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Thermodynamics and Equilibria in Earth System Sciences: An Introduction

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About this book

Thermodynamics is needed to understand many processes on Earth, be they physical, chemical, or biological. Thermodynamics is critical to study the atmosphere (lapse rate, fohn winds, circulation), hydrosphere (latent and sensible heat, pressure dependence of freezing/boiling points), geosphere (geothermal gradients, mineral stability) and the biosphere (redox zonation, evolution of biogeochemical cycles). This introduction to thermodynamics and equilibria aims to provide the basic concepts of relevance for atmospheric, marine, climate, and environmental sciences and to prepare students for more advanced classes in physical chemistry, mineralogy, and petrology.

This is an open access book.

Table of Contents

Frontmatter

Thermodynamics

Frontmatter

Open Access

Chapter 1. Introduction
Abstract
This chapter introduces the macroscopic approach to matter and defines thermodynamic systems and their exchange with the surroundings. The state variables temperature and pressure are presented and linked via the ideal gas law (an equation of state for gas).
Jack J. Middelburg

Open Access

Chapter 2. The First Law: Work, Heat and Thermochemistry
Abstract
This chapter presents the first law of thermodynamics in terms of heat exchange and work. Internal energy, heat capacity and enthalpy are defined and enthalpy changes during reactions and phase changes are discussed. Latent and sensible heat are introduced, and adiabatic processes are related to the atmospheric lapse rate, potential temperature, and the geothermal gradient.
Jack J. Middelburg

Open Access

Chapter 3. Entropy and the Second Law
Abstract
This chapter presents the second and third laws of thermodynamics, both at the macroscopic and microscopic scale. The state variable entropy is introduced, and it changes during reactions are quantified. A spontaneous process is recognized to cause an increase in entropy.
Jack J. Middelburg

Open Access

Chapter 4. The Gibbs Free Energy
Abstract
This chapter introduces the Gibbs free energy and its relevance for the direction of phase changes and reactions. The dependence of Gibbs free energy on temperature and pressure is presented and used to derive the (Clausius-)Clapeyron relation. One-component phase diagrams and Gibb’s phase rule are presented.
Jack J. Middelburg

Equilibria: Solutions, Minerals, Acid-Base and Redox Reactions

Frontmatter

Open Access

Chapter 5. Introduction to Equilibrium
Abstract
This chapter defines equilibrium in mixtures and ideal solutions and introduces the equilibrium constant, its relationship with the Gibbs free energy and its dependence on temperature. Homogenous and heterogenous equilibria are distinguished and solid–gas, liquid–gas and mineral-solution equilibria are presented, including Henry’s law and the solubility product.
Jack J. Middelburg

Open Access

Chapter 6. Acid-Base Equilibria
Abstract
This chapter presents acid-base equilibria and simple methods to calculate the pH of solutions. The inorganic carbon system in water is introduced, including the concept of alkalinity, and methods to solve carbon dioxide equilibria in water are discussed. Earth system science relevant examples such as rainwater, surface waters in equilibrium with calcium carbonate minerals, soda lakes and the physical chemistry of karst systems are presented.
Jack J. Middelburg

Open Access

Chapter 7. Redox Equilibria
Abstract
This chapter focuses on equilibria involving electron transfers (redox reactions). A systematic approach to identify electron transfers and to balance redox reactions is introduced. Redox potential and the Nernst equation are linked to the Gibbs free energy.
Jack J. Middelburg
Backmatter
Metadata
Title
Thermodynamics and Equilibria in Earth System Sciences: An Introduction
Author
Jack J. Middelburg
Copyright Year
2024
Electronic ISBN
978-3-031-53407-2
Print ISBN
978-3-031-53406-5
DOI
https://doi.org/10.1007/978-3-031-53407-2

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