0.

Introduction

physical chemistry establishes and develops the

principles of chemistry
concepts used to explain and interpret observations
on the physical and chemical properties of matter
central theme:

systems
states
processes
topics of physical chemistry:
(1) the study of the macroscopic properties of systems of many atoms or molecules
(2) the study of processes which such systems can
undergo
(3) the study of the properties of individual atoms and
molecules
PChem I

1.1

(4) the study of the relationship between microscopic (atomic or molecular) properties and macroscopic
properties
main areas of physical chemistry
thermodynamics

(1) and (2)

quantum mechanics

(3)

statistical mechanics

(4)

kinetics and transport

(2) and (3)

this semester: topics (1) and (2), i.e., equilibrium

thermodynamics and kinetics
focus on systems of many elementary building
blocks, large (classical) systems N = O(N A )
macroscopic viewpoint:
atoms and molecules

forget the existence of

physical chemistry more abstract (and more

mathematical) than other chemistry courses
example of a thermodynamic system: water, pure
H2O, say 1 L at ambient pressure (1 atm)
PChem I

1.2

states: ice (solid)

water (liquid)
vapor (gas)

32 F

212 F

processes: heat the system; sharp transition from ice

to water at 32 F and from water to vapor at 212 F

macroscopic properties change, no change in the
molecules or the forces between them!
Can we understand these changes? Can we predict the transition temperature, i.e., the melting temperature Tm and the boiling temperature Tb , or the
macroscopic properties of the different phases, e.g.,
the molar volumes, or the dependence of the transition temperatures on pressure P , on impurities (e.g.
salt), etc.
Can two or more different phases exist for the same
external conditions?
carbon: 1) diamond: transparent, colorless, hard;
2) graphite: black, slippery, soft; 3) buckminsterfullerene: ?
properties: topic (1)
processes (transformations, reactions): melting ice,
evaporating water, burning methane, . . .
PChem I

1.3

Tobacco Mosaic Virus (TMV)

2130 identical subunits in protein coat, closely
packed in a helical array around a single-stranded
RNA molecule (6390 nucleotides)
TMV can be dissociated by acetic acid into coat subunits and RNA
spontaneously reassemble under suitable conditions into virus particles
indistinguishable from original TMV in structure and
infectivity
self-assembly
process
1) Can it occur?
2) Will it occur spontaneously?
3) How fast will it occur?
thermodynamics: 1) and 2); kinetics: 3)
How can we influence a process?
applications: reactor design, catalysts, corrosion, . . .
PChem I

1.4

m xylene
o xylene
toluene + methanol

p xylene

0.50
0.25
0.25

oxidized
p xylene terepthalic acid
polyester (Dacron)
ethylene glycol
How can we increase the yield of p-xylene?
zeolite: crystalline aluminosilicate framework, exten4
5
4+
sive 3-D network of SiO4 and AlO4 ions and Si
3+
and Al ions
ZSM-5: channels and chambers 1 nm

PChem I

1.5

Thermodynamics
large systems
two types of variables:
intensive
T , P, . . .

extensive
V , m, . . .

historically: empirical observations concerning relations between such variables

example: PV = nRT
origins of thermodynamics:
practical interest: heat generates motion
evolved into a theory that describes transformation
of states of matter in general
thermodynamics is particular good in dealing with
complex systems, since the exact nature of the constituents and microscopic processes is irrelevant
two conceptual innovations of thermodynamics
First Law: conservation of energy
Second Law: entropy
PChem I

1.6

1. The Properties of Gases

Notation: (i) I use an overbar to denote molar quantities; the textbook uses a subscript m. Example: molar volume, these notes V , textbook Vm. (ii) I use a
capital P for pressure; the textbook uses p .
simple system to learn the concepts and methods of
thermodynamics
gas: fills any container
dilute gas; chemically pure
macroscopic description
state of pure gas: V volume of container, T temperature of the gas, P pressure of the gas, n amount of
the gas = number of moles
assume no electric or magnetic properties

pressure
PChem I

P=

F
A
1.7

F force perpendicular to area A

2

units: Pa = Nm , 1 N = 1 kg m s

1 bar 100. kPa = 105 Pa = P

standard pressure

1 atm 101.325 kPa

1 atm 760 torr = 760 mmHg
hydrostatic pressure P = g h ; density of fluid; g
gravitational acceleration; h height of fluid column

temperature

gas A

gas B

diathermic wall
diathermic wall: thermal contact between the two
compartments, flow of energy (heat) possible
as t : thermal equilibrium
PChem I

1.8

mechanical properties of each compartment, e.g., P ,

do no longer change with time!
for t sufficiently large: P A(t ) P A, P B(t ) P B
for a fixed, rigid wall, in general P A 6= P B

Zeroth Law of Thermodynamics

If A is in thermal equilibrium with B and if B is in thermal equilibrium with C, then A is in thermal equilibrium with C.
(empirical observations)

[Figure: Thermal equilibrium and the Zeroth Law; Atkins 9th ed., Fig. 1.3]

= existence of a property common to all systems

that are in thermal equilibrium with each other: temperature
PChem I

1.9

thermodynamic temperature scale: C, melting

point of ice: 0 C at 1 atm; boiling point of water:

100 C at 1 atm

T
+ 273.15
K
C

thermodynamic equilibrium
= thermal equilibrium, TA = TB
and
mechanical equilibrium, P A = P B
thermodynamic equilibrium states

P = f (n,V, T )
ideal gas

PV = nRT
3

SI units: V m , P Pa, T K: R = 8.314 J K mol

PChem I

1.10

1J = 1Nm
3

alternative units: V L, (1 L = 1 dm = 10

m3) P atm:

R = 8.206 102 L atm K1mol1

consider a system with n = const

isotherm: T = const, PV = const, P 1/V , hyperbolas

[Figure: Ideal gas isotherms; Atkins 9th ed., Fig. 1.4]

PChem I

1.11

isobar: P = const, V T

[Figure: Ideal gas isobars; Atkins 9th ed., Fig. 1.6]

PChem I

1.12

isochore: V = const, P T

[Figure: Ideal gas isochores; Atkins 9th ed., Fig. 1.7]

PChem I

1.13

surface of equilibrium states

[Figure: Ideal gas: surface of possible states; Atkins 9th ed., Fig. 1.8]

standard temperature and pressure (STP): = 0 C,

P = 1 atm = V = RT /P = 22.414 dm3mol1 = 22.414 L

mol1
standard ambient temperature and pressure (SATP):
PChem I

1.14

T = 298.15 K, P = 1 bar
dm3mol1

= V = RT /P = 24.789

mixture of ideal gases

Daltons law

P = P1 + P2 + . . . =

X
j

mole fraction

xj =

nj
n

n=

Pj,

Pj =

n j RT
V

nj

Pj = xjP

for nonideal gases: P j x j P

Real Gases
deviations from ideal gas law: due to intermolecular
forces
PChem I

1.15

[Figure: Potential energy between two molecules; Atkins 9th ed., Fig. 1.13]

attractive: dipole-dipole forces, H-bonds, dispersion

forces
repulsive: repulsion of electrons
measure for deviations
compression factor
PChem I

Z=

PV
RT
1.16

RT
ideal gas (superscript ) V =
Z 1
P

Z=

V
V

[Figure: Compression factor; Atkins 9th ed., Fig. 1.14]

Z > 1 V > V repulsive forces dominate

Z < 1 V < V attractive forces dominate

PChem I

1.17

equation of state for real gases? no general form!

Try: PV = RT f (P ), f (P ) to be determined
f (P ) 1 for ideal gases
as P 0, all gases follow the ideal gas law = f (P )
1 as P 0
try power-law ansatz for f (P ), i.e., expand f (P ) in
powers of P

PV = RT [1 + B 0(T )P +C 0(T )P 2 + . . .]
virial expansion or virial equation of state

B 0(T ) second virial coefficient (depends only on pair

0
interactions), C (T ) third virial coefficient (note: the
0

does not denote a derivative; it is simply used to

distinguish these coefficients from those in the alternative form)
alternative, but equivalent form of the virial equation
of state
ideal gas law is valid for dilute gases, i.e., small or
V large ( = m/V = M /V or 1/V )
PChem I

1.18

PV = RT f(V ), f(V ) 1 for ideal gas

expand f(V ) in powers of 1/V

"
PV = RT 1 + B (T )

1
V

+C (T )

1
V

#
+...

left as an exercise to show that

2
C
(T
)

B
(T
)
B
(T
)
, C 0(T ) =
B 0(T ) =
RT
(RT )2

Z = 1 + B 0(T )P +C 0(T )P 2 + . . .
dZ
= B 0(T ) + 2C 0(T )P + . . .
dP

PChem I

1.19

Boyle temperature TB: B (TB) = 0 or B (TB) = 0

P 0: if T = TB then Z 1 and dZ /dP 0

extended range of ideal behavior

[Figure: Boyle temperature; Atkins 9th ed., Fig. 1.16]

Boyle temperatures for some gases: H2 109 K,

CH4 510 K, C2H4 720 K, NH3 1030 K [Estrada-Torres,
R.; Iglesias-Silva, G. A.; Ramos-Estrada, M. & Hall, K. R., Boyle temperatures for pure substances, Fluid Phase Equilib., 258, 148154 (2007),
http://dx.doi.org/10.1016/j.fluid.2007.06.004]

PChem I

1.20

real gas isotherms: example CO2

[Figure: CO2 isotherms; Atkins 9th ed., Fig. 1.15]

phase transition: condensation, gas liquid

critical point: critical temperature = maximum temperature at which a gas can be liquefied
PChem I

1.21

phase diagram

critical temperature Tc , critical pressure P c , critical

molar volume V c : critical constants

as the critical point is approached along the vapor

pressure curve: (l ) (g ) 0 or V (g ) V (l ) 0

PChem I

1.22

[Figure: Approaching the critical point; Atkins 9th ed., Fig. 4.6]

critical opalescence: strong density fluctuations near

the critical point, (l ) u (g ); characteristic length of
fluctuations on the order of the wavelength of visible
light = strong scattering = milky appearance
law of rectilinear diameter (Cailletet and Mathias
1886)
1
((l ) + (g )) =
2

A + BT

[Figure: rectilinear diameter]

PChem I

1.23

[Figure: isobaric path]

[Figure: nonisobaric path]

PChem I

1.24

continuity of states: the substance changes from

liquid-like to gas-like in the supercritical region without ever changing phases
virial equation of state good for quantitative work,
B (T ), C (T ), . . . are tabulated for gases, but it does
not provide understanding of the above phenomena
of real gases
find a general model; best known and most widely
used: van der Waals gas
repulsive interactions: hard spheres excluded volume, V V nb

b is a material constant, equal to the volume of 1 mol

of densely packed gas particles

P (V nb) = nRT
or

P=

nRT
V nb

PChem I

1.25

attractive forces: diminish pressure; pressure is the

result of collisions of the gas particles with the walls;
as a particle is about to hit the container wall, it is
held back, and its impact is diminished, by the attractive forces from surrounding gas particles; this is
2
a pair effect number of pairs of particles (n/V ) =

n 2
nRT
a
P=
V nb
V
van der Waals equation

a is a material constant; a and b are tabulated for real

gases

a
P + 2 V b = RT
V

compare van der Waals equation with virial equation

B (T ) = b
PChem I

a
RT
1.26

How good is the van der Waals model?

2

(V b)V P = RT V a(V b)
3

V P V bP = RT V aV + ab

RT
a
ab
3
2
V b+
V + V
=0
P
P
P
cubic equation for fixed T and P , three real roots
or one real root and two complex conjugate roots
isotherms for the van der Waals equation for ammonia

PChem I

1.27

T < Tc : between the minimum and the maximum of

the isotherm we have

dP
dV

> 0,

and since

dP
dV

dV
dP

!1

we have

dV
>0
dP

unstable!!

replace the unphysical van der Waals loop by the

Maxwell equal area construction
PChem I

1.28

branch BB and AA are metastable states

AA: fast compression:
chamber
BB: fast expansion:
chamber

supersaturated gas, cloud

superheated liquid, bubble

critical point = coalescence of minimum and maximum = disappearance of van der Waals loop
minimum or maximum: first derivative vanishes
PChem I

1.29

between a minimum and a maximum is an inflection

point (curvature changes): second derivative vanishes
critical point: at (Tc , P c , V c )

dP

d 2P

= 0 and

dV

dV

=0

there are three critical constants, need one more

equation: equation of state

P=
dP

RT
V b
=

dV
d2P
dV

=
2

V
RT

(1)

(V b)

+
2

2a
V

= 0 at critical point

2RT

6a

= 0 at critical point
4
3
(V b) V

equation (2) RTc =

PChem I

2a(V c b)2
3
Vc

(2)

(3)

(4)

1.30

insert this result into equation (3)

4a(V c b)2
3
V c (V c

6a
4
Vc

b)
2
3

=0
V c b V c

=0

(5)

2V c = 3V c 3b V c = 3b
insert into equation (4)

RTc =

2a(3b b)2
(3b)

2a 4b 2
27b 3

8a
27bR

Tc =

insert into equation (1)

Pc =
Pc =

8a
27b

3b b
a

PChem I

a
9b

8a
2 27b

a
9b 2

27b 2
1.31

critical compression factor:

Pc V c
=
Zc =
RTc
Zc =

a
3b
27b 2
8a
27b

3
8

independent of the material constants a and b

ZcvdW = 0.375; compare with experimental data

range: 0.12 HF 0.47 N2O4
mode: 0.27; 27% of all organic and inorganic substances have this value of Zc
61% Zc in [0.26, 0.28]; 77% Zc in [0.25, 0.29]; 90%
Zc in [0.23, 0.31]
van der Waals gas: simple model that captures the
essential aspects of real gases
critical point is a very characteristic point for real gases use critical constants as units
reduced variables P r =

PChem I

T
P
V
,Vr =
, Tr =
Pc
Tc
Vc
1.32

RT

P=

a
2

V b V
RTr Tc
a
Pr Pc =
2 2
V rV c b V rV c
Pr

a
27b

Pr =

8
T
3 r

8a
T
27b r

3bV r b

Vr 3

3
2
Vr

a
2
V r 9b 2

material independent

law of corresponding states

universality

PChem I

1.33

[Figure: Law of corresponding states; Atkins 9th ed., Fig. 1.21]

PChem I

1.34

other equations of state for real gases:

Berthelot P =

RT

a
2

Zc = 0.375

V b TV

a
RT
exp
, Zc = 0.271
Dieterici P =
V b
RT V
RT
a
Redlich-Kwong P =
p
, Zc = 0.333
V b
T V (V + b)

PChem I

1.35