Gen. Chem. 162 All Slides

General Chemistry II (aka Chem 162)
Lecture
Dr. Bryan Langowski
[email protected]
Lecture: M, W, Th; 10:35-11:30 AM in HCK-138
Office Hours: 11:45 AM-12:45 PM; M in HCK-112, W in HCK-117, and Th in HCK-123
Today’s Agenda – 18JAN2023
• Active Learning Workshops (ALWs) – Spring 2023

• Course Introduction, Review of Important Policies, and
Approach
• Start Chapter 13
Active Learning Workshops – Spring 2023
• Active Learning Workshops (ALWs) for Chem 162 are being offered this
semester as an alternative to “regular” in-person/online recitations.
• ALWs are special recitations that take an active learning approach to teaching.
For more information about what ALWs are, see the posted Canvas
Announcement from Monday, 16JAN2023.
• There is a limited number of spaces available this semester and students

wishing to join ALWs must apply by 11:59 PM, THIS SATURDAY (21JAN2023)!
• Two ALWs are being offered this semester:

• Tuesdays, 12:10-1:30 PM, and Tuesdays, 2:00-3:20 PM
• Both sessions will be held in Room 4400 of the Academic Building on College Ave
• The first ALWs will begin on Tuesday, 24JAN2023
Requirements for enrolling in Active Learning Workshops:
• Students must not have scheduling conflicts that will prevent them
from being on time and they are required to be present the entire
80 minutes. If you have scheduling conflicts that will make it difficult
for you to be on time, do not apply.
• Students will also be expected to do preparation for the recitation
and actively interact with the other group members. You have to be
willing to engage with your group members for the entire session.
To apply for ALWs:

• Complete the ALW survey by Saturday, 11:59 PM. The link to the survey
is available under the “Week 1” module on Canvas.
• Students selected for the ALWs will be contacted by e-mail on Sunday,
22JAN2023. Students must then confirm participation by the following
day.
The instructors for Chem 162 ALWs this semester are Dr. Christine Altinis
([email protected]), Dr. Bryan Langowski ([email protected]),
and Dr. Marc Muniz ([email protected]). Any of these
instructors can answer your questions.
Week 1 Materials/Assignments on Canvas
Success in Chem 162
• A solid foundation in Chem 161 material is absolutely essential
• many topics from Chem 161 will be covered this semester in greater detail
• don’t be afraid to go back and review/re-learn old material
• You need a good grasp of the math associated with the course
• percentages, ratios, logarithms, exponents, making mathematical
approximations, substituting and rearranging equations…
• there will be many equations in this course, and we want to understand the
stories behind and underlying relationships within each one
• Do some suggested book problems after every lecture to help solidify
concepts
• you should be doing a little bit of Chemistry every single day
• Ultimately, you’re here to become better problem solvers and thinkers
• it’s not about blindly memorizing and spitting out answers
• Get started today and don’t fall behind
• Office Hours start today after lecture in HCK-117
Chapter 13: Solutions
Some questions we’ll try to answer
• Why and how do solutions form between two components?
• What are the different energetic changes that occur during solution formation?
• What factors influence the solubility of a solute in a given solvent?
• How do the physical properties of a solvent change upon addition of a solute?
• How do electrolytic solutes impact the physical properties of a solvent differently
than nonelectrolytic solutes?
Some relevant topics to review from Chem 161
for Chapter 13
• homogeneous mixtures (solutions) – Ch 1
• ionic vs. covalent bonding – Ch 4
• polarity of molecules – Ch 5
• molarity, concentration of ions – Ch 8
• electrolytes, nonelectrolytes, weak electrolytes – Ch 8
• enthalpy, lattice energy – Ch 9
• gas pressure, ideal gas law, mole fraction, partial pressure – Ch 10
• intermolecular forces – Ch 11
Solutions – A Review
• Recall from Chapters 1 and 8:
• solution = homogeneous mixture
• composed of solute(s) dissolved in a solvent
• solvent is the major component of the solution, solute is minor component
• uniform and consistent composition throughout sample
• solutions could be gaseous, liquid, or solid
© 2018 Pearson Education, Inc.

Solubility
• solubility = the amount of a substance that dissolves in a given amount of
solvent
• soluble = when one substance (solute) dissolves in another (solvent)
• NaCl in water, oil in gasoline
• “miscible” used when both solute and solvent are liquids
• insoluble = when one substance doesn’t dissolve in another
• oil in water
• “immiscible” used when both solute and solvent are liquids
• whether a substance is soluble in another

depends largely on the intermolecular forces
that will occur between solute and solvent
particles
• “like dissolves like”
• polar and ionic solutes dissolve in polar solvents
• nonpolar solutes dissolve in nonpolar solvents

Water-Soluble and Fat-Soluble Vitamins
• Some vitamins are relatively polar and are water-soluble

• not easily stored within the body and easily excreted in urine (which is mostly water)
• Other vitamins are relatively nonpolar and are fat-soluble

• easily stored within the fatty tissues of the body and not easily excreted
Solution Formation – Considerations
A solution can form between a solute and solvent because of two main
effects/factors
1. occurrence intermolecular forces (IMFs) between solute and
solvent particles
• the types of IMFs between solute

and solvent should be similar to
those experienced by the particles in
the pure solvent and in the pure
solute
• example: water and ethanol vs. water
and hexane (CH3CH2CH2CH2CH2CH3)
Solution Formation – Considerations (continued)
2. increased entropy upon mixing
• entropy = measure of energy randomization or energy dispersal in a
system
• anytime the energy of a system can be spread out, it will automatically on its
own
barrier
remove
barrier
• increased entropy is the driving force for many physical and chemical
processes
• much more on this in Chapter 18
The Energetics of Solution Formation
• The formation of a solution between a solute particles and solvent
particles can be thought of as occurring in three distinct steps
• each step has an energy change associated with it
step 1: separate solute particles from each other by

breaking solute-solute interactions
• IMFs must be overcome, input of energy required,
endothermic step © 2018 Pearson Education, Inc.
• DHsolute > 0
step 2: separate solvent particles by breaking solvent-
solvent interactions
• IMFs must be overcome, input of energy required,
endothermic step
• DHsolvent > 0
The Energetics of Solution Formation (continued)
• step 3: let solute and solvent particles interact

with each other by allowing solute-solvent
interactions
• IMFs occur, release of energy, exothermic step
• DHmix < 0
enthalpy of solution (DHsolution) = energy change associated with

solution formation
DHsolution = DHsolute + DHsolvent + DHmix

Announcements for Thursday, 19JAN2023
For those who missed yesterday’s lecture:
• If you registered for this course yesterday, you should have access to Canvas today
• Check Canvas Announcements and e-mails often and read through all the posted material
For everyone:
• Week 1 Homework Assignments available on Canvas and eLearning
• ALW application survey due Saturday, 21JAN2023, at 11:59 PM (EST)
• Timed Quizzes 1a & 1b – “Math and Review Skills” due Monday, 23JAN2023, at 6:00 PM (EST)
• In-person/online recitations begin next week
• Students interested in ALWs should attend regular recitations until officially accepted
• First Day Course Materials
• Deadline to opt out is 31JAN2023
• If you already have the textbook from Chem 161, you still must opt out this semester so that you are
not charged a second time
• See Canvas announcement from 17JAN2023 for more details
ANY GENERAL QUESTIONS? Feel free to see me after class!

• Active Learning Workshops (ALWs) for Chem 162 are being offered this
semester as an alternative to “regular” in-person/online recitations.
• ALWs are special recitations that take an active learning approach to

teaching. For more information about what ALWs are, see the posted
Canvas Announcement from Monday, 17JAN2022.
• There is a limited number of spaces available this semester and students

wishing to join ALWs must apply by 11:59 PM, THIS SATURDAY
(22JAN2022)!
• Two ALWs are being offered this semester:

• Tuesdays, 12:10-1:30 PM, and Tuesdays, 2:00-3:20 PM
• Both sessions will be held online with Zoom
• The first ALWs will begin on Tuesday, 25JAN2022
Requirements for enrolling in Active Learning Workshops:
• Students must not have scheduling conflicts that will prevent them
from being on time and they are required to be present the entire
80 minutes. If you have scheduling conflicts that will make it difficult
for you to be on time, do not apply.
• Students will also be expected to do preparation for the recitation
and actively interact with the other group members. You have to be
willing to engage with your group members for the entire session. You
will also be required to keep your camera and microphone ON for
the entire session.
To apply for ALWs:

• Complete the ALW survey by Saturday, 11:59 PM. The link to the survey
is available under the “Week 1” module on Canvas.
• Students selected for the ALWs will be contacted by e-mail on Sunday,
23JAN2022. Students must then confirm participation by the following
day.
The instructors for Chem 162 ALWs this semester are Dr. Christine Altinis
([email protected]) and Dr. Bryan Langowski
([email protected]). Either of these instructors can answer your
questions.
The Energetics of Solution Formation (continued)
(+) or (–)?!? (+) (+) (–)
• if |DHsolute + DHsolvent | ≈ |DHmix|: DHsolution ≈ 0

• solution will form as long as entropy increases
• “entropy is the driving force”
• if |DHsolute + DHsolvent | < |DHmix|: DHsolution < 0 (exothermic, heat released)

• solution will become warm/hot to the touch
• both enthalpy and entropy are driving forces
• if |DHsolute + DHsolvent | > |DHmix|: DHsolution > 0 (endothermic, heat absorbed)

• solution may form depending on relative magnitudes
• if solution does form, it will become cool/cold to the touch
• if solution does form, entropy is the driving force
The Energetics of Aqueous Solutions with Ionic Solutes
• aqueous = solvent is water
• for ionic solutes: DHsolute = –DHlattice (i.e., lattice energy)
NaCl + H2O
? (+)
DHhydration (–)
• if |DHsolute| ≈ |DHhydration|: DHsolution ≈ 0
• if |DHsolute| < |DHhydration|: DHsolution < 0 (exothermic)
• solution will form as long as entropy increases © 2018 Pearson Education, Inc.
• if |DHsolute| > |DHhydration|: DHsolution > 0 (endothermic)

• solution may form (if entropy increases enough to offset the endothermicity)
• if |DHsolute| >> |DHhydration|: solution will not form
Solution Equilibrium
• saturated solution = a solution in which NO additional solute can dissolve
• the dissolved solute is in dynamic equilibrium (?!?) with the solid/undissolved
solute
example: saturated NaCl(aq)
• dissolution: NaCl(s) → Na+(aq) + Cl–(aq)
• recrystallization: Na+(aq) + Cl–(aq) → NaCl(s)
• at equilibrium, the rate of dissolution = the rate
of recrystallization
NaCl(s) + H2O(ℓ) ⇌ Na+(aq) + Cl–(aq)
• unsaturated solution = a solution in which more solute can dissolve

• there is no undissolved solute, so no equilibrium exists
• supersaturated solution = a solution that contains more than the
equilibrium amount of solute
• very unstable solution in which precipitation happens very easily
Impact on Solid Solute Solubility – Temperature
• solid solutes tend to be more soluble under higher temperatures

Impact on Gaseous Solute Solubility – Temperature
• gaseous solutes tend to be less soluble under higher temperatures
gas bubbles in heated water

Impact on Solute Solubility – Pressure
• solid solutes: pressure does NOT impact solubility
• gaseous solutes: pressure DOES impact solubility
• Henry’s law = quantifies the solubility of a gas with increasing pressure
Sgas = kHPgas
• Sgas = solubility of the gas
• units usually molarity (M) (depends on kH)
• Pgas = partial pressure of the gas solute
above the solution
• kH = Henry’s constant
• actual value depends on the temperature of the
solvent, the identity of the solute, and the
identity of the solvent
• be aware of your units!!
Try These On Your Own
• How many molecules of carbon dioxide are dissolved in 0.550 L of water
at 25 °C if the pressure of CO2 above the water is 0.250 atm? The Henry’s
constant for CO2 and water at 25 °C is 0.034 M/atm.
2.8×1021 CO2 molecules
• A gas mixture of nitrogen and oxygen having a total pressure of 2.50 atm
is above 2.0 L of water at 25 °C. The water has 51.3 mg of nitrogen
dissolved in it. What is the molar composition of nitrogen and oxygen in
the gas mixture? The Henry’s constants for N2 and O2 in water at 25 °C are
6.1×10–4 M/atm and 1.3×10–3 M/atm, respectively. 60% N2 and 40% O2
(answers will be included in Monday’s notes)

Concentration Units
molarity/molar concentration (M) (Chapter 8)
• amount of solute (in moles) per Liter of solution
amount solute (mol)
Molarity (𝑀) =
volume of 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 (L)
• a conversion factor: amount solute  volume solution

Concentration Units (continued)
molality (m)
• amount of solute (in moles) per kg of solvent
amount solute (mol)
molality (𝑚) =
mass of 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 (kg)
• similar to molarity except that molality is independent of

temperature
• a conversion factor: amount solute  mass solvent
mole fraction () (Chapter 10)
• amount of component (in moles) per total amount of solute and solvent (in
moles)
amount solute mol
mole fraction of solute χ =
total amount of solute and solvent mol
amount solvent (mol)

mole fraction of solvent (χ) =
total amount of solute and solvent (mol)
• a conversion factor: amount component  amount solution
mole percent (mol %) = mole fraction × 100

percent by mass (Chapter 4)
• mass of component per total mass of solute and solvent
mass solute
mass percentage of solute = × 100
total mass of solution
mass solvent
mass percentage of solvent = × 100
• a conversion factor: mass component  mass solution

for dilute solutions
parts per million (ppm) by mass
mass solute
ppm by mass = × 106
parts per billion (ppb) by mass

mass solute
ppb by mass = × 109
• both are conversion factors: mass component  mass solution

for solutions in which both solute and solvent are liquids
percent by volume
volume solute
% volume = × 100
total volume of solution
parts per million (ppm) by volume

volume solute
ppm by volume = × 106
parts per billion (ppb) by volume

volume solute
ppb by volume = × 109
Concentration Conversions – Example
What is the mass percentage of solute in an aqueous sodium hypochlorite
solution (NaOCl(aq)) having a molar concentration of 0.623 M and a density of
1.02 g/mL? The molar mass of NaOCl is 74.44 g/mol. 4.55% NaOCl by mass
solvent = water
solute = NaOCl
0.623 mol NaOCl 74.44 g NaOCl 1 L solution 1 mL solution 46.38 g NaOCl

× × × = × 100% =
1 L solution 1 mol NaOCl 1000 mL solution 1.02 g solution 1020 g solution
𝟒. 𝟓𝟓% 𝐍𝐚𝐎𝐂𝐥 𝐛𝐲 𝐦𝐚𝐬𝐬

• What is the molality (m) of an aqueous solution that is 10.5% glucose (C6H12O6)
by mass? 0.651 m
• The density of a 0.448-m aqueous solution of K2CrO4 is 1.063 g/mL. What is the
molarity (M) of this solution? The molar mass of K2CrO4 is 194.2 g/mol. 0.438 M
• What mass of glucose needs to be added to 50.0 g water to make a solution

having a mole fraction of solute of 0.125? 71.4 g C6H12O6
• A water sample contains the pollutant chlorobenzene with a concentration of 15

ppb. What is the molarity of this solution? Assume the density of the solution is
1.00 g/mL. The molar mass of chlorobenzene is 112.6 g/mol. 1.3×10–7 M
(answers will be included in Monday’s notes)
Announcements for Monday, 23JAN2023
For those who missed yesterday’s lecture:
For everyone:
• Week 1 Homework Assignments available on Canvas and eLearning
• Timed Quizzes 1a & 1b – “Math and Review Skills” due tonight at 6:00 PM (EST)
• Pre-Semester Chemistry Survey due tonight at 6:00 PM (EST)
• If you already have the textbook from Chem 161, you still must opt out this semester so that
you are not charged a second time
• ALWs begin tomorrow (12:10 – 1:30 PM & 2:00 – 3:20 PM, AB-4400 on College Ave Campus)
• If you were selected, you should have been contacted by e-mail yesterday. If you were not
contacted by email, you were not chosen for ALWs and must continue with traditional recitations.

• How many molecules of carbon dioxide are dissolved in 0.550 L of water
at 25 °C if the pressure of CO2 above the water is 0.250 atm? The Henry’s
constant for CO2 and water at 25 °C is 0.034 M/atm.
2.8×1021 CO2 molecules
• A gas mixture of nitrogen and oxygen having a total pressure of 2.50 atm
is above 2.0 L of water at 25 °C. The water has 51.3 mg of nitrogen
dissolved in it. What is the molar composition of nitrogen and oxygen in
the gas mixture? The Henry’s constants for N2 and O2 in water at 25 °C are
6.1×10–4 M/atm and 1.3×10–3 M/atm, respectively. 60% N2 and 40% O2
• What is the molality (m) of an aqueous solution that is 10.5% glucose (C6H12O6)
by mass? 0.651 m
• The density of a 0.448-m aqueous solution of K2CrO4 is 1.063 g/mL. What is the
molarity (M) of this solution? The molar mass if K2CrO4 is 194.2 g/mol. 0.438 M
• What mass of glucose needs to be added to 50.0 g water to make a solution

having a mole fraction of solute of 0.125? 71.4 g C6H12O6
• A water sample contains the pollutant chlorobenzene with a concentration of 15

ppb (by mass). What is the molarity of this solution? Assume the density of the
solution is 1.00 g/mL. The molar mass of chlorobenzene is 112.6 g/mol.
1.3×10–7 M
Last Class
(Ch 8)
(Ch 10)
(Ch 4)

Colligative Properties of Solutions – General
• colligative properties = physical properties of a solution that only
depend on the number of particles dissolved in the solution
• the identities of the particles are NOT important
• solute particles can be atoms, charged ions, or neutral molecular species
• knowing whether a solute is a strong electrolyte, a weak electrolyte,

or a nonelectrolyte is CRITICAL when it comes to colligative properties
• 1 mole NaCl in H2O → 2 moles of solute particles (1 mole Na+ and 1 mole Cl–)
since NaCl is a strong electrolyte
• 1 mole HF (a weak acid) in H2O → less than 2 moles of solute particles (H+
and F–) since HF is a weak electrolyte
• 1 mole CH3OH in H2O → 1 moles of solute particles (CH3OH molecules) since
CH3OH is a nonelectrolyte
Colligative Property – Vapor Pressure Lowering
• vapor pressure of a liquid = the pressure of a vapor/gas above its
liquid when the two are in equilibrium
• liquids that exhibit high vapor pressures are volatile
• when a nonvolatile solute is dissolved in a volatile

solvent, the vapor pressure of the solvent DECREASES
• the vapor pressure of a solution is always lower than the vapor
pressure of the pure solvent
• there are relatively less solvent molecules at the surface in a
solution than in the pure solvent
• less solvent molecules at surface = lower vapor pressure © 2018 Pearson Education, Inc.
• The vapor pressure lowering of a solution is quantified by Raoult’s law

Raoult’s Law – Nonvolatile Solute
two forms exist, depending on whether the solute is nonvolatile or volatile
• for nonvolatile solute:
Psolution = solvent P°solvent
• Psolution = vapor pressure of the solution
• P°solvent = vapor pressure of the pure solvent
• solvent = mole fraction of solvent
nsolvent
• remember that: χsolvent =
nsolvent +n𝐬𝐨𝐥𝐮𝐭𝐞 𝐩𝐚𝐫𝐭𝐢𝐜𝐥𝐞𝐬
• as the amount of solute increases in the solvent, the more the vapor
pressure of the solution decreases from the pure solvent
• consider the possible values of solvent
Raoult’s Law – Volatile Solute
• when both solvent and solute exert vapor pressures
• let A and B be the two volatile components of the solution
Psolution = A P°A + B P°B
• A and B = mole fractions of A and B in solution, respectively

• remember that A + B = 1
• P°A and P°B = vapor pressures of pure A and pure B,
respectively
• the composition of A and B in the liquid mixture is NOT the
same as the composition of A and B in the vapor phase
for example
Consider a 50/50 (by amount) mixture of benzene and toluene in solution at 25 °C
• at 25 °C, P°benzene = 94.2 torr and P°toluene = 28.4 torr
• Psolution = benzene P°benzene + toluene P°toluene
= (0.500)(94.2 torr) + (0.500)(28.4 torr)
= 47.1 torr
= 61.3 torr
Pbenzene
+ 14.2 torr
Ptoluene
?
Ptotal
• however, mole fractions in the vapor:

Pbenzene Ptoluene
= 0.768 and = 0.232 50% benzene
Ptotal Ptotal 50% toluene
vapor composition: 76.8% benzene and 23.2% toluene
Ideal Solutions
• ideal solution = a solution in Vapor pressure

which the solvent-solute of pure B (when B = 1.0)
interactions are similar in Vapor pressure
magnitude to both the solute- of pure A
(when A = 1.0)
solute interactions and the
solvent-solvent interactions
Partial pressure
• a solution that obeys Raoult’s law of component B
at all concentrations of solute and
solvent
Partial pressure
• consider a mixture of 2 volatile of component A
liquids (A and B)

Nonideal Solutions and Deviations from Raoult’s Law
© 2018 Pearson Education, Inc. © 2018 Pearson Education, Inc.

negative deviation positive deviation
• when the solute-solvent interactions • when the solute-solvent interactions
are significantly stronger than the are significantly weaker than the
solvent-solvent interactions solvent-solvent interactions
• What amount of sucrose (C12H22O11) should be added to 5.83 mol water to lower the
vapor pressure of water at 50 °C to 72.0 torr? The vapor pressure of pure water at 50
°C is 92.6 torr. 1.67 mol sucrose
• What mass of carbon tetrachloride (CCl4) is needed to dissolve 356 g iodine (I2(s)) so
that the vapor pressure of CCl4 decreases by 25.0 % its initial amount? 647 g CCl4
• Equal masses of carbon disulfide (CS2) and acetone (CH3COCH3) are mixed at 35 °C.
What is the vapor pressure of the resulting solution? The vapor pressures of pure
carbon disulfide and acetone at 35 °C are 515 torr and 332 torr, respectively. 411 torr
• A solution of benzene and toluene at 25 °C exerts a total vapor pressure of 66.6 torr.
What is the mole fraction of benzene in the vapor phase? The vapor pressures of pure
benzene and toluene at 25 °C are 94.2 torr and 28.4 torr, respectively. 0.821
Colligative Property – Freezing Point Depression
• when a solute is dissolved in a solvent, the
freezing point of the solvent decreases
• the solution must be brought to a lower temperature
for it to freeze
• the reason why we use salt on the roads to prevent ice
DTf = m × Kf
• DTf = change in freezing point (in °C) from the freezing point of the pure
solvent (FPsolvent – FPsolution)
• m = molality of the solution
• Kf = freezing point depression constant for the solvent
the more concentrated the solution, the more the freezing point is lowered
Colligative Property – Boiling Point Elevation
• when a solute is dissolved in a solvent, the boiling
point of the solvent increases
• the solution must be brought to a higher temperature
for it to boil
• why we use coolant rather than pure H2O in engines
DTb = m × Kb
• DTb = change in boiling point (in °C) from the boiling point of the pure
solvent (BPsolution – BPsolvent)
• m = molality of the solution
• Kb = boiling point elevation constant for the solvent
the more concentrated the solution, the more the boiling point is raised
Kf and Kb Values
• values depend on the solvent

• don’t memorize these
Why Boiling Point Elevation and Freezing Point Depression?
• adding a solute lowers the vapor pressure of a solvent and changes

the phase diagram
Colligative Property – Osmotic Pressure
• osmosis = the flow of solvent across a semipermeable membrane from a solution
of low concentration into a solution of high concentration
• semipermeable membrane = allows the flow of solvent particles but not the flow
of solute
• the driving force is dilution of the more concentrated solution by the more dilute
solution
Colligative Property – Osmotic Pressure (continued)
• osmotic pressure (P) = the amount of pressure needed to keep

osmotic flow from taking place
P = MRT
• P = osmotic pressure (atm)
• M = molarity of the solution (mol/L)
• R = gas constant 0.08206 Latm/molK
• T = temperature (K)
Announcements for Wednesday, 25JAN2023
For those who just registered:
• Check Canvas Announcements and e-mails often and read through all the
posted material
For everyone:
• If you already have the textbook from Chem 161, you still must opt out this
semester so that you are not charged a second time

• What amount of sucrose (C12H22O11) should be added to 5.83 mol water to lower the
vapor pressure of water at 50 °C to 72.0 torr? The vapor pressure of pure water at 50
°C is 92.6 torr. 1.67 mol sucrose
• What mass of carbon tetrachloride (CCl4) is needed to dissolve 356 g iodine (I2(s)) so
that the vapor pressure of CCl4 decreases by 25.0 % its initial amount? 647 g CCl4
• Equal masses of carbon disulfide (CS2) and acetone (CH3COCH3) are mixed at 35 °C.
What is the vapor pressure of the resulting solution? The vapor pressures of pure
carbon disulfide and acetone at 35 °C are 515 torr and 332 torr, respectively. 411 torr
• A solution of benzene and toluene at 25 °C exerts a total vapor pressure of 66.6 torr.
What is the mole fraction of benzene in the vapor phase? The vapor pressures of pure
benzene and toluene at 25 °C are 94.2 torr and 28.4 torr, respectively. 0.821
the Van’t Hoff Factor (i)
• ionic and acidic solutes produce multiple solute particles for each formula unit or
molecule
• remember that colligative properties depend only on number of solute particles
• theoretical van’t Hoff factor (i) = the ratio of moles of solute particles to moles of
formula units/molecules dissolved
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑎𝑐𝑡𝑢𝑎𝑙𝑙𝑦 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑖=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑢𝑛𝑖𝑡𝑠 𝑜𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑
• for example: 1 mole HF is added to 1 L water and 50% of the molecules
dissociate into H+ and F–. What is value of i for this solution?
0.5 mol H+
50% dissociates
0.5 mol F–
1.5 mol 𝟏. 𝟓 𝐦𝐨𝐥
1 mol HF particles 𝐢= = 𝟏. 𝟓
𝟏 𝐦𝐨𝐥
0.5 mol HF
50% undissociated
• if the solute dissociates 100%, the theoretical Van’t Hoff factor equals the
number of ions in one unit of the compound
Percent Dissociation and the Van’t Hoff Factor
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑖=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑢𝑛𝑖𝑡𝑠 𝑜𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑
derivation not shown
𝑖−1
% 𝐷𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 = × 100%
𝑖max − 1
imax = iexpected (100% dissociation)
i = iobserved = imeasured
iexpected vs. imeasured
• the observed/measured van’t Hoff factor can be less than the expected value
• due to ion pairing
• ion pairing = oppositely charged ions associate with each other in solution

Colligative Properties – Electrolytic Solutes
• if the solute dissociates when added to a solvent, the Van’t Hoff
factor needs to be included
𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
• Psolution = P°solvent
𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡 + 𝒊×𝑛𝑠𝑜𝑙𝑢𝑡𝑒
• ∆𝑇𝑓 = 𝒊𝑚𝐾𝑓
• ∆𝑇𝑏 = 𝒊𝑚𝐾𝑏
• Π = 𝒊𝑀𝑅𝑇
• for nonelectrolytic solutes, i = 1

• What mass of CaCl2 should be dissolved in 25.0 kg water so that the solution freezes at
–1.50 °C? Assume 100% dissociation. For water, Kf = 1.86 °C/m. 746 g
• What amount of benzene (C6H6) is needed to dissolve 2.10 mol I2(s) to form a solution
that boils at 83.7 °C? For benzene, the normal boiling point is 80.1 °C and Kb = 2.53
°C/m. 19 mol
• What is the osmotic pressure at 25 °C of an aqueous methanol (CH3OH) solution that

boils at 102.52 °C? The density of the solution is 0.963 g/mL. For water, Kb = 0.512
°C/m. 100. atm
• Challenging: At 80 °C, 2.00 mol HF was added to 20.0 mol water, resulting in a solution
with a vapor pressure of 314.3 mmHg. The vapor pressure of pure water at 80 °C is
355.1 mmHg. What percentage of HF dissociated? 30 %
Chapter 14: Chemical Kinetics
• How is the rate of a reaction defined and measured?
• How can the rate of a reaction be described mathematically?
• What factors influence the rate of a reaction and how are these factors
mathematically related to reaction rate?
• How do reactions proceed from reactants to products on the molecular level?
• What are reaction mechanisms and how are they determined?
• How do catalysts change the rate of a reaction?
for Chapter 14
• reaction stoichiometry – Ch 7
• concentration, molarity, solution stoichiometry – Ch 8
• energy, enthalpy, Hess’s law – Ch 9
• gas pressure, ideal gas law, mole fraction, partial pressure,
gas mixtures, gas stoichiometry, kinetic theory – Ch 10
Kinetics – An Overview
• chemical kinetics = the study of the rates/speeds of reactions
• how long does it take for reactants to convert to products?
• what factors impact the rate of a reaction and how can they be changed?
The Collision Model of Kinetics – An Overview
• collision model = a reaction takes place between particles when they
collide
• matter on the atomic level is in
constant motion
• during the collision, bonds can be
broken and new bonds can be made
• any factors that increase the
frequency and/or energy of collisions
between particles will increase the
rate of the reaction
• more collisions = faster rate
• higher energy collisions = faster rate © 2018 Pearson Education, Inc.
Factors Impacting Reaction Rates – An Overview
several factors will impact the speed of a reaction
1. concentration of reactants
• higher concentration = more frequent collisions
2. temperature of the reaction
• higher temperature = more energetic collisions
• enough energy must be supplied to break bonds
3. structure and relative orientation of colliding particles
• colliding particles sometimes must approach each other in a very specific way
• for example: H(g) + HCl(g) → H2(g) + Cl(g)
each of these factors will be studied in more depth in the next few lectures
Defining a Reaction Rate
• the rate of a reaction is measured as the change in amount of a
reactant or product over time
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑎𝑚𝑜𝑢𝑛𝑡 ∆𝑎𝑚𝑜𝑢𝑛𝑡 𝑎𝑚𝑜𝑢𝑛𝑡𝒇𝒊𝒏𝒂𝒍 −𝑎𝑚𝑜𝑢𝑛𝑡𝒊𝒏𝒊𝒕𝒊𝒂𝒍
• 𝑟𝑎𝑡𝑒 = = =
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒 ∆𝑡𝑖𝑚𝑒 𝑡𝑖𝑚𝑒𝒇𝒊𝒏𝒂𝒍 −𝑡𝑖𝑚𝑒𝒊𝒏𝒊𝒕𝒊𝒂𝒍
• usually change in molar concentration (since molarity ∝ moles)
• for example: H2(g) + I2(g) → 2 HI(g)

• rate of change in concentration of hydrogen
∆[𝐻2 ] 𝐻2 𝒇𝒊𝒏𝒂𝒍 − 𝐻2 𝒊𝒏𝒊𝒕𝒊𝒂𝒍
=
∆𝑡 𝑡𝒇𝒊𝒏𝒂𝒍 − 𝑡𝒊𝒏𝒊𝒕𝒊𝒂𝒍
there are three species in the above reaction; which do we use to

define the reaction rate?
Measuring Reaction Rates – an Illustration
Starting Conditions: 4.00 M [X]; no Y or Z present
Person Person Person
→ Y +2C
XA→B+ 2Z
1 2 3
9.00
time [X] [Y] [Z] 8.00 [Z]
(min) (M) (M) (M) 7.00
Concentration (M)
0 4.00 0.00 0.00 6.00
10 2.83 1.17 2.34
5.00
20 2.00 2.00 4.00
30 1.41 2.59 5.17 4.00 [Y]
40 1.00 3.00 6.00 3.00
50 0.707 3.29 6.59 2.00
60 0.500 3.50 7.00 1.00
70 0.354 3.65 7.29 0.00 [X]
…
0 20 40 60 80 100 120 140

120 0.063 3.94 7.88 Time (min)
The three researchers each calculate a reaction rate based on their specific data…
Measuring Reaction Rates – an Illustration (continued)
Let’s focus on the change in concentrations over the first 10 minutes to determine the starting reaction rate
X → Y + 2Z
Person 1 Person 2 Person 3
Person Person Person
1 2 3
∆[𝑋] 2.83 − 4.00𝑀 ∆[𝑌] 1.17 − 0𝑀 ∆[𝑍] 2.34 − 0𝑀
time [X] [Y] [Z] = = =
∆𝑡 10 − 0 𝑚𝑖𝑛 ∆𝑡 10 − 0 𝑚𝑖𝑛 ∆𝑡 10 − 0 𝑚𝑖𝑛
(min) (M) (M) (M)
0 4.00 0.00 0.00 −0.117 𝑀/𝑚𝑖𝑛 +0.117 𝑀/𝑚𝑖𝑛 +0.234 𝑀/𝑚𝑖𝑛
10 2.83 1.17 2.34

20 2.00 2.00 4.00 Problem! We have three different scientists giving three
30 1.41 2.59 5.17 different numerical rates for the same exact reaction.
1. the signs are different and depends on whether a reactant or a product
40 1.00 3.00 6.00 is monitored
50 0.707 3.29 6.59 • reactants will lead to negative values whereas products will lead to
positive values
2. the magnitudes (i.e., absolute values) are different because of the
stoichiometry of the reaction
Generalized Reaction Rate
• the solution is to use the stoichiometric coefficients to normalize the
individual changes in concentration to give us a generalized rate of
the reaction
• Consider the generic reaction
aA + bB→ cC + dD
• where A and B are reactants, C and D are products
• a, b, c, and d are the balanced coefficients
1∆ A 1∆ B 1∆ C 1∆ D
𝑔𝑒𝑛𝑒𝑟𝑎𝑙𝑖𝑧𝑒𝑑 𝑅𝑎𝑡𝑒 = − =− = =
𝒂 ∆𝑡 𝒃 ∆𝑡 𝒄 ∆𝑡 𝒅 ∆𝑡
• the negative signs are used for reactants so that the rate becomes (+)
• the rate of a reaction is a positive value by convention
Generalized Reaction Rate (continued)
• let’s apply this to the previous scenario
X → Y + 2Z
∆[𝐗] ∆[𝐘] ∆[𝐙]
= −0.117 𝑀/𝑚𝑖𝑛 = +0.117 𝑀/𝑚𝑖𝑛 = +0.234 𝑀/𝑚𝑖𝑛
∆𝑡 ∆𝑡 ∆𝑡
1∆ 𝐗 1∆ 𝐘 1∆ 𝐙
Rate = − = =
𝒂 ∆t 𝒃 ∆t 𝒄 ∆t
1 1 1
Rate = − (−0.117) = (+0.117) = (+0.234)
𝟏 𝟏 𝟐
generalized Rate = +0.117 𝑀/min
All three researchers now give the same rate of reaction

Rates – Average vs. Instantaneous
• average rate = the rate of a X → Y + 2Z
reaction over a time tangent at t = 40 min
interval
• the average rate of a
reaction can change as the
reaction proceeds
• instantaneous rate = the
rate of the reaction at a
specific instant of time
• equal to the slope of the
tangent at that time point
on a curve of concentration
vs. time
7.00 − 4.00𝑀
𝐴𝑣𝑔 𝑟𝑎𝑡𝑒 = = 0.075 𝑀/𝑚𝑖𝑛
60 − 20 𝑚𝑖𝑛
Approximating Instantaneous Rate from Average Rate
• the instantaneous rate at a given time can be approximated by taking the average
rate over very narrow time interval centered around the time-point of interest
A → products
• Give the best approximation for the instantaneous rate of change of [A] at 30 s from
the given data
time (s) [A] (M)
0 4.00 𝑖𝑛𝑠𝑡𝑎𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑟𝑎𝑡𝑒 𝒂𝒕 𝟑𝟎 𝒔
10 2.83 𝟏. 𝟎𝟎 𝑴 − 𝟐. 𝟎𝟎 𝑴
20 2.00 𝑨𝒗𝒈 𝒓𝒂𝒕𝒆 𝒇𝒓𝒐𝒎 𝟐𝟎𝒔 𝒕𝒐 𝟒𝟎 𝒔 =
𝟐𝟎 𝒔
Dt ? Dt ? 30 Dt ? 1.41
40 1.00 = −𝟎. 𝟎𝟓𝟎 𝑴/𝒔
50 0.707
60 0.500
Try This On Your Own
• Consider the reaction N2(g) + 3 H2(g) → 2 NH3(g). A sealed 1.00-L
container initially contains 5.00 moles N2 and 5.00 moles H2. After 25.0 s,
1.50 moles NH3(g) is formed. For this time period calculate
a) the rate of change of [H2] –0.0900 M/s
b) the generalized rate of the reaction +0.0300 M/s
Announcements for Thursday, 26JAN2023
For those who just registered:
• Check Canvas Announcements and e-mails often and read through all the
posted material
For everyone:
• Week 2 Homework Assignments available on eLearning
• Graded and Timed Quizzes 2a & 2b – “Solutions” due Monday, 30JAN2023, at
6:00 PM (EST)
• If you already have the textbook from Chem 161, you still must opt out this
semester so that you are not charged a second time

• What mass of CaCl2 should be dissolved in 25.0 kg water so that the solution freezes at
–1.50 °C? Assume 100% dissociation. For water, Kf = 1.86 °C/m. 746 g
• What amount of benzene (C6H6) is needed to dissolve 2.10 mol I2(s) to form a solution
that boils at 83.7 °C? For benzene, the normal boiling point is 80.1 °C and Kb = 2.53
°C/m. 19 mol
• What is the osmotic pressure at 25 °C of an aqueous methanol (CH3OH) solution that

boils at 102.52 °C? The density of the solution is 0.963 g/mL. For water, Kb = 0.512
°C/m. 100. atm
• Challenging: At 80 °C, 2.00 mol HF was added to 20.0 mol water, resulting in a solution
with a vapor pressure of 314.3 mmHg. The vapor pressure of pure water at 80 °C is
355.1 mmHg. What percentage of HF dissociated? 30 %
• Consider the reaction N2(g) + 3 H2(g) → 2 NH3(g). A sealed 1.00-L
container initially contains 5.00 moles N2 and 5.00 moles H2. After 25.0 s,
1.50 moles NH3(g) is formed. For this time period calculate
a) the rate of change of [H2] –0.0900 M/s
b) the generalized rate of the reaction +0.0300 M/s
a) 1.50 𝑚𝑜𝑙 𝑁𝐻3 3 𝑀 𝐻2
= 1.50 𝑀 𝑁𝐻3 × = 2.25 𝑀 𝐻2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 ! 𝑜𝑣𝑒𝑟 25.0 𝑠
1.00 𝐿 2 𝑀 𝑁𝐻3
𝐻2 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 5.00 𝑀, 𝐻2 𝑓𝑖𝑛𝑎𝑙 = 5.00 − 2.25 = 2.75 𝑀
∆[𝐻2] 2.75 − 5.00 𝑀 −2.25 𝑀

= = = −0.0900 𝑀/𝑠
∆𝑡 25.0 − 0 𝑠 25.0 𝑠
1 ∆ 𝐻2 1 𝑀 1 ∆[𝑁𝐻3]
b) 𝑟𝑎𝑡𝑒 = − = − −0.0900 = +0.0300 𝑀/𝑠 (you could have also used )
3 ∆𝑡 3 𝑠 2 ∆𝑡
The Effect of Concentration on Reaction Rate
the effect of concentration on reaction rate is given by the reaction’s rate law
• rate law (AKA the differential rate law) = a mathematical equation that
expresses the relationship between the rate of a reaction and the
concentration of reactant (and, in rare cases, the concentration of product)
• MUST be experimentally determined (!)
• the order(?!?) of the reactants CANNOT be established from the balanced
coefficients
• only exception is when dealing with elementary reactions of a reaction mechanism
(more about this later)
the (differential) Rate Law
A → products
• General form of the rate law: rate = k [A]n
• k = rate constant for the reaction
• [A]n = the molar concentration of A raised to some power, n
• n is called the order of the reactant
• n commonly is 0, 1, or 2 though it could be a fraction and/or negative in rare cases
A + B → products
• General form of the rate law: rate = k [A]m[B]n
• k = rate constant for the reaction
• [A]m = the molar concentration of A raised to some power, m
• [B]n = the molar concentration of B raised to some power, n
Reaction Order (n, m…)
• the order of a reactant reflects the rate’s sensitivity to changing that
reactant’s concentration
• rates of reactions with high orders are much more sensitive to changes in
concentration than rates of reactions with low orders
• for example, consider the reaction O2(g) + 2 NO(g) → 2 NO2(g)
• the rate law is experimentally determined to be
rate = k [O2][NO]2
• the reaction is first-order with respect to O2 (m = 1)
• the reaction is second-order with respect to NO (n = 2)
• the reaction is third-order overall (m + n = 1 + 2 = 3)
The Rate Constant k
• depends on the specific reaction and the temperature
• reaction rate ∝ k
• doubling k will double the rate
• units of k depend on the overall order of the reaction
• Hypothetically, what are the units for a fourth-order rate constant?

M–3s–1
Zero Order Reaction (n = 0)
rate = k [A]0
rate = k
• zero-order k usually has units of M/s (or Ms–1)

• the reaction rate depends only on the value of k
• the rate of a zero-order reaction is constant as the reaction proceeds
• many reactions occurring on surfaces are zero-order reactions
First Order Reaction (n = 1)
rate = k [A]1
• first-order k usually has units of 1/s (or s–1)

• the rate is directly proportional to the reactant concentration
• doubling the concentration of reactant will double the rate
• decreasing the concentration by a factor of 3 will decrease the rate by a factor of 3
• the rate of a first-order reaction decreases as the reaction proceeds since
the concentration of reactant decreases
Second Order Reaction (n = 2)
rate = k [A]2
• second-order k usually has units of 1/Ms (or M–1s–1)

• the rate is directly proportional to the square of the reactant
concentration
• doubling the concentration of reactant will quadruple (i.e., 22) the rate
• tripling the concentration increases the rate by a factor of 9 (i.e., 32)
• the rate of a second-order reaction is more sensitive to changes in
concentration than the rate of a first-order reaction
Reaction Plots – Rate vs. Reactant Concentration
A → products
• zero-order reaction: the rate of
the reaction is constant as
reactant is consumed
• first-order reaction: the rate of

the reaction slows down linearly
(i.e., at a constant rate)
• second-order reaction: the rate of

the reaction slows down at a
faster pace as reactant is
consumed © 2018 Pearson Education, Inc.
Experimentally Determining Rate Laws and Reaction Orders
use “the method of initial rates”:
1. measure the initial rate of a reaction under a set of initial
concentrations for the reactant(s)
2. change the initial concentration of only one reactant (keeping the
concentrations of the other reactants constant) and measure the initial
rate under the new conditions
3. establish the order with respect to only that one reactant
4. go back and repeat the process for all the other reactants until the
order of each reactant is established
5. once all of the orders are established calculate the value of the rate
constant using the data from any one set of experiments
Method of Initial Rates – Example 1
consider the following data for the reaction: A → products
Experiment # [A]o (M) Initial Rate (M/s)
1 0.125 0.00347
2 0.325 0.0234
Establish the full rate law (including the value of k) for this reaction
0.148 = [0.125/0.325] n
Experiment 1: rate1 = k [A]n 0.00347 = k [0.125]n 0.148 = [0.385]n
Experiment 2: rate2 = k [A]n 0.0234 = k [0.325]n log(0.148) = log0.385n)
log(0.148) = n log(0.385)
rate = k [A]2 log 0.148
0.00347 = k (0.125)2 n = log 0.385 n = 2
k = 0.222 M–1s–1
rate = (0.222 M–1s–1)[A]2
Method of Initial Rates – Example 2
consider the following data for the reaction: A + B + C → products
Experiment # [A]o (M) [B]o (M) [C]o (M) Initial Rate
(M/s)
1 0.500 0.100 ↑ 2.10 0.600 ↑
2 0.500 ↑
×3
0.100 ×2 4.20 2.40 ×↑3 × 4 (or 22)
↑
3 × 2.5
0.500 0.300 2.10 no 1.80
change
4 1.25 0.100 4.20 2.40
Establish the full rate law (including the value of k) for this reaction and determine the
initial rate of this reaction when the initial concentration of each reactant is 0.950 M.
rate = (1.36 M–2s–1)[B][C]2 and 1.17 M/s rate = k [A]x [B]y [C]z = k [A]0 [B]1 [C]2 = k [B] [C]2
rate = k [B] [C]2

𝑟𝑎𝑡𝑒 0.600 𝑀Τ𝑠 𝑟𝑎𝑡𝑒 = 1.36 𝑀−2 ∙ 𝑠 −1 0.950 𝑀 0.950 𝑀 2
𝑘= 2
= 2
= 1.36 𝑀−2 ∙ 𝑠 −1
[𝐵] 𝐶 0.100 𝑀 2.10 𝑀 = 1.17 𝑀Τ𝑠
Announcements for Monday, 30JAN2023
For those who just registered for the class on Thursday:
as soon as possible to get current with the class
For everyone:
• Graded and Timed Quizzes 2a & 2b – “Solutions” due tonight at 6:00 PM (EST)
• Lockdown Browser for Hourly Exams
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• Take Practice Quiz on Canvas using lockdown browser as soon as possible
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Try This
consider the following data for the reaction: A + B → products
Experiment # [A]o (M) [B]o (M) Initial Rate (M/s)
1 0.253 8.43×10–2 5.01×10–4
↑ ↑
2 0.380 × 3 0.337 3.01×10–3 ×3
3 0.253 2.81×10–2 1.67×10–4
What are the units for the rate constant of this reaction’s rate law? M–1s–1
rate = k [A]x [B]y
1) Use Exps 1 & 3 to determine order with respect to [B] by inspection (see above)
rate = k [A]x [B]1
2) Use Exps 1 & 2 (or Exps 2 & 3) AND knowing that it is first order with respect to [B] to determine order with respect to
[A] by calculation
rate law Exp 1 Initial Rate of Exp 1 k A x B 1
= =
rate law Exp 2 Initial Rate of Exp 2 k A x B 1
x log 0.66539
0.000501 MΤs k 0.253 x 0.0843 1 0.253 x= = 1 (first order in A )
= 0.66539 = 0.253
0.00301 MΤs k 0.380 x 0.337 1 0.380 log 0.380
rate = k [A]1 [B]1 reaction is 2nd order overall; units for 2nd order reaction = M–1s–1
So far…
mathematically relates reactant

(differential) rate law
concentration (M) and
(instantaneous) rate = k [A]n
instantaneous reaction rate (M/s)
integration
(calculus)
mathematically relates
integrated rate law reactant concentration (M)
to reaction time (s, min…)
Integrated Rate Laws
• used for determining the amount of reactant
present/remaining at a certain time
• different expressions for zero-, first-, and second-order reactions
• we will only focus on integrated rate laws for reactions with
ONLY ONE reactant: A → products
• integrated rate laws for reactions with more than one reactant
(e.g., A + B → products) exist but are beyond the scope of the course
The Integrated Rate Laws
zero order first order second order
1 1
𝐴 = −𝑘𝑡 + 𝐴 𝑜 ln[𝐴] = −𝑘𝑡 + ln 𝐴 𝑜 = 𝑘𝑡 +
[𝐴] 𝐴𝑜
𝑤ℎ𝑒𝑟𝑒 𝐴 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝒑𝒓𝒆𝒔𝒆𝒏𝒕 𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕
𝑘 = 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑡 = 𝑡𝑖𝑚𝑒 𝑜𝑓 𝑖𝑛𝑡𝑒𝑟𝑒𝑠𝑡
𝐴 𝑜 = 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴
To use an integrated rate law, you MUST know the order of the reaction!!
A first-order reaction has k = 1.42×10–3 s–1. How long would it take for
the reactant concentration to change from 1.23 M to 0.625 M? 477 s
Plots of [A] vs. time
zero- vs. first- vs. second-order
the shapes of the plots of [A] vs. time depend on the order of reaction
• zero order: [A] decreases

at a constant rate and A is
consumed faster than in
first-order or second-
order
• second-order: A is
consumed slower than in
first-order

Linear Relationships of the Integrated Rate Laws
y = mx+ b
[A] = –k t + [A]o
ln[A] = –k t + ln[A]o
1/[A] = kt + 1/[A]o
© 2018 Pearson Education, Inc. © 2018 Pearson Education, Inc. © 2018 Pearson Education, Inc.
to experimentally determine order: 1) collect reactant concentration data over time
2) graph the data the three ways above 3) the plot that is linear gives the reaction order
Half-Life (t½)
• half-life = the amount of time it takes for an initial concentration of a species
to decrease by 50%
• the mathematical relationship for half-life depends on reaction order and can
be derived from the integrated rate law
𝐴𝑜
zero order 𝐴 = −𝑘𝑡 + 𝐴 𝑜 t½ =
𝐴𝑜
2𝑘
substitute 𝐴 with
2
first order ln[𝐴] = −𝑘𝑡 + ln 𝐴 ln 2 0.693
𝑜 t½ = =
rearrange and solve for t½ 𝑘 𝑘
1 1 1
second order
[𝐴]
= 𝑘𝑡 +
𝐴𝑜
t½ =
𝑘𝐴 𝑜
• note that the half-life for a first order reaction is independent of initial concentration
• knowing the value of t½ allows the calculation of the rate constant
Successive Half-Lives
100% t1 50% t2 25% t3 12.5%
[A] first [A] second [A] third [A] etc.
half-life half-life half-life
• the pattern of successive half-lives for a reaction can be used to identify order
successive
t1 t2 t3 half-lives
ln 2
first-order t½ = 1000 s 1000 s 1000 s constant
𝑘
𝐴𝑜
zero-order t½ = 1000 s 500 s 250 s decreases × 2
2𝑘
1
second-order t½ = 1000 s 2000 s 4000 s increases × 2
𝑘𝐴𝑜
Try This
→ products,
reaction, AA →
A first-order reaction, products,has
has aa half-life
half-lifeof
of
15.0 minutes. What is the rate of the reaction
reaction when
when
[A] = 0.484 M?
𝐫𝐚𝐭𝐞 = 𝓴 𝐀 𝐧
ln 𝟐
𝐫𝐚𝐭𝐞 = 𝓴 𝐀 𝟏 𝐭 𝟏ൗ =
𝟐 𝓴
= 𝟎. 𝟎𝟒𝟔𝟐 𝐦𝐢𝐧−𝟏 𝟎. 𝟒𝟖𝟒 𝐌 𝟏 ln 𝟐 𝟎. 𝟔𝟗𝟑
𝓴= =
= 𝟎. 𝟎𝟐𝟐𝟒 𝐌Τ𝐦𝐢𝐧 𝐭 𝟏ൗ 𝟏𝟓. 𝟎 𝐦𝐢𝐧
𝟐
= 𝟎. 𝟎𝟒𝟔𝟐 𝐦𝐢𝐧−𝟏
• A zero-order reaction, A → products has a rate constant = 0.174 M/min. If it takes 1.52
minutes for 20.0% of a sample of A to completely react, determine the initial concentration
of A. 1.32 M
• Consider the reaction A → products at a given temperature. A plot of 1/[A] vs. time is
found to be linear with the slope of 0.510 M–1s–1 and a y-intercept of 25.0 M–1. Calculate
the values of the first two successive half-lives for this reaction under the given conditions.
49.0 s and 98.0 s
• The decomposition of N2O5(g) at 67 °C has a rate constant of 5.80×10–3 s–1

2 N2O5(g) → 4 NO2(g) + O2(g)
A sample of pure N2O5(g) at a pressure of 4.68 atm undergoes decomposition for 145
seconds. Determine the total pressure within the reaction container at this point. Assume
constant volume and temperature. 8.67 atm
• The reaction C4H8 → 2 C2H4 has a rate constant of 2.25×10–2 s–1. What is [C2H4] after 15.0 s
if the reaction container initially contained only C4H8 at an initial concentration of 0.500 M?
0.286 M
Announcements for Wednesday, 01FEB2023
• +5 pts on Quiz total for taking Practice Quiz, –5 pts on Quiz total for not taking
Practice Quiz
• Teaching Intern (TI) Office Hours and Problem-Solving Sessions start
this week
• TI Weekly Activities schedule can be found on Canvas under “General Course
Information”

• A zero-order reaction, A → products has a rate constant = 0.174 M/min. If it takes 1.52
minutes for 20.0% of a sample of A to completely react, determine the initial concentration
of A. 1.32 M
• Consider the reaction A → products at a given temperature. A plot of 1/[A] vs. time is
found to be linear with the slope of 0.510 M–1s–1 and a y-intercept of 25.0 M–1. Calculate
the values of the first two successive half-lives for this reaction under the given conditions.
49.0 s and 98.0 s
• The decomposition of N2O5(g) at 67 °C has a rate constant of 5.80×10–3 s–1

2 N2O5(g) → 4 NO2(g) + O2(g)
A sample of pure N2O5(g) at a pressure of 4.68 atm undergoes decomposition for 145
seconds. Determine the total pressure within the reaction container at this point. Assume
constant volume and temperature. 8.67 atm
• The reaction C4H8 → 2 C2H4 has a rate constant of 2.25×10–2 s–1. What is [C2H4] after 15.0 s
if the reaction container initially contained only C4H8 at an initial concentration of 0.500 M?
0.286 M
Last Class

The Effect of Temperature and Structure/Orientation on Rate
• recall that the rate of a reaction  rate constant, k
• but on what does the actual value of k depend?
• Arrhenius equation = the mathematical relationships between the magnitude
of the rate constant and other factors (e.g., temperature, energy, etc.)
• don’t be afraid of it…
−𝐸𝑎 Τ𝑅𝑇
𝑘 = 𝐴𝑒
• k = rate constant (units depend on reaction order)
• A = frequency factor (same units as the rate constant)
• Ea = activation energy (J/mol)
• R = 8.314 J/molK
• we’ll look at some of the individual terms separately and then come back to
the overall equation…
Activation Energy (Ea)
• minimum amount of energy needed for a reaction to take place
• the energy needed to overcome the activation barrier of a reaction
• example: the fuse on a stick of dynamite
• Ea is ALWAYS a positive value since it’s an amount energy that must be

supplied/absorbed for a reaction to proceed
• At constant temperature…
• a numerically large Ea leads to a slow reaction
• a numerically small Ea leads to a fast reaction
Energy Diagram
• a plot of the relative change in energy as the reaction proceeds from
reactants to products
• activation energies and overall reaction enthalpies can be determined
activated complex
activated complex
Ea products
reactants Ea
DHrxn (–) DHrxn (+)
exothermic endothermic
products
reactants
Frequency Factor (A)
• frequency factor = the number of times a reactant APPROACHES an activation barrier
per unit time
• approaching an activation barrier is not the same as overcoming it
• only a fraction of approaches will have enough energy to overcome the barrier (more to come)
• in the collision model, the frequency factor (A) is the number of collisions with the
proper orientation that a reactant undergoes per unit time
improper orientation for Cl2 + H2 → 2 HCl
Cl2 H2 no reaction
vs.
proper orientation for Cl2 + H2 → 2 HCl
2 HCl
H2
Cl2 © 2018 Pearson Education, Inc.
Frequency Factor (A) (continued)
in the collision model, the frequency factor is composed of two
parts (A = pz)
• collision frequency (z) = number of collisions that occur per unit
time
• orientation factor (p) = the fraction of collisions having the
proper orientation for the reaction to proceed
• value of p ranges from 0 to 1
• low orientation factor = the reactants have VERY STRINGENT
ORIENTATION REQUIREMENTS
• high orientation factor = less stringent orientation requirements
Orientation Factor Illustrated
• essentially no orientation
+ requirement
• any collision between the two
Cl-atom (g) Cl-atom (g) Cl2 (g) atoms will result in a reaction
• this reaction has a high orientation
vs. factor (essentially equal to 1)
+
propene (g) Cl2 (g) 1,2-dichloropropane (g)

• very strict orientation requirement
• Cl2 MUST collide with the propene AT THE DOUBLE BOND ONLY
• this reaction has a relatively low orientation factor
Revisiting the Arrhenius Equation
𝑘 = 𝐴𝑒 −𝐸𝑎 Τ𝑅𝑇 exponential factor
frequency factor
• two parts to it: the frequency factor and the exponential factor
• recall that A = number of times the activation barrier IS APPROACHED
(but not necessarily surmounted) per unit time
• What are the possible values of the exponential factor?
• Ea, R and T are all positive numbers, so the value of the exponent will range from
0 to –
• the value of the exponential factor: 0 < 𝑒 −𝐸𝑎Τ𝑅𝑇 ≤ 1
• the exponential factor is the fraction of approaches to the activation
barrier that actually have enough energy TO SURMOUNT THE BARRIER
• the larger the exponential factor, the greater proportion of approaches leading to
a successful reaction
The Impact of Ea and T on Reaction Rate
𝐸𝑎
−𝐸−𝑅𝑇Τ𝑅𝑇
𝑘=
𝑘=𝐴𝑒𝐴 𝑒 𝑎 exponential factor
frequency factor
What is the impact of the magnitude of Ea on the exponential factor and k?

• large Ea → larger negative exponent → smaller decimal value (closer to 0) →
smaller k → slower reaction (at a given temperature)
• small Ea → smaller negative exponent → larger decimal value (closer to 1) →
larger k → faster reaction
What is the impact of the magnitude of T on the exponential factor and k?
• large T → smaller negative exponent → larger decimal value (closer to 1) →
larger k → faster reaction (at a given Ea)
• small T---larger negative exponent---smaller decimal value (closer to 0) → smaller
k → slower reaction
Linearized Form of the Arrhenius Equation
𝐸𝑎 1
𝑘 = 𝐴𝑒 −𝐸𝑎 Τ𝑅𝑇 → → ln 𝑘 = − + ln 𝐴
𝑅 𝑇
y = m x+ b
• the values of Ea and A can be established graphically

𝐸𝑎
• slope (m) = − and y-intercept (b) = ln A © 2018 Pearson Education, Inc.
𝑅
Two-Point Form of the Arrhenius Equation
𝑘2 𝐸 𝑎 1 1
ln = −
𝑘1 𝑅 𝑇1 𝑇2
• see page 610 in the textbook for derivation if interested
• shows the effect of temperature on the rate constant
• k2 is the rate constant at T2 and k1 is the rate constant at T1
• Ea = activation energy and R = 8.314 J/molK
Try This
• From the data below, collected for a first-order reaction A → B, calculate

a) the activation energy for the reaction (kJ/mol) 96.6 kJ/mol (based on T1 = 310 & T2 = 320 K)
k2 Ea 1 1 0.0140 s −1 Ea 1 1
ln = − = ln = − Ea = 9.66 × 104 JΤmol = 96.6 kJΤmol
k 1 R T1 T2 0.00434 s −1 8.314 JΤmol ∙ K 310 K 320 K
b) the rate constant for this reaction at 365 K 1.23 s–1 (based on Ea = 96.6 kJ/mol & T1 = 310 K)
k2 9.66 × 104 JΤmol 1 1
ln = − k 2 = e5.648 0.00434 s −1 = 1.23 s−1
0.00434 s −1 8.314 JΤmol ∙ K 310 K 365 K
• The rate constants for a reaction run at several temperatures was collected. A plot of ln
k vs. 1/T yielded a straight line having a slope of –1.25×104 K. What is the activation
energy for this reaction? 104 kJ/mol
• A reaction has first-order rate constants of 4.82×10–5 s–1 at 25 °C and 1.41×10–2 s–1 at 70.
°C. Calculate the rate constant at 90. °C. 0.11 s–1
• By what factor does the rate constant change for a reaction when the temperature is
increased from 115 °C to 230. °C if the reaction’s activation energy is 28.9 kJ/mol?
it increases by a factor of 7.75
• Consider the first-order decomposition reaction A → 2B + C having an activation energy

of 85.6 kJ/mol. The half-life of A is 17.5 h at 225 °C. What is the half-life of A at 166 °C?
282 h
Announcements for Thursday, 02FEB2023
• Graded and Timed Quizzes 3a & 3b – “Kinetics” due Monday, 06FEB2023, at
6:00 PM (EST)
Practice Quiz
• Teaching Intern (TI) Office Hours and Problem-Solving Sessions start this
week
• TI Weekly Activities schedule can be found on Canvas under “General Course
Information”

• The rate constants for a reaction run at several temperatures was collected. A plot of ln
k vs. 1/T yielded a straight line having a slope of –1.25×104 K. What is the activation
energy for this reaction? 104 kJ/mol
• A reaction has first-order rate constants of 4.82×10–5 s–1 at 25 °C and 1.41×10–2 s–1 at 70.
°C. Calculate the rate constant at 90. °C. 0.11 s–1
• By what factor does the rate constant change for a reaction when the temperature is
increased from 115 °C to 230. °C if the reaction’s activation energy is 28.9 kJ/mol?
it increases by a factor of 7.75
• Consider the first-order decomposition reaction A → 2B + C having an activation energy

of 85.6 kJ/mol. The half-life of A is 17.5 h at 225 °C. What is the half-life of A at 166 °C?
282 h
Summarizing Collision Model Requirements for a Reaction
• the collision between particles
must be “effective” in that the
particles must have the
necessary orientation for a
reaction to take place
• exact orientation depends on the
specific reaction
• but the proper orientation is not
enough
• the collision must also have
enough energy to overcome
the activation barrier
• if either of these two criteria are not
met, no reaction will take place
Chemical Reactions on the Molecular Level
• according to collision theory, reactants must collide for a
reaction to occur
• some simple reactions may proceed in a single step as
suggested by the balanced equation for the reaction
example: I– + CH3Br → CH3I + Br–
• the reaction occurs as a direct result of one effective collision of I– and CH3Br
• now consider the reaction: N2(g) + 3 H2(g) → 2 NH3(g)
• it is highly unlikely that this reaction occurs in one step since it would require
4 molecules to collide simultaneously while all having the proper orientations
• instead, the overall reaction is accomplished in simpler steps
• the simpler steps make up the reaction’s mechanism
Reaction Mechanisms
• a series of simple steps (i.e., elementary reactions) that
reactants go through to become the final products of a
reaction
• elementary reaction = a single reaction that cannot be
broken down into simpler steps
• the particles interact directly through a collision without any other steps
occurring
• may also consist of a single particle rearranging or decomposing
hn +
NO2 NO radical O radical

Reaction Mechanisms (continued)
• reaction mechanisms must be proposed and they must be
validated by experimental evidence
• although a mechanism can never be totally proven, it can be
discarded if it doesn’t agree with experimental observations
Two requirements that must be met for any plausible
mechanism
1. when summed, the individual steps of the mechanism
must add up to overall balanced reaction
• recall adding reactions in the context of Hess’s law…
2. the mechanism must account for the experimentally
determined rate law of the overall reaction
• sometimes a reaction can have more than one plausible mechanism
Elementary Reactions and Molecularity
• molecularity = the number of reactant particles that enter into an
elementary reaction
• represents the actual number of particles interacting in the elementary reaction
unimolecular = only one particle

needed for reaction to proceed
bimolecular = two particles need
to collide for the reaction to
proceed
termolecular = three particles

need to collide for the reaction
to occur
RARE!!
Determining the Rate Law of an Elementary Reaction
 the rate law of an elementary reaction can be
determined directly from stoichiometry

Requirement 1 – Adding Up Reactions
for the reaction 2 NO(g) + 2 H2(g) → N2(g) + 2 H2O(g)
the following mechanism is proposed
2 NO ⇌ N2O2
N2O2 + H2 → N2O + H2O
N2O + H2 → N2 + H2O
2 NO + 2 H2 → N2 + 2 H2O the themechanism adds up to
overall reaction
• In this example NO and H2 are reactants
• N2 and H2O are products
• N2O2 and N2O are reactive intermediates (or “intermediates”)
• species formed in one elementary reaction and then consumed in a subsequent step
• they typically are highly reactive and get consumed as soon as they are produced
Requirement 2 – the Mechanism’s Rate Law
• each elementary step of a mechanism has its own Ea, rate
constant, rate law, and rate associated with it
• the rate of the slowest step of the reaction mechanism
determines the rate of the entire mechanism
• the overall reaction can go no faster than the slowest step
• the slowest step of the mechanism is the rate-determining
step
• it is the step with the highest activation energy (Ea)
• the rate law of the rate-determining step must agree with
the experimentally determined rate law of the overall
reaction for a reaction mechanism to be considered plausible
Determining the Rate Law from a Mechanism
• unlike an overall reaction, the rate law of an elementary reaction
CAN be established directly from its stoichiometry
for the overall reaction H2(g) + 2 IBr(g) → I2(g) + 2 HBr(g), the
experimentally determined rate law is rate = k [H2] [IBr]
a proposed mechanism:
step 1: H2 + IBr →
k1
HI + HBr (slow) rate = k1[H2][IBr]
k2
step 2: HI + IBr → I2 + HBr (fast) rate = k2[HI][IBr]
• the rate-determining step is step 1 (i.e., the slowest step)

• the rate law of step 1 should (and does) agree with the
experimentally determined rate law for the overall reaction
• requirements 1 and 2 are met: the mechanism is plausible!
Mechanisms with a Fast Equilibrium Step
consider the proposed mechanism for the reaction
2 NO(g) + O2 (g) → 2 NO2(g)
step 1: 2 NO ⇌ N2O2 (fast)
k2
step 2: N2O2 + O2 → 2 NO2 (slow) rate = k2[N2O2][O2]
• the rate-determining step is step 2

PROBLEM: the rate law for step 2 includes [N2O2]
• N2O2 is a reactive intermediate! It doesn’t last long enough for
its concentration to be measured.
• the rate law for the overall reaction must only contain reactants
(NO and O2) and (maybe) products (NO2)
• intermediates are NOT allowed in the overall rate law
Mechanisms with a Fast Equilibrium Step (continued)
the solution: use the fact that step 1 is a fast equilibrium and substitute
[N2O2] with measurable quantities
kf
step 1: 2NO ⇌kr N2O2 (fast)
step 2: N2O2 + O2 k→
2 2 NO (slow)
2 rate = k2[N2O2][O2]
• in step 1, the forward reaction is in equilibrium with the reverse reaction

rate forward reaction = rate of reverse reaction
• if rates are equal, then the rate laws are also equal
kf [NO]2 = kr [N2O2]
• rearrange and solve for [N2O2] in terms of constants and reactant
concentrations
kf
[N2O2] = [NO]2 = k’ [NO]2 (where k’ is simply another constant number)
kr
• now substitute back into rate law for step 2 to get the overall rate law
rate = k2 [N2O2] [O2] = k2k’ [NO]2 [O2] = k [NO]2 [O2] (the overall rate law)
Announcements for Monday, 06FEB2023
• Graded and Timed Quizzes 3a & 3b – “Kinetics” due tonight at 6:00 PM (EST)
Practice Quiz

Try This
determine the overall reaction and rate law from the following
reaction mechanism
step 1: H2 ⇌ 2 H (fast equilibrium)
step 2: H + 2 NO → N2O + OH (slow)
step 3: OH + H → H2O (fast)
overall reaction: H2 + 2 NO → N2O + H2O

𝒌𝒇
rate = k [NO]2[H2]½ where k = 𝐤𝟐 ×
𝒌𝒓
Energy Diagrams of Reaction Mechanisms
• each step of a reaction transition
mechanism can be shown on state 1
an energy diagram transition
state 2
• number of energy humps =
number of elementary
Ea2
energy
reactions in the mechanism
• each step has its own
activation energy (Ea),
transition state, etc., reactants Ea1
DHrxn
• the step with the largest Ea is
rate-determining products
step 1 step 2
• note that you can establish
information about the reverse reaction progress
reactions as well
What is the rate-determining step for the reverse reaction?

Catalysts
catalyst = a chemical species that increases the rate of a reaction
• a catalyst takes part in the reaction but is not ultimately consumed
• it is introduced at the beginning of a reaction and regenerated at the end
• a catalyst LOWERS THE ACTIVATION ENERGY

of the reaction by changing the mechanism
of the reaction
• reactants convert into products via a lower
energy pathway
• a homogeneous catalyst is in the same
phase/physical state as the reactants
• decomposition of O3(g) catalyzed by gaseous
chlorine atoms
• a heterogeneous catalyst is in a different
phase than the reactants
• hydrogenation of ethene gas on the surface of a
solid palladium catalyst

Catalysts and Reaction Rates
a catalyst speeds up a chemical reaction by lowering the activation energy
• the value of the rate constant, k, is increased
• relationship given by the Arrhenius equation
−Ea ΤRT
k = Ae
k2 = rate constant of the Ea2 = activation energy of the

catalyzed reaction 𝐤𝟐 𝐄𝐚𝟏 − 𝐄𝐚𝟐 catalyzed reaction
k1 = rate constant of the ln = Ea1 = activation energy of the
uncatalyzed reaction
𝐤𝟏 RT uncatalyzed reaction
shows the impact of a catalyst on the reaction rate at a given temperature (T)
Heterogeneous Catalysis – Alkene Hydrogenation
• a very common and pertinent reaction in organic chemistry
H2(g) + H2C=CH2(g) → H3C–CH3(g)
• the catalyzed reaction takes place on the surface of a metal such as palladium,
platinum, or nickel

Biological Catalysts
• enzyme = biological catalyst that greatly increases the rate of a specific
biochemical reaction
• the biochemical molecule (i.e., the “substrate”) binds to the active site of an
enzyme to form an enzyme-substrate complex
• the binding occurs in a lock-and-key manner
• products are released from the complex and the enzyme is regenerated

Try This
The presence of a catalyst reduces the activation energy of a certain
reaction from 100. to 50. kJ/mol. By what factor does the rate of
the reaction increase at 127 °C, all other factors being equal?
𝐤𝟐
= 𝟑. 𝟒 × 𝟏𝟎𝟔
𝐤𝟏
k2 Ea1 − Ea2
ln =
k1 RT
k2 100. −50. kJ/mol

ln =
k1 (0.008314 kJ )(127 + 273)
molK
k2
= e15.03 = 3.4 × 106
k1
• Exam I is Wednesday, 15FEB2023, 9:20-10:50 PM (EST)
• Coverage: Chapters 13-14; exam consists of 25 questions (mixture of open-answer,
multiple-choice, etc.); see “Other Resources” on Canvas for periodic table and formula
sheet to be used on the exam
• See Canvas announcement from Feb 7 about Exam Locations
• A working, fully charged laptop will be required to take the exam
• Make sure you know how to correctly input numerical answers
• Practice Exam 1 on Canvas
• Lockdown Browser Required!
• located on the “Quizzes” tab
• for maximum benefit, only give yourself 90 minutes and take it under exam conditions
• Practice Quiz on Canvas must be completed by Friday, 10FEB2023, to get 5 points added
to your Quiz total. If not, then 5 points will be deducted from your Quiz total.

Chapter 15: Chemical Equilibrium
• What is the equilibrium state and how is it connected to reaction rates?
• What does the equilibrium constant for a reaction tell us about the reactions
tendency to go in a certain direction?
• How is an equilibrium constant calculated, and how does changing the direction
and/or stoichiometry of the reaction impact its equilibrium constant?
• How are equilibrium concentrations calculated using an ICE table and a
equilibrium constant?
• How do we determine if a reaction is at equilibrium, and if it is not, which
direction will the reaction go to achieve equilibrium
• What mathematical approximations can be made when a reaction has either a
very large equilibrium constant or a very small equilibrium constant?
• How can a system be taken out of equilibrium and how will the system respond?
for Chapter 15
• concentration, molarity – Ch 8
• energy, enthalpy, Hess’s law – Ch 9
• gas pressure, ideal gas law, mole fraction, partial pressure,
gas mixtures, gas stoichiometry, kinetic theory – Ch 10
Assumptions About Reactions Thus Far…
• recall stoichiometry from Chapter 7
N2(g) + 3 H2(g) → 2 NH3(g)
• up until this point (and without knowing it) we’ve been making the
assumptions that:
1. the reaction only goes in the direction indicated by the equation
2. completion of the reaction occurs when the limiting reactant(s) is
completely consumed
• i.e., only products remain and absolutely no reactants are left (assuming all
reactants were limiting)
• the truth is that this was an oversimplification…
Reversible Reactions
• the truth is that many reactions are reversible
initially some HI forms some H2 and I2 re-forms
• some reactions may be reversible to such a small extent that they

would appear un-reversible to the naked eye
Dynamic Equilibrium
dynamic equilibrium = the condition in which the rate of the forward

reaction equals the rate of the reverse reaction
• the concentrations of the product(s) and the reactant(s) no longer change
• on the molecular level, however, both reactions continue to occur
• both products AND reactants are present (to some extent)
What Equilibrium Is NOT
• it is NOT a ceasing of molecular activity
• the reactions do not stop!
• it is NOT a state where all of the concentrations are the same
≠
• at equilibrium, [reactants] [products] !!
• in fact in the vast majority of the cases, the concentrations are different
• the concentrations of reactants and products at equilibrium can be
experimentally measured and used to define an EQUILIBIUM
CONSTANT (K)
The Equilibrium Constant (K) and Equilibrium Expression
• equilibrium constant = the ratio AT EQUILIBRIUM of the concentrations
of the products raised to their stoichiometric coefficients divided by the
concentrations of reactants raised to their stoichiometric coefficients
• it gives the relative concentrations of products and reactants present at equilibrium
• the relationship between the expression for K and the balanced chemical equation is
called the law of mass action
consider the generic reaction aA + bB ⇌ cC + dD
C 𝑐 D 𝑑 the equilibrium
𝒆𝒒 𝒆𝒒 expression
𝐾𝒄 = 𝑎 𝑏
A B 𝒆𝒒 𝒆𝒒
[A]eq – [D]eq are the concentrations of products/reactants at equilibrium
a – d are the stoichiometric coefficients from the balanced equation
K is unitless
The Equilibrium Constant (K) (continued)
aA + bB ⇌ cC + dD
the value of K for a given reaction reflects the extent to which that
reaction goes in the forward direction to achieve equilibrium
• numerically large values of K = the

forward reaction is strongly favored
• at equilibrium, products are favored over
reactants and relatively more products will
be present in the equilibrium mixture
• numerically small values of K = the
reverse reaction is strongly favored
• at equilibrium, reactants are favored over
products
aA + bB ⇌ cC + dD
• intermediate values of K = appreciable

amounts of both reactants and products
will be present in the equilibrium
mixture
• the reaction has no significant preference in
going in either direction
• for gas phase reactions the pressures at
equilibrium can be used in place of
concentrations (more on this…)
• the value of K depends on temperature
and stoichiometry © 2018 Pearson Education, Inc.
• if you change T, you change the value of K
• for a given temperature, the equilibrium constant will always be the same regardless
of the initial concentrations of reactants and/or products
• if a reaction is not at equilibrium, it will react in the direction that will lead it to equilibrium

The Dependence of K on the Balanced Reaction
changing the direction and/or the coefficients of a reaction greatly
impacts the value of K
• the actual equilibrium expression gets modified
1. changing the direction of a reaction INVERTS the equilibrium

constant
𝑁𝑂2 4𝑒𝑞 𝑂2 𝑒𝑞
2 N2O5(g) ⇌ 4 NO2(g) + O2(g) 𝑲𝒇𝒐𝒓𝒘𝒂𝒓𝒅 =
𝑁2𝑂5 2𝑒𝑞
𝑁2𝑂5 2𝑒𝑞 1
4 NO2(g) + O2(g) ⇌ 2 N2O5(g) 𝐾𝒓𝒆𝒗𝒆𝒓𝒔𝒆 = =
𝑁𝑂2 4𝑒𝑞 𝑂2 𝑒𝑞 𝑲𝒇𝑜𝑟𝑤𝑎𝑟𝑑
The Dependence of K on the Balanced Reaction (continued)
2. multiplying the coefficients of a reaction by a certain factor raises K
to that factor
𝑁𝑂2 4𝑒𝑞 𝑂2 𝑒𝑞
2 N2O5(g) ⇌ 4 NO2(g) + O2(g) 𝑲=
𝑁2𝑂5 2𝑒𝑞
×2
𝑁𝑂2 4×𝟐 𝑂2 1×𝟐
4 N2O5(g) ⇌ 8 NO2(g) + 2 O2(g)
𝑒𝑞 𝑒𝑞
𝐾′ = = 𝑲𝟐
𝑁2𝑂5 2×𝟐
𝑒𝑞
The Dependence of K on the Balanced Reaction (continued)
3. when adding two or more individual reactions to obtain an overall
equation, the corresponding equilibrium constants are multiplied to
obtain the equilibrium constant for the overall equation
𝐵 2𝑒𝑞
reaction 1: A ⇌ 2B 𝐾1 =
𝐴 𝑒𝑞
𝐶 3𝑒𝑞
reaction 2: 2B ⇌ 3C 𝐾2 =
𝐵 2𝑒𝑞
overall reaction: A ⇌ 3C 𝐾𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = 𝐾1 × 𝐾2

Expressing K in Terms of Partial Pressures (Kp)
• for reactions in the gas phase, the equilibrium constant can be
expressed in terms of the partial pressures, in atm, of reactants and
products at equilibrium
• recall PV=nRT
• this is because the concentration of a gas in a mixture is proportional to its
partial pressure under constant temperature
for example: 2 N2O5(g) ⇌ 4 NO2(g) + O2(g)
𝑃𝑁𝑂2 4 𝑃𝑂2
𝑲𝐩 =
𝑃𝑁2𝑂5 2
remember: equilibrium pressures must be converted into atm!

How Are Kc and Kp Related?
consider 2 NO(g) + O2(g) ⇌ 2 NO2(g) where Kc = 4.67×1013 at 25 °C
𝑟𝑒𝑐𝑎𝑙𝑙 𝑃𝑉 = 𝑛𝑅𝑇
𝑁𝑂2 2 𝑃 𝑛
𝐾c = 2
→ 𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑒 𝑓𝑜𝑟 → 𝑠𝑒𝑒 𝑡𝑒𝑥𝑏𝑜𝑜𝑘 →
𝑁𝑂 𝑂2 𝑅𝑇 𝑉
Kp = Kc(RT)Dn
R = 0.08206 Latm/molK
T = temperature in Kelvin
Dn = moles of gaseous products – moles of gaseous reactants
What is Kp for the above reaction at 25 °C?
Kp = (4.67×1013) [(0.0826 L∙atm/mol∙K)(298 K)](2-3) = 1.91×1012

• Consider: CO(g) + Cl2(g) ⇌ COCl2(g) Kc = 1.2×103 at 395 °C. If the
equilibrium concentrations of Cl2 and COCl2 are the same at 395 °C,
find the equilibrium concentration of CO in the reaction.
• The equilibrium constant for the reaction ½ H2(g) + ½ I2(g) ⇌ HI(g) at

718 K is 7.07. What is the value of K at 718 K for the reaction
4 HI(g) ⇌ 2 H2(g) + 2 I2(g)?
• No “Graded and Timed Quizzes” this week
• Coverage: Chapters 13-14; exam consists of 25 questions (mixture of open-answer, multiple-
choice, etc.); see “Other Resources” on Canvas for periodic table and formula sheet to be used on
the exam
• Practice Quiz on Canvas must be completed by Friday, 10FEB2023, to get 5 points added to your
Quiz total. If not, then 5 points will be deducted from your Quiz total.

• Consider: CO(g) + Cl2(g) ⇌ COCl2(g) Kc = 1.2×103 at 395 °C. If the
equilibrium concentrations of Cl2 and COCl2 are the same at 395 °C,
find the equilibrium concentration of CO in the reaction. 8.3×10–4 M
• The equilibrium constant for the reaction ½ H2(g) + ½ I2(g) ⇌ HI(g) at

718 K is 7.07. What is the value of K at 718 K for the reaction
4 HI(g) ⇌ 2 H2(g) + 2 I2(g)? 4.00×10–4
Last Class – Kc vs. Kp
2 N2O5(g) ⇌ 4 NO2(g) + O2(g)
4
NO2 4eq O2 eq PNO2 PO2
eq eq
𝑲𝐜 = 𝑲𝐩 = 2
N2 O5 2eq PN2 O5
eq
[X]eq = concentration in mol/L (PX)eq = pressure in atm

at equilibrium at equilibrium
Kp = Kc(RT)Dn
Heterogeneous Equilibria
• we’ve established K by using equilibrium concentrations (solution phase or
gas phase) and by using equilibrium partial pressures (only gas phase)
How do we treat pure solids and pure liquids in an equilibrium reaction?
consider 2 CO(g) ⇌ CO2(g) + C(s)
• as long as there is enough C(s) for the © 2018 Pearson Education, Inc.
reaction to take place, the
equilibrium is not affected by carbon decrease
𝐶𝑂2 𝑒𝑞 C(s)
𝐾=
𝐶𝑂 2𝑒𝑞
• pure solids and liquids DO NOT
APPEAR IN THE EQUILIBRIUM CO(g) and CO2(g) [CO] and [CO2]
EXPRESSION!! at equilibrium remain
• as the reaction proceeds, the unchanged!
concentration of a pure solid or liquid
remains constant
• amount changes but volume changes
proportionally
Calculating Equilibrium Amounts of Products and Reactants
• Chem 161: we treated a reaction as going in only one direction and
going to completion
• we had to determine limiting reactant and use the limiting reactant to
calculate the amount of products formed and amount of excess reagent left
over
• for equilibrium reactions we must use a very different approach
since the concept of limiting reactant doesn’t really apply (…unless K
is extremely large)
• ICE table = a systematic approach to calculating the equilibrium
concentrations of all products and reactants from initial
concentrations and an equilibrium constant
• the relative changes in concentrations of the reactants and products is
dictated by the stoichiometry of the reaction
ICE Table Demonstrated
Consider the reaction H2(g) + I2(g) ⇌ 2 HI(g) Kc = 54.3 at 698 K
If we start with 5.00 mol H2(g) and 5.00 mol I2(g) in a 5.25-L vessel at
698 K, what will be the equilibrium concentrations of each gas?
5.00 𝑚𝑜𝑙
[H2]o = [I2]o = = 0.952 𝑀 [HI]o = 0 𝑀
5.25 𝐿
1 H2(g) + 1 I2(g) ⇌ 2 HI(g)

Initial Concentration 0.952 M 0.952 M 0M
Change – 1x – 1x + 2x
Equilibrium Concentration 0.952 - 1x 0.952 - 1x 2x + 0 = 2x
2
𝐻𝐼 𝑒𝑞 2𝑥 2
𝐾𝑐 = = 2
= 54.3 … 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑥 … 𝑥 = 0.749
𝐻2 𝑒𝑞 𝐼2 𝑒𝑞 0.952 − 𝑥
𝐻2 𝑒𝑞 = 𝐼2 𝑒𝑞 = 0.952 − 𝑥 = 0.952 − 0.749 = 0.203 𝑀
𝐻𝐼 𝑒𝑞 = 2𝑥 = 2 0.749 = 1.50 𝑀
ICE Table Demonstrated (continued)
What if we used the REVERSE REACTION as the basis for the ICE table?
1
2 HI(g) ⇌ H2(g) + I2(g) Kc = = 0.0184
54.3
2 HI(g) ⇌ 1 H2(g) + 1 I2(g)
Initial Concentration 0M 0.952 M 0.952 M
Change + 2x – 1x – 1x
Equilibrium Concentration 2x 0.952 - 1x 0.952 - 1x
𝐻2 𝐼2 0.952 − 𝑥 2
𝑒𝑞 𝑒𝑞
𝐾𝑐 = 2 = = 0.0184 … 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑥 … 𝑥 = 0.749
𝐻𝐼 𝑒𝑞 2𝑥 2
𝐻2 𝑒𝑞 = 𝐼2 𝑒𝑞 = 0.952 − 𝑥 = 0.952 − 0.749 = 0.203 𝑀
𝐻𝐼 𝑒𝑞 = 2𝑥 = 2 0.749 = 1.50 𝑀
SAME ANSWERS!
ICE Table Demonstrated
Consider the reaction H2(g) + I2(g) ⇌ 2 HI(g) Kc = 54.3 at 698 K
If we start with 5.00 mol H2(g) and 5.00 mol I2(g) in a 5.25-L vessel at
698 K, what will be the equilibrium concentrations of each gas?
5.00 𝑚𝑜𝑙
[H2]o = [I2]o = = 0.952 𝑀 [HI]o = 0 𝑀
5.25 𝐿
1 H2(g) + 1 I2(g) ⇌ 2 HI(g)

Initial Concentration 0.952 M 0.952 M 0M
Change – 1x – 1x + 2x
Equilibrium Concentration 0.952 - 1x 0.952 - 1x 2x + 0 = 2x
If a reaction is not at equilibrium, how do we know which direction the

reaction will go to get to equilibrium?
Reaching Equilibrium – the Reaction Quotient (Q)
Consider the reaction H2(g) + I2(g) ⇌ 2 HI(g) Kc = 54.3 at 698 K where
initially [H2] =0.250 M, [I2] = 0.185 M and [HI] = 2.40 M
• How do we determine if the system is already at equilibrium, and if it’s not,
which direction the reaction will go to reach equilibrium?
• reaction quotient (Q) = a value derived from INITIAL CONCENTRATIONS of
reactants and products that, when compared to K, will allow us to
determine the direction the reaction will proceed to reach equilibrium
• the expression for Q is the same as for K except that you use initial (i.e.,
non-equilibrium) concentrations of all the species
𝐻𝐼 2 2
𝒆𝒒 𝐻𝐼 𝒊𝒏𝒊𝒕𝒊𝒂𝒍
𝐾𝑐 = 𝑸𝑐 =
𝐻2 𝒆𝒒 𝐼2 𝒆𝒒 𝐻2 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝐼2 𝒊𝒏𝒊𝒕𝒊𝒂𝒍
Reaction Quotient (Q) (continued)
𝐻𝐼 2𝒊𝒏𝒊𝒕𝒊𝒂𝒍 2.40 2
𝑸𝑐 = 𝑸𝑐 = = 125
𝐻2 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝐼2 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 (0.250)(0.185)
compare the value of Q to the value of K
• if Q = K the system is already at equilibrium
• if Q < K, the system needs more products and less reactants (so that Q
becomes equal to K)
• the reaction will go right (towards products) to reach equilibrium
• if Q > K, the system needs less products and more reactants
• the reaction will go left (towards reactants) to reach equilibrium
• in the above example, Q = 125 (and is more than K = 54.3) so the reaction
will proceed to the LEFT to reach equilibrium
• HI will be consumed to form more H2 and I2
Reaction Quotient (Q) (continued)
Q = 125 and reaction goes left to reach equilibrium
What will be the equilibrium concentrations for each species?
H2(g) + I2(g) ⇌ 2 HI(g)
Initial Concentration 0.250 0.185 2.40
Change +x +x – 2x
Equilibrium Concentration 0.250 + x 0.185 + x 2.40 – 2x
2
𝐻𝐼 𝑒𝑞 2.40 − 2𝑥 2
𝐾𝑐 = = = 54.3 … 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑥 … 𝑥 = 0.0865
𝐻2 𝑒𝑞 𝐼2 𝑒𝑞 0.250 + 𝑥 (0.185 + 𝑥)
𝐻2 𝑒𝑞 = 0.250 + 𝑥 = 0.250 + 0.0865 = 0.337 𝑀
𝐼2 𝑒𝑞 = 0.185 + 𝑥 = 0.185 + 0.0865 = 0.271 𝑀
𝐻𝐼 𝑒𝑞 = 2.40 − 2𝑥 = 2.40 − 2 0.0865 = 2.23 𝑀
solve for x
2
𝐻𝐼 𝑒𝑞 2.40 − 2𝑥 2
𝐾𝑐 = = = 54.3 … 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑥
𝐻2 𝑒𝑞 𝐼2 𝑒𝑞 0.250 + 𝑥 (0.185 + 𝑥)
2.40 − 2𝑥 2 4𝑥2 − 9.60𝑥 + 5.76

= = 54.3
0.250 + 𝑥 (0.185 + 𝑥) 𝑥2 + 0.435𝑥 + 0.04625
4𝑥2 − 9.60𝑥 + 5.76 = (54.3)(𝑥2 + 0.435𝑥 + 0.04625)

4𝑥2 − 9.60𝑥 + 5.76 = 54.3𝑥2 + 23.62𝑥 + 2.511
50.3𝑥2 + 33.22𝑥 − 3.249 = 0
−𝑏 ± 𝑏2 − 4𝑎𝑐 −33.22 ± (33.22)2 −4(50.3)(−3.249)

𝑥= 𝑥=
2𝑎 2(50.3)
−33.22 ± 41.92
𝑥=
100.6
𝑥 = −0.747 𝑜𝑟 𝑥 = 0.0865
• A mixture of 3.00 mol of Cl2 and 2.10 mol I2 is initially placed into a rigid 1.00-L container at
350 °C. When the mixture has come to equilibrium, the concentration of ICl is 2.32 M. What is
the equilibrium constant for this reaction at 350 °C? Cl2(g) + I2(g) ⇌ 2 ICl(g) 3.11
• For the reaction H2S(g) + I2(s) ⇌ S(s) + 2 HI(g) Kp = 1.33×10–5 at 333 K. What will be the total
pressure of the gases above an equilibrium mixture if, at equilibrium, PHI = 0.010 × PH2S ?
0.134 atm
• Given that 2 H2O(g) + 2 Cl2(g) ⇌ 4 HCl(g) + O2(g) Kp = 0.0366 at 450 °C, determine Kc at 450 °C for
the reaction HCl(g) + ¼ O2(g) ⇌ ½ H2O(g) + ½ Cl2(g). 6.35
• The following quantities of substances are added to a 15.5-L reaction vessel at 773 K: 25.2 g CO,
15.1 g H2, 130.2 g CH4, and 125.0 g H2O. In which direction will a net reaction occur to reach
equilibrium? CO(g) + 3 H2(g) ⇌ CH4(g) + H2O(g) Kc = 102 at 773 K
Q = 35.8 < K, reaction goes to the right
• CO(g) + Cl2(g) ⇌ COCl2(g) Kp = 22.5 at 395 °C . A sample of COCl2(g) is introduced into a constant-
volume vessel at 395 °C and observed to exert an initial pressure of 0.351 atm. When equilibrium
is established, what will be the total pressure within the vessel? 0.456 atm
• H2(g) + I2(g) ⇌ 2 HI(g) Kc = 54.3 at 430 °C . What will be the concentrations of all species at
equilibrium at this temperature if we start with the following initial concentrations: [H2] =0.00623
M, [ ] = 0.00414 M, and [HI] = 0.0424 M?
[H2]eq =0.00675 M, [I2]eq = 0.00466 M, and [HI]eq = 0.0413 M
• Lecture on Wednesday will be a review
• Coverage: Chapters 13-14; exam consists of 25 questions (mixture of open-answer,
• Lockdown Browser MUST be installed on your device!

• A mixture of 3.00 mol of Cl2 and 2.10 mol I2 is initially placed into a rigid 1.00-L container at
350 °C. When the mixture has come to equilibrium, the concentration of ICl is 2.32 M. What is
the equilibrium constant for this reaction at 350 °C? Cl2(g) + I2(g) ⇌ 2 ICl(g) 3.11
• For the reaction H2S(g) + I2(s) ⇌ S(s) + 2 HI(g) Kp = 1.33×10–5 at 333 K. What will be the total
pressure of the gases above an equilibrium mixture if, at equilibrium, PHI = 0.010 × PH2S ?
0.134 atm
• Given that 2 H2O(g) + 2 Cl2(g) ⇌ 4 HCl(g) + O2(g) Kp = 0.0366 at 450 °C, determine Kc at 450 °C for
the reaction HCl(g) + ¼ O2(g) ⇌ ½ H2O(g) + ½ Cl2(g). 6.35
• The following quantities of substances are added to a 15.5-L reaction vessel at 773 K: 25.2 g CO,
15.1 g H2, 130.2 g CH4, and 125.0 g H2O. In which direction will a net reaction occur to reach
equilibrium? CO(g) + 3 H2(g) ⇌ CH4(g) + H2O(g) Kc = 102 at 773 K
Q = 35.8 < K, reaction goes to the right
• CO(g) + Cl2(g) ⇌ COCl2(g) Kp = 22.5 at 395 °C . A sample of COCl2(g) is introduced into a constant-
volume vessel at 395 °C and observed to exert an initial pressure of 0.351 atm. When equilibrium
is established, what will be the total pressure within the vessel? 0.456 atm
• H2(g) + I2(g) ⇌ 2 HI(g) Kc = 54.3 at 430 °C . What will be the concentrations of all species at
equilibrium at this temperature if we start with the following initial concentrations: [H2] =0.00623
M, [I2] = 0.00414 M, and [HI] = 0.0424 M?
[H2]eq =0.00675 M, [I2]eq = 0.00466 M, and [HI]eq = 0.0413 M
Common Mathematical Approximations with Equilibria
• often times mathematical approximations can be made to make the
calculations easier when solving for equilibrium concentrations
• the approximations are based on the size of K relative to initial
concentrations of reactants and products
• the “small-K” approximation
• the “large-K” approximation
• the logic behind these two approximations is quite different
• try to understand the logic behind the approximations so you’ll know when to
apply them properly
the Small-K Approximation
2 NO2(g) ⇌ 2 NO(g) + O2(g) Kc = 1.6×10–10 at 25 °C
[NO2]o = 0.500 M; what is the equilibrium concentration of O2(g)?
2 NO2(g) ⇌ 2 NO(g) + O2(g)
Initial Concentration 0.500 0 0
Change – 2x + 2x +x
Equilibrium Concentration 0.500 – 2x 2x x
𝑁𝑂 2𝑒𝑞 𝑂2 𝑒𝑞 2𝑥 2(𝑥) 4𝑥3 −10

𝐾𝑐 = = = = 1.6 × 10
𝑁𝑂2 2𝑒𝑞 0.500 − 2𝑥 2 0.500 − 2𝑥 2
because the magnitude of K is so small, it means that very little NO2 will decompose and that the size of the change (2x)
relative to the starting amount (0.500 M) is so small that we can neglect its effect and we can approximate (0.500 – 2x)
≈ 0.500
4𝑥3 −10
3 (0.250)(1.6 × 10−10 )
0.500 − 2𝑥 ≈ 0.500 𝑠𝑜 2
= 1.6 × 10 𝑥= = 2.2 × 10−4 𝑀 = 𝑂2
0.500 4 𝑒𝑞
Is the Small-K Approximation Valid?
the 5% rule
• in the previous problem, (0.500 – 2x) ≈ 0.500 because it was assumed
that 2x << 0.500
• for the approximation to be valid 2x should be 5% or less of 0.500
x = 2.2×10–4 so 2x = (2)(2.2×10–4) = 4.4×10–4
4.4 × 10−4
× 100% = 0.088%
0.500
2x is well below 5% of 0.500 so the approximation was totally valid

What if it wasn’t? You’d have to solve the 3rd degree polynomial…
the Large-K Approximation
Co3+(aq) + 6 NH3(aq) ⇌ Co(NH3)63+(aq) Kc = 2.3×1033 at 25 °C
[Co3+]o = 1.00 M & [NH3]o = 2.00 M; what is the equilibrium concentration of NH3(aq)?
excess reactant limiting reactant
Co3+(aq) + 6 NH3(aq) ⇌ Co(NH3)63+(aq)

Initial Concentration 1.00 2.00 0
Change 2.00/6 = – 0.33 – 2.00 + 0.33
Equilibrium Concentration 0.67 x 0.33
𝐶𝑜 𝑁𝐻3 3+
6 𝑒𝑞 0.33 33
𝐾𝑐 = 3+ 6 = (0.67) 𝑥 6
= 2.3 × 10
𝐶𝑜 𝑒𝑞 𝑁𝐻3 𝑒𝑞
because the magnitude of K is so large, we can treat the reaction as if it essentially goes to completion
to calculate amounts of products and the excess reagent, we use stoichiometry
to calculate the amount of limiting reactant remaining at equilibrium, we solve for it in an equilibrium expression
6 0.33
𝑥= 33
= 2.4 × 10−6 𝑀 = 𝑁𝐻3 𝑒𝑞
0.67 2.3 × 10
• Consider the reaction SO2Cl2(g) ⇌ SO2(g) + Cl2(g) Kc = 2.99×10–7 at 227 °C. If a
reaction mixture initially contains 0.447 M SO2Cl2, what is the equilibrium
concentrations of SO2Cl2 and SO2 at 227 °C?
[SO2Cl2]eq = 0.447 M and [SO2]eq = 3.65×10–7 M
• Consider the reaction CO(g) + 3 H2(g) ⇌ CH4(g) + H2O(g) Kc = 7.7×10–23 at 25 °C.

1.50 mol CH4 and 2.50 mol H2O are added to an empty 2.00-L container at 25 °C
and allowed to reach equilibrium. What are the equilibrium amounts (in moles)
of each species? 1.5 mol CO, 4.5 mol H2, 1.0 mol H2O, and 2.6×10–21 mol CH4
• Consider the reaction 2 COF2(g) ⇌ CO2(g) + CF4(g) Kc = 2.00 at 1000 °C. A pure
sample of COF2 is heated to 1000 °C in an evacuated container and allowed to
reach equilibrium. At equilibrium, [CF4] is 0.266 M. What percentage of the
original sample of COF2 decomposed to reach equilibrium? 73.9 %
Stressing Systems Out of Equilibrium
• when a chemical system is at equilibrium, it will stay in equilibrium unless
it is taken out of equilibrium by an outside stress
• types of outside stresses
1. changing the concentration of a reactant or product
2. changing the pressure within the reaction container
• adding or removing reactant or product
• adding an inert gas
• changing the volume of the reaction container
3. changing the temperature of the reaction
• Le Châtelier’s Principle = a chemical system, when taken out of
equilibrium, will respond to the added stress by going in a certain
direction to lessen the effect of the stress and, thereby, re-establish
equilibrium
The Effect of a Concentration Change on Equilibrium
• when a species (i.e., a reactant or product) is added to a chemical system
at equilibrium, the reaction will shift in the direction that consumes the
added species to re-establish equilibrium
• when a species is removed from a chemical system at equilibrium, the
reaction will shift in the direction that produces the removed species to
re-establish equilibrium
2 N2O5(g) ⇌ 4 NO2(g) + O2(g)
• adding N2O5 or removing NO2 or O2 will cause the reaction to go to the right
• removing N2O5 or adding NO2 or O2 will cause the reaction to go to the left
• the added or removed species must appear in the equilibrium
expression for it to impact the equilibrium
2 CO(g) ⇌ CO2(g) + C(s)
• adding or removing C(s) from the reaction at equilibrium does not impact the
equilibrium
The Effect of Pressure Change on Equilibrium
A. by adding or removing a gaseous reactants or products
• changing the partial pressure of a species has the same effect as
changing its concentration
• at constant V and T, pressure  concentration
• the species must appear in the equilibrium expression
B. by adding an inert gas

adding He(g) to N2(g) + 3 H2(g) ⇌ 2 NH3(g)
• since an inert gas does not take place in the reaction or appear in the
equilibrium expression, adding it does NOT impact the equilibrium
The Effect of Pressure Change on Equilibrium (continued)
C. by changing the volume of the reaction container
N2(g) + 3 H2(g) ⇌ 2 NH3(g)
• the reaction will go in the direction that best utilizes the space available to it
decrease increase
volume volume

© 2018 Pearson Education, Inc. reaction at equilibrium © 2018 Pearson Education, Inc.
• reaction will go towards • reaction will go towards
products to generate less reactants to generate more gas
gas to take up less volume to take up the added volume
• NH3 will be formed • N2 and H2 will be formed
• 4 moles gas → 2 moles gas • 2 moles gas → 4 moles gas
The Effect of a Temperature Change on Equilibrium
• this is the only stress that impacts the value of K for the reaction
• all of the previous stresses only impacted the value of Q, not K
• to establish the impact of temperature change , we must know the
enthalpy of reaction (DHrxn)
• exothermic = heat released
• treat heat as a product in the reaction
• endothermic = heat absorbed
• treat heat as a reactant in the reaction
• temperature change can be thought of as adding or decreasing an
amount of heat
• increasing temperature = adding heat
• decreasing temperature = removing heat
The Effect of a Temperature Change on Equilibrium (continued)
C2H4(g) + Cl2(g) ⇌ C2H4Cl2(g) + heat DH (–)
• increasing temperature will cause the rxn to go to the left
• the value of K will decrease
• decreasing the temperature will cause the rxn to go to the right
• the value of K will increase
heat + C(s) + H2O(g) ⇌ CO(g) + H2(g) DH (+)

• increasing temperature will cause the rxn to go to the right
• the value of K will increase
• decreasing the temperature will cause the rxn to go to the left
• the value of K will decrease
Temperature and Equilibrium Demonstrated
endothermic reaction

• Consider the reaction N2O4(g) ⇌ 2 NO2(g). At equilibrium, a 2.00-L reaction
vessel contains NO2 at a pressure of 0.269 atm and N2O4 at a pressure of 0.500
atm. The reaction vessel is then compressed to 1.00 L. What will be the
pressures of NO2 and N2O4 once equilibrium is re-established?
P(NO2) = 0.394 atm and P(N2O4) = 1.07 atm
• Graded and Timed Quizzes 4a & 4b – “Equilibrium” due Monday, 20FEB2023,
at 6:00 PM (EST)

• Consider the reaction SO2Cl2(g) ⇌ SO2(g) + Cl2(g) Kc = 2.99×10–7 at 227 °C. If a
reaction mixture initially contains 0.447 M SO2Cl2, what is the equilibrium
concentrations of SO2Cl2 and SO2 at 227 °C?
[SO2Cl2]eq = 0.447 M and [SO2]eq = 3.65×10–4 M
• Consider the reaction CO(g) + 3 H2(g) ⇌ CH4(g) + H2O(g) Kc = 7.7×10–23 at 25 °C.

1.50 mol CH4 and 2.50 mol H2O are added to an empty 2.00-L container at 25 °C
and allowed to reach equilibrium. What are the equilibrium amounts (in moles)
of each species? 1.5 mol CO, 4.5 mol H2, 1.0 mol H2O, and 2.6×10–21 mol CH4
• Consider the reaction 2 COF2(g) ⇌ CO2(g) + CF4(g) Kc = 2.00 at 1000 °C. A pure
sample of COF2 is heated to 1000 °C in an evacuated container and allowed to
reach equilibrium. At equilibrium, [CF4] is 0.266 M. What percentage of the
original sample of COF2 decomposed to reach equilibrium? 73.9 %
• Consider the reaction N2O4(g) ⇌ 2 NO2(g). At equilibrium, a 2.00-L reaction
vessel contains NO2 at a pressure of 0.269 atm and N2O4 at a pressure of 0.500
atm. The reaction vessel is then compressed to 1.00 L. What will be the
pressures of NO2 and N2O4 once equilibrium is re-established?
P(NO2) = 0.394 atm and P(N2O4) = 1.07 atm
Chapter 16: Acids and Bases
• What are the different definitions for acids and bases?
• How is acid strength related to molecular structure?
• What are the differences between strong and weak acids/bases?
• How do we express the strength or weak acids and weak bases?
• How are acid strengths and base strengths calculated?
• What are the acid-base properties of ions?
• How do we determine the acidity of a polyprotic acid solution?
for Chapter 16
• atomic/ionic radii trend – Ch 3
• electronegativity, bond polarity, Lewis structures, bond
energy, molecular shape – Ch 5
• molarity, dilution, solution stoichiometry, net ionic equations,
concentrations of ions, solubility rules, electrolytes, acids and
bases (strong vs. weak) – Ch 8
• functional groups – Ch 21
Recall from Chapter 8 – Acids
• Arrhenius definition of an acid = a molecular
compound that dissociates in water to generate
H+/H3O+ ions (and the associated anions)
HNO3(ℓ) + H2O(ℓ) → H3O+(aq) + NO3–(aq)
• H3O+ (hydronium ion) = H+; they are used interchangeably
• strong acids dissociate 100% in water
• HA + H2O → H+(aq) + A–(aq)
• the single-headed arrow indicates it goes to completion
• weak acids dissociate partially
• HA(aq) ⇌ H+(aq) + A–(aq)
• you should already have memorized the 6 strong acids
• HCl, HBr, HI, HNO3, HClO4, and H2SO4
Recall from Chapter 8 – Bases
• Arrhenius definition of base = a compound
(either ionic or molecular) that generates OH–
(hydroxide) ions when placed into water
strong bases = metal hydroxides (NaOH, KOH, Ca(OH)2, etc)

• they generate OH– ions directly
• NaOH + H2O → Na+(aq) + OH–(aq)
weak bases generate OH– ions indirectly by reacting with water and
removing H+
• NH3(aq) + H2O(ℓ) ⇌ NH4+(aq) + OH–(aq)
don’t confuse alcohols (R–OH) with ionic bases (NaOH)
Brønsted-Lowery Definitions of Acids and Bases
• Brønsted-Lowery acid = a proton (H+) donor
• Brønsted-Lowery base = a proton (H+) acceptor
• neutralization reaction = H+ gets transferred from an acid to a base
• you can’t have one without the other
• amphoteric = substances that can act as both an acid or a base
• example: H2O can lose a proton to become OH– or gain a proton to become
H3O+
• how water will act depends on the other species present
• conjugate acid-base pairs = two substances related to each other by
the transfer of a proton
• when an acid loses its H+, it becomes a conjugate base
• when a base gains one H+, it becomes a conjugate acid
• what are the conjugate acid and the conjugate base of the hydrogen
sulfate ion (HSO4–)? H2SO4 and SO42–, respectively
Acid Strength and Molecular Structure
Why do strong acids generate H+ ions easily whereas weak acids do not?
• note the generic structure of a monoprotic(?!?) acid: H–X
• H is the ionizable hydrogen and X represents the rest of the molecule
• to generate a proton, the H–X bond must be broken
• the more easily the H–X bond is broken, the more acidic the compound will
be
• any structural feature that can weaken the H–X bond will lead to a
stronger acid
• a strong H–X bond leads to a weak acid (or even a neutral compound)
• the role of X on acid strength depends on the type of acid
• binary acids vs. oxyacids
Acid Strength and Molecular Structure – Binary Acids
1. DOWN A GROUP in the periodic table
acid strength increases HF < HCl < HBr < HI
• down a group, atoms have larger radii, leads to weaker H–X bonds
• same trend is shown with H2O < H2S < H2Se
2. ACROSS A PERIOD in the periodic table
acid strength: CH4 (not acidic), NH3 (basic) < H2O < HF
• across a period (left-to-right), atoms have greater electronegativities,
leads to more polar bonds that are easier to break
NOTE that for binary acids, electronegativity is the more important
factor only when comparing acids within the same period and NOT
when comparing acids within the same group
Acid Strength and Molecular Structure – Oxyacids
for oxyacids, H is bonded to an oxygen (which is bonded to the rest of the molecule)
H–O–Y
• any structural features of Y that can weaken the H–O bond will lead to a
stronger acid
• acid strength increases HIO < HBrO < HClO

• electronegativity of Y: I < Br < Cl
• the more electronegative the central atom of an oxyacid, the weaker the H–O
bond
Acid Strength and Molecular Structure – Oxyacids (continued)
acid strength increases HClO < HClO2 < HClO3 < HClO4
• the more oxygens bound to the central chlorine atom, the stronger
the acid
• oxygens are highly electronegative and draw electron densities within the
covalent bonds towards them
• the H–O bond gets more polarized and weakened
• acid strength increases CH3COOH < CH2ClCOOH < CHCl2COOH < CCl3COOH
• chlorine is much more electronegative than H
• the more chlorines on the carbon adjacent to the carboxylic acid group, the
stronger the acid
• Graded and Timed Quizzes 4a – “Kinetics” & 4b – “Equilibrium” due tonight at
6:00 PM (EST)

Quantifying Acid Strength
the DISSOCIATION OF AN ACID (HA) IN WATER can be treated as an
equilibrium process
• for strong acids, the equilibrium lies FAR TO THE RIGHT towards
products (H3O+ and A–)
HA(aq) + H2O(ℓ) → H3O+(aq) + A–(aq)
• virtually no intact HA molecules exist
• 1 mole of HA dissolved in 1 L H2O would lead to [H3O+] = [A–] = 1.0 M
• for weak acids, the equilibrium lies to the left towards reactants (HA
and H2O)
• the acid consists mostly of intact HA molecules
• 1 mole of HA dissolved in 1 L H2O would lead to [H3O+] and [A–] much less
than 1.0 M
• not all weak acids dissociate to same extent, however…
Quantifying Weak Acid Strength – Ka
how much a weak acid dissociates can be quantified by the equilibrium
constant for the reaction
HA(aq) + H2O(ℓ) ⇌ H3O+(aq) + A–(aq)
• this equilibrium constant has a very specific name and a very specific
equilibrium expression: the Acid Ionization Constant (Ka)
𝐻3𝑂+ 𝒆𝒒 𝐴− 𝒆𝒒 𝐻 + 𝒆𝒒 𝐴− 𝒆𝒒
𝐾𝐚 = =
𝐻𝐴 𝒆𝒒 𝐻𝐴 𝒆𝒒
• remember: H2O(ℓ) doesn’t show up in the expression
• for strong acids in water, the value of Ka is so large that the concept of
Ka does not apply
• for weak acids: the larger the Ka, the stronger the acid
Some Common Ka Values at 25 °C

Water as an Acid and a Base – Kw
• water can act as a base or as an acid…even with itself
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq)
• water is ionizing itself (i.e., autoionizing)
• this equilibrium constant has a very specific name and equilibrium
expression: the Water Dissociation Constant (Kw) (or Ion Product
Constant for Water)
Kw = [H3O+]eq [OH–]eq = 1.0×10–14 at 25 °C
• for pure water at 25 °C, what is [H3O+]eq??
[H3O+]eq = [OH–]eq = 1.0 × 10−14 = 1.0×10–7 M at 25 °C
• for ANY aqueous solution at 25 °C
[H3O+]eq × [OH–]eq = 1.0×10–14
• if [H3O+] increases, [OH–] must necessarily decrease, and vice-versa
Designating Solutions: Neutral vs. Acidic vs. Basic
the relative concentrations of H+ and OH– present in an aqueous solution at
equilibrium can be used to designate the acidity/basicity of the solution
1. [H3O+]eq = [OH–]eq
• the solution is neutral
• at 25 °C, [H3O+] = [OH–] = 1.0×10–7 M
2. [H3O+]eq > [OH–]eq
• the solution is acidic
• at 25 °C, [H3O+] × [OH–] = 1.0×10–14 M
3. [OH–]eq > [H3O+]eq
• the solution is basic
• at 25 °C, [H3O+] × [OH–] = 1.0×10–14 M neutral
What is [OH–] in an aqueous solution at 25 °C that has [H+] = 2.6×10–9 M?
[OH–] = 3.8×10–6 M; [OH–] > [H+] so solution is basic
IMPORTANT: When you know [H3O+] at a given temperature, you indirectly
also know [OH–]
Quantifying Solution Acidity – the pH Scale
1. the acidity (or basicity) of a solution can be numerically
expressed by giving [H+] at equilibrium
• at 25 °C, 1.0 M CH3COOH(aq) has [H+]eq = 4.2×10–3 M
(acidic solution as [H+]eq > 1.0×10–7 M)
2. the acidity of a solution can be more conveniently given as

a pH
pH = –log[H3O+]eq
• for 1.0 M CH3COOH: pH = –log 4.2×10–3 = 2.38
• two significant figures in [H+] leads to two decimal places in pH
Quantifying Solution Acidity – the pH Scale (continued)
• the greater the [H+], the smaller the pH and the more acidic
the solution
In general, solutions at 25 °C
• pH = 7, neutral solution
• pH < 7, acidic solution
• pH > 7, basic solution
• What is [H3O+] of a solution having pH = 10.233?
5.85×10–11 M (three sig figs)
• none

pOH
• the acidity (or basicity) of a solution can also be given by [OH–]eq or by pOH
pOH = –log[OH–]eq
• the greater the [OH–], the smaller the pOH and the more basic the solution
recall that at 25 °C: [H3O+]eq[OH–]eq = 1×10–14

take the negative log of both sides, substitute and rearrange…
pH + pOH = 14 (at 25 °C)
always assume 25 °C unless otherwise stated
 If you know a solution’s pH, you also indirectly know [H+]eq, [OH–]eq, and pOH
• pKa = –logKa; pKb = –logKb, etc.
• What is the pOH of a solution having [H3O+] = 2.22×10–8 M?
6.346 (three decimal places)
What is the pOH of a solution having [H3O+] = 2.22×10–8 M?
Approach 1:
at 25 ℃, H3 O+ eq OH− eq = 1.00 × 10−14
1.00 × 10−14 1.00 × 10−14

OH− eq = = = 4.50 × 10 −7 M
H3 O+ eq 2.22 × 10−8
pOH = − log OH− eq = − log 4.50 × 10−7 = 6.346
Approach 2:
pH = − log H3 O+ eq = − log 2.22 × 10−8 = 7.654
at 25 ℃, pH + pOH = 14.000
pOH = 14.000 − pH = 14.000 − 7.654 = 6.346
n
neutral solution: [H+]eq = [OH–]eq
acidic solution: [H+]eq > [OH–]eq
basic solution: [OH–]eq > [H+]eq
the acidity (or basicity) of a solution can be quantified by:

1. the molar concentration of H3O+ at equilibrium ([H3O+]eq)
2. the pH of the solution (pH = –log([H+]eq)
3. the molar concentration of OH– at equilibrium ([OH–]eq)
4. the pOH of the solution (pOH = –log([OH–]eq)
for any aqueous solution at 25 °C:

[H3O+]eq[OH–]eq = 1.0×10–14
pH + pOH = 14.00
Percent Ionization/Dissociation
• all weak acids only partially dissociate, but the extent of
dissociation can differ between acids and even between
concentrations
• percent ionization of an acid (HA) = the percentage of added
acid molecules that actually dissociate into H3O+ and anion (A–)
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑖𝑜𝑛𝑖𝑧𝑒𝑑 𝑎𝑐𝑖𝑑
𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = × 100%
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑐𝑖𝑑
𝐻3𝑂+ 𝒆𝒒
= × 100%
𝐻𝐴 𝑜
Percent Ionization/Dissociation (continued)
observed calculated
% ionization
pH [H+]eq
4.2 × 10−3 𝑀
1.0 M CH3COOH 2.37 4.2×10–3 M × 100% 0.42%
1.0 𝑀
1.3 × 10−3 𝑀
0.10 M CH3COOH 2.87 1.3×10–3 M × 100% 1.3%
0.10 𝑀
4.2 × 10−4 𝑀
0.010 M CH3COOH 3.37 4.2×10–4 M × 100% 4.2%
0.010 𝑀
• the concentration of H3O+ at equilibrium decreases as acid concentration decreases

• the percent ionization of a weak acid increases as acid concentration decreases
Calculating the pH of Acid Solutions – In General
• before you calculate the pH of a solution, you have to identify the type(s) of acid(s)
present in the solution
• one strong acid in water? 0.500 M HClO4(aq)
• one weak acid in water? 0.500 M HClO2(aq)
• a mixture of strong acids in water? 0.500 M HCl(aq) + 0.845 M HNO3(aq)
• a mixture of strong and weak acids in water? 0.655 M HBr(aq) + 0.200 M HCN(aq)
• a mixture of weak acids in water? 0.100 M HNO2(aq) + 0.100 M HClO(aq)
Is there more than one source of H3O+ ions in the solution?
If there is more than one, which source(s) will predominate?
Can some sources be neglected?
• These steps are essential because they direct you to the proper
way to calculate [H3O+] at equilibrium (and ultimately pH)
What is the pH of 0.089 M HI(aq)?
2 sources of H+/H3O+: the autoionization of water & the dissociation of HI
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq)
1×10–7 M
HI(aq) + H2O(ℓ) → H3O+(aq) + I–(aq)

STRONG 100%
0.089 M 0.089 M
dissociation
ACID
𝐭𝐨𝐭𝐚𝐥 H + eq = 𝟎. 𝟎𝟖𝟗 + 𝟏 × 𝟏𝟎 −𝟕
= 0.089 M
insignificant!
pH = − log 0.089 = 𝟏. 𝟎𝟓
Calculating the pH of STRONG Acid Solutions
for a single strong acid in water
• calculate [H3O+] from the complete dissociation of the acid
• neglect the contribution of [H3O+] from the autoionization of water unless the
strong acid is very dilute (≈ 10–5 M or less)
• for example: 1.0 M HCl(aq) vs. 1.0×10–6 M HCl(aq) vs. 1.0×10–10 M HCl(aq)
• use [H3O+] to calculate resulting pH of the solution
for a mixture of two strong acids

• calculate moles of H3O+ separately from the complete dissociation of each acid
and add to get total moles of H3O+
• divide total moles of H3O+ by total volume of solution (in L) to get total [H3O+]
• use [H3O+]total to calculate resulting pH of the mixture
Calculating the pH of WEAK Acid Solutions
for a single weak acid in water
• calculate [H3O+] from the partial dissociation of the weak acid by using an ICE
table and the Ka of the acid
• typically neglect the contribution of [H3O+] from the autoionization of water
• solve for the value of x using an equilibrium expression
• look to make the small-K approximation to make the calculations simpler
Calculate the pH of a 2.5 M HNO2 solution given that its Ka = 4.6×10–4. 1.47
for a mixture of two weak acids (with each component having approximately the
same concentration)
• the weak acid with the larger Ka value will dictate the pH of the overall mixture
(provided that the Ka of the stronger acid is larger by a factor of at least several
hundred)
Calculating the pH of Strong Acid/Weak Acid Mixtures
1. calculate [H3O+] from the complete dissociation of the strong acid
• use this [H3O+] as the initial [H3O+]o in an ICE table for the weak acid dissociation
2. use ICE table to calculate [H3O+] from the partial dissociation of the weak acid to
determine if it contributes significantly to the total [H3O+]
Calculate the pH of a solution that is 0.50 M HNO3(aq) and 0.25 M HF(aq) (Ka = 3.5×10–4)
step 1: [H3O+] from HNO3 = 0.50 M HF(aq) ⇌ H+(aq) F–(aq)
step 2: [H3O+] from HF: initial 0.25 0.50 0
change –x +x +x
equilibrium 0.25 – x 0.50 + x x
(0.50 + 𝑥)(𝑥) (0.50)(𝑥)
𝐾a = = 3.5𝑥10−4 = 3.5𝑥10−4 𝑥 = 1.75𝑥10−4
(0.25 − 𝑥) (0.25)
𝐻+ 𝑡𝑜𝑡𝑎𝑙 = 0.50 + 1.75𝑥10−4 = 0.50 𝑀 𝒑𝑯 = − 𝐥𝐨𝐠 𝟎. 𝟓𝟎 = 𝟎. 𝟑𝟎
Compared to the HNO3, HF and H2O were NOT significant sources of H3O+
Strong Bases and Calculating pOH/pH
• recall that strong bases are metal hydroxides that dissolve (and
dissociate) when added to water
KOH(aq) → K+(aq) + OH–(aq)
• in this scenario the metal cation simply acts as a counterion
• using compound/solution stoichiometry, determine [OH–] at equilibrium
• report basicity as either pOH or pH (i.e., 14 – pOH)
What is the pH of 0.22 M Sr(OH)2(aq)? 13.64
• weak bases form OH– by removing H+ from water

• not all weak bases remove H+ equally well from water
• not all weak bases hold on to H+ equally strongly once they are protonated
at 6:00 PM (EST)

Quantifying Weak Base Strength – Kb
the ionization of a WEAK BASE (B) IN WATER can be treated as an
equilibrium process
B(aq) + H2O(ℓ) ⇌ BH+(aq) + OH–(aq)

equilibrium expression: the Base Ionization Constant (Kb)
𝐵𝐻 + 𝒆𝒒 𝑂𝐻− 𝒆𝒒
𝐾𝐛 =
𝐵 𝒆𝒒
• for weak bases: the larger the Kb, the stronger the base
• the base more easily takes H+ away from an acid and the more tightly it holds
on to the H+
Some Common Weak Bases and Kb Values at 25 °C

Structural Features of Weak Bases
• to act as a base, the species must have a lone pair with which it can
make a bond with H+ from the acid
• a base can either be neutral or negatively charged (but not positively charged)
• many common weak bases contain nitrogen
NH3 CH3NH2 C5H5N


Find the pH of a 0.65 M NH3(aq) (Kb = 1.76×10–5)
NH3(aq) + H2O(ℓ) ⇌ NH4+(aq) + OH–(aq)
initial 0.65 0 ≈0
change –x +x +x
equilibrium 0.65 – x x x
NH4+ eq OH− eq (x)(x) small-K x2

Kb = −5
= 1.76 × 10 = approx. = 1.76 × 10−5
NH3 eq (0.65 − x) (0.65)
x = OH − eq = 3.38 × 10 −3 M pOH = − log 3.4 × 10−3 = 2.47
𝐩𝐇 = 𝟏𝟒. 𝟎𝟎 − 𝐩𝐎𝐇 = 𝟏𝟒. 𝟎𝟎 − 𝟐. 𝟒𝟕 = 𝟏𝟏. 𝟓𝟑

• Kw at 50 °C is 5.5×10–14. Use Le Châtelier’s principle to determine whether the
autoionization of water is an endothermic or exothermic process. endothermic
• 0.336 moles of a weak, monoprotic acid added to a final volume of 2.00 L
exhibits 2.14% ionization. What is the pOH of the solution? 11.56
• A 1.35-M solution of HA(aq) has a pOH of 10.25. Determine the Ka of this acid.
2.3×10–8
• A 1.5-L solution of hypochlorous acid has pH = 4.58. What mass of HClO was
added to water to yield this solution? The Ka of HClO is 2.9×10–8. 1.9 g
• What mass of HNO3 should be added to 0.250 L of 0.00455 M HCl to give a
solution with pH = 2.000. Assume that the volume of solution does not change.
85.9 mg HNO3
• Challenging: What is the pH of a solution that is initially 6.76×10–4 M HClO4 and
1.887 M HCOOH? The Ka of HCOOH is 1.8×10–4 . 1.73
Acid/Base Related Equilibrium Constants Thus Far…
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq)
K 𝐰 (of H2 O) = H3 O+ eq OH− eq
CH3COOH(aq) + H2O(ℓ) ⇌ H3O+(aq) + CH3COO–(aq)

𝐇𝟑𝐎+ eq CH3 COO− eq
K 𝐚 of CH3 COOH =
CH3 COOH eq

NH4+ eq 𝐎𝐇 − eq
K 𝐛 of NH3 =
NH3 eq
Calculating pH – Master List of Solutions/Scenarios
you should be able to calculate the pH of the following:
✓pure water at a given temperature/Kw
✓strong acid(s) in water
✓mixture of strong/weak acids in water
✓weak acid(s) in water
✓strong base(s) in water
✓mixture of strong/weak bases in water
✓weak base(s) in water
✓a salt in water
✓
✓
✓
✓
Acid-Base Properties of Ions
• some ions have acid-base properties
and can impact the pH/pOH of
water when in solution
• we can determine the acid-base
properties of an ion by focusing of the
strength of its conjugate
Does Cl– have acid-base properties?

• the conjugate acid of Cl– is HCl (i.e.,
a strong acid).
• Cl– has no basic properties and makes
a neutral solution
• if Cl– had basic properties, HCl would
be a weak acid (NOT strong)
Acid-Base Properties of Salts
• recall that salts are ionic compounds that contain cations and anions
• salts that are soluble in water completely dissociate
• if a salt contains (an) ion(s) with acid-base properties, an aqueous
solution of the salt will have a non-neutral pH
• you must consider the acid-base properties of each ion separately
Ions that DO NOT impact the pH of a solution

1. anions that are the conjugate bases of monoprotic strong acids
• Cl–, Br–, I–, NO3–, ClO4–
2. cations that are the counterions of strong bases
• Li+, Na+, K+, Rb+, Ca2+, Sr2+, Ba2+
• example: aqueous solutions of NaCl, Ca(NO3)2, KBr have pH = 7
Acid-Base Properties of Salts (continued)
Ions that make solutions BASIC (pH > 7)
• anions that are the conjugate bases of weak acids
• F–, NO2–, ClO–, CH3COO–, CN–, etc.
consider NaF(aq)
• Na+: counterion of a strong base; doesn’t impact pH
• F–: acts as a weak base with strongest acid present (in this case,
water):
F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq)
• note that this is a Kb reaction (specifically the Kb of F–)
Ions that make solutions ACIDIC (pH < 7)
1. cations that are the conjugate acids of weak bases
• NH4+, CH3NH3+, CH3CH2NH3+, C5H5NH+, etc.
consider NH4Cl(aq)
• Cl–: conjugate base of a strong acid; doesn’t impact pH
• NH4+: acts as a weak acid with the strongest base present:
NH4+(aq) + H2O(ℓ) ⇌ H3O+(aq) + NH3(aq)
• note that this is a Ka reaction (specifically the Ka of NH4+)
2. cations that are small and highly charged

• usually period 3 and period 4
• charges of at least 2+
• the cations make a complex ion (?!?) with water
• one of the H+ on water becomes ionizable
consider Al3+(aq)
Al3+(aq) + 6 H2O(ℓ) → Al(H2O)63+(aq)
Al(H2O)63+(aq) + H2O(ℓ) ⇌ Al(H2O)5(OH)2+(aq) + H3O+(aq)
H2O(ℓ) H3O+(aq)
Al(H2O)63+(aq) Al(H2O)5(OH)2+(aq)
What if BOTH the cation and anion have acid-base properties?
consider NH4F(aq)
• NH4+ acts as a weak acid in water (Ka = 5.7×10–10)
• F– acts as a weak base in water (Kb = 2.9×10–11)
• the overall pH of a solution of NH4F can be determined by comparing the Ka of
NH4+ to the Kb of F–
Ka(NH4+) > Kb (F–)
the solution will be acidic
The Relationships of Ka, Kb, and Kw
Consider HF and F–
• they are acid-base conjugate pairs of each other
• HF acts a weak acid in water and has a Ka value associated with it
HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq)
• F– acts a weak base in water and has a Kb value associated with it
Note what happens when you add up the two reactions:
HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq) Ka of HF

F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq) Kb of F–
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq) Ka × Kb = Kw
Ka × Kb = Kw
• remember: the acid and base MUST be conjugate pairs!
for example: Ka (HF) × Kb (NH3) ≠ Kw!!
• Now, when you know a Ka, you automatically know the Kb of its
conjugate and vice-versa
• a related equation is pKa + pKb = 14.00 (where pKa = –log Ka, etc.)
Calculate the pH of 1.0 M NaF(aq) given Ka of HF = 3.5×10–4

• Which reaction should you be using?
HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq)?
OR
F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq)?

Initial 1.0 0 ≈0
Change –x +x +x
Equilibrium 1.0 – x x x
𝐾w 1×10−14
Kb of F–= = = 2.86x10−11
𝐾a HF 3.5×10−4
𝐻𝐹 𝑒𝑞 𝑂𝐻 − 𝑒𝑞 (𝑥)(𝑥) 𝑥2
Kb of F–= = = 2.86𝑥10−11 = 2.86𝑥10−11
𝐹 − 𝑒𝑞 (1.0−𝑥) (1.0)
𝑥 = 𝑂𝐻 − = 5.35𝑥10−6 𝑀
𝑝𝑂𝐻 = − log 5.35𝑥10−6 = 5.27 𝒑𝑯 = 𝟏𝟒 − 𝒑𝑶𝑯 = 𝟏𝟒 − 𝟓. 𝟐𝟕 = 𝟖. 𝟕𝟑

• What is the pH of a solution in which 1.50 g NaOH and 2.44 g Ca(OH)2
are added to enough water to give a final volume of 2.0 L? 12.71
• Calculate the pH of 0.668 M ethylamine solution (CH3CH2NH2(aq)) given

that its Kb = 5.6×10–4. 12.29
• What mass of LiNO2 needs to be added to water to give a 1.0 L-solution

with pH = 8.88? For HNO2, Ka = 4.6×10–4. 140 g
• Determine the equilibrium constant for the reaction

NH4+(aq) + OH–(aq) ⇌ H2O(ℓ) + NH3(aq)
given that the Ka of NH4+ is 5.68×10–10. 5.68×104
• Graded and Timed Quizzes 5a & 5b – “Equilibrium” due tonight at 6:00 PM (EST)

2.3×10–8
85.9 mg HNO3

that its Kb = 5.6×10–4. 12.29


✓a salt in water
✓polyprotic acid in water
✓
✓
✓
Polyprotic Acids
• some acids have more than one ionizable proton per molecule
• H2SO4(aq), H2CO3(aq), H3PO4(aq), H2SO3(aq)…
• diprotic acid = an acid with two ionizable protons
• triprotic acid = an acid with three ionizable protons
a polyprotic acid loses its H+s in a step-wise fashion

• each dissociation step has its own Ka value
• H3PO4(aq) + H2O(ℓ) ⇌ H3O+(aq) + H2PO4–(aq) Ka1 = 7.5×10–3
• H2PO4–(aq) + H2O(ℓ) ⇌ H3O+(aq) + HPO42–(aq) Ka2 = 6.2×10–8
• HPO42–(aq) + H2O(ℓ) ⇌ H3O+(aq) + PO43–(aq) Ka3 = 4.2×10–13
• it gets increasingly more difficult for any polyprotic acid to lose
subsequent H+s
Polyprotic Acids (continued)
• H2SO4 is a special case in that the first dissociation step is complete

but the second dissociation step is partial
Calculating the pH of a Polyprotic Acid Solutions
• the values of Ka for the 2nd (and 3rd ) dissociations are usually
very small compared to Ka1
• usually the pH of a polyprotic acid will be calculated solely by the
first dissociation step
• see example: calculate the pH and [S2–]eq of 0.25 M H2S(aq)
• important exception: dilute solutions of H2SO4, where the

2nd dissociation step can contribute significantly to the
overall pH of the solution
calculate the pH and [S2–]eq of 0.25 M H2S(aq)
for H2S, Ka1 = 8.9×10–8, Ka2 = 1.0×10–19
First Dissociation Step: H2S(aq) ⇌ H+(aq) + HS–(aq)

Initial 0.25 ≈0 0
Change –x +x +x
H+ eq HS −
eq (x)(x) x2
𝐾a1 = = = 8.9 × 10−8
small K
approximation
= 8.9 × 10−8
H2S eq (0.25 − 𝐱) (0.25)
x = H+ eq = HS −
eq = 1.5 × 10 −4 M
pH = − log 0.00015 = 𝟑. 𝟖𝟑 (from first dissociation step)

for H2S, Ka1 = 8.9×10–8, Ka2 = 1.0×10–19
Second Dissociation Step: HS–(aq) ⇌ H+(aq) + S2–(aq)

Initial 0.00015 0.00015 0
from 1st
Change – x dissociation + x +x
Equilibrium 0.00015 – x 0.00015 + x x
H+ eq S 2− eq (0.00015 + 𝐱)(x) small K

𝐾a2 = = = 1.0 × 10−19 approximations
HS − eq (0.00015 − 𝐱)
(0.00015)(x)
= = 1.0 × 10−19 x = 𝐒𝟐− 𝐞𝐪 = 𝟏. 𝟎 × 𝟏𝟎−𝟏𝟗 𝐌
(0.00015)
H + eq = HS − eq = 1.5 × 10−4 M
𝐩𝐇 = 𝟑. 𝟖𝟑 (determined solely from first dissociation step)
calculate the pH of 0.0100 M H2SO4(aq)
for H2SO4, Ka1 = large, Ka2 = 0.012
1st dissociation is complete: 0.0100 M H2SO4 → 0.0100 M H3O+ and 0.0100 M HSO4–
HSO4–(aq) + H2O(ℓ) ⇌ H3O+(aq) + SO42–(aq)
Initial 0.0100 0.0100 0
Change –x +x +x
Equilibrium 0.0100 – x 0.0100 + x x
𝐻3𝑂+ 𝒆𝒒
𝑆𝑂42− 𝒆𝒒 (𝟎.𝟎𝟏𝟎𝟎+𝑥)(𝑥)
Ka2 = − = = 0.012
𝐻𝑆𝑂4 𝒆𝒒 (0.0100−𝑥)
𝑥2 + 0.0100𝑥 = 0.00012 − 0.012𝑥 𝑥2 + 0.022𝑥 − 0.00012 = 0

(use quadratic formula) 𝑥 = 0.0045
𝐻3𝑂+ = 𝟎. 𝟎𝟏𝟎𝟎 + 0.0045 = 0.0145 𝑀 𝑝𝐻 = − log 0.0145 = 1.84
Lewis Acids and Bases – a Third Definition
• Gilbert Lewis further expanded the definitions of acids and bases to
include species that would not be considered acids or bases under
the Arrhenius or Brønsted-Lowry definitions
the focus is on the donation of electron pairs (not H+s)
• Lewis acid = a lone-pair acceptor
• Lewis base = a lone-pair donor
for example: H+ + ꓽNH3 → [H–NH3]+

• H+ is the Lewis acid
• NH3 is the Lewis base
• NH4+ is the resulting product
Lewis Acids and Bases (continued)
• structural feature of Lewis bases
• an atom with a lone pair to donate
• not much different than Brønsted-Lowry bases
• structural features of Lewis acids
• atoms with incomplete octets (to allow bonding with a lone pair)
B B

• atoms that can rearrange their electrons to become electron deficient (and
allow bonding with a lone pair)
H

• Determine the [NH4+]eq of 1.00 L of 0.010-M NH4Cl(aq) after the
addition of 0.500 mol NaOH(s) given that Kb of NH3 = 1.76×10–5
(assume no change in volume). [NH4+]eq = 3.6×10–7 M
Consider the following questions:
What is the relevant reaction that will be taking place after the addition
of NaOH(s) to NH4Cl(aq)? NH4+(aq) + OH–(aq) ⇌ H2O(ℓ) + NH3(aq)
What is the associated value of K for the relevant reaction?

𝟏 𝟏 𝟒
𝐊= = = 𝟓. 𝟔𝟖 × 𝟏𝟎
𝐊 𝐛 𝐨𝐟 𝐍𝐇𝟑 𝟏. 𝟕𝟔 × 𝟏𝟎−𝟓
What can be said about the magnitude of K for the relevant reaction and
how will that impact the calculations? use the Large-K approximation
• Graded and Timed Quizzes 4a – “Kinetics” & 4b – “Equilibrium” due tonight at
6:00 PM (EST)

Quantifying Acid Strength
the DISSOCIATION OF AN ACID (HA) IN WATER can be treated as an
equilibrium process
• for strong acids, the equilibrium lies FAR TO THE RIGHT towards
products (H3O+ and A–)
HA(aq) + H2O(ℓ) → H3O+(aq) + A–(aq)
• virtually no intact HA molecules exist
• 1 mole of HA dissolved in 1 L H2O would lead to [H3O+] = [A–] = 1.0 M
• for weak acids, the equilibrium lies to the left towards reactants (HA
and H2O)
• the acid consists mostly of intact HA molecules
• 1 mole of HA dissolved in 1 L H2O would lead to [H3O+] and [A–] much less
than 1.0 M
• not all weak acids dissociate to same extent, however…
Quantifying Weak Acid Strength – Ka
how much a weak acid dissociates can be quantified by the equilibrium
constant for the reaction
HA(aq) + H2O(ℓ) ⇌ H3O+(aq) + A–(aq)
equilibrium expression: the Acid Ionization Constant (Ka)
𝐻3𝑂+ 𝒆𝒒 𝐴− 𝒆𝒒 𝐻 + 𝒆𝒒 𝐴− 𝒆𝒒
𝐾𝐚 = =
𝐻𝐴 𝒆𝒒 𝐻𝐴 𝒆𝒒
• remember: H2O(ℓ) doesn’t show up in the expression
• for strong acids in water, the value of Ka is so large that the concept of
Ka does not apply
• for weak acids: the larger the Ka, the stronger the acid
Some Common Ka Values at 25 °C

Water as an Acid and a Base – Kw
• water can act as a base or as an acid…even with itself
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq)
• water is ionizing itself (i.e., autoionizing)
• this equilibrium constant has a very specific name and equilibrium
expression: the Water Dissociation Constant (Kw) (or Ion Product
Constant for Water)
Kw = [H3O+]eq [OH–]eq = 1.0×10–14 at 25 °C
• for pure water at 25 °C, what is [H3O+]eq??
[H3O+]eq = [OH–]eq = 1.0 × 10−14 = 1.0×10–7 M at 25 °C
• for ANY aqueous solution at 25 °C
[H3O+]eq × [OH–]eq = 1.0×10–14
• if [H3O+] increases, [OH–] must necessarily decrease, and vice-versa
Designating Solutions: Neutral vs. Acidic vs. Basic
the relative concentrations of H+ and OH– present in an aqueous solution at
equilibrium can be used to designate the acidity/basicity of the solution
1. [H3O+]eq = [OH–]eq
• the solution is neutral
• at 25 °C, [H3O+] = [OH–] = 1.0×10–7 M
2. [H3O+]eq > [OH–]eq
• the solution is acidic
• at 25 °C, [H3O+] × [OH–] = 1.0×10–14 M
3. [OH–]eq > [H3O+]eq
• the solution is basic
• at 25 °C, [H3O+] × [OH–] = 1.0×10–14 M neutral
What is [OH–] in an aqueous solution at 25 °C that has [H+] = 2.6×10–9 M?
[OH–] = 3.8×10–6 M; [OH–] > [H+] so solution is basic
IMPORTANT: When you know [H3O+] at a given temperature, you indirectly
also know [OH–]
Quantifying Solution Acidity – the pH Scale
1. the acidity (or basicity) of a solution can be numerically
expressed by giving [H+] at equilibrium
• at 25 °C, 1.0 M CH3COOH(aq) has [H+]eq = 4.2×10–3 M
(acidic solution as [H+]eq > 1.0×10–7 M)
2. the acidity of a solution can be more conveniently given as

a pH
pH = –log[H3O+]eq
• for 1.0 M CH3COOH: pH = –log 4.2×10–3 = 2.38
• two significant figures in [H+] leads to two decimal places in pH
Quantifying Solution Acidity – the pH Scale (continued)
• the greater the [H+], the smaller the pH and the more acidic
the solution
In general, solutions at 25 °C
• pH = 7, neutral solution
• pH < 7, acidic solution
• pH > 7, basic solution
• What is [H3O+] of a solution having pH = 10.233?
5.85×10–11 M (three sig figs)
• none

pOH
• the acidity (or basicity) of a solution can also be given by [OH–]eq or by pOH
pOH = –log[OH–]eq
• the greater the [OH–], the smaller the pOH and the more basic the solution
recall that at 25 °C: [H3O+]eq[OH–]eq = 1×10–14

take the negative log of both sides, substitute and rearrange…
pH + pOH = 14 (at 25 °C)
always assume 25 °C unless otherwise stated
 If you know a solution’s pH, you also indirectly know [H+]eq, [OH–]eq, and pOH
• pKa = –logKa; pKb = –logKb, etc.
• What is the pOH of a solution having [H3O+] = 2.22×10–8 M?
6.346 (three decimal places)
What is the pOH of a solution having [H3O+] = 2.22×10–8 M?
Approach 1:
at 25 ℃, H3 O+ eq OH− eq = 1.00 × 10−14
1.00 × 10−14 1.00 × 10−14

OH− eq = = = 4.50 × 10 −7 M
H3 O+ eq 2.22 × 10−8
pOH = − log OH− eq = − log 4.50 × 10−7 = 6.346
Approach 2:
pH = − log H3 O+ eq = − log 2.22 × 10−8 = 7.654
at 25 ℃, pH + pOH = 14.000
pOH = 14.000 − pH = 14.000 − 7.654 = 6.346
n
neutral solution: [H+]eq = [OH–]eq
acidic solution: [H+]eq > [OH–]eq
basic solution: [OH–]eq > [H+]eq
the acidity (or basicity) of a solution can be quantified by:

1. the molar concentration of H3O+ at equilibrium ([H3O+]eq)
2. the pH of the solution (pH = –log([H+]eq)
3. the molar concentration of OH– at equilibrium ([OH–]eq)
4. the pOH of the solution (pOH = –log([OH–]eq)
for any aqueous solution at 25 °C:

[H3O+]eq[OH–]eq = 1.0×10–14
pH + pOH = 14.00
Percent Ionization/Dissociation
• all weak acids only partially dissociate, but the extent of
dissociation can differ between acids and even between
concentrations
• percent ionization of an acid (HA) = the percentage of added
acid molecules that actually dissociate into H3O+ and anion (A–)
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑖𝑜𝑛𝑖𝑧𝑒𝑑 𝑎𝑐𝑖𝑑
𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = × 100%
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑐𝑖𝑑
𝐻3𝑂+ 𝒆𝒒
= × 100%
𝐻𝐴 𝑜
Percent Ionization/Dissociation (continued)
observed calculated
% ionization
pH [H+]eq
4.2 × 10−3 𝑀
1.0 M CH3COOH 2.37 4.2×10–3 M × 100% 0.42%
1.0 𝑀
1.3 × 10−3 𝑀
0.10 M CH3COOH 2.87 1.3×10–3 M × 100% 1.3%
0.10 𝑀
4.2 × 10−4 𝑀
0.010 M CH3COOH 3.37 4.2×10–4 M × 100% 4.2%
0.010 𝑀
• the concentration of H3O+ at equilibrium decreases as acid concentration decreases

• the percent ionization of a weak acid increases as acid concentration decreases
Calculating the pH of Acid Solutions – In General
• before you calculate the pH of a solution, you have to identify the type(s) of acid(s)
present in the solution
• one strong acid in water? 0.500 M HClO4(aq)
• one weak acid in water? 0.500 M HClO2(aq)
• a mixture of strong acids in water? 0.500 M HCl(aq) + 0.845 M HNO3(aq)
• a mixture of strong and weak acids in water? 0.655 M HBr(aq) + 0.200 M HCN(aq)
• a mixture of weak acids in water? 0.100 M HNO2(aq) + 0.100 M HClO(aq)
Is there more than one source of H3O+ ions in the solution?
If there is more than one, which source(s) will predominate?
Can some sources be neglected?
• These steps are essential because they direct you to the proper
way to calculate [H3O+] at equilibrium (and ultimately pH)
What is the pH of 0.089 M HI(aq)?
2 sources of H+/H3O+: the autoionization of water & the dissociation of HI
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq)
1×10–7 M
HI(aq) + H2O(ℓ) → H3O+(aq) + I–(aq)

STRONG 100%
0.089 M 0.089 M
dissociation
ACID
𝐭𝐨𝐭𝐚𝐥 H + eq = 𝟎. 𝟎𝟖𝟗 + 𝟏 × 𝟏𝟎 −𝟕
= 0.089 M
insignificant!
pH = − log 0.089 = 𝟏. 𝟎𝟓
Calculating the pH of STRONG Acid Solutions
for a single strong acid in water
• calculate [H3O+] from the complete dissociation of the acid
• neglect the contribution of [H3O+] from the autoionization of water unless the
strong acid is very dilute (≈ 10–5 M or less)
• for example: 1.0 M HCl(aq) vs. 1.0×10–6 M HCl(aq) vs. 1.0×10–10 M HCl(aq)
• use [H3O+] to calculate resulting pH of the solution
for a mixture of two strong acids

• calculate moles of H3O+ separately from the complete dissociation of each acid
and add to get total moles of H3O+
• divide total moles of H3O+ by total volume of solution (in L) to get total [H3O+]
• use [H3O+]total to calculate resulting pH of the mixture
Calculating the pH of WEAK Acid Solutions
for a single weak acid in water
• calculate [H3O+] from the partial dissociation of the weak acid by using an ICE
table and the Ka of the acid
• typically neglect the contribution of [H3O+] from the autoionization of water
• solve for the value of x using an equilibrium expression
• look to make the small-K approximation to make the calculations simpler
Calculate the pH of a 2.5 M HNO2 solution given that its Ka = 4.6×10–4. 1.47
for a mixture of two weak acids (with each component having approximately the
same concentration)
• the weak acid with the larger Ka value will dictate the pH of the overall mixture
(provided that the Ka of the stronger acid is larger by a factor of at least several
hundred)
Calculating the pH of Strong Acid/Weak Acid Mixtures
1. calculate [H3O+] from the complete dissociation of the strong acid
• use this [H3O+] as the initial [H3O+]o in an ICE table for the weak acid dissociation
2. use ICE table to calculate [H3O+] from the partial dissociation of the weak acid to
determine if it contributes significantly to the total [H3O+]
Calculate the pH of a solution that is 0.50 M HNO3(aq) and 0.25 M HF(aq) (Ka = 3.5×10–4)
step 1: [H3O+] from HNO3 = 0.50 M HF(aq) ⇌ H+(aq) F–(aq)
step 2: [H3O+] from HF: initial 0.25 0.50 0
change –x +x +x
equilibrium 0.25 – x 0.50 + x x
(0.50 + 𝑥)(𝑥) (0.50)(𝑥)
𝐾a = = 3.5𝑥10−4 = 3.5𝑥10−4 𝑥 = 1.75𝑥10−4
(0.25 − 𝑥) (0.25)
𝐻+ 𝑡𝑜𝑡𝑎𝑙 = 0.50 + 1.75𝑥10−4 = 0.50 𝑀 𝒑𝑯 = − 𝐥𝐨𝐠 𝟎. 𝟓𝟎 = 𝟎. 𝟑𝟎
Compared to the HNO3, HF and H2O were NOT significant sources of H3O+
Strong Bases and Calculating pOH/pH
• recall that strong bases are metal hydroxides that dissolve (and
dissociate) when added to water
KOH(aq) → K+(aq) + OH–(aq)
• in this scenario the metal cation simply acts as a counterion
• using compound/solution stoichiometry, determine [OH–] at equilibrium
• report basicity as either pOH or pH (i.e., 14 – pOH)
What is the pH of 0.22 M Sr(OH)2(aq)? 13.64
• weak bases form OH– by removing H+ from water

• not all weak bases remove H+ equally well from water
• not all weak bases hold on to H+ equally strongly once they are protonated
at 6:00 PM (EST)

Quantifying Weak Base Strength – Kb
the ionization of a WEAK BASE (B) IN WATER can be treated as an
equilibrium process
B(aq) + H2O(ℓ) ⇌ BH+(aq) + OH–(aq)

equilibrium expression: the Base Ionization Constant (Kb)
𝐵𝐻 + 𝒆𝒒 𝑂𝐻− 𝒆𝒒
𝐾𝐛 =
𝐵 𝒆𝒒
• for weak bases: the larger the Kb, the stronger the base
• the base more easily takes H+ away from an acid and the more tightly it holds
on to the H+
Some Common Weak Bases and Kb Values at 25 °C

Structural Features of Weak Bases
• to act as a base, the species must have a lone pair with which it can
make a bond with H+ from the acid
• a base can either be neutral or negatively charged (but not positively charged)
• many common weak bases contain nitrogen
NH3 CH3NH2 C5H5N


Find the pH of a 0.65 M NH3(aq) (Kb = 1.76×10–5)
initial 0.65 0 ≈0
change –x +x +x
equilibrium 0.65 – x x x
NH4+ eq OH− eq (x)(x) small-K x2

Kb = −5
= 1.76 × 10 = approx. = 1.76 × 10−5
NH3 eq (0.65 − x) (0.65)
x = OH − eq = 3.38 × 10 −3 M pOH = − log 3.4 × 10−3 = 2.47
𝐩𝐇 = 𝟏𝟒. 𝟎𝟎 − 𝐩𝐎𝐇 = 𝟏𝟒. 𝟎𝟎 − 𝟐. 𝟒𝟕 = 𝟏𝟏. 𝟓𝟑

2.3×10–8
85.9 mg HNO3
Acid/Base Related Equilibrium Constants Thus Far…
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq)
K 𝐰 (of H2 O) = H3 O+ eq OH− eq
CH3COOH(aq) + H2O(ℓ) ⇌ H3O+(aq) + CH3COO–(aq)

𝐇𝟑𝐎+ eq CH3 COO− eq
K 𝐚 of CH3 COOH =
CH3 COOH eq

NH4+ eq 𝐎𝐇 − eq
K 𝐛 of NH3 =
NH3 eq
✓a salt in water
✓
✓
✓
✓
Acid-Base Properties of Ions
• some ions have acid-base properties
and can impact the pH/pOH of
water when in solution
• we can determine the acid-base
properties of an ion by focusing of the
strength of its conjugate
Does Cl– have acid-base properties?

• the conjugate acid of Cl– is HCl (i.e.,
a strong acid).
• Cl– has no basic properties and makes
a neutral solution
• if Cl– had basic properties, HCl would
be a weak acid (NOT strong)
Acid-Base Properties of Salts
• recall that salts are ionic compounds that contain cations and anions
• salts that are soluble in water completely dissociate
• if a salt contains (an) ion(s) with acid-base properties, an aqueous
solution of the salt will have a non-neutral pH
• you must consider the acid-base properties of each ion separately
Ions that DO NOT impact the pH of a solution

1. anions that are the conjugate bases of monoprotic strong acids
• Cl–, Br–, I–, NO3–, ClO4–
2. cations that are the counterions of strong bases
• Li+, Na+, K+, Rb+, Ca2+, Sr2+, Ba2+
• example: aqueous solutions of NaCl, Ca(NO3)2, KBr have pH = 7
Ions that make solutions BASIC (pH > 7)
• anions that are the conjugate bases of weak acids
• F–, NO2–, ClO–, CH3COO–, CN–, etc.
consider NaF(aq)
• Na+: counterion of a strong base; doesn’t impact pH
• F–: acts as a weak base with strongest acid present (in this case,
water):
• note that this is a Kb reaction (specifically the Kb of F–)
Ions that make solutions ACIDIC (pH < 7)
1. cations that are the conjugate acids of weak bases
• NH4+, CH3NH3+, CH3CH2NH3+, C5H5NH+, etc.
consider NH4Cl(aq)
• Cl–: conjugate base of a strong acid; doesn’t impact pH
• NH4+: acts as a weak acid with the strongest base present:
NH4+(aq) + H2O(ℓ) ⇌ H3O+(aq) + NH3(aq)
• note that this is a Ka reaction (specifically the Ka of NH4+)
2. cations that are small and highly charged

• usually period 3 and period 4
• charges of at least 2+
• the cations make a complex ion (?!?) with water
• one of the H+ on water becomes ionizable
consider Al3+(aq)
Al3+(aq) + 6 H2O(ℓ) → Al(H2O)63+(aq)
H2O(ℓ) H3O+(aq)
What if BOTH the cation and anion have acid-base properties?
consider NH4F(aq)
• NH4+ acts as a weak acid in water (Ka = 5.7×10–10)
• F– acts as a weak base in water (Kb = 2.9×10–11)
• the overall pH of a solution of NH4F can be determined by comparing the Ka of
NH4+ to the Kb of F–
Ka(NH4+) > Kb (F–)
the solution will be acidic
The Relationships of Ka, Kb, and Kw
Consider HF and F–
• they are acid-base conjugate pairs of each other
• HF acts a weak acid in water and has a Ka value associated with it
HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq)
• F– acts a weak base in water and has a Kb value associated with it
Note what happens when you add up the two reactions:
HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq) Ka of HF

F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq) Kb of F–
2 H2O(ℓ) ⇌ H3O+(aq) + OH–(aq) Ka × Kb = Kw
Ka × Kb = Kw
• remember: the acid and base MUST be conjugate pairs!
for example: Ka (HF) × Kb (NH3) ≠ Kw!!
• Now, when you know a Ka, you automatically know the Kb of its
conjugate and vice-versa
• a related equation is pKa + pKb = 14.00 (where pKa = –log Ka, etc.)

• Which reaction should you be using?
HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq)?
OR
F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq)?

Initial 1.0 0 ≈0
Change –x +x +x
𝐾w 1×10−14
Kb of F–= = = 2.86x10−11
𝐾a HF 3.5×10−4
𝐻𝐹 𝑒𝑞 𝑂𝐻 − 𝑒𝑞 (𝑥)(𝑥) 𝑥2
Kb of F–= = = 2.86𝑥10−11 = 2.86𝑥10−11
𝐹 − 𝑒𝑞 (1.0−𝑥) (1.0)
𝑥 = 𝑂𝐻 − = 5.35𝑥10−6 𝑀
𝑝𝑂𝐻 = − log 5.35𝑥10−6 = 5.27 𝒑𝑯 = 𝟏𝟒 − 𝒑𝑶𝑯 = 𝟏𝟒 − 𝟓. 𝟐𝟕 = 𝟖. 𝟕𝟑


that its Kb = 5.6×10–4. 12.29


• Graded and Timed Quizzes 5a & 5b – “Equilibrium” due tonight at 6:00 PM (EST)

2.3×10–8
85.9 mg HNO3

that its Kb = 5.6×10–4. 12.29


✓a salt in water
✓
✓
✓
Polyprotic Acids
• some acids have more than one ionizable proton per molecule
• H2SO4(aq), H2CO3(aq), H3PO4(aq), H2SO3(aq)…
• diprotic acid = an acid with two ionizable protons
• triprotic acid = an acid with three ionizable protons
a polyprotic acid loses its H+s in a step-wise fashion

• each dissociation step has its own Ka value
• H3PO4(aq) + H2O(ℓ) ⇌ H3O+(aq) + H2PO4–(aq) Ka1 = 7.5×10–3
• H2PO4–(aq) + H2O(ℓ) ⇌ H3O+(aq) + HPO42–(aq) Ka2 = 6.2×10–8
• HPO42–(aq) + H2O(ℓ) ⇌ H3O+(aq) + PO43–(aq) Ka3 = 4.2×10–13
• it gets increasingly more difficult for any polyprotic acid to lose
subsequent H+s
Polyprotic Acids (continued)
• H2SO4 is a special case in that the first dissociation step is complete

but the second dissociation step is partial
Calculating the pH of a Polyprotic Acid Solutions
• the values of Ka for the 2nd (and 3rd ) dissociations are usually
very small compared to Ka1
• usually the pH of a polyprotic acid will be calculated solely by the
first dissociation step
• see example: calculate the pH and [S2–]eq of 0.25 M H2S(aq)
• important exception: dilute solutions of H2SO4, where the

2nd dissociation step can contribute significantly to the
overall pH of the solution
for H2S, Ka1 = 8.9×10–8, Ka2 = 1.0×10–19
First Dissociation Step: H2S(aq) ⇌ H+(aq) + HS–(aq)

Initial 0.25 ≈0 0
Change –x +x +x
H+ eq HS −
eq (x)(x) x2
𝐾a1 = = = 8.9 × 10−8
small K
approximation
= 8.9 × 10−8
H2S eq (0.25 − 𝐱) (0.25)
x = H+ eq = HS −
eq = 1.5 × 10 −4 M
pH = − log 0.00015 = 𝟑. 𝟖𝟑 (from first dissociation step)

for H2S, Ka1 = 8.9×10–8, Ka2 = 1.0×10–19
Second Dissociation Step: HS–(aq) ⇌ H+(aq) + S2–(aq)

Initial 0.00015 0.00015 0
from 1st
Change – x dissociation + x +x
Equilibrium 0.00015 – x 0.00015 + x x
H+ eq S 2− eq (0.00015 + 𝐱)(x) small K

𝐾a2 = = = 1.0 × 10−19 approximations
HS − eq (0.00015 − 𝐱)
(0.00015)(x)
= = 1.0 × 10−19 x = 𝐒𝟐− 𝐞𝐪 = 𝟏. 𝟎 × 𝟏𝟎−𝟏𝟗 𝐌
(0.00015)
H + eq = HS − eq = 1.5 × 10−4 M
𝐩𝐇 = 𝟑. 𝟖𝟑 (determined solely from first dissociation step)
calculate the pH of 0.0100 M H2SO4(aq)
for H2SO4, Ka1 = large, Ka2 = 0.012
1st dissociation is complete: 0.0100 M H2SO4 → 0.0100 M H3O+ and 0.0100 M HSO4–
HSO4–(aq) + H2O(ℓ) ⇌ H3O+(aq) + SO42–(aq)
Initial 0.0100 0.0100 0
Change –x +x +x
Equilibrium 0.0100 – x 0.0100 + x x
𝐻3𝑂+ 𝒆𝒒
𝑆𝑂42− 𝒆𝒒 (𝟎.𝟎𝟏𝟎𝟎+𝑥)(𝑥)
Ka2 = − = = 0.012
𝐻𝑆𝑂4 𝒆𝒒 (0.0100−𝑥)
𝑥2 + 0.0100𝑥 = 0.00012 − 0.012𝑥 𝑥2 + 0.022𝑥 − 0.00012 = 0

(use quadratic formula) 𝑥 = 0.0045
𝐻3𝑂+ = 𝟎. 𝟎𝟏𝟎𝟎 + 0.0045 = 0.0145 𝑀 𝑝𝐻 = − log 0.0145 = 1.84
Lewis Acids and Bases – a Third Definition
• Gilbert Lewis further expanded the definitions of acids and bases to
include species that would not be considered acids or bases under
the Arrhenius or Brønsted-Lowry definitions
the focus is on the donation of electron pairs (not H+s)
• Lewis acid = a lone-pair acceptor
• Lewis base = a lone-pair donor
for example: H+ + ꓽNH3 → [H–NH3]+

• H+ is the Lewis acid
• NH3 is the Lewis base
• NH4+ is the resulting product
Lewis Acids and Bases (continued)
• structural feature of Lewis bases
• an atom with a lone pair to donate
• not much different than Brønsted-Lowry bases
• structural features of Lewis acids
• atoms with incomplete octets (to allow bonding with a lone pair)
B B

• atoms that can rearrange their electrons to become electron deficient (and
allow bonding with a lone pair)
H

• Determine the [NH4+]eq of 1.00 L of 0.010-M NH4Cl(aq) after the
addition of 0.500 mol NaOH(s) given that Kb of NH3 = 1.76×10–5
(assume no change in volume). [NH4+]eq = 3.6×10–7 M
Consider the following questions:
What is the relevant reaction that will be taking place after the addition
of NaOH(s) to NH4Cl(aq)? NH4+(aq) + OH–(aq) ⇌ H2O(ℓ) + NH3(aq)
What is the associated value of K for the relevant reaction?

𝟏 𝟏 𝟒
𝐊= = = 𝟓. 𝟔𝟖 × 𝟏𝟎
𝐊 𝐛 𝐨𝐟 𝐍𝐇𝟑 𝟏. 𝟕𝟔 × 𝟏𝟎−𝟓
What can be said about the magnitude of K for the relevant reaction and
how will that impact the calculations? use the Large-K approximation
Announcements for Wednesday, 01MAR2023
• none

• Determine the [NH4+]eq of 1.00 L of 0.010-M NH4Cl(aq) after the addition of 0.500 mol
NaOH(s) given that Kb of NH3 = 1.76×10–5 (assume no change in volume).
[NH4+]eq = 3.6×10–7 M
𝟏 𝟏
NH4+(aq) + OH–(aq) ⇌ H2O(ℓ) + NH3(aq) 𝐊= =
𝐊 𝐛 𝐍𝐇𝟑 𝟏. 𝟕𝟔 × 𝟏𝟎−𝟓
Initial 0.010 M 0.500 M – 0
Change – 0.010 – 0.010 + 0.010 = 𝟓. 𝟔𝟖 × 𝟏𝟎𝟒
use large-K approximation
Equilibrium x 0.490 M 0.010 M
(0.010) (0.010) +
K= = 5.68 × 104 x= = 𝟑. 𝟔 × 𝟏𝟎 −𝟕
𝐌 = 𝐍𝐇𝟒 𝐞𝐪
(x)(0.490) (0.490)(5.68 × 104 )
Chapter 17: Aqueous Ionic Equilibrium
• What is a buffer and how does it work?
• What is the common ion effect?
• What are the different ways to prepare a buffer?
• How can we calculate the pH of a buffer before and after the addition of strong
acid or strong base?
• How does the pH of a solution change during an acid-base titration?
• What are pH indicators and how do they work?
• How do we determine the solubility of sparingly soluble ionic compounds?
• How do we determine if a precipitate forms when two solutions of ionic
compounds are mixed?
• What are complex ions and how can their formation in solution be described by
equilibrium processes?
• What factors impact the solubility of a sparingly soluble compound?
for Chapter 17
• ionic compounds, ionic compound nomenclature, metals that
form cations with different charges – Ch 4
• electronegativity, bond polarity, Lewis structures, bond
energy, molecular shape – Ch 5
• molarity, dilution, solution stoichiometry, net ionic equations,
concentrations of ions, solubility rules, electrolytes,
precipitation reactions, acids and bases – Ch 8
• functional groups – Ch 21
✓ mixture of strong/weak acids in water
✓ mixture of strong/weak bases in water
✓a salt in water
✓weak acid in salt solution containing its conjugate base
✓weak base in salt solution containing its conjugate acid
✓strong acid in a weak base solution
✓strong base in weak acid solution
✓strong acid/strong base in a buffer solution
Buffers
• buffer = a solution that resists pH changes
• the solution contains components that can react with (and neutralize) added
strong acid (H+/H3O+) or added strong base (OH–)
• many physiological processes occur in a very narrow pH range
• buffering keeps the pH of the reaction environment relatively constant
essential components of a buffer

1. significant amounts of a weak acid and its conjugate base
• example: HF and F– (from NaF or KF or LiF…)
2. significant amounts of a weak base and its conjugate acid
• example: NH3 and NH4+ (from NH4Cl or NH4NO3 or NH4Br…)
• BOTH components must be present in significant amounts for the

solution to be considered a buffer!
The Common Ion Effect
• we will see that buffers are able to maintain constant pHs largely
because of the common ion effect
• when a weak acid is added to a solution that already contains the anion of the
acid, the acid will dissociate less and will be less acidic
compare the pH of 1.0 M HF in water vs. 1.0 M HF in 1.0 M NaF(aq)
pH = 1.72 pH = 3.45
• because the NaF(aq) contains an ion common to HF (i.e., F–) the HF will not
dissociate as much
• remember Le Châtelier’s principle:
• the presence of F– from NaF disrupts the acidity of HF
HF(aq) ⇌ H+(aq) + F–(aq)
• but the basicity of F– is also impacted by the presence of HF…
compare the pH of 1.0 M HF in water vs. 1.0 M HF in 1.0 M NaF(aq)
Ka of HF = 3.5×10–4
pure water 1.0 M NaF(aq)
HF(aq) ⇌ H+(aq) + F–(aq) HF(aq) ⇌ H+(aq) + F–(aq)
I 1.0 ≈0 0 I 1.0 ≈0 1.0
C –x +x +x C –x +x +x
E 1.0 – x x x E 1.0 – x x 1.0 + x
𝑥2 (𝑥)(𝟏. 𝟎 + 𝒙)
𝐾𝑎 = = 3.5𝑥10−4 𝐾𝑎 = = 3.5𝑥10−4
(1.0 − 𝒙) (1.0 − 𝒙)
𝑥2 (𝑥)(𝟏. 𝟎)
𝐾𝑎 = = 3.5𝑥10−4 𝐾𝑎 = = 3.5𝑥10−4
(1.0) (1.0)
𝑥 = 𝐻 + = 0.019 𝑀 𝑥 = 𝐻 + = 3.5𝑥10−4 𝑀
𝑝𝐻 = − log 0.019 = 1.72 𝑝𝐻 = − log 3.5𝑥10−4 = 3.45
Calculating the pH of 1.0 M HF in 1.0 M NaF(aq)
Ka of HF = 3.5×10–4 and Kb of F– = 2.8×10–11
1.0 M HF in 1.0 M NaF (from HF point-of-view) 1.0 M HF in 1.0 M NaF (from F– point-of-view)
HF(aq) ⇌ H+(aq) + F–(aq) F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq)
I 1.0 ≈0 1.0 I 1.0 1.0 ≈0
C –x +x +x C –x +x +x
E 1.0 – x x 1.0 + x E 1.0 – x 1.0 + x x
(𝑥)(1.0 + 𝒙) (1.0 + 𝒙)(𝑥)
𝐾𝑎 = = 3.5𝑥10−4 𝐾𝒃 = = 𝟐. 𝟖𝒙𝟏𝟎−𝟏𝟏
(1.0 − 𝒙) (1.0 − 𝒙)
𝑥 = 𝐻 + = 3.5𝑥10−4 𝑀 𝑥 = 𝑂𝐻 − = 2.8𝑥10−11 𝑀
pOH = − log 2.8𝑥10−11 = 10.55
𝑝𝐻 = − log 3.5𝑥10−4 = 𝟑. 𝟒𝟓
𝑝𝐻 = 14 − 𝑝𝑂𝐻 = 14 − 10.55 = 𝟑. 𝟒𝟓
• we are able to calculate the pH of this buffer solution by doing an ICE table from either
the point-of-view of the weak acid or the conjugate base
• there’s any easier way to calculate the pH of a buffer solution without doing an ICE table…
the Henderson-Hasselbalch Equation
• equivalent to solving an ICE table for a buffer solution in which the
small-K approximation holds for the concentrations of the buffer
components
• a weak acid and its conjugate base OR a weak base and its conjugate acid
• it is derived from the expression of Ka for the weak-acid component
of the buffer 𝐛𝐚𝐬𝐞
𝐩𝐇 = 𝐩𝐊 𝐚 + 𝐥𝐨𝐠
𝐚𝐜𝐢𝐝
• pH = the pH of the buffer
• pKa = – log Ka of the weak-acid component of the buffer
• [base] and [acid] = the concentrations of the buffer components
Remember that the small-K approximation must be valid in order for

Henderson-Hasselbalch to be applied
• the concentrations of buffer components must not be too dilute
• the size of Ka should be several orders of magnitude smaller than
concentrations
the Henderson-Hasselbalch Equation
consider again a solution that is 1.0 M HF and 1.0 M F–
HF(aq) ⇌ H+(aq) + F–(aq)
𝐻+ 𝐹 − rearrange for 𝐾𝑎 𝐻𝐹 take – log of 𝐾𝑎 𝐻𝐹
𝐾𝑎 = [H+] 𝐻+ = both sides −𝑙𝑜𝑔 𝐻+ = −𝑙𝑜𝑔
𝐻𝐹 𝐹− 𝐹−
𝐻𝐹 substitute 𝐻𝐹
−𝑙𝑜𝑔 𝐻 + = − log 𝐾𝑎 − 𝑙𝑜𝑔 𝑝𝐻 = 𝑝𝐾𝑎 − 𝑙𝑜𝑔
𝐹− 𝐹−
𝐹−
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
𝐻𝐹
remember that these

generalize
𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑏𝑎𝑠𝑒
refer to the
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 components of the
𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑
buffer
Try This
What is the pH of a buffer solution that is 1.50 M NH3 and 1.80 M
NH4Cl? The Kb of NH3 = 1.76×10–5. 9.167
𝐾𝑤 1 × 10−14
𝐾𝑎 𝑜𝑓 𝑁𝐻4+ = = −5
= 5.68 × 10−10
𝐾𝑏 1.76 × 10
𝑝𝐾𝑎 𝑜𝑓 𝑁𝐻4+ = − log 5.68 × 10−10 = 9.246
𝑏𝑎𝑠𝑒 = 𝑁𝐻3 = 1.50 𝑀
𝑎𝑐𝑖𝑑 = 𝑁𝐻4+ = 1.80 𝑀
𝑏𝑎𝑠𝑒
𝑝𝐻 = 𝑝𝐾𝑎 + log
𝑎𝑐𝑖𝑑
1.50
𝑝𝐻 = 9.246 + log
1.80
𝑝𝐻 = 9.246 − 0.079 = 9.167

Preparing Buffers
• remember that the solution must contain significant amounts of weak
acid/conjugate base or weak base/conjugate acid
• how it gets those significant amounts is unimportant
1. adding an amount of weak acid and an amount of salt that contains
the conjugate base of the weak acid
• adding 2.0 mol HNO2 and 1.4 mol KNO2 to a total volume of 500 mL
• Ka HNO2 = 4.6×10–4 (pKa = 3.34)
• pH = 3.19 (do the calculations on your own to verify)
2. adding an amount of weak base and an amount of salt that contains
the conjugate acid of the weak base
• adding 25.0 g CH3NH2 and 55.0 g CH3NH3NO3 to a total volume of 2.0 L
• Kb CH3NH2 = 4.4×10–4
• pH = 10.78 (do the calculations on your own to verify)
Preparing Buffers (continued)
3. adding a small amount of strong base to a sample of weak acid to
deprotonate a portion of the acid and generate an amount of
conjugate base
adding 0.50 mol OH– to 1.50 mol HF in 1.0 L water
this is a net-ionic equation
OH– + HF → F– + H2O(ℓ)
(no spectator ions shown)
before 0.50 mol 1.50 mol 0 mol
after 0 mol 1.00 mol 0.50 mol
• Ka HF = 3.5×10–4 (pKa = 3.45)

0.50 M significant amounts of
pH = 3.45 + log = 𝟑. 𝟏𝟓
1.00 M both components
3. adding a small amount of strong base to a sample of weak acid to
What deprotonate a portion
if 2.50 mol OH of thetoacid
– was added 2.00and
molgenerate an amount
HF in a total volumeofof 1.0 L?
conjugate base
adding 2.50 mol OH– to 2.00 mol HF in 1.0 L water
OH– + HF → F– + H2O(ℓ)
after 0.50 mol 0 mol 2.00 mol
0.50 𝑚𝑜𝑙 𝑂𝐻 − pOH = − log 0.50 = 0.30

−
𝑂𝐻 = = 0.50 𝑀
1.0 𝐿 pH = 14.00 − 0.30 = 𝟏𝟑. 𝟕𝟎
• it would NOT be a buffer; it would be a basic solution with pH = 13.70

Announcements for Thursday, 02MAR2023
• Graded and Timed Quizzes 6a & 6b – “Acid and Bases” due Monday,
06MAR2023, at 6:00 PM (EST)

4. adding a small amount of strong acid to a sample of weak base to
protonate a portion of the base and generate an amount of
conjugate acid
adding 0.50 mol H+ to 1.50 mol NH3 in 1.0 L water
H+ + NH3 → NH4+
• Kb NH3 = 1.76×10–5
−14
K w 1.0 × 10
K a NH4+ = = = 5.68 × 10 −10
K b NH3 1.76 × 10−5
1.00 M
pH = 9.25 + log = 𝟗. 𝟓𝟓
0.50 M
How Do Buffers Work?
consider 1 L buffer solution that initially is 1 M HF(aq) and 1 M NaF(aq)
adding strong acid (H+/H3O+) to the buffer
A. H3O+(aq) + F–(aq) → HF(aq) + H2O(ℓ)
• will go to completion until all added H+ is consumed
• HF will be formed and F– will be consumed (this stresses the system out of equilibrium)
B. HF(aq) + H2O(ℓ) ⇌ H3O+(aq) + F–(aq)
• HF and F– will then come back into equilibrium with each other
adding strong base (OH–) to the buffer

A. OH–(aq) + HF(aq) → F–(aq) + H2O(ℓ)
• will go to completion until all added OH– is consumed
• F– will be formed and HF will be consumed (this stresses the system out of equilibrium)
B. F–(aq) + H2O(ℓ) ⇌ HF(aq) + OH–(aq)
• F– and HF will then come back into equilibrium with each other
Calculating pH of Buffer After Addition of Strong Base/Strong Acid
2-step process
step 1 = stoichiometry step
• allow the added strong base or strong acid to react to completion
with the appropriate buffer component
• calculate final amounts of weak acid and conjugate base (or weak
base and conjugate acid)
step 2 = equilibrium step

• use the Henderson-Hasselbalch equation and final amounts of buffer
components (from stoichiometry step) to calculate final pH of the
buffer
• remember to use the pKa of the acid component of the buffer
Consider 1.0 L of a buffer that is initially 0.50 M CH3COOH and 0.75 M CH3COO–.
What is the pH of the buffer after 0.22 mol HCl is added?
Ka CH3COOH = 1.8×10–5
step 1: stoichiometry step
H+ + CH3COO– → CH3COOH
before 0.22 mol 0.75 mol 0.50 mol
step 2: equilibrium step
𝐶𝐻3 𝐶𝑂𝑂−
𝐶𝐻3 𝐶𝑂𝑂𝐻
−5
0.53 𝑀
𝑝𝐻 = − log 1.8 × 10 + log
0.72 𝑀
𝑝𝐻 = 4.74 − 0.13 = 4.61
Characteristics of an Effective Buffer
1. the relative concentrations of [weak acid] and [conj. base] should be
equal (…or close to it)
• this allows the buffer to be equally effective at neutralizing added acid and
added base
• the closer the concentrations are to one another, the more resistant to
pH changes the buffer is
[base]
• should range from 0.10 to 10
[acid]
2. the absolute concentrations of the buffer components should be high
• this gives the buffer a higher capacity (i.e., it can neutralize more added acid or
added base)
• concentrated buffers are better than dilute buffers
• remember that a buffer can be exhausted if too much acid or base is added
Buffering Range
• buffering range = the range of pHs over which the buffer is effective
at maintaining constant pH
• since the relative concentrations of [weak acid]/[conj. base] (or [weak
base]/[conj. acid]) should not differ by more than a factor of 10, the buffering
range can be easily established in relationship to the pKa of the buffer
𝑏𝑎𝑠𝑒
𝑎𝑐𝑖𝑑
𝟏 𝟏 𝟏𝟎
𝑝𝐻 = 𝑝𝐾𝑎 + log 𝑝𝐻 = 𝑝𝐾𝑎 + log 𝑝𝐻 = 𝑝𝐾𝑎 + log
𝟏𝟎 𝟏 𝟏
𝑝𝐻 = 𝑝𝐾𝑎 −1 𝑝𝐻 = 𝑝𝐾𝑎 𝑝𝐻 = 𝑝𝐾𝑎 + 1
lower end of buffering range an optimal buffer higher end of buffering range
a buffer is most effective over a pH range = pKa  1

Fine-Tuning the pH of a Buffer
• the pH needed for the buffer depends on its specific application
• not all weak acid/conjugate base pairings will be suitable for a given buffer pH
𝑏𝑎𝑠𝑒
𝑎𝑐𝑖𝑑
• the pH of a buffer can be modified by changing the weak acid
component
• changes the pKa in Henderson-Hasselbalch
• the pH of a buffer can also be modified by slightly adjusting the
relative ratio of base-to-acid components in the buffer
• [base] > [acid] pH of buffer will increase
• [acid] > [base] pH of buffer will decrease
• [base] = [acid] pH of buffer equals pKa of the acid component
• Which combination(s) of solutions could be used to produce an
effective buffer at pH = 4.70? Assume any volumes you want.
All of them
I. 1.0 M KOH(aq) + 1.0 M CH3COOH (Ka = 1.8×10–5)
II. 1.0 M HCl(aq) + 1.0 M C6H5NH2 (Kb = 3.9×10–10)
III. 1.0 M NaH2C6H5O7(aq) + 1.0 M Na2HC6H5O7 (Ka of H2C6H5O7– = 1.7×10–5)

• What is the pH of a buffer that is 0.76 M in HF and 0.98 M in KF? Ka of HF
= 3.5×10–4. 3.57
• 1 L of a buffer that is 0.85 M in HX and 1.4 M X– has a pH of 3.99. What is
the Kb of X–? 5.9×10–11
• Consider 1.00 L of a buffer that is 1.50 M in HCN and 1.20 M in NaCN.
Calculate the pH of the solution before and after the addition of 0.25 mol
NaOH. Assume no change in volume. Ka of HCN = 4.9×10–10.
9.21 (before) and 9.37 (after)
• What volume of 0.660 M NH3 should be added to 50.0 mL of 0.850 M
NH4NO3(aq) to give a solution with pOH = 4.556? Kb of NH3 = 1.76×10–5.
102 mL
• Challenging: What amount of HCl should be added to 1.00 L of 1.25 M
pyridine (C5H5N, Kb = 1.7×10–9) to give a buffer solution with pH = 5.50?
0.44 mol HCl
Announcements for Monday, 06MAR2023
• Graded and Timed Quizzes 6a & 6b – “Acid and Bases” due tonight at 6:00 PM (EST)
• Week 8 Homework Assignments will be available today on eLearning
• Graded and Timed Quizzes 7a – “Acid and Bases” & 7b – “Buffer Solutions” will be
due Saturday, 11MAR2023, at 6:00 PM (EST)
• Spring Break next week
• no classes, recitations, office hours, etc.

• Which combination(s) of solutions could be used to produce an
effective buffer at pH = 4.70? Assume any volumes you want.
All of them
pH = 4.70 needs to be within the effective range of the buffer
I. 1.0 M KOH(aq) + 1.0 M CH3COOH (Ka = 1.8×10–5) effective pH range: 3.74 – 5.74
pKa = – log(1.8×10–5) = 4.74 YES!
II. 1.0 M HCl(aq) + 1.0 M C6H5NH2 (Kb = 3.9×10–10) effective pH range: 3.60 – 5.60
𝟏.𝟎×𝟏𝟎−𝟏𝟒
pKa = – log( −𝟏𝟎 ) = 4.60 YES!
𝟑.𝟗×𝟏𝟎
III. 1.0 M NaH2C6H5O7(aq) + 1.0 M Na2HC6H5O7 (Ka of H2C6H5O7– = 1.7×10–5)

pKa = – log(1.7×10–5) = 4.77 YES! effective pH range: 3.77 – 5.77
• What is the pH of a buffer that is 0.76 M in HF and 0.98 M in KF? Ka of HF
= 3.5×10–4. 3.57
• 1 L of a buffer that is 0.85 M in HX and 1.4 M X– has a pH of 3.99. What is
the Kb of X–? 5.9×10–11
• Consider 1.00 L of a buffer that is 1.50 M in HCN and 1.20 M in NaCN.
Calculate the pH of the solution before and after the addition of 0.25 mol
NaOH. Assume no change in volume. Ka of HCN = 4.9×10–10.
9.21 (before) and 9.37 (after)
• What volume of 0.660 M NH3 should be added to 50.0 mL of 0.850 M
NH4NO3(aq) to give a solution with pOH = 4.556? Kb of NH3 = 1.76×10–5.
102 mL
• Challenging: What amount of HCl should be added to 1.00 L of 1.25 M
pyridine (C5H5N, Kb = 1.7×10–9) to give a buffer solution with pH = 5.50?
0.44 mol HCl
Try This
• Consider 1.0 L of a solution that is 0.50 M in both CH3COOH and CH3COO–.
Calculate the pH of the solution before and after 0.50 mol NaOH is added.
Ka of CH3COOH = 1.8×10–5. Assume no volume change. 4.74 and 9.37
Consider the kind of solution we are starting with.

What kind of species is NaOH?
With which species in the initial solution will NaOH react? To what extent?
What species will remain (and how much) once NaOH reacts?
How will the remaining species impact the pH of the solution?
Try This
• Consider 1.0 L of a solution that is 0.50 M in both CH3COOH and CH3COO–. Calculate the pH of the
solution before and after 0.50 mol NaOH is added. Ka of CH3COOH = 1.8×10–5. Assume no volume
change. 4.74 and 9.37
initial solution: 0.50 M in both CH3COOH and CH3COO–…a BUFFER solution! Use Henderson-Hasselbalch to get initial pH
𝐶𝐻3𝐶𝑂𝑂− 0.50 𝑀
𝑝𝐻 = 𝑝𝐾𝑎 + log = − log 1.8 × 10−5 + log = 𝟒. 𝟕𝟒; 𝑝𝐻 = 𝑝𝐾𝑎
𝐶𝐻3𝐶𝑂𝑂𝐻 0.50 𝑀
OH– will react to completion with CH3COOH in the buffer to make more CH3COO–…work with moles here!
OH– + CH3COOH → CH3COO–
after all of the OH– reacts, all that is left is CH3COO–(aq)
before 0.50 mol 0.50 mol 0.50 mol a WEAK BASE SOLUTION
after 0 mol 0 mol 1.00 mol NOT A BUFFER!
Now calculate the pH of 1.0 M CH3COO– (aq) using an ICE table and the Kb of CH3COO–
• since we’re doing an ICE table, we MUST go back into Molarity
(𝑥)(𝑥)
CH3COO– + H2O ⇌ CH3COOH + OH–(aq) 𝐾𝑏 = = 5.6𝑥10−10
(1.0 − 𝑥)
I 1.0 M 0 ≈0
𝑥 = 𝑂𝐻 − = 2.36𝑥10−5 𝑀
C –x +x +x
pOH = − log 2.36𝑥10−5 = 4.63
E 1.0 – x x x
𝑝𝐻 = 14 − 𝑝𝑂𝐻 = 14 − 4.63 = 𝟗. 𝟑𝟕
Recall from Chapter 8 – Titration
titrant (in buret)
• a common laboratory procedure in
which a substance in a solution of
known concentration (the titrant)
is reacted with another substance
in a solution (the analyte)
• the titrant is slowly added to the
analyte using a buret
• equivalence point = the point of a
titration in which all of the analyte
has been reacted with the titrant
• the titrant and analyte are present in analyte
exact stoichiometric ratios
• indicator = a chemical compound
that changes color at the
equivalence point
Titration Curves (pH Curves)
• titration curve = a plot of pH of a
solution (i.e., the analyte) during a
titration
• the overall shape of a pH curve will
depend on the type of titration
1. the strength of analyte
• strong acid or base
• weak acid or base
2. the strength of the titrant
• strong acid or base
• weak acid or base © 2018 Pearson Education, Inc.
Titration Curves (pH Curves) (continued)
• we will investigate separately four types
of titration curves
• titration of a strong acid with a strong base
• titration of a strong base with a strong acid
• titration of a weak acid with a strong base
• titration of a weak base with a strong acid
• for each type of titration we will focus on
• calculating the initial pH (i.e. before the

titration begins)
• calculating pH at various points before
equivalence
• calculating the pH AT equivalence point
• explaining and understanding the overall © 2018 Pearson Education, Inc. © 2018 Pearson Education, Inc.
shapes of each curve

Titration of a Strong Acid with a Strong Base
Consider the titration of 25.0 mL of 0.100-M HCl(aq)
with 0.100-M NaOH(aq) 0.100 M
titrant = NaOH and analyte = HCl NaOH(aq)
What is the initial pH of the analyte

(i.e. before the titration begins)?
• HCl is a strong acid
• [HCl] = [H+] = 0.100 M
• pH = – log 0.100 = 1.000
0.100 M
HCl(aq)
Now let’s start adding some NaOH…

Titration of a Strong Acid with a Strong Base (continued)
What is the pH of the solution after 5.0 mL of 0.100-M NaOH has been
added to 25.0 mL of 0.100-M HCl?
• First, consider what will happen to the OH– as it is added
• neutralization reaction will be H+ + OH– → H2O (net-ionic equation)
• How much HCl will be neutralized by OH–?
H+ + OH– → H2O
before 0.00250 mol 0.00050 mol
after 0.0020 mol 0 mol
• final volume of solution? 0.00200 𝑚𝑜𝑙 𝐻 +
𝐻+ 𝑓𝑖𝑛𝑎𝑙 = = 0.0667 𝑀
25.0 mL + 5.0 mL = 30.0 mL 0.0250 + 0.0050 𝐿
𝑝𝐻 = − log 0.0667 = 1.176

the pH of the HCl(aq) has increased due to the addition of strong base
What is the pH of the solution after 15.0 mL of 0.100-M NaOH has
been added to 25.0 mL of 0.100-M HCl?
2 ways to proceed
start from the end of previous start from the beginning and
step and add 10.0 mL NaOH(aq) add 15.0 mL NaOH(aq)
H+ + OH– → H2O
H+ + OH– → H2O
• final volume of solution 0.00100 𝑚𝑜𝑙 𝐻 +

𝐻+ 𝑓𝑖𝑛𝑎𝑙 = = 0.0250 𝑀
25.0 mL + 15.0 mL = 40.0 mL 0.0400 𝐿
𝑝𝐻 = − log 0.0250 = 1.602
the pH of the HCl(aq) continues to increase

H+ + OH– → H2O
after 0 mol 0 mol equivalence point!
𝐻+ 𝑓𝑖𝑛𝑎𝑙 = 1.0 × 10−7 𝑀
𝑝𝐻 = − log 1.0 × 10−7 = 7.00
for ANY strong acid-strong base titration at equivalence point

pH = 7
H+ + OH– → H2O
after 0 mol 0.00050 mol
0.00050 𝑚𝑜𝑙
• final volume of solution 𝑂𝐻 − 𝑓𝑖𝑛𝑎𝑙 = = 0.0091 𝑀
0.0550 𝐿
25.0 mL + 30.0 mL = 55.0 mL
𝑝𝑂𝐻 = − log 0.0091 = 2.04
𝑝𝐻 = 14 − 2.04 = 11.96
after the equivalence point, the pH drastically increases and the

solution becomes strongly basic
titration calculations – a clarification
two conceptual approaches/methods can be used
0.100 M HCl
0 mL NaOH added initial pH = 1.000
add 5 mL
NaOH(aq)
pH = 1.176
add 15 mL
add 10 mL NaOH(aq)
NaOH(aq) add 25 mL
calculate pH
NaOH(aq) add 30 mL
starting from pH = 1.602
previous step NaOH(aq)
add 10 mL
NaOH(aq)
calculate pH starting pH = 7.000

add 5 mL
NaOH(aq) from the beginning
pH = 11.96
drastic pH changes solution gets more basic as

around equivalence titration continues
pH = 7 at equivalence
very acidic initial pH

Titration of a Strong Base with a Strong Acid
Consider the titration of 25.0 mL of 0.100-M KOH(aq)
with 0.100-M HNO3(aq)
0.100 M
titrant = HNO3 and analyte = KOH HNO3(aq)
What is the initial pH of the analyte

(i.e. before the titration begins)?
• KOH is a strong base
• [KOH] = [OH–] = 0.100 M
• pOH = – log 0.100 = 1.000
• pH = 14.000 – 1.000 = 13.000 0.100 M
KOH(aq)
Now let’s start adding some HNO3…
Titration of a Strong Base with a Strong Acid (continued)
What is the pH of the solution after 5.0 mL of 0.100-M HNO3 has been
added to 25.0 mL of 0.100-M KOH?
• First, consider what will happen to the H+ as it is added
• neutralization reaction will be OH– + H+ → H2O (net-ionic equation)
• How much KOH will be neutralized by H+?
OH– + H+ → H2O
• final volume of solution? 0.00200 𝑚𝑜𝑙 𝑂𝐻 −
𝑂𝐻− 𝑓𝑖𝑛𝑎𝑙 = = 0.0667 𝑀
25.0 mL + 5.0 mL = 30.0 mL 0.0250 + 0.0050 𝐿
𝑝𝑂𝐻 = − log 0.0667 = 1.176
𝑝𝐻 = 14.000 − 1.176 = 12.824
the pH of the KOH(aq) has decreased due to the addition of strong acid
What is the pH of the solution after 15.0 mL of 0.100-M HNO3 has
been added to 25.0 mL of 0.100-M KOH?
OH– + H+ → H2O
• final volume of solution 0.00100 𝑚𝑜𝑙 𝑂𝐻−

𝑂𝐻− 𝑓𝑖𝑛𝑎𝑙 = = 0.0250 𝑀
25.0 mL + 15.0 mL = 40.0 mL 0.0400 𝐿
𝑝𝑂𝐻 = − log 0.0250 = 1.602
𝑝𝐻 = 14.000 − 1.602 = 12.398
the pH of the KOH(aq) continues to decrease

OH– + H+ → H2O
after 0 mol 0 mol equivalence point!
𝑂𝐻 − 𝑓𝑖𝑛𝑎𝑙 = 1.0 × 10−7 𝑀
𝑝𝑂𝐻 = − log 1.0 × 10−7 = 7.00
𝑝𝐻 = 14.00 − 7.00 = 7.00
for ANY strong base-strong acid titration at equivalence point

pH = 7
OH– + H+ → H2O
after 0 mol 0.00050 mol
0.00050 𝑚𝑜𝑙
• final volume of solution 𝐻+ 𝑓𝑖𝑛𝑎𝑙 = = 0.0091 𝑀
0.0550 𝐿
25.0 mL + 30.0 mL = 55.0 mL
𝑝𝐻 = − log 0.0091 = 2.04
after the equivalence point, the pH drastically decreases and the

solution becomes strongly acidic
Titration of a Strong Base with a Strong Acid
Consider the titration of 25.0 mL of 0.100-M NaOH(aq) with 0.100-M HCl(aq)
titrant = HCl and analyte = NaOH
• highly basic initial pH

• pH =7 at equivalence
• drastic pH changes around
equivalence
• solution gets more acidic
after equivalence

Titration of a Weak Acid with a Strong Base
Consider the titration of 25.0 mL of 0.100-M HCOOH(aq) (Ka = 1.8×10–4)
with 0.100-M NaOH(aq)
titrant = NaOH and analyte = HCOOH
What is the initial pH of the analyte? HCOOH ⇌ H+ + HCOO–
• HCOOH is a weak acid I 0.100 M ≈0 0
• [HCOOH] = 0.100 M C –x +x +x
• use ICE table to calculate [H+] E 0.100 – x x x
• pH = 2.37 (𝑥)(𝑥)
𝐾𝑎 = = 1.8 × 10−4
• not as acidic as HCl (0.100 − 𝑥)
𝑥 = 𝐻 + = 4.2 × 10−3 𝑀
Start adding the NaOH… 𝑝𝐻 = − log 4.2 × 10−3 = 𝟐. 𝟑𝟕

Titration of a Weak Acid with a Strong Base (continued)
What is the pH of the solution after 5.0 mL of 0.100-M NaOH has been
added to 25.0 mL of 0.100-M HCOOH(aq) (Ka = 1.8×10–4)?
HCOOH + OH– → HCOO–
before 0.00250 mol 0.00050 mol ≈ 0 mol
• the final solution contains both weak acid and its conjugate base
• it’s a buffer!
• final volume = 0.0300 L
• pH can be calculated using Henderson-Hasselbalch
0.00050 𝑚𝑜𝑙
0.0300 𝐿 note that the solution volumes cancel
𝑝𝐻 = − log 1.8 × 10−4 + log
0.00200 𝑚𝑜𝑙 out of H-H
0.0300 𝐿
𝑝𝐻 = 3.74 − 0.60 = 3.14
the pH of the HCOOH(aq) has increased from 2.37 to 3.14

• Exam II is Wednesday, 22MAR2023, 9:20-10:50 PM (EDT)
• Coverage: Chapters 15.1-17.4; exam consists of 25 questions (mixture of open-
answer, multiple-choice, etc.); see “Other Resources” on Canvas for periodic table
and formula sheet to be used on the exam
• Same Locations as Exam I
• A working, fully charged laptop with LOCKDOWN BROWSER will be
required to take the exam
• Practice Exam 2 available on Canvas (lockdown browser required)

been added to 25.0 mL of 0.100-M HCOOH(aq) (Ka = 1.8×10–4)?
0.00100
𝑝𝐻 = − log 1.8 × 10−4 + log
0.00150
𝑝𝐻 = 3.74 − 0.18 = 3.56
the pH of the HCOOH(aq) has slightly increased from 3.14 to 3.56

halfway to equivalence point
−4
0.00125
𝑝𝐻 = − log 1.8 × 10 + log
0.00125
𝑝𝐻 = 3.74 + 0 = 3.74
at the halfway point, pH = pKa
the pH continues to slightly increase from 3.56 to 3.74
0.00150
𝑝𝐻 = − log 1.8 × 10−4 + log
0.00100
𝑝𝐻 = 3.74 + 0.18 = 3.92
the pH continues to slightly increase from 3.74 to 3.92

after 0 mol 0 mol 0.00250 mol
• final volume = 0.0500 L equivalence point! all that remains is
conjugate base
the solution is no longer a buffer

it’s a weak base in water (HCOO–(aq))
to get pH we use an ICE table with the Kb of HCOO–…
What is the pH of the solution after 25.0 mL of 0.100-M NaOH has been added to
25.0 mL of 0.100-M HCOOH(aq) (Ka = 1.8×10–4)?
• final volume = 0.0500 L HCOO–(aq) + H2O(ℓ) ⇌ HCOOH(aq) + OH–(aq)

I 0.050 M 0 ≈0
0.00250 mol
HCOO− = = 0.050 𝑴 C –x +x +x
𝟎. 𝟎𝟓𝟎𝟎 𝐋
E 0.050 – x x x
(x)(x)
𝐾b = = 5.6 × 10−11
(0.050 − x) x = OH − = 1.7 × 10−6 M
(x)(x) pOH = − log 1.7 × 10−6 = 5.78
𝐾b = = 5.6 × 10−11
(0.050)
pH = 14 − pOH = 14 − 5.78 = 𝟖. 𝟐𝟐
the pH at equivalence point for a weak acid-strong base titration is basic

a mixture of a strong base and a weak base
0.00050 𝑚𝑜𝑙
𝑂𝐻 − 𝑓𝑖𝑛𝑎𝑙 = = 0.0091 𝑀
0.0550 𝐿
𝑝𝑂𝐻 = − log 0.0091 = 2.04
𝑝𝐻 = 14 − 2.04 = 11.96
as the titration continues, the solution becomes increasingly basic

same as strong acid-

strong base titration
basic pH at
equivalence
pH changes not
as drastic
moderately
acidic initial pH
buffering zone
halfway point, pH = pKa

Titration of a Weak Acid with a Strong Base – Summary of Calculations
pH of a strong base/weak base mixture
pH = 14 + log OH − eq
base
pH = pK a + log
acid pH of a single weak base in water
BH + eq OH − eq
Kb =
B eq
H+ eq A− eq
pH of a single weak acid in water K a = HA eq
Titration of a Weak Base with a Strong Acid
Consider the titration of 25.0 mL of 0.100-M NH3(aq) (Kb = 1.8×10–5)
with 0.100-M HCl(aq)
titrant = HCl and analyte = NH3
What is the initial pH of the analyte?
• NH3 is a weak base NH3(aq) + H2O(ℓ) ⇌ NH4+(aq) + OH–(aq)
• [NH3] = 0.100 M I 0.100 M 0 ≈0
• use ICE table to calculate [OH–] C –x +x +x
• moderately basic pH E 0.100 – x x x
(𝑥)(𝑥)
𝐾𝑏 = = 1.8 × 10−5
(0.100 − 𝑥)
Start adding the HCl… 𝑥 = 𝑂𝐻− = 1.3 × 10−3 𝑀

𝑝𝑂𝐻 = − log 1.3 × 10−3 = 2.87
𝑝𝐻 = 14 − 2.87 = 𝟏𝟏. 𝟏𝟑
Titration of a Weak Base with a Strong Acid (continued)
What is the pH of the solution after 5.0 mL of 0.100-M HCl has been
added to 25.0 mL of 0.100-M NH3(aq) (Kb = 1.8×10–5)?
NH3 + H+ → NH4+
• a buffer solution containing both weak base and its conjugate acid results
• pH can be calculated using Henderson-Hasselbalch
0.00200 𝑚𝑜𝑙ൗ
𝑝𝐻 = − log 5.6 × 10−10 + log 0.0300 𝐿
0.00050 𝑚𝑜𝑙ൗ
𝐾𝑤 1 × 10−14 0.0300 𝐿
𝐾a 𝑁𝐻4+ = = = 5.6 × 10 −10
𝐾𝑏 𝑁𝐻3 1.8 × 10−5
𝑝𝐻 = 9.26 + 0.60 = 9.86
the pH of the NH3(aq) has decreased from 11.13 to 9.86

NH3 + H+ → NH4+
0.00150
𝑝𝐻 = − log 5.6 × 10−10 + log
0.00100
𝑝𝐻 = 9.26 + 0.18 = 9.44
the pH of the NH3(aq) has slightly decreased from 9.86 to 9.44

NH3 + H+ → NH4+
halfway to equivalence point
0.00125
𝑝𝐻 = − log 5.6 × 10−10 + log
0.00125
𝑝𝐻 = 9.26 + 0 = 9.26
the pH continues to slightly decrease from 9.44 to 9.26

NH3 + H+ → NH4+
−10
0.00100
𝑝𝐻 = − log 5.6 × 10 + log
0.00150
𝑝𝐻 = 9.26 − 0.18 = 9.08
the pH continues to slightly decrease from 9.26 to 9.08

NH3 + H+ → NH4+
• final volume = 0.0500 L equivalence point! all that remains is
conjugate acid
the solution is no longer a buffer

it’s a weak acid in water (NH4+(aq))
to get pH we use an ICE table with the Ka of NH4+…
What is the pH of the solution after 25.0 mL of 0.100-M HCl has been added to
25.0 mL of 0.100-M NH3(aq) (Kb = 1.8×10–5)?
NH3 + H+ → NH4+
• final volume = 0.0500 L NH4+(aq) + H2O(ℓ) ⇌ H3O+(aq) + NH3(aq)

I 0.050 M ≈0 0
0.00250 mol
NH4+ = = 0.050 𝑴 C –x +x +x
𝟎. 𝟎𝟓𝟎𝟎 𝐋
E 0.050 – x x x
(x)(x)
𝐾𝑤 1× 10−14 𝐾a = = 5.6 × 10−10
𝐾a 𝑁𝐻4+ = = = 5.6 × 10 −10 (0.050)
𝐾𝑏 1.8 × 10−5
x = H3O+ = 5.3 × 10−6 M
(x)(x)
𝐾a = = 5.6 × 10−10 pH = − log 5.3 × 10−6 = 𝟓. 𝟐𝟖
(0.050 − x)
the pH at equivalence point for a weak base-strong acid titration is acidic
NH3 + H+ → NH4+
a mixture of a strong acid and a weak acid
+
0.00050 𝑚𝑜𝑙
𝐻 𝑓𝑖𝑛𝑎𝑙 = = 0.0091 𝑀
0.0550 𝐿
𝑝𝐻 = − log 0.0091 = 2.04
as the titration continues, the solution becomes increasingly acidic

moderately basic
initial pH
buffering zone
acidic pH at
equivalence
strongly acidic after

equivalence

halfway point, pH = pKa
Titration of a Weak Base with a Strong Acid – Summary of Calculations
BH + eq OH − eq
Kb =
B eq
pH of a single weak base in water
H+ eq A− eq
Ka =
HA eq
pH of a single weak acid in water

base
pH = pK a + log
acid
pH of a strong acid/weak acid mixture
pH = − log H + eq
Titration of a Polyprotic Acid
Consider titration curve of H2SO3(aq) with NaOH(aq)
• distinctive pH curve with multiple

equivalence points
• H2SO3(aq) ⇌ H+(aq) + HSO3–(aq)

Ka1 = 1.6×10–2
• HSO3–(aq) ⇌ H+(aq) + SO32–(aq)

Ka2 = 6.4×10–8
• volume of titrant needed to reach

first equivalence point is the same as
the volume to reach 2nd equivalence
point © 2018 Pearson Education, Inc.
Indicators
• weak organic acids (with Ka values) that are different colors than their conjugate bases
• used to identify a certain target pH (usually the equivalence point of a titration)
• during titration, the protonated acid (HIn) is in

equilibrium with its conjugate base (In–)
HIn (aq) + H2O (ℓ) ⇌ H3O+ (aq) + In– (aq)
color 1 color 2
• when the analyte of the titration is relatively acidic,

[HIn] will predominate over [In–] effective pH range
of Methyl Red
• color 1 will be prevalent
• when the analyte of the titration is relatively basic,
[In–] will predominate over [HIn]
• color 2 will be prevalent
• a typical indicator changes color within a range of 2 pH
units (≈  1 pKa of indicator)
Indicators (continued)
• phenolphthalein, pKa = 9.7

• colorless under relatively acidic conditions (HIn)
• pink under relatively basic conditions (In–)
In−
pH = 9.7 + log
HIn
1M
8.7 = 9.7 + log In− < HIn colorless © 2018 Pearson Education, Inc.
10 M
1M
9.7 = 9.7 + log In− = HIn light pink
1M
10 M
10.7 = 9.7 + log In− > HIn pink
1M
Indicators (continued)
• the choice of indicator depends on the target pH

• Calculate the pH of 25.0 mL of 0.215 M benzoic acid (pKa = 4.19) being
titrated with 0.116 M NaOH(aq)
(a) initially pH = 2.43
(b) after the addition of 5.0 mL of base pH = 3.27
(c) after the addition of a further 5.0 mL of base pH = 3.63
(d) at the equivalence point pH = 8.53
(e) after the addition of 5.0 mL base beyond the equivalence point
pH = 11.88
(f) after 10.0 mL of base beyond the equivalence point pH = 12.15
(g) Pick a suitable indicator from Table 17.1 (page 769 of the textbook)
for this titration. Thymol Blue or maybe o-Cresolphthalein
(h) Sketch the resulting pH curve using answers from (a) – (f)
• Practice Exam 2 available on Canvas (lockdown browser required)

• Calculate the pH of 25.0 mL of 0.215 M benzoic acid (pKa = 4.19) being
titrated with 0.116 M NaOH(aq)
(a) initially pH = 2.43
(b) after the addition of 5.0 mL of base pH = 3.27
(c) after the addition of a further 5.0 mL of base pH = 3.63
(d) at the equivalence point pH = 8.53
(e) after the addition of 5.0 mL base beyond the equivalence point
pH = 11.88
(f) after 10.0 mL of base beyond the equivalence point pH = 12.15
(g) Pick a suitable indicator from Table 17.1 (page 769 of the textbook)
for this titration. Thymol Blue or maybe o-Cresolphthalein
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
0 10 20 30 40 50 60
volume of titrant added (mL)
Solubility

Recall from Ch 8: Solubility Rules – Ionic Compounds in Water
• a set of empirical rules that

allow us to determine an
ionic compound’s water-
solubility
• compounds were
categorized as either
soluble or insoluble
• the truth is there are
degrees of solubility
• many compounds that
were considered insoluble
are actually sparingly
soluble

Quantifying the Solubility of Sparingly Soluble Compounds – Ksp
sparingly soluble ionic compounds can dissolve in water to some extent
• the dissolution of an ionic compound is an equilibrium process
• the extent of dissolution can be quantified by an equilibrium constant
for example, the solubility of CaF2(s) in water can be represented by

CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)
or
CaF2(s) + H2O(ℓ) ⇌ Ca2+(aq) + 2 F–(aq)
• note that the water may or may not be shown in the overall reaction
• the equilibrium constant for this reaction has a very specific name and
equilibrium expression: the Solubility-Product Constant (Ksp)
𝐾𝐬𝐩 = 𝐶𝑎2+ 𝒆𝒒 𝐹− 𝟐
𝒆𝒒
• remember: pure solids and H2O(ℓ) don’t show up in the equilibrium expression
• the Ksp is a rough measure of a compound’s solubility (more on this…)
Some Ksp Values at 25 °C
• a large range of values
• Ksp can be used directly to

compare solubilities of
compounds ONLY when the
compounds have the same
dissociation stoichiometry
(?!?)
• i.e., the number of ions
formed upon dissolution
• BaSO4 → 2 ions
• BaF2 → 3 ions

to compare compounds having different dissociation stoichiometries,
actual molar solubilities must be calculated
Ksp and Molar Solubility
• recall from Ch 13 that solubility is the quantity of a compound that dissolves in a
certain amount of liquid
• molar solubility of a compound (s) = number of moles of a compound that
dissolves per liter of aqueous solution (M or mol/L)
• the molar solubility (s) can be calculated from the compound’s Ksp value
calculate the solubility of CaF2 at 25 °C given its Ksp = 1.46×10–10
CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq) 𝐾s𝐩 = 𝐶𝑎2+ 𝒆𝒒 𝐹− 𝟐

𝒆𝒒
Initial 0M 0M 𝐾s𝐩 = 𝒔 𝟐𝒔 2
Change −s +s + 2s
𝐾s𝐩 = 4𝒔3 = 1.46 × 10−10
Equilibrium s 2s
s = molar solubility
3 1.46 × 10−10
𝑠= = 𝟑. 𝟑𝟐 × 𝟏𝟎−𝟒 𝑴
4
Dissociation Stoichiometry, Ksp and Molar Solubility
 the exact relationship between Ksp and molar solubility depends on
the dissociation stoichiometry
2 ions: MX
example: AgBr
MX(s) ⇌ M+(aq) + X–(aq) 𝐾𝑠p = 𝑀+ 𝒆𝒒 𝑋− 𝒆𝒒
Initial 0M 0M
𝐾𝑠p = 𝒔 𝒔
Change –s +s +s
Equilibrium s s 𝐾𝑠p = 𝒔2
𝒔= 𝐾sp
Dissociation Stoichiometry, Ksp and Molar Solubility (continued)
3 ions: MX2
example: BaF2
𝐾𝑠p = 𝑀2+ 𝒆𝒒 𝑋− 𝟐
𝒆𝒒
MX2(s) ⇌ M2+(aq) + 2 X–(aq)
𝐾𝑠p = 𝒔 2𝒔 2
Initial 0M 0M
Change –s +s + 2s
Equilibrium s 2s 𝐾𝑠p = 𝟒 𝒔3
3 𝐾sp
𝒔=
4
4 ions: MX3
example: LaF3
MX3(s) ⇌ M3+(aq) + 3 X–(aq) 𝐾𝑠p = 𝑀2+ 𝒆𝒒 𝑋− 𝟑

𝒆𝒒
Initial 0M 0M
𝐾𝑠p = 𝒔 3𝒔 3
Change –s +s + 3s
Equilibrium s 3s
𝐾𝑠p = 𝟐𝟕 𝒔4
4 𝐾sp
𝒔=
27
Calculate the solubility of Ca3(PO4)2(s) at 25 °C given its Ksp = 2.07×10–33
Ca3(PO4)2(s) ⇌ 3 Ca2+(aq) + 2 PO42–(aq) 𝐾s𝐩 = 𝐶𝑎2+ 𝟑

𝒆𝒒 𝑃𝑂43− 𝟐
𝒆𝒒
Initial 0M 0M 2.07 × 10−33 = 𝟑𝒔 3 2𝒔 2
Change –s + 3s + 2s 2.07 × 10−33 = 27𝑠3 4𝒔2

Equilibrium 3s 2s 2.07 × 10−33 = 𝟏𝟎𝟖 𝒔5
5 2.07 × 10−33
𝒔= = 𝟏. 𝟏𝟒 × 𝟏𝟎−𝟕 𝑴
108
5 ions: M3X2
example: Ca3(PO4)2
𝐾𝑠p = 𝑀2+ 𝟑
𝒆𝒒 𝑋 3− 𝟐
𝒆𝒒
M3X2(s) ⇌ 3 M2+(aq) + 2 X3-(aq)
Initial 0M 0M 𝐾𝑠p = 𝟑𝒔 3 2𝒔 2
Change –s + 3s + 2s
Equilibrium 3s 2s 𝐾𝑠p = 𝟏𝟎𝟖 𝒔5
5 𝐾sp
𝒔=
108
Ksp and Relative Solubility – an Illustration
rank the following compounds in order of increasing solubility
CaSO4 (Ksp = 7.1×10–5), PbBr2 (Ksp = 4.7×10–6), and Ag2SO4 (Ksp = 1.2×10–5)
CaSO4 < PbBr2 < Ag2SO4
least soluble most soluble
dissociation s and Ksp molar

stoichiometry relationship solubility
CaSO4 2 𝒔= 𝐾sp 𝒔= 7.1 × 10−5 8.4×10–3 M
3 𝐾sp 3 4.7 × 10−6

PbBr2 3 𝒔= 𝒔= 1.1×10–2 M
4 4
Ag2SO4 3
3 𝐾sp 3 1.2 × 10−5 1.4×10–2 M
𝒔= 𝒔=
4 4
• At 25 °C, 35.66 mg of silver phosphate dissolves in 2.00 L water
to form a saturated solution. Calculate the Ksp of Ag3PO4(s).
The molar mass of Ag3PO4 = 418.6 g/mol. 8.89×10–17
• Determine the moles of Pb2+(aq) and Br–(aq) dissolved in 400.

mL of water at 25 °C in a saturated solution of PbBr2 given that
the Ksp of PbBr2 is 4.67×10–6.
4.21×10–3 mol Pb2+ and 8.42×10–3 mol Br–
• What percentage of MgCO3(s) dissolves when 125 mg is added

to 335 mL water at 25 °C given that the Ksp of MgCO3 is
6.82×10–6? 59.0%
• Practice Exam 2 available on Canvas
• for maximum benefit, only give yourself 90 minutes and take it under exam
conditions

• At 25 °C, 35.66 mg of silver phosphate dissolves in 2.00 L water
to form a saturated solution. Calculate the Ksp of Ag3PO4(s).
The molar mass of Ag3PO4 = 418.6 g/mol. 8.89×10–17
• Determine the moles of Pb2+(aq) and Br–(aq) dissolved in 400.

mL of water at 25 °C in a saturated solution of PbBr2 given that
the Ksp of PbBr2 is 4.67×10–6.
4.21×10–3 mol Pb2+ and 8.42×10–3 mol Br–
• What percentage of MgCO3(s) dissolves when 125 mg is added

to 335 mL water at 25 °C given that the Ksp of MgCO3 is
6.82×10–6? 59.0%
Last Class
• the dissolution of a sparingly soluble ionic compounds is an
equilibrium process and extent of dissolution can be
quantified by an equilibrium constant (the solubility-product
constant Ksp)
CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq) where 𝐾𝐬𝐩 = 𝐶𝑎2+ 𝒆𝒒 𝐹 − 𝟐𝒆𝒒
• the mathematical relationship between a compound’s molar
solubility (s) and its Ksp value depends on the compound’s
dissociation stoichiometry
3 𝐾sp
• 2 ions: s = 𝐾sp ; 3 ions: s = , etc …
4
• if the Ksp value is known, an ICE table can be used to

determine the molar solubility of a compound in water
The Common Ion Effect and Solubility
• the solubility of sparingly soluble compound will be decreased if the
solution already contains a common ion
• when an ionic compound is added to a solution that already contains the cation or
anion of the ionic compound, the compound will dissociate less and will be less
soluble
for CaF2, Ksp = 1.46×10–10
compare the solubility of CaF2 in water vs. CaF2 in 1.0 M NaF(aq)
s = 3.32×10–4 M s = 1.46×10–10 M
• because the NaF(aq) contains an ion common to CaF2 (i.e., F–) the CaF2 does not
dissociate as much
Le Châtelier’s principle:
• the presence of F– from NaF disrupts the solubility of CaF2
CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)
• the solubility equilibrium does not go as much to the right as it does in
pure water
compare the solubility of CaF2 in water vs. CaF2 in 1.0 M NaF(aq)
Ksp of CaF2 = 1.46×10–10
pure water 1.0 M NaF(aq)
CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq) CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)
I 0 0 I 0 1.0
C –s +s + 2s C –s +s + 2s
E s 2s E s 1.0 + 2s
2
𝐾𝑠𝑝 = 𝑠 2𝑠 = 1.46𝑥10−10 𝐾𝑠𝑝 = 𝑠 1.0 + 𝟐𝒔 2
= 1.46𝑥10−10
4𝑠 3 = 1.46𝑥10−10 𝐾𝑠𝑝 = 𝑠 1.0 2 = 1.46𝑥10−10

3 1.46𝑥10−10
𝑠= = 3.32𝑥10−4 𝑀 𝑠 = 1.46𝑥10−10 𝑀
4
The Effect of pH on Solubility
• the solubility of sparingly soluble compound containing a strongly
basic anion or a weakly basic anion increases with increasing acidity
• strongly basic anion: OH–
• weakly basic anion: F–, NO2–, CH3COO–, CN–, ClO–, CO32–, S2–, etc.
• WHY?
Consider the solubility equilibrium of CaF2 in acidic solution
CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)
• at acidic pH, the H+ in solution will react with F– to form HF
H+(aq) + F–(aq) → HF(aq)
• this effectively decreases the free [F–] in solution
• according to Le Châtelier’s principle, more CaF2 will dissolve in an attempt to
increase [F–] in solution
• the solubility equilibrium goes more to the right than it does in pure water or
basic solution
Precipitation
• when ions in solution combine to form an insoluble ionic compound, the
compound precipitates out of the solution as a solid
consider the precipitation of CaF2(s) (Ksp = 1.46×10–10)
Ca2+(aq) + 2 F–(aq) → CaF2(s)
• Is the use of a single-headed arrow warranted?
• What is Kprecipitation for the reaction
Ca2+(aq) + 2 F–(aq) → CaF2(s)?
• note that the precipitation reaction of CaF2 is the reverse
of its Ksp-reaction
1 1
• 𝐾precipitation = = = 6.85 × 109
𝐾sp 1.46×10−10
• large K! Treat the precipitation of CaF2 as going to
completion precipitation of Ag2CrO4
• whether precipitation occurs depends on the value of the reaction

quotient, Q, immediately after mixing
Precipitation and Q
Consider mixing 500 mL 1.5×10–4 M Ca(NO3)2(aq) with 250 mL 2.0×10–3 M KF(aq)
Will CaF2(s) (Ksp = 1.46×10–10) precipitate out of solution?
before mixing:
Ca2+ = 1.5 × 10−4 𝑀 and F − = 2.0 × 10−3 𝑀
after mixing: use M1V1 = M2V2

500 mL 1.5 × 10−4 M
Ca2+ = = 1.0 × 10−4 𝑀
750 mL
250 mL 2.0 × 10−3 M

F− = = 6.7 × 10−4 𝑀
750 mL
𝑄 = Ca2+ F − 2 = 1.0 × 10−4 6.7 × 10−4 2 = 4.4 × 10−11

Precipitation and Q (continued)
Consider mixing 500 mL 1.5×10–4 M Ca(NO3)2(aq) with 250 mL 2.0×10–3 M KF(aq)
Will CaF2(s) (Ksp = 1.46×10–10) precipitate out of solution?
after mixing
𝑄 = Ca2+ F − 2 = 1.0 × 10−4 6.7 × 10−4 2 = 4.4 × 10−11
Compare Q to Ksp
• if Q > Ksp, the solution is above saturation and precipitation WILL occur
• if Q < Ksp, the solution is unsaturated and precipitation will NOT occur
• more CaF2 could be dissolved if added
• if Q = Ksp, the solution is at equilibrium and saturated
• precipitation will just begin to occur though it may not be detectable
• for the above, Q < Ksp (4.4×10–11 < 1.46×10–10) so precipitation will NOT occur
• No new quiz assignments will be released this week

Selective Precipitation
• When solutions contain several different cations, the cations may be
separated by adding the appropriate solution to selectively precipitate
them out
• to be useful, the Ksp values of the possible precipitates must differ from each
other by at least three orders of magnitude
Consider a solution containing both Ca2+ and Ba2+

Should we precipitate the ions out with
CO32–(aq) or F–(aq)?
precipitate Ksp
Ba2+ Ca2+ Ba2+ Ca2+
CaCO3 4.96×10–9
Ca2+ Ca2+
Ba 2+ BaCO3 2.58×10–9
Ba 2+
Ba2+ Ca2+ CaF2 1.46×10–10
BaF2 2.45×10–5
Selective Precipitation (continued)
consider 1.0 L of a solution that is 0.100 M Pb2+(aq) and 0.100 M Sr2+(aq) to which
Na2CrO4(aq) is added for selective precipitation
Ksp SrCrO4 = 3.6×10–5 and Ksp PbCrO4 = 2.8×10–13
CrO42– • initially the solution only contains H2O, Pb2+ and

Sr2+ but no CrO42–
• as CrO42– is added, [CrO42–] slowly increases
until it reaches a high enough concentration
that Pb2+ begins to precipitate out as PbCrO4
• this begins when Q of PbCrO4 = Ksp of PbCrO4
• as more CrO42– is added, more Pb2+ precipitates
Pb2+ Sr2+ Pb2+ Sr2+ out
Sr2+ Sr2+ • once all Pb2+ precipitates out, additional CrO42–
Pb 2+
Pb2+ will cause [CrO42–] to slowly increase again until
Pb2+ Sr2+ it starts to precipitate out Sr2+ as SrCrO4
• this begins when Q of SrCrO4 = Ksp of SrCrO4
A. Why does Pb2+ precipitate out before Sr2+?

calculate [CrO42–] needed to precipitate each cation
remember: precipitation begins when Q = Ksp
Q of PbCrO4
Pb2+ Ksp of PbCrO4 Sr2+
[Pb2+]o [CrO42–]o = 2.8×10–13 [Sr2+]o [CrO42–]o = 3.6×10–5
(0.100 M)[CrO42–]o = 2.8×10–13 (0.100 M)[CrO42–]o = 3.6×10–5

[CrO42–]o needed to precipitate out Pb2+ [CrO42–]o needed to precipitate out Sr2+
= 2.8×10–12 M = 3.6×10–4 M
due to the lower Ksp of PbCrO4, Pb2+ precipitates out at a much lower [CrO42–] than Sr2+
B. What is [Pb2+] at the point when SrCrO4 just starts to precipitate out?
from previous slide: [CrO42–] = 3.6×10–4 M when Sr2+ begins to precipitate out
[Pb2+]eq [CrO42–]eq = Ksp
[Pb2+]eq (3.6×10–4 M) = 2.8×10–13
[Pb2+]eq = 7.8×10–10 M
[Pb2+] in solution has dropped substantially from 0.100 M to 7.8×10–10 M!

• At 25 °C the pH of a saturated solution of magnesium
hydroxide in water is 9.872. Calculate the Ksp of magnesium
hydroxide. 2.06×10–13
• Calculate the solubility of Fe(OH)3 in buffer solutions having
the following pHs: a) pH = 4.50; b) pH = 7.00; c) pH 9.50. The
Ksp of Fe(OH)3 is 2.8×10–39.
a) 8.9×10–11 M; b) 2.8×10–18 M; c) 8.9×10–26 M
• Challenging: What is [PO43–] at equilibrium when 75 mL of
0.80 M Pb(NO3)2(aq) is mixed 10. mL of 0.10 M Na3PO4(aq) at
25 °C given that the Ksp of Pb3(PO4)2 is 1.0×10–54? 1.8×10–27 M
Increasing the Solubility of a Sparingly Soluble Solid - In General
• the solubility of sparingly soluble compound can be increased (in relation to pure
water) if the compound is added to a solution that already contains an ion that
will react with one of the ions of the compound
• according to Le Châtelier’s principle, if the concentration of one of the compound’s ions is
decreased, more of the solid compound will dissolve to maintain equilibrium
• we already saw that the solubility of ionic compounds containing basic anions will
increase in acidic solution
Consider the solubility of Al(OH)3 in acidic solution

Al(OH)3(s) ⇌ Al3+(aq) + 3 OH–(aq)
• at acidic pH, the H+ in solution will react with OH– to form H2O
• this effectively decreases [OH–] and causes more Al(OH)3 to dissolve in response
Increasing the Solubility of a Sparingly Soluble Solid - In General
(continued)
Now consider the solubility of AgI

AgI(s) ⇌ Ag+(aq) + I–(aq)
• pH doesn’t impact the solubility of AgI as I– has no acid-base
properties
• however, according to Le Châtelier’s principle, the solubility of AgI can
also be increased by decreasing [Ag+]
• How?
Complex Ion Formation
• some metal cations can act as Lewis acids (i.e., electron-pair acceptors) and
form complex ions(?!?) with Lewis bases (i.e., electron-pair donors) in
solution
• complex ion = ion composed of a central metal cation bonded to one or
more ligands (i.e., Lewis bases)
• the ligands can be charged or neutral; monatomic or polyatomic
• more on this in Chapter 22
for example, Ag+ forms a complex ion with NH3 according to the following
equilibrium reaction
Ag+(aq) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) Kf = 1.7×107
central cation ligands complex ion
• Kf = the formation constant of the complex ion
+
Ag NH3 +2 𝐞𝐪 7
𝐾𝐟 Ag NH3 2 = = 1.7 × 10
Ag + 𝐞𝐪 NH3 𝟐𝐞𝐪
Recall Complex Ions from Chapter 16
Al3+(aq) + 6 H2O(ℓ) → Al(H2O)63+(aq)

H2O(ℓ) H3O+(aq)
complex ion complex ion
Some Common Kf Values in Water at 25 °C
• relatively large magnitudes; remember the large-K approximation

• be able to identify species as complex ions and writing Kf reactions
from complex ion formulas
The Effect of Complex Ion Formation on Solubility
• Now let’s go back to the solubility of AgI
• as Ag+ forms a complex ion with NH3, the solubility of AgI (Ksp =
8.51×10–17) should be increased (relative to pure water) if it’s added
to NH3(aq)
• two different equilibrium processes occur
AgI(s) ⇌ Ag+(aq) + I–(aq) Ksp = 8.51×10–17
Ag+(aq) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) Kf = 1.7×107
AgI(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + I–(aq) K = Ksp × Kf
K = (8.51×10–17 )(1.7×107)
K = 1.4×10–9
The Effect of Complex Ion Formation on Solubility - Illustrated
compare the solubility of AgI(s) in pure water vs. 2.0 M NH3(aq)
pure water 2.0 M NH3(aq)
AgI(s) ⇌ Ag+(aq) + I–(aq) AgI(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + I–(aq)
I 0 0 I 2.0 0 0
C –s +s +s C –s – 2s +s +s
E s s E 2.0 – 2s s s
𝐾𝑠𝑝 = 𝐴𝑔+ 𝐼− = 8.51𝑥10−17 𝐴𝑔 𝑁𝐻3 2+ 𝐼 − −9
𝐾= = 1.4𝑥10
𝑁𝐻3 2
𝑠 𝑠 = 8.51𝑥10−17
𝑠 𝑠 𝑠 2 −9
𝑠2 = 8.51𝑥10−17 = = 1.4𝑥10
2.0 − 𝟐𝒔 2 2.0 2
𝑠= 8.51𝑥10−17 = 9.22𝑥10−9 𝑀
𝑠= (4.0)(1.4𝑥10−9 ) = 7.6𝑥10−5 𝑀
AgI(s) is over 8000 times more soluble in NH3(aq) than in H2O because of complex ion formation
Amphoteric Metal Hydroxides
recall amphoteric = a species that can act both as an acid or as a base
• all metal hydroxides act as bases due to the presence of OH–
• even if the hydroxide is relatively insoluble in water, it can still neutralize
strong acid (H+ or H3O+)
Al(OH)3(s) + 3 H+(aq) → Al3+(aq) + 3 H2O(ℓ)
• some metal hydroxides can also act as Lewis acids under basic
conditions
• they usually contain a transition-metal cation like Cr3+, Zn2+, Pb2+, Sn2+
• they can form complex ions with additional OH–(aq) (Lewis base)
Al(OH)3(s) + OH– (aq) → Al(OH)4–(aq)
lone pair acceptor lone pair donor
complex ion
Lewis Acid Lewis Base
• Calculate the concentration of free Fe2+(aq) at equilibrium
after 0.10 mol Fe(NO3)2 is added to 1.00 L of 3.00 M NaCN(aq)
at 25 °C given that the Kf of Fe(CN)64– is 1.5×1035. 3.5×10–39 M
• Wednesday’s office hour is cancelled this week

• At 25 °C the pH of a saturated solution of magnesium
hydroxide in water is 9.872. Calculate the Ksp of magnesium
hydroxide. 2.06×10–13
• Calculate the solubility of Fe(OH)3 in buffer solutions having
the following pHs: a) pH = 4.50; b) pH = 7.00; c) pH 9.50. The
Ksp of Fe(OH)3 is 2.8×10–39.
a) 8.9×10–11 M; b) 2.8×10–18 M; c) 8.9×10–26 M
• Challenging: What is [PO43–] at equilibrium when 75 mL of
0.80 M Pb(NO3)2(aq) is mixed 10. mL of 0.10 M Na3PO4(aq) at
25 °C given that the Ksp of Pb3(PO4)2 is 1.0×10–54? 1.8×10–27 M
• Calculate the concentration of free Fe2+(aq) at equilibrium after 0.10
mol Fe(NO3)2 is added to 1.00 L of 3.00 M NaCN(aq) at 25 °C given that
the Kf of Fe(CN)64– is 1.5×1035. 3.5×10–39 M
LARGE K!!
Limiting Reactant Fe2+(aq) + 6 CN–(aq) ⇌ Fe(CN)64– (aq)
I 0.10 M 3.00 M 0
C – 0.10 – (6)(0.10) + 0.10
E x 2.40 M 0.10 M
4−
Fe CN 4−
6 𝐞𝐪 0.10 35
K f Fe CN 6 = 2+ − 𝟔
= 𝟔
= 1.5 × 10
Fe 𝐞𝐪 CN 𝐞𝐪 (x) 2.40
2+
0.10 −39
Fe 𝐞𝐪 = x = = 3.5 × 10 𝑀
(1.5 × 1035 ) 2.40 𝟔
Chapter 18: Free Energy and Thermodynamics
• What is a spontaneous process and why is a process spontaneous?
• What is entropy?
• How can we qualitatively predict the entropy change for a process?
• How can we quantitatively calculate the entropy change for a process?
• What is free energy and how can it be used to determine spontaneity?
• How do enthalpy and entropy impact changes in free energy?
• How are changes in free energy for a reaction calculated?
• What are nonstandard conditions and how do they impact free energy changes?
• How is the standard free energy change of a reaction related to the reaction’s
equilibrium constant?
• How does an equilibrium constant depend on temperature?
for Chapter 18
• energy, system/surroundings, state function, heat, gas
expansion, enthalpy, calculating enthalpy change of a reaction,
standard states, enthalpy of formation, Hess’s law – Ch 9
• gas properties – Ch 10
• changes of state – Ch 11
Spontaneous vs. Nonspontaneous Processes
• spontaneous = a process that occurs without any ongoing outside intervention
• ball rolling down a ramp, a glass shattering when it hits the floor, spreading of thermal energy
through a heated metal bar
 spontaneous DOES NOT MEAN FAST
• nonspontaneous = a process that needs ongoing outside intervention to occur
• nonspontaneous does not mean impossible
• it just means that outside intervention (and/or energy) will be needed for the process to
occur
• for reversible processes, if one process is spontaneous, the opposite process must
be nonspontaneous and vice versa

On what does spontaneity depend?
enthalpy (H)
• many exothermic reactions are observed to occur spontaneously
• combustion: CH4(g) + 2 O2(g) → CO2(g) + H2O(g)
• rust formation: 4 Fe(s) + 3 O2(g) → 2 Fe2O3(s)
• however, there are plenty of endothermic processes that are spontaneous
• spilled water evaporating on a table top
• NaCl dissolving in water (where DHsolution is slightly endothermic)
• enthalpy has an impact BUT it is not the sole criteria
entropy (S)
• first introduced in Ch 13 with solution formation
• it can roughly be thought of as a measurement of the disorder or
randomness of a system (though this definition has fallen out of fashion)
• it is difficult to completely define conceptually (i.e., non-mathematically)
Entropy (S)
• entropy (S) = a thermodynamic function that is related to the dispersal
(or spreading out) of energy within a system at a given temperature
• the more highly dispersed (or more highly randomized) a given amount of
energy within a system, the more entropy the system has
• alternatively, entropy is related to the to the number of energetically
equivalent ways to arrange the components of a system (i.e.,
microstates) to achieve a particular macroscopic state (i.e., a
macrostate)
• macroscopic state = the state of a system defined by a given set of macroscopic
conditions such as pressure, volume, and temperature
• the energy of a macroscopic state remains constant as long as the conditions remain
constant
• on the microscopic level, components of a system can adopt numerous arrangements that
are constantly changing
• microstate = a snapshot of a macrostate that gives the exact internal energy
distribution of all the components at a specific instance in time
• the more possible microstates available in a system, the more entropy the system has
Macrostates, Microstates, and Entropy Demonstrated
Expansion of a Gas in a Vacuum
the gas is not expanding against an external force

DE for expansion = 0
initially stopcock is
closed
what do we expect
to happen once the
stopcock is
opened?
gas is enclosed in
the left chamber
Expansion of a Gas in a Vacuum (continued)
initially What do we expect to

happen once the stopcock
is opened?
D E
Why is State C favored over the other possible states ? ENTROPY!

D E
• States A – E represent five possible macrostates that can result

• Let’s investigate the number of microstates that make up States A – C
to see why C is favored
• States D and E will be left out for simplicity
there is only one way

atoms 1 – 4 can
arrange to achieve
Macrostate A
there is only one way

atoms 1 – 4 can
arrange to achieve
Macrostate B

there are six ways

atoms 1 – 4 can
arrange to achieve
Macrostate C

one microstate one microstate six microstates
D E
four microstates four microstates

(not shown) (not shown)
• as State C has the most microstates, it has the greatest entropy than any of the
other states
• the energy of the atoms are dispersed more in State C than in any of the other
states
• State C has the greatest probability of occurring
Entropy (S) (continued)
• a mathematical definition of entropy that includes the notion of microstates was
expressed by Ludwig Boltzmann
𝑆 = 𝑘 ln 𝑊
• S = entropy (in J/K)
• k = Boltzmann’s constant, 1.38×10–23 J/K
• W = number of possible microstates that can result in a given macrostate
• as W increases, entropy increases
The Second Law of Thermodynamics
• an expression of the relationship between spontaneity and entropy:
For any spontaneous process the entropy of the universe increases
DSuniv > 0
• entropy of the universe is the criterion that determines the direction of a

spontaneous chemical or physical change
• the universe is composed of a system and its surroundings
• recall that DS = Sfinal – Sinitial

• DS (+) entropy increases (energy is more dispersed)
• DS (–) entropy decreases (energy is less dispersed)
• like enthalpy, entropy is a state function and an extensive property

• many of the mathematical approaches we used in Ch 9 dealing with enthalpy
changes (DH) can be used with DS (…and DG)
Qualitatively Predicting Entropy Changes (DS) for Phase Transitions
• entropy of a sample of matter increases as it changes from solid to liquid to gas
• a gas has more ways of arranging

its particles and dispersing its
energy than either a liquid or solid
entropy increases (DS > 0)

• solid → liquid phase change
• liquid → gas phase change
• solid → gas phase change
• increase in # of moles of gas © 2018 Pearson Education, Inc.
during a chemical reaction
2 NH3(g) → 1 N2(g) + 3 H2(g)  Note that increasing the temperature
of a given sample of matter in a given
CaCO3(s) → CO2(g) + CaO(s) physical state increases its entropy
o )
Entropy Changes Associated with Chemical Reactions (ΔSrxn
the entropy change for a chemical reaction can be calculated from the standard
molar entropies (S°) of the reactants and products
𝐨 = ෍ 𝐧 𝐒 𝐨 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬 − ෍ 𝐧 𝐒 𝐨 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
𝚫𝐒𝐫𝐱𝐧 𝐩 𝐫
• standard molar entropy of a substance (S°) = the energy dispersed into one mole
of that substance in its standard state at a given temperature (usually 25 °C)
• this value depends on the specific structure and state of the substance (see next slide)
• recall standard state of a substance from Ch 9
• for a Gas: the pure gas at a pressure of exactly 1 atmosphere (atm)
• for a Liquid or Solid: the pure substance in its most stable form at a pressure of 1 atm and
at the temperature of interest
• for a Substance in Solution: concentration of exactly 1 M
• all substances have positive standard molar entropies, even elements in their
standard states
• unlike enthalpies of formation (DHf°) for elements (which are zero)
Standard Molar Entropy (S°) at 298 K
the entropy of a
substance depends on
several factors
• molar mass
• physical state
(s)(ℓ)(g)(aq)
• molecular complexity
• allotropes
• all values of S° are relative to the entropy of a perfect crystal at absolute

zero (0 K) (where S = 0) (this is the Third Law of Thermodynamics)
Standard Molar Entropy – Molar Mass
• in general, the larger the

molar mass, the greater the
entropy
• the reason for this is beyond
the scope of this class
• molar mass is only ONE factor
to consider (and not always
the most important one)
• many exceptions exist

Standard Molar Entropy – Physical State
• at a particular temperature,
the gas state has a larger
entropy than the liquid state
and the liquid state has
a larger entropy than the solid
state
• dissolved solids generally
have larger entropy
(compared to undissolved
solids) as particles can be
distributed throughout the
mixture
• Today’s office hour is cancelled

Standard Molar Entropy – Molecular Complexity
• at a particular temperature,
physical state, and molar
Substance Molar Mass S° (J/mol  K)
mass, a more complex
molecule has greater entropy (g/mol)
than a less complex molecule NO(g) 30.01 210.8
• the more complex molecule C2H6(g) 30.07 229.2
has its energy dispersed in
more ways than a less complex
molecule
Standard Molar Entropy – Allotropes
• allotropes = different
structures of a given element
in the same state of matter
• diamond has less entropy
than graphite because its
carbon atoms are more
ordered and constrained by
network covalent bonds
• in graphite, the sheets of
carbon atoms are not tightly
bound

• Use the following standard molar entropies to determine the
standard entropy change for the reaction S° (J/molK)
N2O4(g) + 4 H2(g) → N2(g) + 4 H2O(g) H2(g) 130.7
H2O(g) 188.8
N2(g) 191.6
N2O4(g) 304.4
DSuniv – System (DSsys) vs. Surroundings (DSsurr)
recall that in thermodynamics the universe is divided into a system and its
surroundings
DSuniv = DSsys + DSsurr
• note that when a subscript is not used, the thermodynamic variable is from the
system’s point-of-view (DS = DSsys)
• entropy changes of a system (i.e., a chemical reaction) can be readily
determined and calculated from standard molar entropies (S°) of the
reactants and products
• however, it is not possible to determine the entropy change for the
surroundings (DSsurr) by using standard molar entropies
• DSsurr can be determined using enthalpy changes of the system (DHsys)
Entropy Change of the Surroundings (DSsurr)
let system = a reaction of interest and surroundings = surrounding air,
container, table, etc.
• when a reaction is exothermic (DHsys (–)), the system releases its
energy into the surroundings
• this results in an entropy change in the surroundings
• would entropy of the surroundings increase or decrease? DSsurr(+)
• when a reaction is endothermic (DHsys (+)), the system absorbs energy
from the surroundings
• this also results in an entropy change in the surroundings
• would entropy of the surroundings increase or decrease? DSsurr(–)
• note how the signs of DHsys and DSsurr are always opposite
• at constant P and T the exact relationship between DHsys and DSsurr is
𝑞𝑠𝑦𝑠 Δ𝐻𝑠𝑦𝑠
Δ𝑆𝑠𝑢𝑟𝑟 = − =−
𝑇 𝑇
Entropy Change of the Surroundings (DSsurr) (continued)
Δ𝐻𝑠𝑦𝑠
Δ𝑆𝑠𝑢𝑟𝑟 =− (constant P, T)
𝑇
note that the impact of enthalpy on DSsurr depends on the temperature
• the higher the temperature, the LESS the enthalpy impacts the
surrounding’s entropy
• at high temperature, the surroundings already has large amount of entropy
• consider releasing an amount of heat into an oven vs. releasing the

same amount of heat into a freezer
• in which scenario will the added energy cause greater dispersal? the freezer
Impact of Temperature on Spontaneity Illustrated
consider the freezing of water at –10 °C (263 K)
• is this a spontaneous process at this temperature?
YES or NO
• what is the sign of DSsys for H2O(ℓ) → H2O(s)?
negative or positive
• how can this be spontaneous if DSsys for H2O(ℓ) → H2O(s) is negative?
This is DS of the system and NOT of the universe! We must also
consider DSsurr
• what is the sign of DH for H2O(ℓ) → H2O(s)?
negative (exothermic) or positive (endothermic)
• what is the sign of DSsurr?
negative or positive
Impact of Temperature on Spontaneity Illustrated (continued)
consider the freezing of water at –10 °C (263 K)
DSsys (–) and DSsurr (+)
does NOT favor DOES favor
spontaneity spontaneity
• why is the process spontaneous at –10 °C (263 K)?

• DSuniv (+) = DSsys + DSsurr = (–) + (+), therefore DSsurr > DSsys
• above 0 °C (273 K), the freezing of water is NOT spontaneous
• DSuniv is (–) and DSsys > DSsurr
• raising the temperature makes DSsurr less positive
• the reaction’s exothermicity impacts the entropy of the
surroundings to a lesser extent at higher temperatures
Determining Spontaneity Using Change in Free Energy (DG)
Δ𝑆𝑢𝑛𝑖𝑣 = Δ𝑆𝑠𝑦𝑠 + Δ𝑆𝑠𝑢𝑟𝑟 replace DSsurr
Δ𝐻𝑠𝑦𝑠
Δ𝑆𝑢𝑛𝑖𝑣 = Δ𝑆𝑠𝑦𝑠 − multiply through by –T
𝑇
−𝑇(Δ𝑆𝑢𝑛𝑖𝑣 ) = −𝑇(Δ𝑆𝑠𝑦𝑠 ) + Δ𝐻𝑠𝑦𝑠 replace with DG
and rearrange
𝜟𝑮 = 𝜟𝑯 − 𝑻𝜟𝑺
(all variables are now from the system’s POV)
note that DG = –T(DSuniv)
spontaneity can now be determined from the sign of DG
• when DG < 0, process is spontaneous
• when DG > 0, process is nonspontaneous
• when DG = 0, process is at equilibrium
What Actually is Gibbs Free Energy (G)?
• formally defined as G = H – TS
• the absolute free energy of a system cannot be established; only changes in
free energy can be calculated
• an absolute free energy has no real meaning
• if DG is negative, the change in free energy for a reaction (DGrxn)
theoretically represents the maximum amount of energy available to
do work
• in real reactions the amount of energy to do work is less than DG due to the
loss of heat to the surroundings
• if DG is positive, the change in free energy represents the minimum
amount of energy required for a reaction to occur
The Effects of DH and DS on Spontaneity
DG = DH –TDS
DH DS DG
– + spontaneous at all T
ex: C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(g) DHrxn = –2044 kJ
+ – nonspontaneous at all T
ex: 3 O2(g) → 2 O3(g) DHrxn = +285.4 kJ
– – spontaneous at LOW T
ex: H2O(ℓ) → H2O(s) DHrxn = –6.01 kJ
+ + spontaneous at HIGH T
ex: H2O(ℓ) → H2O(g) DHrxn = +40.7 kJ
o
Methods to Calculate ΔGrxn
o is a state function, it can be calculated by similar methods
as ΔGrxn
o ) (Chapter 9)
used to calculated enthalpy changes for a reaction (ΔHrxn
1. using the Gibbs equation

𝑜 = Δ𝐻 𝑜 − 𝑇Δ𝑆 𝑜
Δ𝐺𝑟𝑥𝑛 𝑟𝑥𝑛 𝑟𝑥𝑛
2. using Standard Free Energies of Formation Δ𝐺𝑓𝑜

o = ෍ n Δ𝐺 𝑜 products − ෍ n Δ𝐺 𝑜 reactants
Δ𝐺rxn p 𝑓 r 𝑓
3. using Hess’s law

o (continued)
1. using the Gibbs equation
o = ΔH o − TΔS o
ΔGrxn rxn rxn
• strictly speaking, since tabulated values for Δ𝐻𝑓𝑜 and S° are typically at 25 °C, the
equation above should be valid only at 25 °C
• however, it is often assumed that the values of DHrxn and DSrxn do not change appreciably
over a limited temperature range
• therefore the Gibbs equation can be used to calculate at temperatures other than 25 °C
o (continued)
• Calculate the standard free energy changes for the reaction
N2(g) + 3 H2(g) → 2 NH3(g) at 25 °C and at 85 °C given
𝐨 = ෍ 𝐧 ∆𝑯𝒐 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬 − ෍ 𝐧 ∆𝑯𝒐 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
𝚫𝐇𝐫𝐱𝐧
𝚫𝑯𝒐𝒇 (𝒌𝑱Τ𝒎𝒐𝒍) 𝒐
𝑺 𝑱Τ𝑲 𝐩 𝒇 𝐫 𝒇
N2(g) 0 191.6 = [(2)(–45.9)] – [(1)(0) + (3)(0)] = –91.8 kJ

H2(g) 0 130.7
𝐨
NH3(g) –45.9 192.8 𝚫𝐒𝐫𝐱𝐧 = ෍ 𝐧𝐩 𝐒 𝐨 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬 − ෍ 𝐧𝐫 𝐒 𝐨 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
= [(2)(192.8)] – [(1)(191.6) + (3)(130.7)]
= –198.1 J/K = –0.1981 kJ/K
at 25 °C (298 K) at 85 °C (358 K)
𝑜 = Δ𝐻 𝑜 − 𝑇Δ𝑆 𝑜
Δ𝐺𝑟𝑥𝑛 𝑜 = Δ𝐻 𝑜 − 𝑇Δ𝑆 𝑜
Δ𝐺𝑟𝑥𝑛
𝑟𝑥𝑛 𝑟𝑥𝑛 𝑟𝑥𝑛 𝑟𝑥𝑛
= (–91.8 kJ) – (298 K)(–0.1981 kJ/K) = (–91.8 kJ) – (358 K)(–0.1981 kJ/K)
= –32.8 kJ = –20.9 kJ
• Graded and Timed Quizzes 8a – “Solubility Equilibrium” & 8b – “Solubility -
Complex Ion” due Monday, 03APR2023, at 6:00 PM (EDT)

• Use the following standard molar entropies to determine the
standard entropy change for the reaction S° (J/molK)
N2O4(g) + 4 H2(g) → N2(g) + 4 H2O(g) H2(g) 130.7
H2O(g) 188.8
reactants products N2(g) 191.6
N2O4(g) 304.4
𝐨 = ෍ 𝐧 𝐒 𝐨 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬 − ෍ 𝐧 𝐒 𝐨 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
𝚫𝐒𝐫𝐱𝐧 𝐩 𝐫
𝐨 =
∆𝐒𝐫𝐱𝐧 𝟏 𝐦𝐨𝐥 𝐍𝟐 𝟏𝟗𝟏. 𝟔 + (𝟒 𝐦𝐨𝐥 𝐇𝟐 𝐎)(𝟏𝟖𝟖. 𝟖) − 𝟏 𝐦𝐨𝐥 𝐍𝟐 𝐎𝟒 𝟑𝟎𝟒. 𝟒 + (𝟒 𝐦𝐨𝐥 𝐇𝟐 )(𝟏𝟑𝟎. 𝟕)
𝐨 = 𝟏𝟗𝟏. 𝟔 + 𝟕𝟓𝟓. 𝟐 − 𝟑𝟎𝟒. 𝟒 + 𝟓𝟐𝟐. 𝟖

𝚫𝐒𝐫𝐱𝐧
𝐨
𝐉
𝚫𝐒𝐫𝐱𝐧 = 𝟗𝟒𝟔. 𝟖 − 𝟖𝟐𝟕. 𝟐 = +𝟏𝟏𝟗. 𝟔
𝐊
o (continued)
2. using Standard Free Energies of
Formation (DGf°)
• the change in free energy when 1 mole
of a compound in its standard state is
formed from its constituent elements
in their standard states
• like DHf°, the DGf° for an element in its
standard state is zero
o
Δ𝐺rxn = ෍ np Δ𝐺𝑓𝑜 products − ෍ nr Δ𝐺𝑓𝑜 reactants
where np and nr = stoichiometric coefficients of the products and reactants, respectively

𝚫𝐆𝐟𝐨 𝐤𝐉Τ𝐦𝐨𝐥 –50.5 0 –394.4 –228.6
Calculate DGrxn° at 25 °C for CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g)
o =
ΔGrxn −394.4 + 2 −228.6 − −50.5 − 2 0
DGrxn° = –801.1 kJ (highly spontaneous)
o (continued)
3. Hess’s Law
• recall from Ch 9 that Hess’s law is a computational approach to determine energy
changes for reactions
• the change in free energy for a stepwise process is the sum of the free energies of each step
What is DG° for N2O(g) + NO2(g) → 3 NO(g) given
a) 2 NO(g) + O2(g) → 2 NO2(g) DG° = –71.2 kJ
b) N2(g) + O2(g) → 2 NO(g) DG° = +175.2 kJ
c) 2 N2O(g) → 2 N2(g) + O2(g) DG° = –207.4 kJ
c) × ½ N2O(g) → N2(g) + ½ O2(g) DG° = ½ (–207.4) = –103.7 kJ

reverse a) and × ½ NO2(g) → NO(g) + ½ O2(g) DG° = ½ (+71.2) = +35.6 kJ
leave b) N2(g) + O2(g) → 2 NO(g) DG° = +175.2 kJ
add up reactions N2O(g) + NO2(g) → 3 NO(g) DG° = (–103.7) + 35.6 + 175.2
DG° = +107.1 kJ
Free Energy Changes
Standard (DG°) vs Nonstandard (DG) Conditions
• standard free energy change (DG°)
• when all reactants and products are in their standard states
• partial pressure of each gas is 1 atm
• concentration of each dissolved species is 1 M
• nonstandard free energy change (DG)
• partial pressures of gases are other than 1 atm
• concentrations of dissolved species are other than 1 M
• at a given temperature there is only one way for standard
conditions to occur but an infinite number of ways for
nonstandard conditions to occur
Nonstandard Conditions Illustrated
consider the evaporation of 1 mol of spilled water at 25 °C
H2O(ℓ) ⇌ H2O(g) where ΔHrxn o o
= +44.0 kJ and ΔSrxn = +118.8 J/K
o
• using this information, calculate ΔGrxn
o = ΔH o − TΔS o
ΔGrxn rxn rxn
44.0 kJ – (298 K)(0.1188 kJ/K) = 44.0 – 35.4 = +8.6 kJ
o is positive (i.e., nonspontaneous), yet we know that spilled water
ΔGrxn
spontaneously evaporates at 25 °C. What gives?
• the above scenario is NOT occurring under standard conditions
• for the above scenario to be standard conditions, water vapor would
have to be present at a partial pressure of 1 atm along with pure liquid
water present at 1 atm of external pressure
• nonstandard ΔGrxn needs to be calculated from standard ΔGrxn o
o
the Relationship between ΔGrxn and ΔGrxn
o
ΔGrxn = ΔGrxn + RT ln 𝑄
• ΔGrxn = nonstandard free energy change (kJ/mol)
o = standard free energy change (kJ/mol)
• ΔGrxn
• R = 0.008314 kJ/molK
• Q = reaction quotient (unitless)
• for reactions involving gases Q = Qp
• for reactions involving dissolved species Q = Qc
o
• when Q = 1, standard state conditions exist so ΔGrxn = ΔGrxn
Nonstandard Conditions Illustrated (continued)
back to the evaporation of 1 mol of spilled water at 25 °C
H2O(ℓ) ⇌ H2O(g) ΔGrxn o = +8.6 kJ
on a typical dry day at 25 °C the partial pressure of H2O(g) in the air is

approximately 0.00500 atm
• this corresponds to a relative humidity of 16%
• this is MUCH less than 1 atm of H2O(g) (i.e., standard state)
for H2O(ℓ) ⇌ H2O(g) Qp = PH2O = 0.00500 atm
ΔGrxn = 𝚫𝐆𝐫𝐱𝐧 𝐨 + 𝐑𝐓 𝐥𝐧 𝑸
𝐤𝐉
ΔGrxn = 𝟖. 𝟔 𝐤𝐉 + (𝟎. 𝟎𝟎𝟖𝟑𝟏𝟒 )(𝟐𝟗𝟖 𝐊) 𝒍𝒏 𝟎. 𝟎𝟎𝟓𝟎𝟎
𝐊
ΔGrxn = 𝟖. 𝟔 𝐤𝐉 − 𝟏𝟑. 𝟏 𝐤𝐉 = −4.5 kJ (spontaneous!)
• the evaporation of water is spontaneous under these nonstandard
conditions
Try This
• Consider this reaction at 25 °C
CO2(g) + CCl4(g) ⇌ 2 COCl2(g) ΔGrxn
o = +46.9 kJ/mol
Calculate ΔG for this reaction under the following conditions at 25 °C

PCO2 = 0.112 atm, PCCl4 = 0.174 atm, and PCOCl2 = 0.744 atm
𝚫𝐆𝐫𝐱𝐧 = +𝟓𝟓. 𝟐 𝐤𝐉Τ𝐦𝐨𝐥
o PCOCl2 2 0.744 2
ΔGrxn = ΔGrxn + RT ln Q where Q = = = 28.4
PCO2 PCCl4 0.112 0.174
kJ kJ
ΔGrxn = 46.9 + 0.008314 298 K ln 28.4
mol mol ∙ K
kJ kJ kJ
ΔGrxn = 46.9 + 8.29 = +55.2
mol mol mol
Change in Free Energy and Equilibrium
• both the sign of a free energy change (DG) and the magnitude of an
equilibrium constant (K) give information about the spontaneity of a
reaction in a given direction
• for a reaction with a (–) DG, the forward direction is spontaneous

(and the reverse is nonspontaneous)
• for a reaction with a large value of K, the forward direction is much

more favored than the reverse direction
Change in Free Energy and Equilibrium (continued)
2 NO(g) ⇌ N2(g) + O2(g) at 25 °C where DG° = –175.2 kJ and K = 5×1030
• standard conditions = the partial pressure of each gas is 1 atm
• at standard state, Q = 1 and Q <<< K

• reaction goes in the forward direction to reach equilibrium
• at standard state, DG° = –175.2 kJ

• the forward reaction is highly spontaneous
• since both DG and K relate to spontaneity, they must be related

mathematically
the Relationship between DG° and K
o
ΔGrxn = ΔGrxn + RT ln Q
at equilibrium
DGrxn = 0
Q=K
o
𝟎 = ΔGrxn + RT ln 𝑲
rearrange
o
ΔGrxn = −RT ln 𝐾
o
ΔGrxn = −RT ln 𝐾
note the mathematical relationship between DG° and K
• when DG° has a large magnitude and is negative, the value
of K is relatively large
• K > 1 since ln K (+)
• both indicate a spontaneous reaction
• when DG° has a large magnitude and is positive, the value of
K is relatively small
• 0 < K < 1 since ln K (–)
• both indicate a nonspontaneous reaction
• note that the above equation also shows the effect of
temperature on a value of K
Try This
• Consider this reaction at 25 °C
CO2(g) + CCl4(g) ⇌ 2 COCl2(g) ΔGrxn o = +46.9 kJ/mol
What is the value of K for this reaction at this temperature? 6×10–9

o = −RT ln 𝐾
ΔGrxn
+46.9 kJΤmol = −(0.008314 kJΤmol ∙ K)(298 K) ln 𝐾
ln 𝐾 = −18.9
𝐾 = e−18.9 = 𝟔 × 𝟏𝟎−𝟗
the Effect of Temperature on the Equilibrium Constant
• recall from Ch 15 that the value of K for a reaction changes ONLY
when temperature changes
• how K changes depends on DHrxn
• what is the exact relationship between T, DH, and K?
𝐨 = −RT ln 𝐾
𝚫𝐆𝐫𝐱𝐧 𝐨 = ΔH o − TΔS o
𝚫𝐆𝐫𝐱𝐧
and rxn rxn
o − TΔS o
−RT ln 𝐾 = ΔHrxn rxn
rearrange
𝑜
Δ𝐻𝑟𝑥𝑛 1 𝑜
Δ𝑆𝑟𝑥𝑛 similar to the Arrhenius
ln 𝐾 = − +
𝑅 𝑇 𝑅 equation from Ch 14
y = m x + b
linearized form
the Effect of Temperature on the Equilibrium Constant (continued)
two-point form
𝐾2 o
ΔHrxn 1 1
ln =− −
𝐾1 R T2 T1
• K1 is the equilibrium constant at temperature 1 (T1 in K)

• K2 is the equilibrium constant at temperature 2 (T2 in K)
• o is the standard enthalpy of reaction
ΔHrxn
• R = 0.008314 kJ/molK
o o
• strictly speaking, because ΔHrxn and ΔSrxn are slightly temperature
dependent, the above equation works best over a limited
temperature range
• Recall that the normal boiling point of a substance is the temperature
at which the liquid and gas phase of that substance are in equilibrium
at 1 atm. Calculate the approximate normal boiling point of carbon
disulfide (CS2) given the following information
CS2(ℓ) → CS2(g)
𝚫𝐇𝐟𝐨 (𝐤𝐉Τ𝐦𝐨𝐥) 𝐒 𝐨 𝐉Τ𝐊
CS2(g) 116.7 237.8
CS2(ℓ) 89.0 151.3
normal boiling point = 47 °C

• Consider the reaction at 25 °C N2O4(g) ⇌ 2 NO2(g) ΔGrxn o
= 5.4 kJ Determine if
the reaction is spontaneous at 25 °C when the initial pressures of N2O4(g) and
NO2(g) are 0.453 atm and 0.122 atm, respectively .
DGrxn = –3.1 kJ (spontaneous)
• Determine the value of Kp at 25 °C for the reaction I2(g) + Cl2(g) ⇌ 2 ICl(g)
given that the standard free energies of formation for I2(g) and ICl(g) are 62.42
kJ/mol and 25.75 kJ/mol, respectively. 82.0
• What is the molar solubility of thallium(I) iodide at 25 °C given
TlI(s) ⇌ Tl+(aq) + I–(aq) ΔGrxn
o =41.00 kJ. 2.5×10–4 M
• Calculate DSsub for the sublimation of iodine in a closed container at 45 °C.

I2(s) → I2(g) DHsub = 62.4 kJ/mol. 196 J/molK
• Consider the reaction MgCO3(s) ⇌ MgO(s) + CO2(g) ΔHrxn o =100.7 kJ where K
p
= 0.026 at 377 °C. What will be the equilibrium pressure of CO2(g) at 400 °C?
0.049 atm
Announcements for Monday, 03APR2023
• Graded and Timed Quizzes 8a – “Solubility Equilibrium” & 8b – “Solubility -
Complex Ion” due tonight at 6:00 PM (EDT)

• Recall that the normal boiling point of a substance is the temperature at which the liquid and gas
phase of that substance are in equilibrium at 1 atm. Calculate the approximate normal boiling
point of carbon disulfide (CS2) given the following information 𝚫𝑯𝒐𝒇 (𝒌𝑱Τ𝒎𝒐𝒍) 𝑺𝒐 𝑱Τ𝑲
CS2(ℓ) → CS2(g) CS2(g) 116.7 237.8
normal boiling point = 47 °C CS2(ℓ) 89.0 151.3
recall from Ch 11 that the normal boiling point is when the vapor pressure of CS2(ℓ) (i.e., the pressure of CS2
vapor/gas) = 1 atm. Also recall that at the normal boiling point, the liquid and vapor are in equilibrium with each
other. Since the pressure of CS2(g) is 1 atm at this point, both the CS(ℓ) and CS(g) are under standard conditions.
Since the system is AT EQUILIBRIUM under STANDARD CONDITIONS, DG° = 0 (IT IS VERY UNCOMMON FOR A
REACTION TO BE AT EQUILIBRIUM UNDER STANDARD CONDITIONS, BUT IT DOES HAPPEN)
if DG° = 0, we can use DG° = DH° – TDS° to solve for the temperature (T) at which DG° = 0
o = Σ n ΔH o products − Σ n ΔH o reactants = 116.7 − 89.0 = +27.7 kJ
ΔHrxn p f r f
o J kJ
ΔSrxn = Σ np So products − Σ nr So reactants = 237.8 − 151.3 = +86.5 = +0.0865
K K
o o o o o ΔHo
rxn 27.7 kJ
ΔGrxn = ΔHrxn − TΔSrxn 0= ΔHrxn − TΔSrxn T= = = 320 K
ΔSo 0.0865 kJ/K
rxn or
47 °C
• Consider the reaction at 25 °C N2O4(g) ⇌ 2 NO2(g) ΔGrxn o
= 5.4 kJ Determine if
the reaction is spontaneous at 25 °C when the initial pressures of N2O4(g) and
NO2(g) are 0.453 atm and 0.122 atm, respectively .
DGrxn = –3.1 kJ (spontaneous)
• Determine the value of Kp at 25 °C for the reaction I2(g) + Cl2(g) ⇌ 2 ICl(g)
given that the standard free energies of formation for I2(g) and ICl(g) are 62.42
kJ/mol and 25.75 kJ/mol, respectively. 82.0
• What is the molar solubility of thallium(I) iodide at 25 °C given
TlI(s) ⇌ Tl+(aq) + I–(aq) ΔGrxn
o =41.00 kJ. 2.5×10–4 M
• Calculate DSsub for the sublimation of iodine in a closed container at 45 °C.

I2(s) → I2(g) DHsub = 62.4 kJ/mol. 196 J/molK
• Consider the reaction MgCO3(s) ⇌ MgO(s) + CO2(g) ΔHrxn o =100.7 kJ where K
p
= 0.026 at 377 °C. What will be the equilibrium pressure of CO2(g) at 400 °C?
0.049 atm
to Clarify: DG at Equilibrium
• if a system/reaction is at equilibrium under standard conditions
DG° = 0
• if a system/reaction is at equilibrium under NONstandard conditions

DG = 0
• it is your job to determine whether a reaction in question is under

standard conditions or not
Chapter 19: Electrochemistry
• How can electricity be generated from a chemical reaction?
• What are the necessary components of a voltaic/galvanic cell?
• What are standard electrode potentials?
• How can the spontaneity of a reaction be predicted from its standard cell
potential?
• How are free energy and the equilibrium constant related to a reaction’s
standard cell potential?
• How does cell potential depend on concentration?
• How are changes in free energy for a reaction calculated?
• How can electricity be used to cause a nonspontaneous reaction to occur?
• What is electrolysis and how does an electrolytic cell differ from a voltaic cell?
• How do batteries work and what are the different types?
• What is corrosion and what are some ways to prevent it?
for Chapter 19
• dimensional analysis – Ch E
• balancing equations, reaction stoichiometry – Ch 7
• molarity, oxidation-reduction reactions, assigning oxidation
states, identifying redox reactions, oxidizing and reducing
agents – Ch 8
• energy, standard states – Ch 9
Electrochemistry – an Overview
• a main focus of electrochemistry is the study of the interconversion of
chemical and electrical energies
• using a chemical reaction to produce electricity
• using electricity to cause a chemical reaction to occur
• electrochemistry has significant relevance

in our everyday lives © 2018 Pearson Education, Inc.
• batteries
• corrosion
• converting minerals into pure metals
• important biochemical processes
• the bases of electrochemistry are oxidation-reduction

reactions
• first covered in Chapter 8
Oxidation-Reduction Reactions (Redox) – a Brief Review
• oxidation = the loss of electrons and reduction = the gain of electrons
• oxidation-reduction reaction = an electron-transfer reaction
• electrons are transferred from one reactant (i.e., the reducing agent) to another
(i.e., the oxidizing agent)
• oxidizing agent = the reactant that gets reduced during the process and
allows another reactant to be oxidized
• reducing agent = the reactant that gets oxidized during the process and
allows another reactant to be reduced
2 Na(s) + Cl2(g) → 2 NaCl(s)
reducing oxidizing
agent agent
Na → Na+ (oxidation) and Cl → Cl– (reduction)
• during a redox reaction, the oxidation numbers of two species must
change
• one increases its ox # and another decreases its ox # (could be the same element)
Recall: Oxidation States/Numbers
• oxidation number = the fictitious charge an atom would have
in a compound if all electrons were assigned to the more
electronegative atom in that compound
• oxidation numbers are assigned to help keep track of the transfer of
electrons during a redox reaction
• for monatomic ions in an ionic compound, oxidation states
have the same value as the ions’ charges
• for neutral atoms in a molecular compound, oxidation states
are the imaginary charges the atoms WOULD have IF the
compound was ionic
• oxidation numbers are assigned based on a strict set of rules
Recall: Rules for Assigning Oxidation Numbers
• oxidation numbers are assigned to every atom or ion in a compound
according to a specific procedure
• oxidation numbers can be positive, negative, or fractional
the rules for assigning oxidation numbers MUST be applied in a specific
order since certain rules take priority over others
1. the sum of oxidation numbers for each atom or ion in a compound
must equal the overall charge of the compound
• atoms in elemental forms have oxidation numbers of zero: H2(g), O3(g), Na(s),
P4(s), etc.
• monatomic ions have oxidation numbers equal to their charge: Cu+ ox # = +1, S2-
ox # = –2, etc.
2. Assign oxidation numbers of +1 to Group 1A metal cations and +2 to
Group 2A metal cations
• Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+
3. Assign fluorine an oxidation number of –1
Recall: Rules for Assigning Oxidation Numbers (continued)
4. Assign hydrogen an oxidation number of +1 unless otherwise dictated
by previous rules
• NaH, CaH2
5. Assign oxygen an oxidation number of –2 unless otherwise dictated by
previous rules
• H2O2, OF2, NaO2
6. Assign Group 7A nonmetals (Cl, Br, I) oxidation numbers of –1 unless
otherwise dictated by previous rules
7. Assign Group 6A nonmetals (S, Se, Te) oxidation numbers of –2 unless
8. Assign Group 5A nonmetals (P, As, Sb) oxidation numbers of –3 unless
The rules for assigning oxidation numbers must be MEMORIZED!

Balancing Redox Reactions in General
• balancing chemical reactions was first covered in Chapter 7
• in Chem 161 we only focused on balancing the numbers of atoms
• balancing redox reactions require that we BALANCE CHARGES as well

as balancing numbers of atoms
• the step-by-step process to balance a redox reaction is much more

involved
• separating the overall reaction into two half-reactions
• balancing charges using electrons
• balancing the overall redox reaction under neutral, acidic (H+), or basic (OH–)
conditions
Steps for Balancing a Redox Reaction
MnO4–(aq) reacts with Cl–(aq) to form MnO2(s) and ClO3–(aq)
balance this reaction under acidic conditions and then under basic conditions
acidic conditions
2 H+(aq) + Cl–(aq) + 2 MnO4–(aq) → 2 MnO2(s) + ClO3–(aq) + H2O(ℓ)
–1 net charge –1 net charge
basic conditions
H2O(ℓ) + Cl–(aq) + 2 MnO4–(aq) → 2 MnO2(s) + ClO3–(aq) + 2 OH–(aq)
–3 net charge –3 net charge

Steps for Balancing a Redox Reaction
MnO4–(aq) reacts with Cl–(aq) to form MnO2(s) and ClO3–(aq)
balance this reaction under acidic conditions and then under basic conditions
1. assign oxidation numbers to all species in the overall reaction to establish which
reactant is undergoing oxidation and which reactant is undergoing reduction
+7 –2 –1 +4 –2 +5 –2
MnO4–(aq) + Cl–(aq) → MnO2(s) + ClO3–(aq)
reduction
oxidation
2. separate the overall reaction into an oxidation half-reaction and a reduction half-
reaction
• usually each half-reaction will have its own reactant and its own product (both of which
contain a species that is undergoing a change in oxidation number)
• H2O, H+ or OH– should be included at this point only if it contains an atom that is undergoing
a change in oxidation number (like when H2O2 converts into H2O)
• sometimes a reactant can form more than one product
• for disproportionation reactions, the reactant will be the same in both half-reactions
oxidation: Cl–(aq) → ClO3–(aq)
reduction: MnO4–(aq) → MnO2(s)
Steps for Balancing a Redox Reaction (continued)
3. for each half-reaction balance all atoms except O and H
oxidation: Cl–(aq) → ClO3–(aq)
reduction: MnO4–(aq) → MnO2(s)
4. now balance oxygens by adding H2O(ℓ)

oxidation: 3 H2O(ℓ) + Cl–(aq) → ClO3–(aq)
reduction: MnO4–(aq) → MnO2(s) + 2 H2O(ℓ)
5. then balance hydrogen by adding H+(aq)

oxidation: 3 H2O(ℓ) + Cl–(aq) → ClO3–(aq) + 6 H+(aq)
reduction: 4 H+(aq) + MnO4–(aq) → MnO2(s) + 2 H2O(ℓ)
6. balance the charge of the oxidation half-reaction by adding electrons (e–) to the right
side of the equation so that both sides of the equation has the same charge
oxidation: 3 H2O(ℓ) + Cl–(aq) → ClO3–(aq) + 6 H+(aq) + 6 e–
reduction: 4 H+(aq) + MnO4–(aq) → MnO2(s) + 2 H2O(ℓ)
7. balance the charge of the reduction half-reaction by adding electrons (e–) to the left
side of the equation so that both sides of the equation has the same charge
• note that same charge does not necessarily mean neutral
reduction: 3 e– + 4 H+(aq) + MnO4–(aq) → MnO2(s) + 2 H2O(ℓ)
8. multiply through one or both half-reactions by a necessary number so that the
number of electrons in both half-reactions is the same
reduction: 2 × (3 e– + 4 H+(aq) + MnO4–(aq) → MnO2(s) + 2 H2O(ℓ) )
6 e– + 8 H+(aq) + 2 MnO4–(aq) → 2 MnO2(s) + 4 H2O(ℓ)
9. add up half-reactions and cancel species appropriately
2 1
reduction: 6 e– + 8 H+(aq) + 2 MnO4–(aq) → 2 MnO2(s) + 4 H2O(ℓ)
this is the balanced redox reactions under acidic conditions
10. if balancing under basic conditions, add enough OH–s to the side of the equation with
H+s to neutralize them into water. To keep the equation balanced, add the same # of
OH–s to the opposite side. Re-cancel the appropriate number of H2Os
+ 2 OH– + 2 OH–
1
2 H2O
H2O(ℓ) + Cl–(aq) + 2 MnO4–(aq) → 2 MnO2(s) + ClO3–(aq) + 2 OH–(aq)
this is the balanced redox reactions under basic conditions
Try This
Balance the following redox reaction:
+7 –2 +1 –1 +3 –2 0
Cl2O7(g) + H2O2(aq) → ClO2 (aq) + O2(g) (basic conditions)
–
reduction: 8 e– + 6 H+(aq) + Cl2O7(g) → 2 ClO2–(aq) + 3 H2O(ℓ)

oxidation: ( H2O2(aq) → O2(g) + 2 H+(aq) + 2 e– ) × 4
2
oxidation: 4 H2O2(aq) → 4 O2(g) + 8 H+(aq) + 8 e–
4 H2O2(aq) + Cl2O7(g) → 2 ClO2–(aq) + 4 O2(g) + 3 H2O(ℓ) + 2 H+(aq)

+ 2 OH–(aq) + 2 OH–(aq)
2 H2O(ℓ)
2 OH–(aq) + 4 H2O2(aq) + Cl2O7(g) → 2 ClO2–(aq) + 4 O2(g) + 5 H2O(ℓ)

Balance the following redox reactions under the indicated conditions
• Fe2+(aq) + Cr2O72–(aq) → Fe3+(aq) + Cr3+(aq) (acidic media)
14 H+(aq) + 6 Fe2+(aq) + Cr2O72–(aq) → 6 Fe3+(aq) + 2 Cr3+(aq) + 7 H2O(ℓ)
• Fe3+(aq) + NH2OH2+(aq) → Fe2+(aq) + N2O(g) (acidic media)
4 Fe3+(aq) + 2 NH2OH2+(aq) → 4 Fe2+(aq) + N2O(g) + H2O(ℓ) + 6 H+(aq)
• S8(s) + O2(g) → SO42–(aq) (acidic media)
8 H2O(ℓ) + S8(s) + 12 O2(g) → 8 SO42–(aq) + 16 H+(aq)
• Br2(ℓ) → Br–(aq) + BrO3–(aq) (a disproportionation rxn in basic media)
6 OH–(aq) + 3 Br2(ℓ) → 5 Br–(aq) + BrO3–(aq) + 3 H2O(ℓ)
• OCN–(aq) + OCl–(aq) → CO32–(aq) + N2(g) + Cl–(aq) (basic media)
2 OH–(aq) + 2 OCN–(aq) + 3 OCl–(aq) → 2 CO32–(aq) + N2(g) + 3 Cl–(aq) + H2O(ℓ)
Announcements for Wednesday, 05APR2023
• Replacement Grade Policy
• See Canvas announcement from Apr 3 for more details

Balance the following redox reactions under the indicated conditions
• Fe2+(aq) + Cr2O72–(aq) → Fe3+(aq) + Cr3+(aq) (acidic media)
14 H+(aq) + 6 Fe2+(aq) + Cr2O72–(aq) → 6 Fe3+(aq) + 2 Cr3+(aq) + 7 H2O(ℓ)
• Fe3+(aq) + NH2OH2+(aq) → Fe2+(aq) + N2O(g) (acidic media)
4 Fe3+(aq) + 2 NH2OH2+(aq) → 4 Fe2+(aq) + N2O(g) + H2O(ℓ) + 6 H+(aq)
• S8(s) + O2(g) → SO42–(aq) (acidic media)
8 H2O(ℓ) + S8(s) + 12 O2(g) → 8 SO42–(aq) + 16 H+(aq)
• Br2(ℓ) → Br–(aq) + BrO3–(aq) (a disproportionation rxn in basic media)
6 OH–(aq) + 3 Br2(ℓ) → 5 Br–(aq) + BrO3–(aq) + 3 H2O(ℓ)
• OCN–(aq) + OCl–(aq) → CO32–(aq) + N2(g) + Cl–(aq) (basic media)
2 OH–(aq) + 2 OCN–(aq) + 3 OCl–(aq) → 2 CO32–(aq) + N2(g) + 3 Cl–(aq) + H2O(ℓ)
Electrical Energy and Current
• in electrochemistry, chemical energy is converted into electrical energy
by carrying out a redox reaction in an electrochemical cell
• specifically by causing electron flow to occur through a wire
• flow of electric charge = current
• amount of charge passing a point over a given amount of time
• flow of electrons through a wire
• flow of ions through a solution
• current is measured in units of amperes (A)
1 A = 1 C/s (a conversion factor!)
• the charge of an electron = 1.602×10–19 C so 1 ampere is equivalent to
the flow of 6.242×1018 e–s per second
Spontaneous Redox Reaction Illustrated
consider the spontaneous reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
• reduction: Cu2+(aq) + 2 e– → Cu(s)
• oxidation: Zn(s) → Zn2+(aq) + 2 e– • soluble copper(II) ions are
converted to insoluble copper
metal which deposits onto the
surface of the Zn strip
• the disappearance of the blue
color indicates the consumption
of Cu2+(aq)
• rust-colored copper forms over
the silvery zinc
• zinc metal is converted into zinc
ions causing the metal strip to
© 2018 Pearson Education, Inc. dissolve
• electron transfer occurs directly in solution from the surface of Zn(s) to Cu2+(aq)
• however, if electron transfer were to occur through a wire, an electrical current would be
produced
Voltaic/Galvanic Cell – in General
an apparatus that produces an electrical current from a spontaneous redox reaction
Zn(s) → Zn2+(aq) + 2 e– and Cu2+(aq) + 2 e– → Cu(s)
• the places where oxidation and
reduction occur are separated
• each “place” is called a half-cell
• each half-cell is composed of an electrode
and components for a given half-reaction
• electron transfer between reducing
agent and oxidizing agent occurs
indirectly through a wire connecting
the two half-cells
• this flow of electrons constitutes a current
oxidation half-cell (anode) reduction half-cell (cathode)
• the driving force for electron flow is the difference in the electrons’ potential energy
between the two half-cells/electrodes
• electrons will spontaneously flow from the electrode of greater potential energy to the
electrode of lower potential energy
Cell Potential (Ecell)
Ecell = the potential difference between the two half-cells in a voltaic cell
• also known as voltage
• the cell potential gives rise to the force that results in electron flow
• the greater the difference of potentials between the half-cells, the greater the force of e– flow
• cell potential/voltage is measured in volts (V)

1 V = 1 J/C (another conversion factor!)
• 1 coulomb of charge will experience 1 J of energy difference between the two half-
cells
 cell potential is a measure of a redox reaction’s spontaneity
• when Ecell = (+) the reaction is spontaneous in the forward direction
• when Ecell = (–) the forward reaction is nonspontaneous (reverse reaction is
spontaneous)
𝐨
• standard cell potential (𝐄𝐜𝐞𝐥𝐥 ) = the cell potential under standard conditions
• solutions at 1 M and gases at partial pressures of 1 atm
Key Components of a Voltaic Cell
• electrodes = conductive surfaces through which
the electrons enter and leave the half-cells
through an attached wire
• anode = the electrode where oxidation occurs
• acts as a source of electrons
• designated by a negative sign (–)
• cathode = the electrode where reduction occurs
• consumes the electrons formed at the anode
• designated by a positive sign (+)
electrons flow from the anode to the cathode
• salt bridge = typically a U-shaped tube filled with a strong electrolyte used to
prevent charge build-up and complete the circuit
• as e– s flow, positive and negative charges builds-up in the anode and cathode, respectively
• anions in the salt bridge migrate towards the anode
• cations in the salt bridge migrate towards the cathode
Inert Electrodes
consider a voltaic cell based on the following half-reactions
anode (oxidation): Fe(s) → Fe2+(aq) + 2 e–
cathode (reduction): MnO4–(aq) + 8 H+(aq) + 5 e– → Mn2+(aq) + 4 H2O(ℓ)
• What would serve as the electrode in the anode half-cell? Fe(s)

• What would serve as the electrode in the cathode half-cell? Problem!
• all of the species are aqueous
• a metal surface is needed to serve as the electrode
 in half-cells where all of the principal species are in the aqueous
and/or gas phases, an INERT ELECTRODE must be employed
• typically platinum (Pt) or graphite
Electrochemical Cell Notation
• shorthand way of expressing the components (and amounts) of a voltaic cell
• AKA: cell diagram or line notation
electrode (s) | (s) | (aq) | (g) || (aq) | (g) | (s) | electrode (s)
anode half-cell cathode half-cell

first second
|| denotes the salt bridge

| denotes a phase boundary (i.e., a different physical state)
• if there is more than one (aq) component in a half-cell,
separate with comma(s) and list them in the order that
they appear in the half-reaction for that half-cell
Electrochemical Cell Notation (continued)
Zn2+ Cu2+

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s)
Fe(s) | Fe2+(aq) || MnO4–(aq), H+(aq), Mn2+(aq) | Pt(s)

Try This
• Determine the balanced redox reaction being used to generate
electricity in the following voltaic cell
Pt(s) | Sn2+(aq), Sn4+(aq) || NO3–(aq), H+(aq) | NO(g) | Pt(s)
8 H+(aq) + 2 NO3–(aq) + 3 Sn2+(aq) → 2 NO(g) + 3 Sn4+(aq) + 4 H2O(ℓ)
Standard Electrode Potentials (E°)
• recall that a potential difference between the two electrodes forces
electrons to flow spontaneously
• the greater the difference in potentials between the two electrodes, the greater
the force for electrons to flow
• analogous to the flow of water downhill
• the greater the differences in height, the greater the flow
• standard electrode potential = the potential of an electrode to

attract/consume electrons
• standard = standard state (1 atm pressure and 1 M concentrations)
• by convention, standard electrode potentials are given as reduction potentials
• the more positive the standard electrode potential, the greater the tendency of
the electrode to draw electrons towards it for reduction to take place
Standard Electrode Potentials (E°) (continued)
• a positive electrode potential reflects a high tendency for reduction

Cl2(g) + 2 e– → 2 Cl–(aq) E° = +1.36 V (Cl2 is a strong oxidizing agent)
• a negative electrode potential reflects a low tendency for reduction

(and a high tendency for oxidation)
Na+(aq) + e– → Na(s) E° = –2.71 V 
Na(s) → Na+(aq) + e– E° = +2.71 V (Na is a strong reducing agent)
• coupling an electrode having a high tendency for reduction with an

electrode having a high tendency for oxidation leads to an
electrochemical cell with a large overall cell potential
Announcements for Thursday, 06APR2023
• Graded and Timed Quizzes 9a & 9b – “Thermodynamics” due Monday,
10APR2023, at 6:00 PM (EDT)
• Replacement Grade Policy

Standard Electrode Potentials (E°) (continued)
Reduction Half-Reaction E°(V)
Stronger F2(g) + 2 e– → 2 F–(aq) 2.87 Weaker
oxidizing agent reducing agent
MnO4–(aq) + 4 H+(aq) + 3 e– → MnO2(s) + 2 H2O(ℓ) 1.68
Sn4+(aq) + 2 e– → Sn2+(aq) 0.15
2 H+(aq) + 2 e– → H2(g) 0
Fe3+(aq) + 3 e– → Fe(s) –0.036
Weaker
Ca2+(aq) + 2 e– → Ca(s) –2.76 Stronger
oxidizing agent Li+(aq) + e– → Li(s) –3.04 reducing agent
• the more positive the E°, the more readily the indicated half-reaction undergoes
reduction
• the more negative the E°, the more readily the indicated half-reaction goes in the
reverse direction and undergoes oxidation
• in a voltaic cell, electrons will flow spontaneously from the electrode with the lower
E° to the electrode with the higher E°
Standard Hydrogen Electrode (SHE)
• the absolute potential of a given electrode cannot be measured
• an electrode’s potential can only be measured when the electrode is coupled
with a second electrode in a voltaic cell
• for 2 H+(aq) + 2 e– → H2(g), E° is arbitrarily assigned

the value of 0 V
• all other electrode potential values are established
relative to this standard
• the half-cell is called the standard hydrogen electrode
(SHE)
• half-reactions with a stronger tendency toward reduction
than the SHE have a positive value for E°red
• half-reactions with a stronger tendency toward oxidation
than the SHE have a negative value for E°red
• for an oxidation half-reaction, E°oxidation = −E°reduction
Standard Electrode Potentials (E°) Revisited
• the E° values AS THEY ARE WRITTEN
indicate the potentials of the half-
reactions to go in the direction of
Half-Reaction
reduction
• half-reactions with higher E° values have a
greater tendency to undergo reduction than
those with lower E° values
• changing the sign of E° gives the potential
of the half-reaction to go in the opposite
direction towards oxidation
• the value of E° would then represent the
electrode’s OXIDATION POTENTIAL
whenever two half-reactions are chosen from the above table to form a
voltaic cell (from a spontaneous redox rxn)
• the half-reaction higher above in the table will act as the cathode (undergoes reduction)
• the half-reaction lower in the table will act as the anode (undergoes oxidation)
o
Determining Standard Cell Potential (Ecell )
• all components are under standard conditions (1 atm and 1 M)
• the overall cell potential depends on the difference between individual electrode potentials
 a standard electrode/reduction potential is an intensive property
 when determining the cell potential, do not multiply the half-cell E° values, even if you need to
multiply the half-reactions to balance the redox equation!
𝐨
two different conceptual approaches to determining 𝐄𝐜𝐞𝐥𝐥
1. difference in electrode potentials between the cathode and the anode
𝐨 𝐨 𝐨
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐚𝐭𝐡𝐨𝐝𝐞 − 𝐄𝐚𝐧𝐨𝐝𝐞
o o
where Ecathode and Eanode are standard electrode potentials of the cathode and anode
Half-Reaction
• when using this equation, use the values of E° exactly as they are from a table of electrode
potentials
o
Determining Standard Cell Potential (Ecell ) (continued)
o
2. alternatively Ecell can be thought of as the sum of the reduction
potential of the reaction in the cathode and the oxidation potential of
the reaction in the anode
𝐨 𝐨 𝐨
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐫𝐞𝐝 + 𝐄𝐨𝐱
o
• Ered = E° from the table
o = –(E°) from the table
• Eox
• when using this approach, the oxidation potential of a half-reaction can be
determined by changing the sign of its standard electrode potential
Half-Reaction for Ba(s) → Ba2+(aq) + 2 e–
o = –(–2.90) = + 2.90 V
Eox
o
o
determine Ecell for Cr(s) + Pb2+(aq) → Cr3+(aq) + Pb(s) given
E° (V)
Pb2+(aq) + 2 e– → Pb(s) –0.13
Cr3+(aq) + 3 e– → Cr(s) –0.73
o o o
1. using Ecell = Ecathode − Eanode
cathode: Pb2+(aq) + 2 e– → Pb(s)
o
Ecathode = −0.13 V
anode: Cr3+(aq) + 3 e– → Cr(s)
o
Eanode = −0.73 V
o o o
Ecell = Ecathode − Eanode = −0.13 − −0.73 = +0.60 V
𝐨
𝐄𝐜𝐞𝐥𝐥 is positive indicating that Cr(s) + Pb2+(aq) → Cr3+(aq) + Pb(s) is spontaneous
under standard conditions
o
o
determine Ecell for Cr(s) + Pb2+(aq) → Cr3+(aq) + Pb(s) given
E° (V)
Pb2+(aq) + 2 e– → Pb(s) –0.13
Cr3+(aq) + 3 e– → Cr(s) –0.73
o o o
2. using Ecell = Ered + Eox
reduction: Pb2+(aq) + 2 e– → Pb(s)
o
Ered = −0.13 V
oxidation: Cr(s) → Cr3+(aq) + 3 e–
o = − −0.73 V = +0.73 V
Eox
o o o
Ecell = Ered + Eox = −0.13 + 0.73 = +0.60 V
• remember that 𝑬𝒐𝒓𝒆𝒅 is an INTENSIVE PROPERTY(!!) and does NOT
change when multiplying the half-reaction by a certain factor
Try This
• determine if the following reaction is spontaneous under standard conditions
Mn2+(aq) + 2 Cu2+(aq) + 2 H2O(ℓ) → MnO2(s) + 2 Cu+(aq) + 4 H+(aq)
given
MnO2(s) + 4 H+(aq) + 2 e– → Mn2+(aq) + 2 H2O(ℓ) E° = 1.21 V
Cu2+(aq) + e– → Cu+(aq) E° = 0.16 V
𝐨
𝐄𝐜𝐞𝐥𝐥 = –1.05 V; reaction is NOT spontaneous
o
• write the cell diagram (and give Ecell ) for the voltaic cell employing the
following two half-cells
PbO2(s) + 4 H+(aq) + SO42–(aq) + 2 e– → PbSO4(s) + 2 H2O(ℓ) E° = 1.69 V
Au3+(aq) + 3 e– → Au(s) E° = 1.50 V
Dissolving Metals in Acid (H+)
• a metal will dissolve in acid (like HCl) when the
potential for the reduction of H+(aq) to H2(g) is
greater than the reduction potential of the metal’s
cation
• in the table of electrode potentials, any metal listed
below the standard hydrogen electrode will dissolve in
strong acid
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
Free Energy and Cell Potential
• an electrochemical reaction is spontaneous when Ecell (+) and nonspontaneous
when Ecell (–)
• recall from Ch 18 that a process is spontaneous when DG (–) and
nonspontaneous when DG (+)
• since both predict spontaneity, DG and Ecell must be related
o
ΔGo = −nFEcell
• ΔGo = standard free energy change (J)
o
• Ecell = standard cell potential (V or J/C)
• n = number of moles of electrons transferred in the balanced redox reaction
• F = Faraday’s constant = 96 485 C/mol e– (another conversion factor!)
• gives the charge (in C) of 1 mole of electrons
• note that DG  Ecell but opposite in sign
Determine ΔGo for Pb(s) + Cr3+(aq) → Pb2+(aq) + Cr(s) given Ecell
o
= – 0.60 V
𝚫𝐆𝐨 = +350 kJ (nonspontaneous)
Relating an Equilibrium Constant (K) to Cell Potential
recall from Ch 18: ΔGo = −RT ln K
substitute DG° with –nFE°cell and divide by –nF
o RT
Ecell = ln K (at any T)
nF
at 25 °C (298 K) substitute values for T, R, and F
o 0.02569 V o 0.0592 V
at 25 °C, Ecell = ln K or Ecell = log K
n n
o
a positive value of Ecell = a value of K > 1
• products favored over reactants
o
a negative value of Ecell = a value of K < 1
• reactants favored over products
Nonstandard Cell Potential (Ecell)
• recall from Ch 18 that there are relationships among
• the reaction quotient, Q; the equilibrium constant, K; and the free energy change, ΔG°
• changing the concentrations of the reactants and products to concentrations
other than 1 M will impact the free energy change, ΔG
• because ΔG is related to the cell potential, Ecell, the voltage for the cell will be different
when the ion concentrations are not 1 M

• Updated Exam Replacement Policy
• Exam III is Wednesday, 19APR2023, 9:20-10:50 PM (EDT)
• Coverage: Chapters 17.5-19.5; exam consists of 25 questions (mixture of open-answer,
• Same Locations as Exams I & II
• Practice Exam 3 available on Canvas

o
• write the cell diagram (and give Ecell ) for the voltaic cell employing the
following two half-cells
PbO2(s) + 4 H+(aq) + SO42–(aq) + 2 e– → PbSO4(s) + 2 H2O(ℓ) E° = 1.69 V
Au3+(aq) + 3 e– → Au(s) E° = 1.50 V
𝐨
Au(s) | Au3+(aq) || PbO2(s), PbSO4(s) | SO42–(aq), H+(aq) | Pt(s) 𝐄𝐜𝐞𝐥𝐥 = 0.19 V
Exam III goes up to and includes Chapter 19.5
The following material will NOT be on Exam III but

will be on the Final Exam
Concentration and Nonstandard Cell Potential (Ecell) Related
recall from Ch 18: ΔG = ΔGo + RT ln Q
substitute DGs with –nFEcell and divide by –nF
o RT
Ecell = Ecell − ln Q the Nernst equation
nF
at 25 °C (298 K) substitute values for T, R, and F
o 𝟎.𝟎𝟐𝟓𝟔𝟗 V o 𝟎.𝟎𝟓𝟗𝟐 V
at 25 °C, Ecell = Ecell − ln Q OR Ecell = Ecell − log 𝑄
n n
o
• when Q = 1, all species are at standard conditions and Ecell = Ecell
o
• when Q < 1, Ecell > Ecell
o
• when Q > 1, Ecell < Ecell
• when Q = K, reaction is at equilibrium and Ecell = 0 V
Try This
• determine the potential of an electrochemical cell represented by the
following cell diagram
o
Ni(s)|Ni2+(aq, 2.0 M) || VO2+(aq, 0.010 M), H+(aq, 1.0 M), VO2+ (aq, 2.0 M)|Pt(s) Ecell = 1.23 V
𝐄𝐜𝐞𝐥𝐥 = 1.08 V
oxidation half-reaction: Ni(s) → Ni2+(aq) + 2 e–
reduction half-reaction: 2 × (2 H+(aq) + VO2+(aq) + e– → VO2+(aq) + H2O(ℓ))
4 H+(aq) + 2 VO2+(aq) + 2 e– → 2 VO2+(aq) + 2 H2O(ℓ)
balanced redox reaction: 4 H+(aq) + Ni(s) + 2 VO2+(aq) → Ni2+(aq) + 2 VO2+(aq) + 2 H2O(ℓ)
𝑁𝑖 2+ 𝑉𝑂2+ 2 2.0 2.0 2 4 o 0.0592 V

𝑄= + = = 8.0 × 10 Ecell = Ecell − log 𝑄
𝐻 + 4 𝑉𝑂2 2 1.0 4 0.010 2 n
0.0592 V
Ecell = 1.23 V − log 8.0 × 104
𝟐
Ecell = 1.23 V − 0.15 V = 𝟏. 𝟎𝟖 𝐕
Concentration Cells
concentration cell = a voltaic cell that employs the same half-reaction
within the anode and cathode
• a difference in concentration between the half-cells drives
spontaneous electron flow from the anode to the cathode
• anode is the half-cell with the lower concentration
• cathode is the half-cell with the higher concentration
• electron flow continues until the concentrations within both half-
cells become equal
• concentration within the anode increases and concentration within the cathode
decreases
𝐨
• because the same half-reaction is used for both half-cells, 𝐄𝐜𝐞𝐥𝐥 =0V
• the potential of a concentration cell can be calculated using the
Nernst equation 𝐨 0.0592 V
Ecell = 𝐄0𝐜𝐞𝐥𝐥
V − log 𝑄
n
0.0592 V anode x 0.0592 V lower x
Ecell = − log OR Ecell = − log
n cathode n higher
x = coefficient from balanced reaction
Concentration Cell Illustrated
1
0.0592 V anode
Ecell =− log
n cathode
1
0.0592 V 0.010
Ecell =− log
𝟐 2.0
Ecell = 𝟎. 𝟎𝟔𝟖 𝐕
oxidation © 2018 Pearson Education, Inc. reduction
Cu(s) → Cu2+(aq, 0.010 M) + 2 e– Cu2+(aq, 2.0 M) + 2 e– → Cu(s)
[Cu2+] will increase [Cu2+] will decrease
“overall reaction” Cu2+(aq, 2.0 M) → Cu2+(aq, 0.010 M)

Try This
• determine the [Fe3+] of the solution in the anode within the following
concentration cell
Fe(s) | Fe3+(aq, ? M) || Fe3+(aq, 2.0 M) | Fe(s)
Ecell = 0.0340 V
[Fe3+] = 0.038 M
oxidation half-reaction (anode): Fe(s) → Fe3+(aq, ? M) + 3 e–
reduction half-reaction (cathode): Fe3+(aq, 2.0 M) + 3 e– → Fe(s)
overall reaction: Fe3+(aq, 2.0 M) → Fe3+(aq, ? M)
o 0.0592 V anode 1 xM 1
Ecell = Ecell
− log 𝑄 where 𝑄 = =
n cathode 2.0 M
0.0592 V x 1
0.0340 V = 0 − log
3 2.0
x = [Fe3+] = 0.038 M
• determine E° for Mn2+(aq) + 2 e– → Mn(s) given
Fe3+(aq) + 3 e– → Fe(s) E° = –0.036 V
3 Mn(s) + 2 Fe3+(aq) → 3 Mn2+(aq) + 2 Fe(s) DG°rxn = –662 kJ
Announcements for Thursday, 20APR2023
• Week 11 Homework Assignments have been reopened
• Graded and Timed Quizzes 9a & 9b – “Thermodynamics” due Monday,
24APR2023, at 6:00 PM (EDT)
• Graded and Timed Quizzes 10a & 10b – “Electrochemistry” due Monday,
24APR2023, at 6:00 PM (EDT)

• determine E° for Mn2+(aq) + 2 e– → Mn(s) given
Fe3+(aq) + 3 e– → Fe(s) E° = –0.036 V
3 Mn(s) + 2 Fe3+(aq) → 3 Mn2+(aq) + 2 Fe(s) DG°rxn = –662 kJ
oxidation E° = –1.18 V
3 Mn(s) + 2 Fe3+(aq) → 3 Mn2+(aq) + 2 Fe(s) o o
∆Grxn = −nFEcell
reduction o
–6.62×105 J = –(6 mol e-) (96485 C/mol e-) Ecell
2 Fe3+(aq) + 6 e– → 2 Fe(s) o
Ecell = +1.14 V
reduction in cathode
o
Ecathode = –0.036 V
3 Mn(s) → 3 Mn2+(aq) + 6 e– o
Ecell o
= Ecathode o
− Eanode
oxidation in anode o
1.14 V = –0.036 V – Eanode
o
Eanode =?V o
Eanode = –0.036 – 1.14 = – 1.18 V
Electrolytic Cells
electrolytic cell = an electrochemical cell that utilizes an electrical current to
force a nonspontaneous chemical reaction to occur
• it’s the “opposite” of a voltaic cell
• oxidation still takes place in the anode
• reduction still takes place in the cathode
• electron flow is still from anode to cathode
 an outside power source is required to
drive electron flow
• a battery or DC power supply
• anode of electrolytic cell attaches to
(+) terminal of external battery
• cathode of electrolytic cell attaches to
(–) terminal of external battery © 2018 Pearson Education, Inc.
• without an outside power source, the nonspontaneous redox reaction of
Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s) will not occur
Electrolysis of Water
electrical current causes water to decompose into its constituent elements
2 H2O(ℓ) → 2 H2(g) + O2(g) (nonspontaneous)
anode (oxidation)
2 H2O(ℓ) → O2(g) + 4 H+(aq) + 4 e–
cathode (reduction)
2 H2O(ℓ) + 2 e– → H2(g) + 2 OH–(aq)
O2(g) and H2(g) produced in a 1:2 anode cathode

molar ratio © 2018 Pearson Education, Inc.
Voltaic Cells vs. Electrolytic Cells
voltaic a brief comparison electrolytic
both
• oxidation at the anode
• reduction at the cathode
• e–s flow from anode to
cathode
• redox reaction → electrical current • electrical current → nonspontaneous reaction

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s)
• anode (–) is the source of electrons • anode attached to (+) terminal of battery
• cathode (+) draws electrons towards it • e–s pulled out of anode by the battery
• spontaneously occurs • cathode attached to (–) terminal of battery
• e–s forced into the cathode by the battery
Some Practical Applications of Electrolytic Cells
• extraction
extraction and
and purification
purificationof
of
metals from
from minerals
minerals
• electrolysis of molten ionic
compounds
• electroplating
electroplating metal extraction
• electrolysis of Ag(+) solution for
silver deposition
• production of H2(g) for fuel cells
silver plating
Predicting Products of Electrolysis – Molten Salts
consider the electrolysis of pure molten NaCl(ℓ) (mp = 801 °C)
• only Na+(ℓ) and Cl–(ℓ) present
oxidation at the anode
theoretically two possible reactions:
2 Cl–(ℓ) → Cl2(g) + 2 e– or Na+(ℓ) → Na2+(ℓ) + e–
• Na+ already at its highest oxidation state
• oxidation of Cl–(ℓ) to Cl2(g) will occur much more readily
reduction at the cathode
again, theoretically two possible reactions:
Cl–(ℓ) + e– → Cl2–(ℓ) or Na+(ℓ) + e– → Na(s)
• Cl– already at its lowest oxidation state; can only undergo
oxidation © 2018 Pearson Education, Inc.
• reduction of Na+(ℓ) to Na(s) will occur
Predicting Products of Electrolysis – Molten Salts (continued)
now consider the electrolysis of a molten mixture of NaCl(ℓ) and KCl(ℓ)
Na+, K+, and Cl– present
What products will result from electrolysis?
• at the anode: Cl– will oxidize to Cl2
• at the cathode, two possible reductions :
• Na+(ℓ) + e– → Na(s) Na+(aq) + e– → Na(s) E° = –2.71 V
• K+(ℓ) + e– → K(s) K+(aq) + e– → K(s) E° = –2.92 V
• which will occur more readily?
• K+ has a more negative reduction potential than Na+
• Na+ is more easy to reduce than K+
• Na(s) will preferentially form at the cathode over K(s)
• a mixture of anions (example NaCl(ℓ) and NaBr(ℓ))
• the same approach would be followed but the anions’ oxidation potentials
must be compared instead of their reduction potentials
Predicting Products of Electrolysis – Aqueous Solutions
consider the electrolysis of NaI(aq)
• Na+(aq), I–(aq), and H2O(ℓ) present
• more difficult to predict the products than in molten
NaI because water can undergo electrolysis
oxidation at the anode: two possible reactions
• 2 I–(aq) → I2(s) + 2 e– o
Eox = –0.54 V
• 2 H2O(ℓ) → O2(g) + 4 H+(aq) + 4 e– 𝐄𝐨𝐱 = –0.82 V
• remember Eox o = –(E o )
• ox. potential for water at pH = 7 (nonstandard conditions)
• oxidation of I–(aq) will occur over H2O(ℓ)
reduction at the cathode: two possible reactions
• Na+(aq) + e– → Na(s) E o = –2.71 V
• 2 H2O(ℓ) + 2 e– → H2(g) + 2 OH–(aq) 𝐄 = –0.41 V
• red. potential for water at pH = 7 (nonstandard
conditions) © 2018 Pearson Education, Inc.
• reduction of H2O(ℓ) will occur over Na+(aq)

Electroplating and Stoichiometry of Electrolysis
• in electroplating, metal cations are reduced at the cathode to form the
neutral metal
• the metal gets deposited onto the exterior of the cathode
• in this reduction, electrons act as a reactant along with the metal cation
and the plated metal is the product
• the electrons are added via an electrical current that’s added to the electrolytic cell
over a period of time
experimentally it is observed that
• the higher the electrical current, the more metal deposited at the cathode
• the longer the duration of current, the more metal deposited at the cathode
 the amount of metal deposited at the cathode over a given time with a
given current is related stoichiometrically to the reduction reaction and the
amount of electrons added
• it can be calculated by a dimensional analysis approach using current (C/s) and
Faraday’s constant (96 485 C/mol e–) as conversion factors
Electroplating and Stoichiometry of Electrolysis (continued)
consider the electroplating of copper from

aqueous solution using an electrolytic cell
• a 3.5-A current is run through the
electrolytic cell on the right for 70.0 s. What
mass of copper (mg) will be deposited at the
cathode during that time? The molar mass
of Cu = 63.55 g/mol 81 mg
Cu2+(aq) + 2 e– → Cu(s)
F = 96 485 C/mol e–
𝟑. 𝟓 𝐂 1 mol e− 𝟏 𝐦𝐨𝐥 𝐂𝐮(𝐬) 𝟔𝟑. 𝟓𝟓 𝐠 1000 mg

70.0 s × × × −
× × = 81 mg
𝟏𝐬 96 485 C 𝟐 𝐦𝐨𝐥 𝒆 𝟏 𝐦𝐨𝐥 𝐂𝐮 1g
Batteries and Corrosion

• read on your own…

Try This
• What magnitude of current is required to deposit 17.7 mg Al(s) at the
cathode in 0.3986 h in the electrolysis of molten AlCl3? 0.132 A
at the cathode: Al3+(ℓ) + 3 e– → Al(s)
17.7 mg Al 1h 1 min 1g 1 mol Al 3 mol e− 96 485 C

× × × × × × −
= 0.132 C/s
0.3986 h 60 min 60 s 1000 mg 26.98 g 1 mol Al 1 mol e or
0.132 A
• Determine Ecell of the following reaction when carried out in a voltaic cell
ClO3–(0.65 M) + 3 Mn2+(0.25 M) + 3 H2O(ℓ) → Cl–(1.50 M) + 3 MnO2(s) + 6 H+(1.25 M)
o
given Ecell = 0.22 V. 0.19 V
• Using standard electrode potentials from your textbook, predict the probable
products and the approximate minimum voltage required in the electrolysis
with inert platinum electrodes of MgBr2(ℓ). Mg(s) and Br2(ℓ); 3.46 V
• How many mL of H2(g), measured at 23.5 °C and 749 mmHg, are produced at
a graphite cathode in the electrolysis of water by 2.45 A of current in 5.00
min? 94.1 mL
• Challenging: Consider the voltaic cell with the following cell diagram
Pt(s)|H2(g, 1 atm)|H+(aq, x M) || H+(aq, 1 M)|H2(g, 1 atm)|Pt(s) Ecell = 0.108 V What is the
pH of the unknown solution? pH = 1.82
• Week 11 Homework Assignments have been reopened
• Graded and Timed Quizzes 9a & 9b – “Thermodynamics” due tonight at
6:00 PM (EDT)
• Graded and Timed Quizzes 10a & 10b – “Electrochemistry” due tonight at
6:00 PM (EDT)
• Final Exam is Monday, 08MAY2023, 12:00-3:00 PM (EDT)
• Coverage: Chapters 13-20
• See the Canvas Announcement from today for full details
• Exam locations will be in a separate Canvas Announcement

Today’s Agenda – 24APR2023
• Start Chapter 20, only sections 1–6

• radioactive decay, nuclear stability, radioactive decay
kinetics, and radiometric dating
• we are NOT covering sections 7-12 and you are not
responsible for that material
• Determine Ecell of the following reaction when carried out in a voltaic cell
ClO3–(0.65 M) + 3 Mn2+(0.25 M) + 3 H2O(ℓ) → Cl–(1.50 M) + 3 MnO2(s) + 6 H+(1.25 M)
o
given Ecell = 0.22 V. 0.19 V
• Using standard electrode potentials from your textbook, predict the probable
products and the approximate minimum voltage required in the electrolysis
with inert platinum electrodes of MgBr2(ℓ). Mg(s) and Br2(ℓ); 3.46 V
• How many mL of H2(g), measured at 23.5 °C and 749 mmHg, are produced at
a graphite cathode in the electrolysis of water by 2.45 A of current in 5.00
min? 94.1 mL
• Challenging: Consider the voltaic cell with the following cell diagram
Pt(s)|H2(g, 1 atm)|H+(aq, x M) || H+(aq, 1 M)|H2(g, 1 atm)|Pt(s) Ecell = 0.108 V What is the
pH of the unknown solution? pH = 1.82
Chapter 20: Radioactivity and Nuclear Chemistry
• What is radioactivity and why are certain isotopes radioactive?
• What are the different types of radioactivity?
• How can the stability of an isotope be determined and how can the mode of
radioactive decay be predicted?
• How are nuclear equations written and balanced?
• How is radioactivity detected and measured?
• What are the kinetics of radioactive decay?
• How does carbon-14 dating work?
• What are nuclear fission and nuclear fusion?
• How is mass converted into energy in a nuclear reaction and how are energy
changes quantified?
• How are new elements synthesized?
for Chapter 20
• atomic nucleus and subatomic particles, A-Z notation,
isotopes, isotopic abundance, average atomic mass – Ch 1
• radiation– Ch 2
• charge balancing – Ch 4
• balancing equations – Ch 7
• energy – Ch 9
Nuclear Chemistry – an Overview
• up until this point a primary focus has been the impact of an
element’s electronic structure on physical and chemical
properties
• the identity of the elements had not changed as a result of the
reactions we’ve encountered so far
• as the name implies, with nuclear chemistry the focus is on
the nucleus of the element
• how the protons and neutrons within a nucleus impact the
stability of an isotope
• how one element can be transformed into another element
• the energy changes associated with nuclear transformations
• tremendous amounts of energies are associated with nuclear processes
A Brief Review of Nuclear Notation and Representations
• nuclide = a term used specifically in nuclear chemistry for a particular
isotope of an element
A
ZX notation vs. X–A notation
• X = chemical symbol of nuclide
• A = mass number (sum of the number of protons (p+) and neutrons (no))
• Z = atomic number (number of protons)
• # no = A – Z
• in nuclear chemistry, protons and neutrons are collectively referred to
as nucleons
nuclide of carbon with 6 p+ and 8 no: 146C or carbon–14
nuclide of uranium with 92 p+ and 146 no: 238 92U or uranium–238
• symbols representing subatomic particles
• proton ( 11p) neutron ( 10n) electron ( −10e)
Radioactivity
• radioactivity = emission of subatomic particles or high-energy
radiation by the nucleus of an atom
• a mechanism by which unstable nuclei spontaneously decompose to gain
greater stability
• a parent nuclide decays into one or more daughter nuclides
• different types of natural radioactivity exist
• alpha (a) decay, beta (b) decay, gamma (g) ray emission, positron emission,
and electron capture
• emitted radioactive particles differ from each other based on
1. their abilities to penetrate into materials (penetrating power)
2. their abilities to ionize other molecules (ionizing power)
• how the nucleus is impacted also depends on the type of radioactive
decay
• all nuclei with 84 or more protons are radioactive
• polonium (Po) and above
Radioactive Decay – Alpha (a) Emission
alpha (a) particle = a helium nucleus
• represented as 42He or 42α
• the +2 charge is omitted
• because it is a relatively massive particle, it is the most ionizing but
least penetrating of the types of radioactivity
• most dangerous to biological molecules within cells
• protection from a-decay by paper or light cloth
• if an alpha-emitter is ingested it can cause serious harm
• when a nuclide undergoes a-emission, the number of protons and
neutrons each decrease by two
• leads to a slight increase in N/Z ratio (neutron-to-proton ratio) in heavier
isotopes
Balancing Nuclear Equations
• in nuclear reactions elements often change their identities
• however, like a chemical equation, a nuclear equation still needs to be
balanced
• the sum of the atomic numbers on both sides of the equation must be equal
• the sum of the mass numbers on both sides of the equation must be equal
determine the daughter nuclide that results from the alpha decay of
polonium-216 (Z = 84)
216 4 212
212
? Pb
84Po → 2He + ?X
82
82?X
Radioactive Decay – Beta (b) Emission
beta (b) particle = an electron emitted as a result of nuclear decay
• represented as −10e or −10β
• it is less ionizing but more penetrating than a-emission
• protection from b-decay by heavy cloth, metal, or wood
• when a nuclide undergoes b-emission, the net result is that a neutron
changes into a proton
1 1 0
0 n → 1 p + −1e
• the atomic number of the nuclide increases by 1
• leads to a decrease in N/Z ratio
228 228
88Ra → 89Ac + −10e
140 no 139 no
88 p+ 89 p+
Radioactive Decay – Gamma (g) Emission
gamma (g) radiation = high-energy electromagnetic radiation
• represented as 00γ
• has no charge and no mass so mass number and atomic number of a nuclide
remains unaffected by gamma emission
• usually emitted in conjunction with other types of particles

238 234
92U → 90Th + 42He + 00γ
• least ionizing but most penetrating out of the three

• protection from g-emission by thick lead plates or cement slabs
Radioactive Decay – Positron Emission
positron = the antiparticle of an electron
• represented as +10e or +10β
• same mass as an electron but opposite charge
• similar to a beta particle in terms of ionizing and penetrating powers
• when an electron and a positron combine, they annihilate each other
and form gamma rays
0 0 0
+1 e + −1 e → 2 0γ
• when a nuclide undergoes positron emission, the net result is that a
proton changes into a neutron
1 1 0
1 p → 0 n + +1e
• the atomic number of the nuclide decreases by 1
• leads to an increase in N/Z ratio
30 30 0
15P → 14 Si + +1e
15 no 16 no
15 p+ 14 p+
Radioactive Decay – Electron Capture
the nucleus absorbs an electron from an inner orbital
• like positron emission, the net effect is that a proton is converted into
a neutron
1 0 1
1 p + −1 e → 0n
• the atomic number of the nuclide decreases by 1

• leads to an increase in N/Z ratio
76 76
36Kr + −10e → 35Br
40 no 41 no
36 p+ 35 p+
Nuclear Stability – the Neutron-to-Proton Ratio (N/Z)
the neutron-to-proton ratio (N/Z) is an important factor in determining
nuclear stability
• for lighter elements (Z ≤ 20), N/Z = 1 for stability
• for heavier elements, higher N/Z ratios are needed
a plot of number of N vs. number of Z for all stable

nuclei shows that they all cluster in a region called
the Valley of Stability
• nuclides above the Valley of Stability have N/Z
ratios that are too high
• too many nos and not enough p+s
• b emission favored
• nuclides below the Valley of Stability have N/Z
ratios that are too low
• not enough nos and too many p+s
• decays in which p+ → no are favored
• positron emission and electron capture (usually not
alpha emission)

Nuclear Stability – Predicting Type of Radioactivity
• the type of radioactive decay undergone by a nuclide can be predicted
by consulting the previous plot of N vs Z for all stable nuclei
• alternatively, the mass number of the nuclide can be compared to the
average atomic mass of that element on the periodic table
• the avg. atomic mass is a weighted average of the most stable isotopes of an
element
1. nuclides with mass numbers close to the avg. atomic mass are stable
2. nuclides with mass numbers < avg. atomic mass
• number of neutrons not high enough
• nuclides will undergo positron emission or electron capture
3. nuclides with mass numbers > avg. atomic mass
• number of neutrons too high
• nuclides will undergo beta emission
Try This
• determine the likely mode(s) of decay for the following nuclides
Avg. Atomic Mass
from Periodic Table
Pb-192 207.2 positron emission or electron capture
Pb-212 207.2 beta emission
Xe-114 131.3 positron emission or electron capture
Announcements for Wednesday, 26APR2023
• Lectures on Thursday and Monday will be reviews
• Final Exam is Monday, 08MAY2023, 12:00-3:00 PM (EDT)
• Coverage: Chapters 13-20
• Please arrive at least 20 minutes before the start of the exam
• Know your 9-digit RUID number
• See Canvas announcement from 24APR2023 for full details
• Exam locations are posted on Canvas
• See Canvas announcement from 25APR2023 for details

Types of Radioactive Decay – a Summary

Nuclear Stability – Numbers of Protons and Neutrons
• in addition to N/Z ratio, the actual number of nucleons (i.e., protons
and neutrons) can help predict nucleus stability
• even numbers of protons and/or neutrons are favored over odd numbers for
stability
Magic Numbers for stability

nuclides with a “magic number “of
protons or neutrons are particularly
stable
• Z = 2, 8, 20, 28, 50, 82, and 126
• related to the energy levels of the
protons and neutrons within the nucleus

Decay Series
• a nuclide may undergo a series of decay

events with more than one type of decay
occurring
• usually a combination of a and b decays
• uranium-238 decays into lead-206 in a

series of 14 decay events

Detecting Radioactivity
high-energy particles emitted by radioactive nuclei can be readily detected
1. film-badge dosimeters
• exposure to photographic film film-badge
dosimeter
2. scintillation counters
• interactions with light-emitting materials
3. Geiger counter
• particles emitted by radioactive
nuclei pass through an argon-
filled chamber
• argon atoms become ionized
and complete a circuit within Geiger
the detection chamber causing counter
an electrical signal
• signal is displayed by a meter or
as an audible click

Kinetics of Radioactive Decay
all radioactive nuclei decay via first-order kinetics
(differential) rate law: rate = k N
• decay rate in units of number of decaying nuclei per unit time
• k = rate constant
• higher rate constant = faster decay rate
• different nuclei decay with different rate constants
• for radioactive decay, k is INDEPENDENT of temperature
• N = NUMBER of radioactive nuclei
• higher value of N = faster decay rate
• half-life of a radioactive nuclei: © 2018 Pearson Education, Inc.

• the time it takes for one-half of the parent nuclide to decay to the daughter nuclide
ln 2 0.693
t½ = =
𝑘 𝑘
Kinetics of Radioactive Decay (continued)
recall from Ch 14 the first-order integrated rate law
A
ln = −𝑘t
Ao
• first-order integrated rate law for radioactive decay

Nt
ln = −𝑘t
No
• Nt = NUMBER of radioactive nuclei remaining at time, t
• No = initial NUMBER of radioactive nuclei
• k = rate constant and t = time of interest
• the decay rate of a nuclei is proportional to the number of radioactive nuclei

ratet
ln = −𝑘t
rateo
• rateo = initial decay rate and ratet = decay rate at time, t
Try This
• How long will it take for a 10.0-mg sample of plutonium-236 to decay
by 35.0 % given that its half-life is 2.86 years? 1.78 yr
decaying BY 35.0 % means having 65.0 % of the sample present at time, t
Nt ln 2
ln = −𝑘t 𝑘= = 0.242 yr −1
No 2.86 yr
0.65
ln = −(0.242 yr −1 )(t)
1
t = 1.78 yr
Applied Radioactivity – Radiometric Dating
radiometric dating = analytical technique whereby a sample’s age is
estimated based on the amount of a radioactive nuclei contained
within the sample
radiocarbon dating
• based off the beta-emission of carbon-14
• only suitable for organic artifacts (i.e.,
carbon-containing artifacts)
• only useful for artifacts < 50 000 yrs old
uranium/lead dating
• based off the radioactivity of uranium-238
• suitable for inorganic samples that are
billions of years old
Radiocarbon Dating – an Overview
• all living things contain carbon
• mostly as 12C, but with small amounts of 13C and 14C (radioactive)
• the ratio of 14C:12C within an organism is the same as the 14C:12C within the
environment with which it interacts
• the 14C:12C ratio within an organism is “set” and fixed at the time of
death
• it reflects the 14C:12C ratio in the atmosphere at that time
• no new 14C is introduced into the organism
• the 14C within the organism will start to decrease at a very specific rate
due to radioactive decay
• the half-life of 14C = 5715 years
• the 14C:12C ratio of an artifact is compared to the 14C:12C ratio within a
fresh sample of same mass
• it is assumed that the 14C:12C ratio in the atmosphere remains relatively
constant over long periods of time
14C:12C atmosphere
14C:12C
paper
papyrus cut down
to make paper becomes fixed
14C:12C papyrus
14C:12C atmosphere = 14C:12C papyrus as paper ages, 14C:12C decreases
𝐍𝐭
𝐥𝐧 = −𝒌𝐭
𝐍𝐨
14C in artifact = Nt vs
14C in fresh paper = N
o
k = 1.213×10–4 yrs–1
14C:12C artifact 14C:12C fresh paper
solve for t (i.e., age)
Try This
• A wooden object from an Egyptian tomb is subjected to radiocarbon
dating. The decay rate observed for its carbon-14 is 7.2
disintegrations/min per gram of carbon. What is the age of the wood
in the object? The half-life of carbon-14 is 5715 years and the decay
rate for carbon-14 within a freshly cut wood sample is 15 dis/min per
gram of carbon. 6.1×103 yr
ln 2
Nt t½ =
ln = −𝑘t 𝑘
No ln 2
7.2 𝑘= = 1.213 × 10−4 yr −1
ln = −(1.213 × 10−4 yr −1 )(t) 5715 yr
15
t = 6100 yr
Uranium/Lead Dating
238 206
92U → 82Pb
• half-life = 4.5×109 yr
• assuming a sample contained no inherent lead-206 originally, its age can be
determined from the relative amounts of uranium-238 and lead-206 currently in
the sample
A rock contains a lead-206 to uranium-238 mass ratio of 0.145:1.00. Assuming that
the rock did not contain lead-206 at the time of its formation, determine its age.
1.0×109 yr N t 0.693
ln = −𝑘t 𝑘= 9
4.5 × 10 yr
= 1.54 × 10−10 yr −1
No
1.00 g
Nt = amount of U-238 currently present at time, t = 1.00 g ln = −(1.54 × 10−10 yr −1 )(t)
1.00 + 0.1675
No = amount of U-238 originally present = 1.00 g + mass U-238 decayed
mass U-238 decayed can be calculated stoichiometrically from mass Pb-206 formed t = 1.0×109 yr
206 238 238
1 mol 82 Pb 1 mol 92U 238 g 92U
0.145 g 206
82Pb × 206 × 206 × 238
238 = 0.1675 g 92U
206 g 82Pb 1 mol 82Pb 1 mol 92U

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General Chemistry II (aka Chem 162)

• Active Learning Workshops (ALWs) – Spring 2023

• There is a limited number of spaces available this semester and students

• Two ALWs are being offered this semester:

To apply for ALWs:

© 2018 Pearson Education, Inc.

• whether a substance is soluble in another

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

• the types of IMFs between solute

© 2018 Pearson Education, Inc.

step 1: separate solute particles from each other by

• step 3: let solute and solvent particles interact

enthalpy of solution (DHsolution) = energy change associated with

DHsolution = DHsolute + DHsolvent + DHmix

ANY GENERAL QUESTIONS? Feel free to see me after class!

• ALWs are special recitations that take an active learning approach to

• There is a limited number of spaces available this semester and students

• Two ALWs are being offered this semester:

To apply for ALWs:

• if |DHsolute + DHsolvent | ≈ |DHmix|: DHsolution ≈ 0

• if |DHsolute + DHsolvent | < |DHmix|: DHsolution < 0 (exothermic, heat released)

• if |DHsolute + DHsolvent | > |DHmix|: DHsolution > 0 (endothermic, heat absorbed)

• if |DHsolute| > |DHhydration|: DHsolution > 0 (endothermic)

• unsaturated solution = a solution in which more solute can dissolve

© 2018 Pearson Education, Inc.

gas bubbles in heated water

(answers will be included in Monday’s notes)

• a conversion factor: amount solute  volume solution

• similar to molarity except that molality is independent of

amount solvent (mol)

• a conversion factor: amount component  amount solution

mole percent (mol %) = mole fraction × 100

• a conversion factor: mass component  mass solution

parts per billion (ppb) by mass

• both are conversion factors: mass component  mass solution

parts per million (ppm) by volume

parts per billion (ppb) by volume

0.623 mol NaOCl 74.44 g NaOCl 1 L solution 1 mL solution 46.38 g NaOCl

𝟒. 𝟓𝟓% 𝐍𝐚𝐎𝐂𝐥 𝐛𝐲 𝐦𝐚𝐬𝐬

• What mass of glucose needs to be added to 50.0 g water to make a solution

• A water sample contains the pollutant chlorobenzene with a concentration of 15

ANY GENERAL QUESTIONS? Feel free to see me after class!

• What mass of glucose needs to be added to 50.0 g water to make a solution

• A water sample contains the pollutant chlorobenzene with a concentration of 15

© 2018 Pearson Education, Inc.

• knowing whether a solute is a strong electrolyte, a weak electrolyte,

• when a nonvolatile solute is dissolved in a volatile

• The vapor pressure lowering of a solution is quantified by Raoult’s law

Psolution = A P°A + B P°B

• A and B = mole fractions of A and B in solution, respectively

• however, mole fractions in the vapor:

• ideal solution = a solution in Vapor pressure

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc. © 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

© 2018 Pearson Education, Inc.

• adding a solute lowers the vapor pressure of a solvent and changes