Corrosion science, Vol. 23, No. 4. pp. 391-430, 1983 0010-938X/83/040391-39 $03.

00/0
Printed in Great Britain. Pergamon Press Ltd.

ELECTROCHEMICAL MEASUREMENTS IN
FLOWING SOLUTIONS
BRYAN POULSON

N.E.I. Power Engineering Ltd., Gateshead, Type and Wear, U.K.

Abstract--Fluid flow can influence both the rate and type of corrosion. Despite this most corrosion
tests especially those involving electrochemical measurements are carried out under poorly charac-
terized and unrepresentative hydrodynamic conditions. This paper reviews the characteristics of
existing specimens and then describes the development of a new design. Both the practical, including
monitoring, and mechanistic significance of electrochemical measurements in flowing environments
are then discussed.
INTRODUCTION
ELECTROCHEMICALmeasurements are now widely used in most fields of corrosion.
Detailed reviews are available which deal with the application of electrochemical
techniques in general 1,2,3 or specifically to pitting 4 galvanic corrosion, 5 intergranular
corrosion,8, 7 crevice corrosion, s stress corrosion crackingg, 1° and high temperature
high pressure situations? ~ However cautionary remarks have been made by LaQue, 1~
which should be digested with care. These include: (a) that much of what is termed
basic corrosion research has nothing to do with corrosion, e.g. pure Fe in de-
oxygenated 1 N H2SO4. Similarly those involved with real corrosion situations are
often not interested in mechanisms, (b) that fashionable equipment (he mentions
potentiostats) are used to grind out impressive looking data, often of doubtful
relevance, and (c) that size effects and the separation of anodic and cathodic areas
have a significance that is often overlooked.
Many if not most cases of corrosion involve some relative motion between the
corroding metal and its environment. Such movement can increase or decrease pro-
cesses occurring under static conditions; it can also introduce different types of attack,
e.g. erosion-corrosion, or cause problems due to deposition. Some typical examples
are shown in Fig. 1. Often solution movement is neglected or measurements are
carried out under poorly characterized and/or unrepresentative hydrodynamic
conditions.
Electrochemical measurements in flowing solutions can provide data on (a) the
rate of general corrosion and the possibility of other forms of attack, (b) mechanism,
by using the effect of flow as a diagnostic criterion, (c) the characteristic hydrodynamic
parameters, e.g. the rate of mass transfer, the degree of turbulence or the surface shear
stress, and (d) the composition of the solution by electro-analytically monitoring
compositions or measuring redox potentials, pH's, etc.
This paper is intended to review the application of electrochemical measurements
in flowing environments.
Manuscript received 10 February 1982.
Presented at the Meeting on "Electrochemical Techniques in Corrosion Testing and Research"
held at the Corrosion & Protection Centre in the University of Manchester Institute of Science &
Technology, 4-6 January 1982.
391
392 BRYAN POULSON

CONCEPTS AND TERMINOLOGY

At low relative velocities between metal and solution flow is laminar and at high
velocities it is turbulent. The transition occurs over a velocity range and depends on:
the geometry, the viscosity of the liquid and the roughness of the surface. The dimen-
sionless Reynolds number (Re) is used to take account of such effects and allows the
prediction of transitions.

Vd
Re -- (1)
Y

where V is the relevant velocity (m s-l), d is the characteristic specimen length (m)
and y is the kinematic viscosity (m2 s-X).
In turbulent flow there is still a thin laminar sublayer (thickness 8h) close to the
metal surface which results from viscous drag. If mass transport is occurring at the
surface there will also be a diffusional boundary layer (thickness 8d). The relationship
between the thickness of these two boundary layers is governed by the dimensionless
Schmidt number (Sc)

Sc = -7- (2)
D

where D is the diffusivity of the relevant species (m2 s-X).

The higher Sc is the thinner will be the diffusion layer and the more rapid will be its
formation. If both 8d and 8h start to develop together then ~h/Sd ~ Sc t. Associated
with the velocity gradient across these boundary layers is a frictional force which
may be expressed as a surface shear stress (Ts). It has been suggested that this may
control the mechanical stability of surface films.
The overall transport to the surface consists of bulk convection and turbulent
convection. With the former there is a net transport of fluid involved, e.g. along the
pipe: with the latter there is an exchange of fluid between the boundary layer and the
bulk. Both depend on the concentration driving force: bulk convection on D, while
turbulent convection is a function of the eddy diffusivity ~ (m z s-X). With some
approaches the molecular diffusivity is added to the eddy diffusivity in a modified
Ficks law. In other approaches the overall resistance to mass transfer is seen as the
sum of the resistances of the laminar and turbulent regions. Empirically this is by-
passed by defining a mass transfer cofficient Kas

rate of reaction
K = (3)
concentration driving force.

Mass transfer rates are also expressable in a non-dimensionless group in this case the
Sherwood number Sh, though sometimes the Stanton number (St) is used

Kd
Sh-- (4)
D
 FIG. l(a). Carbon steel bolt after erosion corrosion in pure water.
Fl6. l(b). Surface morphology of erosion corrosion on carbon steel in pure water.
 FIG. l(c). Deposition of magnetite on orifice plate causing increased pressure drop.
FIG. l(d). Dendritic morphology of deposit suggests electrocrystallization rather than
sticking particles.
E

G
C~

C~
Fro. 4. Impinging jet cell showing choice of jets and specimens.
 (b)
FIG. 19. Dissolution patterns in impinging jet tests. (a) C a r b o n steel after 18 h in
4 M NH4NO3 at 75°C. (b) Copper after 1 h in 0.1 N HCI containing 2 g 1-] Fe a~ at
35°C.
 Electrochemical measurements in flowing solutions 399

K
S t -- (5)
V
or
Sh
S t -- . (6)
ReSc

It can be shown by dimensional analysis that Sh nmst be a function of R e and Sc.

Such relationships can be derived theoretically, e.g. for the rotating disc this preceded
experimentation. However they are usually obtained as empirical correlations of
experimental data obtained within certain limits; they are usually of the form

Sh = constant Re x Scy (7)

x is usually between 0.3 and 1, y is typically 0.33.

For a reaction that is diffusion controlled

rate = K . A C (8)

where AC is concentration driving force.

This is how K is measured by chemical dissolution, e.g. transcinnamic acid in

water. Or in electrochemical terms when the rate = the limiting current density
(LCD)
LCD = KnFAC. (9)

Thus the basis of the LCD technique in determining Kis to measure LCD at fixed AC.
Using a small electrode, fluctuations in LCD are directly proportional to fluctuations
in velocity and information about turbulence can be obtained. Similarly if K is
known then measuring LCD allows the determination of AC, which will be the bulk
concentration. This is the basis of the analytical method known as voltammetry.
If this approach can be applied to a corrosion process in which both an anodic
and a cathodic reaction occur, if neither reaction is diffusion controlled then the rate of
corrosion will be given by

corrosion current = n F A C K . (lo)

The value of AC will be the bulk concentration of cathodic reactant for systems which
are cathodically controlled and will equal the solubility limit of the relevant product
when the anodic reaction is diffusion controlled (Fig. 2).
If we then substitute for K we obtain

corrosion current = n F A C D ~D ( V
\ d?_ )/X ( D ) Y x c o n s t a n t , (11)

i.e. corrosion rates can be predicted wkhout any tests if relevant parameters are known.
400 BRYAN POULSON

CATHODIC REDUCTION RATE CONTROLLING

i,(j MILDSTEEL IN SEAWATER

02] :BLLK VALUE

STEEL SE/~ATER

ANODIC REACTION RATE CONTROLLING

aa Him STEEL IN CONCENTRATEDSULPHURICACID

I
[Fe so4] i= SATD~ATION~.UE
STEEL d~
Ol,
CONCENTRATED H2SO4

1
IFFUSION.__t|
LAYER
FIG. 2. Anodic and cathodically controlled corrosion reaction.

However this would predict no corrosion at zero velocity and natural convection
would have to be added at low to zero flow velocities.

A P P A R A T U S F O R E L E C T R O C H E M I C A L M E A S U R E M E N T S IN
FLOWING SOLUTIONS
Apparatus
Apparatus for examining the effects of flow on corrosion is similar to that used in
static tests except that either the specimen (rotating discs and cylinders) or the solution
must be moved, and more thought must be given to the placement of reference and
counter electrodes. Wranglen 13 has argued strongly that the rotating disc and par-
ticularly the rotating cylinder have advantages over flowing systems when electro-
chemical measurements are to be made. The solution volume to specimen area ratio
affects the sensitivity of chemical analysis to monitor corrosion but this should in any
case be relevant to the practical problem. As I see it the advantages of rotating systems
are convenience based, i.e. they are cheap and easy to use, small, etc. The advantages
of a flowing system are the ability to test representative geometries and realistic
materials and the ability to maintain a constant environment if this is desirable.
A description of a rig used to make electrochemical measurements in flowing
acid cleaning solutions should illustrate some relevant considerations. The rest of
this section will then be a review of the characteristics of various specimens which are
used (Fig. 5). The mass transfer characteristics of pipes and orifices together with some
other geometries encountered in practice have recently been comprehensively reviewed
by Coney. 14
The rig is shown in Fig. 3 and is constructed nearly entirely out of Polyvinyliden
fluoride (PVDF). This was chosen because its chemical resistance is nearly as good as
PTFE, it can be used up to 140°C, it can be welded and machined easily and is readily
 Electrochemical measurements in'flowing solutions 401

available as valves, pumps, elbows, bends and other fittings. Solution is stored in a
20 1. PVDF glass fibre reinforced tank with facilities for de-oxygenation, positioning of
auxiliary electrodes and a level control. Temperature is controlled (d: 0.25°C)by a
silica enclosed 1.5 kW heater with a contact thermometer operating a relay. Tempera-
tures in various parts of the loop can be measured or recorded using thermometers
or thermocouples. The pump is a PVDF centrifugal pump with a Hastalloy C shaft;
similar magnetically coupled pumps in PVDF are now available. Solution flow is
measured using a rotometer because they are simple, cheap, clear and compatible with
a wide range of fluids.
The cell for holding straight tubes, bends and orifice specimens is shown in Fig. 3.
Both a remote or co-axial counter electrode can be used depending on the specific
requirements. A versatile PVDF impinging jet cell is also included in the loop and
shown in Fig. 4 allowing a variety of nozzle and specimen types to be used. The three
nozzles shown include the conventional jet producing a wide range of mass transfer
rates across a specimen, a similar jet having a larger diameter producing relatively
constant mass transfer across a small specimen under laminar conditions and finally a
multiple jet which it is hoped will produce constant mass transfer across a small
specimen under highly turbulent conditions. So it will be possible to examine corrosion
under conditions of equal mass transfer with laminar or turbulent conditions.

ROTATING R e : ~)r 2 S-"hL = .6205 Res Sc~

-y
DISC
Rec =1"7-35x10s S"hT : "00"/8 Re" Sc:~

ROTATING .•~ , ~ . . 0 7 9 Re SC~'~

CYCLINDER Rec,,.2O0 . . . . . (1.25 *5"76100od/F-i~ Re Sc,~6

o

i IMRNOING Re= ¢~ S-"h,;A : 1.12 Re Sc~(Hld)~

JET x Rec ~2000 Shw; : .65 Re~" (x/d) ~

,~j ~ T j
NOZZLE Reo =~LY~ 51%,: = "276 Re:it Sc ~
OR
ORIFICE
Re ,,, 600
y
_Sh,
_
Sh,~
.: 1 *A, I+ B , [ ~.~6
L'0165 Re~'
-2
~" !

Re =- (:I~ ~hL =}61LIReSc d/L) '~ ~-h~ : .2?6R~Id/L) 3~

TUBE Y
* .... L- .... Jo Rec ~ 2000 S'h,~ ='0165 Re~ ~

FIG. 5. Summary of specimen types examined in detail.

The rotating disc

As the disc is rotated surface drag causes swirling of the fluid which is forced
radially over its surface; axial flow bringing fresh solution to the disc. With this
centrifugal flow the surface is uniformly accessible. However, at low Re values
( < l0 s) alternative flow patterns (reverse and toroidal flow) have been proposed for
402 BRYAN POULSON

both Newtonian x5 and non-Newtonian fluids 15 but these are unimportant in this
context.
At higher R e values three flow regimes can exist simultaneously on the surface
of the disc. The position of each will depend on R e but will be modified by, among
other things, the surface roughness. The most detailed study of such transitions has
been by Chin and Litt x7 using fluctuations in the limiting diffusion controlled current
density at a point electrode. Briefly it was found i f R e < 1.7 × 105 flow was laminar;
if R e > 1.7 × 105 < 3.5 × 105 flow is transitional and if R e > 3.5 × 105 flow is
turbulent (see Fig. 6 and Table 1).
The rotating disc is important in that theory preceded experimental results and
exact solutions to the theoretical equations have been obtained for mass transfer
under laminar conditions by Levich~a who showed

Sh ---- 0.6205 R e °.5 Sc °.33. (12)

This was derived assuming a reasonably high value of Sc. Modifications have been
proposed by Sparrow and Gregg, ~9 Riddiford ~° and Newmann. 2~ Recently Mishra
and Singh ~2 reviewing all the data proposed

Sh = Sc [0.5657 q- Sc °.°°] 0.62048 Re °.5 (13)

but the degree of improvement, if any, that this gives was not quantified and the
simpler Levich equation is adequate for use in corrosion studies. Other modifications
have been proposed for disc eccentricity or edge effects. The situation where mass
transfer is limited to part of the disc has been treated by Chin and Litt, ~3 they showed
that mass transfer could be ten times greater at a point electrode for a given rotational
speed.
When Re > 2 x 105 the overall mass transfer rate comprises a contribution from
the laminar and transition regions and above 3.5 × 105 the turbulent region. Above
Re ~ 105 this dominates the overall rate and various equations have been proposed
such as:

Sh = 0.0078 Re °.9 Sc °.3 (24) (14)

Sh = 0.0117 Re0 °.896 Sc °~.46 (25) (15)
Sh = 317.16 Sc °.33 ÷ 0.00838 R e °.9 S c °.8311 -- (2.6 × 105/Re)°.~-5](22) (16)

In corrosion studies it is more important to know how the mass transfer rate varies
locally. At Re values up to Recrit mass transfer is uniform and as given by the Levitch
equation. Above Recrit a central laminar region is surrounded by transition and
turbulent zones where mass transfer will be increasing with increasing radial distance;
this has been treated by Newman ~4 and French workers. ~6

The rotating cylinder

Like the rotating disc, a rotating cylinder will cause swirling of the fluid because
of surface drag. The extent will depend on the exact geometry, particularly the degree
 Electrochemical measurements in flowingsolutions 403

"1 LAMINAR TRANSITION J TURBULENT

VORTEX INTEI:~4EDIATE
oOTURBULENT
• 08 - - Probe dmm Pwfr

o &oA,~
d-
o "381 60.1
+ "381 54
'06 °d'+ ^ " .381 47.7
-- • b• • .254 6O'3
. a • o .25# 41 "3
+oo or&Joe • •
.o4 • O e O

__ ~ , °~°u
. , . ~ ÷o~ % o +
o ooo

.O2
-- 1'7 + a I
I+o o 3"5
Ot3TA A !
O
2 3 4 S 6 7
Re * 16~
FIG. 6. Transitions on the rotating disc electrode using variations in the LCD (Chin
and Litt).

of baffling. A favoured experimental arrangement is one involving the presence of a

concentric stationary outer cylinder around the inner rotating cylinder. Eisenberg 27
e t aL showed that the critical dimension, at least for mass transfer in the turbulent
region, was the diameter of the inner rotating cylinder. Laminar flow only occurs at
low rotational speeds, e.g. 10 r.p.m, giving a critical R e of -~ 200; this may be increased
if the outer cylinder is also rotated. Newman 28 considers that three flow regimes need
to be defined: (1) at low rotational speeds flow is tangential and laminar, (2) secondly,
above a critical value of Ta* (see Fig. 7) flow regains laminar but Taylor vortices develop
giving superimposed radial and axial motion, (3) thirdly, above a critical R e true
turbulence develops.
This has been examined in detail by Mizushina 29 using the LCDT technique with
71-point electrodes in the stationary outer cylinder. His results are summarized in
Fig. 7 and show the situation is even more complicated than that postulated by
Newman. The non-uniformities in mass transfer at intermediate speeds were also found
by Holman and Asher. a° In their experiments Taylor vortices produced peaks and
troughs in their benzoic acid cylinders rotating in water.
Relatively little mass transfer data is available on the laminar region. Cornet and
Kappesser 3~ found that for S c = 46

Sh = 37 (between 5 < R e < 200) (17)

which suggests that the fluid is rotating with the inner cylinder and not contributing
to mass transfer. This simple picture does not agree with theoretical predictions 3~ or
some work using a rotating wire. z3 However, this region has little practical significance.
Above a R e of ~ 200 it is surprising in view of the complicated transitions and
apparent non-uniformities of the process that a single mass transfer correlation exists.
404 BRYANPOULSON

Ta=ReF do- di"I

L di .}
.,uA Sh/S¢ 33 To

EAMINAR .4I " <41'2

.01 i i i I

LAMINAR .1[ __ 20 i ~ ~ (8OO

VORTEX I I I
•3 ~¢
TRANSITION
"3~1., ~ "V'I 50i i ~ t ~ ~.10oO

TURBULENTVORTEX1 ~ ~ ~ 100i ~ ~ 2000,lSOOO

t / 1 I I

TURBULENT 2i ~ ~ 1 I 60 t I ,~15000
O 1 2 3 0 5 10
TIME DISTANCEcm
FlO. 7. Transition on the rotating cylinder electrode using LCDT (Mizushina).

Eisenburg et aL were the first to study this comprehensively using both chemical
dissolution and LCDT and suggested? 7

Sh = 0.079 Re °.~ ScO °.aSe. (18)

It has been pointed out u that this correlation is remarkable in that it can bring
together data on heat transfer, mass transfer and friction on cylinders rotating in
gases and liquids over ranges of Sc and Re of 4 and 5 orders of magnitude respectively.
Newman 35 has suggested that the ratio of inner to outer diameters should be
incorporated in the correlation by modifying Re, i.e. [Re dl/do] °.~ but the effect will be
small in most cases. Gabe and Robinson 3s have pointed out there are slight variations
in the Re and Sc power indices but again these are small. King sT,sa has insisted that
in ~t well baffled system the Re index should approach unity. Since most of Kings'
experiments have been with dissolving cylinders it is probable that increasing frictional
forces have been responsible for the effects. This has been examined in detail by
Kappesser et al. ~9 who introduced a dimensionless roughness term (d/e). This is the
ratio of specimen diameter to roughness height. Their results are shown in Fig. 8.
Essentially: (a) for smooth specimens the Einsenburgh correlation holds, (b) with
increasing roughness a decreasing critical Re is reached above which mass transfer is
above the smooth value, and (c) above the critical Re value
 Electrochemical measurements in flowing solutions 405

Io'
" d/t Sh:{1.2S.STSlogd,~ fr~e S~~ ,d/* x j
- o \
' , ls6 \ ~'//o3/
o ~2xIO

ld
_-- <do4-
Sh S ~ _ u/ o.O-

:
_ o,°~
1°-%f",1"
Q~" , t , l] l I t ,J I I I I
10 ~ 10 ~ I0 s
Re
FIG. 8, Mass transfer correlations for rough and smooth rotating cylinders using
LCDT (Kappesser et al.).

Sh = (1.25 + 5.76 loglo d/c) -2 Re Sc °.33B, (19)

i.e. the mass transfer rate is directly proportional to Re. Gabe 4° has recently re-
examined the effects of roughness and found mass transfer can be increased by up to
50 times by a combination of increasing surface area and microturbulence.

The impinging jet

This comprises a submerged jet impinging, usually at 90 °, on to a flat specimen.
The hydrodynamics of this geometry have been extensively examined 4~.42 and are
summarized in Fig. 9.
In general mass transfer depends on both the jet to plate distance (H/d) and the
radial position on the plate (x/d), i.e.

Sh = ~ Re ~ ScY f ( H / d ) f ( x / d ) . (20)

For both round and slot nozzles the local variation in mass transfer coefficient
is the same. At (H/d) values greater than approx 5 a monotonically decreasing bell-
shaped curve is obtained 43 (Fig. 10). For smaller (Hid) values one or two peaks at
(x/d) values of ~ 0.5 and 2 as shown in Fig. 1 1.44 These peaks have not been found
by all workers (e.g. Fig. 10) and are also promoted by high Re values. It is thoughO ~
that the outer peak is caused by the sudden rise in turbulence due to the disappearance
of the stabilizing pressure gradient.
The detailed analysis of such behaviour has tended to concentrate on the region
of uniform accessibility (x/d < 0.5 or 1) and the wall jet region (x/d > 5). A pre-
liminary analysis 45 of the secondary peaks at (x/d ~ 2) suggests a dependency on
Re °.vS, but in general little attention has been paid to such features.
406 BRYANPOULSON

CONICAL POTENTIAL CORE

~'6.-1.4d IWALL JET REGION

\ ~5-4 d
!STAGNATION
I REGION

""b
// -- '25

•9[-----~ ,o'4b-~.,o /~ n
I -\ d o-.. ,,
81 \4 :" "~t 2
"F- P ?'- vAs
•7 1 / • ,' I~"'., m ) ' V'
/ ' \ ' = m/'b"'-8 ""m I
•6 :/ ~ ",,....~..,~
Yx o
V I.
•s / . . .
-

o -•
t~', l /
.../"
.,)'i
=
h-1',o,
....
5 n

.....o..~.~'V~

Px• I ./ ,&~ /
•31 ; /' 4 /
P
\,,
•I II-"
L - ~ . - . o " ..~/
P 4x
• /

RADIAL DISTANCE ( x/d )

FIo. 9. Impinging jet electrode: terminology and hydrodynamics (Lush et al.,
Gordon et al.).

In the uniformly accessible region mass transfer is proportional to Re and decreases

with increasing (H/d), having a different constant in different flow regions. Chin and
Tsang 46 suggested from LCDT measurement for H i d values between 0.2 and 6.

Laminar jet: Sh = 1.51 Re °.~ Sc °.33 (H/d) -°'°~4 (21)

(if Re < 2000, x / d between 0.1 and 0.5)

Turbulent jet: Sh = 1.12 Re °'5 Sc °'38 (H/d) -°'°~7 (22)

(if Re between 4000 and 16,000 and x / d between 0.1 and 1).

The wall jet region begins at ~ 3-5 nozzle diameters and in this region mass
transfer fails with radial distance as (x/d)-l. Patrick et al. 47 utilizing LCDT suggested
 Electrochemical measurements in flowing solutions 407

"-0~°-"'°~ d =-156"
"~ ~ n ~. Ok Re:- 114300
u~u~ 5c=900
lo'

Sh
_ u ~8
-- A 19.2

3
lO

I IIIII I II
1 2 3 4567810
RADIAL DISTANCE (x/d}
FIG. 10. Mass transfer from impinging jet obtained by chemical dissolution of trans-
cinnamic acid into water (Rao and Trass).

Sh - 1.14 Re °.s2 (x/d)-1.°5 (5120 < Re ~< 13498; 8 <~ x/d < 17; 5 < Hid < 20) (23)

From trans-cinnomic acid dissolving in water the following correlation was obtained :48

Sh = 0.65 Re °'84 (x/d) -1.2 (25000 ~< Re < 12500; 0.2 < Hid < 19.23). (24)

This paper also included a very interesting discussion on the effects of pure erosion
and how it could be measured using a saturated solution.
Overall mass transfer coefficients have been obtained for both single and arrays
of round nozzles. For the latter: 44

- - 1 ~ 2.2 f o~_ ] 1ReO.6e (25)

Sh = Sc o.'2 [1 + \ 6 / f ° ' V -1 0.2 (H/d -- 6)f0.5/_!

where f is the relative nozzle area. The equation's limits are 2000 < Re < 100,000;
2 < Hid < 12; 0.004 < f ~< 0.04.
If the jet instead of impinging at 90 ° to the surface is inclined at 45 ° (as in the
BNFL test) the overall mass transfer remains constant but the stagnation point moves
nearer to the vertical than expected. 44 The effect of 2-phase flow on mass transfer,
i.e. the common practice of injecting air into the impinging jet has not been examined;
but it clearly makes the test more severe, for electrochemical or mechanical reasons.

Tubular specimens
Flow in tubes is probably the most commonly encountered geometry. The lower
limit for the laminar to turbulent transition is Re ~ 2 × 103 when there are large
408 BRYAN PouLSoN

51

Re

37~X~0

250000

124000
78000
34000
1O0O0
5000
VO 2 4 6 8 2500
RADIAl- DISTANCE (x/d)
FIG. 11. Mass transfer from impinging jet showing characteristic secondary peaks
(Martin).

TABLE ] . DETAILS OF FLOW REGIMES ON ROTATING DISC AFTER CHIN AND LITT

Reynolds No.
Region range Comments

Laminar < 1.7 × 105 Some imprinted spirals at 60 ° to the radius

have been found possibly caused by pro-
trusions or gas bubbles.

•~ Vortex > 1.7 < 2.6 x 10 s Stationary vortices are amplified producing
O spirals at 76 ° to the radius.

Intermediate > 2.6 < 3.5 × 10 ~ Stationary vortices are breaking down into
t- turbulent smaller eddies.

Turbulent > 3.5 x 10 ~ Stable eddies have been formed.

 Electrochemical measurements in flowingsolutions 409

disturbances and it is probably that the flow will always b e turbulent when R e ~ 105.
This has been examined in detail by a number of workers, Reiss and Hanratty49 used
the LCDT at a point electrode, they found: (a) at low R e flow is laminar and there are
no current fluctuations, (b) at a R e of 2140 a slight wavy disturbance was noted, (c)
at slightly higher R e intermittent patches of turbulent flow (turbulent plugs) and non-
turbulent flow was indicated (Fig. 12a), (d) as R e increases the fraction of time the
motion is turbulent--known as the intermittency factor--is increased, (e) at a Re
number of 3740 the flow is completely turbulent (Fig. 12b), and (f) further increases
in Re increase the frequency of the fluctuations in the LCD (Fig. 12c).
There is very little mass transfer data available for fully developed laminar flow.
Firstly, because it is not of practical interest and secondly, because of the long entry

,,ol- .

F I I I I I~
10 20 30. 40 50

100 - - :t . . . . . ,

eve°rcx~] 8O

6 ° 11 12 13141 51 16 17 18 191101 111

TIME s

,oF, '
1 2 3 4 5 6 7 8 9 10 11
,,,, I
-I
I0

O~ O~
-

o/
/

16~I0 , I I ] I ] [ I I [ I
10 ~' 10 s
Re
FIG. 12. Transitions in pipe flow obtained using LCDT and effectof Re on turbulence
(Reiss and Hap.ratty).
410 BRYANPOUt,SON

lengths involved. However, both theory and available heat transfer data suggest it is
independent o f R e : the theoretical constant N u value (heat transfers equivalent o f S c )
o f 4.1 is to be c o m p a r e d with the experimental value o f 3.65.5°
F o r the case o f fully developed turbulent flow in smooth straight tubes there is a
large choice o f correlations to choose f r o m (Table 2), the most c o m m o n being the
Chilton-Colburn analogy? 1

S h = 0.023 R e °.8 S c °.3~. (26)

Coney t4 has reviewed such correlations pointing out how the C h i l t o n - C o l b u r n

analogy gives results which diverge from m o r e recent correlations at high R e values
and predicts low values at high S c numbers. Coney t4 recommends the Berger and
Hue s2 correlation which was based on their own L C D T results and other available
data

S h = 2 + c R e 2 S c °.3 (26)

where c : 0.0165 + 0.011 S c e-SO; a = 0.86 -- 10/(4.7 + S c ) ~ (27)

which is valid 0.6 < S c < 104, 104 < R e < 10e.
They also proposed a simpler equation for high S c values

TABLE2. SOMECORRELATIONSFOR FULLYDEVELOPEDTUBEFLOW

Originator Correlation Origin

Chilton-Colburn Sh = 0.023 Re °'8 Sc °'3a Analogy with heat transfer.

Berger-Hue Sh = 2 + c R # Sc °'a Their own LCDT data and

c ----0.0165 + 0.011 Sc e -so other experimental data.
a = 0.86 - 10/(4.7 + Sc) 3

Berger-Hue Sh = 0.0165 Rc °'8~ Sc °'an For Sc > 10 only 3%

error.

Harriot-Hamilton Sh -- 0.0096 Re°'91a Sc°'s46 From their chemical

dissolution experiments
involving benzoic acid in
glycerine-water mixtures.

Notter-Sleicher Sh --- 0.0149 Re °'Ss Sc °'83 Theoretical e diffusivity

with constants from
experimental work.

Re Sc Empirical analogy with

Churchill Sh --- Sho + 0.079 a/[
(I + Sc°'S) °'ass friction.
Re Sc Boundary layer integration.
Jayattilleke Sh = Total resistance to mass
2 7.81] transfer is sum of
resistances in laminar and
where P = F(Sc) turbulent regions.
 Electrochemical measurements in flowing solutions 411

Sh = 0.0165 Re °.se SC0'33. (28)

This fitted all their data between Re 8000-200,000 and Sc 1000-6000. At a Sc of 10 the
maximum difference between simple and full equation is only 3 ~o.

Entry effects
On any test specimen if there is a low concentration of the dissolving substance
at the beginning enhanced mass transfer will occur. This is particularly important
with tubular specimens and it has been common practice to provide separate lengths of
tubes prior to the specimen so that established mass transfer conditions will be
obtained before the specimen is reached. This makes it easier to obtain data pertinent
to fully established conditions if for example specimens are simply weighed or corrosion
rates obtained from solution analysis.
The required mass transfer entry lengths can be estimated from theoretical or
empirical correlations obtained over various (d/L) ratios. For laminar flows this has
been examined by Ross and Wragg 57 who showed graphically both the Graetz 5s and
Leveque ~9 solutions. Only the former predicts an approach to constant Sh, or fully
developed mass transfer, at sufficiently long tubes. For a typical solution with S¢ =
2000 and Re = 500 the required entry length would be 125,000 tube diameters, i.e.
for a 1 cm dia. tube it would be about a mile. Up to lengths of about 500 tube dia-
meters mass transfer should be obtained from the Leveque equation

Sh = 1.614 (Re Sc d/L) °.33. (29)

In turbulent flow, using the LCDT Berger and Hae s2 found:

Sh = 0.276 Re °.5~3 Sc °.33 ._d°'Z3 (30)

L

Coney 14 differentiated this wrt L to obtain local Sh values

Sh L = 0.184 Re °.ss3 Sc °.33 (d/L) 0"33. (31)

Then by dividing this by the simplified Berger and Hae equation for fully developed
tube flow he obtained

Sh
-- 11.15 Re -0"277(d/L) °'a3. (32)
Shfd

This predicts entrance effects decrease with increasing Re and even at an Re of 104
they will have disappeared before 1 tube dia. It is interesting that this suggests entry
effects will be Sc independent. However, Coney 14 points out at low Sc this is not so
and entry effects will be larger and extend further. In laminar flow the reverse is true
and at a Sc of 1 only ~ 1 m would be required as compared to ~ 1 mile at a Sc of
2000.
412 BRYANPOULSON

It is also necessary to provide a sufficient length of straight tube prior to the speci-
men so the hydrodynamic boundary layer may be fully established. Ross and Jones 6°
summarized these requirements as being"

For laminar flow L min = 0.035 Re d (Re < 2000). (33)

For turbulent flow L min = 0.693 Re °'~5 d (Re > 3000). (34)

This gives entry lengths of 3.5-70d for Re between 100 and 1000 and 5.2-12.3d for Re
between 3000 and 100,000.

Orifices, ferrules and flow expansions

Recently it has been realized that such geometries provide in many environments
the necessarily severe hydrodynamic conditions to produce erosion corrosion. They
are thus useful specimens for studying the effects of varying hydrodynamic factors on
corrosion as well as being relevant to practical situations.
In the ease of a ferrule or sudden expansion, fluid emerges as a round turbulent
jet and, being unable to satisfy its entrainment appetite with ambient fluid, causes
circulation of fluid from further downstream (Fig. 5). The downstream limit of the
recirculation zone is marked by the attachment of the separated streamlines to the pipe
wall. The flow downstream then slowly readjusts until after about 7 tube dia it is
fully re-established. The case of an orifice differs slightly in that a vena contractor is
produced the area of which is typically only 60 ~ of the orifice, thus increasing Reo.
Both the heat transfer data of Krall and Sparrowel (KS) and the mass transfer
data, using LCDT, of Tagg, Pattrick and Wragg62 (TPW) show that the maximum
mass transfer rate can be obtained from

[
Shmax = 0.276 Reo°'e6 Sc °'3z where Re o Re\] (35)

as shown in Fig. 13. This will be reduced slightly if mass transfer is taking place prior
to the orifice, probably reducing the numerical factor to 0.2 under conditions mini-
mizing mass transfer. 14 This enhancement over fully developed pipe values increases
with increasing dido values and decreasing Re values and occurs at approx. 2 tube
diameters downstream of the orifice. The enhancement can be obtained by dividing
the correlation equation for the maximum mass transfer downstream of an orifice by
that for fully developed flow. After simplification this becomes

Shmax__ 0.27 ( _ d y .e8 1

Shfd 0.0165\do~ Re 0"19 (36)

The actual mass transfer profile has been examined in some detail by Coney paying
particular attention to the KS and TPW data he obtained.

[ Re cO 3_21)] 37,
S h f d - - [ + A~ I + Bx \ Shfd
 Electrochemical measurements in flowing solutions 413

ld

ShS

18 ~,,~B ~w
/ S,.27Rg SE
10 3
I
10 4
I
10 S
Re
FIG. 13. Mass and heat transfer correlations for peak rate following a sudden expan-
sion (Tagg, Pattrick and Wragg, Krall and Sparrow).

Values o f the constants A a n d B at different tube diameters f r o m the orifice, o b t a i n e d

f r o m g r a p h s o f C o n e y are given in Table 3. T h e fit o f such an a p p r o a c h c a n be j u d g e d
in Fig. 14 t a k e n f r o m C o n e y ' s paper. F u r t h e r simplification can be o b t a i n e d by sub-
stituting for Shfd, from the simplified B.H. equation.

Shx (\0.0i65~ee0.86
Reo°" 21)] (38)
Shfa - - [ -}- A x [ I ÷ Bx

A s u m m a r y o f o t h e r specimens t h a t have been used is given in Fig. 15.

TABLE 3. VALUES OF CONSTANTS IN CONEY'S EQUATION FOR MASS TRANSFER

PROFILES OF ORIFICES

Distance from orifice A B

in tube diameter KS TPW KS TPW

0.5 2.72 2.12 0.057 0.073

1.0 3.67 3 0.051 0.049
1.5 4.52 3.75 0.059 0.062
2.0 4.7 4.2 0.066 0.072
2.5 4.5 4.17 0.068 0.079
3.0 4 3.74 0.067 0.078
3.5 3.15 2.92 0.065 0.073
4.0 2.45 2.25 0.064 0.069
4.5 1.72 1.62 0.063 0.064
5.0 i .45 1.27 0.062 0.063
5.5 1.22 0.98 0.059 0.062
6.0 1 0.77 0.058 0.062
6.5 0.82 0.6 0.056 0.062
7.0 0.67 0.45 0.055 0.062
KS datavalid:2 ~<d/do ~4, 104 ~< Re ,< 1.3 × 105; 3 ~ P r <~6.
T P W d a t a v a l i d : 2 .~d/do ~ 6, 8 × l0 s ~ Re ~2.2 × 104; Sc = 1450.
414 BRYAN P O ~ N

il
d/d, Re
n 6 15672
o 3 10126
A 3 21700

5 m
o°/OO \ o\ I
o o
/A A-A'A\ \
Sh __ ,C\

A/A~n. 1+ + '~ 1

A °"~-.9o •

1 2 3 4 5 6 7
TUBE DIAMETERS FROM'NOZZLE (x/d)
Fie. 14. Enhancement of mass transfer downstream of a nozzle: comparison of
experimental LCD data (Tagg, Pattrick and Wragg) with Coney's correlation.

Relationship between corrosion rates for different specimen geometries

The purpose of using well characterized specimens is to be able to compare results,
with that predicted from the mass transfer correlation, with that obtained with
different specimens, and more importantly to be able to relate the results to practical
geometries, e.g. bends, pump impellers, etc. However, the mass transfer characteristics
of such components are not always known.
Because rotating discs and cylinders are easy to use a number of workers have
suggested either empirical correlations or correlations based on an equality of mass
transfer.
Poluboyartseva83 carried out an extensive investigation using laminar rotating
discs and turbulent pipe flow with a number of different material/environment com-
binations. Empirical equations obtained are given in Table 4 together with their
theoretical equations. The differences between the two, i.e. the numerical constant
is the result of natural convection.
Heir# 4 used the reaction Zn + Is = ZnI~, which is diffusion controlled, to study
the relationship between turbulent corrosion on discs and cylinders and tubes, he
obtained
velocity in tube (m/s) = 6.6 x rotation speed (rpm) x [dise radius (em)]°4
= 37 x (rpm) °'~ x [cylinder radius cm]°'L (39)
 Electrochemical measurements in flowing solutions 415

ROTATING DISC IN HOUSING ROTATINGRING DISC

I 1

PLATES IN ANNULUS
SINGLE PLATE DUCT WALL

.............. P [
p
I V.H...H.~ I

BOILER WATER
EROSION-CORROSIONTEST MULTIPLE PLATES IN PIPE

i l • • ....... .r/~,.,
[r ii
I ,,, J

BNFRA IMPINGING
JET TEST
i

PLAN OE A

FIG. 15. Summary of some other specimens that have been used in flow experiments.

W r a n g l e r 18 u s i n g t h e E i s e n b e r g c o r r e l a t i o n (for cylinders) a n d t h e C h i l t o n - C o l b u r n
a n a l o g y (for t u b e s ) e q u a t e d m a s s transfers a n d o b t a i n e d

l o g Re t u b e : 0.67 + 0.833 log Re cylinder. (40)

TABLE 4. PIPE TO DISC CORRELATIONS PROPOSED BY POLUBOYARTSEVA el ¢d.

Temperature
Material Environment °C Empirical equation Theoretical equation

Steel 9 4 - 9 8 % H~SO4 60 V = - 0.05 + V ----0.7 Se~°'e6v/Tn

0.7C~tn

Cu 0.1 N HC1 + 30 V = - 0.21 + V = 0.5 Set°'=s~/?n

198 g 1-1 Fe 3. 0.5~/7n

Pb 2MNaOH + 40 V= - 0.94 ÷ V = 0.9 Sc,°'=SCyn

0.1 N NaNOa 0.6C~'n

V is pipe velocity in m s -1, n is number of rpm to give same corrosion rate, Sct is turbulent Sc
number (ratio of ~ diffusivity for momentum transfer to that for mass transport).
416 BRYANPOULSON

Ellison and SchmeaP ~ appear to have confirmed this approach in a study of carbon
steel dissolving in concentrated sulphuric acid. They used both rotating cylinders and
pipe flow measuring corrosion both electrochemically and by weight loss. Their results
are shown in Fig. 16 together with the predictions using known or measured data on
the solubility of FeSO4, the diffusivity of ferrous ions, and the kinematic viscosity of
HzS04 with the Eisenborg and the Harriot Hamilton correlations. The agreement
between predicted and measured corrosion rates was impressive.
However there are a number of pieces of evidence that such simple approaches do

1~ ~___ CARBON STEEl_ PIPE 68%wt H2SOI, 60°cJ

~- - FRIEND
andMETZNE / ]
--HARRIOTond HAIti-TON//// |
Sh'° s"cx~R'~ /
LIN" ~ DEISSL.ER I

,Oio , , ,, l,ll,I,
Re
°

ld
-- *20%-"

Sh-'079 Re' S~ s6 ""'"i~"'-20°/° o

__ " . ..='"/~ ....." A 60 C
-- _x . ' o . / ~ . . . . . . . . ~ . . . ........ o 40 °C
Sh~ _ /'"
~~-'-~. ~ , . , , ' ~..o'"
J~.." a 27
o
C

.,,~..j~........."o.'"^ ROTATINGSTEEl_ CYLINDER 6OO/owt,Hz$Ot,

""~:/"i""
U"~ ' J ' J [['ll ' I J I ' [ ['
ICI03 10~ 10s
Re
FIo. 16. Data for carbon steel pipe and rotating cylinders exposed to 68% HaSO,
comparedto predictedbehaviourfrommasstransfercorrelations(Ellisonand Schmeal).
 Electrochemical measurements in flowing solutions 417

not always work. For example LaQue 66 showed that the response of rotating iron
and copper discs rotating in sea water was radically different. Bignold e t al. e¢ examined
the erosion-corrosion behaviour of carbon steel in pure water at around 150°C using
an orifice specimen geometry. They found that the erosion corrosion rate under their
test conditions varied as the cube of the mass transfer (Fig. 17) rate instead of being
directly related to it. This was explained in terms of a model based on the electro-
chemical dissolution of magnetite. We have examined this using different material,
environmental combinations with both orifice and impinging jet geometries. Typical
corrosion rate profiles for iron and copper specimens dissolving in 0.1 N HC1
containing 2 g 1-* ferric ion (as Fe CIa) are shown in Fig. 18.45 In this solution corrosion
is thought to be controlled by the rate of reduction of ferric to ferrous ions, so the
profiles for the two materials should be the same and similar to the mass transfer
profile. This is the case with copper, but iron behaves anomalously. In particular it
appears that iron dissolution downstream of the peak is less than predicted, pro-
ducing a high apparent enhancement factor. A possible reason for this is the local-
ization of anodic and cathodic areas. Cross sections through impinging jet electrodes
are shown in Fig. 19. With Cu exposed to the 0.1 N HC1 + 2 g 1-1 Fe 3+ the profile

10
~ " DECgYGENATED PURE WATER pH905 157°C
m

m kg h~
a 920
~-- FLOW RATES o 574
287
d = 8-34mm
do= 2.72mm [~3 SL.OPE =3
E
7h
UJ

¢r
z
o

8
Z
O
666 AAA~~°
8
EZ
u.I
o7
I I l lllll[ 1 I I i lllll 10
MASS TRANSFER COEFFICIENT (ms~g)] )
FIo. 17. Effect of mass transfer rate on erosion-corrosion rate of carbon steel orifice
specimens exposed to pure water (Bignold).
418 BRYAN POULSON

DISTANCE cr.
I 2 3 4 5 6 7 8 9 I 0 II 12 13 14 15 .16
IIIIIIIII / III111
EMCAt~EHENT
FACTOR
0 CARBON STEEL |03
• COPPER 5"/.

0
__ ,q",, °
0 O0
| Oo

tu oo

•o
z
M
o
U~ •o
0 0
,v
m
3 6
0
000000000000000000
O

I 2I 3I
I 4 5 6 7 8 9 IO l l 12 13
DISTANCE DOWNSTREAM OF ORIFICE IN TUBE DIAMETERS

FIG. 18. Effect of material on enhancement of corrosion in 0.1 N HC1 containing

2 g 1-1 Fe =+ at 50°C, following on orifice. Reynolds number was 27,309, d/dO of 2.67,
giving predicted enhancement of 4.6.

is again similar to that expected from the mass transfer profile (Fig. 11). With
carbon steel exposed to NH4NO8 which is a solution that produces a protective
film the corrosion is much more localized at the region of highest mass transfer which
is also the region of highest turbulence.
In corrosion situations, in which both anodic and cathodic reactions occur, often
on separate areas--simple relationship with mass transfer do not always hold. The
relationship between corrosion rate and mass transfer, or other hydrodynamic para-
meter, needs to be determined for each system of interest.

THE A P P L I C A T I O N OF E L E C T R O C H E M I C A L M E A S U R E M E N T S IN
FLOWING SOLUTIONS
Practical corrosion situations
Early uses o f electrochemical techniques in measuring corrosion rates were based
on unsound theory. Examples included T o d t ' s Corrosimeter (which measured the
 Electrochemical measurements in flowingsolutions 419

galvanic current between the specimen and a Pt electrode) and the Polarization break
method (which depended on arbitrary breaks in polarization curves). The basic
equation from which the corrosion rate I~o,~ can be obtained from the current I
measured at potential E is. as

[ E - Eoo,1 i-E or - E1
I = l¢or, exp L-0.4-3~,~ _1 -- I~°~ exp L 0~-34-b~- d (41)

from this have developed a number of different approaches:

(a) Tafel extrapolation. With this method the linear portion of curve is extrapolated
from high potentials to Ecorr to obtain/corr. 69
(b) Polarization resistance. 7° This method utilizes the slope of the Eli curve (Rp) close
to Ecor~ (or impedance techniques) 71 in relation of the form

Icorr = ba be I
2.303 (ba 4- b~) Rp.

Unknowns are obtained empirically, by other techniques (e.g. a) or by educated

guessing.
(c) Curve fitting or Barnartt's 3 point technique. This method uses data at both high
and low values of E with graphical, TM computer 7z,74 or unique solutions. 7s
Before any confidence is given to the use of electrochemical techniques in a given
metal/environment system, the values obtained should be plotted against actual
corrosion rates (weight loss, solution analysis, etc.) and a reasonable degree of
correlation be obtained over the range of interest.
As long ago as 1969 South in a M Tech thesis TM made an extensive study of the
corrosion of mild steel tubes in flowing inhibited HC1 in a rig very similar to that shown
in Fig. 3. An excellent correlation between polarization resistance and corrosion rates
was obtained with different inhibitors, temperatures and redox potentials as shown
in Fig. 20 and an empirical relationship between the two defined as"

log corrosion rate (mgcm -2 hr -1) = 1.903 -- log polarization resistance (f~cm :). (42)

Potential dependent adsorption effects occur in this system so bearing in mind

their effects in other systems (H~SO, plus propargylic alcohol) such a good correlation
is surprising. South then went on to examine the effect of varying Re. Over the range
10z ~< Re ~< 5 × 10a the corrosion rate was a linear function of log Re. At higher
values of Re a log/log fit was obtained as expected from mass transfer correlations.
In a similar way Prazak v7 examined both static and rotating steel discs in con-
centrated sulphuric acid with the results shown in Fig. 21. A good correlation between
electrochemical and weight loss measurements was obtained over 3 orders of magnitude
with the same relationship for flowing and static conditions in a system which has
relatively thick corrosion products.
Very few electrochemical measurements have been carried out in flowing solutions
with the aim of predicting or measuring localized forms of corrosion. A number of
420 BRYANPOULSON

100C
m

'E
m

m
X• A
V
VARIOUS INHIBITORS
IN FLOWING 5Olo HCl
>
m

m
~o.~ • AT 80°C
uJ sto~=-I %.e.X o
o
z correlation m,~icie~t
= ,99 ~ A
e~
tOC m

z m

o m

"\
m

re %
,¢ m

,\
" I t Jtlal t t I = I=ltl t t .i i i JJl
o.1 1 10
CORROSION RATE (mg cm2 I~1 }

Fro. 20. Correlation between polarization resistance and corrosion rate in flowing
inhibited 5~o HC1 at 80°C (South).

1(2

~'S 5

1 400~

i
u • Fe 96O/o H2SO.at 22°c o ~

"O51~-L20 ~ 500 1OOO2OCX)5000

POLARISATION RESISTANCE (V ,~1 cn~2 )
Flo. 21. Correlation between corrosion rate and polarization resistance for rotating
steel discs in 96 ~o HsSO4 at 22°C (Prazak).
 Electrochemical measurements in flowing solutions 421

workers have suggested that monitoring the free corrosion potential and its relation-
ship to values known to cause SCC, pitting, erosion-corrosion etc. is a valuable
technique). ~s Such techniques should be examined in practical situations. The recent
analysis of electrochemical noise and its empirical relation to corrosion ratC 9 is most
interesting especially in view of similar effectss° when acoustic emission techniques
are used to monitor noise. It would be valuable to see if such approaches could be
used in practical flowing systems.

Mechanistic applications
There are a number of situations in which differentiation can be made between
different corrosion mechanisms by moving the corrosive environment in some pre-
determined way; this has been sadly neglected as a diagnostic technique.

Dissolution mechanisms. The effect of flow has been used in a number of instances
to determine if corrosion is under activation, diffusion or mixed control. A striking
example is provided by the work of Zemburasx examining the corrosion of Cu discs
rotating in air-saturated 0.1 N H2SO4 at different temperatures (Fig. 22).
At a more fundamental level the rotating disc and in particular the rotating ring-
disc electrode has been used by MiUers~ and Picketings3 to study the dissolution of
metals and alloys. For example a Cu 10 9/o Au disc electrode was subjected to anodic
dissolution and the ring was kept at a potential when it would only detect the discharge
of Au *+. At all currents applied to the disc the ring current was less than 2 vtA (i..e.
Au was not dissolving from the disc in accord with expectations from its potential), s3

Mechanism of passivation
There are two general, postulated mechanisms of passivation: (a) dissolution and

10 /
Cu In air saturated .1N H:SO~
75 °C
8

oc
0
u 2

sOc
I I I I
0 1 2 3 4
ANGULAR VELOCITY ( rod/sec i s
FIG. 22. Effect of angular velocity and temperature on Cu discs rotating in air-saturated
0.! N H=SO4 (Zembura).
422 BRYAN P O ~ N

subsequent precipitation, (b) solid state reaction (oxide or adsorption) in parallel

with metal dissolution. Armstrong a4 has examined possible criterion for deciding
between the two and suggested that the active-passive transition should be rotation
(or flow) dependent if (a) occurs as long as the nuclei are formed at a distance from the
surface which allows them to be swept away: no effect should occur if (b) was opera-
tive. This was used by Turner and Brook 85 examining the behaviour of Cu in HC1
solutions and found no effect of flow on the formation of CuCI~; they concluded it
formed by a solid state mechanism. Wilde sa examining the behaviour of iron in
1 M LiCI has shown the reverse situation. In static solutions no passivation occurs
because of acidity build up which is removed by using a rotating cylinder and passiva-
tion occurs.
There are two interesting ad hoc observations: Richardson 87 showed that Type 304
stainless steel was passive in hot strong HNO3 or N a O H or mixtures of the two.
However if it was exposed to each intermittently it was not and corroded at 5 ram/year.
This clearly suggests that different oxides are responsible for passivity in each case.
The effect of emptying and refilling a cell containing a mild steel specimen potentio-
statically controlled in liquid ammonia was examined, ss It was found that large current
transients occurred at each flush/refill cycle but the magnitude decreased with time.
It was suggested that initially the current decay was due to an adsorbed species which
was lost during the flush cycle. However at longer times a passive film did form,
indicated by interference colours, preventing the high initial currents.

Mechanism o f pitting
There are a number of postulated models for the breakdown of passivity and the
initiation of pitting. One such model suggests passivity breakdown is associated with
the localized build-up of acidity at the metal surface. It was suggested that this could
be tested by examining the effects of fluid flow on the breakdown potential. This
has been done by a number of workers whose results are summarized in Table 5 and
typified by the results of Mansfeld s9 shown in Fig. 23. It would appear that the flow

TABLE 5. SUMMARYOF EFFECTS OF "FLOW" ON PITTING POTENTIALS

Metal Environment Specimentype Effect Ref.

AI 3.5 YoNaCI Rotating cylinder None Mansfeld
304SS 3.5 % NaC1 Rotating cylinder

Iron 1 M LiC1 Rotating cylinder None Wilde

Al 0.1 N NaCI Rotating cylinder Increase Ep by Franz et al.
50 mV
304L 0.2 M NaC1 + Rotating cylinder Almost no effect Sato et al.
0.I M NaISO~

304 0.1 NaCi Flat specimen in solution ,,, 200 mV more Nakayama
vibrated with 200 kH~ noble
waves
 Electrochemical measurements in flowing solutions 423

30G

PITTING
20~ m

ttl
t)
03 10(

E
_J

o
O.

10C j o o
/o \o/\
~ ~ o / PROTECTION o

2013

O
I
4
I
8 12 16
ANGULAR VELOCITY (rad/s¢ci s
FIG. 23. Effect of rotation on pitting of Type 304 stainless steel in 3½~ NaC1
(Mansfeld).

conditions examined so far have little effect on the pitting potential although the
ultrasonic vibrations clearly do.
Pit growth is certainly markedly influenced by solution flow, in that solution flow
minimizes the growth of pits. This is recorded 93 and shown by the general recom-
mendation 94 that velocities greater than 5 ft./s are required to avoid pitting of stainless
steel in seawater. More recently Beck and Chan 95 have examined the effect of flow
on the growth of pits. They concluded that a salt fihn is more important than low pH
in maintaining pitting and above a critical velocity (mass transfer rate ?) the salt film
is removed and repassivation occurs. They developed a theory that suggests that
such processes depend on the size of the pit and the higher the velocity the smaller
will be the critical pit size at which repassivation occurs (V critical ~ Pit radius4/3).

Stress-corrosion cracking
It would appear from a number of papers that control of pH by using a large
volume of solution and pumping this through the normally small ( ~ 50 cm 3) test
cell would be well worthwhile in mechanistic studies. Although the mechanism of
environmental crack growth has not yet proved assessable by flow control the occur-
rence of cracking has. Under conditions of constant potential it has been shown that
424 BRYANPOUL~N

solution flow increased the initiation time and it was suggested that micro-turbulence
decreased local concentrating effects?s However it can be speculated that under
freely corroding conditions flowing solutions would increase the rate of transport, 97
of (say) oxygen, and this could increase or reduce the susceptibility depending on the
effect on the free corrosion potential and the potential cracking zone.

Erosion-corrosion
A paper by Lush et al. 41 examined the relationship between erosion-corrosion
(EC) and the hydrodynamics modelled in an air rig with a hot wire anemometer.
With an impinging jet electrode, using both current measurements between concentric
rings and corrosion depth measurements, they looked at the behaviour of Cu discs in
sea water. It was suggested that the corrosion rate was dependent on the diffusion of
copper ions away from the surface and that this was proportional to rs. In the central
laminar region this could be obtained from mean velocities measured near the wall
and was in fact constant: in the turbulent region it was assumed that rs could be
obtained from the T1 (because distribution of TI and corrosion were similar). The
radial distribution of attack at a single jet velocity agreed very well with their pre-
dictions. However the effect of varying jet velocity on the rate of laminar (V °'~) and
turbulent (V °.') was less than predicted (V °'5) and (V °'ee) respectively. It was suggested
that this was because the reaction was under mixed control. Further it was shown
that it was only at high values of T1 (above 0.75 ms -1 rms) that the surface remained
film free and impingement attack occured; this could it was suggested be a design
parameter. However it is not clear (a) why the available or measured mass transfer
rates (and also incidentally Tl's using the LCDT), were not correlated with the experi-
mental profile, and (b) since the mass transfer rate peaks in the same region as the TI
it is not clear if the surface is kept clean for electrochemical (i.e. it dissolves away)
or mechanical (i.e. it breaks away) reasons. The mechanical stability could be examined
by using a solution saturated w.r.t, the film, e.g. saturating cone. H~SO4 with FeSO4.
Some preliminary work has examined the effect of potential and environment in
systems where stress corrosion cracking (SCC) occurs, i.e. carbon steels in nitrate
and carbonate solutions.45 Interestingly the potential range over which EC occurs
(Fig. 24) is similar, but wider, than that causing SCC. Furthermore the maximum
rates of attack are similar to the crack velocities suggesting that in these systems,
similar electrochemical parameters may be important in both cases. It would appear
that potential monitoring might be a valuable tool for predicting the possibility of EC.

Hydrodynamic applications
The application of electrochemical techniques to determining hydrodynamic
parameters has been the subject of two excellent reviews. ~9,9s The basis is that many
electrode reactions are controlled by diffusion if they are driven at a fast enough rate,
their limiting current density (LCD). This is obtained in practice by slowly increasing
the potential driving the reaction and measuring the current until the plateau is reached.
The mass transfer coefficient can then be obtained from the time averaged local (on
a small electrode) or average LCD
LCD
K -- - - . (43)
n FAC
 Electrochemical measurements in flowing solutions 425

MILD STEEL in solution 1Nwrt NotCO3r, NaHCO 3

-50C at 80°C with 3mm jet impIn~g at 7m/s onto
25rnm dla speclrnen 3ram awe4,
UJ

-600

>
E
.d -700
I-
z
I-- -800
0
o.. / e ~ e
-900

AVERAGE CORROSION RATE (rag cni2 fil )

Fro. 24. Effect of potential on erosion-corrosion of mild steel in carbonate solution.

The intensity of turbulence (T1) can be obtained in a manner analogous to the hot
wire anemometer, with certain assumptions," from the RMS value of fluctuations in
the LCD and is usually quoted as:

Tl = V ' ~
V
-C~~
K
(44)
where v and k are fluctuations in velocity or mass transfer coefficient from mean values.

The local velocity in a system can be obtained by empirically calibrating a small

probe under impingement conditions obtaining:"

LCD = ~ -~- ~ V°''5 (45)

where 0c is a constant representing natural convection and ~ is an empirical constant.

The surface shear stress can also be obtained. 47,1°°
A typical experimental set-up is shown in Fig. 25. Precautions which must be taken
include (a) operating at a flow rate where there is a limiting current, (b) choosing an
electrolyte having an excess of ( + ) and (--) ions so that reacting species do not
migrate in the electric field, (c) choosing a potential at which only the reaction of
interest is occurring, (d) positioning the electrodes so that the current distribution is
as even as possible and neither effects the flow, and (e) if local mass transfer coefficients
are to be obtained the small electrodes must be surrounded by large active electrodes.
The two common solutions used in the L C D T are:
426 BRYAN POUL$ON

FOR RfT..,O~NOLeD
/
l RECORDER
POTENTIOSTAT
I_..~ECTRUM ANALYZER ~'--

"FOR RECORDINGAND ANALYZING

FLUCTUATIONSIN LCD ON A
POINT ELECTRODETO GET Tldc

COUNTER ELECTRODE

FIG. 25. Typical experimental set-up for LCD measurements.

(a) That based on the ferrocyanide/ferricyanide containing an excess of sodium and

hydroxyl ions, e.g. 2 M N a O H plus equimolar KaFe(CN)s and K4Fe(CN) e to
0.005 M de-oxygenated and shielded from the light. The LCD for the reduction

Fe(CN)~- q- 6e ~ Fe(CN)~- (46)

is usually measured on an inert Ni electrode (glassy carbon would seem a possible

alternative) at the anode the oxidation

Fe(CN)~- --~ Fe(CN)g- q- 6e (47)

occurs keeping the solution unchanged.

(b) The deposition of Cu from an acid copper sulphate solution, e.g. 1.5 M H2SO4 q-
0.05 M Cu SO4. 57 Mizushina ~a has suggested a correction to allow for the com-
mittal reduction of hydrogen ions but earlier results 57 of Ross show a clear
plateau. The reactions occurring are:

At the cathode: Cu 2+ + 2e --~ Cu (48)

At the Cu anode: Cu ~ Cu 2÷ + 2e. (49)

Other workers have utilized the reduction of oxygen in a 3.5 ~o NaCI solution. 2s
All the reactions discussed so far are used so that the surface does not change with
 Electrochemicalmeasurementsin flowingsolutions 427

time, indeed this is usually given as an advantage of the LCDT. However during
corrosion both dissolution and deposition can occur leading to surface roughness
and overall shape changes. Gabe 1°1 has presented some results using a Cu cylinder
dissolving at its LCD, and this approach would be valuable with other geometries.
Similarly we are examining the possibility of modelling deposition processes (e.g.
Fig. 1) using Cu deposition but allowing it to proceed and develop thick deposits.
Numerous examples of the use of the LCDT have been given in the specimen
characteristics section.

Analytical applications
As indicated the LCD of an electrode reaction depends on both the mass transfer
coefficient and the concentration driving force which is the bulk concentration when
the transport of the relevant species to the electrode is rate controlling. Thus in voltam-
metry a given geometry is used and LCD obtained in solutions of known strengths. A
calibration curve then allows the determination of any unknown concentration. For
some geometries a theoretical curve can be obtained if solution parameters are known.
There are a number of factors which in the past have limited this technique: (a)
difficulty in keeping the solid electrode clean, (b) sensitivity, and (c) interfering currents
from reactions not of direct interest.
This has led to a number of modifications to the simple voltammetric approach.
Pulse voltammetry, in which the electrode is kept clean by a programmed pulse
sequence, x02
Anodic stripping voltammetry, in which the species are preconcentrated by cathodic
deposition then anodically stripped using either a one or two electrode arrangement. 1°3
Normally the ring-disc set-up is used but other hydrodynamic geometries, i.e. a
series of concentric rings in the impinging jet, could be used.
Hydrodynamic modulation, or by varying the rotation speed about a certain value
the convective-diffusion component can be extracted in extremely unfavourable

PLATINUM ELECTRODE AND EXIT TUBE

o ~
I
GLASSY CARBON DISC 3,4ram dial
I

.2mm di0intet jet I

....

FIG. 26. Cell used for voltammetry studies (Fleet).

428 BRYAN P O ~ N

112

O. _

I I I I i

101 107 106 105

CONCENTRATION Cd 2"
FIG. 27. Typical calibration curve for voltammetry (Fleet).

circumstances, s2 It would in principle be possible to do this using other geometries

and varying flow rate.
ISO surface voltammetry (ISCVA), or controlling the surface concentration (Cs)
by simultaneously scanning id and rotation to while keeping the ratio id too,5 constant
can give both kinetic and thermodynamic information about the system,s2
An example of the type of cell that has been used in such applications is shown in
Fig. 261°~ and a typical calibration curve for this cell using anodic stripping voltam-
metry is shown in Fig. 27. There are not many examples where such techniques are
used in situations relevant to corrosion. We are currently examining the possibility
of monitoring ferric ions in acid cleaning solutions by monitoring the current necessary
to reduce them to ferrous ions.

CONCLUSIONS
1. Electrochemical measurements in flowing solutions can provide data on: (a)
corrosion rates, (b) corrosion mechanisms, (c) characteristic hydrodynamic features,
and (d) solution composition.
2. A number of possible specimens have been described and their mass transfer charac-
teristics summarized. These are not as simple as sometimes suggested.
3. An impinging jet type cell, with a choice of jet and specimen types, has been
developed which it is hoped will enable us to test the importance of certain hydro-
dynamic variables on corrosion processes.
4. Corrosion rates, even when controUed by diffusion, are not always simply related
to mass transfer, especially for specimens with non-uniform flow conditions.
Acknowledgements--The author wishes to thank the management of N.E.I. Power Eagine¢riag Ltd
for permission to publish this paper, and M. Coney, G. J. Bisnold and I. Woolsey of C.E.R.L. for
helpful discussions.
 Electrochemical measurements in flowing solutions 429

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