Thermodynamics 1
Thermodynamics 1
Thermodynamics 1
Instructional Objectives
After seeing this module the student should be able to:
• Understand the differences and limitations among standard PVT tests (CCE,DL,
etc.)
• Select the appropriate fluid model based upon fluid characteristics and production
data.
Phase behavior is the study of changes of the intensive properties of fluids (either
single component or mixtures) as a function of changes in pressure, temperature and
compositions. These properties include:
• Compressibility
• Surface tension
• Heat capacity
We will concentrate in property and phase changes of Hydrocarbon Species and fluids
used for EOR purposes.
Definitions
Before beginning this course we must become familiar with certain definitions.
System: A body of matter with finite boundaries (physical or virtual), which can be
considered as isolated from surroundings if desired.
• Closed System: Does not exchange matter with surroundings but may exchange
energy (heat).
Phase: A portion of the system which has homogeneous intensive properties and it is
bounded by a physical surface. Homogeneous means that it is possible to move from
one point to another within that region without detecting a discontinuous change in a
property. An abrupt change in a property is observed when an interface is crossed. An
interface separates two or more phases. These phases are solid, liquid(s), and gas. A
phase can be a system by itself since the selection of a system is arbitrary. Examples:
• Compressibility
• Surface tension
• Heat capacity
• Thermal conductivity
Equilibrium State: When all intensive properties remain unchanged with time. In
thermodynamics it is taken to mean not only the absence of change but the absence of
any tendency toward change on a macroscopic scale. At equilibrium, there are not
driving forces:
Phase Behavior Diagrams: These diagrams are called phase envelopes. The dew
point curve and the bubble point curve converge at the mixture critical point.
Process: Any change of a system is called a thermodynamic process which may occur
with no restrictions or under arbitrarily prescribed conditions ( i.e. T constant, P
constant, V constant)
Mathematical Concepts
The following is a list of the mathematical concepts required for this course.
“Space” Coordinates: Here we will not deal with space coordinates but the axes will
be: P, V, T, and the composition of a selected component (pseudocomponent).
• Integration
The overall objectives of this course are to understand and to be able to predict the
phase behavior and fluid phase properties using a variety of methods, mainly equations
of state (EOS). This requires a sequence of steps which will be covered along the
course, beginning with pure substances and extending to binary and multicomponent
systems.
Crude oil is always associated with gas under any condition in the production system.
The pressure-volume behavior of oil is intimately affected by the type and amount of
gas in solution.
As the reservoir pressure decreases, the gas evolves from solution to form a two-phase
system. The relative rates of the gas and oil being removed from the reservoir would
affect the oil volume behavior in the reservoir as well as at stock tank conditions.
o
Location Pressure (psia) Temperature ( F)
The oil and gas properties of interest to reservoir engineers from a Black Oil model
perspective are:
Separator gas
Separator gas
Rv =
Standard
Separator gas
Conditions
Bg =
STB
gas
P4 P3 Reservoir
P2 P1
gas gas
oil oil
oil oil
Decreasing Pressure
Separator gas
Separator gas
Standard oil
Conditions
STB Bo= Rs=
STB STB
Figure 2 - Definition of oil and gas PVT properties based on their volumetric behavior.
Light in color
+
C7 composition < 12.5%
Separator conditions lie within phase envelope and liquid is produced at surface
Its main use is for converting reservoir gas volume to surface gas volume, and vice
versa. The mathematical expression is:
VR
Bg = (1)
V SC
… mathematically using the real gas EOS …
ZnRT
Bg = P
Z SC nRTSC
(2)
PSC
Replacing values for the standard pressure and temperature and considering that the
compressibility factor at standard conditions is essentially equal to one we have:
ZRT RCF
Bg =
380 .7 P SCF (3)
This property is expressed in terms of the gas compressibility factor (Z) as follows
where SCF = standard cubic feet & RCF = reservoir cubic feet
Other common units for the gas formation volume factor are (reservoir barrels /
standard cubic feet). In that case:
ZRT RB
Bg = 0.00502 (4)
P SCF
The key is how to determine the compressibility factor “Z” for the gas in question, at
different pressures, & at different temperatures and gas compositions.
Z Tr
Pr
Only one compressibility factor chart can be used to determine volumetric properties for
any pure hydrocarbon fluid and mixtures. That is accomplished by using the
corresponding states principle and reduced properties (Pr & Tr)
Isothermal Compressibility
1 dV g
Cg = − (5)
V g dP
Numerically can be evaluated as …
(B g1 − B g 2 )
Cg = −=−
B g1 (P1 − P2 )
(6)
-1
The units for isothermal compressibility are: psia
The following figures show the typical behavior of reservoir engineering properties such
as Bo, Rs, Bg, Co, etc. with pressure. The student should review these properties and
their definitions from McCain book.
B
t
Bt, Bo
B =B
t o
Bo
Pb
Pressure
Figure 4 - Oil formation volume factor.
The phase behavior of reservoir fluids (oil and gas) is determined from a laboratory
analysis of a reservoir fluid sample. The pressure-volume-temperature relationship can
be used to evaluate the reservoir oil behavior under different pressure and temperature
conditions. It can also be used to classify the type of reservoir and the reservoir fluid.
Pressure
Figure 5 - Gas formation volume factor.
Oil Viscosity
Viscosity
Pb
Pressure
Figure 6 - Oil viscosity.
Gas Solubility
Gas in Solution
Pb
Pressure
Figure 7 - Gas solubility.
Isothermal Compressibility
Specific Volume
ry
da
un
Bo
ase
T
Ph
∆V
∆P Pressure
Thermal Expansion
Specific Volume
DV
∆Τ Temperature
Figure 9 - Thermal expansion.
• separator tests
FLASH VAPORIZATION
The flash vaporization is a process of gas-oil separation in which the gas and oil are
always in contact throughout the entire life of the separation. It is conducted at the
reservoir temperature.
The following figure shows the flash separation process in which the temperature of the
test equals the reservoir temperature.
Flash Vaporization
Flash Separation (Liberation)
1 2 3 4 5
gas gas
Vt3=Vb
V t1 V t2
V t4 V t5
oil oil oil oil
oil
Hg Hg Hg
Hg
Hg
This test is used to determine bubble point pressures by intersecting the lines
representing volume variations in the liquid and two phase regions.
Pressure
Pb
Vb
Volume
Figure 11 - Bubble point determination.
DIFFERENTIAL SEPARATION
The differential separation is a gas-oil separation process in which the gas separated at
one stage is removed before the remaining oil is subjected to the next stage of
separation. The separation process is conducted at the reservoir temperature and
pressure except the last stage which is conducted at standard conditions (P = 14.7
o
psia, T = 60 F).
gas gas
gas
oil
oil oil oil
oil
Hg Hg oil
Hg
Hg
Hg
P1 = P b P2 < P b P2 < P b P2 < P b P3 < P2 < Pb
Figure 12 - Differential liberation process.
These tests are used to determine formation volume factors and solution gas oil ratios.
SEPARATOR TESTS
Separator-Separation
Separator
Reservoir
Standard
Conditions
Gas
Oil
Other oil properties of interest are oil compressibility, thermal expansion, and viscosity.
These oil properties can either be determined from laboratory tests or from available
correlations.
Production System
Stock Tank
Well Head
Water
Oil Sales
Lab Tests
Reservoir
• Volumetric
• Production Test
• Well Completion
This section reviews qualitative and quantitative aspects of phase behavior that will be
used through the reminder of the course.
As oil and gas are produced from the reservoir, they are subjected to a series of
pressure and temperature changes. Such changes affect the volumetric and transport
behavior of these reservoir fluids and, consequently, the produced oil and gas volumes.
We need to quantify the real oil and gas volumes under various pressures and
temperatures. There are basically two models to do this.
Compositional Model
• Oil and gas are mixtures of several components
• Has only two components named as the phases: Gas (G) and Oil (O).
• The G component may be dissolved in the oil phase and this is taken into account
through the solution gas oil ratio (Rs). However the oil component (O), cannot
dissolve in the gas phase.
• Volumetric properties are determined from separate correlations for gas and oil
phases.
The phase behavior of crude oil, water, and EOR fluids is a common ground for
understanding the displacement mechanisms of EOR processes. This behavior
includes the two or more phases formed in crude oil – miscible solvent injection
processes, the gas–oil–water phases of steam flooding, and the two – and three –
phase behavior of surfactant–brine–oil systems.
Cricondenbar
Bubblepoint Curve
Critical
Quality
Pressure
75% Lines
50%
Cricondentherm
25%
Temperature
Bubble Point Curve Boundary between liquid phase and 2-phase region
Dew Point Curve Boundary between gas phase and 2-phase region.
Critical Point Location where bubble point and dew-point curves meet.
Initial Reservoir
Conditions
CP
Pressure
Path of Production
Separator Conditions
Temperature
CP Initial Reservoir
Conditions
Pressure
Path of Production
Separator Conditions
Temperature
Separator conditions are within the phase envelope, therefore some liquid will be
produced at surface
Initial Reservoir
Conditions
CP
Pressure
Path of Production
Separator Conditions
Temperature
Initial Reservoir
Conditions
CP
Path of Production
Pressure
Separator Conditions
75%
25%
50%
Temperature
Initial Reservoir
Conditions
Path of Production
CP
Pressure
75% 50%
25%
Separator Conditions
Temperature
If we overlap the phase envelopes for all fluid types in one diagram we will have a
series of phase envelopes in which the critical points of the mixtures have the following
trend:
• Critical Pressures increase from dry gas, to condensate and volatile where they
reach a maximum and drop again for black oils.
The following plot contains calculated phase envelopes with hydrocarbon mixtures with
the same components but with different proportions.
7000
TR Critical Points
6000
Volatile I
5000
Condensate Volatile II
Pressure (psia)
4000
3000
Dry Gas
0
-200 -100 0 100 200 300 400 500 600 700 800
o
Temperature F
Component Black Oil Volatile Oil Gas Condensate Wet Gas Dry Gas
Reservoir fluids also contain other chemical species that may complicate the phase
behavior even further. Table 3 provides a general guideline of reservoir fluid
compositions, while Table 4 contains information about typical petroleum gases and
heavy oil fractions.
Table 4 - Typical compositions of petroleum gases and heavy crude oil fractions.
Pressure versus temperature diagrams can be used to visualize the fluids production
path from the reservoir to the surface, and to classify reservoir fluids according to the
location of its critical temperature with respect to the reservoir temperature.
Based upon this classification one may decide to use a black oil model or a
compositional model.
The following diagram indicates the region of applicability for a black oil model.
Pressure versus temperature diagrams are called phase envelopes. The dew point
curve and the bubble point curve converge at the mixture critical point.
The region of application for a compositional model is indicated in the following figure.
Compositional
Equations of state models are calibrated with properties of pure components and later
generalized to mixtures by using mixing rules and molar compositions.
Single Component
Fusion Curve
2 phases Critical
Point
Pc
Solid Liquid
(1 phase)
Pressure
(1 phase)
Vapor Pressure
Curve (2 phases)
Tc
Temperature
The petroleum engineer is usually interested in a smaller region of this phase diagram.
The region covering vapor-liquid-equilibrium (VLE).
Pc Critical Point
ρl
Pressure
Liquid
ρv
Vapor
Tc
Temperature
Figure 25 - Vapor pressure curve for a single component.
Figure 25 illustrates the vapor pressure curve for a pure component. As the
temperature increases the vapor pressure increases until the critical point. At
temperatures higher than the critical temperature there is not a phase transition (from
vapor to liquid and vice versa) at any pressure.
The state of the component at a P or/and T greater than its critical values is a “fluid”
state and as pressure increases its density varies smoothly from low (gas-like) to high
(liquid-like).
This graph also illustrates two lines of constant density (isochores): a vapor and a liquid
density.
For a single component fluid the vapor pressure curve is a line with dew-point and
bubble-point being identical.
The phase envelope represents ALL possible states that a reservoir fluid with
CONSTANT (or fixed) overall composition (zi) would exhibit at different pressures and
temperatures. As production takes place, when the average reservoir pressure is the
bubble point pressure there will be compositional changes.
Reservoirs with a gas-cap can be illustrated as. Intersecting two phase diagrams for
fluids of different composition, intersecting at a given Tres,Pres.
The following diagram illustrates how compositional changes occur during production
shifting the phase envelope towards a heavier oil, or gas injection shifting the envelope
towards a lighter oil.
t2
Pressure
Gas
Injection
t3
Temperature
Figure 26 - Composition changes due to production and gas injection. Review from
McCain (Petroleum Fluids,1990).
Typically gas and oil are both mixtures made up of alkanes which impart to them
distinct physical properties (densities, viscosities, heat capacities, color, smell, etc.)
Gases contain mainly C1 to C3, while oil includes higher hydrocarbon numbers, usually
+
denoted as C7 .
On a more elementary basis crude oils are made of … (Table from McCain)
M
n= (7)
Mw
where M is the mass expressed in grams or pounds and Mw is the molecular weight of
the component which is tabulated.
1 lbm
n= =
18lbm / lb − mol (8)
We cannot say that one pound of water contains the same amount of moles as a pound
of gasoline (C8 mainly).
The following tables (taken from McCain book) contain physical property data for pure
substances.
When a pure substance is isobarically liquefied from the solid state or vaporized from
the liquid state, there is no change in temperature but there is a definite transfer of heat
from the surroundings to the substance. These heat effects are the latent heats of
fusion for the solid-liquid transition and the latent heat of vaporization for the liquid-
vapor transition.
The fundamental relationship between the latent heat accompanying the phase change
and PVT data for the system is provided by the Clapeyron equation.
sat
∆ H vap = T∆ V dP
dT (9)
Where
Thus latent heats of vaporization can be calculated from vapor pressure and volumetric
data.
∆ V ≈ V v = RT
P (10)
ln (P sat ) = A - B
T (12)
This equation is useful for many purposes, but not sufficiently precise. The Antoine
equation, is more widely used and it has the form:
ln (P sat ) = A - B
C+T (13)
Where A, B, and C are constants specific for each component (i.e propane,
cycloheptane, benzene etc.)
An even more accurate equation is the Riedel equation (obviously, with more
parameters):
B
ln P sat = A − + D ln T + FT 6
(14)
T
n
f = n +g n
g l (15)
Then for a given saturation point provided by the coordinate pair (P sat, T sat):
Vapor pressures can also be read from the COX charts in the following figures.
Notice that the temperature scale in the horizontal coordinate in neither linear nor
logarithmic. Made up such that, curves are essentially straight.
T
Pressure (psia)
CP
Tc
2-phase
VL Vv
• The CP is the highest temperature and pressure at which a vapor an a liquid phase
can coexist.
• Isotherms are steeper in the liquid region than in the gas region to reflect lower
liquid compressibilities.
The following phase diagrams for single and binary mixtures serve to illustrate the
behavior of multicomponent fluids at different pressures, temperatures, and
compositions.
Left Right
CP1 T = Ta
Liquid
P1v P1v
urve
C
Pressure
b ble
Bu 2-phases
CP2 rve
Cu
P2v w
De
P2v
Vapor
Ta Temperature x1, y1
The left side of Figure 31 illustrates two vapor pressure curves for component [1] and
v
[2]. At Ta, the vapor pressures are P1 , P2v and component [1] is the most volatile.
Heavier components, in general, exhibit high critical temperatures and lower critical
pressures than more volatile components. For example:
o
C2 (ethane) Tc = 89.92 F Pc = 706.5 psia
o
C10 (decane) Tc = 652.0 F Pc = 305.2 psia
The right hand side of Figure 31 illustrates the phase behavior of all possible mixtures
between [1] and [2] at the selected temperature Ta.
By convention the most volatile component is plotted in the x-axis. The two extremes
indicate the vapor pressures of the pure components.
The two lines enclosing the two-phase region indicate the bubble pressures (above),
and the dew pressures (below) as a function of composition at T = Ta..
Note that bubble point pressures increase as the composition of the most volatile
component increases.
Hydrocarbon Composition
May be expressed on a weight basis and on a molar basis. For compositional modeling
we use a molar basis. The relationship between moles and mass is given through the
molecular weight.
Mi
ni = (18)
Mw i
Molecular weights for pure components are tabulated, and for undefined chemicals are
determined from correlations.
By convention liquid compositions (mole fractions) are indicated with an x and gas
compositions with a y.
Thus
n1
x1 = (19)
1
n + n 2 liquid
n1
y1 = (20)
n1 + n2 gas
And
x1 + x 2 = 1 (21)
y1 + y 2 = 1 (22)
The left side of Figure 32 illustrates the two vapor pressures of components [1] and [2]
and two phase envelopes (shaded lines) that result from two different mixtures of
components [1] and [2]. Each phase envelope has a constant overall composition. The
envelope closer to component [1] represents a higher concentration of that component.
Left Right
P = Pa
T2v De Vapor
wC
CP1 urv
e
Pressure
Bu 2-phases
bb
CP2 le
Cu
Pa rve T1v
Liquid
At a fixed pressure Pa, the two vapor pressures are intersected at their corresponding
saturation temperatures T1v , T2v .
The right side of Figure 32 shows a temperature composition projection at the selected
pressure Pa. The state of all mixture combinations between [1] and [2] at P = Pa are
depicted in this figure.
Supercritical Components
Up to this point we selected pressures and temperatures such that we could intersect
the vapor pressures of both components. However, there are temperatures and
pressures at which one or both pure components are supercritical (single phase) while
certain mixtures may exhibit VLE.
Left Right
Ta Tb Tg
Tg
Tb P1
[1]
Ta
[2]
P2v
Temperature x1, y 1
Figure 33 - Vapor pressures (left) and (Px)T diagram (right) showing supercritical
behavior.
Note that at Tg both components are supercritical. But there may be a region of two-
phase equilibria.
Similarly, in the following figure, we have three different pressure projections that
indicate the same features.
Left Right
Pg
Pg
Pb
Pb T2v
Pressure
Temperature
Pa Pa
T1v
T1v Temperature T2v x1, y1
Figure 34 - Vapor pressures (left) and (Tx)P diagram (right) showing supercritical
behavior.
Depletion Path
All diagrams up to this point indicate the vapor and liquid composition in the same axis.
Next we will identify three different compositions in the same diagram.
Figure 35 illustrates an isothermal reservoir depletion process for a reservoir oil with
two components.
At pressure A, the reservoir fluid is undersaturated, at single phase above the Bubble
Point pressure and has a composition z1. As production occurs, pressure drops to point
B. At this location, the fluid is at its bubble point, the reservoir fluid is said to be
The vapor mole fraction is read along the DEW curve, while the liquid mole fraction is
read from the BUBBLE curve.
Relative amounts of [1] and [2] in the two-phase mixture are obtained from a mass
balance.
Left Right
z1 = fixed T = Ta A
CPM
PB B
C
Pressure
Pressure
PD
Ta Temperature 0 x1 z1 y1 1
Note that any overall mixture composition bounded by the horizontal line joining x1 and
y1 has the SAME equilibrium compositions. What changes are the relative amounts of
vapor and liquid.
z1 = x1 f l + y1 f v (23)
z1 = x1 (1 − f v ) + y1 f v (24)
That is:
( n1 + n2 ) v
fv =
(n1 + n2 )v + (n1 + n2 )l (25)
Or
z1 − x 1
fv = (26)
y1 − x1
Equation (26) is valid for any number of components, and for all components. That is:
zi − xi
fv = (i = 1, 2, 3, … Nc) (27)
yi − xi
Separator gas and separator oil are recombined to reconstruct the reservoir
composition. When working in a recombination problem, the producing GOR is
converted into a molar basis and thus the reservoir composition can be found. This will
be covered later.
Figure 36 shows VLE for a mixture using a temperature-composition projection. All the
concepts are equivalent to those indicated in the previous Figure.
Any state in the two phase region requires pressure and temperature to be specified
(Flash calculations). To obtain other physical properties such as: densities,
compressibilities, and interfacial tensions the modeling equation used to predict VLE
(usually a cubic EOS) is solved at the corresponding P, T and set of equilibrium vapor
and liquid compositions. The flash type of calculations is the work-horse in any
compositional reservoir simulation package.
Left Right
z1 = fixed P = Pa
CPM
TD
TB
Pa
TD Ta
Pressure
TB
Ta Temperature 0 x1 z1 y1 1
Figure 36 - Phase equilibrium compositions at Ta, Pc are x1 for the liquid and y1 for the
gas.
Ternary Diagrams
Review - Conventions
Each corner of a diagram represents 100% of a set component the opposite sites are
0% of that component.
Binary mixtures are represented on the sides of the triangular diagram, ternary mixtures
(compositions) are represented within the triangle.
A 100% of the lightest component is drawn at the top, the intermediate is at the right,
and the heavy is at the left
.1 .9
.2 .8
.3 .7
.4 .6
.5 .5
.6 .4
.7 .3
.8 .2
.9 .1
1 0
H0 .1 .2 .3 .4 .5 .6 .7 .8 .9 1 I
Figure 38 represents the evolution of a mixture of methane (C1), propane (C3) and n-
o
pentane (C5) at a specific temperature, 160 F, and at various pressures (remember that
one ternary diagram represents the equilibrium of the mixture at one pressure and one
temperature). This figure represents actual data, and it has been redrawn from
McCain’s book.
o
Following these ternary phase diagrams at the same temperature (160 F) and at
different pressures, you can visualize typical phase behavior changes in the mixture as
the pressure changes.
C1 C1
Ga
s
Gas
2-phase
Liquid
nC5 C3 nC5 C3
p=14.7 psia p=200 psia
C1 C1
Ga
Ga
s
s
2-phase 2-phase
Liquid Liquid
nC5 C3 nC5 C3
p=380 psia p=500 psia
C1 C1
Ga
Ga
s
s
2-phase 2-phase
Liquid Liquid
nC5 C3 nC5 p=1500 psia C3
p=1040 psia
C1 C1
G
Gaas
s
2-phase
Liquid
Liquid
nC5 C3 nC5 C3
p=2000 psia p=2350 psia
Figure 38 - Evolution of a mixture of methane (C1), propane (C3) and n-pentane (C5) at
o
160 F and at various pressures.
Dilution lines
When representing phase behavior relations in a ternary diagram, the compositions of
ALL possible mixtures from mixing two fluids will fall in the straight line connecting the
points indicating the compositions of the two source fluids. For example, ALL mixtures
of n-C4 and bubble point fluid X in the figure are miscible in all proportions, while
mixtures of X with C1 are miscible at high concentrations of C1.
C1
.1 .9
.2 .8
.3 .7
.4 .6
.5 .5
.6 .4
.7 .3
.8 .2
.9 x .1
1 0
C10 0 .1 .2 .3 .4 .5 .6 .7 .8 .9 1 n-C4
Tie lines join equilibrium conditions of the gas and liquid at a given pressure and
temperature.
All mixtures whose overall composition (zi) is along a tie line have the SAME equilibrium
gas (yi) and liquid composition (xi), but the relative amounts on a molar basis of gas and
liquid (fv and fl) change linearly (0 – vapor at B.P., 1 – liquid at B.P.).
in other words,
nv 1 + nv 2 + nv 3
fv = (29)
nt 1 + nt 2 + nt 3
where,
z i = xi f l + yi f v (31)
or
zi = xi (1 − f v ) + yi f v (32)
thus,
This is also known as the Lever Rule, and fv can be determined graphically as well.
C1
.1 .9
.2 .8
.3 .7
.4 .6
.5 .5
CP
.6 .4
.7 .3
.8 .2
.9 .1
1 0
C10 0 .1 .2 .3 .4 .5 .6 .7 .8 .9 1 n-C4
Figure 40 - A ternary phase diagram illustrating the phase envelope and tie lines.
• heavy (C7+)
• intermediate (C2-C6)
For computational purposes using EOS (Equation of States) a set of ‘critical properties’
must be assigned to pseudocomponents. These are usually characterized in terms of
their normal boiling point, molecular weight and/ or density at standard conditions.
Several correlations are available to characterize these fractions.