Metallic Soaps 1

Metallic Soaps
Angelo Nora, FACI S.p.A., Carasco, Italy
Alfred Szczepanek, Faistenlohestr. 5, München, Federal Republic of Germany
Gunther Koenen, Peter Greven Fettchemie GmbH, Bad Münstereifel, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 1 5.3. Lithium Soaps . . . . . . . . . . . . . . 6

2. Production . . . . . . . . . . . . . . . . 2 5.4. Magnesium Soaps . . . . . . . . . . . . 7
2.1. Raw Materials . . . . . . . . . . . . . . 2 5.5. Calcium Soaps . . . . . . . . . . . . . . 7
2.2. Industrial Processes . . . . . . . . . . 3 5.6. Barium Soaps . . . . . . . . . . . . . . 8
2.2.1. Double Decomposition . . . . . . . . . 3 5.7. Aluminum Soaps . . . . . . . . . . . . 8
2.2.2. Direct Reaction with Metal Com- 5.8. Lead Soaps . . . . . . . . . . . . . . . . 9
pounds . . . . . . . . . . . . . . . . . . . 3 5.9. Copper Soaps . . . . . . . . . . . . . . 10
2.2.3. Direct Reaction with Metals . . . . . . 4 5.10. Zinc Soaps . . . . . . . . . . . . . . . . 11
2.3. Plant Equipment . . . . . . . . . . . . 4
5.11. Cadmium Soaps . . . . . . . . . . . . . 12
2.4. Storage . . . . . . . . . . . . . . . . . . . 5
5.12. Manganese Soaps . . . . . . . . . . . . 12
3. Fire and Explosion Protection . . . . 5
4. Occupational Health and Environ- 5.13. Iron Soaps . . . . . . . . . . . . . . . . . 13
mental Protection . . . . . . . . . . . . 5 5.14. Cobalt Soaps . . . . . . . . . . . . . . . 13
5. Individual Metallic Soaps . . . . . . . 6 5.15. Nickel Soaps . . . . . . . . . . . . . . . 14
5.1. Sodium Soaps . . . . . . . . . . . . . . 6 6. Quality Specifications . . . . . . . . . 14
5.2. Potassium Soaps . . . . . . . . . . . . . 6 7. References . . . . . . . . . . . . . . . . . 15

1. Introduction no longer have great significance. Naphthenic

Originally the term metallic soaps was only
used for metal salts of fatty acids of natu-
rally occurring animal fats (mainly tallow and
lard) and vegetable fats. Today, metallic soaps
are understood to refer to the sparingly solu-
ble or insoluble salts of saturated and unsatu-
rated, straight-chain and branched, aliphatic car-
boxylic acids with 8 – 22 carbon atoms. Exam-
ples are saturated fatty acids like stearic acid
(octadecanoic acid), lauric acid (dodecanoic
acid), 12-hydroxystearic acid, and mixtures of
acids with 8 – 22 carbon atoms; unsaturated fatty
acids like oleic acid (cis-9-octadecenoic acid)
and linoleic acid (9,12-octadecadienoic acid)
(→ Fatty Acids); synthetic carboxylic acids like
isostearic acid, 2-ethylhexanoic acid (→ Car-
boxylic Acids, Chap. 10.4.), dimethylhexanoic
acids, trimethylhexanoic acids; and mixtures of
synthetic aliphatic isocarboxylic acids.
The salts of the alicyclic naphthenic acids and
resin acids (abietic acid) are also frequently re-
garded as metallic soaps due to properties related
to their manufacture and applications. How-
ever, the metal salts of resin acids (resinates)
acids are a byproduct of oil refining (→ Oil Re-
fining). The byproduct is a mixture of linear and
cyclic aliphatic hydrocarbons containing car-
boxylic acid groups.
The production and properties of soaps of al-
most all metals are described in the literature.
However, only the metallic soaps of the follow-
ing metals (arranged according to the periodic
table) are industrially important: lithium, potas-
sium, sodium (group 1); magnesium, calcium,
barium (group 2); zirconium (group 4); man-
ganese (group 7); iron (group 8); cobalt (group
9); nickel (group 10); copper (group 11); zinc,
cadmium (group 12); aluminum (group 13); lead
(group 14); as well as cerium and mixtures of
rare earths.
Uses. Metallic soaps are used as thickeners
for oils and other organic media, as lubricants
(→ Lubricants and Related Products, Chap. 9.)
and release agents, as well as drying agents (dry-
ers). Dryers are metallic soaps that accelerate
drying as, for example, in the film formation
of paints based on drying oils and alkyd resins
→ Paints and Coatings). Metallic soaps are used

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

10.1002/14356007.a16 361
2 Metallic Soaps
as acid scavenger and lubricants both internally
and externally in polyolefins and PVC. Sodium
and magnesium soaps are important as additives
in the pharmaceutical and cosmetics industries,
as well as in the building industry. Lithium soaps
are especially important as components of lubri-
cating greases.
Properties. The physicochemical properties
of metallic soaps are determined by the nature
of the metal ion and the organic acid. The metal-
lic soaps of saturated straight-chain carboxylic
acids are solids and either have a sharp melting
point or melting range, or carbonize on heating
without melting. Pastelike products contain wa-
ter.
Unsaturated fatty acids and branched syn-
thetic acids form metallic soaps with plastic
properties. They are therefore usually produced
and used in solution.
Types. Metals can form the following metal-
lic soaps depending on their valence and prop-
erties:
Neutral soaps: RCOOMI
(RCOO)2 MII
(RCOO)3 MIII
Acid soaps: (RCOO)2 MII · RCOOH
(RCOO)3 MIII · RCOOH
Acid soaps contain bound free organic acid
that can be removed by extraction.
In basic soaps (RCOO)2 MII · (MO)x (x = 1,
2), complexed metal oxides can also be present
in the form of metal hydroxides or as mixtures
of metal oxides and hydroxides.
Mixed soaps (RCOO)(R COO)MII consist of
mixed crystals or mechanically produced mix-
tures.
Complex soaps: Lead can form complex basic
salts: (PbO)x · PbSO4 · [(RCOO)2 Pb]y . Other
inorganic anions can also be present instead of
sulfate.
Overview. A selection of commercially
available metallic soaps and those described
in the literature is given in Table 1. The soaps
are listed in alphabetical order according to the
chemical symbol of the metal. The products se-
lected are representative of other homologous
soaps. At least one metallic soap of each type is
described in the list of references.
2. Production
2.1. Raw Materials
The organic acids used for the production of
metallic soaps are either solid or liquid. They
are supplied in sacks, drums, containers, or tank
cars. The use of products packed in paper sacks
should be minimized because of high handling
costs and danger of impurities. Acids purchased
in drums and containers should be stored at the
recommended temperature to avoid total or par-
tial crystallization. For large-scale production,
molten acids are generally supplied in tank cars.
A tank farm is required, and the tanks should
preferably be made of stainless steel to avoid
attack on the tank material and darkening and
contamination of the product.
Blanketing with an inert gas (e.g., nitrogen
or carbon dioxide) may be necessary to prevent
darkening caused by oxidation. Acids such as
stearic acid, which are solid at room tempera-
ture and are supplied as liquids, must be kept
above the melting point, preferably by circula-
tion of warm water to avoid overheating at the
wall. Stainless steel and aluminum are used as
tank materials.
The acids are best dosed in the liquid state; the
accuracy of pumps working by volume dosage
is sufficient if temperature and density are taken
into consideration. Nowadays, mass flow meters
are used with better accuracy.
The melting of solid organic acids in the reac-
tion vessel reduces throughput; a separate melt-
ing vessel should therefore be used.
The metal salts, which are usually solids, are
supplied in sacks, drums, or containers; they are
dosed by means of weighing systems. Because
the salts may be very toxic, appropriate mea-
sures for personal and environmental protection
must be taken.
The majority of metallic soaps marketed are
stearates. These are salts of stearin, a mixture
of mainly C16 – C18 fatty acids that can be de-
rived both from animal fats (tallow or lard)
or from vegetable oils. Recently, the demand
for stearates from vegetable sources has in-
creased, mainly for applications in foods, animal
feeds, pharmaceuticals, and cosmetics due to the
bovine spongiform encephalopathy (BSE) prob-
lem, even though stearin from tallow is largely
deactivated during its production.
 Metallic Soaps 3
Table 1. Metallic soaps

Element Stearate 12-Hydroxy- Laurate Oleate Naphthenate Resinate 2-Ethyl- Reference

stearate hexanoate

Ag + + + + + + [1], [2]
Al + + + + + + [3–5]
Ba + + + + + [6]
Be + + [7]
Bi + + + + [8]
Ca + + + + + [9]
Cd + + + + + + [10]
Ce + + [11]
Co + + + + + [12]
Cr + + + [13]
Cu + + + + [14]
Fe + + + + [13]
Hg + + + + [7]
K + +
Li + + [15]
Mg + + + + + + [16]
Mn + + + + + [17]
Na + +
Ni + + + + + [13]
Pb + + + + + [18]
Sb + [19]
Sn + + + + [20]
Sr + + [7]
Th + [7]
Ti + + [21]
U + + [7]
V + [22]
Zn + + + + + + + [23]
Zr + + + + [21]

2.2. Industrial Processes
Because of the great number of possible com-
binations of metal and acid groups, only gen-
eral production processes can be described here.
Three types of reaction are possible:
1) Double decomposition (precipitation)
2) Direct reaction with metal oxides, metal hy-
droxides, or metal salts of volatile acids
3) Direct reaction with metals
2.2.1. Double Decomposition
The soap solution can also be added to the metal
salt solution, or both solutions can be run si-
multaneously into a separate precipitation ves-
sel. For sparingly soluble alkali soaps, alkaline
solutions are used as the reaction medium. Plas-
tic metallic soaps are precipitated in the presence
of a water-immiscible solvent which absorbs the
metallic soaps formed.
2.2.2. Direct Reaction with Metal
Compounds

In the first step of the double decomposition (pre-
cipitation) process the organic acid is saponified
with alkali. In the second step, the resulting al-
kali soap is precipitated by addition of a solution
of a water-soluble metal salt:
RCOOH + 2 NaOH −→ 2 RCOONa + 2 H2 O
2 RCOONa + Ca2+ −→ (RCOO)2 Ca + 2 Na+
The reaction of organic acids with metal oxides,
metal hydroxides, or salts of volatile acids, such
as carbonates, acetates, or formates can be car-
ried out by the following types of process:
1) Melt process
2) Reaction in the aqueous phase
3) Reaction in solvents or lubricants
4 Metallic Soaps
Melt Process. In the melt process, metal ox-
ides, metal hydroxides, or metal salts of volatile
acids are fed into a stirred melt of the organic
acid at elevated temperature. The rate of addi-
tion should be adapted to the reaction rate to
prevent foaming caused by evaporation of wa-
ter or volatile acid. With unreactive metal com-
pounds, delays can occur in the initial phase. To
initiate the reaction, small quantities of water
or, for metal oxides, volatile acids such as acetic
acid are often added.
The melt process is suitable for metallic soaps
with melting points below 140 ◦ C, which pro-
duce relatively nonviscous melts. These are gen-
erally metallic soaps with sharp melting ranges
such as calcium, magnesium, lead, zinc, or cad-
mium stearate. Alkaline earth stearates are often
used in combination with low-melting metal-
lic soaps (e.g., as PVC stabilizers in the com-
binations barium – cadmium, barium – zinc, or
calcium – lead), a low-melting acidic metallic
soap is first produced in the melt; the high-
melting soap is then formed in the melt of the
low-melting one [24].
Reaction in the Aqueous Phase. In the
aqueous-phase reaction, metal oxides or hy-
droxides react in the presence of catalysts such
as amines, sparingly soluble alcohols, or other
wetting agents. The processes are applicable
only to solid metallic soaps (e.g., barium, mag-
nesium, zinc, lead, and calcium stearates) [17].
Reaction in solvents is preferred if the di-
rect melt process is impossible or gives low-
quality products, or if the metallic soaps are to be
used in solution. Dryers and liquid PVC stabi-
lizers based on branched-chain aliphatic carbox-
ylic acids and naphthenic acids are mainly pro-
duced by this process. The solvent (e.g., solvent
naphtha or white spirits) also acts as an entrainer
for removing reaction water by azeotropic dis-
tillation [25].
For solid metallic soaps the solvent can be
replaced by organic compounds such as alkanes
or fatty alcohols which are solid at room temper-
ature and cannot be saponified by metal oxides.
The reaction medium cannot be removed and
remains in the final product, which may, for ex-
ample, be used as a lubricant for plastics [26].
Lubricating greases provide a further example
of a reaction product that remains in the reac-
tion medium (→ Lubricants and Related Prod-
ucts, Chap. 9.).
Continuous Process. Metal oxides are dis-
solved in aqueous ammonia and converted to ba-
sic metal carbonates by passage of gaseous car-
bon dioxide. The molten fatty acids in aqueous
ammonia are converted to saponified emulsions.
The two components are continuously mixed in
the blade region of a rotor – stator mixer with in-
terlocking radial surfaces. The metallic soaps are
produced in pastelike to semidry form; they are
removed continuously, dried, and ground [27].
Dust-Free Granules. For many uses, metal-
lic soaps do not have to be in powder form. To
prevent explosion and promote better handling
and dosage, dust-free granules are preferred. The
granules are produced from straight-chain fatty
acids (C8 – C22 ) and metal oxides, hydroxides,
or carbonates. Granule formation is controlled
by the rate of addition of the metal compound,
stirring rate, temperature, and water content of
the reaction mixture, which is adjusted to ca.
10 wt %. The reactors are mixers equipped for
vacuum drying. In the case of unreactive metal
oxides (e.g., zinc oxide), chelating acids like cit-
ric, tartaric, or glycolic acid are added as cat-
alysts. Because of the small quantity of water
involved and the absence of filtration, drying,
and pulverization stages, the process runs very
economically by using the heat of reaction [28].
2.2.3. Direct Reaction with Metals
Organic acids are treated with metal granules,
powders, or gauze at elevated temperature, usu-
ally with a solvent as the reaction medium. Di-
rect reaction with metals is used when it offers
economic advantages or allows the replacement
of unreactive metal oxides by metals [29].
2.3. Plant Equipment
Direct Reaction in Aqueous Media. Reac-
tion vessels, filtration, and drying equipment are
necessary for reaction in aqueous media (the pre-
cipitation process).
Stainless steel reaction vessels are preferred
for the production of alkali soaps. The acids

are saponified at 60 – 90 ◦ C at a dilution of
1 : 5 – 1 : 10 depending on the type.
Metal compounds are dissolved at 40 – 50 ◦ C,
depending on their solubility, in stainless steel
containers. Tanks for intermediate storage of re-
action mixtures are equipped with slow stirrers
or recirculation pumps.
In the filtration of metallic soaps, the fil-
ter cake should be as dry as possible for eco-
nomic reasons. Nutsche (pan) filters, drum filter
presses, and plate filter presses have now been
largely replaced by membrane filter presses or
continually functioning automatic filters. In the
direct reaction in the aqueous phase, the filter
water produced is used as circulation water and
must be put into intermediate storage.
Belt, drum, and rotary dryers have proved
successful as drying units. In drying units with-
out integrated pulverization and classifying fa-
cilities, pulverization units are necessary.
Melt Process. For direct reaction by the melt
process or in lubricants, stainless steel or glass-
lined reactors fitted with stirrers, heaters (up
to 160 ◦ C), and vapor extractors are used. The
melts are then processed into a solid, dust-
free form by using flaking equipment, cooling
belts, or spraying devices. If desired they can be
ground.
Precipitation or Direct Reaction in Sol-
vents. For precipitation in the presence of sol-
vents or direct reaction in solvents, stainless steel
or glass-lined steel reactors are used that are fit-
ted with stirrers, heaters (up to 160 ◦ C), vacuum
connections, and reflux condensers with water
separators. Suitable filter equipment is neces-
sary for filtration of viscous solutions. Reaction
with metals is also possible in this type of plant.
Finally, the product is ground in various mills to
obtain different particle size distributions.
2.4. Storage
The liquid to pastelike, solvent-containing
metallic soaps are generally stored in packag-
ing forms ready for sale (e.g., cans, drums, or
containers). Bags or big bags are often used for
powdered metallic soaps. For storage in large
silos, protective measures against fire and ex-
plosion are necessary (see Chap. 3).
Metallic Soaps 5
3. Fire and Explosion Protection
Fire Protection. Metallic soaps are flam-
mable substances that burn with intense smoke
production. The resulting oxides are carried into
the air and may be toxic (heavy metals). This
should be taken into consideration during fire
fighting. Foam and carbon dioxide extinguish-
ers are suitable fire-fighting agents.
For metallic soap solutions in organic media,
local regulations for the handling and storage
of flammable liquids must be observed. Plas-
tic metallic soaps are not readily flammable
because of their small surface area. Powdered
metal soaps have a relatively large surface area
and are flammable. With metallic soaps based on
unsaturated fatty acids such as oleic and linoleic
acids, self-ignition can occur if the packed prod-
ucts are not cooled sufficiently. Self-ignition is
promoted by soaps of heavy metals, which are
oxidation catalysts.
Explosion Protection. When organic sol-
vents are used in the production of metallic
soaps, plants must be protected against explo-
sion by suitable equipment in compliance with
prevailing regulations. Metallic soaps in pow-
der form can, like other organic dusts, cause
dust explosions, which are most likely to occur
during drying, pulverizing, and storage. To pre-
vent buildup of static charge (ignition source),
good grounding (earthing) should be ensured.
Formation of sparks by metal particles is dif-
ficult to avoid. Magnetic separators do not of-
fer any safety improvements because the metals
are either nonmagnetic or coated by the metallic
soaps. To avoid serious damage, relevant parts of
the plant must be equipped with pressure-release
devices. If this precaution is not taken, a pressure
wave can lead to severe secondary dust explo-
sions and destruction of the plant.
4. Occupational Health and
Environmental Protection
Occupational Health. Soaps of calcium,
sodium, magnesium, potassium and zinc are
nontoxic substances and do not require partic-
ular protective measures. Soaps of heavy met-
als are toxic substances that can lead to acute
6 Metallic Soaps
or chronic poisoning. Suitable measures to pro-
tect the worker are dust extraction, protective
clothing, dust masks (when dust sources cannot
be avoided), and regular medical checkups. The
MAK and TLV values are given for individual
metals (Chap. 5).
Wastewater. The filter water produced in the
direct reaction in the aqueous phase is col-
lected and reused as reaction water; complete
circulation eliminates wastewater production. In
the double decomposition reaction, considerable
quantities of neutral salts such as sodium sul-
fate, sodium chloride, and sodium nitrate are
produced, which are difficult or impossible to
remove by water treatment. This fact should be
given particular consideration in the choice of
plant location. Other sources of water pollution
are bleeding of the filter presses and excess metal
salts used for precipitation. Before wastewater
is sent to the water treatment plant, the heavy
metals are therefore precipitated by addition of
lime and/or passing through CO2 to give a pH
of 8.5 – 9.
Air Pollution. Solvent emissions must be re-
duced in accordance with local regulations by
means of a scrubber or absorption tower. Steam-
or water-jet vacuum pumps are often used
and entrain small quantities of mostly water-
immiscible solvents; oil separators are therefore
necessary.
The dryers for powdered metallic soaps may
release residual dust-laden or water-vapor-con-
taining air into the surroundings. To purify
the air, filtration units with large surface areas
are necessary. Automatic dust-measuring instru-
ments built into the exhaust stack switch off the
plant if the dust concentration becomes too high
(e.g., because of a tear in the filter). The residual
emission is discharged into the surroundings via
a high exhaust stack. Permitted emission values
are stipulated in national air purity regulations.
5. Individual Metallic Soaps
5.1. Sodium Soaps
Production. The sodium soaps of stearic and
oleic acid have the most industrial importance.
They are produced by direct reaction. A solution
of sodium hydroxide is added to the fatty acid,
and when the reaction is complete, the product
is dried and grounded.
Properties. See Table 2.
Uses. Sodium stearate is used in various
fields, but mainly in the pharmaceutical and cos-
metics industries as an emulsifying and gelling
agent. Sodium oleate is largely used in the build-
ing industry as an initial dispersing agent that be-
comes a waterproofing agent after application.
5.2. Potassium Soaps
Producton. The potassium soaps are pro-
duced by direct reaction. A solution of potas-
sium hydroxide is added into the fatty acid, and
after completion of the reaction the product is
dried and ground.
Properties. See Table 2.
Uses. Potassium soaps, mainly stearate and
oleate, are used for their swelling properties.
They are used to thicken natural and synthetic
oils and to raise the melting point and flexibility
of waxes and paraffins.
5.3. Lithium Soaps
Production. The lithium soaps of stearic and
12-hydroxystearic acid have the most industrial
importance. They are produced by direct reac-
tion in aqueous medium. A very dilute solution
of lithium hydroxide hydrate, LiOH · H2 O (con-
centration ca. 1 : 40, i.e., 2.5 wt %), is slowly
added with intense stirring to the fatty acid dis-
persed in water in the ratio 1 : 20 at 90 ◦ C.
Lithium soaps are difficult to filter; floccula-
tion is therefore improved by using an excess of
lithium hydroxide or by adding neutral salts. The
resulting lithium soap dispersion is, however, of-
ten not filtered but spray-dried, even though this
involves evaporation of a large quantity of wa-
ter. Under modified reaction conditions, lithium
hydroxide hydrate can be replaced by lithium
carbonate and ammonia.
 Metallic Soaps 7
Table 2. Technical data for some commercial soaps of sodium, potassium, lithium, and magnesium

Compound CAS registry Appearance Free fatty Total ash or Moisture∗, Bulk density∗, Melting
no. acid∗, metal content, wt % g/L range,
◦
wt % wt % C

Lithium stearate [4485-12-5] white powder 1 2.4 Li 0.5 230 190 – 210
Lithium 12-hydroxy-
stearate [7620-77-1] white powder 1 2.3 Li 0.5 400 > 200
Magnesium stearate,
technical [557-04-0] white powder 2 7–8 4–5 250 115 – 135
Magnesium behenate [43168-33-8] white powder 2 6–7 6.0 250 ca. 140
Sodium oleate [143-19-1] yellowish powder 0.1 22 – 24 4 350 200 – 210
Sodium stearate [822-16-2] white powder 1 22 – 24 2 250 210 – 220
Potassium stearate [593-29-3] white powder 2 12 K 1.5 300 215 min.

∗ Approximate values.

Properties. See Table 2. Properties. See Table 2. Magnesium soaps

Uses. Lithium soaps have particularly good
swelling properties. Lithium stearate is used to
thicken natural and synthetic oils; to raise the
melting point and flexibility of microcrystalline
waxes and paraffins; as an additive for coating
waxes to increase water repellence; and as a lu-
bricant in the production of injection-molded ar-
ticles from light metal. Multipurpose lubricat-
ing greases have particularly good penetration
properties, high oxidation stability, and drop-
ping points up to ca. 200 ◦ C. Lithium 12-hy-
droxystearate is used primarily for the produc-
tion of lubricating greases based on synthetic
oils (e.g., from silicon and ester oils). These lu-
bricants cannot be produced by the usual saponi-
fication in mineral oil because the synthetic oils
are attacked under the saponification conditions
employed.
of long-chain fatty acids have a high specific sur-
face area and can absorb considerable quantities
of liquid, giving a creamy consistency. They are
insoluble in alcohols, esters, ketones, ethers, and
hydrocarbons.
Uses. Magnesium soaps are used in the plas-
tics industry as lubricants and mold-release
agents for thermosetting plastics and thermo-
plastics; in the pharmaceutical industry as pro-
cessing aids in the production of dragées and as
lubricants for tablet pressing; in the cosmetics
industry as powder components and for consis-
tency in water-free ointments; in the wax indus-
try to increase the retention of creams based on
semisolid wax products and in the production of
lubricating waxes; and as a waterproofing agent
for the building industry.

5.5. Calcium Soaps

5.4. Magnesium Soaps
Calcium soaps are generally neutral salts. They
Magnesium soaps are produced as neutral salts
are obtained by double decomposition or direct
by the double decomposition process, using
reaction. The raw materials consist of saturated
water-soluble magnesium salts (primarily mag-
straight-chain aliphatic acids (C8 – C22 ), montan
nesium chloride) and alkali salts of organic acids
wax acids, unsaturated straight-chain carboxylic
in an aqueous medium, or by direct reaction with
acids (e.g., oleic and linoleic acids), branched-
magnesium oxide. Magnesium soaps in powder
chain aliphatic carboxylic acids (e.g., ethylhex-
form based on stearic acid are particularly im-
anoic acids), naphthenic acids, and resin acids.
portant. The degree of purity required, especially
Calcium chloride and calcium hydroxide are
with regard to heavy-metal impurities, deter-
used as the metal compounds.
mines the choice of raw materials in pharmaceu-
Very finely divided calcium soaps of the
tical products. Pharmaceutical quality must ful-
aliphatic straight-chain carboxylic acids are pro-
fill the requirements of the European, Japanese,
duced by double decomposition in aqueous
and U.S. pharmacopoeias.
8 Metallic Soaps
medium. Stearates, myristates, and laurates are
commercial products, but the most important
calcium soaps are stearates.
Direct reaction 2.2.2 (Melt process) is the
most common production method for solid cal-
cium soaps.
In both cases the products are free of water-
soluble salts; their purity depends on the quality
of calcium hydroxide used.
Calcium soaps are also produced as neutral
soaps by the double decomposition process from
water-soluble calcium salts and sodium soaps in
an aqueous medium. This process can be used
to obtain a very high specific surface area, but
is mainly used to produce highly crystalline cal-
cium soaps.
Aqueous calcium stearate pastes with a solid
content of 40 – 50 % are also produced by the di-
rect process and are used as additives for paper
coating (slips).
Calcium soaps which are not in powder form
and are therefore used mostly as solutions in or-
ganic media (e.g., 2-ethylhexanoates and naph-
thenates) are produced by direct reaction in an
appropriate medium.
Properties. See Table 3.
Uses. Calcium stearate is the most important
calcium soap. Calcium stearate is widely used
in polyolefins (PE, PP) and in PVC as a lubri-
cant (internal or external), release agent, and acid
scavenger. Calcium soaps are used as physiolog-
ically inert lubricants and secondary stabilizers
in the plastics industry to improve the flow prop-
erties and prevent the caking of hygroscopic sub-
stances; as lubricants and mold-release agents
along with magnesium soaps in pharmaceuti-
cal tablet pressing; as waterproofing additives
in agents used for building protection and for
surface treatment of fillers; and in the paper in-
dustry in recording paper, diagram paper, and
coating slips.
5.6. Barium Soaps
The most important organic acids in bar-
ium soaps are 12-hydroxystearic, lauric, 2-
ethylhexanoic, and naphthenic acids. The metal
compounds used are barium chloride and barium
hydroxide (mono- or octahydrate). The TLV –
TWA value for barium is 0.5 mg/m3 .
Properties. See Table 3.
Uses. Barium soaps are used in the paint in-
dustry for wetting pigments and as dispersion
agents; in metal forming as a component of wire-
drawing and other auxiliaries; and in the plastics
industry as lubricants and costabilizers.
5.7. Aluminum Soaps
Commercial aluminum soaps are generally pro-
duced by treating alkali soaps with water-soluble
aluminum salts. In precipitation in aqueous sys-
tems, agglomerates of aluminum hydroxide and
carboxylic acids are first produced which then
react with each other to form salts during the
subsequent drying process.
Because aluminum is trivalent, three types of
soap are possible:
1) Aluminum monosoaps Al(OH)2 (OOC−R)
2) Aluminum disoaps Al(OH) (OOCR)2
3) Aluminum trisoaps Al(OOCR)3
The polymeric structure of aluminum soaps is
not conveyed by the formulas [30].
All types of organic acids are used for alu-
minum soaps, but particularly stearic, oleic,
naphthenic, and 2-ethylhexanoic acids. Alu-
minum sulfate is preferred as the water-soluble
aluminum salt, along with potassium aluminum
sulfate and aluminum chloride. In industrial pro-
duction of the three types of aluminum soap, the
organic acids are saponified with 1, 2, or 3 mol of
alkali, respectively. Because the three types dif-
fer greatly in their thickening properties, com-
mercial products are available with intermedi-
ate metal contents. The metal, ash, and free fatty
acid contents are given to characterize the soaps.
To achieve special thickening properties,
above all for the production of lubricating
greases based on mineral oil, fatty acids are com-
bined with aromatic acids (e.g., benzoic or ph-
thalic acid) or with dimeric fatty acids. Lubri-
cating grease with high fastness to fulling resis-
tance and a high dropping point is obtained in
this way.
Aluminum soaps in powder form are obtained
by double decomposition in aqueous medium.
 Metallic Soaps 9
Table 3. Technical data for some commercial soaps of calcium and barium

Compound CAS registry Appearance Free fatty Total ash, Moisture∗, Bulk density, Melting
no. acid∗, wt % wt % wt % g/L range, ◦ C

Calcium stearate, [1592-23-0] white powder 1–2 9 – 10 2–3 120 – 130 120 – 160
precipitated
Calcium stearate, direct [1592-23-0] white powder 0.5 9 – 10 2 200 120 – 160
reaction
Calcium arachidate [22302-43-8] white powder 1 8–9 1.5 200 (tapped) ca. 150
Calcium [3159-62-4] white powder 1 8.5 – 9.5 2–3 250 (tapped) ca. 140
12-hydroxy-stearate
Calcium laurate [4696-56-4] white powder 1 13 – 14 2–3 300 (tapped) ca. 140
Calcium oleate [142-17-6] yellow mass 2 10 – 11 1 ca. 120
Calcium [136-51-6] yellowish 2 16 – 17 1 ca. 160
2-ethyl-hexanoate
powder
Calcium ricinoleate [6865-33-4] yellowish 2 10 – 11 1.5 ca. 130
powder
Calcium naphthenate [61789-36-4] solid brown 11 – 12 1
mass
Barium stearate [6865-35-6] white powder 1 27 – 28 0.5 250 200
Barium laurate [4696-57-5] white powder 1 35 – 36 0.5 275 200
Barium 2-ethyl-hexanoate [2457-01-4] yellowish paste 29 – 30 0.6
Barium naphthenate [61789-67-1] dark paste 24 – 25 2

∗ Approximate values.

Catalyzed reactions between fatty acids and
freshly precipitated aluminum oxide hydrate
are known but not used industrially. Aluminum
oxide hydrate ages too quickly and is not suit-
able for melting or direct reaction processes in
nonaqueous media because of its low reactiv-
ity. An exception is the in situ production of lu-
bricating greases in which aluminum alkoxides
and freshly precipitated aluminum hydroxide
hydrate are used. The TLV – TWA value for alu-
minum is 10 mg/m3 for metal dust and 5 mg/m3
for pyro powders and welding fumes.
Properties. See Table 4. Aluminum soaps of
long-chain fatty acids are insoluble in water,
lower alcohols, esters, and ketones; they are sol-
uble in hydrocarbons, toluene, xylene, ethylene
glycol, chlorinated hydrocarbons, and vegetable
and mineral oils. The most striking property of
aluminum soaps is their capacity for thicken-
ing organic media and for forming solid gels
with them. Gel consistency increases in the order
trisoaps, disoaps, and monosoaps. The gels are
destroyed by polar substances such as primary
amines, ammonia, pyridine, and lower alcohols.
Uses. The gel-forming property of aluminum
soaps is exploited in the mineral oil, cosmetics,
and pharmaceutical industries. They are also em-
ployed in the paint industry as antisettling and
matting agents and for wetting pigments. Alu-
minum soaps in powder form are used as lubri-
cants in thermosetting plastics and thermoplas-
tics, as waterproofing agents in building protec-
tion, and as flow promoters for caking powders.
5.8. Lead Soaps
Neutral lead soaps are produced by double
decomposition, by direct reaction in the melt, or
by direct reaction in aqueous media in the pres-
ence of catalysts such as triethanolamine and
sparingly soluble alcohols [17].
Basic lead soaps are produced by direct re-
action in the presence of catalysts in aqueous
media. The addition salts contain a maximum of
two molecules of lead(II) oxide to one molecule
of neutral lead soap:
3 PbO + 2 HOOCR → 2 PbO · Pb(OOCR)2 + H2 O
Direct reaction in the melt does not go be-
yond the addition of one molecule of lead(II)
oxide because of an increase in the melting point.
In the presence of a fusible organic medium
10 Metallic Soaps
Table 4. Technical data for some commercial aluminum soaps

Compound CAS registry Appearance Free fatty Total ash, Moisture∗, Tapped bulk Melting
no. acid∗, wt % wt % wt % density, g/L range, ◦ C

Aluminum tristearate [637-12-7] white powder 16 – 22 7–8 1.2 300 110 – 130
Aluminum distearate [300-92-5] fine white 3–7 10 – 11 1.2 82 150 – 160
powder
Aluminum monostearate [7047-84-9] white powder 1–3 13 – 14 1.2 170 180 – 250
Aluminum [7047-84-9] fine white 4–6 7.5 – 8.5 1.5 110 ca. 140
di-12-oxystearate
powder
Aluminum dipalmitate [14236-50-1] fine white 5–7 10.5 – 11.5 1 300 ca. 160
powder
Aluminum [555-35-1] very fine white 2–4 15.5 – 16.5 1.5 280 ca. 200
monopalmitate
powder
Aluminum dimyristate [56639-51-1] fine white 6–9 10.5 – 11.5 1 300 ca. 145
powder
Aluminum dilaurate [817-83-4] white powder 4–6 10.5 – 11.5 1 280 ca. 150

∗ Approximate values.

(e.g., C16 – C18 fatty alcohols, or a combina-
tion of fatty alcohols and paraffin or long-chain
fatty acid esters), however, a further molecule of
lead(II) oxide can be added to give dispersions
of dibasic lead soaps [24]. The basicity of ba-
sic lead soaps in the direct reaction in solvents
depends on their solubility. In general, only one
molecule of lead(II) oxide can be added.
Basic Lead Complex Soaps. The starting
material for basic lead complex soaps is an
aqueous dispersion of a basic inorganic lead salt
which reacts with fatty acids in the presence of
catalysts in an aqueous medium [31]:
4 PbO · PbSO4 + 2 HOOCR →
3 PbO · PbSO4 · Pb(OOCR)2 + H2 O
Production. Technical-grade stearic, oleic,
2-ethylhexanoic, and naphthenic acids are used
for the production of the most important lead
soaps. The principal metal source is lead oxide.
Lead acetate is used as the water-soluble lead
salt in the double decomposition process. Di-
rect reaction in aqueous medium is performed
with reactive lead(II) oxide (litharge, commer-
cial specification “canary yellow”). The red lead
oxide content should be very low because this
modification cannot form basic addition salts.
The red modification is, however, suitable for
the production of neutral salts in the melt or in
an aqueous medium. In the melt process, the lead
metal content of the lead oxide should be very
low to avoid blockage of valves by agglomera-
tion.
Regulations for personal and environmental
protection must be observed, particularly with
lead soaps in powder form. Even the absorption
of small quantities of lead can lead to chronic
illness (→ Lead, Chap. 9.; → Lead, Chap. 10.).
The MAK value for lead is 0.1 mg/m3 and the
TLV – TWA value is 0.15 mg/m3 .
Properties. See Table 5.
Uses. Neutral and basic lead stearates are
used as heat stabilizers and lubricants in PVC
processing; as lubricants in the pencil industry;
and as additives for specialty papers. Lead 2-
ethylhexanoate, naphthenates, and resinates are
used in the paint industry for wetting pigments
and as dryers, and in the mineral oil industry as
components of high-pressure lubricants.
5.9. Copper Soaps
Copper forms neutral soaps which are produced
either by double decomposition or by the direct
process in the melt or in organic media. Produc-
tion from metallic copper is also known: cop-
per powder is dispersed in solvent naphtha; cop-
per soaps that are soluble in solvent naphtha are
formed by passage of air in the presence of an
organic acid.
 Metallic Soaps 11
Table 5. Technical data for some commercial soaps of lead and copper

Compound CAS registry Appearance Free fatty Total ash or Moisture∗, Bulk Melting
no. acid∗, metal content, wt % density, range,
◦
wt % wt % g/L C

Neutral lead stearate [1072-35-1] white powder 1 27 – 28 Pb 0.2 500 105 – 110
Monobasic lead stearate [90459-52-2] white powder 1 41 – 42 Pb 1 250 – 300 110 – 120
Dibasic lead stearate [56189-09-4] white powder 1 51 – 52 Pb 0.5 450 > 200
(decomp.)
Lead 2-ethylhexanoate [16996-40-0] white, plastic 1 ca. 45 0.5
Lead oleate [1120-46-3] brown mass 1 30 – 31 1 ca. 65
Lead naphthenate [61790-14-5] dark, viscous mass 1 30 – 31 1
Copper stearate [7617-31-4] blue-green powder 1 14 – 15 1 ca. 155
Copper laurate [19179-44-3] blue-green powder 2 17 – 18 1 ca. 125
Copper 2-ethylhexanoate [22221-10-9] blue mass 23 – 24 1
Copper oleate [10402-16-1] blue-green mass 13 – 14 1
Copper naphthenate [1338-02-9] gray-green paste 14 – 15 1

∗ Approximate values.

Commercial copper soaps are produced from
stearic, naphthenic, oleic, and 2-ethylhexanoic
acids. Water-soluble copper salts, mainly cop-
per sulfate, are used as copper source for the
double decomposition; copper hydroxide or ba-
sic copper carbonate is used for direct reaction.
Production of copper soaps in powder form
by double decomposition requires a separate
plant, because cleaning the drying and filtration
units is almost impossible. The MAK values
for copper are 0.1 mg/m3 (fume) and 1 mg/m3
(dust); the TLV – TWA values are 0.2 mg/m3
(fume) and 1 mg/m3 (dusts and mists).
reaction of zinc oxide with fatty acids below the
melting point of the soaps.
Basic zinc soaps produced by double
decomposition are obtained in powder form;
the basic moiety can be in the form of a basic
soap, zinc oxide, or zinc carbonate. In organic
media, soluble zinc soaps (particularly naph-
thenates, 2-ethylhexanoate, and oleates) can be
rendered basic during the direct reaction by ad-
dition of excess zinc hydroxide. Soaps with 1.7
equivalents of zinc hydroxide to 1 equivalent of
acid can be obtained.

Commercial zinc soaps are produced from

Properties. See Table 5.
Uses. Copper soaps are used mainly as fungi-
cides in wood and ship paints, textiles (e.g.,
tents, awnings, sandbags, camouflage netting,
ropes), paper, and cardboard. Compared with in-
organic copper compounds, they have the advan-
tage of being difficult to wash out. Naphthenates,
oleates, and 2-ethylhexanoate are used as solu-
tions in organic media.
5.10. Zinc Soaps
The most important zinc soaps are the zinc
stearates.
Neutral zinc soaps are produced by double
decomposition, direct reaction in the melt, di-
rect reaction in aqueous or organic media, and
stearic, lauric, oleic, 2-ethylhexanoic, and naph-
thenic acids. Those derived from stearic acid
are produced on the largest scale. Water-soluble
salts, preferably zinc sulfate and chloride, are
used as zinc source for double decomposition;
zinc oxide, hydroxide, carbonate, and acetate
are employed for direct reaction. When several
types of product are prepared in a single plant,
attention must be paid to the production order
because zinc stearate acts as a gel breaker with
gels from aluminum soaps. Normally calcium,
magnesium, zinc, and aluminum soaps are pro-
duced in a single plant.
Properties. See Table 6.
Uses. Zinc soaps are used for the following
purposes:
1) In the plastics industry as lubricants, release
agents, and components of PVC stabilizers
12 Metallic Soaps
Table 6. Technical data for some commercial soaps of cadmium and zinc

Compound CAS registry Appearance Free fatty Total ash, Moisture∗, Bulk Melting
no. acid∗, wt % wt % wt % density, range, ◦ C
g/L

Cadmium stearate [2223-93-0] white powder 2 19 – 20 1 180 105 – 115

Cadmium [69121-20-6] white powder 2 18 – 19 1 220 110 – 118
12-hydroxy-stearate
Cadmium laurate [2605-44-9] white powder 2 26 – 27 1 300
Cadmium oleate [10468-30-1] brown mass 19 – 20 2
Cadmium 2-ethyl-hexanoate [2420-98-6] yellowish paste 32 – 33 2
Zinc stearate, precipitated [557-05-1] white powder 0.5 13 – 14 1 140 118 – 122
Basic zinc stearate, direct [557-05-1] white powder 0.5 15 – 17 1 300 118 – 122
reaction
Zinc stearate, direct reaction [557-05-1] white powder 0.5 13 – 14 1 300 118 – 122
Zinc 12-hydroxystearate [35674-68-1] white powder 1 12.5 – 13.5 1 220 145 – 155
Zinc laurate [2452-01-9] white powder 1 17 – 18 1 220 122 – 126
Zinc arachidate [22302-43-8] white powder 1.5 12 – 13 1 180 120 – 124
Zinc oleate [557-07-3] bright mass 13 – 14 0.3
Zinc 2-ethylhexanoate [136-53-8] clear, highly 23 – 24 1
viscous liquid
Zinc naphthenate [12001-85-3] brown mass 14 – 15 0.4

∗ Approximate values.

2) In the rubber industry, as release agents
for unvulcanized products (wettable zinc
stearate soaps and zinc stearate dispersions
in water are also used)
3) In paints, as matting agents and abrasives
4) In building protection, as waterproofing
agents
5) For textiles, also as waterproofing agents
6) In the cosmetics and pharmaceutical indus-
tries, as additives to body and face powders
7) As components of wire-drawing greases
(special zinc arachidate is used in tube draw-
ing because of its low ash content)
8) In paints, as components of dryers and as
anticaking agents for powdered products
5.11. Cadmium Soaps
Neutral and basic cadmium soaps are produced
by double decomposition, direct reaction in
the melt, or direct reaction in organic media.
Stearic, lauric, 12-hydroxystearic, oleic, and 2-
ethylhexanoic acids are commonly used. Cad-
mium sulfate, chloride, and nitrate are used in
double decomposition; cadmium oxide and hy-
droxide in the direct reaction. Cadmium soaps
are highly toxic. Cadmium accumulates in or-
gans such as the liver and adrenal gland and is
released very slowly. Absorption of very small
quantities of cadmium over a long period there-
fore leads to chronic illness. The TLV – TWA
value is 0.05 mg/m3 .
Properties. See Table 6.
Uses. The use of cadmium soaps as compo-
nents of PVC stabilizers is decreasing because
of their toxic properties. Solid PVC stabilizers
contain cadmium soaps of saturated fatty acids,
whereas liquid stabilizers contain soaps of un-
saturated or branched, short-chain fatty acids.
The soaps act as heat and light stabilizers, and
soaps of saturated fatty acids are used as lubri-
cants in the processing of PVC. Unlike other
metallic soaps used in the PVC sector, cadmium
soaps do not affect transparency and are suitable
for hard, transparent PVC products.
5.12. Manganese Soaps
Neutral manganese(II) soaps are produced
by double decomposition from alkali soaps and
water-soluble manganese salts in an aqueous
medium or in the presence of organic solvents,
and by direct reaction in the melt or in organic
media with manganese oxides, hydroxides, or
salts of volatile acids. The oxides and hydrox-
ides are very unreactive and must be freshly pre-
pared; conversion is generally incomplete. In

the reaction with metallic manganese in pow-
der form or as divided gauze, lower carboxylic
acids (e.g., acetic acid) are added to the solvent
as catalysts.
Basic manganese(II) soaps are produced
by double decomposition in an aqueous
medium; oversaponified alkali soaps (i.e., more
than 1 mol of alkali is used per mole of acid)
react with water-soluble manganese salts. The
excess alkali forms manganese hydroxide or
manganese oxide hydrate, which adds to the
neutral manganese soap. Whether a true ad-
dition salt or a simple mixture is formed is
unclear. The basic manganese soaps are insol-
uble or sparingly soluble in organic solvents.
Stearic, oleic, naphthenic, and 2-ethylhexanoic
acids are commonly used. Sources of manganese
for the double decomposition are water-soluble
manganese salts such as manganese chloride
and sulfate; for the direct reaction, manganese
oxide, hydroxide, and acetate.
Manganese soaps are hazardous to health. A
particular danger arises from dust formation by
products in powder form. Because of their brown
color, separate production plants are necessary
for the powdered products. The TLV – TWA
values for manganese are 5 mg/m3 (dust) and
1 mg/m3 (fume).
Properties. See Table 7.
Uses. Manganese soaps are used mainly as
dryers in paints, printing inks, and varnishes
based on drying oils or alkyd resins. Basic pow-
dered products are also added to printing inks.
Manganese soaps can be used as catalysts
(e.g., in paraffin oxidation or the reduction of
fatty acids to alcohols).
5.13. Iron Soaps
Only neutral iron(III) soaps are produced indus-
trially. Formation of basic soaps by addition of
iron oxide or hydroxide is known but is not ex-
ploited commercially.
Iron soaps are obtained by double decompo-
sition from alkali soaps and water-soluble iron
salts in an aqueous medium with or without or-
ganic solvents. Direct reaction in the melt with
iron oxides does not go to completion and is very
Metallic Soaps 13
slow; the unreacted free fatty acid is extracted
with alcohol.
Raw materials used are stearic, oleic, naph-
thenic, and 2-ethylhexanoic acids. In double
decomposition, iron(III) chloride is generally
used as the iron source; in the direct reaction,
iron oxide, hydroxide, or carbonate are used. Be-
cause of the intense color of iron soaps, separate
precipitation units are necessary. Although iron
soaps do not pose a danger to health, local reg-
ulations regarding personal and environmental
protection for dust-producing products must be
observed during handling.
Properties. See Table 7.
Uses. Iron soaps are components of dryer
mixtures. Because of their intense color, they
are used only with dark colors. The function of
the iron as a dryer is based on polymerization
at elevated temperature rather than catalysis of
oxidation.
Further uses are as hydrogenation catalysts,
as dry-film lubricants in the form of monomolec-
ular adhesive layers, in the production of fast-
copy paper, in waterproofing, and in pharma-
ceuticals as oil-soluble iron compounds for the
treatment of anemia.
5.14. Cobalt Soaps
Neutral and weakly basic cobalt(II) soaps are
known. They are produced by double decom-
position using alkali soaps with water-soluble
cobalt salts in an aqueous medium with or with-
out organic solvents, or by direct reaction via the
melt process, or in solvents. Reaction of metallic
cobalt in powder or gauze form in organic media
is also possible; air acts as an oxidizing agent.
Stearic, oleic, naphthenic, and 2-
ethylhexanoic acids are used. For double decom-
position, cobalt(II) sulfate is used as the water-
soluble salt; for the direct reaction, cobalt ac-
etate, cobalt(II) hydroxide, and cobalt(II) oxide
are used.
Cobalt soaps have an intense blue-violet
color. Soaps in powdered form must be pro-
duced in separate plants. Dust from cobalt soaps
is hazardous to health. Local regulations con-
cerning personal and environmental protection
and the compulsory labeling of packaging must
14 Metallic Soaps
Table 7. Technical data for some commercial soaps of iron, cobalt, nickel, and manganese

Compound CAS registry Appearance Free fatty Total ash or Moisture∗, Melting
no. acid∗, metal content, wt % range,
◦
wt % wt % C

Iron(III) stearate [555-36-2] red-yellow powder 5 14 – 15 1 ca. 90

Iron oleate [23335-74-2] red paste 9 – 10 2
Iron [6535-20-2] reddish paste 16 – 17 1
2-ethylhexanoate
Cobalt stearate [13586-84-0] blue – violet 1 13 – 14 1 ca. 150
powder
Cobalt [136-52-7] blue – violet mass 22 – 23 1
2-ethylhexanoate
Cobalt [61789-51-3] dark blue mass 10 – 11 Co
naphthenate
Nickel stearate [2223-95-2] bright green 1 14.5 – 15.5 1 80 – 86
powder
Nickel oleate [13001-15-5] greenish paste 1 22 – 23 1
Nickel [4995-91-9] green paste 22 – 23 1
2-ethylhexanoate
Nickel [61788-71-4] deep green mass 1 8.5 – 11.5 Ni 1
naphthenate
Manganese [3353-05-7] bright brown 13 – 14 1 ca. 80
stearate powder
Manganese(II) [23250-73-9] brown mass 12 – 13 1
oleate
Manganese [15956-58-8] brown mass ca. 16 Mn
2-ethylhexanoate
Manganese [1336-93-2] dark brown mass ca. 10 Mn 1
naphthenate
∗ Approximate values.

be observed. The TLV – TWA value for cobalt is
0.05 mg/m3 .
Properties. See Table 7.
Uses. Cobalt soaps are very effective dryers
for printing and writing inks because they cat-
alyze oxidation. Cobalt stearate is used as an
adhesive for rubber – metal bonding.
Nickel soaps in powder form must be pro-
duced in separate plants because of their in-
tense green color. Dust from nickel soaps is
hazardous to health. Local regulations concern-
ing personal and environmental protection and
compulsory labeling must be observed. In pro-
cessing nickel oxide and carbonate, protective
measures must be taken because of their car-
cinogenic properties. The TLV – TWA value for
nickel is 1 mg/m3 .

5.15. Nickel Soaps Properties. See Table 7.

Divalent nickel forms neutral to weakly basic
soaps. They are produced by double decompo-
sition from alkali soaps and water-soluble nickel
salts in an aqueous medium in the presence of or-
ganic solvents or by direct reaction in the melt or
in solvents with nickel oxide, hydroxide, or salts
of volatile acids. In the melt process, decompo-
sition occurs above 200 ◦ C with formation of a
black powder. The usual acids are stearic, oleic,
2-ethylhexanoic, and naphthenic acids. Nickel
sulfate and chloride are used as water-soluble
salts for double decomposition, and nickel(II)
hydroxide, oxide, acetate, or carbonate for the
melt process.
Uses. Nickel soaps are used as oxidation cat-
alysts in dryers; as oil-soluble hydrogenation
catalysts, which liberate finely divided nickel on
heating or decomposition; as detergents in petro-
leum ether; and as additives in lubricating oils
for preventing cyclization and resinification.
6. Quality Specifications
Metallic soaps can be characterized by a series
of data. Certain application-orientated proper-
ties, such as solubility and swelling, may have

to be determined in special tests on test formu-
lations.
Solid Metallic Soaps. The following param-
eters are determined:
Moisture Content. The sample is weighed be-
fore and after heating at 110 ◦ C for 2 h in a drying
oven.
Metal Content. Metal content is determined
by one of the usual analytical methods after acid
decomposition of the metallic soap in an aque-
ous extract.
Total Ash. The substance is preheated care-
fully in an incinerator and then heated slowly
to 800 – 1000 ◦ C in a muffle furnace as soon as
all the organic substance has decomposed. After
being cooled in a desiccator, the ash is deter-
mined by back-weighing. For lead soaps, atten-
tion must be paid to reduction to metallic lead.
Washed Ash. Residue from the determination
of total ash is boiled in distilled water and fil-
tered; the residue and the filter paper are incin-
erated. The final residue is expressed as a per-
centage of the weight of substance used for the
total ash determination. This method is not ap-
plicable to water-soluble metal oxides.
Water-Soluble Salts. The difference between
total ash and washed ash is described as soluble
ash or water-soluble salt. For metallic soaps pro-
duced by double decomposition, this parameter
gives a good indication of whether the salts have
been washed sufficiently.
Free Fatty Acids. The substance is refluxed
with acetone for 10 min and filtered; the fatty
acid content is determined by titration with al-
coholic potassium hydroxide using thymol blue
and cresol red as a mixed indicator.
Particle Size. Particle size is determined as
residue on a 71 µm air-stream sieve or by wet
sieving of an aqueous dispersion with a surfac-
tant.
Tapped Bulk Density. Tapped bulk density is
determined in a commercial tamp volumeter by
using a fixed number of impacts.
Bulk Density. The substance is passed
through a 500-µm sieve into a measuring cylin-
der up to the 100-mL mark and weighed.
Melting Range. Melting range can be deter-
mined in a commercial melting point apparatus.
pH value.pH determination on the soap dis-
persion.
Metallic Soaps 15
Fatty Acids Composition.Fatty acids compo-
sition is determined by gas chromatography with
direct injection of a methyl esters solution ob-
tained from the soap.
Metallic Soap Solutions. For metallic soap
solutions (e.g., used as PVC stabilizers or dry-
ers), metal content, density, viscosity, solid con-
tent, and Gardner color index must be deter-
mined. Industrial supply conditions are to be ob-
served for metallic soap dryers [32].
7. References
1. I. W. H. Oldham, A. R. Ubbelohde, J. Chem.
Soc. 1941, 368 – 375.
2. P. N. Cheremisinoff, J. Am. Oil. Chem. Soc. 28
(1951) 278 – 279.
3. Colgate-Palmolive-Peet Co., US 2 447 064,
1948.
4. G. H. Smith et al., J. Amer. Chem. Soc. 70
(1948) 1053 – 1054.
5. The Commonwealth Eng. Co., US 2 768 996,
1954.
6. C. I. Boner, Ind. Eng. Chem. 29 (1937) 58.
7. A. S. C. Laurence, Trans. Faraday Soc. 34
(1938) 665 –669.
8. E. A. Nikitina et al., J. Gen. Chem. 19 (1949)
1108 –1114.
9. G. H. Smith, S. Ross, Oil Soap (Chicago) 23
(1946) 77 – 80.
10. H. I. Braun, Chem. Ztg. 53 (1929) 913 – 914.
11. C. W. Hill, C. W. Stoddart, Am. Soc. 33 (1911)
1076.
12. I. Marwendel OHG, DE 845 800, 1950.
13. P. N. Cheremisinoff, Am. Paint. J. 37 (1953)
90 – 94.
14. A. Davidsohn, Ind. Chem. 26 (1950)
385 – 394.
15. Battenfeld Grease and Oil Corp., US
2 753 364, 1951.
16. Socony Vacuum Oil, US 2 389 873, 1945.
17. IG Farben, GB 335 863, 1929.
18. National Lead Co., US 2 650 932, 1953.
19. IG Farben, GB 478 587, 1938.
20. Socony Vacuum Oil, US 2 311 310, 1943.
21. L. W. Ryan, W. W. Pletscher, Ind. Eng. Chem.
26 (1934) 909 – 910.
22. IG Farben, US 2 095 508, 1937.
23. R. C. Pink, Trans. Faraday Soc. 37 (1941) 181.
24. Hoesch-Chemie GmbH, US 3 519 571, 1967.
25. Tenneco Chemicals Inc., DE-AS 2 159 347,
1971.
16 Metallic Soaps

26. US 3 779 962, 1970, (G. Koenen, A.
Szczepanek).
27. Supraton F. I. Zucker GmbH, US 4 376 079,
1981.
28. Mallinckrodt, Inc., EP 0 086 362, 1983.
29. Tenneco Chemicals Inc., EP-A 0 058 792,
1981.
30. Alexander Gray, J. Phys. Colloid Chem. 53
(1949) 9 – 39.
31. Chemische Fabrik Hoesch KG, DE 1 068 237,
1955.
32. ISO 4619: “Driers for Paints and Varnishes,”
Jan. 1982.