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Volumetric Properties of Pure

Fluids
Major Definitions
• System:
A body of matter with finite boundaries (physical
or virtual)
• Closed System:
Does not exchange matter with surroundings but
may exchange energy (heat).
• Open System:
Does exchange matter and energy with
surroundings.
Phase:
A portion of the system which has
homogeneous intensive properties and it is
bounded by a physical surface.
Interface:
Separates two or more phases. These phases
are solid, liquid(s), and gas.
Intensive Properties:

An intensive property is a physical


quantity whose value does not depend on the
amount of the substance for which it is
measured.
temperature, T boiling point
refractive index, n molality, m
density, ρ pressure, p
hardness of an object, η specific heat capacity, cp
color surface tension
concentration thermal conductivity
melting point viscosity
Extensive Properties:
An extensive property is a physical quantity
whose value is proportional to the size of
the system it describes, or to the quantity of
matter in the system.
amount of substance, n heat capacity, Cp
energy, E internal energy, U
enthalpy, H mass, m
entropy, S volume, V
Gibbs energy, G
Dividing one extensive property by another
extensive property generally gives an intensive
value—for example: mass(extensive) divided
by volume (extensive) gives density (intensive).
Homogeneous System:
Intensive properties change continuously and
uniformly (smoothly).
A substance that has uniform thermodynamic
properties throughout is said to be homogeneous.

Heterogeneous System:
System made up of two or more phases in which the
intensive properties change abruptly at phase-contact
surfaces
Pure Substance
A pure substance has a homogeneous and invariable chemical
composition and may exist in more than one phase.
A substance that has a fixed chemical composition throughout is
called a puresubstance such as water, air, and nitrogen.

A pure substance does not have to be of a single element or compound. A


mixture of two or more phases of a pure substance is still a pure substance
as long as the chemical composition of all phases is the same.

Examples:
1. Water (solid, liquid, and vapor phases)
2. Mixture of liquid water and water vapor
3. Carbon dioxide, CO2
4. Nitrogen, N2
5. Mixtures of gases, such as air, as long as there is no change of
phase.
Phases of a Pure Substance
A pure substance may exist in different phases. There are
three principal phases solid, liquid, and gas.
A phase: is defined as having a distinct molecular
arrangement that is homogenous throughout and
separated from others by easily identifiable boundary
surfaces.

A substance may have several phases within a principal


phase, each with a different molecular structure.
For example,
 Carbon may exist as graphite or diamond in the solid
phase
 Ice may exist in seven different phases at high
pressure.
Solid:

The molecules are arranged in a three-


dimensional pattern (lattice) throughout the
solid. The molecules cannot move relative to
each other; however, they continually
oscillate about their equilibrium position.
Liquid:
The molecular spacing in liquid phase is not
much different from that of the solid phase
(generally slightly higher), except the
molecules are no longer at fixed positions
relative to each other.
Gas:
The molecules are far apart from each other,
and a molecular order does not exist. Gas
molecules move randomly, and continually
collide with each other and the walls of the
container they are in.
Molecules in the gas phase are at a
considerably higher energy level than they are
in liquids or solid phases.
Phase-Change Processes of Pure
Substances
Consider a process where a pure substance starts as a solid
and is heated up at constant pressure until it all becomes
gas. Depending on the prevailing pressure, the matter will
pass through various phase transformations. At P0:
1. Solid
2. Mixed phase of liquid and solid
3. Sub-cooled or compressed liquid (means it is not about to
vaporize)
4. Wet vapor or saturated liquid-vapor mixture, the
temperature will stop rising until the liquid is completely
vaporized.
5. Superheated vapor (a vapor that is not about to condense).
Let's consider the results of heating liquid
water from 20C, 1 atm. while keeping the
pressure constant.

Process 1-2:
The temperature and specific volume will increase from the compressed
liquid, or subcooled liquid, state 1, to the saturated liquid state 2. In the
compressed liquid region, the properties of the liquid are approximately
equal to the properties of the saturated liquid state at the temperature.
Process 2-3:
At state 2 the liquid has reached the temperature at which it begins to
boil, called the saturation temperature, and is said to exist as a saturated
liquid. Properties at the saturated liquid state are noted by the subscript f
and v2 = vf. During the phase change both the temperature and
pressure remain constant At state 3 the liquid and vapor phase are in
equilibrium and any point on the line between states 2 and 3 has the
same temperature and pressure.
Process 3-4:
At state 4 a saturated vapor exists and vaporization is complete. The
subscript g will always denote a saturated vapor state. Note v4 = vg.
Process 4-5:
If the constant pressure heating is continued, the temperature
will begin to increase above the saturation temperature, 100 C
in this example, and the volume also increases. State 5 is called
a superheated state because T5 is greater than the saturation
temperature for the pressure and the vapor is not about to
condense.
Volumetric Properties of Pure Fluids
After the completion of this topic, it is expected
that students have the ability to:

• Determine the state/phase of a given fluid at


given conditions.
• Calculate the volumetric properties using the
equations of state and generalized correlations
for a given system.
• Identify the applicability and limitation of every
equation of state.
• Determine the volumetric properties from
thermodynamic tables and diagrams.
PHASE RULE
The state of a pure homogeneous fluid is fixed
whenever two intensive properties are set at
specific values.

For example, a system of steam & liquid water


in equilibrium at 101.33 kPa and at 100 oC. It is
impossible to change the temperature without
changing pressure if equilibrium between
vapour and liquid is to be maintained.
Degrees of freedom F
The number of independent variables that
must be fixed to establish the intensive state
of any system.
F=2–π+N
Where
π = number of phases
N = number of chemical species
• Phase rule variable are intensive properties.

• The phase rule gives the number of variables


from the set of intensive properties which
must be specified to fix all the remaining
phase rule variables.
Example 1.
An aqueous solution of ethanol in equilibrium with its
vapor.
Here
number of phases = π = 2, and
number of chemical species = N= 2
F = 2 − π + N 
= 2 − 2 + 2 
= 2
It has two degrees of freedom.
This means we are free to specify 2 thermodynamics
variable (e.g. T and P), the rest of thermodynamic
properties (e.g. U, H, V etc.) will depend on these two
variables
Example 2:
Liquid water in equilibrium with its vapours
number of phases = π = 2
number of chemical species = N = 1
F=2–π+N=2–2+1=1
For a given pressure water has only one
boiling point. Either temperature or pressure
may be specified for such a system
Example 3:
Liquid water in equilibrium with a mixture of
water vapour and nitrogen

Example 4:
A three-phase system of a saturated aqueous
salt solution at its boiling point with excess
salt crystals present.
PROBLEMS
How many phase rule variables must be
specified to fix the thermodynamic state of
each of the following systems?
a) A sealed flask containing a liquid ethanol-
water mixture in equilibrium with its vapor.
b) A sealed flask containing a liquid ethanol-
water mixture in equilibrium with its vapor
and nitrogen.
c) A sealed flask containing ethanol, toluene,
and water as two liquid phases plus vapor.
This is called phase diagram since all three phases
are separated from each other by three lines. Most
pure substances exhibit the same behavior.
the sublimation line separates the solid and the vapor.

the vaporization line separates the liquid and vapor regions

the melting or fusion line separates the solid and liquid.

these three lines meet at the triple point.


if P<PTP , the solid phase can change directly to a vapor phase

at P<PTP the pure substance cannot exist in the liquid phase.
Normally (P>PTP ) the substance melts into a liquid and then
evaporates.

matter (like CO2) which has a triple point above 1 atm.


sublimate under atmospheric conditions (dry ice)

for water (as the most common working fluid) we are


mainly interested in the liquid and vapor regions.
Hence, we are mostly interested in boiling and
condensation.
PT diagram does not provide any information about volume; it
merely displays the boundaries between single-phase regions.
On a PV diagram [Fig.(a)] these boundaries in turn become
regions where two phases—solid/liquid, solid/vapor, and
liquid/vapor—coexist in equilibrium.
Single-Phase Regions
From PV diagram where a single phase exists,
there is a unique relation connecting P, V, and T.

• V for gas is highly dependent on T and P. i.e.


gas is highly compressible.
• V for liquid phase, however, is almost
independent of T and P i.e. incompressible
liquid
The correlation for PVT is known as Equation
Of State (EOS)
f (P, V, T) = 0,
It relates pressure, molar or specific volume, and
temperature for a pure homogeneous fluid at
equilibrium.

An equation of state may be solved for any one of


the three quantities P, V, or T, given values for
other two.
i.e degree of freedom =F=2
For example, if V is considered a function of T and
P, then
V = V(T, P)
V = V(T, P)

This equation is mostly applicable for liquid phase


For liquids, β is almost always positive, and κ is
necessarily positive.

At conditions not close to the critical point, β and κ are weak


functions of temperature and pressure. Thus for small changes
in T and P little error is introduced if they are assumed constant.

Integration of the above equation then yields:


𝑉2 𝑑𝑉 𝑇2 𝑃2
𝑉1 𝑉
= 𝑇1
𝛽𝑑𝑇 - 𝑃1
𝜅𝑑P

For incompressible liquid, β and κ is 0, hence ΔV or Δρ is 0,


Therefore V and ρ is constant.
Problem # 1
For liquid acetone at 20°C and 1 bar,
β = 1.487 ×  10 −3 ° C −1 κ = 62 ×  10 −6 bar −1
V = 1.287 cm 3 ⋅g −1
For acetone, find:
a) The value of (∂ P / ∂ T) V at 20°C and 1 bar.
b) The pressure after heating at constant V
from 20°C and 1 bar to 30°C.
c) The volume change when T and P go from
20°C and 1 bar to 0°C and 10 bar.
• Problem # 2
a)Express the volume expansivity and the
isothermal compressibility as functions of
density ρ and its partial derivatives.
b) For water at 50°C and 1 bar,
κ = 44.18 ×  10 −6 bar −1 . To what pressure
must water be compressed at 50°C to change
its density by 1%?
Assume that κ is independent of P.
Problem # 3
For a liquid ‘A’ at 350K and 1 bar, κ = 50x10-6
bar-1 . To what pressure must water be
compressed at 350 K to change its density by
0.5%? Assume that κ is independent of P.
Problem # 4
• Liquid water at 25oC and 1 bar fills a rigid vessel.
If heat is added to the water until its temperature
reaches 50oC, what pressure is developed? The
average value of β between 25 and 50oC is 36.2 x
10-5 K-1. The value of κ at 1 bar and 50oC is 4.42 x
10-5 bar-1, and may be assumed independent of P.
The specific volume of liquid water at 25oC is
1.0030 cm3 g-1