7.1. Alloys of copper and nickel Copper and nickel are infinitely soluble in both liquid and solid states. The phase diagram of Cu – Ni is shown in Fig. 7.1. The structure of all binary copper-nickel alloys is a solid solution of these elements. Crystal cell -

Long before the discovery of nickel, Saxon miners knew a mineral that resembled copper ore and was used in glass making to color glass green. All attempts to obtain copper from it were unsuccessful, and therefore it received the name “kupfernickel”, which roughly means “Copper Devil” (cf. German Nickel - mischievous). This mineral (red nickel pyrite NiAs) was studied by the Swedish mineralogist and chemist Kronstedt in 1751. He managed to obtain green oxide and, by reducing the latter, a new metal called nickel.

Being in nature, receiving:

Nickel is quite common in nature - its content in the earth's crust is 0.01% (wt.). In iron meteorites (up to 8%). In plants, on average, 5 * 10 -5 weight percent, in marine animals - 1.6 * 10 -4, in terrestrial animals - 1 * 10 -6, in the human body - 1 ... 2 * 10 -6
The bulk of nickel is obtained from garnierite and magnetic pyrites in several ways:
1. Silicate ore is reduced with coal dust in rotary tube kilns to iron-nickel pellets (5-8% Ni), which are then cleaned of sulfur, calcined and treated with an ammonia solution. After acidifying the solution, metal is obtained from it electrolytically.
2. Carbonyl method (Mond method). First, copper-nickel matte is obtained from sulfide ore, over which CO is passed under high pressure. Highly volatile tetracarbonylnickel is formed by thermal decomposition, which releases a particularly pure metal.
3. Aluminothermic method. Reduction of nickel from oxide ore with aluminum: 3NiO + 2Al = 3Ni +Al 2 O 3.

Physical properties:

Metallic nickel has a silvery color with a yellowish tint, is very hard, tough and malleable, polishes well, and is attracted by a magnet. Density of a simple substance at no. 8.902 g/cm 3, melting point = 1726 K, boiling point = 3005 K.

Chemical properties:

At normal temperatures, nickel is characterized by high corrosion resistance - it is stable in air, water, alkalis, and a number of acids. Reacts with nitric acid, forming nickel(II) nitrate Ni(NO 3) 2 and the corresponding nitric oxide.
When heated, nickel reacts with many non-metals: halogens, sulfur, phosphorus, carbon. With atmospheric oxygen at 800°C, nickel forms the oxide NiO.
Nickel is capable of absorbing large volumes of hydrogen, resulting in the formation of solid solutions of hydrogen in nickel.
With carbon(II) monoxide, nickel easily forms volatile and highly toxic carbonyl Ni(CO)4.

The most important connections:

In compounds, cobalt exhibits an oxidation state of +3, +2, 0.
Nickel(II) oxide, NiO - solid from light to dark green or black. Basic properties prevail; it is reduced to metal by hydrogen and other reducing agents.
Nickel(II) hydroxide, Ni(OH) 2- green in color, slightly soluble in water and alkalis, good in many acids, basic properties predominate. When heated, it decomposes to form NiO.
Nickel(II) salts- usually obtained by reacting NiO or Ni(OH) 2 with various acids. Nickel salts soluble in water usually form crystalline hydrates, for example, NiSO 4 *7H 2 O, Ni(NO 3) 2 *6H 2 O. Insoluble nickel compounds include Ni 3 (PO 4) 2 phosphate and Ni 2 SiO 4 silicate. Crystal hydrates and solutions are usually colored green, and anhydrous salts are yellow or brownish-yellow.
Nickel(II) complex compounds very numerous (number = 6). Their formation explains, for example, the dissolution of nickel oxide in an ammonia solution. Nickel dimethylglyoximate Ni(C 4 H 6 N 2 O 2) 2, which gives a clear red color in an acidic environment, is used as a qualitative reaction to nickel (II) ions.
Nickel(III) compounds- less typical. Known, for example oxide Ni 2 O 3 *H 2 O, a black substance, is obtained by the oxidation of nickel(II) hydroxide in an alkaline medium with hypochlorite or halogens:
2Ni(OH) 2 + 2NaOH + Br 2 = Ni 2 O 3 *H 2 O + 2NaBr + H 2 O
Strong oxidizing agent.
There are also complex compounds nickel(III), for example, K 3.
Nickel carbonyl, Ni(CO) 4. Diamagnetic colorless liquid, very volatile and toxic. It hardens at -23°C, and when heated to 180-200°C, it decomposes into metallic nickel and carbon monoxide (II). Ni(CO) 4 is slightly soluble in water, well in organic solvents, and does not react with dilute acids and alkalis.

Application:

Nickel is a component of many alloys - heat-resistant, resistance alloys (nichrome: 60% Ni + 40% Cr), jewelry (white gold, cupronickel), coins.
Nickel is also used for nickel plating - creating a corrosion-resistant coating on the surface of another metal. They are also used for the production of batteries, winding strings of musical instruments...
Nickel is one of the trace elements necessary for the normal development of living organisms. It is known to take part in enzymatic reactions in animals and plants.
Nickel can cause allergies (contact dermatitis) to metals that come into contact with the skin (jewelry, watches, denim rivets). The European Union limits the nickel content in products that come into contact with human skin.

Rudagina Olga
HF Tyumen State University, 581gr., 2011

Sources: Wikipedia: http://ru.wikipedia.org/wiki/Ni, etc.,
Popular library of chemical elements. Nickel. http://n-t.ru/ri/ps/pb028.htm
Website of the Department of General and Inorganic Chemistry of the Russian Chemical Technical University named after. DI. Mendeleev. Table D.I. Mendeleev: Nickel

REISSUE (November 1991) with Amendments No. 1, 2, 3, 4, approved in August 1980, March 1983, July 1985, June 1990 (IUS 10-80, 7-83, 10 -85, 9-90)


This standard applies to powdered nickel oxide used in enterprises manufacturing enameled products.

Formula NiO.

Molecular mass (according to international atomic masses 1971) - 74.709.

1. TECHNICAL REQUIREMENTS

1. TECHNICAL REQUIREMENTS

1.1a. Nickel oxide must be manufactured in accordance with the requirements of this standard according to technological regulations approved in the prescribed manner.

(Introduced additionally, Amendment No. 2).

1.1. Nickel oxide should be produced in the form of a powder with a particle size of no more than 0.5 mm.

Table 1

Note. By agreement with the consumer it is allowed mass fraction malleable grains of nickel oxide no more than 0.01%.

(Changed edition, Amendment No. 4).

1a. SAFETY REQUIREMENTS

1a.1. Nickel oxide dust has a carcinogenic effect and affects hematopoiesis and carbohydrate metabolism; hazard class 1 according to GOST 12.1.007-76; the maximum permissible concentration in the air of the working area of ​​industrial premises (in terms of nickel) is 0.05 mg/m according to the standards approved by the USSR Ministry of Health.

1a.2. The maximum permissible concentration of nickel in the water of reservoirs for sanitary use is 0.1 mg/dm according to the standards approved by the USSR Ministry of Health.

1a.3. Nickel oxide cannot be neutralized or destroyed. Spilled product after dry and subsequent wet cleaning is disposed of in technological processes nickel production.

1a.4. Nickel oxide under normal conditions is non-flammable, fire- and explosion-proof, in air and wastewater does not form toxic compounds in the presence of other substances.

1a.5. Those working with nickel oxide must be provided with personal protective equipment in accordance with GOST 12.4.103-83.

To protect the respiratory system, depending on the concentration, filtering anti-aerosol respirators of the 2nd and 1st degree of protection should be used in accordance with GOST 12.4.011-89, GOST 12.4.034-85 *, GOST 12.4.041-89 *.
______________
GOST 12.4.034-2001;
*8 On site Russian Federation GOST 12.4.041-2001 is valid

1a.6. Those working with nickel oxide must be provided with household premises equipped with devices according to group IIIa production processes according to the norms and rules approved by the USSR State Construction Committee.

Production and laboratory premises in which work with nickel oxide is carried out must be equipped with supply and exhaust ventilation in accordance with GOST 12.4.021-75, ensuring the air condition of the working area in accordance with the requirements of GOST 12.1.005-88.

The air condition of the working area is monitored in accordance with GOST 12.1.007-76 and methods approved by the USSR Ministry of Health and the corresponding GOST 12.1.016-79.

1a.7. Everyone working with nickel oxide must undergo training in accordance with GOST 12.0.004-79 *.
________________
*Probably an error in the original. You should read GOST 12.0.004-90. - Database manufacturer's note.

1a.8. The analysis of nickel oxide must be carried out in accordance with GOST 12.3.002-75 and regulatory and technical documents on the safe performance of work in a laboratory environment, approved in the prescribed manner.

1a.9. When loading and unloading nickel oxide, the safety requirements in accordance with GOST 12.3.009-76 must be observed.

Section 1a. (Changed edition, Amendment No. 3).

1.2. By physical and chemical parameters Nickel oxide must comply with the standards specified in Table 1.

2. ACCEPTANCE RULES

2.1. Nickel oxide is taken in batches. The batch includes a product that is homogeneous in its quality indicators, in an amount of no more than 10 tons, simultaneously sent to one address and accompanied by one quality document containing:



Product name;

results of the analyzes performed;

batch number and date of manufacture;

gross and net weight of the batch;

number of packaging units of the batch;

2.2. A combined sample of nickel oxide is taken by weight of at least 1% of the batch. The number of packaging units from which samples must be taken are indicated in Table 2.

It is allowed to take samples directly from the stream at regular intervals throughout the loading and unloading of a batch of the finished product.

table 2

(Changed edition, Amendment No. 2).

2.3. If unsatisfactory analysis results are obtained for at least one of the indicators, a re-analysis of twice the number of samples taken from the same batch is carried out. The results of repeated analyzes are considered final and apply to the entire batch.

3. METHODS OF ANALYSIS

3.1. A spot sample of nickel oxide is taken using a probe consisting of two tubes - external and internal. The outer tube must have a closed end and be equipped with a slot-like slot along the entire length of the probe insertion.

The inner tube must have one or more slots located so that when the tubes rotate in different directions relative to each other, the slots can open and close. The tubes must fit freely into one another so that even the largest particles between them do not interfere with rotation.

The probe is inserted into the drum, bag or barrel to the depth of the packaging unit with the slots closed. When the probe reaches the depth of the packaging unit, the slots must be opened so that the probe is filled with powder along the entire length of the slots, after which the slots are closed and its contents are poured into a collection for a combined sample.

The selected pooled sample is reduced using a divider. In this case, nickel oxide from the filling device is poured evenly into the chambers of the left and right collections.

The combined sample is reduced to a mass of at least 0.5 kg. The resulting average laboratory sample is divided into two parts, one part of which is ground to 0.15 mm and sent for chemical analysis, the second part is sent for qualitative determination of the content of solid grains of metallic nickel.

3.2. Preparation of an analyzed solution for the determination of nickel, cobalt, iron, copper, aluminum, magnesium

3.2.1. Reagents and solutions used:

hydrochloric acid according to GOST 3118-77;

nitric acid according to GOST 4461-77, density 1.38 g/cm;

sulfuric acid according to GOST 4204-77, diluted 1:1;

acid potassium sulfate according to GOST 4223-75;

hydrofluoric acid (hydrofluoric acid) according to GOST 10484-78;

distilled water according to GOST 6709-72;

perchloric acid with a density of 1.60 g/cm.

3.2.2. Chemical sample processing

To determine the mass fraction of nickel and cobalt, take separate sample samples of 1 g, respectively. To determine the mass fraction of iron, copper, aluminum, take a total sample equal to 1 g. The resulting samples are decomposed as follows: a sample weighed to the nearest 0.0002 g, dissolve in a glass with a capacity of 200-300 cm in 30 cm of hydrochloric acid when heated for 10-15 minutes. Then add 10-20 cm nitric acid and continue heating, covering the glass with a watch glass. After dissolving the bulk of the glass, remove it and wash it with 3-5 cm of water. Carefully add 20 cm of sulfuric acid to the sample and evaporate the solution until sulfuric anhydride vapor begins to release. Cool, wash the walls of the glass with 3-5 cm of water and evaporate again until sulfuric anhydride vapor begins to release. After cooling, add about 50 cm of water. If an insoluble residue remains, it is filtered through an ash-free filter and melted with acidic potassium sulfate. To do this, the residue on the filter is washed with hot water, dried, transferred with the filter into a platinum crucible, the filter is ashed and calcined. The precipitate is moistened with a few drops of water, 2-3 drops of sulfuric acid and 2-3 cm of hydrofluoric acid are added, heated and evaporated to dryness. The dry residue is fused with a small amount of acidic potassium sulfate (0.2-0.3 g). The melt is dissolved in warm water acidified with sulfuric acid and added to the main solution - solution A.

When determining iron, copper, aluminum, solution A, obtained from a separate sample, is transferred to a 100 cm3 volumetric flask and the volume of the solution is adjusted to the mark with water - solution

3.3. Determination of the mass fraction of nickel is carried out according to GOST 13047.1-81 * (Section 2). In this case, solution A is taken for analysis (clause 3.2), transferred to a beaker for electrolysis, 3 g of ammonium sulfate is added and subjected to electrolysis.
______________
* GOST 13047.1-2002 and GOST 13047.2-2002 are in force on the territory of the Russian Federation. - Database manufacturer's note.

3.4. Determination of the mass fraction of cobalt is carried out according to GOST 13047.6-81 * (section 4). In this case, solution A is taken for analysis (section 3.2).
______________
* GOST 13047.4-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

3.2.1-3.4. (Changed edition, Amendment No. 4).

3.5. Determination of the mass fraction of iron is carried out according to GOST 13047.14-81 * (section 3). In this case, an aliquot of solution B (clause 3.2), equal to 20 cm, is taken for analysis; an aliquot containing 10-100 μg of iron is taken for colorimetry.
______________
* GOST 13047.17-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

3.6. Determination of the mass fraction of copper is carried out according to GOST 13047.7-81 * (Section 2). In this case, an aliquot of solution B (section 3.2), equal to 20 cm, is taken for analysis; For colorimetry, an aliquot containing 10-100 μg of copper is selected.
______________
* GOST 13047.10-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

3.7. Determination of the mass fraction of sulfur is carried out according to GOST 13047.3-81 * (section 3).
______________
* GOST 13047.7-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

3.8. Determination of the mass fraction of aluminum is carried out according to GOST 13047.16-81 * (Section 2). In this case, for analysis, take an aliquot of solution B (clause 3.2), equal to 10 cm, and carry out electrolysis with a mercury cathode; For colorimetry, an aliquot containing 10-100 μg of aluminum is selected.
______________
* GOST 13047.19-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

3.9. Determination of the mass fraction of silicon is carried out according to GOST 13047.4-81 * (section 3). In this case, 1.0000-2.0000 g of sample is decomposed in 30 cm of hydrochloric acid and 20 cm of perchloric acid. The insoluble residue is fused with 0.3-0.5 g of a mixture of potassium carbonate and sodium and leached with water. The combined solutions are evaporated until white vapor appears (within 15 minutes).
______________
* GOST 13047.8-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

The permissible discrepancies between the results of parallel determinations, characterizing the convergence of the method (), and the results of the main and repeated analyzes, characterizing the reproducibility of the method (), should not exceed the values ​​​​given in Table 3.

3.10. Determination of the mass fraction of magnesium is carried out according to GOST 13047.17-81 * (section 2). In this case, 1.0000 g of sample is dissolved by heating in 30 cm of hydrochloric acid. After the dissolution reaction stops, add 10 cm of nitric acid and continue dissolution, add 5 cm of hydrofluoric acid, boil for 5 minutes, add 5 cm of perchloric acid and evaporate to abundant vapor.
______________
* GOST 13047.20-2002 is in force on the territory of the Russian Federation. - Database manufacturer's note.

The permissible discrepancies between the results of parallel determinations, characterizing the convergence of the method (), and the results of the main and repeated analyzes, characterizing the reproducibility of the method (), should not exceed the values ​​​​given in Table 3.

Table 3

3.11. Determination of the mass fraction of malleable grains of nickel oxide

To check the presence of malleable grains of nickel oxide, indicating the presence of continuous, alloyed particles of metallic nickel, take a 15 g sample from one of the parts of the reduced total sample, place it in a porcelain, agate or metal mortar, grind for 5 minutes and sift through a sieve with mesh N 025K GOST 6613-86. If grains remain on the mesh and are attracted to the magnet, then the analysis result is considered negative.

By agreement with the consumer, the presence of malleable grains of nickel oxide is allowed. Their mass fraction () in percent is calculated by the formula

where is the mass of grains attracted to the magnet from the mesh after sifting, g;

Weight of sample, sample, g.

3.8-3.11. (Changed edition, Amendment No. 4).

3.12. It is allowed to carry out analyzes by other methods that ensure the accuracy of determination within the limits established by the standard.

In case of disagreement in the assessment of results, analyzes are carried out according to paragraphs 3.3-3.11.

(Introduced additionally, Amendment No. 4).
or steel drums, class 9, subclass 9.2, classification code 923.
______________
* GOST 14192-96 is in force on the territory of the Russian Federation. - Database manufacturer's note.

In addition, the transport container is marked with the following information:

name of the manufacturer and its trademark;

batch number;

designation of this standard.

(Changed edition, Amendment No. 2, 3).

4.3. (Deleted, Amendment No. 2).

4.4. Nickel oxide is transported by all types of transport in accordance with the rules for the transportation of (dangerous) goods in force for this type of transport.

The product, packaged in specialized containers, is transported by railway on open rolling stock; loading and fastening of containers is carried out according to the conditions for loading and fastening of cargo, approved by the Ministry of Railways of the USSR.

Nickel oxide, packed in barrels and drums, must be transported in cargo packages in accordance with the rules for the transportation of goods by the USSR Ministry of Railways, GOST 26663-85 using pallets in accordance with GOST 9078-84. Means of fastening cargo into transport packages - in accordance with GOST 21650-76.

(Changed edition, Amendment No. 3, 4).

4.5. Nickel oxide should be stored in packaged form in a dry, closed area of ​​the manufacturer's or consumer's warehouse.

Electronic document text
prepared by Kodeks JSC and verified against:
official publication
M.: Standards Publishing House, 1992

Physical properties

Nickel(II) oxide is a crystalline substance, depending on the method of preparation and heat treatment, its color ranges from light to dark green or black. It has two crystal modifications:

Receipt

In nature, nickel oxide occurs in the form of the mineral bunsenite - octahedral crystals, the color ranges from dark green to brownish-black depending on the impurities. Chemical composition non-stoichiometric NiO x, Where x= ~1 with Bi, Co, As impurities. Very rare, found in Johanneorgenstadt, Saxony.

Nickel oxide can be synthesized directly from elements by oxidation of Ni when heated in air or oxygen:

$\backslash mathsf(2Ni\; +\; O\_2\backslash \; \backslash xrightarrow(500-1000^oC)\backslash \; 2NiO)$

Nickel(II) oxide can be obtained by thermal decomposition into nickel(II) hydroxide or some salts of divalent nickel (carbonate, nitrate, etc.):

$\backslash mathsf(Ni(OH)\_2\backslash \; \backslash xrightarrow(230-250^oC)\backslash \; NiO+H\_2O)$ $\backslash mathsf(NiCO\_3\backslash \; \backslash xrightarrow(>300^oC)\backslash \; NiO+CO\_2)$

Chemical properties

Thermally, nickel oxide is very stable. Only at temperatures above 1230 °C does its reversible dissociation become noticeable:

$\backslash mathsf(2NiO\backslash \; \backslash rightleftarrows\backslash \; 2Ni\; +\; O\_2)$

It exhibits amphoteric properties (the main ones predominate), and is practically insoluble in water:

$\backslash mathsf(NiO\; +\; 7H\_2O\backslash \; \backslash rightleftarrows\backslash \; ^(2+)\; +\; 2OH^-)$ p PR = 15.77

Reacts with acids:

$\backslash mathsf(NiO\; +\; 2HCl\backslash \; \backslash xrightarrow\backslash \; NiCl\_2\; +\; H\_2O)$

During sintering, it interacts with alkalis and oxides of typical metals:

$\backslash mathsf(NiO\; +\; 2NaOH\backslash \; \backslash xrightarrow(400^\backslash circ\; C)\backslash \; Na\_2NiO\_2\; +\; H\_2O)$ $\backslash mathsf(NiO\; +\; BaO\backslash \; \backslash xrightarrow(1200^\backslash circ\; C)\backslash \; BaNiO\_2)$

With concentrated ammonia solution it forms ammino complexes:

$\backslash mathsf(NiO\; +\; 6(NH\_3\backslash cdot\; H\_2O)\backslash \; \backslash xrightarrow(T)\backslash \; OH\; +\; 5H\_2O)$

Reduced by hydrogen or other reducing agents (C, Mg, Al) to metal:

$\backslash mathsf(NiO\; +\; H\_2\backslash \; \backslash xrightarrow(200-400^\backslash circ\; C)\backslash \; Ni\; +\; H\_2O)$

When fused with acid oxides, it forms salts:

$\backslash mathsf(2NiO\; +\; SiO\_2\backslash \; \backslash xrightarrow(1200^\backslash circ\; C)\backslash \; Ni\_2SiO\_4)$

Application

The main use of nickel oxide is as an intermediate product in the preparation of nickel(II) salts, nickel-containing catalysts and ferrites. NiO is used as a green pigment for glass, glazes and ceramics. The production volume of nickel oxide is about 4000 tons/year.

Safety

Like all nickel compounds, its oxide is also poisonous. The maximum permissible concentration in the air for the working area is 0.005 mg/m³ (in terms of Ni).

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Notes

Literature

• Chemical Encyclopedia: In 5 volumes: volume 3: Editorial Board: Knunyants I.L. et al.-M., Great Russian Encyclopedia, 1992, 639 p.
• Lidin R. A., Molochko V. A., Andreeva L. L., Chemical properties inorganic substances, M., Chemistry, 2000.
• Ripan R., Ceteanu I., Inorganic chemistry, vol. 2 Chemistry of metals, M., Mir, 1972.

An excerpt characterizing Nickel(II) Oxide

Nickel(II) oxide

Nickel(II) oxide - inorganic binary compound of divalent nickel with oxygen. Chemical formula NiO. Occurs in nature as the rare mineral bunsenite.

Receipt

In nature, nickel oxide occurs in the form of the mineral bunsenite - octahedral crystals, color from dark green to brownish-black, depending on impurities. The chemical composition is non-stoichiometric NiOx, where x = ~1 with impurities of Bi, Co, As. Very rare, found in Johanneorgenstadt, Saxony.

Nickel oxide can be synthesized directly from elements by oxidation of Ni when heated in air or oxygen:

Nickel(II) oxide can be obtained by thermal decomposition into nickel(II) hydroxide or some salts of divalent nickel (carbonate, nitrate, etc.):

Physical properties

Nickel(II) oxide is a crystalline substance, depending on the method of preparation and heat treatment, its color ranges from light to dark green or black. cobalt nickel chemical hydrogen

Solid state

Molar mass74.69 g/mol

Density b-NiO 6.67 g/cm³

Thermal properties

Melting point 1682 °C

Decomposition temperature1230 °C

Molar heat capacity (st. conv.) 44.3 J/(mol K)

Enthalpy of formation (st. conv.) -239.7 kJ

Chemical properties

Thermally, nickel oxide is very stable. Only at temperatures above 1230 °C does its reversible dissociation become noticeable:

It exhibits amphoteric properties (the main ones predominate), and is practically insoluble in water:

Reacts with acids:

During sintering, it interacts with alkalis and oxides of typical metals:

With concentrated ammonia solution it forms ammino complexes:

Reduced by hydrogen or other reducing agents (C, Mg, Al) to metal:

When fused with acidic oxides, it forms salts

Application

The main use of nickel oxide is as an intermediate product in the preparation of nickel(II) salts, nickel-containing catalysts and ferrites. NiO is used as a green pigment for glass, glazes and ceramics. The production volume of nickel oxide is about 4000 tons/year. Like all nickel compounds, its oxide is also poisonous. The maximum permissible concentration in the air for the working area is 0.005 mg/m³ (in terms of Ni).