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Documentation:CHBE Exam Wiki/5.9 - Thermo Cheat-Sheet

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5.9 – Thermo Cheat Sheet

5.9.0 – Learning Objectives

By the end of this section you should be able to:

  1. Have a list of helpful cases in thermodynamics.
  2. Understand what keywords signify in practice problems.
  3. Have an in-depth understanding of certain cases.


5.9.1 – Introduction

The first law of thermodynamics is used in chemical engineering very often. To help, it is important to know when simplifications of the first law can be used to help analyze problems. Recall the equation of the first law:

Etot=QW

This notebook will cover cases when you can add simplifications and the rationale behind the simplifications.


5.9.2 – List of cases

Energy:

  1. If a problem says no change in height and no acceleration kinetic energy Ek and potential energy Ep are 0. These are safe assumptions for chemical reactors.
  2. An ideal gas undergoing an isothermal reaction has U=0.
  3. An ideal gas' change in internal energy ΔU can be written as nCvdT.
  4. ΔU alone, can only be used in a closed system.
  5. Open systems require enthalpy instead of internal energy.
  6. An ideal gas' change in enthalpy ΔH can be written as nCpdT.

Heat:

  1. If the temperature of the system is equal to the surrounding or is perfectly insulated, the system is adiabatic.
  2. An adiabatic system has ΔQ=0

Work:

  1. If there is no shaft work, no flow work and no electrical generation, work = PΔV
  2. In ideal, isothermal systems PΔV turns into nRTln(VfVi) by the ideal gas law
  3. In ideal, adiabatic systems Work is PVγ(Vf1γVi1γ)1γ where γ=CpCv and PVγ is often referred as K a constant.


5.9.3 – Explanation of certain cases

Energy:

  1. Self explanatory
  2. See 3
  3. Recall that internal energy is the vibrational energy held on a molecular level. An ideal gas exhibits elastic collisions by collision theory and has no interactions in between other gas molecules. As temperature rises, the amount of collisions increases proportionally thereby directly raising the internal energy.
  4. Assume a closed system where there is no work done by the system (U=Q). The key for an open system is that the volume in an open system changes and pressure remains constant with the surrounding. This contradicts the definition of U=nCvdT where Cv is the heat capacity at constant volume.
  5. Enthalpy is the correction for the open system that is also explained in the article above.
  6. Self explanatory.

Heat:

  1. Self explanatory.
  2. Self explanatory.

Work:

  1. Wnet=Wflow+Wshaft+Welectrical+pΔV This will collapse to the final term.
  2. The pressure term in work PΔV is exchanged for nRTV and then integrated where the limits of the integrand are Vf and Vi.
  3. There is a long and complicated derivation of this equation that was covered in first-year physics. It is better to just memorize this fact.