Last Class

• Thermodynamics vs kinetics: Haber-Bosch process

• Gibbs free energy and reaction quotients**
Example
Determine the equilibrium constant for the following reaction at 298 K.

Cl(g) + O3(g) → ClO(g) + O2(g) ΔG° = - 34.5 kJ kJ

mol rxn

a) 𝐾!" = 8.9×10#$
b) 𝐾!" = 1.1×10%
c) 𝐾!" = 0.98
d) 𝐾!" = 1.0
Example
Phosphorous and chlorine gases combine to produce phosphorous trichloride:

P2(g) + 3 Cl2(g) → 2 PCl3(g)

kJ
ΔG° at 298 K for this reaction is -642.9 kJ/mol.
mol rxn The value of ΔG at 298 K for a reaction mixture
that consists of and 0.55 atm PCl3 is ________.
['()! ]"
𝐾!" =
[()" ]! [' " ]
-#
𝐾!" = (𝑅𝑇)+ 𝐾, assuming the ideal gas relation = 𝐴
./

012
Recall that in atm, the gas constant 𝑅 = 0.08205
345

BUT…
Example
Phosphorous and chlorine gases combine to produce phosphorous trichloride:

P2(g) + 3 Cl2(g) → 2 PCl3(g)

kJ
ΔG° at 298 K for this reaction is -642.9 kJ/mol.
mol rxn The value of ΔG at 298 K for a reaction mixture
that consists of and 0.55 atm PCl3 is ________.

In using pressures vs concentration, numerical values for the Gibbs free energy differ
because ∆𝑮𝐨 measures the difference between the equilibrium state and a standard state.
If a different standard state is chosen, then the standard free energy changes as well.

- $%&! "
𝐾6 =
- %&" ! - $ "
7
∆𝐺 = ∆𝐺 + 𝑅𝑇 ln 𝑄, Because ΔG < 0,
89 89 (<.>>012)" then K > Q, and the
∆𝐺 = −642.9 + 8.314×10#: ×298K ln
27) 27)45 @.A012×(+.>012)! reaction must
kJ kJ
∆𝐺 = −642.9 + 8.314×10#: ×298K×(−4.59) proceed forward
mol mol C K for equilibrium to
kJ
∆𝐺 = −654.1 be attained.
mol
Acids and Bases
CHEM 110: Honors Chemistry
Recall: Properties of Equilibria

aA + bB cC + dD
Same equilibrium
achieved whether
starting with pure
reactants or pure
“products”

Oxtoby, Block et al.

 The Chemistry of Water

In pure H2O:
 Arrhenius Acid-Base Definition

Bases increase [OH-]. [H3O+] [OH−] = 𝐾E

− log[H3O+] − log[OH−] = − log 𝐾E

pH + pOH = 14

Pure H2O (neutral conditions):

pH = − log(1.0×10!" ) pH = 7

pOH = − log(1.0×10!" ). pOH = 7

In an ccidic solution, [H3O+]>[OH-], so pH<7

 The Two Types of Acids
HCl, HBr, HI,
HClO4, HClO3,
𝐾!" ≫ 1 H2SO4, HNO3 𝐾!" ≲ 1

Recall that HF is polar

covalent bond type.

Only H3O+ and Cl− (and water)

Tro, Chemistry: A Molecular Science

Stronger and Weaker Terminology

A larger 𝑘% gives a smaller p𝑘% and

corresponds to more product.
Beyond Arrhenius: Brønsted-Lowry acids
A Brønsted-Lowry acid is a proton (hydrogen ion) donor.
A Brønsted-Lowry base is a proton (hydrogen ion) acceptor.

Conjugate base Conjugate acid

Conjugate acid Conjugate base

Question

Consider the following acids values at 25oC.

HOCl, Ka=2.9 × 10-8
HC6H5O, Ka= 1.3 × 10-10
Which species is the strongest CONJUGATE base?
HNO2, Ka= 4.6 × 10-4
HCHO2, Ka= 1.8 × 10-4 A.) ClO-
HClO2, Ka= 1.1 × 10-2 B.) C6H5O-
C.) NO2-
D.) CHO2-
E.) ClO2-
Conjugate Acid-Base Pairs
Guidelines for Salts
6 anions, not hydrolyzed (conjugate bases of strong acids)
Their Kb corresponds to a negligible amount of OH- relative
to the autoionization of water.
Cl –, Br –, I –, NO3–, ClO3–, ClO4–
5 cations, not hydrolyzed (conjugate acids of strong bases)
Their Ka corresponds to a negligible amount of H+ relative to
the autoionization of water.
Li+, Na+, K+, Rb+, Cs+ (alkali metal cations)

Hydrolysis of Result
Conjugate base anions of weak acids Raise pH Take a proton from H2O

Conjugate acid cations of weak bases Lower pH Donate a proton to H2O

21
For other salts
A solution of 0.50M NH4CN is: Ka of NH4+ = 5.6×10-10M
A) pH < 7 Ka of HCN = 4.9×10-10M
B) pH = 7
C) pH > 7
Why Titrate?
1) Determine the exact
concentration of an acid
or a base.
2) Compute Ka or Kb.
3) Determine the identity of
unknown analytes.
Titration Curves
HCl eq + NaOH aq → NaCl aq + H& O(l)
Titration of a
strong acid with a strong base

The quantity of acid

equals that of the base at
the equivalence point.
Last Class
• Arrhenius acids/bases
• pH/pOH
• Strong and weak acids
• Brønsted-Lowry acids**
• NaOH(aq) -> Na+ (aq)+ OH- (aq)
• In this case, OH- is the base; Na+ is just a spectator ion.
• Strong acid-strong base titration
Question
What is the pH of a 10-8 M HI (strong acid) solution? (Enter an integer
value.)
Titration: Part I
100.0 mL sample of 0.10 M NH3 is titrated with 0.10 M HNO3. Determine the pH of the
solution before the addition of any HNO3. The Kb of NH3 is 1.8 × 10-5.
A) 4.74
B) 9.26
C) 11.13
D) 13.00
E) 12.55
Titration: Part II
A 100.0 mL sample of 0.10 M NH3 is titrated with 0.10 M HNO3. Determine the pH of the
solution after the addition of 50.0 mL of HNO3. The Kb of NH3 is 1.8 × 10-5.
A) 4.74
B) 7.78
C) 7.05
D) 9.26
E) 10.34
Part II: Henderson-Hasselbach Equation
Derivation and assumptions thereof…
Assuming that (at equilibrium): NH' ≫ H' O( and NH' ≫ OH ) and NH*( ≫ H' O( …

1) Acid dissociation: NH*( aq + H& O l ⇋ H' O( aq + NH' (aq)

2) Base ionization: NH' (aq) + H& O l ⇋ OH ) aq + NH*( aq

Part II: Henderson-Hasselbach Equation
Derivation and assumptions thereof…
𝐾D NH: = 1.8×10#>
H' O( [NH' ]
𝐾% =
[NH*( ]
(
[NH*( ]
H' O = 𝐾%
[NH' ]
[NH' ]
p𝐻 = p𝐾% + log
[NH*( ]
Titration: Part III
A 100.0 mL sample of 0.10 M NH3 is titrated with 0.10 M HNO3. Determine the pH of the
solution after the addition of 100.0 mL of HNO3. The Kb of NH3 is 1.8 × 10-5.
A) 6.58
B) 10.56
C) 8.72
D) 3.44
E) 5.28
Titration: Part IV
A 100.0 mL sample of 0.10 M NH3 is titrated with 0.10 M HNO3. Determine the pH of the
solution after the addition of 200.0 mL of HNO3. The Kb of NH3 is 1.8 × 10-5.
A) 6.44
B) 1.48
C) 2.00
D) 12.52
E) 12.00
Weak Base Titrated with a Strong Acid

II

5.3 III

IV

pH varies more in region II than for a strong base

Summary – Four Regions in a Titration Curve
1) Initial – weak acid (or base)
a) Simple equilibrium problem using initial concentration of weak acid (or base)
2) Buffer region
a) Use reaction stoichiometry between weak acid (or base) and strong base (or acid) to
carry out calculation
b) Use resulting acid (or base) & conjugate base (or acid) concentrations to carry out
weak acid (or base) equilibrium (or Henderson-Hasselbalch Equation)
3) Equivalence point
a) # moles of weak acid (or base) = # moles of strong base (or acid) added
b) All weak acid (or base) is converted into its conjugate
c) Calculate new concentration of conj. base (or acid) and determine pH from equilibrium
of the conj. base (or acid)
4) Past the equivalence point – Excess Titrant
a) Strong base (or acid) is now in excess – calculate the moles of strong base (or acid) that
was not neutralized by the weak acid (or base) and then divide by the new solution
volume to determine final concentration
Polyprotic Acids

Zumdahl & DeCoste, Chapter 7

Problem: pH of 1.0 M Phosphoric Acid
Amphoteric pH Calculation
What is the pH of 1.2 M NaHSO3 solution?
Amphoteric: both acid and based
Last Class
• Titration of weak acid/base by strong base/acid
• Henderson-Hasselbach Equation
• Polyprotic acids
Question
What is the pH of the resulting solution if 30. mL of 0.432 M methylamine, CH3NH2, is added
to 15 mL of 0.234 M HCl? Assume that the volumes of the solutions are additive. Ka = 2.70 ×
10-11 for CH3NH3+.
A) 3.00
B) 3.86
C) 10.14
D) 11.00
E) 5.99
Color Indicators

yellow blue

Bromothymol blue is a weak acid with pKa=7.0

Why does is change color around pH=7.0?

Why is the color changing over a range of pH?

 Coral reefs are formed by thin layers of CaCO3. Why does
Example increasing acidity reduce the availability of carbonate ions
that reef-building corals need to produce their skeletons?
To get a hint of the underlying acid-base chemistry, calculate the
fraction of carbonate at pH = 10. [H2CO3(aq), HCO3- (aq), CO32- (aq)]
 pKa1 = 3.4

Malic Acid pKa2 = 5.2

Consider a titration of 20 mL of 1.0 M malic acid. If 1.0 M NaOH is used as the titrant, calculate
the pH after 20 mL of 1.0 M NaOH and 25 mL of 1.0 M NaOH. pKa1 = 3.4, pKa2 = 5.2.
 Aqua acids
Solvated cations sometimes change pH. Mm+ pKa Mm+ pKa
Aqua acids are acids with water coordinated to a Th4+ 3.2
central species. Al3+ 5.0 Sc3+ 4.3
[M(OH2)n]m+ + H2O ⇌ [M(OH2)n-1OH](m-1)+ + H3O+ Y3+ 7.7 Cr3+ 4.0
La3+ 8.5 Fe3+ 2.2
Mg2+ 11.4 Cr2+ 10.0
Ca2+ 12.8 Mn2+ 10.6
Sr2+ 13.3 Fe2+ 9.5
Ba2+ 13.5 Co2+2 9.6
z= z / (r + d)
2+
z Ni 9.9
= charge on ion
r Zn
= ionic
2+ radius9.0
The acidity of a solution of metal ions depends on Li+ 13.6 d Ag
= diameter
+ in water
12.0
the ionic size and charge. Na+ 14.2 Tl+ 13.2
𝐸 ∝ 𝑞2 𝑞& /𝑟
K+ 14.5
Covalency leads to deviations from linear trend.
Smaller pKa -> greater dissociation, stronger acid.
Last Class
• Polyprotic titration
• Aqua acids**

Monday, Nov. 25 Class: Announcement

• In-class trivia contest!
• Using MS Forms: have your browsers oiled and ready!
• Send me your (one per person) multiple-choice (text-based, no chemical
structures) Chem 110-related question for extra participation credit by Nov
18.
• Actual prizes for trivia winners!
 Aqua acids
Solvated cations sometimes change pH. Mm+ pKa Mm+ pKa
Aqua acids are acids with water coordinated to a Th4+ 3.2
central species. Al3+ 5.0 Sc3+ 4.3
[M(OH2)n]m+ + H2O ⇌ [M(OH2)n-1OH](m-1)+ + H3O+ Y3+ 7.7 Cr3+ 4.0
La3+ 8.5 Fe3+ 2.2
Mg2+ 11.4 Cr2+ 10.0
Ca2+ 12.8 Mn2+ 10.6
Sr2+ 13.3 Fe2+ 9.5
Ba2+ 13.5 Co2+2 9.6
z= z / (r + d)
2+
z Ni 9.9
= charge on ion
r Zn
= ionic
2+ radius9.0
The acidity of a solution of metal ions depends on Li+ 13.6 d Ag
= diameter
+ in water
12.0
the ionic size and charge. Na+ 14.2 Tl+ 13.2
𝐸 ∝ 𝑞2 𝑞& /𝑟
K+ 14.5
Covalency leads to deviations from linear trend.
Smaller pKa -> greater dissociation, stronger acid.
 Buffer

A buffer acts so as to maintain a

narrow pH range (roughly one unit).

Acetic acid /Sodium acetate

Sources: Oxtoby; Tro, Chemistry: A Molecular Science

Blood and Buffers
How Buffers Work
Carbonic anhydrase enzymes catalyze the
conversion of carbon dioxide and water into
carbonic acid.

As long as the limiting reagent (LR) is the added

base/acid.
Buffer Exercise
Take a 100 mL buffer solution of 1.0M CH3CO2H and 0.9M CH3CO2Na. Add 10 mL of 1.0M HCl.
What is the pH of the resulting solution? pKa(CH3CO2H)=4.74
 Question
What change will be caused by the addition of a small
amount of HCl to a HF/NaF buffer?
a) [H3O+] will increase significantly
b) [F–] and [H3O+] will both increase
c) [HF] will decrease and [F–] will increase
d) [F–] will decrease and [HF] will increase
e) The fluoride ions will precipitate out of solution
as its acid salt.
Example
What volume of 0.5 M HCl must be added to a 500 mL solution of 0.250 M
ammonia to make a buffer with a pH of 9.00? Kb(NH3) = 1.8 x 10–5
Question
Which of the following acids would be the best choice to combine
with its sodium salt to make a buffer with pH 4.25?
A.) Chlorous Acid, HClO2 pKa = 1.95
B.) Nitrous Acid, HNO2 pKa = 3.34
C.) Formic Acid, HCHO2 pKa = 3.74
D.) Hypochlorous Acid, HClO pKa = 7.54
Lewis Acid-Base Theory LUMO acid + HOMO base ->
lower energy (more stable) MO
Lewis Acid: electron pair acceptor

Lewis Base: electron pair donor

85
How to Recognize a Lewis acid or a Lewis base
●Molecules for which a simple Lewis structure indicates an atom does not have
four pairs of electrons in its valence shell (an octet) will behave as Lewis acids.

●Molecules whose Lewis structures indicate an atom to have an octet as a result

of forming one or more multiple bonds will often function as Lewis acids.

●Molecules that have central atoms that are capable of expanding their valence
shell to include more than four pairs of sigma-bonding electron pairs, i.e., use
hybrid orbitals that involve d orbitals, are Lewis acids.

●Lewis bases are molecules with lone pairs of electrons.

• In some molecules the energies of the orbitals containing lone pairs are too
low in energy to interact appreciably with most Lewis acids.
86
 Oxides: Lewis Acids and Bases

Metal oxides -> bases

Generation of hydroxide

Li& O aq → 2 Li( aq + O&) aq

O&) aq + H& O(l) → 2 OH ) (aq)

Non-metal oxides -> acids

Shriver & Atkins, Inorganic Chemistry

Arrow Pushing Mechanisms
Carbon dioxide in water

Source: Everyday Health

Arrow Pushing Mechanisms
Sulfur dioxide and sulfur trioxide in water

Source: https://allchemical.com.au/shop/sulphuric-acid-98/
Last Class
• Buffers
• Lewis acids/bases
• Metal oxide bases
• Arrow pushing mechanisms

Monday, Nov. 25, Class: In-class trivia contest!

• Using MS Forms: have your browsers oiled and ready!
• Send me your (one per person) multiple-choice (text-based, no chemical
structures) Chem 110-related question for extra participation credit by
Nov 18.
• Actual prizes for trivia winners!
Factors Influencing Acid Strength
• Electronegativity (binary, HX)
• Polarizability/Solvation Effects (binary, HX)
• Resonance (eg, oxoacids)
• Inductive effects
• Hybridization

What do weaker conjugate bases imply about acid strength?

->Base stability is inversely related to acid strength.

To rationalize acid strength, we need to analyze base strength.

95
Binary Acids (HX)
pKa values for binary acids.
CH4 NH3 H2O HF
(51) (35) (14) (3.2)

SiH4 PH3 H2S HCl

(35) (27) (7) (-7)

GeH4 AsH3 H2Se HBr

(25) (23) (3.8) (-9)

H2Te HI
(2.3) (-11)

What is the strongest conjugate base from the set of binary acids?

96
Case I: Binary Acids (within a Row)

Acid CH4 NH3 H2O HF

pKa 51 35 14 4

Conjugate Base CH3- NH2- OH- F-

Case II: Binary Acids (within a Column)
Reaction pKa Electronegativity of Atom

HF H+ (aq) + F- (aq) 3.2 4.0

HCl H+ (aq) + Cl- (aq) -7 3.5

HBr H+ (aq) + Br- (aq) -9 2.7
Hi H+ (aq) + I- (aq) -11 2.2

o
Size (A)
Acid Strength Increasing

As atomic size increases,

the atom becomes more
polarizable. A more
flexible charge distribution
becomes is more
energetically favorable.
Non-Binary Acids (oxoacids)
O
HO O HO Cl
OH
formic acid acetic acid hypochlorous acid

O O
F O Cl OH
OH
F O
F
2,2,2-trifluoroacetic acid perchloric acid

HOBr
hypobromous acid
Resonance Effects & Number of Oxygen Atoms

pKa=7.52 pKa=-6

Strongest base Weakest base

How is electron density being dispersed for the conjugate base?

What are the charges on oxygen in the conjugate bases of each structure?
Resonance weakens the overall charge at a given site, thus increasing stability.
Inductive Effects (Valence Bond Picture)

pKa = 0.1 pKa = 1.3 pKa = 0.23 pKa = 4.7

106
 Hybridization
Caution: Always consider resonance
BEFORE hybridization!

pKa = 5.2 pKa = 10

Ka = 10-5.2 Ka = 10-10

Kb = 1.6 x 10-9 Kb = 10-4

sp2 holds onto the electron density more tightly

than sp3. It also results in less steric repulsion.

For the same atom, an sp hybridized atom is more

electronegative than sp2 hybridized atom, which is
more electronegative than sp3 hybridized atom.
108
Solubility and Equilibrium
What is the molar solubility of AgCl? Note that Ksp =[Ag+][Cl-]=1.8x10-10
Question
The molar solubility of CuI is 2.26 × 10-6 M in pure water. Calculate the Ksp for CuI.
A) 5.11 × 10-12 M
B) 4.52 × 10-6 M
C) 1.50 × 10-3 M
D) 4.62 × 10-17 M
E) 1.02 × 10-11 M
Solubility Problem
Determine the mass of lead(II) iodate (MW = 557 g/mol)
dissolved in 2.50 L of a saturated aqueous solution of
Pb(IO3)2 at 25oC. The Ksp[Pb(IO3)2]=2.6 ´ 10-13.
Question
Give the equation for a saturated solution in comparing Q with Ksp.
A) Q > Ksp
B) Q < Ksp
C) Q = Ksp
D) Q ≠ Ksp
E) none of these
Application
Kidney stones typically form in the kidney outlet ducts and eventually pass through the ureter where they
cause extreme pain. Kidney stones are frequently composed of sparingly soluble calcium oxalate

Ca(C2O4)(s) ⇄ Ca2+(aq) + C2O42-(aq) Ksp = 2.3×10-9

(a) Calculate the molar solubility for calcium oxalate.

(b) The typical volume of urine excreted into the kidney ducts in 24 hours is 1.5L. The typical total calcium
excreted into the kidney ducts is 3.0mmol. What is the minimum number of moles of oxalate that will yield
a precipitate?
Application (cont’d)
A common therapy for patients with recurrent calcium oxalate stones is orally administered
potassium citrate, which causes excretion of increased amounts of citrate, C6H5O73-(aq), into the
kidney ducts, which favors the formation of the calcium citrate anionic complex, Ca(C6H5O7)-(aq):

Ca2+(aq) + C6H5O73-(aq) ⇄ Ca(C6H5O7)-(aq) Keq = 7.0×104

Determine Keq for the reaction below.

Ca(C2O4)(s) + C6H5O73-(aq) ⇄ Ca(C6H5O7)-(aq) + C2O42-(aq)

Application (cont’d)
The typical volume of urine excreted into the kidney ducts in 24 hours is 1.5L. The typical total calcium
ion excreted into the kidney ducts is 3.0mmol, and the typical total oxalate excreted into the kidney ducts
is 0.15mmol. Consider a patient who consumes citrate. Assuming the values listed above can be used to
compute the equilibrium concentration of calcium citrate and oxalate, what is the equilibrium
concentration of free citrate?

Ca(C2O4)(s) + C6H5O73-(aq) ⇄ Ca(C6H5O7)-(aq) + C2O42-(aq)

x 0.0020M 1.0x10-4M

Keq=[Ca(C6H5O7)-][C2O42-]/[C6H5O73-]

1.6x10-3=2.0x10-3 1.0x10-4/x [C6H5O73- ]=x=1.2x10-3M

Review
• Factors influencing acid strength
• Electronegativity
• Polarizability
• Resonance
• Inductive effects
• Hybridization
• Solubility and equilibrium

Monday, Nov 25 Class Announcement

• In-class trivia contest!
• Using MS Forms (text based): have your browsers ready!
• Send me your multiple-choice Chem 110-related question for extra participation
credit by Nov 18.
• Prizes for trivia winners!
Question
Which of the following processes has a ΔSsys > 0?
A) H2O(l) → H2O(s)
B) N2(g) + 3 H2(g) → 2 NH3(g)
C) CH4(g) + H2O(g) → CO(g) + 3 H2(g)
D) Li2CO3(s) + H2O(g) + CO2(g) → 2 LiHCO3(s)
Example: Arrhenius Law
Raw milk sours in 4.0 h at 28°C but in 48 h in a refrigerator at 5°C.
Calculate the activation energy for the souring of milk.
Example: Reaction Kinetics
In 6 M HCl, the complex ion Ru(NH3)63+ decomposes to a variety of products. The reaction is
first order in Ru(NH3)63+ and has a half-life of 14 h at 25°C. Under these conditions, how long
will it take for the [Ru(NH3)63+] to decrease to 53.0% of its initial value?
Example: Reaction Rate
In 1967, it was shown that the reaction

H2 (g) + I2 ® 2HI (g)

proceeds by the following mechanism:

I2 Û 2I

2I + H2 ® 2HI

The rate constants are defined according to the convention given in the lecture.

(A) Obtain the rate law. Use the steady state method where appropriate.

(B) Obtain the rate law under the assumption that the first reaction step is a
rapid equilibrium with equilibrium constant K.
Example: Amphoteric substance
The amino acid glycine has the following chemical structure:

This compound has pKa1 = 2.34 for the O-H proton and pKa2 = 9.60 for the -NH3+ protons. What
glycine form is dominant in blood with pH = 7.4. What fraction is it?

A) B) C)
Example: Titration
If we have 100 mL of 0.100 M CH3COOH and 0.100 M CH3COO-, what is the pH
after the addition of 11 mL of 1.0 M NaOH? pKa(CH3CO2H)=4.74
Exercise: Buffer
A 1.00 L buffer solution is 0.250 M in HF and 0.250 M in LiF. Calculate the pH of the solution
after the addition of 0.150 moles of solid LiOH. Assume no volume change upon the addition of
base. The Ka for HF is 3.5 × 10-4.
A) 3.46
B) 4.06
C) 2.85
D) 3.63
E) 4.24

Final pH=4.06
Exercise: Lewis Acids
Predict the products for the following acid-base reactions. Is Keq greater than 1, less than
1, or equal to 1?