!"#$%"&$%' ) * +,-,%,.

/, 01,/&%$2,3


4#5,/&67,

In this lab you will leain how a iefeience electioue is constiucteu by assembling a
CuCuS04 iefeience electioue. You will then use this iefeience electioue anu two otheis, a
silveisilvei chloiiue anu satuiateu calomel, to measuie the coiiosion potential (Ecoii) of
seveial uiffeient alloys. 0sing numbei lines, you will then leain how to conveit Ecoii foi
each mateiial to othei iefeience systems. When complete, you will have constiucteu a
galvanic seiies foi these mateiials anu calculateu the conveision factoi between the thiee
iefeience electioues. The conveision factoi foi one of these electioues will then be
compaieu to the theoietical value you calculate using the Neinst equation.

8"/9:%$;.2 * <=,%>$2'.">6/3 $- ?"1- @,11 +,"/&6$.3

The equilibiium ieaction occuiiing at the suiface of an electioue in equilibiium is calleu a
half cell ieaction. Foi the coppei electioue in the CuCuS04 iefeience electioue the half cell
ieaction is equal to:

!"
!!
!!!
!
! !" (1)

!"#$%& #($) $) *+$##&, -) - +&./%#$", +&-%#$",0 This ieaction is associateu with
a change in uibb's eneigy, !u:

!! ! !!
!
!!!!"!!"#$%& (2)

wheie !u
o
is the stanuaiu uibbs eneigy foi the ieaction anu K is the equilibiium constant
anu is equal to:

! !
!!!"#$%&'(!
!!!"#$%#&%!
(3)


wheie a is activity.

It is possible to coveit Eq. 2 to uiffeient eneigy systems, foi example, since this is an
electiochemical ieaction involving the passage of cuiient, it is moie convenient to
expiession the change in eneigy in teims of electiical potential, E, using the ielationships:

!! ! !!"# and !!
!
! !!"!
!
(4)

wheie E
o
is the stanuaiu ieuuction potential foi the ieaction on the noimal hyuiogen scale
(NBE), n is equal to the numbei of elections tiansfeiieu in the ieaction (2 foi Cu
++
) anu F is
Faiauay's constant 96,Suu Cequiv. Substituting the expiessions in S anu 4 into 2 we have:

! ! !
!
!
!!!"!!"
!"
!"#$ (5)

Equation S is iefeiieu to as the Neinst equation anu is useu in the analysis of many
electiochemical cells as well as the constiuction of Pouibaix uiagiams. Beie we will use
this expiession to evaluate the CuCuS04 electioue system.


0AB,%6>,.&"1 C%$/,2;%,3
1-2&#3
Be suie to follow all safety pioceuuies outlineu in the S0P foi hanuling chemicals anu
weaiing peisonal piotective equipment.

4-#&+$-5) - Check that youi station is set up with:
1. A Biologic potentiostat tuineu on anu softwaie.
2. Nateiials foi constiucting a CuCuS04 iefeience electioue.
S. Satuiateu calomel iefeience electioue (SCE)
4. 1(-+&. silveisilvei chloiiue iefeience electioue
S. A uiip tiay containing a beakeiflask of u.1N souium sulfate solution (pB=9)
6. The following metal electioues in solution:
- Aluminum (99.999%)
- Caibon steel 1u18
- Coppei
- Stainless steel Su4L

C"%& D * E="&F3 D.362, " %,-,%,./, 01,/&%$2,G
In the fiist pait of this lab you will assemble a CuCuS04 iefeience electioue. The
instiuctions foi uoing this aie below:

1. Nake suie the coppei iou is fully buinisheu. Remove any anu all contaminants by using a
new, unuseu, non-metallic scouiing pau oi sanupapei. uieen scouiing paus aie
iecommenueu foi the pioceuuie. When gieen scouiing paus aie unavailable, sanupapei
can be useu. Be suie to iinse the electioue aftei buinishing.

2. 0nce the coppei iou assembly has been fully buinisheu, avoiu any contamination, which
may occui befoie the iou assembly is ieattacheu to the tube foi example, the pB fiom
ungloveu fingeis, uiit, oil anu any othei foieign substance that may come in contact
with befoie being ieattacheu to the tube. may cause incoiiect ieauings.

S. Reattach the iou assembly to the tube. Banu tighten only as not to uamage the iubbei o-
iing by ovei toiqueing. But, be suie to tighten well enough that the electioue uoes not
leak.

4. Auu coppei sulfate to the tube (see cioss-iefeience chait foi amount) anu then auu
watei up to the bottom of the plug assembly thieaus. Be suie to iemove any ciystals
that may have stuck to the thieaus of the tube. @$BB,% 3;1-"&, 63 /$%%$367, ".2
B$63$.$;3 B1,"3, ;3, /"%,H

S. Sciew the piesatuiateu plug assembly onto the tube enu, making suie again not to ovei
toique the o-iing.

6. Shake the electioue until the CuS04 anu B20 solution becomes uaik blue in coloi anu
completely satuiateu with the CuS04. Theie shoulu always be CuS04 ciystals at the
bottom of the electioue to insuie a satuiateu solution.


C"%& DD * 0/$%% I,"3;%,>,.& J36.: K L6--,%,.& +,-,%,./, 01,/&%$2,3H
The potential foi an electioue in an enviionment is ielateu to the kinetics of the oxiuation
anu ieuuction ieactions. When these ieactions aie at "steauy state" (i.e., not changing) we
iefei to the coiiesponuing potential as the coiiosion potential, Ecoii. While this may be
similai to equilibiium it uiffeis because the coiiosion ieactions aie not ieveisible at this
potential.

1. Place the CuCuS04 iefeience electioue in the flask containing the solution anu
electioues.

2. Connect the iefeience electioue to the coiiesponuing alligatoi clip on the potentiostat.
Connect the C1u18 electioue in the solution to the "woiking electioue" alligatoi clip.
Nonitoi the potential foi 1u minutes on the computei anu iecoiu the steauy state value in
the table in the Results section.

S. Repeat pioceuuie 2 foi all of the metal electioues placing the measuieu value in the
table.

4. Remove the CuCuS04 iefeience electioue fiom the flask containing the solution anu
electioues anu ieplace it with the AgAgCl iefeience electioue. Connect the iefeience
electioue to the coiiesponuing alligatoi clip on the potentiostat. Recoiu Ecoii foi each
electioue as befoie.

S. Repeat pioceuuie 4 foi the satuiateu calomel iefeience electioue placing the measuieu
steauy state value of Ecoii in the table below.



+,3;1&3

Table 1. Steauy state values of Ecoii in u.1N souium sulfate.
ECuS04
v
EAgCl
v
ESCE
v
Coppei
C1u18
SS Su4L
Al


M336:.>,.&

C"%& D * @$.7,%&6.: C$&,.&6"1 I,"3;%,>,.&3 8,&N,,. O/"1,3
It is common foi investigatois to use uiffeient iefeience electioues (scales) foi uiffeient
electiochemical systems oi applications. Foi example, a scientist may want to maintain a
chloiiue fiee enviionment foi a piecise stuuy of pitting potential oi a fielu engineei may
neeu a iobust "pioblem fiee" electioue to withstanu the iigois of pipe-to-soil
measuiements. Even within one application moie than one type of iefeience electioue can
be useu anu it is typical to conveit electioue potentials back anu foith between scales.
Potentials fiom the vaiious types of iefeience electioues aie typically conveiteu to the
noimal hyuiogen electioue (NBE) foi compaiison on a common scale. Conveiting between
iefeience electioues is similai to conveiting between Celsius anu Kelvin tempeiatuie
scales. In this section you will leain how to conveit between scales anu the NBE using
numbei lines.

1. The conveision factoi between SCE anu the NBE is u.271 v. To conveit fiom SCE to NBE
you must auu u.271v. To conveit fiom NBE to SCE you must subtiact u.271v. That is, if
you measuie the potential of an SCE ielative to NBE, the SCE woulu be u.271 v moie
positive than the NBE electioue. To visualize this, fiist wiite the values foi Ecoii you
iecoiueu using the SCE on the numbei line below, placing tick maiks anu the
coiiesponuing Ecoii value foi each alloy above the line. 0n the NBE scale below the numbei
line conveit each of the Ecoii potentials measuieu with the SCE to NBE. Copy these values
into Table 2 oiueiing them fiom highest (most noble) to lowest (most active). The table
you have cieateu is a galvanic seiies. Note that it is specific to souium sulfate solution.




Table 2. ualvanic seiies foi u.1N souium sulfate solution.
mateiial Ecoii, v vs. NBE








S. As you founu in pioblem 2, the potential of a given electioue is not changing when you
change iefeience electioues, just the fiame of iefeience is changing. In auuition, if you
measuie the potential between an electioue anu two iefeience electioues in the same
solution it is possible to calculate the conveision factoi between the two iefeiences. To
apply this knowleuge to a new system, in the uiagiam below, wiite in the Ecoii values you
measuieu foi the Cu18 electioue using the SCE anu the CuCuS04 iefeience electioues.




Now calculate the conveision factoi, !, to conveit !"#$ CuCuS04 %# SCE. BE CAREF0L 0F
TBE SIuN (+-):

! = ______________________________

4. 0sing the conveision factoi to conveit fiom CuCuS04 to SCE you calculateu in Pioblem
S, anu the conveision factoi we pioviueu in Pioblem 2, calculate the conveision factoi
!"#$ CuS04 %# NBE (be caieful of the sign):

Conveision to NBE = ______________________________



S. 0sing a similai pioceuuie as in Pioblem 4 except this time using the Ecoii you measuieu
foi C1u18 using the AgAgCl iefeience electioue,






!"#"$
&
'())
*+!&,-
&
'())
*!.+/
0
,-
#1# 2 +!&
#1# 2 !.+/
0
3
calculate the conveision factoi, !, to conveit !"#$ AgCl %# SCE. BE CAREF0L 0F TBE SIuN
(+-):

! = ______________________________



6. Now, calculate the conveision factoi !"#$ AgAgCl %# NBE (be caieful of the sign):

Conveision to NBE = ______________________________



C"%& DD * <=,$%,&6/"1 01,/&%$2, C$&,.&6"13

In Pait I, Pioblem 4 you calculateu an empiiical potential foi the CuCuS04 electioue vs.
NBE (a conveision factoi). It is also possible to use the Neinst equation, Eq S, to calculate
the theoietical electioue potential foi the CuCuS04 electioue ielative to NBE.

To uo this, foi the CuCuS04 iefeience electioue:

! !
!!!"!
!!!"
!!
!
!
!
!!!"
!!
!
! !
!
! !!!"#!

and a
Cu++
= m"+/# where "+/ is the activity coefficient and m is CuSO
4
concentration in molal (g
solute/g solvent). The satuiation concentiation foi CuS04 at 2u
o
C is S2g 1uug B20 anu the
activity coefficient (") can be calculateu by inteipolating the concentiation uata (x) in the
following table fiom Ajayi anu Wigwe (1978):

m
Cu/CuSO4

ggB20
"+/#
u.u9 u.1uu
u.1 u.144
u.2 u.1uS
u.S u.u8S
u.4 u.u7u

anu the ielationship:


!!!
!
!
!
!!
!
!
!!!
!
!
!
!!
!


wheie: yu<y<y1 anu xu<x<x1.

Now, using these values, calculate the theoietical potential foi the CuCuS04 electioue vs.
NBE anu compaie this value to the conveision factoi you calculateu in Pait I - Pioblem 4
above.

Empiiical:

CuCuS04 is _________________________v vs. NBE

Theoietical:

CuCuS04 is _________________________v vs. NBE