Analytical Chemistry II

Juan Luis Pérez Bernal

2016-2017
Analytical Chemistry II

1.- Introduction
Analytical Chemistry II

• What is Analytical Chemistry?

Starting Point • The Analytical Perspective
• Common Analytical Problems

1.- Introduction
Analytical Chemistry II

• What is Analytical Chemistry?

Starting Point • The Analytical Perspective
• Common Analytical Problems

Analytical chemistry is often described as the area

of chemistry responsible for characterizing the
composition of matter, both qualitatively and
quantitatively

1.- Introduction
Analytical Chemistry II

• What is Analytical Chemistry?

Starting Point • The Analytical Perspective
• Common Analytical Problems

Analytical chemistry is not performing a routine analysis on a

routine sample (chemical analysis), but improving
established analytical methods, extending existing analytical
methods to new types of samples, and developing new
analytical methods for solving problems

1.- Introduction
 CH3
that selectively precipitates Ni2+ and Pd2+, led to an improved analytical
method for the quantitative analysis of nickel.4 The resulting analysis, as
Analytical Chemistry II HO
N
N
OH
shown in Figure 1.2, requires fewer manipulations and less time after com-
pleting the sample’s dissolution. By the 1970s, flame atomic absorption
CH3 spectrometry replaced gravimetry as the standard method for analyzing
Chapter 1 Introduction to Analytical Chemistry 3
dimethylglyoxime nickel in ores,5 resulting in an even more rapid analysis. Today, the standard
analytical method utilizes an inductively coupled plasma optical emission
Original Sample Start spectrometer.
Solids 1:3 H2SO4/HNO3, 100°C for 8-10 hrs
dilute w/H2O, digest for 2-4 hr A more appropriate description of analytical chemistry is “the science
Solutions of inventing and applying the concepts, principles, and…strategies for
key PbSO4; Sand Cu2+, Fe3+, Co2+, Ni2+ 14 hours measuring the characteristics of chemical systems.”6 Analytical chemists
dilute; bubble H2S(g)
4 Kolthoff, I. M.; Sandell, E. B. Textbook of Quantitative Inorganic Analysis, 3rd Ed., The Mac-
millan Company: New York, 1952.
Fe3+, Co2+, Ni2+ CuS 16 hours 5 Van Loon, J. C. Analytical Atomic Absorption Spectroscopy, Academic Press: New York, 1980.
cool, add NH3 6 Murray, R. W. Anal. Chem. 1991, 63, 271A.
digest 50o-70o for 30 min

Approximate Elapsed Time

Fe(OH)3 Co2+, Ni2+ 17 hours
HCl slightly acidify w/HCl Original Sample

Approximate Elapsed Time

Start
Fe3+ heat, bubble H2S(g)

neutralize w/NH3 HNO3, HCl, heat

add Na2CO3, CH3COOH Waste CoS, NiS 20 hours
add aqua regia and heat
add HCl until strongly acidic
basic ferric acetate
bubble H2S(g) Residue Solution 14 hours

Co2+, Ni2+ CuS, PbS 20% NH4Cl

* heat
22 hours
10% tartaric acid
add Na2CO3 until alkaline make alkaline w/ 1:1 NH3
add NaOH
Solids
Co(OH)2, Ni(OH)2 Waste 23 hours Solutions Is
heat; H2(g) yes solid
key present?
mass A Co, Ni
26 hours
add HNO3, K2CO3, KNO3,
and CH3COOH and digest for 24 hours no make acidic w/ HCl
%Ni = mass A x 0.2031 x 100 1% alcoholic dmg
mass sample
Ni2+ K3Co(NO3)5 make alkaline w/ 1:1 NH3
51 hours
add dilute HCl

mass A Ni(dmg)2 18 hours

Co2+ Waste 54 hours
follow procedure
from point * above
Co %Ni = mass A - mass B x 100 58 hours
mass B mass sample
Figure 1.2 Gravimetric analysis for Ni in ores by precipitating Ni(dmg)2. The timeline shows that
Figure 1.1 Fresenius’ analytical scheme for the gravimetric analysis of Ni in ores. Note that
the mass of nickel is not determined directly. Instead, Co and Ni are isolated and weighed it takes approximately four hours to complete an analysis after digesting the sample, which is 10x
(mass A), and then Co is isolated and weighed (mass B). The timeline shows that after shorter than for the method in Figure 1.1. The factor of 0.2301 in the equation for %Ni accounts for
digesting a sample, it takes approximately 44 hours to complete an analysis. This scheme the difference in the formula weights for Ni and Ni(dmg)2; see Chapter 8 for further details.
is an example of a gravimetric analysis in which mass is the important measurement. See
Chapter 8 for more information about gravimetric procedures.

1.- Introduction
Analytical Chemistry II

Stages of an Analytical Method

Problem Requirements

Conception of analytical method (birth). 


Successful demonstration that the analytical

method works. 


Establishment of the analytical method’s

capabilities. 


Widespread acceptance of the analytical method. 


Continued development of the analytical method

leads to significant improvements. 


Analytical method can no longer compete with

newer analytical methods or requirements (death). 


1.- Introduction
Analytical Chemistry II

• What is Analytical Chemistry?

Starting Point • The Analytical Perspective
• Common Analytical Problems

Step 1. Identify and Define Problem Step 5. Propose Solution to Problem

What is the problem’s context? Is the answer sufficient?
What type of information is needed? Does answer suggest a new problem?

Step 2. Design Experimental Procedure Step 4. Analyze Experimental Data

Establish design criteria. Reduce and transform data.
Identify potential interferents. Complete statistical analysis.
Establish validation criteria. Verify results.
Select analytical method. Interpret results.
Establish sampling strategy.

Feedback
Loop

Step 3. Conduct Experiment & Gather Data

Calibrate instruments and equipment.
Standardize reagents.
Gather data.
Flow diagram show-
1.- Introduction
Analytical Chemistry II

• What is Analytical Chemistry?

Starting Point • The Analytical Perspective
• Common Analytical Problems

Qualitative Analysis
give information about species (atomic, molecular, functional group)
present in a sample

Quantitative Analysis
are used to obtain information about the relative amount of one or several
species

Characterization
Determinations of chemical structure, equilibrium constants, particle size, and
surface structure

1.- Introduction
Analytical Chemistry II

Vocabulary is part of the analytical chemistry toolbox

Analyte
The component of interest in the sample

Matrix
the remainder of the sample
Analysis
determination of the physical properties or chemical composition of samples

Determination
What is being stablished

Measurement
the process of associating numbers with physical/chemical quantities and
phenomena

Samples are analyzed to determine the presence/

concentration of analytes by adequate measurements
1.- Introduction
Analytical Chemistry II

Vocabulary is part of the analytical chemistry toolbox

Techniques
chemical or physical principle used to study an analyte

Methods
application of a technique for a specific analyte in a specific matrix

Procedures
set of written directions telling us how to apply a method to a particular
sample

Protocols
set of stringent guidelines specifying a procedure that must be followed
if an agency is to accept the results

1.- Introduction
 in Figure 3.2, the American Public Health Agency and the American Soci-
ety for IITesting Materials publish separate procedures for determining the
Analytical Chemistry
concentration of lead in water.

Vocabulary is part of the analytical chemistry toolbox

1 Taylor, J. K. Anal. Chem. 1983, 55, 600A–608A.
2 Fitch, A.; Wang, Y.; Mellican, S.; Macha, S. Anal. Chem. 1996, 68, 727A–731A.

Graphite Furnace Atomic Absorption Spectroscopy

Techniques
(GFAAS)

Methods Pb in Soil Pb in Water Pb in Blood

Figure 3.2 Chart sho

chical relationship amo
Procedures APHA ASTM methods using that tec
cedures and protocols
The abbreviations are
can Public Health Asso
Protocols American Society for
EPA als, EPA: Environme
Agency.

1.- Introduction
Analytical Chemistry II

Selection Criteria: Not a matter of taste

1.- Introduction
Analytical Chemistry II

Selection Criteria: Not a matter of taste

1.- Introduction
Analytical Chemistry II

Developing a Procedure

1. Compensating for Interferences

2. Performing Calibration
3. Sampling Procedure
4. Validation

1.- Introduction
Analytical Chemistry II

Developing a Procedure

1. Compensating for Interferences

2. Performing Calibration
3. Sampling Procedure
4. Validation

Stotal =SA +Sreag =kCA +Sreag

In a sample free of interferents, the total signa is the

sum of the signal due to the analyte and the signal
due to interferents in the reagents

1.- Introduction
Analytical Chemistry II

Developing a Procedure

1. Compensating for Interferences

2. Performing Calibration
3. Sampling Procedure
4. Validation

Determining the relation between the measured signal and the analyte
concentration, usually done measuring one or more standard samples,
each containing a known concentration of analyte

1.- Introduction
Analytical Chemistry II

Developing a Procedure

1. Compensating for Interferences

2. Performing Calibration
3. Sampling Procedure
4. Validation

Is impossible to obtain good results from a bad sample

1.- Introduction
Analytical Chemistry II

Developing a Procedure

1. Compensating for Interferences

2. Performing Calibration
3. Sampling Procedure
4. Validation

Is the practical demonstration of the method suitability for the

intended purpose.

1.- Introduction
Analytical Chemistry II

Basic concepts (that you should know)

Concentration Units
• Molarity and Formality
• Normality
• Molality
• Weight, Volume, and Weight-to-Volume Ratios
• Parts Per Million and Parts Per Billion
• Converting Between Concentration Units
• p-Functions
• Stoichiometric Calculations

1.- Introduction
Analytical Chemistry II

Basic concepts (that you should know)

Methods Properties
• Accuracy
• Precision
• Sensitivity
• Specificity and Selectivity
• Robustness and Ruggedness
• Scale of Operation
• Equipment, Time, and Cost

1.- Introduction
Analytical Chemistry II

Basic concepts (that you should know)

Measurements in Analytical Chemistry
• Units of Measurement
• Uncertainty in Measurements
• Characterizing Measurements and Results
• Measures of Central Tendency
• Measures of Spread
• Characterizing Experimental Errors
• Errors Affecting Accuracy
• Errors Affecting Precision
• Error and Uncertainty
• Propagation of Uncertainty

1.- Introduction
Analytical Chemistry II

Basic concepts (that you should know)

Statistical Analysis of Data
• SignificanceTesting
• Constructing a Significance Test
• One-Tailed and Two-Tailed Significance Tests
• Errors in Significance Testing
• Statistical Methods for Normal Distributions
• Comparing X to μ
• Comparing s2 to σ2
• Outliers
• Comparing Two Sample Variances
• Comparing Two Sample Means
• Detection Limits
1.- Introduction
Analytical Chemistry II

Instrumental Analysis. Signals and Noise

Further readings: Dealing with noise

1.- Introduction
Analytical Chemistry II

Instrumental Analysis

Treated Sample

Instrument

Signal

1.- Introduction
Analytical Chemistry II

Calibration
Operation that, under specified conditions, in a first step, establishes a relation
between the quantity values with measurement uncertainties provided by
measurement standards and corresponding indications with associated
measurement uncertainties (of the calibrated instrument or secondary standard)
and, in a second step, uses this information to establish a relation for
obtaining a measurement result from an indication
(BIPM JCGM 200:2008 International vocabulary of metrology )

1.- Introduction
Analytical Chemistry II

Calibration

Calibration is a comparison that

allows to establish the relationship
between the measured signal and
the concentration or mass of the
analyte being determined. In the
simplest form is performed
measuring the analytical signal of
samples with known concentration
(calibration standards)

1.- Introduction
Analytical Chemistry II

Calibration

1.- Introduction
Analytical Chemistry II
Calibration

• External Calibration
Sample Standard

• Internal Standard
Sample+Internal Standard Standard+Internal Standard

• Standard Addition Sample Sample+Standard

1.- Introduction
Analytical Chemistry II
Calibration

Further Reading:

• Linear Regression Of Straight Line Calibration Curves

• How a Linear Regression Works
• Uncertainty in the Regression Analysis
• Obtaining the Analyte’s Concentration from a Regression
Equation
• Blank Corrections

1.- Introduction