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Acids and Bases

Some Properties of Acids


 Produce H+ (as H3O+) ions in water (the hydronium ion is a hydrogen
ion attached to a water molecule)

 Taste sour

 Corrode metals

 Electrolytes

 React with bases to form a salt and water

 pH is less than 7

 Turns blue litmus paper to red ―Blue to Red A-CID‖


Some Properties of Bases
 Produce OH- ions in water

 Taste bitter, chalky

 Are electrolytes

 Feel soapy, slippery

 React with acids to form salts and water

 pH greater than 7

 Turns red litmus paper to blue ―Basic Blue‖


Acid Nomenclature Review
Anion
Ending Acid Name
No Oxygen -ide hydro-(stem)-ic acid

-ate (stem)-ic acid


w/Oxygen
-ite (stem)-ous acid
An easy way to remember which goes with which…
―In the cafeteria, you ATE something ICky‖
Acid/Base definitions
Definition 1: Arrhenius

Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

4.3
Acid/Base Definitions
Definition #2: Brønsted – Lowry

Acids – proton donor

Bases – proton acceptor

A “proton” is really just a hydrogen atom


that has lost it’s electron!
A Brønsted-Lowry acid is a proton donor
A Brønsted-Lowry base is a proton acceptor

base acid conjugate conjugate


acid base
ACID-BASE THEORIES
The Brønsted definition means NH3 is a BASE in
water — and water is itself an ACID

NH3 + H2O NH4+ + OH-


Base Acid Acid Base
Conjugate Pairs
Learning Check!
Label the acid, base, conjugate acid, and conjugate
base in each reaction:

HCl + OH-  Cl- + H2O


Acid Base Conj.Base Conj.Acid

H2O + H2SO4  HSO4- + H3O+


Acid Base Conj.Base Conj.Acid
Acids & Base Definitions
Definition #3 – Lewis

Lewis acid - a substance that accepts


an electron pair

Lewis base - a substance that


donates an electron pair
Lewis Acids & Bases
Formation of hydronium ion is also an
excellent example.
••
•• O—H ••
+ H O—H
H
H
H
ACID BASE

•Electron pair of the new O-H bond


originates on the Lewis base.
Lewis Acid/Base Reaction
The pH scale is a way of
expressing the strength of acids
and bases. Instead of using very
small numbers, we just use the
NEGATIVE power of 10 on the
Molarity of the H+ (or OH-) ion.

Under 7 = acid
7 = neutral
Over 7 = base
Calculating the pH
pH = - log [H+]
(Remember that the [ ] mean Molarity)

Example: If [H+] = 1 X 10-10


pH = - log 1 X 10-10
pH = - (- 10)
pH = 10
Example: If [H+] = 1.8 X 10-5
pH = - log 1.8 X 10-5
pH = - (- 4.74)
pH = 4.74
Try These!
Find the pH of these: pH = - log [H+]
pH = - log 0.15
1) A 0.15 M solution of
Hydrochloric acid pH = - (- 0.82)
pH = 0.82

pH = - log 3 X 10-7
2) A 3.00 X 10-7 M pH = - (- 6.52)
solution of Nitric acid pH = 6.52
pH calculations – Solving for H+
If the pH of Coke is 3.12, [H+] = ???
Because pH = - log [H+] then
- pH = log [H+]
Take antilog (10x) of both
sides and get
10-pH = [H+]
[H+] = 10-3.12 = 7.6 x 10-4 M
*** to find antilog on your calculator, look for ―Shift‖ or
―2nd function‖ and then the log button
More about water
H2O can function as both an ACID and a BASE.

In pure water there can be AUTOIONIZATION

Equilibrium constant for water = Kw


Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC
More about water
Autoionization OH-

H3O+

Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC

In a neutral solution [H3O+] = [OH-]

and so [H3O+] = [OH-] = 1.00 x 10-7 M


pOH
Since acids and bases are opposites,
pH and pOH are opposites!
pOH does not really exist, but it is
useful for changing bases to pH.
pOH looks at the perspective of a
base
pOH = - log [OH-]
Since pH and pOH are on opposite
ends,
pH + pOH = 14
pH [H+] [OH-] pOH
[H3O+], [OH-] and pH
What is the pH of the 0.0010 M NaOH solution?
[OH-] = 0.0010 (or 1.0 X 10-3 M)
pOH = - log 0.0010
pOH = 3
pH = 14 – 3 = 11

OR Kw = [H3O+] [OH-]
[H3O+] = 1.0 x 10-11 M
pH = - log (1.0 x 10-11) = 11.00
What is the pH of a 2 x 10-3 M HNO3 solution?
HNO3 is a strong acid – 100% dissociation.
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
Start 0.002 M 0.0 M 0.0 M
End 0.0 M 0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7

What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?


Ba(OH)2 is a strong base – 100% dissociation.
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
Start 0.018 M 0.0 M 0.0 M

End 0.0 M 0.018 M 0.036 M

pH = 14.00 – pOH = 14.00 + log(0.036) = 12.56


15.4
Strong and Weak Acids/Bases
The strength of an acid (or base) is
determined by the amount of IONIZATION.

HNO3, HCl, HBr, HI, H2SO4 and HClO4 are the


strong acids.
Strong and Weak Acids/Bases
Generally divide acids and bases into STRONG or WEAK
ones.

STRONG ACID: HNO3 (aq) + H2O (l) 


H3O+ (aq) + NO3- (aq)

HNO3 is about 100% dissociated in water.


Strong and Weak Acids/Bases
Weak acids are much less than 100% ionized in water.

*One of the best known is acetic acid = CH3CO2H


Strong and Weak Acids/Bases
Strong Base: 100% dissociated in water.
NaOH (aq)  Na+ (aq) + OH- (aq)
Other common strong bases
include KOH and Ca(OH)2.
CaO (lime) + H2O 
Ca(OH)2 (slaked lime)

Strong bases are the group I hydroxides


Calcium, strontium, and barium
CaO hydroxides are strong, but only soluble
in water to 0.01 M
Strong and Weak Acids/Bases
Weak base: less than 100% ionized in water
One of the best known weak bases is ammonia
NH3 (aq) + H2O (l) ↔ NH4+ (aq) + OH- (aq)
Weak Bases
Equilibria Involving
Weak Acids and Bases
Consider acetic acid, HC2H3O2 (HOAc)
HC2H3O2 + H2O ↔ H3O+ + C2H3O2 -
Acid Conj. base
+ -
[H3O ][OAc ]
Ka   1.8 x 10-5
[HOAc]

(K is designated Ka for ACID)


K gives the ratio of ions (split up) to molecules (don’t split up)
Ionization Constants for Acids/Bases

Acids Conjugate
Bases
Increase
strength

Increase
strength
Equilibrium Constants
for Weak Acids

Weak acid has Ka < 1


Leads to small [H3O+] and a pH of 2 - 7
Equilibria Involving A Weak Acid
You have 1.00 M HOAc. Calc. the equilibrium
concs. of HOAc, H3O+, OAc-, and the pH.
Step 1. Define equilibrium concs. in ICE table.

[HOAc] ↔ [H3O+] [OAc-]


1.00 0 0
initial
-x +x +x
change

equilib 1.00 - x x x
Equilibria Involving A Weak Acid
You have 1.00 M HOAc. Calc. the equilibrium
concs. of HOAc, H3O+, OAc-, and the pH.
Step 2. Write Ka expression
+ ][OAc - ] 2
[H O x
Ka  1.8 x 10-5 = 3 
[HOAc] 1.00 - x

This is a quadratic. Solve using quadratic


formula.

or you can make an approximation if x is very small!


(Rule of thumb: 10-5 or smaller is ok)
Equilibria Involving A Weak Acid
You have 1.00 M HOAc. Calc. the equilibrium
concs. of HOAc, H3O+, OAc-, and the pH.
Step 3. Solve Ka expression
+ ][OAc - ] 2
[H O x
Ka  1.8 x 10-5 = 3 
[HOAc] 1.00 - x

First assume x is very small because Ka is so


small.
-5 x2
Ka  1.8 x 10 =
1.00
Now we can more easily solve this approximate
expression.
Equilibria Involving A Weak Acid
You have 1.00 M HOAc. Calc. the equilibrium concs. of
HOAc, H3O+, OAc-, and the pH.

Step 3. Solve Ka approximate expression


-5 x2
Ka  1.8 x 10 =
1.00

x = [H3O+] = [OAc-] = 4.2 x 10-3 M


pH = - log [H3O+] = -log (4.2 x 10-3) = 2.37
Equilibria Involving A Weak Acid
Calculate the pH of a 0.0010 M solution of formic acid,
HCO2H.
HCO2H + H2O ↔ HCO2- + H3O+
Ka = 1.8 x 10-4
Approximate solution
[H3O+] = 4.2 x 10-4 M, pH = 3.37
Exact Solution
[H3O+] = [HCO2-] = 3.4 x 10-4 M
[HCO2H] = 0.0010 - 3.4 x 10-4 = 0.0007 M
pH = 3.47
Equilibrium Constants
for Weak Bases

Weak base has Kb < 1


Leads to small [OH-] and a pH of 12 - 7
Relation
of Ka,
Kb,
[H3O+]
and pH
Equilibria Involving A Weak Base
You have 0.010 M NH3. Calc. the pH.
NH3 + H2O ↔ NH4+ + OH-
Kb = 1.8 x 10-5
Step 1. Define equilibrium concs. in ICE table
[NH3] [NH4+] [OH-]

initial 0.010 0 0

change -x +x +x

equilib 0.010 - x x x
Equilibria Involving A Weak Base
You have 0.010 M NH3. Calc. the pH.
NH3 + H2O  NH4+ + OH-
Kb = 1.8 x 10-5
Step 2. Solve the equilibrium expression
-5 [NH4+ ][OH- ] x2
Kb  1.8 x 10 = =
[NH3 ] 0.010 - x
Assume x is small, so
x = [OH-] = [NH4+] = 4.2 x 10-4 M
and [NH3] = 0.010 - 4.2 x 10-4 ≈ 0.010 M
The approximation is valid !
Equilibria Involving A Weak Base
You have 0.010 M NH3. Calc. the pH.

NH3 + H2O  NH4+ + OH-

Kb = 1.8 x 10-5

Step 3. Calculate pH
[OH-] = 4.2 x 10-4 M

so pOH = - log [OH-] = 3.37

Because pH + pOH = 14,

pH = 10.63
Types of Acid/Base Reactions:
Summary
Weak Bases are weak electrolytes
F- (aq) + H2O (l) OH- (aq) + HF (aq)
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs:


• The conjugate base of a strong acid has no measurable
strength.
• H3O+ is the strongest acid that can exist in aqueous
solution.
• The OH- ion is the strongest base that can exist in
aqueous solution.
15.4
15.4
Strong Acid Weak Acid

15.4
percent ionization = Ionized acid concentration at equilibrium x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

15.5
Ionization Constants of Conjugate Acid-Base Pairs

HA (aq) H+ (aq) + A- (aq) Ka

A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb

H2O (l) H+ (aq) + OH- (aq) Kw

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka

15.7
Molecular Structure and Acid Strength
H X H+ + X- • Bond strength

The stronger The weaker • Polarity


the bond the acid

HF << HCl < HBr < HI

15.9
Molecular Structure and Acid Strength
d- d+
O O- + H
Z H Z +

The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state

15.9
Molecular Structure and Acid Strength
1. Oxoacids having different central atoms (Z) that are from the same
group and that have the same oxidation number.

Acid strength increases with increasing electronegativity of Z


•• ••
••

O
••

••
••
•• •• •• ••
••

••
H O Cl O H O Br O
•• •• •• •• •• ••

Cl is more electronegative than Br

HClO3 > HBrO3

15.9
Molecular Structure and Acid Strength
2. Oxoacids having the same central atom (Z) but different numbers
of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

15.9
Acid-Base Properties of Salts
Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal ion
(except Be2+) and the conjugate base of a strong acid (e.g. Cl-,
Br-, and NO3-).
H2 O
NaCl (s) Na+ (aq) + Cl- (aq)
Basic Solutions:
Salts derived from a strong base and a weak acid.
H2O
NaCH3COO (s) Na+ (aq) + CH3COO- (aq)

CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)

15.10
Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.
H2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)

NH4+ (aq) NH3 (aq) + H+ (aq)

Salts with small, highly charged metal cations (e.g. Al3+, Cr3+,
and Be2+) and the conjugate base of a strong acid.

Al(H2O)3+
6 (aq) Al(OH)(H2O)52+(aq) + H+ (aq)

15.10
Acid-Base Properties of Salts
Solutions in which both the cation and the anion hydrolyze:

• Kb for the anion > Ka for the cation, solution will be basic
• Kb for the anion < Ka for the cation, solution will be acidic
• Kb for the anion  Ka for the cation, solution will be neutral

15.10
Henderson Hasselbalch
Equation
Henderson-Hasslebalch:
Problem solving tips

Use this for buffer problems only.

Be sure you are using the Ka NOT the Kb

As with all equations, get good at manipulating them.

Only use if weak acid approximation is valid


Example: Using the Henderson-
Hasslebalch equation

0.20M CH3COOH and 0.30M CH3COONa are


mixed. Find the pH.
Review
The Henderson Hasselbalch equation comes from
solving a generic acid problem where both an acid and
its conjugate base are present.

You can use this equation to solve problems whenever


the 5% approximation is valid (note: you don’t have to
show me, but you do need to check in case it doesn’t
work)
Introduction to Buffers
Real life importance check:
pH of blood=7.4

Acidosis <7.35 Alkalosis> 7.50

Some products of your metabolism:


Ammonia
Urea (a base)
Uric acid Urea
CO2 (acidic when reacting with
water)
Real life importance check:
pH of blood=7.4

Acidosis <7.35 Alkalosis> 7.50


Products of your metabolism: Urea
Ammonia
Urea (a base)
Uric acid
CO2 (acidic when reacting with water)

So how can your body


control your pH so well?
Buffers
Acid and its conjugate base, or a base and its
conjugate acid
Essentially the systems we’ve talked about in the
common ion effect questions

It works by converting a strong acid into a weak acid,


or a strong base into a weak base.
A strong base can’t exist in solution with a weak acid
A strong acid can’t exist in solution with a weak base
Real life importance check:
pH of blood=7.4
Acidosis <7.35 Alkalosis> 4.5
Products of your metabolism:
Ammonia Urea
Urea (a base)
Uric acid
CO2 (acidic when reacting with water)

So how can your body control your pH so well?

It uses buffers!!!!
Buffers in the Body:

We discussed how CO2 can become acid in the body

This equilibrium is as follows, if both are present it’s a buffer


Buffers in the Body:
Hypoventilation
increased
How do we regulate CO2 levels? CO2
acidosis
Breathing levels Hyperventilation
decreased
What happens to the CO2 if we breath CO2
shallowly? alkalosis
Respiratory acidosis

Why is this bad?


Many reasons: here is one:
Hemoglobin in red blood cells binds either
O2 or H+
𝐻𝑏𝐻 + + 𝑂2 ⇌ 𝐻𝑏𝑂2 + 𝐻 +
Which of the following are buffers:
KNO2/HNO2 yes

KCl/HCl no

KHSO4/ H2SO4 no

Na2HPO4/NaH2PO4 Yes

KCN/HCN Yes

Na2SO4/NaHSO4 Yes

NH3/NH4NO3 Yes
Review
Buffers prevent large changes in pH caused by the addition of
acids or bases.

This is needed in many systems. Our blood buffer system uses


buffers to keep the pH in a very narrow range.

Buffers work by having both an acid and its conjugate base, or a


base and its conjugate acid present.
Therefore if an acid is added, it reacts with the base
If a base is added, it reacts with the acid
This keeps the pH change small.

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