INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 5Solutions
1. McQuarrie and Simon, 512. Paraphrase: Compute U, H, q, and w for
the reversible compression of a mona
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 3Solutions
1. McQuarrie and Simon, 38. Paraphrase: For what temperature is the ratio
of spindown to spinup proton
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 4Solutions
1. McQuarrie and Simon, 44. Paraphrase: What fraction of sodium ions
will be in the first excited electr
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 6Solutions
1. McQuarrie and Simon, 66. Paraphrase: Compute qrev and S for a
reversible cooling of one mole of an id
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 7Solutions
1. McQuarrie and Simon, 71. Paraphrase: Derive Eqs. 7.7 and 7.8 for the
temperature and pressure depende
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 8
1. McQuarrie and Simon, 81 and 82. Paraphrase: Benzene boils at 80.09
C with an enthalpy of vaporization of 30.7
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 9 Solutions
1. McQuarrie and Simon, 94. Paraphrase: Given expressions for the liquid
and solid vapor pressures of C
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 10 Solutions
1. McQuarrie and Simon, 1013. Paraphrase: Use the GibbsDuhem
equation to establish the relationship b
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 11Solutions
1. McQuarrie and Simon, 1127. Paraphrase: If a solution of 1.47 g of
dichlorobenzene in 50 g of benzene
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 12Solutions
1. (Based on McQuarrie and Simon, 131.) Write balanced halfcell
chemical reactions, and balanced compl
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 2Solutions
1. McQuarrie and Simon, 26. Paraphrase: How many molecules are there
in 1 cm3 of gas at 298 K and 1012 t
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2010
Chem (3/5)501
Introduction to Thermodynamics,
Kinetics, and Statistical Mechanics
3 Credits
Fall Semester 2010
Homework Problem Set Number 1Solutions
1. Light having a wavelength of 400 nm has a lovely purple color. What
atomic transition of hydrogen woul
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Entropy and the Second Law of Thermodynamics"
Prof. Gianluigi Veglia
So far, we have described: The zeroth law of thermodynamics: two bodies that are in thermal equilibrium with a third body are in thermal equilibrium with each other. The first law": t
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Boltzmann Factor and Partition Function"
Prof. Gianluigi Veglia
Statistical Thermodynamics provides the link between the microscopic properties of matter and its bulk (macroscopic) properties. It answers one of the most important question in Chemistry: h
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"The First Law of Thermodynamics"
Prof. Gianluigi Veglia
We are now ready to begin studying the subject of thermodynamics. What is thermodynamics? Definition: We can define thermodynamics as the study of the energy in all its various forms, and how it i
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Gibbs and Helmholtz Energies"
Prof. Gianluigi Veglia
So far we have discussed thermal equilibrium (equalization of temperature) and mechanical equilibrium (equalization of forces, i.e. pressures). What about material equilibrium? (i.e. the most stable di
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Phase Equilibria"
Prof. Gianluigi Veglia
The chemical potential
So far we have discussed only systems of fixed compositions that are closed for which: where G=G(T,P) What about an open system (e.g. liquid water evaporating) or a closed system of changing
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Liquid Solutions I Liquid/Liquid"
Prof. Gianluigi Veglia
Partial Molar Quantities: when 1+12. We are getting ready to talk about mixtures, especially liquid solutions: benzene and toluene, methanol and water, sugar and water etc. We begin by introduci
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Chemical Potential and Free Energy expressed as partition functions" MQ: Sections 23.5, 26.8, 26.9
Prof. Gianluigi Veglia
So far we used the "macroscopic" approach to thermodynamics to define our standard chemical potential. For an ideal gas, we obtained
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
Kinetics
Kinetics vs thermodynamics So far we have focused our attention on the thermodynamic properties of the chemical systems. Thermodynamics tell us what is possible, but does not necessary tell use when actually happens. For instance, the change in f
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Kinetic Theory of Gases" MQ Chapter 27
Prof. Gianluigi Veglia
Let's recall the definition of an ideal gas: The gas molecules which have mass m and diameter d are in constant motion The molecules are small compared to the distances they travel between col
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Transition State Theory"
Prof. Gianluigi Veglia
Last lecture, we closed with the introduction of the Arrhenius equation:
k = Ae  Ea / RT
We also concluded that this expression can be easily linked to the thermodynamics using the following:
k (T ) = c e
INTRODUCTION TO THERMODYNAMICS, KINETICS, AND STATISTICAL MECHANICS
CHEM 3501

Fall 2009
"Properties of Gases"
Prof. Gianluigi Veglia
The physical state of a substance is defined by its physical properties. These properties are linked through the equation of state. The general form of the equation of state is:
p = f (T , V , n )
PV = nRT
A