Pure & App!. Chem., Vol. 57, No. 6, pp. 855864, 1985.

Printed in Great Britain.

1985 IUPAC

INTERNATIONAL UNION OF PURE

AND APPLIED CHEMISTRY
ANALYTICAL CHEMISTRY DIVISION
COMMISSION ON ELECTROANALYTICAL CHEMISTRY*

RECOMMENDED METHODS FOR

THE PURIFICATION OF SOLVENTS
AND TESTS FOR IMPURITIES
METHANOL and ETHANOL
Prepared for publication by
Methanol: Y. MARCUS and S. GLIKBERG
Ethanol: Y. MARCUS
Department of Chemistry, The Hebrew University of Jerusalem,
Jerusalem 91904, Israel

*Membershjp of the Commission for 198385 is as follows:

Chairman: J. Jordan (USA); Secretary: K. Izutsu (Japan); Titular Members: A. K. Covington
(UK); J. Juillard (France); R. C. Kapoor (India); E. Pungor (Hungary); Associate Members:
W. Davison (UK); R. A. Durst (USA); M. Gross (France); K. M. Kadish (USA); R. Kalvoda
(Czechoslovakia); H. Kao (China); Y. Marcus (Israel); T. Mussini (Italy); H. W. NUrnberg
(FRG); M. Senda (Japan); N. Tanaka (Japan); K. Tth (Hungary); National Representatives:
D. D. Perrin (Australia); B. Gilbert (Belgium); W. C. Purdy (Canada); A. A. Vlek
(Czechoslovakia); H. Monien (FRG); M. L'Her (France); Gy. Farsang (Hungary); H. C. Gaur
(India); W. F. Smyth (Ireland); E. Grushka (Israel); S. R. Cavallari (Italy); W. Frankvoort
(Netherlands); Z. Galus (Poland); G. Johansson (Sweden); J. Buffle (Switzerland);
H. Thompson (UK); J. G. Osteryoung (USA); I. Piljac (Yugoslavia).
Republication of this report is permitted without the need for formal JUPAC permission on condition that an
acknowledgement, with full reference together with JUPAC copyright symbol ( 1985 IUPAC), is printed.
Publication of a translation into another language is subject to the additional condition of prior approval from the
relevant JUPAC NationalAdhering Organization.
 Methanol

Abstract - Specifications for the corrnercially available solvent, relevant

physicochemical and key solvent properties are given. The procedures for
purification include removal of water, production of conductivity-grade
solvent, and removal of bases and heavy metals. Gas chromatography is best
for detection of organic impurities and flameless atomic absorption for
heavy metals. Methods for the determination of water depend on its concen-
tration.

INTRODUCTION

The classical method for the production of methanol, the destructive distillation of wood,
has long ago been replaced by synthetic methods. These methods yield a quite pure product,
and the change has caused one of the more important impurities in the methanol employed in
the older literature, namely acetone, to be no longer a pressing problem. The commercial
grade A of methanol is nowadays sufficiently pure for practically all synthetic uses and for
its use as a solvent, except for very specific requirements. The specifications of manufac-
turers for their guaranteed reagents generally conform to those in the American Chemical
Society "Reagent Chemicals" (ref. 1), see Table 1.

TABLE 1. Examples of specifications for commercially available methanol

ACSa Merckb FlUkaC Bajcerd AJe

Impurity Maximal content in ppm

Free acid, as HCO2H 20 20 25 20 9
Free alkali, as NH3 3 3 1 2 2
Chloride 0.5
Heavy metals 0.1 0.5 1
Magnesium 0.1
Ethanol 1000
Acetone 10 1001 10 } 10 50
Formaldehyde 1 10
Chloroform 50
Water 2000 500 500 300 1000
Nonvolatile substances 10 10 20 3 10
Substances reducing 5 min with 15 mm with pass pass 20 mm with
i<ivinOf lOpmol/2OmL 5ijmol/12.6mL test test 2.5mol/10mL

Other specifications

Boiling range,0C 1.0 1.0 2.0(100%) 1.0(95%)

% Transmittance
at2l0nm 16 20 16
at22Onm 40 50 25 40
at240nm 79 80 79
at280nm 98 98 99 98

aRef. 1; bMerck Standards for guaranteed purity reagent; Fluka specifica-

tions for puriss. p.a. absolute and acetone-free eagent; J.T. Baker spec-
ifications for "Baker Instra-Analyzed" reagent; AnalaR Standards fo
Laboratory Chemicals, AnalaR Standards Ltd., London, 7th ed., 1977; Pink
color persists for at least the specified tiji at
15C when the specified
amount of aqueous KNnO, is added to the specified Xolume of methanol;
Bracketting the normal boiling point of 64.7C; Minimal light transmittance
in 1 cm light-path cells.

The physical and thermodynamic properties of methanol have recently been critically reviewed
(ret. 2). Selected other properties are given
in a book dealing with organic solvents
(ref. 3). Values for selected properties of methanol taken from these and other sources are
listed in Table 2.

856
 Purification of solvents and tests for impurities: methanol 857

TABLE 2. Selected properties of methanol

Property Value Ref.

Molar rrass, M/Kg mor' 0.032042

Freezing temperature, tm/C 97 .56 2
Boiling temperature at 0.101325M Pa, tb/C 64.70 2
Flash point, tf1/C 12 3
Density at 25 00, p/kg drn3 0.78664 2
Thermal expansivity, isobaric, at 20 c, (Xp/K1 1.182x103 4
Compressibility, isothermal, at 25 C, KT/Pa' 1. 195x109 4
Surface tension at 25 00, y/N m 0.02212 5
Dynamic viscosity at 25 00, Tl/Pas 0.5445x103 3
Vapor pressure at 25 00, p/kPa 16.725 2
1
Enthalpy of vaporization Aif"/kJ rnol at 25 00. 37.40 2
at normal boiling temperature 34.48 2
Standard molar entropy at 25 00, S0/JIC1IrD1_' 239.7 2
Molar heat capacity at 25 00, c/JK 'mol' 81.17 2
Relative permittivity at 25 00, c 32.70 3
Volume susceptibility at 25 00, Xv/cm3 mol -21.42x106 5
Refractive index, D-line, at 25 00, D 1.32652 2
Electrolytic conductivity at 25 00, K/S cm' 1.5x109 3
Dipole moment, kl/D 2.87 3
Polarizabiity, c/m3 molecule' 3.26x103 5
Intermolecular potential energy minimum 255 5
(divided by Boltzmann' s constant), (u/k)/K
Collision diameter, a/nm 1 0.371 5
Polarity index, Reichardt, ET/kcal mol 55. 5 6
Polarity index, Koower, Z/kcal mol' 83. 6** 7
Acceptor number, Gutmann, AN 41.3 8
Donor number, Gutmarth, DN/kcal mol' 33. 8** 9
Polarity index, Taft Kamlet, ir 0.586 10
Fidrogen bond donor power, Taft Kamlet, c 0.990 11

= 3.33564 x i0C in. 1 cal = 4.184 J.

Methanol, being a protic solvent but having also electron-pair donation capabilities , is an
amphoteric solvent , similar in many respects to water . It is capable of solvating both cat-
ions and anions , and although its dielectric constant (relative permittivity) is modest
(32.7 at 25 00), in comparison with water (78.5 at 25 00), it supports the ionic dissociation
of most electrolytes. On the other hand, it is well miscible with most organic solvents,
except the higher alkanes and perfluoroalkanes, and is a good solvent for organic compounds
in general. These properties have made methanol a very extensively utilized and studied
solvent.

The low freezing point of methanol (-97.6 C) permits the study of electrolytes by, e.g.,
n.m.r. techniques, at low temperatures, where line widths are much reduced and solvent ex-
change is considerably slowed down compared with room temperature. The relatively low normal
boiling point of methanol (64.7 00) can be turned into an advantage, when it permits the
ready removal of the sOlvent from temperature-sensitive reaction products. The low viscosity
of methanol is an advantage too.

Since methanol itself is a rather reactive solvent, in terms of

reversible donor-acceptor
interactions with solutes, it requires a relatively high concentration of even more reactive
impurities (water, acids, bases) to falsify the results obtained with methanol of' ordinary
purity. For certain very demending purposes, however, these impurities must be removed, and
precautions must be taken against tiiefr re-introduction from the atmosphere.
These and. other properties, such as ready availability, inexpensiveness, and low toxicity of
moderate concentrations of the vapors (< 260 mg rn-3, contrasted with high toxicity of the
ingested substance) contribute to the general utility of methanol as a solvent.

STRUCTURE OF LIQUID METHANOL

The main feature of thestructure of liquid methanol is its association by hydrogen bonding.
Unlike water molecules, which can both donate and accept two hydrogen bonds and therefore
produce an extensive three- dimensional associated network, methanol molecules can donate one
and accept two hydrogen bonds. As a consequence, chain-like associates are formed in the
liquid. It is remarkable, though, that the angular correlation factor g has the value 0.99,
i.e ,nearly unity, which is characteristic of non-associated liquids (compare with g = 2.67
858 COMMISSION ON ELECTROANALYTICAL CHEMISTRY

:inwater and g = 3 . 01 in ethanol , all the values pertaining to 25 C) (ref . 12) . On the other
hand, the entropy of vaporization at the normal boiling point , S' 102 . 06 JK'rro1' , is
definitely higher than the expectation value fran Louton' s rule , 86 JX mo1 , and this
is in agreement with the associated nature of the liquid.

t
The infrared and n.m.r. spectra of methanol , too , indicate its associated nature , in that
few "free" OH groups, but many hydrogen-bonded ones, are seen (ref.. 13). The shifts produced
by solutes, whether polar aprotic solvents or anions, in the relative populations of these
classes of OH groups are typical for the interactions.

IKE? SOLVENT PROPERTIES OF METhANOL

Methanol is a good solvent for polar organic substances. Nonpolar substances, as far as the
solubiity can be judged from the solubiity parameter o '[p(" RT)/M]*) = 29.3 J.
-3 /2 (ref. 12), should be dissolved in methanol to at least 1 mole % for substances which
have solubiity parameters above 18.6. The practical limit seems to be a little lower, say
16.5. This limit excludes the alkanes and perfluoroalkanes, which indeed are not well soluble
in methanol, but includes haloaJJzanes and arometic hydrocarbcns, which are generally well
soluble in, or completely miscible with, methanol.
Methanol is a good solvent for electrolytes. Its dielectric constant and solvating power for
ions are adequate for producing complete ionic dissociation of a dissolving electrolyte,
although some ion pairing nay occur. For 1:1 electrolytes ion pairing will occur (ref. 14)
when the sum of the radii of the olvated ions of opposite charge is less than 0.857 mm. The
radii of solvated ions in methanul are generally in the range 0.3 to 0.5 mm, so that ion
pairing should not be a rare occurrence.
The solvation power of methanol tcwards ions is sinilar to that of water. The standard Gibbs
free energy of transfer of monovalent ions from water to methanol is generally <15 kJ rnoL .
(ref. 15). The solubiity of sparingly soluble 1:1 electrloytes should therefore, be at most
400 times smaller than in water, and, for example, in the case of silver chloride the factor
is 53 (ref. 16). Electrolytes which are well soluble in water are generally also soluble in
methanol, with some noteworrthy exceptions, such as sodium fluoride, potassium chloride, and
the sulfates. The solubiities of some salts of the alkali metals are shown in Table 3.

Methanol is less acidic than water. In aqueous solutions at 25 C pK= 15.5530.016 (one
standard deviation) (ref. 19) (Ka in mol/dm3). A more recent but less precise estinate is
pKa = 15.20.3 (ref. 20). The autoprotolysis constant has been reported as pK = 16.70
(ref. 21 and 22), and a more recent determination has given pK5 = 16.91 (ref. 23) (Ks in
mel2 dm6). Since methanol is a typical ampholytic protic solvent it has a levelling effect
on the reactivities of acids and bases.
TABLE 3. Molal solubiities of some salts of the alkali metals, (mel/kg
solvent) at 25 C (ref. 17)
F Cl Br I NO3 003 SO,

Li 0.0068 4.95 3.95 vsa 6.23 0.0075 0.0115

Na 0.0055 0.240 1.56 4.17 0.345, 0.0293 0.0008
K 0.394 0.071 0.175 1.029 0.0376 0.447 3x105
Rb 0111b
Cs 0.215 0.0121

aVery soluble bFrom ref. 18.

PURIFICATION OF MEFHANOL

In view of the fact that corrmercial methanol is now sufficiently pure for most applications,
the purification methods that have been utilized in the past for precise laboratory rk are
generally no longer required. These methods have been listed in ref. 3 and 24 and need to be
applied only under exceptional circumstances.
Still, one of the more cainnon impurities, water, is present in cainrrcial pure methanol to
an appreciable extent (ca. 500 ppm, see Table 1). This amount of
water is not expected to
have a profound effect on dilute solutions of solutes in methanol, in view of the hydroxylic
nature of this solvent itself and its low
molar volume, hence high concentration of hydroxyl
groups. There are 24.55 mol/dm3 of OH graips in methanol, and only 0.022 mol/dm3 of water
molecules (at the level of 500 ppm). For those applications where this impurity is still.
critical, following is a reccnnnended method of purification.

Procedure I (remcaal of water)' (ref. 25)

Step 1. Distill the methanol with a good fractionating column under the exclusion of mois-
ture. The water content is reduced to ca. 100 ppm. From this step proceed to either step 2
or step 3, according to requirements.
 Purification of solvents and tests for impurities: methanol 859

Step 2 . Pass the methanol slowly through a column of dry molecular sieves (Linde type LA),
store the methanol over a lump of calcium hydride. As long as the calcium hydride retains
its lump form, the water content is <7 ppm.

Step 3 . For a reduction of the water content to 0 . 5 ppm, the methanol is distilled twice in
.anall-glass still frc*n metallic sodium. Freshly cut pieces , 1-2 g per L methanol are used,
the first few tens of mL of distillate are discarded, and the rest, boiling within 0.01 00
of the boiling point , is used inunediately (ref . 26).
Caution: Anhydrous magnesium perchiorate is not suitable for the drying of methanol : danger
of EXPLOSION! Nor are drierite or calcium oxide effective drying agents for methanol . Calcium
metal is apt to contaminate the methanol with ammonia from its calcium nitride npurity.
Procedure II (conductivity grade) (ref. 27)
Step 1. Reflux 4.5 L methanol for 2th over 50 g magnesium. Distill 4 L and reflux these over
silver nitrate for 24h , under exclusion of atmospheric moisture and carbon dioxide.
Step 2 . Distill the methanol and shake it with activated alumina for 24h . Filter through a
sintered glass filter into a vessel which contains an atmosphere of pure nitrogen, from which
the methanol is distilled again in an all-glass system.
Specific conductances of 5x10 S are readily obtained with this method. With a conductivity
cell sealed between
specific conductance observed was 1 . 5x10 S cin .
the condenser and receiver in the last distillation step , the mininal

Procedure III (removal of bases and heavy metal$) (ref. 28 and 29)
Step 1 . Condition a dry macroreticular (e .g. Amberlyst 15) or macro-porous sulfonated-
polystyrene-type cation exchange resin in the hydrogen-ion form for 24h with methanol to pre-
swell it and eliminate the removable water.
Step 2 . Prepare a 1 : 2 mixture (by volume) of a strongly acidic cation exchange resin (e.g.,
Duolite C-20 , pretreated successively with 2 NHC1 1, . 5N NaOH , and 2N HC1) and a strongly
basic anion exchange resin (e.g., Duolite A-162, pretreated successively with 1. 5N NaOH,
2N HC1, and 1. 5N NaOH), wash with water, dry and preswell it in methanol for 24h.

Step 3. Pass the methanol to be purified successively through a 6 to 10 cm column of the

mixed exchanger from Step 2, then through a 6 to 10 cm column of the corditioned resin from
Step 1 at a rate of 3 rnLlmin.
This treatment reduces the concentration of amines, that produce an obnoxious odor in the
methanol, to <0.1 ppm, and remeves this odor (ref. 28). The concentration of ions, such as
Na, K, Mg2 , Ca2 +, Cl,
N0j, and SO is reduced from 2-10 ppm to <0.02 ppm each (ref. 29).
Many heavy metal ions will also be retained on these columns. Specific removal of Fe3+, Cu2+,
Co2 +, Pb2 +, etc.,on polymers with anchored chelating agents, such as tiron, is described in
ref. 30 and 31.

Other impurities are either not obnoxious and can be tolerated at the levels at which they
are present in high grade commercial methanol, or, like carbon dioxide and other acidic im-
purities, are removed by procedures I or III. For the removal of other impurities, such as
acetone or formaldehyde, from technical grade methanol, consult ref. 3, 24, or 26. Purified
methanol should be prevented from being oxidized to formaldehyde by exclusion of air.

DETECFION OF IMPURITIES
Gas chromatography is the generally useful method for the determination of the residual impur-
ities in methanol. High sensitivity detectors, such as flame ionization, are requirod for the
determination of the impurities at the <10 ppm level. As a stationary phase, a mixture of 67%
polyethylene glycol 4000 and 33% diethyl sebacate, applied as 5% on silanized kieselguhr, has
been recommended; as the operating temperature 60 C (ref. 32). See also ref. 33 for a study
of several column packings for the gas chromatography of methanol, and ref. 34 for the analy-
sis of methanol by high performance liquid chromatography.
Ethanol can be detected in methanol down to a level of 3 ppm by gas chromatography (ref. 35).
Amines and other reactive impurities cai-i be detected by means of a copper(II)-ion-selective
electrode (ref. 37).
Water i generally determined by Karl-Fischer titration down to <500 ppm (ref. 32). For a
determination at the 70 ppm level, by measurements in the UV of the displacement of the keto-
ketal equilibrium after acidification with HBr, see ref. 36. For determinations by means of
physico-chemical measurements at the <10 ppm level (ebulliometry and critical solution tem-
perature of cyclohexane) see ref. 26.

Trace concentrations of heavy metals can be determined by flameless atomic absorption or by

X-ray fluorescence, after concentration of these impurities on chelating ion exchangers based
on cellulose (ref. 31).
 Ethanol

Abstract - Specifications for the corrunerciafly available solvent, relevant

physicochemical and key solvent properties are given. The procedures for
purification include the removal of water and of organic impurities. The
latter are best detected by gas chromatography and heavy metals by flame-
less atomic absorption. Water is detennined by coulometric Karl Fischer
titration at >5 ppm.

INTRODUCTION

Ethanol is produced either by fermentation or synthetically, and the impurities it is likely

to contain depend somewhat on the source. Ethanol produced by fermentation may contain higher
alcohols ("fusel oil", mainly pentanol isomers), whereas that produced synthetically may con-
tain diethyl ether, in addition to aldehydes, ketones and esters that may be present in the
products from both methods. A ubiquitous impurity, of course, is water, and since it is
often removed by azeotropic distillation with benzene, this hydrocarbon may also be present
as an impurity that is troublesome for spectroscopic studies in the ultraviolet region.

Ethanol is available commercially in quite pure form, either as the azeotrope with water
(containing ca. 5% water) or as so-called "absolute" ethanol, containing only 0.2% water. The
specifications of manufacturers for their purest grades generally conform to those in the
American Chemical Society "Reagent Chemicals" (ref. 1), see Table 1.

The physical and thermodynamic properties of ethanol have recently been reviewed (ref. 2).
Selected other properties are given in a book dealing with organic solvents (ref. 3) and in a
few other sources. Values for selected properties of ethanol taken from these sources are
listed in Table 2.

TABLE 1. Examples of specifications of commercially available ethanol

ACSa Merckb FlUkaC AnalaRd

Impurity Maximal content in ppm

Free acid, as CH3CO2H 30 10 5 10
Free base, as NH3 3 3 5
Chloride 0.5
Heavy metalse 0.1 0.1 0.05
Iron 0.1 0.5 0.05
Light metalsf 0.05
Methanol 1000 . 500 2000 500
Higher alcohols 3Q7 500 iOOtl
Formaldehyde 10 10
Aldehydes, as CH3 CHO 10 10
Ketones, as CH3 COCH3 10 500 100 10
Water 2000 2000 2000 2000
Nonvolatile substances 10 5 10 5
Substances reducing KNnOk k 3 4k

Other specifications
Boiling range, C 2 1
% mansmittanceh
at2lOnm 35 30
at220nm 55 52
at23Onm 72 73
at250nm 90 90
at >270 mm 98

aRef. 1; 0Merck Standards for guaranteed purity reagent; cFluj< specifica-

tions for puriss. reagent; dAnalaR specifications for ARISTAR grade reagent
(except for higher alcohols and substances reducing KNn0, not specified

860
 Purification of solvents and tests for impurities: ethanol 861

there but specified for AnalaR grade reagent which also has a boiling range
of only 0.5C); eMn, Co, Ni, Cu, Zn, Cd, Pb, Hg (most stringent specifica-
tion for ARISTAR grade reagent: Hg 0.002 ppm, Pb 0.01 ppm, Cd 0.005 ppm);
fMg, Al, 1<, Ca, but for Na the linit is 0.5 ppm; Bracketing the normal
boiling temperature of 78.3C; light transmittance in 1 cm light-
path cells; aThe 30 ppm liniit applies specifically to isopropyl acohol;
the test for fusel oil is the absence of odor, after 10 cm3 ethanol has been
mixed with 5 cm3 water and 1 m3 glycerol, the mixture placed on a filter
paper and left to evaporate; 'The pink color should persist for >5 mm. when
20 cm3 are treated with 0.1 cm3 of 0.1 N KNnO at 15C.

Table 2. Selected properties of ethanol

Property Value Ref.

Molar mass, M/kg mol' 0.046068
Freezing temperature, tm/C -114.1 2
Boiling temperature at 0.101325 MPa
tb/C 78.29 2
Flash point, tf1/C 13 3
Density at 25e, p/kg dm 0.78509 2
Thermal expansivity, isobaric, at
25C, ar/K' 1.063 X 10 5
Compressibility, isothermal, at 25C,
Kq/Pa' 1.187 x i0
Surface tension at 25C, i/N m1 0.02189 5
Dynamic viscosity at 25C, r/?3-s 1.078 x 10 3
Vapor pressure at 25C, p/kPa 7.969 2
Enthalpy of vaporization, M"/kJ mo11,
at 25C 42.30 2
at normal boiling temperature 38.72
Standard molar entropy at 25C, S/JIC1 mol1 161.04 2
Molar heat capacity at 25C, c/JK1 mol' 111.96 2
Relative permittivity at 2 5C, 24.55 3
Volume susceptibility at 25C, Xv/cm3 mol' -33 .61 x 106 5
Refractive index, D-line, at 2 5C, D 1.35941 2
Electrolytic conductivity at 25C, K/S cm' 1.35 x i0 3
Dipole moment, /D 1. 66' 3
Polarizability, a/m3 molecule1 5.12 x 10-30 5
Intermolecular potential energy minimum
(divided by Boltzmann' s constant)
(u/k)/K 324 5
Collision diameter, c/mi 0.434 5
Polarity index, Reichardt, ET/kcal mol1 51. 9 6
Polarity index, Kosower, Z/kcal mol' 76. 6** 7
Acceptor number, Gutniann, AN 37.1 8
Donor number, Gutmann, D N /kcal mol' 30. 4 9
Polarity index, Taft Kamlet, i' 0.54 10
Hydrogen bond donor power, Taft Kamlet, a 0.85 11

3.33564 x 1030Cm '1 cal 4.184 J.

Ethanol, being a protic solvent but having also electron-pair donating capabilities, is an
amphoteric solvent, and is capable of solvating both cations and anions. It has only a
modest dielectric constant (relative perrnittivity), 24.55 at 25 C, hence most electrolytes,
when not too dilute, will be extensively ion-pafred in it. Ethanol is miscible with most
organic solvents , including alkanes, and is a good solvent for' organic compounds in general.
Mixtures of ethanol with water are better solvents for electrolytes than neat ethanol, and
have been used extensively for the investigation of many properties of electrolytes in mixed
aqueous solvents.

Ethanol is fairly reactive regarding reversible donor-acceptor ,interactions with solutes,

hence many impurities need be present at relatively high concentrations in order to affect
appreciably measurements on solutions in ethanol. A notable exception is water, which may
still have adverse effects on many properties even in so-called "absolute' ethanol, where it
is present to the extent of 0.2 mass %, or 0.5 mole %.

The physical properties of ethanol, its properties as a solvent, and its ready availability
in pure form contribute to its general utility as a solvent. The vapors are non-toxic even
862 COMMISSION ON ELECTROANALYTICAL CHEMISTRY

at rrderate1y high concentrations, at which they are readily detectalle by their odor
(ref. 3) . The physiological effects of ingestion, of course, need not be described here, but
they place some legal restrictions on the free use of ethanol.

STRUCTURE OF LIQUID EIHANOL

Ethanol is an associated liquid, and forms short chains by hydrogen bonding. Ethanol mole-
cules can donate one but accept two hydrogen bonds , hence the aggregates formed are
irregular. Evidence for the association arises fran many properties of liquid ethanol . For
example, the entropy of vaporization at the normal boiling temperature is
&SV 110.18 JKmol', much higher than the value given by Trouton' s rule for nonassocia-
ted liquids, "86 JIC' irol '. The angular correlation factor g has the value of 3.01 at 25C,
ccznpared with 2.67 for water (ref. 12), typical of highly associated liquids (nonassociated
ones have g 1).

The association of ethanol has also been studied spectroscopically, meinly by infrared
(ref. 38) and n.m.r. (ref. 39) methods. The relaxation time of the ethyl group has been
found to be shorter than that of the hydroxyl group, since the latter is hydrogen bonded to
other similar groups.

KEY SOLVENT PROPERTIES OF EThANOL

Many organic liquids are completely miscible with ethanol, including the alkanes on the one
hand and highly polar liquids such as - gyopl on the other. The solubility parameter of eth --
anol, calculated as [p(iHV - RT)/M} 26,1 J cm3 /2, is sufficiently near those of
nonpolar substances"(e.g., tin tetrachlride, 6 17.8 J an3/2 or iodine,
(S 28.8 J cur3 /2) to make it a good solvent for these.
The ability of ethanol to solvate both cations and anions is related to its polarity as mea-
sured by the donor number D A 30.4 kcal mo11 and the acceptor number AN 37.1, (see Table
2) which makes it a fairly good solvent for electrolytes. The standard Gibbs free energy of
the transfer of monovalent ions fran water to ethanol is 5 to 20 kJ mol' (ref. 15), so that
the solvation of the ions by ethanol is only to that extent worse than by water. Hcwever,
the solvated ions are apt to associate in ethanol to solvent-shared and contact ion pairs,
since the sum of the radii of the ions rarely exceeds the maximal distance of 1.14 nm for
two oppositely single charged ions to be counted as an ion pair (ref. 14), in this solvent
having c 24.55 at 25C.

These considerations are relevant to the solubility of electrolytes in ethanol. For electro-
lytes that have an appreciable solubility in water, the ionic interactions are too complica-
ted for the present state of the theory to prnnit a prediction of what the solubility should
be in ethanol. For electrolytes kf low solubility such predictions are more nearly feasible.
For example, silver chloride shi6uld be 139 times less soluble in ethanol than in water
(ref. 16) whereas the actual ratio is 149 (ref. 40). The solubilities of some salts in eth-
anol are given in Table 3.

Table 3. Molal solubilities of some salts of the alkali metals, ammonium

and tetraethylarnrioniiin (mol/kg solvent) at 25C (ref. 41)

OH F Cl Br I ClO CO3 B(C6H5h

Li 5.83 8.35 18.74 14.26
Na 431a 0.024 0.031 0.225 2.84
< 69oa 0.0174 0.0288 0.0405 0.1054 8.9x1r3
Rb 0.0065 5.jx10'
0.0318 0.0014b
Cs O.O232c 5.1x10 0,34b o.ooicP
NH 0.354 0.162 0.28
(C2H5)kN 8.51 2.76 0.048

aAt 28C; bAt 20C; CRef 17.

Ethanol is less acidic than water, the equilibrium constants for the reactions
C2H5OH + H,O = C2H5OH2 + H2O and C2H5OH + 0H C2H5O + H20 being 6 x 10' and 63, respec-
tively (ref. 21). The acidity constant has been estimated as pKa = 16 for ethanol in aqueous
solutions (ref. 19). The autoprotolysis constant has been givers as p1<5 19.1 (ref. 21),
18.95 (ref. 22), 18.75 or 19.28(ref. 23) and 18.67 (K in rnol2 kg2) and 18.88
(K in mo12 dm-6) at 25t (ref. 42).
 Purification ofsolvents and tests for impurities: ethanol 863

PURIFICATION OF ETHANOL

Ethanol is available ncwadays in highly pure form, see Table 1 , so that the methods that have
been used :in the past (ref. 3 , 24) for the purification of thj solvent for most laboratory
work are generally no longer required.
Of the impurities remaining in the best reagent grade ethanol are the other alcohols (metha-
nol, propanol) , acetone, and water. The last mentioned is the most reactive and likely to
interfere, and procedures for its removal have been recommended ( see below) . Benzene is an
impurity not nonilly encountered, but it may. be present in a sample dried by ternary azeo-
tropic distillation. It can be renoved frun dry ethanol by careful fractional distillation,
forming an azeotrope with a normal boiling temperature of 68 . 2C (ref. 2L) . Aldehydes , if
present, can be removed by the passage of the ethanol through a column of a strong base anion
exchange resin in the HSO3 form (ref. 3).
Procedure I (removal of organic impurities) (ref. 44)
Step 1. Add carefully concentrated sulfuric acid to the ethanol, and distill the ethanol.
The H, SO1 acts as an oxidizing agent for aldehydes, and this step also reduces the content
of amines.

Step 2. Redistill the ethanol from solid sodium hydroxide, to remove entrained sulfuric acid
and acidic impurities.

Step 3. Fractionally distill the ethanol with a good rectification column.

This combined treatment is said to reduce the content of aldehydes and ketones to <1 ppm, and
make the ethanol a solvent suitable for spectroscopic studies of solutes in the ultraviolet
region.

For the removal of water from so-called "absolute" ethanol, containing about 2000 ppm of
water, the following procedures are recommended.

Procedure II (removal of water) (ref. 45)

Step 1. Dehydrate "absolute" ethanol down to <1000 ppm water by reflux over calcium oxide,
and distill it, taking precautions to exclude water.

Step 2. Treat a portion of 200 cm3 of the dehydrated ethanol with 3.5 g calcium hydride
crushed to a powder until all of it dissolves by gentle boiling. This treatment produces cal-
cium ethoxide. Distill two th-ixds of the alcohol off, to remove ammonia originating in
calcium nitride possibly present in the hydride.

Step 3. Transfer the remeining solution of calcium ethoxide in ethanol into 2 dm3 of dehy-
drated ethanol in a distilling apparatus provided with a double condenser. Boil the solution
gently for 20 h, allowing 100 cm3 to distill over in a slow current of dried pure hydrogen.
Discard this distillate.
Step 4. Distill the bulk of the ethanol slowly in the current of hydrogen, discarding the
last 1Q0cm3.

The purity of the ethanol so obtained is checked by its

density, being
0.789334 + 0.000003 n an3 at 20C (ref. 45), compared with the accepted value of
0.78934 0.00007 gm cm3 (ref. 2).

Procedure III (removal of water) (ref. 3)

Step .1. Add about 5p of hexane, cyclohexane, or 2,2, 4-trimethyl-1-pentane to "absolute" eth-
anol, and fractionate to remove the aqueous azeotrope containing the water. This step reduces
the water content to <500 ppm.

Step 2., Pass the dehydrated ethanol slowly through a coli,mn of dry molecular sieves (Linde
type 4A'). This step reduces the water content further (a sinilar treatment reduces the water
content of methanol to 7 ppm).

DETECTION OF IMPURITIES

Trace concentrations of heavy metals can be determined by flameless atomic absorption, using
a graphite furnace and a tantalum boat (ref. 46.), or by anodic stripping voltammetry in the
residue after evaporation (ref. 47).

Organic impurities are generally determined by gas chrartography, with a stationary phase
made up of 2 portions of polyethyleneglycol 1000 to one portion of bis(2-ethThexy1)sebacate,
applied 15% on silanized kieselgi.thr (ref. 47), or of polyethyleneglycol 300, applied 25% on
Chromosorb W (ref. 48). In the latter case the limit of determination is 5 ppm. Flame
 864 COMMISSION ON ELECTROANALYTICAL CHEMISTRY

ionization detection is used at these 1ci levels.

Water can be qualitatively detected dcn to 500 ppm by the formation of a precipitate when
aluminum ethoxide in benzene is added to a sample of the ethanol . Quantitative deteniiination
o water is carpied out by Karl Fischer titration. An autanated coulometric Karl Fischer
titration has been described (ref. 't9) that has a limit of detennination of 5 ppm. Some
corrmercial instruments have by nci an even better performance.

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