MODULE 5: ACID-BASE EQUILIBRIA Bronsted – Lowry Acids and Bases generalized equation:

At the end of this lecture, you should be able to: HA + B ⇄ A- + HB

1. Understand the basic concepts of acid-base equilibria Acid Base Conjugate Conjugate
2. Interpret pH values through the pKa method base acid
3. Provide solutions through computation for the different
concepts of the pH, pOH, and Henderson-Hasselback
formula Example:
4. Recognize buffers and their significant importance on HCl + H2O ⇄ H3O+ + Cl-
acid base conjugate conjugate
chemical reactions as well as in the body Acid base
5. Establish foundation on the importance of salts on
neutralization reactions and salt hydrolysis. HSO4 - + CO3 2- ⇄ SO42- + HCO3-
acid base conjugate conjugate
base acid
Overview of module:
• Acid – Base Theories
Conjugate: Acid – conjugate base
o Bronsted-Lowry Acid – Base Theory
Base- conjugate acid
o Arrhenius Acid – Base Theory
o Ionization and Dissociation Write the formula for the conjugate pair of
• Chemical Equilibrium Constant the following. Identify the species.
o Chemical Equilibrium constant (Keq)
o Ion-product constant of water (Kw) 1. HClO4 = ClO4- - conjugate base
o Acid ionization/ dissociation constant (Ka) 2. CN- = HCN+ - conjugate acid
o Base ionization/ dissociation constant (Kb) 3. SO42- = HSO4 – conjugate acid
• pH and pOH o what is pH? o what is pOH? 4. H2S = HS – conjugate base
o Integral vs Nonintegral pH values 5. PH4 = PH3 – conjugate base
o pKa method
o pH interpretation
o Acid – Base strength
• Buffers o what are buffers?
o Buffer solution and system Arrhenius Acid-Base Theory
o Buffer solution equilibria Species Definition Product in
o Buffer capacity Water
o Biological buffers Arrhenius Hydrogen-containing Hydrogen ions
• Neutralization and Salt hydrolysis Acid compound (H+)
o Neutralization reaction Arrhenius Hydroxide-containing Hydroxide ions
o Salt hydrolysis Base compound (OH-)
• Henderson-Hasselbach Equation
Arrhenius Acid generalized equation:
ACID-BASE THEORY

HA → H+ + A-
HO2
Species Definition
Bronsted – Lowry Donate a proton* to some other Arrhenius Acid Hydrogen ion Negative ion
ACID substance
* proton/H+ donor Example:
Bronsted – Lowry Accept a proton from some other H2O
HCl → H+ + Cl-
BASE substance Arrhenius Hydrogen Negative
* proton/H+ acceptor Acid ion ion
Conjugate Acid Species formed when a proton is H2O
added to a Bronsted – Lowry base HNO3 → H+ + NO3-
* it is originally the base before Arrhenius Hydrogen Chlorine
accepting the proton from the BL Acid ion ion
acid.
Conjugate Base Species that remains when a Arrhenius Base generalized equation:
proton is removed from a
H 2O
BOH → B+ + OH-
Bronsted – Lowry acid
* it is originally the acid that lost a Arrhenius Base Positive ion Hydroxide ion
proton and gave it to the BL base.
* proton is always the hydrogen ion (H+) (when taking about
Bronsted-Lowry Acid-Base)
 Factors that affect the equilibrium state of a chemical
Example: B OH → B+ + OH-
H 2O
reaction
NaOH → Na+ + OH- • Le Chatelier’s principle – the position of an equilibrium
always shifts in the direction as to relieve a stress that
is applied to the system.
HO • mass-action effect – shift is caused by adding one
LiOH →2 Li+ + OH-
Arrhenius Lithium Hydroxide reactants or products to a system
Base ion ion
The following equilibrium constants are at a condition of 25°C.

Chemical Equilibrium constant (Keq)

• amounts of reactants and products (in mole) at
Ionization and Dissociation
equilibrium for a chemical reaction
Definition Reactant
compound
Ionization Process in which Molecular Keq generalized equation:
individual positive compound
and negative ions * compounds aA + bB ⇄ cC + dD
are produced in a bonded
dissolved solution covalently (nm uppercase A, B, C, and D = molar concentration of species A
(also called partial +nm) and so forth
dissociation) * CH3COOH lowercase a, b, c, and d = coefficients of the species which
Dissociation process in which Ionic compound will then become exponents
individual positive * ionicly bonded
and negative ions (m+ nm) Keq expression:
are released in a * NaCl [𝐶]𝑐 [𝐷]𝑑
𝐾𝑒𝑞 =
dissolved solution [𝐴]𝑎 [𝐵]𝑏
𝑝𝑟𝑜𝑑𝑢𝑐𝑡
Identify the Arrhenius species for each chemical 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
reaction, and state if ionization or dissociation
reaction: • [x] – molar concentration
HO
• Xy – y is exponent
1. HC2O4- →
2
H+ + C2O42- Arrhenius acid - ionization
* In cases where a product is in state of pure solid, pure liquid,
H2O and excess solvent, cancel out that particular product.
2. KOH → K+ + OH- - Arrhenius base - dissociation
Pure liquid = disregard
Pure solids = disregard
3. C4H11NO2 H→
2O
C4H12NO2+ + OH- - Arrhenius base - Spectator ions = disregard (ions present in both sides)
ionization
Example: aA + bB ⇄ cC + dD
dD = H2O(aq) - just cancel out water
Equilibrium-constant
• the relationships among reactants and products which [𝐶]𝑐 [𝐷]𝑑
𝐾𝑒𝑞 =
maintains an equilibrium [𝐴]𝑎 [𝐵]𝑏
• All chemical equilibrium constants have a
predetermined value [𝐶]𝑐
𝐾𝑒𝑞 =
• All chemical equilibrium constants that will be [𝐴]𝑎 [𝐵]𝑏
discussed are reacting at 25°C.
o Hence, a change in temperature will have a different Ion-product constant of water (Kw)
equilibrium-constant value which follows the Le • equilibrium constant of water
Chatelier’s Principle. • self-ionization of water (autoprotolysis)
• The importance of having a knowledge on equilibrium- • spontaneous reaction between molecules of
constant expressions permit the calculation of error water to give a pair of ions (H3O and OH)
in analysis • concentration of hydronium (H3O+) and
• K – equilibrium constant hydroxide ions (OH-)
• at 25°C, this constant is the basis of pH
* Example: Keq = 1.0 x 10-18
• Kw – concentration of H+/H3O+ and OH- ions
X = 1.2 x 10-17 – calculation error
* this is the main basis of the pH
* H2O is amphiprotic: can act as acid and base Acid ionization/ dissociation constant (Ka)
• the equilibrium constant for the ionization/
Kw generalized equation: dissociation of an acid
H2O + H2O ⇄ H3O+ + OH RULE: Conservation • equilibrium constant for the reaction of a weak
acid with water
sometimes it is represented as: of mass
• main species involved (found in the denominator
H2O ⇄ H+ + OH- of the equation): HA or the weak acid
*theoretically, both are correct. However, in the actual Ka expression:
laboratory setting, water is abundant, hence, the former
HA + H2O ⇄ H3O+ + A-
equation (with hydronium ion) is much acceptable.
• water is pure liquid, hence, it is not included in
Kw expression: the Ka expression.
Kw = [H3O+][OH-] = 1.0 x 10-14 [𝐻3 𝑂+ ][𝑂𝐻 − ]
𝐾𝑤 = • HA as weak acid (at the denominator)
[𝐻2 𝑂][𝐻2 𝑂]
Or • A- as conjugate base
Kw = [H+][OH-] = 1.0 x 10-14 𝐾𝑎 =
[𝐻3 𝑂+ ][𝐴− ]
[𝐻𝐴]
this is the reason why the pH is scale is 1 til 14.

hence, Predetermined Kw Example:

constant value at 25°C =
[H+] or [H3O+] = [OH-] 1.0 x 10-14 A 0.0100 M solution of an acid
HA = 15 % ionized = (M=?)
[H+] or [H3O+] = 1.0 x 10-7 This value is the basis of A-=?
OH- = 1.0 x 10-7 the pH, that’s why the H3O+ = ?
pH scale is up to 14.
H3O+ = (0.15) x (0.0100 M) = 0.0015 M
this is the reason why the neutral pH is at 7, meaning, there A- = H3O+ , 1:1 ratio = 0.0015 M
is an equal amount between hydronium and hydroxide ions.
HA = original conc. – ionized conc. =
Calculate the concentration of H+ in a: 0.0100 M – 0.0015 = 0.0085 M
[0.0015][0.0015]
1. solution wherein OH- is 0.010 M 𝐾𝑎 =
[0.0085]
2. solution wherein OH- is 1.8 x 10-9
Ka = 2.6 x 10 -4
Calculate the concentration of OH in a:

1. solution wherein H+ is 2 x 10-6

2. solution is [H+] = [OH-] Base ionization/ dissociation constant (Kb)
• the equilibrium constant for the ionization/
dissociation of a base
Le Chatalier’s principle on the change of temperature • equilibrium constant for the reaction of a weak
base with water
with Kw (H2O + H2O ⇄ H3O+ + OH)
• main species involved (found in the denominator
• stress is applied to the molecules that will of the equation): A- or the conjugate base/ strong
compensate for the actual equilibrium base
• ￪Temperature = shift to the right, the H3O+ and Kb expression:
OH- ions are too excited due to high temp, and will
compensate for the equilibrium B + H2O ⇄ HB+ + OH-
• @100°C, Kw= 49 x 10-14/4.9 x 10-13 • again, water is pure liquid, hence, it is not
o The maximum pH, instead of 14, would included in the Kb expression
increase to 15. • B base (at the denominator)
• ￬Temperature = shift to the left, water molecules [𝑂𝐻 − ]𝐻𝐵 + ]
𝐾𝑏 =
are too slow, and will compensate for the [𝐵 − ]
ionization of H3O+ and OH- ions Percent ionization
• @0°C, Kw = 0.11 x 10-14
• measurement of the strength of a weak acid
• The optimum temperature for the ionization
• ration of the concentration of the ionized acid to
constant of water is at 25°C, with an integral value
the initial acid concentration, times 100
of 1.0, this is the main reason why Kw is the basis
% ionization expression:
for a solution’s pH. [𝐻3 𝑂+ ] 𝑒𝑞
% 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = 𝑥 100%
[𝐻𝐴]0
 pH and pOH Calculate the pH of the given hydronium and
hydroxide ions.
pH concept
• The “p” in pH, pOH, and pKa technically can mean 1. [H3O+] = 1.0 x 10-3
as: power or the power of 10 2. [OH-] = 1.0 x 10-8
• negative logarithm of: 3. [H3O+] = 7.23 x 10-8
o Acids: pH = -log [H+] 4. [H3O+] = 5.70 x 10-3
o Bases: pOH = -log [OH-] 5. [OH-] = 8.92 x 10-6
• hydronium concentration increases/ decreases 10
folds per 1 unit change in pH
o relatively high values up to 10 M and The pKa method
extremely small values of 10-14 M • used for expressing or measurement of the acid
ionization strength
pH scale
• scale of small numbers that is used to specify general equation:
molar hydronium ion concentration in an aqueous
solution pKa = -log [ [𝐻3𝑂 +][𝐴 −] [𝐻𝐴] ]
• the calculation of pH scale values is expressed as: pKa = - log Ka

pH = -log[H3O+] Example:
or
Determine the pKa for the acetic acid, HC2H3O2,
pKa = -logKa given that Ka for this acid is 1.8 x 10-5
pKa = pH
Ka = 1.8 x 10-5
pKa = ?
Integral vs Nonintegral pH values
pKa = -log Ka
Integral pH values
pKa = -log (1.8 x 10-5)
o any hydronium ion concentration expressed in
exponential notation in which the coefficient is pKa = 4.74
1.0
o the pH is given directly to the negative of the exponent
value of the power of 10
o for hydroxide ion concentration, however, subtract the
value to 14 to obtain the pH Interpreting pH values
general equation: 1. The higher the concentration of hydronium ion, the
lower the pH value, and vice versa
[H3O+] =1.0 x 10-x 2. A change of 1 unit in pH always corresponds to a
pH = x tenfold change in hydronium ion concentration
[H+] pH [OH-] pOH
[OH-] = 1.0 x 10-x 100 0 10-14 14
pH = 14 - x
10-1 1 10-13 13
Nonintegral pH values 10-2 2 10-12 12
o if the coefficient in the exponential expression for the 10-3 3 10-11 11
molar hydronium ion concentration is not 1.0
o the pH will not be a whole number 10-4 4 10-10 10
o use the LOG function of an electronic calculator to 10-5 5 10-9 9
obtain the nonintegral pH value 10-6 6 10-8 8
Example: 10-7 7 10-7 7
10-8 8 10-6 6
[H3O+] = 1.0 x 10-11 pH = 11
10-9 9 10-5 5
[OH-] = 1.0 x 10-10 pH = 14-10 = 4
10-10 10 10-4 4
[H3O+] = 6.3 x 10-5 pH = 4.20
[OH-] = 5.3 x 10-5 pH = 14-4.28 = 9.72 10-11 11 10-3 3
10-12 12 10-2 2
10-13 13 10-1 1
10-14 14 100 0
Acid – Base strength Buffer system
• the strength varies in the ability of an acid to transfer 2 active chemical species of Buffers:
protons and produce H3O+ ions in aqueous solution. 1. a substance to react with and remove added base
• The pKa method is one way for expressing the acid 2. a substance to react with and remove added acid
strength of a solution
Buffer system composition:
Type of Solution Relationship of [H+] and [OH-] 1. Weak acid (HA)
Acidic Solution [H+] > [OH-] 2. Conjugate base (A-)
Basic Solution [H+] < [OH-]
pH of Buffer solution
Neutral Solution [H+] = [OH-]
• to calculate the pH of the buffer solution, the Henderson
– Hasselbach equation is to be utilized
Strong vs Weak
- measured through the extent of proton transfer [𝐴− ]
- measured through the strength of ionization/ pH = pKa + log
[𝐻𝐴]
dissociation ability of a solution
Strong Completely or almost Acid: release of Properties of Buffer solution
completely dissociates H3O+ ions
1. Dilution
in water Base: release of
2. Added acids and bases
OH- ions
3. Alpha values (α) – relative equilibrium of conjugate pair
Weak Partially dissociates Acid: produce
with water (ionization) H3O+ ions 4. Buffer capacity (β)
Base: Produce Buffer capacity
OH- ions
• number of moles of a strong acid or strong base that
causes 1.00 L of the buffer to undergo a 1.00-unit
Concentrated vs Diluted
change in pH
- measured through the value of concentration of a
• it is usually determined through titration, in which a
specific solution
- 100% concentrated solution is much stronger than known volume and concentration of a base or acid is
a 50% diluted solution added to the analyte of unknown concentration
•
Commonly encountered strong acids and bases 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻3 𝑂+ 𝑜𝑟 𝑂𝐻 − 𝑎𝑑𝑑𝑒𝑑
𝛽=
(𝑝𝐻 𝑐ℎ𝑎𝑛𝑔𝑒)(𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑢𝑓𝑓𝑒𝑟/𝐿)
Strong Acids Strong Bases
HCl LiOH
HBr NaOH
HI KOH Addition of base (OH-) to the buffer
HNO3 Ca (OH)2 1. Added OH- ion reacts with H3O+ ion, producing H2O
HClO3 Sr (OH)2 → neutralization reaction
HClO4 Ba (OH)2 2. Stress is not enough because the H3O+ ion is
H2SO4 *other members of consumed in the neutralization reaction
Group IA and IIA 3. Shift to the right and will produce more H3O+ ion to
bonded with OH- maintain pH close to original level

Buffers Addition of acid (H3O+) to the buffer

• an aqueous solution containing substances that
prevent major changes in a solution pH when small 1.
amounts of acid/ base are added to it
• maintain a particular or an optimum pH condition 2.
when added to the solution 3.
• plays a very vital role in many chemical and
biochemical systems
Added H3O+ ion increases the overall amount if H3O+
present
Stress is too much H3O+ ions present
Shift to the left and will consume more H3O+ ion to
maintain pH close to original level

Buffer solution Biological buffers

• resist/ prevent changes in pH when it is diluted, or
when acids or bases
• prepared from conjugate acid-base pair
• body regulators that prevent drastic changes in pH
from taking place
• organic substances that maintain a constant pH over a
given range by neutralizing the effects of H+ ions in the
body.
• provide a pH environment conducive to critical
biochemical processes
3 major buffer systems in the body: Strong acid +
1. Bicarbonate buffer (HCO3- / CO3-) Strong base Salt and Water 7
o most important buffer system in blood plasma Strong acid +
o HA: H2CO3 Weak base Acid <7
o A-: HCO3- Weak acid +
o Application of Henderson–Hasselbach equation Strong base Base >7
to detect any problem in homeostasis pH <7 if Ka > Kb
o pKa is 6.1 Weak acid + pH =7 if Ka = Kb
o HA: A- is 20:1 Weak base Depends on Ka/Kb pH >7 if Ka < Kb
o normal pH: 7.4
Salt Hydrolysis
2. Protein buffers
o reaction of a salt with water to produce H3O+ ion or
o most abundant, most powerful buffer system in
OH- or both
whole organism
o amino acids (may contain acid or basic side o Hydrolysis depends on neutralization parentage of
chains) salt
o hemoglobin – most important protein o Not all salts hydrolyze

3. Urine buffers Types of Salt Hydrolysis

o ammonium buffer Salt parentage Nature if Aqueous
o inorganic and organic phosphate buffers sol’n
Strong acid + Neutral
Strong base
Neutralization and Salt Hydrolysis Strong acid + weak Acidic
base
Hydrolysis Neutralization reaction Weak acid + Basic
Strong base
o an acid and a base react to produce salt and water. Weak acid + Weak Depends on the salt
o Salts – ionic compounds consisting of an anion from an base
acid and a cation from a base
o the product is always salt and water
o it is essential to balance the equation Chemical Equations for Salt Hydrolysis Reactions
AB + CD → CB + AD 1. Basic hydrolysis
acid base salt water - reaction of the negative ion from a salt with water
to produce the ion’s conjugate acid and hydroxide
Examples: ion
HCl + NaOH ⇄ NaCl + H2O
B + HA → HB + OH-
HNO3 + Ba(OH)2 ⇄ H2O + Ba(NO3)2
B= base
2HNO3 + Ba(OH)2 ⇄ 2H2O + Ba(NO3)2
HA = acid
H3PO4 + Ca(OH)2 ⇄ H2O + Ca(PO4)2 HB = weak acid/ conjugate acid
2H3PO4 + 3Ca(OH)2 ⇄ 6H2O + Ca(PO4)2 OH- = makes the solution basic

Example:
Write the neutralization reaction between the
following compounds CN- + H2O → HCN + OH-
1. H2SO4 and Sr(OH)2 Cyanide water hydrogen cyanide hydroxide

conjugate acid-base pair: CN- and HCN

2. HCl and Fe(OH)3 makes the solution basic: OH-

3. HBr and NaOH

Acid-Base reactions: 2. Acidic hydrolysis

Acid-Base reactions:

Reactants Product pH
- reaction of the positive ion from a salt with
water to produce the ion’s conjugate base and Example:
hydronium ion.
the bicarbonate/ carbonic acid buffer system
HA + B → A- + H3O+ pK = 6.1
HCO3- = 24
HA = acid H2CO3 = 1.2
B = base [𝐻𝐶𝑂3 − ]
A- = weak base/ conjugate base 𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
[𝐻2 𝐶𝑂3 ]
H3O+= makes solution acidic
[24]
𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
Example: [1.2]

𝑝𝐻 = 6.1 + 1.3
CH3COOH + H2O → H3O+ + CH3COO-
𝑝𝐻 = 7.4
acetic acid water hydronium ions acetate*
pK = 6.1
conjugate acid-base pair: CH3COOH and CH3COO- HCO3- = 29
pCO2 = 80
makes the solution acidic: H3O+

[𝐻𝐶𝑂3 − ]
𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
[𝑃𝐶𝑂2 𝑥 0.03]
Henderson – Hasselbach
[29]
𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
Equation indicates that: [80 𝑥 0.03]
• if there is more A- than HA in a solution, the pH is
[29]
higher than pKa 𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
• if there is more HA than A-, the pH is lower than pKa [2.4]
• the best use of H-H equation is in the H2CO3 - HCO3 𝑝𝐻 = 6.1 + 1.08
blood buffer system
• sometimes, H2CO3 is converted as pCO2 (partial 𝑝𝐻 = 7.18
pressure of carbon dioxide) multiplied by 0.03
general equation: Calculate the pH of the following

[𝐴− ] 1. HCO3- of 32 and H2CO3 of 3.6

− log[𝐻3 𝑂 + ] = −𝑙𝑜𝑔𝐾𝑎 + 𝑙𝑜𝑔
[𝐻𝐴]

hence,
2. HCO3- of 26 and pCO2 of 94
[𝐴− ]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐻𝐴]

Henderson – Hasselbach of bicarbonate-carbonic acid 3. pKa of 4.75, 0.01 CH3COOH, and 100
buffer system CH3COO-
[𝐻𝐶𝑂3 − ]
𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
[𝐻2 𝐶𝑂3 ]

Or

[𝐻𝐶𝑂3 − ]
𝑝𝐻 = 6.1 + 𝑙𝑜𝑔
[𝑃𝐶𝑂2 𝑥 0.03]
ICE Method:
pH = 6.1 (normal pKa of bicarbonate)
• used to correct constants
• if there are changes