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Introduction Analytical Chemistry-

Equilibrium Constants for Chemical
Reactions

What Is Analytical Chemistry?

“Analytical chemistry is what analytical chemists do.”*

The tools and methods necessary for research

 - for traditional areas of chemistry,
 - fostering multidisciplinary research
 - medicinal chemistry, clinical chemistry, toxicology,
 - Forensic chemistry, material science, geochemistry,
and environmental chemistry.

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The Analytical Perspective

Identify and define the problem.

2. Design the experimental procedure.
3. Conduct an experiment, and gather data.
4. Analyze the experimental data.
5. Propose a solution to the problem

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Discussions pertaining to each of the five steps

outlined in Figure 1.3.

1. What is the analytical problem?

2. What type of information is needed to solve the problem?
3. How will the solution to this problem be used?
4. What criteria were considered in designing the
experimental procedure?
5. Were there any potential interferences that had to be
eliminated? If so, how
were they treated?

Discussions pertaining to each of the five steps outlined

in Figure 1.3.

6. Is there a plan for validating the experimental method?

7. How were the samples collected?
8. Is there evidence that steps 2, 3, and 4 of the analytical
approach are repeated more than once?
9. Was there a successful conclusion to the problem?

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Common Analytical Problems

 Qualitative analysis
An analysis in which we determine the
identity of the constituent species in a sample.
 Quantitative analysis
An analysis in which we determine how
much of a constituent species is present
in a samp

Common Analytical Problems

Characterization analysis
An analysis in which we evaluate a
sample’s chemical or physical properties.
Fundamental analysis
An analysis whose purpose is to improve
an analytical method’s capabilities.

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SUMMARY

 Analytical chemists work to improve the ability of all

chemists to make meaningful measurements.
 The need to work with smaller quantities of material,
with more complex materials
 Typical problems on which analytical chemists work

Case study

Read a recent article from the column “Analytical

Approach,” published in Analytical Chemistry, or an
article assigned by your instructor, and write an essay
summarizing the nature of the problem and how it was
solved. As a guide, refer back to Figure 1.3 for one model
of the analytical approach.

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Basic Tools of Analytical Chemistry

SI units: Stands for Système International d’Unités.

These are the internationally agreed on units for
measurements
Scientific notation
A shorthand method for expressing very
large or very small numbers by indicating powers of
ten; for example, 1000 is 1 × 103.

Basic Tools of Analytical Chemistry

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Basic Tools of Analytical Chemistry

Significant figures

The digits in a measured quantity,including all digits

known exactly and one digit (the last) whose quantity is
uncertain.
For example, if we weigh a sample on a balance and
record its mass as 1.2637 g,
the sum of 135.621, 0.33, and 21.2163 is 157.17 since
the last digit that is significant for all three numbers is in
the hundredth’s place.
135.621 + 0.33 + 21.2163 = 157.1673 = 157.17

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Significant figures

To the correct number of significant figures using the

following simple rules.
- Retain the least significant figure if it and the digits
that follow are less than halfway to the next higher
digit 12.442 to the nearest tenth gives 12.4

- Increase the least significant figure by 1 if it and the

digits that follow are more than halfway to the next
higher digit 12.476 to the nearest tenth gives 12.5

- If the least significant figure and the digits that follow

are exactly halfway to the next higher digit:
12.550 to the nearest tenth gives 12.6

Basic Equipment and Instrumentation

Balance An apparatus used to measure mass.

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Basic Equipment and Instrumentation

Balances should be placed on heavy

surfaces to minimize the effect of vibrations
in the surrounding environment and should
be maintained in a level position

Equipment for Measuring Volume

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Equipment for Drying Samples

Commercial laboratory ovens are used a muffle furnace used for heating
when the maximum desired samples to maximum temperatures of
temperature is 160–325 °C 1100–1700 °C.

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(a) Desiccator. (b) Desiccator with stopcock for evacuating the desiccator.

Desiccator: A closed container containing a desiccant; used to

store samples in a moisture-free environment.
Desiccant: A drying agent

Equilibrium Chemistry
Reversible Reactions and Chemical Equilibria
In 1798, the chemist Claude Berthollet (1748–1822)
forming NaCl and a precipitate of CaCO3 as products.

equilibrium
A system is at equilibrium
when the concentrations of
reactants and products remain
constant

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Thermodynamics and Equilibrium Chemistry

 The solutes A, B, C, and D, with stoichiometric

coefficients a, b, c, and d.

 Equilibrium constant: For a reaction at equilibrium, the

equilibrium constant determines the relative concentrations
of products and reactant

Manipulating Equilibrium Constants

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Manipulating Equilibrium Constants

Add together two reactions to obtain a new reaction, the

equilibrium constant for the new reaction is the product of
the equilibrium constants for the original reactions.

Example
 Calculate the equilibrium constant for the
reaction, given the following information

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solution
The overall reaction is given as

If Rxn 3 is reversed, giving

then the overall reaction is

and the overall equilibrium constant is

Equilibrium Constants for Chemical Reactions

 Precipitation Reactions
 Precipitate: An insoluble solid that forms when two or
more soluble reagents are combined.

 the reverse reaction describing the dissolution of the

precipitate is more frequently encountered.

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Equilibrium Constants for Chemical Reactions

 The equilibrium constant for this reaction is called

the solubility product, Ksp,

 Solubility product: The equilibrium constant for a

reaction in which a solid dissociates into its ions
(Ksp).
 Remember: Ksp valid only if PbCl2(s) is present and
in equilibrium with the dissolved Pb2+ and Cl–

Acid—Base Reactions

 Brønsted-Lowry definition, acids are proton donors,

and bases are proton acceptors.

 Strong and Weak Acids

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Acid—Base Reactions

 The equilibrium constant for this reaction is called

an acid dissociation constant, Ka, and is written as

 acid dissociation constant:The equilibrium constant

for a reaction in which an acid donates a proton to
the solvent (Ka).

Acid—Base Reactions

 Polyprotic acids

Phosphoric acid, has

three acid issociation
reactions and acid
dissociation constants

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Strong and Weak Bases

 strong base is an alkali metal hydroxide

 Weak bases only partially accept protons from the

solvent and are characterized by a base dissociation
constant, Kb.

 Base dissociation constant: The equilibrium constant

for a reaction in which a base accepts a proton from
the solvent (Kb)

Strong and Weak Bases

Amphiprotic Species Some species can behave as either an

acid or a base. For example, the following two reactions show
the chemical reactivity of the bicarbonate ion, HCO3–, in
water.

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The pH Scale

 Dissociation of Water Water is an amphiprotic

solvent in that it can serve as an acid or a base.

 which has a value of 1.0000 × 10–14 at a temperature of

24 °C. The value of Kw varies substantially with
temperature. For example, at 20 °C, Kw is 6.809 × 10–15,
but at 30 °C Kw is 1.469 × 10–14. At the standard state
temperature of 25 °C, Kw is 1.008 × 10–14, which is
sufficiently close to 1.00 × 10–14

The pH Scale

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Example

Tabulating Values for Ka and Kb

The equilibrium constant Kw may

also be expressed as the product of
Ka for CH3COOH and Kb for
CH3COO–. Thus, for a weak acid,
HA, and its conjugate weak base, A–

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Example
Calculate the following equilibrium constants
(a) Kb for pyridine, C5H5N
(b) Kb for dihydrogen phosphate, H2PO4

Solution

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Complexation Reactions

 ligand
A Lewis base that binds with a metal ion.
The following reaction between the metal ion Cd2+
and the ligand NH3 is typical of a complexation
reaction
 Metal–ligand complex

 Formation constant: The equilibrium constant for a

reaction in which a metal and a ligand bind to form a
metal–ligand complex (Kf).

 the reaction between Cd2+ and NH3 involves four

successive reactions

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Oxidation—Reduction Reactions

 Oxidation: A loss of electrons.

 Reduction: A gain of electrons.

Oxidation—Reduction Reactions

Nernst equation: An equation relating electrochemical

potential to the concentrations of products and reactants.

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Example
Calculate (a) the standard-state potential, (b) the equilibrium
constant, and (c) the potential when [Ag+] = 0.020 M and
[Cd2+] = 0.050 M, for the following reaction taking place at
25 °C.

Solution
(a) In this reaction Cd is undergoing oxidation, and Ag+ is
undergoing reduction. The standard-state cell potential,
therefore, is

Solution
b) To calculate the equilibrium constant, the values for the
standard-state potential and number of electrons into
equation

Solving for K gives the equilibrium constant as

log K = 40.6558
K = 4.527 × 1040

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Solution
C). The potential when the [Ag+] is 0.020 M and the
[Cd2+] is 0.050 M is calculated using equation

p-function
A function of the form pX, where
pX = -log(X).
the pH of a solution that is 0.10 M H+ is

 and the pH of 5.0 × 10–13 M H+ is

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Example
What is pNa for a solution of 1.76 × 10–3 M Na3PO4?
SOLUTION
Since each mole of Na3PO4 contains three moles of Na+,
the concentration of
Na+ is

Example
What is the [H+] in a solution that has a pH of 5.16?

SOLUTION
The concentration of H+ is

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Preparing Solutions

Stock solution: A solution of known concentration from

which other solutions are prepared.
Dilution: The process of preparing a less
concentrated solution from a more concentrated
solution.

EX: A laboratory procedure calls for 250 mL of an

approximately 0.10 M solution of NH3. Describe how
you would prepare this solution using a stock solution
of concentrated NH3 (14.8 M).

The Laboratory Notebook

The most important tool when working in the lab,

providing a complete record of all the work
should be able to look back at the laboratory notebook
several years from now and reconstruct the experiments
on worked maner
A laboratory notebook is also a legal document that helps
establish patent rights and proof of discovery

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Problem

1. Indicate how many significant figures are in each of

the following numbers.
a. 903 b. 0.903 c. 1.0903
d. 0.0903 e. 0.09030 f. 9.03 × 102
2. Round each of the following to three significant
figures.
a. 0.89377 b. 0.89328 c. 0.89350
d. 0.8997 e. 0.08907
3. A 250.0-mL aqueous solution contains 45.1 µg of a
pesticide. Express the pesticide’s concentration in
weight percent, parts per million, and parts per billion.

The Language of Analytical Chemistry

Analysis: A process that provides chemical or physical

information about the constituents in the sample or the
sample itself
Analytes: The constituents of interest in a sample
Matrix: All other constituents in a sample except
for the analytes
Determination: An analysis of a sample to find the
identity, concentration, or properties of the analyte
Measurement: An experimental determination of an
analyte’s chemical or physical propertie

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Techniques, Methods, Procedures, and Protocols

Technique: A chemical or physical principle that can

be used to analyze a sample.
Method: A means for analyzing a sample for a
specific analyte in a specific matrix.
Procedure: Written directions outlining how to
analyze a sample
Protocol:
A set of written guidelines for analyzing
a sample specified by an agency
signal:
An experimental measurement that is
proportional to the amount of analyte (S).

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Selecting an Analytical Method

A method is the application of a technique to a specific

analyte in a specific matrix : design criteria: accuracy,
precision, sensitivity, selectivity, robustness, ruggedness,
scale of operation, analysis time, availability of
equipment, and cost
Accuracy is a measure of how closely the result of an
experiment agrees with the expected result.

Selecting an Analytical Method

Precision An indication of the reproducibility of a

measurement or result.
Sensitivity A measure of a method’s ability to
distinguish between two samples; reported as the change in
signal per unit change in the amount of analyte (k).

Detection limit A statistical statement about the smallest

amount of analyte that can be determined with confidence
Selectivity A measure of a method’s freedom from
interferences as defined by the method

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Robust: A method that can be applied to analytes

in a wide variety of matrices is considered robust.
Rugged : A method that is insensitive to changes
in experimental conditions is considered rugged.
method blank:
A sample that contains all components
of the matrix except the analyte.
Calibration The process of ensuring that the signal
measured by a piece of equipment or an instrument is
correct
standardization The process of establishing the
relationship between the amount of analtye and a
method’s signal.
Validation The process of verifying that a procedure
yields acceptable results.

The
Importance
of Analytical
Methodology

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