Foundations of Chemical Kinetics. Lecture 30: Transition-state theory in the solution phase
|
|
- Kelley Palmer
- 5 years ago
- Views:
Transcription
1 Foundations of Chemical Kinetics Lecture 30: Transition-state theory in the solution phase Marc R. Roussel Department of Chemistry and Biochemistry
2 Transition-state theory in solution We revisit our original derivation of the thermodynamic formalism of transition-state theory. We decompose the reaction A + B k product(s) into A + B K TS k product(s) For this representation, v = k [TS]. The equilibrium constant K is related to the activities of the transition state and reactants by a TS K = a A a B = γ TS [TS]c γ A γ B [A][B]
3 Transition-state theory in solution (continued) The derivation is completed as follows: [TS] = K c γ A γ B γ TS [A][B] v = k [TS] = k K c γ A γ B γ TS [A][B] k = k K γ A γ B c γ TS For an ideal solution, all the activity coefficients are equal to unity, and we get the limiting value k 0 = k K c Therefore k = k 0 γ A γ B γ TS
4 Transition-state theory in solution Constancy of first-order rate constants If we repeat the above derivation for a first-order reaction R product(s), we get k = k 0 γ R γ TS In a unimolecular reaction, the reactant and transition state are typically very similar, the difference between the two involving small changes in charge distribution and geometry. Accordingly, γr γ TS, so various factors that affect the activity coefficients (e.g. pressure, ionic strength) should have little effect on the rate constant.
5 Transition-state theory in solution Constancy of first-order rate constants (continued) Now imagine slowly decreasing the density of the solvent. In the limit, this operation converts a reaction in solution to one in the gas phase. By the argument above, the ratio of activity coefficients shouldn t change much, so the rate constant should be more-or-less constant throughout this operation. This explains the experimental observation that, for first-order reactions, k is roughly the same whether the reaction occurs in the gas phase or in solution.
6 Variation of rate constant with pressure We return to the ideal solution case. In the thermodynamic formulation of transition-state theory, we have, for second-order reactions, k 0 = k BT c h exp ( G ) Recall that dg = V dp S dt or, for a reaction, d G = V dp S dt so that G p = V T
7 Variation of rate constant with pressure (continued) For k0, we have ( ) kb T ln k 0 = ln c G h p ln k 0 = 1 G T p T = V where V is the change in the molar volume (change in volume of solution per mole of reaction) on accessing the transition state. If V > 0, the rate constant decreases as p increases. The reverse is true if V < 0.
8 Gas-phase vs solution-phase rate constants We now consider the thermodynamic formulation of transition-state theory, which gives, for second-order reactions, k 0 = k BT ( c h exp G ) The above equation should apply both in solution (k 0,s G s ) and in the gas phase (k 0,g G g ). We want to figure out how the two rate constants are related.
9 Gas-phase vs solution-phase rate constants (continued) Now consider the following thermodynamic cycle: solv G (A) solv G (B) A (sol) + B (sol) A (g) + B (g) G s TS (sol) G g TS (g) solv G (TS) where solv G is the standard free energy of solvation. Reading off the cycle, we have G s = G g + solv G (TS) [ solv G (A) + solv G (B)] = G g + solv G
10 Gas-phase vs solution-phase rate constants (continued) From and k 0,s = k ( BT c h exp Gs ) G s = G g + solv G we get ( ) k 0,s = k BT c h exp Gg exp ( solv G ) = k 0,g exp ( solv G )
11 Gas-phase vs solution-phase rate constants (continued) k 0,s = k 0,g exp ( solv G ) TS better solvated than reactants: solv G < 0 In this case, the argument of the exponential involving this solvation term is positive and k 0,s > k 0,g. Reactants better solvated than TS: solv G > 0 We then have the exponential of a negative value, so k 0,s < k 0,g.
12 Gas-phase vs solution-phase rate constants (continued) Under what conditions might we expect solv G < 0? One example might involve hydrophobic reactants and TS. If the TS is more compact (exposes less surface area to the solvent) than the two reactants, which will often be the case, then each of the individual solv G terms will be positive, but the solvation free energy of the transition state would be much smaller than that of either reactant. Differences in solvation free energies of 10 kj mol 1 are not unreasonable under these conditions, which would give exp ( solv G ) = 56 at 25 C. Rate enhancements of this order of magnitude have been seen in some reactions.
Chemistry 2000 Lecture 11: Chemical equilibrium
Chemistry 2000 Lecture 11: Chemical equilibrium Marc R. Roussel February 4, 2019 Marc R. Roussel Chemical equilibrium February 4, 2019 1 / 27 Equilibrium and free energy Thermodynamic criterion for equilibrium
More informationFoundations of Chemical Kinetics. Lecture 12: Transition-state theory: The thermodynamic formalism
Foundations of Chemical Kinetics Lecture 12: Transition-state theory: The thermodynamic formalism Marc R. Roussel Department of Chemistry and Biochemistry Breaking it down We can break down an elementary
More informationFoundations of Chemical Kinetics. Lecture 17: Unimolecular reactions in the gas phase: Lindemann-Hinshelwood theory
Foundations of Chemical Kinetics Lecture 17: Unimolecular reactions in the gas phase: Lindemann-Hinshelwood theory Marc R. Roussel Department of Chemistry and Biochemistry The factorial The number n(n
More informationExpress the transition state equilibrium constant in terms of the partition functions of the transition state and the
Module 7 : Theories of Reaction Rates Lecture 33 : Transition State Theory Objectives After studying this Lecture you will be able to do the following. Distinguish between collision theory and transition
More informationChemistry 2000 Lecture 12: Temperature dependence of the equilibrium constant
Chemistry 2000 Lecture 12: Temperature dependence of the equilibrium constant Marc R. Roussel February 12, 2019 Marc R. Roussel Temperature dependence of equilibrium February 12, 2019 1 / 15 Temperature
More informationLattice protein models
Lattice protein models Marc R. Roussel epartment of Chemistry and Biochemistry University of Lethbridge March 5, 2009 1 Model and assumptions The ideas developed in the last few lectures can be applied
More informationChemistry 2000 Lecture 9: Entropy and the second law of thermodynamics
Chemistry 2000 Lecture 9: Entropy and the second law of thermodynamics Marc R. Roussel January 23, 2018 Marc R. Roussel Entropy and the second law January 23, 2018 1 / 29 States in thermodynamics The thermodynamic
More informationReaction Dynamics (2) Can we predict the rate of reactions?
Reaction Dynamics (2) Can we predict the rate of reactions? Reactions in Liquid Solutions Solvent is NOT a reactant Reactive encounters in solution A reaction occurs if 1. The reactant molecules (A, B)
More informationMixtures. Partial Molar Quantities
CHEM 331 Physical Chemistry Fall 2017 Mixtures Our current discussion takes up some general results for systems that are mixtures and/or open. The former involve systems that contain multiple components;
More informationLecture 2. Review of Basic Concepts
Lecture 2 Review of Basic Concepts Thermochemistry Enthalpy H heat content H Changes with all physical and chemical changes H Standard enthalpy (25 C, 1 atm) (H=O for all elements in their standard forms
More informationThermodynamics of Reactive Systems The Equilibrium Constant
Lecture 27 Thermodynamics of Reactive Systems The Equilibrium Constant A. K. M. B. Rashid rofessor, Department of MME BUET, Dhaka Today s Topics The Equilibrium Constant Free Energy and Equilibrium Constant
More informationwhere R = universal gas constant R = PV/nT R = atm L mol R = atm dm 3 mol 1 K 1 R = J mol 1 K 1 (SI unit)
Ideal Gas Law PV = nrt where R = universal gas constant R = PV/nT R = 0.0821 atm L mol 1 K 1 R = 0.0821 atm dm 3 mol 1 K 1 R = 8.314 J mol 1 K 1 (SI unit) Standard molar volume = 22.4 L mol 1 at 0 C and
More informationWe can see from the gas phase form of the equilibrium constant that pressure of species depend on pressure. For the general gas phase reaction,
Pressure dependence Equilibrium constant We can see from the gas phase form of the equilibrium constant that the equilibrium concentrations of species depend on pressure. This dependence is inside the
More informationCHEM-UA 652: Thermodynamics and Kinetics
1 CHEM-UA 652: Thermodynamics and Kinetics Notes for Lecture 13 I. PHASE DIAGRAMS The different phases of substances are characterized by different ranges of thermodynamic variables in which these phasesarethestablephases.
More informationGeneral Chemistry revisited
General Chemistry revisited A(g) + B(g) C(g) + D(g) We said that G = H TS where, eg, H = f H(C) + f H(D) - f H(A) - f H(B) G < 0 implied spontaneous to right G > 0 implied spontaneous to left In a very
More informationLecture 6 Free Energy
Lecture 6 Free Energy James Chou BCMP21 Spring 28 A quick review of the last lecture I. Principle of Maximum Entropy Equilibrium = A system reaching a state of maximum entropy. Equilibrium = All microstates
More informationFoundations of Chemical Kinetics. Lecture 19: Unimolecular reactions in the gas phase: RRKM theory
Foundations of Chemical Kinetics Lecture 19: Unimolecular reactions in the gas phase: RRKM theory Marc R. Roussel Department of Chemistry and Biochemistry Canonical and microcanonical ensembles Canonical
More informationThe Second Law of Thermodynamics (Chapter 4)
The Second Law of Thermodynamics (Chapter 4) First Law: Energy of universe is constant: ΔE system = - ΔE surroundings Second Law: New variable, S, entropy. Changes in S, ΔS, tell us which processes made
More informationStoichiometry, Chemical Equilibrium
Lecture 3 Stoichiometry, Chemical Equilibrium http://en.wiipedia.org/wii/category:physical_chemistry http://en.wiipedia.org/wii/category:thermodynamics Stoichiometry = Constraints for Kinetics Q?: for
More informationEnthalpy and Adiabatic Changes
Enthalpy and Adiabatic Changes Chapter 2 of Atkins: The First Law: Concepts Sections 2.5-2.6 of Atkins (7th & 8th editions) Enthalpy Definition of Enthalpy Measurement of Enthalpy Variation of Enthalpy
More informationChemical Reaction Engineering. Lecture 2
hemical Reaction Engineering Lecture 2 General algorithm of hemical Reaction Engineering Mole balance Rate laws Stoichiometry Energy balance ombine and Solve lassification of reactions Phases involved:
More informationTransition Theory Abbreviated Derivation [ A - B - C] # E o. Reaction Coordinate. [ ] # æ Æ
Transition Theory Abbreviated Derivation A + BC æ Æ AB + C [ A - B - C] # E A BC D E o AB, C Reaction Coordinate A + BC æ æ Æ æ A - B - C [ ] # æ Æ æ A - B + C The rate of reaction is the frequency of
More informationUnit 7 Kinetics and Thermodynamics
17.1 The Flow of Energy Heat and Work Unit 7 Kinetics and Thermodynamics I. Energy Transformations A. Temperature 1. A measure of the average kinetic energy of the particles in a sample of matter B. Heat
More informationCHEMISTRY Topic #2: Thermochemistry and Electrochemistry What Makes Reactions Go? Fall 2018 Dr. Susan Findlay See Exercises in Topic 8
CHEMISTRY 2000 Topic #2: Thermochemistry and Electrochemistry What Makes Reactions Go? Fall 208 Dr. Susan Findlay See Exercises in Topic 8 Vapour Pressure of Pure Substances When you leave wet dishes on
More information7. Kinetics controlled by fluctuations: Kramers theory of activated processes
7. Kinetics controlled by fluctuations: Kramers theory of activated processes Macroscopic kinetic processes (time dependent concentrations) Elementary kinetic process Reaction mechanism Unimolecular processes
More informationChemistry 2000 Lecture 15: Electrochemistry
Chemistry 2000 Lecture 15: Electrochemistry Marc R. Roussel February 21, 2018 Marc R. Roussel Chemistry 2000 Lecture 15: Electrochemistry February 21, 2018 1 / 33 Electrochemical cells Electrochemical
More informationThe Chemical Potential
CHEM 331 Physical Chemistry Fall 2017 The Chemical Potential Here we complete our pivot towards chemical thermodynamics with the introduction of the Chemical Potential ( ). This concept was first introduced
More informationEffect of adding an ideal inert gas, M
Effect of adding an ideal inert gas, M Add gas M If there is no change in volume, then the partial pressures of each of the ideal gas components remains unchanged by the addition of M. If the reaction
More informationThermodynamic and Stochiometric Principles in Materials Balance
Thermodynamic and Stochiometric Principles in Materials Balance Typical metallurgical engineering problems based on materials and energy balance NiO is reduced in an open atmosphere furnace by excess carbon
More informationChemical Kinetics. Topic 7
Chemical Kinetics Topic 7 Corrosion of Titanic wrec Casón shipwrec 2Fe(s) + 3/2O 2 (g) + H 2 O --> Fe 2 O 3.H 2 O(s) 2Na(s) + 2H 2 O --> 2NaOH(aq) + H 2 (g) Two examples of the time needed for a chemical
More informationGeology 633 Metamorphism and Lithosphere Evolution. Thermodynamic calculation of mineral reactions I: Reactions involving pure phases
Geology 633 Metamorphism and Lithosphere Evolution Thermodynamic calculation of mineral reactions I: Reactions involving pure phases The formulation for the free energy change of any reaction involving
More informationThermodynamics: Lecture 6
Thermodynamics: Lecture 6 Chris Glosser March 14, 2001 1 OUTLINE I. Chemical Thermodynamics (A) Phase equilibrium (B) Chemical Reactions (C) Mixing and Diffusion (D) Lead-Acid Batteries 2 Chemical Thermodynamics
More informationChapter 17: Spontaneity, Entropy, and Free Energy
Chapter 17: Spontaneity, Entropy, and Free Energy Review of Chemical Thermodynamics System: the matter of interest Surroundings: everything in the universe which is not part of the system Closed System:
More informationlet: rate constant at sea level be ks and that on mountain be km ks/km = 100 ( 3mins as opposed to 300 mins)
homework solution : "egg question" let: rate constant at sea level be ks and that on mountain be km ks/km = 100 ( 3mins as opposed to 300 mins) ln ks/km = Ea x 10 / 373 x 363 x 8.314 x 10-3 4.605 = 10Ea/1125.7
More informationChemical Kinetics. Chapter 13. Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chemical Kinetics Chapter 13 Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Chemical Kinetics Thermodynamics does a reaction take place? Kinetics how fast does
More informationCHAPTER 9 LECTURE NOTES
CHAPTER 9 LECTURE NOTES 9.1, 9.2: Rate of a reaction For a general reaction of the type A + 3B 2Y, the rates of consumption of A and B, and the rate of formation of Y are defined as follows: Rate of consumption
More informationChemical Kinetics. Kinetics versus Thermodynamics
Chemical Kinetics Petrucci, Harwood and Herring (8th edition) Problem Set: Chapter 5 questions 29, 33, 35, 43a, 44, 53, 63, 8 CHEM 3. Chemical Kinetics Kinetics versus Thermodynamics - thermodynamics tells
More informationLecture 27. Transition States and Enzyme Catalysis
Lecture 27 Transition States and Enzyme Catalysis Reading for Today: Chapter 15 sections B and C Chapter 16 next two lectures 4/8/16 1 Pop Question 9 Binding data for your thesis protein (YTP), binding
More informationEEC 503 Spring 2009 REVIEW 1
EEC 503 Spring 2009 REVIEW 1 1. Why are chemical reactions important to energy, environmental and process engineering? Name as many reasons as you can think of. 2. What is a chemical reaction? 3. What
More informationSome properties of the Helmholtz free energy
Some properties of the Helmholtz free energy Energy slope is T U(S, ) From the properties of U vs S, it is clear that the Helmholtz free energy is always algebraically less than the internal energy U.
More informationThe underlying prerequisite to the application of thermodynamic principles to natural systems is that the system under consideration should be at equilibrium. http://eps.mcgill.ca/~courses/c220/ Reversible
More informationThermodynamics. For the process to occur under adiabatic conditions, the correct condition is: (iii) q = 0. (iv) = 0
Thermodynamics Choose the correct answer. A thermodynamic state function is a quantity (i) used to determine heat changes (ii) whose value is independent of path (iii) used to determine pressure volume
More informationBioinformatics: Network Analysis
Bioinformatics: Network Analysis Reaction Kinetics COMP 572 (BIOS 572 / BIOE 564) - Fall 2013 Luay Nakhleh, Rice University 1 Reaction kinetics is the study of how fast chemical reactions take place, what
More informationOCN 623: Thermodynamic Laws & Gibbs Free Energy. or how to predict chemical reactions without doing experiments
OCN 623: Thermodynamic Laws & Gibbs Free Energy or how to predict chemical reactions without doing experiments Definitions Extensive properties Depend on the amount of material e.g. # of moles, mass or
More informationChapter 14 Chemical Kinetics
7/10/003 Chapter 14 Chemical Kinetics 14-1 Rates of Chemical Reactions 14- Reaction Rates and Concentrations 14-3 The Dependence of Concentrations on Time 14-4 Reaction Mechanisms 14-5 Reaction Mechanism
More informationFoundations of Chemical Kinetics. Lecture 18: Unimolecular reactions in the gas phase: RRK theory
Foundations of Chemical Kinetics Lecture 18: Unimolecular reactions in the gas phase: RRK theory Marc R. Roussel Department of Chemistry and Biochemistry Frequentist interpretation of probability and chemical
More informationCY T. Pradeep. Lectures 11 Theories of Reaction Rates
CY1001 2015 T. Pradeep Lectures 11 Theories of Reaction Rates There are two basic theories: Collision theory and activated complex theory (transition state theory). Simplest is the collision theory accounts
More informationChemistry 2000 Lecture 14: Redox reactions
Chemistry 2000 Lecture 14: Redox reactions Marc R. Roussel February 8, 2018 Marc R. Roussel Chemistry 2000 Lecture 14: Redox reactions February 8, 2018 1 / 12 Review: Oxidation states The oxidation state
More informationrate of reaction forward conc. reverse time P time Chemical Equilibrium Introduction Dynamic Equilibrium Dynamic Equilibrium + RT ln f p
Chemical Equilibrium Chapter 9 of Atkins: Sections 9.1-9.2 Spontaneous Chemical Reactions The Gibbs Energy Minimum The reaction Gibbs energy Exergonic and endergonic reactions The Description of Equilibrium
More informationLecture 20. Chemical Potential
Lecture 20 Chemical Potential Reading: Lecture 20, today: Chapter 10, sections A and B Lecture 21, Wednesday: Chapter 10: 10 17 end 3/21/16 1 Pop Question 7 Boltzmann Distribution Two systems with lowest
More information[ A] 2. [ A] 2 = 2k dt. [ A] o
Chemistry 360 Dr Jean M Standard Problem Set 3 Solutions The reaction 2A P follows second-order kinetics The rate constant for the reaction is k350 0 4 Lmol s Determine the time required for the concentration
More informationmacroscopic view (phenomenological) microscopic view (atomistic) computing reaction rate rate of reactions experiments thermodynamics
Rate Theory (overview) macroscopic view (phenomenological) rate of reactions experiments thermodynamics Van t Hoff & Arrhenius equation microscopic view (atomistic) statistical mechanics transition state
More informationThermodynamic condition for equilibrium between two phases a and b is G a = G b, so that during an equilibrium phase change, G ab = G a G b = 0.
CHAPTER 5 LECTURE NOTES Phases and Solutions Phase diagrams for two one component systems, CO 2 and H 2 O, are shown below. The main items to note are the following: The lines represent equilibria between
More informationLiquids and Solutions Crib Sheet
Liquids and Solutions Crib Sheet Determining the melting point of a substance from its solubility Consider a saturated solution of B in a solvent, A. Since the solution is saturated, pure solid B is in
More informationRate of Heating and Cooling
Rate of Heating and Cooling 35 T [ o C] Example: Heating and cooling of Water E 30 Cooling S 25 Heating exponential decay 20 0 100 200 300 400 t [sec] Newton s Law of Cooling T S > T E : System S cools
More informationANSWER KEY. Chemistry 25 (Spring term 2016) Midterm Examination
Name ANSWER KEY Chemistry 25 (Spring term 2016) Midterm Examination 1 Some like it hot 1a (5 pts) The Large Hadron Collider is designed to reach energies of 7 TeV (= 7 x 10 12 ev, with 1 ev = 1.602 x 10-19
More informationCH1020 Exam #1 Study Guide
CH1020 Exam #1 Study Guide For reference see Chemistry: An Atoms-focused Approach by Gilbert, Kirss, and Foster Chapter 12: Thermodynamics Definitions & Concepts to know: Thermodynamics: the study of the
More informationLecture 6. NONELECTROLYTE SOLUTONS
Lecture 6. NONELECTROLYTE SOLUTONS NONELECTROLYTE SOLUTIONS SOLUTIONS single phase homogeneous mixture of two or more components NONELECTROLYTES do not contain ionic species. CONCENTRATION UNITS percent
More informationThe first law of thermodynamics continued
Lecture 7 The first law of thermodynamics continued Pre-reading: 19.5 Where we are The pressure p, volume V, and temperature T are related by an equation of state. For an ideal gas, pv = nrt = NkT For
More informationSolutions to Problem Set 6
Solutions to Problem Set 6 1. non- ideal gas, 1 mol 20.0 L 300 K 40.0 L 300 K isothermal, reversible Equation of state: (a)b is a constant independent of T Given du = ( U/ T) V dt + ( U/ V) T dv U = U(T,V)
More informationChapter 14 Chemical Kinetics
4//004 Chapter 4 Chemical Kinetics 4- Rates of Chemical Reactions 4- Reaction Rates and Concentrations 4-3 The Dependence of Concentrations on Time 4-4 Reaction Mechanisms 4-5 Reaction Mechanism and Rate
More informationPhysical Chemistry Chapter 6 Chemical Kinetics
Physical Chemistry Chapter 6 Chemical Kinetics by Azizul Helmi Sofian Faculty of Chemical & Natural Resources Engineering azizulh@ump.edu.my Chapter Description Aims To define rate laws accordingly To
More informationSolutions to Problem Assignment 1 (Kinetics) Oxtoby Problems -- see Solutions Manual. Solutions to Lecture Problems I # 1-6
Solutions to Problem Assignment 1 (Kinetics) Oxtoby Problems -- see Solutions Manual Solutions to Lecture Problems I # 1-6 I-1. This problem illustrates how the differential rate law (DRL) can be simplified
More informationCourtesy of Marc De Graef. Used with permission.
Courtesy of Marc De Graef. Used with permission. 3.01 PS 5 3.01 Issued: 10.31.04 Fall 005 Due: 10..04 1. Electrochemistry. a. What voltage is measured across the electrodes of a Zn/Cu Daniell galvanic
More informationPhase Equilibrium: Preliminaries
Phase Equilibrium: Preliminaries Phase diagrams for two one component systems, CO 2 and H 2 O, are shown below. The main items to note are the following: The lines represent equilibria between two phases.
More informationFrom what we know now (i.e, ΔH and ΔS) How do we determine whether a reaction is spontaneous?
pontaneous Rxns A&G-1 From what we know now (i.e, Δ and Δ) ow do we determine whether a reaction is spontaneous? But Δ and Δ are not enough... here is competition between lowering energy and raising entropy!
More informationChapter 19 The First Law of Thermodynamics
Chapter 19 The First Law of Thermodynamics The first law of thermodynamics is an extension of the principle of conservation of energy. It includes the transfer of both mechanical and thermal energy. First
More informationClass XI Chapter 6 Thermodynamics Question 6.1: Choose the correct answer. A thermodynamic state function is a quantity (i) used to determine heat changes (ii) whose value is independent of path (iii)
More informationLecture 12 Elementary Chemical Kinetics: Concepts
Lecture 12 Elementary Chemical Kinetics: Concepts Is it possible to understand the feasibility of processes? Yes - thermodynamics - thermodynamic state functions. Time dependence of chemical processes
More informationGeneral Physical Chemistry I
General Physical Chemistry I Lecture 11 Aleksey Kocherzhenko March 12, 2015" Last time " W Entropy" Let be the number of microscopic configurations that correspond to the same macroscopic state" Ø Entropy
More information1. Why are chemical reactions important to energy, environmental and process engineering? Name as many reasons as you can think of.
EEC 503 Spring 2013 REVIEW 1: BASIC KINETIC CONCEPTS 1. Why are chemical reactions important to energy, environmental and process engineering? Name as many reasons as you can think of. 2. What is a chemical
More informationSo far in talking about thermodynamics, we ve mostly limited ourselves to
251 Lecture 33 So far in talking about thermodynamics, we ve mostly limited ourselves to discussions of thermochemistry, a quantification of the heat absorbed or given off as the result of a chemical reaction.
More informationExam 3 Solutions. ClO g. At 200 K and a total pressure of 1.0 bar, the partial pressure ratio for the chlorine-containing compounds is p ClO2
Chemistry 360 Dr. Jean M. Standard Fall 2016 Name KEY Exam 3 Solutions 1.) (14 points) Consider the gas phase decomposition of chlorine dioxide, ClO 2, ClO 2 ( g) ClO ( g) + O ( g). At 200 K and a total
More informationAdvanced Physical Chemistry CHAPTER 18 ELEMENTARY CHEMICAL KINETICS
Experimental Kinetics and Gas Phase Reactions Advanced Physical Chemistry CHAPTER 18 ELEMENTARY CHEMICAL KINETICS Professor Angelo R. Rossi http://homepages.uconn.edu/rossi Department of Chemistry, Room
More informationThe Rate Expression. The rate, velocity, or speed of a reaction
The Rate Expression The rate, velocity, or speed of a reaction Reaction rate is the change in the concentration of a reactant or a product with time. A B rate = - da rate = db da = decrease in concentration
More informationThere are five problems on the exam. Do all of the problems. Show your work
CHM 3400 Fundamentals of Physical Chemistry Second Hour Exam March 8, 2017 There are five problems on the exam. Do all of the problems. Show your work R = 0.08206 L atm/mole K N A = 6.022 x 10 23 R = 0.08314
More informationCalculate the mass of L of oxygen gas at 25.0 C and 1.18 atm pressure.
148 Calculate the mass of 22650 L of oxygen gas at 25.0 C and 1.18 atm pressure. 1 - Convert the volume of oxygen gas to moles using IDEAL GAS EQUATION 2 - Convert moles oxygen gas to mass using formula
More informationChemistry 123: Physical and Organic Chemistry Topic 2: Thermochemistry
Recall the equation. w = -PΔV = -(1.20 atm)(1.02 L)( = -1.24 10 2 J -101 J 1 L atm Where did the conversion factor come from? Compare two versions of the gas constant and calculate. 8.3145 J/mol K 0.082057
More informationEnthalpy, Entropy, and Free Energy Calculations
Adapted from PLTL The energies of our system will decay, the glory of the sun will be dimmed, and the earth, tideless and inert, will no longer tolerate the race which has for a moment disturbed its solitude.
More informationShort Announcements. 1 st Quiz today: 15 minutes. Homework 3: Due next Wednesday.
Short Announcements 1 st Quiz today: 15 minutes Homework 3: Due next Wednesday. Next Lecture, on Visualizing Molecular Dynamics (VMD) by Klaus Schulten Today s Lecture: Protein Folding, Misfolding, Aggregation
More informationChemistry 201: General Chemistry II - Lecture
Chemistry 201: General Chemistry II - Lecture Dr. Namphol Sinkaset Chapter 19 Study Guide Concepts 1. The First Law of Thermodynamics is also known as the Law of Conservation of Energy. 2. In any process
More informationTOPIC 6: Chemical kinetics
TOPIC 6: Chemical kinetics Reaction rates Reaction rate laws Integrated reaction rate laws Reaction mechanism Kinetic theories Arrhenius law Catalysis Enzimatic catalysis Fuente: Cedre http://loincognito.-iles.wordpress.com/202/04/titanic-
More informationA First Course on Kinetics and Reaction Engineering Unit 4. Reaction Rates and Temperature Effects
Unit 4. Reaction Rates and Temperature Effects Overview This course is divided into four parts, I through IV. Part II is focused upon modeling the rates of chemical reactions. Unit 4 is the first unit
More informationMODULE No. 24: Solution Kinetics Part - III
Subject Paper No and Title Module No and Title Module Tag 6 and PHYSICAL CHEMISTRY-II (Statistical 24 and Solution Kinetics - III CHE_P6_M24 TABLE OF CONTENTS 1. Learning outcomes 2. Introduction 3. Primary
More informationStoichiometric Reactor Module
Reactor Analysis Types of Reactors Stoichiometric Reactor Module Stoichiometric Reactors (1) Stoichiometric Reactors (2) Stoichiometric Reactors (3) Equilibrium Reactors Gibbs Reactor RGibbs Module Equilibrium
More informationRRK theory. Marc R. Roussel Department of Chemistry and Biochemistry University of Lethbridge. April 3, 2009
RRK theory Marc R. Roussel Department of Chemistry and Biochemistry University of Lethbridge April 3, 2009 Isomerization reactions as a test of theories of unimolecular reactions Gas-phase unimolecular
More informationThermodynamic Variables and Relations
MME 231: Lecture 10 Thermodynamic Variables and Relations A. K. M. B. Rashid Professor, Department of MME BUET, Dhaka Today s Topics Thermodynamic relations derived from the Laws of Thermodynamics Definitions
More informationmacroscopic view (phenomenological) microscopic view (atomistic) computing reaction rate rate of reactions experiments thermodynamics
Rate heory (overview) macroscopic view (phenomenological) rate of reactions experiments thermodynamics Van t Hoff & Arrhenius equation microscopic view (atomistic) statistical mechanics transition state
More informationCHAPTER 21: Reaction Dynamics
CHAPTER 21: Reaction Dynamics I. Microscopic Theories of the Rate Constant. A. The Reaction Profile (Potential Energy diagram): Highly schematic and generalized. A---B-C B. Collision Theory of Bimolecular
More informationCHEM-UA 652: Thermodynamics and Kinetics
CHEM-UA 652: hermodynamics and Kinetics Notes for Lecture 6 I. SAISICAL MECHANICS OF SOLVAION: SOLVAION FREE ENERGIES We consider a solvent with coordinates r (a),...,r(a) N a in to which a solute with
More informationChemical reactors. H has thermal contribution, pressure contribution (often negligible) and reaction contribution ( source - like)
Chemical reactors - chemical transformation of reactants into products Classification: a) according to the type of equipment o batch stirred tanks small-scale production, mostly liquids o continuous stirred
More informationSolutions to Chem 203 TT1 Booklet
Solutions to Chem 03 TT1 Booklet Chem03 TT1 Booklet Solutions to Gases Practice Problems Problem 1. Answer: C Increasing the temperature increases the kinetic energy of the molecules in the liquid causing
More informationThe lattice model of polymer solutions
The lattice model of polymer solutions Marc R. Roussel Department of Chemistry and Biochemistry University of Lethbridge February 25, 2009 1 The lattice model of polymer solutions In the last note, we
More informationln( P vap(s) / torr) = T / K ln( P vap(l) / torr) = T / K
Chem 4501 Introduction to Thermodynamics, 3 Credits Kinetics, and Statistical Mechanics Fall Semester 2017 Homework Problem Set Number 9 Solutions 1. McQuarrie and Simon, 9-4. Paraphrase: Given expressions
More informationSaturday Study Session 1 3 rd Class Student Handout Thermochemistry
Saturday Study Session 1 3 rd Class Student Handout Thermochemistry Multiple Choice Identify the choice that best completes the statement or answers the question. 1. C 2 H 4 (g) + 3 O 2 (g) 2 CO 2 (g)
More informationFree energy, electrostatics, and the hydrophobic effect
Protein Physics 2016 Lecture 3, January 26 Free energy, electrostatics, and the hydrophobic effect Magnus Andersson magnus.andersson@scilifelab.se Theoretical & Computational Biophysics Recap Protein structure
More informationLecture 7 Enthalpy. NC State University
Chemistry 431 Lecture 7 Enthalpy NC State University Motivation The enthalpy change ΔH is the change in energy at constant pressure. When a change takes place in a system that is open to the atmosphere,
More informationThermodynamics. Chem 36 Spring The study of energy changes which accompany physical and chemical processes
Thermodynamics Chem 36 Spring 2002 Thermodynamics The study of energy changes which accompany physical and chemical processes Why do we care? -will a reaction proceed spontaneously? -if so, to what extent?
More informationPHEN 612 SPRING 2008 WEEK 1 LAURENT SIMON
PHEN 612 SPRING 2008 WEEK 1 LAURENT SIMON Chapter 1 * 1.1 Rate of reactions r A A+B->C Species A, B, and C We are interested in the rate of disappearance of A The rate of reaction, ra, is the number of
More informationThermodynamics (Classical) for Biological Systems Prof. G. K. Suraishkumar Department of Biotechnology Indian Institute of Technology Madras
Thermodynamics (Classical) for Biological Systems Prof. G. K. Suraishkumar Department of Biotechnology Indian Institute of Technology Madras Module No. # 02 Additional Thermodynamic Functions Lecture No.
More information