} Definition #1: Arrhenius (traditional)

Acids – produce H+ ions (or hydronium ions H3O+)

Bases – produce OH- ions

(problem: some bases don’t have hydroxide ions!)

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

Arrhenius base is a substance that produces OH- in water

} 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

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

NH3 + H2O NH4+ + OH-

Base Acid Acid Base
Label the acid, base, conjugate acid, and
conjugate base in each reaction:

HCl + OH- à Cl- + H2O

H2O + H2SO4 à HSO4- + H3O+

Definition #3 – Lewis
Lewis acid - a
substance that
accepts an electron
pair

Lewis base - a
substance that
donates an electron
pair
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.
 } The heme group
in hemoglobin
can interact with
O2 and CO.
} The Fe ion in
hemoglobin is a
Lewis acid
} O2 and CO can
act as Lewis
bases
Heme group
 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
Find the pH of
these:
1) A 0.15 M
solution of
Hydrochloric acid
2) A 3.00 X 10-7 M
solution of Nitric
acid
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
} A solution has a pH of 8.5. What is
the Molarity of hydrogen ions in the
solution?
pH = - log [H+]
8.5 = - log [H+]
-8.5 = log [H+]
Antilog -8.5 = antilog (log [H+])
10-8.5 = [H+]
3.16 X 10-9 = [H+]
 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
 Autoionization OH-

H3O+

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

oC

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

so Kw = [H3O+]2 = [OH-]2
and so [H3O+] = [OH-] = 1.00 x 10-7 M
} 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
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
The pH of rainwater collected in a certain region of the
northeastern United States on a particular day was
4.82. What is the H+ ion concentration of the
rainwater?

The OH- ion concentration of a blood sample is

2.5 x 10-7 M. What is the pH of the blood?
 -1
4 [OH-]
10
x -]
.0 H

10
1 O -1
4

-p
[
10

OH
-L
og
x
.0 +]

[O
1 [H

H
-]
[H+] pOH
H
pO
10

-
-p

14
H
-L
o

p H
g[

-
H

14
+]

pH
 Calculating [H3O+], pH, [OH-], and pOH
Problem 1: A chemist dilutes concentrated
hydrochloric acid to make two solutions: (a) 3.0
M and (b) 0.0024 M. Calculate the [H3O+], pH,
[OH-], and pOH of the two solutions at 25°C.

Problem 2: What is the [H3O+], [OH-], and pOH

of a solution with pH = 3.67? Is this an acid,
base, or neutral?

Problem 3: Problem #2 with pH = 8.05?

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

HNO3, HCl, H2SO4 and HClO4 are among the

only known strong acids.
}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)
CaO
 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) à NH4+ (aq) + OH-
(aq)
 Consider acetic acid, HC2H3O2 (HOAc)
HC2H3O2 + H2O à 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)
Larger Ka→stronger acid→more product→more H+
 Acids Conjugate
Bases
Increase
strength

Increase
strength
Weak acid has Ka < 1
Leads to small [H3O+] and a pH of 2 - 7
Weak base has Kb < 1
Leads to small [OH-] and a pH of 12 – 7
Larger Kb→stronger base→more product→more oH-
You have 1.00 M HOAc. Calc. the
equilibrium concs. of HOAc, H3O+, OAc-,
and the pH. HOAc H3O++ OAc-
Step 1. Define equilibrium concs. in ICE
table.
[HOAc] [H3O+] [OAc-]

initial 1.00 0 0
change -x +x +x
equilib 1.00-x x x
 You have 1.00 M HOAc. Calc. the equilibrium concs.
of HOAc, H3O+, OAc-, and the pH.
Step 2. Write Ka expression
+ - 2
[H O ][OAc ] 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)
You have 1.00 M HOAc. Calc. the equilibrium concs.
of HOAc, H3O+, OAc-, and the pH.
Step 3. Solve Ka expression
+ - 2
[H O ][OAc ] x
Ka = 1.8 x 10-5 = 3 =
[HOAc] 1.00 - x

First assume x is very small because

Ka is so small.
x 2
Ka = 1.8 x 10-5 =
1.00
Now we can more easily solve this
approximate expression.
You have 1.00 M HOAc. Calc. the equilibrium concs.
of HOAc, H3O+, OAc-, and the pH.
Step 3. Solve Ka approximate expression
x 2
Ka = 1.8 x 10-5 =
1.00

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

pH = - log [H3O+] = -log (4.2 x 10-3) = 2.37
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
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
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 !
HONORS ONLY!
} There are several ways to test pH
◦ Blue litmus paper (red = acid)
◦ Red litmus paper (blue = basic)
◦ pH paper (multi-colored)
◦ pH meter (7 is neutral, <7 acid, >7
base)
◦ Universal indicator (multi-colored)
◦ Indicators like phenolphthalein
◦ Natural indicators like red cabbage,
radishes
H2C2O4(aq) + 2 NaOH(aq) --->
acid base
Na2C2O4(aq) + 2 H2O(liq)
Carry out this reaction using a TITRATION.

Oxalic acid,
H2C2O4
Setup for titrating an acid with a base
1. Add solution from the
buret.
2. Reagent (base) reacts
with compound (acid) in
solution in the flask.
3. Indicator shows when
exact stoichiometric
reaction has occurred.
(Acid = Base)
This is called
NEUTRALIZATION.
35.62 mL of NaOH is
neutralized with 25.2
mL of 0.0998 M HCl by
titration to an
equivalence point.
What is the
concentration of the
NaOH?
Add water to the 3.0 M solution to
lower its concentration to 0.50 M
Dilute the solution!
But how much water
do we add?
How much water is added?
The important point is that --->

moles of NaOH in ORIGINAL solution =

moles of NaOH in FINAL solution
Amount of NaOH in original solution =
M•V =
(3.0 mol/L)(0.050 L) = 0.15 mol NaOH
Amount of NaOH in final solution must
also = 0.15 mol NaOH
Volume of final solution =
(0.15 mol NaOH) / (0.50 M) = 0.30 L
or 300 mL
Conclusion:
add 250 mL
of water to
50.0 mL of
3.0 M NaOH
to make
300 mL of
0.50 M
NaOH.
 A shortcut

M1 • V1 = M2 • V2
} You have a stock bottle of hydrochloric
acid, which is 12.1 M. You need 400
mL of 0.10 M HCl. How much of the
acid and how much water will you
need?
aA(phase) + bB(phase) Û cC(phase) + dD(phase)
The concentrations of each reagent are
constant at equilibrium, even though
individual molecules are constantly
reacting.

Another way of saying this is that the

reaction rate in one direction is equal to the
reaction rate in the reverse direction.
} If you write a reaction in reverse, the new K
is the inverse of the original K
aA(phase) + bB(phase) Û cC(phase) + dD(phase)
[C]c ´ [D]d
K"Forward" = a b
K is the equilibrium constant (unitless)
[A] ´ [B]
1
cC(phase) + dD(phase) Û aA(phase) + bB(phase) K"Reverse" =
K"Forward"
} If we add reactions, K values are multiplied
K1
Rxn 1 : aA(phase) + bB(phase) Û cC(phase) + dD (phase)
K2
Rxn 2 : eE (phase) + fF(phase) Û gG (phase) + hH (phase)
If we add the reactions together, the new K (call it K new ) is..
K new = K1 ´ K 2
 N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4]

aA + bB cC + dD

[C]c[D]d
K=
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products

K << 1 Lie to the left Favor reactants

14.1
Heterogenous equilibrium applies to reactions in which reactants and products
are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constant

‘
Kc =
[CaCO3]
[CaO] = constant

[CaCO3]
Kc = [CO2] = ‘
Kc x
[CaO]
Kp = PCO
2

The concentration of solids and pure liquids are not included in the
expression for the equilibrium constant.

14.2
} Calculate Reaction Quotient, Q
} The expression for Q is the same as K BUT
nonequilibrium concentrations rather than
equilibrium concentrations are put into the
expression
} Compare the value of Q to K.
 The reaction quotient (Qc) is calculated by substituting the initial concentrations
of the reactants and products into the equilibrium constant (Kc) expression.

IF
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium

14.4
1. System starts at equilibrium.
2. A change/stress is then made to system
at equilibrium.
– Change in concentration
– Change in volume
– Change in pressure
– Change in Temperature
– Add Catalyst
3. System responds by shifting to reactant
or product side to restore equilibrium.
 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the system adjusts in such
a way that the stress is partially offset as the system reaches a new equilibrium
position.

• Changes in Concentration

N2 (g) + 3H2 (g) 2NH3 (g)

Equilibrium
shifts left to Add
offset stress NH3

14.5
 Le Châtelier’s Principle

• Changes in Concentration continued

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left

Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
14.5
 Le Châtelier’s Principle

• Changes in Volume and Pressure

(Only a factor with gases)

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas

Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

14.5
 Le Châtelier’s Principle

• Changes in Temperature
vOnly factor that can change value of K

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases

Decrease temperature K increases K decreases

14.5
 Le Châtelier’s Principle

• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner
 Le Châtelier’s Principle

Change Equilibrium
Constant
Change Shift Equilibrium

Concentration yes no

Pressure yes no

Volume yes no

Temperature yes yes

Catalyst no no

14.5
 Calculating Equilibrium Concentrations
from K and Initial Concentrations
1. Balance chemical equation.
2. Determine Q to see which way reaction will proceed to get to equilibrium
3. Define changes needed to get to equilibrium. Use ‘x’ to represent the change
in concentration to get to equilibrium. Determine expression for equilibrium
concentration.
4. Write the expression for equilibrium constant, K.
5. Substitute expressions defined in step 3 into the equilibrium constant (step 4).
6. Solve for x and plug value back to table made in step 3.

14.4
 At 12800C the equilibrium constant (Kc) for the reaction

Br2 (g) 2Br (g)

Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M and [Br] = 0.012
M, calculate the concentrations of these species at equilibrium.

Let x be the change in concentration of Br2

Br2 (g) 2Br (g)

Initial (M) 0.063 0.012

Change (M) -x +2x

Equilibrium (M) 0.063 - x 0.012 + 2x

[Br]2 (0.012 + 2x)2

Kc = Kc = = 1.1 x 10-3 Solve for x
[Br2] 0.063 - x

14.4
 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x

4x2 + 0.0491x + 0.0000747 = 0

ax2 + bx + c =0 x=
Ö
-b ± b2 – 4ac
2a

x = -0.0105 x = -0.00178

Br2 (g) 2Br (g)

Initial (M) 0.063 0.012

Change (M) -x +2x

Equilibrium (M) 0.063 - x 0.012 + 2x

or 0.00844 M
At equilibrium, [Br] = 0.012 + 2x = -0.009 M
At equilibrium, [Br2] = 0.062 – x = 0.0648 M
14.4
} Kw (dissociation of water)
} Ksp (solubility of salts in saturated
solutions)
} Ka (acid dissociation)
} Kb (base hydrolysis)
} bx (complex ion formation)
} Kredox (redox reaction) and Kd (distribution
coefficient). We’ll not spend much time with
these two in CHEM 361.