Introduction to Physical Chemistry

Chapter 1
Week Topic Topic Outcomes
2 Introduction to Physical
Chemistry

Definition of Physical Chemistry

Overview of fundamental of
physical chemistry

First and second laws of
thermodynamics

Illustrative examples of
application physical chemistry
It is expected that students are
able to:

Determine basic fundamental of
physical chemistry

Identify and apply the First and
Second Laws of Thermodynamics
Topic Outcomes
Scope of Lecture
Introduction

Overview of fundamental of physical chemistry

1
st
& 2
nd
laws of thermodynamics

Application physical chemistry
Introduction
Definition
Physical chemistry: study of the underlying physical principles that
govern the properties & behavior of matter (chemical systems).
Chemical
Systems
Microscopic viewpoint based on the
concept of molecules.
Macroscopic viewpoint studies large-
scale properties of matter without explicit use
of the molecule concept.
Central theme:
Processes Systems States
Example 1
A thermodynamic SYSTEM: water (pure H
2
O), 1 L at ambient P (1
atm)
What are the states & process happened at 0 C and 100 C?
How do we understand this changes???
STATES: ice (solid) water(liquid) vapor (gas)
PROCESSES: heat the system; Sharp transition from
Ice water at 0 C
Water vapour at 100 C
Topics of Physical Chemistry
STUDY
Processes which such
systems can undergo
Properties of individual
atoms & molecules
Macroscopic properties
of systems of many
atoms or molecules
Relationship between
microscopic &
macroscopic properties
Macro & Micro
Equilibrium in macroscopic
systems
THERMODYNAMICS
ELECTROCHEMISTRY
Change of concentration as a
function of time
(macroscopic) KINETICS
(ELECTROCHEMISTRY)

Stationary states of particles
(atoms, molecules, electrons,
nuclei) e.g. during translation,
rotation, vibration
STRUCTURE OF MATTER
CHEMICAL BOND



Bond breakage &formation
Transitions between quantum
states
STRUCTURE OF MATTER
(microscopic) KINETICS
CHEMICAL BOND

STATISTICAL THEORY
OF MATTER
Macroscopic
Phenomena
Microscopic
Phenomena
Static phenomena Dynamic phenomena
Areas of Physical Chemistry
4 Branches
Thermo.
Quantum
Chemistry
Statistical
Mechanics
Interrelationships
Various equil. propert.
A in equil. propert.
Molecules, e

& nuclei -
not obey classical
mechanics.
Their motions
Governed by the laws
of quantum mechanics.
Molecular macro.
Rate processes
Uses relevant portions
Thermodynamics
Quantum chemistry
Statistical
Kinetics
Macro & Micro Description
Overview of Fundamental of
Physical Chemistry
Thermodynamics
Describes the behavior of matter & the transformation
between different forms of energy on macroscopic
scale, or the human scale and larger
DOES NOT refer to structure & behavior at
microscopic level
Example: Thermodynamics
1 mol of gaseous water at a sufficiently low density.
MACROSCOPIC SCALE: describes 2 of 3 macroscopic
variables of pressure, volume and temperature.
IF MICROSOPIC LEVEL: dimensions of molecules and water is
dipolar triatomic molecule, H
2
O, with bond angle of 104.5
An important concept in thermodynamics thermodynamic systems
Thermodynamics Systems
Interacts and exchanges energy with the area around it :
transformation of energy
Everything outside the system
Surrounding
System
Boundary
Universe
A region of universe that we
direct our attention to
Wall separates a system
from its surroundings
System & surroundings can be described by 1/more system variables
i.e: P, T, conc.
Note: P, pressure; T, temperature
Example: Manometer
Manometer
Const. T bath
Study the p
vap.
of H
2
O o T
Sealed container of H
2
O (const. T) in a bath & connect a manometer
to the container to measure the P.
System: consists of the liq. H
2
O & the H
2
O vap. in the container.
Surroundings: const.-T bath & the mercury in the manometer
Example: Burning Fuel
System: burning fuel package
Surroundings: compartment
System: building containing the fire
Surroundings: exterior environment
Small scale Large scale
Systems
Energy transfer is studied in 3 types of systems:
An open system can exchange matter and energy
with its surroundings.
A closed system can exchange energy with its
surroundings, but it cannot exchange matter.
An isolated system can exchange neither energy
nor matter with its surroundings.
Systems (Cont.)
System
Exchange with
surrounding
Total amt.
of energy
Example Illustration
Open Energy and
matter
Does not
remain
constant
Solution kept in
a flask
Closed Only energy Does not
remain
constant
Solution kept in
a sealed flask
Isolated Neither energy
nor matter
Remains
constant
Solution kept in
a thermo flask
Walls
A system may be separated from its surrounding by various kinds
of walls.
Rigid
Nonrigid
Permeable
Impermeable
Adiabatic
Nonadiabatic
movable
Allows no matter to
pass trough it
Does not conduct
heat at all
Does conduct heat
Equilibrium is a state of balance
Equilibrium
Thermodynamic equilibrium: conditions in which equilibrium
exists with respect to P, T & conc.
NO net flows of matter/energy, NO phase changes, & NO
unbalanced potentials (or driving forces), within the system
Thermal equilibrium: 2 systems with the same T
Adiabatic: P1P2
Diathermal: P1=P2 T1=T2
Isolated system: EQUILIBRIUM when macroscopic properties
remain const. with time.
Isolated & Nonisolated
Nonisolated system: in EQUILIBRIUM when the following 2
conditions hold,
a) The systems macroscopic properties remain constant with
time
b) Removal of the system from contact with its surroundings
causes no change in the properties of the system.
Hold
Does
not
System is in a steady state
Types of Equilibrium
Material equilibrium
No net chemical rxns occur,
No net transfer of matter
Conc. of the chemical species const. in time.
Thermal equilibrium
No change in the properties of the system or
surroundings when they are separated by a
thermally conducting wall.
Equilibria in Thermodynamics:
H
2
O (water)
25C
1 bar
stable
H
2
+ O
2
25C
1 bar
metastable
Equilibria in Mechanics:
unstable metastable stable
Mechanical equilibrium
No unbalanced forces act on the system
System undergoes no acceleration
No turbulence
Temperature
Temperature Scale
Qualitative: either HOT or COLD
Quantitative: transferable measure that does not depend on
individual experience
E.g.: a dilute gas under conditions which ideal gas law apply:
PV=nRT P=RT; =n/V
So, T=P/R; quantifiable!
A key property in thermodynamics is T, & thermodynamics is sometimes
defined as the study of the relation of T to the macroscopic
properties of matter.
The Concept
The concept
T is a thermodynamic quantity, & not known in mechanics.
The concept of T springs from the observation that a change in
physical state (e.g., a change of volume) may occur when 2 objects
are in contact with 1 another (as when a red-hot metal is plunged
into water):
A B A B
+
If, upon contact of A and B, a change in any physical property of these
systems is found, we know that they have not been in thermal
equilibrium.
The Zeroth Law
If A B, B C, C A
All these systems have a
common property: same T.
Thermal equilibrium
2 systems that are each found to be in thermal equilibrium with a third
system will be found to be in thermal equilibrium with each other.
The zeroth law allows us to assert the existence of T as a state
function.
T
A
T
B
T
C
T
A
= T
B
= T
C
Energy Transfer
Thermal energy always flows from a region of higher T to a
region of a lower T.
Thermal energy transferred
from human (|T) ice
water (+T)
Water filled with
ice cubes (0
C)
Warm water
(37 C)
Boiling water
(100 C)
Human body (37
C)
Neither hot nor cold
(Thermal equilibrium)
Hot thermal energy from the
boiling water (|T) is
transferred to the human (+T)
Thermodynamic Properties
Extensive properties Intensive properties
A property that depends on
the amount of substance
in the sample.
A property that is
independent on the
amount of substance in
the sample.
Mass
Volume
Internal energy
Length
Temp.
Density
Pressure
Example
Homogenous & Heterogeneous System
Homogenous system:
The macroscopic properties are identical in all parts of the
system.
E.g. Mixture of gases or true solution of solid in liquid
Heterogeneous system:
The macroscopic properties jump at the phase boundary
2 or more different phases which are homogenous but
separated by a boundary
E.g. Ice in water
Homogenous part of a (possibly)
heterogeneous system
If the P of He is measured as a
function of V for different T
Equations of State & Ideal Gas Law
Note: P, pressure; V, volume; T, temperature
T PV =
nRT PV=
NkT PV=
0.010 mol He & fixed T
Real Gases
At extremely low T or sufficiently high P, a value of predicted with the
ideal gas law becomes SIGNIFICANTLY INACCURATE, especially when
the gas contains a mixture of several gas species.
EoS for real (i.e. non-ideal or imperfect) gases
Note: EoS, equation of state; BWR, Benedict-Webb-Rubin; SRK, Soave-Redlich-Kwong
Virial EoS (BWR)
Compressibility
factor
Cubic EoS (SRK)
Van der Waals
Gas mixture
Kays rule Daltons law Amagats law
Van der Waals
More accurate in calculating the relationship between P, V, T for gases
than ideal law.
a & b have been optimized using experimental results
2
2
V
a n
nb V
nRT
P

=
Table 7.4 (selected gases)
Wide range Other EoS more accurate than Van der Waals
Example 2
Consider the composite system, which is held at 298 K. Assuming ideal gas
behaviour, calculate the total P, & the partial P of each component if the
barriers separating the compartments are removed. Assume that volume of
the barriers is negligible.
He
2.00 L
1.50 bar
Xe
1.00 L
1.00 bar
Ne
3.00 L
2.50 bar
1
st
& 2
nd
Laws of
Thermodynamics
1
st
Law of Thermodynamics
pd dT c dq
v
+ =
Heating
Sensible heating
Latent heating
Evaporational cooling
Radiational heating
Radiational cooling
Change in
Internal Energy
Work Done
Expansion
Compression
Statement of Energy Balance / Conservation:

Energy in = Energy out
Heat in = Heat out
Says nothing about the direction of energy transfer
Says nothing about the efficiency of energy transfer
2
nd
Law of Thermodynamics
Often called the Supreme Law of Nature

Application of the second law reveals that there are three types of
thermodynamics processes that can occur without external forcing:

Natural (or Irreversible)
Impossible
Reversible
The Second Law of Thermodynamics determines whether a given process
can naturally occur
Preferred direction of energy transfer
Fraction of heat that can be converted into work
Combining the 1
st
& 2
nd
Laws
T
dQ
dS
rev
>
pdV dT c dQ
v
+ =
1
st
Law of Thermodynamics 2
nd
aw of Thermodynamics
pdV dT c TdS
v
+ >
dW dH TdS >
dW dU TdS + >
There are many other forms since the 1
st
Law takes many forms
Vdp dT c TdS
p
>
Recall
1
st
Year (Sem II) & 2
nd
Year (Sem II)
Important in Physical Chemistry & their applications
Isothermal
Adiabatic
Isentropic
Isochoric
Isobaric
G
S
H
VLE
Fugacity
Residual properties
Excess properties
Note: G, Gibbs energy; S, entropy; H, enthalpy; W, work; U, internal energy; VLE, Vepor-liquid equilibrium

SO ON..
W
U
Application Physical Chemistry
Organic Chemist
Note: NMR, nuclear magnetic resonance
Use
Kinetic
study
Mechanisms of
reactions
Quantum-chemistry
calculations
Structures & stabilities of
rxn intermediates
Symmetry
rules
Predict the course of
many reactions
NMR and infrared
spectroscopy
Determine the structure of
compound
Inorganic Chemist
Use
Quantum
chemistry &
spectroscopy
NMR &
infrared
spectroscopy
Spectroscopy
Symmetry
rules
Study bonding
Predict the course
of many reactions
Analyzing samples
Determine the structure
of compound
Biochemist
Kinetics
Thermodynamics
Spectroscopy
X-ray diffraction
Rates of enzyme-catalyzed reactions
Biological energy transformations,
osmosis, & membrane equilibrium, & to
determine MW of biological molecules
Processes at the molecular level (e.g.
Intramolecular motions in proteins are
studied using NMR)
Structure of protein & nucleic acid
Note: NMR, nuclear magnetic resonance; MW, molecular weight
Environmental Chemist & Chemical Engineer
Environmental Chemist
Chemical Engineer
Thermodynamics
Chemical kinetics
Physical kinetics
Equilibrium composition
of lakes & streams
Reactions of pollutants
in the atmosphere
Rate of dispersion of
pollutants in the environment
Thermodynamics Principles of
thermodynamics
phase equilibria
Chemical kinetics
Predict the equilibrium
composition of rxn mixtures
Calculate how fast
product will be formed
Design separation procedure
such as fractional distillation
Geochemist & Polymer Chemist
Polymer chemist
Use thermodynamics, kinetics, & statistical mechanics to
investigate the
Kinetics of polymerization
MW of polymers
Flow of polymer solutions
Distribution of conformations of a polymer molecule
Geochemist
Use thermodynamic phase diagrams to understand
processes in the earth.
Note: MW, molecular weight