Sodium Hydroxide 1

Sodium Hydroxide
Cetin Kurt, Bayer MaterialScience AG, Leverkusen, Germany
Jürgen Bittner, Bayer MaterialScience AG, Leverkusen, Germany

1. Introduction . . . . . . . . . . . . . . ... 1 3.3. Forming . . . . . . . . . . ......... 6

2. Properties . . . . . . . . . . . . . . . ... 1 3.4. Specifications . . . . . . . ......... 8
2.1. Properties of Sodium Hydroxide ... 1 3.5. Storage, Packaging, and
2.2. Properties of Sodium Hydroxide Transportation . . . . . . . . . . . . . . . 8
Solution . . . . . . . . . . . . . . . . . ... 2 4. Uses . . . . . . . . . . . . . . . . . . . . . . 9
3. Production . . . . . . . . . . . . . . . ... 3 5. Safety Precautions . . . . . . . . . . . . . 11
3.1. Production of Sodium Hydroxide 6. Economic Aspects . . . . . . . . . . . . . 11
Solution . . . . . . . . . . . . . . . . . ... 3 7. References . . . . . . . . . . . . . . . . . . 12
3.2. Production of Solid Sodium
Hydroxide . . . . . . . . . . . . . . . ... 6

1. Introduction dependent physical properties of aqueous solu-

Pure sodium hydroxide, NaOH, is a colorless
solid. It does not occur in nature, but is manu-
factured on a large scale from fairly readily ob-
tainable raw materials and is used in numerous
chemical processes. Because of its corrosive ac-
tion on many substances, it is known as caustic
soda.
Sodium hydroxide solution is one of the
oldest man-made chemicals. The reaction of
sodium carbonate with calcined limestone
(causticization of soda) was already known in
early Afro-Oriental cultures. Alabaster vessels
containing 3 % sodium hydroxide solution have
been found in Egyptian tombs dating from 3rd
century b.c. near the Pyramid of Cheops. The
first written records of caustic soda production
during the early years a.d. came from Egypt and
India.
2. Properties
Because pure sodium hydroxide has a high affin-
ity for water, the physical and chemical prop-
erties of the pure substance are difficult to de-
termine. Many of the data are obtainable only
by extrapolating values for impure sodium hy-
droxide. The same is true for the concentration-
tions of sodium hydroxide, since these solutions
have a strong tendency toward supersaturation.
2.1. Properties of Sodium Hydroxide
Some physical properties of solid sodium hy-
droxide are as follows:
Mr 40
Appearance white, crystalline
Density (liquid, 350 ◦ C) 1.77 g/cm3
mp (soda and water free) 322 ± 2 ◦ C
Heat of fusion 6.77 kJ/mol
Boiling point at 0.1 MPa 1388 ◦ C (calculated)
Specific heat capacity at 20 ◦ C 3.24 J kg−1 K−1
Chemical Properties. Pure sodium hydrox-
ide is strongly hygroscopic. It dissolves in water
with liberation of heat and forms six defined hy-
drates (see Figs. 1 and 2, and Table 1). When
transporting and storing sodium hydroxide so-
lution, the containers must be heated or insu-
lated because the melting points of some of the
hydrates are much greater than 0 ◦ C. In the pres-
ence of moisture, NaOH reacts readily with at-
mospheric carbon dioxide to form sodium car-
bonate. Sodium hydroxide reacts with carbon
monoxide under pressure and in the presence of
moisture to yield sodium formate.

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a24 345.pub2
2 Sodium Hydroxide

The high affinity of sodium hydroxide for wa- 2.2. Properties of Sodium Hydroxide
ter causes a reduction in water vapor pressure Solution
(e.g., to 0.36 kPa for 50.3 wt % NaOH at 30 ◦ C).
Physical Properties. The concentrations of
Sodium hydroxide is therefore a very effective
the aqueous solutions in equilibrium with solid
drying agent. It is fairly readily soluble in meth-
NaOH at various temperatures are given below:
anol and ethanol.

Table 1. Stability of the hydrates of sodium hydroxide

Formula Stability range, ◦ C

NaOH · 7H2 O − 23.5 to − 28.3 a

NaOH · 5H2 O − 12.2 to − 31.9 a
α-NaOH · 4H2 O + 7.6 to − 21.4 a
β-NaOH · 4H2 O (unstable) − 1.7 to − 14.5 a
NaOH · 3.5H2 O + 15.6 to − 8.8 b
9NaOH · 28H2 O (unstable) + 2.7 to − 2.5 a
NaOH · 2H2 O 0 to + 12.5 c
NaOH · H2 O + 4.5 to + 64.3 b
a
Unstable melting point.
b
Clearly defined melting point.
c
Melting point can be determined only by extrapolation.

Figure 2. Melting diagram of the NaOH–H2 O system [1]

t, ◦ C 10 18 30 40 53 64
wt % NaOH 49.8 51.0 53.3 55.4 59.7 69.0

The heat of solution is ca. 44 kJ/mol at 18 ◦ C.

Figure 1. The NaOH – H2 O system
Anhydrous sodium hydroxide reacts very
slowly with most substances. For example, it at-
tacks many metals only slightly at room temper-
ature (e.g., Fe, Mg, Ca, and Cd). However, corro-
sion rates increase rapidly with increasing tem-
perature. More noble metals such as nickel, sil-
ver, gold, and platinum are attacked only slightly
even when heated, especially if oxidizing atmo-
spheres are excluded. Anhydrous sodium hy-
droxide does not react with dry carbon dioxide.
The surface tension at 20 ◦ C increases from
7.46×10−2 N/m for a 5 wt % solution to 0.1
N/m for a 35 wt % solution [2]. A 1 mol % so-
lution has a surface tension of 7.43×10−2 N/m
at 20 ◦ C, which decreases to 6.23×10−2 N/m at
90 ◦ C.
The density of aqueous sodium hydroxide
solution in the concentration range 0 – 20 wt %
can be calculated from the formula:
d1 = d2 +(1.16027×10−2 −2.511×10−5 t+
1.0222×10−7 t2 )p−(1.0817×10−5 −
3.6748×10−7 t+2.034×10−10 t2 )p2
where
d 1 , g/cm3 = density of solution at t ◦ C
t, ◦ C = temperature

p, wt % = g NaOH/100 g solution
d 2 , g/cm3 = density of water at t ◦ C
The densities of more concentrated aqueous
sodium hydroxide solutions at 20 ◦ C are as fol-
lows:
[NaOH], wt % Density, g/cm3
20 1.219
30 1.328
40 1.430
50 1.525
The boiling point curve is shown in Figure 1.
In the concentration range 0 – 60 wt % NaOH,
the boiling point increases approximately lin-
early with temperature.
NaOH concentration, wt % 5.9 23.1 33.8 48.3
Boiling point, ◦ C 105 110 120 140
A 5 g/L solution of sodium hydroxide in wa-
ter is almost completely dissociated. Activity co-
efficients are in the range a = 0.784 (0.1 M at
10 ◦ C) and a = 3.922 (15 M at 70 ◦ C).
Chemical Properties. Amphoteric metals
such as zinc, aluminum, tin, and lead are at-
tacked by dilute sodium hydroxide solution
at room temperature. Iron, stainless steel, and
nickel are fairly resistant.
3. Production
Sodium hydroxide is produced commercially in
two forms: as 50 wt % solution (the most com-
mon form) and in the solid state (caustic soda)
as prills, flakes, or cast shapes.
3.1. Production of Sodium Hydroxide
Solution
Electrolysis of Sodium Chloride. Sodium
hydroxide solution is produced industrially
mainly by the electrolysis of sodium chloride.
This yields sodium hydroxide solution, chlorine,
and hydrogen in the mass ratio 1: 0.88: 0.025 in
accordance with the following overall equation:
2 NaCl+2 H2 O→2 NaOH+Cl2 +H2
In the early 1980s, the membrane process was
introduced, the other processes in operation at
Sodium Hydroxide 3
that time being the amalgam and diaphragm pro-
cesses. Chlor-alkali production in 2004 was di-
vided between the different processes as shown
in Table 2.
Membrane technology continued to gain
market share in 2004. Based on announced ca-
pacity changes, membrane processes will ac-
count for about 44 % of the total installed chlor-
alkali capacity by 2009. Membrane technology
saves approximately 30 % electrical power and
is the best available technique, so it will be in-
creasingly used in new units.
In Japan, by 1988 all plants based on the
amalgam process had been either shut down
or converted to the membrane process. Some
Japanese diaphragm plants were also replaced
54.6 by membrane plants for reasons of both cost
150 and quality. Details of the three electrolytic pro-
cesses are given in → Chlorine.
Treatment of the liquor from the electrolytic
cell is shown schematically in Figure 3. In the
amalgam process, sodium hydroxide solution is
produced from sodium amalgam and water over
a graphite catalyst at 80 – 120 ◦ C. The 50 wt %
solution produced is very pure. It is cooled, mer-
cury is removed by centrifugation or filtration
through cartridge or pressure plate filters, and it
is then sold without further treatment.
In the diaphragm cell, the depleted sodium
chloride solution from the anode compartment
is transferred quantitatively to the cathode com-
partment, so that the cell liquor produced there
contains ca. 18 wt % sodium chloride and 10 –
15 wt % sodium hydroxide. During evaporation
to give a 50 wt % NaOH solution, all the im-
purities carried over with the depleted sodium
chloride solution are removed to their limiting
solubility by fractional crystallization; thus the
sodium chloride content can only be reduced to
ca. 1 – 1.5 wt %. In the DH process of the PPG
Company, further purification is carried out by
extraction with anhydrous liquid ammonia. This
gives a product comparable to that from the
amalgam process (rayon quality), but the pro-
cess is seldom used because of cost. This is also
true of a Japanese process in which a relatively
pure sodium hydroxide solution is obtained by
cooling the 50 wt % diaphragm liquor and re-
covering the crystals of pure NaOH · 3.5 H2 O
formed. Details of the evaporation and purifica-
tion processes are given in → Chlorine. Methods
of optimizing the various evaporation systems
4 Sodium Hydroxide
Table 2. Distribution of chlor-alkali production among the three most widely used processes (percentage of installed capacity in 2004)

Process North Western Japan

America Europe

Amalgam 19 44 0
Diaphragm 39 7 3
Membrane 25 34 82
Others 17 15 15

Figure 3. Treatment of the sodium hydroxide solution from electrolysis cells

Figure 4. Membrane cell caustic evaporation (Bertrams process)

a) Vacuum pump; b) Condenser; c) Caustic cooler; d) First evaporator; e) Caustic pump; f ) First caustic heat exchanger;
g) Second heat exchanger; h) Caustic pump; i) Second evaporator; j) Caustic pump; k) Second caustic heat exchanger; l) First
heat exchanger; m) Third evaporator

used for treating liquor from the diaphragm cell
are described in [3].
In the membrane process, a hydraulically
impermeable membrane prevents mixing of
the electrolytes. This process produces a high-
purity, virtually chloride-free sodium hydroxide
solution comparable to that of the amalgam pro-
cess. However, the chloride content increases by
a factor of ca. 10 if operation of the cell is in-
terrupted, due to diffusion of Cl− ions through
the membrane. The sulfate and chlorate present
in the anolyte also affect the concentration of
these impurities in the caustic liquor from the
membrane cell, since the cation-selective mem-
brane has an appreciable residual permeability
for anions. Most membrane cells give optimum
economic performance at a NaOH concentra-
tion of 30 – 35 wt %. An ion-exchange mem-
brane has now been developed that enables a
50 wt % sodium hydroxide solution to be pro-
duced in the cell [4], although a considerable in-
crease in voltage is required. Such membranes
are viable only if steam costs are high and elec-
tricity costs low [5]. The 30 – 33 wt % sodium
hydroxide solution is usually concentrated in a
two- or three-stage falling-film evaporator (de-
pending on steam costs and plant size) to give
a commercial 50 wt % solution (see Fig. 4). For
a three-stage evaporator, the steam consumption
is 0.55 t per ton NaOH (100 %), and for a two-
stage evaporator, 0.71 t per ton NaOH (100 %),
with sodium hydroxide solution and steam in
counter current flow.
The evaporation of membrane cell liquor (un-
like that of diaphragm cell liquor) does not pro-
duce any solid material that can foul the heat
exchanger or erode the pipework. The pickup
of metals during evaporation is ca.1 wt ppm
if appropriate construction materials are used
(nickel, stainless steel). The various evaporation
techniques are described in [3], with special ref-
erence to the concentration of membrane cell
liquor.
As shown in Table 3, the three electrolytic
processes have different energy requirements.
The membrane process consumes the least
electrical energy (2200 – 2500 kW · h per ton
NaOH) but requires an additional 200–300 kW ·
h per ton NaOH in the form of steam to pro-
duce a 50 wt % solution. The diaphragm process
consumes less electrical energy than the amal-
gam process but requires 700–900 kW · h per
Sodium Hydroxide 5
ton NaOH as steam for the evaporation stage
and therefore has the highest total energy re-
quirement.
Because of the high consumption of electrical
energy, much research has been aimed at reduc-
ing the cell voltage. A ca. 1 V reduction can be
achieved by using an oxygen diffusion cathode
(as in a fuel cell) in the membrane cell process,
although in this case no byproduct hydrogen is
produced. This technology is gaining increasing
interest. Cell design, oxygen diffusion cathode,
and integration of the cathode into the cell design
are priority points of development. Also the in-
vestigation of operation parameters and the pe-
riphery of the cells are in focus. Currently (in
2005) these cells have not been used on a pro-
duction scale [7 – 9].
The electrolysis of fused NaCl at 350 ◦ C
with a β-Al2 O3 diaphragm is also of interest.
In laboratory-scale cells, a power consumption
of 2350 kW · h per ton NaOH can be attained
[10]. This technique, too, has yet to be used on
a commercial scale.
Other Processes. The causticization of
sodium carbonate solution is the oldest method
of producing sodium hydroxide and was the
only method available until the introduction
of electrolysis. Although it had almost disap-
peared from use, it is now of special interest
for companies with access to synthetic sodium
carbonate from the Solvay process or to natural
sodium carbonate (e.g., trona, Na3 H(CO3 )2 · 2
H2 O). In this process, a hot, ca. 12 % solution of
sodium carbonate is mixed with quicklime. The
calcium carbonate that precipitates according to
the equation.
Na2 CO3 +CaO+H2 O→2 NaOH+CaCO3
is removed, and the ca. 12 % solution of
sodium hydroxide is evaporated in several
stages. The impurities that precipitate, mainly
NaCl and Na2 SO4 , are filtered off. Further de-
tails on the causticization of sodium carbonate
are given in [11].
In a combination of electrolytic and dialysis
cells, sodium salts can be split into the corre-
sponding acids and alkalis, e.g.,
Na2 SO4 +2 H2 O→2 NaOH+H2 SO4
This reaction can be carried out in a two-
chamber cell with a cation- or anion-exchange
6 Sodium Hydroxide
Table 3. Energy requirements for the production of 1 t of sodium hydroxide (as 50 wt % solution) by the three electrolytic processes
Energy, kW · h/t NaOH a
Electricity b
Steam (equivalent) c
Total
Relative energy costs, %
a
The energy requirement given is based on the production of 1 t NaOH, 0.88 t Cl2 , and 0.025 t H2 .
b
In dependence on the current density.
c
1 t steam is taken to be equivalent to 400 kWh of electrical energy.
membrane; in a three- chamber cell with a
cation-exchange and an anion-exchange mem-
brane; or in a multichamber cell with a combi-
nation of cation, anion, and bipolar membranes
[12 – 15] (→ Sodium Sulfates, Chap. 1.4.1).
However, in all industrially operated cells, the
product is a dilute sodium hydroxide solution
(15 – 30 wt %), which also contains some of the
salt used as starting material. For this reason,
this type of process is most suitable for treat-
ing sodium-salt containing wastewater from pro-
cesses in which the dilute sodium hydroxide so-
lution obtained can be recycled for neutraliza-
tion purposes.
An alternative method of producing sodium
hydroxide solution for small paper pulp plants,
the ferrite recovery process, is described in [16].
Here, waste liquor containing sodium salts and
organic substances is evaporated, and the residue
is mixed with Fe2 O3 and calcined. The sodium
ferrite formed is decomposed by water to give
NaOH and Fe2 O3 .
3.2. Production of Solid Sodium
Hydroxide
Solid sodium hydroxide (caustic soda) is ob-
tained by evaporating sodium hydroxide so-
lution until the water content is < 0.5 – 1.5
wt %. The most efficient utilization of energy is
achieved with multistage equipment. A flow di-
agram of a plant constructed by Bertrams, Basel
(Switzerland), is shown in Figure 5.
A 50 wt % solution is vacuum evaporated in
a preconcentration unit, by using the heat of
the vapor from the main concentrator, until the
concentration reaches ca. 60 wt %. In the sec-
ond stage, a concentration of ca. 99 wt % is at-
tained by heating with a molten salt heat-trans-
Process
Amalgam Diaphragm Membrane
2800 – 3200 2500 – 2600 2200 – 2500
0 700 – 900 90 – 180
2800 – 3200 3200 – 3500 2290 – 2680
90 100 70
fer medium (NaNO2 – NaNO3 – KNO3 ) at >
400 ◦ C in a falling-film evaporator. The prod-
uct is fed to a flash evaporator that operates as a
gaslift pump. Molten NaOH is raised by vacuum
into a heated riser pipe, causing the remaining
water to evaporate. The rising steam bubbles lift
the melt to the highest point of the system, where
the steam is pumped off. The almost anhydrous
melt passes through a downcomer pipe into the
holding vessel, from which it is pumped to the
conditioning plant. The holding vessel, pumps,
and pipes must be heated to prevent premature
crystallization.
3.3. Forming
When the NaOH melt is cooled and formed, both
the solidification point of NaOH (322 ◦ C) and
that of the monohydrate, NaOH · H2 O (62 ◦ C),
must be passed through quickly to prevent cak-
ing due to unsolidified monohydrate.
Solid sodium hydroxide is supplied in the
form of flakes, prills, cast blocks, and less com-
monly as tablets, briquettes, or granules. Flakes
have a bulk density of ca. 0.9 kg/dm3 , a thick-
ness of ca. 1.5 mm, and a diameter of 5 – 20 mm,
and are easily broken so that some dust is always
formed on handling. Prills have a bulk density of
> 1 kg/dm3 and consist of spheres with a diam-
eter of 0.1 – 0.8 mm (microprills) or 0.5 – 2.5
mm.
Flakes. To produce flakes, molten NaOH is
fed into a trough in which an internally cooled
drum rotates. The molten material solidifies on
the surface of the partially immersed drum and is
scraped off by a knife, which breaks up the sheet
of NaOH into flakes. These are taken to a small
intermediate storage silo and packed as soon as
possible in sacks or steel drums. The material

Figure 5. High-Concentration unit for caustic soda (Bertrams process)
a) Vacuum pump; b) Condenser; c) Condensate pump; d) Furnace unit; e) Salt melt pump; f ) Heated salt melt tank; g) Precon-
centration unit; h) Vacuum pump; i) Condenser; j) Falling-film concentrator; k) Flash evaporator; l) Heated caustic melt tank;
m) Caustic melt pump
tends to bridge due to its particle shape, so that
it cannot be stored in large silos or be transported
by compressed air.
Figure 6. Production of sodium hydroxide prills (Bertrams
process)
a) Caustic melt tank; b) Caustic melt pump; c) Spray tower;
d) Rotating spray system; e) Product cooler; f ) Elevator;
g) Exhaust air treatment; h) Silo; i) Bagging and pelletiz-
ing
Sodium Hydroxide 7
Prills are produced by spraying the molten
material at ca. 360 ◦ C to form droplets. The
spray equipment used can be nozzles (outdated),
or a spinning disk or basket. The finely divided
melt forms spheres of fairly uniform diameter
due to surface tension. These are cooled to ca.
250 ◦ C as they fall down a shaft in which air
flows upward. The prills are collected in a fun-
nel from which they run into a cooling drum
where they are cooled to ca. 50 ◦ C. The finished
product is stored in silos (see Fig. 6).
Unlike flakes, prills are free flowing. Also,
they do not cake as readily and thus can be stored
in silos, transported in containers or other large
vessels, or moved by compressed air, because
they are almost dust free.
Cast Blocks. Molten NaOH is directly cast
into iron drums or similar containers. The drums
are externally cooled intensively by spraying
with water, so that a solid film of sodium hy-
droxide forms immediately on the walls of the
container, preventing further contamination by
the iron.
8 Sodium Hydroxide
Special Shapes. Tablets, pills, or pellets are
produced by the droplet process. Molten NaOH
drops from a special device made of silver onto
a slowly rotating cooled table or conveyor belt
(pill machine). The product has a very low con-
tent of metallic impurities, so that this process
is especially suitable for producing small quan-
tities (e.g., for analytical purposes).
3.4. Specifications
A review of the grades of 50 wt % sodium hy-
droxide solution produced by the various pro-
cesses is given in → Chlorine. Diaphragm liquor
cannot be used in all applications (e.g., for vis-
cose manufacture or various organic processes)
because of the amounts of chloride, chlorate, and
heavy metals present.
When corrosion-resistant materials are used
for sodium hydroxide production (nickel and
stainless steel), the pickup of metal (Ni, Fe) is
< 1 ppm. Solid caustic soda should have a pure
white appearance. The most important impuri-
ties in solid sodium hydroxide are listed in Table
4.
3.5. Storage, Packaging, and
Transportation
Iron, stainless steel, and nickel are suitable ma-
terials for containers used for transport and stor-
age, as well as for pipelines. However, corrosion
resistance is not the sole criterion for the choice
of material. Stress corrosion cracking, changes
in the crystal structure, and pitting can cause sud-
den material failure, so that a more expensive
material is often chosen for safety reasons.
Vessels for holding aqueous solutions of
sodium hydroxide are usually constructed of
alkali-resistant steel. However, at > 50 ◦ C or
in the presence of oxygen, iron is slowly at-
tacked by sodium hydroxide solution. For a
high-quality product (e.g., with iron content <
1 mg/kg), cladding (rubber or plastic coating) is
required. At < 50 ◦ C the solution can be trans-
ported by pipes of alkali-resistant steel or plas-
tic (e.g., PVC). Iron pipes are always kept full to
prevent corrosion due to ingress of air and conse-
quent black coloration of the solution. At higher
temperature, coated materials such as rubber-
lined steel, austenitic Cr – Ni steel (e.g., DIN
1.4541), nickel, Hypalon, epoxy resin, polypro-
pylene, or glass fiber reinforced composites are
suitable. In the latter case, an inner lining must
be used to prevent contact between the glass
fiber and the solution. Heat exchangers are usu-
ally constructed of nickel, nickel alloys, or stain-
less steel because of the high temperature. For
equipment handling highly concentrated solu-
tions, nickel is the most commonly used material
because of its outstanding corrosion resistance.
Metals that have been in contact with solutions
are difficult to weld, so that repairs to pipework
and equipment which have carried sodium hy-
droxide solutions are difficult. A comprehensive
review of materials that can be used with sodium
hydroxide is given in [17].
Pipelines carrying 50 wt % sodium hydrox-
ide solution in cold regions are provided with
thermostatic heating. Solutions are transported
by road, rail tanker, or ship.
Caustic soda prills are stored in steel or stain-
less steel hoppers with a capacity of 30 – 50 m3 .
The hoppers have conical bases with an angle of
25◦ to the vertical and are provided with exter-
nal hammering equipment. Even when the prod-
uct is stored under dry air, a storage time of
3 – 6 d should not be exceeded to ensure that
the prills do not cake under their own weight.
Solid sodium hydroxide is usually packed in 25
– 50-kg hermetically sealed polyethylene sacks.
For transport, the sacks are stacked on wooden
palettes and shrink wrapped in polyethylene.
Caustic soda prills are also carried in 50- or
200-kg steel drums, loose in 1000-kg- capacity
steel or flexible containers, or in transportable
hoppers. In the closed system delivery (CSD)
method of the PPG Company, containers coated
with epoxy resin are transported by road and rail.
Pneumatic transport is carried out with dry air
and causes very little damage to the product [18].
4. Uses
Most users of sodium hydroxide require dilute
aqueous solutions.
The sodium hydroxide produced in Europe
(9.86×106 t/a NaOH) and in North America in
2004 was divided among various areas of use,
 Sodium Hydroxide 9
Table 4. Product quality: typical percentage analyses of sodium hydroxide from chlor-alkali electrolytic processes

Amalgam process Membrane process Diaphragm process

NaOH 99 – 99.5 99 – 99.5 98 – 99

NaCl 0.03 – 0.05 0.01 – 0.02 1–2
Na2 CO3 0.2 – 0.4 0.2 – 0.4 0.65
Na2 SO4 0.03 0.001 – 0.01 0.035
Ca 0.002 0.00002 0.001
Mg 0.0005 0.00002 0.0004
Fe 0.001 0.0001 – 0.001 0.0006 – 0.0015
Al 0.001 0.00002 0.0005
Ni 0.0002 – 0.0004 0.0002 – 0.0004 0.0002 – 0.0004
Hg 0.000001 – 0.00001 Hg free Hg free
mp, ◦ C 322 322 322

Figure 7. Demand of sodium hydroxide in Europe in 2004 broken down by major end uses (Source Bayer MaterialScience AG)

as shown in Figure 7 and 8. More than 56 % of 4) The textile industry uses sodium hydroxide
production is used in the chemical industry: solution to manufacture viscose and viscose
staple fibers (→ Cellulose, Chap. 3.1). The
1) In inorganic chemistry, sodium hydroxide is
sodium hydroxide solution used must con-
used in the manufacture of sodium salts, for
tain only traces of chloride ions (rayon qual-
alkaline ore digestion, and for pH regulation.
ity). The surface of cotton can be improved
2) The organic chemical industry uses sodium
by treatment with sodium hydroxide solution
hydroxide for saponification reactions, pro-
(mercerization).
duction of nucleophilic anionic intermediates,
5) Considerable quantities of sodium hydroxide
etherification and esterification, basic cataly-
are used for sodium phosphate production in
sis, and the production of free organic bases.
the detergent industry. Soaps are manufac-
Sodium hydroxide solution is used for scrub-
tured by the saponification of fats and oils with
bing waste gases and neutralizing wastewater.
sodium hydroxide solution, and detergents
3) In the paper industry (→ Paper and Pulp,
are produced from organic sulfonic acids and
Chap. 1.3.1,→ Paper and Pulp, Chap. 1.3.2),
sodium hydroxide.
sodium hydroxide solution is used for cook-
6) In the aluminum industry, sodium hydroxide
ing wood (removal of lignin).
is used mainly for the treatment of bauxite.
10 Sodium Hydroxide

Figure 8. Demand of sodium hydroxide in North America in 2004 broken down by major end uses (Source Bayer Materi-
alScience AG)

Figure 9. World production capacity of sodium hydroxide by region (total: 59 557 000 t in 2004) (Source Bayer Materi-
alScience AG)

Figure 10. U.S. production of chlorine and sodium hydroxide solution (Source Bayer MaterialScience AG)
7) Waterworks use dilute sodium hydroxide so-
lution to regenerate ion exchangers for water
purification and wastewater treatment.
8) Other users of sodium hydroxide include
electroplating technology, the natural gas and
petroleum industries, the glass and steel in-
dustries, and gold extraction (cyanide leach-
ing). In the food industry, sodium hydroxide is
used for degreasing, cleaning, and for peeling
potatoes.
Consumption of caustic soda in pulp and pa-
per accounts for about one quarter of global
caustic demand. The pulp and paper markets
are relatively mature markets, so demand growth
will be rather slow. The remaining 75 % of global
NaOH demand is inclined to follow the health
of the local manufacturing base, which is tied to
the local gross domestic product (GDP).
5. Safety Precautions
Because of its strongly caustic action, all contact
with sodium hydroxide during handling must be
prevented by the use of suitable protective equip-
ment (protective goggles, safety gloves, and, if
needed, dust masks). Any clothing or shoes that
come in contact with sodium hydroxide must be
removed immediately and can be reused only af-
ter thorough cleaning. First aid to affected parts
of the body consists of washing with copious
amounts of water. The skin can be neutralized
with a dilute solution of a buffered weak acid
(e.g., acetic acid – sodium acetate). For irriga-
Sodium Hydroxide 11
tion of the eyes, a special hygienic eyewash so-
lution is used. The product poses no direct envi-
ronmental risk and has therefore been removed
from the list of chemicals (e.g., in the United
States) whose emission must be reported to lo-
cal and national environmental authorities.
6. Economic Aspects
Chlor – alkali plants are operated to meet chlo-
rine demand; therefore outputs are typically con-
nected to chlorine production. Chlor – alkali op-
erating rates will be on a steady climb, as global
economics growth is stable.
Global chlorine demand is primarily driven
by production of commodities such as PVC,
used, for example in construction parts, and iso-
cyanates, going into construction parts, furni-
ture, shoe industry, consumer durables, and au-
tomobiles. These markets follow the local GDP
trend, thus more mature economies will typi-
cally have a lower GDP and a lower growth in
chlorine demand for these end uses.
The world production capacity of sodium hy-
droxide in 2004 is estimated to be approx. 60 ×
106 dry metric tons (dmt) per year. Today 41 %
of sodium hydroxide is produced in Asia (Fig.
9). In contrast the chlor – alkali production in
the US has shown a decreasing tendency in re-
cent years due to increasing energy costs and a
smaller share in production of vinyl compounds
(Fig. 10). Even though the same trend holds true
for Western Europe, the production remains on
a constant level. From 2004 to 2009 the global
12 Sodium Hydroxide
Figure 11. Sodium hydroxide production in Germany and the United States, 1999 – 2005 (Source Bayer MaterialScience AG)
market for caustic soda will increase by 2.8 %
on average (demand in 2004 is estimated to be
approx. 51 × 106 t, 100 %). Growing markets
are textiles, water treatment, alumina produc-
tion, and pulp and paper.
In order to show the different growth rates in
the USA and Germany, the development of the
US market is shown in Figure 10. and a compar-
ison of the two markets in Figure 11.
7. References
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