Scribd Logo
Upload

Welcome to Scribd!

  • 43 views

    Gas Phase Thermochemistry (Tabular Data Available)

    Uploaded by

    TARIQ467
    This document discusses methods for estimating thermodynamic properties like heat capacity, enthalpy, and entropy from tabular temperature-dependent data using the Shomate equation and least squares regression. Key steps include: 1) Fitting heat capacity data to the Shomate equation to obtain coefficients using least squares regression. 2) Integrating the fitted heat capacity equation to determine enthalpy and entropy as a function of temperature. 3) Evaluating additional constants by applying reference state values at a specified temperature.

    Copyright:

    © All Rights Reserved
    Download as DOCX, PDF, TXT or read online from Scribd

    Gas Phase Thermochemistry (Tabular Data Available)

    Uploaded by

    TARIQ467
    43 views1 page
    This document discusses methods for estimating thermodynamic properties like heat capacity, enthalpy, and entropy from tabular temperature-dependent data using the Shomate equation and least squares regression. Key steps include: 1) Fitting heat capacity data to the Shomate equation to obtain coefficients using least squares regression. 2) Integrating the fitted heat capacity equation to determine enthalpy and entropy as a function of temperature. 3) Evaluating additional constants by applying reference state values at a specified temperature.

    Original Description:

    xdf

    Original Title

    ThermochemicalData.docx

    Copyright

    © © All Rights Reserved

    Available Formats

    DOCX, PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    This document discusses methods for estimating thermodynamic properties like heat capacity, enthalpy, and entropy from tabular temperature-dependent data using the Shomate equation and least squares regression. Key steps include: 1) Fitting heat capacity data to the Shomate equation to obtain coefficients using least squares regression. 2) Integrating the fitted heat capacity equation to determine enthalpy and entropy as a function of temperature. 3) Evaluating additional constants by applying reference state values at a specified temperature.

    Copyright:

    © All Rights Reserved
    Download as DOCX, PDF, TXT or read online from Scribd
    Download as docx, pdf, or txt
    43 views1 page

    Gas Phase Thermochemistry (Tabular Data Available)

    Uploaded by

    TARIQ467
    This document discusses methods for estimating thermodynamic properties like heat capacity, enthalpy, and entropy from tabular temperature-dependent data using the Shomate equation and least squares regression. Key steps include: 1) Fitting heat capacity data to the Shomate equation to obtain coefficients using least squares regression. 2) Integrating the fitted heat capacity equation to determine enthalpy and entropy as a function of temperature. 3) Evaluating additional constants by applying reference state values at a specified temperature.

    Copyright:

    © All Rights Reserved
    Download as DOCX, PDF, TXT or read online from Scribd
    Download as docx, pdf, or txt
    of 1

    GAS PHASE THERMOCHEMISTRY

    (TABULAR DATA AVAILABLE)

    Shomate equation gives molar heat capacity as a function of temperature.


    𝐽 𝐸 𝑇[𝐾]
    𝐶𝑃0 [ ] = 𝐴 + 𝐵𝑡 + 𝐶𝑡 2 + 𝐷𝑡 3 + 𝑤𝑖𝑡ℎ 𝑡= … (1)
    𝑚𝑜𝑙.𝐾 𝑡2 1000

    When tabular data for molar heat capacity versus temperature are available, coefficients of Shomate equation can be
    estimated through regression using the method of least squares. The objective function can be written as
    2
    𝑚𝑖𝑛𝑖𝑚𝑖𝑧𝑒 𝐹(𝑡) = ∑𝑛𝑖=1[𝐶𝑃,𝑖
    0
    − 𝐶𝑃0 (𝑡𝑖 )] 𝑤𝑖𝑡ℎ 𝑛 = 𝑛𝑜. 𝑜𝑓 𝑑𝑎𝑡𝑎 𝑝𝑜𝑖𝑛𝑡𝑠 … (2)
    0 2
    ⇒ 𝑚𝑖𝑛𝑖𝑚𝑖𝑧𝑒 𝐹(𝑡) = ∑[𝐶𝑃,𝑖 − (𝐴 + 𝐵𝑡𝑖 + 𝐶𝑡𝑖2 + 𝐷𝑡𝑖3 + 𝐸𝑡𝑖−2 )] … (3)
    Analytical solution can be easily determined using Microsoft Excel. Once a polynomial for molar heat capacity is
    obtained, molar enthalpy and molar entropy can be obtained by integration.
    𝑘𝐽 𝐵𝑡 2 𝐶𝑡 3 𝐷𝑡 4 𝐸
    (𝐻0 − 𝐻𝑅0 ) [ ] = 𝐴𝑡 + + + − +𝐹−𝐻 𝑤𝑖𝑡ℎ 𝐻 = ∆𝑓 𝐻0 | … (4)
    𝑚𝑜𝑙 2 3 4 𝑡 𝑇𝑟𝑒𝑓

    𝐽 𝐶𝑡 2 𝐷𝑡 3 𝐸
    𝑆0 [ ] = 𝐴 ln 𝑡 + 𝐵𝑡 + + − +𝐺 … (5)
    𝑚𝑜𝑙.𝐾 2 3 2𝑡 2

    The unknown constants F and G can be evaluated by using the specified values of molar enthalpy and molar entropy
    at the reference temperature, respectively.
    𝐵𝑡 2 𝐶𝑡 3 𝐷𝑡 4 𝐸
    𝐹 = (𝐻0 − 𝐻𝑅0 )| 𝑇𝑟𝑒𝑓 − (𝐴𝑡 + + + − − 𝐻)|
    2 3 4 𝑡 𝑇𝑟𝑒𝑓
    … (6)
    𝑘𝐽
    𝑤𝑖𝑡ℎ (𝐻0 − 𝐻𝑅0 )| 𝑇𝑟𝑒𝑓 = 0.0 [ ]
    𝑚𝑜𝑙
    𝐶𝑡 2 𝐷𝑡 3 𝐸
    𝐺 = 𝑆 0 | 𝑇𝑟𝑒𝑓 − (𝐴 ln 𝑡 + 𝐵𝑡 + + − )| … (7)
    2 3 2𝑡 2 𝑇𝑟𝑒𝑓

    The calculated values of molar enthalpy and molar entropy can be used to evaluate the enthalpy, entropy and Gibbs
    free energy of formation of a substance at any given temperature.
    𝑘𝐽
    ∆𝑓 𝐻0 [ ] = ∆𝑓 𝐻0 | + ∑𝑃(𝐻0 − 𝐻𝑅0 ) − ∑𝑅(𝐻0 − 𝐻𝑅0 ) … (8)
    𝑚𝑜𝑙 𝑇𝑟𝑒𝑓

    𝐽
    ∆𝑓 𝑆 0 [ ] = ∑𝑃 𝑆 0 − ∑𝑅 𝑆 0 … (9)
    𝑚𝑜𝑙.𝐾

    𝑘𝐽 𝑇∆𝑓 𝑆 0
    ∆𝑓 𝐺 0 [ ] = ∆𝑓 𝐻0 − … (10)
    𝑚𝑜𝑙 1000

    Note that a factor of 1000 appears in Eqn. 10 for unit consistency.

    You might also like