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Chapters 18 & 19

Acids & Bases


H2O + HF(aq)

H3O+(aq) + F(aq)

Acids & Bases 2

Acid and Base Definitions

Arrhenius
Acid increases H + concentration
Base increases OH- concentration
Brnsted-Lowry (1923)
Acid donates a H +
Base combines with or accepts H +
Lewis
Acid electron acceptor
Base electron donor

Acids & Bases 3

Water itself has some ionic character:


H2O(l) + H2O(l)
H3O+(aq) + OH(aq)

Shorthand:
H2O(l)

H+(aq) + OH(aq)

This is called self-ionization. Although most chemists simply


write H+, it is important to realize that H+ by itself represents
a naked proton. In water the H+ is hydrated, that is, it forms
ionic-diople interactions with other water molecules. A
common way of more accurately representing the fact that it
is hydrated (interacting with waters) is to write H3O+.

Acids & Bases 4

H2O(l)

H+(aq) + OH(aq)

[H + ] [OH ]
Keq =
[H2O]
But H2O is a pure liquid and its concentration is
constant ([H2O] = 55.6 M, activity = 1), so it is not
included in the equilibrium expression:

K w = [H+ ][OH]
K w = 1.0 10 14 @ 20 DC
[H+] [OH] = 1 1014
[H+] = [OH] = 1 107 M
So the [H+] and [OH] concentration in pure water
is 1 107 M
We use Kw to indicate the water self- or autoionization. This is still a Keq or Kc. Chemists use
many subscripts on the equilibrium constant K to
indicate specific types of equilibria:
Kb = base equilibria
Ka = acid equilibria
Ksp = slightly soluble (solubility product) equilibria
Because of the often very small nature of H+
concentrations, chemists (and others) have devised

Acids & Bases 5

a logarithmic scale to simplify expressing these


values:
pH = log [H+]
The negative sign in front of the log makes sure
that most small concentrations of acid are given by
positive values.
[H+] = 1 107 M
pH = log(1 107) = 7.0
The greater the [H+] concentration, the LOWER
the pH value!!!

pH < 7.0
pH = 7.0
pH > 7.0

Acidic
Neutral
Basic (Alkaline)

Acids & Bases 6

Substance

pH

10 M HCl

1.0

1 M HCl

0.0

Stomach Acid (HCl)

1.4

Lemon Juice

2.1

Orange Juice

2.8

Wine

3.5

Black Coffee

5.0

Urine

6.0

Pure Water

7.0

Blood

7.4

Baking Soda Solution

8.5

Ammonia Solution

11.9

1 M NaOH

14.0

10 M NaOH

15.0

Acids & Bases 7

We can also define:

pOH = log

[OH ]

Although most chemists mainly use pH, pOH can


be useful in base equilibrium numerical problems
that we will run into later.
Another definition we use is:

pKw = log Kw = 14
So, for a given water solution:

pOH + pH = pKw = 14
or:

pOH = 14 pH
pH = 14 pOH

Acids & Bases 8

Example: The pH of wine is 3.5. What is the


[H+]? What is the [OH]? What is the pOH?
pH = log[H+] = 3.5
[H+] = antilog(3.5) = 103.5 = 3.16 104 M
14
1

10
K
w
11
=
3.1

10
[OH ] = + =
[H ] 3.16 10 4

pOH = log[OH] = log(3.1 1011) = 10.5


---- or ---pOH = pKw pH = 14 3.5 = 10.5

Problem: The pH in your stomach is around 1.


What is the [H+]? What is the [OH]? What is the
pOH?

Acids & Bases 9

Dissociation Equilibrium Constants


An acid is a compound that will ionize in solution
(usually water) to form a H+(aq) and a counteranion. This can be writen in a general fashion as:
HA(aq)
H+(aq) + A(aq)
The equilibrium expression for this reaction is:
[H+ ][ A ]

Keq =

[HA]

The equilibrium constant, Keq, is often given a


special name for acids: Ka or the acid dissociation
constant. The larger the Ka value the more H+ is
being produced (the lower the corresponding pH),
therefore, the stronger the acid!!!!
Just as with pH we can also define pKa as:

pKa = log Ka
The smaller (and more negative) the pKa the
stronger the acid!!!! This can be confusing, but is
very important: pKas are commonly used in
biology & chemistry!

Acids & Bases 10

Acid Dissociation Constants and pKa Values


Acid

HA

A-

Ka

pKa

hydroiodic

HI

1010

10

hydrobromic

HBr

Br

1010

10

perchoric

HClO4

ClO4

108

hydrochoric

HCl

Cl

108

sulfuric

H2SO4

HSO4

108

nitric

HNO3

NO3

108

trichloroacetic

Cl3COOH

Cl3COO

2 102

0.7

oxalic

HOOCCOOH

HOOCCOO

5.9 102

1.2

sulfurous

SO32

1.5 102

1.8

SO42

1.2 102

1.9

phosphoric

H2SO3
HSO4H3PO4

H2PO4

7.5 103

2.1

nitrous

HNO2

4.6 104

3.3

hydrofluoric

HF

NO2
F

3.5 104

3.5

formic

HCOOH

HCOO

1.8 104

3.8

benzoic

C6H5COOH

C6H5COO

6.5 105

4.2

oxalic (2nd H+)

HOOCCH2COO OOCCH2COO

6.4 105

4.2

acetic

CH3COOH

carbonic
hydrogen sulfide

sulfuric (2nd H+)

1.7 105

4.7

H2CO3

CH3COO
HCO3

4.3 107

6.4

H2S

HS-

9.1 108

7.1

HPO42

6.2 108

7.2

ammonium ion

H2PO4
NH4+

5.6 1010

9.2

hydrocyanic

HCN

NH3
CN-

4.9 1010

9.3

phosphoric (2nd)

Acids & Bases 11

Strong Acids
These are acids that are essentially completely
dissociated in solution (usually water).
H+(aq) + Cl(aq)
HCl(aq)
[H+ ][Cl ]
10 8
K =

[HCl]

In general, Ka > 1 for a strong acid (although there


is no firm dividing line!)
The common strong acids that you are expected to
know are:

HCl, HBr, HI (the hydrohalic acids)


H2SO4 (sulfuric acid) HNO3 (nitric acid)
HClO4 (perchloric acid)
HCl, H2SO4, and HNO3 are often referred to as mineral acids.

A strong acid completely dissociates the first H+, so


the H+ concentration is the same as the given acid
concentration. the pH of a strong acid is just
log of the acid concentration (= log[H+]).

Acids & Bases 12

Problem: What are the pH's of the following


solutions?
a) 0.001 M HCl
b) 0.1 M HNO3
c) 1 105 M H2SO4
d) 10 M HBr
e) 1 M HI
f) 0.1 M HF
g) 0.01 M HCl
h) 1 104 M HNO3
i) 1 M acetic acid
j) 1 1014 M HCl

Acids & Bases 13

Explanation for j) on the last page:


The actual proton concentration for any acid
dissolved in water is more precisely defined as:
[H+]total = [H+]acid + [H+]water
Normally, [H+]water is 1 107 M and is much less
than [H+]acid, so that we usually ignore it.
BUT, in this example, [H+]acid turns out to be
only 1 1014 M, which is much, much less than
the [H+]water.
So in this example we can actually ignore the tiny
amount of H+ contributed from the strong acid and
only consider the H+ naturally present in water:

This will work for acid concentrations of 1 108 M and


lower. It gets complicated mathematically right around
1 107 M (not dealt with in this course).

Acids & Bases 14

Lewis Dot Structures: Wheres the Proton?

When we write the formula for HNO3, it does NOT


mean that the proton (H+) is attached to the
nitrogen atom. The proton always binds to, or is
associated with a lone pair of electrons, usually on
one of the outer negatively charged atoms of a
polyatomic anion. Consider the Lewis Dot
structures for NO3, SO42, and ClO4:
when N has 4 bonds,
it is f or mally cationic

S can hav e
mor e than 8 ve-

O
O

N
O

Cl can hav e
mor e than 8 v e-

O
O

Cl

nitrate anion

sulfate dianion

perchlorate anion

Resonance, of course, will spread out the negative


charges and bonding over all the O atoms. H+ in
each of these cases binds to the oxygen atom(s) that
is (are) negatively charged:
H

N
O

O
O

O H

Cl

O H

O
O H

nitric acid

sulfuric acid

O
perchloric acid

Acids & Bases 15

Problem: Draw the Lewis Dot structure that best


minimizes the formal charges for the following
acids (some strong, some weak). Cleary show
where the H+ is coordinated.
a) HBF4 (fluoroboric acid, strong)

b) H2CO3 (carbonic acid, weak)

c) H3PO4 (phosphoric acid, weak)

d) CF3SO3H (triflic acid, strong)

e) HCO2H (formic acid, weak)

Acids & Bases 16

Strong & Weak vs. pH


A common mistake is to confuse pH with strong or
weak acids/bases. For example, if I tell you a
solution has a pH of 5.0, most of you would
incorrectly assume that it is a weak acid. Maybe,
maybe not.
A pH of 5.0 tells you that it is a weakly acidic
solution. This solution might have been made
from a medium to considerable amount of a weak
acid, or a very small amount of a strong acid.
Without knowing the concentration (or amount
and nature) of the acid used (not just the resulting
H+ concentration or pH), you cant tell whether it is
composed of a strong or weak acid.
It is true that solutions with very low pHs (for
example, 1.0) can pretty much only be composed
of strong acids.
So you need to be very careful with your language
in dealing with strong & weak acids and solutions
that are strongly or weakly acidic.

Acids & Bases 17

Polyprotic Acids
Sulfuric Acid:

H2SO4(aq)

H+(aq) + HSO4 (aq)

HSO4 (aq)

H+(aq) + SO42 (aq)

Ka1 108
Ka2 10-2

Phosphoric Acid:
H3PO4(aq)

H2PO4 (aq)

HPO42 (aq)

H+(aq) + H2PO4 (aq) Ka1 10-3

H+(aq) + HPO42 (aq) Ka2 10-8

H+(aq) + PO43 (aq) Ka3 10-13

Carbonic Acid:

H2CO3(aq)

H+(aq) + HCO3 (aq)

HCO3 (aq)

H+(aq) + CO32 (aq)

Ka1 10-7
Ka2 10-11

Acids & Bases 18

Note that for polyprotic acids only the first


dissociation (the first H+) is likely to occur. The
second (or third) dissociation process is far less
likely, so the contribution of these subsequent
dissociations to the overall [H+]total .

So, generally we only have to worry about the


first proton and the first dissociation constant
unless one is doing a titration or other acidbase reaction!!

Acids & Bases 19

Strong Bases
These are usually (and most commonly) alkali
metal hydroxides that dissociate completely in
solution:
NaOH(aq)

Kb =

Na+(aq) + OH(aq)
[Na + ][OH ]
10 8

[NaOH]

The common strong bases that you are expected to


know are:

LiOH, NaOH, KOH, RbOH, & CsOH


The alkaline earth hydroxides Ca(OH)2, Sr(OH)2,
Ba(OH)2 are medium strong bases.
Be(OH)2 & Mg(OH)2 are considered to be weak
bases since they only partially dissociate in water.
The smaller ionic radius of Be2+ and Mg2+ cations
polarize coordinated H2O enough to promote
hydrolysis (that is, loss of H + from H2O).

Acids & Bases 20

It is very important to remember that


there are almost always two steps in
converting from [OH] to pH:
1) convert [OH] to [H+]:
14
K
1

10
w
[H+ ] =
=
[OH ]
[OH ]

2) then convert [H+] to pH.


---- or ---1) convert [OH] to pOH
2) then convert pOH to pH:

pH = 14 pOH

Acids & Bases 21

Problem: What are the pH's of the following


solutions? What are the pOH's?
a) 0.001 M NaOH
b) 0.1 M CsOH
c) 1 105 M KOH
d) 10 M RbOH
e) 1 M NaOH
f) 0.1 M Be(OH)2
g) 0.01 M LiOH
h) 1 104 M NaOH
i) 1 M ammonia
j) 1 1014 M KOH

Acids & Bases 22

Explaination for j) on the last page:


The actual hydroxide concentration for any base
dissolved in water is more precisely defined as:
[OH]total = [OH]base + [OH]water
Normally, [OH]water is 1 107 M and is much
less than [OH]base, thus we can usually ignore it.
BUT, in this example, [OH]base turns out to be
only 1 1014 M, much less than the [OH]water.
So in this example we can actually ignore the tiny
amount of OH contributed from the base and only
consider the OH naturally present in water:

This will work for base concentrations of 1 108 M and


lower. It gets complicated mathematically right around
1 107 M (not dealt with in this course).

Acids & Bases 23

Conjugate Acid-Base Pairs


Bronsted-Lowry Definition of a Base: a substance
that combines or accepts a H+. Consider the
dissociation of an acid:
H2O + HF(aq)
H3O+(aq) + F(aq)

Because this is an equilibrium, F(aq) is back reacting with


H+(aq) to produce undissociated acid HF(aq). Therefore,
F(aq) is acting like a base! Since it was originally part of the
acid (HF), theres a special name for it: conjugate base.

Strong acids have weak conjugate bases.


Weak acids have stronger conjugate bases
(but usually not as strong as OH).
To indicate that an equilibrium favors one side of a
rxn chemists sometimes use the double equilibrium
arrows where one arrow is shorter. For a strong
acid (weak conjugate base) one could write:
HCl(aq)
H+(aq) + Cl(aq)

Acids & Bases 24

Bronsted-Lowry Definition of a Acid: a substance


that donates a H+.
Consider the reaction of a weak base with water:
NH3(aq) + H2O

NH4+(aq) + OH(aq)

Because this is an equilibrium, NH4+(aq) donates a H+(aq)


that reacts with OH(aq) to produce the original NH3 (and
water). Therefore, NH4+(aq) is acting like an acid! Since it
started as a weak base (NH3), we call NH4+ a conjugate acid.

Strong bases have weak conjugate acids.


Weak bases have stronger conjugate acids.
In the two reactions shown on this page and the previous,
water is acting as either an acid or a base. Any chemical that
can act as either an acid or base is called amphoteric.

In the following reaction, Na+ is more accurately called


a conjugate Lewis Acid (not a proton donor).

NaOH(aq)

Na+(aq) + OH(aq)

Acids & Bases 25

Weak Acids
These are acids that only dissociate to produce a
small amount of H+ in solution:

HF(aq)

H+(aq) + F(aq)

[H+ ][F ]
Ka =
= 3.5 10 4
[HF]

Most of a weak acid is dissolved in solution in its


undissociated, neutral form. An acid is weak
because its conjugate base (counter-anion) is a
good base and likes to bind to H+.
A weak acid typically has Ka < 1 103
Most weak acids are organic acids based on the
carboxylic group:

Some of the more common weak acids that we run


into on a daily basis include:

Acids & Bases 26

Acetic Acid

Carbonic Acid

Phosphoric Acid

H3C

OH

HO

active ingredient
in vinegar

HO

OH

OH
OH

used in soda
(Coke, Pepsi)

formed when CO2


dissolves in water

Acetylsalicylic Acid

Ascorbic Acid

O
HO
H3C

O
C

O
C

C
C

HO

CH2

OH

HO

OH

H
Aspirin

Vitamin C

Note that the OH groups in all these examples are not


hydroxides!! The oxygen atom of the OH is strongly bonded
to the atom they are attached to and will not fall off as OH .
Instead they dissociate H+ due to the Os electronegativity
and ability to stabilize negative charge(s).

Acids & Bases 27

Example: What is the pH of a 0.1 M solution of

acetic acid? Ka 1 105


Abbreviation for acetic acid: HOAc
Initial Cond: 0.1 M
HOAc(aq)
@ Equilib:

0.1 - x

0M
0M
H+(aq) + OAc(aq)
x

Substitute our x values into the equilibrium


expression and solve for x:
[H+ ][ OAc ]
K =
= 1 10 5

[HOAc]
( x )( x )
= 1 10 5
(0.1 x )

But, this will be a quadratic expression and we'll


have to use the quadratic formula to solve for x
(ugh!).
There is, however, a very good approximation we
can make to dramatically simplify the algebra.

Acids & Bases 28

Because Ka is fairly small (105) we know that


acetic acid is a weak acid and that we are only
going to make small quantities of H+. That means
that x should be a rather small number as well.
This in turn means that 0.1 x should be 0.1.
Our assumption, therefore, will be that x will be
much less than 0.1 M (initial concentration of
acid). This really simplifies the algebra:

( x )( x )
= 1 10 5
(0.1 x )
assume that x << 0.1 and drop from deonominator

( x )( x )
= 1 10 5
(0.1)

Important Approximation!!

x 2 = 1 10 6 } take square root of each side


x = [H+] = [OAc] = 1 103 M
pH = log(1 103) = 3.0

Acids & Bases 29

When can I drop x??


When is it a good approximation??
When Keq is 1 103 or smaller and x works out to
be at least an order of magnitude smaller than the
initial concentration that one is subtracting x from.
This also works when one is adding x to the initial
concentration (e.g., common ion problems).
Problem: What is the pH of a 10 M solution of
hydrogen sulfide? Ka 1 107
H2S(aq)

H+(aq) + HS(aq)

Acids & Bases 30

Problem: Prof. Stanley makes a new organic acid.


He prepares a 0.01 M solution and finds that the
pH is 4.0. What is the Ka for this new acid?
HA(aq)

H+(aq) + A(aq)

Problem: What is the pH of a 0.01 M solution of


HCN? Ka 4 1010

Acids & Bases 31

Effect of Structure on Acid/Base Behavior


Hydrohalic Acids
A combination of factors affects the acid strength
of hydrohalic acids:
1) Polarity of the H-X bond
Electrostatic
2) Strength of the H-X bond
attraction!!
3) Stability of the conjugate base, X
Thus, HF is a weak acid because the rather small
fluoride ion (F) has a concentrated negative
charge that very effectively and strongly attracts
the H+ cation, not allowing it to dissociate and
become a strong acid (like HCl, HBr, or HI).
HF
HCl
HBr
HI

Acids & Bases 32

Oxyacids
Oxyacids are those acids in which the central atom
(most commonly N, Cl, S or P) is bonded to at least
one, and usually more, oxygen atoms. The
resulting negative charge on this unit is balanced
by the proper # of H+ that associate with the
oxygen atoms (one per oxygen atom).
A list of common oxyacids and their names:
HNO2

HNO3

Nitrous

Nitric

HClO

HClO2

HClO3

HClO4

Hypochlorous

Chlorous

Chloric

Percloric

H2SO3

H2SO4

Sulfurous

Sulfuric

H3PO2

H3PO3

H3PO4

Hypophosphorous

Phosphorus

Phosphoric

Acids & Bases 33

The strength of oxyacids increases for a series of


compounds as follows:
1) given the same central atom, the more oxygens
present the stronger the acid
Reasoning: the more electronegative oxygen atoms
present, the more the negative charge on the anion is
spread out over a larger volume. This means that the
negative charge will be less concentrated on any single
oxygen. Thus, there will be a lower electrostatic attraction
to the H+ cations, allowing them to dissociate more easily.

2) for the same # of oxygens, the more electronegative the central atom, the stronger the acid
Reasoning: the more electronegative the central atom, the
more the negative charge on the anion will be pulled
towards the central atom and away from the outlying
oxygens. Thus, there will be a lower electrostatic
attraction to H+ cations, allowing easier dissociation.

3) For almost all acids, the higher the negative


charge on the anion (conjugate base), the lower
the acidity of the acid.
Reasoning: the higher the negative charge on the anion
(mono- or polyatomic) the stronger the electrostatic
attraction to the H+ cations. This makes it harder for the
H+ cation to dissociate.

Acids & Bases 34

4) For almost all acids, the more electronegative


atoms present (like O or F) the higher the
acidity of that acid.
Reasoning: the more electronegative atoms present, the
more the negative charge on the anion will be pulled
towards these atoms and away from the atom that the H+ is
associated with.

Example:
HClO

HClO2

HClO3

HClO4

Hypochlorous

Chlorous

Chloric

Percloric

Ka = 3 x 108

Ka = 1 x 102

Ka = 5 x 102

Ka 1 x 1010

Electrostatic charge potential (ECP) surface plots for ClO


through ClO4 anions (no H+). The red color (dark) indicates
more negative charge and a stronger electrostatic attraction
to the H+ cation (weaker acid). Positive charge is indicated
by the blue color (darker color on center atom).

Acids & Bases 35

Here are the ECP surface plots for the acids:


HClO
HClO2
HClO3

HClO4

Note that the blue area around the H atom indicating positive
charge is increasing as O atoms are added.

Problem: Which is the stronger acid of the pair?


a) H2SO4 or H3PO4
b) HNO2 or HNO3
c) HOBr or HOI
d) H2SeO4 or H2SeO3
e) HI or HF
f)

H2SO3 or H2SO4

g)

O
H
H

C
C

OH

or

F
F

C
C

OH

Acids & Bases 36

Weak Bases
These are bases that only react to a relatively small
extent with H+ in solution:
:NH3(aq) + H+(aq)
NH4+(aq)
The convention, however, for writing equilibria for
weak bases is to react the base with water, which
generates a small quantity of OH-:
NH4+(aq) + OH(aq)
:NH3(aq) + H2O
This is the equilibrium we use to define our base
equilibrium constant, Kb:
[NH4 + ][ OH ]
= 1.8 10 5
K =

[NH3]

In this equilibrium NH4+(aq) is called the


conjugate acid (it acts like a weak acid).

Acids & Bases 37

Some weak bases are shown in the table below:


Base

Formula

Structure

Kb

methylamine

NH2CH3

H N CH 3

4.4 x 10-4

carbonate ion

CO32-

2-

1.8 x 10-4

C
O

ammonia

NH3

H N H

1.8 x 10-5

hydrosulfide ion
nicotine

HS-

1.8 x 10-7

H S

C10H14N2

N
CH 3
N

hydroxylamine

NH2OH

H N OH

7 x 10-7
1.4 x 10-11
1.1 x 10-8

pyridine

C5H5N

1.9 x 10-9

Note that all bases have atoms with lone pairs of


electrons that can interact with a H+. Remember
that a H+ doesn't have any electrons and has a
positive charge. It will be attracted to atoms with
negative charges and/or lone pairs of electrons.

Acids & Bases 38

Example: What is the pH of a 0.1 M solution of

ammonia? Kb 1 105

Init:

0.1 M

0M

:NH3(aq) + H2O

0M

NH4+(aq) + OH(aq)

@ Eq: 0.1 - x

Substitute our x values into the equilibrium


expression and solve for x:
[NH4+ ][ OH ]
= 1 10 5
K =

[NH3]

( x )( x )
= 1 10 5
(0.1 x )
But, this will be a quadratic expression and the
quadratic formula is needed to exactly solve for x
(ugh!).
But lets use the very good approximation from
weak acid equilibria problem solving that will
dramatically simplify the algebra.

Acids & Bases 39

Because Kb is pretty small (105) we know that


ammonia is a weak base and that we are only going
to make small quantities of OH. That means that
x will be a pretty small number. This in turn
means that 0.1 - x will be 0.1.
Our assumption, therefore, will be that x will be
much less than 0.1 M (initial concentration of acid).
This now really simplifies our algebra:

( x )( x )
= 1 10 5
(0.1 x )
assume that x << 0.1 and drop from deonominator
Important Approximation!
( x )( x )

= 1 10 5
(0.1)
x 2 = 1 10 6 } take square root of each side

x = [OH] = [NH4+] = 1 103 M


pOH = log(1 103) = 3.0

pH = 14 pOH = 11

DANGER!!
VERY
Common
mistake!!

Acids & Bases 40

Problem: What is the pH of a 1 M solution of


sodium carbonate? Kb 1 104
CO32(aq) + H2O

HCO3(aq) + OH(aq)

Problem: What is the pH of a 0.01 M solution of


NH2OH? Kb 1 108

Acids & Bases 41

Lewis Acids & Bases


Acid
electron acceptor
electron donor
Base
Although the Lewis definition includes the
traditional Arrhenius and Brnsted-Lowry acids
& bases mentioned so far, it also encompasses
molecules that dont. Foremost are metal atoms
that form bonds to other molecules using empty
orbitals on the metal (Lewis acid) and filled lone
pairs on the donor atoms (Lewis bases).
Transition metal atoms typically form the
strongest bonds, followed by actinide and
lanthanides. Some examples are shown below:
PR3
Cl

Cl

Os

O
H

PhO

H3C

Cl

H2
N

R3P

Pd

PR3

N
PR3
Cl
O H2
Problem: Identify the Lewis Base and Acid parts of
each compound shown above. Extra: What is the
oxidation state of the metal in each compound?

Acids & Bases 42

Another class of important Lewis acids are


trivalent compounds of boron and aluminum that
have an empty orbital present. These are typically
very reactive to donor molecules including water.
BF3, for example, is considered a superacid.
F
Cl
B

Al

F
F
Cl
Cl
BCl3 will form a moderately strong bond to :NH3:
Cl
B

Cl

Cl

Cl
B

N
H

Cl

Cl

N
H

Problem: What is the hybridization of the B in BCl3?


What about the B in Cl3B:NH3?

Acids & Bases 43

Relationship Between Ka and Kb


Consider our ammonia equilibrium:
:NH3(aq) + H2O
NH4+(aq) + OH(aq)

[NH4+ ][ OH ]
Kb =
[NH3]
Kw
but remember that : [OH ] =
[H+ ]
substituting this in for [OH ] we now have :
[NH4+ ] Kw
Kb =
[NH3] [H+]

This expression now corresponds to the following


equilibrium multiplied times Kw:

:NH3(aq) +

H+(aq)

NH4+(aq)

The reverse of this reaction, however, is the "acid"


equilibrium:
NH4+(aq)

:NH3(aq) +

H+(aq)

Writing the reaction this way means that we can


now set-up a Ka equilibrium expression:

Acids & Bases 44

[NH3][H+ ]
Ka =
[ NH+4 ]
But note that the reciprocal of this expression is
already in the Kb relationship:

[NH3][H+ ]
Ka =
[ NH+4 ]

[NH4+ ] Kw
Kb =
[NH3] [H+]

Therefore, Ka and Kb are related via Kw.


Here are the very important Ka / Kb relationships
you need to know/understand:

Kw
Kb =
Ka

-or-

Kw
Ka =
Kb

Kw = Ka Kb

Acids & Bases 45

Knowing the mathematical relationship between


Ka and Kb is very important. Many references
only list Ka values for bases and not the Kb values
that you would expect.
When a Ka value is given for a base it is really the
value for the conjugate acid of that base. For
example:
Kb = 1.8 105
Base = NH3
Conjugate Acid = [NH4]+ Ka = 5.6 1010
(Kb)(Ka) = (1.8 105)(5.6 1010) = 1 1014
Kw
If a reference gives a Ka value for the base you are
looking up, you'll have to convert it to a Kb value
in order to calculate the [OH], and then the pH.
You must, therefore, pay close attention to what
data the problem is giving you and what you need
to use. READ CAREFULLY!!
DANGER!!
VERY Common mistake!!

Acids & Bases 46

Problem: What is the pH of a 0.1 M solution of the

weak base triethyl amine (NEt3)? Ka = 1 1011

Problem: What is the pH of a 0.01 M solution of

hydroxyamine (NH2OH)? Ka = 1 106

Acids & Bases 47

Salts of Weak Acids and Bases


When a weak acid (e.g., acetic acid) reacts with a
strong base (e.g., an alkali hydroxide like NaOH)
water and the salt of the weak acid is formed:

Note that the acetate anion formed in the reaction


is itself a weak base. Thus it can react with water
to produce a small amount of [OH].
Therefore, dissolving sodium acetate (the salt of
acetic acid) in water will make a basic solution.

Acids & Bases 48

Similarly, the reaction of a weak base with a strong


acid will produce the salt of a weak base, which will
act as a weak acid. Shown below we have the
reaction of ammonia with HCl to produce
ammonium chloride (the salt of a weak base):

Dissolving ammonium chloride in water, therefore,


produces an acidic solution (NH4+ is a weak acid).

Acids & Bases 49

The big question is How the heck do I tell whether


a salt will produce an acidic, basic, or neutral
solution??
The KEY is to remember the strong acids and
bases:
Strong Acids:
HCl(aq)
HBr(aq)
HI(aq)
HNO3(aq)
H2SO4(aq)
HClO4(aq)

H+(aq)
H+(aq)
H+(aq)
H+(aq)

+
+
+
+

Cl(aq)
Br(aq)
I(aq)
NO3(aq)

2H+(aq) + SO4(aq) *
H+(aq) + ClO4(aq)

These are
extremely
weak
conjugate
bases -Neutral
Anions!

Strong Bases:
LiOH(aq)
NaOH(aq)
KOH(aq)
RbOH(aq)
CsOH(aq)

Li+(aq)
Na+(aq)
K+(aq)
Rb+(aq)
Cs+(aq)

+
+
+
+
+

OH(aq)
OH(aq)
OH(aq)
OH(aq)
OH(aq)

These are
extremely
weak
conjugate
acids -Neutral
Cations!

Putting these Neutral (neutral here refers to their


acid-base properties, NOT their charges!!) anions
and cations together generates Neutral (not acidic
or basic) salts (Ca2+, Sr2+, Ba2+ salts not shown):

Acids & Bases 50

Neutral
Cation
Li+
Na+
K+
Rb+
Cs+

Neutral
Anion
Cl
Br
I
NO3
SO42
ClO4

Neutral Salts
LiCl, LiBr, LiI, LiNO3, Li2SO4,
NaCl, NaBr, NaI, NaNO3, Na2SO4,
KCl, KBr, KI, KNO3, K2SO4,
RbCl, RbBr, RbI, RbNO3, Rb2SO4,
CsCl, CsBr, CsI, CsNO3, Cs2SO4,
Perchlorate salts are explosive !!!

Solutions of these Neutral Salts are neither acidic


nor basic, but rather have a pH = 7 (Neutral!).
A simple set of guidelines, therefore, are:
CATIONS other than Li+, Na+, K+, Rb+, Cs+ (&
Ca2+, Sr2+, Ba2+) will generate ACIDIC solutions
(that is, the cation is a good conjugate acid)
ANIONS other than Cl, Br, I, NO3, SO42 will
generate a BASIC solution (that is, the anion is a
good conjugate base)

Acids & Bases 51

SALTS
Cation(+)Anion(-)
Cation comes from the base Anion comes from the acid
Identify the Cation
Is the cation from a strong base (Group 1A or Ca 2+, Sr 2+, Ba 2+)
YES

NO

Identify the anion


Is it from a strong acid?
YES
Salt Solution
will be
Neutral
(Salt of a
strong
acid & base)

Cation is from a weak base


(cation is a conjugate acid)

NO
Anion is from
a weak acid
(anion is a
moderate to
good conjugate
base)

Salt solution
will be basic
(salt of a
weak acid)

Identify the anion


Is the anion from a strong acid?
YES
Salt solution
will be acidic
(salt of a
weak base)

NO

Salt of a
weak acid &
a weak base!
Complicated!
Dont worry

Acids & Bases 52

Problem: Will the following salts make an acidic,


basic or neutral solution when dissolved in water?
a) NaF
Ka (HF) = 3.5 10-4
b) NaCl

c)

N H+ Cl-

Ka (HCl) = 1 108
Ka (pyridineH+) = 5 10-6

d) C6H5COONa Ka (C6H5COOH) = 6.5 10-5


e) RbBr

Ka (HBr) = 1 1010

f) CH3COOCs

Ka (CH3COOH) = 1.7 10-5

g) Cs2S

Ka (H2S) = 9.1 10-8

h) NH4NO3

Ka (NH4+) = 5.6 10-10

i) KCN

Ka (HCN) = 4.9 10-10

j) KNO3

Acids & Bases 53

Example: What is the pH of 1 M NaF?


Ka (HF) = 1 104. Neutral

Basic
Anion

Cation

Initial:

@ Eq:

1M

F(aq) + H2O

HF(aq) + OH(aq)

1-x

This is a basic equilibrium, so we need to convert


Ka into Kb:
14

Kw
1 10
10
Kb =
=
=
1

10
Ka
1 10 4

DANGER!!
VERY
Common
mistake!!

Our equilibrium expression, therefore, is:


[HF][OH ]
10
Kb =
=
1

10
[F ]
( x )( x )
= 1 10 10
(1 x )
assume that x << 1 and drop from deonominator

( x )( x )
= 1 10 10
(1)
x 2 = 1 10 10 } take square root of each side

x = [OH] = [HF] = 1 105 M

Acids & Bases 54

So the [OH] = 1 105 M. The pOH is:


pOH = -log(1 105) = 5
The pH, then, is given by:
pH = 14 - pOH = 14 - 5 = 9

DANGER!!
VERY
Common
mistake!!

Acids & Bases 55

Problem: What is the pH of a 0.1 M solution of


NH4Cl. Ka (NH4+) = 1 x 109.

Acids & Bases 56

Reactions of Acids & Bases


Strong Acids and Strong Bases:
The reaction of a strong acid and strong base is the
simplest type of acid-base reaction.
Consider the rxn of NaOH and HCl:
Na+(aq) + OH(aq) + H+(aq) + Cl(aq)
H2O + Na+(aq) + Cl(aq)
The rxn above shows all the aqueous species. Note that
NaCl(aq) is one of the products. When acids react with
bases, water and the salt of the acid/base are formed (the
base provides the cation and acid the anion).

The net ionic equation is shown below:


H2O
OH(aq) + H+(aq)
A key point to remember is that when we react
acids and bases we are usually reacting solutions of
acids and bases. When one mixes two solutions
together the overall volume increases and the
concentrations of all species will decrease!
Because of the change in volume due to the mixing
together of two solutions one has to take this into
account.
DANGER!! VERY Common mistake!!
We do this by dealing directly with MOLES and
not Molarity. So you have to:

Acids & Bases 57

convert molarity into moles,


do your calculations, then
convert back to molarity using the NEW total
(combined) solution volume
Example: What is the pH if we mix 100 mL of 0.1
M HCl with 50 mL of 0.1 M NaOH?
First, convert concentrations into moles:
(100 mL)(0.1 M) = 10 mmol HCl
(50 mL)(0.1 M) = 5 mmol NaOH
Now for the reaction: 5 mmol NaOH will react
with only 5 mmol HCl, leaving behind 5 mmol HCl.
But now we have 150 mL of solution, so [H+] is:

DANGER!! VERY Common mistake!!

5 mmol
= 0.033 M H+
150 mL

p H = 1.5

Acids & Bases 58

Problem: What will be the pH when 100 mL of


0.1 M HNO3 is mixed with 300 mL of 0.2 M KOH?

Problem: What will be the pH when 100 mL of


0.1 M HNO3 is mixed with 200 mL of 0.05 M
KOH?

Acids & Bases 59

Strong Acids and Weak Bases:


Strong Bases and Weak Acids:
Things get more complicated (well, not too bad)
when you react a strong acid with a weak base or a
strong base with a weak acid.
For this case, however, we will simplify things a
little by only using equivalent amounts of the acid
and base.
The key thing to remember when you react a weak
acid or base with a strong base or acid is that one
ends up with the SALT of that weak acid or base.
Remember that the SALT of a weak acid is actually
a weak base and gives a basic solution.
Similarly, the SALT of a weak base generates an
acidic solution.

DANGER!!
VERY Common mistake!!

Acids & Bases 60

Example: What is the pH if 150 mL of 0.5 M


acetic acid is mixed with 150 mL of 0.5 M NaOH?
Ka (HOAc) 1 105.
H2O + OAc(aq)
HOAc(aq) + OH(aq)
The OAc produced is a weak base and will
realizing this - DANGER!!
produce a weakly basic solution: NotVERY
Common mistake!!
H2O + OAc(aq)
HOAc(aq) + OH(aq)
Since this is a base equilibrium, we need to use Kb:

Kw
1 10 14
9
Kb =
=
=
1

10
Ka
1 10 5
Not realizing this - DANGER!!
Kb =

[HOAc][OH ]
[OAc ]

VERY Common mistake!!

= 1 10 9

Calculate the concentration of OAc :


(150 mL)(0.5 M) = 75 mmol HOAc
(150 mL)(0.5 M) = 75 mmol OH

Acids & Bases 61

Thus, we will produce 75 mmol of OAc. The


concentration of OAc, therefore, will be:
Volume Change DANGER!!
VERY Common
mistake!!

75 mmol
= 0.25M OAc
300 mL

Now we can set-up our initial and @eq conditions:


Initial:

0.25 M
H2O + OAc(aq)

@ Eq:

HOAc(aq) + OH(aq)

0.25 - x

[HOAc][OH ]
9
1
10
=

Kb =
[OAc ]
( x )( x )
= 1 10 9
(0.25 x )
assume that x << 0.25 and drop from deonominator
Approximation
( x )( x )
9
= 1 10
(0.25)
x 2 = 2.5 10 10 } take square root of each side
x = 1.6 10 5 = [OH ]

pOH = 4.6 } so the pH = 14 - 4.6 = 9.4


Forgetting to convert pOH to pH - DANGER!! VERY Common mistake!!

Acids & Bases 62

Problem: What is the pH of the reaction of


500 mL of 2 M NH3 and 500 mL of 2 M HCl?
Ka (NH4+) 1 1010.

Acids & Bases 63

Titrations
A titration is the careful measured addition of a
known concentration of one substance that will
react with another unknown material in order to
determine the concentration of the unknown
material.
Determining the concentrations of unknown materials is a
routine procedure in chemistry. Titrations are commonly
used to determine the concentrations of acids and bases in
solution, as well as many other chemicals. Titrations are also
often the simplest and least expensive way of determining
concentrations of unknown materials.

If we are titrating an unknown acid with a known


amount of base with a known concentration, we
can use the (M1)(V1) = (M2)(V2) relationship to
find the unknown's concentration at the
equivalence point (the point at which we've added
just enough base to react with all the acid).
In order to determine when we have reached the
equivalence point in an acid base reaction, we
generally use an indicator.

Acids & Bases 64

Indicators
An indicator is a weak organic acid or base that
has sharply different colors in its associated and
dissociated forms:
HIn(aq)
H+(aq) + In(aq)
red acidic
blue basic
Indicators usually have very intense colors so one
only has to use a very small amount (a few drops)
so it will not affect the titration of the solution.
Remember that the indicator is an acid or base so if
you add a lot it will affect the titration!!
OH

Phenophtalein

OH

H+

HO

HO
acidic form - colorless

anionic basic form - red

Methyl Red
O

O
OH
N N

acidic form - red

O
N

N N

anionic basic form - yellow

H+

Acids & Bases 65

Some Common Acid-Base Indicators


Name

pH color change
region

Acid color

Base color

Methyl violet

0-2

yellow

violet

methyl yellow

1.2 - 2.3

red

yellow

methyl orange

2.9 - 4.0

red

yellow

methyl red

4.2 - 6.3

red

yellow

bromthymol blue

6.0 - 7.6

yellow

blue

thymol blue

8.0 - 9.6

yellow

blue

phenolphthalein

8.3 - 10

colorless

pink

Alizarin yellow

10.1 - 12

yellow

red

HIn(aq)

H+(aq) + In(aq)

[H+][In ]
Ka =
[HIn]
At the color change [H+] = [In] = [HIn], so:

Acids & Bases 66

Titrating an unknown strong acid with a known


amount of strong base:

Acids & Bases 67

Titrating an unknown strong base with a known


amount of strong acid:

Acids & Bases 68

Titrating an unknown weak base with a known


amount of strong acid:

Acids & Bases 69

Titrating an unknown weak acid with a known


amount of strong base:

Acids & Bases 70

Buffer Solutions
Consider an acetic acid solution:

HOAc(aq)

H (aq) + OAc (aq)

If we add enough NaOAc (the salt of acetic acid) to


increase the OAc concentration roughly equal to
HOAc, we now form the following mixture:

HOAc(aq)

+
H (aq)

OAc(aq)

The added OAc, which is a weak base, will consume


some of the free H+ causing the pH to rise (become less
acidic).
Note that if we add H+ to this solution, it will react with
the large pool of weak base OAc to form HOAc. The
H+ concentration, therefore, will stay about the same.
Similarly, if we add some OH it will react with the H+
present. Since we have an equilibrium, however, some
HOAc will, in turn, dissociate to replace the missing H+,
keeping it about the same.
A solution of a weak acid and the salt (conjugate base)
of a weak acid or a weak base and the salt
(conjugate acid) of a weak base is called a BUFFER!

Acids & Bases 71

If the concentration of the two components is high


enough and you dont add too much acid or base, the
buffer solution will be very resistant to changes in the pH
due to added acid or base.
Buffer solutions are critically important to biological
systems (i.e., keeping us alive!).
For a solution of a weak acid or base and their salt, one
can write the following equations for calculating the
[H+] and [OH] of the buffer solution generated:

[OH ]

[Base]
= Kb

[
acidic
salt
]

[Acid]
= Ka

[
basic
sal
t]

These are called the Henderson-Hasselbalch


equations.
The log form of these equations:
[H+]

[basic salt]
pH = pK a + log

[
acid
]

[acidic salt]
pOH = pKb + log

[
base
]

Acids & Bases 72

If the acid/base concentration is the same as the


salt concentration, then we can write:
[OH] = Kb
[H+] = Ka
or
pOH = pKb
pH = pKa
By varying the weak acid or base and the salt being
used to make the buffer solution, as well as their
concentration ratio, one can set the pH of the
buffer to almost anything you want.
The more concentrated the buffer components, the
more effective the buffer solution will be at
resisting pH changes. But remember that you can
always overload a buffer by adding too much acid
or base to it.
One of the trickiest things for you to determine is
just what salts will work to make a buffer. The
salts of strong acids and bases (i.e., NaCl, KBr,
Na2SO4, CsNO3) do NOT usually make buffers,
nor do mixtures of strong acids and bases with
their salts!

Acids & Bases 73

Note, however, that reacting equivalent of a


strong base with a weak acid, generates a buffer
solution!

This is the region where we


have a buffer solution present

Acids & Bases 74

Problem: Which of the following solutions is a


traditional buffer prepared from a weak acid/base
and a conjugate salt?
a) 0.1 M NaOH + 0.1 M NaOAc
b) 0.01 M HCl + 0.01 M NaCl
c) 0.5 M NH4Cl + 0.5 M NH3
d) 2 M NaOAc + 2 M HOAc
e) 0.01 M citric acid + 0.01 M sodium citrate
f) 0.3 M H3PO4 + 0.3 M NaH2PO4
g) 2 M HNO3 + 2 M NaNO3
h) 0.05 M H2CO3 + 0.05 M KHCO3
i) 0.5 M HI + 0.5 M CsI
j) 0.2 M benzoic acid + 0.2 M cesium benzoate
k) 1 M NaOAc + 1 M KBr
l) 0.001 M HCl + 0.001 M KOH
m) 0.1 M KOAc + 0.1 M NH3
n) 0.2 M HOAc + 0.2 M KHCO3
b) Which will be the most effective buffer solution
at maintaining a given pH?
c) What are the pHs of the buffer solutions?