CHEM 301 Physical Chemistry I

Dr. Robert E. Barletta

rbarletta@jaguar1.usouthal.edu
Phone: 460-7424
Tuesday and Thursday, 9:30 a.m. - 10::45 a.m. Room 107
Text: Physical Chemistry, 7th Edition, Peter Atkins and J. de Paula
Rules of the Road
Attendance: encouraged, not mandatory
Except for exams(see below)
Responsible for any supplemental
material covered in lectures
Cell phones/pagers off during class
Students are expected to remain in class
throughout period
Disabilities
Certify through Office of Special Student
Services
Help
Office: Room 133
Hours: Tues. & Thurs. 11-noon
Other - by appointment
Homework: Problems assigned at the
start of each chapter
Due the day after the test on material
To received credit for an assignment all
work must be shown
Exams - A non-programmable calculator
only may be used
3 Hour Exams
Exam : 1 After Chapter 4 covering
Chapters 1, 24a, 2,3, and 4
Exam 2 After Chapter 8 covering
Chapters 5-8
Exam 3 After Chapter 26 covering
Chapters 9, 10, 24b, 25, and 26
1 Final comprehensive, Ch. 27 and
portion to include ACS Thermodynamics
test
Make-up exams given only for
documented excused absences
Grading
Homework - 5%
Hour exams - 15% each
Laboratory Grade - 25%
Final Exam - 25%
Physical Chemistry
Application of physics to the study of chemistry
Develops rigorous and detailed explanations of central, unifying
concepts in chemistry
Contains mathematical models that provide quantitative predictions.
Mathematical underpinning to concepts applied in analytical, inorganic,
organic, and biochemistry
Includes essential concepts for studying advanced courses in
chemistry
Source: American Chemical Society
Divisions of Physical Chemistry
Main Problems
Position of Chemical Equilibrium
A + B <=> C + D
Rate of Chemical Reactions - Kinetics
Other special topics
Approaches
Top down (Traditional/Analytical/Historical
Approach)
Begin with things we observe in the
world/laboratory
Examine how those observables relate to the
underlying structure of matter
Bottom up (Synthetic/Molecular Approach)
Consider the underlying structure of matter
Derive observables
Traditional Approach
Equilibrium Thermodynamics
Chapters 1-10
Chemical Kinetics
Chapters 24, 25, 26, 27
Quantum Theory/ Spectroscopy
Statistical
Thermodynamics
Special Topics
Chapter 1: Properties of Gases
Homework:
Exercises (a only) : 1.4,6, 9, 11, 14, 16, 17, 18, 21
Problems: 1.1, 3, 12(a & b only), 20, 32

Equations of State
Gases are the simplest state of matter
Completely fills any container it occupies
Pure gases (single component) or mixtures of components
Equation of state - equation that relates the variables defining its physical properties
Equation of state for gas: p = f (T,V,n)
Gases (pure) Properties - four, however, three specifies system
Pressure, p, force per unit area, N/m
2
= Pa (pascal)
Standard pressure = p

= 10
5
Pa = 1bar
Measured by manometer (open or closed tube), p = p
external
+ gh
g = gravitational acceleration = 9.81 m/s
-2
Mechanical equilibrium - pressure on either side of movable wall will equalize
Volume, V
Amount of substance (number of moles), n
Temperature, T, indicates direction of flow of energy (heat) between two bodies;
change results in change of physical state of object
Boundaries between objects
Diathermic - heat flows between bodies. Change of state occurs when bodies of
different temp. brought into contact
Adiabatic - heat flows between bodies. No change of state occurs when bodies of
different temp brought into contact
Heat Flow and Thermal Equilibrium
Thermal equilibrium - no change of state occurs when two objects are in
contact through a diathermic boundary
Zeroth Law of Thermodynamics - If A is in thermal equilibrium with B and B
is in thermal equilibrium with C then A is in thermal equilibrium with C
Justifies use of thermometer
Temperature scales:
Celsius scale, O, (C) degree defined by ice point and B.P. of water
Absolute scale, thermodynamic scale , (K notK)
T (K) = O + 273.15
A B
Heat
Diathermic Wall
A B
Diathermic Wall
High
Temp.
Low
Temp.
A B
Adiabatic Wall
No Heat
No Heat
T
A
= T
B

Equation of State for Gases ( p = f(V,T,N)
Ideal (Perfect) Gas Law
Approximate equation of state for any gas
Product of pressure and volume is proportional to product
of amount and temperature
PV = nRT
R, gas constant, 8.31447 JK
-1
mol
-1
R same for all gases, if not gas is not behaving ideally


Increasingly exact as P 0 a limiting law
For fixed n and V, as T 0, P 0 linearly
Special cases (historical precident): Boyles Law (1661),
CharlesLaw [Gay-Lussacs Law (1802-08)]; Avogodros
principle (1811)
Used to derive a range of relations in thermodynamics
Practically important, e.g., at STP (T= 298.15, P = p

=1bar), V/n (molar volume) = 24.789 L/mol
For a fixed amount of gas (n, constant) plot of properties
of gas give surface
Isobar - pressure constant - line, V o T
Isotherm - temperature constant, hyperbola, PV = constant
Isochor - volume constant - line P o T
http://www.chem1.com/acad/webtext/gas/gas_2.html#PVT
Ideal (Perfect) Gas Law - Mixtures
Daltons Law: Pressure exerted by a mixture of gases
is sum of partial pressures of the gases
Partial pressure is pressure component would exhibit if
it were in a container of the same volume alone
p
total
= p
A
+ p
B
+ p
C
+ p
D
+ . (A, B, C, D are individual gases in
mixture)
p
J
V = n
J
RT
This becomes :

If x
J
is the fraction of the molecule, J, in mixture {x
J

= n
J
/ n
Total
), then E x
J
=1
If x
J
is the partial pressure of component J in the
mixture, p
J
= x
J
p, where p is the total pressure
Component J need not be ideal
p = E p
J
= E x
J
p this is true of all gases, not just
ideal gases
p
total
=
n
J
J

( )
RT
V
0 1
Mole Fraction B, x
B

P
p = p
A
+ p
B

p
B
= x
B
p

p
A
= x
A
p

Real Gases - General Observations
Deviations from ideal gas law are particularly important at
high pressures and low temperatures (rel. to condensation
point of gas)
Real gases differ from ideal gases in that there can be
interactions between molecules in the gas state
Repulsive forces important only when molecules are nearly in
contact, i.e. very high pressures
Gases at high pressures (spn small), gases less compressible
Attractive forces operate at relatively long range (several molecular
diameters)
Gases at moderate pressures (spn few molecular dia.) are more
compressible since attractive forces dominate
At low pressures, neither repulsive or attractive forces dominate -
ideal behavior
Compression Factor, Z
Compression factor, Z, is ratio of the
actual molar volume of a gas to the molar
volume of an ideal gas at the same T & P
Z = V
m
/ V
m
, where V
m
= V/n

Using ideal gas law, p V
m
= RTZ
The compression factor of a gas is a
measure of its deviation from ideality
Depends on pressure (influence of
repulsive or attractive forces)
z = 1, ideal behavior
z < 1 attractive forces dominate, moderate
pressures
z > 1 repulsive forces dominate, high
pressures
Real Gases - Other Equations of State
Virial Equation
Consider carbon dioxide
At high temperatures (>50C) and high
molar volumes (V
m
> 0.3 L/mol),
isotherm looks close to ideal
Suggests that behavior of real gases can
be approximated using a power series
(virial) expansion in n/V (1/V
m
)
{Kammerlingh-Onnes, 1911}




Virial expansions common in physical
chemistry

CO
2
pV
m
= RT 1+
B
V
m
+
C
V
m
2
+.......
|
\

|
.
|
Virial Equation (continued)
Coefficients experimentally determined (see Atkins, Table 1.3)
3
rd
coefficient less impt than 2
nd
, etc.
B/V
m
>> C/V
m
2

For mixtures, coeff. depend on mole fractions
B = x
1
2
B
11
+ 2 x
1
x
2
B
12
+ x
2
2
B
22
x
1
x
2
B
12
represents interaction between gases
The compressibility factor, Z, is a function of p (see earlier figure) and T
For ideal gas dZ/dp (slope of graph) = 0
Why?
For real gas, dZ/dp can be determined using virial equation
Substitute for Vm (V
m
= Z V
m
); and V
m
=RT/p
Slope = B + 2pC+ .
As p 0, dZ/dP B, not necessarily 0. Although eqn of state approaches ideal behavior
as p 0, not all properties of gases do
Since Z is also function of T there is a temperature at which Z 1 with zero slope -
Boyle Temperature, T
B

At T
B
, B 0 and, since remaining terms in virial eqn are small, p V
m
= RT for real gas

2
nd
Virial Coefficients
Equimolar Mixtures of CH
4
and CF
4
K B
1
(CH
4
)
(cm
3
/mol )
B
1
(CH
4
)
(cm
3
/mol )
B
12
(cm
3
/mol )
273.15 -53.35 -111.00 -62.07
298.15 -42.82 -88.30 -48.48
373.15 -21.00 -43.50 -20.43
Critical Constants
Consider what happens when you compress a real
gas at constant T (move to left from point A)
Near A, P increases by Boyles Law
From B to C deviate from Boyles Law, but p still
increases
At C, pressure stops increasing
Liquid appears and two phases present (line CE)
Gas present at any point is the vapor pressure of the
liquid
At E all gas has condensed and now you have liquid
As you increase temperature for a real gas, the
region where condensation occurs gets smaller and
smaller
At some temperature, T
c
, only one phase exists
across the entire range of compression
This point corresponds to a certain temperature, T
c
,
pressure, P
c
, and molar volume, V
c
, for the system
T
c
, P
c
, V
c
are critical constants unique to gas
Above critical point one phase exists (super critical
fluid), much denser than typical gases
CO
2
2 phases
Real Gases - Other Equations of State

Virial equation is phenomenolgical, i.e., constants depend on the
particular gas and must be determined experimentally
Other equations of state based on models for real gases as well as
cumulative data on gases
Berthelot (1898)
Better than van der Waals at pressures not much above 1 atm


a is a constant
van der Waals (1873)


Dieterici (1899)
p+
n
2
a
TV
2
|
\

|
.
| (V nB) = nRT
p =
nRT
V nb
a
n
V
|
\

|
.
|
2
=
RT
V
m
b

a
V
m
2
p =
RTe
a/ RTV
m
V
m
b
van der Waals Equation
Justification for van der Waals Equation
Repulsion between molecules accounted for
by assuming their impenetrable spheres
Effective volume of container reduced by a
number proportional to the number of
molecules times a volume factor larger than
the volume of one molecule
Thus V becomes (V-nb)
b depends on the particular gas
He small, Xe large, b
Xe
>b
Ar
Attractive forces act to reduce the pressure
Depends on both frequency and force of
collisions and proportional to the square of
the molar volume (n/V)
2

Thus p becomes p + a (n/V)
2

a depends on the particular gas
He inert, CO
2
less so, a
CO2
>>a
Ar

p =
nRT
V nb
a
n
V
|
\

|
.
|
2
=
RT
V
m
b

a
V
m
2
van der Waal s Constants
gas a
(atm L
2
/ mol
2
)
b
(10
-2
L
2
/ mol)
Ar 1.337 3.20
CO2 3.610 4.29
He 0.0341 2.38
Xe 4.137 5.16
van der Waals Equation - Reliability
Above Tc, fit is good
Below Tc, deviations

van der Waals Loops (cont.)
CO
2
Critical Temperature 304.2 K (31.05C)
Below Tc, oscillations occur
van der Waals loops
Unrealistic suggest that increase in p can increase V
Replaced with straight lines of equal areas (Maxwell construction)

van der Waals Equation - Reliability
CO
2
van der Waals @T/Tc
van der Waals Equation
Effect of T and V
m
Ideal gas isotherms obtained
2nd term becomes negligible at high enough T
1st term reduces to ideal gas law at high enough V
m
At or below T
c
Liquids and gases co-exist
Two terms come into balance in magnitude and oscillations occur
1st is repulsive term, 2nd attractive
At T
c
, we should have an flat inflexion point, i.e., both 1st and 2nd derivatives of equation w.r.t
V
m
= 0
p =
nRT
V nb
a
n
V
|
\

|
.
|
2
=
RT
V
m
b

a
V
m
2
dp
dV
m
=
d
RT
V
m
b

a
V
m
2
|
\

|
.
|
dV
m
=
RT
V
m
b ( )
2
+
2a
V
m
3
= 0
d
2
p
dV
m
=
d
RT
V
m
b ( )
2
+
2a
V
m
3
|
\


|
.
|
|
dV
m
= +
2RT
V
m
b ( )
3

6a
V
m
4
= 0
Solving these equations for p,V
m
and T gives p
c
,V
c
and T
c
in terms
of a and b
Hint: you must use original eqn to do this
p
c
= a/27b
3
, V
c
p
c
= 3b


and T
c
= 8a/27Rb
Critical compression factor, Z
c
, can be calculated using
definition for Z:

pVm = RTZ


This should be a constant for all gases and is (Table 1.4 )
Z =
p
c
V
c
RT
c
=
a
27b
2
|
\

|
.
| 3b ( )
27Rb
R8a
|
\

|
.
| =
3
8
Comparing Different Gases
Different gases have different
values of p, V and T at their
critical point
You can compare them at any
value by creating a reduced
variable by dividing by the
corresponding critical value
p
reduced
= p
r
= p / p
c
; V
reduced
= V
r
=
V
m
/ V
c
; T
reduced
= T
r
= T/ T
c
This places all gases on the same
scale and they behave in a regular
fashion; gases at the same
reduced volume and temperature
exert the same reduced pressure.
Law of Corresponding States
Independent of equations of state
having two variables
p
r

p (atm)