PROPERTIES AND USES

2.1 PHYSICAL PROPERTIES:

Acetaldehyde is a colorless, mobile liquid having a pungent suffocating odor that
is somewhat fruity and pleasant in dilute concentrations. Some physical properties of
acetaldehyde are given in Table 1.1.
The freezing points of aqueous solutions of acetaldehyde are as follows:
4.8 wt %, -2.50C; 13.5 wt %, - 7.80 C, and 31.0 wt %, - 23.00 C.
Acetaldehyde is miscible in all proportions with water and most common organic
solvents: acetone, benzene, ethyl alcohol, ethyl ether, gasoline, paraldehyde, toluene,
xylenes, turpentine, and acetic acid.

Table 2.1. PHYSICAL PROPERITIES OF ACETALDEHYDE

Properties Values
Formula weight 44.053
Melting point -123.5
Boiling point at 101.3 kPa (1 atm), °C 20.16
Density, d4 º 0.8045
d4 11 0.7901
d4 15 0.7846
d4 20 0.7780
Coefficient of expansion per °C (0-30 °C) 0.00169
Refractive index, nD20 1.33113
Vapor density (air = 1 ) 1.52
Surface tension at 20 °C,mN/ma 21.2
Absolute viscosity at 15 °CmPa.s b 0.02456
Specific heat at 0 °C,J/(g.K) 2.18
At 25 °C c 1.41
α = C p / C v at 30 °Cand 101.3 kPa c 1.145
Latent heat of fusion, kJ/mol c 3.24
Latent heat of vaporization, kJ/mol 25.71
Heat of solution in water at 0 °C, kJ/mol - 8.20
At 25 °C c - 6.82
Heat of combustion of liquid at constant 11867.9
pressure, kJ/mol c
Heat of formation at 273 K, kJ/mol c -165.48
Free energy of formation at 273 K, kJ/mol c -136.40
Critical temperature, °C 181.5
Critical pressure, MΡa (atm) 6.40(63.2)
Dipole moment, C-m (debyes ) 9.04 x 10 – 30
(2.69)
Ionization potential, Ev 10.50
Dissociation constant at 0 °C, K a 0.7 x 10 – 14
Flash point, closed cup, °C -38
Ignition temperature in air, °C 165
Explosive limits of mixtures with air, vol % 4.5 – 60.5
acetaldehyde

2.2 CHEMICAL PROPERTIES:

Acetaldehyde is a highly reactive compound exhibiting the general reactions of

aldehydes; under suitable conditions, the oxygen or any hydrogen can be replaced.
Acetaldehyde undergoes numerous condensation, addition, and polymerization reactions.

2.2.1 Decomposition: Acetaldehyde decomposes at temperatures above 400°C, forming

principally methane and carbon monoxide. The activation energy of the pyrolysis
reaction is 97.7 kJ/mol (408.8 kcal/mol). There have been many investigations of the
photolytic and radical – induced decomposition of acetaldehyde and deuterated
acetaldehydes.
2.2.2 The Hydrate and Enol Form: In aqueous solutions, acetaldehyde exists in
equilibrium with the hydrate, CH3CH(OH)2. The degree of hydration can be computed
from an equation derived by Bell and Clunie. The mean heat of hydration is – 21.34
kJ/mol (89.29kcal/mol); hydration has been attributed to hyper conjugation. The enol
form, vinyl alcohol (CH2 = CHOH) exists in equilibrium with acetaldehyde to the extent
of approximately one molecule per 30,000. Acetaldehyde enol has been acetylated with
ketene to form vinyl acetate.

2.2.3 Oxidation: Acetaldehyde is readily oxidized with oxygen or air to acetic acid,
acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal
product isolated depends on reaction conditions. Acetic acid is produced commercially by
the liquid – phase oxidation of acetaldehyde at 65°C with cobalt or manganese acetate
dissolved in acetic acid as a catalyst. Liquid – phase oxidation of acetaldehyde in the
presence of mixed acetates of copper and cobalt yields acetic anhydride. Peroxyacetic
acid or a perester is believed to be the precursor of acetic acid and acetic anhydride.
There are two commercial processes for the production of peracetic acid. Low
temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet
irradiation, or ozone yields acetaldehyde monoperacetate, which can be decomposed to
peracetic acid and acetaldehyde. Peracetic acid can also be formed directly by liquid –
phase oxidation at 5 - 50°C with a cobalt salt catalyst. The nitric acid oxidation of
acetaldehyde yields glyoxal. Oxidations of p – xylene to terephthalic acid and of ethanol
to acetic acid are activated by acetaldehyde.

2.2.4 Reduction: Acetaldehyde is readily reduced to ethanol. Suitable catalysts for

vapor-phase hydrogenation are supported nickel and copper oxide. Oldenberg and Rose
have studied the kinetics of the hydrogenation of acetaldehyde over a commercial nickel
catalyst.

2.2.5 Polymerization: Paraldehyde,2,4,6- trimethyl – 1,3,5 – trioxan, a cyclic trimer of

acetaldehyde is formed when a mineral acid, such as sulfuric, phosphoric, or hydrochloric
acid, is added to acetaldehyde. Paraldehyde can also be formed continuously by feeding
acetaldehyde as a liquid at 15 - 20°C over an acid ion – exchange resin.
Depolymerization of paraldehyde occurs in the presence of acid catalysts. After
neutralization with sodium acetate, acetaldehyde and paraldehyde are recovered by
distillation. Paraldehyde is a colorless liquid, boiling at 125.35 °Cat 101 kPa (1 atm).
Metaldehyde, a cyclic tetramer of acetaldehyde, is formed at temperatures below
0°C in the presence of dry hydrogen chloride or pyridine – hydrogen bromide. The
metaldehyde crystallizes from solution and is separated from the paraldehyde by
filtration. Metaldehyde melts in a sealed tube at 246.2°C and sublimes at 115 °C with
partial depolymerization.
Travers and Letort first discovered Polyacetaldhyde, rubbery polymer with an
acetal structure, in 1936. More recently, it has been shown that white, nontacky, and
highly elastic polymer can be formed by cationic polymerization with BF3 in liquid
ethylene. At temperatures below - 75°C with anionic initiators, such as metal alkyls in a
hydrocarbon solvent, a crystalline, isotactic polymer is obtained. This polymer also has
an acetal structure [poly (oxymethylene) structure]. Molecular weights in the range of
800,000 – 3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes
in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have
not been successful with polyacetaldehyde and the polymer has no practical significance
(see Acetal resins).

2.2.6 Reactions with aldehydes and ketones: The base catalyzed condensation of
acetaldehyde leads to the dimmer, acetaldol, which can be hydrogenated to form 1,3
butandiol or dehydrated to form crotonaldehyde. Crotonaldehyde can also be made
directly by the vapor-phase condensation of acetaldehyde over a catalyst. Crotonaldehyde
was formerly an important intermediate in the production of butyraldehyde, butanol, and
2-ethylhexanol. However it has been replaced completely with butyraldehyde from the
oxo process. A small amount of crotonaldehyde is still required for the production of
crotonic acid.
Acetaldehyde forms aldols with other carbonyl compounds containing active
hydrogen atoms. Kinetic studies of the aldol condensation of acetaldehyde and deuterated
acetaldehydes have shown that only the hydrogen atoms bound to the carbon adjacent to
the –CHO group takes part in the condensation reactions and hydrogen exchange. A
hexyl alcohol, 2-ethyl-1 butanol, is produced, industrially by the condensation of
acetaldehyde and butaraldehyde in dilute caustic solution followed by hydrogenation of
the acrolein intermediate. (see alcohols, higher aliphatic) condensation of acetaldehyde in
the presence of dimethylamine hydrochloride yields polyenals which can be
hydrogenated to a mixture of alcohols containing from 4 to 22 carbon atoms.
The base catalyzed reaction of acetaldehyde with excess formaldehyde is the
commercial route to pentaerythritol. The aldol condensation of three moles of form
aldehyde with one mole of acetaldehyde is followed by a crossed cannizzaro reaction
between pentaerythrose, the intermediate product, and formaldehyde to give
pentaerythritol. The process proceeds to completion without isolation of the intermediate.
Pantaerythrose has been made by condensing acetaldehyde and formaldehyde at 450 C
using magnesium oxide as a catalyst. The vapor-phase reaction of acetaldehyde and
formaldehyde at 450C over a catalyst composed of lanthanum oxide on silica gel gives
acrolein.
Ethyl acetate is produced commercially by the Tischenko condensation of
acetaldehyde with an aluminum ethoxide catalyst. The Tischenko reaction of
acetaldehyde with isobutyraldehyde yields a mixture of ethyl acetate, isobutyl acetate,
and isobutyl isobutyrate.

2.2.7 Reactions with Ammonia and Amines: Acetaldehyde readily adds ammonia to
form acetaldehyde ammonia. Diethyl amine is obtained when acetaldehyde is added to a
saturated aqueous or alcoholic solution of ammonia and the mixture is heated to 50-750C
in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12atm). Pyridine and
pyridine derivates are made from paraldehyde and aqueous ammonia in the presence of a
catalyst at elevated temperatures; acetaldehyde may also be used by the yields of pyridine
are generally lower than when paraldehyde is the staring material. Levy and Othmer
have studied the vapor- phase reaction of formaldehyde, acetaldehyde, and ammonia at
3600 C over oxide catalysts; a 49% yield of pyridine and picolines was obtained using an
activated silica-alumina catalyst. Brown polymers result when acetaldehyde reacts with
ammonia or amines at a PH of 6-7 and temperature of 3-250C. With acetaldehyde, a
primary amines can be condensed to Schiff bases: CH3CH=NR, the schiff base rivets to
the starting materials in the presence of acids.

2.2.8 Reactions with Alcohols and Phenols: Alcohols add readily to acetaldehyde in the
presence of a trace of mineral acid to form acetals; eg, ethanol and acetaldehyde form
diethyl acetal. Similarly, cyclic acetals are formed by the reactions with glycols and
other polyhydroxy compounds; eg, the reaction of ethylene glycol and acetaldehyde gives
2 – methyl – 1,3 – dioxolane.
Mercaptals, CH3CH(SR)2, are formed in a like manner by the addition of
mercaptans. The formation of acetals by a noncatalytic vapor – phase reactions of
acetaldehyde and various alcohols at 3500C has been reported. Butadiene can be made
by the reaction of acetaldehyde and ethyl alcohol at temperature s above 3000C over a
tantala – silica catalyst. Aldol and crotonaldehyde are believed to be intermediates.
Butyl acetate has been prepared by the catalytic reaction of acetaldehyde with butanol at
3000C.
Reaction of one mole of acetaldehyde with excess phenol in the presence of a
mineral acid catalyst gives 1,1 – bis (p-hydroxyphenyl) ethane. With acid catalysts
acetaldehyde and three moles or less of phenol yield soluble resins. Hardenable resins
are difficult to produce by the alkaline condensation of acetaldehyde and phenol as
acetaldehyde tends to undergo aldol condensation and self-resinification.

2.2.9 Reactions with Halogens and Halogen compounds: Halogens readily replace the
hydrogen atoms of the methyl group: eg, chlorine reacts with acetaldehyde or
paraldehyde at room temperature to give chloroacetaldehyde; increasing the temperature
to 700-800C gives dichloroacetaldehyde; and at a temperature of 80-900C chloral is
formed. The catalytic chlorination with an antimony powder or aluminum chloride ferric
chloride has been described. Bromal is formed by an analogous series of reactions. It
has been postulated that acetyl bromide is an intermediate in the bromination of
acetaldehyde in aqueous ethanol. The gas – phase reaction of acetaldehyde and chlorine,
has prepared acetyl chloride.
 The oxygen atom in acetaldehyde can be replaced by reaction of the aldehyde
with phosphorus pentachloride to produce 1,1 – dichloroethane. Hypochlorite and
hypoiodite react with acetaldehyde yielding chloroform and iodoform, respectively.
Phosgene is produced by the reaction of carbon tetrachloride with acetaldehyde in the
presence of anhydrous aluminum chloride. Chloroform reacts with acetaldehyde in the
presence of potassium hydroxide and sodium amide to form 1,1,1 – trichloro – 2-
propanol.

2.2.10 Miscellaneous Reactions: Sodium bisulfite adds to acetaldehyde to form a white

crystalline addition compound, insoluble in ethyl alcohol and ether. The bisulfite
addition compound frequently is used to isolate acetaldehyde from solution and for
purification; the aldehyde is regenerated with dilute acid. Hydrocyanic acid adds to
acetaldehyde in the presence of an alkali catalyst to form the cyanohydrin; the
cyanohydrin may also be prepared by reaction of sodium cyanide with the bisulfite
addition compound. Acrylonitrile can be made by reaction of acetaldehyde with
hydrocyanic acid and heating the cyanohydrin to 600 – 7000C. Alanine can be prepared
by reaction of ammonium salt and alkali metalo cyanide with acetaldehyde; this is the
Strecker amino acid synthesis, a general method for the preparation of α-amino acids.
Grignard reagents add readily to acetaldehyde, the final product being a secondary
alcohol. Thioacetaldehyde is formed by reaction of acetaldehyde with hydrogen sulfide;
thioacetaldehyde polymerizes readily to the trimer.
Acetic anhydride adds to acetaldehyde forming ethylidne diacetate in the presence
of dilute acid; boron fluoride is also a catalyst for the reaction. Ethylidene diacetate is
decomposed to the anhydride and aldehyde at temperatures of 220-2680C and initial
pressures of 1.5 – 6.1 kPa (110- 160 mm Hg), or by heating to 1500C with a zinc chloride
catalyst. Acetone has been prepared in 90% yield by heating an aqueous solution of
acetaldehyde to 4100C in the presence of a catalyst. Acetaldehyde can be condensed with
active methylene groups. The reaction of isobutylene with aqueous solutions of
acetaldehyde in the presence of 1-2% sulfuric acid yields alkyl-m-dioxanes, the principal
product being 2,4,4,6-tetramethyl – m dioxane in yields up to 90%.
2.3 Uses:
The manufacturers use about 95% of the acetaldehyde produced internally as an
intermediate for the production of other organic chemicals. Figure 1 illustrates the
significant variety of organic products ( and their end uses) derived from acetaldehyde.
Acetic acid and acetic anhydride are the derivatives of acetaldehyde followed by
n-butanol and 2-ethylhexanol. Twenty percent of the acetaldehyde is consumed in variety
of other products, the most important being pentaerythritol, trimethylolpropane,
pyridines, peraceticacid, crotonaldehyde, chloral, lactic acid.