UNIT 3

ACIDS AND BASES

Acid-Base Reactions
Acids reacted with bases are
Neutralization rxns.
HCl (aq) + NaOH (aq) H
2
O (l) + Na
+
(aq) + Cl
-
(aq)
The net ionic eqn is
H
+
(aq) + OH
-
(aq) H
2
O (l)
Na
+
and Cl
-
and spectator ions.
Objective 16.2
Define Acids and Bases:
Arrhenius
Bronsted-Lowry
Lewis
ACID/BASE Behavior in H
2
O
Arrhenius Bronsted-
Lowry
Lewis
Acid
Defn
Produces
H
+
in H
2
O
Proton
Donor
Electron-
pair
acceptor

Base
Defn
Produces
OH
-
in
H
2
O
Proton
Acceptor
Electron-
pair donor


ACID/BASE THEORIES
OVERLAP

Lewis
Lowry-
Bronsted
Arrhenius
Simplest but
poorest definition
Most commonly
used
In this class
Broadest
definition
Acids/Bases
Arrhenius definition:
Acid- yields H
+
in water solution;
Base- yields OH
-
in water solution.
Bronsted-Lowry definition:
Acid donates H
+
, H is ionizable
Base accepts H
+
, the base must have a lone
pair of electrons to accept H
+
.
. .
H N H
H
Lone Pair e-
Cmpds with N are indicative of a B-L base, but this is not a
sure-fire means of identifying a base (i.e. HCN is an acid).
This is a base, NH
3
Behavior of SA, SB, WA, WB
ACID/BASE ARE ELECTROLYTES
ELECTROLYTES DISS'C IN WATER
STRONG ACIDS/BASES TOTALLY
DISS'C IN WATER
WEAK ACIDS/BASES ONLY PARTIALLY
DISS'C IN WATER
No SA
remains
in soln
Very little
WA dissc
Strong vs. weak acids
Strong Weak
K
a
value large() small
Equil. position far,far right far left
[H
+
]
eq
& [HA] [H
+
]
eq
[HA]
o
[H
+
]
eq
<<[HA]
Conj. Base strength A
-
<<H
2
O A
-
>>H
2
O
How do you determine the direction/extent of a
reaction?
SA/SB~ complete diss'c -reactions proceeds
completely to the right
WA/WB ~ Dissc indicated by K
a
or K
b
values
The larger a K
a
or K
b
value, the stronger the acid
or base. (The greater the degree of dissc.)
The reaction always proceeds from the
stronger acid/base to the weaker acid and
base.
Strong Acids vs Weak Acids
Strong acids: MEMORIZE THESE
HCl, HBr, HI, H
2
SO
4
, HNO
3
, HClO
4
Identify Weak Acids
Acids with Ionizable Hydrogen(s)
Cations of Weak Bases (CA of WB),
Acidic Salts (also a CA of WB)
i.e. HC
2
H
3
O
2
(which may also be written
CH
3
COOH), H
2
CO
3
, NH
4
+
, NH
4
Cl
Objective 16.5
Strong Bases vs Weak Bases
Strong bases MEMORIZE THIS:
Hydroxides of Grp I and II, and M
2
O
molecules
i. e. Mg(OH)
2
Mg
2+
+ 2 OH
-
K
2
O + 2 H
2
O 2 K
+
+ 4 OH
-
Identify Weak Bases
Ammonia and amines,
Anions of WB (CB of WA),
Basic salts (also CB of WA)
Examples: NH
3
, CH
3
NH
2
, F
-
, NaF, K
2
SO
4
,
Compare SA/WA and SB/WB
SA have no K
a
value.
WA have a K
a
(even if it must be calculated).
SB have no K
b
value.
WB have a K
b
value (even if it must be
calculated).
Auto Ionization of Water
H
2
O (l) + H
2
O (l) H
3
O
+
(aq) + OH
-
(aq)
K
w
= [H
3
O
+
] [OH
-
]
K
w
= [H
3
O
+
][OH
-
]=1.0 x 10
-14
@ 25C
In pure water,
[H
3
O
+
] = [OH
-
] = 1.0 x 10
-7
H
3
O
+
is called a proton,
the hydrogen ion,
and the hydronium ion.
H
3
O
+
is also H
+
A note on H
+
As shorthand, H
+
is also often used to represent
H
3
O
+
. But neither of these is actually an
accurate reflection of the nature of a proton.
The proton is hydrated the proton is
surrounded by water molecules and could be
represented as H
3
O
+
, H
5
O
2
+
, or H
7
O
3
+
, etc.
H
2
O
H- Bond
H
2
O
Relationship of H
+
and OH
-
.
K
w
= [H
+
][OH
-
] (K
w
= 1.0 x 10
-14
at 25C)
1.0 x 10
-14
= [H
+
][OH
-
]
Notice that [H
+
] and [OH
-
] are inversely
proportional.
When one increases the other must decrease.
Thus [H
+
] = K
w
/[OH
-
] and [OH
-
] = K
w
/[H
+
]
K
w
= [H
+
] [OH
-
] = 1.0 x 10
-14
@ 25C
When [H
+
] = 1.0 x 10
-7
M , [OH
-
] = 10
-7
M (initially neutral)
Le Chateliers Principle and the Inverse relationship leads to
these conclusions:
1. If you Increase [H
+
], [OH
-
] Decreases
[H
+
] > 1.0 x 10
-7
M thus [OH
-
] < 1.0 x10
-7
M
2. If you Increase [OH
-
], [H
+
] Decreases
[H
+
] < 1.0 x 10
-7
M thus [OH
-
] > 1.0 x 10
-7
M
When [H
+
] > 1.0 x 10
-7
M, the solution is acidic.
When [H
+
] < 1.0 x 10
-7
M, the solution is basic.
Example
What is [OH
-
] if [H
+
] is 3.2 x 10
-4
M?
[OH
-
] = 3.1 x 10
-11
M
= [OH-]
1.0 x 10
-14
3.2 x 10
-4
= 3.1 x 10
-11
K
w
[H
+
]
Example: K
w
= [H
+
][OH
-
]
What is [H
+
] if [OH
-
] is 4.5 x 10
-6
?
[H
+
] = 1.0 x 10
-14
/4.5 x 10
-6
[H
+
] = 2.2 x 10
-9
M
K
w
[OH
-
]
= [H
+
]
What is pH?
pH is a shorthand method of expressing [H
+
] in
dilute sol'ns.
pH = -log [H
+
]
If [H
+
] = 1.0 x 10
-7
M, what is the pH?
pH = -log (1.0 x 10
-7
)
pH = 7.0
pH Ranges
0-7.00 -- Acidic
7.00 -- Neutral
7.00-14 -- Basic
Sig fig of log numbers Review Appendix
pH & pOH
Since K
w
= [H
+
][OH
-
] = 1.0x10
-14
- log(K
w
) = -log([H
+
][OH
-
])
- log(1.0x10
-14
) = -log[H
+
] + -log[OH
-
]
- (-14) = pH + pOH
or,
pH + pOH = 14.00
Relationships
Special K Box
[H
+
]
[OH
-
]
pH
pOH
K
w
=
[H
+
][OH
-
]
pH+pOH
= 14
pH=-log[H
+
]
pOH=-log[OH
-
]
[OH
-
]=10
-pOH
[H
+
]=10
-pH
Relationships
[H
+
]
[OH
-
]
pH
pOH
pH=-log[H
+
]
[H
+
]=10
-pH
pH + pOH = 14 K
w
= [H
+
][OH
-
]
pOH=-log[OH
-
]
[OH
-
]=10
-pOH
Note: One CANNOT
move directly from
pH to [OH-] or from
[H+] to pOH and
vice versa
What is pH given [OH
-
]?
Two methods to solve:
What is the pH of a
solution that has [OH
-
] =
1.8 x 10
-5
?
K
w
= [H
+
][OH
-
]
K
w
/ [OH
-
] = [H
+
]
[H
+
] = 1.0 x10
-14
/1.8x10
-5
[H+] = 5.6 x 10
-10
pH = -log [H
+
] = -log (5.6 x 10
-10
)
pH = 9.26
Or Alternative Method:
[OH
-
] = 1.8 x 10
-5
pOH = -log (1.8 x 10
-5
)
pOH = 4.74
pH + pOH = 14
14 pOH = pH
pH = 9.26
Find [H
+
] or [OH
-
] given
pH/pOH.
The pH of a sol'n = 2.6:
1. Is sol'n acidic, basic, neutral?
2. What is the pOH?
3. What is the [H
+
]?
4. What is the [OH
-
]?
pH of a soln is 2.6 (cont)
The pH is less than
7.00, therefore the
soln is acidic.
What is pOH
pOH = 14 pH
pOH = 14 2.6
pOH = 11.4
What is [H
+
]?
[H
+
] = 10
-pH
[H
+
] = 10
-2.6
[H+] = 2.5 x 10
-3
M
What is [OH-]?
[OH
-
] = 10
-pOH
or K
w
/[H
+
]
= 10
-11.4
or K
w
/(2.5 x10
-3
)
[OH-] = 4.00 x 10
-12
Bronsted-Lowry acid- a species that
donates an H
+
. (HCl, NH
4
+
,and HNO
2
)
Bronsted-Lowry base- any species that
accepts an H
+
. (OH
-
, NH
3
, CH
3
NH
2
)
We will spend a lot of time working with
these. Learn construction and terminology.
Hydrolysis reactions
(also called dissociation)
Acids:
HA(aq) + H
2
O(l) A
-
(aq)+H
3
O
+
(aq)
Or (Lazy, short-hand way)
HA (aq) H
+
(aq) + A
-
(aq)
For WEAK ACIDS:
K
a
= [H
+
][A
-
]/[HA]
For once
this is
acceptable,
If you are
comfortable
with the full
rxn
Hydrolysis/Dissociation
Reactions
Bases:
B(aq) + H
2
O(l) BH
+
(aq) + OH
-
(aq)
For WEAK BASES
K
b
= [BH
+
][OH
-
]/[B]
Teacher Rant: While it is acceptable to use the shortcut balanced eqns, it is not acceptableto skip
writing the balanced chem rxn altogether. As you will see, having this eqn to refer to after
a lot of analysis is invaluable.
Proton Transfer
Notice the arrows. The first rxn is a SA, the 2
nd
is a WB.
Amphoteric Species
Amphoteric species (like H
2
O) can act
as an acid or a base, depending upon
the system.
H
2
O can act as either an acid or a base
as shown in the examples.
Objective 18.2
Identify conjugate acid/base pairs
Acid Dissociation in Water
H
2
O(l) + HA(aq) H
3
O
+
(aq) + A
-
(aq)
Conjugate acid-base pairs:
HA(aq)/A
-
(aq) & H
2
O(l)/H
3
O
+
(aq)
For WEAK ACIDS
Equilibrium Expression:
[HA]
[H
3
O
+
][A
-
]
K
a
=
eq
Conjugate A/B Pairs
HCl(aq) + H
2
O(l) Cl
-
(aq) +H
3
O
+
(aq)

Acid Base
Base Acid
Conjugate Acid/Base Pairs
HCl/Cl
-
and H
2
O/H
3
O
+
Important point: each side of the rxn has an acid and a base.
Conjugate Acid/Base Pairs
of Weak Acids
HCN (aq) + H
2
O (l) H
3
O
+
(aq) + CN
-
(aq)
Conjugate Acid/Base Pairs:
HCN/CN
-
, H
2
O/H
3
O
+
Acid
Base
Base Acid
Conjugate Acid/Base Pairs for
a Weak Base
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)
Conjugate Acid/Base Pairs
NH
3
/NH
4
+
and H
2
O/OH
-
Base
Acid
Acid
Base
What are the Conjugate
Acid/Base Pairs?
HC
7
H
5
O
2
+ H
2
O(l) H
3
O
+
+ C
7
H
5
O
2
-
CH
3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH
-
CH
3
NH
2
+ HCl CH
3
NH
3
+
+ Cl
-
HBr + (CH
3
)
2
NH Br
-
+ (CH
3
)
2
NH
2
+
Identify Acid/Base Pairs
A = Acid, CB = Conjugate Base, B = Base, CA = Conjugate Acid
HC
7
H
5
O
2
+ H
2
O(l) H
3
O
+
+ C
7
H
5
O
2
-
HC
7
H
5
O
2
/C
7
H
5
O
2
-
(A/CB) & H
2
O/H
3
O
+
(B/CA)
Important Point: Conjugate Acid/Base pairs have
only an H difference in formula!
CH
3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH
-
H
2
O/OH
-
(A/CB) & CH
3
NH
2
/CH
3
NH
3
+
(B/CA)
Identify Acid/Base Pairs
A = Acid, CB = Conjugate Base, B = Base, CA = Conjugate Acid
CH
3
NH
2
+ HCl CH
3
NH
3
+
+ Cl
-
HCl/Cl
-
(A/CB) and CH
3
NH
2
/CH
3
NH
3
+
(B/CA)
HBr + (CH
3
)
2
NH Br
-
+ (CH
3
)
2
NH
2
+
HBr/Br- (A/CB) & (CH
3
)
2
NH/(CH
3
)
2
NH
2
+
(B/CA)
Practical Pointer
Important Point: Each side of the balanced rxn has
an acid and a base.
However, when dissociating Strong bases, do
NOT use H
2
O, it gets too complicated- it actually
cancels out.
NaOH Na
+
+ OH
-
But H
2
O does act as an acid in this rxn.
Find the pH of 0.10 M HCl sol'n
H
2
O(l) + HCl(aq) H
3
O
+
(aq) + Cl
-
(aq)
I - 0.10 0 0
C -0.10 +0.10 + 0.10
F 0 +0.10 + 0.10
pH = -log [H
+
]
pH = -log 0.10 = 1.00
Just a little note: The table has an F for final rather than an E for
equilibrium. It is still the same form as an ICE table, but since this rxn goes to
completion, it has a slightly different form but works in same fashion.
What are the [OH
-
] and pOH
of STRONG Acids
What are the [OH
-
]
and pOH of a 0.10
M HCl sol'n?
Once you solve for
[OH
-
], then apply to
pOH formula.
pOH = -log 1 x 10
-13
pOH = 13
[OH
-
] = 10
-pOH
[OH
-
] = 10
-13
[OH-] = 1 x 10
-13
M
or
[OH
-
] = K
w
/[H
+
]
[OH
-
] = 1.0 x 10
-14
/0.10
[OH-] = 1.0 x 10
-13
M
What is the pOH of a 0.10 M NaOH sol'n?
NaOH Na
+
+ OH
-
I 0.10 0 0
C -0.10 + 0.10 + 0.10
F 0 + 0.10 + 0.10
pOH = -log (0.10) =1.0
STRONG Bases
What are the [H
+
] and pH of a 0.100 M NaOH sol'n?
[H
+
] = 1.0 x 10
-14
/[OH
-
]
[H
+
] = 1.0 x 10
-13
pH = -log (1.0 x 10
-13
); pH = 13
Or
pH = 14 pOH
pH = 14 1 = 13
Solving WA or WB problems
Steps
Do you have a balanced eqn?
Are the units M?
Write the K
a
or K
b
expression based on the
balanced eqn. Do you have an H
+
or an OH
-
as a
product in the balanced eqn?
If you have H
+
as a product, the eq exp should be a K
a
.
If you have an OH
-
as a product, the eq exp should be a K
b
.
Substitute values into eq exp, and solve for
appropriate [H+], [OH-], Ka, Kb, or requested
data.
Simplifications in WA or WB problems
Weak Acids
HA + H
2
O H
3
O
+
+ A
-
[H+] = [A-] b/c for every H+ produced, A- is also
produced (in a 1:1 rxn).
K
a
=
[H
3
O
+
][A
-
]
[HA]
K
a
=
[H
3
O
+
]
2
[HA]
Simplification in solving WA or WB problems
Weak Bases
B + H
2
O BH
+
+ OH
-
[BH
+
] = [OH
-
]
[BH+][OH-]
[B]
Kb =
[BH
+
]
2
[B]
K
b
=
Ex: Given the pH and [HA]
init
, find K
a
If the pH of a 0.52 M HA solution is 3.20,
what is the K
a
?
HA + H
2
O H
3
O
+
+ A
-
Units okay, (conc is given in M), so proceed
with set-up. H
+
is product, need a K
a
.
[H
+
]
2
[HA]
K
a
=
Ex cont: Given the pH and [HA], find K
a
If the pH of a 0.52 M HA solution is 3.20, what is the K
a
?
[H
+
] = 10
-3.20
[H
+
] = 6.3 x 10
-4
K
a
= [H
+
]
2
/[HA]
K
a
= (6.3 x 10
-4
)
2
/ 0.52
K
a
= 7.7 x 10
-7
What is K
a
when [H
+
] = 4.32 x 10
-5
and [HA] = 3.20 x 10
-2
?
K
a
= [H
+
]
2
/[HA]
K
a
= (4.32 x 10
-5
)
2
/ 3.20 x 10
-2
K
a
= 5.83 x 10
-8
How does this differ from previous
example? [H
+
] provided in the problem, so
you dont have to calculate it from pH.
Given the pH and [B], find K
b
The pH of a 0.50 M solution of a WB, B, is 9.90. What is the K
b
?
Units okay given in M.
B + H
2
O BH
+
+ OH
-
OH
-
is the product, need an [OH
-
].
pOH = 14- pH = 4.10
[OH
-
] = 10
-pOH
= 10
-4.1
= 7.9 x 10
-5
M
Given the pH and [B], find K
b
(cont)
[OH
-
] = [BH
+
]
K
b
= (7.9 x 10
-5
)
2
/0.50
K
b
= 1.3 x 10
-8
[OH
-
]
2
[B]
K
b
=
Soln of WA or WB - Shortcut
Soln of WA
HA H
+
+ A
-
Soln of WB
B + H
2
O BH
+
+ OH
-
[H
+
] = K
a
[HA]
o
[OH
-
] = K
b
[B]
o
Shortcut Proof:
Solving WA or WB problems
Weak Acids
HA + H
2
O H
3
O
+
+ A
-
[H+] = [A-] b/c for every H+ produced, A- is also
produced (in a 1:1 rxn).
[H
+
]= K
a
[HA]
init
[H
+
]
2
[HA]
K
a
=
Find the [H
+
]given an initial [HA] conc and K
a
.
What is the [H
+
] of a 0.10 M sol'n of HC
7
H
5
O
2
,
K
a
= 6.4 x 10
-5
H
2
O(l) + HC
7
H
5
O
2
(aq) H
3
O
+
(aq) + C
7
H
5
O
2
-
(aq)
I ~ 0.10 0 0
C ~ - x + x +x
E ~ 0.10 x x x
K
a
= 6.4 X 10
-5
= [H
+
]
2
/[HC
7
H
5
O
2
]
Important Assumption:
WA/WB Problems
In ICE tables like the problem we are solving,
(i.e. when the eq position is E = 0.10 x).
Use the assmpt that x << Initial concentration
(i.e. x << 0.10 M = [HC
7
H
5
O
2
]
0
).
Solving WA/WB Problems
Rearranging to solve for [H
+
]
[H
+
] = (6.4 x 10
-5
)(0.10)
[H
+
] = 2.5 x 10
-3
Note the problem could have asked
for the pH (rather than [H
+
]) and you
have one more step to take.
pH = -log (2.5 x 10
-3
)
pH = 2.60
Review: What is the [OH
-
] and pOH of a Weak Acid Prior
example con't
(pH = 2.60, [H
+
] = 2.5 x 10
-3
M)
pOH = 14.00-2.60 = 11.40
[OH
-
] = K
w
/[H
+
] = 1.0 x 10
-14
/2.5 x 10
-3
Note: you could calculate [OH-] and pOH from
either method we learned earlier.
Shortcut Proof:
Solving WA or WB problems
Weak Bases
B + H
2
O BH
+
+ OH
-
[OH
-
] = K
b
[B]
init
[OH
-
]
2
[B]
K
b
=
Ex: Find [OH
-
] for Weak bases from
K
b
values
Find [OH
-
] for a 0.20 M sol'n (CH
3
)
2
NH.
(CH
3
)
2
NH + H
2
O (CH
3
)
2
NH
2
+
+ OH
-
Step back a minute, how do you figure out this is a base?
Is it on your memorized list of SA or SB? No.
So, look in the K
a
and K
b
table if the species is
exactly like the species in the table, then you
know whether it is an acid or a base.
Find pH for Weak bases from
K
b
values
(CH
3
)
2
NH + H
2
O (CH
3
)
2
NH
2
+
+ OH
-
K
b
= 5.9 x 10
-4
(from K
b
table)
K
b
= x
2
/[(CH
3
)
2
NH]
0
x = K
b
[(CH
3
)
2
NH]
0
x = 5.9 x 10
-4
(0.20 M) = 0.011
[OH-]
2
[(CH
3
)
2
NH]
Kb =
Note: I have substituted x for [OH
-
]. This is dangerous.
Find pH for Weak bases from
K
b
values
x = 0.011 M
Common Student mistake happens here!
What does x stand for? Its [OH
-
]! Many
students forget to input the right variable
and solve for H
+
here. So be careful!
[OH
-
] = 0.011 M
pOH = -log 0.011 = 1.96
pH = 14-1.96 = 12.04
Ex: Find pH for a 0.20 M sol'n (CH
3
)
2
NH.
The previous problem can be much more
complicated.
If the problem had asked for the pH
(rather than [OH-]), there are more steps
to undertake. Recall [OH
-
] = 0.11 M:
pOH = -log 0.011 = 1.96
pH = 14-1.96 = 12.04
Solving WA/WB Problems
By making the assumption that x << [ ]
0
,
you can safely skip the ICE table, and
proceed to the shortcut to solve WA/WB
problems.
However, always write the balanced eqn,
check that units are in M, and write the K
a
or K
b
expression as required!
Soln of WA or WB - Shortcut
Soln of WA
HA H
+
+ A
-
Soln of WB
B + H
2
O BH
+
+ OH
-
[H
+
] = K
a
[HA]
o
[OH
-
] = K
b
[B]
o
Objective 21.1
Identify K
w
= K
a
K
b
relationship
Calculate K
a
given K
b
Calculate K
b
given K
a
Conjugate K
a
and K
b
Relationships
Example to show relationship
HCN(aq) + H
2
O(l) H
3
O
+
(aq) + CN
-
(aq)
K
a
= 6.2 x10
-10
CN
-
(aq) + H
2
O(l) HCN(aq) + OH
-
(aq)
K
b
= ?
2 H
2
O (l) H
3
O
+
(aq) + OH
-
(aq)
K
w
= 1.0 x 10
-14
Conjugate K
a
and K
b
Relationships
Example to show relationship cont
K
a
= [H
3
O
+
][CN
-
] / [HCN]
K
b
= [OH
-
] [HCN] / [CN
-
]
K
w
= [H
3
O
+
] [OH
-
]
{[H
3
O
+
][CN
-
] / [HCN]} x {[OH
-
] [HCN] / [CN
-
]}
= [H
3
O
+
] [OH
-
]
Therefore: K
a
K
b
= K
w
K
b
= K
w
/K
a
= 1.0 x 10
-14
/ (6.2 x 10
-10
) = 1.6 x 10
-5
K and pK relationships
K
w
= K
a
x K
b
pK = pK
a
+ pK
b
You must be able to convert back and
forth between these.
Find K
a
given a K
b
value.
Find the K
a
given a pK
b
, and etc.
Relationships
Special K2 Box
K
a
K
b
pK
a
pK
b
K
w
=
K
a
K
b
pK
a
+ pK
b
= 14
pK
a
=-logK
a
pK
b
=-logK
b
K
a
=10
-pKa
K
b
=10
-pKb
Example
What is the K
a
of CH
3
NH
3
+
if K
b
(CH
3
NH
2
) is 4.4 x 10
-4
?
K
a
= K
w
/K
b
= 1.0 x 10
-14
/4.4 x 10
-4
K
a
= 2.3 x 10
-11
Calculate pH of an anion of a WA;
Ex: What is the pH of 0.75 M NaF sol'n?
Step 1: Identify the soln
Is NaF in your strong acid/base
memorized list? No, so it must be weak.
You look in the tables and there is no K
a
or K
b
value for NaF!! Now what are we
going to do?
Think salt.
What is the pH of 0.75 M NaF sol'n?
Step 2: Write balanced eqns and decide
whether you need a K
a
or K
b
.
NaF Na
+
+ F
-
F
-
+ H
2
O HF + OH
-
NaF is a salt. It will completely dissociate (see 1
st
balanced eqn)
But F- must equilibrate in the water solution (see the
2
nd
eqn).
Need a K
b
b/c the product side has an OH-.
What is the pH of 0.75 M NaF sol'n?
Step 3: Calculate K
b
.
You can find a K
a
in the table for HF, use
that to calculate K
b
.
K
w
/K
a
= K
b
K
b
= 1.0 x 10
-14
/6.8 x 10
-4
K
b
= 1.47 x 10
-11
What is the pH of 0.75 M NaF sol'n?
Step: Calculate [OH
-
] using the calculated K
b
.
[OH
-
] = Kb[F
-
]
init
[OH
-
] = ((1.47 x 10
-11
)(0.75))
1/2
[OH-] = 3.3 x 10
-6
M
Kb =
[OH-]
2
[F-]
What is the pH of 0.75 M NaF sol'n? cont
Finish the problem:
pOH = - log (3.3 x 10
-6
) = 5.48
pH = 14 5.49 = 8.52
Calculate pH of a cation of a WB
What is the pH of a sol'n containing 3.45 g
of CH
3
NH
3
NO
3
in 250 mL sol'n?
You must get this into M units.
3.45 g CH
3
NH
3
NO
3
(mol/94.1 g CH
3
NH
3
NO
3
) =
3.66 x 10
-2
mol
3.66 x 10
-2
mol/0.250 L = 0.150 M CH
3
NH
3
NO
3
Calculate pH of a cation of a WB (cont)
This is a salt it will undergo a two step rxn
CH
3
NH
3
NO
3
CH
3
NH
3
+
+ NO
3
-
CH
3
NH
3
+
+ H
2
O H
3
O
+
+ CH
3
NH
2
H
+
is a product, so you need a K
a
You have a K
b
for CH
3
NH
2
so you can
calculate the K
a
K
a
= K
w
/K
b
= 1.0 x 10
-14
/ 4.4 x 10
-4
= 2.3 x 10
-11
Calculate pH of a cation of a WB
(cont)
Now solve for [H
+
]with our usual shortcut.
[H
+
] = K
a
[CH
3
NH
3
+
]
0
[H
+
] = (2.3 x 10
-11
)(0.150 M)
[H
+
] = 1.85 x 10
-6
M
pH = 5.73
Objective 22.1
Analyze salt solutions to
determine whether the
solution is acidic, basic, or
neutral.
Salts -- General
Salt formation: acid + base salt + H
2
O
e.g., HCl + NaOH NaCl + H
2
O
But, two kinds of acids (SA/WA) & two
kinds of bases (SB/WB).
Thus, four kinds of salts (by source):
SA/SB SA/WB
WA/SB WA/WB
Overview
Formation of acidic and basic salts
ACID + BASE SALT + WATER
SA SB Neutral + H
2
O
WA SB Basic Salt + H
2
O
SA WB Acidic Salt + H
2
O
WA WB Depends
Note:The water must be removed to isolate the solid salt.
Summary:
Acidity/Basicity of Salts
Salt Source Salt Soln
SA/SB neutral
SA/WB acidic
WA/SB basic
acidic if K
a
(CA)>K
b
(CB)
WA/WB basic if K
a
(CA)<K
b
(CB)
neutral if K
a
(CA)=K
b
(CB)
{
Identifying Solns: Is C
6
H
5
NHBr neutral,acidic, or basic?
Salt dissociation:
C
6
H
5
NHBr C
6
H
5
NH
+
+ Br-
Soln re-equilibration
C
6
H
5
NH
+
+ H
2
O C
6
H
5
N + H
2
O
Most Salt solns - have recognizable ions like K
+
, Na
+
, Cl
-
,
Br
-
, NO
3
-
, etc. Dissociate these in a one way completion
reaction. Write an equilibration rxn for the other entity.
Look in the K
a
and K
b
tables. If the reactant in the equil eqn
looks EXACTLY like the K
a
or K
b
then you know it is either an
acid or a base.
If the reactant is different by an H, then it is a CA or CB (and
you may have to calculate K
a
or K
b
depending on the question).
Write the appropriate acid or base dissociation reaction.
Identifying Solns: Is C
6
H
5
NHBr
neutral,acidic, or basic? (cont)
What is the Br thing on the end of the salt?
This is the counterion. It makes the charge on
the molecule neutral.
What does Br
-
do to the pH of the solution?
Nothing! It is the CB of the SA (HBr) and is sooo
weak that it has no pH affect.
Identifying Solns: Is C
6
H
5
NHBr
neutral,acidic, or basic?(cont)
Salt dissociation:
C
6
H
5
NHBr C
6
H
5
NH
+
+ Br
-
Soln re-equilibration
C
6
H
5
NH
+
+ H
2
O C
6
H
5
N + H
3
O
+
How do you know whether the salt is
acidic/basic/neutral?
When you look in the K
a
and K
b
tables you
cant find C
6
H
5
NH
+
, but you can find C
6
H
5
N in
the K
b
table. It is different by 1 H so it is the
CA of the WB. This is an acidic soln.
(The difference could be more than one H in polyprotics).
Another analyzing Soln Example
Is LiNO
2
acidic, basic, or neutral?
Is it on your memorized list of SA or SB?
No, but watch out- HNO
3
is on the SA list.
Can you find it in either the K
a
or K
b
table?
No, but HNO
2
is in the K
a
table.
LiNO
2
is a basic salt. Li
+
is the CA of a SB
(LiOH). The NO
2
- is the CB of a WA and the
only difference between HNO
2
and NO
2
- is
the H.
Another analyzing Soln Example (cont)
What reactions occur when solid LiNO
2
is
added to water?
It will undergo a two step eq process.
Step 1 the salt completely dissociates:
LiNO
2
Li
+
+ NO
2
-
Step 2 the species re-equilibrate with H
2
O:
NO
2
-
+ H
2
O HNO
2
+ OH-
This is a basic soln. The product side of the eqn
contains an OH
-
! The HNO
2
is a WA in the K
a
table. You need to calculate a K
b
if you are solving
a problem.
Another example
What are the species and reactions for a
soln of CH
3
NH
3
ClO
4
?
Tricky huh?
ClO
4
-
is the CB of a SA (HClO
4
); watch for
NO
3
-
, Br
-
, Cl
-
, I
-
too.
When you dissociate this:
CH
3
NH
3
ClO
4
CH
3
NH
3
+
+ ClO
4
-
Another example (cont)
The CH
3
NH
3
+
is the CA or a WB and will
undergo an equilibrium rxn:
CH
3
NH
3
+
+ H
2
O CH
3
NH
2
+ H
3
O
+
The solution is acidic (note the H
+
as a
product).
Note: you would have to find a K
a
to answer
most questions here b/c the product is H
+
but
all you have is a K
b
for CH
3
NH
2
.
A Hard One: Analyze the solution
WA/WB salt
What are the species and eqns for a
solution containing C
6
H
5
COOCH
3
CH
2
NH
3
?
Even more difficult to see but:
C
6
H
5
COOCH
3
CH
2
NH
3
C
6
H
5
COO
-
+ CH
3
CH
2
NH
3
+
C
6
H
5
COO
-
is the CB of the WA, C
6
H
5
COOH
CH
3
CH
2
NH
3
+
is the CA of the WB CH
3
CH
2
NH
2
A Hard One: Analyze the solution
(cont) WA/WB salt
To decide if this is an acidic or basic salt,
you have to compare the K
a
of the WB to
the K
b
of the WA:
Rxn 1:
CH
3
CH
2
NH
3
+
+ H
2
O CH
3
CH
2
NH
2
+ H
3
O
+
You have to have a K
a
b/c H
+
is a product.
You only have a K
b
, so calculate K
a
.
A Hard One: Analyze the solution
(cont) WA/WB salt
Rxn 2:
C
6
H
5
COO
-
+ H
2
O C
6
H
5
COOH + OH
-
You have to have a K
b
because OH
-
is a product.
You have to calculate it! (b/c C
6
H
5
COOH is only found in the
K
a
table)
Final Step:
In this example, you compare the K
a
of CH
3
NH
3
+
with the K
b
of C
6
H
5
COO
-
to decide if this soln is
acidic or basic. The larger K
a
or K
b
tells you
which it is. (See next slide.)
A Hard One: Analyze the solution
(cont) WA/WB salt
Lets look at these:
C
6
H
5
COO
-
+ H
2
O C
6
H
5
COOH + OH
-
K
b
= K
w
/K
a
= 1.0 x 10
-14
/ 6.3 x 10
-5
K
b
= 1.6 x 10
-10
CH
3
CH
2
NH
3
+
+ H
2
O CH
3
CH
2
NH
2
+ H
3
O
+
K
a
= K
w
/K
b
= 1.0 x 10
-14
/4.3 x 10
-4
K
a
= 2.3 x 10
-11
Kb > Ka, soln is basic
Further examples: Is the salt
acidic, basic, or neutral?
NaCHO
2
NaNO
3
NH
4
Br
NH
4
F
Is the salt acidic, basic, or neutral?
NaCHO
2
Do a two step dissociation when working these problems.
Step 1: Dissociate the salt
NaCHO
2
Na
+
+ CHO
2
-
Analyze the products, Na
+
is neutral, CHO
2
-
is the weak
conjugate base of a weak conjugate acid. (See K
a
table
HCHO
2
is in the table.)
Step 2:
CHO
2
-
+ H
2
O HCHO
2
+ OH
-
OH- is a product in the second step, therefore NaCHO
2
is a
basic salt.
Is the salt acidic, basic, or
neutral?
NaNO
3
Step 1:
NaNO
3
Na
+
+ NO
3
-
Both of the products are conjugates of
Strong species (Na
+
from NaOH and NO
3
-
from HNO
3
), so the solution is neutral a
neutral salt.
Is the salt acidic, basic, or
neutral?
NH
4
Br
Step 1:
NH
4
Br NH
4
+
+ Br
-
Br
-
is the conjugate base of a SA (HBr) so it is
neutral.
Step 2:
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
H
+
is a product, so the solution is acidic and
NH
4
Br is an acidic salt.
Is the salt acidic, basic, or
neutral?
NH
4
F
Step 1:
NH
4
F NH
4
+
+ F
-
NH
4
+
is the CA of a WB (NH
3
) and F
-
is
the CB of a WA (HF).
This problem is more complicated!
Is the salt acidic, basic, or
neutral? (NH
4
F cont)
Step 2 must do the rxn for each
component
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
F
-
+ H
2
O HF + OH
-
You will have to find the K
a
of NH
3
(b/c
H
+
is a product in the 1
st
eqn)and the K
b
of HF (b/c OH- is a product in the 2
nd
eqn) to decide the type of salt.
Is the salt acidic, basic, or
neutral? (NH
4
F cont)
K
a
for NH
4
+
= K
w
/K
b
K
a
= 1.0 x 10
-14
/ 1.8 x 10
-5
K
a
= 5.56 x 10
-10
K
b
for F
-
= K
w
/K
a
K
b
= 1.0 x 10
-14
/6.8 x 10
-4
K
b
= 1.47 x 10
-11
K
a
> K
b
, thus this is an acidic salt.
Review: What is the pH of 0.500 M soln of NH
4
F?
As we have just seen this solution is acidic.
Therefore:
K
a
= [H
+
]
2
/[NH
4
F]
[H
+
] = (K
a
[NH
4
F]
o
)
1/2
[H
+
] = (5.56 x 10
-10
x 0.500)
1/2
[H
+
] = 1.7 x 10
-5
M
pH = 4.78
Lesson 23
Polyprotic Acids
These contain more than one H
+
that can
diss'c. Following is a step-wise dissociation
of a polyprotic acid
H
2
CO
3
H
+
+ HCO
3
-
K
a1
= 4.3 x 10
-7
HCO
3
-
H
+
+ CO
3
2-
K
a2
= 5.6 x 10
-11
What is the pH of Strong Polyprotic Acids?
H
2
SO
4
+ H
2
O H
3
O
+
+ HSO
4
-
K
a
= large
HSO
4
-
+ H
2
O H
3
O
+
+ SO
4
2-
K
a2
= 1.2x10
-2
Depends on concentration--
If 1 M sol'n, the 2nd H
+
makes almost no difference.
If the concentration is low, however, the 2nd H
+
does make a difference.
What is the pH of a 0.50 M weak
polyprotic acid?
H
3
PO
4
H
+
+ H
2
PO
4
-
K
a1
= 7.5 x 10
-3
H
2
PO
4
-
H
+
+ HPO
4
2-
K
a2
= 6.2 x 10
-8
HPO
4
2-
H
+
+ PO
4
3-
K
a3
= 4.8 x 10
-13
Second H
+
makes almost no difference.
Calculate pH based upon K
a1
.
[H
+
] = K
a1
[H
3
PO
4
]
init
[H+] = 0.087
pH = 1.21
Analyze a salt soln that contains a
polyprotic conjugate.
Lets look at NaHCO
3
sodium bicarbonate- a
common household chemical and a salt that
creates the CB of a WA.
NaHCO
3
completely dissociates:
NaHCO
3
Na
+
+ HCO
3
-
HCO
3
-
will re-equilibrate with H
2
O but
does it form H
2
CO
3
or CO
3
2-
?
Analyze a salt soln that contains a polyprotic conjugate.
(cont)
To decide you have to write the eqn both
ways and compare K
a
and K
b
.
The eq rxn could be:
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
This solution is basic (OH
-
is a product). You have to
calculate K
b
for H
2
CO
3
.
The eq rxn could be:
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
The solution is acidic so you have to use K
a2
provided in the table.
Analyze a salt soln that contains a polyprotic conjugate.
Lets step back now and think about
these K
a
s, K
b
s, and eqns:
It helps to do stepwise H
+
dissociation
and associate it with the proper Ka
value for this analysis.
H
2
CO
3
+ H
2
O H
3
O
+
+ HCO
3
-
K
a1
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
K
a2
Analyze a salt soln that contains a polyprotic conjugate. (cont)
Now compare the possible eqns with the
step-wise acid dissociation rxn
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
Compare to step-wise dissociation:
H
2
CO
3
+ H
2
O H
3
O
+
+ HCO
3
-
K
a1
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
K
a2
The possible eqn looks EXACTLY like one of
the step-wise dissociations use the K
a
associated with this eqn. (K
a2
here)
Analyze a salt soln that contains a polyprotic conjugate. (cont)
What about the other possible rxn?
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
Compare to step-wise dissociation:
H
2
CO
3
+ H
2
O H
3
O
+
+ HCO
3
-
K
a1
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
K
a2
This one isnt as easy to see but note that the two
CA/CB species in our potential rxn are the same
two CA/CB species in K
a1
step-wise dissociation.
Use this K
a1
to determine the K
b
Analyze a salt soln that contains a polyprotic conjugate. (cont)
The eq rxn could be:
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
This solution is basic (OH- is a product). You have to
calculate K
b
for H
2
CO
3
.
The eq rxn could be:
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
The solution is acidic so you have to use K
a2
provided
in the table.
K
b
= K
w
/K
a1
= 1.0 x 10
-14
/ 4.5 x 10
-7
= 2.2 x 10
-8
K
a
= K
a2
= 4.7 x 10-
11
K
b
>K
a
, solution is basic and rxn was
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
What is the pH of a 0.500 M NaHCO
3
soln: Review first
NaHCO
3
Na
+
+ HCO
3
-
Na
+
is the conj of a strong base - so neutral.
You must evaluate the species for H+ and OH-.
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
K
a2
= 5.6 x 10
-11
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
K
b
= K
w
/ K
a1
= (1 x 10
-14
)/(4.3 x 10
-7
)
= 2.3x10
-8
K
b
> K
a
therefore HCO
3
-
is a base
H+ product
OH- product
Must calculate
a Kb.
What is the pH of a 0.500 M
NaHCO
3
soln: (cont)
We know from our previous analysis that the
soln is basic.
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
K
b
= [OH
-
]
2
/[HCO
3
-
]
2.3 x 10
-8
= [OH
-
]
2
/[HCO
3
-
]
[OH
-
] = ((2.3 x 10
-8
)(0.500))
1/2
[OH
-
] = 1.1 x 10
-4
M
pOH = 3.97
pH = 10.03
Lesson 24
Rank solutions in terms of
increasing or decreasing strength.
Rank solution in terms of
increasing or decreasing pH.
Strength of Soln
Two types of questions from analysis of
the strengths of solns:
1. Determine the increasing (or decreasing)
strength in a series of acids or bases.
2. Determine the increasing or decreasing
pH (or pOH) in a series of solns.
Strength of Soln
Question Type One
1. Soln analysis (the series must all be either
acidic or basic for this shorter analysis).
2. Find or calculate K
a
or K
b
3. Rank strength of soln as required by the
question according to size of K
a
and K
b
.
Practical Pointer: Be careful here.
1.0x 10
-2
> 1.0 x 10
-5
> 1.0 x 10
-8
0.010 > 0.000010 > 0.000000010
Strength of Soln
Question Type 2 Requires:
1. Soln analysis (Note: the series can contain both
acids and bases.)
2. Identifying or calculating the appropriate K
a
or K
b
.
3. Calculate the [H
+
] or [OH
-
].
4. Calculate the pH or pOH
5. Rank soln as required by the question.
Acid/Base Relative Strength
In water solutions all strong acids are equally
strong and all strong bases are equally
strong.
Weak acids and bases have relative strengths
based on their eq constants, K
a
or K
b.
The stronger the acid or base, the weaker the
conjugate.
Example
Rank the following in terms of acid strength
from strongest to weakest.
HI, HC
2
H
3
O
2
, CH
3
NH
3
NO
3
, HNO
2
You must analyze each one of these.
HI = SA;
HC
2
H
3
O
2
has a K
a
= 1.8 x 10
-5
,
CH
3
NH
3
NO
3
(forms CH
3
NH
3
+
and NO
3
-
)
calculated K
a
= 2.27 x 10
-11
;
HNO
2
has K
a
= 7.1 x 10
-4
Rank Strength of Acids
Answer: Largest K
a
is stronger acid.
HI > HNO
2
> HC
2
H
3
O
2
> CH
3
NH
3
NO
3
> 7.1 x 10
-4
>1.8 x 10
-5
> 2.3 x 10
-11
Rank Strength of Bases
Rank the following from strongest to weakest bases:
Do the soln analysis yourself.
NH
3
, KOBr, Ca(OH)
2
, C
6
H
5
NH
2
NH
3
: K
b
= 1.8 x 10
-5
KOBr (the CB of a WA), calculated K
b
= 4.3 x 10
-6
Ca(OH)
2
= SB
C
6
H
5
NH
2
: K
b
= 4.0 x 10
-10
Rank Strength of Bases
Answer: Largest K
b
is stronger base
Ca(OH)
2
> NH
3
> KOBr > C
6
H
5
N
> 1.8 x 10
-5
> 4.3 x 10
-6
> 4.0 x 10
-10
Rank the following 0.10 M solns
in order of increasing pH
Na
2
CO
3
, KCOOH, KHSO
4
, C
5
H
10
NH
2
Cl
This is a long, time consuming problem.
Some of these solution are a little tricky, so
we will take several slides to analyze each
one separately and them answer the
question at the end.
Rank the following 0.10 M salts in
order of increasing pH
Na
2
CO
3
2 Na
+
+ CO
3
2-
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-
CO
3
2-
is the CB of a polyprotic acid.
Generally, when you have a polyprotic, you must
analyze whether the conjugate will add or gain an H
+
.
But, in this case, there is no H for the CO
3
2-
to lose, so
there is only one direction for the reaction to proceed.
You will use K
a2
to find the K
b
b/c a step-wise
dissociation of the polyprotic has the SAME two
carbonate species.
Step-wise dissc to show you:
H
2
CO
3
+ H
2
O H
3
O
+
+ HCO
3
-
K
a1
HCO
3
-
+ H
2
O H
3
O
+
+ CO
3
2-
K
a2
K
b
= K
w
/4.7 x 10
-11
= 2.13 x 10
-4
[OH
-
] = ((K
b
)([CO
3
2-
]))
1/2
= 4.6 x 10
-3
, pH = 11.66
Rank the following 0.10 M salts in order of increasing pH
KHSO
4
K
+
+ HSO
4
-
HSO
4
-
+ H
2
O H
3
O
+
SO
4
2-
HSO
4
-
is also a conjugate of a polyprotic acid.
Normally you would have to evaluate whether a CB of a
polyprotic acid gains or loses an H
+
ion. However, in this
case, the only direction the rxn can proceed is to lose an
H
+
. Why? B/c H
2
SO
4
is a SA and a SA is never going to
re-associate in water. Therefore, this is an acidic salt
Step-wise dissociation to show you:
H
2
SO
4
+ H
2
O H
3
O
+
+ HSO
4
-
K
a1
=
HSO
4
-
+ H
2
O H
3
O
+
SO
4
2-
K
a2
K
a2
= 1.0 x 10
-2
[H
+
] = ((K
a2
)[HSO
4
-
]))
1/2
= 0.032 M
pH = 1.5
Rank the following 0.10 M salts in
order of increasing pH
KCOOH K
+
+ COOH
-
COOH
-
+ H
2
O HCOOH + OH
-
This soln produces a basic soln the product
contains an OH
-
. Need a K
b
K
b
= K
w
/ K
a
= 1.0 x 10
-14
/1.8 x 10
-4
K
b
= 5.6 x 10
-11
[OH
-
] = ((K
b
)([COOH
-
])
1/2
= 2.4 x 10
-6
pH = 8.37
Rank the following 0.10 M salts in
order of increasing pH
C
5
H
10
NH
2
Cl C
5
H
10
NH
2
+
+ Cl
-
C
5
H
10
NH
2
+
+ H
2
O H
3
O
+
+ C
5
H
10
NH
C
5
H
10
NH
2
+
is the CA of a WB. You need to
find a K
a
.
K
a
= K
w
/K
b
= 1.0 x 10
-14
/1.3 x 10
-3
K
a
= 7.69 x 10
-12
[H
+
] = ((K
a
)([C
5
H
10
NH
2
+
])
1/2
= 8.77 x10
-7
pH = 6.06
Rank the following 0.10 M salts in
order of increasing pH
Okay now lets answer the question:
Rank the following salts in order of increasing
pH.
Na
2
CO
3
KHSO
4
KCOOH C
5
H
10
NH
2
Cl
pH =11.66
pH = 1.5
pH = 8.4
pH = 6.1
HSO
4
-
< C
5
H
10
NH
2
+
< COOH- < CO
3
2-
Lewis Acids and Bases
Lewis Acid- an electron pair acceptor.
Contains a vacant orbital which can accept
an electron pair.
Lewis Base- an electron pair donor.
A molecule or species with lone pairs of
electrons.
Examples
Lewis Acids: AlCl
3
, FeCl
3
High charge to mass ratio
Lewis Bases: NH
3
, H
2
O