Acids and bases

1. Autoionization reaction of liquid water

2. pH, pOH, and pKw
3. conjugate acid-base pairs
4. acid or base strength and the magnitude of Ka, Kb, pKa, and pKb
5. leveling effect
6. To be able to predict whether reactants or products are favored in an
acid-base equilibrium
7. use molecular structure and acid and base strengths
8. use Ka and Kb values to calculate the percent ionization and pH of a
solution of an acid or a base
9. calculate the pH at any point in an acid-base titration
10.common ion effects and the position of an acid-base equilibrium
11. how a buffer works and how to use the Henderson-
Hasselbalch equation to calculate the pH of a buffer
 Table of Common Ions
Common Positive Ions (Cations)
Monovalent Divalent Trivalent
Hydronium (aqueous) O+
H3 Magnesium Mg2+ Aluminium Al3+
Hydrogen (proton) H+ Calcium Ca2+ Antimony III Sb3+
Lithium Li+ Strontium Sr2+ Bismuth III Bi3+
Sodium Na+ Beryllium Be2+
Potassium K+ Manganese II Mn2+
Rubidium Rb+ Barium Ba2+
Cesium Cs+ Zinc Zn2+
Francium Fr+ Cadmium Cd2+
Silver Ag+ Nickel II Ni2+
Ammonium NH4+ Palladium II Pd2+
Thalium Tl+ Platinum II Pt2+
Copper I Cu+ Copper II Cu2+
Mercury II Hg2+
Mercury I Hg22+
Iron II Fe2+ Iron III Fe3+
Cobalt II Co2+ Cobalt III Co3+
Chromium II Cr2+ Chromium III Cr3+
Lead II Pb2+
Tin II Sn2+
 Table of Common Ions
Common Negative Ions (Anions)
Monovalent Divalent Trivalent
Hydride H- Oxide O2- Nitride N3-
Fluoride Fl- Peroxide O22-
Chloride Cl- Sulfide S2-
Bromide Br- Selenide Se2-
Iodide I- Oxalate C2O42-
Hydroxide OH- Chromate CrO42-
Permangante MnO4- Dichromate Cr2O72-
Cyanide CN- Tungstate WO42-
Thiocynate SCN- Molybdate MoO42-
Acetate CH3COO- Tetrathionate S4O62-
Nitrate NO3- Thiosulfate S2O32-
Bisulfite HSO3- Sulfite SO32-
Bisulfate HSO4- Sulfate SO42-
Bicarbonate HCO3- Carbonate CO32-
Dihydrogen phosphate H2PO4- Hydrogen phosphate HPO42- Phosphate PO43-
Nitrite NO2-
Amide NH2-
Hypochlorite ClO-
Chlorite ClO2-
Chlorate ClO3-
Perchlorate ClO4-
 Acids and bases
• There are three classes of strong electrolytes.
1 Strong Water Soluble Acids
Remember the list of strong acids from Chapter 4.

HNO3( )  H 2O (  )  
 H 3O (aq)
100% 
 NO3(aq)
2 Strong Water Soluble Basesor
The entire list of these bases  introduced
 in Chapter 4.
HNO3( )  H (aq)  NO3(aq)
100% was also

2 O 100% 
KOH(s) H  K (aq)  OH-(aq)
3 Most Water Soluble 2O 
Salts 2
Sr(OH) 2(s) H   Sr(aq)
100%
 2 OH-(aq)
The solubility guidelines from Chapter 4 will help you remember these
salts.
2 O 100% 
NaCl(s) H  Na (aq)  Cl-(aq)
H 2 O 100% 2 
• Weak acids
Ca(NO )      Ca
3 2 s  and bases ionize(aq)  2 NO
or dissociate
3(aq) partially,
much less than 100%, and is often less than 10%.
 Acids and bases
• Most salts of strong or weak electrolytes can dissolve in water to produce a neutral,
basic, or acidic solution, depending on whether it contains the conjugate base of a
weak acid as the anion (A–) or the conjugate acid of a weak base as the cation
(BH+), or possibly both.

• Salts that contain small, highly charged metal ions produce acidic solutions in H2O.

• The most important parameter for predicting the effect of a metal ion on the acidity
of coordinated water molecules is the charge-to-radius ratio of the metal ion.

• The reaction of a salt with water to produce an acidic or basic solution is called a
hydrolysis reaction, which is just an acid-base reaction in which the acid is a
cation or the base is an anion.
 Acids and bases
Acid (HCl) Base (NaOH)
Arrhenius
Brönsted-Lowery
Lewis
Two species that differ by only a proton constitute a conjugate acid-base pair.
1. Conjugate base has one less proton than its acid; A– is the conjugate base of HA
2. Conjugate acid has one more proton than its base; BH+ is the conjugate acid of B
3. Conjugates are weaker than strong parents and stronger than weak parents.
4. All acid-base reactions involve two conjugate acid-base pairs.

• HCl (aq) + H2O (l)  H3O+ (aq) + Cl– (aq)

parent acid parent base conjugate acid conjugate base

Water is amphiprotic: it can act as an acid by donating a proton to a

base to form the hydroxide ion, or as a base by accepting a proton from
an acid to form the hydronium ion, H3O+. Substances that can behave
as both an acid and a base are said to be amphoteric.
Acids and bases can be defined in different ways:
1. Arrhenius definition: An acid is a substance that dissociates in water
to produce H+ ions (protons), and a base is a substance that
dissociates in water to produce OH– ions (hydroxide); an acid-base
reaction involves the reaction of a proton with the hydroxide ion to
form water.
– Three limitations
1. Definition applied only to substances in aqueous solutions.
2. Definition restricted to substances that produce H+ and OH– ions
3. Definition does not explain why some compounds containing
hydrogen such as CH4 dissolve in water and do not give acidic
solutions
2. Brønsted–Lowry definition: An acid is any substance that can
donate a proton, and a base is any substance that can accept a
proton; acid-base reactions involve two conjugate acid-base pairs and
the transfer of a proton from one substance (the acid) to another (the
base). Not restricted to aqueous solutions, expanding to include other
solvent systems and acid-base reactions for gases and solids. Not
restricted to bases that only produce OH– ions . Acids still restricted to
substances that produce H+ ions. Limitation 3 not dealt with.
3. Lewis definition: A Lewis acid is an electron-pair acceptor, and a
Lewis base is an electron-pair donor .
 1. Add solution from the buret.
Titration 2. Reagent (base) reacts with
compound (acid) in solution
in the flask.
3. Indicator shows when exact
stoichiometric reaction has
occurred.
4. Net ionic equation
H+ + OH-  H2O
5. At equivalence point
moles H+ = moles OH-
Titrant
Equivalence Point
Primary Standard
End Point
Secondary Standard
Titration
 pH, a Concentration Scale
pH: a way to express acidity -- the concentration of H+ in solution.

Low pH: high [H+] High pH: low [H+]

Acidic solution pH < 7
Neutral pH = 7
pH = log (1/ [H+]) = - log [H+] Basic solution pH > 7
Acid Formula pH at half
equivalence
point
Acetic CH3COOH 4.7
Nitrous HNO2 3.3
Hydrofluoric HF 3.1
Hypochlorous HClO 7.4
Hydrocyanic HCN 9
 You should know the
strong acids & bases
Everything else is weak.
 It’s all because of
Gibbs Free Energy
No acid stronger than H3O+ and no base
stronger than OH– can exist in aqueous
solution, leading to the phenomenon known
as the leveling effect.

Any species that is a stronger acid than the

conjugate acid of water (H3O+) is leveled to
the strength of H3O+ in aqueous solution
because H3O+ is the strongest acid that can
exist in equilibrium with water.

In aqueous solution, any base stronger than

OH– is leveled to the strength of OH–
because OH– is the strongest base that can
exist in equilibrium with water

http://www.chem1.com/acad/webtext/abcon/abcon-2.html
 Acids and bases
CO2 + H2O H2CO3
Baking Soda NaHCO3 H2CO3 + H2O HCO3- + H+
Soda Pop CO2
HCO3- + H2O CO32- + H+
Atmosphere
.8317 2.5×10−4 5.61×10−11
KH K1 K2
CO2+3H2O H2CO3+2H2O HCO3-+H3O++H2O CO32-+2H3O+

CO2 + CaCO3 + H2O 2HCO3- + Ca2-

Biological Calcification
(not a reversible reaction)
Critter's shells
 use an indicator
use a pH meter to detect the
to detect the

Acid/Base Equilibrium end point

http://www.chem1.com/acad/webtext/abcon/abcon-2.html
 Autoionization of Water
• Because water is amphiprotic, one water molecule can react with another to form an
OH– ion and an H3O+ ion in an autoionization process:
2H2O(l)⇋H3O+ (aq) + OH– (aq)
• Equilibrium constant K for this reaction can be written as
Kc = [H3O+] [OH–]
[H2O]2

 
• 1 L of water contains 55.5 moles of water. In dilute aqueous solutions: H O  55.5M
2
• The water concentration is many orders of magnitude greater than the ion
concentrations. The concentration is essentially that of pure water. Recall that the
activity of pure water is 1.
• When pure liquid water is in equilibrium with hydronium and hydroxide ions at
25ºC, the concentrations of hydronium ion and hydroxide ion are equal:

[H3O+]=[OH–] = 1.0 x 10–7 M [H3O+][OH–] = 1.0 x 10–14 M = Kw

pH = pOH = 7 pH + pOH = pKw = 14
Kc [H2O]2 = Kw = [H3O+][OH–] = 1.0 x 10–14
 Ionization Constants for Weak Acids and Bases
When is a 1M solution not a 1 M solution?
 A 1 M solution is prepared by dissolving 1 mol of acid or base in water
and adding enough water to give a final volume of exactly 1 L.

 If the actual concentrations of all species present in the solution were

listed, it would be determined that none of the values is exactly 1 M
because a weak acid or a weak base always reacts with water to some
extent.

 Only the total concentration of both the ionized and unionized species
is equal to 1 M.

 The analytical concentration (C) is defined as the total concentration of

all forms of an acid or base that are present in solution, regardless of
their state of protonation.

 Thus; a 1 M solution has an analytical concentration of 1 M, which is

the sum of the actual concentrations of unionized acid or base and the
ionized form.
 Ionization Constants for Weak Monoprotic Acids and Bases
• The equation for the ionization of acetic acid is:
CH3COOH(aq)  H 2 O(l)  H 3O   CH3COO- (aq)
• The equilibrium constant for this ionization is expressed as:

• We can define a new equilibrium constant for weak acid equilibrium, Ka, the acid
ionization constant, using this definition.
– The symbol for the ionization constant is Ka.

– The larger the Ka value the stronger the acid and the higher the equilibrium [H+]
– The larger the Kb value the stronger the base and the higher the equilibrium [OH–]
 Acids, Bases, and ionization constants
• Acid and Base strengths can be compared using Ka and Kb values. The larger the Ka or Kb
value the more product favored the dissociation.
• An acid-base equilibrium always favors the side with the weaker acid and base.
stronger acid + stronger base weaker acid + weaker base
• In an acid-base reaction the proton always reacts with the strongest base until totally
consumed before reacting with any weaker bases.
• Any substance whose anion is the conjugate base of a weak acid weaker than OH- reacts
quantitatively with water to form more hydroxide ions.
H2O
Step 1. NaCH3COO → Na+ + CH3COO-
Acetate ion is the conjugate base of acetic acid, a weak acid.
Step 2. CH3COO- + H2O CH3COOH + OH-
• Hydrolysis: Aqueous solutions of salts that dissociate into both:
1. A strong conjugate acid and a strong conjugate base are neutral (KNO3).
2. A strong conjugate acid and a weak conjugate base are acidic (HCl).
3. A strong conjugate base and a weak conjugate acid are basic (NaOH).
4. A weak conjugate base and a weak conjugate acid can be neutral, basic or acidic:
• The comparison of the values of Ka and Kb determine the pH of these solutions.
a. Kbase = Kacid make neutral solutions (NH4CH3OO)
b. Kbase > Kacid make basic solutions (NH4ClO)
c. Kbase < Kacid make acidic solutions (CH3)3NHF
Ionization Constants for Weak Monoprotic Acids and Bases
• The ionization constant values for several acids are given below.
– Which acid is the strongest?
– Are all of these acids weak acids?
– What is the relationship between Ka and strength?
– What is the relationship between pKa and strength?
– What is the relationship between pH and strength?

Acid Formula Ka value pKa value pH of 1M

-log Ka analytical [HA]
Acetic CH3COOH 1.8 x 10-5 4.7 2.4
Nitrous HNO2 4.5 x 10-4 3.3 1.7
Hydrofluoric HF 7.2 x 10-4 3.1 1.6
Hypochlorous HClO 3.5 x 10-8 7.5 3.7
Hydrocyanic HCN 4.0 x 10-10 9.4 4.7
Ionization Constants for Weak Monoprotic Acids and Bases
the MATH
– To determine the ionization constant you need the
analytical concentration of the acid or base, one must be
able to measure the concentration of a least one of the
species in the equilibrium constant expression in order to
determine the value of Ka or Kb.

– Two common ways to obtain the concentrations

1. By measuring the electrical conductivity of the
solution, which is related to the total concentration of
ions present
2. By measuring the pH of the solution, which gives [H+]
or [OH–]
 Ionization Constants for Weak Monoprotic Acids
the MATH
In a 0.12 M solution of a weak monoprotic acid, HY, the acid is 5.0% ionized.
Calculate the ionization constant for the weak acid.

R HY H3O+ + Y-
I
C
E

• Use the concentrations that were just determined in the ionization constant
expression to get the value of Ka.
 Ionization Constants for Weak Monoprotic Acids
the MATH
• The pH of a 0.10 M solution of a weak monoprotic acid, HA, is found to be 2.97.
What is the value for its ionization constant?

• Use the [H3O+] and the stoichiometry R HA H3 O + + A-

of the ionization reaction to determine
concentrations of all species. I
Simplifying Assumption: Is the change C
significant? Later we will find that in
general, if the Ka/[] is < 1x10-3 you E
can apply the simplifying assumption.

• Calculate the ionization constant from this information.

 Ionization Constants for Weak Monoprotic Acids
the MATH
Calculate the concentrations of the various species in 0.15 M acetic acid, CH3COOH,
solution.
1. It is always a good idea to write down the ionization reaction and the ionization
constant expression.

2. Next we combine the basic chemical concepts with some algebra to solve the
problem + -
R CH3COOH H3O + CH3COO
I
C
E
 Ionization Constants for Weak Monoprotic Acids
the MATH
• Substitute these algebraic quantities into the ionization expression.

• Solve the algebraic equation, using a simplifying assumption that is appropriate

for all weak acid and base ionizations.

• Complete the algebra and solve for the concentrations of the species.

• Note that the properly applied simplifying assumption gives the same result as solving the
quadratic equation does.
x
  1.8  10 
 1.8  10  5  5 2

 41  2.7  10  6 
21
x  1.6  10  3 and - 1.6  10- 3
 Ionization Constants for Weak Monoprotic Acids
the MATH
• Calculate the concentrations of the species in 0.15 M hydrocyanic acid, HCN, solution.
Ka= 4.0 x 10-10 for HCN
R HCN H3O+ + CN-
I
C
E

• Substitute these algebraic quantities into the ionization expression.

• Solve the algebraic equation, using the simplifying assumption that is appropriate
for all weak acid and base ionizations.
 Ionization Constants for Weak Monoprotic Acids
• Let’s look at the percent ionization of two previous weak acids as a function
of their ionization constants.

Solution Ka [H+] pH % ionization

0.15 M acetic acid 1.8 x 10-5 1.6 x 10-3 2.80 1.1

0.15 M HCN 4.0 x 10-10 7.7 x 10-6 5.11 0.0051

• Note that the [H+] in 0.15 M acetic acid is more than 200 times greater than for
0.15 M HCN.

[ionized HY]
% ionization = x 100%
[unionized HY]
 Ionization Constants for Weak Monoprotic Bases
the MATH
• All of the calculations and understanding we have at present can be applied to
weak acids and weak bases. Calculate the concentrations of the various species
in 0.15 M aqueous ammonia. Kb = 1.8E-5

R NH3 NH4+ + OH-

I
C
E
 Ionization Constants for Weak Monoprotic Bases
the MATH
• The pH of an aqueous ammonia solution is 11.37. Calculate the molarity (original
concentration) of the aqueous ammonia solution

R NH3 NH4+ + OH-

I
C
E

• Examination of the last equation suggests that our simplifying assumption can be
applied. In other words (x-2.3x10-3)  x.
– Making this assumption simplifies the calculation.
 Polyprotic Acids

• Polyprotic acids contain more than one ionizable proton, and

the protons are lost in a stepwise manner.
• The fully protonated species is always the strongest acid
because it is easier to remove a proton from a neutral molecule
than from a negatively charged ion; the fully deprotonated
species is the strongest base.
• Acid strength decreases with the loss of subsequent protons,
and the pKa increases.
• The strengths of the conjugate acids and bases are related by
pKa + pKb = pKw, and equilibrium favors formation of the
weaker acid-base pair.
 Polyprotic Acids
• Many weak acids contain two or more acidic hydrogens.
– Examples include H3PO4 and H3AsO4.
• The calculation of equilibria for polyprotic acids is done in a
stepwise fashion.
– There is an ionization constant for each step.
• Consider arsenic acid, H3AsO4, which has three ionization
constants.
1 Ka1 = 2.5 x 10-4
2 Ka2 = 5.6 x 10-8
3 Ka3 = 3.0 x 10-13
• Notice that the ionization constants vary in the following fashion:

K a1  K a2  K a3
• This is a general relationship.
– For weak polyprotic acids the Ka1 is always > Ka2, etc.
 Polyprotic Acids
• The first ionization step for arsenic acid is:

• The second ionization step for arsenic acid is:

• The third ionization step for arsenic acid is:

 Polyprotic Acids The MATH
• Calculate the concentration of all species in 0.100 M arsenic acid, H3AsO4,
solution.
1 Write the first ionization step and represent the concentrations.
Approach this problem exactly as previously done.

R H3AsO4 H3O+ + H2AsO4-

I
C
E

The simplifying assumption cannot be used.

Using the quadratic equation x =
 Polyprotic Acids The MATH
2. Next, write the equation for the second step ionization and represent the
concentrations and work as before.

R H2AsO4 - H3O+ + HAsO4-2

I
C
E

The simplifying assumption can be used.

 Polyprotic Acids The MATH
3. Finally, repeat the entire procedure for the third ionization step.

R HAsO4 -2 H3O+ + AsO4-3

I
C
E

The simplifying assumption can be used. 3.0x10-13/5.6x10-8 = 5.4x10-6<1.0x10-3

 Polyprotic Acids
• A comparison of the various species in 0.100 M H3AsO4 solution follows.

Species Concentration
H3AsO4 0.095 M
H+ 4.9 x 10-3 M
H2AsO4- 4.9 x 10-3 M
HAsO42- 5.6 x 10-8 M
AsO43- 3.4 x 10-18 M
OH- 2.0 x 10-12 M

When a strong base is added to a solution of a polyprotic acid, the

neutralization reaction occurs in stages.
1. The most acidic group is titrated first, followed by the next most acidic, and so
forth
2. If the pKa values are separated by at least three pKa units, then the overall
titration curve shows well-resolved “steps” corresponding to the titration of
each proton
Polyprotic Acids
 The Common Ion Effect
• The ionization equilibrium of a weak acid (HA) is affected by
the addition of either the conjugate base of the acid (A–) or a
strong acid (a source of H+); LeChâtelier’s principle is used to
predict the effect on the equilibrium position of the solution
• Common-ion effect—the shift in the position of an
equilibrium on addition of a substance that provides an ion in
common with one of the ions already involved in the
equilibrium; equilibrium is shifted in the direction that reduces
the concentration of the common ion

The Common Ion Effect is important to

1. Buffers
2. Solubility Equilibrium
 The Common Ion Effect and Buffer Solutions
The Derivation of a Powerful Shortcut
• The general expression for the ionization of a weak monoprotic acid is:

• The generalized ionization constant expression for a weak acid is:

• If we solve the expression for [H+], this relationship results:

• By making the assumption that the concentrations of the weak acid and the
salt are reasonable, taking the logarithm of both sides, multiplying both sides
by –1, and replacing the negative logarithms the expression reduces to:
 The Common Ion Effect and Buffer Solutions
• Simple rearrangement of this equation and application of algebra
yields the

Henderson-Hasselbach equation
Buffers are characterized by the following:
1. the pH range over which they can maintain a constant pH—depends strongly on
the chemical properties of the weak acid or base used to prepare the buffer (on K)
2. buffer capacity, is the number of moles of strong acid or strong base needed to
change the pH of 1 Liter of buffer solution by 1 pH unit.
a. depends solely on the concentration of the species in the buffered solution
(the more concentrated the buffer solution, the greater its buffer capacity)
b. A general estimate of the buffer capacity is 40% of the sum of the molarities
of the conjugate acid and conjugate base
3. observed change in the pH of the buffer is inversely proportional to the
concentration of the buffer
 Henderson-Hasselbalch - Caveats and Advantages
• Henderson-Hasselbalch equation is valid for solutions whose
concentrations are at least 100 times greater than the value of
their Ka’s
• The Henderson-Hasselbach equation is one method to calculate the
pH of a buffer given the concentrations of the salt and acid.
• A special case exists for the Henderson-Hasselbalch equation when
[base]/[acid] = some power of 10, regardless of the actual
concentrations of the acid and base, where the Henderson-
Hasselbalch equation can be interpreted without the need for
calculations:
[base]/[acid] = 10x
log 10x = x
in general pH = pKa + x
Examples:
1. when [base] = [acid], [base]/[acid] = 1 or 100, log 1 = 0, pH = pKa,
(corresponds to the midpoint in the titration of a weak acid or base)
2. when [base]/[acid] = 10 or 101, log 10 = 1 then pH = pKa + 1
3. when [base]/[acid] = .001 or 10-2, log 10 = -2 then pH = pKa -2
 Buffer Solutions
There are two common kinds of buffer solutions:

I. Commonly, solutions made from a weak acid plus a soluble ionic salt of the
conjugate base of the weak acid.
II. Less common, solutions made from a weak base plus a soluble ionic salt of
the conjugate acid of the weak base.

Both of the above may also be prepared by starting with a weak acid (or weak
base) and add half as many moles of strong base (acid)
 Buffer Solutions Weak Acids Plus
Salts of Their Conjugate Bases
One example of the type I of buffer system is:
The weak acid - acetic acid CH3COOH CH3COOH H3O+ + CH3COO-
~100%
The soluble ionic salt - sodium acetate NaCH3COO NaCH3COO →Na+ + CH3COO-
• This is an equilibrium problem with a starting concentration for both the
cation and anion. After calculating the concentration of H+ and the pH of a
solution that is 0.15 M in both acetic acid sodium acetate yields:

R CH3COOH H3O+ + CH3COO-

I
C
E
 Buffer Solutions Weak Acids Plus
Salts of Their Conjugate Bases
Alternatively you might have noticed:
0
[base]/[acid] = 1 = 10
log 100 = 0
pH = pKa + 0 = pKa = 4.74
[H+] = Ka = 1.8E-5
Solution [H+] pH
0.15 M CH3COOH 1.6 x 10-3 2.80
0.15 M CH3COOH & 1.8 x 10-5 4.74
0.15 M NaCH3COO buffer

 [H+] is ~90 times greater in pure acetic acid than in buffer solution.
Note that the pH of the buffer equals the pKa of the buffering acid.
Weak Bases plus Salts of Their Conjugate Acids

• We can derive a general relationship for buffer solutions that contain a

weak base soluble and an ionic salt of the conjugate acid of the weak base
similar to the acid buffer relationship.
– The general ionization equation for weak bases is:

Henderson-Hasselbach equation
Buffer Solutions: Weak Bases Plus Salts of Their Conjugate Acids
One example of the type II of buffer system is:
The weak base – ammonia NH3 NH3 NH4 ++ OH -

→ NH
~100%
The soluble ionic salt – ammonium nitrate NH4NO3 NH4NO3 4
++ NO -
3

• This is an equilibrium problem with a starting concentration for both the cation
and anion. After calculating the concentration of OH- and the pOH of the
solution that is 0.15 M in aqueous ammonia, NH3, and 0.30 M in ammonium
nitrate, NH4NO3 yeilds:

R NH3 NH4+ + OH-

I
C
E
Buffer Solutions Weak Bases Plus Salts of Their
Conjugate Acids
• A comparison of the aqueous ammonia concentration to that of the buffer
described above shows the buffering effect.

Solution [OH-] pH
0.15 M NH3 1.6 x 10-3 M 11.20

0.15 M NH3 & 9.0 x 10-6 M 8.95

0.15 M NH4NO3 buffer

 The [OH-] in aqueous ammonia is 180 times greater than in the buffer.
 The pKa of the base is 9.26

How effective is this buffer system?

 Buffering Action
• If 0.020 mole of gaseous HCl is added to 1.00 liter of a buffer solution that is
0.100 M in aqueous ammonia and 0.200 M in ammonium chloride, how much
does the pH change? Assume no volume change due to addition of the HCl.

1 Calculate the pH of the original buffer solution.

NH4NO3 → NH
~100%
4
++ NO -
3

NH3 NH4 ++ OH -

R NH3 NH4+ + OH-

I
C
E

• Substitute the quantities determined in the previous relationship into

the ionization expression for ammonia.
 Buffering Action
2 Next, calculate the concentration of all species after the addition of the
gaseous HCl.
– The HCl will react with some of the ammonia and change the
concentrations of the species.
– This is another limiting reactant problem.
→ H + Cl
~100%
HCl + -

NH3 + H+ NH4 +

R NH3 NH4+ + OH-

I
C
E
 Buffering Action
3 Using the concentrations of the salt and base and the Henderson-
Hassselbach equation, the pH can be calculated.

4 Finally, calculate the change in pH.

 Buffering Action

1. If 0.020 mole of NaOH is added to 1.00 liter of solution that is

0.100 M in aqueous ammonia and 0.200 M in ammonium
chloride, how much does the pH change? Assume no volume
change due to addition of the solid NaOH.

→ Na + OH
~100%
NaOH + -

NH4 + + OH- NH3

R NH3 NH4+ + OH-

I
C
E
 Buffering Action
2. Using the concentrations of the salt and base and the Henderson-
Hassselbach equation, the pH can be calculated.

3. Finally, calculate the change in pH.

 Buffering Action

Original Acid or base New

Original Solution pH
pH added pH

1.00 L of solution 0.020 mol NaOH 9.08 +0.13

containing
8.95
0.100 M NH3 and
0.200 M NH4Cl 0.020 mol HCl 8.81 -0.14

• Notice that the pH changes only slightly in each case.

 Preparation of Buffer Solutions
• Calculate the concentration of H+ and the pH of the solution prepared by
mixing 200 mL of 0.150 M acetic acid and 100 mL of 0.100 M sodium
hydroxide solutions.
• Determine the amounts of acetic acid and sodium hydroxide prior to the
acid-base reaction.
• NaOH and CH3COOH
react in a 1:1 mole ratio.
• After the two solutions
are mixed, Calculate
total volume.
• The concentrations of
the acid and base are:
• Substitution of these
values into the ionization
constant expression (or the
Henderson-Hasselbach
equation) permits
calculation of the pH.
 Preparation of Buffer Solutions
• For biochemical situations, it is sometimes important to prepare a buffer
solution of a given pH. Starting with a solution that is 0.100M in aqueous
ammonia prepare 1.00L of a buffer solution that has a pH of 9.15 using
ammonium chloride as the source of the soluble ionic salt of the conjugate
weak acid.
~100% H2O
NH4Cl NH4 + + Cl- NH3 NH4++ OH-
• The Henderson-Hasselbalch equation is used to determine the ratio of the
conjugate acid base pair

• pOH can be determined from the pH:

• pKb can be looked up in a table:
• [base] concentration is provided:
• Solve for [acid]:

• Does this result make sense?

 Titration Curves
Strong Acid/Strong Base Titration Curves
• These graphs are a plot of pH vs. volume of acid or base added
in a titration.
• As an example, consider the titration of 100.0 mL of 0.100 M
perchloric acid with 0.100 M potassium hydroxide.
– In this case, we plot pH of the mixture vs. mL of KOH
added.
– Note that the reaction is a 1:1 mole ratio.

HClO 4  KOH  KClO4  H2O

 Strong Acid/Strong Base Titration Curves
(An M1V1M2V2 problem)
• Before any KOH is added the pH of the HClO4 solution is 1.00. Remember perchloric
acid is a strong acid that ionizes essentially 100%.

HClO 4  KOH  KClO4  H2O

mL KOH mMol KOH† mMol HClO4 mL soln. Ұ pH
0 0 10* 100 1.00
20 2 8‡ 120 1.18
50 5 5‡ 150 1.48
90 9 1‡ 190 2.28
100 10 0‡ 200 7.00
†mMol KOH = ml KOH∙NaOH M ҰmL soln = mL HClO4 + mL KOH
= 100 mL + total base added
*mMol HClO4 = ml HClO4∙ HClO4 M mMol H+ = mMol HClO4
1:1 mole ratio [H+] = mMol HClO4 / mL soln.
‡mMol HClO4 = ml HClO4- mMol KOH pH = -log[H+]
 Strong Acid/Strong Base
Titration Curves
• We have calculated only a few points on the titration curve. Similar
calculations for remainder of titration show clearly the shape of the titration
curve.
 Weak Acid/Strong Base
Titration Curves
• The pH changes much more gradually around the equivalence point in the
titration of a weak acid or a weak base.

• [H+] of a solution of a weak acid (HA) is not equal to the concentration of the
acid (HA)

• [H+] depends on both its Ka and the analytical concentration of the acid (HA).

• Only a fraction of a weak acid dissociates, so [H+] is less than [HA];

therefore, the pH of a solution of a weak acid is higher than the pH of a
solution of a strong acid of the same concentration.
 Weak Acid/Strong Base Titration Curves
• As an example, consider the titration of 100.0 mL of 0.100 M
acetic acid, CH3 COOH, (a weak acid) with 0.100 M KOH (a
strong base).
– The acid and base react in a 1:1 mole ratio.
• Before the equivalence point is reached, both CH3COOH and
KCH3COO are present in solution forming a buffer.
– The KOH reacts with CH3COOH to form KCH3COO.
• A weak acid plus the salt of a weak acid’s conjugate base form a
buffer.
• Hypothesize how the buffer production will effect the titration
curve.
 Weak Acid/Strong Base Titration Curves
(a RICE problem)
CH3OOH  KOH  KCH3OO  H 2O
1. Determine the pH of the acetic acid solution before the titration is begun.

K 
H O CH COO   1.8x10
 
5 1.8x105 CH3COOH
 


 
3 3
H O
CH3COOH
a
CH3COO
3

2. Solve the algebraic equation for each addition of strong base, using a simplifying
assumption that is appropriate for all weak acid and base ionizations.

• At the equivalence point, the solution is 0.500 M in KCH3COO, the salt of a

strong base and a weak acid which hydrolyzes to give a basic solution.
3. The solution cannot have a pH=7.00 at equivalence point.
– Both processes make the solution basic. Concentrations must now be
calculated using the equation for Kb. Remember that Kw = KaKb and
that pH + pOH = 14
 Weak Acid/Strong Base Titration Curves

mL KOH mMol OH† [CH3COOH] [CH3COO- ] [H3O+] mL soln. Ұ pH

0 0 0.100 1.34E-02 1.34E-02 100 1.87
20 2.0 0.0800 1.67E-02 8.64E-05 120 4.06
50 5.0 0.0500 3.33E-02 2.70E-05 150 4.57
90 9.0 0.0100 4.74E-02 3.80E-06 190 5.42
100 10 5.30E-06 5.00E-02 1.89E-09 200 8.72
110 10 0.000 5.00E-02 2.10E-13 210 12.68

• After the equivalence point is reached, the pH is determined by the excess

KOH just as in the strong acid/strong base example.
 Weak Acid/Strong Base Titration Curves
• We have calculated only a few points on the titration curve. Similar calculations
for remainder of titration show clearly the shape of the titration curve.

Identity of the weak acid or base being titrated strongly affects the shape of the
titration curve.
The shape of titration curves as a function of the pKa or pKb shows that as the acid
or base being titrated becomes weaker (its pKa or pKb becomes larger), the pH
change around the equivalence point decreases significantly.
 Weak Acid/Weak Base
Titration Curves

• Weak Acid/Weak Base Titration curves have very short

vertical sections.
• Visual indicators cannot be used.
• The solution is buffered both before and after the equivalence
point.
• Comparison of the respective Ka and Kb values can be used to
determine the pH of the equivalence points of these titrations.

a. Kbase = Kacid neutral solutions

b. Kbase > Kacid basic solutions
c. Kbase < Kacid acidic solutions
 Acid-Base Indicators
• The point in a titration at which chemically equivalent amounts of acid and
base have reacted is called the equivalence point.
• The point in a titration at which a chemical indicator changes color is called
the end point.
• A symbolic representation of the indicator’s color change at the end point


is:
 
HIn  H  In
Color 1 Color 2
• The equilibrium constant expression for an indicator would be expressed as:
 Acid-Base Indicators
• If the preceding expression is rearranged the range over which the indicator
changes color can be discerned.