ELECTROCHEMISTRY

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600200067-7
• Release Decision: RIPPUB
• Original Classification: R
• Document Page Count: 6
• Document Creation Date: December 22, 2016
• Document Release Date: June 29, 2011
• Sequence Number: 67
• Publication Date: May 28, 1948
• Content Type: REPORT

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THIS IS UNEVALUATED INFORh9ATIDN FOR TI?IE RESG;ftCri
USE OF TRAINED INTELLIGENCE ANALYSTS
Russian pariodicai, Zhurrnel Fizicheskoy Khitei3, Vol XYt, No 3p 1$'a7, (FDB)
Per Abs 2T54 -- Translation specificaLy requeated.)~
T! B fAVICR ~ Ati l[tOPi EIEti'1'FigUC
IPl A ILI 301UTI0NS AT L014 TF21F'IIUTURF.3
Zeo 1Sal~:y;tova letid?S;` Lt)vi~a
Ph;~sico-l~temical Institute inte~l
L. Y.a. Karpov, l8oscow
8 Attguot T~lr6
IL is known that an electrode pressed from pondered Yron serves as the cotho;;t
in an Edison bati,arv. 7'he 5ehavior of tFia electrode at law temperatures is dis-
4.~notfiahed bo A number of oeculiaritioA. In particular, the basicoheracteriatio
of the eleett?ode, 3ta capacity (exprAeaed in'ampere-hours), greatly decressas wicit
t cara-
l
tooa
a lowerin8 of temperature, end at -25 to -3V degreoa the electrode e
pletaly breaks dovm. Since a Jungner-type ferrocadmfua electrode e~orks at these
temperatures, the cause of the Toes of capacity mey be considered to be in the
change of the properties of these electrodes nt low temperaturea.? This efx'cet
cannot be explained by fire cnalu;a of the properties of the solution because the
Ltter is the same in both casea~ This work will attempt to explain the cause
of the loan of capacity of en iron cathode at low temperatures.
The. tests ~rere made in an apparatus conatructod almilarly to tiwt described
3n the work of Lukovtaev, Levine, sad Frtuixlrt (Zhurn. t1+t khimi1.13, 915, ].y2d).
aea ,
d i
pawdere roe pr
t11xt of caustic potash xi.th a sgacific gravity of 1>28 - 1?30, i.e., an optimum
canrontration ioY' uors,? a". l~.R temparbturea, was used as the electra],7ta. A
DeMar flask with a mixture ox~ eacuhol and sc;lid carbonic acid served as a cryoalaR~
Rssnlts of the lisaauremvnt .Afar' Diacussioa?
The apparatus was considerrbly smaller in order that. tkte entire apparatus cou
be.placztd in a 10-cm diameter De~sar ilaak for the low-temperature testa. Purb
d uhder 1 OCJ =tmvapheres tea the object of study. A aclu-
e
Curves of cathodic red enodSc polarization at X20 degreoa C end -30 degrees C
? _l_.
CIASSI F ICATIaN ~~': _. _ ?.
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are ahosvn in Pigott: 1. (al:t -..slues o;. p~tentiaia era given with raterencp to the
roperaible hydrogen electrode in the same solution end. at the same tempox!sture),.
Tho cuawe et a low temperature in the Yield oY hydrogen ocorvoltaga has a ateopar
elope and lion 160 my higher, i,o., thn temperature rxetficiont oY overvo~tage is
9 my morn per degrees The anads curve also is steeper and 3nteraect,s the~abecr.asa
at a current lying approximately one ordor~cs7.e division on carv~lo-aor than at
room temperature.
At very loev rind no-current potentiUl4, tht fallowing phenoteenan is obse1rved.
At -30 depress, ar. io seen Erosr tile. frsy.dt, the steady potential ;s BO my more
negrt*.ive than at 0 degrees. Upor. connacti.rtt, the current, the potential mairtaine
a high negative value Tar sap tits an~i ';;hen'iradualls fells anti stops at a
potential approximately 20 ttxv mare negative than at 20 degrees. A hi~yh not?ative .
value of the standy potential is observed if the cooling is carried out in ?Lhe',
presence of a current; in the seer studied, t??tN current hrd a str$ng~tt: of severtiT
il
m
liempereo. If, however, the cooling is cr_rried out without a currant, this
potential has a more FositSvo vaL~e than at rontn temperature, bet nevertheless
1t is more negative than the t~pdie.en., Noaevexr, it trLe electrode is gub3ected
to cathodic polaritaiion even with a very emaLl current, the value of the poter_-
tlel sharply Changes to the negative side end, With a further increase of the
current, follows a curve which is obtained when a measLreaept is made frost thin
Zianre 1. Cathode (O,C~ asxQ Anode (4) Costae on
Poedered Iron at {20 awA -30o C.
ins curves of cathodic polarisaation at { 20 degrees and -30 degrees C on
omooth iron era compared In Figure 2. Aa for the possdared electrode, here also
the temperature coefficienC is appr.-xiatstely 3 tsv per degree. Rhe.pa~Lh of Lhe
esurvs ie steeper with a aY~ps of 0.12. Apparentliy this is due to the fact that
the sieasuremanta nn_thw ~g+i+th electrode are mstde in a field of considerably greater
dsasities of entrant. YJith regard to the ro-current potential at -g0 degrees, it
is l6 sav >AOae negative then the reversible, but more positive than at room tem-
peratara.
.STAY
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l
-~`'-~._
FSQnro ;, ~aLho3? Curses on Smaoth'Iron at ~?20 an3 -30o C'? .
Comps*ia~:n of the curves at room end lox t?enpe~raturea leads to the fol?ar-
ing retulte. First, the path of polsrization cux^rdo at lbx tc;;xperct,itre: has a
:noticeable atagrpor~?alope. second, the temperaturo aoeffici.ant of ovarvoltage is
amore tr:'ez 3 xr 'pcr degree, v.t:.ich i::; ai,coraz'.lY P,r~ot "or this interval of currocit
desteity,
?rh4+c drte tsrcea ue to suppose t2s?t at lsnv tamperaturea ttti.re is a fi.La
of oxtaea nr' aee7rL~d aaygan +tz! 'l:ron, even with rMgatS.ve f~ antiala~ Aa
tiiebarcte and Behr (Ztaohr. pUgaik. Chem. 58, 301, 1907) have already ahrnm, the.
potential of the iron. electrode in a ealuLion of its ealt? in an etmonp~here of
hpdrosen ip established ?sry aloxly ae a roault of tho diftYnulty of aeoarating
azygete from the aurlaae of the OlecCrode. At lax LemperaLttrea t'ne ldnetice ~t
this proasso ere probably aloxal down Sven more.nnd oxygen forme a stable layer
rf oxides on the attrfaae of the iron electrode. Apparea?.ly the influence of
this laver exrn~sraea itself both in rsteexier polarize:tion crtrvee and in a com-~
~nnn t*nm the ~en*Ie un evaluLion afaoa on iron Lhat if a small amount of oxygen
re~esine on the surface of a cathode after raatoratian, the overnoltage sharply .
ehitLe to Lhe negative aide and Lhe wh~~le curve has a conBidarablJ steeper slopes)
k
ed
The nature of thin tilu romgir_a unnxplainod? On the one hand, iL sea be loo
npm as a diesquilibriua< toraaetion xhich rPSUlts fray the oxidetior~ of iron by
traces of axygen in the solution and xhich is not removed in cathodic polariza-
tion beeeuae of the sloa~neba of the reetoratior. proaesa nt a lox temperature. L'n
Lho other bend, it la possible Lo suppose that with a decrease in temperature and
xitE praetiesl2y realisable potentials and a complete absence of moleoula~ oxygen
in the a~pstem, both the bonding.stability of the oxygen and its eaauttt on tna
surtsce increase. Yne exper3msrrtal data xFi^.it i'o M1~oa et p,aaent is i:.sutfictc.'t
to arks a choice between these two szpppsitione. ?t is entiroly probable that
the tilr, stable sL a lotR teaiperaturo and less stable at room temperature, not
an1J increases the overvoltage, bnt also peeairates the iron, caueinhr the shar*~
decrease in capacity of tho imn cathode at lox temperat,urea~;
Coneidarirrg the dual aotion of Lhe oxide tilts, it is possible to explain the
garLiaular ehanp,,es of the steady potential at Ctigh testpereturea os S:he fawdered
eu~ eoooth iron e3-idr are da ~eri.b.td above,. An increase of the overwltege causes
a shift of the steady poterntial Lo the negative aide, end pesaivatior.
STAT
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of the anode process to the positive: xida. Iii t'~c cage oY' o pc'derdd e.cecui?dda,'
the shift of the steady pctontiel and f.he currel;;.zcss Fotantia3 ici the nepAive
aide Can be traated as the fi:'~t stage of action of the .oxide film. In the case
of as eleotrode ai.thouti a ourrant, tho paspivatiea is increased and the potential
gx?ad-rally shifts to the p~sitivc aide, t+ut nevarthelaae remaining somewhat more
negative that, at xoott tomparatura, lf, honever, Eha coeli.ng is done without a
cwxent, the?paaalvation of the eLectrade,'aecumes considerably stronger and its
potentisl aequiroa a value which. is wsi~ positive than at roon temjx:rature. Ai
the case of n smooth claotrode the pasaivation baCOmea faster and its steady po-
t+enLlal at a lvae.r temperature niaaye has a ;Taro positive value than at room
temperature.
for a further explanation of the role of the passlvmting film a8 lorr tenr?
peretures, curvos of discharge and charge at room temperature end at -25 degrees
ware compared. It is aJ.Teedv kaovn [ram the classic Work of Foerster (2tschr~'
Blwlrtxwcham. lbal,ol, 1910} that ire the discharge of an iron clxtctrode at a
constant current, a horieontal platform, rorreaFwnding to the reaction Fe -^~ Fo"?
is a~b iorru~j a1`ter rhi.ch 'fie potential sharply ahiSta to the positive aide cad
a new plat$orn