CHEM 301 Physical Chemistry I

Dr. Robert E. Barletta

[email protected]
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  Exams - A non-programmable calculator
» Except for exams(see below) only may be used
» Responsible for any supplemental » 3 Hour Exams
material covered in lectures  Exam : 1 After Chapter 4 covering
» Cell phones/pagers off during class Chapters 1, 24a, 2,3, and 4
» Students are expected to remain in class  Exam 2 After Chapter 8 covering
throughout period Chapters 5-8
 Disabilities  Exam 3 After Chapter 26 covering
Chapters 9, 10, 24b, 25, and 26
» Certify through Office of Special
Student Services » 1 Final comprehensive, Ch. 27 and
 Help portion to include ACS
Thermodynamics test
» Office: Room 133
» Make-up exams given only for
» Hours: Tues. & Thurs. 11-noon
documented excused absences
» Other - by appointment
 Homework: Problems assigned at the
 Grading
start of each chapter » Homework - 5%
» Due the day after the test on material » Hour exams - 15% each
» To received credit for an assignment all » Laboratory Grade - 25%
work must be shown » 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 Traditional Approach

» Position of Chemical Equilibrium
A + B <=>C + D Equilibrium Thermodynamics
Chapters 1-10
» Rate of Chemical Reactions - Kinetics
» Other special topics
 Approaches
Chemical Kinetics
» Top down (Traditional/Analytical/Historical
Chapters 24, 25, 26, 27
Approach)
 Begin with things we observe in the
world/laboratory
 Examine how those observables relate to the
underlying structure of matter Quantum Theory/ Spectroscopy
» Bottom up (Synthetic/Molecular Approach)
 Consider the underlying structure of matter
 Derive observables 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/m2 = Pa (pascal)
 Standard pressure = pø = 105 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
High Low TA = T B
Temp. Temp.

A B
A B A B No Heat
Heat No Heat

Diathermic Wall Diathermic Wall Adiabatic Wall

 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, , · (°C) degree defined by ice point and B.P. of water
 Absolute scale, thermodynamic scale , (K not°K)
 T (K) =  + 273.15
 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-1mol -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): Boyle’s Law (1661),
Charles’Law [Gay-Lussac’s Law (1802-08)]; Avogodro’s
principle (1811)
 Used to derive a range of relations in thermodynamics
» Practically important, e.g., at STP (T= 298.15, P = p ø =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  T
» Isotherm - temperature constant, hyperbola, PV = constant
» Isochor - volume constant - line P  T

http://www.chem1.com/acad/webtext/gas/gas_2.html#PVT
 Ideal (Perfect) Gas Law - Mixtures

 Dalton’s 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 = pA + pB
» ptotal = pA + pB + pC + pD + ……. (A, B, C, D are individual gases in
pB = xBp
 n RT
mixture)
 pJ V = nJRT J

p 
J

This becomes : V
total


P
 If xJ is the fraction of the molecule, J, in mixture {x J
= nJ / nTotal ), then  xJ =1
 If xJ is the partial pressure of component J in the pA = xAp
mixture, pJ = xJ p, where p is the total pressure
0 1
» Component J need not be ideal
Mole Fraction B, xB
» p =  pJ =  xJ p this is true of all gases, not just
ideal gases
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 = Vm/ Vm°, where Vm = V/n
 Using ideal gas law, p Vm = 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 CO2
» At high temperatures (>50°C) and high
molar volumes (Vm > 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/Vm)
{Kammerlingh-Onnes, 1911}

 B C 
pV  RT 1    .......
 V V 
m 2
m m

» Virial expansions common in physical

chemistry
 Virial Equation (continued)
 Coefficients experimentally determined (see Atkins, Table 1.3) 2nd Virial Coefficients
» 3rd coefficient less impt than 2nd, etc. Equimolar Mixtures of CH4 and CF4
 B/Vm >> C/Vm2
K B1(CH4) B1(CH4) B12
 For mixtures, coeff. depend on mole fractions (cm3/mol) (cm3/mol) (cm3/mol)
273.15 -53.35 -111.00 -62.07
» B = x12B11 + 2 x1x2B12 + x22B22 298.15 -42.82 -88.30 -48.48
» x1x2B12 represents interaction between gases 373.15 -21.00 -43.50 -20.43

 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 (Vm = Z Vm°); and Vm°=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, TB
 At TB , B’  0 and, since remaining terms in virial eqn are small, p V m = RT for real gas
Critical Constants
 Consider what happens when you compress a real gas
CO2 at constant T (move to left from point A)
» Near A, P increases by Boyle’s Law
» From B to C deviate from Boyle’s 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, Tc, only one phase exists across
the entire range of compression
» This point corresponds to a certain temperature, T c,
pressure, Pc , and molar volume, Vc , for the system
2 phases  Tc, Pc , Vc are critical constants unique to gas
» Above critical point one phase exists (super critical
fluid), much denser than typical gases
 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
 n a 
2

p  (V  nB)  nRT

 TV  2

 a is a constant
» van der Waals (1873)
n 
2
nRT RT a
p  a    
V  nb V  V  b V m m
2

Dieterici (1899)
»
RTe  a / RTVm

p
V b m
 n 
2
nRT RT a
van der Waals Equation p  a   
V  nb V  V  b V

m m
2

 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 van der Waals Constants
the volume of one molecule
gas a b
 Thus V becomes (V-nb) (atm L2/ mol2) (10 L2/ mol)
-2

 b depends on the particular gas Ar 1.337 3.20

 He small, Xe large, bXe >bAr CO2 3.610 4.29
He 0.0341 2.38
» Attractive forces act to reduce the pressure Xe 4.137 5.16
 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, CO2 less so, aCO2 >>aAr
van der Waals Equation - Reliability
Ideal vs van derWaals Isotherms @ n = 1
60

Ideal Gas (150K)

Xe (150K)
50
Ideal Gas (450K)
Xe (450 K)
Ideal Gas (289.75K)
Xe (Tc=289.75K)
40

30

20

10

0
0.1 1 10
V (Liters)

 Above Tc, fit is good

 Below Tc, deviations
 van der Waal’s Loops (cont.)
T = 260K; n = 0.25 moles
400

350
Ideal Gas
300
CO2 (van der Waals)
250

200

150

100

50

0
0.01 0.1 1
V (L)

 CO2 Critical Temperature 304.2 K (31.05°C)

 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
CO2

van der Waals @T/Tc

 n 
2
nRT RT a
van der Waals Equation p  a   
V  nb V  V  b V

m m
2

 Effect of T and Vm
» 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 Tc
» Liquids and gases co-exist
» Two terms come into balance in magnitude and oscillations occur
 1st is repulsive term, 2nd attractive
» At Tc, we should have an flat inflexion point, i.e., both 1st and 2nd derivatives of equation w.r.t
Vm = 0 » Solving these equations for p,Vm and T gives pc,Vc and Tc in terms
 RT a  of a and b
d   Hint: you must use original eqn to do this
V  b V 
2
dp RT 2a
 m

m
 0 pc= a/27b3, Vc pc= 3b and Tc = 8a/27Rb
V  b  V
2
dV dV
3
m m m m
Critical compression factor, Zc, can be calculated using
 RT 2a 
d   definition for Z:
  
  
2
 V b V 
3
dp
2
2RT 6a pVm = RTZ
   0
m m

p V  a  27Rb  3
V  b V
3
dV dV Z  c c   3b 
4

RTc 27b   R8a  8

m m m m
2

This should be a constant for all gases and is (Table 1.4 )

 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 (atm)
» preduced = pr = p / pc; Vreduced = Vr =
Vm / Vc; Treduced = Tr = T/ Tc
» 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
pr