ELECTRODEPOSITION OF ALKALI METALS FROM

NON-AQUEOUS SOLVENTS IN A HORIZONTAL

MERCURY CELL AT ROOM TEMPERATURE
AND LOWER
ROBERT POMPE
Department of Inorganic Chemistry, Chalmers University of Technology and University of G8teborg,
P.O. Box S-402, 20 Gateborg 5, Sweden

(Receioed injfinalfnrm 4 June 1976)

Abstract-Metallic sodium and potassium was obtained at high current efficiencies and low cell voltages
by electrolysing solutions of various salts in pyridine, acetone and dimethylformamide at low tempera-
tures in a mercury cell. The cathode compartment of the cell was separated from the anode compart-
ment bv a horizontallv nlaced amakamated mercury electrode. The influence of the different solvents
and salis as well as tlk ;emperature-is discussed.

INTRODUCIlON satisfactorily achieved and maintained. The cell which

The possibility of obtaining-deposits of active metals has been found most suitable for this purpose pro-
such as Li, Na or K by electrolysing solutions of their duces continuously alkali metal amalgam which
salts in non-aqueous solvents, ie systems where the serves as an anode and has an inert electrode as a
molecules of solvent are more stable against cathodic cathode. As follows from Fig. 1 the cell is separated
reduction, was studied already in 1895 by Laszc- by the mercury electrode in two parts that can be
zynski[l] and later by Laszczynski and Gorski[2]. denoted the cathode and the anode compartment_
They reported deposition of Li from the solution of In the anode compartment, a concentrated solution
LiCl in acetone and K from KSCN in acetone and of KCI or NaCl in water was used as the anolyte
in pyridine. The results of their work, however, were and a graphite electrode served as the anode while
partly challenged by Levi and Voghera[3] who found the amalgam was made cathode in this compartment.
some of the deposits to be compounds of the metal The cathode compartment consisted of a crucible
and the solvent. Deposition of Na, K and Li from containing a porous plate. This supported the amal-
pyridine and acetone and Li from a number of other gam which rested on a layer of a fine-grained moist
organic solvents was also investigated by Patten and
Mott[4] and a number of other authors[>9]. The
field of non-aqueous deposition was critically
reviewed by Brenner[lO]. It was found that Na, K
and particularly Li could be efficiently deposited from
a number of salts in non-aqueous liquids such as
ethylene diamine, alkylamines, liquid ammonia and
others. On the other hand, only Li seems to be de-
positable in pyridine and acetone. In the experiments
where some detectable deposit of K or Na was
obtained, the cell voltages often exceeded 1OOV sug-
gesting that the operating conditions of the cells used
were not under control.
The chief purpose of the present work is to deter-
mine the character of the cathode deposits as well
as the cell voltage and current efficiency of the cells
as a function of the different solvents and salts used
when the operating conditions ie the concentration
and composition of electrolyte as well as the tempera-
ture remain essentially unchanged during the electro-
lysis.
The electrolytes investigated are the solutions of
sodium and potassium salts in acetone, pyridine and
dimethylformamide.
I-_ --I
APPARATUS Fig. 1. 1. cathode; 2. glass tube; 3. catholyte; 4. mercury
electrode; 5. layer of wet salt; 6. diaphragm; 7. anolyte;
The electrolysis cell had to be designed in a way 8. anode; 9. movable wire cathode; 10. movable glass tube;
such that the stable conditions of operation could be 11. graphite anode; 12. sulphuric acid solution.
1111
E.*. x,12--*
1112 ROBERT POMPE

A/dm’. The temperature in the catholyte, referred

n 7-1 to as room temperature, was 22 f 2°C. In the low
temperature experiments the temperature was varied
within the range 5” to -20°C. The duration of the
electrolyses was not permitted for the most part to
exceed 30min in order to avoid absorption of mois-
1 ture in the solutions. In each experiment, the electro-

1
lysis was terminated by raising the cathode from the
electrolyte and immersing it for CQ 3 s in 50ml of
2
0.001 M solution of H,SO,, its concentration being
low enough that the iron cathode would not dissolve.
The solution was then titrated with 0.005 M NaOH
to determine the current efficiency.

Chemicals
The non-aqueous solvents were used as received
and their quality and particularly their water content
were as follows: Acetone p.a. Merck, 0.2% H,O;
Dimethylformamide p.a. Mallinckrodt, O.lo”/, H20;
Pyridine (dried) p.a. Merck, 0.01% H20. The salts
used in preparation of the non-aqueous solutions
Fig. 2. 1. thermometer; 2. cooling gas outlet; 3. cooling were selected according to their general solubility in
gas inlet; 4. Dewar flask; 5. dry ice. the organic solvents. Perchlorates, rhodanides,
cyanides, nitrates and halides except of fluorides of
salt (NaCl or KCl) to insure a high concentration potassium and sodium were found to be the most
of salt in the region of contact between the mercury suitable for these purposes.
and the anolyte. The catholyte consisted of a solution All of them were of pro-analysi quality except for
of alkali metal salt in a non-aqueous solvent and an KClO,. The rhodanides were dried for about 2 h at
iron plate was employed as the cathode. In order to 120°C and stored in a dessicator containing silica gel.
prevent the catholyte from being polluted by the ano-
lyte, the alkali metal deposition occurred in a glass RIBULTS AND DISCUSSION
tube of a somewhat smaller diameter. The values df voltage and current efficiency which
An electrolytic potentiometer, represented in Fig. were characteristic of the runs in acetone, pyridine
1, was filled with 0.1 M H,SO, and the resistance and dimethylformamide are summarized in the Tables
varied by moving the connecting wire up and down l-3. The observations made during the electrolyses
within the glass tube. are presented below with respect to the different sol-
The cooling device employed in the low tempera- vents and salts used.
ture experiments was, in principle, composed of a
Dewar flask filled with dry ice. As indicated in Fig. Ace tone
2, the stream of air was first allowed to flow through At room temperature the sodium metal which de-
a spiral tube within the flask and the mixture of posited reacted strongly with this solvent accom-
cooled air and CO, was then passed through the panied by gas evolution. The reaction product
space between the crucible and the tube containing appeared on the cathode and dissolved gradually. In
the catholyte. The cooling system thus allowed the
temperature to be regulated within the cathode com-
partment by increasing or lowering the flow of air Table 1. Values of voltage and current efficiency obtained
through the flask. A selenium Tudor rectifier was used in electrolyses of Na- and K-salts in acetone at room tem-
as a power source and the measurements of voltage perature (22 + 2°C) and lower (0” to - 10°C)
and electric current were made with a general instru-
ment Normameter E. Room temperature Decread temp.
Voltage Curr. eff. Voltage Curr. eff.
0 (%) (VI (%)
EXPERIMENTAL
Na 1G20 2&&l 54 85-95
Perjinmance of the measurements K 1CKXJ 40-80
The operation of the cell was begun by electrolys-
ing the anolyte ie the aqueous solution of the salt Table 2. Values of voltage and current efficiency obtained
(KC1 or NaCl) until the alkali metal concentration in electrolyses of Na- and K-salts in pytidine at room tem-
in the mercury reached roughly 1 weight ‘/& Approxi- perature (22 f 2°C) and lower (5” to -YC)
mately 1 ml of the non-aqueous solution was trans-
ferred to the glass tube in the cathode compartment Room temperature Decreased temp.
(Fig. 1) and the iron cathode, loosely held in a rubber Voltage Curr. eff. Voltage Curr. EST
lid, was fitted into the tube, so that the distance (VI (%I (v) (%I
between its lower part and the mercury was 1 mm.
Na X-10 97-100 4.56.5 95-100
The electric current during the operations was K l&15 100 6-10 9248
3-10 mA producing a current density of CQ 0.5-1.0
 Electrodeposition
Table 3. Values of voltage and current efficiency obtained
in electrolyses of Na- and K-salts in dimethylfor-ide at
room temperature (22 f 2°C) and lower (5” to -3°C for
Na and 0” to -10°C for K)
Decreased temp.
Room temperature
Voltage Curr. eff. Voltage Curr. eff.
w-
WI- (%) (%I
Na 12-15 95-100 4-5 95-100
K 12-m 9%loo* 15-25 85-95
* 4&60 for KC103 and KSCN.
the case of potassium the metal reacted so fiercely
that no deposits were obtained. The catholyte even-
tually attained the yellow-red colour typical of the
reaction product between potassium and acetone.
At low temperatures (0” to - lO*C) the deposits
of Na appeared metallic. At 0°C these deposits
reacted slightly with acetone while at - 10°C no reac-
tion could be observed. The potassium deposited
seemed to react considerably even at -10°C. The
product on the cathode appeared non-metallic in KI
and KClO+ solutions. In KSCN solution the deposit
was of metallic appearance and seemed to react less
vigorously at -10°C. The metallic deposits reacted
violently when the cathode was immersed in the
0.001 M H,SO,.
Pyridine
Metallic deposits of both K and Na were obtained
at room temperature. In the solutions of NaNO,,
NaC104 and NaSCN these deposits seemed to react
slightly with the solvent. The dark-green reaction
product was reminiscent of that obtained by treating
Na with the pure solvent.
In low temperature electrolyses (5” to -5°C) only
the rhodanides and NaClO, were sufficiently soluble.
The deposits obtained were also of metallic character.
In the solution of rhodanides, Na and, unexpectedly,
even K metal appeared to react markedly with the
solvent. In both cases a dark-green product was
formed. The metallic deposits as well as this reaction
product reacted rapidly with 0.001 M H2S04 and dis-
solved.
Dimethylformamide
The deposits of Na and K at room temperature
were initially of metallic character in all salt solutions
used. In the course of the electrolyses, however, the
deposited Na seemed to react slightly and K more
vigorously with the solvent in the solutions of rho-
danides, cyanides, perchlorates and KI. A whitish
reaction product was formed.
At low temperatures (5” to -3°C for Na and 0°C
to - 10°C for K) metallic deposits of Na were
obtained except for the NaCN solution. No reaction
with the solvent could be noted. The deposits of K
appeared metallic only in the case of KNO,, KBr
and KCl. In KClO,, KSCN and KI a whitish well-
adhering deposit appeared gradually on the cathode.
The metallic deposits reacted violently with 0.001 M
HzS04. A fairly vigorous reaction was also observed
between the whitish deposits and the acid, suggesting
that some free metal was present.
of alkali metals 1113
Comparison of the above observations and the data
in Tables l-3 shows that the outcome of the electro-
lyses is primarily dependent on the rate of reaction
between the metal deposited and the solvent, and on
the properties of the reaction products formed.
At room temperature, metallic deposits are gener-
ally obtained in pyridine and dimethylformamide at
high current efficiencies. The cell voltages are rather
high because insulating films are formed on the cath-
ode as a result of slow reaction of the alkali metals.
In acetone, the deposited alkali metals react rapidly
with the solvent. The reaction is followed by a gra-
dual increase in the cell voltage and low values of
current efficiency are obtained. When the catholyte
temperature is decreased the reaction between the
metals and the solvents is drastically suppressed
except in the case of pyridine. The alkali metals are
then in the most of cases deposited at current efficien-
cies close to one hundred percent and at low cell
voltages.
From a consideration of the results obtained the
following features of the electrolyses also should be
mentioned.
(a) Cathode deposits. The character of cathode
deposits appears to be a function of the type of salt
used in the electrolysis. In dimethylformamide, and
to some extent in pyridine and acetone also, the elec-
trolysis of solutions of more “salt-like” compounds
such as chlorides, bromides or nitrates always
resulted in deposition of metal while electrolysing
solutions of rhodanides, iodides and even compounds
as ionic as perchlorates often led to notable gas evolu-
tion at the cathode and ill-defined deposits.
The differing behaviour of these two groups of salts
may be attributed to the particular tendency of the
latter ones to form addition compounds with the sol-
vent molecules such as those described in the refer-
ence literature on solubility[ 111. Lowering the tem-
perature may in general have promoted association,
but the simultaneous decrease in solubility, on the
other hand, may be assumed to act in the opposite
direction ie, in favour of dissociation of these com-
pounds thereby improving conditions for obtaining
the metallic deposits.
(b) Cell voltage. The value at which the potential
across the cell finally stabilized appeared to be depen-
dent on the properties of reaction products formed
on the cathode. As both metals, except K in pyridine,
tended to react with the solvents at room tempera-
ture, a very thin, often invisible film of reaction prod-
uct was formed on the cathode after a very short
time, making the electric current fall. It was necessary
to gradually increase the voltage to maintain the cur-
rent at a fixed value. At room temperature, this was
most evident in the case of dimethylformamide where
the thin layer of initially formed reaction product
caused large polarization effects, although it adhered
poorly and was often of a loose nature in the bulk.
The conductivity of a number of non-aqueous solu-
tion&was found[2] to exhibit a maximum at low salt
concentrations, hence some experiments were also
carried out in diluted solutions, especially in cases
where the saturated solutions were particularly vis-
cous. Out of eight quantitative measurements that
were performed on salts in dimethylformamide and
pyridine, only the electrolysis of diluted solutions of
1114 ROFIERTPOMPE

NaSCN in pyridine resulted in some measurable lity of the deposits obtained from these salts it may
effect. The voltage on the cell decreased but, on the be assumed that association in the electrolytes is con-
other hand, a previously unobserved gas evolution siderably stronger for potassium, with the result that
began at the cathode while the deposited metal the electric current is consumed mostly in decompos-
seemed to react with the electrolyte. Since in the qua- ing the catholyte rather than in depositing the metaL
litative experiments conducted with diluted solutions In the experiments conducted with diluted solutions
the reactivity of the deposits also appeared to be pro- where the electrolyte was particularly viscous, there
moted, the subject was not investigated more exten- was a slight increase of current efficiency only in the
sively. electrolysis of the sodium salts in dimethylformamide.
(c) Current efficiency. One of the principal aims of
the experiments was to determine the current effi-
ciency as the fraction of the electricity transported REFERENCES
between the electrodes in the cathode compartment
and resulting in deposition of metal on the cathode. 1. S. V. Laszczvnslci. 2. Electrochem. 2. 55 (lg951.
It proved, therefore especially valuable that the titra- 2. S. V. Las&ynski and S. V. Gor& Z.‘Elec’wochem.
tion method also permitted determination of the 43 290 (1897).
3. M G. Levi and M. Voghera, Garz. Chim Ital. 35, 277
eventual reaction products as these readily dissolved
(1905).
in 0.001 M H,SO, and were titratable with a solution 4. H. E. Patten and W. R. Mott, Electrochem. Ind. 1,
of hydroxide. On the other hand, this implied that 417 (1903).
a considerably lower current efficiency would be 5. R. Miiller et al, Sitrungsberichte, Abt. II.b, 131 Bd, 6
found when the deposited metals formed reaction HeR, 371, 289 (1922).
products which dissolved in the solvents (acetone) or 6. H. C. Mandell et al, J. Electrochem. Sac. 102, 269
adhered poorly on the cathode. The efficiency could (1955).
also be decreased when the decomposition of electro- 7. A. Siemens, Z. anorg. alIgem. Chemie 4&42, 27&272
lyzable solvents (acetone, dimethylformamide ) was (1904).
favored by diluting the solutions or because of the 8. G. L. Putham and K. A. Kobe. Trans. electrochem.
sot. 74, 15 pp. (1938).
low solubility of certain salts (eg NaCl in dimethylfor-
9. L. J. Mimmick and C. Presgrave, E.P. 642 034 (Aug.
mamide or NaNO, in acetone).
23, 1950).
In experiments where the perchlorate, rhodanide or IO. A. Bremer, Adv. Electrochem. electrochem. Engng. 5,
iodide of potassium was electrolysed, the current effi- 205-248 (1967).
ciency was markedly lower in comparison to the 11. W. F. Linke, S&hilities of Inorganic and metal-organic
other groups of salts and to the sodium salts of these Compwnds, 4th edn. Am. Chem. Sot Washington
anions. Considering simultaneously the inferior qua- (1958).