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Transcript
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! 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 - TS
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?