Aly Designation: G3 14
Conventions Applicable to Electrochemical Measurements
nahh
‘Standard Practice for
in Corrosion Testing’
1. Sempe
1.1 This practice covers conventions for reponing and
spaying electrochemical omraion data, Conventions for
ppolntal, cutest demily, electrochemical impedance and
{Adminance x well x conventions fr graphical presentation
‘ofeach data are slides.
1.2 The valves sttad in ST its ate to be regard as
Sandu. No oer units of measurement are included in thi
Sandu. See alo 7
13 This standead does not purpert 10 address al of the
safety concemts, it ats ascot sth Hts ee It #8
responsi ofthe user ofthis standard te establish appro
priate sajery and heath practices and determine the applic
bits of regulary lineation privet we
2. Referenae Dacsents
ASTIN Satan
EIASTM SL 10Stanfan! for Use of the Inerationa
System of Units SI the Mosera Mesie System)
3. Significance and Use
SI This practice provides guidance for reporting
displaying. snd pling elecichemical comnion data apd
Includes fecommendstons on signs and conventions. Use of
this practice wil result im the reporting of elecracherical
sorrnon data in a standard format, fasating comparian
Tetween data developed at diferent laboratories ora diferent
1 The resommendations olin in hi stn my he
Ublized when recording and eporig corosion datwobuained
trom electrochemical tests such potion and poentio-
dynamic polateation, polarization resistance, elcewchemical
impodance and admitunce messunmens galvare comexion,
and open circuit potential measurements
4 Sign Convention for Electrode Potential
4.1 The Stackholm sign invariant convention is reson
mended for use in reporting the results of specimen potential
tmessurements in comosion texding. In thie convention. the
Postve dieeton of elecuude potcatial implies an increasingly
‘oxaizing condition a the elected in question, The positive
“rection ss alo been denote the noble direction besans
the corosionpotetals of ment noble metal, sch as gl ate
‘more poniive than the nonpusive base meals. On te eer
Tand, the negative direction, often called the active direction,
twocialed with cedicii and comeqietly the covesion
Potentials of active metal, ach as magnesium. This conven
on ws adopted unanimously By the 1083 Interadonal Union
‘of Pure ant Applied Cherisry as the standard fr electrode
Potent
42 In the comtext of a specimen elestode of unknown
potential nan ages elect, conser the cite owe
1 with a toereneselectode connacted ta the ground
‘enminal ofan easiometr. the electrometer readsen scale
‘shen the poirty sich i negative the specimen elec
Potmial 1s neguve (telatve 10 the relerence elas
Conversely, ifthe electrometer eads on scale when olay i
prtve the specimen potentials positive. Om the other and,
Htbe specimen clacrode is connetied othe growod trial
the potential willbe postive ithe mete ison Scale When the
polarity switch isnegative, and vee versa
ott simple steam ean be peromed follows imme the
‘Sich Wacom the dy ecatage The orden noe
ei end main aaa@ oo
"1G. Schematic lagramotan apparatus to Measure Eectrode
Potential ofa Specimen
5, Sign Convention for Electrode Potential Temperature
Coctients
S11 Thor ate two types of temperate coelcients of
cecode pote: other ampere coefficients ad he
thermal eoeticienl. The sign convention recommended fe
both ype temperature coeicens i tht the temperate
oeficent is postive when an insteae in temperate po
‘duces an increase (ait besomes oe postive) i the
lestcde poeta. Likewhe, the second tenigeraure coc
‘ents postive when an increase in tempestore produces an
Increase that is. it becomes more positive) in the fst em
perature coefficient,
6. Sign Convention for Current and Curtest Density
161 The sign convention in which ane coments and
cure densites are considered postive and eathoecuseats
fn eurrent demsties ae negative te recommended, When the
ppt pled esi the logarithm of the cure dens
nly the absolute values ofthe current density can be pleted,
Tn sch pts, the values which ae cae shoul e ley
dlifereoisted from the anode vale f ath ate presen
7. Conventions for Displaying Polarization Data
“711. Sign Conventions The standard mathematical practice
for plating graph ts recommended for displaying electron
chemical coronon data. In this practice, posite Yalu ae
Plotted above the origin on th ordinate ain and othe ht of
the origin om the avcisa axis. to logarithmic plot. the
fascias ae increases from el 0 sgt and the oxnte
‘alu meres fo Botom oo,
“12 Cunrent Desi Potential Plots uniform convention
js recommended for pling carent deity potenti dts,
rarely plot erent density alg the abscnsa and penta
fone the oni, In caren density potential pots, the
urent density maybe plotted on near foarte axes. Ta
‘ener loguitonc plots are beller suited to incnporition of
‘vide ranges of curten density dataand fr demenstatin Tae
Felitinsiaps. Linear plots are recommended for sies
‘Which he caren dens or potential range ysl orn cases
vere the region in which he curren ensity changes from
anodic w cathodic is imporsant Linear pot re also used for
the determination of he polarization revistance B,- which in
‘ened asthe slope of a potental-curtent density plo at the
comovion potential Fg. The relationship between the pot
[ation shane Rath erosion cute dees a 835
follows 2.3
(rd.
node Tafel slope,
alae Tall slope, and
the dlls = Fog. where F is the spe
poeta
Fig 2 a plot of polation, EF... venus cament
densi (old ine) Irom which he polanvationresistnce
ts bovn determined tthe slope a the curve al the common
potenti Ea
1.3 Potential Reference Points plats whexe elestrode
potentials are displayed, some indeation of He conversion of
the values displayed to both the standard hydrogen electrode
sale(SHE) ane saturted calomel electode scale (SCE) is
‘eommended if they ae known. For example. when lect
ternal plod atthe ordinate. then the
Shown the extrem let of he plo and the SHE sale shown
Atte exlmme right, An aliwutive, in cases where the
TERE TECTOIE Wan HT ETRET SCE OF SATE WoT BET
‘how on he potential axis the potemials ofthese electrodes
rence wed, Incanee whe
Showa onde plo an
For example, i te ease of a silversier chloride reference
sleetrode (1M RCD, the conversion cull be shown nei
owas
where F represents electrode potential measured against the
‘Sher iter corde siandard UI M RCD.
7A Unite—The commended unit of potenti the ol In
cases where only snl potential anges are covers, ilivlts
‘oemicrowoitsmay housed, The Sunt for erent density re
“ere per square meteor mllmpere per square centimctte
(EEEASTM St 10). Stil in use are unite expressed
amperes per square ceamete, and microumperes Per sauare
75 Sample Polwzaion CurvesSample polarization plow.
employing these recommended practices are shown in Figs
246, Fig, and Fig. ¢ ae hypothetical curves showing at
sndactivepusive anode behavior espetively, Fig. Sand
6 are aul porzation data fr Type 480 sales see UNS,
410) (4) and 10 aluminum samples), Fis 3 and i
exhibied to Mlustate graphically the location of various points
trod in gisevoion of lestochemicl methidh of corrosion
testing The purpone of Fig. Sand Fig (is 40 shoe how variosG
Polarization E-E corr
Current Density (+)
(1G.2 Hypoteical LinearPolrizaton Pot
‘pes of electrode behavior canbe ploted in aceoedance with
the proposed conventions
‘8. Conventions for Displaying Electrochemical
pedance Data
8.1 Thee grpbical forts in common we for repting
leccchemcal impedance dats ae the Nya, Bod, and
‘Admitance formats, These formals are dscissed Fora simple
‘ectode stem modalld by an evant electrical ecu as
‘Shown in Fig 7. nthe convention uilized the impedance is
detined
where
‘eal or inphase component of impedance,
the imaginary or ouret phase component of
impedance, and
”
‘The impoance magnitude or modulus is defined as
(Zp 7). Forth equivalent elececalcrcitshown a
Fig. 7. the imaginary componeat of impedance
whee
requeney in yet per second (er he, He, whe one
He fees o 2x adn, and r= 29h, where the its
few are radians), and
cite in ral
“The phase angle is delino s
“The admitanc, Yi defined as
herewe a 8
FIG.3 Hypomtiea Catnsic and Anode Poleraston Digrom
Ta Gein
jor rssnee
se sO8
fag" NAL ef
So seat
ai
{or CIN DOSITY Ce. le
FIG.4 Hypotieties Catneic and Anodic Polarzntion Pets tor a Passive Anodeee
SORES ta te
fonda.
Feel component of impedance ate plotted t the eight of the
‘origin patallel othe + axis (abscisa) Nepative vals ofthe
e
UP cimeecamer aur Fr
esses
it
ee
gt
16.6 Typical Plarition Plots or Alaminum lateralnin 2 WAC Soliton
sminanee, and imaginary coraponce
impedance ae pled vertically fron
adinance. the origin parallel othe y aus
iB hous a Nyquist pl fe the equivalent ict
7-The frequency dependence of the data snot shown
is typo plo. However the frequency coe
heappropria impedance
fy from the origin of——
rs
F107 Easier Sine Conon
ASTM EQUIVALENT CRCUT
4
oy
* sed eistnce hn)
‘rigin etfs chinen st appropriate nonzero values of impede
tance magnitae antec.
"E32 Fig 9 shows atypical plot for the simple electrical
clscuit node of Fig. 7. The magoitude of the high fequcncy
Inpesancewheve he iapedanee magnitde is independent oF
fegueney correspond to The difernce in magninae
etwean thelon Fequency and thehigh frequency feguonsy~
Independent regions of innpedance magnitude cvresponds to
2, Tha rsisunces are identical to thine on the Nyguat
Format pot shown in Fig 8
"83 Inthe sewn tye of Hole pot, the negative ofthe
hase angle, = pleted om the inate and the base ten
Jogarithm of the fegueney is plowed onthe abscica Ta his
practice increasing values ofthe negative of the pase angle
fe plated inthe vertical direction frm the origi long the y
‘ti (onfinate). In this ema a pure capacitive behavior 8
plotsd sa postive value of 90". Fig. 10 shows aypial plot
forthe simple electra roel shown in Fig 7.
1K The ants for dhe Tesuoncy on bok pts are either
hertz (cycles per second) or radians per second (radians pet
second 2x radian per cycle mubigied by dhe number of
‘eles per second). The units af the impedance magnate are
‘haven. The units chnvci are obtained by multiplying the
‘eauzed resistance or impedance bythe exposed specimen
ara, The units ofthe phase angle are depree.
Kt Adminance Format (Compler Pane) The real comp
ent of admiuance's plot om the absetsaad the imasiary
comporent of amitunce i plted on the ovina. In this
Fratice posse vals ofthe real component of samitance
fr plowed to che righ of the ovsin pall tothe sax
‘seis. Values ofthe imaginary component of impedance
fare plot veriedly ro the origin parallel to the y ax
(Grate). Recommended unt for both ates te ob ca
‘he unis ofc’ are obtained by dividing the messured
te coneyponling axes. Higher freusy date points are
typically located towards the origi a the plot while ower
Frequency pins comespoa tthe increasing aside of he
itmpedance componens,
122.3 Recommended units for both axes are chavem?. The
unis ofmem® are obuined by mubiphing the meswed
resistance oF impedance by the exposed spocimen ares. For 8
resistor and capacitor. or dummy cell equivalent circuit, the
sssumedareas | em Regarding the impedance data shown in
Fig 8 forthe circuit of Fg, 7 the distance from the origi to
te fs (high frequency) intescept withthe absisa come
sponds to R, The distance between the fst intercept and the
secondo feguency) imercept withthe abscisstemespons
OR.
3 ade Forma:
82.1 Blectrechemical impedance data may be repre ss
‘wo ypos of Bode plo Inthe ist oase tho hase on Loavtha
‘ofthe impedance magnitude ce Modulus Zi plozed om the
‘udinate andthe base en logarithm ofthe fiequency is ploed
‘a he abscissa.Inthis practice increasing Fegue acy values ast
Ploted tote rightof ie origin pale! tothe # axis abscissa)
fd increasing saltes of impedance magnitude are pleted
‘ercaly fom the nein paae othe ass rat), Me
[ASTM EQUVALENT CROUT
a
i passamasanscney,
Impedane® Magnitude (oh)
Frequency )
‘Fla. Typical Plt for Simao Elected Model of.”[ASTM EQUNALENT GROUT
o
$6 oN
g :
2 . ‘
i a
B . :
& “
: : ‘
0"
Frequency (ha)
1. 10 Tplet Pot r Simpl Eecrodo tooo Shown nF. 7
ec od et lt
‘sdiitance (on) by the exposed ypecimen area. The re-
‘quency dependence ofthe ata not shoe explicit on his
‘ype of plo. The magnindss of the appoqrste admittance
‘components ines when moving away rom the ogi of the
‘omesponsiag ates.
9, Keywords
9.1 ac impedance: Bode: coaveatio: electrochemical im
pace specioncoyy: eleceechemical measurement elec
‘Mode penal linear poaszation, Nyquist poatzation ex
tance; paeatodynanic poluizaion; ference electrade
APPENDIXES.
X11 Comparison of Gibhs-Ostwald Convention to
[Nernst Latimer Convention
XII. Another sign comention the Nemst Latimer
‘coment, hs been used esters by physica anal
‘al chemist in deserting electrcheriea reactions. This
convention i based on the relationship
‘mea, Tables of potentials forthe oxidation of various metals
relane tothe stands tate hy open potential hive had we
‘Geculition (6) These Salus have been called “oxidation
Potential” 0 denote the use ofthe Nera conve
‘Thus theterm "eleewode petcaial” now implies the use of the
Gibby Stockholm conveaton.
whee
AG = change in Gis fice ener.
‘numberof chates per ato.
Cleewechemical equivalen in faradays, and
potetal according to the News atimerconveation.
A comequence of this convertion is thatthe sign ofthe
potenual depends upon the way hat the ection is Witten. For
cap, the adie disoltion of copper ean be expres
r
&
where
cu ‘metalic copy crystlline. wit activ:
Cu"jaq) = cupic fon in aguenus solution, and
= One uot gate charge (a eleceon)
‘while the plating of copper can be writen a
Cx" (a) ce 26 vay
Io these two cases. the potential would have opposite signs
even though bth reactions occur simultncously on 4 spec
NL? Consequences ofthe Gbs-Stockhlm Convention
X121 To explore the comesences of the Git
Stockiolm comerticn, futher comider a conodiag met
surface
Mata) 20 wy
“The whole cllreation with a hydigen ference electade
would then be:
2a)
(aie) X15
The Gibts fine enemy change would be given hy the
expression:
here
= measured elaeode porntal of Fg 4Tr ths clecnade potential wee neste, then the metal
surface would be active und the reaction woul! wad tose
‘Spontancousy because the fre energy Is negative
X1.22 Consider the eect of increasing the concentration of
‘themetl ions ia solution in Fy 4. The egitim lecode
potential of te metal swface would become mare neble
ascoaling othe relationship
Ae= Haran Wes) wy
here
4 Snproprite gas Taw constant, and
‘AE = eleeuale poteal athe concenated solution miaus
levee potential inte itt solution,
‘Thus increases in he activity of the oxidized species. for
‘example, Ma, endo nea he electrode penta! On
the other hand at increas inthe activity ofa redused species
‘will decree he electrode ponent. Por example, colder the
alec eatin
Increasing the hydrox ion concentration reduces the elec-
‘nae potetial ofthis reaction,
‘X13 Fleetrae Potential Temperature Coefidents
X11 There are ro Epes of temperate coefciens for