Crude Oil/Brine Inter fa cial Ten sions

1
Jill S. Buckley
2
and Tianguang Fan
2
INTRODUCTION
Crude oil/brine inter faces
Inter fa cial ten sion (IFT) val ues between crude oil and
aque ous solu tions are time-depend ent. This may be due in
part to slow dif fu sion of some com po nents across the inter -
face, although changes with time are not elim i nated by
pre-equil i bra tion of the oleic and aque ous phases (Freer et
al., 2003). Molec u lar rear range ment at the inter face may
also con trib ute to IFT val ues that change with inter face age.
Reac tions of the acidic and basic func tional groups of
heavier crude oil com po nents can occur when the aque ous
phase pH is very high or very low, gen er at ing in-situ sur fac -
tants that can fur ther alter the IFT as a func tion of time. Vis -
i ble evi dence of slow changes to the oil/brine inter face is
pro vided by the grad ual devel op ment of rigid films, first
reported by Bartell and Niederhauser (1949) and fre quently
observed since (e.g., Asekomhe et al., 2005 and ref er ences
cited therein).
Because crude oil/brine IFT is time-depend ent, dif fer ent
val ues can be found by dif fer ent tech niques. Ball et al.
(1996) clas si fied IFT mea sure ments based on changes in
the oil to aque ous phase mass ratio and inter fa cial area dur -
ing the mea sure ment. If both mass ratio and inter fa cial area
are con stant the method is static. An exam ple is the widely
used du Nouy ring (Adam son and Gast, 1997). Static mea -
sure ments pro duce a sin gle value of IFT. Donaldson et al.
(1969) reported IFT val ues for 43 crude oils and 0.1M
NaCl; they ranged from a low of 9.9 to a high of 31.5 mN/m.
Although the mea sure ment method was not men tioned and
inter fa cial age was unspec i fied, it is likely these val ues
were mea sured stat i cally.
June 2007 PETROPHYSICS 175
PETROPHYSICS, VOL. 48, NO. 3 (JUNE 2007); P. 175185; 11 FIGURES, 2 TABLES
ABSTRACT
Inter fa cial ten sion between crude oil and brine is an
impor tant vari able in water/oil and water/oil/gas dis place -
ments. Inter fa cial ten sion influ ences cap il lary pres sure,
cap i l l ary num ber, adhe si on t en si on, and t he
dimensionless time for imbi bi tion. Despite its impor -
tance, there is lit tle data avail able for crude oils and even
less data that can be related to key crude oil chem i cal
prop er ties such as acid and base num ber. We pres ent the
results of a study of inter fa cial ten sions for well-char ac -
ter ized stock-tank crude oil sam ples. Tran sient ten sions
mea sured by the pen dant drop tech nique were mon i tored
as a func tion of time. The effects of salin ity and pH have
been inves ti gated and cor re la tions observed between
inter fa cial ten sion and an oils acid num ber, base num ber,
amount of asphaltenes, and vis cos ity. This data set can be
used to com pare cap il lary pres sures mea sured with dif fer -
ent fluid pairs or to design core floods with model flu ids,
among many other appli ca tions. It can also be used to
exam ine mech a nis tic expla na tions for the mag ni tude of
inter fa cial ten sion between a crude oil and brine.
Keywords: inter fa cial ten sion, cap il lary pres sure
Manu script received by the Edi tor August 25, 2005; revised manu script received Decem ber 14, 2006.
1
Paper orig i nally pre sented at the Soci ety of Core Ana lysts Sym po sium in Toronto, Ontario, Can ada 21-25 August 2005. Paper num ber
2005-01 (12 pages).
2
PRRC, New Mex ico Tech, Socorro, NM, USA; E-mail: jill@prrc.nmt.edu
2007 Soci ety of Petrophysicists and Well Log Ana lysts. All rights reserved.
If both mass ratio and inter fa cial area are chang ing (e.g.,
drop vol ume mea sure ments) the method is dynamic. For
sys tems with IFT chang ing with time, the results of such
mea sure ments can depend on the rate of drop for ma tion
(Mollet et al., 1996). In tran sient meth ods, the mass ratio is
set at the begin ning of an exper i ment and changes in inter -
fa cial area are mon i tored as a func tion of inter face age. In
this work, we use the pen dant drop method to mea sure tran -
sient IFT between crude oils and a selec tion of aque ous
phases as a func tion of inter face age.
Mea sure ments and cal cu la tions of crude oil/brine IFT
Few com par a tive stud ies of IFT of dif fer ent crude oils
are avail able in the lit er a ture and none pro vide suf fi cient
details about crude oil com po si tion to allow exam i na tion of
the effect of oil com po si tion on IFT. Hocott (1939) reported
IFT as a func tion of pres sure for three crude oils. He
observed that the results were sim i lar (25-36 mN/m),
despite dif fer ent sources and ages of the three oils and sug -
gested other sweet crudes might also have IFTs in this
range.
Mea sure ments are not rou tinely made for a range of ther -
mo dy namic con di tions. Instead, IFT val ues are cal cu lated
based on a sin gle mea sure ment and the cal cu lated den si ties
of oil and water at res er voir con di tions using rela tion ships
sim i lar to that first sug gested by Macleod (1923). Macleod
observed that the sur face ten sion between a liq uid and its
vapor obeyed equa tion (1)
s r
1 4 /
=CD (1)
where s is the sur face ten sion in mN/m, Dr is the dif fer ence
in den sity in g/cm
3
, and C is known as Macleods con stant,
which is equiv a lent to P/M, where P is the parachor
(Sugden, 1930) and M is molec u lar weight. Fowler (1937)
showed the o ret i cally that equa tion (1) should apply near the
crit i cal tem per a ture, but sug gested that its more gen eral
appli ca bil ity was prob a bly for tu itous. Schechter et al.
(1994) explained that equa tion (1) results from crit i cal scal -
ing behav ior as the two flu ids approach mis ci bil ity. Both
IFT and Dr approach zero at mis ci bil ity, but not at the same
rate. Near mis ci bil ity, plots of log(IFT) ver sus log(Dr) are
lin ear with slopes of 3.88 for many fluid pairs near a crit i cal
point and this rela tion ship often extends to IFT val ues
greater than 1 mN/m.
The first appli ca tion of Macleods con stant to crude
oil/water IFTs was by Ramey (1973) who reported mea -
sure ments with an equil i brated pen dant drop as a func tion
of tem per a ture and pres sure. These and other data appear to
be well cor re lated by C and adap ta tions of this approach are
widely used in the oil indus try to esti mate crude oil/brine
IFTs from a very lim ited amount of mea sured data. How -
ever, since crude oil/water IFTs are influ enced by sur face
active mate ri als and are not approach ing mis ci bil ity, it is
not clear why rela tion ships such as that expressed by equa -
tion (1) should apply to these sys tems.
We have obtained oil sam ples from res er voirs world -
wide; their phys i cal, chem i cal, and sur face prop er ties are
col lected in the Crude Oil-Wettability (CO-Wet) data base
described pre vi ously (Buckley, 2001; Buckley and Wang,
2002). Oils with a wide range of prop er ties were selected to
eval u ate the appli ca bil ity of the Macleods con stant
approach to esti ma tion of water/crude oil IFT and to deter -
mine whether any of the phys i cal and chem i cal prop er ties
we mea sure, or their com bi na tions, are pre dic tive of IFT.
EXPERIMENTAL MATERIALS AND METHODS
Crude oil sam ples
Forty-two oil sam ples were selected from the pop u la tion
of the CO-Wet data base. Five are heavy oils (API grav ity <
22.3), 22 are medium grav ity, and the remain ing 15 are
light oils (API grav ity > 31.1). Oil prop er ties rou tinely
mea sured for these sam ples include den sity and vis cos ity as
a func tion of tem per a ture, aver age molec u lar weight,
SARA frac tions, refrac tive index, asphaltene sta bil ity con -
di tions, isoelectric points, and wet ting of mica under sta ble
and unsta ble water film con di tions. Lin ear multivariate cor -
re la tions were tested between all avail able oil char ac ter iza -
tion data and IFTs. The oil prop er ties giv ing the best cor re -
la tions (amount of n-C
7
asphaltenes, acid num ber, base
num ber and vis cos ity) and API grav ity are sum ma rized in
Table 1. Mea sure ment tech niques have been described pre -
vi ously (Buckley, 2001; Buckley and Wang, 2002). The
sam ples range in amount of n-C
7
asphaltenes from a low of
0.05% to a high of 8.75%; acid num bers range from the
limit of detec tion (about 0.01 mg KOH/g oil) to a high of
3.92 mg KOH/g oil; base num bers vary from 0.11 to 5.19
mg KOH/g oil; vis cos i ties are in the range 1.2 to 661 cP at
20C. Although not shown here, sim i lar cor re la tions would
be obtained if the amounts of n-C
6
asphaltenes were sub sti -
tuted for the n-C
7
val ues.
Aque ous phase
Sev eral aque ous phase com po si tions were tested includ -
ing dou ble-dis tilled water (DDW), 0.1M NaCl, and syn -
thetic sea water (SSW). The pH of the DDW and sodium
chlo ride solu tions was adjusted by addi tion of small
amounts of HCl or NaOH. pH mea sure ments were made
imme di ately before the solu tions were used in IFT tests. A
pH meter (Orion Model 520A) equipped with a com bi na -
tion pH elec trode (Corn ing) was used to mea sure pH.
176 PETROPHYSICS June 2007
Buckley and Fan
June 2007 PETROPHYSICS 177
Crude Oil/Brine Inter fa cial Ten sions
TABLE 1 Selected properties of crude oil sam ples and test sum mary.
API n-C
7
Vis cos ity DDW 0.1M NaCl SSW
grav ity asph. Acid # Base # at 20C pH: pH: pH:
Oil Sam ple () (wt%) (mg KOH/g oil) (cP) 3 6 9 3 6 9 6
B-1-00 37.1 0.62 0.04 0.85 4.7 x x x x x x
C-A1-00 33.7 1.66 0.34 3.44 10.6 x x
C-AG-03 40.3 0.14 0.08 0.50 1.9 x x
C-AL-03 18.7 2.40 1.79 4.94 661.0 x x
C-Br-01 48.0 0.05 0.08 0.11 1.2 x x x x x x
C-F2-03 27.9 1.97 0.70 1.32 28.6 x x x x x x
C-GC-T1-03 31.1 4.56 0.03 1.69 17.0 x x
C-K-01 18.9 3.46 2.44 5.19 396.0 x x x x x x
C-Lb-01 31.7 1.60 0.05 2.50 22.6 x x x x x x
Cot ton wood-03 26.4 2.51 0.04 1.87 26.1 x x x x x x
C-R-01 31.1 1.30 0.01 0.40 17.8 x x x x x x
C-T-02 34.2 1.36 0.01 1.30 9.4 x x
E-1XCO-01 33.8 0.65 0.18 1.93 9.3 x x
E-1XD-00 22.3 2.54 1.56 2.98 137.4 x x x x x x x
E-1XFR-01 40.0 0.26 0.16 0.65 3.7 x x
E-1XO-00 21.9 0.76 3.42 2.57 15.3 x x x x x x x
E-2XR-00 25.4 1.33 0.91 2.46 47.0 x x
E-8XFR-01 38.6 0.30 1.03 0.74 4.7 x x
E-BL-00 31.3 3.58 0.17 1.33 23.4 x x
E-S1XCA-01 23.2 2.08 0.48 3.42 80.6 x x
E-S1XG-01 33.3 0.54 0.14 1.57 9.6 x x
E-S1XL-01 33.5 0.42 0.48 1.83 10.3 x x
E-S3XR-01 30.0 0.92 0.23 2.03 19.8 x x
GOM(2)-00 21.2 8.63 2.02 1.79 122.3 x x x x x x
Gullfaks-96 27.1 0.40 0.24 1.19 15.8 x
LB-03 30.6 0.07 1.57 0.59 13.1 x x x x x x x
Mars-P 16.5 4.77 3.92 2.30 481.0 x x x x x x
Minnelusa-02 24.3 8.75 0.01 2.01 60.5 x x x x x x
Minnelusa-03 24.5 7.20 0.12 1.71 58.1 x x
MY1-02 27.0 1.59 0.50 1.17 27.7 c*
MY2-02 28.8 0.91 0.17 1.16 18.3 x x x x x x x
MY3-02 28.0 0.99 0.20 1.17 21.7 x x x x x x x
MY4-02 28.1 1.03 0.22 1.23 21.6 x x x x x x x
P-VE-00 30.6 3.43 0.05 1.54 16.3 x x x x x x
SQ-95 37.2 1.30 0.17 0.62 5.8 x x x
S-Ven-39 28.8 5.79 0.14 1.68 29.8 x x
S-Ven-40 30.2 6.08 0.13 1.62 23.7 x x
S-Ven-41 28.7 7.17 0.43 1.78 33.7 x x
Tensleep-99 31.1 4.10 0.10 1.03 18.7 x x x
W-Br-03 32.7 0.41 0.12 1.56 12.3 x x
W-Lo-03 28.1 1.68 0.39 0.94 17.8 x
W-TH-05 31.8 2.92 0.18 1.37 13.5 c*
*c = con tam i nated oil sam ple, not included in correlations
Tran sient IFT mea sure ment
IFT was mea sured as a func tion of drop age using a Data
Phys ics OCA20 pen dant drop appa ra tus with SCA20 soft -
ware. IFT was cal cu lated from drop shape and den sity dif -
fer ence by fit ting to the Young-Laplace equa tion. The pen -
dant drop method of IFT mea sure ment requires that a sta ble
drop be formed. At ten sions less than about 0.5 mN/m, oil
streams con tin u ously out of even the small est avail able
drop-form ing nee dle. Accu rate mea sure ments can be made
by other meth ods, such as the spin ning drop tech nique
(Adam son and Gast, 1997), but such obser va tions were
beyond the scope of the pres ent study.
Mea sure ment pro to col and mod el ing of IFT versus time
Pre lim i nary stud ies showed that if drop vol umes were
less than about 6 ml, IFT val ues were lower than were mea -
sured using larger drop vol umes. Drops vary ing in vol ume
from about 7 to 30 ml gave iden ti cal results. In this study, a
nee dle with OD of 0.7 mm and ID of 0.52 mm was used to
form a 10 ml drop. Drop for ma tion time was two sec onds.
Data record ing began imme di ately after the drop vol ume
reached 10 ml and con tin ued for 2000 s (about 33 min). A
sum mary of the oil/aque ous phase com bi na tions tested is
included in Table 1. Most of the data could be fit to an equa -
tion of the form
g g g g
t
= + - *
-
eq o eq
t
e ( )
/
(2)
where g is inter fa cial ten sion (mN/m) with sub scripts eq for
equi lib rium and o for ini tial read ing at zero time, t is time, t
is a char ac ter is tic time con stant with the same units as t.
Jeribi et al. (2002) used equa tion (2) to fit time-depend ent
IFT data for asphaltene solu tions and either air or aque ous
solu tions. They inter pret the long-term changes in IFT as
indi cat ing slow rear range ment of large mol e cules or aggre -
gates, anal o gous to the inter fa cial behav ior of pro teins.
Sta tis ti cal anal y sis
Sta tis ti cal cor re la tions were tested in Microsoft Excel
using Ana lyze-It ver sion 1.62 (Ana lyze-It Soft ware, Ltd.).
RESULTS AND DISCUSSION
IFT as a func tion of time
A typ i cal IFT mea sure ment is shown in Fig ure 1 for
crude oil E-1XCO-01 and SSW. The change in IFT from
for ma tion of a new drop to a drop age of 2000 s is 2.9 mN/m
and the final IFT is 21.2 mN/m. The data were fit to equa -
tion (2) using a time con stant t of 140 s.
Detailed results of more than 250 such tests with 42 dif -
fer ent crude oils were reported by Fan and Buckley (2004).
The aver age decrease in IFT from ini tial to equi lib rium con -
di tions was 4.7 2.9 mN/m (or about 23% of the ini tial IFT
val ues) with larger changes occur ring mainly in mea sure -
ments with higher pH aque ous phases. The larg est change
observed over 2000 s was 15.6 mN/m for C-Br-01 crude oil
mea sured in 0.1M NaCl with pH adjusted to 9.
IFT as a func tion of pHcom par i son of low-
and high-acid-num ber oils
Acid num ber is widely rec og nized as an impor tant crude
oil prop erty with respect to IFT, espe cially at high pH
(Cooke et al., 1974; Ramakrishnan and Wasan, 1983; Lake,
1989). The effect of pH on IFT was inves ti gated for two
suites of oils, selected from those with the low est and high -
est acid num bers, as shown in Fig ures 2a and 2b, respec -
tively.
If the results near pH 6 are com pared, both sets span the
range from about 10 to 30 mN/m, but the responses to
changes in pH away from pH 6 are some what dif fer ent.
(Note that cases where ten sion was too low to form a sta ble
drop are shown as zero, although the phases are still immis -
ci ble and low ten sions would be mea sur able by other meth -
ods.) Two of the low-acid-num ber sam ples have IFTs that
decrease con tin u ously with increas ing pH and four have
mea sur able IFTs at the high est pH tested (about 11). All of
the high-acid-num ber oils exhibit a pla teau or a max i mum
IFT value at low to inter me di ate pH and IFTs that are below
the mea sur able level in the high est pH tests. No dis tinc tions
were found between high-acid-num ber oils with low base
num bers and to those with high base num bers. IFT would
likely decrease if pH were reduced to val ues less than a pH
178 PETROPHYSICS June 2007
Buckley and Fan
FIG. 1 IFT decreases with drop age for crude oil E-1XCO-01
and SSW. The data are fit by the smooth line, which has the fol -
low ing param e ters in equa tion (2): g
o
= 24.1 mN/m, g
eq
= 21.2
mN/m, t = 140 s.
of 3, but such extremely acidic con di tions were not con sid -
ered in this series of tests.
It is clear that oils with a high-acid num ber give more
con sis tently low IFTs at high pH, but beyond that expected
result, few gen er al iza tions can be made from the com par i -
sons in Fig ure 2.
IFT mea sure ments for a wide range of crude
oils and brines
Exam i na tion of data with exist ing cor re la tions
IFT data were mea sured for the oil/aque ous phase com -
bi na tions indi cated in Table 1. In Fig ure 3, the IFT val ues
mea sured for dif fer ent crude oils with aque ous phases of pH
of 6 (DDW or 0.1M NaCl) are plot ted in terms of the
Macleod con stant and den sity dif fer ence, along with the
trends estab lished by Ramey (1973). The data appear to fit
well with the lower of the pub lished trends where the data
sets over lap and to extend the trends to lower val ues of Dr.
How ever, if they are plot ted as log IFT ver sus log Dr and
June 2007 PETROPHYSICS 179
Crude Oil/Brine Inter fa cial Ten sions
FIG. 2 pH depend ence of IFT for low- and high-acid num ber
oils mea sured against pH-adjusted 0.1M NaCl for (a)
low-acid-num ber oils and (b) high-acid-num ber oils.
FIG. 3 IFTs of crude oils with DDW or 0.1M NaCl (pH~6, 25 C,
drop age = 2000s) are plot ted as C
ow
ver sus Dr (after Ramey,
1973). These data appear to extend Ramey's pub lished trend to
lower val ues of Dr. Where the val ues of Dr over lap, there is a
ten dency for the val ues of C
ow
from this study to fall below the
main trend (dashed line) and to agree with the sec ond ary trend
(solid line) that was reported for res er voirs A and B.
FIG. 4 The 1/4-power rela tion ship between IFT and Dr was
shown by Schechter et al. (1994) to reflect the approach to zero
of both quan ti ties at mis ci ble con di tions. The change is much
steeper for IFT than for Dr. These authors dem on strated that a
crit i cal scal ing expo nent of 3.88 applied to a wide vari ety of near
mis ci ble sys tems. A log-log plot of IFT ver sus Dr for the data
from Fig ure 3 clearly shows that there is no such rela tion ship to
the crit i cal scal ing slope for the crude oil/aque ous phase IFT
data in this study.
com pared to the crit i cal scal ing slope found by Schechter et
al. (1994), it is clear that the data are not rep re sen ta tive of
an approach to mis ci ble con di tions (Fig ure 4).
As dis cussed in the intro duc tory sec tion, crude oil/brine
IFTs are influ enced by the pres ence of surfactant-like mol e -
cules in the oil that can accu mu late at the oil/water inter face
and affect the inter fa cial energy. Lower ten sions are asso ci -
ated with greater sur face activ ity of surfactant-like mol e -
cules, higher con cen tra tions of sur face-active mol e cules,
and inter ac tions with the aque ous phase that depend on pH
and ionic com po si tion. Lower ten sions in these sys tems are
not asso ci ated with the approach to mis ci bil ity that gives
rise to crit i cal scal ing. The ques tion that should be raised
there fore is why do the oil/water data fit the Macleod con -
stant ver sus Dr plot? To answer that ques tion, con sider the
data from Fig ures 3 and 4, replot ted as log C
ow
ver sus log
Dr (Fig ure 5). On a log-log basis, the data appear to be lin -
early cor re lated with R
2
equal to 0.98 for either DDW or
0.1M NaCl as the aque ous phase. Note, how ever, that a plot
of 1/Dr ver sus Dr has a very sim i lar slope and is off set from
the IFT data by a fac tor of just over two, the aver age of the
mea sured IFT data raised to the power. It is the dom i nant
effect of Dr in this plot that gives the appear ance of cor re la -
tion, but pro vides min i mal infor ma tion about IFT. Thus, the
Macleods con stant cor re la tion of oil/water IFT data with
den sity dif fer encewell away from any crit i cal pointis
unsup ported by the ory and is rather mis lead ing in prac tice
as it pro vides lit tle infor ma tion about IFT.
Cor re la tions with crude oil prop er ties
All of the avail able chem i cal and phys i cal prop er ties of
the crude oils were tested indi vid u ally for cor re la tion with
both ini tial and equi lib rium val ues of IFT. No sig nif i cant
cor re la tions were found. How ever, multivariate lin ear sta -
tis ti cal anal y sis of the final or equi lib rium IFT data pro -
duced the cor re la tion shown in Fig ure 6 with aque ous phase
pH, n-C
7
asphaltenes, acid num ber, base num ber, and vis -
cos ity at 20C. The pre dicted IFTs were cal cu lated from the
val ues shown in the imbed ded table (lower right-hand
quad rant of Fig ure 6) and oil prop erty data in Table 1. Other
vari ables tested included den sity, refrac tive index, SARA
frac tions, and iso-elec tric points, none of which improved
the rela tion ship shown in Fig ure 6.
The effects of brine pH on IFT are expected from ear lier
work (e.g., Reisberg and Doscher, 1956; Buckley, 1996;
Skauge and Fosse, 1996). In addi tion to pH, the amount of
n-C
7
asphaltene, acid and base num bers, and vis cos ity all
appear to be cor re lated with IFT. Sig nif i cance of indi vid ual
vari ables is indi cated by the value of p (Fig ure 6, imbed ded
table). The p-value is the prob a bil ity that a given vari able
has been included in the cor re la tion in error. All of the
p-val ues are low; the high est, for vis cos ity, is 0.023, well
under the value of 0.05 that is often used as a cut-off for sig -
nif i cance.
180 PETROPHYSICS June 2007
Buckley and Fan
FIG. 5 Log-log plots of Macleod's con stant ver sus Dr are lin -
ear, sug gest ing strong cor re la tion, but in real ity these plots
show lit tle more than the exact cor re la tion that must exist
between Dr and 1/Dr, also shown. Real dif fer ences between
IFTs are min i mized by the 1/4-power depend ence and appear
only as scat ter in the plot that mainly depends on Dr and 1/Dr.
FIG. 6 Equi lib rium IFT val ues cor re late with pH of the aque ous
phase, the amount of n-C
7
asphaltenes (A
s
), acid num ber (A),
base num ber (B), and vis cos ity (m) of each oil. Equa tion of the
cor re lat ing line is:
g
eq
= 21.7 1.14 pH + 0.745 A
s
1.21 A + 1.15 B + 0.0073 m.
There is too much scat ter for a rela tion ship such as that
shown in Fig ure 6 to be used to pre dict IFT from oil prop er -
ties, but it is instruc tive with regard to dif fer en ti at ing the oil
prop er ties that influ ence the equi lib rium val ues of tran sient
IFT at oil/water inter faces. Increas ing amounts of n-C
7
asphaltenes, higher base num ber, and higher vis cos ity cor -
re spond to higher IFT with brine of a given pH. The cor re la -
tion with pH is neg a tive because large decreases in IFT can
occur at the high est pH con di tions tested in this study. IFT
can also decrease at low pH, but this effect was much
smaller over the range stud ied. Increas ing acid num ber con -
trib uted to a decrease in IFT.
Oil vis cos ity was found to be a sig nif i cant vari able only
in com bi na tion with acid num ber. When acid num ber was
omit ted from the set of cor re lat ing oil prop er ties, vis cos ity
was no lon ger sig nif i cant. We tested for cor re la tions
between vis cos ity and acid num ber by exam i na tion of 139
oil sam ples in the CO-Wet data base. The log of vis cos ity at
20C cor re lated to a group of prop er ties that include base
num ber, amount of n-C
7
asphaltene, den sity at 20C (or API
grav ity), and aver age molec u lar weight, as shown in Fig ure
7. Only a weak rela tion ship between acid num ber and vis -
cos ity was found (p = 0.07); no other vari ables in the data -
base were sig nif i cantly cor re lated with vis cos ity.
IFT at con stant pHcor re la tion with oil prop er ties
The IFT data were sub di vided into groups with con stant
brine com po si tion (DDW, 0.1M NaCl, and SSW) and pH
(3, 6, and 9 0.5 pH unit). The data sub sets were tested for
sin gle and multivariate lin ear cor re la tions with all of the
infor ma tion stored in the CO-Wet data base. A set of cor re lat -
ing vari ables (n-C
7
asphaltene amount, acid and base num -
bers, and vis cos ity) was selected on the basis of these pre lim -
i nary tests. Each group was tested with the full set of vari -
ables; those with p-val ues greater than 0.05 were elim i nated.
The results of the sta tis ti cal tests, sum ma rized in Table 2
and plot ted in Fig ure 8 for the 0.1M NaCl solu tions, show
that the weight per cent of n-C
7
asphaltenes cor re lates pos i -
tively with IFTs in all cases. Oils with larger amounts of
asphaltenes have higher IFTs, with the great est effect evi -
dent at pH 6. Note that asphaltenes do not behave as
expected for sur fac tants, i.e., they do not decrease oil/water
IFT.
At acidic con di tions (pH 3), IFTs are lower for oils with
higher acid num bers, but this effect is off set some what by a
small pos i tive cor re la tion with vis cos ity. As noted pre vi -
ously, vis cos ity is sig nif i cant only in com bi na tion with acid
num ber, per haps indi cat ing that the acid num ber includes
June 2007 PETROPHYSICS 181
Crude Oil/Brine Inter fa cial Ten sions
FIG. 7 Cor re la tion of crude oil vis cos ity with oil prop er ties for
139 sam ples from the CO-Wet data base.
TABLE 2 Best correlations with oil properties for IFTs at con stant pH.
coeffiecients
Aque ous n-C
7
asph Acid # Base # vis cos ity at
phase pH n R
2
inter cept (wt%) (mg KOH/g oil) 20C (cP)
0.1M NaCl 3 17 0.74 16.8 0.598 -1.297 0.014
0.1M NaCl 6 20 0.70 11.6 1.243 1.691
0.1M NaCl 9 15 0.56 6.3 1.165 2.576
DDW 3 19 0.52 18.7 0.446 -1.602 0.020
DDW 6 43 0.46 18.3 0.461 -1.649 0.855 0.011
DDW 9 23 0.42 13.2 0.898 1.460
some spe cies that are interfacially active and other spe cies
that can asso ci ate with one another in the oil phase and
exert an influ ence on vis cos ity rather than IFT.
At pH 6, IFT increases with base num ber. The same is
true at pH 9, but IFTs are gen er ally lower, as shown by the
reduced value of the inter cept. Sim i lar results were
obtained for the DDW data, but the cor re la tions showed
more scat ter.
Syn thetic sea water
Syn thetic sea water con tains diva lent cal cium and mag -
ne sium cat ions that may have spe cific inter ac tions with
ionizable spe cies at the oil/water inter face. Nev er the less
there does appear to be some cor re la tion between equi lib -
rium IFT mea sured in DDW (pH 6) and mea sure ments with
the same oils and SSW, as shown in Fig ure 9. Only a few
direct com par i sons are avail able for 0.1M NaCl (pH 6) and
SSW mea sure ments, but they also appear to be related.
Iden ti fi ca tion of con tam i nated sam ples
Inter fa cial ten sion can be affected by amounts of sur -
face-active con tam i nants that would be dif fi cult to quan tify
ana lyt i cally in a mix ture as com plex as a crude oil. Iden ti fi -
ca tion of sam ples that may be con tam i nated with a wide
vari ety of drill ing and oil field chem i cals, many of which are
sur face-active, is impor tant for mak ing valid lab o ra tory
182 PETROPHYSICS June 2007
Buckley and Fan
FIG. 8 Com par i son between mea sured and cal cu lated IFT val -
ues. Mea sure ments are for crude oils and pH-adjusted 0.1M
NaCl. Cal cu lated IFTs were obtained using the correlations in
Table 2: (a) pH 3, (b) pH 6, and (c) pH 9.
FIG. 9 Com par i sons of IFT val ues for crude oils with either
SSW or DDW (pH6) show a weak rela tion ship between mea -
sure ments for the same oil. A better correlation exists for IFTs
mea sured with a given crude oil and either SSW or 0.1M NaCl
(pH6) as the aque ous phase.
mea sure ments. Hirasaki and Zhang (2003) sug gested that
oils with low IFTs that change with time may be con tam i -
nated, but no quan ti ta tive lim its were sug gested. Exam i na -
tion of the data in this study shows a wide range of IFTs that
depend on aque ous phase com po si tion as well as the com -
po si tion of the oil. Some guid ance is needed to pick out
con tam i nated sam ples based on low IFT or tran sient effects.
We cal cu lated the change in IFT from g
o
to g
eq
(after 2000 s)
for the pH 3, 6, and 9 data. The results (g
o
g
eq
) could be
expressed in abso lute terms (i.e., in mN/m), but that might
be mis lead ing for sam ples with low g
o
val ues. Instead a fre -
quency dis tri bu tion is shown as a frac tion of g
o
in Fig ure 10.
At pH 3, all of the frac tional decreases [(g
o
g
eq
) / g
o
] are
less than 0.4. At pH 6, most of the results are still in that
range, but sev eral oils decrease more than that, with the
larg est change being observed for the oil MY1-02 that was
iden ti fied by Hirasaki and Zhang (2003) as con tam i nated.
At pH 9, it is not pos si ble to ascribe tran sient IFT exclu -
sively to con tam i na tion.
An alter nate test for con tam i na tion is pro vided by com -
par i sons of mea sured IFT to the IFT pre dicted from the cor -
re la tions with crude oil prop er ties (Table 2). Fig ure 11
shows two exam ples of oils that clearly do not fit the cor re -
la tion that relates IFT with 0.1M NaCl at pH 6 to amount of
asphaltene and base num ber in the oil. One of these sam ples
is MY1-02, pre vi ously iden ti fied as con tam i nated. Both
have IFTs that are much lower than would be pre dicted on
the basis of their chem i cal prop er ties. The cor re la tion
method can be used in addi tion to obser va tions of tran sient
IFT to help dis tin guish cases where IFT is low because of
con tam i na tion from those where IFT is expected to be low
due to char ac ter is tics of the crude oil/brine com bi na tion.
CONCLUSIONS
IFT of crude oils var ies pre dict ably with pH and com po -
si tion of the aque ous phase. Key oil prop er ties that cor re late
with IFTs mea sured with pH-adjusted dis tilled water and
0.1M NaCl solu tions are the amount of n-C
7
asphaltenes,
acid num ber, base num ber, and vis cos ity. Dif fer ent com bi -
na tions of these vari ables dom i nate in acidic, near-neu tral,
weakly basic, and high pH ranges.
Amount of asphaltenes, as mea sured by pre cip i ta tion
with n-heptane, is an impor tant param e ter at all con di tions.
IFT increases with increas ing amount of asphaltene.
Acid num ber and vis cos ity mainly affect IFT at acidic
con di tions. IFT decreases with higher acid num ber and
increases with higher vis cos ity. Base num ber affects IFT at
near-neu tral and weakly basic con di tions. IFT increases
with increas ing base num ber. Acid num ber is impor tant in
the very basic range above pH 10. Ultralow ten sions are
con sis tently achieved only if acid num bers exceed 0.1 mg
KOH/g oil.
The IFT trends estab lished in this work for a wide range
of crude oils can be used to help iden tify oil sam ples that
June 2007 PETROPHYSICS 183
Crude Oil/Brine Inter fa cial Ten sions
FIG. 10 The extent of change in IFT over a mea sure ment time
of 2000 s var ies for dif fer ent oils. For the same oils mea sured
with aque ous solu tions of dif fer ent pH the extent of change
increases with increas ing pH, mask ing the effect of surfactant
con tam i na tion.
FIG. 11 Con tam i nated sam ples clearly depart from a trend
estab lished for many other crude oil sam ples that relates IFT
between oil and 0.1M NaCl (pH 6) to the weight per cent of n-C
7
asphaltenes in the oil and the oil's base num ber.
may be con tam i nated with sur face-active oil field chem i -
cals.
NOMENCLATURE
C Macleods con stant
C
ow
Macleod's con stant for oil/water inter faces
DDW Dou ble-dis tilled water
IFT Interfacial ten sion
s Sur face ten sion (mN/m)
M Molec u lar weight
P Parachor
SSW Syn thetic sea water
t Time
Dr Den sity dif fer ence (g/cm
3
)
g Inter fa cial ten sion (mN/m)
g
eq
Inter fa cial ten sion at equi lib rium
g
o
Inter fa cial ten sion at zero time
t char ac ter is tic time con stant with the same units as t
ACKNOWLEDGEMENTS
This work was sup ported by the NPTO office of the US
DOE under con tract DE-FC26-01BC15164, by the State of
New Mex ico, and by indus trial spon sors includ ing BP,
Chev ron, and Total.
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184 PETROPHYSICS June 2007
Buckley and Fan
ABOUT THE AUTHORS
Jill Buckley is a Senior Sci en tist and head of the Petrophysics
and Sur face Chem is try Group at the New Mex ico Petro leum
Recov ery Research Cen ter at New Mex ico Tech in Socorro, New
Mex ico. She has BS and MS degrees in Chem is try (from UCLA
and New Mex ico Tech, respec tively) and a PhD in Petro leum
Engi neer ing from Heriot-Watt Uni ver sity in Edin burgh, Scot land.
Her research focuses on inter fa cial inter ac tions between crude oils,
brine, and min eral sur faces, with empha sis on the role of
asphaltenes.
Tianguan Fan is a Research Chem ist with the Petrophysics
and Sur face Chem is try Group at the New Mex ico Petro leum
Recov ery Research Cen ter at New Mex ico Tech in Socorro, New
Mex ico. He holds a BS in Pho to graphic Mate rial Engi neer ing
from East China Uni ver sity of Chem i cal Tech nol ogy in Shang hai
and an MS in Chem is try from New Mex ico Tech. He spe cial izes in
instru men tal anal y sis with empha sis on crude oils.
June 2007 PETROPHYSICS 185
Crude Oil/Brine Inter fa cial Ten sions