Chapter 2 Lecture 1 Kinetics/Thermo & Acids/Bases

I. Review of Simple Kinetics and Thermodynamics

A. Definitions
1) Thermodynamics = changes in energy during a process or reaction.
Determines extent of completion of the reaction or process

2) Kinetics = rate of a process or reaction. Determines how fast the reaction

or process occurs.

B. Equilibria
1) Equilibrium = state of a system in which the concentrations of reactants
and products are no longer changing.

2) Equilibrium Constant
a) If K is large, reaction goes forward
b) If K is small, reaction goes in reverse
[C][D]
A  B  C  D
K K
[A][B]
II. Equilibrium Constants
A. The Law of Mass Action
1. This is an empirical law discovered in 1864
2. Every reaction has a constant associated with it telling us where the
equilibrium position is.

K [C]l [D]m
jA + kB lC + mD K
[A] j[B]k
3. K = Equilibrium Constant = tells us where the equilibrium position is
a) K > 1 tells us the equilibrium lies to the right
b) K < 1 tells us the equilibrium lies to the left

4. If we know the concentrations, we can find K from its equation

5. K is written without units, even in cases where there are units left not
cancelled. This is correct for nonideal behavior of molecules.

6. Sample Ex. 13.1 Write K for: 4NH3 + 7O2 4NO2 + 6H2O

7. Don’t include solvents, pure liquids or pure solids in the K equation

III. Kinetics
A. Rate Laws
a) Describe how fast a reaction occurs and how we can effect that speed
A + B C k = a constant unique to each reaction
[A], [B] = concentration of reactants (M)
rate = k[A][B]

1. For simple organic reactions, we can directly write the rate law based
on the stoichiometry of the reactants

1. NO2 + NO2 NO3 + NO rate = k[NO2]2

2. NO3 + CO NO2 + CO2 rate = k[NO3][CO]

c) Other examples:
A + A + B products rate = k[A]2[B]
A + B + C products rate = k[A][B][C]
IV. Bronsted-Lowery Model of Acids and Bases
a) Acid is an H+ donor
b) Base is an H+ acceptor
c) HCl + H2O H3O+ + Cl-
acid base hydronium ion

H O + H Cl H O H + Cl
H H

1) General Acid Equation

conjugate conjugate
acid base acid base
HA + H2O H3O+ + A-

a) Conjugate base = what is left after H+ leaves acid

b) Conjugate acid = base + H+
c) Conjugate acid-base pair are related by loss/gain of H+
d) Competition for H+ by A- and H2O; strongest base wins
 2) Ka = acid dissociation constant
[H 3O ][A  ] [H  ][A  ]
Ka  
[HA] [HA]
3) Sample Exercise: Write simple Ionizations for:
HCl, HC2H3O2, NH4+, C6H5NH3+, Al(H2O)63+

4) Bronsted-Lowery theory allows for non-aqueous solutions

NH3 + HCl NH4Cl
H H
H N + H Cl H N H + Cl
H H
B. Acid Strength
1) Acid strength describes the equilibrium position of the ionization reaction
HA + H2O H3O+ + A-

2) Strong Acid = equilibrium lies far to the right (Large Ka)

a) Almost all HA has ionized to H+ and A- ([H+] = [HA]0)
b) A strong acid has a weak conjugate base
i. To ionize fully, the conjugate base must have low proton affinity
ii. The conjugate base must be weaker that water

3) Weak Acid = equilibrium lies far to the left (Small Ka)

a) Almost all HA remains unionized ([H+] << [HA]0)
b) A weak acid has a strong conjugate base
c) The conjugate base is much stronger than water

Strong acid Weak Acid

C. Water as an Acid and Base
1) An amphoteric substance can behave as an acid or a base (water)
2) Autoionization of water (reaction with itself)
H2O + H2O H3O+ + OH-

3) Ionization constant for water = KW = [H3O+][OH-] = [H+][OH-]

a) For any water solution at 25 oC, [OH-] x [H+] = KW = 1 x 10-14
b) Neutral solutions (pure water) have [OH-] = [H+] = 1 x 10-7
c) Acidic solutions: [H+] > [OH-]
d) Basic solutions: [OH-] > [H+]

e) Sample Ex. Calculate [OH-] or [H+] for the following:

i. [OH-] = 1 x 10-5 M
ii. [OH-] = 1 x 10-7 M
iii. [H+] = 10 M
 D. pH Scale
1) pH = -log[H+] (simplifies working with
small numbers)

2) If [H+] = 1.0 x 10-7, pH = -log(1 x 10-7)

= -(-7.00) = 7.00

3) pOH = -log[OH-] pKa = -logKa

4) pH changes by 1 unit for every power

of 10 change in [H+]
a) pH = 3 [H+] = 10 times the [H+] at
pH = 4
a) pH decreases as [H+] increases
(pH = 2 more acidic than pH = 3)
E. Meaning of pKa
HA + H2O H3O+ + A-

Ka 
H A   1 x 10
 
5
pK a  -logK a  -log(1 x 10-5 )  5
HA 
The lower the pKa, the stronger the acid
 B. Predicting Acid/Base Strength
1) Size of A-: HI > HBr > HCl > HF
a) F- is small, more concentrated charge, holds on to H+
b) I- is large, less concentrated charge, gives up H+

2) Electronegativity of A-: HF > H2O > NH3 > CH4

3) Resonance Forms of A-

C. Lewis Acids and Bases

1) Lewis Acid = electron pair acceptor = Electrophile
2) Lewis Base = electron pair donor = Nucleophile
3) Some covalently bonded molecules can be considered Lewis Acid/Base
pairs

NH3 + BCl3 H3N BCl3

4) Dissociation of a Lewis Acid/Base Pair (Mechanisms)

CH3 CH3 OH2 CH3 CH3
Cl C CH3 Cl- + + C CH3 H2O+ C CH3 H+ + HO C CH3
CH3 CH3 CH3 CH3