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!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! EXAM REVIEW !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! The examination is scheduled for Thurs., Oct. 30. The exam will have two sections, that is it will follow a format similar to the last examination. During the problem solving part, you will again be provided with a sheet of equations that you may need to solve a particular problem but you may be asked to derive an eqn. in one or more instance. There will be more eqns. than you need. You will be expected to know basic equations like the ideal gas law. Remember if you set up the problem correctly you will get major credit, so you may want to set up the problems without using your calculator and then go back at the end and punch in the numbers. The review sheets follow. They are words and concepts that should be very familiar to you. As before, I will take the multiple choice questions from these sheets. Also the problem solving will be problems based on concepts taken from problems assigned for homework, given on a quiz, and listed on the review sheets. Look over the sheets and ask questions about them on Tuesday, or at the Review Session on Wed Oct. 29 from 4-6pm in Room 240. Review for Chapter 3 Definitions: (The meanings of these words and phrases should be very familiar. System Work Reversible Heat Criteria for Exactness Heat Capacity Heat Specific Heat Law of Conservation of Energy 1st Law of Thermodynamics Isothermal Isochoric Isobaric Adiabatic Reversible State Variable Path Dependent Closed System Expression for dH for Ideal Gas Isenthalpic Expression for dE for Ideal Gas Internal Energy Molar Internal Energy Enthalpy Exothermic Endothermic Hess' Law Enthalpy of Formation H= E + PV Standard State for Entropy dE = q + w Cp = Cv + nR Cpm = Cvm + R Gibb Free Energy of Formation 2nd Laws of Thermodynamics Carnot Heat Engine & Assumptions dS = dqrev / T dS > dqirr / Tsurr State Function State Variable Entropy is a State Function Srev cycl = cycle dqre /T = 0 S = k ln W Absolute zero Efficiency and Carnot Efficiency 3rd Law of Thermodynamics Absolute Entropy Heat Engine A = E-TS Spontaneity Criteria, based on system prop. G = H - TS Gibbs Energy of Reaction H = E + PV Standard State Conditions G = H - TS activity activity coefficients peptide protein primary structure hydrogen bond London Forces dipole-dipole RNA common nuclides G,C,T,A Gibbs-Helmholtz Equilibrium Constants G0 = -RTln(Keq) reversibility and phase changes van’t Hoff Eq. ln nucleotide nucleic acid secondary structure van der Waals attraction ion-dipole polarizability DNA recognize amino acid names Calculations: (you should be familiar with the following in terms of calculations) Use of Expressions for Work, Heat, Enthalpy etc of adiabatic, reversible, isothermal etc. process Use of Heat Capacity to Determine the Enthalpy Change Expression for dH and dE for ideal gas Expressing E in Terms of Heat and Work Use of Expressions for Work, Heat, Enthalpy etc of adiabatic, reversible, isothermal etc. process Expression for dH and dE for ideal gas Use of the 2nd Law to test if a process is realizable (spontaneous). Carnot Efficiency Calculation Calculation of the Standard Gibbs Energy of Reaction Derivation of Equations used to calculate the entropy changes for various processes. Relation of Exactness and State Function and Deriving Maxwell’s Relations Writing out a differential given information on its variables. Calculations to find G at a different temperature Calculations to find G at a different pressure Use of the definition of the Chemical Potentials Expression for the molar Gibbs free energy of a gas Expression for the Fundamental Eqn of Chemical Thermodynamics for an open system General statements that define natural processes talk about the observed efficiencies in converting heat into work, the direction of heat flow, and the fact that the disorder of the universe seems to be increasing. The Carnot efficiency tells about the maximum efficiency realizable for a process which converts heat to work. The expression for the Second Law of Thermodynamics Stot > 0 for an irreversible process is strictly applicable to the system and the surroundings. HOWEVER, new thermodynamic state variables, named the Helmholtz Free Energy and Gibbs Free Energy, were defined to allow one to determine the spontaneity of a process based on the system properties and the mechanical variables. Thus (dA)T,V < 0 and (dG)T,p < 0 (closed; PV). Which property tells about the max non PV work? Which tells about the maximum amount of work the system can do Know how the expression for the Fundamental Equation of Thermodynamics. It is essentially a combination of the 1st and 2nd Laws. Remember it was derived based on a reversible process, but is it applicable to any process within the restrictions of its derivation? What are the best (natural) thermodynamic variables for U? Be able to show how more Thermodynamic information comes from the definition of the exact differential and the exactness criterion. What are Maxwell’s relations? How are they derived from the equation for dU? What about dG? What are the natural thermodynamic variables for dG? Be able to write out dG for these variables? These variables are derived from the basic definition of G=H-TS. (Gsys)T,P tells us about the spontaneity of the process, and whether the system is at equilibrium. How does it change with P and T? What is the Gibbs Helmholtz relation? Be able to use it. Does the Gibbs free energy change very much with a pressure change on a solid or liquid? Why? Review for Chapter 4 Definitions: (The meanings of these words and phrases should be very familiar. RNA DNA common nuclides G,C,T,A recognize amino acid names chemical potential partial molar Gibbs free Energy other partial molar variables chemical potential and directionality Equilibrium Constant Pressure Dependence of Gibbs Free energy activities and the equilibrium constant Standard States Std. states for pure solids or liquids Solvent and solute standard states Molarity Molality Biochemists std state Activity coefficient Activity coefficient of Ions Debye-Huckel Equation ionic strength activity coefficient of ion reaction quotient G and the reaction quotient Acid Dissociation Constant Base Dissociation Constant Van’t Hoff’s Eqn. Electrochemical Cell Galvanic Cell Electrolytic Cell Half Reaction Reduction Oxidation Std. Reduction Potential Faraday’s Constant anode cathode electrochemical cell notation Nernst Eqn Eo and K o and Go E and G + pH = -log[H ] glycolysis metabolism function of ATP function of NADH Le Chatelier’s Principle physiological conditions Metabolic Regulation primers Double Strand Formation G(initiation) PCR Calculations: (you should be familiar with the following types of calculations) Calculation of the Standard Gibbs Energy of Reaction Calculations to find G at a different temperature Calculations to find G at a different pressure Use of the definition of the Chemical Potentials Expression for the molar Gibbs free energy of a gas Calculation of the Equilibrium Constant from Gorxn or the reverse of this. (K2/K1)=-Ho/R(1/T2-1/T1) for calculating the Temp dependence of the equilibrium constant Equilibrium Constant Calculations using ICE or Henderson-Haselbach Calculation of the activities or concentrations of the species present at equilibrium Calculation of G at conditions other than at equilibrium Calculation of Go and the equilibrium constant, and find it at other temps. Determination of the cell reaction from cell notation and vice versa Determination Eooverall from Eo of the oxidation and reduction half reactions Determination of Eo reduction or oxidation from Go or Eo overall and table information Use of the Nernst Eqn. to get cell potential Moving easily between G, E, K Understanding of the various steps of glycolysis and how ATP plays a role (spontaneity) Ability to do Redox Calculations for Biological Redox Reaction PCR and Calulations regarding Double Strand Formation in Nucleic Acids What is the fundamental equation of chemical thermodynamics? The chemical potential of a pure substance is (G/n)p,T and for a perfect gas = o + RT ln(p/po) how does this change for a real gas. In general = o + RT ln a where a is the activity. For ideal gas a = p/po. For real gas a = f/po. What is the fugacity coefficient? What is the activity coefficient? Be able to calculate the equilibrium constant given pressure or concentration information and information about the activity coefficients. You should also be able to calculate what the equilibrium constant will be at some temperature of interest. Are there many standard state conditions, why?