CHEMICAL PROPERTIES OF HYDROGEN

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000100240001-4
• Release Decision: RIPPUB
• Original Classification: K
• Document Page Count: 120
• Document Creation Date: December 22, 2016
• Document Release Date: March 20, 2012
• Sequence Number: 1
• Content Type: MISC

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Chemical Properties of ;Hydrogen
At room temperature hydrogen `diuplays'little activity`
if it is in the molecular state; but in the nascent state its ac~
tivity is considerably increased.
At h~:gh,temperatures. the activity of molecular hydrogen in-
creases,- Hydrogen has the property off' being absorbed by metals?
The amount of hydrogen absorbed depends to a large extent upon the
specific surface of the metal. The largest amount of hydrogen is
berg absorbed by palladium which not only adsorbs but also dis?
solves hydragen~ The solubility of hydrogen is connected with
its property of permeating through red hot irony platinum and
even mare readily through palladium, which it permeates readily
even at 210 degrees. Hydrogen permeates through rubber but ,nat.
through glasso
Hydrogen combines. very: readily wa.th metalloids. Tt comp
banes most readily with fluorine, Even liquid hydrogen and solid
fluorine eombane explasiv~ly, Wath chlorine the reaction takes
place explosively only under the action of light of'short'wave
length or at a high temperature,
A mixture of two volumes of hydrogen .and, one volume of
oxygen is known as detonating gas. The reaction begins to an
appreciable extent at 180 degrees and is rapidly accelerated on
further heating,.. The. reaction velocity.can be greatly influenced
by the catalytic action of the containier material and the amount
o~ water vapor present in the gases. Under the acta.on of a flame'.
Spark or high temperature, detonating gas explodes; however, dry
37
~,~~.
~~s:~~~:
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increase even up to 150 atmospheres does not cause explosion, but
the presence of a catalyst, far example platinum black, may be the
cause of an explasion. Other catalysts promote explosion anl~ on
detonating gas. does not exp~.ode even at 960 degrees. Slotir pressure
heatingo
Corz'esponds to a content (by volume} of 5 percent H2 and 9~ percent
Mixtures at other proportions are a1.so explosion hazards..
~Che lower limit of explosibility of ahydrogen-oxygen mixture
The upper limit corresponds to 9l~.3 percent H~ and ~.'~ percent
Mixtures of hydrogen with air also constitute explosion hazards.
The lower 1~.mit of explosibility corresponds 'to the proportions of
5 percent H2 and 9a percent air, the upper limit to ?3.a~ percent
H2 and 26,E percent air.
Hydrogen can combine with various organic substances in the
presence of catalysts -a nickel, platinum, palladium, In this
manner liquid vegetable oils can be converted into solids. This
process is called hydrogenation. On reactions wherein hydrogen
combines with carbon monoxide are based the production of methyl
alcohol (methanol} and of liquid fuel.
2, processes Taking Place at the Electrodes in Electrolysis
..d.,..Y._......_...~~.4..~.._...,~ ....,......~,....~.....~._...~.
of Water
Pure distilled water has,an electroconductivity of from
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t convenient for use in electrolysis. But water, acidi -
water is no
' d' solved salts or hydroxides of alkali met~.l.s,
fled or contaa.n~.ng a.
? f electrical currents and when insoluble elec-
~.s a good conductor o
for exam le electrodes made of platinum, there is
trodes are used, p
a decom osition o~ the waterwith evolution of oxygen on.
observed P
the anode and of hydrogen on the cathode.
On .electrolysis of water,.. ac~,.dified, for instance w~.th sul-
ution of h drogen on the cathode is the result of
fur~.c acid, evol y
a~ rocess that is, of direct discharge of hydrogen ions
a prym ry p ~
in accordance. with .the reaction;
insofar as no other positive ions are present ~.n the solution?
volution of oxygen on the anode can be the result of two
E
el . r~imary discharge of 504" ions according to
processes, nam y. p
and a secondary reaction of the S0~ radical with water,~to give
oxygen and sulfuric acid:
SO + H~0 ~ H2S0~ ~' 1 0
4 ~ 2
On it can be the result of a primary discharge of hydroxyl ions
wa,th formation of water and evolution of oxygen, according to the
reaction:
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with water to give .caustic soda and hydrogen, in accordance with the
discharge of the Na+ ion and the reaction of the neutral sodium ion
for examplei caustic soda, on the other hand, evolution of hydro-
gen at the cathode could be, in principle, the effect either of a
On electrolysis of water containing in solution an alkali,
e~uat~.anS ;
NaOH ~ 1 H
or of pra.mary discharge of hydrogen ions formed. on dissociation of
Anodic evolution of oxygen from an alkaline electrolyte is
only possible as a result of the primary process of discharge of
OH'? ions, since in the alkaline solution there are absent any other
~reva.ously it was believed that in electrolysis of an
alkaline electrolyte the cathoda.c evolution of hydrogen is a
secondary process, that is, primarily the Na+ ion. is dischargedm
However this does not correspond to actual facts, and cannot be
attained if the electrolysis of water is conducted in accordance
with the practice of using as a cathode not mercury but a solid
metal,
Hydrogen is generated at the cathode, from an acidic as
well as from an alkaline solution, as a_result of a primary processr
the equation of Nernst 'to effect
f rare
xn order
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to male possible separatian from the neutral solution of ions of
Na+9 the normal potential of which zs equal to -2'71 volts, it is
necessary that the more electronegative potential of Na+ ions.
separation approximates the value of the potential of H~ ions
separation. Theoretically this can be attained if the concen-
tration of sodium ions in the solution is increased to such an
extent that the value of the potential of Na? ions separation is
equal, to W0.~.1,~ volts, Qn using x to denote the concentration
of Nay ions in the equation of Nernst we have
wherefram
-O.l~.l~ = -2071 * 0,08 lg x
The figure thus obtained indicates a fatally unreal cone
centration. Even on taking into account that evolution of hydro-
gen from the. alkaline solution occurs at a more negative potential
and in addition that a certain overvoltage exists, still computa-
tion shows that in such a ,.case separation of sodium does not take
place, and only discharge of hydrogen ions occurs.
Anodic evolution of oxygen from an acid solution was also
considered as being a secondary process. However, this assumption
also apparently does not`correspard to the actual facts, In spite.
of the law concentration of DH" ions in acid solution, under cans
ditions of not too high a current density, OH` ions are discharged
first. This follows from measurements of decomposition voltages
of various acids and bases. It was found that decomposition volt-
age of normal soluti.ans `of various acids and bases on smooth
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odes has a value of about 1.7 volts.
platinum electr
nts are given in Table 21.
Results of the measureme
Table 21
s of acids and bases on smooth
m osition voltage of normal solution
Deco p
platirnam electrodes
lts
on vo
'
Substance in soluta~ ~~
14h7 Caustic potash
Sulfuric acid 1.?~
1.69 ,Ammon~.um hydroxide
id
Nitric ac
Phosphoric acid
Dichloro-~acetic
Decomposition
voltage;
Substance in solution
1.70 Methylammonium hydroxide
0 12~N) 1.? ~
acid 1,66 ( .
Malonic acid
1.69
Chloric acid
1.6~
Tartaric acid
1.62
Caust~.c soda
1469
Dimethylammonium
0 ~N) 1.68
hydroxide ( ?
Tetramethylammoniwn
h droxide (0?~-2~Nj 1.71
y
decom osit~-on voltages of acids and.
Close coincidence of p he
' t does not depend on the .nature of t
bases, and the fact that ~.
to belief that in all instances the same
acrd and base9 lead ne would expect
ace on the electrodes. Otherwise o
process takes pl
e of the .acid, or base, would depend upon
that decomposition voltag
'on o r base cation.. The.only process on
the nature of the acid.ani
n to~the different acids and .bases is
the anode which can be commo
ions with ~epa,ration of oxygen.
the discharge. of OH
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Decomposition voltage of normal solutions of hydrogen halide
acids was found to be less than 1.7 volts, namely: hydrochloric
acid 1.31 volts; hydrobromic acid 0,91 volts; hydriodic acid 0.~2
volts?
However in this instance there is liberated on the anode
not oxygen but halogeno Hence decomposition of water does not
take placer if electrolysis is conducted using hydrochloric ,acid
diluted to a concentration of if 32 N, the decomposition potential
increases to 1,h9 volts and evolution of oxygen begins at the anode,
1t is apparent that the potential of Cl? ion discharge in a
normal solution of hydrochloric acid is lower than that of OH" ian
d~.scharge; because of this, electrolysis of water does not take
places In more dilute solutions of-hydroch:loric acid reverse cor-~
relation of discharge potentials, of ions OH'? and C1", obtains,
The chlorine ion is discharged at a higher potential, and de-
composition voltage of the dilute acid, to give chlorine end
hydrogen, should be higher than 1,6q volts; hence, as soon as the
voltage reaches this value there occurs evolution of oxygen an
the anodes
Thus on electrolysis of acidic, or alkaline, electrolyte
with platinum electrodes at not toa high current density; evop
lution of hydrogen on the cathode and of oxygen on the anode
constitute primary processes.
Electrolysis of water takes place according to the
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From this it is readily apparent that while two moles of
water are being decomposed, on the anode there takes place simulw
taneously the formation of one mole of water. As a res~rlt of this,
on prolonged electrolysis the electrolyte in the vicinity of the
anode is depleted of acid or alkali, while near the cathode the
amount of acid or alkali increases. Tn an alkaline solution de-
crease of alkali near the anode also promotes current transfer
by alkali metal cations from anode to cathode. Due to difference
in concentrations there arises concentration polarizati.an, which
could be of considerable magnitude at large differences of cony
centration. However the diffusion process has the opposite
effect -a that of equalizing the concentrations. Therefore a
stable condition is reached after which the difference in con-
centrations does not increase.
According to Faraday's law 2C~o8 ampere hours liberate at
0 degree and ?60 millimeters pressure, 11.2 liters af' hydrogen
and 5.6 liters of oxygen. Qne cubic meter of hydrogen and 0,5
cubic meters of oxygen require, in theory, the expenditure of
2383,8 ampere hours,
3. Theoretical Voltage. of Water Decomposit.~on
Tf electrolysis of water is conducted under reversible
conditions, then the work e~cpended must be numerically equal to
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the work performed'by the reversibly operating galvanic hydrogen-
o en cell, in .which the same reaction takes place in the opposite
xyg
direction.
Tf ~'1 is the. work expended on .decomposition of water,. and
A the works yielded by the galvanic cell, it follows that under
2
reversible conditions
wherein
ffi nF x E~ Q~)
n -number of reacting or obtained
chemical equivalents
F -Faraday's number
E~, -voltage of reversible decomposition
of water
E2 - electromotive force of reversib7~y
operating hydrogen-oxygen cell.,
nFxEl = nFxE
since nF in bath members of the equation relates 'to the same reactions
which merely .proceeds in opposite directions, we have br
E~ = E~ (o)
Therefore for a reversible decomposition of water there is required
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a voltage equal to the electromotive force of the reversibly operating
hydrogen-oxygen galvanic cell.
irreversible processes, for example overvoltage at the electro des
This is the least voltage determined solely by the decompo~
~itio n wark,. without taking into account any losses, that is,
From equations (3) and (1~) it follows that
n~'
the value of maximum work A cf the reaction
2H2 ~ 0~ ~ 2H2O
is given by the isotherm equation
wherein
OH2' 002' OH O p the initial concentrations of the reactin h dro en
2 g y g
On substituting in equation (~7) the value of A from equation (8) we
since
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- are the equilibrium concentrations
en and o en, We can write equation (q) in the
of water, hydrag ~'g
following farms
F ~
n
CL H x C x CH U ~~).
1
,42 2
~ 2
Bearin in mind that the volumes at which the reaction takes place
g
'n such a manner that C , H2O ~ cH2O, that
can always be selected i 1
entration of the water .found is equal to the equ:ilibri.um
~s, the conc
value, we have
Replacing molar concentrations by partial pressures which are
tional to them introducing the numerical values of R, F and
propor s
~.,, ; and con~rerting to decimal logarithms, we have
If the process takes place; at atmospheric pressure, that is~
if the partial. pressures of hydrogen and oxygen PH~
mosphere, equation (l3) assumes the form
either on the basis of
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on the basis of values of partial equilibrium pressures..
equation (7)~
of hydro den .and oxygen.
partial equilibrium pressures can be compul~ed from values
of degree of dissociation of water vapor,
moles of oxygen. Tn total
foaled ~ -moles of hydrogen and ~ _~
f the degree. of dissociation of water is q(,, then for each.
x
here remains ld t1~ moles of undi.ssacia,ted wa~~er, there are
mole t
we have 1 ~ ~ molesp .
2
' e ratio of artia.l pressures of gases to .the total
S~.nce th p
' he same as the ratio of their molar concentrations to
pressure x.s t
the total molar concentration, we have
pl s D 2 ~ ~ 0~-
,~.,,, ~ and P ~" 2 (1 ~ -.~-~
1 + ~,,
2
where F is the total pressure of the mixture at equilibrium.
t low tem eratures the degree of dissociation of water is
A p
o.
mall therefore. the value
Very s 9
~i
can be disregaz?ded9 and then
ire have
2
Let us calculate the theoretical voltage of water decompos~.tion for
~~ ' ons in racta.ce, that is at 80 ..`degrees (T ~ 3~3
orda.nax,~ cond~ta~ A .
degrees) and pressure of one atmosphere?
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Dependence of true heat capacities on the temperature;.
cp, x2 ~ b. ~o + o ?ooa9 T
in the case of our reaction at a constant pressti~xe has the foam;
the values of the equilibrium constant, using an equation which
small. value, but for these conditions it can be calculated from
of water cannot be determined experimentally because of its very
Tl~e val~.e of the equilibrium constant at constant pressure
we can find by means of isochore equation of Van t~Hoff,
For this let us use the following experimental data;
thermal effect of the reaction
at 2~ degrees (T ~ 29~ degrees) and constant pressure Qp is equal
to 11,670 calorieso
OOlq T + 0.00000222 T2
Let us findthe general expression far Qp (T) as a function
of T from the equati?n;
b m 50 + o, oolo T
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is the algebraic sum of stoichiametric co-
efficients of our reaction, we have
2(6.,0 + 0.0009} + ~6.~ + a.ooloT} -~
.~ 8 - 0 00197 + 0.0000022272
2 ~ 8. l )
3
11~. 8~6 + 1,88 T ~ oaoo33 72 - 0.00000 11,.8 73
Substituting the value Qp(T} in equation X17) and integrating,
7 - 0.0000001618 T2 + c
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.-. 1,88 + 0moo667 ~ O.oooool~~4T2
Substituting into equation X18) values of Qp X298 degrees} and
~ Op, and integrating we have
"1'_
+ 1 88 + 0.0066 T - Oe000001~1~~72 ~'
~p(~) 11~=670 ?
~~~~
w 11,670 ~. 1.88 x 298 - 000066 2982 + 0.0~ 00001~11~. X 2983 +
2 3
~ 188 7 + 0.0066 72 _ 0,00000~.1~~ 73
~~
we obts.in
1nK ~ - lll~., S ~b + 1. 88 In T + 0.03 3 T - 0.00000071 T2
RT~ R R R
Substituting the values of R and converting to dec~.mal
logarithms, we have
lgK ~ - 11~ 8~6 + 1 88 lg ~~ .~ 0 7 - 0.0000007.
~ 37
1.956 4. ~7 3 l~. ~7 3
25116, ~. ~ o e 9166 x lg xi ~~ 0.0007 2a.6 7
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such use of the experimental data the mean.value;C = + 1.71.x. was
equation (19~ the experimentally determinedvalue of lg ~. B3''
The integration constant C can be formed by substituting in
found.
Using this value of C and substituting T ~ 353 degrees we
lgxs~6b,78o~
Let us now determine
3lg~,algK_lg~.*1g2
lg K ~ 25116,E ~ o.946b x lg 353. * 0,0007216 x 353
2
- 0,00oooolbl8 x 353 + 1071
In view of the small value of c~?at 80 degrees, we can take
as .the total pressure of the gaseous mixture the water vapor pressure
which at 8o degrees is equal to 0.l~.82 atmospheres.
3 lg at= ? bb,78o5 - i~b83o + 0.3010
3 lg ~~ - bb,1b25
lg cK.~ - 22.0511 ~ 23 ~ 9.59
~. ~ 8.828 x 10.23
wherefram
ffi p 7114 + 2mla.ll7 + 0?15.7 ?0.02093 ~ 1.71
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and finally
0.00005 x 353 lg
l
001.82 x 8.82 x 10-23j~a.5 x oAli.82 x 8.82 x l0?23)
( (
w 0.01765 lg 1 A [ 2(1g001~,82 + lg 8,82 x 10"23) +
~ (18005 + lg 001,82 + lg 8082 x 10?23) )~
0, 017 65 ~o. oo _ r 2 (~ 0 6830 + , 9459 } + Ci, 6990 + ~, 6830 +
+ 2309~.59)]~ ffi 0001765 (o.oU p 68.5857)
000176 x 670~.1~.3 ~ 1,18 volts0
Calculation of theoretical potential on electrolysis at normal
pressure (l atmosphere) can be simplit"aged ~.f there is known the
equilibrium constant far the required temperature.
Tn such case one may start directly from the isotherm
equation;
Far 80 degrees we have found the value lg K ~ - 66078050
phere .that was adapted. by us, ~to, the actual; pressure of 0.l~.82 at-
par~sian of water:. vapor from the conventional :pressure of l atmos-
of one atmosphere, while water vapor has a presence of only 00.$2
atmospheres0 Hence i~ is necessary ~o introduce into the obtained
value of maximum work a connection, that ie~ 'add the .work of ex-
But at 80 degrees only hydrogen and o~~ygen can have a pressure.
P
A ~ ~ 20303 x1,986 x 3~3(.~6607805) ~ 107,800 calaries0
Substituting the numerical values of R, T. and lgxp, we have the
maximum work of the reaction
mospheres~
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For two rr~oles of water this work is equal to
A~=2RTxln 1
....~...~=
wherefrom
Al
P ~ 10$,$75_ -- --- ~ 1Q1.8 volts
nF x 0.238
Maximum work Ap can be calculated also directly from equation
X20), since on the basis of equation X19)
~. ~~.14,8564Z~88Tx23031gT-0,0033 T2 +
p
~ 0~0000007~ T3 -2.303 C x RT
Taking the value C ~ 1~71~., we have for 80 degrees
Ap ~ 107,821 calories
Ap ~ 107,821 ~ 1075 ~ 108,8q~ calories
E-l.l8volts
5im~.lar computations for an electrolyte temperature of l7
degrees give a theoretical decomposition voltage of 1.23 volts,
The theoretical voltage thus decreases with increasing
temperature, and the temperature coefficient of electromotive.
force of hydrogen-oxygen circuit, within this temperature range
is equal to
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2x2~303x1?986x353x1n 1
0,1;.8 2 0.. 2
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When the temperature coefficient of the electromotive force
is known, the theoretical potential can be calculated on the basis.
of thermal effect values of the reaction, by using Gibbs-Helmholtz
equation
Balance of Cell Voltage
Tn practice, of course, electrolysis cannot b~ effected
in reverse since it is not possible to operate at vanishingly .small
c~~rrent densities so as to avoid paver losses by overcoming of a
number of harmful resistances, .like overvaltage of gases on electrodes
electrolyte resistance, diaphragm resistance, resistance of electrodes'
of contacts and the like. Hence the cell voltage always exceedsi
to a larger or smaller extent, the theoretical voltage.
~. the cell voltage V, that is, the difference of potentials
between the electrodes, is thus equal to the arithmetical sum. of
the voltage decrease within the individual areas of the cello
where- ~ a and E k are reversible potentials of anode and cathode
the sum of which is equal to the theoretical decomposition
voltage~a and ~k -- respectively, overvoltage of oxygen
on the anode and of hydrogen on the cathode4
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!~. Balance of Voltage
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- voltage loss in the ,electrolyte.
voltage loss in the diaphragm
voltage loss in conductors of the first kind -
in electrodes
voltage loss in contacts
concentration polarization
Depending upon operational conditions and design of
the cell, harmful resistances can be very substantial, as a result
of which, the actual cell voltage may exceed the theoretical lad
? 2 times, Most important are losses due to overcoming avervoltage
at the electrodes and resistance of the electrolyte?
Losses e3 and ?!~, if the cell is properly designed and ade.~
qua~tely maintained, can be very small, Just as small are the values
e2 and e5 which ordinarily have no substantial a ~'
pr c u~cal sxgnifi?
cancer
As is known avervaltage of gases is not a constant
quantity and depends upon many factors; current densit nature
y,
of the. electrode surfaces, temperature of the electrolyte material.
a
of the electrodes,, duration of electrolysis. In the last 20 .ear
y s
theoretical. electrochemistry,has attained signal successes in the
domain of the stud~r of gas overvoltages, nonetheless it has not
suaGeeded_fully to establish the theory of dependence, of over?
voltage am the above listed factr~rs, ~herofore in estimatin th
g e
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magnitudes of hydrogen and oxygen o uervoltage, it is necessary to
resort to experimental data, But experimental data also are of
overvoltage, because experimental conditions cannot be readily
--- - ---_
relative value and provide but an approximate estimai;e of the
duplicated,
densities and temperatures on different materials, in the electrolys3:s
of a 16 percent solution of .caustic soda, are shown in Tables 22 and
Values of hydrogen and oxygen overvoltage at various current'
23.
Table 22
Hydrogen overvoltage in a 16 percent solution of caustic
soda; in volts
Material
06 0.08 0,095 0.01 0,03 0,~~.5 0.055
containing O,ll 0.1.6 0..1.0 0.21, 0,02.. 0,06 0.0$ 0?~.0
Platinized platinum
Galvanic nickel, Sulfur
Iron, nickel coated 0.25 0.39 0.19 o.5d O.lb 0.2~. OQ26 0.30
Iran, .cobalt coated .? .. O,L~2 0,x.7 `..0.20. Oo30 0,36. 0.12
blasted Oo 21 Os31 0,36 0,~~0 o.ll 0,1.5 0.18 0.23 A
Nickel, rolled 0.37 a,1~7 0.51 0.55. 0.3 0.39. 0,13 O,1~7 ..
Iron, sand .blasted 0.26. 0,3~ 0,39 0.45 0.12 0.18 0,22 0.27 0/3~.~
Nickel steel, sand
at 18 degrees
at 8o degrees
loo 500 lo0a 20ao loa 5oa ~loo0 2000 3500
Current density amp,~m2
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Table 23
Oxygen overvoltage in a In percent solution of caustic.
----s o-da-;-~.~-wits--
Material
Galvanic nickel
Current density amp.~m2 Current density amp.~,~2
at 18 degrees at 80 degrees
100 X00 1000 2000 100 X00 1000 2000 3500
Nickel steep
d blasted 0.3~ 0?40 0,14 0?1~.$ Om25 0?275 OW29 031 0.3~
san
Nickel' rolled o~~~ 0.77 oo8z o.8~ 0.31 Oo36 0~~~0 0?~3
Iron, cobalt
coated oe31 0.35 0.37 ~.3~ 023 0.2~ 0.27 0.29 ?~
As can be seen from the table overvoltage of both gases, in
accordance with the general rule, increases with increasing current
.density, lnerease of temperature considerably decreases overvoltage.
The overvoltage is affected not only by the material of the eleco
trodes but also by the condition of their surface, On rough sur~
.faces, the overvoltage is lower than on smooth and shiny surfaces.,
Apparently this is connected ,with the fact that the actual working
surface of rough electrodes, is considerably greater than their
geometrical surface, as a 'xesult ;"ofwhich, an rough surfaces the.
less' than on smooth `ones.,
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and the economic factors, one uses. for the cathode soft iron' in
values on different materials, metal corrosion in the electrolyte
In construction, on taking into consideration the. overvoltage
of sand-blast machines; as the anode there is used soft iron gah
mast instances treated with sand, to rougheM et surface, -means
vanically coated with a mat Layer of nickel9
Voltage Loss in the Electrolyte
xri modern practice of water electrolysis there are used
as electrolytes excJ.usively, solutions of caustic soda or caustic
potash, ss.nce acidic electrolytes cause strong corrosion afthe
equipment? The choice of one or the other of these alkalies is
determined by working conditions and cast of the alk:alio Usually9
if electrolysis is conducted at less elevated ternperat;ures, caustic
potash is used, because under these conditions it has a higher
electrical conductivity than caustic sadaa At higher temperatures
this advantage of the potassium salt becomes less pronounced.
Since caustic potash causes strong corrosion of the equi.pment~ es-
pecially at an elevated temperature, and its cost is higher than
than of caustic soda it is more exped~.ent to use caustic soda for
electrolysis at a., high temperature,
Loss of voltage in overcor~ing resistance of the
electrolyte can be calcu,~~.ted according to the law of Ohm?
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squaxe centimeters
Actually9 however, voltage decrease in the electrolyte is
always somewhat greater than that computed on the basis of Qhm~s
law/ This deviation becomes the more pronounced with increasing
current density at equal distance bet~reen the electrodesm
This is due to the fact that in electrolysis the electro-
lyte is filled with ascending gas bubbles which decrease the ac-
tive cross section of the electrolyte. Therefore calc~:~,ation
of the actual voltage decrease requires the taking into account
of the degree of so-called gas saturation of the electrolyte
The gas saturation of sn electrolyte is ea~pressed as the ratio
(in percent) of gas bubbles volume to the total volume of the
electrolyte Cliquid + gas}~
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specific resist~.nce of electrolyte
current intensity
distance between electrodes in
cross section of the electrolyte in
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Table 2~~
Specific resas~ance of aqueous solui~ions of caustic
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 ,,~
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+,
s..
,~
,,
,,t
}f
;,,
Gas saturation depends on current density, temperature of
~ ,;
i r
electrolyte' size of gas bubbles, cell design, and is de-
the ~ ~~
+.Arm;ned experimentally. ~ r
-figure-77~~ewe the-r~la~-iv? ; nrreas~ o~ electrolyte re- ~
w,
~? ~C ~ ~.
sistance a.t various degrees. of gas ~a~r~:t~:on. As can be seen
v 7.
Y
the di.a ramw this factor is of substantial importa7icem Thus ~ -
,M
from ~_ `~
_~. ,..,., c,~+,~,a~.;~n r,~ ~~ percent the resistance i5 increased. to a
value equal twice that of the electrolyte free of gas bubbles..
4
5
Voltage Lass in the electrolyte, as is apparent from
equation (22), is proportional to its specific resistance. Con-
sequently. it is very important to use ari electrolyte of least
re$1sta.nceQ
Coe ic~.en~ o~'"~resis ante increase
Figure 7'lo Effect of gas saturation on electrolyte resistance
1 -measured resistance; 2 -calculated resistance
Table 21~ shows the values of specific resistance of caustic
alkali solutions at various concentrations and different tem-
peratures.
This table shows that with increasing temperature the value
of minimum specific resistance is shifted toward the more concentrated
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of electrical current, .that is,
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solutions. Consequently, selection of concentration of the solution
having least resistance must be made in accordance with the prop
-po~e~pe~-a-tuz e ?f ~;~~,.+~~~-~r-r-e~-e-e~t-~.-e-p~s-~
duction of hydrogen and. oxygen at 60-6~ degrees, there are used
25-2g percent solutions of caustic potash or 16-1~ percent so-
lutions of caustic sodao
Power and Material Balance
Power Expenditure and Yield on Electrical Current Basis
P~~Zagnitude of electrical pawe~? is proportional to voltage
and amount of electricity
Tt follows that the theoretical expenditure of electrical power per
cubic meter of hydrogen and 0. K cubic meters of oxygen at 0 degrees
and 760 millimeters of mercury pressure, is
1.23 2 x 96,00 x 1000 = 2.95 Kilowatt-hour.
22.E x 3,600 x 1000
wherein 1.23 is the theoretical reversible voltage of water de-
The actual power expenditure. is considerably greater than the
theoretical, which is primarily due to the higher voltage of the cell
and also to the somewhat greater expenditure of electricity in com-
parison. with the theory. The ratao.(in percent) of the theoretical
f substance, forinstance of 1
moles of, oxygen, to the amount ps actua~.ly
required according to Faradays law for
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The yield an the basis of electrical current of an electro-
chemical process characterizes the process from the sta
ndpoint of
efficacious utilization of electricity and. the talon 'n
g ~. to account
of electricity losses in el.ectrachemical and chemical side-reactions
within the cell+
We have seen previously that the basic electrochemical pro-
cess -- discharge of H+ and OHS- ions, is not accom anied b
p y any
side reactions; therefore yield on the current bas's '
i in this in-
stance depends solely on efficiency of separation of the ases and
g
absence of leaks of electricity,
Sn modern designs and installations these losses are ne li-
g
Bible (not in excess of 1 percent) and only in cells of the old
types (filter press, bipolar) lasses due to electrical leaks
were
substantial and reached 10 percent,
Thus, in practice, power expenditure is given by the
equation
In view of the high yields, on the basis of electrical. cur-
rent, which render the value of A appraximal equal to one
power.
expenditure may be considered, for every practical pur ose a
p , s being
dependent only on the cell voltage. We have ahead sta
Y ted thai;
expenditure of over '
p
ce11 voltage exceeds the theoretical: by 1,~-2 times, and the a
dual
~ygen at 0 degrees and. 760
milla
met;er f
in Kilowatt-hours per one cubic meter of
hydrogen and 0~~ cubic meters of o
.
s o mercury; fluctuates wi~thi~n the range of ~.. to 6
5
Kilowatt-haurs~
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Foundation of one cubic meter of hydrogen and 0.~ cubic
s of .o en under normal conditions, uses_up, in theory, 805.
meter xyg
Actually, expenditure of water in ~~.e e -1
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hawever somewhat greater because hydrogen and oxygen withdrawn from.
the cell carry with them water vapors.
Tf the temperature in the cell is t, the pressure of
moist gases P atmospheres, and the pressure of water vapor above
the electrolyte of a given concentration at t is equal to p atmos~
pheres, the amount of water vapor carried away by the gases can be
calculated as follows;
The voll~ne, in liters, of l male of hydrogen and 0.5
mole of oxygen, under the given conditions~is,
v ~ (22.4 + 11.2) X273 ~ t) 760
273 (~' ? p)
The weight of l liter of water vapor, in grams, under
the same conditions is,
or, the amount of water vapor, in grams, which is carried out of the
cell by the gases per one cubic meter of hydrogen at no anal conditions
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~~~?~ ~ 11.?} l8 x p x 1000
22.?~ x 22.l~ (P - p} P ? p
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Thus the amount of water vapor removed with the gases
will be greater with higher cell. temperature, which determines the
volume V of .the gases evolved, and also the pressure of saturated
water vapor over the electrolyte. The amount of water vapor re-
moved, will be smaller with increasing pressure of the gases in
the cell and with increasing concentration of the electrolyte,
factors determining the boiling temperature of the electrolyte
and depression of water vapor pressure,
Boiling temperature curves of solutions of caustic
soda and caustic potash of various concentration are shown in
figure 7~0
caustic?soda ands- potash .upon' concentration; ,
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the water expended in the decomposition
Ta compensate
r va or it is necessary to intro
ved. with .the gases as Ovate p
m
o
and re
inuousl additional: amounts
uce into the ce , e-~~~-s-e-r--~oxt ~
d
t
o
to the ce1.1 must be previously puz'~-died
of water. ~'ater added ~.n
o
t
s
l
? xed 3.m urines and dissolved mineral sa
remove mechanscally adm~. p
d either by distillation or by elects-
This is usually eff ecte
~, ~ ater is considered suitable for use tin
osmotic pur~.f 1Gation. w
cific resistance is not less than 60
electrolysis 1f its spe
sidue content not more than 7 milli-
thousandohms and the .dry re
grams per liter.
Heat Balance of theme
' rin the balance of voltage and power eX?
On conside g
60-~0 percent of the electrical
penditure, we have seen that only
cell is expended for decomposition of water.
energy supplied to the
consumed in overcoming internal reM
The remainder of this energy,
? utes a loss and is given off in form of heat
s~.stances, const~.t
amount of heat evolved, ~, increases with
within the cell. The
e and with increasing current intensity;
increasing cell voltag .
cause excessive overheating of the cell.
it can be so great as to
's available to auxiliary cooling by pro-
To avoid this, recourse i
? water cooling jacket, or more commonly,
viding the cell ~.th a
'Z Thus excess heat is dissipated and
with a water cooling coy.
re is regulated to maintain it at the
electrolyses temperatu
conditions the heatregimen of a cell.
desired level. Under ,.such,..,,
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wherein
- heat consumed in heating the feed water to
electrolysis temperature
- heat consumed in evaporation. of water
- heat removed with the hydrogen and oxygen
heat lost to the .surrounding medium
1.23 x nF;x 0x.238 calories (27~
;reversible theoretical vo~.tage of water decomposition,
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At constant temperature of electrolysis, and of the
surrounding medium, q~, q3, q~ and q5 are constants and con-
sequently q~ which determines expenditure of cooling water depends
upon the amount of heat Q, generated in the cell, Tt would appear
that ~ should be equivalent to the difference between the amount
of electrical energy, actually expended in the cell, and that
theoretically required for the decomposition of water,
Energy expended is equal to
W~ V x nF x 0 238 calories (26)
where V is cellvoltage.
Energy theoretically required for decomposition of
water is equal to the .maximum work of the hydrogen-oxygen galvanic
celh,
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or the electramotive foxce of the hydrogen-oxygen cell.
nF(V) - 1.23 0.238 calories (28)
However, this correlation is but a specific instance,
which holds where maximum work performed by the system, is nu-
merically equal to the total change of the internal energy of the
system, that a.s, to the, thermal effect of the reaction, In other
wards, when in the equation of dependence of maximum work. and
thermal effect
A..q+q (~9)
q is equal. to zero
In our case, at 2~ degrees and 1 atmosphere, the thermal
effect of the reaction
A 1.,23 x nP' x 0,23$ ~ 1.23 x 2.x 96,000 x a.238~ ;6,;60 calories.
amounts to ? 68 330 calorie,s~
Whereas maximum work is
Hence
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Hence, Q must be equal to
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also enere.tes the amount of heat q = 11,770, calories per l
but g
mole of watero
Consequently in the reverse process -- electrolysis
water --~ there will be expended nat only the electrical energy
of
Wl but also absorbed the. heat q,
Therefore the amount of heat liberated in the cell
V x nF x Oe238 _ (1,23 x nF x 0.238 + q) y
y V x nF x Oa238 - 68,330 calories
Expressing, for convenience of calculation, the
subtrahend in units of the same dimensions as the minuend, we have
~ = V x nF x 0238 ~ 1~G8 x nF x 0.238 =
nF x 0?238 (~ - 1.~~8)
Substituting the amount of electricity nF by current
intensit and multiplying by 3600 (number of seconds in an hour}
Y,
we have the hourly amount of liberated heat (in calories hour)
~ x 3boo x 0.238 (~ - 1?~8) ~ z x 0,8;6(v - 1,~8) (30}
1,000
we see that the amount of heat generated depends only
on current intensity and cell voltage and increases in proportion,
to their increase.
~,~hus the conclusion can be arrived at, that should it
be ossible to conduct decomposition of water at reverse potential
p
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d o erate endothermacally and in order to maintain
1.~3 the cell woul p
' it would be necessary to supply-external.
the the rural e qu.~.llbri um
. 0 calories (q) for..each mole. of water
.heat ~n the amount of 11,77
decomposed,
rind les of Design .and Operation of Cells for water
P _~?-
he roblem of any efficiently run production, besides
'~ P
conditions and obtaining a high quality
providing best working
' 'n minimum production expenses, that is, least
product, ~.s attalna. g
of roducts obtained, Production costs in the present case
cost p
' of ex enditures for electrical power, labor
consist essentially P
a es re airs and amortization of the equipment. It is necessary
wg , P
for such a regimen of the technological process at which
to str~,ve
ure of electric power, which constitutes the primary factor,
expendit
determines the cost of electrolysis, is at a man~.mum? The
which
lar e volumetric output, they must be cheap and
cells must have g
maintained, Fulfi 1lrr~rst of these conditions constitutes
be read~~.~'
ver cam 1ex technolog~.ca1 problem, which as far from being com-
a y P
a d if we bear in rnirld that utila~ataon of power stall
pl~,tely solve ,
fluctuates at only about 5~ percent.
From the foregoing at fa L1ows that power expenditure must be
affected by overvoltage at electrodes, gas saturation
very matera.ally
of electrolyte and its resastance? Decrease of overvoltage can be
' c eosin electrolysis temperature, by selection of
ach~.eved by ~.n r g
the~~electrodes, and by decreasing current density.
suitable material. ,for
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vet increase of temperature, under conditions of electrolysis
Howe ,
atmos heric ressure, is limited,. as is apparent from the
at .normal p P
diagram shown in figure 78, by the boiling temperature of the
trot to and increased corrosion of iron parts of the cell.
elec. y
Selection of electrode material is also limited by economic factors,
'n tactics the cells are constructed solely of steel and iron
and i p
coated within individual areas with nickel.
~1'he most expedient measure, .therefore, is decreasing current
densit at the electrodes, which in practice is attained by various
Y
constructive embodiments and electrode processing methods, intended
to provide increased surfa.ces~ ~~hus, .for example, the electrodes
are subjected to sand blasting; the cathodes are coated with molten
oxides of iron which on reduction form a layer of spongy iron, or,
final/ the electrodes are galvanically coated with iron or nickel
Y~
containing sulfur, and with metallic alloys?
Gas saturation can be decreased by increasing the distance
between the electrodes and decreasing current densitya But both
these measures cannot be considered efficacious since the first
by increasing ohmic resistance of the electrolyte correspondingly
increases power expenditure, while the second decreases output of
the cell, One strives to decrease gas satura~ri.on by a choice of
an of fec~~ive form of the electrodes and by an increase of electro-
lyte circulation velocity, so as to remove rapidly the gas bubbles
from the path of-the current. It has also been proposed to add cer-
tain ingredients to the electrolyte, for instance to add finely
powdered graphite, in the presence of which small gas bubbles com-
bins into larger ones and are more rapidly removed from the electrolyteo
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sis under increased pressure also decreases gas saturation,
Electroly
m' c resa.sta.nce of the electrolyte is achieved,
Decreased oh a.
choice of a solution concentration havj-ng maximum con-
bes~des the
' ased electrolysis temperature by lessening the
ductiva.ty and a.ncre
t een electrodes But since shorter distance between
distance be w
' ceases as saturation, perforated or reticulate elec-
electrodes inc g
sed in these cases so us to render them permeable ~
trodes are u
.gases.
2? Electrode types
The great variety of electrode des~.gns for use in
~~en cells w}~~.ch have been proposed and are used in electrolysis
hydrab ,
racta.ce is due prec:t.sely to efforts aimed at attainment of minimum
p
ex enditure with concomitant increase of the output of the cell.
power p
us review the most important designs which have found utilization
Let
in practice.
Simple plate Electrodes
An electrode of most primitive design consists of a
smooth Iran sheet from l.~ to 2 millimeter thick with twa iron rods
d on which are used to suspend the electrode in the cell and
welde ,
e current, Such a construction being mast simple is of
to conduct th
' from the standpoint of measures tending to decrease
poor efficiency
v to e Gas saturation, on use of such electrodes, will be very
of g .
substantial? it wi71 be the more pronounced the greater the current
he hei ht of the electrode. Therefore such electrades
density and t g
are of small height which must not exceed one half of their length
accent density at the electrades must also be low (from 200 to 300
C
ampere per square meter)..
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The electrode (figure 79) consists of two flat
parallel sheets, provided for added strength with embossed r'b
~. s e
The sheets are 2 mill~.meters thick, the distance bei~ween t
he sheets
is b millimeters, Tine size of the sheets is 100 ,
0 x 1000 m~.ll~.-
metcrse An iron rod is riveted to the sheets for sus en '
p dz.ng there,
Current is supplied through a capper bus bare
Considerable height of the electrode unavoidably
increases gas saturation especially in the upper part of the cell,
were it eat for the fact that the des~,gn of the electrode
promotes.
circulation of the electrolyte along the workin surfac
g e of the
e~.ectrode. The working faces of the electrode are on]. its outer
y
surfaces; the inner surfaces are inactive, and the electrol to be-
Y
tween the sheets remains free of gas bubbles, The d
e nsity of the
electrolyte at the outer surfaces of the electrode becomes lower
3
due to the presence of gas bubbles, than that of the e
lectralyte
between the sheets. Hence electrolyte between the .sheets flow
downward, forcing the electrolyte at the outer surf
aces to rise.
upward and carry the gas bubbles out of the path of the
.current.
Thus the design of the double electrode promotes
decreased gas saturation. This however is still ins
uff~.cxent for
achieving a considerable voltage reducing effect within
the
electrolytic bath and for that reason electrodes of this t e a
yp re
used with low current densities (about 100 am eyes er
p p square
meter)e
Figure 79. Double plane electrode,
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In electrodes of this type an attempt. is made to
the working surface of the electrode thereby decreasing
decrease
rent densit + Zaininary electrode (figure $0)
the effective cur y
? f vertically disposed parallel narrow iron strips 1.
consa.sts o
are dis osed at an equal distance from one anather~
mhe str~.ps p
'ch is attained by means of iron rings 2 located between there,
why.
the stri s are held together as`a unit with halts 3? The
A.ll p
ode is suspended on iron rods I~ which serve also to con-
electr
;l the current. ~ Some e7 ectrodes of this type consist of a
duc, ~
lar e number (up to 360) strips. An electrode 1100 milli-
very g
meters long and 96~ millimeters high, consisting of 360 strips,
22 millimeters wide a,nd 0.~ millimeters thick has an effective
surface of 18.32 square meters, that is exceeds nine times the
surf ace of an electrode of identical lengths and height, but
shaped in the farm of a flat sheet.
Current density on such an electrode varies over
its surface. It reaches highest value at the end surf aces of
the stri~s and decreases with increasing distance from end toward
p
the middle portion of the strips
Therefore the mean density of
current on the electrode decreases not nine times in .comparison
with the plate electrodes but somewhat less, but is still con-
lower. Use of laminary electrodes apparently also
siderably
decreases somewhat gas saturation of the electrolyte in the
ath of the current and by so doing also promotes voltage decrease
p
in the cell. In view of their extensive surface area larr~inary
electrodes ermit application of a considerably higher density
p
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of current, up to 1,00 amperesper one square meter of geometric
o'ection, that is, about five times .more than that of a simple
pr J
plane electrode
Figure 80~ Laminary electrodes l - iron slats; 2 -iron
rings; 3 -bolts; ~. - iron rods,
and as current conductorso Welded to both sides of the bars are
iron strips disposed at a certain angle with respect to the ver-
cross section terminated at their upper end by circular cross
section rods, These bars are used as supports of the electrode
is eliminated, The electrode consists of two iron bars of square
lower. xn the louvered electrode (figure 8l} this disadvantage
the upper paxtion of the cell is considerably greater than in the
Louvered Electrodes
In all of the hitherto described electrodes the.
as saturation increases with decreasing distance from the sur-
g
.face of the electrolyte, and the resistance of the electrode in
~~ ti cal axis of the barsp The straps. are positioned one underneath
the other in close proximity, so that they are separated from one
another by narrow slanted slits,. Gas bubbles on detaching them-
selves from the strip rise upwards and impinging upon .the next-above
strip, slide along its inclined surf ace into the inner space. of the
electrode within which they then rise to the surface of the electra-
lyte.
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Figure 82. Perforated electrode.
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.Thus, in theory, no gas bubbles.enterthe
tween consecutive electrodes -- anode and cathode, and are sa
pletely removed from the path of the currents In the path of the
current between strips there are present but a few bubbles, and
their number is practically the same at the lower and at the upper
portion of the electrodes This arrangement unquestionably greatly
decreases the harmful effect of gas saturation. In addition there
takes place circulation of the electrolyte, upwards inside the
.electrode and downwards between two consecutive. electrodes,-which
further facilitates rapid elimination of gas from the electrolytes
Finally, the increase ~_n comparison with a plane surface of the
electrode induces decreased current density,
All this makes it possible when the number of
strips is extensive to utilize with such electrodes current den-
shies up to 2500 amperes per square meter of geometrics.l pro-
jection of the electrode. A shortcoming of the louvered elec-
trade as well as of the laminary electrode is complexity of con-
structions
Perforated Electrodes
The desire to simplify and to render less costly
manufacture of electrodes while retaining at the same time the
advantages of electrodes of extensive surface and permeable to
gases, has led to the construction of perforated electrodes.
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Such an electrode (figure 82) consists of two iron
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sheets welded to two iron bars which serve to suspend the electrode
and to conduct the current. The iron sheets are 3 millimeters thick.
and are perforated with a great number of circular apertures..
Although it would appear that perforation would de-
crease the surface of the electrode, it is possible by adequate
selection of apertures diameter and distances between them to at-
tain an increase of the working surface, since in the punching out
of the holes a new lateral surface is formed, ~ Furthermore perfor-
anion makes possible utilization of 'the back side of the sheets
which increases the overall working area of the electrode in com-
parison with a plane one, On a perforated electrode a consider-
able portion of the gas passes into the inner space of the elec-
trode and there talces place intensified circulation of the electro-
lyte This decreases gas saturation in the zone between adjacent
electrodes and permits to place them more closely together, thereby
decreasing the resistance of the electrolytem
Removal of gases into the internal space, utiliza~
Lion of the reverse side, induced circulation and especially close
proximity of the electrodes make it possible to use current den-
sities up to 200 amperes per square meter of electrode projectiono
In addition an advantageous feature of perforated electrodes is
their greatly simplified manufacture in comparison with laminary
and louvered electrodes,
In other designs the same principles are utilized and.
they differ only in cotastructional features..
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Separation of the Gases
.Y.,.....,..d...... --- -~...~.......
By means of electrolysis completely pure gases can be
produced. This requires only a careful separation of hydrogen and
oxygen, thereby precluding contamination of one gas by the other as
a result of mechanic mixture or of di.ffusa.on. Separation of the
gases is importa?lt not only because it is necessary to produce therr>.
in a pure state., but also because a question of safety is involved
namely avoidance of detan.a~ting gas farmat7.on,
The s~.mplest method of gas separation consists in the
use of wide, deeply immersed belts as is shown in figure 83. Elec-
trodes 1 arad 2 are located inside the iron bells ~ and ~. which are
deeply immersed in the electrolyte. To prevent evolution of gases
on the external surfaces of the bells, the electrodes are provided
with insulators ~~ The generated gases rise vertically, enter the
bells and are removed separately through suitable gas outlet pipes,
Such a scheme though dependable and simple is not
expedient for large industrial cellsa Wide bells make it necessary
to space the electrodes wide apart and in addition by shielding a
large portion of the electrodes lengthen the path of the current.
This causes great losses of voltage in overcoming resistance of
the electrolyte
figure 83o Separation of gases by means of bells;
l and 2 a electrodes; 3 and L~ -iron bells; ~ -insulators
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For this reason in the large modern cells there is used
for separation of the gases, only a diaphragm, that is a porous
partition, readily permeable to ions but impermeable to small gas
bubbles. The electrodes, as this is shown in figure 8Z~, are still
placed inside of bells l and 2; the lower part of the bells is
immersed in the electrolyte but the height of the bells is con-
siderably smaller. At the lower end of one of the bells, and in
some cases of every bell, there is provided a bag-like porous
diaphragm 3 which completely surrounds the electrodes In such
an arrangement the electrodes can be placed considera'aly closer
together, and still the gases practically da not mix if the
diaphragm is in good working condition, It is merely necessary
to make certain that the electrolyte level in the cel_1 does not
drop below the rim of the bell and the diaphragm does not pro-
Crude above the electrolytes Otherwise the gases diffuse readily
through the diaphragms
Figure 8~.~ Separation of gases by means of diaphragm.
., r. ~...... r....,.......
1 and 2 -bells; 3 m poroas diaphragms
Diaphragms used for the separation of gases must meet
the following prerequisites; (1) Possess low electrical resistance
(2) Be sufficiently dense to preclude passage of gas bubbles through
the diaphragm (3) Be sufficiently strong mechanically (~.) Be chemi-
ally resistant toward the electrolyte.
Asbestos diaphragms; The above listed conditions are
~,.,, IWaY ~~, ~?zgYk ,~P n w~~ 1tu?' rt'r'r~s q^r P'W~'~`udrq
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 he li:t'e of ar asbestos diaphragm is usually of several
T
~~ ~ation 3-~ or more) if the diaphragm is not subjected in
yearn dur (
of its use to drastic mechanical action, which may take
the course
exam le as a result of hydrogen and oxygen pressure fluc-
pldce fol p
tuations.
Metal diaphragms; Much less frequently porous metal
ms are used, xn practice diaphragms of thin nickel foil
d~.aphrag
nte,ininJ a large number of small apertures (800-1100 apertures
co 6
centimeter square) are being utilized Such a diaphragm is
per
b electroplating methods? Nickel is deposited by electro-
made y
rt'n on a co per matrix the surface of which is covered with
plC~ a. g p
minute dot-la.ke recesses. The matrix is coated with an in-
sulatin varnish which fills the recesses. When the varnish has
g
dried it is scraped off the surface but is re~ta.ined in 'the recesses.
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. asbestos fabric, which is used almost exclusively
mo s~ fully met by
In the r~,nufacture of strong asbestos fabric there
in modern cells.
~ali resistant long fiber asbestose The best grade
is used puxe, alk
d rocessed ~+crude" asbestos with fibers from
is considered to be han p
'meters long. From the long fibers can be made a strong
l~ to ~~ m~.lla-
hich the asbestos fabric is kToven. The fabric must
yarn, out of w
ven must appear opaque when viewed against the light
be closely wo ,
ess su:ffi_oient tensile strength? Tn most cases single
ar~d pops
ave fabric from l.~ to ~ millimeters thick is adequate?
plain we
beau r dut~ there is used double twill weave fabric from
Fox more ~ Y
~ ' lliraeters thicken Sometimes for increased mechanical
~ to 3,, m.1
weft thresds are reinforced with nickel wire 0.16
strength the v
millimeters in diameter.
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'x is then nickel-plated. zn the course of this operation
the matri
'ckel is deposited upon the entire surf ace of the matrix ex-
the n~.
t the Dints retaining tY~e varnish caatirlg, The nickel
cept a p
d surface is then slightly oxidized and on the o~.dized sur-
plate
e the diaphragm foil is then produced, and can be readily re-
fac
ved therefrom? Nickel diaphragms are stronger than asbestos
mo
dia hragms but by the action of the electrolyte ;hey also are
p
ected and require periodic overhauling which is
adversely off
effected by fastening patches aver the damaged areas.
metal diaphragms on breaking down may cause short cir-
ultin of the electrodes, and are in this respect less satin-
c g
cto than those made of asbestos. For this reason it is
f a ry
dangerous to place the electrodes very close togetherq
Cooling, Washing and Rego-ati~ne Pressure of the
Gase s
The gases leave the cell at a temperature of 60 ded
rees-80 degrees, and carry with them, as wa.s pointed out pre
g
viously considerable amounts of water vapor. Moreover together
with the water vapors there are being entrained particles of the
electrolyte in the f orrr~ of m~,nute droplets and of alkaline mist.
Since removal, with the gases, of large armu.nts of
va or would cause ~.ncreased expenditure of distilled water, while
p
removal. of electrolyte -~ incz?eased expenditure of caustic, an
effort is made to cool the gases ~.mmediately upon egress from the
cell On cooling the greatest part of the vapor condenses and
flaws ba.clt into the cell. To attain this, cooling with water is
resorted to of the covers or of the bells under which the gases
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collect, gas outlet pipes are made sufficiently long, and finally
the gas is made to bubble through a layer of cold feed water, In
the 1G.tter treatment, purification of the gases tapes place simul-
taneously from a considerable portion of the alkali contained therein
and equalization o~f pressures within the hydrogen and the oxygen c~m-
partments of the cell?
Differences of gas pressure in the cel..1. can arise as a
result of various conditions; for example, different resistances in
the pipe manifolds, formation of liquid seals in the pipes, unequal
rate of gas removal, and so forth, At tree same time maintenance of
a caristant pressure of the gases is of great importance, since ex~
cessive pressure increase of one gas within the bell, may cause
lowering of the electrolyte level below the rim of the bell, ex~
posing the diaphragm, or even project the electrolyte aver the .rim
of the cell, Exposure of the diaphragm, as pointed out previously,
will cause mixing of the gases, with possible formation of an ex-
plosive mixture, pn the other hand, frequent and drastic fluc-
tuation of gas pressure by subjecting the diaphragm to excessive
mechanical action will result in its rapid deterioration. Hence
regulation of the gas pressure is most important, It can be
effected for each individual cell, or more commonly, fora given
group of cells
Figure 85 shows diagramn~atica.lly a hydraulic gas
pressure regulator in which scrubbing of gases also takes place.
The regulator consists of two vessels l and 2 connected at their
hydrogen flaw through connecting pipes into the vessels of the
bottom by a ,junction pipe and filled with water, Qxygen and
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h a layer of water, pass into
e ulator and after bubbling throug
r g ~ es the pressure of
for ipes ? If in the collector pa-p
the colleC p on the
s a change, this has no effect up
one of the gases undergoe
es within the bells of the cell.
pressure of the gas
draulic regulator of gas pressure?
~; pure 8~. Hy
1 and 2 ~ connected vessels
ressure of the hydrogen increases9
If far exsnlple the p
asel 2, through the junction pipes
grater will be expelled from ve
ssels there will be established, a
Into vessel le xn the ve
d which w~-11 caunterbale~nCe the pressure
difference in level ese con-
h drogen and axygeno But under th
di~'ference between y
in vessel 1, through a layer of
ditions the oxygen ~~- bubble
bile h drogen in vessel 2, through
11 uid having the height K, w Y
q ressure
e h ~, d ~ k, it is obvious that the p
a layer hs S~.nc f the
remain the same for both gases I
w-l,th.in the bells well
. een the vessels is of sufficiently large
junct~.an p~.pe betty
water from one vessel into the other can
diameters the flow of tus.tion
'dl that no appreciable pressure floc
take place so rape Y
will occur within the bellsm
~., ~Jater Feed of the Cells
asitian of the water, the level of
Because of the decomp nd
e cell drops continuously and may desce
the electrolyte in th
l
t
y
e
,t if the cell is not being adequa
L _, .... ~~o r,F~rmi_ ssible lzm~. ~
Fresh feed water. xn small installations tine ~~ ~,~-,
supplied with
rs
h
s
ou
' +e~,v.ttently at intervals of several.
water can be added ~.n ~
b the
' ~e of the cell Volume not filled y
depending upon the s~
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ctrol e. Small periodic changes of alkali concentration in the
ele ~
electrolyte are of no importance since the resistance of the electro-
lyte is altered but littlea
This method, however, becomes impracticable in large instal-
lations. In these, addition of water is made automatically. This
is done by providing the cells with float controlled level regu?
lators. A common water supply pipe is installed alongside the
cells fram which individual conn.ection.s lead to each. cell
Water flows into the cell from a pressure tank. Depending
upon the position of the electrolyte level., the float opens or
closes the water intake pipe? Far simplicity of operation, a single
float actuated regulator is provided far an entire group of cell s
Tn such a case the float is contained in a separate vessel con
netted with the cells .by means of a system of pipes. Into ~h~3
vessel flows the water from the pressure tank; the water level
in the vessel is maintained by the regulator at the same height
as that of the electrolyte in the cells. This simplification is
inconvenient in this respect that it may cause forcing of the
electrolyte into tha feed system and its passage into other
cells. To avoid this it is expedient to install the feed pipes
above the cells and to provide inlet pipes extending downward
into each cell almost to its bottom.
Feed and automatic regulation of the electrolyte level
in the cells which are hermetically closed by means of a cover,
can be readily attained by using a pressure regulator the design
of which is shown diagrammatically in figure 86.
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Feed
Water
Figure 86~ Diagram of regulation of the electrolyte level
__..
in the cells 1 and 2 - gas bubblers
Feed water in the necessary amount is periodically charged'
or continuously introduced, into the pressure regulator from which
it passes through the pipes into the cel]-, The gas bubblers 1 and
2, are positioned in the regulator at a height approximately equal
to that at which it is desired to maintain the electrolyte level
in the Bello The level of the electrolyte in the cell w~.ll be
below that of the bubblers by a height difference equal to ~ h.
The value of L~ h depends an the density of the electrolyte and the
location of the feed pipe outlet and does not depend on the water
level and gas pressure in the regulataro
xndee d~ let us consider the pressure in the pipes to the
left and to the right of the section f, assuming that the pressure
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of the gases in the regulator is equal to atmospheric
Pressure of the gases in the cell, with a scrubbing height
h and a density of the feed water r~' is
Then the pressure at section f from the left hand side'
~ is the density of the electrolyte, will be
p ~ ~, atma sphere ~ h ~' ~ h' 1 ~ ~ ~ 3 ~ }
f
and the pressure from the right hand side;
p o , ~ l atmosphere ~ h~ ~ hl ~' ~ 33 ~
f
At the state of equilibrium when the liquid does nat flow
in either direction, we have
that is, the level of the electrolyte in the cell wall tend to be
equal. with. that of the bubbler with decreasing difference between
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'n the regulator and that of the electrolyte,
density of solutyon ~.
asin height h ~ that is the distance of the
and also wa.th decre g 1
he cell from the level of the bubblers.
feed p~.pe outlet zn t
d ~ are equal, the level of the electrolyte
When ~ an
t exceed that level since
wall be that of the bubblers, but canno
? A drop of the electrolyte level be-
canriat be greater than ~ .
'cannot occur, because disruption of the state
low the height hl
' be immediately compensated by inflow of water
of eq~.librium w~.ll
which will take place until the water level
from the regula,tar,
'n the regulator drops below that of the bubblers
a
ndustrial Cells for the Electr 1ys~ o,
B? l
Industrial Cell Types and Their Classification
1? -._.w?
the ractice of electrolytic production of hydrogen
In p
are being utilized, cells of widely different
and oxygen there
'n s ite of thea.r apparent dissimilarities can be
designs, which ~, p
ted into several groups on the basis of design characN
segrega
teristics common to all members of each group.
Cells of all types can be divided into two basic groups
bi olar. The common feature of all cells in each
monapolar and p
' he s stem of connecting the cell electrodes to the
group ~,s t y
electrical circuit.
afar cells (figure 87) have a number of parallel
Monap
es 1 One half of these electrodes is connected in
electrod
to the ositive terminal of electrical circu~.t. These
parallel p
'cute the anodes. The other half is connected in
electrodes canstl
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the same manner with the negative terminals these electrodes serve
as cathodes xn such a connection system, each electrode considered
separately has but one polarity, that is, constitutes either an
anode or a cathode.
Figure 87, Diagram of a monopolar cells Z ~ electrodes;
Current intens~.ty in the cell is proportional to current
density and the surface of all the electrodes of the same polarity9
while the cell voltage is deter~~.ned by the difference of potential
of one pair of electrodes ( cathode and anode) , Therefore the
characteristic electrical feature of monopolar cells is the fact
that current intensity in such cells is always many hundred and
even thousand times greater than the voltage
Bipolar cells figure 88), the same as monopolar, have a
number of parallel electrodes 1, which are, however, connected to
the circuit in series Current is conveyed on1.y to the terminal
electrodes, ~ the anode 2 and the cathode 3. Fxom the anode the
current flows to the electrolyte, is transferred by the ions to
the intermediate electrode 1, imparting to it a negative charge
passes through it and from its opposite side enters again the
electrolyte, imparting to this opposite side of the electrode a
positive charge. Thus the current flows through the entire cell
anal reaches cathode 3. The terminal electrodes 2 and 3 are thus
monopolar, while all the intermediate electrodes are bipolar, that
is, one side of each of them operates as a cathode and the other as
an anode
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bipolar
trodes? 2 - anode; 3 - cathode; ~ - sectionb
elec ~
Figure $~? Diagram of bipalar cell:
in a bipolar cell depends only on current
Current lnter~slty
the surface of one morLOpolar electrode (anode or
density and
t de end upon the number of bipolar electrodes.
cathode) and does no p
the other hand depends an the difference of
Voltage of the cell on
tween consecutive electrodes and is directly propor~
potential be
ber of aiz~s of cathodes and anodes. 2f the
tonal to the num p
. _ ntial between anode and catl~.ode is equal to 2
d.~.ffer~;ncc of pote
-caa.e of the cell shown in figure 8a is equal
volts then the vol ~;
-ta 2 x 6 ~ 12 volts ?
? cells the characteristic electrical feature is
In b;~polay
' valta~e is several times ten, or even several
the fact that thea.r a
r over that of monapolar cells, ,chile current
~~,:~mes one hund_eds
considerably smallor. Thus the electrical
~.ntens~.ty is usuall,~
' olar cells exceeds that of monopolar cel7.s by a
capacity of bap
several. tames ten factor.
ar and bipalar cells can be divided into bar cell-s
Monopol
~n~ s cells, Monopolar cells are almost exclusively
and f~.lter ~,~es
of the bar type.
essential portion of box cells 9.s a container of any
The
holdin the electrolyte, rota which are immersed
sua.table shape, g
The container can be open at the top (in which
the electrodes.
e is in contact with the atmosphere) or closed
case the electrolyt
s are mare complex in construction and of
by a cover.. Clawed cell
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mare costly production than the open ones, but in them losses of gas
are smaller, the electrolyte is protected from impurities (car-
bonization by carbon dioxide of the air), and it is possible to pro-
duce in them the gas~;s under higher pressure, The conta~.r~er9 or
bax, 2 of monopolar. cells (figure 8?) is made of iron and must
meet only the prerequisites of mechanical and chemical durability,
Monopolar electrodes of ane of either signs may be in contact with
the bax, but the box should not be in contact with both the cathodes
s,nd the anodes?
The bax of a bipolar cea.l (figure 88) must be ~r~~de nonce
conducting for the electrical currents The electroces must
part~.tion the space within the box into a number of sections ~.~
inslz.lated from one another, and which can be connected only through
narrow gas channels and channels fax the introduction of feed water
into the sections. Construction of such boxes is costly and comW
plicated,
The essential parts of a filter-press bipolar cell (figure
8q) are the steel frames 1, rectangular or circular in crosses
sectiona and the bipolar electrodes 20 The electrodes are located
between the frame; and are separated from them by insulating and
sealing gaskets 3, Frames and electrodes a.re tightly drawn to-
gether by means o:F bolts and forma single cell unit composing
any given number of electrodesv
Further classification of monopolar cela.s can be made by
type of electrodes, thus subdividing them into cells with simple
plane electrodes and cells w~.th complex electrodeso The latter
group cornpases most monopolar box cells,
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i ure 89. Diagram of filter press cell: 1 ~- steel
F ~,,.~...,.~.~
fraanes; 2 -bipolar electrodes; 3 ~ sealing gaskets
~. ~ola.r filter press cells can be further. subdivided into
B~ .
cells without external circulation.
Final~.y cells of all types can be divided in~tra cel~,s
operating at normal atmospheric pressure, or at a pressure
a roa:imately equal thereto, and cells operating at high pressures.
pp
2. Monopolar Cel:Ls with S:t.mple ~Electrs
Cell with 'lane wElectr
`maternal appearance of a cell with plane electrodes
and its internal configuration are shown ~.n figure 90. In an
Iran ba~x eleetrades 1 are disposed in parallel relation made
from :Lane smooth, sheet iron having a thickness of 2 to 3 m~.lli~
p s
me; ters. The anodes are ccaated electrol'yt~.cally with a layer of
nickel 'to pral;ect the ~.ron :from anodic o:cidatian and ~to deco^ease
o en overvoltage, which is less an nickel than on iron, '.Che
xYg
electrodes are sus~aended from iron rods 2 connecting them to 'the
collecting bells 3 w}~ich in their turn are supported by lugs
rest~i.ng on the rim of the box. Rods 2 also serve to conduct the
current and are insulated froze the bellso
Figure 90. Cell with plane eleetrades; 1 -electrodes;
2 .. 3.ron rods; 3 -~ bells; ~ -asbestos diaphraglr~s; 5~
pipe, 6 - manifold pipe lines,
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The manner of suspending the electrodes and insulating
them from the beJ1s is shown more in detail in figure 9ld Ta the
bell 1 there is welded a spacer tube 2, inside of this extends sus-
pension support 3, enclosed in insulator tune ?~. Bottom and top
of the suspension support are covered bar insulating collars ,~ and
6, The electrode is fastened by means of nuts 7 between which is
held the current conveying bus bar $~
Fie 9l? Suspensi.on of plane electrode: 1 ? bell;
-~ iron spacing tube; 3 ? support; ~ ? isolator. tube; ~ and 6 -
isolation bushings; 7 a nut; 8 ? bus bar?
To effect separata.on of gases the cathodes are sur-
rounded by asbestos diaphragms ~. (figure 9Q7 fastened to the bottom
rim of the hydrogen callect~.ng bells and depending therefrom in the
foz~rl of open-bottom bags? Bells 3 are immersed into the electrolyte;
gas pressure within them must be such as to maintain the elecj:roM
lyte within the bell at 5-7 centimeters above the lower insula~
Lion collarv Hydrogen and oxygen rising vertically called under
the corresponding bells and pass through the outlets into col-
lecting pipes ~ and frorn these into the manifold pipes 6. The
Latter are of zigzag shape to promote cooling of gases and con-
densation of water vapo.rs? Due to the sloping angle of these
pipes, the condensed water together with the entrained alkali
flows back into the cell The manifold gas pipes are provided
with glass sections with rubber connections, located between each
pair of cells by the provision of which electrical leaks are
obviatede From the manifold pipes the gases pass into scrubbers
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a er of water they are freed of alkali..
.here on bubbling through a 1 y
e an 18-20 percent solution of caustic
As the electrolyt
e uently a solution of caustic potash.
soda is used and much Jess fr q
11 ermits contact of electrolyte ~.th
ppen construction of .the Ce p al
ult of which there takes place a gradu
the atmosphere as a res
atmos heric carbon dioxide and a
carbonisation of the alkali. by p
,? ~t of the electrolyte ? Therefore at
decrease of the conduct. y kali
bout once every two-three years, the al
periodic intervals, a ed and in~
? ~ ~ aced at which time the cell is also clean
is being reel ~
spected`
thy; diaphragm is, on the average, ~ -7 years?
Life of
. '~ d a~t a temperature of 60 degrees ? In ce11s
Electralys~.s ~.s conduce
ds a cooling coil is provided on the
desa.gned for heavy amperage loo
bottom far temperature regulation.
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? ter into the cell is done either manually
Feeda,ng of era
from a small. pressure tank provided with.a can
or automatically
The feed tank is connected through pipes
scant leVe1 regulator.
so that in these also the water level is
.~ th the gas scrubbers,
scant thereby ensuring a constant gas pressure
maintaa.ned con ,
within the bel~..s. .
of a breakdown, or of insufficient feed
In the event
he electrolyte level can be readily, and
of water, lower:>^ng o.~ t ~
? rl detected because the gases begin to escape
suf fzc~ently ea y
rorn the cell? This takes place when the
the atmosphere, f
w collar ~ and the gases are afforded a
electrolyte drops belo
? e 2 by the leaky connections provided an
free outlet, through p~.p ~
this method of attacking the electrodes.
purpose in
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s are built for different loads (from 166 up to
cell
accordance with which dimensions and number of
10400 ampere, } in
va Cells of 10000 amperes have ~.1 electrodes; are
electrodes ry
ion ? 2.00 millimeters wide, and 1270 millimeters
12a~0 mill~.meters ~,
rent density is maintained low -- about 3~0 amperes per
h~.gh. Cur
vet the voltage of the cell even at this current
square meter, howe
' ual to 2.2~ volts, while an increase of the load up
density is eq
to 1,000 amperes rises to 2?~ volts?
is ram of figure q2 shows dependence of ce11 voltage
D ~
ad Paper expenda.ture with a voltage of 2.2~ volts
on ampere la
1. ~.lowatt-hours per cubic meter of hydrogen at 0
am0 Llnt a t0 ~ ~ G
tees and 7 60 millimeters of mercury.. Pus`a.ty of the gases
deg
hydrogen 99?~ percent and oxygen 99?0~~
Voltage
,.n
Load in thousand of amperes.
~'a,~pry!ure 92. Dependence of voltage on load in cell with
Figure 93 shows the general appearance of the instal-
' the zi za shape of the manifold pipes which is characteristic
latzon, g g
of these installations can be seen.
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Fi re 93e Overall view of installation wa.th plane
electrode cells.
Open_Cell with Double Plate Electrodes
Figure 91~ shows the longitudinal and transversal vertu
sections of the cell This is also an apen ce11, a charac~
t~.ral
'stir feature of which is the simplicity of canstruction?
tera.
Each of the electrodes 1, consists of two plane iron
].000 ~ 1000 millimeters in size and 2 m3.llimeters thick
sheets9
l.el to each other and disposed at a distsnce of 6 milli
tiaral_
,.
To the electrode is riveted an iron rod 2 by means of
meters.
' h the electrode is suspended from the gas bell? Each bell
wh~c
' is of a narrow Iran box having a small cupola ~~ through
3 cons:~s
sses the electrode rod, 1.nsulated from the cupola and
wh~.ch pa
stened b a nuts De11s 3 are supported by lugs resting on the
fa y
'ron casing of the cell. To the edge of each bell is attached a
dia hragm of asbestos fabric, surrounding the electrode. The
p
electrodes are located at a distance from one another, amounting
to 0 millimeters at their cen~~ers. In order to retain the plane
5
form of the electrodes? in view of their relatively small thickness
the sheets are provided with several embossed ribs 6, which impart
rigid~.ty to the sheets o The anodes are nickel coated,
Current is supp~?:Led to the electrodes by means of a
nickel plated capper bus bar 7 and is carried off by a similar bar
then electrode at the opposite side. The bar is riveted
from ono
is of the electrode and. passes through the bell 3@ It
to the shoe
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is insulated from tie bell and the electrolyte by an eternit bush-
ing and cement lining which seal the paint of passage of the bar
through the bell and preclude leakage of gas.
Hydrogen collecting in bells !~, passes through open-
ing $' in the upper part of the cupola, and collects in a single
overall collecting bell ~~ which covers all of the cupolas of
hydrogen be11s 4? From the collecting bells the gas passes rota
the collecting manifold pipes. Tn the same manner by means of a
collecting bell 10~ is effected the removal of oxygen.
Figure q~.. diagram of cell with double plane elec-
trodes: 1 -electrode; 2 p iron rod; ~ ~ gas bell; ~. - cupola
of bell; ~ - cell casing; 6 - ernbassed ribs; 7 -copper bad;
$ - aperture in bell cupola; 9 d collecting bell far hydrogen;
10 -collecting bell far o:~ygen.
As the electrolyte a solution of caustic soda or
potash of suitable concentration is usedm The level of electro-
lyte is maintained above the surface of the electrode bells.
Above the surface of the electrolyte are only the cupolas ~o
Gas collecting bells 9 and 10 have their lower edge immersed in
the electrolyte thereby forming a seal for the gases. The large
area of elE:ctroly~te in contact with the atmosphere causes, after
2-2.~ years, carbonization of almost one ha:~f of the total amou~it
of alkali in. the electrolyte. Carbonized electrolyte is removed
from the cells and is regenerated ~causticized) by treatment with
limy. Temperature of electrolyte is maintained at 6Q to 70 de?
grew . Temperature regulation in high-load cells is attained by
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flowing water over the external, surfaces of the cell casing. For
this purpose there is installed along the upper edge of the cell
wall a perforated water pipes The water flows from the cell wall
an the floor and is then discarded to the sews r
Feed water is supplied to the cells from a common
tan's supplying a group of cells and provided with a constant
level device? Electrolyte level is maintained by a float ac~
tuated regulator, each ce11 being so equipped
Cells with double plane electrodes are built for
loads of 6000 to 11.000 amperes. The 11000 amperes cell has 11
cathodes and 10 anodes. The length of the cell is 1080 miL1i-
meters, its width 860 m3.11ameters, and its height 1220 milla?
meters. Use of double electrodes increases electrolyte carcu~
lotion, decreasinb gas saturation; therefore, in spate of the
plane form of the electrodes and almost double height of the
electrodes, as compared with 'the plane electrodes described above
the voltage of the cell with double plane electrodes is somewhat
lowero
Figure 95 shaves the dependence of cell voltage on
current density. The cells are usually operated at current
densities of 100-600 amperes .per square meter, which results
in voltage fluctuation from 2.1 to 2.3 voltsm
Closed Ce11 with Double Electrodes
Electrodes of this cell consist of two parallel. plane
iron sheets welded to two iron current conveyers, The distance
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Voltage
in
volts
Figure 9Sm Dependence of voltage upon curxent density'
in position by means of ebonite nuts. These bolts are about 12
millimeters long, located between the electrodes they hold the
diaphragm in fixed position half way between the electrodes. The
body of the cell is made of welded iron sheets 3 millimeters thick'
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betYaeen the sheets of the electrode is about 50 rnilla.meters; that
betTaeen the working surfaces of anode and cathode about 12 milli-
meterso The upper part of each sheet is provided with several
apertures to permit circulation of the electrolyte. Anodes are
nickel plated while the cathodes are sand blasted
The electrodes are fastened to the cast iron or steel
cover provided with partitions forming a single overall bell for
hydrogen and several bells for the oxygen, ~p;~y~en is removed
through outlet pipes from each of the bells To the oxygen bells
is attached a diaphragm of asbestos cloth, In view of the short
distance between electrodes ~~12 millimeters) to avoid adherence
of the diaphragm to one of the electrodes small ebonite bolts are
inserted through the cloth in several places and are maintained
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flanged at the topo 2'he cell cover is bolted on to this flange;
seal is provided by a, rubber gaskete
Normal current density of the cell is 600 amperes per
square meter' but due to the decreased distance between electrodes'
amounting to 12 millimeters, and the efficient circulat~.on of elec-
trolyte, attained by the same principle as in the cell having
double plane electrodes, the voltage is of only about 2005 volts
Low cell voltage makes it possible to dispense with auxiliary
cooling? Spontaneous dissipation of heat through the cell walls
holds the temperature within the limits of I~0 to 50 degrees,
Caustic soda or caustic potash are used as the electralyte~ The
cells are fed with distilled water, manually,
Small load cells are built for 1240 and Z~00 amperes
having three and five electrodes, respectively, but, of courses
the passiba.lity of constructing larger capacity cells is not ex-
cluded?
3. Monopolar Cells w-th Complex Electrodes
Cell with Louvered Electrodes
The primary and essential purpose of the design of
cells with louvered electrodes is to achieve separation of gases
without the use of a diaphragmm
Arrangement of a cell without diaphragm is shown in
figure 96. Louvered electrodes 1, the construction principle of
which has been described on page 209 [of original document] ter-
rni.nate at the tap by wide slats 2. The electrodes are suspended
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f rorn the cell. cover 1~, and held by
through Insulation bushings 3,
is divided in longitudinal direction by iron
nuts. The covex
'nto a number of compartments which serve as gas
paxtit~-ons ~, 1
fastened to the cover are located in the
bells. The electrodes
iron casing of the cell b.
' re 6o cell with louvered electrodes: 1 ~?
F~.gu 9
~~
~ - cell cover;
ectrodes? 2 -slats; 3 -isolation 1~
louvered el ~
' ions ? 6 -iron cell casing; ? -outlet pipes;
? iron party-t ,
rol e is maintained at such a level that
The elect yt
' erred into it to a depth sufficient to f orrn
the gas bell, are Zmm
The ases axe removed through exit pipes ~
a hydraul~.c sealo g
nd Into a common main. Gas bubbles on de-
and collectors 8 a 9
themselves from the slats of the electrode rise ver-
taching
Merin the slat disposed above slide along its
t~:cally and encoun g
'nner s ace of the electrode without penetrating
surf ace into the ~. P
between the electrodes. The saturation of the
into the space
of the electrode with gas causes intensified cir-
inner space
f electrolyte which promotes the suckingbin of gas
culat~on o
e inner space of the electrode, The gas emulsion
bubbles ~.nto th
es the interior of the bells; at the electrolyte
an rising reach
es se crate from the liquid which descends aga~.n
surf ace the gas P
into the interelectrode space,
On using louvered electrodes it is passible under
? ons to separate tyre gases without resorting to a
certaa.n condxti
't is readily apparent that completeness of
dis.phragm. However i
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ss o eration of such a device will depend
gas separation arld f a,ultle p
t u on the maintenance of a constant gas pressure
to a great eaten p
uctuatian of the pressure the liquid within
within the bells. On fl
? and rise, d.istur'bing the circulation and ex-
the bell. s wall fall
1 the inner space of the electrodes rota the
pell~.ng the gases fror~
ctrod.es. Good separation is attained only in
area between the ele
'mited loads, that is precisely in those instances
small ce11s, at 11
ensure constant pressure of the gases. Tn large
when it is easy to
' stallat1.ons fluctuation of pressure always takes
industrial xn
r. the reason of d~,~'ferent resistances of gas pipe
place, ~.f only f o
? ~ ~ atian oaf lz.quid seals in the pipe l~.nes, unequal gas
l~.nea~ form
d the like, as a result of which. operation without a
removal a an
diaphragm is found to be unsatisfactory.
herefore in later desa.gned cells lou~rered electrodes
T
' d bu.t only for the purpose of decreasing gas sa.tura.tion
are reta.~.ne
' crease the surface areas; to obta~.n separation of the
and to ~.n
'nodes are surrounded by a diaphragm of asbestos fabric
gases the cat
suspended from the rz.m of the gas bells.
Electrodes used in these cells consist of a large
number of vertically disposed thin and narrow non strips,
fastened together by means of bolts.
A cell of this type is shoran in figure 97 ~ The iron
asin is closed with a co'~er ~., sealed either by means of a
c g3
1 or a flange c~,osuree The coyer is provided with
hydraultic sea
artitions forming the .bells to which are suspended asbestos
p
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diaphragms closed at the bottamti For the circulation of the elec-
trolyte, small round openings are provided at the lower end of the
di aphragm.
Figure 97 ? Cell ,nth laminar electrodes ; 1 -~ larrunar
electrodes (ca.thodes}; 2 -clamping bolts; 3 -iron cell casing;
- cell cover; ,~ - rods for suspension of cathodes (current
conductors}; 6 -anodes; 7 -lugs for fastening of anodes;
8 - negative current bar; 9 -gas outlet pipes; 10 -connecting
channel for hydrogen.
lnsic'ae the diaphragm bag are located the lantinaz^
cathode 1, suspended from the cell cover by meaxls of rods ~'
which serve as current conductors. Anodes 6 located outside of
'the diaphragms are fastened by means of bolts and lugs 7 to the
cell casa.ng? Correspondingly the current conducting positive
bus bar. is fastened to the cel]_ casing, while the negative one
8, to the cathodic conductor 5, With this system of electrode
attachment the cover has fewer current conductors far th.e
electrodes which simplifies assembling work, Moreover the cover
ha.s fewer seal.ings, and finally a more even distribution of
current to the electrodes is obtained
'I'he cell cover has only two gas outlets g; the
right-hand outlet for ohygen, which collects between the hydrogen
bells, and the J.eft~?hand outlet for the removal of hydrogen; to
make this possible all the hyt~rbgen bells are connected inside
the cell b3T channels l4.
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tral to there is used a solution of caustic
As the elec y
e to the closed construction of .the cell,
soda ar caustic potash. ~
t in contact with the atmosphere and is not
the electrolyte r.s no
surf ace of the electrodes makes it possible
carbonized. Increased
current densities, Tr1e cells are built for
to operate at high
0 am eyes. Average voltage of the cell at a
loads up to 1800 p
oad is 2.1,9 voltsm Fur'ity of the gases: hydrogen
10000 amperes 1
.~-99.9 percent and oxygen 990 Percent.
99
n be installed in series of 2~Ow3~0 cells w~.th
Ce],1 s ca
d of voltage from X00 to 700 volts. To save floor
a curren~~ fee
a.ce the cells can beinsta.lled in se~reral tiers.
sp
somewhat different construction of a cell of the
A~
is shown in figure 98. This cell operates at very
same type
current density, and accordingly the electrodes are
ha. gh
? ~ e r closely together and provision is made for inM
pos~.tianed v ~
c~.rculatian? The cell casing 1 is hermetically
tensive electrolyte
r 2 bolted to the casing flanges. Welded to the
closed by cove
1e a: Ten bell 3. To the flanged ram of the bell
cover r.s s, sing ~~
a rectangular Iran frame ~. having welded on sections
~s fastened
e iron, forming an inversed trough, To the angle iron
~ o.f. angl
,stened bl small bolts diaphragm bags 6, open at the
ledge are fa ~
de of asbestos fabric, which surround the anodes 7.
bottom? acid ma
Anodes and cathodes are assembled of iron strips 11~
2 millimeters wide and are 0.25 millimeters thick in
why. ch are ~
bode and 0.63 ~-1lameters ~th~.ck in the anode, Round
the cat
es are embossed on the straps, their height being 1
pratuberanc
? ~ 'n the cathode and 1..~9 millimeters in the anode, which
m~.11.a.meter ~.
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mainta~.n the strips at an equal distance from one anothere The
cathode cansi.sts of 600 strips and. the anode of 220, After being
assembled the anodes are nickel plated. The strips are welded at
one end to the current conductor plates 8, The entire electrode
is also held. together by two bolts passing through suitable
apertures in the strips. The electrodes are suspended from the
ceJ.l cover by means of iron rods which are welded to the current
conducting p~l:tes 8. Location of the rods which serve also to
conduct the current is such that the rods supporting the anode
are within the bell while those of the cathode are outside of its
Figure 98~ Cell w~.th slat electrodes far high
current density operation;. 1 -cell casing; 2 -iron cell cover-
3 -common oxygen bell; !~ -iron frarne; 5 -sections of angle iron
6 -diaphragm bags; 7 -anodes; 8 -current distributing plates;
9 -gas scrubbers and coolers; 10 -empty diaphragm bag; ll -iron
electrode strips?
The anodes, as was mentioned, one Located within the
diaphragm bags, hence the oxygen passes inside the bell. The
rising hydrogen is led by the angle iron trough into the space
bet~reen the bell and the cell casing. The gases then pass into
scrubbers and coolers 9. Here the gases are cooled, are freed of
alkali and then pass into the manifold pipe lines. dater which
condenses in the scrubber^s flogs off through syphon tunes ex-~
tending to the bottom of the bell and is returned to the cell
into the cathodic ar the anodic section respectively.
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'rculs.tion of electrolyte is Produced in the
Forced cl
m t dia hragm bag 10, which hangs parallel
cell by the use of an e p Y p
fram the. edge of the bell. `Z~he electrolyte
to the electrodes
en flows through the bag to the bottom of
separated from the oryg ,
'n fram the space between the electrodes the
the cell, d~,splaci g
li hter electrolyte containing gas bubblesm
g
trol to used is a solution of caustic potash?
The elec y
? d in the electrolyte to a depth suff~.dent to
The bell ~.s ~.mmerse
n adequate hydraulic seal. Distilled feed
ensure formation of a a
cell through an inlet pipe welded to the cell
water flaws into the
f the electrolyte level below the normal limit
casing. Lotiaern.ng o
he noise caused by the gas escaping thraugh the
is detected by t
the scrubbers 9. Electrolysis is conducted at
syphon tubes ~.nto
55_C~ degrees.
c~,eristic features of this cell (figure 99) are
Ohara
the electrodes and the method of gas removal fram
the design of
odes l are made of a double iron screen welded
the cell. E1,ectr s
urrent conducting plate 2. At the bottom the screens are
to the c
small channel iron bar, and have to increase their
welded to s
' several spacers 3~ Dimensions of the electrodes are:
riga.d~.ty,
' ' meters width ].000 ma.llimeters, thickness ~0
height 1300 ma.lla. ~
? sh of the anodes is nickel p],ated. The
millimeters. The iron me
rted b ten current conductors from the gas
elec~~rodes are suppo Y
ire electrically a:nsulated from the bell s
collecting bells and
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Cell with screen electrades~ 1 -screen
~. gul_~?
nt distributing plate; 3 a screen spacers;
electrodes; 2 - curre
collecting bells= ~ -outlet pipes for
~ -lugs supporting gas
. - collecting pipes for the gases, 7 - Ver-
oxygen and hydrogen, 6
.n i es; g _ bell pockets; 9 - bell
t,ical extensions of collects g p p
? as i es; 11 a rubber sections for in-
run strip; 10 - ma~.fold g p p
sulatiorl of cells from pipe lines?
bells are supported by lugs ~. resting
Gas collecting
' n ce11 casing. The cell casing has two
on the rim of the fro
? es far the removal, of hydrogen and oxygen?
welded in outlet p~.p ~ s
hese outlet pipes are welded collect~.ng p1Pe
Inside the cell/. t? t hese ex~
rtical extensions 7? The number of t
6, provided with ve
? i e is equal to the number of
tensions in the oxygen collecting p P
o en collecting pipe it is equal to the
the anodes, in the hydr g
Each bell has a poc~iEt 8~ into which pro
number of cathodesw
' n of the gas collecting pipe. The hydrogen
jests the extens~.o
ort the diaphragm which is open at the
collecting bells supp
is fastened to t~~le bell by bolts and
bottom? The diaphragm
0 gen collecting bells have no diaphragm
shaped strips 9~ ~
hotter than the hydrogen bells. The bottom
acid are somewhat s
ell, extends below the upper rim of the strip
edge of the oxygen b
e escape of a portion of the or~rgen into the
9? This prevents th
space between two adjacent bells.
collecting within the bells pass through the
Gases
et i es 7 into gas collecting pipes 6 and then
pockets, and out/ p p
'nle~ ipe enter the mani~'old gas pipelines 10,
through an ~. p
e cell casing. To avoid leakage of current, tie
supported by th
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cells are insulated from the pipeline by rubber inserts 11.
The electrad.es are maintained at a distance of 65
millimeters from each other at their center, which with a 50
Millimeter thickness of the electrode corresponds to a distance
of 1~ millimeters between cathode and anode surfaces, The cell
operates at a current density of x.50 amperes per square ~ ter
and at a temperature of b5 degrees; the voltage under these con-
ditions is of 2,Q~-2,1 volts The load of the cell. is ~Q00
amperes, ~.Chis load can be increased, of course, if the number
of electrodes is increased
wash periodically the diaphragm.
iron deposit, increases its resistance and makes it necessary to
of the diaphragm, reslr~.ting in obstruction of the por. es by the
mation of a spongy iron deposit on the cathadesb Meta11~_zation
anodes, a progressive meta,lli~ation of the diaphragm and for-
on an iron screen results in a gradual dissolution of the iron
not as good. The difficulty of producing a good deposit of nickel
having double plane electrodes, the circulation of electrolyte is
has an extensive electrode surface; but in comparison with a cell
of gas removal it is most readily assembled a.nd dismantled acid
In camparisori with other cells of the open type
the cell possesses the advantage that due to the original method
Tn the USaR cells have been designed of several types
for different loads Cell V-3 with double perforated electrodes
is intended for use at large hydrogen producing installations and
is accordingly designed fora load of 1L~000 amperes.
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The arrangment of the cell is shown in figure 100.
The cell casing 1 is of welded sheet iron 5 millimeters thick
and it is provided at the top with an angle iron flange. The
cell is closed hermetically by a bolted cover, sealed by means of
an asbestos-rubber cement gasket coated with asphalt. Fastened to
the cell cover are 21 electrodes; 10 anodes and 11 cathodes,
The anodes are Located inside the gas collecting bells l~~
welded 'Lo the cover, and are surrounded by an asbestos. diaphragm
which is attached to the bottom rim of the bells by means of
strips and bolts.
O~~ygen passes from t~~.e bells into callecting pipe
2, the hydrogen from the space between. the bells into the parallel
pipe 3~ The hat and moist gases carrying droplets of electrolyte9
pass for cooling and scrubbing into small columns 1~, whic~i are
identical in construction for both the hydrogen and the ox~rgen~
The gas scrubbing columns are supportecl directly on the cell
and consist of an iron cylinder l~0 m~.llim.eters in diameter
and 1000 millimeters high, Inside the column is a cooling coil
5, a g~~s bubbler 6, and a screen "l, for breaking up the foam
From collecting pipe lines 2 and 3 the gases having a temperature
of about 70 degrees enter into their respective scrubber sunder
the bubbler)e The gases then pass through a layer of water (or
more accurately a weak alkaline solution) filling the scrubber;
thus they are washed free of droplets of entrained alkali and
cooled to 3Q degrees. The cooled gases pass through screen 7
and into the corresponding manifold pipe lines 8.
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Fi rure 100. Cell V~-3: 1 -cell casing; 2 -- cal-
g
i e for oxygen; 3 ~- hydrogen pipe; ~. -column for gas
lect~.ng p p
- coolie coil; 6 -gas bubbler; ~r -foam breaking
scrubbing; ~ g
~ .. as pipe manifolds; 9 - cooling tails; la .. water
screen, g
~? cooling water pipes; 12 -sewer discharge; 13 and
~p~pel~.ne , ll
1~~ -cooling water valves; 15 -gas collecting bells.
To maa_ntain the temperature within the cell at the
level of 7a degrees the cell is equipped w~.th two cooling
normal
thraufh which circulates cooling water which flaws from
caa.ls 9, g
0 throe h two parallel pipes first into the coils of the
p~.pe 1 g
s and then through pipes 11 into the cooling coils of the
scrubber
from the coils the water is discharged, through a funnel
cell,
sewer i e 12~ Caoli_ng water system is prava.ded with valves
Into p p
1 b means of which cooling of the cel~_ can be cut out and
13 and 1 !. y
only the scrubbers cooled?
The gas scrubbers, as described on page 211 [of
on inaJ. document) serve also concurrently for automatically
g
su 1 ing the cells with distilled feed water, for maintaining
pP y
the electrolyte level at the proper height, and far equal.iLing
h drogen and oxygen pressures wa.thin the bells. The cell can
y
o erate with gas pressure fluctuations in the manifold collectors
p
a0 millimeters of water colw~n height. Under such cone
up to ~
ditions inside the cell the pressure of hydrogen. and o ~~ gee
9
constant value equal approximately to boa-bra
remains at a
millimeters of water.
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the electrodes of cell V-3 (f~-gure lOl),
DeS:~gn of
from the designs of previously d1scussed elec-
~?f fers somEwhat
lectrodes, anodes and cathodes, consist of two
erodes. The e
n sheets 2 millimeters thick, measuring 1000 x
perforated iro :
ed at a distance of 30 millimeters from
1000 millimeters, dispos
sheets of the electrode are welded to three iron
each other, The
l T.nto the tap pare of the current conductors
current conductors
er ins 2 by means of which the electrodes are
are scre~4red Copp p
and the current is led in. At the point of
fastened to the cover
ent conductors through -the civet, seals and an-
passage of curt
ductars from tY~e cover., are provided by asbestos-
sulata..on of con
hers and vulcanized fiber bushings ~., fitted
rubber cement was 3
over the lead in pinso
101 Electrodes of cell V-3: 1 -iron current
Fl gore ~.
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-asbestos-rubber cement gaskets;
`s a anent from the description of monopolar cells,
As ~- pp
eeded in their operation does not exceed 3~-1~0
the amount of power n
Conse uently at large hydrogen producing installations
Kilowatts. q
'n o eratiorl several hundred individual units, which re-
there are z p
ar e area of buildings, large expenditures far leads'
quire a 1 g
' on of long pipe lanes and .finally complicates servicing
installati
' in small installations with m~nppolar cells there arise
On e quzpp g
' ection of direct current sources since they
d7.fficulties Unth sel
of hi h intensity and relatively low voltage. In
require curl, ent g
,.
' mechanical converters of such characteristics as
seallat~.on of
~nes themselves require much space. The use
costly, and the ~rnachi
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of mercury rectifiers is here not expedient because of their poor
efficiency in low voltage operations,
Therefore in spite of the very simple construction,
ready assemblage and maintenance of the monopolar ce11s, in recent
years the bipalar cells are being utilized increasingly more of tens
~, Bipolar Cells
Box Cell.
The main dii'ficulty in the construction of a bipolar
box cell is the arrangement of the box which must not be a con-
ductor of electricity, Sn the cell of figure 142, the box con-
sists of separate frames 1 and 2 bent to a rectangular Upshapee
The channels of frames 1 face inwardly those of frames 2 toward
the exterior of the baxm `rl~.c~ ~fr