INTRODUCTION TO

ANALYTICAL CHEMISTRY

Leslie H. Reynoso
MTY1103 – Analytical Chemistry
FEU-IAS-MT
What is Analytical Chemistry?

Analytical chemistry is a
measurement science consisting of a
set of powerful ideas and methods
that are useful in all fields of science
and medicine.
 1A The Role of Analytical
Chemistry
• Analytical chemistry is applied throughout
industry, medicine, and all the sciences.

• Quantitative analytical measurements also play a

vital role in chemistry, biochemistry, biology,
geology, physics, and the other sciences.

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1A The Role of Analytical Chemistry

Figure 1-1
The relationship
between analytical
chemistry, other
branches of chemistry,
and the other sciences.
The central location of
analytical chemistry in
the diagram signifies
its importance and
the breadth of its
interactions with
many other disciplines.

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 Analysis, Qualitative, Quantitative, &
Standardized Value
• Analysis: detailed examination of elements or something being observed

• Qualitative: measurement of the quality of something; measurement of

what a material is made of

• Quantitative: measurement of the quantity or number of a material

• Standardized value: values already founded; values that can be compared

against from test to test
Qualitative Analysis Quantitative Analysis

Gives the description, content, Measured amount of substances

component, origin of certain chemicals
Describes the nature of a substance Has standard units or standardized
values
Examples: flame tests, precipitation test Exmples volumetric
(volumes/concentration of substances)
or gravimetric (measures
masses/weights of substances)
Qualitative Analysis vs.
Quantitative Analysis
• Qualitative analysis reveals the identity
of the elements and compounds in a
sample.

• Quantitative analysis indicates the

amount of each substance in a sample.

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1B Classifying Quantitative
Analytical Methods
The results of a typical quantitative analysis are
compute from two measurements:
1. The mass or the volume of sample is to be
analyzed.
2. The second is the measurement of some
quantity that is proportional to the amount of
analyte in the sample, such as mass, volume,
intensity of light, or electrical charge.

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1B Classifying Quantitative
Analytical Methods
We classify analytical methods according to
the nature of this final measurement.
1. Gravimetric methods determine the mass of the
analyte or some compound chemically related to it.
2. Volumetric method determines the volume of a
solution containing sufficient reagent to react
completely with the analyte.

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 1B Classifying Quantitative
Analytical Methods (cont.)
3. Electroanalytical methods involve the measurement
of such electrical properties as voltage, current,
resistance, and quantity of electrical charge.
4. Spectroscopic methods are based on measurement of
the interaction between electromagnetic radiation and
analyte atoms or molecules or on the production of
such radiation by analytes.

1-12
Chemical Equilibrium

Leslie H. Reynoso
MTY1103 – Analytical Chemistry
FEU-IAS-MT
Outline
• Electrolytes
• Acids and Bases (and conjugate base-pairs)
• pH, pOH calculations
• Writing Equilibrium Constant Expression
• Chemical Equilibrium
Classifying Solutions of Electrolytes
• Electrolytes - form ions when dissolved in water (or certain other solvents) and
thus produce solutions that conduct electricity.

• Strong electrolytes ionize essentially completely in a solvent, but weak electrolytes

ionize only partially.
Classifying Solutions of Electrolytes
Acids and Bases
Acids and Bases
• According to the Brønsted-Lowry theory, an acid is a proton donor, and
a base is a proton acceptor. For a molecule to behave as an acid, it must
encounter a proton acceptor (or base). Likewise, a molecule that can
accept a proton behaves as a base if it encounters an acid.
• A salt is produced in the reaction of an acid with a base. Examples
include NaCl, Na2SO4, and NaOOCCH3 (sodium acetate).
Conjugate Acids and Bases
• The product formed when an acid gives up a proton is a potential proton
acceptor and is called the conjugate base of the parent acid. Similarly,
every base accepts a proton to produce a conjugate acid.
Amphiprotic Species
• Species that have both acidic and basic properties are amphiprotic. An
example is dihydrogen phosphate ion, H2PO4-, which behaves as a base
in the presence of a proton donor such as H3O+.
• In the presence of a proton acceptor, such as hydroxide ion, however,
H2PO4- behaves as an acid and donates a proton to form the conjugate
base HPO42-.
Autoprotolysis
• Autoprotolysis (also called autoionization) is the spontaneous reaction
of molecules of a substance to give a pair of ions.
• Amphiprotic solvents undergo self-ionization, or autoprotolysis, to
form a pair of ionic species. Autoprotolysis is yet another example of
acid/base behavior, as illustrated by the following equations:
 pH and pOH: Measure of acidity and basicity

• pH (power of Hydrogen)
- concentration of [H+]
-lower pH; more acidic
pH = -log [H+] or pH = -log [H3O+]

• pOH (Hydroxide ion)

- concentration of [OH-]
-higher pOH, more basic
pOH = -log [OH-]
 pH and pOH: Measure of acidity and basicity
• Take note of the following:

[H+] = 10-pH
[OH-] = 10-pOH

pH = -log[H+]
pOH = -log[OH-]

pH + pOH = 14
Examples:
1. If [H+] = 2.3 x 10-4 M, what is the pOH?
Solution: K = [H+][OH-] pOH = -log [OH-]

= -log 4.35 x 10-11

pOH = 10.36

1.0 x 10-14
2.3 x 10-4
4.35 x 10-11
 2. pOH = 2.34; get the pH, [H+] and [OH-]

Solution: pKw = pH + pOH = 14.00

[H+] = ?
pH = 14 – 2.34
pH = -log [H+]
pH = 11.66
antilog [-pH] = [H+]
[OH-] = ? [H+] = antilog (-11.66)
pOH = -log [OH-] [H+] = 2.19 x 10-12
antilog [-pOH] = [OH-]
[OH-] = antilog (-2.34)
[H+] = 4.57 x 10-3
 Determine the [H+], [OH-], pH, and pOH
given the ff:
[H+] [OH-] pH pOH
1. 2.3x10-4
2. 6.3x10-2
3. 10.67
4. 2.34
pH= -log [H+]
pOH = –log [OH-]
[H+]= 10[-pH]
[OH-]= 10[-pOH]
Determine the [H+], [OH-], pH, and pOH
given the ff:
[H+] [OH-] pH pOH
2.3x10-4 4.3x10-11 3.64 10.36

1.6x10-13 6.3x10-2 12.80 1.20

2.1x10-11 4.7x10-4 10.67 3.33

2.2x10-12 4.6x10-3 11.66 2.34

Chemical Equilibrium
• Rates of the forward and reverse reactions are equal and the
concentration of the reactants and product remain constant

• Chemical reactions do not cease at equilibrium. Instead, the amounts of

reactants and products are constant because the rates of the forward and
reverse processes are identical.
Reversible Reactions
Reversible reaction: A reaction that can be made
to go in either direction; products may reform
original reactants

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Equilibrium Constants
Equilibrium constant, K: The product of the concentrations of a
chemical equilibrium divided by the concentrations of reactants, each
raised to the power equal to its coefficient in the balanced chemical
equation.
• For the general reaction:

• The equilibrium constant expression is:

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Equilibrium Constants
Problem: Write the equilibrium constant expression for
this reversible reaction:

Solution: The equilibrium constant expression is:

• Note that no exponents are shown in this equilibrium

constant expression; by convention the exponent “1” is
understood but not written.
Equilibrium Constants
Heterogeneous solutions- phases of reactants and products are
different
Eg. 6Ca(s) + 2NH3(g)  3CaH2(g) + Ca3N2(s)
Homogeneous solutions-phases of reactants and products are
the same
Eg. 2NO(g) + Cl2(g)  2NOCl(g)
Rules in writing equilibrium constant
1. Coefficients in front of elements are written as superscripts
2. For heterogeneous solutions, concentration of pure solids and liquids
are not included; AQUEOUS AND GASES ARE INCLUDED
• 6Ca(s) + 2NH3(g)  3CaH2(g) + Ca3N2(s)
𝐶𝑎𝐻2 3
Keq=
𝑁𝐻3 2

• 2NO(g) + Cl2(g)  2NOCl(g)

𝑁𝑂𝐶𝑙 2
Keq=
𝑁𝑂 2[𝐶𝑙2]
Write the equilibrium expression (K)
 Determining the value of the
equilibrium constant
Problem: When H2 and I2 react at 427°C, the following equilibrium is
reached:

• The equilibrium concentrations are [I2] = 0.42 mol/L, [H2] = 0.025 mol/L,
and [HI] = 0.76 mol/L. Using these values, calculate the value of K.

Solution:

Equilibrium constants are usually written without units. Note that in the
above solution, the units of concentration cancel.
A mixture of H2, S and H2S is held in a closed vessel at 90OC until the
equilibrium is reached.
H2(g) + S(S) ↔ H2S(g)

At equilibrium, the concentration of H2 is 0.40 M and H2S is 0.027 M.

Calculate the equilibrium constant for the given reaction.

[𝐻2𝑆]
𝐾𝑒𝑞 =
[𝐻2]

[0.027𝑀]
𝐾𝑒𝑞 =
[0.40 𝑀]
= 0.068
 H2 + I2 ↔ 2HI
Keq=49

At equilibrium, [I2]= 0.200 M, [HI]=0.050 M

Calculate the concentration of [H2].

𝐻𝐼 2
𝐾=
𝐻2 [𝐼2]

0.0500 𝑀 2
49=
[H2](0.200𝑀)

0.0500 𝑀 2
[H2]=
[49](0.200𝑀)
=2.6 x 10-4 M of H2
Extent of Reaction
• Keq is greater than 1010
Reaction goes to completion; favors product side

• Keq is less than 10-10

No visible reaction; favors the reactant side

• Keq is equal to 1
 equilibrium: reactants=products
Reaction Quotient
• The reaction quotient, Q, is useful in determining if a chemical reaction
is at equilibrium.
• Comparing Q to K determines which direction the reaction shifts in order
to reach equilibrium.
• Describes the reaction at a non-equilibrium state.
Reaction Quotient
• When Q = K then our chemical reaction is at equilibrium and no
shifting will occur.
Reaction Quotient
• If Q is larger than K then the • If Q is smaller than K then the
reaction will shift in reaction will shift in
the reverse direction to attain the forward direction to attain
equilibrium. equilibrium.
Reaction Quotient
• Example #1: Consider the hypothetical reaction below
3 A (g) + B (g) ↔ 2 C (g) Kc = 1.5 x 10-3

Which of the following statements is correct if the initial concentrations are [A]
= 0.85 M, [B] = 0.36 M, and [C] = 0.005 M.

A. At equilibrium, the amount of C will increase.

B. At equilibrium, the amount of A will increase.
C. At equilibrium, the amount of B will increase and C will increase.
D. At equilibrium, the amount of A will increase and B will decrease.
E. The reaction is at equilibrium.
Reaction Quotient
• Example #2: For the reaction: 2CO2(g) ↔ 2CO(g) + 2O2(g), the equilibrium
constant is 7.22 x 10-4 at 400 K, while the reaction quotient is 6.63 x 10-2. If
initially we have 0.20 atm CO2, 0.30 atm CO and 0.15 atm O2, which of the
following statements is not true?

a) The pressure of CO2 will be greater than 0.20 atm.

b) The pressure of CO will be less than 0.30 atm.
c) The pressure of O2 will be greater than 0.15 atm.
d) The pressure of O2 will be less than 0.15 atm.
e) The reaction will favor reactants.
Le Chatelier’s Principle
• discusses the shifting pattern of a chemical reaction in order to maintain an
equilibrium state.

Chemical Thermodynamics:

1. Addition/Removal of Reactants or Products

2. Increasing or decreasing of pressure or volume
3. Increasing or decreasing temperature
4. Addition or removal of noble gas
5. Liquids, Solids and Catalyst
Le Chatelier’s Principle
• Concept #1: The addition or removal of products or reactants causes the chemical
reaction to shift in the direction necessary to re-establish equilibrium.

• Concept #2: Increasing or decreasing pressure or volume causes the reaction to

shift in the direction necessary to re-establish equilibrium.
Le Chatelier’s Principle
• Concept #3: Increasing or decreasing temperature causes the reaction to shift in
the direction necessary to re-establish equilibrium.
Le Chatelier’s Principle
• Concept #4: Depending on the conditions, the addition or removal of a noble gas
can potentially cause the reaction to shift in the direction necessary to re-establish
equilibrium.
Ka and Kb of Compounds
• The acid dissociation constant, Ka, and the base dissociation constant, Kb,
determine the strengths of weak acids and weak bases respectively.

• Ka examines the strength of a weak acid while Kb examines the strength of a weak
base.
Ka and Kb of Compounds
Example #1: Which of the following compounds has the strongest conjugate acid?

a) C2H5NH2 (Kb = 5.6 x 10-4)

b) H2NNH2 (Kb = 1.3 x 10-6)
c) NH3 (Kb = 1.75 x 10-5)
d) HONH2 (Kb = 1.1 x 10-8)

Example #4: At 0 oC, the ion product constant of water is 1.2x10–15. The pH of pure
water at this temperature is:
a) 6.88
b) 7.00
c) 7.46
d) 7.56