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SODIUM HYDRIDE / SODIUM HYDROXIDE 867

Uses
Sodium hydride is used as a reducing agent and reduction catalyst. It also
reduces oxide scale on metals.

Physical Properties
Silvery needles; refractive index 1.470; density 0.92 g/cm3; decomposes at
800°C; decomposes explosively in water; reacts violently with lower alco-
hols;dissolves in molten sodium and molten sodium hydroxide; insoluble in
liquid ammonia, benzene, carbon tetrachloride and carbon disulfide.

Preparation
Sodium hydride is prepared by passing hydrogen gas into molten sodium
metal dispersed in oil. Alternatively, the hydride can be made by passing
hydrogen into sodium dispersed over the surface of an inert solid, such as,
hydrocarbon above 200°C

2Na + H2 → 2NaH

Reactions
Sodium hydride is a powerful reducing agent. It reduces metal oxides,
metal chlorides, and a number of oxidizible substances. Its reactions with
water can proceed with explosive violence:

NaH + H2O → NaOH + H2

Also, its reactions with alcohols can be vigorous to violent. With lower alco-
hols the reaction is usually violent:

NaH + CH3OH → NaOCH3 + H2

Analysis
Elemental composition: Na 95.79%, H 4.21%. The hydride is dissolved in
water in small amounts (violent reaction occurs with water) very cautiously
and the solution is analyzed for sodium. Another aliquot of solution is mea-
sured to determine concentration of OH– (of the product NaOH) formed by
acid-base titration.

SODIUM HYDROXIDE

[1310-73-2]
Formula: NaOH; MW 39.997
Synonyms: caustic soda; white caustic; sodium hydrate

Uses
Sodium hydroxide is one of the most important industrial chemicals. In vol-
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868 SODIUM HYDROXIDE

ume, it is in the top ten chemicals produced in the United States. It is used in
manufacturing a large number of compounds including several sodium salts,
in treating cellulose for producing rayon and cellophane, and in manufactur-
ing soaps, detergents, pulp, and paper. Sodium hydroxide is a common neu-
tralizing agent for acids in acid-base titrations and petroleum refining.
Another major application is extracting metals from their ores where alkali
fusion, such as fusion with caustic soda, often is applied to open the ores.
Additionally, sodium hydroxide is used to precipitate metals as hydroxides.
Other uses are in reclaiming rubber, dissolving casein in plastics production,
refining vegetable oils, processing textiles, as an eluant in ion chromatogra-
phy, etching and electroplating, and as a laboratory reagent. Sodium hydrox-
ide also is used as a strong base in many organic synthesis and base-catalyzed
reactions.

Physical Properties
White orthorhombic crystals, produced in the form of pellets, lumps, sticks,
beads, chips, flakes or solutions; hygroscopic; very corrosive; rapidly absorbs
CO2 and water from the air; density 2.13 g/cm3; melts at 323°C; vaporizes at
1388°C; vapor pressure 1 torr at 739°C and 5 torr at 843°C; very soluble in
water (110 g/100mL at room temperature), generating heat on dissolution;
aqueous solutions highly alkaline, pH of 0.5% solution about 13 and 0.05%
solution about 12; soluble in methanol, ethanol and glycerol (23.8 g/100 mL
methanol and 13.9 g/100 mL ethanol at ambient temperatures.)

Thermochemical Properties
∆Ηƒ° –101.7 kcal/mol
∆Gƒ° –90.7kcal/mol
S° 15.4cal/deg mol
Cρ 14.2cal/deg mol
∆Ηfus 1.58 kcal/mol
∆Ηvap 41.8 kcal/mol
∆Ηsoln –10.64 kcal/mol

Production
Sodium hydroxide is manufactured together with chlorine by electrolysis of
sodium chloride solution. Various types of electrolytic cells are used commer-
cially. They include the mercury cell, the diaphragm cell, and the membrane
cell.
A saturated solution of brine is electrolyzed. Chlorine gas is liberated at the
anode and sodium ion at the cathode. Decomposition of water produces hydro-
gen and hydroxide ions. The hydroxide ion combines with sodium ion forming
NaOH. The overall electrolytic reactions may be represented as:

_ energy
2Na+ + 2Cl + 2H 2O → Cl2 (g) + H 2 (g) + 2NaOH (aq)

The mercury cell proceeds in two stages that occur separately in two cells. The
first is known as the brine cell or the primary electrolyzer in which sodium ion
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SODIUM HYDROXIDE 869

deposits on the mercury cathode forming amalgam, while chlorine gas is lib-
erated at the anode:

Na+ + Cl– → Na-Hg (cathode) + ½Cl2(g) (anode)

In the second cell, known as the decomposer cell, a graphite cathode is used
while sodium amalgam serves as the anode. Water reacts with the sodium
metal of the amalgam in the decomposer:

Na-Hg + H2O → Na+ + OH– + ½H2↑ + Hg

In chlor-alkali diaphragm cells, a diaphragm is employed to separate chlo-

rine liberated at the anode from the sodium hydroxide and hydrogen generat-
ed at the cathode. Without a diaphragm, the sodium hydroxide formed will
combine with chlorine to form sodium hypochlorite and chlorate. In many
cells, asbestos diaphragms are used for such separation. Many types of
diaphragm cells are available.
Sodium hydroxide is produced either as an anhydrous solid or as a 50%
aqueous solution.

Reactions
Sodium hydroxide is a strong base. The most important reactions are the
neutraliztion reactions with acids that form salts and water. Thus with sul-
furic, hydrochloric, and nitric acids, the corresponding sodium salts are
obtained when solutions are evaporated for crystallization. Neutralization
with weak acids forms basic salts. Reactions with organic acids produce their
soluble sodium salts.
Another type of reaction is double decomposition producing metal hydrox-
ides. Thus, insoluble heavy metal hydroxides may be precipitated by treating
caustic soda with a soluble metal salt:

PbCl2 + 2NaOH → Pb(OH)2 + 2NaCl

Reactions with the oxides and hydroxides of amphoteric metals form solu-
ble sodium salts of metal oxides:

Ga2O3 + 2NaOH → 2NaGaO2 + H2O

Al2O3 + 2NaOH → 2NaAlO2 + H2O

Al(OH)3 + NaOH → NaAlO2 + 2H2O

Sodium hydroxide reacts with weak acid gases to form salts:

SO2 + NaOH → Na2SO3 + H2O

H2S + NaOH → Na2S + H2O