ME523 Advanced Thermodynamics

Assignment 7: Thermodynamic Property Relations

Instructions:
• Make suitable assumptions and state them.
• Assignments are to be written by hand in A4 sheets.
• A single PDF file is the preferred mode of submission.

N.B.: The aim of this assignment is to evaluate the applicability of the Clausius-Clapeyron Equation for
estimation of saturation pressure from a known point by comparing against known data and to find a method
to improve the calculation based on the Principle of Corresponding States.

Introduction:

If saturation pressure 𝑃"#$,&'( is known for a certain temperature 𝑇&'( , using the Clausius-Clapeyron
Equation (CCE), saturation pressure 𝑃"#$ at a nearby temperature 𝑇 can be estimated. This approach is
useful for mathematical or numerical modelling of substances whose properties have not been extensively
studied and have not been expressed as approximate mathematical expressions. For known substances,
the experimentally determined thermodynamic properties are often expressed as tables or numerically fitted
mathematical relations. The International Association for the Properties of Water and Steam (IAPWS)
provides formulations for various properties of water. IAPWS-95 formulation is highly accurate and
recommended for scientific calculations but is also complex to use. ChemicaLogic SteamTab Companion
(available as steamtab.exe) uses IAPWS-95 to calculate properties of water at different states. Complexity
of any IAPWS equations sometimes necessitates simpler tools for modelling. IAPWS-1992 supplementary
release gives a less accurate but comparatively easier to implement formulation for water (Annexure 3).
Thus, we can use IAPWS-95 relations (through SteamTab) as the baseline values to evaluate other
relations (IAPWS-1992 and CCE) and also for calculating reference values for interpolation. According to
the Principle of Corresponding States (PCS), the compressibility factor (𝑍) describes the deviation of a real
gas from ideal gas behaviour and is used as a correction multiplier to the Ideal Gas Equation (IGE). It is
defined as the ratio of the specific volume of a real gas to the one calculated from the ideal gas law
.
,𝑍 = . /012 5. With this, the gas law can be written as 𝑃𝑣 = 𝑍𝑅𝑇. SteamTab Companion calculates 𝑍 for
34012
steam assuming IAPWS-95 values as real gas properties of steam.

Questions:

1. (a) Starting with the differential form of CCE, derive an approximate relation for estimation of 𝑃"#$ (𝑇).
Use IGE and assume ℎ(< to be constant for a small change in 𝑇"#$ . (b) Using PCS, modify the relation
derived in part (a) to get a more accurate expression for real gases. Assume 𝑍 to remain constant for
small changes in temperature.

2. Using at least 3 different reference values (𝑇&'( ) between the room temperature and the critical
temperature, calculate the saturation pressure of water at (𝑇&'( + 5°C) using IGE, PCS, and IAPWS-
1992 relations. Tabulate and compare your values as shown below against baseline values.

3. Discuss your findings.

𝑇"#$ (°C) 𝑃"#$ (SteamTab) 𝑃"#$ (IAPWS-1992) 𝑃"#$ (IGE) 𝑃"#$ (PCS)
𝑇&'(,@ + 5