Chemistry 28

Quantitative Inorganic Analysis

 Course Description
• This course is designed to give students an
understanding of the principles and practice
of common analytical techniques and data
analysis.
 Course Objectives
At the end of this course, the students should
be able to:
• Demonstrate ability to select the appropriate
instruments and laboratory apparatus to perform
measurements of physical and chemical properties
of substances
• Recognize the concepts of stoichiometry: moles,
concentrations, dilution, and aliquot; and apply
these to solving problems in quantitative analysis.
 Course Objectives
• Apply the concepts of equilibrium constant, ionic
equilibria, activity, and activity coefficient in solving
problems in quantitative analyses in acid-base equilibria,
solubility equilibria, complex ion equilibria, and redox
equilibria
• Solve problems applying concepts of volumetric analyses
in acid-base, precipitation, complexometric, and redox
titrations
• Demonstrate an understanding of the concepts of solubility
products and factors affecting solubility
• Demonstrate an understanding of UV-visible spectroscopy
 Course Outline and Timeframe
DATE Topic
21 Jan INTRODUCTION
 Importance of Analytical Chemistry
 Role of Analytical Chemistry in the Sciences
 Classification of Quantitative Methods of Analysis
 Steps in the Typical Quantitative Analysis

25 Jan ERRORS IN CHEMICAL ANALYSIS, STATISTICAL EVALUATION OF ANALYTICAL DATA

 Definition of Terms
 Types of Errors in Experimental Data
1 Determinate Errors
2 Indeterminate Errors
3. Gross Errors
 Methods of Reporting Analytical Data
 The Statistical Treatment of Indeterminate Errors (Laboratory Part)
 Detection of Error
28 Jan REVIEW OF CALCULATIONS IN ANALYTICAL CHEMISTRY
01 Feb
04 Feb CHEMICAL EQUILIBRIUM
15 Feb  The Equilibrium State
 Equilibrium-Constant Expressions
 Types of Equilibrium Constants Encountered in Analytical Chemistry
29 Feb FIRST LONG EXAM
 Course Outline and Timeframe
DATE Topic
03 Mar GRAVIMETRIC METHODS OF ANALYSIS
07 Mar  Calculation of Results from Gravimetric Data/Stoichoimetry
10 Mar  Properties of Precipitates
 A Critique of the Gravimetric Method
 Application of Gravimetric Method
14 Mar TITRIMETRIC METHODS OF ANALYSIS
17 Mar  General Aspects of Volumetric Titrimetry
 Standard Solution
 Volumetric Calculations
 Weight Titrimetry
21 Mar ACID-BASE TITRATIONS
28 Mar  Acid-Base Equilibrium
 Titration Curves
 Acid-Base Indicators
31 Mar
SECOND LONG EXAM
 Course Outline and Timeframe
DATE Topic
04 Apr APPLICATIONS OF ACID-BASE TITRATIONS
07 Apr  Standardization
 Kjeldahl
 Carbonate mixture
11 Apr PRECIPITATION TITRATIONS
14 Apr  Solubility Equilibria
18 Apr  Factors Affecting Solubility
 Titration Curves
 Indicators of Precipitation Titrations
 Application/Computations
21 Apr COMPLEX FORMATION TITRATIONS
25 Apr  Types of Indicator Action Used
 Titration Curves
 EDTA Titration
 Calculations
28 Apr
THIRD LONG EXAM
 Course Outline and Timeframe
DATE Topic
02 May REDOX TITRATIONS
05 May  Redox Equilibria
09 May 1. Standard Electrode Potentials
2. Nernst Equation
 Redox Indicators, Titration Curve
12 May Instrumentation
16 May  Spectrophotometry

19 May FOURTH LONG EXAM

 Suggested Textbooks
• Skoog, D.A., West D.M., Holler, F.J.,
Crouch, S.R., Fundamental of Analytical
Chemistry, 9th edition, Brooks/Cole,
Singapore, 2013.

• Gary Christian, “Analytical Chemistry”, 6th

ed. John Wiley and Sons Inc., 2003.
 Class Policies
• UNIVERSITY RULES REGARDING ABSENCES WILL
APPLY.
• COME TO CLASS PREPARED.
• Casio Scientific Calculator is highly recommended.
• Removals will be given at a specified date and time. No
specials removals will be given before or beyond the
scheduled removal exam period.
• Grades will be computed based on the following criteria:
15% quizzes, problem sets, assignments
60% exams (4)
25% finals
 Grading Scale
• 1.00 93 - 100 • 3.00 60 - 63
• 1.25 89 - 92 • 4.00 55 - 59
• 1.50 85 - 89 • 5.00 0 - 55
• 1.75 80 - 84
• 2.00 76 - 79
• 2.25 72 - 75
• 2.50 68 - 71
• 2.75 64 - 67
 Groupings
• Chubby Bunny • Paris • Snow
– Dominic – France – John
– Angelica – Guen – Al
– Najela – Patricia – Danielle
• Legend of Karra – Ruther – Marianne
– Karra • Rowling • Chubby Bunny III
– Leondro – JK – Adrian
– Faye – Nadja – Lexine
• Tita’s of 28 – Dann – Jeanne
– Liza – Evan – Carmen
– Celine • Chubby Bunny II
– Chedy – Earl
– MM – Heather
– Dane
– Bea
 Groupings
• ma-ARAM • CHEM Tiu • Bieber
– Annyka – Roy – CJ
– Rezzy – Lucile – Andrea
– Airisse – Gian – Lois
– Marvelous • Pabebe Girls – Exl
• Chanels – Kyleen • The Guardian
– Shanel – Manuela – Azila
– Jona – Isabel – Von
– Martina – Isza – Zach
– Shielo • Karay-a – Ernah
• Hogwarts – Joshua • Forever
– Dame – Marvee – Mark
– Robert – Clide – Aira
– Camille – Kherson – Reyn
– Claudine
 Introduction to Chemical
Analysis
• Chemical analysis includes any aspect of
the chemical characterization of a sample
material.

• Analytical Chemistry?
– “Science of Chemical Measurements”
Qualitative analysis is what.
Quantitative analysis is how much.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Areas of Chemical Analysis and
Questions They Answer
• Quantitation:
– How much of substance X is in the sample?
• Detection:
– Does the sample contain substance X?
• Identification:
– What is the identity of the substance in the sample?
• Separation:
– How can the species of interest be separated from the
sample matrix for better quantitation and identification?
 What do Chemical Analyst Do?
• Analyst:
• Applies known measurement techniques to
well defined compositional or
characterization questions.
• Research Analytical Chemist
 What do Chemical Analyst Do?
• Senior Analyst:
• Develops new measurement methods on
existing principles to solve new analysis
problems.
 What do Chemical Analyst Do?
• Research Analytical Chemist:
• Creates and /or investigates novel
techniques or principles for chemical
measurements.
• Conducts fundamental studies of
chemical/physical phenomena underlying
chemical measurements.
 What is Analytical Science?
• Analytical Chemistry provides the methods and
tools needed for insight into our material
world…for answering four basic questions about a
material sample.
• What?
• Where?
• How much?
• What arrangement, structure or form?
An analysis involves several
steps and operations which
depend on:
• the particular problem
• your expertise
• the apparatus or
equipment available.
The analyst should be
involved in every step.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Fig. 1.1. Steps in an analysis

 Different methods provide a range of precision, sensitivity, selectivity,
and speed capabilities.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 The sample size dictates what measurement techniques can be used.

Sample constituents may be classified as:

• Major (>1%)
• Minor (0.1-1%)
• Trace (<0.1%)
• Ultratrace (<<ppm)
 Deer Kill
• Problem: Dead whitetail deer near pond in
the Land Between the Lakes State Park in
south central Kentucky.
• Chemist state veterinary diagnostic
laboratory helped find the cause
 Site Investigation
• Careful visual observation of a two acre
area around the site:
• Observation: grass around nearby power-
poles was wilted and discolored.
• Speculation: Herbicide used on grass.
• Ingredient: Arsenic in a variety of forms
– CH3AsO(OH)2 very soluble in water.
 Select Method
• Association of Official Analytical Chemists
(AOAC)
• Distillation of arsenic as arsine which is
then determined by colorimetric
measurements.
 Representative Sample
• Dissect both deer. Removed kidneys for
analysis.
• Laboratory Sample. Preparation
• Cut kidney into pieces and blend in a high
speed blender to homogenize the sample.
 Defining Replicate Samples
• Three 10-g samples of the homogenized
tissue were placed in porcelain curcibles
and dry ashed. Dry ashing serves to free the
analyte from organic material and convert
the arsenic present to As2O5. Samples of
the discolored grass were treated in a
similar manner.
 Dissolving the Samples
• The dry solid in each of the sample
crucibles was dissolved in dilute HCl,
which converted the As2O5 to soluble
H3AsO4.
 Eliminating Interferences
• Reactions to Eliminate Interferences:
• H3AsO4 + SnCl2 + 2HCl --> H3AsO3 + SnCl2 + H2O
• H3AsO3 + 3Zn + 6HCl --> AsH3(g) + 3ZnCl2 + 3H2O
• Bubble gas into collectors with silver
diethyldithiocarbamate to form a colored complex
compound shown below.
 Measuring the Amount of
Analyte
• Spectrophotometer: Highly colored
complex of arsenic was found to absorb
light at a wavelength of 535 nm.
Conc. Absorbance
ppm
0 0 Absorbance vs Concentration
5 0.16
10 0.28
15 0.41
20 0.595 0.8 y = 0.0282x + 0.005

Absorbance
25 0.7 2
0.6 R = 0.9961
deer 1 0.61
deer 2 0.43 0.4
0.2
0
0 5 10 15 20 25 30
Conc., ppm
 Calculating the Concentration
• ppm = (Absorbance -.005)/0.0282
• Deer 1: (0.61 - 0.005)/0.0282 = 22 ppm
• Deer 2: (0.43 -0.005)/0.0282 = 15 ppm
• Arsenic in the kidney tissue of animals is
toxic at levels above about 10 ppm.
• Grass Samples showed about 600 ppm
arsenic.
 Reliability of the Data
• The data from these experiments could be
analyzed using the statistical methods we
will describe in Section 3.