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Zinc Compounds

Chapter · June 2017

DOI: 10.1002/0471238961.2609140307151504.a02.pub3

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 ZINC COMPOUNDS
1. Introduction

Zinc usually occurs as the sulfide, but significant quantities of the oxide, carbonate,
silicate [14374-77-7], and basic compounds of the latter two are also mined (see
ZINC AND ZINC ALLOYS).
Zinc is in group 12 (IIB) of the periodic table and exhibits a valence of +2 in all
its compounds. Being high on the electromotive series, zinc forms quite stable
compounds and, as such, resembles magnesium. Bonding in zinc compounds
tends to be covalent, as in the sulfide and oxide. With strongly electropositive
elements, eg, chlorine, the bond is more ionic. Zinc also tends to form stable
covalent complex ions, eg, with ammonia [Zn(NH3)2]2+, cyanide [Zn(CN)4]2 , and
hydroxyl [Zn(OH)4]2 . The coordination number is usually 4, to a lesser degree 6,
and in some cases 5. A good review of zinc compounds is given in Reference 1.
Zinc forms salts with acids, but since it is amphoteric, it also forms zincates,
eg, [Zn(OH)3
H2O] and [Zn(OH)4]2 . The tendency of zinc to form stable hydroxy
complexes is also important because some basic zinc salts are only slightly soluble
in water. Examples are 3Zn(OH)2
ZnSO4 [12027-98-4] and 4Zn(OH)2
ZnCl2 I,
which may precipitate upon neutralization of acidic solutions of the salts.
Properties of zinc salts of inorganic and organic salts are listed in Table 1 with
other commercially important zinc chemicals. In the dithiocarbamates, 2-mercap-
tobenzothiazole, and formaldehyde sulfoxylate, zinc is covalently bound to sulfur.
In compounds, such as the oxide, borate, and silicate, the covalent bonds with
oxygen are very stable. Zinc–carbon bonds occur in diorganozinc compounds, eg,
diethylzinc [557-20-0]. Such compounds were used much more in organic synthesis
prior to the development of the more convenient Grignard route (see GRIGNARD
REACTION).
The water solubility of zinc compounds varies greatly, as shown in Table 1.
For example, the dissolution of zinc oxide can create several ionic species, includ-
ing Zn+2, ZnOH+, ZnO2H , and ZnO2 2, each of which is in equilibrium with water
Q1 at a specific pH for a given temperature (3). Water-soluble compounds not listed
are zinc formate [557-41-5], chlorate [10361-95-2], fluorosilicate [16871-71-9], and
thiocyanate [557-42-6]. Also, the water-soluble amino and cyanide complexes have
many uses.
Zinc compounds are generally colorless unless the other component, eg,
chromate, is colored. The lack of color of most zinc compounds in visible light is
a great advantage in that they do not color paint films, plastics, rubber, cosmetics,
etc. However, when excited by various types of radiation and at various tempera-
tures, zinc oxide, sulfide, selenide [1315-09-9], and related compounds exhibit
luminescence, ie, they emit colored light (see LUMINESCENT MATERIALS). Zinc-based
phosphors can be produced in many colors, depending on the added dopants. They
are used in television tubes, luminescent glasses, and various specialty products.

2. Zinc Oxide

2.1. Physical Properties. Some of the physical properties of zinc oxide

are listed in Table 2. Of great importance is the fact that it completely absorbs

Kirk-Othmer Encyclopedia of Chemical Technology. Copyright  2017 John Wiley & Sons, Inc. All rights reserved.
DOI: 10.1002/0471238961.2609140307151504.a02.pub3
 Table 1. Properties, Prices, and Uses of Zinc Compounds
Solubilitya, g/100 g solvent water Priceb, $/kg (Aug. 1981)
CAS Registry a
Zinc compound Formula, synonym No. Sp gr mp, °C Other Uses
acetate Zn(C2H3O2)
2H2O [5970-45-6] 1.735 237 4025°C 67100°C 325°C alcohol 3.53 wood preservative, mordant antiseptics,
catalyst, waterproofing
0°C 30°C
ammonium chloride ZnCl2
2NH4Cl [52628-25-8] 1.88 150 dec 66 69 0.71 galvanizing, solder flux, adhesives
diborate ZnO
B2O3
2H2O [27043-84-1] 3.64 0.00725°C sl sol HCl 1.21 fireproofing, ceramics, fungicide
dodecaborate 2ZnO
3B2O3
3.5H2O [12513-27-8] 4.22 980 insol 1.54 fire retardant
bromide ZnBr2 [13550-22-6] 4.21 394 47125°C 675100°C sol alcohol, ether 62.00c photographic paper, catalyst, batteries
carbonate ZnCO3 [3486-35-9] 4.40 CO2 at 300 0.00115°C insol alcohol 45.40c ceramics, rubber, astringent (lotions)
chloride ZnCl2 [7646-85-7] 2.91 275 43225°C 614100°C sol ether 0.41 textiles, adhesives, flux, wood preservative,
antiseptic, astringent
cyanide Zn(CN)2 [557-21-1] 1.85 800 dec 0.00520°C sol alkali, CN 3.63 electroplating, gold extraction
dithiocarbamates S
dibutyl Zn SCN(C4H9)2 [136-23-2] 1.21 106 insol sol C6H6, CS2, CHCl3 3.17 vulcanization accelerator, lube oil
2
S
diethyl Zn SCN(C2H2)2 [14324-55-1] 1.48 176 insol sol C6H6, CS2, CHCl3 3.32 vulcanization accelerator
2
S
ethylenebis Zn SCNHCH2 [12122-67-7] insol sol C6H6, CS2, CHCl3 5.50 fungicide, insecticide
2
zineb S

dimethyl Zn SCN(CH3)2 [137-30-4] 1.71 249 0.006525°C sol CS2, acetone, alkali 3.06 vulcanization accelerator, fungicide
2
ziram
2-ethylhexanoate Zn(C8H16O2)2 [136-53-8] 0.90 insol sol hydrocarbon 1.87 paint drier, silicone rubber cure
fluoroborate Zn(BF4)2
6H2O [13826-88-5] H2O at 60°C >10025°C sol alcohol 0.60 plating, bonderizing, textile resin cure
fluoride ZnF2 [7783-49-5] 4.95 872 1.618°C sol hot acid, NH4OH 100.00c ceramics, impregnating wood, galvanizing
formaldehyde sulfoxylate Zn(HSO2
CH2O)2 [24887-06-7] 90 dec 6025°C insol alcohol 2.31 reducing agent, drying, polymerization
hydrosulfite [7779-86-4] 200 dec 4020°C 2.25 bleach, especially textile, paper, reducing

2
ZnS2O4
2H2O
agent
iodide ZnI2 [10139-47-6] 4.70 446 43218°C 510100°C sol alcohol 182 medicine, photography
2-mercaptobenzothiazole Zn(SC6H4NCS)2 [155-04-4] 1.70 300 dec insol insol sol C6H6, CS2, CHCl3 3.17 vulcanization accelerator for latex
naphthenate Zn[(C2H)5CHCOO]2 [12001-85-3] insol insol sol hydrocarbon, acid 1.17 paint film improver, rot proofer
nitrate Zn(NO3)2
6H2O [10196-18-6] 2.065 18 93 90070°C sol alcohol 0.75 textiles as resin catalyst, mordant latex
coagulant
oxide ZnO [1314-13-2] 5.47, 5.61 1800 sublimes 0.0004218°C sol acid, alkali, NH4OH 1.05–1.12 vulcanization accelerator, mildewstat,
pigment, supplement in feed and
fertilizer, catalyst, ceramics, intermediate
peroxide ZnO2 [1314-22-3] 1.57 212 explodes insol sol acid 5.50 cosmetic powders as antiseptic
phosphate Zn3(PO4)2 [7779-90-0] 4.00 900 2.625°C insol sol NH4OH, insol alcohol 1.85 metal coatings, dental cement
potassium chromate 4ZnO
K2O
4CrO3
3H2O, [37300-23-5] 3.36–3.46 0.2425°C 2.47 rust-inhibiting pigment
zinc yellow
resinate Zn(C20H30O2)2 [9010-69-9] 1.24 205 insol insol sol hydrocarbon 0.99 inks, paint drier
selenide ZnSe [1315-09-9] 5.42 1100 insol sol acid 330.0 phosphor
silicofluoride ZnSiF6
6H2O [18433-42-6] 2.10 100 dec 7710°C 9360°C 0.37 laundry sour, wood preservative, plaster
additive
stearate Zn(C17H35COO)2 [557-05-1] 1.09 120 insol insol sol hydrocarbon 1.90 lubricant, mold release, vinyl stabilizer,
anticake, water repellant
0°C 70°C
sulfate ZnSO4 [7733-02-0] 3.54 680 dec 41.9 91 sol glycerol 0.77 rayon bath, agriculture, zinc plating,
intermediate, flotation, mordant
sulfate ZnSO4
H2O [7446-19-7] 3.28 238 dec 10170°C 87105°C 0.58 rayon bath, agriculture, zinc plating,
intermediate, flotation, mordant
sulfide ZnS [1314-98-3] 3.98, 4.10 1185 sublimes 0.000718°C insol sol acid 1.76d phosphor, white pigment, dental materials
tetroxychromate 4Zn(OH)2
ZnCrO4 [13530-65-9] 3.87–3.97 0.0125°C 2.57 wash primer
undecylenate Zn[CH2 CH(CH2)8
COO]2 [557-08-4] 115 insol insol sol hydrocarbon 9.70 dermal fungicide

a
Insol = insoluble, v sol = very soluble, dec = decompose.
b
Ref. 2.
c
Reagent price.
d
Pigment price.
 ZINC COMPOUNDS 3

Table 2. Selected Physical Properties of Zinc Oxide

Property Value Reference
mp,a °C ∼ 1975 (subl) 7
color white in finely divided form
refractive index, 0.5 μm 2.015, 2.068 8
specific gravity 5.68
water solubility, minimum at pH 9.7 3
Ksp Zn(OH)2 4.5 × 10 17
heat capacity (at 25°C), J/(mol °C)a 40.26
ΔHformation (at 419.5–907°C), kJ/mola 356.1 7
ΔFformation (at 419.5°C), kJ/mola 281.6 9
ΔFformation (at 907°C), kJ/mola 229.0
S formation (at 25°C), J/mola 43.65 9
coefficient of expansion, × 10 6/°C 4.0 10
conductivity, W/(m
K) 25.2 11
crystal structure hexagonal, wurtzite
conductivity (n-type), S/cm 10 7–103 12
piezoelectricity (lithium-doped) ∼ 4 × that of quartz 13
magnetic susceptibility 0.20 14
(at 196°C), × 10 6 Hz units
pyroelectric current density, MA/(m2
s
K) 6.8 15
E° of Zn + ½O2 = ZnO (at 25°C), V 1.649 16
a
To convert J to cal, divide by 4.184.

ultraviolet (UV) light < 366 nm and, thus, is unique among white pigments (4). Its
high refractive indexes make it a good white pigment where its mean diameter for
maximum light scattering is 0.25 μm. The crystal structure of zinc oxide is likely to
stabilize defects, eg, zinc excess or deficiency and inclusion of foreign ions, and
therefore, has useful semiconductor properties. Variously doped oxides are used
for photocopying and as catalysts and phosphors (5,6) (see REPOGRAPHY; CATALYSTS;
SEMICONDUCTOR).
2.2. Chemical Properties. Zinc oxide, as an amphoteric material, reacts
with acids to form zinc salts and with strong alkalies to form zincates. This is
illustrated by the following reactions:

ZnO ‡ 2HCl ! ZnCl2 ‡ H2 O …reaction with acid†

ZnO ‡ 2 NaOH ! Na2 ZnO2 ‡ H2 O

Zinc oxide slurries are chemically neutral, with slurries measuring 7.5 < pH < 7.9.
This combination of amphoteric properties and neutrality permits the use of zinc
oxide in a wide range of applications from sunscreens to house paints.
In the vulcanization of rubber, the chemical role of zinc oxide is complex and
the free oxide is required, probably as an activator (see RUBBER CHEMICALS). Zinc
soaps result from the oxide’s interaction with organic acids and their interaction
with the accelerator. The oxide is used alone as an accelerator in certain elas-
tomers, eg, neoprene and thiokols, which contain chlorine and sulfur in the
polymer molecules. Zinc oxide reacts with carbon dioxide in moist air to form
oxycarbonate. Acidic gases, eg, hydrogen sulfide, sulfur dioxide, and chlorine, react
4 ZINC COMPOUNDS

with zinc oxide, and carbon monoxide or hydrogen reduce it to the metal. At
high temperatures, zinc oxide replaces sodium oxide in silicate glasses. An
important biochemical property of the oxide is its fungicidal/moldewstatic action
(see FUNGICIDES) (17). It is also soluble in body fluids and soils (18). Zinc reacts with
HCl to form Zn2OCl2, a rapidly reacting dental cement. ZnO combines with
phosphoric acid to produce several complex compounds such as Zn(H2PO4).H2O
that are used to pretreat automobile bodies for painting.
2.3. Production and Processing. Primary zinc oxide is manufactured
by oxidizing zinc vapor in burners wherein the concentration of zinc vapor and
the flow of air is controlled so as to develop the desired particle size and shape.
The hot gases and particulate oxide or fume pass through tubular coolers, and
then the ZnO is separated in a baghouse. The purity of the zinc oxide depends on
the source of the zinc vapor. Zinc oxide of great purity is required for pharma-
ceutical, photoconductive, and certain other grades, and these are made by the
indirect (French) process, which accounted for 60% of world zinc production in
2003. Zinc vapor from previously purified zinc metal is burned (19,20). Less pure
zinc oxide is manufactured by the direct (American) process, by which impure
zinc oxide is reduced to zinc vapor that is then burned (19). The American process
accounted for 40% of world zinc oxide production in 2003. Certain impurities in
the original crude ore and carbonaceous reductant are inseparable from the
product oxide. Nevertheless, the uses dictate that certain impurities be at low
levels. For example, cadmium, lead, iron, sulfur, copper, and manganese can be
deleterious in rubber if they exceed certain concentrations (21,22). Some scrap
zinc materials undergo both French and American processes; other processes are
used to produce secondary zinc oxide from zinc scrap, zinc-containing sludges,
and metallurgical slags. Worldwide sources for zinc oxide production in 2003
were from galvanizers scrap (40%), primary zinc (40%), and old roofing, die
castings, etc (20%).
Direct (American) Process. Grate Furnaces. In the eastern Wetherill
furnace, four or more firebrick furnaces (called a block) having common walls are
charged in cyclic fashion. Coal that is hot from the previous charge is first spread
on the grate and, after ignition, a damp, well-blended mixture of zinciferous
material and coal is added. The bed is maintained in a reducing condition with
carbon monoxide to produce zinc and lead, if present. Metal vapors are drawn into
a chamber above the furnace, where combustion air oxidizes them to pigment.
The hot pigment–gas stream enters a cooling duct common to the whole block
and, in this way, the product becomes a uniform blend. The raw material contains
15–75 wt% zinc, but usually >60 wt%, and the coal is adjusted accordingly. For
best results, anthracite or coke is used (see COAL). Calcium, iron, and silica
influence the nature of the clinker and the elimination of zinc and must, therefore,
be minimized.
The western Wetherill furnace is like the eastern furnace except that a block
of 12 or more furnaces has a common combustion chamber. This results in
improved control and uniformity of product. Clinker usually contains 8–15 wt%
zinc, which is often recovered in a Waelz kiln (23).
The traveling grate furnace requires less labor, increases the output per unit
of grate area, and produces more uniform product than the Wetherill furnaces. The
traveling grate is an endless chain of cast iron bars, driven by sprockets, which
 ZINC COMPOUNDS 5

traverses a firebrick chamber. Anthracite briquettes are fed to a depth of ∼15 cm.
After ignition by the previous charge, the coal briquettes are covered by 15–16.5 cm
of ore/coal briquettes. The latter are dried with waste heat from the furnace. Zinc
vapor evolves and burns in a combustion chamber and the spent clinker falls into
containers for removal (23,24).
Rotary Kilns. The pigment-grade oxide kiln, because of its high tempera-
ture, produces pigment-quality zinc oxide and makes possible higher recovery as
compared to the grate furnaces. The kilns, which are 2.4 m diameter and 12.1–
15.2-m long, are fed in the firing end with a mixture of 65 wt% sinter and 35 wt%
anthracite. Very slow rotation and small slope give sufficient retention time for
good zinc elimination. The atmosphere in the kiln is reducing. Air is then control
fed into a firebrick combustion chamber, where the zinc is burned to the desired
size and shape. The exiting solid residue is water quenched.
The Waelz process is used to beneficiate many metals, including zinc, and
produces a relatively impure oxide (25). This is true because the loose feed is
charged at the end of the kiln where metal vapors are exiting and because the
feed materials are usually quite impure. Where the process is used to make crude
zinc oxide, feeds include oxidized and sulfide zinc ores, residues, zinc-bearing
iron ores and flue dusts, lead furnace slags, mill slimes, electrolytic-zinc leach
residues, and ores of various other metals, eg, tin and gold (26). The metallurgy
of the process is similar to the preceding processes, but it is complicated by the
presence of other materials in the feed, eg, sulfates, sulfides, carbonates, and
silicates. Conditioners, eg, silica, lime, and iron oxide, are often added to control
the fluidity of the charge (27). Also, lime can be used to fix sulfur as calcium
sulfide, so that materials containing up to 20 wt% sulfur can be introduced into
the kiln. Any sulfur dioxide formed tends, because of the high temperature and
long retention time, to be oxidized to trioxide and reacts with metallic oxides to
form sulfate.
The charge, which contains ∼25 wt% carbon, progresses through the 11–30-m
long kiln, countercurrent to the hot gases from the fuel burner and the burning
carbon in the bed. Lifters give the bed a considerable mixing action, as the kiln
rotates at 1–1.5 rpm. The particles are reduced when submerged in the bed and are
oxidized on the surface. Conditions are adjusted so that the products in the exiting
gas are zinc and cadmium vapors, stannous oxide, germanium monoxide, carbon
monoxide, and often further oxidized states of these compounds. They are fully
oxidized in the combustion chamber, which may also serve as a settling chamber
for fly ash from the kiln. Settled material is recycled to the kiln. The fume is cooled
and collected in a baghouse. Very often, the crude ZnO is sintered to remove
cadmium, sulfur, and lead and used for the production of zinc oxide or zinc metal.
Electrothermic Process. Electrothermic zinc smelting is described in
Reference 28. The oxide furnaces in a U.S. plant are 11-m high, three are
1.75-m in diameter and the fourth is 2.44-m in diameter with eight graphite
electrodes at each of two levels. The electrical resistance path through
the descending charge of 70 wt% sinter and 30 wt% coke is 9-m long, and it
supplies the energy for smelting. The zinc vapor and carbon monoxide pass
through exit ports at four levels between the upper and lower electrodes into
manifolds where pigment forms by oxidation with added air. After cooling and
passing through a cleaning cyclone, the oxide is collected in a baghouse (29).
6 ZINC COMPOUNDS

Indirect (French) Process. Zinc metal vapor for burning is produced in

several ways. Because all the vapor is burned in a combustion chamber, the purity
of the oxide depends on that of the zinc feed. Oxide of the highest purity requires
special high grade zinc and less-pure products are made by blending in Prime
Western and even scrap zinc.
Another method involves an electric-arc vaporizer that is >2000 °C before
burning (24,30). One of the features of the process is a rapid quench of the hot gas
flow to yield very fine oxide particles (0.15 nm). This product is quite reactive and
imparts accelerated cure rates to rubber. Internally fired rotary kilns are used
extensively in Canada and Europe and, to a limited extent, in the United States
(23). The burning occurs in the kiln and the heat is sufficient to melt and vaporize
the zinc. Because of the lower temperatures, the particles are coarser than those
produced in the other processes. In a fourth process, zinc metal that is purified in a
vertical refining column is burned. In essence, the purification is a distillation and
impure zinc can be used to make extremely pure oxide. Also, a wide range of
particle sizes is possible (31).
Secondary Zinc Oxide. Secondary oxide is made from scrap, eg, galva-
nizer’s dross, trimmings, automotive zinc scrap, and is largely used by rubber and
ceramics manufacturers. About half of the oxide produced in the United States is
from secondary material, although some of it is made by primary producers. Most
secondary oxide is of the French type in that the starting zinc is metallic. The zinc
is usually vaporized in upright retorts in such a way that the higher boiling
impurities, eg, lead, do not vaporize and relatively pure oxide is produced (32).
Another procedure for manufacturing secondary oxide is precipitation of zinc
carbonate from waste zinc solution followed by drying, calcining, and grinding
to a coarse oxide suited for ceramics. A similar product results from the calcination
of zinc hydrosulfite [7779-86-4] sludge. Such sludges are by-products of the use of
zinc hydrosulfite as a bleaching agent.
Leaded Zinc Oxide. Oxides containing >5 wt% basic lead sulfate are
classified as leaded and are made in the American process from high lead
materials, usually lead sulfide mineral, or by blending zinc oxide and basic
lead sulfate. There is only one manufacturer in the United States and the product
contains 20–28 wt% basic lead sulfate. Leaded oxides are used only in rubber in the
United States.
Slag Fuming Process. Three plants in the United States, two in Canada,
and one in Mexico process slag from blast furnaces (usually lead) and residues to
make zinc oxide fume. The oxide is impure and most is sent to zinc smelters for
conversion into metal; however, a small amount is sold as pigment. The process
consists of blowing powdered coal into a bath of molten slag via multiple double
inlet tuyeres (33). Zinc is eliminated from the 10–18 wt% zinc charge in ∼2 h, and
the coal is the fuel and the reductant, ie, carbon monoxide, source. The direct
method of introduction of the coal combines drying and grinding with the
feeding of coal into the furnace feed lines. Indirect feeding uses previously
dried and ground coal from a bin. In either case, the coal–air mixture must
be carefully controlled to minimize excess coal yet avoid too low a temperature.
The slag temperature is maintained at 1150–1200 °C. Recovery is ∼90% or better
for both lead and zinc, and results in fume of ∼70 wt% zinc oxide and 7–10 wt%
lead.
 ZINC COMPOUNDS 7

Zinc Oxide Treatments. There are a number of treatment procedures in

addition to the customary screening and pulverizing. Various chemical materials
are added to improve ease of incorporation and dispersibility of the oxide in rubber
and paint (see PAINT). Commonly, these are fatty acids, eg, propionic and stearic,
and oils (34,35). Phosphoric acid is added to reduce chemical activity and trialkyl
phosphates to combat dusting (36,37). American process zinc oxide may contain
acidity in the form of oxysulfur compounds; this can be removed by washing with
solutions of ammonia or ammonium salts (38). However, improved American
process oxides, which do not need washing, are being produced. Unless recalcined,
zinc oxide tends to be bulky, dusty, and have poor dry flow. These characteristics
are especially objectionable to those who use the oxide in ceramics and rubber.
Therefore, some grades are pelleted in rotating drums or densified by passing
through rolls.
2.4. Economic Aspects. Tires and rubber have dominated zinc oxide
consumption for many years, with some regional variations. In the United States,
the rubber industry is the major market for zinc oxide and accounts for ∼60% of
usage, while in Europe ∼40% of zinc oxide is used in rubber production. For Japan,
the proportion is ∼50%. Zinc oxide is important in rubber processing because of its
effectiveness as an activator in the vulcanization process. In its raw state, rubber
consists of long randomly linked hydrocarbon chains that can slide past each other.
Vulcanization chemically links the rubber chains together by cross-links, forming
a three-dimensional (3D) network. Vulcanization has remained the key process in
rubber production for over a century and during this time zinc oxide has been the
most cost efficient vulcanization process activator (Table 3).
Zinc oxide also protects rubber from thermal effects caused by internal
friction and acts as a heat sink that accepts frictional energy without large
increases in internal temperature. It also improves the performance of uncured
rubber during processing by decreasing shrinkage of molded rubber products
and maintaining cleanliness of the molds. Tire wear, abrasion, performance,
and degradation by ultraviolet radiation are also moderated by zinc oxide
additions.
2.5. Health and Safety Factors. Zinc oxide is considered nontoxic, but
inhalation of freshly formed fume can cause zinc chills also known as brass-
founder’s ague. The symptoms are fever and cough followed by chills after ∼4–8 h
(39). No aftereffects have been noted and workers who are continually exposed
quickly develop a resistance (40). So-called chronic zinc poisoning is caused by
toxic impurities, eg, lead, cadmium, arsenic, and antimony, which commonly
contaminate zinc ores (41). The U.S. Occupational Safety and Health

Table 3. World Zinc Oxide Consumption, 2003

Product Amount, metric tons
tires 30,000
rubber 210,000
chemicals 160,000
ceramics/glass 130,000
agriculture 70,000
paints 60,000
others 40,000
 8 ZINC COMPOUNDS

Administration (OSHA) has set a maximum concentration limit for zinc oxide
fumes in workplace air of 5 mg of zinc/m3 of air for an 8-h workday over a 40-h work
week (28).
2.6. Uses. The uses of zinc oxide can be divided into two groups based on
the chemical and physical properties of the compound (42). The largest user, the
rubber industry, uses it chemically as a vulcanization activator and accelerator
and to slow rubber aging by neutralizing sulfur and organic acids formed by
oxidation. Fine oxides are used for fast cures and coarse, sulfated grades for slow
cures. Physically, it is a reinforcing agent, a heat conductor, a white pigment, and
an absorber of ultraviolet (UV) light.
In paints, zinc oxide serves as a mildewstat and acid buffer as well as a
pigment. In exterior house paints, zinc oxide additions allow absorption of UV rays
of the sun. For many years, paint was the second largest market for zinc oxide, but
the introduction of latex coatings into exterior house paints reduced market share.
Latex paints were sensitive to mold growth and originally carried mercury
compounds as fungicides, which were zinc oxide free. Because of the elimination
of mercury compounds during the 1970s, the paint industry has since developed
zinc oxide containing exterior latex paints, accounting for much of current usage.
Its chemical action in cosmetics (qv) and drugs is varied and complex but, based
upon its fungicidal activity, it promotes wound healing. It is also essential in
nutrition. Zinc oxide is used to prepare dental cements in combination with
eugenol and phosphoric and poly(acrylic acid)s (43) (see DENTAL MATERIALS).
Because of zinc oxide’s UV radiation absorption capabilities, it is an active
ingredient in many sun tan lotions. Recently, use of nanometer-sized zinc oxide
has allowed transparent sun protection formulations to be developed rather than
the traditional white colored sun preparations made with larger sized zinc oxide
particles. Zinc oxide is present in dietary supplements and vitamin tablets as a
source of the essential micronutrient zinc for the human body. The oxide is also a
starting material for many zinc chemicals. The oxide supplies zinc in animal feeds
and is a fertilizer supplement used in zinc-deficient soils.
Zinc oxide functions in ceramics in several ways. Added to glasses, it imparts
low thermal expansion, low melting, and increased chemical resistivity. Low
melting point zinc oxide-containing glasses are used for metal-to-glass seals
and in the electronics industry. The semiconducting property of a great variety
of glasses and ceramics is based on their zinc oxide content. Zinc oxide varisters are
used to protect against low voltage surges in electronics applications, such as
computers, and also for high voltage surges in lightening arrestors. Zinc ferrites
are basically zinc–ferrite oxide spinels, which are highly magnetic. Usually they
Q2 also contain other oxides, eg, nickel and manganese oxides, (qv) are used in many
electrical and electronic devices. The oxide is used as a catalyst in alkylation,
oxidation, hydrogenation, and dehydrogenation. The oxide is also used in coated
photocopy paper (see ELECTROPHOTOGRAPHY). For many years, zinc oxide has been
used in amounts up to 2–3 wt% in transparent raw glazes for artware or dinner-
ware and in larger amounts in semitransparent glazes for stoneware. Zinc oxide is
also widely used in tile glazes and its content in certain glaze types may exceed
10%. The higher percentages are used for the development of a matte finish.
Miscellaneous applications of zinc oxide include zinc dialkyldithiophosphate
(ZDTP), which is a major additive in the production of lubricant for engines where
 ZINC COMPOUNDS 9

it helps reduce oxidation and engine corrosion and wear. In plastics, zinc oxide
imparts fire resistance and helps degradation caused by UV light, such as in lawn
furniture and other outdoor applications.
Nutrition. Zinc is essential to the proper functioning of plants and animals
(including human beings) and, as oxide, it is used as a feed and crop fertilizer
supplement (44–46) (see MINERAL NUTRIENTS; FEED AND FEED ADDITIVES). Most crops
use less than a kilogram of zinc per 1000 m2/year, so that zinc salts added at 1.3–
4.5 kg/ha gradually build up the zinc reserve (47). Animals, including humans,
store relatively little available zinc and, thus, require a constant supply in the diet.
For example, beef cattle require 30–40 mg/kg dry feed, dairy cattle 47–60 mg/kg,
and breeding hens 65 mg/kg (48). Zinc from plants is considered less available to
monogastric animals than zinc from animal protein.
Zinc is second only to iron as a trace metal in humans. A 70-kg human body
has ∼4.0 g iron, 2.0 g zinc, 0.2 g manganese, 0.1 g copper, and < 0.1 g of all other
elements combined (49). The recommended dietary allowance of zinc is 15 mg/day
for adults and 25 mg/day for lactating females (50). Supplemental zinc is admin-
istered in the form of sulfate, chloride, acetate, gluconate [4468-02-4], stearate, or
oxide but the anion is not involved in the processes of utilization. Supplementary
zinc is prescribed for zinc deficiency and certain disorders. Deficiency is thought to
be more widespread in the United States than previously assumed (51). Although
excessive zinc produces toxic symptoms, such symptoms rarely occur. Large doses
or continued ingestion of zinc may cause gastrointestinal distress; eg, 2 g of zinc
sulfate is recommended as an emetic. However, 18 patients given 660 mg zinc daily
for 16–26 weeks showed no ill effects, but a 16-year-old boy who ingested 12 g of
elemental zinc in 2 days did develop noticeable ill effects (52).
Insufficient zinc results in slowed growth, delayed wound healing, poor
appetite, mental lethargy, and sexual immaturity and it interferes with the
immune response. The main function of zinc in metabolism is enzymatic and
there is evidence of other physiologic roles, eg, in stabilization of membrane
structure (53).

3. Zinc Chloride

Zinc chloride melts at 275 °C, boils at 720 °C, and is stable in the vapor phase up to
900 °C. It is very hygroscopic, extremely water soluble, and soluble in organic
liquids, eg, alcohols, esters, ketones, ethers, amides, and nitrides. Hydrates with 1,
1.5, 2.5, 3, and 4 molecules of water have been identified and great care must be
exercised to avoid hydration of the anhydrous form. Aqueous solutions of zinc
chloride are acidic (pH = 1.0 for 6 M) and, when partially neutralized, can form
slightly soluble basic chlorides, eg, ZnCl2
4Zn(OH)2 [11073-22-6] and Zn(OH)Cl
[14031-59-5]. Many other basic chlorides have been reported (54).
Anhydrous zinc chloride can be made from the reaction of the metal with
chlorine or hydrogen chloride. It is usually made commercially by the reaction of
aqueous hydrochloric acid with scrap zinc materials or roasted ore, ie, crude zinc
oxide. The solution is purified in various ways depending on the impurities
present. For example, iron and manganese precipitate after partial neutralization
with zinc oxide or other alkali and oxidation with chlorine or sodium hypochlorite.
10 ZINC COMPOUNDS

Heavy metals are removed with zinc powder. The solution is concentrated by
boiling, and hydrochloric acid is added to prevent the formation of basic chlorides.
Zinc chloride is usually sold as a 47.4 wt% (sp. gr. 1.53) solution, but is also
produced in solid form by further evaporation until, upon cooling, an almost
anhydrous salt crystallizes. The solid is sometimes sold in fused form.
The fumes of zinc chloride are highly toxic and can damage mucous mem-
branes and cause pale gray cyanation. It can also ulcerate the skin of workers using
it as a soldering flux or those handling wood impregnated with it (55). OSHA has
set a maximum concentration limit for zinc chloride fumes in workplace air of 1 mg
of zinc per cubic meter of air for an 8-h day over a 40-h work week (28).
The largest use of zinc chloride in the United States is in wood preservation,
fluxes, and batteries (qv). Zinc chloride solution dissolves vegetable fiber and is
widely used in mercerizing (qv), swelling fibers, as a mordant in dyeing, parch-
mentizing paper, etc. It dissolves metal oxides and is used as a flux, especially in
galvanizing. Zinc electroplating is often done with a chloride bath. In medicine, it is
used in antiseptics, deodorants, dental cements, and qv. Zinc chloride solutions
preserve wood and textiles and are used in (qv) and embalming fluids. Other uses
are in organic synthesis, eg, in the preparation of methyl chloride and diethylzinc,
as a dehydrant, in rubber vulcanization, and in oil refining.

4. Zinc Sulfate

Anhydrous zinc sulfate forms when its hydrates are heated at >238 °C. At
∼680 °C, sulfur trioxide separates from the compound, forming 3ZnO
2SO3
[12037-14-8] and at >930 °C the compound is decomposed to zinc oxide. The
three stable hydrates are ZnSO4
H2O [7446-19-7], ZnSO4
6H2O [13986-24-8],
and ZnSO4
7H2O (orthorhombic) [7446-20-0]. The latter heptahydrate occurs in
a few small deposits as the mineral goslarite [7446-20-0]. Three unstable
hydrates are ZnSO4
4H2O [33309-49-8], ZnSO4
2H2O [80867-26-1], and
ZnSO4
7H2O (monoclinic).
The solubility of zinc sulfate increases almost linearly with temperature from
27.6 wt% (as ZnSO4) at 7 °C to 41.4 wt% at 39 °C. In this range, the heptahydrate
is the solid phase. As the temperature rises, the solid phase becomes the hexa-
hydrate and its solubility increases to a maximum of 47.7 wt% at 70 °C. Above this
temperature, the solid phase is the monohydrate and solubility declines with
temperature to 44.0 wt% at the boiling point (105 °C). Many basic zinc sulfates
have been reported but probably the only true compounds are hydrates of 3Zn
(OH)2
ZnSO4 [12027-98-4] (56).
Zinc sulfate is usually made from secondary materials (93%) and from
roasted ore, ie, zinc oxide (7%). The zinciferous material reacts with sulfuric
acid to form a solution, which is purified. After filtration, the solution is heated
to evaporation and heptahydrate crystals are separated. It is sometimes sold in
this form but usually as the monohydrate [7446-19-7], which is made by dehydra-
tion at ∼100 °C. Very pure zinc sulfate solution is made in the manufacture of the
pigment lithopone [1345-05-7], ZnS
BaSO4, and of zinc by electrowinning.
Zinc sulfate is used in (qv), sprays, and animal feeds in which it serves as a
valuable trace element and disease-control agent. In the manufacture of rayon, it is
 ZINC COMPOUNDS 11

a crenulating agent in the precipitation bath. It is also the starting material for the
manufacture of many zinc chemicals and is used in textile dyeing and printing, (qv)
reagents, electrogalvanizing, paper bleaching, and glue. In 1950, rayon accounted
for 46% of zinc sulfate consumption, in 1960 55%, and in 1966 39%. Statistics for
rayon are not available beyond 1966, but the use in agriculture grew from 39% in
1966 to 49% in 1977, to 72% in 1979, and to 78% in 1980. The actual tonnage used
in agriculture has also increased steadily. Zinc consumption in 2015 for agricul-
tural application was 255,000 tons. Zinc in zinc sulfate comprised 65% of the total,
with zinc in zinc oxide comprising 34%. Within the agricultural use of zinc sulfate,
77%, or 420,000 tons per year of contained zinc, was used for fertilizer and 23%, or
125,000 tons per year of contained zinc was used in animal feed. China, India, and
the United States are the major markets for zinc compounds used in agriculture,
accounting for 80% of the world market (57).

BIBLIOGRAPHY

“Zinc Compounds” in ECT 1st ed., Vol. 15, pp. 275–281, by A. P. Thompson and H. W. Schutz,
the Eagle-Picher Co.; in ECT 2nd ed., Vol. 22, pp. 604–613, by A. P. Thompson, Eagle-Picher
Industries, Inc.; in ECT 3rd ed., Vol. 24, pp. 851–863, by T. B. Lloyd, Gulf and Western
Natural Resources Group; in ECT 4th ed., Vol. 25, pp. 840–853, by F. E. Goodwin,
International Lead and Zinc Research Organization, Inc., published online: Dec. 4, 2000;
in ECT 5th ed., Vol. 26, pp. 605–621, by F. E. Goodwin, International Zinc Association, Inc.,
published online: Feb. 17, 2006.

CITED REFERENCES

1. M. Farnsworth and C. H. Kline, Zinc Chemicals, Zinc Institute, Inc., New York, 1973.
Q3 2. Chem. Market. Rep. 220(9), 40 (1981).
3. L. Blok and P. L. DeBruyn, J. Colloid Interface Sci. 32, 518 (1970).
4. G. F. A. Stutz, J. Franklin Inst. 202, 89 (1926).
5. H. E. Brown, Zinc Oxide, Properties and Applications, International Lead Zinc Organi-
zation, Inc., New York, 1976, pp. 56–59, rev. 1986.
6. H. E. Brown, Zinc Oxide, Properties and Applications, International Lead Zinc Organi-
zation, Inc., New York, 1976, pp. 88–89, rev 1986.
7. F. D. Rossini and co-workers, Circular 500, U.S. Bureau of Standards, Washington,
D.C., 1952.
8. W. Bond, J. Appl. Phys. 36, 1974 (1964).
9. T. C. Wilder, Trans. Metall. Soc. AIME 245, 1370 (1969).
Q4 10. K. K. Kelley, U.S. Bur. Min. Bull. 584 (1960).
11. D. D. Wagman and co-workers, U.S. Bureau of Standards Technical Note, U.S. Bureau
of Standards, Washington, D.C., 1968, pp. 270–273.
12. P. Pascal, Nouveau Traite de Chemic Minerals, Vol. V, Masson et Cie, Paris, 1956.
13. M. Seitz and D. Whitmore, Phys. Chem. Solids 29, 1033 (1968).
14. Ceram. Ind. (Chicago) 84, 157 (1965).
15. J. Turkevich and P. W. Selwood, J. Am. Chem. Soc. 63, 1077 (1941).
16. H. Ibach, Solid State Commun. 4, 353 (1966).
17. S. B. Salvin, Ind. Eng. Chem. 36, 336 (1944).
12 ZINC COMPOUNDS

18. A. M.van Rij and W. J. Pories, in J. O. Nriagu, ed., Zinc in the Environment, John Wiley
& Sons, Inc., New York, 1980, Part 2, pp. 215–236.
19. E. H. Bunce and H. M. Haslam, Trans. AIME 121, 678 (1936).
20. C. D. Holley, The Lead and Zinc Pigments, John Wiley & Sons, Inc., New York, 1909,
pp. 152–153.
21. M. Morton, ed., Introduction to Rubber Technology, Reinhold Publishing Co., New York,
1959, p. 222.
22. A. P. Thompson, in C. H. Mathewson, ed., Zinc, Reinhold Publishing Co., New York,
1959, p. 646.
23. J. H. Calbeck in Ref. 23, pp. 344–367.
24. U.S. Pat. 1,522,097 (Jan. 6, 1925), F. G. Breyer, E. C. Gaskill, and J. A. Singmaster, (to
The New Jersey Zinc Co.).
25. U.S. Pat. 959,924 (May 31, 1910) E. Dedolph.
26. W. E. Harris, Trans. AIME 121, 702 (1936).
27. C. W. Morrison, in Ref. 23, pp. 298–306.
28. Agency for Toxic Substances and Disease Registry (ATSDR), Available at http://www.
emla.hu/korkep/chems/tfacts60.html, Sept. 19, 2005.
29. R. E. Lund and co-workers, in C. H. Cotterill and J. M. Cigan, eds., Extractive Metallurgy
of Lead and Zinc, Vol. II, AIME, New York, 1970, pp. 549–580.
30. U.S. Pat. 1,522,096; 1,522,098 (Jan. 6, 1925), F. G. Breyer, E. C. Gaskill, and J. A.
Singmaster, (to The New Jersey Zinc Co.).
31. W. A. Thomas and W. A. Handwerk, Min. Eng. 5, 1203 (1953).
32. T. R. Janes, in Ref. 23, p. 385.
33. H. E. Lee and W. T. Isbell, in Ref. 23, pp. 307–314.
34. U.S. Pat. 2,303,330 (Dec. 1, 1942), B. R. Silver and E. R. Bridgewater (to The New Jersey
Zinc Co. and E. I. du Pont de Nemours & Co., Inc.).
35. U.S. Pat. 1,997,925 (April 16, 1953) A. C. Eide (to American Zinc Lead and Smelting Co.).
36. U.S. Pat. 2,251,869 (Aug. 5, 1941), D. L. Gamble and J. H. Haslam (to The New Jersey
Zinc Co.).
37. U.S. Pat. 4,270,955 (June 2, 1981), D. M. Eshelman (to The New Jersey Zinc Co.).
38. U.S. Pat. 2,372,367 (March 27, 1945), H. A. Depew (to American Lead Zinc & Smelting
Co.).
39. Assembly of Life Sciences, Zinc: Medical and Biologic Effects of Environmental Pollu-
tants, Subcommittee on Zinc, National Research Council, University Park Press,
Baltimore, Md., 1979, pp. 251–253.
40. P. Drinker and co-workers, J. Ind. Hyg. 3, 98 (1927).
41. R. P. Batchelor and co-workers, J. Ind. Hyg. 8, 322 (1926).
42. Ref. 16, pp. 6–7.
43. R. G. Silvey and G. E. Myers, in Ref. 19, Part 2, pp. 237–253.
44. Ref. 19, Parts 1 and 2.
45. Ref. 41, Chapt. 7.
46. G. J. Brewer and A. S. Prasad, eds., Progress in Clinical and Biological Research, Vol. 14,
A. R. Liss, New York, 1977.
47. Ref. 41, pp. 73–83.
48. National Research Council, Nutrient Requirement Series, National Academies Press,
Washington, DC, updated editions 1994–2001.
49. Ref. 41, p. 123.
50. Ref. 19, Part 2, pp. 4–5.
51. Ref. 41, p. 187.
52. Ref. 41, p. 249.
53. Ref. 19, Part 2, pp. 45–53.
54. J. W. Hoffman and I. Lander, Aust. J. Chem. 21, 1439 (1968).
 ZINC COMPOUNDS 13

55. N. L. Sax, Dangerous Properties of Industrial Materials, 5th ed., Van Nostrand Reinhold,
New York, 1979, pp. 1100–1104.
56. L. C. Copeland and O. A. Short, J. Am. Chem. Soc. 62, 3285 (1940).
57. S. Schlag,“ZnO and Zinc Chemicals Market Update”, Proceeding of the 2016 Zinc and
Zinc Oxide Industries Conference, Scottsdale, AZ, International Zinc Assn., Durham,
NC, February 21–14, 2016.
58. W. J. Hamer, J. Electroanal. Chem. 10, 140 (1965).
59. Chem. Market. Rep. 198, 43 (1970); 208, 35 (1975); 214, 37 (1978); 216, 37 (1979); 218,
37 (1980); 250, 38 (1996).

GENERAL REFERENCES

N.S. Berke and M.A. Caldarone, Concr. Int. 42–26 (2013).

M. Darroudia and co-workers, Ceram. Int. (2013). doi: http://Dx.Doi.Org/10.1016/J.
Ceramint.2013.09.032.
A. Moezzi and co-workers, Chem. Eng. J. (2010), doi: 10.1016/j.cej.2012.01.076.
J. Wu and D. Xue, Sci. Adv. Mater. 3 (2), 127–149 (2011).

FRANK E. GOODWIN
International Lead and Zinc Research Organization, Inc,
Durham, NC, USA
 Keywords/Abstract
Dear Author,

Keywords and abstracts will not be included in the print version of your article but only
in the online version. The abstract and keywords are included in the print version only
for your review.

Abstract:

Zinc is in group 12 (IIB) of the periodic table and exhibits a valence of +2 in all its
compounds. Being high on the electromotive series, zinc forms quite stable compounds
and, as such, resembles magnesium. Bonding in zinc compounds tends to be covalent, as in
the sulfide and oxide.
In this article, the properties of zinc compounds are provided, with special attention given
to zinc oxide, zinc chloride, and zinc sulfate. Production and processing of these compounds
are discussed. Zinc is needed for the proper functioning of plants and animals and this is
discussed along with health and safety aspects, uses, and economics.

Keywords: essential micronutrient; zinc chloride; zinc compounds; zinc oxide; zinc sulfate.
 Author Query
1. References [2, 58,59] are not cited in the text. Please cite them in the text or
remove them from the reference list.
2. Please check the usage of (qv) as some text preceding it appears to be missing.
3. Please provide the author/corporate author in References [2,14,59].
4. Please provide the volume no. in Reference [10].

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