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    Unit 2

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    pedro_ergueta
    The document discusses the volumetric behavior of real substances, including: 1. Solids and liquids can be approximated as having constant volume under small temperature and pressure changes. Larger changes require considering compressibility and thermal expansion. 2. Real gases are more complex than ideal gases. Equations of state like van der Waals, Redlich-Kwong, and virial equations incorporate parameters like critical temperature and pressure to better model volumetric behavior. 3. The corresponding states principle and acentric factor allow improved modeling and estimation of real gas properties based on their critical point characteristics.

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    Unit 2

    Uploaded by

    pedro_ergueta
    8 views13 pages
    The document discusses the volumetric behavior of real substances, including: 1. Solids and liquids can be approximated as having constant volume under small temperature and pressure changes. Larger changes require considering compressibility and thermal expansion. 2. Real gases are more complex than ideal gases. Equations of state like van der Waals, Redlich-Kwong, and virial equations incorporate parameters like critical temperature and pressure to better model volumetric behavior. 3. The corresponding states principle and acentric factor allow improved modeling and estimation of real gas properties based on their critical point characteristics.

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    The document discusses the volumetric behavior of real substances, including: 1. Solids and liquids can be approximated as having constant volume under small temperature and pressure changes. Larger changes require considering compressibility and thermal expansion. 2. Real gases are more complex than ideal gases. Equations of state like van der Waals, Redlich-Kwong, and virial equations incorporate parameters like critical temperature and pressure to better model volumetric behavior. 3. The corresponding states principle and acentric factor allow improved modeling and estimation of real gas properties based on their critical point characteristics.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    8 views13 pages

    Unit 2

    Uploaded by

    pedro_ergueta
    The document discusses the volumetric behavior of real substances, including: 1. Solids and liquids can be approximated as having constant volume under small temperature and pressure changes. Larger changes require considering compressibility and thermal expansion. 2. Real gases are more complex than ideal gases. Equations of state like van der Waals, Redlich-Kwong, and virial equations incorporate parameters like critical temperature and pressure to better model volumetric behavior. 3. The corresponding states principle and acentric factor allow improved modeling and estimation of real gas properties based on their critical point characteristics.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 13

    CHEMICAL ENGINNERING

    THERMODYNAMICS

    Unit 2
    VOLUMETRIC BEHAVIOR OF
    REAL SUBSTANCES
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real
    substances:
    2.1 Solids and Liquids

    2.2 Real Gases


    2.2.1 Ideal Gases
    2.2.2 The corresponding states principle
    2.2.3 Volumetric cubic equations of state
    2.2.4 Correlations
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real
    substances:
    2.1 Solids and Liquids I
    Idealization: VS or VL constants for any T or P variations
    Valid for small to moderate ΔT or ΔP when no high precise
    estimations are needed.

    For big ΔT or ΔP or high precise estimations:


    Isothermal compressibility:
    kT = - (1/V) (∂V/∂P)T
    Isobaric coefficient of thermal expansion:
    αP = (1/V) (∂V/∂T)P
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real
    substances:
    2.1 Solids and Liquids II
    Thermal Physical Properties Constants for Selected pure
    Substances at 298 K, 1 bar
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real
    substances:
    2.2 Real Gases
    2.2.1 Ideal Gases
    As P → 0, PV → NRT, and U only changes with T and no with P,
    CP = f(T, P) ≈ g(T)
    But as P increases PV = ZNRT and U = u(T, P)
    Where Z≠ 1, compressibility factor

    2.2.2 The corresponding states principle


    Pc and Tc are added to get better estimations
    Relative properties Pr = P/Pc, Tr = T/Tc, Vr = V/Vc and Pr Vr = NRTr
    generates more precise estimations but in many cases not enough
    precise.
    Not only Pc and Tc must be known to describe the volumetric behavior of
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real
    substances:
    2.2.2 The corresponding states principle
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real substances:
    2.2 Real Gases
    2.2.3 Cubic state equations
    Equation of state f(T, P, V) = 0, where V = V/N
    Van der Waals: P = RT/(V – b) – a/V2
    Where a and b can be estimated from experimental data or calculated from
    the critical variables of the corresponding substance. At the critical point:
    (∂P/∂V)Tc = (∂2P/∂V2)Tc = 0
    This two equations allow the estimation of a and b if the critical values of
    the substance are known
    a = 27 R2 Tc2 / (64Pc) and b = R Tc / (8 Pc)
    In reduced variables vdW eq: Pr = 8 Tr / (3 Vr -1) – 3 / Vr 2
    Therefore Zc = 3/8 = 0.375, which is not true for all the real gases. A third
    parameter
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real substances:
    2.2 Real Gases

    From the different third parameter proposed (in addition to Tc and Pc, Zc
    was proposed), the most used one is the acentric factor:
    Z = Z(0)(Tr, Pr) + ω Z(1)(Tr, Pr)

    Where ω = - log10 Pvap,r│Tr = 0.7 – 1 is the acentric factor

    Pvap,r│Tr = 0.7 = Pvap(0.7 Tc)/Pc, just one experimental measurement for each
    fluid allows the determination of the corresponding acentric factor

    Z(0)(Tr, Pr) from the volumetric behavior of Argon (monoatomic noble gas).
    And for Argon ω = 0. Other gases ω > 0
    CHEMICAL ENGINEERING THERMODYNAMICS
     2. Volumetric behavior of real substances:
    2.2 Real Gases
    CHEMICAL ENGINEERING THERMODYNAMICS
    CHEMICAL ENGINEERING THERMODYNAMICS

    For example:
    RKS:
    a = ac f(ω, Tr) = ac [1 + k (1-Tr1/2)]2
    Where ac = 0.42748 R2 Tc2.5/Pc, b = 0.08664 R Tc/Pc
    k = 0.48508 + 1.55171 ω – 0.15613 ω2

    PR:
    a = ac α(ω, Tr) = ac [1 + k (1-Tr1/2)]2

    Where ac = 0.445724+ R2 Tc2/Pc, b = 0.07780 R Tc/Pc


    α(ω, Tr) = [1 + k (1-Tr1/2)]2
    2
    CHEMICAL ENGINEERING THERMODYNAMICS
    Virial equations of state:

    P = RT/V + BRT/V2 + CRT/V3 + … = RT (ρ+Bρ2+Cρ3+…)


    Or Z = PV/(RT) = 1 + B/V + C/V2 + … = 1+Bρ+Cρ2+…
    Or Z = 1 + B´P + C´P2 + D´P3 + ….
    B´= B/(RT), C´= (C - B2)/(RT)2, D´= (D - 3BC - 2B3)/(RT)3

    This equation is used truncated with 2 or 3 terms only

    For gases if ρr < 0.5, just 2 terms provide good results:


    Z = PV/(RT) = 1 + BP/(RT) or P = RT/(V - B)
    And B = RT[B(0)) + ω B(1)]/Pc
    B(0) = 0.083 – 0.422/Tr1.6 and B(1) = 0.139 – 0.172/Tr4.2
    CHEMICAL ENGINEERING THERMODYNAMICS

    For non-polar or slgihtly polar compounds a generalized


    correlation can be used. In order to use computers the
    original correlation (Z = Z(0)(Tr, Pr) + ω Z(1)(Tr, Pr), where
    Z(0)(Tr, Pr) and Z(1)(Tr, Pr) were taken from the Lee-Kessler
    tables) was modified to:

    Z = Z(0)(Tr, Pr) + (ω/ω(r)) Z(r)(Tr, Pr)

    Where the 0 superindex corresponds to fluids with ω(0) = 1


    (monoatomic noble gases) and the r (reference)
    superindex corresponds to n-Octane ω(r) = 0.398. ω is the
    acentric factor of the fluid whose Z is to be estimated.

    Both Z(0) and Z(r) where calculated from the Benedict-


    Webb-Rubin equations for Argon and n-Octane.

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