Syllabus is entirely online - don't actually need to buyDr. Ray - professor, from Michigan, PhD in 2005 here
On CompassSyllabus is there
Course website:
[email protected] - better for email
Tues: 10-11:30Wed: 9-10:30Thurs: 13:30-15:30Online - thurs: 10:30-12:00
Office hours
Any Edition of Zumdahl will do (7th edition)The organic chemistry book (option c) is NOT necessary - all information can be found online (esp. on wikipedia…)
Kinetics and thermodynamics-
Organic chemistry-
Critical thinking-
Appreciate chemistry-
Course objectives - on the handout in more details
Look through outline-
Look at book - no need to read every sentence-
Watch the video he makes before each class-
Before each lecture must
We will use clickers - 32 classes, 20 clicker points - 1 point per classGrading
Work Points
Exam Corrections 45
Electronic Homework 85
Clickers 20
Quizzes (top 5 of 6) 150
Exams 450
Final Exam 250
Total 1000
LON CAPA is on compassMay want to get discussion booklet
18 December 13:30 to 16:30Final Exam (last possible one):
10 point scale is 'worst possible'
15% A35% B40% C10% D,F
Percentages though (worst case scenario)
Grading
Can read through the rest
Will use LON CAPA
First ClassMonday, August 24, 2009
14:55
Notes Page 1
Burning cheetos - a chemical reaction - what we will be studyingChapter 6: ThermochemistryChapter 16: Spontaneity, Entropy, and Free EnergyChapter 17: ElectrochemistryChapter 12: Chemical Kinetics
How organic chemists think about bonding and electron flowFunctional groupsReactions of alkanes, alkenes, alcohols, carbonyl containing compoundsMechanisms behind reactionsStereochemistryPeptides and how they work
Then Organic Chemistry
Real Chemistry!Monday, August 24, 2009
15:41
Notes Page 2
Can't create or destroy it
Energy is conserved-
Potential (PE) = position
Kinetic (KE) = motion
When drop book, energy is transferred to surroundings□
Other varieties too
Energy -
1st Law of Thermodynamics
State function: only based on present state, not past○
Energy is a state function-
Path matters○
Work is NOT a state function-
Where are the PE and KE in this system?
System contains reactants and products of interest - everything else is surroundings
Glove filled with dry ice - inside glove is system
Energy (heat) and CO2 are both transferred out of system□
Energy is transferred and mass is transferred
Open-
Glove filled with dry ice and tied shut
Energy comes out (heat/cold), but mass is inside□
Energy is transferred, but mass is not
Closed-
No energy or mass transfer
Only isolated system is the universe
We won't deal with these
Isolated-
Multiple types of systems
Electrons repelling
-
Nuclei repelling
-
Electron-nucleus attractions
-
Intermolecular forces
-
PE is found in bonds, based primarily on charges
Flying across the room
Translation-
Rotating as it flies
Rotation-
It vibrates too (if you throw a slinky) - molecules are like springs
Vibration-
KE
Internal Energy (E) = sum of kinetic energy of all particles + sum of potential energy of all particles-
We can learn the change of energy in the system-
Energy
Heat something => q is positive, endothermic-
Heat out => q is negative, exothermic-
In this class, we will ALWAYS take the sign with respect to the system.
1 L.atm = 101.3J
1st Law of ThermodynamicsWednesday, August 26, 2009
14:58
Notes Page 4
http://pubs.acs.org
Doing work on system => +veWork being done by system => -ve
Science of measuring heat flow-
Calorimetry
Which are false?A: Enthalpy is the heat of a reaction at constant pressure.B: The heat flow measured at a bonfire is equal to the enthalpy change of the bonfire.
2H2 +O2=>2H2OdeltaH = deltaE
C: For the reaction:
D: The heat flow of an exothermic reaction measured in a sealed rigid wall container will be the enthalpy of the reaction.E: More than one of the above is false.
A is not false as it is the definition of entropy.B is not false because it is open to the atmosphere.C is false because the volume changes.D is false because it is not open to the atmosphere.
Therefore E is correct answer.
Intensive property - independent of the amount of substanceExtensive property - depends on the amount of substance
Enthalpy is an extensive property
Looks at T change as we heat and cool something
Heat capacity, c□
c= (heat absorbed)/(increase in T)□
Specific c is amount of heat necessary to raise the temperature of 1 gram by 1 degree celsius (J/(gC))
□
Molar heat capacity is for moles mol/(gC)□
One major concept
Calorimetry-
How to determine ΔH experimentally?
Table of Common specific heat capacities
Substance Specific Heat Capacity (J/g C) Molecules
Air (primarily N2) 1.012 Pretty simple
Water (liquid) 4.184 Pretty complex
Aluminum (solid) 0.89 Very simple
Iron (solid) 0.45 Very simple
Lecture 2: Enthalpy and CalorimetryMonday, August 31, 2009
14:58
Notes Page 6
How much heat does it take to raise the temperature of a 5.5 kg cast iron skillet from 25 C to 260 C. (c=0.45 J/gC)?
5500*0.45*(260-25)=581625 J~5.8*10^5 J, ~582 kJ
If I throw the 5.5 kg, 260 C skillet into 10 kg of 10 C water, what will the final temperature be?
5500*0.45*260=6435005500*0.45=247510000*4.184=41840.010000*4.184*-10=-418400.0643500-2475x=41840x-418400643500+418400=106190041840+2475=443151061900=44315x1061900/44315=23.9625Final temperature = 24°C (to 2sf)
Notes Page 7
Quiz: 5 questions, 6 marks eachFirst 2 - basic3rd - theory4-5 - more difficultNo Hesse's law
Gas - 1 atmSolid/Liquid - pure elementBoth at 25 C(Form at room temperature of elemental state)
Elemental forms = always have ΔHf0 = 0.
ΔHf0 of methane (CH4)
Energy is stored in the bonds of the moleculesChange in bond energy ~= ΔHrxn
Common Bond Dissociation Energies (BDE)
Bond BDE (kJ/mol)
C-H 413
C-C 347
C=C 614
O-H 467
C-O 358
H-H 435
Make and break all bonds, list them all1.Cancel out bonds on both sides2.Solve3.
3 Steps
Takes energy to break bonds
Hess's LawWednesday, September 09, 2009
15:02
Notes Page 14
C=C 614
O-H 467
C-O 358
H-H 435
Solve3.
Takes energy to break bonds
(614+467)-(413+347+358)=-37
(614+467)-(413+347+358+435)=-472
Notes Page 15
Entropy wins.
In any spontaneous process there is always an increase in the entropy of the universe. -
Spontaneous: no outside intervention□
Yes - diamond will turn into graphite (over millions of years)□
Spontaneous doesn't take into account time □
Is this spontaneous?
Diamond => graphite-
Solids - very low entropy
Liquids - higher entropy than solid
The gas is really what determines the entropy□
Gas - has a lot more entropy
The entropy of phases (ping pong demonstration)-
2nd law of thermodynamics
Chapter 16Wednesday, September 09, 2009
15:40
Notes Page 16
-2538/298=-8.5168
-976-8.5=-984.5
Question from Pre-lectureSunday, September 13, 2009
14:27
Notes Page 17
Exam: all multiple choice (first 2, third has free response)
ΔSuniv=ΔSsystem+ΔSsurroundings
If Δsuniverse is greater than 0 then spontaneous in direction written, if less than zero then non-spontaneousNon-spontaneous means "spontaneous in reverse direction"If ΔS=0 then equilibrium
If ΔS positive, forming C, if negative forming A and BA+B =>C
Δssystem Positional probability
An endothermic reaction at high temperatureA.An exothermic reaction at high temperatureB.An endothermic reaction at low temperatureC.An exothermic reaction at low temperatureD.
Which of these situations would lead to largest negative value for Δssurroundings?
Entropies: solid < liquid << gas-
Positional probability
Reaction ΔSsurroundings ΔH ΔSuniverse
Endothermic -ve +ve
Exothermic +ve -ve
Can't measure absolutely - only know change in it-
Gibb's Free Energy (ΔG)
Absolute minimum energy lost to entropy (heat/thermal motion)
Heat of reaction -energy stored in bonds -maximum energy we could get out - best case scenario
Maximum energy free to do work
ΔG0=ΔH0-TΔS0
Divide by -T
Δsuniverse ΔG
+ve -ve Spontaneous
-ve +ve Spontaneous in opposite direction
0 0 Equilibrium
All temperaturesA.Which of these will be spontaneous if ΔHrxn
0 is negative and ΔS0rxn is negative.
Gibb's Free Energy and 3rd Law of Thermodynamics ΔSMonday, September 14, 2009
14:56
Notes Page 18
All temperaturesA.No temperaturesB.Low temperaturesC.High tempearturesD.Not sure yetE.
ΔH0 ΔS0 ΔG0 Temperature of spontaneous Type of reaction
-ve +ve -ve All temperatures
+ve -ve +ve No temperatures
-ve -ve ??? Low temperatures
+ve +ve ??? High temperatures
4Ag(s)+O2(g) =>2Ag2O(s), ΔHrxn0=-62.0 kJ, and ΔSrxn
0=-133 J/K, what is ΔGrxn0?
-62000-298*-133=-22366
This a spontaneous reaction.
How to calculate ΔSrxn?
Notes Page 19
-33300+8.314*298*ln(0.01)=-44709.64070803889-44.7 kJ
Prelecture QuestionTuesday, September 15, 2009
18:57
Notes Page 20
Standard Heat of FormationEntropy (theory)EntropyHess's LawGibb's Free EnergyDetermining ΔH, ΔS, ΔG - not directly
Quiz info on compass
Last quiz average: 18-19 out of 30Typically averages are 65-70%Average is typically C+/B-
4Ag(s) + O2(g) <=> 2AG2O(s)
ΔH0rxn= -62.2 kJ, ΔS0
rxn=-0.133 kJ/K
We often assume that they are not temperature dependent - close, but this is not completely accurate
ΔG0=ΔH0-TΔS0
With this, we can detarnish silver - heat it up and then you get silver and oxygen gasT=300 C=> ΔG0=14.0 kJ
This is truei.At Teq all species are in equilibrium I.
This is truei.The Teq can be used for any phase changeII.
This is falsei.At Teq the forward reaction rate may be faster than the reverse reaction rate.III.
This is truei.At Teq ΔG0 is equal to zero.IV.
At Tequilibrium which are false?
True - by definitioni.ΔG=ΔG0+RTln(Q)I.
Falsei.ΔG>ΔG0 when no products are presentII.
Falsei.ΔG<ΔG0 when no reactants are presentIII.
Truei.
When a nonstandard reaction is at equilibrium, Δgnonstandard=0
IV.
Which are true?
R=8.314Allows to determine if spontaneous or not at any conditions
ΔG=ΔG0+RTln(Q)If we have ΔG0, T, and concentrations
ΔG0 is 3.0 kJΔG=ΔG0+RTln(Q)
K is simply Q at equilibriumΔG0=-RTln(K)K is equilibrium constant
At equilibrium: 0=ΔG=ΔG0+RTln(Q)G0+RTln(K)
What is K for this reaction:K=e^(-1.21)=0.3002.718281828 -̂3000/(8.314*298)=0.300=K
CH3OH(l) <=> CH3OH(g)
Tequilibrium, Δgnonstandard, and equilibriumWednesday, September 16, 2009
15:00
Notes Page 21
He will give us a review sheet and it will have exactly what is on the exam on it (giving on Wednesday)Conflict is at 5pm on same day22 questions, 1.5 hours (90/22= 4 minutes each) (quizzes are 5 questions, 35 minutes = 5 minutes each)
Exam:
Spontaneous or not1.Equilibrium (ΔG0=-RTln(K))2.ΔG=wmax - equal to maximum work to be done by a system3.
ΔG
Can only get 100% of work when dealing with a reversible system. In chemistry, a reversible system is a system in which through 1 cycle system and surroundings are unchanged. In real life there are no reversible systems.
ΔG and wmax, standard reduction potential, line notationMonday, September 21, 2009
14:56
Notes Page 23
Electricity-
Study of interchange between chemical and electrical energy-
Electrochemistry:
Loss of electrons = oxidation-
Gain of electrons = reduction-
(LEO says GER or OIL RIG)-
Things to remember
Thing that is oxidized is the reducing agent, the thing that is reduced is the oxidizing agent.
Fe2O3 + 2Al => Al2O3 + 2Fe
A lot of heat is produced - could we harness it as energy?
Oxygen has a -2 charge, so each Iron is +III. Aluminum is zero, as in elemental form. On other side Iron is zero, oxygen is -2 and AL is +III
Oxidation states
Fe3++3e-=>Fe0 - reductionAl0=> Al3++3e- - oxidation
Fe3++Al => Al3++FeInstead of the thermite reaction
Example
Salt bridge allows ions to flow
Always have reduction at the cathode and oxidation at anode. Electrons flow from anode to cathode. (Anode Oxidation - vowels, Cathode Reduction - consonants)For a galvanic cell to work must have wires, anode, cathode, salt bridge.
Galvanic Cells
By convention, the anode is drawn to the left and the cathode to the right. (He will use this all the time, but not all homework will). Galvanic cells are the same thing as voltaic cells.
Fe3++3e => Fe SRP = -0.036V cathode
Al3++3e => Al SRP = -1.66V (difficult to reduce) anode
Question:
The Fe reaction will be at the cathode because you want to reduce the voltage and it has the Which will be at the cathode and why?
ElectrochemistryMonday, September 21, 2009
15:12
Notes Page 24
largest SRP. The higher a SRP the easier it is to reduce it.
Fe3++3e => Fe SRP = -0.036V
Al => Al3+ + 3e SRP = 1.66V
Fe3++Al=>Al3++Fe 1.62V - the potential of this cell
Describes the pull towards the cathode-
Can also be called the cell potential -
1.62V can be referred to a the electromotive force or emf
Standard reduction potential is an intensive property.
EMF = cathode-anode
Balanced chemical equation, EMF and line notation for this cell
Notes Page 25
Fe3+(0.2M) + e- => Cu2+(0.3M) SRP = 0.77 V
Cr2+(0.7M) => Cr3+(0.9M)+e- SRP = 0.5 V
Fe3+(0.2M)+Cr2+(0.7M)=>Cu2+(0.3M)+Cr3+(0.9M) SRP = 1.27 V
Line Notation:Pt | Cr3+(0.9M), Cr2+(0.7M) || Fe3+(0.2M), Cu2+(0.3M) | Pt
Line Notation PrelectureTuesday, September 22, 2009
09:29
Notes Page 26
Review sheet is on compass - it is EXACTLY what is on the examNO free response questions - 22 MCQ questions - 7 points each, worth 150 total.9-7-6: easy-medium-hard~6 theory questions with NO numbersFirst 7.5 lectures (no electrochemistry)Equation sheet online too
Exam 1 next week - email him to take it in morning.
Au3+(1.0M)+3e-=>Au SRP = 1.50 V (cathode)
Cu2+(0.5M)+e-=>Cu1+(0.1M) SRP= 0.16 V (anode)
Pt|Cu+(0.1M), Cu2+(0.5M)||Au3+(1.0M)|AuV=1.34VAu3+
(aq)+3Cu1+(aq)=>3Cu2+
(aq)+AuElectrodes on ends| = phase change|| = salt bridge
Cell based on:
We try to harness this energy in JoulesEMF=-(work (J))/(charge (C))
EMF is the same as cell potential - it is the pull of electrons towards the cathode
F=faraday's constant = charge on 1 mol of electrons
ΔG EMF
Spontaneous reactions -ve +ve
Non-Spontaneous +ve -ve
Spontaneous electrochemical reactions always have a positive cell potential
ΔG=ΔG0+RTln(Q)-nFε=-nFε0+RTln(Q)
εnonstandard=ε0-RTln(Q)/nF
1.34-8.314*298*ln(125)/(96485*3)=1.2986723500276191.30 V to 3sf = potential at nonstandard conditions
1 V = 1 JC-1
Nernst Equation
Example:
Line Notation, Nernst Equation, Concentration CellsWednesday, September 23, 2009
15:01
Notes Page 27
Example:
Galvanic cells work by going towards equilibrium
-8.314*310*ln(.001/.1)/(1*96485)=0.123014865804576V=0.123 V = 123 mV
Ln(.001/.1)=-4.605170185988091
This is a concentration cell - only thing that matters is concentration.
Notes Page 28
Can use whatever calculator you wantNo LON-CAPA his weekNo quiz this week
Can be done anytime before the end of the term-
IVL's
Pb2++2e-=>Pb SRP=-0.13 (anode)
Cu2++e-=>Cu+ SRP=0.16 (cathode)
What will the EMF be when Cu2+ has changed by 0.5 MEMF0=0.29
2Cu2+ + Pb => Pb2+ + 2Cu+
1 solid 1 1
-0.5 solid 0.25 0.5
0.5 solid 1.25 1.5
Q= 1.25*1.5^2/0.5^2=11.25Emf=emf0-RTln(Q)/nF0.29-8.314*298*ln(11.25)/(2*96485)=0.2589245151824810.26V
Increase the concentration of Cu+ - noI.Increase the mass of the Pb electrode in the cell - noII.Increase the concentration of Cu2+ - yesIII.Add one liter of water to both half reactions - yesIV.Decrease the concentration of Pb2+ - yesV.
How many of the following will increase the EMF of this cell?
Galvanic cells took chemical energy and changed it to electrical energy-
Electrolytic cells use electrical energy to create chemical change. -
Reduction at the cathode
Oxidation at the anode
Electrons flow anode to cathode
Things that stay the same-
Not spontaneous anymore
Lowest SRP is the cathode (opposite)
Highest SRP is the anode (opposite)
Things that change-
Electrolytic Cells
O2+4H++4e-=>2H2O SRP = 1.23 V - anode oxidation
4H2O+4e-=>2H2+4OH- SRP = 0.83 V - cathode reduction
4H2O+4e-=>2H2+4OH- SRP = -0.83 V2H2O=>O2+4H++4e- SRP = -1.23 V6H2O=>O2+2H2+4H++OH-
4H++OH-=4H2O
We have to add at least 2.06 V to make this work2H2O=>O2+2H2 SRP = -2.06 V
Review, Electrolytic cells, electroplating, intro to kineticsMonday, September 28, 2009
14:57
Notes Page 29
Electroplating
There is no salt bridge(to do it well you need Cyanide gas -not done in lecture halls)
Takes more volts to plate something than we would predict - solutions aren't really conductive sometimes
-
Over voltage
Gives a lot of energy, but a bit explosive and difficult to harness-
How much H2 gas formed at STP when we have voltage >2.06 V at 10 Amps for 1 hour?-
2H2O=>O2+2H2-
1 h = 60 min = 3600s-
Therefore 3600*10 C = 36000 C-
96485 C/mol - 4 mol of electrons per 2 mol hydrogen-
60*60*10*2/(96485*4)=0.1866-
1 mol Hydrogen = 22.4 L-
So 4.18L of hydrogen in 1 hour-
Combusting Hydrogen
Notes Page 30
Past exams feel easierReally CANNOT remove pages - cheating issues
FRQ is difficult to grade fairly, so droppedThere will only be FRQ on the 3rd exam. (and only kind of)
Conflict exams may be in discussion sectionsGrades will be in online gradebook soonWill be an exam corrections assignment
High score = 22; Median = 12; Mean = 12.33
Grade # correct
A+ 19
A 18
A- 17
B+ 15
B 14
B- 13
C+ 12
C 10
C- 8
D+ 7
D 7
D- 6
F <6
Curves
Exam StuffWednesday, September 30, 2009
15:01
Notes Page 31
Done with Electrochemistry
C6H12O2+6O2 => 6CO2+6H2O ΔG0=-2877 kJ Spontaneous
rxn
E
Thermodynamics doesn't tell us about blue area
Helps to understand the rate of a reaction1.Allows us to understand the detailed steps of how a reaction takes place2.
Why kinetics?
Model with Boltzmann 3D - can downloadCollisions of molecules
Reactions: what are they based on?
Energy matters-
Orientation matters (dependent on reaction) -
For collisions
The activation energy is the minimum energy needed for a reaction to take place.
The lower activation energy, the faster reaction
Change the activation energy-
Higher concentration then faster reaction
More collisions, so more will have a higher energy
Increase the concentration-
Increase the temperature-
How can we make a reaction occur more quickly?
Blue has a higher activation energy
Arrhenius Equation
Kinetics Intro, Collision Theory and Arrhenius, Rate Law (Chapter 12)Wednesday, September 30, 2009
15:10
Notes Page 32
Ea is activation energy,
Higher if more likely to happenTakes into account reaction conditionsMust be experimentally determined for each reaction
A is the Arrhenius constant
A linear equation - can graph
k is the rate constant (always lower case)-
Deals with T and EA, but not concentration-
What is k?
Describes what the rate of a reaction will be-
Rate Law
Notes Page 33
Electrochemistry-
Quiz Thursday
LON-CAPA on Friday
He will post slides before lectures
Rate = -Δ[A]/Δt (rates are always +ve)-
Rate = -Δ[B]/Δt-
Rate = Δ[C]/Δt (no need for negative sign, as it is already positive)-
A + B => C
Because C has coefficient 2, multiply by 1 over 2.□
Rate = -Δ[A]/Δt=-Δ[B]/Δt = Δ[C]/(2Δt)-
A+B => 2C
Rate
B 2.0E-3
C ?
Rate of C= 2*rate of B = 4.0E-3What about -ve signs? - they go away as a negative rate is never possible
A+B=>2C
Rate = change/time=Δ[]/Δt
t (min) [A] (M) [B] (M) [C] (M) Ins. rate Rate/[react]
0 100 100 0 33.0 0.33
1 72 72 28 23.8 0.33
2 52 52 48 17.2 0.33
3 37 37 63 12.2 0.33
4 27 27 73 8.9 0.33
5 19 19 81 6.3 0.33
-
Avg. rate = D[C]/Dt = 16.2 M/min-
Avg. rate = D[A]/Dt = 16.2 M/min-
1st min. 28.0 M/min-
5th min. 8.0 M/min-
Average rate doesn't give best one-
Usually only care about the one at t=0.□
Why? Because then we don't have to worry about the reverse reaction□
Take tangent line - it is the rate-
Data-
Rate is proprotional to concentration of reactants-
Ratio fo rate/[react] is essentially constant-
2 big things:-
k is the rate constant (note: lower case k)□
k takes into account temperature/pressure□
Rate = k[A]a[B]b-
Summarize with rate law:-
Rate
Exp Initial Rate (M/s) [A] [B]
1 5.5E-6 0.1 0.1
2 2.2E-5 0.2 0.1
3 1.65E-5 0.1 0.3
DO NOT TRUST COEFFICIENTS -THEY ARE NOT THE RATE LAW.
Reaction rate, determining the rate law, reaction orderMonday, October 05, 2009
14:58
Notes Page 34
2 2.2E-5 0.2 0.1
3 1.65E-5 0.1 0.3
Rate = k[A]2[B]1
Rate/([A]2[B]) = kk = 5.5*10^-6/(0.1^2*0.1)=0.0055s-1M-2
(Use whichever experimental data you like - same rate constant)Units for rate constant depend on the reaction - be careful (dimensional analysis is best here)
Determine k here:
Tell us the order of the reaction-
2nd order with respect to A
1st order with respect to B
Sum of the other orders□
3rd order overall
Rate = k[A]2[B]-
2nd order => 2*[] means 4*rate
1st order => 2*[] means 2*rate
Why does order matter?-
Orders can be any integer, decimal, negative number (any real number) (most commonly 1 or 2)
0 order means the concentration of the reactant doesn't affect the reaction
What about 0 order?-
2nd order is two things colliding together
First order still has collision, but just excites one molecule and it does a reaction on its own (energy can also be dissipated)
Order tells us how many molecules are colliding-
Must have proper speed and orientation of molecules-
The exponents
Notes Page 35
Galvanic cellElectroplatingTheory of galvanic cellConcentration cellNernst equation and ICE tables
Quiz:
LON-CAPA due Friday
Differential rate law:
Allows us to determine how the rate of reaction depends on concentrationOrder of the reaction tells us what is collidingA => products
Zero order 1st order 2nd order
Rate=k Rate=k[A] Rate=k[A]2
How do we determine which one? - ExperimentsDifferential rate laws tell us nothing about time
Rate= k[A]a
Integrate wrt time
0 order 1st order 2nd order
[A]t=-kt+[A]0 ln[A]t=-kt+ln[A]0 1/[A]t=kt+1/[A]0
All in form y=mx+b (2nd order is +ve k times t, others are -ve k times t)Plot to determine what order it isUse axes to determine units
Determine order and k. 1.Apply data with correct integrated rate law2.
Rules
Integrated rate laws
ln[A]t=-kt+ln[A]0, (first order, k=0.0031min-1)(ln(0.05)-ln(0.4))/(-0.0031)=670.7875940902694671 minutes
How long will it take to go from 0.4M to 0.05M penicillin, using our earlier test1.
Ln[A] = -0.0031*8*60+ln(2.0)=-0.794852819440055[penicillin]= 2.718281828^-0.79485=0.4516489770.45M
What will [penicillin] be after 8 hours if [penicillin]0=2.0M2.
Problems:
Half life-
0 1st 2nd
T1/2 [A]0/(2k) Ln(2)/k 1/(k[A]0)-
First order is always constant-
Another thing
A+B+C => D+E-
Rate = k[A][B][C]-
This is a 3rd order reaction
Pseudo-order reactions
Integrated rate laws, half life, pseudo-order reactionsWednesday, October 07, 2009
15:01
Notes Page 36
This is a 3rd order reaction-
A B C D E
I 0.002 2 2 0 0
C -.001 -.001 -.001 .001 .001
E .001 1.999 1.999 .001 .001
-
Concentration of A big, but for B and C essentially constant-
Rate = k[A][B][C], but [B] and [C] ess. Constant-
Therefore redescribe it as k'=k[B][C]-
Now a first order reaction - pseudo first order k= slope/([B][C])
Thus rate = k'[A]-
Notes Page 37
Study guide next Monday/TuesdayExam II next Thursday at 19:00
2 LON-CAPAs due this week
KineticsQuiz this Thursday
Silkworm silk dissolve in methanol, pass through water is almost the same as spider silk - email for more
Spider silk
Rate = k[A][B][C]
A B C D E
I 0.001 2.0 3.0 0 0
C Small Small
E
Plot ln[A] vs t{s} gives straight line with slope = -2.5E-5. What is k?
This is third order, but can be approximated to first order
k'=2.5E-5=k[B][C] k'is a pseudo-constant
4.167E-4 is k□
Therefore, k = (2.5/6)*10^-5=0.4167
A+B+C=>D+E-
Pseudo Order Reactions
Spontaneous, but not quickly
But not much I- around, where do we get it from?□
Reaction mechanisms□
Rate=k[H2O2][I-]
2H2O2=>2H2O + O2, ΔG0=-212.6 kJ-
Definition: detailed description of how the reaction takes place (which molecules collide); typically broken down into elementary steps
-
Rate = k[H2O2][OI-]
Step 1: H2O2 + I- => H2O +OI--
Rate = k[H2O2][OI-]
Step 2: H2O2 + OI- => H2O2+I--
Overall rate law (exp) = k[H2O2][I-]-
This mechanism is not valid because the sum of the elementary steps is equal to the overall balanced equation
False
The rate law for step 1 would be rate =k[H2O2][I-] True
I- is an intermediate in this process False
Step 2 is a unimolecular process False
True or false:-
Reaction Mechanisms
Pseudo order reactions, Mechanisms, elementary steps, rate determining stepMonday, October 12, 2009
14:57
Notes Page 38
We can write the rate law of step 2 from the coefficients because an elementary step describes molecularity
True
(1) Sum of the elementary steps must equal the overall balanced reaction.
(2) Mechanism must agree with experimentally determined rate law
To determine if a reaction mechanism is valid - 2 rules (can never absolutely say it is correct, say this is plausible but cannot prove)
-
Slow step is called the rate determining step
The overall rate of a reaction is based only on the rate of the slow step-
Initially only look at the slow step
When doing kinetics-
H2(g)+I2(g)=2HI(g)
Rate law = k[H2][I2]
Sunny day rate is faster, dark day rate is slower
Step 1: I2 <=> I* (I* is I-radical - unstable state of I)□
Step 2: H2+2I* => 2HI (slow)□
Sum: H2(g)+I2(g)=2HI(g)□
Does not match experimentally determine rate law
keq =[I*]2/[I2]
I* is an intermediate, and we don't want intermediates in the reaction
[I2]=keq[I*]2
Therefore, rate = k[H2][I2]keq - make a new k, kobs=keqk
Rate = kobs[H2][I2]
So actually it does match - is a valid mechanism
Rate law = k[H2][I*]2□
Proposed mechanism:
Example-
Notes Page 39
Isolation methodDetermining rate of reaction from a rate lawDetermine the order of a reaction from integrated rate law dataTheory questions about pseudo-order reactionsHalf lifeDetermining which mechanisms are valid given experimental dataALL EQUATIONS will be given with orders
Quiz:
Fumigate strawberry fields in California - to kill bugsThis (on side) is Thymine - R is the rest of the structureDrawing is messy, so use line angle notation instead
Methyl Iodide, CH3I
Line Angle Notation
At the end of each line, and at each angle assume a Carbon is present1.Omit all hydrogens attached to carbon2.
Rules:
2 Mechanisms for CH3I
Rate = k[CH3I]
Step 1: CH3I => CH3+ + I--
Rate=k[CH3+][DNA] => even simplifying not second order - has an extra factor of [I-]
Step 2: DNA + CH3+ => DNA-CH3
First
Rate = k[DNA][CH3I] - second order, therefore more correct
Step 1: DNA + CH3I => DNA-CH3 + I--
Second
1st order with respect to CH3I
Second order wrt DNA - if they are equal then it can be their product, like in the second mechanism
[DNA]=[CH3I], plot of 1/[DNA] vs. time gives straight line
Data:
Which of these are valid?
Mech 1
Kinetics overview, drawing organic structures, hybridization Wednesday, October 14, 2009
14:59
Notes Page 40
Which of these are valid?
Mech 1 Mech 2Mechanism 1 has 2 stepsThe highest point on the graph is the rate determining stepMechanism 2 has 1 step
Mech 1 Mech 1
Hybridization
Notes Page 41
It is national chemistry week.Exam II is 19:00 on Thursday (conflict is at 17:30)No LON-CAPA this weekRooms are online, as is review sheet, as is equation sheet - will have a table with SRP'sMaterial from last week and before - not today
Correct=7 pointsFor partial credit (some questions only): 2 pointsAsterix indicates partial credit
All are MCQ's
22 questions
Characteristic group of atoms that react similarly -
Functional Groups:
Look for things other than Carbon1.Look for non-single bonds2.
How to do things:
Be able to go through and tell where the different functional groups are.
IUPAC conventions for naming-
Computer programs name the really complicated ones - no reason for us to
Nomenclature:
Functional Groups, Nomenclature of AlkanesMonday, October 19, 200914:59
Notes Page 42
IUPAC conventions for namingComputer programs name the really complicated ones - no reason for us to-
Trunk = main chain
Branches = substituents
Like a tree:-
Have to practice naming-
Always take the longest carbon chain
Form base name for molecule
Number the carbon chain - start numbering closest to first substituent
2-methyl□
Name substituents
2-methylpentane □
Write it out:
Rules:-
2,4-dimethylhexane
4-chloro-3-ethyl-2-methylhexane
Pick the path giving the greatest number of constituentsPut them in alphabetical order
Notes Page 43
Hydrocarbons
O containing
Carbonyl containing(has a C=O bond)
Aunt ester (Esther) gives you coco (cocoa).
Functional GroupsMonday, October 19, 200915:12
Notes Page 44
Memorize these numbering schemes
Looks like a fish tailLooks like a long fish tailLooks like a chicken foot
We'll need these too.
Naming HandoutMonday, October 19, 200915:13
Notes Page 46
Carbon hybridization is sp3 each-
C-C single bonds - sigma bonds-
Butane
Alkanes are typically unreactive
Alkanes can rotate easily - sp3 bonds are symmetrical in a conal type wayAlkanes are non-polar as they are both symmetrical and have the same electronegativity
Combusts to CO2+H2O - very complex
Combustion:-
Hexane is colorless, Bromine is orangish□
Very slow reaction - going to stay orange for a while□
Reaction goes through a radical mechanism - difficult to balance□
CH4+Br2 =>(heat)CH3Br+CH2Br2+CHBr3+CBr4
Halogenation - relatively complex - important (watch video he will post) - substitution-
Reactions with Alkanes
Can bring models to exams/quizzes-
Electrons want to be spread out from one another-
Newman projections:-
Molecule shapes
'look' at it so you can only see the front carbon
Molecules in front go all the way to centre, molecules in back only to the edge
Rotate C2 by 60 deg. Clockwise, then again
Staggered
Alkane properties, Alkane reactions, Alkane conformational analysisWednesday, October 21, 2009
15:00
Notes Page 49
again
A: it is the most stable-
This is true because the CH3's are as far away as they can be-
B is the highest energy as it is 'on top' of each other (of these 3)-
EA<EC<EB-
If we rotated it another 60 degrees it would be the total highest energy-
Which of these structures has the lowest energy (A, B or C)?
Staggered
Eclipsed
Staggered
Notes Page 50
Exam results will be up tonight or tomorrow morning
Tamiflu
Cyclohexane
Not planar - chair shaped is more stable
Point towards outside-
Equatorial positions
Point straight up or down-
Alternate between up and down-
Axial positions
Axial substituents become equatorial, and equatorial substituents become axial
-
Takes energy to happen-
Ring flip
T-butyl group is in an axial position
T-butyl group is equatorial position
T-butyl groups are equatorial in cyclohexal rings
The sameDifferentCan't tell
Are 1 and 2
Organic Structures/ShapesMonday, October 26, 2009
14:54
Notes Page 51
Can't tell
3D shape mattersThey are different
Different compounds with the same molecular formula are called isomers.
Constitutional isomers is like taking Mr. Potato head and putting him together in different waysStereoisomers are like taking Mr. Potato Head and rotating his arms and legs around.
Look for stereocenters Stereocenter= a carbon with 4 different groups (must be different, can't have 2 the same)Most enantiomers have stereocenters, but a stereocenter doesn't necessarily mean it is an enantiomer.
Enantiomers: non-superimposable mirror images (like your hands)
Cis: on the same side-
Trans: on the opposite side (ie Transatlantic) -
Diastereomers
The two chains are different as one runs into the Br after 2 and the other 4
Circled in red-
No line of symmetry indicates this-
If there is a line of symmetry it indicates a lack of stereocenter
Stereocenters
Notes Page 52
No line of symmetry indicates thisIf there is a line of symmetry it indicates a lack of stereocenter-
CisTrans
Can you have it?1.Which is it?2.
When thinking about cis/trans:
Notes Page 53
No raw score for this exam
Geometric - cis/trans
Isomers-
Naming-
Functional groups-
Conformation-
Hybridization-
Basic arrow pushing-
So far…
Much faster than alkane halogenation-
Alkene halogenation
It's the double bond that makes the difference
True
The pi electrons are higher energy and more reactive
True (see picture)
The alkene doesn't have free rotation, so can't react
False (it does not have free rotation, but that is unrelated to reaction)
The double bond is a better nucleophile
True (there are now 4e- in the space that used to have 2e-, so they attract more nuclei)
N/A
True or false
All single bonds-
Add 2 Br instead of 1-
Gives trans product-
No need to add light to alkenes
-
Rate=k[alkene][Br2] (2nd order)
-
Compare products:
Proposed mechanism:
What we know so far, Alkene halogenation, Alkene hydrohalogenationWednesday, October 28, 2009
14:56
Notes Page 54
Double bonds-
Lone pairs-
Partial negative charges-
High e- density = nucleophile
Partial positive charges-
Low e- density = electrophile
Nucleophiles attack electrophiles Halogens will always have a partial positive on one side and partial negative on the other.
Notes Page 55
Quiz on Thursday, LON-CAPA HMWK due FridayOn compass there is an organic text in HTML - better than a bookLectures 17 and 19 are up now.
Mechanism of hydrohalogenation
Major Intermediate
Minor intermediate
True/false
Markovnikov's rule tells us that H adds to the side with more H
True
The more stable carbocation intermediate will be formed
True - this is the reason for Markovnikov's rule
A primary carbocation is the most stable carbocation
False (tertiary more stable than secondary more stable than primary)
Follow these rules in order to make the major and minor intermediates and thus products
Contemplate this mechanism:
Alkene hydrohalogenation, Markovnikov's rule, Alkene hydrationMonday, November 02, 2009
14:56
Notes Page 57
Arrows are like sticky frog handsThe arrows are the mechanism
New reactions:
Need to have an acid catalyst
-
Alkenes reacting with water:
Follows Markovnikov's rule
SAME AS IN PREVIOUS REACTIONRate=k[alkene][H+]
Notes Page 58
Add water - no, goes in reverse-
Add acid - no doesn't change anything-
Remove alkene (decrease concentration) - causes formation of alkene (removes products)-
Heat the reaction to above the boiling point of water - causes formation of alkene (removes products)
-
Which of these will favor the formation of alkene?
More substitution gives a more stable double bond
Alkene hydration, alcohol dehydration, alcohol reactionsWednesday, November 04, 2009
15:15
Notes Page 60
No MCQExam next Thursday
AlcoholsAldehydesKetonesAlkanesAlkenes
Naming
Last weekToday
Reactions
Radical halogenation alkane (needs light/heat)Halogenation alkene (gives a trans relationship)Hydrohalogenation of alkeneDehydration alcohol (needs an acid catalyst - dry)Hydration of alkene (needs acid catalyst)
Mechanism
Alcohols oxidize to carbonyl
Alcohol Oxidation, Carbonyl reduction, ether formationMonday, November 09, 2009
14:59
Notes Page 63
Will take a carboxylic acid, ketone, or an aldehyde and transform it to an alcohol
Will take a ketone or aldehyde and transform it to an alcohol, but no reaction with carboxylic acid.
Will take a ketone or aldehyde and transform it to an alcohol, but no reaction with carboxylic acid. Takes an alkene and changes it to an alkane.
The carbonyl oxygen ends up being the alcohol oxygen.
Notes Page 64
LON CAPA on Friday - kind of long
Naming alcohols aldehydes and ketonesIdentifying functional groupsPredict the products (fill in reagents) for alcohol oxidation, alkene hydrohalogenation, carbonyl reduction, alkane halogenation, and alkene hydrationAlcohol dehydration mechanismFill in blank like in class
Quiz tomorrow:
GEO strike - may or may not happen, but probably will not occur here or matter to us
Easy to make from alcohols1.Can easily get to complex structures in products2.Can produce stereocenters3.
Based on Ketones and aldehydes - important for 3 reasons-
Nucleophilic Addition to a carbonyl
Ketone: R != H, it is a carbon chainAldehyde: R == HSAME REACTIVITY
The carbon is not a strong enough electrophile for the reaction to take place immediately. Must add an acid catalyst
The protination of carbonyl makes the carbon in the carbonyl a better electrophile.
Where do we see this?
Nucleophilic Addition to a Carbonyl, General Mechanism, ApplicationsWednesday, November 11, 2009
15:00
Notes Page 66
Partial creditFill in the box/line - they won't look elsewhereGrading will be done by Friday, posted on Monday/TuesdayNo MCQ's3 naming questions (alkane, alkene, ketone)Newman projectionsChair conformationWednesday: lecture optional, review material; Thursday discussion also
Exam: 22 questions, 7 marks each
Substitutes a new nucleophile forming water
Nucleophilic Substitution (on exam), Polymers (not on exam)Monday, November 16, 2009
14:56
Notes Page 69
Easily reversible if have water involved-
Reversible reactions
Tert-butyl is always equatorialGroups are always equatorial if given a chance
No need for diastereomers/enantiomers
ReviewWednesday, November 18, 2009
15:02
Notes Page 72
Because a tertiary carbocation is the most stable (the other attached groups 'donate' electrons and make it less)
Review SheetThursday, November 19, 2009
13:02
Notes Page 73
No class next WednesdayFinal will be comprehensive
Everything in the brackets is repeated n times (here n is very large - millions/billions)
Polyethylene-
Polymers:
The molecule is very large and the OH group is not drawn here, since it doesn't really matter
Take the monomer name and put 'poly' in front of itNaming polymers:
Polymers and Amino Acids and Acid/BaseMonday, November 30, 2009
14:54
Notes Page 74
More cross links means more brittle polymer
Nylon is amine and carboxylic acid polymerized (a specific amide)
This is condensation - getting rid of water in the processThis is a polyamide
Like natural polymers-
Peptides
Acids lose Hydrogens easily
Isoelectric - balanced positive and negative charges so it is neutralIn the one with a neutral pH, has both a negative and positive charge - a zwitterionic molecule
Notes Page 75
Isoelectric - balanced positive and negative charges so it is neutralIn the one with a neutral pH, has both a negative and positive charge - a zwitterionic molecule
Notes Page 76
55 MCQ3 hours available, should take approximately 2Conflict available only for valid reasons
Exam
Amine acts as base, carboxylic acid acts as acid
pKa(acid)=2.34, Ka=4.57E-3pKa(amine)=9.69
What is pH of a 0.1M solution of this:
If pH is less than pKa => protonatedIf pH is greater than pKa => deprotonated Proton will be removed from acid first
Henderson-Hasselbalch equationWeak acid and conjugate base is a buffer
Point where charge is 0: isoelectric point
Be able to identify halfway points, equivalence points, and starting points and plot them-
On titration curves:
pH milk = 6.3, pH casein = 4.7 - this is why milk curdles on addition of acidAt isoelectric points, has both positive and negative charge in molecule
Acid/base and amino acidsWednesday, December 02, 2009
15:02
Notes Page 77
Final exam: 13:30 on 18 NovemberAll LON-CAPA is in gradebookGo through gradebook before 15-12 and email him if anything is incorrectReview sheet and room assignments and equation sheet are up for the final55 questions - each will be slightly easier than on hour examsSome conceptual questions, 5-10 or soQuite a few will require calculator math (Nernst, K, k, q…)No partial credit - correct or incorrectNo 'how many of the above' are true (he thinks)T/F questions are therei-clicker points will be in soon
Acid-base properties
Class of proteins will be onlineAmides, Peptides, Amino acids
First we have the peptide strand itself (primary structure)-
Alpha helix and beta sheets are the most common secondary structure motifs
Then a secondary structure (chain), based on IMF's and how peptides are organized in space-
Based on solubility - if parts are hydrophobic they will come together
Tertiary structure takes the secondary structures and brings them into a larger 3D structure-
Done partially by solubility, and partially with metal ions (in body sometimes iron) - metal binding important here
Quaternary structures take multiple tertiary structures and link them together-
If this happened in this way exactly our body would collapse, doesn't happen without help
We add a nucleophile to the body - add chymotrypsin (or something else) - an enzyme
Only some are protonated - depends on pKa, lower pKa more base□
Asparatate makes histatine more basic, so it deprotonates serine□
Have catalytic triads: asparatate, histidine, serine
Then uses water to regenerate the enzyme and free it from the bonding pocket□
Be able to pick what will be in the active site (it will be the hydrophobic one) (in the binding pocket formed by the alpha helixes and beta sheets)
See hydrolysis of amide online, carbon forms a tetrahedral intermediate, then water comes onto carbonyl and pushes off the amine
-
Have alpha helixes and beta sheets to form pockets
Most things based on solubility and IMF's
Important things-
How do we get different types?
Final bit of stuff and explosionsMonday, December 07, 2009
14:58
Notes Page 79
Brandon Lange-
Office: 340 Roger Adams Lab-
Wednesdays
2 to 5 pm
Chem Learning Center
212 Chem Annex
Office Hours-
TA:
Discussion Section 1Tuesday, August 25, 2009
12:59
Discussion Sections Page 80
Equations:Energy is conserved - neither created nor destroyed
Discussion Section 2Wednesday, August 26, 2009
21:04
Discussion Sections Page 81
What is the problem asking?1.List all information.2.Determine if an equation can solve the problem.3.Solve.4.Does it make sense?5.
Process for Problem Solving
45J of heat are added to a gas, and 10J of expansion work is performed.1.60J of heat are removed, and the gas is compressed to its original state. 2.
Process over 2 steps.
What is the work in step 2?
Problem from Book:
Discussion Sections Page 82
2-3pm Monday4-5pm Wednesday340 Roger Adams Lab
Office hours:
ΔH, heat of a reaction at constant pressureΔH=q
Enthalpy is extensive -depends on mass
Heat capacity, color, density, temperature
Intensive
Enthalpy,Extensive
c, the heat needed to raise something by 1°Specific heat capacity: units J/(g°C)Molar heat capacity: units J/(mol°C)
Measure heat flow, q=mcΔTm is mass or moles
Plastic will be wet, stoneware dryStoneware dries because it is much more massive than the plastic containerIf they were the same mass, then the plastic would dry faster
They transfer heat more quickly. Plastic has more heat in it, stoneware has less
Discussion Section 3Monday, August 31, 2009
19:07
Discussion Sections Page 83
The one with the greater heat capacity. - use q=mcΔT, therefore ΔT=q/(mc), m1=m2, q1=q2, therefore ΔT=1/c
Discussion Sections Page 84
If something gaining heat, then something else loses heatΔH=q=mcΔT (where q is at ct pressure)
When you go from reactant to product, it doesn't matter if we take one step or many - the same answerExtensiveIf you double one, double the other; reverse one, reverse the other
Can find ΔH using experimental data
Heating Curve (water)
T
Heat added
How much heat is required to raise the temperature of water from -5 C to 60 C?
ΔH=mcΔT=q-
Ct. Pressure
ΔE=mcΔT=q=ΔH-
Ct. Volume
ΔH and ΔE are close to one another in reactions with the same amount of moles of gas on each side. (Le Chatelier's Principle)
Bomb if we want to find ΔE.-
Why one over other?Do high heat, or gas reactions in a bomb over coffee cup.
Discussion Section 4Thursday, September 03, 200911:54
Discussion Sections Page 85
35 minutes for quizProb. 4-5 questionsProb. Formula sheet
Quiz Thursday.
LON-CAPA Friday, 5 pm
Discussion Sections Page 86
P4O10 => P4 + 5O2 2967.3
10PCl3+5O2=>10Cl3PO -2857
P4O10 + 10PCl3 => P4 + 10Cl3PO 110.3
P4 + 6Cl2 => 4PCl3 -1225.6
P4O10 + 6PCl3 + 6Cl2 =>10Cl3PO -1115.3
6PCl5 => 6PCl3 + 6Cl2 505.2
P4O10+6PCl5=>10Cl3PO -610.1
-610.1
Discussion Sections Page 87
Measure of disorder (chaos) - naturally want to be disorderedΔSuniverse=ΔSsystem+ΔSsurroundings - positive for spontaneous reaction 1 atm, 25 Celsius-
ΔG0 - Standard Gibb's Free Energy
Entropy of a perfect crystal at 0K is 0
Discussion Section 6Monday, September 14, 200921:03
Discussion Sections Page 90
ΔG0=0 at equilibriumΔG=ΔG0+RTln(Q)ΔG0=-RTln(Q)
Temperature at which there is no change
ΔG at a nonstandard T and P
Discussion Section 7Wednesday, September 16, 200920:47
Discussion Sections Page 93
Exam: 22-23 questions
ΔG is the maximum amount of work we can get from a system (but we really won't even get this much)
Oxidation occurs here
Anode-
Reduction occurs here
Cathode-
Allows ions to flow
Salt bridge-
Connects the anode and cathode
Wire-
Components of Galvanic cell
LEO says GER or OIL RIG
The standard "pull" of electrons vs a standard hydrogen electrode
See above
Shorthand way to represent a cell. Anode solid | Anode solution || Cathode solution | Cathode solid Cr3+
(aq)+Cl2(g) => Cr2O72-
(aq)-+Cl-(aq)
7H2O+2Cr3+(aq)+3Cl2(g)=>Cr2O7
2-(aq)+6Cl-
(aq)+14H+
ΔG=ΔH-TΔS, ΔH=-34000 J/mol;
See above
Platinum - it's inert (also graphite (Carbon))
Potato = salt bridge; copper wire = electrode; nails = electrode; wire = wire
ΔG0=-RTln(K)=-8.314*298*ln(1.96*10^18)= -104354 J/molΔS=(ΔG-ΔH)/(-T)=(-104354-(-34000*2))/-298=122 J/K
ΔS>0 as more mol gas in product
Discussion Section 8Tuesday, September 22, 200909:18
Discussion Sections Page 95
Cells based solely on concentrations
Double Lead: decreaseDouble Copper: increaseHalve each: decrease
2Cr2+ + Co2+ => 2Cr3+ + Co
0.3 0.2 2.0
-0.1 -0.05 +0.1
0.2 0.15 2.1
Ag+ Ag => Ag Ag+
I 2.5 0.02
C -x +x
E 2.5-x 0.02+x
Cu2++e-=>Cu+ 0.16 V Cathode
Pb=>Pb2++2e- 0.13 V Anode
2Cu2+(1.0M)Pb=>2Cu+(1.0M)+Pb2+(1.0M) 0.29 V
2Cu2+ => 2Cu+ Pb2+
I 1.0 1.0 1.0
C -0.5 +0.5 +0.25
E 0.5 1.5 1.25
n=2Emf0=0.29
Discussion section 9Thursday, September 24, 2009
10:24
Discussion Sections Page 97
Determine the final temperature of a solution when 150g of ice at 0 C is mixed with 300g of water at 50 c.Cice=2.087 J/gCCwater=4.184 J/gCCsteam=1.996 J/gCΔHfusion=6.02 kJ/molΔHvaporization = 40.7 kJ/mol
ΔE = q + w-
w=-pextΔV-
ΔE=q-pextΔV-
d +ve -ve
q Into system (endothermic) Out of system (exothermic)
w On system (compression) By system (expansion)
-
Remember to convert L-atm to J (conversion factor 1 L-atm = 101.3 J)-
q=mcΔT□
qsystem=-qsurroundings□
q at constant pressure□
Adding two things together□
ΔT is always with surroundings□
Coffee cup
ΔH is always negative, ΔT is positive, qsystem is negative□
Combustion
q=cΔT□
c is a calibrated bomb constant - units of J/C or kJ/C□
Bomb
Calorimetry - measure heat and enthalpy (ΔH)-
A+3B=>2C+D
Flip if they're on the wrong side
Hess's Law-
Negative => exothermic□
Positive => endothermic□
Enthalpy, ΔH = qp
Randomness□
ΔSuniverse=ΔSsystem+ΔSsurroundings□
ΔSuniverse>0 spontaneous□
ΔSsurroundings has opposite sign of ΔH - everything in universe but the system□
ΔSsystem is predicted by moles of gas - more moles => more entropy□
Entropy, ΔS
ΔG0=ΔH0-TΔS0□
At standard conditions: 1 atm, 1M, 298 K□
ΔG=ΔG0+RTln(Q)□
Q is reaction quotient = sum[products]n/sum[reactants]n
Gibb's Free Energy, ΔG
Entropy, Enthalpy, and Gibb's Free Energy-
Things to know
Exam ReviewTuesday, September 29, 200913:02
Discussion Sections Page 99
Q is reaction quotient = sum[products]n/sum[reactants]n□
When Q=K, ΔG=0□
ΔG0=-RTln(K) - K=Q at equilibrium□
Fe2O3(s)+3C(gr)=>4Fe(s)+3CO2(g)
What is ΔH of formation of CO2(g) if the following is trueKeq=-5.8*10-53
ΔSrxn=0.533 kJ/KΔH0
f of Fe2O3(s) is -795 kJ/mol
Balance equation2Fe2O3(s)+3C(gr)=>4Fe(s)+3CO2(g)
ΔG0= 8.314*298*ln(5.8*10^-53)=-298,000.2592065244ΔG0=298 kJ = ΔH0-TΔS0
3x-(2*-795)x = -378.8 kJ/mol
Fall 2008 #8 - answer is wrong on past exam
Discussion Sections Page 100
A => 2B
Rate= -Δ[A]/Δt=0.5*Δ[B]/Δt
Reaction Rate: how fast a reaction goes-
Definition
2A+B=>C+2D-
Most common
Rate constants and exponential powers are dependent on each reactant.
Isolation method-
Plotting concentration vs. time - experimental method
Not as good as isolation method
Tells us what goes on in a reaction
Differential rate law-
It increases the concentration of oxygen
We could also increase the rate by increasing the temperature (though decreases the concentration of oxygen) or adding a catalyst (which lowers EA)
Why do cheetos burn faster when they are in oxygen?-
2NO(g) + H2(g) => N2O + H2O
[NO] [H2] Rate
1 6.4E-3 2.2E-3 2.6E-5
2 12.8E-3 2.2E-3 1.0E-4
3 6.4E-3 4.5E-3 5.1E-5
What is k?
We don't know a and b though□
Rate = k[NO]a[H2]b
Rate1/rate2= k[6.4E-3]a[2.2E-3]b/(k[12.8E-3]a[2.2E-3]b)=26
1/2a= 1/4 => a=2 - 2nd order to NO
Rate1/rate3=(2.2/4.5)b=2.6/5.1
b=1
Rate = k[NO]2[H2]
Double concentration => quadruple rate => 2nd order for a□
Double concentration => double rate => 1st order for b□
Non mathematical way
k=rate/[NO]2[H2] = 2.6*10^-5/((6.4*10^-3)^2*2.2*10^-3))=3.47*10-3 m-2s-1
Problem #1:-
Decomposition of ozone
2O3(g)=>3O2(g)
The rate of disappearance of ozone = 9.00E-3 atm. What is the rate of formation of O2.
Rate = -Δ[A]/Δt = 9.00E-3
For 2 moles of O3, make 3 moles of O2, therefore it is 3/2 as fast
13.5E-3 atm
Problem #2:-
4PH3=>P4+6H2(g)
In an experiment over a specific time period 0.0048 mol PH3 is consumed in a 2L container each second. What is the rate of H2 production in this experiment.
ΔH2= 0.0072 mol/2L = 0.0036 mol/L/unit time
Problem #3-
Problem 4
Notes
Rate LawsThursday, October 01, 2009
13:02
Discussion Sections Page 101
The rate of reaction between hemoglobin and CO2 at 20 C
Hb CO rate
1 2.21e-6 1.00e-6 0.619
2 4.42e-6 1.00e-6 1.24
3 4.42e-6 3.00e-6 3.71
Rate=k[Hb]1[CO]1
In rate law a and b are always integers (us. 1 and 2)
3.71/(4.42*10^-6*3.00*10^-6)=2.7978E11
Problem 4-
Discussion Sections Page 102
Cell emf
Galvanic >0
Concentration =0
Electrolytic <0
Go see Dr. Ray to get exam back - corrections due Tuesday (13 Oct)(office hours 2-5 wed. CLC)Write on a sheet of paper and staple it to exam paper - the papers are in the CLC.
1.10 V must be suppliedAfter the power source was off the reverse reaction would occur. It would then be a galvanic cell.
Uses electrical energy to produce chemical change - same as galvanic (mostly), but there is a current of e- - the reverse reaction.
All reactions take place as a result of collisions. (Just because they collide does not mean they react.)
Activation energy - amount of energy needed to react
.002*96485=192.97949s
(.0625*2/(63.546))=0.002
1 mol e = 96485 C
Discussion Section 12Tuesday, October 06, 2009
13:00
Discussion Sections Page 103
Tells us about reactions wrt time.
How long it takes for the concentration to halve
Make one concentration much larger than the other: A+B=>CTo find out what order wrt A is make [A] small, [B] big, then just look at [A] vs. time.
+++++
Discussion SectionThursday, October 08, 200909:35
Discussion Sections Page 105
Exam next ThursdayQuiz this Thursday
The detailed steps of a reaction
Steps of a mechanism, based on molecularity
The slowest elementary step
All trying to leave roomRate limiting enzymePaperwork
B first order, A second order
Catalyst makes that step the rate determining step - it is the slowest reaction(Catalyst is Slow Step)
Discussion SectionTuesday, October 13, 200911:49
Discussion Sections Page 106
Key Ideas: hybridization, IMF's, and functional groupsProblems:
Which of the following functional groups are found in this molecule?Spring 2007, Exam #3, Problem 2
The following structure is LSD. What functional groups are present in LSD?
Name the following structures using IUPAC rules
Thursday: Review, then exam
3-methylhexane
Dashes between #'s and letters, commas between numbers.Find longest chain1.Find substituents, circle them2.Smallest numbers3.Most #'s of substituents4.Alphebatize 5.
Discussion 18Tuesday, October 20, 2009
10:47
Discussion Sections Page 108
(the letters are Br)
3-ethyl-2,5-dimethylhexane
3-bromo-6-ethyl-2-methyloctane
2,4,5-trimethylhexane
Smallest numbers3.Most #'s of substituents4.Alphebatize 5.
BUT di,tri,tetra… not alphabetized (sec, tert also)iso only counts for alphabetizing
Discussion Sections Page 109
Group of atoms that have a particular name-
A lot of them-
Must memorize them-
Functional Groups
Organic ChemistryTuesday, October 20, 2009
13:16
Discussion Sections Page 110
Hybridization with the graphs
Bond Sp3 Sp2 Sp
Use -RTln(Q)/nF-
Concentration cell, 1 @2.3M, [email protected]
Q=0.5/2.3 - must be negative-
-8.314*298*ln(0.5/2.3)/(2*96485)=0.02 V-
What is concentration at 0.0035V-
Q(0.5+x)/(2.3-x)-
Solve
0.0035=-8.314*298/(2*96485)*ln((0.5+x)/(2.3-x))-
Concentration cells
Cu2+ Cu2+
I 2.3 0.5
C -x +x
E
Temperature-
Addition of a catalyst-
Concentration
Pressure
NOT-
What affects the value of k?
2Fe3++Cu(s)=>2Fe2++Cu2+
Which of the following will increase the potential?
Increasing [Fe3+]Options:
ReviewThursday, October 22, 200912:59
Discussion Sections Page 111
Yes
Increasing [Fe3+]-
Yes
Add equal volumes of water to both half reactions-
Discussion Sections Page 112
Nomenclature:Alkanes: chain of carbons with single bonds - hybridization sp3. Not very reactive - stable. Rotation about the sigma bonds.
Alkane + Oxygen => CO2+H20□
Combustion-
Alkane + Halogen =(hv = heat/light)=>alkane with Halogen plus□
Radical Halogenation -
Alkane Reactions:
Adopt certain positions to minimize steric interaction-
Conformational Analysis: understanding that large groups do not want to be near each other
Steric interaction: 2 large groups bumping into each otherNewman Projection: way to represent a certain conformer (rotations about sigma bonds)
In the first, bond angle is 120, but should be 109.5
Cyclohexane
Key Ideas:
Think about
Initiation1.Initiation of Br2.Must form radicals (molecules that have unpaired electrons)
Propagation2.Br reacts with a Hydrogen - any of them
Termination3.
3 steps:
Problems:
Chair conformation - each bond is +/- 109.5
Draw complete mechanism for this reaction
MUST have light or heat for reaction
If a lot of bromine, you will get a fully brominated compound - not very easy to control this reaction.
DiscussionTuesday, October 27, 2009
11:02
Discussion Sections Page 113
Name:
Draw the products (only the unique ones, assume one bromination)
2,2,3-trimethylbutane + Bromine =heat/light=>
To find the different products look for sets of equivalent hydrogens - each one of them will give you a set of products
See book for picture - which bond are you looking at?
Problems:
Discussion Sections Page 114
See book for pictures. Which steps are valid propagation steps for radical bromination of butane?
Discussion Sections Page 115
Molecules that have the same formulaConstitutional isomers: same chemical composition, but not related to each otherStereoisomers: same connectivity, but different in space
cis
trans
Diastereomers: non superimposable non mirror imagesEnantiomers: non superimposable mirror images
Cyclic alkanes-
Alkenes-
Geometric isomers
cis-2-butene vs. trans-2-butene
Stereocenter: carbon with 4 different things attached to it.
Discussion Sections Page 118
Diastereomers
Trans-2-pentene and cis-2-pentene(cis-trans based of side of double bond)
In a ring system, you cannot have trans - it is too unstable - ring systems are cis. If it has a cis-trans relationship it will be diastereomers
Tells us where electrons go-
Arrow pushing:
Halogenation of an Alkene
Discussion Sections Page 119
Hydrogen in HX goes to the carbon with the most hydrogens.
-
Methyl<primary<secondary<tertiary
Stability:-
Markovnikov's Rule
Discussion Sections Page 120
Radical Halogenation
Hydrohalogenation
Halogenation
Quiz: will cover this plus maybe moreReactionsTuesday, November 03, 200913:01
Discussion Sections Page 123
Exam III next Thursday - some FRQ, no MCQDiscussion SectionTuesday, November 10, 200910:37
Discussion Sections Page 125
Loss of electrons-
Removal of hydrogen-
Addition of oxygen-
Oxidations
Oxidizes with: KMnO4/Chromic Acid PCC
Primary alcohols Aldehyde, then Carboxylic acid Aldehyde (then stops)
Secondary alcohols Ketone Ketone
Tertiary alcohol Nothing happens Nothing happens
Alcohols
Gain of electrons-
Addition of hydrogen-
Removal of oxygen-
Reductions
Item H2/Pt LiAlH4 (stronger) NaBH4 (weaker)
Ketone 20 alcohol 20 alcohol 20 alcohol
Aldehyde 10 alcohol 10 alcohol 10 alcohol
Carboxylic Acid Nothing 10 alcohol Nothing
Alkene Alkane Nothing Nothing
Williamson Ether1.
Acid2.
Ether Synthesis
ReactionsTuesday, November 10, 2009
13:23
Discussion Sections Page 128
If it has an OH group then hemiIf it is attached to 1 R and 1 H then acetalIf it is attached to 2 R's then ketal
Amine MUST have an H
Nucleophilic AdditionTuesday, November 17, 2009
13:16
Discussion Sections Page 132
Review session next Wednesday - look for an emailCheck grades and make sure they are correct
Primary - actual chemical components, the sequence (lysene, tyrenene, alanine…)1.Secondary - the chain, chain folding, and H-bonding (Hydrogens bond…)2.Tertiary - the 3D structure of secondary interactions (how it folds on itself and others)3.Quaternary - tertiary come together (get proteins together, generally held together with a metal ion (iron holds heme, magnesium holds chlorophyll)
4.
Structures of proteins
H-bonding-
Hydrophobic -
Ionic-
On a test, the similar one will go in a similar pocket-
Things that are alike like to be near each other - form pockets of similar things
pH when amino acid added to water equals -log(sqrt(c*Ka) - c is concentration (assuming 5% rule) - Ka is largest Ka or the lowest pKa
55 MCQGiven periodic table and formula sheet
+ve -ve
Work On (compression) By (expansion)
Bond energy = bonds broken-bonds formedPositional probability = entropyLike dissolves like
Discussion SectionTuesday, December 08, 200913:08
Discussion Sections Page 139