CHAPTER 2
Thermodynamics
and Nanoscience
OVERVIEW
Before we delve into the structure and function of nanomaterials, we
need to understand the fundamental thermodynamics and kinetics that
control their formation and reactivity. Thermodynamics is concerned with
heat and work and explains, on a macroscopic level, relative stability and
the feasibility of change. Kinetics, on the other hand, deals with experimental factors governing reaction rates. Changes in rate with respect to
the concentrations of different materials involved in the reaction often
give insight into the mechanism of a chemical process. In order to
understand the kinetic and thermodynamic factors governing processes
such as self-assembly, phase behavior, and chemical reactivity in nanosystems, we need to review some of the well-established ideas pertaining
to macroscopic bulk phase matter. This chapter provides a concise review
of equilibrium thermodynamics, while Chapter 3 discusses kinetics. These
crucial topics serve as an important prelude to material covered in subsequent chapters, where these ideas are extended to materials on the
nanoscale. It should be appreciated that thermodynamics and kinetics are
enormous areas of study, and therefore we have been selective in covering
concepts most relevant to the study of nanomaterials.
2.1 TERMINOLOGY IN THERMODYNAMICS
2.1.1 The system and surroundings
In thermodynamics, the specific region of interest (often the material
sample) is always denoted as the system. Everything else is referred to as
the surroundings. Energy, such as heat and/or matter, may transfer
between the system and surroundings. We say the system is isolated if no
Thermodynamics
and Nanoscience
OVERVIEW
Before we delve into the structure and function of nanomaterials, we
need to understand the fundamental thermodynamics and kinetics that
control their formation and reactivity. Thermodynamics is concerned with
heat and work and explains, on a macroscopic level, relative stability and
the feasibility of change. Kinetics, on the other hand, deals with experimental factors governing reaction rates. Changes in rate with respect to
the concentrations of different materials involved in the reaction often
give insight into the mechanism of a chemical process. In order to
understand the kinetic and thermodynamic factors governing processes
such as self-assembly, phase behavior, and chemical reactivity in nanosystems, we need to review some of the well-established ideas pertaining
to macroscopic bulk phase matter. This chapter provides a concise review
of equilibrium thermodynamics, while Chapter 3 discusses kinetics. These
crucial topics serve as an important prelude to material covered in subsequent chapters, where these ideas are extended to materials on the
nanoscale. It should be appreciated that thermodynamics and kinetics are
enormous areas of study, and therefore we have been selective in covering
concepts most relevant to the study of nanomaterials.
2.1 TERMINOLOGY IN THERMODYNAMICS
2.1.1 The system and surroundings
In thermodynamics, the specific region of interest (often the material
sample) is always denoted as the system. Everything else is referred to as
the surroundings. Energy, such as heat and/or matter, may transfer
between the system and surroundings. We say the system is isolated if no