Downs Cell

Downs cell
Downs' process is an electrochemical method for the commercial preparation of metallic

sodium, in which molten NaCl is electrolyzed in a special apparatus called the Downs cell.
The Downs cell was invented in 1923 (patented: 1924) by the American chemist James Cloyd
Downs (1885–1957).[1][2]
Diagram of a downs cell electrolyzing

molten NaCl into chlorine gas and
sodium metal
Operation
The Downs cell uses a carbon anode and an iron cathode. The electrolyte is sodium chloride
that has been heated to the liquid state. Although solid sodium chloride is a poor conductor
of electricity, when molten the sodium and chloride ions are mobilized, which become charge
carriers and allow conduction of electric current.
Some calcium chloride and/or chlorides of barium (BaCl2) and strontium (SrCl2), and, in some
processes, sodium fluoride (NaF)[3] are added to the electrolyte to reduce the temperature
required to keep the electrolyte liquid. Sodium chloride (NaCl) melts at 801 °C (1074 Kelvin),
but a salt mixture can be kept liquid at a temperature as low as 600 °C at the mixture
containing, by weight: 33.2% NaCl and 66.8% CaCl2. If pure sodium chloride is used, a
metallic sodium emulsion is formed in the molten NaCl which is impossible to separate.
Therefore, one option is to have a NaCl (42%) and CaCl2 (58%) mixture.
The anode reaction is:
2Cl− → Cl2 (g) + 2e−

The cathode reaction is:
2Na+ + 2e− → 2Na (l)

for an overall reaction of
2Na+ + 2Cl− → 2Na (l) + Cl2 (g)

The calcium does not enter into the reaction because its reduction potential of -2.87 volts is
lower than that of sodium, which is -2.38 volts. Hence the sodium ions are reduced to
metallic form in preference to those of calcium.[4] If the electrolyte contained only calcium
ions and no sodium, calcium metal would be produced as the cathode product (which indeed
is how metallic calcium is produced).
Both the products of the electrolysis, sodium metal and chlorine gas, are less dense than the
electrolyte and therefore float to the surface. Perforated iron baffles are arranged in the cell to
direct the products into separate chambers without their ever coming into contact with each
other.[5]
Although theory predicts that a potential of a little over 4.07 volts should be sufficient to
cause the reaction to go forward, in practice potentials of up to 8 volts are used. This is done
in order to achieve useful current densities in the electrolyte despite its inherent electrical
resistance. The overvoltage and consequent resistive heating contributes to the heat required
to keep the electrolyte in a liquid state.
The Downs' process also produces chlorine as a byproduct, although chlorine produced this
way accounts for only a small fraction of chlorine produced industrially by other methods.[5]
References
1. Downs, James Hamzs "Electrolytic

process and cell," (http://pdfpiw.uspto.go
v/.piw?Docid=01501756) Archived (http
s://web.archive.org/web/2018072518395
4/http://pdfpiw.uspto.gov/.piw?Docid=01
501756) 2018-07-25 at the Wayback
Machine U.S. Patent no. 1,501,756 (filed:
1922 August 18 ; issued: 1924 July 15).
2. Hardie, D. W. F. (1959). Electrolytic

Manufacture of Chemicals from Salt.
Oxford, England: Oxford University Press.
pp. 14, 65.
3. Keppler, Stephen John; Messing, Thomas

A.; Proulx, Kevin Bernard; Jain, Davendra
Kumar (2001-05-18). "Molten salt
electrolysis of alkali metals, U.S. Patent
6669836" (http://pathhft.uspto.gov/netac
gi/nph-Parser?Sect1=PTO1&Sect2=HITOF
F&d=PALL&p=1&u=%2Fnetahtml%2FPT
O%2Fsrchnum.htm&r=1&f=G&l=50&s1=66
69836.PN.&OS=PN/6669836&RS=PN/666
9836) . Retrieved 2010-07-17.
4. "Sodium Production by Electrowinning" (ht

tp://www.corrosion-doctors.org/Electrowi
nning/Sodium.htm) . corrosion-
doctors.org. Retrieved 2007-12-20.
5. Pauling, Linus, General Chemistry, 1970

ed. Dover Publications, pp 539-540
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Downs' process is an electrochemical method for the commercial preparation of metallic

Diagram of a downs cell electrolyzing

The anode reaction is:

2Cl− → Cl2 (g) + 2e−

2Na+ + 2e− → 2Na (l)

2Na+ + 2Cl− → 2Na (l) + Cl2 (g)

1. Downs, James Hamzs "Electrolytic

2. Hardie, D. W. F. (1959). Electrolytic

3. Keppler, Stephen John; Messing, Thomas

4. "Sodium Production by Electrowinning" (ht

5. Pauling, Linus, General Chemistry, 1970

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