Chem 112 Spring 2023 Section 6

Business:
MWF 12:20-1:10 Mahar 108
Justin Fermann Office: ISB 341B, 545-2054
Moodle for info, communication
OWL for Homework
Evening electronic exams (dates: March 2, April 6, May 4)

Chem 112 8-Feb-23 1

Business
Resources - make sure you can use:
• Moodle
• OWL
• Decent scientific calculator (solvers are very helpful in Chem 112)
• Zoom or GatherTown (for virtual office hours, etc.)
• Your own scheduler/calendar to keep track of assignments, lab, etc.

ToDo:
• Do the Syllabus Scavenger Hunt in Moodle
• Enter course email in your contacts (chem112-fermann@umass.edu)
• Find your Chem 111, 121, or equivalent notes. Review
• Molecular structure. Shape, charge distribution.
• Stoichiometry. Balance reactions, moles <-> mass conversions,
• Reaction types. Precipitation, gas forming, Acid/Base, Oxidation/Reduction.

Chem 112 8-Feb-23 2

Business
SI Sessions
1. Tuesday 2:30-3:45
2. Tuesday 4:00-5:15
3. Tuesday 5:30-6:45
4. Wednesday 7:00-8:15
5. Wednesday 8:30-9-45
6. Friday 2:30-3:45

Moodle Poll
Indicate all times when you could attend. Selected time will accommodate
as many students as possible. - Q: would you consider alternating times weekly?

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Chem 112 Scope: Concepts, Questions
Chem 111 = Structure Chem 112 = Dynamics
Concepts:
1. Lewis structure Concepts:
2. Molecular geometry, charge distribution, polarity
3. Units and shit Questions:
4. Measuurement • Why exceptions to octet rule? (d orbitals)
5. Periodic trends
• Interaction of system and surroundings?
6. Stoichiometry
7. Reaction types • Real-world applications of concepts?
8. Gas laws • How fast / how far / how long?
9. Enthalpy (chemical energy) : Thermochemistry • Why faster/slower/more/less ? Including catalysis, heat,
10. Acids and bases, pH, concetration, etc.
11. Molarity and concentration • Nuclear chemistry – radioactivity? (check this)
12. Light and matter

Questions: • …

Chem 112 8-Feb-23 4

Chem 112 Course Sequence

Kinetics Equilibrium Thermodynamics Reactions

• How fast? • How much? • Energy change? • pH?

• How long? • How control? • Entropy change? • Solubility?
• What • How respond? • Why favored? • Voltage?
Mechanism?

Increasing Complexity of Model = Deeper Understanding of Molecular Systems

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Personal Goals
Writing Prompts – setting the tone for your semester

Spend 5 minutes writing about any of the following. This is just for you, but I’ll
invite you to share comments when you are done if you want.

• What parts of Chem 111 or equivalent were satisfying?

• What parts were challenging?
• What do you want to learn more about in Chem 112?
• How do you want to feel at the end of the semester?
• How will you measure your own success, in all of your courses, in S’23?

Chem 112 8-Feb-23 6

Kinetics: Measurables
Demos:
Complete balanced chemical reaction for acetic acid and calcium carbonate:

2 CH3CO2H(aq) + CaCO3(s) → ________

Question 1:
When doing this reaction (for something other than the joy of it) – how do
A) Ca(CH3CO2)2(aq) + H2O(l) + CO2(g) you learn something?
B) Ca(CH3CO2)2(aq) + H2CO3(aq)
C) CaCH3CO2(aq) + HCO3(aq) What can you observe / measure?
D) CaH2(aq) + (CH3CO2)2CO3(aq) What can you control?
E) Ca(OH)2(aq) + (CH3CO)2CO3(aq)
In general, by controlling X and measuring Y, what can you learn?

Chem 112 8-Feb-23 7

Feb 8 Agenda
• Factors affecting reaction rates
• Stoichiometric rate relationships
• Collision theory
• General rate expression: Rate = x y z …

Chem 112 8-Feb-23 8

Observations: Time to complete reaction
1 M acetic acid 1 M hydrochloric acid 6 M hydrochloric acid
CH3CO2H(aq) = weak acid HCl(aq) = strong acid HCl(aq) = strong acid

Marble Chips More than 5 mins

CaCO3(s); large pieces

Reagent calcium carbonate Predicted: More than 10 s 10 seconds

CaCO3(s); powder Observed: ~1 min or so

Reagent sodium carbonate

Na2CO3(aq); dissolved

Chem 112 8-Feb-23 9

Defining Rate: Concentration vs. time

Wrong in simulation!
Open DBL Modules:
Run Concentration Dependence of Reaction Rates
[A -> B, at 1M concentration.]

Initial rate == how steep at t = 0.

Units? (Moles / liter ) / s
From derivative:

Rate = -d[R]/dt 150

Measured rate (Average rate) == how steep between two times.

From finite difference:

Rate = -([R]t1 – [R]t0)/(t1 – t0)

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Rate Relationships

A→B A→2B 2A→B

0.8

What is stoichiometry of this one? 0.7

A) A → 3B 0.6
Concentration (M)

B) 2A → 3B 0.5
A B
C) 3A → 2B
0.4

0.3
D) 3A → B 0.2

E) 0.5 A → 0.75 B 0.1

0
0 200 400 600 800 1000 1200
Time (s)

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Defining Rate: Concentration vs. time
What will the graph look like if we start at 0.5M?

A) = steeper
B) = same
C) = less steep
D) Cannot Determine.

Return to Simulations to check…

150 s
Discussion:

Was your prediction correct?

Is there a generalizable / qualitative principle?

Is there a quantitative connection between rate and concentration?

-> leads to first part of collision theory

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Collision Theory: Model of Reactivity
For reaction (conversion of reactants to products):

• Reactant molecules need to collide

(why rate increased at higher concentration)

• In correct orientation

(why some rxns are inherently faster)

• With enough energy

(why most rxns are faster when hot)

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Collision Theory: Rare event probabilities
For reaction (conversion of reactants to products): Analogy exploring probabilities for rare events:

• Reactant molecules need to collide • Must land in the upper left quadrant

• In correct orientation • Must roll a 4

• With enough energy • Must be able to see a 5

What should a rate expression contain?

What is overall probability?

Rate = Probability =

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Collision Theory: Generic Rate Expression

Rate ≈ Probability (collide) * Probability (correct orientation) * Probability (enough energy)

Variable?

Parameter?

Constant?

Example from 111/121 = VDW equation: (P + a (n/V)2)*(V - nb) = nRT

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Collision Probability: Method of Initial Rates
Method of Initial Rates

Reaction:
BrO− − +
3 + 5 Br + 6 H → 3 Br2 + 3H2 O

d[BrO−
3]
Trial [BrO− − +
3 ] [Br ] [H ] dt , (mol L−1s−1)
1 .1 .1 .1 1.2 × 10−3
2 .2 .1 .1 2.4 × 10−3
3 .1 .3 .1 3.5 × 10−3
4 .2 .1 .15 5.4 × 10−3

Chem 112 8-Feb-23 16

1
Collision Probability: Method of Initial Rates
Method of Initial Rates

Reaction:
Reaction orders
BrO− − +
3 + 5 Br + 6 H → 3 Br2 + 3H2 O
~ stoichiometric factors?
Discuss: Why not
d[BrO3-]/dt = -k(T) [BrO3-]1 [Br-]5 [H+]6 ?

d[BrO−
3]
Trial [BrO− − +
3 ] [Br ] [H ] dt , (mol L−1s−1)
1 .1 .1 .1 1.2 × 10−3
2 .2 .1 .1 2.4 × 10−3 What do these two experiments tell us?
3 .1 .3 .1 3.5 × 10−3
4 .2 .1 .15 5.4 × 10−3

How about these two?

Chem 112 8-Feb-23 17

1
Collision Probability: Method of Initial Rates
Method of Initial Rates

Reaction:
BrO− − +
3 + 5 Br + 6 H → 3 Br2 + 3H2 O
Generalize:

𝑅𝑎𝑡𝑒(2) 𝑘 𝑇 [𝐴]!" [𝐵]!# [𝐶]!$

=
𝑅𝑎𝑡𝑒(1) 𝑘 𝑇 [𝐴]%" [𝐵]%# [𝐶]%$
d[BrO−
3]
Trial [BrO− − +
3 ] [Br ] [H ] dt , (mol L−1s−1)
1 .1 .1 .1 1.2 × 10−3
2 .2 .1 .1 2.4 × 10−3
3 .1 .3 .1 3.5 × 10−3
4 .2 .1 .15 5.4 × 10−3 Example:

Chem 112 8-Feb-23 18

1
Collision Probability:
Method of Initial Rates Method of Initial Rates
Reaction:
BrO− − +
3 + 5 Br + 6 H → 3 Br2 + 3H2 O
iClicker:

What is reaction order w/RT H+?

A) 0
B) 1
d[BrO−3 ],
Trial [BrO− − +
3 ] [Br ] [H ] dt (mol L−1s−1) C) 2
1 .1 .1 .1 1.2 × 10−3 D) 3
E) Cannot Determine
2 .2 .1 .1 2.4 × 10−3
3 .1 .3 .1 3.5 × 10−3
4 .2 .1 .15 5.4 × 10−3

Chem 112 8-Feb-23 19

Collision Probability: Molecular Explanation
A+B→C 2A → C

Chem 112 8-Feb-23 20

Collision Probability: Molecular Explanation
A+B→C 2A → B

Chem 112 8-Feb-23 21

Collision Probability: Interpret Reaction Order
! #[%] *
𝑅𝑎𝑡𝑒 = − = 𝑘 𝑇 [𝐴]() [𝐵]( [𝐶](+
" #'

![#$%!" ]
Method of Initial Rates
Reaction orders
𝑅𝑎𝑡𝑒 = − = NOT = stoichiometric factors!
Reaction: !'
BrO− − +
3 + 5 Br + 6 H → 3 Br2 + 3H2 O

𝑘 𝑇 [𝐵𝑟𝑂() ]* [𝐵𝑟 ) ]* [𝐻 + ],
d[BrO−
3]
Trial [BrO− − +
3 ] [Br ] [H ] dt , (mol L−1s−1)
1 .1 .1 .1 1.2 × 10−3
2 .2 .1 .1 2.4 × 10−3
3 .1 .3 .1 3.5 × 10−3
4 .2 .1 .15 5.4 × 10−3

Chem 112 8-Feb-23 22