A TEXT BOOK OF QUANTITATIVE INORGANIC ANALYSIS INCLUDING ELEMENTARY INSTRUMENTAL

ANALYSIS
ARTHUR I. VOGEL, D.Sc. (LOND), D.I.C., F.R.I.C.
1961 , THIRD EDITION
LONGMANS, GREEN AND CO LTD
LONDON
PAGE 564-566

LITHIUM

Discussion, Lithium, if present as a salt of a volatile acid, may be determined as lithium sulphate,
Li2SO4, by repeated evaporation with sulphuric acid and subsequent heating at 600-700 ⁰C. No other
elements may be present. Here the change from the acid sulphate to the normal sulphate takes
place comparatively easily, so that the addition of ammonium carbonate is not essential.
When the present with sodium and potassium as chlorides, the lithium may be determined :
a) By the n-butyl alcohol-ethyl acetate method
b) By extraction of the lithium chloride with dry isoamyl alcohol or dioxan (diethylene
dioxide) or an anhydrous acetone, sodium and potassium chlorides being sparingly
soluble in these solvents. The best results are obtained with 2-ethylhexanol, although
those with n-hexyl alcohol are usually quite satisfactory. The solubilities of the chlorides
in anhydrous isoamyl, n-hexyl alcohol, and in 2-ethylhexanol (iso-octyl alcohol),
expressed in grams dissolved by 100 ml. of the anhydrous solvent at 25⁰ C., are-

isoAmyl Alcohol n-Hexanol 2-Ethylhexanol

LiCl 7.3 5.8 3.0

NaCl 0.0016 0.0008 0.0001

KCl 0.0006 0.00004 <0.00001

The methods utilising dioxan and 2-etylhexanol, ilustrating two different techniques, will be
described.
Lithium may also determined as lithium aluminate by precipitation with excess of sodium
aluminate solution in the cold, the final pH of the solution being adjusted to 12.6-13.0. the
precipitate has the composition LiH(AlO2)2,5H2O; it is washed with water until free from alkali and
weighed as 2Li2O,5Al2O3 after heating at 500-550⁰ C. The solubility in water in 0.008 g. per litre at
room temperature; it is 0.09 g. per litre at pH 12.6.

Determination of lithium in the presence of sodium and potassium.

Procedure A. Dioxan method. Heat the mixed chlorides at 120⁰ C in a weighed sinterred glass
filtering crucible for 2 hours, and weigh after cooling in a desiccator. Suspend the crucible by means
of platinum wires about 1 cm above 20-30 ml of pure dry dioxan contained in a wide-monthed
250ml flask, which is attached to a reflux condenser having a calcium choride guard tube at the top.
Reflux for at least 4 hours, remove the crucible, heat at 120⁰ C for 1 hour, cool, and weigh. Repeat
the process until the weight is constant. The loss in weight is due to the lithium chloride.
Procedure B. 2-Ethylhexanol method. Treat a concentrated solution prepared from 0.3-0.4 g or
less of the mixed chlorides, accurately weighed, with a suitable volume of 2-ethylhexanol, introduce
a little platinum foil or a few fragments of porous porcelain to prevent bumping, and distil until the
water has passed over and the boiling point becomes constant (175-180⁰C) for same time. Sodium
and potassium chlorides are deposited, and lithium chlorides is dehydrated and held in solution.
Allow to cool, filter through a sintered glass filtering crucible, and wash thotoughly with successive
small volumes of the anhydrous alcohol. Dry the crucible at 200-210 ⁰ C to volatilise the residual
solvent, and weigh. The loss in weight is due to the lithium chloride.
If the weight of the lithium chloride exceeds 20mg, a second extraction is nesessary in a order to
remove the small quantity of lithium hydroxide present in a residual solid (formed by hydrolysis at
the boiling point of the 2-etylhexanol): the solid must be dissolved in a little water containing a few
drops of hydrochloric acid.
Determination of lithium as lithium aluminate. Procedure. The sample solution (20 ml) may
contain up to 10 mg of lithium, and the pH should be about 3.0. Add of the cold reagent (1) for each
10 mg of lithium. Adjust the pH to 12.6 by the addition of 1 N-sodium hydroxide solution: use a pH
meter. Allow to stand for 30 minutes, and collect the voluminous precipitate in a porcelain filtering
crucible. Wash with small volumes of ice-cold water until the washings are no longer alkaline to
phenolphtalein. Ignite at 500-550⁰ C, in an electric muffle furnace. Weigh as 2Li 2O,5AlO3.
Note 1. Prepare the precipitating reagent by dissolving 5.0 g of A.R potassium aluminium sulphate
(potash alum) in 90 ml of warm watercool and add dropwise with stripping-while cooling in ice, a
solution of 2.0 g of sodium hidroxide in 5.0 ml of water unit the initially formed precipitate
redissolves. after standing for 12 hours. filter adjust the pH to 12.6 and dilute to 100 ml with water.