Exam 1 Review
The exam will have two sections. One section that is multiple choice, largely based on
definitions given below in the Chapter Reviews. Then there will be a second part which
is a problem solving part. During the problem solving part, you will be provided with a
equations that you may need to solve a particular problem. There will be more equations
than you need. You may be asked to derive an eqn. in one or more instance. 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. Again, 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 Wed at the review. Note that I have included the Constants
and eqns. sheet at the bottom which will be included with your exam.
Review for Chapters 1,2, and 3
Definitions: (The meanings of these words and phrases should be very familiar to
you!)
System
State of the System
Processes
Surroundings
Closed System
Absolute Temp. Scale
Open System
Adiabatic
Isolated System
Reversible Process
Irreversible Process
Kinetic Theory of Gases
Isothermal
Isobaric
Isochoric
mean free path
Macroscopic System
Microscopic System
Thermodynamic State
State Functions or State Variables
Equilibrium State
Kinetic Theory of Gas
Ideal Gas Law
Dalton’s Law of Partial Pressure
Boyles Law
Charles Law
SI Units
P, T Phase Diagram
Dependent Variable
Independent Variable
Equation of State
Extensive Variable
Intensive Variable
Phase Transitions
Gibbs Phase Rule
Component
Heat of Melting (Fusion)
Freezing Point
Heat of Vaporization
Enthalpy of Sublimation
Isotherms on PV diagram
Adiabat on PV diagram
Kinetic Energy
Potential Energy
1st Law of Thermodynamics
Internal Energy
Probability Ditribution
Maxwell-Boltzmann Distribution
Van der Waals Eqn of State
Work
Heat
Hess’ Law
Reversible
Constant Pressure Heat Capacity
Endothermic
Thermochemical Eqn.
Combustion
Molar Internal Energy
Root Mean square speed
H = U+ PV
Momentum, Pressure
Average Speed of a Gas (how can you get it)
Virial Eqn.
Compressibility Factor
External Pressure
Adiabatic
Bomb Calorimeter
Constant Volume Heat Capacity
Exothermic
Heat of Formation, Enthalpy of Formation
Average Bond Energies
Collision Frequency
Kirchoff's Law
Ideal Monatomic Gas Cpm = 5/2 R
Calculations: You should be familiar with the following types of Calculations
Using the Ideal Gas Law, or a form of it such as Boyles or Charles’ Law to Solve for P,V,
T, or n, Use of nonideal eqns. such as virial eqn. or compressibility factor
Expressing U in terms of Heat and Work, Use of the 1st Law of Thermodynamics
Use and/or derivation of Expressions for Internal Energy, Work, Heat, Enthalpy of
different types of processes such as reversible, isothermal, adiabatic, isobaric, isochoric
from the basic definitions
Use of the Gibbs Phase Rule
Dependence of Enthalpy on Temperature
Use of Heat Capacity to determine enthalpy or internal energy changes
Calculation of H and U for a chemical reaction from heats of formation, heats of
combustions, bond enthalpies, or a more general use of Hess’s Law
Calculation of H or U at an elevated temperature (Kirchoff's Law)
Expressions for dH and dU for an ideal gas
Converting between H and U
Finding H for phase changes or heating a material that not only is heated, but goes
through phase changes
Use of the concept of a State Function in calculations
REMEBER that if you do your calculation using SI units, your answer will also be
in SI units. Units are your friend.
Review for Chapter 3,4
Definitions: (The meanings of these words and phrases should be very familiar.
Some of these are also in Chapters 1 and 2.)
Path Dependent
Closed System
Expression for dH for Ideal Gas
Isenthalpic
Expression for dU for Ideal Gas
Internal Energy
Molar Internal Energy
Enthalpy
Exothermic
Endothermic
Hess' Law
H= U + PV
dU = q + w
Cpm = Cvm + R
2nd Laws of Thermodynamics
dS = dqrev / T
State Function
Entropy is a State Function
Efficiency and Carnot Efficiency
S = k ln W
Enthalpy of Formation
Standard State for Entropy
Cp = Cv + nR
Carnot Heat Engine & Assumptions
dS > dqirr / Tsurr
State Variable
Srev cycl = cycle dqrev /T = 0
Heat Engine
Absolute zero
Calculations: (you should be familiar with the following in terms of calculations)
Explanation of the Carnot Engine
Use of the 2nd Law to test if a process is realizable (spontaneous).
Calculation of the Carnot efficiency.
Calculation of the Entropy change for a heating process.
General procedure for calculating entropy change in a closed system.
Calculation of entropy changes for processes that include phase transitions
.Specification of the sign of the entropy change for a process.
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. These can be formulated into a mathematical statement
of spontaneity which involves the entropy. In any irreversible process the entropy of the
universe increases. Because entropy is a state variable, the entropy change of the system
can be calculated using a reversible process having the same initial and final states as the
irreversible process. In any reversible process the entropy of the universe remains
constant and therefore this constitutes the minimal or maximal work case.
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.
Constants and Equations
PV = nRT,
Vi/Ti = Vf/Tf,
Z1 = 1 / 2 d2 cav(N/V)
PiVi = PfVf,
Etrans = n 3/2 RT
Pi/Ti = Pf/ Tf
(P+(an2 /V2 ) (V-nb)=nRT
f(c) = 4c2 (m/2kT)3 / 2 exp(-mc2 /2kT)
Z1 = 1 / 2 d2 cav(PNav/RT) Z11 = (2)½ /2 d2 cav(PNav/RT)  = cav/z1 c = (3RT/Mm)1 / 2
c =(2RT/Mm)1 / 2 c = (8RT/(m))1 / 2
F = ma
F = -kx
PE=mgh
KE = ½ mv2
U = Q + W, W = -Pext V, W=  F dl W= - P dV, W = -nRT ln(Vf/Vi) F= C-P+2
W = -nRT ln(Pi/Pf) Q = n C  Q = m C  dU = Cv dT,
dH = Cp dT, H=U +PV,
Review for the 2nd Exam
The examination is scheduled for Thurs., Oct. 27. The exam will have two sections,
like on 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. The equations and constants that you will be given are listed
below. 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 part will be problems based on concepts taken from the
assigned homework, given on a quiz, and listed on the review sheets. Look over the
sheets and ask questions about them at the review.
Review
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= U + PV
Standard State for Entropy
dU = 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 = U-TS
spontaneity criteria based the system
G = H - TS
Gibbs Energy of Reaction
H = U + PV
Gibbs-Helmholtz Eqn
Standard State Conditions
G = H - TS
Gibbs Duhem eqn.
Phase equilibria
critical point
Chemical Potential
(phase 1) = (phase 2) etc
Clapeyron Eqn
liquid-vapor equilibrium curve
Vaporization
slope of liquid-solid equil line
Raoult’s Law
Graph of Pressure vs mole fraction
nonideal solution
intermolecular interactions of solvent
freezing pt. depression
i = moles particles/mole solute
osmotic pressure
vapor pressure lowering
boiling pt. elevation constant
 = o + RT ln(p/po)
 = o + RT ln a
partial molar volume
partial molar Gibbs free energy
Fundamental Law of Thermo
Gibbs Phase rule
triple point
Phase Diagram
reversibility and phase changes
Claussius Clapeyron
Sublimation
Fusion
solution chemical potential, 
Henry’s Law
ideal solution
intermolecular interaction of solute
Colligative properties
boiling pt. elevation
osmosis, reverse osmosis
molecular weight determination
Freezing point depression constant
non-PV work
activity
Calculations: (you should be familiar with the following in terms of calculations)
Use of Heat Capacity to Determine the Enthalpy Change
Expression for dH and dU for ideal gas
Use of Expressions for Work, Heat, U,H, S, G for different process types (i.e.
adiabatic, reversible, isothermal etc.)
Use of the 2nd Law to test if a process is realizable (spontaneous).
Derivation of Equations used to calculate the entropy changes for various processes.
Calculation of the Standard Gibbs Energy of Reaction
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 temp. (either Gibbs Helmholtz or G = H - TS
(what are the assumptions))
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
Partial Molar volume
Clapeyron or Claussius Clapeyron Eqn to Phase equilibria
Ideal Solutions Calculations and use of Henry's and Raoults Laws, Plot of P vs x A
Colligative Property Calculations
Overview
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?
What is the fundamental equation of chemical thermodynamics? The chemical
potential of a pure substance is  = 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? What is
chemical potential for ideal solution? How does the chemical potential of the pure liquid
change when a nonvolatile solute is added to it? What are the colligative properties?
How is the boiling pt., melting pt., of the solvent in solution affected by the solute? What
is the vant Hoffs constant i?
Constants and Equations
U = Q + W
rxno = prod n Hfo - react n Hfo dH = CpdT dU=CvdT
 S = nR ln(Vf/Vi)
 S = -nR ln(Pf/Pi) S= nCpm ln(Tf/Ti) Strs = trs/Ttrs
S= nCvm ln(Tf/Ti)
Cpm = R + Cvm rSo=Srxno= prodnSo -reactnSo  = 1 - Tc/Th
o
o
 = Wnet /Qin
S = Qrev/T
S (T2) = S (T1) + T rCp dT/T
o
o
o
o
Grxn = prod n fG - react n fG
Gm = Gm + RT ln(P/Po) G = H - T S
G(pf) = G(pi) + p ∫ VdP (d(G/T)/dT)P = -H/T2
G/T)f - (G/T)i = H (1/Tf - 1/Ti)
j = (G/nj)P,T,n  j = (U/nj)S,V,n
j = (H/nj)P,S,n
j = (A/nj)V,T,n
*
G = -W rev W = -pex V, W = -nRT ln(Vf/Vi), q = C V=nAVA + nBVB
VA = (∂V/∂nA)T,P,nB
G = nAGA + nBGB
GA = (∂G/∂nA)T,P,nB
dU = TdS - P dV H=U+PV G=H-TS A=U-TS dG = VdP - SdT + adna + bdnb
Go=Ho-TSo (dUsys)S,V < 0 (dSsys)U,V > 0 (dGsys)T,,P < 0
(dAsys)T,V < 0
(dHsys)P,S < 0 dH = TdS + VdP
dA = -SdT - PdV
dP/dT =trsH/trsV)
dP/dT = trsS/ trsV ln(p/p*) = (-Htrs/R) (1/T - 1/T*) p=p*exp((-trsH/R) x (1/T-1/T*))
dG=VdP-SdT + adna + bdnb  = o + RT ln(p/po)
a = a* + RT lnxa
 = o + RT ln a Pb = xbKb
Pb=mKb'
Pa = xaPa*
Tf = iKf m
b= iKbm
*
*
 = iMRT
ya = Pa/P
P = xBPA
a = x
P=Pb + (Pa*-Pb*)xa
*
P = Pa + Pb + Pc + Pd + ….
aA = pA/pA
F = C-P+2
R = 8.314 J/(mol K) R = 0.08206 L atm/(mol K) 1atm = 760 Torr 1 atm = 14.7 psi
1atm = 101325 Pa
1 bar = 105 Pa
g = 9.81 m/s2 1L = 0.001 m3
K = oC +
273.15
3rd Exam Review
The examination is scheduled for Thurs., Dec 1. 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. If you set up the problem correctly you will
get major credit.
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.
Definitions: (The meanings of these words and phrases should be very familiar.
A = Ao + RTln aA
critical point
triple point
Chemical Potential
Phase Diagram
(phase 1) = (phase 2) etc
A(phase 1) = A(phase 2) etc
Colligative properties
boiling pt. elevation constant
vapor pressure
vapor pressure lowering
freezing pt. depression
boiling pt. elevation
i = moles particles/mole solute
osmosis, reverse osmosis
osmotic pressure
molecular weight determination
vapor pressure lowering
Freezing point depression constant
Equilibrium Constant
Kp, Kc, Keq
Pressure Dependence of Gibbs Free energy activity of a pure solid or pure liquid
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
mean ionic activity
Debye-Huckel Equation
ionic strength
mean ionic activity coefficient
reaction quotient
G and the reaction quotient
Acid Dissociation Constant
Base Dissociation Constant
Van’t Hoff’s Eqn.
G at equilibrium
pH = -log[H+]
glycolytic pathway and glycolysis
metabolism
function of ATP
function of NADH
physiological conditions
diffusion
viscosity
Einsteins Relationship
root mean square displacement
sedimentation
concentration gradient
frictional coefficient
thermal transport
fluid mosaic model
transmembrane potential
surfactants
hydrophillic
lipid bilayer
transition temperature
headgroup
active transport
simple diffusion
Equilibrium Dialysis
Protein binding site
Ka, association constant
Schatchard Eqn.
fractional saturation of sites
binding constant
protein
Donnan Effect
sodium potassium pump
Le Chatelier’s Principle
Metabolic Regulation
Fick's 1st and 2nd Laws
Stokes Law
Diffusion coefficient
non-Newtonian viscosity
ultracentrifuge
flux
velocity gradient
lipids
membrane transport
amphiphilic molecules
hydrophobic
membranes
DTA and DSC
hydrocarbon tails
surface tension
passive transport
facilitated diffusion
fractional saturation of sites
Kd, dissociation constant
Intrinsic dissociation constant
Cooperative Binding
Double Reciprocal plot
identical binding sites
macromolecule
Donnan Potential
ATP hydrolysis
Calculations
Should be able to calculate osmotic pressure, molecular weight of solute, concentration
Calculation of colligative properties or the Molar Mass from the Colligative Properties
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.
Calculating the Temp dependence of the equilibrium constant
Use of LeChatliers Principle
Relationship between Kp, Kc write expression for K in activities or Kp in partial pressures
Equilibrium Constant Calculations using ICE or Henderson-Hasselbach
Equilibrium Constant and G for coupled Eqns
Calculation of the activities or concentrations of the species present at equilibrium
Calculate the Diffusion coefficient, the viscosity, the friction coefficient
Calculate the mean squared displacement based on diffusion, also the specific viscosity
Use of Debye Huckel, calculation of ionic strength, mean ionic activity,
Calculation of the mean ionic activity coefficient
Calculation of G at conditions other than at equilibrium
Calculation of Go and the equilibrium constant, and find it at other temps.
Structure of Membranes
Explain the Donnan Effect.
Understand equilibrium dialysis and the use of the Schatchard Eqn.
Relationship for  when transmembrane potential is present
Understanding of how detergents work, lipid bilayers
Know about transition temperatures in membranes
Equations and Constants
dE = TdS - P dV H=E+PV G=H-TS
A=E-TS dG = VdP - SdT + adna + bdnb
 = o + RT ln(p/po)
a = a* + RT lnxa
 = o + RT ln a Pb = xbKb
Pb=mKb'
Pa = xaPa*
Tf = iKf m
b= iKbm
*
 = iMRT
ya = Pa/P
P = xBPA
a = x
P=Pb* + (Pa*-Pb*)xa
*
P = Pa + Pb + Pc + Pd + ….
aA = pA/pA
F = C-P+2
o
o
o
o
 =  + RT ln a  =  + RT ln(P/P )
a = a + RT lnaa
a = a* + RT lnxa
o
o
RT ln(ain/aout) + ZFV =   = (r + + s - ) + v RTln a+- Kp = Kc (RT) n Po -  n
m+- = (m+r m-s )1 / v
v=r+s
m+- = m [rr ss ]1 / v
a+- = a+r a-s
r
s 1/v
½
a+- = +- m+- +- = (+ - )
log +- = -/ z+z- / AI A = 0.509
I = ½ i zi2 (mi /mo ) Go=Ho-TSo Go = - RT ln(K) G = Go + RT lnQ
ln[K(T2)/K(T1)] = -o/R (1/T2 - 1/T1) <x2 >=2Dt <d2 > = 6Dt D = kT/f
f = 6r
.Y[L] + KY = n[L] Y = ([PL]) /([P] + [PL]) Y/[L] = n/K - Y/K 1/Y = 1/n + k/(n [L])
Ki = ( i / (n-i+1)) K
R = 8.314 J/(mol K) R = 0.08206 L atm/(mol K) 1atm = 760 Torr 1 atm = 14.7 psi
1atm = 101325 Pa 1 bar = 105 Pa g = 9.81 m/s2 1L = 0.001 m3 K = oC + 273.15
k = 1.38 x 10- 2 3 J/K Nav = 6.023 x 10- 2 3