Phys. Chem.

I
Chemical Thermodynamics

Chapter 1: Fundamental Concepts of Thermodynamics

1.1 What Is Thermodynamics and Why Is It Useful?

1.3 Basic Definitions Needed to Describe Thermodynamic

Systems

1.2 The Macroscopic Variables Volume, Pressure,

and Temperature:
Elements of the Kinetic Theory of Gases
The Zero Law
Absolute Thermodynamic Temperature

1.4 Equations of State and the Ideal Gas Law

1.5 A Brief Introduction to Real Gases

Sep-18 Chapter-1 1
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Thermodynamics describes the properties and behavior of matter (composed

of a large number of microscopic particles) and the transformation between
different forms of energy on a macroscopic scale. Chemical Thermodynamics
deals with materials and properties where the chemical composition and its
change are especially important.

Postulational S U , V , N  What is It?

Thermodynamics Phenomenological
(Math formalism) Thermodynamics
(experimentally
Molecular
Thermodynamic
-based)
Statistical Laws: Very fruitful!
Thermodynamics
>1 mL
Chemists understand macro properties
in terms of molecular properties 1 atm
~ (105 Pa)
water

Molecular Scale
Macroscopic Scale
Sep-18 Chapter-1 2
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Why Is It Useful?

Thermodynamics concepts and laws give us the tools to control the

properties of many substances and materials and the outcome of
chemical processes that reach the equilibrium state.

Thermodynamic variables (P, V, T, n, …) are operational!

• Thermodynamics predicts the actual yield of

chemical reactions

• Thermodynamics defines absolute and relative

efficiencies of energy transformations

• Thermodynamic data and tools guide the

design of chemical compounds and materials. P↓ V↑, T↓,
• …. n ↑, …?
Sep-18 Chapter-1 3
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

1.3 Basic Definitions Needed to Describe Thermodynamic Systems

Types of Systems
Universe = Surroundings System
Isolated E  0 , m  0
energy mass

Surroundings Closed E  0 , m  0
boundary
Open E  0 , m  0
Permeable/semipermeable
System
Rigid or Flexible
V  0 or V  0
Adiabatic
Simple systems: isotropic and Esimple w  q0
homogeneous, electrically uncharged, closed system

surface effects neglected, Diathermic

not acted on by external fields. Esimple closed  q  0
rigid system
Sep-18 Chapter-1 4
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Chemical Thermodynamics is mainly (but not

exclusively) concerned with systems at equilibrium

Universe = Surroundings System Simple systems at

thermodynamic
equilibrium
Surroundings Fixed composition and
boundary thermodynamic variables

No previous History
System

Stable against small

perturbations
Equilibrium state
Neither matter nor energy exchange
across the system’s boundary
Sep-18 Chapter-1 5
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Subtleties of Equilibrium
• There exist materials (e.g., glass and steel) whose properties depend
on their manufacturing procedure, not only on the actual values of the
thermodynamic variables. Failure of the Thermodynamic description
can be used a posteriori to detect frozen nonequilibrium states.
• Thermodynamic systems can be in a less stable or more stable
equilibrium state. Solids and mixtures of chemical reactants are often
stuck in metastable states. Thermodynamic description of
metastable equilibria is normally valid.

T1 P1
V1 m1
… T1 P1
V1 m1
… T2 P2
V2 m2
t=0 t=t1
t=∞
Metastable equilibrium state
Sep-18 Chapter-1 6
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
Subtleties of Equilibrium
• For non-equilibrium systems (e.g., chemical reactors), the hypothesis
of local equilibrium is generally valid.
N 1
  106
N N 1) A given dV (1 (mm)3) contains a big
number of molecules (>1010). The
T r  Gas time interval between two successive
collisions between molecules is
1 m m   1015 L
3
around 10−12 s at normal P and T.

2) Kinetic theory shows that the frequency of collisions is ~1016

(mm)-3 s-1. A local perturbation of T or any other thermodynamic
variable is dumped out with a relaxation time t < 1010 s.

perturbation time t: is a
Validity of the t
local equilibrium De  << 1 macroscopic time related
t to the duration of an
hypothesis Deborah Number
Sep-18
experiment (e.g. 1 s)
Chapter-1 7
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

1.2 The Macroscopic Variables Volume, Pressure,

and Temperature (The Zero Law)

What constitutes a complete set of Experiment!

thermodynamic variables?

Equilibrium states of simple systems are characterized completely

by two (intensive) thermodynamic variables (pressure, molar volume,
density, ..) and the amount of the chemical components (n1, n2, …nK)

Equations of state f  P,  , X   0
For a pure fluid: you set 2
intensive variables, you get
absolute control!

Sep-18 Chapter-1 8
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Pressure (P) is an intensive property derived from

other (fundamental) physical quantities.

SI Unit N
Pressure: is defined as the (Pascal)
Pa  2
applied force per unit of area m
Other P units
F
F 105 Pa 101325 Pa
Pressure P 1bar 1 atm
A A 760 mm Hg
1 atm
As we are still experiencing a transition period between the widespread
use of atm and mmHg on one hand and the use of SI units, bar and Pa,
on the other hand, students must be proficient in both sets of units.

Sep-18 Chapter-1 9
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Modern pressure gauges (manometers) can measure exceedingly

small pressure (10-14 mm Hg) or changes in pressure

P down to 0.001 mmHg

P down
to 10-11 mmHg

Capacitance manometer: As the gas
molecules strike the diaphragm, the force of
the collisions determines the space between
the diaphragm and the fixed electrode
assemblies.
Sep-18
Ionization Gauge: Electrons emitted from the hot
filament collide with gas molecules and knock an
electron free. The resulting cations are collected at
the center of the gauge, and the current they
produce is a measure of the gas pressure.
Chapter-1 10
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

The ideal gas, which is the simplest thermodynamic system, is the

starting point to introduce P and T as thermodynamic variables.
Monoatomic
Elements of Kinetic Theory of Gases gas
• The pressure exerted by a gas on the
container confining the gas arises from Momentum
collisions of randomly moving gas change
molecules with the container walls.
• Temperature is a function of the
distribution of molecular speeds. Elastic collision

2
nN A m v 2U
P  Collisional
V 3 3V P
nRT volume
Ideal V
monoatomic
M v2 3
gas
Um   RT
 Avx t   
nN A 1
2 2 N coll 
Sep-18 Chapter-1 V 2 11
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Collisions between gas molecules establish a statistical

distribution of molecular speeds. The equilibrium
distribution is rapidly reached upon an external perturbation.

The Maxwell-Boltzmann distribution of speeds

• . If there is no preferred direction (i.e. isotropic gas), each velocity
component is independent and the distribution function f is factorized.

f  vx , v y , vz  dvx dv y dvz  f  vx  f  v y  f  vz  dvx dv y dvz

Symmetry considerations
and Normalization Link with
ideal gas
state eq. Mvx2
M 
f v 2
 a
e  avx2 f  vx   e 2 RT
x
 2 RT
Spherical
distribution 3
Mv 2
 M  2 
f  v   4 
2
 ve
2 RT

Sep-18 Chapter-1  2 RT  12
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

The Maxwell-Boltzmann distribution of speeds

3
The Maxwell-  M  2 
Mv 2
f  v   4 
2
 ve
2 RT
Boltzmann distribution 
 2 RT 
describes the influence
of M and T on
molecular speeds and
allows the calculation
of average properties.

 8RT 2 RT
v  v f  v  dv  vmp 
0 M M
 3RT
 v f  v  dv 
2 2 Most experimental observations (like T itself)
v
0 M depend upon averages of molecular speeds

Sep-18 Chapter-1 13
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Temperature and Thermometers (The Zero Law)

The Zero Law expresses the logical and physical
consequences of thermal equilibrium

2 State Eq. 1 State Eq.

f1  P1 , 1 , 1   0 f 2  P2 ,  2 ,  2   0 Diathermal wall f12  P1 ', 1 ', P2 ',  2 '  0

P1  1 P2  2 P1  1 P2  2 P1’ 1’ P2’ 2’

Initial state: Isolated Energy Final state:

simple rigid & closed systems at thermal
systems at equilibrium. equilibrium (the
two systems are not
independent
anymore)

Sep-18 Chapter-1 14
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Temperature and Thermometers (The Zero Law)

Zero-Law: Thermal equilibrium is a transitive property.
Two systems that are separately in thermal equilibrium with a third
system are also in thermal equilibrium with one another.
Diathermal walls
1-2 2-3 1-3
Thermal Eq. Thermal Eq.
Thermal Eq.

P1  1 P2  2 P3  3 P1  1 P3  3

f12  P1 , 1 , P2 ,  2   0 f 23  P2 ,  2 , P3 , 3   0
(b) f13  P1 , 1 , P3 , 3   0
(a) P2  w12  P1 , 1 ,  2   w23   2 , P3 , 3 

If (a) and (b) hold simultaneously   w1  P1 , 1   w3  P3 , 3 

then 2 must drop out in (a)
Sep-18 Chapter-1 15
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Temperature measurement is based on the Zero Law

Thermal equilibrium
1   2  2  3
Equal ranking
P1  1 P2  2 P3  3
in terms of 

  w1  P1 , 1   w2  P2 ,  2   w3  P3 , 3 
Reference Operational
thermometer Thermometer Sample

Thermocouple

Acoustic gas
thermometer
T  106 K
Sep-18 Chapter-1 16
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Temperature measurement is based on the Zero Law

Thermometers transduce a change
of a thermometric property into a temperature value.
Acoustic and microwave resonance frequencies   f  v 
(acoustic gas thermometer)
Gas pressure (ideal gas thermometer)   f  P 
Liquid expansion (Hg thermometer)   f  L 

Electric resistance (Pt wire thermometer)   f  R 

Potential difference at metal junctions (thermocouple)   f  V 
Spectrum of thermal radiation (pyrometers for   f  j 
non-contact measurement)
A practical thermometer should be small enough to come into thermal equilibrium
with a system without changing the system’s temperature significantly.
Sep-18 Chapter-1 17
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Empirical temperature scales

Practical temperature scales are needed to assign temperature
values to the thermometric properties.

P=1 bar
H 2O
Thermometric relationship Boiling
  a  bL point

L
Fixed T points H 2O
freezing
For calibration & point
parameterization purposes

Fahrenheit Centigrade
38.8 oC < Hg(l) < 356.7 oC
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Absolute Thermodynamic Temperature ↔ Ideal Gas Temperature

P (bar) 2.5 ideal gas thermometer

V=0.1 L at constant V
2.0

1.5
Ideal Gas P
thermometric
P  a  b 1.0
V=0.3 L
relationship
in the centigrade scale
V=0.6 L
100  P  P0 
0.5

  P   lim
0.0  P0 0 P100  P0
-300 -200 -100 0 100 200 300

Size of degree
T  K     o C  Kelvin-Celsius relationship
Conventions
Water
in Kelvin and
Celsius scales
P
T  T3
triple point T / K   / C  273.15
o
(0.01 ºC)
P3 Water freezing point
273.16 K
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

1.4 Equations of State and the Ideal Gas Law

Experimental
Molecular
bounds
perfect gas
of ideal gases
•Intermolecular Boyle’s
interactions are law •Low or moderate
1 pressure (P <10
negligible. V
P bar, excepting for
•Molecules are V n gas thermometers
point-like particles. P<0.01 bar )
P T
Avogadro’s
•Molecules move •High Temperature
rapidly and randomly Ideal gas V n ( T > 273K).

•The total kinetic •Small molar mass

energy is conserved Charles’s (M< 50 g/mol)
law
Sep-18 Chapter-1
V T 20
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

1.4 Equations of State and the Ideal Gas Law

Ideal Gas Laws The three laws of ideal gases are
merged into a single equation: The
Boyle’s ideal gas equation. The required R
1
V  constant T and n  constant can be expressed in various
units.
P
Charles’ nT
nT
V T  constant P and n  V V R
Avogadro’s
P P
 constant P and T 
Ideal Gas
V n constant

Ideal Gas Equation atm L bar L

R  0.08206 R  0.083145
K mol K mol
PV = nRT
Pa m3 J
P,T: Intensive properties R  8.3145 
K mol K mol
n,V: Extensive properties
Sep-18 Chapter-1 21
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

PV=nRT is valid either for pure substances (individual gases

like N2(g), He(g), …) or mixtures (e.g., air).

The pressure of a mixture of gases is the sum of the

partial pressures of the component gases (Dalton’s Law)

Gaseous mixture (A, B,…)

PV  nRT   nA  nB  ... RT  nA RT  nB RT  ... 

 PAV  PBV  ...   PA  PB  ...V
P  PA  PB  ...
Partial pressures account for the composition (concentration) of the
gaseous mixture
nA RT
PA
 V 
nA
 XA PA  P·X A
P nRT n
V
Sep-18 Chapter-1 22
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

1.5 A Brief Introduction to Real Gases

ideal gas regime ↔ P < 0.1-10 bar and T > 273 K and M < 50 g/mol.
Large speed and long mean free path~70Å

Intermolecular interactions can be safely ignored. They are negligible …

Real (non-ideal) gas regime ↔ P > 0.1-10 atm or T < 273 K or M > 50 g/mol;
Low speed and/or short mean free path~1-5Å

P↑
…then intermolecular interactions DO count
and influence gas properties. Condensation of
real gases into liquids can be achieved either T↓
by gas compression and/or gas cooling.

Sep-18 Chapter-1 23
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics

Potential energy of interaction u(r) of two

molecules as a function of their separation r.
When PV = nRT becomes inexact,
repulsive

we employ state equations

containing parameters related to
intermolecular forces and the
actual size of the gas molecules.

van der Waals Equation

 n2 a 
attractive

 P  2  V  nb   nRT
 V 

Lennard-Jones Other relationships that are satisfied

 potential by ideal gases, such as Dalton's law,
  12   6  are equally inaccurate.
u  r   4      
 r   r  
Sep-18 Chapter-1 24