Chromium Compounds 1

Chromium Compounds
Gerd Anger, Leverkusen, Federal Republic of Germany (Chap. 2)
Jost Halstenberg, Bayer AG, Leverkusen, Federal Republic of Germany (Chaps. 3 – 4.1, 4.3 – 8, and 14)
Klaus Hochgeschwender, Bayer AG, Leverkusen, Federal Republic of Germany (Chaps. 9 – 13)
Christoph Scherhag, Bayer AG, Uerdingen, Federal Republic of Germany (Chaps. 9 – 13)
Ulrich Korallus, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 13)
Herbert Knopf, Bayer AG, Leverkusen, Federal Republic of Germany (Chaps. 3 – 4.1, 4.3 – 7, and 14)
Peter Schmidt, Bayer AG, Leverkusen, Federal Republic of Germany (Chaps. 3 – 4.1, 4.3 – 7, and 14)
Manfred Ohlinger, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chaps. 4.2 and
13)

1. Introduction . . . . . . . . . . . . . . . . . 2 5.2. Chromium(III) Sulfates and Chrome

2. Chromium Ores . . . . . . . . . . . . . . 2 Tanning Agents . . . . . . . . . . . . . . . 17
2.1. Ore Deposits . . . . . . . . . . . . . . . . . 4 5.3. Other Chromium(III) Salts . . . . . . . 19
2.2. Ore Beneficiation . . . . . . . . . . . . . 7 6. Chromic Acids and Chromates(VI) . 21
3. Production of Sodium Dichromate . . 7 6.1. Chromic Acids . . . . . . . . . . . . . . . 21
3.1. Alkaline Roasting . . . . . . . . . . . . . 7 6.2. Alkali Chromates and Dichromates . 22
3.2. Leaching of the Roast . . . . . . . . . . . 8 6.3. Other Chromates . . . . . . . . . . . . . 24
3.3. Acidification . . . . . . . . . . . . . . . . . 10 7. Other Chromium Compounds . . . . . 26
3.4. Crystallization . . . . . . . . . . . . . . . 11 8. Analysis . . . . . . . . . . . . . . . . . . . . 26
4. Chromium Oxides . . . . . . . . . . . . . 11 9. Transportation, Storage, and Han-
4.1. Chromium(III) Oxide and Chromium dling . . . . . . . . . . . . . . . . . . . . . . 27
Hydroxide . . . . . . . . . . . . . . . . . . 11 10. Environmental Protection . . . . . . . . 27
4.2. Chromium(IV) Oxide (Chromium 11. Ecotoxicology . . . . . . . . . . . . . . . . 28
Dioxide) . . . . . . . . . . . . . . . . . . . . 13 12. Nutrition . . . . . . . . . . . . . . . . . . . 28
4.3. Chromium(VI) Oxide . . . . . . . . . . . 14 13. Toxicology and Occupational Health . 29
5. Chromium(III) Salts . . . . . . . . . . . 16 14. Economic Aspects . . . . . . . . . . . . . 32
5.1. General Properties . . . . . . . . . . . . 16 15. References . . . . . . . . . . . . . . . . . . 33

1. Introduction quantities for the oxidation of chemical inter-

mediates. With the advent of the 20th century,
Historical. Chrome iron ore (chromite) was chrome tanning was introduced in leather facto-
discovered in 1798. A few decades later this ries and in many areas replaced vegetable tan-
ore was being subjected to oxidative roasting ning.
in the presence of soda and lime in manu- The manufacture of chromium compounds
ally operated furnaces to produce water-soluble received a further boost after 1930, when metal-
sodium dichromate. This was processed further lic chromium was successfully precipitated from
to yield yellow, red, and green chromium pig- chromic acid solutions by special additives.
ments which were used, among other things, for Since then this possibility has been used ex-
dyeing wallpaper; they replaced the toxic arsenic tensively in electroplating for bright and hard
dyes that had been used until then. Chromium chromium plating.
salts soon found their way into the textile indus- Chromium compounds are used in numerous
try as mordants for the dyeing of wool. fields. In addition to the applications mentioned,
The importance of dichromates increased chromates have long been used in printing as an
considerably in the period following 1870 when aid in photomechanical reproduction. For some
the rising coal tar dye industry needed large time, chromium dioxide has been a component

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a07 067
2 Chromium Compounds

of magnetic tapes for information storage. Ta- try, chromite is processed in conjunction with
ble 1 lists important applications of chromium magnesite (sintered magnesia, calcined magne-
chemicals. sia) and binders (clay, lime, gypsum, bauxite,
Table 1. Uses of chromium compounds
corundum). The products are intended to have
good resistance to pressure, fire, and tempera-
Branch of Product Use ture change, as well as good insulating properties
industry
between basic and acidic masonry. The chemical
Building chromium(III) oxide pigment for coloring building industry uses chromium ores in the production
industry materials of chromium compounds (Chaps. 34567). Ta-
Chemical dichromates, oxidation of organic
industry chromium(VI) oxide compounds, bleaching of ble 3 shows quality requirements of chromium
montan ores for different areas of application.
waxes, manufacture of
chromium complex dyes
chromium(III) oxide catalysts Minerals. Of the many minerals that contain
Printing dichromates photomechanical reproduction
industry processes
chromium only the chromium spinels are of eco-
chromium(VI) oxide chromium plating of printing nomic importance. The formula for the series of
cylinders isomorphous mixtures of chromium spinels that
Petroleum chromates(VI) corrosion protection
industry form geological deposits is
Paints and chromates, pigments (FeII , Mg)O · (Cr, Al, FeIII )2 O3
lacquers chromium(III) oxide
Refractory chromium(III) oxide additive for increasing slag
The proportion of Cr2 O3 in the chromium
industry resistance spinels varies widely, causing the Cr : Fe ra-
Electro- chromium(VI) oxide bright and hard chromium tio (also known as the Cr – Fe factor) to vary as
plating plating
Wood chromates, in mixtures of salts for well; this can have a profound effect on the eval-
industry chromium(VI) oxide protecting wood against fungi uation of a deposit. In an ideal chromium spinel
and insects
Leather basic chromium(III) tanning of smoothed skins (FeO · Cr2 O3 ; 67.8 % Cr2 O3 , 32.2 % FeO) the
industry sulfates chromium : iron ratio is 2. As a result of the iso-
Metal chromium boride, flame sprays morphous inclusion of MgO, the Cr : Fe ratio
industry chromium carbide
chromium(III) oxide polishing agents may rise to between 2.5 and 5. Figure 1 shows
Metallurgy chromium(III) oxide aluminothermic extraction of the region of isomorphism with varying compo-
pure chromium metal
Textile dichromates dyeing with chrome dyes sition of the spinels. Natural chromium spinels
industry usually contain 33 – 55 % Cr2 O3 , 0 – 30 %
basic chromium(III) mordanting of textiles Fe2 O3 , 0 –30 % Al2 O3 , 6 – 18 % FeO, and
acetates and
chromium(III) 10 – 32 % MgO. Table 4 lists some physical
fluorides properties of chromium spinels.
Recording chromium(VI) oxide magnetic information storage
industry
Pyrotechnicsdichromates additive to igniting mixtures
industry

2. Chromium Ores [4–16]

The distribution of chromium in terrestrial rocks
is closely linked to magmatic intrusions and their
crystallization. The average content in the ten-
mile crust of the earth is 100 ppm of chromium
[10]. Table 2 contains a worldwide estimate of Figure 1. Ternary spinel system showing main isomorphous
chromium ore resources. region
The most important applications of
chromium ores are in the manufacture of stain- Chromium also occurs in all groups of sil-
less steel, grey cast iron, iron-free high-tempe- icates where chromium replaces Al3+ , Fe3+ ,
rature alloys, and chromium plating for surface and Mg2+ . Sulfidic chromium ores do not oc-
protection. In the nonmetallic mineral indus- cur on earth. Chromates and chromium iodates
 Chromium Compounds 3
Table 2. Estimated reserves of chromium ore [70]

Reserves, 106 t

Total Metallurgical a , Chemical a , Refractory a ,

> 45 % Cr2 O3 > 40 % Cr2 O3 > 20 % Al2 O3

Republic of South Africa 2000 b 100 (5 %) 1900 (95 %) –

Zimbabwe 600 300 (50 %) 300 (50 %) –
Turkey 10 9 (90 %) – 1 (10 %)
Philippines 7.5 1.5 (20 %) – 6 (80 %)
United States 8 0.4 (5 %) 7.4 (92.5 %) 0.2 (2.5 %)
Canada 5 – 0.5 (100 %) –
Finland 7.5 – 7.5 (100 %) –
Others 11.35 8.175 (72 %) 0.2 (2 %) 2.975 (26 %)

Total 2649.35 419.075 (16 %) 2220.1 (84 %) 10.175 (0.4 %)

Former USSR and other Eastern

bloc countries 51.5 26.5 (51 %) 15 (29 %) 10 (20 %)

Total worldwide (rounded off) 2701 446 (17 %) 2235 (83 %) 20 (1 %)

a
Graded according to Cr2 O3 or Al2 O3 contents.
b
Ores containing 30 – 50 % Cr2 O3 .

Table 3. Quality requirements (mass fractions in %) for chromium ores (according to U.S. Bureau of Mines)

Metallurgical a Refractory b Chemical c

(high-chromium chromite) (high-aluminum chromite) (high-iron chromite)

Cr : Fe ratio 3 : 1 or higher – –
Cr2 O3 >48 >31 >44
Cr2 O3 + Al2 O3 – >58 –
Fe – <12 –
SiO2 <8 <6 <5
S <0.08 – –
P <0.04 – –
CaO – <1 –
a
Zimbabwe, South Africa, Turkey, former USSR.
b
Turkey, Philippines.
c
South Africa, former USSR.

are described, which originate from the weather- 2.1. Ore Deposits
ing zone of sulfidic lead deposits (e.g., crocoite,
PbCrO4 ). Chromium ore deposits can be divided into two
genetically different types:
Table 4. Physical properties of chromium spinels
1) Seam-like deposits, also called stratiform or
Properties Notes anorogenic deposits. Main representatives
Specific density: 3.8 – 4.8 increases as Fe and Cr are Bushveld, Great Dyke, and Stillwater.
contents increase 2) Deposits which are shaped like sacks or
Hardness (Mohs): 4.5 – 8 increases with increase in the
ferrochromite component,
tubes; they are called podiform or orogenic
very high for Al spinels deposits. Main representatives are Selukwe,
Melting point: 1545 – 1730 ◦ C inclusion of Mg raises Guleman, and Tiébaghi.
melting point, inclusion of
Fe2+ reduces it
Color: dark brown to black reddish with high Cr2 O3 Various intermediate types such as adjacent
content “seam” pockets, striated chromite slabs, mottled
Streak on porcelain plate; important feature for
differentiating
ores, and vein-like deposits also occur. “Placer”
hammer striking mark: brown from serpentine deposits, i.e., enrichment due to chromite lumps
4 Chromium Compounds

and grains on or near primary deposits, are now chromium ore in the world. All the deposits are
achieving economic importance. distributed in ultrabasite massifs in the Central
The seam-like deposits reveal layers or strata and Southern Urals. The deposits that are most
of chromite enrichment, with thicknesses rang- important at present were found in the late 1930s
ing from centimeters to decimeters; the layers in the Akhtiubinsk region (North Kazakhstan).
are regularly interlaminated with banded series The Donskoye deposit, which is associated with
of olivine-rich or pyroxene-rich rocks. The Main the mining settlement of Khrom Tau, contains
Seam of the Western Bushveld is, for example, high-grade chromium ores for ferrochromium
1.10 – 1.30 m thick and can be traced for over production and low-grade ores for chemical pur-
65 km without any significant change in the min- poses. Mining is carried on in numerous open-
eral composition or thickness. pit mines, which implies that the ore bodies are
The demarcation between the chromite en- small. A new open-cast mine was put into pro-
richment and the underlying bed is usually razor- duction near Donskoye, as is a processing plant
sharp; in the direction of the overlying layer, dis- with a throughput of 106 t/a. Strong prospection
integration into layers or mottled ores as a result effort for new occurrences is being made in the
of increased silicate content is observed. Northern Urals, but because of the rough climate
The chromite bodies that are sack-like to no mine has been opened up to 1986.
tube-like in appearance are usually aligned with
the direction of the magmatic stratification, i.e., Bushveld. In the Bushveld (Republic of
the lowest sections are massive chromite ores; in South Africa) mining began in the 1920s in
the direction of the overlying layer, these merge two districts: the Lydenburg district (Eastern
into striated slabs or mottled ores. Bushveld) and the Rustenburg district (Western
The internal texture of the chromite ore bod- Bushveld).
ies varies widely. The closest chromite crystal From a geological and petrological point of
packing results in the formation of massive ores view this is a large intrusion of 500×250 km
containing 75 – 85 vol% of chromite. Sphere or with a thickness of over 5 km. The chromite
leopard ores, which consist of round chromite “seams” are located in the pyroxenite – norite
crystal aggregates 0.5 – 2 cm in diameter in a sil- zone of the basal section of the intrusion, always
icate matrix (olivine, pyroxene, serpentine), are below the platinum-bearing Merensky Reef. In
also characteristic. Banded ores are closely re- the case of Rustenburg there are up to 25
lated to the massive ores, but they are frequently chromite seams on top of each other. The thick-
richer in silicate and then form a link with the ness of the individual seams varies from a few
mottled ores (chromite single crystals in silicate centimeters to 1.80 m. The seams are workable
matrix). from 0.35 m upward, especially if they can be
During transformation (serpentinization), the combined into mining units (Cr2 O3 content in
silicate content within the chromite ore bodies the crude ore 30 – 40 %; Cr : Fe ratio = 1.6 – 2.3).
has resulted in the formation of friable and pul- In the Lydenburg district, which is genetically
verizable masses (friable ore) which are encoun- very similar to the Rustenburg district, only two
tered not only near the surface but also at depths seams are being mined; the Cr2 O3 content is
of several hundred meters below the present-day 44 % and the chromium : iron ratio 1.6 – 1.7. The
land surface. iron content is frequently high, which may cause
Chromite transformation in the course of difficulties in the case of metallurgical ores;
more recent tectonic superficial modification un- however, these ores are highly valued as chemi-
der pneumatolytic or hydrothermal conditions cal ores.
has resulted in the striking colors of recent
uvarovite, smaragdite, and kammererite forma- Great Dyke. The Great Dyke (Zimbabwe) is
tions which act as pathfinders in prospecting and an intrusion which is 610 km long and 6 – 9 km
exploring for chromite deposits. Table 5 shows thick – a remarkable length : thickness ratio
some analyses of selected chromium ores. which is unique in the world. The internal struc-
ture is similar to that of the Bushveld. From north
Former Soviet Union. The former Soviet to south, the individual complexes are Musen-
Union is one of the most important producers of gezi, Hartley, Selukwe, and Wedza. Selukwe
 Chromium Compounds 5
Table 5. Chemical analyses (mass fractions in %) of some chromium ores (crude ores, concentrates)

Country Cr2 O3 FeO SiO2 MgO Al2 O3 CaO V2 O5 Cr : Fe ratio

South Africa
Rustenburg (c) a 44.5 26.4 3.5 10.6 14.4 n.d. b 1.7 : 1
Lydenburg (c) 44.3 24.6 2.3 11.2 16.1 0.4 1.8 : 1

Zimbabwe
Great Dyke (m) a 48.5 18.3 5.6 13.4 11.5 0.8 2.6 : 1
Great Dyke (r) a 50.7 16.4 4.3 13.2 13.0 0.8 3.1 : 1
Selukwe (m) 47.0 12.0 5.7 15.5 12.6 1.8 3.9 : 1
Selukwe (r) 42.0 15.7 8.6 15.8 13.8 0.3 2.7 : 1

Turkey
(m) 48.3 14.1 5.1 16.8 13.0 0.9 3.4 : 1
(r) 37.0 15.2 4.3 17.7 24.3 0.2 2.4 : 1

Philippines
(Masinloc) (r) 33.3 13.2 4.6 19.6 28.2 0.4 2.5 : 1

Finland (Kemi)
Crude ore 26.5 15.0 18.5 19.5 9.5 – 0.04 – 0.1 1.8 : 1
Concentrate 45.7 33.8 0.4 2.9 13.6 n.d. 0.1 1.4 : 1

Albania
(m, r) 43.0 16.2 9.8 22.2 7.9 0.1 2.6 : 1

Former USSR
(m) 53.9 12.6 5.8 13.3 9.6 1.1 4.3 : 1
(r) 39.1 14.0 9.4 16.1 17.4 0.7 2.8 : 1
a
(m) = metallurgical, (r) = refractory, (c) = chemical.
b
n.d. = not determined.

Table 6. Analysis of chromium ores from Zimbabwe

Cr2 O3 Cr : Fe ratio Proportion,

content, wt % wt %

Metallurgical over 48 over 2.8 80

Chemical 45 – 48 2.2 – 2.5 17
Refractory 42 – 46 1.8 – 2.0 3

consists of sack-like deposits containing 48 % Other Ore Deposits

Cr2 O3 and even more, with a chromium : iron
ratio greater than 2.8 (a highly valued metal- Madagascar. On the island of Madagascar,
lurgical ore). In the Hartley region, on the other chromium ores are being mined since 1967 with
hand, numerous bands and seams 2 – 75 cm thick an annual production of around 60 000 t of met-
are being mined; these are separated by serpen- allurgical grade ore. Total output is calculated
tinized peridotite layers, some of which are very to be almost 2×106 t since the beginning of the
thick and make mining very difficult. However, operation (50 – 52 % Cr2 O3 ). The reserves are
the Cr2 O3 content varies between 48 and 57 %, said to be around 5.5×106 t.
and the chromium : iron ratio is over 2.8 (Ta-
ble 6). Turkey. Turkey still is the traditional coun-
According to conservative estimates, 1 km2 try for chromite deposits of metallurgical qual-
of the Great Dyke contains around 1.4×106 t of ity, but because of falling prices on the world
crude ore, which corresponds to assured reserves market and exhaustion of reserves, many mines
of 600×106 t (geologically 4.6×109 t are possi- have been forced to close. The most important
ble). regions belong essentially to the alpidic era, e.g.,
Bursa, Mugla district, and Elazig, including the
Guleman chrome ore field. Open-pit mining, and
6 Chromium Compounds

in some places underground mining at shallow to the podiform type and normal grades are
depths, are employed. reported to be 43 % Cr2 O3 with a Cr : Fe
ratio of 3 : 1. The largest chrome ore mines
Iran. Chromite deposits are described in two are Bulquize and Matanesh with concentration
regions of Iran: northwest of Sabzawar near plants of 300 000 t/a each.
Mashad and 200 km northeast of the Gulf port of
Bandar Abbas. These deposits are pocket-like,
sometimes containing only 500 t of ore. Extrac- 2.2. Ore Beneficiation
tion is by open-pit mining and by primitive un-
derground mining. Only hard lump ore for met- The simplest method of concentrating chromite
allurgical applications is sometimes exported. is by hand picking; this is still employed today
at many pits, including those in Turkey, Brazil,
Philippines. On the Philippine island of Lu- Iran, and the Philippines. Because the mining
zon the most important chromite deposits are of richer ores continues to decline, concentrat-
to be found in the Coto region (near Masin- ing procedures, chiefly using the gravity method,
loc, province of Zambales). These are chromite have been developed to separate the serpentine
seams and pockets within layered dunites and from the chromite. For example, in South Africa
harzburgites. They are classical metallurgical or Brazil the chromite ores are enriched by
and refractory ores. More recently a new type crushing, milling, screening, and sophisticated
of chrome ore has been put into production: gravity procedures. In South Africa, spirals and
chromite from lateritic soils. The concentrates diamond pans are standard equipment. A com-
are suited for the chemical industry. bination of Reichert cones and Reichert spirals
has also been employed. Although the costs are
Finland. In 1959 a fairly large deposit higher, the use of hydrocyclones for separating
of chromite was discovered near Kemi, the fine chromite grains from waste is of great
which has been developed into a pro- importance in the recycling of tailing dumps.
ductive mine. Chromium ore occurs in a Some chromium ores contain magnetite which
serpentinite – anorthosite massif 12 km long and can be removed by means of magnetic separa-
1 – 2 km wide; the ore zone, however, is only tion. However, if the magnetite is present as an
15 – 100 m thick and dips at an angle of 60◦ to- individual phase within the chromite grains or as
ward the north. The Cr2 O3 content of the crude a fringe around the grains, this method is only
ore of the various ore bodies varies between 17.5 suitable if Cr2 O3 is further enriched. Flotation
and 21.9 % (locally even up to 30.5 % Cr2 O3 ); and electrostatic processes have so far enjoyed
the chromium : iron ratio is low (0.81 – 1.87). little success in the concentration of chromium
ores. If the Cr2 O3 content or the chromium : iron
Former Yugoslavia. The deposits of ratio is sufficient, fine-grained chromite concen-
chromite in former Yugoslavia are restricted to trates can be briquetted or pelleted with the aid
the Raduša massif near Skopje, but the mining of of binders.
metallurgical ores there has fallen considerably. The yield (65 – 85 % of the chromite actually
Native ores are being processed in a new plant, contained in the crude ore) depends on many
whereas ores imported from Albania are being factors including the nature of the chromite –
processed in the old one. The chromium ores serpentine intergrowth, grain size, and Cr2 O3
are always associated with serpentinized ultrab- content of the ore or individual grain.
asites. The striated slab type predominates, but At the chromite concentration plant at Kemi
massive chrome ores are encountered in some in Finland a fraction of the crude ore (70 %)
places. is crushed to below 10 mm in a primary crusher
plant at the open-pit mine. After further grinding
Albania. Since 1960, Albania has become (rod and ball mill) and removal of sludge, the in-
the third largest producer in the world. All termediate product is dried in a rotary kiln. The
actual data are based on estimates because magnetic separation (a combination of weak and
the Albanian government withholds production strong fields) produces two concentrates: con-
and export figures. Albanian deposits belong centrate 1 containing 45.9 % Cr2 O3 , which is
 Chromium Compounds 7

sold or used as molding sand, and concentrate 2 the type of ore used and the composition of the
containing 42.0 % Cr2 O3 for the production of mixture.
ferrochromium.
Process Description. A typical roast mix-
ture contains 100 parts of ore, 60 – 75 parts
3. Production of Sodium Dichromate of sodium carbonate, 0 – 100 parts of lime or
dolomite, and 50 – 200 parts of inert materials.
Directly or via several intermediate stages, The components are first finely ground, then
sodium dichromate [7789-12-0], Na2 Cr2 O7 · mixed, and fed into the furnace. Annular hearth
2 H2 O, is the starting material for the production furnaces or rotary kilns are commonly used in
of all chromium compounds and pure chromium large plants today.
metal. The annular hearth furnace (Fig. 2) is made
Sodium dichromate is made in a three-step from steel with a refractory lining (inner diame-
process: (1) alkaline roast of chromite under ox- ter ca. 20 m; outer diameter ca. 30 m); it is driven
idizing conditions (Eq. 1), (2) leaching, and (3) by a gear wheel underneath and has rails running
conversion of sodium monochromate to sodium on rollers. The rotating hearth is sealed from the
dichromate by means of an acid (Eq. 2). stationary parts of the furnace by sheets of metal
dipping into annular water troughs. The furnace
is heated by several burners from the side or from
the top with gas, coal dust, or oil. The exhaust gas
can be utilized to preheat the burner air or to gen-
erate steam. The mixture is fed to the outer edge
of the annular hearth by a feed screw. A water-
cooled ribbon screw transports the mixture in-
3.1. Alkaline Roasting ward, each time the annular hearth revolves, and
finally removes it in the middle.
Soda ash (sodium carbonate) is generally used In the annular hearth furnace, the mixture is
as the alkali component but sodium hydroxide uniformly heated to the reaction temperature and
may also be employed [17–19]. The degree of made to travel toward the center of the hearth
solubilization of chromites by the roasting pro- with a well-defined layer thickness. The furnace
cess depends on their composition. For optimum process is fairly independent of the sintering
results, the process is controlled by adding so- of the roast; it allows the production of melts
called carrier materials. These ensure sufficient that contain 40 wt % of water-soluble sodium
porosity of the material so that oxygen can dif- chromate. The yield is 80 – 95 %, based on the
fuse into the roast. Porosity is maintained by chromite feed. The roast takes 2 – 6 h, depending
means of such materials as iron oxide, bauxite, on the composition of the mix.
or dried leach residue; CO2 -emitting additives Most of the kiln tube of the rotary kiln (Fig. 3)
include lime and/or dolomite. The inert addi- between the feed point and the reaction zone is
tives dilute the sodium carbonate and sodium used to heat the mixture. Shortly before the mix
chromate, which both melt at the reaction tem- reaches the actual reaction zone, the soda melts
perature. In the low-lime process the carbon- and calcines. At this point the mixture bakes, and
ates evolve CO2 , decrease the reaction temper- pellets or wreath-shaped cakes may be formed.
ature to below 1000 ◦ C, and raise the melting If the furnace is operated inexpertly (tempera-
point of the reaction products; the amount of ture too high) or the composition of the mixture
lime added must be controlled so that the com- is wrong (too little carrier material) the kiln tube
pound 5 Na2 CrO4 · CaCrO4 [20] is produced may get substantially clogged. In such cases, the
in the roast. Temperatures above 1150 ◦ C must constriction can be cleared by using an industrial
be avoided because they result in the subsidiary gun.
components of the ore being attacked. At still The roast from the rotary kiln contains up to
higher temperatures the degree of conversion is 30 wt % of water-soluble sodium chromate. The
markedly decreased. The optimum temperature yield is 75 – 90 %, based on the chromite feed.
range is very narrow and depends strongly on
8 Chromium Compounds

Figure 2. Annular hearth furnace

a) Mixture silo; b) Scales; c) Feed screw; d) Furnace; e) Annular hearth; f) Water-cooled ribbon screw; g) Wet tube mill;
h) Stirred vessel; i) Pump for filtering system; j) Waste heat boiler; k) Electrostatic gas purification; l) Exhaust gas fan; m) Dust
drag chain; n) Bin filter; o) Rotation axis

The roast takes 3 – 8 h, depending on the compo- haust gas cooling system, with optional energy
sition of the mixture. The hot exhaust gas from recovery, for example, steam generation; and (2)
the rotary kiln can be used to preheat the burner the exhaust gas purification system, usually an
air. electrostatic separator. The size and the design
Gas Purification. Exhaust gas purification of the purification system depend on the type
systems able to achieve a high degree of sep- of furnace. In the rotary kiln, ca. 10 % of the
aration are required for dust collection. They es- feed mixture is carried off by the exhaust gas,
sentially consist of two components: (1) an ex- whereas in the annular hearth furnace, less than
 Chromium Compounds 9

Figure 3. Rotary kiln for roasting chromium ores

a) Mixture silo; b) Scales; c) Elevator; d) Drag chain; e) Inlet tube; f) Rotary kiln; g) Combustion chamber; h) Burner;
i) Crusher; j) Wet tube mill; k) Stirred vessel; l) Pump for filtering system; m) Kiln inlet; n) Waste heat boiler; o) Electrostatic
gas purification; p) Exhaust gas fan; q) Dust drag chain; r) Bin filter; s) Air inlet

1 % is carried off. However, operation of the an- The roast is first cooled on a Fuller grate or
nular hearth furnace necessitates a considerable in a cooling drum. Then it is either ground in
expenditure on gas cooling. a wet tube mill after addition of water or wash
solution (see below) with carbonates or acids
Other Processes. In the literature, other pro- added, or it is dissolved in a stirred vessel. The
cesses are proposed but so far these have not insoluble residue is separated from the sodium
achieved any industrial significance. Thus, at- chromate solution and thoroughly washed with a
tempts have been made to roast chromium ore countercurrent of water. Continuous multistage
in a shaft furnace [21] or in a fluidized-bed reac- Dorr plants or rotary filters are used; after sep-
tor [22]. A fundamentally different process in- aration, the insoluble residue is extracted two
volves the reaction of the chromium ore and soda to three more times in counterflow. Dorr plants
in a molten salt mixture with oxygen-containing only exhibit satisfactory separation of residue
gases being injected [23]. and solution if the sodium chromate concentra-
tion is not too high. Rotary filter plants can be
employed without difficulty for nearly saturated
3.2. Leaching of the Roast hot sodium chromate solutions; such filters are
frequently preferred because the higher water
After the oxidative process, the roast is a mix- consumption of the Dorr plant results in unnec-
ture of soluble salts and insoluble compo- essary steam costs in the subsequent evaporation
nents. It contains sodium chromate, sodium process.
aluminate, magnesium oxide, sodium vana- After removal of residual aluminum hydrox-
date(V), iron(III) oxide, unused alkali, un- ide and other undissolved components in a final
changed chromite, and small amounts of sodium purification process (e.g., thickener), the con-
chloride originating from the soda. centrated sodium chromate solution is acidified
When the roast is extracted with hot water, a (Section 3.3).
pH of 10.5 – 11.2 results. The pH is controlled Some of the filter residue is dried and added
by adding acids or carbonates so that all chro- to the roasting mix (Section 3.1). The remain-
mate dissolves, whereas the alkali-soluble im- der is subjected to reducing treatment to con-
purities hydrolyze and form a readily filterable vert the residual chromate content into an eco-
precipitate along with the iron hydroxide and the logically harmless form. To do this, the residue
unchanged ore components.
10 Chromium Compounds

is suspended in water and treated with sulfu- The sodium hydrogen carbonate is removed
ric acid and sodium hydrogen sulfite or iron(II) by centrifugation or filtration, preferably under
sulfate; chromate residues are converted into pressure to prevent reaction (4) from being re-
chromium(III) compounds in this way. Subse- versed. After it has been washed, water can be
quent addition of alkali precipitates trivalent removed in a pusher centrifuge. Still moist, the
chromium (and iron(III), if present) as hydrox- sodium hydrogen carbonate is then transferred
ide. The suspension is then filtered and the cake to a calcining furnace. The carbon dioxide pro-
(optionally after further removal of water) is duced in the furnace may be fed back to the
dumped. acidification autoclaves [2]; the sodium carbon-
ate obtained is recycled for alkaline ore roasting
[24].
3.3. Acidification To obtain commercial sodium dichromate so-
lution, further evaporation to a concentration
The sodium chromate solution is converted of 1000 g of sodium dichromate per liter is re-
into sodium dichromate solution by acidifica- quired. This is then followed by a second acidi-
tion with sulfuric acid (Eq. 3) or carbon diox- fication with carbon dioxide or sulfuric acid.
ide (Eq. 4). The sequence of individual steps de- Production of soda is the main advantage of
pends on the acid. carbon dioxide acidification. However, this is
offset by a number of difficulties, particularly the
2 Na2 CrO4 + H2 SO4 −→ Na2 Cr2 O7 + Na2 SO4 + H2 O(3) formation of deposits on the evaporator during
the concentration of the sodium monochromate
2 Na2 CrO4 + 2 CO2 + H2 O
Na2 Cr2 O7 + 2 NaHCO3 (4)
solution. Other problems include mastering the
pressure technology and cooling, separation of
the sodium hydrogen carbonate, yield loss due to
Sulfuric Acid Acidification. Sulfuric acid reverse reaction, and clogging of the calcination
is added to the concentrated sodium monochro- furnace.
mate solution in an agitated vessel until the pH is
about 4. The sodium dichromate solution is then
concentrated in a continuous evaporation plant. 3.4. Crystallization
Each liter of sodium dichromate solution yields
400 – 500 g of anhydrous crystalline sodium sul- For the purpose of crystallization the sodium
fate. The sulfate is removed by centrifugation. dichromate solution (950 – 1200 g/L) is further
The clear, dark-red sodium dichromate solution concentrated and may, if necessary, be filtered
contains 900 – 1200 g of Na2 Cr2 O7 · 2 H2 O per while hot to remove additional sodium sulfate
liter and additional small amounts of sodium sul- or sodium chromate. It is then slowly cooled
fate; it is dispatched in tanks, e.g., of steel. The to 30 – 35 ◦ C with constant stirring to obtain
solution is either used directly as an oxidizing orange-red crystals of Na2 Cr2 O7 · 2 H2 O.
agent or processed to yield dichromate crystals. Today continuous vacuum crystallization is
carried out to an increasing extent. The initial
Carbon Dioxide Acidification. After filtra- difficulties of this process, particularly in obtain-
tion the sodium monochromate solution from ing coarse, dust-free crystals, have largely been
the first filtration stage is concentrated to ca. overcome. The crystalline slurry is continuously
850 g of Na2 CrO4 per liter. The saturated sodium separated from the mother liquor and dried. Pre-
chromate solution is then acidified with a coun- cise control of the drying temperature is impor-
tercurrent of carbon dioxide at 0.5 – 1.5 MPa tant because hydrated sodium dichromate is con-
(5 – 10 bar) to yield sodium dichromate and verted into anhydrous sodium dichromate above
sodium hydrogen carbonate. A series of stirred 84.6 ◦ C and, therefore, cakes if overheated.
autoclaves is preferred for this reaction. They For reasons of occupational health, care
must be cooled to remove the heat of neutral- should be taken to ensure that workplaces and
ization; the slurry leaves the last reactor at room production plants are dust free when sodium
temperature. The degree of conversion is about dichromate, especially the dried product, is be-
80 – 90 %. ing handled. In such locations, extensive venti-
 Chromium Compounds 11

lation and dust removal systems (wet scrubbers, by sulfur [25], with sodium thiosulfate being
electrostatic separators) are necessary. produced as a coproduct. The hydrate initially
obtained is washed by decanting, filtered, and
calcined to form the oxide.
4. Chromium Oxides Chromium(III) oxide destined for alu-
minothermic production of pure chromium
4.1. Chromium(III) Oxide and metal must be heated additionally at 1000 ◦ C
Chromium Hydroxide to increase its grain size. If products partic-
ularly low in sulfur are to be produced for
Chromium(III) oxide [1308-38-9], Cr2 O3 , this purpose, charcoal can be used for the re-
M r 151.99,
5.2 g/cm3 , is green in finely dis- duction instead of sulfur. High-purity oxides
persed form, whereas fairly large crystals have can also be obtained by thermal decomposition
a blackish green hue and a metallic luster. The of chromium(VI) oxide or ammonium dichro-
crystals have a hexagonal rhombohedral struc- mate(VI), the latter yielding a material of very
ture of the corundum type. The compound melts low density.
at 2435 ◦ C, but begins to evaporate at 2000 ◦ C Chromium (III) oxide pigments contain
to form clouds of green smoke; the boiling point 99.1 – 99.5 % Cr2 O3 . The aluminum oxide
is estimated to be 3000 – 4000 ◦ C. The enthalpy and silicon dioxide impurities each amount
of formation is − 1141 kJ/mol. Macrocrystalline to ca. 0.1 %; the annealing loss at 1000 ◦ C is
chromium(III) oxide has a hardness of 9 on the about 0.3 %. The individual particles are spher-
Mohs scale. An amorphous form of the oxide is ical, with a diameter of 0.3 µm predominating.
also known; this crystallizes on heating. Chromium(III) oxide finds widespread applica-
Chromium(III) oxide does not dissolve in wa- tion as a green pigment resistant to atmospheric
ter, acid, alkali, or alcohols. It is converted by conditions and heat. In addition, it is used as a
a molten bath of sodium peroxide into solu- colorant in glass products and printing inks, as a
ble sodium monochromate(VI). Chromium(III) vitrifiable pigment in the ceramics industry, and
oxide and chromates(III) are used in organic as a polishing agent because of its considerable
chemistry as catalysts, e.g., in the hydrogenation hardness (→ Pigments, Inorganic).
of esters or aldehydes to form alcohols and in the
cyclization of hydrocarbons. They also catalyze Chromium(III) Aquoxides [12292-46-5],
the formation of ammonia from hydrogen and [12182-82-0]. Pure chromium(III) hydroxide
nitrogen. [1308-14-1], Cr(OH)3 , M r 103.02, can only be
Production. The industrial production of prepared with difficulty because the hydrates
chromium(III) oxide involves the reduction of initially obtained by precipitation are subject to
solid sodium dichromate, generally with sul- aging.
fur. The finely divided components are thor- After drying in air, specimens prepared by
oughly mixed, fed into a brick-lined furnace, precipitation with alkali in the cold from violet
and brought to dark-red heat. The reaction pro- chromium(III) salt solutions have a composition
ceeds exothermically. After the reaction mass corresponding to Cr2 O3 · 9 H2 O [12182-81-9],
has cooled, it is broken up and the sodium sulfate and are usually formulated as Cr(H2 O)3 (OH)3
produced is leached out with water. The remain- [41993-26-4]. They are bright bluish green pow-
ing solid is separated, rinsed, dried, and ground. ders with limited life. All three hydroxyl groups
To obtain 100 kg of chromium(III) oxide, 200 kg react immediately with acids. Upon careful heat-
of sodium dichromate must react with at least ing, dehydration occurs in steps and compounds
22 kg of sulfur; usually an excess of sulfur is containing 8, 5, 3, and 1 mol of water are formed.
used. Additives such as ammonium chloride or The density increases as the water content falls.
starch in the crude mixture affect the pigment Above 50 ◦ C, conversion to a gelatinous green
properties. When sodium dichromate is replaced aging product occurs, and the solubility and
by the corresponding potassium salt, the hue of chemical reactivity decrease; oxygen bridges are
the pigment becomes more bluish. formed through the elimination of water, and
The compound can also be prepared by a wet polynuclear complexes are produced. The com-
route involving reduction of sodium chromate position approaches that of chromium(III) oxide
12 Chromium Compounds

hydroxide, CrO(OH) [20770-05-2]. Aging is ac- It is produced by heating a ground mixture of

celerated by the presence of hydroxide ions. one part by weight of potassium dichromate and
In freshly precipitated hydroxides a three parts by weight of boric acid in a muffle
crystalline phase isomorphic with bayerite furnace to a faint red heat, which results in the
[Al(OH)3 ] is observed (→ Aluminum Oxide), formation of chromium(III) and potassium tetra-
whereas aged compounds are X-ray amorphous. borates. The molten mass still contains 6 – 7 %
The chromium(III) hydroxide hydrates are am- water and, after cooling, already has a deep
photeric compounds. With acids they form Cr3+ green color. When this mass is boiled with wa-
salts, whereas they dissolve in strong hydrox- ter, it decomposes into chromium(III) oxide
ide solution to form chromates(III), e.g., the hydrate and boric acid. The product is coarse-
deep green sodium chromate(III), Na2 Cr2 O4 grained and difficult to grind. Use of sodium
(previously known as sodium chromite). When dichromate as raw material results in a more
ammonium hydroxide is added, red solutions yellowish color, whereas addition of thiourea or
are formed. Oxidizing agents in the presence polysulfide to the reaction mixture produces a
of alkali produce chromates(VI). With halogens pigment with a bluish hue. The composition of
this takes place immediately on gentle heating, the commercial products varies; typical values
but with oxygen several hours are required at a are: Cr2 O3 79.3 – 82.5 %, H2 O 16.0 – 18.0 %,
pressure of 4 MPa (40 bar) at 175 ◦ C. B2 O3 1.5 –2.7 %.
Chromium(III) hydroxide forms a stable col- Hydrated chromium oxide green is a pig-
loid solution, whose isoelectric point is at pH ment with properties similar to those of
5. At higher pH the sol becomes negatively Guignet’s green but with a somewhat less inten-
charged and adsorbs cations, whereas below pH sive coloration. This pigment is prepared by re-
5 the charge is positive and anions are adsorbed. ducing sodium chromate or sodium dichromate
The adsorption capacity of chromium(III) hy- in aqueous solution with sulfur or sodium for-
droxide sols is higher than that of aluminum or mate in a stirred autoclave or pressure tube [28].
iron(III) hydroxide sols. Sols containing 127 g of The temperature required is 250 – 270 ◦ C. The
Cr2 O3 per liter have been obtained from concen- solid is separated by filtration, washed, dried,
trated chromium(III) chloride solution by addi- and ground. The finished pigment consists of
tion of ammonium carbonate and dialysis while fine needles, with a particle size of 0.02×0.1 µm
the solution is hot [26]. predominating. The product contains 79 – 80 %
Production. In industry chromium(III) hy- Cr2 O3 , the annealing loss is about 19 %, and the
droxide hydrates are usually produced from so- density 3.7 g/cm3 . The coloration changes at ele-
lutions of chromium(III) sulfate or chromium vated temperature. Because of its high reflecting
alum by precipitation with soda, sodium hy- power at infrared wavelengths the product had at
droxide solution, or ammonium hydroxide. Pro- times been of special importance in camouflage
duction by reduction of sodium chromate with paints.
sodium sulfide [27] has also been proposed.
For production from potassium chromium
alum 54 kg of soda is dissolved in 300 L of wa- 4.2. Chromium(IV) Oxide (Chromium
ter and a solution of 180 kg of alum in 900 L Dioxide)
of water is added slowly. After the evolution
of carbon dioxide has subsided, about 220 kg Wöhler discovered ferromagnetic chromium
of moist chromium hydroxide containing 12 % dioxide in 1859 when he decomposed chromyl
Cr2 O3 is obtained by filtration. Chromium(III) chloride [29]. About 100 years later, Du Pont
hydroxide hydrates are used for the production produced it in pure form by decomposition of
of chromium(III) salts by reaction with the cor- chromic acid under hydrothermal conditions
responding acids. [30], [31]. Industrial exploitation began after
Hydrated chromium(III) oxide, Cr2 O3 · the morphological and magnetic properties had
x H2 O, is a brilliant emerald-green pigment been modified by doping chromium dioxide with
known as Guignet’s green [12001-99-9] that heavy metals [32], [33] in order to meet the re-
consists of very finely divided chromium(III) quirements for a magnetic pigment [34]. The
oxide to which water is bonded by adsorption. marketing of chromium dioxide at the begin-
 Chromium Compounds 13

ning of the seventies initiated the development chromium dioxide is soluble in concentrated sul-
of cobalt-doped iron oxides which are nowadays furic acid or concentrated alkali solution.
used as an alternative to chromium dioxide for
information storage. Production [50]. Chromium dioxide is made
by decomposition of chromyl chloride, chromic
Physical and Chemical Properties [35]. acid anhydride [50], and chromium(III) chro-
Chromium dioxide [12018-01-8], CrO2 , M r mate [51], or by oxidation of chromium(III)
84.00, crystallizes in black tetragonal needles. compounds with oxygen, hydrogen peroxide,
The lattice is of the rutile type and belongs to chromic acid anhydride [52], or ammonium per-
the space group 4/mmm. The dimensions of the chlorate [43].
unit cell are a = b = 44.21 nm and c = 29.16 nm. Industrial production employs a process orig-
The X-ray density is 4.89 g/cm3 , and the phase inally carried out under licence from Du Pont
width is between CrO1.89 and CrO2.02 [36]. The [42], which involves hydrothermal oxidation of
enthalpy of formation is − 590 kJ/mol [37]. The chromium(III) oxide with excess chromic acid:
temperature coefficient for the c-axis is negative
[38]. At 100 ◦ C, agglomerated blocks have a lin- Cr2 O3 + 3 CrO3 −→ 5 CrO2 + O2
ear coefficient of expansion of − 6×10−6 K−1
[39]. Iron(III) oxide and antimony(III) oxide are used
At room temperature chromium dioxide as a dopant. Finely divided chromium(III) oxide
is ferromagnetic, the magnetic moment be- is obtained either by thermal decomposition of
ing 2 Bohr magnetons. The Curie tempera- ammonium dichromate or by dehydration of
ture is 120 ◦ C and increases to 155 ◦ C as chromium(III) hydroxide [52].
a result of doping with iron [40]. Finely A highly viscous paste (50 – 100 Pa · s) is pro-
crystalline needle-shaped chromium dioxide duced by intensively homogenizing the starting
has a specific magnetic saturation M s /
of materials. This paste is heated at 300 ◦ C and
77 – 92 A m2 /kg, whereas in single crystals M s /
35 MPa (350 bar) to form a hard agglomerate of
rises to 100 A m2 /kg [32]. The magnetocrys- fine chromium dioxide needles which must be
talline anisotropy constant is 22×103 J/m3 [41]. drilled out of the reactor trays, broken, and care-
The coercivity H c depends on the size of the fully ground. If the residual moisture exceeds
crystals and on their shape and magnetocrys- 5 %, the product is reheated in a rotary kiln. The
talline anisotropies. The coercivity is affected to chromium dioxide is deagglomerated in an aque-
differing extents by various heavy metals [42]. ous sodium sulfite suspension, and the crystal
Iron, antimony, and tellurium increase H c from surface is simultaneously reduced; this forms a
35 kA/m to 60 kA/m, whereas iridium increases chromium(III) oxide hydroxide layer about 1 nm
it to 220 kA/m [43]. thick. To do this, the suspension is circulated
Chromium dioxide behaves as a metallic con- through a mill which generates intense shear
ductor [35], [44], with a specific electrical re- fields and the fine component is removed by us-
sistivity between 2.5×10−4 and 4×10−2 Ω cm ing a hydrocyclone. After filtration and wash-
[38], [45]. ing, drying is carried out in a spray tower. The
At room temperature and normal pressure chromium dioxide obtained has a bulk density
chromium dioxide is metastable; when heated to of 0.8 g/cm3 .
temperatures above 350 ◦ C, it decomposes into Production is carried out to a large extent
chromium(III) oxide and oxygen. Chromium in closed equipment. Less than 2 mg of dust
dioxide has an oxidizing action on reactive or- is emitted per 1 m3 of exhaust air (STP). The
ganic compounds [46]; the reactivity is consid- chromium-containing wastewater from the pro-
erably decreased by enveloping it with iron(III) duction is worked up by reduction.
and chromium(III) oxides [47–49]. Chromium
dioxide is insoluble in water. Reaction with wa- Use and Economic Importance. Chromium
ter occurs at the crystal surface, with dispro- dioxide is used as a magnetic pigment. So far no
portionation to chromate and Cr3+ ions. The other uses have achieved any significance [33].
aqueous suspension has a pH of 3. However, In the audio field, chromium dioxide is used
in mono- and multilayer tapes, the layers in the
14 Chromium Compounds
Table 7. Powder data for typical chromium dioxide pigments

Application Particle geometry Magnetic data d

SSA a , l̄ b , l̄/d c V c, Hc, M r / e , M s / f ,

m2 /g µm 10−4 µm kA/m A m2 /kg A m2 /kg

Audio 28 0.29 9 2.5 41 35 77

Video 35 0.29 11 1.5 49 34 74
Data storage 24 0.32 8 3.5 39 35.5 79
a
Specific surface area (SSA) determined by N2 adsorption using the BET method (1-point measurement).
b
Mean length l̄ determined by electron microscope photography with a magnification of 20 000 times.
c
Diameter d and volume V calculated from SSA and l̄.
d
Measured with a vibration magnetometer, H m = 800 kA/m.
e
M r / = specific remanent magnetization.
f
M s / = specific saturation magnetization.

latter containing chromium dioxide of differ- 20 ◦ C and 199 g of CrO3 at 90 ◦ C per 100 mL
ent coercivity. In video tapes, it is employed of water. The compound also dissolves in sulfu-
either on its own or mixed with cobalt-doped ric acid and nitric acid. Chromium(VI) oxide is
iron oxides. Because of its low Curie point, a powerful oxidizing agent, particularly in the
chromium dioxide allows high-speed thermo- presence of acids. Reactions with alkali met-
magnetic copying of prerecorded audio and als and numerous organic compounds, e.g., low-
video tapes [53]. Chromium dioxide has been boiling hydrocarbons, acetone, or benzene and
used in digital data storage since 1985. Since the its derivatives, proceed explosively with consid-
magnetostriction of chromium dioxide is low, re- erable heat being produced. Esters of chromic
peated playing results in virtually no level losses acid are also known, e.g., with such cyclic ter-
[54]. Table 7 contains data on chromium dioxide tiary alcohols as methylfenchol and methylbor-
powder intended for various applications. neol.
In 1984 the demand for magnetic pigments Chromium(VI) oxide is made by the reaction
was about 50 000 t, about 10 % of this being of sodium dichromate with sulfuric acid. The
chromium dioxide. The most important manu- reaction can be carried out with solid sodium
facturers are Du Pont (United States) and BASF dichromate or with solutions or suspensions.
(Federal Republic of Germany). In addition, Both methods are in use industrially. The re-
there is a chromium dioxide plant in the former action proceeds rapidly and completely after
Soviet Union. the components have been mixed, with heat be-
ing evolved. Isolation of chromium(VI) oxide
from the reaction mixture or purification of
4.3. Chromium(VI) Oxide the crude product obtained from the aqueous
solution is difficult. Quantitative separation of
Chromium trioxide [1333-82-0], chromic acid sodium hydrogen sulfate is possible only if the
anhydride, chromic acid, CrO3 , M r 99.99,
chromium(VI) oxide is melted, but at this tem-
2.7 g/cm3 , forms dark red crystals which del- perature the product begins to decompose. The
iquesce in air. The enthalpy of formation is melting process must therefore be controlled
− 594.5 kJ/mol. The oxide melts at 198 ◦ C and very precisely.
starts to decompose, giving off oxygen and
brownish red vapors with a pungent smell. The Dry Process. Even today the old discontinu-
rate of decomposition reaches a maximum at ous process is in use to some extent. The reaction
290 ◦ C, chromium(III) oxide, Cr2 O3 , being pro- vessels are made from carbon steel or stainless
duced as the final product via various interme- steel. The conical containers are equipped with
diate stages. Chromium(VI) oxide dissolves in stirrer, exhaust facilities, and external heating.
water to form chromic acids (see 6.1); the sol- Sulfuric acid and sodium dichromate are added
ubility depends only slightly on temperature. simultaneously with stirring. The paste heats up
A saturated solution contains 166 g of CrO3 at to 80 ◦ C during mixing and is heated further
 Chromium Compounds 15

to evaporate water. At 170 ◦ C sodium hydrogen If a highly concentrated solution is used in-
sulfate melts, followed by chromium(VI) oxide stead of dichromate crystals, the kiln can be
at 198 ◦ C. As soon as the reaction products are heated directly [56].
liquid, the heating and the stirrer are turned off.
After a few minutes the heavier chromium(VI) Wet Process. A hot saturated solution of
oxide (
2.2 g/cm3 ) settles at the bottom, and is sodium dichromate, which may still con-
covered by a layer of the lighter sodium hydro- tain dichromate crystals, reacts with sulfuric
gen sulfate (
2.0 g/cm3 ). Liquid chromium(VI) acid [57]. In the course of 30 – 60 min the
oxide is drawn off the bottom and conveyed chromium(VI) oxide precipitates from the hot
to a cooling drum where it solidifies to form solution. On filtration a crude product is ob-
scales. Sodium hydrogen sulfate is subsequently tained, with a yield of about 80 %. Sodium hy-
drained. The yield of chromium(VI) oxide is drogen sulfate must be removed from the crude
about 85 %; 175 kg of sodium dichromate and product by fusion. The filtrate can be recycled for
140 kg of 96 % sulfuric acid are required to converting sodium monochromate into dichro-
obtain 100 kg of chromium(VI) oxide. About mate; it can also be used in a fresh reaction mix-
150 kg of sodium hydrogen sulfate is obtained ture [58] if sodium hydrogen sulfate is first crys-
as byproduct. tallized and removed at 20 – 25 ◦ C. The crude
Figure 4 shows a continuous dry process chromium(VI) oxide is purified by continuous
[55]. The raw materials are fed to a mixing successive fusion and decanting [59].
screw for intimate mixing. A viscous paste of As an alternative to production by reaction
chromium(VI) oxide, sodium hydrogen sulfate, with sulfuric acid, Diamond – Shamrock devel-
and water forms which is fed into a heated ro- oped an electrochemical process [60–62] in
tary kiln of stainless steel where it is melted. which chromic acid is produced from sodium
The heating must be controlled very carefully. dichromate in a two- or three-compartment cell.
The melt flows into a separator, where the heav- Chromium trioxide is usually sold in the form
ier chromium(VI) oxide collects at the bottom of of flakes, but the coarsely or finely ground prod-
the trough, is removed by means of a rising pipe, uct is also marketed. Good commercial products
and is converted into scales on cooling drums. contain 99.5 – 99.7 % CrO3 and a maximum of
The upper sodium hydrogen sulfate layer leaves 0.1 % of sulfate. In the form of flakes, the prod-
the separating cell via an overflow and is also uct has a bulk density of 1.1 kg/L whereas that
cooled on drums. Exhaust air from the various of the ground product is 1.4 kg/L. Steel drums
pieces of equipment is purified in a wash tower. must be used as containers and they must be
The yield of this process is over 90 %. tightly sealed because the product absorbs mois-
ture from the air.
Chromium trioxide is classified as a dan-
gerous substance in the EEC list and must
be marked as fire-promoting and corrosive. In
the IMDG code chromic acid has been put in
class 5.1., UN No. 1463. The MAK of CrO3 is
0.1 mg/m3 .
Electroplating is the most important field of
application of chromium(VI) oxide. Numerous
mixtures containing chromium trioxide are on
the market; these “compounds” often contain
hexafluorosilicates which improve the proper-
ties of the chromium coatings. Chromic acid so-
lutions are also used for passivating zinc, alu-
Figure 4. Continuous production of chromium(VI) oxide minum, cadmium, and brass. Proprietary mix-
a) Metering device; b) Wash tower; c) Mixer; d) Rotary tures predominantly contain additions of fluo-
kiln; e) Separation cell; f) Cooling drum for chromium(VI)
oxide; g) Cooling drum for sodium hydrogen sulfate
ride, nitrate, and phosphate ions. Other uses for
chromic acid are in the production of chromium
dioxide and in wood preservation.