Chapter 2: Volumetric Properties

of Pure or Real Fluids

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
The quantities of heat and work are carry out industrial processes calculating some
thermodynamic properties such as internal energy and enthalpy. For fluids, these properties
are evaluated from measurements of molar volume as a function of T and P, yielding PVT
relations, which may expressed mathematical as Equation of State (EoS).
The least complex equation, PV = RT, provides the simplest model of fluid behaviour.
Equation of state serve for the metering of fluids and the sizing of vessel and pipelines.
This Chapter will cover the following:
Nature of the PVT behaviour of pure fluids
The treatment of the ideal gas
 EoS provide the foundation for quantitative description of real fluids behaviour.
Generalized correlation that allow prediction of the PVT behaviour of fluids for which
experimental data are lacking.
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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
PVT behavior of pure substance

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
A vapour is a gas below the critical temperature
A gas is a phase which may be condensed by decreasing T at constant P
A fluid above the critical T and P is supercritical fluid where a phase
considered a liquid if vaporization results from pressure reduction at
constant temperature, a phase considered a gas if condensation results
from temperature reduction at constant pressure.
The line between the phases also have special description
Solid-vapour = sublimation curve
Solid-liquid = fusion curve (melting curve)
Liquid-vapour = vaporization 4
 Chapter 2: Volumetric
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 Chapter 2: Volumetric
Properties of Pure or Real
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The vapour pressure is described by the vaporization curve (boiling point), and
melting is described by the fusion curve
PV diagram

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Properties of Pure or Real
Fluids
A vapour pressure is liquids and vapours that are saturated and coexisting phases are
connected by the horizontal segment of the isotherm at the saturated pressure specific to the
isotherm.
Before critical point is subcooled-liquid
After critical point is the superheated –vapour
Single phase region
For the regions of the diagram where a single phase exists, it implies a relation connecting P, V,
and T. This can be expressed as f(P,V,T) = 0, it is known as PVT equation of state. It relates
pressure, molar or specific volume, and temperature for a pure homogenous fluid in
equilibrium states. The ideal gas equation of state, PV = RT.
An equation of state may be solved for any one of the three quantities P, V, or T as a function of
the other two. For example: if V is a function of T and P, then V = V(T, P), and the expression is
……………………………………………………………(1) 7
 CHAPTER 2: Volumetric
Properties of Pure or Real
Fluids
The partial derivatives in this equation have physical meanings of two
properties called volume expansivity and isothermal compressibility
Volume expansivity:

Isothermal compressibility

Combine the two equation yield to

Example 3.1

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 CHAPTER 2: Volumetric
Properties of Pure or Real
Fluids
Example 3.1
For liquid acetone at 200C and 1 bar = 1.487 x 10-3 0C-1, = 62 x 10-6 bar-1, V = 1.287
cm3/g
For acetone find the following:
(a) The value of at 200C and 1 bar
is determined by assuming V is constant and dV = 0 in equation 1

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 CHAPTER 2: Volumetric
Properties of Pure or Real
Fluids
(b) The pressure generated by heating at constant V from 200C and 1
bar to 300C.
If and are assumed constant in the 100C temperature interval, then
the equation derived in (a) may be written (V is constant)

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 CHAPTER 2: Volumetric
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(c) The change in volume for a change from 200C and 1 bar to 00C and
10 bar

V2 = (0.9702)(1.287) = 1.249 cm3/g

ΔV = V2 – V1 = 1.249 – 1.287 = -0.038 cm3/g

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
Another useful quantity used when dealing with equation of state (EOS) is the
compressibility factor, Z which is

VIRIAL EQUATION OF STATE

The virial equation of state expresses the pressure of a system of many
particles, in equilibrium, as a power series. While not very convenient at times,
it can be derived directly from statistical mechanics. Isotherms for gases and
vapours lying above the saturation curve, when V decreases and P increases,
the product PV for given T is given in a power series.
PV = a + bP + cP2 + dP3 + ……
The terms b, c, d etc are known as the virial coefficients.
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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
If
Therefore:
Where a, B’, C’ and D’ are constant for a given temperature and a
chemical species
For ideal gas temperature, where you can make PV is direct
proportional to T with R (PV = RT), the PV = a = RT
Assign the value 273.15 K to the triple (t) point of water
(PV)t = R x 273.15 K
(various units)
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 Chapter 2: Volumetric
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PVT data cannot be taken at zero pressure, the data taken at finite
pressures are extrapolated to the zero-pressure state 14
 Chapter 2: Volumetric
Properties of Pure or Real
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Recall

PV = a = RT

or

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where

Parameters

Example 3.8
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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
The ideal gas
The terms B/V, C/V2 etc., of the viral coefficient expansion arise on account of
molecular interactions, the viral coefficient B, C, etc., would be zero if there is no
interactions exist, therefore:
Z=1 or PV = RT
If molecular interactions do exist in the system and influence the behaviour of real
gases. As pressure is reduced at constant temperature, V is increase and the
contributions of the terms (B/V), C/V2), (D/V3), (E/V4)…… decreases.
As and not because of any change in the viral coefficient, but because V becomes
infinite.

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
The ideal gas is a hypothetical gas whose molecules occupy negligible space and
have no interactions, and which consequently obeys the gas laws exactly.
A real gas is a gas that does not behave as an ideal gas due to interactions
between gas molecules. A real gas is also known as a nonideal gas because the
behaviour of a real gas in only approximated by the ideal gas law
Equation of state for ideal gas: PV = RT
An internal energy that is function of temperature only for ideal gas: U = U(T)

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
Property relation for an ideal gas
Heat capacity at constant volume:
For enthalpy: H = U + PV = U(T) +RT = H(T)
Heat capacity at constant pressure:
Useful relation between CP and CV for an ideal gas: + R
This equation does not imply that CP and CV are constant for an ideal gas, but only
vary with temperature in such a way that their difference is equal to R
dU = CVdT
dH = CPdT

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
For process calculation for an ideal gas
Recall: For work of a mechanical reversible closed system: dW = –PdV …………(1)
For an ideal gas in any closed system process: dQ + dW = CV dT……………………..(2)
Substitute (1) into (2): dQ = CVdT + PdV for ideal gas and reversible in close system, it
contains the variables P, V, and T, only two of which are independent.
dQ and dW depends on the pair of these variables (P, V, and T)
With :

With T , and with Cv:

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Isothermal process (Constant T)
Recall: and : therefore ΔU = ΔH = 0
and : thus
and : thus W
NB: Q = –W
(constant T)

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 Chapter 2: Volumetric
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Isobaric process (Constant P)
Recall:
becomes
becomes W = –R(T2 – T1)
NB: Q = ΔH therefore
(Constant P)

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Isochoric process (Constant V)
Recall: this apply again
becomes
dV becomes
NB: Q = ΔU: therefore
(Constant V)

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Adiabatic Process and constant heat capacities
Adiabatic process: there is no heat transfer between the system and surroundings:
dQ = 0. integration with CV and CP constant then yields simple relations among T, P,
and V for mechanically reversible adiabatic compression or expansion of ideal gas
becomes
Integration with CV constant:
becomes
becomes these equation can be expressed
where
For Polytropic process: where
Example 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 24
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CUBIC EQUATIONS OF STATE
Van der Waals EOS
Peng and Robinson (PR-EOS)
Redlich and Kwong (RK-EOS)
Pitzer correlation
Soave EOS
Soave-Redlich-Kwong (SRK-EOS)

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
CUBIC EQUATIONS OF STATE
Van der Waals (EOS):
Peng and Robinson (PR-EOS):
Redlich and Kwong (RK-EOS):
Pitzer correlation: and
Soave-Redlich-Kwong (SRK-EOS):
Parameters a and b have different equation for each EOS

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
The van der Waals EOS
The first cubic EOS was proposed by van der Waals in 1873 which
includes parameters accounting for both repulsive and attractive
interaction between molecules (a and b parameters)

Given parameters of a and b, then P can be calculate as function of

V.
At the critical point, consider two important relations

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
Generic cubic equation of state

Where ϵ and σ are pure numbers, the same for all substances, a(T) and b are
temperature dependence.
Determination of the parameters a and b, which are species dependent on T.
To estimate parameters for a and b critical properties must known.

NB: Parameters a and b have different equation for each EOS

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 Chapter 2: Volumetric
Properties of Pure or Real
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Recall compressibility

At critical point
, the substitute Vc

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Properties of Pure or Real
Fluids
Analogous procedure applied to the generic cubic EoS, which
yield expressions for parameters a(Tc) and b.

In an extended to temperature other than the critical by

introduction of a dimensionless function α(Tr) that becomes
unity at the critical temperature

is an empirical expression, specific to a particular EoS

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Parameter b

Where Ω and Ψ are pure numbers, independent of substance and determined for
a particular EoS from the values assigned to ϵ and σ.
The dimensionless thermodynamic coordinates provide the basis for the simplest
form of the theorem of corresponding states: All fluids, when compared at the
same reduced temperature and reduced pressure, have approximately the same
compressibility factor, and all deviate from ideal-gas behaviour to about the same
degree.

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 Chapter 2: Volumetric
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Acentric Factor

The acentric factor for a pure chemical species is defined with

reference to its vapour pressure. It was introduced by Pitzer and co-

workers. It is an addition parameter on Tc and Pc to improve results

can be determined for any fluid Tc, Pc, and a single vapour
pressure measurement made at Tr = 0.7. Values of Tc, Pc, and Vc for
a number of fluids are listed in Appendix B
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 Chapter 2: Volumetric
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Vapour and Vapour –like roots of the generic cubic EoS
Recall:
Multiple through by
V; an initial estimate V is ideal gas RT/P
Solve can be solve by trial and error or iterations
For compressibility, Z: recall
therefore

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Lets ……..(1) …………..(2)
Then

Combine (1) and (2) with

Therefore
and

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Liquid and Liquid –like roots of the generic cubic EoS
Recall: V
VP
V
V can be solve by trial and error or iterations, but the roots must
positive.
Z

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Generalized correlation for gases:
If focus on compressibility factor and second virial coefficient
Pitzer correlation

Where Z0 and Z1 are function of both Tr and Pr :These parameters can find in
Tables

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 Chapter 2: Volumetric
Properties of Pure or Real
Fluids
Pitzer correlation for the second virial coefficient

Therefore

Example 3.10, 3.11, 3.12

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Generalized correlations for liquids
The molar volume of liquids can be calculated using cubic equation of
state, the results are often not of high accuracy. In addition, the
generalized equation for the estimation of molar volumes of saturated
liquids was proposed by Rackett, 1978

Example 3.13

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 Chapter 2: Volumetric
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Tutorial Section

Tuesday 11h00 to 12h00

Contact: Dr MG Ntunka
Email: [email protected]

NB: Attempt All tutorials and problems in the text book first before
meet the Tutor

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 Aim and Objectives
Evaluate the photocatalytic activity of a locally produced TiO2
pigment on the degradation of bacteria in river water for potable
water purposes and hence optimize the process. The specific
objectives are as follows:

Evaluate the photocatalytic activity of the mTiO2 on degradation of

organics in river water to produce clean water.
Optimize process parameters of temperature, starting pH of the
solution and mTiO2 loading on the degradation of bacteria in river
water.
Investigate the percentage removal of mTiO2 and bacteria in treated
water using a Polyester Woven Microfiltration Membrane (PEWMM).
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