Physical Chemistry 1

School of Chemical Science and Engineering

Introduction to Thermodynamics:

Definitions, Mathematical tools, Properties of Gases

PART A

Floralba López González

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Physical Chemistry I

Technological developments
2 concerned with the behavior
of molecules involve Ph.Ch
research

Challenging
courses for
Physical General properties
common in different
many students Chemistry materials despite their
chemical diversity

Applications in chemistry, biochemistry,

and chemical engineering, as well as
many students majoring in the
atmospheric, environmental, and the
biological sciences. 2
Physical Chemistry I

The recognition of Physical Chemistry as a discipline

began in 1887, with the founding of the journal:
Zeitschrift für Physikalische Chemie
(Journal of Physical Chemistry)
by Wilhelm Ostwald with J. H. van’t Hoff as coeditor.
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Physical Chemistry I

Wilhelm Ostwald and Josiah Willard Gibbs Svante August Arrhenius

Jacobus Henricus van’t Hoff

Francois Marie Raoult Diderik van der Waal 4

Gilbert Newton Lewis Walther Hermann Nernst
Physical Chemistry I

Chemistry è Molecules and their interactions

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Physical Chemistry

Experimental Equipment
Molecular beam machines è the molecular details of gas-phase chemical
reactions.
High vacuum machines è the structure and reactivity of molecules on solid
interfaces.
Lasers è the structures of individual molecules and the
dynamics of chemical reactions.
Spectrometers è the structure and dynamics of molecules.
(Infrared, Ultra-violet, Photoemission and diffraction of X Ray, Nuclear magnetic
resonance spectrometers)

Theoretical research
Classical mechanics, Quantum chemistry, Statistical Thermodynamics along
with computers to develop a detailed understanding of chemical phenomena
in terms of the structure and dynamics of the molecules involved. 5
Physical Chemistry I

6 Thermodynamics
(Energetics of chemical
reactions)

Quantum Chemical
Chemistry Kinetics
(Electronic structures (rates of chemical
of molecules) reactions)

Physical
Chemistry

Physical Chemistry is difficult with mathematics; impossible without it. 6

Physical Chemistry I

7
A Chemical System can be studied from:

Microscopic Macroscopic
viewpoint viewpoint

Is based on Studies large-

the concept
Molecular
scale properties
Thermodynamic
of molecules
description
of matter description

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Physical Chemistry I

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Thermodynamics (*)

Greek words Dealing with the

Dealing heat Therme Dynamis motion of bodies
exchange
and the reasons
between bodies. (Heat) (Ability to act) why they move.

Heat Energy Work

Study of heat, work, energy, and the changes they
produce in the states of systems.

(*) It is the branch of science that describes the behavior of matter and the transformation
between different forms of energy on a macroscopic scale (the human scale and larger),
and the interrelationships of the various equilibrium properties of a system, during a process.

Thermodynamics describes a system of interest in terms of its bulk properties. 8

Physical Chemistry I

Thermodynamics
9

Makes it possible to understand the

Branch of the science that studies:
•  Energy transformations
•  Changes of the relations between the
properties of the substances.
basic principles governing the
physicochemical behavior of matter,
establishing relations between the
properties of matter.

Only a few such variables are needed to describe

the system, and the variables are generally directly
accessible through measurements.

Equilibrium Thermodynamics Incorporation of definitions, mathematical

tools, Laws, fundamentals equations,
(deals with systems in equilibrium)
conventions, ….

Irreversible Thermodynamics
(deals with non equilibrium systems
and rate processes) 9
Physical Chemistry I

Thermodynamics was developed by the interpretation

10 of how steam engines, or in a wider sense and after later
inventions, heat engines in general operate.

This is the reason why its traditional treatment is

based on conclusions drawn from the operation
of those engines.

Chemical Thermodynamics
In addition to what physicists and civil and mechanical engineers usually learn as thermodynamics
– Chemical Thermodynamics deals with materials and properties, where the chemical composition
and its change are especially important.

•  Quantitative relations concerning composition and its change are usually rather complicated.

•  There is a special role of conventions established during the development of this science to
describe the “chemical” aspects. 10
Physical Chemistry I

Thermodynamics includes and connects all interactions involved in the matter:

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Thermal Interactions
Mechanical interactions
Electric interactions è Electrostatics Includes the influence on interaction
energies of the state of “hotness” (or
Magnetic interactions è Magnetostatics
coldness) of matter.

There are numerous forms of energy: thermal, mechanical, electrical, magnetic,

surface, chemical and nuclear, even mass can be considered a form of energy.

Energy = Heat + Work + Energy Flow

EK + EP + U Associated with It is caused by a force Related with the amount of

a ΔT acting through a distance mass flowing through a cross-
section. 11
Physical Chemistry I

Energy
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Macroscopic Energy Microscopic Energy

That has a system as a whole That are related to the molecular structure of the
in relation to a certain system and the degree of molecular activity. It is
external frame of reference independent of the external reference frames

Microscopic kinetic Energy of

ΔEtotal = ΔEkinetic + ΔEpotential + ΔEinternal molecules (don’t spin the wheel)

Extrinsic Properties Intrinsic Properties

(not depend on nature system) (depend on nature system)

Macroscopic kinetic
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Energy (spin the wheel)
Physical Chemistry I

Macroscopic quantities:
13 Pressure, Volume, Temperature

The behavior of a large number of microscopic

particles (molecules, atoms, ions, molecular
aggregates) determines the properties of
macroscopic body.

Microscopic quantities:
Kinetic motion of atoms, collision force

Analyzing this connection is the task of

Statistical Thermodynamics.

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Physical Chemistry I

A certain amount of gaseous water at a sufficiently low density is completely described by:
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Macroscopic Microscopic
description description

1.  Number of moles Position

2.  Pressure Momentum
3.  Volume Spin
4.  Temperature Geometry
Interactions (Intra e
Only it is required to know Intermolecular)
3 of these 4 macroscopic
Dipolar moment
variables.
….

Of each one of the

The macroscopic quantities experimentally molecules in the container!
measured are the consequence (or result) The number of particles in a macroscopic
of the molecular modes (that cannot be piece of matter if of the order of Avogadro
measured directly). constant (6.022x1023 molec/mol) 14
Physical Chemistry I

The macroscopic part of the universe under study in

Thermodynamic
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Systems thermodynamics is called the System. The parts of the universe
that can interact with the system are called the Surroundings.

Region of three-dimensional space or a quantity of matter bounded by an arbitrary surface is the

System, all the materials involved in the process under study. This material could be:
•  The contents of an open beaker containing reagents.
•  The electrolyte solution within an electrochemical cell.
•  The contents of a cylinder and movable piston assembly in an engine.
•  A piece of metal or wood.
•  A cell of a living being.
•  ….
Specific region that interacts with the
The rest of the universe is referred to as the Surroundings. system and has an influence on it that can
be detected + Environment.

The arbitrary surface that delimits the system is called Border or Boundary. It can be real or imaginary,
be at rest or in motion, and can vary in size and shape, rigid or movable and permeable or non
permeable. 15
Thermodynamics
16 is a phenomenological science,
Related to the Latin word of Greek origin phenomenon è An observable event.

Four Laws of Thermodynamics:

Zero Law of Thermodynamics è Temperature

First Law of Thermodynamics è Energy Quantity

Energy
Conversion Second Law of Thermodynamics è Energy Quality

Third Law of Thermodynamics è Entropy

Energy Energy 16
Physical Chemistry I

Any thermodynamic analysis begins with the choice of the system, its
17 boundary and its surroundings.

If a system can exchange matter with the If it can exchange energy but not
surroundings, it is called an Open System. matter, it is a Closed System.

If it can exchange neither matter nor energy

with the surroundings, it is an Isolated System. 17
Physical Chemistry I

The characteristics of the boundary define the system,

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and therefore define the thermodynamic process.

The chemical composition of the

ü  Real or virtual boundaries (walls) matter contained in a closed
systems can change.
ü  Fixed or movable boundaries (walls)

ü  Diathermal or Isolating thermal boundaries (walls)

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Physical Chemistry I

19 Animal and plant cells are Open Systems

The contents of the animal cell include the cytosol fluid and
the numerous organelles (e.g., nucleus, mitochondria, etc.)
that are separated from the surroundings by a lipid-rich
plasma membrane.

The plasma membrane acts as a boundary layer that can

transmit energy and is selectively permeable to ions and
various metabolites.

A plant cell is surrounded by a cell wall that similarly

encases the cytosol and organelles, including chloroplasts,
that are the sites of photosynthesis.

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 20 It is an Open, Closed, or Isolated System?
System: The content in the reaction beaker

Surroundings:

Boundary surface: The inner wall of the beaker.

Energy can be exchanged freely between the system and

surroundings through the side and bottom walls.
Open System
Both, matter and energy can be exchanged between the
system and surroundings through the open top boundary.
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Physical Chemistry I

21 It is an Open, Closed, or Isolated System?

System: Earth’s oceans

Surroundings: The rest of the universe.

The System – Surroundings Boundary:

consists of the solid–liquid interface between
the continents and the ocean floor and the
water–air interface at the ocean surface.

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Physical Chemistry I

Rigid or nonrigid (movable) wall Permeable or impermeable wall

22 Fabric used in raingear è
Selectively permeable wall
(permeable to water vapor,
but not liquid water)

Surface of balloons è Movable wall Adiabatic or nonadiabatic wall

Glasswool è Does not allow the

heat conduction.

An adiabatic wall is an idealization,

Double walls of a Dewar flask or thermos bottle,
but it can be approximated. 22
which are separated by a near vacuum.
Physical Chemistry I

Two separate systems A and B, each of whose properties are observed to be constant
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with time.

A and B are in equilibrium !

A W B

A and B get into contact via a rigid, impermeable wall (W).

If, no matter what initial values of the properties of

If it is observe changes in the properties of A
A and B are, no change in the values of these
and B with time, then this wall is called non
properties is observed with time, then the wall
adiabatic or thermally conducting.
separating A and B is said to be adiabatic.

When two systems at different temperatures are brought in contact through a thermally conducting
wall, heat flows from the hotter to the colder system, thereby changing the temperatures and other
properties of the two systems; with an adiabatic wall, any temperature difference is maintained. 23
Physical Chemistry I

A property is a feature of a system, and its value is

24 independent of the history of the system. Sometimes its
value is directly measurable, and in other cases, it is
A W B defined by a mathematical combination of other
properties.
It has associated dimensions and its numerical
value depends on the set of units used.

V = 3 mL P = 1.5 bar
PA , TA , PB , TB , T = 20 oC m = 0.2 kg
VA , nA . VB , nB .

Properties of the systems The specification of the properties of a system

A and B.
defines the State of the system.
The value of a property is unique and is The State can be specified only by a few of
fixed by the equilibrium condition of the properties of the system, from which it is
system at the time of the measurement. possible determine others properties by an
Equation of State.
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Physical Chemistry I

Properties
25 are classified in extensive and intensive.
A property is extensive when its value depends on the size or quantity of matter in
the system.

An intensive properties has values independent of the size or quantity of matter in

the system, it has the same value anywhere in a equilibrium system

V y E are extensive properties

Esystem = E1 + E2 Vsystem = V1 + V2

T y P are intensive properties

Psystem = P1 = P2 = P Tsystem = T1 = T2 = T
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Physical Chemistry I

A heterogeneous system, which is usually the most common, which is

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composed of two or more phases within its boundary.

If a system is not homogeneous, it may consist of a

number of homogeneous parts. A homogeneous
part of a system is called a phase.

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