Chemical Thermodynamics

LECTURE 1/14

Gerard Krooshof, Sr. Expert Thermodynamics @ DSM DEM

Lecturer of 2021 PPD Course TU/

Chemical Engineering & Chemistry PPD TU/e

Content of Lecture 1

• Introduction (me & DSM) 5 min

• Course overview – Set-up – Approach 10 min

• Introduction in Chemical Thermodynamics 30 min

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Introducing your Lecturer

Gerard Krooshof (see Linked-In).

Background: Physics RUU (1988), TOP TU/e (1991),

Chemical Technology UT (1998), Phd. TU/e (2019)

• Work experience DSM

1989 R&D project leader Stanyl® Fiber grade
1996 Group leader/Sr. Expert Thermodynamic lab Geleen.
2006 Global Thermodynamic expertise mng.
2016 Sr. Expert Thermodynamics.

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Course Set-up

Book: Chemical Thermodynamics for process simulation (Ch. 2-10)

by prof. J. Gmehling et al.

Lectures: 10:00-10:45 : Part 1: Book Chapter

11:00-11:45 : Part 2: Chapter related examples/discussion

Afternoon: Q&A related to tasks

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Course Philosophy

What can you expect?

Thermodynamics is a topic in science with a lot of terminology and equations.
We will focus on terminology and equations essential for Chemical Engineering.

We will learn:
• How to read these equations, what they tell us, what is their purpose
• When to use a particular equation
• How to apply these in solving thermodynamic problems

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Course Philosophy
Further:
Chemical thermodynamics is mainly chemical process oriented for making a
specific product, implying:

Understand models to describing processes like:

• Reactions (Chemical equilibrium, P/T & solvent effect, safety)

• Crystallization. (Solid-Liquid equilibrium, (anti)solvent, oiling)
• Liquid extraction (Liquid (Fluid)-Liquid equilibrium, (anti)solvent selection)
• Distillation (Vapor Liquid equilibrium, azeotropic, P/T swing, extractive)

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Course Philosophy
But chemical thermodynamics is also

Product related:
• Specification of a product. (process/feed quality variation)
• Stability of end products (non-equilibrium, storage conditions)

Safe the planet:

• Down-stream processing. (waste treatment, water/heat pinching)
• Sustainability. (exergy study, carbon footprint)

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Introduction to Chemical Thermodynamics

A historical review to understand why models were developed.

What was the motivation of scientists and engineers to introduce or

improve a thermodynamic model or equation?

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 Early developments: Farewell to Aristoteles. Air composition => Ideal gas laws

Who: Otto von Guericke E. Torricelli R. Boyle D. Fahrenheit A Celsius J. Charles L. Gay-Lussac A. Avogadro
1602 – 1686 1608 – 1647 1627 – 1691 1686 – 1736 1701 –1744 1764 – 1823 1778 – 1819 1776 – 1856

What: Vacuum pump Barometer PV=cst Accurate T-scale V/T=cst P/T=cst V/n=cst
When: (1649) (1643) (1662) Thermometer (1741) (1802) (1809) (1811)
(1662)

Air properties
Is H2 different
from O2 ?
Why: Horror Vacui Weather Life & air Invention Easier scale 1st H2 balloon Explanation
forcast Income flight, needed 2H2+O2=2H2O
hot H2.

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 Industrialization: Steam engines, efficiency => Thermodynamic laws (1+2)

Who: J. Watt S. Carnot B. Clapeyron J. Joules H. Helmholtz R. Clausius

1736–1819 1796-1832 1799–1864 1818–1889 1821-1894 1822 – 1888

What: Steam Engine Efficiency Carnot Work/Heat 1st law 2nd law
When: (1776) of engines Diagram (1845) (1847) (1854)
(1824) (1834)

Why: Instrument Efficiency Locomotiv Heat is Fysiology Defining

maker, of steam steam loss of study on Heat
engineer engines engines mech. work (flow)
energy

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Industrialization: => Real gas theory Statistical Mechanics, Equation of state,…

Who: J. Gibbs J. Maxwell L. Boltzmann J. van de Waals J. van Laar Peter Debeye
1839-1903 1831-1879 1846-1906 1837-1923 1837-1923 1884-1966

What: G=H-TS U= 3/2 kT S=k log W Eq. of state Act. Model Phonon model
When: (1879) (1866) (1877) (1873) (1910.) (1912)

Why: Chemical Kinetic (probability) Noble gases Volatilty Ion Act. Model
Thermo- theory for gases Behavior of solvents (1923)
dynamics Pure in mixtures
compounds Heat capacity
of solids at
low T

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 Oil Era: New materials, predictive methods, improved equations methods

Who: E. Guggenheim P. Flory J. Hildebrand J. Barker J. Prausnitz D-Y. Peng J. Gmehling A. Klamt J. Gross
1901-1970 1910-1985 1881-1983 1925-1995 1928- 1940- 1941- 1960- 1967-

What: Quasi- Polymer Solubility Perturbation NRTL Cubic EoS Unifac COSMO-RS PC-SAFT
When: Chemical Solution parameter theory (1968) (1974) (1977) (1995) (2001)
theory theory (1950) (1967) Uniquac
(1926) (1941) (1975)

Why: Statistical & Polymer Prediction Computer Improve New Pharma Non-cubic
chemical solubility of Simulations vd Waals Chemicals molecules EoS
thermo. solubility Flowsheets by groups by QM
combined

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 Data Era: Property prediction by molecular descriptors

Who: J. Ferguson H. Wiener M. Randic Various

? ? 1930- scientists

What: Chemical potential Wiener index Zagreb index QSPR-3D

Toxicity (QSPR-1D) (QSPR-1D) (QSPR-2D)

When: 1939 1947 1974 1980-90

Why: Understanding Boiling point Boiling point Pharmaceutical

toxicity oil fragments hydrocarbons Octanol/water
partitioning

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Summary: Lecture 1

• Thermodynamics has evolved from a curiosity to a mature topic in science

• Inventions (thermometer - computer) gave the scientist tools to improve theory

• Motivation to apply thermodynamics is related to

the innovation of new material

the reduction in energy consumption (efficiency)

the purity of produced materials / the reduction of waste/side products

the (process) safety and (product) health of people

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