Physical Properties
PETROLEUM RESERVOIR
ENGINEERING
Physical Properties
JAMES W. AMYX
DANIEL M. BASS, JR.
ROBERT L. WHITING
The Agricultural and Mechanical College of Texas
efill'>'APITtn
McGRAWHILL
CLASSIC
TEXTB<PK
REISSUE
         
PREFACE
15 16 VBAVBA 8 9 3 2 I 0 9 8
ISBN
0070016003
TI
PREFACE
Jame. W. Amyx
Daniel M. Bass, Jr.
Robert L. Whiting
CONTENTS
Preface .
Key to Symbols
xi
1. Introduction
General Composition of PetroleumPhysical Properties of HydrocarbonsOrigin of PetroleumTrapsDistribution of Hydrocarbon Fluids in TrapsLithology of Petroleum ReservoirsDrillingCabletool DrillingRotary
DrillingWell Completion and ProductionReservoir Performance.
2. Fundamental Properties of Fluid Permeated Rocks
36
36
Introduction
Porosity
. . . . . .
36
Laboratory Measurement of PorosityPrecision of Porosity ~feasurements
Carbonate RocksCompressibility of Porous Rocks.
Permeability . . . . .
.
64
Horizontal FlowVertical FlowRadial FlowPermeability of Combination
Layerscb.annels and Fractures in ParallelAnalogy of Darcy's Law and
Other Physical LawsMeasurement of PermeabilityFactors Affecting Permeability MeasurementsFactors in Evaluation of. Permeability from Other
Parameters.
100
Fluid Saturations
. . .
Methods of Determining Fluid SaturationDetermination of Fluid Saturations from Rock SamplesFactors Affecting Fluid Saturations of CoresThe
Use of Coredetermined Fluid Saturations.
110
Electrical Conductivity of _Fluid Saturated Rocks
Resistivity RelationsMeasurement of Electrical Resistivity of RocksEmpirical Correlation of Electrical Properties.
S. Properties of Porous Media Containing Multiple Fluid Saturations
133
133
Surface Forces and Capillary Pressure .
Fundamentals of Surface and Capillary ForcesLaboratory Measurements of
Capillary PressureInterstitial Water SaturationsCalculation of WettabilityPoresize Distribution and Calculation of Permeability from Capillarypressure Data.
174
Effective and Relative Permeability
. .
Laboratory Investigations of Relative PermeabilityThreephase Relative
PermeabilityMeasurement of Relative Permeability DataUse of Effective
and Relative Permeability Data.
4. Fundamentals of the Behavior of Hydrocarbon Fluids
211
Introduction
Basic Concepts of Phase Behavior .
211
212
vii
viii
CONTENTS
CONTENTS
359
Introduction
Sampling Reservoir Fluids
Bottomhole Sampling~combination SamplesSplitstream Sampling.
Laboratory Analysis of Reservoirfluid Samples
.
Relative Total VolumeDifferential Oil Formation Volume Factor and Gas in
SolutionFlash Separation TestGas CompressibilityFluid VIScosityDifferentialflash Oil Formation Volume Factors and Gas in SolutionEquilibrium RatiosFluid CompositionPresentation of a Fluid Analysis
for .a GasCrudeoil System.
Preparation of Fluidanalysis Data for Use in Reservoir Calculations
.
Smoothing Laboratory DataCorrection of Laboratory Sample Data for Separator ConditionsTotal Volume FactorsCorrecting Fluidanalysis Data to
Reservoir Bubblepoint Pressure.
Fluidanalysis Data on Gascondensate Systems
Laboratory Measurements.
Applications of Fluidanalysis Data
. .
. . .
Fitting Published Equilibriumratio Data to Laboratory Fluidanalysis Data
Other Methods of Determining Hydrocarbon Fluid Properties .
Modified Ideal SolutionsEmpirical MethodsCalculating Reservoir Volumes for Gascondensate SystemsCorrelations for Fluid \Tiscosities.
359
6. Properties of Water
360
365
411
415
417
425
448
473
Introduction
473
Field Records .
475
Completion and Workover RecordsProduction RecordsWell Tests.
497
Average Fluid Properties
Reservoir Fluids Existing in the Gaseous StateReservoir Fluids Existing in
the Liquid State.
Evaluation of Rock Volume
517
Areal ExtentIsopach Maps.
561
561
562
Introduction
Derivation of Materialbalance Equation
Solutiongas DriveSolutiongasGascap DriveSimple SolutiongasGascapWaterdrive ReservoirsSolutiongasGascapWa~erdrive with F~uid
InjectionSlightly Compressible Hydrocarbon ReservorrsGas ReservorrComparison of Drives.
575
Data for Material Balance . . .
Fluidproduction DataReservoir TemperaturesReservoir PressuresFluid
AnalysisCore Analysis and Laboratory Rock Data.
589
Calculation of Oil in Place Using the Materialbalance Equation .
Estimation of Oil in Place for a Solutiongasdrive ReservoirEstimation of
Oil in Place for Slightly Compressible FluidsEstimates of Gas in Place from
Material Balance.
599
Name Index
Subject Index
383
Introduction
448
Physical Properties of Water
450
Solubility of Natural Gas in WaterCompressibility of WaterThermal Expansion of WaterWater Formation Volume Factor:Density, Specific Volume,
and Specific GravityViscosity of WaterSolubility of Water in Natural
GasElectrical Resistivity of Water.
470
Chemical Properties of Water
7. Data Evaluation for Reservoir Calculations
Hydrocarbon Volume
. . . . . . . . . . . . . . . .
Evaluation of Porosity and PermeabilityWater SaturationCalculation of
Hydrocarbon Volume.
ix
536
603
KEY TO SYMBOLS
ENGLISH LETI'ER SYMBOLS
a
A
A
AT
Aa
b
B
Bfl
Bae
B;
Bo
B,
B.,,
c
C
C
co
1
Cg
Co
c,,
c,.
c,.
c'UI
C'
d
D
e,
e.
ew
xii
f
F
F
F
f'
g
G
G
g,
Gdh
G.,
G,
t;.G,
G,
t;.G,
G,
t;.G,
G,,.
G,,.
G,.
h
h
H
h,
H,
H,
H,
i
I
I
i,
iw
I,
J
J,
k
K
K
k,
k,
k.
k,,
k ..
k,w
kw
k,
L
L
L,
m
m
m
m
m
m
M
n
n
n
N
N,
t;.N,
N,
t;.N,
p
p
P,
P~
p,
p,
P,
P,
P,r
Po.
P ..
p,
PD
P,
Pr
p,
P,
P,.
P,,
p,
xiii
xiv
P ,1
Pt
PVL
P,,,
p wf
p w
Q
qD
q,
qo
qw
r
r
R
R
R
R
rn
r,
r,
rw
Re
RL
R.
R..
R11
R,
Raw
RT
R.
0
S
S
sq
Sac
Sa.,.
S0
Sor
SP
SP
S,
S,,,
Swc
SW'r'
t
t
T
tD
Tc
T,
Tse
u
v
v
V
V
Vs
v2:
VB
Vm
VP
V.
w
w
W
We
D.W,
W;
D.W;
WP
.6. WP
x
X
y
Y
z
XY
fl
'Y
1 When the mobilities involved are on opposite sides of an interface, the mobility
ratio is defined as the ratio of the displacing phase mobility to the displaced phase
mobility or as the ratio of the upstream mobility to the downstream mobilit.y.

xvi
'Yo
"tu
il.
e
~
>.
>.
Au
>.
Aw
I'
l'u
l'o
l'w
v
p
Pu
P
Pw
"
"r
"'
<l?
'1'
av
a
a
a
b
b
B
c
c
c
cf
cp
cs
d
d
average
atmospheric
air
actual
bubble point, or saturation
base conditions
d
D
e
e
f
f
f
f
g
he
i
i
i
L
L
m
m
m
max
min
M
nwt
0
p
p
p
p
p
pv
r
r
r
r
R
R
s
s
s
SC
sp
st
SW
t1 T
differential separation
dimensionless qun.ntity
cumulative influx or encroachment
external boundary conditions
flash separation
front, or interface
formation or rock
flowing
gas
hydrocarbon
initial value, or conditions
ith component, etc.
cumulative injected
laboratory
liquid
mean
mercury
mixture
maximum
minimum
molal
nonwetting
oil
pseudo (preceding)
cumulative produced
pure
perforations
pore (used with volume only)
pore volume
reduced
relative
reservoir
residual
residual
reservoir
gasoil solution (used in R, only)
shutin
solid
standard conditions
separator conditions
stock tank
gaswater solution (used in R,w only)
total
xvii
xviii
T
T
if
ts
v
VL
w
wt
w
wf
ws
threshold
tension (used with adhesion tension)
tubing, flowing (used with pressure only)
tubing, static (used with pressure only)
vapor.
volumetric
water
wetting
well conditions
MATHEMATICAL NOTATIONS
dx
notation of derivative of x
f( )
g( )
In
log
function of
function of
logarithm to the base e (natural logarithm)
logarithm to the base 10 (common logarithm) or with appropriate
subscript to base indicated by subscript.
s
distance along direction of flow
x,y, z notation of coordinate axes in threedimensional space
ax
notation of partial derivative of x
finite increment
2:
ABBREVIATIONS
av
0
API
bbl
cc
cm
cp
cu
ft
FVF
gm
GOC
GOR
gpM
lb
M
MM
Mscf
PI
PSI
res
scf
sec
sep
SG
SPI
sq
STO
woe
average
cubic
feet
oil formation volume factor
gram
gasoil contact
gasoil ratio, standard cubic feet per stocktank barrel
gallons per thousand standard cubic feet
pound
thousands
millions
specific gravity
specific productivity index
square
stocktank oil
wateroil contact
xix
MODIFYING SIGN
CHAPTER
INTRODUCTION
Beginning with the Industrial Revolution of the early nineteenth century, man has turned more and more to the use of mineral fuels to supply
the energy to operate his machines. The first commercial well drilled
solely for oil was completed in the United States in 1859. The drilling was
supervised by Col. Edwin L. Drake; thus the well came to be known as the
Drake Well. Following the success of the Drake Well, petroleum production and processing rapidly grew into a major industry in the United
States. In the early history of the petroleum industry, petroleum products
were largely used for lubricants and for illuminating fuel.
With the development of internalcombustion engines and other devices, the use of petroleum for fuel became increasingly important. In
1900, the total mineral energy production in the United States was 7,643
trillion British thermal units (Btu); of this, 92 per cent came from coal,
about 5 per cent from oil, and 3 per cent from natural gas. By 1925, mineral energy production in the United States reached 21,000 trillion Btu, ol
which 73 per cent was from coal, 21 per cent from oil, and 6 per cent from
natural gas. In 1950, the demand for energy reached 33,000 trillion Btu
in the United States; of this, 45 per cent was supplied by coal, 35 per cent
from oil, and 20 per cent from natural gas. 1*
Through 1956, the cumulative crudeoil production for the world was
95 billion barrels, of which about 55 billion barrels was produced in the
United States. Today, petroleum is used not only as a fuel and a source
of lubricants but as a raw material for many modern industrial materials,
such as paints, plastics, rubber, and so forth.
General Composition of Petroleum
What is petroleum? Petroleum is a mixture of naturally occurring hydrocarbons which may exist in the solid, liquid, or gaseous states, depending
upon the conditions of pressure and temperature to which it is subjected.
Virtually all petroleum is produced from the earth in either liquid or gaseous form, and commonly, these materials are referred to as either crude
oil or natural gas, depending upon the state of the hydrocarbon mixture.
*Superscript numbers refer to references at end of chapter.
1
INTRODUCTION
Crude oil is the material most sought after of these naturally occurring
hydrocarbons, but natural gas is commonly produced along with the crude
oil. In the early years of the petroleum industry, natural gas was considered to be a nuisance and was burned at the well site. In recent years with
the advent of transcontinental transmission lines and petrochemical industries, the demand for natural gas as a fuel and a raw product has increased the value of natural gas to the point where it is no longer a nuisance
but a valuable raw material.
Petroleum consists chemically of approximately 11 to 13 wt % hydrogen
and 84 to 87 wt % carbon. Traces of oxygen, sulfur, nitrogen, and helium
may be found as impurities in crude petroleum. Although all petroleum is
constituted primarily of carbon and hydrogen, the molecular constitution
of crude oils differs widely. About 18 series of hydrocarbons' have been
recognized in crude petroleum. In Table 11 are listed the group formulas
carbon atoms but with word endings and prefixes designating the group to
which the compound belongs. The word ending "ane" designates saturated
hydrocarbons while "ene" designates unsaturated hydrocarbons that have
double bonds between carbon atoms. If more than one double bond exTABLE 12. CLA.sSIFICATION OF HYDROCARBONsS
Marsh gas
Gaseous
Natural gas
Petroleum{
Crude oil
Fluid
Asphaltite
Brea
Gilsonite: uintahite
Hydrocarbo
No. of
carbon atoms
Pennsylvania
MidContinent
California and
Gulf Coast
lid Coal
C,.H21<+2
IO
c.H...,
15
20
25
40
C,.H2n+t
C,.H2,.
C ..H2.. and CJI2n2
C,.Hta and C..H:z..'
C..H2n4 and C..Hi..8
C,.H2..1 and C,.H2n8
50
80
C,.H2ns
CnH:ma
30
illi
C,.IL,.+2
CJI2n+2 and C..H:..
C,.H,,._,
C,.H2>1.'
L"gnite
bbituminous
tuminous
mibituminous
thracite
C,.ffi,.t
C,.H,,...,
C,.H2n....s and C,.H2nu
CJitna and C..H212
C,.H2n8 and CnH:iu
C,.H:z,,.1a
CJI:z..._14
C..H:..20
of series identified in petroleum. Of these series, the most commonly encountered are the paraffins, the olefines, the polymethylenes, the acetylenes,
turpenes, and benzenes. Natural gas is composed predominantly of the
lowermolecular weight hydrocarbons of the paraffin series.
Hydrocarbons can be classified into essentially four categories depending
on the structural formula. Two of the categories refer to the structural
arrangement of the carbon atoms in the molecule. These are (1) open
chain and (2) ring or cyclic compounds. The remaining two categories
refer to the bonds between the carbon atoms. These are (1) saturated or
single bond and (2) unsaturated or multiplebond compounds.
The names of the various individual hydrocarbon molecules are derived
in a systematic fashion from rules established by the International Union
of Chemistry. The established names of the individual hydrocarbons of
the paraffin series are utilized for compounds having the same number of
Kerogen
Bituminous shale
Petroliferous
Cereous
c..H211+2
H H H H H H
I I
HCCCCCCH
H H H H H H
Normal Hexane, CJI14
H H H H H H
HCCCCC~
H H H H
Normal Rexene, CJI1:r


INTRODUCTION
H0
/I
H/
~~
H/
"/ H
0
~
/"
"
Cyclohexane, C6H 12
Benzene, CaH6
Alkadiene, C,.H211:
H H
H H H
Degrees
API
0H
I"
H
0H
H0
~ /H
H" /
/H
I I
H H
I
H
Hexadiene1,5, CJI1n
or
'Y
where
'Y
Degrees Weight
of
of
specific gallon,
lb
gravity
API
of
of
Degrees
API
specific
gallon,
gravity
lb
Weight
of
Degrees
Degrees Weight
Degrees
of
specific
gravity
gallon,
lb
8.962
8.895
8.828
8.762
8.698
8.634
36
37
38
39
40
0.8448
0.8398
0.8348
0.8299
0.8251
7.034
6.993
6.951
6.910
6.870
71
72
73
74
75
0.6988
0.6953
0.6919
0.6886
0.6852
5.817
5.788
5.759
5.731
5.703
1.0000
8.571
8.509
8.448
8.388
8.328
41
42
43
44
45
0.8203
0.8155
0.8109
0.8063
0.8017
6.830
6.790
6.752
6.713
6.675
76
77
78
79
80
0.6819
0.6787
0.6754
0.6722
0.6690
5.676
5.649
5.622
5.595
5.568
11
12
13
14
15
0.9930
0.9861
0.9792
0.9725
0.9659
8.270
8.212
8.155
8.099
8.044
46
47
48
49
50
0.7972
0.7927
0.7883
0.7839
0.7796
6.637
6.600
6.563
6.526
6.490
81
82
83
84
85
0.6659
0.6628
0.6597
0.6566
0.6536
5.542
5.516
5.491
5.465
5.440
16
17
18
19
20
0.9593
0.9529
0.9465
0.9402
0.9340
7.989
7.935
7.882
7.830
7.778
51
52
53
54
55
0.7753
0.7711
0.7669
0.7628
0.7587
6.455
6.420
6.38/i
6.350
6.316
86
87
88
89
90
0.6506
0.6476
0.6446
0.6417
0.6388
5.415
5.390
5.365
5.341
5.316
21
22
23
24
25
0.9279
0.9218
0.9159
0.9100
0.9042
7.727
7.676
7.627
7.578
7.529
56
57
58
59
60
0.7547
0.7507
0.7467
0.7428
0.7389
6.283
6.249
6.216
6.184
6.151
91
92
93
94
95
0.6360
0.6331
0.6303
0.6275
0.6247
5.293
5.269
5.246
5=
5.199
26
27
28
29
30
0.8984
0.8927
0.8871
0.8816
0.8762
7.481
7.434
7.387
7.341
7.296
61
62
63
64
65
0.7351
0.7313
0.7275
0.7238
0.7201
6.119
6.087
6.056
6.025
5.994
96
97
98
99
100
0.6220
0.6193
0.6166
0.6139
0.6112
5.176
5.154
5.131
5.109
5.086
31
32
33
34
35
0.8708
0.8654
0.8602
0.8550
0.8498
7.251
7.206
7.163
7.119
7.076
66
67
68
69
70
0.7165
0.7128
0.7093
0.7057
0.7022
5.964
5.934
5.904
5.874
5.845
0
1
2
3
4
5
1.076
1.068
1.060
1.052
6
7
8
9
10
1.029
1.022
1.014
1.007
C=C000=0
I
H
AP!,
"cf
H" /
1.044
1.037
 



INTRODUCTION
TABLE 14. VALUES FOR CONVERTING KINEMATIC VISCOSITY TO
noted that the API gravity yields numbers greater than 10 for all materials
having specific gravities less than 1. Since the density of a liquid is a func
Equivalent Saybolt
Universal viscosity, sec
Equivalent Saybolt
Universal viscosity, sec
Kinematic
viscosity,
cs
At 100F
(basic
values,
see Note)
At
130F
At
210F
2.0
2.5
3.0
3.5
4.0
32.6
34.4
36.0
37.6
39.1
32.7
34.5
36.1
37.7
39.2
32.8
34.6
36.3
37.9
39.4
4.55.0
40.7
42.3
40.8
42.4
41.0
42.6
6.0
7.0
8.0
9.0
10.0
45.5
48.7
52.0
55.4
58.8
45.6
48.8
52.1
55.5
58.9
45.8
49.0
52.4
55.8
59.2
11.0
12.0
13.0
14.0
15.0
62.3
65.9
69.6
73.4
77.2
62.4
66.0
69.7
73.5
77.3
16.0
17.0
18.0
19.0
20.0
81.1
85.1
89.2
93.3
97.5
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0
29.0
30.0
Kinematic
viscosity,
cs
31
32
33
34
35
_..\.t 100F
(basic
values,
see Note)
145.3
149.7
154.2
158.7
163.2
130F
At
210F
145.6
150.0
154.5
159.0
163.5
146.3
150.7
155.3
159.8
164.3
At
conditions for reporting specific grayity and API gravity. The petroleum
industry has adopted as standards a temperature of 60F and atmospheric
pressure. Table 13 lists the refationship between API gravity and other
commonly used expressions of the density of petroleum liquids.
The viscosity of crude oil ranges from about 0.3 centipoise for a g'd.Ssaturated oil at reservoir conditions to about 1,000 centipoises for a gasfree crude oil at atmospheric pressure and 100F. Viscosities of crudeoil
and liquidpetroleum products are frequently reported in terms of the time
39
40
167.7
172.2
176.7
181.2
185.7
168.0
172.5
177.0
181.5
186.l
168.9
173.4
177.9
182.5
187.0
62.7
66.4
70.l
73.9
77.7
41
42
43
44
45
190.2
194.7
199.2
203.8
208.4
190.6
195.1
199.6
. 204.2
208.8
191.5
196.1
200.6
205.2
209.9
81.3
85.3
89.4
93.5
97.7
81.7
85.7
89.8
94.0
98.2
46
47
48
49
50
213.0
217.6
222.2
226.8
231.4
213.4
218.0
222.6
227.2
231.8
214.5
219.1
223.8
228.4
233.0
101.7
106.0
lI0.3
l14.6
l18.9
101.9
106.2
110.5
114.8
119.1
102.4
106.7
lII.l
l15.4
l19.7
55
60
65
70
254.4
277.4
300.4
323.4
254.9
277.9
301.0
324.0
256.2
279.3
302.5
325.7
123.3
127.7
132.1
136.5
140.9
123.5
127.9
132.4
136.8
141.2
124.2
128.6
133.0
137.5
141.9
Over 70
Saybolt
Saybolt
see = cs
x 4.629
36
37
38
sec =cs
x 4.620
Saybolt
= cs
x 4.652
sec
fore, standard tests with the Saybolt viscosimeter are conducted at 100F.
Other physical properties of liquid petroleum are frequently correlated
with API gravity and viscosity. In general, such correlations have rather
limited application.
Crude oils are frequently classified by "base." The earliest such classification system provided three classifications:
1. Paraffinbase, or oils containing predominantly paraffin series hydrocarbons
2. Asphaltbase, or oils containing predominantly polymethylene or
olefin series hydrocarbons
3. Mixedbase, or oils containing large quantities of both paraffin and
polymethylene series hydrocarbons
The U.S. Bureau of Mines' introduced a somewhat more elaborate system of classification which provides for nine possible classifications. This
system is based on a modified Hempel distillation of the crude oil and upon
the API gravity of certain fractions obtained upon distillation.
The distillation is conducted in two phases: one at atmospheric pressure
and one at an absolute pressure of 40 mm of mercury. The fraction boiling
between 482 and 527F at atmospheric pressure is key fraction 1. The
fraction boiling between 527 and 572F at 40 mm absolute is key fraction 2.
The nine possible classifications of a crude oil are summarized in Table 15.
The U.S. Bureau of Mines reported the average results of distillations of
Key fraction 1, F
Key fraction 2, F
Paraffin
40 or lighter
Paraffinintermediate
Intermediateparaffin
Intermediate
Intermediatenaphthene
Naphtheneintermediate
Naphthene
40 or lighter
30 or lighter
2()30
30 or lighter
2()30
20 or heavier
2()30
20 or heavier
20 or heavier
30 or lighter
Oil
Para:ffinnaphthene
N aphtheneparaffin
3340
3340
3340
33 or heavier
33 or heavier
40 or lighter
33 or heavier
303 crudeoil samples from throughout the world. These results appear in
Table 16. Analyses of this type are useful in evaluating crude oils for refining purposes. Note that of the 303 samples analyzed, 109 samples are
classified as intermediate and 83 samples are naphthene base.
Natural gas is composed largely of hydrocarbons of the paraffin series.
Methane and ethane frequently comprise 80 to 90 per cent by volume of a
natural gas. Other hydrocarbons, ranging in molecular weight from 44
(propane) to in excess of 142 (decane), together with impurities compose
the remaining percentage. Carbon dioxide, nitrogen, and hydrogen sulfide
are the more common impurities found in natural gas. Helium and other
inert rare gases occasionally occur in small concentrationf? in natural gases.
Gas gravity is widely used to characterize natural gases. Gas gravity is
the ratio of the density of a gas at atmospheric pressure and temperature
to the density of air at the same condition of pressure and temperature.
Since at atmospheric pressure and temperature the densities of gases are
directly proportional to the molecular weight, the gravity is the ratio of
the molecular weight of the gas to the molecular weight of air. The molecular weight of methane is 16. Therefore, the gravity of pure methane is
0.55 or 16 + 29. Gas gravities for natural gases range from 0.6 to 1.1, depending on the relative concentration of the heavier hydrocarbons present
in the gas.
Compositional analyses of natural gases are readily obtained by lowtemperature distillation, chromatography, or mass spectrometry. Volume
or mole percentages of the individual components present are ordinarily
reported through heptanes plus. The heptanesplus fraction includes heptane and all heavier hydrocarbons.
Natural gases are also described as dry or wet gases depending on the
amount of condensable hydrocarbons present in the mixture. Pentane
and heavier components are considered to be condensable hydrocarbons,
as at atmospheric pressure and temperature pure pentane exists as a liquid.
"'
"'
"'.,,
oci c:i

<a
.,,
oci
"'
1~
.....
co
00
u;;
co
u;;
~i.q
10""1"
ai
oci
"'
1~
"'
"'
0
10
"o. :ab
.
5~
""
0 d
os
s~
z~
" 0
~
.. 0
~]
"
~d
;io
"'

d
0
""
"""
>
~ >,
oo
~
~
.s
d
0
0
>
i:: b
do
.;~
o~
s=
az
>.~
~
~~
0
0
~
_.g b
 >,
> g
..
~~
00
~] g
=d~
;:;
11
a
>,
"'~~~
 0
.
~r5b
""5b;::
.0
l'il
:0 >,
.;J
,g
~""
.~
~:~
c:oo""' !!
~:S g
~
<Cl
~<*
&'ii 2> E
o.o+>
""'d""'
g_g~s
:i;
:i;
.
12
petroleum must migrate from the source beds to the reservoir rock in order
that sufficient quantities accumulate to form the commercial deposits that
the petroleum industry exploits. This evidence of migration indicates a
third requirement: a carrier bed. The carrier bed may be a part of the
reservoir rock in which the accumulation occurs, or it may be an adjacent
reservoir rock having interconnected pores.
4. Monoclinehomocline flexure
5. Plunging syncline
6. Absence of controlling structural
condition~
Traps
The primary forces causing the migration of petroleum are bouyancy
and capillarity. As oil and gas are lighter than the ground water which
permeates the porous rocks below the water table, it is evident that the
upward movement of petroleum must be restricted in order that accumulations exist at depth. A natural barrier, or trap, must exist for a petroleum accumulation to form. Traps associated. with oil fields are, in general,
complex.
Wilhelm' proposed a classification system for traps which differentiates
between factors indicating the structural environment of a reservoir in an
area and the actual attitude or situation of the reservoir bed. The classification system is expressed by means of a group of structural environment
indicators and by a group of trap indicators.
Trap indicators are grouped as follows:
A. Convex trap reservoirs, which are completely surrounded by edgewater, as the porosity extends in all directions beyond the reservoir areas.
The reservoir peripheries are therefore defined by uninterrupted edgewater
limits. The trap is due to convexity alone.
B. Permeability trap reservoirs, with a periphery partly defined by edgewater and partly by the barrier resulting from the loss of permeability in
the reservoir layer. In the extreme case, the reservoir may be entirely surrounded by such a permeability barrier.
C. Pinchout* trap reservoirs, with the periphery partly defined by edgewater and partly by the margin due to the pinchout of the reservoir bed.
F. Fault trap reservoirs, with the periphery partly defined by edgewater
and partly by a fault boundary.
G. Piercement trap reservoirs, with the periphery partly defined by
edgewater and partly by piercement contact.
13
INTRODUCTION
~~
"' ~ '"
(C)
lei
{d)
!di
(el
!fl
(g)
~]
{f)
rnmtrnf:t(
Porous bed
FrG. 12. Contours of structural environments. (a) Dome; (b) anticline; (c)
piercement salt dome; (d) structural
salient; (e} structural terrace; (f} monocline; (g.} plunging syncline. (From Wilhelm:'}
one of the elementary reservoir traps and one of the structural environment indicators. That is, the structure in the area in which the trap exi>3ts
defines the structural environment; the actual attitude or configuration of
a petroleum reserroir determines the trap clas.....tjfication. Some reservoirs,
14
of course, a.re complex and result from a combination of two or more of the
elementary trap features.
For an accumulation of oil or gas to exist, there must be closure* in the
trap. The classification ~ystem discussed recognizes this requirement for
closure and further recognizes that the reservoir rock must be overlain by
impermeable beds so that oil or gas accumulation cannot seep from the
trap and migrate to higher beds in the stratigraphic sequence. The classification system allows differentiation between an oil field and a reservoir.
An oil field is defined simply by its areal extent on the surface of the ground,
while a petroleum reservoir involves a continuity of reservoir rock and
fluid. An oil field may encompass several oil reservoirs.
In general, in petroleum exploration, it is possible to evaluate and define
structural environment indicators from geophysical and regional geologic
information. Furthermore, it is possible to define from such information
some of the trap indicators, such as a convex trap, a fault trap, or a piercement trap. The permeability trap and the pinchout trap, however, are
disclosed only by the drill. Even though traps exist, there is no assurance
that a commercial petroleum accumulation exists. A trap is a necessary
but not sufficient condition for a petroleum accumulation. Therefore, not
a.11 traps form petroleum reservoirs.
Distribution of Hydrocarbon Fluids in Traps
Porous rocks are fluidpermeated, containing oil, gas, or water. Gravitational and capillary forces largely control the distribution of these fluids
in petroleum accumulations.
The gravitational forces cause the less dense fluids to seek the higher
positions in the trap. Capillary forces tend to cause a wetting fluid to rise
into pore space containing a nonwetting fluid. Water, in general, is a
wetting fluid with respect to oil and gas, and oil is a wetting fluid with
respect to gas. Capillarity tends to counteract the force of gravity in
segregating the fluids. Prior to the disturbance of the accumulation, an
equilibrium exists between the capillary and gravitational forces.
Typical fluid distributions resulting from the equilibrium of these forces
are shown schematically by sectional views of a domal trap in Fig. 13.
Also illustrated in the figure are the possible modes of occurrence of gas:
(1) solution gas, (2) associated free gas, (3) nonassociated free gas.
The accumulation of crude oil is shown in Fig. l3a. At the conditions
of pressure and temperature existing in the trap, only oil and water are
present. The oil is accumulated in the top of the trap and is underlain by
water. Between the oil zone and the water zone, an oilwater transitional
zone exists. The pore space of the rock in the oil zone contains a small
amount of water (commonly called connate water). The fraction of the
*Closure is the height between the lowermost closed contour and the top of the trap.
15
INTRODUCTION
pore space occupied by water increases with ~epth in the transitional zone
so that the base of the transitional zone is delineated by completel.y
watersaturated pore space. Natural gas initially occurs in such a reservoir
only as solution gas.
Oil wafer
~.,
transiflon zone
_ _1~::
tronstf1on zone~~~~~~.;:~,
1~~""'''''
(C)
FIG. 13. Sketch showing typical fluid di~tributions in hy~rocarbon reserv?irs (a) Oil
P,servoir; (b) associated oilgas reservoir; (c) nonassoc1ated gas reservoir.
An accumulation in which both crude oil (liquid phase) and natural ?as
(free gas phase) occur at the conditions of pressure and tem~erature _exist;n~ in the trap is shown in Fig. I3b. The natural gas occup~es the highest
position of the trap and for:r:is a Hgas cap.". The crude 011 occupies an
intermediate position and is, Ill turn, underlain by water.
Transitional zones are shown both between the gas and the oil and between the oil and water. These are zones of variable saturation in the wetting and nonwetting fluids. Connate ~ate: exists in the gas ca~ as _well as
in the oil zone. The natural gas occumng in such an accu~ula~1on is co~
prised of the associated free gas in the gas cap and the solut10n gas d1&solved in the crude oil.

16

An accumulation of only natural gas is shown in Fig. 13c. The gas zone
is underlain by a gaswater transitional zone and water. The gas zone contains connate water, which increases with depth in the transitional zone to
complete water saturation in the water zone. The gas in this accumulation
is nonassociated gas, as no crude oil exists in the accumulation.
17
INTRODUCTION
classified sandstones into ortboquartzite, graywacke, and arkose. An orthoquartzite is a sedimentary quartzite developed as a result of excessive
silicification without the impress of metamorphism and is comprised primarily of quartz and other stable minerals. The cementing material is
Sandstone
100%
Shaly sandstone
Limy sandstone
It is appropriate therefore in the study of petroleumreservoir engineering to review briefly some of the rocks with which engineers must deal.
Virtually all oil and gasbearing rocks are sedimentary in origin. Therefore, this discussion is confined to sedimentary rocks. While it is possible
to classify sedimentary materials according to their mineralogical composition or other similar classifications, it is convenient to blassify them according to their origin. Two major subdivisions, then, can be considered: the
Sandy limestone
Limestone
100"/o
L.......,.,..,'
Shaly limestone
Limy shale
Shale
100/o
dominant'.y fragmental sediments and the partly fragmental, partly precipitated sediments. The dominantly fragmental sediments can conveniently
be subdivided according to textural considerations into the conglomerates
dolomites are important petroleum reservoir rocks which are partly fragmental, partly precipitated in origin. Limestones and dolomites may be of
mechanical or chemical origin or may be developed as a result of both
processes of deposition.
Pyrite
CJ
Pore space
Scale in mm
FIG. 15. Dolomite quartzite of Wilcox, Okla., oilsand type. (From Pirson.')

18

19
INTRODUCTION
The Frio formation of the Gulf Coast of Texas and Louisiana is a typical
graywacke.
An arkose or arkosic sandstone contains 25 per cent or more feldspar
.Contrnentol shelf
Old sediments
Coast line
Scale in mm
FIG. 16. Idealized land and sea conditions which give rise to quartzosetype sediments. (From Pirson.i)
cementing materials are clays and carbonate. The land and sea conditions
which give rise to graywacketype sediments are depicted in Fig. 17.
Note that the land from which the sediments are derived is of moderate
relief. Because of the more rapid erosion and transport of the rock fragments from the land area to the site of deposition, a greater variety of rock
Land of moderate
relief~
Old sediments
Short
+Geosyncline
+continental shelf+
Sond bar.
Thin limestone
_ ... 
,,,....
Metamorphic
,.., "'basement
,,,.
~ complex """ ""
v
~
Fro. 17. Idealized land and sea conditions which give rise to graywacketype sediments. (From Pirson.8 )
fragments remains unaltered than in an orthoquartzite. Figure 18 illustrates the rocks and rock materials comprising a typical graywacke such
as encountered in the Gulf Coast area. Note in particular the occu~ence
of clay and other micaceous material. Illite is believed to be the principal
clay mineral occurring in graywacke. Graywackes are frequently lenticular
C::J Quartz
~ Carbonate
t~:!!fr~~ Chert
~ Mica flake
EIEJ
l.c:rzllll
Quartzite fragment
F1a. 18. Graywacke of the Bradford and Guif Eocene oilsand type. (From Pirson.8 )
derived from acid igneous rock. Arkose is usually coarse grained and is
derived from lands of steep relief during periods of intense diastrophism.
Since transport of the materials from the uplands to the site of deposition
is relatively rapid, many unstable minerals do not decompose. The cementing material is chiefly clay containing a large percentage of kaolinite but
also high proportions of reactive clays, such as montmorillonite. The
sediments are characterized by thick sections of poorly sorted material.
Because of the poor sorting and the variety of minerals composing arkose,
the physical properties of the rock are quite variable. Figure 19 illustrates
the conditions giving rise to arkosic sediments, while Fig. 110 illustrates
the minerals and rock materials comprising a typical arkose. Note the
poor sorting and the relative angularity of the materials comprising an
arkose.
Limestones, dolomites, and other carbonate reservoir rock materials are
frequently derived by precipitation. Limestones are typically extensive
and massive. A pure limestone or dolomite rarely occurSowing to the
presence of varying amounts of detrital material. Carbonate reservoir
rocks can be divided into the following lithologic types: oolitic limestone,
limestone, chalk, dolomitic limestones, dolomites, and cherty limestones
and dolomites. Of these materials the physical properties of only the oolitic
limestone are largely determined by the depositional environment. The
remaining carbonate rocks are largely finely crystalline, and their physical
properties depend greatly on such processes as deformation and solution
after deposition. A limestone has little resistance to tension, and when it
20
INTRODUCTION
of step relief.,
Ve!'}'short or
non existent
continental shelf
    Deep geosyncline ~...LSeo level
  ,,,.

.....
Metomcirphic
basement
complex
~ ~
1~: .) Quartz
W't
~
~ 0 o@
 MicmcHne (fresh)
~
rt:JI& ==:~iii~close
Microcline (weathered)
~Po?
.
CJ ~~~:;;0::teriol
FIG. 110. Arkose of the Stevens, Calif., oilsand type. (From Pirson.8 )
21
22
23
INTRODUCTION
Drilling
on and gas are producea from the earth by means of wells drilled to the
reservoir rock. Any drilling method must meet two requirements: (1) a
means of breaking or abrading the formations to be penetrated and (2) a
means of removing the cuttings or the rock fragments which are produced
in the drilling operation. Although many methods may be conceived which
can accomplish these two purposes, oilwell drilling has been restricted
largely to two methods. These methods may be identified as (1) churn
drilling and (2) rotary drilling. A third category is sometimes included, a
combination of the two foregoing drilling methods.
Cabletool Drilling
While there are many variations of the churndrilling method, that commonly used in the United States is known as cabletool drilling. Approximately 15 per cent of all the holes drilled in the United States each year
are drilled by the cabletool method. Cabletool drilling is used to a great
extent in the Appalachian area. The cabletool rigs used are spudders,
drilling machines, or American Standard cabletool rigs. The principal
components of the cabletool drilling rig together with a sectional view of
the hole with the drilling tools are shown in Fig. 111. The drilling tools
are comprised of ? bit, a drill stem, jars, and rope socket suspended on a
wire rope. To drill, the tools are lowered to the bottom of the hole and the
drilling line attached to the walking beam which imparts a reciprocating
motion to the tools. This reciprocating motion causes the tools to strike
repeated blows on the formations at the bottom of the hole, thus causing
breaking or abrading of the formation by a simple pounding or chipping
action. After a certain amount of material has been broken from the formation, the drilling motion is interrupted and the drilling tools are removed
from the hole.
After the tools l1ave been retrieved to the surface and set back, a bailer
is lowered into the hole to remove the broken formation material or cuttings. Water is added to the hole periodically as drilling progresses. Thus
the cuttings in cabletool drilling are suspended in a thin mud slurry. In
" cabletool drilling, the fluid to suspend the cuttings is maintained at a low
level, only partially filling the hole. More effective blows are struck by
the tools if a low head of fluid is maintained during the drilling operation.
B""L
WHEEL
CASLE
ROPE
TOOL
SOCKET
JOINT
JARS
TOOL
DRIL?.
JOINT ~STEM
tSlT
FIG. 111. Principal components of a cabletool drilling rig with drilling tools in the
hole. (From Uren.9 )
25
pump. The sand pump is so designed that a suction is created to aid in
INTRODUCTION
26
27
INTRODUCTION
Rotary table
Drow works
Mudflow lines
F'1G.
113. Rotary drilling rig. (Adapted from "Primer of Oil Well Drilling." 10)
pending upon the base of the drilling fluid. These categories are (1) waterbase fluids, (2) oilbase fluids, and (3) air or gas in the order of frequency of
use. Both waterbase and oilbase muds consist of a continuous liquid
phase, the base, and dispersed solids. The dispersed solids increase the
density of the fluid and impart desirable colloidal properties to the mud
28
29
INTRODUCTION
removing the water from the well stream. Water is removed by gunbarrel
or other types of water knockouts and then siphoned off from the liquid
petroleum. The generalized production system for an oil well is shown in
Fig. 115.
Gosoil separator
Wei! head
Oil,
woter
L'='~t.FTo
gos
pipeline
Oil, water
Oi! to
pipeline
Well stream
gos, oil, water mixture
___
,,,..........
Qi I reservoir
FrG. 115. Generalized production system. (Adapted from "Primer of Oil and Gas
Production." 12)
30
31
INTRODUCTION
TABLE 18. STANDARD PRESSURES FOR GAS MEASUREMENT
tion of fluids within the formation, and the data requirements of the reservoir engineer. While this text is essentially a text on reservoir engineering,
its purpose is also to report and discuss those subjects in which reservoir
engineering, drilling engineering, and production engineering have common interests.
IN VARIOUS STATES
State or
province
Base
presaure,
Base
temp.,
OF
Arkansas
California
Colorado
Illinois
Kansas
Louisiana
Michigan
Mississippi
New Mexico
Oklahoma
Texas
Utah
West Vrrginia
Wyoming
14.65
14.73
15.025
14.65
14.65
15.025
14.73
15.025
15.025
14.65
14.65
15.025
14.85
15.025
60
60
60
60
60
60
60
60
60
60
60
60
60
60
Canada:
Alberta
British Columbia
Saskatchewan
14.4
14.4
14.65
60
60
60
4,000
'""'
~
a. 3,00 0
,,[
~
~
Q_
'~
2,000
1,000
Pressure
3,00 0
Compiled from data supplied by state agencies, U.S. Bureau of Mines, and
Phillips Petroleum Company.
SOURCE:
fluid volumes and of reservoir pressu1e are necessary for engineering analysis of well and reservoir problems. Typical field data are shown graphically
in Fig. 116.
2,00 0
:a
/'.
/: _,,.
;g' i,000
qjjsoil ratio
\)
>'
Cumu!ah've
qasoi! ratio
'
!:"'"
"'
'
15,000
~
'~
10,000
e
:I
..,_
L u
Reservoir Performance
The reservoir engineer is, of course, concerned with the production of
oil ~nd ga~ from the reservoir and primarily with the methods of stimulating
or increasing the recovery from the reservoir as a whole. A basic understanding of drilling and production operations is required in reservoir engineering, as the hydrocarbon fluids are withdrawn from the earth through
the well bore. In addition, virtually all the information upon which a
reservoir engineer can base his studies must be obtained from these same
well bores in terms of well logs, formation samples, samples of oil and gas
'
oil and gasproduction statistics, and reservoir pressures.
Efficient drilling and completion operations depend upon the physical
properties of the rocks which are penetrated and in particular upon the
properties of the producing formation. In addition, efficient production
operations depend on a knowledge of formation characteristics, distribu
r' /nsfantoneou5
5,000
Q_
I/
''.
V
~L
Cumulative 011
production
Ooilyoil
producflon {av)  2
>
"'
10 x 10 6 ~
/
..
40x10 6
. '
.....
'
'
~~~~~~~~~~~~~~~~~~~~~~~~~~~~
E
u
~~~c~~~o~~~o~~~c~~~c~~~c~~~c
1937
1938
1939
1940 1941
1942
1943
32
33
INTRODUCTION
sources of energy exist in the formation. One of these sources is the expansive energy of the hydrocarbon fluid. In the case of gas the material is
confined under pressure, and when the formation is opened to a well bore
existing at a lower pressure, the fluid will tend to expand and flow toward
the pressure sink. This, too, is true of crude oil or liquid petroleum. If the
well constitutes a pressure sink, then fluid will migrate through the porous
reservoir material to the well bore. In the case of liquid petroleum, the
natural energy is the expansive energy of the liquid petroleum and the gas
dissolved in the liquid petroleum at the elevated pressure at which the
petroleum was confined. Frequently oil fields are found in which a part of
the reservoir is liquidsaturated and a part of the reservoir rock is gassaturated. This type of accumulation is referred to as an oil reservoir with
a gas cap. The liquid petroleum may be forced toward the well bores by
the expansive energy not only of the liquid petroleum and the dissolved gas
but of the overlying gas cap. In addition to the expansive energy of the
reservoir almost as rapidly as the hydrocarbon fluid is withdrawn, therefore preventing any substantial decline in pressure.
The force of gravity does not become important as a driving mechanism
until the reservoir becomes substantially depleted. However, as previously
mentioned, gravitational forces are present in all the three preceding mechanisms and play a substantial role in the distribution of the fluids in that
gravity tends tO promote segregation of the fluids contained within the
water. The oil accumulation may be surrounded by waterbearing formations. This water also is subjected to elevated pressures in the subsurface,
and upon withdrawal of fluid from the petroleum reservoir, the reservoir
reservoir.
2
0 80
60
\
' drive
Water
~
'

becomes a pressure sink and the contiguous water expands into the petro
leum reservoir, thus displacing oil or gas toward the well bores. In addition
to the expansive energies present, there is also the force of gravity acting
at all times upon the fluids. The primary effect of the force of gravity
throughout most of the history of petroleum reservoirs is to promote the
segregation of the various fluids. That is, gas tends to occupy the higher
places in the accumulation; oil, being more dense than gas and less dense
~ 20
::
~
"'
20
80
100
Fra. 117. TYPical pressureproduction histories of the three major drives. (From
Clark.1/J)
than water, tends to occupy the intermediate position; and water, of course,
on the size of the gas cap relative to the oil zone and on the production
procedure used. Water drive is the most efficient in maintaining reservoir
gascap drive, managed to secure the greatest aid from gravitational forces,
may yield a greater recovery efficiency than a water drive.
Most petroleum reservoirs are suQjected to one or more drives either
as solutiongasgascap drive.
For instance, a large reservoir after initial discovery may behave in its
34
INTRODUCTION
lished in the adjacent aquifer so that water drive may become an important
part of the reservoir mechanism. Reservoirs having more than one type of
drive present are referred to as combinationdrive reservoirs. Petroleum
reservoirs 'Containing only material in the gaseous phase at reservoir conditions are generallY referred to as gas or condensate reservoirs.
The reservoir engineer must identify the drive mechanisms of a reservoir
and develop production procedures to secure the maximum economic recovery efficiency. The production procedures recommended may include
supplementation of natural energy by fluid injection. The fluid injection
may involve the return of gas, water, or gas and water to the reservoir.
One of the many possible injection procedures is shown schematically in
Fig. 118.
Woterinjection
Oilproducing
well
well
Gosinjection
well
2. Hager, Dorsey: "Practical Oil Geology," 6th ed., McGrawHill Book Company.
Inc., New York, 1951.
3. Kraemer, A. J., and E. C. Lane: Properties of Typical Crude Oil from Fields of
the Eastern Hemisphere, U.S. Bur. Mines Bull. 401, 1937.
4. Wilhelm, 0.: Classification of Petroleum Reservoirs, Bull. Am. Assoc. Petro.
Geologists, vol. 29, 1945.
5. Uren, L. C.: "Petroleum Production Engineering: Oil Field Exploitation," 3d ed.,
McGrawHill Book Company, Inc., New York, 1953.
6. Vance, Harold: "Elements of Petroleum Subsurface Engineering," Educational
Publishers, Inc., Saint Louis, Mo., 1950.
7. Krynine, P. D.: Sediments and the Search for Oil, Mineral Ind., vol. 13, no. 3,
December, 1943.
8. Pirson, S. J.: "Elements of Oil Reservoir Engineering," 1st ed., McGrawHill
Book Company, Inc., New York, 1950.
9. Uren, L. C.: "Petroleum Production Engineering: Oil Field Development," 4th
ed., McGrawHill Book Company, Inc., New York, 1956.
10. "Primer of Oil Well Drilling,'' Industrial and Business Training Bureau, and the
A.A.0.D.C., Texas Education Agency, July, 1951.
11. Brantly, J. E.: "Rotary Drilling Hand Book," 4th ed., Palmer Publications, Los
Angeles, 1948.
12. "Primer of Oil and Gas Production," American Petroleum Institute, New York,
1954.
13. Clark, N. J.: Review of Reservoir Engineering, World Oil, May, 1951.
F1a_ 118. Diagram showing the supplementing of natural reservoir energy by water
injection into the water zone and gas injection into the gas cap.
35
CHAPTER
FUNDAMENTAL PROPERTIES OF
FLUIDPERMEATED ROCKS
INTRODUCTION
Naturally occurring rocks are in general permeated with fluid, water, oil,
or gas or combinations of these fluids. The reservoir engineer is concerned
with the quantities of fluids contained within the rocks, the transmissivity
of fluids through the rocks, and other related properties.
These properties depend on the rock and frequently upon the distribution
or character of the fluid occurring within the rock. In this and the following chapter, properties of rocks containing fluids will be discussed.
This chapter deals with the properties which are considered fundamental
and from which other properties and concepts can be developed. The
properties discussed are the porositya measure of the void space in a
rock; the permeabilitya measure of the fluid transmissivity of a rock;
the fluid saturationa measure of the gross fluid distribution within a
rock; and the electrical conductivity of fluidsaturated rocksa measure
of the conductivity of the rock and its contained fluids to electrical current.
These properties constitute a set of fundamental parameters by which the
rock can be quantitatively described.
POROSITY
37
Porosity= 47.6/o
Porosity= 25.96/o
(bl
(a)
FIG. 21. Unit cells and groups of uniform spheres for cubic and rhombohed.ral packing. (a) Cubie, or widepacked; (b) rhombohedral, or closepacked. (After Graton
and Frru;er .~)
The unit cell is a cube with sides equal to 2r where r is the radius of the
sphere. Therefore,
Bulk volume
= (2r) 3 = Sr'
4;

38
Pore volume X
_ bulk volume  grain volume
100
Bulk volume
bulk volume
X lOO
8r3  %71'1"3
=
Sr'
7r
Silt
Framework
/ fraction
~
:;;
E
0
0
"'
Clay
Decreasing
Grain diameter
0.01
Q001
Diam, mm
0.2
Pore space
);OJ Cloy
IE) Calcite cement
QtzQuartz
Kf Potash feldspar
Plogioclose
feldspar
Ch Chert
Pf
Ls Limestone
FIG. 22. Thin section of sandstone illustrating grain and pore configuration.
(From Nanz.a)
100
Sand
Silt'
Clay
~
~
.
u
50
0
1.0
0.1
of the rock.
(al
c
c
~Modal size
Legend
Mox
o'""'~.....L~~~~=~,~'
8 50
Nicols cr:ossed
50
1!c
mm
Interstitial material
and mud fragments
:;::
'
39
Of particular interest is the fact that the radii cancel and the porosity of
packings of uniform spheres is a function of packing only.
The investigators recognized that naturally occurring materials were
composed of a variety of particle sizes and that not only the arrangement
but the angularity and distribution of particle size would affect porosity.
The angularity of particles comprising a sandstone is shown in the thin
section of Fig. 22. The configuration of the pore space is obviously dif100
  ..
0,01
0.001
Diam, mm
{bl
F1a. 23. Cumulative grainsize distributions of graywacke. (a) Sand; (b) shaly
sand. (From N anz.3 )
f~rent from that which would be obtained from the packing of uniform
spheres. Furthermore, a portion of the space is filled with clay and cement
40
41
37
/
/
34
33
/ .
\
\.,"
!"' r;.._
32
0.10 0.0B 0.06 0.04 0.02
(a)
Skewness
FIG. 25. Variation of porosity with skewness of Ottawa sand. (From Tickell et al.4 )
of the framework fraction, the type of interstitial material, and the type
and degree of cementation. The influence of these various factors can be
evaluated as statistical trends. Hovvever, a quantitative evaluation of the
porosity resulting from the interaction of the various factors is possible
only by laboratory measurements.
Materials having induced porosity such as the carbonate rocks shown in
Fig. 27 have even more complex pore configurations. In fact, two or more
systems of pore openings may occur in such rocks. The basic rock material
is usually finely crystalline and is referred to as the matrix. The matrix
contains uniformly small pore openings which comprise one system of pores.
This system is the result of the crystalline structure of the rock. One or
more systems of larger openings usually occur in carbonate rocks as a result
of leaching or fracturing of the primary rock material. Vugular pore openings are frequently as large as an ordinary lead pencil and are usually attributed to leaching of the rock subsequent to deposition. Fractures also
may be quite large and contribute substantially to the volume of pore
openings in the rock. Both fractures and vugs may be closed or partially
closed by precipitated calcite or other similar material. Vugs and fractures
are highly variable in size and in distribution. Therefore, even more than
lb!
F1a. 26. Cast of pore space of typical reservoir rocks. (a) Fine. i~te~granular sandstone; (b) coarse intergranular sandstone. (From Nuss and Whiting.)
42
43
for intergranular materials, laboratory measurements are required for quantitative evaluation of porosity.
F~o. 2? Typic3:1 carbonate reservoir rocks. (a) Vugular porosity; (b) vugular with
pmpoint porosity;
(c) fractured dense dolomite (d) conglornerate. (From Core
1
Laboratories, Inc.6 )
44
Fie. 28. Electric pycnometer for measurement of bulk volume of small samples.
(Courtesy of Refinery Supply Co.)
45
(Bulk volume based on cubical cores, about 10 cc; round cores, about 7 cc)
Method
Accuracy, cc
(estimated)
Time
Precision on
90%ofdeter. required
minatioIU1, cc per core,
min
Saturation
with tetrachloroethane
0.03
0.02
'
Mercury
pyonometer
:;1:;0.02
0.01
10
0.06
0.06
'
0.015 to 0.20
(with correction
(actor of
0.16 co)
O.Oli
0.03
0.6
:!;
F.Jfects
Preparation
Possible oil
exttaction
Reclamation
dev~~f~~~~om
saturation or
mercury
pycnomoter
method
Cylindrical
Hi h
Cubical
Drainage
0.0Hi
Drainage
0.03
Cores with
Nilvery slight Noneexcept
high permefor satumercurr
abUity aatucontamrnarated corea
rate with
tion, satutettaehlororation
etlui,ne to
elfecte
prevent
mercury
penetfation
Trapped air,
0.01
Tr8.~~ed air,
Saturate with
tettachloroethane
Drainage
0.lli
Drainage
0.03
Trapped air,
0.20
Trapped air,
0.20
Saturate with
teUachloroethane
Core must be
dried2 hr at
100 alld
evacuated
30 min
Poesible oil
extraction
permea~ility
Ex001:111ive
drai11age
0.05
None
Grind surface
to 90Q
angles
None
Nolle
0.03
None
Nilslight
mercurf
contamm11tion
None
Coatin~
None
Extraction of
coating
Method not
applicaWe
Lo:is
of wei~t
m water y
Ins11fficient experimental
data
Eat. 0.04
COating
Conl11mina
tion with
paraffin
Extraction or
paraffin
Not
applleable
paraffin
penetration
D~ri:~~ent
0.10 to
+o.30
Saturat'lon
with wllter
Ruaka inetrument
Coatln~ with
cello ion:
volume by
Kand F
instrumento
paraffincoated core
0.30 to
+0.20
dippmg and
drying
0.03
"'
Ree.ding11aver Drainage
0.03
a~e 0.20 oc
higher than
Ruska instrument
and lluSBell
volumeter
Drainage
0.06
0.1/i
Miseellaneoll!I
0.08
Mechanical
lllOl'lllUrement
Excessive
drainage
0.0li
""'""

~
49
48
voir; the air in the core and chamber is expanded into the evacuated system
Mercury
reservoir.
1
f
wt of dry sample in air
20
G ram voume o sample=
d
. d .
=   = 7.5 cc
san grain ens1ty
2.67
100
10
)
"effective" grain volume, the volume of the grains plus any sealed pore
space. Thus if the effective grain volume is subtracted from the bulk volume, the volume of interconnected or effective pore space is obtained. The
Stevens method is an adaptation of the WashburnBunting procedure,
which will be described in the section on measurement of pore volume.
50
Pressure
bomb
51
Mercury
reservoir
~I
Detail of
pressure bomb
Surette
10
porosity. The methods are based on either the extraction of a fluid from
the rock or the introduction of a fluid into the pore space of the rock.
The WashburnBunting porosimeter, shown in Fig. 212, measures the
volume of air extracted from the pore space by creating a partial vacuum
52
53
Effeotivo poroaity
Effective poroaity
Effective poroaity
Effective poroaity
(be11t method)
Effective poroaity
Effective porosity
Total )lOrosity
'
Method
W1111hburn
Bunting
Stevena
Kobe porosimeter
Boyle's law
poroeimeter
Typo
Preparation
&!vent extraction
and oven drying.
Occasionally use
retort samples
&!vent extraction
and oven drying.
Occa.11ionally use
retort samples
Solvent extraction
and oven d~ying.
Oecasionally \Jae
retort samplea
Solvent extraction
and oven drying.
Ckcasio11ally uae
retort samples
Solvent extraction
and oven dryiog.
Occa.11ionally WIB
retort samples
None
FunctioDS
measured
Saudgrain volume
and unconnected
POre volume and
bulk volume
Sandgrain volume
and unconnected
,pore volume and
bulk volume
Sandgrain volume
i:md unconnected
pore volume and
bulk volume
Volumes of gae
space, oil and
water, and bulk
voJume
Sandgrain volume
and unconnected
pore volume a11d
bulk volume
Man11cr or
me1111ure
mtmt
Reduction of preio
sure on a confi11ed
sample and meas
urement of air
evolved. Bulk
volume from mercury pye11ometer
sampling
ft:
'
Errors
Saturation
Core laboratories
Wot sample
23.
c 
Cure laboratorioo
Dry sample
Type of
material
Sample
No.
Approximate
gas permeability,
roillidarcys
Limestone
Fritted glass
Sandstone
Sandstone
Semiqua.rtzitic
sandstone
Serriiquartzitic
sandstone
Alundum
Alundum
Chalk
Sandstone
1
2
3
4
1
2
20
1,000
Sand density
Bulk volume of
sample and
volume of saod
grains
Weight of dry
sample, weight of
saturated sample
imm8flled weight,
and volume of
sand grains
Porosity,
g:
Effective porosity
11
Value from
Average from
saturation methods high observation
Value from
low observation
Average
Average from
gas methods
17.47
28.40
14.00
3029
17.81
28.68
14.21
31.06
16.90
27.97
13.70
29.13
18.50
29.30
15.15
31.8
16.72
27.56
13.50
26.8
0.2
3.95
4.15
3.66
4.60
3.50
BZE
BZG
0.8
1,000
3
1.6
45
3.94
28.47
16.47
32.67
19.46
4.10
28.78
16.73
33.10
19.68
3.71
28.00
16.08
32.03
19.12
4.55
29.4
17.80
33.8
20.2
3.48
27.8
16.00
31.7
18.8
61A
722
1123
1141A
.... ~

35
::

30
..
.
,_
_
"
:~
25

~ ~
20
~
e
g__ 15
L..
~
~
~~
~ ~
~
IO
~
~,....,
 .....,n
~l~~I ~!Pf~
2
,
0
57
56
SZE
BZG
61A
722
_ff23
1141A
Sample no.
Fra. 215. Results of porosity check. Dotcl.a.sh lines represent maximum values dash
lines represent minimum values. Compare with Table 23 for more informati~n on
the samples. (After Dotson et al. 12 )
Carbonate Rocks
The foregoing discussion is applicable to materials of intergranulartype
porosity. Carbonate rocks are more heterogeneous, as was shown in Fig.
27. Small samples, such as used in the routine techniques, yield values
of porosity which do not include the effect of vugs, solution cavities, etc.
The saturation methods of determining pore volume and bulk volume ar
unsatisfactory, as drainage will occur from the larger pore spaces. Th
various other techniques also have inherent errors when applied to vugular
materials. It is necessary, therefore, to use larger core samples and to determine the bulk volume by measurement of the core dimensions. The
effective grain volume is obtained by using a large gasexpansion porosimeter similar to the Bureau of Mines type. Kelton13 reported results of
whole core analysis, a method utilizing large sections of the full diameter
core. Figure 216 and Table 24 summarize a part of Kelton's work.
Group
1.98
1.58
2.56
2.21
2.62
3.17
7.92
8.40

58
o[\
,.__
.
\
___ 
...,, Sandstones
~,..
10
~
...........
i ,000
59
c, = (1/V,) (dV,/dP), where V, is the volume of solids and Pis the hydrostatic pressure. The value of c, for a particular rock can be determined
simply by saturating the rock with a fluid, immersing the saturated rock
in a pressure vessel containing the saturating fluid, then imposing a hydrostatic pressure on the fluid and observing the change in volume V, of.
the rock sample. The compressibility of the solids is considered for most
rocks to be independent of the imposed pressure.
Reservoir rocks are subjected to other conditions of loading than described above. Therefore, it is necessary to introduce other compressibility
concepts. A rock buried at depth is
Inferno!
subjected to an overburden load due
pressure.
to the overlying sediments. This
gouge
overburden load may be considered
to exert an external hydrostatic
!0
Reservoir
stress, which is in general greater
than the internal hydrostatic stress
0
0
of the formation fluids.
0
0
In the laboratory it is possible to
0
2,000
3,000
4,000
r
5,000
6,000
Depth of burial, ft
Frc. 217. Effect of natural compaction on porosity. (From Krumbein and Sloss.1')
tional chang~ in pore volume of the rock with a unit change in pressure.
Ro?ks b'.'ned at depth are subjected to internal stress exerted by fluids
contamed .m the pores and to external stress which is in part exerted by
the overlymg rocks. The internal stress is hydrostatic, while the external
stresses may have different values in different directions.
The depletion of fluids from the pore space of a reservoir rock results in
a change in the internal stress in the rock,. thus causing the rock to be subjected to~ different resultant stress. This change in stress results in changes
m the gram, pore, and bulk volume of the rock. Of principal interest to the
;eservoir engineer is the change in the pore volume of the rock. The change
m bulk volume may be of importance in areas where surface subsidence
could cause appreciable property damage.
Geerts1Il3;" and o_thi;rs have developed a theory of rock compressibility
which provides an ms1ght into the mechanics of rock deforniation under
oilfield conditions.
. The th~ory can best be explained in terms of experimental techniques.
First co.ns1der the material forming the grains or solid portion of the rock.
The solids when subiected to a hydrostatic stress will deform uniformly.
The bulk deforniation of this material can be expressed as a compressibility
  
Gland nut
Overburden
pressure
Carpenter and Spencer in testing Woodbine cores with similar equipment varied only the external pressure. Typical curves obtained are shown
in Fig. 219. The ordinate is the reduction in pore space resulting from a
change in overburden load. The change in pore space VP was determined
by measuring the volume of water expelled from the jacketed core on increasing the overburden pressure. VB is the bulk volume, and <P the porosity fraction. Therefore, Vs.P = V., the pore volume. The slope of the
curves shown is a compressibility of the form (1/V,)(aV,/oP*)p where P*
60
,,
3.0
,#
7
2. 5
'/
.,
o Limestone
0
...
g6
11l+l+ll
~;;
i'\.~
O::g~5~
~
"q;+fl:::::
...
~
~
~E~4 ~\"!..>
.J.f!iS ......_ "
8~
'~IOI
'
c:g3
~~
..
~ g_ 2 ~e
o=
ct
LL.~
~
g 1
"q;
r
B
0o
'
&
~ 
~
~ ~
<:) .....
'
oi>+++++l++1
~J.:
~.
:::.~
10
+++f1+++I
<:3 ~
I
6
~
~
I I
I I
~
: :.
...
12
/
/
~'_.L1
Sandstone
(Bureau of Mines data )
'
14 f6 f8
Porosity, 0/o
20
22
24
26
28
30
32
Hall.1 8 )
,.. x,:Ii'...
g_
7!/
Core No. I
61
<J
2.0
~~
1i
, ,
"
15
.~ 1.5
c
.'
I
//
"
,'
111.
~
u
'I I
I I
f.0
t0
';;
x0
O
98 
::;... :>
~ ~ 7
~g_
e~
<t>.j..
0.5
OE
Woodbine sand
4,000
Pressure, psi
6,000
8,000
1;a.
~ ..s 2
'
Vj
.,,
+++o_;p=i=++~1
~ +l'fl\1 ~
i"
~ ~
 ~
~Q;;  _...,...._a,:..,
~ ~ 1++l :::::.
~
~o;;;_g
.,.,r::.
q,
....,!Q;)
~~~
~
.,,p
~
""
"<;[
6~
~
~< 5
o Limesrone
g Sandstone
"IS
c::
O.;u
2,000
ftx"o
~10~~~~~~~~~~~~~~
..... e:;::;.':'
.;:; : .....
~.s: ~r~
ij<;\i
~ 1++l++l
~
f""
&
'l++1++.Jl1l1++I
c 1
0
<3
0'''~''''~''.,0,~.,.,__,''
0
2
4
6
8 fO f2 f4 f6 f8 20 22 24 26
Porosity, 0/o
62
;:.
~\
:l
~ 25
20
~?,\
v,
30
</>
and that
15
\\
>
10
e
0
a.
' ~
,.._
'..:::::: ~
......
r r_
dV,~!dVB
v,
since
v, =</>VB
~ </>
VB
dV,"" dVB
This states simply that the total change in volume is equal to the change
in pore volume. Carpenter made use of this principle in his experimental
technique.
Furthermore, if the external hydrostatic pressure P* on a rock is constant
in all directions as in a laboratory test of a jacketed core, dP* = 0, and
dV, = _'!!>. dP
or
_ _!_ dV, = '!!>.
V,
</>
V, dP
</>
such that co/</> may be defined as the pore volume compressibility c,.
Geertsma has stated, however, that in a reservoir only the vertical component of hydrostatic stress is constant and that the stress components in
the horizontal plane are characterized by the boundary condition that there
is no bulk deformation in those directions. For these boundary conditions,
he developed the following approximation for sandstones:
,.... 10
1
c
2 '
1'
!'...
~r
r
~ r
>
1''
~
\~\""'
~~
Thus, the effective pore compressibility for reservoir rocks on the depletion
of internal pressure is only onehalf of that determined by present methods
in the laboratory.
Fatt reported results of tests on a limited number of samples having porosities ranging from 10 to 15 per cent with one sample having a porosity
near 20 per cent. The results of these studies are presented in Figs. 222
and 223. Fatt, 16 in effect, determined (I/V,)(aV,/aP)P* for .a range of
values of P*. The data reported are correlated with a socalled "net overburden pressure" defined as (P*  0.85P). The factor 0.85 is introduced
to take into account that the internal pressure does not wholly react against
'f
;;
~
:<;
ldV
le, __
::::..!.J!,..._,, __
V, dP ~ 2 </> 

65
the external pressure. The factor is believed to be dependent on the structure of the rock and to range from 0.75 to 1.00 with an average of 0.85.
Fatt found, as illustrated in the curves, that the pore compressibility
was a function of pressure. Within the range of data considered, he did
not find a correlation with porosity.
In summary, it can be stated that pore volume compressibilities of consolidated sandstones are of the order of 5 X 10 to 10 X 10 reciprocal
psi.
flow in cubic centimeters per second, and the other terms are as previously
defined.
If the reservoir rock system is considered to be a bundle of tubes such
that the flow could be represented by a summation of the flow from all the
tubes, then the total flow would be
t;p
Q, = n "''
8L
PERMEABILITY
v = 32L
\'
,,,.i. t;p
j=l
Q,=Ln'8L
where
ni
Qt
t;p
l
k
8 L
n3r;4
(24)
i=l
If
(25)
(21)
k
where
= ~l
4
n3Tj
(26)
j=l
v'
2d11P
fpL
(22)
Q = 7r'f' t;P
8L
(23)

66
flow channels and their flow relationship to one another. It becomes appar
ent that some means other than Poiseuille's law had to be found to define
the flow coefficient of a rock.
In the preceding section on porosity, it was shown that the porosity was
independent of sandgrain size but dependent on the mode of packing. Iri
the same section, it was shown that the size of the openings between the
sand grains decreased as the sandgrain size decreased. Therefore, perhaps
108
107
10
~1
...
"
Sample.No.
~
.
'
'~
~ '>
'~
"
~1~ 10'
"~
"
2
3
4
5
,,
7
8
'
.>~.,
~
~'~
to
""
'
t3
t4
..
15
~~
17
<9
"...
Leed
shot~
24
25
26
27
..::::: {9
~' ~
'
10
.........
~
K
"
Fra. 224. Metallic cast of pore spaces in a consolidated sand. (Courtesy of Humble
Oil & Refining Co.)
u nconsolidoted sand/
102
0.001
0.01
Porosity
~2.5
f2.3
16.9
37.0
20.3.
37.8
{9.7
15.9
H.9
19.5
18.4
22.3
t6.3
f9.2
2t.4
20.6
33.2
21.9
23.8
26.9
27.7
22.t
28.8
Unccnsolidotecl
~~ ~K ~
<
22
23
~'\
21
"'~'
"...
Sond
Consolidated
Sroclfonl
Srodford
3rd Venango
Ceramie A
Robinson
Ceromie B
Woodbine
WHeo:t
3rd Venango
Robinson
Robinson
3rd Venango
Wileox
Warran
3rd Venango
Robinson
Ceromie C
3rcl venongo
Woodbine
20
~z;.
104
67
385
Ottawo
2030 Ottawa
Lead shot
34.5
34.5
30.9
~.
<
"'" '
10
0.1
Flint
r. ,_
100
10
00
dp
R=yF10. 225. Correlation of friction factor wit~ Reynqlds numbe_r for flow of homogeneous fluids through porous media, where d is defined as the diameter of the av~rag~
grain and v is the apparent velocity, i.e., volume rate of flow/total crosssectiona
area. (After Fancher, Lewis, and Barnes.ro)
The preceding attempts to determine a means of calculatin!' .the cond'.'ctance of a rock were made to augment or supplant the empirical relationship of permeability as developed by Darcy. 21 The pore structure of rocks

68
does not permit simple classification, and therefore empirical data are required in most cases.
In 1856, Darcy" investigated the flow of water through sand filters for
water purification. His experimental apparatus is shown schematically in
Fig. 226." Darcy interpreted his
observations so as to yield results
essentially as given in Eq. (27).
0
Q=KAh,h,
(27)
k(dP pg dz
)
v, =  ; ds 1.0133 ds X 1()<
Here,
(28)

ft9
dz/ds can be expressed as sin 8 where 8 is the angle between s and the
horizontal. v, can further be defined
z
as Q/A where Q is the volume rate
of flow and A is the average crosssectional area perpendicular to the
lines of flow. The coordinate system
5 ,.. ... I
applicable to Eq. (28) is shown in
/
I
I
Fig. 227. The convention of sign is
that v. should be positive when the
fluid is flowing toward increasing
values of the coordinate s. The
quantity of Eq. (28) in parentheses
can be interpreted as the total
pressure gradient minus the gradi+.r
+z
ent due to a head of fluid. Thus if
FIG. 227. Coordinate system ,to which
generalized Darcy's law is referred.
the system is in hydrostatic equilibrium, there is no flow and the
quantity inside the parentheses will be zero. Equation (28) can be
written as follows:
k d (pgz X 106
)
v. = ;. ds
1.0133  p
c29l
...
(211)
where the plus sign corresponds to the upward direction of the positiv~ z
coordinate and the minus sign to the downward direction of the positive
z coordinate. The concept of a flow potential is shown to be useful in later
applications.

70
Va=
M
=LT
M
= L'
M
P =LT'
dP
M
ds = L'T'
L
g = T'
dz
. 1ess
ds = dimenSion
T=
k
( M
ML)
M/LT L'T'  L' T'



71
and the porous medium must not react; that is, ~ a reactive fluid fl~ws
through a porous medium, it alters the porou~ medium, therefore changing
the permeability of the medium as flow contmues.
Equation (28) is a useful generalization of Darcy's law. However, several simple flow systems are so frequently encountered in the measurement
and application of permeability that it
0
is appropriate to obtain the integrated
form for these systems.
Horizontal Flow
Horizontal rectilinear steadystate
flow is common to virtually all meas0
urements of permeability. Consider a
block of a porous medium as in Fig.
228. Here Q, the volume rate of flow, FrG. 228. Sand model for rectilinear
is uniformly distributed over the inflow flow of fluids.
face of area A. If the block is 100 per
cent saturated with an incompressible fluid and is horizontal, then
dz/ds = O, dP/ds = dP/dx, and Eq. (28) reduces to
kdP
V:.:
M M)
kLT(
= M L'T'  L'T'
;dx
(213)
=LT
separating variables,
g_dx =
k = L'
A rational unit of permeability in the English system of units would be
the foot squared and in the cgs system, the centimeter squared. Both
were found.to be too large a measure to use with porous media. Therefore,
the petroleum industry adopted as the unit of permeability, the darcy,
which is defined as follows:
A porous medium has a permeability of one darcy when a singlephase fluid of
one centipoise viscosity that completely fills the voids of the medium will flow
through it under conditions of viscous flow at a rate of one cubic centimeter per
second per square centimeter crosssectional area under a pressure or equivalent
hydraulic gradient of one atmosphere per centimeter.
Conditions of viscous flow mean that the rate of flow will be sufficiently
low to be directly proportional to the pressure or hydraulic gradient.
Darcy's law holds only for conditions of viscous flow as defined above.
Furthermore, for the permeability k to be a property of the porous medium
alone, the medium must be 100 per cent saturated with the flowing fluid
when the determination of permeability is made. In addition, the fluid
~ dP
integrating between the limits 0 and Lin x and P1 and P,, where P, is the
pressure at the inflow face and P2 the pressure at the outflow face,
Q
A
Q
A
f,L dx
 (L  O)
or
= 
f,p, dP
P1
= k (P,
= k
 P 1)
_ kA(P1  P,)
QL
(P,  P,)
(214)
i l
nfr;
j=l

72
expressed in. Eq. (28), is still valid. However, for steady flow, the mass
rate of flow 1s constant through the system rather than the volume rate of
flow:.. Therefore, the integrated form of the equations differs. Considering
rectilinear flow and steady flow of compressible fluids, Eq. (28) becomes
pv. = _ kp dP
dx
pV:
Qo = kA P1  P2
therefore
since v. =
pressed as
po13cP
(216)
dP
since p
V:i: =
9.
dx =
1"
 (L  0) =   (p,  pi)
A
c
m=kAp1 p,
c
P1 = Po
P2 = Po
then
Pl 
P,Q,
or
Pl
+ PoCP1
+ PoCP2
p, = PoC(P,  P2)
poQo = m = kA PoC(P1  P 2)
c
L
2L
P,
(2_20)
P2')
PQ
(217)
dp
kA (P1
\cpdx
_.E_
P,2)
Q,
~ ..! dp)
~PdP
dx
dx = dp
A
C
then
dx
if
~pdP
(219)
but pQ = p,Q, = constant where Q and Q, are defined at flowing temperature, and p = p,(P /P,).
A
substituting the above quantities in Eq. (215),
PA!.J. =
P,Q,
A
by definition
xJ.L
dP
dx
p
QIA,
= p,,ecP
1 dp
dP
cpdx = dx
= Cp dx
integrating,
(218)
Therefore
dp
dP
 = Cpc13cP_
dx
dx
p 9. =
A
pV;1;
is a constant.
73
(215)
w~ere both the righthand and lefthand members of Eq. (28) are multiplied by the density.
For steady flow
P,
PQ
P, Q =
:;i, (P1
P,2 )
Q = kA (P1  P,)
P2)
(221)
which is the same form as (214). Therefore flow rates of ideal gases can
be computed from the equations for incompressible liquids as long as the
volume rate of flow is defined at the algebraic mean pressure.
Vertical Flow
Figures 229 to 231 illustrate three vertical flow systems frequently encountered in practice. Each system is of uniform crosssectional area A. (In
the developments which follow the fluids are considered incompressible.)
First consider the case when the pressures at the inlet and outlet are
74
equal (free flow) such that only the gravitatioual forces are driving the
fluids (Fig. 229).
s= z
and
dz= 1
ds
75
=;(~+pg)=~
=k: pg(~+ 1)
(223)
When the flow is upward and the driving head is h (Fig. 231) (z defined
as positive downward),
dz
ds
Flow under
head h
dP
ds
1
v =
Flow under
dP
pgh
dz= ypg
head h
Free flow
 kpgh
i

~
]
. . . . . 1
g_
'~
Q = kApgh
Therefore
::.:~;:.
... ,
'.'
.L
(224)
.L
/~~ ~'. JL
/ : ..~:~;:
i
 ....
downward.
/
/
T
h

'1_14~
 Fit~erbed
//
4tJ/
1=====...:.==='=l~
k
Q
v. =pg= .
kA
Q =pg
.
FIG. 232. Vertical flow through filter bed with constant head.
(222)
Next consider the case of downward flow when the driving head (difference
in hydraulic head of inlet and outlet) is h (Fig. 230). Then
dz
;I:;
Therefore from Eq. (28)
= 1
Data:
Quantity of water to be filtered = 5,000 gal/hr
Thickness of sand filter bed = 4 ft
Permeability of sand filter bed = 1,200 millidarcys
Crosssectional area of pit (also sand filter bed) = 1,800 sq ft
Viscosity of water at 20C = 1.0 centipoise
Barometric pressure = 14.7 psi, 760 mm Hg, 29.92 in. Hg
 
76
What level of water must be kept in the pit above the sand filter bed b.
order to filter 5,000 gal of water per hour? Assume that the solids temoved
from the water do not alter the permeability of the bee::.
By definition
(!J + 1)
v, = +~dP
dr
y, + 1 =
2.12
dz= O
ds
ds = dr
_
kApg
Q  1.0133 X 10' L
77
9. =
A
51._
2mh
(225)
+v,
51._ = ~ dP
Therefore
2mh
dr
_9._ (' dr
27rh
Radial Flow
Jr,,,
= 1!_ {
P,
dP
.} P,,,
Q = 2,,kh(P,  P w)
(226)
In (r./rw)
Equation (226) can be appropriately modified for the flow of compressible fluids. The details of modifying the foregoing equation are omitted,
as they are essentially the same as the ones used in the horizontal, rectilinearflow systems.
After modification for variations in flowing volumes with changing
pressures Eq. (226) becomes
1. Slightly compressible fluids:
m=
or
Considering the cylinder horizontal and radial flow inward as equal ';or,
it is possible to integrate Eq. (28) and obtain an equacion ~nrtoadystate
mdfal flow of an incompressible fluid.
(227)
Q _ 2,,kh(P,  P w)
0

F1a. 233. Sand model for radial flow of fluids to central well bore.
2,,kh(p,  Pw)
c Jn (r ,/rw)
. ln (re/rw)
p,.
(228)
78
Q = 27rkh(P,  P w)
Qr
In (r,/rw)
(22g)
Pe+ Pw
Conversion of Units in Darcy's Law. In Darcy's law and the special
.Row equations developed therefrom, the units \Vere presumed to be either
B. consistent set or those obtained from the definition of the darcy, the
accepted unit for the petroleum industry.
It is convenient in many applica.tions of Darcy's law to introduce
commonly used oilfield units. The following is a summary of the more
common equations with the conversion factors to convert to oilfield terminology.
Linear Flow: Liquids (or Gases with Volume at Mean Pressure).
79
where Q is the volume rate of flow, P" and P w are in pounds per square
inch, k is in darcys, is in centipoises, his in feet, and re and r 10 are in consistent units.
The above equations describe the flow in the porous medium when the
rock is 100 per cent saturated with the flowing fluid. Appropriate modifications will be discussed in later sections to take into account presence of
other fluids. Since the above equations describe the flow in the medium,
appropriate volume factors must be introduced to account for changes in
the fluids due to any decrease in pressure and temperature from that of
the medium to standard or stock tank conditions.
Example 29 lists various unit conversions to change from the unit of
the darcy to other systems of units.
Example 29.
kA(P,  P,)
Q = 11271
.
L
1 dare
(231)
where Q is the volume rate of flow, P 1 and P 2 are in pounds per square inch,
k is in darcys, is in centipcise, A is in square feet, and L is in feet.
Gases at Base Pressure P& and Average F"lawing Temperature T 1.
Linear:
_ 3.1615kA(P22
Q 
P 22)
P,,L
= 19.88kh(P.'  P w 2 )
P, Jn (r,/rw)
(cc/sec)(cp)
(sq cm)(atm)/cm
= 9 869 X 10'
(cc/sec)(cp)
sq cm[dyne/(sq cm)(cm)]
= 9.869 X lo" sq cm
= 1.062 X 1011 sq ft
(232)
(233)
Q=
Radial:
Q.
.= (A)(M')/L
k'
(230)
_
kh(P,  Pw)
7 082
In (r,/rw)
(234)
Q = 39.76 kh(P,  p w)
In (r,/r.)
(235)
(sq ft)(psi)/ft
9 _679 X lQ4
[bbl/(day)](cp)
1127
(sq ft)(psi)/ft
= 1424 X 102
[cu ft/(sec)](cp)
(sq cm)(cm water)/cm
[gal/(min)](cp)
(sq ft)(ft water)/ft
80
FUNDAMENTAL PROPERTIES OF
Consider the oase where the flow system is comprised of layers of porous
rock separated from one another
by infinitely thin impermeable
.,,._P..:.'~">?,
barriers as shown in Fig. '234.
h,
The average permeability 7i can be
Q+~,''!,.'2LICh;:21Q computed as follows:
Q, = Q,
+ Q, + Q,
h, = h,
+ h, + h, =
f':w
~L<
FIG. 234. Linear flow, para11el combination of beds.
FLUID~PERMEATED
BOCKS
81
As all these terms are the same in each of the parallel layers, an evaluation
of the parallel radial system would yield the same solution as obtained in
the linear case.
Bed
ft
20
15
10
5
1
2
3
4
_ 7iwh,(P1  P,)
Q' .L
Horizontal permeability,
millidarcys
Pay thickness,
100
200
300
400
_ k 1wh1(P1  P2)
Q' Q,
7i =
= k,wh,(P,  P,)
L
so
7i = 100
Therefore
L
and
7ih,
w(P~"i,
or
+ k,wh,(P1 
L
P2)
P2)
+ k,wh,(P1 
P,) (k1h1
P,)
.L
w(P~"i,
+ k,,h, + k,h,)
7iih;=Ik;h;
i=l
R,
j=l
,.,,,,,, ,,,,,.,,,,,,.,,,..
Q,
then generalizing,
l k;h;
l h;
20
1<P,
(},_
(236)
= 200 millidarcys
P,  p,
f!.P,
Q+
+ f!.P, + f!.P,
3
L = L 1 + L, + L, =
L;
combina~
network as in the linear system. The only difference in the two systems is
the manner of expressing the length over which the pressure drop occurs.
Q, = 7iwh(P1  P,)
.L
Q, = k,wh fJ.P2
.L,
of beds.
;=l
;1
10,000
50
Q, = Q, = Q, = Q,
T'.
i=l
"=
n  
i=l
Q, = k,wh,(P,  P,)
l k;h;
l h;
~i=~'~
Q _ k 1wh tJ.P,
1
Q3
Li
_ k 3whtJ.P3

.L,
I
82
Linear system
Solving for pressure and substituting for t!.P in the equations above,
Q,L = Q1L 1
'fwh
k,wh
+ Q,,,L, + Q,,,L,
k,wh
k,wh
or
and
If
f= i=l
2 000
=25=
then generalizing,
r:
n
l~'I'
k, = ____!,__
I
I
I
I
I
I
I
_b
(237)
I
I
equation
(237)
log r,/r w
k, =
L, kJ
80 millidarcys
2 000
10+5+5+5
Radial system
j=l
83
f.
L,
il
log r1/r;1
k
J
lo 2,000/0.5
log 250/0.5 +log 500/250 +log 1,000/500 +log 2,000/1,000
25
50
100
200
= 30.4 millidarcys
(238)
=
k, =
log r,/rw
log r;/r,_,
L,
;1
k]
(238)
Bed
I
2
3
4
Length of hed,
ft
Horizontal permeability,
millidarcys
250
250
500
1000
25
50
100
200
nels and fractures do not change the permeability of the matrix but do
change the effective permeability of the flow network. In order to determine the contribution made by a fracture or channel to the total conductivity of the system, it is necessary to express their conductivity in terms
of the darcy.
Channels. Recalling Poiseuille's equation for fluid conductivity of
capillary tubes,
Q = "'"' t!.P
8,,
The total area available to flow is
"1"'
Q=Act!.P
8 L
(23)

84

t:,.p
Q = Ak L
k = 54.4 X lO'h'
10'(2.54)'r2
:r,
 0.785(2254.2)(0.0001)
144
0 785
= l2vL
h'
kA~
(0.01/12) (1) (1)
1(1)
1.1271(5,440)
1.1271(5,440)(0.00083)
5.1095 bbl/day
Th
b . ed rate is 5 12077 bbl per day, or an increase of 45,437 per
situ fractures and so1ut1on
cavities contribute
t e Itcom
m
bvious that in
cen.
iso
.
substantially to the productivity of any reservoir.
,,d'
l
1.1271(2,000) 4(144) 1(1)
(241)
= 80 x lO'r' = 20 x 10'd2
where d is the diameter of the opening in inches.
Therefore, the permeability of a circular opening 0.005 in. in radius is
2,000 darcys or 2,000,000 millidarcys.
Consider a cube of reservoir rock 1 ft on the side and having a matrix
permeability of 10 millidarcys. If a liquid of 1centipoise viscosity flows
linearly through the rock, under a pressure of gradient I psi per ft, the rate
of flow will be 0.011271 bbl per day. If a circular opening 0.01 in. in
diameter traverses the same rock, then the rate of flow can be considered
to be the above value plus the rate of flow Q' through the circular opening.
Then
Q' = l.l271kA
12
h'
= 84.4 X lO'h'
k = 12(9.869) (10')
x lO'r'
h'
k=
then
vL
D _
=k
85
( 40)
2
l=T
where I
current, amp
voltage drop, volts
r = resistance of the circuit, ohms
(242)
      

l
I
86
but
or
where
= resistivity, ohmcm
= I/p = conductivity
r=uA
samples of media.
Two methods are used to evaluate the permeability of cores. The method
most used on clean, fairly uniform formations utilizes small cylindricai
samples, perm plugs, approximately 7i in. in diameter and 1 in. in length.
Therefore
AE
pL
(243)
(244)
tion prior to the determination of the permeability. Perm plugs are drilled
from the larger cores parallel to the bedding planes. The perm plugs are
dried in an oven or extracted by a soxhlet extractor and then subsequently
Q=~Alll'
L
note that
k
!!.P
~;;=uy~z
(245)
dried. The residual fluids are thus removed, and the core sample becomes
100 per cent saturated with air. The perm plug is then inserted in a core
where
(246)
From (244)
.,
~~k'
f!.P ~f!.T
87
(247)
As in t~e case of Ohm's law, further analogies are possible and will be
discussed in later sections.
The abovelisted analogies are useful in that many complex problems of
both heat and _electrical conduction have been solved.analytically so that
the mathe~at10s can ?~ extended readily to problems of flow through
porous media. In add1t1on, many fluidfio,v problems involving complex
~eometry _can b~ solved by appropriate electrical or heat models scaled
own in Size or time for convenient laboratory performance.
Measurement of Permeability
The permeability of a porous medium can be determined from samples
extracted from the formation or by inplace testing. The procedures dis~
25

88
holder of a permeability device such as illustrated in Fig. 238. An appropriate pressure gradient is adjusted across the perm plug, and the rate of
flow of air through the plug is observed. The requirement that the permeability be determined for conditions of viscous flow is best satisfied by
obtaining data at several flow rates and plotting results as shown in Fig.
21!9 from either Eq. (220) or (221). For conditions of viscous flow, the
6
I I
.~
Turbulence
89
Viscous/ V"
2
I/"'
o 0 .l
0.2
Q3
0.4
0.5
Q6
Q7
0.8
0.9
1.0
IP,P,l/L
(a)
I/
FrG. 240. Ruska universal permeameter: (A) Rubber stopper; (B) corehol~er
sleeve (C) core holder; (D) Howmeter selector valve; (E) pressur~regulat1ng
valve.' (F) pressure gauge (G) fill nipple; (H) liquidgas valve; (I) dischargefill
valve~ (J) burette. (From Stevens.:.)
Viscous/
,V
~
M M
IP' P'J/2L
'
(bl
FrG. .239. (a) Plot of experimental results for calculation of permeability, from
k=QL/A(P1P:1.); (b) plot of experimental result.s for calculation of permeability,
from k=2Q,,Pi,L/A(P~ P~). (From Stevens.)
data should plot a straight line, passing through the origin. Turbulence is
indicated by curvature of the plotted points. The slope of the straight!ine portion of the curve is equal to k/, from which the permeability can
be computed. To obtain k in darcys, Q must be in cubic centimeters per
second, A in square centimeters, P1 and P 2 in atmospheres, L in centimeters, and . in centipoises.
narily taken from this device at only one flow rate. To assure conditions
of viscous flow, it is the ln\vest possible rate which can be accurately
measured.
Example 212. Permeability Measurement. 1. The following da'.3. were
obtained during a routine permeability test. Compute the permeability of
this core.
Flow rate = 1 000 cc of air at 1 atm abs and 70F in 500 sec
Pressure, do~tream side of core = 1 atm abs, flowing temperature,
70F
Viscosity of air at test temperature = 0.02 centipoise
Crosssectional area of core = 2.0 sq cm
Length of core = 2 cm
Pressure, upstream side of core = 1.45 atm abs
p,v,
P,v, = Pv
90
p,
+ p, =
2
x 1,000
1.45 + 1 = 1.225
2
1.225V
v 815 cc
Q = tv = 815
500 =
=
L 53
k=9._!:_,.
TABLE
AM'
=
~
1.6;i~~i~)02) x
1,000
k =
15~0 =
Q L
AM'
Core group
10
409
0.6
1.2
.0.3
0.2
23
94
10
38
0.3
3.7
2.0
2(1)(2)
..
= 2 (0.4S) X 1,000 = 4.450 millidarcys
pressurelOJ
r;:::
Low ar"r
Rubber
tubing
Core
Screen
Low air
~~~11
Vacuum
Rubber diSC!JL_.J\!,
To f/owmefer
Vertical flow
(o)

72.5 millidarcys
25.
2. Assuming that the data indicated above were obtained but water
was used as the flowing medium, compute the permeability of the core.
The viscosity of water at test temperature was 1.0 centipoise.
91
Horizontal flow
(bl
Fra. 241. Permeameters for large core samples. (a) Clamp type; (b) Hassler type.
(From Kelton.13 )
92
93
of the gas with which the permeability of the porous medium is determined.
Figure 242 is a plot of the permeability of a porous medium as determined
at various mean pressures using hydrogen, nitrogen, and carbon dioxide as
the flowing fluids. Note that for each gas a straight line is obtained for the
The constant b in the above equation depends on the mean free path of
the gas and the size of the openings in the porous medium. Since permeability is, in effect, a measure of the size openings in a p.orous medium, it is
found that b is a function of permeability. Figure 243 represents a corre
~
~
5.o~~~
~
0
:<e 4.51++,l'+t,..f+l
3
2
4.0l+f;..+,7"f+1+J
:c
t; D.5
3.5j:b"~f>"'Jb'9;::=:::=::;J
.E
e' 0.3
Hydrogen
8_
l:
c
~,~<""''+++j o Nitrogen
0.4
0.6
Reciprocal
0.8
mean
1.0
1.2
.: o.
"
1.4
pressure, ATMt
+ (b/P)
k, 
mp1
(248)
where kL
'
...... ......
'.
 ..........
.......
~
r... ....
r...... ,....._
0.05
0.03
FIG. 242. Permeability of core sample L to hydrogen, nitrogen, and carbon dioxide
at different pressures. Permeability to isooctane, 2.55 millidarcys. (From Klinkenberg.:rr)
0.2
!1
'
'
....
0.02
o.o
'
                                 
94
95
graywackes common to the Gulf Coast and the arkosic sediments of California. The degree of hydration of the clays is a function of the salinity of
the water. Permeability changes of 50fold or more may be noted between
that determined with air and that determined with fresh water. The effect
of water salinity on the observed permeability is illustrated in Table 2..fl
N ATU.RA.L
K.
Kum
Kwo
K,.
s
s
s
s
s
34
34
34
34
34
4,080
24,800
40,100
39,700
12,000
1,445
11,800
1,290
10,000
23,000
20,400
5,450
1,380
10,600
18,600
17,600
4,550
s
s
s
s
s
34
34
34
34
34
4,850
22,800
34,800
27,000
12,500
1,910
13,600
23,600
21,000
4,750
1,430
6,150
7,800
15,400
2,800
925
4,010
5,460
s
s
s
s
13,600
7,640
11,100
5,160
1,788
4,640
4,250
2,520
1,500
866
6,500
2,630
2,380
2,180
2,080
1,585
34
34
34
34
36
2,140
2,080
1,230
2,150
T
T
T
T
T
36
36
36
36
36
3,340
2,640
2,820
2,040
2,500
3,180
2,080
2,730
1,920
2,400
2,900
1,900
2,700
1,860
2,340
2,860
Field
K,,.
K,.,
K.
1,190
885
7,400

3,360
4,020
3,090
1,840
15,300
17,300
4,600
13,100
1,680
4,200
2,010
1,750
17,100
4,510
14,300
3,280
17.2
147
270
1,680
167
736
3,490
326
1,970
3,860
10,900
157
5.0
19.5
9.9
1,030
2.4
2,790
2,020
180
794
197
119
6.2
4.1
1,960
9,000
13,800
5,220
12,900
973
4,150
2,540
8,200
2,010
2,690
1,860
2,490
2,340
2,820
1,630
2,280
2,650
1,860
1,490
2,460
1,550
2,060
2,460
1,040
,,
"'
While fresh water may cause the cementation material in a core to swell
owing to hydration it is a reversible process. A highly saline water can be
flowed through the core and return the permeability to its original value.
The reversibility of the effect of reactive liquids is illustrated in Fig. 244.
Care must be taken that laboratory permeability values are corrected
to liquid values obtained with water whose salinity corresponds to formation water. An example of the variation of air permeability and formation
water permeability is shown in Fig. 245. California and Gulf Coast sands
will normally exhibit lower formation permeabilities than those measured
by air in the laboratory.
1
"
. .. .y.
640
~320
"For example. K,. means permeability to air; K 000 means permeability to 500 grains
p'er gal chloride solution; K,,, means permeability to fresh water.
160
80
:c0 40
1'
~
,/
20
,,.
\
10
20
v.
v. '
,. ,/
40
80
Fra. 245. Relationship of permeabilities measured with air to those measured with
water having a concentration of 20,000 to 25,000 ppm chloride ion.
9i
and other v ..rial>les have been made. The reasoning behind some of the
correlations among porosity, permeability, and surface area are presented
here to enable the reader to gain some understanding of the interrelation
of the physical properties of rocks. Although these relations are not
Darcy's law, holds for viscous conditions of flow. It has previously been
shown that
r'
(239)
k=8
96
"
,,F
.~
>:::::
'....
G,
H
C"
.,,.,..
Therefore
!il
(ol
~ 100
~
Q. 90
~ ....._
A;
 _,_ 
~""
'..:::: .....~ ;...__
!" c
:~
~.e 80
o~
~
;=:
D
4r' 8
Q = .!._m'AP = kAP
e<D
if
</> =
si: 600
Therefore
gE
32
If the arrangement of the tubes is the most compact possible, the number of tubes per unit area is given by
~
1
4 sin 60 + .,,.,.. = 3.46r'
70
~ 0 60
~ ~
&'.~
50
k =
~000
(bl
FIG. 246. Changes in permeability with overburden pressure. (a) Curve AColorado; 3.96 millidarcys; BSouthern California coast, 40.9; CSan Joaquin Valley,
Calif., 45.0; DArizona, 4.36; EArizona, 632; FSan Joaquin Valley, Calif., 40.5;
GSanJoaquin Valley, Calif., 55.5; HSouthern California coast, 318.8. (b) Abasal
Tuscaloosa, Miss., 229 millidarcys, 15 per cent porosity; Bbasal Tuscaloosa, Miss.,
163, 24; CSouthern California coast, 335, 25; DLos Angeles basin, Calif., 110, 22.
(From Patt and Davis.30 )
Note, therefore, that the permeability for this simple case is a function
not only of the pore size but of the arrangement of the tubes. The arrangement of the tubes is defined by the porosity </> for these simple cases.
Consider a system comprised of a bundle of capillary tubes of the same
radii and length; k, the permeability, can be written as a function of porosity as follows:
k = <Pr'
8
The internal surface area per unit of pore volume can be derived as
follows:
Surface area = n21'TL
Pore volume = n.,,.,..L
2
n21'TL 2
r=Therefore S =   = S,
n.,,.,..L
r

l
98
where SP is the internal surface area per unit pore volume. Substituting
the above into the preceding expression gives
flow path L. as compared with the length L across the porous medium.
Then
v =vL.

I <I>
4<p
k =SS,'=
if, for the constant
~.
2s;
v La
<I>
(249)
k.S.'
where
"L=koL.
v = <t>m'
or
(!:..)'
f;.p
ko L L.
In a porous medium, m is equal to the ratio of the pore space per unit
volume of the medium q, to the surface per unit volumes, so that
s
The surface per unit volume of the medium s is related to the surface
per unit volume of pore space SP as follows:
s = q,S,
m2 6.P
m = p_
m = 2..rL =
<I>
I/k, is substituted,
99
m=
therefore
S,
v_
Then
From Darcy's law
k f;.p
v=
(214)
m' 11P
v=2 L
_p__11P(L)'
 koS.' L L.
(L )'
<I>
koS.'
L.
then
(L./L)'
kz
= koT
= Kozeny constant
(249)
Carman" reported that the value of k, was in all cases about 5. To apply
Eq. (249) to the calculation of permeability, the porosity </>, the surface
area per unit pore volume Sp, and the Kozeny constant kz must be kn~~
Rapoport and Leas" have reported a method of calculation of permeability
based on Eq. (249) and determination of S, from capillary data. Other
investigators have reported discrepancies in the assumpti~n that kz = 5.
In consolidated porous media there is little reason to believe k, to be a
constant, but rather, k, depends on ko and r for the particular medium.
l
101
Wyllie" and ot.hers have report.ed that k, can be evaluat.ed from electrical
properties of the porous material when saturated with an electrolyt.e.
100
FLUID SATURATIONS
In the previous sections of this chapter the storage and conduction capacity of a porous rock were discussed. To the engineer there is yet another
important factor to be determined. What is the fluid content of the rock?
In most oilbearing formations it is believed that the rock was completely
saturat.ed with wat.er prior to the invasion and trapping of petroleum. The
les.i dense hydrocarbons are considered to migrate to positions of hydrostatic and dyoamic equilibrium, thus displacing water from the interstices
of the structually high part of the rock. The oil will not displace all the
water which originally occupied these pores. Thus, reservoir rocks normally will contain both petroleum hydrocarbons and water (frequently
referred to as connate water) occupying the same or adjacent pores. To
determine the quantity of hydrocarbons accumulated in a porous rock formation, it is necessary to determine the fluid saturation (oil, water, and
gas) of the rock material.
Methods of Determining Fluid Saturation
There are two approaches to the problem of determining the original
fluid saturations within a reservoir rock. The direct approach is the selecting of rock samples and measuring the saturations of these samples as they
are recovered from the parent formations. The indirect approach is to determine the fluid saturation by measuring some other physical property of
the rock. The direct approach is all that will be discussed here. The indirect approach, such as using electric logs or capillarypressure measurements, will be discussed in later chapt.ers.
Determination of Fluid Saturations from Rock Samples
In det.ermining fluid saturations directly from a sample removed from a
reservoir, it is necessary to understand first how these values are measured;
second, what these measured values represent; and third, knowing what
they represent, how they can be applied.
In order to measure values of original rock saturations there have been
essentially three methods devised. These methods involve either the evaporation of the fluids in the rock or the leaching out of the fluids in the rock
by extraction with a solvent.
One of the most popular means of measuring the initial saturations is
the retort method. This method takes a small rock sample and heats the
sample so as to vaporize the water and the oil, which is condensed and
collected in a small receiving vessel. An electric retort is shown in Fig.
102
103
tends to decrease the liquid volume and also in some cases coats the internal
walls of the rock sample itself. The effect of cracking and coking in a retort is shown in Fig. 249, wherein 0.4 cc of oil actually in the sample yields
about 0.25 cc in the receiving vessel. Thus a fluid correction must be made
on all sample data obtained with a retort. Before retorts can be used, calibration curves must be prepared on various gravity fluids to correct for
the losses from cracking and coking with the various applied temperatures.
Another correction curve can also be obtained which correlates recovered
2
1.2
_v
!/""
.I
~ 0.6
0.4
0.2
10
'
8 0.8
LO
20
[/
10
30
40
50
60
,.
I/
.
V"
I
0.2
Time, min
0.4
0.6
0.8
1.0
1.2
Oil recovery, cc
API oil gravity with initial API oil gravity. It is normal for the oil gravity
of the recovered liquid to be less than the oil gravity of the liquid originally
in the rock sample. These curves can be obtained by running "blank"
runs (retorting known volumes of fluids of known properties). The retort
is a rapid method for the determination of fluid saturations, and utilizing
the corrections yields satisfactory results. It gives both the water and oil
volumes, so that the oil and water saturations can be calculated from the
following formulas:
Sw =
water, cc
(250)
pore volume, cc
80
s, =
oil, cc
pore volume, cc
1 
s.  s.
(251)'
(252)
VJ
104
clean the core sample in a device sjmilar to the soxhlet extractor or one
which uses centrifugal force. Thus, using the ASTM distillation only one
additional step is required to obtain information from which to calculate
fluid saturations in the core.
Another method of determining
water saturation is to use a centrifuge (Fig. 252). A solvent is injected
into the centrifuge just off center.
Owing to centrifugal force it is
thro,vn to the outer radii, being
Condenser
forced to pass through the core
sample. The solvent removes the
water and oil from the core. The
outlet fluid is trapped, and the quantity of water in the core is measured.
The use of the centrifuge provides a
very rapid method because of the high
forces which can be applied. At the
Soxh/ef extractor
same time that the water content is
determined, the core is cleaned in
Thimble
preparation for the other measurements. The values of v..rater and oil
saturation are calculated by using
Eqs. (250) to (253) as for the ASTM
extraction method.
There is another procedure for
saturation determination which is
used with either of the extraction
methods. The core as received from
the well is placed in a modified mercury
porosimeter (Fig. 214) wherein
Electric heater
the bulk volume and gas volume are
measured. The volume of water is
determined by one of the extraction
methods. The fluid saturations can
Fra. 251. Soxhlet extractor.
be calculated from these data.
In connection with all procedures for determination of fluid content, a
value of pore volume must be established in order that fluid saturations
ca.n be expressed as percentage of pore volume. Any of the porosity procedures previously described can be used. Also the bulk volume and gas
volume determined from the mercury porosimeter can be combined with
the oil and water volumes obtained from the retort to calculate pore volume, porosity, and fluid saturations.
105
106
and water from the core. Thus, the contents of the core at the surface have
been changed from those which existed in the formation. The core has
been invaded with water, and the contents subsequently subjected to a
solutiongasdrive mechanism. As the invasion of the filtrate precedes the
core bit, it is not possible to use pressurized core barrels to obtain undisturbed samples.
In the case of drill cuttings, chips, or cores from cabletool drilling, they
also have undergone definite physical changes. If little or no fluid is maintained in the well bore, the formation adjacent to the well surface is depleted owing to pressure reduction. As chips fall into the well, they may
or may not be invaded, depending on the fluids in the well bore and the
physical properties of the rock. In all probability, fluid will permeate this
depleted sample, resulting in flushing. Thus, even cabletool cores have
undergone the same two processes as was noted in the case of rotary coring
but in reverse order.
107
cent, the watersaturation values obtained with oilbase muds may be considered to be representative of the initial water saturations in the reservoir.
Hence, it is possible to obtain fairly representative values of inplace water
saturations by selecting the fluids with which the core samples are obtained.
Kennedy et al. studied cores with permeabilities ranging from 2.3 to 3,040
Amico fitting top
Neoprene gosket
fin. st~el tubing
~in. steel tubing
and the amount was measured at the outer boundary. The values gave
the change in saturation caused by the flushing action of the filtrate. The
pressure on the core was reduced to atmospheric pressure, and the amount
'Neoprene gasket
Brass end plate
of water and oil that remained in the core was determined. The total
effect of both flushing and expansion because of pressure reduction was
thus measured.
Schematic illustrations of the changes in saturation resulting from these
tto processes for oilbase and waterbase muds are shown in Fig. 254. It
is noted that the original flushing action reduced the oil saturation by
approximately 14 per cent. The expansion to surface pressure displaced
water and additional oil. The final water saturation was greater than the
"o"ring seol
Steel ring
Compression screw
Amico fitting top
FIG. 253. Sectional view of test cell with core in place. (From Kennedy, Van Meter,
and Jones.~)
filtrate is oil, so that the flushing action did not alter the initial water
saturations but did result in replacement ot approximately 20 per cent of
millidarcys and porosities ranging from 5.2 to 21.7 per cent. The drilling
the initial oil. On pressure depletion a small fraction of the water was ex
fluids used were clay bentonite, lime starch, and oilbase muds with viscosities from 65 to 133 centipoises and water losses from zero fof the oil
pelled, reducing the water saturation from 49.1 to 47.7 per cent. The oil
aturation was reduced by both processes from 50.9 to 26. 7 per cent. Thus,
even when high water saturations are involved, up to approitlmately 50 per
108
Gas
Oil
67.6
Oil
53.4
34.8
Oil
26.7
calculate the volume of filtrate and reservoir water in the core. A large
fraction of the initial reservoir water may have been displaced by the invading filtrate, so the tracer method would give low values of reservoir
water saituration.
c
Water
32.4
Original saturation
46.6
Saturation ofter
Weter
38.5
Residua I
100
e so
"
~
:g
~
Water
109
60
40
15
c
;:;:
20
,
Core
Permeability, md
o LimeskJne No.3
5.6
6.7
Limestone No.4
+Limestone No. 5
saturot1on
10
20
30
40
50
60
70
10.0
80
90
100
pressure reduction
(a)
Cal
100
Gas
Oil
32.9
25.6
filtrate
18.0
Oil
26.7
Water
Water
49.1
49.1
Water
Oil
50.9
47.7
!3
+:
e
"g
60
 +. + ..
0
~
+
~
40
20
I>~
Soturotion ofter
Residual saturation
{bl
F10. 254. Typical changes in saturation of cores :flushed with waterbase and oilbase
muds. (a) Waterbase mud; (b) oilbase mud. (From Kennedy, Van Meter, and
Jones.m)
i
i
Core
Permeability, md
o Limestone No. I
127.?
Limestone No. 2
103.2
111.0
Woll Creek No. 2
+WOodblne
304.0
;:;:
Original saturation

80
10
20
30
40
50
60
70
80
90 100
...

111
The determination of contacts is made by carefully studying the residual oil saturations of the cores as a function of depth. In the oilsaturatr.<l
regions the samples will have essentially a constant value for residual oil
saturations, probably 15 per cent or greater. In the gas region the oil saturation is small or vanishes. Thus the depth of the gasoil contact is defined
by a sharp increase in oil saturation. In the water zone, the oil saturation
gradually disappears with depth. By observing these changes in oil saturation, it is possible to choose the depth of the wateroil contact.
It is possible to establish a correlation of the water content of cores and
permeability from which it can be determined whether a formation wiJLDe
prpductive of hydrocarbons. Such
a
correlation is shown in Fig. 256,
1001~~~~r;,.,.l~wherein it can be noted that low5011++++H~~~~
permeability formations with core
Upi;er. limit of
"'
..;..
total water for
water
saturations as high as 55 per
E 2011r.+il'~.+:.H ail and gas ,___
cent may be considered productive.
,._~
~
sands
~ 1011+++_:+~~ff+++1
For higher permeability formations
the upper limits of water satura~ sf++"i.,.'.P";,_;~+++f1
if
. :=:
tions may be slightly less than 50
2:1++l':~+"~:~lt+++1
per cent. Thus, from the investigation of saturation values of cores
1
o 10 20 30 40 50 60 70 so 90 100 one can gather that a formation
Total water content, lo pore space
would be productive if the water
FIG. 256. Limiting values of total core saturation in the surface samples
water for oil and gas productionwater were less than 50 per cent.
base muds. (From Emdahl.
Another reason for measuring fluid
saturations of surface samples is to
obtain other correlations such that direct or indirect measurements of other
physical properties may also give indications of initial fluid distributions.
The measurement of electrical resistivity of the core samples, prior to
cleaning, permits correlations of electrical resistivities with other physical
properties to aid in electrical log interpretation.
Thus, in summary, it is seen that although fluidsaturation determinations made on core samples at the surface may not give a direct indication
of the saturations within the reservoir, they are of value and do yield very
useful and necessary information.
of the voids and the fluids with which those voids are filled. The fluids of
interest in petroleum reservoirs are oil, gas, and water. Oil and gas are
nonconductors. Water is a conductor when it contains dissolved salts.
Current is conducted in water by movement of ions and can therefore be
termed electrolytic conduction. The resistivity of a. material is the reciprocal of conductivity and is commonly used to define the ability of a
material to conduct current. The resistivity of a material is defined by.the
following equation:
rA
p=(254)
L
where p = resistivity
r = resistance
A = crosssectional area of the conductor
L = length of the conductor
llO
.. 
:,_: \
81
For electrolytes, p is commonly reported in ohmcentimeters, r is expressed in ohms, A in square centimeters, and L in centimeters. In the
study of the resistivity of soils and rocks, it has been found that the resistivity can be expressed more conveniently in ohmmeters. To convert to
ohmmeters from ohmcentimeters, divide the resistivity in ohmcentimeters by 100. In oilfield practice, the resistivity in ohmmeters is commonly represented by the symbol R with an appropriate subscript to define
the conditions to which R applies.
Formation Factor. The most fundamental concept in considering electrical properties of rocks is that of formation factor.
As defined by Archie", the formation factor is
(255)
where R. is the resistivity of the rock when saturated with water having a
resistivity of Rw.
The relationships between the electrical properties and other physical
9roperties of the rock are complex but can be illustrated by the following
developments.
Consider a cube of salt water (cube 1, Fig. 257) having a crosssectional
area A, a length L, and a resistivity Rw. If an electrical current is caused
to flow across the cube through an area A and a length L, the resistance of
the cube can be determined. Let this resistance be r,. Then
RwL
T1=A
Resistivity Relations
Porous rocks are comprised of an aggregate of minerals, rock fragments..
and void space. The solids, with the exception of certain clay minerals, ar~
nonconductors. The electrical properties of a rock depend on the geometry
In Fig. 257 cube 2 represents a cube of porous rock of the same dimension8 of cube 1 and 100 per cent saturated with water of resistivity Rw.
Considering the solids to be nonconducting, the electrical flow must then
112
L~.
113
RwL~
A~
R ,  r,A
L
1 cubic meter
(257)
and
(258)
I_ A.IA~
(259)
R,
Therefore
(b)
I= R,
 L./L:
Both the formation factor and the resistivity index are shown to be
functions of effective path length and effective crosssectional area. It is
desirable to relate these quantities
with other physical parameters of
the rock. To do so requires the use
of idealized models of porous sys
analytically.
Three idealized representations
have been introduced in the litera
(From Winn.31 )
By definition,
Hence
Therefore
_ RwL.A
0
LAa
F = R, = L./L =
Rw
A./A
Yr
A./A
(256)
1
1
A.
A1
+ A, =
q,A
q,A/A
L q,
(260)
=========~
11.j,

A:= q,SwA
then substituting q,SwA into Eq. (259),
(261)
L./L;   L. S.
f<L
therefore
Aa = Af
but
Af =A'!:_
and
A 1 = q,A
Therefore
A.= q,A L.
(L)' ~1= ~
= q,A(L/L.)/A = L
(262)
L
A 1" = A 1 L~
I _ q,A(L/L.)'jq,S.A(L/L;)
L./L;
(L:)'
l_
La Sw
(263)
FIG 260. Capillary tube model of porous media. (After Wyllie and Gardner.')
A. = (<I>) 2 A
F =
A~= A~'
L./L
therefore A: = q,SwA L;
therefore
L.
A 1 = q,SwA
I _ q,A/q,SwA _ L; l_
and
115
L./L
q,'A/ A
L.L
L <J}
A;
(q,S.)'A
L~=La=L
and
Substituting in Eq. (259),
(<P)'A/q,'S.'A
L./L;
1
Sw'
(265)
11~,
that the correlation with porosity was the better correlation and that the
formation factor could be expressed
(268)
F=</>
116
where C is some function of the tortuosity and m is a function of the number of reductions in pore opening sizes or closedoff channels. Since C is a
function of the ratio L./L, it is suggested that C should be 1 or greater.
The value of m has been shown from theory to range from 1 to 2.
Both the formation factor F and the resistivity index I depend on ratios
of path length or tortuosities. Therefore, to compute the formation factor
or resistivity index from the equations developed above, it is necessary to
determine the electrical tortuosity. Direct measurement of the path length
is impossible. Therefore, reliance has been placed primarily on e~pirical
correlations based on laboratory measurements. Winsauer41 et al. devised
a method of determining tortuosity by transit time of ions f!owiog through
the rock under a potential difference. The observed tortuosities were believed to be reliable. The data obtained were correlated with the product
F<t> as suggested by Eq. (262), rearranged as follows:
=F<t>
(L)'"
L
Cubic
Rhombic
Porosity,
%
47.6
39.5
Perpendicular
Parallel
Hexagonal
25.9
}to ofplane
paper
~~
unconsolidatedf.3
(267)
Packing
where</> is the fractional porosity and mis tbe cementation factor. Archie
further reported that the cementation factor probably ranged from 1.8 to
2.0 for consolidated sandstones and for clean unconsolidated sands was
about 1.3. Figure 261 presents the family of curves defined by Eq. (268)
2.64p..,
4.40p..,
3.38p..,
5.8lp..,
uniform spheres arranged systematically. Archie", in 1942, correlated observed formation factors with porosity and permeability. He suggested
Rhombic
pockinq~
I i
Hexagonal packi/Jg ~
:z
I
Cubic packing'1++",
1
10
20 30 4050
Porosity if>, per cent
F1G. 261. Formation factor F versus per cent porosity for various reservoir characters or cementation classes. (From Pirson.i3)
and cementation factors ranging from 1.3 to 2.2. The dashed lines indicate
the values computed for systematic packing of uniform spheres.
Measurement of Electrical Resistivity of Rocks
Laboratory measurements of electrical properties of rocks have been
made with a variety of devices. The measurements require a knowledge
of the dimension of the rock, the fluid saturation of the rock, the resistivity
of the water contained in the rock, and a suitable resistivity cell in which
to test the sample.
118
119
A simple cell is shown in Fig. 202. A sample cut to suitable size is placed
in the cell and clamped between electrodes. Current is then passed
A second type of cell is shown in Fig. 203 which is a combined capillarypressure and resistivity cell. This device has the advantage that two different tests can be performed simultaneously. The disadvantage is the
length of time required for a capillarypressure test. Capillarypressure
tests are discussed in Chap. 3 of this
volume.
4>
For dispersed spheres, not necessarily in contact, Maxwell states that
F1a. 262. Core sample resistivity cell. (From Rust.")
F=34>
2  4>
through the sample, and the potential drop observed. The resistance of
the sample is computed from Ohm's 13.w:
(269)
 L
(270)
where A is the crosssectional area of the sample and L is the length of the
sample. The saturation conditions of the test can be established at known
values prior to measurement or determined by an extraction procedure
after measurement.
Archie's and Slawinski's equations fit the data reasonably well except for
the aggregate of cubes. The data for the cubes fall above the other data
as well as above all three lines calculated from the equations. This could
possibly be indicative of a greater tortuous path length in such a system.
Observed formation factors for artificially cemented aggregates are shown
in Fig. 205. It may be noted that cementation results in increased values
of formation factor over that observed for uncemented aggregates. Fur

120
 
 

x Ottawa sand
BMCh sand
E
&
3
ondcrel!k
sand
"'
~
0
water resistivity on the formation factor for sands containing clay minerals
a Gloss sphere
so
10=~~,~o~~,~o~~o_.,..so,.,Jo'~soL..L>100
Porosity, 0/o
Wyllie:"
11
)
60
40
30
25
o
t::..
.2 20
,i::
mixture, grades
7ond3
Gloss sphere
mixture, grades
5ond9
Gloss sphere
mixture, grades
5ondf2
Gloss spheras
Gian spheflls
Beach sand
Archie_
.g 15
c
.2
e '
6
5
relation, is
50
121
is shown in Fig. 267. The formation factor for a comparable clean (clayfree) sand is a constant. The formation factor for the clayey sand increases
F = Cq,
(266)
where m is a constant depending
on cementation and C a constant
controlled by the porosity of the
.2u

,..,,,.,
UnconsoJidofed
1
10
20
30 40 50 60
Porosity, 0/o
80 100
Fta. 265. Effect of artificial cementation on the formation factorporosity relationship of unconsolidated aggregates. (From W yllie.46 )
was calculated from the definition of the formation factor and observed
values of R,. and R.. Wyllie proposed that the observed effect of clay
minerals was similar to having two electrical circuits in parallel: the con
a  RtD
where
R~
and
_!_
Roa
_!_
Re
1+ FRw
(272)
with water of resistivity RtD, Re is the resistivity due to the clay minerals;
FR. is the resistivity due to the distributed water, and F is the true for

 
122


mation factor of the rock (i.e., the constant value of formation factor
approached when the rock contains lowresistivity water).
,,
60 0
400
I\ I\
~Tixier's
''
relation for
consolidated formation
100
80
"
'"
60
\\\
I\ \\\
,~
n~
unconsolidated formation
\ I~
'
0
8
i
06 '...'.'.'.''
.
Humble relation F = 4'
2. f's ,
R,
R...0
,,..
345678910
20
_Porosity,
30 40 50 60
11
80 fOO
0
10
Roa
m
Rw
+b
1
1
m =  
Rw
FRw
R, = FRw
or
+ (R,/F)
and
R,
'= Rw
+ (RJF)
(272)
cnTrokd foro'T'
Roa
\
2
Then 
RoRw
'" = Rw
'
1
2
1
b = = 0
I\
200
123
(273)
where m is the slope of the line and b is the intercept. Comparing Eq.
(272) with Eq. (273), it may be noted that m = 1/F and b = 1/R,. The
curve labeled suite 1, No. 40, indicates a clean sand, since the line passes
through the origin, therefore
(2,74)
where F 0 .01 is the formation factor of the rock when saturated with water
having a resistivity of 0.01 ohmm. The quantity bin the exponent is defined as a shaliness factor and was correlated with the cationexchange
capacity. The cation<0xchange capacity is related to the clay content of
the rock and provides an independent determination of the amount of
shale in a rock.
Additional work is required to determine how the effect of clay in a rock
can best be evaluated.
The experimental data discussed are largely from measurements on sandstones or similar materials having intergranular porosity. Little data are

124
I= C'S111n
cnm~r_~~~~..
1.7
1.6
~Suite
1.5
1.4
f No. 40
(276)
Suite f No. 4
o Suite 2 No. f3
a Suite 6 No. 2
1.2
/"
1.0
09
lo? 0.8
~:
0.4
0.3
0.2
kA/x
~x
~
!/:::.:.

0.1~
0
1.3
o
_o
10 12 14 16 18
_1_ _
(275)
x Suite f No. 2f
1.1
125
20 22 (llm)1
Rw
Fla. 268. Watersaturated rock conductivity as a function of water conductivity.
I.From de Witte.")
tion. Equations (261), (263), and (265) indicate that the resistivity index is a function of the water saturation and the path length. From the
theoretical developments, the following generalization can be drawn:
f,000
and

126
100
0
60
00~
r
r
*a
1
127
101r
r
.....
20
'
' ,t'.. ,....
10
Resistivity index
I\
111
"3
, 0
n2 = 2.34
\12.33
40
40
20
10
= Resistivity at partial
60 80KX>
saturation
FrG. 271. Connate water saturation versus resistivity ratios. Curve 1 is composite of
data from Wycoff, Leverett, Jakosky, and Martin; curve 2 is for brineair displacement results of Morse et al. on artificially consolidated sands; curve 3 is for brineoil displacement results. (From Pirson.' 8 )
100r
~
1~
1r
r
~, 0 2.40
o~
n4 =2.36
'\
'\
r
r
~
1
I~
1
'~ o Nonequilibrium
100
Dynamic airbrine
o Dynamic air
+Static air
Core No 2
Core No 6
Core No 5
1.0
saturation values
1
The data are presented in Fig. 272. The resistivity ratio plotted is the
reciprocal of the resistivity index. The effect of the method of changing
the saturation was also investigated in these tests. The trends of the curves
are the same as for sandstones. The three methods of changing the saturation in the test specimens were:
1. Dynamic air brine in which the desired water saturation was obtained
by flowing air and water simultaneously through the sample
1~2.31
0.30
~ 0.20
0
\2.36
IJ
0
IO ~
r
r
r
I
1
'
0,1
\
I'
1
o.z
Pl
~~
. '"
0.4.0.60.81.0
'
Q.2
0.03
' "
0.4 Q.6QB1.0
F1a. 270. Resistivity index versus brine saturation. Fourelectrode method. Woodbine outcrop. Gas permeability 1,130 millidarcys; effective porosity, 38.8 per cent(From Rust.")
'I
0.02
0.01
10
20 30
10
100
10
20 30
20 30
100
100
F1a. 272. Comparison of electrical resistivitybrine saturation relationships obtained in dynamic and static experiments. (From Whiting et al.a)
128
129
2. Dynamic air in which only air was introduced at the inlet, displacing
b<Jth air and water from the outlet
3. Static air in which air displaced water from the sample through a
capillary barrier which prevented the flow of air from the samP.le
By definition,
r =
(i)'
r =
!!'</>'
(278)
(279)
80
60
40
30
(280)
I
k = koFS,'
'
20
Without conductive
Fq,
r =
solids~
.(281)
\
\
'
or
r =
(L.)UT
(?)'
= F<P
(267)
(F<P)'''''
(282)
"
3
2
'
_;;p.,.,.
8 10
Water saturation
20
"'
30 40
(283)
The quantity
'\
s. =
'
60 80 100
k = k,::S;
(249)
(284)
Tm
where Tm is the mean hydraulic radius. Thus, the general form of the relationship can be stated
(285)
(286)
or
The above relations have been partially verified by experiment.
REFERENCES
130
131
28. Johnston, Norris, and Carrol M. Beeson: Water Permeability of Reservoir Sands,
Trans. AI1VIE, 1945, p. 292.
29. Muskat, Morris: "Physical Principles of Oil Production," p. 142, McGrawHill
Book Company, Inc., New York, 1949.
30. Fatt, I., and D. H. Davis: Reduction in Permeability with Overburden Pl;'essure,
Trans. AI1l1E, 1952, p. 329.
31. Wyllie, M. R. J., and M. B. Spangler: Application of Electrical Resistivity
Measurements to Problems of Fluid Flow in Porous Media, Bull. Am. Assoc. Petrol.
Geo'logists, February, 1952.
32. Carman, P. C.: J. Soc. Chem. Ind., vols. 57 and 58, 1939.
33. Rapoport, L.A., and W. J. Leas: Relative Permeability to Liquid in GasLiquid
Systems, Trans. AIME, vol. 192, 1951.
34. Emdahl; Ben A.: Core Analysis of Wilcox Sands, World Oil, June, 1952.
35. Kennedy, H. T., 0. E. Van Meter, and R. G. Jones: Saturation Determination
of Rotary Cores, Petrol. Engr., January, 1954.
36. Archie, G. E.: The Electrical Resistivity Log as an Aid in Determining Some
Reservoir Characteristics, Trans. AIME, 1942.
37. Winn, R. H.: The Fundamentals of Quantitative Analysis of Electric Logs,
Symposium on Formation Evaluation, AIME, October, 1955.
38. Wyllie, M. R. J., and M. B. Spangler: Application of Electrical Resistivity Measurements to Problem of Fluid Flow in Porous Media, Bull. Am. Assoc. Petrol. Geo'logist..'1,,
February, 1952, p. 359.
39. Cornell, D., and D. L. Katz: Ind. Eng. Chem., vol. 45, 1953.
40. Wyllie, M. R. J., and G. H.F. Gardner: The Generalized KozenyCarman Equation, World Oil, March and April, 1958.
41. Winsauer, W. 0., H. M. Shearin, P.H. Masson, and M. Williams: Resistivity of
Brinesaturated Sands in Relation to Pore Geometry, Bull. Am. Assoc. Petrol. Geologists,
February, 1952.
42. Sundberg, Karl: Effect of Impregnating Waters on Electrical Conductivity of
Soils and Rocks, Geophysical Prospecting, AIME, 1932.
43. Pirson, S. J.: 'Oil Reservoir Engineering," 2d ed., McGrawHill Book Company,
Inc., New York, 1958.
44. Rust, C. F.: Electrical Resistivity Measurements on Reservoir Rock Samples by
the Twoelectrode and Fourelectrode Methods, Trans. AIME, 1952.
45. Wyllie, M. R. J.: Formation Factors of Unconsolidated Porous Media: Influence
of Particle Shape and Effect of Cementation, Trans. AIME, 1953.
46. Slawinski, A.: Conductivity of an Electrolyte Containing Dielectric Bodies,
J. chem. phys., 1926.
47. Owen, Joe D.: Well Logging Study: Quinduno Field, Roberts County, Texas,
Symposium on Formati<m Evaluation, AIME, October, 1955.
48. Patnode, H. W., and M. R. J. Wyllie: The Presence of Conductive Solids in
Reservoir Rocks as a Factor in Electric Log Interpretation, Trans. AIME, 1950.
49. deWitte, A. J.: Saturation and Porosity from Electric Logs in Shaly Sands, Oil
Gas J.~ Mar. 4, 1957.
50. Ifill, H. J., and J. D. Milburn: Effect of Clay and Water Salinity on Electrochemical Behavior of Reservoir Rocks, Trans. AIME, 1956.
51. Tixier,.M. P.: Porosity Index in Limestone frQm Electrical Logs, Oil Gas J., 1951.
52. Wyckoff, R. D., and H. G. Botset: Flow of Gas Liquid Mixtures through Sands,
l 1hysic8, 1936, p. 325.
53. Leverett, M. C.: Flow of OilWater Mixtures through Unconsolidated Sands,
Trans. AI..ZllE, 1939.
~
132
54. Jak.osky, J. J., and R. H. Hopper: The Effect of Moisture on the Direct Current
Resistivities of Oil Sands and Rocks, Geophysics, vol. 2, 1937.
55. Martin, M., G. H. Murray, and W. J. Gillingham: Determination of the Potential
Productivity of Oilbearing Formations by Resistivity Measurements Geophysics
~~~
.
'
'
56. Williams, Milton: Estimation of Interstitial Water from the Electrical Log
Trans. AIME, 1950.
'
57. Morse, R. A., et al.: Relative Permeability Measurements on Small Core Samples
Oil Gas J., Aug. 23, 1947.
'
58. Whiting, R. L., E. T. Guerrero. and R. M. Young: Electrical Properties of Limestone Cores, Oil Gas J., July 27, 1953.
CHAPTER
In preceding chapters the physical properties of reservoir rocks are defined in terms of singlefluid systems. Such a simplified case is seldom
found in actual petroleum reservoirs. In petroleum reservoirs two fluids
are present, and many times three fluid phases are involved. All the basic
definitions must be modified and other definitions added for a complete
classification of the properties of a petroleum reservoir.
The simultaneous existence of two or more fluids in a porous rock requires that terms such as ~:@1)~_ pressure, rg__~:ti:ve pepn~bility, and
wettability be defined. When only one fluid exists in the pore spaces,
tli.erefS. OiliY One set of forces to consider, the attraction between the rock
and the fluid. When more than one fluid phase is present, there are at
least three sets of active forces affecting capillary pressure and wettability.
In the preceding chapter, permeability was defined and discussed in terms
of a rock saturated with a single fluid. The material which follows amplifies
the previous definitions and introduces concepts which are required for
multifluid systems. The measurements and use of these various factors
also will be discussed.
SURFACE FORCES AND CAPILLARY PRESSURE
134
The resulting forces are unbalanced and give rise to interfacial tension.
The unbalanced attractive force between the molecules creates a membranelike surface. A certain amount of work is required to move a water
molecule from within the body of the liquid through the interface. This
work is freq~e_nt_ly_I"eferI"egJ;{)ll,S t_he free surface energyof_theJiqllid. ~rne
~:.:ice_ ~nergy, __ in ~rgs per square centfffie_ter, _may be defined as the work
necessary to create a ullit area of neW s~rface. The interfacial tension i~
the force per unit length required to create a new surface. Interfacial tension...and surface tension are commonly expressed in dynes per centimeter,
which is numerically equal to the surface energy in ergs per square centimeter. Surface tensi?n is measured in the laboratory by standard means
such as a tensiometer, the drop method, or other methods which can be
found described in physical chemistry texts.
135
Organic
liquid
Jsooctone
lsooctane +5.7"/o
isoquinoline
!soquinoline
Nophthenic ocid
Bartell.1 )
(31)
AT is the adhesion tension, u,.o is the interfacial tension between the solid
and lighter fluid phase, uaw is the interfacial tension between the solid and
denser phase, and u wo is the interfacial tension between the fluids.
A positive adhesion tension indicates that the denser phase preferentially wets the solid surface. An adhesion tension of zero indicates that
both phases have an equal affinity for the surface. The maguitude of the
adhesion tension, as defined by Eq. (31), determines the ability of the
wetting phase to adhere to the solid and to spread over the surface of the
.<olid. If the adhesion tension value is large or the contact angle e is small,
the denser phase will readily spread and tend to coat the surface. If the
AT
Uao 
Uaw
F10. 32. Interfacial contact angles. (a) Silica surface; (b) calcite surface. (From
Benner and Bartell.1 )
surfaces. It is noted that when water and isooctane are used, the water
preferentially wets both the calcite and silica surfaces. When naphthenic
acid is used, it is observed that water preferentially wets the silica surface
with a contact angle of 35 whereas naPhthenic acid preferentially wets
the calcite surface with a contact angle of 106. The other two systems,
waterisooctaneplus and waterisoquinoline, yield resnlts similar to the
two previously discussed systems. This illustrates the effects that might
be expected from varying the mineralogy of the rock and the composition
of the two liquid phases. It further illustrates that for an oilwatersolid
system, it is possible to have either a waterwet or oilwet surface, depending on the chemical composition of the fluids and rock.
Rise of Fluids in Capillaries. Consider the case of capillary tubes
wherein the internal diameter of the tube is extremely small. If the tube
is placed in a large open vessel containing liquid, liquid will rise in the
capillary tube above the height of the liquid in the large vessel. This rise
in height is due to the attractive forces (adhesion tension) between the
tube and the liquid and the small weight represented by the column of
liquid in the tube. The adhesion tension is the force tending to pull the
liquid up the wall of the tube. The liquid will rise in the tube until the
total force acting to pull the liquid upward is balanced by the weight of
the column of liquid being supported in the tube .
The total upward force can be expressed as
Ar X 2.r
force up
(32)
136
force down
(3Za)
the water at the top of the water column is equal to the pressure in the
water at the bottom minus the pressure due to a head of water h. By denoting the pressure in the water at the top by P w and P. as the pressure
in the gas at both the top and bottom and the pressure in the water at the
bottom, from hydrostatics
P.  P w = p,,gh = P,
Equating these two quantities would yield a force balance such that the
total adhesion tension force would be just balancing the gravitational pull
on the column of liquid. The pressure existing in the liquid phase beneath
the airliquid interface is less than the pressure which exists in the gaseou8
phase above the interface. This difference in pressure existing across the
interface is referred to as the capillary pressure of the system. This pres:'.
sure can be calculated on the basis of a U tube, balancing the pressure
between the two points.
Figure 33 represents the conditions that exist when a capillltry tube is
immersed in a beaker of water. If the equilibrium height h of the interface
137
(33)
Since the pressure in the air at the top is also P. and by definition the
capillary pressure is the pressure difference across an interface, an expression for the height of fluid rise in the tube is obtained by balancing the upward and downward forces.
2.rAr = 7rr'hgpw
h = 2"1'Ar = 2Ar
Kr2gp.,,
rgp.,,
T
h
Pa
A'
Pw
B'
B
Pqp 8
P;b a
'afer
Oil
Air
Paa
Water
FIG. 33_ Pressure relations in
capillary tubes.
Substituting the above value for the height in Eq. (33), an expression for
capillary pressure in terms of the surface forces is obtained.
Pc= 2owq
A'
COS
P:a
8.,,f/
r
Wafer
is small, the head of the air is negligible. Therefore, the pressure in the air
immediately above the interface is essentially equal to the pressure in the
air immediately above the free water level in the large vessel. However,
owing to the greater density of the water, the pressure in the water just
beneath the interface differs from that at the bottom of the column due to
the head of water h. Since the beaker is large compared with the capillary
tube, the gaswater interface in the beaker is essentially horizontal. The
capillary pressure is zero in a horizontal or plane interface. Therefore the
pressure in the water at the bottom of the column is equal to the pressure
i11 the gas at the surface of the >vater in the large vessel. The pressure in
(34)
(35)
Poa
Pwa
at the free water level in the beaker. The density of both the oil and the
water must be considered in deriving the pressure relationship at point B.
P,, =
P~
 p.gh
Pw, =
P~
 p,,gh
.
138
(36)
COS
81110
(37)
139
When the radius of the tube or the adhesion tension is changed, the
capillary pressure is altered accordingly. From the variation indicated .by
Fig. 35, the following statements can be made: (1) The greater the affimty
of the denser phase for the solid, the greater will be the capillary pressure
across the interface for a given size tube; (2) the smaller the radius when
the wetting characteristics are the same, the greater will be the capillary
pressure.
Capillary Pressure in Packings of Uniform Spheres. A general expression for capillary pressure as a function of interfacial tension and curvature
of the interface is due to Plateau' and is given in Eq. (38).
P, = ,,
(1R, + 1)
R,
(38)
where R 1 and R 2 are the principal radii of curvature of the interface and u is
the interfacial tension between the two fluids. The distribution and measurement of these two radii in a porous system are sholNn in Fig. 36. It is
noted that these two radii are measured in perpendicular planes. Comparing Eq. (38) with the equation for capillary pressure as determined by the
capillary tube method, it is found that the
mean radius Rm is defined by
(1 1)
(o)
(bl
FIG. 35. Dependence of interfacial curvature upon pore size and contact angle.
(a) Same contact angle, different pore size; (b) same pore size1 different contact
angle.
_!__ =
+
= 2 cos 8 = D.pgh (39)
Rm
Ri
R2
Tt
u
It is practically impossible to measure the
values of R 1 and R 2, so they are generally referred to by the mean radius of curvature and
empirically determined from other measurements on a porous medium.
The distribution of the liquid in a porous
system is dependent upon the wetting characteristics. It is necessary to determine which is.
the wetting fluid so as to ascertain which fluid
occupies the small pore spaces (Fig. 36). From
packings of spheres, the wettingphase distribution within a porous system has been described as either funicular or pendular in
nature. In funicular distribution, the wetting
FIG. 36. Idealized conphase is continuous, completely covering the
tact for wetting fluid and
surface of the solid. The pendular ring is a
spherical grains. (From
Leverett.3 )
state of saturation in which the wetting phase
is not continuous and the nonwetting phase is
in contact with some of the solid surface. The wetting phase occupies the
smaller interstices. These distributions are illustrated in Fig. 37a and b.
the pendular ring distribution in Fig. 37a, and the funicular saturation





141
distribution in Fig. 37b. It is noted in Figs. 36 and 37 that as the wettingphase saturation progresses from the funicular to the pendular ring distribution, the quantity of the wetting
phase decreases and the mean curvature or values of R 1 and R, both tend
to decrease in size. ReferringtoEq.
(38), it is seen that if R1 and R,
both decreased in size, the magnitude of the capillary pressure would
in turn have to increase in size. It
is therefore possible to express the
capillary pressure as a function of
(al
(b)
rock saturation when two immisciFrG. 37. Idealized representation of disble phases are used within the porous
tribution of wetting and nonwetting
matrix. As will be illustrated later,
fluid phase about intergrain contacts of
it is also po&.,.ible to approximate
spheres. (a) Pendularring distribution;
the pore ditribution of this parti(b) funicular distribution.
(From
Fancher et al!)
cular system because the capillary
pressure would be dependent upon
the radii of the various pores for any particular value of saturation.
For the capillary pressure to be zero in a porous system with two liquid
phases, it would be necessary that R, and R, be infinitely large or that the
interfacial tension u be zero.
It was previously shown in the case of the capillary tube that the greater
pressure is always on the concave side of the interface. It can be seen from
Figs. 36 and 37 that the curvature of the interface is such that the pressure in the nonwetting phase is greater than the pressure in the v1retting
phase. Therefore the wetting phase in a porous material is at a lower
pressure than the nonwetting phase.
Saturation History. To study the effect of saturation history, it is
necessary to consider varioussize interconnected pores. In the case of a
capillary tube of varying diameter, the height to which the fluid will rise
in the tube depends on the adhesion tension, fluid density, and variation
of tube diameter with height. If pressure is applied to the interface, the
interface moves to a new equi]ibrium position, thus decreasing the volume
of water within the tube. This decrease in water volume means a reduction
in saturation and is accompanied by an increase in capillary pressure.
This fact is illustrated in Fig. 38 wherein the capillary pressure would be
greater for the small radius of curvature than for the large radius of curvature. This behavior indicates that there is an inverse functional relationship between capillary pressure and the wettingphase saturation. Also, it
indicates that the lower the saturation, the smaller will be the radii of
curvature and the wettingphase material will then exist in the smaller
crevices and openings of the system, leaving the large open channels to the
nonwetting phase.
Not only is saturation a function of capillary pressure, but it is also a
function of the saturation history of the particular pere matrix that is
140
Saturation= f00%
Saturation = 800/o
Capillary. pressure= Pc
(a)
Safurotion
=0
Saturation = fQo/,.
Capillary pressure= Pc
lb)
F1a. 39. Dependence of equilibrium fluid saturation upon the saturation history in a
nonuniform pore. (a) Fluid drains; (b) fluid imbibes. Same pore, same contact angle,
same capillary pressure, different saturation history. (From McCardell.5 )
or it is being saturated with the wetting fluid. Forcing the entry of a nonwetting fluid into a tube saturated with a wetting fluid causes the wetting
fluid to be displaced to a point such that the capillary pressure across the
interface is equal to the applied pressure plus the pressure due to the column
of suspended fluid. In the case of Fig. 39, the rock is 80 per cent saturated
142
143
with the wetting phase for the higher value of capillary pressure. Now
consider the case where the tube is initially saturated with a nonwetting
phase and is immersed in a container filled with a fluid which will preferent.ially wet the tube. The wetting fluid will be imbibed owing to the adhesion force between the wetting fluid and the surface of the tube until
the adhesion force is equal to the weight of the column of fluid. The saturation thus obtained as illustrated in Fig. 39 is only IO per cent. In this
example, saturations of 10 and 80 per cent are obtained for identical values
of capillary pressure. From this oversimplified example, it is seen that the
relationship between the wettingphase saturation and capillary pressure is
dependent on the saturation process. A higher value of saturation for a
given capillary pressure would be obtained if the porous system were being
desaturated than if the porous system were being resaturated with the
wettingphase fluid.
It is thus seen that the capillarypressure saturation relationship is dependent upon (I) the size and distribution of the pores, (2) the fluids and
solids that are involved, and (3) the history of the saturation process.
mean radius of curvature, Eq. (39), and the square root of the permeability
divided by the porosity (l!.p gh/u)(k/</>) 112 The correlating function was
proposed so that capillarypressure data from different sands could be expressed in generalized form. If the correlating function were universally
1
t4
"
"
I "
I
I
1.2
lmbibition
Sand U
c
Oroinoge
,.
""'
II ""
I
I
Sand
Sand I'll
Sand ::SZ:
QS
be taken into consideration before the data are actually applied to reservoir calculations.
II
l~
Q6
0.4
..
't
I
~~ .......
~
/Druinoqe
~~
/mbibifio;;/
Q2
'f. 0
""
r: rt~
 );{.
,. 11:
~
20
40
60
Water saturation,
80
0
100
1..
FrG. 310. Correlation of data from heightsaturation experiments on clean uuconsolidated sands. (From Leverett.3 )
applicable, one curve would be obtained for all samples. This particular
correlating function will be considered in more detail later in the text.
It is not possible to determine the capillary properties of naturally
occurring rock materials by a method such as used by Leverett. Core
samples of natural materials are necessarily small and are not available
in continuous sections of sufficient length for study by the simple drainage
method. Therefore other means of measuring capillary pressure have been
devised. Essentially five methods of measuring capillary pressure on small
core samples are used. These five methods are (!) desaturation or displacement process through a porous diaphragm or membrane (restored
state method of W elge'), (2) the centrifuge or centrifugal method, (3) the
144
145
Nitrogen pressure
oil
Scafe of
squared
paper
Neoprene stopper
Nickelploted
spring
Seal of
red oil
Core
Kleenex
paper
Ulfrofi'ne
!rifted
gloss disk
Utube manometer
Lucite window
oj~Brlne
<'

FrG. 311. Porous diaphragm capillarypressure device. (From Welge and Bruce.e)
not penetrate the diaphragm when the pressures applied to the displacing
phase are bel6\v some selected maximum pressure of investigation. Various
materials including fritted glass, porcelain, cellophane, and others have
been used successfully as diaphragms. The membrane is saturated with
the fluid to be displaced; the test sample is placed on the membrane with
some suitable material, such as Kleenex, to aid in establishing contact;
The core sample is inserted in the mercury chamber and evacuated. Mercury is forced in the core under pressure. The volume of mercury injected
at each pressure determines the nonwettingphase saturation. This procedure is continued until the core sample is filled with mercury or the injection
pressure reaches some predetermined value. Two important advantages
are gained: The time for determination is reduced to a few minutes, and
the range of pressure investigation is increased as the limitation of the
properties of the diaphragm is removed. Disadvantages are the difference
in wetting properties and permanent loss of the core sample.
146
147
Window
Tube body
(From
When the sample is rotated at various constant speeds, a complete capillarypressure curve can be obtained. The speed of rotation is converted
into force units in the center of the core sample, and the fluid removed is
read visually by the operator. The cited advantage of the method is the
increased speed of obtaining the data. A complete curve can be established
in a few hours, while the diaphragm method requires days. It is difficult
Pcm
Pew =
taking
O"m
u"' =
Gos
Gos
outlet
To atmosphere
Oil burette
inlet
plate.
Poree loin
dmCOS
U'w
140
COS
(310)
with the diaphragm method, since the same resisting forces appear to be
involved in the core.
The agreement of the data when corrected by this ratio is good, as shown
in Fig. 315.
There is some doubt as to the validity of incorporating the contact angle
into the ratio of pressures. The geometry of the pores of a rock is complex,
and the relationship between the curvature of the interface and the radius
of the pore is not necessarily a function of the cosine of the contact angle.
It appears that an equally valid assumption is that the mean curvature
of an interface in rock is a unique function of fluid saturation. This assump
                         
148
20
10
I I
f0
1.2
~ 0.8
4 ~
~g
;:;;
~ 0.4
>
H20~
0
Hg fOO
20
80
40
60
60
40
~ ~
80
1o8 HzO
..
0.8
"
6
2
Hg
"
OO
Hg 100
20
40
60
80
80
60
40
20
f08 H20
0
(c)
o.
::: a.a
Perm. 35 md
Par. 19/o
'
ri 1.6
6 ~
20
 "
:a.8 0.8
Por. 16%
so
100
HzO
10
6
4
~ ..__Hg
20
i
0
40
60
~
~
2 ~
HzO
00
.E
2 "
Hg 100
80
60
40
20
O
Total pore space occupied by liquid,",{,
Ce)
1.2
so
40
"i .""'
Son Andres
limestone
Perm. 43 md
HzO
a e
~~
.E0
limestone
"
20
OO
20
40
60
BO
iOOOHzO
Hg 100
80
60
40
20
O
Total pore spoce occupied by liquid, 0/ 0
(d)
10
San Andres
~ f. 2
if.
HzO
4 '5.
20
HzO
0.4
60
40
P= =am= 480 = 6 57
(311)
Pew
Uw
70
.
With the exception of curves C and D in Fig. 315, a superior correlation
is established using a conversion
factor of 6.57 rather than 5. Brown' ij_ 30,.,,.,.,..,225.0
found that the correlating factor ~
o Restored state
187.5 ~
25
Mercury injection
~
between the diaphragm and mer u;
,
curyinjection methods was not ~ 20H.L.....L....L~tf50.0 m
Sandstone core
C.
solely a function of interfacial ten ;;>Porosity
28.1/o
5
~
112
sions and contact angles. It is noted '5. 15
Permeobilityf.43 dorcys
..2
in Fig. 316 that for a sandstone
Factor  7.5
g.
75.0
~ fO
core, the correlating factor is 7.5.
~
~
For the same fluids it is shown that ~ sl~+...J..+!!37.5 ,~
the correlating factor for a lime~
~
~
stone core is 5.8. It appears that a ~ 0.L~~~:=~3lo
o 20 40 60 80 100
universal conversion factor cannot
be defined, as it is different for each
0
20
100 80
type of porous rock.
Hg
Good agreement of centrifuge
Liquid saturation,%
(a)
data with those from the diaphragm method was reported by
 60~~~348
Slobod.8 A typical curve showing :!:.
reproducibility bet\veen successive
290
determinations with the centrifuge
as well as the correlation with data
obtained by the diaphragm method 0
is shown in Fig. 317. Unlike the ,._ 3;of++""'d\1174
;;.
mercuryinjection method, there is
no need of conversion factors to correct for wetting properties. The
58
same fluids are used in the centrifugal and diaphragm methods.
The excellent correlation obtained by Brown' between the
20
0
100 80
diaphragm and dynamic methods is
illustrated in Fig. 318. The dynaLiquid saturation, "lo
(bl
mic data were obtained by simultaneous steady flow of oil and gas Fra. 316. Capillary pressures by restoredthrough the porous sample at a state and mercuryinjection methods
predetermined level of pressure dif (From Brown.
ference between the fluids. Care was
taken to maintain uniform saturations throughout the core as well as to conduct the test so that a close correspondence to drainage conditions existed.
SO
0
0
"
10
Uppl!f"
Wilcox sandstone
Perm. 430 md
Por. 22'Yo

~ 0.8
149
00
Hg
20
40
60
80
iOO HzO
Hg fOO
SO
60
40
20
0
Total pore space occupied by liquid, 0fo
(b)
PaJuxy sandstone _
Perm, f,150md
Par. 20/o
~ .__,._
Hz~
l 0.4
10
'!;
,g
(a)
i.2
20
0
Total pore space occupied by liquid, o/o
Perm. 170 md
Por. 26/o
Frio sandstone _
~ 1.6
10
Perm. 23 md
Por. 23%
"'
20
"
iOO H.zll
Hg !00
SO
20
0
Toto! pore space occupied by liquid,%
(f)
FIGd. 315. Typical capillarypressure curves obtained from displacement cell (HJ))
an from mercury apparatus (Hg). (From Purcell.~)
0
0
0
0
150
32
2 a~
24
._., _
K0 =i,030md
+24.9%
Disk method
151
10,000.,~~r,~,.,.,..
100
,
,
~
ie
Sandstone core
~
0.2
''
0.6
0.4
0.8
0
0
" 1""'9
Brine saturation
Brown.Q)
40
60
80
Liquid saturation,%
20
=W(IShington
:E/k Basin
=Rangely
=Creole
=Syntfletic alundum
=Loire St. John
I
20
1.0
1,0001++J+\"IP"<++{
s.
c
3
4
5
6
7
8
Porosity: 23.8%
Permeability: l!00111d
:: 4 0
8
4
t =Howkins
5,0001t++1lt 2 =Magnolia
I I
I :ft:~;ic
_
100
ff =North BelrklgeCo!ifornio
ffA :Nortfl Be!tidgeCO!fforniu
core analysis dotu
=Dominguez second zone
'3 =Ohio sandstone
Interstitialwater Saturations
Essentia~y t'.""ee methods are available to the reservoir engineer for
the deterininat1on of connate or interstitialwater saturations Th
methods are (1) coring formations with oilbase or tracerbearfug flu:':
(2) calculated from electric log analysis and (3) determined from capilla
ry
pressure data.
100
~
80
..
:;:.
~
'
60
"'
..:
40
.. .,.. '"
101l++l'lc\c+l+~'l<1
..
...
,,...
OOL~10,2~0,~3L04L0~5LO...i60L..~7L08~0,90l_....J100
Connote water, 0/o
FrG. 320. Comparison of the connatewaterpermeability relationships for various
formations. (From Welge and Bruce.15 )
~ 20
00
6 810
20
40 60 100
Air permeability, millidorcys
200
400
FIG. 319. Rela(Ftion of the air permeability to the water content of the South Coles
L evee cores.
rom Gates et al.10)
termined from cores cut with oilbase mud reflects closely the water saturation as it exists in a reservoir except in transition zones, where some of
the interstitial water is replaced by filtrate or displaced by gas expansion.
In Fig. 320 are shown permeabilityconnatewater relationships reported in the literature for a number of fields and areas. There is no gen
..
152
8 40
'
'
8 50
86 0
870
P,
.
'
90 0
electric toqs
91 0
92 0
.2
93 0
'ff.
940
C>
95 0
g.
'
"'
970
\
990
1,000
'
"
,0
'
1,010
........ ,..._
~~
1 020
10 20
gh(p,  p,)
(36)
P, = u
(.!.R, + R,.!.)
(38)
When these equations are put in oilfield tenns, the capillary pressure
in pounds per square inch can be stated as
h
P, =
(p1  p2)
(312)
144
960
980
153
88 0
89 0
          
30
40
so
60
70
80
90 100
P, = 2u cos 9
r
Considering a specific case wherein the laboratory values are determined
with gas and water, the capillary pressure becomes
(Pc)L = 2<1'1011
COS
610 11
(35)
  
154
where er wa is the interfacial tension bet\veen gas and water used in laboratory tests, and r is the radius of the capillary. The capillary pressure which
would exist if reservoir fluids, oil and water, were used in the same capillary
would be
155
therefore
j(Sw) = P,L = P,R
O"L
qR
so that
where
u wo
(313)
Thus reservoir capillary pressure can be calculated from laboratory capillary pressure when the interfacial tensions and contact angle bet\veen oil
and water in the reservoir and gas and water in the laboratory are knovvll.
This relationship assumes that the saturations as measured in the laboratory remain equal to the saturations in the reservoir so that the height of
rise in capillary tubes of equal radii are the same. It is difficult, if not
impossible, to determine the exact value of the contact angle for fluids in
a porous matrix. The cosine of the contact angle can vary bet\veen 1
and I, which can cause considerable variation in the resulting conversion
of laboratory data, and therefore it 'is often desirable to neglect the contact
angle in Eq. (313).
A second technique, a relationship neglecting the contact angle, for converting laboratory data to reservoir conditions can be obtained by stating
the capillary pressure as
P, =
where
"(1+
1)
R1
R2
(38)
where f(S.) is a function of saturation which can be determined by a laboratory test for laboratory conditions, so that
Pea=
<J'R
<TL
PcL
(314)
~' G)~
(315)
e (where e
 
~
156
cos(}
(316)
</>
The inclusion of the cos e term will not be used herein by the authors, and
the J function will be as defined by Eq. (315).
The J function was originally proposed as a means of converting all
capillarypressure data to a universal curve. There are significant differences in correlation of the J function with water saturation from formation
to formation, so that no universal curve can be obtained.
Correlation of the J function with water saturation for a number of
materials is illustrated in Fig. 322. Note that there is an independent
!. 5
1. 4
'
form<Jtion
"I\
Ha.tins
RonQ.iy
Er Roble
Woodbirie
Weber
.
I
Hawkins,
o.a
0.7
a.
0.5
""
0.4
0.3
'
~3
~11
Deese
Devon ion
0.4f9
., ~\

,\
<\.
:i:
~
Morena
~
....._
"""..I
.. 1~~
_.Rangely
'"'
' oo oo
_!!_,___ (~))ll
ucosO q,
80
40
60
Liquid saturation, lo
ll
100
le)
..
..
'
.
..":\ ... .
'
I~
. . ....
~..:.:o0o o
.., . .
40
60
80
Liquid saturation, %
Id)
20
100
100
o::::
:;.:;:
....
n.
~~.
80
.....
~ '.,&,, . .
40 ~ oo ro
Water saturation, Sw
J(Sw)
100
Liquid saturation, %
lb)
..
o.447
Kinsella shale/
m m
100
3;F1+++l.J
Theoatical limiting
vakll for ~ular
pacted spheres/
"\_
.
Ka:ie./
O.l
oo
....1.j.
0.2
IN
\A!u!'dum
~'
\~ 
.,
g 1.
60
80
Liquid soturation, %.
lo)
0.37~
'\!"
'\
Q.3!5
o.H6.:.,.._
0.114
Viking
Ltduc
10
""""~1 ...
0:1a
""~~
I
Kinsella
! \
,i
0
O.l5f
I~
\\
}!,:~>
Alundum {a>nsalidatt'd l
Leverett ( unconsolidated J
I"
11:
I '
Leverttt_,,>:
Katie
Leduc
Figure 323a shows the correlation obtained for all samples available from
the field. There is considerable dispersion of data points, although the
trend of the correlation is good. Brown found that the correlations could
be improved by dividing materials on a textural basis. The core materials
were subdivided into limestone and dolomites, both materials occurring
within the productive section of the Edwards formation. The correlation
___________
Kinsella
I' I
0.9
"'"
i'
v,
3
2
157
""..g" "
~.
20
 
158


159
for the limestone samples is shown in Fig. 323b and for the dolomite samples in Fig. 323c. The dolomite samples indicate a good correlation, while
the limestone samples exhibit a scattering of data in the range of low water
saturations. In an attempt to obtain a better correlation, the limestone
of the correlation is used (Fig. 325). In the lower portion of the figure are
shown curves of constant porosity resulting from correlations using Eq.
(319). A better correlation is obtained using Eq. (319) rather than Eb.
S
greater for the coarsegrained limestone samples than any other group.
This is to be expected, as the coarsegrained limestone contains solution
cavities, vugs, and channels which are not capillary in size, hence the de
='14' + o2 log
k +C
log k
lag k
Capillary pressure
= 5 psi
'
~
Sw=alogk+C
(317)
There are indications, however, that water saturation at constant capillary pressure is not only a function of permeability but also some function
of porosity. In Fig. 324, the results of fitting an equation
Sw = a,q,
+ a,. log k + C
(318)
to the field data for 5psi capillary pressure is shown. The upper portion
of Fig. 324 shows the threedimensional aspect of such a correlation. The
lower part shows lines of constant porosity (light dashed lines) fitted to
the data. The heayy black dashed line is the straight line [Eq. (317)]
fitted to the data wherein the effect of porosity is omitted.
In Eq. (317) and (318), Sw is the water saturation, q, the porosity,
k the permeability, and a 1 , a 2, and C are constants which must be determined from the sample data. The method of least squares can be used to
determine the constants of the best fitting lines as described by (317) and
(318). The effect of ignoring the porosity is to predict lower water saturations for lowpermeability materials. Equation (318) can be modified
to a polynomial form so that
Sw = a1q,
(319)
~f+'H"1~:.++l
:;;
0
fl'ff~
~'h+fJ
:0
0
2>+
..."
...
2JtO',.t~="<t'cJ
..i :
L___
_J__
"
.:rg
_ t_ _ _j__2{'2,/5:
30
Porosity
Brine soturotion S
Brine
burger.12)
burger.12)
(317), but for most engineering purposes, with limited data, correlations
as implied by the latter equation are satisfactory.
Fluiddistribution curves are reported for several values of permeability,
160
ranging from IO to 900 millidarcys in Fig. 326. These data may be considered also to be capillarypressure curves. The ordinate on the right
reflects values of capillary pressure determined by displacing water with
air in the laboratory. The ordinates on the left include the corresponding
30
200
27 .:::: 180
24
~ 160
~ ~ 21
~ 140
~w
.
90
,,\
~ ~ ~ ~~
18
~ 120
15
g. 100
63 ~w o
w54 ii..g
~>
45 E 0
~~
12
ao
.... ~
~
E~9~60
f
81
"'
~~
8 ~
"~
28
~6
~ ~ ~
..c
6 ~
..c:
40
3 ~ 20
J:
'
10
20
'
.'.
8 .&
wo
water saturation in the gas zone varies from 24 to 20 per cent. Such a
large variation of water saturation in the oil zone could cause a large error
in the estimated oil reserve if not properly accounted for. It therefore becomes imperative that the water distribution with height within the oil
zone be determined so that a inean
water saturation for the oil zone is
obtained for use in determining oil
reserves.
To convert capillarypressuresaturation data to height saturation, it
is only necessary to rearrange the
terms in Eq. (312) so as to solve
for the height instead of the capillary pressure so that
~
"o
\ \
36
27
I8
"
30 40 50 60 70 80 90
Water saturation, o/o
.!.
<(
10g
161
h = P, X 144
Pw 
Po
By use of this equation, it is possible to convert laboratory capillarypressure data into a watersaturation curve as a function of height as was
shown in Fig. 321. This type of system, then, would be represented by
an idealized fluid distribution as shown in Fig. 328. Here, two cores are
used for illustrative purposes where core A represents a core sample within
the_ oil zone and core B represents a core sample within the oilgas zone.
By use of capillarypressure data, it is possible to calculate the water saturations that exist in cores A and B.
It is emphasized here that all height measurements are from the free
water surface. This surface is not necessarily defined by the level at which
only water is produced but is that surface defined by zero capillary pres

102
~UTe. r!'~e free Water surface is dependent Upon the capillary pressure and
the relative permeability of the porous system. For this reason, the means
of ~lect1ng or calculating the proper free water surface will be delayed
until after the discussion of relative and effective permeabilities for multi
163
calculating the height of a saturation plane above the free water surface is
not valid.
It is possible to determine the range over which the conversion equation
is valid from the laboratory data. The wetting phase is said to be discontinuous when the capillary pressure increases without changing its saturation. Referring to Fig. 326, it is seen that the wetting phase, water,
becomes discontinuous at a height of approximately 130 ft above the free
water surface.
By determining the free water surface from coring, electric logs, or drillstem tests, it is possible to calculate the water saturations as a function of
height above the free water surface by using Eq. (314).
Example 31. Calculation of Height of Saturation Plane from Laboratory Capillarypressure Data.
If P,L
er wo
Pw =

u wo =
p,
P,R
level
P,R(l44)
Pw 
Pu
18(;;) = ~ = 6psi
8
6(144)
68  53
6(144) ""'58 ft
15
Fro. 328. Fluid distribution in a petroleum reservoir. (From Welge and Bruce.8 )
phase systems. For the time being, it will be considered that the free water
surface can be defined and that all measurements can be made from that
surface. Ii;i order that the relationship used to convert capillarypressure
data to h".1ght ab~v.e the free water surface be valid, it is necessary that
the followmg cond1t10ns be satisfied:
1. The pressure in the oil and water are equal at the free surface.
2. The water and oil columns are continuous and connected throughout
the range of the calculations.
3. The system is in static equilibrium.
If any of these three conditions are not satisfied, then the equation for
To calculate the fluid saturation in the gas zone, it is necessary to consider all three phases: oil, water, and gas. If all three phases are continuous, it can be shown that
\>here (P,)w, = capillary pressure at given height above free water surface
determined by using water and gas
(Pc)wo = capillary pressure at given height above free water surface
using oil and water
(P,),, = capillary pressure at height above free oil surface using oil
and gas
If the wetting phase becomes discontinuous, then the wettingphase
saturation takes on a minimum value, and at all heights above the point
of discontinuity the wettingphase saturation cannot be less than this mini
164
mum value. It is then possible to calculate the fluid saturations above the
free oil surface by the following relations:
1. S. at h, calculated using oil and water as the continuous phases
2. S, at h, calculated using oil and gas as the continuous phases and
height denoted by the free oil surface
3. S, = 1  S,
s. = S,  s.
4.
" = 72 dynes
Po
""' = 50 dynes
" = 25 dynes
= 53 lb/cu ft
p. =
p, =
68 lb/cu ft
7 lb/cu ft
= h1.  h, = 120  70 = 50 ft
= 144
50
(53  7) = 144
46
= 15.96 psi
S, = 18 per cent
S,  S. = 18  16 = 2 per cent
S, = 100  S, = 100  18 = 82 per cent
s. =
165
somewhat different from the calculated values might exist. As the capillary pressure for a discontinuous phase could vary from pore to pore, it is
impossible to ascertain the exact relationships that should exist. Rene~,
the preceding method of calculating fluid distributions is not exact bu_t lS
usually as accurate as the data available for making the computat10n.
Calculation of W ettability
Wettability of Reservoir Rocks. As mentioned earlier in th_e discussio_n
of capillary pressure, the curvature of an interface confined m a pore IS
some function of the contact angle,
which, in turn, is a functiori of the
wetting properties of the fluids and
the rock surfaces. The degree to
which fluids wet a solid surface was
shown to depend on the interfacial
tensions between the various contacts, fluidsolid and fluidfluid.
occupied D Pore space occupied
There are t\VO means of expressing 0Pore space
by HzO
by HzO
the degree of wettability. The first BaRock matrix
m Rock matrix
is expressed in terms of the contact
occupied Pore space occupied
angle. A contact angle of zero would .Pore space
by oil
by oil
indicate complete wetting by the
(b)
(a)
more dense phase, an angle of 90
FrG. 329. Wetting in idealized pores of
indicates that neither phase prefer reservoir rocks. (a) Oil wet; (b) water
entially wets the solid, and an angle wet. (From Calhoun.ll;)
of 180 indicates complete wetting by
the less dense phase. The contact angle is, therefore, a measure of the
relative wetting of a solid by a fluid.
Another convenient index of wettability is the sessile drop ratio, defined as the ratio of the height of
a droplet on a surface to the
breadth of the droplet. A sessile
drop ratio of 1 indicates complete
nonwetting, whereas a ratio of zero
indicates complete wetting.
The wettability of reservoir rocks
R _ 217 cos 8
to the fluids present in these rocks
cr
Fra. 330. Illustration of relation between is of great importance in that the.
distribution of the fluids within the
wettability and capillary pressure.
interstices is a function of the wettability. Figure 329 is an idealized representation of.the change in fluid
distribution in a given pore due to a change from oil wettmg to water
166
thresho~d
1,00 0
700
500
300
,.._.
0
'~
....

10 0
70
50
~
30
,_
'
C ontact ang1e
PTwo Uoa
167
(321)
100
where
cos (j oa = 1
cos Bwo = contact angle between water and oil in core
cos Ooa = contact angle between air and oil in core
PT10o = threshold pressure of core for oil to enter when core
initially saturated with water
PToa = threshold pressure of core for air to enter when core
initially saturated with oil
aoa and <Iwo = interfacial tensions between air and oil and oil and
water, respectively
Table 31 summarizes the data presented by Slobod. 17 A wettability
number of 1.0 would indicate complete wetting by water; of zero, complete
wetting by oil. In general, intermediate wetting is exhibited for the core
samples reported on in Table 31.
The effects of wettability must be considered in all laboratory determinations of residual oil saturations, capillary pressure, and other similar
tests. Important changes in the physical properties of core samples have
been noted which are apparently due to changes which occurred in the
rockwetting characteristics during laboratory extraction with solvents .
Some of the unexplained irregularities in capillary pressure and other
laboratory core data could possibly be attributed to the uncertainties in
the wetting properties of the rock samples and possible changes in these
wetting properties due to aging and laboratory procedures.
10
.
Q3
o.s
0.1
to
'.
3
5 7 10
30
50 70 100
dashe~ curv~
(320)
168
31.
Core
No.
Description
Initial desaturation
pressure' (threshold.
pressure, psi)
Airoil
Apparent
contact
angle, deg
Devonian
limestone
6.5
6.8
6.25
6.4
6.1
6.2
6.0
3.9
0.835
0.811
0.854
0.541
33.4
35.8
31.3
57.2
1588
1589
1590
1591
Yates
sandstone
0.86
0.85
0.85
1.00
0.32
0.3
0.31
0.4
0.331
0.314
0.324
0.356
70.7
71.4
71.1
69.l
1542
1543
1544
1545
Alundum
(RA 1139)
0.70
0.70
0.68
0.67
0.25
0.28
0.4
0.28
0.318
0.356
0.522
0.372
71.5
69.1
58.5
68.2
0.72
0.54
1.58
2.90
0.24
0.32
0.32
0.45
0.297
0.528
0.180
0.138
72.7
58.l
79.6
82.l
0.86
0.86
0.68
0.86
0.21
0.21
0.12
0.27
0.217
0.217
0.157
0.280
77.5
77.5
81.0
73.8
1592
1593
1594
1595
!620
1621
1622
1623
Clearfork
Limestone
Tensleep
sand
" Routine extraction with chloroform preceded wettability tests except alundum,
which has been regenerated at 1400 F for 3 hr.
h Airoil surface tension = 24.9 dynes/cm.
Oilwater interfacial tension = '..'8.U
dynes/cm.
The flow rate from a single tube of radius r is given by Poiseuille's law
!!.P
Q = ""'
8L
(322)
Q=
v;L:i;
(,,cos 8) 2 V !!.P
2L'(P,) 2
Qt
(323)
' _ kAL!!.P
(324)
_L.,
,_,
2AL
(P,)l
(325)
V~ =Si
pressure.
PurcelF and Burdine 18 both have reported on computation of peru1eability from capillarypressure data obtained by the mercurypenetration
method. Purcell utilized the concept of poresize distribution without
evaluating the distributions. He applied the data directly to the computation of permeability. Burdine reported poresize distributions as well a.s
the results of computation of permeability.
The equation presented by Purcell for the calculation of permeability
from the pore properties of a rock is developed as follows:
(35)
Oilwater
BTL
BTN
BTO
BTP
Synthetic
Wettability
numberh
169
Since AL is the bulk volume of the system and <P is the fractional porosity,
Vr
AL
<P = 
___;__
L.,
,_,
(P,)l
(326)
To account for the deviation of the actual pore space from the simple
geometry used in the derivation, Purcell introduced a lithology factor X
into the final equation. Introducing conversion factors and generalizing,
Eq. (326) reduces to
I70
ls
dS
(P )'
s~1
8=0
Sample no.
(327)
dS
(s~i
1
2"
3
4
5
6
7
8
9
10
11
12
13
14
15
16
(328)
0.56
12
048
Pc
l(
\
"
g
a. 4
~
100
80
e"
~
0.16
v
~.
60
<;:!..:
1'
0.24
~v
'~
'E
./
(f'c)
17
18
19
20
21
22
23
24
25
26
27
0.40"' ~
9"
0.32
"
g
a.
0
40
20
F10. 332. Graphical presentation of capillarypressure data for calculating permeability. (After Purcell.1 )
0.085
0.122
0.168
0.149
0.200
0.165
0.257
0.256
0.191
0.107
0.216
0.273
0.276
0.185
0.282
0.363
3.04
21.2
17.3
53.5
61.9
91.6
92.3
97.5
163
680
430
348
388
902
816
865
1.2
12.0
13.4
36.9
57.4
70.3
110
116
144
336
430
439
496
772
1,070
1,459
0.182
0.158
0.231
0.276
0.215
0.163
0.284
0.272
0.338
0.003
0.10
42.2
54.9
172
183
308
422
383
502
734
<0.1
<0.1
35.7
40.2
184
235
307
320
506
634
1,150
Av 0.216
0.08 '$.
Observed air
permeability,
millidarcys
Paluxy Formation
;>.
Purcell assumed that the contact angle for mercury was 140 and that
the interfacial tension of mercury was 480 dynes/cm. Therefore, using
mercury capillarypressure data, Eq. (327) further reduces to
k
171
"Cuttings."
Table 32 presents Purcell's summary of observed and computed permeabilities as well as computed values for the lithology factor, X. Figure 333
shows the correlation obtained between observed and computed data using
an average lithology factor of 0.216. Good agreement is indicated between
172

L:::,,.
E 1,000
!ff 500
Po/uxy plugs
I/ '
/~
:E
g
a.
173
where Po,
ri
capillary pressure
u = interfacial tension
e = contact angle
Sm = mercury saturation, per cent of pore volume
The distribution function can be evaluated by graphically taking slopes
of the mercury capillarypressure curve at different values of mercury saturation, computing the pore radius from the capillary pressure corresponding to the point at which the slope was taken by means of Eq. (35), and
evaluating Eq. (329) for the distribution function D(r;).
A typical mercury capillarypressure curve and the corresponding distribution curve are presented in Fig. 334a and b. The area under the
distribution curve to a given radius is the fraction of the volume having
pores larger than the given radius.
100
n/
50
,/
fO
I/
(a)
/
0
0
0
0
0
"' 3
!O
0 oL=~,~00~7
ZO~o~,+oo~~o~o~,+oo~s~o~oooro~o'"""'ado~o;;:900!:;;~,p~o~o~~Joo''
Pressure, cm Hg
calculating permeability from this distribution. The method involves injection of mercury into an evacuated core sample, thus obtaining a mercury
capillarypressure curve. The equations presented by Burdine for calculating the pore size and rock permeability are derived as follows:
A distribution function is defined as D(r,), so that
where dV is the total volume of all pores having a radius between r; and
r,  dr. The quantity D(r;) can be computed from the mercury capillarypressure data by using the following two equations:
and
c
0
(b)
1,000
.,
.~
dV = D(r;) dr
2,000
c
.2
(35)
(329)
~
0
14
12
10
ErG. 334. (a) Mercury capillarypressure curve. Sample No. 173 C, permeability
20.l millidarcys, porosity 14.3 per cent. (From Burdine et al.u) (b) Equival~~t pore
entry radius relation with distribution function. Sample No. 173 C, permeability 20.l
millidarcys, porosity 14.3 per cent. (From Burdine et al.l8)

174
18
k _
100q)
;~n t!.Sm f;'
 8(9.87 X 101 ) _L, x.'fi'
. (330)
t=l
where
q) = fractional porosity
v~
Voa
Vwa
175
_,k, (dP,
_ NI dsdz)
ds
_ k, (dP, _ Ml dz)
,
ds
ds
_ k. (dP _
dz)
.
ds
ds
Pwf/
l4
_g
"
iO
u
0
'Q
g' 8
'5
0%
' '
8
Q
Q
'
o'~4~0,~BL0,2~0,.....1~6L02L002~4028L0_32~0~3L6L040L04"'40
(From
The various equations presented here are better known examples and
can be used to yield reasonable estimates of permeability. The chief value
of these relationships, however, is in computing relative permeabilities.
The procedure of calculating relativepermeability relations will be presented in the next section of this work.
EFFECTIVE AND RELATIVE PERMEABILITY
In the above equations, the subscripts o, g, and w refer to oil, gas, and
water, respectively.
The effective permeability is a relative measure of the conductance of
the porous medium for one fluid phase when the medium is saturated with
more than one fluid. This definition of effective permeability implies that
the medium can have a distinct and measurable conductance to each phase
present in the medium.
Experimentation has established that effective permeability is a function
of the prevailing fluid saturation, the rockwetting characteristics, and the
geometry of the pores of the rock. It becomes necessary, therefore, to specify the fluid saturation when stating the effective permeability of any
particular fluid in a given medium. The effective permeability is stated as
some numerical value at some given saturation conditions. Just ask is the
accepted symbol for permeability, ko, kw, and ku are the accepted symbols
for the effective permeability to oil, water, and gas, respectively. The
saturations, if known, should be specified to define completely the conditions at which a given effective permeability exists. Unlike the previously
defined permeability, many values of effectiYe permeability now exist, one
for each particular condition of fluid saturation. Symbolically, ko(so.1a) is
the effective permeability of the medium to oil when the fluid saturations
are 60 per cent oil, 13 per cent water, and 27 per cent gas. The saturation
succession given above, that is, oil and water, is always followed. The gas
saturation is understood to be the difference of the sum of oil and water
saturations from 100 per cent.
Effective permeabilities are normally measured directly in the laboratory
on small core samples. However, owing to the many possible combinations
of saturation for a single medium, laboratory data are usually summarized
and reported as relative permeability. Relative permeability is defined as

176
the ratio of the effective permeability of a fluid at a given value of saturation to the effective permeability of that fluid at 100 per cent saturation.
It is normally assumed that the effective permeability is the same for all
fluids at 100 per cent saturation, this permeability being denoted as the
permeability of the porons medium. Thus, relative permeability can be
expressed symbolically as
k ro(S0,30) =
ko(50,30)
1.
_
l\.>rw(S0,30) 
k,,,,so .zo1
k rq(50,30) =
177
The second feature is the rapid rise in the relative permeability of the
nonwetting phase for very small increases in nonwettingphase saturations
above the equilibrium saturation. The third general characteristic is the
attainment of a nonwettingphase relative permeability of nearly 100 per
cent at nonwettingphase saturations much less than 100 per cent.
ku<50.30>
which are the relative permeabilities to oil, water, and gas, respectively,
when the medium is saturated with 50 per cent oil, 30 per cent water, and
20 per cent gas, and k is the permeability at 100 per cent saturation of one
of the fluid phases.
SW, Ofo
Fra. 336. Relative permeability to gas and water. (a) Unconsolidated sand;
(b) consolidated sand. (After Botset.tt)
Some indication of the distribution of the fluid within the porous medium
can be deduced from a study of relativepermeability data. The rapid
decline in relative permeability to the wetting phase indicates that the
larger pores or larger flow paths are occupied first by the nonwetting fluid.
As the saturation of the nonwetting phase increases, the average pore size
saturated with wetting fluid becomes successively smaller. This is confirmed by the rapid rise in the relative permeability to the nonwetting
phase. In other words, at a saturation above the socalled equilibrium
saturation, the nonwetting fluid occupies larger pores than does the wetting
fluid. The attainment of 100 per cent relative permeability to the nonwetting phase at saturations of less than 100 per cent indicates that a
portion of the available pore space, even though interconnected, contributes little to the fluidconductive capacity of the porous medium.
In Chap. 2, it was shown that the pore space is proportional to the square
of the diameter of the pore openings and the fluidconductive capacity is
proportional to the diameter of the pore openings to the fourth power.

178


 
Using the relations of Chap. 2 it is possible to use capillary tubes to illustrate the effective reduction in permeability caused by the introduction of
a second fluid.
Example 33. Effect of Saturation on Fluid Conductance. Consider
four capillary tubes of length L and diameters of 0.001, 0.005, 0.01, and
0;05 cm. The total pore volume of the four capillary tubes would be
given by
,,.L
,,.
(0.001'
(0.002626) cc
The total conductive capacity for the four tubes under the same imposed
pressure drop can be expressed by Poiseuille's law as
t;p 7r d'
Q, = ;128
Q, =
Q = t;p,,. (0.000006260626)
'
L.
128
1:'"ow if the larger tube is saturated with a second fluid of the same viscosity as the first fluid, then it is possible to express the conductive capacity
when two fi~ds are saturating the system to the conductive capacity when
only one flmd saturates the system. Thus, it is seen that the ratios of the
conductive capacities are
Q, 0.000,006,25
Q,  0.000,006,260,626 = 0 9983
and from Darcy's law
Q,
Qt
Q, = kics..s,, = 0.0017
Q,
kt(0,81)
179
tion Si, was changed by 95 per cent, and the effective permeability to this
phase was decreased by 99.8 per cent. The relativepermeability values for
the two fluids in Example 33 sum up to 1; that is, (QifQ,) + (Q,/Q,) = 1.
This behavior is not true in .actual porous systems. It would not be the
case in this example if the minute film which would wet the surface were
considered. This film would decrease the diameter of the larger tube, thus
reducing the flow capacity for the second fluid, and yet the film itself would
contribute no flow capacity to the wetting fluid. Thus, the total fluid
capacity of the tubes would be decreased. This is a rather normal feature
of most relativepermeability curves, where it is found that the total of all
values of relative permeability seldom add up to 1.
As most reservoirs are comprised of consolidated porous media, Botset22
subsequently reported results of similar relativepermeability tests conducted on consolidated sandstone. These tests were performed with water
and carbon dioxide, and the results are indicated in Fig. 336 as curves 2.
Again, water was the wetting fluid and carbon dioxide the nonwetting
phase. Note the similarity of the curves for the consolidated and unconsolidated cores. Both cores give the same general results, the differences
being in the slopes of the curves and watersaturation value at which the
relative permeability to water vanishes. It is noted that the relative permeability to water vanishes at a much greater wettingphase saturation
for the consolidated core. This difference in flow behavior indicates that
the relative permeability of a pore system is dependent in some fashion
upon the pore geometry of that system.
The average results of 26 tests on relativepermeability for Permian dolomites by Bulnes and Fitting" are shown in Fig. 337. The reader will
note that the general trend and shape of these curves on a Permian dolomite are essentially the same as those found for consolidated and unconsolidated sandstones. The same three characteristic points are noted: (1)
The wettingphase saturation declines very rapidly for small increases in
noni.vettingphase saturations; (2) all the cores indicate an eqllil!.brium gas,
nonwettingphase saturation somewhere between 10 and 30 per cent;
(3) the relative permeability to the wetting phase, which in this case is
oil, tends to vanish at saturations between 20 and 40 per cent. Thus, it
seems that the trends are very similar to those obtained for sandstones,
indicating that materials with intergranular porosity possess similar relativepermeability saturation characteristics.
It would be expected that data obtained on small core samples of fractured or vugular material would give very erratic reJativepermeability
results, i.vhich would differ from those obtained for rocks with intergranular porosity. The behavior of fractured or vugu1ar material should more
closely approximate that of Example 33, where the conductive capacity
is in the fractures and the pore volume is largely in the matrix of the sys
180
0 .8
:t' o.7
:g
0.6
0.5
'
',
\ \\
,fi
vj
\ \\
I! i
1
I/
Oil I.,
\~\ Gas
'
\\
..
"'Q 3
,
.
J
'\
0. 1
0. 8
~
~
'
, I/
K.
~ 0. 6
1/'
/
cj
..~ 0
0.5
~ 0. 4
~\
\.0
"
Jv
,,,
<>
ic
>: z.
"' 0. 3
0. 2
'~
0. 1
...
0.f
0.2
0.3
~.I'
0.4
0.5
0.6
.
'i..::
"
0.7
0.8
0.9
f.0
FrG. 338. The effect of the viscosity ratio (oil to water) on the relative permeabilities in a IOO to 200mesh sand. (After Leverett.s)
/L'
/,
Liquid saturation,
Water soturdtion
,''
"'.
;~=90.0
'
0, 7
0.
/, I
''
!'\\.\
02
o w w
!Lo =180
0. 9
0.4
1.0
'~
181
100
/0
Fra. 337. :"Relative permeability to gas and oil for West Texas dolomites. (   )
Wasson Field data; (       ) Slaughter Field data; (  ) average
r~u~ts of 26 cores from three West Texas Permian dolomites. (From Bulnes and
Fitting .zi)
the data, "'.hich are shown in Fig. 338, that relative permeability was SU.bstantially mdependent of the fluid viscosity but was some function of
poresi~e distribution, displacement pressure, pressure gradient, and fluid
saturat10ns. Subsequent work to that of Leverett has indicated that the
displacement pressure and pressure gradient are parameters which are
peculiar to laboratory measurements. These parameters have been given
the notation "end effects." As these parameters are essentially properties
?f laboratory measurements, the means of measuring relative permeability
m the laboratory must take them into consideration. End effects will be
discussed in more detail in the section covering the laboratory measurement of relative permeability.
182
This behavior is dependent upon the saturation history of the porous medium and is true if a desaturation process were followed at all times. ~
The relative permeability to gas and oil was found to depend on the
saturation values existing for all three phases in the rock. Fignres 340
100'Yo qas
100
"'i
,,
.I
80
~60
"~ 40
Q
~
~
~ 20
Q
&!
.
20
..,/
60
80
40
Water saturation, %
109
100/o wofer
and 341 show the relativepermeability data for gas and oil in a threephase system. The data are plotted on triangnlar diagrams to define the
saturation condition of the rock. The relativepermeability data are plotted
as lines of constantpercentage relative permeability.
The dependency of the oil relative permeability on the saturations of
the other phases can be established by the following reasoning: The oil
phase has a greater tendency than the gas to wet the solid. In addition,
the interfacial tension between water and oil is less than that bet,veen
water and gas. The oil occupies portions of the rock adjacent to the water
or pores that are dimensionally between those occupied by the water and
the gas. At lower water saturations the oil occupies more of the smaller
pores. The extended flow path length caused by this phenomenon accounts
for the change in relative permeability to oil at constant oil saturations and
varying water saturations.
For an oil saturation of 60 per cent and a water saturation of 40 per cent,
the relative permeability to oil as read from Fig. 340 is approximately 34
per cent. For the same oil saturation and a water saturation of 20 per cent,
it is noted that the relative permeability to oil increases to approximately
38 per cent. For a water saturation of zero, the relative permeability to
oil is approximately 18 per cent. Thus, it is seen that by changing the
183
water and gas saturation the flow characteristics of the oil are changed so
that the oil assumes more tortuous paths.
.
The variation of the gas relative permeability at constant gas saturat10ns
to the saturations of the other phases is indicated in Fig. 341. The reason
for the particular behavior indicated
f00% gos
is not definite, as other investigators
indicate that the relative permeability to gas should be a unique
function of gas saturation. Other
studies of threephase flow systems
will be necessary to establish definitely the relative permeability for
gas in threephase systems. It would
be expected that when gas is in a
system, it is the fluid least likely to
wet the surface of the rock and,
therefore, should take on a property ;?O"J., water
which is dependent only upon the FIG. 341. kru, relative permeability to gas
total fluid saturations of the other as a function of saturation. Curves are
lines of constant permeability as per
two phases. The other phases, oil cent of relative permeability. (From
and water, should occupy the Leverett and Lewis.'i!S)
smaller pore openings and wet the
surface of the rock. Therefore, the gas phase should be dependent only
upon the total liquid saturations and independent of how much of that
total is composed of either phase.
.
. .
It is noted from a study of Leverett's data that the saturation reglOn m
which simultaneous flow of all three phases occurs is quite ~all. The regions in which singlephase, twophase, and threephase. flmds flow will
normally occur are indicated in Fig. 342. For gas saturations 1n excess of
35 per cent essentially only gas is flowing in the system. For gas saturations betw:en 18 and 35 per cent and for water saturations less than. approximately 40 per cent, oil and gas are both.flowing. For water saturatlOns
between 18 and 85 per cent and oil saturat10ns rangmg from 15 to 82 per
cent, where the gas saturation does not exceed approxrmately _15 per cent,
only oil and water are flowing. The region of. threephase flow rs extremely
small and essentially centers around the reg10n of 20 per cent gas, 30 per
cent oil, and 50 per cent water saturation. This region is _illustrat:d in
Fig. 342 by the "hatched" area. The singlephase flow regions are illustrated by the shaded area, and the twophase flow regions are illustrated
by the white area. From these data it is evident. that in most c~ses tw:ophase relativepermeability curves are qmte satisfactory: For rmmo~ile
water saturations it is possible to define gas and 01! relativepermeability
184
185
curves using twophase techniques. Also in this twophase flow region, the
used in the test are introduced simultaneously at the inlet end through
different piping systems. Most tests are started with the core sample at
100 per cent saturation in the wetting phase, and the tests are ~own ~s
desaturation tests. The two fluids are introduced at a predeternuned flmd
ratio and are flowed through the core until the produced ratio is equal to
the injected ratio. At this time, the core system is considered to be in a
steadystate flow condition and the existing saturations are considered to
be stable.
The saturation of the various fluids are determined in one of three fashions: (1) Electrodes have been inserted in the test section, and the saturations are determined by measurement of the core resistivity; (2) the core
section is removed and weighed to determine the saturation conditions; or
(3) a volumetric balance is maintained of all fluids injected and produced
from the sample. Once the saturation has been measured by one of the
above methods, the relative permeability of the two phases at these satu.ration conditions can be calculated. The injected ratio is increased, removmg
more of the wetting phase, unti1 once
Gos
Gos
again the system is flowing in steadyinlet
outlet
state condition. The process is continually repeated until a complete
relativepermeability curve is obtained.
An alternate method is to use the
resaturation process where the test
section is originally 100 per cent saturated by the nonwetting phase. In
this method the injection ratios start
out at high nonwettingphase values
and decline to 100 per cent wetting
To
phase. The results obtained using the
atmosphere
Porcelain
desaturation and resaturation proplate~
cesses illustrate a hysteresis effect of
Oil burette
the same type discussed earlier in
connection with capillarypressure
Fro. 343. Relativepermeability apcurves.
paratus (Hassler's principle). From
Some of the equipment and results Osoba et al.m)
obtained using the steadystate process
are illustrated in Figs. 343 to 349. Four of the apparatus which
have been developed for testing small core samples are shown in Figs. 343
to 346. The four apparatus illustrated represent the Hassler method,
Penn State method, Hafford method, and dispersedfeed method. In order
to eliminate end effects, porous material has been placed in cont~wt with
the outflow face of the test section. In the Hafford apparatus (Fig. 345)
curves obtained for twophase systems, gas and liquid, are essentially the
same as would be obtained if a third immobile phase is present. The relative permeability to the mobile liquid phase is essential~y dependent on
t00% gas
~
100% oil
FIG. 342. Approximate limits of saturations giving 5 per cent or more of all components
flow strean;i. Fluids: nitrogen, kerosene, brine. Arrows point to increasmg fraction of respective components in stream. (From Leverett and Lewis.:is)
!n
the total liquid saturation. Thus the relative permeability to oil at 60 per
cent oil and 20 per cent water and that at 80 per cent oil and zero per cent
water are not greatly different, as illustrated by Fig. 340. This behavior
is attributed to the fact that the smaller saturation values of the wetting
phase contribute little to the fluid conductance of the porous matrix.
Measurement of Relativepermeability Data
There are essentially four means by which relativepermeability data
can be obtained. They are (I) direct measurement in the laboratory by a
steadystatefiuid flow process, (2) measurement in the laboratory by a displacement or a pseudounsteadystate process, (3) calculations of relativepermeability data from capillarypressure data, and (4) calculations from
fieldperformance data. The methods most used are the laboratory stead;state flow and displacement processes.
There are numerous steadystate methods which can be used in the
laboratory to measure relative permeability, but essentially, all of tbem
depend upon tbe following technique. A small core sample is chosen and
prepared for tbe test. It is mounted either in lucite or in a pressurized
rubber sleeve. Either the flow system is designed for a high rate of flow
and large pressure differential, or each end of the sample is suitably prepared with porous disks and test sections to minimize end effects.
The phases oil and gas, oil and water, or gas and water which are to be

186
Thermometer
Pocking
//
nut
Copper
Electrodes
/"..
Inlet
orifice
plate
:.:&,(!:.. =. >7e~t::
:: Sectio; : :Section.:

187
and in the dispersedfeed apparatus (Fig. 346), end effects are materially
reduced by maintaining a high rate of flow through the test section. All
the apparatus depend on the same flo'v mechanism and are different only
in the manner in which they introduce the two fluids and in the manner
in which they adjust for end effects. As some of the steadystate relativepermeability measuring devices depend on the rate of flow or pressure drop
Gas meter
. ......
.  ..
:: ..:: :.
Lucffe
Differential _
press1.1re tops
Outlet
Bronze
screen
Inlet
Gos
?uclfemounted
core
Gos
pressure
gauge
Oil burette
Oil
Dispersing
section face
Oil
pressure
Fro. 346. Dispersedfeed relativepermeability apparatus. (From Richardson et al.28 )
Oil burette
188
from 2 to 16 psi per in. The same is true for other ratios. In the case of
the 100:1 oilwater ratio, when the pressure gradient gets below 0.678 psi
per in., the permeability ratio of oil to water increases, so that at Iowpressure .differttntials it is apparent that end effects are becoming a dominate factor in the control of the flow mechanism.
189
100,~~,~..,,.~c;c.,..~~~~~~~~
80
,,::
~ 60t~~t~~~j\~~t~~~+~+i
Oilwater
flow ratio
k 0 /k,,,
Average
brine
saturation,
Pressure
gradient,
psi/in.
Infinite
Infinite
14.2
2.04
100:1
100:1
100:1
100:1
150.6
149.4
149.4
152.3
36.9
37.2
37.3
37.7
4.71
9.16
1.27
0.678
47.3
45.9
46.3
14.34
4.93
0.994
10:1
IO:!
10:1
15.76
15.36
15.04
I :I
1:1
I.488
1.510
53.5
52.9
1.24
3.05
1:10
1:10
1:10
0.1507
0.1507
0.1537
56.0
55.6
55.I
16.47
8.14
2.43
57.7
20
00!;~......,2~0,...~4~0'.,..,....~;:..._~~,,,..:.'.'.:::'l;..,,,olo
Oil saturation, 0 /o
100
A
kq
o. kg
15.91
40r~~r~~~t~TI;r~~~t~~1
.,,a:~
fi
""
80
*kg
0
kg
c kg
.. kg
ko
+ ko
* k,ko
ko
< ko
(From Richardson
I
Penn State
Singlecore dynamic
Dispersed feed
Hofford. technique
Hassler technique
Gasdrive technique
60
.>
40
.,,"'a:
0
20
00
20
40
100
Oil saturation, %
'
190
is injected into the core. The gasdrive technique then is a nonsteadystate process in that only one fluid is entering the core and two fluids are
leaving. If the core and both fluids are taken as a whole, the process can
be treated as a steadystate volume process but not a steadytate mass
flow system.
The gasdisplacement process for determining relative permeabilities as
proposed by Welge" is dependent upon the frontal advance fluidflow concept. This procedure actually determines relativepermeability ratios and
is dependent upon the actual relativepermeability values being determined
by some independent means, such as calculating the relative permeability
to oil from capillarypressure data or measuring in the laboratory. The
procedure for performing a gasdisplacement test is relatively simple and
fast. The procedure is essentially as follows: An approximately homogeneous sample is selected, and its physical properties of permeability,
bulk volume, and porosity are determined. The sample is properly mounted
in a holder, similar to those used in the steadystate tests (Figs. 343 to
346), and 100 per cent saturated with the wetting phaRe, which is normally
oil and will be considered as oil in the discussion which follows. The sample is desaturated by injecting gas at one end and producing both oil and
gas at the other end of the small sample. In the calculations of the data
obtained from such a test, there are essentially three necessary conditions
or asswnptions which must be satisfied. First, the pressure drop across
the core sample must be large enough to make any capillary end effects
negligible. Second, the gas saturation can be described at a mean value
of pressure defined as
(331)
where Pi represents the pressure at the injection end of the core and P 0
represents the pressure at the production end of the core. Third, flow is
horizontal, and the core sample is small enough and the test time is short,
s,o that all effects of gravitational forces can be neglected.
If these three conditions are satisfied, then it is necessary to measure
only the following quantities during the test: (!) the cumulative gas injected as a function of time and (2) the cumulative oil produced as a function of time. With these two measured quantities and with the pressures
at the injection and production ends remaining constant, the relativepermeability ratio of gas with respect to oil can be calculated.
From the measured data, the cumulative volume of gas injected in terms
of mean pressure is expressed as a multiple of the total pore volume of the
sample and can be calculated by the following equation:
(332)
where (G;),,.
191
S,,..,
A quantity known as
may be calculated simply by dividing the
cumulative oil produced by the pore volume of the sample. Both the gas
injected and oil produced have been measured with respect to time and
therefore can be cross plotted so that a plot of S""'' as a function of the
cumulative pore volumes of gas injected can be obtained. The slope of
the sg{av)injected gas curve represents the fraction of the total outflow
volume from the sample that is oil at any given time, which defines the
following equation:
(333)
where f. represents the fraction of the total outflow that is oil. The relativepermeability ratio of gas to oil can be calculated from the following
equation:
k,
1  f.
(334)
k; = f.(,/ .)
where k,/k. = relative permeability ratio of gas to oil
JLo = viscosity of gas
" = viscosity of oil
f. = fractional flow of the oil as previously defined
This particular value of the relativepermeability ratio applies at the gas
saturation at the outflow face. The gas saturation at the outflow face is
expressed by the following equation:
(335)
(S,). = (S,).v  (G,),,..f.
Hence the relativepermeability ratios are obtained as a function of saturation by solving the above series of equations.
In order to determine the actual value of the relative permeability to
either gas or oil, it is necessary that one or the other be independently determined. It would be possible to measure or else to calculate the other
functions by one of the means previously discussed in this chapter.
The gasdisplacement method has several advantages in that it can be
performed with a small amount of equipment and can be performed rapidly
and on relatively small core samples. It has the disadvantage in that it
cannot determine relativepermeability ratios at low values of gas saturation except by the use of highviscosity oils. The equations do not apply
until such time as gas is being produced at the outflow end of the core.
Depending upon the permeability of the core and the pore geometry, the
gas saturation at the outflow face at the time gas is initially produced
192
193
may vary between 2 and 15 per cent, depending upon the viscosities of the
gas and oil in the syst,,m. The lower the viscosity of the oil, the greater
will be the gas saturation at the outflow face at the time that gas production begins. Thus, by using oil samples of various viscosities, it would be
tory is eliminated.
Field Determination of Relativepermeability Ratios. The third means
of determining relative permeability has the same drawback as the displacement process in that the data obtained are actually determined as
relativepermeability ratios. Thi.<:! process is a calculating procedure utiliz
effects and of the fact that in many of the techniques developed special
precautions had been taken to eliminate these effects from the laboratory
measurement. End effects arise from the saturation discontinuity existing at the outflow face of a porous medium when mounted for a flow
test. The fluids flowing through the core are discharged into a region void
of the porous medium. Therefore, at the outflow face, all the fluids exist
at the same pressure, whereas iinmediately within the pores of the rock at
Darcy's equation were written for gas and oil flow, both phases being con
of the wetting phas.. approach 100 per cent. There is, then, a saturation
gradient established in the wetting phase of the flow system.
The theory of "end effect" can be developed as follows:
Q, _ A(k,/,)(M',/M,)
Q,  A(k,/,)(M',/t:.L)
From Darcy's law for a linear system and the concept of effective permeability, when more than one phase is present in a rock,
(336)
(337)
_where BfJ represents the formation volume factor of the gas expressed as
reservoir cubic feet of gas per standard cubic foot of gas and B represents
the oilformation volume factor expressed as reservoir barrels of oil per
stocktank barrel of oil. RP represents the producing gasoil ratio, and
R" represents the solutiongasoil ratio, both expressed a.";! standard cubic
foot per stocktank barrel. /Lg is the gas viscosity and 0 is the oil viscosity
at reservoir conditions of pressure and temperature.
The normal procedure is to use field average gasoil ratios, which are
(338)
dP
,,..,
 Q
dL
knweA
,.wt 
dP, ~ dP ,  dP.,
(340)
where the subscripts nwt and wt refer to the nonwetting and wetting fluids,
respectively, other symbols as previously defined.
normally the most accurate values obtainable. The field average gasoil
ratios are preferably obtained from gasplant production figures. The solution ratio Rs is dependent upon the reservoir pressure and is taken at the
average reservoir pressure which is in existence at the time the produced
(339)
(341)
where dPJdL is the capillarypressure gradient within the core. Since
capillary pressure has been shown to be a function of saturation and in
any displacement system the saturation can be expressed as a function of
dP., dSIDt
dL = dS., dL
where S., is the wettingphase saturation. Eq. (341) then becomes
as., ~ l. (Q.,.,
dL
k.,
_Qk,""')
1
,
dP,/dS.,
(342)
194
Gospressure tops
Neoprene~
sleeve
Sealingpressure fop
/o;/pressure po~s
_"'
100
V Theoretical
,. 80
~
Oil i/1
To gos flowmeter
.~
e
60
~
~
t To oil bureffe
195
40
gradient
<...::
.
saturation
<!
~
80
'~
Theoreficq/ soturolion
grqdienl
~'

 ..
I
!
~
I
Inflow face....,.!
I'
10
5
15
20
25
Distance from outflow face, cm
!
iI
20
fOO
1
Inflow face,
i5
1 0 0 1 ,   ,    .    ,    ,     , 100
\o
20
25
15
20
5
Distance from outflow face, cm
kr0 =f0? md
,.
;;
~
80
:/?.?%
L =30.?cm t+~f1180
0 =6.85cm
."'
0
3
60t++++.ll
"E
.5
~
~
40t+t."<l+l'l
0o~;;2~0~~40;:_..::;_::':::::':"'..J
Oil saturation,
/0
To determine the magnitude of end effects, Richardson" studied saturation gradients in a long core apparatus (Fig. 349). The test apparatus
was designed to determine the pressure in each of the flowing phases at
different positions along the core. The relativepermeability relationships
were determined for different rates of flow and pressure gradients across
the core. In addition, capillarypressure characteristics were measured.
Figure 350 presents the results of these tests as well as the physical properties of the core. The relativepermeability data shown are for conditions
eliminating end effects and therefore are correct.
Figures 351 and 352 illustrate both the computed and measured saturation gradients measured by Richardson on the long core shown in Fig.
349. Note the good correspondence of theory and experimental results
and the reduction of end effect resulting from using higher rates of flow
(Fig. 352).
Calculation of Relative Permeability from Capillarypressure Data. In
the discussion of capillary pressure, several equations were presented for
the calculation of permeability from capillarypressure data.
196
[8
dS
}s=o (P,)'
)>.<p
197
(327)
(348)
rss., (P,)'
dS
Js=o
(343)
where k., is the effective permeability to the wetting phase. The relative
permeability to the wetting phase is given then by
k.,
1s::s.
=
1s::
dS/(P,J'
(344)
dS/(P,) 2
where the lithology factor >. is assumed to be a constant for the porous
medium.
The effective permeability to the nonwetting phase (k,.,) can be calculated in a similar fashion as in Eq. (343) by assuming that the nonwetting
phase is contained in tubes or pores, free of the wetting phase of radius as
defined by the capillarypressure relation in the wettingphase saturation
interval Swt = Swt to Swt = 1.
k,,., = 10.24(. cos 8)'>.<t>
f.
S=l
dS
(P )'
S=8.r1
Is::'..
that the lithology factor >. was a function of saturation. The lithology
factor is essentially a correction for deviation of the path length from the
length of the porous medium. Fatt and Dykstra assumed that the deviation of the path length was a function of the radius of the conducting pores,
so that
(349)
where r is the radius of a pore and a and b are constants for the material.
The equation for relative permeability for the wetting phase (k,.,) then
becomes
(345)
(350)
dS/(P,)'
(346)
which is of the same form as Eq. (344), where b is a correction for deviation of the flow paths from straight tubes.
Fatt and Dykstra further assumed that b = ~, thus reducing (350) to
k,., =
Jos.. dS/(P,)'
lo' dS/(P,)'
(351)
Eqs. (344) and (351). There are significant differences in the computed
and observed data.
(347)
for both the wetting and nonwetting phases. His equations can be shown
to reduce to a form similar to that of Purcell for permeability. Burdine's
contribution is principally in handling tortuosity.
198
20
80
\
P,I
\
'J
"' 8
~
"
r   Co/cu/afed from
Eq. 1352)
''
4    Calcufoted from
Eq. 1345)
'
I I,
'1
//
~60
Observed
'
'
20
40
60
Io
k,.,
40
)s~~ dS/(X,)'(P,)l
20
0
100
/o
k,.,
= (!.,.wt)
J:~:s., dS/(P,)l
1is~1
S=O
.2
(p)
c ~
(353)
(352)
80
hs.,rs
Then
Weter saturation,
f\wti
:g
1';;
..g
0
A;
= ~
Arwti
ff
o.
0
Defining the tortuosity factor for a pore as A; when the porous medium
is saturated with only one fluid and x ., for the wettingphase tortuosity
factor when two phases are present, a tortuosity ratio can be defined as
100
199
k~
f,s~i dS/(P,)l
fs:~' dS/(P,)'
(354)
_ S.,  Sm
l _ S.,.
flrwt 
s, %
100
95
p"
1/Pc3,
cm Hg
(cmHg)
85
3.8
4.1
4.4
4.8
18.2
14.5
11.7
9.0
80
75
70
65
5.3
5.8
6.4
7.1
9Q
60
55
50
45
8.0
9.4
11.6
15.0
103
Area from
0 toS,
sq in.
krwt,
100
75
56
40
6.7
5.1
3.8
2.8
1.19
0.82
0.54
0.34
29
20
13
8.2
2.0
1.2
0.6
0.3
0.20
0.10
0.04
0.01
4.8
2.4
1.0
0.2
103
where S.,. is the minimum wettingphase saturation from a capillarypressure curve. The nonwettingphase tortuosity can be approximated by a
straightline function also and is given by
~.,
4.15
3.13
2.31
1.68
(355)
Snwt  Se
(1  Sm)  S,
(3 56)

the same degree, then the data taken with an oilgas system would be the
same as the data taken with a "'~atergas system or a wateroil system.
AB all fluids do not wet a solid to the same degree and as water may not
be the fluid which preferentially wets the rock, investigations have been
made of the effect rock wettability has on relativepermeability data for
oilbrine systems. The relativepermeability values are affected by the



201
change in the fluid distribution brought about by different wetting characteristics. Figure 355 illustrates changes in relative permeability caused
by different wetting characteristics. Curves 1 and Z are indicative of a
waterwet system, while curve 3 indicates that the system is preferentially
oilwet. It is noted that when the rock is preferentially waterwet, the
water loses its mobility at a higher value of water saturation than when
the rock is preferentially oilwet. This fact would indicate that the oil is
200
1.0~~ 1.0
Tortuosity ratio
o Fractional permeability
o.a: 1.J'I\'.
0.9
Relative permeability
(calcpsd l
Relative permeability
(meas)
100...,..;,
_,__,___,,_, 0.8
0.7 ~e.
..
;;
"'
0.6 '.3
0
~
:;;
0.5
0.4 ~
0
0.3 6
0.2
"'
0.2
~
"&1 25
'
50
:"t
~
~
~ 0.3
75
2/l.
0.1
100
00
Brine saturation, '"lo pore space
Liquid saturation, 0/o pore volume
FIG. 355. Effect of wettability on flow behavior. Nellie Bly sandstone. (From
Geffen et al.'Z1)
FlG.
higher values of saturation than does the drainage technique. The two
methods have similar effects on the wettingphase (water) curve. The
drainage method causes the wetting phase to lose its mobility at higher
values of wettingphase saturation than does the imbibition method.
In the discussion of both porosity and permeability, it was noted that
overburden pressure affected the values obtained. Fatt31 reported, as
shown in Fig. 358, that overburden pressure did not affect the relativepermeability data although the effective permeabilities are altered.
In Figs. 359 and 300 are presented relativepermeability and permeability ratio data for typical tests of various media. These data indicate
retained in some of the smaller, more tortuous paths within the medium.
It thus becomes necessary to classify reservoir rocks as being oilwet,
\vnter~et, or intermediate so as to define relative permeability properly.
As was discussed for capillarypressure data, there is also a saturationhistory effect for relative permeability. The effect of saturation history on
relative permeability is illustrated in Figs. 356 and 357. If the rock sample is initially saturated with the wetting phase and relativepermeability
data are obtained by decreasing the wettingphase saturation while flowing
202
the effect of pore configuration and poresize distribution on relative permeability. The curves should not be interpreted as representative of the
types of media but should be viewed as illustrations of the effects of pore
geometry on relative permeability. It is apparent then that universal permeability curves cannot be established. Rather, each reservoir rock (each
~
:E
203
120>~~+~.....~+~~+~~~+~~1
.~ 1oof~~+~~\\+~~+~~~+~~.!
.0
.g
Drainage
1 so1~~+~~~;r..,_~+~~~+~~_,.;/
"'t
:0
1
60'1~~t~~~+~Tt~~~t~11
&!
40>~~~~~~~~111~~~+~0'I
AD1rection of
0.011~~~tr1
o Increasing gas
Decreasing gas, oi'rbrine system
t::.. Increasing oil
.&. Oecreoslng oil, oilbrine system
A Direction of soturation change
satvration change
201
20
80
Brine soturotion, 0/o pore space
100
FIG. 356. Oilwater flow characteristics. Nellie Bly sandstone, permeability 143
millidarcys, porosity 26.1 per cent. (From Geffen.27 )
o.000 1 0
~""""'20;;;4;;,o,6C:o;;,a~o:.F100
Brine saturation, 0/o pore space
sample, for that matter) has a characteristic pore geometry which affects
relative permeability.
In Fig. 361 is shown the effect of connatewater saturation on the gasoil permeability ratio. In general, low water saturations do not appreciably affect the permeability ratio, simply because the water occupies
space which does not contribute substantially to the flow capacity of the
rock.
204
205
point of 100 per cent water saturation. Knutsen" recognized the fact that
two water tables e.'<ist. These two water tables can be defined as:
1. The free water or zerocapillarypressure level
2. The level below which fluid production is 100 per cent water
These two definitions for the water table in an oil reservoir are illustrated
in Fig. 362.
200
oo
60
40
20
.,.~
'
~ ~
~ ~
...._~\ ~~ ~.
% % 0. ~
~='=..  ,_~
.... ~
~
\
\
'
0.02
0.
\"
9 \
~Q 8
.,....
.......
'\ \
~ 0.3
..\1
, / \. '
10
I
I
\,,,\ lX' I,
\ '><' \ ?I if 4j.
// I
..\4
~3
g 0.2
0.1
~ 0.5
_; 0.4
""
0.6
/,
\\
0.7
I.0
><
20
'
>;: :;...
30
40
,V
(;)' r....'
50
I
....:: ......
><
60 70 80 90
0.01
0.9

,~
,~
'%
I=
~
~ ~
20
40
_,.o
0.7 ~
0.6 :0
0
 connote
/lfater
80
2 f.40%
connote
1 'water
':l.c""' 0.6
0.4
o.
\
60
>2
...__
i/
/lfOfer
0.02
mo
o.o
'0
' .J
'
'
!tt
'
0.06
0.04
\
0
0.2
Liquid saturation, 0; 0
0.8~
0.5
0.
'
0.04
1.0
%;\
0.
0.06
C~o
connote 
0.2
T T
20%
'6
c.~C">
\?
0
'2,~
0.4
FIG. 358. Relative gas permeability in the gasoil system with and without overburden pressure. (From Fatt.tsJ.)
20
(">
0.6
Oil soturotion, 0/ 0
~\
'6
.,::
...__
'40600
'
I
20
40
60
80
iOO
~
~
0.4 ~
03
.
0.2
0.1
100
Fro. 3:59. _Relative permeability for various types of media. (1) Capillary tube
(Martinell~, Putnam, and Lo.chart, Trans. Am. Inst. Chem. Engrs., Aug. 25, 1946);
(2)_ dolonnte (Bulnes and F1tting23); (3) unconsolidated sand (Botset=); (4) consolidated sand Botset22 ) .
Note that the water table by definition 2 rises as the permeability in the
formation decreases while the water table by definition 1 is a horizontal
surface, providing static conditions prevail in the reservoir. From a production engineering standpoint, a contact defined as the highest point of
water production is useful.. From a reservoir engineering standpoint, a
contact defined by zero capillary pressure is a more appropriate definition.
The actual location of water tables 1 and 2 can be determined by the
use of electric logs, drillstem tests, and relativepermeability and capillarypressure data. From electric logs and drillstem test data, it is possible to
determine the depth at which 100 per cent water flow occurs or the point
of zero oil permeability. From relativepermeability data the engineer can
0
0
"'~
:c0
0
0
;.
:;}
'
"
:;;
~J
I'
..c:~
12
...
.~3"'
t%~
<:) I
~~"'
O\.._
1;;
~aO\
~~"'"
~~
<t
"'
"
(O/o}
00
Jlf
"
:t:
~"'
"''
:g
.s
""Q.
:S
\t%>t::
,
0'
"'~<:)
~"""~
"
'
"
00
!i~,;
~ <b
<b~
~1:>:5
ti"%
,~
~1
'
"
~ 'i\
3:
..,,
"'g
00
"
;i~
' 'i
"
Ci
0
0
=
t
.w =1
l'o
0.4
"
!l
"
!l
0.2
.,,a
=
=
)3
0.6
t>
0
tl:
<>:!:::
<::>
"''
~~'3
<t
.,,"'
0
~
""
=
:a
.,,"'=
~%
.I!?
0
~~
~
"
.s
\\
tl
I
I
0.8
0.
~~
1.0
40
60
Water saturation, 0/o
20
80
that a formation be 100 per cent watersaturated in order for that formation
to produce 100 per cent water. By use of the fractional flow equation*
0
0
0
0
:;}
.,;
"';);
~
J..
where
. 111 /
100
F1a. 363. Effect of water saturation on fractional flow of water through a homogeneous medium.
0
0
0
207
determine what the fluid saturations must be at the point of zero oil permeability. When the fluid saturations determined from well test data and
relativepermeability curves are used, the capillary pressure can be determined and the height above the free water surface or zone of 100 per cent
water saturation can be calculated. The above procedure is illustrated in
Fig. 362. The existence of two distinct water tables materially aids in explaining the occurrence of some "tilted 'Yater tables." It is noted that the
more permeable the formation, the more closely the pore structure approaches a supercapillary system and the smaller the divergence between
the two water tables.
Aid in Evaluating Drillstem and Production Tests. As indicated in the
preceding discussion on the location of the water table, it is not necessary
.~%~
6>
a
o~
=o0 3"'
~12
' "'
<t
'?
0
"
~"' :~1
~I
(l
2?i
c:::.J
E=
,
0.
~
II
."'.~!
:~J
0
0
::,
I
0
;;
'<=
o~
"
0
0
in a companion volwne.
208
MEDIA
and relativepermeability data, the engineer can calculate the height above
the free water surface at which both water and oil can be produced. Using
the resultant solution of the fractional flow equation shown in Fig. 363
and the capillarypressure data shown in Figs. 326 and 327, the height
of the twophase producing interval was determined for permeabilities
from 10 to 900 millidarcys. The results of these calculations are shown
in Fig. 364.
16 0
140
12 0
~ 10 0
\omd
~
60
~
40
\
~md
20
\
~ ,...___
~....._
r._
0d
9'oOmd......5,00md
40
60
209
REFERENCES
\
20
\md
"
CONTAI;t~ING
80
100
Fro. 364. Fraction of water in produced fluid as a function of height above the
free water level (using capillarypressure data shown in Fig. 327).
It is noted from the fractional flow curve (Fig. 363) that water flows at
oil saturation as high as 65 per cent. Thus, from the capillarypressure
curve (Fig. 326), it is determined that water would be produced on a drillstem test 10 ft above the free water surface for a formation with a per
1. Benner, F. C., and F. E. Bartell: The Effect of Polar Impurities upon Capillary
and Surface Phenomena in Petroleum Production, Drilling and Production Practices,
American Petroleum Institute, 1941.
2. Plateau, J. A. F.: Experimental and Theoretical Research on the Figures of Equilibrium of a Liquid Mass Withdrawn from the Action of Gravity, Smith Inst. Ann.
Repts., 18631866.
3. Leverett, M. C.: Capillary Behavior in Porous Solids, Tram. AIME, 1941.
4. Fancher, G. H., J. A. Lewis, and K. B. Barnes: Penn. State Coll Mineral Ind.
Expt. Sta. Bull. 12, 1933.
5. McCardell, W. M.: A Review of the Physical Basis for the Use of the Jfunction,
Eighth Oil Recovery Conference, Texas Petroleum Research Committee, 1955.
6. Welge, H.J., and W. A. Bruce: The Restored State Method for Determination of
Oil in Place and Conn.ate Water, Drilling and Producti<m Practices, American Petroleum Institute, 1947.
7. Purcell, W.R.: Capillary PressuresTheir Measurement Using Mercury and the
Calculation of Permeability Therefrom, Trans. AIME, 1949.
8. Slobod, R L., Adele Chambers, and W. L. Prehn, Jr.: Use of Centrifuge for Determining Connate Water, Residual Oil and Capillary Pressure Curves of Small Core
Samples, Tram. AIME, 1951.
9. Brown, Harry W.: Capillary Pressure Investigations, Trans. AIME, 1951.
10. Gates, George L., Frank C. Morris, and W. Hodge Caraway: Effect of Oilbase
Drilling Fluid Filtrate on Analysis of Core from South Coles Levee, California and
Rangely, Colorado Field, U.S. Bur. Mines Rept. Irwest. 4716, August, 1950.
210
11. Owen, J. F.: Electric Logging in the Quinduno Field Roberts County T
Symposium on Formation Evaluation, AIME, October, 1955~
' exa.,
12. Guthrie, R. K.,_ and Martin H. Greenburger: "The Use of Multiple Correlation
~nalyses for Interp~eti~g P~tr_o~eum Engineering Data.," presented at the Spring Meetmg of the S. W. DlStnct D1vis1on of Production, New Orleans, La., Mar. 911, 1955:
13. R~se, Walter, and W. A. Bruce: Evaluation of Capillary Characters in Petroleum
Reservoir Rock, Trans. AIME, 1949.
14. W~gh:t, :S: T., Jr., and L. D. Wooddy, Jr.: Formation Evaluation of the Borregas
and See~on Field, Brooks and Jim Wells County, Texas, Symposium on Formation
Evaluation, AIME, October, 1955.
15. Calhoun, John C., Jr.: "Fundamentals of Reservoir Engineering,'' University of
Oklahoma Press, Norman, Okla., 1953.
16. Calhoun, J. C., and S. T. Yust.er: Effect of Pressure Gradients and Saturations
on Recovery in Water Flooding, Proc. 8th Tech. Canf. an Petrol. Production, Pennsylvania
State College, 1944.
17. Slobod, R. L., and H. A. Blum: Method for Determining Wettability of Reservoir
Rocks, Trans. AIME, 1952.
18. B?1'dine, N. T., L. S. Gournay, and P. 0. Reicherty: Pore Size Distribution of
Reservou Rocks, Trans. AIME, 1950.
19. Ritter, H. L., and L. C. Drake: Pore Size Distribution in Porous Materials Ind
Eng. Chem., December, 1945.
'
32. Knutsen, Carroll F.: Definition of Water Table, Am. Assoc. Petrol Geologists
vol. 38, pt. 2, 1954.
.
'
CHAPTER
INTRODUCTION
212
erties of the associated waters are of interest to the engineer, as this water
occupies space in the reservoir, contributes energy to the production of oil,
and may be produced with oil and gas. Succeeding chapters will deal with
the applications of these physical properties of hydrocarbon fluids and with
the properties of formation waters.
In order to study properly the physical properties of fluids, it is first
necessary to gain some understanding of simple systems. A singlecomponent hydrocarbon can be obtained only after extensive processing and
does not exist in natural occurrences. However, the physical properties
of a singlecomponent hydrocarbon and its behavior when subjected to
changes in pressure and temperature are qualitatively similar to those of
more complex systems. It is convenient, therefore, to introduce the basic
definitions and to review the concepts of thermodynamics and physical
chemistry in terms of a single hydrocarbon.
Physical properties of interest to an engineer ordinarily are defined in
terms of the pressure and temperature at which a hydrocarbon exists.
Fluids in general are classified as gases, vapors, or liquids. It should be
pointed out that these particular words convey ideas only when conditions
of pressure and temperature are specified. A material may exist as a gas
or as a liquid, depending upon the pressure and temperature to which that
material is su\Jjected. Vapor is defined in the dictionary as any substance
in the gaseous state which, under ordinary conditions:,. is usually a liquid
or solid. By ordinary conditions are meant atmospheric conditions of pressure and temperature. In dealing with hydrocarbons it is convenient to
think of the words gas and vapor as being synonymous.
As in other fluid systems, a hydrocarbon system may be homogeneous
or heterogeneous. In a homogeneous system, all parts of the system have
the same physical and chemical properties. A heterogeneous system is one
in which the physical and chemical properties are not the same throughout.
A heterogeneous system is comprised of phases. A phase is defined by
Daniels2 as "a definite part of a system which is homogeneous throughout
and physically separated from other phases by distinct boundaries." An
example of a heterogeneous system is that of water, ice, and water vapor
in which three phases are present. The degree of dispersion does not enter
in consideration of the number of phases. In the example cited the ice is
a single pha.".!e whether it exists in one piece or several.
BASIC CONCEPTS OF PHASE BEHAVIOR
Singlecomponent Systems
Ethane is the hydrocarbon chosen for an example of a singlecomponent
system. Ethane is ordinarily thought of as being a gas and quite properly
(from the dictionary definition), as at ordinary conditions ethane exists as
213
,/
/A
214
215
0.05
0.10
0.15
Q20
0.25
3
Specific volume, ft /lb
+ v,(W,)
216
+ W,)
= VL(W L)
+ v,(W,)
which can be reduced to an expression for the weight ratio of liquid to gas.
Vg Vcom 
Vcom.
VL
Wcom 1 WL,
tion of the principle of average composite densities. A straight line is obtained by plotting the arithmetic average of the densities of the vapor and
liquid defined at the pressures and temperatures of the vaporpressure
curve. This line paSSe,5 through the critical point as illustrated by the
dashed line of Fig. 43. The critical point is defined by the convergence
of the vapor, liquid, and average com~osite density curves.
Binary Systems
When a second component is added to a hydrocarbon system, the phase
behavior becomes more complex. This increase in complexity is caused by
the introduction of another variable, composition, to the system.
The effect of this variable can be noted by contrasting the pressuretemperature curve plotted in Fig. 41 with that of Fig. 44. For a single
1,400~~,~,;lC,om_p_o_,,"t;coni
C
2
No. Wt % ethane
'f~'1'+'<"c1g1
/
'
,C
1,2QQi
Figure 43 shows the relation between the liquid and vapor densities of
ethane. Considering the material at point A,, in the twophase region, the
density of the liquid in equilibrium
with its coexisting vapor is specified
by point A. The density of the
coexisting vapor is specified by
point A'. Note that at the critical
point the density, one of the intensive properties of ethane, becomes
singlevalued. This is to be ex0.1
pected, as by definition, the critical
point is that point at which the
vapor and liquid phases become
90
Temperature F
continuously identical. In other
Fra. 43. Saturated liquid and vapor den words, as the critical point is apsities of ethane. (From Brown et al.')
proached along the dewpoint curve,
the density of the vapor progressively increases. As the critical point is approached along the bubble
1~g~g
50. 25
Further inspection of Fig. 42 indicates that the state of the ethane can
be specified completely by the pressure and specific volume. However,
only outside the twophase region can the physical state be completely
specified by the pressure and temperature. This, of course, corresponds
to the observation that can be made from the vaporpressure curve.
217
!C3
\ C7
9.78
Nheptane
\
\
c
~aool~l1111+l+Tl1
Ao
400
500
Temperature, F
component system the vaporpressure curve represents the trace of both the
bubblepoint and dewpoint curves on the pressuretemperature plane. For
218
219
600
700
Temperature, F
FIG. 45. Illustrating effect of divergence in composition on critical point loci. (From
Brown et al.')

220
    

221
Cricondenbar (T). The highest pressure at which the liquid and vapor
can coexist in equilibrium. (Some authorities name this point the Crivaporbar.)
Retrograde region (shaded area). Any region where condensation or
vaporization occurs in reverse to conventional behavior, i.e., retrograde
condensation in which liquid is condensed upon either lowering the pres
Liquid
,.
Vol %
~
liquid ~~0\r.
"f:>\e
.,,.. ...
~~'O 010
... ! ...
,oo ......... I L
Multicomponent Systems
Naturally occurring hydrocarbon systems are composed of a wide range
of constituents. These constituents include not only the paraffin series of
hydrocarbons but components from various other series. The phase behavior of a hydrocarbon mixture is dependent on the composition of tli6
mixture as well as the properties of the individual constituents.
A phase diagram for a multicomponent system is shown in Fig. 46.
Before discussing the significance of the diagram, a number of important
physical concepts associated with phase diagrams must be defined.
Critical point (C of Fig. 46). That state of pressure and temperature
at which the intensive properties of each phase are identical.
Critical temperature (C). The temperature at the critical point.
Critical pressure (C). The pressure at the critical point.
lntewfive properties. Those properties that are independent of the
amount of material under consideration.
Extensive properties. Those properties that are directly proportional to
the amount of material under consideration.
Bubblepoint curve. The locus of the points of pressure and temperature
at which the first bubble of gas is formed in passing from the liquid to the
twophase region.
Dewpoint curve. The locus of the points of pressure and temperature at
which the first droplet of liquid is formed in passing from the vapor to the
twophase region.
Twophase region. That region enclosed by the bubblepoint line and
dewpoint line wherein gas and liquid coexist in equilibrium.
Criconde:ntherm (M). The highest temperature at which a liquid and
vapor can coexist in equilibrium.
,;~""
,,~'J
I
,,. ,
I ,,. ... '
...
,' '
,,
I
I
d:
!
,,
Separator
I
I
7i
I
I
I
10
I
J
,/
,J
J
I
I
I
I
I
I
I
I
......... z
,, '
,,
,.,r. .
,'
, ,'
IE
(,,1:/~e
."I
o'
oe"'
Gas
I
I
I
I
I
I
I
1r,
I
I
I
I
I
7i1
Temperature
FIG. 46. Phase diagram to illustrate nomenclature of retrograde condensation.
I
!
222
and the dewpoint curve represents zero per cent liquid by volume. The
shaded areas represent regions of retrograde phenomena. The region defined by points C, B, M, D is the region of isothermal retrograde condensation.
In oilfield nomenclature multicomponent systems are broadly classified
as oils or gases. These broad classifications are further subdivided depending on the changes in state of the hydrocarbon mixture in the reservoir and
the surface yield of hydrocarbon fluids.
Gases. Systems which exist in the gaseous state in the reservoir are
classified as gases and subdivided into
1. Condensate or retrograde gases
2. Wet gases
3. Dry gases
The phase diagram and prevailing reservoir conditions determine the
classification of the system. If a reservoir contains a mixture having a
phase diagram such as that of Fig. 46, the reservoir temperature is between the critical temperature and the cricondentherm and the initial
reservoir pressure is equal to or greater than the dewpoint pressure. Then
the reservoir contains a condensate gas.
A reservoir temperature and an initial reservoir pressure corresponding
to point B of Fig. 46 are typical of reservoir conditions associated with
condensate gases. The hydrocarbon mixture originally exists as a singlephase dewpoint gas. Fluids produced from the reservoir are brought to
the surface and are separated at separator conditions such as shown on
the diagram.
Two phenomena associated with the production are of interest. As
fluids are produced, the reservoir pressure declines and isothermal retrograde condensation occurs in the reservoir, since the pressure decline occurs
along the path BD. The produced fluid is subjected to both pressure decline and temperature decline. Liquid is accumulated in the separator as a
result of normal condensation associated with a decline in temperature.
A portion of the phase diagram of a naturalgasnaturalgasoline mixture
is presented in Fig. 47. The diagram is more typical of a condensate gas
than that of Fig. 46. Although the range of investigation did not define
the cricondentherm, it is obvious that both the cricondenbar and cricondentherm exist at higher temperatures than the critical temperature. This
is commonly true of condensate gases. The region of isothermal retrograde
condensation is larger for such a material than for that shown in Fig. 46.
Another important observation which can be made from both phase diagrams discussed is that the reservoir temperature must be between the
critical temperature and the cricondentherm for the fluid to be a condensate
gas. The relative position of the critical point is determined by the amount
223
I ,,,
 f::;7
''" ~ /"I/
o;t~/ /
/
~~/ /
0
o~""
'0
' \' ~
, s~
'
'
2,40
~ 1,800
~
::::J
l"
ii.
1,60
oW
1,400
i,200
1,000
800
600
L<
./
Vi6
....(5
v
./
.,..
/
I
I
,,,
I/
/
~o
""'
40~0
/"'
__.,,...
~
_I
'
2,200
2,00
'
::::~
'
...... i.

\ /
oRun A
.&Run 8
5
30
HO
oo
ITT
m m
Temperature, F
FIG. 47. Phase diagram for naturalgasnaturalgasoline mixture. (From Katz and
Kurata.s)

224
Temperature

225
that the separator conditions lie in the twophase region and a liquid phase
is condensed in the separator. Wet gases ordinarily differ from condensate
gases in the following respects:
I. Isothermal retrograde condensation does not occur in the reservoir
during pressure depletion.
2. Separator liquid yields are lower than for a condensate.
3. Less heavy components are present in the mixture.
A dry gas is comprised largely of methane and ethane with small percentages of heavier components. A phase diagram of a dry gas, together
with typical reservoir and operating conditions, is shown in Fig. 49. The
separator conditions as well as the reservoir conditions lie in the singlephase region. Hydrocarbon liquid is not condensed from the mixture
either in the reservoir or at the surface. Dry gases may contain water
vapor, which will condense. "Dry" in this instance means free of hydrocarbon liquids, not necessarily free of water.
Oils. Hydrocarbon mixtures which exist in the liquid state at reservoir
conditions are commonly classified as crude oils and subdivided on the basis
of liquid yield at the surface into low and highshrinkage oils.
A phase diagram for a lowshrinkage oil is shown in Fig. 410. Two
characteristics are apparent. The critical point lies to the right of the
Pressure depletion at
reservoir temperature
Pressure depletion
_   ......,
/
at reservoir t7eperature
'
'\
I/
I
I
I
f
I
Liquid
75
/ /
TA
I
I
I
I
I

_::::;.  
Gas
of
1
I
I
J
I
Gos
/
&Separator
Temperature    
1
I
?'/50
,,.
_,../250,,.
feparotor
"I
J
J
liquid
J
I
Temperature 
cricondenbar, and the quality lines (volume per cent liquid) are closely
spaced near the dewpoint curve. Furthermore, at atmospheric pressure
and reservoir temperature, the mixture is in the twophase region. At separator conditions, substantial liquid recoveries are obtained even though
the liquid volume per cent is quite low. This phenomenon is caused by the
226
mining the behavior along the isotherm corresponding to reservoir temperature and a group of tests at various separator conditions.
Characteristic analyses of typical reservoir fluids are presented in Table
41. These data are to be considered typical but not necessarily characteristic of the classes. A wide range of possible compositions and reservoir
conditions exist for naturally occurring hydrocarbon accumulations. Therefore, each reservoir fluid presents a different problem in analysis and classification.
The gasliquid ratio that is initially produced and the API gravity of
the produced liquid are indicative in general of the classification of the
reservoir fluid.
Dry gas is indicated by lack of condensed fluids at separator conditions.
Wet gases are usually indicated by gasliquid ratios of 60,000 to 100,000
cu ft per bbl with liquid gravities higher than 60APL Condensate gases
yield gasliquid ratios of 8,000 to 70,000 cu ft per bbl with liquid gravities
between 50 and 60APL
TABLE 41. COMPARISON OF COMPOSITION AND LIQUID YIELDS OF
HYDROCARBON RESERVOIR FLUIDS7
Fluid
Pressure depletion at
reservoir temperoture_:f:'
' ....
'\
Liquid
\
I
I
227
Condensate gas,
mole 3
Lowshrinkage oil,
91.32
4.43
2.12
1.36
0.42
0.15
87.07
4.39
2.29
1.74
0.83
0.60
57.83
2.75
1.93
1.60
0.20
3.08
33.15
Methane
Ethane
Propane
Putan es
Pentanes
Hexanes
mole%
1.15
1.59
Hep tan es
and heavier
I
I
Gravity
of
0 /
liquid,
OAP!
Gas
Reservoir conditions
Gasliquid
ratio, cu ft
Temperature,
Pressure,
per bbl
F
psi
Dew Bubble
point, point,
psi
psi
Temperature    
both in the reservoir and at the surface. A highshrinkage oil may be either
saturated (point A) or undersaturated (point A').
The various classifications of hydrocarbon fluids may be characterized
by composition, API gravity of liquid yields, and gasliquid ratios as well
as by phase diagrams. In fact, usually only a partial phase diagram is obtained on laboratory analysis of reservoir fluids. This consists of deter
Gas:
Wet gas
Condensate gas
Oil:
Low shrinkage
High shrinkage
65
55
67,000
18,500
160
203
1,700
4,810
38
58
900
2,700
211
203
4,750
4,700
4,470
4,600
3,855
    
228

Reservoir gos
~
I

229
reservoir consists of an oil accumulation with a gas cap. The gascap gas
is classified as associated free gas and is usually in equilibrium with the
contiguous oil accumulation. Thus, the gas is at its dew point and the
liquid at its bubble point. This is shown schematically in Fig. 412, in
which the phase diagrams for the equilibrium phases are superimposed
on the original phase diagram for the total mass of hydrocarbon in the
reservoir. The equilibrium gas contains larger percentages of light hydrocarbons and lesser percentages of heavy hydrocarbons than does the eqUIlibrium liquid. The gascap gas may be dry, wet, or condensate, depending
on the composition and phase diagram of the gas. That shown in Fig. 412
is a wet gas.
If the reservoir temperature corresponds to T, (Fig. 46) and the reservoir pressure to that for point B, then as previously mentioned the
reservoir fluid is a condensate gas. The gas is saturated, or at the dew
point. However, if initial reservoir conditions correspond to point A, the
reservoir contains a singlephase gas which is. several hundred pounds per
square inch above the dewpoint pressure and is undersaturated.
For a reservoir temperature of T 3, such as at point F, the reservoir contains a wet gas.
From the foregoing discussion it can be observed that hydrocarbon mixtures may exist in either the gaseous or liquid state, depending on the
reservoir and operating conditions to which they are subjected. The
qualitative concepts presented may be of aid in developing quantitative
analyses.
I
PROPERTIES OF THE GASEOUS STATE
I
I
Reservoir
liquid
l,' ,/
\Ct
//F reservoir
lnifio/ .
/"' / I
I
,,
,,,,.,,,,.
,,,,
,,,,,.,,,
,,..'""SepOrator 1 1
"/
,,
,,
1 I
/1 I
pressure
I
I
I
II
I
I
I
I
I
Temperature   
v o:p1
or
PV= C'
for T = constant
1
230
P=KT
V=K'T
for V = constant
for P = constant
C', K, and K' are constants of proportionality dependent upon the units
used for volume, pressure, and temperature and the natur'e and weight of
gas present. The pressure and temperature in Boyle's and Charles's laws
are in absolute units.
From the above laws it is possible to derive the general or perfect gas
w=M
where M is the molecular weight. Substituting for win Eq. (43),
law. In brief it can be shown that by using only one part of Charles's law
and Boyle's law, it is possible to write for a unit weight of gas
at T1 from Boyle's law
v2T1
Vn==
T,
From which
= P2v2
T1
R'
T,
(41)
Since the conditions were chosen at random, it can also be shown that
P1v1
T1
PaV3
= R'
T,
where conditions P.,, 1 va, and Ta represent any other state of pressure, volume, and temperature. Therefore, the above can be generalized as
Pv = R'T
MR'T
v = p
From Avogadro's law, for a given pressure and temperature, V must have
the same value for all ideal gases. Thus, MR' must be a constant. This
where v.,.. is the specific volume at P2 and T1, v2 is the specific volume at
P2 and T2. Then v1 is the specific volume at P1 and Ti.
P1v1
p,
PV = MR'T
or
P1v1
(42)
the type of gas and the units used. The gas constant for a number of gases
fact has been verified by experiment on gases such as oxygen, helium, and
nitrogen. The product MR' is called the universal gas constant and desig
R = 1,544 ftlb/(mole)(F)
pressure and 32F, R' = 96.2 ft lb per (lb)( 0 R), with P in pounds per
and if the pressure is in pounds per square inch, other units as above,
square foot absolute, v in cubic feet per pound, and T in degrees Rankine.
If both sides of Eq. (42) are multiplied by w, the weight of gas, then
or
231
Pwv = wR'T
PV = wR'T
(43)
i~!4
V
RT
Specific volume v = w = p M
(46)
  .
232


v.ARIOUS
Pressure
Volume
Atm
Atm
Atm
Liters
Cu ft
Psi
Psi
Cu ft
Cult
Cc
FOR
UNITS
Temperature,
Kelvin
Kelvin
Rankine
Gmmoles
Gmmoles
Lbmoles
Rankine
Lbmoles
Lbmoles
82.057
0.082054
0.7302
10.72
1,544
deg
Rankine
..

thus the density and specific volume of gases are functions of pressure,
temperature, and molecular weight. For a particular gas the conditions of
pressure and temperature must be specified to define the density or specific volume.
The number of impacts per unit time is the reciprocal of the time per
impact, so that the impacts per unit time can be expressed as
1
ii
I= 2L =
Example 41. Calculation of Density from Ideal Gas Equation of State.
Find the density of methane at 0 psig and 60F when atmospheric pressure is 14.7 psia.
M ethane d ens1ty 
l 4_. 7 (l6)
(
)  O.04 122
10 72 520
M ethane dens1ty
. =
647 (l 6)
_ (
) = O. 1962
10 72 492
233
(rnIJ)
2rnIJ
Therefore, the change in momentum per second per molecule is the product
of the number of impacts per unit time and the change in momentum per
impact:
mV 2
<27rWl 2L
To obtain the total rate of change in momentum at one wall it is necessary to consider all the molecules which are hitting the wall. The total
change in momentum. per second is force.
Force=
n1 mV2
where n' is the number of molecules. Since force equals the product of
pressure and area, the pressure on the wall is
n' mi!'
2n'
P=3y+V=av
as
(12mif')
L3 =volume
PV
2
;'
(~mv)
234
&mlJ
n'
P' =a
V'
or
where K is a constant of proportionality; that is, as the temperature is increased, so is the kinetic energy of the molecules. Then
2
PV = Kn'T
3
It can be shown that K is a constant independent of the gas. If T remains
PV = constant
which is Boyle's law.
Charles's law can also be obtained from the equation of state by arbitrarily letting the pressure or volume be constant.
Let PV
1(~KA )r
PV = nRT
235
.
n'
Slllce A= n
V2 (V  nb) = nRT
(P + n'a)
(p + ;,) (V  b) =RT
(44)
(47)
(48)
a,,
Carbon dioxide
Ethane
Hydrogen
Methane
Nitrogen
Oxygen
Formula
bt
co,
3.59
5.49
0.244
2.25
1.39
1.36
0.0427
0.0638
0.0266
0.0428
0.0391
0.0318
C2HG
H,
CH,
N,
o,
GASE'%
*a in atmliter2 mole2.
t b in liter moleI.
The. perfect gas law holds rather well for the socalled "permanent"
gases m the lowpressure ranges. Van der Waals's equation applies over
a greater pres~ure range for the same gases. The increased range of pressure does not include pressures of the order of the reservoir pressures encountered in many oil and gas fields.
Furthermore, the equation contains two arbitrary constants which depend on the properties of the gas and limit the usefulness of van der Waals' s
equation in describing the behavior of mixtures of gases. To a large extent
the constants a and b depend on the size of the molecules. Therefore in
a mixt~re of gases it is evident that the attractive forces depend on ~he
proportion of the varioussize molecules present. No adequate method has
been devised for evaluating the effect on a and b of the molecular interaction in mixtures.


236
The BeattieBridgeman equation of state, involving five arbitrary constants, describes the behavior of pure substances with considerable precision. It, too, is limited in application for mixtures of gases. To apply
this equation to mixtures requires the simultaneous solutions of equations
comparable to the number of constituents in the mixture.
The BeattieBridgeman equation of state for a pure substance is as
follows:
237
(49)
where P
T
V
=
=
=
pressure,
temperature, K
volume, liters per mole
and Ao, Bo, a, b, care constants empirically defined for each pure gas.
The Benedict, Webb, Rubin9 equation of state for a mixture of hydrocarbons
P = RTPm
+ ( BRT 
A 
where B
A
C
b
a
c
= (Zy,b,*)'
= (Zy,a,")'
= [Zy,c,"]'
= [Zy;a<;"]'
a)pm3
(410)
= Zy;IJ,
= (Zy;A,")'
=
'Y=
(Zy ,C /')'
[Zy,y,>']'
and Bi, Ai, Ci, bi, ai, Ci, ai, and 'Yi are constants defined empirically for the
ith component; Pm is the molal density; P is the absolute pressure; R is
the universal gas constant; e is the base of the natural logarithm; and Tis
the absolute temperature.
The petroleum industry has adopted the concept of a compressibility
factor Z for describing the behavior of mixtures of gases at moderate to
high pressure. The compressibility factor Z is simply a correction factor
to the perfect gas law; that is,
(411)
PV = ZnRT
and, by definition,
= PV = PV
(412)
P 0 V 0 nRT
Po and Vo are the pressure and volume, respectively, which would be calculated from the perfect gas Jaw.
Pressure, psio
238
Charts such as Figs. 413 through 416 can be prepared from experimental data for a particular gas. Compressibility factors determined from
such charts can be used together with Eq. (411) to calculate the volume
of the gas.
t.1
239
Propane
"C
"f
560 1,040
480 596
440 2 4
52
J60 680
320 508.
JOO "72
968F
75 __ !,..__
6
680
zsO
36
z60 500
.,
,,
""
...
0.5
.::.
0.4
0.3
0.2
0.1
7,000
8,000
t~
9,000
10,000
Pressure, psia
Densitles of the gas can be deterrnined from the same experimental data
from \Vhich the compressibility factors were calculated. For pure gases,
charts correlating the density \Vith pressure and temperature are perhaps
as useful as correlations of compressibility factors. In Figs. 417 through
420 are presented density correlations of methane, ethane, propane, and
normal butane. The twophase regions are outlined by dashed curves on
500
1,000
1,500
Pressure, psia
the charts for ethane, propane, and normal butane. It may be noted that
the density of the gas approaches that of a liquid at elevated pressure.
Mixtures of Gases. Natural gases are mixtures of hydrocarbons which,
as stated earlier, may be characterized by composition. The composition
of any mixture may be reported in terms of per cent by weight, per cent
by volume, or mole per cent. For gases, according to Avogadro's law, mole
and volume per cent are identical, since 1 mole of any gas occupies the

240



0.6
oc
520 968
480 896
440 824
o.1
400 752
0.08
0.06
J80 716
J60 580
'o.o ...._
;zo
f:
50B
~ 0.02
512
C>
(}.0 1
,,o
0.008
0.006
0.6

0.004
s.ooo
.J.Ooo
.?.ooo
'SOO
'OOO
I
800
500
500
<oo
Joo
0
''o
r._
"'/'
0.. <>:
"
raooo
~ ~ ~ :::::::
;40 544
,,, ,,o"'
"'
50,000ps;a
.J0.000
0. 2~
"F
300
'
o.4
nbutane
'00
eo
 r r.
0.002
0.5
0.00 I 0
100
200
60
300
400
"'
500
600
700
800
900
1,000
1,100
1,200
Temperature, F
0.4
1.00
oc
0.3
,.,,'
0.2
Cl
' 0
400
390
360
340
0.1
80 100
Pressure
500
1,000
f,500
Pressure, psia
FJG.
:t
~
f:
320
300
00
sooo
0.96
....
'
.....
'
...__
.......
."'.
 

r
100
200
0.2
.?.ooo
0.1
0.08
0.06
.~oo
t.ooo
0.04 .............
Q
oo
oo
f:
0.02 ~
400
Joo
C>
Jo
0.01
0.008
0.006
'50
'O"
80
0.004
5n
so
40
0.002
30
<o
300
400
500
u
0
1 6'00

0.4
440
0.6
~
~
520
480
0.98
~
,1:ii
50,000 DsiO
30,000
'0.0oo
600
700
800
900
1,000
Temperature, F
l,100
o.oot
1,200

50,000
~I\\
,\'""'
~
0
@
"'"
="
~
~
.' '
~

%
'
' .......
"'
""'


100
 
O.t
0.08
0.06
300
400
;
~
~
~
0.02
<oJ
0 .002
600
700
800
900
1,000
1,100
0 .OOf
f,200
Temperature, F
<
"",
<:'.".
'
_o
_,,,"""%
r....
/!:::_
,t
'
'
I .....
'
....
~~
;;:;
10.000
.....
=I
o.s
50,000 psiQ
\'

30,00_0
sooo
i!oo0 
~
!'..._
'OOo
oo
~
60o

30
40
30
16.04
30.07
44.09
I.87
J.33
068
3.88
48.2
34.3
17.5
100.0
c,
c,
c,

v = v, + v, + v, + ... + v. = .l v,
0.6
11
0.4
'
oo
""'
~
Mole%
Component
For many purposes the physical constants of pure_ hydrocarbons are required. These constants are tabulated in Table 44 for the paraffin hydrocarbons through normal heptane.
The equation of state (411) can be applied to a mixture of gases by
means of Amagat's law of partial volume. Amagat's law states that the
total volume of a gaseous mixture is equal to the sum of the volumes of
the individual components of the mixture, all at the same temperature and
pressure; i.e.,
0 .004
'
.....,__ ..........._
(4)
(2) + (3)
Moles/100 lb
(2)
0 .Of
0.008
0 .006
20
500
Weight%
(3)
Molecular
weight
(1)
u
0.04
'OO
o
60
so
40
_,
0.2
'5
200
ooo
oo
oo
soo
oo
'Oo

243
example calculation of the mole analysis of a gas when given the weight
analysis is given in Example 42.
0.4
'.ooo
I.
....._ ,___
.ooo 3 0.ooo
.
'. ~
~oo
11
0.8
0.6
0.2
0.1
0.08
0.06
0 .04
0.02
'50
I
'OO
o
60
so
<o
20
=          Temperature, F
0 .Of
0 .008
0 .006
.z
QI
~
~
y,V = V;;
where
Yi is the mole fraction of the ith component in the gaseous phase, V is the
volume of the system, and Vi is the partial volume of the ith component.
The application of this principle to calculation of the volume of a gaseous
mixture is given in Example 43.
Example 43. Gas Volume Calculated Using Partial Volumes. Determination of the volume at 1,000 psia and !04F occupied by 1,000 scf of
gas whose composition is given below:
Gas analysis
Mole fraction
v.,
y;
sci
0.70
0.20
0.10
1.000
700
200
100
0. 004
0. 002
~00
Methane
Etp.ane
Propane
Z at
1,000 psia
and 104F
0.918a
0.274b
0.236'
Pa Tr
v.
Pr Ta
Vi at
1,000 psia
and 104F
11.13
3.18
1.59
15.90
10.217
0.871
0.375
11.463
0.
245
Volume at 1,000 psia and 104F calculated as if the mixture were a perfect
gas is 15.90 cu ft. Actual volume occupied by gas at 1,000 psia and 104F
is 11. 463 cu ft .
11.463
Zmix =
_ = 0.721
15 90
,._
b)
(49)
0"" ~
~ 0
a;
~
+ a(V 
,..;
244
246
That is, the change i:Q. pressure with a small change in volume is zero
(aPjOV),, = 0, and the change in slope with the change in volume i~
zero, (a'P/aV'),, = O.
Solving van der Waals's equation for pressure yields for 1 mole
p =
v,a + vRT
b
(413)
aP)
(+2a
( av c11 = Vc3
RT,
(Ve  b) 2 cp
By using the values of a, b, and R stated in terms of the critical properties of pressure, volume, and temperature of the gas involved, it is possible
to rewrite van der Waals's equation in the following form:
Reduced volnme
2RT
RT
Vr=V,
(416)
which reduces to
Equating the two equations for a and solving for b in terms of Tc, Pc,
Ve, and R,
2 (V,  b)' =
(415)
a= V,;' RTc
3 (V,  b)'
V.'
~P.V, T
3 T,
and substituting in Eq. (415) for the pressure temperature and volnme,
obtain
also
6a
T
Reduced temperature = T, = T,
RTcVc
a= 2(V,  b)'
(
+ 3P.V.')
(v  3! V)'
V'
a'P)
( aV' ,,
247
Vc4 RT,,.
3 (V,  b)'
V,  b = %V,
b = }iV,
= ~P,V,
3 T,
(414)
2 v.
(417)
=ST,
from which
a= 3PcVc2
1)
,P.
11
yJ'..
and
pTc =
i1
YiTci

248
0.
0.
S CH4_/
C3 Ha
~~0.7
~
tl
0.6
C5 H;{
Tr,
:0
0.4
Q3
0.2
~
'
Co; H12
C,. Ha;
Tr,12><
0.91\'Tr1.0 '\
~
~~
I
'
Tr=1.1
""
rL
C., H12
C3 Ha
C~4
C5 H12
C3 Ha
Tr  z.o
'8
''
,6
1.5.
 '
1 CH4 C3 Ha
0.8
CH4
C5 Hi
~
0.7
0.8 1.0
1.2
1.4
1.6
1.8
Reduced pressure,
2.8 3.0
fJ.
;pc
where
pTc =
Pei
C3 H8
01
0
0
249
Tr=1.5
~~
\Jj \ .\ '
~ 0.5

...
and
Tei
Yi =
n =
pseudocritical pressure
pseudocritical temperature
critical pressure and temperature respectively of ith
component
mole fraction of ith component in mixture
number of components
0.6
"""
"l'0.5
Q..
Cl:::
0.4
0.3
0.2
T
,,P, = and
,,P, = ,,P,
,T,
Compressibility factors, experimentally determined, for a large number
of natural gases were correlated with pseudoreduced pressure and tern
perature. The results of these correlations are presented in Figs. 423 tc
4U. Since most natural gases contain large amounts of methane, the
correlations for natural gases are superior to the correlations het,veen individual hydrocarbons such as previously shown in Fig. +22. The petroleum industry has universally adopted the charts of Figs. +23 to 425 to
determine the compressibility factor for use in the equation
PV
ZnRT
(4.11)
Thus, if any analysis of the gaseous mixture is available, the pseudocritical
=
0.1
0.5
1.0
Reduced pressure
Pr
1.5
FIG. 423. Generalized plot of compressibility factors at low reduced pressures. (From
Brown et al.4 )
:a~:e
251
250
r,.2.0
1.10
f.6
.1
~.?.
'
.6
Z.4
It
2.2
~P
lo
0.98
'
1.4
0.99
J.1 .
.L~
r
,:
f.9
f.
1:
.90
0.8
0.97
.f
"'I'
""'
"...,
2
~ 0.6
<?~
0.95
~ 0.5
a.E.
0.94
'',;
'
:c
"'
"
"
;g
<S"
1.6
f.35
...,
'?<90
,J
<4
0.7
0.96
f.45
qo>s
1.5
1!
1.4 ~
E
~~'J
<J'
,g
:c
;;
<..>
cr
...,
,,
0.4
0.93
1.2
0.3
0.25
0.92
1.f
0.91
0.90
0
1.0
0.01
0.02
0.04
Reduced pressure, P,
0.03
0.05
0.06
0.07
Fra. 424. Compressibility factors for gases near atmospheric pressure. (From Brown
et al.')
M ~
j=l
y;M;
(418)
12
11
iO
Pseudo reduced pressure
13
14
150.9
FrG. 425. Compressibility factors for natural gases. (From Brown et al.')
where Mi is the molecular weight of the ith component and Yi is the mole
fraction of the ith component in the mixture.
The gas gravity can be calculated from the average molecular weight.
By definition, the gas gravity is the ratio of the density of the gas to the
density of air, both densities defined at atmospheric conditions. Since the
252
ideal gas laws hold at atmospheric conditions, the density of a gas is directly
proportional to its molecular weight. Thus
G=M
M.
M
28.06
(4~
where G is the gas gravity, Ai is the average molecular weight, and 1lla is
the molecular "\veight of air.
Calculations of the average molecular \veight, gas gravity, pseudocritical
pressure, and pseudocritical temperature are illustrated in Example 44.
Example 44. Calculation of Molecular Weight, Gas Gravity, and
Pseudocritical Properties for Hydrocarbon Gas.
(I)
Component
c,
c,
c,
(2)
Molecular
weight
(3)
Mole
fraction
(4)
(5)
/',
T.
16.04
30.07
44.09
0.70
0.20
0.10
673
343
550
666
708
617
(2) x (3)
11.23
6.01
471.1
4.41
61.7
674.4
21.65
141.6
240.1
110.0
66.6
416.7
Temp, F
Pressure,
68 c2ocJ
60
60
60
60
14.696
14.65
psi a
15.025
14.4
14.7
253
Volume of
1 mole, cu ft
385.51.
380.69
371.35
387.47
379.56
included to emphasjze the deviation of real gases from the perfect gas law.
The volume of gas at 1,000 psia and 104F as calculated from the perfect
gas law is in error by more than 20 per cent.
Method 2, treatment of the gas using additive volumes and compressibility factors of individual components, v.ras illustrated in a slightly different form in Example 41.
Method 3, treatment of the gas using additive volu1ne~ and densities of
the individual components, is simply a variation of method 2, as the density
curves were plotted from the same data from \vhich the compressibility
curves were plotted. The values obtained in Example 45 from these two
methods are in very close agreement, certainly \Vithin the accuracJ of reading the charts.
Both methods 2 and 3 are limited in applicability by the lack of data on
heavier hydrocarbons which have t'INophase regions extending across temperatures of interest in oilfield applications.
The use of the pseudoreduced concepts and the compressibilityfactor
chart for natural gases is illustrated in method 4 of Example 45. The
values obtained differ about 10 per cent from the values from methods
2 and 3. The difference can be attributed largely to the composition of
the gas selected. The generalized charts include data from gases having
heavier components and higher concentration of methane present. Therefore, method 4 is more applicable to gases having more methane and a
greater variation in other hydrocarbons than the gas in the example.
Example 45. Methods of Calculating Volume Relations for Mixtures
of Real Hydrocarbon Gases. Calculation of specific volume, density, compressibility factor, and the volume occupied at 1,000 psia and I04F for
1,000 cu ft at 14.65 psia and 60F of a gas having the composition given
in Example 43:
l. Treated as a perfect gas having an av mo! wt M = 21.65 (from Example 44).
a. Compressibility factor of the mixture Z = 1.000 (definition of perfect gas)


254
.
RT
10.72(564)
b. Specific volume v = MP = 2 1.65 (!,000) = 0.2795 cu ft/lb
.
c. Density P
MP
21.65(1,000) _ _
I__
lb/ f
= RT = 10.72(564)  0.2795  3 578 cu t
21.65(1,000)
I
4 963 lb/ ft
vI MP
ZRT = 0.721(10.72)(564) = 0.2015 = .
cu
=WU
w =M
~: =
21.65
1g:
b. Specific volume v
p1
= <~i
.f',
= 674.4
Therefore
c. Density
16.04(0.7)
2.916
V=
;i3 ~;
i1
+ 30.07(0.2) + 44.09(0.1)
19.020
21.65
31.066
= 0.1990 cu ft/lb
M
M,y,/p;
,T,
and
I,000
674.4
564
.f', = .f', =
= L 4S3
= 0.798
.
c. Density
MP
= ZRT =
1
v1 = 0.2231
= 4.48 lb/cu ft
14.65(564)(0.798)
Therefore
= 11.30 cu ft
M,y,/p,
= 56.9 lb
v = 56.9(0.1990)
Therefore
255
~ = O.l~90 =
5.03 lb/cu ft
The composition of natural gases is usually reported through the heptanesplus fraction. The heptanesplus fraction as obtained from a fractional distillation is a liquid residue which contains heptanes and heavier
hydrocarbons. In the laboratory analysis 1 two properties, molecular weight
and specific gravity, of the heptanes plus are determined. These properties
have been correlated with pseudocritical pressure and temperature of the
heptanesplus fraction. The results of these correlations are presented in
Figs. 426 and 427, which differ only in that the specific gravity is used in
in Fig. 426 and API gravity is used in Fig. 427. These correlations, together with the physical constants from Table 44, enable the engineer to
calculate pseudoreduced properties of natural gases for which conventional analyses are available.
In many instances analyses are notavailable. Therefore, correlations
with gas gravity of pseudocritical properties of natural gases have been
2~6
The difference is about 1.5 per cent. A gas having a wider range of composition would yield a closer check if the appropriate curves are selected.
1,400
Sp.qr.
1,300
a.95
o.9o
o.B5
1"
8 1,200
:c
u
!
1"
'g f,fOO
1,100
o.70
0..
if
i,000
1,000
0..
~ 400
8
0
0..
,;
"'s
Q&o
Q>o
600
Q.9s
Q..90
500
,...
1,200
o.75
1,300
c:
a.BO
= 665 psia
,T,
1,400
g::
c:
257
500
0..
Qrs
300
;=
400
0..
200
100
120
140
160
180
200
220
240
300
if
Molecular weight
densate well fluid curves should be used for gases having large fractions of
intermediates.
The gas gravity can be readily determined in the field by the AcMe
balance method or similar techniques. Thus compressibility data can be
obtained even though a gas analysis is not available. The accuracy of the
correlations of reduced properties v.ith gas gravity can be ascertained by
comparing the pseudocritical pressure and temperature calculated in
Example 44 with those determined from Fig. 430. The gas gravity (from
Example 44) is 0.75. The pseudocritical pressure and pseudocritical
temperature are
200
100
160
Molecular weight
B _ZRT
o V,..P
(420)
258

FUNDAME..~TALS
700
675
:e
" 650
11"
,e
Q_
g
:
0
,'
o
~
Q_
~ 625
"'
~
o'b"
,;
00 5 .00~
450
?e es'
Q_
425
;;;
../
"'
700
.''.?
e
5
0'
600
Q_
sorb''
v;;\ob~e
i(\~
i.\v{ob"'/
sid
400
,; 375
Q_
350
0 0
Q_
=~
0
.g.
, 550
0.6
0.7
0.9
0.8
if
Gos gravity
500
11"
~
675
"'
. .

650
625
Q_
575
Q_
550
.
~
475
' g 450
+:
.g
~ ~ 425
Q_
.,
0
350
325
0.5
~.
""'
B, = C
0.7
0.8
al.~)
During the depletion history the reservoir pressure ordinarily will decline.
As the reservoir temperature is constant, Bg can be defined as a function
of pressure. 1~hus, for a particular gas reservoir and a particular set of
standard conditions,
>
0.6
0.7
Gos gravity (air=1)
FIG.
400
" 375
Q_
0.6
I/
~ 500
~ ~
350
~ 525
400
450
:2
600
700
650
:l
e
""
325
0.5
C"
2.'\9
0.9
1.0
1.f
1.2
Gos gravity
Fro. 429. Pseudocritical properties of Oklahoma City gases. (From Brown et al,')
(~)
where C
RT
=

~
260
261
...
(1)
Component
Mole
fraction
Methane
0.8686
0.0609
0_0261
0.0048
0.0077
0.0031
0.0022
0.0038
0_0228
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
Hexanes
Heptanes plus
(2)
Critical
temp,
OR
(3)
Critical
pressure,
psi a
343
550
666
733
765
830
847
914
11I8a
673
708
617
530
551
482
485
434
415
(1) X (2)
pTc
297_93
33.50
17_38
3.52
589
2.57
1.86
3.47
25.49
391.61
(1)
(3)
584.57
43.12
16.10
2.54
4.24
1.49
1.07
1.65
9.46
,P, = 664.24
Mc,.= 128
SGc.,.
0.8195
T = 600R
B, = C !!_
p
Pressure,
psi a
100
400
700
1,000
1,500
2,000
2,500
3,000
3,500
60U
0.151
0.602
L054
L505
2.258
3_011
3.7G4
4.516
0.985
0.950
0_918
0885
0.823
0.795
0.790
0.805
08!15
5.25B
z
p
0.009850
0.002375
0001314
0000885
0.000549
0.000:~98
0.000316
0_000268
0.000239
B,
0.166415
0040125
0.022200
0014952
0.009275
0.006724
0005339
0.004528
0.004038
Compound
Carbon dioxide
Helium
Hydrogen sulfide
Oxygen
Nitrogen
Water
Formula
co,
He
H,S
0,
N,
H,O
1vlolecular
weight
Critical
temp, H.
Critical
pressure,
psi a
44.01
4_00
34.08
32.00
2802
18.016
548
9.4
673
278
227
1165
1,073
33
1,306
731
492
3,206
z.
z.
y.
.
         
0
0
0
'
CoNTAI:\'IN"G
'"'
fltt
"'
Pressure,
psi a
0
0
0
,,,
,,,
I
1
"
0
0
<
"'
0
0
"'
"
i
i
0
~
,,,
"'
0
.;;;
.;
'{:
;}
0
0
,,,
;;}
0
0
Q
0
0
0
0
8
$
~=.s~!'~c
d
262
a
,,,
ri ~ .
a: "
0
0
0
i1"'
"
""'
~
0
0
N ITIWGEN
,,,0
263
5,00Q
4,750
4,500
4,250
4,00U
3,750
100
130
160
190
1.0010
1.0011
1.0046
1.0047
1.0049
1.0010
1.0055
1.00:18
I.0048
I.0050
1.0014
1.0016
1.0053
1.0063
I.0054
1.0059
1.0061
I.0068
1.0034
1.0048
1.0053
1.0059
1.0062
70
1.0056
1.0032
1.007:~
1.0076
1.0060
1.0066
;~,500
1.0056
1.0081
l.OOS:l
1.0078
3,250
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
14.4
1.0073
1.0101
1.0094
1.0083
l.OOD:J
l.0115
l.0101)
1.0101
1.0085
l.0118
I.OJ 22
1.0124
1.0l31
1.0128
1.0110
l.0108
l.0103
1.0087
1.0101
J.009:l
l.0079
l.0064
I.0000
l.0086
l.0086
l.0086
l.0086
J.0085
1.0079
1.0069
1.0056
1.0000
1.0124
1.014:)
1.0165
1.0162
LO 168
1.0150
l.0116
l.0000
l.01;~5
1.0108
1.0096
1.0000
1.0065
1.0070
1.0070
1.0074
1.0073
1.0076
1.0080
1.0081
1.0081
1.0073
1.0062
1.0047
l.0000
220
250
280
1.0037
I.0044
I.0044
I.0049
1.0034
1.0035
1.0038
1.0040
1.0043
1.0047
1.0049
1.0048
1.0050
l.0050
1.0054
l.0056
l.0055
1.0055
1.0050
1.0038
1.0019
1.0000
1.0046
1.005:3
1.0053
1.0053
1.0057
l.0059
1.0054
I.0058
l.0055
1.0057
1.0054
1.0061
1.0064
1.0065
1.0066
1.0066
1.0068
1.0064
1.0053
1.0038
l.0000
1.0051
1.0054
1.0055
1.0055
1.0055
1.0052
1.0049
J.0040
1.0027
1.0000
1.0052
~
"
"iip
% (25.013 mass %)
added nitrogen
Additive volume correct.ion factors C at indicated temperature, F
0.
"I
'2
"'
5,000
4,750
4,500
4,250
4,000
3,750
3,500
3,250
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
14.4
1.0035
1.0048
1.0055
1.0065
1.0076
1.0103
l.0136
1.0173
1.0201
1.0236
1.0264
1.0288
I.0314
1.0319
1.0322
l.0284
1.0235
1.0000
1.0079
1.0079
1.0090
l.0106
1.0120
1.0137
l.0158
l.0182
l.0204
1.0222
1.0233
1.0240
1.0248
1.0250
1.0239
1.0199
1.0172
1.0000
!.0088
!.0101
1.0107
L0ll6
l.Ol:l4
1.0149
I.0161
1.0176
J.0190
J.0201
1.0199
1.0199
1.0202
1.0195
1.0177
1.0157
1.0134
1.0000
1.0086
1.0095
1.0104
1.0115
1.01:27
1.0135
1.0146
1.0159
l.0163
1.0166
1.0173
1.0175
1.0170
1.0160
1.0147
1.0134
1.0109
LOOOO
l.0089
1.0096
1.0104
1.0111
1.0122
1.0132
l.0139
1.0142
1.0146
1.0147
1.0152
1.0153
1.0147
l.0140
1.0132
1.0117
1.0094
1.0000
1.0093
1.0098
1.0106
l.0111
1.0116
1.0121
1.0123
1.0125
1.0129
1.0134
l.0131
1.0125
1.0117
1.0115
1.0108
1.0092
1.0092
1.0095
J.0103
1.0107
1.0112
J.0115
1.0113
J.0113
1.0113
J.0114
J.0111
I.0107
1.0102
1.0098
J.0091
1.0076
1.0071
1.0071
1.0075
1.0079
1.0088
1.0092
1.0096
J.0094
1.0096
1.0092
1.0092
1.0093
1.0090
1.0087
l.0079
1.0000
I.0000
1.0000
~~
264

z = cz.
FUNDA~!ENTALS
___/
(422)
48.
18,280 mole
nitrogen
Temp, F
70
100
130
160
190
220
250
280
Occurs at
pressure,
psia
Value of
1,800
2,000
2,200
2,400
2,400
2,800
3,750
3,500
7,907 mole%
nitrogen
Occurs at
pressure, psia
Value of
1.0322
1.0250
1.0202
1.0175
1.0153
1.0134
1.0115
1.0096
2,200
1,800
2,800
2,2002,800
2,0002,200
2,000
2,2002,600
2,400
1.0165
1.0135
1.0110
1.0086
1.0081
1.0068
1.0055
1.0056
mums ar~ i~~icative of the error associated with using the additive volume
compress1b1hty factor Za \vithout correction. The maximum value of C
and the pressure at \vhich that
3
maximum occurs are tabulated in
Table 48 as a function of tempera1.02
ture. In general, less than 2 per
",
c
cent error in the additive compressI'1.0
ibility factor is possible at temper\
atures in excess of 130F.
\
too
The effect of composition on the
0
100
N i~~ogen ~~ mixt~~. mol~o %
additive volume correction factor
is illustrated in Fig. 432. Using
F1G. 432. Variation of additive volumeEilerts's data and procedure, four
correction factor at a constant pressure
and temperature due to nitrogen concen points are known for the value of
tration. (Aftrr Eilerts et al.13 )
C, at a constant temperature and
pressure, as a function of the nitrogen concentration. By definition of the correction factor, C must be
1.0000 at 0 and 100 mole 3 nitrogen in the mixture. Values of C are
,/
~
265
available from Table ~7 for 7.907 and 18.280 mole 3 nitrogen. The
curve of li'ig. +32 \Yil.8 constructed from this type of information. 1~he
dashed portion represents the extrapolation necessary. The maximum
was estimated from a similar curve presented by Eilerts 1s \Vhich included
data up to 56 mole 3 nitrogen. The maximum of that curve occurred
at about 46 mole 3 nitrogen.
The computation of the compressibility factor by Eilert8' method and
by the la\Y of corresponding states is presented in Example 47 for a natural
gas containing 10 mole 3 nitrogen. The Z factors compare as follo\vs:
Z (Eilerts's method) = 0.892
Z (corresponding states) = 0.885
Difference = 0. 77 per cent
(,T,),
620
3,000
z.
+ 0.90000(0.86)
c = 1.0104
z = cz. =
1.0104(0.88255) = 0.89173
<).
Eilerts calculated a compressibility factor of 0.885 for the same gas composition reported in Example 47. The difference in the Z factor ca.1culated
by Eilerts and that obtained in Example 47 resulted from slightly different critical properties and reading of the gascompressibilityfactor curve.
It then becomes apparent that if the engineer exercises due care, he can
have about a I per cent error regardless of the calculation method used.
Carbon Dioxide, The effect of carbon dioxide on compressibility factors
of hydrocarbon mixtures has not been so extensively investigated as has
that of nitrogen. Sage and Lacey15 " have presented data on the binary
~~~~



267
systems methanecarbon dioxide and ethanecarbon dioxide. They suggested that a computation procedure based on partial residual volumes
utilizing their basic data be used to correct volume calculations for impurities. The partial residual volume method is not presented in this text1
but a carbon dioxide compressibilityfactor chart developed from the data
of Sage and Lacey is presented in Fig. 433. This chart can be used to cal1.2
I I
I
I
1.0
....
l*i

...
~"i'.'=!~':'1.0.00.~~
"<t'~c:i~_C':JC\10
C'l
 '="' ro
~
280F
226F
0.6
"~
~
I I
'40F
0 0.8
t;
~1...,,oou:i'c<:i
~r::
F
F
I l
160"F .......
too
0;4
"
0.2
1,000
2,000
3,000
7,000
8,000
9,000
10,000
F1a. 433. Compressibility factor for carbon dioxide. (From Olr.k et al.u)
oc:.~~1C'1000C'10
O'TOOc::Nu:iooo...,..
Otr.OOQ"'1<"'f<IN.c:i
ov000000
oc.:00000000
0000000000
z. =
Yco,(Zco..)
+ (1
 Yeo,) (Z,)
(421)

268
   

Component
(I)
Mole
fraction
Yi
0.0236
0.8481
0.0595
0.0255
0.0047
0.0075
0.0030
0.0021
0.0037
0.0223
Carbon dioxide
Methane
Ethane
Propane
!sobutane
nButane
Isopentane
nPentane
Hexanes
Heptanes plus
(2)
(3)
T,,, 0 R
Pc, psia
548
343
550
666
733
765
830
847
914
1073
673
708
617
530
551
482
485
434
415"
1118
(4)/
y,Tc
(I) X (2)
(5)
Yipe
(I) X (3)
12.93
290.90
32.73
16.98
3.45
5.74
2.49
1.78
3.38
24.93
pTc = 395.31
25.32
,P,
570.77
42.13
15.73
2.49
4.13
1.45
1.02
1.61
9.25
673.90
OF
= ,T, =
600
395.31
1.52
0.805
+ (1  Yeo.) (Z,) =
+ 0.786 = 0.797
Yco.(Zco,)
0.011
0.0236(0.453*)
(0.9764) (0.805)
The validity of the two methods presented in Example 48 are compared
in Table 49 with observed data and with results from the residual volume
method of ca!culation. All three methods of computation yield values
which are about 2 per cent below observed data. As the accuracy of the
three methods is comparable, the method of corresponding states is preferred because of its simplicity of application. If this method is applied
with care, the ratios of observed Z to calculated Z reported in Table 49
can be used to adjust calculated values of Z for greater accuracy. For
gases containing more than 4 mole % carbon dioxide, the deviations computed from observed values may be greater than indicated in this comparison. Laboratory tests should be made on such materials if accuracy greater
than about 4 per cent is required.
From Fig. 433.
Zco2
Observed,a
Method of
residual vol"
'
Method of
corresponding
states
Additive
vol method
z;z,
z,
Z/Z,
z,
Z/Z,
100
500
1,000
2,000
3,000
0.841
0.580
0.299
0.411
0.928
0.860
0.775
0.787
0.916
0.844
0.753
0.758
1.01
1.02
1.03
1.04
0.915
0.847
0.750
0.760
1.01
1.02
1.03
1.04
0.919
Q.842
0.747
Q.763
1.01
1.02
1.04
1.03
160
500
1,000
2,000
3,000
0.889
0.759
0.479
0.479
0.951
0.908
0.856
0.860
0.941
0.893
0.836
0.836
1.01
1.02
1.02
1.03
0.945
0.895
0.830
0.830
1.01
I.QI
103
l.04
0.944
0.894
0.830
0.830
1.01
1.02
1.03
1.04
500
1,000
2,000
3,000
0.921
0.838
0.684
0.607
0.967
0.940
0.910
0.916
0.957
0.926
0.889
0.882
LOI
1.02
1.02
1.04
0.962
0.928
0.888
0.885
LOI
LOI
1.02
1.04
0.962
0.929
0.886
0.886
1.01
LOI
1.03
1.03
220
p
 .._  3,000  4 4"
,,,_  ,P.  673.90  . "
Pressure,
psia
z,
,T.
269
Mole fraction"
Methane
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
Hexanes plusr.
Carbon dioxide
0.83845
0.06366
0.03744
0.00390
0.00951
0.00160
0.00110
0.00230
0.04204

1
270
Z. = Zco,(Yco,)
z = c.z.
+ Z.(y,) + (1
 Yeo.  y,)Z,
(423)
1,2 ,....,..~
,~,r~.~~~~~~r~.~~~~~T,~rr~
,T~
,~I
271
p =
(424)
where P is the pressure of the mixture and Pi is the partial pressure of the
ith constituent.
It follows from this statement that the volume fraction of a constituent
in the vapor phase is given by
P,
y, = p
P,
i=l
(425)
~~40i11'++il+l++ll+lll+ll+ll+l++lL40F
1.0
~.[~
""
:;
71 1..too~;
t00k
~
{t'H;++f++e++1+++1++1Jf60F
,. 3,/0!
,,,,280~F :
f
Q8
,g
~
"
'"
'
,2~/JF
?20L 1.34d f
16 F
'
220F
Cl6
!;,
E
0
<.>
where Yi is the volume (or mole) fraction of the constituent in the vapor
phase.
The partial pressure of water in the vapor phase is its vapor pressure at
the prevailing temperature. Thus
(426)
The laboratory analysis can be corrected for water content as follows:
0.4
(427)
Cl2
0~~'L..C..LLULLLLLL'_l_.Ll..J_l...J._J_LL_LJ_l__LJ_LLJ_L.LL_Ll...J._j_J
1,000
2,000
3,000
7,000
8,000
9POO 10,000
'vhere (yi)c is the corrected mole fraction of any constituent other than
water and (y,)L is the mole fraction of that constituent from the laboratory analysis.
The water content of a gas is usually expressed. in pounds of water per
million standard cubic feet of hydrocarbon gas. This can be calculated
from the mole fraction of water in the corrected analysis.
The weight of water per mole of the mixture is given by
Yw(Mw)
~
272
~

Temperature,
w.. =
Pressure,
OF
p8ia
60
70
80
90
100
0.2561
0.3628
0.5067
0.6980
0.9487
110
120
130
140
150
1.274
1.692
2.221
2.887
3.716
160
170
180
190
200
4.739
5.990
7.510
9.336
11.525
210
220
230
240
250
14.123
17.188
20.78
24.97
29.82
260
270
280
290
300
35.43
41.85
49.20
57.55
67.01
Example 49. Correction of Gas Analysis for Water Vapor and Calculation of Water Content of Gas.
Components
c,
c,
c,
c.
c,
y~,
W ho
PvwM wl06
=
(P  P )380.69
Gas analysis
from laboratory,
mole fraction
Analysis corrected
for water vapor,
mole fraction
0.85
0.o7
0.04
0.03
0.01
0.8488
0.0699
0.0399
0.0300
0.0100
0.0014
1.0000
H,O
1.000
Determination of mole fraction of water in vapor phase when gas is watersaturated at a reservoir temperature of 140F and a reservoir pressure of
2,000 psia:
2 887
Yw = ~
p = 2 000* = 0 .0014435
'
The number of pound moles of gas per million standard cubic feet (MMscf)
at 14.65 psia and 60F is
106 scf
380.69
or substituting for
(429)
1  Yw
.)IO'
W ho  (1 y.(M
 Yw)380.69
P,.(4.73 X IO')
P  Pvw
where M w is the molecular weight of water. The weight of water per mole
of hydrocarbon gas is, then,
Yw(Mw)
273
Who
is
( 28)
4
P  P,w
2,000  2.89
1997.11
68 45 lb/MMSCf
A number of investigators found that at higher pressures and temperatures, the simple relations presented above yielded low water contents.
This m~,y be expected, as in the theory presented no provision was made
for the attraction of the hydrocarbon molecules for the water molecules.
McCarthy, Boyd, and Reid" summarized the available data in charts
which are presented in Figs. 435 and 436.
The water content in pounds per MMscf can be estimated from the chart
if the pressure and temperature are known. The results obtained from the
chart and by calculations as illustrated in Example 49 are compared in
Table 411. The charts are based on experimental data and have been
verified by use in field applications. The engineer should choose to use the
*From Table 410.

274
charts when they are available. Not only are the data;;;ore accurate but
the charts are easier to use.
Hydrates. Water vapor is usually not considered in volume calculations
as the concentrations are quite low. Ho,vever, transmission lines require
~i
40,00 0
4,000
2,oooH+tit+tt+H+H++H++1++1+++J., 1<,,q_Jjl..J. . I
G

,,
g:~~
11i.ooolllll/vlll/
,.,
:;!:
:;
400
20 6
HtttHtt+H+++H+fr.tHi~V
;:::
.,,_
0
~
.E
_,,.
"'
8,000
B0
60
40
=rn
,oo
,,.
3Q,D
"
10
.:'.!
100
I"
v I/
//
:1111~
fOO
BO
60
40
mm
.,,..
r:
~1500'"'
;
20 0
,_
40 0
400
20
""
""
o
2,00 0
80
60
.....
6,00 0
1,00
4,00 0
, ,.
.!!'
0
10,000
100
..:
.!!'
20,00 0
;
100,00
80,00
60,00 0
~:~~~1111~111111
~
275
6,000


 ,_
1/ k>'.
'
L"' .ooo
~
::;::
4
20
2
flL+V'1J,4/~/G~:'.4/,,;;f71'+l/fH+++++!ll++ll....J..:.lliJ.~
,
I
1
60 50 40
30 20 10
10
20
30
40
50
60
70
80
90
100 110
Temperature, F
fO
no1w~~1m1w1ro1w1m~o==~===
Temperature,F
Figs. 435 and 436). When the gas is produced to the surface, the temperature and pressure are reduced. The decrease in temperature tends to
decrease the weight of water which can be maintained in the vapor state
while the decrease in pressure tends to increase the weight of water in ~
saturated gas. For example, consider a gas existing at 2,000 psia and l 40F
at reservoir conditions. The water content (from Fig. 436) is 108 lb per
276
CoNTE~TS~AS
277
Water content,
lb/MMscf
Calculated
2,000
108
1,000
200
174.0
830.0
68.15
137.09
693.51
MMscf. If the pressure and temperature of the surface choke were 1,000
psia and 100F, the saturated gas would contain only 61 lb per MMscf.
Thus, 47 lb of free water would be present for each million standard cubic
feet of gas, and one condition for hydrate formation would be satisfied. If
the pressure were 500 psia, the water content would be 108 lb per MMscf
and no free water would be condensed from the gas.
The composition of the gas determines the equilibrium conditions
of pressure and temperature at
which a hydrate can form even if
free water is present. Carson and
~ 1,500
Katz" developed experimental data
on hydrate equilibrium, and Katz"
presented correlations of conditions
~';o,:;4':::05::'0::6:'::0:"70::'80
Temperature, F
Fra. 438. Temperature change due to pressure drop. (From Vondy et al.=.)
a choke. The temperature drop associated with given pressure drops can
be estimated from the chart (Fig. 438) presented by Vondy."
A number of possible situations can be analyzed readily by using data
from Figs. 435 through 438. Solutions for some of the more co=on
problems are illustrated in Example 410.
Example 410. Determination of Hydrateformation Conditions. .A
0.7gravity natural gas exists in the reservoir at 180"F and 3,000 ps1a.
278
reservo~nditions?
Therefore (from Fig. 4'l7), no hydrate will form even though free
water is available
b. for a 1,500psi pressure drop across choke?
Pressure= 500 psia;temperature
51F
Therefore (from Fig. 437), hydrate will form, since conditions fall
in hydrate region for a 0.7gravity gas
Viscosity of Gases
_The petroleum engineer deals continuously with problems of fluid flow.
Orifield fluids flow through the reservoir rock to the well bore, through
the well bore to the surface, and thence to the separator and stock tank.
The_ visc_osi~y of a fluid is required to solve these many flow problems.
Vrscosrty rs defined loosely as the internal resistance of the fluid to flow.
F
dv
= .A
dy
(430)
or
FIA
. =
(4'll)
dv/dy
let
279
Thus
but
Therefore
F = 1 dyne
A=lsqcm
dv = 1 cm/sec
dy = 1 cm
. =
1 dyne/sq cm
1 cm/(sec)/(cm)
1 dyne/sec
sq cm
1 dyne = gm/(cm)/(sec')
. = 1 gm/(cm)(sec) = 1 poise
The poise is a large unit for hydrocarbon fluids under normal operating
conditions. Therefore, viscosities are usually reported in centipoises. One
poise equals 100 centipoises.
The viscosity of gases are difficult to measure accurately, particularly at
elevated temperature and pressure. The engineer ordinarily must rely on
correlations developed by careful experimentation rather than on limited
laboratory measurements on the fluids at hand.
Eicher and Katz 22 presented the first correlations for hydrocarbon gases
at elevated temperature and pressure. They found the viscosity to be a
function of the temperature, pressure, and molecular weight (gas gravity)
280
r:
,...
>
ooops}2..
~(120L40Q2....
_I
__
3000
L'
''

tOOO
J,.~
r__.
/
v
i./
v .
I / r/
I / v'
.
I/
v \/
v,
_v
~
v
f/
\/
2000
1500
v
60"'
.......
 v. v.
v_,,
~ /
siJfe .......p~~j..../ 1.,./ I /
!. ,
  Extropo!Oted
1.,
,_
0.0 6
,woP
.!!>
6oqg,P!.f. ..........
~o
400l1J..
I
2000
!500
1.000

v
0.6
0.7
0.8
Q9
L::, v_
/
,_,.
I/
V,
1.0
2
0
0.03 .::
0
;:
0.02 ~
1000
1000
100
400
0.01
~ 0.06
~
~ 0.05
.;r
31?~.
0,04
.
I
on
L
,_
,_
_,__
o'!J~iO
1~
5002.i.,OQ! L
'
3 oQ
,ooo

L~
i
t.500
hose regt
f,00
700
;.0'19
O.JO
0.09
lll 0.08
~ 0.07
..:0.04
f~?
rwoP
[....
L1 ~
oO
I/
,__
~~
1~
L
/ v,,
14.7
0.01
0.5
L
 ,_
~
",
/00
0
..
=
0.01
""
sst.1re
, . c  1~
L
3000
.; 0.02
v
~ v
__
pre
;;
,_,...___
0.06 ~
OPsiO:::
0
00: , 10.05 ~
.
,_,, cE
~
0.02;
region
~ 0 se
   
!00F
wo1
  ExfrtJpoltJfed
.___  ..__
~
0
pr~s_....._.. . . . . . ~
0.03
"'
w
,,,
~ 0.05
,_
g 0.0
0.04
0.03
0.08
0
t"/#
f
I
14.7
0.05
0.10
0.09
0.08
0.07 ::
0.06 ~
"'
0.1 0
0.0 9
0.07
0.10
0.09
0.08
0.07
281
/4,7
~
1.1
1.2
0.0 1
0.5
0.6
0.7
0.8
0_9
1.0
1.1
1.2
F1a. 440. Viscosity of natural gases. Data from methanepropane mixtures. Use
only for samples containing less than 5 per cent nitrogen. Deviation, 5.8 per cent.
(From Bicker and Katz.112)
FrG. 441. VIBcosity of natural gases. Data from methanepropane mixtures. Use
only for samples containing le..c::s than 5 per cent nitrogen. Deviation, 5.8 per cent.
(From Eicher and Katz.22 )
of the gas. Correlation charts for four temperatures (60, 100, 200, and
300F) are presented in Figs. 440 and 441. The charts are based on data
from methanepropane mixtures. Katz stated that the correlations should
be used for gases containing less than 5 per cent nitrogen. The average
deviation of the data and the correlations is 5.8 per cent.
282
PETROLEU~f
RESERVOIR ENGINEERING
The distance bet\veen the molecules is decreased; thus more collisions occur
at the same level of kinetic energy.
Another trend is that of generally increasing 'S~cosity at higher gas
gravities for pressures greater than about 1,000 pSia. At lower pressures
the trend is reversed, higher gas gravity materials have lower viscosities.
These trends are temperaturesensitive in that the inversion pressure is a
function of temperature. This phenomenon can also be explained in terms
of kinetic energy. At a given temperature (same level of kinetic energy)
the heavier molecules have a lesser velocity; therefore, fewer molecular
collisions occur. As the pressure is increased, however, the distance between molecules is reduced sufficiently that the attractive forces between
the molecules become significant. The heavier molecules have greater forces
of attraction than the lighter molecules.
Carr and coworkers~ 3 have presented more complete correlations than
those of Katz. It is also believed that their correlations yield better data
for the viscoi!ity of naturalgas mixtures. The correlation of Carr is based
un the correlation of the viscosity ratio/ 1 with pseudoreduced pressure
~.
o~ li.O
ID
"~
,.;
:ill)ii:
~
0
0
0
0
0
,.;
0
0
0
"
~~
~.:,0.;.
"'
N
"
0
!ti
g
z
_,..
0
0
~"
" "
0
0
<IS]Od!~U<l:l .(,!SO:lS]A.
'
"'
"'
diO~e
'~
Q016
~
fid8
~,.drO ~
"
~<::.
"
Q014
'
,,"""
0.012
3
j~B
proPori8
0.010
0.008
100
150
ti
, Marie
'
~ uica"'
':
~
N
~
"
1r~
""'''
' ''
n:...Octo11'
0.006
0.004
50
m
u
if.
!S
"ii;}
"Ii.
O.Qf8
"l
S>
oi pappo UO!P3IIOJ
t1e\ill!1\
:g
''1fltrs
&
~
0.022
II
ON
o~
"
~.$16
'
'
'
"'
OJ pap po UO!P<IHO:J
0.020
<IS!Od!~Ua:> ',(HSO:>S]A
0.024
Oo
u
O'
u
0
ID
n~NOnatl
0
0
0
0
"
0
0
0
Q
"'
3S\Od!JU3:> '.(HSO:IS!A
o, pappo UO!P3JJO:J
q
200
250
300
Temperature, F
350
400
Fra. 442. Viscosity of natural gases at atmospheric pressure. (From Carr et al.zi)
0


,o

285
sented in Fig. 443. The insert charts in the figure provide means of correcting the viscosity for the presence of nonhydrocarbon components.
. Data for mixtures of gases read from Fig. 443 were compared by Carr
Wo1th those calculated from a mixture rule proposed by Heming and
Z1pperer. 24 The viscosity JLm of a mixture of gases is given by
284
6. 0
'..,'/
*'
5. 5
,,
i'::
SD
ff/
'ti
i:
,.
2.0
/J /,
1.5
_Q~:..
0.2
0.3 0.4
~~
//
/
0.6 0.8 1
3.5
~
E 2.5
~
~7
0
/ I /
I/
4.0
~
0
I/ I
5.0
f
{'
I ,
I
I
/~
~ 2.0
>
1.5
..?
f I
1D
2
y;M,
I,,
I 9r:il_
I I I
I
'
7 I I/ t
(432)
i=I
I I
ij>/
,. ~
I/
,y;M,
i=I
m
,.:;;r,
2.5
Q1
~.o
tO
J
I
::; ...,ii;!
I'
3.5
'
"/
~ 1<)J
Q?/
~ 4.0
"'
.'2
'
~,_
...,
4.5
I/
!!~~
...,
.l
.l
8 10
20
FIG. 444. Viscosity ratio versus pseudoreduced pressure. (From Carr et al.#)
0.8
11
1D
1.2
1.4
1.6
1.8
2.0
2.2
Pseudo reduced temperature,
r;
2.4
2.6
2.8
3.0
FIG. 445. Viscosity ratio versus pseudoreduced temperature. (From Carr et al.m)
       
286
 

Therefore,
. at 224F
= 0.024 
Therefore,
., = 0.0119 (from Fig. 443)
,T,
Therefore,
,T,  684  1.507 and ,,P,  3,010  4.581
454
657
287
A liquid is a fluid without independent shape but having a definite volume for a fixed mass under given conditions. Thus, a liquid will assume
the shape of but not necessarily fill a vessel within which it is confined.
A liquid seeks its own level and is incapable of supporting shearing stresses.
In the discussion of the properties of gases, the kinetic theory was introduced to describe theoretically the behavior of molecules in the gaseous
state. Inherent in the treatment of gases was the assumption that the
distance between molecules was great enough so that the attractive forces
between molecules were negligible. In the case of liquids, the distance between molecules is much less and the force of attraction between molecules
is substantial. The proximity of the molecules and the force of attraction
between molecules in the liquid state result in substantial differences in the
physical properties of liquids as compared with gases. Liquids have less
fluidity (greater viscosity) and less volumetric changes with changes in
temperature and pressure than do gases.
In general terms, liquids are frequently conceived to be either condensed
vapors or melted solids. These concepts are useful in visualizing many
processes to which substances are subjected. The continuity of the various
concepts can be illustrated by the generalized phase diagram for a onecomponent system presented in Fig. 446. The curves represent conditions
C Critical
. = E. ., = 1.92(0.0119) = 0.0228 cp
.,
point
Temperature

F:rs. 446. Generalized phase diagram for a pure substance. (Adapted from Daniels. 2 )
288
containing a fixed mass of the material in the state prescribed by the region within which the inset is located. Characteristic of the solid phase is
the definite shape of the mass of substance, independent of the shape of
the confining vessel. The liquid assumes the shape of the vessel but fills
only a portion equal to the definite volume of liquid corresponding to the
mass of material and the given conditions of pressure and temperature.
The molecules are relatively close together in both the solid and liquid
states. The vapor, inset III, occupies the entire vessel and aS&lllles the
shape of the vessel. The distance between molecules is substantially
greater than for either solid or liquid.
)
Volumetric Behavior of Liquids
The volumetric behavior of liquids as a function of pressure and temperature has been studied intensively in many fields of science. Nevertheless, Dauiels2 states "the theory of liquids is in a much less satisfactory
state than the theories of gases and crystals, but important progress is
being made in our understanding of the structure of liquids." The state
of progress is such that a simple generalized equation of state has not been
developed for liquids.
As in the case of gases, the petroleum engineer is primarily concerned
with the change in volume of liquids with a change in pressure and temperature. The state changes discussed in this section will be confined to
those in which the material remains wholly within the liquid phase.
An ideal liquid is defined mathematically by the following partial derivatives:
( av)
aT P
and
( av)
aP T
(433)
where (av /aT)P is the isobaric thermal expansion and (aV /aP)T is the
isothermal compressibility. The relations expressed in Eq. (433) state
that changes in volume with pressure and temperature are zero for an ideal
liquid. Furthermore, an ideal liquid is conceived to have no internal fric. tion between molecules; consequent1y, the viscosity of an ideal liquid is
zero. Thus, the concept of an ideal liquid is of little quantitative value in
predicting the volumetric behavior of liquids but does provide an insight
into the behavior of liquids. The volume of real liquids does change with
variations in pressure and temperature, but these changes are so small
compared with gas that they are represented as a fractional change of some
standard or reference volume.
A comparison of the relative changes in volume of liquid and gases can
be obtained from inspection of Fig. 42. For the conditions specified by
the segment of the 80F isotherm between points A and B, ethane is in the
gaseous state. For the conditions specified by the segment between points
A and F, ethane is in the liquid state. The isothermal compressibility
289
v=
0.005 cu ft/lb
and
or
(~;)T
0.0000371
CU
ft/(Jb)(psi)
and
or
(~)T
0.000894
CU
ft/(Jb)(psi)
The gas is 24.1 times as compressible as the liquid in the ranges considered.
r.rhe isobaric thermal expansion can also be expressed in finite form as
(d VI dT)p. At a pressure of 700 psia and temperatures between 60 and
85F, ethane is in the liquid state .. The average isobaric thermal expansion
is approximately
0 3
= 0.00052 CU ft/(Jb)(F)
g;
Also at 700 psia and for temperatures between 100 and 160F, ethane is a
gas. The average isobaric thermal expansion is about
Oi~g
0.00131
CU
ft/(lb)(F)
The thermal expansion of the gas is about 2.5 times that of the liquid.
The effect of pressure on the specific volume of propane is shown in
Fig. 447a. The curves are for constant temperatures and are called isotherms. The slope of an isotherm is the isothermal compressibility. The
compressibility is always negative, indicating that increasing pressures result in smaller volumes. The magnitude of the isothermal compressibility
decreases with increasing pressure, 'vhereas it increases 'vith increasing
temperature. Thus, the effect of pressure variations are greater at low
pressure and high temperature. The change in slope with pressure can
be stated mathematically as the second partial derivative.
a(aV/aP)T
aP
(a'V)
api
..
= pos1t1ve number
(434)
29]
line. Hence, the variation in the specific volume of the fluids at 70F can
be represented (in the range 100 to 2,500 psi) by
v=vo+bP
"'
.;
0.035t~~E~~~~~~~~~i~~
0.030
(
500
1,000
1,500
2,000
where Vo is the intercept with the y axis at zero pressure and bis the average
slope or isothermal compressibility. The volume rather than the specific
volume is usually the desired quantity, so that
V = wv
Vo
WVo
bP
V=wvo+wvoVo
2,500
v=
or
Pressure, psi
(a)
vo(1 + ~P)
(435)
Vo
,..... ....
500
1,000
where
1,500
2,000
2,500
3,000
CT =
Vo
V
Pressure
(437)
(b)
.........__
0.5f+++t1
.
o~_j__:::::t:::::\==J=1
0.51++t+1
1.0''~.....,~,..,.c,.,'=,,o!
500
1,000
1,500 2,000
(436)
2,500
Pressure
The coefficient of compressibility as defined by Eq. (437) is a point function and can be computed from the slope of isothermal specific volume
curve for each value of pressure. The minus sign_ arises from the mathematical convention with respect to slope. As the slope of the curves are
always negative, v is always a positive number and it is desired that c be
a positive number; then c must be defined as the negative of the slope
divided by the specific volume.
The coefficient of compressibility of a fluid is the reciprocal of the bulk
modulus. The bulk modulus is analogous to the modulus of elasticity of a
solid. That is,
1
(stress)
~ = strain T
(c)
The stress in a fluid is the change in pressure from some reference pressure
Fia. 447. (a) Effect of pressure upon the volume of liquid propane. (From Sage
and Lacey.D) (b) Isothermal compressibility of liquid propane at 160F. (c) The
change in the isothermal compressibility of liquid propane at 160F.
290
Po, and the strain is the change in volume per unit volume at the reference
conditions. Therefore
292
1 P P0
c  Ll V /Vo
(438)
The bulk_ n;>?dulus has the dimensions of pressure, while the coefficient of
compresSibility has the dimensions of reciprocal pressure.
8
6
~1
!fig. 448~. The isobaric thermal expansion (aV /oT)p is the slope of the
isobars (lines of constant pressure). The slope of the isobars (Fig. 448b)
2
~
roo
0.045
200
300
(c)
:t:
0.040
~000
150
Temperature
Fra. 448. (a) Volume of liquid propane. (From Sage and Lacey.") (b) Isobaric
expansion of liquid propane. (c) Variation of isobaric expansion of liquid propane.
'
293
.;
Bubble point
500 lb/sq in
t,000
>
increases with increasing temperature and decreases with increasing pressure. The slope is at all times positive, indicating that an increase in tem
perature increases the volume of the fluid. Stated analytically, the change
of slope with temperature is the second partial derivative.
1,500
.,,
;g 0.035 2,000
3,000
~
~
a(aVaT
/oT)p
"'
(a'V)
aT' P
..
pos1t1ve number
(439)
Results of Eq. (439) (Fig. 448c) confirm the observation that the isobaric
expansion increases with increasing temperature.
The coefficient of isobaric thermal expansion f3 is defined as
0,030
100
150
(av)
(440)
13 = lV aT P
The isobars of Fig. 448a are sensibly straight over a part of the range of
200
Temperature,
(a)
V = V0 [l
6
<:i
2
__,... v
3,000 psi
Temperature, 0 f
(b)
(441)
150
To)]
100
+ /3,(T 
200
30()
and
For compressibility,
v = Vo[l + {3,(T  T0 )]
= Po[l  /3,(T  To)]
(442)
(443)
(444)
V =

and

et:i>.ci~tcii00
"1""""
p,[l
+ cr(P
MC'l C'l
or
0
COCON60
C'l 
C\I
00000
C:.O'lc<:l<:OO"'OO
ININMMCQ
0000000
o:>O>r.i>.0:tt":t'
NO'le<::OOOO:.tcicci....jc;i~..,,.iici
MM ":t' "'1' "":f'.:!< "'1'<
c:.ou:ii:oC\I
.0 ci qi N .0 M lO
"'::!' C':l t C\I t oooooic:.oo

'
Poec<PPo>
(446)
Component
>.OOto:>
.!"
(445)
 Po)]
000:.INNO'lO'lC"l
>r.l
295
o:i et:i ci
ci >.O 0
OOOOMO'lCO"';!<N
LIQUID
ANALYSES
Stocktank liquid,
mole fraction"
Reservoir liquid,
mole fractionl>
0.0019
0.0098
0.0531
0.0544
0.0555
0.0570
0.7681c
1.0000
0.3396
0.0646
0.0987
0.0434
0.0320
0.0300
0.3917'
1.0000
"<:l''<t'"'::i"MMe<:lM
t":t'<:OC'l":t'OOt
~~0:~'q~'=!
 "'
>t:10'1<ooo
0:.00>r.l0>.00..,..
,.....C'l C\I M C<:I
CO<:OCNOO":t!OCO
"<l'"<l<t0:.C>llQtNC<IN
 
ciC'i'ccici~ocici
tt000,.....IN"':i"
,....,
Methane
Ethane
Propane
Butanes
Pentanes
Hexanes
Heptanes plus
263; density

296
297
40
:J;
10
0 .6
0
~
0
,;
c
""'
0 .5
j;v
0 .4
i
_,r
j,
"'
70
g 50
~
c.
~
"
60~
_.10
50 g
30
20
..... 0.3
,;
c
Q
~
~ 0.2
L/
.._.A
A
lY

A
'
";..Y
C.0'
u'
Ef/J(JneNBvfone
/honeHeptane
+
;:f /honeCrystal oil
" MethoneCyclo Hexoni
MethaneBenzene
o Melho11ePentane
o MethaneHexane
MethaneHeptane
t::,,. MethanePropane
0.4
g'
g"
"
30.
30 E
.;;
"
10
F1a. 450. Pseudoliquid density of systems containing methane and ethane. (From
Standing.3 )
?
f
9 Meth'1neCrvde oil
'
' 0.7' ' 0.8'
0.6
0.5
Density of system, 60F aotm.pressure
"E
~
0.
'91
0.3
40
'
o.4
0.9
FIG. 449. Variation of apparent density of methane and ethane with density of the
system. (Standing and Katz.w)

298
where W; =
Wi = xMi
weight of ith component in 1 lbmole of mixture
(447)
to use the corrective charts for methane and ethane. The weight per cent
ethane in the ethanes plus is
M;
299
wt of C,
(wt % C2)e2+ = wt of c,+ =
x,M,
(453)
2: x;M;
Wm=
wt of C1
(wt% C1)ei+ = wt of C1+ =
(448)
i=l
Vm
l:V;
Example 412.
Anay
I sis
Vm
The method of Standing and Katz assumes that the propanesplus fractions can be treated by additive volumes. The abovecited equations must
be modified as follows:
We'+=~
(1)
(2)
Component
Mole
fraction
in liquid
phase X;:
Mole wt
M;
0.0019
0.0098
0.0531
0.0544
0.0555
0.0570
0.7681
16.04
30.07
44.09
58.12
72.15
86.17
263
Methane, C1
Ethane, C2
Propane, C3
Butanes, C,
Pentanes, c~
Hexanes, CG
Heptanes plus, C;+
Total
(3)
(4)
Relative
weight,
lb/mole,
z.;l11i
(2)
(3)
.0305
.2947
2.3412
3.1617
4.0043
4.9203
202.0366
216.7893
x;M;
i=3
i=3
and
Ve'+=
2: V;
where the summations are taken over the C3 (propane) and heavier components. Two additional definitions must be stated in mathematical form
x;M,
Wm
The molecular weight and specific volume at 14.65 psia and 60F can be
obtained from Table 44 for the lighter hydrocarbons, methane through
heptane. The molecular weight and specific gravity of the heptanesplus
fraction are normally determined in the laboratory and reported as a part
of the fractional fluid analysis.
(454)
i=l
x11l11
m
11
_
Density of C1+ = 216.7893
= 53 49 lb/cu ft
4 0531
(5)
Liquid
density,
lb/cu ft at
60"F and
14.65 psia
(18.70)
(23.26)
31.64
35.71b
39.08'
41.36
55.28a
(6)
Liquid
volume,
cu ft/mole
(4)  (5)
(0.0016)
(0.0127)
0.0740
0.0885
0.1025
0.1190
3.6548
4.0388
(4.0531)
300
301
x.M;
Density of C'+ = ''''''. ~ x,M,
i3
Pi
= 53.59 lb/cu ft
Wt
30 c, in c
'+
x,M,
100 =
{'
L, xMi
i=2
= 0.136
Wt
O"f
/O
C 1 in C
= x,M,
'+
100
{'
1
0 014
x~i
i=l
c,. = c(,,P,)
Since
or
Pr=,,P,
= cP =
are known, the compressibility can be determined from Eq. (456) and the
correlation of Cr with pseudoreduced temperature and pres.sure presented
in Fig. 452.
At the higher reduced pressures an appreciable segment of the constant
reducedtemperature lines have a constant slope. An equation for the
straightline segment has the form
(455)
c,.P,
c11P1
= c,,P, = c,,P,
(456)
(457)
where n is the slope of the line and a is the intercept of the straightline
segment at P, = 1. Substituting from Eq. (457) for c,. in Eq. (456)
(aP,~)P, =
aPr""+1
cP
cP
302
p~+1 =
constant = A = cP
0.1~~~~
1+'<+*Ar!+J..+l.L+++r++++I
/_i_"<f.'>.+"~ tt+=J
303
in the manner described previously for gases. These values can be used
together with Fig. 452 to calculate the compressibility of the fluid. F01
many liquids adequate estimates of critical properties are not available.
Trube also developed procedures for estimating the critical properties of
reservoir liquids.
Thermal Expansion of Liquids. The most frequent application of the
thermal expansion of liquids is in correcting the volume and density of
stocktank liquids to 60F, the standard temperature. The Bureau of
Standards published in Circular C410" extensive tables for this purpose.
Abridged volumecorrection tables are presented in the ASTM" and Tag''
manuals. Coefficients of thermal expansion at atmospheric pressure are
listed in Table 412 for the paraffin hydrocarbons pentane through decane.
For the more complex stocktank oils, the coefficients of thermal expansion
I I i
:::
~ 8
'
c,
"'
~
""
~
!! 6
~
.e

,
w
.=
~ 3
"'
~
..0
~
~
men ts of Fig. 452 are very clo;.;e to minu8 one (  I). If it is assumed that
n = 1, then
A = cP = c,P, = c,P,
(459)
The pseudoreduced propertie::;; ca.n be calculated from the liquid analysis
F1a. 453. Density correction for thermal expansion of liquids. (From Standing.s)


304
are correlated with the API gravity of the oil. In Table 414 are listed the
average coefficients of thermal expansion used in prepariug abridged volumecorrection tables for oils.
TABLE 414. AVERAGE COEFFICIENTS OF
TliEmuL
Density of C,.._ =
ATMOSPHERIC PRESSURE3 11
Group
No.
Coefficient of
thermal expansion
at 60F
0.00035
0.00040
0.00050
0.00060
0.00070
0.00080
0.00085
0.00090
2
3
4
5
6
7
Wt
Up to 14.9
1534.9
3550.9
5163.9
6478.9
791l8.9
6
22
44
58
72
86
Reservoir
Component
fiuid
analysis Zi
Mol wt
0.3396
0.0646
0.0987
0.0434
0.032
0.03
0.3917
16.04
30.07
44.09
58.12
72.15
86.17
263
c,
c,
c,
c,
c,
c,
c,.
Total
From Table H.
(4)
Relative
weights,
lb/mole
(2) x (3)
C,
lil
(5)
Density at
60F and
Wt% C1
X;M;
Pi
C... =
x,M 2
in
Table 413.
(6)
cu ft/mole
(4) + (5)
lb/cu ft4
31.64
35.71b
39.08'
41.36
55.28'
'
xJv[;
.
ill
X1M1
total =
xJv[;
i=l
Liquid
volume,
14.7 psia,

9.9
5.4472
I.9425
4.3517
2.5224
2.3088
2.5851
103.0171
122.1748
~From.
~:3.9
91
97
(3)
xJvf;
i=2
= 52.34 lb/cu ft
Gravity range
of group, 0 API
For correction of liquid densities for thermal expansion, Fig. 453 can
be used. The chart yields satisfactory results except in the lowdensity
and hightemperature regions. This chart, like Fig. 451, is based on a
large number of observations of specific volumes of hydrocarbons. The
density at 60F is the only composition parameter.
The calculation of the density of a liquid at reservoir conditions from a
fractional analysis requires data on both compressibility and thermal expansion. The procedure for such a calculation is shown in Example 413,
using the reservoir liquid of Table 413.
(I)
l
''"~"l
i=3
Corresponding
gravity, 0 API
305
0.1375
0.0706
0.0591
0.0625
1.8636
2.1933
pc,.= !9.4
+ 1.0 =
Surface Tension
The surface tension at the interface between a liquid phase and an equilibrium vapor phase is a function of pressure, temperature, and the compositions of the phases.
For pure substances only the temperature or pressure must be specified
to define the surface tension. As a tension exists only if two phases are
present, then either temperature or pressure can be specified a~d the oth~r
will be defined by the vaporpressure curve. The surface tenSions ot vanous pure paraffin hydrocarbons are shown as a function of temperature in
Fig. !54. The value of zero surface tension occurs at the critical point of
the hydrocarbon.
The surface tensions of mixtures of hydrocarbons have been investigated
experimentally by Katz, 33 who, from the experimental data, developed a


306
q~ = ~
25
c
~20
..
vapor
. ..
liqwa
vapor
900
c
15
~
,
V>
10
(461)
~
c
2
~
h._.)
Yi M11
;>;
Xi
30
PL
x, J.lfL
i=l
where
35
(
pchi
307
Afol. Wt
800
240
220
200
180
150
700
140
600
I
I
1
0 500
;,
"
400
I
200
100
100
300
200
Temperature, F
400
500
300
600
FIG. 454. Surface tension of paraffin hydrocarbons. (From Katz and Saltman.3'))
200
100
uM = pckPL 
p,,
'
(460)
0
where p ch = parachor
PL = density of the liquid phase, gm/cc
p, = density of the vapor phase, gm/cc
u = surface tension, dynes/cm
M = molecular weight
Parachors for pure hydrocarbons, nitrogen, and carbon dioxide are given
in Table 415. A correlation of the parachor with molecular weight is presented in Fig. 455. For a mixture the surface tension is defined by the
following relation:
100
200
300
400
Molecular weight
.&,
The densities PL and p,, must be in grams per cubic centimeter to use in
Eq. (461) with the parachors of Table 415 or F~g. 455.
The calculation of surface tension is presented m Example 414. In Fig.
456 are presented comparisons of experimental and calculated surface ten~
sions of mixtures of hydrocarbons.
309
308
30
'
25
,\
_,
ul< =
\'l
':'. 2on
~
<
"
~ 15
<
.:e
"
~10
"
~
"'
i P,,,,,(x,; 
i=l
y,
J,;)
11
0 729
.EL =
= 0.005938
ML
119.9
+'\
\
'.
'
{\
(3)
Mole
Com fraction fraction
ponent liquid
vapor
(I)
).. \~
(2)
0 093
h = 20.48
= 0 .004541
M.
(4)
(5)
(6)
(8)
(7)
Mole
i~
I/
'\!\ \'
''
1,000
'
2,000
~..,,.,,
..._
3,000
4,000
5,000
6,000
F1a. 4_56. Experimental and calculated surface tension of crude oils. () (+) ()
expenmental data at 88F; (A), experimental data at 95F (o) (..6.) calculated
data at 120F. (After Katz et al.33 )
'
'
'
TABLE 415. PARACHORS FOR PURE SUBSTANCES
Component
Methane
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
nHexane
nHeptane
nOctane
Parachor
77.o
108.0
150.3
181.5
190.0
225
232
271
311
352
41.0
78.0
c,
c,
c,
c.
c,
c,
c,.
" C1+
"'
0.2752
0.0657
0.0665
0.0584
0.0454
0.0432
0.4456
1.0000
0.8424
0.0752
0.0405
0.0217
0.0095
0.0052
0.0055
1.0000
mol wt
PL
Zi ML
Y M.
0.001634
0.000390
0.000395
0.000347
0.000270
0.000257
0.002645
0.003825
0.000341
0.000184
0.000099
0.000043
0.000024
0.000025"
(4)  (5)
P""
parachor
0.002191
+0.000054
+0.000211
+0.000248
+0.000227
+0.000233
+0.002620
77.0
108.0
150.3
190.0
229.0
271.0
575.00
(6)
(7)
0.169
+0.006
+0.032
+0.047
+0.052
+0.063
+l.511
1.542
225.
(462)
310
The kinematic viscosity exhibits a linear trend when plotted as a function o~ ~empern.tu:e on a special chart available from the American Society
of Testmg Mate'."'als (ASTM). Thus, observations at only two temperatures enable.the investigator to determine the viscosity at other tempera..
l.
...,.
tures.
where
10
8
I
I
311
(463)
Vapor space
Tube
1. 0
"'
o. 8
:C
0. 6
0.4
;;;
>
Q2
(b)
(a)
FIG. 458. (a) Ostwald viscosimeter. (From ASTM .) (b) Rollingball Yiscosimeter.
oo4 ;';!;;'::f:::'..,c:1:,~L_L~1.....l.~..L_j~_L_J
40
80
120
160
200
240
280
Molecular weight
(From
TABLE 416
312
Hydrocarbon
Temp,
Temp.,
1.6 1  ,    ,    , ,   .    .   . . , ,
500
f,000
1,500
2,000
2,500
PSP'
3,000
Pressure, psi
Fla. 459. The viscosity of a crystal oil under pressure as compared with its
viscosity at atmospheric pressure .,,. (After Sage, Sherbome, and Lacey.f/JIJ)
Vapor Pressure
Vapor pressure is a characteristic of a pure substance which is generally
associated with properties of liquids. Actually, for a substance to exhibit
a vapor pressure, the conditio_ns of pressure and temperature must be such
that the substance exists in the twophase region.
The vapor pressures of light hydrocarbons are tabulated in Table 416
as a function of pressure. Methane is not listed as its critical temperature
is 117F, well below ordinary temperatures. A substance which exists at
a pressure and temperature corresponding to a point on the vaporpressure
l?urve may exist as a liquid, a gas, or a mixture of the two phases depending
on the total energy of the system. The change of energy levels is the subject of thermodynamics and will not be considered here. From energy concepts, however, it can be shown that the logarithm of the vapor pressure of
a substance is linear with the reciprocal of the temperature.
A more co=on method for graphically presenting vaporpressure data
of hydrocarbons is the Cox chart (Fig. 460). The pressure scale is logarithmic, and the temperature scale is determined by drawing an arbitrary
line on the chart for the vapor pressure of water. At each pressure point
on the line, a temperature corresponding to the vapor pressure of water
is defined. The vapor pressures for hydrocarbons plotted on such a chart
are linear and tend to converge to a common point. This property is
useful in extrapolating vapor pressures of pure substances to temperatures
'F
Ethane
Propane
Isobutane
Butane
32
34
36
38
40
348
358
367
377
387
69.6
71.4
73.4
75.3
77.4
25.9
27.1
28.3
29.6
30.9
14.9
15.5
16.1
16.7
17.4
5.0
5.3
5.6
5.9
6.2
3.5
3.7
3.9
4.1
4.3
.87
.92
.98
1.04
1.10
0.0
1.1
2.2
3.3
4.4
42
44
46
48
50
79.6
82.0
84.5
87.1
89.8
32.2
33.5
34.8
36.1
37.4
18.1
18.9
19.7
20.5
21.4
6.5
6.8
7.1
7.4
7.7
4.5
4.7
4.9
5.1
5.4
1.16
1.22
1.29
1.36
1.43
5.6
6.7
7.8
8.9
10.0
52
54
56
58
60
92.7
95.8
99.0
102.2
105.5
38.9
40.0
41.3
42.6
43.9
22.3
23.2
24.1
25.1
26.1
8.0
8.3
8.6
8.9
9.2
5.7
6.0
6.3
6.6
6.9
1.50
1.58
1.66
1.74
1.83
11.1
12.2
13.3
14.4
15.6
62
66
68
70
108.9
112.4
115.9
119.4
122.9
45.2
46.5
47.8
49.2
50.7
27.1
28.1
29.1
30.1
31.1
9.6
10.0
10.4
10.8
11.2
7.2
7.5
7.8
8.1
8.4
1.93
2.03
2.14
2.25
2.37
16.7
17.8
18.9
20.0
21.1
72
74
76
78
80
126.4
130.0
133.6
137.3
141.1
52.2
53.7
55.3
56.9
58.6
32.l
33.1
34.2
35.3
36.4
11.6
12.1
12.6
13.1
13.7
8.7
9.0
9.4
9.8
10.2
2.49
2.62
2.76
2.90
3.05
22.2
23.3
24.4
25.6
26.7
145.0
149.0
153.1
157.3
161.5
60.3
62.1
63.9
67.7
37.5
38.7
39.9
41.2
42.5
14.3
14.8
15.5
16.2
16.9
10.6
11.0
11.5
12.0
12.5
3.21
3.37
3.53
3.70
3.87
27.8
28.9
30.0
31.1
32.2
165.8
170.2
174.7
179.2
183.7
69.7
71.7
73.7
75.8
77.9
43.8
45.2
46.7
48.3
49.9
17.6
l.3
19.0
19.7
20.4
13.0
13.5
14.1
14.7
15.3
4.05
4.23
4.42
4.62
4.83
33.3
34.4
35.6
36.7
37.8
102
104
106
108
110
188.3
193.0
197.8
202.7
207.7
80.1
82.3
84.6
86.9
89.3
51.5
53.2
55.0
56.9
58.9
21.1
21.8
22.6
23.4
24.3
15.9
16.5
17.2
17.9
18.6
5.05
5.28
5.52
5.77
6.03
38.9
40.0
41.1
42.2
43.3
112
114
116
118
120
212.7
217.8
223.0
228.3
233.7
91.7
94.2
96.7
99.3
101.9
61.0
63.2
65.5
67.8
70.1
25.2
26.1
27.1
28.1
29.2
19.3
20.0
20.8
21.6
22.4
6.29
6.56
6.84
7.13
7.43
44.4
45.6
46.7
47.8
48.9
64
82
84
86
88
Critical
temp
90
92
94
96
98
100
65.8
313
IsoPentane Hexane
pentane
'C
='c
"
'
:Q:i~ .,
~,}X
~'IT
,".
' "
' ''
\
'"
1.' '
"\ \
The qualitative phase behavior of hydrocarbon systems and the quantitative behavior of the vapor and liquid states have been discussed. 1~he
quantitative analysis of twophase systems will be discussed in the remainder of this chapter. Twophase, gas and liquid, systems exist at conditions of pressure and temperature within the region enclosed by the
bubblepoint and dev.rpoint curves.
The quantitative analysis of twophase systems involves the determination of the mole fractions of gas and liquid present at a given condition
and the computation of the composition of the coexisting phases. The
physical properties of the gas and liquid phases within this twophase region can then be computed by the procedures previously described.
As was shown in Fig. 46, if a fluid existing at its bubble point is subjected to a pressure decline at constant temperature, two phases are formed.
The proportion of the gas phase increases, \Vith decreasing pressure, because of two phenomena. The more volatile constituents escape from the
liquid phase and enter the gas phase. Also, the gas formed at higher pressures expands and occupies a larger volume.
The idealized volume relations during such a process are shown in Fig.
461. A portion of the gas volume Vu is shown to be gas released between
'
'
~,.
'%..,~
0
~
..
'
..
I\
'
,\
j\
'
ca
'
OL
'.
09
'
r.
OS
'', 0
\
O'
'
'' '
01
0
01
00
I'
,\
0
001
" "
'. ~
'
i\ '
''
'
\
\i\
.
"
'
06
r:
"'
09
,.
I'
'
/'
.
'
,j
'
''
..,,\ I
.
"
''
~\~
o o=.\
'
. ~~~ ~
"
"
1.
.,.
'
~\~
"
I\
. "'' .
~
' '
~ \.'l
'
~\I'
;..\
.\
I\ \
\I
oa
'
'
'\
\\
00
00
It.
I' '
O'
1.~o=.
'"~
'
'
.._.,.I
'
.:
II
. .
'
oa
.~~'
' '..
\
"c
,_ o~
'p
?~
0
,. .
'
,\
\\
' ,~
'
0'0
T= Constant
f?Z:l
~
~
~
O>
cs
Pressure~
314
315
316
stocktank conditions.
If a given mass of fluid is subjected to the processes described above,
then the following definitions can be made:
1. The volume of liquid v. at reservoir temperature and the prevailing
pressure divided by the volume of oil collected in the stock tank V,, is
defined as the oil formation volume factor B .
2. The total volume of the system v, divided by the volume of stocktank oil is defined as the total formation volume factor B,.
In equation form,
B 0  V.
V.,
B  V,
t V.rt
I
I
Removed from
system at
I
I
separator
I
I
Removed
 _,... ~}
Vg
system at from
d
Lj_____ _

Vsep
P=
fb,
T= Tres
Stock tonk.
v,1

P= ~ep T= ~ep
19 ~ 100
Vo
ditions, as the density of the gas is usually quite low. The liquid volume
shrinks substantially because of decreased temperature and the escape of
a portion of the fluid into the gas phase. In most instances the greater
part of the mass of the system remains in the liquid phase. Because of the
greater density of the liquid, this liquid mass occupies much less volume
than the gas. The liquid and gas phases formed in the separator are withdrawn separately (hence the name of the device, separator). The separator
liquid is collected in the stock tank, at which point additional temperature
and pressure drop may occur. Gas may or may not be released in quantity
317
(464)
p,
(424)
i=l
and
p,
y, = p
(425)
The statement of Ra.cult's law is "the partial pressure exerted by a constituent of the liquid phase is equal to the vapor pressure of that consti tuent times the mole fraction of that constituent in the liquid phase."
That is,
(465)
Pi= x,.P,,i
319
318
11..i = fLi = Ki
Xi
fgi
or
XiPvi
?/i=p"i=K
Xi
'
and
(fLi)m<x = Xi(fLi)pure
10
'
'
"'.
0""'
'
'\,,
'
"". "'
o~
'
''
"'\.~o
'('o"'@
'!'.,
~
~
'
t'..
'<o~
@
'\,,
'1'
' I'
r,,_
o~
@~
'
"''
'...._
=~
@~
""
'
"'..
' ....._
'<>"'@
c:i.,., 'I
0. I
<',.
"'
'
""' ',%,
""
'
~'
K I
"'
'
...... ....
/'
"'.;,
""
$<;::>..,__
'@
(468)
where the subscript "mix" refers to the mixture and "pure" to the component in the pure state, fui is the fugacity of a component in the gas phase,
and fL, is the fugacity of that component in the liquid phase. The fugacity
of a component in the gas phase is equal to the fugacity of that component
in the liquid phase if the phases are in equilibrium. Thus
Yi(fai)pure = Xi(fL.;)pure
(466)
where Ki is defined as the equilibrium ratio of the ith component at pressure P and some temperature T.
Certain limitations are placed on the above defi11ition by Raoult's la\v
and Dalton's law. It is evident that any pure con:;tituent has a vapor
pressure only up to its critical tempen1ture. Beyon<l this temperature there
is no true vaporpressure curve for a pure constituent. The vaporpressure
curves of such constituents can be extrapolated to higher temperatures.
However, this practice does not yield satisfactory results in most cases.
Since the critical temperature of methane is 1l7F, it becomes evident then that some other means must be obtained for the determination
of equilibrium ratios if they are to be used for hydrocarbon mixtures.
Lewis39 introduced the concept of fugacity for the extrapolation or correction of vapor pressures to use in equilibrium calculations. The fugacity
of a component is a thermodynamic quantity defined in terms of the change
in free energy in passing from one state to another state. Dodge and
Newton 40 have shown that the fugacity of a component in a phase of a
mixture is equal to the fugaclty of that component in the same phase in
the pure state and at the same conditions of pressure and temperature as
the mixture times the mole fraction that component represents of the mixture. Thus
(467)
(fai)mix = Yi(fui)pure
(469)
"\..
0.01
IO
100
'"
./.
"~
1,000
10,000
Pressure, psio
F10. 463. Equilibrium ratios at 200F for a lowshrinkage oil. (From Katz anci
Hachmuth.0 )

320
321
463), and Roland, Smith, and Kaveler" presented data for condensate
fluids (Fig. 464).
Development of Equations for Calculating Equilibrium Relations
40
1"
"" ""
20
'
lO
8
6
'
E
E
o.s
'<%o.,.~
1'
<<t>"I
~"';:_
~0
'"
' I'
'
~0.4
'
't..
'~"'"~
'
01
.,
I
"'~s
!'..
(470)
n=L+ V
That is, the total number of moles of composite is equal to the moles in the
liquid phase plus the moles in the vapor phase.
From which, by definition of the mole fraction,
z,(n) = x,(L) + y;(V)
(471)
"'~
This states simply that the moles of the ith constituent in the total must
be equal to the sum of the moles of the ith constituent in the vapor and
liquid phases.
A third equation by definition of the equilibrium ratio is
ODS
006
I
004
001
100
'
K '.  Ii!
~s
002
By definition,
~
total
mole
x, = mole
Yi = mole
=
Zi =
"'~s
~
; 0.6
0.2
'
r...~
"i ~
o_,.~
"..
n = total moles of both gas and liquid present at any state of pres
%~
'
'
position of the equilibrium gas and liquid phases and the fraction of the
mixture existing in each phase can be calculated.
In deriving the various equations describing phase equilibrium, it is
convenient to define a group of terms and symbols as follows:
1,000
(472)
X;
As Xi, Yi, and Zi represent mole fractions, three more relations can be
stated from the definitions.
10,000
Pressure, psio
.X;
FI0. 464. Equilibrium ratios at 200<>F for a condensate fluid. (From Roln.nd et al.~ )
y;
i=l
i=1
Z;
(473)
i=l
V+L=l
therefore
z, = x;L
+ y,V
(474)
(475)
+ K,V)
            
322
Z;
x; = L
+ K;V
If on the right side of the above equation both the numerator and denominator are divided by V, the results are as follows:
v1 (L/V) + K,
Zi
X;
(476)
As Xi represents the mole fraction of the ith constituent in the liquid phase,
the sum of the mole fractions of all the constituents is 1. Therefore,
{'
i., x, =
i:1
1 {'
Z;
V i=l
i., (L/V) + K;
{'
Z;
= i., L
i=l
+ VK,
= l
(474) to solve for Land V, the mole fractions of liquid and vapor, respectively. The two equations thus available for the solution for two unknowns
must be solved by a trialanderror procedure. Several alternative forms of
Eqs: (477) through (480) can be derived. The form selected depends on
the estimated magnitude of L and the computing method to be used.
At the bubblepoint pressure, L = 1 and V:::: 0, since all the mixture
can be considered as a singlephase liquid. Equations (476) through (478)
become meaningless at the bubble point. Likewise at the dew point, L '.:::::" 0
and V = I and Eqs. (479) and (480) are meaningless. However, at the
bubble point
(477)
or
or
(L/V~'+ K, =
i=l
(478)
and
y, = (L/K;)
+V
{'
{'
_L., Y<
i.=
Z;
_L., (L/K;)
i=
y,
(481)
z,K, = 1
i=l
+V
= l
(479)
or
i=l
i=l
Yi= zJ(i
and
323
(L/K,~) + 1 =
(480)
These equations apply within the twophase region. In equilibrium calculations, the con1position of the composite fluid or feed must be ~own
together with the pressure and temperature at which the equilibrium exists.
Suitable equilibrium ratios for each component must be available as defined by the conditions of pressure and temperature and the composition
of the composite. In general if the system is comprised of m components,
the number of unkno"\V"IlS in the calculations are equal to 2m + 2, m values
of xi, m values of Yi, and the values of L and V. There are available m
equations Yi = Ktxi and m equations Zi = xiL + YiV. In addition for 1
mole of feed V + L = 1 and l:z, = l:x; = l:y, = I. Thus there are available 2m + 2 equations to solve for 2m + 2 unknowns. As can be noted
from Eqs. (474) through (477), it is not possible to solve analytically for
explicit values of the unknowns. However, in Eqs. (474) through (477)
the number of unknowns have been reduced by substitution to two, Land
V. Thus any of Eqs. (477) through (480) can be used together with Eq.
and
"'
i=l
i=l
Z;
x,. =Ki
.z:x,=.Z:;;=l
(482)
z,
Ki
x=i
X;
The value of Ki is dependent upon the pressure, temperature, and composition of the hydrocarbon system. Equilibrium ratios for a lowshrinkage
oil and a condensate at temperatures of 200F are shown in Figs. 463 and
464 as functions of pressure. The equilibrium ratios for all constituents
324
325
FIG. 465. Equilibrium ratios for methane, 5,000psia convergence pressure. (From
NGAA.")
l
326
F1a. 466. Equilibrium ratios for ethane, 5,000psia convergence pressure. (From
NGAA.~)
327
Fra. 467. Equilibrium ratios for propane, 5,~psia convergence pressure. (From
NGAA.~)
...   

l
328
F:rc. 468. Equilibrium ratios for isobutane1 5 000psia convergence pressure. (From
NGAA.43 )
'
329
FIG. 469. Equilibrium ratios for normal butane, 5,000psia convergence pressure.
(From NGAA.~}
330
331
I tl~~
i<o '"
F1a. 470. Equilibrium ratios for isopentane, 5,000psia convergence pressure. (From
NGAA.~)
FIG. 471. Equilibrium ratios for normal pentane, 5,000psia convergence pressure.
(From NGAA.'3)
332
333
PRESSURE, PSIA
'"'
F1G. 472. Equilibrium ratios for hexane, 5,000psia convergence pressure. (From
NGAA.~)
FIG. 473. Equilibrium ratios for heptane, 5,000psia con,ergenee pressure. (From
1VGAA.43 )
334
(From
335
(From
336
Fra. 476. Equilibrium ratios for decane, 5,000psia convergence pressure. (From
NGAA.g)
337
Fro. 477. Equilibrium ratios for nitrogen, 5,000psia convergence pressure. (From
NGAA.~)
338
1. ?or...i_
r._
339
PRESSURE, PSIA
I 7 '110.000
'""'
'
100
1. Petrol.T....... AIMEl98226!195JJ
2. Petrol. T.. AIM!i 195 99 (\9")
""""
J_
~!P.is~l?'l~bi''fr~'""
3. C.E.P.
Equ;l;t,,;,, s.,.mpa.iurn
Vol. 48 No. 2 P. 121 0952)
'
.t,
FIG. 478. Equilibrium ratios for carbon dioxide, 4,000psia convergence pressure.
(From NGAA.~)
F1a. 479. Equilibrium ratios for hydrogen sulfide, 4,000psia convergence pressure.
(From A'GAA.'43)
340
10 0
""
r...
~ T"..
~
,... ,..
r.....
........... f'=:: ,.,
~
i....._
0J
~
0.0
'
f~
~ t
~~~
,..~
:::. ,.._
K
c, 
!.. [,
t
~ ,._
c.
! 1
...
....... .; ""';..
r. ~ "'~"'"~ ~ ~ r. !. ....
~
c;,
r.::: ~ ,_ ~ '~
)'.
t.:L
...
,._
sired accuracy.
)',
""'
~
~ ~ ""~~ ~ ~
1 "'
r..... ~ ,..
r_
I/II
I ,f J
/)
/
t~
0.00 f
0..000 f
341
O
N
0
0
...,
0
0
..,.
00
00
In <D
" L !?
./
o.t~~~~
'
"'
,
..
I I I I!!
~ ~",h ~
'
~
~
'i
gg
=s
Q.
N
Pressure, psia
F1G. 480. Comparison of equilibrium ratios at l00F for 1,000 and 5,000psia convergence pressure. (From NGAA. 43 )
Hachmuth" and Roland, Smith, and Kaveler4' are plotted in Fig. 481. The
data of Katz are preferred for crudeoil systems, and the data of Roland
et al. are preferred for condensate fluids.
Calculating Procedures for Solution of Equilibrium Problems. The
basic relations developed in Eqs. (474) through (477) apply to hydroca.rbon systems which exist at pressures and temperatures within the twophase region. Equations (478) and (479) apply to the special conditions
existing at the bubblepoint and dewpoint pressures.
The solution of the equations to determine the dewpoint and bubblepoint pressures requires the selection of appropriate equilibrium ratios at
the temperature of interest. An estimate of the pressure is made, and the
O.OOOttLOL...L...Ll..l..U.LtOOL...LLll...lW<L!,0:!0:::0:'''''"10!;;oPOO
Pressure, psio
FIG. 481. Equilibrium ratios of heptanesplus fraction. (Adapted from Katz and
Hachmuth'1 and Roland et al.'':l)

342
L +V = 1
4. Solve the following equations:
(474)
Z;
VK,
(477)
5. If
X; =
i=l
L is the correct value. The values calculated for x/s represent the analysis
m
of the liquid. If
X;
6a. If the calculated value (V)=" is not equal to the assumed value
a new assumption for V must be made and the calculation repeated.
7a. By several successive trials V can be calculated to an accuracy of
about 0.0001.
The procedure outlined is in most convenient form for solution with a
desk calculator which has a cumulative multiplication feature. Successive
trials can be made with a minimum transcription of numbers from the
calculator to a table. A plot of the calculated V as a function of the assumed V is of aid in making estimates for later trials. The number of
trials required depends on the experience of the engineer in estimating
values of V.
The above relations apply when liquid is expected to be the major mole
fraction. Although they are valid even though the vapor is the major fraction, it is desirable to use in that case either Eq. (479) or (480). This
results in determining the composition of the major phase with greater
accuracy.
The solution of equilibrium problems on highspeed computers has stimulated greater interest in flash calculations, particularly in solving reservoir equilibrium problems and multistage separator problems.
.
Rachford 44 has reported on a procedure 'vhich utilizes a form of the equilibrium relation developed as follows:
01
(483)
i=l
o,nd
Since
L=lV
X;=
(L/V
K, = (V)Q,.
(478)
5a. If the calculated value (V),.1o is equal to the assumed value V., the
problem is solved and the composition of the liquid can be determined from.
1
X; =
=~'z"'=~.,
(K,l)V+l
y, = (K,  1) V
J, J' +
and
Therefore,
2';xi = 2';yi =
L,
i=l
Zi
v (L/V) + K;
(476)
343
(K;  l)z;
L, (K,  1) V
i1
+1
Kz)
+ 1 J(V
' " '
 0

(484)
344
the graph of the function has the form shown in Fig. 482. The function
has the unique property of yielding negative values if V (assumed) is too
great and positive values if V (assumed) is too small. Trials can be made
by a_lways assuming V = 0.5 for the initial trial, then successively moving
to higher ~r lower values in a systematic fashion by successive halving of
the steps In the assumed values. This procedure yields rapid convergence
on the correct value.
Another procedure proposed by Holland and Davison" uses the following
form of the equilibrium rel a tion:
evaluated. If the function is not equal to zero within the desired accuracy,
a new L is assumed as follo\'\ts:
J,
m
g(L,K,,z,) =
1  L(i"'_ l/K,)  1 = O
(485)
In this relation Lis assumed and the function is calculated. If the function is not equal to zero 'vith the desired degree of accuracy, a new value
0
Vassumed
0
L assumed
1.0
FIG. 482. Graph of Rachford's equilib FIG. 483. Graph of Holland's equilibrium
rium function. (From Rachford and function. (From Holland and Davison.e)
Rice.'1)
L1  L

ii
 g(L,K,,Z;);1
g'(L,K.,zi)i1
345
(486)
(487)
i=l
Li1
Separator Problems
The application of equilibrium calculations to separator problems requires a brief discussion of the separation process. In a separator, a stream
of fluid, referred to as the feed, is brought to equilibrium at the separator
temperature and pressure. The pressure of the separator i8 subject to
direct control by means of pressureregu1ating devices. The temperature
is usually determined by the temperature of the fluid entering the separator
and the prevailing atmospheric temperature. Thus, the temperature of an
oilfield separator may vary from a low at night to a high during the day.
SP. asonal variations also occur. In some instances separator temperatures
arP. controlled by heating or by refrigeration.
The vapor and liquid are removed from contact on leaving the separator.
Several separators may be operated in series, each receiving the liquid
phase from the separator operating at the next higher pressure. Each condition of pressure and temperature at "\vhich vapor and liquid are separated
is called a stage of separation. Examples of two and threestage separation
processes are sho"\vn in Fig. 484. It can be noted that a process using one
separator and a stock tank is a t\vostage process unless the conditions of
oressure and temperature of the t\vo are identical.
Separator calculations are performed to determine the composition of
the products, the oil volume factor 1 and the volume of gas relea."3ed per
barrel of oil and to determine optimun1 separator conditions for the particular conditions existing in a field.
Example 415 presents a sample calculation of t'vostage separation
applied to the reservoir fluid of Table 413. The equilibrium ratios were
taken from Figs. 465 through 472 and 481. Two calculating procedures
are presented in detail in the example. The calculations are illustrated in
suitable form for the application of desk calculators. Graphs for estimating
the value of V to be used in additional trials after the first two trials are
illustrated in Figs. 485 and 486 for methods A and B, respectively. In
method A, V (assumed) is plotted for each calculated :Zx,. The correct
c==:::;
~
347
346
1.0
Vo or
~
0.9
I~
Vent
Feed
,,
0.8
,_~To
pipeline
Liquid
pt
Separator
Psep and Tsep
0.7
Stocktank
at Pst and Tst
Twostage separation
0.6
,,,, First _
~ assumption
0.5
,,.
E
~
5
1st stage vapor
Vent
Li uid
0.4
0.90
0.4
Feed
To pipeline
Second
assumption
2d sto e vapor
Third
assumption
~
~
1.0
Lxi
0.3
Li uid
15t stage
separator
ot {Psep\ and (T5 epl1
zd
stage
separator
at (Pseplz
Stocktonk
at P5 + and Tst
02
First stage, method A
and { Tseplz
Three stage sepor::ition
0. 1
through the origin. The intersection of the 45 and a curve through the
calculated points yields the new estimate for V.
The calculation procedure by method A yields directly the values of x;,
the mole fraction of a component in the liquid. The mole fractions of the
components in the vapor are calculated from the definition of the equilibrium ratio.
2.0
4.0
5.0
6.0
Fra. 485. Solution of equilibrium ratio equation.:, Eq. (477), for various assumed
gas fractions.
Yi= KiXi
3.0
Lx,
relation i: (L/K:J
'ti 0
0
~
g.t30
l:t
..,
"
'8"' .,......
g f .!'.'
11 J II
g~
et
?'
"C l::I
"
00
EN~
"'
...
~'.jl.t>
::i. ~ 'I
&:' ~ ~
2,
s~.l::I
"' g
g'
~ ~ s::
O"'
e. ~
"" ""' "e.
" ~ s::
~ .:i !r
"'
:<" . &
::=i' bi
0
p..
.g
,.
S '!'
~.
'ii~
"
~.
:!!
;a
(")
!!.
0
m
:t
II
Q N
o.
~
?,1
"'
i~~
"l
0
;;
!!.
g.
Iff z
~
"
0.
'""'
.....
)'
)1'
!1.
"z
;,
"'
g. ~
i!.
.8.
'I
r;;
ff
!i
$1
e.
,."'
p~
'il
11 ;j'
.:Ji!"
Assumed V
p
1t
.0
i::
"' 11l
~ & ~
~ 8. a:
.@ ..... g
)'
~
0 " s::
w wg
~ "'
[ff
{'!)
~
g,
c.
" &."
II
'I
g "' S
'f
g ~.,.
p.. " [
o~
~ 0
"'g!.~ ""'"
? ffl
If~
I!..
.. "'
c.
@!;" ~
l:l'
Assumed V
[~
'!'
p.."'
"
s13 " +
'l
E:
~~
~ C"
g: " "'
"' p.. "'
('[)
[g
"'"o~"
s s
& 1:1" g.
C'D ro """"'
&:~~~~~L~l.~~
a.
__j
(35
PSIA,
40F)
Com
poncnt
c,
c,
c,
c,
c,
c.
c,.
Total
First assumption:
L .0.5. V ... 0.5
Reservoir
fluid
analyeis
K, at
35 psia
"
40F4
YK1
0.3396
0.0646
0.0987
0.0434
0.0320
0.0300
0.3917
61.0000
9.000
2.2000
O.OIOOb
O.l570b
0.0350
0.0032
30.5000
4.5000
'"d
I.0000
0.3050
0.0785
0.0175
0.0016
+ rK1
31.0000
5.0000
1.6000
0.8050
0.5785
0.5175
0.5016
Second assumption:
L  0.55, V "' 0.45
+"l'K;
= x;
0.0109
0.0129
0.0610
0.0539
0.0553
0.0579
0.7809
L+ VK;
x,
L+"VK1
VK;
L+ VK;
27.4500
4.0500
28.0000
4.0600
1.5400
0.8245
0.620(1
0.5657
0.5514
0.0121
0.0159
0.0641
0.0526
0.0510
0.0530
0.7103
29.2214
4.3113
1.0539
0.2922
0.0752
0.0107
0.0015
28.0000
OJ.IOOO
0.2745
0.0706
0.0157
0.0014
0.9596
~From
b
Equations used:
,,
"'
L+ VK;
i= 1
X;
=I
y, = K,:c,
1/io
Y
= m
,: ... 1
Final answer:
0.52096 mole liquid
0.47904 mole vapor
,,
VK;
1.0336
1.0000
Third assumption:
L 0.52096, V  0.4790!
y;
48.3232
J.5748
0.8131
o.5961
0.5377
0.5224
Y1
:1;;K;
L+VK;x;
Q.0114
Q.0133
0.0627
0.0533
Q.0537
0.0559
0.7497
0.6965
0.1203
1.0000
1.0000
0.1379
0.0326
0.0084
0.0019
0.0024
(35
PSIA1
40F)
J(,
Reservoir
fluid
Component
analysis z;
c,
c,
c,
c,
c,
c,
psia and
40F"'
L
v +K.
61.0000
9.0000
2.2000
0.6100'
0.1570'
0.0350
0.0032
62.0000
10.0000
3.2000
1.6100
1.1570
1.0350
1.0032
0.3396
0.0646
0.0987
0.0434
0.0320
0.0300
0.3917
C;+
g]
L  0.5, V  0.5
at 35
0.0055
0.0065
0.0308
0.0269
0.0276
0.0290
0.3905
v, 
Total
a
z
L/V +K,
L  0.55, V  0.45
L K
v:+ '
z
L/V +IC.
62.2222
10.2222
3.4222
1.8322
1.3792
1.2572
1.2254
L
y+K,
0.0054
0.0063
0.0288
0.0237
0.0232
0.0239
0.3196
v
0.5168
L  0.52096, V  0.47904
X;
z
L/V +K;
62.0875
10.0875
3.2875
1.6975
1.2445
1.1225
1.0907
0.0055
0.0064
0.0300
0.0255
0.0257
0.0268
0.3591
v
0.4309
0.4790
y,
0.0114
0.0133
0.0627
0.0533
0.0537
0.0559
0.7497
1.0000
J(,x1
0.6965
0.1203
0.1379
0.0326
0.0084
0.0019
0.0024
1.0000
Equations used:
i1
z;
/.., L/V
+ K,
= J(;x;
 V
y,c
X;
Z;
VL/V +K,
_}jj__
i"' I
Finu.l answer:
0.52096 1nole liquid
0.47004 1nolc vapor
_JI
CALCULATION FOR SECOND STAGE OF SEPARATION
METHOD
Reservoir
Component
fluid
analysis z;
c,
c,
c,
c,
c,
c,
c,.
Total
0.0114
0.0133
0.0627
0.0534
0.0537
0.0558
0.7497
K; at 35
psia and
40F"
145.0000
20.5000
5.1000
1.4000'
0.3750'
0.0750
0.0030
PSIA 1
40F)
First assumption:
Second assumption:
L  0.95, V  0.05
L  0.9789, V  0.0211
y;
VK.:
7.2500
1.0250
0.2550
0.0700
0.0178
0.0037
0.0001
1.0000
(15
+ VK,
8.2000
1.9750
1.2050
1.0200
0.9678
0.9537
0.9501
z
L + VK,  x;
0.0013
0.0067
0.0520
0.0523
0.0554
0.0584
0.7890
1.0154
VK,
3.0595
0.4325
0.1076
0.0295
0.0075
0.0016
0.0006
+ VK;
4.0384
1.4114
1.0865
1.0084
0.9864
0.9805
0.9789
=[(;Xi
+ VK,
0.0028
0.0095
0.0577
0.0529
0.0544
0.0569
0.7658
1.0000
Y
corrected
X;
0.4103
0.1941
0.2942
0.0741
0.0194
0.0043
0.0023
0.0087
0.4109
0.1944
0.2945
0.0742
0.0194
0.0043
0.0023
1.0000
~=

1
352
n1Il Li
nuT
ln
0i
n1
i=l
il
j=l
l Vi if L;
1
n1  n.,
Ifni= 1, then
ii,,, =
i1
V,
i=l
Il L;
:i=l
where n,,, is the mole fraction of total gas in the feed, such that n, =
_ ii,,M.,

p.,
(489)
i=l
V1n1
nl12
V2n2 = V2L1n1
(492)
(493)
If ni = 1, then
n,, +
i=l
=II L,
(491)
(488)
fi.t
(490)
nat
353
p~
where (V,~)m is the volume occupied by 1 mole of feed at reservoir conditions and M = is the molecular weight of the feed. By definition, the
oilformation volume factor
354
(V res),,. =
(Vst)m
Mres
Pst
Prea .Llfdnst
(495)
The calculation of API gravity, total gasoil ratio, and oil formation volume factor is illustrated in Example 416.
The application of equilibrium calculations to the determination of the
optimum firststage separator pressure in a twostage system (one separator
and the stock tank) is illustrated by the data of Table 417 and the graphs
in Fig. 487. The optimum pressure is defined as that pressure at which
33.6
:0
33.4
:t
t:; 33.2
~
a_
gt
33.0
~
~
(2)
(3)
Mole fraction
in liquid
Mole wt,
Component
lb/molel>
phase at
15 psia, 40F"
(4)
(I)
Cr+
Total
16.042
30.068
44.094
58.120
72.146
86.172
263'
0.00283
0.00947
0.05768
0.05292
0.05441
0.05690
0.76579
1.00000
Relative wt,
lb/mole
(2) x (3)
(5)
Liquid.
density
at 60F,
14.7 psiab
(6)
Liquid
volume
cu ft/mole
(4) + (5)
31.64
35.7ld
39.08d
41.36
55.28
0.0803837
0.0861302
0.1004468
0.1185490
3.6433207
4.0108304
0.045399
0.284744
2.543342
3.075710
3.925464
4.903187
201.402770
216.180616
.g
;:
540 ttt\tttrt1.30
,E
.g
580
.g
:;,
u
<D
Example 416. Calculation of Stocktank Gravity Separator and Stocktank GasOil Ratios and Formation Volume Factor.
c,
c,
c,
c,
c,
c,
600 l.Jr1i:;::=::i::::1Tlu 6
355
32.8
eu
.
Density of C"+
520
of c"+
215.850
8 7 lb/ f
= wt
l f Cs+ = 4 .Ol 1 = 53. I
cu t
VO  O
u;
32.6
32.4
g. 500
"'
4800
Firststage separator pressure, psi
the maximum liquid volume is accumulated in the stock tank per volume
of reservoir fluid produced. This pressure corresponds to a maximum in
the API gravity and a minimum in the gasoil ratio and oil formation volume factor. The optimum firststage separator pressure for the system
evaluated in Table 417 and Fig. 487 is 75 psia. The effect of additional
stages can be evaluated in a similar manner.
Equilibrium, or "flash," calculations can be used in many other applications. The applications of the methods to calculating the perlormance of
reservoirs containing condensate fluids or volatile oils are becoming incnasingly important. Many of these applications will be reviewed latoc
in this text.
Wt
% 0 2 in
C'+
Wt
% C, in
C,+
2~~~~ 1 X 100
0.021
(380.69V;)p,,
M,,1L1L2
380.69(.47904) (53.5) (5.61}
216.181 (.52096)(.9789)
= 496.47 cu ft/bbl
l
356
380.69Vz,o,,(5.61)
mol wt ST liq. XL,
REFERENCES
= 380.69(0.0211)(53.5)(5.61)
216.181(.9789)
=
Total GOR
11.35 cu ft/bbl.
separator GOR
+ stocktank GOR
(495)
M,~
P=
122.1748
46.6(5.61) = 0.4 57
Stocktank vol/mole stocktank oil =
=
5~~~;~~)
0. 72027792 bbl/mole
0.467
= 0.367 = 1.2723
TABLE 417. EFFECT OF SEPARATOR PREssURES ON FLUID PROPERTIES
Separator pressure,
psiaa
!st stage
2d stage
(stock tank)
Separator
Stock tank
15
35
75
135
15
15
15
15
587.2
507.7
450.4
368.1
8.5
39.9
135.7
357
Total
Stocktank
oil gravity,
0
API
582.2
516.2
490.3
503.8
32.58
33.26
33.58
33.12
B.,
oil formation
volume
factorb
1.340
1.283
1.265
1.276
l
358
CHAPTER
INTRODUCTION
360
There are essentially three sampling techniques for obtaining reservoirfluid samples for analysis of the pressure, volume, and temperature (PVT)
relations. These three techniques are commonly known as:
I. Bottomhole sampling
2. Recombination sampling
3. Splitstream sampling
The general manner of preparing a well and obtaining a sample for each
of these three testing techniques is presented in the following sections.
Bottomhole Sampling
A well must be selected and properly prepared before any of the sampling techniques can be applied. The engineer should select a well with a
high productivity so as to maintain as high a pressure as possible in the
formation surrounding the \Yell. It is suggested that the well be as new as
possible so as to minimize free gas saturation. The i.vell selected should not
be producing free water. If the only available well does produce water,
special care must be exercised in locating the sampling bomb. A,1Series of
productivity tests should be conducted on the well to deterfulne the
bottomhole flo,ving pressures which exist at various rates of flow. These
tests aid in selecting the well which "~II have the highest flowing bottomhole pressure at the stabilized flow rate. The producing history of the wells
should be studied. The well selected for sampling should have been producing \Vith a stabilized gasoil ratio. If a \Vell exhibits a rapidly increasing gasoil ratio, the saturation conditions \vould probably prohibit the
collecting of a representative sample.
Once the \Yell to be san1pled has been selected and all necessary tests
performed, it must be properly prepared. The time required for well preparation is dependent upon the past history and the productivity of the
well. The well should be flowed at as low a stabilized rate as possible.
The stabilized rate of flow should be continued until such time as a constant gasoil ratio is indicated on the surface. It is desired, but not al~vays
obtained 1 that the lo\V flow rates ,,;JI cause such a small pressure gradient
around the ""ell bore that the gas saturation in the surrounding area will
be reduced, by solution and compression, to an immobile state.
The length of time required to reach a constant producing gasoil ratio
is dependent upon the free gas saturation when the well preparation began.
The well is then shut in to permit the pressure to build up in the formation
adjacent to the well bore. The duration of the shutin period will be de
RESERVOIRFLUID PROPERTIES
361
pendent upon the productivity of the well. In some instances, the time
period may be 2 to 3 hr, whereas in others, it may be as high as 72 hr.
Fluid entering the well bore during the shutin period enters under increasing back pressures. The fluid which is opposite the perforations after
the maximum well pressure is obtained should be gassaturated at the
pressure and temperature at the bottom of the hole.
A tubing pressure survey is conducted to locate the gasoil and wateroil interfaces. A special sampling bomb is run on a wire line. This bomb
is activated at the surlace so as to retrieve a bottomhole fluid sample
under pressure. There are several
different types of bottomhole sampTripping
ling devices on the market. In Fig.
arm
51 is a schematic drawing of a
sampler. The valves are locked open
at the surface, the bomb is located
at the desired sampling position, and
the valves are activated by dropping
a metal bar or by a preset clock
mechanism. Instruction for the operSpring ond
Locking
ation of these various devices will device for
quide for
normally accompany the instrument lower volve
closing bomb
and hence will not be discussed here.
If properly used, all the devices are
successful in obtaining appropriate
samples.
The foregoing well preparation
and sampling procedure can be used
\vith any normal gascrudeoil system. This procedure is often modified
Lower valve
\Vhen reservoir fluid and well conditions meet special requirements.
'\Vhen, at a low stabilized flow rate, Fra. 5L Schematic drawing of bottomhole fluidsample bomb. (From Pirthe fiolving bottomhole pressure of son.1)
the test well is thought to exceed the
bubblepoint pressure of the reservoir fluid, a bottomhole sample can be
collected with the well flowing. An additional step is added to the wellprep~ration procedure previously discussed. After the shutin period, the
'vell 1s allowed to flow at a low stabilized rate. The sample bomb is run,
and the sample collected with the well flowing. The sample collected
s~ould be representative of the reservoir fluid. This is the ideal sampl~ng procedure, as the oil entering is fresh oil at all times and is representative of the reservoir fluid.
The bomb and its fluid sample are brought to the surface. The bomb is

362

____ ________ _
____ .
RESERVOIRFLUID PROPERTIES
checked at the surface for possible leaks. The pressure in the bomb at the
surface is rneasured to indicate whether or not the bomb was properly
activated in the hole. The pressure in the bomb should be slightly less
than the bottomhole pressure at which the sample was collected. Normally, the saturation pressure of the collected sample at surface temperature is measured by pumping water or mercury into the sample and
observing the pressurevolume behavior. Once again, this pressure should
be less than the pressure at which the sample was collected. If it exceeds
the sampling pressure, then the sampling device either collected free gas
or leaked oil. To protect against possible leakage, at least t'vo fluid samples are collected and checked against each other.
If the reservoir were initially at its saturation pressure, the bottomhole
sample obtained would probably indicate a solutiongasoil ratio and
bubblepoint pressure different from that of the original reservoir fluid.
The saturation pressure obtained from the bottomhole fluid sample will
normally be lower than the bubblepoint pressure of the original reservoir
fluid. As the pressure around the well declines with production, gas is
released from solution. This gas either remains in the reservoir or is produced. The oil that enters the well bore has a lower saturation pressure
than that originally existing in the reservoir. Any free gas that enters the
well will migrate upward in the tubing O\Ving to gravity. Hence the oil
collected by t.he bottomhole sampler exhibits a saturation pressuf"e corre' initial
spending to the existing reservoir pressure rather than to the
reservoir pressure.
These inaccuracies in sampling can be corrected either by a mathematical
technique, which will be discussed later in this chapter, or by adding additional gas to the samples in the laboratories. Both methods have limitations but yield a sufficiently close approximation to the actual reservoir
fluid for use in reservoir calculations.
These checks may be over 2hr, 4hr, or longer time intervals if necessary
to oMain the desired stability of the producing gasoil ratio. Once the producmg gasoil ratio stabilizes, the well is ready for sampling.
Gas and liquid samples are collected from the same separator at the
same flow conditions. A larger quantity of separator gas must be collected
because of its high compressibility compared with the liquid. The manner
of collecting these fluid samples varies with company and individual preference. Pressurecontrol devices are attached to the separator to maintain
stabilized conditions. The sampling containers can be attached to the separator as indicated in Fig. 52. The oilcontrol valve should be regulated
Recombination Samples
A second technique used in obtaining fluid samples from which to deter1nine PVT relations is kno,vn as recombination sampling. For a recombination sample, the fluids are collected at the surlace. A sample of separator
oil and separator gas are collected, and these samples are recombined in
the laboratory in the proper proportions as determined by production characteristics measured at the surface during sampling operations.
The selection of the well from which to collect the sample is based upon
the san1e conditions specified for bottomhole sampling. The same presampling tests are desired.
Once the '>vell is selected, it is flowed for a period of time sufficient to
stabilize the producing gasoil ratio at the surlace. It is desired to have
the gasoil ratio checked over at least three comparable time intervals.
363
Pressure
control
Gos
sampling
point
We!I fluid
Liquid
sample
point
Norma! liquid
Internally operated
oillevel control
Se po rotor
meosu rement
point
~~
Stocktank
FIG. 5~. Schematic layout of production facilities with indicated sample poinUI for
recombined samples.
so that the oil sample outlet is always submerged. Regardless of the method
of collecting the fluid samples, the following data should be recorded:
1. A volume of oil in the separator compared with a volume of oil in the
stock tank. This information permits the field calculation of a shrinkage
factor for separator oil. The final shrinkage factor for separator oil is determined in the laboratory by flashing to stocktank conditions.
2. The temperature and pressure of the separator.
3. The temperature and pressure of the stock tank.
4. The specific gravity of the stocktank oil.
5. The amount of separator gas produced per stocktank barrel (GOR
gasoil ratio).
'
6. The gravity of the separator gas obtained in field or laboratory to
correct meter measurements.
7. The flowing bottomhole pressure and temperature.
8. The shutin bottomhole pressure and temperatnre.

364
With these data it is possible to obtain an analysis of the fluid entering the
separator by properly recombining the separator liquid and separator gas.
The recombination method of sampling is just as good as the bottomhole sampling technique for reservoirs where the flowing pressure exceeds
the bubblepoint pressure of the reservoir fluid. When the bottomhole
flowing pressure is less than the bubblepoint pressure, free gas is produced
from the reservoir. The bubblepoint pressure for a recombination sample
may be in excess of the original bubblepoint pressure of the reservoir
fluid owing to the excess gas. In most cases, these errors can be found and
corrections made by taking into account the other data measured while
collecting the sample.
Splitstream Sampling
The third method of sampling is splitstream sampling. This method is
primarily used in sampling of gas condensate wells. The same qualifications
and procedures are used in selecting and preparing a well for splitstream
sampling as were used for obtaining a recombination sample. In addition
to the data measured for recombination sample, it is necessary to note the
temperature and pressure of the flow stream of the point at which the sample is collected.
In splitstream sampling, a smalldiameter tube is inserted into the
middle of the flow stream. Part of the flow is diverted throuiffe this tube
into either an auxiliary separator or sampling bottles. In most cases, this
sample is obtained by inserting the tube in tubing to 8 or 10 ft below the
surface well head connections or in the flow stream just upstream of the
separator. Precaution must be taken to center the tube properly in the
main flow stream. The velocity of fluid flow in the sampling tube should
be maintained equal to the velocity in the pipe. The quantity of fluid removed by the sampling tube should not exceed the quantity of fluid which
is flowing in a comparable area within the main flow stream. This method
is fast. and, if used in conjunction with a small, temperaturecontrolled
separator, will permit an analysis of the reservoir fluid in the field.
The sampling tube can be connected directly to the sample bottle. The
sample thus collected is comparable to a bottomhole sample taken under
flowing conditions. The fluid from the sampling tube can be separated so
as to collect separate gas and liquid samples as in the recombination
method. Greater accuracy is obtained by separating the sample stream
and collecting individual gas and liquid samples. Any variations in instantaneous gasliquid rates are usually averaged out during the period of
separation.
The splitstream method of sampling loses its accuracy with highliquidcontent fluids. It is difficult to ensure the proper entry of gas and liquids
into the sampling tube for high flowing liquidgas ratios. Much of the
I
I
I
RESERVOIRFLUID PROPERTIES
365
liquids will be concentrated along the wall of the pipe owing to friction.
The sample tube located ill the middle of the pipe collects a greater proportion of gas than actually exists. More detailed information on sampling
techniques is available in the literature."'
Once the samples have been collected, they are shipped to a laboratory
for complete analysis. The type of laboratory analysis is dependent upon
the type of reservoir and the information desired.
Laboratory analyses are the same regardless of the method used in collecting the sample. Before any tests can be performed, it is necessary that
a certain amount of preparation be made on the field sample.
In the case of a bottomhole sample it is necessary to raise the temperature and pressure of the field sample to reservoir conditions. The sample
is then transferred to an appropriate test cell for analysis.
The preparation of a recombination sample is more complex. The gas
and oil must be recombined in correct proportions to obtain a representative reservoirfluid sample. The quantities which must be measured in the
laboratory prior to recombination are briefly enumerated. A mole analysis
of the separator liquid and gas sample are obtained usually by means of a
fractional distillation column. A small volume of the separator liquid is
raised to field separator test conditions and flashed to field stocktank test
conditions. The volume of separator liquid and the resulting volume of
stocktank liquid are used in calculating a separator shrinkage factor.
.
volume stocktank oil
S, = separator shrinkage factor =
to .
(51)
vo1ume separa r 011
This shrinkage factor is used to determine the ratio of separator gas to
separator liquid. The separator gasoil ratio is then calculated, and the
number of cubic feet of gas to be recombined with a given volume of separator liquid is determined.
R,,S, = R,.
(52)
366
(2)
Mole
fractiona
Component
c,
c,
c,
0.0238
0.0069
0.0155
0.0230
0.0239
0.0329
0.0440
0.0610
O.i690
iC4
nC,
iC:;
nC,
c,
C7+
(3)
(4)
(5)
(6)
Wt
Molwt
Relative wt,
lb/mole
(2) x (3)
Liquid
density,
16.042
30.068
44.094
58.120
58.120
72.146
72.146
86.172
188.00
0.38180
0.20747
0.68346
1.33676
1.38907
2.37360
3.17442
5.25649
144.57200
159.37507
fraction
(4)/1:(4)
lb/cu ft
(7)
(Liquid
i volume,
cu ft/mole
(4)/(6)
31.64
35.08
36.35
38.90
39.27
41.36
52.77
0.02160
0.03810
0.03821
0.06102
0.08084
0.12709
2.73966
3.10652
D ens1ty
. of C,. = 159.37507  0.38180
 0.20747 =
_10
51 .11372
3 652
Wt % C1 in C,. = 0.239
159.37g0~0~4~.38180
(9)
Mole
Comfraction
ponent
gas, Y>*
N
CO,
H,S
c,
c,
c,
iC4
nC,
iC5
nC,
c,
0.0088
0.0260
0.0140
0.6929
0.1401
0.0731
0.0119
0.0210
0.0049
0.0046
0.0010
0.0017
1.0000
(11)
(12)
Mole
fraction
liquid,
Component
in liquid,
(10)
Component
in gas,
lbmoles/bbl
325 x (9)
380.69
0.00751
0.02220
0.01195
0.59154
0.11960
0.06241
0.01016
0.01793
0.00418
0.00393
0.00085
0.00145
Xi*
0.0238
0.0069
0.0155
0.0230
0.0239
0.0329
0.0440
0.0610
0.7690
lbmoles/bbl
1.79672 x (11)
0.04276
0.01240
0.02785
0.04132
0.04294
0.05911
0.07906
0.10960
1.38168
(13)
(10)
+ (12)
(14)
Mole
fraction
composite,
(13)/1:(13)
Z;
0.00751
0.02220
0.01195
0.63430
0.13200
0.09026
0.05148
0.06087
0.06329
0.08299
0.11045
1.38313
2.65043
0.00283
0.00838
0.00451
0.23932
0.04980
0.03405
0.01942
0.02297
0.02388
0.03131
0.04167
0.52186
1.00000
Wt% C, inc,. =
Cr+
0.00239
0.00130
0.00429
0.00839
0.00872
0.01489
0.01992
0.03298
0.90712
1.00000
367
RESERVOIRFLUID PROPERTIF.S
0.1304

368
 


369
RESERVOffiFLUID PROPERTIES
such as Fig. 46. The gas liberated from solution is the equilibrium vapor
phase which forms in the twophase region.
and the volume change for each pressure increment recorded. This procedure is repeated until a large change in the pressurevolume slope is indicated. This change in slope occurs when gas is liberated from solution.
The pressure at which the large change in the pressurevolume slope occurs
is considered the bubble point (see Fig. 54). After gas is liberated, the
procedure is altered and the sample is brought to equilibrium after each
change in volume. To obtain equilibrium, the sample is thoroughly agiIncipient
for motion
of gos
Vi,
3
,,,.~
Oil
Oil
II
~
,,,.~
Oil
"
r
l
v,,
tated, either with an internal mixing device or by shaking the test cell.
i
.,..,
0v
,,,.N
Oil
"
Oil
>.N
Hg
~=fb
of1
,,,..
j_
.,:>
,,,..,
Oil
>.
volume capacity of the laboratory cell is reached. The resulting data are
expressed as the relative total volume. A procedure will be discussed later
for calculating the total formation volume factor using relative total volume data.
The pressurevolume test is conducted on a hydrocarbon mixture of
definite composition. As no hydrocarbon material is removed from the
cell during the test, the composition of the total hydrocarbon mixture in
the cell remains fixed at the original composition. The test is equivalent
to determining the volume relations along an isotherm of a phase diagram
,,,..,
,,,..
Hg
Hg
Oil
v
,,,.~
j_
Hg
Hg
f2<1
Pa<Po
Pa<fb
~<~<~
After
aqitation
Oisplacinq
qas at a
constant
pressure
All
After
agltatian
.displaced
'"

370
~
371
RESERVOIRFLUID PROPERTIES
Gas Compressibility
The compressibility of the liberated gas or of the separator gas can be
determined in much the same manner as the composite volume factor of
the oil. The gas sample is charged into an evacuated pressure cell, and
the mass of gas in the cell is calculated. The pressure of the gas is increased
by injecting mercury into the cell. The volume of gas in the cell, at the cell
pressure, is determined by the amount of mercury injected. From these
measurements it is possible to calculate the compressibility factor for the
gas by utilizing equations shown in Chap. 4.
The compressibility factor of the gas liberated at each pressure decrement during a differential liberation process can be calculated from the
volumes occupied by the displaced gas at cell pressure and at atmospheric
pressure as measured in a receiver.
The analysis or gas gravity of the gas liberated at each pressure decrement can be determined. Using the analysis or gravity of the gas displaced
at each pressure step, the compressibility factor as a function of pressure
is calculated by the use of pseudocritical properties and compressibility
curves. The methods of calculation are presented in Chap. 4. A sample
calculation from the measured gas gravity for a sample is presented later
in this chapter.
There are numerous other laboratory tests which are often requested on
reservoirfluid samples. These analyses are normally considered in addition
to conventional PVT analysis. Some of the more frequently requested
analyses are fluid viscosity, differentialflash formation volume factors,
equilibrium ratios, and fluid composition. Following are brief discussions
of the procedures used in performing some of these laboratory tests.
Fluid VIScosity
If the oil viscosity is desired at reservoir pressure and temperature, it is
necessary to use a highpressure rollingball viscosimeter. This instrument
measures the time required for a precision steel ball to roll a given distance
in a tube filled with oil. The time of travel is converted to viscosity by
means of a calibration curve for the instrument. The clearance between
the ball and tube can be changed by changing the ball diameter. The lower
the fluid viscosity, the smaller the clearance used.
  
372
In order to measure the reservoiroil viscosity, the rollingball viscosimeter is charged with a reservoirfluid sample at a pressure in excess of the
original reservoir pressure. The pressure in the viscosimeter is lowered by
differential separation of gas and liquid inside the viscosimeter. The viscosity of the liquid remaining from the separation is measured. To reduce
the pressure in the rollingball viscosimeter, the top valve of the viscosimeter is opened slightly, permitting some liberated gas to escape. The
pressure on the system is lowered, and more gas is liberated. The flow of
gas is stopped, and the viscosimeter is rotated, permitting the ball to travel
up and down the tube. This agitates the system and permits the oil and
gas to reach equilibrium. The pressure existing in the cell when equilibrium is reached is the pressure at which the liquid viscosity is measured.
A sample can be differentially liberated in a rollingball viscosimeter
provided the fluid shrinkage is not greater than approximately 50 per cent.
There is excess volume in the top of the viscosimeter for the accumulation
of the free gas, thus keeping the tube completely immersed in oil at all
times. Should the sample have a shrinkage greater than 50 per cent, it
would be necessary to perform the tests in two stages. The first stage
would be with a sample above the original bubble point. This sample
would be permitted to shrink approximately 50 per cent. The viscosimeter
would then be charged with a sample already differentially liberated 'to
some intermediate pressure. The viscosity of the liquid phase over the
remaining pressure range would then be measured.
The rollingball viscosimeter can also be used for measuring gas viscosities. It is rather difficult, as the clearance between the ball and the
tube must be extremely small. Any impurities or any small obstruction
causes the ball to hang, yielding inaccurate readings. In most cases, the
gas viscosity can be calculated from the gas analysis and the curves presented in Figs. 440 through 445. Thus, the engineer is able to calculate
a gas viscosity at each pressure at which he has the analysis of the liberated
gas. This is cheaper, easier, and perhaps more accurate than measuring
these data in the laboratory.
 
RESERVOIRFLUID PROPERTIES
373
is differentially liberated to a pressure. The oil resulting from this differential liberation is then flashed to stocktank conditions. The gas liberated
by the flash is the gas in solution, and the oil volume discharged from the
cell compared with the resulting oil volume is the formation volume factor.
The differential process is continued to a lower value of pressure. The resulting liquid at this lower pressure is flashed to stocktank conditions,
yielding data as in the previous flash. The process is repeated over a number of pressure steps to secure the complete analysis. The above laboratory
procedure can be utilized to obtain a more accurate representation of the
actual separation imposed upon an oilgas system in the production process.
This behavior will be discussed more thoroughly later, where means of
approximating combination formation volume factors will be discussed.
These tests are more expensive and timeconsuming than the conventional
tests. The question arises, Does the reservoir warrant such an expenditure,
or is it necessary for the type of calculations desired? This question
must be answered by the engineer.
Equilibrium Ratios
One of the more expensive laboratory tests is the determination of equilibrium ratios (K values) for a reservoir fluid. This particular type of test
is a modification of the flash test previously described. The test is performed in the following fashion: A cell is charged with a reservoirfluid
sample above its saturation pressure and at reservoir temperature. The
sample is then flashed by dropping the pressure in the cell until gas is
liberated within the cell. The oil and gas are agitated until a state of
equilibrium is reached. The oil and gas are both removed individually
from the cell at the cell pressure, and each analyzed by means of a Podbielniak fractional distillation column. The equilibrium ratios at this particular value of pressure and temperature can be calculated from these
analyses. The cell is recharged with another sample of oil above the original saturation pressure. This sample is flashed to a lower pressure than
the previous sample. Once again the gas and liquid are removed individually at this sampling pressure, and the analysis of each phase determined.
Equilibrium ratios at another pressure and at reservoir temperature are
thus obtained. This procedure is continued over a desired range of pressure. The equilibrium ratios obtained by this procedure apply only to a
material having the composition of the bubblepoint fluid and do not necessarily apply to the gasliquid systems which actually exist in the reservoir
after fluid has been produced.
Fluid Composition
The composition of hydrocarbon fluids is normally determined by frationation. A lowtemperature fractionating column is used for gases, and

374
~
~~
375
RESERVOIRFLUID PROPERTIES
(53)
(54)
VRf
V:i
1
Boa
(55)
% shrinkage differential=
(57)
Rd
(58)


376
RESERVOIRFLUID PROPERTIES
i,
(59)
and
Relative total vol = V,
v,
377
pressure is zero, whereas the gas in solution is a maximum at the bubblepoint pressure.
The numerical values obtained for the gas in solution and gas liberated
will depend upon the process of liberation, flash or differential. In most
cases the gas liberated by a differential liberation process is reported
as the pressure is progressively decreased. Most engineers consider
that the liberation process in the
reservoir more closely approaches a 80
differential process than a flash
1.1 t;;,...C,,""''rj
process. The fluid produced from
Bubblj point
the reservoir to the surface is con1.0r~~The=rm~o~!_s~h~'~'"~'~~~i
sidered to undergo a flash process,
as it is felt that the liberation in
0
the tubing and in the surface equipReservoir pressure, psig
ment closely approaches a true
FIG. 56. Idealized comparison of flash
flash liberation system.
and differential formation volume facIdealized flash and differential
tors.
formation volume factors Bo and
solutiongasoil ratios R11 are presented in Figs. 56 and 57. It is noted
that the flash liberation values are less than those of the differential
process. This relationship between the two processes may occur as shown
or in reverse. The exact relation of the two processes depends on the
composition of the fluid, reservoir
temperature, and the surface separation process.
An illustration of one form in
which the results of a laboratory
analysis of a crude oilgas sample
I
are reported is shown in Tables 51
I
through 53 and Figs. 58 through
R
II
511. The pressures at which the
laboratory measurements were
Bubble point
~
pressure
made are listed in Table 51,
column 1. The relative total vol150~'....J
umes resulting from a flash liberReservoir pressure+, psig
ation process are listed in Table
F1a. 57. Idealized comparison of flash
51, column 2, and are presented
and differential solutiongasoil ratios.
graphically in Fig. 58. It is noted
that a marked change in slope occurs in the relative volume curve at the
bubblepoint pressure. The viscosities of the reservoir liquid resulting from
a differential liberation are reported in Table 51, column 3. It will be noted
s,

TABLE
(1)
Pressure,
psi
51.
(3)
Pressurevolume
relation at 220F,
relative volume of
0.9739
Q.9768
~:
(4)
(5)
(6)
v
v,.,
1.355
1.359
that the viscosity decreases with pressure until the bubble point is reached
and that above the bubble point the viscosity increases with pressure. The
volumes reported in columns 4, 5, and 6 of Table 51 were all measured
during.one laboratory test, a differential liberation of the reservoir sample
from pressures above the bubble point to stocktank conditions of 14. 7 psia
and 60F. The gas liberated from solution expressed as standard cubic
feet per stocktank barrel of oil resulting from the differential liberation is
1.004
4.0
1.363
1.367
0.9799
Q.9829
379
RESERVOIRFLUID PROPERTIES
(2)
5,000
4,700
4,465
4,400
4,100
3,970
3,800
3,600
3,530
3,400
3,200
3,130
3,000
2,900
2,820
2,800
2,695
2,663
2,607
2,560
2,512
2,503
2,358
2,300
2,197
2,008
2,000
1,960
1,773
1,702
1,550
1,470
1,351
1,315
1,180
1,010
992
940
711
705
540
450
410
405
289
150
0

0.968
0.9862
0.9886
0.9909
0.9934
Q.9960
Q.9972
0.9985
1.0000
1.0038
1.0101
1.372
1.375
0.931
1.378
1.382
0.908
1.385
1.387
0.889
0.880
1.389
1.391
638
42
596
l.3n.
89
549
1.351
2.0
1.0
1.0727
~
150
488
1.323
213
425
1.295
200
348
1.260
351
287
1.232
Fro. 58. Volumetric behavior of hydrocarbon sample. (Courtesy of Core Laboratories, Inc.)
412
226
1.205
474
164
1.175
539
638
99
0
l.141
1.066a
reported in column 4. It is noted that as the pressure is progressively decreased, the amount of gas liberated progressively increases. The gas differentially liberated is shown as a function of reservoir pressure in Fig. 59.
The gas in solution in the reservoir liquid at reservoir pressure and temperature is tabulated in Table 51, column 5, and illustrated graphically
in Fig. 510. The differential formation volume factors are presented in
Table 51, column 6, and Fig. 59.
The results of flash liberation of a bubblepoint oil sample through various combinations of stage separation are indicated in Table 52 and Fig.
511. These data were obtained by flashing bubblepoint oil through a
0.997
l.1814
1.2691
0.890
J.0233
1.0447
1.1160
3.0
1.124
1.3792
0o
1,000
2.000
3,000
4,000
5,000
6,000
Pressure, psig
1.5117
1.7108
I.300
2.2404
2.8606
1.570
3.7149
5.1788
2.872
0
At 60F ~ I.ODO
V = volume at given pressure
Vb =volume at saturation pressure at
specified temperature
378
380
381
RESERVOIRFLUID PROPERTIES
stage separator system. The flash separation values reported in Table 52
are used in conjunction with the values in Table 51 to calculate the fluid
properties needed for reservoir calculations. The procedure for calculating
the required fluid characteristics is discussed later in this chapter.
The last major part of a standard fluid analysis is the composition of
the bubblepoint liquid expressed as both weight and mole per cent. The
sample analysis is indicated in Table 53. In all such analyses the liquid
1.70
3.20
1.60
"'
2.80
1.50
2.4 0
1.40 0>
c
~
0
1.30
~
0
"'
c
;:.
.e
;;;
>
"'
c
1.20 1'
2.00
:;:
1.60
1.20
\,
""
iS
1.10
o c......~:='::,."::::'::c,.::::':::::~ 1.00
1,000
2,000
3,000
4,000
5,000
Pressure, psig
Sotvrotlon pressure
I
0.80
f,000
"'...
2poo
3,000
Pressure, psig
4,000
5,000
The t0tal gasoil ratio, which is the sum of the gas liberated in the separator and stock tank (sum of columns 3 and 4), reached a minimum value
for a separation pressure of approximately 100 psig, after which it began
to increase. The gravity of the stocktank oil reached a maximum value
for a firststage separator pressure of approximately 100 psig. The shrinkage factor, which is the reciprocal of the flash formation volume factor,
also reached a maximum at a firststage separator pressure of 100 psig.
The specific gravity of the flashed gas is reported as 0.9725 for the single
density, the molecular weight, and the API gravity of the heptanesplus
fraction are reported. The reporting of these properties is necessary in
choosing satisfactory pseudocritical properties and equilibrium ratios.
A fluid analysis where the values are reported in terms of a unit volume
of oil at the bubblepoint pressure and reservoir temperature is presented
in Table 54.
It is important that the engineer analyze the form in which the fluidanalysis data are reported. The engineer must convert the reported fluid
382
f .39
32.0
640
:;;
~
:::
~~'.;..
0 31.5 ~62 0 .
(I)
".;:
a:
~\
>
=

0
0
:: 30.5: 58 0
0
u
_e
E
'
I
:
2300256
0
(I)
__
f .37 ~
2
//
..
I .36 ~
0
I .35
~~ _
:';
~
54 00
29.5
._
Component
I .38
.'
x'
: 31.0 'f'so

l     ~
0,,it1
I
1"411
1.34
Toto/ gosoil ratio
_Formation volume foc_f!!. ~
L33
200
150
fQO
analysis to the basis of field operating conditions. For example, the gas..
production is normally that liberated at the separator with no record of
the gas liberated from the stocktank oil. In the standard analysis, no
data are reported which relate liberated and solutiongasoil ratios with
respect to separator conditions. If differential data were used, an error
(1)
Separator
pressure,
psi
0
50
100
200
(2)
52
(3)
Sep aSeparator
gasoil
rater
ratioa
temp, F
i4
75
76
77
620
539
505
459
Methane
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
Hexanes
Heavier
Hydrogen sulfide
Weight
4.45
1.59
3.56
0.63
1.43
0.74
1.14
2.12
84.20
0.14
100.00
Mole%
33.78
6.42
9.82
1.33
2.99
1.25
1.93
2.99
38.97
0.52
100.00
Density at 60F,
gm/cc
0.8859
0
API
at 60F
28.l
Mol wt
263
50
TABLE
383
RESERVOIRFLUID PROPERTIES
(4)
Stocktank
gasoil
ratioa
23
49
98
(7)
(6)
(5)
StockFlash
Shrinkage formation
tank
factor,~
gravity,
volume
API at VR1/Vb
factorc
60F
0
29.9
31.5
31.9
31.8
0.7236
0.7463
0.7491
0.74i9
1.382
1.340
1.335
1.337
(8)
Specific
gravity
of
flashed
g!l.'l
0.9725
a Separator and stocktank gasoil ratio in cubic feet of gas at 60F and 14.7 psia per
barrel of stocktank oil at 60F.
b Shrinkage factor: VR1/Vb is barrels of stock tank oil at 60F per barrel of saturated
oil at 2,695 psig and 220F.
c Formation volume factor: Vb/V Rf is barrels of saturated oil at 2,695 psig and 220F
per barrel of stocktank oil at 60F.
approaching 20 per cent for high separator pressures may be made in certain calculations.
In the next section the correction of the reported laboratory data for
fallacies in technique in obtaining samples, for technique of measuring
properties in the laboratory, and for field measurement practices are
presented.
PREPARATION OF FLUIDA.."l"ALYSIS DATA FOR USE
IN RESERVOIR CALCULATIONS
The manner in which fluid samples are collected, analyzed, and reported
has been discussed. It was mentioned that certain corrections of reported
data were required before application to a field problem. The type of corrections required will be dependent upon the state of depletion at which
the fluid sample was collected and the sampling method used. It is desirable to obtain a fluid sample as early in the life of a field as possible so
that the sample will closely approximate the original reservoir fluid. Collection of a fluid sample early in tbe life of a field reduces the chances of
free gas existing in the oil zone of the reservoir.
There are three series of calculations which must be made on laboratory
fluidanalysis data so that they can be used in reservoir calculations. First,
the laboratory data as reported must be smoothed. This smoothing is to
reduce any errors which might have been introduced in laboratory measurements. The smoothing is applied to the relative total volume and
differential oil volume data.
The second series of calculations involves the computation of combination (often called flash) formation volume factors and gasoil ratios. These
parameters are calculated assuming that differential liberation occurs in

384
RESERVOffiFLUID PROPERTIES
the reservoir and that flash liberation occurs between the reservoir and
the stock tank.
The other corrections which are necessary depend upon the sample and
when it was obtained. If, from field data, it is apparent that the bubble
point of the laboratory sample is in error, it becomes necessary to alter all
the values reported in the fluid analysis to fit observed field conditions.
There are several field conditions which might be used to indicate the
accuracy of a fluid analysis. These conditions will be discussed in more
detail when the correcting procedures are amplified.
Smoothing Laboratory Data
The smoothing of laboratory data is accomplished by two means. The
total relative volume is fitted to a dimensionless compressibility curve
which is referred to as the Y function. The Y function usually is linear with
pressure when plotted on rectangular coordinate paper. The relative oil
volume factor is fitted to a dimensionless volume change function. This
function is referred to as the AV or Hurst' function. The logarithm of AV
is usually linear with the logarithm of the difference in pressure and the
bubblepoint pressure.
In determining the best line which will fit the laboratory data points,
two methods are recommended: the mean leastsquares method and ~
method of averages.
Relative Total Volume Data. The pressurevolume relationship of a
crudeoildissolvedgas system is a flash liberation process. A given mass
of the reservoir fluid is expanded in a cell maintained at reservoir tempera
ture, and the equilibrium pressure and volume observed. The laboratory
data are usually expressed as relative total volume V,/V,. These data
frequently require smoothing to correct for laboratory inaccuracies in
measuring small volume changes. A dimensionless compressibility func
tion is used to smooth the values reported by the laboratory. This function is defined as
(510)
be erratic near the bubblepoint pressure owing largely to difficulties associated with measuring small changes in volume in the laboratory pressure
cell.
3.000 o
/
0. I
I ;:
a:~ wooo
;;::'
_, .....
"
_.,.
'
.....
'
II
>.
1.000 o
oo
800
1,600
2,400
3,200
4,000
Pressure, psia
FIG. 512. Smoothing of relative total volume data. Bottomhole sample BHS46C.
. Calculation of Best Y Curve. Straightline relationships are conveu1ently expressed mathematically in the form
Y = a + bx
(511)
where b is the slope and a the intercept.
Several methods are available for fitting an expression such as Eq. (511)
to an array of data point. Two of these methods will be considered here.
P,P
Y =p
==[<""v~,;""v'""',J~.,,1J
where
385
4.000o
stants a and b such that the resulting straightline equation will closely
express the relationship throughout the range of the data. The method of
least squares and m~thod of averages can be used to obtain the equation
of the best curve which can be fitted to the measured data points.
The leastsquares fitting method can be applied to the Y function regardless o.f its curvature. If the data points approximate a straight line,
the equation t? be fitted is Y = a + bP. A value of Y corresponding to
each pressure .IS calculated and then plotted as a fun~tion of pressure.
The curve which best fits these points can then be calculated using the
method of least squares. The laboratory relative volume data in Table 54
are srr_ioothed by means of the leastsquares method in Example 52. The
resultmg leastsquares fit is shown in Fig. 512.
TAilLE
54.
BIIS46C
SAMPLE ANALYSIS OF
AT
224F
Fla.!!h liberation
....
Pres~ure,
5,010
4,910
4,810
4,710
4,610
4,510
4,410
4,310
4,260
4,228
4,210
4,185
4,120
4,060
3,998
3,885
3,810
3,780
3,590
3,410
3,215
3,010
2,930
2,610
2,415
2,210
1,938
1,810
1,578
1,410
1.380
1,200
1,010
976
826
716
630
616
670
246
(3)
(2)
(!)
p~
 P,
pei
(4)
Relative
total
volume
.!'.!
L _1
v.
Differential liberation
p~
Relative
oil
 p
y  P[(V1/V~)  1]
volume~
r..
v.
v.
0
18
43
108
168
230
343
410
448
638
818
1,013
1,218
1,298
1,618
1,813
2,018
2,290
2,418
2,650
2,818
2,848
3,028
3,218
3,253
3,403
3,513
3,598
3,618
3,058
3,Q83
0.9859
0.9875
0.9893
0.9909
0.9028
0.9946
0.0066
O.ll985
0.9905
l.0000
I.0014
1.0036
1.0077
1.0124
1.0172
1.0268
0
O.OII4
0.0036
0.0077
0.0124
0.0172
0.0268
3.0639
2.8541
3.4043
3.3373
3.3446
3.2013
l.0363
1.0555
0.0363
0.0555
3.2649
3.2021
1.1038
0.1038
3.0355
1.1524
0.1524
2.9068
1.2794
0.2794
2.6869
1.4757
0.4757
2.48a9
1.7220
0.7220
2.3259
l.IH9fi
2.1663
0.9105
l.1663
2.2444
2.1635
2.6111
3.0561
3.5012
3.9464
1.6111
2.0561
2.5012
2.9464
2.0709
2.0062
1.9644
1.9383
4.3918
3.3918
1.8021
(8)
(7)
(6)
(6)
D.V  1 
L
v.
Gae expaneion
factor v,
cu ft at S.C.
per cu ft at P
and 227F
compreesibility
factor Z
gravity
0.9286
0.9245
a..
a ..
(12)
(11)
a ..
Relative
libera~d,
volume~
cu It
at S.C .
per bbl
eatun.ted
oil
0.0863
102.7
I.0000
0.0474
0.0526
212.2
0.9050
0.0950
196.0
0.8991
0.9070
0.0782
188.5
0.8709
0.1291
175.8
0.8855
0.9080
0.0770
264.3
331.1
0.8386
0.1614
152.9
0.8832
0.0046
0.0779
0.8091
0.1909
129.1
0.8852
0.8956
0.0858
393.4
0.7812
0.2188
105.4
0.8885
0.8972
0.1002
452.9
0.7552
0.2448
80.7
0.9029
0.9064
0.1231
508.4
0.7307
0.2693
54.8
0.9532
0.9333
0.1709
561.2
0.7039
0.2961
32.8
0.9604
1.0052
0.2945
015.6
0.6735 /
0.3205
12.6
l.0061
1.2272
0.7005
071.7
TABLE
64 (Continued)
__ or t.e5W
Separato:
(10)
(9)
Fluid analysis
(13)
Separator
prenure, psig
(14)
Separator
g11eoil ratio,
OU ft/bbl
(15)
Shrinkage factor,
bbl STO/bbl
saturated oil
(16)
Separator
gas gravity
(17)
STO
gravity, 0 API
100
76
50
30
16
0
1,017
1,054
1,0&1
I,lOQ
1,154
1,202
0.6207
0.6160
0.6130
0.60QO
0.5Q84
O.fi920
0.7447
0.7570
0.7776
0.8015
0.8260
0.8643
38.75
38.65
38.33
37.96
37.42
36.81
(18)
(19)
Components
Separator gas
N,
0.20
1.73
76.39
10.22
7.63
1.04
1.77
0.27
0.38
0.37
co,
c.
c,
c.
iC~
nc,
iC
nC,
c,
c ..
(20)
Separator oil,
mole%
0.0
0.0
2.01
1.71
4.40
1.98
4.01
2.17
2.49
5.62
75.61
(21)
Reeervoir fluid
0.13
I.II
49.05
7.16
6.47
1.38
2.57
0.95
1.14
2.26
27.18

388
RESERVOIR,..FLU!D PROPERTIES
y,=a+bx1
y,=a+bx,
y,=a+bx,
y,a+bx,
(512)
(519)
To verify the goodness of fit of the calculated line, the standard deviation is computed (see Example 52). The standard deviation is calculated
by the following equation:
where n
y; = 4a
+b
i=l
(513)
X;
i=l
y,x, = a
i=l
+b
x;'
na
i=l
+b
i=l
and
Xi!!< = a
x, + b
(516)
x;'
(517)
i=l
i=I
Equations (516) and (517) are the generalized normal equations for
two dimensions. The constants a and b are evaluated by solving Eqs.
(516) and (517) simultaneously, so that
I !
x,
i=l
i=l
y,  n
(xm,)
i=l
nix;(Ix.)'
ii'.=l
i=l
(518)
(520)
The standard deviation has the same units as the data. From Fig. 512 it
is noted that several points near the bubble point were omitted from the
calculations. These were eliminated on the basis of possible errors as
previously mentioned.
Example 52. Smoothing of Relative Volume Data. A calculation of
the bestfitting line by the method of least squares follows ( Y function,
BHS460):
(2)
(3)
(4)
'"  p
P[(V,/Vo)  l]
Pressure
P,psia
yp
P'
3.4043
3.3373
3.3446
3.2943
3.2649
3.2021
3.0355
2.9068
2.6869
2.4839
2.3259
2.2444
2.2207
2.0709
2.0062
1.9644
1.9383
1.8921
47.6235
4,120
4,060
3,998
3,88.5
3,780
3,590
3,215
2,930
2,415
1,938
1,578
1,380
1,200
975
825
715
630
570
41,804
14,025.72
13,549.44
13,371.71
12,798.35
12,341.32
11,495.54
9,759.13
8,516.92
6,488.86
4,813.79
3,670.27
3,097.27
2,664.84
2,019.13
1,655.12
1,404.54
1,221.13
1,078.49
123,971.57
16,974,400
16,483,600
15,984,004
15,093,225
14,288,400
12,888,100
10,336,225
8,584,900
5,832,225
3,755,844
2,490,084
1,904,400
1,440,000
950,625
680,625
511,225
396,900
324,900
128,919,682
(1)
Y*
x,
i=l
i~I
(yo;  y")'
(515)
Generalizing Eqs. (513) and (515) so that they apply ton points
y,
= S = [ ~ '~'
x,
i=l
]1/2
Standard deviation
390
391
RESERVOIRFLUID PROPERTIES
(1)
47.6235
+ b~P
+ 41,804b
na
18a
47.6235  41,804b
18
a=
+ bU"
~YP = a~P
(2)
123,971.57
+ 128,919,682b
b = Y,  Y 1
41 804
'
b + 128,919,682b
41,804a
From the foregoing equation which defines the coordinate points I and 2,
it is possible to calculate the slope of the straightline curve by the following equation:
+ 128,919,682b
31,832,215b = 13,368.64
b = 0.00041997
then
 47.6235  (41,804)(0.00042)
a 18
+ bP =
1.6703
= 30.0658 = 1 6703
18
+ 0.000420P
P1 =
l P,
1
k
= Y,  bP, = Y 1
bP,
(523)
t.V = V,  V = 1  .!:'._
v.
v.
(524)
where V /Vb is the relative oil volume, volume of oil at P per volume of oil
at the bubblepoint pressure. The pressure difference term is denoted as
AP and is expressed as
!!J' = p,  p
(525)
where Po = bubblepoint pressure
P = reservoir pressure at which V /Vb is determined
Y, =
(522)
P,  p,
y,
i1
(521)
Hurst found that the logarithm of t. V and logarithm of t.P should plot as
a straight line. The equation of the resulting straight line is
log t.V = B +Clog t.P
n1
Y,=1
.l
nk i=k+l
y,
or
where
t.V
D t.P 0
D =JOB
C = slope of resulting curve
B = value of log t. V when t.P
(526)
= 1, log !!J' = 0
392
393
RESERVOIRFLUID PROPERTIES
=1DAJ'C
v,
(527)
B 00
v v,
= 
=
v, VRd
C\
B,,., (1  D AP
"
/.
log (P,  P)
av
logD. V
log a V log( p,  P)
410
818
1,218
1,618
2,018
2,418
2,818
3,218
3,618
3,983
2.612784
2.912753
3.085647
3.208979
3.304921
3.383456
3.449941
3.507586
3.558469
3.600210
32.624746
6.826640
8.484130
9.521217
10.297546
10.922503
11.447774
11.902093
12.303160
12.662702
12.961512
107.329277
0.0526
0.0950
0.1291
0.1614
0.1909
0.2188
0.2448
0.2693
0.2961
0.3265
1.279014
1.022276
0.892451
0.792096
0.719194
0.659953
0.611189
0.569764
0.528562
0.486117
7.560616
3.341787
2.977637
2.753789
2.541819
2.376879
2.232922
2.108566
1.998496
1.880871
1.750123
23.962889
7.560616 = lOa
32.624746b
23.962889 = 32.624746a + 107.329277b
a=
23.962889
32.624746
 32 62474~~ 
7 560616
A.
Jog flV: 3.320536
+(0.786052) log(.O,Pl
a=
0.01
1,000
6P, psi
1.0,000
32.624746(0.788709)  7.560616
10
3.329301
log LiV
=a+
blog (P,  P)
0.788709 log (P,  P)
= 3.329201
+ 107.329277b
+ 107.329277b
~~
100
32.624746b  7.560616
10
<l
'
Pi,P
""
(I)
(2)
(1)
(2)
(528)
An illustrative example of this type of calculation for bottomhole sample 46C, Table 54, is shown in Examples 53 and 54, and the resulting
graphical plot is shown in Fig. 513.
0.1
     

394
    "     
Example 54.
for BHS46C.
(1)
(2)
(3)
(4)
0.788709
p,,  p log (P,  P)
log (P,  P)
4,228
3,690
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
0
538
818
1,218
1,618
2,018
2,418
2,818
3,218
3,618
3,983
RESERVOIRFLUID PROPERTIES
2.73078
2.91275
3.08565
3.20898
3.30492
3.38346
3.44994
3.50759
3.55847
3.60021
2.15379
2.29731
2.43367
2.53095
2.60662
2.66856
2.72099
2.76646
2.80659
2.83951
(5)
(6)
log 6.V
Positive
mantissa
of
log 6.V
AV
0.824592
0.968302
0.104471
0.201761
0.277421
0.339361
0.391791
0.437261
0.477391
0.510311
0.06677
0.09296
0.1272
0.1591
0.1894
0.2185
0.2465
0.2737
0.3002
0.3238
1.17541
1.03170
0.89553
0.79825
0.72258
0.66064
0.60821
0.56274
0.52261
0.48969
(7)
(8)
Smoothed
relative
oil
volume
v;v,
1.00000
0.93323
0.90704
0.8728
0.8409
0.8106
0.7815
0.7535
0.7263
0.6998
0.6762
il.V = 1  .!'._
v.
in Example 53.
395
(529)
396
397
RESERVOIRFLUID PROPERTIES
(530)
Example 55. Gas in Solution Corrected for Field Separation Conditions of 50 Psig and 76F.
R, = R,.  (RL)o B,fb
(531)
Bo1b*
where (R,). is the standard cubic feet of gas in solution at P per barrel of
bubblepoint oil.
Multiplying (R,). by the flash bubblepoint formation volume factor
converts the gas in solution per bubblepoint barrel to gas in solution per
stocktank barrel of oil, so that
R. = (R,),,J3,1b
= [(R.1J. = R,. 
(RL).JB,fb
(532)
[(RL),,] BBofb
oob
= 0. 6130 = 1.63132
Pressure
(RL)i,*
(RL),,Bof'
R,
4,228
3,810
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
0
102.7
188.5
264.3
331.l
393.4
452.9
508.4
561.2
615.6
671.7
0
167.54
307.50
43Ll6
540.13
641.76
738.82
829.36
915.50
1,004.24
1,095.76
1083.0
915.46
775.50
651.84
542.87
441.24
344.18
253.64
167.50
78.76
12.76
*Table 54.
Example 56. Determination of Combination Formation Volume Factors for 50 Psig and 74F Separator Conditions (BHS46C).
B
* BQ1i,
o.
Bo1b
od Bodb
VB
Vb
ofb
398
Pressure
v;v,t
Bo
4,228
3,810
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
1.00()0
0.9474
0.9050
0.8709
0.8386
0.8091
0.7812
0.7552
0.7307
0.7039
0.6735
1.63132
1.54551
1.47634
1.42072
1.36802
1.31990
1.27439
1.23197
1.19201
1.14829
1.09869
399
RESERVOIRFLUID PROPERTIES
Table 55 and Figs. 514 and 515 present a comparison of Iaboratorymeasured differential and composite volume factors and solution ratios
and values calculated by the methods described previously. The calcu. lated values closely agree with the measured values to approximately 500
psia.
TABLE 55. COMPARISON OF MEASURED AND CALCULATED COMPOSITE VOLUME
FACTORS AND SoLU""'TION RATIOS
Pressure,
psig
Temp, F
Separator
Stock tank
Total
2,730
1,986
511
140
140
140
566.3
403.3
136.8
36.7
40.6
58.5
603
443.9
195.3
Formation volume
factor Ba
1.2552
1.1752
1.0776
Differential data'
Pressure, psig
Formation volume
factor B"d
2,730
1,986
511
0
180.86
501.0
1.3442
1.2733
1.1430"
Calculated composite
"'
~
.._
~ 4001~~+~~~1~~,j'~79'.,i;f'~~t~~j
Total
566.3
397.4
98.5
603
434.1
135.2
2,730
1,986
511
Oo'~~,..L,,~~~~~..,.l~~~l~~'~~'
500
1,000
1,500
2,000
Pressure, psig
1.2552
1.1890
1.0722
Formation volume
factor Bo/
2,500
3,000

 
400
RESERVOIRFLUID PROPERTIES
can be computed. The three total volume factors result from the different
gas liberation processes: flash, differential, and a combination of the two
processes.
Flash Total Volume Factor. The total volume factor for flash liberation
is computed from data in the fluidanalysis report. The total relative vol
401
This volume factor can also be calculated from data in the fluidanalysis
report. The differential total volume factor is expressed by the following
relation:
(535)
where
g
'0>
:
i.4 f++l\,_ _
_,,_,+'
~
~
~
B,,.,
~ 1.3f+++l~><;;,+,,l
Flo. 515. Comparison of measured and calculated composite oil ,,.olume factors.
(Adapted from Dodson.4 )
volume to the total volume factor. The flash total volume factor is given
by the following relationships:
B
where
Vt
V,
V Rf
V, V,
<!
V, B
v, VRJ = v, "1'
V,
v, (SH).
(534)
differential liberation occurs in the reservoir and flash liberation from the
reservoir to the surface. For the computation of a more realistic total volume factor, the two liberation processes should be combined. The combination total volume factor is dependent upon the same assumptions used
B,
B.1 B,
(RL )"B,,.,
5.61
B.
B.r [ ;,
(536)

402
are calculated by all three methods iu Example 57. The results of Example 57 are graphically compared iu Fig. 516.
Example 57. Calculation of Flash, Differential, and Combination
Total Formation Volume Factors for BHS46C. Separator conditions,
50 psig and 74F. (See table, page 403.)
B,"
B,,,,, =
I
0.6130
vb vR1
"2;
"'
..,;
,_
vb
"
"''
"'
'
"'
.;
"'
"""'
'
;:i
'
'
",_
:':
,_
"'
"'
8 "'
,_
"'"'"' "'"'
"' "'
"'
.."'"'"'
...
00
,_
"'
"'"'
"'
'
"'
'
"'$"'
..
"'~ 00
,,;
"' ,,;"'
0
. "'"' "'"'
"'
 ""'
"'
"'"' 0"'
"'' "'
00
00
00
,_
"'
"'
q
"'
"'"'
"'
00
'
..""'
,_
00
,_
"
00
.. "'..
....  ..
s
,_
0
0
0
0
"'"' "'"'0
'
"''
00
,_
"'"' "'
':
"'
00
"'"'"l
,_
,_
00
0
0
"'
V, B,,,,,,
"'
"'
"'
_
= 1.52671
0 655
V, .!'.'...
"';:i
,_
;;;
&;
"'
00
"'
,_
"'
oi
,,;
.;
;::
""',_ ,_
"'
0
..
"'"'
"'
"'
00
0
0
"'
!::.
(RL)o B6I
5
.;
"'
"'
"'000
"'
e;;
Correcting Fluidanalysis Data to Reservoir Bubblepoint Pressure
Sampling procedures sometimes are in error, so that the samples obtained have an erroneous bubblepoint pressure. In partially depleted
fields or iu fields which originally existed at the bubblepoint pressure, it
is difficult to obtain a fluid sample which actually represents the original
oil in the reservoir at the time of discovery. In these cases it is necessary
to utilize other field data to determine the actual bubble point of the oil
in the reservoir and correct the bubblepoint pressure of the sample to
this value.
In correlating laboratory bubblepoint pressures with field data there
are generalities in behavior 'Yhich will aid in the determination of the actual
, bubblepoint pressure. If the reservoir contained an initial gas cap, it is
ordinarily assumed that the reservoir liquid was saturated at the original
gascap pressure. Exceptions to this rule occur when there is great structural relief. Often, the oil in the lower segments of these reservoirs is undersaturated.
If the reservoir fluid was a singlephase system, it can be assumed that
either the reservoir fluid was undersaturated or the bubblepoint pressure
was the original reservoir pressure. In most fields the production data and
pressure behavior can be used to determine whether the fluid is undersaturated or not. If the producing gasoil ratio remains stable and the
reservoir pressure declines very rapidly for small changes in cumulative
production, it would be suspected that the reservoir fluid was undersatu
'"
~
;;:
,_
0
0
0
e<:l
C':)
~
lQ
t
0
0
C:O<C<:e<C
>OO"""'CO
CJO<:O
Cl 0 0
C'l
Cl 0 0 0
0,...:;,...:;,...:;
00
. "'
"' 00
o

"'....i,...:;,_"'
0"'
"'
0
00
'
oi
"'"'
,_
"'
00
'
"'
"'0
00
 "'...
"0
00000.00
00
r_
0 0><':1 0
Cl
~ ...:<_
C't
o_
MMMMM
::::l
00
,_
"'
 
"'
,_
"'
"'
,_
0
,_
"'
"'
"'
"'
"'
"'
"' "
"' eQ"" 00"""'
"'"' "'
'
,_
"'"'
,_
,_
,_
00>.0000
M
M
Cl<O"':t'C'lCl
C'\1 C'I C'l <N  
403
'
,_
,_
"'
"'
,_
"
0
"'
.....
"'0
....
 "'"' "',_.. ..""'
. :e
"' ""' "'
"' "' .."'"' ""'
"'
,_
00
"'
!'i
"' "'
,_
"'
::i
<Xi
;:i
00
"'
~
&;
00
0
00
"'"'
oi
':
.;
::::l
.. ..
:s"' "' .."'
  "'
00
55
'
00
"'
"000
"' i2"'
"'
"'
0
CllNO...i<
'<!' M C:O 0
M
:e
"' .
00
"'
"'0
"'
::::i.
:s"'
"'
,_
."'"' .."""
"' "
,_
"'
"'
"'
<Xi
"'
...
"'"'0
00
"'
"'
,_
':;\
~
"'
"0
.;
,,;
..
..""' "'"'"'
:e
0
0
00
"'
::i
a:.
;:;
00
,...:; c4

000000
t co 0
CO_ >.q_ ''_ ~ IN_
......
" ' 00
~<:.6
,.:
c4 e<:.i
"'
OIOOOOlQ
tM1''<!'
3~ c:o c:o lO C'1
           
404

RESERVOIRFLUID PROPERTIES
7.6
7.2
6.8
Flosh
Differential
Combination
6.4
x
6. 0
\\
5. 6
5. 2
.6
1\
~\,\
3. 8
3,4
3.0
2.6
\, ~
""'""" "u.
~
2.2
"x....... ~ 1o..~
".....
1.8
00
800
1,200
1,600
2,000
2.400

2,800
~
3,2.00
x
3,600
4PQO
4,400
Pressure
405
rated. If the gasoil ratios tend to increase early in the life of the field and
the reservoir pressure does not decline at a very rapid rate, it could be concluded that the original reservoir pressure was the bubblepoint pressure
of the fluid. If there is no evidence from field data that the oil is undersaturated, the normal procedure is to consider the original reservoir pressure to'_be the bubblepoint pressure of the oil in the reservoir.
It was mentioned previously that the sample analysis could be corrected
to agree with fieldobserved data by changing the volume of gas recombined with the separator liquid sample. A calculation procedure can be
used \~thich assumes that the error in the laboratorymeasured values is
due to an inaccurat.e solutiongas volume.
The calculating procedure assumes that the gas required to correct the
analysis can be added or subtracted according to the laboratory gas liberation data. All the other fluid factors required in reservoir computations
are corrected using the above assumption.
Correction of Liberated GasOil Ratio. The laboratory reports the gas
liberated with respect to a barrel of fluid at the bubblepoint or stocktank
conditions resulting from differential liberation. A set of total liberated
gasoil ratio values is reported with respect to a stocktank barrel of oil
resulting from flash liberation of a bubblepoint sample through various
separator conditions.
Consider first the necessity of correcting the differential liberation data
to the fieldobserved bubblepoint pressure. Assume that only differential
liberation of the solution gas occurs in the reservoir. Also, assume that the
reason the bubblepoint pressure of the reservoir is in error is that too much
or not enough of the liberated gas was collected in the sample. If this is
the case, then the sample data can be corrected by removing or adding the
quantity of gas required to satisfy the true bubblepoint conditions. Before
the required quantity can be calculated, it is necessary to assume that the
solution behavior exhibited by the reservoir sample "~II be valid for correcting the liberated gas data.
The simplest way to make the desired correction is on a differential solutiongasoil ratio curve such as Fig. 517. If the fielddetermined bubblepoint pressure is greater than the sample bubblepoint pressure, the new
quantity of gas in solution is obtained by extrapolating the curve to the
fielddetermined bubblepoint pressure. When the fielddetermined bubblepoint pressure is less than the sample bubblepoint pressure, just stop the
solutiongasoil ratio curve at the fielddetermined value.
The differential liberated gasoil ratio is corrected by adding or subtracting the difference observed between the total solutiongasoil ratio at
the sample and the field bubble points. When the fielddetermined bubble
point is_ greater than the sample bubble point, add the observed difference
to the sample liberated gas data. If the field bubblepoint value is less than
406
t~e ~mple value, ~ubtr~ct the observed difference from the sample values.
Altenng the gas hberat10n data when the bubble point is changed from
4,228 to 3,690 psia is illustrated in Example 58. Liberated gas is used in
1,200
I
1,000
!"....
"'
800
~ 600
F'.
"J'l'<a._ "
400
_/
200
f,200
'
./
2,000
J
x
log
tion process.
400 ~
"'b I'..
4POO
0
5,000
4,228sample BP
3.690field BP
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
130
188.5
264.3
33L!
393.4
452.9
508.4
561.2
615.6
671.7
v, = D(P, 
P)C
I  
200
(RL)b~*
AV
Rewriting in tenns of the relative oil volume factor, the following is obtained:
v
v,
Pressure P, psia
(526)
Pressure, psio
P)
__,,
600 ~
3,000
Correction of Differential Relative Oil Volume. To correct the differential relative oil volume to bubblepoint conditions other than those
measured in the laboratory it is necessary to assume that the dimensionless
volume change quantity AV used in smoothing the laboratory data will
define the new fluid system. In smoothing the differential liberation data
it was shown that
1,000
1,000
800
[.;
I/
407
RESERVOIRFLUID PROPERTIES
(RL)"  (RL).,j
(RL).!
130
0
58.5
134.3
201.1
263.4
322.9
378.4
431.2
485.6
541.7
62.7
143.9
215.5
282.3
346.1
405.6
462.2
520.5
580.6
* (RL)b. is the gas liberated per barrel of bubblepoint oil for the laboratory sample.
t (RL)ab is the gas liberated from the sample bubblepoint pressure to the observed
field bubblepoint pressure per barrel of sample bubblepoint oil.
t (RL)b is the gas liberated per barrel of field bubblepoint oil. (RL)b =
[(RLh  (RL).b] Vb/V~b, where Vb/Vb is the relative oil volume of the field bubblepoint oil to the sample bubblepoint oil.
1  D(P,  P)c
(527)
The values of C and D are determined from the smoothed sample data.
The fielddetermined bubblepoint pressure is now used as Po. The new
value of the relative oil factor at any reservoir pressure P can be calculated
with this relationship.
The preceding equations must be used to calculate at least one relative
oil volume if the field bubblepoint pressure is greater than the sample
bubblepoint pressure. If the field value is less than the sample value of
the bubblepoint pressure, the relative oil volumes can be calculated from
the existing sample data.
Equation (537) is required to calculate the differential oil fonnation
volume factor at the fielddetermined bubblepoint pressure when that
pressure is above the bubblepoint pressure reported for the laboratory
sample. The formation volume factors reported for the laboratory sample
are still valid for the reservoir fluid sample at all pressures below its reported bubble point.
The differential oil formation volume factor
for field determined
bubblepoint conditions can be calculated using corrected oil volume data
and the sample differential oil volume factor as follows:
B,,,
AV1
B,,,
v,  v VRd = VRd V,
VRd
v.
408
RESERVOIBFLUID PROPERTIES
v v;v.. v;v..
v, = v,;v.. = 0_93301
v
v
B., = Vo. B.,, = Vo. (1.52671)
B,,,,,
""' =
1  dV
B,,,,,
1  D(P,  P)C
B.,,,
v;v,
(5371
v v;v...
v, = v,;v,,
(538)
Correction of Flash Formation Volume Factors for Changes in Bubblepoint Pressure. The asswnptions made in calculating the combination
differentialflash system are used in calculating the new flash formation
volume factor and solutiongasoil ratio. In the case of the combination
system it was shown that
B,,,,
Re~Titing
4,228
3,810
3,410
3,010
2,610
2,210
1,810
l,_410
1,010
610
245
Sample
relative oil
volume
V*/Vb
1.0000
0.93301
0.90687
0.8727
0.8408
0.8106
0.7817
0.7538
0.7267
0.7004
0.6768
Adjusted
relative oil
volume
v;v,
1.0000
0.9720
0.9354
0.9012
0.8688
0.8378
0.8079
0.7789
0.7507
0.7254
Adjusted
differential
formation
volume
factor B""*
1.42444
!.38453
1.33236
1.28366
I.23755
1.19343
1.15083
1.10946
1.06931
1.03328
BB. B.,,
"'
(533)
Bofb
results in
(B.rol. VV,
(539)
V 0/V"
Example 59. Adjustment of Relative Oil Volume and Differential
Formation Volume Factors for BHS46C.
Pressure,
psi a
409
pressure
corrected differential formation volume factor at new
bubblepoint pressure
relative oil volume reported in sample for fluid at
field bubblepoint pressure
The new value of gas in solution is calculated by the same equations used
in calculating the gas in solution for the combination system. It is
(532)
where R,. is the gas in solution from the sample analysis and (RL),, is the
standard cubic feet of gas added to or subtracted from the sample liberated
gas values to correct for the change in bubblepoint pressure. The flash
formation volume factor and solutiongasoil ratio for the fluid sample of
Table 54 are corrected in Example 510.
Pressure,
psia
4,228
3,690
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
B,1,
R,t
Adjusted
relative oil
volume V/Vb
B,t
870.9
775.5
651.8
542.9
441.2
344.2
253.6
167.5
78.8
12.8
1.0000
0.9720
0.9354
0.9012
0.8688
0.8378
0.8079
0.7789
0.7507
0.7254
1.52207
1.47945
1.42374
1.37169
1.32237
1.27519
1.22968
1.18554
1.14262
1.10411
(RL).(B,1,),
212.!
307.5
431.2
540.l
641.8
738.8
829.4
915.5
1,004.2
1,095.8
RESERVOIRFLUID PROPERTIES
= (B,1,).(V,jV,,) = (1/0.6130)0.93301
= 1.52207
(RLJ.(B,1),
a+ bP
P,P
P(V,JV,)  1
Bt1
~: Botb
411
provided both the relative total volume v.;v. and the formation volume
factor Both refer to the new bubblepoint conditions. The above correcting procedure was applied to the fluid sample in Table 54. The calculations are presented in Examples 510 and 511.
FLUIDANALYSIS DATA ON GASCONDENSATE SYSTEMS
"
RESERVOIRFLUID PROPERTIES
TAJ3Llil
56.
413
Pressure, psi
Relativ~
volume
5,000
4,800
4,600
4,400
4,300
0.8293
0.8509
0.8753
0.9034
0.9186
4,200
4,100
3,900
3,830 (dew point)
3,797 (reservoir pressure)
0.9340
0.9513
0.9880
1.0000
1.0094
3,600
3,200
2,803
2,400
2,000
1.0552
1.1662
1.3185
1.5325
1.8424
1,622
1,200
932
756
2.2886
3.1160
4.0870
5.0572
of the cell, simulating a well producing only gas with the liquid remaining
in the reservoir. The volume of gas produced is measured and expressed
in standard units. At predetermined pressures, the produced well stream

414
 
Heptanes plus,
mol wt
gpMM:
Propane plus
Butanes plus
Pentanes plus
3,830
3,797
3,500
2,800
2,100
1,400
600
84.80
5.95
2.55
0.47
84.81
5.95
85.61
5.97
86.07
5.95
85.94
6.08
2.57
0.47
0.70
0.28
0.21
0.34
1.48
2.37
2.55
0.48
0.72
0.27
0.21
0.35
1.03
2.37
0.48
0.73
0.29
0.24
0.41
0.88
2.38
85.41
5.99
2.68
0.49
I 100.00
100.00
100.00
119
119
0.75
0.75
0.30
0.21
0.37
2.24
2.36
0.30
0.21
0.37
2.23
2.36
84.95
5.97
2.60
0.44
0.74
0.29
0.21
0.35
2.09
2.36
100.00
100.00
100.00
100.00
128
128
126
124
2.55
0.47
2.554
1.855
1.465
1.771
1.384
2.57
121
1.929
1.227
0.843
2.144
1.442
1.061
2.470
0.75
0.31
0.25
0.48
1.20
2.44
1.883
1.178
0.791
2.124
1.403
1.007
ILLUSTRATING
Deviation factor Z
Volume % produced
3,500
2,800
2,100
0.9430 0.9351
6.490
0
0.9245
23.571
0.9210
42.462
600
1,400
0.9397 0.9771
6l.730
S.'l.535
99.06()4
Ideal expansion
Deviation factor Z / 0.943 / 0.931
Volume % produced 0
6.602
a
0.907
23.216
0.905
42.174
0.923
62.096

415
tion are reported in Fig. 521 and Table 58. A calculated compressibility
factor where no condensation is considered is also reported in Table 58
for comparison. From this comparison it is noted that the compressibility
factors where no liquid condensation is considered are smaller than the
compressibility factors for the pro4.0
duced gas. This is as would be
expected, as the condensed liquid
occupies less space than the same
number of moles of gas would oc3.0
cupy if it were under like pressure
\
conditions.
Use of Condensate Analysis. A E,
careful study of the condensate g
\
fluid analysis that is reported in
2.0
Dew point
Tables 56 through 58 enables the
\
engineer to evaluate better the be "'
1'.
havior of a gascondensate system.
I',
It also enables him to gain an un1.0
,._
derstanding of fluid behavior as
affected by composition and changes
in pressure and temperature. As
an example, observe the change in
f,000 2,000 3,000 4,000 5,000
well stream composition as affected
Pressure, psig
by retrograde condensation. It is
FIG. 518. Pressurevolume relationship
noted that the fraction of the well
for a gascondensate fluid. (Courtesy
stream comprised of methane and
of Core Laboratories, Inc.
ethane changes very little regardles~ of the pressure of the reservoir. It becomes quite apparent that only
minute volumes of methane and ethane are retained in the condensate in
the reservoir. The prima:r,,component which changes with changing
pressures is the heptanes plus (C7+) It is noted that as the pressure
continues to decline, the heptanesplus (C1+) fraction in the well stream
effluent goes through a minimum. If the pressure depletion study were
carried to an ultimate abandonment pressure of 14.7 psia, it would be
found that all the heptanes plus would not be vaporized. All the heptanes
plus do not revaporize because most of the lighter components, methane
and ethane, have been produced. Thus, insufficient quantities of volatile
constituents remain to cause the heptanesplus fraction to revaporize.
~
RESERVOIRFLUID PROPERTIES
Component:
Methane
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
Hexanes
Heptanes plus
Carbon dioxide

0.961
84.182
1.000
100.000
Residual liquid:
Gallons at 60F per MMscf of original fluid = 426.6
Mol wt= 159
Density at 60F = 0.8344
The data reported in conventional fluidanalysis studies have 1nany applications in reservoir engineering. Perhaps the application with which
416
417
RESERVOIRFLUID PROPERTIES
analysis of the depletion study as was reported in the standard gascondensate fluid analysis. The method of making the necessary calculations
for the determination of the abovementioned quantities was discussed in
Chap. 4.
FITTING PUBLISHED EQUILIBRIUMRATIO DATA TO
LABORATORY FLUIDANALYSIS DATA
iOO
c,
ao
60
There are essentially two methods for using fluidanalysis data to calculate or determine the appropriate equi1ibrium ratios for use in reservoir
calculations. One method uses the laboratory bubblepoint or dewpoint
50
40
30
iOO
20
iO
80
c,
6
5

....._
to
,.
c,
co,
'
0.8
:g
L Vc;;
0.6
iC4
0.3
nC5
1,600
2,000
2,400
2,800
\...
\.
1,000
2,000
3,000
Pressure, psig
3,200
40
'
4,000
0.2
i,200
\.
"\.
' '
800
.,.
,g" 0.96
20
c,
400
0.98
nC 4
0.5
0.4
~,
'
'\
too
\.
3,600
4,000
Pressure, psig
FrG. 519. Variation in well stream composition with pressure decline for a gascondensate sample. (Courtesy of Core Laboratories7 Inc.fl)
0.900
1,000
2,000
3,000
4,000
Pressure, psig

418
10
RESERVOIRFLUID PROPERTIES
'
%
~?~
Jll
~.
!'\.~'
,;_~~
.:;,
1\1 )(.. '
'
.,,_.
...
?~"'
"d
:?_..,
~<" ~1'.r.\..
~o~
?
"""+
~Q?
....
?'
:>
~""'
11"(.o:::C" ~::>
_,
'
""'
~~
:::;;
?~!~ '~~ I
? :
?,"'"'<> ,.
""
~ " f::: ........
~~Q?~
 """
ht"" '
10
,~~
Q?
Q?
,/
1111~
102
10
/,
0V''
/

_,
10
100
1,000
10,opo
Pressure, psi a
P'IG. 522. Equilibrium vaporization ratio K at 220F for converg7nce . press ur;~ls~f
5,000 and 10,000 psi. (From school taught by M. J. Rzasa at University o
,
!948.)
or Fig. 522 can be used as a basic group from which to select the equilibriumratio curves to be tested.
.
. This
An apparent convergence pressure must be estrmated for the fluid.
convergence pressure must be at least 10 per cent greater than the de,vp oint or bubblepoint pressure reported in the fluid analysis. The NGAA
f mg apparent
"Equilibrium Ratio Data Book" 7 presents a chart f or estrma
419
420
RESERVOIRFLUID PROPERTIES
Minimum K
0I
10
02
05
10
1,000
002
005
Of
001
800
;;"
'' '
I
~~'
400
'
~ ~ I
~.,
'
100
w
"'
'
40
, I
w
0
~
I/
0
~>
"'
'
'
10
10,000
8,000
'::i
'::i~o;:::.
i~t<;::i "5 (;:) s:::i ~
I
I
11
10
'IA A I; I
Q:)'io
6,000
~ &r;::,~ ~
'<'J~,G:'::io;:::.
"'i'1,~ ~
4,000
,_
:1
6
6,000
.=+&"<>'
JI
11111
, I 11
0.5
'/
0.1
0.05
Pressure for minimum .K
Apparent convergence pressure
0.2
2,000
1,000
0.01
F1a. 523. Correlation of the pressure at \Vhich minimum equilibrium ratio occurs
with the ratio of apparent convergence pressure to the vapor pressure of the component. (From Standing.10 )
ro?()O
4,000
2,000
,, 11
0.02
/.
7
7 >.1\~ .,
17
I/ 17 7 , ~ i900 0
0
1/r/ /. '/1
,,,?
10,000
8,000
,"'
r,1,1/ I/
1,1,1, 11]1 I/
,,
1'
'
II
(,
 sr
~q
I'
I/
00
'?
C7
'
,,,
. J
ti
'
~ ;;.. 20
w
w ,>
0u
11
80
~
~E
u
'
:; ~ 60
w
~
I/ ~\91
:g,o
"
...'?,,
10 0
'I
ti
t,.,.,
\'?,, ~~ \:1():0() ri
~l~~~9.?oooooo
20 0
'::i"
001
,,
::i.'?.~"A
O~'?,,'
c.~\ c:Pti'1
Clc::l ri
II
o;:::.
\~\O
t ~ '<l~~~~~
ii?
" "
,, I
"
200
40 0
002
80 0
' I'
0 "
1.,~~(;:)~
005
60 0
600
;; ;
02
05
f,O oo
421
0.02
0.01
Minimum K
0.005
0.002
1poo
0.001
FrG. 524. Correlation of minimum equilibrium ratio with the ratio of apparent convergence pressure to the vapor pressure of the component. (From Standing.' 0 )
vapor pressure of that component, thus yielding the second set of equilibriumratio points. A third equilibrium ratio, the minimum value for
each component. is determined empirically from Figs. 523 and 524 using
the vapor pressure of the components and the apparent convergence pres

422
     
..
RESERVOIRFLUID PROPERTIES
,,
'
'
1.0
~O;
"'""'
"
"
~44)~
.
1'
~,
""
~'?
" ""'
'
",
'I.
~
"\
Component
Mol
wt
Analysis
Corrected
analysis
z,
Methane
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
Hexanes
Heptanes plus
16
30
44
58
58
72
72
86
128
0.0223
0.0077
D.0031
0.0022
D.0038
0.0228
Carbon dioxide
46
0.D236
0.0000
I.ODDO
l.ODOD
D.8481
0.0595
0.0255
D.8686
0.06D9
D.0047
O.D075
D.D048
0.0030
O.DD2l
D.OD37
D.0261
Ci+
0.01
Zi/Ki
1.550
0.840
0.650
0.535
0.480
0.405
0.355
0.275
0.56038
0.07250
0.04Dl5
D.00897
O.Dl604
0.00765
O.D0619
O.llD!
D.Dl38l
0.20727
0.082t
0.27804
"  0.93296 f
"  l.DD373t/
"'
K*
K;
1.60
0.81
0.56
0.42
D.35
0.21
0.19
0.125
0.070!
0.059t
"
"::'~
I>
1~
423
Z;/K,
0.54280
0.07518
D.0466D
0.01142
0.02200
0.01476
0.01157
0.03D40
0.32571
0.38644
" ~ 1. 08044t
l: = l.14117t
'
0.00 1
10
100
1,000
10,000
this type of system. Therefore, their data will be used here except for
methane, where Brown's11 data will be used.
Step 1. Roughly sketch the 200F equilibriumratio data presented by
Katz (Fig. 463) on a log plot of K, against reservoir pressure.
Step 2. From Katz's data, detennine a set of K values which will satisfy
the bubblepoint conditions that
y,
= z;K,
J;y,
= 1
L > 1
V> 0
424
425
RESERVOIRFLUID PROPERTIES
that these data apply at the bubblepoint pressure of 2,695 psig. The calculations are presented in tabular form below.
exists. With the use of the same ratio, the magnitude of the minimum K
value is obtained from Fig. 524.
When the four K values determined by the previously discussed methods
for each component and the K values detenhined by Katz at pressures less
than 1,000 psia were used, equilibriumratio curves were constructed for
the fluid at reservoir temperature. The curves constructed for this fluid
are sho"n in Fig. 525.
A sample calculation for determination of minimum K value appears on
page 426.
Mole
Component
Methane
Ethane
Propane
Isobutane
nButane
Isopentane
nPentane
Hexane.<>
Wt%
K, 8 at
%
Mole hydro 200F,
% carbons 3,000
only
psi a
(C,+)
ZiK;,
at
zaK,
K;, 3 at
200F,
2,450
psia
z,K,
    
4.45
1.59
3.56
0.63
1.43
0.74
1.14
2.12
33.78
6.42
9.82
1.33
2.99
1.25
1.93
2.99
33.96
6.46
9.87
2.10
0.95
0.66
0.71316 2.75
0.06137 1.10
0.06514 0.64
0.83542
0.93390 2.46
0.07106 0.995 0.06428
0.06317 0.650 0.06416
4.34
0.43
0.01866 0.38
0.01649
3.20
3.00
0.30
0.22
84.20
38.97
39.17
0.024
0.14
0.52
0.00
Heavier
Hydrogen
sulfide
K,8
200F,
2,000
psia
0.88393
0.395 0.01714


1.10220
1.00039
350y,.
Pc3+
(R,/380)
i=3
5.61
(R,/380)
[y;M;/(p;)LJ
i=3
where
(541)
427
RESERVOffiFLUID PROPERTIES
'Y" =
R, =
(p;)L =
Pco+
The weight per cent of ethane in the ethane plus and weight per cent of
methane in the system are defined by Eq. (5.42).
Wt
01
10
C . C
(R,/380)y,M,
2+
2IIl
(542)
350y,,
(R,/380)
y;}d,
i=2
>O 00
c<llNMl'"<l"
Wt
CO'<t'~IN0
000000
01
10
C . C
1 In
(R,/380)y,M,
i+ 
350y,.
(R,/380)
y,M,
i=l
The apparent density of the total mixture at 14. 7 psia and 60F is determined from Fig. 450. Corrections for reservoir pressure and temperature are made with the use of Figs. 451 and 453. Oil formation volume
factors are calculated by Eq. 544.
No Surface Liquid or Gas Analysis. Katz" further simplified the idealsolution method by the use of an empirical correlation. These correlations
eliminate the necessity of knowing the gas analysis. The engineer need
know only the total gasoil ratio, the stocktank liquid gravity, and the
total produced gas gravity. Using the gas gravity and stocktank gravity,
the apparent gas density is determined from Fig. 526. Knowing the apparent gas density, the total produced gasoil ratio, and the gas gravity, it
is possible to calculate the apparent liquid density of the produced gas.
Thus the apparent total density at surface conditions can be obtained by
use of the following equations:
Lb of gas
:so
'Y,
x 28.96
(543)
(p,),,,
Fig. 526
apparent density of stocktank oil and its dissolved gas expressed at 14.7 psia and 60F
429
RESERVOIBFLUID PROPERTIES
The apparent density at surface conditions having been obtained, the procedure is the same as in the previous method, where the density at reservoir conditions is calculated by the use of Figs. 451 and 453. The density
at reservoir conditions having been obtained, the formation volume factor
corresponding to this produced gasoil ratio and the given reservoir temperature and pressure can be calculated with the following equation:
be used in making preliminary economic studies prior to the time that complete fluidanalysis data are either warranted or available.
428
B. = (350)y,,
+ (R,/380)y,(28.96)
5.61 (p.),.,
( 44)
5
where (p,,)res is the density of the reservoir liquid in pounds per cubic foot
and B,, is the formation volume factor. In all the preceding calculations
Empirical Methods
Empirical methods differ from the modified idealsolution methods in
that they depend on curves or equations derived from correlations of laboratory analysis. The empirical methods usually depend on gas gravity,
stocktank gravity, reservoir pressure, and tem~rature.
.
Katz's Curves. Katz 12 prepared a correlatron from data on MrdContinent crudes for calculation of the reservoir formation volume factor.
The use of these charts requires the reservoir temperature, reservoir pressure, gas in solution, and API gravity of the crude. These two curves are
a

LL
15
~$
0
v
e,
10
~~
="
.S ::5_
.C E
<:J>
v 0E
""'
u
""
o"
60
Fla. 526. Correlation of apparent density of dissolved gas and gas gravity. (From
Katz. 12 )
it should be pointed out that the gasoil ratio represents the total gas produced per stocktank barrel and would be the sum of the gas from each
stage of separation. The gas gravity is the gravity of all the gas produced
and if not measured as such would have to be calculated from the gravity
of gas off each individual stage of separation.
All the preceding means of calculating formation volume factors are
accurate within approximately 3 per cent provided the producing gasoil
ratio actually represents the total solution gas. Of course, if the wells are
producing at excess gasoil ratios, then the volume factors as calculated
cannot be expected to correlate with the formation volume factor resulting
from a laboratory analysis. These calculating and correlating procedures
are invaluable in obtaining a first estimate of formation volume factors to
100
150
200
250
300
Temperature, F
FIG. 527. Fluidvolume correction factor for temperature of residual oil. (From
Katz. 12 )
presented in Figs. 527 and 528. If the gasoil ratio required in Fig. 528
is considered to be the producing gasoil ratio, then these curves can be
used to get an estimate of the formation volume factor at that point. These
two curves can be used in conjunction with a correlating curve presented
by Beal" (Fig. 529), in which the gas in solution is correlated with stocktank gravity and saturation pressure. If the gas in solution is determined
from Fig. 529 as a function of stocktank gravity and reservoir pressure,
Figs. 527 and 528 can be used to calculate the formation volume factor
for the reservoir oil. These three curves will then permit the calculation
of a complete formation volume factor and solutiongasoil ratio curves
by using various pressures and assuming the stocktank gravity to remain
constant.
The procedure for calculating formation volume factors using Beal's and
Katz's empirical curvesis illustrated in Example 514.


430
431
RESERVOIRFLUID PROPERTIES
Ex~ple 514. Calculation of Formation Volume Factor and Solutiongas011 Rat10s by Beal and Katz Charts.
p,
R,'
s,t
4,228
1,202!
1,150
1,035
910
790
670
0.620
0.585
0.515
0.445
0.385
0.325
0.265
0.205
0.150
0.100
0.057
3,810
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
~
~
"
1,000
v
~
550
425
310
210
120
+s'P
1.620
1.585
1.515
1.445
1.385
1.325
1.265
1.205
1.150
1.100
1.057
Bo
1.7415
1.7039
1.6286
1.5534
1.4889
1.4244
1.3599
1.2954
1.2363
1.1825
1.1363
.I'
1i
:0
Standing's Correlation. Another empirical correlation has been presented which requires the total gas<>il ratio, the gravity of the stocktank
oil and produced gas, and the reservoir temperature. This correlation was
presented by Standing" for California fluids. The formation volume factor
is expressed by the following equation:
'
'Y o.::;
Bo = GOR '7o
30
40
50
60
70
0/
0
F 1a. ~28. F!uidvolume correction factor for solubility (corrected for temperature
o1 residual otl). (From Kat.z.1 ~)
lS
(1
+ S,)(l +Sp)
R,. = 1,202
Gas gravity = 0.8643
Oil gravity= 36.81API
Separator pressure = 0 psi
+ l.25t
(545)
where all the symbols are as defined previously except t, which is defined
as the reservoir temperature expressed in degrees Fahrenheit.
Standing further amplified the correlation to permit the calculation of
bubblepoint pressures and total volume factors. It is expected that the
results obtained from these correlations would be more accurate than those
obtained from Beal's and Katz's data, as these charts account for the gas
gravity. These charts are presented in Figs. 530 and through 532. Figure
531 represents a graphical solution of Eq. (545). If it is assumed that
the producing gasoil ratio represents the solution ratio, the formation volume factor can be determined from Fig. 531. Working with Fig. 530, it
is possible to take these same parameters, gasoil ratio, gas gravity, tankoil gravity, and reservoir temperature, and determine the pressure at which
a given amount of gas would be in solution. This curve essentially accomplishes the same results as the data presented by Beal but includes more
variables; therefore, it is felt to be more accurate. By combining Figs. 530
and 531 it is possible to determine the formation volume factor and solutiongasoil ratio pressure relationships. If various gasoil ratios are assumed and either a constant gas gravity and :constant stocktank oil gravity
or some predetermined variation with pressure, the pressure and formation

432
volume factor corresponding to each value of gasoil ratio can be determined. Thus, formation volume factors as a function of pressure and gas
in solution as a function of pressure can be approximated from these two
600
60
,;t1 ;z:. 55
, t grO,,,,,
50
Ap1ot__..
45
500
400
40
300
200
100

~
~
~
c
~ ~
200
400
600
800
Pressure, psi
1,000
t:
1,200
2,000
1,800
,,
,o
l,600
~\ ~
"'
35
30
25
20. t,5:::
10
~
"''
1,400
1,200
\,0
1,000
.,o
.o
800
'
30
600
400
lt&e\~\'e
o"
200 
:?~1?,0
20
10
7:...,i
l,000
2,000
3,000
Saturation pressure, psi
4,000
5,000
FIG. 529. Prediction of solubility from saturation pressure and gravity of crude oil.
Represents average conditions for 508 observations from 164 samples taken from 151
oil fields. Average deviation, 22.0 per cent. (From Beal.13 )
curves. The total formation volume factor can be estimated from Fig. 532.
This volume factor represents the reservoir volume occupied by I bbl of
oil and its complement of liberated gas. It is actually a combination of
Figs. 530 and 531 which permits the calculations of the expansion of the
433
~
~

RESERVOIBFLUID PROPERTIES
~
~
=
"'
:3'
435
.D
.D
s
~
.a
>
=
~
'
s
0
::::
.,,g
3 ::::
.;,
~
~
EXAMPLE'
RE'OUIRE'D:
00
"'
d
00
i=
.,,e
0
.D
d
0
"
Bd
Ci
_.,,"'
"'
00
.S:l~
~
"
g..~
0.. 0
;;\ E
0
0 
~~
434
F1a. 532. Properties of natural hydrocarbon mixtures of gas and liquid; formation
volume of .gas plus liquid phases. (From Standing.H)
~======
436
from surface separation with the separator gas. These correlation procedares convert the produced gas gravity to a reservoir gas gravity. In all
the calculations which follow, it is assumed that the produced material is
a gas in the feservoir and that no liquid was produced from the reservoir.
This does not mean that there cannot be liquid existing in the reservoir,
simply that none of that liquid is produced and included in the calculations.
Recombination with Equation of State. The first method for converting
surface volumes to reservoir volumes requires that the following data be
1. 8
,V;
1.7
c:i
.e
/~/
~
1.6
V/7
/],/ /
Ir.
,E
t5
l.P /
p'
1.4
/
,.,.
1,/4
Ir.
1.3
1.2
# ,,,
'.P
/
//
~Y
/' /
1J.. 
1,000
1,500
2,000
Standing's correlations
2,500
3,000
. 3,500
59.
Bubblepoint
pressure,
psi
4,228
3,810
3,410
3,010
2,610
2,210
1,810
1,410
1,010
610
245
Calculated using
Standing's correlations
4,000
Corrected
laboratory data
B,
R,
B,t
R~t
B,,
1.7415
1.7039
1.6286
1.5534
1.4889
1.4244
1.3599
1.2954
1.2363
1.1825
1.1363
1,202
1.740
1.655
1.595
1.520
1,202
1,090
950
830
700
570
450
335
225
127
41
1.6892
1.6003
1.5287
1.4711
1.4165
1.3667
1.3196
1.2757
1.2343
1.1890
1.1376
1,150
1,035
910
790
670
550
425
310
210
120
1.442
1.366
1.310
1.242
1.189
1.139
1.100
=
R.~
1,202
1,028.5
883.6
755.6
642.7
537.5
437.0
343.2
254.0
162.1
67.4
lated from their respective analyses. The moles of fluid produced per day
can be calculated from the gasoil ratio and daily gas production. The
reservoir voidage per day is then given by
Reservoir voidage = (mole produced/day) (cu ft/mole reservoir gas) (546)
~~ ,,,,.500
TABLE
c
437
RESERVOIRFLUID PROPERTIES
'\500
Pressure, psi
Fra. 533. Comparison of measured and calculated oil formation volume factors.
known: analysis of the produced gas, analysis of the condensate, the total
gasoil ratio, and the reservoir temperature and pressure. Using these data
it is possible to calculate the composition of the reservoir gas by the methods indicated with respect to recombined samples in an earlier section of
this chapter. By means of the recombined composition, the compressibility factor can be determined through the use of reduced temperatures
and pressures. When the value of the compressibility factor is known, the
actual volume in the reservoir can be calculated by use of the equation of
state PV = ZnRT. This would give the volume in the reservoir per mole
of fluid. The mclecular weight of the surface gas and liquid can be calcu
Correlation Charts and Equation of State. Another method of converting surface volumes to reservoir volumes is similar to the one previously
discussed except that correlation charts are used for obtaining the gravity
of the reservoir gas. In order to use the correlation charts presented by
Standing, 10 it is necessary that the following data be known: the produced
gas gravity, the barrels of condensate per million cubic feet, and the condensate gravity. From the correlating chart shown in Fig. 534, it is possible to calculate the gravity of a singlephase fluid which would result
from the recombination of the surface gas and liquid. The correlating
chart refers to this singlephase fluid as the well fluid. When the well fluid
gravity is used, pseudocritical properties and compressibility factors for
the fluid are obtained from the fluid property charts in Chap. 4. When the
compressibility factor is known, the solution is the same as in the preceding
example, where the equation of state is used to calculate the reservoir voidage per day or per standard cubic foot produced. Example 515 illustrates
the calculating procedure.
438
439
RESERVOIRFLUID PROPERTIES
~\
.~
} 0.60
gos gr.
(B
AR,T/P)
.fj
1.4
"'
i:
 5
100
45
50
0
.:t ~
>
>
60
55
API
4<f_
gas gr.
} o.~gr..
go~
"'
(,~
~~ 1.2
Pressure,
psi a
100F
130F
160F
190F
220F
250F
600
800
1,000
1,250
4.58
4.46
4.35
4.21
4.09
3.99
3.93
3.89
3.88
3.89
3.92
4.67
4.57
4.47
4.35
4.25
4.17
4.11
4.08
4.06
4.07
4.10
4.75
4.67
4.59
4.49
4.41
4.34
4.29
4.26
4.25
4.26
4.29
4.83
4.76
4.69
4.62
4.55
4.50
4.46
4.43
4.42
4.44
4.47
4.89
4.83
4.87
1,500
1,750
2,000
2,250
2,500
2,750
~,..
=~
'I~.,
,...,
1.3
A(lO)'
} 0.70
~ 150
~~
u~
$$
3,000
Example 515.
20,000
10,000 CFB
100
80
60
40
Bbl condensate per mmd
F1G. 534. Effect of condensate volume on the ratio of surface gas gravity to well
fluid gravity. (From Standing .1)
B  AR,T

where B
A
R,
T
P
(547)
= reservoir temperature, R
=
4.77
4.8?
4.71
4.66
4.62
4.59
4.57
4.57
4.58
4.61
4.7i
.
3.130(0.6174)
Av gas gravity =
3.130
+ 0.213(1.0900)
+ 0.213
 0 6475

1.125
')'.
4.9~
4.W
4.71
4.69
4.68
4.68
4.69
4.71

        
440
B = 44.5
650
T, = 391 = 1.662
= 0.847
Ii
"d
qui
141.5
141.5
+ 131.5 = 53.3 + 131.5 = 0 7657
= API
0
350(0.7657)
121
 2.03316(114.6711
5.61
+ 2.2148)
5.61
= 42.36145
B = AR,T
p
4.458
4
44.5(76.725)
= 3414.263 bbl/day
p gr
441
= 3340.634 bbl/day
p  2,900  4 367
,  664 
RESERVOmFLUID PROPERTIES
,,P, = 664
,T, = 391
~
.453 C;~~5lC550)
= 43.54036
Viscosity of Oils. Beal13 presented empirical correlations for the determination of reservoir fluid viscosities dependent upon the stocktank

442
443
RESERVOIRFLUID PROPERTIES
that the reservoir oil viscosity is 0.8 centipoise. Figure 537 pennits the
calculation of the oil viscosity for undersaturated crude oils.
These three curves were used to calculate the viscosity of the reservoir
fluid presented in Table 51. A comparison of the empirical and measured
viscosity values are shown in Fig. 538. It is noted that the viscosities calculated by Beal's correlation are slightly greater than the viscosities actually measured in the laboratory. Exact agreement cannot be expected, as
10,000
8,00 0
6,000
4,00 0
2,000
Q,)
g_
'.
~
.,,=
.
~
1,00 0 \ \
80 0
60
0 ' '
400
\ \
o''' \.
20
0 ,\ \ \
10
80
60
40
'
'
20
0
8
6
.,,
'\..r>~.
"'o"'
'" ~"""~~
~o
''
3
2
,...o0
G:
.,
,,.
~ /~!:2
" ~"" ~
0.8
0.6
0.4
0. 3
0.2
1
;.><v..~
f.._
~
20
Crudeoil gravity
30
0
40
.,
'

50
60
535. Gasfree crude viscosity as a function or reservoir temperature and stocktank crude gravity. (From Beal.13 )
FIG.
oil is saturated or undersaturated. Take, for example, the case when the
crudeoil gravity is 32} 0 API at stocktank conditions and reservoir temperature is 175F. Then from Fig. 535 it is found that the viscoity of the
gasfree crude oil at reservoir temperature is 2.3 centipoises. From Fig.
536 entering with the gas in solution, 500 scf at 2,000 psia from Fig. 529
and reading to the gasfree crudeoil viscosity from Fig. 535 1 it is found
]
q
0. 2
0.
'0
100
200
300
400
500
600
700
800
900
l,000
t~OO
l,200
1,300
f.,400
FrG. 536. Reservoir crudeoil viscosity from gasfree crudeoil viscosity and gas in
solution. Correlation based on 351 viscosity observations from 41 crudeoil samples
representing average conditions for 29 oil fields. Average deviation, 13.4 per cent.
(From Beal.' 3 )
________ _________
,.,
444
(1)
p

445
RESERVOIRFLUID PROPERTIES
(2)
(3)
Mo!
Gravity*
wt
(4)
(5)
I ,P,t
pTct
0.9245
0.9070
0.9080
0.9046
0.8956
0.8972
0.9064
0.9333
1.0052
1.2272
26.81
26.30
26.33
26.23
25.97
26.02
26.29
27.07
29.15
35.59
T,
   
Exfrapolafed
3,810
3,410
3,010
2.610
2,210
1,810
1,410
1,010
610
245
(6)
460
454
454
453
451
451
656
657
657
657
658
658
657
656
653
638
454
462
483
555
1.487
1.507
1.507
1.510
1.517
1.517
1.507
1.481
1.416
1.232
(7)
(9)
(8)
(10)
P,
/it
5.808
5.190
4.581
3.973
3.359
2.751
2.146
1.540
0.934
0.384
 2.3
2.1
1.92
1.75
1.6
1.4
1.29
1.19
1.08
1.02
0.0118
0.0119
0.0119
0.0119
0.0120
0.0120
0.0119
0.0118
0.0116
0.0110
0.0271
0.0250
0.0228
0.0208
0.0192
0.0168
0.0154
0.0140
0.0125
0.0112
column 10.
3.20
.,
~
2.80
0 (For more occurote values see i11sert above)
0
l,000
2,000
3,000
4,000
5,000
2 3 4
Pressure,
mpirico/
thousands psi
Fro. 537. Viscosity of crude oil above the bubblepoint pressure. Average deviation,
2.7 per cent. (From Beal. 13 )
Measured
2~0
~
0
~
~ 2.00
tion so far outweighs the effect of pressure that the viscosity of the reservoir fluid decreases with increasing pressure.
Viscosity of Gases. The gas viscosity can be calculated by the procedures of Carr" outlined in Chap. 4. The application of the procedure to
calculation of the viscosity of the liberated gas from sample analysis BHS46C is presented in Example 516.
;;
~
;;; 1.60
0
>
1.20
0.80
Example 516.
\.,\~
"' ' ~
....,
= (;,) 1
1..

2,000
3,000
4,000
5.000
Pressure, psig
446
RESERVOIRFLUID PROPERTIES
California Oils and Gases, Drilling and Production Practice, 275, American Petroleum
0.030
Institute, 1947.
>: 0.022
.;;;
0
<II
0
..,
15. Sage, B. H., and R.H. Olds: Volumetric Behavior of Oil and Gas from Several
San Joaquin Valley Fields, AIME Petrol. Trans., vol. 170, 1947.
16. Carr, N. L., R. Kobayaski, and D. B. Burrows: Viscosity of Hydrocarbon Ga...~
under Pressure, AIME Petrol. Trans., vol. 201, 1954.
0.026
;;:
>
447
0.018
../""'
0.014
/""'
500
t,000
1,500
2,000
2,500
Pressure, psi
3,000
3,500
4,000
REFERENCES
1. Pirson, S. J.: "Oil Reservoir Engineering," 1st ed., McGrawHill Book Company,
Inc., 1950.
2. Reudelhuber, F. 0.: Petroleum Technology, AIME Con! Proc. of 1956, Texas
A and M College.
3. Frank Purdum Co.: "Laboratory Procedures for Testing Samples."
4. Dodson, C. R., D. Goodwill, and E. H. Mayer: Application of Laboratory PVT
Data to Reservoir Engineering Problems, Al1l!E Petrol. Trans., vol. 198, 1953.
5. Hurst, W., Personal Communication.
6. Core Laboratory Example Reservoir Crude Oil Analysis Trade Literature, Core
Laboratories, Inc.
7. "Equilibrium Ratio Data Book," Natural Gasoline Association of America,
Tulsa, Okla., 1957.
8. Katz, D. L., and K. H. Hachmuth: Vaporization Equilibrium Constants in a
Crude OilNatural Gas System, Ind. Eng. Chem., vol. 29, 1937.
9. Roland, C. H., D. E. Smith, and H. H. Kaveler: Equilibrium Constants for a
Gasdistillate System, Oil Gas J., vol 39, no. 46, Mar. 7, 1941.
10. Standing, M. B.: "Volumetric and Phase Behavior of Oil Field Hydrocarbon
Systems," Reinhold Publishing Corporation, New York, 1952.
11. Brown, G. G.: Charts presented in "Natural Gasoline Supply Men's Association
Technical Manual," 5th ed., Natural Gasoline Supply Men's Association, 1946.
12. Katz, D. L., Prediction of the Shrinkage of Crude Oils, Drilling and Production
Practice, 137, American Petroleum Institute, 1942.
13. Beal, C.: The Viscosity of Air, Water, Natural Gas, Crude Oil and Its Associated
Gases at Oil Field Temperatures and Pressures, AIME Petrol. Trans., vol. 165, 1946.
14. Standing, M. B.: A PressureVolumeTemperature Correlation for Mixtures of
PROPERTIES OF WATER
CHAPTER
PROPERTIES OF WATER
INTRODUCTION
449
from the characteristics of the water. The analysis should show the total
solids and the parts per million of each positive and negative ion and/or
radical. From this information it will be possible to represent the analysis
graphically and to calculate reacting values, products, and properties of
reaction.
Whenever possible it is recommended that representative samples of
the particular reservoir water be obtained and their physical and chemical
properties determined through the services of a reputable laboratory.
Quite often this procedure is not feasible owing to timing, economics, or
other reasons. If circumstances are such, the petroleumreservoir engineer
may then find it expedient to resort to empirical data or correlation charts.
The majority of this chapter is devoted to the consideration of solution of
water problems through use of these data and correlations. Prior to the
discussion of the use of these correlations it is appropriate to consider the
scope of the research on which the correlations were developed and the
limitations of their utility.
Historically much confusion exists in the early petroleumreservoir engineering literature regarding identification and classification of reservoir
waters. In an effort to alleviate this difficulty, the American Petroleum
Institute, in 1941, acting through its Subcommittee on Core Analysis, conducted a study on reservoir waters. Questionnaires submitted to petroleum technologists requesting reservoir water classifications yielded some
300 different types and terminology, the majority of which have appeared
in the literature. Although there was considerable difference of opinion,
the subcommittee was successful in establishing widespread and common
usage of such water terms as connate, interstitial, residual, and free, to
name only a few. The discussions which follow in this chapter are applicable to all types and classifications of reservoir 'vaters.
Since reservoir pressures as high as 15,000 psi and temperatures as high
as 350F have been encountered in vastly different geologi~al environments, reservoir waters exhibit widely varying physical and chemical
properties. As a result, salinities in the hundreds of thousands of parts
per million, gas solubilities of 50 cu ft per bbl, waterformation volume
factors exceeding 1.20 bbl per bbl, compressibilities of 4 X 10 bbl per
bbl per psi, and viscosities of less than 0.10 centipoise have been observed.
In this chapter all the gas volumes are expressed at 14.73 psia and 60F
and the water volumes are expressed at 60F unless designated otherwise.
Furthermore, reservoir waters are assumed to be saturated with natural
gas at the reservoir conditions unless specified otherwise.
The physical properties of water are dependent upon its chemical compoSition, temperature, and pressure. Water may be pure or may contain
dissolved, entrained, or suspended salts; inert materials; or gases.
There is much information in the technical literature on the properties
450
PROPERTIES OF WATER
451
22
ture and pressure ranges. There are very few data in the literature on the
effect of pressure, temperature, and composition on the physical properties
of pure or reservoir waters at pressures exceeding 5,000 psia, temperatures
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