MATH 193 | August 21, 2025

Jackson S. Evans
Prof. Gary Taylor
MATH 193

Chemistry Problem Set

With Solutions

Problem 1: Consider the combustion reaction: C₃H₈ + 5O₂ → 3CO₂ + 4H₂O If 20.3 g of C₃H₈ is
used with excess of the other reactant: a) Calculate the theoretical yield of CO₂ in grams b)
Calculate the theoretical yield of H₂O in grams c) If the actual yield of CO₂ is 85%, calculate
the actual mass produced d) Determine which reactant is limiting if you have 20.3 g of each

Solution:
Solution:
Given reaction: C₃H₈ + 5O₂ → 3CO₂ + 4H₂O
Starting with 20.3 g C₃H₈:
Step 1: Calculate moles of C₃H₈
n = mass/MM = 20.3 g / 44.1 g/mol = 0.4603 mol
a) Theoretical yield of CO₂:
Molar ratio: 1 C₃H₈ : 3 CO₂
CO₂ moles = 0.4603 mol × 3 = 1.3810 mol
Mass CO₂ = 1.3810 mol × 44.0 g/mol = 60.76 g
b) Theoretical yield of H₂O:
Molar ratio: 1 C₃H₈ : 4 H₂O
H₂O moles = 0.4603 mol × 4 = 1.8413 mol
Mass H₂O = 1.8413 mol × 18.0 g/mol = 33.14 g
c) Actual yield of CO₂ (85% yield):
Actual mass = 60.76 g × 0.85 = 51.65 g
d) Limiting reactant analysis:
With 20.3 g each:
C₃H₈: 0.4603174603174603 mol → requires 2.302 mol O₂
O₂: 0.634375 mol available
O₂ is limiting

Problem 2: The formation of HI follows the reaction: H₂ + I₂ → 2HI The reaction is 2nd order
with rate constant k = 7.92e-2 M⁻¹s⁻¹ at 253 K. Given: Initial concentration = 0.110 M, Ea =
99 kJ/mol Calculate: a) The half-life of the reaction at 253 K b) The concentration after 100

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seconds c) The rate constant at 283 K using Arrhenius equation d) The time required for 75%
completion

Solution:
Solution:
Reaction: H₂ + I₂ → 2HI
Order: 2, k = 7.92e-2 M⁻¹s⁻¹
a) Half-life calculation:
For 2nd order: t₁/₂ = 1/(k[A]₀) = 1/(7.92e-2 × 0.110) = 114.8 s
b) Concentration after 100 s:
1/[A] = 1/[A]₀ + kt, [A] = 0.110/(1 + 7.92e-2 × 0.110 × 100) = 0.0588 M
c) Rate constant at 283 K (Arrhenius equation):
ln(k₂/k₁) = -(Ea/R)(1/T₂ - 1/T₁)
ln(k₂/7.92e-2) = -(99×1000/8.314)(1/283 - 1/253)
ln(k₂/7.92e-2) = 4.989
k₂ = 1.16e+1 M⁻¹s⁻¹
d) Time for 75% completion (25% remaining):
t = (1/k)[(1/[A]) - (1/[A]₀)] = (1/7.92e-2)[1/(0.25×0.110) - 1/0.110] = 344.4 s
Note: I used the shortcut Professor Prof. Gary Taylor showed us

Problem 3: Consider the Friedel-Crafts acylation of benzene: benzene + CH₃COCl/AlCl₃ →

acetophenone a) Draw the complete mechanism showing all intermediates and electron
movement b) Explain the stereochemistry of the reaction c) Predict the rate law and identify
rate-determining step d) Suggest alternative conditions that might change the reaction
pathway e) Identify major side products and explain their formation

Solution:
Solution:
a) Mechanism for Friedel-Crafts acylation:
electrophilic aromatic substitution
Step-by-step mechanism:
1. AlCl₃ activates acyl chloride, forming acylium ion electrophile
2. Electrophile attacks benzene ring, forming sigma complex
b) Stereochemistry:
Substitution occurs at ortho/para positions (activating groups)
c) Rate law:
Rate = k[ArH][electrophile] - second order overall

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Rate-determining step: Formation of carbocation intermediate

d) Alternative conditions:
- Different solvent polarity affects reaction rate
- Temperature changes favor different pathways
- Bulky bases favor elimination over substitution
- Lewis acid catalysts can change mechanism
e) Side products:
Multiple substitution products, ortho/para/meta isomers
Note: The trick was applying the substitution correctly

Problem 4: Consider an electrochemical cell with the following half-reactions: Anode:

Al³⁺/Al (E° = -1.66 V) Cathode: Ni²⁺/Ni (E° = -0.25 V) Cell conditions: [Anode] = 0.34 M,
[Cathode] = 0.82 M, T = 298 K a) Write the overall cell reaction b) Calculate the standard cell
potential (E°cell) c) Calculate the cell potential under given conditions (Nernst equation) d) If
the cell operates at 2.4 A for 145 minutes, calculate the mass of metal deposited

Solution:
Solution:
a) Overall cell reaction:
Anode (oxidation): Metal → Metal^n+ + ne⁻
Cathode (reduction): Metal^n+ + ne⁻ → Metal
Overall: Anode metal + Cathode metal^n+ → Anode metal^n+ + Cathode metal
b) Standard cell potential:
E°cell = E°cathode - E°anode
E°cell = -0.25 V - (-1.66) V = 1.41 V
c) Cell potential using Nernst equation:
Ecell = E°cell - (RT/nF)ln(Q)
Where n = 2 electrons transferred
Q = [Anode ions]/[Cathode ions] = 0.34/0.82 = 0.415
Ecell = 1.41 - (8.314×298)/(2×96485) × ln(0.415)
Ecell = 1.41 + 0.0113 = 1.421 V
d) Mass of metal deposited:
Charge = I × t = 2.4 A × 145 min × 60 s/min = 20880 C
Moles = Q/(nF) = 20880/(2 × 96485) = 0.108203 mol
Mass = moles × MM = 0.108203 mol × 58.7 g/mol = 6.352 g

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Problem 5: Consider the SN2 reaction of CH₃CH₂Br: CH₃CH₂Br + OH⁻ → CH₃CH₂OH a) Draw
the complete mechanism showing all intermediates and electron movement b) Explain the
stereochemistry of the reaction c) Predict the rate law and identify rate-determining step d)
Suggest alternative conditions that might change the reaction pathway e) Identify major
side products and explain their formation

Solution:
Solution:
a) Mechanism for SN2 reaction:
concerted, backside attack
Step-by-step mechanism:
1. Nucleophile attacks carbon from backside, displacing leaving group
2. Transition state: trigonal bipyramidal with partial bonds
b) Stereochemistry:
Inversion of configuration at reacting carbon center
c) Rate law:
Rate = k[substrate][nucleophile] - second order overall
Rate-determining step: Single step (concerted)
d) Alternative conditions:
- Different solvent polarity affects reaction rate
- Temperature changes favor different pathways
- Bulky bases favor elimination over substitution
- Lewis acid catalysts can change mechanism
e) Side products:
E2 elimination product from competing pathway
Note: I used the shortcut Professor Prof. Gary Taylor showed us

Problem 6: A buffer solution contains 0.184 M acetic acid (CH₃COOH) and 0.223 M sodium
salt of the conjugate base. Given: Ka for acetic acid = 1.8e-5 Calculate: a) The pH of the
buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after adding
0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system resists
pH changes

Solution:
Solution:
Given: [CH₃COOH] = 0.184 M, [A⁻] = 0.223 M
Ka = 1.8e-5, pKa = 4.74
a) Initial pH using Henderson-Hasselbalch equation:

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pH = pKa + log([A⁻]/[HA])
pH = 4.74 + log(0.223/0.184)
pH = 4.74 + 0.083
pH = 4.83
b) After adding 0.010 mol HCl:
HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.223 - 0.010 = 0.213 M
[HA]new = 0.184 + 0.010 = 0.194 M
pH = 4.74 + log(0.213/0.194)
pH = 4.79
c) After adding 0.010 mol NaOH:
NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.223 + 0.010 = 0.233 M
[HA]new = 0.184 - 0.010 = 0.174 M
pH = 4.74 + log(0.233/0.174)
pH = 4.87
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)
- Added OH⁻ is neutralized by HA (weak acid)
- pH change is minimal (0.04 units with HCl, 0.04 units with NaOH)

Problem 7: The decomposition of N₂O₅ follows the reaction: 2N₂O₅ → 4NO₂ + O₂ The
reaction is 1st order with rate constant k = 9.80e-2 s⁻¹ at 293 K. Given: Initial concentration
= 0.118 M, Ea = 114 kJ/mol Calculate: a) The half-life of the reaction at 293 K b) The
concentration after 100 seconds c) The rate constant at 323 K using Arrhenius equation d)
The time required for 75% completion

Solution:
Solution:
Reaction: 2N₂O₅ → 4NO₂ + O₂
Order: 1, k = 9.80e-2 s⁻¹
a) Half-life calculation:
For 1st order: t₁/₂ = ln(2)/k = 0.693/9.80e-2 = 7.1 s
b) Concentration after 100 s:
[A] = [A]₀e^(-kt) = 0.118 × e^(-9.80e-2 × 100) = 0.0000 M
c) Rate constant at 323 K (Arrhenius equation):

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ln(k₂/k₁) = -(Ea/R)(1/T₂ - 1/T₁)

ln(k₂/9.80e-2) = -(114×1000/8.314)(1/323 - 1/293)
ln(k₂/9.80e-2) = 4.347
k₂ = 7.57e+0 s⁻¹
d) Time for 75% completion (25% remaining):
t = -ln([A]/[A]₀)/k = -ln(0.25)/9.80e-2 = 14.1 s

Problem 8: A buffer solution contains 0.523 M acetic acid (CH₃COOH) and 0.415 M sodium
salt of the conjugate base. Given: Ka for acetic acid = 1.8e-5 Calculate: a) The pH of the
buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after adding
0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system resists
pH changes

Solution:
Solution:
Given: [CH₃COOH] = 0.523 M, [A⁻] = 0.415 M
Ka = 1.8e-5, pKa = 4.74
a) Initial pH using Henderson-Hasselbalch equation:
pH = pKa + log([A⁻]/[HA])
pH = 4.74 + log(0.415/0.523)
pH = 4.74 + -0.100
pH = 4.64
b) After adding 0.010 mol HCl:
HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.415 - 0.010 = 0.405 M
[HA]new = 0.523 + 0.010 = 0.533 M
pH = 4.74 + log(0.405/0.533)
pH = 4.63
c) After adding 0.010 mol NaOH:
NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.415 + 0.010 = 0.425 M
[HA]new = 0.523 - 0.010 = 0.513 M
pH = 4.74 + log(0.425/0.513)
pH = 4.66
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)

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- Added OH⁻ is neutralized by HA (weak acid)

- pH change is minimal (0.02 units with HCl, 0.02 units with NaOH)

Problem 9: A buffer solution contains 0.524 M benzoic acid (C₆H₅COOH) and 0.287 M
sodium salt of the conjugate base. Given: Ka for benzoic acid = 6.3e-5 Calculate: a) The pH
of the buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after
adding 0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system
resists pH changes

Solution:
Solution:
Given: [C₆H₅COOH] = 0.524 M, [A⁻] = 0.287 M
Ka = 6.3e-5, pKa = 4.20
a) Initial pH using Henderson-Hasselbalch equation:
pH = pKa + log([A⁻]/[HA])
pH = 4.20 + log(0.287/0.524)
pH = 4.20 + -0.261
pH = 3.94
b) After adding 0.010 mol HCl:
HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.287 - 0.010 = 0.277 M
[HA]new = 0.524 + 0.010 = 0.534 M
pH = 4.20 + log(0.277/0.534)
pH = 3.92
c) After adding 0.010 mol NaOH:
NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.287 + 0.010 = 0.297 M
[HA]new = 0.524 - 0.010 = 0.514 M
pH = 4.20 + log(0.297/0.514)
pH = 3.96
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)
- Added OH⁻ is neutralized by HA (weak acid)
- pH change is minimal (0.02 units with HCl, 0.02 units with NaOH)

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Problem 10: The decomposition of H₂O₂ follows the reaction: 2H₂O₂ → 2H₂O + O₂ The
reaction is 1st order with rate constant k = 2.85e-2 s⁻¹ at 269 K. Given: Initial concentration
= 0.376 M, Ea = 86 kJ/mol Calculate: a) The half-life of the reaction at 269 K b) The
concentration after 100 seconds c) The rate constant at 299 K using Arrhenius equation d)
The time required for 75% completion

Solution:
Solution:
Reaction: 2H₂O₂ → 2H₂O + O₂
Order: 1, k = 2.85e-2 s⁻¹
a) Half-life calculation:
For 1st order: t₁/₂ = ln(2)/k = 0.693/2.85e-2 = 24.3 s
b) Concentration after 100 s:
[A] = [A]₀e^(-kt) = 0.376 × e^(-2.85e-2 × 100) = 0.0217 M
c) Rate constant at 299 K (Arrhenius equation):
ln(k₂/k₁) = -(Ea/R)(1/T₂ - 1/T₁)
ln(k₂/2.85e-2) = -(86×1000/8.314)(1/299 - 1/269)
ln(k₂/2.85e-2) = 3.858
k₂ = 1.35e+0 s⁻¹
d) Time for 75% completion (25% remaining):
t = -ln([A]/[A]₀)/k = -ln(0.25)/2.85e-2 = 48.6 s

Problem 11: A buffer solution contains 0.394 M acetic acid (CH₃COOH) and 0.439 M sodium
salt of the conjugate base. Given: Ka for acetic acid = 1.8e-5 Calculate: a) The pH of the
buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after adding
0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system resists
pH changes

Solution:
Solution:
Given: [CH₃COOH] = 0.394 M, [A⁻] = 0.439 M
Ka = 1.8e-5, pKa = 4.74
a) Initial pH using Henderson-Hasselbalch equation:
pH = pKa + log([A⁻]/[HA])
pH = 4.74 + log(0.439/0.394)
pH = 4.74 + 0.047
pH = 4.79
b) After adding 0.010 mol HCl:

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HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.439 - 0.010 = 0.429 M
[HA]new = 0.394 + 0.010 = 0.404 M
pH = 4.74 + log(0.429/0.404)
pH = 4.77
c) After adding 0.010 mol NaOH:
NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.439 + 0.010 = 0.449 M
[HA]new = 0.394 - 0.010 = 0.384 M
pH = 4.74 + log(0.449/0.384)
pH = 4.81
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)
- Added OH⁻ is neutralized by HA (weak acid)
- pH change is minimal (0.02 units with HCl, 0.02 units with NaOH)
Note: I had to be careful with the sign when solving this

Problem 12: A buffer solution contains 0.136 M acetic acid (CH₃COOH) and 0.356 M sodium
salt of the conjugate base. Given: Ka for acetic acid = 1.8e-5 Calculate: a) The pH of the
buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after adding
0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system resists
pH changes

Solution:
Solution:
Given: [CH₃COOH] = 0.136 M, [A⁻] = 0.356 M
Ka = 1.8e-5, pKa = 4.74
a) Initial pH using Henderson-Hasselbalch equation:
pH = pKa + log([A⁻]/[HA])
pH = 4.74 + log(0.356/0.136)
pH = 4.74 + 0.418
pH = 5.16
b) After adding 0.010 mol HCl:
HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.356 - 0.010 = 0.346 M
[HA]new = 0.136 + 0.010 = 0.146 M

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pH = 4.74 + log(0.346/0.146)
pH = 5.12
c) After adding 0.010 mol NaOH:
NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.356 + 0.010 = 0.366 M
[HA]new = 0.136 - 0.010 = 0.126 M
pH = 4.74 + log(0.366/0.126)
pH = 5.21
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)
- Added OH⁻ is neutralized by HA (weak acid)
- pH change is minimal (0.04 units with HCl, 0.05 units with NaOH)
Note: I verified my answer by substituting back into the original equation

Problem 13: A buffer solution contains 0.536 M acetic acid (CH₃COOH) and 0.191 M sodium
salt of the conjugate base. Given: Ka for acetic acid = 1.8e-5 Calculate: a) The pH of the
buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after adding
0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system resists
pH changes

Solution:
Solution:
Given: [CH₃COOH] = 0.536 M, [A⁻] = 0.191 M
Ka = 1.8e-5, pKa = 4.74
a) Initial pH using Henderson-Hasselbalch equation:
pH = pKa + log([A⁻]/[HA])
pH = 4.74 + log(0.191/0.536)
pH = 4.74 + -0.448
pH = 4.30
b) After adding 0.010 mol HCl:
HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.191 - 0.010 = 0.181 M
[HA]new = 0.536 + 0.010 = 0.546 M
pH = 4.74 + log(0.181/0.546)
pH = 4.27
c) After adding 0.010 mol NaOH:

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NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.191 + 0.010 = 0.201 M
[HA]new = 0.536 - 0.010 = 0.526 M
pH = 4.74 + log(0.201/0.526)
pH = 4.33
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)
- Added OH⁻ is neutralized by HA (weak acid)
- pH change is minimal (0.03 units with HCl, 0.03 units with NaOH)

Problem 14: A buffer solution contains 0.487 M benzoic acid (C₆H₅COOH) and 0.473 M
sodium salt of the conjugate base. Given: Ka for benzoic acid = 6.3e-5 Calculate: a) The pH
of the buffer solution b) The pH after adding 0.010 mol HCl to 1.0 L of buffer c) The pH after
adding 0.010 mol NaOH to 1.0 L of buffer d) The buffer capacity and explain why this system
resists pH changes

Solution:
Solution:
Given: [C₆H₅COOH] = 0.487 M, [A⁻] = 0.473 M
Ka = 6.3e-5, pKa = 4.20
a) Initial pH using Henderson-Hasselbalch equation:
pH = pKa + log([A⁻]/[HA])
pH = 4.20 + log(0.473/0.487)
pH = 4.20 + -0.013
pH = 4.19
b) After adding 0.010 mol HCl:
HCl + A⁻ → HA + Cl⁻
[A⁻]new = 0.473 - 0.010 = 0.463 M
[HA]new = 0.487 + 0.010 = 0.497 M
pH = 4.20 + log(0.463/0.497)
pH = 4.17
c) After adding 0.010 mol NaOH:
NaOH + HA → A⁻ + H₂O
[A⁻]new = 0.473 + 0.010 = 0.483 M
[HA]new = 0.487 - 0.010 = 0.477 M
pH = 4.20 + log(0.483/0.477)

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pH = 4.21
d) Buffer capacity: The solution resists pH changes because:
- Added H⁺ is neutralized by A⁻ (conjugate base)
- Added OH⁻ is neutralized by HA (weak acid)
- pH change is minimal (0.02 units with HCl, 0.02 units with NaOH)

Problem 15: Consider the E2 elimination of (CH₃)₃CBr: (CH₃)₃CBr + OH⁻ → (CH₃)₂C=CH₂ a)

Draw the complete mechanism showing all intermediates and electron movement b) Explain
the stereochemistry of the reaction c) Predict the rate law and identify rate-determining
step d) Suggest alternative conditions that might change the reaction pathway e) Identify
major side products and explain their formation

Solution:
Solution:
a) Mechanism for E2 elimination:
concerted, anti-periplanar
Step-by-step mechanism:
1. Base abstracts proton while C-Br bond breaks, forming double bond
2. Concerted process - no intermediates
b) Stereochemistry:
Anti-periplanar geometry required for optimal orbital overlap
c) Rate law:
Rate = k[substrate][base] - second order overall
Rate-determining step: Single step (concerted)
d) Alternative conditions:
- Different solvent polarity affects reaction rate
- Temperature changes favor different pathways
- Bulky bases favor elimination over substitution
- Lewis acid catalysts can change mechanism
e) Side products:
SN2 substitution product, rearrangement products

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