acetate.

The verdigris obtained by this method consists of crystalline scales of a pale bluish-green colour, which produce a pale blue powder. In crude verdigris grape seeds are often found, and occasionally stalks and pieces of metallic copper. These admixtures are a consequence of the method of manufacture and cannot be regarded as adulterants. Gypsum is to be regarded as an adulterant. Verdigris often contains basic copper carbonate.

Verdigris behaves in a peculiar manner with water. In contact with a small quantity it swells to a bluish-green mass, which becomes quite warm. Neutral copper acetate and the basic salts 2Cu(C₂H₃O₂)₂.Cu(OH)₂.5H₂O and Cu(C₂H₃O₂)₂.2CuO.1½H₂O are formed, the latter of which is insoluble.

By the addition of a larger quantity of water the basic compounds are decomposed, neutral copper acetate dissolves, and a mixture remains of the compound Cu(C₂H₃O₂)₂.2CuO.1½H₂O and a brown basic acetate containing still less acetic acid. On account of this peculiar behaviour of verdigris towards water some care is required when it is used as a water colour. A very dilute solution is not green, but has an indefinite shade.

Distilled or Crystallised Verdigris consists of neutral copper acetate, Cu(C₂H₃O₂)₂.H₂O. It can be made from blue verdigris by treating with the amount of acetic acid required to completely neutralise the copper oxide, or by decomposing copper sulphate with the acetate of a metal which forms an insoluble or difficultly soluble sulphate.

Crystallised verdigris is very simply made from ordinary verdigris; the latter, whilst still moist, but containing only a small quantity of water, or the acetic acid would be too largely diluted, is brought into a pan and strong acetic acid poured over. Strong pyroligneous acid may be used, its empyreumatic odour is without influence on the quality of the product. The pan is heated until the contents almost, but not quite, boil. They are frequently stirred so that the particles at the bottom are brought in contact with the acid. A dark green solution is formed; when its colour no longer increases in depth it is allowed to stand until suspended solids sink to the bottom. The clear solution is then drawn off and rapidly evaporated in shallow copper pans. It is important that the liquid should not contain an appreciable quantity of free acid. When a crystalline skin begins to form on the surface of the solution it is drawn off into the crystallising vessels. These are made of glazed earthenware; wooden rods are placed in them, on which the crystallisation takes place. In order that large crystals shall be obtained, it is necessary to maintain a regular temperature in the room in which the crystallising vessels are placed. It is heated at the commencement, and the temperature is allowed to sink a little towards the end of the operation. From twelve to fourteen days are required to obtain large crystals. The mass of verdigris crystals adhering to each rod weighs 2·5 to 3 kilogrammes. The residual liquid is a saturated solution of verdigris, and is used in the next operation. It is only necessary to heat it with the residue from the first operation and some acetic acid in order to obtain a crystallisable solution of verdigris.

The residue in the pan contains metallic copper, grape stems and seeds, and basic copper acetate. The copper is extracted by moistening with acetic acid and exposing to the air, when verdigris is formed, which is added to a later batch.

It is often advisable to make verdigris from a soluble copper salt; the process varies somewhat according to the salt employed. From copper sulphate verdigris is obtained by the action of calcium acetate. When solutions of these compounds are mixed, calcium sulphate separates as a white precipitate, whilst a solution of the easily soluble copper acetate is left. It is only necessary to mix the solutions in equivalent proportions, separate the liquid from the precipitated gypsum and evaporate. Gypsum is somewhat soluble in water, so that when the solution is evaporated a double salt separates out first. This consists of copper calcium acetate; it may be used as a pigment, but is of less value than verdigris. It is advisable to prevent the formation of this double salt, which is accomplished by adding copper sulphate to a slightly acid solution of calcium acetate until a precipitate is no longer produced. The solution of copper acetate is boiled for several hours to effect the separation of the dissolved gypsum; at the same time the iron contained as impurity in the copper sulphate is also precipitated. The purified solution of verdigris is concentrated and allowed to cool, when a further quantity of gypsum separates; the solution is then evaporated to crystallisation.

If barium salts and lead acetate are cheap, barium acetate can be obtained by double decomposition. When copper sulphate is added to the solution of barium acetate so long as a precipitate is formed, a solution of verdigris is produced, which only requires evaporation to crystallise. The precipitate is barium sulphate, and can be used as enamel white. It obstinately retains a quantity of copper, which, though small, is sufficient to give it a greenish tint. By several washings with acetic acid this copper is removed; the acid can be used to obtain fresh quantities of verdigris, so that none is lost, and the copper retained in the precipitate is regained. The precipitate, after treatment with acetic acid, only requires thorough washing with water to produce permanent white, satisfactory in every respect.

Ammonia may also be used in the manufacture of verdigris from copper sulphate. Strong ammonia is left in contact with copper sulphate in a covered vessel for several hours; gentle warming accelerates the formation of copper ammonium sulphate. The liquid has then a fine blue colour; it should not contain sufficient ammonia to be perceptible by the smell. It is then gently warmed and acetic acid gradually added. On continued heating small green crystals separate from the solution, which is boiled with continual additions of acetic acid in small quantities until small crystals appear on the surface, when it is allowed to cool and the crystals are strained off.

”Distilled” verdigris forms deep bluish-green crystals, which effloresce slightly in the air; they dissolve in 5 parts of boiling water and in 13·4 parts at 20° C. When the solution is boiled for some time the tribasic acetate separates; the liquid becomes brown and acquires an acid reaction.

German Verdigris does not differ essentially from ordinary verdigris. It is a compound of the following basic acetates: 2Cu(C₂H₃O₂)₂.CuO and Cu(C₂H₃O₂)₂.2CuO. The method is similar to that in which grape residues are used; where acetic acid is cheap the process is especially appropriate. In Sweden, where pyroligneous acid is made in large quantities and copper is also cheap, verdigris is made by arranging copper plates and flannel in alternate layers. The plates are frequently turned over and the flannel kept saturated with acetic acid. The same chemical reactions occur as in the process in which grape residues are used. When a layer of verdigris has formed on the copper plates they are taken apart, exposed to the air, and frequently wetted. The formation of the verdigris is thus completed. The difference between this process and that adopted in wine-producing countries lies simply in the use of pure acetic acid; the product is free from the mechanical impurities introduced by the grape residues. In properties German or Swedish verdigris is completely identical with blue verdigris.