MTChem3: Analytical Chemistry for MLS

A.Y.: 2020-2021
WEEK 4:
ACID – BASE EQUILIBRIA Bronsted – Lowry Acids and Bases generalized
equation:
At the end of this lecture, you should be able to:
1. Understand the basic concepts of acid-base
equilibria HA +B ⇄ A- + HB
Acid Base Conjugate base Conjugate acid
2. Interpret pH values through the pKa method
3. Provide solutions through computation for the
different concepts of the pH, pOH, and Example:
Henderson-Hasselback formula
4. Recognize buffers and their significant HCl + H2O ⇄ H3O+ + Cl-
acid base conjugate acid conjugate base
importance on chemical reactions as well as in
the body HSO4- + CO32- ⇄ SO42- + HCO3-
5. Establish foundation on the importance of salts acid base conjugate base conjugate acid
on neutralization reactions and salt hydrolysis.

Overview of module:
• Acid – Base Theories Write the formula for the conjugate pair
o Bronsted-Lowry Acid – Base Theory of the following. Identify the species.
o Arrhenius Acid – Base Theory
o Ionization and Dissociation 1. HClO4 = __________________________
• Chemical Equilibrium Constant 2. CN- = __________________________
o Chemical Equilibrium constant (Keq) 3. SO42- = __________________________
o Ion-product constant of water (Kw) 4. H2S = __________________________
o Acid ionization/ dissociation constant 5. PH4 = __________________________
(Ka)
o Base ionization/ dissociation constant
(Kb)
• pH and pOH Arrhenius Acid-Base Theory
o what is pH?
o what is pOH? Species Definition Product in Water
o Integral vs Nonintegral pH values Arrhenius Hydrogen- Hydrogen ions (H+)
o pKa method Acid containing
o pH interpretation compound
o Acid – Base strength Arrhenius Hydroxide- Hydroxide ions (OH-)
Base containing
• Buffers
compound
o what are buffers?
o Buffer solution and system
o Buffer solution equilibria
Arrhenius Acid generalized equation:
o Buffer capacity
o Biological buffers
HA H+ + A-
H O
2
• Neutralization and Salt hydrolysis Arrhenius acid Hydrogen ion Negative ion
o Neutralization reaction
o Salt hydrolysis
Example:
• Henderson-Hasselbach Equation
HCl H O
2 H+ + Cl-
Acid – Base theories Arrhenius acid Hydrogen ion Chlorine ion

Bronsted – Lowry Acid Base Theory HNO3 H O H+ + NO3-

2
Arrhenius acid Hydrogen ion Nitrate ion
Species definition
Bronsted – Lowry Acid Donate a proton* to some
other substance
Arrhenius Base generalized equation:
Bronsted – Lowry Base Accept a proton from some
other substance
BOH B+ + OH-
H O
2
Conjugate Acid Species formed when a Arrhenius base Positive ion Hydroxide ion
proton is added to a
Bronsted – Lowry base Example:
Conjugate Base Species that remains when a
proton is removed from a
NaOH H O
2 Na+ + OH-
Bronsted – Lowry acid Arrhenius base Sodium ion Hydroxide ion

*proton is always the H+ ion

LiOH H O
2 Li+ + OH-
Arrhenius base Lithium ion Hydroxide ion

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 MTChem3: Analytical Chemistry for MLS
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Ionization and Dissociation Keq generalized equation:

definition Reactant
aA + bB ⇄ cC + dD
compound
Ionization Process in which Molecular
individual compound uppercase A, B, C, and D = molar concentration of
positive and species A and so forth
negative ions are lowercase a, b, c, and d = coefficients of the species
produced in a which will then become exponents
dissolved solution
Dissociation process in which Ionic compound Keq expression:
individual [C]c [D]d
K eq =
positive and [A]a [B]b
negative ions are
released in a Ion-product constant of water (Kw)
dissolved solution • equilibrium constant of water
• self-ionization of water (autoprotolysis)
• spontaneous reaction between molecules of
Identify the Arrhenius species for each water to give a pair of ions
chemical reaction, and state if ionization • concentration of hydronium (H3O+) and
or dissociation reaction: hydroxide ions (OH-)
• at 25°C, this constant is the basis of pH
1. HC2O4- H2O H+ + C2O42-
____________________
____________________ Kw generalized equation:

2. KOH K+ + OH- H2O + H2O ⇄ H3O+ + OH-

H O
2
____________________
sometimes it is represented as:
____________________
H2O ⇄ H+ + OH-
3. C4H11NO2 H O
2 C4H12NO2+ + OH-
____________________
*theoretically, both are correct. However, in the actual
____________________
laboratory setting, water is abundant, hence, the
former equation (with hydronium ion) is much
acceptable.
Chemical Equilibrium Constant
Kw expression:
Equilibrium-constant
Kw = [H3O+][OH-] = 1.0 x 10-14
• the relationships among reactants and products or
which maintains an equilibrium Kw = [H+][OH-] = 1.0 x 10-14
• All chemical equilibrium constants have a
predetermined value this is the reason why the pH is scale is 1 til 14.
• The importance of having a knowledge on
equilibrium-constant expressions permit the hence,
calculation of error in analysis
• K – equilibrium constant H+ or H3O+ = OH-

Factors that affect the equilibrium state of a chemical H+ or H3O+ = 1.0 x 10-7
reaction OH- = 1.0 x 10-7
• Le Chatalier’s principle – the position of an
equilibrium always shifts in the direction as to this is the reason why the neutral pH is at 7, meaning,
relieve a stress that is applied to the system. there is an equal amount between hydronium and
• mass-action effect – shift is caused by adding one hydroxide ions.
reactants or products to a system
Calculate the concentration of H+ in a:

The following equilibrium constants are at a condition 1. solution wherein OH- is 0.010 M
of 25°C. 2. solution wherein OH- is 1.8 x 10-9

Chemical Equilibrium constant (Keq) Calculate the concentration of OH- in a:

• amounts of reactants and products (in mole)
at equilibrium for a chemical reaction 1. solution wherein H+ is 2 x 10-6
2. solution is [H+] = [OH-]
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 MTChem3: Analytical Chemistry for MLS
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Le Chatalier’s principle on the change of temperature Base ionization/ dissociation constant (Kb)
with Kw • the equilibrium constant for the ionization/
• stress is applied to the molecules that will dissociation of a base
compensate for the actual equilibrium • equilibrium constant for the reaction of a
• ￪Temperature = shift to the right, the H3O+ weak base with water
• main species involved (found in the
and OH- ions are too excited due to high temp,
denominator of the equation): A- or the
and will compensate for the equilibrium
conjugate base/ strong base
• @100°C, Kw= 49 x 10-14
• ￬Temperature = shift to the left, water Kb expression:
molecules are too slow, and will compensate
for the ionization of H3O+ and OH- ions B + H2O ⇄ HB+ + OH-
• @0°C, Kw = 0.11 x 10-14
• The optimum temperature for the ionization • again, water is pure liquid, hence, it is not
included in the Kb expression
constant of water is at 25°C, with an integral
• B base (at the denominator)
value of 1.0, this is the main reason why Kw is
the basis for a solution’s pH.
[𝑂𝐻 − ][𝐻𝐵 + ]
Acid ionization/ dissociation constant (Ka) 𝐾𝑏 =
[𝐵]
• the equilibrium constant for the ionization/
dissociation of an acid
• equilibrium constant for the reaction of a
weak acid with water Percent ionization
• main species involved (found in the • measurement of the strength of a weak acid
denominator of the equation): HA or the weak
• ration of the concentration of the ionized acid
acid
to the initial acid concentration, times 100
Ka expression:
% ionization expression:

HA + H2O ⇄ H3O+ + A-
• water is pure liquid, hence, it is not included
[𝐻3 𝑂 + ]𝑒𝑞
in the Ka expression. 0⁄ 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = × 100%
0 [𝐻𝐴]0
• HA as weak acid (at the denominator)
• A- as conjugate base
pH and pOH
[𝐻3 𝑂+ ][𝐴− ]
𝐾𝑎 =
[𝐻𝐴] pH concept
• The “p” in pH, pOH, and pKa technically can
Example: mean as: power or the power of 10
• negative logarithm of:
A 0.0100 M solution of an acid o Acids: pH = -log [H+]
HA = 15 % ionized = (M=?) o Bases: pOH = -log [OH-]
A- = ? • hydronium concentration increases/
H3O+ = ? decreases 10 folds per 1 unit change in pH
o relatively high values up to 10 M and
H3O+ = (0.15) x (0.0100 M) = 0.0015 M extremely small values of 10-14 M
A- = H3O+ , 1:1 ratio = 0.0015 M
HA = original conc. – ionized conc. pH scale
= 0.0100 M – 0.0015 = 0.0085 M • scale of small numbers that is used to specify
molar hydronium ion concentration in an
aqueous solution
[0.0015][0.0015] • the calculation of pH scale values is expressed
𝐾𝑎 =
[0.0085] as:

Ka = 2.6 x 10 -4 pH = -log[H3O+]

or

pKa = -logKa
pKa = pH

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 MTChem3: Analytical Chemistry for MLS
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Integral vs Nonintegral pH values Example:
Determine the pKa for the acetic acid,
Integral pH values HC2H3O2, given that Ka for this acid is 1.8 x 10-5
o any hydronium ion concentration expressed in
exponential notation in which the coefficient is Ka = 1.8 x 10-5
1.0 pKa = ?
o the pH is given directly to the negative of the
exponent value of the power of 10 pKa = - log Ka
o for hydroxide ion concentration, however,
subtract the value to 14 to obtain the pH pKa = - log (1.8 x 10-5)

general equation: pKa = 4.74

[H3O+] =1.0 x 10-x

pH = x Interpreting pH values
1. The higher the concentration of hydronium ion,
[OH-] = 1.0 x 10-x the lower the pH value, and vice versa
pH = 14 - x 2. A change of 1 unit in pH always corresponds to
a tenfold change in hydronium ion
concentration
Nonintegral pH values
o if the coefficient in the exponential expression for [H+] pH [OH-] pOH
the molar hydronium ion concentration is not 1.0 100 0 10-14 14
o the pH will not be a whole number 10-1 1 10-13 13
o use the LOG function of an electronic calculator to 10-2 2 10-12 12
obtain the nonintegral pH value
10-3 3 10-11 11
Example: 10-4 4 10-10 10
10-5 5 10-9 9
[H3O+] = 1.0 x 10-11 pH = 11 10-6 6 10-8 8
[OH-] = 1.0 x 10-10 pH = 14-10 = 4 10-7 7 10-7 7
[H3O+] = 6.3 x 10-5 pH = 4.20 10-8 8 10-6 6
[OH-] = 5.3 x 10-5 pH = 14-4.28 = 9.72 10-9 9 10-5 5
10-10 10 10-4 4
10-11 11 10-3 3
10-12 12 10-2 2
Calculate the pH of the given hydronium 10-13 13 10-1 1
and hydroxide ions. 10-14 14 100 0

1. [H3O+] = 1.0 x 10-3 Acid – Base strength

• the strength varies in the ability of an acid to
2. [OH-] = 1.0 x 10-8 transfer protons and produce H3O+ ions in
aqueous solution.
3. [H3O+] = 7.23 x 10-8 • The pKa method is one way for expressing the
acid strength of a solution
4. [H3O+] = 5.70 x 10-3

5. [OH-] = 8.92 x 10-6 Type of Relationship of [H+] and

Solution [OH-]
Acidic [H+] > [OH-]
Solution
The pKa method Basic [H+] < [OH-]
• used for expressing or measurement of the acid Solution
ionization strength
Neutral [H+] = [OH-]
general equation: Solution

[𝐻3 𝑂+ ][𝐴− ]
pKa = -log [ [𝐻𝐴]
]

pKa = - log Ka

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 MTChem3: Analytical Chemistry for MLS
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Strong vs Weak Buffer system composition:
- measured through the extent of proton
transfer 1. Weak acid (HA)
- measured through the strength of ionization/ 2. Conjugate base (A-)
dissociation ability of a solution

Completely Acid: release of pH of Buffer solution

or almost H3O+ ions
Strong completely • to calculate the pH of the buffer solution, the
dissociates Base: release of OH-
Henderson – Hasselbach equation is to be utilized
in water ions

Partially Acid: produce H3O+

ions [𝑨− ]
dissociates 𝒑𝑯 = 𝒑𝑲𝒂 + 𝐥𝐨𝐠
Weak [𝑯𝑨]
with water Base: Produce OH-
(ionization) ions
Properties of Buffer solution

Concentrated vs Diluted 1. Dilution

- measured through the value of concentration 2. Added acids and bases
of a specific solution 3. Alpha values (α) – relative equilibrium of
- 100% concentrated solution is much stronger conjugate pair
than a 50% diluted solution 4. Buffer capacity (β)
Commonly encountered strong acids and bases

Strong Acids Strong Bases Buffer capacity

HCl LiOH
• number of moles of a strong acid or strong base
HBr NaOH
that causes 1.00 L of the buffer to undergo a 1.00-
HI KOH
HNO3 Ca (OH)2 unit change in pH
HClO3 Sr (OH)2 • it is usually determined through titration, in which
HClO4 Ba (OH)2 a known volume and concentration of a base or
H2SO4 *other members of acid is added to the analyte of unknown
Group IA and IIA concentration
bonded with OH-
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻3𝑂+𝑜𝑟 𝑂𝐻−𝑎𝑑𝑑𝑒𝑑
𝛽=
(𝑝𝐻 𝑐ℎ𝑎𝑛𝑔𝑒)(𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓𝑏𝑢𝑓𝑓𝑒𝑟/𝐿)

Buffers
• an aqueous solution containing substances that Addition of base (OH-) to the buffer
prevent major changes in a solution pH when
small amounts of acid/ base are added to it 1. Added OH- ion reacts with H3O+ ion, producing
• maintain a particular or an optimum pH H2O → neutralization reaction
condition when added to the solution 2. Stress is not enough because the H 3O+ ion is
• plays a very vital role in many chemical and consumed in the neutralization reaction
biochemical systems 3. Shift to the right and will produce more H3O+
ion to maintain pH close to original level
Buffer solution
Addition of acid (H3O+) to the buffer
• resist/ prevent changes in pH when it is diluted,
or when acids or bases 1. Added H3O+ ion increases the overall amount
• prepared from conjugate acid-base pair if H3O+ present
Buffer system 2. Stress is too much H3O+ ions present
3. Shift to the left and will consume more H3O+
2 active chemical species of Buffers: ion to maintain pH close to original level
1. a substance to react with and remove added base
2. a substance to react with and remove added acid

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 MTChem3: Analytical Chemistry for MLS
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Biological buffers
Write the neutralization reaction
• body regulators that prevent drastic changes in pH between the following compounds
from taking place
• organic substances that maintain a constant pH 1. H2SO4 and Sr(OH)2
over a given range by neutralizing the effects of H+
ions in the body. 2. HCl and Fe(OH)3
• provide a pH environment conducive to critical
biochemical processes 3. HBr and NaOH

3 major buffer systems in the body: Acid-Base reactions:

1. Bicarbonate buffer (HCO3- / CO3-) Reactants Product pH

o most important buffer system in blood Strong acid + Salt and Water 7
plasma Strong base
o HA: H2CO3 Strong acid + Acid <7
o A-: HCO3- Weak base
o Application of Henderson–Hasselbach Weak acid + Base >7
Strong base
equation to detect any problem in
Weak acid + Depends on Ka/Kb pH <7 if Ka > Kb
homeostasis
Weak base pH =7 if Ka = Kb
o pK is 6.1
pH >7 if Ka < Kb
o HA: A- is 20:1
o normal pH: 7.4
Salt Hydrolysis
2. Protein buffers
o reaction of a salt with water to produce H 3O+ ion
o most abundant, most powerful buffer
or OH- or both
system in whole organism
o Hydrolysis depends on neutralization parentage
o amino acids (may contain acid or basic
of salt
side chains)
o Not all salts hydrolyze
o hemoglobin – most important protein
o
3. Urine buffers Types of Salt Hydrolysis
o ammonium buffer
o inorganic and organic phosphate Salt parentage Nature if Aqueous sol’n
buffers

Neutralization and Salt Hydrolysis Strong acid + Strong base Neutral

Neutralization reaction
Strong acid + weak base Acidic
o an acid and a base react to produce salt and water.
o Salts – ionic compounds consisting of an anion Weak acid + Strong base Basic
from an acid and a cation from a base
o the product is always salt and water Weak acid + Weak base Depends on the salt
o it is essential to balance the equation

AB + CD → CB + AD
Chemical Equations for Salt Hydrolysis Reactions
acid base salt water
1. Basic hydrolysis
Examples:
- reaction of the negative ion from a salt
with water to produce the ion’s
HCl + NaOH ⇄ NaCl + H2O
conjugate acid and hydroxide ion
B + HA → HB + OH-
HNO3 + Ba(OH)2 ⇄ H2O + Ba(NO3)2

2HNO3 + Ba(OH)2 ⇄ 2H2O + Ba(NO3)2 B= base

HA = acid

HB = weak acid/ conjugate acid

H3PO4 + Ca(OH)2 ⇄ H2O + Ca(PO4)2 OH- = makes the solution basic

2H3PO4 + 3Ca(OH)2 ⇄ 6H2O + Ca(PO4)2

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 MTChem3: Analytical Chemistry for MLS
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Example: Example:

the bicarbonate/ carbonic acid buffer system

CN- + H2O → HCN + OH-
cyanide water hydrogen cyanide hydroxide pK = 6.1

conjugate acid-base pair: CN- and HCN HCO3- = 24

makes the solution basic: OH- H2CO3 = 1.2

2. Acidic hydrolysis [𝑯𝑪𝑶𝟑− ]

𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠
- reaction of the positive ion from a salt [𝑯𝟐𝑪𝑶𝟑]
with water to produce the ion’s
[𝟐𝟒]
conjugate base and hydronium ion. 𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠
[𝟏. 𝟐]
HA + B → A- + H 3 O+ 𝒑𝑯 = 𝟔. 𝟏 + 𝟏. 𝟑
𝒑𝑯 = 𝟕. 𝟒
HA = acid
B = base
A- = weak base/ conjugate base pK = 6.1
H3O+= makes solution acidic
HCO3- = 29
Example:
pCO2 = 80
CH3COOH + H2O → H3O+ + CH3COO- [𝑯𝑪𝑶𝟑− ]
𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠
acetic acid water hydronium ions acetate* [𝑷𝑪𝑶𝟐 𝒙 𝟎. 𝟎𝟑]
conjugate acid-base pair: CH3COOH and CH3COO- [𝟐𝟗]
𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠
makes the solution acidic: H3O+ [𝟖𝟎 𝒙 𝟎. 𝟎𝟑]
[𝟐𝟗]
Henderson – Hasselbach Equation 𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠
[𝟐. 𝟒]
indicates that: 𝒑𝑯 = 𝟔. 𝟏 + 𝟏. 𝟎𝟖
• if there is more A- than HA in a solution, the 𝒑𝑯 = 𝟕. 𝟏𝟖
pH is higher than pKa
• if there is more HA than A-, the pH is lower
than pKa Calculate the pH of the following:
• the best use of H-H equation is in the H 2CO3 -
HCO3 blood buffer system 1. HCO3- of 32 and H2CO3 of 3.6
• sometimes, H2CO3 is converted as pCO2
(partial pressure of carbon dioxide) multiplied
by 0.03 2. HCO3- of 26 and pCO2 of 94

general equation:
[𝑨− ] 3. pKa of 4.75, 0.01 CH3COOH, and 100
−𝒍𝒐𝒈[𝑯𝟑𝑶 +] = −𝒍𝒐𝒈𝑲𝒂 + 𝐥𝐨𝐠 CH3COO-
[𝑯𝑨]

hence,
[𝑨− ] -----End of Week 4-----
𝒑𝑯 = 𝒑𝑲𝒂 + 𝐥𝐨𝐠
[𝑯𝑨] REFERENCES
Henderson – Hasselbach of bicarbonate-carbonic • Skoog, Douglas A. et. al Analytical Chemistry An
acid buffer system Introduction. Brooks/Cole, Cengage Learning.
[𝑯𝑪𝑶𝟑− ] 2000
𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠 • Stoker, Stephen H. General, Organic and
[𝑯𝟐𝑪𝑶𝟑]
Biological Chemistry. Cengage Learning. 2016
OR • Bettelheim, Frederick A. et. al Introduction to
General, Organic and Biochemistry. Thomson
[𝑯𝑪𝑶𝟑− ] Brooks/Cole. 2007
𝒑𝑯 = 𝟔. 𝟏 + 𝐥𝐨𝐠
[𝑷𝑪𝑶𝟐 𝒙 𝟎. 𝟎𝟑] • Brown, LeMay, and Bursten Chemistry: The
Central Science. 9th ed., Pearson, 2004
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