.

SPE
ecfL%4JofF%tdoun

Gv#lem3

SPE 20688
Correlation of Scale Inhibitor Structure With Adsorption
Thermodynamics and Performance in Inhibition of Barium Sulfate
in Low-pH environments
P.J. Breen, Bat., r Performance Chemicals Inc.; B.N. Diel, Chemical
Baker Performance Chemicals Inc.
and H.H, Downs.

Waste Management

Inc.;

SPE Member
n
Copyr,ghl

1990. SocIeIy of Powoleum Engmoors, Inc

Th,s paper was pr6pared tor presontatfion

al the 65th Annue. Techn#c!4 Conference and Exhlbmon ot lhc Somety of Petrolaum Engmeer$ held m New Oljean% IA, September 23-26, 1990

Thts paper was selected for presenlahon

by an SPE Prqram

CommlMee followlng review of mtormahon contained m en abslract subm,tted by the author(s)

Coraents ot the paper.

as presented. have not bean rewawed by the Society of PeIroleum EnQmeer$ and are .W!qecl to Corrochon by the aid her(s) The nlaterwl. M PreSen ted. 100s not necessarily retiecl
any posmon ot the SocIe!y of PeCroleum Engmaers, IIS ofhcers. or mambers Papers presented at SPE meetmgs are subject 10 pubhcation rewew by Eddon,l CommWsas ot me Society
of PoUoleum Engineers Permission to copy la resfmc[od !O an abstra-t of WI more than 300 words Illuswahona may not ba cop,ed The absl.acl should Cc.1am conaplcuous acknowledge.
ment of where and by whOi_IIthO paper IS presented. Wrle Pubhcauons Manager, SPE, P.O Box 833836, R,*hardson, TX 75083.3636 U S A Telex, . 30989 SPi3AL

eXPERIMENTAL

ABSTRACT

All inhibitors were prepared and characterized

In order to de 2(OP inproved bariun sulfate

inhibitors for acidic (pH 4) enviromnents,
thermodynamiccs heave been masured

to check for purity and ccarpleteness of reaction,

adsorption

for severat

hrxnologous series of inhibitors uherein the molecular

Bariun sulfate (pwder)

was purchased from Fisher

Scientific Products ad

was used as recei veal,

structures have been varied systemat ica( [Y.

Correlations betueen thermodynamic,

A.

structural ewl

Static Bottle Test

performance data Hi It be discussed.

lnhibitc, performance
Synthetic

bott(e test.

INTRCWCTION

uas evaluated

in a static

formation and seti uater brines

used in the test uere prepared based on uater ana(yses

The difficulties

from North Sea formation brine and seawater.

associated u,th the inhibition oi

bsriun su(fate ;c~le in acidic (PH 4)

environments Zfre

compositions

ue Li docunwnted - . This has been comnonly attritwted

The formation brine contained

to the decreasing amount of ionized inhibitw

uhi Le the seawater contained

is [o~er~s.
preventing

Overcming

scale formation

as the pH

this prob[em is essential to

730 mg/L barium on,

2650 w/L

The test procedure

with

involved piacing the inhibitor in

the formation brine, foltowd

high (ea. 1000 ppn) tevels of bariun.

by PM adjustment uith H..

to the desired va(ue (usually 4.0).

We have measured scale inhibitor performance

of pH-adjustM

in art

effort to develop a more fl!rdmnenta~ understanding

the mechanisms of scale inhibition.

were

sea water brine.

Upon teqw?aturc

equi Iibration, the sea uater was addad to the formation

water/inhibitor

of

Our sttxiies have

corresfwwds

samples in a 15:8S ML ratio.

nhibitors which are more effective at

one.

to stand in the bath at 85C

overnight (approx. 17 hrs. ).

products uhich \e have

This

to a SOL 2- :Ba2+ ratio of apfwoximatety

The bottles were at~owd

lad tc the deve opnent of several new, proprietary

the c-mercial

San@es

equi tibratad in a water bath (85C) along uith samples

as a

function of systematic changes in structure, arid

adsorption thcwnoclynamics (on boriurt sulfate)

ph 4 than any o

sulfate

ion.

in certain North Sea oi I

fields, uhich tend to have acidic formation briws

barium su(fate

The

of these brines are listed in Tab(e 1.

A~fwot$

uere taken and

di lutad 75% in deionized uater and irmtadiately

analyzed for resfdual bariun using Wait
absorption
spectroscopy.
Fi (tration of the Sanp(ea through a 0.45

tested.

f i(ter was observed to have no ef feet on measured

ievals of bar!un

ion.

A va~ue of O% inhibition uas taken to be the

References and f igurea et end of paper.

711

CORI(ELATION OF SCALE lNHIBITOR STRUCTURE UITH ADSORP71W

AND PERFORMANCE

concentrateior (mg/L ot bsrlun in a %! ankj sanple whi;h

contained
no inhijitor.
100% inhibition was taken to
Percent

be 621 mg/1 bariun.

SPE20W

c~iusions

ar~;in~ from corrperisons of

according to
RESULTS ANO DISCUSSION

equation 1.

Figure 1 is a p[ot of percent inhibition obtained

(sar.$nle- blank)
.

% Inhibition =

(1)

x 100

(621 - blank)

versus log mo, ecular ueight of a horml~gous series of

phosphonete
25 w

inhibitors, for non-seeded conditions at

of inhibitor in the static bottle test.

is also iisted in Table 2.

the performance

Seeded gronth bott(e tests Mere conducted as

described above except

ttrat 0.5 g of pwtiered bariun

goes thrcugh a maximun uith respect to

molecular weight.

This effect most likely reflects

d.anging edsorption characteristics

adjustment.

is varied.

same series of inhibitors versus the me3sured

~~sorption
thermodynamics

of state inhibitors on

sulfate Mere determined

fol(owiny procedure.

as nwle.~iar Height

Figure 2 is a plot of log molecular weight for the

inhibitor Adsorptiti, Test

bsrim

The data

As can be seen ir,the figure,

sulfa*e Has t.kkd to the formation brine prior to PH

B.

AGadS for

simi[ar types of inhibitors. since t is not expected

to vary significantly.

inhibition for any given

inhibitor sanple was ther calculated

THERM(l~YNAMICS

IN .NHIBITION OF BARIUN SULFATE IN I.W PM ENVIiWNHENTS

increases, &a4s

according to the

20 mL of a 500 pgsn solution of

&ads.

The data in Figure 2 illustrate that as molecular iieight

beccmes increasingly negative,

active inhibitor in deionized uat:r were p~aced in a

suggesting that adsorption increases uith increasing

tl to a point.
Such a result is
mlecular
ueigh

test tube conteininS a precise~y ueigh~

consiste).t with ldti-sesvnental

of baritxn sulfate.

amount (5-2Q)

A BET surface anatysis revealed the

neight incr~ases, adsorption

attachment; as molecular

increases and the

bariun sulfate to possess a surface area of 2.994 x 104

reversibility

cm2/g.

increasing nurber of points of attachment.

The tube uas capped and vigorously stsken at

regular intervals over the course of a day and a(lo~ed

Inhibitors uere at(oued to absorb at

to set overnight.

roan temperature and at 85C in a water bath.

tubes uere then centrifuged

for 1-2 minutes.

using a Zr (IV)-arsenazo

this trend is a decrease

in diffusion

Countering

rate with

increasing motecular ueight, resulting in feuer

collisions between inhibitor and bariun sulfate nuclei.

The
The clear

supernatant uas removed ar-d tir~e:xl for phostionate

concentration,

of the adsorption decreases, due to the

The result is that at high mo(ecutar weight, inhibitor

efficiency drops off, as demonstrated

in Figures 1 and 2.

titration
If the primary mechanism

devetoped for this purpose.

OT scale inhibition

invo~ved the blockage of act:ve growth sites on the

Follouing the methods of Naono6, Mads

uas

crystal surface, then it brould be reasonable to expect a

calculated from,

correlation betueen~ads

and percent inhibition.

Such

correlation appears to be absent between Figures 1 and

Gads

(2)

= -RTin[(Ci f)V/gCfATl

for differen: mlecular

Uhere ci=51313ppr?, Cf=fina(

phOSphOf%te

concentration,

surface area pw

gram, T=mono(ayer

una of solution.

thickness and V=voi -

AHadS

was calculated

T1T2

(n cT2ci-cT2cTl

ueights.

a plot of percent

ads

of inhibitors under seeded grouth conditions.

In an

unseeded experiment, barium sulfete partic(es need to

from,

thermodynamically

CR

stable

nucteus) before they are

due to the unfavorable

chemicet potentiai associated uith surfac~ sites versus

T1-T2

so(vated ions.

cTlci-cT2cTl

A very sma(( crystat embryo has a (argc

ratio of surface awns

uhcre CT, orti CT2 are the ffna( phosphonate
concentrations

3, uhich is

inhibition obtained for the same series

exceed a critical size (~itical

AH

An exce~~ent match

occurs, however, betueen Figure 2 and Figure

g=grams of bariun su(fate in the tube, A=bariun sulfate

2,

ho~ever, since the mexirnun in these two figures occurs

at temperatures

AS ads uas calculated

T, and T2.

frMaGads

ati~ads

to tw~k atoms, so that at such e

stage there is an energy barrier to homogeneous

nucleation.

If stabie growh

sites exist, however, such

as on the ualls of the container, or on the surface of

using,

relatively

as ads = ( AHadS-AGadS)/T
Since ue have no info mstion
monoiayer thickness

(4)

about t, the

in equation 2, we have used for the

purpose of our ca~culations

a value of 1X10-7 cm.

This

Large crystat seeds, then there is a greetly

Under such
reducfxl energy barrier to crystallization.
I%eterogcneous$l
corn?itions. b(ockage o jrotith si tes is
expected to be the prllicpv mechanism of inhibition, and
tne good corrc[at ion betueer, _&ad~
in Figure 2 and
Fercent inhibition in Figure 3 support this conclusion.

is the va(ue given by Naono6 for sodium tri~lyphosphate.

The nccuracy of this value should have minimal impact on

An additional mechanism of inhibition, original~y

SPE20. 88
pro~sed

PATRi CK J. BREEN, BRUCE N. DIEL AND HARTLEY If.OWNS

by Naonod, can be used to expiain the

Higher mo(eculai weight. ~lymeric

(t, G, and H in Figure 5) however, ah~

difference in the performance maximum for Figues 1 and

.
c. As illustrated in Table 3, AHads is gmitive

adsorption behavior.

(endothermic

5.5, the amount of aosorbed

tested.

adsorption)

Tnis mrws

for a( 1 of .he inhibitors

imreasi~

that inhibitor adsorption uill

cnuse the chemical potent ia( of surfs@

scale inhibitois,
different

Figure 5 i1lustrates that at pH >

inhibitor decreases

natecu~ar we;ght while at #

uith

< 4.0, adsorption

aeema to irwrease with increasing nm(ecular weight.

&i tes to be

even nmre unf avora~(e, thereby raising the energy

These trends alao seem to corre.ate uith data presented

barrier for further grouth needed to reach cri ticat

in Figure 4, where (OW molecular ueight inhibitors (B and

C; out~rform
higher molecular weight inhibitors (E, I,

nucleus size.

Thus, endothermic

adsorption

increases

and J) at pH ~ 5.5.

the probsbi Iity that the embryo ui II redissolve.

Since the msxirman in Figure 1 OC(WS

at a lower

motecular ueigl,t than in Figure 2, ir a%ars

type of homogeneous
sca!e inhibition
moleculw

contribution

ts more

Literature precedent exists which can ~id in

that this

explaining

t,)the mechanism of

decrease

iJnificant for lower

these resuits. Uillisms #

et i~l
.-. observed o
in the adsorption of sodiun carboxycelluiose on

bsriun sulfate as the pH uas raisd,

weigh: inhibitor:.

and attributed the

effect to increased charge den~ity on the polymer at

higher pH which Leads to J builchp of charge near the

The isoelectric point of bef iun sulfate uas

reported by Williams, et al .8 to corre~pord to a pllof

baritrn sulfate surface duc to msdsorbed

polyner

This shietdi,~y charge! hildtq

segments.

then reps(s

3.8, msaning th,at at PH 4.0 there is a slight excess of

Thus, the
cvera.( negative charge on the surface.

other, similarty charged F~lyners away frcm the surfece.

erdothermicity

Thus, as pH is raised, charge density of the po(ynwr

electrostatic

of the adsorption
xtueen

repuls~-

derives from

increases and adsorption decreases.

the negatively charged

bsriun sulfate :,urface and the negatively chargd

Inhibitors E, 1 md

functiona( groups of the inhibitor motecute.

J represent a hcm(ogous

series

wherein the total nurber of phosF ~nate groups per

In order for adsorption

to be si%mtaneous

(energet ica( \y favorable), the posi tive &lads must be

overc~
by a Large positive &ads.
The dissociation
uater molecules which are hydrogen-bonded

of

molecute

is steadi(y decreased,

decrease

in charge density.

as the nwber

of phosphonate

corresponding

to a

Figure 4 il~ustrates that

groups is decreased

(E > I > J), the area of msximun performance shifts to

higher PH. Thus it a~ars
that there is an optims(

to the

inhibitor motecule, as the inhibitor adsorbs to the

bsriun sulfate surface, can impart such a vaiue to

charge density for such inhibitors which al(ows for the

It is interesting to note that scale

As.
ir %tors
uith ASads < 16 caL;mol K (Tabte 3) give

greatest amount of adsorption, and which

poor performance

in the static btt(e

The Loiiervalues for&ads

smaller hydration s~ere

presmab~y

test (Table 2).

Our dots supports the hypothesis

arise from the

of sca(e inhibition are operative:

such inhibitors possess

endothermic

The data sugges that

prior to adsorption.

content.

This conclusion

also reached by van der Leeden ard van Rosma[en

published $tuiy evaluating wlycarboxylate

adsorption

irreversible

Has

resulting in dir,olution

Wiymer adsorption at the active grouth

scale

important for (OW mtecular

weight inhibitors since such

nwlecules uould have difficulty

since adsorption

The percent inhibition as a functicn of PH is

inhibitors in Figure 4.

Endothermic

c~oser to 2000

cal/mol.

coutd sti [( increase due to an

Asads

SUMMARY

arisin9 from the iar9er

hydration smere 9enerated by the added charge on the

inhibitor. This is exact(y what was observed uhen
were
determined for inhibitor
ad
&ads
ads ads
A at PH 8.0 (Tabte 2). The adsorption curves in Figure
rwxt non-pel~ric

inhibitors such as

A, L and N often have Va(ues for ~ad~

bsriun sulfate embryos, which are smsl{er

In spite of the increasingly
than criticat nucleus size.

5 for inhibitors A and

The thermodynamic date in Table 2

1200 cal/mol, uhereas sma[l motecule

and therefore more (ikely to

destabilize

- +iads

is not as essentia( for polymeric

Wlyneric
inhibitors
such as
supf.wrt such a statement:
inhibitors F, G and H tend to have Vatues Of ~Hads near

bsriun sutfate embryss, shoutd result in adsorption that

increasingly positive

adsorption

crysta( growth sites.

pH, along with an increased negative charge on the

posit ive AHads#

b(ocking gro~th sites

is expected to be highly reversible.

inhibitors since they can irreversib~y adsorb to the

Most inhibitors tested showed in+roved inhibition with

increasing pH. The increased ionization, due to higher

is more endothermic

of bsriun

sites Of bariun sulfate nuclei , resulting in their

The first mechanism is expected to be nwre
biockage.

in a

inhibitors .

presented for severel different

that two mechanisms

one !lvoLving

sulfate embryos, and another invo(ving essentially

successful state inhibitors shou~d possess structures

uith minimal hytiophobic

an be

controt(sd by PH or degree of substitution.

Low nmlecu(ar weight inhibitors perform best in

regions of relatively high pH (z7) where they are
ionized to a greater extent.

D appear to be representative for

Polyneric

especially polymeric phosphonates,

inhibitors,

are lluety to show

performance maxims as a function of pH, due to

scale inhibitors.

713

CORRELATION OF SCALE INHIBITOR STRUCTURE WITH ADSORPTION

AND PERWRWNCE

4
electrostatic

shielding effects at the scale surface,

uhich are deperdent

THERNCOYNAHICS

3.

J. E. Ramsey, L. M. Cenegy, A LalWrriorY

Evacuation of Bariun Sulfate Scale Inhibitors at

on tbe extent of ionizaticm.

Lou pH for Use in Carbn

Effestive

low molecu(ar

su(fa:e txrbrycs through highly

endothermic adsorption,

driven by fabu, able ent,-opy

with the reiease upon aciso-ption

Conference,
4.

iydrophobic

of a Large nunber of waters of hydration.

weight

a mechanism

involving

7862 presented at the SPE International Symywsiun

blockage of active grouth sites is therefore inpl ied fcr

such inhibitors.

For this reason, ~[ymeric

in situations

uhere a significant

sites a[ready

nurber of nucleating

on Oilfield and Geothermal Chemistry, Houston,

inhibitors

are most likely to yie!d good inhibition

D. u. Griffiths, S. O. Roberts, S.-T. Lt1,

l)lnhibit ion of Caicim S ~ifate Dihydrate CrYsta;
Inhibitor Structure and Solution pH, Paper SPE

:to a point) leads to better,

ard less reversible, sdswption:

Texas, 1979.
5.

exist.

U. H. Leung, G. Ii.Nanco(las, J. lnorg. Nucl.

Chem.,

REFERENCES

Las Vegas, Nevada, 1W5.

Grouth by Phosphoric Acids - Influence of

sections are therefore undesi rab[e for good inhibit im.

Increasing molecular

Dioxide [OR Floods,i

Paper S~E 14407, presented at the SPE Smual

weight inhibitors operate

by destebi lizir,g barim

conditions ass~ciated

SPF20688

IN INHICITION Of BARIUM SULFA,. .N LOU PH ENVIRONMENTS

6.

vol.

!Ja-ono,H.

40, p. 1871, 1978,

Butl.

Chem. Sot. Jpn., Vol. 40, p 11OL,

1967.
1.

G. R. Chesnut, G. D. Chappe Ll, D. H. Emnons, The

Development

of Scale Inhibitors and Inhibitor

Evaluation Techniques
Floods, Paper

7.

for Carbon Dioxide EOR

Pergamon Press:

Oxford, London, 1964.

SPE 1A260, presented at the SPE

I,iternational S~siun

on Oilfield Chemistry,

8.

San Antonio, Texas, 1987.

2.

A. E. Nielsen, Kinetics of Precipitation,

E. R. McA,tney, A. E. A(exander,
Vol. 13, p. 383, 1958.

P. A. Uiltiams,

R. Harrop, G. O. +hil(ips, Chem.

Sot. Faraday Trans. 1., Vol 78, p. 1733. 1982.

J. Colioid Sci.,

9.

M. C. wan der Leeden, G. P. van Rosmalen,

~lInhibition of Bariun Sutfate Depaitior, by
Polycarboxy[ates

of Various Molecu(ar Structure, i

Paper SPE 17914, Juiy 1988.

SW
.

Table

Brine Compositions

Synthetic

Formation Brine

Seawater

Salt
NaCl

mu/L
65,520

Salt
NaCJ.

3,919

Na2S04

1,300

Bac12.2H20

*3
.,

Table 2 - Static Bottle Test Results

BaSO
Inhibltora

% Inhibition
Seeded
Unseeded

MW

7
60
49
51
78
57
42
34
71
49
0
0
0
0

436
710
847
984
1,920
3,840
31,800
159,000
1,660
1,390
492
206
205
275

A
B
c
D
E
F
G
H
:
K
L
M
N

4
47
37
39
64
79
$14
35
2
2

aA-H; homologous series, inc. MW.

E,I,J; homologous series, dec. charge
density. K,L; typical commercial
phosphonate inhibitors. M,N; other
phosphonate inhibitors.

Table 3 - Thermodynamic Data for Adso~ption Onto BaS04

Inhibitor
A,
A,
B,
D,
E,
F,
G,
H,
I,
J,
K,

pH
pH
pH
pH
pH
pH
pH
pH
pH
pH
pH

4
8
4
4
4
4
4
4
4
4
4

AHadS(Cal/i:ale)

2061
3139
1243
951
1224
492
1031
1180
1866
1085
2025

t
?
k
t
f
k
t
t
k
t
i

ASad~(Cal/mOle~)

20G
7
663
162
385
280
467
366
247
247
240

19.9

24.8
17.2
16.5
18.0
16.6
17.5
15.7
19.4
15.1
15.8
715

Y
k
t
t
t
t
t
i
i
i

AGad~(Cal/rnOle)

0.9
0.1
2.1
0.4
1.5
0.8
1.6
1.0
2.5
1*O
0.1

-3818
-4214
-3852
-3921
-4112
-4423
-4163
-3468
-3876
-34C0
-2656

t
t
f
?
2
k
t
2
?
i
t

240
48
61
57
252
151
62
66
199
335
250

20688

100

0
:.50

,,.,

J
5.50

4.50

3.s0

~.~

10S MW

10S MW
Figure

1. % inhibition
as a function
of
conditions.
MW for unseeded

Figure

5.s0

4.5e

3,50

2.$0

2.

-,\GwdB on BsS04
MW. T=298
K.

as a function

of

80
-

60

m
MW-710

1/=

40

20
0

c
NW-847
33
Mw-l,szo

80
*O

1
MW-1,640
J
MW-1.3$0

40
20

r-l
o~-

1.s0

$.5e

4.50

3.50

4.3

3.5

2.5

5.5

6.5

7.5

QH

Fi&ure

3. % inhibit
MW for

on as
wedcd

a function
conditions.

>

Figure

of

&

kAw.436
*D
uw.

/
v

3700

% inhibition
PH. unseeded

-A

41eo

4.

n14

-P
UW-3,84Q
-+--

o
Mw-31,800

-H
MW-lj9,000

Ssoo
1.0

2.0

3.0

4,0

$.0

6.0

7.0

8.0

pH
Figuro

5.

-,jGadm

T=298

K.
716

a function

of

PH.

m a function
conditiotim.

of

CORRELATION
?

OF SCALE INHIBITOR STRUCTURE WITH ADSORPTION TtiERkiODYNAMICS

AND PERFORMANCEIN INHIBITION OF BARIUM SULFATE IN LOU fJHENVIRONMENTS

RESULTSAND DISCUSSION
Figure 1 is a plot of percent fnhibftfonobtained
versus log molecularweight of a homologousserfes of
phoaphonateinhibitors,for non-sesdodconditionaat
25 qxn of inhibitorin the static bottle test. The data
is also listed in Table 2. As can be seen fn the ffgure,
the performancegoes througha maxinwm with respectto
molecularweight. Thfa effect most lfkely reflects
chengingadsorptioncharacteristicsas molecularwefght
is varied.

(sample - blank)
x 100

% Inhibition=

(1)

(621 - btank)

Seedei growth bottle tests Mere conductedas

describedabove except that 0.5 g of pouderedbarfum
sulfstewas adciadto the formatfonf>rineprior to pH
adjustmant.

Figure 2 ia a plot of log moleculerweight for tha

the
lnaaSUIWf
&ad5.
same gerfes of inhibitors versus
The data fn Figure 2 illustratethat as Irdecularwefght
increases
#@ads b@c~s increasinglynegative#
suggestingthat adsorptionincreases~ith increasing
molecularweight, up to a pofnt. Such a result is
consistentwith rrdtf-se~mentalattachment;as molecular
weight increases,adsorptionincreasesand the
reversibilityof the adsorptiondecreasea,due to the
increasingnwiber of pofnts of attachment. Countering
this trend is a decrease in diffusionrate wfth
increasingmolecular weight, resultingin fewer
collisionsbetween inhibitorand bariun sutfate nuclei.
The resutt fs that at hfgh molecularweight, inhibitor
efficiencydrops off, as demonstratedfn Figures 1 and 2.

InhibitorAdsorptionTest

Adsorptionthermodynamicsof scele inhibitorson

barium sulfate were determinedaccordingto the
following procedure.
active fnhibitor

20 ml of i?500 Mcolution

of

% defonized water ware placed in a

test tube containing

a precisely

weighed mount

(5-20g)

of barium sulfate. A BET surface analysts revealedthe

ba fum sulfate topo$sess a surface area of 2.994 x 10{
5
cm/g.
The tube was capped arwivigoroustyshaken at
regular intervalsover the course of a day and allowed
to aet overnight. Inhfbftorswera allowed to absorb at
room temperatureand at 85C in a water bath. The
tubes were then centrifugedfor 12 minutes. The clear
supernatantwas removed and titratedfor phosphonete
concentration,using a Zr (W)-arsenezo tibration
deveiopedfor this purpose.
Followingthe methods of Naono6#~ad~
calculatedfrom,

If the prfmarymechanismof scale inhibition

involvedthe btockageof act!ve growth sftes on the
crystal surface, then it wou(d be reasonableto expect a
inhibition. Such
correlationbetween~ads atIdPerCent
correlationappears to be absent between Ffgures 1 and 2,
however,since the maximum in these two figuresoccurs
for differentmolecularweights. An excellentmatch
occurs,howcvar,between Figure 2 and Figure3, which ia
a plot of percent inhibitionobteined for the same series
of inhibitorsunder growth condftfona. In an
unseededexperiment,barium sulfateparticlesneed to
exceed a criticalsize (criticalnuclaus)before thay are
thermodynamicallystable7due to the unfavorable
chernicot
potentialassociatedwith surfacesites versus
aolvated ions. A very small crystol embryo has a large
ratio of surface atoms to bulk atoms, so that at such a
staae there is an energy barriar to hcincganeous
nucleation. If stable growth sftes exfst, however,such
os on the walls of the container,or on the surfaceof
relativelylarge crystat seeds, then there is a greatly
reducadenergy barrier to crystallization.Under such

was

ATl
~Gads = RT1n[(Ci-CfW9Cf

(2)

concentratton~
where Ci=500 ppm, Cf=ffml phosphonate
g.gramsof barf~ sulfatein the tube, A=bariumsulfrNe
surfacearea par gram, T=monolayerthicknessand V=volflom,
ums of solution. ~Hods W8S calculated
T1T2
AHad~ ~ R
T,-T2

cT2ci-cT2cTl
[n...
cTlci-cT2cTl

uhere CT1 and CT2 are the final phosphonate

concentrationsat temperaturesT1 and T2.
&ada was calculetadfr0??lA6ads
Qnd4~Gd~ usfn9#
ASods (~Had~ =&lads)/T .

SPE20688

conclusionsariaing from c~arisons of AGads for

simitar typea of fnf]fbftors,
since t is not expected
to vary significantly.

concentration (mg/L of barium in a btankll

srxmptewhich
containedno fnhfbitor. 100% inhibitionwas taken to
be 621 mg/t barfwn. Percent irrhfbftfon
foranygfven
fnhfbitorsample was then calculatedaccordingto
equation1.

B.

(4)

Ilheterogenaousllconditions, blockaga of growth sites is

Since we have no informationabout t, tha

monolayer thickness in equation 2, we haveused for the

expected to be the primarymechaniem

of inhibition, ati

tha good correlationb@weeT~-&ad$ in Figure 2 and

percent inhibitionin Figure3 support this conclusion.

purposeof our calculations

a valueof lx10-7 cm. This
ia the volue given by Naono6 for sodium tripolyphos~ato,
The accuracyof this va[ua should have minfmal fmpacton

Anaddftional mechanismof inhfbftion,originally

712